KR20090110373A - Lightweight Component in Hybrid Construction - Google Patents

Abstract

The present invention relates to lightweight components in hybrid construction, also referred to as hybrid components or hollow-chamber lightweight components, comprising a shell-like base which is reinforced by means of thermoplastics and is suitable for the transmission of high mechanical loads, the thermoplastic being linear, partially crystalline polyamide in combination with at least one filler and at least one elastomer modifier.

Description

Lightweight Component in Hybrid Construction

The present invention consists of a sheath-shaped parent reinforced with thermoplastic material which is an unbranched linear semicrystalline polyamide in combination with at least one elastomer modifier and at least one filler, suitable for the transfer of high mechanical loads, A lightweight element of a hybrid design, also known as a hybrid element or hollow-chamber lightweight element. In one preferred embodiment, the hybrid element is an element that can be subjected to mechanical and also thermal loads in operation. For the purposes of the present invention, the elements under heat load withstand temperatures of at least 150 ° C. At temperatures above 150 ° C., the resistance of the material to creep is sufficient to allow it to withstand mechanical loads at the same time. In order to ensure that the material has adequate creep resistance when subjected to thermal loads as well as mechanical loads, the temperature should generally not exceed 190 ° C.

Therefore, for the purposes of the present invention, elements under mechanical load are generally not exposed to temperatures above 190 ° C.

Appropriately designed, these lightweight elements are used in load bearing components of vehicles, office equipment, household appliances, or other equipment, or structural elements for decorative purposes. The parts manufactured during vehicle construction are preferably for front ends, headlight frames, pedestrian-protective beams, special slam panels for engine hoods or trunk covers, front roof arches, rear roof arches, roof frames, roof modules (full roof), sliding -Loop support parts, dashboard support parts (cross car beams), steering column retainers, firewalls, pedals, pedal blocks, gear-shift blocks, A, B, or C columns, B-column modules, longitudinal members, longitudinal members Joint elements for connection of column B, joint elements for connection of column A and transverse members, connection of column A, transverse and longitudinal members, connection of transverse members and around the wheels, wheel-peripheral module, crash Box, rear end, spare wheel housing, engine hood, engine cover, engine sump, gearbox sump, oil module, water tank assembly, engine-stiff system (front-end rigidity) Stems, chassis elements, vehicle floors, thresholds, threshold-reinforcement systems, floor reinforcement systems, seat-reinforcement systems, transverse seat members, rear doors, frames, seat structures, backrests, seat wraps, integrated seat belts It may be a seat back shelf with or without a seat back, a lightweight element.

A feature of the lightweight design of the hybrid design, also referred to as hybrid element hereinafter, is the interlocking adhesion of a sheath-like matrix made of almost metal to a plastic part introduced therein or coated thereon.

DE-A 27 50 982 discloses a non-removable connection involving two or more parts, preferably made of metal, wherein the connection is made of plastic and in a mold containing the connected part, for example For example, by injection-molding process. EP-A 0 370 342 has reinforcing ribs whose interior spaces are firmly connected to the parent, the reinforcing ribs consisting of molded-attached plastics, the connection of which to the parent through which the plastic traverses the area of perforation. A lightweight element of a hybrid design consisting of a sheath-like matrix, which occurs at a discontinuous connection site by perforation in the parent, which is stretched to form a tight interlocking bond, is disclosed. EP-A 0 995 668 reinforces this principle in that the hollow-chamber lightweight element further comprises a cover plate or cover sheath made of plastic. However, it is also possible to consider cover plates made of other materials such as metals.

WO 2002/068257 discloses what is known as an integrated structure consisting of metal and plastic, while describing a number of fastening means for firmly connecting the two components to one another. WO 2004/071741 discloses another method, namely using two operations: forming a metal part into plastic, forming the plastic part through a hole in the metal part and leaving the flash material on the other side. In the beginning, additional conversion work is required before the material leads to a tight interlocking bond. EP 1 294 552 B1 discloses that for the production of hybrid elements, it is possible for the metal core, but not completely, to be partially molded by plastic to provide a rigid interlocking bond. WO 2004/011315 discloses another variant in which both metal parts have upper and lower holes to ensure engagement with the molded plastic. WO 2001/38063 describes a composite plastic part consisting of at least two sheet-shaped workpieces of different materials, for example plastics and metals, or of different metals or plastics, the workpieces being connected to each other in their surrounding areas. The connection is made of a molded-attached thermoplastic material. EP 1 223 032 A2 discloses a sheet-shaped lightweight element of hybrid design. US 6,761,187 B1 discloses a hybrid element in the form of a channel or tube with an integrated closure made of thermoplastic. DE 195 43 324 A1 discloses how metal components can be prepared for use as hybrid elements in order to obtain tightly engaged bonds with thermoplastics. EP 1 340 668 A2 or EP 1 300 325 A2 offers the possibility of installing ribs in the exterior as well as in the metal parts for reinforcement.

