JP5518316B2 - Carbon black composite and method for producing the same - Google Patents
Carbon black composite and method for producing the same Download PDFInfo
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- 239000006229 carbon black Substances 0.000 title claims description 48
- 239000002131 composite material Substances 0.000 title claims description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 76
- 229910052799 carbon Inorganic materials 0.000 claims description 61
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 27
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 14
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 13
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 12
- 239000006230 acetylene black Substances 0.000 claims description 11
- 238000001069 Raman spectroscopy Methods 0.000 claims description 10
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 7
- 229930192474 thiophene Natural products 0.000 claims description 7
- 239000003426 co-catalyst Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 description 10
- 229930195733 hydrocarbon Natural products 0.000 description 10
- 150000002430 hydrocarbons Chemical class 0.000 description 10
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 239000002956 ash Substances 0.000 description 7
- -1 for example Natural products 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical compound CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 description 4
- 239000002041 carbon nanotube Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 4
- 239000002134 carbon nanofiber Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
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- 239000010419 fine particle Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Description
本発明は、カーボンブラック複合体及びその製造方法に関する。 The present invention relates to a carbon black composite and a method for producing the same.
従来、ゴム、樹脂等にカーボンブラックを含有させ、導電性を付与させるということが行われている。特にアセチレンブラックは炭素粒子の連鎖構造を有するため、一般のカーボンブラックと比較して導電性の付与能力に優れている。 Conventionally, carbon black is contained in rubber, resin or the like to impart conductivity. In particular, since acetylene black has a chain structure of carbon particles, it has superior conductivity imparting ability compared to general carbon black.
しかしながら、近年、樹脂等の本来の特性を低下させずに高い導電性を付与することが出来る導電剤が求められており、この要求を満たすためには、導電付与効果が一段と優れたカーボンブラックを開発する必要がある。 However, in recent years, there has been a demand for a conductive agent capable of imparting high conductivity without deteriorating the original properties of resins and the like, and in order to satisfy this requirement, carbon black having a further excellent conductivity imparting effect is required. Need to develop.
このような問題に対して、導電剤にカーボンナノチューブを用いることが提案されているが、分散性が悪く、触媒除去や結晶性向上のための後処理を必要とするものが多く、非常に高価である。 In order to solve such problems, it has been proposed to use carbon nanotubes as a conductive agent, but the dispersibility is poor, and many post treatments are required for catalyst removal and crystallinity improvement, which is very expensive. It is.
これらの問題に対して、アセチレンブラックの反応場でカーボンナノチューブ生成するという提案がされているが（特許文献１）、カーボンナノチューブとアセチレンブラックの生成条件が異なり、一つの生成場での同時生成を行うことにより、品質が安定しないことがある。
本発明の目的は、導電性付与能力に優れたカーボンブラック複合体及び、その製造方法を提供することである。本発明のカーボンブラック複合体は、低充填量で樹脂等に高い導電性を付与することが出来る。 An object of the present invention is to provide a carbon black composite excellent in conductivity imparting ability and a method for producing the same. The carbon black composite of the present invention can impart high conductivity to a resin or the like with a low filling amount.
本発明は、上記課題を解決するために、以下の手段を採用する。
（１）アセチレンガスの流量を１０ｍ ３ ／ｈで供給し、２０００℃で熱分解してアセチレンブラックを製造する工程に、炭素源としてベンゼン、触媒としてフェロセン、助触媒としてチオフェンを質量比で９０：８：２として３００℃でガス化し、５０〜１００ｍ／ｓで導入し、温度６００〜１０００℃で熱処理して生成した繊維状炭素を添加し、繊維状炭素とアセチレンブラックを複合化させた、繊維状炭素の含有率が３０〜５０質量％、繊維状炭素のラマン強度比（Ｄ／Ｇ値）が０．２４以下、ＪＩＳ Ｋ １４６９で規定される灰分が０．０１質量％以下であることを特徴とするカーボンブラック複合体。
（２）アセチレンガスの流量を１０ｍ３／ｈで供給し、２０００℃で熱分解してアセチレンブラックを製造する工程に、炭素源としてベンゼン、触媒としてフェロセン、助触媒としてチオフェンを質量比で９０：８：２として３００℃でガス化し、５０〜１００ｍ／ｓで導入し、温度６００〜１０００℃で熱処理して生成した繊維状炭素を添加し、繊維状炭素とアセチレンブラックを複合化させることを特徴とする、繊維状炭素の含有率が３０〜５０質量％、繊維状炭素のラマン強度比（Ｄ／Ｇ値）が０．２４以下、ＪＩＳ Ｋ １４６９で規定される灰分が０．０１質量％以下であるカーボンブラック複合体の製造方法。
（３）繊維状炭素の直径が９０ｎｍ以下であることを特徴とする前記（２）に記載のカーボンブラック複合体の製造方法。
The present invention employs the following means in order to solve the above problems.
