Method for producing a composite fiber material with particularly low fiber strain

Abstract

The present invention relates to a method for manufacturing a fiber composite material including a thermoplastic molding composition A and at least one layer of reinforcing fibers B. The thermoplastic molding composition A has at least one layer of reinforcing fibers B incorporated therein as a matrix, and is realized by the movement of the molding composition in relation to the reinforcing fibers B within a compressing stage in which the reinforcing fibers B remain stationary except for a one-dimensional forward movement during production. The thermoplastic molding composition A has at least one chemically reactive functional group, the surface of the reinforcing fibers B is treated with sizing, and the concentration of the functional groups of the chemically reactive functional groups of the molding composition A is at least 0.3 mol%, the thermoplastic molding composition A.

Description

Technical Field

[0001] The present invention relates to a method for producing a fiber composite material comprising a thermoplastic molding composition A and at least one ply of reinforcing fibers, wherein the thermoplastic molding composition A as a matrix is incorporated into at least one ply of reinforcing fibers B, wherein the incorporation occurs by relative movement of the molding composition with respect to the reinforcing fibers B within a compaction stage in which the reinforcing fibers B remain stationary away from a one-dimensional production feed port, the thermoplastic molding fibers have at least one chemically reactive functional group, the surface of the reinforcing fibers B is treated with a size, and the functional group concentration of the chemically reactive functional groups of the molding composition A is at least 0.3 mol%.

Background Art

[0002] Fiber composite materials, also called planar or two-dimensional organosheets, have a thermoplastic polymer matrix in which one or more fiber weaves and / or one or more fiber scrims are incorporated. The fibers used in the production of fiber composite materials are typically glass fibers, aramid fibers or carbon fibers, which are introduced as continuous fibers or long fibers into the thermoplastic polymer matrix. The fiber length of the long fibers is in the range of 1 to 50 mm here, and those with a fiber length exceeding 50 mm are called continuous fibers. Fiber composite materials based on continuous fibers have the highest rigidity and strength values compared to fiber composite materials with short fibers.

[0003] Fiber composite materials are usually based on a large number of reinforcing fibers incorporated in a polymer matrix. Fiber composite materials have applications in various fields. Fiber composite materials are preferentially used in the automotive and aerospace fields. In this application field, the reinforcing fibers are intended to prevent the polymer matrix from tearing or fragmenting in order to reduce the risk of accidents due to shredding of the parts. Many fiber composite materials can absorb relatively large forces under load before complete destruction. At the same time, fiber composite materials are noted for having high strength and stiffness compared to conventional non-reinforced fibers, and at the same time having low density and other advantageous properties, especially excellent aging resistance and corrosion resistance.

[0004] Another advantage of fiber composite materials is that the strength and stiffness of the fiber composite materials can be adapted to the direction and type of load. In this context, it is mainly the reinforcing fibers that are involved in the strength and stiffness of the fiber composite materials. In addition, the arrangement of the fibers in the fiber composite material determines its mechanical properties. Next, in contrast, the matrix mainly serves to introduce the forces to be absorbed into the individual reinforcing fibers and to hold the spatial arrangement of the reinforcing fibers in the desired direction. In order to ensure optimized force transmission, the reinforcing fibers should be as straight as possible, i.e., the distortion in the polymer matrix should be eliminated. Since both the reinforcing fibers and the matrix material are variable, a large number of possible combinations of reinforcing fibers and matrix materials are available to those skilled in the art in the manufacture of fiber composite materials.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Patent Document 8

Non-Patent Document

[0006]

Non-Patent Document 1

Non-Patent Document 2

Non-Patent Document 3

Non-Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0007] One of the technical problems is that in the case of complete failure, the fiber composite material may undergo brittle fracture, that is, complete failure can produce fragments that rapidly depart from the fracture site. As a result, when products of fiber composite material systems are exposed to high stress or sudden stress and break or fall apart, there can be a significant risk of accidents.

[0008] Therefore, it is desirable to provide a fiber composite material having a wide stress range in which complete failure is unlikely to occur. What is further desired is that the fiber composite material can be used to manufacture various elements having good optical properties and a smooth surface.

[0009] EP 1 923 420 B1 describes a fiber composite material having a matrix made of a thermoplastic plastic in which layers of reinforcing fibers are incorporated. A first group of reinforcing fibers is bonded to the matrix via a first fiber-matrix adhesion. A second group of reinforcing fibers is similarly bonded to the matrix via a second fiber-matrix adhesion. The second fiber-matrix adhesion is weaker than the first fiber-matrix adhesion. The difference in fiber-matrix adhesion is that the fracture characteristics are improved in the case of complete failure. The matrix materials provided in EP 1 923 420 B1 are thermosetting resins, such as polyesters, and thermoplastic polyamides and thermoplastic polypropylenes.

[0010] Therefore, EP 1 923 420 B1 focuses on the bonding of reinforcing fibers and a polymer matrix, called fiber-matrix adhesion, in the manufacture of fiber composite materials.

[0011] To optimize fiber-matrix adsorption and compensate for the "low chemical similarity" between the surface of the reinforcing fibers and the surrounding polymer matrix, the reinforcing fibers are subjected to regular pretreatment. For this purpose, what is called sizing has been found useful, and what are called adhesion promoters are preferably added thereto. The sizing or sizing / adhesion promoter is applied regularly, even during the manufacture of the fibers, for the improvement of their further processability, especially by weaving, laying, or sewing. If the sizing is not required for the further subsequent processing of the reinforcing fibers, it must first be removed by an additional process step, preferably burndown.

[0012] However, in addition to sizing, it can also be advantageous to apply an adhesion promoter to the reinforcing fibers treated in an additional process step. The sizing and / or adhesion promoter forms a layer on the surface of the reinforcing fibers that can significantly determine the interaction between the reinforcing fibers and the environment. Recently, a number of sizings and adhesion promoters have become available. Depending on the field of use, the matrix used, and the reinforcing fibers used, those skilled in the art can select a suitable sizing and a suitable adhesion promoter that are compatible with the matrix and the reinforcing material.

[0013] WO 2016 / 170131 A1 teaches the use of a fiber composite material W with a sandwich structure formed from a thermoplastic layer w containing, as component A, a) a composition A for thermoplastic molding as a matrix, b) a ply of reinforcing fibers B, and c) optionally an additive C, wherein the reinforcing fiber ply B is incorporated into the matrix of the thermoplastic molding composition A, and the thermoplastic molding composition A in the manufacture of the material layer w has at least one chemically reactive functional group that reacts in sequence with the chemical groups on the surface of the reinforcing fibers B; and B) a further thermoplastic layer T and / or a foam layer S, wherein the further layer T and / or S is permanently adhered to the material layer w to improve the mechanical stability of the molded article produced therefrom.

[0014] DE 10 2016 102081 A1 relates to a method for manufacturing a fiber-reinforced component, comprising the steps of laying fibers (16) on a mold (10) having a movable insert (12), injecting a matrix material (22) into the mold (10), and moving the insert (12) in the moving direction (B) during the injection of the matrix material (22). DE 10 2016 102081 assumes that the fibers (16) are introduced transversely to the moving direction (B) with respect to the insert (12) before the injection of the matrix material (22).

[0015] EP 3 286 258 B1 describes a method for manufacturing a fiber composite material comprising a thermoplastic molding composition A and at least 1 ply of reinforcing fibers B, wherein the at least 1 ply of reinforcing fibers B is incorporated into a matrix comprising the thermoplastic molding composition A, the thermoplastic molding composition A has at least one chemically reactive functional group, the surface of the reinforcing fibers B is treated with a silane size, and the concentration of the functional groups of the chemically reactive functional group is at least 0.3 mol%. EP 3 286 258 B1 does not take into account the distortion of the fibers occurring during the manufacture of the fiber composite material. This cannot be prevented by the method described in EP 3 286 258 B1.

[0016] WO 2016 170104 A1 relates to the use of a thermoplastic fiber composite material containing a) at least one thermoplastic molding composition A as a matrix, b) at least 1 layer of reinforcing fibers B, and optionally c) at least one additive C, wherein the at least 1 layer of reinforcing fibers B is incorporated into the matrix of the thermoplastic molding composition, and the thermoplastic molding composition A has at least one chemically reactive functional group which reacts with chemical groups on the surface of the component B during the manufacturing process of the fiber composite material for the manufacture of white goods, for example household appliances, enabling lightweight products.

[0017] Reinforcing fibers, especially glass fibers, are frequently sized in the prior art to protect the reinforcing fibers from each other when they rub against each other. For example, DE-A 2160778 discloses a size-treated glass fiber-based glass fiber-reinforced styrene polymer. It is said that mutual damage due to wear is prevented and cross-breaking (fragmentation) does not occur in the case of mutual mechanical interaction.

[0018] The sizing enables the cutting operation of the reinforcing fibers to be made easier in order to obtain equal stack lengths. In addition, the sizing can prevent the agglomeration of the reinforcing fibers. The dispersibility of the short fibers in water is improved by the sizing, and it becomes possible to obtain uniform fabrics by the wet laying method.

[0019] The sizing also contributes to establishing improved integrity between the glass fiber and the polymer matrix, and the glass fiber functions as a reinforcing fiber. This principle is especially adopted in the case of glass fiber-reinforced plastics (GFRP).

[0020] In addition to the adhesion promoters as already described, the sizing used for glass fibers preferably contains a number of other components, more preferably a film-forming agent, a lubricant or a wetting agent.

[0021] The film-forming agent protects the glass fibers or glass filaments from rubbing against each other and can further enhance the affinity with the synthetic resin in order to promote the strength and integrity of the fiber composite material based on glass fibers. The film-forming agents preferably used are starch derivatives, polymers and copolymers of vinyl acetate and acrylic esters, epoxy resin emulsions, polyurethane resins and polyamides. The film-forming agent is preferably used in a proportion of 0.5% to 12% by mass based on the total size.

[0022] Lubricants impart flexibility to glass fibers and glass fiber-based products, particularly weaves, and reduce the mutual friction of glass fibers. However, in many cases, the adhesion between glass fibers and synthetic resins is impaired by the use of lubricants. The lubricants used are preferably grease, oil or polyalkyleneamine. These lubricants are preferably used in an amount in the range of 0.01% to 1% by mass based on the total size.

