JPS6354466A - Antistatic thermoplastic resin composition - Google Patents
Antistatic thermoplastic resin compositionInfo
- Publication number
- JPS6354466A JPS6354466A JP61196857A JP19685786A JPS6354466A JP S6354466 A JPS6354466 A JP S6354466A JP 61196857 A JP61196857 A JP 61196857A JP 19685786 A JP19685786 A JP 19685786A JP S6354466 A JPS6354466 A JP S6354466A
- Authority
- JP
- Japan
- Prior art keywords
- thermoplastic resin
- resin composition
- antistatic
- composition according
- antistatic thermoplastic
- 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 26
- 239000011342 resin composition Substances 0.000 title claims description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 6
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 6
- 229920001577 copolymer Polymers 0.000 claims abstract description 5
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 5
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 5
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 8
- 239000004793 Polystyrene Substances 0.000 claims description 6
- 229920002223 polystyrene Polymers 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 150000007524 organic acids Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 2
- 150000001450 anions Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 125000000547 substituted alkyl group Chemical group 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- 150000003242 quaternary ammonium salts Chemical group 0.000 abstract description 4
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract 2
- 238000007786 electrostatic charging Methods 0.000 abstract 1
- 230000002085 persistent effect Effects 0.000 abstract 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 1
- 238000000034 method Methods 0.000 description 13
- -1 polyethylene Polymers 0.000 description 10
- 239000002216 antistatic agent Substances 0.000 description 8
- 229920005601 base polymer Polymers 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000008188 pellet Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000000576 coating method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000009864 tensile test Methods 0.000 description 4
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 229920005990 polystyrene resin Polymers 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920000638 styrene acrylonitrile Polymers 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 1
- AWFYPPSBLUWMFQ-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,6,7-tetrahydropyrazolo[4,3-c]pyridin-5-yl)ethanone Chemical group C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=C2 AWFYPPSBLUWMFQ-UHFFFAOYSA-N 0.000 description 1
- QLIBJPGWWSHWBF-UHFFFAOYSA-N 2-aminoethyl methacrylate Chemical compound CC(=C)C(=O)OCCN QLIBJPGWWSHWBF-UHFFFAOYSA-N 0.000 description 1
- WWJCRUKUIQRCGP-UHFFFAOYSA-N 3-(dimethylamino)propyl 2-methylprop-2-enoate Chemical compound CN(C)CCCOC(=O)C(C)=C WWJCRUKUIQRCGP-UHFFFAOYSA-N 0.000 description 1
- OAKUJYMZERNLLT-UHFFFAOYSA-N 4-(dimethylamino)butyl 2-methylprop-2-enoate Chemical compound CN(C)CCCCOC(=O)C(C)=C OAKUJYMZERNLLT-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920011250 Polypropylene Block Copolymer Polymers 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000006177 alkyl benzyl group Chemical group 0.000 description 1
- 150000001347 alkyl bromides Chemical class 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 229920006147 copolyamide elastomer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 description 1
- CZXGXYBOQYQXQD-UHFFFAOYSA-N methyl benzenesulfonate Chemical compound COS(=O)(=O)C1=CC=CC=C1 CZXGXYBOQYQXQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 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〕
本発明は良好且つ恒久的な帯電防止性を育する熱可塑性
グ（脂組酸物に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a thermoplastic acid compound that develops good and permanent antistatic properties.
一般にプラスチックスは電気抵抗値が大キく。 Plastics generally have a high electrical resistance value.
摩擦、剥離等によって容易に帯電し易く、ごみや埃を吸
引して外観を損ねる等成形品、フィルム、シート、繊維
等の分野で様々なトラブルの原因となっている。It is easily charged with electricity due to friction, peeling, etc., and causes various problems in the fields of molded products, films, sheets, fibers, etc., such as attracting dirt and dust and damaging the appearance.
