WO2014181999A1 - Polyoxymethylene composition - Google Patents

Polyoxymethylene composition Download PDF

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Publication number
WO2014181999A1
WO2014181999A1 PCT/KR2014/003840 KR2014003840W WO2014181999A1 WO 2014181999 A1 WO2014181999 A1 WO 2014181999A1 KR 2014003840 W KR2014003840 W KR 2014003840W WO 2014181999 A1 WO2014181999 A1 WO 2014181999A1
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Prior art keywords
weight
polyoxymethylene
parts
aramid
powder
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PCT/KR2014/003840
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French (fr)
Inventor
Seung Chin Park
Hyo Je SEONG
Gyung Seob Byun
Chang Ho Lee
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Korea Engineering Plastics Co.,Ltd
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Publication of WO2014181999A1 publication Critical patent/WO2014181999A1/en

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
    • 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
    • C08K5/20—Carboxylic acid amides
    • 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
    • C08K5/21—Urea; Derivatives thereof, e.g. biuret
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/02—Polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino-carboxylic acids or of polyamines and polycarboxylic acids

Definitions

  • the present invention relates to a polyoxymethylene composition, capable of having excellent thermal stability, reducing formaldehyde, improved tribology property including friction, wear and lubrication properties so as to be usable in an article moving with respect to another component contacting the article itself, and improved hardness.
  • a polyacetal resin has excellent mechanical property, creep resistance, fatigue resistance, and friction and wear properties to be applied to various fields such as not only electrical and electronics and automobiles but also general merchandise, and the like, as an engineering plastic, such that the application range thereof becomes large.
  • a polyoxymethylene polymer has disadvantages in that thermal stability is insufficient and it is easily decomposed by thermal shock, mechanical shock or additives during a molding process.
  • thermal shock mechanical shock
  • additives during a molding process.
  • a degree of decomposition is significant, thereby causing an increase in fragility and processing failure during a molding process.
  • Korean Patent Laid-Open Publication No. 10-2002-0088195 discloses a polyoxymethylene resin composition including (A) 100 parts by weight of polyoxymethylene polymer being a homopolymer or a copolymer of oxymethylene and having a molecular weight of 10,000 to 200,000 g/mol; (B) 0.01 to 5 parts by weight of melamine resin; and (C) 0.01 to 5 parts by weight of polyoxymethylene polyoxypropylene block copolymer having an average molecular weight of 7,000 or more to less than 10,000 and represented by the following Chemical Formula 1 in order to improve thermal stability.
  • A 100 parts by weight of polyoxymethylene polymer being a homopolymer or a copolymer of oxymethylene and having a molecular weight of 10,000 to 200,000 g/mol
  • B 0.01 to 5 parts by weight of melamine resin
  • C 0.01 to 5 parts by weight of polyoxymethylene polyoxypropylene block copolymer having an average molecular weight of 7,000 or more
  • Korean Patent Laid-Open Publication No. 10-2006-0031395 discloses a polyoxymethylene resin composition including (A) 100 parts by weight of polyoxymethylene polymer, (B) 0.005 to 2 parts by weight of amine-substituted triazine compound, (C) 0.01 to 5 parts by weight of compound obtained by grafting 0.05 to 5 wt% maleic anhydride in ethylene-propylene copolymer and ethylene-propylene terpolymer, and (D) 0.001 to 2 parts by weight of 1,12-dodecane dicarboxylic acid dihydrazide.
  • the above-listed Patent Documents are inventions to reduce generation of formaldehyde gas and improve thermal stability; however, tribology property and hardness may not be improved and essential components are different from those of the present invention.
  • Korean Patent Laid-Open Publication No. 10-2010-0085981 discloses a polyacetal composition including (i) a polyacetal resin, (ii) p-aramid particles, and (iii) a vinyl-terminated dimethyl-siloxane polymer, wherein tribology property of the composition are improved.
  • the vinyl-terminated dimethyl-siloxane polymer is not uniformly mixed in compounding due to high viscosity, such that long-term dimensional stability of a molded article is deteriorated, moldability is poor, and compatibility with polyoxymethylene is deteriorated, thereby causing exfoliation phenomenon at the time of injection and extrusion molding process.
  • siloxane is present on a surface of the molded article, such that there is a limitation in silicone-free products when developing application.
  • Patent Document 1 Korean Patent Laid-Open Publication No. KR 10-2002-0088195 (January 27, 2002)
  • Patent Document 2 Korean Patent Laid-Open Publication No. KR 10-2006-0031395 (April 12, 2006)
  • Patent Document 3 Korean Patent Laid-Open Publication No. KR 10-2010-0085981 (July 29, 2010)
  • An object of the present invention is to provide a polyoxymethylene composition capable of having excellent thermal stability, improved tribology property and hardness, excellent long-term dimensional stability, significantly improved mechanical properties including wear resistance, tensile strength, and the like, and improved moldability, of a molded article.
  • a polyoxymethylene composition contains polyoxymethylene, aramid powder, ethylene bis stearamide, and ethylene urea.
  • thermal stability may be excellent, tribology property and hardness may be improved, and long-term dimensional stability, wear resistance, tensile strength, and moldability of a molded article may be excellent, thereby completing the present invention.
  • the tribology property in the present invention indicates a combination of friction, wear, and self-lubrication properties.
  • ethylene bis stearamide and 0.01 to 2 parts by weight of ethylene urea may be contained, based on 100 parts by weight of a resin composition containing 70 to 99 wt% of polyoxymethylene and 1 to 30 wt% of aramid powder.
  • the polyoxymethylene composition may further contain 0.01 to 2 parts by weight of polytetrafluoroethylene powder, ultra high molecular weight polyethylene powder having a weight average molecular weight of 1x10 6 to 5x10 6 g/mol, or mixtures thereof, based on 100 parts by weight of the resin composition.
  • the polyoxymethylene composition according to the present invention may have excellent thermal stability, tribology property, and hardness.
  • the molded article using the polyoxymethylene composition according to the present invention may have excellent long-term dimensional stability and significantly improved moldability.
  • the polyoxymethylene composition according to the present invention may be widely applied to various fields in which thermal resistance, self-lubrication property and moldability are required.
  • An embodiment of the present invention is to provide a polyoxymethylene composition containing polyoxymethylene, aramid powder, ethylene bis stearamide, and ethylene urea.
  • the present invention is to provide a polyoxymethylene composition containing 0.01 to 2 parts by weight of ethylene bis stearamide and 0.01 to 2 parts by weight of ethylene urea, based on 100 parts by weight of a resin composition containing 70 to 99 wt% of polyoxymethylene and 1 to 30 wt% of aramid powder.
  • Another embodiment of the present invention is to provide a polyoxymethylene composition containing polyoxymethylene, aramid powder, ethylene bis stearamide, ethylene urea, and polytetrafluoroethylene powder, ultra high molecular weight polyethylene powder having a weight average molecular weight of 1x10 6 to 5x10 6 g/mol, or mixtures thereof.
  • the present invention is to provide a polyoxymethylene composition containing 0.01 to 2 parts by weight of ethylene bis stearamide, 0.01 to 2 parts by weight of ethylene urea, and 0.01 to 2 parts by weight of polytetrafluoroethylene powder, ultra high molecular weight polyethylene powder having a weight average molecular weight of 1x10 6 to 5x10 6 g/mol, or mixtures thereof, based on 100 parts by weight of a resin composition containing 70 to 99 wt% of polyoxymethylene and 1 to 30 wt% of aramid powder.
  • polyoxymethylene is a polymer having oxymethylene repeating units and may be a homopolymer having oxymethylene repeating units, oxymethylene-oxyalkylene copolymer, or mixtures thereof.
  • the homopolymer may be prepared by polymerizing formaldehyde or a cyclic oligomer thereof, for example, trioxane, and the copolymer may be prepared by polymerizing formaldehyde or a cyclic oligomer thereof with alkylene oxide or a cyclic formal, for example, 1,3-dioxolane, diethyleneglycolformal, 1,4-propanediol formal, 1,4-butanediol formal, 1,3-dioxepan formal, 1,3,6-trioxocane, and the like.
  • one or two or more monomers selected from ethylene oxide, 1,3-dioxolane, 1,4-butanediol formal, and the like, are used, and the monomers are added to trioxane or formaldehyde which is a main monomer and random-copolymerized with a Lewis acid as a catalyst, thereby preparing an oxymethylene copolymer having a melting point of 150°C or more and having two or more bond carbon atoms in a main chain.
