JPH0510391B2 - - Google Patents
Info
- Publication number
- JPH0510391B2 JPH0510391B2 JP19730483A JP19730483A JPH0510391B2 JP H0510391 B2 JPH0510391 B2 JP H0510391B2 JP 19730483 A JP19730483 A JP 19730483A JP 19730483 A JP19730483 A JP 19730483A JP H0510391 B2 JPH0510391 B2 JP H0510391B2
- Authority
- JP
- Japan
- Prior art keywords
- carbon black
- weight
- furnace
- conductive carbon
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 45
- 239000000203 mixture Substances 0.000 claims description 41
- 229930195733 hydrocarbon Natural products 0.000 claims description 29
- 150000002430 hydrocarbons Chemical class 0.000 claims description 29
- 238000010521 absorption reaction Methods 0.000 claims description 24
- 239000004215 Carbon black (E152) Substances 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 18
- 229920003051 synthetic elastomer Polymers 0.000 claims description 14
- 229920003002 synthetic resin Polymers 0.000 claims description 14
- 239000000057 synthetic resin Substances 0.000 claims description 14
- 239000005061 synthetic rubber Substances 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000002309 gasification Methods 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001882 dioxygen Inorganic materials 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 description 29
- 235000019241 carbon black Nutrition 0.000 description 29
- 239000003921 oil Substances 0.000 description 26
- 150000001875 compounds Chemical class 0.000 description 13
- -1 polypropylene Polymers 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 229920001971 elastomer Polymers 0.000 description 11
- 239000005060 rubber Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 239000006230 acetylene black Substances 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 241000872198 Serjania polyphylla Species 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 239000000295 fuel oil Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 2
- 229920000299 Nylon 12 Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000011231 conductive filler Substances 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- FEXBEKLLSUWSIM-UHFFFAOYSA-N 2-Butyl-4-methylphenol Chemical compound CCCCC1=CC(C)=CC=C1O FEXBEKLLSUWSIM-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- REUJCMPVVNETJW-UHFFFAOYSA-N 6-tert-butyl-2-[(3-tert-butyl-2-hydroxy-6-methylphenyl)methyl]-3-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1CC1=C(C)C=CC(C(C)(C)C)=C1O REUJCMPVVNETJW-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241000239290 Araneae Species 0.000 description 1
- 235000010893 Bischofia javanica Nutrition 0.000 description 1
- 240000005220 Bischofia javanica Species 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- CVWPHEFABQVDCW-UHFFFAOYSA-N C1(=CC=CC=C1)O.C=C(C(=O)O)CC1=CC(=C(C(=C1)C(C)(C)C)O)C(C)(C)C.C=C(C(=O)O)CC1=CC(=C(C(=C1)C(C)(C)C)O)C(C)(C)C.C=C(C(=O)O)CC1=CC(=C(C(=C1)C(C)(C)C)O)C(C)(C)C.C=C(C(=O)O)CC1=CC(=C(C(=C1)C(C)(C)C)O)C(C)(C)C Chemical compound C1(=CC=CC=C1)O.C=C(C(=O)O)CC1=CC(=C(C(=C1)C(C)(C)C)O)C(C)(C)C.C=C(C(=O)O)CC1=CC(=C(C(=C1)C(C)(C)C)O)C(C)(C)C.C=C(C(=O)O)CC1=CC(=C(C(=C1)C(C)(C)C)O)C(C)(C)C.C=C(C(=O)O)CC1=CC(=C(C(=C1)C(C)(C)C)O)C(C)(C)C CVWPHEFABQVDCW-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 229920002633 Kraton (polymer) Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-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
- 235000013312 flour Nutrition 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- AJCDFVKYMIUXCR-UHFFFAOYSA-N oxobarium;oxo(oxoferriooxy)iron Chemical compound [Ba]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O AJCDFVKYMIUXCR-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Conductive Materials (AREA)
Description
本発明は、導電性に優れ、かつ熱安定性、成形
加工性、成形品外観の優れた組成物に関するもの
である。
合成樹脂や合成ゴムは一般に非導電性である
が、これらに導電性を付与することができれば、
他の導電性材料では満足が得られなかつた分野で
の利用が多いに期待される。このため合成樹脂や
合成ゴムに導電性のフイラーを配合して導電性の
組成物を得ることが種々検討されている。導電性
のフイラーの中ではカーボンブラツクが最も一般
的に検討され、その中でもケツチエンブラツク
（AKZO社商品名）が少量で高度の導電性を与え
る特徴により最も適しているということが知られ
ている。しかしながら従来のケツチエンブラツク
は不純物金属残渣（灰分）が多いためにこれを配
合した高導電性樹脂またはゴム組成物は、耐熱老
化性が極めて悪く、また、この残渣自体が“ブ
ツ”として成形品表面を悪化させたり、あるいは
この残渣によりポリマーゲルが誘発され成形品外
観を悪化させる傾向にある。また組成物の導電性
に大きく関係するDBP吸油量がカーボンブラツ
クの中では高い水準にあり樹脂またはゴムには難
分散の傾向にあつたが、製造方法の制約があるた
めに一定水準以下の吸油量のものは得られなかつ
た。
