JPH09302247A - Conductive resin composition - Google Patents
Conductive resin compositionInfo
- Publication number
- JPH09302247A JPH09302247A JP8123554A JP12355496A JPH09302247A JP H09302247 A JPH09302247 A JP H09302247A JP 8123554 A JP8123554 A JP 8123554A JP 12355496 A JP12355496 A JP 12355496A JP H09302247 A JPH09302247 A JP H09302247A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- conductive filler
- structural unit
- antistatic
- conductive
- 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
- 239000011342 resin composition Substances 0.000 title claims description 24
- 239000011231 conductive filler Substances 0.000 claims abstract description 35
- 229920003118 cationic copolymer Polymers 0.000 claims abstract description 25
- 229920000620 organic polymer Polymers 0.000 claims abstract description 13
- 239000002861 polymer material Substances 0.000 claims abstract description 13
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 abstract description 26
- 239000011347 resin Substances 0.000 abstract description 26
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 4
- 239000005977 Ethylene Substances 0.000 abstract description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract description 4
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 125000003710 aryl alkyl group Chemical group 0.000 abstract description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 125000005843 halogen group Chemical group 0.000 abstract 1
- 238000000034 method Methods 0.000 description 23
- 238000012360 testing method Methods 0.000 description 17
- 239000002216 antistatic agent Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- -1 polyethylene Polymers 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 235000019241 carbon black Nutrition 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000001143 conditioned effect Effects 0.000 description 3
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000007112 amidation reaction Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- PMNLUUOXGOOLSP-UHFFFAOYSA-M 2-sulfanylpropanoate Chemical compound CC(S)C([O-])=O PMNLUUOXGOOLSP-UHFFFAOYSA-M 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006378 damage Effects 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
- 238000007865 diluting Methods 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- CGPRUXZTHGTMKW-UHFFFAOYSA-N ethene;ethyl prop-2-enoate Chemical compound C=C.CCOC(=O)C=C CGPRUXZTHGTMKW-UHFFFAOYSA-N 0.000 description 1
- QHZOMAXECYYXGP-UHFFFAOYSA-N ethene;prop-2-enoic acid Chemical compound C=C.OC(=O)C=C QHZOMAXECYYXGP-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- SWVGZFQJXVPIKM-UHFFFAOYSA-N n,n-bis(methylamino)propan-1-amine Chemical compound CCCN(NC)NC SWVGZFQJXVPIKM-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- AAJFCINGYYYJGX-UHFFFAOYSA-N phenoxybenzene;hydrobromide Chemical class Br.C=1C=CC=CC=1OC1=CC=CC=C1 AAJFCINGYYYJGX-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、導電性樹脂組成物
（以下、「帯電防止性樹脂組成物」ともいう）に関し、
詳しくは、優れた帯電防止性を有する樹脂製品を得るこ
とができる導電性樹脂組成物に関する。TECHNICAL FIELD The present invention relates to a conductive resin composition (hereinafter, also referred to as “antistatic resin composition”),
More specifically, the present invention relates to a conductive resin composition capable of obtaining a resin product having excellent antistatic properties.
【０００２】[0002]
【従来の技術と発明が解決しようとする課題】熱可塑性
樹脂等の有機高分子材料は、樹脂自身の本質的性質とし
て、一般的に電気絶縁性が極めて高く、また導電性に乏
しい。このため、静電気の発生が避けられず、一端発生
した静電気は逃げずに蓄積される傾向がある。2. Description of the Related Art Organic polymer materials such as thermoplastic resins generally have extremely high electrical insulating properties and poor electrical conductivity as the essential properties of the resins themselves. For this reason, the generation of static electricity is unavoidable, and the static electricity generated once tends to accumulate without escape.
【０００３】この静電気の蓄積により、熱可塑性樹脂よ
りなる部品が空気中の埃を吸引付着して故障の原因とな
ったり、当該部品の組立工程中にその生産能率を低下さ
せたりしていた。また、静電気が原因で電子部品を損傷
する問題も生じた。Due to the accumulation of static electricity, a component made of a thermoplastic resin attracts and attaches dust in the air to cause a failure, or the production efficiency of the component is lowered during the assembly process of the component. In addition, the problem of damaging electronic components due to static electricity also occurred.
【０００４】そこで、従来、有機高分子材料の帯電を防
止する方法として、次のような提案がなされた。Therefore, conventionally, the following proposal has been made as a method for preventing the electrification of the organic polymer material.
【０００５】帯電防止剤を樹脂成形品等の表面に塗布
する方法 有機高分子材料として熱可塑性樹脂を用いる場合にあ
っては、樹脂の可塑化温度以上で帯電防止剤を練り込む
方法。Method of applying an antistatic agent to the surface of a resin molded article, etc. When a thermoplastic resin is used as the organic polymer material, a method of kneading the antistatic agent at the plasticizing temperature of the resin or higher.
【０００６】しかしながら、上記、には次のような
問題点があった。However, the above problems have the following problems.
【０００７】でいう塗布型の帯電防止剤は、その殆ど
が界面活性剤である。界面活性剤には、アニオン系活性
剤、カチオン系活性剤、非イオン系活性剤、両性活性剤
があり、これらを水またはアルコール等で希釈し塗布す
る。この方法は簡便ではあるが、帯電防止効果の持続性
及び湿度依存性という点で問題があった。Most of the coating type antistatic agents referred to above are surfactants. Surfactants include anionic activators, cationic activators, nonionic activators, and amphoteric activators, which are diluted with water or alcohol before coating. Although this method is simple, it has a problem in terms of durability of the antistatic effect and humidity dependency.
【０００８】の練り込み型帯電防止剤としては、前述
の界面活性剤の他に高分子系帯電防止剤も使用されてい
る。また、高分子系帯電防止剤としては、ポリエーテル
系、ポリエーテルエステル系、ポリアクリル酸系、ポリ
スチレンスルホン酸系が実用化されている。この帯電防
止剤は、帯電防止効果が湿度の影響を受けにくい等の利
点があるが、効果を得るためには添加量を多くする必要
があった。このため、熱可塑性樹脂の物性に影響を与
え、必要とした物性を得ることが難しいという問題があ
った。As the kneading type antistatic agent, a polymeric antistatic agent is also used in addition to the above-mentioned surfactant. As the polymer antistatic agent, polyether type, polyether ester type, polyacrylic acid type, and polystyrene sulfonic acid type have been put into practical use. This antistatic agent has an advantage that the antistatic effect is not easily affected by humidity, but it is necessary to increase the addition amount in order to obtain the effect. Therefore, there is a problem that the physical properties of the thermoplastic resin are affected and it is difficult to obtain the required physical properties.
