WO2016170143A1

WO2016170143A1 - Method for producing a fibre-composites based on styrol- copolymers

Info

Publication number: WO2016170143A1
Application number: PCT/EP2016/059061
Authority: WO
Inventors: Achim Bernhardt
Original assignee: Ineos Styrolution Group Gmbh
Priority date: 2015-04-22
Filing date: 2016-04-22
Publication date: 2016-10-27

Abstract

The invention relates to a method for producing a fibre-composite (V) containing reinforcing fibres (B) and a thermoplastic styrol-copolymer moulding compound (A), comprising the following steps: a) producing a flat or 3-dimensional textile structure (G) made from reinforcing fibres (B) and thermoplastic styrol-copolymer-fibres (F), said styrol-copolymer-fibres (F) consisting of the material of the thermoplastic styrol-copolymer-molding compounds (A); b) warming the textile structure (G) to a temperature which is above the melting range of the thermoplastic styrol-copolymer-fibres (F); c) cooling the fibre composite material (V) obtained in step b.

Description

Process for the production of thermoplastic fiber composite materials based on styrene copolymers

description

The present invention relates to a process for producing a thermoplastic fiber composite material V (also called organic sheet) comprising a thermoplastic styrene copolymer molding compound A and reinforcing fibers B, the process comprising the production of a textile structure G from the reinforcing fibers B and thermoplastic styrene Copolymer fibers F, which consist of the material of the thermoplastic styrene copolymer molding composition A.

Fiber composite materials consist of reinforcing fibers 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 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. For this purpose, it is necessary to achieve a complete and uniform penetration of the structure formed by the reinforcing fibers B with the matrix material. The production of fiber composite materials from reinforcing fibers and synthetic resins is usually carried out in the form that textile structures, so-called fiber semi-finished products (eg fabrics, scrims or fiber mats) are impregnated with a synthetic resin, which is then brought to cure. As a rule, the synthetic resin consists of a pre-polymer and a hardener. The pre-polymer here is a polymer or oligomer with a comparatively low molecular weight. Therefore, the synthetic resin initially has a low viscosity and can penetrate the semi-finished fiber quickly. The hardener added shortly before impregnation initiates the polymerization of the pre-polymer.

This increases the viscosity of the synthetic resin until finally a high molecular weight, often thermosetting plastic is obtained which uniformly surrounds the reinforcing fibers of the fiber composite material. Since the thermosetting synthetic resins used are infusible after curing, the fiber composite materials must be produced in the form in which they are to be used later. A simple forming is not possible. By producing preimpregnated fibers or semi-finished fiber products, so-called prepregs, it is possible to reduce the effort involved in the actual production of the final component. For this purpose, semi-finished fiber products are impregnated with pre-polymer and then stored under a protected atmosphere (low temperature, low oxygen content). The curing can be done later at e.g. done by heating. Thus, the place and time of the impregnation and the shaping polymerization can be separated from each other. Thermoplastics have the advantage that they can be repeatedly reshaped by heating above the melting point of the polymer. This property is made use of in organic sheets which consist of reinforcing fibers which are embedded in a thermoplastic polymer matrix and can thereby be transformed under heating.

The disadvantage is that suitable thermoplastics are high molecular weight. They therefore have a high viscosity even in the molten state. It is therefore very time-consuming to achieve complete penetration of the semi-finished fiber products. US 2014/0232042 describes a method for the production of fasteners based on composite materials, which are produced from thermoplastic resin interspersed fiber flakes. These fiber flakes are made by first preimpregnating the fibers with thermoplastic resin and then cutting them into short sections. Such composites have the disadvantage that they are relatively less stable due to the short fiber lengths.

In the prior art, the use of hybrid yarns is known for producing reinforcing fiber mats comprising thermoplastic materials. For example, TW-B 235970 describes such yarns used as reinforcing fibers. These are obtained by twisting the reinforcing fibers together with thermoplastic fibers. The component is obtained by laying the fibers twisted together and then heating to a temperature sufficient to achieve penetration of the reinforcing fibers with the thermoplastic polymer. Textile prepregs obtained in this way are characterized by good drapability, freedom from solvents and the use of efficient textile processing processes. However, these advantages are offset by the high expense of producing the polymer filaments (see "Handbuch der Verbundwerkstoffe, M. Neitzel, P. Mitschang, U. Breuer (ed.), Carl Hanser Verlag, Munich, 2014, pages 182 to 183).

Other processes for producing thermoplastic textile prepregs are described in the prior art. The "Handbuch der Faserverbundkunststoffe / Composites", AVK - Industrievereinigung Reinforced Plastics eV (ed.), 4th edition, Springer Fachmedien, Wiesbaden, 2014, page 236, refers to co-weaving and co-knitting, both techniques in which reinforcing fibers and fibers, which consist of the matrix material, are combined in the planar textile process, ie during weaving or knitting, but these techniques do not entail a shortening of the flow path to be covered and therefore no acceleration of the production process (see also "Handbuch the composite materials, M. Neitzel, P. Mitschang, U. Breuer (ed.), Carl Hanser Verlag, Munich, 2014, pages 182 to 183, and "Polymer Rheology and Processing", AA Collyer, LA Utracki (ed. Elsevier Science Publishing Co., Inc., New York, 1990, pages 392-393).

DE 690 10 059 describes fabric structures in which fibers of non-thermoplastic reinforcing materials such as glass, aramid, carbon or silicon dioxide are woven or entangled together with fibers of thermoplastic materials such as polyetherimides, polyetheretherketones, polycarbonates, liquid-crystal polymers, polyphenylene sulfides or polyether sulfones. This fabric is stacked together with other fabrics of the above materials to form multilayer laminates, which can be heat-formed and worked to obtain various rigid articles. No statement is made about the duration of the melting process.

US 201 1/0020572 describes organic sheet components having a hybrid design of, for example, a high flow 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.

An object of the invention is to provide a process for producing a thermoplastic fiber composite material (organic sheet), which ensures a thorough and rapid penetration of the reinforcing fibers with the thermoplastic polymer matrix. The fiber composite material should be easy to produce. Furthermore, the method should be versatile and easily adaptable to the desired results.

It has surprisingly been found that it is possible to produce a thermoplastic fiber composite material V containing at least one thermoplastic styrene copolymer molding composition A as polymer matrix and at least one reinforcing fiber B, by first a textile structure G of the reinforcing fibers B and thermoplastic Styrene copolymer fibers F, prepared from the thermoplastic styrene copolymer molding compound A, which is then by heating the textile structure G to a temperature which is above the melting range of the thermoplastic styrene copolymer fibers F. and then cooling the obtained fiber composite material V, is obtained.

The resulting fiber composite material V is characterized in that the remaining after the melting of the thermoplastic styrene copolymer fibers F textile structure of the reinforcing fibers B is particularly uniformly penetrated by the thermoplastic styrene copolymer molding compound A. A particularly advantageous feature of this process is that the time required to melt the styrene copolymer molding compound A and to penetrate the reinforcing fibers B with the styrene copolymer molding compound A can be significantly reduced, since the reinforcing fibers B and the thermoplastic styrene copolymer fibers F are already uniformly distributed in the textile structure G. Thus, the comparatively thin thermoplastic styrene copolymer fibers F can be rapidly melted. The molten thermoplastic styrene copolymer molding compound A thus obtained does not have to penetrate far into the fabric of the reinforcement due to the uniform distribution. fibers B penetrate. After only a short time, a fiber composite material V uniformly interspersed with the styrene copolymer molding compound A is obtained. This is also possible with complicated molded parts such as, for example, shaped parts having different layer thicknesses in different regions of the molded part.

