JP4565384B2 - Method for producing carbon nanofibers with excellent dispersibility in resin - Google Patents
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- JP4565384B2 JP4565384B2 JP2004345423A JP2004345423A JP4565384B2 JP 4565384 B2 JP4565384 B2 JP 4565384B2 JP 2004345423 A JP2004345423 A JP 2004345423A JP 2004345423 A JP2004345423 A JP 2004345423A JP 4565384 B2 JP4565384 B2 JP 4565384B2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims description 61
- 239000002134 carbon nanofiber Substances 0.000 title claims description 60
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 239000011347 resin Substances 0.000 title description 24
- 229920005989 resin Polymers 0.000 title description 24
- 239000007789 gas Substances 0.000 claims description 42
- 239000003054 catalyst Substances 0.000 claims description 40
- 239000002245 particle Substances 0.000 claims description 30
- 238000010521 absorption reaction Methods 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 10
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims description 9
- 239000011812 mixed powder Substances 0.000 claims description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 8
- 239000001569 carbon dioxide Substances 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 238000001947 vapour-phase growth Methods 0.000 claims description 7
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 22
- 238000010438 heat treatment Methods 0.000 description 11
- 239000011342 resin composition Substances 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
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Description
本発明は樹脂に対する分散性に優れたカーボンナノファイバーの製造方法に関する。より詳しくは、表面が親油性の無定形炭素層を有し、従って、ジブチルフタレート吸油量（ＤＢＰ給油量：以下単に吸油量と云う場合がある）が高く、樹脂に対する分散性に優れたカーボンナノファイバーの製造方法に関する。本発明のカーボンナノファイバーはプラスチック、セラミックス、塗料などのフィラーとして好適であり、各種成形材料、部品、電池やキャパシターなど各種分野の導電性付与材や補強材などに広く用いることができる。
The present invention relates to a method for producing carbon nanofibers excellent in dispersibility for a resin. More specifically, the surface has a lipophilic amorphous carbon layer, and therefore has a high dibutyl phthalate oil absorption amount (DBP oil supply amount: hereinafter sometimes referred to simply as oil absorption amount), and has excellent dispersibility for resins. The present invention relates to a fiber manufacturing method . The carbon nanofibers of the present invention are suitable as fillers for plastics, ceramics, paints, etc., and can be widely used for various molding materials, parts, conductivity imparting materials and reinforcing materials in various fields such as batteries and capacitors.
従来、この種のカーボンナノファイバーは電極放電法、気相成長法、レーザ法などによって合成されている。このうち、触媒を用いた気相成長法は、加熱した装置内に原料ガスを供給して熱分解させ、鉄やニッケルなどの金属触媒粒子を核として長さ方向にカーボンを成長させる方法である。この方法は、量産性に優れるとのことから、各種の改良方法が試みられており、触媒粒子についても各種検討されている。一般的に、鉄、ニッケル、コバルトなどの金属微粒子あるいは金属微粒子を担持した酸化物（アルミナ、シリカ、ゼオライトなど）が知られている（特許文献１）。 Conventionally, this type of carbon nanofiber has been synthesized by an electrode discharge method, a vapor phase growth method, a laser method, or the like. Among these, the vapor phase growth method using a catalyst is a method in which a raw material gas is supplied into a heated apparatus and thermally decomposed, and carbon is grown in the length direction using metal catalyst particles such as iron and nickel as nuclei. . Since this method is excellent in mass productivity, various improvement methods have been attempted, and various studies have been made on catalyst particles. Generally, metal fine particles such as iron, nickel and cobalt or oxides carrying metal fine particles (alumina, silica, zeolite, etc.) are known (Patent Document 1).
