JPH08143883A - 耐熱性グリース組成物 - Google Patents

耐熱性グリース組成物

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Publication number
JPH08143883A
JPH08143883A JP6308121A JP30812194A JPH08143883A JP H08143883 A JPH08143883 A JP H08143883A JP 6308121 A JP6308121 A JP 6308121A JP 30812194 A JP30812194 A JP 30812194A JP H08143883 A JPH08143883 A JP H08143883A
Authority
JP
Japan
Prior art keywords
grease
heat
grease composition
formula
compound
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.)
Pending
Application number
JP6308121A
Other languages
English (en)
Inventor
Shishiyou Chin
志昌 沈
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.)
DuPont Toray Specialty Materials KK
Original Assignee
Dow Corning Asia Ltd
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 Dow Corning Asia Ltd filed Critical Dow Corning Asia Ltd
Priority to JP6308121A priority Critical patent/JPH08143883A/ja
Priority to EP95308254A priority patent/EP0717099A1/en
Publication of JPH08143883A publication Critical patent/JPH08143883A/ja
Priority to US08/837,663 priority patent/US5908815A/en
Pending legal-status Critical Current

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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00Compositions 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
    • C08L83/04Polysiloxanes
    • C08L83/08Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
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Abstract

(57)【要約】 (修正有) 【目的】 フッ素系グリースの高温条件での劣化現象を
防止して、1.耐熱性に優れること、2.耐熱性が長期
的に安定であること、の特性を有するグリース組成物の
提供。 【構成】 フルオロシリコーンオイル(イ)、フッ素樹
脂系増ちょう剤(ロ)と 変性ウンデカン混合物 変性ブタン Cuフタロシアニン Caスルフォネート等で表される添加剤(ハ)の少なく
とも1種以上を含有することを特徴とする耐熱性グリー
ス組成物。

