JPS6353226B2 - - Google Patents
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- Publication number
- JPS6353226B2 JPS6353226B2 JP60150069A JP15006985A JPS6353226B2 JP S6353226 B2 JPS6353226 B2 JP S6353226B2 JP 60150069 A JP60150069 A JP 60150069A JP 15006985 A JP15006985 A JP 15006985A JP S6353226 B2 JPS6353226 B2 JP S6353226B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- monomer
- copolymer
- monomers
- 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.)
- Expired
Links
- 239000000178 monomer Substances 0.000 claims description 68
- 229920002554 vinyl polymer Polymers 0.000 claims description 26
- 229920002614 Polyether block amide Polymers 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 20
- 229920000578 graft copolymer Polymers 0.000 claims description 19
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 14
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 12
- 239000011342 resin composition Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 229920001971 elastomer Polymers 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 229920005992 thermoplastic resin Polymers 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 22
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 12
- 239000002202 Polyethylene glycol Substances 0.000 description 12
- 229920001223 polyethylene glycol Polymers 0.000 description 12
- -1 acrylic ester Chemical class 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- 150000004985 diamines Chemical class 0.000 description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 5
- 239000004816 latex Substances 0.000 description 5
- 229920000126 latex Polymers 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical group O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- VTPNYMSKBPZSTF-UHFFFAOYSA-N 1-ethenyl-2-ethylbenzene Chemical compound CCC1=CC=CC=C1C=C VTPNYMSKBPZSTF-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- TVONJMOVBKMLOM-UHFFFAOYSA-N 2-methylidenebutanenitrile Chemical compound CCC(=C)C#N TVONJMOVBKMLOM-UHFFFAOYSA-N 0.000 description 1
- UFFRSDWQMJYQNE-UHFFFAOYSA-N 6-azaniumylhexylazanium;hexanedioate Chemical compound [NH3+]CCCCCC[NH3+].[O-]C(=O)CCCCC([O-])=O UFFRSDWQMJYQNE-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002947 alkylene 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
- 125000003277 amino group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- FFPQSNUAVYJZDH-UHFFFAOYSA-N diazanium;terephthalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 FFPQSNUAVYJZDH-UHFFFAOYSA-N 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
〔産業上の利用分野〕
本発明は永久帯電防止性を有し、かつ耐衝撃性
に代表される機械的特性がすぐれた熱可塑性樹脂
組成物に関する。
〔従来の技術〕
合成高分子材料は、そのすぐれた特性によつて
広範な分野で使用されている。これらの材料は、
材料の持つ機械的強度に加え、帯電防止性を付与
されればさらにその用途を拡大することができ
る。すなわち、静電気による障害を防止したい複
写機、各種防塵用部品などへの用途展開が可能と
なる。
合成高分子材料の制電性を向上させる方法とし
ては、共役ジエン又は／およびアクリル酸エステ
ルとアルキレンオキサイド基を有するビニル系単
量体を共重合して得られる親水性ゴム状重合体に
ビニル系単量体又はビニリデン単量体をグラフト
重合して得る方法（特開昭55−36237号公報）な
どがあり、実用制電性を達成している。
〔発明が解決しようとする問題点〕
しかしこれらの制電性樹脂は特殊な親水性ゴム
状重合体を使用しているため、その製造方法が煩
雑なこと、および得られる樹脂の機械的特性が劣
る欠点があり、十分満足できるものではない。
本発明者らは永久帯電防止性を有し、かつ耐衝
撃性に代表される機械的特性が優れた制電性樹脂
を提供することを目的として鋭意検討した結果、
特定のポリエーテルアミドとゴム質重合体に特定
のビニル系単量体をグラフト重合してなるグラフ
ト共重合体および／または特定のビニル系単量体
の重合体を混合することにより上記目的が効率的
に達成されることを見出し本発明に到達した。
〔問題点を解決するための手段〕
すなわち本発明は、
(A) ポリエーテルアミド共重合体５〜80重量部と
(B) ゴム質重合体１〜80重量部の存在下に（メ
タ）アクリル酸エステル単量体および／または
芳香族ビニル系単量体100〜40重量％およびこ
れらと共重合可能な他のビニル単量体０〜60重
量％からなる単量体または単量体混合物99〜20
重量部を重合させたグラフト共重合体および／
または
(C) （メタ）アクリル酸エステル単量体および／
または芳香族ビニル単量体100〜40重量％およ
びこれらと共重合可能な他のビニル単量体０〜
60重量％からなる単量体または単量体混合物を
