EP3285999A1

EP3285999A1 - Use of a fibre composite material having sandwich structure and foam component

Info

Publication number: EP3285999A1
Application number: EP16720075.7A
Authority: EP
Inventors: Norbert Niessner; Philipp Deitmerg; Eike Jahnke
Original assignee: Ineos Styrolution Group GmbH
Current assignee: Ineos Styrolution Group GmbH
Priority date: 2015-04-22
Filing date: 2016-04-22
Publication date: 2018-02-28
Also published as: US20180086022A1; WO2016170131A1

Abstract

The use of a fibre composite material W having a sandwich structure, constructed from: A) a thermoplastic material layer w, containing as components: a) a thermoplastic moulding compound A as a matrix, b) a ply made from reinforcing fibres B, and c) optionally additive C, wherein the ply of reinforcing fibres B is embedded in the matrix of the thermoplastic moulding compound A, and, in the production of the material layer w, the thermoplastic moulding compound A comprises at least one chemically reactive functionality, which reacts with chemical groups of the surface of the reinforcing fibres B; and B) a further thermoplastic layer T and/or a foam layer S, wherein said further layer T and/or S is permanently connected to the material layer w; provides increased mechanical stability for the production of moulded parts.

Description

Use of a fiber composite material with sandwich structure and foam component

description

The present invention relates to a fiber composite material with foam component as a solid, lightweight sandwich structure. The subject matter is also the use of a sandwich structure composed of at least one fiber composite material W (organic sheet), containing a thermoplastic molding compound A and at least one layer of reinforcing fibers B. The at least one layer of the reinforcing fibers B is in the matrix with the embedded thermoplastic molding material A, wherein the thermoplastic molding material A has at least one chemically reactive functionality. The fiber composite material has a further thermoplastic layer T and / or at least one foam layer S, it is suitable for the production of molded parts.

Fiber composite materials (or organo sheets) consist of a plurality of reinforcing fibers embedded in a polymer matrix. The fields of application of fiber composite materials are manifold. Fiber composite materials are used in the vehicle and aviation sectors. In this case, fiber composite materials should prevent the tearing or other fragmentation of the matrix in order to reduce the risk of accidents caused by distributed component networks. Many fiber composite materials are able to absorb relatively high forces under load before it comes to a total failure. At the same time, fiber composite materials are distinguished by high strength and rigidity, combined with low density and other advantageous properties, such as, for example, good aging and corrosion resistance, compared with conventional, non-reinforced materials.

The strength and rigidity of the fiber composite materials can be adapted to the load direction and load type. Here, the fibers are primarily responsible for the strength and rigidity of the fiber composite material. In addition, their arrangement determines the mechanical properties of the respective fiber composite material. The matrix, on the other hand, usually serves primarily to introduce the forces to be absorbed into the individual fibers and to maintain the spatial arrangement of the fibers in the desired orientation. Since both the fibers and the matrix materials are variable, numerous combinations of fibers and matrix materials come into consideration.

In the production of fiber composite materials, the connection of fibers and matrix to one another plays an essential role. The strength of the embedding of the fibers in the polymer matrix (fiber-matrix adhesion) can also have a considerable influence on the properties of the fiber composite material. In order to optimize fiber-matrix adhesion and to compensate for "low chemical similarity" between the fiber surfaces and the surrounding polymer matrix, reinforcing fibers are regularly pretreated by the addition of regular adhesion agents to the so-called sizing agents In order to improve the further processability of the fibers (such as weaving, laying, sewing), if the sizing is undesirable for subsequent further processing, it must first be removed in an additional process step, for example by burning glass fibers are also processed without sizing, and then a further adhesion promoter is applied in an additional process step for the production of the fiber composite material Sizing agents and / or adhesion promoters form a layer on the surface of the fibers which interacts with the fibers can significantly determine the environment. Today, a variety of different adhesion agents are available. Depending on the field of application, the matrix to be used and the fibers to be used, the person skilled in the art can select a suitable adhesion promoter which is compatible with the polymer matrix and with the fibers.

A technical challenge is that the fiber composite material can suffer a brittle fracture when the total failure occurs. Consequently, for example, in the construction of moldings which are exposed to high mechanical stress, a significant risk of accident of torn components arise.

Therefore, it is desired to provide lightweight sandwich structures containing fiber composite materials with a wide loading range in which total failure is unlikely. In addition, good optical properties are desired, such as the possibility of being able to produce various elements with smooth surfaces by means of the fiber composite materials with sandwich structures. WO 2008/058971 describes molding compositions which use two groups of reinforcing fibers. The groups of reinforcing fibers are each provided with different adhesion promoter components which effect the different fiber matrix adhesions. The second fiber-matrix adhesion is less than the first fiber-matrix adhesion, and the near-surface layers of reinforcing fibers of reinforcing fibers of the first group are formed with greater fiber matrix adhesion. The matrix materials proposed are thermosetting plastics such as polyester and the thermoplastics polyamide and polypropylene.

WO 2008/1 19678 describes a glass fiber-reinforced styrene-acrylonitrile copolymer (SAN) which is improved in its mechanical properties by using maleic anhydride group-containing styrene copolymer and chopped glass fibers. It is therefore taught the use of short fibers. However, there is no indication of fiber composite materials.

CN 102924857 describes mixtures of styrene-maleic anhydride copolymers which are mixed with chopped glass and then show relatively high strengths. However, the stress cracking resistance of such a material to solvents is too low. The strength compared to fiber optic connections is clearly too low.

CN 101555341 describes mixtures of acrylonitrile-butadiene-styrene (ABS), glass fibers, maleic anhydride-containing polymers and epoxy resins. In the manufacture of ABS and the maleic anhydride-containing polymer are initially charged to add the epoxy resin and then the glass fibers. The fluidity of such a mixture containing a (thermoset) epoxy resin is very limited. KR 100376049 teaches mixtures of SAN, maleic anhydride and N-phenylmaleimide-containing copolymer, chopped glass fibers and an amino silane-based coupling agent. The use of such a coupling agent leads to additional processing steps and thus increases the production costs. WO 2014/163227 discloses a method for producing composite panels, and CA 2862396 describes a method for producing composite materials consisting of a core structure and at least one surface plate which is bonded to the core structure. US-A 201 1/0020572 describes organic sheet components having a hybrid design of, for example, a high flow polycarbonate component. Polycarbonate (PC) is rendered flowable by suitable additives, such as hyperbranched polyesters, ethylene / (meth) acrylate copolymers or low molecular weight polyalkylene glycol esters. DE 20 2010 001 918 teaches the preparation of composites wherein the fibers react with non-reactive molding compositions using adhesion and compatibilizers.

WO 2008/1 10539 teaches single-layer composites in which glass fibers are embedded in a molding compound.

(Glass) fibers are often treated in the prior art with a sizing, which protect each other especially the fibers. Mutual damage due to abrasion should be prevented. When mutual mechanical action should not come to the transverse fragmentation (fracture).

Furthermore, by means of the sizing, the cutting process of the fiber can be facilitated in order to obtain, above all, an identical staple length. In addition, the size can be used to avoid agglomeration of the fibers. The dispersibility of short fibers in water can be improved. Thus, it is possible to obtain uniform sheets by the wet laying method. A sizing may help to produce improved cohesion between the glass fibers and the polymer matrix in which the glass fibers act as reinforcing fibers. This principle is mainly used in glass fiber reinforced plastics (GRP). So far, the glass fiber sizes generally contain a large number of constituents, such as film formers, lubricants, wetting agents and adhesion promoters.

A film former protects the glass filaments from mutual friction and, in addition, can enhance an affinity for synthetic resins, thus promoting the strength and cohesion of a composite material. Starch derivatives, polymers and copolymers of vinyl acetate and acrylic esters, epoxy resin emulsions, polyurethane resins and polyamides in a proportion of 0.5 to 12 wt .-%, based on the total size, are mentioned. A lubricant gives the glass fibers and their products suppleness and reduces the mutual friction of the glass fibers, as well as in the production. Often, however, the adhesion between glass and resin is compromised by the use of lubricants. Fats, oils and polyalkyleneamines in an amount of 0.01 to 1 wt .-%, based on the total size, are mentioned. A wetting agent causes a lowering of the surface tension and an improved wetting of the filaments with the size. For aqueous sizes, for example, polyfatty acid amides in an amount of 0.1 to 1, 5 wt .-%, based on the total size to name.

Often there is no suitable affinity between the polymer matrix and the glass fibers.

This bridging can take over adhesion promoters which increase the adhesion of polymers to the fiber surface. Most organo-functional silanes, such as aminopropyltriethoxysilane, methacryloxypropyltrimethoxysilane, glycidyloxypropyltrimethoxysilane and the like can be mentioned.

Silanes which are added to an aqueous sizing are usually hydrolyzed to silanols. These silanols can then react with reactive (glass) fiber surfaces and thus form an adhesive layer (with a thickness of about 3 nm).

Consequently, low molecular weight, functional agents can react with Siianoigruppen on the glass surface, which then further terreagieren low molecular weight agents (for example, in epoxy resins), thereby ensuring a chemical bonding of the glass fiber to the polymer matrix. However, such a preparation is time-consuming and lasts until complete curing of the polymers (for example the abovementioned epoxy resins) approximately between 30 minutes to more than one hour.

It therefore appears desirable to bring already polymerized melts in conjunction with glass fibers or other reinforcing fibers in an improved process. A functionalization by reaction with polymers is also known. Thus, by using low-molecular-weight polycarbonate types, it is possible to impregnate the glass fiber fabric and to perform a "grafting" by reacting functional groups on the glass fiber surface with the polycarbonate, which increases the compatibility with the polymer - Part that polycarbonate (PC) has a very high viscosity and low-molecular, ie low-viscosity PC must be used for this impregnation, which has an extremely poor usability, such as a low resistance to stress cracking agents, such as polar solvents has. A technical object of the invention is to produce a fiber composite material having a sandwich structure, containing a fiber composite material (organic sheet), which has suitable properties for the construction of molded parts.

The fiber composite material contained should be based on an easy-to-process, largely solvent-resistant, good stress-crack-resistant, solid composite material and have a smooth surface. Ideally, the fiber composite material comes without adhesion promoter.

It has surprisingly been found that sandwich structures composed of at least one thermoplastic material layer w and a further thermoplastic layer T and / or at least one foam layer S fulfill the desired criteria. The thermoplastic material layer w contains at least one thermoplastic molding compound A as a matrix, at least one layer of reinforcing fibers B, and optionally at least one additive C, wherein the at least one layer of the reinforcing fibers B is embedded in the matrix. In this case, the thermoplastic molding composition A at least one chemically reactive functionality, which reacts with chemical groups of the surface of component B during the manufacturing process of the fiber composite material. The resultant fiber composite material W with a sandwich structure has good strength and is stress cracking and solvent resistant.

A first aspect of the present invention relates to the use of a fiber composite material W having a sandwich structure, composed of:

A) at least one thermoplastic material layer w,

containing as components in the production

a) at least one thermoplastic molding compound A as matrix,

b) at least one layer of reinforcing fibers B, and

c) optionally at least one additive C, wherein the at least one layer of the reinforcing fibers B is embedded in the matrix of the thermoplastic molding composition A, and

wherein the thermoplastic molding material A in the production of the material layer w has at least one chemically reactive functionality which reacts with chemical groups of the surface of the reinforcing fibers B; and B) at least one further thermoplastic layer T, which is different from the layer w, and / or at least one foam layer S, said further layer T and / or S being permanently connected to the material layer w; for the production of molded parts.

