JPH0228246A - Resin composition having excellent impact resistance - Google Patents
Resin composition having excellent impact resistanceInfo
- Publication number
- JPH0228246A JPH0228246A JP17486388A JP17486388A JPH0228246A JP H0228246 A JPH0228246 A JP H0228246A JP 17486388 A JP17486388 A JP 17486388A JP 17486388 A JP17486388 A JP 17486388A JP H0228246 A JPH0228246 A JP H0228246A
- Authority
- JP
- Japan
- Prior art keywords
- polyphenylene ether
- modified
- ether resin
- lower alkyl
- resin composition
- 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 claims description 12
- 229920001955 polyphenylene ether Polymers 0.000 claims abstract description 39
- -1 olefin compound Chemical class 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 17
- 239000011347 resin Substances 0.000 claims abstract description 13
- 229920005989 resin Polymers 0.000 claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004711 α-olefin Substances 0.000 claims abstract description 10
- 229920006122 polyamide resin Chemical class 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 229920000428 triblock copolymer Polymers 0.000 claims abstract description 4
- 150000008065 acid anhydrides Chemical group 0.000 claims description 21
- 229920001971 elastomer Polymers 0.000 claims description 19
- 239000000806 elastomer Substances 0.000 claims description 19
- 150000007513 acids Chemical class 0.000 claims description 10
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 12
- 229920001577 copolymer Polymers 0.000 abstract description 8
- 238000001746 injection moulding Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 229920002554 vinyl polymer Polymers 0.000 abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 150000008064 anhydrides Chemical class 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 239000004677 Nylon Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 229920001778 nylon Polymers 0.000 description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 229920001400 block copolymer Polymers 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229920002633 Kraton (polymer) Polymers 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 2
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical group O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical group OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical group NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Chemical group 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000001815 facial effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、変性ポリフェニレンエーテル圏脂とポリアミ
ド樹脂からなる低温耐衝撃性に優れた樹脂組成物に関す
るものであり、種々の機械的性質、耐薬品性、耐熱性に
優れており、自動車分野、ＯＡ機器分野、家電・雑貨分
野等に好適な材料を提供するものである。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a resin composition comprising a modified polyphenylene ether resin and a polyamide resin and having excellent low-temperature impact resistance. It has excellent chemical resistance and heat resistance, and provides a material suitable for the automobile field, OA equipment field, home appliance/miscellaneous goods field, etc.
（従来技術及びその問題点）
ポリフェニレンエーテル樹脂は、熱的性質、機械的性質
、電気的性質等諸性質に優れているが、溶融加工温度が
高く、かつ流動性が低いためｒこ成形加工性に劣る欠点
がある。又、酸、アルカリ等の無機系薬品に対しては強
い抵抗性を有するが、ある種の有機溶剤に対しては溶解
、膨潤等力３おこり、耐溶剤性、耐油性の改善が強く求
められている。(Prior art and its problems) Polyphenylene ether resin has excellent properties such as thermal properties, mechanical properties, and electrical properties, but it has a high melt processing temperature and low fluidity, so it has poor rico-molding processability. There are disadvantages that are inferior to. In addition, although it has strong resistance to inorganic chemicals such as acids and alkalis, it dissolves and swells when exposed to certain organic solvents, so there is a strong need to improve its solvent resistance and oil resistance. ing.
この成形加工性と耐油性を共に改良する試みがいくつか
為されている。例えば、ポリフェニレンエーテルにポリ
アミドを２０％以下のｊＬ配合する方法（特公昭４５−
９９７号公報）、ポリフェニレンエーテルにポリアミド
を３０〜９５％の範囲で配合する方法（特公昭５９−４
１６６３号公報）などがある。ポリアミドを少１配合し
た場合は、成形加工性がある程度改善されるものの、耐
油性という面からすると充分な改善とはいい難く、また
、比較的配合量が多いと耐溶剤性は改良されるものの、
靭性が無く脆い材料にしかならない。これは、本質的に
ポリフェニレンエーテル樹脂とポリアミド樹脂との相溶
性が悪いことに起因している。このポリフェニレンエー
テル樹脂（以下、ＰＰＥと略称する）とポリアミド樹脂
（以下、ＰＡと略称する）との相溶性を高める方法がい
くつか提案されている。Several attempts have been made to improve both moldability and oil resistance. For example, a method of blending 20% or less of polyamide with polyphenylene ether (Japanese Patent Publication No. 45-
997), a method of blending polyamide with polyphenylene ether in a range of 30 to 95% (Japanese Patent Publication No. 59-4
Publication No. 1663). When a small amount of polyamide is blended, molding processability is improved to some extent, but from the perspective of oil resistance, it is difficult to say that the improvement is sufficient, and when a relatively large amount is blended, solvent resistance is improved, but ,
It becomes a brittle material with no toughness. This is essentially due to the poor compatibility between the polyphenylene ether resin and the polyamide resin. Several methods have been proposed to improve the compatibility between polyphenylene ether resin (hereinafter abbreviated as PPE) and polyamide resin (hereinafter abbreviated as PA).