It has been found that fiber composite materials V with regions of different thickness can be produced in this way, in particular, in an advantageous manner.

One aspect of the present invention thus relates to a process for producing a fiber composite material V comprising reinforcing fibers B and a thermoplastic styrene copolymer molding compound A comprising the steps: a. Production of a sheet-like or spatial textile structure G from the reinforcing fibers B and thermoplastic styrene copolymer fibers F, wherein the styrene copolymer fibers F are made of the material of the thermoplastic styrene

Consist of copolymer molding compound A;

b. Heating the textile fabric G to a temperature higher than the melting range of the thermoplastic styrene copolymer fibers F;

c. Cooling of the fiber composite material V. obtained in step b.

A fiber composite material V for the purposes of this invention is a material comprising a thermoplastic styrene copolymer molding compound A and at least one reinforcing fiber B, wherein the reinforcing fibers B are embedded in the thermoplastic styrene copolymer molding compound A.

Thermoplastic styrene copolymer molding compound A in this context means that it is a styrene copolymer molding compound A comprising at least one thermoplastic styrene-containing copolymer. Suitable co-monomers are, for example, a-methylstyrene, acrylonitrile, methacrylonitrile, and methyl methacrylate (MMA), conjugated dienes and / or acrylates. Preferably, the thermoplastic styrene copolymer molding composition A is at least 50 wt .-% of a thermoplastic styrene copolymer, in particular at least 70 wt .-%, particularly preferably at least 90 wt .-%. In one embodiment, the styrene copolymer molding composition A is 100% by weight of a styrene copolymer.

The invention particularly relates to the use of a thermoplastic fiber composite material V as described above, containing (or consisting of): a) 30 to 95 wt .-% of the thermoplastic styrene copolymer molding composition A, preferably 35 to 90 wt .-%, in particular 40 to 80 wt .-%

b) 5 to 70 wt .-% of the reinforcing fibers B, preferably 10 to 65 wt .-%, in particular 20 to 60 wt .-% and

c) 0 to 40 wt .-%, preferably 0 to 30 wt .-%, in particular 0.1 to 25 wt .-% of the additive C.

In one embodiment, the invention relates to a process wherein the styrene copolymer of styrene copolymer molding material A is a styrene-butadiene block copolymer.

Alternatively or additionally, the styrene copolymer molding composition A may also contain polystyrene or (largely) consist of polystyrene. The invention also relates to a process in which the thermoplastic styrene copolymer fibers F at least one copolymer from the group styrene / acrylonitrile copolymer (SAN), acrylonitrile / butadiene / styrene copolymers (ABS) and acrylonitrile / styrene / acrylic ester -Copolymers (ASA) included. In one embodiment, the invention relates to a process wherein the reinforcing fibers B are selected from the group consisting of carbon fibers, glass fibers and aramid fibers.

The invention also relates to a method in which the textile structure G is a woven fabric, scrim, knitted fabric, braid, knitted fabric, nonwoven fabric or felt, wherein in each case the thermoplastic styrene copolymer fibers F and the reinforcing fibers B are processed together. In particular, the invention relates to a method in which the textile structure is a woven, knitted, laid or knitted fabric. The textile structure G is particularly preferably a woven fabric, in particular a woven fabric which contains at least 5% by weight of reinforcing fibers B, more preferably at least 10% by weight of reinforcing fiber B.

The invention also relates to a thermoplastic fiber semi-finished product H containing thermoplastic styrene copolymer fibers F and reinforcing fibers B, wherein the thermoplastic styrene copolymer fibers F and the reinforcing fibers B by a textile manufacturing process to form a sheet-like or spatial textile entity G together were connected. In one embodiment, the invention relates to a semifinished fiber H in which the styrene copolymer of the styrene copolymer molding compound A is a styrene-butadiene block copolymer. In a further embodiment, the invention also relates to a semi-finished fiber H, wherein the thermoplastic styrene copolymer fibers F at least one copolymer from the group styrene / acrylonitrile copolymer (SAN), acrylonitrile / butadiene / styrene copolymers (ABS) and acrylonitrile / styrene / Acrylic ester copolymers (ASA) included. In one embodiment, the invention relates to a semifinished fiber H in which the reinforcing fibers B are selected from the group consisting of carbon fibers, glass fibers and aramid fibers.

The invention also relates to a semi-finished fiber H, wherein the textile structure G is a woven, knitted, scrim, knitted, braided, knitted, nonwoven or felt, wherein each of the thermoplastic styrene copolymer fibers F and the reinforcing fibers B were processed together.

Preferably, the semi-finished fiber H is a fabric, in particular a fabric containing at least 5 wt .-% of reinforcing fibers B, more preferably at least 10 wt .-% of reinforcing fibers B.

Further, a molded article T is the subject of the invention, produced by a process comprising the following steps: a. Producing a semi-finished thermoplastic fiber H as described above; b. Shaping melting of the semi-finished fiber H to obtain the desired molding T;

c. Cooling of the obtained molding T.

In one embodiment, the invention relates to a molding T, in which the semi-finished fiber H is provided on at least one side with a layer containing another thermoplastic material before the step of shaping. The invention also relates to a molded part T, in which the shaping melting takes place by compression molding, hot pressing, diaphragm molding or hydroforming.

Styrene copolymer molding compound A (component A) The fiber composite material V or the semi-finished fiber H contains at least 20 wt .-%, usually at least 30 wt .-%, based on the total weight of the fiber composite material V, the thermoplastic styrene copolymer molding material A. The styrene Copolymer molding compound A preferably comprises from 30 to 95% by weight, more preferably from 35 to 90% by weight, often from 40 to 80% by weight and in particular from 45 to 75% by weight, based on the fiber composite material V, the semi-finished fiber H or the finished fiber composite material V from.

Suitable thermoplastic styrene copolymer molding compositions A are all thermoplastic see styrene copolymer molding compounds, which can be processed into fibers.

The thermoplastic styrene copolymer molding compound 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 styrene copolymer molding compound A has amorphous, thermoplastic properties, is therefore fusible and (largely) non-crystalline. As a result, the shrinkage of the thermoplastic styrene copolymer molding compound A, and therefore also of the entire fiber composite material V, is comparatively low. It can be obtained particularly smooth surfaces in the moldings.

Alternatively, the component A contains a partially crystalline fraction of less than 60 wt .-%, preferably less than 50 wt .-%, more preferably less than 40 wt .-%, based on the total weight of component A. Semi-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 styrene copolymer molding compound A may be a blend of amorphous thermoplastic polymers and semi-crystalline polymers. The thermoplastic styrene copolymer molding compound A can be, for example, a blend of a styrene copolymer with one or more polycarbonate (s) and / or one or more partially crystalline polymers (such as polyamide), the proportion of partially crystalline mixed components in the entire component A being less than 50 wt .-%, preferably less than 40 wt .-% should be. The styrene copolymer molding compound A comprises at least styrene copolymer, in particular one suitable for the production of fiber composite materials V. Amorphous thermoplastics are preferably used for the styrene copolymer molding compound A. For example, styrene copolymers 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) used. In particular, SAN, ABS and ASA are used. Very particular preference is given to using ABS copolymers as thermoplastic styrene copolymer molding compound A.

Blends of the abovementioned copolymers with polycarbonate or semicrystalline 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.

