WO2017130931A1 - Heat-aging-resistant polyamide resin composition - Google Patents
Heat-aging-resistant polyamide resin composition Download PDFInfo
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- 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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- 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
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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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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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
- 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
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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
- 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
Abstract
The present invention provides a heat aging-resistant polyamide resin composition having heat aging resistance that can withstand a high-temperature environment of about 200°C; the polyamide resin composition contains 0.1-5 parts by mass of polyacrylonitrile microparticles having an average particle size of 200 μm or less per 100 parts by mass of polyamide resin. The polyacrylonitrile microparticles preferably comprise a polyacrylonitrile polymer containing 50 mass% or more of an acrylonitrile component, and preferably also contain a copper compound and glass fibers.
Description
本発明は、耐熱老化性の優れたポリアミド樹脂組成物に関する。
The present invention relates to a polyamide resin composition having excellent heat aging resistance.
ポリアミド樹脂は、機械的特性を始めとして、耐薬品性及び成形加工性などに優れた特性を有するため、従来より自動車部品、電気電子部品、工業機械部品などの各種部品に広く利用されている。ポリアミド樹脂は、比較的耐熱老化性に優れる部類の樹脂ではあるが、熱及び光の作用による劣化は不可避であり、耐熱老化性向上法として、ハロゲン化銅、ハロゲン化カリウム、オキサゾール化合物などを熱安定剤として添加する方法が古くから知られている（例えば、特許文献１）。
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).
これらの技術により、ポリアミド樹脂は、自動車部品や電気、電子部品の分野において、１４０℃程度の高温環境下に曝される用途の部品に用いられている。
しかしながら、例えば自動車のエンジンルームに関して、近年、エンジン出力の増加、部品の高密度化などに伴い、エンジンルーム内の環境温度が高くなり、これまでにない耐熱老化性が求められるようになっている。 With these techniques, 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.
However, for example, in the engine room of an automobile, 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. .
しかしながら、例えば自動車のエンジンルームに関して、近年、エンジン出力の増加、部品の高密度化などに伴い、エンジンルーム内の環境温度が高くなり、これまでにない耐熱老化性が求められるようになっている。 With these techniques, 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.
However, for example, in the engine room of an automobile, 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. .
これに対して、ポリアミドに微粒元素鉄を配合する方法（特許文献２）、ポリアミドに微粒分散化金属粉末を配合する方法（特許文献３）、融点が異なる２種類のポリアミド混合物に銅化合物と酸化鉄を配合する方法（特許文献４）、沃化銅と沃化カリウムなどの熱安定剤と四三酸化鉄（酸化鉄（ＩＩ）を含む）などの複合酸化物とを配合する方法（特許文献５）などが提案され、２００℃程度の高温環境下でも耐熱老化性に優れているとされている。
しかしながら、特許文献２や特許文献３の方法では、組成物の製造中に発火する危険性があり製造が容易でなく、特許文献４の方法では、非常に限定された組成でしか効果が発現しない欠点があり、特許文献５の方法では、耐熱老化性や機械的強度の安定性、再現性が劣ることがあり、それぞれ改善の余地があるのが現状である。 In contrast, a method of blending fine elemental iron with polyamide (Patent Document 2), a method of blending finely dispersed metal powder with polyamide (Patent Document 3), and a copper compound and oxidation in two types of polyamide mixtures having different melting points A method of blending iron (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) etc. are proposed, and it is said that it is excellent in heat aging resistance even in a high temperature environment of about 200 ° C.
However, in the methods of 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. In the method of Patent Document 4, the effect is exhibited only with a very limited composition. There are drawbacks, and 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.
しかしながら、特許文献２や特許文献３の方法では、組成物の製造中に発火する危険性があり製造が容易でなく、特許文献４の方法では、非常に限定された組成でしか効果が発現しない欠点があり、特許文献５の方法では、耐熱老化性や機械的強度の安定性、再現性が劣ることがあり、それぞれ改善の余地があるのが現状である。 In contrast, a method of blending fine elemental iron with polyamide (Patent Document 2), a method of blending finely dispersed metal powder with polyamide (Patent Document 3), and a copper compound and oxidation in two types of polyamide mixtures having different melting points A method of blending iron (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) etc. are proposed, and it is said that it is excellent in heat aging resistance even in a high temperature environment of about 200 ° C.
However, in the methods of 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. In the method of Patent Document 4, the effect is exhibited only with a very limited composition. There are drawbacks, and 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.
２００℃程度の高温環境に耐える耐熱老化性を有し、かつ機械的物性に優れたポリアミド樹脂組成物を提供する。
Provided is a polyamide resin composition having heat aging resistance that can withstand a high temperature environment of about 200 ° C. and excellent mechanical properties.
本発明者等は上述の問題を解決するため鋭意研究を重ねた結果、本発明に到達した。
即ち本発明は、以下の通りである。
［１］ ポリアミド樹脂１００質量部に対して、平均粒子径が２００μｍ以下のポリアクリロニトリル系微粒子を０．１～５質量部含有することを特徴とするポリアミド樹脂組成物。
［２］ 前記ポリアクリロニトリル系微粒子が、アクリロニトリル成分を５０質量％以上含有するポリアクリロニトリル系重合体からなる［１］に記載のポリアミド樹脂組成物。
［３］ 銅化合物をポリアミド樹脂１００質量部に対して、銅として０．０００１～１質量部含有することを特徴とする［１］または［２］に記載のポリアミド樹脂組成物。
［４］ ポリアミド樹脂１００質量部に対して、ガラス繊維を５～１４０質量部含有することを特徴とする［１］～［３］のいずれかに記載のポリアミド樹脂組成物。 The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the present invention is as follows.
[1] A polyamide resin composition comprising 0.1 to 5 parts by mass of polyacrylonitrile-based fine particles having an average particle diameter of 200 μm or less with respect to 100 parts by mass of a polyamide resin.
[2] The polyamide resin composition according to [1], wherein the polyacrylonitrile-based fine particles are composed of a polyacrylonitrile-based polymer containing 50% by mass or more of an acrylonitrile component.
[3] The polyamide resin composition according to [1] or [2], wherein the copper compound is contained in an amount of 0.0001 to 1 part by mass as copper with respect to 100 parts by mass of the polyamide resin.