[0023] Wetting agents lower the surface tension and improve the wetting of sized glass fibers or glass filaments. In the case of aqueous sizes, a polyfatty acid amide in an amount of 0.1% to 1.5% by mass based on the total size should preferably be referred to as a wetting agent.

[0024] The adhesion of the polymer on the surface of the reinforcing fiber is preferably improved by using an organofunctional silane as an adhesion promoter. Organofunctional silanes that are particularly preferably used as adhesion promoters are aminopropyltriethoxysilane, methacryloyloxypropyltrimethoxysilane, or glycidyloxypropyltrimethoxysilane. These silanes added to the aqueous size are usually hydrolyzed here to become silanols. Subsequently, these silanols can react with the reactive reinforcing fiber surface and, thus, preferably form an adhesion layer with a thickness of about 3 nm.

[0025] When using glass fibers as reinforcing fibers, low molecular weight functional agents of the matrix polymer can react with the silanol groups on the surface of the glass fibers, and these low molecular weight functional agents can further react (especially in epoxy resins), in which case, ensuring chemical bonding organofunctional silanization with the polymer matrix. However, such a process takes time and it takes approximately 30 minutes to over 1 hour until the polymer (especially the aforementioned epoxy resin) is completely cured.

[0026] Also, functional groups of silane sizes due to reaction with polymers are known. By functionalizing low molecular weight polycarbonate types, it is possible to efficiently impregnate glass fibers or glass fiber scrims with polycarbonate and bring about "grafting" by the reaction between the functional groups in the polycarbonate and the glass fiber surface. However, such a process has the drawback that it cannot generally be applied to polycarbonate (PC). Only low molecular weight, i.e., low viscosity, polycarbonate can be used in this method, which has extremely poor usability and low resistance to agents that induce stress cracking, especially polar solvents.

[0027] Therefore, an object of the present invention is to provide a process for producing a fiber composite material based on a reinforcing fiber weave, advancing from the prior art, such that the fiber composite material and the molded body produced therefrom are based on the same matrix polymer but have improved properties, particularly properties relating to its flexural strength, compared to the prior inventions described above.

[0028] The fiber composite material produced according to the present invention and the molded body produced therefrom are based on a strong composite material (quantifiable by flexural strength) of a reinforcing fiber weave and a matrix polymer that is easy to process, generally inert to conventional solvents, has good stress cracking resistance, and has minimal fiber distortion.

[0029] Fiber distortion in the context of the present invention means any deviation from the ideal weave form defined in DIN ISO 9354. In the ideal weave used as the woven fabric F according to the present invention, the fibers are ideally in a form stretched parallel, and usually continuous fibers are used. Low or no fiber distortion in the context of this invention means that in the two-dimensional projection of the glass fiber weave in the plane of the weave, the deviation of the center line of the fiber from the filament length is 15% or less.

[0030] The glass fiber weaves used as the fabric F according to the present invention cannot be manufactured in an ideal form by physical and technical means. These are the result of weaving continuous fibers, especially rovings. The weaving of glass fibers necessarily involves undulations of the fibers. The undulations have a specific effect of reducing the compressive strength parallel to the fibers. It is characteristic of the undulations that the fibers move alternately up and down with respect to the plane of the fabric F and thus are not in an ideally parallelly extended form. Considering the two-dimensional projection of the undulating fabric, the fibers are in an ideally extended form in the directions of the warp and weft of the fabric. The ideal parallelism is extremely important for optimal force transmission within the fibers. When a thermoplastic polymer matrix is incorporated into the fabric F according to the present invention, the ideal parallelism of the fibers can be maintained. The deviation from the ideal parallelism is called fiber distortion and is measured by visual monitoring according to DIN EN ISO 13015, for example, with the aid of suitable instruments or a camera-based system. The position of the fiber center line is determined in the main direction with respect to the filament length. The filament defines a bundle of fibers called a roving, yarn, fiber bundle, or filament bundle.

Brief Description of the Drawings

[0031]

Figure 1

Figure 2

Figure 3

DETAILED DESCRIPTION OF THE INVENTION

[0032] The present invention is a method for manufacturing a fiber composite material comprising a thermoplastic molding composition A as a polymer matrix M and reinforcing fibers B, i) providing at least one woven fabric F in the form of a fabric made of reinforcing fibers B treated with a silane size; ii) providing a thermoplastic molding composition A that functions as matrix M, the thermoplastic molding composition having at least 0.3 mol% of chemically reactive functional groups based on component A in the form of functional monomers; iii) optionally, incorporating at least one additive C into the thermoplastic molding composition A; iv) introducing at least one woven fabric F by incorporating the thermoplastic molding composition A that functions as matrix M into the reinforcing fiber B by relative movement while keeping the thermoplastic molding composition A away from the continuous or discontinuous one-dimensional production supply port of the reinforcing fiber B and compacting the composite material composed of at least one woven fabric F and matrix M; v) reacting the chemically reactive functional groups of the thermoplastic molding composition A with the polar groups on the surface of the reinforcing fiber B treated with a silane size; vi) cooling the fiber composite material, and optionally further process steps, Here, the chemically reactive functional group of the thermoplastic molding composition A is based on a component selected from the group consisting of maleic anhydride, N-phenylmaleimide, and glycidyl (meth)acrylate. Steps iv) to vi) are carried out at a temperature of at least 150°C, and steps v) to vi) are carried out by pressurization under increased pressure, providing a method for producing a fiber composite material.

[0033] Surprisingly, the process of the present invention produces a fiber composite material that is particularly free of strain.

[0034] One feature of the process of the present invention is the introduction of the matrix M into at least one woven fabric F. The matrix M flows into the gaps between the reinforcing fibers B treated with a silane size. Excess size is removed from the rovings, warp and weft yarns, fiber bundles, or filament bundles of the reinforcing fibers B. The fiber composite material produced according to the present invention is characterized in that all individual fibers are completely covered with the matrix M. This results in both optimized fiber-matrix adhesion and improved fixation of the reinforcing fibers in their spatial arrangement. As a result, the fiber composite material produced according to the present invention has a lower strain compared to the fiber composite material produced according to the prior art.

[0035] The matrix M is preferably introduced into at least one woven fabric F in process step iv) via the melting of the thermoplastic molding composition A and the contact with at least one woven fabric F consisting of the reinforcing fibers B as provided in process step i).

[0036] The melting of the thermoplastic molding composition A and the contact of this melt with the reinforcing fibers B can be effected by any method suitable for the purpose. In such impregnation, the matrix M based on the thermoplastic molding composition A is converted into a free-flowing state, and the reinforcing fibers B are wetted to form an interfacial layer.

[0037] Engineering steps iii), iv), v) and vi) are also carried out simultaneously. According to the present invention, at least one thermoplastic molding composition A contains at least 0.3% of chemically reactive functional groups in the form of functional monomers based on component A. Preferably, at least one thermoplastic molding composition A contains at least one copolymer A-1 containing a monomer A-I that covalently bonds to the polar group or functional group B-I of the reinforcing fiber B. Immediately after the contact between at least one thermoplastic molding composition A and the reinforcing fiber B, when steps iv), v) and vi) are carried out simultaneously, a chemical reaction occurs in which the monomer A-I forms a covalent bond with the surface of the reinforcing fiber B (generally through bonding to the functional group B-I). This is preferably an esterification, in particular the esterification of the silanol groups in the reinforcing fiber with maleic anhydride monomers. Alternatively, the formation of the covalent bond can also be initiated at different stages, in particular by an increase in temperature, a free radical initiator, or a photoinitiation method, or a combination thereof. This can be carried out at any suitable temperature.

[0038] Steps iv) to vi) are carried out at a temperature in the range of at least 150 °C, preferably at least 175 °C, more preferably at least 200 °C, particularly preferably 230 °C to 300 °C. Here, preferably, thermal decomposition should occur as little as possible, and it should be ensured that the reactants used and the components used do not undergo thermal destruction.

[0039] In a preferred embodiment, in the execution of steps iv) to vi), the residence time at a temperature of 200 °C or higher is 10 minutes or less, preferably 5 minutes or less, more preferably 2 minutes or less, particularly preferably 1 minute or less. The engineering steps iv) to vi) and the heat treatment carried out therein are often sufficient in 1 to 60 seconds.

[0040] The processes, in particular steps iv) to vi), can in principle be carried out at any pressure. Steps v) and vi) are preferably carried out at an increasing pressure which can improve the properties of the produced fibre composite material. In particular, surprisingly, it was possible to improve the surface appearance in this way. Experiments in the context of the present invention have shown that, in particular when step vi) is not carried out at an increasing pressure, the surface roughness and the proportion of air inclusions in the fibre composite material increase.

[0041] In a preferred embodiment, therefore, steps iv) to vi) are carried out at a pressure in the range from 5 to 100 bar and a pressing time in the range from 1 to 60 seconds, more preferably at a pressure in the range from 10 to 30 bar and a pressing time in the range from 2 to 40 seconds.

[0042] The polypropylene providing at least one chemically reactive functional group (A-I) is preferably used as the thermoplastic moulding composition A in the matrix M. The use of an amorphous thermoplastic, in particular a styrene copolymer or a polycarbonate, can significantly improve the surface quality of the produced fibre composite material, since the shrinkage rate of the amorphous thermoplastic is lower compared to that of the semi-crystalline thermoplastic, and thus the surface topology is improved by the fibre-rich regions (intersections of the woven fabric) and the fibre-poor regions. When step vi) is carried out at an increasing pressure according to the present invention, surprisingly, an equivalent surface quality can also be achieved with a semi-crystalline plastic.

[0043] During the consolidation in steps v) and in particular step vi), the relative movement of the thermoplastic moulding composition A with respect to the reinforcing fibres B replaces the air present between the reinforcing fibres, thereby reducing the air encapsulated in the fibre composite material with respect to the produced composition and establishing a good bond between the thermoplastic moulding composition A and the reinforcing fibres B. A preferred object of the present invention is to obtain a (very substantially) pore-free composite material after impregnation and consolidation. What "pore-free" means in the context of the present invention is the case where the fibre composite material, detectable by optical testing methods, X-ray imaging, density measurement, ashing, in particular according to ASTM D2734-09, contains less than 5% by volume of air or pores.

