JPS63105022A - Polyphenylene ether resin composition - Google Patents
Polyphenylene ether resin compositionInfo
- Publication number
- JPS63105022A JPS63105022A JP25027886A JP25027886A JPS63105022A JP S63105022 A JPS63105022 A JP S63105022A JP 25027886 A JP25027886 A JP 25027886A JP 25027886 A JP25027886 A JP 25027886A JP S63105022 A JPS63105022 A JP S63105022A
- Authority
- JP
- Japan
- Prior art keywords
- polyphenylene ether
- modified
- weight
- olefin polymer
- resin
- 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.)
- Granted
Links
- 229920001955 polyphenylene ether Polymers 0.000 title claims abstract description 47
- 239000011342 resin composition Substances 0.000 title abstract 3
- 229920000098 polyolefin Polymers 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 30
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920005989 resin Polymers 0.000 claims abstract description 18
- 239000011347 resin Substances 0.000 claims abstract description 18
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 6
- 239000003607 modifier Substances 0.000 claims abstract description 5
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims abstract 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract 2
- 150000001875 compounds Chemical class 0.000 claims abstract 2
- 229920000642 polymer Polymers 0.000 claims description 22
- 239000004593 Epoxy Substances 0.000 abstract description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- 229920001577 copolymer Polymers 0.000 description 12
- 239000003921 oil Substances 0.000 description 10
- -1 polyphenylene Polymers 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 229920001971 elastomer Polymers 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 7
- 239000000806 elastomer Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000001993 dienes Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229920005672 polyolefin resin Polymers 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229920000265 Polyparaphenylene Polymers 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- WLQXEFXDBYHMRG-UPHRSURJSA-N (z)-4-(oxiran-2-ylmethoxy)-4-oxobut-2-enoic acid Chemical compound OC(=O)\C=C/C(=O)OCC1CO1 WLQXEFXDBYHMRG-UPHRSURJSA-N 0.000 description 1
- ATGFTMUSEPZNJD-UHFFFAOYSA-N 2,6-diphenylphenol Chemical compound OC1=C(C=2C=CC=CC=2)C=CC=C1C1=CC=CC=C1 ATGFTMUSEPZNJD-UHFFFAOYSA-N 0.000 description 1
- FYELSNVLZVIGTI-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-5-ethylpyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1CC)CC(=O)N1CC2=C(CC1)NN=N2 FYELSNVLZVIGTI-UHFFFAOYSA-N 0.000 description 1
- DKGHOKHCDQLFCD-UHFFFAOYSA-N 2-[[4-[4-(oxiran-2-ylmethyl)phenoxy]phenyl]methyl]oxirane Chemical compound C=1C=C(OC=2C=CC(CC3OC3)=CC=2)C=CC=1CC1CO1 DKGHOKHCDQLFCD-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- 229920002943 EPDM rubber 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
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229920001890 Novodur Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- ADFPJHOAARPYLP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1 ADFPJHOAARPYLP-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000314 poly p-methyl styrene Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
１）背景
本発明は、エボキク変性ポリフェニレンエーテルおよび
、ボリフエニレンエーテ／ｌ−またはそのスチレン系樹
脂稀釈組成物と酸変性オレフィン系重合体およびオレフ
ィン系重合体組成物とからなる、成形加工性、耐熱性、
耐油性、耐衝撃性にすぐれた組成物に関する。DETAILED DESCRIPTION OF THE INVENTION 1) Background The present invention relates to a polyphenylene ether modified with Ebokiku, polyphenylene ether/l- or a styrene resin diluted composition thereof, an acid-modified olefin polymer, and an olefin polymer composition. consisting of moldability, heat resistance,
This invention relates to a composition with excellent oil resistance and impact resistance.
ポリフェニレンエーテルは、優れた耐熱性、機械的特性
、耐水性、耐アルカリ性、自己消火性等を備えた極めて
有用な熱可塑性樹脂であり、エンジニアリングプラスチ
ックス材料として、多くの応用展開が図られつつある。Polyphenylene ether is an extremely useful thermoplastic resin with excellent heat resistance, mechanical properties, water resistance, alkali resistance, self-extinguishing properties, etc., and is being used in many applications as an engineering plastic material. .
しかしながら、ガラス転移温度が高いことと関連して溶
融粘度が高く、成形加工性が悪いという大きな欠点を有
している。However, it has major drawbacks such as high melt viscosity associated with high glass transition temperature and poor moldability.
また射出成形時の雛形性が悪いこと、エンジニアリング
プラスチックスとしては耐衝撃性が劣ること、また耐油
性に劣９、ガソリン、灯油、各種ワツクス、潤滑油など
と接触する構造部品材料として使用できないことなどの
問題点がある。本発明者らは、ポリフェニレンエーテル
の優れた諸性質を大きくは損なわない範囲で、とのよう
な間厘点を解決すべく、研究を進め、特定の変性ポリフ
ェニレンエーテルと特定の変性オレフィン系重合体組成
物を含有する組成物が良好な物性バランスを示すことを
見い出した。In addition, the patternability during injection molding is poor, the impact resistance is poor as an engineering plastic, and the oil resistance is poor9, so it cannot be used as a material for structural parts that come into contact with gasoline, kerosene, various waxes, lubricating oils, etc. There are problems such as: The present inventors have conducted research in order to solve the problem of compromise without significantly impairing the excellent properties of polyphenylene ether, and have developed a combination of a specific modified polyphenylene ether and a specific modified olefin polymer. It has been found that a composition containing the composition exhibits a good balance of physical properties.