[4] The polyamide resin composition according to any one of [1] to [3], which contains 5 to 140 parts by mass of glass fiber with respect to 100 parts by mass of the polyamide resin.
即ち本発明は、以下の通りである。
［１］ ポリアミド樹脂１００質量部に対して、平均粒子径が２００μｍ以下のポリアクリロニトリル系微粒子を０．１～５質量部含有することを特徴とするポリアミド樹脂組成物。
［２］ 前記ポリアクリロニトリル系微粒子が、アクリロニトリル成分を５０質量％以上含有するポリアクリロニトリル系重合体からなる［１］に記載のポリアミド樹脂組成物。
［３］ 銅化合物をポリアミド樹脂１００質量部に対して、銅として０．０００１～１質量部含有することを特徴とする［１］または［２］に記載のポリアミド樹脂組成物。
［４］ ポリアミド樹脂１００質量部に対して、ガラス繊維を５～１４０質量部含有することを特徴とする［１］～［３］のいずれかに記載のポリアミド樹脂組成物。 The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the present invention is as follows.
[1] A polyamide resin composition comprising 0.1 to 5 parts by mass of polyacrylonitrile-based fine particles having an average particle diameter of 200 μm or less with respect to 100 parts by mass of a polyamide resin.
[2] The polyamide resin composition according to [1], wherein the polyacrylonitrile-based fine particles are composed of a polyacrylonitrile-based polymer containing 50% by mass or more of an acrylonitrile component.
[3] The polyamide resin composition according to [1] or [2], wherein the copper compound is contained in an amount of 0.0001 to 1 part by mass as copper with respect to 100 parts by mass of the polyamide resin.
[4] The polyamide resin composition according to any one of [1] to [3], which contains 5 to 140 parts by mass of glass fiber with respect to 100 parts by mass of the polyamide resin.
本発明によれば、ポリアミド樹脂に２００℃程度の高温環境下での耐熱老化性を簡便に安定的に付与することができ、また得られたポリアミド樹脂組成物は、優れた耐熱老化性や機械的物性を有する。
According to the present invention, 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.
以下に本発明を具体的に説明する。
本発明におけるポリアミド樹脂としては、特に限定されるものではないが、例えば、環状ラクタムの開環重合物、アミノカルボン酸の重縮合物、二塩基酸とジアミンとの重縮合物、これらの共重合物などが挙げられ、具体的にはポリカプロアミド（ポリアミド６）、ポリヘキサメチレンアジパミド（ポリアミド６６）、ポリテトラメチレンアジパミド（ポリアミド４６）、ポリヘキサメチレンセバカミド（ポリアミド６１０）、ポリヘキサメチレンドデカミド（ポリアミド６１２）、ポリ－ラウリルラクタム（ポリアミド１２）、ポリ－１１－アミノウンデカン酸（ポリアミド１１）等の脂肪族ポリアミド、ポリ（メタキシレンアジパミド）（ポリアミドＭＸＤ６）、ポリ（ヘキサメチレンテレフタルアミド）（ポリアミド６Ｔ）、ポリ（ヘキサメチレンイソフタルアミド）（ポリアミド６Ｉ）、ポリ（ノナメチレンテレフタルアミド）（ポリアミド９Ｔ）、ポリ（テトラメチレンイソフタルアミド）（ポリアミド４Ｉ）などの脂肪族－芳香族ポリアミド、およびこれらの共重合体や混合物を挙げることができる。特に本発明に好適なポリアミドとしてはポリアミド６、ポリアミド６６、ポリアミド６／６６共重合体、ポリアミド６６／６Ｔ共重合体、ポリアミド６Ｔ／１２共重合体、ポリアミド６Ｔ／１１共重合体、ポリアミド６Ｔ／６Ｉ共重合体、ポリアミド６Ｔ／６Ｉ／１２共重合体、ポリアミド６Ｔ／６１０共重合体、ポリアミド６Ｔ／６Ｉ／６共重合体を挙げることができる。 The present invention will be specifically described below.
The polyamide resin in the present invention is not particularly limited. For example, 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. Specifically, 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.
本発明におけるポリアミド樹脂としては、特に限定されるものではないが、例えば、環状ラクタムの開環重合物、アミノカルボン酸の重縮合物、二塩基酸とジアミンとの重縮合物、これらの共重合物などが挙げられ、具体的にはポリカプロアミド（ポリアミド６）、ポリヘキサメチレンアジパミド（ポリアミド６６）、ポリテトラメチレンアジパミド（ポリアミド４６）、ポリヘキサメチレンセバカミド（ポリアミド６１０）、ポリヘキサメチレンドデカミド（ポリアミド６１２）、ポリ－ラウリルラクタム（ポリアミド１２）、ポリ－１１－アミノウンデカン酸（ポリアミド１１）等の脂肪族ポリアミド、ポリ（メタキシレンアジパミド）（ポリアミドＭＸＤ６）、ポリ（ヘキサメチレンテレフタルアミド）（ポリアミド６Ｔ）、ポリ（ヘキサメチレンイソフタルアミド）（ポリアミド６Ｉ）、ポリ（ノナメチレンテレフタルアミド）（ポリアミド９Ｔ）、ポリ（テトラメチレンイソフタルアミド）（ポリアミド４Ｉ）などの脂肪族－芳香族ポリアミド、およびこれらの共重合体や混合物を挙げることができる。特に本発明に好適なポリアミドとしてはポリアミド６、ポリアミド６６、ポリアミド６／６６共重合体、ポリアミド６６／６Ｔ共重合体、ポリアミド６Ｔ／１２共重合体、ポリアミド６Ｔ／１１共重合体、ポリアミド６Ｔ／６Ｉ共重合体、ポリアミド６Ｔ／６Ｉ／１２共重合体、ポリアミド６Ｔ／６１０共重合体、ポリアミド６Ｔ／６Ｉ／６共重合体を挙げることができる。 The present invention will be specifically described below.
The polyamide resin in the present invention is not particularly limited. For example, 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. Specifically, 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.
このようなポリアミド樹脂の分子量は特に制限はないが、９８％（９８質量％）硫酸中、濃度１質量％、２５℃で測定する相対粘度が１．７～４．５のポリアミド樹脂を使用することが好ましい。ポリアミド樹脂の相対粘度は、より好ましくは、２．０～４．０、さらに好ましくは２．０～３．５である。
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.
