JPH0425551A - Thermoplastic resin composition and molded article - Google Patents
Thermoplastic resin composition and molded articleInfo
- Publication number
- JPH0425551A JPH0425551A JP13080890A JP13080890A JPH0425551A JP H0425551 A JPH0425551 A JP H0425551A JP 13080890 A JP13080890 A JP 13080890A JP 13080890 A JP13080890 A JP 13080890A JP H0425551 A JPH0425551 A JP H0425551A
- Authority
- JP
- Japan
- Prior art keywords
- thermoplastic resin
- resin
- component
- resin composition
- polymer
- 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 31
- 239000011342 resin composition Substances 0.000 title claims description 16
- 229920005989 resin Polymers 0.000 claims abstract description 31
- 239000011347 resin Substances 0.000 claims abstract description 31
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 229920001971 elastomer Polymers 0.000 claims description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 230000000379 polymerizing effect Effects 0.000 claims description 9
- 238000004898 kneading Methods 0.000 claims description 6
- 150000008360 acrylonitriles Chemical class 0.000 claims description 5
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 230000002794 monomerizing effect Effects 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 abstract description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 abstract description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 abstract description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 abstract 1
- 125000005250 alkyl acrylate group Chemical group 0.000 abstract 1
- 229920000058 polyacrylate Polymers 0.000 abstract 1
- 238000000034 method Methods 0.000 description 14
- 239000004816 latex Substances 0.000 description 9
- 229920000126 latex Polymers 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- -1 aromatic vinyl compound Chemical class 0.000 description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- 239000011231 conductive filler Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 229920000578 graft copolymer Polymers 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 229920003244 diene elastomer Polymers 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- FYBFGAFWCBMEDG-UHFFFAOYSA-N 1-[3,5-di(prop-2-enoyl)-1,3,5-triazinan-1-yl]prop-2-en-1-one Chemical compound C=CC(=O)N1CN(C(=O)C=C)CN(C(=O)C=C)C1 FYBFGAFWCBMEDG-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 101100208721 Mus musculus Usp5 gene Proteins 0.000 description 1
- 206010040844 Skin exfoliation Diseases 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000000217 alkyl 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
- 235000011126 aluminium potassium sulphate Nutrition 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229940050271 potassium alum Drugs 0.000 description 1
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、電磁波シールド性をもつ熱可塑性樹脂組成物
及び成形品に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a thermoplastic resin composition and a molded article having electromagnetic shielding properties.
（従来の技術）
電子機器の急速な発展にともなって、マイクロコンピュ
ータ、ワードプロセンサーなどのディジタル寛子機器が
普及し、これらに使用されているＩＣやＬＳＩなどから
発生する電磁波が周辺機器に影響を与える電磁波障害の
問題が起っている。(Prior art) With the rapid development of electronic devices, digital devices such as microcomputers and word processor sensors have become widespread, and the electromagnetic waves generated from the ICs and LSIs used in these devices have an impact on peripheral devices. The problem of electromagnetic interference is occurring.
しかも、装置の小型化、量産化が進み、プラスチック成
形品が、各種電子機器の筐体として使用されているため
、プラスチックに対する効果的な電磁波シールド技術が
要求されている。Moreover, as devices become smaller and more mass-produced, plastic molded products are being used as housings for various electronic devices, so effective electromagnetic shielding technology for plastics is required.
プラスチック成形品をシールドする方法とじては、プラ
スチックの表面に導電層を形成する方法や導電性フィラ
ーを練り込む方法が用いられている。ＩＬＬば、亜鉛溶
射やメツキによる金属薄膜コーティングや導電性塗料塗
布があげられる。また。Methods for shielding plastic molded products include forming a conductive layer on the surface of the plastic and incorporating conductive filler. Examples of ILL include metal thin film coating by zinc spraying or plating, and conductive paint coating. Also.
導電フィラーとしては、ステンレス繊維、黄銅繊Ｍ、ｍ
稙ｉ、アルミフレーク等があげられ、プラスチック中に
これらを練り込むことにより、シールド性を与えること
ができる（「工業材料」第３０巻第１０号第１７〜２４
頁９日刊工業新聞社１９８２年発行参照）。As conductive filler, stainless fiber, brass fiber M, m
By kneading these into plastic, it is possible to impart shielding properties ("Industrial Materials" Vol. 30, No. 10, No. 17-24).
(See page 9, published by Nikkan Kogyo Shimbun, 1982).
（発明が解決しようとする課題）
プラスチックの表面に導電層を形成する方法では、いず
れも、成形品を成形した後、各穐の表面処理を行なって
から、更に二次加工するために。(Problems to be Solved by the Invention) In all methods of forming a conductive layer on the surface of plastic, after the molded product is molded, each piece is subjected to surface treatment, and then further secondary processing is performed.
