JPH02158641A - Thermoplastic resin composition - Google Patents
Thermoplastic resin compositionInfo
- Publication number
- JPH02158641A JPH02158641A JP31187188A JP31187188A JPH02158641A JP H02158641 A JPH02158641 A JP H02158641A JP 31187188 A JP31187188 A JP 31187188A JP 31187188 A JP31187188 A JP 31187188A JP H02158641 A JPH02158641 A JP H02158641A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogenated
- weight
- pts
- block copolymer
- 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
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 13
- 239000011342 resin composition Substances 0.000 title abstract description 17
- -1 poly(2,6-dimenthyl-1,4-phenylene) Polymers 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 19
- 229920001400 block copolymer Polymers 0.000 claims abstract description 18
- 229920001971 elastomer Polymers 0.000 claims abstract description 16
- 239000000806 elastomer Substances 0.000 claims abstract description 16
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 15
- 150000001993 dienes Chemical class 0.000 claims abstract description 5
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229920001955 polyphenylene ether Polymers 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000005826 halohydrocarbons Chemical class 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 7
- 238000000465 moulding Methods 0.000 abstract description 4
- 239000004743 Polypropylene Substances 0.000 abstract description 2
- 229920001155 polypropylene Polymers 0.000 abstract description 2
- 239000004721 Polyphenylene oxide Substances 0.000 abstract 2
- 229920006380 polyphenylene oxide Polymers 0.000 abstract 2
- 241001082241 Lythrum hyssopifolia Species 0.000 abstract 1
- 238000000034 method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 229920006132 styrene block copolymer Polymers 0.000 description 4
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 4
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 3
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-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
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229960002317 succinimide Drugs 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- FPZQYYXSOJSITC-UHFFFAOYSA-N 1-(4-chlorophenyl)pyrrole-2,5-dione Chemical compound C1=CC(Cl)=CC=C1N1C(=O)C=CC1=O FPZQYYXSOJSITC-UHFFFAOYSA-N 0.000 description 1
- BLLFPKZTBLMEFG-UHFFFAOYSA-N 1-(4-hydroxyphenyl)pyrrole-2,5-dione Chemical compound C1=CC(O)=CC=C1N1C(=O)C=CC1=O BLLFPKZTBLMEFG-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- RGWXSQCOYFRTKU-UHFFFAOYSA-N 2,6-didodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC(CCCCCCCCCCCC)=C1O RGWXSQCOYFRTKU-UHFFFAOYSA-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
- KUNNUNBSGQSGDY-UHFFFAOYSA-N 2-butyl-6-methylphenol Chemical compound CCCCC1=CC=CC(C)=C1O KUNNUNBSGQSGDY-UHFFFAOYSA-N 0.000 description 1
- YCUALLYXPZGZFN-UHFFFAOYSA-N 2-cyclohexyl-6-methylphenol Chemical compound CC1=CC=CC(C2CCCCC2)=C1O YCUALLYXPZGZFN-UHFFFAOYSA-N 0.000 description 1
- MFUPLJQNEXUUDW-UHFFFAOYSA-N 2-phenylisoindole-1,3-dione Chemical compound O=C1C2=CC=CC=C2C(=O)N1C1=CC=CC=C1 MFUPLJQNEXUUDW-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
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920004939 Cariflex™ Polymers 0.000 description 1
- 229920002633 Kraton (polymer) Polymers 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 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
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- KNCYXPMJDCCGSJ-UHFFFAOYSA-N piperidine-2,6-dione Chemical compound O=C1CCCC(=O)N1 KNCYXPMJDCCGSJ-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-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、ｒｚｏｄ衝撃強度に代表される耐衝撃性、熱
変形温度に代表される耐熱性、メルトフローインデック
スに代表される成形加工性が共に優れた熱可塑性樹脂組
成物に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention provides improved impact resistance as represented by rzod impact strength, heat resistance as represented by heat distortion temperature, and moldability as represented by melt flow index. Both relate to excellent thermoplastic resin compositions.