Acrylonitrile-butadiene-styrene copolymer according to the invention as thermoplastic styrene copolymer molding composition A can be prepared by known methods from styrene, acrylonitrile, butadiene and optionally a functional further monomer, such. Methyl methacrylate (MMA), maleic anhydride (MSA) or N-phenylmaleimide (N-PMI).

The ABS copolymer may, for. From 35 to 70% by weight of butadiene, from 20 to 50% by weight of styrene and from 9 to 38% by weight of acrylonitrile and from 0.1 to 5% by weight, preferably from 0.1 to 3% by weight. % of another functional monomer. 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 wt .-% of another functional monomer.

In a further preferred embodiment, the component A of the invention is a styrene / butadiene copolymer such as e.g. Impact-resistant polystyrene, a styrene-butadiene block copolymer, e.g. Styrolux®, Styroflex® (both from Styrolution, Frankfurt), K-Resin®, Clearen®, Asaprene®.

In a further embodiment, the styrene copolymer molding compound A may consist of at least two mutually different thermoplastic styrene copolymer molding compositions. For example, these different molding material types may have a different melt volume flow rate (MVR) and / or different coalescing volume flow rate (MVR). Have monomers or additives. For example, in a preferred embodiment, ABS molding compounds and SAN molding compounds can be combined. The styrene copolymer molding composition A comprises, for example, 30 to 70% by weight of ABS molding composition and 70 to 30% by weight of SAN molding composition, in particular 50 to 70% by weight of ABS molding composition and 50 to 30% by weight. % SAN molding compound.

In a preferred embodiment, the component A has a MVR 240 ° C / 10 kg according to ISO 1 133 of at least 10 cm ³ / 10min, preferably at least 15 cm ³ / 10min, in particular at least 20 cm ³ / 10min. Preferably, the thermoplastic matrix also has a MVR 240 ° C / 10 kg according to ISO 1 133 of at least 10 cm ³ / 10min, preferably at least 15 cm ³ / 10min, in particular at least 20 cm ³ / 10min.

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. 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, it being possible to determine Mw 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%.

Suitable preparation processes for the styrene copolymer molding compositions A are emulsion, solution, bulk or suspension polymerization, preference being given to solution polymerization (see GB 1472195). In a preferred embodiment of the invention, the styrene copolymer molding compound A after the preparation is isolated by processes known to those skilled in the art and preferably processed into granules. Thereafter, the preparation of the thermoplastic styrene copolymer fibers F can be carried out by a method known to the person skilled in the art, in particular by melt extrusion. Reinforcing fibers B (component B)

The thermoplastic fiber composite material V (organic sheet) contains at least 5 wt .-% of the reinforcing fibers B (component B), based on the fiber composite material V. The reinforcing fibers B are in the fiber composite material V vor- zugt of 5 to 70 wt .-%, particularly preferably from 10 to 65 wt .-%, often from 20 to 60 wt .-% and in particular from 25 to 55 wt .-%, based on the fiber composite material V, included , As the material of the reinforcing fibers B, all materials can be used which are processable into fiber and have a melting temperature which is greater than the melting temperature of the thermoplastic styrene copolymer molding composition A. Preferred are differences in the melting temperature of component A to B of at least 50 ° C, especially 70 ° C. In one embodiment, materials are used which have no thermoplastic behavior.

Suitable fibers are glass fibers, ceramic fibers, aramid fibers, carbon fibers, boron fibers, basalt fibers, steel fibers, and natural fibers such as flax, hemp, jute, kenaf ramie or sisal fibers. Particularly preferred are glass fibers, carbon fibers and aramid fibers.

The provision of the reinforcing fibers B can be effected by all methods known to the person skilled in the art and depends on the respective fiber type. The reinforcing fibers B preferably have:

a filament number of more than 500, especially more than 1000, and

a yarn count of 10 to 5000 tex, especially from 50 to 4000 tex.

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

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

A film former protects the glass filaments from mutual friction and may additionally enhance affinity for synthetic resins, thus promoting the strength and cohesiveness 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, even during manufacture. 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 organofunctional silanes, such as, for example, aminopropyltriethoxysilane, methacryloxypropyltrimethoxysilane, glycidyloxypropyltrimethoxysilane and the like, may 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. 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 or fabric well and to perform a "grafting" by reaction of functional groups on the glass fiber surface with the polycarbonate, which increases the compatibility with the polymer.

However, this procedure has 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 extremely poor usability, such as low resistance to stress cracking agents, such as polar solvents.

The reinforcing fibers B are present in the fiber semifinished product H according to the invention together with the thermoplastic styrene copolymer fibers F as a woven, knitted, folded, knitted, braided, nonwoven or felt. Preferably, the textile structure G is a woven, knitted fabric, scrim or knit. Particularly preferably, the textile structure G is a fabric, in particular one which contains at least 5 wt .-% of reinforcing fibers B. A scrim is a sheet consisting of one or more layers of parallel, stretched threads. At the crossing points, the threads are usually fixed. The fixation is done either by material bond or mechanically by friction and / or positive locking. The thread layers in multi-layered layers can all have different orientations, and can also consist of different thread densities and different thread counts.

A fabric is a textile fabric made up of at least two thread systems crossed at right angles or at right angles. Knitted fabric and knitwear are both among the knits, in which a thread loop is looped into another. Knitted fabrics (also called knits or hosiery) are made of thread systems by stitching on a knitting machine industrially produced fabrics. When knitting, however, one stitch is made next to the other (thread runs horizontally, along one course), while in effect the thread forms stitches on top of each other (thread runs vertically and forms a wale with the adjacent thread). A braid is a textile structure, which is obtained by the regular interlacing of several strands of flexible material. The difference to weaving lies in the fact that when braiding the threads are not fed at right angles. 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. Felt is a textile fabric made of a disordered, difficult to separate fiber material and is produced by dry needling (needle felting) or by solidification with under high pressure emerging from a nozzle beam water jets.

In the fiber composite material V are the reinforcing fibers B in the form of a textile structure G ', which differs from the textile structure G of the semifinished fiber H that the textile structure G forming thermoplastic styrene copolymer fibers F by melting in the thermoplastic styrene Copolymer molding compound A have been transferred. The textile structure G 'is thus formed only from the reinforcing fibers B and can thus differ in its structure from the structure G of the semifinished fiber product. Nevertheless, the textile structure G 'in the fiber composite material V is preferably a scrim, a woven fabric, a knitted fabric or a knitted fabric. Particularly preferably, the textile structure G 'is a scrim or a fabric.

The reinforcing fibers B are preferably embedded in the fiber composite material V in a structurally defined and aligned form. Preferably, a laminate-like or laminar structure of the fiber composite material V is assumed. Laminated laminates formed in this way comprise laminations of sheet-like reinforcing layers (of reinforcing fibers B) and layers of the styrene copolymer molding compound W moistening and holding them together. According to a preferred embodiment, the reinforcing fibers B are embedded in layers in the fiber composite material V. They can be obtained by arranging the textile structures G in several layers one above the other and optionally fixing them together. This fixation can be carried out by all methods familiar to the person skilled in the art, for example by knotting, linking, entangling, sewing or by the use of a suitable binder.

The textile structure G may be designed flat or spatially. Flat in this context means that the structure G extends essentially in two dimensions and the third dimension only by the natural layer thickness a single-layer textile layer, which is given by the fiber thickness, is taken. Spatially means in this context that the layer thickness of the structure G at least in some areas is greater than is predetermined by the natural layer thickness of a single-layer textile layer.