このため、DBP吸油量の比較的低い導電性カ
ーボンブラツク（たとえばアセチレンブラツクな
ど）を配合した導電性樹脂またはゴム組成物に比
べ、カーボンブラツクの分散性の差から成形品外
観等が劣位にあつた。
本発明は、灰分含有量が低く、従来よりも低い
DBP吸油量を有する特殊なカーボンブラツクを
合成樹脂または合成ゴムに配合することによつ
て、高度の導電性と熱安定性、成形加工性、成形
品外観に優れた組成物を得ることに成功したもの
である。
すなわち、本発明は、
(a)合成樹脂または合成ゴム97〜30重量％、およ
び、(b)液状炭化水素を炉内において分子状酸素及
び水蒸気の存在下部分酸化反応せしめて合成ガス
化と同時に導電性カーボンブラツクを製造するに
あたり、該液状炭化水素の炭素原子／水素原子が
重量比で９以上、該炉が炉内温度範囲1200〜1500
℃、炉内圧力10〜80Kg／cm2、炉内へ供給される水
蒸気の量が該炭化水素１トン当たり200〜800Kgの
条件で運転して得られ、かつDBP吸油量が220
ml／100ｇ以上350ml／100ｇ未満で不純物金属残
渣が0.3重量％以下の導電性カーボンブラツク３
〜70重量％からなることを特徴とする高導電性カ
ーボンブラツク配合組成物である。
本発明組成物は、高い導電性レベルで成形加工
性、成形品外観に優れ、しかも耐熱老化性などの
安定性が飛躍的に向上したもので、産業上利用性
の著しく高いものである。
本発明で使用できる上記(a)成物の合成樹脂若し
くは合成ゴムのうち、合成樹脂としては熱可塑性
樹脂または熱硬化性樹脂が用いられる。熱可塑性
樹脂としては低密度、高密度あるいは直鎖低密度
ポリエチレン、ポリプロピレン、プロピレン・エ
チレンブロツクまたはランダム共重合体などのポ
リａ−オレフイン、ポリスチレン、アクリロニト
リル・ブタジエン・スチレン三元共重合体、ポリ
メタクリル酸メチルなどのアクリル系樹脂、ポリ
塩化ビニルなどのポリホロゲン化ビニル、ナイロ
ン６、ナイロン66、ナイロン12などのポリアミ
ド、ポリエチレンテレフタレート、ポリブチレン
テレフタレートなどの飽和ポリエステル、ポリフ
エニレンオキサイドなどのポリエーテル、ポリス
ルホン、ポリフエニレンスルフイド、ポリフツ化
ビニリデン、ポリテトラフロロエチレン、エチレ
ン・酢酸ビニル共重合体、エチレン・アクリル酸
またはそのエステル共重合体、エチレン・メタク
リル酸またはそのエステル共重合体などのａ−オ
レフイン・ビニルモノマー共重合体、無水マレイ
ン酸変性ポリプロピレン、無水マレイン酸変性ポ
リエチレン、無水マレイン酸変性ポリスチレン、
ビニルシラン変性ポリプロピレン、ビニルシラン
変性ポリエチレンなどの変性樹脂、スチレン・ブ
タジエンブロツク共重合体の水添加物等の単独ま
たは混合物が用いられる。
熱硬化性樹脂としてはエポキシ樹脂、フエノー
ル樹脂、不飽和ポリエステル樹脂、メラミン樹
脂、ポリウタレン等の単独または混合物が用いら
れる。
また、合成ゴムとしてはエチレン・プロピレン
ゴム、スチレン・ブタジエンゴム、イソブレンゴ
ム等の単独または混合物が用いられる。
合成樹脂または合成ゴムには２，６−ジ−ｔ−
ブチル−４−メチルフエノール、11，３−トリ−
（２−メチル−４−ヒドロキシ−５−ｔ−ブチル
フエニル）ブタン、テトラキス〔メチレン（３，
５−ジ−ｔ−ブチル−４−ヒドロキシヒドロケイ
皮酸エステル）〕メタンなどのフエノール系酸化
防止剤、ジラウリル−チオ−ジプロビオン酸エス
テル、ジステアリル−チオ−ジプロビオン酸エス
テルなどのイオウ系酸化防止剤などの安定剤類の
ほかに紫外線吸収剤、中和剤、滑剤などを配合す
ることができる。
一方、本発明で用いる上記(b)成分のカーボンブ
ラツクは、「液状炭化水素を炉内において分子状
酸素及び水蒸気の存在下部分酸化反応せしめて合
成ガス化と同時に導電性カーボンブラツクを製造
するにあたり、該液状炭化水素の炭素原子／水素
原子が重量比で９以上、該炉が炉内温度範囲1200
〜1500℃、炉内圧力10〜80Kg／cm2、炉内へ供給さ
れる水蒸気の量が該炭化水素１トン当たり200〜
800Kgの条件で運転されることを特徴とする導電
性カーボンブラツクの製造方法」で製造される特
殊なものである。
ここで使用される液状炭化水素はＣ重油、Ａ重
油、ナフサの熱分解油（エチレンヘビーエンド）、
芳香族系液状炭化水素にカーボンブラツクを混合
した液状炭化水素（カーボンオイル）、芳香族系
液状炭化水素にＣ重油などを混合した混合オイル
などがある。これらの中でも元素分析により求め
た炭素原子及び水素原子の重量組成の比（炭素原
子／水素原子）が９以上の液状炭化水素例えばエ
チレンヘビーエンド、カーボンオイル、芳香族系
液状炭化水素にＣ重油などを混合した混合オイル
等が好ましい。更には、特に炭素原子／水素原子
の重量組成の比が12以上の例えばエチレンヘビー
エンド、カーボンオイル等が、得られるカーボン
ブラツク中の灰分量を特に低くできるので好まし
い。炭素原子／水素原子の重量比が９未満では、
該炉内の処理条件を変更してもカーボンブラツク
のDBP吸油量が著しく低下したり、又収量が小
さくなるなど好ましいカーボンブラツクの製造を
維持することが難かしい。上記原料である液状炭
化水素は、その炭素原子／水素原子の重量比が９
以上のものであつてもそれ未満のものであつても
固体状となつたり、高粘度の液状炭化水素又はカ
ーボンオイル等となつて該炉への供給が困難とな
るものなどは好ましくない。即ち、該炉内に供給
する原料炭化水素は液状であつても供給時に粘度
30cst以上如何であることが好ましい。
具体的な運転条件としては、部分酸化反応を行
う炉が炉内温度が1200〜1500℃、好ましくは1300
〜1450℃、炉内圧力10〜80Kg／cm2、好ましくは25
〜80Kg／cm2、炉内へ供給される水蒸気の量が原料
炭化水素１トン当り200〜800Kg、好ましくは300
〜800Kgの条件で運転される。これらの運転条件
と前記原料炭化水素の特徴をとを同時に満たすこ
とによつて、従来公知の条件では達成し得なかつ
た、優れた導電性を有しつつある限定された
DBP吸油量をもちしかも灰分の少ないカーボン
ブラツクを収量良く製造することができるように
なつた。
本発明の組成物に適用される導電性カーボンブ
ラツクは上記の新規な製造法で得られるもので、
かつDBP吸油量が200ml／100ｇ以上350ml／100
ｇ未満、好ましくは250ml／100ｇ以上320ml／100
ｇ以下であり、不純物金属残渣（灰分）が0.3重
量％以下のものである。ここで、DBP吸油量は
JIS−K6221−1970の測定法による。
液状炭化水素を原料とする部分酸化法は、該炭
化水素を炉内で分子状酸素及び水蒸気と反応せし
めて合成ガスを製造すると同時にカーボンブラツ
クを副生するシエルガス化プロセス、テキサコガ
ス化プロセス等が知られており、AKZO社の
「ケツチエンブラツク」はシエルガス化プロセス
により製造されたカーボンブラツクとして知られ
ている。
従来の液状炭化水素を原料とする部分酸化法に
より製造されたカーボンブラツクは、「ケツチエ
ンブラツク」に見られるように灰分が多く、
DBP吸油量もある水準のものしか得られず、樹
脂またはゴムへの分散性にも限界があつた。
これに対して本発明での特定の炉内温度、炉内
圧力、炉内供給水蒸気量によつて製造されたカー
ボンブラツクは灰分が少なく、しかも従来のもの
より低いDBP吸油量を有するものである。
本発明組成物中の上記(a)および(b)成分の配合割
合は、(a)成分の合成樹脂または合成ゴム97〜30重
量％および(b)成分の新規な導電性カーボンブラツ
ク３〜70重量％である。合成樹脂または合成ゴム
の配列割合が30重量％未満では組成物の成形性が
不良であり、97重量％超過では、高導電性が期待
されない。具体的な配合量は用途毎の要求性によ
つて設定される。
本発明の組成物として合成樹脂または合成ゴ
ム、新規な等電性カーボンブラツクにさらに無機
または有機のフイラーを好ましくは60重量％以下
配合することができる。無機フイラーとしては炭
酸カルシウム、タルク、マイカ、ガラス繊維、ウ
オラストナイト、ガラスビーズ、水酸化マグネシ
ウム、水酸化アルミニウム、硫酸バリウム、黒
鉛、二酸化モリプデン、炭素繊維、シリカ、炭素
ケイ素繊維、アルミニウム繊維、黄銅繊維、ステ
ンレススチール繊維、アルミニウムフレーク、ア
ルミニウム粉末、バリウムフエライト、ストロン
チウムフエライトなどを用いることができる。有
機フイラーとしては木粉、芳香族ポリアミド繊維
などを用いることができる。
本発明組成物はバンバリーミキサー、ロール、
ブラベンダープラストグラフなどのバツチ式の混
練機のほかに、一軸押出機、二軸押出機などの連
続式の押出機で得ることができる。配合順序は特
に限定されるものがなく、配合物を一度に混合し
て混練する方法のほかに、初めにバツチ式あるい
は連続式の押出機で合成樹脂または合成ゴムの一
部とカーボンブラツクとを混練しておき、その混
練物と合成樹脂または合成ゴムの残部とを混練す
ることもできる。
本発明組成物は、特定の導電性カーボンブラツ
クを用いることによつて次に示す予期せざる効果
を得た。
(1) 組成物の耐熱老化性などの耐久性が著しく改
良される。
(2) 合成樹脂または合成ゴムに対する分散性が改
良され成形品外観が良好である。
(3) 従来のケツチエンブラツクに比らべ同一充填
基準で配合樹脂またはゴムの溶融粘度が小さく
流動性に優れるため成形加工性が良好である。
また、アセチレンブラツクや一般の導電フアー
ネスブラツクに比らべ所定の導電率を与えるた
めの充填量が大幅に低滅化できるために材料強
度および成形加工性に優れる。
(4) 導電性の指標とされているDBP吸油量が従
