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EP1539881A2 - Corps moules contenant des polyacetales et procedes de fabrication de ces corps moules - Google Patents

Corps moules contenant des polyacetales et procedes de fabrication de ces corps moules

Info

Publication number
EP1539881A2
EP1539881A2 EP03794995A EP03794995A EP1539881A2 EP 1539881 A2 EP1539881 A2 EP 1539881A2 EP 03794995 A EP03794995 A EP 03794995A EP 03794995 A EP03794995 A EP 03794995A EP 1539881 A2 EP1539881 A2 EP 1539881A2
Authority
EP
European Patent Office
Prior art keywords
shaped body
body according
polyacetal
melt
wall thickness
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Withdrawn
Application number
EP03794995A
Other languages
German (de)
English (en)
Inventor
Bernhard Pfeiffer
Rainer Bernstein
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ticona GmbH
Original Assignee
Ticona GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Ticona GmbH filed Critical Ticona GmbH
Publication of EP1539881A2 publication Critical patent/EP1539881A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
    • 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
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2359/00—Characterised by the use of polyacetals containing polyoxymethylene sequences only
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]

Definitions

  • the present invention relates to molded articles containing polyacetal with wall thickness differences which have particularly outstanding mechanical and chemical properties.
  • the present invention furthermore relates to processes for producing these polyacetal moldings.
  • Moldings made from polyacetals have been known for a long time, and these moldings already have a good property profile.
  • some applications require moldings that have a particularly high mechanical stability.
  • the mechanical properties are improved by adding additives.
  • this option is expensive, and in particular the recyclability of the plastics is impaired.
  • the wall thickness of the moldings can be increased.
  • this possibility is material-intensive and therefore complex, the parts also being heavier.
  • attempts are made to save weight by reducing the wall thickness of the moldings. Accordingly, this possibility also has disadvantages.
  • the object of the present invention was therefore to provide moldings containing polyacetal with wall thickness differences which have a particularly high mechanical stability.
  • the moldings of the present invention should be particularly simple and inexpensive to manufacture.
  • the moldings should be recyclable without any particular effort.
  • Claim 1 This provides moldings that have high mechanical stability.
  • the moldings according to the invention in particular based on the low weight, show a high screw-in torque and a high over-torque, each measured with a 2 D screw-in depth and 500 rpm at 23 ° C.
  • the molded articles of the present invention show a particularly low tendency to form stress cracks.
  • the wall thickness of the moldings according to the invention can be in a wide range.
  • the moldings preferably have a wall thickness of up to 100 mm, in particular up to 10 mm and particularly preferably up to 5 mm.
  • the wall thickness of the molded body can also differ.
  • Preferred moldings are distinguished by differences in wall thickness, the difference between the minimum wall thickness and the maximum wall thickness being in particular at least 1 mm, preferably at least 3 mm and particularly preferably at least 5 mm.
  • the ratio of maximum wall thickness to minimum wall thickness is preferably in the range from 1.1 to 100, in particular 2 to 50 and particularly preferably 4 to 20.
  • the mean wall thickness of the shaped body can be calculated by dividing the volume of the mass forming the shaped body, including the microcellular structure, by the area of the shaped body, this area resulting from the entire surface of the shaped body. The entire surface is divided by two to get to the surface.
  • the mean wall thickness of the shaped body is preferably in the range from 0.1 to 100 mm, preferably 0.5 to 10 mm and particularly preferably 1 to 5 mm.
  • An essential component of the shaped bodies according to the invention are polyacetals.
  • polyoxymethylene homopolymers and / or copolymers in the context of the invention this being understood to mean both a homopolymer alone, several homopolymers in a mixture with one another, a copolymer alone, a plurality of copolymers in a mixture with one another and mixtures which are one or more homopolymers have together with one or more copolymers.