For example, rib-like thickenings can be incorporated into the textile fabric by means of suitable textile processes. The spatial textile structures G also include, for example, hollow bodies such as tubes or hoses. A spatial configuration can be achieved by a method familiar to the person skilled in the art. The reinforcing fibers B may additionally comprise auxiliaries which serve to produce and process the reinforcing fibers B, increase the durability of the reinforcing fibers B or improve the interaction of the reinforcing fibers B with the thermoplastic styrene copolymer molding material A. For this purpose, the so-called size regularly adhesion promoters are added. Such a sizing is applied regularly to the reinforcing fibers B during manufacture in order to improve the further processability of the reinforcing fibers B (such as weaving, laying, sewing). If the sizing is undesirable for subsequent processing, it must first be removed in an additional process step, such as by burning down. Then, for the production of the fiber composite material V, a further adhesion promoter is applied in an additional process step. Sizing and / or adhesion promoters form on the surface of the reinforcing fibers B a layer which can substantially determine the interaction of the reinforcing fibers B with the environment. Today, a variety of different adhesion agents are available. Depending on the field of application, the styrene copolymer molding composition A to be used and the reinforcing fibers B to be used, the person skilled in the art can select a suitable adhesion promoter which is compatible with the styrene copolymer molding compound A and with the reinforcing fibers B.

Additives (component C)

As further component C, the fiber composite material V optionally contains 0 to 40% by weight, preferably 0 to 30% by weight, particularly preferably 0.1 to 25% by weight, based on the sum of components A to C, one or more additive other than components A and B (auxiliaries and additives).

Examples of additives include particulate mineral fillers, processing aids, stabilizers, oxidation retarders, anti-heat and ultraviolet light decomposition agents, lubricants and mold release agents, flame retardants, dyes and pigments, and plasticizers. Even esters as low molecular compounds are mentioned. Also, according to the present invention, two or more of these compounds can be used. In general, the compounds are present with a molecular weight of less than 3000 g / mol, preferably less than 150 g / mol.

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

UV stabilizers include, for example, various substituted resorcinols, salicylates, benzotriazoles and benzophenones, which can generally be used in amounts of up to 2% by weight.

According to the invention, oxidation inhibitors and heat stabilizers may be added to the thermoplastic molding compound. Sterically hindered phenols, hydroquinones, substituted representatives of this group, secondary aromatic amines, optionally in combination with phosphorus-containing acids or their salts, and mixtures of these compounds, preferably in concentrations of up to 1% by weight, based on the weight of the mixture , are usable.

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

Flame retardants can be both halogen-containing and halogen-free compounds. Suitable halogen compounds, 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 halogen-free compounds, such as phosphorus compounds, in particular phosphine oxides and Derivatives of acids of phosphorus and salts of acids and acid derivatives of phosphorus used. 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.

Suitable pigments are, for example, white pigments such as zinc oxide, zinc sulfide, lead white (2 PbC0 ₃ -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 (Fe ₃ O ₄ ), spinel black (Cu (Cr, Fe) ₂ O ₄ ), manganese black (mixture of manganese dioxide, silicon oxide and iron oxide), cobalt black and antimony black, and particularly preferred Carbon black, which is usually used in the form of furnace or gas black (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 of the thermoplastic fiber composite materials V

The process for producing a fiber composite material V comprising reinforcing fibers B and a thermoplastic styrene copolymer molding compound A comprises the steps: a. Producing a sheet-like or spatial textile structure G of the reinforcing fibers B and thermoplastic styrene copolymer fibers F, wherein the styrene copolymer fibers F are made of the material of the thermoplastic styrene copolymer molding compound A;

c. Cooling of the fiber composite material V. obtained in step b.

To produce the fiber composite material, a sheet-like or spatial textile structure G comprising the reinforcing fibers B and thermoplastic styrene copolymer fibers F is provided in a first production step a.

The styrene copolymer fibers F consist of the thermoplastic styrene copolymer molding material A. Suitable thermoplastic styrene copolymer molding compositions A are all thermoplastic styrene copolymer molding compositions which can be processed into fibers. Further, with respect to the styrene copolymer fibers F, all embodiments made regarding the styrene copolymer molding compound A are applicable.

With regard to the reinforcing fibers B, reference is made to the statements made above. The sheet-like or spatial textile structure G comprises any structure of textile fibers which can be produced by means of known textile production methods. Suitable textile structures G can be woven, knitted, laid, knitted, braided, nonwoven or felts. Preferably, the textile structure G is a woven, knitted fabric, scrim or knit. Particularly preferably, the textile structure G is a fabric.

The sheet-like or spatial textile structures G are characterized in that they are obtained by processing fibers of at least two materials with one another in the textile production process. The fibers of at least two materials are at least one reinforcing fiber B and at least one styrene copolymer fiber F. The joint processing can be carried out such that a part of the fibers in the textile manufacturing process for producing a textile structure G from the reinforcing fibers B by styrene Copolymer fibers F is replaced. Thus, a single textile structure G is obtained, in which both fibers are incorporated.

The proportion of the at least one styrene copolymer fiber F can be kept constant or varied over the entire extent of the textile structure G. In areas with a higher proportion of styrene copolymer fibers F, a fiber composite material V with an egg is thus obtained after completion of the production process. property profile which to a higher degree corresponds to that of the styrene copolymer molding compound A (eg greater strength at room temperature), whereas areas with a smaller proportion of styrene copolymer fibers F are more similar in their property profile to the composite fiber fabric (eg greater flexibility at room temperature) ,

Textile production processes for the production of such textile structures in which a multiplicity of different fibers are processed with one another are known to the person skilled in the art (see "Handbuch der Verbundwerkstoffe", M. Neitzel, P. Mitschang, U. Breuer (ed.), Carl Hanser Verlag, Munich, 2014, pages 182 to 183; Handbuch der Verbundwerk-Stoffe, M. Neitzel, P. Mitschang, U. Breuer (ed.), Carl Hanser Verlag, Munich, 2014, pages 182 to 183, and "Polymer Rheology and Processing ", AA Collyer, LA Utracki (ed.) Elsevier Science Publishing Co., Inc., New York, 1990, pages 392-393).

Examples are, in particular, co-weaving, in which a part of the warp threads and / or a part of the weft threads consists in each case of styrene copolymer fibers F. Preferably, the styrene copolymer fibers F are incorporated regularly into the fabric thus produced, e.g. in that every second warp and / or weft thread is a styrene copolymer fiber F. The proportion of the styrene copolymer fibers F can be reduced by incorporating them at lower repetition rates, so that e.g. only every third or every fourth warp and / or weft yarn is a styrene copolymer fiber F. In addition, for example, the styrene copolymer fibers F can be used exclusively as a warp or weft. Both measures for varying the proportion of styrene copolymer fibers F can be combined or made independently.

Similar to co-weaving, it is possible to produce scrims in which a part of the reinforcing fibers is replaced by styrene copolymer fibers. In multilayered layers, the individual layers may have a different content of styrene copolymer fibers F.