【０００９】この問題に鑑み、本発明者等は先に、特開
平５−３２０５２６号公報、特開平６−２７１７８０号
公報等に示されるカチオン性共重合体を用い、比較的少
ない添加量で高い帯電防止性能を示す樹脂組成物を提案
している。In view of this problem, the inventors of the present invention previously used the cationic copolymers disclosed in JP-A-5-320526 and JP-A-6-27178, and used a comparatively small amount of the cationic copolymer. A resin composition showing antistatic performance is proposed.
【００１０】しかしながら、上記技術を以てしても、得
られる樹脂組成物の表面固有抵抗はせいぜい１０12〜１
０9 Ωであり、１０9 Ω程度あるいはそれ以下の表面固
有抵抗値を得ようとする場合には、やはり添加量を多く
する必要が生じた。However, even with the above technique, the surface resistivity of the resulting resin composition is at most 10 12 -1.
In order to obtain a surface specific resistance value of 0 9 Ω and about 10 9 Ω or less, it is necessary to increase the addition amount.
【００１１】前述したように、従来の帯電防止性材料を
用いた場合、得られる樹脂製品の表面固有抵抗率は１０
11Ω前後である。このレベルは、通常の埃付着防止等を
目的とするという点では充分満足できるレベルである。As described above, when the conventional antistatic material is used, the surface resistivity of the obtained resin product is 10
It is around 11 Ω. This level is a level that is sufficiently satisfactory in terms of ordinary dust adhesion prevention and the like.
【００１２】しかしながら、近年の帯電防止に対する要
求の高度化（例えば、電子部品の組立、搬送、包装材料
等の使用に対する要求の高度化）により、表面固有抵抗
値が１０10〜１０8 Ωに正確にコントロールされた帯電
防止性材料が求められてきている。However, due to the recent sophistication of antistatic requirements (for example, sophistication of requirements for assembling electronic components, transportation, and use of packaging materials, etc.), the surface specific resistance value is accurate to 10 10 to 10 8 Ω. There is a demand for antistatic materials that are controlled by the above.
【００１３】導電性をさらに向上させる方法として、 カーボンブラック、金属粉などの導電性物質を、有機
高分子材料に配合して導電性を付与する方法が行なわれ
てきた。すなわち、カーボンブラック、カーボンファイ
バー、金属微粉末、金属酸化物、非導電性フィラーに金
属または金属酸化物を被覆した材料などの導電性材料
を、有機高分子材料に配合して導電性を付与する方法が
行なわれてきた。As a method for further improving the conductivity, a method has been used in which a conductive substance such as carbon black or metal powder is blended with an organic polymer material to impart conductivity. That is, a conductive material such as carbon black, carbon fiber, fine metal powder, metal oxide, or a material obtained by coating a metal or a metal oxide on a non-conductive filler is added to an organic polymer material to impart conductivity. The method has been done.
【００１４】上記の方法は、前述の帯電防止剤を用い
る方法（、）に比べて帯電防止効果は永続的であ
り、導電性材料の耐熱性も良好である。In the above method, the antistatic effect is more permanent and the heat resistance of the conductive material is better than that of the method (,) using the antistatic agent.
【００１５】しかしながら、導電性フィラーとして体積
抵抗率が１０-1Ω・ｃｍ程度のカーボン系導電性フィラ
ーを用いた場合、製品の表面固有抵抗値を１０8 〜１０
10Ωの範囲に精度良く制御することが極めて困難となっ
た。つまり、導電性フィラーの添加量に対する帯電防止
性樹脂組成物の表面固有抵抗値の変化が急激となり、僅
かな添加量の変動に対しても表面固有抵抗率は１０12Ω
以上〜１０4 Ω程度まで変化した。However, when a carbon-based conductive filler having a volume resistivity of about 10 −1 Ω · cm is used as the conductive filler, the surface specific resistance value of the product is 10 8 to 10
It became extremely difficult to control it within the range of 10 Ω with high precision. In other words, the surface resistivity of the antistatic resin composition changes rapidly with respect to the amount of the conductive filler added, and the surface resistivity is 10 12 Ω even with a slight change in the amount added.
Above, it changed to about 10 4 Ω.
【００１６】このため、成形部品等では、混練条件、成
形条件等による抵抗値のロット間の変動、また同一部品
内の局所的な抵抗値の変動が大きな問題となった。その
結果、成形部品等の抵抗値が高い場合には、静電気によ
る各種の障害が生じた。また逆に成形部品等の抵抗値が
低い場合には、例えば電気部品等に使用した場合、漏電
等の原因になった。For this reason, in molded parts and the like, there has been a big problem that the resistance value varies from lot to lot due to kneading conditions, molding conditions and the like, and the local resistance value varies within the same component. As a result, when the resistance value of the molded part or the like is high, various failures due to static electricity occur. On the contrary, when the resistance value of the molded part or the like is low, for example, when it is used for an electric part or the like, it causes a leakage current.
【００１７】また、導電性フィラーとして体積抵抗率が
０．５〜１０4 Ω・ｃｍの非カーボン系導電性フィラー
を用いた場合には、カーボン系導電性フィラーを使用し
たときよりも、添加量に対する表面固有抵抗率の変化は
多少緩やかではある。しかしながら、それでも、樹脂に
添加する際の混練条件の僅かな不均一性が原因で表面固
有抵抗値が１０12Ω以上〜１０5 Ω程度まで大きく変化
する場合があった。Further, when a non-carbon conductive filler having a volume resistivity of 0.5 to 10 4 Ω · cm is used as the conductive filler, the addition amount is larger than that when the carbon conductive filler is used. The change in the specific surface resistivity with respect to is slightly gradual. However, even then, there was a case where the surface specific resistance value was significantly changed to 10 12 Ω or more and 10 5 Ω or less due to a slight non-uniformity of the kneading conditions when adding to the resin.
