US20030162912A1 - Impact-resistant polyoxymethylene moulding compounds with a low emission, the use thereof and moulded bodies produced therefrom - Google Patents

Impact-resistant polyoxymethylene moulding compounds with a low emission, the use thereof and moulded bodies produced therefrom Download PDF

Info

Publication number
US20030162912A1
US20030162912A1 US10/381,501 US38150103A US2003162912A1 US 20030162912 A1 US20030162912 A1 US 20030162912A1 US 38150103 A US38150103 A US 38150103A US 2003162912 A1 US2003162912 A1 US 2003162912A1
Authority
US
United States
Prior art keywords
weight
component
polyoxymethylene
molding composition
stabilizer
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.)
Abandoned
Application number
US10/381,501
Other languages
English (en)
Inventor
Stefan Disch
Kurt Witan
Ernst Hofmann
Klaus Kurz
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
Priority claimed from DE10047488A external-priority patent/DE10047488B4/de
Priority claimed from DE2001126787 external-priority patent/DE10126787A1/de
Application filed by Ticona GmbH filed Critical Ticona GmbH
Assigned to TICONA GMBH reassignment TICONA GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HOFMANN, ERNST, KURZ, KLAUS, DISCH, STEFAN, WITAN, KURT
Publication of US20030162912A1 publication Critical patent/US20030162912A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • 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

