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JP3488920B2 - 自動車潤滑剤 - Google Patents

自動車潤滑剤

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Publication number
JP3488920B2
JP3488920B2 JP51373293A JP51373293A JP3488920B2 JP 3488920 B2 JP3488920 B2 JP 3488920B2 JP 51373293 A JP51373293 A JP 51373293A JP 51373293 A JP51373293 A JP 51373293A JP 3488920 B2 JP3488920 B2 JP 3488920B2
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JP
Japan
Prior art keywords
oil
weight
white oil
antioxidant
white
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 - Fee Related
Application number
JP51373293A
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English (en)
Other versions
JPH07503494A (ja
Inventor
オスチン・マルセル・アルフォンス・ヨセフ
アルベス・ドミニーク
ブーフェ・アラン・ガブリエール
スタイゲルバルト・エドガー・アンドレアス
Original Assignee
エッソ ソシエテ アノニム フランセ
エクソンモービル リサーチ アンド エンジニアリング カンパニー
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Publication of JPH07503494A publication Critical patent/JPH07503494A/ja
Application granted granted Critical
Publication of JP3488920B2 publication Critical patent/JP3488920B2/ja
Anticipated expiration legal-status Critical
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Description

【発明の詳細な説明】 この発明は、エンジンオイル、ギア油及び自動変速機
流体の如き自動車潤滑剤に関する。
従来、自動車潤滑剤は一般的な鉱油を基本にしてき
た。これらは過去には適切であることが立証されている
が、鉱油の基本原料は、優れた潤滑特性、特に動作寿命
を求めて日々増大する要請には必ずしも適合しない。こ
れらの特性は、添加剤を使用することによってある程度
は改善することはできるが、その基本原料の修正・変更
についての研究も行ってきた。最近、潤滑剤メーカは、
合成基本原料、例えば、ポリアルファオレフィンとエス
テル、を基本にして自動車潤滑剤を製造してきた。これ
らによって機能は改善されるが、欠点は高価であるとい
うことである。
それ故、それに代わる価格の安い基本原料による改善
された特性をもたらす自動車潤滑剤が必要となってい
る。
英国特許737,392は、酸化防止剤として有機ースズ化
合物を含有する潤滑油を開示している。基本原料は、通
常の方法で精製される石油留出物と残余、水素化鉱油、
ホワイト鉱油、または単独あるいは鉱油の潤滑剤と混ぜ
合わせて用いられるポリエーテルとポリエステル潤滑剤
から誘導することができる。その潤滑剤は、クランク室
油、加熱油、水圧油、切削油、タービン油または変圧器
油として応用することができる。
米国特許3,853,773は、精密機械装置に使用する抗ガ
ムおよび溶媒和潤滑剤を開示している。それは（本特許
で定義される）Ａタイプの変速機流体と高精製ホワイト
油との組合わせを基本としている。
米国特許4,652,385は、一組の三置換亜リン酸塩と立
体障害のフェノール性安定剤を酸化防止剤として含有す
る潤滑剤を開示している。基本原料は、水素化処理油、
