WO2015022404A1 - Matière de moulage thermoplastique renforcée par fibres, à résistance renforcée des lignes de soudure - Google Patents

Matière de moulage thermoplastique renforcée par fibres, à résistance renforcée des lignes de soudure Download PDF

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Publication number
WO2015022404A1
WO2015022404A1 PCT/EP2014/067433 EP2014067433W WO2015022404A1 WO 2015022404 A1 WO2015022404 A1 WO 2015022404A1 EP 2014067433 W EP2014067433 W EP 2014067433W WO 2015022404 A1 WO2015022404 A1 WO 2015022404A1
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weight
fibrous reinforcing
proportions
sum
thermoplastic
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PCT/EP2014/067433
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German (de)
English (en)
Inventor
Gabriel CLAUS
Christian Schmidt
Heiko Heß
Sven WENIGMANN
Matthias Scheibitz
Uwe Gleiter
Andreas Wollny
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Basf Se
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Publication of WO2015022404A1 publication Critical patent/WO2015022404A1/fr

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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
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • 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
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers

Definitions

  • the invention relates to a process for producing a fiber-reinforced thermoplastic molding composition with improved weld line strength, and to a molding composition obtainable from this process. Furthermore, the invention relates to moldings which are produced from the thermoplastic molding composition according to the invention.
  • the complexity of injection molded components is increasing steadily. Binding sutures are almost inevitably produced on components that are manufactured by injection molding, when two different melt streams are brought together or when the melt stream flows around an obstacle. For example, if breakthroughs are present in a component, or if a component is injection-molded from several different positions, weld lines are an unavoidable problem.
  • the structure of the component on which these weld lines are located differs from the structure of the rest of the component. For example, in fiber-reinforced plastics, the fibers line up parallel to the weld line, but do not intersect it, whereas the fibers in the other part line up parallel to the flow direction.
  • the resulting weld lines are a weak point of the respective components and cause not only optical markings on the surface but also insufficient strength of the component.
  • Sousa et al. (Journal of Applied Polymer Science 2006, 14, 3592-3601) relates to the influence of hybridization of short glass fibers with talc on the mechanical processing properties of polypropylene composites.
  • the addition of short glass fibers imparts high rigidity and strength to the plastic but disadvantageous weld line properties. This is counteracted by stepwise replacement of the reinforcing fiber with talc.
  • Favis et al. (Advances in Polymer Technology 1995, 14 (3), 169-196) gives an overview of the properties of weld lines in components produced by injection molding. It has been shown that long glass fiber reinforced plastics have a lower weld line strength than the corresponding unreinforced or short glass fiber reinforced compositions. It has also been shown on the example of polypropylene that the weld line strength steadily decreases as the proportion of long glass fibers increases.
  • An object of the invention was therefore to provide a process for producing fiber-reinforced thermoplastic molding compositions which improved the weld line strength while maintaining the mechanical strength in comparison with known fiber-reinforced having thermoplastic molding compositions. Furthermore, it was an object of the present invention to provide moldings of thermoplastic molding compositions prepared in this way.
  • thermoplastic molding composition comprising the following steps:
  • Melting a mixture comprising a first granulate comprising at least one thermoplastic polymer A1 and at least one fibrous reinforcing material B2 having an average fiber length of 4.5 to 13.0 mm and a second granulate containing at least one thermoplastic polymer A2 and at least one fibrous reinforcing material B1 having a middle one Fiber length from 0.15 to 1, 2 mm,
  • thermoplastic polymers A1 and A2 15.2 to 85.0 wt .-% and the sum of the weight fractions of the fibrous reinforcing materials B1 and B2 is 15.0 to 84.8 wt .-%, wherein the quantities each refer to the sum of all components in the thermoplastic molding material; wherein the ratio of the sum of the weight proportions of the thermoplastic polymers A1 and A2 to the sum of the weight proportions of the fibrous reinforcing materials B1 and B2 is between 1: 5.5 and 5.5: 1; and wherein the ratio of the weight proportions of the fibrous reinforcing materials B1 and B2 is between 20:80 and 80:20.
  • the total amount of all components A1, A2, B1, B2 and optionally C to F in the thermoplastic molding composition according to the invention is 100% by weight. It has now surprisingly been found that the addition of both short and long reinforcing fibers, the Bindenahtfesttechnik of fiber-reinforced thermoplastic molding compositions can be increased while maintaining the mechanical strength.
  • the sum of the weight proportions of the thermoplastic polymers A1 and A2 in the thermoplastic molding composition is according to the invention 15.2 to 85.0 wt .-%, preferably 25.0 to 75.0 wt .-%, preferably 35.0 to 70.0 wt .-%, particularly preferably 40 to 60 wt .-%.
  • the sum of the weight fractions of the thermoplastic polymers A1 and A2 in the thermoplastic molding composition is 17.0 to 53.0% by weight, preferably 23.0 to 45.0% by weight, preferably 29, 0 to 38.0% by weight.
  • thermoplastic polymers A1 and A2 are preferably selected independently of one another from acrylonitrile-butadiene-styrene (ABS), polyamide (PA), polymethyl methacrylate (PMMA), polycarbonate (PC), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene (PE ), Polypropylene (PP), polystyrene (PS), polyetheretherketone (PEEK), polyoxyethylene (POM) and polyvinylchloride (PVC).