Definitions

  • the present invention relates to impact-modified polyoxymethylene molding compositions which are suitable for producing molding or extrudates.
  • the products produced therewith are particularly stable during processing and have low formaldehyde emission and little odor.
  • polyoxymethylenes have become established as extremely useful technical materials in many applications.
  • Polyoxymethylene is particularly widely used as an engineering material in automotive construction, in the electrical industry, and in medical technology.
  • polyoxymethylene molding compositions are subject to a requirement for a certain level of mechanical properties, such as stiffness, hardness, and toughness, this level being an essential requirement for the use of these materials for technical components like gear wheels and levers, among many other examples.
  • the published values for yield stress are from 60 to 70 N/mm 2 .
  • the values found for the tensile modulus of elasticity of unmodified copolymers are from 2400 to 3100 N/mm 2 .
  • the values found for tensile strain at break are from 10 to 30%.
  • polyoxymethylenes can be toughened by adding impact modifiers.
  • Impact modifiers used comprise organic additives, such as crosslinked or non-crosslinked elastomers, or graft copolymers made from an elastomeric, single-phase core and from a hard outer graft layer.
  • Impact-modified polyoxymethylene molding compositions are known from the patent literature, e.g.
  • polyoxymethylene modified with polyurethanes (DE 1 193 240), polyoxymethylene modified with a 2-phase mixture made from polybutadiene and styrene-acrylonitrile (ABS) (DE 1 931 392), polyoxymethylene modified with a graft copolymer prepared from acrylatebutadiene (DE 1 964 156), a polyoxymethylene provided with modified polysiloxanes and, respectively, silicone rubbers (DE 2 659 357), and finally polyoxymethylene modified with a graft copolymer composed of an elastomeric, single-phase core based on polydiene and of a hard, single- or multiphase outer graft layer, e.g. made from poly(alkyl)acrylates, poly(alkyl)acrylonitriles or polystyrene (EP 0156285 B1).
  • a particular requirement during the processing of impact-modified polyoxymethylene molding compositions is that the degradation of the material is surpressed, to avoid any impairment of the properties of the product or of the material.
  • Stabilizers are added for this purpose.
  • EP 0156285 mentions the following stabilizers for the polyacetal phase: polyamides, amides of polybasic carboxylic acids, amidines, hydrazines, ureas, poly(N-vinyllactams), and the alkaline earth metal salts of aliphatic mono- to tribasic carboxylic acids having from 2 to 20 carbon atoms and preferably containing hydroxy groups. Mention is also made of oxidation stabilizers and light stabilizers. However, even the addition of stabilizers has not hitherto removed the shortcoming of high emission. Known stabilizers and stabilizer systems which reduce formaldehyde emission moreover cause impairment of mechanical property profile.
  • the object of the present invention is to provide polyoxymethylene molding compositions in which the formaldehyde emission found hitherto has been reduced while mechanical property profile is retained.
  • the moldings produced from these molding compositions are to have little odor.
  • the polyoxymethylene molding compositions of the invention have substantially reduced formaldehyde emission when compared with the prior art.
  • the reduction in emission is brought about by the interaction between the cyclic stabilizer having at least one ring nitrogen atom and the carboxylic salt.
  • the level of mechanical properties, particularly strength and impact strength is retained.
  • the molding composition of the invention comprises from 0.01 to 1.0% by weight, preferably from 0.03 to 0.3% by weight, of a cyclic stabilizer, component (A), which contains at least one nitrogen atom in the ring.
  • a cyclic stabilizer, component (A) which contains at least one nitrogen atom in the ring.
  • a cyclic stabilizer, component (A) which contains at least one nitrogen atom in the ring.
  • a cyclic stabilizer, component (A) which contains at least one nitrogen atom in the ring.
  • a cyclic stabilizer, component (A) which contains at least one nitrogen atom in the ring.
  • a cyclic stabilizer, component (A) which contains at least one nitrogen atom in the ring.
  • Examples are pyrrolidine, piperidine, pyrrole, pyridine, purine, indole, carbazole, tryptophan, oxazole, imidazole, thiazole, picoline, lutidine, collidine
  • Advantageous compounds are heterocyclic compounds having at least one nitrogen atom as heteroatom adjacent either to an amino-substituted carbon atom or to a carbonyl group, examples being pyridazine, pyrimidine, pyrazine, pyrrolidone, aminopyridine, and compounds derived therefrom.
  • Advantageous compounds of this type are aminopyridine and compounds derived therefrom.
  • any of the aminopyridines is suitable, e.g. melamine, 2,6-diaminopyridine, substituted and dimeric aminopyridines, and also pyrrolidone and compounds derived therefrom, and mixtures made from these compounds.
  • suitable pryrolidones are imidazolidinone and compounds derived therefrom, e.g.
  • hydantoin the derivatives of which are particularly advantageous, and of these compounds allantoin and its derivatives are particularly advantageous.
  • Other particularly advantageous compounds are triamino-1,3,5-triazine (melamine) and its derivatives, e.g. melamine-formaldehyde condensates and methylolmelamine.
  • melamine triamino-1,3,5-triazine
  • melamine-formaldehyde condensates methylolmelamine.
  • cyclic stabilizers which contain at least one nitrogen atom in the ring may be used individually or in combination.
  • the component (B) used comprises from 0.001 to 0.5% by weight of a metal salt of a carboxylic acid.
  • Salts of fatty acids are advantageous, in particular salts of higher fatty acids having from 10 to 32 carbon atoms, preferably from 14 to 32 carbon atoms, and particular preference is given to salts of montanic acids and stearic acid.
  • Preferred metals are those which occur in the form of mono- or divalent ions, e.g. alkali metals and alkaline earth metals, in particular alkaline earth metals. Particular preference is given to magnesium and calcium, an example being calcium stearate. Magnesium stearate is very particularly preferred as component (B).
  • the component (C) used comprises from 5 to 50% by weight, preferably from 5 to 40% by weight, particularly preferably from 7 to 30% by weight, of an impact modifier.
  • Impact modifiers which may used, individually or as a mixture, are polyurethanes, 2-phase mixtures made from polybutadiene and styrene-acrylonitrile (ABS), modified polysiloxanes and, respectively, silicone rubbers, or graft copolymers made from an elastomeric, single-phase core based on polydiene and from a hard outer graft layer (core-shell structure).
  • component (C) is composed of particles most of which, preferably more than 70% of which, have a structure of core and outer layers.
  • the core here is formed from an elastomeric polymer phase onto which has been grafted the hard outer layer, which may also be composed of two or more layers.
  • the core is preferably single-phase, meaning that the core is composed mainly, preferably completely, of the elastomeric soft phase and comprises only small amounts of, preferably no, inclusions made from hard polymer constituents of the outer layer.
  • the graft copolymer is mostly composed of from 40 to 95% by weight, advantageously from 60 to 90% by weight, particularly advantageously from 70 to 80% by weight, of the elastomeric core.
  • the proportion of the outer layers (shells) is from 5 to 60% by weight, advantageously from 10 to 40% by weight, particularly advantageously from 20 to 30% by weight.
  • the core is generally composed of polydienes, e.g. polybutadiene or polyiosprene, and can contain up to 10% by weight, advantageously up to 5% by weight, of comonomer units. Styrene or acrylonitrile may advantageously be used as comonomer.
  • the core polymer may also have been crosslinked and have a gel content, measured in toluene, generally greater than 70%, and preferably greater than 80%.
  • An example of a crosslinker which may be used is divinylbenzene.
  • the outer layer of the particles is composed of hard polymers which have been grafted onto the core as graft substrate.
  • the outer layer here may have a single- or multishell structure, advantageously a dual-shell structure. If there is more than one outer layer, it is advantageous for the various layers to be composed of different polymers or copolymers. It is advantageous here for the first layer to have been crosslinked. However, where appropriate, the other layers may also have been crosslinked.
