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JP4571776B2 - Lubricating oil composition - Google Patents

Lubricating oil composition Download PDF

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Publication number
JP4571776B2
JP4571776B2 JP2002321754A JP2002321754A JP4571776B2 JP 4571776 B2 JP4571776 B2 JP 4571776B2 JP 2002321754 A JP2002321754 A JP 2002321754A JP 2002321754 A JP2002321754 A JP 2002321754A JP 4571776 B2 JP4571776 B2 JP 4571776B2
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Japan
Prior art keywords
group
lubricating oil
molecular weight
average molecular
oil composition
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JP2002321754A
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JP2004155873A (en
Inventor
直純 有本
哲夫 大川
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Eneos Corp
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JX Nippon Oil and Energy Corp
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Application filed by JX Nippon Oil and Energy Corp filed Critical JX Nippon Oil and Energy Corp
Priority to JP2002321754A priority Critical patent/JP4571776B2/en
Priority to US10/533,710 priority patent/US20060105921A1/en
Priority to EP03770108A priority patent/EP1559772B1/en
Priority to CNB2003801029219A priority patent/CN100455646C/en
Priority to PCT/JP2003/014032 priority patent/WO2004041977A1/en
Priority to AU2003280701A priority patent/AU2003280701A1/en
Publication of JP2004155873A publication Critical patent/JP2004155873A/en
Publication of JP4571776B2 publication Critical patent/JP4571776B2/en
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M161/00Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04Mixtures of base-materials and additives
    • C10M169/044Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084Acrylate; Methacrylate
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/086Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type polycarboxylic, e.g. maleic acid
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/24Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
    • C10M2215/28Amides; Imides
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01Physico-chemical properties
    • C10N2020/02Viscosity; Viscosity index
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02Pour-point; Viscosity index
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/04Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/042Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/04Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/045Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for continuous variable transmission [CVT]
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2060/00Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/14Chemical after-treatment of the constituents of the lubricating composition by boron or a compound containing boron

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Description

【0001】
【発明の属する技術分野】
本発明は潤滑油組成物に関し、詳しくは、摩耗防止性に優れ、特に長期間摩耗防止性を維持できる低粘度の潤滑油組成物に関する。
【0002】
【従来の技術】
近年、環境問題を背景に、炭酸ガス排出量の削減が急務となっており、自動車の燃費向上は従来にも増して重要な課題となっている。自動車の燃費向上の手段には、使用する潤滑油の低粘度化による攪拌抵抗の低減及び摩擦低減剤使用による、境界潤滑油領域における摩擦低減が有効であると考えられ、効果をあげている。
【0003】
低粘度の内燃機関用潤滑油においては、高分子量の粘度指数向上剤を配合した、あるいはさらに有機モリブデン化合物等の摩擦低減剤を使用した省燃費エンジン油が提案されている(例えば、特許文献1参照)。また、トルクコンバータ、湿式クラッチ、歯車軸受機構、オイルポンプ及び油圧制御機構から構成される自動変速機においては、湿式クラッチの摩擦特性を最適化する必要があることから、有機モリブデン化合物のような摩擦低減剤は通常使用されず、潤滑油の低粘度化が有効であると考えられ、トルクコンバータやオイルポンプの攪拌抵抗の低減によって燃費向上が期待される。しかしながら、潤滑油の低粘度化は摩耗防止性の悪化に直結するため低粘度化による燃費向上と摩耗防止性を両立することは困難であり、必然的に摩耗防止性が優先されることになる。
【0004】
従来の自動車用変速機油としては、変速特性等の各種性能を長期間維持できるものとして、合成油及び/又は鉱油系の潤滑油基油、摩耗防止剤、極圧剤、金属系清浄剤、無灰分散剤、摩擦調整剤等を最適化して配合したものが開示されている(例えば、特許文献2〜4参照)。また、粘度指数向上剤としては、一般に平均分子量が1,000〜1,000,000のものから選択されるが、低分子量の粘度指数向上剤を配合する潤滑油としては、例えば、数平均分子量1,000〜10,000のモノオレフィンの重合体又は共重合体を1〜15重量%と、平均分子量5,000〜50,000の飽和脂肪族1価アルコールとメタクリル酸とのエステルの共重合体を1〜5質量%とを併用した自動変速機油組成物(特許文献5参照)や、数平均分子量が26,000〜40,000のエチレン−α−オレフィンコポリマーを3〜5重量%を含有する半合成の自動変速機油組成物(特許文献6参照)、あるいは、数平均分子量19,000〜23,000のポリメタクリレートを27重量%〜34重量%含有する半合成の自動変速機油組成物(特許文献7参照)等が開示されている。
【特許文献1】
特開2001−181664号公報
【特許文献2】
特開平3−39399号公報
【特許文献3】
特開平7−268375号公報
【特許文献4】
特開2000−63869号公報
【特許文献5】
特開昭61−9497号公報
【特許文献6】
特開平1−168798号公報
【特許文献7】
特開平1−271494号公報
【0005】
【発明が解決しようとする課題】
しかしながら、これらの組成物はいずれも燃費向上を目的としたものではないためその動粘度は高く、潤滑油を低粘度化した際の最も重要な課題である初期及び長期間使用時の摩耗防止性への影響については全く検討されていないだけでなく、粘度指数向上剤とその他の添加剤との最適化の検討は十分になされていない。さらには、現在市場にある自動車用自動変速機油の動粘度は、40℃において30〜50mm/sの範囲にあるのが一般的であり、従って燃費向上と摩耗防止性が両立された低粘度の変速機油は実質的に存在しないと考えられる。
【0006】
そこで、本発明はこのような実情に鑑みなされたものであり、その目的は、低粘度でありながら、初期及び長期間使用後も十分な摩耗防止性を有する潤滑油組成物、特に自動変速機用あるいは無段変速機用に好適な低粘度の潤滑油組成物を提供することにある。
【0007】
【課題を解決するための手段】
本発明者らは、上記課題を解決するために鋭意検討した結果、潤滑油基油に、特定の含窒素化合物と特定の分子量の粘度指数向上剤とを最適化して配合した低粘度の潤滑油組成物が上記課題を解決できることを見出し、本発明を完成するに至った。
【0008】
