JPH02228358A - Polyamide resin composition - Google Patents
Polyamide resin compositionInfo
- Publication number
- JPH02228358A JPH02228358A JP5092289A JP5092289A JPH02228358A JP H02228358 A JPH02228358 A JP H02228358A JP 5092289 A JP5092289 A JP 5092289A JP 5092289 A JP5092289 A JP 5092289A JP H02228358 A JPH02228358 A JP H02228358A
- Authority
- JP
- Japan
- Prior art keywords
- nylon
- present
- amine
- compd
- polytetramethyleneadipamide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title description 8
- 229920006122 polyamide resin Polymers 0.000 title description 5
- 150000001412 amines Chemical class 0.000 claims abstract description 19
- -1 copper halide Chemical class 0.000 claims abstract description 14
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 5
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 230000003712 anti-aging effect Effects 0.000 claims description 20
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 claims description 10
- 239000005749 Copper compound Substances 0.000 claims description 8
- 150000001880 copper compounds Chemical class 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 150000002497 iodine compounds Chemical class 0.000 claims description 8
- 229920003189 Nylon 4,6 Polymers 0.000 abstract description 14
- 239000011347 resin Substances 0.000 abstract description 14
- 229920005989 resin Polymers 0.000 abstract description 14
- 230000007774 longterm Effects 0.000 abstract description 11
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 5
- 229910021589 Copper(I) bromide Inorganic materials 0.000 abstract description 4
- 229910021595 Copper(I) iodide Inorganic materials 0.000 abstract description 4
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 abstract description 4
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 abstract description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 abstract 2
- 239000011630 iodine Substances 0.000 abstract 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 13
- 239000003921 oil Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 239000003365 glass fiber Substances 0.000 description 5
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000010687 lubricating oil Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- DGZQEAKNZXNTNL-UHFFFAOYSA-N 1-bromo-4-butan-2-ylbenzene Chemical class CCC(C)C1=CC=C(Br)C=C1 DGZQEAKNZXNTNL-UHFFFAOYSA-N 0.000 description 1
- VETPHHXZEJAYOB-UHFFFAOYSA-N 1-n,4-n-dinaphthalen-2-ylbenzene-1,4-diamine Chemical compound C1=CC=CC2=CC(NC=3C=CC(NC=4C=C5C=CC=CC5=CC=4)=CC=3)=CC=C21 VETPHHXZEJAYOB-UHFFFAOYSA-N 0.000 description 1
- ZRMMVODKVLXCBB-UHFFFAOYSA-N 1-n-cyclohexyl-4-n-phenylbenzene-1,4-diamine Chemical compound C1CCCCC1NC(C=C1)=CC=C1NC1=CC=CC=C1 ZRMMVODKVLXCBB-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- UUNBFTCKFYBASS-UHFFFAOYSA-N C(CCCCCCC)C=1C(=C(C=CC1)NC1=CC=CC=C1)CCCCCCCC Chemical compound C(CCCCCCC)C=1C(=C(C=CC1)NC1=CC=CC=C1)CCCCCCCC UUNBFTCKFYBASS-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 description 1
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N N-phenyl aniline Natural products C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 235000010582 Pisum sativum Nutrition 0.000 description 1
- 240000004713 Pisum sativum Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- 239000012208 gear oil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
ａ、産業上の利用分野
本発明は、自動車、２輪車などのトランスミッション、
エンジン機構部などで使用されるプラスチック保持器な
どを形成するために有用なプラスチック組成物に関し、
さらに詳しくはポリテトラメチレンアジパミドに対し、
特定量のＣｕ ／ Ｉと特定量のアミン系老化防止剤を
併用添加してなる組成物である。この発明のポリアミド
樹脂組成物は、エンジン周りの上記部品などに成形され
た場合に、その部品の高温使用時の長期熱安定性および
高温油上使用時での高温耐油性の両特性が優れたもので
ある。DETAILED DESCRIPTION OF THE INVENTION a. Field of Industrial Application The present invention relates to transmissions for automobiles, two-wheeled vehicles, etc.
Concerning plastic compositions useful for forming plastic cages used in engine mechanisms, etc.
More specifically, for polytetramethylene adipamide,
This is a composition in which a specific amount of Cu/I and a specific amount of an amine anti-aging agent are added together. When the polyamide resin composition of the present invention is molded into the above-mentioned parts around an engine, the parts exhibit excellent properties in both long-term thermal stability when used at high temperatures and high-temperature oil resistance when used on high-temperature oil. It is something.