本発明におけるポリアクリロニトリル系微粒子は、平均粒子径が２００μｍ以下であり、アクリロニトリル（ＡＮ）成分を主体とする重合体からなり、好ましくはアクリロニトリル（ＡＮ）成分を５０質量％以上含有する重合体からなる。アクリロニトリル（ＡＮ）成分の含有率は、より好ましくは６０質量％以上であり、さらに好ましくは７０質量％以上であり、特に好ましくは８０質量％以上であり、最も好ましくは９０質量％以上である。該ポリアクリロニトリル系微粒子は、アクリロニトリル以外に、アクリル酸エステル、メタアクリル酸エステル、スチレン、酢酸ビニル、メタアクリル酸グリシジル、メタアクリル酸ジグリシジル、ジビニルベンゼン、ポリエチレングリコール（ｎ＝１～９）ジメタクリレートからなる群より選ばれた１種以上の単量体を共重合せしめたものが推奨される。
アクリル酸エステル、メタアクリル酸エステルで例示できるエステルとしては、メチル（すなわちアクリル酸メチル、メタアクリル酸メチル）、エチル、ｎ－プロピル、ｉｓｏ－プロピル、ｎ－ブチル、ｓｅｃ－ブチル、ｔｅｒｔ－ブチル、シクロヘキシル、２－エチルヘキシル、ラウリル、ステアリル等が挙げられる。これらのコモノマーの選択や重合方法との組み合わせにより、微粒子の屈折率や形態特性が調整できる。 The polyacrylonitrile-based fine particles in the present invention have an average particle size of 200 μm 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. The polyacrylonitrile-based fine particles include, in addition to acrylonitrile, acrylic ester, methacrylic ester, styrene, vinyl acetate, glycidyl methacrylate, diglycidyl methacrylate, divinylbenzene, polyethylene glycol (n = 1 to 9) dimethacrylate. 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.
アクリル酸エステル、メタアクリル酸エステルで例示できるエステルとしては、メチル（すなわちアクリル酸メチル、メタアクリル酸メチル）、エチル、ｎ－プロピル、ｉｓｏ－プロピル、ｎ－ブチル、ｓｅｃ－ブチル、ｔｅｒｔ－ブチル、シクロヘキシル、２－エチルヘキシル、ラウリル、ステアリル等が挙げられる。これらのコモノマーの選択や重合方法との組み合わせにより、微粒子の屈折率や形態特性が調整できる。 The polyacrylonitrile-based fine particles in the present invention have an average particle size of 200 μm 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. The polyacrylonitrile-based fine particles include, in addition to acrylonitrile, acrylic ester, methacrylic ester, styrene, vinyl acetate, glycidyl methacrylate, diglycidyl methacrylate, divinylbenzene, polyethylene glycol (n = 1 to 9) dimethacrylate. 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.
また、ポリアクリロニトリル系微粒子は石油系、芳香族系、アルコール系溶剤中での膨潤度が１０体積％未満である架橋したポリアクリロニトリル系微粒子であることが好ましい。
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.
架橋したポリアクリロニトリル系微粒子の場合も、アクリロニトリルの含有率は、好ましくは５０質量％以上であり、より好ましくは６０質量％以上であり、さらに好ましくは７０質量％以上であり、特に好ましくは８０質量％以上であり、最も好ましくは９０質量％以上である。アクリロニトリルの含有率が高くなるほど粒子表面に形成される微細な凹凸が緻密となり、また微細な凹凸の領域も増加するため、比表面積は増加する。この比表面積の増加に伴い、酸素遮蔽性が向上していく。
Also in the case of cross-linked polyacrylonitrile-based fine particles, 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. As 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.
架橋させるために用いる架橋性ビニル単量体としては、ラジカル重合可能な不飽和二重結合を２個以上有する架橋性単量体であれば特に限定されるものではない。例えば、１，４－ジビニロキシブタン、ジビニルスルホン等のビニル化合物；ジアリルフタレート、ジアリルアクリルアミド、トリアリル（イソ）シアヌレート、トリアリルトリメリテート等のアリル化合物；（ポリ）エチレングリコールジ（メタ）アクリレート、（ポリ）プロピレングリコールジ（メタ）アクリレート等の（ポリ）オキシアルキレングリコールジ（メタ）アクリレート；ペンタエリスリトールテトラ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート及びグリセロールトリ（メタ）アクリレート、グリセロールジ（メタ）アクリレート、ジビニルベンゼン等が挙げられる。これらの架橋性ビニル単量体は２種以上混合して用いることができる。
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. For example, 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 (meth) acrylate, dipentaerythritol penta (meth) acrylate and glycerol tri (meth) acrylate Rate, glycerol di (meth) acrylate, divinylbenzene, and the like. These crosslinkable vinyl monomers can be used in combination of two or more.
架橋ポリアクリロニトリル系微粒子は、モノマーとしてアクリロニトリル、架橋性ビニル単量体以外にラジカル重合可能なビニルモノマーを適宜使用しても良い。該モノマーはラジカル重合可能なものであれば、特に限定されるものではない。例えば、アクリル酸メチル、アクリル酸エチル、アクリル酸２－エチルヘキシル、アクリル酸ラウリル、ジメチルアミノエチルアクリレート、ジエチルアミノエチルアクリレート等のアクリル酸エステル系単量体、メチルメタクリレート、エチルメタクリレート、メタクリル酸ラウリル、ジメチルアミノエチルメタクリレート等のメタクリル酸エステル系単量体、スチレン、ｐ－メチルスチレン等のスチレン系単量体、メチルビニルエーテル、エチルビニルエーテル等のアルキルビニルエーテル、酢酸ビニル、酪酸ビニル等のビニルエステル系単量体、Ｎ－メチルアクリルアミド、Ｎ－エチルアクリルアミド等のＮ－アルキル置換（メタ）アクリルアミド、メタクリルニトリル等のニトリル系単量体が挙げられる。このような単量体は、２種類以上を組み合わせて用いてもよい。
For the crosslinked polyacrylonitrile-based fine particles, 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. For example, 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.