【００１８】すなわち、導電剤としてこれらの導電性フ
ィラーを用いた場合、樹脂中に導電性フィラーによる電
荷の漏洩回路が形成されて初めて表面固有抵抗値が低下
し、その表面固有抵抗値は導電性フィラーの体積固有抵
抗値の値に大きく依存することから、このような急激な
表面固有抵抗値の変化は避けて通れず、これにより表面
固有抵抗値を１０8 〜１０10Ωの範囲に精度良く制御す
ることが極めて困難であった。That is, when these conductive fillers are used as the conductive agent, the surface specific resistance value is lowered only after a charge leakage circuit is formed by the conductive filler in the resin, and the surface specific resistance value is conductive. Since it largely depends on the value of the volume resistivity of the filler, such a sudden change in the surface resistivity cannot be avoided, and thus the surface resistivity can be accurately controlled within the range of 10 8 to 10 10 Ω. It was extremely difficult to control.
【００１９】さらには、カーボン系導電性フィラーに比
べて非カーボン系導電性フィラーは多量に添加する必要
があり、これにより帯電防止樹脂組成物の物性が変化す
る問題が生じ、また高価な導電性フィラーを多量に使用
するためコスト高を招くという問題もあった。Further, it is necessary to add a large amount of the non-carbon type conductive filler as compared with the carbon type conductive filler, which causes a problem that the physical properties of the antistatic resin composition are changed, and the expensive conductivity is high. There is also a problem that the cost is increased because a large amount of filler is used.
【００２０】［発明の目的］本発明は上記の実情に鑑み
てなされたものであり、その目的は、帯電防止性に優
れ、かつ有機高分子材料本来の特性である絶縁性および
その他の物性は維持され得る、表面固有抵抗率が１０8
〜１０10Ωの範囲に精度良く制御された樹脂製品を安価
に得ることのできる導電性樹脂組成物を提供するところ
にある。[Object of the Invention] The present invention has been made in view of the above circumstances, and its object is to provide excellent insulating properties and other physical properties that are excellent in antistatic properties and are inherent properties of organic polymer materials. Surface resistivity that can be maintained is 10 8
An object of the present invention is to provide a conductive resin composition which can inexpensively obtain a resin product accurately controlled in the range of 10 10 Ω.
【００２１】[0021]
【課題を解決するための手段】本発明の導電性樹脂組成
物は、（Ａ）有機高分子材料、（Ｂ）下記一般式［化
２］で示される構造単位（Ｉ）〜（ＩＩＩ）を含有する
カチオン性共重合体、（Ｃ）体積抵抗率が０．１〜１０
4 Ω・ｃｍの導電性フィラーが配合されてなるものであ
る。A conductive resin composition of the present invention comprises (A) an organic polymer material, (B) structural units (I) to (III) represented by the following general formula [Chemical formula 2]. Cationic copolymer contained, (C) volume resistivity of 0.1 to 10
It is made by blending a conductive filler of 4 Ω · cm.
【００２２】[0022]
【化２】 。Embedded image .
【００２３】なお、従来、本発明者らが先に、例えば特
開平７−１２６４４６号公報、特開平７−９００２６号
公報、特願平８−１９９９４号等で述べた、樹脂の機械
的物性の改良技術や、着色を目的とした充填剤の併用技
術を以てしても、本発明の効果は全く得られない。Conventionally, the present inventors have previously described, for example, Japanese Patent Application Laid-Open No. 7-126446, No. 7-90026, Japanese Patent Application No. 8-19994, etc. The effect of the present invention cannot be obtained at all even with the improved technique and the technique of using a filler for the purpose of coloring.
【００２４】[0024]
【発明の実施の形態】（Ａ）成分 本発明で用いる有機高分子材料（Ａ）の例を挙げると、
熱可塑性樹脂としては、ポリオレフィン樹脂（ポリエチ
レン、ポリプロピレン、エチレン−プロピレン共重合
体、エチレン−αオレフィン共重合体等）、ポリ塩化ビ
ニル、スチレン系樹脂（スチレンモノマーの単独重合体
（ポリスチレン）スチレンと他の共重合可能なモノマー
との共重合体（ＡＢＳ樹脂等）、ポリスチレンまたは前
記共重合体と他の熱可塑性樹脂とのポリマーアロイ
等）、（メタ）アクリル樹脂、ポリアミド樹脂（ナイロ
ン６，６、ナイロン６等）、ポリエステル樹脂（ポリエ
チレンテレフタレート、ポリブチレンテレフタレート、
ポリカーボネート等）、変性ポリフェニレンエーテル等
が例示され、これら各種熱可塑性樹脂を単独もしくはポ
リマーアロイの如く併用して使用できる。BEST MODE FOR CARRYING OUT THE INVENTION (A) Component Examples of the organic polymer material (A) used in the present invention include:
As the thermoplastic resin, polyolefin resin (polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-α-olefin copolymer, etc.), polyvinyl chloride, styrene resin (styrene monomer homopolymer (polystyrene), styrene and others A copolymer with a copolymerizable monomer (ABS resin or the like), polystyrene or a polymer alloy of the above copolymer and another thermoplastic resin), a (meth) acrylic resin, a polyamide resin (nylon 6,6, Nylon 6 etc.), polyester resin (polyethylene terephthalate, polybutylene terephthalate,
Examples thereof include polycarbonate) and modified polyphenylene ether, and these various thermoplastic resins can be used alone or in combination as polymer alloys.
【００２５】熱硬化性樹脂ではフェノール樹脂、不飽和
ポリエステル樹脂、エポキシ樹脂、ジアリルフタレート
樹脂、ポリウレタン樹脂、シリコーン等が挙げられる。Examples of the thermosetting resin include phenol resin, unsaturated polyester resin, epoxy resin, diallyl phthalate resin, polyurethane resin and silicone.
【００２６】（Ｂ）成分 本発明に使用されるカチオン性共重合体（Ｂ）は、上記
［化１］の構造単位（Ｉ）〜（ＩＩＩ）を有するもので
ある。以下に詳しく説明する。 Component (B) The cationic copolymer (B) used in the present invention has the structural units (I) to (III) of the above [Chemical Formula 1]. This will be described in detail below.