ｂ、従来の技術
テトラメチジ゛ンジアミンとアジピン酸および、それ等
の機能誘導体からなるポリアミド樹脂は、ポリテトラメ
チレンアジパミド樹脂（以下、ナイロン４６という）と
して知られている。b. Prior Art A polyamide resin made of tetramethyldiamine, adipic acid, and functional derivatives thereof is known as polytetramethylene adipamide resin (hereinafter referred to as nylon 46).
このナイロン４６は、引張強度、曲げ強度などの機械的
強度に優れ、また耐熱性、摺動特性に優れているために
有用なエンジニアリングプラスチックとして、その実用
上の価値が大きい。Nylon 46 has excellent mechanical strength such as tensile strength and bending strength, as well as excellent heat resistance and sliding properties, so it has great practical value as a useful engineering plastic.
しかし、自動車、２輪車などのトランスミッション、エ
ンジン機構部などでは使用温度条件が定常的には８０℃
程度であるが、走行条件、環境および車の形式などによ
り１２０〜１３０℃、場合によっては１５０℃以上の温
度にまで達する場合がある。また、このような用途にお
いては一般にプラスチック成形品は高温下において使用
すること、および各種の添加剤が含まれている潤滑油に
接触することにより、プラスチック成形品に悪影響を与
え、その結果、プラスチック成形品の強度低下、成形外
観性の低下などの原因となる。However, in transmissions and engine mechanisms of automobiles, motorcycles, etc., the operating temperature is normally 80 degrees Celsius.
However, depending on the driving conditions, environment, type of car, etc., the temperature may reach 120 to 130°C, and in some cases even reach 150°C or more. In addition, in such applications, plastic molded products are generally used at high temperatures and come into contact with lubricating oil containing various additives, which adversely affects the plastic molded products. This causes a decrease in the strength of the molded product and a decrease in the appearance of the molded product.
これ等の欠点を改善する方法として、例えばガラス繊維
を添加する方法が用いられるが、この方法では耐熱性、
機械的特性、寸法安定性などは改善されるが、長期熱安
定性と高温耐油性を同時に改善するには未だいたってい
ない。As a method to improve these drawbacks, for example, a method of adding glass fiber is used, but this method does not improve heat resistance,
Although mechanical properties and dimensional stability have been improved, it has not yet been possible to simultaneously improve long-term thermal stability and high-temperature oil resistance.
Ｃ０発明が解決しようとする問題点
本発明者等は、ナイロン４６の長期熱安定性と高温耐油
性を同時に改良すべく検討を行なった結果、Ｃｕと■と
を特定割合で含有させ、かつアミン系老化防止剤を併用
した樹脂組成物は極めて優れた長期熱安定性、および高
温耐油性が同時に得られることを見い出し、かかる知見
に基づいて本発明に到達した。Problems to be Solved by the C0 Invention The present inventors conducted studies to simultaneously improve the long-term thermal stability and high-temperature oil resistance of Nylon 46, and found that they contained Cu and It has been discovered that a resin composition containing an anti-aging agent can simultaneously provide extremely excellent long-term thermal stability and high-temperature oil resistance, and based on this knowledge, the present invention has been achieved.
ｄ１問題点を解決するための手段
すなわち本発明は、ナイロン４６樹脂とハロゲン含有鋼
化合物、無機ヨウ素化合物およびアミン系老化防止剤と
からなり、ナイロン４６樹脂に対し、Ｃｕとして１２０
〜１５０１）ｐｍ、■として１１００ ｐｐｍ以上含有
し、かつアミン系老化防止剤を、好ましくはジアリール
−ｐ−フェニレンジアミン系老化防止剤を、ナイロン４
６樹脂１００重量部に対し、０．１〜５重量部含有して
いることを特徴とする安定化されたポリアミド樹脂組成
物を提供するものである。A means for solving the d1 problem, that is, the present invention, consists of a nylon 46 resin, a halogen-containing steel compound, an inorganic iodine compound, and an amine-based anti-aging agent.
~1501) pm, 1100 ppm or more as
The object of the present invention is to provide a stabilized polyamide resin composition characterized in that it contains 0.1 to 5 parts by weight per 100 parts by weight of 6 resin.