ポリフェニレンエーテル樹脂は機械的性質、耐熱性に優
れた樹脂であることが広く知られているが、溶融粘度が
高く、成形時に高温を要するため変色、酸化劣化を生じ
、−船釣には単独では使用されていない０通常はポリス
チレン、ゴム変性ポリスチレンとからなる樹脂組成物と
して使用されている。しかしながら、この樹脂組成物は
ポリフェニレンエーテル樹脂の成形加工性を改善しては
いるが、熱変形温度が大幅に低下している。また、耐衝
撃性、耐薬品性についても充分満足できるものではなか
った。特開昭５４−８８９６０にはポリフェニレンエー
テル樹脂、ポリオレフィン樹脂、オよびＡ−Ｂ−Ａ’型
ブロック共重合体エラストマーよりなる組成物が開示さ
れている。耐衝撃についてはかなり改良されてはいるが
、ポリオレフィン樹脂の割合が３０重重景以下のために
耐薬品性については充分に満足されるものではない。ま
た、ポリオレフィン樹脂の割合が３０重量％を超えると
、ポリオレフィン樹脂とポリフェニレンエーテル樹脂と
の相溶性が悪く、成形物の外観不良、成形加工片の強度
の低下、および層割れが見られる。Polyphenylene ether resin is widely known to be a resin with excellent mechanical properties and heat resistance, but it has a high melt viscosity and requires high temperatures during molding, which causes discoloration and oxidative deterioration, making it difficult to use alone for boat fishing. Not used 0 Usually used as a resin composition consisting of polystyrene or rubber-modified polystyrene. However, although this resin composition improves the moldability of polyphenylene ether resin, the heat distortion temperature is significantly lowered. Furthermore, the impact resistance and chemical resistance were not fully satisfactory. JP-A-54-88960 discloses a composition comprising a polyphenylene ether resin, a polyolefin resin, and an A-B-A' type block copolymer elastomer. Although the impact resistance has been considerably improved, the chemical resistance is not fully satisfied because the proportion of polyolefin resin is less than 30% by weight. Furthermore, when the proportion of the polyolefin resin exceeds 30% by weight, the compatibility between the polyolefin resin and the polyphenylene ether resin is poor, resulting in poor appearance of the molded product, decrease in strength of the molded piece, and layer cracking.
本発明の目的は、ポリフェニレンエーテル樹脂とポリオ
レフィン樹脂との相溶性を改良し、耐熱性、耐衝撃性、
加工性、耐薬品性、耐吸湿性が共に優れたエンジニアリ
ングプラスチックスを提供することにある。The purpose of the present invention is to improve the compatibility between polyphenylene ether resin and polyolefin resin, and improve heat resistance, impact resistance,
Our objective is to provide engineering plastics with excellent processability, chemical resistance, and moisture absorption resistance.
［問題を解決するための手段］
本発明者らは、上記問題を解決すべく鋭意検討した結果
、特願昭６３−２０３７１８において、ポリフェニレン
エーテル樹脂、ポリオレフィン樹脂、ＡＢ−Ａ’型ブロ
ック共重合体エラストマーおよび炭素−炭素二重結合を
有し、且つ官能基として、カルボン酸基、酸無水物基、
アミド基、イミド基、カルボン酸エステル基、エポキシ
基、アミノ基、水酸基のいずれか一種以上を有する不飽
和化合物を特定の割合で配合し、溶融混練して得られる
樹脂組成物が上記目的を達成できることを見い出したが
、さらに引き続き検討した結果、ポリフェニレンエーテ
ル樹脂、ポリオレフィン樹脂、水添Ａ−Ｂ−Ａ’型ブロ
ック共重合体および酸イミド化合物を特定の割合で配合
し、溶融混練して得られる樹脂組成物が最も好ましいも
のであることを見い出し、本発明に到達したものである
。[Means for Solving the Problems] As a result of intensive studies to solve the above problems, the present inventors disclosed in Japanese Patent Application No. 63-203718 a polyphenylene ether resin, a polyolefin resin, and an AB-A' type block copolymer. It has an elastomer and a carbon-carbon double bond, and as a functional group, a carboxylic acid group, an acid anhydride group,
A resin composition obtained by blending and melt-kneading unsaturated compounds having one or more of amide group, imide group, carboxylic acid ester group, epoxy group, amino group, and hydroxyl group in a specific ratio achieves the above objective. However, as a result of further investigation, we discovered that polyphenylene ether resin, polyolefin resin, hydrogenated A-B-A' type block copolymer, and acid imide compound can be blended in specific proportions and melt-kneaded. It was discovered that the resin composition is the most preferable, and the present invention was achieved.
