WO2017130931A1 - Composition de résine de polyamide résistante au vieillissement thermique - Google Patents

Composition de résine de polyamide résistante au vieillissement thermique Download PDF

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Publication number
WO2017130931A1
WO2017130931A1 PCT/JP2017/002240 JP2017002240W WO2017130931A1 WO 2017130931 A1 WO2017130931 A1 WO 2017130931A1 JP 2017002240 W JP2017002240 W JP 2017002240W WO 2017130931 A1 WO2017130931 A1 WO 2017130931A1
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mass
parts
polyamide resin
polyamide
polyacrylonitrile
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PCT/JP2017/002240
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English (en)
Japanese (ja)
Inventor
友宏 伊藤
信宏 吉村
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東洋紡株式会社
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Priority to JP2017510683A priority Critical patent/JPWO2017130931A1/ja
Publication of WO2017130931A1 publication Critical patent/WO2017130931A1/fr

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    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/18—Homopolymers or copolymers of nitriles
    • C08L33/20—Homopolymers or copolymers of acrylonitrile
    • 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

Definitions

  • the present invention relates to a polyamide resin composition having excellent heat aging resistance.
  • Polyamide resins have been widely used in various parts such as automobile parts, electrical and electronic parts, and industrial machine parts because they have excellent characteristics such as mechanical properties, chemical resistance and molding processability.
  • Polyamide resins are a class of resins that are relatively excellent in heat aging resistance, but deterioration due to the action of heat and light is inevitable.
  • As a method for improving heat aging resistance copper halide, potassium halide, oxazole compounds, etc. are heated.
  • a method of adding as a stabilizer has been known for a long time (for example, Patent Document 1).
  • polyamide resins are used for parts that are exposed to a high temperature environment of about 140 ° C. in the field of automobile parts, electrical and electronic parts.
  • the environmental temperature in the engine room has increased with the increase in engine output and the density of parts in recent years, and unprecedented heat aging resistance has been demanded. .
  • Patent Document 2 a method of blending fine elemental iron with polyamide
  • Patent Document 3 a method of blending finely dispersed metal powder with polyamide
  • Patent Document 4 a method of blending a heat stabilizer such as copper iodide and potassium iodide and a complex oxide such as iron trioxide (including iron (II) oxide)
  • Patent Document 5 a method of blending a heat stabilizer such as copper iodide and potassium iodide and a complex oxide such as iron trioxide (including iron (II) oxide)
  • Patent Document 2 and Patent Document 3 there is a risk of catching fire during the production of the composition, and the production is not easy.
  • the method of Patent Document 4 the effect is exhibited only with a very limited composition.
  • the method of Patent Document 5 is inferior in heat aging resistance, stability of mechanical strength, and reproducibility, and there is room for improvement in each situation.
  • a polyamide resin composition having heat aging resistance that can withstand a high temperature environment of about 200 ° C. and excellent mechanical properties.
  • a polyamide resin composition comprising 0.1 to 5 parts by mass of polyacrylonitrile-based fine particles having an average particle diameter of 200 ⁇ m or less with respect to 100 parts by mass of a polyamide resin.
  • the polyamide resin can be easily and stably imparted with heat aging resistance under a high temperature environment of about 200 ° C., and the obtained polyamide resin composition has excellent heat aging resistance and mechanical properties. Has physical properties.
  • the polyamide resin in the present invention is not particularly limited.
  • a ring-opening polymerization product of cyclic lactam a polycondensation product of aminocarboxylic acid, a polycondensation product of dibasic acid and diamine, and a copolymer thereof.
  • polycaproamide polyamide 6
  • polyhexamethylene adipamide polyamide 66
  • polytetramethylene adipamide polyamide 46
  • polyhexamethylene sebacamide polyamide 610
  • Aliphatic polyamides such as polyhexamethylene dodecamide (polyamide 612), poly-lauryl lactam (polyamide 12), poly-11-aminoundecanoic acid (polyamide 11), poly (metaxylene adipamide) (polyamide MXD6)
