JP3970932B2 - ミストオイル潤滑剤 - Google Patents

ミストオイル潤滑剤 Download PDF

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JP3970932B2
JP3970932B2 JP53356497A JP53356497A JP3970932B2 JP 3970932 B2 JP3970932 B2 JP 3970932B2 JP 53356497 A JP53356497 A JP 53356497A JP 53356497 A JP53356497 A JP 53356497A JP 3970932 B2 JP3970932 B2 JP 3970932B2
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oil
mist
polyisobutylene
weight
carbon atoms
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JP2000507288A (ja
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ジェリーンスキ，ジェイムズ
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エクソン ケミカル パテンツ インコーポレイテッド
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Description

この発明は、合成エステル基油に基づくミストオイル潤滑組成物に関する。
ミストオイル潤滑組成物はエアロゾルの形態の油組成物の微小液滴を、種々の機械部品の潤滑させるべき領域に分配する。
オイルミストはいろいろな方法で生じさせることができる。典型的な系では、ベンチュリ管に向けて開放されている貯蔵器から成る装置を採用している。圧縮ガスをこのベンチュリ管から吹出すと、それで生じた吸引作用によって潤滑剤は貯蔵器から引っ張られ、その空気乱流によってその潤滑剤は機械的に小さな液滴に断裂される。その混合物は下方に向かってじゃま板に衝突し、そこで運搬が困難な大きい液滴は合体して貯蔵器へ戻る。多くの油粒子は粒径が0.1〜20μｍのエアロゾルを形成する。
この油滴の粒径の制御は、オイルミスト潤滑系の重要な側面である。粒子が大きすぎる場合には、その液滴はベアリング又はその他の表面を直ちに潤滑するが、供給輸送管路内に凝縮し易い。一方、粒子が小さすぎてその速度が遅すぎる場合には、合体が起きず漂遊ミストは深刻な問題を生じる。微エアロゾルは再分級（reclassification）により合体することが困難であり、過剰な漂遊ミストが生じて大気をくすぶらせる結果になる。
そのため、漂遊ミストはミストオイル潤滑系の最も厄介な問題である。通常潤滑された機械部品は大気に開放されており、再分級されないミストは大気中に拡散し、環境設備や呼吸器系に堆積するため、健康や安全性にとって潜在的に有害になりうる。
オイルミスト潤滑系は、例えば、英国特許第1,099,450号(1966)に開示されており、それは漂遊ミストを制御するために高分子量ポリマーを使用する方法を開示している。この高分子量ポリマーとして、数平均分子量が少なくとも100,000の酢酸ビニル、アルキルフマル酸塩又はエステル及びＮ−ビニルピロリドンから成るコポリマーが好ましい。数平均分子量が少なくとも10,000、例えば44,000、のポリイソブテンもまた開示されている。これらの漂遊ミスト抑止添加剤は石油鉱油に基づくオイルミスト潤滑組成物中に用いられる。
またAltgeltらの米国特許第3,805,918号(1974)も、望ましくない漂遊ミストの生成を抑止するための比較的高分子量のポリマーを使用する方法を開示している。特にこの引例は粘度平均分子量が20,000以上のオレフィン系コポリマーを開示している。特にこの引例の７欄25行目には、分子量が50,000〜800,000の高分子量のポリイソブチレンは漂遊ミスト抑止剤としてより有効である旨が記載されている。
英国特許第1,333,882号は炭素数が６以下のアルコール及び炭素数が16〜22のジカルボン酸のエステル並びに分子量が1,200〜4,500のブテンポリマーから成る合成潤滑剤を開示している。
Zehlerらの米国特許第4,589,990号(1986)は改良されたミスト潤滑組成物を開示しており、それはある種の合成エステル基油（例えば、ポリオールエステル、トリメリット酸塩若しくはエステル、又は高分子量脂肪酸エステル）を含み、その油の漂遊ミスト性を改善するために添加量の平均分子量が25,000〜300,000のポリイソブチレンを含有している。
この発明は、基油としてのアルキルポリカルボン酸エステルに基づくミストオイル潤滑組成物が、一定量の比較的低分子量のポリイソブチレンを使用することにより、その漂遊ミスト性を顕著に改善することを見出した。
この発明によれば、
a）ポリカルボン酸のアルキルエステル又はそのエステルの混合物である基原料エステル油であって、前記アルキルが直鎖又は分枝であってその炭素数が５〜18であり、その油の40℃における粘度が10〜150cStである油90〜95重量％、
b）さび止め剤、腐食防止剤、耐摩耗剤、酸化防止剤、乳化破壊剤、破泡剤及び極圧剤から成る群から選択される一種以上の添加剤であってポリイソブチレンではない添加剤３〜５重量％、及び
c）漂遊ミスト抑止剤として、数平均分子量が約400〜2,500であるポリイソブチレン１〜５重量％から成りかつそれらを結合することにより合成され、その漂遊ミスト性を低減した、ミスト潤滑に適した潤滑組成物が見出された。
この発明のこの他の実施態様は、潤滑剤として前記の組成物を用いて、加圧下で潤滑剤のミストを空中に発生させ、それを潤滑させるべき金属表面に空気圧で移送し、より大きな液滴に合体させ、その金属表面に付着させるミスト潤滑方法である。
一般的に適した基原料エステル油は、アルキルが直鎖又は分枝であってその炭素数が５〜18である芳香族又は脂肪族のポリカルボン酸のアルキルエステルから成り、その油の40℃における粘度は10〜150cStである。炭素数が８〜14である芳香族ジカルボン酸、炭素数が４〜12である脂肪族ジカルボン酸、及び炭素数が８〜12である脂環式ジカルボン酸のアルキルエステルが好ましい。適した酸には、フタル酸、アジピン酸、トリメリト酸、ピロメリト酸、マレイン酸、アゼライン酸、スベリン酸、セバシン酸、リノール酸ダイマー、マロン酸、アルキルコハク酸、アルケニルコハク酸等がある。
この発明で用いる好ましい基原料エステル油は、フタル酸ジトリデシル約80〜85重量％及びアジピン酸ジトリデシル約10〜15重量％から成る分枝鎖のフタル酸トリデシル及びアジピン酸トリデシルの混合物であり、より好ましくはフタル酸ジトリデシル約81重量％及びアジピン酸ジトリデシル約15重量％から成る40℃における粘度が約68cStである分枝鎖のフタル酸トリデシル及びアジピン酸トリデシルの混合物である。
この発明の組成物は添加剤として耐摩耗剤であるホスホロチオン酸トリフェニル、さび止め剤であるベンゾトリアゾール及びアルキル化ベンゾトリアゾール、酸化防止剤であるフェニチアジン及びジノニルジフェニルアミン、並びに乳化破壊剤であるオキシアルキル化（プロピレンオキシド70％及びエチレンオキシド30％）アミルフェノールなどを含むものが好ましい。
この発明の組成物に用いられる特定の目的を有する添加剤はこの分野で公知であり、各添加剤の含有量は約0.02〜2.0重量％であり、これらの添加剤の全含有量は３〜５重量％である。
酸化防止剤にはフェノール系及びアリールアミン系があるが、特にフェノチアジン及びジノニルジフェニルアミンが好ましい。
耐摩耗剤及び極圧剤には硫化脂肪酸又は脂肪酸エステル、有機ポリスルフィド、アミンホスフェート及びジアルキルホスフェート等の有機亜リン酸誘導体などがあり、特にホスホロチオン酸トリフェニルが好ましい。
さび止め剤及び腐食防止剤には二塩基酸、キノリン及びキノン、アルケニルコハク酸無水物のエステル又はアミド誘導体、アルキルスルホネートなどがあり、ベンゾトリアゾール並びにアルキルの炭素数が１〜20であるアルキル化ベンゾトリアゾール及びアルキル化アミノメチレンベンゾトリアゾールが好ましい。
典型的な乳化破壊剤にはアルコキシアルキル化アルキルフェノール、一価アルコール、アルキレングリコールなどがあり、オキシアルキル化（プロピレンオキシド70％及びエチレンオキシド30％）アミルフェノール樹脂が好ましい。
破泡剤にはポリジメチルシロキサンのようなシリコンオイル、アクリル酸塩又はエステルがある。
この発明の組成物の漂遊ミスト抑止剤は数平均分子量(Mn)が400〜2,500（ゲル透過クロマトグラフィーで測定した。）のポリイソブチレンであり、ミスト潤滑剤組成物中のその含有量は約１〜５重量％であってもよい。Mnが1,300のポリイソブチレンを１重量％含むオイル又はMnが950のポリイソブチレンを３重量％含む油が好ましい。
ここで用いた“ポリイソブチレン”という用語は、一般的に炭素数が４のオレフィンの重合から生成し、Mnが約400〜2,500の分子量を有する、ポリ−n−ブテン及びポリイソブチレンの混合物を意味する。
この発明で用いるためのポリイソブチレンは、イソブチレンを約６〜50重量％含み、その残りがシス又はトランスのブテン及びイソブチレンの混合物であり、ブタジエンを１重量％以下含む炭素数が４の精油所ガス流から合成されるポリブテン及びポリイソブチレンの混合物が好ましい。特にイソブチレンを約６〜45重量％、飽和ブテンを約25〜35重量％、１−及び２−ブテンを約15〜50重量％から成る炭素数が４の精油所ガス流から合成されるポリマーが好ましい。このポリマーはルイス酸触媒により合成される。
この発明の油は、空中で油の液滴のミスト分散として発生するときに、0.4μｍAED以下の液滴粒子及び0.4〜0.7μｍAEDの粒子である１μｍ以下の微粒子の量が顕著に少ない。ここでAEDとは空気動力学的等価直径(Aerodynamic Equivalent Diameter)であり、静止空気中の粒子と同じ重力による終末沈降速度を有する単位密度球体の直径で定義される。
実施例では、Texas AVM大学のA.Shamin及びC.F.Kettlebroughによる“Aerosol Aspects of Oil Mist Lubrication Reclassification and Deposition in Bearings”the Energy Resources Technology Conference and Exhibition, Houston, Texas(1996.1)により公開された液滴サイズの測定方法を用いた。
この発明は更に以下の実施例で例証される。すべての％は重量％を意味する。
実施例
入手可能なミストオイル潤滑剤基油は以下の組成で合成されている：
Figure 0003970932
この発明の油１〜７は前記基油95〜99％を下表に記載の量のポリイソブチレンと混合することにより作られた。
Figure 0003970932
実験手順：
基油及びこの発明の７つの各油の漂遊ミスト性、特に１μｍ以下の液滴粒子のサイズ、を評価した。これらの極微粒子は肺の敏感な器官に進入することができるので、その量を減らすことは重要である。
すべての試験に４０Ｂ１渦型のミスト発生器を用いた。その油弁を完全に開き、その空気の側管を完全に閉じた。貯蔵タンクの中の油を24℃に保持した。すべての試験において、その発生器の中の油のレベルを一定に保った。すべての試験において、オイルミスト供給系における配管の配置を同じにした。試験ベアリングの前後で発生後の粒子の量−サイズの分布を測定した。これらの試験に希釈室を備えた内部カスケードインパクターを用いた。各試験について３回測定を行った。全部で45回の測定を行い450のデータポイントを得た。ミストタイプ再分級器はミストオイルの量−サイズの分布について無視できる誤差しか生じなかった。そのため、加圧されたオイルミストがミストタイプ再分級器を通過した後で、発生したオイルミストの液滴の量−サイズの分布を測定した。このことはサンプリングのプロセスを簡単にした。これらの試験において、試験ベアリング（ピッチ円直径が77.5mm）を2,400rpmで稼動した。試験ベアリングを潤滑するためにNo.501ミストタイプ再分級器（流量が0.09SCFM（標準立方フィート／分））を用いた。
粒子径分布をポリイソブチレン漂遊ミスト抑止剤を含まない基油の粒子径分布と比べることにより、上記の７つの各油の漂遊ミスト性を測定した（表１）。基油の粒子径分布と比べると、１〜７の各油について0.0〜0.4μｍの範囲の粒子及び0.4〜0.7μｍの範囲の粒子が実質的に減少していることが観察された。Andersen １ACFM（有効立方フィート／分）発展不可能な(non-viable)カスケードインパクターを用いてオイルミストの液滴の量−サイズの分布を測定した。粒子のAEDを見ると、カスケードインパクターを通して真空ポンプでアエロゾルを吸引した場合には、カスケードインパクターの種々の段階において空中浮揚の粒子を集めたことがわかる。
Figure 0003970932

Claims (6)

  1. ａ）炭素数が８〜１４である芳香族ジカルボン酸、炭素数が４〜１２である脂肪族ジカルボン酸、及び炭素数が８〜１２である脂環式ジカルボン酸から成る群から選択されるポリカルボン酸のアルキルエステル又はそのエステルの混合物である基原料エステル油であって、前記アルキルが直鎖又は分枝であってその炭素数が５〜１８であり、その油の４０℃における粘度が１０〜１５０ｃＳｔである油９０〜９５重量％、
    ｂ）さび止め剤、腐食防止剤、耐摩耗剤、酸化防止剤、乳化破壊剤、破泡剤及び極圧添加剤から成る群から選択される特定の目的を有する一種以上の添加剤３〜５重量％、及び
    ｃ）漂遊ミスト抑止剤として、数平均分子量が４００〜２，５００であるポリイソブチレン１〜５重量％から成るミスト潤滑用組成物。
  2. 前記ポリイソブチレンのＭｎが９５０〜１，３００である請求項１に記載の組成物。
  3. 前記ポリイソブチレンのＭｎが１，３００でありその含量が１重量％である請求項１に記載の組成物。
  4. 前記ポリイソブチレンのＭｎが９５０でありその含量が３重量％である請求項１に記載の組成物。
  5. 前記エステル油が分枝鎖のフタル酸ジトリデシル８０〜８５重量％及びアジピン酸ジトリデシル１０〜１５重量％から成る請求項１に記載の組成物。
  6. 前記特定の目的を有する添加剤がフェノチアジン及び／又はジノニルジフェニルアミンを含む酸化防止剤、ベンゾトリアゾール及び／又はアルキル化ベンゾトリアゾールを含むさび止め剤、オキシアルキル化アミルフェノール樹脂を含む乳化破壊剤並びにホスホロチオン酸トリフェニルを含む耐摩耗剤を含む請求項１〜５のいずれか一項に記載の組成物。
JP53356497A 1996-03-18 1997-03-14 ミストオイル潤滑剤 Expired - Lifetime JP3970932B2 (ja)

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JP4049916B2 (ja) 1998-12-25 2008-02-20 出光興産株式会社 高温用潤滑油組成物
DE19931218B4 (de) * 1999-07-06 2005-06-02 Clariant Gmbh Verwendung von Polymeren als Anti-Nebel-Additiv in wasserbasierenden Kühlschmierstoffen
WO2001030945A1 (fr) * 1999-10-25 2001-05-03 Nippon Mitsubishi Oil Corporation Composition de fluide pour systeme de coupe ou de meulage utilisant une quantite de fluide a peine decelable
JP2008062361A (ja) * 2006-09-11 2008-03-21 Nippon Oil Corp 極微量油剤供給式切削・研削加工方法および極微量油剤供給式切削・研削加工用油剤組成物
WO2011047285A1 (en) * 2009-10-16 2011-04-21 University Of Virginia Patent Foundation Gas-expanded lubricants for increased energy efficiency and related method and system
WO2011113707A1 (en) * 2010-03-17 2011-09-22 Exxonmobil Chemical Patents Inc. Plasticiser blends and compositions and articles made therefrom
JP5804568B2 (ja) 2012-09-27 2015-11-04 信越化学工業株式会社 シリコーンミスト抑制剤

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