JP3086727B2 - 低リンエンジン油製造用の添加剤組成物 - Google Patents

低リンエンジン油製造用の添加剤組成物

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Publication number
JP3086727B2
JP3086727B2 JP03223664A JP22366491A JP3086727B2 JP 3086727 B2 JP3086727 B2 JP 3086727B2 JP 03223664 A JP03223664 A JP 03223664A JP 22366491 A JP22366491 A JP 22366491A JP 3086727 B2 JP3086727 B2 JP 3086727B2
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Japan
Prior art keywords
engine oil
weight
engine
zinc dialkyldithiophosphate
oil
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Expired - Fee Related
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JP03223664A
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English (en)
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JPH0641568A (ja
Inventor
守国 中里
次郎 曲渕
昭博 望月
比呂志 田辺
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オロナイトジャパン株式会社
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Priority to JP03223664A priority Critical patent/JP3086727B2/ja
Priority to CA002075433A priority patent/CA2075433C/en
Priority to EP92307279A priority patent/EP0528610B1/en
Priority to SG9607506A priority patent/SG80545A1/en
Priority to AT92307279T priority patent/ATE164621T1/de
Priority to DE69224943T priority patent/DE69224943T2/de
Priority to US08/162,681 priority patent/US5629272A/en
Publication of JPH0641568A publication Critical patent/JPH0641568A/ja
Priority to US08/222,495 priority patent/US6531428B2/en
Application granted granted Critical
Publication of JP3086727B2 publication Critical patent/JP3086727B2/ja
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    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • C10M2227/063—Complexes of boron halides
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • C10M2227/065—Organic compounds derived from inorganic acids or metal salts derived from Ti or Zr
    • 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
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • C10M2227/066—Organic compounds derived from inorganic acids or metal salts derived from Mo or W