ポリアルファオレフィン油またはパラフィンホワイト
油、あるいはそれらの混合物である。その潤滑剤は高温
度用途、例えば、コンプレッサ油、熱交換油、水圧流体
または蒸気タービン油に用いられる。
本発明は、下記成分から成る自動車潤滑剤を提供する
ものである： （ａ） 少なくとも30重量％がホワイト油である基本原
料；及び （ｂ） ジチオリン酸ジアルキル亜鉛、ジチオリン酸ジ
アリール亜鉛、ジチオリン酸アリールアルキル亜鉛、ア
ルキル化ジフェニルアミン、立体障害フェノール、リン
硫化アルキルフェノール、硫化フェノール、ジメルカプ
ト・ジチアジアゾール、及び銅ベースの酸化防止剤化合
物の１つ以上から選択された酸化防止剤。
この場合、潤滑剤はスズ含有酸化防止剤または有機的
に置換された亜リン酸塩または二リン酸塩酸化防止剤を
包含しないものとする。
本発明によるホワイト油を基本とした自動車潤滑剤
は、鉱油に基づく自動車潤滑剤と比べて優れた酸化安定
特性を有するという利点があり、それにもかかわらず合
成油に基づく潤滑剤と比べて製造コストが低いという利
点がある。このようにその潤滑剤は動作時間が長いとい
う利得を有し、即ち、それは機械装置、例えば、エンジ
ンまたは歯車箱の注油においてその流出および交換が必
要になる時まで延長期間にわたって使用することが可能
である。ある応用では、寿命充当潤滑剤として、即ち、
潤滑剤の動作寿命時がその注油している機械部品のそれ
と一致するかまたはそれを越える潤滑剤として使用でき
る。
ホワイト油は、“連邦規定である食品及び薬物管理規
約”、1991において規定されている。仕様書FDA 21 CFR
178−3620（ａ）に準拠した薬用ホワイト油または仕様
書FDA 21 CFR 178−3620（ｂ）に準拠した工学ホワイト
油の何れも本発明に用いることができる。
ホワイト油は、慣用のホワイト油であって、一般的な
硫黄及び窒素を含まない飽和炭化水素を生成する溶媒抽
出及び水素化法を使って得られる。比較的高いナフテン
含量を有するホワイト油はパラフィン質の多いホワイト
油に比べ改善された特性を表わすことが知られている。
好ましくは、本発明に使用されるホワイト油は、少なく
とも25重量％のナフテン含量を有する、ここで“ナフテ
ン含量”とは、標準試験、ASTM D 2140に従い、ホワイ
ト油の全炭素含量のうちのパーセントで表したナフテン
炭素の量で定義される。より好ましくは、ホワイト油の
ナフテン含量は30から50重量％、最も好ましくは、30か
ら40重量％である。高ナフテンホワイト油は、軽い水素
化条件を使って得られ、そのため油に含まれる環式分子
は実質的に破壊されない。典型的な軽水素化条件は、温
度:150と250℃の間、圧力:1000と20,000kPaの間であ
る。
本発明に有利に使用される高ナフテンホワイト油のナ
フテン組成は、好ましくは次の通りであり、その測定値
は標準試験法ASTM D 2786を使って得られる： １環:20−30重量％、好ましくは24−32重量％ ２環:13−27重量％、好ましくは17−23重量％ ３環:4−21重量％、好ましくは８−17重量％ ４環:3−19重量％、好ましくは７−15重量％ ５環以上:0−９重量％、好ましくは２−５重量％ 本発明に使用できる適当なFDA規定の食料級品質のホ
ワイト油の例としては、MARCOL 52（ナフテン含量34
％）、MARCOL 82（ナフテン含量32％）、MARCOL172（ナ
フテン含量34％）、PRIMOL 352（ナフテン含量32％）お
よびPLASTOL 352（ナフテン含量32％）が挙げられ、こ
れらの全てはExxon/Essoから供給される。本発明に使用
できる適当なFDA規定の工学級のホワイト油の例として
は、BAYOL 52（ナフテン含量34％）とPLASTOL 135（ナ
フテン含量36％）が挙げられ、これらは両方ともExxon/
Essoから供給される。MARCOL、PRIMOL、PLASTOL及びBAY
OLはExxon社の商標である。ナフテン含量は標準試験法A
STM2140に従って測定される。
基本原料は100％ホワイト油から成ってもよいし、ま
たはホワイト油と１つ以上の他の種類の油との混合物、
例えば、鉱油および／またはポリアルファオレフィンの
ような合成油またはポリオールエステルまたはポリオー
ルジエステルのようなエステル、および／または水素化
分解型の基本原料から成ってもよい。基本原料が混合物
なら、その基本原料中のホワイト油の好ましい割合は、
少なくとも30％、より好ましくは30と60％の間、最も好
ましくは30と40％の間である。もしホワイト油が合成油
と混合される場合は、その合成油は、好ましくはポリア
ルファオレフィンの、例えばPAO 4および／またはPAO 6
であり、ここで４と６は100℃においてセンチストーク
スで表したそれぞれのPAOの粘度である。基本原料がホ
ワイト油、鉱油及び合成油の混合物である場合、その好
ましい割合は、ホワイト油30−80重量％、鉱油10−70重
量％及び合成油５−50重量％である。
自動車潤滑剤はまた他の添加剤、例えば、エンジン
油、ギヤ油または自動車変速機流体に典型的に含まれて
いるようなものも適宜含んでよい。それらには洗剤、例
えば、アルカリ土類金属のスルホン酸塩、カルシウム・
サルシレート、アルカリ土類金属の硫化フェネート；無
灰分散剤、例えば、ポリイソブテンスクシンイミド、抗
ー摩損／極圧剤、例えば、ジチオリン酸ジアルキル（ま
たはジアリルまたはアリルアルキル）亜鉛、およびリン
／硫黄またはホウ酸塩化合物；耐食剤、例えば、スルホ
ン酸バリウムアルキルナフタレンおよびメルカプトベン
ゾトリアゾール；粘度指数向上剤、例えば、オレフィン
共重合体、ポリアルファオレフィン、ポリメタクリル酸
及びスチレン・ブタジエン；凝固点降下剤、例えば、ポ
リエステル；泡防止剤、例えば、シリコン素地のもの；
及び摩擦変性剤、例えば、モリブデン化合物、無灰化合
物及び抗スクオーク剤が含まれる。各添加剤について
は、その自動車潤滑在中に含まれる量は添加剤の種類お
よび潤滑剤の応用目的によって変化する。しかし一般的
には、各添加剤は、粘度指数向上剤は除き、潤滑剤の全
重量に基づき６重量％までの量が添加され、粘度指数向
上剤の場合は約10重量％までの量（活性成分）が添加さ
れる。添加剤の一部あるいは全部は、アドパックを使っ
て自動車潤滑剤に混合してもよい。
一般条件では、この発明による自動車潤滑剤は、100
℃で４−50mm2/sの粘度、及び80から200の粘度指数を持
つ。より明確には、潤滑剤がエンジン油の場合、それ
は、好ましくは100℃で４−35mm2/s、より好ましくは５
−25mm2/sの粘度、及び85から160、より好ましくは95か
ら150の粘度指数を持つ。潤滑剤がギア油の場合、それ
は、好ましくは100℃で５−50mm2/s、より好ましくは８
−25mm2/sの粘度、及び80から180、より好ましくは95か
ら160の粘度指数を持つ。潤滑剤が自動車変速機流体の
場合、それは、好ましくは100℃で４−10mm2/s、より好
ましくは５−8mm2/sの粘度、及び100から200、より好ま
しくは150から200の粘度指数を持つ。
ホワイト油が酸化防止添加剤を含むことは重要であ
る。意外にも、酸化防止剤を添加しないで試験したホワ
イト油は酸化しやすく、鉱油より性能が劣ることがあり
得るということが見出された。しかし、酸化防止剤がホ
ワイト油の潤滑剤処方に含まれている場合、その酸化に
関する性能は鉱油を基本とした対照品の処方より優れて
いる。
酸化防止剤は、ジチオリン酸ジアルキル亜鉛、ジチオ
リン酸ジアリール亜鉛、ジチオリン酸アリールアルキル
亜鉛、アルキル化ジフェニルアミン、立体障害フェノー
ル、リン硫化アルキルフェノール、硫化フェノール、ジ
メルカプト・ジチアジアゾール、及び銅ベースの酸化防
止剤、例えば、オレイン酸銅及びポリイソブチレン無水
コハク酸銅またはそれらの誘導体のうちから１つ以上選
択する。潤滑剤に添加される酸化防止剤の量は、好まし
くは、潤滑剤の全重量を基にして0.05から３重量％、よ
り好ましくは0.1から２重量％、最も好ましくは、0.2か
ら1.0重量％である。
ギア油または自動変速機流体のホワイト油は、好まし
くは上述の通りであり、鉱油または合成油またはその両
方と混合して混合ホワイト油の基本原料を形成してもよ
い。混合の場合、基本原料は、好ましくは基本原料の重
量に基づき少なくとも50重量％を包含する。
本発明を以下の実施例によって説明する。実施例には
下記添付図面に対する説明を含む： 図１は、ホワイト油、鉱油及び合成油を素地とした極
めて高い性能を有するディーゼル油の酸化安定性を示す
グラフである。
図２は、ホワイト油及び鉱油を素地とした自動車ギア
油の酸化安定性を示すグラフである。
（実施例） （実施例１） 次の性質を持ったホワイト油を一般に行われている溶
媒抽出および軽水素化法により得た： ホワイト油は下記実施例に記述するように種々の自動