In other words, the present invention also relates, in other words, to a method for producing a fiber composite material W with a sandwich structure, comprising the following steps: (i) providing

at least one thermoplastic material layer w,

containing as components (or consisting of the components) in the preparation

a) at least one thermoplastic molding compound A as matrix,

b) at least one layer of reinforcing fibers B, and

c) optionally at least one additive C,

wherein the at least one layer of the reinforcing fibers B is embedded in the matrix of the thermoplastic molding compound A, and

wherein the thermoplastic molding material A in the production of the material layer w has at least one chemically reactive functionality which reacts with chemical groups of the surface of the reinforcing fibers B; and

(ii) application of

at least one further thermoplastic layer T, which is different from the layer w, and / or at least one foam layer S, this further layer T and / or S being permanently connected to the material layer w; for the production of molded parts.

The polymer matrix may be an amorphous plastic (polymer) matrix into which the fibers are embedded as reinforcing fibers B and coupled to the matrix via fiber-matrix adhesion.

According to the invention, the material layer w comprises the components A and B. The reinforcing fibers B are embedded in a thermoplastic molding compound A. The corresponding material layer w is connected to at least one thermoplastic layer T or foam layer S.

The invention particularly relates to the use of a fiber composite material W having a sandwich structure as described above, constructed (or consisting of): A) 10 to 70 wt .-% of at least one thermoplastic material layer w, containing

a) 30 to 95% by weight of the thermoplastic molding composition A,

b) 5 to 70% by weight of the reinforcing fiber B,

c) 0 to 40 wt .-% of at least one additive C, and

B) 30 to 90 wt .-% of at least one further thermoplastic layer T and / or at least one foam layer S. The invention particularly relates to the use of a sandwich structure as described above, wherein the thermoplastic molding material A is amorphous.

In a further embodiment, the invention relates to the use of a sandwich-type fiber composite material as described above, wherein the thermoplastic molding compound A is amorphous and is based on a styrene copolymer modified by a chemically reactive functionality.

In a further embodiment, the invention relates to the use of a sandwich-structured fiber composite material as described above, wherein the thermoplastic molding compound A is selected from the group of copolymers modified by a chemically reactive functionality and consisting of: styrene-acrylonitrile Copolymers, α-methylstyrene-acrylonitrile copolymers, toughened acrylonitrile-styrene copolymers, in particular acrylonitrile-butadiene-styrene copolymers (ABS) and acrylonitrile-styrene-acrylic ester copolymers (ASA), and blends of said copolymers with polycarbonate or polyamide. The thermoplastic molding compound A is z. A maleic anhydride modified styrene-acrylonitrile copolymer or acrylonitrile-butadiene-styrene copolymer (ABS).

In a further embodiment, the invention relates to the use of a fiber composite material having a sandwich structure as described above, wherein the chemically reactive functionality of the thermoplastic molding composition A is based on components selected from the group consisting of maleic anhydride, N-phenylmaleimide and glycidyl (meth) acrylate , In a further embodiment, the invention relates to the use of a sandwich-type fiber composite material as described above, where the thermoplastic molding composition A is from 0.1 to 10% by weight, often from 0.15 to 5% by weight, monomers ( Al), based on the amount of component A, wherein these monomers have a chemically reactive functionality. In a further embodiment, the invention relates to the use of a thermoplastic fiber composite material as described above, wherein the reinforcing fibers B consist of glass fibers which preferably contain as chemical-reactive functionality silane groups on the surface.

In a further embodiment, the invention relates to the use of a fiber composite material having a sandwich structure as described above, wherein the reinforcing fibers B contain on the surface one or more chemically reactive functionalities from the group hydroxy, ester and amino groups.

In a further embodiment, the invention relates to the use of a fiber composite material having a sandwich structure as described above, wherein the reinforcing fibers B consist of glass fibers which contain silanol groups on the surface as chemically reactive functionality.

In a further embodiment, the invention relates to the use of a composite sandwich material structure as described above, wherein the reinforcing fiber B is used in the form of a mat, a fabric, a mat, a nonwoven or a knitted fabric.

In a further embodiment, the invention relates to the use of a composite fiber composite material as described above, wherein the reinforcing fibers B in the form of a mat, a fabric, a mat, a nonwoven or a knitted fabric in a maleic anhydride-modified styrene copolymer as Molding compound A are used.

In a further embodiment, the invention relates to the use of a fiber composite material having a sandwich structure as described above, wherein the material layer w has a thickness of <100 mm, in particular of <20 mm, preferably of <10 mm, especially of <5 mm.

In a further embodiment, the invention relates to the use of a fiber composite material having a sandwich structure as described above, wherein the material layer w has a ribbing.

In a further embodiment, the invention relates to the use of a fiber composite material W having a sandwich structure as described above, wherein the material layer w is constructed in a layered manner and contains a plurality of layers. In a further embodiment, the invention relates to the use of a fiber composite material having a sandwich structure as described above, wherein the sandwich structure is layered and more than three layers, for. B. 4 or 5 layers contains.

In a further embodiment, the invention relates to the use of a fiber composite material W having a sandwich structure as described above, wherein the at least one thermoplastic layer T and / or at least one foam layer S by lamination or (co-) extrusion with the thermoplastic material - Layer w are connected.

In a further embodiment, the invention relates to the use of a fiber composite material having a sandwich structure as described above, wherein the thermoplastic layer T is reinforced with at least one short, long or continuous fiber S, in particular with carbon or basalt fibers.

In a further embodiment, the invention relates to the use of a sandwich-type fiber composite material as described above, wherein the foam layer S consists of expanded thermoplastic molding materials (such as expanded polystyrene) prepared by chemical or physical blowing agents.

Another aspect of the invention relates to a fiber composite material W having a sandwich structure, containing (or consisting of):

A) at least one thermoplastic material layer w,

containing as components in the production

a) at least one thermoplastic molding compound A as matrix,

b) at least one layer of reinforcing fibers B, and

c) optionally at least one additive C,

B) at least one further thermoplastic layer T, which is different from the layer w, and / or at least one foam layer S, wherein said further layer T and / or S is permanently connected to the material layer w. It will be understood that this is preferably a fiber composite material W having a sandwich structure made according to the use described herein and / or having one or more other features as described herein. The definitions and preferred embodiments as defined with respect to use apply equally to the fiber composite material W as such.

Component A The material layer w contains at least 20% by weight, generally at least 30% by weight, based on the total weight of the material layer w, of the thermoplastic matrix M or of the thermoplastic molding compound A. The thermoplastic matrix ( M), which contains (or consists of) the molding compound A, in the material layer w is preferably from 30 to 95% by weight, particularly preferably from 35 to 90% by weight, often from 35 to 70% by weight .-% and in particular from 38 to 70 wt .-%, based on the material layer w, present. The thermoplastic matrix M preferably corresponds to the thermoplastic molding compound A.

The person skilled in the art will understand that the thermoplastic molding composition A according to the invention comprises at least one (co) polymer having at least one chemically reactive functionality which reacts with chemical groups on the surface of the reinforcing fiber component B during the manufacturing process of the fiber composite material , Such a (co) polymer comprises at least one functional monomer A-1 whose functionality reacts with chemical groups on the surface of the reinforcing fiber component B during the production process of the fiber composite material. The (co) polymer comprising monomer A-1 is also referred to herein as polymer component (A-a).

Optionally, the thermoplastic molding composition A may contain one or more (co) polymers which are optionally also free of such a chemically reactive functionality (therefore contain no functional monomer Al) and thus not with chemical groups on the surface during the manufacturing process of the fiber composite material the reinforcing fiber component B react. Such a (co) polymer is also referred to herein as polymer component (A-b).

Preferably, the thermoplastic molding composition A consists mainly (more than 50%) of a copolymer (A-1). According to one embodiment, the thermoplastic molding composition A is at least 75% by weight, preferably at least 90% Wt .-% of the copolymer A-1. The thermoplastic molding compound A can also consist only of copolymer A-1.

Such a styrene copolymer, when used as the polymer component (A-a), may be about a M-1-containing styrene copolymer (exemplified by a maleic anhydride-containing styrene copolymer).

For a material layer w according to the invention, any desired thermoplastic polymers are suitable as thermoplastic molding material A, but in particular modified styrene copolymers, in particular SAN, ABS and ASA, are used.

As already explained above, the skilled person will understand that according to the 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 functionality as described herein (polymer component (Aa)) , Accordingly, it is preferred that at least one of the abovementioned polymer components (therefore at least one (optionally modified) polystyrene and / or at least one copolymer A-1 (styrene copolymer, in particular SAN, ABS and ASA)) comprises at least one monomer Al ,

For example, in the case of using maleic anhydride (MA) as the monomer Al, the polystyrene can therefore be a polystyrene-maleic anhydride copolymer (S-MA), the copolymer A-1 is exemplified by styrene-acrylonitrile-maleic anhydride copolymer (SANMA), Acrylonitrile-butadiene-styrene-maleic anhydride copolymer (ABS-MA), acrylic ester-styrene-acrylonitrile-maleic anhydride copolymer (ASA-MA).

Optionally, in addition to the at least one polymer component (A-a), one or more further (co) polymers without such functionality (as polymer component (A-b)) can be used. It will be understood that this may optionally also be polystyrene, SAN, ABS and / or ASA (each not comprising a monomer A-1).

The thermoplastic molding compound A (component A) is preferably an amorphous molding compound, wherein the amorphous state of the thermoplastic molding compound (thermoplastic) means that the macromolecules are arranged completely randomly without regular arrangement and orientation, ie without a constant spacing. Preferably, the entire thermoplastic molding composition A has amorphous, thermoplastic properties, is therefore meltable and (largely) non-crystalline. As a result, the shrinkage of the thermoplastic molding compound A, and therefore also of the entire material layer w, is comparatively low. It can be obtained particularly smooth surfaces in the moldings. Alternatively, the component A contains a partially crystalline fraction, generally less than 50 wt .-%, preferably less than 40 wt .-%, often less than 25 wt .-%, based on the total weight of component A. Semi-crystalline thermoplastics form both chemically regular , as well as geometric areas, ie there are areas where crystallites form. Crystallites are parallel bundles of molecular segments or folds of molecular chains. Individual chain molecules can partially pass through the crystalline or the amorphous region. Sometimes they can even belong to several crystallites at the same time.

The thermoplastic molding compound A may be a blend of amorphous thermoplastic polymers and semi-crystalline polymers. The thermoplastic molding compound A may be e.g. a blend of a styrene copolymer with one or more polycarbonate (s) and / or one or more partially crystalline polymers (such as polyamide), the proportion of partially crystalline mixed components in the entire component A being less than 50% by weight, preferably less 40% by weight, often less than 25% by weight.

According to the invention, the thermoplastic molding composition A used comprises at least one copolymer A-1 which comprises monomers A-1 which form covalent bonds with the functional groups B-1 of the embedded reinforcing fibers B. The proportion of monomers A-l in the thermoplastic molding composition A can be chosen variable. The higher the proportion of monomers A-1 and the functional groups (B-1), the stronger the bond between the thermoplastic molding compound A and the reinforcing fibers B can be. Monomers A-1 may still be present as monomers in copolymer A-1 or may be incorporated into copolymer A-1. Preferably, the monomers A-1 are incorporated into the copolymer A-1.