(1) Supplying acetylene gas at a flow rate of 10 m 3 / h and thermally decomposing at 2000 ° C. to produce acetylene black, benzene as a carbon source, ferrocene as a catalyst, and thiophene as a co-catalyst at a mass ratio of 90: 8: 2 is a fiber that is gasified at 300 ° C., introduced at 50 to 100 m / s, and added with fibrous carbon produced by heat treatment at a temperature of 600 to 1000 ° C., and the fibrous carbon and acetylene black are combined. The carbon content is 30-50 % by mass, the fibrous carbon Raman intensity ratio (D / G value) is 0.24 or less, and the ash content defined by JIS K 1469 is 0.01% by mass or less. Characteristic carbon black composite.
(2) In the step of supplying acetylene gas at a flow rate of 10 m 3 / h and thermally decomposing at 2000 ° C. to produce acetylene black, benzene as a carbon source, ferrocene as a catalyst, and thiophene as a co-catalyst at a mass ratio of 90: 8: 2 gasified at 300 ° C., introduced at 50 to 100 m / s, added with fibrous carbon produced by heat treatment at 600 to 1000 ° C., and combined with fibrous carbon and acetylene black The fibrous carbon content is 30 to 50% by mass, the fibrous carbon Raman intensity ratio (D / G value) is 0.24 or less, and the ash content defined by JIS K 1469 is 0.01% by mass or less. A method for producing a carbon black composite.
(3) The method for producing a carbon black composite as described in (2) above, wherein the fibrous carbon has a diameter of 90 nm or less.
本発明のカーボンブラック複合体は、従来のカーボンブラックよりも導電性付与能力に優れている。 The carbon black composite of the present invention is more excellent in conductivity imparting ability than conventional carbon black.
本発明のカーボンブラック複合体は、繊維状炭素とカーボンブラックが連結しているものである。本発明のカーボンブラック複合体は、ＪＩＳ Ｋ １４６９で規定される灰分が１．０質量％以下であることが好ましい。灰分は主に繊維状炭素製造時の触媒や金属不純物（Ｆｅ、Ｎｉ、Ｃｏ等）やその酸化物からなる。灰分が１．０質量％を超えると、例えばＬｉイオン二次電池とした場合、充電時に負極上への金属の析出が起こり易くなり、充放電容量の低下やセパレータを突き破り短絡して発火する危険性を生ずる恐れがある。 The carbon black composite of the present invention is one in which fibrous carbon and carbon black are linked. The carbon black composite of the present invention preferably has an ash content defined by JIS K 1469 of 1.0% by mass or less. The ash is mainly composed of a catalyst for producing fibrous carbon, metal impurities (Fe, Ni, Co, etc.) and oxides thereof. If the ash content exceeds 1.0% by mass, for example, in the case of a Li ion secondary battery, metal deposition on the negative electrode is likely to occur during charging, and the risk of ignition due to a decrease in charge / discharge capacity or a short circuit through the separator. May cause sex.
連結とは単なる接触ではなく、炭素質で物理的に融着していることを意味し、通常の機械的操作では容易に分離されることなく、連結された繊維状炭素とカーボンブラック間で接触抵抗なしで電子が自由に移動できるものである。そのため、樹脂等と混合した際もカーボンブラック複合体のまま存在し、良好な分散性が得られると同時に高導電性が保たれる。繊維状炭素単独では、樹脂等の他の材料と混合する場合、配向や繊維同士の絡み合いのため、良好な分散性を得ることが困難であり、導電性にバラツキが生じる。カーボンブラックと繊維状炭素を単純に混合した場合は形状が異なるため更にバラツキが大きくなるが、本発明のカーボンブラック複合体は導電性の安定性に優れていることが特長の一つである。ここで繊維状炭素は１０〜５０質量％であることが好ましい。繊維状炭素が１０質量％未満であると、十分な導電性が得られず、５０質量％を超えるとカーボンブラックとの連結が十分でなくなると同時に、繊維状炭素の凝集などのため分散性が著しく低下する。 Coupling is not just contact, it means that it is physically fused with carbonaceous matter, and it is not easily separated by normal mechanical operations, but between the connected fibrous carbon and carbon black. Electrons can move freely without resistance. Therefore, even when mixed with a resin or the like, the carbon black composite remains as it is, and good dispersibility can be obtained and high conductivity can be maintained. When the fibrous carbon alone is mixed with other materials such as a resin, it is difficult to obtain good dispersibility due to orientation and entanglement between fibers, resulting in variations in conductivity. When carbon black and fibrous carbon are simply mixed, the shape is different and the variation further increases. However, one feature of the carbon black composite of the present invention is that it has excellent conductivity stability. Here, the fibrous carbon is preferably 10 to 50% by mass. When the fibrous carbon is less than 10% by mass, sufficient conductivity cannot be obtained, and when it exceeds 50% by mass, the connection with the carbon black is not sufficient, and at the same time, the dispersibility is due to aggregation of the fibrous carbon. It drops significantly.