例えば、マレイン酸やマレイミド等の分子内に炭素−炭
素二重結合とカルボン酸基、酸無水物基、酸アミド基、
イミド基等の官能基を有する化合物を第三成分として配
合する方法（特開昭５６−２６９１３号公報）、スチレ
ン系化合物とα、β−不飽和ジカルボン酸との共重合体
を配合する方法（特公昭５９−３３６１４号公報）など
がある。無水マレイン酸やマレイミドを第三成分として
配合しても充分なる相溶性の改善は為し得す、射出成形
のような高温、高速成形では、層状剥離、外観不良を呈
し、しかも充分なる靭性を有する材料が得難い。ｔだ、
無水マレイン酸とスチレンの共重合体を配合する場合に
は、耐熱性が低下する。For example, in molecules such as maleic acid and maleimide, carbon-carbon double bonds and carboxylic acid groups, acid anhydride groups, acid amide groups,
A method of blending a compound having a functional group such as an imide group as a third component (JP-A-56-26913), a method of blending a copolymer of a styrene compound and an α,β-unsaturated dicarboxylic acid ( Japanese Patent Publication No. 59-33614). Compatibility can be sufficiently improved even if maleic anhydride or maleimide is added as a third component, but in high-temperature, high-speed molding such as injection molding, delamination and poor appearance occur, and, moreover, sufficient toughness is not achieved. It is difficult to obtain materials with It's t.
When a copolymer of maleic anhydride and styrene is blended, heat resistance decreases.
（発明が解決しようとする問題点）
ＰＰＨに酸無水物構造を有する１、２−置換オレフィン
化合物を無触媒下熱的にグラフト化せしめた変性ポリフ
ェニレンエーテル樹脂（以下、変性ＰＰＥと略称する）
Ｋ、ＰＡを配合すると、未変性のＰＰＥとＰＡの配合の
場合と異なり、広い組成範囲において靭性のある樹脂組
成物が得られることが知られている（特開昭６２−１３
２９２４号公報）。(Problems to be Solved by the Invention) Modified polyphenylene ether resin (hereinafter abbreviated as modified PPE) in which a 1,2-substituted olefin compound having an acid anhydride structure is thermally grafted to PPH without a catalyst.
It is known that when K and PA are blended, a resin composition with toughness can be obtained over a wide composition range, unlike when unmodified PPE and PA are blended (Japanese Patent Laid-Open No. 62-13
2924).
しかしながら、この樹脂組成物は、耐・１ｌＩＩ！性の
一つの測定法である、ノツチ付アイゾツト衝撃強度にお
いて極めて低い値しか得られない。However, this resin composition has resistance to 1lII! Only an extremely low value was obtained for notched Izot impact strength, which is one method of measuring strength.
アイゾツト衝撃強度の改良を目的として種々のエラスト
マーを添加することが試みられているが必ずしも充分と
は言えない。また、エラストマーを添加することにより
初期のアイゾツト衝撃強度は改良されるものの、高温雰
囲気環境ではアイゾツト衝撃強度が著しく低下したり、
更に射出成形時の熱安定性が悪いと言う欠点がある。更
に、低温雰囲気環境下でのアイゾツト衝撃強度が低下す
るという欠点がある。Attempts have been made to add various elastomers to improve the Izod impact strength, but this is not always sufficient. In addition, although the initial Izot impact strength is improved by adding an elastomer, the Izot impact strength decreases significantly in a high-temperature atmosphere environment.
Furthermore, it has the disadvantage of poor thermal stability during injection molding. Furthermore, there is a drawback that the Izod impact strength is reduced in a low-temperature atmosphere environment.