According to a preferred embodiment, the copolymer A is constructed with a proportion of monomers A1 of at least 0.1 wt .-%, for example 0.1 to 10% by weight, preferably from 0.15 to 5 wt .-%, preferably from 0.5 to 5 wt .-%, in particular of 1 wt .-%, z. B. 1 to 3 wt .-%, based on component A.

As monomers Al, which can form covalent bonds with the functional groups Bl of the fibers B, all monomers are suitable which have such properties. have. As monomers A1, preference is given to those which can form covalent bonds by reaction with hydroxyl or amino groups.

Preferably, the monomers A-1 have:

(a) at least one functionality capable of entering into covalent bonds with the functional groups B-1 of the surface of the fibers B (such as by reaction with hydroxyl and / or amino groups); and

(B) at least one second functionality capable of being incorporated in the copolymer A-1, for example a double bond, preferably a terminal double bond, which is incorporated by means of radical polymerization in the copolymer A-1.

Optionally, the copolymer A-1 or another (co) polymer contained in the thermoplastic molding composition A may contain one or more further monomers capable of forming covalent or non-covalent bonds with the fibers B.

According to a preferred embodiment, the monomers A-I are selected from the group consisting of:

Maleic anhydride (MA),

N-phenylmaleimide (PM),

tert-butyl (meth) acrylate and

Glycidyl (meth) acrylate (GM).

According to a more preferred embodiment, the monomers A-1 are selected from the group consisting of maleic anhydride (MA), N-phenylmaleimide (PM) and glycidyl (meth) acrylate (GM).

Also, two of these monomers Al may be contained in the copolymer A-1. The copolymer A-1 of the molding compound A may optionally include further functional monomers A-II. The matrix component M contains at least one thermoplastic molding compound A, in particular one suitable for the production of fiber composite materials. Preferably, amorphous thermoplastics are used for the molding compound A. For example, styrene copolymers (in each case optionally containing monomers Al) are used, such as styrene-acrylonitrile copolymers (SAN) or α-methylstyrene-acrylonitrile copolymers (AMSAN), impact-modified styrene-acrylonitrile copolymers, such as acrylonitrile-butadiene-styrene -Copolymers (ABS), styrene-methyl methacrylate copolymers (SMMA), methacrylate-acrylonitrile-butadiene-styrene copolymers (MABS) or acrylic ester-styrene-acrylonitrile copolymers (ASA), wherein the corresponding molding materials with monomers (Al) are modified ,

Blends of the abovementioned copolymers with polycarbonate or partially crystalline polymers such as polyamide are also suitable, provided that the proportion of partially crystalline mixed components in component A is less than 50% by weight. Very particular preference is given to using ABS copolymers (with modification by monomers A-1) as thermoplastic molding material A. It will be understood that in this case at least one of the polymer components in the thermoplastic molding composition A is modified with monomer A-1 (polymer component (A-a)), preferably one or more of the abovementioned styrene copolymers is modified with monomer A-1. Any other polymer components (for example styrene copolymers, preferably those as mentioned above) may optionally be additionally present in the thermoplastic molding composition A, which are not optionally modified with monomer A-1 (polymer component (A-b)).

Blends of the abovementioned copolymers (one or more polymer components (Aa) and optionally (Ab)) with polycarbonate or partially crystalline polymers such as polyamide are also suitable, provided that the proportion of partially crystalline mixed components in component A is less than 50% by weight. , Very particular preference is given to using SAN (M-1) copolymers (with modification by monomers A-1) as component of the thermoplastic molding composition A (optionally also as sole polymeric constituent).

A modified (a-methyl) styrene-acrylonitrile copolymer used according to the invention as thermoplastic molding material A is prepared from, based on the (o-methyl) styrene-acrylonitrile copolymer, 60 to 85 wt .-%, preferably 65 to 80 wt. -%, (a-methyl) styrene, 14.9 to 37 wt .-%, preferably 19.9 to 32 wt .-%, acrylonitrile and 0.1 to 5 wt .-%, preferably 0.1 to 3 wt .-%, maleic anhydride. Further to be mentioned as component A of the invention: styrene / maleic anhydride copolymer, methyl methacrylate / maleic anhydride copolymers or styrene / maleic anhydride / N-phenylmaleimide copolymer. Mixtures of modified styrene-acrylonitrile copolymer with a-methyl-styrene-acrylonitrile copolymer may also be mentioned.

An inventive acrylonitrile-butadiene-styrene copolymer as thermoplastic molding material A is prepared by known methods from styrene, acrylonitrile, butadiene and a functional further monomer A-l, such as. For example, methyl methacrylate.

The modified ABS copolymer may, for. For example, up to 70% by weight (about 35 to 70% by weight) of butadiene, up to 99.9% by weight (about 20 to 50% by weight) of styrene and up to 38% by weight. % (about 9 to 38 wt%) of acrylonitrile and 0.1 to 20 wt%, preferably 0.1 to 10, more preferably 0.1 to 5, especially 0.1 to 3 wt% of a monomer A- I, such as maleic anhydride. Component A can also be prepared from 3 up to 70% by weight (about 35 to 70% by weight) of at least one conjugated diene, up to 99.9% by weight (about 20 to 50% by weight) of at least one vinylaromatic monomer and up to 38% by weight (about 9 to 38% by weight) of acrylonitrile and 0.1 to 20% by weight, preferably 0.1 to 10, more preferably 0.1 to 5, especially 0.1 to 3% by weight of a monomer Al such as maleic anhydride.

An (a-methyl) styrene-methyl methacrylate copolymer (as polymer component (Aa)) according to the invention as thermoplastic molding compound A is prepared from, based on the (a-methyl) styrene-methyl methacrylate copolymer, at least 50% by weight, preferably 55 to 95 wt .-%, particularly preferably 60 to 85 wt .-%, (a-methyl) styrene, 4.9 to 45 wt .-%, preferably 14.9 to 40 wt .-% of methyl methacrylate and 0.1 to 20 wt .-%, preferably 0.1 to 10, more preferably 0.1 to 5 wt .-%, in particular 0.1 to 3 wt .-%, of a monomer Al, such as maleic anhydride. The (o-methyl) styrene-methyl methacrylate copolymer may be random (random) or block polymer.

Component A can also be prepared from based on component A, at least 50 wt .-%, preferably 55 to 95 wt .-%, particularly preferably 60 to 85 wt .-%, vinylaromatic monomer, 4.9 to 45 wt. -%, preferably 14.9 to 40% by weight, methyl methacrylate and 0.1 to 5 wt .-%, preferably 0.1 to 3 wt .-%, of a monomer Al, such as maleic anhydride. In a further preferred embodiment, the inventive component A is a styrene / butadiene copolymer such as (in each case optionally chemically mofifiziertes) impact-resistant polystyrene, a styrene-butadiene block copolymer such as Styrolux®, Styroflex®, K-resin, cleares, asaprenes , a polycarbonate, an amorphous polyester or an amorphous polyamide. The person skilled in the art will understand that according to the invention at least one of the (co) polymer components of the thermoplastic molding composition A is a (co) polymer which has at least one chemically reactive functionality as described herein (polymer component (Aa)). This may also be a polymer component as described above, which contains at least one functional monomer Al in said molding composition. Optionally, one or more other (co) polymers without such functionality (as the polymer component (Ab)) can be used.

In a further embodiment, the matrix M can consist of at least two mutually different thermoplastic molding compositions A. For example, these various molding compound types may have a different melt flow index (MFI), and / or other co-monomers or additives.

According to the invention, the term molecular weight (Mw) in the broadest sense can be understood as the mass of a molecule or a region of a molecule (eg a polymer strand, a block polymer or a small molecule) which is in g / mol (Da) and kg / mol (kDa) can be specified. Preferably, the molecular weight (Mw) is the weight average which can be determined by the methods known in the art.

The thermoplastic molding compositions A preferably have a molecular weight Mw of from 60,000 to 400,000 g / mol, particularly preferably from 80,000 to 350,000 g / mol, where Mw can be determined by light scattering in tetrahydrofuran (GPC with UV detector). The molecular weight Mw of the thermoplastic molding compositions A can vary within a range of +/- 20%.

Preferably, the thermoplastic molding composition A contains a modified by a chemically reactive functionality styrene copolymer, which, except for the addition of the monomers Al, essentially composed of the same monomers as the "normal styrene copolymer", wherein the monomer content +/- 5 %, the molecular weight +/- 20% and the melt flow index (determined at a temperature of 220 ° C. and a loading of 10 kg according to ISO Method 1 133) +/- 20% ISO 1 133-1: 2012-03.

According to a preferred embodiment, the melt volume rate (MVR) of the thermoplastic polymer composition used as polymer matrix is A reduction from 10 to 70 cm ^3/10 min, preferably 12 to 70 cm ^3/10 min, particularly 15 to 55 cm ^3/10 min at 220 ° C / 10kg (measured according to IS01 133).

According to a particularly preferred embodiment, the melt flow rate is (Melt Volume rate, MVR) of the thermoplastic polymer composition used as the polymer matrix A 10 to 35 cm ^3/10 min, preferably 12 to 30 cm ^3/10 min, particularly 15 to 25 cm ^3/10 min at 220 ° C / 10kg (measured according to IS01 133).

Alternatively, the melt flow rate (melt volume rate MVR) of the thermoplastic polymer composition used as the polymer matrix A 35 to 70 cm ^3/10 min, preferably 40 to 60 cm ^3/10 min, in particular 45 to 55 cm ^3/10 min at 220 ° C / 10kg (measured according to IS01 133).

Alternatively or additionally, the viscosity number determined by means of a capillary viscometer (J = (η / η ₀ -1) ^.sup.1 / c) of the thermoplastic polymer composition A used as polymer matrix, measured at room temperature (20.degree. C.) for dimethylformamide dissolved Granules, 50 to 100 ml / g, preferably 55 to 85 ml / g. According to a preferred embodiment, the viscosity number is 55 to 75 ml / g, preferably 60 to 70 ml / g, in particular 61 to 67 ml / g. According to an alternative preferred embodiment, the viscosity number is 60 to 90 ml / g, preferably 65 to 85 ml / g, in particular 75 to 85 ml / g.

Suitable preparation methods for component A are emulsion, solution, bulk or suspension polymerization, preference being given to solution polymerization (see GB 1472195).

In a preferred embodiment of the invention, component A is isolated after the preparation by processes known to those skilled in the art, and preferably processed into granules. Thereafter, the production of the material layer w can take place. Component B

The material layer w contains at least 5 wt .-%, based on the material layer w, the reinforcing fiber B (component B). The reinforcing fiber B in the material layer w is preferably from 5 to 70% by weight, more preferably from 10 to 65% by weight, often from 25 to 65% by weight, and more preferably from 29.9 to 61.9 % By weight, based on the material layer w.

The reinforcing fiber B is preferably used as the sheet F. The reinforcing fiber B may be any fiber whose surface functional groups Bl which can form a covalent bond with the monomers Al of component A, which have a chemically reactive functionality.

Fabrics F may preferably be fabrics, mats, nonwovens, scrims or knits. Alternatively, the reinforcing fibers B are present as continuous fibers (including fibers which are the product of a single fiber twist). The reinforcing fibers B are therefore preferably not short fibers ("chopped fibers") and the fiber composite material W is preferably not a short glass fiber reinforced material At least 50% of the reinforcing fibers B preferably have a length of at least 5 mm, more preferably at least 10 mm or more 100 mm, the length of the reinforcing fibers B also depends on the size of the molded part T, which is made of the fiber composite material W.