生産性が劣る。二次加工のための設備が必要であるなど
の欠点がある。また、長期間にわたって使用する際に９
表面の導電層がはく離するおそれがあるために耐久性、
信頼性に乏しいという欠点がある。Productivity is poor. There are drawbacks such as the need for equipment for secondary processing. Also, when using it for a long time,
Durability due to the risk of peeling off of the conductive layer on the surface.
The drawback is that it is unreliable.
一方、プラスチック中に導電性フィラーを混入させる方
法においては、導電性フィラーを多量に混入させないと
十分なシールド効果が得られない。On the other hand, in the method of mixing conductive filler into plastic, a sufficient shielding effect cannot be obtained unless a large amount of conductive filler is mixed.
導電性フィラーを多量に混入させると機械的特性が著し
く低下する等の弱点を有する。また、銅繊維は表面が酸
化され易いため、そのまま練り込んでも十分なシールド
効果が得られ難く、防錆処理を施す等の工夫が必要であ
る。If a large amount of conductive filler is mixed in, it has weaknesses such as a significant decrease in mechanical properties. Further, since the surface of copper fibers is easily oxidized, it is difficult to obtain a sufficient shielding effect even if the copper fibers are kneaded as is, and measures such as applying rust prevention treatment are required.
本発明はこのような問題点を解決するものである。The present invention solves these problems.
（課題を解決するための手段）
本発明は、（Ａ）ゴム状重合体に芳香族ビニル化合物、
シアン化ビニル化合物及びメタクリル酸エステルのうち
、少なくとも一種の単量体をグラフト重合させて得られ
る熱可塑性樹脂並びに（Ｂ）直径が１〜１００μｍ樹脂
被覆銅線を該被覆樹脂の軟化温度以上の温度で混練して
得られる熱可塑性樹脂を
組成物及び該熱可塑性樹脂組成物を成形して得られる成
形品に関する。(Means for Solving the Problems) The present invention provides (A) an aromatic vinyl compound in a rubbery polymer;
A thermoplastic resin obtained by graft polymerizing at least one monomer among vinyl cyanide compounds and methacrylic acid esters and (B) a resin-coated copper wire with a diameter of 1 to 100 μm at a temperature higher than the softening temperature of the coated resin. The present invention relates to a composition obtained by kneading a thermoplastic resin and a molded article obtained by molding the thermoplastic resin composition.
１ず１本発明の（Ａ）成分圧ついて説明する。First, component pressure (A) of the present invention will be explained.
本発明の人）成分は、アクリル酸アルキルエステル重合
体、ポリブタジェン等のジエン系ゴムなどのゴム状重合
体に、芳香族ビニル化合物、シアン化ビニル化合物及び
メタクリル酸エステルのうち。The components of the present invention include rubber-like polymers such as acrylic acid alkyl ester polymers, diene rubbers such as polybutadiene, aromatic vinyl compounds, vinyl cyanide compounds, and methacrylic esters.
少なくとも一種の単量体音グラフト重合させて得られる
。上記ゴム状重合体としてアクリル酸アルキルエステル
重合体を用いる方が好ましい。該アクリル酸アルキルエ
ステル重合体の製造に使用される単量体としては、アク
リル酸ｎ−ブチルが特に適しているが、アクリル酸エチ
ル、アクリル酸プロピル、アクリル酸ヘキシル、アクリ
ル酸２エチルヘキシル等の炭素数１−１３個のアルキル
基を有するものが単独でまたは組み合わせて使用できる
。また、ゴム状重合体としてのアクリル酸アルキルエス
テル重合は、交叉結合した重合体であることが必要であ
り、交叉結合していないものを使用すると、耐衝撃性の
低い成形品しか得られない。このアクリル酸アルキルエ
ステル重合体に交叉結合を導入するには、有機過酸化物
で架橋する方法及び多官能性単量体を共重合させる方法
がめる。多官能性単量体とは、アクリル酸アルキルエス
テルと共重合可能な２個以上の官能基を有する七ツマ−
であり、これを共重合させることにより、ゴム弾性の優
れたアクリル系ゴム状重合体が得られるー。この多官能
性単量体としてｔま、トリアリルイソシアヌレート、ト
リアリルシアヌＬ／ −トウジビニルベンゼン、トリア
クリルホルマール。Obtained by graft polymerizing at least one monomer. It is preferable to use an acrylic acid alkyl ester polymer as the rubbery polymer. As the monomer used for producing the acrylic acid alkyl ester polymer, n-butyl acrylate is particularly suitable, but carbonaceous compounds such as ethyl acrylate, propyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, etc. Those having 1 to 13 alkyl groups can be used alone or in combination. Furthermore, when polymerizing an acrylic acid alkyl ester as a rubbery polymer, it is necessary to use a cross-linked polymer, and if a non-cross-linked polymer is used, only a molded product with low impact resistance will be obtained. In order to introduce crosslinking into this acrylic acid alkyl ester polymer, a method of crosslinking with an organic peroxide and a method of copolymerizing a polyfunctional monomer are used. A polyfunctional monomer is a monomer having two or more functional groups that can be copolymerized with an acrylic acid alkyl ester.