[0044] Alternatively, the process steps may be carried out in separate sequences. Thus, for example, it is possible to prepare a ply of reinforcing fiber B with separately prepared reinforcing fiber B, where impregnation of the matrix M of the thermoplastic molding composition A and the reinforcing fiber B takes place. Thereafter, there may be an impregnated ply with reinforcing fiber B having different fiber-matrix adhesions, which is compacted in a further step and can give a composite material as a fiber composite material. Before the ply of reinforcing fiber B is laminated with the matrix of the thermoplastic molding composition A, it is possible for at least a part of the reinforcing fibers to be pretreated, in the process affecting subsequent fiber-matrix adhesion. The pretreatment may preferably include a coating process, an etching process, a heat treatment process or a mechanical surface treatment process. However, in particular, it is also possible to partially remove an already applied adhesion promoter by heating a part of the reinforcing fiber B.

[0045] The reinforcing fiber plies may be completely bonded to each other during the production of the present invention, which is called lamination. Such a bonded composite material mat has improved strength and rigidity in the direction of the reinforcing fibers and may be further processed particularly advantageously.

[0046] Particularly preferred embodiments and process reactants

[0047] Process step i) At least one fabric F provided by the method of step i) is preferably based on a fabric consisting of continuous fibers, including fibers which are products of the twist of individual fibers. According to "http: / / de.wikipedia.org / wiki / Faser-Kunststoff-Verbund", in the case of reinforcing fibers, in particular glass fibers, chopped fibers, also called short fibers, having a length in the range of 0.1 to 1 mm, are distinguished from long fibers having a length in the range of 1 to 50 mm and continuous fibers having a length L > 50 mm.

[0048] Accordingly, in accordance with the present invention, the reinforcing fibers F being processed into a fabric are preferably not short fibers (chopped fibers), and the composite material manufactured in accordance with the present invention is therefore preferably not a short reinforced fiber composite material. Preferably in accordance with the present invention, at least 50% of the reinforcing fibers have a length of at least 5 mm, more preferably at least 10 mm or more than 100 mm, and the length of the reinforcing fibers B depends on the size of the molded article T produced from the fiber composite material F.

[0049] The fabric used in accordance with the present invention in process step i) is preferably based on continuous fibers in the form of rovings, yarns, fiber bundles, or filament bundles before processing to give the fabric. Accordingly, the use of roving fabrics, yarn fabrics, or filament fabrics is particularly preferred.

[0050] It is preferred to use the fabric used as the fabric F in process step i). Accordingly, in a preferred embodiment, the subject matter of the present invention also encompasses a method for manufacturing a fiber composite material having a layer structure and at least two layers of weaves in the fabric F.

[0051] The layers may preferably be constructed the same or differently. Accordingly, in a preferred embodiment, the present invention relates to a method for manufacturing a fiber composite material which is a layer structure and includes more than two layers, preferably more than three layers of weave layers. Preferably, all the layers may be constructed the same, and some of the layers may be constructed differently, where "differently" means the type of weave, the pattern of the weave, and the material of the weave. The pattern of the weave is determined by the way the warp and weft threads alternate and the distance they run over or under each other.

[0052] The fiber composite material produced by the method of the present invention is penetrated by at least one fabric, preferably mostly penetrated. Here, what "mostly penetrated" means is that at least one fabric F penetrates more than 50% of the length of the fiber composite material produced according to the present invention, preferably at least 70%, particularly at least 90%. Here, the length of the fiber composite material is the maximum range in any of the three spatial directions. More preferably, at least one fabric F penetrates more than 50% of the area of the fiber composite material produced by the process of the present invention, even more preferably at least 70%, particularly preferably more than at least 90%. Here, the area is the area of the maximum range in two of the three spatial directions.

[0053] The method of the present invention preferably produces a planar or two-dimensional fiber composite material. In the case of a preferred planar or two-dimensional fiber composite material according to the present invention, the individual filaments of the fabric F or the filament centerlines of the continuous fibers used in the fabric pass within a window having a height of within 15%, preferably within 10%, particularly within 5% along the length of the two-dimensional fiber composite material.

[0054] The flatness of the fiber composite material produced according to the present invention is determined through its thickness. The fiber composite material is flat for the purposes of the present invention if the thickness does not differ by more than 10% from the average sheet thickness at any point on a 300 mm × 300 mm sheet of the fiber composite material, where the sheet thickness is measured at at least 4 points more than 100 mm apart from each other using a thickness gauge with a flat measuring head. In the case of smaller plate dimensions, the fiber composite material is considered flat for the purposes of the present invention if it is measured using the same test method, measuring the limit values described using the ratio of the smaller plate dimension to the 300 mm × 300 mm plate dimension.

[0055] Preferably, at least one fabric F provided in process step i) is based on at least one fabric made of reinforcing fibers B treated with a silane size. More preferably, the reinforcing fibers B used are glass fibers having silane groups on the surface as chemically reactive functional groups.

[0056] Most preferably, the invention provides, in process step i), at least one fabric F based on at least one fabric made of glass fibers having silanol groups on the surface as chemically reactive functional groups.

[0057] Preferably, based on 100 parts by mass of the fiber composite material produced by the process of the present invention, 5 to 80 parts by mass, more preferably 10 to 75 parts by mass, still more preferably 20 to 70 parts by mass, and particularly 25 to 68 parts by mass of reinforcing fibers B are used.

[0058] The reinforcing fibers B are used in the form of the fabric F. The reinforcing fibers B can be any fibers having a surface with a functional group B-I that can enter into a covalent bond with the monomer A-I of the component A.

[0059] As is well known, the physicochemical properties of reinforcing fiber-based fiber composite materials, particularly glass fiber-based fiber composite materials, and resins are affected by the affinity, adhesion, and consequently shear strength at the phase boundary of the reinforcing fibers or glass fibers and the polymer matrix. The function of the size is both to establish an appropriate bond between the reinforcing fibers, particularly glass fibers, and the surrounding resin and to ensure the productivity and processability of rovings or prepregs.

[0060] Reinforcing fibers, particularly glass fibers, are sensitive to creases and refining regardless of their chemical composition. Therefore, even during the fiber drawing process, it is necessary to take preventive measures by applying a size to protect the reinforcing fibers, which are glass fibers, from the polishing effect of glass on glass and to protect it from the risk of mechanical damage.

[0061] The size composition affects not only the integrity, hardness, degree of rigidity, or surface characteristics of products made of reinforcing fibers or glass fibers, especially fabrics, but also technical processes such as fiber drawing processes (fiber tension), winding processes (package build), and drying processes (drying temperature, drying time), and in particular, further affects processability.

[0062] The size for reinforcing fibers, especially glass fibers, mainly consists of one or more film-forming agents, lubricants, wetting agents, and one or more adhesion promoters (coupling agents). The film-forming agent imparts the integrity required for the entire filament, especially for rovings, protects the glass filaments from mutual friction, and can contribute to the affinity with synthetic resins and, consequently, the strength of the fiber composite material manufactured according to the present invention. By dissolving the film-forming layer in the matrix through possible chemical reactions with the polymer matrix, it is possible to increase the adhesive force and shear strength at the phase boundary between the reinforcing fiber or glass fiber and the synthetic resin, and as a result, it is possible to increase the strength and toughness of the composite material.

[0063] The film-forming agent used is preferably an amount in the range of 0.1 to 12.0 parts by mass based on 100 parts by mass of the total size, which is a starch derivative, a polymer and copolymer of vinyl acetate and acrylic ester, an epoxy resin emulsion, an epoxy polyester resin (see EP-A-0 027 942), a polyurethane resin, a polyolefin resin, or a mixed emulsion of polyvinyl acetate and polystyrene.

[0064] The lubricant in the size imparts the necessary flexibility to the product, especially textile glass rovings treated with the lubricant, and reduces the mutual friction of the reinforcing fibers, preferably glass fibers, during both its production and further processing, especially weaving. However, many lubricants adhere to the reinforcing fibers, especially glass fibers, and the resin. The lubricant used is an amount in the range of 0.01 to 1.0 parts by mass based on 100 parts by mass of the total size, especially grease, oil, wax, or polyalkyleneamine.

[0065] As a sizing component, the wetting agent reduces the surface tension of water and improves the wetting of the reinforcing fibers, preferably glass fibers, and the sizing. Preferably, the wetting agent used as an aqueous sizing in the form of an emulsion is present in an amount in the range of 0.1 to 1.5 parts by mass, particularly poly(fatty acid amide), based on 100 parts by mass of the total sizing.

[0066] Most polymers used as matrices have low affinity, if any, for glass fibers and, by extension, glass fibers preferentially used as reinforcing fibers according to the present invention. The adhesion promoter forms a crosslink between the glass fiber and the polymer, enabling complete transfer of force in the fiber composite material or composite. The adhesion promoter increases the adhesion of the polymer at the glass surface. The adhesion promoters preferentially used according to the present invention are organofunctional silanes, particularly γ-aminopropyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane. In the case of glass fibers, these adhesion promoters are preferably present in an amount in the range of 0. to 1.0 parts by mass based on 100 parts by mass of the total sizing used.

[0067] Before the silane used as an adhesion promoter is added to the aqueous sizing, it is preferably hydrolyzed to silanol. There is a limit to the stability of such a hydrolysis solution, which tends to condense. The adhesion promoter-containing layer, called polymer sizing, may further contain other additives, preferably primers, rust inhibitors, or emulsifiers, intended to achieve specific effects.

[0068] The auxiliary components used in terms of size are a well-known fact and are described, for example, in K. L. Lowenstein - The Manufacturing Technology of Continuous Glass Fibres, Elsevier Scientific Publishing Corp. Amsterdam - Oxford - New York, 1983.