It is known to the person skilled in the art that flat fabrics F (therefore, for example, fabrics, mats, nonwovens, scrims or knitted fabrics) differ from short fibers, since the former have coherent, larger structures, which will generally be longer than 5 mm. The person skilled in the art knows that in this case the fabrics F are preferably present in such a way that they pass (largely) through the fiber composite material W (and thus also the component T produced therefrom). Passing through substantially means here that the fabrics F pass through more than 50%, preferably at least 70%, in particular at least 90%, of the length of the fiber composite material W. The length here is the largest extent in one of the three spatial directions. More preferably, the fabrics F pass through more than 50%, preferably at least 70%, in particular at least 90%, of the surface of the fiber composite material W. In this case, the surface is the area of maximum expansion in two of the three spatial directions. The fiber composite material W is preferably a (largely) flat fiber composite material W (therefore also the molding T preferably a flat molding T).

In a preferred embodiment, the functional groups B-1 on the surface of the reinforcing fiber B are selected from hydroxy, ester and amino groups. Particularly preferred are hydroxy groups.

According to a more preferred embodiment, the reinforcing fibers B are glass fibers having hydroxy groups in the form of silanol groups as surface functional groups B-1.

The reinforcing fibers B can be embedded in the material layer w in any orientation and arrangement. The reinforcing fibers B are present not uniformly distributed in the material layer w, but in planes with higher and those with lower proportion (therefore as more or less separate layers). Preferably, a laminate-like or laminar structure of the material layer w is assumed.

The reinforcing fibers B may be present, for example, as fabrics, mats, nonwovens, scrims or knitted fabrics.

Such laminar laminates formed in this way comprise laminations of sheet-like reinforcing layers (of reinforcing fibers B) and layers of the polymer matrix which moistens and holds them, containing at least one thermoplastic molding compound A.

According to a preferred embodiment, the reinforcing fibers B are embedded in layers in the material layer w. Preferably, the reinforcing fibers B are present as a flat structure F.

In a clutch, the fibers are ideally parallel and stretched. There are usually used endless fibers. Tissues are created by the interweaving of continuous fibers, such as rovings. The interweaving of fibers inevitably involves an ondulation of the fibers. The ondulation causes in particular a reduction of the fiber-parallel compressive strength. Mats are usually made of short and long fibers, which are loosely connected by a binder. Through the use of short and long fibers, the mechanical properties of components made of mats are inferior to those of fabrics. Nonwovens are structures of limited length fibers, filaments or cut yarns of any kind and of any origin which have been somehow joined together to form a nonwoven and joined together in some manner. Knitted fabrics are thread systems by stitching. The fabric F is preferably a scrim, a fabric, a mat, a nonwoven or a knitted fabric. Particularly preferred as a fabric F is a scrim or a fabric.

Component C

As further component C, the material layer w used optionally contains 0 to 40 wt .-%, preferably 0 to 30 wt .-%, particularly preferably 0.1 to 10 wt .-%, based on the buzzer of the components A to C. , one or more, to the components A and B of different additives (auxiliaries and additives). Particulate mineral fillers, processing aids, stabilizers, oxidation retarders, agents against heat decomposition and decomposition by ultraviolet light, lubricants and mold release agents, flame retardants, dyes and pigments and plasticizers are to be mentioned. Also esters as low molecular weight compounds are mentioned. Also, according to the present invention, two or more of these compounds can be used. In general, the compounds are present with a molecular weight of less than 3000 g / mol, preferably less than 150 g / mol. Particulate mineral fillers can be, for example, amorphous silica, carbonates such as magnesium carbonate, calcium carbonate (chalk), powdered quartz, mica, various silicates such as clays, muscovite, biotite, suzoite, tin malite, talc, chlorite, phlogopite, feldspar, calcium silicates such as wollastonite or kaolin, especially calcined kaolin.

UV stabilizers include, for example, various substituted resorcinols, salicylates, benzotriazoles and benzophenones, which can generally be used in amounts of up to 2% by weight. According to the invention, oxidation inhibitors and heat stabilizers may be added to the thermoplastic molding compound. Sterically hindered phenols, hydroquinones, substituted representatives of this group, secondary aromatic amines, optionally in combination with phosphorus-containing acids or their salts, and mixtures of these compounds, preferably in concentrations of up to 1% by weight, based on the weight of the mixture , are usable.

Furthermore, according to the invention lubricants and mold release agents, which are usually added in amounts of up to 1 wt .-% of the thermoplastic composition. These include stearic acid, stearyl alcohol, stearic acid alkyl esters and amides, preferably Irganox®, and esters of pentaerythritol with long-chain fatty acids. It is possible to use the calcium, zinc or aluminum salts of stearic acid and also dialkyl ketones, for example distearyl ketone. Furthermore, ethylene oxide-propylene oxide copolymers can also be used as lubricants and mold release agents. Furthermore, natural and synthetic waxes can be used. These include PP waxes, PE waxes, PA waxes, grafted PO waxes, HDPE waxes, PTFE waxes, EBS waxes, montan wax, carnauba and beeswaxes.

Flame retardants can be both halogen-containing and halogen-free compounds. Suitable halogen compounds, wherein brominated compounds chlorinated are preferable, remain stable in the production and processing of the molding composition of the invention, so that no corrosive gases are released and the effectiveness is not impaired. Preference is given to using halogen-free compounds, for example phosphorus compounds, in particular phosphine oxides and derivatives of acids of phosphorus and salts of acids and acid derivatives of phosphorus. Phosphorus compounds particularly preferably contain ester, alkyl, cycloalkyl and / or aryl groups.

Likewise suitable are oligomeric phosphorus compounds having a molecular weight of less than 2000 g / mol, as described, for example, in EP-A 0 363 608.

Furthermore, pigments and dyes may be included. These are generally in amounts of 0 to 15, preferably 0.1 to 10 and in particular 0.5 to 8 wt .-%, based on the buzzer of components A to C, included. The pigments for coloring thermoplastics are generally known, see, for example, R. Gächter and H. Müller, Taschenbuch der Kunststoffadditive, Carl Hanser Verlag, 1983, pp. 494 to 510. As the first preferred group of pigments, white pigments such as zinc oxide, Zinc sulfide, lead white (2 PbC03.Pb (OH) 2), lithopone, antimony white and titanium dioxide. Of the two most common crystal modifications (rutile and anatase-type) of the titanium dioxide, in particular the rutile form is used for whitening the molding compositions according to the invention.

Black color pigments which can be used according to the invention are iron oxide black (Fe304), spinel black (Cu (Cr, Fe) 204), manganese black (mixture of manganese dioxide, silicon oxide and iron oxide), cobalt black and antimony black, and particularly preferably carbon black, which is usually in the form of Furnace or gas black is used (see G. Benzing, pigments for paints, Expert Verlag (1988), p 78ff). Of course, inorganic color pigments such as chromium oxide green or organic colored pigments such as azo pigments and phthalocyanines can be used according to the invention to adjust certain hues. Such pigments are generally available commercially. Furthermore, it may be advantageous to use said pigments or dyes in a mixture, for example, carbon black with Kupferphtha- locyaninen, since in general the color dispersion in the thermoplastics is facilitated. According to a particularly preferred embodiment, the fiber composite material W used according to the invention with a sandwich structure is composed of:

A) 10 to 70 wt .-% thermoplastic material layer w containing

a) 30 to 95% by weight of the thermoplastic molding composition A,

b) 5 to 70% by weight of the reinforcing fibers B,

c) 0 to 40 wt .-% of at least one additive C, and B) 30 to 90 wt .-% of at least one further thermoplastic layer T and / or at least one foam layer S,

wherein the reinforcing fibers B in the form of a gel, a fabric, a mat, a non-woven or a knitted fabric in a maleic anhydride-modified styrene copolymer are used as molding compound A and

wherein the material layer w optionally contains more than three layers.

According to a specific embodiment, the fiber composite material W used according to the invention with a sandwich structure is composed of:

A) 10 to 70 wt .-% thermoplastic material layer w of a thickness of <100 mm, containing. a) from 30 to 95% by weight of a thermoplastic, amorphous molding composition A, based on a styrene copolymer modified by a chemically reactive functionality, wherein the chemically reactive functionality of the thermoplastic molding composition A is preferably based on, 1 to 10% by weight. %, based on the amount of component A, of monomers selected from the group consisting of maleic anhydride, N-phenylmaleimide and glycidyl (meth) acrylate. b) 5 to 70 wt .-% of the reinforcing fibers B, wherein the reinforcing fibers B on the surface one or more chemically reactive functional groups selected from the group hydroxyl, ester and amino groups, wherein the reinforcing fibers B preferably in the form of a Geleges , a fabric, a mat, a fleece or a knit be used. c) 0 to 40 wt .-% of at least one additive C, and

wherein the thermoplastic molding composition A is used in the production of the material

Layer w has at least one chemically reactive functionality which reacts with chemical groups of the surface of the reinforcing fibers B; and

B) 30 to 90 wt .-% of at least one further thermoplastic layer T and / or at least one foam layer S, which is optionally reinforced with at least one short, long or continuous fiber S, in particular with carbon or basalt fibers, wherein the material layer w optionally has a ribbing and / or more than three layers.

Thermoplastic layer T and foam layer S

The thermoplastic layer T and / or foam layer S is or are in the fiber composite material W with a sandwich structure of 10 to 99 wt .-%, preferably from 20 to 95 wt .-%, particularly preferably from 30 to 90 wt .-%, often from 35 to 85 wt .-%, based on the fiber composite material W with sandwich structure included.

For the thermoplastic layer T, the thermoplastics known to those skilled in the art come into question. For example, styrene copolymers such as acrylonitrile-butadiene-styrene copolymers (ABS), styrene-acrylonitrile copolymers (SAN), styrene-methyl methacrylate copolymers (SMMA) and acrylic ester-styrene-acrylonitrile copolymers (ASA), polyolefin Copolymers such as polyethylene (PE) and polypropylene (PP), polycarbonate copolymers (PC), polyethylene terephthalate copolymers (PET), polyetheretherketone copolymers (PEEK) and polyvinyl chloride copolymers (PVC) can be used as component T.

The thermoplastic layer T is preferably processed by injection molding and extrusion.

In a further embodiment, the thermoplastic layer T can be reinforced by the incorporation of short, long or continuous fibers or by appropriate carbon or basalt fibers. The thermoplastic layer T may contain up to 20% by weight, preferably up to 10% by weight, of fibers for reinforcement. Short fibers have an average length of 30 to 100 mm. Long fibers have an average length of 100 to 1000 mm and continuous fibers (also called filaments) have an average length of at least 1000 mm. Even short fibers with a length of a few millimeters can be used.

The polymeric foam layer S has a porous cellular structure, which cells may be open, interconnected or closed. For foaming, almost all known plastics are suitable.

The foam layer S can be foamed physically, chemically or mechanically. In physical foaming, the material is foamed by a physical process such as pressure or temperature change. Physical leavening For example, the gases may be carbon dioxide or nitrogen. During chemical foaming, a propellant, usually in the form of a so-called masterbatch granulate, is added to the plastic granules. For example, chemical leavening agents may be a mixture of sodium bicarbonate and citric acid or carbodiimide. By supplying heat, a volatile constituent of the blowing agent separates, which leads to foaming of the melt. In mechanical foaming, for example, air is stirred into the resin or paste to be foamed. By crosslinking the resin or by gelling the paste, this foam solidifies. Thermoplastic foams such as PS-E (expanded polystyrene), PP-E (expanded polypropylene), PE-E (expanded polyethylene) and PVC-E (expanded polyvinyl chloride), elastomeric foams such as soft polyurethane foam (flexible polyurethane foam), NBR (nitrile rubber) or nitrile-butadiene rubber) and thermosetting foams such as rigid polyurethane foam (rigid polyurethane foam), PF (phenoplast) are mentioned.