  • an amount of the comonomer is 20 wt% or less, preferably, 15 wt% or less, and most preferably, 4 to 5 wt%.
  • the homopolymer or the copolymer may be stabilized by capping by esterification or etherification of end groups thereof.
  • a polyoxymethylene copolymer may be stabilized by obtaining a stabilized copolymer having -CH 2 CH 2 OH end groups through removal of an unstable end-oxymethylene group in accordance with a method disclosed in US Patent No. 3,219,623, which is incorporated herein by reference.
  • the polyoxymethylene used in the composition of the present invention may be branched or linear.
  • a polyoxymethylene homopolymer or oxymethylene-oxyethylene copolymer having a melting point of about 160°C or more, crystallization of 65 to 85%, a weight average molecular weight of from 10,000 to 200,000 g/mole, preferably 20,000 to 90,000 g/mole, and more preferably 25,000 to 70,000 g/mole may be used.
  • the weight average molecular weight may be measured by gel permeation chromatography in an m-cresol using a DuPont PSM bimodal column kit having a nominal pore size of 60 to 1000 ⁇ .
  • a melting flow has a purpose for an injection molding process
  • Various ranges of melting viscosity may be used in other structures and processes such as a film, a fiber, and a blow molding.
  • F10-01, F10-02, F10-03H, F15-33, F20-03, F25-03, F25-03H, F30-03, F40-03, and the like manufactured by KEPITAL Plastics Co., LTD., may be commercially used, but the present invention is not limited thereto.
  • the homopolymer or the copolymer of polyoxymethylene is preferably used in 70 to 99 wt%, preferably, 80 to 95 wt% in the resin composition.
  • a content of polyoxymethylene is less than 70 wt%, thermal stability may be deteriorated, such that polyoxymethylene polymer may be decomposed and mechanical physical properties may be deteriorated.
  • tribology property may be deteriorated.
  • a content of polyoxymethylene is more than 99 wt%, since a content of the used aramid is relatively and significantly small, an effect of improving hardness and tribology may be insignificant.
  • an aramid powder which is used for improving hardness and tribology property, is used by mixing with the polyoxymethylene resin.
  • a content of the aramid powder is preferably 1 to 30 wt%, more preferably, 5 to 20 wt% in the resin composition.
  • a content of an aramid powder is less than 1 wt%, an effect of improving hardness and tribology may be insignificant, and in a case where a content of an aramid powder is more than 30 wt%, cost may be increased, an improved effect according to the use of excessive content thereof may not be expected, and thermal stability of the polyoxymethylene composition may be deteriorated, such that polyoxymethylene polymer may be decomposed and mechanical physical properties may be deteriorated.
  • aramid particles having a para structure in which the following Chemical formula I is repeated may be used as the aramid powder.
  • the aramid particle having a para structure may be preferably used in the polyoxymethylene composition due to excellent thermal resistance, high strength, high elasticity, flame retardance, and the like.
  • poly (p-phenylene terephthalate) particle may be used as the aramid particle.
  • poly(p-phenylene terephthalate) a homopolymer prepared by mol-to-mol polymerization of p-phenylene diamine and terephthaloyl chloride and a copolymer prepared by polymerizaiton of diamine including p-phenylene diamine and diacid chloride including terephthaloyl chloride may be used.
  • Teijin Aramid Twaron 5011 Grade, Hyosung Company Aramid, and the like may be commercially used, but the present invention is not limited thereto.
  • the aramid powder is not limited to any specific shape, but for example, may have a single fiber, fibril, fibrid, non-uniform, sphere, disc shape, and the like.
  • the aramid powder particle has an average particle size of 0.1 to 500 ⁇ m, more preferably, 0.1 to 200 ⁇ m. In a case where the aramid powder has an average particle size more than 500 ⁇ m, tribology property and mechanical physical properties, and the like, may not be uniformly implemented, and may be unfavorable in view of thermal stability of polyoxymethylene and surface roughness of a molded article.
  • the aramid powder particle may be prepared by pulverizing a non-radiative aramid polymer with a desired size.
  • ethylene bis stearamide is used for decreasing shear stress at the time of a compounding process to improve thermal stability and tribology property of the composition.
  • a content of ethylene bis stearamide is preferably 0.01 to 2 parts by weight, more preferably, 0.1 to 1.0 part by weight, based on 100 parts by weight of a resin composition containing a polyoxymethylene resin and an aramid powder.
  • a content of ethylene bis stearamide is less than 0.01 parts by weight, the above-described effect is insignificant, and in a case where a content of ethylene bis stearamide is more than 2 parts by weight, mechanical physical properties may be deteriorated, exfoliation may occur on a surface of a molded article, and additional improvement effect may be insignificant, such that ethylene bis stearamide is preferably used in the above-described range.
  • ethylene urea may be 2-imidazolidone or imidazolidin-2-on, and by adding ethylene urea to the composition of the present invention, surprisingly, thermal resistance may be significantly improved, and a tissue of a specimen in processing may be uniform, thereby improving moldability, long-term dimensional stability and mechanical physical properties, and reducing emission amount of formaldehyde to remarkably improve thermal stability.
  • ethylene urea a material industrially obtained by reaction with 1,2-ethylenediamine and urea may be used. Flake, pellet, or particle shape thereof may be used.
  • Ethylene urea is preferably used in 0.01 to 2 parts by weight, more preferably, 0.2 to 1.0 part by weight, based on 100 parts by weight of a resin composition containing a polyoxymethylene resin and an aramid powder.
  • ethylene urea is used less than 0.01 parts by weight, the above-described effect may be insignificant, and even though ethylene urea is used more than 2 parts by weight, the effect is not increased, which is not economical.
  • polytetrafluoroethylene which is used for more improving friction, wear and lubrication properties, may be further added thereto, as needed.
  • an ultra high molecular weight polyethylene powder may be used as needed, and in a case of adding the powder, surprisingly, surface properties of a molded article may be significantly improved, and wear resistance and mechanical strength, particularly, tensile strength may be improved, thereby completing the present invention.
  • the ultra high molecular weight polyethylene powder is a particle having a weight average molecular weight of 1X10 6 to 5X10 6 g/mol and an average particle size of 50 to 300 ⁇ m.
  • the average particle size is more than 300 ⁇ m, wear resistance may be deteriorated, and wear resistance and mechanical strength may be improved within the above-described range.
  • ultra high molecular weight polyethylene powder Hostalen GUR 4113 ® Ticona GmbH, Germany), and the like, may be commercially used, but the present invention is not limited thereto.
  • the polytetrafluoroethylene, the ultra high molecular weight polyethylene powder, or mixtures thereof is preferably used in 0.01 to 2 parts by weight, more preferably, 0.1 to 1.0 part by weight, based on 100 parts by weight of a resin composition containing a polyoxymethylene resin and an aramid powder.
  • polytetrafluoroethylene, ultra high molecular weight polyethylene powder, or mixtures thereof is used less than 0.01 parts by weight, the above-described effect may be insignificant, and even though it is used more than 2.0 parts by weight, physical properties more improved than those of the above description may not be expected, which is not economical.
  • additives used in the conventionally corresponding field may be further added, as needed.
  • examples of other additives may include antioxidant, formaldehyde or formic acid remover, end group stabilizer, filler, colorant, lubricant, release agent, antistatic agent, flame retardant, reinforcing agent, light stabilizer, pigment, and the like.
  • the additives may be used within a content range in which physical properties of the composition of the present invention is not negatively and substantially affected.
  • examples of the antioxidant include a sterically hindered bisphenol, more preferably, tetra-bis [methylene (3,5-di-t-butyl-4-hydrocinnamate)] methane, Irganox 1010 as a trade name from Ciba-Geigy Corporation.
  • a nitrogen-based compound may be used, wherein examples of the nitrogen-based compound include at least one or two kinds of compounds selected from a reactive hot melt nylon resin containing amine groups at the end thereof or a non-reactive hot melt nylon without a reaction group at an end thereof, and a low molecular weight amine-based compound.
  • the nitrogen-based compound any one selected from a hot melt nylon resin, a nylon resin and a low molecular weight amine-based compound may be used; however, a low molecular weight amine-based compound having a melting point of 230°C or less may be appropriate.
  • the low molecular weight amine-based compound a compound selected from triazines, hydrazines, ureas, dicyandiamide, and the like, wherein examples of triazines include melamine, acetoguanamine, acryloguanamine, benzoguanamine, and the like, and examples of hydrazines include adipic acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, naphthalic acid dihydrazide, and the like, and examples of ureas include urea, thiourea, and the like. One kind alone or a combination of two or more thereof may be used.
