EP3286000A1

EP3286000A1 - Styrene-polymer-based organic sheets for white goods

Info

Publication number: EP3286000A1
Application number: EP16721376.8A
Authority: EP
Inventors: Philipp Deitmerg; Norbert Niessner; 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: WO2016170104A1

Abstract

The invention relates to the use of a thermoplastic fiber composite material, comprising a) at least one thermoplastic molding material A as a matrix, b) at least one layer of reinforcing fibers B, and c) optionally at least one additive C, the at least one layer of reinforcing fibers B being embedded in the matrix of the thermoplastic molding material, and the thermoplastic molding material A having at least one chemically reactive functionality which reacts with chemical groups of the surface of component B during the production process of the fiber composite material, for the production of white goods, such as domestic appliances, enabling lightweight products.

Description

The present invention relates to the use of a fiber composite material (also called organic sheet) in the field of white goods, the fiber composite material comprising a thermoplastic molding compound A and a reinforcing fiber B, wherein the layers of the Reinforcing fiber B are embedded in the matrix of the thermoplastic molding composition A, and wherein the thermoplastic molding compound A at least one chemically reactive functionality.

Fiber composite materials or organic sheets usually consist of a multiplicity of reinforcing fibers which are embedded in a polymer matrix. The fields of application of fiber composite materials are manifold. For example, 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 loading 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. On the other hand, the matrix 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 the fiber-matrix adhesion and to compensate for a "low chemical similarity" between the fiber surfaces and the surrounding polymer matrix, reinforcing fibers are regularly pretreated by adding adhesion promoters to the so-called sizing agent on a regular basis ) is applied to the fiber at regular intervals during production 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, such as by burning down In some cases, glass fibers are also processed without sizing.

Then, a further adhesion promoter is applied in an additional process step for the production of the fiber composite material. Sizing and / or adhesion promoters form on the surface of the fibers a layer which can substantially determine the interaction of the fibers with the environment. Today, a large number of different bonding 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 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 elements that are exposed to high mechanical stress, a significant risk of accident of torn components arise.

Therefore, it is desired to provide fiber composite materials with a wide loading range in which total failure is unlikely. Desirable also good optical properties are desired, such as the ability to be able to produce various elements with smooth surfaces by means of fiber composite materials. 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-phenyl maleimide-containing copolymer, chopped glass fibers and an aminosilane-based coupling agent. The use of such a coupling agent leads to additional processing steps and thus increases the production costs.

US 201 1/0020572 describes organo-sheet components with a hybrid design of, for example, a highly flowable polycarbonate component. In this process, polycarbonate (PC) is rendered flowable by suitable additives, such as hyperbranched polyesters, ethylene / (meth) acrylate copolymers or low molecular weight polyalkylene glycol esters.

EP-A 2 251 377 describes organo-sheets which have been treated with an aminosilane size. It is not taught to use organo sheets for the production of white goods.

(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, through the sizing an agglomeration of the fibers are avoided. 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). As a result, low molecular weight functional agents can react with silanol groups on the glass surface, with these low molecular weight agents subsequently reacting further (for example, in epoxy resins), thereby providing chemical bonding of the glass fiber to the polymer matrix. 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 the disadvantage that polycarbonate (PC) has a very high viscosity and for this impregnation step low molecular weight, ie low viscosity PC must be used, which has an extremely poor usability, such as a low resistance to stress cracking agents, such as polar solvents. A technical object of the invention is to produce a fiber composite material (organogelc) which has suitable properties for the "white goods" sector. The fiber composite material should be based on an easily processed, against conventional solvent largely inert, 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 a fiber composite material comprising at least one thermoplastic molding composition A as matrix, at least one reinforcing fiber B, and optionally at least one additive C, wherein the layers of reinforcing fiber B are embedded in the matrix, and wherein the thermoplastic molding composition A has at least one chemically reactive functionality, which reacts during the manufacturing process of the fiber composite material with chemical groups of the surface of component B, especially in the field of white goods, such as household appliances, is well suited. The resulting fiber composite Material has good strength and is resistant to tearing and solvents and thus suitable for use in white goods.

One aspect of the present invention therefore relates to the use of a thermoplastic fiber composite material comprising (or consisting of): 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 and the thermoplastic molding compound A has at least one chemically reactive functionality which reacts with chemical groups of the surface of component B during the manufacturing process of the fiber composite material to produce white Goods, such as Household appliances.

Therefore, in other words, the present invention also relates to a process for the production of white goods, e.g. Household appliances, comprising the following steps:

(i) providing

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 and the thermoplastic molding compound A has at least one chemically reactive functionality which reacts with chemical groups of the surface of component B during the manufacturing process of the fiber composite material;

(ii) contacting the components A and B, and optionally C, with each other, in particular by loading or coating the component B with a (preferably obtained by heating) viscous or liquid thermoplastic molding compound A, optionally further containing at least one additive C; and

(iii) reacting the at least one chemically reactive functionality of component A with chemical moieties of the surface of component B; and optional (iv) shaping the fiber composite obtained from the preceding steps; and optional

(v) Curing the fiber composite obtained from the preceding steps.

The polymer matrix may be an amorphous plastic matrix in which the reinforcing fibers B are embedded as reinforcement and coupled to the matrix via fiber-matrix adhesion. According to the invention, the fiber composite material has at least the components A and B. The fibers B (reinforcing fibers) are embedded in a thermoplastic molding compound A.

As used herein, it will be understood that a polymer, unless otherwise defined, may also be a copolymer (including a terpolymer, etc.). Accordingly, a polymer matrix can also be a copolymer matrix.

The invention particularly relates to the use of a thermoplastic fiber composite material as described above, containing (or consisting of): a) 30 to 95% by weight of the thermoplastic molding composition A,

b) 5 to 70 wt .-% of the reinforcing fibers B, and

c) 0 to 40 wt .-% of the additive C.