（問題を解決するための手段）
本発明者らは、この変性ＰＰＥ、ＰＡ、及びエラストマ
ーから成る樹脂組成物の耐衝撃性、耐熱性、射出成形時
の熱安定性を改善すべく鋭意検討した結果、ＰＰＥを特
定のエラストマー即ち、水素添加Ａ−Ｂ−Ａ型ブロック
共重合体及び不飽和酸無水物などで変性されたエチレン
−α−オレフィン系共重合体の存在下に１．２−置換オ
レフィン化合物と溶融状態で反応せしめた変性ＰＰＥと
ＰＡを混合することにより、上記の欠点が著しく改良さ
れることを見いだし本発明に到達した。(Means for Solving the Problem) The present inventors have conducted extensive studies to improve the impact resistance, heat resistance, and thermal stability during injection molding of the resin composition made of modified PPE, PA, and elastomer. As a result, PPE was 1,2-substituted in the presence of a specific elastomer, that is, a hydrogenated A-B-A type block copolymer and an ethylene-α-olefin copolymer modified with an unsaturated acid anhydride. The inventors have discovered that the above drawbacks can be significantly improved by mixing PA with a modified PPE reacted with an olefin compound in a molten state, and have thus arrived at the present invention.
すなわち、本発明は、
（式中、Ｒ１は炭素数１〜３の低級アルキル基、Ｒ２、
Ｒ３は水素原子又は炭素数１〜３の低級フルキル基であ
る。）
で表される構造単位な主鎖に持つポリフェニレンエーテ
ル樹脂を水素添加Ａ−Ｂ−Ａ型プ゛ロック共重合弾性体
（ここで、Ａはビニル芳香族炭化水素の重合体ブロック
をＢは共役ジエン系炭化水素化合物の重合体ブーツクを
意味する）と不飽和酸無水物及び不飽和酸から選ばれた
少なくとも一種で変性されたエチレン−α−オレフィン
系共重合体の共存下に酸無水物構造を有する１、２−置
換オレフィン化合物と溶融状態で反応せしめて得られる
変性ポリフェニレンエーテル樹脂と、
（ｂ） ポリアミド樹脂 から成る低温耐衝撃性に優
れた新規な樹脂組成物である。That is, the present invention provides the following: (wherein R1 is a lower alkyl group having 1 to 3 carbon atoms, R2,
R3 is a hydrogen atom or a lower furkyl group having 1 to 3 carbon atoms. ) Hydrogenated A-B-A type block copolymer elastomer of polyphenylene ether resin having the structural unit main chain represented by (where A is a vinyl aromatic hydrocarbon polymer block and B is a conjugated An acid anhydride structure is formed in the coexistence of a diene-based hydrocarbon compound polymer (bootsk) and an ethylene-α-olefin copolymer modified with at least one selected from unsaturated acid anhydrides and unsaturated acids. This is a novel resin composition with excellent low-temperature impact resistance, consisting of a modified polyphenylene ether resin obtained by reacting in a molten state with a 1,2-substituted olefin compound having the following: and (b) a polyamide resin.
ＰＰＥを特定のエラストマーの共存下に酸無水物構造を
有する１、２−置換オレフィン化合物と溶融状態で反応
させて得られた変性ＰＰＥを使用した本発明組成物は従
来法で得られた組成物と比較して、耐衝撃性、（特に低
温雰囲気下での耐衝撃性）、耐熱性、射出成形時の熱安
定性が大幅に改良されることは全く新しい発明であり驚
くべき事である。The composition of the present invention, which uses modified PPE obtained by reacting PPE with a 1,2-substituted olefin compound having an acid anhydride structure in a molten state in the presence of a specific elastomer, is different from a composition obtained by a conventional method. It is a completely new invention and surprising that the impact resistance (especially impact resistance in a low-temperature atmosphere), heat resistance, and thermal stability during injection molding are significantly improved compared to the previous invention.