即ち、本発明は
（ａ）一般式
（式中Ｒ，、Ｒ，、Ｒ３、およびＲ４はそれぞれ独立に
ハロゲン、水素、炭化水素、ハロ炭化水素、炭化水素オ
キシおよびハロ炭化水素オキシで構成される群から選択
され、ｎはモノマー単位の総数を表わし、２０以上の整
数である）で示されるポリフェニレンエーテル樹脂２０
〜９５重量％、（ｂ）ポリオレフィン樹脂８０〜５重量
％、（Ｃ）前記（ａ）＋ （ｂ）合計１００重量部に対
して、水添Ａ−Ｂ−Ａ’型ブロック共重合体エラストマ
ー（ここで、Ａ、Ａ’は重合されたビニル系芳香族炭化
水素ブロックであり、Ｂは重合された共役ジエンブロン
クが水素添加されたものである）１〜３０重量部、およ
び（ｄ）酸イミド化合物 １〜２０重量部よりなる熱可
塑性樹脂組成物を提供するものである。That is, the present invention relates to (a) the general formula (wherein R, , R, , R3, and R4 are each independently composed of halogen, hydrogen, hydrocarbon, halohydrocarbon, hydrocarbonoxy, and halohydrocarbonoxy) polyphenylene ether resin 20 selected from the group (n represents the total number of monomer units and is an integer of 20 or more)
~95% by weight, (b) polyolefin resin 80~5% by weight, (C) hydrogenated A-B-A' type block copolymer elastomer ( Here, A and A' are polymerized vinyl aromatic hydrocarbon blocks, B is a hydrogenated polymerized conjugated diene block) 1 to 30 parts by weight, and (d) acid imide compound. A thermoplastic resin composition comprising 1 to 20 parts by weight is provided.
本発明の熱可塑性樹脂組成物を構成する（ａ）成分のポ
リフェニレンエーテル樹脂は前記一般式で示される単位
を一種以上含存するホモポリマーまたはコポリマーが望
ましい。ポリフェニレンエテル樹脂の製造方法は特に限
定しないが、米国特許第３３０６８７４号、同第３３０
６８７５号、同第３２５７３５７号および第３２５７３
５８号に記載の方法でフェノル類の反応によって製造で
きる。これらフェノール類としては、２．６−シメチル
フエノール、２６−ジニチルフエノール、２，６−シブ
チルフェノール、２，６−ジラウリルフェノール、２６
−ジプロピルフェノール、２．６−ジフェニルフェノー
ル、２−メチル−６−ニチルフエノール、２−メチル−
６−シクロヘキジルフエノール、２−メチル−６−メド
キシフエノール、２−メチル−６−ブチルフェノール、
２，６−シメトキシフエノール、２．３６−ドリメチル
フエノール、２，３，５．６−チトラメチルフエノール
および２．６−ジニトキシフエノールが含有されるが、
これらに限定されるものではない。The polyphenylene ether resin component (a) constituting the thermoplastic resin composition of the present invention is preferably a homopolymer or copolymer containing one or more units represented by the above general formula. The method for producing polyphenylene ether resin is not particularly limited, but US Pat. Nos. 3,306,874 and 330
No. 6875, No. 3257357 and No. 32573
It can be produced by the reaction of phenols according to the method described in No. 58. These phenols include 2,6-dimethylphenol, 26-dinitylphenol, 2,6-sibutylphenol, 2,6-dilaurylphenol,
-dipropylphenol, 2,6-diphenylphenol, 2-methyl-6-nitylphenol, 2-methyl-
6-cyclohexylphenol, 2-methyl-6-medoxyphenol, 2-methyl-6-butylphenol,
Contains 2,6-simethoxyphenol, 2,36-drimethylphenol, 2,3,5,6-titramethylphenol and 2,6-dinitoxyphenol,
It is not limited to these.
