DE10055190A1 - Production of back-injected plastic moldings, e.g. vehicle parts, involves back-injection with a mixture of plastic and long glass fibres which is melt-compounded in a machine with a special mixing element - Google Patents

Abstract

A method for the production of back-injected plastic parts by placing a sheet material in a mold and back-injecting with plastic reinforced with long fibres involves melt-compounding the plastic with the fibres before back injection, using an extruder or injection molding machine with a distributive mixing element in the zone after the compression zone. An Independent claim is also included for back-injected plastic moldings obtained by this method.

Description

The present invention relates to a method for manufacturing molded plastic parts, this plastic mold parts and their use as interior or exterior bodywork parts, aircraft interior components, housings of household and electrical appliances, garden furniture, battery carriers, window profiles, facades cladding, doors, flooring, cell phone housing or seat peel.

Process for the production of reinforced with plastic material Films or composite layer films are known to the person skilled in the art. For example, EP-A 0 285 071 describes a multilayer film described from clear layer, color layer and carrier layer, the with a substrate material made of unreinforced ABS polymer, Polybutylene terephthalate, polyamide, polyethylene or polypropylene is poured out. The clear layer used serves as protection layer for the decorative layer and preferably consists of a Mixture of a fluorinated polymer and an acrylic resin. The Layer structure of the composite layer film is described in accordance with the NEN process obtained by film casting. You get there in this way to composite moldings, but it does Manufacturing process drying steps required and is tech nically complex and therefore labor and time intensive. In addition is the breadth of application of the moldings obtained inevitably very much limited, because a practical access to fiber-reinforced Ver shaped bodies are not shown.

The production of a composite is similarly complex Layered film according to EP-A 0 352 298. According to this regulation is first a film composite of color layer and clear layer produced on a cast film, which is then replaced by the Cast film from the clear coat with the side of the paint coat on a substrate film is laminated. The individual film layers agree in their composition with those in EP-A 0 285 071 described essentially match. Furthermore, in the EP-A 0 352 298 a plastic mixed with a filling material Molding compound used to reinforce the composite film is disclosed. However, this has reinforced plastic molding compound on a non-flawless surface and therefore requires the overlay with the said composite layer film. by is also part that even with the overlying ver bundle film irregularities in the surface of the ver  Do not always avoid strong plastic material completely or have hidden.

EP-A 0 442 128 discloses a simplified method for manufacturing Positioning multi-layer moldings from a deformable film and thermoplastic or thermosetting resins in which these thermoformable film, e.g. B. made of polycarbonate, which is also printed can be in a non-preformed state in an injection molding plant stuff placed and about the pressure of the melt-shaped rear molded and held in place at the same time becomes. Whether there is a multi-layer according to the described method Process composite foils perfectly into plastic molded parts leave as open as the question of whether the position nation of the film in the injection mold and filling this injection molding tool also with fiber-reinforced art fabric materials succeed. Furthermore, EP-A 0 442 128 not addressed in what condition the film is used to has to be.

According to German patent application Az. 109 28 774.0 are behind injected molded plastic parts, which is a multilayer composite Have film, accessible in that a multilayer film made of top and decorative layers, if necessary with an intermediate layer layer, coextruded in a single process step and directly subsequently injection molded with a thermoplastic material becomes. The moldings thus obtained, for. B. with a substrate layer made of glass fiber reinforced PBT / ASA, but do not show in a flawless, required for all desired applications mechanical behavior, especially with regard to breakage elongation and tensile strength. Furthermore, it can if very long Fiber materials are used after temperature change bela stance to a poor visual impression, what An Applications in the area of visible components such as B. the body excludes exterior parts. When using glass fiber reinforced substrate injection molding compounds, especially when used of long glass fibers, so-called glass is often observed nests on the surface of the molded parts obtained. This glass ster both adversely affect the optical properties ten of the moldings obtained and locally on their mechani property profile. Even if it is on the described Way succeeds in producing molded parts that are initially flawless Surfaces, can be unevenness and given if also impairments in gloss and color in the climate change Do not always avoid the test due to these glass nests.  

It would therefore be desirable to inject molded composite parts obtained, which do not have the aforementioned disadvantages and for a wide variety of indoor and outdoor applications in question come. It would also be advantageous if the bottom or back side of a molded plastic part a uniform Er would have an appearance that is free of glass nests or similar visible or noticeable glass fiber residues, so that these components are optically perfect in every respect seem and also the back of these components can be seen can be cash such. B. with housing or tailgate lids.

The present invention was therefore based on the object Process for the production of molded plastic parts len to provide, in which one is reproducible and on technically simple way, molded plastic parts receives long fiber reinforced mate for injection molding rial is used and that in mechanical and optical Hin meet the highest requirements.

Accordingly, a process for producing film has been made injection molded plastic parts from a film and a langfa server-reinforced plastic material found, in which the film in positioned a mold and with a with a fiber reinforced plastic material to a molded part behind is injected, taking the plastic material and the fiber material before back injection in an extruder or a Injection molding machine that is in the compression zone closing zone at least one distributive mixing element point, combine, melt and mix.

Furthermore, the fo molded plastic parts and their use as interior and exterior body components, aircraft interior components, Housings of household and electrical appliances, garden furniture, batteries beams, window profiles, cladding, doors, floor coverings would be found, cell phone housing or seat shells.

The structure and composition of the films according to the invention injection molded plastic parts and their manufacture who described in detail below.

Both single-layer and two-layer or multilayer films come as films Slides in question. Preference is given to two or more layers Foils, d. H. resorted to composite layer films. suitable Single-layer films are e.g. B. from mixtures of polyamides and Polyethylene ionomers, e.g. B. entene / methacrylic acid copolymers ent holding, for example, sodium, zinc and / or lithium counterions  (inter alia available under the trademark Surlyn® from DuPont), or formed from copolyesters. Composites are particularly suitable layered films that are composed in this series follow at least one substrate layer (1), optionally min least an intermediate or decorative layer (2), and at least a transparent cover layer (3).

The substrate layer (1) generally contains ASA polymers, ABS polymers, polycarbonates, polyesters such as polyethylene terephthalate or polybutylene terephthalate, polyamides, polyethers imides, polyether ketones, polyphenylene sulfides, polyphenylene ethers or mixtures of these polymers.

ASA polymers are preferably used for the substrate layer. ASA polymers are generally understood to mean impact-modified styrene / acrylonitrile polymers in which graft copolymers of vinyl aromatic compounds, in particular styrene, and vinyl cyanides, in particular acrylonitrile, on polyalkylacrylate rubbers (component A) in a copolymer matrix composed in particular of styrene and acrylonitrile ( Component B) are present. In a further preferred embodiment, blends of ASA polymers and polycarbonates are used. Particularly suitable ASA polymers consist of a graft copolymer (component A)

• 1. 1 to 99% by weight, preferably 55 to 80% by weight, in particular 55 to 65% by weight, of a particulate graft base A1 with a glass transition temperature below 0 ° C., preferably less than -20 ° C., especially preferably less than -30 ° C,
  a2) 1 to 99% by weight, preferably 20 to 45% by weight, in particular 35 to 45% by weight, of a graft A2 composed of the monomers, based on A2,
  a21) 40 to 100 wt .-%, preferably 65 to 85 wt .-% units of styrene, a substituted styrene or a (meth) acrylic ester, or mixtures thereof, in particular styrene and / or α-methylstyrene as component A21 and
  a22) 0 to 60% by weight, preferably 15 to 35% by weight, of units of acrylonitrile or methacrylonitrile, in particular of acrylonitrile as component A22.