本発明のカーボンブラック複合体で使用される繊維状炭素とは、炭素繊維（カーボンファイバー）、気相成長炭素繊維（ＶＧＣＦ）、カーボンナノチューブ、カーボンナノファイバー等である。本発明においては繊維状炭素を適宜選択可能であるが、繊維状炭素は直径が２００ｎｍ以下であることが好ましい。 The fibrous carbon used in the carbon black composite of the present invention is carbon fiber (carbon fiber), vapor grown carbon fiber (VGCF), carbon nanotube, carbon nanofiber, or the like. In the present invention, fibrous carbon can be appropriately selected, but the fibrous carbon preferably has a diameter of 200 nm or less.
本発明のカーボンブラック複合体に用いられる繊維状炭素は、通常の市販品のすべてを使用できる。また、ラマン強度比（Ｄ／Ｇ値）が高く、結晶性が低いものでも、炭化水素の熱分解中に導入し複合化することにより、ラマン強度比（Ｄ／Ｇ値）を０．３０以下にすることが出来るため、使用することが可能である。 As the fibrous carbon used in the carbon black composite of the present invention, all ordinary commercial products can be used. In addition, even when the Raman intensity ratio (D / G value) is high and the crystallinity is low, the Raman intensity ratio (D / G value) is 0.30 or less by introducing it into the hydrocarbon during the pyrolysis and combining it. Can be used.
本発明のカーボンブラック複合体は、繊維状炭素を炭化水素の熱分解中に導入する方法で製造される。この製造方法を用いることでカーボンブラック複合体のＪＩＳ Ｋ １４６９に規定される灰分を１．０質量％以下にすることが出来る。 The carbon black composite of the present invention is produced by a method in which fibrous carbon is introduced during the thermal decomposition of hydrocarbons. By using this production method, the ash content defined in JIS K 1469 of the carbon black composite can be reduced to 1.0% by mass or less.
本発明のカーボンブラック複合体に用いる繊維状炭素は、炭化水素の熱分解温度以上の高温場に供給し、熱処理することにより生成することができる。炭化水素の熱分解温度は、特に６００〜１０００℃であることが好ましい。炭化水素として、例えばメタン、エタン、プロパン、ブタン等の飽和炭化水素、例えばエチレン、プロピレン、ブテン、ブタジエン等の２重結合を有する不飽和炭化水素、アセチレン、プロピン、ブチン等の３重結合を有する不飽和炭化水素、ベンゼン、トルエン、キシレン等の芳香族炭化水素等を用いることが出来る。中でも、芳香族炭化水素は常温で液体であり、繊維状炭素化触媒と事前に混合調整しやすいので特に好ましい。また、炭化水素の供給速度は５〜１００ｍ／ｓが好ましい。 Fibrous carbon used in the carbon black composite of the present invention can be produced by supplying heat to a high temperature field that is equal to or higher than the thermal decomposition temperature of the hydrocarbon and heat treating it. The thermal decomposition temperature of the hydrocarbon is particularly preferably 600 to 1000 ° C. As hydrocarbons, for example, saturated hydrocarbons such as methane, ethane, propane, butane, etc., unsaturated hydrocarbons having double bonds such as ethylene, propylene, butene, butadiene, etc., and triple bonds such as acetylene, propyne, butyne, etc. Unsaturated hydrocarbons, aromatic hydrocarbons such as benzene, toluene and xylene can be used. Among these, aromatic hydrocarbons are particularly preferable because they are liquid at room temperature and can be easily mixed and adjusted in advance with the fibrous carbonization catalyst. The hydrocarbon feed rate is preferably 5 to 100 m / s.