  • a glass fiber As a filler, a glass fiber, a glass flake, a glass bead, talc, mica, potassium titanate, whisker, and the like, may be used.
  • the polyoxymethylene composition of the present invention is a melted and mixed blend, wherein all polymer components are well dispersed, and every non-polymer components are well dispersed into the polymer matrix to be mixed with each other, thereby forming an integrated blend as a whole body.
  • the polyoxymethylene composition of the present invention may be prepared by performing a blending process using a conventional mixer, for example, Brabender mixer and then performing a melt-kneading process on the blend at a temperature range higher than a melting point of a polyoxymethylene-based resin, for example, at 180 to 230°C, preferably, 190 to 210°C, using a conventional single axis or twin axis extruder. Before the blending process, it is preferred to dry each component. The drying may be performed at 70 to 110°C for 2 to 6 hours, using a dried air having a temperature of about -30 to -40°C.
  • Molded articles manufactured by using the polyoxymethylene composition of the present invention may be manufactured by any well-known methods by a person skilled in the art, for example, extrusion, injection molding, compression molding, blow molding, thermal molding, rotational molding, and melting casting.
  • Examples of the molded articles may include bearing, gear, cam, roller, sliding plate, lever, guide, conveyor component.
  • This measurement is a method for measuring an emission amount of formaldehyde generated from components and molded articles using polyoxymethylene composition, wherein the emission amount of formaldehyde among volatile organic compounds (VOCs) was tested the next day after a test specimen was molded, in accordance with German Automobile Industrial Association Standard VDA275 (automobile interior parts - Quantitative measurement of emission amount of formaldehyde by revised flask method). The higher the numerical value is, the worse the thermal stability is.
  • An emission amount of formaldehyde satisfies the required level at a range of 0.1 ⁇ 500mg/kg.
  • Hardness of test specimen was measured in accordance with ISO 2039-2 test method.
  • a specimen having a ring shape was mounted on a tester and rotated with a selected and predetermined load and rate, and the amount of applied power and wear loss accordingly were evaluated and friction and wear properties were analyzed.
  • the specimen having a ring shape is made of plastic materials and metals (S45C, copper, SUS, and the like), and as needed, is made of other materials. Tribology property was measured at a load of 0.1 kgf to 500 kgf and a rate of 1mm/sec to 1000 mm/sec.
  • a molding shrinkage was measured by ASTM D955 method.
  • the mixture was introduced into a hopper of a twin screw compounding machine(JSW Co., Ltd.) (Japan) to be subjected to a compounding process.
  • a screw rate was 180 rpm and a temperature was 190°C.
  • Thus prepared resin composition was injected through an injection molder (Fanac Co., Ltd., electric injection machine and injection rate: 20 mm/s, injection pressure 700 kgf, measurement: 50 mm, cooling time: 10 sec, and mold temperature: 80°C) and molded as a sample.
  • the mixture was introduced into a hopper of a twin screw compounding machine(JSW Co., Ltd.) (Japan) to be subjected to a compounding process.
  • a screw rate was 180 rpm and a temperature was 190°C.
  • Thus prepared resin composition was injected through an injection molder (Fanac Co., Ltd., electric injection machine and injection rate: 20 mm/s, injection pressure 700 kgf, measurement: 50 mm, cooling time: 10 sec, and mold temperature: 80°C) and molded as a sample.
  • the mixture was introduced into a hopper of a twin screw compounding machine(JSW Co., Ltd.) (Japan) to be subjected to a compounding process.
  • a screw rate was 180 rpm and a temperature was 190°C.
  • Thus prepared resin composition was injected through an injection molder (Fanac Co., Ltd., electric injection machine and injection rate: 20 mm/s, injection pressure 700 kgf, measurement: 50 mm, cooling time: 10 sec, and mold temperature: 80°C) and molded as a sample.
  • the mixture was introduced into a hopper of a twin screw compounding machine(JSW Co., Ltd.) (Japan) to be subjected to a compounding process.
  • a screw rate was 180 rpm and a temperature was 190°C.
  • Thus prepared resin composition was injected through an injection molder (Fanac Co., Ltd., electric injection machine and injection rate: 20 mm/s, injection pressure 700 kgf, measurement: 50 mm, cooling time: 10 sec, and mold temperature: 80°C) and molded as a sample.
  • a resin composition containing 95 wt% of polyoxymethylene (KEPITAL Plastics Co., LTD. F10-03H) and 5 wt% of aramid powder (Teijin Aramid, Twaron 5011, average particle size 100 ⁇ m) 0.2 parts by weight of EBS, 0.2 parts by weight of ethylene urea,
  • the mixture was introduced into a hopper of a twin screw compounding machine(JSW Co., Ltd.) (Japan) to be subjected to a compounding process.
  • a screw rate was 180 rpm and a temperature was 190°C.
  • Thus prepared resin composition was injected through an injection molder (Fanac Co., Ltd., electric injection machine and injection rate: 20 mm/s, injection pressure 700 kgf, measurement: 50 mm, cooling time: 10 sec, and mold temperature: 80°C) and molded as a sample.
  • a resin composition containing 95 wt% of polyoxymethylene (KEPITAL Plastics Co., LTD. F10-03H) and 5 wt% of aramid powder (Teijin Aramid, Twaron 5011, average particle size 100 ⁇ m) 0.2 parts by weight of EBS, 0.2 parts by weight of ethylene urea,
  • the mixture was introduced into a hopper of a twin screw compounding machine(JSW Co., Ltd.) (Japan) to be subjected to a compounding process.
  • a screw rate was 180 rpm and a temperature was 190°C.
  • Thus prepared resin composition was injected through an injection molder (Fanac Co., Ltd., electric injection machine and injection rate: 20 mm/s, injection pressure 700 kgf, measurement: 50 mm, cooling time: 10 sec, and mold temperature: 80°C) and molded as a sample.
  • Examples 7 and 8 were conducted as the same as Example 1 above except for changing each content of EBS and ethylene urea of Example 1.
  • PTFE ultrahigh molecular weight polyethylene powder
  • the mixture was introduced into a hopper of a twin screw compounding machine(JSW Co., Ltd.) (Japan) to be subjected to a compounding process.
  • a screw rate was 180 rpm and a temperature was 190°C.
  • Thus prepared resin composition was injected through an injection molder (Fanac Co., Ltd., electric injection machine and injection rate: 20 mm/s, injection pressure 700 kgf, measurement: 50 mm, cooling time: 10 sec, and mold temperature: 80°C) and molded as a sample.
  • PTFE ultrahigh molecular weight polyethylene powder
  • the mixture was introduced into a hopper of a twin screw compounding machine(JSW Co., Ltd.) (Japan) to be subjected to a compounding process.
  • a screw rate was 180 rpm and a temperature was 190°C.
  • Thus prepared resin composition was injected through an injection molder (Fanac Co., Ltd., electric injection machine and injection rate: 20 mm/s, injection pressure 700 kgf, measurement: 50 mm, cooling time: 10 sec, and mold temperature: 80°C) and molded as a sample.
  • EBS ethylene bis stearamide
  • the mixture was introduced into a hopper of a twin screw compounding machine(JSW Co., Ltd.) (Japan) to be subjected to a compounding process.
  • a screw rate was 180 rpm and a temperature was 190°C.
  • Thus prepared resin composition was injected through an injection molder (Fanac Co., Ltd., electric injection machine and injection rate: 20 mm/s, injection pressure 700 kgf, measurement: 50 mm, cooling time: 10 sec, and mold temperature: 80°C) and molded as a sample.
  • the mixture was introduced into a hopper of a twin screw compounding machine(JSW Co., Ltd.) (Japan) to be subjected to a compounding process.
  • a screw rate was 180 rpm and a temperature was 190°C.
  • Thus prepared resin composition was injected through an injection molder (Fanac Co., Ltd., electric injection machine and injection rate: 20 mm/s, injection pressure 700 kgf, measurement: 50 mm, cooling time: 10 sec, and mold temperature: 80°C) and molded as a sample.
  • the mixture was introduced into a hopper of a twin screw compounding machine(JSW Co., Ltd.) (Japan) to be subjected to a compounding process.
  • a screw rate was 180 rpm and a temperature was 190°C.
  • Thus prepared resin composition was injected through an injection molder (Fanac Co., Ltd., electric injection machine and injection rate: 20 mm/s, injection pressure 700 kgf, measurement: 50 mm, cooling time: 10 sec, and mold temperature: 80°C) and molded as a sample.