By copolymerizing this, an acrylic rubber-like polymer with excellent rubber elasticity can be obtained. The polyfunctional monomers include triallyl isocyanurate, triallyl cyanide L/-vinylbenzene, and triacryl formal.
エチレングリコールジメタクリレート等の多価ビニル化
合物や多価アクリル化合物が有効であるが。Polyvalent vinyl compounds and polyvalent acrylic compounds such as ethylene glycol dimethacrylate are effective.
この中でも特に、トリアリルイソシアヌレ−トドトリア
リルシアヌレートが好ましい。この多官能性単量体の添
加量は全単量体に対して０．１〜１０重量％が好１しく
、特に好ましくは、０．５〜５重量％が用いられる。０
．１重量％未満では、十分な架橋度が得られＫ＜＜、１
０重量％を超えると架橋度が過剰で、いずれの場合も十
分な耐衝撃性を付与しにくくなる。着た。上記アクリル
酸アルキルエステル重合体は、アクリル酸アルキルエス
テル成分が５０重量％以上含まれていれば、スチレン、
アクリロニトリル等の他の成分を含んでいてもよく、マ
た。ポリブタジェン等のジエン系ゴム存在下に、先に示
したようなアクリル酸エステル類をグラフト重合したも
のも好ましいゴム状重合体として使用できる。Among these, triallyl isocyanurate and triallyl cyanurate are particularly preferred. The amount of the polyfunctional monomer added is preferably 0.1 to 10% by weight, particularly preferably 0.5 to 5% by weight based on the total monomers. 0
．． If it is less than 1% by weight, a sufficient degree of crosslinking is obtained and K<<, 1
If it exceeds 0% by weight, the degree of crosslinking will be excessive and in either case it will be difficult to impart sufficient impact resistance. worn. If the acrylic acid alkyl ester polymer contains 50% by weight or more of the acrylic acid alkyl ester component, styrene,
It may also contain other ingredients such as acrylonitrile. A preferred rubber-like polymer may also be one obtained by graft polymerizing acrylic acid esters as shown above in the presence of a diene rubber such as polybutadiene.
上記ゴム状重合体にグラフト重合させる単量体としては
、芳香族ビニル化合物として、スチレン。As the monomer to be graft-polymerized to the above-mentioned rubbery polymer, styrene is used as an aromatic vinyl compound.
α−メチルスチレン、ビニルトルエン、クロロスチレン
、ｔ−ブチルスチレン等があり、シアン化ビニル化合物
として、アクリロニトリル、メタクリロニトリル等があ
り、メタクリル酸エステルとして、メチルメタクリレー
ト、エチルメタクリレ−４，ｎ−ブチルメタクリレート
、ｔ−ブチルメタクリレート、２−エチルへキシルメタ
クリレート等がめる。特に、芳香族ビニル化合物として
スチレン、シアン化ビニル化合物としてアクリロニトリ
ルが有効である。There are α-methylstyrene, vinyltoluene, chlorostyrene, t-butylstyrene, etc., vinyl cyanide compounds include acrylonitrile, methacrylonitrile, etc., and methacrylic acid esters include methyl methacrylate, ethyl methacrylate-4, n- Butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, etc. In particular, styrene is effective as the aromatic vinyl compound, and acrylonitrile is effective as the vinyl cyanide compound.
本発明においては９以上の単量体の少なくとも一種がグ
ラフト成分として使用される。グラフトさせる単量体の
組成としては、芳香族ビニル化合物１００重量％以下、
好ましくは６０〜８０重量％、シアン化ビニル化合物が
好ましくけ４０重量％以下、特に好ましくけ２０〜４０
重量％の範囲が挙げられる。また、メタクリル酸エステ
ルは１００重量％以下の範囲で、他の単量体と共に全体
が１００重ｆ％になるように１更用されるのが好ましい
。In the present invention, at least one of nine or more monomers is used as a graft component. The composition of the monomer to be grafted is 100% by weight or less of an aromatic vinyl compound,
Preferably 60 to 80% by weight, preferably vinyl cyanide compounds, but not more than 40% by weight, particularly preferably 20 to 40% by weight.