即ち、本発明は、成分（１）：ポリフェニレンエーテル
２０〜１００重量％、スチレン系樹脂８０〜ＯＭｍ％の
割合の樹脂（ａ） １Ｏ〜９０重量シ、成分（２）：エ
ポキシ変性ポリフェニレンエーテル０．１〜４０重量％
、成分（３）ニオレフイン系重合体２〜８０重贋％、及
び、成分（４）：酸変性オレフィン系重合体０．１〜６
０重量％からなる成形性及び耐油性の改良されたポリフ
ェニレンエーテル組成物を提供するものである。That is, the present invention includes component (1): 20 to 100% by weight of polyphenylene ether, 80 to OMm% of styrene resin (a) 10 to 90% by weight, component (2): 0.0 to 100% by weight of epoxy-modified polyphenylene ether. 1-40% by weight
, component (3) niolefin polymer 2-80%, and component (4) acid-modified olefin polymer 0.1-6
The object of the present invention is to provide a polyphenylene ether composition containing 0% by weight and having improved moldability and oil resistance.
２）先行技術
ポリフェニレンエーテルの欠点、特に成形加工性を改良
することを目的として、ポリオレフィン、またはポリス
チレン、ゴム変性ポリスチレン、スチレン−アクリロニ
トリル−ブタジェン共重合体などのスチレン系ポリマー
をブレンドすることが行なわれ、特公昭４２−７０６９
号、特公昭４３−１７８１２号公報、アメリカ特許第３
３８３４３５号明細書等に公開されている。2) Prior Art In order to improve the disadvantages of polyphenylene ethers, especially their moldability, it has been attempted to blend them with polyolefins or styrenic polymers such as polystyrene, rubber-modified polystyrene, and styrene-acrylonitrile-butadiene copolymers. , Special Publication No. 42-7069
No. 43-17812, U.S. Patent No. 3
It is disclosed in the specification of No. 383435, etc.
しかし、スチレン系樹脂は、ポリフェニレンエーテルと
相溶性が良好であり両者の配合物は広く実用に供されて
いるが両成分ともに、耐油性に劣るから、得られるブレ
ンド物の耐油性は不充分なものであり、大幅な耐油性の
改良が望まれている。However, although styrene resin has good compatibility with polyphenylene ether and blends of the two are widely used in practical use, both components have poor oil resistance, so the oil resistance of the resulting blend is insufficient. Therefore, significant improvement in oil resistance is desired.
ポリフェニレンエーテルとポリオレフィンとよしなる組
成物においては耐油性向上効果は大きいが、両成分の相
溶性が乏しいために、その混合組成物は粗大な分散構造
を有し、その相界面には極めて弱い親和力しか働かない
。この結果、得られる組成物は衝撃強度が低下する。ま
た、成形加工物において、樹脂の流れ方向に各構成成分
が配向し、その界面で薄膜状罠はく離が生じる現象、い
わゆるデラミネーションのため実用には供し得ないもの
となる。この点を改良する為に、高分子量ポリオレフィ
ンに代えて、低分子の結晶性ポリオレフィンを用いるこ
とが提案されている（特公昭４８−３９０１５）が、ポ
リフェニレンエーテルとポリオレフィンが本質的に相溶
性を持たないことから、根本的な問題解決にはなってい
ないのが実状である。A composition containing polyphenylene ether and polyolefin has a great effect on improving oil resistance, but due to poor compatibility between the two components, the mixed composition has a coarse dispersed structure and has extremely weak affinity at the phase interface. only works. As a result, the resulting composition has reduced impact strength. In addition, in the molded product, the constituent components are oriented in the flow direction of the resin, and a thin film-like trap peeling occurs at the interface between the components, so-called delamination, which makes the product unusable for practical use. In order to improve this point, it has been proposed to use a low molecular weight crystalline polyolefin instead of a high molecular weight polyolefin (Japanese Patent Publication No. 48-39015), but polyphenylene ether and polyolefin are essentially compatible. The reality is that it does not solve the fundamental problem.
また、ポリフェニレンエーテル及び（又は）ポリオレフ
ィン変性体と反応して得られるポリフェニレングラフト
ポリオレフィンを用いることによす、ポリフェニレンエ
ーテルとポリオレフィンの相溶性を改良し、ポリフェニ
レンエーテル及びスチレン系重合体よ抄なる組成物の成
形加工性衝撃強度を改良することが、本発明者らによっ
て特開昭５８−７４４８に提示されている。特開昭５８
−７４４８の実施例６には、グリシジル化ポリフェニレ
ンエーテルと無水マレイン酸変性ポリプロピレンからな
る反応生成物１０重量部、及びポリフェニレンエーテル
５０ を散部、ホリス？ ｖンｓ。In addition, the compatibility of polyphenylene ether and polyolefin is improved by using a polyphenylene graft polyolefin obtained by reacting with polyphenylene ether and/or a modified polyolefin, and a composition made of polyphenylene ether and a styrene polymer is produced. The present inventors have proposed in Japanese Patent Application Laid-open No. 58-7448 an improvement in the moldability and impact strength of . Japanese Unexamined Patent Publication 1983
Example 6 of -7448 contained 10 parts by weight of a reaction product consisting of glycidylated polyphenylene ether and maleic anhydride-modified polypropylene, and 50 parts of polyphenylene ether dispersed in Hollis®-7448. vs.