  • suitable monomers which give suitable polymers for the outer layer of the particles are unsaturated nitrites, acrylates, methacrylates, vinyl esters, styrene derivatives, advantageous monomers being acrylonitrile, methacrylonitrile acrylates and methacrylates having an alcohol component which has from 1 to 6, preferably from 1 to 4, carbon atoms, examples being methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, and tert-butyl methacrylate.
  • Vinyl compounds which may also be used with advantage are vinyl acetate, vinyl ethers, N-vinyl-N-methylacetamide, and vinylpyrrolidone, and examples of styrene derivatives which may be used with advantage are styrene, ⁇ -methylstyrene and vinyltoluene.
  • Copolymers made from at least two of the abovementioned monomer groups and monomers may also be used in the structure of the outer layer, in particular copolymers of the specified styrene derivatives with the other monomers.
  • Particularly advantageous copolymers are those prepared from a mixture comprising from 20 to 80% by weight of acrylonitrile or methacrylonitrile with from 80 to 20% by weight of the other specified monomers, in particular acrylates, methacrylates and vinyl esters.
  • crosslinking monomers used may in principle comprise any of the compounds suitable for this purpose, for example multifunctional olefins, such as bivinylbenzene, ethylene glycol dimethacrylate, butylene glycol dimethacrylate, or else triallyl cyanurate.
  • multifunctional olefins such as bivinylbenzene, ethylene glycol dimethacrylate, butylene glycol dimethacrylate, or else triallyl cyanurate.
  • the glass transition temperature of the component (C) described above is from ⁇ 40 to ⁇ 120° C., preferably below ⁇ 60° C., in particular from ⁇ 80 to ⁇ 120° C.
  • the preparation of the graft copolymers which can be used as component (C) and have a core-shell structure is known and can use single-stage polymerization in the case of a single-shell outer layer or multistage polymerization in the case of a multishell outer layer, for example as described in the Patent Specification U.S. Pat. No. 39,875,704, which is incorporated herein by way of reference.
  • the graft copolymerization is carried out using water-soluble initiators or using activated initiator systems of which one component at least is water-soluble, for example as described in C. B. Bucknall, “Toughened Plastics”, p. 98, Applied Science Publishers Ltd. 1977 (London)).
  • the starting material is a polydiene, preferably in the form of an aqueous latex with defined average particle size, particularly preferably in the range from 0.1 to 5 ⁇ m, where the polydiene has particularly preferably been partially crosslinked.
  • the monomer or the monomer mixture is polymerized in the presence of the polydiene, whereupon the major portion of the monomers is grafted onto the polydiene particles.
  • the amount of polydiene is generally 40 to 95% by weight, and the amount of the monomers or monomer mixture is generally from 5 to 60% by weight, based in each case on the total amount.
  • the graft yield achieved varies from 60 to 95%, preferably from 80 to 90%.
  • the graft polymerization is carried out in solution or emulsion, preferably in aqueous dispersion.
  • the fine-particle polydiene latex forms an initial charge with addition of the usual polymerization auxiliaries, such as emulsifying agents or suspending agents, free-radical initiators, regulators, etc., and the monomer or the monomer mixture is added and polymerized at temperatures from 30 to 95° C., preferably from 50 to 80° C.
  • the initiator is water-soluble, and examples of initiators which may be used are water-soluble peroxides, percarbonates or perborates.
  • redox system multicomponent initiator system at least one component has to be water-soluble.
  • emulsifiers which may be used, and are also termed dispersing agents, are aliphatic and aromatic sulfates, sulfonates, and salts of carboxylic acids, for example dresinates.
  • dispersing agents are aliphatic and aromatic sulfates, sulfonates, and salts of carboxylic acids, for example dresinates.
  • the compounds suitable for this purpose are well known to the skilled worker.
  • a monomer or a monomer mixture such as styrene
  • the core polymer such as butadiene-styrene copolymer
  • another monomer or monomer mixture is used, where appropriate in the presence of a crosslinker.
  • the average particle size of the particles is advantageously from 0.1 to 5 ⁇ m.
  • graft copolymers for component (C) are those in which the core is composed mainly or completely of, preferably partially crosslinked, polyacrylates or polymethacrylates, the alcohol component of which contains from 1 to 15 carbon atoms, preferably from 1 to 8 carbon atoms.
  • Olefinic monomers may be used as comonomers, advantageously butadiene, cyclooctadiene, vinyl ethers and haloalkyl acrylates.
  • the gel content, measured in toluene is preferably at least 50%, particularly preferably at least 70%.
  • For the outer graft layer use may be made of the monomers and monomer mixtures described above. The particle sizes, too, are in the same range.
  • Graft polymers based on polyacrylates and on polymethacrylates are described by way of example in DE 1964156, DE 2116653, EP 50265, EP 60601 and EP 64207, incorporated herein by way of reference.
  • the core of the graft polymer may also be composed entirely or partially of a silicone rubber and/or of non-crosslinked organopolysiloxanes.
  • the other monomers and/or monomer mixtures described above may be grafted onto this core, which preferably contains functional groups having graft activity. These materials are described by way of example in DE 2659357, incorporated herein by way of reference.
  • Component (C) preferably comprises a diluent, and in particular if the core of the graft polymer is composed of partially crosslinked polyacrylates or polymethacrylates.
  • the diluent is a low-melting, advantageously polymeric substance which has good miscibility in the melt with the graft polymer used as impact modifier. It is particularly advantageous to use this diluent if the level of crosslinking of the graft polymers is sufficiently high to make them insoluble in the diluent, and a two-phase system forms, and the surface tension can lead to fine distribution of the graft polymers in the diluent.
  • the graft polymer is preferably present mainly in the peripheral region of the two-phase system.
  • the amount of graft polymer increases it is also increasingly present in the core, and, with a further increase in the amount of the graft polymer, also outside the two-phase system within the matrix polymer, component (G). It is particularly advantageous to have uniform distribution of the two-phase system and of the graft polymer in component (G), in particular if the graft polymer is mainly present at the periphery of the two-phase system.
  • the melting point of the diluent should be below 250° C., preferably from 180 to 210° C.
  • the amount of the diluent is from 10 to 95%, advantageously from 30 to 70%, particularly preferably from 40 to 60%, based on the entirety of graft polymer and diluent.
  • diluents Materials which may be used with very particular advantage as diluents are polyurethanes and segmented copolyesters and ethylene-vinylacetate copolymers. Other suitable diluents are known to the skilled worker and are described by way of example in DE 2818240 and DE 2523991, incorporated herein by way of reference. The diluent may advantageously be mixed with the graft polymer prior to addition to component (G).
  • component (C) which may be used are polyurethanes, preferably thermoplastic polyurethanes.
  • the polyurethanes which may be used according to the invention are known products described by way of example in DE 1193240 and DE 2051028, and in Kunststoff-Taschenbuch, [Plastics Handbook] (Saechtling, 27th edition, Hanser Verlag 1998) on pages 523-542, incorporated herein by way of reference.
  • polyisocyanates in particular diisocyanates, polyesters, polyethers, polyesteramides, polyacetalas or other suitable hydroxy or amino compounds, such as hydroxylated polybutadiene, or mixtures of the abovementioned compounds.
  • chain extenders such as low-molecular-weight polyols, in particular diols, polyamines, in particular diamines, or water.
  • diisocyanates examples are diisocyanates of the formula I
  • R is a divalent, straight-chain or branched aliphatic radical having from 1 to 20, preferably from 2 to 12, carbon atoms, or a divalent cycloaliphatic radical having from 4 to 20, preferably from 6 to 15, carbon atoms, or a divalent, substituted or unsubstituted aromatic radical having from 6 to 25, preferably from 6 to 15, carbon atoms.
  • Diisocyanates of this type which are particularly preferred are hexamethylene diisocyanate, and 2,2,4- and 2,4,4-trimethylhexamethylene diisocyanate.
  • R in formula I above is a cycloaliphatic radical, this is preferably the unsubstituted or substituted cyclohexane radical.
  • diisocyanates of this type are 1,2- or 1,4-di(isocyanatomethyl)cyclohexane or isophorone diisocyanate.
  • R in formula I above may also be a combination of divalent, open-chain aliphatic or cycloaliphatic radicals, for example