Weight % ranges may be mentioned. The methacrylic acid ester is preferably used in an amount of 100% by weight or less together with other monomers so that the total amount is 100% by weight.
（Ａ）成分の熱可塑性樹脂を製造するとき、上記ゴム状
重合体は１５〜６０重量％使用されるのが好ましく、特
に２０〜６０重量％使用されるのが好ましい。１５重量
％未満では十分な耐衝撃性が得られず、６０重量％をを
超えると、剛性ｆ流動性が低下する傾向にある。When producing the thermoplastic resin of component (A), the rubbery polymer is preferably used in an amount of 15 to 60% by weight, particularly preferably 20 to 60% by weight. If it is less than 15% by weight, sufficient impact resistance cannot be obtained, and if it exceeds 60% by weight, stiffness and fluidity tend to decrease.
上記のゴム状重合体としてのアクリル酸アルキルエステ
ル重合体を製造するための重合法および（Ａ）成分の熱
可塑性樹脂を製造するためのグラフト重合法としては特
に制限はなく、公知の方法が適用できる。例えば、乳化
重合によ勺、ゴム状重合体としてのアクリル酸アルキル
エステル重合体を製造することができ、得られるゴム状
重合体のラテックスにさらにグラフトさせる重合体を添
加して、乳化重合により、（Ａ）成分の熱可塑性樹脂を
製造することができる。この場合１重合触媒としては、
過硫酸カリウム、過硫酸アンモニウム、過酸化水素など
の通常の水溶性重合開始剤、あるいはキュメンハイドロ
パーオキサイドとロンガリットの併用などのレドックス
系を形成する重合触媒を用いることができる。乳化重合
の乳化剤としては。There are no particular restrictions on the polymerization method for producing the acrylic acid alkyl ester polymer as the rubbery polymer and the graft polymerization method for producing the thermoplastic resin as component (A), and known methods can be applied. can. For example, an acrylic acid alkyl ester polymer as a rubbery polymer can be produced by emulsion polymerization, and a polymer to be grafted is further added to the resulting rubbery polymer latex, and then by emulsion polymerization, The thermoplastic resin of component (A) can be produced. In this case, as a single polymerization catalyst,
Common water-soluble polymerization initiators such as potassium persulfate, ammonium persulfate, and hydrogen peroxide, or polymerization catalysts that form a redox system such as a combination of cumene hydroperoxide and Rongalit can be used. As an emulsifier for emulsion polymerization.
アニオン系界面活性剤、カチオン系界面活性剤。Anionic surfactants, cationic surfactants.
非イオン系界面活性剤のいずれを用いても良い。Any nonionic surfactant may be used.
本発明における（Ａ）成分の熱可塑性樹脂としては。The thermoplastic resin as component (A) in the present invention includes:
上記方法により、ゴム状重合体存在下洗単量体を重合し
て得られる比較的高いゴム含有量のグラフト重合体と、
ゴム状重合体の非存在下に、前記に例示した単量体のみ
を重合して得られる重合体との組成物、いわゆるグラフ
トルブレンド法によるグラフト重合体組成物も包含され
る。この場合。A graft polymer with a relatively high rubber content obtained by polymerizing a washed monomer in the presence of a rubbery polymer by the above method,
Also included are compositions with polymers obtained by polymerizing only the monomers exemplified above in the absence of a rubbery polymer, so-called graft polymer compositions produced by the so-called graftle blend method. in this case.
高いゴム含有量のグラフト重合体中のゴム成分の量は、
−概には言えないが、２５重重量板上であるのが好まし
い。The amount of rubber component in the high rubber content graft polymer is
-Although it cannot be said generally, it is preferable to use a 25-weight board.
次に１本発明の（Ｂ）成分について詳述する。Next, component (B) of the present invention will be explained in detail.
本発明に用いられる（Ｂｌ成分の樹脂被覆銅線としては
、直径が１〜１００μｍの極細銅線を厚さ１〜ｌＯμｍ
の樹脂でコーティングしたものである。As the resin-coated copper wire of the Bl component used in the present invention, an ultrafine copper wire with a diameter of 1 to 100 μm and a thickness of 1 to 10 μm is used.
It is coated with resin.
