EP1999194A1 - Fiber-reinforced thermoplastic - Google Patents
Fiber-reinforced thermoplasticInfo
- Publication number
- EP1999194A1 EP1999194A1 EP07727015A EP07727015A EP1999194A1 EP 1999194 A1 EP1999194 A1 EP 1999194A1 EP 07727015 A EP07727015 A EP 07727015A EP 07727015 A EP07727015 A EP 07727015A EP 1999194 A1 EP1999194 A1 EP 1999194A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fiber
- reinforced thermoplastic
- fibers
- airlaid
- thermoplastic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/045—Reinforcing macromolecular compounds with loose or coherent fibrous material with vegetable or animal fibrous material
Definitions
- the invention relates to a fiber-reinforced thermoplastic as well as molded or manufactured from it. Furthermore, the invention relates to the use of airlaid cellulosic fiber material for producing such fiber-reinforced thermoplastics.
- Fiber-reinforced thermoplastic-based composites are increasingly being used in place of metallic materials in many fields of technology because they promise significant weight reduction, with mechanical parameters that are otherwise comparable in many respects.
- the composite material includes a fibrous component which has a considerable influence on mechanical properties, in particular tensile and flexural strength as well as impact resistance of the composite material.
- fibrous components are used (i) fibers of inorganic materials such as glass, carbon and boron, (ii) metallic fibers, e.g. As steel, aluminum and tungsten, (iii) synthetic organic fibers, for.
- Other auxiliaries and fillers may be added to the composite.
- glass fiber reinforced thermoplastics in vehicle construction, eg for vehicle interior trim.
- the production of glass fibers requires the use of significant amounts of energy and the base materials are not of biological origin, so that the sustainability of the manufacturing process is environmentally critical to criticize.
- the disposal of glass fiber reinforced thermoplastics is difficult, as even with thermal decomposition of the material considerable amounts of residues remain, which can be fed to a landfill usually only.
- glass fiber has a high abrasiveness, so that the processing of the materials is difficult in the context of conventional processing methods for thermoplastics.
- DE 103 35 139 A1 discloses a method for producing a component from a fiber composite material, in which 3-10 mm long artificial cellulose regenerated fibers are mixed with a thermoplastic as the fiber-reinforcing component. The resulting material is used as a base material for the production of lightweight components.
- WO 97/30838 A1 describes a fiber composite material of natural cellulose fiber material, here wood flour and a thermoplastic. The material is extruded directly to the component.
- natural fiber materials as a fiber-reinforcing component is offset by inferior mechanical properties of the resulting composite materials as compared to fiber-reinforced composites with glass fiber content.
- natural fibers such as flax, hemp or even wood particles of varying composition: Depending on the growing area, cultivation period, storage and possibly pretreatment, individual batches of the material differ. However, this also varies the mechanical characteristics of the fiber-reinforced thermoplastics to be produced, which makes the technical use difficult. The material can continue to change its shape and appearance due to progressive degradation processes. Finally, the natural sulfur and nitrogen content in natural products can lead to the outgassing of undesirable odors.
- WO 03/104309 A1 describes a fiber composite material to which cellulosic fibers are added from pulp, wherein the cellulose used is an ⁇ -cellulose with a degree of purity of> 80%.
- the polymeric matrix is a polymer having a melting point of ⁇ 200 ° C, z. B. a polypropylene.
- the composite further contains at least one water-soluble binder, at least one lubricant and at least one adhesion promoter.
- the use of cellulose fibers has the advantage that the stiffness and impact resistance of the resulting composite material is increased, there is a global availability of cellulose fibers and the consistency of the starting materials and the composite material is increased.
- the object of the present invention is to utilize the advantages associated with the use of organic materials of natural origin, while further improving the processing and use-relevant properties of the composite material.
- thermoplastic comprising:
- thermoplastic matrix b
- the spreading material accordingly contains, as a fiber-reinforcing component, a cellulose fiber material in the form of an airlaid. It has been found that the use of this fiber material leads to an increase in the impact resistance and impact strength as well as tensile and flexural strength compared to the use of cellulose fibers not subjected to this processing process, from fibrous cellulose, but also to wood-discarded thermoplastics. The reason for this behavior is not fully understood yet. It is believed that nonwoven production results in a fiber bond between individual cellulosic fibers, which is at least partially retained even in the subsequent comminution or processing of the web.
- An airlaid cellulose fiber material in the context of this invention is a material containing cellulose fibers, in particular made from fiber pulp by the sulphate or sulphite process and fragments of a corresponding airlaid nonwoven.
- the airlaid nonwoven fiber pulp is separated mechanically with the aid of hammer mills.
- the fibers are randomly deposited over a stream of air onto a belt to form a sheet-like body (air laid web forming).
- Subsequent binding of the fibers can be achieved by bonding with aqueous dispersions (eg polyacrylates, polyvinyl acetates, ethylene vinyl acetates, styrene butadiene and other latexes), by heat treatment of binder fibers or treatment with ultrasound or high frequency.
- aqueous dispersions eg polyacrylates, polyvinyl acetates, ethylene vinyl acetates, styrene butadiene and other latexes
- the fleece density can be adjusted by controlled roller pressure and temperature. Details of the airlaid process can be found inter alia in the patents US 4,494,278, US 5,527,171 and US 4,640,810. the content of which is hereby incorporated by reference for purposes of disclosure
- a fiber-reinforcing component it is particularly preferred to use a spreading material which is obtained by comminution of a fleece made of lignin-free fiber pulp produced by the airlaid process.
- Shredding in the sense of the invention involves the mechanical dismemberment of the nonwovens.
- the processed airlaid nonwovens preferably have an average length-weighted fiber length in the range of 0.5 to 5 mm, more preferably 2 to 3 mm, prior to comminution.
- the length-weighted fiber length is calculated as the quotient of the sum of all fibers multiplied by the corresponding squares of the length by the sum of all fibers multiplied by the corresponding lengths (measurement method: ISO 16065-1 standard 2001-09) Fiber materials - Determination of the fiber length by automatic optical analysis - Part 1: Method with polarized light).
- This fiber length specification refers to the average length of the cellulosic fibers, not the length of the shredded airlaid cellulosic fiber material. This length is no longer clearly determinable after passing through agglomeration, but certainly greater than that of the cellulose fibers.
- thermoplastic according to the invention it is conceivable not only to collect a comminuted airlaid nonwoven itself, but also preferably residual waste from the industrial production and processing of airlaid nonwoven, to comminute it and to use it in the sense according to the invention.
- Remnants of nonwoven production after the airlaid process or in the further processing stages of the material are so far nert, pressed and dumped or burned.
- the combustion of the material requires a quality control of the combustion process, so that it can only be carried out in special plants.
- absorbent hygiene products include, in particular, feminine and diaper hygiene products.
- Fiber pulp which is particularly preferred as the major constituent of the cellulosic fiber material, is a specialty product of industrial pulp production and can be obtained via both the acid sulfite and the alkaline sulfate (Kraft) processes.
- the lignin content is lowered from previously typically 30% to 10%.
- the hemicellulose content is also attacked, but is about 12% greater in the widely used sulphate process after treatment over the sulphite process.
- delignifying bleaching steps to increase the degree of whitening with oxygen (oxygen delignification), hydrogen peroxide brighteners (peroxide brightening) and ozone bleaching. Used for bleaching chlorine-oxygen compounds are hardly used.
- the delignified fiber pulp is converted into a transportable form by a wet paper-laying process, dewatering, drying and rolling or cutting of plates.
- This flaky, easily shredded fiber pulp (Fluff PuIp) can be processed well in the airlaid process.
- Fiber pulp is the name given to the fine, predominantly cellulose pulp resulting from the pulping of wood or other plant fibers Dimensions. It is a refined natural product, is present as a white, fibrous solid at room temperature and has a cellulose content of over 95 wt.%.
- Fiber pulp is largely free of lignin, with lignin-free in the context of the invention referring to a lignin content of ⁇ 0.5% by weight of the total weight of the (dry) fiber pulp.
- Lignin can be determined as a hydrolysis residue taking into account the residue of ignition by acid hydrolysis of the cellulosic constituents.
- NIR near-infrared
- the residual lignin content determined in accordance with DIN 54356 and as a visible property by specifying the spectral reflection factor brightness according to ISO 2469 / ISO 2470, usually over 75%, better over 85%.
- the properties of the fiber pulp depend both on the type of wood used, as well as on the manufacturing process used and are subject to fluctuations.
- airlaid cellulosic fiber material with longer-fiber softwood softwood fiber pulp is used as a fiber-reinforcing component of the thermoplastics because it is based on e.g. Pine-made fibers have a higher tensile strength.
- the hemicellulose content in the case of fiber pulp is about 12%, based on the total weight of the (dry) fiber pulp.
- Chemical pulp is used in the food, cosmetics and pharmaceutical industries and in the production of synthetic fibers from regenerated cellulose such as viscose, cellulose acetate, lyocell, cellulose carbamate u.a.
- Cellulose is the isotactic beta-1,4-polyacetal of cellobiose and forms unbranched, water-insoluble chains.
- the average molar masses are 50,000 - 500,000.
- alpha-cellulose is called the at 20 ° C in 17.5% iger NaOH or 24% KOH insoluble fraction with an average degree of polymerization>200; the fraction which precipitates from the sodium-alkaline solution with methanol becomes beta-cellulose and the non-precipitable fraction gamma-cellulose, the latter both together also called hemicellulose.
- the cellulosic fibers are based on the so-called elementary fibril, which is visible with the electron microscope. Several elementary fibrils form microfibrils and macrofibrils.
- Thermoplastic is the name given to polymeric materials which are soft or hard at service temperature and which have a flow transition region above the service temperature.
- Thermoplastics consist of linear or branched polymers, which in the case of amorphous thermoplastics above the glass transition temperature (T g ), in the case of (partially) crystalline thermoplastics above the melting temperature (T m ) are in principle fluid. They can be processed in the softened state by molding, extrusion, injection molding or other molding processes to form parts.