In a further embodiment, the sandwich structure contains both at least one thermoplastic layer T and at least one foam layer S.

Production and use of the sandwich structure

The material layer w is in the fiber composite material (organic sheet) W with a sandwich structure of 1 to 90 wt .-%, preferably from 5 to 80 wt .-%, particularly preferably from 10 to 70 wt .-%, often from 15 to 65 wt .-%, based on the fiber composite material W with sandwich structure included.

The material layers w of the organic sheets W with a sandwich structure are preferably processed by injection molding or pressing. Thus, by functional integration, e.g. the injection molding or pressing of functional elements, a further cost advantage can be generated because of further assembly steps, e.g. the welding of functional elements can be dispensed with.

The method of making a sandwich structure comprises the steps of: (i) providing:

(A) at least one thermoplastic molding material A as matrix M containing at least one copolymer A-1 which contains monomers Al (and optionally one or more further (co) polymers (Aa) and / or (Ab)); (B) at least one reinforcing fiber B whose surface has functional groups Bl which can form a covalent bond with the monomers Al;

(C) optionally at least one additive C;

(ii) melting the thermoplastic molding compound A and contacting it with at least one reinforcing fiber B from step (i);

(iii) reacting at least a portion of the monomers A-1 of the copolymer A-1 with at least a portion of the functional groups B-1 of the at least one

Reinforcing fiber B of step (ii) to form covalent bonds;

(iv) optionally, the production of a molding T; (v) optionally curing the product obtained from one of steps (iii) or (iv); and

(vi) contacting the material layer w obtained in steps (i) to (iii), (iv) or (v) with at least one thermoplastic layer T and / or at least one foam layer S.

The manufacturing process of the material layer w may include the phases of impregnation, consolidation and solidification (consolidation) common in the manufacture of composites, which process may be influenced by the choice of temperature, pressure and times employed.

According to a preferred embodiment, the material layer w (a) contains (or consists of) 30 to 95% by weight, often 38 to 70% by weight, of at least one thermoplastic molding compound A,

b) 5 to 70 wt .-%, often 29.9 to 61, 9 wt .-%, at least one reinforcing fiber B, and

c) 0 to 40 wt .-%, often 0.1 to 10 wt .-% of at least one additive C.

Step (ii) of the process, melting the thermoplastic molding composition A and contacting this melt with the reinforcing fibers B, may be accomplished in any suitable manner. In such an impregnation, the matrix M in be transferred to a flowable state and the reinforcing fibers B are wetted to form a boundary layer.

Steps (ii) and (iii) can also be performed simultaneously. Then, immediately upon bringing the thermoplastic molding composition A into contact with the reinforcing fibers B, a chemical reaction takes place in which the monomers Al form a covalent bond with the surface of the reinforcing fibers B (usually via a bond to the functional groups B1) , This may be, for example, an esterification (for example, the esterification of maleic anhydride monomers with silanol groups of a glass fiber). Alternatively, the formation of a covalent bond may also be initiated in a separate step (e.g., by temperature elevation, radical starter, and / or photo-initiation). This can be done at any suitable temperature. The steps (ii) and / or (iii) are carried out at a temperature of at least 200 ° C, preferably at least 250 ° C, more preferably at least 300 ° C, especially at 300 ° C-340 ° C.

In this case, it should preferably be ensured that as far as possible no pyrolysis occurs and that the components used are thermally not decomposed (or only slightly (therefore <50%)). An exception may be: a composition which releases reactive groups by thermal cleavage, such as tert-butyl (meth) acrylate, isobutene is released by thermal elimination at temperatures of about 200 ° C and the remaining functional group (essentially - lend an acid function) can then react with the fiber surface.

According to a preferred embodiment, therefore, when carrying out steps (ii) and / or (iii), the residence time at temperatures of> 200 ° C. is not more than 10 minutes, preferably not more than 5 minutes, more preferably not more than 2 minutes, in particular not more than 1 min. Often 10 to 60 seconds are sufficient for the thermal treatment.

The process, in particular the steps (ii) and (iii), can in principle be carried out at any pressure (preferably atmospheric pressure or overpressure), with and without pressing of the components. When pressed with overpressure, the properties of the material layer w can be improved. According to a preferred embodiment, therefore, the steps (ii) and / or (iii) at a pressure of 5-100 bar and a pressing time of 10-60 s, preferably at a compression pressure of 10-30 bar and a pressing time of 15-40 s, performed. Preferably styrene copolymers provided with at least one chemically reactive functionality (A1), ie amorphous thermoplastic matrices, are used as thermoplastic molding material A. Thus, for the applications described below, the surface quality can be substantially increased compared to the semicrystalline thermoplastics for such cladding parts, because the lower shrinkage of the amorphous thermoplastics, the surface topology, due to the fiber-rich (intersection point in tissues) and fiber-poor regions substantially is improved.

During consolidation, air pockets in the material layer w are reduced and a good bond between thermoplastic molding compound A and reinforcing fibers B (in particular, when it is stratified reinforcing fibers fibers B) is produced. It is preferred, after impregnation and consolidation to obtain a (as far as possible) non-porous composite material. Alternatively, said steps (i) to (iii), (iv) or (v) may be carried out in separate sequence. For example, first layers of reinforcing fibers B can be prepared with differently prepared reinforcing fibers B, wherein an impregnation of the reinforcing fibers B takes place with the matrix of thermoplastic molding material A. Thereafter, impregnated layers of reinforcing fibers B with different fiber-matrix adhesion can be present, which can be consolidated in a further working step to form a material composite as a material layer w.

Before the layers of reinforcing fibers B are laminated with the matrix of thermoplastic molding material A, at least a part of the reinforcing fibers B may be subjected to a pretreatment in the course of which the subsequent fiber-matrix adhesion is influenced. The pretreatment may include, for example, a coating step, an etching step, a heat treatment step or a mechanical surface treatment step. In particular, for example, by heating a part of the reinforcing fibers B, an already applied adhesion promoter can be partially removed.

The reinforcement layers can be completely interconnected during the manufacturing process (laminating). Such fiber composite material mats offer optimum mierte strength and stiffness in the fiber direction and can be processed particularly advantageous.

The method can also include the production of a molded part T. According to a preferred embodiment, the method comprises, as a further step (iv), a three-dimensional shaping to form a molding T.

This can be done in any way, such as by mechanical shaping by a shaping body, which may also be a roller embossed. Preferably, the still mouldable material layer w, in which the thermoplastic molding material A still present (partially) melted shaped. Alternatively or additionally, a hardened material layer w can be cold-formed.

Preferably, a (substantially) solid molding T is obtained at the end of the process.

Preferably, therefore, the process comprises as a further step (v) the curing of the product obtained from one of the steps (iii) or (iv).

This step can also be called solidification. The solidification, which generally takes place with removal of heat, can then lead to a ready-to-use molded part T. Optionally, the molding T may be further finished (e.g., deburred, polished, colored, etc.).

The process can be carried out continuously, semicontinuously or discontinuously. According to a preferred embodiment, the process is carried out as a continuous process, in particular as a continuous process for producing smooth or three-dimensionally embossed films. Alternatively, it is also possible to produce shaped parts T semi-discontinuously or discontinuously. The material layer w preferably has a thickness of <100 mm, in particular of <20 mm, preferably of <10 mm, especially of <5 mm.

The corresponding fiber composite material W with sandwich structure has a thickness of wherein the material layer w has a thickness of <1000 mm, preferably of <100 mm, often of <10, especially <4 mm.

The material layers w have an amorphous, thermoplastic matrix M. These can be applied by injection molding with a ribbing, laminated on a foamed thermoplastic core or on a honeycomb core as cover layers (welded). The improvement of the component stiffness by a ribbing (formation of a ribbed structure) is justified by the increase of the area moment of inertia. In general, optimal rib dimensions include production, aesthetics and design considerations.

The reinforcing fibers B may be layer-wise impregnated and consolidated in layers of (or as sheets of F) reinforcing fibers B in a single processing step with the matrix M containing a thermoplastic molding material A. The production of the material layer w can be carried out in this way in a particularly efficient manner.

An advantage of the styrene copolymers as amorphous thermoplastics (for example SAN) is the partially high scratch resistance of these materials W. This has the advantage in the application examples described below that the covering parts do not scratch during assembly and later use.

The required rigidity and strength of the material layer w is achieved by a sandwich composite or z. B. achieved by a ribbing.

As core material in the sandwich composite both a foam core (e.g., Rohacell from Evonik) and a honeycomb core (e.g., Honeycomps from EconCore) can be used. In order to achieve a cohesive bond between the material layer w and the core, the core consists of a chemically compatible thermoplastic in order to be able to weld by means of heat and to facilitate lamination in the production process.

A preferred way to achieve sufficient rigidity for, for example, covering, is the injection molding or pressing back of a ribbing in the injection molding or in the pressing process.

In order here to achieve a material connection between the ribs and the material layer w, a suitable thermoplastic molding composition, in particular one of the o.g. Styrene copolymers are used. Preferably, a SAN, ABS or ASA-based thermoplastic molding composition is used.

Functional integration can add another cost advantage to the injection molding process. For example, assembly steps can be saved in the holder, guides, locks, snap hooks, etc. can be molded directly with. In a further embodiment, it is provided that further groups of reinforcing fibers B are coupled to the matrix M via further, differing fiber matrix adhesions.

If three or more groups of reinforcing fibers B with different fiber-matrix adhesions are used, the behavior of the material layer w and thus also of the fiber composite material W with a sandwich structure can be influenced in a targeted and highly individual manner. In each case different types of fibers or the same types of fibers can be used.

For example, groups of reinforcing fibers B may each be provided with different adhesion promoter compositions effecting the different fiber matrix adhesions. The different compositions may differ only in the concentrations or have other compositions. It is essential that significantly different fiber-matrix adhesions are set by the different adhesion promoter compositions.

Already in the production of the reinforcing fibers of the primer can be applied as part of the size. However, it may also be provided an additional process of thermal desizing or other desizing that destroys or removes the already applied sizing. Subsequently, the reinforcing fiber can then be coated with a finish containing the coupling agent and adapted to the particular matrix and the desired fiber-matrix adhesion. Alternatively, plastic layers can also be used.

For example, in the material layer w according to the invention, it is possible to use adhesion promoters which comprise crosslinkable polyether urethane and polyester urethane polymers which act as film formers, together with an aminosilane adhesion promoter.

In step (vi), the at least one thermoplastic layer T and / or at least one foam layer S are brought into contact with the material layer w, preferably by lamination or (co) extrusion.

Furthermore, by means of the tool wall, an additional amorphous thermoplastic layer T on the material layer w and a nonwoven, which has at least a grammage of 50 g / m ² and is sandwiched between the material layer w and the thermoplastic layer T a Narbung be molded, bringing the Surface can be additionally functionalized (scratch resistance, concealment of sink marks). Depending on requirements, the additional thermoplastic layer T can be colored opaque, so that optically no material layer w can be assumed, or one can specifically induce a so-called "fiber look" by the use of a transparent layer.