重量部からなる組成物の成形加工性、衝撃強度改良効果
が示されている。しかしながら、広範な用途に使用する
には、なおいっそうの諸性質の改良、特に、成形性及び
耐油性の改良が望まれている。The effect of improving moldability and impact strength of the composition consisting of parts by weight is shown. However, in order to use it in a wide range of applications, further improvements in various properties, particularly in moldability and oil resistance, are desired.
本発明者らは、かかる目的のため、さらに研究を進めた
結果、未変性プロピレン系樹脂の適当量とエポキシ変性
ポリフェニレンエーテル及び、酸変性オレフィン系樹脂
をポリフェニレンエーテルに配合した組成物が好適な物
性バランスを示すことを見い出し、本発明にいたった。For this purpose, the present inventors conducted further research and found that a composition in which an appropriate amount of an unmodified propylene resin, an epoxy-modified polyphenylene ether, and an acid-modified olefin resin were blended with polyphenylene ether had suitable physical properties. It was discovered that this shows a balance, leading to the present invention.
３）発明の詳細な説明
本発明における成分（＆）として用いられるポリフェニ
レンエーテル、！：ハ、一般式
％式％
（式中、Ｒ１−Ｒ５は水素、ハロゲン化炭化水素、炭化
水素基もしくは置換炭化水素基から選ばれたもの）で示
されるフェノール化合物の１窪又は複数を酸化カップリ
ング重合して得られる重合体である。3) Detailed Description of the Invention Polyphenylene ether used as component (&) in the present invention! : C. One or more phenol compounds represented by the general formula % (wherein R1-R5 are selected from hydrogen, halogenated hydrocarbons, hydrocarbon groups, or substituted hydrocarbon groups) are oxidized into oxidized cups. It is a polymer obtained by ring polymerization.
フェノール化合物として好ましいものとして、２．６−
シメチルフエノール、２．６−ジフェニルフェノール、
２．３．６− ）リメチルフェノール、２，６−イツプ
ロビルフエノール、２−メチル−６−イングロビルフエ
ノール、２−メチル−ａ−ｔ−−ｙチルフェノール、な
どがあげられる。又クレゾール、２．４，６−）リメチ
ルフェノールなどを共重合成分の小景部として選ぶこと
もできる。また、これらの構成成分の一部が重合反応中
に、酸化又は触媒種による変性を受けたものも同様に好
適である。また、ポリフェニレンエーテルにスチレン系
重合体あるいは他の重合体が少量部結合しているグラフ
ト重合体を使用することができる。As a preferable phenol compound, 2.6-
dimethylphenol, 2,6-diphenylphenol,
2.3.6-) Limethylphenol, 2,6-iprobylphenol, 2-methyl-6-inglobylphenol, 2-methyl-a-t-y-thylphenol, and the like. Also, cresol, 2,4,6-)limethylphenol, etc. can be selected as a small part of the copolymerization component. Furthermore, those in which some of these constituent components have been oxidized or modified by catalyst species during the polymerization reaction are also suitable. Furthermore, a graft polymer in which a small amount of a styrene polymer or other polymer is bonded to polyphenylene ether can be used.
本発明にあって、ポリフェニレンエーテルと混合するの
に用いられるスチレン系樹脂とは、スチレン誘導体、具
体的にはスチレン、ｐ−メチルスチレン、α−メチルス
チレンなどから選ばれた１種又は複数の重合単位を２５
重量％以上含有する重合体、又は共重合体である。具体
例として、ポリスチレン、ポリ−α−メチルスチレン、
ポリ−ｐ−メチルスチレン、スチレン−α−メチルスチ
レン共重合体、スチレン−無水マレイン酸共重合体、ス
チレン−アクリル酸共重合体、スチレン−メチルメタア
クリレート共重合体、スチレン−グリシジルメタアクリ
レート共重合体、スチレン−ブタジェンランダム共重合
体及びそのジエン成分の７０％以上の水添物、スチレン
−ブタジェンブロック共重合体及びそのジエン成分の７
０％以上の水添物、スチレン−イソプレンブロック共重
合体及びそのジエン成分の７０％以上の水添物、などが
挙げられる。また、これらの重合体のゴム強化組成物、
具体的にはＡＢＳ樹脂、ハイインパクトポリスチレンも
本発明にいうスチレン系樹脂として使用することができ
る。In the present invention, the styrene resin used to mix with polyphenylene ether is a styrene derivative, specifically one or more polymers selected from styrene, p-methylstyrene, α-methylstyrene, etc. 25 units
It is a polymer or copolymer containing at least % by weight. Specific examples include polystyrene, poly-α-methylstyrene,
Poly-p-methylstyrene, styrene-α-methylstyrene copolymer, styrene-maleic anhydride copolymer, styrene-acrylic acid copolymer, styrene-methyl methacrylate copolymer, styrene-glycidyl methacrylate copolymer 70% or more hydrogenated product of styrene-butadiene random copolymer and its diene component, styrene-butadiene block copolymer and its diene component
Examples include 0% or more hydrogenated products, 70% or more hydrogenated products of styrene-isoprene block copolymers and their diene components, and the like. Also, rubber reinforced compositions of these polymers,
Specifically, ABS resin and high impact polystyrene can also be used as the styrenic resin referred to in the present invention.