  • Example 1 Polyoxymethylene(wt%) Aramid(wt%) EBS(Part by Weight) Ethylene Urea (Part by Weight) Antioxidant (Part by Weight) PTFE(Part by Weight) UHMWPE(Part by Weight)
  • the polyoxymethylene composition according to the present invention had significantly low emission amount of formaldehyde, excellent hardness, and significantly improved tribology property.
  • Example 1 63 11 90 2860 Excellent 1100 1.8%
  • Example 2 63 11 90 2860 Excellent 1160 1.7%
  • Example 3 80 15 95 2980 Excellent 1110 1.8%
  • Example 4 50 6 76 1870 Excellent 1106 1.7%
  • Example 5 65 13 92 2980 Excellent 1180 1.5%
  • Example 6 72 15 95 3200 Excellent 1200 1.3%
  • Example 7 63 11 80 2860 Excellent 1100 1.8%
  • Example 8 63 12 90 2860 Excellent 1100 1.8%
  • Example 9 64 13 92 2970 Excellent 1150 1.5%
  • Example 10 70 13 94 2985 Excellent 1160 1.4%
  • Comparative Example 1 63 11 90 2860 Defective 500 3.0% Comparative Example 2 62 11 89 2850 Defective 490 3.0% Comparative Example 3 60 10 87 2730 Defective 450 3.1%

Abstract

Provided is a polyoxymethylene composition capable of having excellent thermal stability, reducing formaldehyde, improved tribology property including friction, wear and lubrication properties so as to be usable in an article moving with respect to another component contacting the article itself, and improved hardness.

Description

POLYOXYMETHYLENE COMPOSITION
The present invention relates to a polyoxymethylene composition, capable of having excellent thermal stability, reducing formaldehyde, improved tribology property including friction, wear and lubrication properties so as to be usable in an article moving with respect to another component contacting the article itself, and improved hardness.
A polyacetal resin has excellent mechanical property, creep resistance, fatigue resistance, and friction and wear properties to be applied to various fields such as not only electrical and electronics and automobiles but also general merchandise, and the like, as an engineering plastic, such that the application range thereof becomes large.
However, a polyoxymethylene polymer has disadvantages in that thermal stability is insufficient and it is easily decomposed by thermal shock, mechanical shock or additives during a molding process. In particular, in a case of using colorant (pigment) of additives, a degree of decomposition is significant, thereby causing an increase in fragility and processing failure during a molding process.
Accordingly, in order to improve thermal stability of polyoxymethylene, various methods have been suggested, for example, Korean Patent Laid-Open Publication No. 10-2002-0088195 (November 27, 2002) discloses a polyoxymethylene resin composition including (A) 100 parts by weight of polyoxymethylene polymer being a homopolymer or a copolymer of oxymethylene and having a molecular weight of 10,000 to 200,000 g/mol; (B) 0.01 to 5 parts by weight of melamine resin; and (C) 0.01 to 5 parts by weight of polyoxymethylene polyoxypropylene block copolymer having an average molecular weight of 7,000 or more to less than 10,000 and represented by the following Chemical Formula 1 in order to improve thermal stability. In addition, Korean Patent Laid-Open Publication No. 10-2006-0031395 (April 12, 2006) discloses a polyoxymethylene resin composition including (A) 100 parts by weight of polyoxymethylene polymer, (B) 0.005 to 2 parts by weight of amine-substituted triazine compound, (C) 0.01 to 5 parts by weight of compound obtained by grafting 0.05 to 5 wt% maleic anhydride in ethylene-propylene copolymer and ethylene-propylene terpolymer, and (D) 0.001 to 2 parts by weight of 1,12-dodecane dicarboxylic acid dihydrazide. The above-listed Patent Documents are inventions to reduce generation of formaldehyde gas and improve thermal stability; however, tribology property and hardness may not be improved and essential components are different from those of the present invention.
In addition, Korean Patent Laid-Open Publication No. 10-2010-0085981 (July 29, 2010) discloses a polyacetal composition including (i) a polyacetal resin, (ii) p-aramid particles, and (iii) a vinyl-terminated dimethyl-siloxane polymer, wherein tribology property of the composition are improved. However, the vinyl-terminated dimethyl-siloxane polymer is not uniformly mixed in compounding due to high viscosity, such that long-term dimensional stability of a molded article is deteriorated, moldability is poor, and compatibility with polyoxymethylene is deteriorated, thereby causing exfoliation phenomenon at the time of injection and extrusion molding process. In addition, at the time of molding the composition, siloxane is present on a surface of the molded article, such that there is a limitation in silicone-free products when developing application.
[Related Art Document]
(Patent Document 1) Korean Patent Laid-Open Publication No. KR 10-2002-0088195 (November 27, 2002)
(Patent Document 2) Korean Patent Laid-Open Publication No. KR 10-2006-0031395 (April 12, 2006)
(Patent Document 3) Korean Patent Laid-Open Publication No. KR 10-2010-0085981 (July 29, 2010)
An object of the present invention is to provide a polyoxymethylene composition capable of having excellent thermal stability, improved tribology property and hardness, excellent long-term dimensional stability, significantly improved mechanical properties including wear resistance, tensile strength, and the like, and improved moldability, of a molded article.
In one general aspect, a polyoxymethylene composition contains polyoxymethylene, aramid powder, ethylene bis stearamide, and ethylene urea. The present inventors surprisingly found that in a case of mixing the components to be used, thermal stability may be excellent, tribology property and hardness may be improved, and long-term dimensional stability, wear resistance, tensile strength, and moldability of a molded article may be excellent, thereby completing the present invention.
The tribology property in the present invention indicates a combination of friction, wear, and self-lubrication properties.
In addition, 0.01 to 2 parts by weight of ethylene bis stearamide and 0.01 to 2 parts by weight of ethylene urea may be contained, based on 100 parts by weight of a resin composition containing 70 to 99 wt% of polyoxymethylene and 1 to 30 wt% of aramid powder.
Further, the polyoxymethylene composition may further contain 0.01 to 2 parts by weight of polytetrafluoroethylene powder, ultra high molecular weight polyethylene powder having a weight average molecular weight of 1x106 to 5x106g/mol, or mixtures thereof, based on 100 parts by weight of the resin composition.
The polyoxymethylene composition according to the present invention may have excellent thermal stability, tribology property, and hardness.
In addition, the molded article using the polyoxymethylene composition according to the present invention may have excellent long-term dimensional stability and significantly improved moldability.
Therefore, it is expected that the polyoxymethylene composition according to the present invention may be widely applied to various fields in which thermal resistance, self-lubrication property and moldability are required.
Hereinafter, a polyoxymethylene composition according to a preferred exemplary embodiment of the present invention will be specifically described. The following Examples are given by way of illustration but are not intended to limit the protective scope defined by the attached claims of the present invention.
An embodiment of the present invention is to provide a polyoxymethylene composition containing polyoxymethylene, aramid powder, ethylene bis stearamide, and ethylene urea.
More specifically, the present invention is to provide a polyoxymethylene composition containing 0.01 to 2 parts by weight of ethylene bis stearamide and 0.01 to 2 parts by weight of ethylene urea, based on 100 parts by weight of a resin composition containing 70 to 99 wt% of polyoxymethylene and 1 to 30 wt% of aramid powder.
Another embodiment of the present invention is to provide a polyoxymethylene composition containing polyoxymethylene, aramid powder, ethylene bis stearamide, ethylene urea, and polytetrafluoroethylene powder, ultra high molecular weight polyethylene powder having a weight average molecular weight of 1x106 to 5x106g/mol, or mixtures thereof.
More specifically, the present invention is to provide a polyoxymethylene composition containing 0.01 to 2 parts by weight of ethylene bis stearamide, 0.01 to 2 parts by weight of ethylene urea, and 0.01 to 2 parts by weight of polytetrafluoroethylene powder, ultra high molecular weight polyethylene powder having a weight average molecular weight of 1x106 to 5x106g/mol, or mixtures thereof, based on 100 parts by weight of a resin composition containing 70 to 99 wt% of polyoxymethylene and 1 to 30 wt% of aramid powder.
Hereinafter, each component of the present invention will be described in detail.
(A) Polyoxymethylene
In an embodiment of the present invention, polyoxymethylene (POM or polyacetal) is a polymer having oxymethylene repeating units and may be a homopolymer having oxymethylene repeating units, oxymethylene-oxyalkylene copolymer, or mixtures thereof.