しかし、従来の方法によって製造されたカーボンナノファイバーは化学的安定性に劣り、また製造温度が高く、また結晶性を高めるために黒鉛化処理を行っているのでコスト高であると云う問題があり、これを解消するために、特定の金属微粒子を触媒に用い、かつ原料ガスを従来のハイドロカーボンに代えて一酸化炭素ガスまたは二酸化炭素ガスと水素ガスの混合ガスを用いることによって化学的安定性の高いカーボンナノファイバーを従来よりも低温で製造する方法が開発されている（特許文献２）。
従来のカーボンナノファイバーは形状、構造等について検討されているが、樹脂中の分散性については考慮されていない。しかし、カーボンナノファイバーの分散性はこれを含有する組成物の物性に大きな影響を与える。例えば、樹脂に対する分散性の指標となるＤＢＰ給油量について、従来のカーボンナノファイバーは１０〜５０ml/100ｇ程度である。このようなＤＢＰ吸油量が小さく、従って分散性の低いカーボンナノファイバーを含有した樹脂組成物では、カーボンナノファイバーの含有量が多くなると樹脂の物性がしだいに損なわれ、樹脂組成物の伸長性が大幅に低下して紡糸不能になり、また導電性が不均一になり、温度湿度に対する比抵抗の変化も大きく、混練性や成形性が低下するなどの問題を生じる。 Conventional carbon nanofibers have been studied for shape, structure, etc., but dispersibility in the resin is not considered. However, the dispersibility of the carbon nanofiber has a great influence on the physical properties of the composition containing the carbon nanofiber. For example, the conventional carbon nanofiber is about 10 to 50 ml / 100 g with respect to the DBP oil supply amount serving as an index of dispersibility for the resin. In a resin composition containing carbon nanofibers having such a low DBP oil absorption amount and thus low dispersibility, the physical properties of the resin are gradually impaired as the carbon nanofiber content increases, and the extensibility of the resin composition is reduced. This greatly reduces the spinning ability, makes the conductivity non-uniform, causes a large change in specific resistance with respect to temperature and humidity, and causes problems such as a decrease in kneadability and moldability.
本発明は、従来の上記課題を解決したものであって、樹脂に対してＤＢＰ吸油量を指標とする分散性に優れたカーボンナノファイバーの製造方法を提供する。なお、本発明においてカーボンナノファイバーとは、例えば直径が数十ナノメータ以下、長さが数百ミクロンメータ以下であるナノサイズの極微細炭素繊維であり、内部が中空構造のカーボンナノチューブに限らず、内部が充填された構造のものを含み、炭素層が単層構造あるいは多層構造の何れの場合も含み、炭素層が螺旋構造に限らず、また炭素層が繊維の軸長方向に伸びた構造に限らず、炭素層が径方向に伸びた構造のものも含む。
This invention solves the said conventional subject, Comprising: The manufacturing method of the carbon nanofiber excellent in the dispersibility which uses DBP oil absorption amount as a parameter | index with respect to resin is provided. In the present invention, the carbon nanofiber is, for example, a nano-sized ultrafine carbon fiber having a diameter of several tens of nanometers or less and a length of several hundreds of micrometers or less, and is not limited to a carbon nanotube having a hollow structure. Including the structure filled inside, including the case where the carbon layer is either a single layer structure or a multilayer structure, the carbon layer is not limited to a spiral structure, and the carbon layer extends in the axial direction of the fiber. Not only the thing of the structure where the carbon layer extended in the diameter direction is included.
本発明は、以下のカーボンナノファイバーの製造方法に関する。
〔１〕触媒粒子としてＦｅ、Ｎｉ、Ｃｏ、Ｍｎ、Ｃｕの酸化物から選ばれた１種または２種以上と、Ｍｇ、Ｃa、Ａｌ、Ｓｉの酸化物から選ばれた１種または２種以上の混合酸化物粉末を用い、４００℃〜８００℃の温度で、一酸化炭素および/または二酸化炭素と水素の混合ガスを上記触媒粒子に接触させて、カーボンナノファイバーを製造する気相成長法において、触媒および混合ガス組成を調整することによって、表面が親油性の無定形炭素層を有するカーボンナノファイバーを製造することを特徴とする方法。
〔２〕上記[１]の製造方法において、触媒としてＣｏ 3 Ｏ 4 とＭｇＯの混合粉末、またはＭｇＯの表面がＣｏ 3 Ｏ 4 によって被覆された粉末を用い、原料混合ガスのＣＯ/Ｈ 2 比を５０/５０〜９９/１に調整し、反応後に連続して反応温度と同一温度下で水素ガスで１０分間以上処理することによって、ＤＢＰ吸油量が１５０ml/100ｇ以上のカーボンナノファイバーを製造する方法。
The present invention relates to the following method for producing carbon nanofibers.
[1] As catalyst particles, one or more selected from oxides of Fe, Ni, Co, Mn, and Cu, and one or more selected from oxides of Mg, Ca, Al, and Si In the vapor phase growth method for producing carbon nanofibers, the mixed oxide powder is used, and the catalyst particles are brought into contact with carbon monoxide and / or a mixed gas of carbon dioxide and hydrogen at a temperature of 400 ° C. to 800 ° C. A method for producing a carbon nanofiber having an amorphous carbon layer having a lipophilic surface by adjusting a catalyst and a mixed gas composition.