重合してなる重合体95〜20重量部からなる組成
物100重量部に対して
(D) スルホン酸の金属塩０〜５重量部を配合して
なる制電性樹脂組成物である。
以下に本発明を具体的に説明する。
本発明の組成物は(A)ポリエーテルアミド共重合
体、(B)グラフト共重合体および／または(C)ビニル
系単量体の重合体、更に(D)スルホン酸の金属塩よ
りなる。
本発明における(A)ポリエーテルアミド共重合体
の構成成分は、実質的にポリエチレングリコール
ジアミンとジカルボン酸、脂肪族ジアミン、ε−
カプロラクタムを主たる成分とする共重合体をい
う。
ポリエチレングリコールジアミンには、分子量
200〜6000のポリエチレンオキシド基を主鎖とし、
例えばポリエチレングリコールをシアノエチル化
した後水素添加して得られる両末端ジアミンが使
用できる。
このジアミンの分子量は、本発明の組成物の帯
電防止性能を決定すると同時に、ポリエーテルア
ミド共重合体とグラフト共重合体との相溶性、組
成物の加工性にも影響を与える。すなわち、分子
量が低い場合は、相溶性や加工性は良いが、帯電
防止性能が悪くなる。また、分子量が大きくなる
と、帯電防止性は良いが、相溶性、分散性が悪
く、加工性が悪い。好ましい分子量はポリエチレ
ンオキシド基で200〜600の範囲である。
ポリエチレングリコールジアミンの添加量はポ
リエーテルアミド共重合体に対して20〜80重量％
が好ましい。20重量％以下では、最終の組成物の
帯電防止性能が不十分となる。80重量％以上にな
るとポリエーテルアミド共重合体とグラフト共重
合体の相溶性が悪く、層状剥離を起こすため好ま
しくない。
ポリエチレングリコールジアミンはジカルボン
酸塩として使用される。ジカルボン酸としては、
アジピン酸、セバシン酸、アゼライン酸、、ベン
ゼンジカルボン酸などが、単独もしくは混合物と
して使用できる。特に脂肪族ジカルボン酸とベン
ゼンジカルボン酸の混合使用が好ましい。
脂肪酸ジアミンは実質的にはヘキサメチレンジ
アミンが経済的な理由から好ましいが、その一部
を他の脂肪族ジアミンと置換することも可能であ
る。脂肪族ジアミンは、ベンゼンジカルボン酸の
添加量が増え、重合速度が低下した場合に、ポリ
エチレングリコールジアミンと等モル以内の添加
量で添加することができる。脂肪族ジアミンは、
ジカルボン酸の塩として添加することが望まし
い。
上記ポリエチレングリコールジアミン、ジカル
ボン酸、脂肪族ジアミンの混合物はε−カプロラ
クタムの共存下、窒素雰囲気下に220〜270℃に加
熱することにより、ポリエーテルアミド共重合体
を与える。この重合に際して、着色防止剤とし
て、ホスフアイト類、ヒンダードフエノール類な
どを添加することができる。
本発明において用いる(B)グラフト共重合体の構
成成分であるゴム質重合体としては、ガラス転移
温度が０℃以下のものが好適であり、具体的には
ポリブタジエン、ポリスチレン−ブタジエン、ポ
リアクリロニトリル−ブタジエン等のジエン系ゴ
ム、ポリイソプレン、ポリクロロプレン、ポリア
クリル酸ブチル等のアクリル系ゴムおよびエチレ
ン−プロピレン−ジエンモノマー三元共重合体等
ゴム質重合体を使用できる。特にブタジエン又は
ブタジエン共重合体が好ましい。
（メタ）アクリル酸エステル単量体としてはメ
タクリル酸メチル、メタクリル酸エチル、メタク
リル酸プロピルおよびアクリル酸メチルなどがあ
げられるが特にメタクリル酸メチルが好ましい。
芳香族ビニル系単量体としてはスチレン、α−
メチルスチレン、ビニルトルエン、ｏ−エチルス
チレン、ｏ−ｐ−ジクロロスチレンなどがあげら
れるが特にスチレンが好ましい。
またこれらと共重合可能な他のビニル単量体と
してはアクリロニトリル、メタクリロニトリルな
どのシアン化ビニル系単量体、アクリル酸、メタ
クリル酸、マレイン酸、無水マレイン酸などの
α，β−不飽和カルボン酸、マレイミド、Ｎ−フ
エニルマレイミドなどのマレイミド系単量体が挙
げられるが、特にアクリロニトリルが好ましい。
また(B)グラフト共重合体はゴム質重合体１〜80重
量部、好ましくは10〜60重量部に（メタ）アクリ
ル酸エステル単量体よび／または芳香族ビニル系
単量体100〜40重量％およびこれらと共重合可能
な他のビニル単量体０〜60重％からなる単量体ま
たは単量体混合物99〜20重量部、好ましくは90〜
40重量部を公知の重合法、例えばゴム質重合体ラ
テツクスの存在下に前記した割合の単量体又は単
量体混合物と重合開始剤を連続的に供給して乳化
グラフト重合する方法などによつて得ることがで
きる。
この重合における単量体の組成比は（メタ）ア
クリル酸エステル単量体および／または芳香族ビ
ニル系単量体が全単量体に対し40〜100重量％と
する必要があり、好ましくは50〜100重量％であ
る。
（メタ）アクリル酸エステル単量体および／ま
たは芳香族ビニル系単量体の割合が40重量％未満
ではポリエーテルアミド共重合体との親和性が悪
く、成形品の外観を悪くするため好ましくない。
本発明において用いる(C)重合体の構成成分であ
る（メタ）アクリル酸エステル単量体としてはメ
タクリル酸メチル、メタクリル酸エチル、メタク
リル酸プロピルおよびアクリル酸メチルなどがあ
げられるが特にメタクリル酸メチルが好ましい。
芳香族ビニル系単量体としてはスチレン、α−
メチルスチレン、ビニルトルエン、ｐ−メチルス
チレン、ｐ−ｔ−ブチルスチレン、ｏ−エチルス
チレン、ｏ−ｐ−クロロスチレンなどがあげられ
るが特にスチレン、α−メチルスチレンが好まし
い。
またこれらと共重合可能な他のビニル単量体と
しては、アクリロニトリル、メタクリロニトリ
ル、エタクリロニトリルなどのシアン化ビニル系
単量体、アクリル酸、メタクリル酸、エタクリル
酸、マレイン酸、フマル酸などのα，β−不飽和
カルボン酸、マレイミド、Ｎ−フエニルマレイミ
ドなどのマレイミド系単量体が挙げられるが、特
に、アクリロニトリルが好ましい。
また(C)重合体は（メタ）アクリル酸エステル単
量体および／または芳香族ビニル系単量体100〜
40重量％およびこれらと共重合可能な他のビニル
単量体０〜60重量％の範囲から選ばれた単量体ま
たは単量体混合物を公知の重合法で得ることがで
きる。
この重合における単量体の組成比は（メタ）ア
クリル酸エステル単量体および／または芳香族ビ
ニル系単量体が使用する全単量体に対し40〜100
重量％好ましくは50〜100重量％である。（メタ）
アクリル酸エステル単量体および／または芳香族
ビニル系単量体の割合が40重量％未満ではポリエ
ーテルアミド共重合体との相溶性が悪く、十分な
衝撃強度が得られないばかりか成形品の外観が悪
いものとなり好ましくない。
かくして得られた(A)ポリエーテルアミド共重合
体５〜80重量部、特に好ましくは５〜60重量部と
(B)グラフト共重合体および／または(C)重合体65〜
20重量部、特に好ましく95〜40重量部からなる樹
脂組成物は後述するスルホン酸金属塩とともに混
合することができる。
(A)ポリエーテルアミド共重合体が５重量部未満
では樹脂組成物の帯電防止性が不足し、80重量部
を越えると樹脂組成物が柔軟になり、機械的特性
が劣るため好ましくない。
本発明の(D)の構成成分であるスルホン酸金属塩
は、核置換ベンゼンスルホン酸金属塩が好まし
く、その具体例として、たとえば下記に挙げるス
ルホン酸のLi、Na、Ca、Mg、Znの塩が挙げら
れる。
[Industrial Application Field] The present invention relates to a thermoplastic resin composition that has permanent antistatic properties and excellent mechanical properties such as impact resistance. [Prior Art] Synthetic polymeric materials are used in a wide range of fields due to their excellent properties. These materials are