Furthermore, co-knitting (co-knitting) is known to the person skilled in the art. In this case, textile structures G are produced in that a knitted fabric of reinforcing fibers B and styrene copolymer fibers F is formed. In the same way, knitted fabrics, braids or nonwovens may also be produced in which part of the reinforcing fibers B has been replaced by thermoplastic styrene copolymer fibers F. The proportion of styrene copolymer fibers F in the textile structure G is 30 to 95 wt .-% based on the textile structure, preferably 35 to 90 wt .-%, in particular 40 to 80 wt .-%. The reinforcing fibers B make up 5 to 70 wt .-%, preferably 10 to 65 wt .-%, in particular 20 to 60 wt .-% of the textile structure G. Furthermore, the textile structure may contain 0 to 40 wt .-% of one or more additives C, preferably 0 to 30 wt .-%, in particular 0.1 to 25 wt .-%.

In a particularly preferred embodiment, the textile structure G is designed such that it has at least one rib-like thickening on at least one surface of the structure G. Such a thickening represents a larger amount of material. In this way, a targeted stiffening of the finished fiber composite material V can be achieved.

In a second production step b for producing the fiber composite material V, the textile structure G is heated. The temperature is chosen so that it is above the melting range of the thermoplastic styrene copolymer fibers F. Preferably, the temperature is at least 10 ° C above the melting temperature of the thermoplastic styrene copolymer fibers F, more preferably at least 25 ° C, especially at least 50 ° C.

Step b is 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 to 400 ° C. In this case, it should preferably be ensured that as far as possible no pyrolysis occurs and the components used are not thermally decomposed.

According to a preferred embodiment, therefore, when carrying out step b, the residence time at temperatures of> 200 ° C. is not more than 10 min, preferably not more than 5 min, more preferably not more than 2 min, in particular not more than 1 min. Often 10 to 60 seconds are sufficient for the thermal treatment.

The process, in particular the steps b, 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 V can be improved. According to a preferred embodiment, therefore, the step b at a pressure of 5-50 bar and a pressing time of 10-60 s, preferably at a pressure of 10-30 bar and a pressing time of 15-40 s performed.

The step of heating softens the thermoplastic styrene copolymer fibers F incorporated in the fabric G until the styrene copolymer fibers F finally melt and form the styrene copolymer molding compound A.

The molten styrene copolymer molding compound A can now penetrate the cavities of the remaining textile structure G 'formed by the reinforcing fibers B and uniformly impregnate this. Since the styrene copolymer molding compound A in the form of the styrene copolymer fibers F is already present uniformly in the textile structure G 'formed by the reinforcing fibers B, a uniform and complete impregnation of the textile structure G' can take place within a shorter time and / or at lower temperatures are achieved.

Therefore, the elevated temperature of the step b is maintained until the styrene copolymer fibers F have had time to melt and uniformly fill the voids in the remaining textile fabric G 'of reinforcing fibers B. For this purpose, the structure G is preferably heated for at least 10 seconds, in particular for at least 20 seconds. The duration is dependent on the set temperature, so that a higher Temperaturn requires a shorter heating time, while at a temperature which is closer to the melting temperature of the styrene copolymer fibers F, a longer time is necessary to the styrene copolymer molding compound A, which has uniformly impregnated the textile structure G 'of reinforcing fibers B.

In a third production step c, the fiber composite material V obtained in step b is cooled. This can be done by suspending the ambient temperature or by actively cooling the fiber composite material V or the device by means of which the heating is carried out.

The cooling is preferably carried out in such a way that the fiber composite material V obtained from step B is made of reinforcing fibers B and still softened or melted styrene copolymer molding compound A without changing the shape of the fiber composite material V. For this purpose, obtained in step b fiber composite material V of reinforcing fibers B and still softened or molten styrene copolymer molding compound A is preferably cooled in the mold used for heating until the fiber composite material V has a temperature below the melting range of styrene Copolymer molding compound A is located. Preferably, the Fiber composite material V of the device removed only when sufficient strength of the styrene copolymer molding compound A has been established. Preferably, the fiber composite material V of the device is removed only when the fiber composite material V on the surface has a temperature which is at least 5 ° C below the melting temperature of the styrene copolymer molding compound A, more preferably at least 10 ° C.

In this consolidation, air pockets in the fiber composite material V are reduced and a good bond is made between thermoplastic styrene copolymer molding compound A and reinforcing fibers B (particularly when it is layered reinforcing fibers B). After consolidation, it is preferable to obtain a (as far as possible) non-porous composite material.

The fiber composite material V produced by the method described above is characterized in that it comprises at least one sheet-like or spatial textile structure G 'of reinforcing fibers B, which is embedded in the thermoplastic styrene copolymer molding compound A, wherein the styrene copolymer Formmasse A, the cavities between the reinforcing fibers B substantially fills. "Substantially fills in" in this context means that the cavities to at least 80 vol .-%, preferably 90 vol .-%, in particular 95 vol .-% are filled with the styrene copolymer molding composition A.

Alternatively, said steps of the manufacturing process may be carried out in separate sequence. For example, first textile structures G can be prepared, which can be consolidated in a further step to a composite material as fiber composite material V.

Accordingly, the invention also relates to a semifinished fiber product H. This corresponds to the planar or spatial textile structure G provided in step a comprising reinforcing fibers B and styrene copolymer fibers F. It can be obtained by using at least one reinforcing fiber B and at least one styrene copolymer. Fibers F are processed together in a textile processing process to a holding textile composite. The styrene copolymer fibers F consist of the thermoplastic styrene copolymer molding compound A. Suitable thermoplastic styrene copolymer molding compositions A are all thermoplastic styrene copolymer molding compositions which can be processed into fibers. Furthermore, with respect to the material from which the styrene copolymer fibers F are made, all designs that were made regarding the styrene copolymer molding compound A.

The thermoplastic styrene copolymer fibers F can be effected by all methods known to the person skilled in the art, in particular by melt extrusion. The thermoplastic styrene copolymer fibers F preferably have a filament number of more than 500, in particular more than 1000, and a yarn count of from 10 to 5000 tex, in particular from 50 to 4000 tex. With regard to the reinforcing fibers B, reference is made to the statements made above.

To provide the textile structure G, the reinforcing fibers B are processed into fabrics together with the styrene copolymer fibers F by a textile-technical process familiar to the person skilled in the art. Common methods are weaving, knitting, knitting, laying, braiding, felting and knotting. The sheet-like textile structures G in the context of this invention are preferably fabrics, scrims, knits, braids, knitted fabrics, nonwovens or felts according to the abovementioned definitions. Preference is given to tissue. Possible weave types of weave include canvas weave, twill weave and satin weave.

The semi-finished fiber H according to the invention is characterized in particular by the fact that the fibers are dimensionally stable connected to each other in order to fix them. This is achieved either by achieving a mechanical fixation, such as by knotting, linking, entangling, sewing or by the friction of the fiber surfaces together. The semi-finished fiber H can also be bound to each other by the BeSchichtung by means of a suitable binder. Suitable binders are known to the person skilled in the art. Preference is given to a mechanical fixation of the fibers with one another, so as to achieve a sufficient dimensional stability, so that the semi-finished fiber H is storable and transportable. The fiber semifinished product H thus obtained can be stored and transported in a space-saving manner in rolled-up form and subsequently brought into the fiber composite material V of the desired shape by the method described above according to steps b and c.

The fiber composite material V can also be reinforced by the fact that in the manufacturing step b in addition to at least one side of the semifinished fiber H a layer of a thermoplastic molding material A 'is applied. The molding compound can be the same or different from the styrene copolymer molding composition A. The molding composition may be, for example, a styrene-containing polymer, a polycarbonate, a polyolefin, or another thermoplastic polymer known to the person skilled in the art. Preferably, A is a styrene copolymer or a polycarbonate. In one embodiment, the styrene copolymer molding compositions A and A 'are identical. Reference is made to the comments on the styrene copolymer molding compound A. For example, styrene copolymers 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).