ここで本発明の樹脂組成物に用いられるポリフェニレン
エーテルｔｔｉＷｆｔトｔｔ、一般式（式中、ＲＩ
は炭素数１〜３の低級アルキル基、Ｒ２、Ｒ３は水素原
子又は炭素数１〜３の低級アルキル基である。）
で表される構造単位な主鎖にもつ重合体であって、ホモ
ポリマーであってもコポリマーであってもよく、具体的
には、例えば、ポＩＪ（２，６−シメチルー１．４−フ
ェニレン）エーテル、ポリ（２，６−ジニチルー１，４
−）１二しン）エーテル、ポリ（２，６−ジプロビルー
１，４−７エニレン）エーテル、ポリ（２−メチル、６
−エチル−１，４−フエニレン）エーテル、ポリ（２−
メチル−６−６−ブロビルー１．４−フェニレン）エー
テル等があげられるが、特に、ポリ（２，６−シメチル
ー１．４−）１二しン）エーテル、２．６−シメチルフ
エノール／２，３．６−ドリメチルフエノール共重合体
が好ましい。また、ＰＰＥと反応させる酸無水物構造を
有する１、２−置換オレフィン化合物としては、例えば
、無水マレイン酸、無水イタコン酸、無水シトラコン酸
等があげられ、特に無水マレイン酸が好ましい。Here, the polyphenylene ether ttiWfttt used in the resin composition of the present invention has the general formula (wherein, RI
is a lower alkyl group having 1 to 3 carbon atoms, and R2 and R3 are a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms. ) is a polymer having a main chain of a structural unit represented by the following formula, which may be a homopolymer or a copolymer. Specifically, for example, polyJ (2,6-cymethyl-1,4- phenylene) ether, poly(2,6-dinityl-1,4
-) 1-dipropylene) ether, poly(2,6-diprobyl-1,4-7enylene) ether, poly(2-methyl, 6
-ethyl-1,4-phenylene)ether, poly(2-
Examples include methyl-6-6-brobyl-1,4-phenylene) ether, particularly poly(2,6-dimethyl-1,4-)1-dishine) ether, 2,6-dimethylphenol/2 , 3,6-dolimethylphenol copolymer is preferred. Further, examples of the 1,2-substituted olefin compound having an acid anhydride structure to be reacted with PPE include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like, with maleic anhydride being particularly preferred.
次に、本発明の樹脂組成物に用いられる水素添加ブロッ
ク共重合弾性体は、Ａ−Ｂ−Ａ型の構造をしており、Ａ
およびＢはそれぞれ重合体ブロックを示し、中心ブロッ
クＢは、共役ジエン系炭化水素化合物、通常はブタジェ
ンの重合体から成り、水添する前はポリブタジェンブロ
ックであるが、水素添加することにより、ポリブタジェ
ン中の二重結合が飽和炭化水素に転化されているブロッ
クであり、末端ブロックＡはビニル芳香族炭化水素の重
合体ブロックを示し、好適にはポリスチレンからなるブ
ロックである。Next, the hydrogenated block copolymer elastomer used in the resin composition of the present invention has an A-B-A type structure.
and B each indicate a polymer block, and the central block B is composed of a polymer of a conjugated diene hydrocarbon compound, usually butadiene, and is a polybutadiene block before hydrogenation, but by hydrogenation, This is a block in which the double bonds in polybutadiene are converted into saturated hydrocarbons, and the terminal block A represents a vinyl aromatic hydrocarbon polymer block, preferably a block made of polystyrene.
末端ブロックへの分子量は、４，０００〜１１ｓ、ｏｏ
ｏ、好ましくは、ｓ、ｏｏｏ〜１５゜０００、中心ブシ
フクＢの分子量は、２０，０００〜４５０，０００、好
ましくは、２５，０ＯＯ〜１００，０００であることが
望ましい。The molecular weight to the end block is 4,000-11s, oo
o, preferably s, ooo to 15°000, and the molecular weight of the central Bushifuku B is preferably 20,000 to 450,000, preferably 25,000 to 100,000.
かかる水素添加ブロック共重合弾性体は、容易に市場で
入手でき、たとえばシェル化学より［クレイドア Ｇ１
６５０Ｊ、「クレイトン Ｇ１６５１Ｊ、「クレイトン
Ｇ１６５７Ｊ等の商品名及びグレード名で市販されて
いる。Such hydrogenated block copolymer elastomer is easily available on the market, for example from Shell Chemical Co., Ltd. [Claydoor G1
650J, "Krayton G1651J,""Klayton G1657J, etc." are commercially available under trade names and grade names.