来のケツチエンブラツクよりも低いにもかかわ
らず高度の導電性を示す。
参考例 １
原料液状炭化水素の性状が、
初留温度 180〜190℃
10％留出温度 205〜215℃
50％留出温度 250〜260℃
97％留出温度 320〜340℃
粘度（80℃） 約10cst
炭素原子／水素原子（重量比） 12.5
なるエチレンヘビーエンドをシエルガス化プロセ
スの炉に使用した。
導電性カーボンブラツク１；Ｃ−１
該炉の炉内温度1400℃、炉内圧力30Kg／cm2で炉
内へ供給する水蒸気の量を原料炭化水素に対して
300Kg／トン、メタン濃度0.3容量％の条件で反応
させて、DBP吸油量が290ml／100ｇ、灰分が0.02
重量％のカーボンブラツクを得た。
導電性カーボンブラツク２；Ｃ−２
該炉の炉内温度1350℃、炉内圧力30Kg／cm2で炉内
へ供給する水蒸気の量を原料炭化水素に対して
300Kg／トン、メタン濃度0.7容量％の条件で反応
させて、DBP吸油量が230ml／100ｇ、灰分が0.01
重量％のカーボンブラツクを得た。
導電性カーボンブラツク３；Ｃ−３
該炉の炉内温度1400℃、炉内圧力30Kg／cm2で炉
内へ供給する水蒸気の量を原料炭化水素に対して
400Kg／トン、メタン濃度0.3容量％の条件で反応
させて、DBP吸油量が320ml／100ｇ、灰分が0.1
重量％のカーボンブラツクを得た。
導電性カーボンブラツク４；Ｃ−４
炉内へ供給する水蒸気の量を原料炭化水素に対
して500Kg／トンとした以外は上記Ｃ−３の製造
時と同様にして、DBP吸油量418ml／100ｇ、灰
分が0.05重量％のカーボンブラツクを得た。
導電性カーボンブラツク５；Ｃ−５
炉内へ供給する水蒸気の量を原料炭化水素に対
して730Kg／トンとした以外は上記Ｃ−３の製造
時と同様にして、DBP吸油量490ml／100ｇ、灰
分が0.07重量％のカーボンブラツクを得た。
実施例 １
ポリプロピレン（MI4｝と参考例１の導電性カ
ーボンブラツク１（Ｃ−１）の所定量をブラベン
ダープラストグラフにて230℃、ローター回転数
60rpmの条件で５分間混練して得られたコンパウ
ンドを用いて厚さ２mmのプレスシートを作製し
た。このシートを用いてSRIS規格2301のホイー
トストンブリツジ法による体積抵抗率を測定し
た。なお、比較として従来のケツチエンブラツク
を用いたものについても測定した。結果を第１図
に示す。
第１図より明らかなようにポリプロビレン系に
おいてはケツチエンブラツク（DBP吸油量340〜
360ml／100ｇ）よりもDBP吸油量が小さいにか
かわらず同様の優れた導電性レベルを示すことが
把握された。
実施例 ２
ポリプロビレン（MI4）にDBP吸油量が異な
る各種導電性カーボンブラツクを組成物の体積抵
抗率が1.0〜1.5×10°Ω−cmになるよう所定量充填
した組成物について加工性の一つの目安となる
MFR（230℃、10.73Kg荷重）を測定した。結果を
第１表に示す。
The present invention relates to a composition that has excellent conductivity, thermal stability, moldability, and appearance of molded products. Synthetic resins and synthetic rubbers are generally non-conductive, but if they could be made conductive,
It is expected that it will be used in many fields where other conductive materials are unsatisfactory. For this reason, various studies have been made to obtain conductive compositions by blending conductive fillers with synthetic resins and synthetic rubbers. Among the conductive fillers, carbon black is the most commonly considered, and among these, Ketsuchen Black (trade name of AKZO) is known to be the most suitable due to its characteristics of providing a high degree of conductivity in small amounts. . However, since conventional ketchen black has a large amount of impurity metal residue (ash), the highly conductive resin or rubber composition in which it is blended has extremely poor heat aging resistance, and this residue itself forms molded products as "pieces". This tends to deteriorate the surface, or the residue induces polymer gel, which deteriorates the appearance of the molded product. In addition, the DBP oil absorption, which is greatly related to the conductivity of the composition, is at a high level among carbon blacks and tends to be difficult to disperse in resins or rubber, but due to restrictions in the manufacturing method, the oil absorption is below a certain level. I couldn't get anything in quantity. For this reason, compared to conductive resin or rubber compositions containing conductive carbon black with relatively low DBP oil absorption (such as acetylene black), the appearance of molded products was inferior due to the difference in the dispersibility of carbon black. . The present invention has a low ash content, lower than conventional
By blending a special carbon black with DBP oil absorption into synthetic resin or synthetic rubber, we succeeded in obtaining a composition with excellent conductivity, thermal stability, moldability, and molded product appearance. It is something. That is, the present invention involves subjecting (a) 97 to 30% by weight of a synthetic resin or synthetic rubber and (b) a liquid hydrocarbon to a partial oxidation reaction in the presence of molecular oxygen and water vapor in a furnace to simultaneously convert it into a synthetic gas. In producing conductive carbon black, the carbon atom/hydrogen atom weight ratio of the liquid hydrocarbon is 9 or more, and the furnace temperature range is 1200 to 1500.
℃, the furnace pressure is 10 to 80 Kg/cm 2 , the amount of steam supplied to the furnace is 200 to 800 Kg per ton of the hydrocarbon, and the DBP oil absorption is 220
Conductive carbon black 3 with impurity metal residue of 0.3% by weight or less in ml/100g or more and less than 350ml/100g
