WO1999050351A1 - Corps moules en polyoxymethylene - Google Patents

Corps moules en polyoxymethylene Download PDF

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Publication number
WO1999050351A1
WO1999050351A1 PCT/EP1999/002004 EP9902004W WO9950351A1 WO 1999050351 A1 WO1999050351 A1 WO 1999050351A1 EP 9902004 W EP9902004 W EP 9902004W WO 9950351 A1 WO9950351 A1 WO 9950351A1
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Prior art keywords
weight
component
shaped body
polyoxymethylene
monomers
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PCT/EP1999/002004
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German (de)
English (en)
Inventor
Christoph Plachetta
Peter Rieger
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Basf Aktiengesellschaft
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Priority to EP99916888A priority Critical patent/EP1080151A1/fr
Publication of WO1999050351A1 publication Critical patent/WO1999050351A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
    • C08L59/02—Polyacetals containing polyoxymethylene sequences only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
    • C08L59/04—Copolyoxymethylenes

Definitions

  • the invention relates to moldings obtainable by multi-component injection molding or multi-component extrusion processes, characterized in that part of the molding consists of a conductive polyoxymethylene composition A) and the other part consists of a non-conductive polyoxymethylene composition B).
  • Polyoxymethylene molding compositions containing carbon black include known from DE-A 196 380 36, EP-A 327 384, DE-A 40 07 766, EP-A 247 765 and EP-A 327 384.
  • Ultraform ® N2520 L registered trademark of Ultraform GmbH
  • Hostaform ® C 9021 ELS registered trademark of Hoechst AG
  • molded parts are, for example, general treatises such as H.J. Mair, electrically conductive plastics, Hanser Verlag 1989, pp. 1 to 18 or R.G. Gilg, carbon black for conductive plastics, Kunststoff Chain 22, p. 262 (1977) and 22, p. 312 (1977; S. Roth, HJ Mair, electrically conductive plastics, GAK, year 48 (volume 9), pp. 634-639 (1995).
  • general treatises such as H.J. Mair, electrically conductive plastics, Hanser Verlag 1989, pp. 1 to 18 or R.G. Gilg, carbon black for conductive plastics, Kunststoff Chain 22, p. 262 (1977) and 22, p. 312 (1977; S. Roth, HJ Mair, electrically conductive plastics, GAK, year 48 (volume 9), pp. 634-639 (1995).
  • thermoplastic polyurethane TPU
  • TPU thermoplastic polyurethane
  • the object of the present invention was to provide moldings made of partially conductive polyoxymethylenes which have a requirement profile which can be varied for the respective application.
  • the mechanics and chemical resistance, in particular to fuel, are to be improved, with the conductivity at least being maintained.
  • the chemical resistance is improved and the specific surface resistance is significantly reduced, i.e. the surface conductivity is significantly improved.
  • the composition A) according to the invention contains molding compositions 70 to 99, preferably 75 to 97% by weight and in particular 75 to 94% by weight of a polyoxymethylene homo- or copolymer.
  • these polymers have at least 50 mol% of recurring units -CH 2 O- in the main polymer chain.
  • the homopolymers are generally prepared by polymerizing formaldehyde or trioxane, preferably in the presence of suitable catalysts.
  • polyoxymethylene copolymers Kom ⁇ component A in particular those which in addition to the repeating units -CH2O-, up to 50, preferably 0.1 to 20 and in particular from 0.3 to 10 mol% of recurring units 3
  • R 1 to R 4 independently of one another are a hydrogen tom, a C 1 -C 4 -alkyl group or a halogen-substituted alkyl group with 1 to 4 C atoms and R 5 is a -CH 2 -, -CH 2 0-, a Ci-bis
  • n has a value in the range from 0 to 3.
  • groups can advantageously be introduced into the copolymers by ring opening of cyclic ethers.
  • Preferred cyclic ethers are those of the formula
  • R 1 to R 5 and n have the meaning given above.
  • ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 1,3-butylene oxide, 1,3-dioxane, 1,3-dioxolane and 1,3-dioxepane may be mentioned as cyclic ethers and linear oligo- or polyformals such as polydioxolane or polydioxepane as comonomers.
  • component AI oxymethylene terpolymers which, for example, by reacting trioxane, one of the cyclic ethers described above with a third monomer, preferably bifunctional compounds of the formula
  • Preferred monomers of this type are ethylene diglycide, diglycidyl ether and diether from glycidylene and formaldehyde, dioxane or trioxane in a molar ratio of 2: 1, and diether from 2 mol of glycidyl compound and 1 mol of an aliphatic diol with 2 to 8 C-atoms such as for example the diglycidyl ethers of ethylene glycol, 1,4-butanediol, 1,3-butanediol, cyclobutane-1,3-diol, 1,2-propanediol and cyclohexane-1,4-diol, to name just a few examples.
  • the preferred polyoxymethylene copolymers have melting points of at least 150 ° C. and molecular weights (weight average) M w in the range from 5000 to 200000, preferably from 7000 to 150,000.
  • End group-stabilized polyoxymethylene polymers which have C-C bonds at the chain ends are particularly preferred.