In addition to the mechanical strength of the material, if it is given antistatic properties, its uses can be further expanded. In other words, it is possible to expand the application to copying machines and various dustproof parts where it is desired to prevent failures due to static electricity. As a method for improving the antistatic properties of synthetic polymer materials, a hydrophilic rubber-like polymer obtained by copolymerizing a conjugated diene or/and an acrylic ester with a vinyl monomer having an alkylene oxide group is added to a vinyl-based polymer. There are methods such as graft polymerization of monomers or vinylidene monomers (Japanese Patent Application Laid-open No. 55-36237), which have achieved practical antistatic properties. [Problems to be solved by the invention] However, since these antistatic resins use a special hydrophilic rubber-like polymer, the manufacturing method is complicated, and the mechanical properties of the resulting resins are poor. It has some disadvantages and is not completely satisfactory. As a result of intensive studies aimed at providing an antistatic resin that has permanent antistatic properties and excellent mechanical properties such as impact resistance, the present inventors found that
The above purpose can be achieved efficiently by mixing a graft copolymer obtained by graft polymerizing a specific vinyl monomer with a specific polyether amide and a rubbery polymer and/or a polymer of a specific vinyl monomer. The present invention was achieved by discovering that this can be achieved in a similar manner. [Means for Solving the Problems] That is, the present invention provides (meth)acrylic in the presence of (A) 5 to 80 parts by weight of a polyether amide copolymer and (B) 1 to 80 parts by weight of a rubbery polymer. Monomers or monomer mixtures consisting of 100 to 40% by weight of acid ester monomers and/or aromatic vinyl monomers and 0 to 60% by weight of other vinyl monomers copolymerizable with these 99 to 99% 20
Part by weight of the graft copolymer and/or
or (C) (meth)acrylic acid ester monomer and/or
or 100 to 40% by weight of aromatic vinyl monomers and 0 to 40% of other vinyl monomers copolymerizable with these
(D) 0 to 5 parts by weight of a metal salt of sulfonic acid is added to 100 parts by weight of a composition consisting of 95 to 20 parts by weight of a polymer obtained by polymerizing 60% by weight of a monomer or a monomer mixture. This is an antistatic resin composition. The present invention will be specifically explained below. The composition of the present invention comprises (A) a polyetheramide copolymer, (B) a graft copolymer and/or (C) a vinyl monomer polymer, and (D) a metal salt of sulfonic acid. The constituent components of the polyetheramide copolymer (A) in the present invention are essentially polyethylene glycol diamine, dicarboxylic acid, aliphatic diamine, and ε-
A copolymer whose main component is caprolactam. Polyethylene glycol diamine has a molecular weight
200 to 6000 polyethylene oxide groups as the main chain,