- Important thermoplastics are polyethylenes, polypropylene, polystyrene, polyvinyl chloride, polyacrylonitrile, polyamides, polyesters and polyacrylates. It is also possible to use blends of various thermoplastic polymers as the polymeric matrix.
- the thermoplastic need not be a homopolymer, but may also be present as a copolymer, polypolymer, block polymer, or otherwise modified polymer.
- the thermoplastic matrix is a polypropylene or contains a polypropylene as a main component in a blend, ie polypropylene has a weight fraction of ⁇ 50% of the thermoplastic matrix.
- Composite materials on this polymeric basis are easy to process - also in granular form or as a semi-finished product - and show favorable mechanical characteristics, in particular for use in vehicle construction, eg. B. for interior trim.
- to increase the tensile or flexural strength - in each case with the focus on the desired application to increase the adhesion between the polymeric matrix and the fiber-reinforcing component.
- a polypropylene modified to enhance an interaction with cellulose in particular polypropylene-maleic anhydride graft copolymer (MAPP).
- MAPP polypropylene-maleic anhydride graft copolymer
- the modified polypropylene or other adhesion-enhancing component is added to the polymeric matrix or / and the fiber-reinforcing component.
- the airlaid cellulosic fibrous material comprises a binder for maintaining a bond between fibers of the airlaid cellulosic fiber material selected from the group consisting of (i) a fibrous or granulated thermoplastic, preferably polyethylene and / or polypropylene and / or polyethylene terephthalate, (ii) thermoplastic encapsulated fibers, (iii) a latex, preferably a self-crosslinking or crosslinked EVA latex, a vinyl emulsion including vinyl acetate or other vinyl ester based emulsions in the form of homopolymers or copolymers with ethylene and ethylene or acrylic monomers, acrylic emulsions in the form of homopolymers or copolymers, or other crosslinked adhesives, and mixtures of two or more of these binders according to (i) to (iii).
- a binder for maintaining a bond between fibers of the airlaid cellulosic fiber material selected from the group consisting of
- the so-called two-component fibers which have a core of polypropylene or of polyethylene terephthalate, and a sheathing of polyethylene are to be emphasized as binders.
- the polyethylene of the sheath acts as the actual binder between the bicomponent or bicomponent fibers, which retain their fibrous structure when melting the polyethylene due to their higher melting core and are thus suitable to keep the cellulose fibers.
- suitable binders are polyester-copolyester core-sheath fibers and multicomponent fibers.
- Polyester-copolyester core-sheath fibers are particularly suitable since low-melting copolyesters with similar temperature windows as polyethylene are also available.
- the binders usually allow that binding between the fibers of the cellulose fiber material is maintained even when liquid contact.
- the binders further promote the reinforcing effect of the airlaid cellulosic fibrous material in the fiber reinforced thermoplastic by improving the bulk of the fibrous material during processing and in the final thermoplastic. This is particularly advantageous when using a spreading material made of airlaid cellulose fiber material.
- thermoplastics which contain superabsorbent polymers (SAP).
- SAPs superabsorbent polymers
- SAPs are polymeric gelling compounds that are capable of binding very large amounts of water without deliquescing, such as the water-insoluble starch produced by alkaline hydrolysis of starch / acrylonitrile copolymers.
- Acrylamide / acrylic acid graft copolymers or also crosslinked polyacrylic acids After processing the granules into shaped parts, a reduction of the outgassing can be achieved.
- auxiliaries and additives may be present in the thermoplastic according to the invention.
- Auxiliaries may be, in particular, fillers, stabilizers, antistatic agents, flame retardants, masterbatch colorants in the form of 1-3% based on total granules, flexibilizers and plasticizers, adhesion promoters, blowing agents, antibacterial agents and fungicides.
- Suitable fillers are inorganic materials such as chalk, limestone, marble, aluminum, quartz, metal, mica, etc.
- thermoplastic preferably has the following composition:
- thermoplastic matrix 30 - 90 parts by weight of thermoplastic matrix
- thermoplastic of said composition can be easily processed, be it granules, semi-finished or otherwise suitable for processing.
- the components are mixed together in a conventional manner and optionally pieced.
- the thermoplastic contained by thermal or physico-thermal agglomeration of the components is preferably provided as granules or semi-finished products for further processing.
- the resulting thermoplastic is storable granules, logistically easy to handle and easy to use in further processing.
- Cellulose fibers made of fiber pulp are white, so that the addition of colorants compared to natural fibers is significantly expanded.
- thermoplastic in vehicle construction, in particular for the production of components of3.1innenraumverklei- Phys, such as side door covers, front area, parcel shelf and vehicle roof.
- components of3.1innenraumverklei- Phyg such as side door covers, front area, parcel shelf and vehicle roof.
- the fiber-reinforced thermoplastic or granules or semi-finished product based on the thermoplastic is for the manufacture of housings and packaging materials, e.g. of containers, especially in vehicle construction, particularly suitable.
- thermoplastic according to the invention is advantageously suitable for forming a molded part, in particular for use in the automotive industry. Particularly advantageous in such a molded part is the high impact strength and notched impact strength achievable by using a thermoplastic according to the invention while at the same time saving material of the cost-intensive thermoplastic matrix.
- Example 1 Remnants of airlaid nonwoven production / processing
- the grit obtained typically has the following composition:
- the core is predominantly polypropylene or polyethylene terephthalate and the shell is a polyethylene-derived polymer.
- the fiber length is 3 - 18 mm.
- a superabsorbent polymer namely a polyacrylate.
- SAP superabsorbent polymer
- modified starch or other water-insoluble gel-forming polysaccharides can be used.
- Remnants from the manufacture and processing of diapers are shredded in a shredder.
- the grit obtained has the following typical composition:
- Nonwovens come from.
- the fiber length is 2 - 3 mm.
- a superabsorbent polymer namely a polyacrylate.
- SAP superabsorbent polymer
- modified starch or other water-insoluble gel-forming polysaccharides can be used.
- the core is predominantly made of polypropylene or polyethylene terephthalate, and in the case of two-component fibers, the shell of a polyethylene-derived polymer.
- the fiber length is 3 - 18 mm.
- the remnant is mixed in a weight ratio of 1: 1 with pellets of pure polypropylene and agglomerated by thermomechanical processing. Pelleting the product provides a granule.
- thermoplastics according to the invention Comparison of impact strength and notched impact strength of thermoplastics according to the invention with other materials
- Polypropylene granules (hereafter "PP”, Borealis HK 060 AE) were mixed with wood flour (hereinafter “wood”) or airlaid cellulose fiber material (“cell”) mixed and injection-molded into 4 mm thick ISO standard bars in the ratios given in Table 1:
- the mold temperature was 25 ° C, o.
- the airlaid cellulosic fiber material contained 70% by weight fluff pulp cellulose, 10% by weight synthetic fibers of polyethylene, polypropylene and / or polyethylene terephthalate, 8% by weight latex, 10% by weight superabsorbent polymer particles, balance polypropylene carrier ,
- the ISO standard bars produced were reinforced in accordance with DIN EN ISO 179/1 eAU with a pendulum percussion hammer at 23 ° C. (impact resistance pendulum without notch: 5 J unreinforced [100% PP], 2 J [remainder]; impact value pendulum with notch: 0.5 J) for impact resistance and notched impact strength. Table 2 shows the results:
- thermoplastics according to the invention Comparison of the outgassing values of thermoplastics according to the invention with other materials
- the fiber-reinforced thermoplastics according to the invention in some cases significantly better, in comparison with wood-reinforced thermoplastics and pure polypropylene, in particular from a proportion of 25 wt .-% of airlaid cellulose fiber material. lower, have condensate values and so a significant requirement of the automotive industry for reduced condensation of volatiles to discs o.a. progeny.
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Abstract
The invention relates to a fiber-reinforced thermoplastic comprising airlaid cellulose fiber material, and to its uses.
Description
Berlin, 16. März 2007 unser zeichen: CB 1 1 16-02WO JVO/JAN/HSE/kli/ralBerlin, March 16, 2007 our sign: CB 1 1 16-02WO JVO / JAN / HSE / kli / ral
Durchwahl: 030/841 887 0Direct dial: 030/841 887 0
Anmelder / Inhaber: CONCERT GmbHApplicant / owner: CONCERT GmbH
Amtsaktenzeichen: NeuanmeldungOfficial file: new registration
CONCERT GmbHCONCERT GmbH
Gewerbepark Prignitz/FalkenhagenBusiness park Prignitz / Falkenhagen
Am Lehmberg 10, 16928 PritzwalkAm Lehmberg 10, 16928 Pritzwalk
Faserverstärkter ThermoplastFiber reinforced thermoplastic
Die Erfindung betrifft einen faserverstärkten Thermoplasten sowie daraus hergestellte oder herstellbare Formteile. Weiterhin betrifft die Erfindung die Verwendung von Airlaid-Zellulosefasermaterial zum Herstellen solcher faserverstärkten Thermoplasten.The invention relates to a fiber-reinforced thermoplastic as well as molded or manufactured from it. Furthermore, the invention relates to the use of airlaid cellulosic fiber material for producing such fiber-reinforced thermoplastics.