本発明で用いるポリアクリロニトリル系微粒子は、上記のモノマーを用い、懸濁重合（パール重合）、懸濁沈殿重合、乳化重合などの重合方法を採用し、特開平９－２８６８１７号公報、特開２００３－２２６７２０号公報、特開２０１２－１８４４２０号公報などに開示された方法によって製造することができる。
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.
本発明で用いるポリアクリロニトリル系微粒子は、平均粒子径が２００μｍ以下の大きさで、ポリアミド樹脂中で均一的に分散できる状態のものであれば特に限定されないが、好ましくは平均粒子径が１００μｍ以下、より好ましくは６０μｍ以下、さらに好ましくは４０μｍ以下、特に好ましくは２０μｍ以下である。２００μｍを超えると、ポリアミド中での不均一分散になりやすく機械的物性が低下しやすい傾向がある。ポリアクリロニトリル系微粒子の大きさの下限は特に限定されないが、製造技術や製造コストの点で１μｍ程度である。ポリアクリロニトリル系微粒子の下限としては、３μｍがより好ましく、５μｍがさらに好ましい。
ポリアクリロニトリル系微粒子の平均粒子径は、実施例の項に記載の通り、レーザー回折式粒度測定装置を使用して測定できる。 The polyacrylonitrile-based fine particles used in the present invention are not particularly limited as long as the average particle size is 200 μm or less and can be uniformly dispersed in the polyamide resin, but preferably the average particle size is 100 μm 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 μm, 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 μm in terms of manufacturing technology and manufacturing cost. The lower limit of the polyacrylonitrile-based fine particles is more preferably 3 μm and even more preferably 5 μm.
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.
ポリアクリロニトリル系微粒子の平均粒子径は、実施例の項に記載の通り、レーザー回折式粒度測定装置を使用して測定できる。 The polyacrylonitrile-based fine particles used in the present invention are not particularly limited as long as the average particle size is 200 μm or less and can be uniformly dispersed in the polyamide resin, but preferably the average particle size is 100 μm 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 μm, 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 μm in terms of manufacturing technology and manufacturing cost. The lower limit of the polyacrylonitrile-based fine particles is more preferably 3 μm and even more preferably 5 μm.
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.
ポリアクリロニトリル系微粒子の含有量は、ポリアミド樹脂１００質量部に対して、ポリアクリロニトリル系微粒子を０．１～５質量部であり、好ましくは０.３～３質量部、より好ましくは０．４～２質量部である。５質量部を超えてもそれ以上の耐熱老化性の向上効果は得られず、組成物の機械的物性が低下し、０．１質量部未満では、配合効果が得られにくい。
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.
本発明における前記ポリアクリロニトリル系微粒子の耐熱老化性向上効果が発現する理由については不明であるが、ポリアクリロニトリル系微粒子がポリアミド樹脂の表層付近に存在することで、酸素の遮蔽効果が発現されるためではないかと考えられる。
The reason why the effect of improving the heat aging resistance of the polyacrylonitrile-based fine particles in the present invention is unclear, but because the polyacrylonitrile-based fine particles are present in the vicinity of the surface layer of the polyamide resin, an oxygen shielding effect is exhibited. It is thought that.
本発明においては、前記のポリアクリロニトリル系微粒子以外に、公知の熱安定剤も使用することができる。
In the present invention, in addition to the polyacrylonitrile-based fine particles, a known heat stabilizer can also be used.
本発明で用いることができる銅化合物としては、酢酸銅、沃化銅、臭化銅、塩化銅、フッ化銅、ラウリン酸銅、ステアリン酸銅等を挙げることができる。これらの銅化合物は単独で用いても良く、また併用しても良い。酢酸銅、沃化銅、臭化銅、塩化銅が好ましく、臭化第二銅が特に好ましく使用される。銅化合物の含有量は、ポリアミド樹脂１００質量部に対して、銅化合物中の銅として０．０００１～１質量部であることが好ましい。０．０００１質量部未満では、高温雰囲気かつ紫外線照射下のより厳しい環境下における変色防止効果が不十分であり、１質量部より多いと、前記の厳しい環境下における変色防止の効果が頭打ちになり、さらには金型や押出し機や成形機のスクリュー、シリンダー等を腐蝕する等の問題を発生する懸念がある。より好ましい含有量は、０．０００５～１質量部であり、さらに好ましい含有量は、０．００５～０．２質量部である。
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. If the amount is less than 0.0001 parts by mass, the effect of preventing discoloration in a high temperature atmosphere and a severer environment under ultraviolet irradiation is insufficient, and if the amount is more than 1 part by mass, the effect of preventing discoloration in the severe environment will reach its peak. Furthermore, there is a concern that problems such as corrosion of molds, screws, cylinders, etc. of extruders and molding machines may occur. 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.
また、銅化合物を添加する場合には、沃化カリウム、臭化カリウム等のハロゲン化アルカリ金属化合物を併用することが好ましい。併用により、銅の析出を防止することができる。銅化合物の添加方法としては、ポリアミド樹脂の製造の任意の段階において添加しても良く、その添加方法は限定されない。例えば、ポリアミドの原料塩水溶液に添加する方法、溶融重合の途中で溶融ポリアミド中に注入添加する方法、重合を終了して造粒したポリアミドペレットと該銅化合物の粉体またはマスターバッチをブレンドした後に押出し機や成形機等を用いて溶融混練する方法等のいずれであっても良い。
In addition, 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. As 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.
さらに、本発明においてには、ヒンダードフェノール系酸化防止剤、リン系酸化防止剤、硫黄系酸化防止剤、アミン系酸化防止剤などの酸化防止剤、光安定剤といった補助安定剤を配合することができる。
Furthermore, in the present invention, 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.
ヒンダードフェノール系酸化防止剤としては、公知の化合物が使用可能である。これらの化合物は単独で、あるいは組み合わせて使用することができる。このようなヒンダードフェノール系酸化防止剤の中でも、２官能以上のフェノールが好ましく、トリエチレングリコール－ビス〔３－（３－ｔｅｒｔ－ブチル－５－メチル－４－ヒドロキシフェニル）プロピオネート〕（ＩＲＧＡＮＯＸ２４５）などのセミヒンダードタイプが変色しにくさの点で好ましい。
Known compounds can be used as the hindered phenol antioxidant. These compounds can be used alone or in combination. Among such hindered phenolic antioxidants, phenols having two or more functional groups are preferable, and triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] (IRGANOX245) A semi-hindered type such as is preferable in terms of difficulty in discoloration.