【００２７】本発明に用いるカチオン性共重合体（Ｂ）
において、エチレン構造単位（Ｉ）の割合は、分子内に
８０〜９８モル％である。この含有割合が８０モル％未
満であればマトリックス樹脂への相溶性が極端に悪化
し、押出機を用いての樹脂組成物の製造が困難になるば
かりでなく、得られた樹脂組成物を用いて成形した成形
体の耐水性と機械的物性が著しく低下する。また、含有
割合が９８モル％を超える場合には本発明の目的とする
表面固有抵抗値を安定的に発現できない。相溶性、物性
と帯電防止能の安定性との観点から、エチレン構造単位
（Ｉ）の含有割合は、８５．０〜９７．５モル％が好ま
しい。Cationic copolymer (B) used in the present invention
In, the proportion of the ethylene structural unit (I) is 80 to 98 mol% in the molecule. If this content ratio is less than 80 mol%, the compatibility with the matrix resin is extremely deteriorated, making it difficult to manufacture the resin composition using an extruder, and using the obtained resin composition. The water resistance and mechanical properties of the molded article molded by the above method are significantly reduced. On the other hand, if the content exceeds 98 mol%, the surface resistivity of the present invention cannot be stably exhibited. From the viewpoints of compatibility, physical properties, and stability of antistatic ability, the content ratio of the ethylene structural unit (I) is preferably 85.0 to 97.5 mol%.
【００２８】また、（Ｂ）成分において、アクリレート
構造単位（ＩＩ）は、分子内に０〜１５モル％含有され
ている。アクリレート構造単位（ＩＩ）が含有されてい
ることにより、カチオン性共重合体とマトリックス樹脂
との相溶性が向上する。アクリレート構造単位（ＩＩ）
の含有割合が１５モル％を超える場合には樹脂組成物の
物性が悪化する。なお、相溶性の観点からアクリレート
構造単位（ＩＩ）の含有割合は３〜１３モル％程度が好
ましい。アクリレート構造単位において、Ｒ１はメチル
基又はエチル基を表し、Ｒ１は構造単位毎に同一であっ
ても異なってもよい（すなわち、メチル基とエチル基が
１分子中に混在してもよい）。In the component (B), the acrylate structural unit (II) is contained in the molecule in an amount of 0 to 15 mol%. When the acrylate structural unit (II) is contained, the compatibility between the cationic copolymer and the matrix resin is improved. Acrylate structural unit (II)
When the content ratio of is more than 15 mol%, the physical properties of the resin composition are deteriorated. From the viewpoint of compatibility, the content of the acrylate structural unit (II) is preferably about 3 to 13 mol%. In the acrylate structural unit, R 1 represents a methyl group or an ethyl group, and R 1 may be the same or different for each structural unit (that is, a methyl group and an ethyl group may be mixed in one molecule). ).
【００２９】カチオン性共重合体におけるアクリルアミ
ド構造単位（ＩＩＩ）は、４級アンモニウム塩の形にし
たカチオン性のアクリルアミド構造単位であり、その割
合は分子内に２〜２０モル％含有されている。この含有
割合が２モル％未満の場合には樹脂組成物が安定的に１
０8 〜１０10Ωの表面固有抵抗値を示さない。また、含
有割合が２０モル％を超える場合にはカチオン性共重合
体のマトリックス樹脂への相溶性が悪化し、押出機を用
いての樹脂組成物の製造が困難であるばかりか、該樹脂
組成物を用いて成形した成形体の耐水性と機械的物性が
低下する。帯電防止能の安定性と相溶性、物性との観点
から、アクリルアミド構造単位（ＩＩＩ）の含有割合は
２．５〜１５モル％が好ましい。The acrylamide structural unit (III) in the cationic copolymer is a cationic acrylamide structural unit in the form of a quaternary ammonium salt, the proportion of which is 2 to 20 mol% in the molecule. When this content ratio is less than 2 mol%, the resin composition is stably 1
It does not show a surface specific resistance value of 0 8 to 10 10 Ω. On the other hand, if the content exceeds 20 mol%, the compatibility of the cationic copolymer with the matrix resin deteriorates, making it difficult to produce a resin composition using an extruder, The water resistance and mechanical properties of the molded product molded from the product are reduced. From the viewpoint of stability of antistatic ability, compatibility, and physical properties, the content ratio of the acrylamide structural unit (III) is preferably 2.5 to 15 mol%.
【００３０】なお、アクリルアミド構造単位の一般式Ｒ
２は、エチレン基又はプロピレン基を表しこれらは１分
子中に混在してもよく、Ｒ３及びＲ４は、メチル基を表
し、Ｒ５は製造の容易さや良好な帯電防止能が得られる
といった観点から、メチル基、エチル基等の低級直鎖状
アルキル基又はベンジル基等のアリールアルキル基を表
す。さらに、ＸはＣｌ、Ｂｒ、Ｉ等のハロゲン化物イオ
ン、ＣＨ３ＯＳＯ３、ＣＨ３ＣＨ２ＯＳＯ３を表す。The general formula R of the acrylamide structural unit
2 represents an ethylene group or a propylene group, and these may be mixed in one molecule, R 3 and R 4 represent a methyl group, and R 5 provides easy production and good antistatic ability. From the viewpoint, it represents a lower linear alkyl group such as a methyl group or an ethyl group, or an arylalkyl group such as a benzyl group. Further, X represents a halide ion such as Cl, Br, I, CH 3 OSO 3 , CH 3 CH 2 OSO 3 .