被覆樹脂としては、ウレタン樹脂、ポリアミド樹脂、ポ
リビニルホルマール、エポキシ樹脂、ポリエチレンテレ
フタレート樹Ｑｌｔ、 シリコーン樹脂等が挙げられる
。中でもいわゆるエナメル線と称されるものが好ましく
、被覆樹脂としては（Ａ）成分との混練におけるマツチ
ングが良好なウレタン樹脂が特に好ましい。銅線の直径
が１μｍ未満では強度に難点があり、一方１００μｍを
超えると十分なンールド効果が得られない傾向がある。Examples of the coating resin include urethane resin, polyamide resin, polyvinyl formal, epoxy resin, polyethylene terephthalate resin, silicone resin, and the like. Among these, so-called enameled wires are preferred, and as the coating resin, urethane resins that have good matching when kneaded with component (A) are particularly preferred. If the diameter of the copper wire is less than 1 μm, there is a problem in its strength, while if it exceeds 100 μm, there is a tendency that a sufficient rolled effect cannot be obtained.
銅線の直径としては１０〜５０μｍが特に好ましい。混
練する鋼線の好ましい長さは混線法によって異なり、特
に制限はない。但し、シールド特性の面からは、成形品
中で長い方が好ましい。The diameter of the copper wire is particularly preferably 10 to 50 μm. The preferred length of the steel wire to be kneaded varies depending on the wire crossing method and is not particularly limited. However, from the viewpoint of shielding properties, the longer the length in the molded product, the better.
本発明において（Ａ）成分の熱可塑性樹脂と（Ｂ）成分
の樹脂被覆銅線の混合する比率は、 （Ａ）／（Ｂ）が
容量比で９５１５〜５０１５０の範囲が好ましく、特に
９０／１０〜７０／３０の範囲が好ましい。In the present invention, the mixing ratio of the thermoplastic resin as the component (A) and the resin-coated copper wire as the component (B) is preferably such that (A)/(B) is in the range of 9515 to 50150 in terms of capacity ratio, particularly 90/10. A range of 70/30 is preferred.
（Ｂｌ成分の比率が５容量チ未満では、シールド効果が
不十分で、５０容量チを超えると、熱可塑性樹脂との均
一混線が困難となり、その結果、耐衝撃性が低下する傾
向にある。(When the ratio of the Bl component is less than 5% by volume, the shielding effect is insufficient, and when it exceeds 50% by volume, uniform crosstalk with the thermoplastic resin becomes difficult, and as a result, impact resistance tends to decrease.
本発明において（Ａ）成分と（Ｂ）成分の混合は、一般
に使われているタンブラ−、ヘンシェルミキサーなどで
混合後、押出機などで混練する方法により行うことがで
きる。また、サイドフィード型押出機を用いて、樹脂被
覆を線をサイドフィードして。In the present invention, components (A) and (B) can be mixed by a method in which they are mixed in a commonly used tumbler, Henschel mixer, etc., and then kneaded in an extruder, etc. Alternatively, use a side-feed extruder to side-feed the resin coating wire.
混線、ペレタイズすることもできる。ＬＬ二−タ、ロー
ル、バンバリーミキサ−などで混練する方法も用いるこ
とができる。いずれにしても、 （Ａｌ成分と（Ｂ）成
分の混線は、（Ｂ）成分の被覆樹脂の軟化温度以上の温
度で混練することが必要である。軟化温度未満では、充
分な電磁波シールド性が付与できない。Can also be mixed and pelletized. A method of kneading with an LL kneader, roll, Banbury mixer, etc. can also be used. In any case, (to mix the Al component and the (B) component, it is necessary to knead at a temperature higher than the softening temperature of the coating resin of the (B) component. Below the softening temperature, sufficient electromagnetic shielding properties are not achieved. Cannot be granted.
以上のようにして得られる本発明に係る熱可塑性樹脂組
成物には、顔料、可塑剤、各攬安定剤等の公知の添加剤
を含有させることができる。The thermoplastic resin composition according to the present invention obtained as described above may contain known additives such as pigments, plasticizers, and various stabilizers.
本発明の熱可塑性樹脂組成物は、圧縮成形法。The thermoplastic resin composition of the present invention can be produced by compression molding.
射出成形法など公知の成形法例よシ成形され９本発明の
成形品とすることができる。得られる成形品は、優れた
電磁波シールド効果を有すると共に耐衝撃性等の機械的
特性にも優れる。The molded article of the present invention can be obtained by molding using a known molding method such as injection molding. The molded product obtained has an excellent electromagnetic shielding effect and also has excellent mechanical properties such as impact resistance.
（実施例）
次に本発明の実施例を示す。以下、「部」は特にことわ
らない限り１重量部を意味する。(Example) Next, an example of the present invention will be shown. Hereinafter, "part" means 1 part by weight unless otherwise specified.
実施例１
（熱可塑性樹脂の製造）
反応器に、ポリブタジェンラテックス（住友ノーガタッ
ク■製、５Ｎ−８００Ｔ、平均粒径０．３５μｍ、ゲル
含有率８０％）３００部（固形分換算）及び均一に溶解
した下記の成分■
を仕込んで混合攪拌した後、トリアリルイソシアヌレー
ト１４部をアクリル酸ブチル７００部に溶解して添加し
、窒素置換後、昇温した。６０〜６５℃で約４時間重合
させた後、冷却して重合を停止させた。Example 1 (Manufacture of thermoplastic resin) 300 parts (solid content equivalent) of polybutadiene latex (manufactured by Sumitomo Naugatac ■, 5N-800T, average particle size 0.35 μm, gel content 80%) and After uniformly dissolving the following component (1) and mixing and stirring, 14 parts of triallylisocyanurate dissolved in 700 parts of butyl acrylate was added, and after purging with nitrogen, the temperature was raised. After polymerizing at 60-65° C. for about 4 hours, the polymerization was stopped by cooling.
一方、均一に溶解した下記成分■及び■を反応器に仕込
み、均一に混合した後、上記の方法で得られたゴム重合
体ラテックス３００部（残アクリル酸ブチル単量体を含
む固形分換算）を添加し。On the other hand, uniformly dissolved components (1) and (2) below were charged into a reactor and mixed uniformly, followed by 300 parts of rubber polymer latex obtained by the above method (calculated as solid content including residual butyl acrylate monomer). Add.
窒素置換しなから更に３０分攪拌混合した。その後、６
５℃で約６時間重合し９重合率が９０慢以上であること
を確認した後、更に９０℃で２時間重合し、樹脂ラテッ
クスを得た。この樹脂ラテックスをカリミョウバン水溶
液中で塩析し、脱水乾燥して樹脂粉末を得た。The mixture was stirred and mixed for an additional 30 minutes without replacing the mixture with nitrogen. After that, 6
Polymerization was carried out at 5°C for about 6 hours, and after confirming that the polymerization rate was 90% or higher, polymerization was further carried out at 90°C for 2 hours to obtain a resin latex. This resin latex was salted out in an aqueous potassium alum solution and dehydrated and dried to obtain a resin powder.
（熱可塑性樹脂組成物及び成形品の製造）上記樹脂粉末
４０部（８５容量部）及び直径が３０μｍのエナメル線
（日立電線■製、ＶＥＷ−Ｌ軟化温度１８０℃のポリウ
レタンで被覆、被覆厚２μｍ）６０部（１５容量部）を
***プラベンダー社製、プラスチコーダＰＬＤ６５１型
（ミキサーＷ５０型）を用いて、各糧温度で約３分間か
けて３ Ｑ ｒｐｍで混練した。得られた組成物から。(Production of thermoplastic resin composition and molded product) 40 parts (85 parts by volume) of the above resin powder and an enameled wire with a diameter of 30 μm (manufactured by Hitachi Cable ■, VEW-L) Covered with polyurethane with a softening temperature of 180°C, coating thickness 2 μm ) 60 parts (15 parts by volume) were kneaded at 3 Q rpm for about 3 minutes at each grain temperature using a Plasticorder model PLD651 (mixer model W50) manufactured by Plabender, West Germany. From the resulting composition.
１９０℃／３分で１５０■角２ａ＋厚の樹脂板を圧縮成
形した。タケダ理研工業■製ディジタルマルチメータＴ
Ｒ６８４１型を用いて、この樹脂板の体積抵抗を室温下
で測定した。結果を図１図に示す。また、１９０℃で混
練したものを成形した樹脂板のアイゾツト衝撃強さ（ｋ
ｇ・ｃｍ ／ ｃｍ、ノツチ付、ＡＳＴＭ−Ｄ−２５６
による。以下同様）を測定したところ１３．３ｋｇｃｍ
／■と良好な値が得られた。A resin plate of 150 square square 2a + thickness was compression molded at 190° C. for 3 minutes. Takeda Riken Kogyo Digital Multimeter T
The volume resistance of this resin plate was measured at room temperature using a model R6841. The results are shown in Figure 1. In addition, the isot impact strength (k
g・cm/cm, with notch, ASTM-D-256
by. The same applies below) was measured and it was 13.3 kgcm.
A good value of /■ was obtained.
実施例２
実施例１で得られた樹脂粉末５０部と同様のエナメル線
５０部を３０ａａｎφの２軸押比機を用いて。Example 2 50 parts of the resin powder obtained in Example 1 and 50 parts of the same enameled wire were prepared using a 30 aanφ twin-screw presser.
２３０℃の条件下でエナメルａをサイドフィードしなが
ら溶融混練してベレント化した。樹脂成分とエナメル線
の容量比は８９．５／１０．５となる。Enamel a was melt-kneaded under conditions of 230° C. while side-feeding to form a belent. The capacity ratio of the resin component to the enameled wire is 89.5/10.5.
射出成形機を用いて２４０℃の条件下で５０×１００１
００Ｘ３（の大きさの試験片を作表し１％性試験を行っ
た。シールド効果はタヶダ理研工業■製のＴＲ４１７２
）ランキングジェネレータ付スペクトルアナライザーを
用いて測定した。５００ＭＨｚにおけるシールド効果は
４３ ｄＢであった。50×1001 at 240℃ using an injection molding machine
A test piece with a size of 00X3 was prepared and a 1% test was conducted.
) Measured using a spectrum analyzer with a ranking generator. The shielding effect at 500MHz was 43 dB.
また、実施例１と同様にしてアイゾツト衝撃強さ（ノン
チ付）を測定したところ１４．７ ｋｇｃｍ／ ａｍと
良好な値を示した。Further, when the Izot impact strength (with a non-touch) was measured in the same manner as in Example 1, it showed a good value of 14.7 kgcm/am.
実施例３
（アクリル酸ブチルゴム状重合体の製造）反応器に各々
均一に溶解させた下記成分Ｉ及び成分■を仕込み、攪拌
しながら窒素ガスで置換した後、６０℃に昇温し、４時
間反応させた。その後、８０℃で更に３時間反応させて
アクリル酸ブチルゴム状重合体のラテックスを得た。Example 3 (Production of butyl acrylate rubber-like polymer) Component I and component ① below, each uniformly dissolved, were charged into a reactor, and after purging with nitrogen gas while stirring, the temperature was raised to 60°C and heated for 4 hours. Made it react. Thereafter, the reaction was further carried out at 80° C. for 3 hours to obtain a latex of butyl acrylate rubber-like polymer.
（熱可塑性樹脂の製造）
ＴＫホモミキサー（特殊機化工業■製）を備えた容器に
均一に溶解した成分■と成分■を仕込み。(Manufacture of thermoplastic resin) In a container equipped with a TK homo mixer (manufactured by Tokushu Kika Kogyo ■), uniformly dissolved components ■ and ■ are charged.
窒素置換後、４ｍ／秒の攪拌速度で１０分間ホモミキシ
ングした後、前記アクリル酸ブチルゴム状重合体のラテ
ックス３００部（固形分換算）を添加してホモミキシン
グを３０分間行った。After nitrogen substitution, homomixing was performed for 10 minutes at a stirring speed of 4 m/sec, and then 300 parts (in terms of solid content) of the latex of the butyl acrylate rubber polymer was added and homomixing was performed for 30 minutes.
その後、窒素置換した反応器に移し、７０℃で１０時間
更に９０℃で４時間重合を行い１重合体ラテックスを得
た。このラテックスをＨｅマグネシウムを溶解した熱水
中で塩析し、脱水乾燥して樹脂粉末を得た。Thereafter, the mixture was transferred to a reactor purged with nitrogen and polymerized at 70°C for 10 hours, and further at 90°C for 4 hours to obtain a monopolymer latex. This latex was salted out in hot water in which magnesium He was dissolved, and then dehydrated and dried to obtain a resin powder.
（熱可塑性樹脂組成物及び成形品の製造）上記樹脂粉末
３５部と、５０μｍ径エナメル線（ポリウレタン被覆銅
線）６５部を***ブラベンダー社製プラスチコーダＰＬ
Ｄ６５１型を用いて２００℃、３０ｒｐｍにて溶融混練
した。得られた組成物を用いて１９０℃／３分で１５０
聰角２鴫厚の樹脂板を圧縮成形した。実施例２と同様に
してシールド効果を測定したところ、４０ｄＢと良好な
値を示し念。また、実施例１と同様にしてアイゾツト衝
撃強さ（ノンチ付）を測定したところ１１．８ ｋｇｃ
ｍ／ ｃｍと良好な値を示した。(Manufacture of thermoplastic resin composition and molded product) 35 parts of the above resin powder and 65 parts of 50 μm diameter enameled wire (polyurethane coated copper wire) were mixed into Plasticorder PL manufactured by Brabender, West Germany.
Melt kneading was carried out at 200° C. and 30 rpm using a D651 model. 150 at 190°C/3 minutes using the obtained composition.
A resin plate with a thickness of 2 mm was compression molded. When the shielding effect was measured in the same manner as in Example 2, it was found to be a good value of 40 dB. In addition, when the Izotsu impact strength (with a non-stop) was measured in the same manner as in Example 1, it was 11.8 kgc.
It showed a good value of m/cm.
（発明の効果）
本発明に係る熱可塑性樹脂組成物及びこれによって得ら
れる成形品は、電磁波シールド性に優れ。(Effects of the Invention) The thermoplastic resin composition according to the present invention and the molded product obtained therefrom have excellent electromagnetic shielding properties.