  • ABS acrylonitrile-butadiene-styrene
  • PA polyamide
  • PMMA polymethyl methacrylate
  • PC polycarbonate
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PE polyethylene
  • PE Polypropylene
  • PS polystyrene
  • PEEK polyetheretherketone
  • POM polyoxyethylene
  • PVC polyvinylchloride
  • A1 and A2 independently of one another, being polyamide (PA), polypropylene (PP), polybutylene terephthalate (PBT) or polyoxymethylene (POM).
  • PA polyamide
  • PP polypropylene
  • PBT polybutylene terephthalate
  • POM polyoxymethylene
  • A1 and A2 are independently polybutylene terephthalate (PBT) or polyoxymethylene (POM). Particularly preferably, A1 and A2 are independently selected from polyamide or polypropylene.
  • Suitable polyamides are aliphatic, partially aromatic or aromatic polyamides.
  • aliphatic polyamides means that the polyamides are exclusively composed of aliphatic monomers
  • partially aromatic polyamides means that the polyamides are composed of both aliphatic and aromatic monomers.
  • aromatic polyamides means that the polyamides are exclusively composed of aromatic monomers
  • the polyamides according to the invention generally have a viscosity number from 70 to 350, preferably from 70 to 200 ml / g, determined in 96% strength by weight sulfuric acid at 25 ° C according to ISO 307.
  • the polyamide is preferably selected from polyamides derived from lactams having 7 to 13 ring members, such as polycaprolactam, polycapryllactam and polylaurolactam and polyamides obtained by reacting dicarboxylic acids with diamines.
  • Suitable dicarboxylic acids are alkanedicarboxylic acids having 6 to 12, in particular 6 to 10, carbon atoms and aromatic dicarboxylic acids, in particular adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and terephthalic and / or isophthalic acid.
  • Suitable diamines are in particular alkanediamines having 6 to 12, preferably 6 to 8 carbon atoms and m-xylylenediamine, di- (4-aminophenyl) methane, di- (4-aminocyclohexyl) methane, 2,2-di (4- aminophenyl) -propane, 2,2-di- (4-aminocyclohexyl) -propane or 1, 5-diamino-2-methylpentane.
  • Preferred polyamides are Polyhexamethylenadipinklamid, Polyhexamethylensebacin Text- reamid and polycaprolactam and Copolyamide 6/66, in particular with a proportion of 5 to 95 wt .-% of caprolactam units.
  • polyamide 6 Suitable polyamides are obtainable from ⁇ -aminoalkyl nitriles such as in particular aminocapronitrile (polyamide 6) and adiponitrile with hexamethylenediamine (polyamide 66) by so-called direct polymerization in the presence of water.
  • polyamide 6 aminocapronitrile
  • polyamide 66 adiponitrile with hexamethylenediamine
  • polyamides may also be mentioned which are obtainable, for example, by condensation of 1,4-diaminobutane under elevated temperature (polyamide 4,6). Production processes for polyamides of this structure are known to the person skilled in the art.
  • polyamides which are obtainable by copolymerization of two or more of the abovementioned monomers or mixtures of a plurality of polyamides are suitable, the mixing ratio being arbitrary.
  • PA 46 tetramethylenediamine, adipic acid
  • PA 66 hexamethylenediamine, adipic acid
  • PA 610 hexamethylenediamine, sebacic acid
  • PA 612 hexamethylenediamine, decanedicarboxylic acid
  • PA 613 hexamethylenediamine, undecanedicarboxylic acid
  • PA 1212 1, 12-dodecanediamine, decanedicarboxylic acid
  • PA 1313 1, 13-diaminotridecane, undecanedicarboxylic acid
  • PA 6T hexamethylenediamine, terephthalic acid
  • PA MXD6 m-xylylenediamine, adipic acid
  • PA 6I hexamethylenediamine, isophthalic acid
  • PA 6-3-T trimethylhexamethylenediamine, terephthalic acid
  • PA 6 / 6T see PA 6 and PA 6T
  • PA 6/66 see PA 6 and PA 66
  • PA 6/12 see PA 6 and PA 12
  • PA 66/6/61 see PA 66, PA 6 and PA 610
  • PA 6I / 6T see PA 61 and PA 6T
  • PA PA PACM 12 diaminodicyclohexylmethane, laurolactam
  • PA 6I / 6T / PACM such as PA 6I / 6T and diaminodicyclohexylmethane
  • thermoplastic polymers A1 and A2 are independently selected from the group consisting of polyamide 6, polyamide 66, polyamide 610 and polyamide 6 / 6T, more preferably polyamide 6 and polyamide 66.
  • A1 and A2 are independently polypropylene.
  • Suitable polypropylenes are for example polypropylene homopolymers, wherein the methyl side chains can be incorporated isotactic, syndiotactic or atactic; Copolymers of polypropylene, for example polypropylene-polyethylene copolymers, wherein the ethylene and propylene units may be arranged randomly, alternately or in blocks, ethylene-propylene-diene copolymers, polypropylene-maleic acid copolymers; as well as semi-crystalline and amorphous polypropylenes.
  • the at least one thermoplastic polymer A1 and the at least one thermoplastic polymer A2 may be the same or different. Preferably, A1 and A2 are the same.