  • Poly (hexamethylene terephthalamide) polyamide 6T
  • poly (f Aliphatic-aromatic polyamides such as samethylene isophthalamide) (polyamide 6I), poly (nonamethylene terephthalamide) (polyamide 9T), poly (tetramethylene isophthalamide) (polyamide 4I), and copolymers and mixtures thereof Can be mentioned.
  • Particularly suitable polyamides for the present invention include polyamide 6, polyamide 66, polyamide 6/66 copolymer, polyamide 66 / 6T copolymer, polyamide 6T / 12 copolymer, polyamide 6T / 11 copolymer, polyamide 6T / 6I copolymer, polyamide 6T / 6I / 12 copolymer, polyamide 6T / 610 copolymer, and polyamide 6T / 6I / 6 copolymer.
  • the molecular weight of such a polyamide resin is not particularly limited, but a polyamide resin having a relative viscosity of 1.7 to 4.5 measured at 25 ° C. in 98% (98% by mass) sulfuric acid at a concentration of 1% by mass is used. It is preferable.
  • the relative viscosity of the polyamide resin is more preferably 2.0 to 4.0, still more preferably 2.0 to 3.5.
  • the polyacrylonitrile-based fine particles in the present invention have an average particle size of 200 ⁇ m or less, and are composed of a polymer mainly composed of an acrylonitrile (AN) component, preferably composed of a polymer containing 50% by mass or more of an acrylonitrile (AN) component. .
  • the content of the acrylonitrile (AN) component is more preferably 60% by mass or more, further preferably 70% by mass or more, particularly preferably 80% by mass or more, and most preferably 90% by mass or more.
  • a copolymer obtained by copolymerizing one or more monomers selected from the group is recommended.
  • Examples of the acrylate ester and the methacrylic acid ester include methyl (that is, methyl acrylate, methyl methacrylate), ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, Examples include cyclohexyl, 2-ethylhexyl, lauryl, stearyl and the like.
  • the refractive index and morphological characteristics of the fine particles can be adjusted by selecting these comonomers and combining them with the polymerization method.
  • the polyacrylonitrile-based fine particles are preferably crosslinked polyacrylonitrile-based fine particles having a degree of swelling of less than 10% by volume in petroleum-based, aromatic-based or alcohol-based solvents.
  • the content of acrylonitrile is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and particularly preferably 80% by mass. % Or more, and most preferably 90% by mass or more.
  • the acrylonitrile content increases, the fine irregularities formed on the particle surface become denser, and the area of the fine irregularities also increases, so that the specific surface area increases. As the specific surface area increases, the oxygen shielding property is improved.
  • the crosslinkable vinyl monomer used for crosslinking is not particularly limited as long as it is a crosslinkable monomer having two or more unsaturated double bonds capable of radical polymerization.
  • vinyl compounds such as 1,4-divinyloxybutane and divinylsulfone; allyl compounds such as diallyl phthalate, diallyl acrylamide, triallyl (iso) cyanurate, triallyl trimellitate; (poly) ethylene glycol di (meth) acrylate (Poly) oxyalkylene glycol di (meth) acrylates such as (poly) propylene glycol di (meth) acrylate; pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate, tri Methylolpropane tri (meth) acrylate, dipentaerythritol hexa
  • a vinyl monomer capable of radical polymerization other than acrylonitrile and a crosslinkable vinyl monomer may be used as appropriate.
  • the monomer is not particularly limited as long as it is capable of radical polymerization.
  • acrylic acid ester monomers such as methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, methyl methacrylate, ethyl methacrylate, lauryl methacrylate, dimethylamino Methacrylic acid ester monomers such as ethyl methacrylate, styrene monomers such as styrene and p-methylstyrene, alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, vinyl ester monomers such as vinyl acetate and vinyl butyrate, Examples thereof include N-alkyl substituted (meth) acrylamides such as N-methylacrylamide and N-ethylacrylamide, and nitrile monomers such as methacrylonitrile. Such monomers may be used in combination of two or more
  • the polyacrylonitrile-based fine particles used in the present invention employ the above-mentioned monomers and employ a polymerization method such as suspension polymerization (pearl polymerization), suspension precipitation polymerization, or emulsion polymerization, and are disclosed in JP-A-9-286817 and JP-A-2003. -226720, Japanese Patent Application Laid-Open No. 2012-184420, and the like.