本発明で使用するポリテトラメチレンアジパミド樹脂は
、酸成分としてアジピン酸またはその機能誘導体を用い
、アミン成分としてテトラメチレンジアミンまたはその
機構誘導体を用いて、縮合反応により得られるポリアミ
ドを主成分とするが、そのアジピン酸成分またはテトラ
メチレンジアミン成分の一部を他の共重成分で置き換え
たものでもよい。The polytetramethylene adipamide resin used in the present invention uses adipic acid or a functional derivative thereof as an acid component, tetramethylene diamine or a mechanical derivative thereof as an amine component, and has a polyamide obtained by a condensation reaction as a main component. However, a part of the adipic acid component or tetramethylenediamine component may be replaced with another copolymer component.
ナイロン４６樹脂の製造方法として好ましい方法は、特
開昭５６−１４９４３０号公報および特開昭５６−１４
９４３１号公報に記載されている方法を挙げることがで
きる。Preferred methods for producing nylon 46 resin are disclosed in JP-A-56-149430 and JP-A-56-14.
The method described in Japanese Patent No. 9431 can be mentioned.
本発明で使用される好ましいナイロン４６樹脂の分子量
は、相対粘度（η ：測定温度３０℃、ｃ１
９７％硫酸を用い、濃度１ｇ／１００ｍ１で測定）１．
５以上、さらに好ましくは２．５〜５．０の範囲にある
ものである。The preferred molecular weight of the nylon 46 resin used in the present invention is the relative viscosity (η: measured at a measurement temperature of 30°C, using c1 97% sulfuric acid, at a concentration of 1 g/100 ml): 1.
5 or more, more preferably in the range of 2.5 to 5.0.
ナイロン４６樹脂の耐久性（長期熱安定性）を向上させ
る目的で、ハロゲン含有銅化合物と無機ヨウ素化合物が
併用して使用される。ハロゲン系銅化合物としては、塩
化第一銅、塩化第二銅、ヨウ化第−銅、臭化第一銅、臭
化第二銅、およびその他の銅化合物が挙げられるが、ヨ
ウ化第−銅、臭化第一銅が好ましく、さらに好ましくは
ヨウ化第−銅である。For the purpose of improving the durability (long-term thermal stability) of nylon 46 resin, a halogen-containing copper compound and an inorganic iodine compound are used in combination. Examples of halogenated copper compounds include cuprous chloride, cupric chloride, cuprous iodide, cuprous bromide, cupric bromide, and other copper compounds, including cuprous iodide. , cuprous bromide is preferred, and cuprous iodide is more preferred.
ハロゲン含有鋼化合物以外の無機ヨウ素化合物としては
、ヨウ化カリウム、ヨウ化ナトリウムおよびその他のヨ
ウ素化合物が挙げられるが、好ま・しくはヨウ化カリウ
ムである。その使用量は、ナイロン４６樹脂に対して、
Ｃｕとして１２０〜５００ｐｐｍ、好ましくは１２０〜
４００１）ｌ）■、さらに好ましくは１５０〜４００１
）ｐｌ特に好ましくは１５０〜３００ ｐｐｍである。Inorganic iodine compounds other than halogen-containing steel compounds include potassium iodide, sodium iodide and other iodine compounds, with potassium iodide being preferred. The amount used is based on nylon 46 resin.
120 to 500 ppm as Cu, preferably 120 to 500 ppm
4001) l) ■, more preferably 150 to 4001
) pl is particularly preferably 150 to 300 ppm.
その使用量が１００ ｐｐｍ未満では耐久性に対する改
良効果が少なく好ましくない。５００ ｐｐｍを超える
と耐久性が低下し、また変色するので好ましくない。■
の使用量は１ｌ１００ｐｐ以上であり、好ましくは１５
００〜６０００ ｐｐＭである。その使用量が少ないと
着色する場合があり、また耐久性が劣るために好ましく
ない。If the amount used is less than 100 ppm, the effect of improving durability is small, which is not preferable. If it exceeds 500 ppm, durability decreases and discoloration occurs, which is not preferable. ■
The amount used is 1l100pp or more, preferably 15
00-6000 ppM. If the amount used is too small, it may cause coloring and the durability will be poor, which is not preferable.