ヒンダードフェノール系酸化防止剤を配合する場合、その配合量（含有量）は、ポリアミド樹脂１００質量部に対して、０．０５～３質量部であることが好ましく、より好ましくは０．１～２質量部である。０．０５質量部未満では、熱変色防止効果が不十分であり、一方、３質量部を超えると、効果が飽和に達したり、成形品表面へのブルーミングが生じることがある。
When a hindered phenol-based antioxidant is blended, 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.
リン系酸化防止剤としては、無機系及び有機系のリン系酸化防止剤から選ばれる少なくとも一種である。無機リン系酸化防止剤としては、次亜リン酸ナトリウムなどの次亜リン酸塩、亜リン酸塩などが挙げられる。
有機リン系酸化防止剤としては、ホスファイト系の市販されている有機リン系酸化防止剤を用いることができるが、熱分解でリン酸を生成しない有機系リン含有化合物が好ましい。かかる有機系リン含有化合物としては、公知の化合物が使用可能である。 The phosphorus antioxidant is at least one selected from inorganic and organic phosphorus antioxidants. Examples of inorganic phosphorus antioxidants include hypophosphites such as sodium hypophosphite and phosphites.
As the 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.
有機リン系酸化防止剤としては、ホスファイト系の市販されている有機リン系酸化防止剤を用いることができるが、熱分解でリン酸を生成しない有機系リン含有化合物が好ましい。かかる有機系リン含有化合物としては、公知の化合物が使用可能である。 The phosphorus antioxidant is at least one selected from inorganic and organic phosphorus antioxidants. Examples of inorganic phosphorus antioxidants include hypophosphites such as sodium hypophosphite and phosphites.
As the 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.
リン系酸化防止剤を配合する場合、その配合量（含有量）は、ポリアミド樹脂１００質量部に対して、０．０５～３質量部であることが好ましく、より好ましくは０．１～２質量部である。０．０５質量部未満では、熱変色防止効果が不十分であり、一方、３質量部を超えると、成形品にフラッシュが生じることがある。
本発明では、無機系及び有機系のリン系酸化防止剤を併用すると、酸化防止剤の配合量を少なくすることができるので好ましい。 When a phosphorus-based antioxidant is blended, 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.
本発明では、無機系及び有機系のリン系酸化防止剤を併用すると、酸化防止剤の配合量を少なくすることができるので好ましい。 When a phosphorus-based antioxidant is blended, 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.
本発明で用いることができるアミン系酸化防止剤としては、公知の化合物が使用可能である。また、第２級アリールアミンもアミン系酸化防止剤として挙げることができる。第２級アリールアミンとは、窒素原子に化学結合した炭素ラジカル２個を含有するアミン化合物であって、少なくとも１つ、好ましくは両方の炭素ラジカルが芳香族である、アミン化合物を意味する。
As the 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. By 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.
アミン系酸化防止剤を配合する場合、その配合量（含有量）は、ポリアミド樹脂１００質量部に対して、０．０５～３質量部であることが好ましく、より好ましくは０．１～２質量部である。０．０５質量部未満では、熱変色防止効果が不十分であり、一方、３質量部を超えると、効果が飽和に達したり、成形品表面へのブルーミングが生じることがある。
When the amine-based antioxidant is blended, 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.
本発明において用いることができる硫黄系酸化防止剤としては、公知の化合物が使用可能である。
As the sulfur-based antioxidant that can be used in the present invention, known compounds can be used.
硫黄系酸化防止剤を配合する場合、その配合量（含有量）は、ポリアミド樹脂１００質量部に対して、０．０５～３質量部であることが好ましく、より好ましくは０．１～２質量部である。０．０５質量部未満では、熱変色防止効果が不十分であり、一方、３質量部を超えると、効果が飽和に達したり、成形品表面へのブルーミングが生じることがある。
When a sulfur-based antioxidant is blended, 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.
本発明において用いることができる光安定剤は、１種または複数種のヒンダードアミン型光安定剤（ＨＡＬＳ）であることが好ましい。
好ましくは、ＨＡＬＳは、置換ピペリジン化合物から誘導される化合物、特にアルキル置換ピペリジニルまたはピペラジノン化合物、およびアルコキシ置換ピペリジニル化合物から誘導される化合物である。かかる化合物としては、公知の化合物が使用可能である。 The light stabilizer that can be used in the present invention is preferably one or more hindered amine type light stabilizers (HALS).
Preferably, 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. As such a compound, a known compound can be used.
好ましくは、ＨＡＬＳは、置換ピペリジン化合物から誘導される化合物、特にアルキル置換ピペリジニルまたはピペラジノン化合物、およびアルコキシ置換ピペリジニル化合物から誘導される化合物である。かかる化合物としては、公知の化合物が使用可能である。 The light stabilizer that can be used in the present invention is preferably one or more hindered amine type light stabilizers (HALS).
Preferably, 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. As such a compound, a known compound can be used.
本発明においては、第２級アリールアミンとＨＡＬＳとの混合物を使用することができる。好ましい実施形態は、少なくとも１つが第２級アリールアミンから選択され、少なくとも１つがＨＡＬＳの群から選択される、少なくとも２種類の補助安定剤を含む。補助安定剤混合物を配合する場合、その全配合量（全含有量）は、ポリアミド樹脂１００質量部に対して、０．５～１０質量部であることが好ましく、より好ましくは０．５～３質量部である。０．５質量部未満では、耐熱老化性を向上する効果が不足し、一方、１０質量部を超えると効果が飽和したり、成形品表面へブルーミングすることがある。
In the present invention, 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. When the auxiliary stabilizer mixture is blended, the total blending amount (total content) 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.