繊維状炭素化触媒、助触媒としては、Ｃｏ，Ｎｉ，Ｆｅ，Ｍｏ，Ｓ，Ｖ，Ｃｒ等の微粒子を用いることが出来る。中でも、フェロセンやチオフェン等の有機物質はベンゼン等の芳香族炭化水素に可溶のため、取り扱いが容易で、しかも化合物中に含まれる元素が原子サイズのため、反応場中では触媒として有効に作用するため特に好ましい。 As the fibrous carbonization catalyst and the cocatalyst, fine particles such as Co, Ni, Fe, Mo, S, V, and Cr can be used. In particular, organic substances such as ferrocene and thiophene are soluble in aromatic hydrocarbons such as benzene, so they are easy to handle, and because the elements contained in the compound are atomic in size, they effectively act as catalysts in the reaction field. Therefore, it is particularly preferable.
本発明のカーボンブラック複合体における繊維状炭素を製造するときの炭化水素と触媒、助触媒の混合比は、質量比で８０：２０〜９９：１が好ましく、特に９０：１０〜９５：５が好ましい。 The mixing ratio of the hydrocarbon, the catalyst and the cocatalyst when producing fibrous carbon in the carbon black composite of the present invention is preferably 80:20 to 99: 1, and particularly 90:10 to 95: 5, in mass ratio. preferable.
本発明のカーボンブラック複合体におけるカーボンブラックは、炭化水素の熱分解温度以上の高温場で生成することが好ましく、特に１８００〜２２００℃で生成することが好ましい。炭化水素として、例えばメタン、エタン、プロパン、ブタン等の飽和炭化水素、例えばエチレン、プロピレン、ブテン、ブタジエン等の２重結合を有する不飽和炭化水素、アセチレン、プロピン、ブチン等の３重結合を有する不飽和炭化水素、ベンゼン、トルエン、キシレン等の芳香族炭化水素等を用いることが出来る。中でもエチレン、アセチレン、ブタジエンは、自己発熱分解反応であるため、反応炉の中心部分でも高温を維持できるため好ましく、特にアセチレンが好ましい。また、炭化水素の供給量は５〜２０ｍ３／ｈであることが好ましく、特に１０〜１５ｍ３／ｈであることが好ましい。 The carbon black in the carbon black composite of the present invention is preferably generated in a high temperature field equal to or higher than the thermal decomposition temperature of the hydrocarbon, and particularly preferably generated at 1800 to 2200 ° C. As hydrocarbons, for example, saturated hydrocarbons such as methane, ethane, propane, butane, etc., unsaturated hydrocarbons having double bonds such as ethylene, propylene, butene, butadiene, etc., and triple bonds such as acetylene, propyne, butyne, etc. Unsaturated hydrocarbons, aromatic hydrocarbons such as benzene, toluene and xylene can be used. Among these, ethylene, acetylene, and butadiene are preferable because they are self-exothermic decomposition reactions and can maintain high temperatures even in the central portion of the reaction furnace, and acetylene is particularly preferable. It is preferable that the supply amount of the hydrocarbon is 5 to 20 m 3 / h, it is particularly preferably 10 to 15 m 3 / h.
本発明のカーボンブラック複合体における繊維状炭素は、カーボンブラックの生成場に導入、複合化されることにより焼成され、ラマン強度比（Ｄ／Ｇ値）０．３０以下になっていることが好ましい。 It is preferable that the fibrous carbon in the carbon black composite of the present invention is fired by being introduced into the carbon black production field and composited to have a Raman intensity ratio (D / G value) of 0.30 or less. .