本発明において、好ましいポリフェニレンエーテル樹脂
はポリ（２，６−シメチルー１．４−フェニレン）エー
テルである。In the present invention, a preferred polyphenylene ether resin is poly(2,6-dimethyl-1,4-phenylene) ether.
本発明の熱可塑性樹脂組成物を構成する（ｂ）成分のポ
リオレフィン樹脂とは、例えばポリブロピレン、ポリエ
チレン、プロピレン−エチレン共重合体、ポリブテン、
ポリメチルペンテン等が挙げられる。これらは商業的に
入手可能であり、当業者に周知の方法によって製造し得
る。The polyolefin resin of component (b) constituting the thermoplastic resin composition of the present invention includes, for example, polypropylene, polyethylene, propylene-ethylene copolymer, polybutene,
Examples include polymethylpentene. These are commercially available and may be manufactured by methods well known to those skilled in the art.
本発明の熱可塑性樹脂組成物を構成する（ｃ）成分の水
添Ａ−Ｂ−Ａ’型ブロック共重合体エラストマーとは、
ビニル系芳香族炭化水素重合体Ａ、Ａ′ブロックと共役
ジエン重合体が水素添加されたＢブロックからなり、ビ
ニル芳香族炭化水素の例としては、スチレン、α−メチ
ルスチレン、ビニルトルエン、ビニルキシレン、ビニル
ナフタレンおよびそれらの混合物などが挙げられる。Ａ
およびＡ′は同一でも異なっていても良い、また共役ジ
エンの例としては、１．３−ブタジェン、２．３−ジメ
チルブタジェン、イソプレンおよび１．３−ペンタジェ
ンなどが挙げられ、水素添加されたものが本発明におい
て好適に使用される。The hydrogenated A-B-A' type block copolymer elastomer as the component (c) constituting the thermoplastic resin composition of the present invention is:
Consisting of vinyl aromatic hydrocarbon polymers A and A' blocks and B block hydrogenated with a conjugated diene polymer, examples of vinyl aromatic hydrocarbons include styrene, α-methylstyrene, vinyltoluene, and vinylxylene. , vinylnaphthalene and mixtures thereof. A
and A' may be the same or different, and examples of conjugated dienes include 1,3-butadiene, 2,3-dimethylbutadiene, isoprene, and 1,3-pentadiene, and hydrogenated are preferably used in the present invention.
本発明に使用される水添Ａ−Ｂ−Ａ’型ブロック共重合
体エラストマーは商業的に入手可能であり、当業者に周
知の方法で製造し得る。The hydrogenated A-B-A' type block copolymer elastomers used in the present invention are commercially available and can be made by methods well known to those skilled in the art.
本発明の熱可塑性樹脂組成物を構成する（ｄ）成分とは
、酸イミド化合物、即ち、−船釣にＮＨまたは第１級ア
ミン化合物と２塩基酸のアシル基から誘導される環状の
イミドが使用される。第一級アミンの例としてはアニリ
ン、シクロヘキンルアミン、Ｐ−ヒドロキシアニリン等
が挙げられ、２塩基酸の例としてはコハク酸、グルタル
酸、フタル酸、マレイン酸等が挙げられる。即ち、酸イ
ミド化合物の代表例としては、コハクイミド、グルタル
イミド、フタルイミド、Ｎ−フェニルフタルイミド、Ｎ
−フェニルマレイミド、Ｎ−シクロへキシルマレイミド
、Ｎ−（４−ヒドロキシフェニル）マレイミド、Ｎ−（
４−カルボキシフェニル）マレイミド、Ｎ−（４−クロ
ロフェニル）マレイミド等が挙げられる。Component (d) constituting the thermoplastic resin composition of the present invention is an acid imide compound, that is, a cyclic imide derived from an acyl group of a dibasic acid and an NH or a primary amine compound. used. Examples of primary amines include aniline, cyclohexylamine, P-hydroxyaniline, etc., and examples of dibasic acids include succinic acid, glutaric acid, phthalic acid, maleic acid, etc. That is, representative examples of acid imide compounds include succinimide, glutarimide, phthalimide, N-phenylphthalimide, N
-phenylmaleimide, N-cyclohexylmaleimide, N-(4-hydroxyphenyl)maleimide, N-(
Examples include 4-carboxyphenyl)maleimide and N-(4-chlorophenyl)maleimide.