For example, a double-terminated diamine obtained by cyanoethylating polyethylene glycol and then hydrogenating it can be used. The molecular weight of this diamine determines the antistatic performance of the composition of the present invention, and at the same time influences the compatibility of the polyetheramide copolymer and the graft copolymer and the processability of the composition. That is, when the molecular weight is low, the compatibility and processability are good, but the antistatic performance is poor. Moreover, when the molecular weight becomes large, antistatic properties are good, but compatibility and dispersibility are poor, and processability is poor. The preferred molecular weight ranges from 200 to 600 based on polyethylene oxide groups. The amount of polyethylene glycol diamine added is 20 to 80% by weight based on the polyetheramide copolymer.
is preferred. If it is less than 20% by weight, the antistatic performance of the final composition will be insufficient. If it exceeds 80% by weight, the compatibility between the polyetheramide copolymer and the graft copolymer will be poor and delamination will occur, which is not preferable. Polyethylene glycol diamine is used as a dicarboxylic acid salt. As a dicarboxylic acid,
Adipic acid, sebacic acid, azelaic acid, benzenedicarboxylic acid, and the like can be used alone or as a mixture. In particular, it is preferable to use a mixture of aliphatic dicarboxylic acid and benzene dicarboxylic acid. Preferred fatty acid diamine is essentially hexamethylene diamine for economical reasons, but it is also possible to partially replace it with other aliphatic diamines. When the amount of benzene dicarboxylic acid added increases and the polymerization rate decreases, the aliphatic diamine can be added in an amount within the same molar amount as the polyethylene glycol diamine. Aliphatic diamines are
It is desirable to add it as a salt of dicarboxylic acid. The above mixture of polyethylene glycol diamine, dicarboxylic acid, and aliphatic diamine is heated to 220 to 270° C. in a nitrogen atmosphere in the coexistence of ε-caprolactam to give a polyetheramide copolymer. During this polymerization, phosphites, hindered phenols, and the like can be added as coloring inhibitors. The rubbery polymer that is a component of the graft copolymer (B) used in the present invention is preferably one having a glass transition temperature of 0°C or lower, and specifically, polybutadiene, polystyrene-butadiene, polyacrylonitrile- Diene rubbers such as butadiene, acrylic rubbers such as polyisoprene, polychloroprene, butyl polyacrylate, and rubbery polymers such as ethylene-propylene-diene monomer terpolymers can be used. Particularly preferred is butadiene or a butadiene copolymer. Examples of the (meth)acrylic acid ester monomer include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and methyl acrylate, with methyl methacrylate being particularly preferred. Styrene, α-
Examples include methylstyrene, vinyltoluene, o-ethylstyrene, op-dichlorostyrene, and styrene is particularly preferred. Other vinyl monomers that can be copolymerized with these include vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, and α,β-unsaturated monomers such as acrylic acid, methacrylic acid, maleic acid, and maleic anhydride. Examples include maleimide monomers such as carboxylic acid, maleimide, and N-phenylmaleimide, with acrylonitrile being particularly preferred.
In addition, (B) the graft copolymer contains 1 to 80 parts by weight of a rubbery polymer, preferably 10 to 60 parts by weight, and 100 to 40 parts by weight of a (meth)acrylic acid ester monomer and/or an aromatic vinyl monomer. % and other vinyl monomers copolymerizable with these 99-20 parts by weight, preferably 90-20 parts by weight of a monomer or monomer mixture consisting of 0-60% by weight of other vinyl monomers copolymerizable with these.