The molding compound A 'can be applied in the form of a film, a melt, a granulate of a powder or another form familiar to the person skilled in the art on at least one side of the semifinished fiber H. Preferably, the molding material A 'is applied in the form of a film or granules on at least one side of the semi-finished fiber H. The molding compound is distributed uniformly over at least part of the entire surface of the semifinished fiber H. Preferably, the molding compound A is applied to at least part of the surface of both sides of the semi-finished fiber H.

If the molding compound A is applied, this is done in an amount of at least 0.1 g / cm ² , preferably at least 1 g / cm ² , more preferably at least 3 g / cm ² on at least one surface of the semifinished fiber H.

The invention also relates to a molded part T which can be obtained or obtained from the semifinished fiber H described by deformation. This can be done in any desired manner, for example by mechanical shaping by means of a shaping body, which can also be a roller with embossing.

Preferably, the still moldable fiber composite material V, in which the thermoplastic styrene copolymer molding compound A and optionally the molding compound A 'still present (partially) molten, ie, during the implementation of step b or subsequently formed thereon. Alternatively or additionally, a cured fiber composite material V can be cold-formed or re-formed with reheating. Particularly preferably, the molded part T is obtained by a method in which the semi-finished fiber H described above is provided in a first step a. In a second step b, the semi-finished fiber H is brought into the desired shape under shaping melting. For this purpose, any method familiar and suitable to the person skilled in the art can be used.

In particular, the semi-finished fiber H is brought into the desired shape of the molded part T by compression molding, hot pressing, diaphragm molding or hydroforming. During compression molding, the textile semifinished product is led into an open mold, heated and pressed under pressure. In hot pressing, the molds are heated. In diaphragm molding, a semifinished product is placed between two elastic membranes, the so-called diaphragms, the space of which is evacuated. The semi-finished product is heated to softening and then placed together with the diaphragm in a forming tool. This preferably consists only of a mold half, which has a temperature below the softening temperature of the material. Diphragma and softened semi-finished products are pressed into the tool half by means of compressed air and the semifinished product cools down under forced pressure and isostatic pressure. In hydroforming, an assembly consisting of upper and lower tools is used, the lower tool forming the counter-mold into or onto which the laminate is to be imaged. The upper tool consists of a closed down by means of a flexible membrane chamber, which can be subjected to the deformation with hydraulic pressure. Before forming, the thermoplastic molding compound must be softened by heating, e.g. by convection ovens or contact heating.

The stability of the molded part T can be increased by the addition of additional amounts of thermoplastic material. For this purpose, the semifinished fiber H can be provided on at least one side with an additional amount of a thermoplastic molding material A 'before the step of shaping melting. The molding material may be the same or different from the styrene copolymer molding compound A, which forms the basis for the styrene copolymer fibers F. With regard to the selection of the styrene copolymer molding compound A, the statements made above apply.

The molding compound A 'can be applied in the form of a film, a melt, a granulate of a powder or another form familiar to the person skilled in the art on at least one side of the semifinished fiber H. Preferably, the molding material A 'is applied in the form of a film or granules on at least one side of the semi-finished fiber H. The molding material is uniformly applied to at least part of the distributed throughout the entire surface. Preferably, the molding compound A 'is applied to at least part of the surface of both sides of the semifinished fiber H.

If the molding compound A 'is applied, this is done in an amount of at least 0.1 g / cm ² , preferably at least 1 g / cm ² , more preferably at least 3 g / cm ² on at least one surface of the semi-finished fiber H.

In step b, the semi-finished fiber H and possibly applied to one or more sides thereof molding compound A 'is heated.

For this purpose, a temperature is used which is above the temperature of the melting range of the styrene copolymer fibers F and possibly the molding compound A '. Preferably, a temperature of at least 200 ° C, preferably at least 250 ° C, more preferably at least 300 ° C, in particular at 300 ° C to 400 ° C is applied. In this case, it should preferably be ensured that as far as possible no pyrolysis occurs and the components used are not thermally decomposed.

The pressing process can basically be carried out at any pressure (preferably atmospheric pressure or overpressure), with and without pressing on the components. When pressed with overpressure, the properties of the fiber composite material V can be improved. According to a preferred embodiment, therefore, the step b at a pressure of 5-50 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. The pressing operation is continued until the thermoplastic styrene copolymer fibers F are melted to an extent sufficient to penetrate the textile fabric G 'as a styrene copolymer molding material A. Preferably, the pressing operation is held until all the voids of the textile structure G 'formed by the reinforcing fibers B are completely filled with the molten styrene copolymer molding compound A. Preferably, the pressing process 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 to avoid pyrolysis of the polymer. As hot pressing all the skilled person for this purpose devices can be used.

According to a particularly preferred embodiment, therefore, at least one sub-step of step b at a temperature of 300 to 340 ° C, in particular from 300 to 320 ° C, for 10 s up to 1 min (for example, from (about) 15 s, 20 s, 25 s, 30 s, 40 s, 50 s or 60 s). This can then improve the connection of the reinforcing fibers with the matrix.

In a last step c, the obtained fiber composite material V is cooled below the melting point of the styrene copolymer molding compound A. As a result, the styrene copolymer molding compound A solid and the fiber composite material V can be removed from the mold used.

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 use of fiber composite materials V as an organic sheet as a substitute for 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 organic sheets are therefore preferably provided with a ribbing or laminated on a foamed thermoplastic core or on a honeycomb core as outer 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 ribbing can take place by means 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 a preferred embodiment of the method according to the invention, however, the ribbing is achieved by already designing the textile structure G by textile production methods in such a way that the structure G has thickenings on at least one surface. Thus, fiber composite materials V are obtained, which contain a ribbing due to this local surplus of material. This can be supported by correspondingly shaped dies. Due to the uniform distribution of the styrene copolymer fibers F within the entire structure G, a rapid and complete penetration of the reinforcing fibers B with the styrene copolymer molding compound A is achieved even at these locations with an increased amount of material.

In the sandwich structure, there is likewise a similarity between the materials used, so that here too a cohesive bond is formed. Alternatively, the foam core can 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.

The achieved weight reduction is advantageous for all moving components, since energy saving can be achieved by reducing the weight of the moving masses.

In comparison to a polypropylene-based molding compound, a further advantage of the thermoplastic molding compositions described here is the non-polar surface, which enables direct coating, pasting and printing.

A further advantage of the molded parts T produced according to the invention is the high rigidity and strength which can be achieved within the shortest residence time in the production process. The stiffness and strength can be achieved by a sandwich composite or z. B. be further increased by a ribbing.

As core material in the sandwich composite both a foam core (e.g., Rohacell from Evonik) and a honeycomb core (e.g., Honeycomps from EconCore) can be used. In order to achieve a cohesive bond between the 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.

One way to achieve sufficient rigidity is the injection molding or pressing back of a ribbing in the injection molding or 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. Preferably, a SAN, ABS or ASA-based thermoplastic molding composition is used. 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 layer of thermoplastic can be colored opaque, so that optically no organic sheet can be assumed, or one can specifically induce a "fiber look" through the use of a transparent layer It is possible to reduce costs and at the same time to reduce the weight, which can facilitate the assembly of the component and of the device.With the use of organ sheets in addition to a cost and weight advantage but also an aesthetic advantage of an amorphous, transparent styrene copolymer molding compound A, a so-called "fiber-look" can be achieved. Even with the use of glass fiber, which is naturally transparent, can be made visible by painting the fibers.