本発明においては、さらに、充填材を添加することにより強度、剛性、耐熱性などを大幅に向上させることができる。このような充填材としては、ガラス繊維、炭素繊維、金属繊維、アラミド繊維、アスベスト、チタン酸カリウムウィスカ、ワラストナイト、ガラスフレーク、ガラスビーズ、タルク、マイカ、クレー、炭酸カルシウム、硫酸バリウム、酸化チタンおよび酸化アルミニウムなどが挙げられ、なかでもチョップドストランドタイプのガラス繊維が好ましく用いられる。
これらを配合する場合、その配合量（含有量）は、ポリアミド樹脂１００質量部に対して５～１４０質量部が好ましく、特に好ましくは５～１００質量部である。 In the present invention, the strength, rigidity, heat resistance and the like can be significantly improved by adding a filler. Such fillers 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.
When these are blended, 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.
これらを配合する場合、その配合量（含有量）は、ポリアミド樹脂１００質量部に対して５～１４０質量部が好ましく、特に好ましくは５～１００質量部である。 In the present invention, the strength, rigidity, heat resistance and the like can be significantly improved by adding a filler. Such fillers 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.
When these are blended, 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.
また、本発明のポリアミド樹脂組成物に対して、本発明の目的を損なわない範囲で紫外線吸収剤（例えばレゾルシノール、サリシレート、ベンゾトリアゾール、ベンゾフェノンなど）、滑剤および離型剤、核剤、可塑剤、帯電防止剤、および染料・顔料を含む着色剤などの通常の添加剤の１種以上をポリアミド樹脂１００質量部に対して５質量部程度まで添加することができる。
本発明のポリアミド樹脂組成物は、上記で説明した各成分を含有することが可能であるが、上記充填材を除いた組成物において、ポリアミド樹脂とポリアクリロニトリル系微粒子の合計で９０質量％以上を占めることが好ましく、９５質量％以上を占めることがより好ましい。 Further, with respect to the polyamide resin composition of the present invention, ultraviolet absorbers (for example, resorcinol, salicylate, benzotriazole, benzophenone, etc.), lubricants and mold release agents, 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.
本発明のポリアミド樹脂組成物は、上記で説明した各成分を含有することが可能であるが、上記充填材を除いた組成物において、ポリアミド樹脂とポリアクリロニトリル系微粒子の合計で９０質量％以上を占めることが好ましく、９５質量％以上を占めることがより好ましい。 Further, with respect to the polyamide resin composition of the present invention, ultraviolet absorbers (for example, resorcinol, salicylate, benzotriazole, benzophenone, etc.), lubricants and mold release agents, 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.
本発明のポリアミド樹脂組成物は、実施例の項で説明する熱老化試験において、２００℃、１０００時間熱処理後の引張強度保持率が８０％以上である。本発明のポリアミド樹脂組成物は、上記で説明した構成を有することで、このような特性を達成できる。
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.
本発明における前記ポリアクリロニトリル系微粒子及び他の添加剤をポリアミド樹脂に含有させる方法は、特に制限されるものではなく、任意の方法で行われる。例えば全成分を予備混合した後、押出機やニーダ中で混練する方法や、予め任意の数成分を押出機やニーダ中で混練して得たペレットに、更に他の成分を混練配合する方法などが挙げられる。
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.
本発明のポリアミド樹脂組成物は、射出成形、押出成形、熱成形、圧縮成形、または、ブロー成形、ダイスライド成形などに代表された、いわゆる中空工法などにより成形体にすることができる。また、それら成形体を二次加工、例えば振動溶着、熱板溶着、超音波溶着などを含む溶着工法など、によっても成形体とすることができる。好ましくは、射出成形またはブロー成形体であり、その二次加工による成形体である。
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. Moreover, 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. Preferably, it is an injection-molded or blow-molded body, and a molded body by secondary processing thereof.
本発明のポリアミド樹脂組成物からなる成形体の用途例としては、自動車、車両分野では、例えば、シリンダー・ヘッド・カバー、エンジン・カバー、インタークーラー用のハウジング、バルブ、エンドキャップ、キャスター、トロリー部品など、さらに、吸気管（エア・ダクト）、特に吸気マニホールドなどの吸気系部品、コネクタ、歯車、ファン・ホイール、冷却材貯蔵コンテナー、熱交換器用のハウジングもしくはハウジング部材、ラジエーター、サーモスタット、クーラント及び送水ポンプ、ヒーター、締結エレメント、油受皿、マフラーなどの排気システムおよび触媒コンバータ用ハウジング、タイミングチェーンベルトフロントカバー、ギアボックス、ベアリングリテイナー、ガソリンキャップ、座席部品、ヘッドレスト、ドアハンドル、ワイパー部品などが挙げられる。
電気／電子機器分野では、例えば回路基板の部品、ハウジング、フィルム、コンダクター、スイッチ、ターミナル・ストリップ、リレー、レジスタ、コンデンサ、コイル、ランプ、ダイオード、ＬＥＤ、トランジスタ、コネクタ、コントローラー、メモリ、ボルト、コイルボビン、プラグ、プラグ部品、メカトロニクス部品、調理用機器、洗濯機、冷蔵庫、エアコンなどの家電機器部品、センサーなどが挙げられる。
生活関連、家具建材関連分野では、例えば車椅子、ベビーカー部品、椅子脚、肘掛け、手摺り、窓枠、ドアノブなどのための部品などが挙げられる。 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. In addition, intake pipes (air ducts), especially 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.
In the electrical / electronic equipment field, for example, 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.
In the fields related to daily life and furniture and building materials, there are, for example, parts for wheelchairs, stroller parts, chair legs, armrests, handrails, window frames, door knobs, and the like.
電気／電子機器分野では、例えば回路基板の部品、ハウジング、フィルム、コンダクター、スイッチ、ターミナル・ストリップ、リレー、レジスタ、コンデンサ、コイル、ランプ、ダイオード、ＬＥＤ、トランジスタ、コネクタ、コントローラー、メモリ、ボルト、コイルボビン、プラグ、プラグ部品、メカトロニクス部品、調理用機器、洗濯機、冷蔵庫、エアコンなどの家電機器部品、センサーなどが挙げられる。
生活関連、家具建材関連分野では、例えば車椅子、ベビーカー部品、椅子脚、肘掛け、手摺り、窓枠、ドアノブなどのための部品などが挙げられる。 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. In addition, intake pipes (air ducts), especially 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.
In the electrical / electronic equipment field, for example, 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.
In the fields related to daily life and furniture and building materials, there are, for example, parts for wheelchairs, stroller parts, chair legs, armrests, handrails, window frames, door knobs, and the like.