[2] In the production method of the above [1], a mixed powder of Co 3 O 4 and MgO or a powder whose surface of MgO is coated with Co 3 O 4 is used as a catalyst, and the CO / H 2 ratio of the raw material mixed gas Is adjusted to 50/50 to 99/1, and after the reaction, carbon nanofibers having a DBP oil absorption of 150 ml / 100 g or more are produced by continuously treating with hydrogen gas at the same temperature as the reaction temperature for 10 minutes or more. Method.
本発明のカーボンナノファイバーはＤＢＰ吸油量が１５０ml/100ｇ以上であるので、樹脂に対する分散性に優れており、従来よりも多量に樹脂に配合しても、樹脂本来の引張強度や伸長性を維持することができる。また、本発明のカーボンナノファイバーは分散性が良いので樹脂に比較的少量配合しても高い導電性や強度の補強効果を得ることができる。 Since the carbon nanofiber of the present invention has a DBP oil absorption of 150 ml / 100 g or more, it has excellent dispersibility in the resin and maintains the original tensile strength and extensibility of the resin even when blended in a larger amount than before. can do. In addition, since the carbon nanofibers of the present invention have good dispersibility, a high electrical conductivity and strength reinforcing effect can be obtained even if a relatively small amount is added to the resin.
本発明に係るカーボンナノファイバーは、例えば、ＤＢＰ吸油量１５０ml/100ｇ以上であって、圧密体の体積抵抗値が１.０Ωcm以下、直径５〜１００nmおよびアスペクト比１０以上、ＢＥＴ比表面積４００m2/g以下である内部が中空構造のカーボンナノファイバー（カーボンナノチューブ）である。これは導電フィラーとして好適であり、樹脂に配合したものは、例えば、導電性シート、導電性糸、導電性コーテング材、導電性塗膜、導電性成形品などの導電性材料として広く利用することができる。また、上記カーボンナノファイバーは補強材として好適であり、樹脂に配合することによって機械的強度を高めた高強度樹脂材料として利用することができる。 The carbon nanofiber according to the present invention has, for example, a DBP oil absorption of 150 ml / 100 g or more, a volume resistance value of the compacted body of 1.0 Ωcm or less, a diameter of 5 to 100 nm, an aspect ratio of 10 or more, and a BET specific surface area of 400 m 2 / The inside which is g or less is a carbon nanofiber (carbon nanotube) having a hollow structure. This is suitable as a conductive filler, and what is blended in a resin is widely used as a conductive material such as a conductive sheet, conductive yarn, conductive coating material, conductive coating film, and conductive molded article. Can do. Moreover, the said carbon nanofiber is suitable as a reinforcing material, and can be utilized as a high-strength resin material which raised the mechanical strength by mix | blending with resin.
本発明のカーボンナノファイバーは、例えば、触媒粒子としてＦｅ、Ｎｉ、Ｃｏ、Ｍｎ、Ｃｕの酸化物から選ばれた１種または２種以上と、Ｍｇ、Ｃa、Ａｌ、Ｓｉの酸化物から選ばれた１種または２種以上の混合酸化物粉末を用い、４００℃〜８００℃の温度で、一酸化炭素または二酸化炭素と水素の混合ガスを上記触媒粒子に接触させて、カーボンナノファイバーを製造する気相成長法において、触媒および混合ガス組成を調整することによって製造することができる。上記方法によって製造したカーボンナノファイバーは表面が親油性の無定形炭素層を有するので、ＤＢＰ吸油量が１５０ml/100ｇ以上のカーボンナノファイバーを得ることができる。 The carbon nanofiber of the present invention is selected from, for example, one or more selected from oxides of Fe, Ni, Co, Mn, and Cu as catalyst particles, and oxides of Mg, Ca, Al, and Si. In addition, one or two or more mixed oxide powders are used, and carbon monoxide or a mixed gas of carbon dioxide and hydrogen is brought into contact with the catalyst particles at a temperature of 400 ° C. to 800 ° C. to produce carbon nanofibers. In the vapor phase growth method, it can be produced by adjusting the catalyst and mixed gas composition. Since the carbon nanofibers produced by the above method have a lipophilic amorphous carbon layer, carbon nanofibers having a DBP oil absorption of 150 ml / 100 g or more can be obtained.