  • R 1 is a saturated, straight-chain or branched aliphatic radical having from 1 to 8, preferably from 1 to 3, carbon atoms.
  • the two rings here are preferably unsubstituted cyclohexane, while R 1 is preferably the methylene, ethylene, methylmethylene, or dimethylmethylene group.
  • R in formula I above is a divalent aromatic radical, it is preferably the toluene, diphenylmethane, phenylene or naphthalene radical.
  • corresponding diisocyanates are toluene 2,4-diisocyanate, toluene 2,6-diisocyanate, diphenylmethane 4,4′-diisocyanate, 3,3′-dimethyldiphenylmethane 4,4′-diisocyanate, 3,3′-dimethyldiphenylene 4,4′-diisocyanate(3,3′-bitoluene-4,4′-diisocyanate), m-phenylene diisocyanate, p-phenylene diisocyanate, o-phenylene diisocyanate, chlorophenylene 2,4-(toluene diisocyanate), 3,3′-dichlorodiphenyl 4,4′-diisocyanate
  • R in formula I above is a cycloaliphatic radical, it is preferably the unsubstituted or substituted cyclohexane radical.
  • diisocyanates of this type are 1,2- or 1,4-di-(isocyanatomethyl)cyclohexane or isophorone diisocyanate.
  • the diisocyanates of formula I may also be used in oligomeric form, for example in dimeric or trimeric form.
  • polyisocyanates instead of the polyisocyanates, use may also be made in a known manner of blocked polyisocyanates, these being obtained from the isocyanates mentioned by reaction with phenol or caprolactam, for example.
  • Aliphatic polyhydroxy compounds which may be used are polyethers, such as polyethylene glycol ethers, polypropylene glycol ethers, and polybutylene glycol ethers, poly-1,4-butanediol ethers or mixed polyethers made from ethylene oxide and propylene oxide.
  • polyethers such as polyethylene glycol ethers, polypropylene glycol ethers, and polybutylene glycol ethers, poly-1,4-butanediol ethers or mixed polyethers made from ethylene oxide and propylene oxide.
  • Other compounds which may be used for this purpose are polyesteramides, polyacetals, and preferably aliphatic polyesters, all of these compounds having free OH end groups.
  • the aliphatic polyesters preferably used are mainly non-crosslinked polyesters with molecular weights of from 500 to 10000, preferably from 500 to 5000.
  • the acid components derive from unbranched and/or branched aliphatic dicarboxylic acids, e.g. dicarboxylic acids of the formula
  • n from 0 to 20, preferably from 4 to 10, in particular adipic acid and sebacic acid.
  • Use may also be made here of cycloaliphatic dicarboxylic acids, such as cyclohexanedicarboxylic acids, or of mixtures with the abovementioned aliphatic dicarboxylic acids.
  • the alcohol component used for these polyesters is in particular an unbranched or branched aliphatic primary diol, e.g. a diol of the formula
  • m from 2 to 12, preferably from 2 to 6. Mention may in particular be made here of 1,4-butanediol, 1,6-hexanediol and 2,2-dimethylpropanediol-1,3 and also diethylene glycol. Cycloaliphatic diols, such as bis-hydroxymethylcyclohexane, are also suitable here, as are mixtures with the aliphatic diols.
  • Each of the polyesters may be prepared from one dicarboxylic acid and one diol, or else, as mentioned, from a mixture of two or more dicarboxylic acids and/or two or more diols.
  • Chain extenders which may be used in preparing the polyurethanes are mainly low-molecular-weight polyols, in particular diols, or else polyamines, in particular diamines, or else water.
  • the polyurethanes used according to the invention are preferably thermoplastic and therefore preferably substantially non-crosslinked, i.e. capable of melting repeatedly without any significant signs of decomposition.
  • Their reduced specific viscosities, measured at 30° C. in dimethylformamide, are generally from 0.5 to 3 dl/g, preferably from 1 to 2 dl/g.
  • the values for the tensile strains at break are advantageously from 800 to 1500%, preferably from 1000 to 1500%, while the Shore hardness A is not more than 90, advantageously not more than 81, preferably from 50 to 85, particularly preferably from 60 to 80, in particular from 65 to 80, and the glass transition temperatures are mostly not above 0° C., advantageously not above ⁇ 10° C., particularly advantageously not above ⁇ 20° C.
  • the amount of sterically hindered phenol compound used, component (D), may be from 0.0 to 2.0% by weight, preferably from 0.1 to 1.0% by weight, particularly preferably from 0.2 to 1.0% by weight.
  • these compounds are pentaerythrityl tetrakis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox 1010, Ciba Geigy), triethylene glycol bis[3-(3-tert-butyl4-hydroxy-5-methylphenyl)propionate] (Irganox 245, Ciba Geigy), 3,3′-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propiono] hydrazide (Irganox MD 1024, Ciba Geigy), hexamethylene glycol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (
  • the component (E) present may comprise at least one stabilizer from the group of the benzotriazole derivatives or benzophenone derivatives or aromatic benzoate derivatives, the amount being from 0.0 to 1.0% by weight, preferably from 0.0 to 0.8% by weight.
  • Preference is given to 2-[2′-hydroxy-3′,5′-bis(1,1,-dimethylbenzyl)phenyl]benzotriazole, obtainable commercially as Tinuvin 234 (Ciba Geigy).
  • the component (F) present in the molding composition of the invention may comprise from 0.0 to 0.8% by weight, preferably from 0.0 to 0.5% by weight, very particularly preferably from 0.4% by weight, of a sterically hindered amine as light stabilizer (HALS).
  • HALS sterically hindered amine as light stabilizer
  • polyoxymethylene may be homopolyoxymethylenes or copolyoxymethylenes.
  • Polymers of this type are known to the skilled worker and are described in the literature.
  • the homopolymers are generally obtained by polymerizing formaldehyde or trioxane, and the polymerization here may be initiated cationically or anionically.
  • polyoxymethylenes described by way of example in DE-A 29 47 490 are generally unbranched linear polymers and generally contain at least 80%, preferably at least 90%, of oxymethylene units (—CH 2 O—).
  • polyoxymethylenes here encompasses homopolymers of formaldehyde or of its cyclic oligomers, such as trioxane or tetroxane, and also corresponding copolymers.
  • Homopolymers of formaldehyde or of trioxane are polymers of this type whose hydroxy end groups have been chemically stabilized in a known manner to resist degradation, e.g. by esterification or etherification.
  • Copolymers are polymers made from formaldehyde or from its cyclic oligomers, in particular trioxane, and from cyclic ethers, cyclic acetals, and/or linear polyacetals.
  • homopolyoxymethylenes or copolyoxymethylenes are known per se to the skilled worker and are described in the literature. These polymers very generally have at least 50 mol % of —CH 2 O— repeat units in the main polymer chain.
  • the homopolymers are generally prepared by polymerizing formaldehyde or trioxane, preferably in the presence of suitable catalysts. Examples of particularly suitable catalysts are boron trifluoride and trifluoromethanesulfonic acid.
  • copolyoxymethylenes as component (G), in particular those which also contain, alongside the —CH 2 O— repeat units, up to 50 mol %, preferably from 0.1 to 20 mol %, and in particular from 0.5 to 10 mol %, of repeat units of the following formula
  • R 1 to R 4 are a hydrogen atom, a C 1 -C 4 -alkyl group, or a halo-substituted alkyl group having from 1 to 4 carbon atoms
  • R 5 is —CH 2 —, —CH 2 O—, or a C 1 -C 4 -alkyl- or C 1 -C 4 -haloalkyl-substituted methylene group, or a corresponding oxymethylene group
  • n is from 0 to 3.
  • These groups may advantageously be introduced into the copolymers by the ring-opening of cyclic ethers.
  • Preferred cyclic ethers are those of the formula
  • R 1 to R 5 and n are as defined above.
  • Cyclic ethers which may be mentioned as examples are ethylene oxide, propylene 1,2-oxide, butylene 1,2-oxide, butylene 1,3-oxide, 1,3-dioxane, 1,3-dioxolane and 1,3-dioxepan, and comonomers which may be mentioned as examples are linear oligo- or polyformals, such polydioxolane or polydioxepan.
  • Particularly advantageous copolymers are those made from 99.5-95 mol % of trioxane and 0.5-5 mol % of one of the above of the above-mentioned comonomers.
  • component (G) Also suitable as component (G) are oxymethyleneterpolymers, for example those prepared by reacting trioxane with one of the abovementioned cyclic ethers and with a third monomer, preferably a bifunctional compound of the formula
  • Z is a chemical bond, —O—, or —ORO— (R ⁇ C 1 -C 8 -alkylene or C 3 -C 8 -cycloalkylene).
  • Preferred monomers of this type are ethylene diglycide, diglycideyl ether, and diethers made from glycidyl compounds and formaldehyde, dioxane or trioxane in a molar ratio of 2:1, and also diethers made from 2 mol of glycidyl compound and 1 mol of an aliphatic diol having from 2 to 8 carbon atoms, for example the diglycidyl ether of ethylene glycol, 1,4-butanediol, 1,3-butanediol, 1,3-cyclobutanediol, 1,2-propanediol or 1,4-cyclohexanediol, to mention just a few examples.
