JPS6038472A - Composite-structure carbon black and production thereof - Google Patents
Composite-structure carbon black and production thereofInfo
- Publication number
- JPS6038472A JPS6038472A JP58146710A JP14671083A JPS6038472A JP S6038472 A JPS6038472 A JP S6038472A JP 58146710 A JP58146710 A JP 58146710A JP 14671083 A JP14671083 A JP 14671083A JP S6038472 A JPS6038472 A JP S6038472A
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- carbon black
- blank
- fibrous
- fibrous carbon
- 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.)
- Granted
Links
- 239000006229 carbon black Substances 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 58
- 239000007789 gas Substances 0.000 claims abstract description 15
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 11
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 7
- 239000010419 fine particle Substances 0.000 claims abstract description 5
- 239000012808 vapor phase Substances 0.000 claims abstract description 4
- 239000012159 carrier gas Substances 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 10
- 150000002736 metal compounds Chemical class 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000013528 metallic particle Substances 0.000 abstract 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 241000872198 Serjania polyphylla Species 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 238000010008 shearing Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- -1 oxides Chemical class 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 239000011231 conductive filler Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011882 ultra-fine particle Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 241000269821 Scombridae Species 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 235000020640 mackerel Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は通常のカーボンブラックの空隙内に気相法によ
り繊維状炭素を成長さ・Ｉることにより、電子部品や感
光紙の輸送包装分野において、帯電防止、静電気除去に
効果のある、電気伝導度、加工性その他の緒特性を改良
した複合構造のカーボンブラック及びその製法に関する
。DETAILED DESCRIPTION OF THE INVENTION By growing fibrous carbon in the voids of ordinary carbon black using a vapor phase method, the present invention can be used to prevent static electricity and eliminate static electricity in the transport packaging field of electronic parts and photosensitive paper. The present invention relates to a carbon black with a composite structure that is effective in improving electrical conductivity, processability, and other properties, and a method for producing the same.
通常のカーボンブラックの一次粒子を電子顕微鏡で観察
すると平均粒径１０〜３００ｍμの球状粒子からなる。When primary particles of ordinary carbon black are observed under an electron microscope, they consist of spherical particles with an average particle size of 10 to 300 mμ.
この粒子は更に折り重なるように二次凝集したり、結合
したりして、大小のストラフチャーを形成している。こ
れが本発明でいう通常のカーボンブランクである。These particles are further folded to form secondary aggregation or bonding, forming large and small stractures. This is the normal carbon blank referred to in the present invention.
カーボンブランクの特性は粒子径の大小、ストラフチャ
ーの大小及び粒子表面に存在する化学的活性基の多少に
依存し、それぞれの特性に応じて、ゴム補強用、カラー
用、電気伝導材用、乾電池用等に利用され、使い分けら
れている。The properties of carbon blanks depend on the size of the particle size, the size of the stracture, and the number of chemically active groups present on the particle surface, and depending on each property, it can be used for rubber reinforcement, colors, electrically conductive materials, and dry batteries. It is used for various purposes and is used differently.
一方、本発明における繊維状炭素としては、ポリアクリ
ロニトリル、レーヨン、ピッチ等を紡糸した有機前駆体
繊維を８００〜３０００１：に加熱して得た有機系繊維
状炭素がある。又、これらとは全く別に、炭化水素ガス
を熱分解し°Ｃ得られる気相成長繊維状炭素がある。気
相成長繊維状炭素は一般に、結晶欠陥が極め°ζ少なく
、引張り強度や弾性率が優れているが、生産効率が低い
欠点がある。On the other hand, the fibrous carbon used in the present invention includes organic fibrous carbon obtained by heating organic precursor fibers spun from polyacrylonitrile, rayon, pitch, etc. to a temperature of 800 to 30,001. In addition, completely apart from these, there is vapor-grown fibrous carbon obtained by thermally decomposing hydrocarbon gas at °C. Vapor-grown fibrous carbon generally has very few crystal defects and has excellent tensile strength and elastic modulus, but has the drawback of low production efficiency.