以下、本発明を具体的な実施の形態に基づいて説明する。
本発明は、触媒粒子としてＦｅ、Ｎｉ、Ｃｏ、Ｍｎ、Ｃｕの酸化物から選ばれた１種または２種以上と、Ｍｇ、Ｃa、Ａｌ、Ｓｉの酸化物から選ばれた１種または２種以上の混合酸化物粉末を用い、４００℃〜８００℃の温度で、一酸化炭素および/または二酸化炭素と水素の混合ガスを上記触媒粒子に接触させて、カーボンナノファイバーを製造する気相成長法において、触媒および混合ガス組成を調整することによって、表面が親油性の無定形炭素層を有するカーボンナノファイバーを製造することを特徴とする方法である。
本発明のカーボンナノファイバーは、ＤＢＰ吸油量が１５０ml/100ｇ以上であり、好ましくはＤＢＰ吸油量が２００ml/100ｇ、より好ましくは３００ml/100ｇ以上である。従って、本発明のカーボンナノファイバーは樹脂に対する分散性に優れており、従来のものより多量に樹脂に配合しても、樹脂本来の物性を損なわず、引張強度や伸長性などを実用範囲内に維持することができる。
Hereinafter, the present invention will be described based on specific embodiments.
In the present invention, the catalyst particles are one or more selected from oxides of Fe, Ni, Co, Mn, and Cu, and one or two selected from oxides of Mg, Ca, Al, and Si. Vapor phase growth method for producing carbon nanofibers by using the above mixed oxide powder and bringing carbon monoxide and / or a mixed gas of carbon dioxide and hydrogen into contact with the catalyst particles at a temperature of 400 ° C. to 800 ° C. In the method, carbon nanofibers having an amorphous carbon layer having a lipophilic surface are produced by adjusting the composition of the catalyst and the mixed gas.
The carbon nanofiber of the present invention has a DBP oil absorption of 150 ml / 100 g or more , preferably a DBP oil absorption of 200 ml / 100 g, more preferably 300 ml / 100 g or more. Therefore, the carbon nanofibers of the present invention are excellent in resin dispersibility, and even if blended in a larger amount than conventional ones, the original physical properties of the resin are not impaired, and the tensile strength and extensibility are within the practical range. Can be maintained.
具体的には、実施例に示すように、本発明のＤＢＰ吸油量が２５０ml/100ｇのカーボンナノファイバーをＰＥＴ樹脂に５wt％配合した樹脂組成物は、これを紡糸して単糸太さ８(dT/f)の導電糸を製造することができ、この導電糸の引張強度は３.０g/dT、伸度１５％であり、ＰＥＴ樹脂本来の引張強度および伸度をやや下回る程度で糸として充分な機械的特性を有する。一方、ＤＢＰ吸油量が８０ml/100ｇである従来のカーボンナノファイバーをＰＥＴ樹脂に５wt％配合した樹脂組成物は樹脂本来の物性が大きく損なわれて紡糸不能であった。 Specifically, as shown in the Examples, a resin composition in which 5 wt% of carbon nanofibers having a DBP oil absorption of the present invention of 250 ml / 100 g are blended with PET resin is spun to obtain a single yarn thickness of 8 ( dT / f) conductive yarn can be produced. The conductive yarn has a tensile strength of 3.0 g / dT and an elongation of 15%. As a yarn that is slightly below the original tensile strength and elongation of PET resin. Has sufficient mechanical properties. On the other hand, a resin composition in which 5 wt% of a conventional carbon nanofiber having a DBP oil absorption of 80 ml / 100 g is blended in a PET resin cannot be spun because the original physical properties of the resin are greatly impaired.
本発明のカーボンナノファイバーは樹脂に対して馴染みやすいので、例えば、ＤＢＰ吸油量１５０ml/100ｇ以上であって、圧密体の体積抵抗値が１.０Ωcm以下、直径５〜１００nmおよびアスペクト比１０以上、ＢＥＴ比表面積２５０m2/g以下である内部が中空構造のカーボンナノファイバー（カーボンナノチューブ）を樹脂に配合した樹脂組成物では、カーボンナノファイバーの配合量が従来のものより少なくても、分散性が良いので、高い導電性と強度の補強効果を得ることができる。 Since the carbon nanofibers of the present invention are easily adapted to the resin, for example, the DBP oil absorption is 150 ml / 100 g or more, the volume resistance value of the compact is 1.0 Ωcm or less, the diameter is 5 to 100 nm, and the aspect ratio is 10 or more. In a resin composition in which carbon nanofibers (carbon nanotubes) having a BET specific surface area of 250 m 2 / g or less and having a hollow inside are blended with a resin, the dispersibility is improved even if the amount of carbon nanofibers is less than that of the conventional one. Since it is good, a high conductivity and strength reinforcing effect can be obtained.