すなわち、本発明は、(A)鉱油、合成油又は、それらの混合油からなる潤滑油基油に、(B)数平均分子量が900以上のアルキル基又はアルケニル基を少なくとも1つ有する含窒素化合物及び/又はその誘導体を組成物全量基準で、窒素含有量として0.01〜0.20質量%、及び(C)重量平均分子量が40,000以下の粘度指数向上剤を、組成物の粘度指数が160以上、かつ、組成物の40℃における動粘度が20〜30mm/sになるように配合してなることを特徴とする潤滑油組成物にある。
【0009】
また、前記(B)成分は、数平均分子量が1200以上のアルキル基又はアルケニル基を2つ有する含窒素化合物及び/又はその誘導体であることが好ましい。
【0010】
また、本発明の潤滑油組成物は、前記(B)成分として、数平均分子量が900以上のアルキル基又はアルケニル基を少なくとも1つ有する含窒素化合物のホウ素変性化合物を、組成物全量基準で、ホウ素含有量として0.002質量%以上、必須として含有することが好ましい。
【0011】
また、本発明の潤滑油組成物は、自動変速機あるいは無段変速機に使用されることが好ましい。
【0012】
また、本発明は、前記潤滑油組成物を使用することを特徴とする自動変速機あるいは無段変速機の摩耗防止性維持方法にある。
【0013】
【発明の実施の形態】
以下、本発明について詳述する。
【0014】
本発明における(A)成分は、鉱油、合成油又は、それらの混合油からなる潤滑油基油であり、特に限定されるものではなく、通常潤滑油組成物の基油として用いられているものであれば、鉱油、合成油を問わず使用できる。
【0015】
鉱油系基油を例示すれば、原油を常圧蒸留及び減圧蒸留して得られた潤滑油留分を、溶剤脱れき、溶剤抽出、水素化分解、溶剤脱ろう、接触脱ろう、水素化精製、硫酸洗浄、白土処理等の精製処理等を適宜組み合わせて精製したパラフィン系、ナフテン系等の鉱油系潤滑油基油やノルマルパラフィン等が挙げられる。
【0016】
また、合成系基油を例示すれば、ポリ−α−オレフィン(ポリブテン、1−オクテンオリゴマー、1−デセンオリゴマー、エチレン−プロピレンオリゴマー等)及びその水素化物、イソブテンオリゴマー及びその水素化物、イソパラフィン、アルキルベンゼン、アルキルナフタレン、ジエステル(ジトリデシルグルタレート、ジ−2−エチルヘキシルアジペート、ジイソデシルアジペート、ジトリデシルアジペート、ジ−2−エチルヘキシルセバケート等)、ポリオールエステル(トリメチロールプロパンカプリレート、トリメチロールプロパンペラルゴネート、ペンタエリスリトール2−エチルヘキサノエート、ペンタエリスリトールペラルゴネート等)、ポリオキシアルキレングリコール、ジアルキルジフェニルエーテル、ポリフェニルエーテル等が挙げられる。
【0017】
本発明の潤滑油基油は、2種類以上の鉱油系基油、又は2種類以上の合成油系基油の混合物であって差し支えなく、鉱油系基油と合成油系基油の混合物であっても差し支えない。そして、上記混合物における2種類以上の基油の混合比は、任意に選ぶことができる。
【0018】
本発明におけるこれら潤滑油基油は、その動粘度に格別の限定はないが、100℃における動粘度の下限値は1mm/s、好ましくは2mm/sであり、一方、100℃における動粘度の上限値は5mm/s、好ましくは4mm/s、特に好ましくは3.5mm/sであることが望ましい。潤滑油基油の100℃における動粘度を1mm/s以上とすることによって、油膜形成が十分であり、潤滑性により優れ、また、高温条件下での基油の蒸発損失がより小さい潤滑油組成物を得ることが可能となる。一方、100℃における動粘度を5mm/s以下とすることによって、流体抵抗が小さくなるため潤滑個所での摩擦抵抗がより小さい潤滑油組成物を得ることが可能となる。
【0019】
また、本発明におけるこれら潤滑油基油は、その粘度指数に格別の限定はないが、粘度指数は80以上、好ましくは90以上、特に好ましくは110以上であることが望ましい。粘度指数を80以上とすることによって、長期間使用後の摩耗防止性に優れた組成物を得ることができる。
【0020】
本発明の(B)成分は、数平均分子量が900以上のアルキル基又はアルケニル基を少なくとも1つ有する含窒素化合物及び/又はその誘導体であり、これらの中から任意に選ばれる1種類あるいは2種類以上を配合することができる。
【0021】
(B)成分としては、具体的には、例えば、
(B−1)数平均分子量が900以上のアルキル基又はアルケニル基を少なくとも1つ有するコハク酸イミド又はその誘導体
(B−2)数平均分子量が900以上のアルキル基又はアルケニル基を少なくとも1つ有するベンジルアミン又はその誘導体
(B−3)数平均分子量が900以上のアルキル基又はアルケニル基を少なくとも1つ有するポリアミン又はその誘導体
の中から選ばれる1種又は2種以上の化合物等が挙げられる。
【0022】
上記の(B−1)コハク酸イミドとしては、より具体的には、下記の式(1)又は(2)で示される化合物等が例示できる。
【化1】

Figure 0004571776
【0023】
上記(1)式中、Rは数平均分子量900以上のアルキル基又はアルケニル基を示し、aは1〜5、好ましくは2〜4の整数を示している。
【化2】
Figure 0004571776
【0024】
上記(2)式中、R及びRは、それぞれ個別に、数平均分子量900以上のアルキル基又はアルケニル基を示し、bは0〜4、好ましくは1〜3の整数を示している。
【0025】
なお、コハク酸イミドとは、イミド化に際しては、ポリアミンの一端に無水コハク酸が付加した、式(1)のようないわゆるモノタイプのコハク酸イミドと、ポリアミンの両端に無水コハク酸が付加した、式(2)のようないわゆるビスタイプのコハク酸イミドがあり、(B−1)成分としては、いずれも使用することができるが、初期及び長期間使用後においても摩耗防止性を維持しやすいことから、ビスタイプ、すなわち数平均分子量900以上のアルキル基又はアルケニル基を2つ有するコハク酸イミドであることが好ましい。
【0026】
上記の(B−2)ベンジルアミンとしては、より具体的には、下記の式(3)で表せる化合物等が例示できる。
【化3】
Figure 0004571776
【0027】
上記(3)式中、Rは、数平均分子量900以上のアルキル基又はアルケニル基を示し、cは1〜5、好ましくは2〜4の整数を示している。
【0028】
このベンジルアミンの製造方法は何ら限定されるものではないが、例えば、プロピレンオリゴマー、ポリブテン、エチレン−α−オレフィン共重合体等のポリオレフィンをフェノールと反応させてアルキルフェノールとした後、これにホルムアルデヒドとジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン等のポリアミンをマンニッヒ反応により反応させることにより得ることができる。
【0029】
上記の(B−3)ポリアミンとしては、より具体的には、下記の式(4)で表せる化合物等が例示できる。
【化4】
Figure 0004571776
【0030】
上記(4)式中、Rは、数平均分子量900以上のアルキル基又はアルケニル基を示し、dは1〜5、好ましくは2〜4の整数を示している。
【0031】
このポリアミンの製造法は何ら限定されるものではないが、例えば、プロピレンオリゴマー、ポリブテン、エチレン−α−オレフィン共重合体等のポリオレフィンを塩素化した後、これにアンモニアやエチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン等のポリアミンを反応させることにより得ることができる。
【0032】
(B)成分における上記のようなコハク酸イミド、ベンジルアミン、ポリアミン等の含窒素化合物の誘導体としては、具体的には例えば、前述したような含窒素化合物に炭素数2〜30のモノカルボン酸(脂肪酸等)やシュウ酸、フタル酸、トリメリット酸、ピロメリット酸等の炭素数2〜30のポリカルボン酸若しくはこれらの無水物、又はエステル化合物、炭素数2〜6のアルキレンオキサイド、ヒドロキシ(ポリ)オキシアルキレンカーボネート等を作用させて、残存するアミノ基及び/又はイミノ基の一部又は全部を中和したり、アミド化したりした、いわゆる酸変性化合物;前述したような含窒素化合物にホウ酸、ホウ酸塩あるいはホウ酸エステル等のホウ素化合物を作用させて、残存するアミノ基及び/又はイミノ基の一部又は全部を中和したり、アミド化した、いわゆるホウ素変性化合物;前述したような含窒素化合物に硫黄化合物を作用させた硫黄変性化合物;及び前述したような含窒素化合物に酸変性、ホウ素変性、硫黄変性から選ばれた2種以上の変性を組み合わせた変性化合物;等が挙げられる。
【0033】
本発明の(B)成分における数平均分子量が900以上のアルキル基又はアルケニル基としては、直鎖状でも分枝状でもよいが、好ましいものとしては、具体的には、プロピレン、1−ブテン、イソブチレン等のオレフィンのオリゴマーやエチレンとプロピレンのコオリゴマーから誘導される分枝状アルキル基や分枝状アルケニル基等、好ましくはポリ(イソ)ブテニル基が挙げられ、その数平均分子量は好ましくは1200以上であり、より好ましく1700以上、さらに好ましくは2000以上、特に好ましくは2300以上である。また、その数平均分子量は、その上限に特に制限はないが、好ましくは5000以下であり、より好ましくは3500以下であり、特に好ましくは3000以下である。アルキル基又はアルケニル基の数平均分子量を900以上とすることで長期間使用後の摩耗防止性を維持しやすく、5000以下とすることで組成物の低温流動性に優れた組成物を得ることができる。
【0034】
(B)成分の含窒素化合物の窒素含有量は任意であるが、耐摩耗性、酸化安定性及び摩擦特性等の点から、通常、その窒素含有量が0.01〜10質量%、好ましくは0.1〜10質量%のものが望ましく用いられる。
本発明の潤滑油組成物における(B)成分としては、上記のような数平均分子量を有するアルキル又はアルケニルコハク酸イミドが摩耗防止性を維持しやすいため、より好ましく使用することができる。また、上記のような数平均分子量、特に数平均分子量が2000以上のアルキル又はアルケニルコハク酸イミドのホウ素変性化合物が、初期及び長期間使用後において最も摩耗防止性に優れるため、当該ホウ素変性化合物を必須として含有させることが特に好ましい。
【0035】
なお、上記含窒素化合物のホウ素変性化合物におけるホウ素及び窒素の質量比(B/N比)は特に制限はなく、通常、0.01〜3であるが、好ましくは0.05以上であり、より好ましくは0.1以上であり、さらに好ましくは0.2以上であり、また、好ましくは1以下であり、より好ましくは0.8以下であり、さらに好ましくは0.6以下である。ホウ素変性化合物のB/N比が上記範囲にあるものを選択することで、初期及び長期間使用後においても摩耗防止性に優れた組成物を得ることができる。なお、上記含窒素化合物とそのホウ素変性化合物を併用する場合、例えば、数平均分子量が900〜2000未満のポリ(イソ)ブテニル基を有するビスタイプのコハク酸イミドと数平均分子量が2000以上のビスタイプのポリ(イソ)ブテニルコハク酸イミドのホウ素変性化合物とを併用した場合、相乗的に初期及び長期間使用後の摩耗防止性を向上させることができる。その場合であっても、ホウ素変性化合物起因のホウ素と(B)成分起因の合計の窒素との質量比も上記範囲となるように調製されることが好ましい。