[0069] According to the present invention, the surface of the reinforcing fiber B used, particularly the glass fiber, is treated with a silane size. This size functions as a lubricant, particularly in the weaving of the reinforcing fiber B or the glass fiber, and can optionally be chemically removed after weaving. The reinforcing fiber B used is more preferably a glass fiber having a hydroxy group in the form of a silanol group as a chemically reactive functional group B-I on its surface.

[0070] In one embodiment, the surface of the reinforcing fiber B or the glass fiber may have further functional groups B-II, particularly hydroxy groups, ester groups, or amino groups.

[0071] The reinforcing fiber B or the glass fiber may be incorporated into the fiber composite material as a fabric F in any direction and arrangement. And they are not statistically uniformly distributed in the fiber composite material manufactured according to the present invention, but are distributed in the form of a fabric, that is, a plane with a larger share and a plane with a smaller share, that is, in the form of more or less separate plies. The starting material is preferably a laminated or thin-layered structure of the fiber composite material manufactured according to the present invention.

[0072] In the production of reinforcing fibers B, especially glass fibers, the adhesion promoter may be applied as part of the size. However, it is also possible to additionally provide a thermal desorption or other desorption operation that destroys or removes the already applied size. Thereafter, it is possible to coat the reinforcing fibers or glass fibers with an adhesion promoter-containing finish that is compatible with the respective matrix and the desired fiber-matrix adhesion. Alternatively, it is also possible to use polymer layers. In one embodiment, it is possible to use an adhesion promoter compatible with a matrix polymer containing a crosslinkable polythiourethane and / or a polyester polyurethane polymer that acts as a film former, together with an aminosilane adhesion promoter.

[0073] Preferential are finished reinforcing fibers or glass fibers, especially in the form of a fabric, with a modified silane size such as FK800 finish; R&G glass filament fabric plane 25 g / m from R&G Faserverbundwerkstoffe GmbH in Waldbrunn, Germany 71111 2 See FK800 glass fabric R&G twill 1901005. Such weaves are very flexible and hardly fray when cut.

[0074] According to the present invention, the fabric F of reinforcing fibers takes the form of a fabric. The two-dimensional laminate obtainable by the method of the present invention from a fabric of reinforcing fibers B preferably contains a composite material formed from two-dimensional reinforcing fiber plies B and a ply of a thermoplastic molding composition A that functions as a matrix and wets and binds these two-dimensional reinforcing fiber plies B. In a preferred embodiment, the matrix is successively incorporated in layers into the reinforcing fiber / fiber layer ply B, and thus forms a fiber composite material produced according to the present invention.

[0075] The weaves used in accordance with the invention as fabric are formed by continuous fiber weaves, in particular roving weaves. The weaves of (continuous) glass fibers necessarily involve undulations of the (reinforcing) fibers. Undulations have a specific effect of reducing the compressive strength parallel to the fibers. With respect to the plane of the fabric, it is characteristic of the undulations that the (reinforcing) fibers move alternately up and down and thus are not in an ideal parallel and extended form. Considering the two-dimensional projection of the undulated fabric, the fibers are in an ideal and extended form in the direction of the warp and weft of the weaves. Ideal parallelism is extremely important for the optimal transmission of forces in the fibers. When the thermoplastic molding composition A functioning as matrix M is incorporated into the fabric F, it is possible to maintain the ideal parallelism of the (reinforcing) fibers. The difference from the ideal parallelism is called fiber strain and is measured in accordance with DIN EN ISO 13015 with the assistance of visual monitoring, in particular, an appropriate instrument or camera-based system. The position of the fiber center line is determined by the main direction with respect to the filament length. The filament means a bundle of fibers, also called roving, yarn, fiber bundle, or filament bundle.

[0076] In a preferred embodiment, in the fiber composite material manufactured in accordance with the invention, the fiber center line changes within 15%, preferably within 10%, more preferably within 5% from an ideal straight line, i.e., a non-distorted form, based on the fiber composite material or the molded article T manufactured therefrom.

[0077] Preferably, the process of the invention results in a fiber composite material having a volume fraction of the reinforcing fibers B in the form of the fabric F defined in accordance with DIN 1310 in the range of 25% to 65%, more preferably 30% to 55%.

[0078] Preferably, the process of the invention results in a fiber composite material having a volume ratio of 5% determined in accordance with ASTM D2734-09, where the remaining volume is preferably completely constituted by the molding composition A.

[0079] Engineering stage ii) Engineering stage ii) relates to providing a thermoplastic molding composition A in the form of a matrix M having chemically reactive functional groups in the form of at least 0.3 mol% of a functional monomer, based on component A.

[0080] Having chemically reactive functional groups, or being modified by chemically reactive functional groups, means comprising a (co)polymer (as a building block) that provides reactive chemical groups in the (co)polymer.

[0081] These chemically reactive functional groups react with the chemical groups on the surface of the reinforcing fiber B during the manufacturing process of the fiber composite material produced according to the present invention. It is preferable to use the thermoplastic molding composition A based on a (co)polymer that functions as a matrix. Such a (co)polymer preferably contains at least one functional monomer A-I, the functionality of which reacts with the chemical groups on the surface of the reinforcing fiber B during the manufacturing process of the fiber composite material. The (co)polymer containing monomer A-I is also referred to as polymer component (A-a) in the context of this application.

[0082] Optionally, the thermoplastic molding composition A may further contain one or more (co)polymers that optionally do not have such chemically reactive functional groups either (and thus do not have functional monomer A-I), and thus do not react with the chemical groups on the surface of the reinforcing fiber B during the manufacturing process of the fiber composite material. Such a (co)polymer is also referred to as polymer component (A-b) in the context of this application.

[0083] Preferably, the thermoplastic molding composition A as the matrix M is based on an amorphous or semi-crystalline polymer. More preferably, the thermoplastic molding composition A used as the matrix M is used in the form of a semi-crystalline polymer. A solid containing both crystalline and amorphous regions (domains) is called a semi-crystal. When the melt of the polymer is cooled, the polymer chains move to a very small extent and start to arrange regularly or crystallize. However, since they are entangled, this process can only occur within the domains and not throughout the melt. In the remaining part of the melt, the chains solidify in a disordered (amorphous) state. The slower the cooling of the melt, the greater the degree of crystallization of the polymer. Polymers with short side chains are more likely to crystallize than those with long side chains. In contrast, crosslinked or branched polymers are less likely to crystallize. According to DE 10 2011 084 519 A1, semi-crystalline polyamides have a melting enthalpy of more than 25 J / g as measured by the DSC method according to ISO 11357 in the second heating run, and this definition can also be applied to other semi-crystalline polymers.

[0084] In process step ii), the matrix M is used in an amount based on the matrix M such that the fiber composite material produced according to the invention is preferably 10 to 95 parts by mass, more preferably 20 to 50 parts by mass, even more preferably 23 to 40 parts by mass, and particularly 27 to 38 parts by mass, based on 100 parts by mass of the fiber composite material.

[0085] In process step ii), the thermoplastic molding composition A provided as the matrix M is preferably based on at least one polymer from the group of polyolefins, polyamides, thermoplastic elastomers, polycarbonates, polybutadiene terephthalate, polylactic acid, polyphenylene sulfide, and styrene copolymers.

[0086] A preferred styrene copolymer is a styrene-acrylonitrile copolymer (SAN), an α-methylstyrene-acrylonitrile copolymer (AMSAN), an impact-modified styrene-acrylonitrile copolymer, an acrylonitrile-butadiene-styrene copolymer (ABS), a styrene-methyl methacrylate copolymer (SMMA), a methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), or an acrylate-styrene-acrylonitrile copolymer (ASA), wherein the styrene polymer is modified with monomer (A-I).

[0087] When the proportion of the semi-crystalline mixture component in Component A is less than 50% by mass, blends of the aforementioned copolymers with polycarbonate or blends with semi-crystalline polymers, especially polyamides, are also suitable.

[0088] Preferably, according to the present invention, at least one of the polymer components in the thermoplastic molding composition A is modified with monomer A-I (polymer component (A-a)). Any further polymer component that is optionally not modified with monomer A-I, preferably a styrene copolymer, especially those mentioned above, may optionally further be present in the thermoplastic molding composition A (polymer component (A-b)).

[0089] It is very particularly preferred to use an SAN-(M-I) copolymer (with modification by monomer A-I) as a component of the thermoplastic molding composition A (optionally as the only polymeric component).

[0090] According to the present invention, at least one of the (co)polymer components of the thermoplastic molding composition A is a (co)polymer having at least one chemically reactive functional group (polymer component (A-a)). Thus, each copolymer component described in the preceding paragraphs with respect to process step ii) may also have reactive functional groups that can react with the surface of the reinforcing fiber B during the production of the fiber composite material, in addition to the monomers explicitly described. Therefore, any of the aforementioned (co)polymers can constitute the polymer component (A-a).

[0091] Accordingly, the polymer component described above may generally also include at least one monomer A-I that imparts chemically reactive functional groups (and thus reacts with the reinforcing fiber B) when used as the polymer component (A-a). In this case, these are preferably also referred to as polystyrene (A-I) copolymers, styrene acrylonitrile (A-I) copolymers, α-methylstyrene-acrylonitrile (A-I) copolymers, impact-modified acrylonitrile-styrene (A-I) copolymers, acrylonitrile-butadiene-styrene (A-I) copolymers (ABS-(A-I)), and acrylonitrile-styrene-acrylic ester (A-I) copolymers (ASA-(A-I)). Blends of the polymers described above with polycarbonate or polyamide are also possible.

[0092] The polymer component described above may optionally further include a second monomer (or third monomer) having chemically reactive functional groups when used as the polymer component (A-a).

[0093] Accordingly, in particular, when maleic anhydride (MA) is used as monomer A-I with respect to the polymer component described above (when used as the polymer component (A-a)), it can also be referred to as a polystyrene-maleic anhydride copolymer, a styrene-acrylonitrile-maleic anhydride copolymer, an α-methylstyrene-acrylonitrile-maleic anhydride copolymer, an impact-modified acrylonitrile-styrene-maleic anhydride copolymer, an acrylonitrile-butadiene-styrene-maleic anhydride copolymer (ABS-MA), or an acrylonitrile-styrene-acrylic ester-maleic anhydride copolymer (ASA-MA). Blends of the polymers described above with polycarbonate or polyamide are also possible. Other monomers A-I apply similarly.