【００３１】上述したカチオン性共重合体（Ｂ）の重量
平均分子量の測定はゲルパーミュエーションクロマトグ
ラフィーで行い、ポリスチレン換算の重量平均分子量で
超高温ＧＰＣ法（絹川、「高分子論文集第４４巻２
号」、１３９〜１４１頁、１９８７）に準じて測定でき
るが、その重量平均分子量の範囲は１，０００〜５０，
０００である。重量平均分子量が１，０００未満の場合
には、カチオン性共重合体がワックス状となり、ハンド
リング性が悪化し、さらには過度のブリードアウトによ
り樹脂表面の粘着性が増すという問題を生じ、重量平均
分子量が５０，０００を超える場合には、マトリックス
樹脂への相溶性が悪化するという問題を生じる。なお、
カチオン性共重合体の好ましい重量平均分子量は３，０
００〜３０，０００である。The above-mentioned weight average molecular weight of the cationic copolymer (B) was measured by gel permeation chromatography, and the weight average molecular weight in terms of polystyrene was used for the ultra-high temperature GPC method (Kinukawa, "Polymer Thesis Collection 44"). Volume 2
No. ”, pp. 139-141, 1987), but the range of the weight average molecular weight is 1,000-50,
000. If the weight average molecular weight is less than 1,000, the cationic copolymer becomes a waxy form, the handling property deteriorates, and further there is a problem that the adhesiveness of the resin surface increases due to excessive bleed-out, and the weight average molecular weight increases. If the molecular weight exceeds 50,000, the compatibility with the matrix resin deteriorates. In addition,
The preferred weight average molecular weight of the cationic copolymer is 3,0.
00 to 30,000.
【００３２】本発明の樹脂組成物において用いるカチオ
ン性共重合体の製造方法としては、例えば、エチレンと
アクリル酸エステルとを高圧重合法により共重合させて
得られるエチレン−アクリル酸エステル共重合体を、特
開昭６０−７９００８号公報に記載の方法により加水分
解と同時に熟減成して所望の分子量とし、さらに、得ら
れたエチレン−アクリル酸エステル−アクリル酸共重合
体をＮ，Ｎ−ジアルキルアミノアルキルアミンでアミド
化した後公知の４級化剤でカチオン変性し単離して上記
カチオン性共重合体を得るというものである。The method for producing the cationic copolymer used in the resin composition of the present invention is, for example, an ethylene-acrylic acid ester copolymer obtained by copolymerizing ethylene and an acrylic acid ester by a high pressure polymerization method. And hydrolysis and aging to obtain a desired molecular weight by the method described in JP-A-60-79008, and the ethylene-acrylic acid ester-acrylic acid copolymer obtained is further treated with N, N-dialkyl. The above-mentioned cationic copolymer is obtained by amidation with an aminoalkylamine, followed by cation modification with a known quaternizing agent and isolation.
【００３３】本発明の樹脂組成物において、前述したカ
チオン性共重合体の配合量は実用的には樹脂組成物中に
１〜１０重量％である。この配合量が１重量％未満の場
合には安定的に１０10〜１０8 Ωの表面固有抵抗値を得
にくくなり、逆に配合量が１０重量％を超える場合には
樹脂の機械的物性、特に衝撃強度が低下する。樹脂にお
ける帯電防止性と機械的物性とのバランスから、カチオ
ン性共重合体の配合量は５〜８重量％が特に好ましい。In the resin composition of the present invention, the compounding amount of the above-mentioned cationic copolymer is practically 1 to 10% by weight in the resin composition. When the blending amount is less than 1% by weight, it becomes difficult to stably obtain a surface specific resistance value of 10 10 to 10 8 Ω. On the contrary, when the blending amount exceeds 10% by weight, the mechanical properties of the resin, Especially, the impact strength is lowered. From the balance between the antistatic property and the mechanical properties of the resin, the amount of the cationic copolymer is particularly preferably 5 to 8% by weight.
【００３４】（Ｃ）成分 本発明で使用される導電性フィラー（Ｃ）は、アセチレ
ンブラック、チャネルブラックなどのカーボンブラック
類に代表されるカーボン系導電性フィラー、アンチモン
をドープした酸化スズ導電層を、酸化チタンあるいはチ
タン酸カリウムの表面に処理した導電性フィラー、Ａｌ
3+をドープした導電性酸化亜鉛などが使用可能である。 Component (C) The conductive filler (C) used in the present invention is a carbon-based conductive filler typified by carbon blacks such as acetylene black and channel black, and a tin oxide conductive layer doped with antimony. Conductive filler treated on the surface of titanium oxide or potassium titanate, Al
Conductive zinc oxide doped with 3+ can be used.
【００３５】本発明において、（Ｃ）成分の体積抵抗率
は０．１〜１０4 Ω・ｃｍに限定される。その好ましい
範囲は、０．１〜５００Ω・ｃｍであり、さらに好まし
い範囲は、０．１〜３００Ω・ｃｍである。In the present invention, the volume resistivity of the component (C) is limited to 0.1 to 10 4 Ω · cm. The preferable range is 0.1 to 500 Ω · cm, and the more preferable range is 0.1 to 300 Ω · cm.
【００３６】また、本発明の導電性樹脂組成物中におけ
る導電性フィラー（Ｃ）の含有割合は、導電性フィラー
の持つ体積抵抗率やフィラーの粒子形状によって異なる
が、概ね１０〜４０重量％であることが好適である。Although the content ratio of the conductive filler (C) in the conductive resin composition of the present invention varies depending on the volume resistivity of the conductive filler and the particle shape of the filler, it is generally 10 to 40% by weight. Preferably.