It has immediately been recognized that the lightweight elements of the hybrid design are well suited for all cases where high stability, high energy absorption, and weight savings in collisions are important, i. EP 0 679 565 B1 is a front end of a vehicle with at least one rigid cross bar, having at least one support part made of plastic, cast over the distal region of the rigid cross bar, extending over most of the length of the front end. It is starting. EP 1 032 526 B1 is a steel sheet matrix, an unreinforced amorphous thermoplastic material, a glass-fibre-reinforced thermoplastic material, and also a load-bearing structure for the front module of an automobile made of a frame made of polyamide, for example It is starting. DE 100 53 840 A1 discloses a bumper system or energy-absorber element consisting of metal sheets arranged oppositely and connecting ribs made of thermoplastic or thermoset material. WO 2001/40009 discloses the use of hybrid technology in brake pedals, clutch pedals or accelerator pedals in motor vehicles. EP 1 211 164 B1 again describes a support structure for an automobile radiator arrangement, using a hybrid structure. DE 101 50 061 A1 discloses a locking cross member in a vehicle front module with a hybrid design. US 6,688,680 B1 describes horizontal members of a hybrid design in a vehicle. EP 1 380 493 A2 provides yet another example of a front end panel of a motor vehicle, wherein the material is not injected around the entirety of the metal part and takes the form of a mesh supporting it. The lightweight element of the hybrid design can be used anywhere on the vehicle's body as well as for the front end or pedals. Examples for this purpose are given in DE 100 18 186 B4 for vehicle doors with door frames, EP 1 232 935 A1 for the actual bodywork of the vehicle, and DE 102 21 709 A1 for elements that withstand the load of the vehicle. .

In contrast to the elements described in the prior art, generators of motor vehicles have elements which are subjected to mechanical and thermal loads for the purposes of the present invention. The generator is driven by running the engine and thus puts a mechanical load. A common method of driving in motor vehicles is by means of drive belts (e.g. multi-bar V-belts or flat V-belts). The automotive sector has also recently started using designs in which the generator is driven directly from the crankshaft, such as with a large number of wheels in the engine.

The speed of rotation of the rotor in the generator is often at least 20 000 rpm. The mechanical stresses generated here are correspondingly high. In the generator there is a high temperature, in particular due to friction.

The casing of the generator is here regularly exposed to temperatures and mechanical loads of 150 ° C to 190 ° C. For cost reasons, the casing is preferably made from metal because the metal withstands mechanical and thermal loads. The casing generally consists of two shells and is equipped with bearings for the shaft of the rotor. In many cases, the shell also has an exhaust slit. The at least one envelope also generally has a fastening element to fasten the generator in the engine compartment of the motor vehicle. The casing also generally has other functional elements of a relatively complex design.

The elements of an electric motor are comparable to generators that are regularly exposed to mechanical and thermal loads for similar reasons.

The valve cover of an automobile is another example of an element for the purposes of the present invention. The valve cover, also called "cylinder head cover", forms the uppermost boundary of the (vertical) internal combustion engine.

This hides the upper actuating element of the valve actuation mechanism and prevents lubricant from escaping into the environment, and also prevents air from entering the engine; Modern engines have internal pressures slightly below atmospheric pressure to prevent combustion gases and vapors from leaking from the engine into the environment. The valve cover also very often has a filler hole for engine oil, with a closing cap.

If the valve actuation mechanism has an overhead camshaft, which is driven by the chain (all Daimler-Benz engines, many BMW engines, some Audi engines, etc.), the valve cover also includes camshaft chain teeth.

There is often a U-shaped plastic gasket that seals the valve cover against the cylinder head. For decades, the valve cover was sealed using a peripheral gasket made of cork or molded thermoset resin, which was also the case with two valve covers of a VW Beetle engine. In order to connect the valve cover to the cylinder head, there are generally a number of bolts screwed to the cylinder head through the perimeter of the valve cover and through the gasket. The design disadvantageously requires multiple bolts to make a leak-tight connection between the valve cover and the cylinder head. In order to reduce the number of bolts, modern implementations allow the bolts to pass through the center of the cover. This embodiment does not have side bolts through the gasket. This method can significantly reduce the number of bolts required. However, in this embodiment, the material of the valve cover is subject to significantly higher mechanical loads. It must withstand particularly creep to maintain sutures for extended periods of time. The valve cover must also withstand an effective working temperature, which is typically 150 ° C. Another example of an element subjected to at least a mechanical load for the purposes of the present invention during operation is an assembly holder of a motor vehicle. For example, assembly holders of this kind are used to secure a generator inside a car. The generator is subjected to a mechanical load by belt drive, so that the mechanical load is transmitted to the assembly holder. If the arrangement has an assembly holder of this type in the vicinity of the hot element, it is also subjected to thermal loads.

If the elements are subjected to mechanical and thermal loads for the purposes of the present invention, the material chosen for the production of the elements is generally metal. The material withstands mechanical and thermal loads.

There are plastics that withstand mechanical and thermal loads in a similarly comparable manner, but these are expensive specialty plastics and are not used for cost reasons.