The use of material layers w in sandwich composite or by means of ribbing can reduce costs and at the same time reduce the weight, which on the one hand can facilitate the assembly of the component and on the other hand of the device.

The inventive use of organo sheets W with sandwich structures as a replacement of metals, the cost and weight can be reduced, since the density of the contained organo sheets W sandwich structure is much lower and the lack of rigidity, compared to steel, by a Ribbing or a sandwich construction can be compensated. The ribbing preferably consists of an injection molding material, which ensures a cohesive connection to the material layer w and thus gives rise to a high moment of resistance. In the sandwich construction, there is also a similarity, so that here, too, creates a cohesive bond. Alternatively, the foam core can be glued to the cover layers or it is caused by an additional thermoplastic layer T on the material layer w a claw in the foam structure.

Applications of the sandwich structure may, for example, be as follows:

The material layers w according to the invention are used in conjunction with further layers. By way of example, the following constructions are mentioned (w = material layer according to the invention, S = foam layer, T = thermoplastic layer): w-X,

w-X-w,

X-w-x, or

w-X-w-X, where X is T and / or S.

Optionally, the thermoplastic layer T may be reinforced by incorporation of short, long or continuous glass fibers or corresponding carbon or basalt fibers. A further embodiment according to the invention comprises the combination of material layer w with a foam layer S, wherein the foam layer S is produced by extrusion, coextrusion, lamination or by foam injection molding. The foam layer S consists of thermoplastic molding compositions which have been produced by chemical (eg sodium bicarbonate / citric acid, carbodiimide) or physical blowing agents (eg CO 2, N 2).

FIG. 1 shows the fiber composite material layers w, which according to test no. 1 were obtained. FIG. 1A shows the visual documentation. FIG. 1B shows the microscopic view of a section through the laminar fiber composite material layer w arranged in a horizontal orientation (left: 25-fold magnification, right: 50-fold magnification), the fibers clearly showing as a horizontally extending dark layer between the light layers of thermoplastic molding material can be seen. Figure 1 C shows the 200-fold magnification, it can be seen that the impregnation is not completed in some places.

FIG. 2 shows the fiber composite material layers w, which after test no. 2 were received. FIG. 2A shows the visual documentation. FIG. 2B shows the microscopic view of a section through the laminar fiber composite material layers w arranged in a horizontal orientation (left: 25-fold magnification, right: 50-fold magnification), wherein the fibers clearly show extending dark layer between the light layers of thermoplastic molding material can be seen. Figure 2C shows the magnification of 200 times, whereby it can be seen that the impregnation is partially not completed.

FIG. 3 shows the fiber composite material layers w, which according to test no. 3 were obtained. FIG. 3A shows the visual documentation. FIG. 3B shows the microscopic view of a section through the laminar fiber composite material layers w arranged in the horizontal orientation (left: 25-fold magnification, right: 50-fold magnification), with no layer is recognizable from fibers. Figure 3C shows the 200-fold magnification, it can be seen that the impregnation is largely completed.

FIG. 4 shows the fiber composite material layers w, which according to test no. 4 were obtained. FIG. 4A shows the visual documentation. FIG. 4B shows the microscopic view of a section through the laminar fiber composite material layer w arranged in a horizontal orientation (left: 25 × magnification, right: 50 × fold magnification), whereby no layer of fibers is recognizable. Figure 4C shows the 200-fold magnification, it can be seen that the impregnation is not completely completed at individual points. FIG. 5 shows the fiber composite material layers w, which according to test no. 5 were obtained. FIG. 5A shows the visual documentation. FIG. 5B shows a microscopic view of a section through the laminar fiber composite material layer w arranged in a horizontal orientation (left: 25-fold magnification, right: 50-fold magnification), wherein no layer of fibers is recognizable. Figure 4C shows the 200-fold magnification, it can be seen that the impregnation is not completely completed in a few places.

FIG. 6 shows the production of the fiber composite material layers w (here: glass fiber fabric) in the press inlet V25-V28. It is clearly recognizable that such a production process allows continuous production. In addition, it can be seen from the embossing of the pattern that the fiber composite material layer w can also be shaped in three dimensions.

FIG. 7 shows schematically the development of undesired formation of surface waves (texture).

The invention is described in more detail in the following examples, figures and claims. Examples

The following experiments were carried out on a commercially available interval hot press, which is capable of producing a fiber / film composite of polymer film, melt or powder, for the quasi-continuous production of fiber-reinforced thermoplastic semi-finished products, laminates and sandwich panels.

Plate width: 660 mm

Laminate thickness: 0.2 to 9.0 mm

Laminate tolerances: max. ± 0.1 mm according to semi-finished product

Sandwich panel thickness: max. 30 mm

Output: approx. 0.1 - 60 m / h, depending on quality and component thickness

Nominal feed 5 m / h

Tool pressure: Press unit 5-25 bar, infinitely variable for minimum and maximum tool size (optional) Mold temperature control: 3 heating and 2 cooling zones

Tool temperature: up to 400 ° C

Tool length: 1000 mm

Opening travel press: 0.5 to 200 mm

preferred direction of production: right to left

Technical data of melt plasticization are:

Discontinuous melt application in middle position for the production of fiber-reinforced thermoplastic semi-finished products:

Screw diameter: 35mm

Max. Stroke volume: 192 cm ³

Max. Screw speed: 350 rpm

Max. Discharge flow: 108 cm ³ / s

Max. Discharge pressure: 2406 bar specific

The described fiber composite materials W (organic sheets) with sandwich structures containing material layer w, in particular with amorphous, thermoplastic matrix are particularly suitable for the production of molded parts. Some examples are shown below.

Unless otherwise stated, the moldings are manufactured by injection molding.

Production of the material layer m

40 wt .-%, based on the material layer, of an acrylonitrile-styrene-maleic anhydride copolymer as thermoplastic molding composition A (prepared from: 75 wt .-% styrene, 24 wt .-% acrylonitrile and 1, 0 wt .-% Maleic anhydride) is with

60 wt .-%, based on the material layer, a glass-based reinforcing fiber with chemically reactive functionality (silane groups) on the surface compounded [GW 123- 580K2 of P-D Glasseiden GmbH].

Production of the material layer n

65 wt .-%, based on the material layer, of an acrylonitrile-butadiene-styrene copolymer as the thermoplastic molding composition A (ABS prepared from: 45 wt .-% butadiene, 30 wt .-% styrene, 24 wt .-% acrylonitrile and 1 wt .-% maleic anhydride) is with 35 wt .-%, based on the material layer, a glass-based reinforcing fiber with chemically reactive functionality (silane groups) on the surface compounded [GW 123- 580K2 of PD Glasseiden GmbH]. The material layer is subsequently ribbed.

Example 1: Production of a fiber composite material with sandwich structure, containing material layer m

The material m is coextruded with an expanded polystyrene (X-PS, made of polystyrene 158 K with C0 ₂ / ethanol as blowing agent) on a tandem extruder with a thickness of 10 mm to obtain a sandwich structure.

The resulting fiber composite material with sandwich structure has a sequence of m / X-PS / m.

Example 2 Production of an Organic Sheet Sandwich Structure Containing Material Layer n

The material n is coextruded with an expanded polystyrene (X-PS, made of polystyrene 158 K with CO 2 / ethanol as blowing agent) on a tandem extruder with a thickness of 10 mm to obtain a sandwich structure.

The obtained fiber composite material having a sandwich structure has a sequence of: n / X-PS / n

The organic sheets according to the invention with sandwich structures from Examples 1 and 2 are more robust than the corresponding organo sheets without sandwich structure m and n.

Further examples for the production of the thermoplasmic fiber composite material layer w

Dangerous thermoplastic combinations A: A1 (comparative): S / AN with 75% styrene (S) and 25% acrylonitrile (AN), viscosity number 60, Mw of 250,000 g / mol (measured via gel permeation chromatography on standard columns with monodisperse polystyrene calibration standards)

A2: S / AN / maleic anhydride copolymer having the composition (wt%): 74/25/1, Mw of 250,000 g / mol (measured via gel permeation chromatography on standard columns with monodisperse polystyrene calibration standards)

A3: mixture of A2: A1 = 2: 1

A4: mixture of A2: A1 = 1: 2

Used fiber textiles B:

B1: Bidirectional glass fiber substrate 0/90 ° (GF-GE) with basis weight

590g / m ² ,

Weft + warp = 1200tex [for example KN G 590.1 from P-D Glasseiden GmbH]

B2: glass fiber fabric twill 2/2 (GF-KG) with basis weight = 576 g / m ² ,

Weft, + chain = 1200tex The combinations and parameter settings made in connection with experiments no. 1 -5 are listed in the following table:

Table 1 . Production conditions of the fiber composite material layers w

Experimental composite ^* Temperature profile Pressing pressure Pressing time Thickness No. (bar) (s) (mm)

1 (See) A1 + B1 220-240-260-160-80 20 20

¹¹

2 (See) A1 + B1 220-280-300-160-80 25 30

¹¹

3 A2 + B1 240-300-320-160-80 20 20

¹¹

4 A3 + B1 240-300-320-160-80 20 30

¹¹

5 A4 + B1 240-300-320-160-80 20 30

¹ ^* Components A + B1: 0.465 mm Thickness Textile structure, 0.653 mm thickness Matrix structure, total volume Matrix: 22 ml, fiber volume fraction: 41.6%, total density Semi-finished product: 1.669 g / ml, total thickness Semi-finished product: 1 .1 17 mm Experiment no , 1 (comparative experiment)

The results are shown in FIG.

Visual assessment on the semi-finished surface:

Macro Impregnation: completed

Micro-impregnation: clearly not completed

Microscopic evaluation in semi-finished products:

Matrix layer in middle position: clearly visible

Matrix layer in top layer: not visible on the roving

Impregnation Warp threads: Central unimpregnated areas, all around slightly impregnated Impregnation Weft threads: in the middle clearly unimpregnated areas, all around slightly impregnated

Air inclusions: little, only in roving

Consolidation: insufficient, damage warp and weft threads

Experiment no. 2

The results are shown in FIG.

Visual assessment on the semi-finished surface:

Macro Impregnation: completed

Micro-impregnation: not completed in several places Microscopic evaluation in semifinished products:

Matrix layer in middle position: recognizable

Matrix layer in top layer: little recognizable by the roving

Impregnation Warp threads: Central unimpregnated areas visible, partially impregnated all around, partially unimpregnated

Impregnation Weft threads: in the middle unimpregnated areas, all around slightly impregnated

Air inclusions: little

Consolidation: insufficient, significant damage weft threads Experiment no. 3

The results are shown in FIG.

Visual assessment on the semi-finished surface:

Macro Impregnation: completed

Micro-impregnation: completed

Experiment No. 3, Microscopic Evaluation in the Semi-Finished Interior:

Matrix layer in middle position: not recognizable

Matrix layer in top layer: easily recognizable

Impregnation Warp threads: hardly any unimpregnated areas visible, all-round well impregnated

Impregnation Weft threads: hardly any unimpregnated areas visible, all-round well impregnated

Air inclusions: many, large bubbles visible

Consolidation: good, no damage

Experiment no. 4

The results are shown in FIG. Visual assessment on the semi-finished surface:

Macro Impregnation: completed

Micro-impregnation: mostly completed

Microscopic evaluation in semi-finished products:

Matrix layer in middle position: hardly recognizable

Matrix layer in cover layer: recognizable

Impregnation Warp threads: Slightly unimpregnated areas visible, all-round well impregnated

Impregnation Weft threads: unimpregnated areas visible, but impregnated all around

Air inclusions: none recognizable

Consolidation: satisfactory, average damage of weft threads visible Experiment no. 5

The results are shown in FIG.