  • Fiber-shaped reinforcing materials B1 and B2 are Fiber-shaped reinforcing materials B1 and B2
  • the sum of the weight proportions of the fibrous reinforcing materials B1 and B2 in the thermoplastic molding composition is according to the invention 15.0 to 84.8 wt .-%, preferably 25.0 to 75.0 wt .-%, preferably 30.0 to 65.0 wt .-%, more preferably 40.0 to 60.0 wt .-%.
  • the sum of the weight fractions of the fibrous reinforcing materials B1 and B2 in the thermoplastic molding composition is 17.0 to 53.0% by weight, preferably 23.0 to 45.0% by weight, preferably 29.0 to 38.0% by weight.
  • the ratio of the sum of the weight fractions of the thermoplastic polymers A1 and A2 to the sum of the weight fractions of the fibrous reinforcing materials B1 and B2 is between 1: 5.5 and 5.5: 1, preferably 1: 3 and 3: 1, preferably 1: 2 and 2: 1.
  • the ratio of the sum of the weight proportions of the thermoplastic polymers A1 and A2 to the sum of the weight proportions of the fibrous reinforcing materials B1 and B2 is 1: 1.
  • the at least one fibrous reinforcing material B1 has an average fiber length of 0.15 to 4.2 mm, preferably 2.0 to 4.1 mm, preferably 3.0 to 4.0 mm. In a further preferred embodiment, the at least one fibrous reinforcing material B1 has an average fiber length of 0.15 to 1.2 mm, preferably 0.17 to 1.0 mm, particularly preferably 0.18 to 0.8 mm, particularly preferably 0, 19 to 0.25 mm.
  • the at least one fibrous reinforcing material B2 has an average fiber length of 4.5 to 13 mm, preferably 5 to 12 mm.
  • the at least one fibrous reinforcing material B1 is a short fiber component in which at least one fibrous reinforcing material B2 is a long fiber component.
  • the analysis of the fiber length for example, optically after the ashing of the material to be examined in a microscope (QX Fiber, Leica) done.
  • the mean values indicated are arithmetic mean values; this means that the given value is the quotient of the sum of all observed values and the number of values.
  • the average fiber length is 0.15 to 4.2 mm, preferably 2.0 to 4.1 mm, particularly preferably 3 , 0 to 4.0 mm.
  • the average fiber length of the at least one fibrous reinforcing material B1 is 0.15 to 1.2 mm, preferably 0.17 to 1, 0 mm, more preferably 0.18 to 0.8 mm, particularly preferably 0.19 to 0.25 mm.
  • the fibrous reinforcing materials B1 and B2 are used in a weight ratio of from 20:80 to 80:20, preferably from 30:70 to 70:30, more preferably from 40:60 to 60:40, and especially preferably in a weight ratio of 50:50.
  • the fibrous reinforcing materials B1 and B2 are independently selected preferably from carbon fibers, aramid fibers, glass fibers, basalt fibers, boron fibers, ceramic fibers and potassium titanate fibers and mixtures thereof. Most preferably, the fibrous reinforcing materials B1 and B2 are independently selected from the group consisting of carbon fibers and glass fibers.
  • the at least one fibrous reinforcing material B1 and the at least one fibrous reinforcing material B2 may be the same or different.
  • B1 and B2 are the same.
  • Particularly preferred B1 and B2 are glass fibers.
  • the at least one fibrous reinforcing material B1 is short glass fibers, these are preferably used as chopped glass fibers. If the at least one fibrous reinforcing material B2 is long glass fibers, these preferably have a diameter of 6 to 20 ⁇ m, preferably 10 to 18 ⁇ m, the cross section of the glass fibers being round, oval or angular. Preferably, the L / D (length / diameter) ratio is 100 to 4000, preferably 350 to 2000 and particularly preferably 350 to 700.
  • suitable sources of glass fibers are E glass, S glass, R glass, M glass, C glass, ECR glass, D glass, AR glass, Q glass, T glass and hollow glass fibers; preference is given to the glass fiber source E-glass, R- or S-glass (fibers with increased strength) as well as C or T-glass (fibers with increased chemical resistance).
  • the production of long glass fiber-reinforced granules can be carried out for example by pultrusion, wherein the endless fiber strand (roving) completely impregnated with the polymer melt and then cooled and cut.
  • the fibrous reinforcing materials B1 and B2 can be pretreated for better compatibility with the at least one thermoplastic polymer A1 and / or with the at least one thermoplastic polymer A2.
  • the fibrous reinforcing materials are preferably coated.
  • Suitable coating agents also called sizing agents, are, for example, silane compounds or isocyanate-based coating compositions.
  • Suitable silane compounds are those of the general formula
  • n is an integer from 1 to 5, preferably from 3 to 4;
  • n is an integer from 1 to 5, preferably 1 to 2;
  • k is an integer from 1 to 3, preferably 1.
  • Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes which contain a glycidyl group as substituent.
  • the silane compounds are generally used in amounts of 0.01 to 2.0 wt .-%, preferably 0.025 to 1, 0 wt .-% and in particular 0.05 to 0.5 wt .-%, based on the amount of glass fibers. In one embodiment, neither the fibrous reinforcing material B1 nor the fibrous reinforcing material B2 is coated.