Hintergrund der ErfindungBackground of the invention
Faserverstärkte Verbundwerkstoffe auf Basis von Thermoplasten werden auf vielen Gebieten der Technik verstärkt an Stelle metallischer Werkstoffe eingesetzt, da sie eine wesentliche Gewichtsreduktion, bei ansonsten in vielen Punkten vergleichbaren mechanischen Kennwerten, versprechen. Der Verbundwerk- stoff beinhaltet dazu neben der thermoplastischen Matrix eine faserartige Komponente, die im erheblichen Maße Einfluss auf mechanische Kennwerte nimmt, insbesondere auf Zug- und Biegefestigkeit sowie Schlagzähigkeit des Verbundwerkstoffs. Als faserartige Komponenten finden Einsatz (i) Fasern aus anorgani-
schen Materialien, wie Glas, Kohle und Bor, (ii) metallische Fasern, z. B. aus Stahl, Aluminium und Wolfram, (iii) synthetisch organische Fasern, z. B. aus aromatischen Polyamiden, Polyvinylalkoholen, Polyestern, Polyacrylaten und Polyvinylchlorid oder (iv) Fasern natürlichen Ursprungs, z. B. aus Hanf und Flachs. Weitere Hilfs- und Füllstoffe können dem Verbundwerkstoff zugesetzt sein.Fiber-reinforced thermoplastic-based composites are increasingly being used in place of metallic materials in many fields of technology because they promise significant weight reduction, with mechanical parameters that are otherwise comparable in many respects. In addition to the thermoplastic matrix, the composite material includes a fibrous component which has a considerable influence on mechanical properties, in particular tensile and flexural strength as well as impact resistance of the composite material. As fibrous components are used (i) fibers of inorganic materials such as glass, carbon and boron, (ii) metallic fibers, e.g. As steel, aluminum and tungsten, (iii) synthetic organic fibers, for. Example of aromatic polyamides, polyvinyl alcohols, polyesters, polyacrylates and polyvinyl chloride or (iv) fibers of natural origin, for. B. from hemp and flax. Other auxiliaries and fillers may be added to the composite.
Von besonderer Bedeutung ist in der Praxis der Einsatz glasfaserverstärkter Thermoplaste im Fahrzeugbau, z B. für die Fahrzeuginnenraumverkleidung. Die Herstellung von Glasfasern erfordert allerdings den Einsatz erheblicher Mengen an Energie und die Grundmaterialien sind nicht biologischen Ursprungs, so dass die Nachhaltigkeit des Herstellungsprozesses unter ökologischen Gesichtspunkten zu kritisieren ist. Weiterhin ist die Entsorgung glasfaserverstärkter Thermoplaste erschwert, da auch bei thermischer Zersetzung des Materials erhebliche Mengen an Rückständen verbleiben, die in der Regel nur einer Deponie zuge- führt werden können. Schließlich besitzt Glasfaser eine hohe Abrasivität, so dass die Verarbeitung der Materialien im Rahmen üblicher Verarbeitungsverfahren für Thermoplaste erschwert ist.Of particular importance in practice is the use of glass fiber reinforced thermoplastics in vehicle construction, eg for vehicle interior trim. The production of glass fibers, however, requires the use of significant amounts of energy and the base materials are not of biological origin, so that the sustainability of the manufacturing process is environmentally critical to criticize. Furthermore, the disposal of glass fiber reinforced thermoplastics is difficult, as even with thermal decomposition of the material considerable amounts of residues remain, which can be fed to a landfill usually only. Finally, glass fiber has a high abrasiveness, so that the processing of the materials is difficult in the context of conventional processing methods for thermoplastics.
Aufgrund der vorgenannten Nachteile, aber auch allgemein zur Verbesserung der Werkstoffeigenschaften wird daher gegenwärtig intensiv nach Möglichkeiten gesucht, die in vielen technischen Anwendungen dominierenden Glasfasern als verstärkungsgebende Komponente zu ersetzen. Organische Fasermaterialien natürlichen Ursprungs erscheinen in diesem Zusammenhang wegen ihrer geringeren Dichte und damit verbundenen Gewichtsreduktion in Verbundwerkstoff sowie der Nachhaltigkeit und besseren Entsorgung besonders attraktiv.Due to the aforementioned disadvantages, but also generally to improve the material properties is therefore currently being intensively sought ways to replace the dominating in many technical applications glass fibers as reinforcing component. Organic fiber materials of natural origin appear particularly attractive in this context because of their lower density and associated weight reduction in composite as well as sustainability and better disposal.
Aus DE 103 35 139 A1 ist ein Verfahren zur Herstellung eines Bauteils aus einem Faserverbundwerkstoff bekannt, bei dem als faserverstärkende Komponente 3-10mm lange künstliche Zelluloseregeneratfasern mit einem Thermoplast vermischt werden. Der erhaltene Werkstoff wird als Basismaterial für die Fertigung von Leichtbauteilen eingesetzt.
WO 97/30838 A1 beschreibt einen Faserverbundwerkstoff aus natürlichem Zellulose-Fasermaterial, hier Holzmehl und einem Thermoplast. Der Werkstoff wird direkt zum Bauteil extrudiert.DE 103 35 139 A1 discloses a method for producing a component from a fiber composite material, in which 3-10 mm long artificial cellulose regenerated fibers are mixed with a thermoplastic as the fiber-reinforcing component. The resulting material is used as a base material for the production of lightweight components. WO 97/30838 A1 describes a fiber composite material of natural cellulose fiber material, here wood flour and a thermoplastic. The material is extruded directly to the component.
Dem Einsatz natürlicher Fasermaterialien als faserverstärkende Komponente stehen allerdings schlechtere mechanische Kennwerte der resultierenden Verbundmaterialien im Vergleich zu faserverstärkten Verbundwerkstoffen mit Glasfaseranteilen gegenüber. Weiterhin sind Naturfasern, wie Flachs, Hanf oder auch Holzpartikel von schwankender Zusammensetzung: Je nach Anbaugebiet, Anbauzeitraum, Lagerung und ggf. Vorbehandlung unterscheiden sich einzelne Chargen des Materials. Damit variieren jedoch auch die mechanischen Kennwerte der herzustellenden faserverstärkten Thermoplaste, was den technischen Einsatz erschwert. Das Material kann weiterhin aufgrund fortschreitender Abbauprozesse seine Form und Aussehen verändern. Schließlich kann der natürliche Schwefel- und Stickstoffgehalt in den Naturprodukten zum Ausgasen uner- wünschter Geruchsstoffe führen.However, the use of natural fiber materials as a fiber-reinforcing component is offset by inferior mechanical properties of the resulting composite materials as compared to fiber-reinforced composites with glass fiber content. Furthermore, natural fibers, such as flax, hemp or even wood particles of varying composition: Depending on the growing area, cultivation period, storage and possibly pretreatment, individual batches of the material differ. However, this also varies the mechanical characteristics of the fiber-reinforced thermoplastics to be produced, which makes the technical use difficult. The material can continue to change its shape and appearance due to progressive degradation processes. Finally, the natural sulfur and nitrogen content in natural products can lead to the outgassing of undesirable odors.
WO 03/104309 A1 beschreibt einen Faserverbundwerkstoff, dem Zellulosefasern aus Zellstoff zugesetzt sind, wobei die eingesetzte Zellulose eine α-Zellulose mit einem Reinheitsgrad von > 80 % ist. Als polymere Matrix dient ein Polymer mit einem Schmelzpunkt von < 200 °C, z. B. ein Polypropylen. Der Verbundwerkstoff beinhaltet weiterhin zumindest ein wasserlösliches Bindemittel, zumindest ein Gleitmittel und zumindest einen Haftvermittler. Gegenüber Naturfasern hat der Einsatz von Zellulosefasern den Vorteil, dass die Steifheit und Schlagzähigkeit des erhaltenen Verbundwerkstoffs erhöht ist, eine globale Verfügbarkeit von Zellulosefasern besteht und die Konsistenz der Ausgangsprodukte und des Ver- bundwerkstoffs erhöht ist.WO 03/104309 A1 describes a fiber composite material to which cellulosic fibers are added from pulp, wherein the cellulose used is an α-cellulose with a degree of purity of> 80%. The polymeric matrix is a polymer having a melting point of <200 ° C, z. B. a polypropylene. The composite further contains at least one water-soluble binder, at least one lubricant and at least one adhesion promoter. Compared with natural fibers, the use of cellulose fibers has the advantage that the stiffness and impact resistance of the resulting composite material is increased, there is a global availability of cellulose fibers and the consistency of the starting materials and the composite material is increased.
Aufgabe der vorliegenden Erfindung ist es, die mit dem Einsatz von organischen Materialien natürlichen Ursprungs verbundenen Vorteile zu nutzen, dabei jedoch die verarbeitungs- und gebrauchsrelevanten Eigenschaften des Verbundwerkstoffs weiter zu verbessern.
Erfindungsgemäße LösungThe object of the present invention is to utilize the advantages associated with the use of organic materials of natural origin, while further improving the processing and use-relevant properties of the composite material. Inventive solution
Die Aufgabe wird gelöst durch einen faserverstärkten Thermoplast umfassend:The object is achieved by a fiber-reinforced thermoplastic comprising:
a) ein Airlaid-Zellulosefasermaterial ina) an airlaid cellulose fiber material in
b) einer thermoplastischen Matrix.b) a thermoplastic matrix.
Erfindungsgemäß enthält das Streugut demnach als faserverstärkende Komponente ein Zellulosefasermaterial in Form eines Airlaids. Es hat sich gezeigt, dass der Einsatz dieses Fasermaterials zu einer Erhöhung der Schlagzähigkeit und Kerbschlagzähigkeit sowie von Zug- und Biegefestigkeit gegenüber dem Einsatz von nicht diesem Verarbeitungsprozess unterworfenen Zellulosefasern aus Fa- serzellstoff, aber auch gegenüber holzmehlversetzten Thermoplasten führt. Der Grund für dieses Verhalten ist noch nicht völlig geklärt. Es wird angenommen, dass die Vliesherstellung zu einer Faserbindung zwischen einzelnen Zellulosefasern führt, die auch bei der nachträglichen Zerkleinerung oder Verarbeitung des Vlieses zumindest teilweise erhalten bleibt.According to the invention, the spreading material accordingly contains, as a fiber-reinforcing component, a cellulose fiber material in the form of an airlaid. It has been found that the use of this fiber material leads to an increase in the impact resistance and impact strength as well as tensile and flexural strength compared to the use of cellulose fibers not subjected to this processing process, from fibrous cellulose, but also to wood-discarded thermoplastics. The reason for this behavior is not fully understood yet. It is believed that nonwoven production results in a fiber bond between individual cellulosic fibers, which is at least partially retained even in the subsequent comminution or processing of the web.