【0036】
本発明の潤滑油組成物において(B)成分の含有量の下限値は、潤滑油組成物全量基準で、窒素量として0.01質量%、好ましくは0.02質量%であり、一方、その含有量の上限値は、潤滑油組成物全量基準で、窒素量として0.2質量%、好ましくは0.18質量%である。(B)成分の含有量が潤滑油組成物全量基準で、窒素量として0.01質量%未満の場合は、(B)成分含有による長期間使用後の摩耗防止性を維持しにくく、0.2質量%を超える場合は、潤滑油組成物の低温流動性が悪化するため、それぞれ好ましくない。なお、(B)成分が、数平均分子量が1200以上のアルキル基又はアルケニル基を2つ有する含窒素化合物の場合、その含有量の上限値は0.07質量%以下とすることもでき、さらに数平均分子量が2000以上のアルキル基又はアルケニル基を2つ有する含窒素化合物の場合であれば、0.04質量%以下としても十分な摩耗防止性を発現することが可能である。
【0037】
また、(B)成分として、含窒素化合物のホウ素変性化合物を必須として含有させる場合、その含有量の下限値は、ホウ素量として好ましくは0.002質量%以上であり、より好ましくは0.004質量%以上、特に好ましくは0.008質量%以上である。また、その含有量の上限値は、ホウ素量として、好ましくは0.05質量%以下、さらに好ましくは0.02質量%以下、特に好ましくは0.015質量%以下である。(B)成分としてホウ素変性化合物をホウ素量として上記好ましい範囲とすることで、初期及び長期間使用後においてもより優れた摩耗防止性を維持することができる。
【0038】
本発明における(C)成分は重量平均分子量が40,000以下の粘度指数向上剤であり、具体的には、重量平均分子量が40,000以下の非分散型粘度指数向上剤及び/又は分散型粘度指数向上剤等が挙げられる。
【0039】
非分散型粘度指数向上剤としては、具体的には、下記の式(5)、(6)及び(7)で表される化合物の中から選ばれる1種又は2種以上のモノマー(C−1)の共重合体あるいはその水素化物等が例示できる。一方、分散型粘度指数向上剤としては、具体的には、一般式(8)及び(9)で表される化合物の中から選ばれる2種以上のモノマーの共重合体又はその水素化物に酸素含有基を導入したものや、一般式(5)〜(7)で表される化合物の中から選ばれる1種又は2種以上のモノマー(C−1)と一般式(8)及び(9)で表される化合物の中から選ばれる1種又は2種以上のモノマー(C−2)との共重合体、或いはその水素化物等が例示できる。
【化5】
Figure 0004571776
【0040】
上記(5)式中、Rは水素又はメチル基を示し、Rは炭素数1〜18のアルキル基を示している。
【0041】
を示す炭素数1〜18のアルキル基としては、具体的には、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基等(これらアルキル基は直鎖状でも分枝状でもよい)等が例示できる。
【化6】
Figure 0004571776
【0042】
上記(6)式中、Rは水素又はメチル基を示し、Rは炭素数1〜12の炭化水素基を示している。
【0043】
を示す炭素数1〜12の炭化水素基としては、具体的には、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基等のアルキル基(これらアルキル基は直鎖状でも分枝状でもよい);ブテニル基、ペンテニル基、ヘキセニル基、ヘプテニル基、オクテニル基、ノネニル基、デセニル基、ウンデセニル基、ドデセニル基等のアルケニル基(これらアルケニル基は直鎖状でも分枝状でもよく、二重結合の位置も任意である);シクロペンチル基、シクロヘキシル基、シクロヘプチル基等の炭素数5〜7のシクロアルキル基;メチルシクロペンチル基、ジメチルシクロペンチル基、メチルエチルシクロペンチル基、ジエチルシクロペンチル基、メチルシクロヘキシル基、ジメチルシクロヘキシル基、メチルエチルシクロヘキシル基、ジエチルシクロヘキシル基、メチルシクロヘプチル基、ジメチルシクロヘプチル基、メチルエチルシクロヘプチル基、ジエチルシクロヘプチル基等の炭素数6〜11のアルキルシクロアルキル基(これらアルキル基のシクロアルキル基への置換位置は任意である);フェニル基、ナフチル基等のアリール基:トリル基、キシリル基、エチルフェニル基、プロピルフェニル基、ブチルフェニル基、ペンチルフェニル基、ヘキシルフェニル基等の炭素数7〜12の各アルキルアリール基(これらアルキル基は直鎖状でも分枝状でもよく、またアリール基への置換位置も任意である);ベンジル基、フェニルエチル基、フェニルプロピル基、フェニルブチル基、フェニルペンチル基、フェニルヘキシル基等の炭素数7〜12の各フェニルアルキル基(これらアルキル基は直鎖状でも分枝状でもよい);等が例示できる。
【化7】
Figure 0004571776
【0044】
上記(7)式中、D及びDは、それぞれ個別に、水素原子、炭素数1〜18のアルキルアルコールの残基(−OR:Rは炭素数1〜18のアルキル基)又は炭素数1〜18のモノアルキルアミンの残基(−NHR:Rは炭素数1〜18のアルキル基)を示している。
【化8】
Figure 0004571776
【0045】
(8)式中、R10は水素原子又はメチル基を示し、R11は、炭素数1〜18のアルキレン基を示し、Eは窒素原子を1〜2個、酸素原子を0〜2個含有するアミン残基又は複素環残基を示している。また、eは0又は1の整数である。
【0046】
11を示す炭素数1〜18のアルキレン基としては、具体的には、エチレン基、プロピレン基、ブチレン基、ペンチレン基、ヘキシレン基、へプチレン基、オクチレン基、ノニレン基、デシレン基、ウンデシレン基、ドデシレン基、トリデシレン基、テトラデシレン基、ペンタデシレン基、ヘキサデシレン基、ヘプタデシレン基、オクタデシレン基等(これらアルキレン基は直鎖状でも分枝状でもよい)等が例示できる。
【0047】
また、Eを示す基としては、具体的には、ジメチルアミノ基、ジエチルアミノ基、ジプロピルアミノ基、ジブチルアミノ基、アニリノ基、トルイジノ基、キシリジノ基、アセチルアミノ基、ベンゾイルアミノ基、モルホリノ基、ピロリル基、ピロリノ基、ピリジル基、メチルピリジル基、ピロリジニル基、ピペリジニル基、キノニル基、ピロリドニル基、ピロリドノ基、イミダゾリノ基、ピラジノ基等が例示できる。
【化9】
Figure 0004571776
【0048】
上記(9)式中、R12は水素原子又はメチル基を示し、Eは窒素原子を1〜2個、酸素原子を0〜2個含有するアミン残基又は複素環残基を示している。
【0049】
を示す基としては、具体的には、ジメチルアミノ基、ジエチルアミノ基、ジプロピルアミノ基、ジブチルアミノ基、アニリノ基、トルイジノ基、キシリジノ基、アセチルアミノ基、ベンゾイルアミノ基、モルホリノ基、ピロリル基、ピロリノ基、ピリジル基、メチルピリジル基、ピロリジニル基、ピペリジニル基、キノニル基、ピロリドニル基、ピロリドノ基、イミダゾリノ基、ピラジノ基等が例示できる。
【0050】
(C−1)成分のモノマーとして好ましいものとしては、具体的には、炭素数1〜18のアルキルアクリレート、炭素数1〜18のアルキルメタクリレート、炭素数2〜20のオレフィン、スチレン、メチルスチレン、無水マレイン酸エステル、無水マレイン酸アミド及びこれらの混合物等が例示できる。
【0051】
(C−2)成分のモノマーとして好ましいものとしては、具体的には、ジメチルアミノメチルメタクリレート、ジエチルアミノメチルメタクリレート、ジメチルアミノエチルメタクリレート、ジエチルアミノエチルメタクリレート、2−メチル−5−ビニルピリジン、モルホリノメチルメタクリレート、モルホリノエチルメタクリレート、N−ビニルピロリドン及びこれらの混合物等が例示できる。
【0052】
なお、上記(C−1)化合物の中から選ばれる1種又は2種以上のモノマーと、(C−2)化合物の中から選ばれる1種又は2種以上のモノマーとを共重合する際の(C−1)成分と(C−2)成分のモル比は任意であるが、一般に、80:20〜95:5程度である。また共重合の反応方法も任意であるが、通常、ベンゾイルパーオキシド等の重合開始剤の存在下で(C−1)成分と(C−2)成分をラジカル溶液重合させることにより容易に共重合体が得られる。
【0053】
(C)成分の具体例としては、非分散型及び分散型ポリメタクリレート類、非分散型及び分散型エチレン−α−オレフィン共重合体及びその水素化物、ポリイソブチレン及びその水素化物、スチレン−ジエン水素化共重合体、スチレン−無水マレイン酸エステル共重合体並びにポリアルキルスチレン等が挙げられる。
【0054】
本発明において(C)成分の分子量は、重量平均分子量で、40,000以下であり、好ましくは35,000以下のものが望ましい。重量平均分子量が40,000を越えると長期間使用後の摩耗防止性劣るため好ましくない。また、(C)成分の重量平均分子量は、特に制限はなく、900以上のものが使用できるが、10,000以上であることが好ましく、20,000以上であることがさらに好ましい。(C)成分の重量平均分子量が10,000未満の粘度指数向上剤、例えば重量平均分子量900〜10,000未満のポリイソブチレンは、粘度指数向上効果が小さく、多量に配合する必要があり、長期間使用後において摩耗防止性を維持しにくくなるため、(C)成分の重量平均分子量としては、10,000以上とするのが良い。
【0055】
本発明における(C)成分としては、重量平均分子量が10,000〜40,000の非分散型のポリメタアクリレートが、長期間使用後の摩耗防止性を維持しやすいため特に好ましい。
【0056】
本発明の潤滑油組成物における(C)成分の含有量は、組成物の粘度指数が160以上、好ましくは165以上となるように設定することが望ましい。一方、組成物の粘度指数の上限は、好ましくは210未満、より好ましくは190未満となるように(C)成分の含有量を設定することが望ましい。また、組成物の40℃における動粘度は、20〜30mm/sになるような量の(C)成分を含有させる必要があり、好ましくは、22〜28mm/sとなるように含有させることが望ましい。本発明においては、組成物の粘度指数及び40℃における動粘度を上記規定範囲となるように、前記のような粘度指数向上剤のなかから任意に選ばれた1種類あるいは2種類以上の化合物を任意の量で配合することができるが、例えばその含有量は1質量%以上、好ましくは5質量%以上、特に好ましくは6質量%以上であり、また、20質量%以下、好ましくは15質量%以下、特に好ましくは12質量%以下である。組成物の粘度指数が160より小さいと、長期間使用後の摩耗防止性が悪化するため好ましくなく、また、40℃における動粘度が上記範囲未満であると初期及び長期間使用後の摩耗防止性が悪化し、40℃における動粘度が上記範囲を越えると攪拌抵抗低減による省燃費性を得にくいためそれぞれ好ましくない。