The homopolymer may be prepared by polymerizing formaldehyde or a cyclic oligomer thereof, for example, trioxane, and the copolymer may be prepared by polymerizing formaldehyde or a cyclic oligomer thereof with alkylene oxide or a cyclic formal, for example, 1,3-dioxolane, diethyleneglycolformal, 1,4-propanediol formal, 1,4-butanediol formal, 1,3-dioxepan formal, 1,3,6-trioxocane, and the like.
Preferably, one or two or more monomers selected from ethylene oxide, 1,3-dioxolane, 1,4-butanediol formal, and the like, are used, and the monomers are added to trioxane or formaldehyde which is a main monomer and random-copolymerized with a Lewis acid as a catalyst, thereby preparing an oxymethylene copolymer having a melting point of 150℃ or more and having two or more bond carbon atoms in a main chain. In a case of using the copolymer, an amount of the comonomer is 20 wt% or less, preferably, 15 wt% or less, and most preferably, 4 to 5 wt%.
The homopolymer or the copolymer may be stabilized by capping by esterification or etherification of end groups thereof. A polyoxymethylene copolymer may be stabilized by obtaining a stabilized copolymer having -CH2CH2OH end groups through removal of an unstable end-oxymethylene group in accordance with a method disclosed in US Patent No. 3,219,623, which is incorporated herein by reference.
The polyoxymethylene used in the composition of the present invention may be branched or linear. In addition, a polyoxymethylene homopolymer or oxymethylene-oxyethylene copolymer having a melting point of about 160℃ or more, crystallization of 65 to 85%, a weight average molecular weight of from 10,000 to 200,000 g/mole, preferably 20,000 to 90,000 g/mole, and more preferably 25,000 to 70,000 g/mole may be used. The weight average molecular weight may be measured by gel permeation chromatography in an m-cresol using a DuPont PSM bimodal column kit having a nominal pore size of 60 to 1000 Å.
In a case where a melting flow has a purpose for an injection molding process, it is preferred to have a range of 0.1 to 100 g/min, preferably, 0.5 to 60 g/min, or more preferably, 0.8 to 40 g/min. Various ranges of melting viscosity may be used in other structures and processes such as a film, a fiber, and a blow molding.
As the polyoxymethylene, F10-01, F10-02, F10-03H, F15-33, F20-03, F25-03, F25-03H, F30-03, F40-03, and the like, manufactured by KEPITAL Plastics Co., LTD., may be commercially used, but the present invention is not limited thereto.
In an embodiment of the present invention, the homopolymer or the copolymer of polyoxymethylene is preferably used in 70 to 99 wt%, preferably, 80 to 95 wt% in the resin composition. In a case of where a content of polyoxymethylene is less than 70 wt%, thermal stability may be deteriorated, such that polyoxymethylene polymer may be decomposed and mechanical physical properties may be deteriorated. In addition, tribology property may be deteriorated. In a case of where a content of polyoxymethylene is more than 99 wt%, since a content of the used aramid is relatively and significantly small, an effect of improving hardness and tribology may be insignificant.
(B) Aramid Powder
In an embodiment of the present invention, an aramid powder, which is used for improving hardness and tribology property, is used by mixing with the polyoxymethylene resin. Here, a content of the aramid powder is preferably 1 to 30 wt%, more preferably, 5 to 20 wt% in the resin composition. In a case where a content of an aramid powder is less than 1 wt%, an effect of improving hardness and tribology may be insignificant, and in a case where a content of an aramid powder is more than 30 wt%, cost may be increased, an improved effect according to the use of excessive content thereof may not be expected, and thermal stability of the polyoxymethylene composition may be deteriorated, such that polyoxymethylene polymer may be decomposed and mechanical physical properties may be deteriorated.
In an embodiment of the present invention, as the aramid powder, aramid particles having a para structure in which the following Chemical formula I is repeated, may be used. The aramid particle having a para structure may be preferably used in the polyoxymethylene composition due to excellent thermal resistance, high strength, high elasticity, flame retardance, and the like.
[Chemical Formula 1]
Figure PCTKR2014003840-appb-I000001
Preferably, poly (p-phenylene terephthalate) particle may be used as the aramid particle. As the poly(p-phenylene terephthalate), a homopolymer prepared by mol-to-mol polymerization of p-phenylene diamine and terephthaloyl chloride and a copolymer prepared by polymerizaiton of diamine including p-phenylene diamine and diacid chloride including terephthaloyl chloride may be used.
As the aramid resin having a para structure, Teijin Aramid Twaron 5011 Grade, Hyosung Company Aramid, and the like, may be commercially used, but the present invention is not limited thereto.
The aramid powder is not limited to any specific shape, but for example, may have a single fiber, fibril, fibrid, non-uniform, sphere, disc shape, and the like.
The aramid powder particle has an average particle size of 0.1 to 500㎛, more preferably, 0.1 to 200㎛. In a case where the aramid powder has an average particle size more than 500㎛, tribology property and mechanical physical properties, and the like, may not be uniformly implemented, and may be unfavorable in view of thermal stability of polyoxymethylene and surface roughness of a molded article.
The aramid powder particle may be prepared by pulverizing a non-radiative aramid polymer with a desired size.
(C) Ethylene Bis Stearamide
In an embodiment of the present invention, ethylene bis stearamide is used for decreasing shear stress at the time of a compounding process to improve thermal stability and tribology property of the composition.
A content of ethylene bis stearamide is preferably 0.01 to 2 parts by weight, more preferably, 0.1 to 1.0 part by weight, based on 100 parts by weight of a resin composition containing a polyoxymethylene resin and an aramid powder. In a case where a content of ethylene bis stearamide is less than 0.01 parts by weight, the above-described effect is insignificant, and in a case where a content of ethylene bis stearamide is more than 2 parts by weight, mechanical physical properties may be deteriorated, exfoliation may occur on a surface of a molded article, and additional improvement effect may be insignificant, such that ethylene bis stearamide is preferably used in the above-described range.
(D) Ethylene Urea
In an embodiment of the present invention, ethylene urea may be 2-imidazolidone or imidazolidin-2-on, and by adding ethylene urea to the composition of the present invention, surprisingly, thermal resistance may be significantly improved, and a tissue of a specimen in processing may be uniform, thereby improving moldability, long-term dimensional stability and mechanical physical properties, and reducing emission amount of formaldehyde to remarkably improve thermal stability.
As ethylene urea, a material industrially obtained by reaction with 1,2-ethylenediamine and urea may be used. Flake, pellet, or particle shape thereof may be used.
Ethylene urea is preferably used in 0.01 to 2 parts by weight, more preferably, 0.2 to 1.0 part by weight, based on 100 parts by weight of a resin composition containing a polyoxymethylene resin and an aramid powder. In a case where ethylene urea is used less than 0.01 parts by weight, the above-described effect may be insignificant, and even though ethylene urea is used more than 2 parts by weight, the effect is not increased, which is not economical.
(E) Polytetrafluoroethylene (PTFE) and Ultra High Molecular Weight Polyethylene Powder
In an embodiment of the present invention, polytetrafluoroethylene (PTFE), which is used for more improving friction, wear and lubrication properties, may be further added thereto, as needed.
In an embodiment of the present invention, an ultra high molecular weight polyethylene powder may be used as needed, and in a case of adding the powder, surprisingly, surface properties of a molded article may be significantly improved, and wear resistance and mechanical strength, particularly, tensile strength may be improved, thereby completing the present invention.
It is preferred that the ultra high molecular weight polyethylene powder is a particle having a weight average molecular weight of 1X106 to 5X106 g/mol and an average particle size of 50 to 300㎛. In a case where the average particle size is more than 300㎛, wear resistance may be deteriorated, and wear resistance and mechanical strength may be improved within the above-described range.
As the ultra high molecular weight polyethylene powder, Hostalen GUR 4113®Ticona GmbH, Germany), and the like, may be commercially used, but the present invention is not limited thereto.
The polytetrafluoroethylene, the ultra high molecular weight polyethylene powder, or mixtures thereof is preferably used in 0.01 to 2 parts by weight, more preferably, 0.1 to 1.0 part by weight, based on 100 parts by weight of a resin composition containing a polyoxymethylene resin and an aramid powder. In a case where polytetrafluoroethylene, ultra high molecular weight polyethylene powder, or mixtures thereof is used less than 0.01 parts by weight, the above-described effect may be insignificant, and even though it is used more than 2.0 parts by weight, physical properties more improved than those of the above description may not be expected, which is not economical.