Furthermore, the organic sheets according to the invention have the advantage that they can be used unpainted, wherein the coating step can be saved in comparison to the steel sheet. By using organic sheets for housing and / or load-bearing structures, the weight of mobile devices can be reduced. This has the advantage that the devices become more manageable or a larger battery can be installed at the same weight 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. The use of organic sheets can therefore substantially reduce the wall thickness since the organic sheet only has to be reshaped and thus can be made with a small thickness even for very large components.

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 sheets of organ made with a ribbing and Umsäumung are very rigid components, since the organo sheet is located in the edge of the shell component, which has an increase in the resistance moment result. Due to the amorphous styrene copolymer molding compound A and thus low shrinkage, the moldings have a very smooth surface, which can still be painted or laminated as needed.

In structural parts, such as a support frame, the organosurfaces can also achieve a large weight advantage. Again, the stiffening of the components can be supported by means of a ribbing. In addition, functional integration can save subsequent assembly steps and addi- tional components, thus providing a cost advantage in addition to weight.

Figures Figure 1 shows the fiber composite materials, the 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 arranged in a horizontal orientation (left: 25-fold magnification, right: 50-fold magnification), the fibers clearly being shown as horizontally extending dark layer between the bright 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, which 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 arranged in a horizontal orientation (left: 25-fold magnification, right: 50-fold magnification), the fibers clearly being in the form of a running dark layer can be seen between the light layers of thermoplastic molding material. 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 which have been tested according to test no. 3 were obtained. FIG. 3A shows the visual documentation. FIG. 3B shows the microscopic view of a section through the laminar fiber composite material arranged in a horizontal orientation (left: 25-fold magnification, right: 50-fold magnification), with no layer of fibers being recognizable is. Figure 3C shows the 200-fold magnification, it can be seen that the impregnation is largely completed. FIG. 4 shows the fiber composite materials 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 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 arranged in a horizontal orientation (left: 25x magnification, right: 50x magnification), whereby no layer of fibers is discernible. FIG. 4C shows a magnification of 200 times, whereby it can be seen that the impregnation is not completely completed in a few places.

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: 0.5 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

The described fiber composite materials V (organo sheets) are particularly suitable for the production of components for the automotive industry, household goods, electrical appliances, sports equipment, construction and construction materials and medical technology.

Example 1 Production of a semifinished fiber product H

By means of a conventional weaving machine, a plain weave fabric is produced.

As threads are used:

- continuous carbon fiber with a filament count of 24k, a yarn count of 1600 tex and a density of 1.81 g / cm ³ (reinforcing fibers B)

Acrylonitrile-butadiene-styrene copolymer continuous fiber obtained from a thermoplastic ABS molding composition prepared from 45% by weight of butadiene, 30% by weight of styrene, and 25% by weight of acrylonitrile (styrene copolymer fibers F) ,

Both fiber types are woven together in such a way that every second weft and warp thread is formed from a carbon fiber or an ABS fiber.

Example 2 Production of the fiber composite material V

The semi-finished fiber H obtained by the process described above is introduced into the interval hot press and pressed at 250 ° C for 30 seconds at a pressure of 15 bar. The fiber composite material V is cooled and removed from the interval hot press.

This gives a fiber composite material V with the following composition:

60% by weight, based on the fiber composite material V, of an acrylonitrile butadiene

Styrene copolymers as thermoplastic styrene copolymer molding compound A and

40 wt .-%, based on the fiber composite material V, carbon reinforcing fibers

B.

Example 3 Production of molded parts T from the fiber composite materials V

From the fiber composite material V molded parts are produced by thermal forming. By using the method according to the invention, it is possible to produce thermoplastic semi-finished fiber products and fiber composite materials V and molded parts thereof, which contain the thermoplastic styrene copolymer molding compound A, layers of reinforcing fibers B and optionally an additive C. The process simplifies the production, in particular by virtue of the fact that the styrene copolymer molding compound A is already penetrated uniformly with the reinforcing fibers B by the preceding step of producing a semi-finished fiber product H in the form of a textile structure G. So textile structures G, which do not have a uniform thickness, can be converted into fiber composite materials V and moldings without the impregnation of thicker areas is incomplete or can be guaranteed only with great expenditure of time.

Production of further fiber composite materials V

Experiments were carried out on an 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

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:

Mid-layer discontinuous melt application for the production of fiber-reinforced thermoplastic semi-finished products;

Screw diameter: 35 mm

Max. Stroke volume: 192 cm ³ Max. Screw speed: 350 rpm

Max. Discharge flow: 108 cm ³ / s

Max. Discharge pressure: 2406 bar specific 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 and chain = 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 made in connection with experiments No. 1 -5 are listed in the following table:

Table 1 . Manufacturing conditions of the fiber composite materials V

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

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

¹¹

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

¹¹

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

¹¹

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

¹¹

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

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

Experiment no. 1 (comparative experiment)

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

Macro Impregnation: completed

Micro-impregnation: clearly not completed

Microscopic evaluation in semi-finished products:

Matrix layer in middle position: clearly visible

Matrix layer in top layer: not visible on the roving

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

Air inclusions: little, only in roving

Consolidation: insufficient, damage warp and weft threads

Experiment no. 2 The results are shown in FIG.

Visual assessment on the semi-finished surface:

Macro Impregnation: completed

Micro-impregnation: not completed in several places

Microscopic evaluation in 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: in the middle unimpregnated areas, all around slightly impregnated

Air inclusions: little

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

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

Macro Impregnation: completed

Micro-impregnation: completed

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

Matrix layer in middle position: not recognizable

Matrix layer in top layer: easily recognizable

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

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

Air inclusions: many, large bubbles visible

Consolidation: good, no damage

Experiment no. 4

The results are shown in FIG.

Visual assessment on the semi-finished surface:

Macro Impregnation: completed

Micro-impregnation: mostly completed Microscopic evaluation in semi-finished products:

Matrix layer in middle position: hardly recognizable

Matrix layer in cover layer: recognizable

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

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

Air inclusions: none recognizable

Consolidation: satisfactory, average damage of weft threads 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 visible Summary of the test results

Table 2. Summary trials and evaluation

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

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

It turned out that the use of higher temperatures leads to even better fiber composite materials.

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

No anhydride surfaces with 45 mdyne

Concentration grade ^* Ink ^**

tion

(% By weight)

1 (Cf.) A1 + B1 0 2 1

2 (Cf.) A1 + B1 0 2

3 A2 + B1 1 1 -2

4 A3 + B1 0.66 1 -2 1

5 A4 + B1 0.33 1 -2

6 Bond Laminates 0 4-5

Composite of approx

60% fiberglass fabric and 40%

polyamide

7 composite from approx. 0 4-5 5

60% fiberglass fabric and 40%

polypropylene

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

^** 1 = perfect, 2 = good, 3 = partial, 4 = low, 5 = poor / no trial 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 V

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

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

28 A1 + B2 240-300-320-160-80 20 20 1 26 A3 + B2 240-300-320-160-80 20 30 1

Table 5. Comparison of flexural strength.

Table 5 shows the fiber composite materials obtained in a series of experiments. In each case, pure SAN (A1) and an S / AN / maleic anhydride copolymer (A2) were combined and tested with a commercially available 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.