プラスチックスに訓電性を付与するには一般的に
１、帯電防止剤の内部ａｐ込み法
Ｚ帯電防止剤の表面塗布法
の二杜の方法がもちいられている。他にもシリコン系化
合物の表面塗布法、又はプラスチックス表面構造の改質
、すなわちプラズマ処理等があるが、いず牡も高価なも
のとなる・
帯電防止剤の内部疎り込み法は、一般的に低分子の界面
活性剤が用いられるが、この方法では恒久的な帯電防止
性を付与することが困難であり１表面に存在する帯電防
止剤を水洗、Ｊ＠擦等の手段で除いてしまうと訓電性が
失われてしまう。又、特開昭５５−１６２３７号公報で
見られる様に制電性ゴムを用いる方法があるが。Generally, the following methods are used to impart electrostatic properties to plastics: 1, an internal apical injection method of an antistatic agent, and 2, a surface coating method of an antistatic agent. There are other methods such as surface application of silicon-based compounds or modification of the surface structure of plastics, that is, plasma treatment, but both are expensive.The method of internally dispersing antistatic agents is generally Generally, low-molecular surfactants are used, but it is difficult to impart permanent antistatic properties with this method. If it is stored away, the training properties will be lost. There is also a method of using antistatic rubber as seen in Japanese Patent Application Laid-open No. 55-16237.
添加量を多く必要とし、プラスチックス本来の耐熱性等
の物性を低下させてしまう上に表面抵抗値もたかだか１
０１１Ω程度であり良好とはいえない。A large amount of additive is required, which deteriorates the physical properties such as heat resistance that are inherent to plastics, and the surface resistance value is only 1.
It is about 0.011Ω, which is not good.
帯電防止剤の表面塗布法は、表面抵装置１０９０程度と
非常に良好な訓電性を示すが、水洗、！＃擦等によって
制電性は簡単に失われてしまう。The surface coating method of antistatic agent shows very good electrostatic properties with a surface resistance of about 1090, but washing with water! #Antistatic properties are easily lost due to rubbing, etc.
その上内部練り込み法と違って表面塗布工程を必要とし
、コスト高となってしまう。Moreover, unlike the internal kneading method, a surface coating process is required, resulting in high costs.
最近ではエレクトロニクス部品の運搬用コンテナーや包
装材で信題性の高い帯電防止性材料が求められている。Recently, highly reliable antistatic materials are required for transportation containers and packaging materials for electronic parts.
しかるに上述の如き、特別な工程を必要とせず、少量の
配合量で良好な制電性を恒久的に示し且つペースポリマ
ー本来の物性も低下させない帯電防止剤がなく、その開
発が望まれている。However, as mentioned above, there is no antistatic agent that does not require a special process, permanently exhibits good antistatic properties with a small amount of addition, and does not deteriorate the inherent physical properties of the pace polymer, and the development of such is desired. .
〔問題点を解決する友めの手段」
本発明者らは上述し几如き現状に鑑み鋭意検討の結果、
特定の四級アンモニウム塩基を有する単量体を重合して
得た重合体をベースポリマーである熱可塑性樹脂に少量
配合することにより、ベースポリマーの耐熱性を殆ど低
下させずに良好で且つ恒久的な訓電性が付与された熱可
塑性樹脂組成物とし得ることを見出し本発明に到達した
・
本発明は熱可塑性樹脂１００重量部に対し、一般式
％式％
（式中、Ｒ１は水素又はメチル基、馬〜Ｒ４は水素又は
置換基を有していてもよい炭素数１〜９のアルキル基、
ｎは１〜１ｏの数、Ｘ−は−価の無機、又は有機の酸基
か又は無機酸あるいは有機酸の相応する等何物を表す。[Friendly Means to Solve Problems] As a result of intensive study in view of the above-mentioned current situation, the inventors of the present invention have found that
By blending a small amount of a polymer obtained by polymerizing a monomer with a specific quaternary ammonium base into a thermoplastic resin that is a base polymer, it is possible to achieve good and permanent heat resistance with almost no reduction in the heat resistance of the base polymer. The present invention has been achieved by discovering that a thermoplastic resin composition can be made into a thermoplastic resin composition that is endowed with electrostatic properties.The present invention is based on the general formula % formula % (wherein R1 is hydrogen or methyl) based on 100 parts by weight of the thermoplastic resin. group, R4 is hydrogen or an alkyl group having 1 to 9 carbon atoms which may have a substituent,
n is a number from 1 to 1o, and X- represents a -valent inorganic or organic acid group or a corresponding inorganic or organic acid.
）で表される四級アンモニウム塩−を有する単量体単位
からなる重合体音α１〜４０重量部配合してなる帯電防
止性熱可塑性樹脂組成物である。) is an antistatic thermoplastic resin composition containing 1 to 40 parts by weight of a polymer consisting of a monomer unit having a quaternary ammonium salt.
本発明におけるベースポリマーとして用いる熱可塑性樹
脂としては％（（］少なくとも一棟のエチレン性不飽和
単量体の重合生成物並びにその共重合体、例えばポリエ
チレン、ポリ１０ピレン、ポリメチルペンテン、更には
ビニル単量体、アクリル単量体をその構成成分とするも
の、例えばポリ塩化ビニル、ポリ酢酸ビニル、エチレン
−酢酸ビニル共重合体、エチレン−エチルアクリレート
共重合体、エチレン系アイオンマー樹脂、ポリメチルメ
タクリレート、ボリスチレ７、スチレン−アクリロニト
リル共１合体、スチレン−アルキル（メタコアクリレー
ト共重合体、ゴムす性ポリスチレン、ムＢ８樹脂％ＭＢ
日樹脂、ＡＡ８樹脂等、（ロ）自己縮合にょ５重合可能
な少なくとも一棟の二官能的反応性化合物の重合体１例
えばポリオキシメチレン、ポリアセメール共重合体、ポ
リフェニレンエーテル、ＰＰＢ樹脂、ポリカプロラクト
ン、ポリカプロラクトン等、ｅ９多縮合によって１合可
能な少なくとも二１の二官能的反応性化合物の１合体、
例えばナイロン−６６、ポリスルフォン、ポリエステル
、ポリエステル−ポリエーテルあるいはポリエステル−
ポリアミドブロック共重合体、ポリイミド、芳香族ポリ
エステル、ポリカーボネイト、ポリエーテルエーテルケ
トン、ポリウレタンエラストマー等が挙げらｎｌこれら
の１合体を単独もしくは組合せて用いることができる。Thermoplastic resins used as base polymers in the present invention include polymerization products of at least one ethylenically unsaturated monomer and copolymers thereof, such as polyethylene, poly10-pyrene, polymethylpentene, and Those whose constituent components are vinyl monomers and acrylic monomers, such as polyvinyl chloride, polyvinyl acetate, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene ionmer resin, polymethyl methacrylate , Boristyrene 7, styrene-acrylonitrile co-monomer, styrene-alkyl (methacrylate copolymer, rubbery polystyrene, MuB8 resin% MB
Polymers of at least one difunctional reactive compound capable of self-condensation (5) such as Japanese resin, AA8 resin, etc. (2) Polymers of at least one bifunctional reactive compound capable of polymerization (1) For example, polyoxymethylene, polyacemel copolymer, polyphenylene ether, PPB resin, poly A combination of at least 21 bifunctional reactive compounds that can be combined by e9 polycondensation, such as caprolactone, polycaprolactone, etc.
For example, nylon-66, polysulfone, polyester, polyester-polyether or polyester-
Polyamide block copolymers, polyimides, aromatic polyesters, polycarbonates, polyetheretherketones, polyurethane elastomers, etc. may be mentioned, and one combination thereof can be used alone or in combination.
これら重合体の内ポリスチレン、スチレン−アクリロニ
トリル共１合体、ＡＢＢｍＨ，ポリメチルメタクリレー
トおよびポリ塩化ビニルが好ましく用いられる。Among these polymers, polystyrene, styrene-acrylonitrile monomer, ABBmH, polymethyl methacrylate and polyvinyl chloride are preferably used.
本発明における訓電性を付与し得る１合体の構成成分’
ｔ７ある四級アンモニウム塩１ｔ−ｖする単量体ユニッ
トは、一般式
％式％
（式中、Ｒ１ｓ Ｒ，〜Ｒ４ｍ ”およびＸ−は上記に
同じ）
で表されるものであり、これはアミンを有するアクリレ
ート又はメタクリレートが四級化剤によって四級化され
たものである。A single integrated constituent component capable of imparting electrification properties in the present invention'
The monomer unit of the quaternary ammonium salt t7 is represented by the general formula % (wherein R1s R, ~R4m'' and X- are the same as above), and this is an amine The acrylate or methacrylate having the following is quaternized using a quaternizing agent.
アミンを有するアクリレート又はメタクリレートの具体
例としてはジメチルアミノエチルアクリレート、ジエチ
ルアミノエチルアクリレート、ジエチルアミノエチルア
クリレート、ジエチルアミノエチルアクリレート、ジメ
チルアミノプロピルメタクリレート、ジメチルアミノブ
チルメタクリレート、ジブチルアミノエチルメタクリレ
ート、ジブチルアミノエチルメタクリレート、ジヒドロ
キシエチルアミノエチルメタクリレート等が挙げられる
。Specific examples of acrylates or methacrylates having amines include dimethylaminoethyl acrylate, diethylaminoethyl acrylate, diethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl methacrylate, dimethylaminobutyl methacrylate, dibutylaminoethyl methacrylate, dibutylaminoethyl methacrylate, dihydroxyethyl. Examples include aminoethyl methacrylate.
四級化剤としてはジメチル硫酸、ジエチル硫酸、ジス０
ビル硫酸等のアルキル硫酸類、Ｐ−トルエンスルホン酸
メチル、ベンゼンスルホン酸メチル等のスルホン散エス
テル類、ジメチル亜（ｉｉｌｔ ａ 等のアルキル亜（
ｊ！酸類、トリメチルホス７エイト等のアルキル硫酸類
、アルキルベンジルクロライド、ベンジルクロライド、
アルキルクロライド、アルキルブロマイド等の各種ハラ
イドが挙げられ、特にアルキル硫酸類およびスルホ／酸
エステル類が耐熱分解性の点より好ましいものである。Quaternizing agents include dimethyl sulfate, diethyl sulfate, and
Alkyl sulfuric acid such as biru sulfuric acid, sulfone dispersion esters such as methyl P-toluenesulfonate and methyl benzenesulfonate, alkyl sulfuric acid (such as dimethyl sulfate), etc.
j! Acids, alkyl sulfates such as trimethyl phos-7ate, alkyl benzyl chloride, benzyl chloride,
Various halides such as alkyl chlorides and alkyl bromides may be mentioned, and alkyl sulfates and sulfo/acid esters are particularly preferred from the viewpoint of heat decomposition resistance.
上記一般式中のｎは１〜１０であるが、ｎが２〜６が特
に好ましいものである。In the above general formula, n is 1 to 10, and preferably 2 to 6.
本発明における訓電性全付与し得る１合体の分子量は１
０００〜１０００００であることが好ましい。分子量が
１０００禾滴であｎげ良好な恒久的制電性が得られない
ば刀為りでなく、賦屋時にスリップ等の問題を起こし、
その上可塑化効果によりベースポリマーの耐熱性を低下
させてしまうｆｃめ好ましぐない。なおこの重合体の重
合方法は特に限定さ九ないが、通常ラジカル重合塊状重
合等の手法を用いることができる。In the present invention, the molecular weight of one coalescence that can impart all electrophoretic properties is 1
It is preferable that it is 000-100000. If the molecular weight is 1,000 droplets and good permanent antistatic properties cannot be obtained, problems such as slipping will occur when applying, not just sword damage.
Moreover, fc lowers the heat resistance of the base polymer due to its plasticizing effect, which is undesirable. The method of polymerizing this polymer is not particularly limited, but methods such as radical polymerization and bulk polymerization can usually be used.
本発明における制電性を付与し得る重合体は四級アンモ
ニウム塩基ｔ−有する単量体を１００チ使用して得られ
るため、ベースポリマーに対し少量の配合で高レベルの
制電性を発現する友めコスト面でも有利である。Since the polymer capable of imparting antistatic properties in the present invention is obtained by using 100 monomers having quaternary ammonium base t-, a high level of antistatic properties can be achieved with a small amount added to the base polymer. It is also advantageous in terms of friend cost.
上記制電性を付与し得る重合体の配合量は。What is the blending amount of the polymer that can impart the above-mentioned antistatic properties?
ベースポリマーである熱可厘性樹脂１ｏｏ！ｆ１部に対
しα１〜４０重量部、好ましくはα５〜３０重量部であ
る。配合量がα１Ｍ量部未満であると良好な訓電性を付
与できず、又４０ｍｆ部を超えるとベースポリマーの本
来の物性を大きく損ねる傾向となり好ましくない。通常
は２重量部程度の配合量で十分であり、仁の場合で表面
抵抗値１０１０Ω〜１０１３Ωとなる。Base polymer thermoplastic resin 1oo! It is α1 to 40 parts by weight, preferably α5 to 30 parts by weight, based on 1 part f. If the amount is less than 1M parts α, good electrical conductivity cannot be imparted, and if it exceeds 40 mf parts, the original physical properties of the base polymer tend to be greatly impaired, which is not preferable. Usually, a blending amount of about 2 parts by weight is sufficient, and in the case of kernels, the surface resistance value is 1010Ω to 1013Ω.
本発明の熱可塑性樹脂組成物が訓電性を発現するのは１
本発明において用いる四級アンモニウム塩基を有する重
合体の独特の性質の友め、本組成物を射出成形や押出成
形等の成形時に成りすることによるものである、ま几か
かる四級アンモニウム塩基含有重合体はポリマーである
ため、かかるｍ放物からの成形品を水洗しても容易に脱
落せず、恒久制電性を付与できる上に可塑化効果もなく
耐熱性も低下させない等優れ次効果を有する。The thermoplastic resin composition of the present invention exhibits electrostatic properties in 1
Due to the unique properties of the polymer containing a quaternary ammonium base used in the present invention, the polymer containing a quaternary ammonium base is Since the polymer is a polymer, it does not easily fall off even when molded products made from m-paraboloids are washed with water, and it has excellent effects such as permanent antistatic properties, no plasticizing effect, and no reduction in heat resistance. have
本発明の熱可星性樹脂組成物には他の帯電防止剤、滑剤
、抗酸化剤、紫外線吸収剤およびその他の添加剤を配合
しても差し支えない。The thermoplastic resin composition of the present invention may contain other antistatic agents, lubricants, antioxidants, ultraviolet absorbers, and other additives.
なお、上記重合体中の四級アンモニウム塩基は酸化され
易いためホスファイト系の抗酸化剤を配合することが好
ましい。In addition, since the quaternary ammonium base in the above polymer is easily oxidized, it is preferable to blend a phosphite-based antioxidant.
以下、実施例により本発明を具体的に説明する。なお、
実施例および比較例中の処理条件および物性評価条件は
下記の方法によつ几。Hereinafter, the present invention will be specifically explained with reference to Examples. In addition,
The processing conditions and physical property evaluation conditions in Examples and Comparative Examples were determined by the following methods.
調 湿 ：ペレットヲ射出成形により１０ｃｒｎ×１０
ｃ１ｎＸ２ｍの板に底形し、２３℃、湿度６５チで１日
調湿し友。Humidity control: 10 crn x 10 by pellet injection molding
The bottom is shaped like a c1n x 2m board, and the humidity is controlled for one day at 23℃ and humidity of 65℃.
水洗処理：測定用試片奮３０℃で超音波洗浄を３０分間
行った。Water washing treatment: The measurement specimen was washed with ultrasonic waves at 30° C. for 30 minutes.
表面抵抗値：超絶縁抵抗計（タケダ理研製、 ＴＲ−８
６０１）を使用し、２３℃、湿度６５係の条件下で印加
電圧５００ｖで１分後の表面抵抗値（Ω）全測定した。Surface resistance value: Super insulation resistance meter (manufactured by Takeda Riken, TR-8
601), the surface resistance value (Ω) was measured after 1 minute at an applied voltage of 500 V under conditions of 23° C. and humidity of 65 parts.
電荷半減時間：スタティックオネストメーター（宍戸商
会製）を使用し、印加電圧１００００Ｖ、試料回転速度
１３００ｒｐｍ、印加時間３０秒、２３℃、湿度６５％
の条件下で側足し、電圧印加時の試料電圧を初期電圧（
Ｖ）、電圧印加後試料電圧が初期電圧の半分になるまで
の時間を電荷半減時間（秒）とし友。Charge half-life time: Using a static honest meter (manufactured by Shishido Shokai), applied voltage 10000 V, sample rotation speed 1300 rpm, application time 30 seconds, 23°C, humidity 65%
Under the conditions of
V), the time it takes for the sample voltage to become half of the initial voltage after voltage application is defined as the charge half-life time (seconds).
熱変形温度（ＨＤＴ）： Ａ８ＴＭ Ｄ６４８に準じ
てＨＤＴ測定用試片全作成し、この試片をアニール後Ａ
３Ｔｌ！ Ｄ６４８に準じてＩ（Ｄ Ｔ タンを測定
し皮。Heat distortion temperature (HDT): All specimens for HDT measurement were prepared according to A8TM D648, and after annealing this specimen
3Tl! Measure I (DT tongue) according to D648.
引張試験： ＡＳＴＭ Ｄ６４８に準じて引張試収を
行い、引張弾性係数お工び引張破壊強度を測定した。Tensile test: A tensile test was conducted according to ASTM D648, and the tensile modulus of elasticity and tensile breaking strength were measured.
表面状態：銀条の有無１！−表し、○は鉄条が全く現れ
ず、Δは銀条が少し現れ次ことを示す。Surface condition: Presence or absence of silver streaks 1! - indicates that no iron stripes appear at all, and Δ indicates that some silver stripes appear.
実施例１
攪拌羽根付き３ｔのガラス製フラスコにジエチルアミノ
エチルメタクリレ−１”５７４１ｆｉｔ、部。Example 1 5741 parts of diethylaminoethyl methacrylate was placed in a 3 ton glass flask equipped with a stirring blade.
ハイドロキノンモノメチルエーテル４ Ｍ Ｊｉｔ Ｈ
Ｖｒ、メタノール４５０ｍ１１部を入ｎ、激しく攪拌し
ながらジメチルｇＩｌ酸２５２１盪部、メタノール８０
ｉ黛部の混合物’ｔ−３０℃以下になるように滴下し次
。滴下終了後３０分間攪拌して刀・らアゾビスインブチ
ロニトリルＭｍｆｆｉ部％ ｎ−オクチルメルカプタン
４１Ｅｉｆｔ部’を加え、６（１’Ｃ，窒素雰囲気下で
４時間点合した。１合後七〇°まま真空乾燥し制電性付
与Ｎ０体（Ｔ−１）をねｆｃ。Hydroquinone monomethyl ether 4 M Jit H
Vr, add 11 parts of 450ml of methanol, add 2521 parts of dimethyl gIl acid and 80ml of methanol while stirring vigorously.
Add the mixture dropwise so that the temperature is below -30°C. After the completion of the dropwise addition, the mixture was stirred for 30 minutes, and 41 parts of n-octyl mercaptan and 41 parts of azobisinbutyronitrile were added, and the mixture was mixed for 4 hours under a nitrogen atmosphere at 6 (1'C). Vacuum dry at 〇° to obtain N0 body (T-1) with antistatic properties.
得ら扛九制電性付与重合体２ｇ量部をポリスチレン樹脂
１００Ｎ量部に混合し、浴融押出機によりペレット化し
た。2 g parts of the obtained antistatic property imparting polymer were mixed with 100 N parts of polystyrene resin and pelletized using a bath melt extruder.
得られたペレットを射出成形により１０６ｒＩＸ１０ｃ
！ＲＸ２ｅｍの板にして〃１ら調湿後側電性を評価した
ところ表面抵抗値８Ｘ１０”Ω、電荷半減時間２秒であ
った〇
又ＨＤＴｆ測定したところ９２℃であった。The obtained pellets were injection molded into 106rIX10c.
! When the side conductivity of the RX2em board was evaluated after humidity conditioning, the surface resistance value was 8 x 10''Ω, and the charge half-life time was 2 seconds.Also, when the HDTf was measured, it was 92°C.
さらに引張試験を行ったところ引張弾性係数２、７ Ｘ
１０’ Ｋ９／ａｎ”、引張破壊強度５６０に９７副
２であつ几。Further tensile tests revealed a tensile modulus of elasticity of 2.7
10'K9/an'', tensile strength at break of 560 and 97 vice 2.
実施例２〜６
実施例１で得た訓電性付与重合体（Ｔ−１）ｔポリスチ
レン樹脂１００重量部に対し表ＩＫ示す各種の配合量で
配合し、溶融押出機によりペレット化した＠
得らｎた谷ペレットを用い実施例１と同じ方法により種
々の物性を評価した結果全表１に示すＯ
実施例７〜１５．比較例１〜５
アミン含有（メタ）アクリレートおよび四級化剤を表２
に示すものを用いる以外は実施例１と同様の方法により
！種の訓電性付与Ｍ合体（Ｔ−２〜Ｔ−６）’ｚ得た。Examples 2 to 6 The electrophoretic polymer (T-1) obtained in Example 1 was blended with 100 parts by weight of polystyrene resin in various amounts shown in Table IK, and pelletized using a melt extruder. The results of evaluating various physical properties using the same method as in Example 1 using pellets shown in Table 1. Examples 7 to 15. Comparative Examples 1 to 5 Amine-containing (meth)acrylates and quaternizing agents are shown in Table 2.
Follow the same method as in Example 1 except for using the one shown in ! M combinations (T-2 to T-6)'z with electrifying properties of seeds were obtained.
表 ２
得られた各制電性付与１合体および前記Ｔ−１の２重量
部を表３に示す各２！！熱可塑性樹脂１００重量部に夫
々配合し、溶融押出機によりペレット化し次。Table 2 2 parts by weight of each antistatic property imparting 1 combination obtained and the above T-1 are shown in Table 3. ! Each was blended with 100 parts by weight of a thermoplastic resin and pelletized using a melt extruder.
得らｎた各ベレットヲ用い実施例１と同じ方法により、
社々の物性全評価し几結果全表３に併せて示す。Using the same method as in Example 1 using each pellet obtained,
All the physical properties of the companies were evaluated and the results are shown in Table 3.
表３中の略号は次の通りである。The abbreviations in Table 3 are as follows.
ｐｓｔ ：ポリスチレン
ＰＡＳ ：スチレンーアクリロニトリル共重合体ｐｖ
ｃ ：ポリ塩化ビニル
ＰＭＭＡ ：ポリメチルメタクリレートＡ１１Ｂ ：
Ａｌ３Ｅ？樹脂
比較例６
ポリスチレン樹脂１００重量部に対しグリセリンモノス
テアレート（低分子界面活性剤）１０！量部を混合し、
溶融押出機によりペレット化し７ｊａ
得らｎたベレットヲ射出成形により１０ ａｍ Ｘ１０
ｃｍＸ２ｍ＋の板にしてから調湿後側電性を評価したと
ころ表面抵抗値ａ３Ｘ１ｏ１χΩ、！荷半減時間五５秒
であった。pst: Polystyrene PAS: Styrene-acrylonitrile copolymer pv
c: Polyvinyl chloride PMMA: Polymethyl methacrylate A11B:
Al3E? Resin Comparative Example 6 10 parts by weight of glycerin monostearate (low molecular surfactant) for 100 parts by weight of polystyrene resin! Mix parts of
The resulting pellets were pelletized using a melt extruder and then injection molded to 10 am x 10 mm.
When we evaluated the side conductivity after humidity conditioning using a board of cmX2m+, the surface resistance value was a3X1o1χΩ! The time for the load to be halved was 55 seconds.
又得られた板に水洗処理を行い、直ちに制電性を評価し
たところ表面抵抗値＆４Ｘ１０１ＳΩ。In addition, the obtained board was washed with water and immediately evaluated for antistatic property, and the surface resistance value was &4X101SΩ.
電荷半波時間２分以上であった。The charge half-wave time was 2 minutes or more.
又ＨＤＴｔ″測定し友ところ６８℃でおった。Also, HDTt'' was measured and found to be 68°C.
さらに引張試験を行ったところ、引張弾性係数Ｚ ５
Ｘ １０’ Ｋ９／ｃｎｔ” ｓ引張破壊強度５００
Ｋ９７ｃｍ”であつ几。Further tensile tests were conducted and the tensile modulus of elasticity Z 5
X 10'K9/cnt" s Tensile breaking strength 500
K97cm" and Atsushi.
比較例７
四級アンモニウム塩基を有する塗布温帯電防止剤の１．
５係水溶液に１０α×１０α×２−のポリスチレン成形
板金１分間浸漬し、風乾後２３℃、湿度６５俤で１日調
湿後制電性を評価し九ところ表面抵抗値１．５Ｘ１０”
Ω、電荷半減時間１．５秒であった。Comparative Example 7 1. Coating temperature antistatic agent with quaternary ammonium base.
A polystyrene molded sheet metal of 10α x 10α x 2- is immersed in a 5-layer aqueous solution for 1 minute, air-dried, and then conditioned for 1 day at 23°C and 65 degrees of humidity.The antistatic property was evaluated, and the surface resistance was 1.5 x 10".
Ω, and the charge half-life time was 1.5 seconds.
又得られた板に水洗処理を行い直ちに訓電性を評価した
ところ表面抵抗値！Ｌ８Ｘ１０１５０、電荷生滅時間は
２分以上であり、恒久制電性に欠けて°い友。In addition, the obtained board was washed with water and immediately evaluated for electrical conductivity, and the surface resistance value was found! L8X10150 has a charge generation/disappearance time of more than 2 minutes and lacks permanent antistatic properties, making it a good friend.
本発明の樹脂組成物は良好且つ恒久的な帯電防止性を有
し、しかもペースポリマー本来の耐熱性を低下させない
ものである九め、ごみや埃を吸引して外観を損ねる等の
成形品、フィルム、シート、繊維等の分野で起る様々な
帯電トラブ＃７５”す（、Ｊｌつエレクトロニクス関連
等の高信顕性を必云とする分野にも使用することができ
る。The resin composition of the present invention has good and permanent antistatic properties and does not reduce the inherent heat resistance of the pace polymer. It can also be used in fields that require high reliability, such as electronics, for various charging troubles that occur in the fields of films, sheets, textiles, etc.
Claims (1)
水素又は置換基を有していてもよい炭素数１ 〜９のアルキル基、ｎは１〜１０の数、Ｘ＾−は一価の
無機、又は有機の酸基か又は無機 酸あるいは有機酸の相応する等価物を表す。 で表される四級アンモニウム塩基を有する単量体単位か
らなる重合体を０．１〜４０重量部配合してなる帯電防
止性熱可塑性樹脂組成物。 ２、一般式中の四級アンモニウム塩基のカウンタ−アニ
オンＸ＾−が ＲＳＯ＾−＿３又はＲＯＳＯ＾−＿３ （但し、Ｒは水素又はフエニル基を有していてもよい炭
素数１〜２０のアルキル基を表 す。） である特許請求の範囲第１項記載の帯電防止性熱可塑性
樹脂組成物。 ３、熱可塑性樹脂がポリスチレンである特許請求の範囲
第１項記載の帯電防止性熱可塑性樹脂組成物。 ４、熱可塑性樹脂がスチレン−アクリロニトリル共重合
体である特許請求の範囲第１項記載の帯電防止性熱可塑
性樹脂組成物。 ５、熱可塑性樹脂がＡＢＳ樹脂である特許請求の範囲第
１項記載の帯電防止性熱可塑性樹脂組成物。 ６、熱可塑性樹脂がポリメチルメタクリレートである特
許請求の範囲第１項記載の帯電防止性熱可塑性樹脂組成
物。 ７、熱可塑性樹脂がポリ塩化ビニルである特許請求の範
囲第１項記載の帯電防止性熱可塑性樹脂組成物。[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 is hydrogen or a methyl group, and R_2 to R_4 are hydrogen or have a substituent. an optionally substituted alkyl group having 1 to 9 carbon atoms, n is a number from 1 to 10, and X^- represents a monovalent inorganic or organic acid group, or a corresponding equivalent of an inorganic or organic acid. An antistatic thermoplastic resin composition containing 0.1 to 40 parts by weight of a polymer consisting of a monomer unit having a quaternary ammonium base represented by the following: 2. The quaternary ammonium base in the general formula A patent claim in which the counter anion The antistatic thermoplastic resin composition according to claim 1. 3. The antistatic thermoplastic resin composition according to claim 1, wherein the thermoplastic resin is polystyrene. 4. The thermoplastic resin composition is polystyrene. The antistatic thermoplastic resin composition according to claim 1, which is an acrylonitrile copolymer. 5. The antistatic thermoplastic resin composition according to claim 1, wherein the thermoplastic resin is an ABS resin. 6. The antistatic thermoplastic resin composition according to claim 1, wherein the thermoplastic resin is polymethyl methacrylate. 7. The antistatic thermoplastic resin composition according to claim 1, wherein the thermoplastic resin is polyvinyl chloride. antistatic thermoplastic resin composition.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61196857A JPS6354466A (en) | 1986-08-22 | 1986-08-22 | Antistatic thermoplastic resin composition |
| US07/087,524 US4859727A (en) | 1986-08-22 | 1987-08-20 | Antistatic thermoplastic resin composition |
| CA000545093A CA1335013C (en) | 1986-08-22 | 1987-08-21 | Antistatic thermoplastic resin composition |
| EP87112178A EP0257592B1 (en) | 1986-08-22 | 1987-08-21 | Antistatic thermoplastic resin composition |
| DE3788544T DE3788544T2 (en) | 1986-08-22 | 1987-08-21 | Antistatic thermoplastic molding compound. |
| KR1019870009191A KR910007310B1 (en) | 1986-08-22 | 1987-08-22 | Antistatic thermoplastic resin compositions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61196857A JPS6354466A (en) | 1986-08-22 | 1986-08-22 | Antistatic thermoplastic resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6354466A true JPS6354466A (en) | 1988-03-08 |
Family
ID=16364808
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61196857A Pending JPS6354466A (en) | 1986-08-22 | 1986-08-22 | Antistatic thermoplastic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6354466A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4916033A (en) * | 1972-06-05 | 1974-02-13 |
-
1986
- 1986-08-22 JP JP61196857A patent/JPS6354466A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4916033A (en) * | 1972-06-05 | 1974-02-13 |
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