Visual assessment on the semi-finished surface:

Macro Impregnation: completed Micro-impregnation: mostly completed

Microscopic evaluation in semi-finished products:

Matrix layer in middle position: not recognizable

Matrix layer in cover layer: recognizable

Impregnation warp threads: little unimpregnated areas visible, all-round well impregnated

Impregnation Weft threads: little unimpregnated areas recognizable, all-round well impregnated

Air inclusions: none recognizable

Consolidation: partly good, partly insufficient, local damage of weft threads recognizable

Summary of the test results

Table 2. Summary trials and evaluation

^* Components A + B1: 0.465 mm Thickness Textile structure, 0.653 mm thickness Matrix structure, total volume Matrix: 22 ml, fiber volume fraction: 41.6%, total density Semi-finished product: 1.669 g / ml, total thickness Semi-finished product: 1 .1 17 mm

^** 1 = perfect, 2 = good, 3 = partial, 4 = low, 5 = poor / none

Table 3. Comparison of the experimental settings according to the invention with conventional organo sheets Experimental composite maleic acid upper printability

No anhydride surfaces with 45 mdyne

Concentration grade ^* Ink ^**

tion

(% By weight)

1 (Cf.) A1 + B1 0 2 1

2 (Cf.) A1 + B1 0 2

3 A2 + B1 1 1 -2

4 A3 + B1 0.66 1 -2 1

5 A4 + B1 0.33 1 -2

6 Bond Laminates 0 4-5

Composite of approx

60% fiberglass fabric and 40%

polyamide

7 composite from approx. 0 4-5 5

60% fiberglass fabric and 40%

polypropylene

^* 1 = completely smooth, 2 = largely smooth, 3 = slightly rough, 4 = moderately rough, 5 = fibers are clearly noticeable

^** 1 = perfect, 2 = good, 3 = partial, 4 = low, 5 = poor / none

Experiment no. 6

The results are shown in Table 5.

The combinations and parameter settings made in connection with experiment No. 6 are listed in the following table:

Table 4. Fabrication conditions of the fiber composite material layers w

4 A1 + B1 220-240-300-160-80 20 20 1

12 A3 + B1 220-240-300-160-80 20 20 1

28 A1 + B2 240-300-320-160-80 20 20 1

26 A3 + B2 240-300-320-160-80 20 30 1 ^* Components A + B1: 0.465 mm Thickness Textile structure, 0.653 mm thickness Matrix structure, total volume Matrix: 22 ml, fiber volume fraction: 41.6%, total density Semi-finished product: 1.669 g / ml, total thickness Semi-finished product: 1 .1 17 mm

Table 5. Comparison of flexural strength.

Table 5 shows the fiber composite material layers w (or fiber composite materials W) obtained in a series of experiments. Pure SAN (A1) and an S / AN / maleic anhydride copolymer (A2) were combined and tested with a commercial scrim and fabric reinforcement in an identical process. The fiber volume content of the composites was 42%. The improved quality of the impregnation and bonding between fiber and matrix is not shown by the flexural rigidity, but clearly by the flexural strength (fracture stress) of the examined samples.

Examples of multilayer organic sheets

The described fiber composite material layers w (organic sheets), in particular with amorphous, thermoplastic matrix, are particularly suitable for the production of moldings, films and coatings. Some examples are shown below. Unless otherwise stated, the moldings are made by injection molding. Example 1: Production of the fiber composite material M

40 wt .-%, based on the fiber composite material layers w, of an acrylonitrile-styrene-maleic anhydride copolymer as thermoplastic molding material A (prepared from: 75 wt .-% of styrene, 24 wt .-% acrylonitrile and 1 wt. % Maleic anhydride) is with 60 wt .-%, based on the fiber composite material layer w, a glass-based reinforcing fiber with chemically reactive functionality (silane groups) compounded on the surface [GW 123-580K2 of PD Glasseiden GmbH]. Example 2: Production of the fiber composite material layer N

65 wt .-%, based on the fiber composite material layer w, of an acrylonitrile-butadiene-styrene copolymer as the thermoplastic molding composition A (ABS prepared from: 45 wt .-% butadiene, 30 wt .-% styrene, 24 wt. % Acrylonitrile and 1% by weight maleic anhydride) is mixed with 35% by weight, based on the fiber composite material layer w, of a glass-based reinforcing fiber with chemically reactive functionality (silane groups) on the surface [GW 123- 580K2 from PD Glasseiden GmbH]. The fiber composite material layer w is subsequently ribbed. Example 3: Production of molded parts from the fiber composite material layers M and N.

Example A: Washing machine window

Example B: Lens covers

Increased rigidity of the window and lens cover over corresponding glass materials is observed. In addition, the Orga- nobleche are less sensitive to scratches and pressure.

Further Bending Stress Tests on Sheet-Reinforced Fiber Composites The components are as defined above. The bending stress and the flexural modulus were determined according to DIN 14125: 201 1 -05.

The combinations and parameter settings for the method described in claim 1 are listed in the following table:

Table 1: Compounds Cf. 1, Vgl. 2, Vgl. 10 and Vgl. 15 as well as the compositions according to invention V3 to V9 and V1 1 to V14. X: weight ratio component A: B = 60: 40 No. A1 A2 A3 A4 B1 B2 T [° C] t [s]

See 1 X X 260 20-30

See 2 X X 300 30-30

V3 X X 280 20-30

V4 X X 280 40

V5 X X 320 30-30

V6 X X 300 20-30

V7 X X 320 20-30

V8 X X 310 20-30

V9 X X 320 20-30

See 10 X X 320 20-30

V1 1 X X 320 20-30

V12 X X 320 20-30

V13 X X 320 20-30

V14 X X 320 20-30

Cf. 15 X X 320 20-30

Table 6 shows the conditions of the experiments carried out.

Here, the educts, and the temperature and the pressing time were varied. The pressing pressure was approximately 20 bar in all test series.

Table 7: Average values of the maximum bending stress of the warp and weft directions of the produced organic sheets according to the blends Cf. 2, V5, V7, V9, Cf. 10, V12 to V14 and Cgl. 15, wherein the production temperature was at least 300 ° C.

No. Fiber direction Average values of maximum bending stress [MPa]

Cf. 2 warp direction 21 1, 23

Weft direction 184.94

V5 warp direction 670.48

Weft direction 271, 05

V7 warp direction 590.98

Weft direction 301, 21

V9 warp direction 371, 73

Weft direction 244.62

Cf. 10 warp direction 319.8

Weft direction 236.01

V12 warp direction 556.15

Weft direction 484,24 V13 warp direction 528.96

Weft direction 386.83

V14 warp direction 513.95

Weft direction 413.86

Cf. 15 warp direction 423.03

Weft direction 301, 40

The values shown in Table 7 are the average of nine measurements each.

Table 7 shows that the organic sheets V5, V7, V9, V12, V13 and V14 according to the invention have a higher mean maximum bending stress than the organo sheets comprising a matrix containing 75% by weight of styrene (S) and 25% by weight of acrylonitrile ( AN) (See Figures 10 and 15). The comparison of V9 with Cf. 10 shows that under the same conditions (T = 320 ° C and t = 30 s), the organic sheet according to the invention has a greater bending stress in both the warp and in the weft direction.

It can be seen that improved products can be obtained by the process for producing the fiber composite material layer w (and thus also of the entire fiber composite material W) with a thermoplastic molding compound A, reinforcing fibers B.

Further investigation of multi-layer fiber composite materials Technical Data of the Interval Hot Press (IVHP):

Quasi-continuous production of fiber-reinforced thermoplastic semi-finished products, laminates

and sandwich panels

Plate width: 660 mm

Laminate thickness: 0.2 to 9.0 mm

Laminate tolerances: max. ± 0.1 mm according to semi-finished product

Sandwich panel thickness: max. 30 mm

Output: approx. 0.1 - 60 m / h, depending on quality and component thickness

Nominal feed 5 m / h

Tool pressure: Press unit 5-25 bar, infinitely variable for minimum and maximum tool size (optional)

Mold temperature control: 3 heating and 2 cooling zones

Tool temperature: up to 400 ° C

Tool length: 1000 mm Opening travel press: 0.5 to 200 mm

Production direction: right to left

Technical data of melt plasticization:

Medium-length discontinuous melt application for the production of fiber-reinforced thermoplastic

semifinished

Screw diameter: 35mm

Max. Stroke volume: 192 cm ³

Max. Screw speed: 350 rpm

Max. Discharge flow: 108 cm ³ / s

Max. Discharge pressure: 2406 bar specific

here:

Melt volume: 22 cc

isobar = pressure-controlled pressing process

isochor = volume-controlled pressing process

T [° C] = temperature of the temperature zones ^* ( ^* The press has 3 heating zones and 2 cooling zones.

p [bar] = pressing pressure per cycle: Isochor 20

s [mm] = travel limit Press thickness: 1 .1 mm

Temperature profile: (i) 210 to 245 ° C, therefore approx. 220 ° C

(ii) 300 to 325 ° C, therefore about 300 ° C

(iii) 270 to 320 ° C, therefore about 280 to 320 ° C

(iv) 160 to 180 ° C

(v) 80 ° C

t [sec] = pressing time per cycle: 20-30 s

Construction / lamination: 6-layer structure with melt middle layer; Manufacturing Method: Melt Direct (SD) Matrix Components A:

M1 (SAN type): styrene-acrylonitrile-maleic anhydride (SAN-MA) terpolymer (S / AN / MA: 74/25/1) with an MA content of 1% by weight and an MVR of 22 cm ³ / 10 min at 220 ° C / 10kg (measured to IS01 133); M1 b corresponds to the abovementioned component M1, the matrix additionally being admixed with 2% by weight of carbon black. M2 (SAN type): styrene-acrylonitrile-maleic anhydride (SAN-MA) terpolymer (S / AN / MA: 73/25 / 2.1) with an MA content of 2.1% by weight and an MVR of 22 cm ^3/10 min at 220 ° C / 10kg (measured according to IS01 133); M2b corresponds to the abovementioned component M2, the matrix additionally being admixed with 2% by weight of carbon black.

M3 (SAN type): blend of 33% by weight of M1 and 67% by weight of the SAN copolymer Luuran VLN, therefore 0.33% by weight of maleic anhydrideMA) in the entire blend;

M3b corresponds to the abovementioned component M3, the matrix additionally being admixed with 2% by weight of carbon black.