As shown in the prior art, hybrid elements can be used for a number of applications. A hybrid element intended for use as an end plate for a generator or electric motor, or as a valve cover, consists of a sheath-shaped matrix reinforced with a thermoplastic. The thermoplastic material generally comprises a filler, preferably a fiber, which reinforces the thermoplastic material. However, the drawbacks of these reinforcing fillers are that they adversely affect the flowability of the thermoplastics such that the thermoplastics cannot be processed as required to provide the hybrid elements, or the elements produced therefrom are mechanically in the sense mentioned in the introduction. Or results in the inability to receive thermal loads.

Therefore, the object of the present invention firstly has the advantages known from the prior art, such as high torsion resistance, high torsional stability and relatively high strength, but furthermore it is characterized by a hollow-characteristic characterized by a relatively low weight and a molding temperature during relatively low production. It is to make a chamber lightweight element, where the viscosity of the polyamide polycondensate composition will allow some kind of loss in properties such as impact resistance and hydrolysis resistance which are exhibited when low viscosity linear polymer resins or additives known in the literature are used. There is no need to lower the use of additives in the polymer melt, but at the same time allowing the use of up to 60% by weight of filler, without the loss of mechanical and / or thermal properties of the molded article made therefrom. In terms of rigidity and final tensile strength, the intention is ideally free of significant differences in this class of polyamide compositions derived from polyamide polycondensates without the use of additives, and thus have a plastic structure based on polyamide. It was to allow problem-free replacement of the material for which it was intended, ie to provide suitable use for the hybrid element.

The object is that the present invention consists of an envelope-like matrix having a reinforcing structure whose outer and / or inner spaces are made of a thermoplastic material which is firmly connected to the mother and molded-attached and which is connected to the mother at discontinuous connection sites,

A) 55 to 10 parts by weight, preferably 50 to 30 parts by weight, particularly preferably 45 to 32 parts by weight, linear, unbranched semicrystalline thermoplastic polyamide,

B) 48 to 80 parts by weight, preferably 50 to 75 parts by weight, particularly preferably 55 to 70 parts by weight of at least one filler, and

C) providing a lightweight element characterized by the use of a polymer composition comprising at least one elastomeric modifier, 0.01 to 10 parts by weight, preferably 0.25 to 6 parts by weight, particularly preferably 1.0 to 4 parts by weight. Is achieved.

However, the present invention also has a reinforcing structure whose outer and / or inner spaces are made of a thermoplastic material which is firmly connected to the mother and molded-attached and connected to the mother at discontinuous connection sites,

A) 55 to 10 parts by weight of linear, unbranched semicrystalline polyamide,

B) 48 to 80 parts by weight of at least one filler, and

C) A polymer molding composition comprising 0.01 to 10 parts by weight of at least one elastomeric modifier is processed by a molding process in a molding die.

The processing of the polymer molding compositions to provide the lightweight elements of the invention with hybrid designs is carried out by molding methods for thermoplastics, preferably injection molding, melt extrusion, compression molding, stamping or blow molding. According to the invention, linear, unbranched semicrystalline thermoplastic polyamides are most suitable for use as hybrid elements. However, it may be contemplated to use other plastics such as polyester, polyethylene, polypropylene, and the like.

One skilled in the art knows various methods for the preparation of polyamides. The effect to be obtained is likewise whether the plastic part completely encapsulates the metal part or simply forms a mesh around it, as in the case of EP 1 380 493 A2, and the plastic part is subsequently applied to, for example, a laser. Known from the prior art mentioned above, whether introduced by adhesion or connection to a metal part by means, or whether the plastic part and the metal part obtain a tight interlocking bond in further work, as in WO 2004/071741. It is obvious with any variation for the use of hybrid techniques. The effect to be obtained is likewise evident in elements of the hybrid design which are subjected to mechanical or thermal stresses or both mechanical and thermal stresses, for example end plates of generators or electric motors.

Techniques for producing elements of hybrid designs may be referred to as methods for weight reduction. The invention therefore relates to a sheath-like matrix having a reinforcing structure in which the lightweight element to be manufactured is made of a thermoplastic material, the outer and / or inner space of which is firmly connected to the mother and which is molded-attached, and connected to the mother at discontinuous connection sites. And the polymer molding composition to be used

A) 55 to 10 parts by weight of linear, unbranched semicrystalline polyamide,

B) 48 to 80 parts by weight of at least one filler, and

C) There is also provided a method for reducing the weight of elements, preferably of any kind of vehicle, characterized in that it comprises 0.01 to 10 parts by weight of at least one elastomeric modifier.

According to the invention, polyamides A) which are particularly preferably used as component A) are linear, which can be prepared starting from diamines and dicarboxylic acids and / or lactams having at least five ring elements, or corresponding amino acids. Unbranched semicrystalline polyamide.