    • C—CHEMISTRY; METALLURGY
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    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/12—Groups 6 or 16
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/251—Alcohol fueled engines
    • C—CHEMISTRY; METALLURGY
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    • C—CHEMISTRY; METALLURGY
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
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    • C—CHEMISTRY; METALLURGY
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
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    • C—CHEMISTRY; METALLURGY
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    • C10N2070/00—Specific manufacturing methods for lubricant compositions
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02F—CYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
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  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Description

【発明の詳細な説明】
【０００１】
【産業上の利用分野】本発明は、リン濃度が低減したに
も拘らず、優れた耐摩耗性、清浄性、酸化安定性、粘度
−温度特性等の諸特性を示す低リンエンジン油（内燃機
関用潤滑油）の調製に適した添加剤組成物に関するもの
である。
【０００２】
【従来の技術】通常の自動車のガソリンエンジンおよび
ディーゼルエンジンにおいて、カム、弁、ロッカーアー
ム等の動弁系が潤滑条件の厳しい部分であり、この部分
の摩耗を防止する能力がエンジン油にとって極めて重要
となる。同時に燃料に起因する未燃焼生成物または不完
全燃焼物の混入、あるいはエンジン油自体の劣化によっ
て生じるエンジン内堆積物の抑制がやはりエンジン油に
とって重要である。
【０００３】エンジン油は、鉱物油あるいは合成油を基
油とするものであるが、この基油のみでは上記の諸性能
を満足できるエンジン油（内燃機関用潤滑油）とはなら
ないため、それらの諸性能を付与するために、従来よ
り、添加剤として、無灰性分散剤、金属系清浄剤、耐摩
耗性向上剤、酸化防止剤、粘度指数向上剤、そして必要
に応じて他の各種の補助機能添加剤を組合せ、配合した
組成物の状態で用いられている。
【０００４】上記の各添加剤には、それぞれ各種のもの
が知られ、かつ用いられているが、特に耐摩耗性向上剤
としては、同時に酸化防止剤としても機能するジアルキ
ルジチオリン酸亜鉛が用いられるのが一般的となってい
る。すなわち、このジアルキルジチオリン酸亜鉛は、耐
摩耗性向上剤として非常に優れた特性を有し、同時に酸
化防止剤としても高い性能を示すことから、実用されて
いる各種のエンジン油の殆ど全てにおいて用いられてい
る。
【０００５】しかしながら、近年、エンジン内の燃焼に
よって生じる排気ガスに含まれてくるＨＣ、ＣＯ、ＮＯ
X などの有毒物質が規制されるようになり、排気ガス中
のそれらの有毒物質を除去するために、自動車の排気ガ
ス出口に、白金、バナジウムなどの金属と金属酸化物を
組合せた触媒コンバーターを付設して、それらの有毒物
質を無毒物質に変換させること（浄化）が一般的となっ
ている。ところが、ジアルキルジチオリン酸亜鉛に含ま