This is a composition containing highly conductive carbon black, characterized in that it consists of ~70% by weight. The composition of the present invention has a high electrical conductivity level, excellent molding processability, excellent molded product appearance, and has dramatically improved stability such as heat aging resistance, and has extremely high industrial applicability. Among the synthetic resins or synthetic rubbers of the product (a) that can be used in the present invention, thermoplastic resins or thermosetting resins are used as the synthetic resins. Thermoplastic resins include low density, high density or linear low density polyethylene, polypropylene, poly(a-olefin) such as propylene/ethylene block or random copolymer, polystyrene, acrylonitrile/butadiene/styrene terpolymer, polymethacrylate. Acrylic resins such as acid methyl, polyhologenated vinyl such as polyvinyl chloride, polyamides such as nylon 6, nylon 66, and nylon 12, saturated polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyethers such as polyphenylene oxide, and polysulfone. , polyphenylene sulfide, polyvinylidene fluoride, polytetrafluoroethylene, ethylene/vinyl acetate copolymer, ethylene/acrylic acid or its ester copolymer, ethylene/methacrylic acid or its ester copolymer, and other a-olefins.・Vinyl monomer copolymer, maleic anhydride-modified polypropylene, maleic anhydride-modified polyethylene, maleic anhydride-modified polystyrene,
Modified resins such as vinylsilane-modified polypropylene and vinylsilane-modified polyethylene, water additives of styrene-butadiene block copolymers, etc. may be used alone or in mixtures. As the thermosetting resin, epoxy resin, phenolic resin, unsaturated polyester resin, melamine resin, polyuthalene, etc. may be used alone or in mixtures. Further, as the synthetic rubber, ethylene/propylene rubber, styrene/butadiene rubber, isobrene rubber, etc. may be used alone or as a mixture. 2,6-di-t- for synthetic resin or synthetic rubber
Butyl-4-methylphenol, 11,3-tri-
(2-Methyl-4-hydroxy-5-t-butylphenyl)butane, tetrakis [methylene (3,
5-di-t-butyl-4-hydroxyhydrocinnamate)] Phenol-based antioxidants such as methane, sulfur-based antioxidants such as dilauryl-thio-diprobionic acid ester, distearyl-thio-diprobionic acid ester, etc. In addition to stabilizers such as, ultraviolet absorbers, neutralizers, lubricants, etc. can be added. On the other hand, the carbon black of the above component (b) used in the present invention is produced by the process of partially oxidizing liquid hydrocarbons in the presence of molecular oxygen and water vapor in a furnace to produce conductive carbon black simultaneously with synthesis gasification. , the carbon atom/hydrogen atom weight ratio of the liquid hydrocarbon is 9 or more, and the furnace has an internal temperature range of 1200
~1500℃, furnace pressure 10~80Kg/ cm2 , amount of steam supplied into the furnace 200~200℃ per ton of the hydrocarbon
This is a special product manufactured using a method for manufacturing conductive carbon black that is characterized by operating under conditions of 800 kg. The liquid hydrocarbons used here are C heavy oil, A heavy oil, naphtha pyrolysis oil (ethylene heavy end),
There are liquid hydrocarbons (carbon oil) which are aromatic liquid hydrocarbons mixed with carbon black, mixed oils which are aromatic liquid hydrocarbons mixed with C heavy oil, etc. Among these, liquid hydrocarbons with a weight composition ratio of carbon atoms and hydrogen atoms (carbon atoms/hydrogen atoms) determined by elemental analysis of 9 or more, such as ethylene heavy end, carbon oil, aromatic liquid hydrocarbons, C heavy oil, etc. It is preferable to use a mixed oil containing the following. Further, ethylene heavy end, carbon oil and the like having a carbon atom/hydrogen atom weight ratio of 12 or more are particularly preferable because they can particularly reduce the ash content in the obtained carbon black. When the weight ratio of carbon atoms/hydrogen atoms is less than 9,
Even if the processing conditions in the furnace are changed, the DBP oil absorption of carbon black is significantly reduced, and the yield is also reduced, making it difficult to maintain the desired carbon black production. The liquid hydrocarbon that is the raw material has a carbon atom/hydrogen atom weight ratio of 9.