【００３７】その他 本発明の樹脂組成物は、前述のカチオン性共重合体
（Ｂ）と導電性フィラー（Ｃ）以外に、他の添加物、例
えば着色、機械的物性の改善等を目的として炭酸カルシ
ウム、タルク、ガラス繊維の無機充填剤、テトラキス
（２，４−ジｔｅｒｔブチルフェニル）−４，４′ビフ
ェニレンジホスホナイト等の熱安定剤、テトラキス［メ
チレン−３（３−５ジｔｅｒｔブチル−４−ヒドロオキ
シ−フェニル）プロピオネート］メタン等のヒンダード
フェノール系、メルカプトプロピオン酸エステル等のチ
オ系酸化防止剤、ヘキサブロモシクロドデカン、テトラ
ブロモビスフェノールＡやその誘導体さらにはジフェニ
ルエーテルの臭素化物等の含臭素系難燃剤や含リン化合
物難燃剤及びＳｂ２Ｏ３等の難燃助剤、非イオン系もし
くはカチオン系界面活性剤、ポリオキシエチレン鎖を持
つポリマー、例えばポリオキシエチレンやポリエチレン
グリコールをエステル結合、アミド結合あるいはイミド
結合で重縮合させた高分子量体もしくはウレタン結合、
エポキシエステル結合、エポキシエーテル結合で重付加
させた高分子量体である帯電防止剤を同時に添加しても
差しつかえない。 Others In addition to the above-mentioned cationic copolymer (B) and conductive filler (C), the resin composition of the present invention comprises other additives such as carbonic acid for the purpose of coloring and improving mechanical properties. Inorganic fillers of calcium, talc, glass fiber, thermal stabilizers such as tetrakis (2,4-ditertbutylphenyl) -4,4'biphenylenediphosphonite, tetrakis [methylene-3 (3-5ditertbutyl-). 4-Hydroxy-phenyl) propionate] Methane and other hindered phenols, mercaptopropionate and other thio antioxidants, hexabromocyclododecane, tetrabromobisphenol A and its derivatives, and bromine compounds such as diphenyl ether bromides. system flame retardants and phosphorus-containing compounds flame retardants and Sb 2 O 3 or the like of the flame retardant aid, nonionic also lay Cationic surfactants, polymers having a polyoxyethylene chain, such as polyoxyethylene or polyethylene glycol ester bond, an amide bond or polycondensation was high molecular weight material or a urethane bond in an imide bond,
It is safe to add an antistatic agent, which is a high molecular weight polymer polyadded with an epoxy ester bond or an epoxy ether bond, at the same time.
【００３８】本発明により得られた帯電防止樹脂組成物
はカレンダー加工並びに射出、押し出し、ブロー、圧縮
成形等の法任意の加工方法並びに成形方法によってシー
トまたは成形体として使用することができる。The antistatic resin composition obtained by the present invention can be used as a sheet or a molded body by any processing method and molding method such as calendering, injection, extrusion, blow, compression molding and the like.
【００３９】本発明は前述の導電性フィラーとカチオン
性共重合体の適量を有機高分子材料に混合分散すること
で帯電防止性を付与することを特徴とする帯電防止方法
である。混合分散方法は任意の方法、例えば混練ロー
ル、バンバリーミキサー、押出機等により行う。混合分
散は導電性フィラーが有機高分子材料中に均一に分散す
るまで充分に行う必要がある。導電性フィラーの分散が
不十分な場合は良好な帯電防止性能が得られない。また
混合分散工程での強い剪断力等による導電性フィラーの
破壊を避ける必要がある。導電性フィラーが破壊された
場合、本来の導電性能が損なわれる。従って、用いる材
料並びに混合分散方法により最適な混合分散条件を適宜
選択する必要がある。また所定濃度以上の導電性フィラ
ーを練り込んだ高濃度組成物を調製し、これを希釈用の
樹脂と混練してもよい。The present invention is an antistatic method characterized by imparting antistatic property by mixing and dispersing an appropriate amount of the above-mentioned conductive filler and cationic copolymer in an organic polymer material. The mixing and dispersing method is performed by any method, for example, a kneading roll, a Banbury mixer, an extruder or the like. The mixing and dispersion must be sufficiently performed until the conductive filler is uniformly dispersed in the organic polymer material. If the dispersion of the conductive filler is insufficient, good antistatic performance cannot be obtained. Further, it is necessary to avoid destruction of the conductive filler due to strong shearing force in the mixing and dispersing process. When the conductive filler is broken, the original conductive performance is impaired. Therefore, it is necessary to appropriately select the optimum mixing and dispersing conditions depending on the materials used and the mixing and dispersing method. Alternatively, a high-concentration composition in which a conductive filler having a predetermined concentration or more is kneaded may be prepared and kneaded with a diluting resin.
【００４０】本発明の用途例としては、電子材料包装材
料（ＩＣトレイ、マガジンレール、キャリアテープ、導
電性発泡プラスチック）等が挙げられる。Examples of applications of the present invention include electronic material packaging materials (IC trays, magazine rails, carrier tapes, conductive foam plastics) and the like.
【００４１】[0041]
【実施例】以下、本発明を実施例に従って説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to embodiments.
【００４２】カチオン性共重合体の合成例（合成例Ａ） 温度例、撹拌機、滴下ロート及びディーン・スターク分
水器を備えた１リットルの４つ口フラスコに、キシレン
４００ｍｌ、エチレン・アクリル酸エチル・アクリル酸
共重合体（エチレン／エチルアクリレート／アクリル酸
＝９３／３／４）１５０ｇ及びパラトルエンスルホン酸
１．０ｇを仕込んだ。次に、Ｎ，Ｎ−ジメチルアミノプ
ロピルアミン２１．１ｇを仕込み、オイルバスを用いて
１４０℃に加熱して生成した水をキシレンとの共沸によ
り連続的に除去し、さらに、１４０℃で１７時間反応
し、生成する水の共沸が認められなくなるまでアミド化
反応を継続した。 Synthesis Example of Cationic Copolymer (Synthesis Example A) 400 ml of xylene and ethylene acrylic acid were placed in a 1 liter four-necked flask equipped with a temperature example, a stirrer, a dropping funnel and a Dean-Stark water diverter. 150 g of an ethyl-acrylic acid copolymer (ethylene / ethyl acrylate / acrylic acid = 93/3/4) and 1.0 g of paratoluenesulfonic acid were charged. Next, 21.1 g of N, N-dimethylaminopropylamine was charged, and water produced by heating to 140 ° C. using an oil bath was continuously removed by azeotropic distillation with xylene. The reaction was continued for an hour, and the amidation reaction was continued until no azeotropic formation of water was observed.
【００４３】得られた反応物４５８ｇを８０℃まで冷却
し、そこへ滴下ロートよりジエチル硫酸３１．１ｇを１
時間かけて徐々に滴下した。この間、発熱が認められた
が、冷却することにより反応温度を９０℃に維持し、滴
下終了後は１００℃で４時間熟成反応を行った。458 g of the obtained reaction product was cooled to 80 ° C., and 31.1 g of diethylsulfate was added to the reaction mixture through a dropping funnel.
It was dripped gradually over time. During this period, heat generation was observed, but the reaction temperature was maintained at 90 ° C. by cooling, and after completion of dropping, aging reaction was performed at 100 ° C. for 4 hours.