本発明の熱可塑性樹脂組成物において、（ａ）ポリフェ
ニレン樹脂、（ｂ）ポリオレフィン樹脂（Ｃ）水添Ａ−
Ｂ−Ａ’型ブロック共重合体エラストマー （ｄ）酸イ
ミド化合物の配合比は、（ａ）が２０〜９５重貴％、好
ましくは４０〜９０重廿％（ｂ）が８０〜５重量％、好
ましくは６０−１０重量％の範囲であり、（ａ）が２０
重量％未満では耐熱と剛性が劣り、（ａ）が９５重量％
を越えると耐衝撃性、耐薬品性、が低下するため好まし
くない。In the thermoplastic resin composition of the present invention, (a) polyphenylene resin, (b) polyolefin resin (C) hydrogenated A-
B-A' type block copolymer elastomer (d) The blending ratio of the acid imide compound is (a) 20 to 95% by weight, preferably 40 to 90% by weight, (b) 80 to 5% by weight, Preferably the range is 60-10% by weight, and (a) is 20% by weight.
If it is less than 95% by weight, heat resistance and rigidity will be poor, and if (a) is 95% by weight
Exceeding this is not preferable because impact resistance and chemical resistance deteriorate.
また、（ｃ）および（ｄ）の配合比は（ａ）＋（ｂ）合
計１００重量部に対して（ｃ）が１〜３０重量部、好ま
しくは３〜２０重量部、（ｄ）が １〜２０！量部、好
ましくは ５〜１５重量部の範囲である。（Ｃ）が１重
量部未満では成形加工性が低下し、３０重量部を越える
と耐熱、耐衝撃が低下し、好ましくない、また、（ｃ）
の水添Ａ−Ｂ−Ａ’型ブロック共重合体エラストマーを
上記組成で添加したものは、水添されていないＡ−Ｂ−
Ａ’型ブロック共重合体エラストマーを同量添加したも
のに比べ、耐衝撃性、成形加工性に著しい効果が表れて
いる。In addition, the blending ratio of (c) and (d) is 1 to 30 parts by weight, preferably 3 to 20 parts by weight, and 1 to 10 parts by weight of (d) to the total 100 parts by weight of (a) + (b). ~20! parts by weight, preferably in the range of 5 to 15 parts by weight. If (C) is less than 1 part by weight, molding processability decreases, and if it exceeds 30 parts by weight, heat resistance and impact resistance decrease, which is undesirable.
The hydrogenated A-B-A' block copolymer elastomer of the above composition is added to the non-hydrogenated A-B-A' block copolymer elastomer.
Compared to the same amount of A' type block copolymer elastomer added, the impact resistance and moldability are significantly improved.
本発明の熱可塑性樹脂組成物の製造方法に関しては特に
制限はなく、通常公知の方法を採用することができる。There are no particular limitations on the method for producing the thermoplastic resin composition of the present invention, and generally known methods can be employed.
すなわち、（ａ）ポリフェニレンエーテル樹脂、（ｂ）
ポリオレフィン樹脂、（Ｃ）水添Ａ−Ｂ−Ａ’型ブロン
ク共重合体エラストマー （ｄ）酸イミド化合物を高速
撹拌機などを用いて均一混合した後、充分な混練能力の
ある一軸または多軸の押出機で溶融混練する方法等を採
用することができる。That is, (a) polyphenylene ether resin, (b)
After uniformly mixing the polyolefin resin, (C) hydrogenated A-B-A' type bronch copolymer elastomer (d) acid imide compound using a high-speed stirrer, etc., A method such as melt-kneading using an extruder can be adopted.