れるリン成分は、上記の触媒成分を被毒させる成分であ
り、リン成分を含むエンジン油を使用することにより触
媒コンバーターの活性低下が発生するとの問題がある。
従って、排気ガス浄化用の触媒コンバーターの活性、耐
久性を高い水準に維持のために、エンジン油中のリン含
量を低減するべきであるとの動向が強くなり、実際に、
米軍規格であるMIL-L-46152Eそして日米の自動車工業会
が作った規格のILSAC GF-1では、エンジン油中のリン濃
度を０．１２重量％以下とするように規定している。
【０００６】通常のジアルキルジチオリン酸亜鉛を含む
エンジン油におけるリン濃度はおよそ０．１重量％であ
り、上記の規定に合格しているが、触媒対策のために望
ましくは、リン源であるジアルキルジチオリン酸亜鉛の
使用量を低減させる必要があり、これに伴なう耐摩耗性
能の低下、そして酸化防止性能の低下が問題となる。こ
のため、同じく酸化防止剤として知られているフェノー
ル誘導体、アミン誘導体などで代替させることも検討さ
れているが、得られる耐摩耗性能および酸化防止性能
は、必ずしも満足できるものとはいえない。また、動弁
系の耐摩耗性能向上にも有効に機能する金属系清浄剤と
して知られているマグネシウムスルホネート系清浄剤を
用いることも検討され、実際にも使用されている。しか
し、マグネシウムスルホネート系清浄剤を含有するエン
ジン油を、吸湿および熱履歴を伴なう条件下に長期間置
くとエンジン油中に結晶性の析出物が生成する場合があ
り、その場合には、エンジン油循環系に取り付けられて
いるフィルターの目詰まりが発生するとの問題がある。
この問題は、特に耐摩耗性能を高くするために、マグネ
シウムスルホネート系清浄剤を多量に使用した場合に発
生しやすく、従ってマグネシウムスルホネート系清浄剤
の使用による耐摩耗性能の向上との解決法も充分満足で
きるものとは言えない。
【０００７】さらに、最近、前記の問題を考慮して、更
なる低リン化についての要望も高くなり、たとえば、リ
ン濃度を０．１重量％以下、さらには、０．０５重量％
程度にまで低減することを求める要望もでている。この
ような、要望は、前記のリン濃度０．１２重量％以下に
も増して厳しいものであり、上記のような公知の代替法
では実用性のある解決とはならない。
【０００８】
【発明が解決しようとする課題】本発明の目的は、リン
濃度を０．１２重量％以下、さらには０．０８重量％以
下あるいは０．０６重量％以下と低減しながらも、従来
レベルのジアルキルジチオリン酸亜鉛を用いたエンジン
油と同等の耐摩耗性および酸化防止性能を示す自動車用
のエンジン油（自動車用潤滑油組成物）の製造に有効に
用いることのできるエンジン油用添加剤組成物およびエ
ンジン油添加剤を提供することにある。
【０００９】
【課題を解決するための手段】本発明は、一般式
（Ｉ）：
【００１０】
【化３】
【００１１】（但し、Ｒ1、Ｒ2、Ｒ3およびＲ4は、それ
ぞれ同一でも互いに異なっていてもよい炭素数１〜１８
のアルキル基を表わし、そして（Ｘ）は、Ｓ、Ｓ−Ｓ、
Ｓ−ＣＨ2−Ｓ−、Ｓ−ＣＨ2ＣＨ2−Ｓ、Ｓ−ＣＨ2ＣＨ
2ＣＨ2−Ｓ、あるいはＳ−ＣＨ2ＣＨ（ＣＨ3）−Ｓを表
わす。）で表わされるアルキルチオカルバモイル化合
物、そして該アルキルチオカルバモイル化合物の重量に
対して０．１〜２０倍の重量のジアルキルジチオリン酸
亜鉛が組み合わされてなることを特徴とする、該ジアル
キルジチオリン酸亜鉛に起因するリン濃度が０．１２重
量％以下の低リンエンジン油の製造用の添加剤組成物に
ある。ここで、ジアルキルジチオリン酸亜鉛は、第二ア
ルキルタイプのジアルキルジチオリン酸亜鉛であること
が好ましい。
【００１２】本発明はまた、上記の一般式（Ｉ）のアル
キルチオカルバモイル化合物、そして該アルキルチオカ
ルバモイル化合物の重量に対して０．２〜１０倍の重量
のジアルキルジチオリン酸亜鉛が組み合わされてなるこ
とを特徴とする、該ジアルキルジチオリン酸亜鉛に起因
するリン濃度が０．１重量％以下の低リンエンジン油の
製造用の添加剤組成物にもある。ここで、ジアルキルジ
チオリン酸亜鉛は、第二アルキルタイプのジアルキルジ
チオリン酸亜鉛であることが好ましい。
【００１３】本発明の上記一般式（Ｉ）のアルキルチオ
カルバモイル化合物は、従来用いられているエンジン油
と同様に、金属系清浄剤、無灰性分散剤、粘度指数向上
剤など、そして必要に応じて更に他の各種の補助機能添
加剤を組合せ、基油に溶解もしくは分散した組成物とし
て用いられる。
【００１４】金属系清浄剤、無灰性分散剤、粘度指数向