【００４４】ここで得られた反応物を多量のメタノール
中へ投入し、生成した沈殿物を回収、乾燥してカチオン
性共重合体Ａを得た。共重合体Ａの重量平均分子量を測
定したところ５，３００であった。The reaction product obtained here was poured into a large amount of methanol, and the produced precipitate was recovered and dried to obtain a cationic copolymer A. The weight average molecular weight of the copolymer A was measured and found to be 5,300.
【００４５】カチオン性共重合体の合成例（合成例Ｂ〜
Ｃ） 合成例Ａと同様の方法でカチオン性共重合体を合成し
た。使用した原料と得られたカチオン性共重合体の構
造、分子量を合成例Ａとともに［表１］に示す。 Synthesis Example of Cationic Copolymer (Synthesis Example B to
C) A cationic copolymer was synthesized in the same manner as in Synthesis Example A. The structures and molecular weights of the used starting materials and the obtained cationic copolymer are shown in [Table 1] together with Synthesis Example A.
【００４６】[0046]
【表１】 。[Table 1] .
【００４７】実施例１〜２、及び比較例１〜３ 下記［表２］に示す成分を、同表に示す割合で混合し、
２軸押出機を使用しシリンダー温度２２０℃に混練して
ペレットを得た。 Examples 1 and 2 and Comparative Examples 1 to 3 The components shown in the following [Table 2] were mixed in the proportions shown in the same table,
Using a twin screw extruder, the mixture was kneaded at a cylinder temperature of 220 ° C. to obtain pellets.
【００４８】さらに射出成形機によりシリンダー温度２
２０℃、金型温度３０℃で一辺６０ｍｍ、厚さ３ｍｍの
平板状の試験片を５０枚成形した。この５０枚の成形品
の中から無造作に５枚を選び、２０℃、相対湿度６５％
の条件下で２４時間調湿した後、表面固有抵抗を測定し
た。測定結果を［表３］に示す。Cylinder temperature of 2 by injection molding machine
At 20 ° C. and a mold temperature of 30 ° C., 50 flat test pieces having a side of 60 mm and a thickness of 3 mm were formed. Five pieces were randomly selected from these 50 pieces, and the temperature was 20 ° C and the relative humidity was 65%.
After conditioning for 24 hours under the above conditions, the surface resistivity was measured. The measurement results are shown in [Table 3].
【００４９】[0049]
【表２】 [Table 2]
【表３】 。[Table 3] .
【００５０】本発明における各試験片間の抵抗値に変動
が少なく、表面固有抵抗値が１０8〜１０10Ωに精度良
く制御されている。In the present invention, there is little variation in the resistance value between the test pieces, and the surface specific resistance value is accurately controlled to 10 8 to 10 10 Ω.
【００５１】比較例における各試験片間の抵抗値は、そ
の変動が大きく、導電性フィラーの添加量が少ない試験
片の抵抗値は１０14Ω以上となっており帯電防止効果が
発現していない。また、導電性フィラーの添加量が多い
場合１０8 Ω以下となる試験片も見られた。The resistance value between the test pieces in the comparative example varied greatly, and the resistance value of the test piece containing a small amount of the conductive filler was 10 14 Ω or more, and the antistatic effect was not exhibited. . In addition, there were test pieces having a resistance of 10 8 Ω or less when the amount of the conductive filler added was large.
【００５２】実施例３〜５、及び比較例４〜７ 下記［表４］に示す成分を、同表に示す割合で混合し、
２軸押出機を使用しシリンダー温度２１０℃にて混練し
てペレットを得た。 Examples 3 to 5 and Comparative Examples 4 to 7 The components shown in the following [Table 4] were mixed in the proportions shown in the same table,
The mixture was kneaded at a cylinder temperature of 210 ° C. using a twin screw extruder to obtain pellets.
【００５３】さらに射出成形機によりシリンダー温度２
２０℃、金型温度３０℃で一辺６０ｍｍ、厚さ３ｍｍの
平板を５０枚成形した。この５０枚の成形品の中から無
造作に５枚を選び、２０℃、相対湿度６５％の条件下で
２４時間調湿した後、表面固有抵抗を測定した。測定結
果を［表５］に示す。Cylinder temperature of 2 by injection molding machine
Fifty flat plates having a side of 60 mm and a thickness of 3 mm were formed at 20 ° C. and a mold temperature of 30 ° C. Five sheets were randomly selected from the 50 molded articles, conditioned at 20 ° C. and a relative humidity of 65% for 24 hours, and then the surface resistivity was measured. The measurement results are shown in [Table 5].
【００５４】[0054]
【表４】 [Table 4]
【表５】 。[Table 5] .
【００５５】本発明における各試験片間の抵抗値に変動
が少なく、表面固有抵抗値が１０8〜１０10Ωに精度良
く制御されている。In the present invention, there is little variation in the resistance value between the respective test pieces, and the surface specific resistance value is accurately controlled to 10 8 to 10 10 Ω.
【００５６】比較例における各試験片間の抵抗値は、そ
の変動が大きく、導電性フィラーの添加量が少ない試験
片の抵抗値は１０14Ω以上となっており帯電防止効果が
発現していない。また、導電性フィラーの添加量が多い
場合１０8 Ω以下となる試験片も見られた。The resistance value between the test pieces in the comparative example has a large variation, and the resistance value of the test piece with a small amount of the conductive filler added is 10 14 Ω or more, and the antistatic effect is not exhibited. . In addition, there were test pieces having a resistance of 10 8 Ω or less when the amount of the conductive filler added was large.
【００５７】実施例６〜８、及び比較例８〜１１ 下記［表６］に示す成分を、同表に示す割合で混合し、
２軸押出機を使用しシリンダー温度２４０℃で混練して
ペレットを得た。 Examples 6 to 8 and Comparative Examples 8 to 11 The components shown in the following [Table 6] were mixed in the proportions shown in the same table,
The mixture was kneaded at a cylinder temperature of 240 ° C. using a twin-screw extruder to obtain pellets.