具体的には、ＤＢＰ吸油量３００ml/100ｇ、圧密体の体積抵抗値５.０×１０-2Ωcm、直径２０nm、スペクト比が平均約１００、ＢＥＴ比表面積４００m2/gの本発明に係るカーボンナノファイバーをＰＣ樹脂に４wt％配合した樹脂組成物を、厚さ１００μmのＰＣフィルムに成形したものは、表面抵抗が１×１０5Ω・cm（100Ｖ電圧下）で、引張強度が６０（ＭＰａ）、引張伸びが１００％である。一方、ＤＢＰ吸油量が１０ml/100ｇであって圧密体の体積抵抗およびＢＥＴ比表面積が上記と同程度である従来のカーボンナノファイバーをＰＣ樹脂に５wt％配合した樹脂組成物では、充分な強度と伸びが得られないためシート化はできなかった。本発明のカーボンナノファイバーを用いたものは、カーボンナノファイバーの配合量が少なくても従来と同等または同等以上の導電性を有することができる。 Specifically, carbon according to the present invention having a DBP oil absorption of 300 ml / 100 g, a volume resistance value of a compacted body of 5.0 × 10 −2 Ωcm, a diameter of 20 nm, an average spect ratio of about 100, and a BET specific surface area of 400 m 2 / g. A resin composition obtained by blending 4% by weight of nanofibers with PC resin and molded into a PC film with a thickness of 100 μm has a surface resistance of 1 × 10 5 Ω · cm (under 100 V voltage) and a tensile strength of 60 (MPa ), The tensile elongation is 100%. On the other hand, a resin composition in which 5 wt% of conventional carbon nanofibers with a DBP oil absorption of 10 ml / 100 g and a compact body having a volume resistance and a BET specific surface area of the same degree as described above are blended with PC resin has sufficient strength. The sheet could not be formed because no elongation was obtained. The thing using the carbon nanofiber of this invention can have the electroconductivity equivalent to or equivalent to the past even if there are few compounding quantities of a carbon nanofiber.
本発明に係るカーボンナノファイバーは、従来よりも低温製造が可能で、黒鉛処理を必要とせずに、本体が結晶質の黒鉛構造を有し、表面が無定形炭素層を有するカーボンナノファイバーの製造方法に基づき、この製造条件を調整して製造することができる。 The carbon nanofiber according to the present invention can be produced at a lower temperature than conventional carbon nanofibers without the need for graphite treatment, and the main body has a crystalline graphite structure and the surface has an amorphous carbon layer. Based on the method, the manufacturing conditions can be adjusted and manufactured.
上記製造方法は、例えば、触媒粒子としてＦｅ、Ｎｉ、Ｃｏ、Ｍｎ、Ｃｕの酸化物から選ばれた１種または２種以上と、Ｍｇ、Ｃa、Ａｌ、Ｓｉの酸化物から選ばれた１種または２種以上の混合酸化物粉末を用い、４００℃〜８００℃の温度で、一酸化炭素または二酸化炭素と水素の混合ガスを上記触媒粒子に接触させて、カーボンナノファイバーを製造する気相成長法である。 The above production method is, for example, one or more kinds selected from oxides of Fe, Ni, Co, Mn, and Cu as catalyst particles and one kind selected from oxides of Mg, Ca, Al, and Si. Alternatively, vapor phase growth in which carbon nanofibers are produced by using two or more mixed oxide powders and contacting carbon monoxide or a mixed gas of carbon dioxide and hydrogen with the catalyst particles at a temperature of 400 ° C. to 800 ° C. Is the law.
上記製造方法において、具体的には、触媒として第ＶIIａ族、第ＶII族I、第Ｉｂ族（遷移金属）元素の酸化物、特にＦｅ、Ｎｉ、Ｃｏ、Ｍｎ、Ｃｕの酸化物から選ばれた１種または２種以上と、Ｍｇ、Ｃa、Ａｌ、Ｓｉの各酸化物の１種または２種以上からなる混合酸化物粉末を用いる。これらの金属酸化物粉末は混合粉末、複合粉末、固溶粉末の何れでも良い。 In the above production method, specifically, the catalyst was selected from Group VIIa, Group VII I, Group Ib (transition metal) element oxides, particularly oxides of Fe, Ni, Co, Mn, and Cu. A mixed oxide powder composed of one or more kinds and one or more kinds of oxides of Mg, Ca, Al, and Si is used. These metal oxide powders may be mixed powders, composite powders, or solid solution powders.