また、本発明の樹脂組成物において水素添加ブロック共
重合弾性体と組み合わせて使用されるエラストマー成分
は、不飽和酸無水物および不飽和酸から選ばれた少なく
とも一種で変性されたエチレン−α−オレフィン系共重
合体であり、この中で特に好ましいのはエチレン−α−
オレフィン系共重合体に不飽和酸及び不飽和酸無水物が
共重合、特にグラフト重合した重合体である。Furthermore, the elastomer component used in combination with the hydrogenated block copolymer elastomer in the resin composition of the present invention is an ethylene-α-olefin modified with at least one selected from unsaturated acid anhydrides and unsaturated acids. ethylene-α-based copolymers, and particularly preferred among these are ethylene-α-
It is a polymer obtained by copolymerizing, especially graft polymerizing, an olefin copolymer with an unsaturated acid and an unsaturated acid anhydride.
ここで使用されるα−オレフィンは、炭素数３〜２０個
を有する不飽和炭化水素化合物であり、具体例としては
プロピレン、ブテン−１、ペンテン−１，ヘキセン−１
、ヘフテン−１゜４−メチルブテン−１，４−メチルペ
ンテンー１等が挙げられるが特に好ましくはプロピレン
である。エチレンとα−オレフィンの配合比は９０：１
０〜１０：９０が好ましい。The α-olefin used here is an unsaturated hydrocarbon compound having 3 to 20 carbon atoms, and specific examples include propylene, butene-1, pentene-1, hexene-1
, heftene-1°4-methylbutene-1,4-methylpentene-1, etc., but propylene is particularly preferred. The blending ratio of ethylene and α-olefin is 90:1
0 to 10:90 is preferred.
また不飽和酸無水物及び不飽和酸としては、無水マレイ
ン酸、無水イタコン酸、クーー無水マレイン酸、無水シ
トラコン酸、ブテニル無水コハク酸、テトラヒドロ無水
フタル酸等及びこれらの酸があり、特に好ましい不飽和
酸無水物または酸は無水マレイン酸またはマレイン酸で
ある。これらの不飽和酸無水物または酸は一種又は二種
以上で使用される。エチレン−α−オレフィン系共重合
体と不飽和酸無水物又は不飽和酸との反応は、過酸化物
の存在下に、エチレン−α−オレフィン系共重合体と不
飽和酸無水物又は不飽和酸を混合し、押出機、ミキサー
等で１００〜２５０℃で１〜１０分混練することによっ
て行うが、この場合、不飽和酸無水物又は不飽和酸の量
は、エチレン−（Ｉ−オレフィン系共重合体に対して０
．１〜５重量９（が好ましい。Examples of unsaturated acid anhydrides and unsaturated acids include maleic anhydride, itaconic anhydride, cou-maleic anhydride, citraconic anhydride, butenyl succinic anhydride, tetrahydrophthalic anhydride, etc., and these acids are particularly preferred. The saturated acid anhydride or acid is maleic anhydride or maleic acid. These unsaturated acid anhydrides or acids may be used alone or in combination of two or more. The reaction between the ethylene-α-olefin copolymer and the unsaturated acid anhydride or unsaturated acid is carried out in the presence of a peroxide. This is carried out by mixing acids and kneading for 1 to 10 minutes at 100 to 250°C using an extruder, mixer, etc. In this case, the amount of unsaturated acid anhydride or unsaturated acid is ethylene-(I-olefin-based 0 for copolymers
．． 1 to 5 weight 9 (preferably.
かかるエラストマーは容易に市場で入手でき、例えば、
エクソン化学株より「エクセロールＶＡ１８０３Ｊ、三
井石油化学株より「タフマＭＰ−０６１０Ｊ等の商品名
及びグレード名で市販されている。Such elastomers are readily available on the market, e.g.
It is commercially available under trade names and grade names such as "Excerol VA1803J" from Exxon Chemical Co., Ltd. and "Tafuma MP-0610J" from Mitsui Petrochemical Co., Ltd.
水素添加ブーツク共重合弾性体、又は、不飽和酸無水物
および不飽和酸から選ばれた少なくとも一種で変性され
たエチレン−α−オレフィン系共重合体は、それぞれ単
独で使用した場合、高温雰囲気下でのアイゾツト衝撃は
改良されるが、低温雰囲気下では低いアイゾツト衝撃値
しか示さない。上記２つのエラストマーを併用しり場合
ニ低温雰囲気下でのアイゾツト衝撃値の向上が達成でき
るのである。Hydrogenated Bootsk copolymer elastomer or ethylene-α-olefin copolymer modified with at least one selected from unsaturated acid anhydride and unsaturated acid can be used alone in a high temperature atmosphere. Although the Izot impact value is improved at low temperatures, it only shows a low Izot impact value in a low temperature atmosphere. When the above two elastomers are used in combination, it is possible to improve the Izot impact value in a low temperature atmosphere.
ＰＰＥの変性に要する酸無水物構造を有する１、２−置
換オレフィン化合物の量は、ＰＰＥ１００重量部に対し
て０．０１〜１０重量％、好ましくは０．１〜３重量％
、特に好ましくは０．１〜２重量％の範囲の量である。The amount of the 1,2-substituted olefin compound having an acid anhydride structure required for modification of PPE is 0.01 to 10% by weight, preferably 0.1 to 3% by weight based on 100 parts by weight of PPE.
, particularly preferably in an amount in the range from 0.1 to 2% by weight.
これより少量では、ＰＰＥ、！：ＰＡの相溶性の改善効
果が小さく、靭性のある組成物が得難いし、この範囲よ
りも多く使用すると、ＰＰＥ粒子の分散径が大きくなる
等の不具合があり、更に耐熱性の低下や外観不良等好ま
しからざる現象が惹起する。In smaller quantities, PPE,! : The effect of improving the compatibility of PA is small, making it difficult to obtain a composition with toughness, and if it is used in an amount exceeding this range, there will be problems such as an increase in the dispersed diameter of PPE particles, and furthermore, a decrease in heat resistance and poor appearance. Undesirable phenomena such as this occur.
又、ＰＰＥの変性の際に共存せしめる水添ブロック共重
合弾性体と不飽和酸無水物および不飽和酸から選ばれた
少゛なくとも一種→唆性さ八Ｔ′
タエチレンーα−オレフィン系共重合体ハソノ今量で、
ＰＰＥ １００重量部に対して２〜４〇七
重量％、好ましくは５〜３０重度％、特に好ましくけ、
１０〜２０重量％の範囲であり、これより少ないと衝撃
強度の改良が不十分で、この範囲より多くすると機械的
強度の低下が生じる。In addition, at least one type of hydrogenated block copolymer elastomer and an unsaturated acid anhydride and an unsaturated acid selected from unsaturated acid anhydrides and unsaturated acids coexist during the modification of PPE. Combined with the amount of hasono,
2 to 407% by weight, preferably 5 to 30% by weight, particularly preferably, based on 100 parts by weight of PPE,
The amount is in the range of 10 to 20% by weight; if it is less than this, the impact strength is insufficiently improved, and if it is more than this range, the mechanical strength will be reduced.
ＰＰＥと水素添加ブロック共重合弾性体、および不飽和
酸無水物および不飽和酸から選ばれた少なくとも一種で
変性されたエチレン−α−オレフィン系共重合体の混合
物と酸無水物構造を有する１、２−置換オレフィン化合
物との反応は、加熱溶融混練すること１こより得られる
が、混練ニはニーダ−、バンバリーミキサ−１押出機等
が用いられるが操作性等から押出機を用し・るのが好ま
しい。1 having an acid anhydride structure and a mixture of PPE, a hydrogenated block copolymer elastomer, and an ethylene-α-olefin copolymer modified with at least one selected from unsaturated acid anhydrides and unsaturated acids; The reaction with the 2-substituted olefin compound can be obtained by heating, melting, and kneading, but for kneading, a kneader, a Banbury mixer-1 extruder, etc. are used, but it is preferable to use an extruder for ease of operation. is preferred.
本発明の樹脂組成物に用いられるポリアミド樹脂（Ｐ
Ａ）は、主鎖に −〇〇−ＮＨ−結合を有する重合体で
あって、例えば、４−ナイロン、４．６−ナイロン、６
−ナイロン、６，６−ナイロン、１２−ナイロン、１１
−ナイロン、６゜１０−ナイロン、ＭＸＤ−ナイロンな
どがあげられる。Polyamide resin (P) used in the resin composition of the present invention
A) is a polymer having -〇〇-NH- bonds in the main chain, such as 4-nylon, 4.6-nylon, 6-nylon, etc.