Starting materials that can be used for this purpose are aliphatic and / or aromatic dicarboxylic acids such as adipic acid, 2,2,4- and 2,4,4-trimethyladipic acid, azelaic acid, sebacic acid, isophthalic acid, terephthalic acid Carboxylic acids and aliphatic and / or aromatic diamines such as tetramethylenediamine, hexamethylenediamine, 1,9-nonanediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, isomer dia Minodicyclohexylmethane, diaminodicyclohexylpropane, bisaminomethylcyclohexane, phenylenediamine, xylenediamine, aminocarboxylic acids such as aminocaproic acid, and the corresponding lactams. Copolyamides consisting of a plurality of monomers mentioned are also included.

Preferred polyamides according to the invention are from caprolactam, very particularly preferably ε-caprolactam, and also most combinations based on copolyamides with PA6, PA66, and other aliphatic and / or aromatic polyamides, respectively. Prepared from the material, there are 3 to 11 methylene groups for every polyamide group in the polymer chain.

The filler used as component B) according to the invention is preferably a fibrous reinforcing material, in particular chopped glass fibers.

In particular when glass fibers are used, it is also possible to use not only silanes but also polymer dispersions, film-forming agents, branching agents, and / or glass fiber-processing aids.

Particularly preferably used according to the invention, glass fibers having a diameter of generally 7 to 18 μm, preferably 9 to 15 μm, are added in the form of continuous-filament fibers or in the form of cut or ground glass fibers. The fibers may be equipped with a suitable size system and / or a coupling agent or coupling agent system, such as for example based on silanes.

By allowing the process to provide a molding composition or molded article, the length of the glass fibers in the molding composition or molded article can be significantly shorter than the length of the glass fibers generally used in the manufacture of the molding compositions.

The elastomeric modifier used as component C) according to the invention

C1 5 to 95% by weight, preferably 30 to 90% by weight of at least one vinyl monomer

C2 at least one of 95-5% by weight, preferably 70-10% by weight of one or more graft substrates having a glass transition temperature of less than 10 ° C, preferably less than 0 ° C, particularly preferably less than -0 ° C. Graft polymers.

The median particle size (d50 value) of the graft base C2 is generally from 0.05 to 10 μm, preferably from 0.5 to 5 μm, particularly preferably from 0.2 to 1 μm.

Monomer C.1 is preferably

C.1.1 50 to 99% by weight of vinylaromatic and / or ring-substituted vinylaromatic compounds, preferably styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, and / or C1-C8-alkyl Methacrylates, preferably methyl methacrylate or ethyl methacrylate, and

C.1.2 1 to 50% by weight of vinyl cyanide, preferably unsaturated nitriles, especially acrylonitrile and methacrylonitrile and / or C1-C8-alkyl (meth) acrylates, preferably methyl methacrylate, n-butyl acrylate, t-butyl acrylate, and / or derivatives, preferably a mixture of anhydrides and imides of unsaturated carboxylic acids, preferably maleic anhydride and N-phenylmaleimide.

Particularly preferred monomers C.1.1 are those selected from at least one of styrene, α-methylstyrene and methyl methacrylate monomers, and preferred monomers C.1.2 are at least one of acrylonitrile, maleic anhydride and methyl methacrylate monomers. Selected from the species.

Very particularly preferred monomers are C.1.1 styrene and C.1.2 acrylonitrile.

Graft bases C.2 suitable for graft polymers to be used in elastomeric modifiers C) are diene rubbers, EP (D) M rubbers, ie ethylene / propylene based rubbers, and other suitable graft bases, where appropriate, dienes, acrylate rubbers, Polyurethane rubber, silicone rubber, chloroprene and ethylene / vinyl acetate rubber.

Preferred graft bases C.2 are diene rubbers (eg those based on butadiene, isoprene, etc.) or diene-rubber mixtures or diene rubbers or other copolymerizable monomers thereof (eg according to C.1.1 and C.1.2). Copolymers with a mixture, provided that component C.2 has a glass transition temperature of less than 10 ° C, preferably less than 0 ° C, particularly preferably less than -10 ° C.

Other preferred graft bases C.2 are DE-A 2 035 390 (= US-A 3 644 574) or DE-A 2 248 242 (= GB-A 1 409 275) or Ullmann's Industrial Chemical Encyclopedia (Ullmann, Enzyklopaedie). der Technischen Chemie [Encyclopedia of Industrial Chemistry], Vol. 19 (1980) pages 280 ff) ABS polymers (emulsion ABS, bulk ABS and suspension ABS). (ABS = acrylonitrile-butadiene-styrene). The gel content of the graft base C.2 is preferably at least 30% by weight, particularly preferably at least 40% by weight (measured in toluene).

Elastomeric modifiers C) are prepared by free-radical polymerization, for example by emulsion polymerization, suspension polymerization, solution polymerization or bulk polymerization, preferably by emulsion polymerization or bulk polymerization.

Suitable acrylate rubbers are based on graft base C2, preferably having a polymer consisting of alkyl acrylates, having up to 40% by weight or less of other polymerizable ethylenically unsaturated monomers based on C.2, if appropriate. Among the preferred polymerizable acrylates, C 1 -C 8 -alkyl esters such as methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; Haloalkyl esters, preferably halo-C 1 -C 8 -alkyl esters such as chloroethyl acrylate, and also mixtures of these monomers.