上記金属酸化物粉末のうち、Ｃｏ酸化物とＭｇの酸化物の混合粉末あるいはＭｇ酸化物表面がＣｏ酸化物によって被覆された粉末、さらに好ましくはＣｏ3Ｏ4とＭｇＯの混合粉末またはのＭｇＯ表面がＣｏ3Ｏ4によって被覆された粉末が好ましい。これらのＣｏ酸化物とＭｇ酸化物からなる混合粉末の重量比（Ｃｏ酸化物／Ｍｇ酸化物）は９０／１０〜１０／９０が適当であり、８０／２０〜５０／５０が好ましい。 Among the above metal oxide powders, a mixed powder of Co oxide and Mg oxide or a powder in which the Mg oxide surface is coated with Co oxide, more preferably a mixed powder of Co 3 O 4 and MgO or an MgO surface Is preferably a powder coated with Co 3 O 4 . The weight ratio (Co oxide / Mg oxide) of the mixed powder composed of Co oxide and Mg oxide is suitably 90/10 to 10/90, and preferably 80/20 to 50/50.
触媒粒子の大きさは、一次粒子の平均粒径が１ｎｍ〜１μｍ、好ましくは５ｎｍ〜１００ｎｍnmの範囲内が好ましい。通常、このような粒径の微粉末は凝集して１００μm前後の凝集粒子を形成する場合があるが、凝集粒子であっても、ガスは粒子表面に浸透するので反応に大きな影響はない。なお、触媒粒子のハンドリング性を高めるには、粒径１００ｎｍ〜５０μmの範囲が好ましい。この触媒粒子をファイバーの成長核として石英などの基板上に配置する。触媒粒子の基板上への配置は、触媒粒子をそのまま均一にボートに振りかければよい。または触媒粒子をアルコール等の溶媒に懸濁させて懸濁液を調製し、この懸濁液を基板上に散布して乾燥することによって均一にボート上に配置してもよい。 The size of the catalyst particles is such that the average primary particle diameter is in the range of 1 nm to 1 μm, preferably 5 nm to 100 nm. Usually, the fine powder having such a particle size may be aggregated to form aggregated particles of about 100 μm. However, even the aggregated particles have no significant influence on the reaction because the gas penetrates the particle surface. In order to improve the handling property of the catalyst particles, the particle size is preferably in the range of 100 nm to 50 μm. The catalyst particles are arranged on a substrate such as quartz as a fiber growth nucleus. The catalyst particles may be arranged on the substrate as long as the catalyst particles are uniformly shaken on the boat. Alternatively, the catalyst particles may be suspended in a solvent such as alcohol to prepare a suspension, and the suspension may be sprayed on a substrate and dried to be uniformly disposed on the boat.
反応室内で０.０８〜１０ＭＰａの圧力下、４５０℃〜８００℃の温度で、原料ガスを上記触媒粒子に接触させて反応させることによって多結晶構造グラファイトナノファイバーを成長させる。このカーボンナノファイバーの気相合成においては、予め十分に合成雰囲気を定常化する必要がある。そのため、水素を１０％程度含む不活性ガスを反応室に導入して合成雰囲気を置換した後に加熱を開始し、合成温度に１〜２時間ほど保持することが望ましい。 Polycrystalline graphite nanofibers are grown by bringing the raw material gas into contact with the catalyst particles and reacting them at a temperature of 450 to 800 ° C. under a pressure of 0.08 to 10 MPa in a reaction chamber. In the gas phase synthesis of carbon nanofibers, it is necessary to sufficiently stabilize the synthesis atmosphere in advance. Therefore, it is desirable to start heating after introducing an inert gas containing about 10% of hydrogen into the reaction chamber to replace the synthesis atmosphere, and to maintain the synthesis temperature for about 1 to 2 hours.
反応室内の温度および雰囲気を定常状態にしてから、原料ガスを導入し、触媒粒子に接触させ、原料ガスを熱分解させてグラファイトを成長させる。原料ガスとしては一酸化炭素および／または二酸化炭素と水素の混合ガスを用いることができる。混合ガスのＣＯおよび／またはＣＯ２に対するＨ2の混合容積比（ＣＯ／Ｈ2）は２０／８０〜９９／１が適当であり、５０／５０〜９９／１が好ましい。この原料ガスを例えば０.０１〜２４時間供給してカーボンナノファイバーを触媒粒子から成長させる。 After bringing the temperature and atmosphere in the reaction chamber to a steady state, the raw material gas is introduced, brought into contact with the catalyst particles, and the raw material gas is thermally decomposed to grow graphite. As the source gas, carbon monoxide and / or a mixed gas of carbon dioxide and hydrogen can be used. The mixing volume ratio (CO / H 2 ) of H 2 to CO and / or CO 2 in the mixed gas is suitably 20/80 to 99/1, preferably 50/50 to 99/1. This raw material gas is supplied, for example, for 0.01 to 24 hours to grow carbon nanofibers from the catalyst particles.