次に実施例により本発明の具体的態様を更に詳細に説明するが、本発明はこれらの例によって限定されるものではない。 EXAMPLES Next, specific embodiments of the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
（実施例１〜３）
繊維状炭素は以下の方法で作製した。炭素源としてベンゼン（関東化学社製試薬、９９％）、触媒としてフェロセン（関東化学社製試薬、９８％）、助触媒としてチオフェン（関東化学社製試薬、９８％）を質量比で９０：８：２として３００℃でガス化したものを、縦型管状炉の上方に設置されたノズルから水素ガスと共に噴霧し、流速５０ｍ／ｓ、温度６００，８００，１０００℃で繊維状炭素を生成した。このときのラマン強度比（Ｄ／Ｇ値）は表１に示す。また、各温度における繊維状炭素の直径は表１に示す。次に、反応炉（炉長６ｍ、炉直径１ｍ）の炉頂に設置された２本のノズルの一方からはアセチレンガス（純度９９％）を流量１０ｍ３／ｈで供給し、２０００℃で熱分解してカーボンブラックを生成し、もう一方からは６００，８００，１０００℃で製造した繊維状炭素を、３０質量％になるように導入し複合化を行った。そのカーボンブラック複合体は炉下部に直結されたバグフィルターから捕集した。このときの繊維状炭素のラマン強度比（Ｄ／Ｇ値）は表１に示す。それらについての評価を行い、結果を表１に示す。
（１）繊維状炭素の直径については透過型電子顕微鏡（ＴＥＭ）により、倍率３万倍で１００本測定し、その平均径を求めた。
（２）ラマン強度比測定については励起レーザー波長５３２ｎｍ、露光時間１．０秒、露光回数３０回でカーボンの固有ピークＧバンド、Ｄバンドを測定した。
（３）灰分についてはＪＩＳ Ｋ １４６９に従い測定した。
（４）粉体抵抗についてはＪＩＳ Ｋ １４６９に従い測定した。
（５）コンパウンド体積固有抵抗値測定による導電性評価
実施例１〜３と比較例１のカーボンブラック複合体１０質量部をＰＳ樹脂（東洋スチレン社製、商品名「Ｈ７００」）９０質量部に配合し、混練機（東洋精機製作所社製、商品名「ラボプラストミル」）を用いて、ブレード回転数３０ｒｐｍ、温度２２０℃で１０分間混練した。この混練物を２００℃に加熱し、９．８×１０６Ｐａの圧力で加圧成形して２×２×７０ｍｍの試験片を作製し、デジタルマルチメーター（横河電機社、商品名「デジタルマルチメータ ７５６２」）を用い、ＳＲＩ２３０１に準じて体積固有抵抗を測定した。
(Examples 1-3)
Fibrous carbon was produced by the following method. Benzene (reagent manufactured by Kanto Chemical Co., 99%) as a carbon source, ferrocene (reagent manufactured by Kanto Chemical Co., 98%) as a catalyst, and thiophene (reagent manufactured by Kanto Chemical Co., 98%) as a co-catalyst in a mass ratio of 90: 8 : 2 gasified at 300 ° C. was sprayed with hydrogen gas from a nozzle installed above the vertical tubular furnace to produce fibrous carbon at a flow rate of 50 m / s and temperatures of 600, 800, 1000 ° C. The Raman intensity ratio (D / G value) at this time is shown in Table 1. Moreover, the diameter of the fibrous carbon at each temperature is shown in Table 1. Next, acetylene gas (purity 99%) was supplied at a flow rate of 10 m3 / h from one of the two nozzles installed at the top of the reactor (furnace length 6 m, furnace diameter 1 m) and pyrolyzed at 2000 ° C. Thus, carbon black was produced, and fibrous carbon produced at 600, 800, and 1000 ° C. was introduced from the other side so as to be 30% by mass, and composited. The carbon black composite was collected from a bag filter directly connected to the lower part of the furnace. The Raman intensity ratio (D / G value) of the fibrous carbon at this time is shown in Table 1. These were evaluated and the results are shown in Table 1.
(1) About the diameter of fibrous carbon, 100 pieces were measured with the transmission electron microscope (TEM) by the magnification of 30,000 times, and the average diameter was calculated | required.
(2) For the Raman intensity ratio measurement, the intrinsic peak G band and D band of carbon were measured at an excitation laser wavelength of 532 nm, an exposure time of 1.0 second, and an exposure frequency of 30 times.
(3) Ashes were measured according to JIS K 1469.
(4) The powder resistance was measured according to JIS K 1469.
(5) Conductivity Evaluation by Measuring Compound Volume Specific Resistance Value 10 parts by mass of the carbon black composites of Examples 1 to 3 and Comparative Example 1 are blended with 90 parts by mass of PS resin (trade name “H700” manufactured by Toyo Styrene Co., Ltd.). Then, the mixture was kneaded for 10 minutes using a kneader (manufactured by Toyo Seiki Seisakusho, trade name “Laboplast Mill”) at a blade rotation speed of 30 rpm and a temperature of 220 ° C. The kneaded product was heated to 200 ° C. and pressure-molded at a pressure of 9.8 × 10 6 Pa to prepare a 2 × 2 × 70 mm test piece. A digital multimeter (Yokogawa Electric Corporation, trade name “Digital” Using a multimeter 7562 "), the volume resistivity was measured according to SRI2301.