Whether it is above or below, it is not preferred if it becomes solid or becomes a highly viscous liquid hydrocarbon or carbon oil, which makes it difficult to feed into the furnace. In other words, even if the feedstock hydrocarbons fed into the furnace are in liquid form, the viscosity is low at the time of feeding.
It is preferable that it is 30 cst or more. As for specific operating conditions, the furnace for performing the partial oxidation reaction has an internal temperature of 1200 to 1500℃, preferably 1300℃.
~1450℃, furnace pressure 10~80Kg/ cm2 , preferably 25
~80Kg/cm 2 , and the amount of steam supplied into the furnace is 200 to 800Kg, preferably 300Kg per ton of raw material hydrocarbon.
Operated under conditions of ~800Kg. By satisfying these operating conditions and the characteristics of the feedstock hydrocarbon at the same time, it is possible to produce a limited number of products with excellent electrical conductivity that could not be achieved under conventionally known conditions.
It has become possible to produce carbon black with high DBP oil absorption and low ash content in good yields. The conductive carbon black applied to the composition of the present invention is obtained by the above-mentioned novel manufacturing method,
and DBP oil absorption of 200ml/100g or more 350ml/100
Less than g, preferably 250ml/100g or more 320ml/100
g or less, and the impurity metal residue (ash content) is 0.3% by weight or less. Here, DBP oil absorption is
Based on the measurement method of JIS-K6221-1970. Partial oxidation methods using liquid hydrocarbons as raw materials include the Shell gasification process and Texaco gasification process, which react the hydrocarbons with molecular oxygen and water vapor in a furnace to produce synthesis gas and at the same time produce carbon black as a by-product. AKZO's ``Ketschen Black'' is known as carbon black produced by the shell gasification process. Carbon black produced by the conventional partial oxidation method using liquid hydrocarbon as raw material has a high ash content, as seen in "Ketschen Black".
Only a certain level of DBP oil absorption could be obtained, and there were limits to its dispersibility into resin or rubber. On the other hand, the carbon black manufactured by the present invention at a specific furnace temperature, furnace pressure, and amount of steam supplied to the furnace has a low ash content and a lower DBP oil absorption than conventional products. . The blending ratio of the above components (a) and (b) in the composition of the present invention is 97 to 30% by weight of synthetic resin or synthetic rubber as component (a) and 3 to 70% by weight of the novel conductive carbon black as component (b). Weight%. If the arrangement ratio of the synthetic resin or synthetic rubber is less than 30% by weight, the moldability of the composition will be poor, and if it exceeds 97% by weight, high conductivity cannot be expected. The specific amount to be blended is determined depending on the requirements of each application. The composition of the present invention may further contain an inorganic or organic filler, preferably 60% by weight or less, in addition to the synthetic resin or synthetic rubber or the novel isoelectric carbon black. Inorganic fillers include calcium carbonate, talc, mica, glass fiber, wollastonite, glass beads, magnesium hydroxide, aluminum hydroxide, barium sulfate, graphite, molybdenum dioxide, carbon fiber, silica, carbon silicon fiber, aluminum fiber, and brass. Fibers, stainless steel fibers, aluminum flakes, aluminum powder, barium ferrite, strontium ferrite, etc. can be used. As the organic filler, wood flour, aromatic polyamide fiber, etc. can be used. The composition of the present invention can be used in Banbury mixers, rolls,
In addition to a batch-type kneader such as a Brabender Plastograph, it can be obtained using a continuous extruder such as a single-screw extruder or a twin-screw extruder. There is no particular restriction on the order of compounding, and in addition to mixing and kneading the compounds all at once, it is also possible to first mix a portion of the synthetic resin or synthetic rubber and carbon black in a batch or continuous extruder. It is also possible to knead the mixture and then knead the kneaded product with the remainder of the synthetic resin or synthetic rubber. The composition of the present invention obtained the following unexpected effects by using a specific conductive carbon black. (1) Durability such as heat aging resistance of the composition is significantly improved. (2) Improved dispersibility in synthetic resins or synthetic rubbers and good appearance of molded products. (3) Compared to conventional butcher blacks, the melt viscosity of the compounded resin or rubber is lower and the fluidity is excellent at the same filling standard, resulting in good moldability.
Furthermore, compared to acetylene black or general conductive furnace black, the filling amount required to provide a predetermined conductivity can be significantly reduced, resulting in excellent material strength and moldability. (4) It shows a high degree of conductivity even though the DBP oil absorption, which is considered an indicator of conductivity, is lower than that of conventional ketchen black. Reference example 1 The properties of the raw material liquid hydrocarbon are: Initial distillation temperature 180-190℃ 10% distillation temperature 205-215℃ 50% distillation temperature 250-260℃ 97% distillation temperature 320-340℃ Viscosity (80℃) Ethylene heavy end with approximately 10 cst carbon atoms/hydrogen atoms (weight ratio) 12.5 was used in the furnace of the shell gasification process. Conductive carbon black 1; C-1 The amount of steam supplied to the furnace at a temperature of 1400℃ and an internal pressure of 30Kg/ cm2 relative to the raw material hydrocarbon.
Reacted under conditions of 300Kg/ton, methane concentration 0.3% by volume, DBP oil absorption 290ml/100g, ash content 0.02
% carbon black by weight was obtained. Conductive carbon black 2; C-2 The amount of steam supplied to the furnace at a furnace temperature of 1350°C and a furnace pressure of 30Kg/cm 2 relative to the raw material hydrocarbon.
Reacted under conditions of 300Kg/ton, methane concentration 0.7% by volume, DBP oil absorption 230ml/100g, ash content 0.01
% carbon black by weight was obtained. Conductive carbon black 3; C-3 The amount of steam supplied to the furnace at an internal temperature of 1400°C and an internal pressure of 30 Kg/cm 2 relative to the raw material hydrocarbon.
Reacted under conditions of 400Kg/ton, methane concentration 0.3% by volume, DBP oil absorption 320ml/100g, ash content 0.1
% carbon black by weight was obtained. Conductive carbon black 4; C-4 DBP oil absorption 418 ml/100 g, except that the amount of steam supplied to the furnace was 500 kg/ton relative to the raw material hydrocarbon, in the same manner as in the production of C-3 above. Carbon black with an ash content of 0.05% by weight was obtained. Conductive carbon black 5; C-5 DBP oil absorption 490 ml/100 g, except that the amount of steam supplied to the furnace was 730 kg/ton relative to the raw material hydrocarbon, as in the production of C-3 above. Carbon black with an ash content of 0.07% by weight was obtained. Example 1 Predetermined amounts of polypropylene (MI4) and conductive carbon black 1 (C-1) of Reference Example 1 were heated at 230°C and rotor rotation speed using a Brabender Plastograph.