ポリフェニレンエーテルとスチレン系樹脂合計量に対す
るスチレン系樹脂の割合は０〜８０重量％、好ましくは
θ〜６０重量％、最も好適なのは０〜４０重量聾である
。スチレン系樹脂の割合が増すと成形性は良好になるが
ポリフェニレンエーテルの特徴セある耐熱性が低下する
。The ratio of the styrene resin to the total amount of polyphenylene ether and styrene resin is 0 to 80% by weight, preferably θ to 60% by weight, and most preferably 0 to 40% by weight. As the proportion of styrene resin increases, moldability improves, but the heat resistance, which is characteristic of polyphenylene ether, decreases.
本発明にいうエポキシ変性ポリフェニレンエーテルとは
、ポリフェニレンエーテル分子にエポキシ基が、化学反
応によって導入されたものであって、エポキシ基のａ［
がポリフェニレンエーテル１００？当抄Ｉ Ｘ １０−
″４モル〜１×１０″″１モルの範囲にあるものである
。The epoxy-modified polyphenylene ether referred to in the present invention is one in which an epoxy group is introduced into a polyphenylene ether molecule through a chemical reaction, and the a[
Is it polyphenylene ether 100? This extract IX 10-
The amount is in the range of 4 mol to 1×10” 1 mol.
エポキシ基の濃度は、赤外分析ｍ、ＮＭＲ分析法によっ
て定めることができる。また、エポキシ樹脂において用
いられる滴定法を採用することも可能である。The concentration of epoxy groups can be determined by infrared analysis, NMR analysis. It is also possible to employ the titration method used for epoxy resins.
ポリフェニレンエーテルへのエポキシ基の導入方法にハ
、ポリフェニレンエーテルのフェノール性水酸基を利用
した反応、具体的にはエピクロルヒドリンの付加反応、
２．２−ビス（４−グリシジルフェニルエーテル）フロ
パン、エポキシ樹脂の付加反応などを用いることができ
る。またアルキル側鎖を利用してグリシジルメタアクリ
レート、モノグリシジルマレートなどをラジカル反応で
導入することもできる。The method for introducing epoxy groups into polyphenylene ether includes a reaction using the phenolic hydroxyl group of polyphenylene ether, specifically an addition reaction of epichlorohydrin,
2.2-bis(4-glycidylphenyl ether)furopane, addition reaction of epoxy resin, etc. can be used. Furthermore, glycidyl methacrylate, monoglycidyl maleate, etc. can also be introduced by radical reaction using the alkyl side chain.
エポキシ変性ポリフェニレンエーテルの割合は０．１〜
４０重量％、好ましくは１〜３０重量％、さらに好まし
くは２〜２０重４％である。エポキシ変性体の割合が大
きくなると、最終生成物の流動性と機械的強度が低下す
る。ゲル体の生成が原因と推定される。また割合が小さ
すぎると分散性改良効果が発揮されず、好ましい性質が
得られない。The ratio of epoxy modified polyphenylene ether is 0.1~
40% by weight, preferably 1 to 30% by weight, more preferably 2 to 20% by weight. The greater the proportion of epoxy modified product, the lower the fluidity and mechanical strength of the final product. It is assumed that the cause is the formation of gel bodies. On the other hand, if the ratio is too small, the effect of improving dispersibility will not be exhibited and desirable properties will not be obtained.
本発明に用いるオレフィン系重合体の好適例としては、
ポリプロピレン、プロピレン−エチレン共重合体などを
挙げることができる。Suitable examples of the olefin polymer used in the present invention include:
Examples include polypropylene, propylene-ethylene copolymer, and the like.
成形性および耐熱性の観点から、結晶性プロピレン連鎖
を有し、融点が１２０℃以上である結晶性成分を３０重
汲置以上含むことが好ましい。この条件を満たす範囲で
プロピレン系重合体と他のオレフィン系重合体からなる
混合組成物を用いることもできる。From the viewpoints of moldability and heat resistance, it is preferable to contain 30 or more times a crystalline component having a crystalline propylene chain and a melting point of 120° C. or higher. A mixed composition consisting of a propylene polymer and another olefin polymer can also be used within a range that satisfies this condition.
本発明にいう酸変性オレフィン系重合体とは、オレフィ
ン重合体又は共重合体であって、カルボン酸あるいは酸
無水物から選ばれた変性剤が、うジカル付加反応や共重
合反応によって、主鎖あるいは側鎖あるいは分子末端に
導入されたものである。その具体例としては無水マレイ
ン酸を過酸化物の存在下、溶用状態または溶液状態でポ
リプロピレンと反応させた生成物、無水マレイン酸に代
えて、無水イタコン酸、アクリル酸、メタクリル酸など
を用いた同様の変性物、エチレンとアクリル酸又はメタ
アクリル俊のラジカル共重合物などが挙げられる。The acid-modified olefin polymer referred to in the present invention is an olefin polymer or copolymer in which a modifier selected from carboxylic acids or acid anhydrides is added to the main chain by a carboxyl addition reaction or a copolymerization reaction. Alternatively, it is introduced into the side chain or the end of the molecule. Specific examples include products obtained by reacting maleic anhydride with polypropylene in a dissolved or solution state in the presence of peroxide, and the use of itaconic anhydride, acrylic acid, methacrylic acid, etc. in place of maleic anhydride. Examples include similar modified products such as radical copolymers of ethylene and acrylic acid or methacrylic acid.