  • a polymerization method such as suspension polymerization (pearl polymerization), suspension precipitation polymerization, or emulsion polymerization
  • the polyacrylonitrile-based fine particles used in the present invention are not particularly limited as long as the average particle size is 200 ⁇ m or less and can be uniformly dispersed in the polyamide resin, but preferably the average particle size is 100 ⁇ m or less, More preferably, it is 60 micrometers or less, More preferably, it is 40 micrometers or less, Most preferably, it is 20 micrometers or less. If it exceeds 200 ⁇ m, non-uniform dispersion in the polyamide tends to occur, and the mechanical properties tend to decrease.
  • the lower limit of the size of the polyacrylonitrile-based fine particles is not particularly limited, but is about 1 ⁇ m in terms of manufacturing technology and manufacturing cost.
  • the lower limit of the polyacrylonitrile-based fine particles is more preferably 3 ⁇ m and even more preferably 5 ⁇ m.
  • the average particle size of the polyacrylonitrile-based fine particles can be measured using a laser diffraction particle size measuring device as described in the Examples section.
  • the content of the polyacrylonitrile-based fine particles is 0.1 to 5 parts by weight, preferably 0.3 to 3 parts by weight, more preferably 0.4 to 4 parts by weight with respect to 100 parts by weight of the polyamide resin. 2 parts by mass. Even if it exceeds 5 parts by mass, no further effect of improving the heat aging resistance is obtained, the mechanical properties of the composition are lowered, and if it is less than 0.1 parts by mass, it is difficult to obtain the blending effect.
  • a known heat stabilizer in addition to the polyacrylonitrile-based fine particles, a known heat stabilizer can also be used.
  • Examples of the copper compound that can be used in the present invention include copper acetate, copper iodide, copper bromide, copper chloride, copper fluoride, copper laurate, and copper stearate. These copper compounds may be used alone or in combination. Copper acetate, copper iodide, copper bromide and copper chloride are preferred, and cupric bromide is particularly preferably used.
  • the content of the copper compound is preferably 0.0001 to 1 part by mass as copper in the copper compound with respect to 100 parts by mass of the polyamide resin.
  • a more preferable content is 0.0005 to 1 part by mass, and a still more preferable content is 0.005 to 0.2 part by mass.
  • a copper compound when adding a copper compound, it is preferable to use an alkali metal halide compound such as potassium iodide or potassium bromide in combination. By using together, precipitation of copper can be prevented.
  • a method for adding the copper compound it may be added at any stage of the production of the polyamide resin, and the addition method is not limited. For example, a method of adding to a raw material salt aqueous solution of polyamide, a method of injecting and adding to a molten polyamide in the middle of melt polymerization, and after blending a granulated polyamide pellet and the copper compound powder or masterbatch after polymerization Any of a method of melt kneading using an extruder, a molding machine or the like may be used.
  • an auxiliary stabilizer such as a hindered phenol antioxidant, a phosphorus antioxidant, a sulfur antioxidant, an amine antioxidant, or a light stabilizer is added. Can do.
  • hindered phenol antioxidant can be used alone or in combination.
  • phenols having two or more functional groups are preferable, and triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] (IRGANOX245)
  • IRGANOX245 triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate]
  • the blending amount (content) is preferably 0.05 to 3 parts by mass, more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the polyamide resin. 2 parts by mass. If it is less than 0.05 part by mass, the effect of preventing thermal discoloration is insufficient, while if it exceeds 3 parts by mass, the effect may reach saturation or blooming on the surface of the molded product may occur.
  • the phosphorus antioxidant is at least one selected from inorganic and organic phosphorus antioxidants.
  • inorganic phosphorus antioxidants include hypophosphites such as sodium hypophosphite and phosphites.
  • organic phosphorus antioxidant commercially available organic phosphorus antioxidants such as phosphites can be used, but organic phosphorus-containing compounds that do not generate phosphoric acid by thermal decomposition are preferable. As such organic phosphorus-containing compounds, known compounds can be used.