車潤滑剤に処方された。各潤滑剤の酸化安定性は、標準
試験GFC TO21A90に従って試験した。
酸化安定性は、次の実施例に記述するように、鉱油、合
成油及び水素化分解の基本原料を素地とした同等の潤滑
剤処方と比較した。
（実施例２） 上記の実施例１で明記されたホワイト油Ａ及びＢの混
合物を素地とした極めて高い性能を有するディーゼル油
（SHPD）のエンジン油を下記のように処方した： ＊このものは8.3重量％のジチオリン酸ジアルキル亜鉛
（“ZDDB"）酸化防止剤を含有し、ここでアルキル基
は、典型的には、C5からC8の線状あるいは分岐アルキル
基、例えば２−エチルヘキシル基である。このように、
前記油処方には1.22重量％のZDDP酸化防止剤が含まれ
る。
比較のため、ホワイト油を同量の（ａ）一般鉱油及び
（ｂ）PAO/エステル合成油と置き換えた同等の処方を準
備した。３つの油のそれぞれの酸化安定性は、温度160
℃、空気流10 l/hr.において300mlのサンプルを試験し
て測定した。その結果を線図で図１に示す。
その結果は、一般に行われている鉱油を素地としたSH
PD油は800時間後には破壊されることを示している。と
ころが、ホワイト油を素地とした同等の油は1000時間後
も満足に動作を続け且つ合成素地油と類似の性能を有す
る。
（実施例３） 上記の実施例１に明記されたホワイト油Ａを素地とし
た自動車ギア油を下記のように処方した： 比較のため、ホワイト油を同量の一般鉱油の基本原料
と置き換えた同等のギア油を処方した。それらの酸化安
定性は、温度150℃、空気流10 l/hr.において300mlのサ
ンプルを試験して測定した。その結果を線図で図２に示
す。
その結果は、粘度の増加率はホワイト油素地のギア油
についてはより低く、それ故、このことは鉱油素地のギ
ア油より酸化安定性が高いことを示している。
（実施例４） 基本原料として、ホワイト油、鉱油およびPAO合成油
の混合物を含有し、そのホワイト油が上記実施例１で明
記されたホワイト油Ｃである自動変速機流体（ATF）を
下記のように処方した： 得られたATFは、100℃（ASTM D 445）で6.9cStの粘度
を、及び−40℃（DIN 51 562 part 1）で22500cStの粘
度を有する。流体の酸化安定性は、鉄／銅触媒（試験DI
N 51587）の存在下、加熱状態（160℃）で、500mlの流
体を流速10 l/分の空気に250時間曝すことにより試験し
た。試験は一般的な鉱油素地のATF（ESSO ATF D−21065
−Esso AGより市販）を使って繰り返し行われた。曝さ
れた流体は、標準試験DIN 51 562に従って100℃（KV 10
0）における動粘度の増加について、また標準試験ASTM
664に従って全酸価（TAN）について測定された。結果を
表１に掲げる。
KV100の増加率が小さければ小さいほど、及びTANが小
さければ小さいほど、ATFは酸化に対してより安定であ
る。従って、その結果は、本発明によるホワイト油を含
有するATFは一般の鉱油素地のATFと比べて酸化特性が優
れていることを示している。
２つのATFの摩擦特性も次の条件で動作するDKA摩擦試
験機を使用して測定した：速度3000/min、サイクル率2/
min、エネルギー密度0.6−1.0J/mm2及び温度80℃。その
結果を表２に掲げる。
その結果は、ホワイト油含有ATFは一般の鉱油ATFに匹
敵し、いくつかの例では摩擦係数はそれより小さいこと
を示している。
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ１０Ｍ 129:40 Ｃ１０Ｍ 133:12 133:12 135:30 135:30 135:36 135:36 137:10 Ａ 137:10 137:14 137:14） Ｃ１０Ｎ 10:02 Ｃ１０Ｎ 10:02 10:04 10:04 30:10 30:10 40:04 40:04 40:25 40:25 (72)発明者 オスチン・マルセル・アルフォンス・ヨ セフ フランス国、ブアーギュラーム 76230、 リ ド ラ エ 2722 (72)発明者 アルベス・ドミニーク フランス国、76130 モン セ エグナ ン、プラス コールベール 18 (72)発明者 ブーフェ・アラン・ガブリエール フランス国、76230 ブアーギュラーム、 リ ド レグリーズ 930 (72)発明者 