40 parts by weight was added by a known polymerization method, such as a method of emulsion graft polymerization by continuously supplying a monomer or a monomer mixture in the above ratio and a polymerization initiator in the presence of a rubbery polymer latex. You can get it. The composition ratio of the monomers in this polymerization must be such that the (meth)acrylic acid ester monomer and/or aromatic vinyl monomer is 40 to 100% by weight based on the total monomers, preferably 50 to 100% by weight based on the total monomers. ~100% by weight. If the proportion of the (meth)acrylic acid ester monomer and/or aromatic vinyl monomer is less than 40% by weight, it is undesirable because it has poor affinity with the polyetheramide copolymer and deteriorates the appearance of the molded product. . Examples of the (meth)acrylic acid ester monomer that is a component of the polymer (C) used in the present invention include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and methyl acrylate, but methyl methacrylate is particularly preferred. preferable. Styrene, α-
Examples include methylstyrene, vinyltoluene, p-methylstyrene, pt-butylstyrene, o-ethylstyrene, and op-chlorostyrene, with styrene and α-methylstyrene being particularly preferred. Other vinyl monomers that can be copolymerized with these include vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, and ethacrylonitrile, acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, and fumaric acid. Maleimide monomers such as α,β-unsaturated carboxylic acid, maleimide, and N-phenylmaleimide can be mentioned, and acrylonitrile is particularly preferred. In addition, the (C) polymer is a (meth)acrylic acid ester monomer and/or an aromatic vinyl monomer from 100 to
Monomers or monomer mixtures selected from the range of 40% by weight and 0 to 60% by weight of other vinyl monomers copolymerizable with these can be obtained by known polymerization methods. The monomer composition ratio in this polymerization is 40 to 100% of the total monomers used (meth)acrylic acid ester monomer and/or aromatic vinyl monomer.
The weight percent is preferably 50 to 100 weight percent. (meta)
If the proportion of the acrylic acid ester monomer and/or aromatic vinyl monomer is less than 40% by weight, the compatibility with the polyetheramide copolymer will be poor, and not only will sufficient impact strength not be obtained, but the molded product will deteriorate. This is not desirable as it gives a bad appearance. 5 to 80 parts by weight of the thus obtained polyetheramide copolymer (A), particularly preferably 5 to 60 parts by weight.
(B) Graft copolymer and/or (C) polymer 65~
The resin composition comprising 20 parts by weight, particularly preferably 95 to 40 parts by weight, can be mixed with the sulfonic acid metal salt described below. If the amount of the polyetheramide copolymer (A) is less than 5 parts by weight, the antistatic properties of the resin composition will be insufficient, and if it exceeds 80 parts by weight, the resin composition will become flexible and have poor mechanical properties, which is not preferable. The sulfonic acid metal salt which is the component (D) of the present invention is preferably a nuclear-substituted benzenesulfonic acid metal salt, and specific examples thereof include the following sulfonic acid salts of Li, Na, Ca, Mg, and Zn. can be mentioned.
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
本発明においてポリエーテルアミド共重合体と
優位量の（メタ）アクリル酸エステル単量体およ
び／または芳香族ビニル系単量体をグラフト重合
したグラフト共重合体あるいは単に重合した重合
体を併用した樹脂は永久帯電防止性を有し、かつ
高い機械的性質を発揮する。この現象はポリエー
テルアミド共重合体との親和性がないゴム質重合
体に（メタ）アクリル酸エステル単量体および／
または芳香族ビニル系単量体をグラフトさせるこ
とにより、ポリエーテルアミド共重合体とグラフ
ト共重合体との親和性が増大する効果と推察され
る。
〔実施例〕
本発明をさらに具体的に説明するために、以
下、実施例及び比較例を挙げて説明する。なお最
終的に得られた樹脂組成物は射出成形法によつて
成形されたのち、下記の試験法により諸物性を測
定した。
アイゾツト衝撃強度 ASTM D256−56A
引張強度 ASTM D638
曲げ弾性率 ASTM D793
体積固有抵抗値：2h×40〓円板を用い、室温23℃、
湿度50％RH雰囲気下で測定した、測定には東
亜電波工業(株)製の超絶縁抵抗計SM−10型を用
いた。
成形品の外観については試験片を目視で判定す
ることにより行ない、◎〜外観が極めて良好、〇
〜良好、×〜成形品の表面が損なわれ不良を判定
基準とした。
また、実施例中の部数および％は重量部および
重量％を示す。
参考例
(1) ポリエーテルアミド共重合体の調整
Ａ−１：数平均分子量4000のポリエチレングリ