  • the preferred copolyoxymethylenes have melting points of 150° C. or above and molecular weights (weight average) M W in the range from 2000 to 1000000, preferably from 7000 to 150000. Particular preference is given to end-group-stabilized polyoxymethylenes whose chain ends have carbon-carbon bonds.
  • the melt index (MVR 190/2.16) of the polyoxymethylenes used is generally from 0.3 to 100 cm 3 /10 min (ISO 1133).
  • polyoxymethylenes substantially having oxymethylene units and oxyethylene units in the polymer chain.
  • the proportion of the oxymethylene units, based on structural units in the polymer chain, is from 0.1 to 15 mol %, preferably 0.2 to 10 mol %.
  • the melt index MFI, measured to ISO 1133 at 190° C. with an applied weight of 2.16 kg is from 0.5 to 76 g/10 min, preferably from 2 to 60 g/10 min, and particularly preferably from 5 to 35 g/10 min.
  • the number-average molar mass is at least 5000 g/mol and at most 100000 g/mol, determined by GPC in dimethylacetamide at from 150 to 160° C.
  • copolyoxymethylenes of differing compositions instead of a single copolyoxymethylene.
  • Well known preparation processes can be used to prepare the copolyoxymethylenes.
  • An example of a possible process is the copolymerization of trioxane with dioxolane in the presence of generally conventional amounts of BF 3 and methylal. Preference is given to polyoxymethylenes whose preparation uses trifluoromethanesulfonic acid.
  • the molding composition of the invention may comprise other conventional additives, individually or as a mixture, at up to 40% by weight, examples being carbon blacks, e.g. conductivity blacks, acid scavengers, antioxidants, UV stabilizers, coupling agents, mold-release aids, substances to improve electrical conductivity, antistats, nucleating agents, such as polyoxymethylene terpolymers or talc, colorants, such as inorganic pigments, e.g.
  • titanium dioxide ultramarine blue, cobalt blue, or organic pigments and colours, such as phthalocyanines, anthrachinones, fillers, such as glass beads, wollastonite, chalk, loam, molybdenum sulfide, or graphite, inorganic or organic fibres, such as glass fibres, carbon fibres or aramide fibers, lubricants, such as soaps and esters, stearyl stearate, montanic esters, partially hydrolyzed montanic esters, stearic acids, polar and/or non-polar polyethylene waxes, poly- ⁇ -olefin oligomers, silicone oils, polyalkylene glycols and perfluoroalkyl ethers, polytetrafluoroethylene, ultrahigh-molecular-weight polyethylene, paraffins, solid and liquid, stearic acids, and thermoplastic or thermoset polymer additives, elastomers, and other polymers, such as EPDM (ethylene-propylene-d
  • the polyoxymethylene molding compositions of the invention may be prepared using the conventional and known mixing methods, such as pelletizing, extrusion, kneading, etc.
  • the molding compositions of the invention are preferably prepared by mixing polyoxymethylene with additives and stabilizers and then pelletizing the mixture.
  • the colored polyoxymethylene molding compositions of the invention have substantially reduced emission.
  • the reduction in formaldehyde release can be observed even during preparation of the molding composition, e.g. during pelletizing, and also during processing.
  • the polyoxymethylene molding composition of the invention therefore contributes to health and safety in the workplace.
  • the formaldehyde emission measured to VDA 275 on plaques of wall thickness 1 mm after 24 h of storage is advantageously less than 40 mg/kg, particularly advantageously less than 30 mg/kg, very particularly advantageously less than 20 mg/kg.
  • the mechanical properties of the molding compositions of the invention comply with the conventional requirements placed upon commercially available polyoxymethylene products, and the conventional application sectors and processing techniques for polyoxymethylene are therefore applicable without restriction.
  • molding compositions of the invention are internal fittings and claddings for means of transport, such as automobiles, aircraft, etc., other application sectors being household goods, toys, baby items, and also devices and components for electronics and electrical engineering.
  • the molding compositions of the invention are particularly suitable for producing apparatus and instruments, or parts thereof, for medical applications.
  • the molding compositions prepared according to the invention have the lowest formaldehyde emission of any currently commercially available products, have defect-free surfaces, and have high colorfastness when the moldings are exposed for a long time to light or heat.
  • Formaldehyde emission Plaques of wall thickness 1 mm were manufactured from the colored polyoxymethylene molding compositions. The formaldehyde emission from the plaques was determined to VDA 275 after a storage time of 24 h (VDA Guideline No. 275, worked Kraftfahrcher e.V. July 1994).
  • test specimens The polyacetal pellets are molded by injection molding to give plaques of dimensions 80*50*1 mm.
  • a Kraus Maffei KM 120/340 B injection molding machine is used with the following injection molding parameters: melt temperature 195° C., flow front velocity 200 mm/s, mold wall temperature 85° C., hold pressure 900 bar, hold pressure time 30 s, cooling time 10 s, back pressure from 0 to 10 bar.
  • the test specimens are stored for 24 h in a cabinet under standard temperature and humidity conditions at 23° C. and 50% relative humidity prior to testing.
  • test specimens are suspended on a stainless steel hook above 50 ml of deionized water in a 1 l glass bottle and stored for 3 h in a circulating-air drying cabinet at 60° C.
  • the test specimens are removed from the test bottle.
  • 5 ml of test solution are pipetted into a test tube, which is heat-conditioned at 95° C. for 10 minutes.
  • 3 ml of acetylacetone and 3 ml of a 20% strength of ammonium acetate solution are then added to the test tube.
  • the formaldehyde forms the diacetyldihydrolutidine complex with the reagents, and the absorption of the complex at 412 nm is determined photometrically.
  • the formaldehyde concentration in the specimen solution is calculated from the absorption.
  • Brabender Test The polyoxymethylene molding composition is sheared at 210° C. in a twin-screw Brabender kneader.
  • the formaldehyde which escapes is discharged with an inert gas stream and absorbed in sodium sulfite solution.
  • the sodium sulfite solution is titrated for quantitative determination of the formaldehyde released.
  • the result obtained is the amount of formaldehyde released as a function of time.
  • the degradation rate is determined from the gradient of the curve by linear extrapolation.
  • the polyoxymethylene used in the examples and comparative examples comprises Hostaform C 9021.
  • the polymer contained 3.4% of dioxolane as comonomer, and trifluoromethanesulfonic acid was used as initiator.
  • the polymer contained 3.4% of dioxolane as comonomer and boron trifluoride was used as initiator.
  • the polymer comprised 5.6% of dioxolane as comonomer, and trifluoromethanesulfonic acid was used as initiator. Irganox 1010 from Ciba Spezialitätenchemie was used as antioxidant.
  • Licowachs E or Licowachs C from Clariant were used as flow aids. Comparative experiments used Eurelon from Vantico and dicyandiamide (DCD), where appropriate in combination with magnesium stearate, to reduce emission.
  • the impact-modifier component used comprised Paraloid EXL 2600 from Röhm & Haas.
  • pellets from the examples and comparative examples were molded by injection molding to give the test specimens for determining tensile modulus of elasticity, yield stress, and tensile strain at break, and also to injection-mold the plaques for determining formaldehyde emission.
  • a Henschel mixer 190 g of acetylene black, 330 g of Kronos 2220, 240 g of Sicotan Yellow K 2112, 20 g of Renol Brown EKX 861, 600 g of Irganox 245, 200 g of Licowachs C, 50 g of Eurelon, 30 g of dicyandiamide, 400 g of Tinuvin 234, 400 g Tinuvin 770, 13 kg of Paraloid EXL 2600 (producer Rohm & Haas), and polyoxymethylene base polymer to 100 kg.
  • a twin-screw extruder is used to pelletize the mixture.
  • the base polymer is identical with the base polymer used in Example 25.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Vehicle Interior And Exterior Ornaments, Soundproofing, And Insulation (AREA)
US10/381,501 2000-09-26 2001-09-17 Impact-resistant polyoxymethylene moulding compounds with a low emission, the use thereof and moulded bodies produced therefrom Abandoned US20030162912A1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE10047488A DE10047488B4 (de) 2000-09-26 2000-09-26 Eingefärbte Polyoxymethylen-Formmassen und daraus hergestellte Formteile
DE10047488.8 2000-09-26
DE10126787.8 2001-06-01
DE2001126787 DE10126787A1 (de) 2001-06-01 2001-06-01 Schlagzähe Polyoxymethylen-Formmassen mit geringer Emission, ihre Verwendung und daraus hergestellter Formkörper