本発明の熱可塑性樹脂組成物は、必要に応じてポリスチ
レン、スチレン−アクリロニトリル共重合体、アクリロ
ニトリル−ブタジェン−スチレン共重合体（ＡＢＳ）、
スチレン−無水マレイン酸共重合体、ゴム変性ポリスチ
レン、α−メチルスチレン−アクリロニトリル共重合体
などの可塑性樹脂を適宜混合することによって、さらに
望ましい物性、特性に調節することも可能である。また
、目的に応じて顔料や染料、ガラス繊維、金属繊維、炭
素繊維などの補強材、タルク、炭酸カルシウムなどの充
填剤、酸化防止剤、紫外線吸収剤、滑剤、難燃剤、およ
び帯電防止剤などを添加することができる。The thermoplastic resin composition of the present invention may optionally contain polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer (ABS),
By appropriately mixing a plastic resin such as a styrene-maleic anhydride copolymer, rubber-modified polystyrene, or α-methylstyrene-acrylonitrile copolymer, it is also possible to adjust the physical properties and characteristics to more desirable ones. Depending on the purpose, we also use pigments, dyes, reinforcing materials such as glass fiber, metal fiber, and carbon fiber, fillers such as talc and calcium carbonate, antioxidants, ultraviolet absorbers, lubricants, flame retardants, and antistatic agents. can be added.
〔実施例］ 以下に実施例を挙げて本発明をさらに詳しく説明する。〔Example] The present invention will be explained in more detail with reference to Examples below.
ただし、本発明はこれらの実施例に限定されるものでは
ない、なお、実施例および比較例に記したポリマーおよ
び成形品の特性評価は、以下の方法に従って実施した。However, the present invention is not limited to these Examples. Characteristic evaluations of the polymers and molded articles described in the Examples and Comparative Examples were carried out according to the following methods.
（１）アイゾツト衝撃強度 ＪＩＳに−７１１０に準拠した。(1) Izotsu impact strength Compliant with JIS-7110.
（２）熱変形温度 ＪＩＳに−７２０７に準拠した。(2) Heat distortion temperature Compliant with JIS-7207.
（３）メルトフローインデックス（成形加工性）ＪＩＳ
Ｋ −７２１０に準拠した。(3) Melt flow index (molding processability) JIS
Compliant with K-7210.
荷重 １６ｋｇ、温度３００°Ｃ
実施例１〜４
ポリフェニレンエーテル樹脂［ＯＥＭポリマー（株）製
］、ポリオレフィン樹脂として、ポリプロピレン−エチ
レンブロック共重合体［三井東圧化学（株）製、商品名
Ｂ Ｊ Ｈ−Ｇ］ 、水添Ａ−ＢＡ′型ブロック共重合
体エラストマーとして（スチレン／水添ブタジェン／ス
チレン）フロック共重合体〔シェル化学（株）製、商品
名クレイトンＧ−１６５０］ 、および酸イミド化合物
としてフタルイミドを表１に示す割合で配合し、これを
２７０〜３００°Ｃの範囲で混練、押出しペレット化し
た。Load: 16 kg, temperature: 300°C Examples 1 to 4 Polyphenylene ether resin [manufactured by OEM Polymer Co., Ltd.], polypropylene-ethylene block copolymer [manufactured by Mitsui Toatsu Chemical Co., Ltd., trade name: B J H] as the polyolefin resin. -G], hydrogenated A-BA' type block copolymer elastomer (styrene/hydrogenated butadiene/styrene) flock copolymer [manufactured by Shell Chemical Co., Ltd., trade name Kraton G-1650], and acid imide compound Phthalimide was blended in the proportions shown in Table 1, and the mixture was kneaded and extruded at a temperature of 270 to 300°C to form pellets.
このペレットから射出成形試験片を作成し、上記物性を
測定した結果を表１に示す、いずれも耐衝撃、耐熱性、
加工性、外観とも優れており、充分な実用価値を有する
ものである。Injection molded test pieces were made from these pellets, and the above physical properties were measured. The results are shown in Table 1.
It has excellent workability and appearance, and has sufficient practical value.
実施例５〜６
実施例２において、（スチレン／水添ブタジェン／スチ
レン）ブロック共重合体を表１に示す割合で配合した以
外は実施例２と同様にした。いずれも耐衝撃、耐熱性、
加工性、外観とも優れており、充分な実用価値を有する
ものである。Examples 5 to 6 Example 2 was carried out in the same manner as in Example 2, except that the (styrene/hydrogenated butadiene/styrene) block copolymer was blended in the proportions shown in Table 1. Both are impact resistant, heat resistant,
It has excellent workability and appearance, and has sufficient practical value.