コールにアクリロニトリルを反応させ、さら
に水素添加反応を行なうことにより、両末端
がアミノ基であるポリエチレングリコールジ
アミンを得た。これとテレフタル酸とを常法
により塩反応を行ない、ポリエチレングリコ
ールジアンモニウムテレフタレートの40％溶
液を得た。
濃縮罐に上記40％のポリエチレングリコー
ルジアンモニウムテフタレート水溶液を120
部、40％ヘキサメチレンジアンモニウアジペ
ート水溶液16部を投入し、常圧で内温が110
℃になるまで約２時間加熱し、80％濃度に濃
縮した。続いて重合罐に上記濃縮液を移行
し、重合罐内に窒素を流しながら加熱を開始
した。
内温が120℃になつた時点で、所定量のド
デシルベンゼンスルホン酸ナトリウムと、
１，３，５トリメチル．２，４，６−トリ
（３，５−ジ−ｔ−ブチル−ヒドロキシベン
ジル）ベンゼンを10部添加し、撹拌を開始し
て内温が245℃になるまで昇温した。245℃で
18時間加熱し重合を完結させた。
重合終了後罐内に窒素で圧力をかけ、重合
体を冷却ベルト上に吐出し、シート状にし
た。冷却固化したシートは、ペレツト状に細
断し、ポリエーテルアミド共重合体（Ａ−
１）を調整した。
Ａ−２：ポリエチレングリコールの数平均分子
量を1000に、ドデシルベンゼンスルホン酸ナ
トリウムムを未添加にした以外は（Ａ−１）
と全く同じ方法でポリエーテルアミド共重合
体（Ａ−２）を調製した。
(2) Ｂグラフト共重合体の調整
Ｂ−１：リブタジエンラテツクス（東レ(株)製、
粒子径0.36μ、ゲル含率＝90℃）30部（固形
分換算）の存在下でメタクリル酸メチル75
％、スチレン21％、アクリロニトリル４％か
らなる単量体混合物70部を乳化重合してグラ
フト共重合体（Ｂ−１）を調整した。
Ｂ−２：Ｂ−１で使用したポリブタジエンラテ
ツクス50部（固形分換算）の存在下でメタク
リル酸メチル85％スチレン15％とからなる単
量体混合物を乳化重合してグラフト共重合体
（Ｂ−２）を調整した。
Ｂ−３：Ｂ−１で使用したポリブタジエンラテ
ツクス40部（固形分換算）の存在下でスチレ
ン70％、アクリロニトリル30％からなる単量
体混合物60部を乳化重合してグラフト共重合
体（Ｂ−３）を調整した。
Ｂ−４：Ｂ−１で使用したポリブタジエンラテ
ツクス90部（固形分換算）の存在下でメタク
リル酸メチル40部円乳化重合してグラフト共
重合（Ｂ−４）を調整した。
Ｂ−５：Ｂ−１で使用したポリブタジエンラテ
ツクス30部（固形分換算）の存在下でスチレ
ン35％、Ｎ−フエニルマレイミド35％、アク
リロニトリル30％からなる単量体混合物70部
を乳化重合してグラフト共重合体（Ｂ−５）
を調整した。
(3) (C)共重合体の調整
Ｃ−１：メタクリル酸メチル75部、スチレン21
部、アリロニトリル４部を共重合して共重合
体（Ｃ−１）を調製した。
Ｃ−２：スチレン75部、アクリロニトリル23
部、アクリル酸２部を共重合して共重合体
（Ｃ−２）を調整した。
Ｃ−３：スチレン65部、Ｎ−フエニルマレイミ
ド10部、アクリロニトリル25部を共重合して
共重合体（Ｃ−３）を調整した。
Ｃ−４：スチレン35部、Ｎ−フエニルマレイミ
ド40部、アクリロニトリル25部を共重合して
共重合体（Ｃ−４）を調整した。
実施例 １
参考例で調整した(A)ポリエーテルアミドと(B)グ
ラフト共重合体および(C)共重合体を表１に示した
配合比で混合し、ベント付40mmφ押出機で、樹脂
温度220℃で溶融混練、押出を行なうことによつ
てペレツトを製造した。次いで射出成型機によ
り、シリンダー温度220℃、金型温度60℃で試験
片を成形し、各物性を測定した。
体積固有抵抗値は射出成形した厚さ２mmの円板
を用い、次の条件で測定した。
(1) 成形直後、洗剤ママレモン（ライオン油脂(株)
製）水溶液で洗浄し、続いて蒸留水で十分洗浄
してから表面の水分を取除いた後、５％RH、
23℃で24時間調湿して測定した。
(2) 成形後、50％RH、23℃中に200日間放置し
た後、洗剤ママレモン水溶液で洗浄し、続いて
蒸留水で十分洗浄してから表面の水分を取除い
た後、50％RT、23℃で24時間調湿して測定し
た。
測定結果を表１に示した。
比較例 １
参考例で調整した(A)ポリエーテルアミドと(B)グ
ラフト共重合体および(C)共重合体を表１に示した
配合比で混合し、実施例１と同様の方法で各物性
を測定した。また(A)ポリエーテルアミド、(B)グラ
フト共重合体および(C)共重合体単独の物性につい
ても同様に測定した。結果を表１に併せて示し
た。
In the present invention, a resin is used in combination with a graft copolymer obtained by graft polymerizing a polyether amide copolymer and a predominant amount of a (meth)acrylic acid ester monomer and/or an aromatic vinyl monomer, or a polymer obtained by simply polymerizing a polyether amide copolymer. has permanent antistatic properties and exhibits high mechanical properties. This phenomenon occurs when (meth)acrylic acid ester monomer and/or
Alternatively, it is presumed that the affinity between the polyetheramide copolymer and the graft copolymer is increased by grafting the aromatic vinyl monomer. [Examples] In order to explain the present invention more specifically, examples and comparative examples will be given below. The resin composition finally obtained was molded by injection molding, and then various physical properties were measured using the following test methods. Izotsu impact strength ASTM D256-56A Tensile strength ASTM D638 Flexural modulus ASTM D793 Volume resistivity: 2 h × 40〓 using a disk, room temperature 23℃,
The measurement was carried out in an atmosphere with a humidity of 50% RH, using a super insulation resistance meter SM-10 manufactured by Toa Denpa Kogyo Co., Ltd. The appearance of the molded product was determined by visual inspection of the test piece, and the criteria were ◎ - extremely good appearance, ○ - good, and × - poor appearance due to damage to the surface of the molded product. In addition, parts and percentages in the examples indicate parts by weight and percentages by weight. Reference Example (1) Preparation of polyetheramide copolymer A-1: Polyethylene glycol diamine having amino groups at both ends was prepared by reacting polyethylene glycol with a number average molecular weight of 4000 with acrylonitrile and further hydrogenating it. Obtained. This was subjected to a salt reaction with terephthalic acid in a conventional manner to obtain a 40% solution of polyethylene glycol diammonium terephthalate. Add 120% of the above 40% polyethylene glycol diammonium tephthalate aqueous solution to a concentration can.