さらに、本発明に使用するアミン系老化防止剤としては
、Ｎ、 Ｎ’−ジフェニル−ｐ−フェニレンジアミン、
Ｎ、Ｎ’ −ジー２−ナフチル−ｐ−フェニレンジアミ
ンなどのジアリール−ｐ−フエらレンジアミン系老化防
止剤、Ｎ−フェニル−Ｎ′−イソプロピル−ｐ−フェニ
レンジアミン、Ｎ−フェニル−Ｎ’ −（１，３−ジメ
チルブチル）−ｐ−フェニレンジアミン、Ｎ−フェニル
−Ｎ′−シクロへキシル−ｐ−フェニレンジアミンなど
のアリールアルキル−ｐ−フェニレンジアミン系老化防
止剤、アルキレ−ティラドジフェニルアミド、４，４′
−ジ−オクチルジフェニルアミンなどのジフェニルア
ミン系老化防止剤およびその他のアミン系老化防止剤と
してフェニル−１−ナフチルアミン、２−メルカプトベ
ンズイミダゾール、２．２．４−トリメチル−１，２−
ジハイドロキノリンのポリマーなどが挙げられるが、こ
れらのアミン系老化防止剤のうち芳香族系アミンが好ま
しく、ジアリール−ｐ−フェニレンジアミン系老化防止
剤が特に効果が著しい。上記老化防止剤は単独で使用し
てもよいし、混合したものであってもよい。また、必要
に応じてアミン系以外の老化防止剤も併用してもよい。Furthermore, the amine anti-aging agent used in the present invention includes N, N'-diphenyl-p-phenylenediamine,
Diaryl-p-phenylenediamine antioxidants such as N,N'-di-2-naphthyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N-phenyl-N'- (1,3-dimethylbutyl)-p-phenylenediamine, arylalkyl-p-phenylenediamine antioxidants such as N-phenyl-N'-cyclohexyl-p-phenylenediamine, alkylene-tiradiphenylamide, 4 ,4'
- Diphenylamine antioxidants such as di-octyldiphenylamine and other amine antioxidants such as phenyl-1-naphthylamine, 2-mercaptobenzimidazole, 2.2.4-trimethyl-1,2-
Among these amine-based anti-aging agents, aromatic amines are preferred, and diaryl-p-phenylenediamine-based anti-aging agents are particularly effective. The above anti-aging agents may be used alone or in combination. Furthermore, anti-aging agents other than amine-based antioxidants may be used in combination, if necessary.
かかる老化防止剤としては、Ｎ、Ｎ−へキサメチレンビ
ス−３−（３，５−ジ−ターシャリブチル−４−ヒドロ
キシフェニル）−プロピオネート、トリエチレングリコ
ールビス−３−（３−ターシャリブチル−４−ヒドロキ
シ−５−メチルフェニル）−プロピオネートなどが挙げ
られる。Such anti-aging agents include N,N-hexamethylene bis-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate, triethylene glycol bis-3-(3-tert-butyl -4-hydroxy-5-methylphenyl)-propionate and the like.
アミン系老化防止剤の使用量は、ナイロン４６樹脂１０
０重量部に対して、０．１〜５重量部、好ましくは０．
２〜３重量部配合することにより、高温下の潤滑油中で
の熱劣化特性が著しく改良され、優れた品質のものが得
られる。これ等アミン系老化防止剤の配合量が０．１重
量部未満では、高温下での潤滑油中での熱劣化特性（高
温耐油性）の改良が小さく、万一 ５重量部を超えると
成形加工性や成形外観が低下する。The amount of amine anti-aging agent used is 10 parts of nylon 46 resin.
0.1 to 5 parts by weight, preferably 0.0 parts by weight.
By blending 2 to 3 parts by weight, the thermal deterioration characteristics in lubricating oil at high temperatures are significantly improved, and products of excellent quality can be obtained. If the amount of these amine anti-aging agents is less than 0.1 part by weight, the improvement in thermal deterioration characteristics (high temperature oil resistance) in lubricating oil at high temperatures will be small, and if the amount exceeds 5 parts by weight, molding will occur. Processability and molded appearance deteriorate.
本発明の安定化されたポリテトラメチレンアジパミド樹
脂組成物は、公知の混練機である各種押出機、バンバリ
ーミキサ−、ニーダ−、ロールなどで混練することによ
って行なうことができる。The stabilized polytetramethylene adipamide resin composition of the present invention can be kneaded using known kneading machines such as various extruders, Banbury mixers, kneaders, rolls, and the like.