Component A1 consists essentially of the monomers

• a) 180 to 99.99 wt .-%, preferably 95 to 99.9 wt .-%, at least one C ₁ - to C ₈ alkyl ester of acrylic acid, preferably as n-butyl acrylate and / or 2-ethylhexyl acrylate as a compo note A11,
• b) 0 to 20% by weight, preferably 0.01 to 5.0% by weight, at least a polyfunctional crosslinking monomer, preferably Diallyl phthalate and / or dihydrodicyclopentadienyl acrylate (DCPA) as component A12.

The acrylate A1 it is preferably alkyl acrylate rubbers of one or more C ₁ - to C ₈ alkyl acrylates, preferably C ₄ - to C ₈ alkyl acrylates, preferably wherein at least some butyl, hexyl, octyl and / or 2 -Ethyl hexyl acrylate, especially n-butyl and / or 2-ethyl hexyl acrylate, can be used.

These acrylate rubbers A1 preferably contain 0.01 to 20 % By weight, preferably 0.1 to 5% by weight, based on the total important from A1, to cross-linking bi- or polyfunctional Monomers (crosslinking monomers). Examples include monomers, the two or more double bonds capable of copolymerization included and which are preferably not conjugated in the 1,3 position are. Suitable crosslinking monomers are, for example, divinyl benzene, diallyl maleate, diallyl fumarate, diallyl phthalate, diethyl phthalate, triallyl cyanurate, triallyl isocyanurate, tricyclodecenyl acrylate, dihydrodicyclopentadienyl acrylate, triallyl phosphate, Allyl acrylate, allyl methacrylate. As a particularly affordable network tion monomer has dihydrodicyclopentadienyl acrylate (DCPA) pointed (see DE-C 12 60 135). In the alkyl acrylate rubbers A1 can also up to 30 wt .-%, based on the total weight of A1, "hard" polymer-forming monomers, such as vinyl acetate, (Meth) acrylonitrile, styrene, substituted styrene, methyl meth be polymerized in acrylate and / or vinyl ether.

According to one embodiment of the invention serve as a graft A1 crosslinked acrylic acid ester polymers with a glass transition temperature below 0 ° C. The cross-linked acrylic ester poly Merisate should preferably have a glass transition temperature below Have -20 ° C, especially below -30 ° C.

According to a preferred embodiment, the graft base A1 is composed of 15 to 99.9, in particular 70 to 99.9% by weight of C ₁ to C ₈ alkyl esters of acrylic acid, 0.1 to 5, in particular 0.1 to 3,% by weight. -% crosslinker and 0 to 49.9, in particular 0 to 20% by weight of one of the specified further monomers or rubbers.

Suitable monomers for forming the graft A2 are as Kom component A21 z. B. styrene, substituted styrenes such as one or multiply substituted alkyl and / or halostyrenes, e.g. B. α-methylstyrene, and (meth) acrylic acid esters such as methyl methacrylate, 2-ethylhexyl acrylate and n-butyl acrylate, especially methyl meth acrylate. Acrylonitrile and methacrylic come as component A22 nitrile, in particular acrylonitrile in question.

Component A is preferably a graft copolymer. The graft copolymers A generally have an average particle size d ₅₀ of 50 to 1000 nm, preferably from 50 to 800 nm and particularly preferably from 50 to 600 nm. Preferred particle sizes of the graft base A1 are in the range from 50 to 350 nm, preferably from 50 to 300 nm and particularly preferably from 50 to 250 nm.

The graft copolymer A can be built up in one or more stages be d. H. the graft core is made up of one or more grafts surrounded by envelopes. Several graft shells are usually through gradual grafting applied to the rubber particles where each graft can have a different composition. to in addition to the grafting monomers, polyfunctional ones crosslinking or reactive groups containing monomers with be grafted (see also EP-A 230 282, DE-AS 36 01 419 and EP-A 269 861).

In a preferred embodiment, component A consists of a multi-stage graft copolymer, the graft stages generally being made of resin-forming monomers and having a glass transition temperature T _g above 30 ° C., preferably above 50 ° C. The multi-stage structure serves, inter alia, to achieve (partial) compatibility of the rubber particles A with component B.

According to a further preferred embodiment of the invention is the particle size distribution of component A bimodal, where usually 60 to 90 wt .-% an average particle size of 50 to 200 nm and 10 to 40 wt .-% an average particle size of 50 to 400 nm, based on the total weight of component A, exhibit.

The sizes determined from the integral mass distribution are specified as the average particle size or particle size distribution. The mean particle sizes according to the invention are in all cases the weight average of the particle sizes, as they are using an analytical ultracentrifuge according to the method: by W. Scholtan and H. Lange, Kolloid-Z, and Z.-Polymer 250 (1972 ), Pages 782-796. The ultracentrifuge measurement provides the integral mass distribution of the particle diameter of a sample. From this it can be seen what percentage by weight of the particles have a diameter equal to or smaller than a certain size. The average particle diameter, which is also referred to as the d ₅₀ value of the integral mass distribution, is defined as the particle diameter at which 50% by weight of the particles have a smaller diameter than the diameter which corresponds to the d ₅₀ value. Likewise, 50% by weight of the particles then have a larger diameter than the d ₅₀ value. In addition to the d ₅₀ value (average particle diameter), the d ₁₀ and d ₉₀ values resulting from the integral mass distribution are used to characterize the width of the particle size distribution of the rubber particles. The d ₁₀ or d ₉₀ value of the integral mass distribution is defined in accordance with the d ₅₀ value with the difference that they are based on 10 or 90% by weight of the particles. The quotient (d ₉₀ - d ₁₀ ) / d ₅₀ represents a measure of the distribution width of the particle size. The smaller Q, the narrower the distribution.

Graft copolymers A can be prepared using emulsion, solution, Bulk or suspension polymerization can be produced. before is the radical emulsion polymerization, in which Presence of latices of component A1 at temperatures up to 90 ° C using water-soluble or oil-soluble initiators such as Peroxodisulfate or benzyl peroxide or with the help of redoxinitia The monomers A21 and A22 are grafted on. Redoxinitia gates can also be used for polymerizations below 20 ° C be set.

Suitable emulsion polymerization processes are e.g. B. described in DE-A 28 26 925, DE-A 31 49 358 and in DE-C 12 60 135.

The graft build-up takes place by means of emulsion polymerization also in DE-A 32 27 555, DE-A 31 49 357, DE-A 31 49 358 and DE-A 34 14 118. The particle size of the component A can preferably be described in DE-C 12 60 135, DE-A 28 26 925 and in Applied Polymer Science, Volume 9 (1965), page 2929 of Set the procedure described, in particular also to values in the Range from 50 to 1000 nm. Polymers with different Particle size distributions are, for example, according to DE-A 28 26 925 and US-A 5 196 480 can be produced.  