[0094] In one embodiment, in step ii), in addition to one or more polymer components (A-a), one or more other (co)polymers having no such functional groups (as polymer component (A-b)) can be used. Here too, preferably, polystyrene, styrene-acrylonitrile copolymer, α-methylstyrene-acrylonitrile copolymer, impact-modified acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer (ABS), and acrylonitrile-styrene-acrylic acid ester copolymer, which are the (co)polymers described above, and blends of the (co)polymers described above with polycarbonate or polyamide can be used, but in that case they have no functional groups (therefore, they do not have reactive monomer A-I).

[0095] The thermoplastic molding composition A used is more preferably a polyolefin, even more preferably polypropylene (PP) or high-pressure polyethylene (HPPE). The thermoplastic molding composition A in this case preferably contains more than 50% polypropylene or copolymer (A-I). In one embodiment, such a thermoplastic molding composition A contains at least 90% of copolymer A-1. The thermoplastic molding composition A in this case may consist only of copolymer A-1.

[0096] Preferably, according to the present invention, at least one component of the thermoplastic molding composition A contains a (co)polymer having at least one chemically reactive functional group described herein and is called polymer component (A-a). More preferably, at least one of the aforementioned polymer components is polypropylene, and / or at least one copolymer A-1 (styrene copolymer, particularly SAN, SMMA, ABS, and ASA) contains at least one monomer A-I.

[0097] Particularly preferably, when maleic anhydride (MA) is used as monomer A-I, the polypropylene contains a polypropylene-maleic anhydride copolymer, and copolymer A-1 is particularly preferably a styrene-acrylonitrile-maleic anhydride copolymer (SAN-MA), a styrene-methyl methacrylate-maleic anhydride copolymer (SMMA-MA), an acrylonitrile-butadiene-styrene-maleic anhydride copolymer (ABS-MA), or an acrylate-styrene-acrylonitrile-maleic anhydride copolymer (ASA-MA).

[0098] In addition to at least one polymer component (A-a), it is optionally possible to use any one or more other (co)polymers that do not have functional groups such as polymer component (A-b). This may preferably be polystyrene, SAN, SMMA, ABS, and / or ASA (none of which contain any optional monomer A-I).

[0099] In an alternative embodiment, the thermoplastic molding composition A is preferably an amorphous molding composition, where the amorphous state of the thermoplastic molding composition (thermoplastic) means that the polymer has no regular arrangement or orientation, i.e., a completely random arrangement with no uniform separation.

[0100] Preferably, in such a case, the entire thermoplastic molding composition A has amorphous thermoplastic properties and is thus soluble and (mostly) amorphous. As a result, the shrinkage of the thermoplastic molding composition A, and thus also the shrinkage of the entire fiber composite material, is relatively low. In the molded article T produced from the fiber composite material manufactured according to the present invention, a particularly smooth surface can be achieved.

[0101] As a preferred amorphous molding composition, component A contains less than 50 parts by mass, more preferably less than 40 parts by mass, of a semi-crystalline inclusion based on 100 parts by mass of component A. Semi-crystalline thermoplastic resins form chemically regular regions and geometrical regions, that is, there are regions where crystals are formed. Crystallites are parallel bundles of molecular cross-sections or folds of molecular chains. Individual chain-like molecular chains may partially pass through crystalline or amorphous regions. They may sometimes belong to multiple crystallites simultaneously.

[0102] The thermoplastic molding composition A may be a blend of an amorphous thermoplastic polymer and a semi-crystalline polymer.

[0103] The thermoplastic molding composition A is preferably a blend of a styrene copolymer A-I, particularly SAN, with one or more polycarbonates and / or one or more semi-crystalline polymers, particularly a blend with a polyamide, where the proportion of the semi-crystalline mixed component in component A is less than 50 parts by mass, preferably less than 40 parts by mass, based on 100 parts by mass of the thermoplastic molding composition A.

[0104] Preferably, according to the present invention, at least one thermoplastic molding composition A contains at least one copolymer A-1 including a monomer A-I that enters into a covalent bond with a functional group B-I of the incorporated reinforcing fiber B. The proportion of the monomer A-I in the thermoplastic molding composition A may be selected in various ways. The higher the proportion of the monomer A-I and the functional group (B-I), the stronger the bond between the thermoplastic molding composition A and the reinforcing fiber B. The monomer A-I may still exist as a monomer in the copolymer A-1 or may be incorporated into the copolymer A-1. The monomer A-I is preferably incorporated into the copolymer A-1.

[0105] In a preferred embodiment, the copolymer A is formed with a proportion of at least 0.3 parts by mass, preferably 0.5 parts by mass, even more preferably 0.5 - 5 parts by mass, particularly preferably at least 1 part by mass, of the monomer A-I based on 100 parts by mass of the copolymer A.

[0106] The concentration of the functional group (chemically reactive functional group) is preferably at least 0.3 mol%, more preferably at least 0.5 mol%, still more preferably 1 mol%, and particularly preferably 1 to 5 mol%, based on 100 mol% of the monomer used in the production of the thermoplastic molding composition A.

[0107] In a preferred embodiment, the functional group of the thermoplastic molding composition A is selected from the group consisting of anhydride, ester, carboxy, amide, imide, acrylate, and glycidyl groups. The monomer A-I capable of entering into a covalent bond with the functional group B-I of the reinforcing fiber B includes all monomers having such properties. Here, the preferred monomer A-I is one capable of entering into a covalent bond by reaction with a hydroxy or amino group.

[0108] The monomer A-I preferably has the following: (a) Preferably, at least one functional group capable of entering into a covalent bond with the functional group on the surface of the reinforcing fiber B by reaction with a hydroxy group and / or an amino group; and (b) Preferably, at least one second functional group capable of being incorporated into the copolymer A-1, preferably a double bond, more preferably a terminal double bond, by free radical polymerization.

[0109] Optionally, the copolymer A-1 or other (co)polymers present in the thermoplastic molding composition A may contain one or more other monomers capable of entering into a covalent or non-covalent bond with the reinforcing fiber B.

[0110] In a preferred embodiment, monomer A-I is selected from the group consisting of maleic anhydride (MA), N-phenylmaleimide (PM), tert-butyl (meth)acrylate, and glycidyl (meth)acrylate (GM). In a particularly preferred embodiment, monomer A-I is selected from the group consisting of maleic anhydride (MA), N-phenylmaleimide (PM), and glycidyl (meth)acrylate (GM). It is also possible for two of these monomers to be present in copolymer A-1.

[0111] The copolymer A-I in the thermoplastic molding composition A may optionally contain a further functional group monomer. Preferred copolymers A-1 are styrene / maleic anhydride, styrene / acrylonitrile / maleic anhydride, styrene / glycidyl methacrylate, styrene / N-phenylmaleimide, styrene / acrylonitrile / N-phenylmaleimide, methyl methacrylate / N-phenylmaleimide, methyl methacrylate / maleic anhydride, methyl methacrylate / maleic anhydride / N-phenylmaleimide, acrylonitrile / styrene / tert-butyl (meth)acrylate, acrylonitrile / butadiene / styrene / tert-butyl (meth)acrylate, and acrylonitrile / butyl acrylate / styrene / tet-butyl (meth)acrylate. Particularly preferred copolymers A-I are styrene / maleic anhydride, styrene / acrylonitrile / maleic anhydride, styrene / glycidyl methacrylate, styrene / N-phenylmaleimide, styrene / acrylonitrile / / N-phenylmaleimide, methyl methacrylate / N-phenylmaleimide, and methyl methacrylate / maleic anhydride / N-phenylmaleimide.

[0112] The method of the present invention preferably provides a thermoplastic molding composition A consisting of polystyrene, particularly glass-clear polystyrene "PS", or impact-resistant polystyrene or high-impact polystyrene "HIPS". The method of the present invention using glass-clear polystyrene preferably provides a (partially) permeable or transparent fiber composite material.

[0113] In a particularly preferred embodiment, the polymer component (A-a) of the thermoplastic molding composition A used according to the present invention is based on polypropylene. In this case, the polypropylene further contains monomer A-I that reacts on the surface of the reinforcing fiber B during the manufacturing process.

[0114] According to the present invention, what is meant by the feature of "modified by a chemically reactive functional group" or "having a chemically reactive functional group" is, in particular, the incorporation of maleic anhydride monomer into the polymer chain of the (co)polymer used according to the present invention.

[0115] The chemically reactive functional group of the thermoplastic molding composition A is very particularly preferably based on a component selected from the group consisting of maleic anhydride, N-phenylmaleimide, tert-butyl (meth)acrylate and glycidyl (meth)acrylate, in particular a component selected from the group consisting of maleic anhydride, N-phenylmaleimide, and glycidyl (meth)acrylate.

[0116] The modified polypropylene particularly preferably used according to the present invention as the thermoplastic molding composition A is produced from 90 to 99.7 parts by mass of unmodified polypropylene, preferably 95 to 99 parts by mass of unmodified polypropylene, and 0.3 to 10 parts by mass, preferably 1 to 5 parts by mass of maleic anhydride, based on 100 parts by mass of the modified polypropylene. More preferably, the maleic anhydride content in component A is in the range of 0.1 to 6 parts by mass, even more preferably 1 to 5 parts by mass, particularly 3 to 4 parts by mass, based on 100 parts by mass of the modified polypropylene.

[0117] It should be mentioned that it is a mixture of an α-methylstyrene-acrylonitrile copolymer and a styrene-acrylonitrile copolymer. The acrylonitrile-butadiene-styrene copolymer preferentially used according to the present invention as the thermoplastic molding composition A is produced by a known method from styrene, acrylonitrile, butadiene, and a further functional monomer A-I, in particular methyl methacrylate.

[0118] Preferably, according to the present invention, at least one of the (co)polymer components of the thermoplastic molding composition A is a (co)polymer having at least one chemically reactive functional group as described (polymer component (A-a)). This may also be the above-described polymer component containing at least one functional monomer A-I in the molding composition described above. Optionally, any one or more other (co)polymers having no such functional groups can be used (as polymer component (A-b)).