好ましい方法は押出機を用いる方法であり、特に好まし
い押出機は二輪押出機を用いる方法である。押出機で混
練する場合、好ましいバレル温度は２９０〜３３０℃の
範囲である。A preferred method is a method using an extruder, and a particularly preferred extruder is a method using a two-wheel extruder. When kneading with an extruder, the preferred barrel temperature is in the range of 290 to 330°C.
押出機を用いる場合、ハロゲン系銅化合物、無機ヨウ素
化合物およびアミン系老化防止剤の添加方法は特に限定
はしないが、■ナイロン４６樹脂、ハロゲン含有銅化合
物、無機ヨウ素化合物およびアミン系老化防止剤をブレ
ンドして一括して混練押出しをする方法。■ハロゲン含
有銅化合物、無機ヨウ素化合物およびアミン系老化防止
剤をブレンドして、または分割して途中添加する方法。When using an extruder, the method of adding the halogen-based copper compound, inorganic iodine compound, and amine-based anti-aging agent is not particularly limited; A method of blending and kneading and extruding all at once. ■A method in which a halogen-containing copper compound, an inorganic iodine compound, and an amine anti-aging agent are blended or added in portions during the process.
■あらかじめナイロン４６樹脂に高濃度のハロゲン含有
銅化合物、無機ヨウ素化合物およびアミン系老化防止剤
を添加したペレットを製造しておき、さらにそれをナイ
ロン４６樹脂と混合し、目的の濃度にする方法などがあ
る。特に好ましいものは、ＣｕＳ Ｉおよびアミン系老
化防止剤の分散性の問題から上記■の方法である。■Preparing pellets by adding high concentrations of halogen-containing copper compounds, inorganic iodine compounds, and amine anti-aging agents to nylon 46 resin, and then mixing them with nylon 46 resin to achieve the desired concentration. There is. Particularly preferred is the above method (2) because of the problem of dispersibility of CuS I and the amine antioxidant.
本発明の樹脂組成物の使用に際して、ガラス繊維、炭素
繊維、金属繊維、ガラスピーズ、アスベスト、ウオラス
トナイト、マイカ、チタン酸カリウム、炭酸カルシウム
、タルク、硫酸バリウム、二硫化モリブデン、フッソ樹
脂などの充填剤を単独または併用して用いることができ
る。これらの充填剤のうち、ガラス繊維、炭素繊維の形
状としては、６〜６０μｍの繊維径と３０μｍ以上の繊
維長を有するものが好ましい。When using the resin composition of the present invention, glass fibers, carbon fibers, metal fibers, glass peas, asbestos, wollastonite, mica, potassium titanate, calcium carbonate, talc, barium sulfate, molybdenum disulfide, fluorocarbon resin, etc. Fillers can be used alone or in combination. Among these fillers, glass fibers and carbon fibers preferably have a fiber diameter of 6 to 60 μm and a fiber length of 30 μm or more.
ガラス繊維を使用する場合、繊維径は特に６〜１３μｍ
が好ましく、ガラス繊維の集束剤としては、ウレタン系
とアクリル系を併用した集束剤が特に好ましく、その比
はウレタン系／アクリル系＝６／４〜９／１が好ましい
。さらに、ウレタン系の集束剤は脂肪族系が好ましい。When using glass fiber, the fiber diameter is particularly 6 to 13 μm.
is preferable, and as a sizing agent for glass fibers, a sizing agent using a combination of urethane type and acrylic type is particularly preferable, and the ratio thereof is preferably urethane type/acrylic type = 6/4 to 9/1. Further, the urethane-based sizing agent is preferably an aliphatic one.
これらの充填剤は、その添加効果を得るためには、本発
明の組成物１００重粗部に対して３〜１５０重量部配合
することが好ましい。In order to obtain the effect of adding these fillers, it is preferable to mix 3 to 150 parts by weight with respect to 100 parts by weight of the composition of the present invention.