(F) Other Additives
In an embodiment of the present invention, additives used in the conventionally corresponding field may be further added, as needed. Specifically, examples of other additives may include antioxidant, formaldehyde or formic acid remover, end group stabilizer, filler, colorant, lubricant, release agent, antistatic agent, flame retardant, reinforcing agent, light stabilizer, pigment, and the like. The additives may be used within a content range in which physical properties of the composition of the present invention is not negatively and substantially affected.
Specifically, examples of the antioxidant include a sterically hindered bisphenol, more preferably, tetra-bis [methylene (3,5-di-t-butyl-4-hydrocinnamate)] methane, Irganox 1010 as a trade name from Ciba-Geigy Corporation.
As the end group stabilizer, a nitrogen-based compound may be used, wherein examples of the nitrogen-based compound include at least one or two kinds of compounds selected from a reactive hot melt nylon resin containing amine groups at the end thereof or a non-reactive hot melt nylon without a reaction group at an end thereof, and a low molecular weight amine-based compound. As the nitrogen-based compound, any one selected from a hot melt nylon resin, a nylon resin and a low molecular weight amine-based compound may be used; however, a low molecular weight amine-based compound having a melting point of 230℃ or less may be appropriate. Meanwhile, as the low molecular weight amine-based compound, a compound selected from triazines, hydrazines, ureas, dicyandiamide, and the like, wherein examples of triazines include melamine, acetoguanamine, acryloguanamine, benzoguanamine, and the like, and examples of hydrazines include adipic acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, naphthalic acid dihydrazide, and the like, and examples of ureas include urea, thiourea, and the like. One kind alone or a combination of two or more thereof may be used.
As a filler, a glass fiber, a glass flake, a glass bead, talc, mica, potassium titanate, whisker, and the like, may be used.
The polyoxymethylene composition of the present invention is a melted and mixed blend, wherein all polymer components are well dispersed, and every non-polymer components are well dispersed into the polymer matrix to be mixed with each other, thereby forming an integrated blend as a whole body.
The polyoxymethylene composition of the present invention may be prepared by performing a blending process using a conventional mixer, for example, Brabender mixer and then performing a melt-kneading process on the blend at a temperature range higher than a melting point of a polyoxymethylene-based resin, for example, at 180 to 230℃, preferably, 190 to 210℃, using a conventional single axis or twin axis extruder. Before the blending process, it is preferred to dry each component. The drying may be performed at 70 to 110℃ for 2 to 6 hours, using a dried air having a temperature of about -30 to -40℃.
Molded articles manufactured by using the polyoxymethylene composition of the present invention may be manufactured by any well-known methods by a person skilled in the art, for example, extrusion, injection molding, compression molding, blow molding, thermal molding, rotational molding, and melting casting. Examples of the molded articles may include bearing, gear, cam, roller, sliding plate, lever, guide, conveyor component.
Hereinafter, although Examples of the present invention have been disclosed for illustrative purposes in detail, the present invention is not limited to the following Examples.
Physical properties were measured by the following measurement.
1) Measurement of Emission Amount of Formaldehyde
This measurement is a method for measuring an emission amount of formaldehyde generated from components and molded articles using polyoxymethylene composition, wherein the emission amount of formaldehyde among volatile organic compounds (VOCs) was tested the next day after a test specimen was molded, in accordance with German Automobile Industrial Association Standard VDA275 (automobile interior parts - Quantitative measurement of emission amount of formaldehyde by revised flask method). The higher the numerical value is, the worse the thermal stability is.
(i) 50 ㎖ of distilled water was added to a polyethylene vessel, a lid thereof was closed in such a state that the test specimen was hung in the air, and the vessel was heated in a sealed state at 60℃ for 3 hours.
(ii) After the vessel was left at room temperature for 60 minutes, the test specimen was taken out.
(iii) An amount of formaldehyde absorbed into distilled water in the polyethylene vessel was pre-treated by acetylacetone colorimetry using a UV spectrometer and measured by an ultraviolet spectrometer.
(Acetylacetone Colorimetry: Formaldehyde reacts with ammonium ion and acetylaceton to form 2,5-diacety-1,4-dihydrolutidin(DDL), wherein DDL is a material showing the maximum absorption wavelength at UV 412nm.)
An emission amount of formaldehyde satisfies the required level at a range of 0.1 ~ 500mg/kg.
2) Hardness
Hardness of test specimen was measured in accordance with ISO 2039-2 test method.
3) Tribology Property
Physical properties were measured in accordance with JIS K7218 method.
A specimen having a ring shape was mounted on a tester and rotated with a selected and predetermined load and rate, and the amount of applied power and wear loss accordingly were evaluated and friction and wear properties were analyzed. The specimen having a ring shape is made of plastic materials and metals (S45C, copper, SUS, and the like), and as needed, is made of other materials. Tribology property was measured at a load of 0.1 kgf to 500 kgf and a rate of 1mm/sec to 1000 mm/sec.
1. Evaluation Conditions of Ring-on-Ring: Relative Material=Metal (S45C), Load=11.8 kgf, Rate=300mm/s, Time=120m
2. Evaluation Conditions of Pin-on-Disk: Relative Material=Same Resin, Load=2kgf, Rate=2Hz, Time=30min
(1) Coefficient of Kinetic Friction
Power applied by friction between two materials was calculated as a coefficient of kinetic friction.
(2) Specific Wear Amount
After measuring weight of the initial test specimen and the molded test specimen, difference in weight was calculated as a specific wear amount.
(3) Lubrication
Noise (db) was measured.
(4) Tensile Strength and Tensile Elongation
Tensile strength and tensile elongation thereof were measured by UTM(United STM-10, USA) in accordance with ISO527.
(5) Flexural Strength and Flexural Modulus
Flexural strength and flexural modulus thereof were measured in accordance with ISO178.
(6) Moldability
After a molded article was manufactured in a mold, a state of attached materials on the mold was measured with the naked eyes and measured as follows:
Excellent: Since an amount of the attached materials is small, the mold is less contaminated, and the molded article has a smooth surface.
Average: Since an amount of the attached materials is small, the mold is less contaminated, but the molded article does not have a smooth surface.
Defective: Since an amount of the attached materials is large, the mold is contaminated, and the molded article does not have a smooth surface.
(7) Weather Resistance
Time until the obtained test specimen was exposed by Sunshine weather O-meter "WEL-SUN-DCH-B" manufactured by Suga Testing Machine Co., Ltd, at 83℃ and deterioration phenomenon such as whitening, crack, and the like, was started being observed by an optical microscope was determined as a crack occurring time. The longer the crack occurring time is, the more excellent the weather resistance is.
(8) Long-Term Dimensional Stability
A molding shrinkage was measured by ASTM D955 method.
As a numerical value becomes small, shrinkage becomes less generated, and long-term dimensional stability is excellent.
[Example 1]
Based on 100 parts by weight of a resin composition containing 95 wt% of polyoxymethylene (KEPITAL Plastics Co., LTD. F10-03H) and 5 wt% of aramid powder (Teijin Aramid, Twaron 5011, average particle size 100㎛), 0.2 parts by weight of ethylene bis stearamide (hereinafter, referred to as EBS) and 0.2 parts by weight of ethylene urea (Finecn Chemical Co., Ltd) (China) were mixed with each other.
The mixture was introduced into a hopper of a twin screw compounding machine(JSW Co., Ltd.) (Japan) to be subjected to a compounding process. A screw rate was 180 rpm and a temperature was 190℃. Thus prepared resin composition was injected through an injection molder (Fanac Co., Ltd., electric injection machine and injection rate: 20 mm/s, injection pressure 700 kgf, measurement: 50 mm, cooling time: 10 sec, and mold temperature: 80℃) and molded as a sample.
Physical properties of the prepared sample were measured by the above-described method, and results thereof were shown in Tables 2 and 3 below.
[Example 2]
Based on 100 parts by weight of a resin composition containing 95 wt% of polyoxymethylene (KEPITAL Plastics Co., LTD. F10-03H) and 5 wt% of aramid powder (Teijin Aramid, Twaron 5011, average particle size 100㎛), 0.2 parts by weight of EBS and 0.2 parts by weight of antioxidant (Ciba-Geigy Co., Ltd, Irganox 1010) were mixed with each other.
The mixture was introduced into a hopper of a twin screw compounding machine(JSW Co., Ltd.) (Japan) to be subjected to a compounding process. A screw rate was 180 rpm and a temperature was 190℃. Thus prepared resin composition was injected through an injection molder (Fanac Co., Ltd., electric injection machine and injection rate: 20 mm/s, injection pressure 700 kgf, measurement: 50 mm, cooling time: 10 sec, and mold temperature: 80℃) and molded as a sample.