  • Products which contain a relatively high proportion (generally> 0.1% by weight) of thermally unstable proportions can in particular also be used as component AI).
  • compositions A) according to the invention contain 1 to 15, preferably 2 to 10 and in particular 5 to 8% by weight of carbon black with a pore volume (DBP dibutyl phthalate adsorption) according to DIN 53 601 of at least 350 ml / g 100 g, preferably at least 370 ml / 100 g.
  • DBP dibutyl phthalate adsorption a pore volume according to DIN 53 601 of at least 350 ml / g 100 g, preferably at least 370 ml / 100 g.
  • the DBP adsorption rate is generally determined in accordance with DIN 53 601 or ASTM-D 2414 and represents a measure of the structure of the respective carbon black. Structure is the chaining of primary carbon black particles to form aggregates. To determine this parameter, 10 g of carbon black, which is placed in a kneader with measurable power transmission (plastograph), is added dropwise until dibutyl phthalate is added until the maximum torque (network point of the carbon black) is exceeded.
  • Component A2) preferably has a specific surface area according to BET (according to DIN 60 132 or ASTM D 3037) of at least 900, preferably 950 m 2 / g and an iodine adsorption of (according to DIN 53 582 or ASTM-D 1510) of at least 950, preferably 1000 and in particular 1050 mg / g. 5
  • the average primary particle size is usually 10 to 50, preferably 25 to 35 nm.
  • Such types of carbon black are, for example, under the trade name Printex ® XE2 (Degussa AG) or Ketjen Black EC DJ 600 (Akzo) available.
  • the molding compositions which can be used according to the invention contain 0 to 2, preferably 10 ppm to 1.5 and in particular 0.001 to 1% by weight, based on the total weight of components AI) to A4), of an alkali and / or alkaline earth compound.
  • alkaline earth and / or alkali metal cations can be used, with lithium, sodium, potassium and calcium cations being preferred.
  • alkali and / or alkaline earth compounds are to be understood as meaning those inorganic or organic salts which have an alkaline reaction in aqueous solution or suspensions.
  • inorganic salts are carbonates, hydrogen carbonates, hydroxides, oxides or phosphates, alkali carbonates such as potassium carbonate and sodium carbonate being particularly preferred.
  • Organic salts are, for example, alcoholates from C 2 to C 12 alcohols, phenolates or salts of carboxylic acids with 2 to 12 C atoms, citrates, oxalates or tartrates being particularly preferred.
  • Alkali metal hydroxides in particular potassium hydroxide and sodium hydroxide, which are preferably added in the form of an aqueous 10 to 70% strength solution, preferably 40 to 60% strength in the preparation of the POM molding compositions, are particularly preferred, it being possible to dose them together with the carbon black.
  • compositions A) according to the invention contain 0 to 15, preferably up to 10 and in particular up to 9% by weight of further additives.
  • the polyamides that can be used as components A4) are known per se. Semicrystalline or amorphous resins, as described, for example, in the Encyclopedia of Polymer Science and Engineering, Vol. 11, pp. 315 to 489, John Wiley & Sons, Inc. 1988, can be used, the melting point of the polyamide preferably being below 225 ° C, preferably below 215 ° C. 6
  • Examples include polyhexamethylene azelaic acid amide, poly hexamethylene sebacic acid amide, polyhexamethylene dodecanedioic acid amide, poly-11-aminoundecanoic acid amide and bis (p-aminocyclohexyl) methane dodecanoic acid diamide or those obtained by ring opening of lactams, e.g. or products obtained from polylaurine lactam.
  • Polyamides based on terephthalic or isophthalic acid as the acid component and / or trimethylhexamethylene diamine or bis (p-aminocyclohexyl) propane as the diamine component and polyamide base resins which have been prepared by copolymerizing two or more of the abovementioned polymers or their components are also suitable.
  • the preparation of these polyamides is also described in the aforementioned document.
  • the ratio of terminal amino groups to terminal acid groups can be controlled by varying the molar ratio of the starting compounds.
  • the proportion of the polyamide in the molding composition according to the invention is 0 to 2, preferably 0.005 to 1.8% by weight, preferably 0.04 to 1.6% by weight.
  • the molding compositions can contain a melamine-formaldehyde condensate as nucleating agent A4).
  • Suitable products are e.g. described in DE-A 25 40 207.
  • Suitable sterically hindered phenols are in principle all compounds with a phenolic structure which have at least one sterically demanding group on the phenolic ring.
  • compounds of the formula are preferably used
  • R 1 and R 2 are an alkyl group, a substituted alkyl group or a substituted triazole group, where the radicals R 1 and R 2 may be the same or different and
  • R 3 is an alkyl group, a substituted alkyl group, an alkoxy group or a substituted amino group.
  • Antioxidants of the type mentioned are described, for example, in DE-A 27 02 661 (US-A 4 360 617).
  • Another group of preferred sterically hindered phenols is derived from substituted benzene carboxylic acids, in particular from substituted benzene propionic acids.