【0057】
本発明においては、(A)成分を基油とし、(B)成分を特定量配合し、(C)成分を組成物の粘度指数を160以上、かつ、組成物の40℃における動粘度が20〜30mm/sとなるような量配合した低粘度の潤滑油組成物とするだけで、初期及び長期間使用後においても摩耗防止性に優れる潤滑油組成物を得ることができるが、その性能を高める目的で、必要に応じて、さらに他の種類の添加剤を配合してもよい。このような添加剤として、摩耗防止剤あるいは極圧剤、金属系清浄剤、摩擦調整剤、錆止め剤、腐食防止剤、流動点降下剤、ゴム膨潤剤、消泡剤、着色剤等を挙げることができる。これらの化合物は単独であるいは数種類組み合わせて用いることができる。
【0058】
本発明の潤滑油組成物に併用可能な摩耗防止剤あるいは極圧剤としては、硫黄系添加剤、リン系添加剤、硫黄及びリン系添加剤等、潤滑油用の摩耗防止剤あるいは極圧剤として通常用いられる任意の化合物が使用可能であるが、例えば、ジスルフィド類、硫化オレフィン類、硫化油脂類等の硫黄系化合物、リン酸モノエステル類、リン酸ジエステル類、リン酸トリエステル類、亜リン酸モノエステル類、亜リン酸ジエステル類、亜リン酸トリエステル類、及びこれらのエステル類とアミン類あるいはアルカノールアミン類との塩等のリン系化合物、ジチオリン酸亜鉛、チオリン酸エステル等の硫黄及びリン系化合物等が使用できる。これら摩耗防止剤あるいは極圧剤の含有量は特に限定されないが、通常、潤滑油組成物全量基準で、0.01〜5.0質量%である。
【0059】
本発明の潤滑油組成物に併用可能な金属系清浄剤としては、潤滑油用の金属系清浄剤として通常用いられる任意の化合物が使用可能であるが、例えば、アルカリ金属又はアルカリ土類金属のスルフォネート、フェネート、サリシレート、ナフテネート等が本発明の組成物に、単独あるいは二種類以上組み合わせて使用できる。ここでアルカリ金属としてはナトリウムやカリウム、アルカリ土類金属としてはカルシウム、マグネシウム等が例示される。また、具体的な金属系清浄剤としてはカルシウム又はマグネシウムのスルフォネート、フェネート、サリシレートが好ましく用いられる。なお、これら金属系清浄剤の全塩基価及び含有量は要求される潤滑油の性能に応じて任意に選択することができるが、通常全塩基価は、過塩素酸法で0〜500mgKOH/gであり、その含有量は0.01〜10質量%である。
【0060】
本発明の潤滑油組成物に併用可能な摩擦調整剤としては、潤滑油用の摩擦調整剤として通常用いられる任意の化合物が使用可能であるが、炭素数6〜30のアルキル基又はアルケニル基、特に炭素数6〜30の直鎖アルキル基又は直鎖アルケニル基を分子中に少なくとも1個有する、アミン化合物、脂肪酸エステル、脂肪酸アミド、脂肪酸金属塩等が挙げられる。
【0061】
アミン化合物としては、炭素数6〜30の直鎖状若しくは分枝状、好ましくは直鎖状の脂肪族モノアミン、直鎖状若しくは分枝状、好ましくは直鎖状の脂肪族ポリアミン、又はこれら脂肪族アミンのアルキレンオキシド付加物等が例示できる。脂肪酸エステルとしては、炭素数7〜31の直鎖状又は分枝状、好ましくは直鎖状の脂肪酸と、脂肪族1価アルコール又は脂肪族多価アルコールとのエステル等が例示できる。脂肪酸アミドとしては、炭素数7〜31の直鎖状又は分枝状、好ましくは直鎖状の脂肪酸と、脂肪族モノアミン又は脂肪族ポリアミンとのアミド等が例示できる。脂肪酸金属塩としては、炭素数7〜31の直鎖状又は分枝状、好ましくは直鎖状の脂肪酸の、アルカリ土類金属塩(マグネシウム塩、カルシウム塩等)や亜鉛塩等が挙げられる。
【0062】
本発明においては、これらの摩擦調整剤の中から任意に選ばれた1種類あるいは2種類以上の化合物を、任意の量で含有させることができるが、通常、その含有量は、潤滑油組成物基準で0.01〜5.0質量%、好ましくは0.03〜3.0質量%であるのが望ましい。
【0063】
本発明の潤滑油組成物に併用可能な酸化防止剤としては、フェノール系化合物やアミン系化合物等、潤滑油に一般的に使用されているものであれば使用可能である。
【0064】
具体的には、2−6−ジ−tert−ブチル−4−メチルフェノール等のアルキルフェノール類、メチレン−4、4−ビスフェノール(2、6−ジ−tert−ブチル−4−メチルフェノール)等のビスフェノール類、フェニル−α−ナフチルアミン等のナフチルアミン類、ジアルキルジフェニルアミン類、ジ−2−エチルヘキシルジチオリン酸亜鉛等のジアルキルジチオリン酸亜鉛類、(3、5−ジ−tert−ブチル−4−ヒドロキシフェニル)あるいは(3−メチル−5−tert−ブチル−4−ヒドロキシフェニル)脂肪酸(プロピオン酸等)と1価又は多価アルコール、例えばメタノール、オクタノール、オクタデカノール、1、6ヘキサジオール、ネオペンチルグリコール、チオジエチレングリコール、トリエチレングリコール、ペンタエリスリトール等とのエステル等が挙げられる。
【0065】
これらの中から任意に選ばれた1種類あるいは2種類以上の化合物は、任意の量を含有させることができるが、通常、その含有量は、潤滑油組成物全量基準で0.01〜5.0質量%であるのが望ましい。
【0066】
本発明の潤滑油組成物に併用可能な腐食防止剤としては、潤滑油用の腐食防止剤として通常用いられる任意の化合物が使用可能であるが、例えば、ベンゾトリアゾール系、トリルトリアゾール系、チアジアゾール系、イミダゾール系化合物等が挙げられる。これらの中から任意に選ばれた1種類あるいは2種類以上の化合物は、任意の量を含有させることができるが、通常、その含有量は、潤滑油組成物全量基準で0.01〜3.0質量%であるのが望ましい。
【0067】
本発明の潤滑油組成物に併用可能な消泡剤としては、潤滑油用の消泡剤として通常用いられる任意の化合物が使用可能であるが、例えば、ジメチルシリコーン、フルオロシリコーン等のシリコーン類が挙げられる。これらの中から任意に選ばれた1種類あるいは2種類以上の化合物は、任意の量を含有させることができるが、通常、その含有量は、潤滑油組成物全量基準で0.001〜0.05質量%であるのが望ましい。
【0068】
本発明の潤滑油組成物は、初期及び長期間使用後においても摩耗防止性に優れ、潤滑油起因の撹拌抵抗を低減できるため、自動車の潤滑油、例えば内燃機関用、変速機用、特に自動変速機用又は無段変速機用として使用することで自動車の燃費の向上に寄与することが可能となる。
【実施例】
以下、本発明の内容を実施例及び比較例によりさらに具体的に説明するが、本発明はこれによりなんら限定されるものではない。
(実施例1〜5及び比較例1〜3)
【0069】
表1又は表2に示す各種の潤滑油基油及び添加剤を配合して、本発明に係る潤滑油組成物(表1の実施例1〜5)及び比較用の潤滑油組成物(表2の比較例1〜3)を調製した。なお、各添加剤の添加量は組成物全量基準である。
【0070】
得られた各組成物について、初期及び長期間使用後の摩耗防止性を以下の(1)に示す摩耗試験により評価した。なお、初期の摩耗防止性評価には新油を用い、長期間使用油の摩耗防止性評価には、予め(2)に示す超音波せん断試験実施により劣化させた劣化油を用いた。その性能評価の結果をそれぞれ表1及び表2に併記した。
【0071】
(1)摩耗試験
ASTM D2714に規定される試験条件に準拠して以下に示す条件でLFW-1摩擦試験を行い、試験後のブロック試験片の摩耗幅を測定した。摩耗幅が小さいほど、摩耗防止性に優れる。
(試験条件)
リング :Falex S−10 Test Ring
(SAE 4620 Steel)
ブロック :Falex H−30 Test Block
(SAE 01 Steel)
試験油温 :100℃
試験荷重 :50lb
すべり速度 :100cm/s
【0072】
(2)超音波せん断試験
JASO M347−95に規定されている自動変速機油せん断安定性試験法に準拠し、8時間のせん断試験を実施した。本試験は、自動変速機油の使用過程における動粘度低下度合いを評価するものであり、8時間のせん断試験は実走行の10万km以上に相当し、本試験終後の油は10万km走行後の油に相当すると考えられる。
【0073】
【表1】
Figure 0004571776
【0074】
【表2】
Figure 0004571776
【0075】
表1に示す結果から明らかなとおり、本発明に係る実施例1〜5の潤滑油組成物は、いずれも劣化油の摩耗防止性が新油時に比べほとんど低下していない。また、(C)成分として重量平均分子量が30,000の非分散型ポリメタアクリレートを使用した場合(実施例2)、(B)成分として数平均分子量が1,300のポリブテニル基を有するビスタイプのコハク酸イミドを使用した場合、(B)成分として数平均分子量が2,500のポリブテニル基を有するビスタイプのコハク酸イミドのホウ素変性化合物を必須として使用した場合(実施例4及び5)、実施例1の組成物に比べ初期及び長期間使用後においても摩耗防止性により優れた結果を示した。さらには、実施例1で使用したコハク酸イミドと実施例5で使用したコハク酸イミドのホウ素変性化合物とを併用した場合(実施例4)、相乗的に摩耗防止性能が向上する結果であった。
【0076】
それに対して、(B)成分の含有量が本発明の規定範囲に満たない場合(比較例1)、組成物の粘度指数が160未満の場合(比較例2)、(C)成分の重量平均分子量が40,000を越えてしまう場合(比較例3)は新油時の摩耗防止性も劣るが、劣化油の摩耗防止性はさらに悪化した。なお、組成物の40℃における動粘度が20mm/s未満の場合、摩耗防止性が比較例よりさらに劣る結果であった。
【発明の効果】
本発明の潤滑油組成物は、低粘度でありながら初期及び長期間使用後においても摩耗防止性に優れ、潤滑油起因の撹拌抵抗を低減できるため、自動車の潤滑油、例えば内燃機関用、変速機用、特に自動変速機用又は無段変速機用として使用することで自動車の燃費の向上に寄与することが可能となる。また、自動車以外の機械・装置用の潤滑油においても、摩耗防止性を維持しながら機械・装置のエネルギー消費を抑制することが可能となるので、例えば、湿式ブレーキ用、油圧作動装置用、圧縮機用、タービン用、ギヤ用、冷凍機用、軸受け用等種々の用途に有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a lubricating oil composition, and more particularly, to a lubricating oil composition having a low viscosity that is excellent in anti-wear properties and particularly capable of maintaining anti-wear properties for a long period of time.
[0002]
[Prior art]
In recent years, against the backdrop of environmental problems, the reduction of carbon dioxide emissions has become an urgent issue, and improving the fuel efficiency of automobiles has become more important than ever. As means for improving the fuel efficiency of automobiles, it is considered effective to reduce the friction resistance in the boundary lubricating oil region by reducing the stirring resistance by reducing the viscosity of the lubricating oil used and by using a friction reducing agent.
[0003]
In low-viscosity lubricating oils for internal combustion engines, fuel-saving engine oils containing a high molecular weight viscosity index improver or using a friction reducing agent such as an organic molybdenum compound have been proposed (for example, Patent Document 1). reference). In an automatic transmission composed of a torque converter, a wet clutch, a gear bearing mechanism, an oil pump and a hydraulic control mechanism, it is necessary to optimize the friction characteristics of the wet clutch. A reducing agent is not usually used, and it is considered that lowering the viscosity of the lubricating oil is effective, and improvement in fuel efficiency is expected by reducing the stirring resistance of the torque converter and the oil pump. However, lowering the viscosity of the lubricating oil directly leads to worsening of wear prevention, so it is difficult to achieve both improved fuel efficiency and wear prevention by lowering the viscosity, and wear prevention is given priority. .
[0004]
As conventional transmission oils for automobiles, various performances such as transmission characteristics can be maintained for a long period of time. Synthetic oils and / or mineral oil base oils, antiwear agents, extreme pressure agents, metallic detergents, The thing which optimized and mix | blended the ash dispersing agent, the friction modifier, etc. is disclosed (for example, refer patent documents 2-4). Further, the viscosity index improver is generally selected from those having an average molecular weight of 1,000 to 1,000,000. As the lubricating oil blended with the low molecular weight viscosity index improver, for example, the number average molecular weight Copolymerization of an ester of 1 to 15% by weight of a polymer or copolymer of 1,000 to 10,000 monoolefin and a saturated aliphatic monohydric alcohol having an average molecular weight of 5,000 to 50,000 and methacrylic acid Contains 3 to 5% by weight of an automatic transmission oil composition (see Patent Document 5) combined with 1 to 5% by mass of a coalescence, and an ethylene-α-olefin copolymer having a number average molecular weight of 26,000 to 40,000 Semi-synthetic automatic transmission oil composition (see Patent Document 6) or semi-synthetic containing 27 to 34% by weight of polymethacrylate having a number average molecular weight of 19,000 to 23,000 Automatic transmission fluid composition (Patent Document 7 references) have been disclosed.
[Patent Document 1]
JP 2001-181664 A
[Patent Document 2]
JP-A-3-39399
[Patent Document 3]
JP 7-268375 A
[Patent Document 4]
JP 2000-63869 A
[Patent Document 5]
JP 61-9497 A
[Patent Document 6]
JP-A-1-168798
[Patent Document 7]
JP-A-1-271494
[0005]
[Problems to be solved by the invention]
However, none of these compositions are intended to improve fuel efficiency, so their kinematic viscosity is high, and the most important issue when reducing the viscosity of a lubricating oil is the ability to prevent wear during initial and long-term use. The influence on the viscosity is not studied at all, and the optimization of the viscosity index improver and other additives is not sufficiently studied. Furthermore, the kinematic viscosity of automatic transmission oil for automobiles currently on the market is 30-50 mm at 40 ° C. 2 In general, it is considered that there is substantially no low-viscosity transmission oil that achieves both improved fuel efficiency and wear resistance.
[0006]
Therefore, the present invention has been made in view of such circumstances, and an object of the present invention is to provide a lubricating oil composition, particularly an automatic transmission, which has a low viscosity and has sufficient wear resistance after initial and long-term use. Another object of the present invention is to provide a low-viscosity lubricating oil composition suitable for use in a continuously variable transmission or a continuously variable transmission.
[0007]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have determined that a low-viscosity lubricating oil in which a specific nitrogen-containing compound and a viscosity index improver having a specific molecular weight are optimized and blended with a lubricating base oil The present inventors have found that the composition can solve the above problems and have completed the present invention.
[0008]
That is, the present invention provides (A) a nitrogen-containing compound having (B) at least one alkyl group or alkenyl group having a number average molecular weight of 900 or more in a lubricating base oil composed of mineral oil, synthetic oil or a mixed oil thereof. And / or a derivative thereof based on the total amount of the composition as a nitrogen content of 0.01 to 0.20 mass%, and (C) a viscosity index improver having a weight average molecular weight of 40,000 or less, a viscosity index of the composition 160 or more, and the kinematic viscosity at 40 ° C. of the composition is 20 to 30 mm. 2 The lubricating oil composition is characterized by being formulated so as to be / s.
[0009]
The component (B) is preferably a nitrogen-containing compound having two alkyl groups or alkenyl groups having a number average molecular weight of 1200 or more and / or a derivative thereof.
[0010]
Moreover, the lubricating oil composition of the present invention contains, as the component (B), a boron-modified compound of a nitrogen-containing compound having at least one alkyl group or alkenyl group having a number average molecular weight of 900 or more, based on the total amount of the composition. The boron content is preferably 0.002% by mass or more and essential.
[0011]
In addition, the lubricating oil composition of the present invention is preferably used for an automatic transmission or a continuously variable transmission.
[0012]
The present invention also lies in a method for maintaining wear resistance of an automatic transmission or a continuously variable transmission, wherein the lubricating oil composition is used.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
[0014]
The component (A) in the present invention is a lubricating base oil composed of mineral oil, synthetic oil or a mixed oil thereof, and is not particularly limited, and is usually used as a base oil of a lubricating oil composition. If so, it can be used regardless of mineral oil or synthetic oil.
[0015]
For example, mineral oil base oils can be obtained by removing solvent oil, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining of lubricating oil fractions obtained by atmospheric and vacuum distillation of crude oil. In addition, paraffinic and naphthenic mineral oil base oils and normal paraffins, etc., which are purified by appropriately combining purification treatments such as sulfuric acid washing and clay treatment, and the like.
[0016]
Examples of synthetic base oils include poly-α-olefins (polybutene, 1-octene oligomer, 1-decene oligomer, ethylene-propylene oligomer, etc.) and their hydrides, isobutene oligomers and their hydrides, isoparaffins, alkylbenzenes. Alkyl naphthalene, diester (ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di-2-ethylhexyl sebacate, etc.), polyol ester (trimethylolpropane caprylate, trimethylolpropane pelargonate, Pentaerythritol 2-ethylhexanoate, pentaerythritol pelargonate, etc.), polyoxyalkylene glycol, dialkyldiphenyl ether, polyphenyl Ether and the like.
[0017]
The lubricating base oil of the present invention can be a mixture of two or more mineral base oils or two or more synthetic base oils, and can be a mixture of a mineral base oil and a synthetic base oil. There is no problem. And the mixing ratio of 2 or more types of base oil in the said mixture can be chosen arbitrarily.
[0018]
These lubricating base oils in the present invention are not particularly limited in their kinematic viscosities, but the lower limit of the kinematic viscosity at 100 ° C. is 1 mm. 2 / S, preferably 2 mm 2 On the other hand, the upper limit of the kinematic viscosity at 100 ° C. is 5 mm. 2 / S, preferably 4mm 2 / S, particularly preferably 3.5 mm 2 / S is desirable. The kinematic viscosity at 100 ° C of the lubricating base oil is 1 mm. 2 By setting it to / s or more, it becomes possible to obtain a lubricating oil composition that has sufficient oil film formation, is excellent in lubricity, and has a smaller base oil evaporation loss under high-temperature conditions. On the other hand, the kinematic viscosity at 100 ° C is 5 mm. 2 By setting it to / s or less, it becomes possible to obtain a lubricating oil composition having a smaller frictional resistance because the fluid resistance is smaller.
[0019]
Further, these lubricating base oils in the present invention are not particularly limited in the viscosity index, but the viscosity index is desirably 80 or more, preferably 90 or more, and particularly preferably 110 or more. By setting the viscosity index to 80 or more, it is possible to obtain a composition having excellent wear resistance after long-term use.
[0020]
The component (B) of the present invention is a nitrogen-containing compound and / or a derivative thereof having at least one alkyl group or alkenyl group having a number average molecular weight of 900 or more, and one or two kinds arbitrarily selected from these compounds The above can be mix | blended.
[0021]
As the component (B), specifically, for example,
(B-1) Succinimide or derivative thereof having at least one alkyl group or alkenyl group having a number average molecular weight of 900 or more
(B-2) Benzylamine or a derivative thereof having at least one alkyl group or alkenyl group having a number average molecular weight of 900 or more
(B-3) Polyamine having at least one alkyl group or alkenyl group having a number average molecular weight of 900 or more or a derivative thereof
1 type, or 2 or more types of compounds chosen from among these are mentioned.
[0022]
More specifically, examples of the (B-1) succinimide include compounds represented by the following formula (1) or (2).
[Chemical 1]
Figure 0004571776
[0023]
In the above formula (1), R 1 Represents an alkyl group or alkenyl group having a number average molecular weight of 900 or more, and a represents an integer of 1 to 5, preferably 2 to 4.
[Chemical 2]
Figure 0004571776
[0024]
In the above formula (2), R 2 And R 3 Each independently represents an alkyl group or an alkenyl group having a number average molecular weight of 900 or more, and b represents an integer of 0 to 4, preferably 1 to 3.
[0025]
The succinimide is a so-called monotype succinimide having the formula (1) in which succinic anhydride is added to one end of the polyamine, and succinic anhydride is added to both ends of the polyamine. There is a so-called bis-type succinimide such as the formula (2), and any of the components (B-1) can be used, but the wear resistance is maintained even after the initial and long-term use. Since it is easy, it is preferable that it is a succinimide which has a bis type, ie, two alkyl groups or alkenyl groups with a number average molecular weight of 900 or more.
[0026]
More specifically, examples of the (B-2) benzylamine include compounds represented by the following formula (3).
[Chemical 3]
Figure 0004571776
[0027]
In the above formula (3), R 4 Represents an alkyl group or alkenyl group having a number average molecular weight of 900 or more, and c represents an integer of 1 to 5, preferably 2 to 4.
[0028]
The production method of this benzylamine is not limited in any way. For example, after reacting polyolefin such as propylene oligomer, polybutene, ethylene-α-olefin copolymer with phenol to form alkylphenol, formaldehyde and diethylenetriamine are added thereto. It can be obtained by reacting polyamines such as triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and the like by Mannich reaction.
[0029]
More specifically, examples of the (B-3) polyamine include compounds represented by the following formula (4).
[Formula 4]
Figure 0004571776
[0030]
In the above formula (4), R 5 Represents an alkyl group or alkenyl group having a number average molecular weight of 900 or more, and d represents an integer of 1 to 5, preferably 2 to 4.
[0031]
Although the production method of this polyamine is not limited at all, for example, after chlorinating polyolefin such as propylene oligomer, polybutene, ethylene-α-olefin copolymer, ammonia, ethylenediamine, diethylenetriamine, triethylenetetramine It can be obtained by reacting polyamines such as tetraethylenepentamine and pentaethylenehexamine.
[0032]
Specific examples of derivatives of nitrogen-containing compounds such as succinimide, benzylamine, polyamine and the like in the component (B) include monocarboxylic acids having 2 to 30 carbon atoms in addition to the nitrogen-containing compounds described above. (Fatty acids etc.), oxalic acid, phthalic acid, trimellitic acid, pyromellitic acid, etc., C2-C30 polycarboxylic acids or their anhydrides, ester compounds, C2-C6 alkylene oxides, hydroxy ( Poly) oxyalkylene carbonate or the like, so-called acid-modified compound obtained by neutralizing or amidating part or all of the remaining amino group and / or imino group; By reacting a boron compound such as an acid, borate or borate ester, a part of the remaining amino group and / or imino group or A so-called boron-modified compound obtained by neutralizing or amidating a part; a sulfur-modified compound in which a sulfur compound is allowed to act on the nitrogen-containing compound as described above; and an acid-modified, boron-modified, sulfur in the nitrogen-containing compound as described above And a modified compound in which two or more kinds of modifications selected from modification are combined.
[0033]
The alkyl group or alkenyl group having a number average molecular weight of 900 or more in the component (B) of the present invention may be linear or branched, but specific examples include propylene, 1-butene, Examples thereof include branched alkyl groups and branched alkenyl groups derived from olefin oligomers such as isobutylene and ethylene / propylene co-oligomers, preferably poly (iso) butenyl groups, and the number average molecular weight is preferably 1200. Or more, more preferably 1700 or more, further preferably 2000 or more, and particularly preferably 2300 or more. Further, the upper limit of the number average molecular weight is not particularly limited, but is preferably 5000 or less, more preferably 3500 or less, and particularly preferably 3000 or less. By setting the number average molecular weight of the alkyl group or alkenyl group to 900 or more, it is easy to maintain the wear prevention property after long-term use, and by setting it to 5000 or less, a composition having excellent low-temperature fluidity can be obtained. it can.
[0034]
The nitrogen content of the component (B) nitrogen-containing compound is arbitrary, but from the viewpoint of wear resistance, oxidation stability, friction characteristics, etc., the nitrogen content is usually 0.01 to 10% by mass, preferably 0.1 to 10% by mass is desirably used.
As the component (B) in the lubricating oil composition of the present invention, the alkyl or alkenyl succinimide having the number average molecular weight as described above can be more preferably used because it can easily maintain the wear resistance. Further, since the boron-modified compound of alkyl or alkenyl succinimide having a number average molecular weight of 2000 or more, particularly the number average molecular weight as described above, is most excellent in wear resistance after initial and long-term use, the boron-modified compound is used. It is particularly preferable to contain it as an essential component.
[0035]
In addition, the mass ratio (B / N ratio) of boron and nitrogen in the boron-modified compound of the nitrogen-containing compound is not particularly limited, and is usually 0.01 to 3, preferably 0.05 or more, and more Preferably it is 0.1 or more, More preferably, it is 0.2 or more, Preferably it is 1 or less, More preferably, it is 0.8 or less, More preferably, it is 0.6 or less. By selecting a boron-modified compound having a B / N ratio in the above range, a composition excellent in wear resistance can be obtained even at the initial stage and after long-term use. When the nitrogen-containing compound and its boron-modified compound are used in combination, for example, a bis-type succinimide having a poly (iso) butenyl group having a number average molecular weight of 900 to less than 2000 and a bis-type having a number average molecular weight of 2000 or more. When used in combination with a boron-modified compound of type poly (iso) butenyl succinimide, it is possible to synergistically improve the wear resistance after initial and long-term use. Even in such a case, it is preferable that the mass ratio of the boron derived from the boron-modified compound and the total nitrogen derived from the component (B) is also in the above range.
[0036]
In the lubricating oil composition of the present invention, the lower limit of the content of the component (B) is 0.01% by mass, preferably 0.02% by mass as the nitrogen content, based on the total amount of the lubricating oil composition. The upper limit of the content is 0.2% by mass, preferably 0.18% by mass as the amount of nitrogen, based on the total amount of the lubricating oil composition. When the content of the component (B) is less than 0.01% by mass as the nitrogen content based on the total amount of the lubricating oil composition, it is difficult to maintain anti-wear properties after long-term use due to the content of the component (B). When it exceeds 2 mass%, the low-temperature fluidity | liquidity of a lubricating oil composition deteriorates, and it is unpreferable respectively. In the case where the component (B) is a nitrogen-containing compound having two alkyl groups or alkenyl groups having a number average molecular weight of 1200 or more, the upper limit of the content can be 0.07% by mass or less, In the case of a nitrogen-containing compound having two alkyl groups or alkenyl groups having a number average molecular weight of 2000 or more, sufficient wear resistance can be exhibited even if the number average molecular weight is 0.04% by mass or less.
[0037]
Further, when the boron-modified compound of the nitrogen-containing compound is essential as the component (B), the lower limit of the content is preferably 0.002% by mass or more, more preferably 0.004 as the boron content. It is at least mass%, particularly preferably at least 0.008 mass%. Moreover, the upper limit of the content is preferably 0.05% by mass or less, more preferably 0.02% by mass or less, and particularly preferably 0.015% by mass or less as the amount of boron. By setting the boron-modified compound as the component (B) in the above preferred range as the amount of boron, it is possible to maintain better wear resistance even after the initial and long-term use.
[0038]
The component (C) in the present invention is a viscosity index improver having a weight average molecular weight of 40,000 or less, specifically, a non-dispersion type viscosity index improver and / or a dispersion type having a weight average molecular weight of 40,000 or less. A viscosity index improver etc. are mentioned.
[0039]
Specific examples of the non-dispersion type viscosity index improver include one or more monomers (C-) selected from compounds represented by the following formulas (5), (6) and (7). Examples thereof include the copolymer 1) or a hydride thereof. On the other hand, as the dispersion type viscosity index improver, specifically, a copolymer of two or more monomers selected from the compounds represented by the general formulas (8) and (9) or a hydride thereof may be oxygenated. One or two or more monomers (C-1) and general formulas (8) and (9) selected from compounds having a group introduced therein or compounds represented by general formulas (5) to (7) Examples thereof include a copolymer with one or more monomers (C-2) selected from the compounds represented by the formula (II), a hydride thereof, and the like.
[Chemical formula 5]
Figure 0004571776
[0040]
In the above formula (5), R 6 Represents hydrogen or a methyl group, R 7 Represents an alkyl group having 1 to 18 carbon atoms.
[0041]
R 7 Specific examples of the alkyl group having 1 to 18 carbon atoms are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and undecyl. , Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group and the like (these alkyl groups may be linear or branched).
[Chemical 6]
Figure 0004571776
[0042]
In the above formula (6), R 8 Represents hydrogen or a methyl group, R 9 Represents a hydrocarbon group having 1 to 12 carbon atoms.
[0043]
R 9 Specific examples of the hydrocarbon group having 1 to 12 carbon atoms are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and undecyl. Group, alkyl group such as dodecyl group (these alkyl groups may be linear or branched); butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group Alkenyl groups such as these (the alkenyl groups may be linear or branched, and the position of the double bond is arbitrary); C5-C7 cycloalkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl Methylcyclopentyl group, dimethylcyclopentyl group, methylethylcyclopentyl group, diethylcyclopentyl group, methyl Alkylcycloalkyl groups having 6 to 11 carbon atoms such as cyclohexyl group, dimethylcyclohexyl group, methylethylcyclohexyl group, diethylcyclohexyl group, methylcycloheptyl group, dimethylcycloheptyl group, methylethylcycloheptyl group and diethylcycloheptyl group (these The substitution position of the alkyl group to the cycloalkyl group is arbitrary); aryl groups such as phenyl group and naphthyl group: tolyl group, xylyl group, ethylphenyl group, propylphenyl group, butylphenyl group, pentylphenyl group, hexylphenyl Each alkylaryl group having 7 to 12 carbon atoms such as a group (these alkyl groups may be linear or branched, and the substitution position on the aryl group is arbitrary); benzyl group, phenylethyl group, phenylpropyl Group, phenylbutyl group, phenyl Pentyl group, each phenyl alkyl group having 7 to 12 carbon atoms such as a phenyl hexyl group (the alkyl group may be branched straight-chain); can be exemplified, and the like.
[Chemical 7]
Figure 0004571776
[0044]
In the above formula (7), D 1 And D 2 Are each independently a hydrogen atom, a residue of an alkyl alcohol having 1 to 18 carbon atoms (-OR: R is an alkyl group having 1 to 18 carbon atoms) or a residue of a monoalkylamine having 1 to 18 carbon atoms (- NHR: R represents an alkyl group having 1 to 18 carbon atoms.
[Chemical 8]
Figure 0004571776
[0045]
(8) where R 10 Represents a hydrogen atom or a methyl group, R 11 Represents an alkylene group having 1 to 18 carbon atoms; 1 Represents an amine residue or a heterocyclic residue containing 1 to 2 nitrogen atoms and 0 to 2 oxygen atoms. E is an integer of 0 or 1.
[0046]
R 11 Specific examples of the alkylene group having 1 to 18 carbon atoms include ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, and dodecylene. Group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group and the like (these alkylene groups may be linear or branched).
[0047]
E 1 Specific examples of the group represented by dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, anilino group, toluidino group, xylidino group, acetylamino group, benzoylamino group, morpholino group, pyrrolyl group, Examples include pyrrolino group, pyridyl group, methylpyridyl group, pyrrolidinyl group, piperidinyl group, quinonyl group, pyrrolidonyl group, pyrrolidono group, imidazolino group and pyrazino group.
[Chemical 9]
Figure 0004571776
[0048]
In the above formula (9), R 12 Represents a hydrogen atom or a methyl group, and E 2 Represents an amine residue or a heterocyclic residue containing 1 to 2 nitrogen atoms and 0 to 2 oxygen atoms.
[0049]
E 2 Specific examples of the group represented by dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, anilino group, toluidino group, xylidino group, acetylamino group, benzoylamino group, morpholino group, pyrrolyl group, Examples include pyrrolino group, pyridyl group, methylpyridyl group, pyrrolidinyl group, piperidinyl group, quinonyl group, pyrrolidonyl group, pyrrolidono group, imidazolino group and pyrazino group.
[0050]
Specific examples of the monomer (C-1) preferably include alkyl acrylates having 1 to 18 carbon atoms, alkyl methacrylates having 1 to 18 carbon atoms, olefins having 2 to 20 carbon atoms, styrene, methylstyrene, Examples thereof include maleic anhydride esters, maleic anhydride amides and mixtures thereof.
[0051]
Specific examples of the monomer (C-2) preferably include dimethylaminomethyl methacrylate, diethylaminomethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-methyl-5-vinylpyridine, morpholinomethyl methacrylate, Examples thereof include morpholinoethyl methacrylate, N-vinylpyrrolidone and a mixture thereof.
[0052]
In addition, at the time of copolymerizing the 1 type (s) or 2 or more types of monomers selected from the said (C-1) compound, and the 1 type (s) or 2 or more types of monomers selected from the (C-2) compound. The molar ratio of the component (C-1) and the component (C-2) is arbitrary, but is generally about 80:20 to 95: 5. Although the reaction method of copolymerization is arbitrary, it is usually easy to carry out copolymerization by subjecting the (C-1) component and the (C-2) component to radical solution polymerization in the presence of a polymerization initiator such as benzoyl peroxide. Coalescence is obtained.
[0053]
Specific examples of the component (C) include non-dispersed and dispersed polymethacrylates, non-dispersed and dispersed ethylene-α-olefin copolymers and hydrides thereof, polyisobutylene and hydrides thereof, and styrene-diene hydrogen. Copolymer, styrene-maleic anhydride ester copolymer, and polyalkylstyrene.
[0054]
In the present invention, the molecular weight of the component (C) is 40,000 or less, preferably 35,000 or less in terms of weight average molecular weight. If the weight average molecular weight exceeds 40,000, the anti-wear property after long-term use is inferior, which is not preferable. Further, the weight average molecular weight of the component (C) is not particularly limited, and 900 or more can be used, but it is preferably 10,000 or more, and more preferably 20,000 or more. (C) Viscosity index improver having a weight average molecular weight of less than 10,000, for example, polyisobutylene having a weight average molecular weight of less than 900 to 10,000 has a small effect of improving the viscosity index and needs to be blended in a large amount. Since it becomes difficult to maintain wear resistance after a period of use, the weight average molecular weight of the component (C) is preferably 10,000 or more.
[0055]
As the component (C) in the present invention, a non-dispersed polymethacrylate having a weight average molecular weight of 10,000 to 40,000 is particularly preferable because it can easily maintain the wear resistance after long-term use.
[0056]
The content of the component (C) in the lubricating oil composition of the present invention is desirably set so that the viscosity index of the composition is 160 or more, preferably 165 or more. On the other hand, it is desirable to set the content of component (C) so that the upper limit of the viscosity index of the composition is preferably less than 210, more preferably less than 190. The kinematic viscosity at 40 ° C. of the composition is 20 to 30 mm. 2 It is necessary to contain the component (C) in such an amount as to be / s, preferably 22 to 28 mm. 2 It is desirable to contain so that it may become / s. In the present invention, one or two or more compounds arbitrarily selected from the above viscosity index improvers are used so that the viscosity index of the composition and the kinematic viscosity at 40 ° C. are within the above specified range. Although it can mix | blend in arbitrary quantity, for example, the content is 1 mass% or more, Preferably it is 5 mass% or more, Most preferably, it is 6 mass% or more, and 20 mass% or less, Preferably it is 15 mass%. Hereinafter, it is particularly preferably 12% by mass or less. When the viscosity index of the composition is less than 160, the wear resistance after long-term use deteriorates, which is not preferable. When the kinematic viscosity at 40 ° C. is less than the above range, the wear resistance after initial and long-term use When the kinematic viscosity at 40 ° C. exceeds the above range, it is difficult to obtain fuel savings by reducing the stirring resistance, which is not preferable.
[0057]
In the present invention, the component (A) is a base oil, the component (B) is blended in a specific amount, the component (C) has a composition having a viscosity index of 160 or more, and the composition has a kinematic viscosity at 40 ° C. of 20 ~ 30mm 2 A lubricating oil composition having excellent anti-wear properties even after initial and long-term use can be obtained simply by using a low-viscosity lubricating oil composition blended in such an amount as to give / s. Then, if necessary, other types of additives may be further blended. Examples of such additives include antiwear or extreme pressure agents, metal detergents, friction modifiers, rust inhibitors, corrosion inhibitors, pour point depressants, rubber swelling agents, antifoaming agents, colorants, and the like. Can do. These compounds can be used alone or in combination of several kinds.
[0058]
Antiwear agents or extreme pressure agents that can be used in combination with the lubricating oil composition of the present invention include sulfur additives, phosphorus additives, sulfur and phosphorus additives, and other antiwear agents or extreme pressure agents for lubricating oils. Any compound that is normally used can be used.For example, sulfur compounds such as disulfides, sulfurized olefins, sulfurized fats and oils, phosphoric monoesters, phosphoric diesters, phosphoric triesters, Phosphorus monoesters, phosphite diesters, phosphite triesters, phosphorus compounds such as salts of these esters with amines or alkanolamines, sulfur such as zinc dithiophosphate and thiophosphate In addition, phosphorus compounds and the like can be used. The content of these antiwear agents or extreme pressure agents is not particularly limited, but is usually 0.01 to 5.0% by mass based on the total amount of the lubricating oil composition.
[0059]
As the metal-based detergent that can be used in combination with the lubricating oil composition of the present invention, any compound that is usually used as a metal-based detergent for lubricating oil can be used. For example, an alkali metal or alkaline earth metal Sulfonates, phenates, salicylates, naphthenates, and the like can be used alone or in combination of two or more in the composition of the present invention. Examples of the alkali metal include sodium and potassium, and examples of the alkaline earth metal include calcium and magnesium. In addition, calcium or magnesium sulfonates, phenates, and salicylates are preferably used as specific metal detergents. The total base number and content of these metal detergents can be arbitrarily selected according to the required performance of the lubricating oil. Usually, the total base number is 0 to 500 mgKOH / g by the perchloric acid method. And its content is 0.01 to 10% by mass.
[0060]
As the friction modifier that can be used in combination with the lubricating oil composition of the present invention, any compound that is usually used as a friction modifier for lubricating oils can be used, but an alkyl group or alkenyl group having 6 to 30 carbon atoms, In particular, amine compounds, fatty acid esters, fatty acid amides, fatty acid metal salts, and the like having at least one straight-chain alkyl group or straight-chain alkenyl group having 6 to 30 carbon atoms in the molecule are included.
[0061]
Examples of the amine compound include linear or branched, preferably linear aliphatic monoamines having 6 to 30 carbon atoms, linear or branched, preferably linear aliphatic polyamines, or fatty acids thereof. An alkylene oxide adduct of a group amine can be exemplified. Examples of fatty acid esters include esters of linear or branched, preferably linear, fatty acids having 7 to 31 carbon atoms with aliphatic monohydric alcohols or aliphatic polyhydric alcohols. Examples of the fatty acid amide include amides of linear or branched, preferably linear fatty acids having 7 to 31 carbon atoms, and aliphatic monoamines or aliphatic polyamines. Examples of the fatty acid metal salt include an alkaline earth metal salt (magnesium salt, calcium salt, etc.) or zinc salt of a linear or branched, preferably linear fatty acid having 7 to 31 carbon atoms.
[0062]
In the present invention, one kind or two or more kinds of compounds arbitrarily selected from these friction modifiers can be contained in any amount, but usually the content thereof is a lubricating oil composition. It is desirable that the content is 0.01 to 5.0% by mass, preferably 0.03 to 3.0% by mass.
[0063]
As the antioxidant that can be used in combination with the lubricating oil composition of the present invention, phenolic compounds and amine compounds that are generally used in lubricating oils can be used.
[0064]
Specifically, alkylphenols such as 2-6-di-tert-butyl-4-methylphenol, and bisphenols such as methylene-4,4-bisphenol (2,6-di-tert-butyl-4-methylphenol). , Naphthylamines such as phenyl-α-naphthylamine, dialkyldiphenylamines, zinc dialkyldithiophosphates such as zinc di-2-ethylhexyldithiophosphate, (3,5-di-tert-butyl-4-hydroxyphenyl) or ( 3-methyl-5-tert-butyl-4-hydroxyphenyl) fatty acid (propionic acid, etc.) and mono- or polyhydric alcohols such as methanol, octanol, octadecanol, 1,6 hexadiol, neopentyl glycol, thiodiethylene glycol , Triethylene glycol Esters of pentaerythritol and the like.
[0065]
One kind or two or more kinds of compounds arbitrarily selected from these can be contained in any amount, but the content is usually 0.01 to 5. based on the total amount of the lubricating oil composition. It is preferably 0% by mass.
[0066]
As the corrosion inhibitor that can be used in combination with the lubricating oil composition of the present invention, any compound that is usually used as a corrosion inhibitor for lubricating oils can be used. For example, benzotriazole, tolyltriazole, and thiadiazole And imidazole compounds. One or two or more compounds arbitrarily selected from these can be contained in any amount, but usually the content is 0.01 to 3. based on the total amount of the lubricating oil composition. It is preferably 0% by mass.
[0067]
As an antifoaming agent that can be used in combination with the lubricating oil composition of the present invention, any compound that is usually used as an antifoaming agent for lubricating oils can be used. For example, silicones such as dimethyl silicone and fluorosilicone can be used. Can be mentioned. One or two or more compounds arbitrarily selected from these can be contained in any amount, but the content is usually 0.001 to 0.00 on the basis of the total amount of the lubricating oil composition. It is desirable that it is 05 mass%.
[0068]
The lubricating oil composition of the present invention is excellent in wear resistance even after initial and long-term use, and can reduce the agitation resistance caused by the lubricating oil. Therefore, the lubricating oil composition for automobiles, for example, for internal combustion engines, transmissions, and particularly automatic By using it for a transmission or a continuously variable transmission, it is possible to contribute to an improvement in the fuel consumption of an automobile.
【Example】
Hereinafter, the content of the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
(Examples 1-5 and Comparative Examples 1-3)
[0069]
Various lubricating base oils and additives shown in Table 1 or Table 2 are blended to form a lubricating oil composition according to the present invention (Examples 1 to 5 in Table 1) and a comparative lubricating oil composition (Table 2). Comparative Examples 1 to 3) were prepared. The amount of each additive added is based on the total amount of the composition.
[0070]
About each obtained composition, the abrasion prevention property after an initial stage and long-term use was evaluated by the abrasion test shown to the following (1). In addition, new oil was used for initial wear prevention evaluation, and deteriorated oil previously deteriorated by the ultrasonic shear test shown in (2) was used for long-term use wear prevention evaluation. The results of the performance evaluation are shown in Table 1 and Table 2, respectively.
[0071]
(1) Wear test
The LFW-1 friction test was conducted under the following conditions in accordance with the test conditions specified in ASTM D2714, and the wear width of the block test piece after the test was measured. The smaller the wear width, the better the wear resistance.
(Test conditions)
Ring: Falex S-10 Test Ring
(SAE 4620 Steel)
Block: Falex H-30 Test Block
(SAE 01 Steel)
Test oil temperature: 100 ° C
Test load: 50 lb
Sliding speed: 100 cm / s
[0072]
(2) Ultrasonic shear test
In accordance with the automatic transmission oil shear stability test method specified in JASO M347-95, an 8 hour shear test was performed. This test evaluates the degree of decrease in kinematic viscosity during the use of automatic transmission oil. The 8-hour shear test is equivalent to 100,000 km or more of actual running, and the oil after this test runs 100,000 km It is thought to correspond to later oil.
[0073]
[Table 1]
Figure 0004571776
[0074]
[Table 2]
Figure 0004571776
[0075]
As is clear from the results shown in Table 1, in all of the lubricating oil compositions of Examples 1 to 5 according to the present invention, the wear prevention property of the deteriorated oil is hardly lowered as compared with the new oil. When a non-dispersed polymethacrylate having a weight average molecular weight of 30,000 is used as the component (C) (Example 2), a bistype having a polybutenyl group having a number average molecular weight of 1,300 as the component (B) When using a succinimide boron-modified compound of bis-type succinimide having a polybutenyl group having a number average molecular weight of 2,500 as the component (B) (Examples 4 and 5), Compared with the composition of Example 1, excellent results were obtained due to wear resistance even at the initial stage and after long-term use. Furthermore, when the succinimide used in Example 1 and the boron-modified compound of succinimide used in Example 5 were used in combination (Example 4), the result was that the anti-wear performance was synergistically improved. .
[0076]
On the other hand, when the content of the component (B) is less than the specified range of the present invention (Comparative Example 1), when the viscosity index of the composition is less than 160 (Comparative Example 2), the weight average of the component (C) When the molecular weight exceeded 40,000 (Comparative Example 3), the anti-wear property of the new oil was inferior, but the anti-wear property of the deteriorated oil was further deteriorated. The kinematic viscosity at 40 ° C. of the composition is 20 mm. 2 In the case of less than / s, the result of inferior wear resistance was inferior to that of the comparative example.
【The invention's effect】
The lubricating oil composition of the present invention is low in viscosity and excellent in wear resistance even after initial and long-term use, and can reduce the stirring resistance caused by the lubricating oil. It can contribute to the improvement of the fuel consumption of an automobile by using it for a machine, particularly for an automatic transmission or a continuously variable transmission. In addition, for lubricants for machines and devices other than automobiles, it is possible to suppress energy consumption of the machines and devices while maintaining wear prevention. For example, for wet brakes, hydraulic actuators, compression It is useful for various uses such as for machines, turbines, gears, refrigerators, and bearings.

Claims (7)

(A)100℃における動粘度が2mm/s以上3.5mm/s以下であり、粘度指数が95以上である、鉱油、合成油又は、それらの混合油からなる潤滑油基油に、
(B)数平均分子量が1000以上2500以下のポリブテニル基を有するビスタイプのコハク酸イミドのホウ素変性化合物を組成物全量基準で、窒素含有量として0.01〜0.20質量%、及び
(C)重量平均分子量が20,000以上30,000以下の非分散型ポリメタアクリレート系粘度指数向上剤を、該(C)成分の含有量が組成物全量基準で1質量%以上20質量%以下となるように、配合してなり、
粘度指数が160以上、かつ、40℃に於ける動粘度が20〜30mm /sである、ことを特徴とする潤滑油組成物。
(A) To a lubricating base oil composed of mineral oil, synthetic oil or a mixed oil thereof having a kinematic viscosity at 100 ° C. of 2 mm 2 / s or more and 3.5 mm 2 / s or less and a viscosity index of 95 or more,
(B) A boron modified compound of a bis-type succinimide having a polybutenyl group having a number average molecular weight of 1000 or more and 2500 or less is 0.01 to 0.20% by mass as a nitrogen content based on the total amount of the composition, and (C ) A non-dispersed polymethacrylate viscosity index improver having a weight average molecular weight of 20,000 or more and 30,000 or less, and the content of the component (C) is 1% by mass or more and 20% by mass or less based on the total amount of the composition. so as to, Ri Na compounded,
A lubricating oil composition having a viscosity index of 160 or more and a kinematic viscosity at 40 ° C. of 20 to 30 mm 2 / s .
前記(B)成分が、数平均分子量が1200以上2500以下のポリブテニル基を有するビスタイプのコハク酸イミドのホウ素変性化合物であることを特徴とする請求項1に記載の潤滑油組成物。The lubricating oil composition according to claim 1, wherein the component (B) is a boron-modified compound of a bis-type succinimide having a polybutenyl group having a number average molecular weight of 1200 or more and 2500 or less. 前記(B)成分を、組成物全量基準で、ホウ素含有量として0.002質量%以上含有することを特徴とする請求項1又は2に記載の潤滑油組成物。The lubricating oil composition according to claim 1, wherein the component (B) is contained in an amount of 0.002% by mass or more as a boron content based on the total amount of the composition. 前記(C)成分の含有量が、6質量%以上12質量%以下であることを特徴とする請求項1〜3のいずれかの項に記載の潤滑油組成物。Content of the said (C) component is 6 mass% or more and 12 mass% or less, The lubricating oil composition in any one of Claims 1-3 characterized by the above-mentioned. 前記(B)成分が、数平均分子量が900以上2000未満のポリブテニル基を有するビスタイプのコハク酸イミドと数平均分子量が2000以上のポリブテニル基を有するビスタイプのコハク酸イミドのホウ素変性化合物とを併用したものであることを特徴とする請求項1〜4のいずれかの項に記載の潤滑油組成物。The component (B) is a bis-type succinimide having a polybutenyl group having a number average molecular weight of 900 or more and less than 2000, and a boron-modified compound of a bis-type succinimide having a polybutenyl group having a number average molecular weight of 2000 or more. The lubricating oil composition according to any one of claims 1 to 4, wherein the lubricating oil composition is used in combination. 自動変速機あるいは無段変速機に使用されることを特徴とする請求項1〜5のいずれかの項に記載の潤滑油組成物。The lubricating oil composition according to any one of claims 1 to 5, which is used for an automatic transmission or a continuously variable transmission. 請求項1〜6のいずれかの項に記載の潤滑油組成物を使用することを特徴とする自動変速機あるいは無段変速機の摩耗防止性維持方法。A method for maintaining wear resistance of an automatic transmission or a continuously variable transmission, wherein the lubricating oil composition according to any one of claims 1 to 6 is used.
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