  • the blending amount (content) is preferably 0.05 to 3 parts by weight, more preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the polyamide resin. Part. If the amount is less than 0.05 parts by mass, the effect of preventing thermal discoloration is insufficient. On the other hand, if the amount exceeds 3 parts by mass, flashing may occur in the molded product. In the present invention, it is preferable to use inorganic and organic phosphorus antioxidants in combination because the amount of the antioxidant can be reduced.
  • amine-based antioxidant that can be used in the present invention
  • known compounds can be used.
  • Secondary arylamines can also be mentioned as amine-based antioxidants.
  • secondary arylamine is meant an amine compound containing two carbon radicals chemically bonded to a nitrogen atom, wherein at least one, preferably both carbon radicals are aromatic.
  • the blending amount (content) is preferably 0.05 to 3 parts by mass, more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the polyamide resin. Part. If it is less than 0.05 part by mass, the effect of preventing thermal discoloration is insufficient, while if it exceeds 3 parts by mass, the effect may reach saturation or blooming on the surface of the molded product may occur.
  • sulfur-based antioxidant that can be used in the present invention, known compounds can be used.
  • the blending amount (content) is preferably 0.05 to 3 parts by weight, more preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the polyamide resin. Part. If it is less than 0.05 part by mass, the effect of preventing thermal discoloration is insufficient, while if it exceeds 3 parts by mass, the effect may reach saturation or blooming on the surface of the molded product may occur.
  • the light stabilizer that can be used in the present invention is preferably one or more hindered amine type light stabilizers (HALS).
  • HALS is a compound derived from a substituted piperidine compound, in particular a compound derived from an alkyl-substituted piperidinyl or piperazinone compound, and an alkoxy-substituted piperidinyl compound.
  • a known compound can be used.
  • a mixture of secondary arylamine and HALS can be used.
  • Preferred embodiments comprise at least two co-stabilizers, at least one selected from secondary arylamines and at least one selected from the group of HALS.
  • the total blending amount is preferably 0.5 to 10 parts by mass, more preferably 0.5 to 3 parts per 100 parts by mass of the polyamide resin. Part by mass. If the amount is less than 0.5 parts by mass, the effect of improving the heat aging resistance is insufficient. On the other hand, if the amount exceeds 10 parts by mass, the effect may be saturated or blooming may occur on the surface of the molded product.
  • the strength, rigidity, heat resistance and the like can be significantly improved by adding a filler.
  • a filler include glass fiber, carbon fiber, metal fiber, aramid fiber, asbestos, potassium titanate whisker, wollastonite, glass flake, glass beads, talc, mica, clay, calcium carbonate, barium sulfate, oxidation Examples thereof include titanium and aluminum oxide. Among them, chopped strand type glass fibers are preferably used.
  • the blending amount (content) is preferably 5 to 140 parts by weight, particularly preferably 5 to 100 parts by weight with respect to 100 parts by weight of the polyamide resin.
  • ultraviolet absorbers for example, resorcinol, salicylate, benzotriazole, benzophenone, etc.
  • lubricants and mold release agents for example, nucleating agents, plasticizers, and the like within a range not impairing the object of the present invention.
  • One or more conventional additives such as an antistatic agent and a colorant containing a dye / pigment can be added up to about 5 parts by mass with respect to 100 parts by mass of the polyamide resin.
  • the polyamide resin composition of the present invention can contain each component described above, but in the composition excluding the filler, the total amount of polyamide resin and polyacrylonitrile-based fine particles is 90% by mass or more. It is preferable to occupy 95% by mass or more.
  • the polyamide resin composition of the present invention has a tensile strength retention of 80% or more after heat treatment at 200 ° C. for 1000 hours in the heat aging test described in the Examples section.
  • the polyamide resin composition of the present invention can achieve such characteristics by having the configuration described above.