実施例４，５として、実施例１に記載の製法で繊維状炭素の炭素源ガスを５，１００ｍ／ｓにして繊維状炭素を製造し、実施例１のアセチレンガス反応炉に導入しカーボンブラック複合体を製造した。また、実施例６，７は、実施例１に記載の繊維状炭素の炭素源ガスを３，１２０ｍ／ｓにして繊維状炭素を製造し、実施例１のアセチレンガス反応炉に導入しカーボンブラック複合体を製造した。 As Examples 4 and 5, fibrous carbon was produced by the production method described in Example 1 with the carbon source gas of fibrous carbon set to 5,100 m / s, and introduced into the acetylene gas reactor of Example 1 to obtain carbon black. A composite was produced. In Examples 6 and 7, fibrous carbon was produced by setting the carbon source gas of the fibrous carbon described in Example 1 to 3,120 m / s, and introduced into the acetylene gas reactor of Example 1 to obtain carbon black. A composite was produced.
実施例８，９では、実施例１に記載の製法で繊維状炭素の含有量を１０％、５０％、実施例１０，１１は実施例１に記載の製法で繊維状炭素の含有量を５％、６０％になるように、繊維状炭素を導入した。 In Examples 8 and 9, the content of fibrous carbon was 10% and 50% in the production method described in Example 1, and in Examples 10 and 11, the content of fibrous carbon was 5 in the production method described in Example 1. % And 60% were introduced into the fibrous carbon.
比較例１については、実施例１に記載された方法で繊維状炭素とカーボンブラックを別々に製造し、それぞれ質量比３０：７０でボールミルにて２００ｒｐｍ、６０ｍｉｎで混合し、カーボンブラック複合体を製造した。 For Comparative Example 1, fibrous carbon and carbon black were produced separately by the method described in Example 1, and mixed at 200 rpm and 60 min in a ball mill at a mass ratio of 30:70, respectively, to produce a carbon black composite. did.
比較例２については、ＷＯ／２００７／０１３６７８に基づき、反応炉（炉長６ｍ、炉直径１ｍ）の上方に設置されたノズルからアセチレンガスを１５ｍ３／ｈで供給し、アセチレンガスを２０００℃で熱分解してカーボンブラックを生成しつつ、更に上方の１０００℃の部分からベンゼン（関東化学社製試薬、９９％、３．７ｋｇ／ｈ）、触媒としてフェロセン（関東化学社製試薬、９８％、０．３ｋｇ／ｈ）、助触媒としてチオフェン（関東化学社製試薬、９８％、０．０５ｋｇ／ｈ）の混合ガスを供給し繊維状炭素を生成し、繊維状炭素が３０質量％になるようにカーボンブラック複合体を製造した。 For Comparative Example 2, acetylene gas was supplied at 15 m 3 / h from a nozzle installed above a reactor (furnace length 6 m, furnace diameter 1 m) based on WO / 2007/013678, and acetylene gas was heated at 2000 ° C. While producing carbon black by decomposition, benzene (Kanto Chemicals reagent, 99%, 3.7 kg / h) from the upper portion of 1000 ° C. and ferrocene as a catalyst (Kanto Chemicals reagent, 98%, 0) .3 kg / h), and a mixed gas of thiophene (reagent manufactured by Kanto Chemical Co., 98%, 0.05 kg / h) is supplied as a co-catalyst to produce fibrous carbon, so that the fibrous carbon becomes 30% by mass. A carbon black composite was produced.
表１から、本発明の実施例又は参考例によって得られたカーボンブラック複合体は、比較例１，２によって得られたカーボンブラック複合体と比べて粉体抵抗、コンパウンド抵抗が低く、従来のカーボンブラック複合体より優れた導電性付与効果を発揮した。 From Table 1, the carbon black composites obtained by Examples or Reference Examples of the present invention have lower powder resistance and compound resistance than the carbon black composites obtained by Comparative Examples 1 and 2, and the conventional carbon. Excellent conductivity imparting effect than the black composite.
本発明のカーボンブラック複合体は樹脂、ゴムへの導電性付与剤の他に、一次電池、二次電池、燃料電池、キャパシタ等の電池用導電剤等として利用することが出来る。
The carbon black composite of the present invention can be used as a conductive agent for batteries such as a primary battery, a secondary battery, a fuel cell, and a capacitor in addition to a conductivity imparting agent for resin and rubber.
Claims (3)
The method for producing a carbon black composite according to claim 2, wherein the diameter of the fibrous carbon is 90 nm or less.
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