Ein Airlaid-Zellulosefasermaterial im Sinne dieser Erfindung ist ein Material enthaltend Zellulosefasern, insbesondere aus Faserzellstoff hergestellt nach dem Sulfat- oder Sulfitverfahren und Bruchstücke eines entsprechenden Airlaid- Vlieses.An airlaid cellulose fiber material in the context of this invention is a material containing cellulose fibers, in particular made from fiber pulp by the sulphate or sulphite process and fragments of a corresponding airlaid nonwoven.
Zur Herstellung des Airlaid-Vlieses wird Faserzellstoff mechanisch mit Hilfe von Hammermühlen vereinzelt. Die Fasern werden über einem Luftstrom wirr auf ein Band unter Bildung eines flächigen Körpers abgelagert (air laid web forming). Eine sich daran anschließende Bindung der Fasern kann durch Verkleben mit wässrigen Dispersionen (z. B. Polyacrylaten, Polyvinylacetaten, Ethylenvinylace- taten, Styren-Butadien und anderen Latices), durch Wärmebehandlung von Binderfasern oder Behandlung mit Ultraschall oder Hochfrequenz erfolgen. Die Vliesdichte kann durch kontrollierten Walzendruck und Temperatureinwirkung eingestellt werden. Einzelheiten zum Airlaid-Verfahren können unter anderem den Patenten US 4,494,278, US 5,527,171 und US 4,640,810 entnommen wer-
den, deren Inhalt hier für Offenbarungszwecke vollständig in Bezug genommen wird.For the production of the airlaid nonwoven fiber pulp is separated mechanically with the aid of hammer mills. The fibers are randomly deposited over a stream of air onto a belt to form a sheet-like body (air laid web forming). Subsequent binding of the fibers can be achieved by bonding with aqueous dispersions (eg polyacrylates, polyvinyl acetates, ethylene vinyl acetates, styrene butadiene and other latexes), by heat treatment of binder fibers or treatment with ultrasound or high frequency. The fleece density can be adjusted by controlled roller pressure and temperature. Details of the airlaid process can be found inter alia in the patents US 4,494,278, US 5,527,171 and US 4,640,810. the content of which is hereby incorporated by reference for purposes of disclosure.
Besonders bevorzugt wird als faserverstärkende Komponente ein Streugut eingesetzt, das durch Zerkleinern eines nach dem Airlaid-Prozess hergestellten Vlieses aus ligninfreiem Faserzellstoff erhalten wird. Zerkleinern im Sinn der Erfindung beinhaltet das mechanische Zerstückeln der Vliese. Die verarbeiteten Airlaid-Vliese besitzen vor dem Zerkleinern vorzugsweise eine durchschnittliche längengewichtete Faserlänge im Bereich von 0,5 bis 5 mm, besonders bevorzugt 2 bis 3 mm. Die längengewichtete Faserlänge ergibt sich als Quotient aus der Summe aller Fasern multipliziert mit den zugehörigen Quadraten der Länge durch Summe aller Fasern multipliziert mit den zugehörigen Längen (Meßverfahren: ISO 16065-1 Norm 2001-09; Faserstoffe - Bestimmung der Faserlänge durch automatische, optische Analyse - Teil 1 : Verfahren mit polarisiertem Licht). Diese Faserlängenangabe bezieht sich auf die Durchschnittslänge der Zellulose- fasern, nicht die Länge des zerkleinerten Airlaid-Zellulosefasermaterials. Jene Länge ist nach Durchlauf durch Agglomeration nicht mehr eindeutig bestimmbar, aber sicher größer als die der Zellulosefasern.As a fiber-reinforcing component it is particularly preferred to use a spreading material which is obtained by comminution of a fleece made of lignin-free fiber pulp produced by the airlaid process. Shredding in the sense of the invention involves the mechanical dismemberment of the nonwovens. The processed airlaid nonwovens preferably have an average length-weighted fiber length in the range of 0.5 to 5 mm, more preferably 2 to 3 mm, prior to comminution. The length-weighted fiber length is calculated as the quotient of the sum of all fibers multiplied by the corresponding squares of the length by the sum of all fibers multiplied by the corresponding lengths (measurement method: ISO 16065-1 standard 2001-09) Fiber materials - Determination of the fiber length by automatic optical analysis - Part 1: Method with polarized light). This fiber length specification refers to the average length of the cellulosic fibers, not the length of the shredded airlaid cellulosic fiber material. This length is no longer clearly determinable after passing through agglomeration, but certainly greater than that of the cellulose fibers.
Da es im Wesentlichen auf die Faserbestandteile des Airlaid- Zellulosefasermaterials ankommt, sind die weiteren Bestandteile von in der Regel untergeordneter Bedeutung für die erfindungsgemäßen Zwecke. Besonders gute Schlagzähigkeiten und Kerbschlagzähigkeiten im Vergleich zu holzmehlversetzten Thermoplasten (insbesondere Polypropylen) sind erreichbar mit solchen erfindungsgemäßen faserverstärkten Thermoplasten, bei denen der Anteil an Airlaid-Zellulosefasermaterial zumindest 25 Gew.-% bezogen auf die Gesamt- menge des faserverstärkten Thermoplasten beträgt.Since it essentially depends on the fiber constituents of the airlaid cellulose fiber material, the further constituents of are generally of minor importance for the purposes of the invention. Particularly good impact strengths and notched impact strengths in comparison to wood-dust-displaced thermoplastics (in particular polypropylene) can be achieved with such fiber-reinforced thermoplastics according to the invention, in which the proportion of airlaid cellulose fiber material is at least 25% by weight, based on the total amount of the fiber-reinforced thermoplastic.
Es ist insbesondere denkbar, nicht nur ein zerkleinertes Airlaid-Vlies selbst, sondern auch vorzugsweise Restposten der industriellen Herstellung und Verarbeitung von Airlaid-Vlies zu sammeln, zu zerkleinern und im erfindungsgemäßen Sinne zu verwenden. Restposten der Vlies-Herstellung nach dem Airlaid-Prozess oder in dem weiteren Verarbeitungsstufen des Materials werden bisher zerklei-
nert, verpresst und deponiert bzw. verbrannt. Die Verbrennung des Materials erfordert jedoch eine Gütekontrolle des Verbrennungsprozesses, so dass sie nur in Spezialanlagen durchführbar ist. Diese Nachteile fallen bei der erfindungsgemäßen Verwendung von Airlaid-Zellulosefasermaterial weg; darüber hinaus können mit dieser Verwendung die oben beschriebenen Vorteile des erfindungsgemäßen Thermoplasten erzielt werden. Daher ist die Verwendung auch von Restposten als faserverstärkende Komponente in Thermoplast- Verbundwerkstoffen besonders bevorzugt.In particular, it is conceivable not only to collect a comminuted airlaid nonwoven itself, but also preferably residual waste from the industrial production and processing of airlaid nonwoven, to comminute it and to use it in the sense according to the invention. Remnants of nonwoven production after the airlaid process or in the further processing stages of the material are so far nert, pressed and dumped or burned. However, the combustion of the material requires a quality control of the combustion process, so that it can only be carried out in special plants. These disadvantages are eliminated in the use according to the invention of airlaid cellulose fiber material; Moreover, with this use, the above-described advantages of the thermoplastic according to the invention can be achieved. Therefore, the use of remnants as fiber-reinforcing component in thermoplastic composites is particularly preferred.
Als Quelle für die zerkleinerten Airlaid-Vliese können vorzugsweise auch Rest- posten eingesetzt werden, die bei der Herstellung und Verarbeitung von saugfähigen Hygieneprodukten anfallen, die Airlaid-Vliese aus ligninfreiem Faserzellstoff enthalten. Saugfähige Hygieneprodukte umfassen insbesondere Hygieneprodukte für Frauen und Windeln.As a source for the comminuted airlaid nonwovens, it is also possible to use residual products which are obtained in the production and processing of absorbent hygiene products which contain airlaid nonwovens of lignin-free fiber pulp. Absorbent hygiene products include, in particular, feminine and diaper hygiene products.
Faserzellstoff, der als Hauptbestandteil des Zellulosefasermaterials besonders bevorzugt ist, ist ein Spezialprodukt der industriellen Gesamtzellstoffproduktion und kann sowohl über das saure Sulfit- als auch das alkalische Sulfat-(Kraft)- Verfahren erhalten werden. Dabei wird der Ligninanteil von vorher typischerweise 30% auf 10% abgesenkt. Es wird auch der Hemizelluloseanteil angegriffen, ist aber beim weit verbreiteten Sulfatverfahren nach Behandlung gegenüber dem Sulfitverfahren mit etwa 12% größer. Üblich sind weiterhin delignifizierende Bleichschritte zur Erhöhung des Weißegrads mit Sauerstoff (oxygen delignificati- on), Wasserstoffperoxid-Aufheller (peroxide brightening) und Ozon Bleiche. Zum Bleichen eingesetzte Chlor-Sauerstoff-Verbindungen werden kaum noch genutzt. Anschließend wird der delignifizierte Faserzellstoff durch ein Nasspapierablege- verfahren, Entwässern, Trocknen und Aufrollen oder Schneiden von Platten in eine transportfähige Form überführt. Dieser flockige, leicht zerfaserbare Faserzellstoff (Fluff PuIp) läßt sich im Airlaidprozess gut weiterverarbeiten.Fiber pulp, which is particularly preferred as the major constituent of the cellulosic fiber material, is a specialty product of industrial pulp production and can be obtained via both the acid sulfite and the alkaline sulfate (Kraft) processes. The lignin content is lowered from previously typically 30% to 10%. The hemicellulose content is also attacked, but is about 12% greater in the widely used sulphate process after treatment over the sulphite process. Also common are delignifying bleaching steps to increase the degree of whitening with oxygen (oxygen delignification), hydrogen peroxide brighteners (peroxide brightening) and ozone bleaching. Used for bleaching chlorine-oxygen compounds are hardly used. Subsequently, the delignified fiber pulp is converted into a transportable form by a wet paper-laying process, dewatering, drying and rolling or cutting of plates. This flaky, easily shredded fiber pulp (Fluff PuIp) can be processed well in the airlaid process.