Experiment no. 12 13 14

Reinforcement fiber (B3)

Matrix (A4) SAN PC PA6

OD

Mean value wave depth 5.2 1 1.7 12.3

MW Wt (m)

Maximum value Wave depth 7.8 22.3 17.2

Max Wt (m)) 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.

Examples of multilayer organic sheets

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

Example: Production of the fiber composite material M

40% by weight, based on the fiber composite material, of an acrylonitrile-styrene-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% by weight, based on the fiber composite material, of a glass-based reinforcing fiber with chemically reactive functionality (silane groups) on the surface [GW 123-580K2 of PD Glasseiden GmbH].

Example: Production of the Fiber Composite Material N 65% by weight, based on the fiber composite material, of an acrylonitrile-butadiene-styrene copolymer as thermoplastic molding material A (ABS produced from: 45% by weight butadiene, 30% by weight Styrene, 24% by weight of acrylonitrile and 1% by weight of maleic anhydride) is mixed with 35% by weight, based on the fiber composite material, of a glass-based reinforcing fiber with chemically reactive functionality (silane groups) on the surface. che [GW 123-580K2 of PD Glasseiden GmbH]. The fiber composite material is subsequently ribbed.

Example: Production of molded parts from the fiber composite materials M and N

Example A: Washing machine window

Example B: Lens covers

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

Further tests on the bending stress on fabrics reinforced with fabrics

Verb and substance e n

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 process described in claim 1 are listed in the table below: TABLE 7 Compositions Compare 1, compare 2, compare 10 and compare 15 and the compositions V3 to V9 according to the invention and V1 to V14. X: weight ratio component A: B = 60: 40

No. A1 A2 A3 A4 B1 B2 T [° C] t [s]

See 1 X X 260 20-30

See 2 X X 300 30-30

V3 X X 280 20-30

V4 X X 280 40

V5 X X 320 30-30

V6 X X 300 20-30

V7 X X 320 20-30

V8 X X 310 20-30

V9 X X 320 20-30

See 10 XX 320 20-30 V1 1 XX 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.

Table 8 shows 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 average maximum bending stress than the organo sheets comprising a matrix containing 75% by weight of styrene (S) and 25% by weight of acrylonitrile ( AN) (See Figures 10 and 15). The comparison of V9 with Cf. 10 shows that under the same conditions (T = 320 ° C and t = 30 s), the organic sheet according to the invention has a greater bending stress in both the warp and in the weft direction.

It can be seen that improved products can be obtained by the process for producing the fiber composite material with a thermoplastic molding compound A, reinforcing fibers B.

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

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

and sandwich panels

Plate width: 660 mm

Laminate thickness: 0.2 to 9.0 mm

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

Sandwich panel thickness: max. 30 mm

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

Nominal feed 5 m / h

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

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

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

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

GmbH & Co. KG)

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

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

All produced composite fiber materials could be produced in each case as (large) sheetlike Orga- nobleche in a continuous process, which could be cut to size (in laminatable, customary transport dimensions such as 1 m x 0.6 m). In the case of the 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 was created. Measurement errors and a general distortion / skew of the sample were compensated by the use of profile filters (noise filter and tilt filter). The 2D height profile of the image was transmitted via defined measuring lines by integrated software in line profiles and evaluated computer-assisted.

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

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

Table 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) Construction SAN (1) PA6 (1)

Construction + Sae (4)

Components M1 b + Sae M2b + Sae

MW Wt 5.535 5.205 17.05

MW Ra 4,261 4,24 4,861

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 of the respective fibers) The following transparent fiber composite materials were produced, into each of which two-dimensional fiber material was introduced. The fiber composite materials produced each had a thickness of about 1, 1 mm. In order to further increase the comparability of the samples, a thin fiberglass mat (GV50, see above) was applied to the produced fiber composite materials on both sides. This one has none noticeable influence on the mechanical or optical properties. The following bending strengths according to DIN EN ISO 14125 were determined for the samples:

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

Optional further processing

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

Summary of the test results

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

Claims

claims

1) A process for producing a fiber composite material V comprising reinforcing fibers B and a thermoplastic styrene copolymer molding compound A, comprising the steps:

a. Producing a sheet-like or spatial textile structure G from the reinforcing fibers B and thermoplastic styrene copolymer fibers F, the styrene copolymer fibers F consisting of the material of the thermoplastic styrene copolymer molding compound A;

b. Heating the textile structure G to a temperature above the

Melting range of the thermoplastic styrene copolymer fibers F is; c. Cooling of the fiber composite material V. obtained in step b.

2) Method according to claim 1, characterized in that the styrene copolymer of the styrene copolymer molding compound A is a styrene-butadiene block copolymer.

3) Method according to claim 1, characterized in that the thermoplastic styrene copolymer fibers F at least one copolymer from the group of styrene / acrylonitrile copolymer (SAN), acrylonitrile / butadiene / styrene copolymers (ABS) and acrylonitrile / styrene / Acrylic ester copolymers (ASA) included.

4) Method according to one of claims 1 to 3, characterized in that the reinforcing fibers B are selected from the group consisting of carbon fibers, glass fibers and aramid fibers.

5) Method according to one of claims 1 to 4, characterized in that the textile structure G is a woven fabric, scrim, knitted fabric, braid, knitted fabric, nonwoven fabric or felt, wherein in each case the thermoplastic styrene copolymer fibers F and the reinforcing fibers B with each other are processed.

6) Method according to one of claims 1 to 5, characterized in that the textile structure G is a fabric which contains at least 5 wt .-% of reinforcing fibers B. 7) Thermoplastic semi-finished fiber H, containing 30 to 95 wt .-% of thermoplastic styrene copolymer fibers F and 5 to 70 wt% of reinforcing fibers B, wherein the thermoplastic styrene copolymer fibers F and the reinforcing fibers B by a textile manufacturing method have been connected to a sheet-like or spatial textile structure G together. 8) semifinished fiber H according to claim 7, characterized in that the styrene copolymer of the styrene copolymer molding compound A is a styrene-butadiene block copolymer.

9) semifinished fiber H according to claim 7, characterized in that the thermoplastic styrene copolymer fibers F at least one copolymer from the group styrene / acrylonitrile copolymer (SAN), acrylonitrile / butadiene / styrene copolymers (ABS) and acrylonitrile / styrene / Acrylic ester copolymers (ASA) included.

10) semifinished fiber H according to any one of claims 7 to 9, characterized in that the reinforcing fibers B are selected from the group consisting of carbon fibers, glass fibers and aramid fibers. 1 1) Hinge H according to one of claims 7 to 10, characterized in that the textile structure G is a woven fabric, scrim, knitted fabric, braid, knitted fabric, nonwoven fabric or felt, wherein in each case the thermoplastic styrene copolymer fibers F and the reinforcing fibers B were processed together. 12) semifinished fiber H according to one of claims 7 to 1 1, characterized in that the textile structure G is a fabric containing 20 to 60 wt .-% of reinforcing fibers B.

13) Molding T, made by a process comprising the following steps: a. Production of a thermoplastic semi-finished fiber H according to one of claims 7 to 12;

b. Shaping melting of the semi-finished fiber H to obtain the desired molding T;

c. Cooling of the obtained molding T.

14) molded part T according to claim 13, wherein the semifinished fiber H is provided on at least one side with a layer containing a further thermoplastic material prior to the step of shaping.

15) molded part T according to claim 13 or 14, wherein the shaping melting is carried out by compression molding, hot pressing, diaphragm shapes or hydroforming.