  • the fibrous reinforcing material B1 is coated and the fibrous reinforcing material B2 uncoated.
  • the fibrous reinforcing material B2 may be coated and the fibrous reinforcing material B1 uncoated.
  • both the fibrous reinforcing material B1 and the fibrous reinforcing material B2 may be coated.
  • the novel molding composition may contain 0 to 5.0% by weight, preferably 0.1 to 4.5% by weight, particularly preferably 0.2 to 3.0% by weight, of at least one additive C.
  • the at least one additive C is particularly preferably selected from stabilizers, oxidation retardants, dyes, pigments, color brighteners, lubricants, plasticizers, lubricants and mold release agents, nucleating agents and mixtures thereof.
  • UV stabilizers or heat stabilizers are preferably mentioned as stabilizers.
  • the UV stabilizers are preferably selected from substituted resorcinols, salicylates, benzotriazoles and benzophenones. UV stabilizers are generally used in amounts of up to 2 wt .-%, based on the sum of all components in the thermoplastic molding composition.
  • Preferred antioxidants and heat stabilizers are phosphites, amines, hydroquinones, their derivatives and mixtures thereof.
  • the heat stabilizers are particularly preferably a) compounds of monovalent or divalent copper, for example salts of monovalent or divalent copper with inorganic or organic acids or mono- or dihydric phenols, oxides of copper, or complex compounds of copper salts with ammonia. ak, amines, amides, lactams, cyanides or phosphines, preferably Cu (l) - or Cu (II) salts of the hydrohalic acids, the hydrocyanic acids or the copper salts of the aliphatic carboxylic acids.
  • the monovalent copper compounds CuCl, CuBr, Cul, CuCN and CU2O and the divalent copper compounds CuC, CuSC, CuO, copper (II) acetate or copper (II) stearate.
  • the copper compounds are preferred in amounts of 0.005 to 0.5 wt .-%, in particular 0.005 to 0.3 wt .-% and particularly preferably from 0.01 to 0.2 wt .-%, based on the sum of all components in the thermoplastic molding material used.
  • the listed copper compounds are commercially available, or their preparation is known in the art.
  • the copper compound can be used as such or in the form of concentrates.
  • Concentrate here is to be understood as meaning a polymer, preferably of the same chemical nature as the thermoplastic polymer A, which contains the copper salt in high concentration.
  • the use of concentrates is a common procedure and is particularly often used when very small amounts of a feedstock are to be dosed.
  • the copper compounds are advantageously used in combination with other metal halides, in particular alkali halides such as Nal, Kl, NaBr or KBr, the molar ratio of metal halide to copper being 0.5 to 20, preferably 1 to 10 and particularly preferably 2 to 5.
  • stabilizers based on secondary aromatic amines these stabilizers preferably in an amount of 0.2 to 2.0 wt .-%, preferably 0.5 to 1, 5 wt .-%, based on the sum of all components in the thermoplastic molding material, are present.
  • Stabilizers based on secondary aromatic amines are known per se to a person skilled in the art and can be used advantageously in the context of the present invention.
  • stabilizers based on sterically hindered phenols these stabilizers preferably in an amount of 0.05 to 1, 5 wt .-%, preferably 0, 1 to 1 wt .-%, based on the sum of all components in the thermoplastic molding composition , present.
  • Preferred dyes and pigments are selected from inorganic pigments such as zinc oxide, antimony white, titanium dioxide, ultramarine blue, chrome oxide green, iron oxide and carbon black and / or graphite, furthermore organic pigments such as pthalocyanines, quinacridones, perylenes and dyes such as nigrosine and anthraquinones.
  • inorganic pigments such as zinc oxide, antimony white, titanium dioxide, ultramarine blue, chrome oxide green, iron oxide and carbon black and / or graphite
  • organic pigments such as pthalocyanines, quinacridones, perylenes and dyes such as nigrosine and anthraquinones.
  • the nucleating agent is preferably selected from talcum, calcium fluoride, sodium phenylphosphinate, aluminum oxide, silicon dioxide or finely divided polytetrafluoroethylene, particularly preferably talc is used.
  • the lubricant is preferably selected from aluminum salts, alkali salts, alkaline earth salts or esters or amides of fatty acids having 10 to 44 carbon atoms, preferably 14 to 44 carbon atoms.
  • the metal ions are preferably alkaline earth or aluminum ions, with calcium or magnesium ions being particularly preferred.
  • Preferred metal salts are calcium stearate and calcium montanate, as well as aluminum stearate. It is also possible to use mixtures of the different salts, the mixing ratio being arbitrary.
  • the carboxylic acids may be monovalent or divalent. Examples which may be mentioned are pelargonic acid, palmitic acid, lauric acid, margaric acid, dodecanedioic acid, behenic acid and particularly preferably stearic acid, capric acid and montanic acid.
  • Suitable lubricants and mold release agents are stearic acid, stearyl alcohol, stearic acid esters, or generally higher fatty acids, their derivatives and corresponding fatty acid mixtures having 12 to 30 carbon atoms. These additives are preferably added in amounts of 0.05 to 1 wt .-%, based on the sum of all components in the thermoplastic molding composition.