and 16 parts of a 40% hexamethylene diammonium adipate aqueous solution, and the internal temperature reached 110 at normal pressure.
It was heated for about 2 hours until it reached ℃ and concentrated to 80% concentration. Subsequently, the concentrated solution was transferred to a polymerization can, and heating was started while flowing nitrogen into the polymerization can. When the internal temperature reaches 120℃, add a predetermined amount of sodium dodecylbenzenesulfonate,
1,3,5 trimethyl. 10 parts of 2,4,6-tri(3,5-di-t-butyl-hydroxybenzyl)benzene were added, stirring was started, and the temperature was raised until the internal temperature reached 245°C. at 245℃
Polymerization was completed by heating for 18 hours. After the polymerization was completed, pressure was applied in the can with nitrogen, and the polymer was discharged onto a cooling belt to form a sheet. The cooled and solidified sheet is shredded into pellets, and polyetheramide copolymer (A-
1) was adjusted. A-2: (A-1) except that the number average molecular weight of polyethylene glycol was set to 1000 and sodium dodecylbenzenesulfonate was not added.
A polyetheramide copolymer (A-2) was prepared in exactly the same manner. (2) Preparation of B-graft copolymer B-1: Ributadiene latex (manufactured by Toray Industries, Inc.,
75 methyl methacrylate in the presence of 30 parts (solid content equivalent) (particle size 0.36μ, gel content = 90℃)
%, 21% styrene, and 4% acrylonitrile were emulsion polymerized to prepare a graft copolymer (B-1). B-2: A monomer mixture consisting of 85% methyl methacrylate and 15% styrene was emulsion polymerized in the presence of 50 parts (solid content equivalent) of the polybutadiene latex used in B-1 to obtain a graft copolymer (B-1). -2) was adjusted. B-3: A graft copolymer (B -3) was adjusted. B-4: Graft copolymerization (B-4) was prepared by emulsion polymerization of 40 parts of methyl methacrylate in the presence of 90 parts (in terms of solid content) of the polybutadiene latex used in B-1. B-5: Emulsion polymerization of 70 parts of a monomer mixture consisting of 35% styrene, 35% N-phenylmaleimide, and 30% acrylonitrile in the presence of 30 parts (solid content equivalent) of the polybutadiene latex used in B-1. Graft copolymer (B-5)
adjusted. (3) (C) Preparation of copolymer C-1: 75 parts of methyl methacrylate, 21 parts of styrene
1 part and 4 parts of allylonitrile were copolymerized to prepare a copolymer (C-1). C-2: 75 parts of styrene, 23 parts of acrylonitrile
1 part and 2 parts of acrylic acid were copolymerized to prepare a copolymer (C-2). C-3: A copolymer (C-3) was prepared by copolymerizing 65 parts of styrene, 10 parts of N-phenylmaleimide, and 25 parts of acrylonitrile. C-4: A copolymer (C-4) was prepared by copolymerizing 35 parts of styrene, 40 parts of N-phenylmaleimide, and 25 parts of acrylonitrile. Example 1 (A) polyether amide, (B) graft copolymer, and (C) copolymer prepared in Reference Example were mixed at the compounding ratio shown in Table 1, and the resin temperature was adjusted using a vented 40 mmφ extruder. Pellets were produced by melt-kneading and extrusion at 220°C. Next, a test piece was molded using an injection molding machine at a cylinder temperature of 220°C and a mold temperature of 60°C, and each physical property was measured. The volume resistivity value was measured using an injection molded disk with a thickness of 2 mm under the following conditions. (1) Immediately after molding, use detergent Mama Lemon (Lion Yushi Co., Ltd.)