  • Particularly preferred compounds from this class are compounds of the formula
  • R 4 , R 5 , R 7 and R 8 independently of one another C 1 -C 8 alkyl groups, which in turn can be substituted (at least one of them is a sterically demanding group) and R 6 is a divalent aliphatic radical having 1 to 10 C atoms , which can also have C-0 bonds in the main chain.
  • R 4 , R 5 , R 7 and R 8 independently of one another C 1 -C 8 alkyl groups, which in turn can be substituted (at least one of them is a sterically demanding group) and R 6 is a divalent aliphatic radical having 1 to 10 C atoms , which can also have C-0 bonds in the main chain.
  • Examples include sterically hindered phenols:
  • the antioxidants which can be used individually or as mixtures, can be used in an amount of 0.05 to 2% by weight, preferably 0.1 to 1.0% by weight.
  • sterically hindered phenols with no more than one sterically hindered group ortho to phenolic hydroxyl groups have proven to be particularly advantageous; especially when assessing the color stability of storage in diffuse light over long periods of time.
  • the dispersibility of the polyamides used can be improved by using a polycondensation product consisting of 2,2-di (4-hydroxyphenyl) propane (bisphenol A) and epichlorohydrin.
  • Such condensation products of epichlorohydrin and bisphenol A are commercially available. Methods for their preparation are also known to the person skilled in the art. Commercial names of the polycondensates are Phenoxy ® (from Union Carbide Corporation) and Epikote ® (from Shell). The molecular weight 10 of the polycondensates can vary within wide limits; in principle, the types available on the market are all suitable.
  • Component A4) can also contain 0.002 to 2.0% by weight, preferably 0.005 to 0.5% by weight and in particular 0.01 to 0.3% by weight, of one or more alkaline earth metal silicates and / or alkaline earth metal glycerophosphates be included.
  • Calcium and in particular magnesium have proven to be excellent as alkaline earth metals for the formation of the silicates and glycerophosphates.
  • Me an alkaline earth metal preferably calcium or especially magnesium
  • x is a number from 1.4 to 10, preferably 1.4 to 6 and
  • n is a number equal to or greater than 0, preferably 0 to 8.
  • Compositions A) according to the invention may also contain further additives.
  • Additives for trapping formaldehyde (formaldehyde scavenger), plasticizers, lubricants, adhesion promoters and light stabilizers are only mentioned here as examples.
  • the proportion of such additives is generally in the range from 0.001 to 5% by weight.
  • Composition B) according to the invention is composed of
  • Bl 20 to 100, preferably 20 to 80 and in particular
  • B2) 0 to 80% by weight, preferably 0 to 50 and in particular 0 to 40% by weight of further additives, 11 where the sum of the percentages by weight of components B1) and B2) each gives 100%.
  • component B2 all compounds which are already listed above under component A4) come into consideration as component B2).
  • the composition B can be varied such that a property profile required for the particular application is achieved.
  • 50% by weight preferably 1 to 40% by weight, may be mentioned, for example, potassium titanate whiskers, carbon and preferably glass fibers, the glass fibers being e.g. in the form of glass fabrics, mats, nonwovens and / or glass silk rovings or cut glass silk made from low-alkali E-glass with a diameter of 5 to 200 ⁇ m, preferably 8 to 50 ⁇ m, the fibrous fillers preferably being a medium one after being incorporated Have a length of 0.05 to 1 ⁇ m, in particular 0.1 to 0.5 ⁇ m.
  • suitable fillers are, for example, wollastonite, calcium carbonate, glass balls, quartz powder, silicon and boron nitride or mixtures of these fillers.
  • Preferred combinations of fillers are: wollastonite with glass fibers, with mixing ratios of 5: 1 to 1: 5 being preferred.
  • additives are, in amounts of up to 50, preferably 0 to 40,% by weight, impact-modifying polymers (also referred to below as rubber-elastic polymers or elastomers).
  • EPM ethylene-propylene
  • EPDM ethylene-propylene-diene
  • EPM rubbers generally have practically no more double bonds, whereas EPDM rubbers can have 1 to 20 double bonds / 100 carbon atoms.
  • diene monomers for EPDM rubbers are conjugated dienes such as isoprene and butadiene, non-conjugated dienes having 5 to 25 carbon atoms such as penta-1, 4-diene, hexa-1, 4-diene, hexa-1 , 5-diene, 2, 5-dimethylhexa-l, 5-diene and octa-l, 4-diene, 12 cyclic dienes such as cyclopentadiene, cyclohexadienes, cycloocadienes and dicyclopentadiene and alkenylnorbornenes such as 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methallyl-5-norbornene, 2-isopropenyl-5- norbornene and tricyclodienes such as 3-methyl-tricyclo (5.2.1.0.2.6) -3, 8-decadiene or mixtures thereof.
  • conjugated dienes such as iso
  • Hexa-1,5-diene-5-ethylidene-norbornene and dicyclopentadiene are preferred.
  • the diene content of the EPDM rubbers is preferably 0.5 to 50, in particular 1 to 8,% by weight, based on the total weight of the rubber.
  • the EPDM rubbers can also be grafted with other monomers, e.g. with glycidyl (meth) acrylates, (meth) acrylic acid esters and (meth) acrylamides.
  • Another group of preferred rubbers are copolymers of ethylene with esters of (meth) acrylic acid.
  • the rubbers can also contain monomers containing epoxy groups. These monomers containing epoxy groups are preferably incorporated into the rubber by adding monomers of general formulas I or II containing epoxy groups to the monomer mixture
  • R 6 - R 10 represent hydrogen or alkyl groups with 1 to 6 carbon atoms and m is an integer from 0 to 20, g is an integer from 0 to 10 and p is an integer from 0 to 5.
  • the radicals R 6 to R 8 are preferably hydrogen, where m is 0 or 1 and g is 1.
  • the corresponding compounds are allyl glycidyl ether and vinyl glycidyl ether.
  • Preferred compounds of the formula II are epoxy group-containing esters of acrylic acid and / or methacrylic acid, such as glycidyl acrylate and glycidyl methacrylate.
  • the copolymers advantageously consist of 50 to 98% by weight of ethylene, 0 to 20% by weight of monomers containing epoxy groups and the remaining amount of (meth) acrylic acid esters. 13
  • Copolymers of are particularly preferred
  • n-butyl acrylate 1 to 50, in particular 10 to 40% by weight of n-butyl acrylate and / or 2-ethylhexyl acrylate.
  • esters of acrylic and / or methacrylic acid are the methyl, ethyl, propyl and i- or t-butyl esters.
  • vinyl esters and vinyl ethers can also be used as comonomers.
  • the ethylene copolymers described above may be prepared by processes known per se, preferably by random copolymerization temperature under high pressure and elevated ⁇ Tem. Appropriate methods are generally known.
  • Preferred elastomers are also emulsion polymers, the production of which e.g. is described in Blackley in the monograph "Emulsion Polymerization".
  • the emulsifiers and catalysts that can be used are known per se.
  • homogeneous elastomers or those with a shell structure can be used.
  • the shell-like structure is determined by the order of addition of the individual monomers;
  • the morphology of the polymers is also influenced by this order of addition.
  • acrylates such as n-Butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene and mixtures thereof.
  • monomers for the production of the rubber part of the elastomers acrylates such as n-Butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene and mixtures thereof.
  • monomers can be combined with other monomers such as e.g. Styrene, acrylonitrile, vinyl ethers and other acrylates or methacrylates such as methyl methacrylate, methyl acrylate, ethyl acrylate and propyl acrylate can be copolymerized.
  • the soft or rubber phase (with a glass transition temperature below 0 ° C) of the elastomers can the core, the outer shell or a middle shell (in the case of elastomers with more than two 14 shell structure); in the case of multi-layer elastomers, several shells can also consist of a rubber phase.
  • one or more hard components are involved in the construction of the elastomer, these are generally obtained by polymerizing styrene, acrylonitrile, methacrylonitrile, - ⁇ -methylstyrene, p-methylstyrene, Acrylic acid esters and methacrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate are produced as the main monomers. In addition, smaller proportions of further comonomers can also be used here.
  • emulsion polymers which have reactive groups on the surface.
  • groups are e.g. Epoxy, amino or amide groups as well as functional groups by using monomers of the general formula
  • R 15 is hydrogen or a C 1 -C 4 -alkyl group
  • R 16 is hydrogen, a C 1 -C 4 -alkyl group or an aryl group, in particular phenyl,
  • R 17 is hydrogen, a -C ⁇ to Cio-alkyl, a C ⁇ to C ⁇ aryl group or -ORis
  • R 18 is a -C ⁇ to Cs-alkyl or C 6 - to -C 2 -aryl group, which can optionally be substituted with 0- or N-containing groups,
  • X is a chemical bond, a C ⁇ to Cio alkylene or C 6 -C 2 arylene group or 15
  • the graft monomers described in EP-A 208 187 are also suitable for introducing reactive groups on the surface.
  • acrylamide, methacrylamide and substituted esters of acrylic acid or methacrylic acid such as (Nt-butylamino) ethyl methacrylate, (N, N-dimethylamino) ethyl acrylate, (N, N-dimethylamino) methyl acrylate and (N, N-diethyl) * called amino) ethyl acrylate.
  • the particles of the rubber phase can also be crosslinked.
  • Monomers acting as crosslinking agents are, for example, buta-1,3-diene, divinylbenzene, diallyl phthalate and dihydrodicyclopentadienyl acrylate, and the compounds described in EP-A 50 265.
  • So-called graft-linking monomers can also be used, i.e. Monomers with two or more polymerizable double bonds, which react at different rates during the polymerization.
  • Compounds are preferably used in which at least one reactive group polymerizes at approximately the same rate as the other monomers, while the other reactive group (or reactive groups) e.g. polymerizes much slower (polymerize).
  • the different polymerization speeds result in a certain proportion of unsaturated double bonds in the rubber. If a further phase is subsequently grafted onto such a rubber, the double bonds present in the rubber react at least partially with the graft monomers to form chemical bonds, i.e. the grafted phase is at least partially linked to the graft base via chemical bonds.
  • graft linking monomers are allyl-containing monomers, in particular allyl esters of ethylenically unsaturated carboxylic acids such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate and the entspre ⁇ sponding monoallyl compounds of these dicarboxylic acids.
  • allyl-containing monomers in particular allyl esters of ethylenically unsaturated carboxylic acids such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate and the entspre ⁇ sponding monoallyl compounds of these dicarboxylic acids.
  • graft linking monomers are also a large number of other suitable graft-crosslinking monomers; for further details, reference is made here, for example, to US Pat. No. 4,148,846.
  • the proportion of these crosslinking monomers in component D) is up to 5% by weight, preferably not more than 3% by weight, based on D).
  • graft polymers with a core and at least one outer shell have the following structure:
  • Buta-1, 3-diene, isoprene and n-butyl acrylate or their copolymers can be used. These products can also be prepared by using crosslinking monomers or monomers with reactive groups.
  • Thermoplastic polyurethanes such as are described, for example, in EP-A 115 846 may be mentioned as further suitable elastomers.
  • compositions B) can contain inorganic and organic colorants, which are usually present in an amount of 0.01 to 10% by weight.
  • thermoplastic compositions A) and B) according to the invention are produced by mixing the components in a manner known per se, which is why detailed information is unnecessary here.
  • the components are advantageously mixed in an extruder.
  • the granules of the compositions A) and B) are then processed by means of multi-component injection molding or multi-component extrusion processes to give the moldings according to the invention. Suitable methods are known to the person skilled in the art and, for example, in 17 of DE-A 40 41 799, DE-A 40 32 499, DE-A 42 24 171 and DE-A 43 30 451.
  • the molded body can consist of layers of A) and B) arranged one above the other as well as a core of A) or B) which is overmolded with A) or B).
  • compositions A) and B are obtainable on the basis of the processes described in EP-A 393 409.
  • composition A For some applications (e.g. hoses) it may be necessary to change from e.g. To design a hose made of rubber-modified composition B) to have composition A) so that the "soft" hose is fluidly connected to a “hard” hose.
  • the moldings according to the invention are notable for good chemical resistance and improved surface conductivity. They are therefore suitable for applications as
  • heated components in the automotive sector headlight and windshield washer nozzles, heated exterior mirrors or door handles and door locks, heated diesel filters
  • Components in the automotive fuel sector where static electricity has to be discharged parts from the filler neck, the petrol pump, installation parts in the tank, etc.
  • Printing rollers laser printers, copiers, offset printers.
  • composition A The following components were used for composition A).
  • Carbon black with a specific surface according to BET (according to DIN 66 132 of 950 m 2 / g, DBP adsorption according to DIN 53 601 of 380 mg / g, and an iodine adsorption according to DIN 53 582 of 1075 mg / g.
  • Component A4a corresponded to component B2a
  • component A4b corresponded to component B2b
  • component A4c corresponded to component B2c
  • component A4d corresponded to component B2d
  • compositions B The following components were introduced ⁇ sets:
  • B2a polyamide with a molecular weight of 3000, made from 37% by weight ⁇ -caprolactam, 63% by weight of an equimolar mixture of adipic acid and hexamethylenediamine, using propionic acid as a regulator.
  • Irganox ® 245 (Ciba -Geigy AG):
  • Si0 content > 59% by weight
  • B2d melamine-formaldehyde condensate according to Example 1 of DE-A 25 40 207.
  • Blb Polyoxymethylene copolymer from approx. 97% by weight trioxane and approx. 3% by weight butanediol formal. The product contained about 5 percent still -.% Of unconverted trioxane and 5 wt -.% Thermally stable in ⁇ shares. After the thermally unstable portions had broken down, the copolymer had a melt index of 11 ml / 10 min at 190 ° C. and 2.16 N, in accordance with ISO 1133.
  • thermoplastic polyurethane prepared by imple ⁇ wetting of 4, 4 'diphenylmethane diisocyanate, 1, 4-butanediol-adipate and poly- 1, 4-butanediol having a Shore A hardness of 85th
  • the copolymer had a melt index of 7.5 ml / 10 min at 190 ° C. and 2.16 N, in accordance with ISO 1133.
  • B2f glass fibers with an average diameter of 10 ⁇ m.
  • the components AI to A3 and the respective components B1 and B2 were introduced in a twin-screw extruder with a degassing device and melted at 230 ° C., degassed in a homogenized manner and pressed out as a strand, cooled and granulated.
  • Plates with the dimensions 110 x 110 x 4 mm were sprayed on a 2-component injection molding machine (Klöckner Feromatik FM 160 machine with monosandwich device).
  • the plate consisted of components AI) to A3).
  • the layer thicknesses obtained were determined by measuring after the panels had been sawn open in the middle (mean values from several measurements or from the two outer layers of one panel each).

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Abstract

L'invention concerne des corps moulés obtenus par moulage par injection de plusieurs composants ou par extrusion de plusieurs composants. L'invention se caractérise en ce qu'une partie du corps moulé se compose d'une composition conductrice de polyoxyméthylène A) et que l'autre partie se compose d'une composition non conductrice de polyoxyméthylène B).
PCT/EP1999/002004 1998-03-31 1999-03-24 Corps moules en polyoxymethylene WO1999050351A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP99916888A EP1080151A1 (fr) 1998-03-31 1999-03-24 Corps moules en polyoxymethylene

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1998114263 DE19814263A1 (de) 1998-03-31 1998-03-31 Formkörper aus Polyoxymethylenen
DE19814263.3 1998-03-31

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WO1999050351A1 true WO1999050351A1 (fr) 1999-10-07

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004058860A1 (fr) * 2002-12-20 2004-07-15 E.I. Du Pont De Nemours And Company Concentres d'amelioration de caracteristiques d'adhesion superficielle de compositions a base de polyacetal

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WO2005007384A1 (fr) * 2003-07-03 2005-01-27 Ticona, Llc Procede de fabrication d'articles coextrudes en polyacetal avec profil façonne et couche elastomere thermoplastique liee par voie fondue, et article ainsi obtenu

Citations (5)

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EP0181587A2 (fr) * 1984-11-07 1986-05-21 Zipperling Kessler & Co (GmbH & Co) Mélanges polymères thermoplastiques antistatiques ou électriquement semi-conducteurs, procédé pour leur fabrication et leur mise en oeuvre
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