  • Suitable plasticizers are dioctyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, hydrocarbon oils, N- (n-butyl) benzylsulfonamide, o- and p-toluene-ethylsulfonamide, which are present in amounts of up to 2.0% by weight, based on the sum of all components in the thermoplastic molding composition, are used.
  • the molding composition of the invention 0 to 25.0 wt .-%, preferably 5.0 to 20.0 wt .-%, more preferably 10.0 to 15.0 wt .-% of at least one flame retardant D included.
  • a suitable flame retardant is, for example, elemental phosphorus.
  • the elemental phosphorus can be phlegmatized or coated with, for example, polyurethane, aminoplasts or dialkyl phthalates, for example dioctyl phthalate.
  • concentrates of red phosphorus for example in a polyamide, elastomer or polyolefin are suitable.
  • Phosphorus compounds such as organic phosphates, phosphonates, phosphinates, phosphine oxides, phosphines or phosphites are also suitable.
  • organic phosphates phosphonates, phosphinates, phosphine oxides, phosphines or phosphites
  • triphenylphosphine oxide and triphenyl phosphate may be mentioned. These may be used alone or mixed with hexabromobenzene or a chlorinated biphenyl and, optionally, antimony oxide.
  • flame retardant D compounds which contain phosphorus nitrogen bonds, such as phosphonitrile chloride, phosphoric acid ester amides, phosphoric ester amines, phosphoric acid amides, phosphonic acid amides, tris (aziridinyl) phosphine oxide or tetrakis (hydroxymethyl) phosphonium chloride. These additives are mostly available commercially. Further suitable flame retardants are hydroxides of magnesium and of aluminum, which are optionally coated with silane compounds or nitrogen compounds such as melamine cyanurate.
  • halogen-containing flame retardants are tetrabromobenzene, hexachlorobenzene and hexa-bromobenzene as well as halogenated polystyrenes and polyphenylene ethers.
  • the molding composition of the invention 0 to 15.0 wt .-%, preferably 5.0 to 15.0 wt .-%, particularly preferably 5.0 to 10.0 wt .-% of at least one filler E.
  • the at least one filler E is preferably selected from talc, calcium carbonate, wollastonite, phlogopite and muscovite.
  • Other suitable fillers are glass beads, glass flakes, powdered quartz, biotite, kaolin, feldspar or mica.
  • suitable fillers are those which impart a metallic appearance to the thermoplastic molding composition, for example aluminum flakes or copper; or those which help the thermoplastic molding composition to an increased thermal conductivity, for example aluminum and copper, and inorganic ceramic fillers, such as aluminum nitride, xagonal xenonitrile, graphite and carbon fibers, furthermore zinc oxide and aluminum oxide.
  • the thermoplastic molding composition may comprise 0 to 20.0% by weight, preferably 5.0 to 20.0% by weight, particularly preferably 10.0 to 15.0% by weight of at least one impact-modifying rubber, in particular graft rubbers.
  • Graft rubbers in the context of the invention are understood to mean core-shell rubbers which may also have a multi-shell structure. It is possible to use conventional impact modifiers which are suitable for thermoplastic polymers.
  • Rubbers which increase the toughness of thermoplastic polymers generally have two important features: they contain an elastomeric fraction which has a glass transition temperature of less than -10.degree. C., preferably less than -30.degree. C., and contain them at least one functional group that can interact with the thermoplastic polymer.
  • Suitable functional groups are, for example, carboxylic acid, carboxylic acid anhydride, carboxylic acid ester, carboxylic acid amide, carboximide, amino, hydroxyl, epoxy, urethane and oxazoline groups.
  • EP or EPDM rubbers which have been grafted with the abovementioned functional groups.
  • Suitable grafting reagents are, for example, maleic anhydride, itaconic acid, acrylic acid, glycidyl acrylate and glycidyl methacrylate. These monomers may be grafted onto the polymer in the melt or in solution, optionally in the presence of a radical initiator such as cumene hydroperoxide.
  • copolymers of ⁇ -olefins may be mentioned.
  • the ⁇ -olefins are usually monomers having 2 to 8 C atoms, preferably ethylene and propylene.
  • Suitable comonomers are alkyl acrylates or alkyl methacrylates derived from alcohols having from 1 to 8 carbon atoms, preferably from ethanol, butanol or ethylhexanol, as well as reactive comonomers such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride or glycidyl (meth) acrylate and furthermore vinyl esters, in particular Vinyl acetate, proved to be suitable.
  • Mixtures of different comonomers can also be used. Copolymers of ethylene with ethyl or butyl acrylate and acrylic acid and / or maleic anhydride have proved to be particularly suitable.
  • the copolymers can be prepared in a high pressure process at a pressure of 400 to 4500 bar or by grafting the comonomers onto the poly- ⁇ -olefin.
  • the proportion of the ⁇ -olefin in the copolymer is generally in the range of 99.95 to 55.0 wt%.
  • elastomers are core-shell graft rubbers. These are graft rubbers made in emulsion, which consist of at least one hard and one soft component.
  • a hard component is usually understood to mean a polymer having a glass transition temperature of at least 25 ° C., and a polymer having a glass transition temperature of at most 0 ° C. under a soft component.
  • These products have a structure of a core and at least one shell, the structure resulting from the order of monomer addition.
  • the soft components are generally derived from butadiene, isoprene, alkyl acrylates, alkyl methacrylates or siloxanes and optionally further comonomers.