For crosslinking, it is possible to copolymerize monomers having two or more polymerizable double bonds. Preferred examples of crosslinking monomers are unsaturated monocarboxylic acids having 3 to 8 carbon atoms and unsaturated monohydric alcohols having 3 to 12 carbon atoms, or saturated polyols having 2 to 4 OH groups and 2 to 20 carbon atoms Esters of, for example, ethylene glycol dimethacrylate, allyl methacrylate; Polyunsaturated heterocyclic compounds such as trivinyl cyanurate and triallyl cyanurate; Polyfunctional vinyl compounds such as di- and trivinylbenzenes; And also triallyl phosphate and diallyl phosphate.

Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds having at least three ethylenically unsaturated groups.

Particularly preferred crosslinking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, triacryloylhexahydro-s-triazine, and triallylbenzene. The amount of crosslinking monomer is preferably from 0.02 to 5% by weight, in particular from 0.05 to 2% by weight, based on the graft base C.2.

In the case of cyclic crosslinking monomers having at least three ethylenically unsaturated groups, it is advantageous to limit the amount to less than 1% by weight of the graft base C.2.

For the preparation of the graft base C.2, examples of preferred "other" polymerizable ethylenically unsaturated monomers that can act with the acrylate, if appropriate, are acrylonitrile, styrene, α-methylstyrene, acrylamide, vinyl C1- C6-alkyl ethers, methyl methacrylate, and butadiene. Preferred acrylate rubbers as graft base C.2 are emulsion polymers having a gel content of at least 60% by weight.

Other suitable graft substrates according to C.2 are DE-A 3 704 657 (= US 4 859 740), DE-A 3 704 655 (= US 4 861 831), DE-A 3 631 540 (= US 4 806 593 ) And silicone rubbers such as those described in DE-A 3 631 539 (= US 4 812 515), which have an active site for grafting.

As an elastomeric modifier based on the graft polymer, component C) is elastomeric, having a glass transition temperature of less than 10 ° C., preferably less than 0 ° C., particularly preferably less than −20 ° C., not based on the graft polymer. It is likewise possible to use modifiers. Examples of these may be elastomers having a block copolymer structure. Another example of these may be elastomers fused by thermoplastics. Preferred examples that may be mentioned here are EPM rubber, EPDM rubber and / or SEBS rubber.

In another preferred embodiment, the polyamide molding compositions to be used for the preparation of the elements of the invention on the basis of hybrid designs are also, if appropriate, in addition to components A), B) and C),

D) 0.001 to 30 parts by weight, preferably 5 to 25 parts by weight, particularly preferably 9 to 19 parts by weight of at least one flame retardant additive.

Flame retardants of component D) may comprise commercially available organic halogen compounds with synergists, commercially available organic nitrogen compounds, or organic / inorganic phosphorus compounds alone or in mixtures. It is also possible to use flame retardant inorganic additives such as magnesium hydroxide or Ca Mg carbonate hydrate (DE-A 4 236 122 (= CA 210 9024 A1)). It is also possible to use salts of aliphatic or aromatic sulfonic acids. Notable examples of halogen-containing, especially brominated and chlorinated compounds are ethylene-1,2-bistetrabromophthalimide, epoxidized tetrabromobisphenol A resins, tetrabromobisphenol A oligocarbonates, tetrachlorobisphenol A Oligocarbonates, pentabromopolyacrylates, brominated polystyrenes and decabromodiphenyl ethers. Suitable organophosphorus compounds are phosphorus compounds according to WO-A 98/17720 (= US 6 538 024), for example triphenyl phosphate (TPP), resorcinol bis (diphenyl phosphate) (RDP) and derived therefrom Oligomers, and also bisphenol A bis (diphenyl phosphate) (BDP) and oligomers derived therefrom, and also organic and inorganic phosphonic acid derivatives and salts thereof, organic and inorganic phosphinic acid derivatives and salts thereof, in particular aluminum tris [di Alkylphosphinates] or metal dialkylphosphinates such as zinc bis [dialkylphosphinate], and also red phosphorus, phosphites, hypophosphites, phosphine oxides, phosphazenes, melamine pyrophosphates and mixtures thereof to be. Nitrogen compounds which can be used are condensates of allantoin derivatives, cyanuric acid derivatives, dicyandiamide derivatives, glycoluril derivatives, guanidine derivatives, ammonium derivatives and melamine derivatives, preferably allantoin, benzoguanamine, glycoluril, melamine, melamine For example, melem, melam or melom, or compounds of this type having higher levels of condensation and melamine with acids such as cyanuric acid (melamine cyanide), (melamine phosphate) or condensation with phosphoric acid Those selected from the group consisting of (eg melamine polyphosphate) adducts with phosphoric acid. Examples of suitable synergists include antimony compounds, in particular antimony trioxide, sodium antimonate and antimony pentoxide, zinc compounds such as zinc borate, zinc oxide, zinc phosphate and zinc sulfide, tin compounds such as tin stannate and tin borate, And also magnesium compounds such as magnesium oxide, magnesium carbonate and magnesium borate. Materials known as carbonizers may be added to the flame retardants, examples being phenol-formaldehyde resins, polycarbonates, polyphenyl ethers, polyimides, polysulfones, polyether sulfones, polyphenylene sulfides, and poly Ether ketone, and also an antidripping agent such as tetrafluoroethylene polymer may be added.