Faserzellstoff ist die Bezeichnung für die beim Aufschluss von Holz oder anderen Pflanzenfasern anfallende, feinfaserige, vorwiegend aus Zellulose bestehende
Masse. Es ist ein veredeltes Naturprodukt, liegt als weißer, faserartiger Feststoff bei Raumtemperatur vor und besitzt einen Zellulosegehalt von über 95 Gew.%.Fiber pulp is the name given to the fine, predominantly cellulose pulp resulting from the pulping of wood or other plant fibers Dimensions. It is a refined natural product, is present as a white, fibrous solid at room temperature and has a cellulose content of over 95 wt.%.
Faserzellstoff ist weitgehend frei von Lignin, wobei sich ligninfrei im Sinne der Erfindung auf einen Ligningehalt von < 0,5 Gew.% am Gesamtgewicht des (tro- ckenen) Faserzellstoffs bezieht. Lignin läßt sich als Hydrolyserückstand unter Berücksichtigung des Glührückstandes über saure Hydrolyse der zellulosischen Bestandteile bestimmen. Es existiert weiterhin eine NIR (Nahinfrarot)- spektroskopische Methode, bei der lignin-spezifische Infrarot-aktive Banden ausgewertet werden. Der Restligningehalt, ermittelt gemäß DIN 54356 und als sichtbares Eigenschaft durch Angabe des spektralen Reflexionsfaktors Weißgrad (brightness) gemäß ISO 2469/ISO 2470, üblicherweise über 75%, besser über 85% . Es existiert ISO 302 zur Ermittlung des Aufschlussgrads als Kappa-Zahl, (gekoppelt mit Faktor 0.15 ergibt Lignin-%) zur indirekten Bestimmung der oxi- dierbaren Bestandteile, wobei Lignin wesentlichen Anteil hat, aber durch Hexenu- ronsäuren verfälscht sein kann.. Deshalb fällt Kappa-Zahl hierbei gegenüber tatsächlichem Ligningehalt zu hoch aus.Fiber pulp is largely free of lignin, with lignin-free in the context of the invention referring to a lignin content of <0.5% by weight of the total weight of the (dry) fiber pulp. Lignin can be determined as a hydrolysis residue taking into account the residue of ignition by acid hydrolysis of the cellulosic constituents. There is also a NIR (near-infrared) spectroscopic method, in which lignin-specific infrared-active bands are evaluated. The residual lignin content, determined in accordance with DIN 54356 and as a visible property by specifying the spectral reflection factor brightness according to ISO 2469 / ISO 2470, usually over 75%, better over 85%. There exists ISO 302 for determining the degree of digestion as kappa number (coupled with factor 0.15 yields lignin%) for the indirect determination of oxidisable constituents, where lignin has a significant proportion, but may be adulterated by hexenuronic acids Kappa number here too high compared to actual lignin content.
Die Eigenschaften des Faserzellstoffs hängen sowohl von der eingesetzten Holzsorte, als auch von dem verwendeten Herstellungsprozess ab und unterliegen Schwankungen. Vorzugsweise wird Airlaid-Zellulosefasermaterial mit länger- faserigem Weichholz-Nadelholz-Faserzellstoff als faserverstärkende Komponente der Thermoplaste eingesetzt, da diese auf Basis von z.B. Kiefern hergestellten Fasern eine höhere Zugfestigkeit besitzen. Als wesentlicher Unterschied zu hochreinem, meist hemizellulosefreien Chemiezellstoff beträgt der Hemizellulo- seanteil bei Faserzellstoff etwa 12%, bezogen auf das Gesamtgewicht des (tro- ckenen) Faserzellstoffs. Chemiezellstoff findet Einsatz in der Lebensmittel-, Kosmetik- und Pharmaindustrie und bei der Herstellung von Kunstfasern aus Zelluloseregenerat wie Viskose, Zelluloseacetat, Lyocell, Zellulosecarbamat u.a.The properties of the fiber pulp depend both on the type of wood used, as well as on the manufacturing process used and are subject to fluctuations. Preferably, airlaid cellulosic fiber material with longer-fiber softwood softwood fiber pulp is used as a fiber-reinforcing component of the thermoplastics because it is based on e.g. Pine-made fibers have a higher tensile strength. As an essential difference to highly pure, mostly hemicellulose-free, chemical pulp, the hemicellulose content in the case of fiber pulp is about 12%, based on the total weight of the (dry) fiber pulp. Chemical pulp is used in the food, cosmetics and pharmaceutical industries and in the production of synthetic fibers from regenerated cellulose such as viscose, cellulose acetate, lyocell, cellulose carbamate u.a.
Zellulose ist das isotaktische Beta-1 ,4-Polyacetal der Cellobiose und bildet unverzweigte, wasserunlösliche Ketten. Die durchschnittlichen Molmassen betragen 50.000 - 500.000. Als alpha-Zellulose bezeichnet man den bei 20°C in 17,5%iger
NaOH od. 24%iger KOH unlöslichen Anteil mit einem durchschnittlichen Polymerisationsgrad > 200; der aus der natronalkalischen Lösung mit Methanol ausfällbare Anteil wird beta-Zellulose und der nicht fällbare Anteil gamma-Zellulose, die letzteren beide zusammen auch Hemizellulose genannt. Den Zellulosefasern liegt als Basis die so genannte Elementarfibrille, die mit dem Elektronenmikroskop sichtbar ist, zugrunde. Mehrere Elementarfibrillen bilden Mikrofibrillen und Makrofibrillen. Diese Anordnung findet man nur in nativen Zellulosefasern, aber nicht in künstlichen Zelluloseregeneratfasern wie Viskose. Die wichtigsten Rohstoffquellen für Zellulose sind Baumwolle und Bastpflanzen: Flachs, Ramie, Jute, Hanf (z. Z. noch sehr geringe Mengen) für die Textilindustrie und Holz für die Papier- und Pulp-Industrie. Für die erfindungsgemäßen Zwecke wird vorzugsweise Holz, insbesondere von Nadelholz, eingesetzt.Cellulose is the isotactic beta-1,4-polyacetal of cellobiose and forms unbranched, water-insoluble chains. The average molar masses are 50,000 - 500,000. As alpha-cellulose is called the at 20 ° C in 17.5% iger NaOH or 24% KOH insoluble fraction with an average degree of polymerization>200; the fraction which precipitates from the sodium-alkaline solution with methanol becomes beta-cellulose and the non-precipitable fraction gamma-cellulose, the latter both together also called hemicellulose. The cellulosic fibers are based on the so-called elementary fibril, which is visible with the electron microscope. Several elementary fibrils form microfibrils and macrofibrils. This arrangement is found only in virgin cellulosic fibers but not in regenerated cellulosic regenerated fibers such as viscose. The most important sources of raw materials for cellulose are cotton and bast plants: flax, ramie, jute, hemp (still very small quantities at present) for the textile industry and wood for the paper and pulp industry. For the purposes of the invention, wood, especially softwood, is preferably used.
Thermoplaste ist die Bezeichnung für polymere, bei Gebrauchstemperatur weiche oder harte Werkstoffe, die oberhalb der Gebrauchstemperatur einen Fließ- Übergangsbereich besitzen. Thermoplaste bestehen aus linearen oder verzweigten Polymeren, die im Falle amorpher Thermoplaste oberhalb der Glasübergangstemperatur (Tg), im Falle (teil)kristalliner Thermoplaste oberhalb der Schmelztemperatur (Tm) prinzipiell fließfähig werden. Sie können im erweichten Zustand durch Pressen, Extrudieren, Spritzgießen oder andere Formgebungsver- fahren zu Formteilen verarbeitet werden. Wichtige Thermoplaste sind Polyethy- len, Polypropylen, Polystyrol, Polyvinylchlorid, Polyacrylnitrit, Polyamide, Polyester und Polyacrylate. Es können auch Verschnitte verschiedener thermoplastischer Polymere als polymere Matrix eingesetzt werden. Der Thermoplast muss kein Homopolymer sein, sondern kann auch als Copolymer, Polypolymer, Block- polymer oder in anderer Weise modifiziertes Polymer vorliegen.Thermoplastic is the name given to polymeric materials which are soft or hard at service temperature and which have a flow transition region above the service temperature. Thermoplastics consist of linear or branched polymers, which in the case of amorphous thermoplastics above the glass transition temperature (T g ), in the case of (partially) crystalline thermoplastics above the melting temperature (T m ) are in principle fluid. They can be processed in the softened state by molding, extrusion, injection molding or other molding processes to form parts. Important thermoplastics are polyethylenes, polypropylene, polystyrene, polyvinyl chloride, polyacrylonitrile, polyamides, polyesters and polyacrylates. It is also possible to use blends of various thermoplastic polymers as the polymeric matrix. The thermoplastic need not be a homopolymer, but may also be present as a copolymer, polypolymer, block polymer, or otherwise modified polymer.
Vorzugsweise ist die thermoplastische Matrix ein Polypropylen oder enthält ein Polypropylen als Hauptbestandteil in einem Verschnitt, d. h. Polypropylen hat einen Gewichtsanteil von ≥ 50 % an der thermoplastischen Matrix. Verbundwerkstoffe auf dieser polymeren Basis sind - auch in Granulatform oder als Halbzeug - leicht verarbeitbar und zeigen günstige mechanische Kennwerte, insbesondere für die Anwendung im Fahrzeugbau, z. B. für Innenraumverkleidungen.