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 a polymer component (Ab). The invention particularly relates to the use of a thermoplastic fiber composite material as described above, wherein the thermoplastic molding material A is amorphous. The thermoplastic molding compound A is preferably selected from the group consisting of:

Polystyrene (clear or impact resistant), styrene-acrylonitrile copolymers, α-methylstyrene-acrylonitrile copolymers, toughened-modified styrene-acrylonitrile copolymers, in particular acrylonitrile-butadiene-styrene copolymers (ABS) and acrylonitrile-styrene-acrylic ester copolymers ( ASA), and blends of said copolymers, in particular with polycarbonate or polyamide.

It will be understood that according to the invention at least one of the (co) polymer components of the thermoplastic molding material A is a (co) polymer which has at least one chemically reactive functionality as described herein (polymer component (A-a)). Each of the copolymer components mentioned in the preceding paragraph can accordingly also have, in addition to the explicitly mentioned monomers, a reactive functionality which can react with the surface of the fibers B during the production of the fiber composite material. Thus, any of the above-mentioned (co) polymers may also be a polymer component (A-a).

Accordingly, the abovementioned polymer components in their use as polymer component (A-a) generally also comprise at least one monomer A-1 which mediates the chemically reactive functionality (hence the reaction with fibers B). These may then also be referred to as: polystyrene (AI) copolymer, styrene-acrylonitrile (Al) copolymer, α-methylstyrene-acrylonitrile (Al) copolymer, impact-modified acrylonitrile-styrene (Al) copolymer, in particular acrylonitrile-butadiene-styrene (Al) copolymer (ABS (AI)) and acrylonitrile-styrene-acrylic ester (AI) copolymer (ASA (AI)). Also, blends of said copolymers with polycarbonate or polyamide are possible.

Optionally, the above-mentioned polymer components in their use as polymer component (A-a) may also additionally comprise a second monomer (or even a third monomer) which mediates the chemically reactive functionality.

By way of example, therefore, the abovementioned polymer components (in their use as polymer component (Aa)) in the case of the use of maleic anhydride (MA) as monomer Al may also be referred to as: polystyrene Maleic anhydride copolymer, styrene-acrylonitrile-maleic anhydride copolymer, o methylstyrene-acrylonitrile-maleic anhydride copolymer, impact-modified acrylonitrile-styrene-maleic anhydride copolymer, in particular acrylonitrile-butadiene-styrene-maleic anhydride copolymer (ABS-MA) and acrylonitrile Styrene-acrylic ester-maleic anhydride copolymer (ASA-MA). Also, blends of said copolymers with polycarbonate or polyamide are possible. It will be understood that the same applies to other monomers Al as well.

Optionally, one or more of any other (co) polymers without such functionality (as polymer component (A-b)) may be used in addition to the one or more polymer component (s) (A-a). Here too, by way of example, the abovementioned (co) polymers (therefore polystyrene, styrene-acrylonitrile copolymers, α-methylstyrene-acrylonitrile copolymers, impact-modified acrylonitrile-styrene copolymers, in particular acrylonitrile-butadiene-styrene copolymers (ABS) and acrylonitrile Styrene-acrylic ester copolymers (ASA), as well as blends of said copolymers with polycarbonate or polyamide), but then without the functionality (therefore without reactive monomer Al) are used.

Particularly preferably, the polymer component (A-a) of the thermoplastic molding composition A is based on a SAN copolymer.

Those skilled in the art will recognize that the SAN copolymer then additionally comprises a monomer A-1 which reacts with the surface of the fibers B during the manufacturing process. Accordingly, the SAN copolymer in its use as a polymer component (Aa) may also be a SAN (III) copolymer (= SAN (MI) terpolymer), for example a SAN-MA copolymer (= SAN-MA copolymer). terpolymer).

The invention accordingly also provides the use of a thermoplastic fiber composite material, wherein the thermoplastic molding composition A comprises (or consists of):

at least one polymer component (Aa) which has at least one chemically reactive functionality which reacts with chemical groups on the surface of the reinforcing fiber component B during the production process of the fiber composite material and is selected from the group 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), each containing at least one functional group, and blends said copolymers with polycarbonate or polyamide; and optional at least one polymer component (Ab), having no such functionality, selected from the group consisting of: polystyrene, styrene-acrylonitrile copolymers, α-methylstyrene-acrylonitrile copolymers, impact-modified acrylonitrile-styrene copolymers, in particular acrylonitrile-butadiene Styrene copolymers (ABS) and acrylonitrile-styrene-acrylic ester copolymers (ASA), as well as blends of said copolymers with polycarbonate or polyamide.

The invention also provides the use of a thermoplastic fiber composite material, wherein the thermoplastic molding composition A comprises (or consists of):

at least one polymer component (Aa) which has at least one chemically reactive functionality which reacts with chemical groups on the surface of the reinforcing fiber component B during the production process of the fiber composite material and is selected from the group 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), each containing at least one functional group, and blends said copolymers with polycarbonate or polyamide; and optional

at least one polymer component (Ab), having no such functionality selected from the group consisting of: polystyrene, styrene-acrylonitrile copolymers, α-methylstyrene-acrylonitrile copolymers, impact-modified acrylonitrile-styrene copolymers, in particular acrylonitrile-butadiene Styrene copolymers (ABS) and acrylonitrile-styrene-acrylic ester copolymers (ASA), as well as blends of said copolymers with polycarbonate or 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 compound A is a (co) polymer which has at least one chemically reactive functionality which, during the production process of the fiber composite material, has chemical groups on the surface of the polymer Reinforcing fiber component B reacts (polymer component (Aa)). Optionally, one or more other (co) polymers without such functionality (as the polymer component (Ab)) can be used. In a further embodiment, the invention relates to the use of a thermoplastic fiber composite material as described above, wherein the chemically reactive functionality of the thermoplastic molding composition A is based on components (Al) from the group: maleic anhydride, N-phenylmaleimide, tert-butyl ( meth) acrylate and glycidyl (meth) acrylate function, preferably selected from Group consisting of: maleic anhydride, N-phenylmaleimide and glycidyl (meth) acrylate function.