For example, according to the process described in DE 12 60 135, the graft base A1 can first be obtained by adding C ₁ - to C ₈ -alkyl esters of acrylic acid and crosslinking monomers, if appropriate together with other comonomers, in an aqueous emulsion in a manner known per se Temperatures between 20 and 100 ° C, preferably between 50 and 80 ° C, polymerized. The usual emulsifiers, such as alkali salts of alkyl or alkylarylsulfonic acids, alkyl sulfates, fatty alcohol sulfonates, salts of higher fatty acids with 10 to 30 carbon atoms or Harzsei fen can be used. Sodium salts of alkyl sulfonates or fatty acids having 10 to 18 carbon atoms are preferably used. According to one embodiment, the emulsifiers are added in amounts of 0.5 to 5% by weight, in particular 1 to 2% by weight, based on the monomers used in the preparation of the graft base A1. In general, the weight ratio of water to monomers is from 2: 1 to 0.7: 1. In particular, the usual persulfates, such as potassium persulfate, serve as polymerization initiators. However, redox systems can also be used. The initiators are generally added in amounts of 0.1 to 1% by weight, based on the monomers used in the preparation of the graft base A1. As further polymerization auxiliaries, customary buffer substances such as sodium bicarbonate or sodium pyrophosphate, with the aid of which pH values of preferably 6 to 9 are set, and 0 to 3% by weight of a molecular weight regulator, such as mercaptans, terpinols or dimeric α-methyl styrene, with be used.

The latex obtained from crosslinked acrylic acid ester polymer is according to an embodiment of the invention with a Monomer mixture from a vinyl aromatic compound (compo nente A21), e.g. B. styrene, and a vinyl cyanide (component A22), z. B. acrylonitrile, the weight ratio of z. B. styrene to acrylonitrile in the monomer mixture in the range of 100: 0 to 40:60, preferably in the range from 65: 35 to 85: 15, lies. This graft copoly is advantageously carried out merization again in aqueous emulsion under the usual, before conditions described above. The graft copoly merisation can expediently take place in the same system as the Emulsion polymerization for the preparation of the graft base A1, if necessary, further emulsifier and / or initiator is admitted. The monomer mixture of styrene and acrylonitrile can the reaction mixture at once, in batches in several stages or preferably continuously added during the polymerization will give. The graft copolymerization of this mixture in The presence of the crosslinked acrylic ester polymer is before moves so that a degree of grafting of 1 to 99 wt .-%,  preferably 20 to 45% by weight, in particular 35 to 45% by weight, based on the total weight of component A, in the graft copoly merisat A results. Since the graft yield in the graft copoly merisation is usually not 100%, an et what larger amount of the monomer mixture of styrene and acrylic nitrile used in the graft copolymerization, as it ge corresponds to the desired degree of grafting. The control of the graft yield in the graft copolymerization and thus the degree of grafting of the finished graft copolymer A is familiar to the person skilled in the art and can, for example, by the dosing speed of the monomers or by adding a regulator (Chauvel, Daniel, ACS Polymer Preprints 15 (1974), page 329 ff.). With the Emul Sion graft copolymerization generally results in about 5 to 15% by weight, based on the graft copolymer A, of free, i.e. H. ungrafted styrene / acrylonitrile copolymer. The share of Graft copolymer A in the in the graft copolymerization Polymerization product obtained is according to the above Method determined.

In the preparation of the graft copolymers A after the emul sion processes are in addition to the given process engineering Advantages also reproducible particle size changes possible Lich, for example, by at least partially agglomerating the Particles to larger particles. This means that in the graft copolymers A also polymers with different particles sizes may exist.

Component B is a copolymer that essentially

• 1. 40 to 100 wt .-%, preferably 60 to 85 wt .-%, units of styrene, a substituted styrene or one (Meth) acrylic acid ester or mixtures thereof, especially the Styrene and / or α-methylstyrene as component B1, and
• 2. 0 to 60 wt .-%, preferably 15 to 40 wt .-%, units of Acrylonitrile or methacrylonitrile, especially acrylic Contains nitrile as component B2.

According to a preferred embodiment of the invention, the Viscosity number of component B 50 to 90, preferably 60 to 80, determined according to DIN 53 726 on a 0.5 wt .-% solution in Dimethylformamide.

Component B is preferably an amorphous polymer, e.g. B. how it is described above as graft A2. According to one Embodiment of the invention as component B is a copoly merisat of styrene and / or α-methylstyrene with acrylonitrile  used. The acrylonitrile content in these copolymers Component B is generally 0 to 60% by weight, preferably 15 to 40% by weight, based on the total weight of component B. Component B also includes those in the graft copolymerization to produce component A free, not ge grafted copolymers of vinyl aromatic compounds and Vinyl cyanides, e.g. B. styrene / acrylonitrile copolymers. Depending on the in the graft copolymerization for the production of Graft copolymer A selected conditions may be possible be that with the graft copolymerization a sufficient Part of component B has been formed. Generally it is however, required in the graft copolymerization products obtained with additional, separately manufactured Kom to mix component B. The components A2 and B need in their Of course, the composition does not match.

With this additional, separately manufactured component B han it is preferably a styrene / acrylonitrile copolymer sat, an α-methylstyrene / acrylonitrile copolymer or an α-Me thylstyrol / styrene / acrylonitrile terpolymer. These copolymers sate can be used individually or as a mixture for component B be used so that it is additional, separate Component B produced, for example, a mixture of a styrene / acrylonitrile copolymer and an α-methylstyrene / Acrylonitrile copolymer can act. In the case where the Component B from a mixture of a styrene / acrylonitrile copo lymerisat and an α-methylstyrene / acrylonitrile copolymer is preferably the acrylonitrile content of the two Copolymers by not more than 10 wt .-%, preferably not more than 5 wt .-%, based on the total weight of the copoly merisats, differ from each other. Component B can, however even from a single copolymer of vinyl aromatic Compounds and vinyl cyanides exist when the graft copolymerizations for the production of component A as well the production of the additional, separately manufactured compo nente B is based on the same monomer mixture.

The additional, separately manufactured component B can according to the conventional methods can be obtained. So according to an out leadership form of the invention, the copolymerization of z. B. styrene and / or α-methylstyrene with acrylonitrile in bulk, solution, Suspension or aqueous emulsion can be carried out.  

In a preferred embodiment, the substrate layer contains (1) in addition to components A and B as an additional component Polycarbonates and possibly other additives, as in the following described.

Suitable polycarbonates are known per se. For the purposes of the invention, polycarbonates also include copolycarbonates. Polycarbonates preferably have a molecular weight (weight average M _w , determined by means of gel permeation chromatography in tetrahydrofuran against polystyrene standards) in the range from 10,000 to 200,000 g / mol. They are preferably in the range from 15,000 to 100,000 g / mol. This means that the polycarbonates generally have relative solution viscosities in the range from 1.1 to 1.5, measured in 0.5% strength by weight solution in dichloromethane at 25 ° C., preferably from 1.15 to 1.33. to have.

Polycarbonates are e.g. B. according to the method of DE-B-13 00 266 by interfacial polycondensation or according to the method DE-A-14 95 730 by reacting diphenyl carbonate with bis phenols available. Preferred bisphenol is 2,2-di (4-hydroxy phenyl) propane, in general - as in the following - as bis called phenol A. Commercially available are e.g. B. the poly carbonate Makrolon® (Bayer) and Lexan® (GE Plastics).

Instead of bisphenol A, other aromatic Dihydroxy compounds are used, in particular 2,2-di (4-hydroxyphenyl) pentane, 2,6-dihydroxynaphthalene, 4,4'-di hydroxydiphenyl sulfane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfite, 4,4'-dihydroxydiphenylmethane, 1,1-di- (4-hydroxyphenyl) ethane, 4,4-dihydroxydiphenyl or dihy droxydiphenylcycloalkanes, preferably dihydroxydiphenylcyclohexanes or dihydroxylcyclopentanes, in particular 1,1-bis (4-hydroxy phenyl) -3,3,5-trimethylcyclohexane and mixtures of the aforementioned dihydroxy compounds.