スタイゲルバルト・エドガー・アンドレ アス ドイツ国、2000 ハンブルク 52、フォ アベックヴェーク 34 (56)参考文献 特開 昭62−89796（ＪＰ，Ａ) 特開 昭63−223094（ＪＰ，Ａ) 特開 昭63−223092（ＪＰ，Ａ) 特開 昭62−240385（ＪＰ，Ａ) 特開 昭63−254196（ＪＰ，Ａ) 特開 平４−234495（ＪＰ，Ａ) 米国特許2892784（ＵＳ，Ａ) 英国特許737392（ＧＢ，Ｂ) (58)調査した分野(Int.Cl.7，ＤＢ名) C10M 169/04 C10M 101/02 C10M 129/10 - 129/14 C10M 129/34 C10M 129/40 C10M 133/12 - 133/14 C10M 135/30 C10M 135/36 C10M 137/10 C10M 137/14 C10N 10:02 - 10:04 C10N 30:10 C10N 40:04 C10N 40:25 - 40:28

Claims (9)

    (57)【特許請求の範囲】
  1. 【請求項１】（ａ） 少なくとも25重量％のナフテン含
    量を有し、少なくとも30重量％がホワイト油である基本
    原料と （ｂ） 少なくとも１つの添加剤がスズ含有酸化防止剤
    以外の酸化防止剤である１つ以上の添加剤とから成るエ
    ンジン油とギア油と自動変速機油との中から少なくとも
    １つ選択された自動車潤滑剤。
  2. 【請求項２】100℃での粘度が４から50mm2/sの範囲にあ
    り粘度指数が80から200の範囲にあることを特徴とする
    請求の範囲１に記載の自動車潤滑剤。
  3. 【請求項３】基本原料が本質的に100％ホワイト油であ
    ることを特徴とする請求の範囲１又は２に記載の自動車
    潤滑剤。
  4. 【請求項４】基本原料がホワイト油と１つ以上のポリア
    ルファオレフィンとの混合物であることを特徴とする請
    求の範囲１又は２に記載の自動車潤滑剤。
  5. 【請求項５】ホワイト油は溶媒抽出と水素化法から成る
    処理によって生成され、前記水素化法は150から250℃の
    温度範囲で且つ1,000から20,000kPaの圧力範囲で実施さ
    れることを特徴とする請求の範囲１〜４の何れか１つに
    記載の自動車潤滑剤。
  6. 【請求項６】（ａ）少なくとも25重量％のナフテン含量
    を有し、少なくとも30重量％のホワイト油から成る基本
    原料と （ｂ）少なくとも１つの添加剤がスズ含有酸化防止剤以
    外の酸化防止剤である１つ以上の添加剤とから成る組成
    物の自動車用ギア油としての使用法。
  7. 【請求項７】（ａ）少なくとも25重量％のナフテン含量
    を有し、少なくとも30重量％のホワイト油から成る基本
    原料と （ｂ）少なくとも１つの添加剤がスズ含有酸化防止剤以
    外の酸化防止剤である１つ以上の添加剤とから成る組成
    物の自動変速機流体としての使用法。
  8. 【請求項８】（ａ）少なくとも25重量％のナフテン含量
    を有し、少なくとも30重量％がホワイト油である基本原
    料と （ｂ）少なくとも１つの添加剤がスズ含有酸化防止剤以
    外の酸化防止剤である１つ以上の添加剤とから成る組成
    物のエンジン油としての使用法。
  9. 【請求項９】１つ以上の内燃機関、歯車箱または自動変
    速機から成る自動車装置の操作法において、請求の範囲
    １〜５の何れか１つに記載の自動車潤滑剤を用いること
    を特徴とする自動車装置操作法。
JP51373293A 1992-02-07 1993-02-01 自動車潤滑剤 Expired - Fee Related JP3488920B2 (ja)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR92/01411 1992-02-07
FR9201411A FR2687165A1 (fr) 1992-02-07 1992-02-07 Lubrifiant pour automobile.
PCT/EP1993/000231 WO1993016151A1 (en) 1992-02-07 1993-02-01 Automotive lubricant

Publications (2)

Publication Number Publication Date