Gegebenfalls ist zur Erhöhung der Zug- oder Biegefestigkeit - jeweils mit dem Fokus auf die angestrebte Applikation - die Haftung zwischen der polymeren Matrix und der faserverstärkenden Komponente zu erhöhen. Hierzu kann vorzugsweise ein zur Verstärkung einer Wechselwirkung mit Zellulose modifiziertes Polypropylen eingesetzt werden, insbesondere Polypropylen- Maleinsäureanhydrid-Pfropfcopolymer (MAPP). Das modifizierte Polypropylen bzw. eine andere, die Haftung erhöhende Komponente wird der polymeren Matrix oder/und der faserverstärkenden Komponente zugesetzt.Preferably, the thermoplastic matrix is a polypropylene or contains a polypropylene as a main component in a blend, ie polypropylene has a weight fraction of ≥ 50% of the thermoplastic matrix. Composite materials on this polymeric basis are easy to process - also in granular form or as a semi-finished product - and show favorable mechanical characteristics, in particular for use in vehicle construction, eg. B. for interior trim. Optionally, to increase the tensile or flexural strength - in each case with the focus on the desired application - to increase the adhesion between the polymeric matrix and the fiber-reinforcing component. For this purpose it is possible to use preferably a polypropylene modified to enhance an interaction with cellulose, in particular polypropylene-maleic anhydride graft copolymer (MAPP). The modified polypropylene or other adhesion-enhancing component is added to the polymeric matrix or / and the fiber-reinforcing component.
Ferner ist es bevorzugt, dass das Airlaid-Zellulosefasermaterial ein Bindemittel zum Aufrechterhalten einer Bindung zwischen Fasern des Airlaid- Zellulosefasermaterials enthält, ausgewählt aus der Gruppe bestehend aus (i) einem faserigen oder granulierten Thermoplasten, vorzugsweise Polyethylen und/oder Polypropylen und/oder Polyethylenterephthalat, (ii) mit einem Thermoplasten ummantelte Fasern, (iii) einem Latex, vorzugsweise einem selbstvernet- zenden oder vernetzten EVA-Latex, einer Vinylemulsion einschließlich auf Vinyl- acetat oder anderen Vinylestern basierenden Emulsionen in Form von Homopo- lymeren oder Copolymeren mit Ethylen- und/oder Acrylmonomeren, Acrylemulsi- onen in Form von Homo- oder Copolymeren, oder anderen vernetzten Haftmitteln, und Mischungen zweier oder mehrerer dieser Bindemittel gemäß (i) bis (iii). Als Bindemittel hervorzuheben sind neben Latex so genannte Zwei- Komponentenfasern, die einen Kern aus Polypropylen oder aus Polyethylenterephthalat besitzen und eine Ummantelung aus Polyethylen. Das Polyethylen der Ummantelung wirkt dabei als das eigentliche Bindemittel zwischen den Zweioder Bikomponentenfasern, die beim Schmelzen des Polyethylens aufgrund ihres höherschmelzenden Kerns ihre faserige Struktur behalten und so geeignet sind, auch die Zellulosefasern zu halten.Further, it is preferred that the airlaid cellulosic fibrous material comprises a binder for maintaining a bond between fibers of the airlaid cellulosic fiber material selected from the group consisting of (i) a fibrous or granulated thermoplastic, preferably polyethylene and / or polypropylene and / or polyethylene terephthalate, (ii) thermoplastic encapsulated fibers, (iii) a latex, preferably a self-crosslinking or crosslinked EVA latex, a vinyl emulsion including vinyl acetate or other vinyl ester based emulsions in the form of homopolymers or copolymers with ethylene and ethylene or acrylic monomers, acrylic emulsions in the form of homopolymers or copolymers, or other crosslinked adhesives, and mixtures of two or more of these binders according to (i) to (iii). Apart from latex, the so-called two-component fibers, which have a core of polypropylene or of polyethylene terephthalate, and a sheathing of polyethylene are to be emphasized as binders. The polyethylene of the sheath acts as the actual binder between the bicomponent or bicomponent fibers, which retain their fibrous structure when melting the polyethylene due to their higher melting core and are thus suitable to keep the cellulose fibers.
Neben diesen Zweikomponentenfasern kommen als Bindemittel auch Polyester- Copolyester Kern-Mantel Fasern und Mehrkomponentenfasern in Frage. Polyes- ter-Copolyester Kern-Mantel Fasern sind insbesondre geeignet, da auch niedrig- schmelzende Copolyester mit ähnlichen Temperaturfenstern wie Polyethylen verfügbar sind. Die Bindemittel ermöglichen es üblicherweise, dass eine Bindung
zwischen den Fasern des Zellulosefasermaterials auch bei Flüssigkeitskontakt aufrechterhalten bleibt. Die Bindemittel unterstützen weiter die verstärkende Wirkung des Airlaid-Zellulosefasermaterials im faserverstärkten Thermoplasten, indem sie bei der Verarbeitung und im fertigen Thermoplasten den Zusammen- halt des Fasermaterials verbessern. Dies ist insbesondere bei Verwendung eines Streugutes aus Airlaid-Zellulosefasermaterial vorteilhaft.In addition to these two-component fibers, suitable binders are polyester-copolyester core-sheath fibers and multicomponent fibers. Polyester-copolyester core-sheath fibers are particularly suitable since low-melting copolyesters with similar temperature windows as polyethylene are also available. The binders usually allow that binding between the fibers of the cellulose fiber material is maintained even when liquid contact. The binders further promote the reinforcing effect of the airlaid cellulosic fibrous material in the fiber reinforced thermoplastic by improving the bulk of the fibrous material during processing and in the final thermoplastic. This is particularly advantageous when using a spreading material made of airlaid cellulose fiber material.
Erfindungsgemäß günstige Ausführungsformen sind weiterhin Thermoplaste, die superabsorbierende Polymere (SAP) enthalten. Superabsorbierende Polymere (SAP; auch „super slurper") sind polymere gelbildende Verbindungen, die in der Lage sind, sehr große Mengen Wasser zu binden, ohne dabei zu zerfließen. Beispiele sind die durch alkalische Hydrolyse von Stärke/Acrylnitril-Copolymeren hergestellten wasserunlöslichen Stärke/ Acrylamid/Acrylsäure-Pfropfcopolymere oder auch vernetzte Polyacrylsäuren. Nach Verarbeiten des Granulats zu Formteilen ist eine Verringerung des Ausgasens erreichbar.Favorable embodiments according to the invention are also thermoplastics which contain superabsorbent polymers (SAP). Superabsorbent polymers (SAPs) are polymeric gelling compounds that are capable of binding very large amounts of water without deliquescing, such as the water-insoluble starch produced by alkaline hydrolysis of starch / acrylonitrile copolymers. Acrylamide / acrylic acid graft copolymers or also crosslinked polyacrylic acids After processing the granules into shaped parts, a reduction of the outgassing can be achieved.
Ferner können im erfindungsgemäßen Thermoplasten weitere Hilfs- und Zusatzstoffe enthalten sein. Hilfsstoffe können insbesondere Füllstoffe, Stabilisatoren, Antistatika, Flammschutzmittel, Farbmittel in Form von Masterbatches als 1-3% bezogen auf Gesamtgranulat, Flexibilisatoren und Weichmacher, Haftvermittler, Treibmittel, antibakterielle Mittel und Fungizide sein. Als Füllstoff kommen anor- ganische Materialien, wie Kreide, Kalkstein, Marmor, Aluminium, Quarz, Metall, Glimmer usw. in Frage.Furthermore, further auxiliaries and additives may be present in the thermoplastic according to the invention. Auxiliaries may be, in particular, fillers, stabilizers, antistatic agents, flame retardants, masterbatch colorants in the form of 1-3% based on total granules, flexibilizers and plasticizers, adhesion promoters, blowing agents, antibacterial agents and fungicides. Suitable fillers are inorganic materials such as chalk, limestone, marble, aluminum, quartz, metal, mica, etc.
Vorzugsweise weist der Thermoplast folgende Zusammensetzung auf:The thermoplastic preferably has the following composition:
10 - 70 Gewichtsteile Airlaid-Zellulosefasermaterial,10 - 70 parts by weight of airlaid cellulose fiber material,
30 - 90 Gewichtsteile thermoplastische Matrix und30 - 90 parts by weight of thermoplastic matrix and
0,01 - 15 Gewichtsteile Hilfs- und Zusatzstoffe.
Ein Thermoplast der genannten Zusammensetzung lässt sich gut verarbeiten, sei es zu einem Granulat, zu einem Halbzeug oder in anderer, zur Verarbeitung geeigneter Form.0.01 - 15 parts by weight of auxiliaries and additives. A thermoplastic of said composition can be easily processed, be it granules, semi-finished or otherwise suitable for processing.
Zur Herstellung des faserverstärkten Thermoplasts werden die Komponenten in an sich bekannter Weise miteinander vermengt und ggf. gestückelt. Der durch thermische oder physiko-thermische Agglomeration der Komponenten enthaltene Thermoplast wird vorzugsweise als Granulat oder Halbzeug für die Weiterverarbeitung bereitgestellt. Der erhaltene Thermoplast ist als Granulat lagerfähig, logistisch gut handhabbar und einfach in der Weiterverarbeitung einsetzbar. Zellulosefasern aus Faserzellstoff sind weiß, so dass der Zusatz von Farbmitteln im Vergleich mit Naturfasern wesentlich erweitert ist. Daher liegt ein weiterer Aspekt der Erfindung in der Verwendung des faserverstärkten Thermoplasts bzw. des Granulates / des Halbzeugs auf Basis des Thermoplasts im Fahrzeugbau, insbesondere zur Herstellung von Bestandteilen der Fahrzeuginnenraumverklei- düng, wie Seitentürabdeckungen, Frontbereich, Hutablage und Fahrzeughimmel. Hier kann durch das Hinzufügen von Masterbatch, typischerweise 1-3 Gewichtsteile, eine Farbeinstellung erfolgen. Auch ist das faserverstärkte Thermoplast bzw. das Granulat oder das Halbzeug auf Basis des Thermoplasts zur Herstellung von Gehäusen und Verpackungsmaterialien, z.B. von Behältern, vor allem im Fahrzeugbau, besonders geeignet.For the production of the fiber-reinforced thermoplastic, the components are mixed together in a conventional manner and optionally pieced. The thermoplastic contained by thermal or physico-thermal agglomeration of the components is preferably provided as granules or semi-finished products for further processing. The resulting thermoplastic is storable granules, logistically easy to handle and easy to use in further processing. Cellulose fibers made of fiber pulp are white, so that the addition of colorants compared to natural fibers is significantly expanded. Therefore, another aspect of the invention in the use of the fiber-reinforced thermoplastic or of the granules / semi-finished product based on the thermoplastic in vehicle construction, in particular for the production of components of Fahrzeuginnenraumverklei- düng, such as side door covers, front area, parcel shelf and vehicle roof. Here can be done by adding Masterbatch, typically 1-3 parts by weight, a color adjustment. Also, the fiber-reinforced thermoplastic or granules or semi-finished product based on the thermoplastic is for the manufacture of housings and packaging materials, e.g. of containers, especially in vehicle construction, particularly suitable.