以下に実施例を用いて本発明を具体的に説明するが、本発明はこれらに限定されるもではない。なお、実施例に記載された測定値は、以下の方法によった。
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, the measured value described in the Example was based on the following method.
（１）使用原料
＊１：ポリアミド６：相対粘度ＲＶ＝２．６、集盛社製 ＴＰ４２０８
＊２：ポリアミド６６：相対粘度ＲＶ＝２．７、ローディア社製 Ｓｔａｂａｍｉｄ２７ＡＥ１Ｋ
＊３：ポリアクリロニトリル系微粒子Ａ（タフチックＡＭ、平均粒子径１０μｍ、ＡＮ含有率９５％、日本エクスラン社製）
＊４：ポリアクリロニトリル系微粒子Ｂ（タフチックＡ－２０、平均粒子径２４μｍ、ＡＮ含有率９５％、日本エクスラン社製）
＊５：酸化鉄（ＩＩＩ）：和光純薬社製
＊６：フェノール系酸化防止剤：ＢＡＳＦ社製 イルガノックス２４５
＊７：臭化第二銅：和光純薬社製 純度９９.９％
＊８：ガラスファイバー：日本電気硝子社製 Ｔ－２７５Ｈ (1) Raw materials used * 1: Polyamide 6: Relative viscosity RV = 2.6, TP4208 manufactured by Shumori Co.
* 2: Polyamide 66: Relative viscosity RV = 2.7, Stadamid27AE1K manufactured by Rhodia
* 3: Polyacrylonitrile-based fine particles A (Toughtic AM, average particle size 10 μm, AN content 95%, manufactured by Nippon Exlan)
* 4: Polyacrylonitrile-based fine particles B (Toughtic A-20, average particle size 24 μm, AN content 95%, manufactured by Nippon Exlan)
* 5: Iron (III) oxide manufactured by Wako Pure Chemical Industries, Ltd. * 6: Phenol antioxidant: Irganox 245 manufactured by BASF
* 7: Cupric bromide: 99.9% purity by Wako Pure Chemical Industries
* 8: Glass fiber: T-275H manufactured by Nippon Electric Glass Co., Ltd.
＊１：ポリアミド６：相対粘度ＲＶ＝２．６、集盛社製 ＴＰ４２０８
＊２：ポリアミド６６：相対粘度ＲＶ＝２．７、ローディア社製 Ｓｔａｂａｍｉｄ２７ＡＥ１Ｋ
＊３：ポリアクリロニトリル系微粒子Ａ（タフチックＡＭ、平均粒子径１０μｍ、ＡＮ含有率９５％、日本エクスラン社製）
＊４：ポリアクリロニトリル系微粒子Ｂ（タフチックＡ－２０、平均粒子径２４μｍ、ＡＮ含有率９５％、日本エクスラン社製）
＊５：酸化鉄（ＩＩＩ）：和光純薬社製
＊６：フェノール系酸化防止剤：ＢＡＳＦ社製 イルガノックス２４５
＊７：臭化第二銅：和光純薬社製 純度９９.９％
＊８：ガラスファイバー：日本電気硝子社製 Ｔ－２７５Ｈ (1) Raw materials used * 1: Polyamide 6: Relative viscosity RV = 2.6, TP4208 manufactured by Shumori Co.
* 2: Polyamide 66: Relative viscosity RV = 2.7, Stadamid27AE1K manufactured by Rhodia
* 3: Polyacrylonitrile-based fine particles A (Toughtic AM, average particle size 10 μm, AN content 95%, manufactured by Nippon Exlan)
* 4: Polyacrylonitrile-based fine particles B (Toughtic A-20, average particle size 24 μm, AN content 95%, manufactured by Nippon Exlan)
* 5: Iron (III) oxide manufactured by Wako Pure Chemical Industries, Ltd. * 6: Phenol antioxidant: Irganox 245 manufactured by BASF
* 7: Cupric bromide: 99.9% purity by Wako Pure Chemical Industries
* 8: Glass fiber: T-275H manufactured by Nippon Electric Glass Co., Ltd.
（２）測定方法
・平均粒子径： 微粒子を２０℃の脱イオン水に分散させ、レーザー回折式粒度測定装置（島津製作所製ＳＡＬＤ２０００）を用い、屈折率１．６０－０．１０ｉ、体積基準で測定、計算したメディアン径を平均粒子径（μｍ）と定義した。 (2) Measuring method / average particle size: 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 (μm).
・平均粒子径： 微粒子を２０℃の脱イオン水に分散させ、レーザー回折式粒度測定装置（島津製作所製ＳＡＬＤ２０００）を用い、屈折率１．６０－０．１０ｉ、体積基準で測定、計算したメディアン径を平均粒子径（μｍ）と定義した。 (2) Measuring method / average particle size: 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 (μm).
（３）試験方法
・引張強度、引張破断伸度： 東芝機械社ＩＳ－１００を用い、シリンダー２８０℃に設定し、金型温度９０℃の条件で成形品を得た後に、ＩＳＯ５２７－１，２に従って測定した。 (3) Test Method / Tensile Strength, Tensile Breaking Elongation: After using a Toshiba Machine Co., Ltd. IS-100, setting the cylinder at 280 ° C. and obtaining a molded product at a mold temperature of 90 ° C., ISO527-1, 2 Measured according to
・引張強度、引張破断伸度： 東芝機械社ＩＳ－１００を用い、シリンダー２８０℃に設定し、金型温度９０℃の条件で成形品を得た後に、ＩＳＯ５２７－１，２に従って測定した。 (3) Test Method / Tensile Strength, Tensile Breaking Elongation: After using a Toshiba Machine Co., Ltd. IS-100, setting the cylinder at 280 ° C. and obtaining a molded product at a mold temperature of 90 ° C., ISO527-1, 2 Measured according to
・熱老化試験： ＩＳＯ２５７８に詳述される手順に従って、再循環エアオーブン（ナガノ科学機械製作所製 熱風循環式乾燥機 ＮＨ－４０１Ｓ）において試験片を熱処理した。２００℃環境下で所定の試験時間（５００時間、１０００時間）で、試験片をオーブンから取り出し、室温に冷却し、試験の準備ができるまで、アルミニウム裏張りバッグ内に密閉した。次いで、ＩＳＯ５２７－１，２に従って、引張強度、引張破断伸度を測定した。３つの試験片から得られた平均値を採用した。
-Thermal aging test: In accordance with the procedure detailed in ISO 2578, the 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.