[0119] In a further preferred embodiment, the matrix M may consist of at least two different thermoplastic molding compositions A. These different molding composition types may preferably be characterized by different melt flow indices (MFI) and / or different comonomers or additives.

[0120] According to the present invention, the term "molecular weight" (Mw) is, in the broadest sense, the mass of a molecule or a molecule, particularly a polymer strand, block polymer, or oligomeric region, which can be reported in g / mol (Da) and kg / mol (kDa). The molecular weight (Mw) is preferably a weight average that can be determined by methods well known to those skilled in the art.

[0121] According to the present invention, the thermoplastic molding composition A used in process step ii) preferably has a molecular weight Mw in the range of 10,000 to 800,000 g / mol, more preferably in the range of 20,000 to 600,000 g / mol, where Mw can be determined by light scattering in tetrahydrofuran (GPC with UV detector). The molecular weight Mw of the thermoplastic molding composition A varies within a range of ±20%. Reference: A. Muller, Polymer Charakterisierung [Polymer Characterization], Hanser Verlag 1996

[0122] The thermoplastic molding composition A preferably contains polypropylene modified by a chemically reactive functional group, and this polypropylene is essentially formed from the same monomers as "normal monomers" except for the addition of monomer A-I. Here, the monomer content may vary by ±5%, the molecular weight by ±20%, and the melt flow index determined at a temperature of 230 °C and a load of 2.16 kg according to ISO 1133 may vary by ±20%. Preferably, according to the present invention, ISO 1133 means DIN EN ISO 1133-1:2012-03.

[0123] In a preferred embodiment, the melt volume flow rate (MVR) of the thermoplastic molding composition A used as the polymer matrix, measured by ISO 1133, is in the range of 0.1 to 400 cm 3 / 10 min at 230 °C / 2.16 kg, more preferably in the range of 0.5 to 200 cm 3 / 10 min, and particularly preferably in the range of 1 to 150 cm 3 / 10 min.

[0124] In a particularly preferred embodiment, the melt volume flow rate (MVR) of the thermoplastic molding composition A used as the polymer matrix, measured by ISO 1133, is in the range of 50 to 200 cm 3 / 10 min at 230 °C / 2.16 kg, more preferably in the range of 70 to 150 cm 3 / 10 min, and particularly preferably in the range of 85 to 125 cm 3 / 10 min.

[0125] This method is particularly preferred according to the present invention when the thermoplastic molding composition contains 0.1 to 6 parts by mass of maleic anhydride based on 100 parts by mass of polypropylene. Most preferably, the mass ratio of maleic anhydride is in the range of 0.2 to 5 parts by mass, particularly preferably 1 to 4 parts by mass, and very particularly preferably 3 to 4 parts by mass, based on 100 parts by mass of polypropylene.

[0126] Process step iii) Regarding optionally incorporating at least one additive C into a thermoplastic molding composition A that functions as matrix M. The matrix M used according to the present invention preferably contains, per 100 parts by mass of the thermoplastic molding composition A, 0.01 to 40 parts by mass, more preferably 0.01 to 30 parts by mass, still more preferably 0.01 to 25 parts by mass, and particularly preferably 1 to 20 parts by mass of at least one additive C, where the additive C is different from the base polymer and reinforcing fiber B of the thermoplastic molding composition A.

[0127] The additives used are preferably particulate mineral fillers, processing aids, stabilizers, antioxidants, thermal decomposition inhibitors, ultraviolet decomposition inhibitors, lubricants and mold release agents, flame retardants, dyes, pigments, or plasticizers. According to the present invention, it is also preferably possible to use two or more of these additives.

[0128] Preferred particulate mineral fillers are selected from the group consisting of amorphous silica, carbonates, particularly magnesium carbonate, calcium carbonate (chalk), powdered quartz, mica, silicates, particularly clay, muscovite, biotite, suzoite, szumareite, talc, chlorite, phlogopite, feldspar and calcium silicate, particularly wollastonite, or kaolin. Kaolin is a very particularly preferred mineral filler.

[0129] Preferred UV stabilizers are selected from the group consisting of substituted resorcinols, salicylates, benzotriazoles and benzophenones.

[0130] Preferred antioxidants, which are also known as thermal decomposition inhibitors, are selected from the group consisting of sterically hindered phenols, hydroquinones, secondary aromatic amines, optionally combinations of phosphoric acid or its salts, and mixtures of these compositions.

[0131] Preferred lubricants and mold release agents are selected from the group consisting of stearic acid, stearyl alcohol, alkyl stearate, stearyl amide, especially Irganox®, and esters of long-chain fatty acids and pentaerythritol. It is possible to use calcium, zinc, or aluminum salts of stearic acid, and dialkyl ketones, especially distearyl ketone. In addition, it is also possible to use ethylene oxide-propylene oxide copolymers as lubricants and mold release agents. In addition, natural and synthetic waxes can be used. These include polypropylene wax, polyethylene wax, polyamide wax, grafted polyolefin wax, HDPE wax, PTFE wax, EBS wax, montan wax, carnauba wax, and beeswax.

[0132] The flame retardant may be a halogen compound or a halogen-free compound. Preferred halogen compounds are bromine compounds rather than chlorine compounds, and remain stable during the production and processing of the molding compound of the present invention, without releasing corrosive gases and thereby impairing the efficacy. However, it is preferred to use halogen-free compounds, more preferably phosphorus compounds, especially phosphine oxides and derivatives of phosphoric acid, and salts of phosphoric acid and acid derivatives, as flame retardants. More preferably, the phosphorus compound contains ester, alkyl, cycloalkyl, and / or allyl groups. Similarly, for example, oligomeric phosphorus compounds having a molecular weight of less than 2000 g / mol as described in EP-A 0 363 608 are also suitable.

[0133] The pigments and dyes used as additives are known; see, for example, R. Gachter and H. Muller, Taschenbuch der Kunststoffadditive [Handbook of Plastics Additives], Carl Hanser Verlag, 1983, pp. 494 to 510. Preferred pigments are white pigments from the group of zinc oxide, zinc sulfate, lead white, lithopone, antimony white and titanium dioxide. Of the two most common crystal modifications of titanium dioxide (rutile type and anatase type), in particular the rutile type is used for the whitening of the thermoplastic molding composition A used according to the invention.

[0134] Black pigments that can likewise be used as additives according to the invention are iron sesquioxide (Fe 3 O 4 ), spinel black (Cu(Cr,Fe) 2 O 4 ), manganese black (= a mixture of manganese dioxide, silicon oxide and iron oxide), cobalt black and antimony black, more preferably usually carbon black used in the form of furnace black or gas black (for this point, see Benzing, Pigmente fur Anstrichmittel [Pigments for Paints], Expert-Verlag (1988), p. 78ff). Of course, according to the invention, it is possible to establish specific color tones using inorganic color pigments, such as chromium oxide green, or organic color pigments, in particular azo pigments and phthalocyanines. This kind of pigment is generally commercially available. In addition, it can generally be an advantage to use mixtures that facilitate color dispersion in thermoplastics, in particular the pigments or dyes described in carbon black with copper phthalocyanine.

[0135] At least one additive is preferably incorporated into the thermoplastic molding composition A by kneading. Kneading is preferably effected in an extruder, in particular a co-rotating twin-screw extruder, a counter-rotating twin-screw extruder, a planetary roll extruder, or a co-kneader. Kneading includes the process operations of conveying, melting, dispersing, degassing, pressure increase, and extrusion (discharge).

[0136] Process steps iv) to vi) After optionally incorporating at least one additive C into the thermoplastic molding composition A that functions as matrix M, this is incorporated into at least one fabric F provided in step iv).

[0137] In process step v), before the fiber composite material is cooled in process step vi), the chemically reactive functional groups of the thermoplastic molding composition A are reacted with the polar groups on the surface of the reinforcing fiber B treated with a silane size, and optionally followed by further steps.

[0138] The processes of the present invention, in particular process steps iv) and v), or optionally process step vi), are preferably carried out in a double belt press, an interval heating press, or a static press. In particular, a double belt press can produce a fiber composite material from a powder-based or film-based thermoplastic molding composition in a semi-continuous manner by conversion to a melt.

[0139] The thermoplastic molding composition A that functions as matrix M is incorporated into at least one fabric F by incorporating the thermoplastic molding composition A into the reinforcing fiber B by relative movement in which the reinforcing fiber B remains stationary away from the one-dimensional production supply port, and then the composite consisting of at least one fabric F and matrix M is compacted.

[0140] The relative movement of the thermoplastic molding composition A with respect to the reinforcing fiber B displaces the air present between the reinforcing fibers F. As a result, especially when the thermoplastic molding composition A is incorporated into the layer, the inclusion of air in the fiber composite material is reduced, preventing a good bond between the thermoplastic molding composition and the reinforcing fiber B. In accordance with the present invention, it is preferred to obtain a (very substantially) pore-free composite material after impregnation and consolidation.

[0141] The relative movement of the thermoplastic molding composition A with respect to the reinforcing fiber B is achieved by fixing the reinforcing fiber B in the direction of the relative movement. This fixing occurs when the movement of the thermoplastic molding composition A is at a temperature at least 10 °C higher than the crystal melting temperature or glass transition temperature in the case of an amorphous plastic, and a surface pressure > 10 bar, and is achieved by fixing the reinforcing fiber B upstream and downstream of the region, with the assistance of mechanical clamps, winding, or fixing elements. This holding is maintained by applying a force under a certain strain. In this way, the reinforcing fiber B is fixed in a position where longitudinal strain prevents movement in any spatial direction. When the reinforcing fiber B is fixed in this way and the thermoplastic molding composition is subjected to the above pressure and temperature for at least 1 second, the thermoplastic molding composition moves into the gaps between the reinforcing fibers. Once the movement of the thermoplastic molding composition is complete, the reinforcing fiber is removed from the temperature and pressure region.