Der erfindungsgemäße Thermoplast, einschließlich der hier beschriebenen bevorzugten Ausführungsformen, ist vorteilhaft geeignet zum Bilden eines Formteils, insbesondere zur Verwendung in der Automobilindustrie. Besonders vorteilhaft an einem solchen Formteil ist die durch Verwendung eines erfindungsgemä- ßen Thermoplasten erreichbare hohe Schlagzähigkeit und Kerbschlagzähigkeit bei gleichzeitiger Einsparung an Material der kostenintensiven Thermoplast- Matrix.The thermoplastic according to the invention, including the preferred embodiments described here, is advantageously suitable for forming a molded part, in particular for use in the automotive industry. Particularly advantageous in such a molded part is the high impact strength and notched impact strength achievable by using a thermoplastic according to the invention while at the same time saving material of the cost-intensive thermoplastic matrix.
Nachfolgend wird die Erfindung anhand der Beispiele weiter erläutert, die jedoch den Schutzbereich der Erfindung nicht beschränken. Alle Angaben beziehen sich
nachfolgend auf Gewichtsteile, soweit nichts anderes angegeben ist.The invention will be further elucidated on the basis of the examples which, however, do not limit the scope of protection of the invention. All information relates below to parts by weight, unless stated otherwise.
Beispiel 1 - Restposten der Airlaid-Vlies-Herstellung/VerarbeitungExample 1 - Remnants of airlaid nonwoven production / processing
Restposten, die bei der industriellen Herstellung oder Verarbeitung von Airlaid- Vliesen anfallen, werden in einem Shredder zerkleinert. Das erhaltene Streugut hat typischerweise folgende Zusammensetzung:Remainders that are incurred in the industrial production or processing of airlaid nonwovens are comminuted in a shredder. The grit obtained typically has the following composition:
(i) 70 Gewichtsteile Zellulosefasern aus Faserzellstoff mit einer Faserlänge von 2 - 3 mm.(i) 70 parts by weight of cellulose fibers made of fiber pulp with a fiber length of 2 - 3 mm.
(ii) 10 Gewichtsteile synthetische Fasern (Zwei-Komponenten-Fasern), die aus einem polymeren Kernmaterial mit höherer Schmelztemperatur und einer eine Hülle bildende zweiten polymeren Komponente bestehen. Der Kern ist vorwiegend aus Polypropylen oder Polyethylen- terephthalat und die Hülle aus einem von Polyethylen abgeleiteten Polymer. Die Faserlänge liegt bei 3 - 18 mm.(ii) 10 parts by weight of synthetic fibers (bicomponent fibers) consisting of a higher melting temperature polymeric core material and a second polymeric component forming a shell. The core is predominantly polypropylene or polyethylene terephthalate and the shell is a polyethylene-derived polymer. The fiber length is 3 - 18 mm.
(iii) 10 Gewichtsteile eines superabsorbierenden Polymers (SAP), nämlich einem Polyacrylat. Alternativ können modifizierte Stärke oder andere wasserunlösliche gelbildende Polysaccharide eingesetzt werden.(iii) 10 parts by weight of a superabsorbent polymer (SAP), namely a polyacrylate. Alternatively, modified starch or other water-insoluble gel-forming polysaccharides can be used.
(iv) 8 Gewichtsteile Latex.(iv) 8 parts by weight latex.
(v) 2 Gewichtsteile Polypropylen.(v) 2 parts by weight of polypropylene.
Der Restposten wird in einem Gewichtsverhältnis von 1 : 1 mit Pellets aus reinem Polypropylen vermengt und durch thermomechanische Bearbeitung agglomeriert. Pelletieren des Produkts liefert ein Granulat.
Beispiel 2 - Restposten der WindelherstellungThe remnant is mixed in a weight ratio of 1: 1 with pellets of pure polypropylene and agglomerated by thermomechanical processing. Pelleting the product provides a granule. Example 2 - Remnants of diaper production
Restposten aus der Herstellung und Verarbeitung von Windeln werden in einem Shredder zerkleinert. Das erhaltene Streugut hat die folgende typische Zusammensetzung:Remnants from the manufacture and processing of diapers are shredded in a shredder. The grit obtained has the following typical composition:
(i) 43 Gewichtsteile Zellulosefasern aus Faserzellstoff, die aus Airlaid-(i) 43 parts by weight of cellulosic fibrous fibers made from airlaid
Vliesen stammen. Die Faserlänge liegt bei 2 - 3 mm.Nonwovens come from. The fiber length is 2 - 3 mm.
(ii) 27 Gewichtsteile eines superabsorbierenden Polymers (SAP), nämlich einem Polyacrylat. Alternativ können modifizierte Stärke oder andere wasserunlösliche gelbildende Polysaccharide eingesetzt wer- den.(ii) 27 parts by weight of a superabsorbent polymer (SAP), namely a polyacrylate. Alternatively, modified starch or other water-insoluble gel-forming polysaccharides can be used.
(iii) 22 Gewichtsteile synthetische Fasern (Ein- oder Zwei-Komponenten- Fasern). Der Kern ist vorwiegend aus Polypropylen oder Polyethy- lenterephthalat und bei Zwei-Komponenten-Fasern die Hülle aus einem von Polyethylen abgeleiteten Polymer. Die Faserlänge liegt bei 3 - 18 mm.(iii) 22 parts by weight of synthetic fibers (one- or two-component fibers). The core is predominantly made of polypropylene or polyethylene terephthalate, and in the case of two-component fibers, the shell of a polyethylene-derived polymer. The fiber length is 3 - 18 mm.
(iv) 3 Gewichtsteile Kleber(iv) 3 parts by weight of adhesive
(v) 1 Gewichtsteil elastische Anteile.(v) 1 part by weight of elastic parts.
Der Restposten wird in einem Gewichtsverhältnis von 1 : 1 mit Pellets aus reinem Polypropylen vermengt und durch thermomechanische Bearbeitung agglomeriert. Pelletieren des Produkts liefert ein Granulat.The remnant is mixed in a weight ratio of 1: 1 with pellets of pure polypropylene and agglomerated by thermomechanical processing. Pelleting the product provides a granule.
Vergleich der Schlag- und Kerbschlagzähigkeit erfindungsgemäßer Thermoplaste mit anderen MaterialienComparison of impact strength and notched impact strength of thermoplastics according to the invention with other materials
Polypropylen-Granulat (nachfolgend „PP", Borealis HK 060 AE) wurde mit Holzmehl (nachfolgend „Holz") bzw. Airlaid-Zellulosefasermaterial nachfolgend („Cell")
in den in Tabelle 1 angegebenen Verhältnissen gemischt und spritzgussverarbeitet zu 4 mm dicken ISO-Normstäben:Polypropylene granules (hereafter "PP", Borealis HK 060 AE) were mixed with wood flour (hereinafter "wood") or airlaid cellulose fiber material ("cell") mixed and injection-molded into 4 mm thick ISO standard bars in the ratios given in Table 1:
Tabelle 1Table 1
Die Werkzeugtemperatur betrug 25 °C, o . Schneckenumfangsgeschwindigkeit 10 m/min, der Staudruck 10 bar, die Einspritzgeschwindigkeit 60 cm3/s und die Restkühlzeit 20 s. Das Airlaid-Zellulosefasermaterial enthielt 70 Gew.-% Fluff Pulp-Zellulose, 10 Gew.-% synthetische Fasern aus Polyethylen, Polypropylen und/oder Polyethylenterephthalat, 8 Gew.-% Latex, 10 Gew.-% superabsorbierende Polymerpartikel, Rest Polypropylen-Carrier.
Die hergestellten ISO-Normstäbe wurden gemäß DIN EN ISO 179/1 eAU mit einem Pendel-Zwickschlagwerk bei 23 °C (Schlagzähigkeit Pendel ohne Kerbe: 5 J unverstärkt [100% PP], 2 J verstärkt [Rest]; Kerbschlagzähigkeit Pendel mit Kerbe: 0,5 J) auf ihre Schlagzähigkeit und Kerbschlagzähigkeit untersucht. Tabelle 2 zeigt die Ergebnisse:The mold temperature was 25 ° C, o. The peripheral speed of the screw 10 m / min, the dynamic pressure 10 bar, the injection rate 60 cm 3 / s and the residual cooling time 20 s. The airlaid cellulosic fiber material contained 70% by weight fluff pulp cellulose, 10% by weight synthetic fibers of polyethylene, polypropylene and / or polyethylene terephthalate, 8% by weight latex, 10% by weight superabsorbent polymer particles, balance polypropylene carrier , The ISO standard bars produced were reinforced in accordance with DIN EN ISO 179/1 eAU with a pendulum percussion hammer at 23 ° C. (impact resistance pendulum without notch: 5 J unreinforced [100% PP], 2 J [remainder]; impact value pendulum with notch: 0.5 J) for impact resistance and notched impact strength. Table 2 shows the results:
Tabelle 2Table 2
Man erkennt, dass die erfindungsgemäßen faserverstärkten Thermoplasten imIt can be seen that the fiber-reinforced thermoplastics according to the invention in the
Vergleich zu holzverstärkten Thermoplasten und gegenüber reinem Polypropylen insbesondere ab einem Anteil von 25 Gew.-% an Airlaid-Zellulosefasermaterial
teilweise deutlich bessere, d.h. größere und trotz schwankender Komposition stabile Schlagzähigkeiten und insbesondere größere Kerbschlagzähigkeiten aufweisen.Compared to wood-reinforced thermoplastics and compared to pure polypropylene, in particular from a proportion of 25 wt .-% of airlaid cellulose fiber material Some have significantly better, ie larger and despite fluctuating composition stable impact resistance and in particular greater impact strengths.
