JPH07503494A - 自動車潤滑剤 - Google Patents

自動車潤滑剤

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Publication number
JPH07503494A
JPH07503494A JP5513732A JP51373293A JPH07503494A JP H07503494 A JPH07503494 A JP H07503494A JP 5513732 A JP5513732 A JP 5513732A JP 51373293 A JP51373293 A JP 51373293A JP H07503494 A JPH07503494 A JP H07503494A
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Japan
Prior art keywords
oil
white oil
automotive
white
weight
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JP5513732A
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English (en)
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JP3488920B2 (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　リサーチ　アンド　エンジニアリング　カンパニー
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    • C10M101/02—Petroleum fractions
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Abstract

(57)【要約】本公報は電子出願前の出願データであるため要約のデータは記録されません。

Description

【発明の詳細な説明】 自動車潤滑剤 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−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、クランク基油、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、一局面においては、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）　ホワイト油基本原料；及び （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種又は２種以上の添加剤。
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”、１９９］　１．：第 １．’テ規定さレテイル。仕様書ＦＤＡ　２１　ＣＦＲ１７８−３６２０（ａ） に準拠した薬用ホワイト油または仕様書ＦＤ＾２１　ＣＦＲ１７ｇ−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　Ｄ２１４ ０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、圧力ニ　１ ０００と２０，０００　ｋＰａ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　Ｄ２７８６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＋７−２３重量％３環＋　４−２１重量％、好ましくは８−１ ７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トシテハ、ＭＡＲＣＯＬ　５２　（ナフテン含量３４％） 、ＭＡＲＣＯＬ　８２　（ナフテン含ｆｆｉ　３２％）、ＭＡｌｌＣＯＬ１７２ 　（＋７テン含！　３４％）、ＰＲＩＭＯＬ　３５２　（す７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Ｅｘｚｏｎ／Ｅｓ５ｏがら供給される。本発明に使用できる適当 なＦＤ＾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　＋３５　（ナフテン含量３６％）が挙げられ 、これらは両方ともＥｘｘｏｎ／Ｅｓ５ｏから供給される。ＭＡＲＣＯＬ、ＰＲ ＩＭＯＬ、ＰＬＡＳＴＯＬ及びＢＡＹＯＬはＥｚｘｏｎ社の商標である。ナフテ ン含量は標準試験法ＡＳＴＭ２１４０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レル、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がら成ってもよい。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３ｏ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ＰＡＯ４および／またはＰＡＯ６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、ポリイソブチンスクシン イミド、抗−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・ブタジェン；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 、アトパン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４−４−５Ｏ！１２ ／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４−３５１ｌＩｌｌ１１１２／ ｓ、より好ましくは５−２５　ｍｍ２／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５−５０闘２／、、より好ましくは８−２５止２／、の粘度 、及び８ｏ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４−１０　ｍｍ” ／ｓ、より好ましくは５−８ｍ１Ｉ１２／ｓの粘度、及び＋００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もあ り得ることが見出された。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より優れている。
酸化防止剤は、好ましくは、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鍛鋼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。
ホワイト油は、以前には自動車のギア油または自動変速機流体用の基本原料とし ては使用されていないものである。それ故、もう一つの局面として、本発明によ り、（ａ）ホワイト油から成る基本原料と、（ｂ）少な（とも１つの添加剤が酸 化防止剤である１種以上の添加剤とから成る自動車ギア油が提供される。更に１ 局面においては１本発明により、（１）ホワイト油から成る基本原料と（ｂ）少 なくとも１つの添加剤が酸化防止剤である１つ以上の添加剤とから成る自動変速 機流体が提供される。
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。混合油の場合、基本原料は、好ましくは基本原料の重量に基づき少な（ とも５０重量％のホワイト油を包含する。
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　ホワイト　ホワイト 油＾　油Ｂ　油Ｃ ナフテン含量（％） （ＡＳＴＭ　Ｄ　２１４０）　３３．８　３２．２　３１．６４０℃での粘度（ Ｃ５ｔ） （ＡＳＴＭ　Ｄ　４４５）　３１．６　７１．４　１４．６粘度指数 （ＡＳＴＭ　Ｄ　ｚ２７０）　１０８　９ｇ　＋０７凝固点（℃） （ＡＳＴＭ　Ｄ　９７）　−６−１８−９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ＧＦ ＣＴＯ２１Ａ９０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１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 ： 成分　重量％ ホワイト油＾　５４．５９８ ホワイト油８　２０．２０ ＳＨＰＤ類型アドパソク＊　１４．７０　ＨＩＴＥＣ８６５（Ｅｌｈｙ１社）■ ！向上剤　１０．５０　０ＣＰ（Ｅｘｘｏｎ　Ｃｈｅｍｉｃａ１社）泡防止剤　 ０．００２　シリコン型ＤＣ−２００／６００００（Ｄｏｔ　Ｃｏｒｎｉｎｇ社 ） ＊このものは８．３重量％のジチオリン酸ジアルキル亜鉛（”Ｚ（ＩＤＢ″）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０８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）Ｉ”ＡＯ／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／ｈ＋、において３００ｍ１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５ＩＩＰＤ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は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： 成分　重量％ ホワイト油　７８．９９８ 酸化防止剤　０．２０フエノール系 ｖ１向上剤　１０．００ポリメタクリル酸ＥＰ添加剤　０．５０亜リン酸塩 凝固点降下剤　０．８０ポリアクリル酸塩ギヤ油アトパツク　６．５０　Ａｕｇ ｌａｍｏｌ　９９　（Ｌｕｂｒｉｔｏ１社）泡防止剤　Ｑ、（ＩＱＺ　０Ｃ−Ｚ （ｔｏ／６ＱＯＱ（１（Ｄｏｔ　ＣＣｏ１ｎ１ｎ社） 抗スクオータ・アトバック　３．００　ＬＺ　６１７ＢＡ　（Ｌｕｂｒｉｘｏ１ 社）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１０１／ｈ＋、 において３００ｍ１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Ｐ＾０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（Ａ ＴＦ）を下記のように処方した：成分　重量％ ホワイト油Ｃ４０，００ 鉱油　２９．２６６ Ｐ＾０４　１０．００ Ｐ＾０６　１０．００ 酸化防止剤（フェノール系）　０．１０　１１１ＴＥｃ　４７８２゜Ｅｌｈ７１ 社（ＵＫ）より市販 酸化防止剤（７ミン）　０．１０　１ＲＧＡＮＯＸＬ５７゜Ｃｉｂｉ−Ｇｅｉｇ Ｙ社より市販 ＡＴＦアトバック　１０．５０　０５８７２５６Ｌｕｂｒｉｔｏ１社 銅不活性化剤　０．０３ 泡防止剤　０．００４　ＡＫＣ５００００Ｗｉｃｋｅｒ−ｃｈｅｍｉｅ社 得られたＡＴＦは、１００℃（ＡＳＴＭ　Ｄ　４４５）で６．９　ｃｓｌの粘度 を、及び−４０℃（ＤＩＮ　５１５６２　ｐａｉｌ　Ｉ）で２２５００　ｃｓＩ の粘度を有する。流体の酸化安定性は、鉄／銅触媒（試験ＤＩＮ　５１５８７） の存在下、加熱状態（１６０℃）で、　５００　ｍｌの流体を流速１０１／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（ ＥＳＳＯＡＴＦ　Ｄ−２１０６５−Ｅｓ５ｏ　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　５１５６２に従って１００℃（Ｋ Ｖ　１００）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。
表１ ホワイト油含有　鉱油 ＡＴＦ　（発ｖ１８３＞　ＡＴＦ　比較ＫＶ１０ｏ）増加率　＋１．５％　＋４ ．５％ＴＡＮ　１．９　ｍｇＫＯＨ／ｇ　６　ｏｇＫＯＨ／ｇＫＶ１００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／ｗｉｎ、サイクル率２７ｍ　ｉ　ｎ、エネルギー密度０． ６−１．ＯＪ／ｍｍ２及び温度８０℃。その結果を表２に掲げる。
表２ ホワイト油含有＾ＴＦ　鉱油ＡＴＦ サイクル　ｕｌ　ｕ２　ｕ３　ｕｌ　ｕ２　ｕ３１０　０、＋３４　０．１２７ 　０．１６９　０．＋３６　０．１３２　０．１６９１ＧＱＯＧ、Ｉ３Ｚ　Ｑ、 ＩＺ２　０．＋５１　０．１４５　０．＋３４　０．１５０９０００　０．１２ ７　０．１１２　０．１２７　０．１２８　０．１１０　０．１２６２２０００ 　０．１１９　０．１０６　０．１３＋　０．１２５　０．＋０９　０．１２４ ３６０００　０．１１９　０．１１１　０．１３２　０．＋２５　０．１１１　 ０．１２６４７０００　０．１１１　０．１０２　０．１３８　０．１２１　０ ．１１２　０．１２８６７０００　０、＋１４　０．１０２　０．＋３９　０． １２４　０．１１６　０．１３４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。
ＦＩＧ、　７ ＴＩＭＥＩ　ｈｏｕｒｓｌ □慣用の鉱油原料 に■１００°Ｃ（ｃｓｔｌ　−→トー　ホワイト油原料平成６年８月４日

Claims (9)

    【特許請求の範囲】
  1. １．（ａ）ホワイト油基本原料；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 種以上の添加剤とから成る自動車潤滑剤。
  2. ２．基本原料が少なくとも３０重量％のホワイト油を含有す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. ３．基本原料がホワイト油と１つ以上の鉱油、合成油及び水素化分解型基本原料 との混合物であることを特徴とする請求の範囲１または２に記載の自動車潤滑剤 。
  4. ４．合成油がポリアルファオレフィンであることを特徴とする請求の範囲３に記 載の自動車潤滑剤。
  5. ５．基本原料が実質的に１００一ホワイト油で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。
  6. ６．ホワイト油が少なくとも２５重量％のナフテン含量を有することを特徴とす る前記請求の範囲１〜５の何れかに記載の自動車潤滑剤。
  7. ７．酸化防止剤が、１つ以上の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・ジチアジアノールの中から選択されることを特徴とする請求の範囲１〜 ６の何れかに記載の自動車潤滑剤。
  8. ８．（ａ）ホワイト油から成る基本原料と；（ｂ）少なくとも１つの添加剤が酸 化防止剤である１つ以上の添加剤とから成る自動車ギア油。
  9. ９．（ａ）ホワイト油から成る基本原料と；（ｂ）少なくとも１つの添加剤が酸 化防止剤である１つ以上の添加剤とから成る自動変速機流体。
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