In a further embodiment, the invention relates to the use of a fiber composite material as described above, wherein the thermoplastic molding composition A at least 0.1 wt .-%, often 0.15 to 0.5 wt .-%, monomers Al, based on the weight of component A, which have a chemically reactive functionality contains. 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 thermoplastic fiber composite material as described above, wherein the surface of the reinforcing fibers B contains one or more of the functions: hydroxyl, ester and amino groups. 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 a chemically reactive functionality silanol groups on the surface. In a further embodiment, the invention relates to the use of a thermoplastic fiber composite material as described above, wherein the reinforcing fibers B in the form of a mat, a fabric, a mat, a nonwoven fabric or a knitted fabric are used. In a further embodiment, the invention relates to the use of a thermoplastic fiber composite material as described above, wherein the fiber composite material has a thickness of <10 mm, preferably of <2 mm, most preferably of <1 mm. In a further embodiment, the invention relates to the use of a thermoplastic fiber composite material as described above, wherein the fiber composite material has a ribbing or a sandwich construction. In a further embodiment, the invention relates to the use of a thermoplastic fiber composite material as described above, wherein the fiber composite material is layered and contains more than two, often more than three layers.

By way of example, the other layers may be the same or different in construction from those described above.

In a further embodiment, the invention relates to the use of a thermoplastic fiber composite material as described above, for the production of large or small appliances, in particular for the household.

In one embodiment, the invention relates to the use of a thermoplastic fiber composite material as described above, for the production of coverings and side coverings. In one embodiment, the invention relates to large or small devices comprising thermoplastic fiber composite materials, consisting of the components A to C as described above.

Component A

The fiber composite material contains at least 20 wt .-%, usually at least 30 wt .-%, based on the total weight of the fiber composite material, the thermoplastic molding material A. The thermoplastic matrix (M), which forms the molding material A, is in the fiber composite material preferably from 30 to 95 wt .-%, particularly preferably from 35 to 90 wt .-%, often from 35 to 75 wt .-% and in particular from 38 to 70 wt .-%, based on the fiber composite -Material, available. Preferably, the thermoplastic matrix M corresponds to the thermoplastic molding material A. Preferably, the thermoplastic molding material A consists mainly (more than 50%, preferably more than 90%) of styrene polymers such as polystyrene (clear "PS" or impact resistant "FIPS") or copolymer A. -1. According to one embodiment, the thermoplastic molding composition A is at least 75 wt .-%, preferably at least 90 wt .-% of the copolymer A-1. The thermoplastic molding compound A can also consist only of copolymer A-1.

For a fiber composite material according to the invention come as thermoplastic molding material A Although any thermoplastics in question, in particular however, PS or styrene copolymers, in particular HIPS, 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) (HIPS) polystyrene and / or at least one copolymer A-1 (styrene copolymer, SAN, ABS and ASA)) at least one Monomer Al includes.

By way of example, in the case of using maleic anhydride (MA) as the monomer Al, the polystyrene can therefore be a (HIPS) polystyrene-maleic anhydride copolymer (S-MA), the copolymer A-1 exemplified by styrene-acrylonitrile-maleic anhydride copolymer (SAN -MA), acrylonitrile-butadiene-styrene-maleic anhydride copolymer (ABS-MA), acrylate-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 (HIPS) polystyrene, SAN, ABS and / or ASA (each comprising no monomer A-1).

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 having at least one chemically reactive functionality as described herein (polymer component (A-a)). Optionally, one or more optional (co) polymers without such functionality (as the polymer component (A-b)) can be used.

The thermoplastic molding compound A (component A) is preferably an amorphous molding compound, wherein amorphous state of the thermoplastic molding compound (thermoplastic) means that the macromolecules without regular arrangement and orientation, i. without constant distance, are arranged completely statistically.

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 fiber composite material, comparatively low. It can be obtained particularly smooth surfaces in the moldings.

Alternatively, component A contains a partially crystalline fraction of less than 60% by weight, preferably less than 50% by weight, particularly preferably less than 40% by weight, based on the total weight of component A. Partially crystalline thermoplastics form both chemically regular, as well as geometric areas, d. H. 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 can be, for example, a blend of a styrene copolymer with one or more polycarbonate (s) and / or one or more semicrystalline polymers (such as polyamide), the proportion of partially crystalline mixed components in the entire component A being less than 50% by weight .-%, preferably less than 40 wt .-% should be. According to the invention, the thermoplastic molding composition A used comprises polystyrene or at least one copolymer A-1 comprising monomers Al which form covalent bonds with the functional groups Bl of the embedded reinforcing fibers B. The proportion of monomers Al in the thermoplastic molding composition A can be chosen variable. The higher the proportion of monomers A1 and the functional groups (B1), the stronger the bond between the thermoplastic molding compound A and the reinforcing fibers B can be. Monomers Al may still be present as monomers in copolymer A-1 or may be incorporated into copolymer A-1. Preferably, the monomers Al are incorporated in the copolymer A-1. According to a preferred embodiment, the copolymer A-1 is constructed with a proportion of monomers A1 of at least 0.1 wt .-%, preferably of at least 0.5 wt .-%, in particular of at least 1 wt .-%, z. B. 1 to 3 wt .-%, based on A-1. 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. As monomers A1, preference is given to those which can form covalent bonds by reaction with hydroxyl or amino groups. Preferably, the monomers Al 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 into 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-1 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 A-1 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 comprises 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 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).

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). 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 as thermoplastic molding material A. An inventively used, modified (a-methyl) styrene-acrylonitrile copolymer (as polymer component (Aa)) as thermoplastic molding material A is prepared from, based on the (a-methyl) styrene-acrylonitrile copolymer, 60 to 85 wt %, preferably 65 to 80% by weight of (α-methyl) styrene, 14.9 to 37% by weight, preferably 19.9 to 32% by weight of acrylonitrile and 0.1 to 5% by weight , preferably 0.1 to 3 wt .-% maleic anhydride. Mixtures of styrene-acrylonitrile copolymer with a-methyl-styrene-acrylonitrile copolymer may also be mentioned.