  • the method of incorporating the polyacrylonitrile-based fine particles and other additives in the present invention into the polyamide resin is not particularly limited, and may be performed by any method. For example, after all the components are premixed, the method is kneaded in an extruder or kneader, or the other components are kneaded and blended with pellets obtained by kneading any number of components in advance in an extruder or kneader. Is mentioned.
  • the polyamide resin composition of the present invention can be formed into a molded body by a so-called hollow method represented by injection molding, extrusion molding, thermoforming, compression molding, blow molding, die slide molding or the like.
  • these molded products can be formed into molded products by secondary processing, for example, welding methods including vibration welding, hot plate welding, ultrasonic welding, and the like.
  • it is an injection-molded or blow-molded body, and a molded body by secondary processing thereof.
  • Examples of applications of the molded body made of the polyamide resin composition of the present invention include, for example, cylinder head covers, engine covers, intercooler housings, valves, end caps, casters, trolley parts, etc.
  • intake pipes air ducts
  • intake system parts such as intake manifolds, connectors, gears, fan wheels, coolant storage containers, housings or housing parts for heat exchangers, radiators, thermostats, coolants and water pumps , Heaters, fastening elements, oil pans, exhaust systems such as mufflers and housings for catalytic converters, timing chain belt front covers, gearboxes, bearing retainers, gasoline caps, seat parts, headrests, doors Bundles, etc. wiper components and the like.
  • circuit board components housings, films, conductors, switches, terminal strips, relays, resistors, capacitors, coils, lamps, diodes, LEDs, transistors, connectors, controllers, memories, bolts, coil bobbins , Plugs, plug parts, mechatronic parts, cooking equipment, washing machine, refrigerator, air conditioner and other home appliance parts, sensors and the like.
  • parts for wheelchairs, stroller parts, chair legs, armrests, handrails, window frames, door knobs, and the like are, for example, parts for wheelchairs, stroller parts, chair legs, armrests, handrails, window frames, door knobs, and the like.
  • Fine particles are dispersed in deionized water at 20 ° C., and a refractive index of 1.60 to 0.10i on a volume basis is measured using a laser diffraction particle size measuring device (SALD2000 manufactured by Shimadzu Corporation). The median diameter measured and calculated was defined as the average particle diameter ( ⁇ m).
  • test piece was heat-treated in a recirculation air oven (manufactured by Nagano Scientific Machinery Co., Ltd., hot air circulation dryer NH-401S). The specimens were removed from the oven at 200 ° C. environment for a predetermined test time (500 hours, 1000 hours), cooled to room temperature and sealed in an aluminum lined bag until ready for testing. Subsequently, the tensile strength and the tensile elongation at break were measured according to ISO527-1,2. The average value obtained from three test pieces was adopted.
  • the retention rate of tensile strength and tensile elongation at break is the retention rate after heat treatment for 500 hours and 1000 hours when the initial value without heat treatment is 100%.
  • Examples 1-7, Comparative Examples 1-4 The resin compositions described as Examples and Comparative Examples were prepared by blending the above raw materials at the ratios (mass ratios) shown in Table 1 using a twin-screw extruder (STS35 manufactured by Coperion Co., Ltd.), and melt-kneading them. To obtain pellets (diameter: about 2.5 mm ⁇ length: about 2.5 mm). The obtained pellets were used after drying at 100 ° C. for 4 hours or more with a hot air circulating dryer. The evaluation results are shown in Table 1.
  • Examples 1 to 7 have high initial tensile strength (before heat treatment) and tensile elongation at break, and high tensile strength retention and tensile elongation at break after heat treatment at 200 ° C. for 500 hours and 1000 hours. ing. Comparative Example 1 has an initial tensile strength lower than that of Examples, and Comparative Examples 2 to 4 all have a tensile strength retention of 80% or less and a tensile elongation retention of less than 50% at 200 ° C. for 500 hours. It was confirmed that
  • the polyamide resin composition obtained according to the present invention has an environment at 200 ° C. because the heat aging resistance in a high temperature environment of about 200 ° C. can be easily and stably improved. It can be used for parts of automobiles and electrical / electronic products that may be exposed to