[0142] The reinforcing fiber is separated from the continuous or discontinuous one-dimensional production supply port and remains stationary here. Preferably, in accordance with the present invention, the reinforcing fiber in the form of weaves is in the form of a roll in a delayed unwind drum shape upstream of the temperature and pressure application region, and as a connected stack downstream of the temperature and pressure application region, and is fixed by an automatic stretching system and held under tension.

[0143] In addition to the one-dimensional production supply port, the compaction associated with process step iv) is important in the process of the present invention. Compaction in a broad sense is a bonding process in which strength is developed at the joint between the matrix M and at least one fabric F in a physical process. In principle, there are four main mechanisms that occur during the compaction process: (where appropriate) impregnation of the fibers, compaction of the laminate, molecular penetration, and solidification.

[0144] The impregnation of the reinforcing fibers B used in accordance with the present invention into the fabric F is not employed in the compaction process when a prepreg or pre-impregnated semi-finished fiber product, called "prepreg", is used as the fabric F and a dried semi-finished product is not used. In the literature, there is often no distinction between the terms "compaction" and "impregnation", because the compaction of the laminate and molecular penetration only account for a very small part of the total compaction time. The proportion of laminate compaction and molecular penetration in the whole process is usually quantified on the order of about 1%. Therefore, the compaction process may optionally be called the direct impregnation process. Thus, in particular, by using a pre-impregnated semi-finished product or fabric, a short cycle time in processing can be achieved.

[0145] During the lamination process, in compaction, the surface of the thermoplastic molding composition such as the matrix polymer and the reinforcing fibers B of the fabric F are joined together until complete intimate contact is formed at high compaction pressure and high temperature. Here, there may be a problem of air inclusion. Air or other inclusions can be minimized only by the compaction pressure and / or optionally by exposure to the original. The intimate contact formed by the compaction of the laminate means that the roughness of the surfaces of the matrix polymer and the fabric, which are the mating parts, is ideally made uniform throughout the surface area. Good contact between the mating parts is important because a mechanically durable bond can only occur in the contact area. Complete intimate contact can be achieved even with low compaction pressure, but in that case the processing time is extended.

[0146] In the region where intimate contact between the matrix polymer and the fabric F has already been formed, molecular penetration of the fabric F begins only at that time. As a result of the thermal activation of the molecules in the matrix and the accompanying increase in molecular mobility, in molecular penetration, mutual diffusion of the polymer chains into the adjacent plies occurs, and as a result, the chain ends of the polymer of the thermoplastic molding composition used as the matrix can newly entangle and form loops with the polymer chains in the adjacent plies.

[0147] The description of molecular diffusion and thus self - aggregation as a result of the diffusion of polymer chains is not only time - dependent but generally also requires a flow effect as a driving force, particularly a micro - scale flow motion due to the applied compaction pressure. When molecular penetration is complete, the laminate is cooled in the final stage and thus dimensionally stabilizes (solidifies). As a result, the pore volume minimized by the application of the compaction pressure is essentially maintained even after the compaction stage ends due to cooling.

[0148] However, the thermally induced intrinsic stresses and deformations associated with the process can also remain frozen in the fiber composite material. While semi - crystalline thermoplastics recrystallize from the molten state in the cooling process, it is equally important that amorphous thermoplastics retain the molecular orientation finally assumed in the diffusion process during cooling. In different cases, it is also the cooling rate that determines the degree of crystallinity and the formation of spherulites in process step iv). The degree of crystallinity is the proportion of the thermoplastic molecular structure in the crystalline form. The mechanical and chemical properties (such as solvent stability, etc.) of a partially crystalline thermoplastic composition ultimately essentially depend on this. Therefore, the compaction of the thermoplastic material used as the matrix M according to the present invention is a highly non - linear process because it involves the different physical processes described above that occur to some extent simultaneously. These processes have a great impact on the quality of the final composite material and thus on the fiber composite material manufactured according to the present invention.

[0149] Therefore, insufficient consolidation may have knock-on effects such as trapped holes, residual stresses, deformations, especially distortions, and in some cases premature mechanical failure of the fiber composite material. Thus, in order to enable accurate prediction regarding consolidation, a meaningful model for the processes proceeding herein is indispensable. Such a process model gives the input-output relationship between the process parameters and the quality of the molded article T produced from the fiber composite material manufactured according to the present invention, thereby reducing the costly "trial and error" optimization of the technical devices used according to the present invention. Therefore, a reliable prediction obtained from the simulation regarding the quality of the molded article T provides an effective route to the optimization of process step iv) or process steps (iv)-(vi). In this way, it can be confirmed whether the quality of consolidation meets the criteria applied to the molded article F to be manufactured. Therefore, a complete simulation of the consolidation process takes into account the consolidation of the laminate, the compression of the holes, the geometrical deformation, the molecular penetration, the thermal degradation, the crystallization, as well as the residual stresses and the intrinsic distortions. The mathematical model cannot completely replace the physical experiments, but by combining them, it enables a simple parameter study that gives extremely important information for the process, which cannot be directly measured in a very difficult and time-consuming way if at all.

[0150] Process steps iv) and v), in particular consolidation, are carried out at a temperature of at least 200 °C, preferably at a temperature of 250 °C, and more preferably at a temperature of 300 °C.

[0151] Process steps iv) and v), in particular consolidation, are carried out at a pressure in the range from 1 bar to 1000 bar, preferably in the range from 5 bar to 500 bar, more preferably in the range from 10 bar to 50 bar.

[0152] Process steps iv) and v) are preferably carried out with a residence time of from 1 second to 60 seconds.

[0153] The method of the present invention is preferably carried out such that during steps ii) to v), the residence time is 10 minutes or less, preferably 5 minutes or less, more preferably 2 minutes or less, and particularly preferably 1 minute or less at a temperature of at least 200°C. At higher temperatures, correspondingly shorter residence times can be applied, which must be selected by a person skilled in the art depending on the thermoplastic used in each case.

[0154] The polar groups on the surface of the reinforcing fiber B treated with the silane size are important for the reaction between the chemically reactive functional groups of the thermoplastic molding composition A in the matrix M set in process step v) and the reinforcing fiber B.

[0155] For this purpose, the size applied to the reinforcing fiber is an impregnating liquid applied to the reinforcing fiber, in particular by spraying or dipping, in order to give the weave used according to the invention before its further processing. The sized fibers are more flexible and more stable against mechanical stress. Without sizing, the warp threads can easily become brittle as a result of the constant friction against the weft threads and can ultimately break.

[0156] In the production of glass fibers, it is preferred to be drawn at high speed from the melt. The thickness of the fiber is determined by the size of the nozzle and the take-up speed. The hot fibers are cooled by spraying water and wetting the size with dipping rolls, after which the individual fragments are immediately bundled into rovings. The size has several functions. The rovings are bound by a size binder and thus have sufficient stability against friction during transport and fraying or breaking of the individual fibers of the rovings. Since the size usually contains moisture as a thinner, the rovings must be dried. For this purpose, they are wound wet and made into a "cake", after which they are dried or processed wet and dried later. The glass fibers thus obtained can then be incorporated into a thermoplastic for reinforcement. Generally, the mass ratio of the size in the dry glass fibers ranges from 0.1% to 10% by mass.

[0157] Engineering stage vi) In engineering stage vi), the fiber composite material is cooled and optionally there is a further subsequent process.

[0158] The further process stage is preferably the production of the molded article T. In a preferred embodiment, the process then includes, as a further process stage, three-dimensional molding onto the molded article T.

[0159] The three-dimensional molding can be brought about in a desired manner, for example, by mechanical molding with a molding body which may be an embossing drum. Preferably, the cooled fiber composite material obtained in process stage vi) is finished in a further process stage, in particular by conventional cutting methods, preferably shear cutting, water jet cutting, laser cutting, or ultrasonic cutting, and then the fiber composite material is heated to a temperature at which it becomes moldable and the thermoplastic molding composition A is in a (partially) molten form and can be molded in a molding body, in particular a two-part steel mold. Alternatively or additionally, cold forming of the cured fiber composite material is also possible.

[0160] Preferably, at the end of the process, after process stage vi), a (mostly) solid fiber composite material sheet is obtained.

[0161] A further process stage or even cooling under increased pressure can also be carried out at a later stage or at another location. Optionally, the molded article T may be subjected to further processing, in particular deburring, polishing, or coloring.

[0162] The process of the present invention including process stages i) to vi) can be carried out continuously, semi-continuously, or batchwise. In a preferred embodiment, the process is carried out as a continuous process, in particular as a continuous process for producing a smooth or three-dimensional fiber composite material sheet.

[0163] Alternatively, it is also possible to manufacture the molded article T in a semi - continuous or discontinuous manner. In the case of a fiber composite material based on an amorphous thermoplastic matrix M, fins may be provided in the injection molding process and may be laminated (welded) as an outer layer to a foamed thermoplastic core or a honeycomb core. The improvement in part rigidity as a result of the fins (formation of a fin - equipped structure) is explained by the increase in the area moment of inertia. Generally, the optimal fin dimensions include considerations related to production, aesthetics, and design.

[0164] In a particularly preferred embodiment, the present invention relates to the method of the present invention for the production of a thermoplastic fiber composite material, wherein component A is produced from 90% - 99.7% polypropylene and 0.1% - 10% maleic anhydride, where the fabric F is a weave, and the residence time for the production of the fiber composite material at a temperature of at least 150°C is 10 minutes or less.

[0165] The present invention is preferably a method for producing a fiber composite material comprising a thermoplastic molding composition A as a polymer matrix M and reinforcing fibers B, i) providing at least one fabric F in the form of a weave of reinforcing fibers B treated with a silane size; ii) providing a thermoplastic molding composition A that functions as matrix M, the thermoplastic molding composition having at least 0.3 mol% of chemically reactive functional groups based on component A in the form of a functional monomer; iii) optionally, incorporating at least one additive C into the thermoplastic molding composition A; iv) introducing at least one fabric F by incorporating the thermoplastic molding composition A that functions as matrix M into the reinforcing fibers B by relative movement while keeping the thermoplastic molding composition A away from the continuous or discontinuous one - dimensional production supply port of the reinforcing fibers B and compacting the composite material composed of at least one fabric F and matrix M; (v) reacting the chemically reactive functional groups of the thermoplastic molding composition A with the polar groups on the surface of the reinforcing fiber B treated with a silane size; (vi) cooling the fiber composite material, and optionally further process steps, including, wherein the chemically reactive functional groups of the thermoplastic molding composition A are based on maleic anhydride, steps (iv) to (vi) are carried out at a temperature of at least 150 ° C, steps (v) to (vi) are carried out by pressurization under increased pressure, and the thermoplastic molding composition A contains 90% to 99.7% polypropylene and 0.1% to 10% maleic anhydride, and also contains 0% by mass to 40% by mass, preferably 0.1% by mass to 25% by mass of at least one additive C, a method for producing a fiber composite material.