In another preferred embodiment, the polymeric molding compositions to be used for the preparation of the elements of the invention in a hybrid design are also suitable, in addition to components A) and B) and C), and if appropriate D), or D ) instead,

E) 0.001 to 10 parts by weight, preferably 0.05 to 3 parts by weight, particularly preferably 0.1 to 0.9 parts by weight of other conventional additives.

For the purposes of the present invention, examples of conventional additives are stabilizers (eg UV stabilizers, heat stabilizers, gamma-ray stabilizers), antistatic agents, flow aids, mold release agents, further flame retardant additives, emulsifiers, nucleating agents , Plasticizers, lubricants, dyes, pigments, additives and compatibilizers for increasing electrical conductivity. The additives mentioned and further suitable additives are described in Gaechter, Mueller, Kunststoff-Additive [Plastics Additives], 3rd Edition, Hanser-Verlag, Munich, Vienna, 1989 and Plastics Additives Handbook, 5th Edition, Hanser-Verlag, Munich, 2001 ] By way of example. The additives may be used alone or in mixtures or in the form of masterbatches.

Examples of stabilizers that can be used include phenols, hydroquinones, aromatic secondary amines such as diphenylamine, substituted resorcinol, salicylates, benzotriazoles and benzophenones, and also such groups with steric hindrance Various substituted representatives of these, and mixtures thereof.

Examples of pigments and dyes that can be used are titanium dioxide, zinc sulfide, ultramarine blue, iron oxide, carbon black, phthalocyanine, quinacridone, perylene, nigrosine and anthraquinone.

Examples of nucleating agents that can be used are sodium phenylphosphinate or calcium phenylphosphinate, aluminum oxide, silicon dioxide, and also particularly preferably talc.

Examples of lubricants and release agents that can be used include ester waxes, pentaerythritol tetrastearate (PETS), long chain fatty acids (eg stearic acid or behenic acid) and esters, salts thereof (eg Ca stearate or Zn stearate), And also amide derivatives (eg ethylenebisstearylamide) or montan ester waxes, and also low molecular weight polyethylene waxes and polypropylene waxes.

Examples of plasticizers that can be used are dioctyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, hydrocarbon oils, N- (n-butyl) benzenesulfonamide.

Additives that can be added to increase electrical conductivity are carbon black, conductive black, carbon fibrils, nanosize graphite fibers and carbon fibers, graphite, conductive polymers, metal fibers, and also other conventional additives. Nanoscale fibers that can preferably be used are those known as "single-wall carbon nanotubes" or "multi-walled carbon nanotubes" (eg, products of Hyperion Catalysis).

The compatibilizer used is preferably a terpolymer of styrene and acrylonitrile in a 2.1: 1 weight ratio comprising a thermoplastic polymer having a polar group, for example 1 mol% maleic anhydride.

Compatibilizers are used in particular when the molding composition comprises the graft polymers described above in the context of component C).

The resulting preferred combination of components in the polymer molding composition for use in the elements of the hybrid design is in accordance with the present invention:

A, B, C; A, B, C, D; A, B, C, E; A, B, C, D, E;

The properties of the lightweight components of the hybrid designs made according to the invention from the polyamide molding compositions used are comparable to moldings consisting of molding compositions having comparable melt viscosities not made from linear, unbranched semicrystalline polyamides. When subjected to mechanical and / or thermal loads, they have improved properties and relatively high impact resistance. When linear, unbranched semicrystalline polyamide as component A) is used in combination with, for example, core-shell acrylate rubber as component C), thanks to the exceptionally high modulus of elasticity of about 19 000 MPa at room temperature The content of the fibers can be significantly doubled from conventional 30% to 60% by weight, resulting in doubled rigidity of the elements of the hybrid design made therefrom without any unacceptable reduction in the toughness of the material. The increase in density of the polymer molding composition here is only about 15-20%. This allows for a significant reduction in the wall thickness of the elements for the same mechanical performance at significantly reduced manufacturing costs. Surprisingly, the method does not result in the loss of the properties required according to the invention in terms of its ability to withstand mechanical and / or thermal loads, for example in the automotive sector, and has a wall thickness of less than 3 mm, preferably 2.5 mm. It can be used to produce lightweight elements of less than, particularly preferably less than 2 mm.

For the purposes of the present invention, the term "tightly connected" refers to a thermoplastic material, ie a polyamide molding composition in which fibers are located therein, for example through a hole in the parent, flowing over its edge on the opposite side of the hole, By solidification it is meant to provide a tight interlocking bond. However, this may also occur in further work, in which the mechanical work is again performed with the extension in such a way as to create a tightly engaged bond to the flash material protruding through the hole. The term "tightly connected" also includes the subsequent introduction of an adhesive using an adhesive or using a laser. However, tight interlocking bonds can also be achieved through the flow surrounding the parent.

In order to obtain a particularly good interlocking bond between a matrix of fiber-reinforced plastic material and the thermoplastic material in which the cut fibers are located, in one embodiment of the invention, the thermoplastic material is used as the fiber-reinforced plastic of the parent. Push it into the material to some extent. This provides an engagement between the thermoplastic and the fibers of the fiber-reinforced plastic material. This type of binding is particularly tight. Some of the thermoplastic material that has not been pushed into the material at this time forms a functional element or reinforcement, for example, and thus is attached in an improved manner to the fiber-reinforced plastics material.

When the thermoplastic material in which the cut fibers are located is pushed into the polyamide of the fiber-reinforced plastic material, the latter softens or liquefies. The thermoplastic material is molded on one side of the fiber-reinforced plastic material in such a way that some of the other plastic material is pushed out of the opposite side. That is, the molded-attached thermoplastic material passes between the fibers of the fiber-reinforced plastic material. The result is an interlocking bond between the molded thermoplastic material and the parent's fiber-reinforced plastic material as well as an adhesive or welded bond.

In one embodiment of the present invention, the interlocking bond is produced only at a few points between the molded thermoplastic material and the fiber-reinforced plastic material. It is technically simple to make the joining only at a few points, especially according to conventional injection molding.

1a and 1b show the shell acting as part of the casing for the generator. In particular, a bearing (end plate) 1 for the shaft of the rotor can be seen. There is an element 2 which acts to fix the generator to the vehicle. The shell also includes a relatively complex structure. These additional elements of the complex structure are believed to have various functions.

2 shows another generator with a relatively large casing consisting of two shells. In particular, a fixing element 2 can be seen, which is used for fixing the generator inside or on the vehicle. The generator shown in FIG. 2 also has a slit 3 which acts to cool the generator.

3 shows an example of a matrix intended for a generator casing. The matrix consists of a steel sheet 1 mm thick. A circular area 1 with a protruding area forms a bearing for the mandrel of the rotor. The element 2 was provided in the form of a fixing protrusion which acts to fix the generator to the vehicle. There are four feet 4 with flanges around them, extending from the bearings 1 around the opposite side of the shell of the generator casing. In other words, the matrix is limited to those elements that are subjected to particularly high mechanical loads in the generator.

The figure shows a number of different applications that can be used in the polymer molding compositions of the present invention, preferably in motor vehicles, in track vehicles, in aircraft, on ships, in sleds, or in other means of transport where the structure must be lightweight but stable, Or in the non-automotive sector of electrical or electronic devices, in household devices, in furniture, in heaters, in motor scooters, in shopping carts, on shelves, on stairs, on escalators, in manhole covers, on generators, or in electric motors. Show that it exists.

The elements used in the vehicle are preferably whole front ends, headlight frames, pedestrian-protective beams, special slam panels for engine hoods or trunk covers, front roof arches, rear roof arches, roof frames, roof modules, sliding-loop support parts. , Connection of dashboard support parts, cross car beams, steering column retainers, firewalls, pedals, pedal blocks, gear-shift blocks, A, B, or C columns, B-column modules, longitudinal members, longitudinal members and B columns Joint elements for connection of column A and horizontal members, column A for connection of horizontal members and longitudinal members, joint elements for horizontal members and around wheels, wheel-peripheral modules, crash boxes, rear ends, Spare wheel housing, engine hood, engine cover, engine sump, gearbox sump, oil module, water tank assembly, engine-stiffness system, front-end rigidity system, car Large elements, vehicle floors, thresholds, threshold-reinforcement systems, floor reinforcement systems, seat-reinforcement systems, transverse seat members, tailgates, frames, seat structures, backrests, seat wraps, seats with or without integrated seat belts, etc. Support, cargo racks, valve covers, end-shields for generators or electric motors, or entire vehicle-door structures.

Examples of particularly preferred implementations:

The matrix was overmolded with a thermoplastic comprising a linear, unbranched semicrystalline polyamide comprising 62% by weight of glass fibers (component B = LANXESS N.V., CS 7928 chopped glass fibers from Antwerp). The length of the glass fibers in the molding composition was 500-20 μm and the diameter was about 11 μm. The polyamide used was a linear unbranched semicrystalline nylon-6 with a relative solution viscosity of 2.4 (5% concentration m-cresol solution at 25 ° C.). The thermoplastic material further included the following additives:

- component C) in a 2% by weight of para-Lloyd ^{(Paraloid ®) EXL 3300 (Rohm} & Haas product, a core-shell acrylate rubber)

100 ppm Mikrotalk, a nucleating agent as component E)

0.09% carbon black as colorant as component E)

0.09% Licowax ^® E F1 (Montan ester wax from Clariant) as a release agent

Injection-molding processes were used for interlocking bonding of the thermoplastics to the parent. The thermoplastic material formed functional elements such as those shown in FIGS. 1 and 2, for example. The thermoplastic material also particularly stabilized the edges of the parent. In other words, unwanted twisting at the edges of the matrix, especially under dynamic loading. Thermoplastics have also been particularly helpful in improving the acoustical properties of generators as compared to generators with casings made of metal. The casing was lighter than a casing made of metal. In particular, the hybrid element could be manufactured at a lower cost compared to a casing made of metal or in particular a special plastic capable of withstanding thermal and mechanical loads.

4 shows a plan view of the cover with holes 6 passing between the periphery 5 and the middle of the cover. The cover is secured by bolts passing through the hole 6. This type of fastening saves a large number of bolts compared to the case where the bolts pass through holes in an array distributed over the perimeter 5. However, in the fastening embodiment shown in FIG. 4, the material of the cover is exposed to more stringent mechanical requirements. It must have creep resistance to ensure closure over long periods of time. Elements produced using the polymer molding compositions of the present invention based on linear, unbranched semicrystalline polyamides satisfy the above requirements even when exposed to thermal loads. Thus, for example, it is possible to produce a cover for a cylinder head from the material of the invention, even if the holes are not in a distributed arrangement over the periphery, but instead pass through the center of the cover to save the bolts and consequently the weight. Do.

Claims (10)

Its outer and / or inner space consists of a sheath-shaped parent with a reinforcing structure which is made of a thermoplastic material firmly connected to the mother and molded-attached and connected to the mother at the discontinuous connection site, A) 55 to 10 parts by weight of linear, unbranched semicrystalline polyamide, B) 48 to 80 parts by weight of at least one filler, and C) A lightweight element characterized by using a polymeric molding composition comprising 0.01 to 10 parts by weight of at least one elastomeric modifier. The light weight element of claim 1 wherein the polyamide used comprises nylon-6 or nylon-6,6 having a relative solution viscosity of 2.3 to 2.7 as measured in m-cresol. The process according to claim 1 or 2, wherein the polymeric molding composition is in addition to components A), B) and C). D) 0.001 to 30 parts by weight of at least one flame retardant additive, and / or E) Light weight element, further comprising 0.001 to 10 parts by weight of other conventional additives. 4. Lightweight element according to claim 1, wherein component B) used comprises chopped glass fibers. 5. A) 55 to 10 parts by weight of linear, unbranched semicrystalline polyamide, B) 48 to 80 parts by weight of at least one filler, and C) a polymer molding composition comprising 0.01 to 10 parts by weight of at least one elastomeric modifier is processed by a molding process in a molding die, the outer and / or inner space of which is firmly connected to the mother and molded- A method of making a lightweight element of hybrid form consisting of an attached thermoplastic material and having a reinforcing structure connected to the parent at discontinuous connection sites. In the light weight element according to any one of claims 1 to 4, in automobiles, track vehicles, aircraft, ships, sleds or other means of transport in which the structure must be lightweight but stable, or in the non-motor vehicle sector of electrical or electronic devices, In household devices, in furniture, in heaters, in motor scooters, in shopping carts, on shelves, on stairs, on escalator stairs, in manhole covers, in generators, or in electric motors. 7. Use of a lightweight element according to claim 6, characterized in that the lightweight element is used in a vehicle part, in an element that bears the load of an office device, a household appliance, or another appliance, or in a structural element for decorative purposes. 7. The light-weight element of claim 6, wherein the lightweight element comprises a full front end, headlight frame, pedestrian-protective beam, special slam panel for engine hood or trunk cover, front loop arch, rear loop arch, roof frame, roof module, sliding-loop support part. , Connection of dashboard support parts, cross car beams, steering column retainers, firewalls, pedals, pedal blocks, gear-shift blocks, A, B, or C columns, B-column modules, longitudinal members, longitudinal members and B columns Joint elements for connection of column A and horizontal members, joints for column A, horizontal and longitudinal members, joint elements for connecting horizontal members and around the wheels, wheel-peripheral modules, crash boxes, rear End, spare wheel housing, engine hood, engine cover, engine sump, gearbox sump, oil module, water tank assembly, engine-stiffness system, front-end rigidity system, chassis Element, vehicle floor, sill, threshold-reinforcement system, floor reinforcement system, seat-reinforcement system, transverse seat member, tailgate, frame, seat structure, backrest, seat wrap, seat backrest with or without integrated seat belt Use of lightweight elements, characterized in that they are used in automobiles for cargo racks, valve covers, generators or end-shields for electric motors, or for whole vehicle-door structures. A polymeric molding composition, using a lightweight element consisting of a sheath-shaped matrix having a reinforcing structure whose outer and / or inner spaces are rigidly connected to the mother and formed of molded-attached thermoplastic and connected to the mother at discontinuous connection sites this A) 55 to 10 parts by weight of linear, unbranched semicrystalline polyamide, B) 48 to 80 parts by weight of at least one filler, and C) 0.01 to 10 parts by weight of at least one elastomeric modifier. 6. The method of claim 5 wherein the molding process used comprises injection molding, melt extrusion, compression molding, stamping or blow molding.

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