A (modified) (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 wt. -%, preferably 55 to 95 wt .-%, particularly preferably 60 to 85 wt .-% (a-methyl) styrene and 5 to 45 wt .-%, preferably 15 to 40 wt .-% of methyl methacrylate. The (a-methyl) styrene-methyl methacrylate copolymer may be random or a block polymer. Component A can also be prepared from based on Component A, at least 50 wt .-%, preferably 55 to 95 wt .-%, particularly preferably 60 to 85 wt .-% vinyl aromatic monomer and 5 to 45 wt .-%, preferably 15 to 40 wt .-% of methyl methacrylate. A modified copolymer used according to the invention (as polymer component (Aa)) of the thermoplastic molding composition A can be prepared from, based on the copolymer, 0.1 to 30% by weight maleic anhydride as component Al and 70-99.9% styrene, preferably 0 , 2 to 20% by weight of maleic anhydride as component Al and 80-99.8% of styrene, more preferably 0.3 to 10% by weight of maleic anhydride as component Al and 90-99.7% of styrene.

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.

According to a preferred embodiment, the modified ABS copolymer may contain: up to 70% by weight (about 35 to 70% by weight) of butadiene, 20 to 99.9% by weight (about 20 to 50% by weight) Styrene and up to 38 wt .-% (about 9.9 to 38 wt .-%) acrylonitrile and 0.1 to 5 wt .-%, preferably 0.1 to 3 wt .-% of a monomer Al, such as maleic anhydride. Component A can also be prepared from 35 to 70% by weight of at least one conjugated diene, 20 to 50% by weight of at least one vinylaromatic monomer and 9 to 38% by weight of acrylonitrile and 0.1 to 5% by weight, preferably 0.1 to 3% by weight of a monomer Al, such as maleic anhydride.

In a further preferred embodiment, the inventive component A is a styrene / butadiene copolymer such as impact polystyrene, a styrene-butadiene block copolymer such as Styrolux, styroflex, K-resin, clears, asaprene, 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 fiber composite materials can take place. Component B

The fiber composite material (organic sheet) contains at least 5 wt .-%, based on the fiber composite material, the reinforcing fiber B (component B). The reinforcing fiber B is in the fiber composite material preferably from 5 to 70 wt .-%, particularly preferably from 10 to 65 wt .-%, often from 25 to 65 wt .-% and in particular from 29.9 to 61, 9 wt .-%, based on the fiber composite material included. The reinforcing fiber B can be any fiber whose surface has functional groups Bl, which can form a covalent bond with the monomers Al of component A. In a preferred embodiment, the functional groups Bl on the surface of the reinforcing fiber B are selected from hydroxy, ester and amino groups. Particularly preferred are hydroxy groups.

According to a more preferred embodiment, the reinforcing fibers B are glass fibers having hydroxyl groups in the form of silanol groups as chemically reactive functionality B-1 at the surface.

The reinforcing fibers B may be embedded in the fiber composite material in any orientation and arrangement. The reinforcing fibers B are preferably present in the fiber composite material not (statistically) uniformly distributed, but in levels with higher and lower levels (therefore as more or less separate layers). Preferably, it is assumed that a laminate-like or laminar structure of the fiber composite material.

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 wets and holds them together, comprising at least one thermoplastic molding compound A.

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

According to a preferred embodiment, the fibers B are embedded in layers in the fiber composite material, preferably embedded as a fabric or scrim, in particular as a fabric, in the fiber composite material.

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 as a rule will be longer than 5 mm. the. The person skilled in the art knows that in this case the fabrics F are preferably present in such a way that they (largely) pass through the fiber composite material (and 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. 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 is preferably a (largely) flat fiber composite material (therefore also the molding T preferably a flat molding T).

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

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 a further component C, the fiber composite material used optionally contains 0 to 40 wt .-%, preferably 0 to 30 wt .-%, particularly preferably 0.1 to 25 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, often less than 150 g / mol.

Particulate mineral fillers may be, for example, amorphous silica, carbonates such as magnesium carbonate, calcium carbonate (chalk), powdered quartz, mica, various silicates such as clays, muscovite, biotite, suzoite, tin malite, talc, chlorite, phlogopite, feldspar, calcium silicates such as wollastonite or kaolin, especially calcined kaolin.

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, if appropriate in conjunction 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 the mixture, can be used.

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, with brominated compounds being preferred over the chlorinated ones, remain stable in the preparation and processing of the molding composition of this invention so that no corrosive gases are released and efficacy is not thereby compromised. Preference is given to using halogen-free compounds, for example phosphorus compounds, in particular phosphine oxides and derivatives of acids of phosphorus and salts of acids and acid derivatives of phosphorus. Phosphorus compounds particularly preferably contain ester, alkyl, cycloalkyl and / or aryl groups. Likewise suitable are oligomeric phosphorus compounds having a molecular weight of less than 2000 g / mol, as described, for example, in EP-A 0 363 608.

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 titanium dioxide, in particular the rutile form is used for the whitening of the molding compositions according to the invention.

Black color pigments which can be used according to the invention are iron oxide black (Fe304), spinel black (Cu (Cr, Fe) 204), manganese black (mixture of manganese dioxide, silicon oxide and iron oxide), cobalt black and antimony black, and particularly preferably carbon black, which is usually present in Form of Furnace- or gas black is used (see G. Benzing, Pigments for paints, Expert-Verlag (1988), p. 78ff). 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.

Production and Use of Fiber Composite Materials (Organic Sheets)

Preferably, organic sheets are processed by injection molding or pressing. Thus, by a functional integration, for example, the molding or pressing of Functional elements, a further cost advantage can be generated because of further assembly steps, such as the welding of functional elements can be dispensed with.