先に述べたように、オレフィン系重合体として、耐熱性
及び成形性の観点から、結晶性プロピレン単位を有する
オレフィン系重合体を用いることが好ましく、この場合
には、酸変性オレフィン系重合体もまた、３０重な５以
上のグロビレン単量体から成るものがオレフィン系重合
体との親和性が良く好ましい。最も好適であるのはプロ
ピレン単徴体含量が５０重口％以上で、示差熱分析など
で結晶性の認められるものである。As mentioned above, from the viewpoint of heat resistance and moldability, it is preferable to use an olefin polymer having crystalline propylene units as the olefin polymer. In this case, an acid-modified olefin polymer may also be used. Further, those consisting of 5 or more 30-fold globylene monomers are preferred because they have good affinity with olefin polymers. The most preferable one is one in which the propylene monomer content is 50% by weight or more and crystallinity is observed by differential thermal analysis.
変性剤の含有量（変性度）は０．０１〜４０重量％、好
ましくは０．１〜４０重険％、さらに好ましくは０．５
〜２０重量警である。変性度が高くなると変性ポリマー
自身の凝集が進み、最終組成物におけるポリフェニレン
エーテル系成分とオレフィン系成分の分散性改良に及ぼ
す効果が低下する。The content of the modifier (degree of modification) is 0.01 to 40% by weight, preferably 0.1 to 40% by weight, more preferably 0.5%.
~20 weight police. As the degree of modification increases, aggregation of the modified polymer itself progresses, and the effect on improving the dispersibility of the polyphenylene ether component and olefin component in the final composition decreases.
酸変性オレフィン系重合体の割合は０．１〜６０重介％
、好ましくは１〜５０重社％、さらに好ましくは２〜３
０重量多である。酸変性体の割合が大きくなると、最終
組成物の流動性や機械的強度が低下する。The proportion of acid-modified olefin polymer is 0.1 to 60%
, preferably 1 to 50%, more preferably 2 to 3%
0 weight. When the proportion of the acid-modified product increases, the fluidity and mechanical strength of the final composition decrease.
全成分を同時に熔融混合する場合、オレフィン系樹脂成
分（成分（３）と成分（４）の合計量）が３０重所％以
上であれば、意外にも過半量に満たない場合においてさ
え、オレフィン系樹脂成分が連続相を形成し、その結果
耐油性改良効果がよりいっそう発現される。When all components are melt-mixed at the same time, if the olefin resin component (total amount of component (3) and component (4)) is 30% by weight or more, the olefin resin can surprisingly be mixed even if it is less than the majority amount. The system resin component forms a continuous phase, and as a result, the effect of improving oil resistance is further expressed.
オレフィン系樹脂成分は、好ましくは、３０〜７５０〜
７５重量部ましくは５０〜７０重驚％の範囲とされる。The olefin resin component preferably has a molecular weight of 30 to 750
The amount is 75 parts by weight or 50 to 70% by weight.
またオレフィン系樹脂成分の割合の増加にしたがって成
形性は向上する一方、同時に耐熱性が低下するので、オ
レフィン系樹脂成分の割合は、目的に応じて、上記の割
合の範囲から選ぶことができる。Furthermore, as the proportion of the olefin resin component increases, the moldability improves, but at the same time the heat resistance decreases, so the proportion of the olefin resin component can be selected from the above range of proportions depending on the purpose.
さらに必要に応じて最終組成物の衝撃強度を補強する目
的でエラストマー成分を配合することができる。エラス
トマーの添加量は、最終組成物１００重量部に対して、
０〜４０重量部が好適である。Furthermore, if necessary, an elastomer component may be added for the purpose of reinforcing the impact strength of the final composition. The amount of elastomer added is based on 100 parts by weight of the final composition.
0 to 40 parts by weight is suitable.
エラストマー成分が４０部を超すと、組成物の高温弾性
率が低下し、ポリフェニレンエーテル組成物の特性が失
なわれる。エラストマーの具体例としては、エチレンプ
ロピレン共重合体、エチレンプロピレンジエン三元共重
合体、エチレンブテン共重合体、などのオレフィン系エ
ラス）−ｒ−、ポリブタジェン、ポリイソプレン、天然
ゴムなどのジエン系エラストマー、スチレンブタジェン
ラバー、スチレンブタジェンブロック共重合体、スチレ
ンイソプレンブロック共重合体などのジエン系共重合体
エラストマー及びそのジエン成分の７０％以上が水素化
された水添ジエン系共重合体エラストマーがあげられる
。If the elastomer component exceeds 40 parts, the high temperature elastic modulus of the composition decreases and the properties of the polyphenylene ether composition are lost. Specific examples of elastomers include olefin elastomers such as ethylene propylene copolymer, ethylene propylene diene terpolymer, and ethylene butene copolymer), diene elastomers such as polybutadiene, polyisoprene, and natural rubber. , styrene-butadiene rubber, styrene-butadiene block copolymer, styrene-isoprene block copolymer and other diene-based copolymer elastomers, and hydrogenated diene-based copolymer elastomers in which 70% or more of the diene component is hydrogenated. can give.
以下に本発明を説明するために実施例を挙げる。Examples are given below to illustrate the present invention.
本発明は実施例によりその範囲を限定されるものではな
い。また実用上の目的に応じて、ガラス繊維、無機フィ
ラー、安定剤、難燃剤、着色剤など添加しうる。The scope of the present invention is not limited by the examples. Depending on the practical purpose, glass fibers, inorganic fillers, stabilizers, flame retardants, colorants, etc. may be added.