Publications (1)

Publication Number Publication Date
US20030162912A1 true US20030162912A1 (en) 2003-08-28

Family

ID=26007159

Family Applications (2)

Application Number Title Priority Date Filing Date
US10/381,501 Abandoned US20030162912A1 (en) 2000-09-26 2001-09-17 Impact-resistant polyoxymethylene moulding compounds with a low emission, the use thereof and moulded bodies produced therefrom
US12/125,603 Expired - Lifetime US8053499B2 (en) 2000-09-26 2008-05-22 Colored polyoxymethylene molding compounds and molded parts produced therefrom

Family Applications After (1)

Application Number Title Priority Date Filing Date
US12/125,603 Expired - Lifetime US8053499B2 (en) 2000-09-26 2008-05-22 Colored polyoxymethylene molding compounds and molded parts produced therefrom

Country Status (8)

Country Link
US (2) US20030162912A1 (enExample)
EP (2) EP1325078B1 (enExample)
JP (4) JP2004522810A (enExample)
AT (2) ATE348860T1 (enExample)
AU (2) AU2001291868A1 (enExample)
DE (2) DE50109172D1 (enExample)
ES (2) ES2260283T3 (enExample)
WO (2) WO2002026884A1 (enExample)

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050080185A1 (en) * 2003-10-10 2005-04-14 Mhetar Vijay R. Poly(arylene ether) composition and method of making
WO2005044916A1 (ja) * 2003-11-10 2005-05-19 Polyplastics Co., Ltd. アルデヒド抑制剤組成物およびポリアセタール樹脂組成物
WO2007012469A1 (de) 2005-07-28 2007-02-01 Ticona Gmbh Emissionsarme, tribologisch modifizierte polyoxymethylen-formmassen und daraus hergestellte formteile
US20070078204A1 (en) * 2003-10-24 2007-04-05 Sumio Komatsu Polyacetal resin composition and article thereof
US20070123617A1 (en) * 2003-10-01 2007-05-31 Hatsuhiko Harashina Polyacetal resin composition
US20070276070A1 (en) * 2003-12-22 2007-11-29 Tak-Kyu Kim Poloyoxymethylene Composition Having High Fuel Resistance And Shaped Article Produced Therefrom
US20080166544A1 (en) * 2007-01-10 2008-07-10 Airbus Deutschland Gmbh Rear-Illuminable Aircraft Interior Component
US20080242800A1 (en) * 1999-08-06 2008-10-02 Ticona Gmbh Low-emission colored polyoxymethylene molding composition
US20090048388A1 (en) * 2007-08-16 2009-02-19 Elia Andri E Wear resistant toughened and reinforced polyacetal compositions
US20100179290A1 (en) * 2009-01-15 2010-07-15 Christian Lietzau Poly(arylene ether) articles and compositions
US20110034610A1 (en) * 2009-08-07 2011-02-10 Ticona, Llc Low Formaldehyde Emission Polyacetal Composition
US20110230602A1 (en) * 2008-09-03 2011-09-22 Mitsubishi Engineering-Plastics Corporation Polyacetal resin composition, resin molded article, and method and agent for improving polyacetal resin raw material composition
US20110236276A1 (en) * 2008-10-20 2011-09-29 Stefan Schosnig Analytical test tape instrument
US20140179840A1 (en) * 2012-12-26 2014-06-26 Ticona Llc Low Emission, UV Stabilized High Strength Acetal Copolymer
WO2014105758A3 (en) * 2012-12-26 2014-10-16 Ticona Llc Stabilized polymer composition containing an impact modifier
US8975313B2 (en) 2011-09-29 2015-03-10 Ticona Llc Polymer composition for producing articles having a metallic appearance
CN105001590A (zh) * 2014-04-18 2015-10-28 奕益实业有限公司 用于聚甲醛的无三聚氰胺复合式添加剂
EP3072927A4 (en) * 2013-11-21 2016-12-07 Polyplastics Co METHOD FOR PRODUCING A POLYOXYMETHYLENE RESIN COMPOSITION
CN107429037A (zh) * 2015-02-25 2017-12-01 三菱化学株式会社 树脂组合物及其成型体
US20190040182A1 (en) * 2016-04-13 2019-02-07 Kaneka Corporation Toughened epoxy resin composition
US20190367703A1 (en) * 2018-06-04 2019-12-05 Celanese International Corporation Polyoxymethylene Composition in Food Handling Applications

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10047614C2 (de) 2000-09-26 2003-03-27 Generis Gmbh Vorrichtung zum schichtweisen Aufbau von Modellen
ES2260283T3 (es) * 2000-09-26 2006-11-01 Ticona Gmbh Masas de moldeo teñidas de poli(oximetileno) y piezas moldeadas producidas a partir de ellas.
DE10238518A1 (de) * 2002-08-21 2004-03-04 Ticona Gmbh Verschleißfeste Polyoxymethylen Formmassen und deren Verwendung
JP5008256B2 (ja) * 2004-04-23 2012-08-22 東レ株式会社 ポリオキシメチレン樹脂組成物の製造方法
JP4815144B2 (ja) * 2005-04-01 2011-11-16 ジャパンコンポジット株式会社 ラジカル硬化性樹脂組成物
US7645821B2 (en) 2005-07-28 2010-01-12 Ticona Gmbh Low-emission, tribologically modified polyoxymethylene molding compositions and moldings produced therefrom
JP5325792B2 (ja) * 2006-11-22 2013-10-23 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 静電気拡散性ポリアセタール組成物
JP4876024B2 (ja) * 2007-05-09 2012-02-15 旭化成ケミカルズ株式会社 ボタン
JP5301794B2 (ja) * 2007-05-23 2013-09-25 旭化成ケミカルズ株式会社 ポリオキシメチレン樹脂組成物およびその成形体
WO2009012003A1 (en) * 2007-07-19 2009-01-22 Ticona Llc Stabilized thermoplastic copolyesters
JP5297640B2 (ja) * 2007-11-29 2013-09-25 ポリプラスチックス株式会社 耐酸性に優れたポリアセタール樹脂成形品
US9090769B2 (en) 2011-04-05 2015-07-28 Ticona Llc Molded articles having a swirl-like or marble-like appearance and compositions for producing same
US9296874B2 (en) * 2011-04-28 2016-03-29 Ticona Llc Polyacetal compositions and molded products made therefrom
EP2796505B1 (en) * 2011-12-21 2017-08-23 Mitsubishi Gas Chemical Company, Inc. Resin composition and shaped article
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
CN106795359A (zh) 2014-09-05 2017-05-31 Sabic环球技术有限责任公司 聚甲醛组合物、 用于制造的方法和由其制备的制品
JP6853020B2 (ja) * 2015-12-11 2021-03-31 旭化成株式会社 ポリアセタール樹脂用顆粒状組成物、及びポリアセタール樹脂組成物
WO2017156053A1 (en) * 2016-03-08 2017-09-14 Ticona Llc Orthopedic device and polymer compositions for making same
EP3526289A1 (en) 2016-10-11 2019-08-21 Celanese Sales Germany GmbH Wear resistant polymer composition having improved surface appearance
US11485856B2 (en) 2017-05-05 2022-11-01 Ticona Llc Polyoxymethylene polymer composition that is chemical resistant
KR102474348B1 (ko) 2017-11-30 2022-12-05 현대자동차 주식회사 폴리 옥시 메틸렌 수지 조성물 및 이로부터 제조된 성형품
KR102792993B1 (ko) * 2018-05-03 2025-04-07 셀라니즈 세일즈 저머니 게엠베하 의료 기술 응용 분야에서 사용하기 위한 매스-착색된 중합체 조성물
JPWO2021002315A1 (enExample) * 2019-07-03 2021-01-07
WO2021002314A1 (ja) * 2019-07-03 2021-01-07 三菱エンジニアリングプラスチックス株式会社 樹脂組成物および成形品
JPWO2021002316A1 (enExample) * 2019-07-03 2021-01-07
JP7257293B2 (ja) * 2019-08-30 2023-04-13 ポリプラスチックス株式会社 ポリアセタール樹脂組成物及びその製造方法