A press sheet with a thickness of 2 mm was produced using the compound obtained by kneading for 5 minutes at 60 rpm. Using this sheet, the volume resistivity was measured by the Wheatstone bridge method of SRIS standard 2301. For comparison, measurements were also made using a conventional butt-en-black. The results are shown in Figure 1. As is clear from Figure 1, in the polypropylene system, Kettien Black (DBP oil absorption 340 ~
360ml/100g), it was found that the same excellent conductivity level was exhibited even though the DBP oil absorption was smaller. Example 2 One of the processability tests was performed on a composition in which polypropylene (MI4) was filled with various conductive carbon blacks with different DBP oil absorption amounts in a predetermined amount so that the volume resistivity of the composition was 1.0 to 1.5 × 10°Ω-cm. serve as a guide
MFR (230℃, 10.73Kg load) was measured. The results are shown in Table 1.
【表】
第１表より、本発明の組成物は同一導電レベル
で優れた流動性を示しており、実際の加工面では
かなりの優位性をもつことが示唆されている。
また、上記組成物100重量部に２，2′−メチレ
ンビス（６−tert−ブチル−３−メチルフエノー
ル）0.1重量部を加えて厚さ0.5mmのプレスシート
を作製した。該シートを150℃ギアオーブンに入
れて劣化開始時間を測定した。結果を第２表に示
す。Table 1 shows that the composition of the present invention exhibits excellent fluidity at the same conductivity level, suggesting that it has considerable superiority in actual processing. Further, 0.1 part by weight of 2,2'-methylenebis(6-tert-butyl-3-methylphenol) was added to 100 parts by weight of the above composition to prepare a press sheet having a thickness of 0.5 mm. The sheet was placed in a gear oven at 150°C and the time at which it began to deteriorate was measured. The results are shown in Table 2.
【表】
第２表より明らかなように本発明の組成物はき
わめて良好な耐熱老化性を示しており、特にカー
ボンブラツク中の不純物金属残渣（灰分）が大き
な影響を有していることが把握された。
実施例 ３
低密度ポリエチレン（MI8.0、密度0.918）と参
考例１の導電性カーボンブラツク１（Ｃ−１）な
いしは同３（Ｃ−３）の所定量をブラベンダープ
ラストグラフにて140℃、ローター回転数50rpm
の条件で５分間混練して得られたコンパウンドを
用いて厚さ２mmのプレスシートを作製した。実施
例１と同様の方法で体積抵抗率を測定した結果を
第２図に示す。
なお比較例してアセチレンブラツク（電気化学
工業社製＜デンカブラツク＞）を20重量部の配合
組成のものの体積抵抗率を同様に測定したが107
Ω−cm以上で導電性レベルに大差のあることが判
明した。
また、上記本実施例の組成物および比較例とし
て導電性カーボンブラツク５（Ｃ−５）の配合組
成物のMFRを測定した。結果は第３表の通り。[Table] As is clear from Table 2, the composition of the present invention exhibits extremely good heat aging resistance, and it is understood that the impurity metal residue (ash content) in carbon black has a particularly large effect. It was done. Example 3 A predetermined amount of low density polyethylene (MI8.0, density 0.918) and conductive carbon black 1 (C-1) or carbon black 3 (C-3) of Reference Example 1 was heated at 140°C using a Brabender plastograph. Rotor rotation speed 50rpm
A press sheet with a thickness of 2 mm was produced using the compound obtained by kneading for 5 minutes under the following conditions. The results of measuring the volume resistivity in the same manner as in Example 1 are shown in FIG. As a comparative example, the volume resistivity of acetylene black (Denka Black, manufactured by Denki Kagaku Kogyo Co., Ltd.) containing 20 parts by weight was measured in the same manner.107
It was found that there is a large difference in conductivity level above Ω-cm. In addition, the MFR of the composition of this example and the blended composition of conductive carbon black 5 (C-5) as a comparative example were measured. The results are shown in Table 3.
【表】
次に、上記組成のものを二軸押出機を用いて
150℃で均一混練してコンパウンドを得た。
該コンパウンドを用いて50mm径インフレ成形機
（スクリユーＬ／Ｄ＝24、ダイスリツプ幅0.75mm、
スパイダースパイラルタイプ）で、成形温度180
℃、スクリユー回転42rpmの条件でフイルム成形
性を検討した。結果を第４表に示す。[Table] Next, the above composition was prepared using a twin screw extruder.
A compound was obtained by uniformly kneading at 150°C. Using the compound, a 50 mm diameter inflation molding machine (screw L/D = 24, die slip width 0.75 mm,
Spider spiral type), molding temperature 180
The film formability was examined under the conditions of ℃ and screw rotation of 42 rpm. The results are shown in Table 4.