さらに、公知の難燃剤、可塑剤、着色剤、シリコンオイ
ルなどの添加物を添加して用いることができる。難燃剤
としては、Ｂｒ系化合物と三酸化アンチモンとの併用系
が好ましく、Ｂｒ系化合物としては、臭素化ポリスチレ
ン、臭素化ポリフェニレンエーテル、臭素化エポキシオ
リゴマーなどが良好な結果を与える。さらに、要求され
る性能に応じて、他の重合体、例えばナイロン６６、ナ
イロン６、ナイロン１１、ナイロン１２、ポリエチレン
、ポリプロピレン、ポリスチレン、ポリスルホン、ＰＰ
Ｓ、ＰＥＴ、ＰＢＴなどを適宜ブレンドすることができ
る。Furthermore, known additives such as flame retardants, plasticizers, colorants, and silicone oil can be added and used. As the flame retardant, a combination system of a Br-based compound and antimony trioxide is preferred, and as the Br-based compound, brominated polystyrene, brominated polyphenylene ether, brominated epoxy oligomer, etc. give good results. Furthermore, depending on the required performance, other polymers such as nylon 66, nylon 6, nylon 11, nylon 12, polyethylene, polypropylene, polystyrene, polysulfone, PP
S, PET, PBT, etc. can be blended as appropriate.
本発明のポリテトラメチレンアジパミド樹脂組成物は射
出成形、シート押出、フィルム押出、真空成形、異形成
形、発泡成形などによって各種成形品を得、自動車、電
気、電子分野などに使用することができる。The polytetramethylene adipamide resin composition of the present invention can be obtained into various molded products by injection molding, sheet extrusion, film extrusion, vacuum molding, irregular molding, foam molding, etc., and can be used in the automobile, electrical, electronic fields, etc. can.
ｅ、実施例
以下、実施例、比較例により本発明をさらに詳細に説明
するが、これらはいずれも例示的なものであって、本発
明の内容を限定するものではない。e. Examples The present invention will be explained in more detail by the following Examples and Comparative Examples, but all of these are illustrative and do not limit the content of the present invention.
表−１に示した組成割合にブレンドし、二軸押出機を用
いてペレット化した。除湿乾燥機で十分乾燥した後、射
出成形し、以下の評価用試験片を得た。The compositions were blended in the composition ratio shown in Table 1 and pelletized using a twin-screw extruder. After sufficiently drying in a dehumidifying dryer, injection molding was performed to obtain the following test pieces for evaluation.
（評価方法）
■ 荷重たわみ温度（ＨＤＴ）：ＡＳＴＭ Ｄ６４８
、荷重１８．６ｋｇ／ｃＪ、アニールなし■ 長期熱安
定性：成形した試験片を１８５℃キヤオーブン中に放置
した後の引張り強度の半減時間（ＨＬ Ｔ）を比較した
。(Evaluation method) ■ Load deflection temperature (HDT): ASTM D648
, load 18.6 kg/cJ, no annealing ■ Long-term thermal stability: The half-life time (HL T) of the tensile strength after the molded test pieces were left in a 185° C. oven was compared.
■ 高温耐油性：成形した試験片を１００℃のギアオイ
ル（シェルスパイラックスＥＰ）に３００時間浸漬し、
引張り強度の保持率を比較した。■ High temperature oil resistance: The molded test piece was immersed in gear oil (Shell Spirax EP) at 100°C for 300 hours.
The retention rate of tensile strength was compared.
（実施例・比較例）
表−１のナイロン４６、ナイロン６６は相対粘度（η、
。１）は３．５のものを用いた。Ｃｕと■は添加量、老
化防止剤は種類と添加量を示している。(Example/Comparative Example) Nylon 46 and nylon 66 in Table 1 have relative viscosity (η,
. For 1), one with a rating of 3.5 was used. Cu and ■ indicate the amount added, and anti-aging agent indicates the type and amount added.
以下余白
実施例
実施例１〜７は、Ｃｕｌ５Ｋｌを用いた例であり、実施
例８は、ＣｕＢｒ、ＫＩを用いた例であり、いずれ表−
１に示した結果から、本発明の成形品は本発明の目的と
する物性のものが得られていることがわかる。Examples 1 to 7 below are examples using Cul5Kl, and Example 8 is an example using CuBr and KI.
From the results shown in 1, it can be seen that the molded article of the present invention has the physical properties targeted by the present invention.
比較例
比較例１〜３は、Ｃｕ、Ｉおよび老化防止剤を添加して
いないものであるが、長期熱安定性、高温耐油性が大巾
に劣る。Comparative Examples Comparative Examples 1 to 3 do not contain Cu, I, or anti-aging agents, but are significantly inferior in long-term thermal stability and high-temperature oil resistance.
比較ｆ１１４．５は、老化防止剤を本発明の範囲を超え
て使用したものであり、高温耐油性が劣る。Comparative f114.5 uses an anti-aging agent beyond the scope of the present invention, and has poor high-temperature oil resistance.