  • Suitable siloxane cores can be prepared, for example, starting from cyclic oligomeric octamethyltetrasiloxane or tetravinyltetramethyltetrasiloxane or tetravinyltetramethyltetrasiloxane. These can, for example, be reacted with ⁇ -mercaptopropylmethyldimethoxysilane in a ring-opening cationic polymerization, preferably in the presence of sulfonic acids, to give the soft siloxane cores.
  • the siloxanes can also be crosslinked by, for example, carrying out the polymerization reaction in the presence of silanes having hydrolyzable groups such as halogen or alkoxy groups such as tetraethoxysilane, methyltrimethoxysilane or phenyltrimethoxysilane.
  • Suitable comonomers here are, for example, styrene, acrylonitrile and crosslinking or graft-active monomers having more than one polymerizable double bond, such as diallyl phthalate, divinylbenzene, butanediol diacrylate or triallyl (iso) cyanurate.
  • the hard constituents are generally derived from styrene, ⁇ -methylstyrene and their copolymers, in which case comonomers are preferably acrylonitrile, methacrylonitrile and methyl methacrylate.
  • Preferred core-shell graft rubbers include a soft core and a hard shell or hard core, a first soft shell and at least one other hard shell.
  • the incorporation of functional groups such as carbonyl, carboxylic acid, acid anhydride, acid Reamide, acid, carboxylic acid ester, amino, hydroxyl, epoxy, oxazoline, urethane, urea, lactam or halobenzyl, is preferably carried out by the addition of suitably functionalized monomers in the polymerization of the last shell.
  • Suitable functionalized monomers are, for example, maleic acid, maleic anhydride, mono- or diesters of maleic acid, tert-butyl (meth) acrylate, acrylic acid, glycidyl (meth) acrylate and vinyl oxazoline.
  • the proportion of monomers having functional groups is generally from 0.1 to 25 wt .-%, preferably 0.25 to 15 wt .-%, based on the total weight of the core-shell graft rubber.
  • the weight ratio of soft to hard components is generally 1: 9 to 9: 1, preferably 3: 7 to 8: 2.
  • graft rubbers which contain no ethylenically unsaturated hydrocarbon radicals (olefinic double bonds).
  • ASA rubbers acrylonitrile-styrene-alkyl acrylate rubbers.
  • thermoplastic molding composition
  • the processing of the at least one thermoplastic polymer A1 and the at least one thermoplastic polymer A2 with the reinforcing materials B1 and B2, and optionally the components C to F can be carried out in any desired manner by all known methods.
  • extruders are used for this purpose, for example single-screw or twin-screw extruders or other conventional plasticizing devices such as Brabender mills, Banbury mills or injection molding machines.
  • first a granulate comprising at least one thermoplastic polymer A1 and at least one fibrous reinforcing material B2 is melted, and then at least one fibrous reinforcing material B1 is admixed.
  • the at least one fibrous reinforcing material B1 preferably has an average fiber length of 0.15 to 4.2 mm, preferably 2.0 to 4.1 mm, preferably 3.0 to 4.0 mm.
  • first a first granulate containing at least one thermoplastic polymer A1 and at least one fibrous reinforcing material B2 is melted with a second granulate containing at least one thermoplastic polymer A2 and at least one fibrous reinforcing material B1.
  • the at least one fibrous reinforcing material B1, contained in the second granulate has an average fiber length of 0.15 to 1.2 mm, in this case preferably 0.17 to 1, 0 mm, more preferably 0.18 to 0.8 mm, particularly preferably 0.19 to 0.25 mm.
  • the at least one thermoplastic polymer A1 and the at least one thermoplastic polymer A2 may be the same or different.
  • the thermoplastic polymers A1 and A2 can each contain mixtures of different thermoplastic polymers.
  • A1 and A2 are the same.
  • the granules according to the invention containing at least one thermoplastic polymer A1 and at least one fibrous reinforcing material B2 can be produced by the known processes for the production of fiber-reinforced granules, in particular by pultrusion processes in which the endless fiber strand (roving) with the polymer melt is completely penetrated. soaked and then cooled and cut. In this way, a long-fiber-reinforced granules, which preferably has a granule length of 3 to 20 mm, in particular from 5 to 14 mm and preferably 8 to 12 mm, obtained. In granules obtained by this method, the average fiber length of the at least one fibrous reinforcing material B2 corresponds to the mean length of the obtained granules.
  • the granulate containing at least one thermoplastic polymer A2 and at least one fibrous reinforcing material B1 is a long rod granulate, the length of the granules being on average 7 mm.
  • the long rod granules according to the invention containing B1 can be prepared by conventional methods, for example by compounding in a twin-screw extruder with subsequent granulation.
  • the invention further relates to molded articles which are produced from the thermoplastic molding composition according to the invention.
  • the moldings according to the invention are preferably produced by the customary processing methods, such as extrusion or injection molding. Preferably, the production of the moldings by injection molding.
  • thermoplastic molding composition according to the invention are used for the production of interior and exterior parts, preferably with supporting or mechanical function in the field of electrical, furniture, sports, mechanical engineering, sanitation and hygiene, medicine, energy and drive technology, automotive and other transport or housing material used for devices and apparatus for telecommunications, consumer electronics, household appliances, mechanical engineering, heating sector or fasteners for installations or for containers and ventilation parts of all kinds.
  • the shaped body according to the invention is preferably a shaped body which has at least one weld line.
  • thermoplastic molding composition with other compatible or incompatible materials, such.
  • thermoplastics thermosets or elastomers is combined.
  • thermoplastic molding composition such as bearings or threaded inserts of the thermoplastic molding composition according to the invention, overmolded with other compatible or incompatible materials, such as thermoplastics, thermosets or elastomers.
  • Outsertmaschine such as frames, housings or supports of the thermoplastic molding composition according to the invention, in which functional elements of other compatible or incompatible materials, such as thermoplastics, thermosets or elastomers are injected.
  • thermoplastic molding composition according to the invention combined with other compatible or incompatible materials, such as thermoplastics, thermosets or elastomers
  • connection injection molding spray welding, assembly injection molding, ultrasonic, friction or laser welding, gluing, stock exchange or riveting.
  • thermoplastic molding composition according to the invention may be the substrate itself or the substrate carrier or Hybrid / Bi injection parts a defined Sub strat Suite, which also by subsequent chemical (eg etching) or physical treatment (for example, machining or laser ablation) to the surface can be brought.
  • Injection molding machine screw diameter 30 mm, melt temperature 295 ° C, mold temperature 80 ° C, holding pressure 600 bar, back pressure 50 bar, injection time 2.15 s, holding pressure 20 s, cooling time 18 s, cycle time 60 s, screw peripheral speed 100 rpm, injection volume flow 16 cm 3 / s.
  • the fiber length was analyzed, unless explicitly stated otherwise, visually after ashing of the material under investigation in a microscope (QX Fiber, Leica).
  • Thermoplastic molding compounds made of glass fiber reinforced polyamide 66 were investigated.
  • the mixture of short and long glass fiber reinforced polyamide 66 was produced by producing a granulate mixture directly before injection molding.
  • G1 long glass fiber reinforced granules, average fiber length 1 1, 20 mm, glass fiber content 50% by weight, available for example as Ultramid® A3WG10 LF sw564 (BASF SE)
  • G2 Short glass fiber reinforced granules, average fiber length 0.21 mm, glass fiber content 50% by weight, available for example as Ultramid®A3WG10 sw564 (BASF SE)
  • the weld line strength of the 50/50 blend of G1 and G2 with a value of 88 MPa is thus significantly higher than the expected value of 83 MPa due to a linear blend rule.
  • Charpy impact tests (in the unnotched state) were carried out.
  • the Charpy impact tests were carried out according to ISO 179-2 / 1 eU: 1997.
  • tests for weld line toughness using Charpy were performed on both sides of molded tensile bars.
  • the corresponding Charpy test specimen was sawed out of the center piece of the double-sided molded tie rod.
  • Table 4 Impact strength a cu according to Charpy in the unnotched state
  • the long glass fiber product G1 showed after 10 cycles salt storage a significant decrease in the yield stress and the elongation at break.
  • the short glass fiber product G2 and the 50:50 blend of G1 and G2 had significantly lower losses in yield stress and elongation at break. It could therefore be shown that the stability can be increased by the admixture of G2 to G1. 3.
  • Thermoplastic molding compounds made of glass fiber reinforced polyamide 66 were investigated. A mixture of long glass fiber granules G1 and long short fiberglass granules G2A was used. Components used:
  • G1 long glass fiber reinforced granules (pellet length 12 mm), 50% by weight glass fiber, available for example as Ultramid®A3WG10 LF sw564 (BASF SE)
  • G2A Short glass fiber reinforced granules (granule length 7 mm), 50% by weight glass fiber, available for example as Ultramid® A27 (BASF SE)
  • the tensile strength at the weld line bar was significantly higher than that of the pure long fiber product G1.
  • Thermoplastic molding compounds of glass fiber reinforced polyamide 66 were investigated. Long glass fiber granules G1 containing short glass fibers were used. For comparison, both pure long glass fiber granules and pure short glass fiber granules were investigated.
  • M1 Long glass fiber-reinforced granules (granule length 12 mm), 55% by weight glass fiber, produced from Ultramid® A24 (BASF SE) with long glass fiber
  • M2 Short glass fiber reinforced granules, 55% by weight glass fiber, made of Ultramid® A24
  • M3A long glass fiber reinforced granules containing short glass fibers, 30% by weight long glass fiber, 25% by weight short glass fiber dosed as chopped glass fiber
  • M3B Long glass fiber reinforced granules containing short glass fibers, 30% by weight long glass fiber, 25% by weight short glass fiber in the form of granules of a short glass fiber reinforced material (for example available as Ultramid® A3WG10, BASF SE)
  • Table 8 Fiber length analysis and content measured on the tensile bar
  • M3A is characterized by very high tensile strength combined with high elongation at break, high rigidity and high impact strength (combining the best properties of M1 and M2).
  • the Bindenahtfestmaschine is at the level of M2 and thus corresponds to the expectation from the experiments of Example A) 1., Table 3.