After cleaning with an aqueous solution (manufactured by Manufacturer Co., Ltd.) and thoroughly cleaning with distilled water to remove surface moisture,
The humidity was adjusted at 23°C for 24 hours and measured. (2) After molding, leave it at 50% RH and 23℃ for 200 days, wash it with Mama Lemon detergent solution, thoroughly wash it with distilled water, remove surface moisture, and then 50% RT. The humidity was controlled at 23°C for 24 hours and measured. The measurement results are shown in Table 1. Comparative Example 1 The (A) polyether amide, (B) graft copolymer and (C) copolymer prepared in Reference Example were mixed at the blending ratio shown in Table 1, and each was mixed in the same manner as in Example 1. Physical properties were measured. The physical properties of (A) polyether amide, (B) graft copolymer, and (C) copolymer alone were also measured in the same manner. The results are also shown in Table 1.
本発明の樹脂組成物は永久帯電防止性、耐衝撃
性等の機械的特性がともに優れたものである。
The resin composition of the present invention has excellent mechanical properties such as permanent antistatic properties and impact resistance.
Claims (1)
部と (B) ゴム質重合体１〜80重量部の存在下に（メ
タ）アクリル酸エステル単量体および／または
芳香族ビニル系単量体100〜40重量％およびこ
れらと共重合可能な他のビニル単量体０〜60重
量％からなる単量体または単量体混合物99〜20
重量部を重合させたグラフト共重合体および／
または (C) （メタ）アクリル酸エステル単量体および／
または芳香族ビニル単量体100〜40重量％およ
びこれらと共重合可能な他のビニル単量体０〜
60重量％からなる単量体または単量体混合物を
重合してなる重合体95〜20重量部とから成る組
成物100重量部に対して (D) スルホン酸の金属塩０〜５重量部を配合して
なる熱可塑性樹脂組成物。[Scope of Claims] 1 (A) 5 to 80 parts by weight of a polyetheramide copolymer and (B) 1 to 80 parts by weight of a rubbery polymer containing a (meth)acrylic acid ester monomer and/or Monomer or monomer mixture 99-20 consisting of 100-40% by weight of aromatic vinyl monomer and 0-60% by weight of other vinyl monomer copolymerizable with these monomers
Part by weight of the graft copolymer and/or
or (C) (meth)acrylic acid ester monomer and/or
or 100 to 40% by weight of aromatic vinyl monomers and 0 to 40% of other vinyl monomers copolymerizable with these
(D) 0 to 5 parts by weight of a metal salt of sulfonic acid per 100 parts by weight of a composition consisting of 95 to 20 parts by weight of a polymer obtained by polymerizing 60% by weight of a monomer or a monomer mixture; A thermoplastic resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15006985A JPS6211759A (en) | 1985-07-10 | 1985-07-10 | Thermoplastic resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15006985A JPS6211759A (en) | 1985-07-10 | 1985-07-10 | Thermoplastic resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6211759A JPS6211759A (en) | 1987-01-20 |
| JPS6353226B2 true JPS6353226B2 (en) | 1988-10-21 |
Family
ID=15488838
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15006985A Granted JPS6211759A (en) | 1985-07-10 | 1985-07-10 | Thermoplastic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6211759A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6381158A (en) * | 1986-09-24 | 1988-04-12 | Japan Synthetic Rubber Co Ltd | Thermoplastic elastomer composition |
| US5395870A (en) * | 1988-12-28 | 1995-03-07 | Asahi Kasei Kogyo Kabushiki Kaisha | Vinyl resin composition |
| JPH02283748A (en) * | 1989-04-25 | 1990-11-21 | Asahi Chem Ind Co Ltd | Thermoplastic resin composition |
| JPH032251A (en) * | 1989-05-31 | 1991-01-08 | Asahi Chem Ind Co Ltd | Permanently antistatic impact-resistant resin composition |
| JPH0339349A (en) * | 1989-07-06 | 1991-02-20 | Asahi Chem Ind Co Ltd | Thermoplastic resin composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5539246A (en) * | 1978-09-11 | 1980-03-19 | Shibaura Eng Works Ltd | Mounting structure of garbage receiving vessel in garbage disposal machine |
| JPS6023435A (en) * | 1983-07-19 | 1985-02-06 | Toray Ind Inc | Antistatic resin composition |
| JPS60170646A (en) * | 1984-02-16 | 1985-09-04 | Daicel Chem Ind Ltd | Resin composition |
-
1985
- 1985-07-10 JP JP15006985A patent/JPS6211759A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5539246A (en) * | 1978-09-11 | 1980-03-19 | Shibaura Eng Works Ltd | Mounting structure of garbage receiving vessel in garbage disposal machine |
| JPS6023435A (en) * | 1983-07-19 | 1985-02-06 | Toray Ind Inc | Antistatic resin composition |
| JPS60170646A (en) * | 1984-02-16 | 1985-09-04 | Daicel Chem Ind Ltd | Resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6211759A (en) | 1987-01-20 |
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| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |