JP2003064280A - Conductive powder, its production method and application - Google Patents
Conductive powder, its production method and applicationInfo
- Publication number
- JP2003064280A JP2003064280A JP2001255813A JP2001255813A JP2003064280A JP 2003064280 A JP2003064280 A JP 2003064280A JP 2001255813 A JP2001255813 A JP 2001255813A JP 2001255813 A JP2001255813 A JP 2001255813A JP 2003064280 A JP2003064280 A JP 2003064280A
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- Japan
- Prior art keywords
- carbon black
- siox
- powder
- conductive
- rubber
- 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.)
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、カーボンブラック
−ＳｉＯｘ複合化合物の粒子を含有してなる導電性粉
末、その製造方法及びそれが樹脂及び／又はゴムに充填
されてなる導電性組成物に関する。TECHNICAL FIELD The present invention relates to a conductive powder containing particles of a carbon black-SiOx composite compound, a method for producing the same, and a conductive composition obtained by filling the resin and / or rubber with the conductive powder.
【０００２】[0002]
【従来の技術】従来、タイヤ等のゴム補強材には、カー
ボンブラックが用いられているが、近年、燃費節減と制
動性を両立させる観点から、シリカも使用されるように
なっている。しかしながら、シリカは絶縁性であるの
で、それの充填されたゴム製品は帯電したり、またシリ
カの自己凝集力によって均一分散させることが容易でな
い問題があった。これを解決するため、カーボンブラッ
クと同等の導電性を示すシリカ・カーボン複合粒子を含
む粉体（特公平７−３０２６９号公報）の利用が試みら
れている。2. Description of the Related Art Conventionally, carbon black has been used as a rubber reinforcing material for tires and the like, but in recent years, silica has also been used from the viewpoint of achieving both fuel economy and braking performance. However, since silica is insulative, the rubber product filled with it has a problem that it is not easy to be charged and it is not easy to uniformly disperse it due to the self-cohesion of silica. In order to solve this, it has been attempted to use a powder (Japanese Patent Publication No. 7-30269) containing silica-carbon composite particles exhibiting conductivity equivalent to that of carbon black.
【０００３】この粉体は、水性媒質中でカーボンブラッ
クをスラリー化し、特定のｐＨ値において、ケイ酸ナト
リウム水溶液からカーボンブラック粒子上に無定型シリ
カを沈積させて製造されるものであり、粉体塗料用とし
て好適であることが記載されている。しかしながら、こ
の方法は、水性媒質中でカーボンブラックに無定型シリ
カを沈積せねばならないという全く別工程が必要であ
り、また再び粉末とするために乾燥、解砕工程やスプレ
ードライヤー工程等も必要となるので、工業的に優位で
あるとはいえなかった。また、導電性の付与効果や、高
温での低い損失正接（tanδ）、低温での高い損失正接
の付与能力も十分でなかった。This powder is produced by slurrying carbon black in an aqueous medium and depositing amorphous silica on carbon black particles from an aqueous sodium silicate solution at a specific pH value. It is described that it is suitable for paints. However, this method requires a completely separate step of depositing amorphous silica on carbon black in an aqueous medium, and also requires a drying step, a crushing step, a spray dryer step, and the like to make powder again. Therefore, it was not industrially advantageous. In addition, the effect of imparting conductivity, the ability to impart low loss tangent (tan δ) at high temperature, and the ability to impart high loss tangent at low temperature were not sufficient.
【０００４】一方、特開平１０−００７９２９号公報に
は、カーボンブラック原料を反応室に供給・燃焼させて
カーボンブラックの生成場を形成すると共に、珪素含有
有機化合物を噴霧して珪素含有のカーボンブラックを製
造することが開示されている。この方法によれば、導電
性の付与効果の大きな粉末が製造されるが、有機化合物
に含まれるアルコール成分がカーボンブラックに残存す
ること、アルコール成分の回収工程が必要となること、
高価な珪素含有有機化合物を用いること、などの課題が
ある。また、高温での低い損失正接（tanδ）、低温で
の高い損失正接の付与能力は十分でなかった。On the other hand, in Japanese Unexamined Patent Publication No. 10-007929, a carbon black raw material is supplied to and burned in a reaction chamber to form a carbon black generation field, and a silicon-containing organic compound is sprayed to form a silicon-containing carbon black. Is disclosed. According to this method, a powder having a large effect of imparting conductivity is produced, but the alcohol component contained in the organic compound remains in the carbon black, and a step of recovering the alcohol component is required,
There are problems such as using an expensive silicon-containing organic compound. Moreover, the ability to give a low loss tangent (tan δ) at high temperature and a high loss tangent at low temperature was not sufficient.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、上記
に鑑み、ゴム及び／又は樹脂に対してシリカ粉末と同等
の充填性を示し、導電性付与能力が十分で、しかも高温
での低い損失正接（tanδ）、低温での高い損失正接を
与えることのできる導電性粉末、その製造方法及びそれ
が樹脂及び／又はゴムに充填された導電性組成物を提供
することである。SUMMARY OF THE INVENTION In view of the above, the object of the present invention is to provide a rubber and / or a resin with a filling property equivalent to that of silica powder, a sufficient conductivity imparting ability, and a low conductivity at high temperature. The purpose of the present invention is to provide a conductive powder capable of giving a loss tangent (tan δ) and a high loss tangent at a low temperature, a method for producing the same, and a conductive composition in which a resin and / or rubber is filled.
【０００６】[0006]
【課題を解決するための手段】すなわち、本発明は、次
のとおりである。
（請求項１） カーボンブラック−ＳｉＯｘ（ｘ＜２）
複合化合物の粒子を含有してなり、単位表面積当たりの
シラノール基数が３〜１０個／ｎｍ2 であることを特徴
とする導電性粉末。
（請求項２） 粒子が、カーボンブラックのコア部、Ｓ
ｉＯｘのシェル部からなるコア・シェル構造であること
を特徴とする請求項１記載の導電性粉末。
（請求項３） 酸素存在下のカーボンブラック発生場
に、ＳｉＯｘ（ｘ＜１．５）粉末を噴霧・気化させてＳ
ｉＯｘのｘ値を増大させた後、それとカーボンブラック
とを化学結合させ、得られた粉末を捕集することを特徴
とする請求項１記載の導電性粉末の製造方法。
（請求項４） 請求項１又は２記載の導電性粉末がゴム
及び／又は樹脂に充填されてなることを特徴とする導電
性組成物。[Means for Solving the Problems] That is, the present invention is as follows. (Claim 1) Carbon black-SiOx (x <2)
An electrically conductive powder comprising particles of a composite compound, wherein the number of silanol groups per unit surface area is 3 to 10 / nm 2 . (Claim 2) The particles are carbon black core, S
The conductive powder according to claim 1, which has a core-shell structure composed of a shell portion of iOx. (Claim 3) SiOx (x <1.5) powder is sprayed and vaporized in a carbon black generation field in the presence of oxygen to obtain S.
The method for producing a conductive powder according to claim 1, wherein after increasing the x value of iOx, it is chemically bonded to carbon black, and the obtained powder is collected. (Claim 4) A conductive composition comprising the conductive powder according to claim 1 or 2 filled in a rubber and / or a resin.
【０００７】[0007]
【発明の実施の形態】以下、本発明について更に詳しく
説明する。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below.
【０００８】本発明のカーボンブラック−ＳｉＯｘ（ｘ
＜２）複合化合物粒子を含む導電性粉末は、酸素存在下
のカーボンブラック発生場に、ＳｉＯｘ（ｘ＜１．５）
粉末を噴霧・気化させ、得られた粉末を捕集することに
よって製造することができる。すなわち、ＳｉＯｘ（ｘ
＜１．５）粉末をカーボンブラック原料と共に燃焼室に
供給するか、反応室へカーボンブラック油等のカーボン
ブラック原料と共に又は単独で供給するか、又はその両
方によって供給すると、ＳｉＯｘ粉末は酸素存在下で気
化してｘ値の増大したＳｉＯｘガスとなり、それがカー
ボンブラックの成長過程でカーボンブラック中に取り込
まれ、化学結合して複合化合物粒子を含む粉末となる。
得られた粉末は、反応室出口に接続されたバッグフィル
ター等の回収装置で副生ガスと分離され回収される。Carbon black of the present invention-SiOx (x
<2) The conductive powder containing the composite compound particles is subjected to SiOx (x <1.5) in the carbon black generation field in the presence of oxygen.
It can be produced by spraying and vaporizing powder and collecting the obtained powder. That is, SiOx (x
<1.5) When the powder is supplied to the combustion chamber together with the carbon black raw material, supplied to the reaction chamber together with the carbon black raw material such as carbon black oil or alone, or both, the SiOx powder is present in the presence of oxygen. And vaporize to form SiOx gas having an increased x value, which is taken into carbon black during the growth process of carbon black and chemically bonded to form powder containing composite compound particles.
The obtained powder is separated from the by-product gas and collected by a collecting device such as a bag filter connected to the outlet of the reaction chamber.
【０００９】本発明に用いられるカーボンブラックとし
ては、ファーネスブラック、アセチレンブラック、チャ
ンネルブラック、サーマルブラック等の何れであっても
よい。これらカーボンブラックは、カーボンブラック油
又はガス状炭化水素等のカーボンブラック原料の燃焼に
よって製造することができる。The carbon black used in the present invention may be any of furnace black, acetylene black, channel black, thermal black and the like. These carbon blacks can be produced by burning carbon black raw materials such as carbon black oil or gaseous hydrocarbons.
【００１０】本発明におけるカーボンブラック発生場を
ファーネスブラックを例にあげて説明すると、カーボン
ブラック発生場は、軽油、重油、天然ガス等のカーボン
ブラック原料を過剰酸素下で燃焼させる燃焼室と、該燃
焼室で生成した高温ガス流にカーボンブラック原料を供
給し高温ガス流に含まれる余剰酸素と不完全燃焼を起こ
させる反応室とが、狭部を介して直結されてなるもので
あることが好ましい。反応室で生成した一酸化炭素、水
素、カーボン等を含んだ混合ガスは、反応室の下流部に
設けられた冷却部で冷却水等により急冷されて反応が停
止する。The carbon black generation field in the present invention will be explained by taking furnace black as an example. The carbon black generation field is a combustion chamber for burning carbon black raw materials such as light oil, heavy oil and natural gas under excess oxygen, and It is preferable that the carbon black raw material is supplied to the high temperature gas flow generated in the combustion chamber and the excess oxygen contained in the high temperature gas flow and the reaction chamber for causing incomplete combustion are directly connected via a narrow portion. . The mixed gas containing carbon monoxide, hydrogen, carbon, etc. generated in the reaction chamber is rapidly cooled by cooling water or the like in the cooling unit provided in the downstream portion of the reaction chamber to stop the reaction.
【００１１】上記方法によれば、複合化合物粒子の各粒
子は、カーボンブラックをコア部、ＳｉＯｘをシェル部
とするコア・シェル構造となりやすい。また、得られた
導電性粉末の単位表面積当たりのシラノール基数（ＯＨ
基数）が３〜１０個／ｎｍ2となる。シラノール基数が
３個／ｎｍ2 未満であると、樹脂、ゴムの充填材とした
際に十分な補強効果が得られず、また十分なｔａｎδ改
質特性が得られない。一方、シラノール基数が１０個／
ｎｍ2 超であると、粉末の凝集により樹脂、ゴムへの分
散性が悪くなる。According to the above method, each particle of the composite compound particles is likely to have a core-shell structure in which carbon black is the core part and SiOx is the shell part. In addition, the number of silanol groups per unit surface area of the obtained conductive powder (OH
The number of bases is 3 to 10 / nm 2 . When the number of silanol groups is less than 3 / nm 2 , a sufficient reinforcing effect cannot be obtained when used as a filler for resins and rubbers, and sufficient tan δ modification properties cannot be obtained. On the other hand, the number of silanol groups is 10 /
When it is more than nm 2 , the dispersibility in the resin and rubber is deteriorated due to the aggregation of the powder.
【００１２】本発明の導電性粉末においては、全ての粒
子が上記コア・シェル構造粒子で構成されていることが
最適であるが、８０％以上の構成比率でも十分である。
上記した方法によれば、ほぼ１００％の構成比率とする
ことができる。In the electroconductive powder of the present invention, it is optimal that all particles are composed of the core-shell structured particles, but a composition ratio of 80% or more is sufficient.
According to the method described above, the composition ratio can be set to almost 100%.
【００１３】導電性粉末中のＳｉＯｘ含有率は、０．１
〜４０質量％であることが好ましい。０．１％未満では
十分なｔａｎδの改質効果が得られず、また４０％超で
あると、ゴム及び／又は樹脂に十分な補強効果を与える
ことができない。The content of SiOx in the conductive powder is 0.1.
It is preferably ˜40% by mass. If it is less than 0.1%, a sufficient tan δ modification effect cannot be obtained, and if it exceeds 40%, a sufficient reinforcing effect cannot be given to the rubber and / or resin.
【００１４】本発明における導電性粉末の単位表面積当
たりのシラノール基数（ＯＨ基数）は、カールフィッシ
ャー水分測定装置を用い、２００℃〜９００℃で脱水さ
れた水分量を測定し、式、ＯＨ＝Ａ×１０-6×（１／１
８）×６．０２×１０23×（１／Ｂ）×１０-18×２、
｛ここで、Ａ：水分量（ｐｐｍ）、Ｂ：導電性粉末の比
表面積（ｍ2／ｇ）｝、によって算出される。２００℃
未満で脱水された水分は物理吸着水分が主体であり、９
００℃超では実質的にシラノール基が存在しない。The number of silanol groups (the number of OH groups) per unit surface area of the conductive powder in the present invention is determined by measuring the amount of dehydrated water at 200 ° C. to 900 ° C. using a Karl Fischer water content measuring device, and the formula: OH = A × 10 -6 × (1/1
8) × 6.02 × 10 23 × (1 / B) × 10 -18 × 2,
{Here, A: water content (ppm), B: specific surface area of conductive powder (m 2 / g)}. 200 ° C
The water dehydrated at less than 9 is mainly composed of physically adsorbed water.
When the temperature exceeds 00 ° C, the silanol group does not substantially exist.
【００１５】上記方法において、ＳｉＯｘ粉末原料のｘ
値（以下、「ｘｓ値」という。）は、１．５以下である
ことが望ましい。１．５超であると、ＳｉＯｘ粉末が気
化し難くなり、カーボンブラックとの複合化が困難とな
る。In the above method, x of the SiOx powder raw material is
The value (hereinafter, referred to as “xs value”) is preferably 1.5 or less. If it exceeds 1.5, the SiOx powder is difficult to vaporize, and it becomes difficult to form a composite with carbon black.
【００１６】ｘｓ値とＳｉＯｘ粉末が気化したＳｉＯｘ
ガスのｘ値（以下、「ｘｐ値」という。）との関係は、
ｘｐ＝１．０５〜１．５ｘｓ、特にｘｐ＝１．１〜１．
３ｘｓであることが好ましい。この関係は、ＳｉＯｘ粉
末原料のｘｓ値、カーボンブラック発生場の酸素濃度、
カーボンブラック発生場の温度、冷却部の冷却条件等に
よって調整することができる。なお、ｘｓ値、ｘｐ値
は、ＦＥＳＥＭ／ＥＤＳを用いてＳｉとＯの質量比を測
定し、モル比に換算して求められる。Xs value and SiOx obtained by vaporizing SiOx powder
The relationship with the x value of gas (hereinafter referred to as “xp value”) is
xp = 1.05 to 1.5xs, especially xp = 1.1 to 1.
It is preferably 3xs. This relationship is represented by the xs value of the SiOx powder raw material, the oxygen concentration in the carbon black generation field,
It can be adjusted according to the temperature of the carbon black generation field, the cooling conditions of the cooling unit, and the like. The xs value and the xp value are obtained by measuring the mass ratio of Si and O using FESEM / EDS and converting it to the molar ratio.
【００１７】本発明の導電性粉末をゴム及び／又は樹脂
に配合することによって、本発明の導電性組成物とな
る。導電性は、複合化合物粒子のＳｉＯｘ含有率、導電
性粉末の充填量によって、制御することができる。The conductive composition of the present invention is obtained by blending the conductive powder of the present invention with rubber and / or resin. The conductivity can be controlled by the SiOx content of the composite compound particles and the filling amount of the conductive powder.
【００１８】本発明の導電性粉末を充填材として用いる
際、その比表面積を３０ｍ2／ｇ以上、特に５０ｍ2／ｇ
以上、更には１００ｍ2／ｇ以上の粉末とすることが好
ましい。比表面積が３０ｍ2／ｇ未満では、導電性組成
物の補強効果が十分でなくなり、特にゴム及び／又は樹
脂の粘性が小さい場合には充填材が沈降する恐れがあ
る。比表面積の上限は、混練性、ハンドリング性の点か
ら、３００ｍ2／ｇ以下が好ましい。When the conductive powder of the present invention is used as a filler, its specific surface area is 30 m 2 / g or more, especially 50 m 2 / g.
As described above, it is preferable that the powder is 100 m 2 / g or more. When the specific surface area is less than 30 m 2 / g, the reinforcing effect of the conductive composition becomes insufficient, and especially when the viscosity of rubber and / or resin is low, the filler may settle. The upper limit of the specific surface area is preferably 300 m 2 / g or less from the viewpoint of kneading property and handling property.
【００１９】本発明の導電性組成物のゴム及び／又は樹
脂としては、天然ゴム、スチレン−ブタジエンゴム（Ｓ
ＢＲ）、ポリブタジエン、ポリイソプレン、ポリクロロ
プレン、１，３ブタジエン、スチレン、イソプレン、イ
ソブチレン、２，３ジメチル−１，３ブタジエン、アク
リロニトリル、エチレン、プロピレン、メチルスチレ
ン、クロロスチレン、２−ビニル−ピリジン、５−エチ
ル２−ビニルピリジン、５−メチル２−ビニルピリジン
等を成分とする単独重合体、共重合体及び三次元重合体
等から選ばれた１種又は２種以上が用いられる。As the rubber and / or resin of the conductive composition of the present invention, natural rubber, styrene-butadiene rubber (S
BR), polybutadiene, polyisoprene, polychloroprene, 1,3 butadiene, styrene, isoprene, isobutylene, 2,3 dimethyl-1,3 butadiene, acrylonitrile, ethylene, propylene, methylstyrene, chlorostyrene, 2-vinyl-pyridine, One or more selected from homopolymers, copolymers, three-dimensional polymers and the like containing 5-ethyl 2-vinyl pyridine, 5-methyl 2-vinyl pyridine and the like as components are used.
【００２０】[0020]
【実施例】以下、実施例、比較例をあげて更に具体的に
本発明を説明する。EXAMPLES The present invention will be described more specifically with reference to Examples and Comparative Examples.
【００２１】本実験で用いた装置は、燃料ノズル及び燃
焼用空気ノズルの設置された燃焼室と反応室との間に狭
部を設け、それらを直結してカーボンブラック生成場を
形成すると共に、反応室の下流部には冷却水導入ノズル
を有する冷却部と、それに続く捕集室（バグフィルタ
ー）とが接続されたものである。なお、上記狭部には原
料導入ノズルが設置されている。In the apparatus used in this experiment, a narrow portion is provided between the combustion chamber in which the fuel nozzle and the combustion air nozzle are installed and the reaction chamber, and they are directly connected to each other to form a carbon black production field. In the downstream part of the reaction chamber, a cooling part having a cooling water introducing nozzle and a collection chamber (bag filter) following it are connected. A raw material introduction nozzle is installed in the narrow portion.
【００２２】実施例１〜３
表１に示す条件で、カーボンブラック燃料（天然ガス）
と燃焼用空気とを燃焼室に、またカーボンブラック原料
油とｘｓ＝１．０のＳｉＯｘ粉末とを狭部に供給した。
生成したカーボンブラック−ＳｉＯｘ（ｘ＜２）複合化
合物粒子を含む混合ガスの反応を冷却部に冷却水を噴霧
して停止させ、バグフィルター（温度１８０〜２００
℃）から導電性粉末を捕集した。Examples 1 to 3 Under the conditions shown in Table 1, carbon black fuel (natural gas)
And combustion air were supplied to the combustion chamber, and the carbon black raw material oil and SiOx powder of xs = 1.0 were supplied to the narrow portion.
The reaction of the mixed gas containing the generated carbon black-SiOx (x <2) composite compound particles is stopped by spraying cooling water to the cooling section, and the bag filter (temperature 180 to 200
Conductive powder was collected from (.degree. C.).
【００２３】比較例１〜５
比較例１は、カーボンブラック市販品（三菱化学社製、
商品名「ダイアブラック ＬＩ）単身、比較例２は、こ
のカーボンブラック市販品８０％とＳｉＯｘ（ｘ＝１．
１）粉末２０％との単なる機械的混合物、比較例３は、
ＳｉＯｘ（ｘ＝１．１）粉末単身である。比較例４及び
５は、実施例において、カーボンブラック生成場の酸素
濃度を調節し、シラノール基数を変えた。Comparative Examples 1 to 5 Comparative Example 1 is a carbon black commercial product (manufactured by Mitsubishi Chemical Corporation,
The product name “Diablack LI” alone, Comparative Example 2 is 80% of this carbon black commercial product and SiOx (x = 1.
1) Mechanic mixture with 20% powder, Comparative Example 3
SiOx (x = 1.1) powder alone. In Comparative Examples 4 and 5, the oxygen concentration in the carbon black production field was adjusted and the number of silanol groups was changed in the examples.
【００２４】[0024]
【表１】 [Table 1]
【００２５】上記で得られた導電性粉末の諸物性を以下
に従って測定した。それらの結果を表２に示す。
（１）導電性粉末のＳｉＯｘ含有率：試料を５５０℃大
気中で加熱して炭素粉末成分を消失させ、その質量減少
率からＳｉＯｘ含有率を算出した。
（２）ＳｉＯｘのｘｓ値、ｘｐ値：ＦＥＳＥＭ／ＥＤＳ
（日本電子社製）により、ＳｉとＯの質量比を測定し、
モル比に換算した。
（３）比表面積：ＢＥＴ式１点法にて測定した。
（４）導電性粉末の単位表面積当たりのシラノール基数
（ＯＨ基数）：上記方法で測定した。Various physical properties of the electroconductive powder obtained above were measured as follows. The results are shown in Table 2. (1) SiOx content of conductive powder: The sample was heated in the atmosphere at 550 ° C. to eliminate the carbon powder component, and the SiOx content was calculated from the mass reduction rate. (2) SiOx xs and xp values: FESEM / EDS
(Manufactured by JEOL Ltd.) to measure the mass ratio of Si and O,
Converted to molar ratio. (3) Specific surface area: measured by the BET one-point method. (4) Number of silanol groups (number of OH groups) per unit surface area of conductive powder: measured by the above method.
【００２６】[0026]
【表２】 [Table 2]
【００２７】つぎに、スチレンブタジエンゴム１００部
（質量部、以下同じ）に対し、導電性粉末４４部、ステ
アリン酸１．５部、老化防止剤：Ｎ−フェニル−Ｎ’−
（１，３−ジメチルブチル）−Ｐ−フェニレンジアミン
０．７部、シランカップリング剤：デクッサ社製「Ｓｉ
６９」２．２部、ＡＨ−１６：アロマ系オイル０．７
部、酸化亜鉛２．２部、硫黄２．９部、促進剤ＮＳ：Ｎ
−ｔｅｒｔ−ブチル−２−ベンゾチアゾリルスルフェン
アミド１．１部、促進剤Ｄ：ジフェニルグアジニンを
１．１部を配合し、混練・加硫してゴムシートを作製し
た。Next, with respect to 100 parts of styrene-butadiene rubber (parts by mass, the same applies hereinafter), 44 parts of conductive powder, 1.5 parts of stearic acid, antioxidant: N-phenyl-N'-
0.7 parts of (1,3-dimethylbutyl) -P-phenylenediamine, silane coupling agent: "Si manufactured by Dexsa"
69 "2.2 parts, AH-16: 0.7 aroma oil
Parts, zinc oxide 2.2 parts, sulfur 2.9 parts, accelerator NS: N
1.1 parts of -tert-butyl-2-benzothiazolylsulfenamide and 1.1 parts of accelerator D: diphenylguadinine were mixed and kneaded and vulcanized to prepare a rubber sheet.
【００２８】ゴムシートの補強効果を評価するため、Ｊ
ＩＳ Ｋ ６３０１に従い、モジュラス（Ｍ１００，Ｍ
３００）、ＴＢ（破断強度）を測定した。また、ｔａｎ
δ（ＪＩＳ Ｋ ６３９４）と電気抵抗率（ＪＩＳ Ｋ
１４９６）を測定した。それらの結果を表３に示す。In order to evaluate the reinforcing effect of the rubber sheet, J
According to IS K 6301, the modulus (M100, M
300) and TB (breaking strength) were measured. Also, tan
δ (JIS K 6394) and electrical resistivity (JIS K
1496) was measured. The results are shown in Table 3.
【００２９】[0029]
【表３】 [Table 3]
【００３０】表３から明らかなように、本発明の導電性
粉末で補強されたゴムシートは、従来のカーボンブラッ
ク粉末（比較例１）、カーボンブラックとＳｉＯｘ粉末
との単なる機械的混合物（比較例２）、ＳｉＯｘ粉末
（比較例３）で補強されたものと比較し、高温での高温
での低い損失正接（tanδ）、低温での高い損失正接を
与え、格段に補強性が向上し、導電性も十分に発現する
ことが分かる。As can be seen from Table 3, the rubber sheet reinforced with the conductive powder of the present invention is a conventional carbon black powder (Comparative Example 1), a mere mechanical mixture of carbon black and SiOx powder (Comparative Example). 2), compared with those reinforced with SiOx powder (Comparative Example 3), it gives a low loss tangent (tan δ) at a high temperature at a high temperature and a high loss tangent at a low temperature, so that the reinforcing property is remarkably improved and the conductivity is improved. It can be seen that the sex is sufficiently expressed.
【００３１】[0031]
【発明の効果】本発明によれば、ゴム及び／又は樹脂に
対してシリカ粉末と同等の充填性を示し、しかも導電性
付与能力が十分であり、高温での低い損失正接（tan
δ）、低温での高い損失正接を与えることのできる導電
性粉末、その製造方法及びそれが樹脂及び／又はゴムに
充填された導電性組成物が提供される。本発明の導電性
粉末は、粉体塗料、タイヤ用充填材として好適である。EFFECTS OF THE INVENTION According to the present invention, rubber and / or resin have the same filling property as silica powder, and have sufficient conductivity imparting ability, and a low loss tangent (tan) at high temperature.
δ), a conductive powder capable of giving a high loss tangent at low temperature, a method for producing the same, and a conductive composition in which the resin and / or rubber are filled. The conductive powder of the present invention is suitable as a powder coating material and a tire filler.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｈ０１Ｂ 1/04 Ｈ０１Ｂ 1/04 1/24 1/24 Ｚ Ｆターム(参考） 4J002 AC011 AC031 AC061 AC081 AC091 BB031 BB121 BB181 BC031 BC081 BC111 BG101 DA036 FB076 FD116 GQ01 4J037 AA02 AA18 CA01 CA24 CC29 DD13 EE02 EE11 EE44 FF11 5G301 BA01 BA05 DA18 DA42 DA43 DA44 DA60 DD10 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) H01B 1/04 H01B 1/04 1/24 1/24 Z F term (reference) 4J002 AC011 AC031 AC061 AC081 AC091 BB031 BB121 BB181 BC031 BC081 BC111 BG101 DA036 FB076 FD116 GQ01 4J037 AA02 AA18 CA01 CA24 CC29 DD13 EE02 EE11 EE44 FF11 5G301 BA01 BA05 DA18 DA42 DA43 DA44 DA60 DD10
Claims (4)
複合化合物の粒子を含有してなり、単位表面積当たりの
シラノール基数が３〜１０個／ｎｍ2 であることを特徴
とする導電性粉末。1. Carbon black-SiOx (x <2)
An electrically conductive powder comprising particles of a composite compound, wherein the number of silanol groups per unit surface area is 3 to 10 / nm 2 .
ｉＯｘのシェル部からなるコア・シェル構造であること
を特徴とする請求項１記載の導電性粉末。2. The particles are carbon black core, S
The conductive powder according to claim 1, which has a core-shell structure composed of a shell portion of iOx.
に、ＳｉＯｘ（ｘ＜１．５）粉末を噴霧・気化させてＳ
ｉＯｘのｘ値を増大させた後、それとカーボンブラック
とを化学結合させ、得られた粉末を捕集することを特徴
とする請求項１記載の導電性粉末の製造方法。3. SiOx (x <1.5) powder is sprayed and vaporized in a carbon black generation field in the presence of oxygen to obtain S.
The method for producing a conductive powder according to claim 1, wherein after increasing the x value of iOx, it is chemically bonded to carbon black, and the obtained powder is collected.
及び／又は樹脂に充填されてなることを特徴とする導電
性組成物。4. A conductive composition comprising the conductive powder according to claim 1 or 2 filled in a rubber and / or a resin.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016034999A (en) * | 2014-08-01 | 2016-03-17 | Dic株式会社 | Polyarylene sulfide resin composition, method for producing the same, molded article, film or sheet, transfer belt for electrophotography and image forming apparatus |
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|---|---|---|---|---|
| JPH09202862A (en) * | 1996-01-26 | 1997-08-05 | Catalysts & Chem Ind Co Ltd | Silica-carbon black composite particle, dispersion sol containing the composite particle and coating solution containing the composite particle |
| JPH107929A (en) * | 1996-04-04 | 1998-01-13 | Degussa Ag | Carbon black, its production, and tire rubber compound containing the same |
| JPH1030067A (en) * | 1996-04-26 | 1998-02-03 | Mitsubishi Chem Corp | Production of surface treated carbon black and rubber composition |
| JPH1046047A (en) * | 1996-04-17 | 1998-02-17 | Mitsubishi Chem Corp | Production of surface treated carbon black and rubber composition |
| JPH1053722A (en) * | 1996-08-12 | 1998-02-24 | Yokohama Rubber Co Ltd:The | Production of surface-treated carbon black for rubber reinforcement |
| JPH11116841A (en) * | 1997-10-17 | 1999-04-27 | Mitsubishi Chemical Corp | Silica-attached carbon black, its production and rubber composition |
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2001
- 2001-08-27 JP JP2001255813A patent/JP5037764B2/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09202862A (en) * | 1996-01-26 | 1997-08-05 | Catalysts & Chem Ind Co Ltd | Silica-carbon black composite particle, dispersion sol containing the composite particle and coating solution containing the composite particle |
| JPH107929A (en) * | 1996-04-04 | 1998-01-13 | Degussa Ag | Carbon black, its production, and tire rubber compound containing the same |
| JPH1046047A (en) * | 1996-04-17 | 1998-02-17 | Mitsubishi Chem Corp | Production of surface treated carbon black and rubber composition |
| JPH1030067A (en) * | 1996-04-26 | 1998-02-03 | Mitsubishi Chem Corp | Production of surface treated carbon black and rubber composition |
| JPH1053722A (en) * | 1996-08-12 | 1998-02-24 | Yokohama Rubber Co Ltd:The | Production of surface-treated carbon black for rubber reinforcement |
| JPH11116841A (en) * | 1997-10-17 | 1999-04-27 | Mitsubishi Chemical Corp | Silica-attached carbon black, its production and rubber composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016034999A (en) * | 2014-08-01 | 2016-03-17 | Dic株式会社 | Polyarylene sulfide resin composition, method for producing the same, molded article, film or sheet, transfer belt for electrophotography and image forming apparatus |
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| JP5037764B2 (en) | 2012-10-03 |
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