実施例７〜８
実施例２において、フタルイミドを表１に示す割合で配
合した以外は実施例２と同様にした。いずれも耐衝撃、
耐熱性、加工性、外観とも優れており、充分な実用価値
を有するものである。Examples 7 to 8 The same procedure as Example 2 was carried out except that phthalimide was blended in the proportions shown in Table 1. Both are impact resistant,
It has excellent heat resistance, workability, and appearance, and has sufficient practical value.
実施例７〜１０
実施例３〜４において、酸イミド化合物としてコハクイ
ミドを表１に示す割合で配合した以外は実施例３〜４と
同様にした。いずれも耐衝撃性、加工性、外観とも優れ
ており、充分な実用価値を有するものである。Examples 7 to 10 In Examples 3 to 4, the same procedures as Examples 3 to 4 were carried out except that succinimide was blended as the acid imide compound in the proportion shown in Table 1. All of them are excellent in impact resistance, workability, and appearance, and have sufficient practical value.
実施例１１〜１２
実施例３〜４において、（スチレン／水添ブタジェン／
スチレン）ブロック共重合体、及び酸イミド化合物とし
てＮ−フェニルマレイミドを表１に示す割合で配合した
以外は実施例３〜４と同様にした。いずれも耐衝撃性、
加工性、外観とも優れており、充分な実用価値を存する
ものである。Examples 11-12 In Examples 3-4, (styrene/hydrogenated butadiene/
The procedure was the same as in Examples 3 and 4, except that the styrene block copolymer and N-phenylmaleimide as the acid imide compound were blended in the proportions shown in Table 1. Both are impact resistant,
It has excellent workability and appearance, and has sufficient practical value.
比較例１
実施例１１において、水添Ａ−Ｂ−Ａ’ブロック共重合
体エラストマーを用いず、水添されていないＡ−Ｂ−Ａ
’型ブロック共重合体エラストマーとして、（スチレン
／ブタジェン／スチレン）ブロック共重合体［シェル化
学（株）製、商品名カリフレックスＴＲｌｌ０Ｉ］を用
いて表１に示す割合で配合した以外は実施例１１と同様
にした。実施例と比較して耐衝撃が著しく低下している
他、メルトフローインデックスも低下している。Comparative Example 1 In Example 11, the hydrogenated A-B-A' block copolymer elastomer was not used, and the non-hydrogenated A-B-A
Example 11 except that a (styrene/butadiene/styrene) block copolymer [manufactured by Shell Chemical Co., Ltd., trade name: CARIFLEX TRll0I] was used as the ' type block copolymer elastomer and blended in the proportions shown in Table 1. I did the same thing. In addition to the impact resistance being markedly lower than in Examples, the melt flow index was also lower.
比較例２
実施例１１において、水添Ａ−Ｂ−Ａ’型ブロック共重
合体エラストマーを添加せずに表１に示す割合で配合し
た以外は実施例１１と同様にした。実施例と比較して外
観の不良、衝撃性の低下がみられる。Comparative Example 2 The same procedure as Example 11 was carried out except that the hydrogenated A-B-A' type block copolymer elastomer was not added and the proportions shown in Table 1 were blended. Poor appearance and decrease in impact resistance are observed compared to Examples.
比較例３
実施例４において、酸イミド化合物を添加せずに表１に
示す割合で配合した以外は実施例４と同様にした。実施
例と比較して外観の不良、メルトフローインデックスの
低下がみられる。Comparative Example 3 The same procedure as Example 4 was carried out except that the acid imide compound was not added and the proportions shown in Table 1 were blended. Compared to Examples, poor appearance and decrease in melt flow index were observed.
比較例４
実施例１において、ポリフェニレンエーテル樹脂を表１
に示す割合で配合した以外は実施例１と同様にした。実
施例と比較して耐熱性の低下がみられる。Comparative Example 4 In Example 1, the polyphenylene ether resin was
The same procedure as in Example 1 was carried out except that the ingredients were blended in the proportions shown in . A decrease in heat resistance is observed compared to the example.