上記製造方法において、ＤＢＰ吸油量が高いカーボンナノファイバーを得るには、触媒粒子の組合せと原料ガス組成を調整し、反応後に水素ガスで処理すると良い。具体的には、触媒としてＣｏ酸化物とＭｇの酸化物の混合粉末あるいはＭｇ酸化物表面がＣｏ酸化物によって被覆された粉末、さらに好ましくはＣｏ3Ｏ4とＭｇＯの混合粉末またはＭｇＯの表面がＣｏ3Ｏ4によって被覆された粉末を用い、ハイドロカーボンを含まない炭素源を使用し、具体的には一酸化炭素および／または二酸化炭素を使用し、合成温度を５５０℃〜６５０℃にし、原料混合ガスのＣＯ／Ｈ２比を５０／５０~９９／１に調整し、反応後に連続して反応温度と同一温度下で水素ガスで１０分間以上処理することによって、ＤＢＰ吸油量が１５０ml/100ｇ以上のカーボンナノファイバーを製造することができる。 In the above production method, in order to obtain carbon nanofibers having a high DBP oil absorption, the combination of catalyst particles and the raw material gas composition are adjusted, and the reaction is preferably performed with hydrogen gas after the reaction. Specifically, as a catalyst, a mixed powder of Co oxide and Mg oxide or a powder in which the surface of Mg oxide is coated with Co oxide, more preferably a mixed powder of Co 3 O 4 and MgO or the surface of MgO is used. Using a powder coated with Co 3 O 4 , using a carbon source that does not contain hydrocarbons, specifically using carbon monoxide and / or carbon dioxide, setting the synthesis temperature to 550 ° C. to 650 ° C. By adjusting the CO / H2 ratio of the mixed gas to 50/50 to 99/1 and continuously treating with hydrogen gas for 10 minutes or more under the same temperature as the reaction temperature after the reaction, the DBP oil absorption is 150 ml / 100 g or more. The carbon nanofiber can be produced.
上記製造方法を実施する装置として、図１に示す熱処理炉２０を用いることができる。この熱処理炉２０は断熱材からなる装置本体２１を有し、この本体２１の内部は２枚の仕切板２６によって仕切ることによって装置中央を貫通するガス流路２７が形成されており、該ガス流路２７を囲むように発熱体２２が設置されている。発熱体２２としては白熱ランプ、ハロゲンランプ、アークランプ、グラファイトヒータ等を用いることができる。このガス流路２７の一方の開口部はガス供給口２４であり、他方の開口部はガス排出口２９である。ガス流路２７には基板２８が取出し台３１の上に載置される。
As an apparatus for performing the above manufacturing method, a heat treatment furnace 20 shown in FIG. 1 can be used. The heat treatment furnace 20 has an apparatus main body 21 made of a heat insulating material, and a
基板２８に触媒粉末３２を載せた後、その基板２８を取出し台３１の上に載せて熱処理炉２０のガス流路内に収納する。次いで、熱処理炉２０の圧力を０.０８〜１０ＭＰａの範囲内に制御して、原料の混合ガスを供給口２４から導入し、発熱体２２によって炉内を４５０℃〜８００℃、好ましくは５５０℃〜６５０℃に加熱し、原料ガスを触媒粒子に接触させて反応させ、グラファイトを成長させてカーボンナノファイバー３３を形成させる。
After the
製造したカーボンナノファイバーには触媒が残存するので、硝酸、塩酸、フッ酸等の酸性溶液に浸漬させて、触媒粒子を除去する。なお、触媒粒子をそのままカーボンファイバーに含有させて担持させた状態で使用してもよい。 Since the catalyst remains in the produced carbon nanofibers, the catalyst particles are removed by dipping in an acidic solution such as nitric acid, hydrochloric acid, or hydrofluoric acid. In addition, you may use it in the state made to carry | support the catalyst particle as it is in carbon fiber.