４）実施例
以下にまず本発明に用いられる変性ポリフェニレンエー
テル及び変性オレフィン系重合体の製造方法を（参考例
→として例示する。4) Examples Below, the method for producing modified polyphenylene ether and modified olefin polymer used in the present invention will be exemplified as (Reference Example →).
１１例−１）エポキシ変性ポリフェニレンエーテルの製
造（変性ポリフェニレン
エーテルＡ）
内容積３０１のステンレス製オートクレーブに、エピク
ロルヒドリンｌＯｔを入れ、次いでポリ−２，６−ジメ
テルー１．４−フ二二しンエーテル重合体粉末（三菱油
化社製、クロロホルム中３０℃における極限粘度がｏ、
４ａｄｔ／ｒ）ａｏｏｒを加える。次いで外部ジャケッ
トよ妙加熱昇温し攪拌しながら、１００℃に約３０分保
ってポリマーを完全に溶解させた後、４０％カセイソー
ダ水溶液５０ｍを加え、窒素雰囲気下還流脱水しながら
１００℃で３時間反応させる。反応終了後、エビク四ル
ヒドリンを減圧にて留去し、得られたポリマーをクロロ
ホルム５ｔに溶解する。ポリマー溶液中に浮遊する固形
物（生成したＮａＣｔおよび過剰のＮａＯＨ）をろ別除
去後、メタノール／水（５０１５０）の混合溶媒を加え
、ポリマーを再沈澱させ、同溶媒１０ｔにて３回洗浄し
た後１００℃で約１０時間乾燥させ、グリシジル化ポリ
フェニレンエーテルを得た。この操作で得られたポリマ
ーを、過塩素酸−〇ＴＡ −Ｂ法で滴定した結果、ポリ
マー１００ｆに含まれるグリシジル基の量は、４Ｘ１０
−’モルであった。Example 11-1) Production of epoxy-modified polyphenylene ether (modified polyphenylene ether A) Into a stainless steel autoclave with an internal volume of 301 cm, 1000 epichlorohydrin was put, and then poly-2,6-dimether-1,4-phenylene ether polymer was added. Powder (manufactured by Mitsubishi Yuka Co., Ltd., intrinsic viscosity at 30°C in chloroform is o,
4adt/r) Add aoor. Next, the temperature was raised gently through the outer jacket and kept at 100°C for about 30 minutes while stirring to completely dissolve the polymer. After that, 50ml of a 40% caustic soda aqueous solution was added, and the mixture was heated at 100°C for 3 hours while being refluxed and dehydrated under a nitrogen atmosphere. Make it react. After the reaction is completed, the shrimp tetrahydrin is distilled off under reduced pressure, and the obtained polymer is dissolved in 5 tons of chloroform. After removing solids (generated NaCt and excess NaOH) floating in the polymer solution by filtration, a mixed solvent of methanol/water (50150) was added to reprecipitate the polymer, and the polymer was washed three times with 10 tons of the same solvent. It was then dried at 100°C for about 10 hours to obtain glycidylated polyphenylene ether. As a result of titrating the polymer obtained by this operation using the perchloric acid-〇TA-B method, the amount of glycidyl groups contained in polymer 100f was 4X10
−'mol.
ＳＥＣ法より求めたポリスチレン換算数平均分子量２０
２０Ｇより、はぼ一分子当り一つのグリシジル基を有す
ることを確認した。Polystyrene equivalent number average molecular weight determined by SEC method: 20
From 20G, it was confirmed that there was one glycidyl group per molecule.
下記の反応がほぼ定量的に進行したことは明らかである
。It is clear that the reaction described below proceeded almost quantitatively.
ＣＨ３ＣＨ３ＣＨ３
（参考例−２）エポキシ変性ポリフェニレンエーテルの
製造（変性ポリフェニレン
エーテル−Ｂ）
ホ１７−２．６−シメチルーフエニレンエーテル重合体
粉末（三菱油化製クロロホルム中３０℃の極限粘度０．
４８ｄｔ／ｆ）１００ｆに対し、２ｆのエポキシ樹脂（
油化シェルエポキシ製エピコート１００２）を１０−の
クロロホルムに溶解した溶液を均一に混ぜて、プラベン
ダープラストグラフ（東洋精機部）にて、２８０℃、５
分間混練した。CH3CH3CH3 (Reference Example-2) Production of epoxy-modified polyphenylene ether (modified polyphenylene ether-B) 17-2.6-dimethyl-phenylene ether polymer powder (intrinsic viscosity at 30°C in chloroform manufactured by Mitsubishi Yuka: 0.
48dt/f) 100f, 2f of epoxy resin (
A solution of Epicoat 1002 (manufactured by Yuka Shell Epoxy) dissolved in 10-chloroform was mixed uniformly and heated at 280°C for 50 minutes in a Prabender Plastograph (Toyo Seiki Department).
Kneaded for a minute.
得られた組成物についてＥ、 ５ｈｃｈｏｒｉ らの
方法（ジャーナルオブ了ブライドポリマーサイエンス。The resulting composition was described by the method of E. Hchori et al. (Journal of Bride Polymer Science).