Description

【発明の詳細な説明】
【0001】
【技術分野】本発明は、フルオロシリコーンオイルを基
油とし、フッ素系樹脂を増ちょう剤とする耐熱性フッ素
系グリース組成物に関する。
【0002】
【従来技術】フルオロシリコーンオイルを基油とし、フ
ッ素系樹脂を増ちょう剤とするグリースは、耐熱性が良
いグリースとして公知である。例えば、US3,31
4,889やUS3,642,626などに開示されて
おり、前記米国特許明細書には、広い温度範囲で使用可
能で、高荷重下にて使用できるグリース組成物を開示し
ており、特に基油としてフロロシリコーンオイルが使用
されている。さらに、特開昭61−113694号に
は、耐熱性に優れたグリースの処方として、フロロポリ
エーテルを基油とし、フッ素樹脂を含む組成物が開示さ
れている。しかし、このようなフッ素系グリースであっ
ても、著しい高温条件下では時間の経過とともに、性状
が不安定になるという問題があった。
【0003】
【目的】本発明は、フッ素系グリースの高温条件での劣
化現象を防止して、以下の特性を有するグリース組成物
の提供を目的とする。 1.耐熱性に優れること 2.耐熱性が長期的に安定であること 具体的には、前記フッ素系グリースからの基油の蒸発抑
止および/またはグリースのゲル化ないしは硬化を防止
することを目的とする。従って、本発明における耐熱性
とは、グリースからの蒸発と、ゲル化の傾向をもって指
標とした。
【0004】
【構成】本発明はフロロシリコーンオイル基油(イ)
と、フッ素樹脂系増ちょう剤(ロ)を含有するグリース
組成物において、従来から見られた高温条件下における
経時でのゲル化や経時での蒸発量の増大といった問題を
解決したものであり、特に自動車用ファンクラッチベア
リングに適用して優れた耐熱性を示すグリース組成物に
関する。本発明はフルオロシリコーンオイルを基油と
し、フッ素系樹脂を増ちょう剤として含有するフッ素系
グリースにおいて、該グリースに特定の酸化剤を含有さ
せることにより、前記の目的を達成した。
【0005】すなわち、本発明者らはフロロシリコーン
オイル基油とフッ素樹脂系増ちょう剤を含有するフッ素
系グリースの高温条件下での使用によるゲル化の防止と
基油の蒸発量の低減化に優れた効果のある添加剤として
多くの添加剤の中から前式(a)〜(g)で表わされる
添加剤よりなる群から選ばれる少なくとも1種以上を使
用することを見い出したことにもとづき、本発明を完成
した。具体的には、上記(a)〜(g)から選ばれる1
種以上を含んだ本発明のグリース組成物は、(a)〜
(g)以外の添加剤を配合したグリース組成物に較べて
特にグリースの高温条件下での使用によるゲル化の防止
と基油の蒸発量の低減化にすぐれた耐熱性、優れた効果
を示すという知見に基づき、本発明は完成されたもので
ある。
【0006】本発明のフッ素系グリースの(イ)成分で
ある基油を構成するフロロシリコーンオイルとは、フッ
素化アルキル基あるいはパーフロロアルキル基を有する
オルガノポリシロキサンであれば、格別限定されるもの
ではない。本発明のフロロシリコーンオイルの粘度とし
ては、グリース化できる範囲であれば、格別限定される
ものではない。通常は100cSt〜100,000c
Stのものが選択されるが、好適には100cSt〜5
0,000cStのものが選択される。また、ファンク
ラッチベアリング用としては、300cSt〜5,00
0cStが望ましい。また、本発明のフロロシリコーン
オイルの使用可能な温度範囲は、−50〜400℃、好
ましくは−30〜300℃の範囲のものである。本発明
に使用されるフロロシリコーンオイルの具体例として、
下式(1)のものを示すが、これらに限定されるもので
はない。さらにこれらフロロシリコーンに、本発明の所
期の目的を防げない限り、他の公知のグリース基油、例
えばパーフルオロポリエーテル、フロロシリコン、メチ
ルフェニルシリコン、ジメチルシリコン等のシリコン、
エステル、ポリエーテル、合成炭化水素油、鉱物油、植
物油を添加、混合してもよい。
【0007】
【化6】 R′:炭素原子数1〜3の炭化水素基 R″:メチル基、エチル基、ビニル基、フェニル基又は
−CH2CH2R基 (R:炭素原子数1〜10のパーフルオロアルキル基で
あり、R″のうち少なくとも50%は−CH2CH2R基
である。また、nは前記の粘度範囲を与える範囲の数で
ある。) 前式(1)で示されるフロロシリコーン化合物のうち、
特に以下のものが望ましい。
【0008】下式(2)で表わされるトリフロロプロピ
ルメチルポリシロキサン
【化7】 (m:粘度範囲100cSt〜100,000cStを
与える範囲の数である。)
【0009】下式(3)で表わされるパーフロロアルキ
ルメチルポリシロキサン
【化8】 (aおよびb:粘度範囲100cSt〜100,000
cStを与える範囲で、互いに任意に選択される数であ
る。)
【0010】
【化9】 (n:粘度範囲100cSt〜100,000cStを
与える範囲の数である。)
【化10】 (mおよびn:粘度範囲100cSt〜100,000
cStを与える範囲で、互いに任意に選択される数であ
る。)
【化11】 (mおよびn:前記に同じ。)
【0011】
【化12】 (n:前記に同じ。)
【化13】 (n:前記に同じ。)
【化14】 (mおよびn:上記に同じ。)
【0012】本発明の耐熱性グリース組成物の(ロ)成
分である増ちょう剤としては、フッ素樹脂系のものであ
れば、格別その種類は限定されないが、例えばポリテト
ラフルオロエチレン(PTFE)、三フッ化エチレン樹