樹脂、ゴノ、等の導電性フィラーとして用いられるカー
ボンブランクの特性としては電気伝導性が優れている他
、樹脂、ゴム等とのなしのがよいこと、混合性がよいこ
と、成形時に溶融樹脂の流動性を損なわず、且つ、成形
された製品の表面状態に平滑性をすえることが重要であ
る。前述の通り、これらカーボンブランクの諸特性し１
口１γ了の大小、ストラフチャーの大小、カーボンブラ
ンク表面の活性基の多少等に依存するものであるが、導
電性フィラーとしての見地から、前記諸特性の中、特に
ストラフチャーが大きな影響を有Ｊ−る。Characteristics of carbon blanks used as conductive fillers for resins, gonos, etc. include excellent electrical conductivity, good compatibility with resins, rubber, etc., good mixability, and molten resin during molding. It is important to maintain smoothness on the surface of the molded product without impairing its fluidity. As mentioned above, the characteristics of these carbon blanks are 1
Although it depends on the size of the pore size, the size of the struture, the number of active groups on the surface of the carbon blank, etc., from the standpoint of a conductive filler, the struture has a particularly large influence among the above-mentioned properties. Ru.
一般に、カーボンブラックを樹脂やゴムに配合する場合
、高度に発達したストラクヂ中−のカー、ポンプランク
を使用しても、混合の際に受りる機械的剪断力により、
ストラフチャーが切断され、電気伝導度が低下する現象
が認められる。この場合、カーボンブランクの充重量を
増加して、電気伝導度の低下を補充することも考えられ
るが、現実には樹脂の加工性が著しく低下する。Generally, when blending carbon black with resin or rubber, even if highly developed struc- ture media and pump cranks are used, the mechanical shearing force received during mixing will cause
A phenomenon in which the strafe is cut and the electrical conductivity decreases is observed. In this case, it is conceivable to increase the filled weight of the carbon blank to compensate for the decrease in electrical conductivity, but in reality, the processability of the resin will be significantly reduced.
以上の現状であるため、導電性フィラーとしてのカーボ
ンブランクを改良するにあたっては、機械的剪断力を受
番ノでも切断されないような強度の結合力を有するスト
ラフチャーを得るか、又は、切断されても一次粒子が再
び互いに接触しあえるよ・うな形状のカーボンブランク
を得ることである。Due to the current situation described above, in order to improve the carbon blank as a conductive filler, it is necessary to obtain a stracture that has a strong bonding force that will not be broken even by mechanical shearing force, or The objective is to obtain a carbon blank with a shape that allows the primary particles to come into contact with each other again.
本発明者らは気相法炭素繊維の製造のｉに用いられるシ
ーディング法（特開昭５７−１１７６２３号公報）を応
用し、通常のカーボンブラックの空隙内に繊維状炭素を
成長さゼることにより、たとえ機械的剪断応力により切
断されても一次粒子が再び互いに接触しあえるような形
状の複合構造のカーボンブランクが得られることを見出
し、本発明を完成するに至った。The present inventors applied the seeding method (Japanese Unexamined Patent Publication No. 117623/1983) used in the production of vapor-grown carbon fibers to grow fibrous carbon within the voids of ordinary carbon black. By doing so, it was discovered that a carbon blank with a composite structure in a shape that allows the primary particles to come into contact with each other again even if they are cut by mechanical shearing stress can be obtained, and the present invention was completed based on this finding.
即ち、本発明は通常のカーボンブラックば高空隙性の構
造であることを利用し、カーボンブラックに金属又は金
属化合物の微粒子・を混在、担持さセ、これを不活性ガ
ス気流中で！１０１３−１５００℃に加熱し、その後炭
化水素ガスを送入゛Ｊることにより、カーボンブラック
の空隙内に繊維状炭素の介在した複合構造のカーボンブ
ラックを得るものであり、本発明によれば電気抵抗が高
い場合でも０．３０＜’２−ｃｍ以下、Ｊ’Ｍは０．２
５Ω−ｃｍ以下（５（ＩＫｇ／ ｃＡ ）となり、樹脂
、ゴム等と混合するとき成形（Ｉ＋がよく、得られた成
形体の電気抵抗も小さい。That is, the present invention takes advantage of the high porosity structure of ordinary carbon black, mixes and supports fine particles of metal or metal compound on carbon black, and then injects this in an inert gas stream! By heating to 1013-1500°C and then introducing hydrocarbon gas, carbon black with a composite structure in which fibrous carbon is interposed in the voids of carbon black is obtained.According to the present invention, electric Even if the resistance is high, 0.30<'2-cm or less, J'M is 0.2
It is 5 Ω-cm or less (5 (IKg/cA)), and when mixed with resin, rubber, etc., the molding (I+) is good, and the electrical resistance of the obtained molded product is also small.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明に使用するカーボンシラツクはアセチレンブラッ
ク、ファーネスブランク、リーーマルブラソク、チャン
ネルブランクその他副生、回収カーボンブランクの全て
を含み、その形状は粉状、プレス状、粒状等、繊維状炭
素を除く通席のカーボンブラックが使用できる。中でも
、それ自体、電気伝導性を付与する目的で製造されたア
セチレン。The carbon silk used in the present invention includes acetylene black, furnace blank, legal blank, channel blank, other by-products, and recovered carbon blank, and its shapes include powder, pressed, granular, etc., and fibrous carbon. Carbon black can be used except for commuting seats. Among these, acetylene itself is manufactured for the purpose of imparting electrical conductivity.
ブラックの粒状品が特に好ましい。Black granules are particularly preferred.
シーディングする、即ちカーボンブラックに担持させる
金属としては周期律表の第４８族、第５８族、第６８族
、第７８族、第８族等を用いることができるが、中でも
Ｆｅ、 Ｃ０％ Ｎ＋、■、Ｎｂ、 Ｔａ、 Ｔｉ、
Ｚｒ等が効果的であり、金属又は金属化合物として使用
できる。金属化合物としては」二記金属の酸化物、炭化
物、その他の化合物が使用できる。この中には気相法炭
素繊維の生成条件下にあって、水素により還元され、金
属になるものもある。これらの金属或いは金属化合物は
超微粒子がよく、特に３００Å以下のものが好ましい。As the metal to be seeded, that is, supported on carbon black, metals from Group 48, Group 58, Group 68, Group 78, Group 8 of the periodic table, etc. can be used, and among them, Fe, C0% N+ , ■, Nb, Ta, Ti,
Zr and the like are effective and can be used as metals or metal compounds. As the metal compound, oxides, carbides, and other compounds of metals can be used. Some of these are reduced to metals by hydrogen under the conditions for producing vapor-grown carbon fibers. These metals or metal compounds preferably have ultrafine particles, particularly those with a particle size of 300 Å or less.
カーボンブランクに担持さ−Ｕた金属超微粒子を起点と
して直径数１００人から数１＋１００人の極めて細い繊
維状の炭素が、金属超微粒子を頭につ＆Ｊたままカーボ
ンブランクの組織間空隙内に成長し、複合構造を形成す
る。Starting from the metal ultrafine particles supported on the carbon blank, extremely thin fibrous carbon with a diameter of several hundred to several 1+100 particles grows into the interstitial voids of the carbon blank with the metal ultrafine particles at the head. and form a composite structure.
カーボンブランクに金属超ｆｆ、？ ｌ’ｔ）子を担持
さ−１るシーディング法としては特に限定はなく、例え
ばアルコール等の溶媒に微粒子を懸濁させ、或いは金属
塩等をアルコールにＶｇ解さゼ、ごの液中にカーボンブ
ランクを投入、攪拌、混合、脱水、乾燥ずればよい。９
濁川或いは溶解ｍを加減ずれば、担持量を調節すること
ができる。シープ、ｆング足は極めて小舟でよく、カー
ボンブラックに対し、０．００１〜０．３虫は５毛の範
囲が適当である。Metal super FF on carbon blank? There are no particular limitations on the seeding method for carrying l't) particles, and for example, fine particles are suspended in a solvent such as alcohol, or metal salts are dissolved in alcohol, and carbon is added to the solution. All you have to do is put in the blank, stir, mix, dehydrate, and dry. 9
By adjusting the turbidity or solubility m, the supported amount can be adjusted. Sheep and feng feet may be extremely small, and a range of 0.001 to 0.3 insects is suitable for carbon black.
使用する炭化水素はベンゼン、トルエン等の芳香族炭化
水素、メタン、エタン等の鎖状炭化水素及びこれらを含
む副生ガス、混合ガス等である。The hydrocarbons used include aromatic hydrocarbons such as benzene and toluene, chain hydrocarbons such as methane and ethane, and by-product gases and mixed gases containing these.
反応炉は外部加ｊ：（）方式の磁性管状炉が灯ましい磁
性管状炉に金属微粒子をシーディングし）コ１’！’／
伏カーボンブランクを供給し、９００〜１５００℃、好
ましくは９５０〜１０５０℃にｆ呆ら、更に上記炭化水
素ガスを水素を含むキ中す−ト−ガスと共に通過させる
ことにより、カーボンブランクの組織間？ど隙内にｆｉ
ｋ １ｆｌｌｌな繊維状炭素がシーディング部位から成
長する。炉内カスノ流速を２００〜２０ｔｌＯｅ＋ｎ
／ 力、１’；！ ｕ’ｌ： ノ；Ｑｉ速とすると、長
さ方向の成長がηｌ＜、１〜１０ｃｍ／／Ｉ′Ｊ程度の
低速とすると太さ方向の戊辰が主となるので、流速の調
節により長さ及び太さをＮＪ１′ｌＩ ｆｆ７できる。The reactor is externally heated: () type magnetic tube furnace is used to seed fine metal particles into a bright magnetic tube furnace) ko1'! '／
By supplying a carbon blank and heating it to 900 to 1500°C, preferably 950 to 1050°C, and passing the hydrocarbon gas together with hydrogen-containing gas, the structure of the carbon blank is heated. ? Fi in the gap
k 1flll fibrous carbon grows from the seeding site. Reduce the flow rate in the furnace to 200 to 20 tlOe+n
/ Power, 1';! u'l: ノ; If the speed is Qi, if the growth in the length direction is slow, such as ηl<, 1 to 10 cm//I'J, the growth in the thickness direction will be the main one, so the length can be increased by adjusting the flow rate. The width and thickness can be set to NJ1'lIff7.
更に、反応方法はバッチ方式に限らず、連続方式も採用
できる。Furthermore, the reaction method is not limited to a batch method, but a continuous method can also be adopted.
カーボンブラックに対する繊維状炭素の割合ＩＪ５０重
量％以下である。又、繊維状炭素の長さは１ｍｍ以下、
太さは５０μ以下である。繊維状炭素の割合が５０重■
％を越えたり、員さ、太さが上記範囲を越えると、カー
ボンブランクと繊維状炭素を別々にｔｌＩＩ備し、混合
、使用した場合と間し状況を呈し、樹脂、ゴム等との混
練時の剪…１応力により、繊維状炭素が折れ易く、導電
性イ＾ｊ与能力が低Ｔする。又、繊維同士の絡め合いに
よりフロックを形成しやすく、均等に混練しがたい。The ratio of fibrous carbon to carbon black is 50% by weight or less. In addition, the length of the fibrous carbon is 1 mm or less,
The thickness is 50μ or less. The proportion of fibrous carbon is 50% ■
If the carbon blank and fibrous carbon exceed the above range, the carbon blank and fibrous carbon may be prepared separately and mixed and used, and when kneaded with resin, rubber, etc. Due to the shearing stress of 1, the fibrous carbon easily breaks and its ability to provide conductivity becomes low. In addition, the fibers tend to form flocs due to entanglement with each other, making it difficult to knead them evenly.
キャリヤーガスとしては水素ガスが最も好まし７いが、
アルゴン等の不活性ガスを混合することもできる。混合
ガスを使用する場合には水素ガスが３０％以上存在して
いることが望ましい。キャリー１′−ガス中の炭化水素
ガス含１’ｌ ’ｔ”ｒ：Ｌ ？：＋！を度、流速等に
よって、適正範囲を選ぶが、一般的には１〜＋３０ ”
ｌ’ｌ’Ｍ％が好ましい。この範囲内で、ベンセン等の
炭素／水素比が大きい炭化水素では：１−、ｔ−’Ｊ−
１・−；す；１、を多くし、メタン等炭素／水素比が小
さい炭化水素では少なくすることが望ましい。Hydrogen gas is most preferred as the carrier gas, but
An inert gas such as argon may also be mixed. When using a mixed gas, it is desirable that hydrogen gas be present in an amount of 30% or more. Contains hydrocarbon gas in carry 1'-gas 1'l 't'r:L ?:+! The appropriate range is selected depending on degree, flow rate, etc., but generally it is 1 to +30.
l'l'M% is preferred. Within this range, for hydrocarbons with high carbon/hydrogen ratios such as benzene: 1-, t-'J-
It is desirable to increase 1.-;S;1, and to decrease it for hydrocarbons with a small carbon/hydrogen ratio such as methane.
太さについては数１００人から２（１／／°であり、カ
ーボンブラックの粒子径と同１−！度の太さも可能であ
る。長さの成長１；ｌ： １〜６０分で数μ〜敗１帥の
範囲のものを得ることができる。発生’ｔｌｆ度４Ｊ：
ｉｌｌ徹・粒子のシーディング量に依存する。The thickness ranges from several hundred to 2 (1//°, and it is possible to achieve a thickness of 1-! degree, which is the same as the particle diameter of carbon black.Length growth 1; l: several microns in 1 to 60 minutes) You can get something in the range of ~1 loss. Occurrence 'tlf degree 4J:
It depends on the amount of particle seeding.
本発明によりｉｑられた複合構造のカーボンブラックは
樹脂、ゴム等に混合した場合、カーボンブラックの空隙
中に微細な繊維状炭素が多方向に伸びているため、混練
時的断力によりσ１′１状ｔＭ造が一部切断されても、
なおかつ一部は接Ｍｌｌｌ シ、或いは至近距離にあり
、ＩＪＪ Ｊｌけやゴムのう１５（電性は非常に良好と
なる。更に、電池用とし”ども使用できる。When the carbon black with the composite structure iq according to the present invention is mixed with resin, rubber, etc., fine fibrous carbon extends in multiple directions in the voids of the carbon black, so the shearing force during kneading causes σ1'1 Even if part of the tM structure is cut off,
In addition, some of the parts are in close contact with each other or at close range, and have very good electrical properties.Furthermore, they can be used for batteries.
以下、実施例を挙げて４−一発明を具体的に説明する。Hereinafter, the 4-1 invention will be specifically explained with reference to Examples.
実施例１
アセヂレンブラック粒状品（Ｔ１気化学（１１１！Ｉｆ
！ ） １ 、０ｇに、エチルアルコール
熔解した溶液の一部を噴霧し、脱水、乾Ｊｙシた。Example 1 Acetylene black granular product (T1 gas chemistry (111! If
! ) A portion of the solution dissolved in ethyl alcohol was sprayed onto 1.0 g, dehydrated and dried.
鉄としての担持量は約０．０２重尾％であっ）ζ。これ
をアルミナ質ボートに装屓し、反応竹径５０ｍｍφの電
気炉に導入し、予め９００〜１０００℃で数分間水嵩ガ
スのみを流した後、ベン゛ゼン（１０ Ｖｏ１％）と水
嵩との混合ガスを１００〜３００ｃｃ ／分で１０〜１
８０ ；３間流した。The amount supported as iron is approximately 0.02%)ζ. This was loaded into an alumina boat, introduced into an electric furnace with a reactor diameter of 50 mmφ, and after flowing only water bulk gas at 900 to 1000°C for several minutes, benzene (10 Vo1%) and water bulk were mixed. 10-1 gas at 100-300cc/min
80; Flowed for 3 minutes.
得られた複合構造のカーボンブランクを電子；１■微鏡
で観察すると第１図（イ＆率１０００倍）及び第２図（
倍率ｉｏｏｏｏ倍）に示ずｊ；・）に、カーボンブラッ
クの空隙内に繊維状炭素が成長しており、この長さは４
０〜１００１１、太サバ２００ 〜５００ 人０）、’
ｌＩ’Ｑ ＩＪＩＪ テ変動し、全体の重量は１．１ｇ
に増加した。When the resulting carbon blank with a composite structure was observed with an electron microscope, the results were as shown in Figure 1 (1000x magnification) and Figure 2 (
As shown in the magnification ioooo times), fibrous carbon grows within the voids of carbon black, and its length is 4
0~10011, thick mackerel 200~500 people 0),'
The total weight is 1.1g.
increased to
電気抵抗をＪＩＳ−Ｋ １４０９にｉｐ！拠して測定し
たところ、原料アセチレンブラックの粒状品が０．３０
９・ｃｍ（５０Ｋｇ／ｃ＋Ｉｌ）であったのに対し、本
発明に係るカーボンブラックは６．１５〜０．０’３（
２・ｃｍ （５’ＯＫｇ／ｃｎりであった。IP electrical resistance to JIS-K 1409! According to the measurement, the raw material acetylene black granules were 0.30
9 cm (50 Kg/c+Il), whereas the carbon black according to the present invention had a carbon black of 6.15 to 0.0'3 (
2 cm (5' OKg/cn).
得られた複合構造のカーボンブラック３０部をＡＢＳ樹
脂（商標名：デンカＧＲ−４０００ ） １００部とラ
ボプラストミルＲ−６０ （東洋楕１１氾１１）ル９）
で２００℃×１０分間混練し、得られたコンパウンドを
圧縮成形機で２３０℃×１０分間加熱プレスし、）７さ
２ｍｍのプレスシートを１ηた。このプレスシートの電
気抵抗をデジタルマルチメーターＴｌｔ−６８５０（タ
ゲダ理？ｉＪＦ ａ＋ｌｌ ｇ ）を用い、Ｓ ＲＩ
Ｓ ２３０１に準１処して測定したところ、３Ω−ｃｍ
であった。30 parts of the resulting composite structure carbon black was mixed with 100 parts of ABS resin (trade name: Denka GR-4000) and Laboplasto Mill R-60 (Toyo Oval 11 Uzu 11) 9)
The resulting compound was heated and pressed in a compression molding machine at 230°C for 10 minutes to form a press sheet with a width of 2 mm. The electrical resistance of this press sheet was measured using a digital multimeter Tlt-6850 (Tageda Ri?
When measured with S 2301 semi-1 treatment, it was 3Ω-cm
Met.
比較のため、本実施例に用いたアセチレンブランク１０
部と繊維状炭素１部を１１１に混合し、その混合物３０
部を上記のへＢＳ樹脂に混合し、その他日実施例と同様
に処理し、電気ａｔ抗を測定しノコところ、３０Ω−ｃ
ｍであった。For comparison, acetylene blank 10 used in this example
and 1 part of fibrous carbon are mixed in 111 parts, and the mixture is mixed with 30 parts of fibrous carbon.
was mixed with the above BS resin, treated in the same manner as in the other examples, and measured for electric resistance.
It was m.
更に、本発明に係る複合構造のカーボンブランクは混練
にあたり、加工性も改良されていた。Furthermore, the composite structure carbon blank according to the present invention had improved workability during kneading.
図面は本発明に係る複合構造のカーボンブラックの結晶
構造を表す電子顕微鏡写真であり、第１図は倍率１００
０倍、第２図は倍率１００００倍である。
特許出願人 電気化学工業株式会は
代理人 弁理士 鈴 木 定 子
第２図The drawings are electron micrographs showing the crystal structure of carbon black with a composite structure according to the present invention, and FIG. 1 is a magnification of 100.
The magnification in FIG. 2 is 10,000 times. Patent applicant Denki Kagaku Kogyo Co., Ltd. is the agent Patent attorney Sadako Suzuki Figure 2
Claims (4)
た繊維状炭素が介在している複合構造のカーボンブラン
ク。(1) A carbon blank with a composite structure in which fibrous carbon obtained by a vapor phase method is interposed in the voids of the carbon blank.
ク１〜９９重量部含まれζいる特許請求の範囲第１項記
載の複合構造のカーボンブランク。(2) The carbon blank having a composite structure according to claim 1, wherein 7 and 1 to 99 parts by weight of the carbon blank are contained per 1 part by weight of the fibrous carbon.
μ以下である特許請求の範囲第１ｒＢ又は第２項記載の
複合構造のカーボンブラック。(3) The length of fibrous carbon is 11 or less and the thickness is 50
The carbon black having a composite structure according to claim 1rB or claim 2, wherein the carbon black has a particle diameter of less than μ.
子をシーディングし、夕１部加熱方式の管状炉に供給し
、９００〜１５００℃に保持した状態で、気化した炭化
水素ガスをキャリヤーガスと共に供給し、カーボンブラ
ックの空隙内に気相法による繊維状炭素を成長させる複
合構造のカーボンブランクの製法。(4) A carbon blank is seeded with fine particles of a metal or a metal compound, and then fed into a tubular furnace with a partial heating method, and while the temperature is maintained at 900 to 1500°C, vaporized hydrocarbon gas is fed together with a carrier gas. , a method for manufacturing carbon blanks with a composite structure in which fibrous carbon is grown in the voids of carbon black using a vapor phase method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58146710A JPS6038472A (en) | 1983-08-12 | 1983-08-12 | Composite-structure carbon black and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58146710A JPS6038472A (en) | 1983-08-12 | 1983-08-12 | Composite-structure carbon black and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6038472A true JPS6038472A (en) | 1985-02-28 |
| JPH0356596B2 JPH0356596B2 (en) | 1991-08-28 |
Family
ID=15413786
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58146710A Granted JPS6038472A (en) | 1983-08-12 | 1983-08-12 | Composite-structure carbon black and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6038472A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62287571A (en) * | 1986-06-05 | 1987-12-14 | Denki Kagaku Kogyo Kk | Material for gas diffusion electrode |
| US5273817A (en) * | 1990-10-12 | 1993-12-28 | Kitagawa Industries Co., Ltd. | Plastic material for wrapping over and carrying food |
| JP2009503182A (en) * | 2005-07-27 | 2009-01-29 | デンカ シンガポール プライベート リミテッド | Carbon black, its production method and use |
| JP2010031214A (en) * | 2008-07-02 | 2010-02-12 | Denki Kagaku Kogyo Kk | Carbon black composite and application thereof |
| JP2010077313A (en) * | 2008-09-26 | 2010-04-08 | Denki Kagaku Kogyo Kk | Carbon black composite body and method for producing the same |
| JP2010248397A (en) * | 2009-04-17 | 2010-11-04 | Denki Kagaku Kogyo Kk | Method for producing carbon black composite |
| WO2012141308A1 (en) * | 2011-04-15 | 2012-10-18 | 電気化学工業株式会社 | Carbon black composite and lithium-ion secondary battery using same |
| WO2022176363A1 (en) * | 2021-02-18 | 2022-08-25 | Dic株式会社 | Carbon black, ink, paint, colorant for plastic, colored molded product, colorant for stationery/writing instrument, printing agent, toner, dispersion/resist for color filter, and cosmetic |
-
1983
- 1983-08-12 JP JP58146710A patent/JPS6038472A/en active Granted
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62287571A (en) * | 1986-06-05 | 1987-12-14 | Denki Kagaku Kogyo Kk | Material for gas diffusion electrode |
| US5273817A (en) * | 1990-10-12 | 1993-12-28 | Kitagawa Industries Co., Ltd. | Plastic material for wrapping over and carrying food |
| JP2009503182A (en) * | 2005-07-27 | 2009-01-29 | デンカ シンガポール プライベート リミテッド | Carbon black, its production method and use |
| KR101255399B1 (en) * | 2005-07-27 | 2013-04-17 | 덴카 싱가포르 프라이비트 리미티드 | Carbon black, method for producing the same, and its use |
| JP2010031214A (en) * | 2008-07-02 | 2010-02-12 | Denki Kagaku Kogyo Kk | Carbon black composite and application thereof |
| JP2010077313A (en) * | 2008-09-26 | 2010-04-08 | Denki Kagaku Kogyo Kk | Carbon black composite body and method for producing the same |
| JP2010248397A (en) * | 2009-04-17 | 2010-11-04 | Denki Kagaku Kogyo Kk | Method for producing carbon black composite |
| WO2012141308A1 (en) * | 2011-04-15 | 2012-10-18 | 電気化学工業株式会社 | Carbon black composite and lithium-ion secondary battery using same |
| WO2022176363A1 (en) * | 2021-02-18 | 2022-08-25 | Dic株式会社 | Carbon black, ink, paint, colorant for plastic, colored molded product, colorant for stationery/writing instrument, printing agent, toner, dispersion/resist for color filter, and cosmetic |
| JP7160228B1 (en) * | 2021-02-18 | 2022-10-25 | Dic株式会社 | Carbon black for ink and ink |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0356596B2 (en) | 1991-08-28 |
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