【表】
高DBPの導電性カーボンブラツク配合系は押
出トルクの上昇、および延展性不足とサージング
発生がかさなり100ミクロン以下の薄膜化は困難
であつた。また得られたフイルムの表面には25〜
100μ程度の径をもつ“ブツ”が多く外観がきわ
めて不良であつた。
実施例 ４
ナイロン12（ダイセルヒユルス社＜ダイアミド
L1801＞）に参考例１の導電性カーボンブラツク
１（Ｃ−１）および同３（Ｃ−３）と比較として
DBP吸油量490ml／100ｇの導電性カーボンブラ
ツク５（Ｃ−５）を所定量ブラベンダープラスト
グラフにて220℃、ローター回転数70rpmの条件
で５分間混練してコンパウンドを得た。該コンパ
ウンドを用いて実施例１と同様の方法で体積抵抗
率を測定した。結果を第３図に示す。
また、上記各カーボンブラツクを15重量％配合
した組成物について高化式フローテスターを用い
て溶融粘度（200℃、ノズルＬ／Ｄ＝0.5／１）を
測定した。結果を第４図に示す。
第３図および４図から明らかなように本発明の
組成物は高DBP吸油量の導電性カーボン配合系
と比較しても遜色ない導電性レベルを有しており
（100〜101Ω−cmレベル達成）、かつ組成物の溶融
粘度が低いためバランスのとれた特性を有してい
る。
実施例 ５
エチレン−酢酸ビニル共重合体（EVA；酢酸
ビニル含量20重量％、MI12.0、密度0.940）に参
考例１の導電性カーボンブラツク１、２、３およ
び比較としてアセチレンブラツク（電気化学工業
社＜デンカブラツク＞）を樹脂100重量部に対し
て12重量部加えて、ブラベンダープラストグラフ
にて150℃、ローター回転数60rpmの条件で５分
間混練してコンパウンドを得た。該コンパウンド
を用いて実施例１と同様の方法にて体積抵抗率を
測定した。結果を第５図に示す。
第５図から明らかなように本発明の導電性カー
ボンブラツク配合系はDBP吸油量見合いの導電
性レベルがアセチレンブラツクとは大幅に異なる
という新しい事実を把握した。
実施例 ６
実施例５のEVAと参考例１の導電性カーボン
ブラツク１又は２またはアセチレンブラツク配合
物について体積抵抗率の温度依存性を測定した。
結果を第６図に示す。
第６図より、本発明の組成物は単に導電性付与
のためのカーボンブラツク添加量が少ないという
点のみならず、環境温度に対してきわめて安定し
た導電性を示すことがわかる。
また、この二つのカーボンブラツク系について
組成物の体積抵抗率がほぼ同等レベルになる配合
比、即ち参考例１の導電性カーボンブラツク１が
12重量部／EVA100重量部、アセチレンブラツク
55重量部／EVA100重量部の組成物について溶融
粘度（120℃、ノズルＬ／Ｄ＝１インチ／0.03イ
ンチ）を測定した。結果を第７図に示す。
実施例 ７
実施例５で用いたEVA100重量部にステアリン
酸亜鉛1.0部と参考例１の導電性カーボンブラツ
ク１（Ｃ−１）12重量部またはアセチレンブラツ
ク60重量部またはケツチエンブラツク12重量部を
各々配合し、ロール混練機にて120℃で10分間混
練してコンパウンドを得た。該コンパウンドを用
いて厚さ１mmのプレスシートを作製し、このもの
の150℃ギヤオーブン中で100時間経過後の引張強
伸度を測定した。結果を第５表に示す。[Table] It was difficult to form a thin film of 100 microns or less with high DBP conductive carbon black compound systems due to increased extrusion torque, insufficient spreadability, and surging. In addition, the surface of the obtained film has 25~
There were many "bumps" with a diameter of about 100μ, and the appearance was extremely poor. Example 4 Nylon 12 (Daicel Hüls <Diamide)
L1801>) as a comparison with conductive carbon black 1 (C-1) and 3 (C-3) of Reference Example 1.
A compound was obtained by kneading a predetermined amount of conductive carbon black 5 (C-5) with a DBP oil absorption of 490 ml/100 g in a Brabender plastograph at 220° C. and a rotor rotation speed of 70 rpm for 5 minutes. Volume resistivity was measured using the compound in the same manner as in Example 1. The results are shown in Figure 3. Furthermore, the melt viscosity (200° C., nozzle L/D=0.5/1) of the composition containing 15% by weight of each of the above carbon blacks was measured using a Koka type flow tester. The results are shown in Figure 4. As is clear from FIGS. 3 and 4, the composition of the present invention has a conductivity level comparable to that of a conductive carbon compound system with high DBP oil absorption (10 0 to 10 1 Ω- cm level) and has well-balanced properties due to the low melt viscosity of the composition. Example 5 Conductive carbon blacks 1, 2, and 3 of Reference Example 1 and acetylene black (Denki Kagaku Kogyo Co., Ltd. 12 parts by weight of Denka Black Co., Ltd.) were added to 100 parts by weight of the resin and kneaded for 5 minutes at 150° C. and 60 rpm in a Brabender Plastograph to obtain a compound. Volume resistivity was measured using the compound in the same manner as in Example 1. The results are shown in Figure 5. As is clear from FIG. 5, we have discovered a new fact that the conductive carbon black formulation system of the present invention has a conductivity level commensurate with DBP oil absorption that is significantly different from that of acetylene black. Example 6 The temperature dependence of volume resistivity was measured for the EVA of Example 5 and the conductive carbon black 1 or 2 of Reference Example 1 or the acetylene black formulation.
The results are shown in Figure 6. From FIG. 6, it can be seen that the composition of the present invention not only has a small amount of carbon black added for imparting conductivity, but also exhibits extremely stable conductivity with respect to environmental temperature. In addition, for these two carbon black systems, the compounding ratio at which the volume resistivity of the compositions is approximately at the same level, that is, the conductive carbon black 1 of Reference Example 1 is determined.
12 parts by weight/100 parts by weight of EVA, acetylene black
The melt viscosity (120° C., nozzle L/D=1 inch/0.03 inch) of the composition was measured at 55 parts by weight/100 parts by weight of EVA. The results are shown in FIG. Example 7 To 100 parts by weight of EVA used in Example 5, 1.0 part of zinc stearate and 12 parts by weight of conductive carbon black 1 (C-1) of Reference Example 1, 60 parts by weight of acetylene black, or 12 parts by weight of Kettien black were added. Each was blended and kneaded for 10 minutes at 120°C using a roll kneader to obtain a compound. A press sheet with a thickness of 1 mm was prepared using the compound, and the tensile strength and elongation of this sheet was measured after 100 hours had passed in a gear oven at 150°C. The results are shown in Table 5.
【表】【table】
【表】
実施例 ８
スチレン−ブタジエンブロツク共重合ゴムの水
素添加誘導体（シエル社＜クレートンＧ−1652、
スチレン／ラバー比：29／71）およびエチレン−
プロピレン共重合ゴム（プロピレン含量28重量
％、ムーニー粘度100℃
１＋４：75）90重量％と参考例
１の導電性カーボンブラツク１（Ｃ−１）、更に比
較として導電性カーボンブラツク５（Ｃ−５）を
10重量％とステアリン酸亜鉛１重量％とをロール
混練機を用いて200℃で10分間混練してコンパウ
ンドを得た。該コンパウンドを用いて実施例１と
同様の方法で組成物の体積抵抗率を測定する一
方、カーボンブラツクのゴム中での分散性をチエ
ツクする意味で40mm径押出機にて直径３mmの円形
ストランドを240℃で押出成形し、成形品の表面
状態（表面凹凸の多少）を測定した。結果を第６
表に示す。[Table] Example 8 Hydrogenated derivative of styrene-butadiene block copolymer rubber (Ciel Co. <Kraton G-1652,
Styrene/rubber ratio: 29/71) and ethylene-
Propylene copolymer rubber (propylene content 28% by weight, Mooney viscosity 100°C 1+4:75) 90% by weight, Conductive Carbon Black 1 (C-1) of Reference Example 1, and Conductive Carbon Black 5 (C-5) for comparison. )of
A compound was obtained by kneading 10% by weight of zinc stearate and 1% by weight of zinc stearate at 200°C for 10 minutes using a roll kneader. Using the compound, the volume resistivity of the composition was measured in the same manner as in Example 1, and in order to check the dispersibility of carbon black in rubber, circular strands with a diameter of 3 mm were prepared using an extruder with a diameter of 40 mm. Extrusion molding was performed at 240°C, and the surface condition of the molded product (the amount of surface unevenness) was measured. 6th result
Shown in the table.