脂等が挙げられる。さらに前記フッ素樹脂系増ちょう剤
に、本発明の目的を妨げない限り、他の公知の増ちょう
剤、例えばLi−石鹸、シリカ、Ca−石鹸、Al−石
鹸、Ca−complex、Al−complex、L
i−complex、ウレア、ベントン等を加えてもよ
い。本発明の耐熱性グリース組成物におけるフルオロシ
リコーンオイルとフッ素樹脂系増ちょう剤との配合比率
は、該グリースを適用する用途に応じて適したちょう度
あるいはその使用温度に合った組み合わせとなるもので
あればよく、格別限定されるものではないが、通常は、
JIS K2220のちょう度番号1番〜3番の範囲が
選択される。また、ファンクラッチベアリング用には、
ちょう度番号2番の範囲が望ましい。本発明の耐熱性グ
リース組成物の(ハ)成分としては、下式(a)、
(b)、(c)、(d)、(e)、(f)および(g)
で表わされる化合物よりなる群から選ばれた少なくとも
1種の化合物、または2種以上の混合物を用いることが
できる。
【0013】
【化15】 3,9−ビス〔1,1−ジメチル−2−{β−(3−t
−ブチル−4−ハイドロキシ−5−メチルフェニル)プ
ロピオニルオキシ}エチル〕−2,4,8,10−テト
ラオキサスピロ〔5,5〕ウンデカン
【0014】
【化16】 (R:炭素原子数12のアルキル基)
【0015】
【化17】 1,1,3−トリス(2−メチル−4−ヒドロキシ−5
−t−ブチルフエニル)ブタン
【0016】
【化18】 銅フタロシアニン(Cu−Phthalocyanin
e)
【0017】
【化19】R−SO3Ca (e) (R:アルキル基) カルシウムスルフォネイト(Ca−Sulfonat
e) アセチルアセトン銅塩 (f) 次のと 両末端が4−(フェニルアミノ)フェノキシ・ジメチ
ルシリル基で封鎖されてなるジメチルポリシロキサン ポリジメチルシロキサンとジルコニウムカルボキシレ
ートの混合物(但し該混合物中のジルコニウム金属の含
有量は、0.1〜10重量%)を不活性雰囲気下でジル
コニウムカルボキシレートを分解できる温度で加熱して
得られたもの。(g) 前記両者の重量比は、0.5:1〜1:0.5が好まし
い。この重量比の範囲外では充分な耐熱性が得にくい。
また、両者は、混合物の形で使用してもよいし、あるい
は両者の1方を先に使用し、残りの1方を後に使用して
もよい。前記両末端4−(フェニルアミノ)フェノール
封鎖ジメチルポリシロキサンの粘度は、50〜300c
Stが好ましい。前記粘度の範囲外では分散性が充分で
ない。
【0018】前式(a)、(b)、(c)、(d)、
(e)、(f)および(g)で表わされる化合物よりな
る群から選ばれる1種又は2種以上の添加剤の配合量は
フルオロシリコーンオイルとフッ素樹脂系増ちょう剤の
合計量に対して0.5〜10重量%配合されることが必
要である。0.5重量%未満では、充分な耐熱性効果を
発揮できない。また10重量%以上ではグリースの性状
自体に影響を与えるものである。本発明の耐熱性グリー
ス組成物は、通常のグリース製造方法で使用される任意
の製造方法を採用することができる。具体的には、たと
えば基油、増ちょう剤および添加剤をニーダー等で充分
に混合した後、ロールを2回通す工程があげられる。本
発明の耐熱性グリース組成物には、上記のフルオロシリ
コーンオイル(イ)、フッ素樹脂系増ちょう剤(ロ)、
前式(a)、(b)、(c)、(d)、(e)、(f)
および(g)で表わされる添加剤(ハ)の他に、通常、
グリースに配合される各種添加剤を添加することができ
る。この様な例として、以下のものが挙げられる。 固体潤滑剤(MoS2、グラファイトなど) 極圧添加剤(ジチオリン酸亜鉛、ジチオカルバミン酸亜
鉛、フォスフェート、アルキルサルファイドなど) 次に本発明のグリース組成物を実施例として、前記の添
加剤を含有しない耐熱性グリースを比較例として、下記
実験1試験方法および実験2試験方法で評価し、その結
果を、下表1〜11に示した。本発明のグリース組成物
は、試料(グリース組成物)を200℃で貯蔵した場
合、貯蔵時間が264時間の段階で蒸発損が16%以
下、グリース性状を維持していることの再条件を満た
しているものである。
【0019】実験1試験方法 1)グリース(10g)をシャーレ(直径:51mm、
高さ:16mm)上に平になるように塗布し秤量する。 2)オーブンで温度:200℃でエージングする。 3)所定時間経過後オーブンからとり出し、放冷後秤量
する。
【0020】実験2試験方法 1)グリースの初期ちょう度は、不混和状態のもの10
gを1/2ちょう度試験器を用いて測定した。(不混和
ちょう度) 測定方法は「JIS K2220−198
4参考11.グリースの1/4及び1/2ちょう度試験
方法」に準じて行った。 2)グリースのエージングは実験1の方法で行った。 3)エージング後の測定は、1/4ちょう度試験器を用
いて不混和ちょう度を測定した。以下に前記の実験1試
験方法および実験2試験方法で使用した配合成分につい
て説明する。
【0021】1.成分1−1(Si・OIL500)お
よび1−2(Si・OIL300)とも下式(10)で
表わされる。両末端がトリメチルシリル基で封鎖されて
おり、主鎖はトリフルオロプロピルメチルシロキサンで
構成されてなる基本構造の点では同じであるが、前者の
成分1−1は粘度が500cStであり、後者の成分1
−2は粘度が300cStのものである。
【化20】 (式中、nは成分1−1の場合には、粘度が500cS
tの範囲のものであり、成分1−2の場合には、粘度が
300cStの範囲のものである。) 2.成分2:PTFE(ポリテトラフルオロエチレン) 3.成分3:変性ウンデカン混合物〔前式(a)と
(b)の化合物の1:1混合物〕 4.成分4:変性ブタン〔前式(c)の化合物〕
【0022】5.成分5:Cuフタロシアニン〔前式
(d)の化合物〕 6.成分6:Caスルフォネート〔前式(e)の化合
物〕 7.成分7:MgO 8.成分8:Caステアリン酸〔カルシウムステアリン
酸塩〕 9.成分9:AcAcCa〔アセチルアセトンカルシウ
ム塩〕 10.成分10:CaSANSA〔セバシン酸モノステ
アリルアミドカルシウム塩〕 11.成分11:ZnSANSA〔セバシン酸モノステ
アリルアミド亜鉛塩〕
【0023】12.成分12:次の式で表わされる化合
物(粘度100cSt)
【化21】 (式中xは粘度100cStを与える値) 両末端が4−(フェニルアミノ)フェノールで封鎖され
たジメチルポリシロキサン 13.成分13:ポリジメチルシロキサンとジルコニウ
ムオクタネイトの混合物(重量比3:1)を窒素雰囲気
下350℃で24時間加熱したもの 14.成分14:成分12と成分13の1:1混合物 15.成分15:フェロセンFe〔Fe(C552
(メタロセンFeとも言う) 16.成分16:AcAcCu〔アセチルアセトン銅
塩〕 17.成分17:Ca(OH)2 18.成分18:PTFEパウダー(商品名 セフラル
ルーブ、セントラルガラス社製) 19.成分19:PTFEパウダー(商品名 フルオン
171J、旭硝子社製)
【0024】実験1(蒸発テスト)のグリースの組成
【表1】
【0025】実験1(蒸発テスト)の結果 〔蒸発損(%)/貯蔵時間(Hrs)〕
【表2】 *貯蔵温度:200℃ 試料:10g *実施例1〜4は、貯蔵時間264時間以降においてもグリース性状を維持
【0026】実験1(蒸発テスト)のグリースの組成
(比較例)
【表3】
【0027】実験1(蒸発テスト)の結果(比較例) 〔蒸発損(%)/貯蔵時間(Hrs)〕
【表4】 貯蔵温度:200℃ 試料:10g *〜 グリース性状を失ったため測定を終了した。
【0028】実験1−2(エージングテスト)のグリー
スの組成およびテスト結果(実施例)
【表5】
【0029】実験1−2(エージングテスト)のグリー
スの組成およびテスト結果(比較例)
【表6】
【0030】実験2(蒸発テスト)のグリースの組成
(実施例)
【表7】
【0031】実験2(蒸発テスト)の結果 〔蒸発損(%)/貯蔵時間(Hrs)〕
【表8】 *貯蔵温度:200℃ 試料:10g *実施例9〜14は、貯蔵時間264時間以降においてもグリース性状を維持
【0032】実験2(蒸発テスト)のグリース組成(比
較例)
【表9】
【0033】実験2(蒸発テスト)の結果(比較例) 〔蒸発損(%)/貯蔵時間(Hrs)〕
【表10】 貯蔵温度:200℃ 試料:10g *比較例13、14、15、16、17については貯蔵時間264時間にて グリース性状を喪失した。
【0034】実験2−2(エージングテスト)のグリー
ス組成(実施例)
【表11】
【0035】本発明の具体的実施態様を、以下、記載す
る。 1.フルオロシリコーンオイル(イ)、フッ素樹脂系増
ちょう剤(ロ)と次式(a)、(b)、(c)、
(d)、(e)、(f)および(g)で表わされる添加
剤(ハ)の少なくとも1種以上を含有することを特徴と
する耐熱性グリース組成物。 2.前記1の耐熱性グリース組成物において、フロロシ
リコーンオイルの粘度が、100〜100,000cS
tの範囲のものである耐熱性グリース組成物。 3.前記1または2の耐熱性グリース組成物において、
フロロシリコーンオイルが、他の公知のグリース基油を
含有するものである耐熱性グリース組成物。 4.前記1、2または3の耐熱性グリース組成物におい
て、フロロシリコーンオイルが、前式(1)で表わされ
るものである耐熱性グリース組成物。 5.前記5の耐熱性グリース組成物において、前式
(1)で表わされるフロロシリコーンオイルが、前式
(2)、(3)、(4)、(5)、(6)、(7)、
(8)および(9)よりなる群から選ばれたものである
耐熱性グリース組成物。 6.前記1、2、3、4または5の耐熱性グリース組成
物において、増ちょう剤がポリテトラフルオロエチレン
および/または三フッ化エチレン樹脂である耐熱性グリ
ース組成物。 7.前記6の耐熱性グリース組成物において、増ちょう
剤が他の公知の増ちょう剤を含有するものである耐熱性
グリース組成物。 8.前記1、2、3、4、5、6または7のグリース組
成物において、添加剤(ハ)として、前式(a)、
(b)、(c)、(d)、(e)、(f)および(g)
で表わされる化合物よりなる群から選ばれた少なくとも
1種の化合物を含有するものである耐熱性グリース組成
物。 9.前記1、2、3、4、5、6、7または8の耐熱性
グリース組成物よりなることを特徴とするファンクラッ
チベアリング用耐熱性グリース組成物。
【0036】
【効果】本発明によると、高温条件下における経時での
ゲル化や経時での基油の蒸発量の増大といった問題を解
決した耐熱性グリース、特に自動車用ファンクラッチベ
アリングに適用して優れた耐熱性を示すグリース組成物
が提供された。
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 FI 技術表示箇所 C10M 129:74 129:10 139:00 135:10 139:06 139:02 139:04) C10N 20:00 A 20:02 50:10

Claims (1)

    【特許請求の範囲】
  1. 【請求項1】 フルオロシリコーンオイル(イ)、フッ
    素樹脂系増ちょう剤(ロ)と下記(a)、(b)、
    (c)、(d)、(e)、(f)および(g)で表わさ
    れる添加剤(ハ)の少なくとも1種以上を含有すること
    を特徴とする耐熱性グリース組成物。 【化1】 3,9−ビス〔1,1−ジメチル−2−{β−(3−t
    −ブチル−4−ハイドロキシ−5−メチルフェニル)プ
    ロピオニルオキシ}エチル〕−2,4,8,10−テト
    ラオキサスピロ〔5,5〕ウンデカン 【化2】 (R:炭素原子数12のアルキル基) 【化3】 1,1,3−トリス(2−メチル−4−ヒドロキシ−5
    −t−ブチルフエニル)ブタン 【化4】 銅フタロシアニン(Cu−Phthalocyanin
    e) 【化5】R−SO3Ca (e) (R:アルキル基) カルシウムスルフォネイト(Ca−Sulfonat
    e) アセチルアセトン銅塩(f) 次のと 両末端が4−(フェニルアミノ)フェノキシ・ジメチ
    ルシリル基で封鎖されてなるジメチルポリシロキサンお
    よびポリジメチルシロキサンとジルコニウムカルボキ
    シレートの混合物(但し該混合物中のジルコニウム金属
    の含有量は、0.1〜10重量%)を不活性雰囲気下で
    ジルコニウムカルボキシレートを分解できる温度で加熱
    して得られたもの。(g)
JP6308121A 1994-11-17 1994-11-17 耐熱性グリース組成物 Pending JPH08143883A (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP6308121A JPH08143883A (ja) 1994-11-17 1994-11-17 耐熱性グリース組成物
EP95308254A EP0717099A1 (en) 1994-11-17 1995-11-17 Heat resistant grease
US08/837,663 US5908815A (en) 1994-11-17 1997-04-22 Heat resistant grease

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP6308121A JPH08143883A (ja) 1994-11-17 1994-11-17 耐熱性グリース組成物

Publications (1)

Publication Number Publication Date
JPH08143883A true JPH08143883A (ja) 1996-06-04

Family

ID=17977138

Family Applications (1)

Application Number Title Priority Date Filing Date
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Country Status (3)

Country Link
US (1) US5908815A (ja)
EP (1) EP0717099A1 (ja)
JP (1) JPH08143883A (ja)

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JP2001354986A (ja) * 2000-06-12 2001-12-25 Nok Kuluver Kk 潤滑グリース組成物
JP2002194379A (ja) * 2000-12-27 2002-07-10 Ge Toshiba Silicones Co Ltd 放熱グリース
JP2011213894A (ja) * 2010-03-31 2011-10-27 Daikin Industries Ltd 組成物、ペレット、樹脂成形品及び電線、並びに、組成物の製造方法
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JP2015151516A (ja) * 2014-02-18 2015-08-24 協同油脂株式会社 シリコーングリース組成物
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JP2001354986A (ja) * 2000-06-12 2001-12-25 Nok Kuluver Kk 潤滑グリース組成物
JP4505954B2 (ja) * 2000-06-12 2010-07-21 Nokクリューバー株式会社 潤滑グリース組成物
JP2002194379A (ja) * 2000-12-27 2002-07-10 Ge Toshiba Silicones Co Ltd 放熱グリース
US8182155B2 (en) 2005-09-02 2012-05-22 Ntn Corporation Lubricating grease and lubricating grease-enclosed roller bearing
US9868877B2 (en) 2009-06-30 2018-01-16 Daikin Industries, Ltd. Composition and method for producing the same, and powder coating material, pellet, resin formed article, and electric wire
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JP2015151516A (ja) * 2014-02-18 2015-08-24 協同油脂株式会社 シリコーングリース組成物
WO2015125805A1 (ja) * 2014-02-18 2015-08-27 協同油脂株式会社 シリコーングリース組成物
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EP0717099A1 (en) 1996-06-19

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