The process for producing a fiber composite material comprises the steps:

(i) providing:

(A) at least one thermoplastic molding composition A as matrix M, containing (or consisting of) polystyrene or at least one copolymer A-1 containing monomers Al (and optionally one or more further (co) polymers (Aa) and / or (Ab ));

(B) at least one reinforcing fiber B, the surface of which has functional groups B-I capable of forming a covalent bond with the monomers A-I;

(C) optionally at least one additive C;

Melting the thermoplastic molding material A and bringing it into contact with at least one reinforcing fiber B from step (i); and

Reacting at least a portion of the monomers A-1 of the polystyrene or 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.

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

According to a preferred embodiment, the fiber composite material contains (or consists of): a) 30 to 95% by weight of at least one thermoplastic molding compound A, b) 5 to 70% by weight of at least one reinforcing fiber B, and

c) 0 to 40% by weight of at least one additive C.

Step (ii) of the process, melting the thermoplastic molding compound A and contacting this melt with the reinforcing fibers B, may be effected in any suitable manner. In such an impregnation, the matrix M, consisting of at least one thermoplastic molding compound A, can be converted into a flowable material. conditions are transferred 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 fiber composite material 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 significantly is improved.

During consolidation, air pockets in the fiber composite material are reduced and a good bond is made between thermoplastic molding compound A and reinforcing fiber B (particularly if it is layered reinforcing fibers B). It is preferred, after impregnation and consolidation, to obtain a (as far as possible) non-porous composite material.

Alternatively, said steps may be performed 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 may be present with reinforcing fibers B with different fiber-matrix adhesion, which can be consolidated in a further step to form a composite material as fiber composite material. 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.

According to an optional embodiment, no adhesion promoter, in particular no adhesion promoter from the group consisting of aminosilanes and epoxy compounds, is used in the production of the fiber composite material.

The 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 may 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 moldable fiber composite material in which the thermoplastic molding composition A is still (partially) melted present. Alternatively or additionally, a cured fiber composite material can also 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 organic sheets 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, aesthetic and constructive aspects. The reinforcing fibers B may be layer-wise impregnated and consolidated as layers of reinforcing fibers B in a single processing step with the matrix M containing a thermoplastic molding material A. The production of the fiber composite material can be done in this way in a particularly efficient manner.

The weight reduction is applied to all moving components, e.g. Washing drums, an advantage, since the weight reduction of the moving masses energy savings can be achieved (reducing the torque during acceleration).

Another advantage of the styrene copolymers as amorphous thermoplastics (e.g., SAN) is the sometimes high scratch resistance of these materials. This has the advantage in the application examples described below that the trim parts do not scratch during assembly and later use.

In comparison with a polypropylene-based matrix, a further advantage of the thermoplastic molding compositions described here is the non-polar surface, which enables direct painting, pasting and printing. Another advantage of the use according to the invention of the organo-sheets for the production of white goods is the high rigidity and strength. Lids for washing machines and dryers must withstand high loads, for example, because the devices are often stacked for space reasons. The upper cover of the lower device must bear the static and dynamic loads of the upper device. The required rigidity and strength is ensured by an organic sheet in a sandwich composite or z. B. achieved by a ribbing.

The core material in the sandwich composite can be either a foam core (eg Rohacell from Evonik) or a honeycomb core (eg Honeycomps from EconCore). In order to achieve a cohesive bond between the organic sheet and the core, the core consists of a chemically compatible thermoplastic in order to heat-weld 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 to achieve a cohesive connection between the ribs and the organic sheet here too, a suitable thermoplastic molding composition, in particular one of the abovementioned styrene copolymers, should be used become. Preferably, a SAN, ABS or ASA-based thermoplastic molding composition is used. in such styrene copolymer, when used as the polymer component (Aa), may be about a M-containing styrene copolymer (exemplified by a maleic anhydride-containing styrene copolymer).

"Based thereon" is to be understood in the broadest sense as containing said component (s), preferably the said component (s) being greater than 50% by weight, more preferably greater than 75% by weight. even more preferably more than 90% by weight, even more preferably more than 95% by weight, or (largely) consisting of said component (s).

According to a particularly preferred embodiment, the present invention relates to the use of a thermoplastic fiber composite material, wherein component A (or a component thereof) is produced from

up to 70% by weight (about 35 to 70% by weight) of at least one conjugated diene, up to 99.9% (about 20 to 50% by weight) of at least one vinyl aromatic monomer and

up to 38% by weight (about 9 to 38% by weight) of acrylonitrile as well

0.1 to 5 wt .-% of a monomer A-l, which has a chemically reactive functionality, in particular maleic anhydride, and wherein the reinforcing fibers B in the form of a gel, a fabric, a mat, a nonwoven or a knitted fabric are used and

wherein the fiber composite material has a ribbing or a sandwich construction, and

wherein the fiber composite material is optionally layered and contains more than two layers and

wherein the fiber composite material optionally has a thickness of <10 mm.

According to a particularly preferred embodiment, the present invention relates to the use of a thermoplastic fiber composite material of a thickness of <10 mm, containing: a) 30 to 95 wt .-% of a thermoplastic, amorphous molding material A, wherein component A is prepared from 35 bis 70 wt .-% of at least one conjugated diene, 20 to 50 wt .-% of at least one vinyl aromatic monomer and 9 to 38 wt .-% of acrylonitrile and 0.1 to 5 wt .-% of a monomer Al, which has a chemically reactive functionality , in particular maleic anhydride, and wherein b) from 5 to 70% by weight of a reinforcing fiber B, the surface of the reinforcing fibers B having one or more of the functions of hydroxyl-containing fibers B being in the form of a fabric, a woven fabric, a mat, a fleece or a knitted fabric. , Ester or amino

Contains groups, and c) 0 to 40 wt .-% of an additive C. wherein the at least one layer of reinforcing fibers B is embedded in the matrix of the thermoplastic molding composition, and the thermoplastic molding composition A at least one chemically reactive functionality, which during the manufacturing process of the fiber composite material reacts with chemical groups of the surface of component B, for the production of white goods, such as household appliances, wherein the fiber composite material preferably has a ribbing or sandwich construction and / or is layered and contains more than two layers. Even more preferably, the fiber composite material has one or more other features as described above.