  • the polyacetals form the main constituent of the molding compositions which are used to produce the moldings according to the invention.
  • the polyoxymethylenes can be, among others, homopolymers of formaldehyde or trioxane or
  • Copolymers of trioxane They can have a linear structure, but can also be branched or networked. They can be used individually or as a mixture.
  • Homopolymers of formaldehyde or trioxane are understood to mean those polymers whose semiacetal hydroxyl end groups are chemically stabilized against degradation, for example by esterification or etherification.
  • Copolymers of trioxane are understood to mean copolymers of trioxane and at least one compound copolymerizable with trioxane.
  • the homopolymers have i. d. R. thermally stable end groups such as ester or ether groups.
  • the copolymers of formaldehyde or trioxane advantageously have more than 50%, in particular more than 75%, of oxymethylene groups.
  • Copolymers which contain at least 0.1% by weight of groups of the copolymer which have at least two adjacent carbon atoms in the chain have proven particularly useful.
  • Polyoxymethylenes which contain 1 to 10% by weight of comonomers have acquired particular industrial importance.
  • polyoxymethylene copolymers are preferred which, in addition to the repeating units -CH2O-, up to 50, preferably 0.1 to
  • R 1 to R 4 independently of one another are a hydrogen atom, a C - ⁇ - to C4-alkyl group or a halogen-substituted alkyl group with 1 to 4 C-atoms and R 5 is a -CH2-, -CH2O-, a Cj- to C4 -Alkyl- or C-
  • n has a value in the range from 0 to 3.
  • These groups can advantageously be introduced into the copolymers by ring opening of cyclic ethers.
  • Preferred cyclic ethers are those of the formula
  • R is a hydrogen atom, an alkyl radical having 1 to 6, preferably X, 2 or 3 carbon atoms, which can be substituted by 1, 2 or 3 halogen atoms, preferably chlorine atoms, an alkoxymethyl radical having 2 to 6, preferably 2, 3 or 4 carbon atoms, a phenyl radical or a phenoxymethyl radical, x is an integer from 1 to 3, where y is zero, y is an integer from 1 to 3, where x is zero and z is 2, and z is an integer Number from 3 to 6, preferably 3 or 4, where x is zero and y is 1.
  • Particularly suitable cyclic ethers are epoxides, e.g. As ethylene oxide, styrene oxide, propylene oxide or epichlorohydrin, and glycidyl ether of mono- or polyhydric alcohols or phenols.
  • Suitable cyclic acetals are, above all, cyclic formals of aliphatic or cycloaliphatic ⁇ , ⁇ -diols having 2 to 8, preferably 2, 3 or 4, carbon atoms, the carbon chain of which can be interrupted by an oxygen atom at intervals of 2 carbon atoms, e.g. B .:
  • Suitable linear polyacetals are both homo- or copolymers of the cyclic acetals defined above and linear condensates of aliphatic or cycloaliphatic ⁇ , ⁇ -diols with aliphatic aldehydes or thioaldehydes, preferably formaldehyde.
  • homopolymers of cyclic formals of aliphatic ⁇ , ⁇ -diols with 2 to 8, preferably 2, 3 or 4 carbon atoms are used, for.
  • B poly- (1,3-dioxolane), poly- (1,3-dioxane) and poly- (1,3-dioxepane).
  • Hexafluoropropanol which is adjusted to pH 8 to 9 with methanolic sodium hydroxide solution, at 25 ° C. in a concentration of 0.3 g / 100 ml) should generally be at least 160 (ml / g).
  • the crystallite melting points of the polyoxymethylenes are in the range from 140 to 180 ° C., preferably 150 to 170 ° C., their densities amount to 1.38 to 1.45 gx mM, preferably 1.40 to 1.43 gx ml _ 1 (measured according to DIN 53479).
  • the polyoxymethylenes used have a number-average molecular weight M n of 2,000 to 200,000, preferably 10,000 to 100,000, and a volume flow index (melt volume rate, MVR) at 190 ° C. and a contact force of 2.16 kg according to DIN ISO 1133 of 0.5 to 200 cm 3/10 min, preferably from 1 to 70 cm 3/10 min.
  • the preferably binary or ternary trioxane copolymers used according to the invention are prepared in a known manner by polymerizing the monomers in the presence of cationically active catalysts at temperatures between 0 and 150 ° C., preferably between 70 and 140 ° C. (cf. e.g.
  • catalysts used here are Lewis acids, such as boron trifluoride or antimony pentafluoride, and complex compounds of such Lewis acids, preferably etherates, for.
  • Protonic acids e.g. B. perchloric acid, as well as salt-like compounds, for. B.
  • the polymerization can take place in bulk, suspension or solution.
  • the copolymers can be subjected to a thermal or hydrolytically controlled, partial degradation down to primary alcohol end groups (see, for example, DE-AS 1445 273 and 1445 294).
  • the homopolymers of formaldehyde or trioxane used according to the invention are likewise prepared in a known manner by catalytically polymerizing the monomer (cf., for example, DE-AS 10 37 705 and 11 37 215).
  • trioxane compounds with a plurality of polymerizable groups in the molecule, for.
  • B. alkyl glycidyl formals Polyglycol diglycidyl ether, alkanediol diglycidyl ether, e.g. B. 1,4-butanediol diglycidyl ether or bis (alkanetriol) triformaIe can be used.
  • B. Diglycerol diformal compounds with a plurality of polymerizable groups in the molecule.
  • alkyl glycidyl formals Polyglycol diglycidyl ether, alkanediol diglycidyl ether, e.g. B. 1,4-butanediol diglycidyl ether or bis (alkanetriol) triformaIe
  • the polyactals are preferably contained in the molded article in an amount of at least 40% by weight, advantageously at least 70% and in particular at least 95% by weight, based on the weight of the molded article.
  • the molding composition for producing the moldings according to the invention can also contain customary additives and reinforcing materials, such as fibers, in particular glass fibers, carbon fibers, aramid fibers, mineral fibers, processing aids, polymeric lubricants, lubricants with external and / or internal lubrication, ultra-high molecular weight polyethylene (PE-UHMW ), Polytetrafluoroethylene (PTFE) or a graft copolymer which is a product of a graft reaction from an olefin polymer and an acrylonitrile / styrene copolymer, antioxidants, adhesion promoters, waxes, nucleating agents, mold release agents, glass balls, mineral fillers such as chalk, calcium carbonate, Wollastonite, silicon dioxide, talc, mica, montmorillonite, organically modified or unmodified, organically modified or unmodified phyllosilicates, with the liquid-crystalline plastic or the polyarylene sulf
  • a mixture of a lubricant with external lubrication and a lubricant with internal lubrication can be used as the lubricant.
  • the mixing ratio of lubricants with internal lubrication to lubricants with external lubrication can be from 0 to 100 to 100 to 0 parts by weight.
  • Poly- ⁇ -olefin oligomers, silicone oils, polyalkylene glycols and perfluoroalkyl ethers can be used. Soaps and esters, also partially saponified, are both lubricants with external and internal lubrication.
  • a high molecular weight, oxidized and thus polar polyethylene wax is preferably used. It improves the tribological behavior and reduces the mechanical properties less.
  • Stearyl stearate is preferably used as the lubricant with predominantly internal lubrication.
  • Solid and liquid paraffins, stearic acids, non-polar and polar polyethylene waxes, poly- ⁇ -olefin oligomers, silicone oils, polyakylene glycols and perfluoroalkyl ethers are lubricants with external lubrication.
  • Soaps and esters, also partially saponified, are lubricants with both external and internal lubrication.
  • Montanic acid esters and montanic acid esters, partially saponified, are lubricants with external lubrication.
  • the preferred oxidized polyethylene wax is a high molecular weight, polar wax and generally has an acid number of 12 to 20 mg KOH / g and a viscosity of 3000 to 5000 mPa * s at 140 ° C.
  • Lubricants are described in Gumbleter / Müller, "Taschenbuch der Kunststoff-Additive", 3rd edition, Carl Hanser Verlag Kunststoff / Vienna 1994, pages 478-504, to which reference is made.
  • microcellular structure denotes that the shaped body comprises cavities or cells that are a few hundred micrometers in size. These cells are generally distributed uniformly in the mass forming the shaped body, without any intention that this should impose a restriction.
  • the cells generally have a spherical shape, but are not intended to restrict them.
  • the term spherical denotes that the cells preferably have a spherical shape, it being obvious to the person skilled in the art that, due to the pressure conditions in the mold, cells with others are also used during injection molding Shape can be contained in the molded body, or that the shape of the cells can deviate from the ideal spherical shape.
  • the term spherical means that the ratio of the largest dimension of the cells to the smallest dimension is at most 4, preferably at most 2, these dimensions being measured in each case by the center of gravity of the cells. At least 70%, particularly preferably at least 90%, based on the number of cells, is preferably spherical.
  • the size of the cells in the case of spherical cells the diameter, is preferably in the range from 1 to 100 ⁇ m, in particular 3 to 80 ⁇ m and particularly preferably in the range from 5 to 50 ⁇ m.
  • This size represents the mean value determined via the number of cells, which can be determined, inter alia, by scanning electron microscope images.
  • the density of the mass forming the shaped body which comprises the volume of the cells of the microcellular structure, is generally below the density of the shaped mass before the production of the shaped body having a microcellular structure.
  • the density of the shaped body is preferably in the range from 1.0 to 1.6 g / cm 3 , in particular from 1.2 to 1.5 g / cm 3 and particularly preferably from 1.3 to 1.4 g / cm 3 . In general, this density is 2 to 50%, preferably 5 to 30% and particularly preferably 10 to 25% below the density of the molding composition before the molding is produced.
  • This size can be determined by measuring the density of the molded body, then melting the molded body, possibly degassing, and determining the density of the cooled melt. As a result of the melting, the mass forming the shaped body loses the microcellular structure.
  • the flow path length of the shaped body according to the invention is not critical per se and can accordingly be in a wide range.
  • this size is preferably in the range from 1 mm to 250 cm, in particular 2 mm to 200 cm and particularly preferably in the range from 5 mm to 140 cm.
  • This quantity describes the length of the path between the injection point and the point of the molded body furthest away from this injection point.
  • This size can be, for example be determined by direct measurement on the molded body or on the tool, the flow path to be covered by the molding compound within the tool being determined,
  • the flow path of the molding compound is measured within a spiral, which has a diameter that corresponds to the average wall thickness of the molding.
  • the flow path length of the molded body can now be determined by determining the intrinsic viscosity of the molding compound.
  • the intrinsic viscosity denotes the maximum viscosity at which the straight tool is completely filled, the viscosity being measured at the injection point. If the viscosity is higher, the tool is not filled completely, so that imperfections occur.
  • the intrinsic viscosity determined in this way is used to determine the flow path of the molding compound within the spiral. It is important here that the same processing conditions are used to determine the flow path length within the spiral as for the production of the shaped body. For example, the viscosity of the molding compound, the mold and melt temperature, the injection pressure, etc. must be identical.
  • the ratio of flow path length to wall thickness difference is in the range from 0.1 to 1000, preferably 1 to 500 and particularly preferably 3 to 100, without this being intended to impose a restriction.
  • breakthrough describes an area in which the wall thickness of the molded body takes on the value zero. This surface is completely surrounded by molding compound, the third dimension representing the wall thickness.
  • preferred shaped bodies have at least one, in particular at least two and particularly preferably at least ten openings.
  • the openings preferably have an area of at least 1 mm 2 , in particular at least 4 mm 2 and particularly preferably at least 10 mm 2 , this size relating to the sum of the area of all openings.
  • the shaped bodies can have, inter alia, sharp corners, edges, ribs, webs, screw domes, snap hooks and / or film hinges.
  • the moldings of the present invention may also contain metal, for example iron, in particular steel, nickel, tin, zinc, chromium, copper and alloys of these metals. Shaped bodies of this type can be obtained, for example, by metal extrusion coating, inter alia by the so-called outsert technique. These moldings are particularly notable for their high strength and durability, and this relates in particular to the cracking of the plastic, which is particularly low in the moldings according to the invention in comparison with conventional moldings.
  • metal for example iron, in particular steel, nickel, tin, zinc, chromium, copper and alloys of these metals.
  • Shaped bodies of this type can be obtained, for example, by metal extrusion coating, inter alia by the so-called outsert technique.
  • the shaped bodies preferably have an overtorque of at least 7.8 Nm, in particular at least 8.0 Nm.
  • the screw-in torque of preferred shaped bodies is at least 2.5 Nm, in particular at least 2.6 Nm. These sizes can be determined with a 2 D screw-in depth and 500 rpm at 23 ° C.
  • the moldings show a particularly low tendency to form stress cracks.
  • Preferred moldings show no stress cracks within 5 minutes, in particular 10 minutes after 5 minutes of immersion in 50% sulfuric acid at 20 ° C.
  • the moldings according to the invention are produced by injection molding.
  • the melt comprising polyacetal is preferably up to 30% by weight, preferably 10 "8 ⁇ 5% by weight, in particular 10 " 4 to 2% by weight, particularly preferably 0.01 to 1% by weight, based on the total weight of the mixture obtained, a fluid added which is in the supercritical state.
  • the fluid and the polymer melt are optionally sheared and mixed according to generally known methods, for example in an extruder or a kneader, the fluid being dissolved in the polymer melt.
  • the amount of the fluid can be selected such that the solution of the fluid in the polymer melt is up to 60% below the viscosity of the pure polymer melt.
  • These viscosity values can be regulated, among other things, by the amount of the fluid.
  • the mixture is quickly filled into an injection mold.
  • the pressure that is taken over by the gas pressure can be reduced to zero.
  • the injection pressure is generally chosen such that it is up to 45%, advantageously up to 30%, in particular up to 20%, below the injection pressure which is usually necessary when using a polymer melt which comprises polyacetals.
  • Preferred values are in the range from 200 to 2000 bar, in particular 300 to 1000 bar and particularly preferably from 300 to 800 bar, these values being set on the injection molding machine (depending on the component conditions).
  • the closing pressure (closing force) of the mold can be reduced to up to 30%, advantageously up to 25%, in particular up to 10% compared to the known methods when using a pure polyacetal melt and is generally in the range of 500 N (0.05 t / cm 2 ) to 10,000 N (1 t / cm 2 ), advantageously from 1000 N (0.1 t cm 2 ) to 7000 N (0.7 t cm 2 ), in particular from 1200 N (0.12 t / cm 2 ) up to 6100 N (0.61 t / cm 2 ).
  • the melt temperature measured at the outlet of the spray nozzle, can be in a wide range and is dependent on the proportion of fluid, the molar mass of the polyacetals and additives, for example fillers.
  • the melt temperature is in the range of 150 to 250 C C, preferably 160 to 230 ° C and particularly preferably in the range of 175 ° C to 210 ° C, without intended that in this way constitute a limitation.
  • the tool temperature can also be in a wide range. Without being restricted thereby, the tool temperature is in the range from 20 ° C. to 160 ° C., in particular 40 ° C. to 140 ° C. and particularly preferably 60 ° C. and 120 ° C.
  • all suitable fluids can be used as the fluid.
  • the term fluid is intended to clarify that the gas or liquid is in the supercritical state. Such fluids are known per se, and the supercritical data of the substances, ie the respective supercritical pressure or the " supercritical temperature", can generally be found in tables or reference works.
  • the preferred substances which can serve as a fluid include carbon dioxide (CO 2 ), nitrogen, nitrous oxide, ethylene, propane and ammonia, but atmospheric gases, in particular carbon dioxide and nitrogen, are preferred.
  • a special machine technology is required to handle supercritical gases in injection molding technology.
  • the plastic granulate is melted, as is usual in conventional injection molding.
  • the supercritical gases are then fed into the thermoplastic melt in the cylinder of the injection molding machine.
  • the mixture of melt and supercritical gas is then injected into the mold at high speed and pressure.
  • Such tools and machines are known and are described, for example, in WO 00/73036 and WO 00/59702.
  • the molded body After the molded body has cooled, it is removed from the mold, the gas escaping into the environment even after a short time.
  • the moldings of the present invention can be used in particular in automobile construction, in the construction industry and in the sanitary area.
  • the strength of the complex component was measured in a quasi-stationary tensile test with a Bowden cable nipple diameter 3 mm at 23 ° C with 10 mm / min tensile speed and related to the cross-sectional area of the nipple.
  • the strength was 338 MPa, the molded body weighing 45 g.
  • Example 1 was essentially repeated, but no fluid was added. A molded body with a weight of 50 g was obtained, the screw-in torque of which was approximately 2.4 Nm and the over-torque of 7.5 Nm. The corresponding strength was 336 MPa.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

La présente invention concerne des corps moulés contenant des polyacétales, présentant une structure microcellulaire. Lesdits corps moulés présentent d'excellentes propriétés mécaniques, et une faible tendance à la formation de fissures de contrainte. L'invention concerne par ailleurs des procédés de fabrication desdits corps moulés.
EP03794995A 2002-09-10 2003-09-06 Corps moules contenant des polyacetales et procedes de fabrication de ces corps moules Withdrawn EP1539881A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10242186 2002-09-10
DE2002142186 DE10242186B4 (de) 2002-09-10 2002-09-10 Formkörper umfassend Polyacetale, Verfahren zur Herstellung dieser Formkörper sowie deren Verwendung
PCT/EP2003/009907 WO2004024819A2 (fr) 2002-09-10 2003-09-06 Corps moules contenant des polyacetales et procedes de fabrication de ces corps moules

Publications (1)

Publication Number Publication Date
EP1539881A2 true EP1539881A2 (fr) 2005-06-15

Family

ID=31724653

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03794995A Withdrawn EP1539881A2 (fr) 2002-09-10 2003-09-06 Corps moules contenant des polyacetales et procedes de fabrication de ces corps moules

Country Status (6)

Country Link
US (2) US20060121282A1 (fr)
EP (1) EP1539881A2 (fr)
JP (1) JP2005538232A (fr)
AU (1) AU2003264273A1 (fr)
DE (1) DE10242186B4 (fr)
WO (1) WO2004024819A2 (fr)

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EP2505609B1 (fr) 2011-04-01 2015-01-21 Ticona GmbH Polyoxyméthylène avec une grande résistance aux chocs pour moulage par soufflage-extrusion
WO2013101624A1 (fr) 2011-12-30 2013-07-04 Ticona Llc Articles moulés imprimables faits d'une composition de polymère de polyoxyméthylène
EP2647666A1 (fr) * 2012-04-05 2013-10-09 Ticona GmbH Polyoxyméthylène modifié du point de vue tribologique
US9745467B2 (en) 2012-12-27 2017-08-29 Ticona, Llc Impact modified polyoxymethylene composition and articles made therefrom that are stable when exposed to ultraviolet light
JP6700178B2 (ja) 2013-10-21 2020-05-27 ティコナ ゲゼルシャフト ミット ベシュレンクテル ハフツング 本質的に低摩擦のポリオキシメチレン
WO2015160592A1 (fr) 2014-04-17 2015-10-22 Ticona Llc Composition élastomère ayant une résistance à l'huile
JP6905515B2 (ja) 2015-09-30 2021-07-21 セラニーズ・セールス・ジャーマニー・ゲーエムベーハー 低摩擦できしり音のないアセンブリ
CN119931278A (zh) 2017-03-10 2025-05-06 塞拉尼斯销售德国有限公司 聚酯聚合物组合物
JP6931312B2 (ja) * 2017-10-04 2021-09-01 旭化成株式会社 ポリアセタール樹脂組成物

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AU2003264273A1 (en) 2004-04-30
DE10242186A1 (de) 2004-03-18
JP2005538232A (ja) 2005-12-15
WO2004024819A3 (fr) 2005-01-13
US20090283931A1 (en) 2009-11-19
DE10242186B4 (de) 2013-05-29
WO2004024819A2 (fr) 2004-03-25
US20060121282A1 (en) 2006-06-08

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