JPH07503494A JPH07503494A (ja) 1995-04-13
JP3488920B2 true JP3488920B2 (ja) 2004-01-19

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KR (1) KR100261820B1 (ja)
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CA (1) CA2129657C (ja)
DE (1) DE69328480T2 (ja)
ES (1) ES2145780T3 (ja)
FR (1) FR2687165A1 (ja)
HK (1) HK1014197A1 (ja)
PT (1) PT633921E (ja)
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WO2004074414A1 (ja) * 2003-02-21 2004-09-02 Nippon Oil Corporation 変速機用潤滑油組成物
US20060063685A1 (en) * 2004-09-22 2006-03-23 Pieter Purmer Lubricant for manual or automated manual transmissions
US20060105920A1 (en) * 2004-11-16 2006-05-18 Dalman David A Performance-enhancing additives for lubricating oils
US20080090742A1 (en) * 2006-10-12 2008-04-17 Mathur Naresh C Compound and method of making the compound
US20080090743A1 (en) * 2006-10-17 2008-04-17 Mathur Naresh C Compounds and methods of making the compounds
US20080125338A1 (en) * 2006-11-29 2008-05-29 Corbett Patricia M Food grade lubricant compositions
US20080269091A1 (en) * 2007-04-30 2008-10-30 Devlin Mark T Lubricating composition
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US10421920B1 (en) * 2016-04-13 2019-09-24 Safe Harbour Products, Inc. Biodegradable, non-toxic lubricant composition processes of making it and methods for its use
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CA2129657C (en) 2003-07-29
DE69328480D1 (de) 2000-05-31
EP0633921A1 (en) 1995-01-18
KR100261820B1 (ko) 2000-07-15
WO1993016151A1 (en) 1993-08-19
PT633921E (pt) 2000-08-31
ES2145780T3 (es) 2000-07-16
ATE192185T1 (de) 2000-05-15
FR2687165A1 (fr) 1993-08-13
SG48186A1 (en) 1998-04-17
HK1014197A1 (en) 1999-09-24
CA2129657A1 (en) 1993-08-19
EP0633921B1 (en) 2000-04-26
US6521570B2 (en) 2003-02-18
KR950700391A (ko) 1995-01-16
JPH07503494A (ja) 1995-04-13
DE69328480T2 (de) 2000-09-07
US20030008783A1 (en) 2003-01-09

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