-Nylon, 6,6-nylon, 12-nylon, 11
-Nylon, 6°10-nylon, MXD-nylon, etc.
変性ＰＰＥとＰＡの配合割合は、広い範囲で選択するこ
とができるが、好ましくは、変性ＰＰＥ／ＰＡ−０，１
〜５の範囲、特に好ましくは、０．３〜３の範囲である
。この範囲より小さい組成物ではＰＰＥの優れた耐水性
、寸法安定性等が損なわれるし、大きい組成物では耐油
性、成形性等の改善効果が充分でない。The blending ratio of modified PPE and PA can be selected within a wide range, but preferably modified PPE/PA-0,1
-5, particularly preferably 0.3-3. If the composition is smaller than this range, the excellent water resistance and dimensional stability of PPE will be impaired, and if the composition is larger than this range, the effects of improving oil resistance, moldability, etc. will not be sufficient.
本発明の樹脂組成物には、所望に応じて、ガラス繊維、
炭素繊維などの繊維強化材料を配合することができる。The resin composition of the present invention may include glass fibers,
Fiber-reinforced materials such as carbon fibers can be blended.
さらには、高分子材料に−般に用いられる各種添加剤、
例えば、安定剤、顔染料、離型剤、滑剤、充填剤などを
適宜配合することができる。Furthermore, various additives commonly used for polymer materials,
For example, stabilizers, facial dyes, mold release agents, lubricants, fillers, and the like can be added as appropriate.
（実施例）
以下、実施例及び比較例によって本発明を具体的に示す
が、実施例中部数は重量基準で表されている。(Examples) Hereinafter, the present invention will be specifically illustrated by Examples and Comparative Examples, and the numbers in the examples are expressed on a weight basis.
実施例 １
２５℃、クロロホルム中で測定した固有粘度が０．５０
ｄＡ’１５＋であるポリ（２，６−シメチルー１．４−
フェニレン）ニー？ル粉末５に９に対し無水マレイン酸
２５．９ 、クレイトンＧ１６５１ （シェル化学製
） ４５（Ｈ’、エクセロール ＶＡ１８０３（エ
クソン化学株製）３００ｇをスーパーミキサーにて３分
間混合した後２軸押出機（池貝鉄工製 ＰＣＭ−３０）
を用いて２９０℃にて溶融混練し、押出を行って変性Ｐ
ＰＥのベレットを得た。Example 1 Intrinsic viscosity measured in chloroform at 25°C is 0.50
Poly(2,6-cymethyl-1,4-
phenylene) knee? Maleic anhydride 25.9, Kraton G1651 (Shell Chemical Co., Ltd.) 45 (H', Excelol VA1803 (Exxon Chemical Co., Ltd.) 300 g were mixed in a super mixer for 3 minutes, and then mixed in a twin screw extruder. (PCM-30 made by Ikegai Iron Works)
The modified P was melt-kneaded at 290°C and extruded.
A PE beret was obtained.
得られた変性ＰＰＥとナイロン−６（東し株製アミラン
ＣＭＩ ０１７）を表−１ｒ−示す割合で配合し、２軸
押用機を用いて２７０℃で溶融混合して得られたベレッ
トを射出成形により各種試験片を成形した。この試験片
を用いて測定した各物性値を表−１に示す。The obtained modified PPE and nylon-6 (Amilan CMI 017 manufactured by Toshi Co., Ltd.) were blended in the proportions shown in Table 1r, and the pellets obtained by melt-mixing at 270°C using a twin-screw extruder were injected. Various test pieces were formed by molding. Table 1 shows the physical property values measured using this test piece.
実施例 ２〜５
エラストマーにクレイトンＧ−１６５０（シェル化学製
）を用いた場合（実施例２）、実施例１で得られた変性
ＰＰＥとナイロン−６，６（東し株製アミランＣＭ３０
０１Ｎ）を用いた場合（実施例３）、エラストマーの添
加量を変えた場合（実施例４．５）について、実施例１
と同様く行った結果を表−１に示す。Examples 2 to 5 When Kraton G-1650 (manufactured by Shell Chemical Co., Ltd.) was used as the elastomer (Example 2), the modified PPE obtained in Example 1 and nylon-6,6 (Amilan CM30, manufactured by Toshi Co., Ltd.) were used.