比較例６は、本発明のアミン系老化防止剤以外の他の老
化防止剤（フェノール系）を用いたもので、高温耐油性
が劣る。Comparative Example 6 uses an anti-aging agent (phenol-based) other than the amine-based anti-aging agent of the present invention, and has poor high-temperature oil resistance.
比較例７は、ナイロン４６以外の他のポリアミド樹脂を
用いた組成物であり、本発明の組成物に競べ、耐熱性や
高温耐油性が劣り好ましくない。Comparative Example 7 is a composition using a polyamide resin other than nylon 46, and although it is comparable to the composition of the present invention, its heat resistance and high-temperature oil resistance are inferior, making it undesirable.
比較例８〜１０は、Ｃｕ、Ｉを本発明の範囲を超えて使
用したものであり、長期熱安定性が劣る。Comparative Examples 8 to 10 used Cu and I beyond the scope of the present invention, and had poor long-term thermal stability.
１０発明の効果
本発明は、長期熱安定性、高温耐油性および耐熱性の優
れたポリテトラメチレンアジパミド樹脂組成物である。10 Effects of the Invention The present invention is a polytetramethylene adipamide resin composition that has excellent long-term thermal stability, high-temperature oil resistance, and heat resistance.
したがって、本発明の組成物から得られる成形品、部品
などは長期熱安定性、高温耐油性、耐熱性に優れている
ことから、高温下あるいは潤滑油にさらされる用途にお
いて著しい効果が発揮され、自動車分野、電気・電子分
野およびその他各分野の種々の成形品、部品などに使用
できる。Therefore, molded articles, parts, etc. obtained from the composition of the present invention have excellent long-term thermal stability, high-temperature oil resistance, and heat resistance, and therefore exhibit remarkable effects in applications where they are exposed to high temperatures or lubricating oil. It can be used for various molded products and parts in the automotive field, electrical/electronic field, and other fields.
特許出願人 日本合成ゴム株式会社Patent applicant: Japan Synthetic Rubber Co., Ltd.
Claims (1)
、ハロゲン含有銅化合物以外の無機ヨウ素化合物および
アミン系老化防止剤とからなり、ポリテトラメチレンア
ジパミドに対し、Ｃｕとして１２０〜５００ｐｐｍ、Ｉ
として１１００ｐｐｍ以上含有し、さらにアミン系老化
防止剤をポリテトラメチレンアジパミド１００重量部に
対し、０．１〜５重量部含有することを特徴とするポリ
アミド樹脂組成物。It consists of polytetramethylene adipamide, a halogen-containing copper compound, an inorganic iodine compound other than the halogen-containing copper compound, and an amine anti-aging agent, and contains 120 to 500 ppm as Cu and I to polytetramethylene adipamide.
1,100 ppm or more of polytetramethylene adipamide, and further contains 0.1 to 5 parts by weight of an amine antioxidant based on 100 parts by weight of polytetramethylene adipamide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5092289A JPH02228358A (en) | 1989-03-01 | 1989-03-01 | Polyamide resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5092289A JPH02228358A (en) | 1989-03-01 | 1989-03-01 | Polyamide resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02228358A true JPH02228358A (en) | 1990-09-11 |
Family
ID=12872292
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5092289A Pending JPH02228358A (en) | 1989-03-01 | 1989-03-01 | Polyamide resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02228358A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996037552A1 (en) * | 1995-05-26 | 1996-11-28 | Idemitsu Petrochemical Co., Ltd. | Polystyrene resin composition and molded articles thereof |
| JP2016117890A (en) * | 2014-12-18 | 2016-06-30 | 旭化成ケミカルズ株式会社 | Polyamide resin composition and molded body |
-
1989
- 1989-03-01 JP JP5092289A patent/JPH02228358A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996037552A1 (en) * | 1995-05-26 | 1996-11-28 | Idemitsu Petrochemical Co., Ltd. | Polystyrene resin composition and molded articles thereof |
| JP2016117890A (en) * | 2014-12-18 | 2016-06-30 | 旭化成ケミカルズ株式会社 | Polyamide resin composition and molded body |
| CN105778493A (en) * | 2014-12-18 | 2016-07-20 | 旭化成株式会社 | Polyamide Resin Composition And Molded Article |
| US9752006B2 (en) * | 2014-12-18 | 2017-09-05 | Asahi Kasei Kabushiki Kaisha | Polyamide resin composition and molded article |
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