Physical properties of the prepared sample were measured by the above-described method, and results thereof were shown in Tables 2 and 3 below.
[Example 3]
Based on 100 parts by weight of a resin composition containing 80 wt% of polyoxymethylene (KEPITAL Plastics Co., LTD. F10-03H) and 20 wt% of aramid powder (Teijin Aramid, Twaron 5011, average particle size 100㎛), 0.2 parts by weight of EBS, 0.2 parts by weight of ethylene urea, and 0.2 parts by weight of antioxidant (Ciba-Geigy Co., Ltd, Irganox 1010) were mixed with each other.
The mixture was introduced into a hopper of a twin screw compounding machine(JSW Co., Ltd.) (Japan) to be subjected to a compounding process. A screw rate was 180 rpm and a temperature was 190℃. Thus prepared resin composition was injected through an injection molder (Fanac Co., Ltd., electric injection machine and injection rate: 20 mm/s, injection pressure 700 kgf, measurement: 50 mm, cooling time: 10 sec, and mold temperature: 80℃) and molded as a sample.
Physical properties of the prepared sample were measured by the above-described method, and results thereof were shown in Tables 2 and 3 below.
[Example 4]
Based on 100 parts by weight of a resin composition containing 99 wt% of polyoxymethylene (KEPITAL Plastics Co., LTD. F10-03H) and 1 wt% of aramid powder (Teijin Aramid, Twaron 5011, average particle size 100㎛), 0.2 parts by weight of EBS, 0.2 parts by weight of ethylene urea, and 0.2 parts by weight of antioxidant (Ciba-Geigy Co., Ltd, Irganox 1010) were mixed with each other.
The mixture was introduced into a hopper of a twin screw compounding machine(JSW Co., Ltd.) (Japan) to be subjected to a compounding process. A screw rate was 180 rpm and a temperature was 190℃. Thus prepared resin composition was injected through an injection molder (Fanac Co., Ltd., electric injection machine and injection rate: 20 mm/s, injection pressure 700 kgf, measurement: 50 mm, cooling time: 10 sec, and mold temperature: 80℃) and molded as a sample.
Physical properties of the prepared sample were measured by the above-described method, and results thereof were shown in Tables 2 and 3 below.
[Example 5]
Based on 100 parts by weight of a resin composition containing 95 wt% of polyoxymethylene (KEPITAL Plastics Co., LTD. F10-03H) and 5 wt% of aramid powder (Teijin Aramid, Twaron 5011, average particle size 100㎛), 0.2 parts by weight of EBS, 0.2 parts by weight of ethylene urea, 0.2 parts by weight of antioxidant (Ciba-Geigy Co., Ltd, Irganox 1010), and 0.1 parts by weight of polytetrafluoroethylene (Solvay, Polymist XPP 511, hereinafter, referred to as PTFE) were mixed with each other.
The mixture was introduced into a hopper of a twin screw compounding machine(JSW Co., Ltd.) (Japan) to be subjected to a compounding process. A screw rate was 180 rpm and a temperature was 190℃. Thus prepared resin composition was injected through an injection molder (Fanac Co., Ltd., electric injection machine and injection rate: 20 mm/s, injection pressure 700 kgf, measurement: 50 mm, cooling time: 10 sec, and mold temperature: 80℃) and molded as a sample.
Physical properties of the prepared sample were measured by the above-described method, and results thereof were shown in Tables 2 and 3 below.
[Example 6]
Based on 100 parts by weight of a resin composition containing 95 wt% of polyoxymethylene (KEPITAL Plastics Co., LTD. F10-03H) and 5 wt% of aramid powder (Teijin Aramid, Twaron 5011, average particle size 100㎛), 0.2 parts by weight of EBS, 0.2 parts by weight of ethylene urea, 0.2 parts by weight of antioxidant (Ciba-Geigy Co., Ltd, Irganox 1010), and 1.0 part by weight of polytetrafluoroethylene (Solvay, Polymist XPP 511, hereinafter, referred to as PTFE) were mixed with each other.
The mixture was introduced into a hopper of a twin screw compounding machine(JSW Co., Ltd.) (Japan) to be subjected to a compounding process. A screw rate was 180 rpm and a temperature was 190℃. Thus prepared resin composition was injected through an injection molder (Fanac Co., Ltd., electric injection machine and injection rate: 20 mm/s, injection pressure 700 kgf, measurement: 50 mm, cooling time: 10 sec, and mold temperature: 80℃) and molded as a sample.
Physical properties of the prepared sample were measured by the above-described method, and results thereof were shown in Tables 2 and 3 below.
[Examples 7 to 8]
As shown in Table 1 below, Examples 7 and 8 were conducted as the same as Example 1 above except for changing each content of EBS and ethylene urea of Example 1.
Physical properties of the prepared sample were measured by the above-described method, and results thereof were shown in Tables 2 and 3 below.
[Example 9]
Based on 100 parts by weight of a resin composition containing 95 wt% of polyoxymethylene (KEPITAL Plastics Co., LTD. F10-03H) and 5 wt% of aramid powder (Teijin Aramid, Twaron 5011, average particle size 100㎛), 0.2 parts by weight of EBS, 0.2 parts by weight of ethylene urea, 0.2 parts by weight of antioxidant (Ciba-Geigy Co., Ltd, Irganox 1010), and 0.1 parts by weight of ultrahigh molecular weight polyethylene powder (Ticona GmbH, Hostalen GUR 4113® hereinafter, referred to as PTFE) having a weight average molecular weight of 3.8x106 were mixed with each other.
The mixture was introduced into a hopper of a twin screw compounding machine(JSW Co., Ltd.) (Japan) to be subjected to a compounding process. A screw rate was 180 rpm and a temperature was 190℃. Thus prepared resin composition was injected through an injection molder (Fanac Co., Ltd., electric injection machine and injection rate: 20 mm/s, injection pressure 700 kgf, measurement: 50 mm, cooling time: 10 sec, and mold temperature: 80℃) and molded as a sample.
Physical properties of the prepared sample were measured by the above-described method, and results thereof were shown in Tables 2 and 3 below.
[Example 10]
Based on 100 parts by weight of a resin composition containing 95 wt% of polyoxymethylene (KEPITAL Plastics Co., LTD. F10-03H) and 5 wt% of aramid powder (Teijin Aramid, Twaron 5011, average particle size 100㎛), 0.2 parts by weight of EBS, 0.2 parts by weight of ethylene urea, 0.2 parts by weight of antioxidant (Ciba-Geigy Co., Ltd, Irganox 1010), 0.1 parts by weight of polytetrafluoroethylene (Solvay, Polymist XPP 511, hereinafter, referred to as PTFE), and 0.1 parts by weight of ultrahigh molecular weight polyethylene powder (Ticona GmbH, Hostalen GUR 4113® hereinafter, referred to as PTFE) having a weight average molecular weight of 3.8x106 were mixed with each other.
The mixture was introduced into a hopper of a twin screw compounding machine(JSW Co., Ltd.) (Japan) to be subjected to a compounding process. A screw rate was 180 rpm and a temperature was 190℃. Thus prepared resin composition was injected through an injection molder (Fanac Co., Ltd., electric injection machine and injection rate: 20 mm/s, injection pressure 700 kgf, measurement: 50 mm, cooling time: 10 sec, and mold temperature: 80℃) and molded as a sample.
Physical properties of the prepared sample were measured by the above-described method, and results thereof were shown in Tables 2 and 3 below.
[Comparative Example 1]
Based on 100 parts by weight of a resin composition containing 95 wt% of polyoxymethylene (KEPITAL Plastics Co., LTD. F10-03H) and 5 wt% of aramid powder (Teijin Aramid, Twaron 5011, average particle size 100㎛), 0.2 parts by weight of ethylene bis stearamide (hereinafter, referred to as EBS) was mixed with each other.
The mixture was introduced into a hopper of a twin screw compounding machine(JSW Co., Ltd.) (Japan) to be subjected to a compounding process. A screw rate was 180 rpm and a temperature was 190℃. Thus prepared resin composition was injected through an injection molder (Fanac Co., Ltd., electric injection machine and injection rate: 20 mm/s, injection pressure 700 kgf, measurement: 50 mm, cooling time: 10 sec, and mold temperature: 80℃) and molded as a sample.
Physical properties of the prepared sample were measured by the above-described method, and results thereof were shown in Tables 2 and 3 below.