以下に本発明の実施例を比較例と共に示す。
〔実施例１〜５、比較例１〜３〕
図１に示す熱処理炉を用い、表１に示す条件下でカーボンナノファイバーを合成した。このカーボンナノファイバーについて、ＤＢＰ吸油量および抵抗率を測定した。抵抗率の測定はカーボンナノファイバーを１００kg/cm2の圧力でプレスし、四端子法で抵抗値を測定することにより求めた。また、製造したカーボンナノファイバーを樹脂に配合して樹脂組成物を形成し、この樹脂組成物を熔融紡糸法により紡糸して、太さ３８０ｄT/48ｆマルチフィラメントを得た。得られた糸について、体積抵抗値、表面状態、強度、伸度を表２に示した。
Examples of the present invention are shown below together with comparative examples.
[Examples 1-5, Comparative Examples 1-3]
Carbon nanofibers were synthesized under the conditions shown in Table 1 using the heat treatment furnace shown in FIG. About this carbon nanofiber, DBP oil absorption and resistivity were measured. The resistivity was determined by pressing carbon nanofibers at a pressure of 100 kg / cm 2 and measuring the resistance value by the four probe method. Further, the produced carbon nanofiber was blended with a resin to form a resin composition, and this resin composition was spun by a melt spinning method to obtain a multifilament having a thickness of 380 dT / 48f. Table 2 shows the volume resistance, surface state, strength, and elongation of the obtained yarn.
表１の結果に示すように、触媒と原料ガス組成を調整することによって、カーボンナノファイバーのＤＢＰ吸油量が異なる。具体的には、触媒としてＣｏ3Ｏ4とＭｇＯの混合粉末を用い、また原料ガスに一酸化炭素と水素の混合ガスを用い、これらの混合比率を変えて製造した。一方、比較例として、鉄ニッケル金属粉末担持アルミナ触媒を使用し、原料ガスにエチレンガスと一酸化炭素の混合ガスを使用した場合を示す。表２の結果に示すように、カーボンナノファイバーを配合した樹脂組成物は、カーボンナノファイバーのＤＢＰ吸油量によって物性が大幅に異なる。 As shown in the results of Table 1, the DBP oil absorption amount of the carbon nanofibers is different by adjusting the catalyst and the raw material gas composition. Specifically, a mixed powder of Co 3 O 4 and MgO was used as a catalyst, a mixed gas of carbon monoxide and hydrogen was used as a raw material gas, and the mixing ratio was changed. On the other hand, as a comparative example, an iron nickel metal powder-supported alumina catalyst is used and a mixed gas of ethylene gas and carbon monoxide is used as a raw material gas. As shown in the results of Table 2, the physical properties of the resin composition containing carbon nanofibers vary greatly depending on the DBP oil absorption of the carbon nanofibers.
２０−熱処理炉、２１−装置本体、２２−発熱体、２４−供給口、２６−仕切板、２７−ガス流路、２８−基板、２９−排出口、３１−取出し台、３２−触媒粉末、３３−カーボンナノファイバー。
20-heat treatment furnace, 21-device main body, 22-heating element, 24-supply port, 26-partition plate, 27-gas flow path, 28-substrate, 29-discharge port, 31-extraction stand, 32-catalyst powder, 33-carbon nanofiber.
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| JP2004300631A (en) * | 2003-03-31 | 2004-10-28 | Mitsubishi Materials Corp | Carbon nanofiber and method for producing the same |
| JP2004299986A (en) * | 2003-03-31 | 2004-10-28 | Mitsubishi Materials Corp | Carbon nanotube, and its production method |
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| JP2004075848A (en) * | 2002-08-19 | 2004-03-11 | Asahi Glass Co Ltd | Conductive fluoro-copolymer composition and laminate using the same |
| JP2004300631A (en) * | 2003-03-31 | 2004-10-28 | Mitsubishi Materials Corp | Carbon nanofiber and method for producing the same |
| JP2004299986A (en) * | 2003-03-31 | 2004-10-28 | Mitsubishi Materials Corp | Carbon nanotube, and its production method |
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| US9505622B2 (en) | 2011-09-30 | 2016-11-29 | Mitsubishi Materials Corporation | Carbon nanofibers encapsulating metal cobalt, and production method therefor |
| EP2838837A4 (en) * | 2012-04-16 | 2015-12-23 | Seerstone Llc | Methods and structures for reducing carbon oxides with non-ferrous catalysts |
| US9796591B2 (en) | 2012-04-16 | 2017-10-24 | Seerstone Llc | Methods for reducing carbon oxides with non ferrous catalysts and forming solid carbon products |
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