As set forth herein, the present invention also encompasses white goods, e.g. a domestic appliance containing (at least one component containing) a) at least one thermoplastic molding compound A as a 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, and the thermoplastic molding compound A has at least one chemically reactive functionality which reacts with chemical groups of the surface of component B during the manufacturing process of the fiber composite material,

Preferably, the whiteness would have further properties as set forth herein.

Particularly preferably, the present invention relates to a household appliance comprising at least one component comprising

a) at least one thermoplastic molding material A as a matrix, prepared from From 35 to 70% by weight of at least one conjugated diene,

20 to 50 wt .-% of at least one vinyl aromatic monomer and

9 to 38 wt .-% acrylonitrile and

0.1 to 5 wt .-% of a monomer A-l, which has a chemically reactive functionality, in particular maleic anhydride, and

b) at least one layer of reinforcing fibers B in the form of a fabric, a fabric, a mat, a nonwoven or a knitted fabric, 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, and the thermoplastic molding compound A has at least one chemically reactive functionality which reacts with chemical groups of the surface of component B during the manufacturing process of the fiber composite material, and

wherein the fiber composite material optionally has a ribbing or a sandwich construction.

Furthermore, by means of an additional amorphous thermoplastic layer on the organic sheet and a nonwoven which has at least a grammage of 50 g / m ² and is embedded between organic sheet and thermoplastic layer, a grain can be shaped by means of the tool wall, whereby the surface additionally can be functionalized (scratch resistance, concealment of sink marks). Depending on requirements, the additional thermoplastic layer can be colored opaque, so that optically no organo sheet can be assumed, or you can deliberately create a "fiber look" by the use of a transparent layer.

The use of organo sheets in the sandwich or by ribbing can be achieved a cost reduction and at the same time the weight can be reduced, which on the one hand facilitate the assembly of the component and the other of the device. Side panels of household appliances often have to withstand high loads during assembly and abuse and therefore consist largely of metals, mainly of painted steel sheets.

The inventive use of organo sheets as a replacement of metals, the cost and weight can be reduced because the density of the organic sheets is much lower and the lack of rigidity, compared to steel, can be compensated by a ribbing or sandwich construction. The ribbing preferably consists of an injection molding material, which ensures a cohesive connection to the organic sheet 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 with be glued to the cover layers or it is caused by an additional thermoplastic layer on the organic sheet, a claw in the foam structure.

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.

The use of organ sheets in the area of household panel covers can, in addition to a cost and weight advantage, also result in an aesthetic advantage. By using an amorphous, transparent matrix, a so-called "fiber-look" can be achieved Even with the use of glass fiber, which is naturally transparent, the fibers can be made visible by painting the fibers Organic sheets according to the invention have the advantage that they can be used unpainted, wherein in comparison to the steel sheet of the painting can be saved.

By using organo sheets for housings and / or supporting structures, the weight of mobile home appliances can be reduced. This has the advantage that the devices become more manageable or, with the same weight, a larger battery can be installed in order to generate a longer battery life.

In the case of the housings, the wall thickness is oversized, often due to inadequate flowability of the injection molding compound or too low a flow path / wall thickness ratio. Through the use of organic sheets, therefore, the wall thickness can be significantly reduced, since the organic sheet only needs to be reshaped and thus can get along even with very large components with a small thickness. The organic sheets according to the invention can be produced, for example, with a thickness of <1 mm, preferably <0.7 mm, particularly preferred <0.5 mm. When these thin organic sheets are provided with a ribbing and Umsäumung, resulting in very rigid components, since the organic sheet is located in the edge fiber of the shell component, which has an increase in the resistance moment result. Due to the amorphous matrix A and thus low shrinkage, the moldings have a very smooth surface, which can still be painted or laminated as needed.

With structural parts, such as a support frame, the organo-sheets can also achieve a large weight advantage. Again, with the help of a Ribbing the stiffening of the components are supported. In addition, a functional integration can save subsequent assembly steps and other components and thus provides a cost advantage in addition to the weight. characters

FIG. 1 shows the fiber composite materials W which have been tested 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 W arranged in a horizontal orientation (left: 25-fold magnification, right: 50-fold magnification), the fibers clearly being horizontal extending dark layer between the light layers of thermoplastic molding material can be seen. Figure 1 C shows the 200-fold magnification, it can be seen that the impregnation is not completed in some places.

FIG. 2 shows the fiber composite materials W which have been tested according to test no. 2 were obtained. FIG. 2A shows the visual documentation. FIG. 2B shows the microscopic view of a section through the laminar fiber composite material 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. FIG. 2C shows a magnification of 200 times, whereby it can be seen that the impregnation is partly not completed. FIG. 3 shows the fiber-composite materials W, which according to test no. 3 were obtained. FIG. 3A shows the visual documentation. FIG. 3B shows a microscopic view of a section through the laminar fiber composite material W arranged in a horizontal orientation (left: 25-fold magnification, right: 50-fold magnification), with no layer of fibers being recognizable , FIG. 3C shows the 200-fold magnification, whereby it can be seen that the impregnation is largely completed.

FIG. 4 shows the fiber composite materials W which have been tested according to test no. 4 were obtained. FIG. 4A shows the visual documentation. FIG. 4B shows the microscopic view of a section through the laminar fiber composite material W arranged in a horizontal orientation (left: 25-fold magnification, right: 50-fold magnification), with no layer of fibers being 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 materials W which have been tested 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 W arranged in a horizontal orientation (left: 25-fold magnification, right: 50-fold magnification), wherein no layer of fibers can be recognized , Figure 4C shows the 200-fold magnification, it can be seen that the impregnation is not completely completed in a few places. FIG. 6 shows the production of the fiber composite materials W (here: glass fiber fabric) in the press inlet V25-V28. It is clearly recognizable that such a production method allows continuous production. In addition, it can be seen from the imprinting of the pattern that the fiber composite material 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 and claims.