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5290858A (en) * 1989-03-31 1994-03-01 Takeda Chemical Industries, Ltd. Core-shell polymer, production and use thereof
US5369177A (en) * 1992-09-05 1994-11-29 Basf Aktiengesellschaft UV-stabilized polyoxymethylene molding materials
US5393813A (en) * 1992-10-24 1995-02-28 Degussa Aktiengesellschaft Polyoxymethylene having improved acid stability
US5919849A (en) * 1994-02-15 1999-07-06 Rohm And Haas Company Impact modified polyacetal compositions
US5948844A (en) * 1995-09-29 1999-09-07 Asahi Kasei Kogyo Kabushiki Kaisha Polyacetal resin composition
US5962623A (en) * 1998-09-08 1999-10-05 Ticona Gmbh Process for the preparation of polyacetal copolymers
US6147146A (en) * 1996-11-13 2000-11-14 Asahi Kasei Kogyo Kabushiki Kaisha Resin composition
US6590020B1 (en) * 1998-06-27 2003-07-08 Basf Aktiengesellschaft Stabilized polyoxymethylene moulding materials
US20030158301A1 (en) * 1996-12-27 2003-08-21 Hatsuhiko Harashina Polyacetal resin composition and moldings

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3151814A1 (de) 1981-12-29 1983-07-07 Hoechst Ag, 6230 Frankfurt "fuellstoff enthaltende kunststoff-formmasse, verfahren zu ihrer herstellung sowie deren verwendung"
JPS5996157A (ja) * 1982-11-25 1984-06-02 Polyplastics Co ポリアセタ−ル樹脂組成物
DE3505524A1 (de) * 1984-03-28 1985-10-10 Hoechst Ag, 6230 Frankfurt Schlagzaeh modifiziertes polyoxymethylen und daraus hergestellte formkoerper
JP2993062B2 (ja) 1990-07-02 1999-12-20 三菱瓦斯化学株式会社 オキシメチレン共重合体組成物
JPH0692476B2 (ja) * 1990-10-05 1994-11-16 旭化成工業株式会社 安定化ポリオキシメチレンの製造法
JP3024802B2 (ja) * 1991-02-04 2000-03-27 ポリプラスチックス株式会社 ポリアセタール樹脂着色組成物
JP3088159B2 (ja) * 1991-12-04 2000-09-18 ポリプラスチックス株式会社 ポリアセタール成形体
JPH06136234A (ja) * 1992-10-28 1994-05-17 Polyplastics Co ポリオキシメチレン組成物
CA2116241A1 (en) * 1992-06-30 1994-01-06 Noriyuki Sugiyama Polyoxymethylene composition
JP3140618B2 (ja) * 1993-09-02 2001-03-05 ポリプラスチックス株式会社 ポリアセタール樹脂組成物
JP3399483B2 (ja) * 1993-12-21 2003-04-21 三菱瓦斯化学株式会社 オキシメチレン共重合体樹脂組成物
JPH07268180A (ja) * 1994-03-30 1995-10-17 Polyplastics Co ポリオキシメチレン組成物
JP3374874B2 (ja) * 1994-06-07 2003-02-10 三菱瓦斯化学株式会社 オキシメチレン共重合体樹脂組成物の製造方法
MY114026A (en) 1995-09-01 2002-07-31 Asahi Chemical Ind Polyacetal resin molded article and process for producing the same
DE19803227B4 (de) 1998-01-27 2007-06-21 Ticona Gmbh Farbmittelzubereitung zur Einfärbung von Polyoxymethylen-Formmassen
JP4167341B2 (ja) * 1998-03-25 2008-10-15 ポリプラスチックス株式会社 ポリアセタール樹脂組成物およびその製造方法
JP4418553B2 (ja) * 1998-05-07 2010-02-17 ポリプラスチックス株式会社 ポリアセタール樹脂組成物
ES2260283T3 (es) * 2000-09-26 2006-11-01 Ticona Gmbh Masas de moldeo teñidas de poli(oximetileno) y piezas moldeadas producidas a partir de ellas.

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5290858A (en) * 1989-03-31 1994-03-01 Takeda Chemical Industries, Ltd. Core-shell polymer, production and use thereof
US5369177A (en) * 1992-09-05 1994-11-29 Basf Aktiengesellschaft UV-stabilized polyoxymethylene molding materials
US5393813A (en) * 1992-10-24 1995-02-28 Degussa Aktiengesellschaft Polyoxymethylene having improved acid stability
US5919849A (en) * 1994-02-15 1999-07-06 Rohm And Haas Company Impact modified polyacetal compositions
US5948844A (en) * 1995-09-29 1999-09-07 Asahi Kasei Kogyo Kabushiki Kaisha Polyacetal resin composition
US6147146A (en) * 1996-11-13 2000-11-14 Asahi Kasei Kogyo Kabushiki Kaisha Resin composition
US20030158301A1 (en) * 1996-12-27 2003-08-21 Hatsuhiko Harashina Polyacetal resin composition and moldings
US6590020B1 (en) * 1998-06-27 2003-07-08 Basf Aktiengesellschaft Stabilized polyoxymethylene moulding materials
US5962623A (en) * 1998-09-08 1999-10-05 Ticona Gmbh Process for the preparation of polyacetal copolymers

Cited By (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080242800A1 (en) * 1999-08-06 2008-10-02 Ticona Gmbh Low-emission colored polyoxymethylene molding composition
US20070123617A1 (en) * 2003-10-01 2007-05-31 Hatsuhiko Harashina Polyacetal resin composition
US20050080185A1 (en) * 2003-10-10 2005-04-14 Mhetar Vijay R. Poly(arylene ether) composition and method of making
US20070078204A1 (en) * 2003-10-24 2007-04-05 Sumio Komatsu Polyacetal resin composition and article thereof
US20090143506A1 (en) * 2003-11-10 2009-06-04 Hatsuhiko Harashina Aldehyde inhibitor composition and polyacetal resin composition
WO2005044916A1 (ja) * 2003-11-10 2005-05-19 Polyplastics Co., Ltd. アルデヒド抑制剤組成物およびポリアセタール樹脂組成物
JP2005137785A (ja) * 2003-11-10 2005-06-02 Polyplastics Co アルデヒド抑制剤組成物およびポリアセタール樹脂組成物
KR101098086B1 (ko) * 2003-11-10 2011-12-26 폴리플라스틱스 가부시키가이샤 알데히드 억제제 조성물 및 폴리아세탈 수지 조성물
US20070276070A1 (en) * 2003-12-22 2007-11-29 Tak-Kyu Kim Poloyoxymethylene Composition Having High Fuel Resistance And Shaped Article Produced Therefrom
WO2007012469A1 (de) 2005-07-28 2007-02-01 Ticona Gmbh Emissionsarme, tribologisch modifizierte polyoxymethylen-formmassen und daraus hergestellte formteile
US20080166544A1 (en) * 2007-01-10 2008-07-10 Airbus Deutschland Gmbh Rear-Illuminable Aircraft Interior Component
US8501311B2 (en) * 2007-01-10 2013-08-06 Airbus Deutschland Gmbh Rear-illuminable aircraft interior component
US20090048388A1 (en) * 2007-08-16 2009-02-19 Elia Andri E Wear resistant toughened and reinforced polyacetal compositions
US8846788B2 (en) 2008-09-03 2014-09-30 Mitsubishi Engineering-Plastics Corporation Polyacetal resin composition, resin molded article, and method and agent for improving polyacetal resin raw material composition
US20110230602A1 (en) * 2008-09-03 2011-09-22 Mitsubishi Engineering-Plastics Corporation Polyacetal resin composition, resin molded article, and method and agent for improving polyacetal resin raw material composition
US20110236276A1 (en) * 2008-10-20 2011-09-29 Stefan Schosnig Analytical test tape instrument
US8383040B2 (en) * 2008-10-20 2013-02-26 Roche Diagnostics Operations, Inc. Analytical test tape instrument
US8110632B2 (en) 2009-01-15 2012-02-07 Sabic Innovative Plastics Ip B.V. Poly(arylene ether) articles and compositions
US20100179290A1 (en) * 2009-01-15 2010-07-15 Christian Lietzau Poly(arylene ether) articles and compositions
US20110034610A1 (en) * 2009-08-07 2011-02-10 Ticona, Llc Low Formaldehyde Emission Polyacetal Composition
US8921471B2 (en) 2009-08-07 2014-12-30 Ticona Llc Low formaldehyde emission polyacetal composition
US8975313B2 (en) 2011-09-29 2015-03-10 Ticona Llc Polymer composition for producing articles having a metallic appearance
US20140179840A1 (en) * 2012-12-26 2014-06-26 Ticona Llc Low Emission, UV Stabilized High Strength Acetal Copolymer
WO2014105758A3 (en) * 2012-12-26 2014-10-16 Ticona Llc Stabilized polymer composition containing an impact modifier
US10738166B2 (en) 2013-11-21 2020-08-11 Polyplastics Co., Ltd. Method for producing polyoxymethylene resin composition
EP3072927A4 (en) * 2013-11-21 2016-12-07 Polyplastics Co METHOD FOR PRODUCING A POLYOXYMETHYLENE RESIN COMPOSITION
CN105001590A (zh) * 2014-04-18 2015-10-28 奕益实业有限公司 用于聚甲醛的无三聚氰胺复合式添加剂
CN107429037A (zh) * 2015-02-25 2017-12-01 三菱化学株式会社 树脂组合物及其成型体
EP3263645A4 (en) * 2015-02-25 2018-02-28 Mitsubishi Chemical Corporation Resin composition and article molded therefrom
US10800901B2 (en) 2015-02-25 2020-10-13 Mitsubishi Chemical Corporation Resin composition and article molded therefrom
US20190040182A1 (en) * 2016-04-13 2019-02-07 Kaneka Corporation Toughened epoxy resin composition
US10947337B2 (en) * 2016-04-13 2021-03-16 Kaneka Corporation Toughened epoxy resin composition
US20190367703A1 (en) * 2018-06-04 2019-12-05 Celanese International Corporation Polyoxymethylene Composition in Food Handling Applications
US12091525B2 (en) * 2018-06-04 2024-09-17 Celanese International Corporation Polyoxymethylene composition in food handling applications

Also Published As

Publication number Publication date
JP2012237009A (ja) 2012-12-06
ES2260283T3 (es) 2006-11-01
AU2001291868A1 (en) 2002-04-08
JP5355763B2 (ja) 2013-11-27
DE50109172D1 (de) 2006-05-04
EP1339794A1 (de) 2003-09-03
WO2002026884A1 (de) 2002-04-04
JP2012237010A (ja) 2012-12-06
EP1325078A1 (de) 2003-07-09
US20080287580A1 (en) 2008-11-20
JP2004522810A (ja) 2004-07-29
ATE348860T1 (de) 2007-01-15
WO2002026885A1 (de) 2002-04-04
US8053499B2 (en) 2011-11-08
DE50111709D1 (de) 2007-02-01
ATE319774T1 (de) 2006-03-15
JP5362165B2 (ja) 2013-12-11
EP1325078B1 (de) 2006-03-08
JP2004510024A (ja) 2004-04-02
EP1339794B1 (de) 2006-12-20
ES2278783T3 (es) 2007-08-16
AU2001289888A1 (en) 2002-04-08

Similar Documents

Publication Publication Date Title
US20030162912A1 (en) Impact-resistant polyoxymethylene moulding compounds with a low emission, the use thereof and moulded bodies produced therefrom
US7829610B2 (en) Impact-resistant polyoxymethylene molding compositions, use thereof and moldings produced therefrom
JPH0615652B2 (ja) 耐衝撃変性されたポリオキシメチレン混合物
JPH07286087A (ja) 安定化変成剤及び耐衝撃性が変性された熱可塑性材料
JPH07316393A (ja) 耐衝撃性改良ポリアセタール組成物
EP3354688B1 (en) Polyacetal resin composition and molded body thereof
US7645821B2 (en) Low-emission, tribologically modified polyoxymethylene molding compositions and moldings produced therefrom
CN101233178B (zh) 低释放、摩擦改性的聚甲醛模制化合物和由其制备的模制品
EP0278349B1 (de) Antistatische, thermoplastische Formmassen auf Basis von Vinylaromatpolymerisaten II
US5047471A (en) Toughened polyoxymethylene and shaped articles produced therefrom
US20040030094A1 (en) Nucleated polyacetal molding materials having increased crystallization speed, their use and shaped molded bodies produced therefrom
KR102855284B1 (ko) 열가소성 수지 조성물, 이의 제조방법 및 이를 포함하는 성형품
KR920002151B1 (ko) 내후성 폴리옥시메틸렌 조성물 및 그의 성형제품
JP4601131B2 (ja) 樹脂組成物及びその成形体
CA2058970A1 (en) Weather-durable polyacetal resin composition
KR102665747B1 (ko) 열가소성 수지 조성물, 이의 제조방법 및 이를 포함하는 성형품
DE10126787A1 (de) Schlagzähe Polyoxymethylen-Formmassen mit geringer Emission, ihre Verwendung und daraus hergestellter Formkörper
JPH05186663A (ja) ポリオキシメチレン組成物及びその使用
JPH02283750A (ja) ポリオキシメチレン塑造成形材料
JP2006291051A (ja) 熱可塑性樹脂組成物および成形品
JPS6261234B2 (enExample)
JPH04213350A (ja) 合成共重合体及びポリアセタールブレンド組成物
DE10209756A1 (de) Polyoxymethylen-Formmasse
JPH0567660B2 (enExample)
JP2006299104A (ja) 熱可塑性樹脂組成物および成形品

Legal Events

Date Code Title Description
AS Assignment

Owner name: TICONA GMBH, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:DISCH, STEFAN;WITAN, KURT;HOFMANN, ERNST;AND OTHERS;REEL/FRAME:013978/0024;SIGNING DATES FROM 20030331 TO 20030407

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION