JPH0339560B2 - - Google Patents

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Publication number
JPH0339560B2
JPH0339560B2 JP60164241A JP16424185A JPH0339560B2 JP H0339560 B2 JPH0339560 B2 JP H0339560B2 JP 60164241 A JP60164241 A JP 60164241A JP 16424185 A JP16424185 A JP 16424185A JP H0339560 B2 JPH0339560 B2 JP H0339560B2
Authority
JP
Japan
Prior art keywords
weight
electrorheological
silica gel
dispersant
parts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
JP60164241A
Other languages
English (en)
Other versions
JPS6144998A (ja
Inventor
Gotsusensu Jon
Opaaman Gyuntaa
Gurape Uorufuganku
Heruteru Fuorukaa
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of JPS6144998A publication Critical patent/JPS6144998A/ja
Publication of JPH0339560B2 publication Critical patent/JPH0339560B2/ja
Granted legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/001—Electrorheological fluids; smart fluids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
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    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/50—Lubricating compositions characterised by the base-material being a macromolecular compound containing silicon
    • C—CHEMISTRY; METALLURGY
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    • C10M113/00—Lubricating compositions characterised by the thickening agent being an inorganic material
    • C10M113/12—Silica
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    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/26—Compounds containing silicon or boron, e.g. silica, sand
    • C—CHEMISTRY; METALLURGY
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    • C10M155/00—Lubricating compositions characterised by the additive being a macromolecular compound containing atoms of elements not provided for in groups C10M143/00 - C10M153/00
    • C10M155/02—Monomer containing silicon
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    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
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    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
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    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
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    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
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    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
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Description

【発明の詳細な説明】
〔産業上の利用分野〕 本発明は、分散相として１〜15重量％の水分含
有量を有するシリカゲルを25重量％よりも多く含
むとともに液相としてシリコーン油を含み、そし
て分散剤も含む電気粘性懸濁液に関するものであ
る。 〔従来の技術およびその問題点〕 電気粘性液体（EVL）は、充分に強い電場の
作用の下で粘度が極めて速やかに、しかも可逆的
に液体からプラスチツクまたは固体の状態に上昇
できる、疏水性で非導電性の油の中に微細に分割
した親水性の固体が分散している分散液である。
粘度を変化させるためには直流の電場だけでなく
交流の電場も使用することができ、その電気粘性
液体を通る電流は非常に低い。したがつて、電気
粘性液体は、低い電力によつて強力な力を、例え
ばクラツチ、水圧弁、シヨツク アブソーバ、バ
イブレータ、あるいはワークピースを正常な位置
に置いて保持するシステムに伝達するのを制御す
るのご望ましいあらゆる用途のために使用するこ
とができる。電気粘性液体を基にした多くの構成
要素において電気粘性液体はゴム状の弾性を有す
る材料と直接接触する。文献に記載された多くの
電気粘性液体は、ゴム状弾性材料を攻撃するかま
たは膨潤させ、そして場合によつてはそれを溶解
もする油または溶剤を含むので、上記のような構
成要素に適していないことがをわかつた。実際に
出会うもう一つの必要条件は、この電気粘性液体
が液体であつて約−50℃〜150℃の温度範囲にわ
たつて化学的に安定であり、しかも少なくとも−
30℃〜110℃の温度において相応の電気粘性作用
を示さなければならないことである。最後に、こ
の電気粘性液体はまた長い期間にわたつて安定に
とどまることが要求され、すなわち相分離を起こ
してはならないし、そして特に再び分散させるの
が困難な沈澱を形成してはならない。 シリカゲル／シリコーン油を基にした電気粘性
液体が米国特許第3047507号に記載されており、
この場合に使用される分散剤、例えばソルビタン
セスキオレート、並びにその他の表面活性剤
は、特に比較的高い温度において不充分な電気反
応性と過度の導電性を示す電気粘性液体をほとん
ど常に導く、導電率が高すぎると、電気粘性液体
を活性化するために極端に高い電流、したがつて
極端に高い電力を必要とするか、あるいは電気粘
性液体中で充分強力な電場を発生させることがで
きない。 〔発明の目的〕 したがつて、本発明の目的は、高い温度（110
℃までの温度）でも高い電気反応性と低い導電率
を示す電気粘性液体を開発することである。 〔問題点を解決するための手段〕 シリカゲルとシリコーン油を基にした電気粘性
懸濁液から出発して、本発明は、800を越す分子
量を有するアミノ官能性、ヒドロキシ官能性、ア
セトキシ官能性またはアルコキシ官能性のポリシ
ロキサンからなる分散剤を添加することによつて
この目的を達成する。これらのポリシロキサンは
シリゲル粒子を基にして１〜30重量％、そして好
ましくは５〜20重量％の濃度で添加される。 分散剤としては使用されるアミノ官能性のポリ
シロキサンは好ましくは次の一般式に該当してお
り、 この式において、 10＜ｎ＜1000、 ｍ＝０〜５、 Ｒ＝ＨまたはC1〜C8アルキル基、そしてＸはＣ、
Ｈおよび、随意に、Ｏおよび／またはＮからなる
二官能性の基である。 これらのアミノ基はSiC結合またはSiOC結合の
どちらかによつてシリコーンに結合している。所
望の結合がSiC結合である場合、Ｘは１〜６個、
そして好ましくは１〜３個の炭素原子を含む二官
能性の炭化水素基を表わしている。好ましいアミ
ノ官能性の基はアミノメチル基およびγ−アミノ
プロピル基である。二官能性の基ＸはＣとＨの他
にＮも含むことができ、例えばＸは基CH2−CH2
−CH2−NH−CH2−CH2−NH2を表わすことが
できる。所望の結合がSiOC結合の場合、アミノ
官能性の基
【式】はアミノアルコキシ基で ある。加水分解安定性の都合上、第二級SiOC結
合が好ましく、この点に関しては１−アミノ−２
−プロポキシ基
【式】または１− アミノ−３−ブトキシン基
【式】が特に適している。 アミノ官能性のポリシロキサンの代わりに、次
の一般式に該当する珪素官能性のポリシロキサン
も分散剤として使用することができる。 この式において、 10＜ｎ＜100、そして Ｙは加水分解できる基、好ましくはヒドロキシ
ル基、アルコキシ基またはカルボキシ基である。 分散剤として使用するのに好適な上述の官能性
ポリシロキサンは好ましくは20〜300のジメチル
シロキサン単位を含んでいる。これらのジメチル
ロキシサン単位は特に、高い固形物含有量と相応
の固有粘度とを結びつける分散液の調製をもたら
す。 本発明によつて次の利益がもたらされる。 本発明による電気粘性液体は、驚くべきことに
は、温度によつて僅かしか影響を受けない高い電
気反応性と低い導電率の両方を示す。 さらに、その電気粘性液体はゴム状弾性を有す
る材料、特に非沈降性で、しかも生理的に不活性
（無毒）なゴムと極めて都合よく共存できる。加
うるに、それらは極めて広い温度範囲にわたつて
耐熱性と耐凍結性を示し、しかも温度と圧力によ
つてその粘度が実質的に悪影響を受けない。さら
に、本発明の電気粘性懸濁液は、温度と周波数に
よつて僅かしか影響を受けない好ましい誘電特性
だけでなく高い誘電強度を示す。本発明による電
気粘性液体のもう一つの利点は、それが比較的扱
い易いので、製造するのに費用がからず、しかも
その商業製品を出発材料として使用できることに
ある。 本発明はグラフと表とともに後の実施例によつ
て説明され、その第１図は、一定の剪断速度にお
ける電場の強さの関数として電気粘性液体中で測
定して剪断力の依存関係を示し、第２図は、一定
の剪断速度における電場の強さの関数として電気
粘性液体の導電率を示しており、そして表は従来
技術と比較した本発明の電気粘性液体の特性デー
タを示している。電気粘性液体の製造に含まれる
プロセス段階、分散剤を製造する化学的な方法、
所望の物理的性質を監視するのに必要な測定技術
および本発明による電気粘性液体の典型的な例を
以下に述べる。 電気粘性液体を製造するために商業的なシリカ
ゲルを使用することができる。シリカゲルの水分
含有量は必要に応じて増大または減少させること
ができる。分散液の製造においてはシリコーン油
および分散剤の全部または一部を初めに導入し、
ついでシリカゲルを連続的に撹拌しながらシリコ
ーン油の中に導入することができる。シリカゲル
をまず第一に迅速に導入し、ついで粘度が上昇す
るにつれ、終わりに向かつてゆつくりと添加する
ことができる。まず第一に分散剤の一部だけを導
入したならば、シリカゲルの添加中に分散剤の残
りを添加する。しかしながら、電気粘性液体の製
造のために使用した方法および分散のために使用
した混合の型によつてその最終特性は余り影響を
受けない。例えば、分散のために通常の撹拌装
置、ボールミルまたは超音波を使用することがで
きる。しかしながら、分散液は一般に強い混合に
よつて速やかに製造することができ、その場合若
干微細にもなる。 分散剤の必要量は使用したシリカゲルの比表面
積によつて大いに左右される。大雑把に言えば、
約１〜４mg／ｍ2のシリカゲルが必要であるが、
正確な必要量はまた使用するシリカゲルの型を使
用する分散剤の型にも左右される。 商業的なシリカゲルは、例えば、ウルトラシル
（Ultrasil）、デユロシル（Durosil）、エクストル
ーシル（Extrusil）（デグサ（Degussa）製）お
よびバルカシル（Vulkasil）、シリカシル
（Silikasil）、およびバイシカル（Baysikal）（バ
イエル製）である。使用されるシリカゲルは純粋
なSio2であつてはならず、20重量％までの
Al2O3、Na2OおよびCaOを容易に含むことがで
き、さらに２、３重量％のSO3、Ｃおよび
Fe2O3も屡々存在することができる。燃焼損失、
すなわち 1000℃における重量損失は一般に10〜15重量％
で、平均してその約６重量％は105℃における乾
燥によつて測定された重量損失に相当している。
BET法によつて測定された比表面積は一般に20
〜200m2／ｇであるが、これは臨界的でなく、こ
れよりも僅かに小さくも、また大きくもなり得
る。しかしながら、比表面積が小さすぎると、生
成した分散体は望ましくないほど粗くなる一方、
過度に大きい比表面積は分散剤の過剰の需要を導
くことになる。 分散媒体として使用するのに好適なシリコーン
油はポリジメチル シロキサンおよび重合体のメ
チルフエニル シロキサンである。好適なシリコ
ーン油は室温で約３〜300mm2／Ｓの粘度を有する
が、こうして電気粘性液体の低い固有粘度が得ら
れ、それで電気粘性効果によつて実質的な粘度変
化を得ることができるので、一般に低粘度（３〜
20mm2／Ｓ）シリコーン油が好ましい。 分散剤として使用されるアミノ変性ポリシロキ
サンの製造は原則として専門家に知られている
が、必要な結合の型によつて変化する。次の式に
該当する化合物は、 （式中、ｎおよびｍは前に定義したとおりであ
り、そしてＸ＝CH2） 次の式に従つて対応するハロゲン誘導体（Clま
たはBr）と対応するアミンから製造される。 塩素含有化合物は所望量のClCH2（CH3）2SiCl、
ClCH2（CH3）SiCl2および（CH3）2SiCl2の共加水
分解によつて製造される。Clの代わりに勿論Br
を使用してもよい。 ＸがC2〜C6アルキル基である前述の型の化合
物は、例えば白金触媒によつてSiH含有化合物に
適当なオレフインを付加することによつて製造で
きる。このようにして、例えば塩化アリルは次の
式に相当するシリコーン油と反応してγ−クロル
官能性のシリコーン油を生成し、これは、Ｘ＝
CH2について上に述べた反応と同様に反応して所
望のアミノ官能性のシリコーン油を生成すること
ができる。 これに代わる方法も原則として専門家に知らせ
ている。 Ｘがアミノアルコキシ基である前述の分散剤の
型の化合物は、例えはSiCl基、SiOCH2H5基、
〔実施例および発明の効果〕
シリカゲル１： SiO2 約80重量％ CaO 約 ６重量％ Na2O 約 ３重量％ Al2O3 0.4重量％未満 DIN 55921／２による燃焼損失： 約７重量％ DIN 55921／２による乾燥損失： 約６重量％ BET表面積 ： 約35
m2／ｇ シリコーン油：ポリジメチル シロキサン 25℃における粘度： ５mm2S-1 25℃における密度： 0.9／cm3 ０℃および50Hzにおける、DIN53483 による誘電率Er： 2.8 ０℃および50Hzにおける、DIN53483 によるロスフアクタ：２・10-4 従来例 １ シリカゲル１ 40重量部 シリコーン油 60重量部 ソルビタン モノオレエート ４重量部 従来例 ２ シリカゲル１ 40重量部 シリコーン油 60重量部 ソルビタン セスキオレエート ４重量部 従来例 ３ シリカゲル１ 40重量部 シリコーン油 60重量部 グリセロール モノオレエートおよび ジオレエート（アトモス（Atmos）300）
４重量部 従来例 ４ シリカゲル１ 40重量部 シリコーン油 60重量部 ２−ヘプタデセニル−４−エチル−２−オキサゾ
リン−４−メタノール ６重量部 実施例 １ シリカゲル１ 40重量部 シリコーン油 60重量部 M′2D16 ２重量部 実施例 ２ シリカゲル１ 40重量部 シリコーン油 60重量部 M″2D28 ４重量部 実施例 ３ シリカゲル１ 40重量部 シリコーン油 60重量部 M′2D′2D69 ２重量部 実施例 ４ シリカゲル１ 50重量部 シリコーン油 50重量部 M′2D120 2.5重量部 実施例 ５ シリカゲル１ 40重量部 シリコーン油 60重量部 HO−D200−Ｈ ４重量部 実施例 ６ シリカゲル１ 40重量部 シリコーン油 60重量部
【式】 ４重量部 ただし、以上のＤ，D′，M′，M″はそれぞれ下
記の基を表わす。
【表】 【図面の簡単な説明】
第１図は本発明の電気粘性液体中で測定され
た、一定の剪断速度における電場の強さと剪断力
の関係を示すグラフであり、そして第２図は同様
に電場の強さと導電率との関係を示すグラフであ
る。

Claims (1)

  1. 【特許請求の範囲】 １ 分散相として１〜15重量％の水分含有量を有
    するシリカゲルを25重量％よりも多く含むととも
    に、液相としてシリコーン油を含み、そして分散
    剤も含む電気粘性懸濁液において、その分散剤が
    800を越す分子量を有する、アミノ官能性または
    ヒドロキシ官能性またはアセトキシ官能性または
    アルコキシ官能性のポリシロキサンからなること
    を特徴とする、前記電気粘性懸濁液。 ２ ポリシロキサンが、シリカゲル粒子を基にし
    て、１〜30重量％、そして好ましくは５〜20重量
    ％の濃度で添加されることを特徴とする、特許請
    求の範囲第１項記載の電気粘性分散液。 ３ アミノ官能性のポリシロキサンが下記の式に
    該当することを特徴とする特許請求の範囲第１項
    または第２項記載の電気粘性分散液。 この式において 10＜ｎ＜1000、 ｍ＝０〜５、 Ｒ＝ＨまたはC1〜C8アルキル基であり、そして
    Ｘ＝Ｃ、Ｈおよび、随意にＯおよび／またはＮか
    らなる二官能性の基である。 ４ アミノ官能性のポリシロキサンが次の式に該
    当することを特徴とする、特許請求の範囲第３項
    記載の電気粘性分散液。 M′2D′nDo この式において、 であり、そしてｍ＝０〜３で、10＜ｎ＜1000であ
    る。 ５ ポリシロキサンが次の式に該当することを特
    徴とする、特許請求の範囲第１項または第２項記
    載の電気粘性分散液。 この式において 10＜ｎ＜1000であり、そしてＹは加水分解できる
    基、特にヒドロキシ基、アルコキシ基またはカル
    ボキシ基である。
JP60164241A 1984-07-26 1985-07-26 電気粘性液体 Granted JPS6144998A (ja)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19843427499 DE3427499A1 (de) 1984-07-26 1984-07-26 Elektroviskose fluessigkeiten
DE3427499.5 1984-07-26

Publications (2)

Publication Number Publication Date
JPS6144998A JPS6144998A (ja) 1986-03-04
JPH0339560B2 true JPH0339560B2 (ja) 1991-06-14

Family

ID=6241578

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Country Link
US (1) US4645614A (ja)
EP (1) EP0170939B1 (ja)
JP (1) JPS6144998A (ja)
KR (1) KR920001052B1 (ja)
AT (1) ATE35824T1 (ja)
AU (1) AU575416B2 (ja)
BR (1) BR8503538A (ja)
CA (1) CA1255091A (ja)
DE (2) DE3427499A1 (ja)
DK (1) DK162106C (ja)
ES (1) ES8704536A1 (ja)
FI (1) FI78500C (ja)
NO (1) NO165728C (ja)
ZA (1) ZA855611B (ja)

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DK338085D0 (da) 1985-07-24
DE3563856D1 (en) 1988-08-25
NO165728B (no) 1990-12-17
ZA855611B (en) 1986-03-26
CA1255091A (en) 1989-06-06
BR8503538A (pt) 1986-04-22
FI78500C (fi) 1989-08-10
ATE35824T1 (de) 1988-08-15
DE3427499A1 (de) 1986-02-13
NO165728C (no) 1991-03-27
EP0170939A1 (de) 1986-02-12
ES8704536A1 (es) 1987-04-01
KR860001180A (ko) 1986-02-24
DK338085A (da) 1986-01-27
ES545527A0 (es) 1987-04-01
DK162106B (da) 1991-09-16
AU575416B2 (en) 1988-07-28
FI78500B (fi) 1989-04-28
DK162106C (da) 1992-02-17
FI852892L (fi) 1986-01-27
US4645614A (en) 1987-02-24
JPS6144998A (ja) 1986-03-04
FI852892A0 (fi) 1985-07-24
AU4528485A (en) 1986-01-30
EP0170939B1 (de) 1988-07-20
KR920001052B1 (ko) 1992-02-01
NO852800L (no) 1986-01-27

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