Examples

The following experiments were carried out on a commercially available interval hot press, which is able to produce 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

Production direction: 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

Transparency was measured on 1 mm organo-sheet specimens in% of white daylight (100%) (Byk Haze gardi transparency meter (BYK-gardner, USA) according to ASTM D 1003 (eg ASTM D 1003-13)).

The described fiber composite materials (organic sheets), in particular with amorphous, thermoplastic matrix are particularly suitable for the production of household goods, such as large and small appliances. Some examples are shown below. Unless otherwise stated, the moldings are manufactured by injection molding. Example 1 Production of the fiber composite material M

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

Example 2 Production of the Fiber Composite Material N

65 wt .-%, based on the fiber composite material, 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 fiber composite material, a glass-based reinforcing fiber GW 123-580K2 of P-D Glasseiden GmbH compounded. The fiber composite material is subsequently ribbed.

Example 3 Production of molded parts from the fiber composite materials

The following molded parts are produced from the fiber composite materials M and N. Example A: Large appliances: extractor hoods, electric cooker, freezer, freezer / freezer combinations, dishwasher, refrigerators, washing machines and tumble dryers, spin dryers, wine refrigerators

Example B: Small appliances: bottle cooler, coffee grinder, blender, coffee machine, microwave oven, stirrers, immersion heater, toaster, kettle

Example C: Fairings

The fiber composite materials M and N are suitable as replacement of metals in the range of panels for the household appliances mentioned in Examples A and B.

Example D: moving parts: washing drums Example E: mobile appliances: hand vacuum cleaner The use of the thermoplastic fiber composite material according to the invention, containing the modified thermoplastic molding compound A, the layers of reinforcing fibers B and the additive C, both a lighter wall can be realized, so also more space indoors to be made in order to accommodate more space for z. B. to get a battery. It is also observed increased rigidity of the components. The difference to the rigidities of metal cladding can be compensated.

Example 4 Preparation of (partially) transparent organic sheets

Hazardous thermoplastic combinations A:

A1 (comparison): 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 ,

Shot, + chain = 1200tex

The combinations and parameter settings related to experiments # 1 -5 are listed in the table below: Table 1 . Manufacturing conditions of the fiber composite materials W

^* 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 semi-finished 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: Central unimpregnated areas, all-round lightly 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 Trial 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 recognizable

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

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

Table 3. Optical and haptic comparison of the experimental settings according to the invention with conventional organo sheets

Experimental Composite Maleic Acid Upper Printability Trans

No. anhydride surfaces with 45 mdyne parenz

Concentration ^* Ink ^** (%) tion

(% By weight)

1 (Cf.) A1 + B1 0 2 1

2 (Cf.) A1 + B1 0 2 3

3 A2 + B1 1 1 -2 1 40

4 A3 + B1 0.66 1 -2 25

5 A4 + B1 0.33 1 -2 1 20

6 Bond Laminates 0 4-5 0

Composite of approx

60% fiberglass fabric and 40%

polyamide

7 composite from approx. 0 4-5 5 0

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. Manufacturing conditions of fiber composite materials W

^* 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.

Experiment no. 8 9 Delta 10 1 1 Delta

(%) (%)

Reinforcement scrim (B1), fabric twill 2/2

Chain direction (B2)

Matrix A1 A3 A1 A3

Bending test:

Module (GPa) 19.7 22.5 14 21, 1 19.6 -7

Breaking stress (MPa) 21 1 462 1 19 423 528 25 Table 5 shows the 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 connection between fiber and matrix is not reflected in the bending stiffness, but clearly in the flexural strength (fracture stress) of the samples investigated.

Experiment no. 7

The results are shown in Table 6.

Table 6. Comparison of the wave depth Wt.

Here the components are defined as follows:

SAN: SAN-MA terpolymer, weight composition (% by weight): 73/25/2, Mw:

250,000 g / mol (as measured via gel permeation chromatography on stan- dard columns with monodisperse polystyrene standards), MVR: 15-25 cm ^3/10 min at 220 ° C / 10kg (IS01 133), viscosity (in DMF) J = 61-67 ml / g PC OD: easy flowing, amorphous optical grade polycarbonate for optical

discs)

PA6: semi-crystalline, easy-flowing polyamide 6

Fibers (B3): glass fiber fabric twill 2/2 (GF-KG) with basis weight = 300 g / m ² ,

Shot, + chain = 320tex

As can be seen in Table 6, the use of SAN-MA terpolymer is particularly advantageous in terms of maintaining a low surface undulation depth. PC OD was sensitive to stress cracks. Example 5 Multilayer Organic Sheets

The described fiber composite materials (organic sheets), in particular with amorphous, thermoplastic matrix are particularly suitable for the production of transparent and translucent molded bodies, films and coatings. Some examples are shown below. Unless otherwise stated, the moldings are made by injection molding. Production of molded parts from fiber composite materials M and N for washing machine windows

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 tests on bending stress on fabric-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: Compositions Comp. 1, Comp. 2, Comp. 10 and Comp. 15 and the compositions V3 to V9 according to the invention 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 XX 310 20-30 V9 XX 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 7 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 8: Average values of the maximum bending stress of the warp and weft directions of the produced organic sheets according to the mixtures Cf. 2, V5, V7, V9, Vgl. 10, V12 to V14 and Cgl. 15, wherein the production temperature was at least 300 ° C.

The values shown in Table 8 are the average of nine measurements each.