  • Thermoplastic molding compounds made of glass fiber reinforced polyamide 6 were investigated. A mixture of long glass fiber granules G1 and short glass fiber granules G2 was used. Components used:
  • G1 long glass fiber reinforced granules, 50% by weight glass fiber, available for example as
  • G2 Short glass fiber reinforced granules, 50% by weight glass fiber, available for example as
  • Ultramid® B3WG10 black 564 (BASF SE) Table 12: Fiber length analysis (QX Fiber, Leica company)
  • the tensile strength of the suture bar is already increased by admixing 20% of the short fiber granulate G2.
  • the tensile strength of the Bindenahtstabs the 50/50 mixture of G1 and G2 is with 86.7 MPa, surprisingly well above the expected by linear mixing rule value of 83.5 MPa. Also, the breaking elongation of the tie rod was improved by the mixture of G1 and G2 versus pure G1.
  • thermoplastic molding compounds made of glass fiber reinforced polypropylene.
  • G1 long glass fiber reinforced granules (fiber length 10.0 mm), 30% by weight glass fiber, for example obtainable as polypropylene Nepol TM GB303HP-8229 (Borealis AG)
  • G2 Short glass fiber reinforced granules, 30% by weight glass fiber, available for example as polypropylene GB366WG (Borealis AG)
  • the tensile strength of the Bindenahtstabs is increased by admixture of 50 wt .-% of the short fiber granules G2 almost to the level of pure short fiber granules G2.
  • the tensile strength of the 50/50 mixture of G1 and G2 measured on the standard tensile bar according to ISO 527-2, with a value of more than 99.56 MPa, is surprisingly higher than the value of 94.4 MPa expected according to the linear mixing rule.

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Abstract

L'invention concerne un procédé pour la préparation d'une matière de moulage thermoplastique comprenant les étapes suivantes : faire fondre un premier granulat, contenant au moins un polymère thermoplastique A1 et au moins une substance de renforcement B2 fibreuse présentant une longueur moyenne de fibre de l'ordre de 4,5 à 13,0 mm; ajouter et mélanger au moins une substance de renforcement B1 fibreuse présentant une longueur moyenne de fibre de l'ordre de 0,15 à 4,2 mm ou un deuxième granulat contenant au moins un polymère thermoplastique A2 et au moins une substance de renforcement B1 fibreuse présentant une longueur moyenne de fibre de l'ordre de 0,15 à 1,2 mm; ou faire fondre un mélange comprenant un premier granulat contenant au moins un polymère thermoplastique A1 et au moins une substance de renforcement B2 fibreuse présentant une longueur moyenne de fibre de l'ordre de 4,5 à 13,0 mm et un deuxième granulat contenant au moins un polymère thermoplastique A2 et au moins une substance de renforcement B1 fibreuse présentant une longueur moyenne de fibre de l'ordre de 0,15 à 1,2 mm.
PCT/EP2014/067433 2013-08-15 2014-08-14 Matière de moulage thermoplastique renforcée par fibres, à résistance renforcée des lignes de soudure WO2015022404A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10661482B2 (en) 2015-02-23 2020-05-26 Volkswagen Ag Method for producing fiber-reinforced components or semi-finished products
WO2022127857A1 (fr) * 2020-12-18 2022-06-23 金发科技股份有限公司 Matériau de polypropylène renforcé, son procédé de préparation et son utilisation

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3014000A1 (de) * 1979-04-16 1980-10-23 Dart Ind Inc Faserverstaerktes, thermoplastisches harzpraeparat
DE4408089A1 (de) * 1994-03-10 1995-09-14 Hoechst Ag Verfahren zur Wiederaufarbeitung eines faserverstärkten Thermoplast-Materials
WO2000040650A1 (fr) * 1999-01-08 2000-07-13 Lear Automotive Dearborn, Inc. Polyurethanne renforce par des fibres
WO2010054933A1 (fr) * 2008-11-11 2010-05-20 Basf Se Polyamide stabilisé

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3014000A1 (de) * 1979-04-16 1980-10-23 Dart Ind Inc Faserverstaerktes, thermoplastisches harzpraeparat
DE4408089A1 (de) * 1994-03-10 1995-09-14 Hoechst Ag Verfahren zur Wiederaufarbeitung eines faserverstärkten Thermoplast-Materials
WO2000040650A1 (fr) * 1999-01-08 2000-07-13 Lear Automotive Dearborn, Inc. Polyurethanne renforce par des fibres
WO2010054933A1 (fr) * 2008-11-11 2010-05-20 Basf Se Polyamide stabilisé

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
FISA, B.; RAHMANI, M.: "Weldline strength in injection molded glass fiber-reinforced polypropylene", POLYMER, ENGINEERING & SCIENCE, vol. 31, no. 18, September 1991 (1991-09-01), pages 1330 - 1336, XP002715822, DOI: 10.1002/pen.760311807 *
MEDDAD, A.; FISA, B.: "Weldline strength in glassfiber reinforced polyamide 66", POLYMER ENGINEERING & SCIENCE, vol. 35, no. 11, June 1995 (1995-06-01), pages 893 - 901, XP002715821, DOI: 10.1002/pen.760351103 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10661482B2 (en) 2015-02-23 2020-05-26 Volkswagen Ag Method for producing fiber-reinforced components or semi-finished products
WO2022127857A1 (fr) * 2020-12-18 2022-06-23 金发科技股份有限公司 Matériau de polypropylène renforcé, son procédé de préparation et son utilisation

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