[0166] Preferably, 5% to 90% by mass of a woven fabric F made of the reinforcing fiber B is used with respect to 10% to 95% by mass of the thermoplastic molding composition A.

[0167] In a further embodiment, a further group of reinforcing fibers is further bonded to the matrix M via a different fiber-matrix adhesion. When groups of three or more reinforcing fibers B with different fiber-matrix adhesions are used, the behavior of the fiber composite material is controlled and further influenced in highly individual ways and can be adjusted according to the respective use of the fiber composite material. Here, it is possible to use different fiber types or the same fiber type in each case.

[0168] Similarly, it is also possible for the warp and weft to consist of different reinforcing fibers and / or to have different thicknesses. In addition, the warp and weft may be treated with different sizes or sizes of different concentrations.

[0169] The groups of reinforcing fibers B may be treated with different adhesion promoter compositions that each provide a different fiber-matrix adhesion. The different compositions may differ only in concentration or may have other compositions. What is important is that different adhesion promoter compositions establish significantly different fiber-matrix adhesions.

[0170] The present invention is described in detail in the following examples, figures, and claims.

Example

[0171] The process of the present invention can be carried out on a double-belt press, an interval press, or a static press that can continuously produce fiber / film composites from polymer films, melts, or powders. Manufacturable laminate thickness: 0.1 - 15.0 mm Output: 0.1 - 1000 m / h, depending on quality and part thickness Forming pressure: Pressure unit 2 - 60 bar, infinitely adjustable at minimum and maximum forming sizes (optional) Forming temperature control: At least one heating zone and at least one cooling zone Forming temperature: Maximum 500 °C The flexural strength is determined according to DIN 14125:2011-05 by a three-point bending test or a four-point bending test. Reference: https: / / de.wikipedia.org / wiki / Biegefestigkeit

[0172] Components: A1: Polypropylene with a melt volume rate (MVR) of 100 cm³ / 10 min at 230 °C / 2.16 kg (measured according to ISO1133) 3 A2: Maleic anhydride (MA) A3: A mixture of A1 and A2, functional group concentration: 3% MA B1: 2 / 2 glass fiber twill weave, reference mass = approximately 600 g / m² 2 Warp + weft = 1200 tex [e.g., GW123-580K2 from P-D Glasseiden GmbH]

[0173] Regarding the achieved flexural strength, the combinations of A1 and B1, and A3 and B1 were compared in Table 1. Both combinations were manufactured with the same processing parameters (pressure, time, and temperature). Flexural strength is a characteristic that evaluates the quality of fiber-matrix adhesion and, thus, the mechanical component quality. For the combinations of A1 + B1 and A3a + B1a, the tested sheets were manufactured by static pressing with the processing of reinforcing fibers according to the prior art and, thus, in a non-distorted manner (indicated by "a"). The combination of A3b + B1b was manufactured by a manufacturing technique that ensures a non-distorted state (indicated by "b") of the reinforcing fibers according to step iv) of the method claimed herein.

[0174]

Table 1

[0175] It was found that the method of the present invention can achieve a fiber composite (material) that is 26% superior to the same matrix and the same reinforcing fiber-based fiber composite (material) manufactured by the method of EP 3 286 258 B1 in terms of flexural strength, rather than in step iv).

[0176] Any further processing Also, it was experimentally shown that the fiber composite material obtained by the method of the present invention has good formability into three-dimensional semi-finished products, such as semi-shell-shaped semi-finished products. The obtained fiber composite material was found to be printable and stackable.

[0177] Summary of experimental results The evaluation in the context of the present invention has shown that fiber composite materials with improved bending strength, i.e., organosheets and semi-finished products that can be manufactured from them, could be reproducibly manufactured by process step iv). The fiber composites / fiber composite materials according to the present invention can be manufactured in either a colorless or colored form. The fiber composites / fiber composite materials further showed good to very good optical, tactile, and mechanical properties, especially with regard to their bending strength. The fiber distortion that generally occurs in the fabric F was prevented by the manufacturing process of the present invention, and as a result, the fiber composites (materials) had only slight fiber distortion. The fiber composites / fiber composite materials that can be obtained by the present invention could be manufactured by a continuous process in a semi-automatic or fully automatic manner. The fiber composites / fiber composite materials (organosheets) that can be manufactured according to the present invention have good formability into three-dimensional semi-finished products.

Claims

1. A method for manufacturing a fiber composite material comprising a thermoplastic molding composition A as a polymer matrix M and a reinforcing fiber B, comprising: i) providing at least one fabric F in the form of a woven fabric made of the reinforcing fiber B treated with a silane size; ii) providing a thermoplastic molding composition A that functions as matrix M, the thermoplastic molding composition having at least 0.3 mol% of chemically reactive functional groups based on component A in the form of functional monomers; iii) optionally, incorporating at least one additive C into the thermoplastic molding composition A; iv) introducing the thermoplastic molding composition A that functions as matrix M into at least one fabric F by incorporating the thermoplastic molding composition A into the reinforcing fiber B by relative movement while keeping the reinforcing fiber B from moving away from a continuous or discontinuous one-dimensional production supply port, and compacting the composite material composed of at least one fabric F and the matrix M; v) reacting the chemically reactive functional groups of the thermoplastic molding composition A with the polar groups on the surface of the reinforcing fiber B treated with the silane size; vi) cooling the fiber composite material, and optionally further process steps, wherein the chemically reactive functional groups of the thermoplastic molding composition A are based on a component selected from the group consisting of maleic anhydride, N-phenylmaleimide, and glycidyl (meth)acrylate, and steps iv) to vi) are carried out at a temperature of at least 150 °C, and steps v) to vi) are carried out by pressurization under increased pressure, a method for manufacturing a fiber composite material.

2. The method for manufacturing a thermoplastic fiber composite material according to claim 1, characterized in that the thermoplastic molding composition A is based on an amorphous plastic or a semi-crystalline plastic.

3. The method for manufacturing a thermoplastic fiber composite material according to claim 2, characterized in that the thermoplastic molding composition A is based on at least one polymer from the group consisting of polyolefins, polyamides, thermoplastic elastomers, polycarbonates, polybutadiene terephthalates, polylactic acid, polyphenylene sulfide supply ports, and styrene copolymers.

4. A method for manufacturing the thermoplastic fiber composite material according to claim 3, wherein the polyolefin used is polypropylene.

5. A method for manufacturing the thermoplastic fiber composite material according to one or more of claims 1 to 4, characterized in that the reinforcing fiber B treated with a silane size is used.

6. A method for manufacturing the thermoplastic fiber composite material according to claim 5, characterized in that the reinforcing fiber B used is glass fiber.

7. A method for manufacturing the thermoplastic fiber composite material according to claim 6, characterized in that the glass fiber used as the reinforcing fiber B has a silanol group on the surface as a chemically reactive functional group.

8. The method for manufacturing the thermoplastic fiber composite material according to one or more of claims 1 to 7, characterized in that the process, particularly process steps iv) and v), or optionally process step vi), is carried out by a double belt press, an interval heating press or a static press.

9. A method for manufacturing the thermoplastic fiber composite material according to one or more of claims 1 to 8, characterized in that the manufacturing temperature of the fiber composite material is at least 150 °C, preferably at least 200 °C, and more preferably at least 250 °C.

10. A method for manufacturing the thermoplastic fiber composite material according to one or more of claims 1 to 9, characterized in that the residence time during the manufacture of the fiber composite material at a temperature of at least 200 °C does not exceed 10 minutes, preferably does not exceed 5 minutes, more preferably does not exceed 2 minutes, and particularly does not exceed 1 minute.

11. A method for manufacturing the thermoplastic fiber composite material according to one or more of claims 1 to 10, characterized in that the relative movement of the thermoplastic molding composition A with respect to the reinforcing fiber B is achieved by fixing the reinforcing fiber B in the relative movement direction.

12. For the movement of the thermoplastic molding composition A, in the case of an amorphous thermoplastic, the fixing of the reinforcing fiber B upstream and downstream in the region where the movement occurs at a temperature at least 10 °C higher than the crystal melting temperature or the glass transition temperature and under a surface pressure exceeding 10 bar is achieved by mechanical clamping, winding, or with the assistance of fixing elements, and this holding is maintained by the application of a reaction force under a constant strain. A method for manufacturing a thermoplastic fiber composite material according to claim 11, characterized in that.

13. A method for manufacturing a thermoplastic fiber composite material according to claim 11 or 12, characterized in that the reinforcing fiber B is fixed in a position where the longitudinal strain prevents movement in any spatial direction.

14. The reinforcing fiber B in the form of a fabric (weaves) is fixed by an automatic draw system in a roll on a delayed unwind drum and held under tension upstream of the temperature and pressure action region, and downstream of the temperature and pressure action region, it is fixed by an automatic draw system as a compacted stack and held under tension. A method for manufacturing a thermoplastic fiber composite material according to one or more of claims 1 to 13, characterized in that.

15. The chemically reactive functional groups of the thermoplastic molding composition A are based on maleic anhydride, steps iv) to vi) are carried out at a temperature of at least 150 °C, steps v) to vi) are carried out by pressurization under increased pressure, and the thermoplastic molding composition contains 90% to 99.7% by mass of polypropylene and 0.1% to 10% by mass of maleic anhydride, and also 0 to 40% by mass, preferably 0.1% to 25% by mass of at least one additive C. A method for manufacturing a thermoplastic fiber composite material according to one or more of claims 1 to 14, characterized in that.

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