Table 8 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, which has a matrix containing 75% by weight of styrene (S) and 25% by weight of acrylonitrile (AN) (see Figure 10 and Figure 15). Also, 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 with a thermoplastic molding compound A, reinforcing fibers B.

Further investigation of multilayer 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

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

Glass filament twill weave (short designations: GF-KG (PD) or PD), twill weave 2/2, basis weight 320 g / m ² , Roving 320tex, finish 350, delivery width 635 mm (type: EC14-320-350, manufacturer and supplier : PD Glasseide GmbH Oschatz) Glass filament scrim (short name: GF-GE (Sae) or Sae) 0 45 90 -45 °, basis weight 313 g / m ² , main roving 300tex, finish PA size, delivery width

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 as (large) flat 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 when examined in detail against the light. 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. 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 found that the MW Wt for all fiber composite materials in which the matrix contains a functional component that can react with the fibers is clearly <10 μm, whereas in composite fiber 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 9. LSM Measurement Results with SAN Matrix System - Wave Depth (Wt) and Stellite (Ra)

This was just as clear when instead of the fabric a scrim (like Sae) is used: Table 10. LSM Measurement Results with SAN Matrix System - Wave Depth (Wt) and Stellite (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 produced fiber composite materials 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. For the samples, the following bending strengths were determined according to DIN EN ISO 14125:

Table 1 1. Transparent fiber composite materials - bending strength

In addition, the following black-colored fiber composite materials were produced, in which 2% by weight of carbon black was added to the matrix 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 12. Intransparent fiber composites - bending strength

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.

In comparison, for the non-inventive fiberglass material Luran 378P G7 reinforced with short glass fibers, only a flexural strength of 150 MPa was found, and therefore 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 was also possible to show experimentally that the resulting fiber composite materials could be formed into three-dimensional semifinished products, for example 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 fiberglass-based textile systems with different matrix systems to form 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 according to the invention (organic sheets) can be well converted to three-dimensional semi-finished products.

Claims

claims

Use of a thermoplastic fiber composite material comprising: 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, and the thermoplastic molding compound A has at least one chemically reactive functionality which reacts with chemical groups of the surface of component B during the manufacturing process of the fiber composite material for the production of white goods, such as household appliances.

Use of a thermoplastic fiber composite material according to claim 1, comprising

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

b) 5 to 70 wt .-% of the reinforcing fibers B, and

c) 0 to 40 wt .-% of the additive C.

Use of a thermoplastic fiber composite material according to claim 1 or 2, wherein the thermoplastic molding material A is amorphous.

Use of a thermoplastic fiber composite material according to one of claims 1 to 3, wherein the thermoplastic molding composition A is selected from the group consisting of polystyrene (clear or impact resistant), styrene-acrylonitrile copolymers, α-methylstyrene-acrylonitrile copolymers, impact-modified acrylonitrile Copolymers, in particular acrylonitrile-butadiene-styrene copolymers and acrylonitrile-styrene-acrylic ester copolymers, and blends of said copolymers with polycarbonate or polyamide.

Use of a thermoplastic fiber composite material according to any one of claims 1 to 4, wherein the chemically reactive functionality of the thermoplastic molding material A is based on components selected from the group consisting of: maleic anhydride, N-phenylmaleimide or glycidyl (meth) acrylate function ,

Use of a fiber composite material according to any one of claims 1 to 5, wherein the thermoplastic molding composition A contains at least 0.1 wt .-% of monomers Al, based on the amount of component A, which have a chemically reactive functionality.

7. Use of a thermoplastic fiber composite material according to any one of claims 1 to 6, wherein the surface of the reinforcing fibers B contains one or more of the functions hydroxy, ester or amino groups.

Use of a thermoplastic fiber composite material according to one of claims 1 to 7, wherein the reinforcing fibers B consist of glass fibers, which preferably contain as chemically reactive functionality silanol groups on the surface.

Use of a thermoplastic fiber composite material according to any one of claims 1 to 8, wherein component A is prepared from 35 to 70% by weight of at least one conjugated diene, 20 to 50 wt .-% of at least one vinylaromatic monomer and 9 to 38 wt % Acrylonitrile and 0.1 to 5% by weight of a monomer Al, which has a chemically reactive functionality, in particular maleic anhydride, and wherein the reinforcing fibers B in the form of a gel, a fabric, a mat, a nonwoven fabric or a knit used become.

Use of a thermoplastic fiber composite material according to one of claims 1 to 9, wherein the fiber composite material has a thickness of <10 mm, preferably of <2 mm, most preferably of <1 mm.

Use of a thermoplastic fiber composite material according to one of claims 1 to 10, wherein the fiber composite material has a ribbing or a sandwich construction.

Use of a thermoplastic fiber composite material according to any one of claims 1 to 1 1, wherein the fiber composite material is layered and contains more than two layers.

Use of a thermoplastic fiber composite material according to one of claims 1 to 12 for the manufacture of large or small appliances.

Use of a thermoplastic fiber composite material according to any one of claims 1 to 12 for the production of covers and side panels.

15. Large or small appliance containing thermoplastic fiber composite materials according to claims 1 to 12.

16. Use of a thermoplastic fiber composite material according to any one of claims 1 to 14, wherein component A is prepared from

From 35 to 70% by weight of at least one conjugated diene,

20 to 50 wt .-% of at least one vinyl aromatic monomer and

9 to 38 wt .-% acrylonitrile and

wherein the fiber composite material has a ribbing or a sandwich construction.

Household appliance comprising at least one component comprising

a) at least one thermoplastic molding composition A as a matrix, prepared from 35 to 70% by weight of at least one conjugated diene,

20 to 50 wt .-% of at least one vinyl aromatic monomer and 9 to 38 wt .-% acrylonitrile and

b) at least one layer of reinforcing fibers B in the form of a fabric, a fabric, a mat, a nonwoven or a knitted fabric, 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, and the thermoplastic molding compound A has at least one chemically reactive functionality which reacts with chemical groups of the surface of component B during the manufacturing process of the fiber composite material.