PA6: semi-crystalline, easy-flowing polyamide Durethan B30S

PD (OD): easy flowing, optical grade amorphous polycarbonate

Discs);

Fiber components B:

Glass filament cooper fabric (short names: GF-KG (LR) or LR), twill weave 2/2, basis weight 290 g / m ² , roving EC9 68tex, finish TF-970, delivery width 1000 mm (type: 01 102 0800-1240; Manufacturer: Hexcel, obtained from: Lange + Ritter)

Glass filament cooper fabric (short designations: GF-KG (PD) or PD), twill weave 2/2, basis weight 320 g / m ² , roving 320tex, finish 350, delivery width 635 mm (type: EC14-320-350, manufacturer and supplier : PD Glasseide GmbH Oschatz)

Glass filament scrim (short name: GF-GE (Sae) or Sae) 0 45 90 -45 °, weight per unit area 313 g / m ² , main roving 300tex, finish PA size, delivery width

655mm (Type: X-E-PA-313-655, No. 7004344, manufacturer and supplier: Saertex

GmbH & Co. KG)

Sae ns = glass filament scrim 300 g / m ² , manufacturer's name: Saertex new sizing, + 457-457 + 457-45 °

Glass fiber fleece (short name: GV50), basis weight 50 g / m ² , fiber diameter 10 μηη, delivery width 640 mm (Type: Evalith S5030, manufacturer and supplier: Johns Manville Europe) Visual rating

All produced composite fiber materials could be produced in each case as (large) sheetlike Orga- nobleche in a continuous process, which could be cut to size (in laminatable, customary transport dimensions such as 1 m x 0.6 m). In the case of transparent fiber composite materials, the embedded fiber material was just recognizable in the backlight when examined in detail. In the fiber composite materials with a (black) colored matrix, the embedded fiber material was not / hardly recognizable even under closer light in the backlight. Microscopic evaluation

In this case, defects (voids, incidence, etc.) were evaluated by incident light microscopy and the surface quality via confocal laser scanning microscopy (LSM). Using LSM, a top view of a three-dimensional (3D) height image (7.2 mm x 7.2 mm) of the local measuring range and a two-dimensional (2D) representation of the height differences after scaling and application of different profile filters was created. Measurement errors and a general distortion / skew of the sample were compensated by the use of profile filters (noise filter and tilt filter). The 2D height profile of the image was transmitted via defined measuring lines by integrated software in line profiles and evaluated computer-assisted.

Fiber-composite materials with four embedded layers of the respective fabric of fibers (here GF-KG (PD) (4) or Sae (4)) were produced in the respective matrix. In order to further increase the comparability of the samples, a thin fiberglass mat (GV50, see above) was applied to the produced fiber composite materials on both sides. This had no noticeable influence on the mechanical properties.

The mean wave depth (MW Wt) and the spatial ration value (Ra) were determined for numerous fiber composite materials. It was shown that the MW Wt is clearly <10 μm for all fiber composite materials in which the matrix contains a functional component that can react with the fibers, whereas in fiber composite materials with comparable PA6 and PD (OD) matrices is clearly <10 μηη. The determined spatial values were also significantly lower for composite fiber materials according to the invention. By way of example, these are the measured values below.

Table 8. LSM Measurement Results with SAN Matrix System - Wave Depth (Wt) and Stellite (Ra) SAN (1) PC (1) PA6 (1)

Construction + GF-KG (PD) (4)

Components PC (OD) + PA6 +

M1 b + PD M2 + PD M2b + PD M3b + PD PD PD

MW Wt 7,141 7,187 5,181 5,425 1 1, 745 12,323

MW Ra 3.995 4.415 4.17 3.451 6.406 4.968

This was just as clear when a clutch (such as Sae) is used instead of the fabric: Table 9. Measurement results of the LSM measurement with SAN matrix system - wave depth (Wt) and spatial resolution (Ra)

In further tests, the strength in the warp and weft directions was examined separately. It could be shown that the fiber composite materials are very stable in both warp and weft directions. In the warp direction, the fiber composite materials are usually even more stable than in the weft direction.

Mechanical properties

Matrix components A

The matrix components A are as described above.

Fiber components B (unless described above)

FG290 = glass filament fabric 290g / m ² , manufacturer's name: Hexcel HexForce® 01202 1000 TF970

FG320 = glass filament fabric 320g / m ² , manufacturer's name: PD Glasseide GmbH Oschatz EC 14-320-350

Sae = MuAx313, glass filament scrim 300g / m ² , manufacturer's name: Saertex XE-PA-313-655 Sae ns = glass filament scrim 300g / m ² , manufacturer's name: Saertex new sizing, + 457-457 + 457-45 ° Number of layers (eg 4x = four layers of the respective fiber fabric or the respective fibers)

The following transparent fiber composite materials were produced, in each of which flat fiber material was introduced. The fiber composite materials produced each had a thickness of about 1, 1 mm. In order to further increase the comparability of the samples, a thin fiberglass mat (GV50, see above) was applied to the produced fiber composite materials on both sides. This has no noticeable influence on the mechanical or optical properties. The following bending strengths according to DIN EN ISO 14125 were determined for the samples:

Table 10. Transparent fiber composite materials - bending strength

The following black-dyed fiber composite materials were also produced in which the matrix was mixed with 2% by weight of carbon black and introduced into the respective flat fiber material. The fiber composite materials produced each had a thickness of about 1, 1 mm. In order to further increase the comparability of the samples, a thin fiberglass mat (GV50, see above) was applied to the produced fiber composite materials on both sides. This has no noticeable influence on the mechanical or optical properties. The following bending strengths according to DIN EN ISO 14125 were determined for the samples:

Table 1 1. Intransparent fiber composite materials - bending strength

No. Composition Glass proportion Matrix Thickness Modulus Bending [g / m ² ] [mm] Strength

F / S_1 4xFG290 1260 M2 1, 07 21, 61 661, 73

F / S_2 4xFG320 1380 M2 1, 20 22.70 673.99 F / S_3 4xSae 1352 M2 1, 15 14,92 385,21

F / S_4 4xSae 1352 PA6 1, 13 14.30 477.77

F / S_5 4xFG320 1380 PA6 1, 1 1 16,95 471, 97

In summary, it was found that the fabrics used (FG290 and FG320) can be processed into fiber composites with particularly high flexural strength. The fiber composite materials according to the invention in which the matrix contains a component which reacts with the fibers (here: maleic anhydride (MA)) have a significantly higher flexural strength than the comparative molding compositions without such a component, such as PC (OD) or PA6.

By comparison, only a bending strength of 150 MPa was found for the fiberglass material Luran 378P G7, which is not according to the invention and reinforced with short glass fibers, and therefore has a significantly lower flexural strength. In addition, the impact resistance and puncture behavior (Dart Test to ISO 6603) was determined for the fiber composite materials. Here, too, the fiber composite materials showed a high stability of Fm> 3000 N. Optional further processing

It could also be shown experimentally that the resulting fiber composite materials were well convertible to three-dimensional semi-finished products, such as semi-shell-shaped semi-finished products. It was also found that the resulting fiber composite materials could be printed and laminated.

Summary of the test results

The evaluation of different textile systems based on glass fibers with different matrix systems to a fiber composite material (organic sheet) has shown that good fiber composite materials (as organic sheets and semi-finished products made from them) can be produced reproducibly. These can be made colorless or colored. The fiber composite materials showed good to very good optical, haptic and mechanical properties (such as with regard to their flexural strength and puncture resistance). Mechanically, the tissues showed somewhat greater strength and rigidity than scrim. The styrene copolymer-based matrices (SAN matrices) tended to result in better fiber composite materials in terms of mechanical properties than the alternative matrices such as PC and PA6. The fiber composite materials according to the invention could be produced semi-automatically or fully automatically by means of a continuous process. The fiber composite materials (organo-nobleche) according to the invention can be easily transformed into three-dimensional semi-finished products.

Claims

claims

1 . Use of a fiber composite material W with sandwich structure,

built from:

A) at least one thermoplastic material layer w,

containing as components in the production

a) at least one thermoplastic molding compound A as matrix,

b) at least one layer of reinforcing fibers B, and

c) optionally at least one additive C,

B) at least one further thermoplastic layer T, which is different from the layer w, and / or at least one foam layer S, said further layer T and / or S being permanently connected to the material layer w; for the production of molded parts.

2. Use of a fiber composite material W with a sandwich structure according to claim 1, wherein it consists of:

A) 10 to 70 wt .-% thermoplastic material layer w containing

a) from 30 to 95% by weight of the thermoplastic molding composition A, b) from 5 to 70% by weight of the reinforcing fibers B,

c) 0 to 40 wt .-% of at least one additive C, and

B) 30 to 90 wt .-% of at least one further thermoplastic layer T and / or at least one foam layer S.

Use of a fiber composite material W with sandwich structure according to claim 1 or 2, wherein the thermoplastic molding material A is amorphous and based on a, modified by a chemically reactive functionality styrene copolymer.

Use of a fiber composite material W with sandwich structure according to one of claims 1 to 3, wherein the thermoplastic molding composition A is selected from the group of, modified by a chemically reactive functionality copolymers consisting of: styrene-acrylonitrile copolymers, o methylstyrene Acrylonitrile copolymers, impact-modified acrylonitrile-styrene Copolymers, in particular acrylonitrile-butadiene-styrene copolymers (ABS) and acrylonitrile-styrene-acrylic ester copolymers (ASA), and blends of said copolymers with polycarbonate or polyamide.

Use of a fiber composite material W with sandwich structure according to one of claims 1 to 4, wherein the chemically reactive functionality of the thermoplastic molding material A based on components selected from the group consisting of maleic anhydride, N-phenylmaleimide and glycidyl (meth) acrylate.

Use of a fiber composite material W with sandwich structure according to one of claims 1 to 5, wherein the thermoplastic molding composition A from 0.1 to 10 wt .-% of monomers (Al), based on the amount of component A, containing, wherein Monomers have a chemically reactive functionality.

Use of a fiber composite material W with sandwich structure according to one of claims 1 to 6, wherein the reinforcing fibers B contain on the surface one or more chemically reactive functionalities from the group hydroxy, ester and amino groups.

Use of a fiber composite material W with sandwich structure according to one of claims 1 to 7, wherein the reinforcing fibers B consist of glass fibers containing as chemically reactive functionality silanol groups on the surface.

Use of a fiber composite material W with sandwich structure according to one of claims 1 to 8, wherein the reinforcing fibers B in the form of a gel, a fabric, a mat, a nonwoven fabric or a knitted fabric in a maleic anhydride-modified styrene copolymer used as the molding material A. become.

10. Use of a fiber composite material W with sandwich structure according to one of claims 1 to 9, wherein the material layer w has a thickness of <100 mm, preferably of <10 mm, especially of <5 mm.

1 1. Use of a fiber composite material W with sandwich structure according to one of claims 1 to 10, wherein the material layer w has a ribbing.

12. Use of a fiber composite material W with sandwich structure according to one of claims 1 to 1 1, wherein the material layer w contains more than three layers. 13. Use of a fiber composite material W with sandwich structure according to one of claims 1 to 12, wherein the at least one thermoplastic layer T and / or at least one foam layer S by lamination or (co-) extrusion with the material layer w are connected. H. Use of a fiber composite material W with sandwich structure according to one of claims 1 to 13, wherein the thermoplastic layer T is reinforced with at least one short, long or continuous fiber S, in particular with carbon or basalt fibers. 15. Composite fiber material W having a sandwich structure, comprising:

A) at least one thermoplastic material layer w,

containing as components in the production

a) at least one thermoplastic molding compound A as matrix,

b) at least one layer of reinforcing fibers B, and

B) at least one further thermoplastic layer T, which is different from the layer w, and / or at least one foam layer S, wherein said further layer T and / or S is permanently connected to the material layer w.

16. Use of a fiber composite material W with a sandwich structure according to one of claims 1 to 14, wherein it consists of:

A) 10 to 70 wt .-% thermoplastic material layer w containing

wherein the reinforcing fibers B are used in the form of a gel, a fabric, a mat, a nonwoven or a knitted fabric in a maleic anhydride-modified styrene copolymer as molding compound A and wherein the material layer w optionally contains more than three layers.