ポリマーシンポジ９４３４巻、１０３ページ）に準じて
、分光光度法によりフェノール性末端基量を測定すると
約”／２ Ｋ減少していた。添加したエポキシ樹脂の一
部が次のように付加反応すると考えられる。When the amount of phenolic end groups was measured by spectrophotometry according to Polymer Symposia Vol. 9434, page 103), it was found that the amount of phenolic end groups had decreased by approximately 2 K. It is thought that a part of the added epoxy resin undergoes an addition reaction as follows. It will be done.
（参考例−３）無水マレイン酸変性ポリプロピレンの製
造（変性ポリオレフィン−
Ａ）
ポリプロピレン樹脂（三菱油化製三菱ノーブレンＭＡ８
）Ｚｏｏ重危重量無水マレイン酸３重量部をスーパーミ
キサーでトライブレンドした。これらにｔ−プチルパー
オキシピパレー） ０．２ 重Ｍ部を添加して、池貝鉄
工社製２軸押出機にて混線した。得られた組成物をアセ
トン抽出した後の、無水マレイン酸残基含量は１．３重
量％であった。(Reference Example-3) Production of maleic anhydride-modified polypropylene (modified polyolefin-A) Polypropylene resin (Mitsubishi Noblen MA8 manufactured by Mitsubishi Yuka Co., Ltd.
) Three parts by weight of Zoo heavy maleic anhydride were tri-blended using a super mixer. To these were added 0.2 parts by weight of t-butylperoxypiparet, and the mixture was mixed in a twin-screw extruder manufactured by Ikegai Tekko Co., Ltd. After the resulting composition was extracted with acetone, the maleic anhydride residue content was 1.3% by weight.
（参考例−４）無水マレイン酸変性エチレンプロピレン
共重合体の製造（変性ポリ
オレフィン−Ｂ）
ポリプロピレン樹脂をエチレン−プロピレン共重合体（
日本合成ゴム■製ＥＰ−０７、プ冒ピレン含量７５％）
とした以外は参考例−３と同様に実施して変性ポリオレ
フィンを得た。(Reference Example-4) Production of maleic anhydride-modified ethylene-propylene copolymer (modified polyolefin-B) Polypropylene resin was converted into ethylene-propylene copolymer (
EP-07 manufactured by Nippon Synthetic Rubber, pyrene content 75%)
A modified polyolefin was obtained in the same manner as in Reference Example 3 except for the following.
（実施例１〜３）
所定の配合割合の組成物を、ブラベンダープラストグラ
フ（東洋精機部）にて２８０℃、５分間混練して最終組
成物を得た。プレス成形にて厚さ２ｍの試験片を作成し
物性評価に供した。成形加工性はＪＩＳ−に７２１０−
１９７５に準拠したメルトインデクサ−により２９０℃
、５＃荷重、１０分間の条件下での流出重量によってメ
ルトフローインデックスとして評価した。耐油性は、ベ
ルゲンの１／４楕円治具（エスピーイー ジャーナル、
１９６２年、６６７ページ）を用い、ヘプタンとトルエ
ンの９対１混合溶媒に３分間浸漬したときの応力割れ部
位の最小歪み量にて評価した。(Examples 1 to 3) A final composition was obtained by kneading a composition having a predetermined blending ratio at 280° C. for 5 minutes in a Brabender Plastograph (Toyo Seiki Department). A test piece with a thickness of 2 m was prepared by press molding and used for physical property evaluation. Molding processability is JIS-7210-
290℃ by melt indexer according to 1975
The melt flow index was evaluated based on the flow weight under the conditions of , 5# load, and 10 minutes. For oil resistance, Bergen's 1/4 oval jig (SPE Journal,
(1962, p. 667), and was evaluated based on the minimum amount of strain at the stress crack site when immersed in a 9:1 mixed solvent of heptane and toluene for 3 minutes.
また、衝撃強度はディンスタット衝撃強度試験法（ＢＳ
−１３３０−１９４６）を用いて実施した。In addition, the impact strength was measured using the Dinstadt impact strength test method (BS
-1330-1946).
結果を（表−１）に示す。The results are shown in (Table 1).
エポキシ変性ポリフェニレンエーテル及び酸変性オレフ
ィン系重合体の添加効果が示されている。The effects of adding epoxy-modified polyphenylene ether and acid-modified olefin polymer are shown.
（実施例４〜６） 表−２に示す割合に混合した結果を表−２に示す。(Examples 4 to 6) Table 2 shows the results of mixing in the proportions shown in Table 2.
酸変性オレフィン重合体及び未変性オレフィン共重合体
の併用において成形加工性の改良が明らかに認められた
。An improvement in moldability was clearly observed in the combined use of an acid-modified olefin polymer and an unmodified olefin copolymer.