比較例５
実施例１において、ポリフェニレンエーテル樹脂、ポリ
オレフィン樹脂、酸イミド化合物を表１に示す割合で配
合した以外は実施例１と同様にした、実施例と比較して
耐衝撃の低下がみられる。Comparative Example 5 The same procedure as Example 1 was carried out except that the polyphenylene ether resin, polyolefin resin, and acid imide compound were blended in the proportions shown in Table 1. A decrease in impact resistance was observed compared to Example 1. .
比較例６
実施例２において、（スチレン／水添ブタジェン／スチ
レン）ブロック共重合体を表１に示す割合で配合した以
外は実施例２と同様にした。実施例と比較して外観の不
良、耐熱性の低下がみられる。Comparative Example 6 The same procedure as Example 2 was carried out except that the (styrene/hydrogenated butadiene/styrene) block copolymer was blended in the proportions shown in Table 1. Compared to the examples, poor appearance and decreased heat resistance are observed.
本発明の熱可塑性樹脂組成物は耐衝撃、耐熱性、成形加
工性共に優れており、自動車部品、工業部品、電気部品
などに好適に用いられる。The thermoplastic resin composition of the present invention has excellent impact resistance, heat resistance, and moldability, and is suitably used for automobile parts, industrial parts, electrical parts, and the like.
特許出願人 三井東圧化学株式会社Patent applicant: Mitsui Toatsu Chemical Co., Ltd.
Claims (1)
れ独立にハロゲン、水素、炭化水素、ハロ炭化水素、炭
化水素オキシおよびハロ炭化水素オキシで構成される群
から選択され、ｎはモノマー単位の総数を表わし、２０
以上の整数である）で示されるポリフェニレンエーテル
樹脂２０〜９５重量％、（ｂ）ポリオレフィン樹脂８０
〜５重量％、（ｃ）前記（ａ）＋（ｂ）合計１００重量
部に対して、水添Ａ−Ｂ−Ａ′型ブロック共重合体エラ
ストマー（ここで、Ａ、Ａ′は重合されたビニル系芳香
族炭化水素ブロックであり、Ｂは重合された共役ジエン
ブロックが水素添加されたものである）１〜３０重量部
、および（ｄ）酸イミド化合物１〜２０重量部よりなる
熱可塑性樹脂組成物。[Claims] (a) General formula▲ Numerical formula, chemical formula, table, etc.▼ (In the formula, R_1, R_2, R_3, and R_4 are each independently halogen, hydrogen, hydrocarbon, halohydrocarbon, hydrocarbon oxy and halohydrocarbonoxy, where n represents the total number of monomer units, and 20
20 to 95% by weight of polyphenylene ether resin (which is an integer above), (b) polyolefin resin 80%
~5% by weight, (c) Hydrogenated A-B-A' type block copolymer elastomer (where A, A' are polymerized A thermoplastic resin consisting of 1 to 30 parts by weight of (a vinyl aromatic hydrocarbon block, B is a hydrogenated polymerized conjugated diene block) and 1 to 20 parts by weight of (d) an acid imide compound. Composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31187188A JPH02158641A (en) | 1988-12-12 | 1988-12-12 | Thermoplastic resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31187188A JPH02158641A (en) | 1988-12-12 | 1988-12-12 | Thermoplastic resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02158641A true JPH02158641A (en) | 1990-06-19 |
Family
ID=18022417
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31187188A Pending JPH02158641A (en) | 1988-12-12 | 1988-12-12 | Thermoplastic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02158641A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63113050A (en) * | 1986-10-31 | 1988-05-18 | Mitsubishi Petrochem Co Ltd | Resin composition |
| JPS63241064A (en) * | 1987-01-19 | 1988-10-06 | ゼネラル・エレクトリック・カンパニイ | Polymer blend of polyphenylene ether and functional polyolefin |
-
1988
- 1988-12-12 JP JP31187188A patent/JPH02158641A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63113050A (en) * | 1986-10-31 | 1988-05-18 | Mitsubishi Petrochem Co Ltd | Resin composition |
| JPS63241064A (en) * | 1987-01-19 | 1988-10-06 | ゼネラル・エレクトリック・カンパニイ | Polymer blend of polyphenylene ether and functional polyolefin |
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