Vergleich der Ausgasungswerte erfindungsgemäßer Thermoplaste mit anderen MaterialienComparison of the outgassing values of thermoplastics according to the invention with other materials
Von den oben angegebenen Materialien wurden gemäß DIN 75201 -B durch kontrolliertes Erhitzen Ausgasungsuntersuchungen flüchtiger Bestandteile durchgeführt. Die Proben (kreisförmige 2 mm dicke Platten mit Durchmesser von 80 mm) wurden vorher 14 Tage über Phosphorpentoxid getrocknet. Die Bestandteile kondensieren an einer kühleren Folie, deren Massedifferenz vor und nach der Messung Auskunft über die niedergeschlagenen Bestandteile, auch Fogging genannt, gibt.Of the above-mentioned materials, outgassing tests of volatile constituents were carried out in accordance with DIN 75201 -B by controlled heating. The samples (circular 2 mm thick 80 mm diameter plates) were previously dried over phosphorus pentoxide for 14 days. The constituents condense on a cooler film whose mass difference before and after the measurement gives information about the precipitated constituents, also called fogging.
Man erkennt, dass die erfindungsgemäßen faserverstärkten Thermoplasten im Vergleich zu holzverstärkten Thermoplasten und gegenüber reinem Polypropylen insbesondere ab einem Anteil von 25 Gew.-% an Airlaid-Zellulosefasermaterial teilweise deutlich bessere, d.h. geringere, Kondensatwerte haben und so einer wesentlichen Forderung der Automobilindustrie nach verringerter Kondensation flüchtiger Bestandteile an Scheiben o.a. nachkommen.
It can be seen that the fiber-reinforced thermoplastics according to the invention in some cases significantly better, in comparison with wood-reinforced thermoplastics and pure polypropylene, in particular from a proportion of 25 wt .-% of airlaid cellulose fiber material. lower, have condensate values and so a significant requirement of the automotive industry for reduced condensation of volatiles to discs o.a. progeny.
Claims
1. Faserverstärkter Thermoplast, umfassend:A fiber reinforced thermoplastic comprising:
a) ein Airlaid-Zellulosefasermaterial ina) an airlaid cellulose fiber material in
b) einer thermoplastischen Matrix.b) a thermoplastic matrix.
2. Faserverstärkter Thermoplast nach Anspruch 1 , dadurch gekennzeichnet, dass das Airlaid-Zellulosefasermaterial ein Bindemittel zum Aufrechterhalten einer Bindung zwischen Fasern des Airlaid-Zellulosefasermaterials enthält, ausgewählt aus der Gruppe bestehend aus (i) einem faserigen oder granulierten Thermoplasten, vorzugsweise Polyethylen und/oder Polypropy- len und/oder Polyethylenterephthalat, (ii) mit einem Thermoplasten ummantelte Fasern, (iii) einem Latex, und Mischungen zweier oder mehrerer dieser Bindemittel.A fiber-reinforced thermoplastic according to claim 1, characterized in that the airlaid cellulosic fiber material contains a binder for maintaining a bond between fibers of the airlaid cellulosic fiber material selected from the group consisting of (i) a fibrous or granulated thermoplastic, preferably polyethylene and / or Polypropylene and / or polyethylene terephthalate, (ii) Thermoplastically encapsulated fibers, (iii) a latex, and mixtures of two or more of these binders.
3. Faserverstärkter Thermoplast nach Anspruch 2, dadurch gekennzeichnet, dass das Bindemittel Polyethylen in Form einer äußeren Schicht von Bi- komponenten-Fasern mit einem Kern aus Polypropylen oder Polyethylenterephthalat vorliegt.3. Fiber-reinforced thermoplastic according to claim 2, characterized in that the binder polyethylene is in the form of an outer layer of bicomponent fibers with a core of polypropylene or polyethylene terephthalate.
4. Faserverstärkter Thermoplast nach Anspruch 2, dadurch gekennzeichnet, dass das Bindemittel ein niedrig schmelzendes Polymer als Bestandteil von Mehrkomponentenfasern oder ein einen Mantel von Polyester-Copolyester Kern-Mantel Fasern bildendes Copolyester ist.4. A fiber-reinforced thermoplastic according to claim 2, characterized in that the binder is a low-melting polymer as a component of multi-component fibers or a coat of polyester-copolyester core-sheath fibers forming copolyester.
5. Faserverstärkter Thermoplast nach einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass die thermoplastische Matrix gänzlich oder zu einem überwiegenden Teil von Polypropylen gebildet ist.5. Fiber-reinforced thermoplastic according to one of the preceding claims, characterized in that the thermoplastic matrix is formed entirely or to a predominant part of polypropylene.
6. Faserverstärkter Thermoplast nach einem der vorherigen Ansprüche, ferner umfassend superabsorbierende Polymere. A fiber-reinforced thermoplastic according to any one of the preceding claims, further comprising superabsorbent polymers.
7. Faserverstärkter Thermoplast nach einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass der Anteil an Airlaid-Zellulosefasermaterial zumindest 25 Gew.-% bezogen auf die Gesamtmenge des faserverstärkten Thermoplasten beträgt.7. Fiber-reinforced thermoplastic according to one of the preceding claims, characterized in that the proportion of airlaid cellulose fiber material is at least 25 wt .-% based on the total amount of the fiber-reinforced thermoplastic.
8. Faserverstärkter Thermoplast nach einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass das Zellulosefasermaterial einen Rest- Ligningehalt von höchstens 0,2 Gew.-% aufweist..8. Fiber-reinforced thermoplastic according to one of the preceding claims, characterized in that the cellulose fiber material has a residual lignin content of at most 0.2 wt .-% ..
9. Faserverstärkter Thermoplast nach einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass die längengewichtete Faserlänge des ZeIIuIo- sefasermaterials 0,5 bis 5 mm beträgt.9. Fiber-reinforced thermoplastic according to one of the preceding claims, characterized in that the length-weighted fiber length of ZeIIuIo- sefasermaterials 0.5 to 5 mm.
10. Faserverstärkter Thermoplast nach einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass der Anteil der thermoplastischen Matrix 30 bis 90 Gew.-% bezogen auf die Gesamtmenge des faserverstärkten Thermoplasten beträgt.10. Fiber-reinforced thermoplastic according to one of the preceding claims, characterized in that the proportion of the thermoplastic matrix is 30 to 90 wt .-% based on the total amount of the fiber-reinforced thermoplastic.
1 1. Formteil, herstellbar oder hergestellt durch Formen eines faserverstärkten Thermoplasten nach einem der vorherigen Ansprüche.1 1. molding, or produced by molding a fiber-reinforced thermoplastic according to one of the preceding claims.
12. Verwendung eines Airlaid-Zellulosefasermaterials als Verstärkung in einem faserverstärkten Thermoplasten. 12. Use of an airlaid cellulosic fiber material as reinforcement in a fiber reinforced thermoplastic.
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DE102006013988A DE102006013988A1 (en) | 2006-03-22 | 2006-03-22 | Fiber reinforced thermoplastic |
PCT/EP2007/052536 WO2007107527A1 (en) | 2006-03-22 | 2007-03-16 | Fiber-reinforced thermoplastic |
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EP (1) | EP1999194A1 (en) |
JP (1) | JP2009530462A (en) |
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US20050054253A1 (en) * | 2003-09-05 | 2005-03-10 | The Procter & Gamble Company | Absorbent article including airlaid mixture material containing thermoplastic fibers treated with phosphate ester or sulfate ester |
JP2005144436A (en) | 2003-10-22 | 2005-06-09 | Kao Corp | Oil treatment material |
JP4498783B2 (en) * | 2004-03-17 | 2010-07-07 | トヨタ紡織株式会社 | Method for producing wooden molded body |
JP4659487B2 (en) | 2005-03-02 | 2011-03-30 | 幸年 渡辺 | Hot embossed dry nonwoven fabric and method for producing the same |
RU2008128835A (en) * | 2005-12-15 | 2010-01-20 | Дау Глобал Текнолоджиз Инк. (Us) | IMPROVED CELLULOSE PRODUCTS CONTAINING AN ADDITIVE COMPOSITION |
US20070137811A1 (en) * | 2005-12-15 | 2007-06-21 | Kimberly-Clark Worldwide, Inc. | Premoistened tissue products |
WO2007087037A2 (en) * | 2005-12-16 | 2007-08-02 | Atlantic Recycling Technologies, Llc. | A wet pulping system and method for producing cellulosic insulation with low ash content |
-
2006
- 2006-03-22 DE DE102006013988A patent/DE102006013988A1/en not_active Withdrawn
-
2007
- 2007-03-16 JP JP2009500836A patent/JP2009530462A/en active Pending
- 2007-03-16 CA CA002645113A patent/CA2645113A1/en not_active Abandoned
- 2007-03-16 CN CN200780010165.5A patent/CN101405328B/en not_active Expired - Fee Related
- 2007-03-16 EP EP07727015A patent/EP1999194A1/en not_active Withdrawn
- 2007-03-16 WO PCT/EP2007/052536 patent/WO2007107527A1/en active Application Filing
- 2007-03-16 US US12/224,975 patent/US8530548B2/en active Active
Non-Patent Citations (1)
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See references of WO2007107527A1 * |
Also Published As
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JP2009530462A (en) | 2009-08-27 |
CN101405328B (en) | 2013-07-03 |
DE102006013988A1 (en) | 2007-09-27 |
US8530548B2 (en) | 2013-09-10 |
CN101405328A (en) | 2009-04-08 |
US20090306253A1 (en) | 2009-12-10 |
CA2645113A1 (en) | 2007-09-27 |
WO2007107527A1 (en) | 2007-09-27 |
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