【表】
＊ 押出トルクが高く、サージング現象も発
生した。
実施例 ９
エポキシ樹脂（油化シエル社製エピコート＃
828）67重量部と硬化剤（シエル化学社製エピキ
ユア＃
3025）33重量部と参考例１の導電性カーボ
ンブラツク３（Ｃ−３）または10重量部を自動撹
拌乳鉢で充分混合した。次にガラス板に紙テープ
でマスキングし該混合樹脂をガラス棒にて塗布
し、長さ10cm、幅１cm、厚み100ミクロンの塗膜
を形成させた。この塗膜の体積抵抗率をSRIS規
格2301のホイートストンブリツジ法でもつて測定
した。結果を第７表に示す。なお比較としてアセ
チレンブラツクまたは導電性カーボンブラツク５
（Ｃ−５）を配合した系についても示す。[Table] * Extrusion torque was high and surging phenomenon also occurred.
Example 9 Epoxy resin (Epicoat # manufactured by Yuka Ciel Co., Ltd.
828), 33 parts by weight of a curing agent (Epicure #3025 manufactured by Schiel Kagaku Co., Ltd.), and 10 parts by weight of the conductive carbon black 3 (C-3) of Reference Example 1 were thoroughly mixed in an automatic stirring mortar. Next, a glass plate was masked with paper tape and the mixed resin was applied using a glass rod to form a coating film with a length of 10 cm, a width of 1 cm, and a thickness of 100 microns. The volume resistivity of this coating film was measured using the Wheatstone bridge method according to SRIS standard 2301. The results are shown in Table 7. For comparison, acetylene black or conductive carbon black 5
A system containing (C-5) is also shown.
【表】
＊ カーボンの分散性不良で均一塗工ができ
なかつた。
[Table] * Uniform coating could not be achieved due to poor carbon dispersibility.
第１，２，３，５および６図は、それぞれ実施
例１、３、４、５および６の各組成物の体積固有
抵抗を示す図面である。また、第４および７図
は、実施例４および６の各組成物の溶融粘度を示
す図面である。
1, 2, 3, 5 and 6 are drawings showing the volume resistivity of each composition of Examples 1, 3, 4, 5 and 6, respectively. Moreover, FIGS. 4 and 7 are drawings showing the melt viscosity of each composition of Examples 4 and 6.
Claims (1)
よび、(b)液状炭化水素を炉内において分子状酸素
及び水蒸気の存在下部分酸化反応せしめて合成ガ
ス化と同時に導電性カーボンブラツクを製造する
にあたり、該液状炭化水素の炭素原子／水素原子
が重量比で９以上、該炉が炉内温度範囲1200〜
1500℃、炉内圧力10〜80Kg／cm2、炉内へ供給され
る水蒸気の量が該炭化水素１トン当たり200〜800
Kgの条件で運転して得られ、かつDBP吸油量が
220ml／100ｇ以上350ml／100ｇ未満で不純物金属
残渣が0.3重量％以下の導電性カーボンブラツク
３〜70重量％からなることを特徴とする高導電性
カーボンブラツク配合組成物。1. (a) 97 to 30% by weight of synthetic resin or synthetic rubber and (b) liquid hydrocarbon are subjected to a partial oxidation reaction in the presence of molecular oxygen and water vapor in a furnace to produce conductive carbon black at the same time as synthesis gasification. During production, the carbon atom/hydrogen atom weight ratio of the liquid hydrocarbon is 9 or more, and the furnace has an internal temperature range of 1,200 to 1,200.
1500℃, furnace pressure 10~80Kg/ cm2 , amount of steam supplied to the furnace 200~800 per ton of hydrocarbon.
Kg, and the DBP oil absorption is
A highly conductive carbon black composition comprising 3 to 70% by weight of conductive carbon black of 220ml/100g or more and less than 350ml/100g and containing impurity metal residues of 0.3% by weight or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19730483A JPS6088073A (en) | 1983-10-21 | 1983-10-21 | Composition containing highly electrically conductive carbon black |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19730483A JPS6088073A (en) | 1983-10-21 | 1983-10-21 | Composition containing highly electrically conductive carbon black |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6088073A JPS6088073A (en) | 1985-05-17 |
| JPH0510391B2 true JPH0510391B2 (en) | 1993-02-09 |
Family
ID=16372230
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19730483A Granted JPS6088073A (en) | 1983-10-21 | 1983-10-21 | Composition containing highly electrically conductive carbon black |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6088073A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62172059A (en) * | 1986-01-27 | 1987-07-29 | Toray Ind Inc | Polyphenylene sulfide resin composition |
| WO2000042093A1 (en) * | 1999-01-12 | 2000-07-20 | Daikin Industries, Ltd. | Molded elastomer |
| JP3514452B2 (en) * | 2002-02-08 | 2004-03-31 | ケッチェン・ブラック・インターナショナル株式会社 | Highly conductive thermoplastic resin composition |
| CN105283514B (en) | 2013-05-14 | 2017-09-19 | 狮王特殊化学株式会社 | Carbon black, conductive resin composition and electrode mixing material |
| JP7309444B2 (en) * | 2018-07-05 | 2023-07-18 | キヤノン株式会社 | RESIN COMPOSITION, RESIN MOLDED PRODUCT, RESIN LAMINATED BODY, CARTRIDGE, IMAGE FORMING APPARATUS, METHOD FOR MANUFACTURING RESIN MOLDED BODY, METHOD FOR MANUFACTURING RESIN LAMINATED BODY, AND METHOD FOR MANUFACTURING CARTRIDGE |
-
1983
- 1983-10-21 JP JP19730483A patent/JPS6088073A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6088073A (en) | 1985-05-17 |
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