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  • 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)

Abstract

La présente invention concerne une composition de résine de polyamide résistante au vieillissement thermique ayant une résistance au vieillissement thermique qui peut supporter un environnement à haute température d'environ 200 °C ; la composition de résine polyamide contient 0,1 à 5 parties en masse de microparticules de polyacrylonitrile ayant une taille de particule moyenne de 200 µm ou moins pour 100 parties en masse de résine polyamide. Les microparticules de polyacrylonitrile comprennent de préférence un polymère de polyacrylonitrile contenant 50 % en masse ou plus d'un composant d'acrylonitrile, et, de préférence, contiennent en outre un composé de cuivre et des fibres de verre.
PCT/JP2017/002240 2016-01-28 2017-01-24 Composition de résine de polyamide résistante au vieillissement thermique WO2017130931A1 (fr)

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JP2017510683A JPWO2017130931A1 (ja) 2016-01-28 2017-01-24 耐熱老化性ポリアミド樹脂組成物

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5358548A (en) * 1976-11-08 1978-05-26 Asahi Chem Ind Co Ltd Resin composition having improved flame retardant characteristics
JP2003292774A (ja) * 2002-04-03 2003-10-15 Asahi Kasei Corp 耐熱性難燃樹脂組成物
JP2004131716A (ja) * 2002-09-17 2004-04-30 Umg Abs Ltd 熱可塑性樹脂組成物
JP2006001970A (ja) * 2004-06-15 2006-01-05 Yokohama Rubber Co Ltd:The 自動車部品用熱可塑性樹脂組成物
JP2011046781A (ja) * 2009-08-25 2011-03-10 Asahi Kasei Chemicals Corp ポリアミド樹脂組成物及びポリアミド樹脂組成物からなる成形品
JP2011080029A (ja) * 2009-09-09 2011-04-21 Daicel Polymer Ltd 塗装成形体用の樹脂組成物
JP2014015594A (ja) * 2012-07-11 2014-01-30 Asahi Kasei Chemicals Corp ポリアミド樹脂組成物及び成形品
JP2015520278A (ja) * 2012-06-18 2015-07-16 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ ポリアクリロニトリルのホモポリマーを有する難燃性ポリアミド

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5358548A (en) * 1976-11-08 1978-05-26 Asahi Chem Ind Co Ltd Resin composition having improved flame retardant characteristics
JP2003292774A (ja) * 2002-04-03 2003-10-15 Asahi Kasei Corp 耐熱性難燃樹脂組成物
JP2004131716A (ja) * 2002-09-17 2004-04-30 Umg Abs Ltd 熱可塑性樹脂組成物
JP2006001970A (ja) * 2004-06-15 2006-01-05 Yokohama Rubber Co Ltd:The 自動車部品用熱可塑性樹脂組成物
JP2011046781A (ja) * 2009-08-25 2011-03-10 Asahi Kasei Chemicals Corp ポリアミド樹脂組成物及びポリアミド樹脂組成物からなる成形品
JP2011080029A (ja) * 2009-09-09 2011-04-21 Daicel Polymer Ltd 塗装成形体用の樹脂組成物
JP2015520278A (ja) * 2012-06-18 2015-07-16 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ ポリアクリロニトリルのホモポリマーを有する難燃性ポリアミド
JP2014015594A (ja) * 2012-07-11 2014-01-30 Asahi Kasei Chemicals Corp ポリアミド樹脂組成物及び成形品

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