[Comparative Example 2]
Based on 100 parts by weight of a resin composition containing 95 wt% of polyoxymethylene (KEPITAL Plastics Co., LTD. F10-03H) and 5 wt% of aramid powder (Teijin Aramid, Twaron 5011, average particle size 100㎛), 0.2 parts by weight of ethylene urea was mixed with each other.
The mixture was introduced into a hopper of a twin screw compounding machine(JSW Co., Ltd.) (Japan) to be subjected to a compounding process. A screw rate was 180 rpm and a temperature was 190℃. Thus prepared resin composition was injected through an injection molder (Fanac Co., Ltd., electric injection machine and injection rate: 20 mm/s, injection pressure 700 kgf, measurement: 50 mm, cooling time: 10 sec, and mold temperature: 80℃) and molded as a sample.
Physical properties of the prepared sample were measured by the above-described method, and results thereof were shown in Tables 2 and 3 below.
[Comparative Example 3]
Based on 100 parts by weight of a resin composition containing 95 wt% of polyoxymethylene (KEPITAL Plastics Co., LTD. F10-03H) and 5 wt% of aramid powder (Teijin Aramid, Twaron 5011, average particle size 100㎛), 0.2 parts by weight of an antioxidant (Ciba-Geigy Co., Ltd, Irganox 1010) was mixed with each other.
The mixture was introduced into a hopper of a twin screw compounding machine(JSW Co., Ltd.) (Japan) to be subjected to a compounding process. A screw rate was 180 rpm and a temperature was 190℃. Thus prepared resin composition was injected through an injection molder (Fanac Co., Ltd., electric injection machine and injection rate: 20 mm/s, injection pressure 700 kgf, measurement: 50 mm, cooling time: 10 sec, and mold temperature: 80℃) and molded as a sample.
Physical properties of the prepared sample were measured by the above-described method, and results thereof were shown in Tables 2 and 3 below.
Table 1
Polyoxymethylene(wt%) Aramid(wt%) EBS(Part by Weight) Ethylene Urea (Part by Weight) Antioxidant (Part by Weight) PTFE(Part by Weight) UHMWPE(Part by Weight)
Example 1 95 5 0.2 0.2 - - -
Example 2 95 5 0.2 0.2 0.2 - -
Example 3 80 20 0.2 0.2 0.2 - -
Example 4 99 1 0.2 0.2 0.2 - -
Example 5 95 5 0.2 0.2 0.2 0.1 -
Example 6 95 5 0.2 0.2 0.2 1.0 -
Example 7 95 5 1.0 0.2 - - -
Example 8 95 5 0.2 1.0 - - -
Example 9 95 5 0.2 0.2 0.2 - 0.1
Example 10 95 5 0.2 0.2 0.2 0.1 0.1
Comparative Example 1 95 5 0.2 - - - -
Comparative Example 2 95 5 - 0.2 - - -
Comparative Example 3 95 5 - - 0.2 - -
Table 2
Emission Amount(mg/kg) of Formaldehyde Hardness(M scale) Ring-on-Ring Type Pin-on-Disk Type
Coefficient of Kinetic Friction Specific Wear Amount(㎣/㎏f㎞) Coefficient of Kinetic Friction Specific Wear Amount(㎣/㎏f㎞)
Example 1 6 M88 0.17 0.03 0.31 6.7
Example 2 3 M88 0.17 0.03 0.32 6.7
Example 3 10 M92 0.11 0.01 0.18 3.3
Example 4 2 M85 0.20 0.2 0.41 7.0
Example 5 3 M88 0.17 0.03 0.30 6.6
Example 6 3 M88 0.16 0.02 0.29 6.0
Example 7 5 M88 0.16 0.03 0.30 6.4
Example 8 1 M88 0.17 0.03 0.31 6.6
Example 9 3 M88 0.15 0.02 0.18 3.3
Example 10 3 M88 0.14 0.01 0.17 3.2
Comparative Example 1 32 M88 0.25 0.5 0.53 8.2
Comparative Example 2 16 M88 0.28 0.7 0.58 8.9
Comparative Example 3 26 M88 0.31 0.8 0.60 9.1
As shown in Table 2 above, it could be appreciated that the polyoxymethylene composition according to the present invention had significantly low emission amount of formaldehyde, excellent hardness, and significantly improved tribology property.
In addition, from results of Comparative Examples 1 to 3, it could be appreciated that in a case where any one component of components of the present invention is excluded, desired physical properties were not expressed.
Table 3
Tensile Strength(MPa) Tensile Elongation(%) Flexural Strength(MPa) Flexural Modulus(MPa) Moldability Weather Resistance(Time) Long-Term Dimensional Stability
Example 1 63 11 90 2860 Excellent 1100 1.8%
Example 2 63 11 90 2860 Excellent 1160 1.7%
Example 3 80 15 95 2980 Excellent 1110 1.8%
Example 4 50 6 76 1870 Excellent 1106 1.7%
Example 5 65 13 92 2980 Excellent 1180 1.5%
Example 6 72 15 95 3200 Excellent 1200 1.3%
Example 7 63 11 80 2860 Excellent 1100 1.8%
Example 8 63 12 90 2860 Excellent 1100 1.8%
Example 9 64 13 92 2970 Excellent 1150 1.5%
Example 10 70 13 94 2985 Excellent 1160 1.4%
Comparative Example 1 63 11 90 2860 Defective 500 3.0%
Comparative Example 2 62 11 89 2850 Defective 490 3.0%
Comparative Example 3 60 10 87 2730 Defective 450 3.1%
As shown in Table 3 above, it could be appreciated that in a case of further including the antioxidant like Example 2, weather resistance and long-term dimensional stability were significantly improved.
In addition, it could be appreciated that in a case of using 20 wt% of aramid powder like Example 3, mechanical physical properties such as tensile strength, tensile elongation, flexural strength, flexural modulus, and the like, were significantly improved.
Further, it could be appreciated that in a case of using 1 wt% of aramid powder like Example 4, mechanical physical properties were slightly decreased; however, was higher as compared to Comparative Examples.
In addition, it could be confirmed that in a case of further including PTFE like Examples 5 and 6, physical properties were significantly improved.
Further, it could be confirmed that in a case of changing each content of EBS and ethylene urea of Example 1 and using the changed content thereof like Examples 7 and 8, physical properties as similar to those of Example 1 above were shown.
In addition, it could be confirmed that in a case of further including UHMWPE like Examples 9 and 10, mechanical physical properties were significantly improved, and moldability was excellent.
Further, it could be appreciated that in a case where the composition is out of the above-described range of the present invention like Comparative Examples 1 to 3, mechanical strength was deteriorated and weather resistance and long-term dimensional stability were also deteriorated.

Claims (8)

  1. A polyoxymethylene composition comprising polyoxymethylene, aramid powder, ethylene bis stearamide, and ethylene urea.
  2. The polyoxymethylene composition of claim 1, wherein the aramid powder is an aramid resin having a para structure in which the following Chemical formula I is repeated:
    [Chemical Formula 1]
    Figure PCTKR2014003840-appb-I000002
  3. The polyoxymethylene composition of claim 2, wherein the aramid powder has an average particle size of 0.1 to 500㎛.
  4. The polyoxymethylene composition of claim 3, wherein the aramid powder has an average particle size of 0.1 to 200㎛.
  5. The polyoxymethylene composition of claim 1, wherein 0.01 to 2 parts by weight of ethylene bis stearamide and 0.01 to 2 parts by weight of ethylene urea are contained, based on 100 parts by weight of a resin composition containing 70 to 99 wt% of polyoxymethylene and 1 to 30 wt% of aramid powder.
  6. The polyoxymethylene composition of claim 1, further comprising: polytetrafluoroethylene powder, ultra high molecular weight polyethylene powder having a weight average molecular weight of 1x106 to 5x106g/mol, or mixtures thereof.
  7. The polyoxymethylene composition of claim 5, further comprising: 0.01 to 2 parts by weight of polytetrafluoroethylene powder, ultra high molecular weight polyethylene powder having a weight average molecular weight of 1x106 to 5x106g/mol, or mixtures thereof, based on 100 parts by weight of the resin composition.
  8. A molded article manufactured by using the polyoxymethylene composition of any one of claims 1 to 7.
PCT/KR2014/003840 2013-05-06 2014-04-30 Polyoxymethylene composition WO2014181999A1 (en)

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US20220332879A1 (en) * 2017-04-07 2022-10-20 Ticona Llc Low Emission Polyoxymethylene Composition
US11661512B2 (en) * 2018-12-12 2023-05-30 Celanese International Corporation Color stable and low wear polymer composition and articles made therefrom

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