上剤、および基油としては各種のものが知られており、
本発明のエンジン油の調製においても、それらの公知の
材料あるいはその類似化合物が用い得る。次にそれらの
各種材料の代表的な例を説明する。
【００１５】金属系清浄剤としては、一般には金属のフ
ェネートあるいはスルホネートが用いられる。金属フェ
ネートは炭素数約８〜３０のアルキル基が付加されたア
ルキルフェノールの硫化物のアルカリ土類金属塩であ
る。この場合において一般的に用いられるアルカリ土類
金属としてはカルシウム、マグネシウムあるいはバリウ
ムが挙げられる。スルホネートは分子量約４００〜６０
０の鉱物油あるいはアルキル置換された芳香族化合物の
スルホン化物のアルカリ土類金属塩である。この場合に
おいて一般的に用いられるアルカリ土類金属としても、
カルシウム、マグネシウムあるいはバリウムが挙げられ
る。これらフェネートあるいはスルホネートはそれぞれ
単独でも、あるい各種組合せても使用することができ
る。また、アルカリ土類金属のサリシレート、ホスホネ
ート、ナフテネートなどの金属系清浄剤を単独に、ある
いは上記のフェネートあるいスルホネートと組み合わせ
て用いることもできる。なお、これらの金属系清浄剤は
中性型でも、あるいは塩基価が３００もしくはそれ以上
の過塩基性型でもよい。
【００１６】金属系清浄剤は、通常は、エンジン油中の
濃度が０．５〜２０重量％となるように配合される。
【００１７】なお、上記のフェネート、スルホネート等
のマグネシウム塩は、耐摩耗性については好ましい性能
を示すが、前述のように、長期保存性について問題が発
生する場合があるため、本発明のアルキルチオカルバモ
イル化合物と組合せて用いるためには、カルシウム塩の
方が、その特徴が生かせるとの利点がある。
【００１８】無灰性分散剤としては、分子量約７００〜
３０００のアルキル基またはアルケニル基が付加された
コハク酸イミド、コハク酸エステル、ベンジルアミンな
どが使用される。無灰性分散剤は、通常は、エンジン油
中の濃度が０．５〜１５重量％となるように配合され
る。
【００１９】粘度指数向上剤としては、一般にポリアル
キルメタクリレート、エチレン−プロピレン共重合物、
スチレンーブタジエン共重合物等が用いられる。あるい
は、分散性能を付与した分散型もしくは多機能型粘度指
数向上剤を用いてもよい。これらの粘度指数向上剤は、
それぞれ単独、あるいは各種組合せて用いることができ
る。粘度指数向上剤は、目的とするエンジン油の所望粘
度にもよるが、通常、エンジン油中の濃度が０．５〜２
０重量％となるように配合される。
【００２０】エンジン油の組成の大部分を占める基油と
しては、鉱物性油あるいは合成油をそれぞれ単独もしく
は組合せて用いることができる。
【００２１】次に、本発明の特徴的要件であるアルキル
チオカルバモイル化合物について説明する。
【００２２】本発明で用いるアルキルチオカルバモイル
化合物は、前述のように下記の一般式（Ｉ）：
【００２３】
【化４】
【００２４】（但し、Ｒ1 、Ｒ2 、Ｒ3 およびＲ4 は、
それぞれ同一でも互いに異なっていてもよい炭素数１〜
１８のアルキル基を表わし、そして（Ｘ）は、Ｓ、Ｓ−
Ｓ、Ｓ−ＣＨ2 −Ｓ、Ｓ−ＣＨ2 ＣＨ2 −Ｓ、Ｓ−ＣＨ
2 ＣＨ2 ＣＨ2 −Ｓ、あるいはＳ−ＣＨ2 ＣＨ（Ｃ
Ｈ3 ）−Ｓを表わす。）で表わされる化合物である。こ
のアルキルチオカルバモイル化合物は、従来より、ゴム
の加硫促進剤、ギヤー油、タービン油などの添加剤とし
て用いられることがあり、化合物としては既知のもので
ある。上記のアルキル基は、直鎖型でも、分岐鎖型のい
ずれでもよく、その例としては、メチル、エチル、プロ
ピル、ｎ−ブチル、イソブチル、ペンチル、イソペンチ
ル、ヘプチル、オクチル、２−エチルヘキシル、ノニ
ル、デシル、ドデシルなどのアルキル基を挙げることが
できる。好ましいのは炭素数１〜１０のアルキル基であ
る。この一般式（Ｉ）のアルキルチオカルバモイル化合
物の具体的な例としては、メチレンビス（ジブチル ジ
チオカーバメート）、ビス（ジメチルチオカルバモイ
ル）モノスルフィド、ビス（ジメチルチオカルバモイ
ル）ジスルフィド、ビス（ジブチルチオカルバモイル）
ジスルフィド、ビス（ジアミルチオカルバモイル）ジス
ルフィド、ビス（ジオクチルチオカルバモイル）ジスル
フィドを挙げることができる。これらの各化合物は、そ
れぞれ単独で、あるいは二種以上を組合せて用いられ
る。
【００２５】このアルキルチオカルバモイル化合物は通
常、エンジン油中にて０．０５〜８重量％の範囲の濃度
となるように配合される。特に０．１〜４重量％の範囲
の濃度となるように配合するのが好ましい。
【００２６】なお、本発明のアルキルチオカルバモイル
化合物は、ジアルキルジチオリン酸亜鉛と組合せて用い
ることもできる。すなわち、現在のところエンジン油中
のリン含量を０にするような厳しい要求は特にないた
め、許容できるリン含量、たとえば０．１２重量％以
下、０．１０重量％以下、０．０８重量％以下、０．０
６重量％以下などを考慮にいれて、所望の耐摩耗性と酸
化防止性を付与できるような比率にて、前記一般式
（Ｉ）のアルキルチオカルバモイル化合物とジアルキル
ジチオリン酸亜鉛とを組合せて用いることが有利であ
る。そのような好ましい比率の範囲は、１：０．１〜
１：２０、特に好ましい比率の範囲は、１：０．２〜
１：１０（アルキルチオカルバモイル化合物：ジアルキ
ルジチオリン酸亜鉛、重量比）である。
【００２７】本発明の添加剤組成物には、上記の各成分
以外に所望に応じて各種の補助機能添加剤を配合するこ
とができる。そのようなの補助機能添加剤の例として
は、公知の極圧添加剤、腐食防止剤、防錆剤、摩擦調整
剤、消泡剤、流動点降下剤などを挙げることができる。
また、他の酸化防止剤（例、ヒンダードフェノール）、
耐摩耗性向上剤などを組合せてもよい。
【００２８】本発明の添加剤組成物を用いるエンジン油
の調製に際しては、基油に各添加剤成分をそれぞれ別々
に添加してもよいが、一般には、金属系清浄剤、無灰性
分散剤および一般式（Ｉ）のアルキルチオカルバモイル
化合物を必須成分として組合せ、その他、任意の添加剤
成分を添加して調製（基油に高濃度に溶解、分散させる
のが一般的である）した配合剤を予め用意し、これと粘
度指数向上剤、そして所望により更に他の任意成分を基
油に添加してエンジン油を調製することが、配合技術上
望ましい。そのような場合には、金属系清浄剤１００重
量部に対して、無灰性分散剤１０〜７００重量部、そし
て一般式（Ｉ）のアルキルチオカルバモイル化合物２〜
２００重量部となるように配合するのが好ましい。
【００２９】
【実施例】現在エンジン油の性能評価は、各種ベンチテ
ストおよびエンジンテストにより実施されている。エン
ジン油の統一規格としてはＡＰＩサービス分類が一般的
に採用されており、現在、サービスステーション向け乗
用車エンジン油の最高規格はＡＰＩ−ＳＧであり、この
ＡＰＩ−ＳＧに合格するために必要なエンジン試験は、
ＳＥＱ（シークエンス）IID 、ＳＥＱ IIIE 、 ＳＥＱＶ
E 、ＣＡＴ１Ｈ2 、ＣＲＣＬ−３８とそれぞれ名付けら
れた各種の台上エンジン試験である。従来一般的なＡＰ
Ｉ−ＳＧ合格エンジン油は、リン濃度（リン含量）が
０．１重量％程度であり、リン濃度を下げるためにジア
ルキルジチオリン酸亜鉛の添加量を減じると、ＳＥＱ I
IIE 、 ＳＥＱＶE の各試験における動弁系摩耗と、ＳＥ
Ｑ IIIE試験での粘度上昇とにおいて不充分な（すなわ
ち、規格に合格しない）結果がでるとされている。従っ
て、低リンエンジン油の評価を、これらの試験に合格す
ることを基準に実施した。また、同時にディーゼルエン
ジン台上試験であるＣＡＴ１Ｈ2 試験も行ないディーゼ
ル油としての評価も実施した。
【００３０】なお特に条件の厳しいエンジン試験はＳＥ
ＱＶE であり、これはフォード社の２．３ｌエンジン
（Ｌ−４、ＯＨＣ）を用い、無鉛ガソリンを使用し、総
試験時間２８８時間に及ぶサイクリック試験であり、中
・低温時におけるスラッジの生成傾向を主としたエンジ
ン清浄性の評価と同時に動弁系摩耗を評価するものであ
る。この試験で動弁系摩耗が不良である（すなわ摩耗が
多い）と、エンジン油中に摩耗により生じた多量の鉄が
微粒子状に分散し、これがスラッジの生成を促進すると
されている。
【００３１】また、ＳＥＱ IIIE はＧＭ（ゼネラルモー
ター）社の３．６ｌ Ｖ−６エンジンを用い、加鉛ガソ
リンを用い、油温１４９℃で６４時間連続で運転して試
験するもので、高温におけるエンジン油の酸化安定性そ
して動弁系の耐摩耗性を評価するものである。ＣＡＴ１
Ｈ2 はキャタピラー社の２．２ｌ単筒ディーゼルエンジ
ンを用い、硫黄分０．４％の軽油を燃料として使用し、
４８０時間運転して、主として高温清浄性を評価する試
験である。
【００３２】試験の対象として用いたエンジン油は、下
記の第１表に示した組成のものである。また、第１表に
は、各々のエンジン油について実施した台上エンジンテ
ストの結果も、それぞれのエンジンテストの評価項目お
よび合格基準（評点もしくは測定値にて規定）とともに
示した。
【００３３】
【表１】
【００３４】
【表２】
【００３５】なお、上記の第１表に示した添加剤の詳細
は下記の通りである。基油は粘度指数１００のパラフィ
ン系鉱油であり、エンジン油は、ＡＰＩサービスに規定
されたＳＡＥ１０Ｗ３０の粘度条件を満たすように調製
された。また、必要により消泡剤などの付加添加剤を加
えた。
【００３６】金属系清浄剤：過塩基性カルシウムスルホ
ネートと中性型カルシウムスルホネートとの混合物 無灰性分散剤：ホウ酸変性コハク酸イミド、試作品Ｎｏ
２のみポリイソブテニルコハク酸エステルを１重量％追
加 カーバメート：メチレンビス（ジブチルジチオカーバメ
ート） ＺｎＤＴＰ：炭素数３〜６の第二アルキルタイプジアル
キルジチオリン酸亜鉛 有機酸化防止剤：ヒンダードフェノールとジアルキルジ
アミンとの混合物 硫黄系極圧剤：硫化ジパラフィン 粘度指数向上剤：分散型エチレン−プロピレン共重合物 流動点降下剤：ポリメタクリレート型
【００３７】また、上記の第１表に示した試験項目等の
詳細は下記の通りである。 （１）ＶE 試験：平均スラッジ、ロッカーカバースラッ
ジ、平均バーニシュ、ピストンスカートバーニシュ、カ
ム摩耗（平均）、カム摩耗（最大） （２）IIIE試験：粘度増加（％）、オイルリングランド
デポシット、ピストンバーニッシュ、平均スラッジ、カ
ム・リフター摩耗（平均）、カム・リフター摩耗（最
大）、 （３）１Ｈ2 試験：ＴＧＦ（トップブルーブカーボン詰
まり）、ＷＴＤ（重量付き総デメリット評点）、各々２
４０時間運転と４８０時間運転
【００３８】第１表に示した試験データから明らかなよ
うに、本発明のアルキルチオカルバモイル化合物を用い
たエンジン油である試作油Ｎｏ４とＮｏ５は、０．０５
６重量％という低リン濃度であるにもかかわらず、市販
の最高クラスであるＡＰＩ−ＳＧグレードのエンジン油
（リン濃度は０．１重量％）と同等な諸性能を示す。こ
れに対して、本発明のアルキルチオカルバモイル化合物
を用いなかった試作油Ｎｏ１、Ｎｏ２、およびＮｏ３は
いずれも、ＡＰＩ−ＳＧグレードに合格することができ
ず、特に、問題のカム摩耗およびスラッジ抑制で市販品
および本発明品に比較して明らかに劣った性能を示す。
【００３９】
【発明の効果】本発明に従う一般式（１）のアルキルチ
オカルバモイル化合物を配合したエンジン油は、そのリ
ン濃度を、従来用いられている市販品のリン濃度に比較
して顕著に低減しても（たとえば半分程度としても）、
耐摩耗性能や酸化防止性を含めた諸性能において、最高
クラスの市販品と実質的に同等な特性を示す。従って、
今後ますます高まるとされる低リン化エンジン油として
の実用性が非常に高いものである。
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭59−11397（ＪＰ，Ａ) 特開 昭63−128099（ＪＰ，Ａ) 米国特許4383931（ＵＳ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C10M 101/00 - 177/00 C10N 10:00 - 80:00 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ) ＷＰＩ（ＤＩＡＬＯＧ)

Claims (3)

    (57)【特許請求の範囲】
  1. 【請求項１】 一般式（Ｉ）： 【化１】 （但し、Ｒ1、Ｒ2、Ｒ3およびＲ4は、それぞれ同一でも
    互いに異なっていてもよい炭素数１〜１８のアルキル基
    を表わし、そして（Ｘ）は、Ｓ、Ｓ−Ｓ、Ｓ−ＣＨ2−
    Ｓ−、Ｓ−ＣＨ2ＣＨ2−Ｓ、Ｓ−ＣＨ2ＣＨ2ＣＨ2−
    Ｓ、あるいはＳ−ＣＨ2ＣＨ（ＣＨ3）−Ｓを表わす。）
    で表わされるアルキルチオカルバモイル化合物、そして
    該アルキルチオカルバモイル化合物の重量に対して０．
    １〜２０倍の重量のジアルキルジチオリン酸亜鉛が組み
    合わされてなることを特徴とする、該ジアルキルジチオ
    リン酸亜鉛に起因するリン濃度が０．１２重量％以下の
    低リンエンジン油の製造用の添加剤組成物。
  2. 【請求項２】 一般式（Ｉ）： 【化１】 （但し、Ｒ1、Ｒ2、Ｒ3およびＲ4は、それぞれ同一でも
    互いに異なっていてもよい炭素数１〜１８のアルキル基
    を表わし、そして（Ｘ）は、Ｓ、Ｓ−Ｓ、Ｓ−ＣＨ2−
    Ｓ−、Ｓ−ＣＨ2ＣＨ2−Ｓ、Ｓ−ＣＨ2ＣＨ2ＣＨ2−
    Ｓ、あるいはＳ−ＣＨ2ＣＨ（ＣＨ3）−Ｓを表わす。）
    で表わされるアルキルチオカルバモイル化合物、そして
    該アルキルチオカルバモイル化合物の重量に対して０．
    ２〜１０倍の重量のジアルキルジチオリン酸亜鉛が組み
    合わされてなることを特徴とする、該ジアルキルジチオ
    リン酸亜鉛に起因するリン濃度が０．１重量％以下の低
    リンエンジン油の製造用の添加剤組成物。
  3. 【請求項３】 ジアルキルジチオリン酸亜鉛が第二アル
    キルタイプのジアルキルジチオリン酸亜鉛であることを
    特徴とする、請求項１もしくは２に記載の低リンエンジ
    ン油の製造用の添加剤組成物。
JP03223664A 1991-08-09 1991-08-09 低リンエンジン油製造用の添加剤組成物 Expired - Fee Related JP3086727B2 (ja)

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JP03223664A JP3086727B2 (ja) 1991-08-09 1991-08-09 低リンエンジン油製造用の添加剤組成物
CA002075433A CA2075433C (en) 1991-08-09 1992-08-06 Low phosphorous engine oil composition and additive compositions
SG9607506A SG80545A1 (en) 1991-08-09 1992-08-10 Low phosphorous engine oil composition and additive compositions
AT92307279T ATE164621T1 (de) 1991-08-09 1992-08-10 Motorölzusammensetzung mit niedrigem phosphongehalt und additivzusammensetzungen
EP92307279A EP0528610B1 (en) 1991-08-09 1992-08-10 Low phosphorous engine oil composition and additive compositions
DE69224943T DE69224943T2 (de) 1991-08-09 1992-08-10 Motorölzusammensetzung mit niedrigem Phosphongehalt und Additivzusammensetzungen
US08/162,681 US5629272A (en) 1991-08-09 1993-12-03 Low phosphorous engine oil compositions and additive compositions
US08/222,495 US6531428B2 (en) 1991-08-09 1994-04-04 Low phosphorous engine oil composition and additive compositions

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WO2012163938A1 (de) 2011-05-31 2012-12-06 Vifor (International) Ag Fe(iii)-2,4-dioxo-1-carbonyl-komplexverbindungen zur behandlung und prophylaxe von eisenmangelerscheinungen und eisenmangelanämien

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DE69224943D1 (de) 1998-05-07
US6531428B2 (en) 2003-03-11
ATE164621T1 (de) 1998-04-15
SG80545A1 (en) 2001-05-22
CA2075433A1 (en) 1993-02-10
US20020098990A1 (en) 2002-07-25
CA2075433C (en) 2000-11-28
EP0528610B1 (en) 1998-04-01
JPH0641568A (ja) 1994-02-15
DE69224943T2 (de) 1998-07-30
EP0528610A1 (en) 1993-02-24

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