耐衝撃性等の機械的特性にも優れる。It also has excellent mechanical properties such as impact resistance.
第１図は実施例の熱可塑性樹脂組成物から得られた樹脂
板の体積抵抗と該組成物を得るための。
混練時の樹脂温度との関係を示すグラフである。
−ｉ５ 、、””ｊ
代理人 弁理士 若 林 邦 彦FIG. 1 shows the volume resistance of a resin plate obtained from a thermoplastic resin composition of an example and the method for obtaining the composition. It is a graph showing the relationship with resin temperature during kneading. -i5 ,,””j Agent Patent Attorney Kunihiko Wakabayashi
Claims (1)
化ビニル化合物及びメタクリル酸エステルのうち、少な
くとも一種の単量体をグラフト重合させて得られる熱可
塑性樹脂 並びに （Ｂ）直径が１〜１００μｍの樹脂被覆銅線を該被覆樹
脂の軟化温度以上の温度で混練して得られる熱可塑性樹
脂組成物。 ２、（Ａ）成分中のゴム状重合体が、アクリル酸アルキ
ルエステル重合体である請求項１記載の熱可塑性樹脂組
成物。 ３、（Ａ）成分の熱可塑性樹脂が、ゴム状重合体１５〜
６０重量％に、単量体８５〜４０重量％配合し、重合し
て得られるものである請求項１または２記載の熱可塑性
樹脂組成物。 ４、（Ａ）成分の熱可塑性樹脂と（Ｂ）成分の樹脂被覆
鋼線の容量比が（Ａ）成分／（Ｂ）成分で９５／５〜５
０／５０である請求項１、２または３記載の熱可塑性樹
脂組成物。 ５、請求項１〜４のいずれかに記載の熱可塑性樹脂組成
物を成形して得られる成形品。[Scope of Claims] 1. (A) A thermoplastic resin obtained by graft polymerizing at least one monomer selected from aromatic vinyl compounds, vinyl cyanide compounds, and methacrylic acid esters to a rubber-like polymer; B) A thermoplastic resin composition obtained by kneading resin-coated copper wires having a diameter of 1 to 100 μm at a temperature equal to or higher than the softening temperature of the coating resin. 2. The thermoplastic resin composition according to claim 1, wherein the rubbery polymer in component (A) is an acrylic acid alkyl ester polymer. 3. The thermoplastic resin of component (A) is a rubbery polymer 15 to
3. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is obtained by blending 60% by weight with 85 to 40% by weight of a monomer and polymerizing the mixture. 4. The capacity ratio of the thermoplastic resin as the component (A) and the resin-coated steel wire as the component (B) is 95/5 to 5 (component (A)/component (B))
The thermoplastic resin composition according to claim 1, 2 or 3, wherein the thermoplastic resin composition is 0/50. 5. A molded article obtained by molding the thermoplastic resin composition according to any one of claims 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13080890A JPH0425551A (en) | 1990-05-21 | 1990-05-21 | Thermoplastic resin composition and molded article |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13080890A JPH0425551A (en) | 1990-05-21 | 1990-05-21 | Thermoplastic resin composition and molded article |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0425551A true JPH0425551A (en) | 1992-01-29 |
Family
ID=15043192
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13080890A Pending JPH0425551A (en) | 1990-05-21 | 1990-05-21 | Thermoplastic resin composition and molded article |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0425551A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014078698A (en) * | 2012-09-20 | 2014-05-01 | Jsr Corp | Electromagnetic wave-absorbing composition and electromagnetic wave absorber |
| DE102014219431A1 (en) | 2013-09-30 | 2015-04-02 | Hitachi Automotive Systems, Ltd. | Cylinder device and manufacturing method for this |
| DE102015203482A1 (en) | 2014-02-28 | 2015-09-03 | Hitachi Automotive Systems, Ltd. | cylinder device |
-
1990
- 1990-05-21 JP JP13080890A patent/JPH0425551A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014078698A (en) * | 2012-09-20 | 2014-05-01 | Jsr Corp | Electromagnetic wave-absorbing composition and electromagnetic wave absorber |
| DE102014219431A1 (en) | 2013-09-30 | 2015-04-02 | Hitachi Automotive Systems, Ltd. | Cylinder device and manufacturing method for this |
| DE102015203482A1 (en) | 2014-02-28 | 2015-09-03 | Hitachi Automotive Systems, Ltd. | cylinder device |
| US9651110B2 (en) | 2014-02-28 | 2017-05-16 | Hitachi Automotive Systems, Ltd. | Cylinder apparatus |
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