Particularly preferred polycarbonates are those based on Bisphenol A or Bisphenol A together with up to 80 mol% of the aromatic dihydroxy compounds mentioned above. It can NEN copolycarbonates according to US 3,737,409 can also be used. Of particular interest are copolycarbonates based on Bisphenol A and bis (3,5-dimethyl-4-hydroxyphenyl) sulfone or 1,1-di- (4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexyl, which is are characterized by a high heat resistance. last Genann Copolycarbonate is also commercial and the trade name Apec®HT (Bayer) available. It is also possible to use mixtures use different polycarbonates.  

The polycarbonates can be used both as regrind and in granu form. They are in the ASA substrate layer usually in amounts of 0 to 50 wt .-%, preferred from 10 to 40% by weight, based in each case on the total molding composition, in front.

The addition of polycarbonates leads, among other things, to higher Thermal stability and improved crack resistance of the composite layer films.

Mixing components A, B and optionally the poly carbonate, can be used in any way according to all known Methods are done. For example, if components A and B have been prepared by emulsion polymerization, it is possible to mix the polymer dispersions obtained then precipitate the polymers together and that Work up polymer mixture. However, this is preferably done Mixing components A and B by extruding them together, Kneading or rolling the components, preferably at temperatures in the range of 180 to 400 ° C, the components, if necessary derlich, previously from the solution obtained in the polymerization or aqueous dispersion have been isolated. The in watery Dispersion products obtained from the graft copolymerization (compo nente A) can also be partially drained and as moist crumbs are mixed with component B, then while mixing the graft completely dry copolymers.

It can be advantageous to premix individual components. Also mixing the components in solution and removing the solution medium is possible. Organic solvents are preferred, for example chlorobenzene, mixtures of chlorobenzene and Methylene chloride or mixtures of chlorobenzene or aromatic Hydrocarbons, for example toluene. Evaporation of the Solvent mixtures can be used, for example, in evaporation extruders respectively. The components can be both together and ge separates / can be metered in one after the other.

The substrate layer (1) from components A, B and given if polycarbonates can also be used as further additives Contain compounds that are for the (co) polymeri sate such as polycarbonates, SAN polymers or graft copoly merisates and their mixtures are typical and common. Examples of additives are: dyes, pig elements, effect colorants, antistatic agents, antioxidants, stabilizers gates to improve the thermal stability, to increase the Light stability, to increase the hydrolysis resistance and  Resistance to chemicals, agents against heat decomposition and especially the lubricants used in manufacturing of moldings or moldings are appropriate. Dosing These other additives can be used at any stage of manufacture development process, but preferably at an early stage Time to start the stabilization effects (or other special effects) of the additive. Wärmestabili catalysts or antioxidants are usually metal halides (chlorides, bromides, iodides), which are derived from metals of the Derive Group I of the Periodic Table of the Elements (such as Li, Na, K).

Suitable stabilizers are the usual hindered phenols, e.g. B. 2,6-disubstituted phenols such as bis (2,6-tert-butyl) -4-methylphenol (BHT), 4-methoxymethyl-2,6-di-tert-butylphenol, 2,6-di-tert -butyl-4-hydroxymethylphenol, 2,2-bis (4-hydroxyphenyl) propane, 4,4'-dihydroxybiphenyl and bis (2,6-methyl) -4-methylphenol, where bis (2,6- (C ₁ - to C ₁₀ -alkyl) -4- (C ₁ - to C ₁₀ -alkylphenols are preferred. Also suitable are vitamin E or compounds with an analog structure. Also known as HALS stabilizers (hindered amine light stabilizers ), such as tetraalkyl piperidine-N-oxy compounds, benzophenones, resorcinols, salicylates and benzotriazoles such as Tinuvin®P (2- (2H-Benzotria zol-2-yl) -4-methylphenol), which are usually used in amounts of up to 2% by weight .-%, based on the total mixture used.

Suitable lubricants and mold release agents are stearic acids, Stearyl alcohol, stearic acid esters or generally higher fatty acids ren, their derivatives and corresponding fatty acid mixtures with 12 up to 30 carbon atoms. The amounts of these additives are in the Be range from 0.05 to 1 wt .-%, based on the total mixture.

Also silicone oils, oligomeric isobutylene or similar substances men as additives, the usual amounts are 0.05 up to 5% by weight, based on the total mixture. Pigments, color substances, optical brighteners, effect colorants, such as titanium dioxide, Carbon black, iron oxides, phthalocyanines, quinacridones, perylenes, anthra quinones, aluminum tinsel can also be used.

Processing aids, e.g. B. lubricants and stabilizers, such as UV stabilizers and antistatic agents are usually too used together in amounts of 0.01 to 5 wt .-%.

Instead of ASA polymers or their blends with poly carbonates or in addition to these can be the substrate layer (1) also ABS polymers (these include  for impact modified styrene / acrylonitrile polymers, at de NEN graft copolymers of styrene and acrylonitrile on polybuta Service rubbers in a copolymer matrix made of styrene and acrylic nitrile present), polycarbonates, polyesters such as polybutylene terephthalate (PBT) or polyethylene terephthalate (PET), polyamides, Polyetherimides (PEI), polyether ketones (PEK), polyphenylene sulfides (PPS), polyphenylene ether or blends of these polymers. The aforementioned polymer materials are generally known for example from H. Domininghaus. The plastics and their egg properties, VDI publishing house, Düsseldorf (1992).

In a preferred embodiment, the substrate layer (1) from ASA polymers, mixtures of ASA polymers and poly carbonates, from ABS polymers, polycarbonates, polybutylene terephthalate, polyethylene terephthalate, polyamides or blends ASA polymers and polybutylene terephthalate are formed. Especially the substrate layer (1) preferably contains a molding compound made of ASA Polymers or mixtures of ASA polymers and poly carbonates. It can also be made up essentially or completely these polymers exist.

The layer thickness of the substrate layer (1) is preferably 100 up to 2000 µm, in particular 150 to 1500 µm and particularly preferred 200 to 1000 µm.

In a further embodiment, the composite layer films have an intermediate layer (2) made of thermoplastic and / or duro plastic plastics, optionally with additional additive fen and / or additives. Suitable thermoplastic art fabrics are e.g. B. the polyalkyl and / or aryl esters (Meth) acrylic acid, poly (meth) acrylamides or poly (meth) acrylic nitrile, also called acrylic resins, furthermore ABS polymers, Styrene / acrylonitrile polymers (SAN), polycarbonates, polyester, z. B. polyethylene or polybutylene terephthalate, polyamides, ins special amorphous polyamide, e.g. B. polyamide 12, polyether sulfones, thermoplastic polyurethanes, polysulfones, polyvinyl chloride or ASA polymers. Also blends of the above (co) polymers are generally suitable, e.g. B. Mixtures of ASA polymer ten and polycarbonates, as above for the substrate layer (1).

Suitable acrylic resins include poly (meth) acrylates, i.e. esters acrylic and methacrylic acid and mixtures of these Polymers or copolymers of acrylates and methacrylates. before is added to polyalklyl methacrylates, also in impact-resistant modifi adorned form, especially on polymethyl methacrylate (PMMA) or impact modified polymethyl methacrylate (HI-PMMA)  attacked. In a preferred embodiment, PMMA contains one Usually not more than 20% by weight of (meth) acrylic latcomonomers such as B. n-butyl (meth) acrylate or methyl acrylate. Impact-resistant PMMA (High Impact PMMA: HI-PMMA) is a polymethyl methacrylate, which is impact-resistant with suitable additives is. As impact modifiers come e.g. B. EPDM rubbers, polybuty acrylates, polybutadiene, polysiloxanes or methacrylate / butadiene / Styrene (MBS) and methacrylate / acrylonitrile / butadiene / styrene copoly merisate in question. Suitable impact modified Poly (meth) acrylates are described, for example, by M. Stick ler, T. Rhein in Ullmann's encyclopedia of industrial chemistry Vol. A21, pages 473-486, VCH Publishers Weinheim, 1992, and H. Domininghaus. The plastics and their properties, VDI-Verlag Düsseldorf, 1992. Suitable polymethyl methacrylates are Expert known for the rest and z. B. under the trademarks Lucryl® (BASF AG) and Plexiglas® (Röhm GmbH) available.

Among the polyesters are the higher to high molecular weight residues tion products of diacids, especially terephthalate acid, with dihydric alcohols, especially ethylene glycol understand. Polyethylene terephthalates include polyethylene terephthalate (PET) particularly suitable. PET products are z. B. Arnite® (Akzo), Grilpet © (EMS-Chemie) and Valox © (GE Plastics).

Finally, thermoplastic polyurethanes (TPU) are the implementation products of diisocyanates with long-chain diols. against over that of polyisocyanates (containing at least three Iso cyanate groups) and polyhydric alcohols (containing at least three hydroxyl groups), especially polyether and polyester polyols, formed polyurethane foams have thermoplastic Polyurethanes have little or no crosslinking on and accordingly have a linear structure. thermoplastic Polyurethanes are well known and found to the person skilled in the art z. B. in the plastic manual, volume 7, polyurethane, ed. G. Oertel, 2nd edition, Carl Hanser Verlag, Munich, 1983, in particular on pages 428 to 473. As commercially available ches product here z. B. Elastolan © (from Elastogran GmbH) ge Nannt.

Suitable thermosetting plastics such. B. polyurethane foams, for example the so-called polyester foam fabrics and especially the polyether foams. This verb tion class is well known to the person skilled in the art and can be found u. a. in the plastics manual, volume 7, polyurethane, ed. G.  Oertel, 2nd edition, Carl Hanser Verlag, Munich, 1983, in particular described on pages 170 to 246.

It is preferred to use acrylic resins and / or styrene (co) polymers resorted.

The intermediate layer (2) can also be used as a color support or decor serve layer. It is preferably made of impact-resistant polymethyl meth acrylates (PMMA), polycarbonates or the above for the sub stratschicht (1) described ASA polymers or their Blends built with polycarbonates. The intermediate layer (2) can also contain effect colorants. These are color, for example fabrics, metal flakes or pigments. As dyes or pigments organic or inorganic compounds come into consideration. As organic pigments are colored, white and black pigments (color pigments) and liquid crystal pigments. As inorganic Pigments are also color pigments as well as gloss pigments and Inorganic pigments usually used as fillers suitable. Of course, various organic, various inorganic or combinations of organic and inorganic pigments can be used.

The layer thickness of the decorative layer (2) is generally in the loading range from 10 to 1000, preferably from 50 to 500 and particularly preferably from 100 to 400 microns.

For the top layer (3) of the composite layer films is more common to use poly (meth) acrylate polymers. Beson polymethyl methacrylates (PMMA) are also suitable as a top layer material, e.g. B. as described in EP-A 0 255 500, PMMA with average molecular weights in the range from 40,000 to 100,000 g / mol is preferred. Suitable PMMA molding compositions are e.g. B. Products, which are available under the trademark Lucryl® (BASF AG).

The cover layer (3) is usually translucent, preferred transparent. Instead of poly (meth) acrylate polymers or Together with these, impact-resistant poly (meth) acrylates, ins special impact-resistant polymethyl methacrylate, fluorine (co) polymers such as polyvinylidene fluoride (PVDF), ABS polymers, polycarbonates, Polyethylene terephthalate, amorphous polyamide, polyether sulfones, Polysulfones or SAN copolymers are used. in the The top layer contains special polymethyl methacrylate, impact tough polymethyl methacrylate or polycarbonates, preferably poly methyl methacrylate, impact-resistant polymethyl methacrylate, PVDF or their mixtures. The polymers or their mixtures are in  usually chosen so that they become a transparent top layer to lead.

Suitable fluorine (co) polymers are formed from olefinically unsaturated monomers or comonomers in which at least one sp ² carbon is covalently linked to at least one fluorine atom. These (co) monomers include z. B. chlorotrifluoroethene, fluorovinyl sulfonic acid, hexafluoroisobutene, hexafluoropropene, per fluorovinyl methyl ether, tetrafluoroethylene, vinyl fluoride and especially vinylidene fluoride. The weight average molecular weight of fluorine (co) polymers is usually in the range from 50,000 to 300,000, preferably in the range from 100,000 to 200,000 g / mol. Mixtures of fluorine (co) polymers and poly (meth) acrylates can also be used. Mixtures of polyvinylidene fluoride (PVDF) and polymethyl methacrylate are preferred. The proportion of PVDF in these mixtures is advantageously in the range from 40 to 80, preferably from 55 to 75,% by weight, based on the total weight of the mixture.

Furthermore, an adhesive layer can consist of an adhesion promoter with a layer thickness of generally 5 to 400, in particular 5 to 100 µm can adhere to the outer surface of the substrate layer connect. The adhesion promoter serves to establish a firm connection with a chosen substrate, which is under the sub strat layer comes to rest (for example, through rear fuel Zen). The adhesive layer is used when the liability ses further substrate with the substrate layer is insufficient (for example with polyolefin substrates). Suitable adhesion middle are known to the expert. Examples of suitable adhesion middle are ethylene-vinyl acetate copolymers for coupling to poly ethylene and maleic anhydride grafted polypropylenes Coupling to polypropylene. In both cases it becomes more common Opinion the liability by introducing polar groups into the non-polar polyolefins achieved.

Back-injection or composite layer films composed of a substrate layer (1), optionally an intermediate or decorative layer (2), a cover layer (3) and optionally an adhesive layer (0) usually have the following layer thicknesses
Substrate layer (1): 100 to 2000 μm, preferably 150 to 1500 μm and particularly preferably 200 to 1000 μm,
Intermediate layer (2): 0 to 1000 μm, preferably 50 to 500 μm, particularly preferably 70 to 400 μm and in particular from 100 to 300 μm,
Cover layer (3): 20 to 300 microns, preferably 50 to 200 microns and particularly preferably 50 to 100 microns as well
Adhesive layer (0): 0 to 400 microns, preferably 10 to 200 microns and particularly preferably 50 to 100 microns.

The total thickness of this composite layer film is usually Range from 150 to 2000 microns, preferably 250 to 1500 microns and esp preferably 200 to 1000 microns.

A three-layer film can, for example, start from one Composite layer film from the two layers (2) and (3) be made by retrofitting with a substrate layer (1) is provided. For the production of the composite layer film it is usually advantageous that the size ratio of the MFI values (melt flow index) of the individual com components of the composite layer films maximum 3: 1, especially before is a maximum of 2: 1. The largest MFI value is therefore one of components (0), (1), (2), (3), provided that they are in the respective Composite layer films are present, at most three times, particularly preferably a maximum of twice the lowest MFI value. here through is a uniform flow behavior of all in the composite components or layers used provides. This coordinated flow behavior is ins particularly advantageous if the composite layer films by Adap ter or die coextrusion of the components are produced. Here, the entire network is preferably in one stage manufactured process. Especially with the adapter coextrusion ver driving is a coordination of the flow properties of the individual Components advantageous for the formation of a uniform layer th.

Die coextrusion, especially using the "Membrandü technology ", for example, has the advantage of a higher orien metal flakes and thus a better appearance to enable a metallic paint. The individual components are made flowable in extruders and via special pre directions in such a way that composite layer films with the layer sequence described above right sultieren. For example, the components can be replaced by a Slot die can be co-extruded. This method is e.g. B. explained in EP-A2-0 225 500.

The production of composite film after the adapter coextru sionsverfahren z. B. in the conference proceedings of the conference Extrusion technology "Coextrusion of foils", 8./9. October 1996, VDI publishing house Düsseldorf, especially in the contribution of Dr. networks,  is described. This economic process comes from the most coextrusion applications.

Furthermore, the composite layer films can be stacked Sheer of the individual film layers in a heatable gap getting produced. Here, the slides of the individual Components manufactured. This can be done by known methods consequences. The desired sequence of layers is then followed by Appropriate superimposition of the foils, whereupon these be guided through a heated nip and under Pressure and heat effects to a composite layer plate or -foil can be connected.

The production of molded parts, in particular motor vehicle parts such as fenders, door panels, bumpers, spoilers and Au ßenspiegelen, from the composite film can according to known Procedure. For example, composite layer films with the three-layer structure consisting of substrate layer, intermediate layer and top layer or the two-layer structure of substrate layer and top layer are preformed by thermoforming. It can Both positive and negative thermoforming processes are used become. Appropriate methods are known to the person skilled in the art. The Composite layer films according to the invention are thermo stretched molding process. Since the gloss or the upper surface quality of the composite layer films according to the invention high aspect ratios, for example up to 1: 5 not the thermoforming processes are almost with the stretching no practical restrictions regarding the possible stretching exposed.

By injecting the composite film with a fiber Reinforced plastic material gives the invention Moldings. Thermopla are preferred as plastic materials static molding compounds based on ASA or ABS polymers, SAN polymers, poly (meth) acrylates, polyether sulfones, poly butylene terephthalate, polycarbonates, folypropylene (PP) or poly ethylene (PE) and blends from ASA polymers and poly carbonates or polybutylene terephthalate and blends made of poly carbonates and polybutylene terephthalate used, where it when using PE and / or PE offers the substrate layer to be provided beforehand with an adhesive layer (0). Particularly suitable are amorphous thermoplastics or their blends. Is preferred on ABS polymers as a plastic material for injection molding resorted.  

The following components contain particularly suitable ABS polymers:

• 1. A1 ') 5 to 70, preferably 8 to 65 wt .-% of at least one Graft copolymers A '), based on A'),
• 2. a1 ') 10 to 90 wt .-% of at least one rubber elastic Graft base with a glass transition temperature below 0 ° C, obtainable by polymerization based on a1 '),
• 3. a11 ') 60 to 100, preferably 70 to 100% by weight of at least one conjugated diene and / or C ₁ to C ₁₀ alkyl acrylate, in particular butadiene, isoprene, n-butyl acrylate and / or 2-ethylhexyl acrylate,
• 4. a12 ') 0 to 30, preferably 0 to 25% by weight of at least one white teren monoethylenischen unsaturated monomers, ins special styrene, α-methylstyrene, n-butyl acrylate, methyl methacrylate or mixtures thereof, among the latter especially butadiene / styrene and n-butyl acrylate / styrene Copolymers, and
• 5. a13 ') 0 to 10, preferably 0 to 6% by weight of at least one ver wetting monomers, preferably divinylbenzene, diallyl maleate, allyl ester of (meth) acrylic acid, dihydrodicyclo pentadienyl acrylate, dinvinyl esters of dicarboxylic acids such as Succinic and adipic acid as well as diallyl and divinyl ethers of bifunctional alcohols such as ethylene glycol or Butane-1,4-diol,
• 6. a2 ') 10 to 60, preferably 15 to 55 wt .-% of a graft a2 ') off, based on a2'),
• 7. a21 ') 50 to 100, preferably 55 to 90% by weight of at least one vinyl aromatic monomers, preferably styrene and / or α-methyl styrene,
• 8. a22 ') 5 to 35, preferably 10 to 30 wt .-% acrylic nitrile and / or methacrylonitrile, preferably acrylonitrile,
• 9. a23 ') 0 to 50, preferably 0 to 30% by weight at least another monoethylenically unsaturated monomer, preferably methyl methacrylate and n-butyl acrylate, and
• 10. B ') 29 to 90, preferably 34 to 88 wt .-% of a hard Copolymers from, based on B '),  
• 11. b1 ') 50 to 100, preferably 55 to 90% by weight of at least one Styrene compound, especially styrene and / or α-methyl styrene,
• 12. b2 ') 0 to 50 wt .-% acrylonitrile or methacrylonitrile or their mixtures,
• 13. b3 ') 0 to 50% by weight of at least one further monoethylenic unsaturated monomers, for example methyl methacrylate and N-alkyl or N-aryl maleimides such as N-phenyl malei mid.

These ABS polymers can furthermore be present Three-block copolymers EO-PO-EO with a middle block PO Propylene oxide units and terminal blocks EO made of ethylene oxide units, e.g. B. the commercial product Pluronic® (from BASF).

As stabilizers, the ABS polymers can also contain ent butylated reaction product of p-cresol with dicyclo pentadiene, for. B. the commercial product Wingsty®L (Goodyear), thiocarboxylic acid esters such as thiodipropionic acid dilauryl ester (e.g. Cyanox® LTPD; American Cyanamid) and alkali or alkaline earth metal salts of a C ₆ - to C ₂₀ -carboxylic acid, e.g. B. magnesium or potassium stearate.

Production and general as well as special embodiments of the ABS polymers mentioned above can be found in the still un published German patent application DE 100 26 858.7 described below, to which express reference is hereby made becomes.

ABS polymers are based on another preferred embodiment

• 1. A ") 5 to 80, preferably 10 to 70 wt .-% of a graft poly merisates A ") with bimodal particle size distribution off, based on A "),
• 2. a1 ") 40 to 90, preferably 45 to 85% by weight of a rubber elastic particulate graft base a1 '), he available by polymerization of, based on a1 "),
• 3. a11 ") 70 to 100, preferably 75 to 100% by weight of at least one conjugated diene, especially butadiene and / or iso pren,  
• 4. a12 ") 0 to 30, preferably 0 to 25% by weight of at least one white teren monoethylenischen unsaturated monomers, ins special styrene, α-methylstyrene, n-butyl acrylate or their mixtures,
• 5. a2 ") 10 to 60, preferably 15 to 55 wt .-% of a graft a2 ") off, based on a2 '),
• 6. a21 ") 65 to 95, preferably 70 to 90% by weight of at least one vinyl aromatic monomers, preferably styrene,
• 7. a22 ") 5 to 35, preferably 10 to 30% by weight of acrylonitrile,
• 8. a23 ") 0 to 30, preferably 0 to 20% by weight of at least one white teren monoethylenically unsaturated monomers, preferred as methyl methacrylate and n-butyl acrylate, and
• 9. B ″) 20 to 95, preferably 30 to 90% by weight of one thermoplastic polymer B ") with a Viscosity number VZ (determined according to DIN 53726 at 25 ° C in 0.5% by weight solution in dimethylformamide) from 50 to 120 ml / g, off, based on B "),
• 10. b1 ") 69 to 81, preferably 70 to 78% by weight of at least one vinyl aromatic monomers, preferably styrene and / or α-methylstyrene,
• 11. b2 ") 19 to 31, preferably 22 to 30% by weight of acrylonitrile,
• 12. b3 ") 0 to 30, preferably 0 to 28% by weight of at least one white teren, monoethylenically unsaturated monomers, for example methyl methacrylate or N-alkyl or N-aryl maleimides such as N-phenyl maleimide.

In one embodiment, the ABS polymers contain compo nenten B ") side by side, which differ in their viscosity pay VZ by at least five units (ml / g) and / or in their Acrylonitrile contents by five units (wt .-%) from each other and differ. Furthermore, the material of the compo can also be used in parts nente B ") in addition to the molding compound described under B") gene, in which the acrylonitrile content above 31 wt .-%, ins is up to 37% by weight. Finally, in addition to the Component B ") and the further embodiments of copolymers Styrene and maleic anhydride or maleimides, from styrene, Maleimides and methyl methacrylate or acrylonitrile, or from  Stryol, maleimides, methyl methacrylate and acrylonitrile his.

In these ABS polymers, the graft polymers A ') or A ") preferably obtained by means of emulsion polymerization Mixing the graft polymers A ') / A ") with the components B ') or B ") and optionally other additives in a mixing device, one essentially melting liquid polymer mixture is formed. It is beneficial that cool the molten polymer mixture as quickly as possible.

Otherwise there are manufacturing and general as well as special Embodiments of the above-mentioned ABS polymers in the German patent application DE-A 197 28 629 described in detail, to which reference is hereby expressly made.

The ABS polymers mentioned can be other conventional auxiliaries and Have fillers. Such substances are, for example, sliding or mold release agents, waxes, pigments, dyes, flame protective agents, antioxidants, light stabilizers kung or antistatic.

The ver for injection molding according to the inventive method The plastic material used has long fibers in an amount of generally 3 to 40% by weight, preferably 7 to 25% by weight and in particular from 10 to 20% by weight. As examples of fiber shaped fillers are carbon, aramid or glass fibers, Cut glass or glass silk rovings called. Particularly preferred are glass fibers. Natural fibers such as Flax, hemp, jute, sisal, ramie or carnaf can be used.

The glass fibers used can be made of E, A or C glass and are preferably with a size and / or a Haftver medium equipped. Their diameter is generally between between 6 and 30 µm. Both continuous fibers (rovings) and also cut glass fibers (staple) with a length of 1 to 30 mm, preferably 3 to 20 mm, are used.

For the purposes of the invention, a long fiber reinforced art material are spoken if the average Liche fiber length greater than or equal to 0.5 mm, preferably 0.7 mm and is particularly preferably 1.0 mm (number average). Langfaserverstärk tes plastic material is also available in particular when back-molded part usually at least 10 wt .-%, preferably at least 30% by weight and particularly preferably at least 50% by weight of all fibers have a length greater than 1 mm, in particular larger Have more than 1.5 mm. Suitable sizes are z. B. too  together from aminosilanes, polyesters or from epoxy, poly urethane or phenolic resins or any mixture of these Sizing and are either commercially available or be is moving from the fiber optic manufacturer to the commercial fiber optic brought.

Carbon black and amorphous pebbles can also be used as particulate fillers acid, magnesium carbonate, powdered quartz, mica, mica, Bentonites, talc, feldspar or in particular calcium silicates such as Wollastonite and kaolin can be used.

For the back injection of composite film with fiber reinforced plastic material becomes plastic and fiber material before the back injection process in an extruder or a spray pouring machine that connects to the compression zone zone have at least one distributive mixing element, put together, melted and blended. Preferably lies behind the compression zone all plastic material in molten form. In the case of extruders, the compression zone also referred to as a transition zone (see also Saechtling, plastic Paperback, 27th edition, Carl Hanser Verlag, Munich, 1998, p. 244 to 247).

Diamond or, for example, come as distributive mixing elements Pin or cam mixed parts or those with openings in the Ge winds in question. Suitable mixing parts can also be found in "Coloring with plastics" Ed. VDI-Gesellschaft Kunststoff technik, VDI-Verlag, Düsseldorf, 1975, pp. 261 to 265, described ben. Preference is given to a separate mixing element Mixing ring used between the housing of the extruder or the injection molding machine (also called stator) and the Snail (also called a rotor) runs freely around the snail ordered and with circumferentially extending rows of Breathings is provided, also called Twente-Mixing-Ring for short. The culverts can be regular as well as irregular geometric Assuming shapes are generally circular or oval worked. They can also be disordered or circulate around the circular paths can be arranged on the mixing ring. Furthermore can the snail, d. H. the rotor, under the mixing ring Einbuch lines have, both with the passages of the mixing ring are brought to cover as well as arranged to these can be net. These indentations can be in their circumferential shape match with the passages in the mixing ring, but can also differ in size and shape from these. The indentations point usually the shape of partial sections of a ball or of an ellipsoid, for example, hemispherical moderate or semi-ellipsoid indentations, with a flowing Transition from rotor surface and indentation towards one  rupte, sharp-edged transition is preferred. Particularly suitable Neither embodiments of extruders or injection molding mix directions containing a separate passage Mixing ring can also be found in EP 340 873 B1 and DE 42 36 662 C2, hereby expressly included in the present disclosure be included.

The molded plastic molded parts are preferably produced in a multi-stage process

• a) producing the film, in particular the composite film by means of adapter or nozzle (co) extrusion of cover, substrate and optionally intermediate layer, the entire film composite, preferably manufactured in a one-step process becomes,
• b) optionally thermoforming the composite layer film in one Mold and
• c) Injection molding of the composite layer film with the fiber reinforced plastic material, taking one plastic material and fiber material before back injection in an extruder or an injection molding machine, which in the comm compression zone adjoining zone at least one distributi ves mixing element, combines, melts and mixed.

The plastic moldings according to the invention can be used in motor vehicles tools area, in particular as motor vehicle body outer parts are used, e.g. B. for smaller motor vehicle bodies Exterior parts such as mirrors or facings or for large areas exterior parts such as fenders, hoods, covers, doors, Bumpers or bumpers. Furthermore, there are also users dung as z. B. interior trim parts of motor vehicles such as Door side panels, A, B and C steering column panels, In instrument panels and cladding components in the footwell area of Motor vehicles in question and applications as aircraft interior parts, ship interior components, housings of household and electrical appliances, garden furniture, battery carriers, window profiles, facades cladding, doors, flooring, cell phone housing or seat peel.

The moldings according to the invention are very satisfactory breaking behavior and very good impact strength low temperatures. This is especially true if ABS Polymers is used as back injection material. It will no bumps, especially no glass nests, on the fo  on the side as well as on the back of the film-injected Partially observed, not even in the climate change test.

Finally, according to the method according to the invention, it is possible plastic material reinforced with long fibers ten that fiber material directly into the plastic material in homo general form is incorporated. Unlike conventional ver It is no longer driving even in large-scale production required, the long fibers over a long fiber containing Polymer granules or polymer pellets in the plastic material contribute. Rather, fiber and plastic material can be used cold addition to the extruder. Likewise, it is possible to separate the fiber material in the mixing and Melting device, e.g. B. an extruder, located polymer to give granules. The polymer granules can be melted partially melted and not melted.

The surface of the moldings according to the invention is covered by Use of fiber-reinforced products not affected. For example, rear injection molded long glass fiber reinforced Pro ABS polymer products (average fiber length under construction some about 0.7 to 2 mm (weight average)) a perfect upper surface. Also show on the non-film coated side no more fibers.

Show during mechanical examinations, such as the head impact test injection molded specimens made with long fiber reinforced art fabric material, e.g. B. ABS polymer are made, ins particularly good fracture resistance even at low temperatures hold and a very good toughness, already with one through Average fiber length of 0.7 mm (weight average) in art material material can have very good mechanical properties, especially with regard to fracture behavior and toughness put.

The combination of long fiber reinforced plastic materials, especially of ABS polymer, as back injection material (thickness preferably 2 to 3 mm) with a composite layer film made of un Strong polymers enable the production of Class A components oils that can be produced without painting and that Modulus of elasticity greater than 3000, preferably greater than 3200 MPa and a thermi length expansion less than 50 e-6 1 / K and at low temperatures show a splinter-free fracture pattern. The fracture pattern after Head impact test at -30 ° C is even cheaper than when using it an unreinforced thermoplastic.  

The invention is further illustrated by the following examples explained.

Examples

The molded parts were injected with an injection molding machine of the Krauss Maffei 1500 type. In the invention Variant became a standard three-zone screw with a through knife of 115 mm and a Twente-Mixing-Ring from Maas In ternational (NL-Wierden) is used. When not fiction according to the variant came a conventional standard three-zone screw from Krauss Maffei with a diameter of 105 mm sentence. The temperature profile of the injection molding machines came up as follows: 210/250/260/260/260 ° C.

For injection molding, the ABS plastic material (I) was used Commercial product Terluran® GP 22 (BASF AG) used.

The following glass fibers (II) were used:

• a) Cratec® 152A-14C (13 mm cutting length, Owens Corning),
• b) Cratec® 183F-11C (4 mm cutting length, Owens Corning).

The back injection film (III) was composed of one Substrate layer (1) as a carrier film (900 microns) from a standard Lichen ASA copolymer (Luran® S. BASF AG), and one Cover layer (3) (100 microns), also from a commercially available Polymethyl methacrylate (Lucryl ©, BASF AG).

The components of the individual layers (1) and (3) were each because melted separately in an extruder at 230 to 250 ° C and homogenized. The melt streams were in a feed block placed on top of each other before entering the slot die and stretched as a layer on the nozzle width (1.2 m).

The ABS (I) and the glass fiber material (II i) and ii)) (15 wt .-%, based on fiber-reinforced ABS polymer) were cold mixed into the injection molding machine. Via an injection molding tool in which the composite film (III) had been positioned, 400 × 1200 × 3.2 mm automotive rear screens were produced.

Further results can be found in the table below 1 summarized.  

Table 1

a) comparative example,
b) The back-molded comparison molded parts according to Examples 2 and 3 were conventionally produced without using the mixing part. They showed glass nests on the side facing away from the film; on the film side, these appeared conspicuously in a climate change test with temperatures in the range from -40 to + 90 ° C. Example 1 in the climate change test showed no impairment or change in the flawless surface and no deterioration in the mechanical properties.

The Ver also manufactured without using the mixing part Uniform molded part according to Example 4, in which the glass fibers have an average length of about 0.3 mm in the polymer matrix (Weight average) shows compared to components according to the invention a significantly lower elongation at break and tensile strength. Here was the glass fibers embedded in a polymer granulate, d. H. as Stick granules, incorporated into the polymer matrix to be melted beitet.

The climate change test was among the following, for the automotive industry part of the usual conditions: 3 cycles of 15 h at 90 ° C, 30 min at 23 ° C, 8 h at -40 ° C and 30 min at 23 ° C.

The impact strength was according to ISO 179 / 1eU from the tailgates mechanically worked out specimens of size 80 × 10 × 3.2 mm determined.

The tensile tests were carried out according to ISO 527-2 at 23 ° C with a trigger speed of 5 mm / min.

Claims (10)

1. A process for the production of molded plastic parts from a film and a long fiber-reinforced plastic material, in which the film is positioned in a molding tool and back-injected with a plastic material reinforced with a fiber material to form a molded part, characterized in that plastic material and fiber material before back injection in an extruder or an injection molding machine, which has at least one distributive mixing element in the zone adjoining the compression zone, combines, melts and mixes. 2. The method according to claim 1, characterized in that the Mixing element is a separate mixing ring, the two the housing of the extruder or the injection molding machine (Stator) and the worm (rotor) freely running around the worm arranged and with Rei extending in the circumferential direction hen is provided by culverts, and that the screw below the mixing ring has indentations. 3. The method according to claims 1 or 2, characterized net that the film is a composite film in order summarizing at least one substrate in this order layer, optionally at least one intermediate layer, and at least one transparent cover layer. 4. The method according to claim 3, characterized in that the composite layer film comprises:

• a) a substrate layer (1) containing ASA polymers, ABS polymers, polycarbonates, polyesters, polyamides, polyetherimides, polyether ketones, polyphenylene sulfides, polyphenylene ethers or mixtures thereof,
• b) optionally an intermediate layer (2) containing poly (meth) acrylates, impact-resistant poly (meth) acrylates, poly (meth) acrylamides, poly (meth) acrylonitrile, ASA polymers, ABS polymers, polycarbonates, polyesters, poly amides , Polyether sulfones, polysulfones, polyvinyl chloride or mixtures thereof, and
• c) a transparent cover layer (3) containing poly (meth) acrylates, impact-resistant poly (meth) acrylates, fluorine (co) polymers, ABS polymers, polycarbonates, polyethylene terephthalate, amorphous polyamide, SAN polymers, polyether sulfones, polysulfones or their mixtures.

5. The method according to claims 3 or 4, characterized net that the substrate layer is essentially constructed from ASA polymers and optionally polycarbonates. 6. The method according to claims 3 to 5, characterized in that ASA polymers are composed essentially of:

• a) from 1 to 99% by weight of a graft copolymer (component A)
• b) 1 to 99% by weight of a particulate graft base A1 from the monomers
• c) 80 to 99.99% by weight of at least one C ₁ to C ₁₈ alkyl ester of acrylic acid as component A11,
• d) 0.01 to 20% by weight of at least one polyfunctional crosslinking monomer as component A12,
• e) 1 to 99% by weight of a graft A2 from the monomers, based on A2,
• f) 40 to 100 wt .-% units of styrene, a substituted styrene or a (meth) acrylic acid ester or mixtures thereof as component A21 and
• g) 0 to 60% by weight of units of acrylonitrile or methacrylonitrile as component A22,
  wherein the graft A2 consists of at least one graft shell and the graft copolymer has an average particle size of 50 to 1000 nm; and
• h) from 1 to 99% by weight of a copolymer (component B)
• i) 40 to 100% by weight of units of styrene, a substituted styrene or a (meth) acrylic acid ester or mixtures thereof as component B1,
• j) up to 60% by weight of acrylonitrile or methacrylonitrile as component B2.

7. The method according to claims 1 to 6, characterized in net that as a plastic material an ABS polymer, Polybutylene terephthalate or a mixture of polycarbonate and polybutylene terephthalate or from an ASA polymer and polycarbonate or an ASA polymer and polybutylene uses terephthalate. 8. The method according to claims 1 to 7, characterized in net that the fibers are injected into the plastic mold behind partly an average fiber length greater than or equal to 0.5 mm (Number average). 9. Injection molded plastic parts, available according to one of the Claims 1 to 8. 10. Use of the plastic moldings according to claim 9 as checks series interior and exterior components, aircraft interior components, Ship interior components, housings for household and electrical appliances garden furniture, battery holders, window profiles, facades cladding, doors, flooring, cell phone cases or Seats.