引張強度および引張破断伸度の保持率は、熱処理なしの初期の値を１００％としたときの５００時間、１０００時間熱処理した後の保持率である。
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%.
実施例１～７、比較例１～４
実施例及び比較例として記載した樹脂組成物は、上記の原材料を、それぞれ二軸押出機（コペリオン社製ＳＴＳ３５）を用いて、表１に記載の割合（質量割合）で配合し、溶融混練してペレット（直径約２．５ｍｍ×長さ約２．５ｍｍ）を得た。得られたペレットは熱風循環式乾燥機にて１００℃で４時間以上乾燥した後に使用した。評価結果を表１に示す。 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.
実施例及び比較例として記載した樹脂組成物は、上記の原材料を、それぞれ二軸押出機（コペリオン社製ＳＴＳ３５）を用いて、表１に記載の割合（質量割合）で配合し、溶融混練してペレット（直径約２．５ｍｍ×長さ約２．５ｍｍ）を得た。得られたペレットは熱風循環式乾燥機にて１００℃で４時間以上乾燥した後に使用した。評価結果を表１に示す。 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.
実施例１～７は、初期（熱処理前）の引張強度、引張破断伸度も高く、２００℃で５００時間、１０００時間熱処理後の引張強度保持率、引張破断伸度保持率も高い値を示している。
比較例１は、初期の引張強度が実施例に比べて低く、比較例２～４は、全て２００℃、５００時間で引張強度保持率は８０％以下、引張伸度保持率は５０％を下回っていることが確認された。 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
比較例１は、初期の引張強度が実施例に比べて低く、比較例２～４は、全て２００℃、５００時間で引張強度保持率は８０％以下、引張伸度保持率は５０％を下回っていることが確認された。 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
本発明によれば、ポリアミド樹脂に２００℃程度の高温環境下での耐熱老化性を簡便に安定的に向上させるこができるため、本発明によって得られたポリアミド樹脂成物は、２００℃の環境に曝される可能性がある、自動車、電気・電子製品の部品用として利用が可能である。
According to the present invention, 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
According to the present invention, 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
Claims (4)
- ポリアミド樹脂１００質量部に対して、平均粒子径が２００μｍ以下のポリアクリロニトリル系微粒子を０．１～５質量部含有することを特徴とするポリアミド樹脂組成物。 A polyamide resin composition comprising 0.1 to 5 parts by mass of polyacrylonitrile-based fine particles having an average particle diameter of 200 μm or less with respect to 100 parts by mass of the polyamide resin.
- 前記ポリアクリロニトリル系微粒子が、アクリロニトリル成分を５０質量％以上含有するポリアクリロニトリル系重合体からなる請求項１に記載のポリアミド樹脂組成物。 2. The polyamide resin composition according to claim 1, wherein the polyacrylonitrile-based fine particles comprise a polyacrylonitrile-based polymer containing 50% by mass or more of an acrylonitrile component.
- 銅化合物をポリアミド樹脂１００質量部に対して、銅として０．０００１～１質量部含有することを特徴とする請求項１または２に記載のポリアミド樹脂組成物。 The polyamide resin composition according to claim 1 or 2, wherein the copper compound is contained in an amount of 0.0001 to 1 part by mass as copper with respect to 100 parts by mass of the polyamide resin.
- ポリアミド樹脂１００質量部に対して、ガラス繊維を５～１４０質量部含有することを特徴とする請求項1～３のいずれかに記載のポリアミド樹脂組成物。
4. The polyamide resin composition according to claim 1, which contains 5 to 140 parts by mass of glass fiber with respect to 100 parts by mass of the polyamide resin.
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| JP2003292774A (en) * | 2002-04-03 | 2003-10-15 | Asahi Kasei Corp | Heat-resistant flame-retardant resin composition |
| JP2004131716A (en) * | 2002-09-17 | 2004-04-30 | Umg Abs Ltd | Thermoplastic resin composition |
| JP2006001970A (en) * | 2004-06-15 | 2006-01-05 | Yokohama Rubber Co Ltd:The | Thermoplastic resin composition for automobile component |
| JP2011046781A (en) * | 2009-08-25 | 2011-03-10 | Asahi Kasei Chemicals Corp | Polyamide resin composition and molded article comprising polyamide resin composition |
| JP2011080029A (en) * | 2009-09-09 | 2011-04-21 | Daicel Polymer Ltd | Resin composition for use in coated molded article |
| JP2014015594A (en) * | 2012-07-11 | 2014-01-30 | Asahi Kasei Chemicals Corp | Polyamide resin composition and molded article |
| JP2015520278A (en) * | 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 | Flame retardant polyamide with polyacrylonitrile homopolymer |
-
2017
- 2017-01-24 WO PCT/JP2017/002240 patent/WO2017130931A1/en active Application Filing
- 2017-01-24 JP JP2017510683A patent/JPWO2017130931A1/en active Pending
Patent Citations (8)
| 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 (en) * | 2002-04-03 | 2003-10-15 | Asahi Kasei Corp | Heat-resistant flame-retardant resin composition |
| JP2004131716A (en) * | 2002-09-17 | 2004-04-30 | Umg Abs Ltd | Thermoplastic resin composition |
| JP2006001970A (en) * | 2004-06-15 | 2006-01-05 | Yokohama Rubber Co Ltd:The | Thermoplastic resin composition for automobile component |
| JP2011046781A (en) * | 2009-08-25 | 2011-03-10 | Asahi Kasei Chemicals Corp | Polyamide resin composition and molded article comprising polyamide resin composition |
| JP2011080029A (en) * | 2009-09-09 | 2011-04-21 | Daicel Polymer Ltd | Resin composition for use in coated molded article |
| JP2015520278A (en) * | 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 | Flame retardant polyamide with polyacrylonitrile homopolymer |
| JP2014015594A (en) * | 2012-07-11 | 2014-01-30 | Asahi Kasei Chemicals Corp | Polyamide resin composition and molded article |
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|---|---|
| JPWO2017130931A1 (en) | 2018-11-15 |
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