01N) (Example 3), and when the amount of elastomer added was changed (Example 4.5), Example 1
Table 1 shows the results obtained in the same manner as above.
比較例 １
エラストマーとしてクレイトン Ｇ１６５１（シェル化
学製）単独で使用した以外は実施例１と同様ｔこ行った
結果を表−１１こ示す。（実施例４と対比）
比較例 ２
エラスト
０３ （エフ
は実施例１
（実施例４
マーとしてエクセロール ＶＡ１８
ソン化学株製）を単独で用いた以外
と同様に行った結果を表−Ｉｔこ示す。Comparative Example 1 The same procedure as in Example 1 was performed except that Kraton G1651 (manufactured by Shell Chemical) was used alone as the elastomer. The results are shown in Table 11. (Compared with Example 4) Comparative Example 2 Elasto 03 (F was conducted in the same manner as Example 1 (Example 4 as EXCELOL VA18 manufactured by Son Kagaku Co., Ltd.) except that it was used alone. The results are shown in Table 1. .
と対比）
比較例 ３
実施例１０ＰＰＢと無水マレイン酸のみを２軸押用機で
溶融混合し、変性ＰＰＥを得た。得られた変性ＰＰＥに
クレイトンＧ１６５１とエクセロールＶＡ１８０３およ
びナイロンを混合して得られた組成物の物性を表−１に
示した。Comparative Example 3 Example 10 Only PPB and maleic anhydride were melt-mixed in a twin-screw press to obtain modified PPE. Table 1 shows the physical properties of a composition obtained by mixing Kraton G1651, Excelol VA1803, and nylon with the obtained modified PPE.
（発明の効果）
実施例、比較例から明らかなようｔこ、本発明の組成物
は耐衝撃性（特に低温耐衝撃性）、耐熱性、射出成形時
の熱安定性に優れており、従来法では得られない特性を
示している。(Effects of the Invention) As is clear from the Examples and Comparative Examples, the composition of the present invention has excellent impact resistance (especially low-temperature impact resistance), heat resistance, and thermal stability during injection molding, and is superior to conventional compositions. It shows characteristics that cannot be obtained by the method.
Claims (1)
２、Ｒ＿３は水素原子又は炭素数１〜３の低級アルキル
基である。） で表わされる構造単位を主鎖に持つポリフェニレンエー
テル樹脂を水素添加Ａ−Ｂ−Ａ型ブロック共重合弾性体
（ここで、Ａはビニル芳香族炭化水素の重合体ブロック
をＢは共役ジエン系炭化水素化合物の重合体ブロックを
意味する）と不飽和酸無水物及び不飽和酸から選ばれた
少なくとも一種で変性されたエチレン−α−オレフィン
系共重合体の共存下に酸無水物構造を有する１，２−置
換オレフィン化合物と溶融状態で反応せしめて得られる
変性ポリフェニレンエーテル樹脂と、 （ｂ）ポリアミド樹脂 からなる低温耐衝撃性に優れた樹脂組成物。[Claims] (a) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 is a lower alkyl group having 1 to 3 carbon atoms, R_
2, R_3 is a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms. ) Hydrogenated A-B-A type block copolymer elastomer of polyphenylene ether resin having a structural unit represented by 1 having an acid anhydride structure in the coexistence of a hydrogen compound polymer block) and an ethylene-α-olefin copolymer modified with at least one selected from unsaturated acid anhydrides and unsaturated acids. , a modified polyphenylene ether resin obtained by reacting it with a 2-substituted olefin compound in a molten state, and (b) a polyamide resin, the resin composition has excellent low-temperature impact resistance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17486388A JPH0228246A (en) | 1988-07-15 | 1988-07-15 | Resin composition having excellent impact resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17486388A JPH0228246A (en) | 1988-07-15 | 1988-07-15 | Resin composition having excellent impact resistance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0228246A true JPH0228246A (en) | 1990-01-30 |
Family
ID=15985972
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17486388A Pending JPH0228246A (en) | 1988-07-15 | 1988-07-15 | Resin composition having excellent impact resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0228246A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020225935A1 (en) | 2019-05-07 | 2020-11-12 | 朝日インテック株式会社 | Guide wire |
-
1988
- 1988-07-15 JP JP17486388A patent/JPH0228246A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020225935A1 (en) | 2019-05-07 | 2020-11-12 | 朝日インテック株式会社 | Guide wire |
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