【００５８】さらに射出成形機によりシリンダー温度２
４０℃、金型温度４０℃で一辺６０ｍｍ、厚さ３ｍｍの
平板を５０枚成形した。この５０枚の成形品の中から無
造作に５枚を選び、２０℃、相対湿度６５％の条件下で
２４時間調湿した後、表面固有抵抗を測定した。測定結
果を［表７］に示す。Cylinder temperature of 2 by injection molding machine
Fifty flat plates having a side of 60 mm and a thickness of 3 mm were formed at 40 ° C. and a mold temperature of 40 ° C. Five sheets were randomly selected from the 50 molded articles, conditioned at 20 ° C. and a relative humidity of 65% for 24 hours, and then the surface resistivity was measured. The measurement results are shown in [Table 7].
【００５９】[0059]
【表６】 [Table 6]
【表７】 。[Table 7] .
【００６０】本発明における各試験片間の抵抗値に変動
が少なく、表面固有抵抗値が１０8〜１０10Ωに精度良
く制御されている。In the present invention, there is little variation in the resistance value between the test pieces, and the surface specific resistance value is accurately controlled to 10 8 to 10 10 Ω.
【００６１】比較例における各試験片間の抵抗値は、そ
の変動が大きく、導電性フィラーの添加量が少ない試験
片の抵抗値は１０14Ω以上となっており帯電防止効果が
発現していない。また、導電性フィラーの添加量が多い
場合１０8 Ω以下となる試験片も見られた。The resistance value between the test pieces in the comparative example varied greatly, and the resistance value of the test piece containing a small amount of the conductive filler was 10 14 Ω or more, and the antistatic effect was not exhibited. . In addition, there were test pieces having a resistance of 10 8 Ω or less when the amount of the conductive filler added was large.
【００６２】実施例９〜１０、及び比較例１２〜１４ 下記［表８］に示す成分を、同表に示す割合で混合し、
２軸押出機を使用しシリンダー温度２１０℃で混練して
ペレットを得た。 Examples 9 to 10 and Comparative Examples 12 to 14 The components shown in the following [Table 8] were mixed in the proportions shown in the same table,
The mixture was kneaded at a cylinder temperature of 210 ° C. using a twin-screw extruder to obtain pellets.
【００６３】さらに射出成形機によりシリンダー温度２
１０℃、金型温度３０℃で一辺６０ｍｍ、厚さ３ｍｍの
平板を５０枚成形した。この５０枚の成形品の中から無
造作に５枚を選び、２０℃、相対湿度６５％の条件下で
２４時間調湿した後、表面固有抵抗を測定した。測定結
果を［表９］に示す。Cylinder temperature of 2 by injection molding machine
Fifty flat plates having a side of 60 mm and a thickness of 3 mm were formed at 10 ° C. and a mold temperature of 30 ° C. Five sheets were randomly selected from the 50 molded articles, conditioned at 20 ° C. and a relative humidity of 65% for 24 hours, and then the surface resistivity was measured. The measurement results are shown in [Table 9].
【００６４】[0064]
【表８】 [Table 8]
【表９】 。[Table 9] .
【００６５】本発明における各試験片間の抵抗値に変動
が少なく、表面固有抵抗値が１０8〜１０10Ωに精度良
く制御されている。In the present invention, there is little variation in the resistance value between the test pieces, and the surface specific resistance value is accurately controlled to 10 8 to 10 10 Ω.
【００６６】比較例における各試験片間の抵抗値は、そ
の変動が大きく、導電性フィラーの添加量が少ない試験
片の抵抗値は１０14Ω以上となっており帯電防止効果が
発現していない。また、導電性フィラーの添加量が多い
場合１０8 Ω以下となる試験片も見られた。The resistance value between the test pieces in the comparative example has a large variation, and the resistance value of the test piece with a small amount of the conductive filler added is 10 14 Ω or more, and the antistatic effect is not exhibited. . In addition, there were test pieces having a resistance of 10 8 Ω or less when the amount of the conductive filler added was large.
【００６７】[0067]
【発明の効果】本発明の帯電防止性（導電性）樹脂組成
物によって得られる樹脂製品は、表面固有抵抗が１０10
〜１０8 Ωに精度良く制御されており、そのため、優れ
た帯電防止性を示すとともに、樹脂本来の持つ絶縁性は
維持される。しかも、前記した帯電防止性は永続的であ
る。The resin product obtained from the antistatic (conductive) resin composition of the present invention has a surface resistivity of 10 10
It is precisely controlled to 810 8 Ω, so that it exhibits excellent antistatic properties and maintains the inherent insulation properties of the resin. Moreover, the above-described antistatic property is permanent.
【００６８】本発明の帯電防止性樹脂組成物は帯電防止
性材料として、電子材料包装材料として好適に使用でき
るものである。The antistatic resin composition of the present invention can be suitably used as an antistatic material and as a packaging material for electronic materials.
Claims (3)
（ＩＩＩ）を含有するカチオン性共重合体、 （Ｃ）体積抵抗率が０．１〜１０4 Ω・ｃｍの導電性フ
ィラーが配合されてなる導電性樹脂組成物。 【化１】 1. An organic polymer material (A), (B) structural units (I) to
A cationic copolymer containing (III), (C) a conductive resin composition containing a conductive filler having a volume resistivity of 0.1 to 10 4 Ω · cm. Embedded image
項１記載の組成物。2. The composition according to claim 1, wherein the component (A) is a thermoplastic resin.
請求項１又は２記載の組成物。3. The composition according to claim 1, which contains 1 to 10% by weight of the component (B).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8123554A JPH09302247A (en) | 1996-05-17 | 1996-05-17 | Conductive resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8123554A JPH09302247A (en) | 1996-05-17 | 1996-05-17 | Conductive resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09302247A true JPH09302247A (en) | 1997-11-25 |
Family
ID=14863481
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8123554A Pending JPH09302247A (en) | 1996-05-17 | 1996-05-17 | Conductive resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09302247A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002060981A1 (en) * | 2001-02-01 | 2002-08-08 | Mitsumi Electric Co., Ltd. | Glass epoxy board and magnetic head device |
-
1996
- 1996-05-17 JP JP8123554A patent/JPH09302247A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002060981A1 (en) * | 2001-02-01 | 2002-08-08 | Mitsumi Electric Co., Ltd. | Glass epoxy board and magnetic head device |
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