（以下余白）(Margin below)
Claims (1)
形性と耐油性の改良されたポリフェニレンエーテル組成
物 （１）ポリフェニレンエーテル２０〜１００重量％、ス
チレン系樹脂８０〜０重量％の割合の樹脂（ａ）、１０
〜９０重量％、 （２）エポキシ基を有する化合物で変性されたポリフェ
ニレンエーテルであって、１００グラム当りの結合エポ
キシ基量が１×１０＾−＾４モル〜１×１０＾−＾１モ
ルの範囲である変性ポリフェニレンエーテル０．１〜４
０重量％ （３）オレフィン系重合体２〜８０重量％ （４）オレフィン系重合体をカルボン酸または無水カル
ボン酸から選ばれた変性剤で変性した樹脂であって変性
剤含有量が０．０１〜４０重量％である酸変性オレフィ
ン系重合体０．１〜６０重量％[Scope of Claims] A polyphenylene ether composition with improved moldability and oil resistance characterized by comprising the following components (1) to (4) (1) 20 to 100% by weight of polyphenylene ether, styrene resin Resin (a) in a proportion of 80-0% by weight, 10
~90% by weight, (2) polyphenylene ether modified with a compound having an epoxy group, the amount of bound epoxy groups per 100 grams being from 1 x 10^-^4 mol to 1 x 10^-^1 mol; Modified polyphenylene ether in the range 0.1-4
0% by weight (3) Olefin polymer 2 to 80% by weight (4) A resin obtained by modifying an olefin polymer with a modifier selected from carboxylic acid or carboxylic anhydride, with a modifier content of 0.01 ~40% by weight of acid-modified olefinic polymers from 0.1 to 60% by weight
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61250278A JPH07116355B2 (en) | 1986-10-21 | 1986-10-21 | Polyphenylene ether resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61250278A JPH07116355B2 (en) | 1986-10-21 | 1986-10-21 | Polyphenylene ether resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63105022A true JPS63105022A (en) | 1988-05-10 |
| JPH07116355B2 JPH07116355B2 (en) | 1995-12-13 |
Family
ID=17205517
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61250278A Expired - Lifetime JPH07116355B2 (en) | 1986-10-21 | 1986-10-21 | Polyphenylene ether resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07116355B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01297456A (en) * | 1988-05-26 | 1989-11-30 | Mitsubishi Gas Chem Co Inc | Solvent-and impact-resistant polyphenylene ether resin composition |
| JPH0236248A (en) * | 1988-04-07 | 1990-02-06 | Sanyo Chem Ind Ltd | Polypropylene based resin composition |
| US5369173A (en) * | 1989-06-13 | 1994-11-29 | Sumitomo Chemical Company, Limited | Glass fiber-reinforced resin composition |
| US7341783B2 (en) * | 2001-09-20 | 2008-03-11 | Asahi Kasei Chemicals Corporation | Functionalized polyphenylene ether |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60258253A (en) * | 1984-06-04 | 1985-12-20 | Mitsubishi Petrochem Co Ltd | Polyphenylene ether composition having improved moldability |
| JPS62257958A (en) * | 1986-05-01 | 1987-11-10 | Toray Ind Inc | Thermoplastic resin composition |
-
1986
- 1986-10-21 JP JP61250278A patent/JPH07116355B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60258253A (en) * | 1984-06-04 | 1985-12-20 | Mitsubishi Petrochem Co Ltd | Polyphenylene ether composition having improved moldability |
| JPS62257958A (en) * | 1986-05-01 | 1987-11-10 | Toray Ind Inc | Thermoplastic resin composition |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0236248A (en) * | 1988-04-07 | 1990-02-06 | Sanyo Chem Ind Ltd | Polypropylene based resin composition |
| JPH01297456A (en) * | 1988-05-26 | 1989-11-30 | Mitsubishi Gas Chem Co Inc | Solvent-and impact-resistant polyphenylene ether resin composition |
| US5369173A (en) * | 1989-06-13 | 1994-11-29 | Sumitomo Chemical Company, Limited | Glass fiber-reinforced resin composition |
| US7341783B2 (en) * | 2001-09-20 | 2008-03-11 | Asahi Kasei Chemicals Corporation | Functionalized polyphenylene ether |
| US7527863B2 (en) | 2001-09-20 | 2009-05-05 | Asahi Kasei Chemicals Corporation | Functionalized polyphenylene ether |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07116355B2 (en) | 1995-12-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0135860B2 (en) | ||
| JP3756133B2 (en) | Graft copolymer and resin composition thereof | |
| US4985495A (en) | Resin composition | |
| EP1165685A1 (en) | Polypropylene and polyester blends containing a graft-modified polyolefin elastomer | |
| Filippi et al. | Reactive compatibilizer precursors for LDPE/PA6 blends, 4 | |
| US4864002A (en) | Process for preparing compatibilized thermoplastic polymer blends and compositions thereof | |
| JPS63105022A (en) | Polyphenylene ether resin composition | |
| WO2002051933A1 (en) | Polypropylene resin composition with improved surface hardness and scratch resistance properties | |
| JP3792189B2 (en) | Graft copolymer and resin composition containing the same | |
| JPH07118518A (en) | Thermoplastic polyphenylene ether resin composition | |
| JPS59176344A (en) | High efficiency rubber-polyester blend | |
| JP2535071B2 (en) | Resin composition | |
| EP0323235B1 (en) | Resin composition | |
| JPS63122757A (en) | Polyphenylene ether resin composition | |
| CA1269778A (en) | Impact-resistant polyamide resin composition and process for producing the same | |
| KR20210091399A (en) | Polypropylene Enhanced Wear-resistance and Impact Strength and Preparing Method thereof | |
| JPH0420546A (en) | Resin composition | |
| JPS587448A (en) | Polyphenylene ether resin composition | |
| JPS6156249B2 (en) | ||
| JPH02173136A (en) | Polyphenylene ether resin composition | |
| JPH0480254A (en) | Thermoplastic resin composition | |
| JPS6160097B2 (en) | ||
| JPS63122756A (en) | Polyphenylene ether resin composition | |
| JPS61271342A (en) | Polyphenylene ether resin composition | |
| JPH1030011A (en) | Modified polyolefin-based polymer and its production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |