JP2004359708A - Additive for lubricating oil and for fuel oil, and lubricating oil composition and fuel oil composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an extreme pressure additive used for a lubricating oil and for a fuel oil, which exhibits excellent functions as the extreme pressure additive or an anti-abrasion agent free from harmful phosphorus and heavy metals. <P>SOLUTION: The additive for the lubricating oil and for the fuel oil is mainly composed of an ether group-containing 2,2',2"-nitrilotriethyl borate represented by formula (I) [wherein R<SP>1</SP>is a CH<SB>2</SB>-O-CR<SB>3</SB>group (wherein Rs are the same or different, hydrogen atom or a 1-20C hydrocarbon group and may be linked together to form a ring; and the hydrocarbon group may contain an oxygen atom, a sulfur atom or a nitrogen atom); and R<SP>2</SP>-R<SP>12</SP>are each independently hydrogen atom, a 1-20C hydrocarbon group or R<SP>1</SP>]. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【００１２】
［式中、Ｒ^１は−ＣＨ_２−Ｏ−ＣＲ_３基を示し（ただし、Ｒは水素原子又は炭素数１〜２０の炭化水素基であって、それぞれ同一でも異なってもよく、Ｒ同士が環を形成してもよい。この炭化水素基は酸素原子、硫黄原子又は窒素原子を含んでいてもよい。）、Ｒ^２〜Ｒ^１２は、それぞれ独立に水素原子、炭素数１〜２０の炭化水素基又はＲ^１を示す。］
で表されるエーテル基含有２，２’，２’’−ニトリロトリエチルボレートを主成分とする潤滑油用添加剤、
（２）一般式（Ｉ）で表されるエーテル基含有２，２’，２’’−ニトリロトリエチルボレートを主成分とする燃料油用添加剤、
（３）（Ａ）潤滑油基油と、（Ｂ）上記（１）の潤滑油用添加剤を含むことを特徴とする潤滑油組成物、
（４）さらに、（Ｃ）酸化防止剤、清浄分散剤及び粘度指数向上剤の中から選ばれる少なくとも一種を含むものである上記（３）の潤滑油組成物、及び
（５）（Ｘ）燃料油と、（Ｙ）上記（２）の燃料油用添加剤を含むことを特徴とする燃料油組成物、
を提供するものである。
【００１３】
【発明の実施の形態】
本発明の潤滑油用及び燃料油用添加剤に用いられる一般式（Ｉ）で表される化合物は、下記の構造
【００１４】
【化４】

【００１５】
を有するエーテル基含有２，２’，２’’−ニトリロトリエチルボレートである。
前記一般式（Ｉ）において、Ｒ^１は−ＣＨ_２−Ｏ−ＣＲ_３基を示す。ここでＲは水素原子又は炭素数１〜２０の炭化水素基であって、それぞれ同一でも異なってもよく、Ｒ同士が結合して環を形成してもよい。この炭化水素基は酸素原子、硫黄原子又は窒素原子を含んでいてもよい。
上記ＣＲ_３は、炭素数１〜１２の炭化水素基が好ましく、さらに炭素数３〜８の炭化水素基が好ましい。炭素数１〜２０の炭化水素基としては、例えば、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基などを挙げることができる。ここで、炭素数１〜２０のアルキル基は直鎖状、分岐状、環状のいずれであってもよく、具体的にはメチル基、エチル基、ｎ−プロピル基、イソプロピル基、各種ブチル基、各種ペンチル基、各種ヘキシル基、各種オクチル基、各種デシル基、各種ドデシル基、シクロペンチル基、シクロヘキシル基、メチルシクロヘキシル基などが挙げられる。炭素数６〜２０のアリール基の例としては、フェニル基、トリル基、キシリル基、ブチルフェニル基、ナフチル基などが、炭素数７〜２０のアラルキル基の例としては、ベンジル基、フェネチル基、ナフチルメチル基などが挙げられる。
【００１６】
一方、Ｒ^２〜Ｒ^１２は、それぞれ水素原子、炭素数１〜２０の炭化水素基又はＲ^１を示す。ここで、炭素数１〜２０の炭化水素基としては、炭素数１〜２０の炭化水素基として前記で例示した基を挙げることができる。Ｒ^２〜Ｒ^１２は、たがいに同一であっても異なっていてもよいが、製造上の理由から、（１）Ｒ^２〜Ｒ^１２が全て水素原子、（２）Ｒ^５＝Ｒ^９＝Ｒ^１であって、その他は水素原子又はメチル基、（３）Ｒ^５＝Ｒ^１であって、その他は水素原子又はメチル基であることが好ましい。
本発明の一般式（１）で示されるエーテル基含有２，２’，２’’−ニトリロトリエチルボレートの代表例としては、２，２’，２’’−ニトリロ−１−アルコキシメチルトリエチルボレート、２，２’，２’’−ニトリロ−１，１’−ジアルコキシメチルトリエチルボレート、２，２’，２’’−ニトリロ−１，１’，１’’−トリアルコキシメチルトリエチルボレートなどが挙げられる。
【００１７】
本発明の一般式（Ｉ）で示されるエーテル基含有２，２’，２’’−ニトリロトリエチルボレートは種々の方法で製造することができるが、通常、エーテル基含有２，２’，２’’−ニトリロトリエタノールを得た後、それをホウ酸などでエステル化することにより製造することができる。
原料のエーテル基含有２，２’，２’’−ニトリロトリエタノールは、例えば、下記の反応式（ａ）、（ｂ）及び（ｃ）
【００１８】
【化５】

【００１９】
（式中、Ｒ^１３は前記ＣＲ_３と同じであり、Ｒ^１４〜Ｒ^２４は前記Ｒ^２〜Ｒ^１２と同じである。）
で示されるように、グリシジルエーテル類（ＩＩ）とアンモニアを反応させて、２，２’，２’’−ニトリロトリエタノール（ＩＩＩ）を製造する方法［反応式（ａ）］、グリシジルエーテル類（ＩＩ）とモノエタノールアミン類（ＩＶ）を反応させて、２，２’，２’’−ニトリロトリエタノール（Ｖ）を製造する方法［反応式（ｂ）］、グリシジルエーテル類（ＩＩ）とジエタノールアミン類（ＶＩ）を反応させて、２，２’，２’’−ニトリロトリタノール（ＶＩＩ）を製造する方法［反応式（ｃ）］などによって、製造することができる。
前記グルシジルエーテル類（ＩＩ）としては、例えばメチルグリシジルエーテル、エチルグリシジルエーテル、ブチルグリシジルエーテル、ｔｅｒｔ−ブチルグリシジルエーテル、２−エチルヘキシルグリシジルエーテル、２−メチルオクチルグリシジルエーテル、フェニルグリシジルエーテル、ｓｅｃ−ブチルフェニルグリシジルエーテル、ベンジルグリシジルエーテルなどが挙げられる。このグリシジルエーテル類は、例えば、エピクロルヒドリンとアルコール類から公知の方法で製造することができる。分岐アルキル基をもつグリシジルエーテル類が好ましく、２−エチルヘキシルグリシジルエーテルが特に好ましい。また、前記モノエタノールアミン類（ＩＶ）としては、例えばエタノールアミン、１−アミノ−２−プロパノール、２−アミノ−１−プロパノール、１−アミノ−２−ブタノール、２−アミノ−２−メチル−１−プロパノール、２−アミノ−１−フェニルエタノール、フェニルアラニノールなどが挙げられる。このモノエタノールアミン類は、例えばエポキシ化合物とアンモニアを反応させる公知の方法により製造することができる。さらに前記ジエタノールアミン類（ＶＩ）としては、例えばジエタノールアミン、ジプロパノールアミン、２，２’−イミノジ（１−フェニルエタノール）などがある。このジエタノールアミン類は、例えばエポキシ化合物とアンモニア又はエタノールアミン類を反応させる公知の方法により製造することができる。
【００２０】
前記方法で得られたエーテル類含有２，２’，２’’−ニトリロトリエタノールをホウ酸、メタホウ酸、ホウ酸トリエステルなどのホウ素化合物と反応させて、エーテル基含有２，２’，２’’−ニトリロトリエチルボレートを得ることができる。反応時に生成する水、アルコールを蒸留などにより除去する。目的物は必要に応じて再結晶などの方法で精製する。
前記一般式（Ｉ）で表されるエーテル基含有２，２’，２’’−ニトリロトリエチルボレートの具体例としては、３−メトキシメチル−２，８，９−トリオキサ−５−アザ−１−ボラビシクロ［３．３．３］ウンデカン、３，７−ジメトキシメチル−２，８，９−トリオキサ−５−アザ−１−ボラビシクロ［３．３．３］ウンデカン、２，２’，２’’−ニトリロトリ−１−メトキシメチルエチルボレート、３−エトキシメチル−２，８，９−トリオキサ−５−アザ−１−ボラビシクロ［３．３．３］ウンデカン、３，７−ジエトキシメチル−２，８，９−トリオキサ−５−アザ−１−ボラビシクロ［３．３．３］ウンデカン、２，２’，２’’−ニトリロトリ−１−エトキシメチルエチルボレート、３−ブトキシメチル−２，８，９−トリオキサ−５−アザ−１−ボラビシクロ［３．３．３］ウンデカン、３，７−ジブトキシメチル−２，８，９−トリオキサ−５−アザ−１−ボラビシクロ［３．３．３］ウンデカン、２，２’，２’’−ニトリロトリ−１−ブトキシメチルエチルボレート、３−（２−エチルヘキソキシメチル）−２，８，９−トリオキサ−５−アザ−１−ボラビシクロ［３．３．３］ウンデカン、３，７−ジ（２−エチルヘキソキシメチル）−２，８，９−トリオキサ−５−アザ−１−ボラビシクロ［３．３．３］ウンデカン、２，２’，２’’−ニトリロトリ−１−（２−エチルヘキソキシメチル）エチルボレート、３−フェノキシメチル−２，８，９−トリオキサ−５−アザ−１−ボラビシクロ［３．３．３］ウンデカン、３，７−ジフェノキシメチル−２，８，９−トリオキサ−５−アザ−１−ボラビシクロ［３．３．３］ウンデカン、２，２’，２’’−ニトリロトリ−１−フェノキシメチルポレート、３，７−ジメチル−１０−（２−エチルヘキソキシメチル）−２，８，９−トリオキサ−５−アザ−１−ボラビシクロ［３．３．３］ウンデカン、３，７−ジ−２−エチルヘキソキシメチル−１０−メチル−２，８−９−トリオキサ−５−アザ−１−ボラビシクロ［３．３．３］ウンデカン、３，７−ジ−２−エチルヘキソキシメチル−１０−フェニル−２，８，９−トリオキサ−５−アザ−１−ボラビシクロ［３．３．３］ウンデカンなどを挙げることができる。
【００２１】
これらのエーテル基含有２，２’，２’’−ニトリロトリエチルボレートは、有害なリンや重金属を含有しない極圧添加剤として、耐荷重能及び耐摩耗性に優れており、潤滑油用及び燃料用添加剤として用いられる。
本発明の潤滑油用及び燃料油用添加剤においては、前記一般式（Ｉ）で表されるエーテル基含有２，２’，２’’−ニトリロトリエチルボレートを一種含んでいてもよく、二種以上含んでいてもよい。
次に、本発明の潤滑油組成物は、（Ａ）潤滑油基油と、（Ｂ）前述のエーテル基含有２，２’，２’’−ニトリロトリエチルボレートを含む潤滑油用添加剤を含有するものである。なお、本発明でいう潤滑油組成物には、内燃機関や、自動変速機、緩衝器、パワーステアリングなどの駆動系機器、ギヤなどに用いられる自動車用潤滑油、切削加工、研削加工、塑性加工などの金属加工に用いられる金属加工油、油圧機器や装置などの油圧システムにおける動力伝達、力の制御、緩衝などの作動に用いる動力伝達流体でもある作動油などとして用いられるものなどを含む。
【００２２】
本発明の潤滑油組成物において、（Ａ）成分として用いられる潤滑油基油としては特に制限はなく、該組成物の使用目的や使用条件などに応じて鉱油や合成油の中から適宜選ばれる。ここで、鉱油としては、例えばパラフィン基系原油、中間基系原油又はナフテン基系原油を常圧蒸留するか、あるいは常圧蒸留の残渣油を減圧蒸留して得られる留出油、又はこれらを常法に従って精製することによって得られる精製油、具体的には溶剤精製油、水添精製油、脱ロウ処理油、白土処理油などが挙げられる。
また、合成油としては、例えば低分子量ポリブテン、低分子量ポリプロピレン、炭素数８〜１４のα−オレフィンオリゴマー及びこれらの水素化物、さらにはポリオールエステル（トリメチロールプロパンの脂肪酸エステル、ペンタエリスリトールの脂肪酸エステルなど）や二塩基酸エステル、芳香族ポリカルボン酸エステル、リン酸エステルなどのエステル系化合物、アルキルベンゼン、アルキルナフタレンなどのアルキルアロマ系化合物、ポリアルキレングリコールなどのポリグリコール油、シリコーン油などが挙げられる。
【００２３】
これらの基油は、一種を用いてもよく、二種以上を適宜組み合せて用いてもよい。
本発明の潤滑油組成物における（Ｂ）成分の潤滑油用添加剤の含有量は、該組成物の使用目的や使用条件などに応じて適宜選定されるが、一般に０．０１〜５０質量％の範囲である。そして、自動車用潤滑油や作動油の場合、通常０．０１〜３０質量％、好ましくは０．０１〜１０質量％の範囲であり、金属加工油の場合、添加剤単独でも使用することができるが、通常０．１〜６０質量％、好ましくは０．１〜５０質量％の範囲で選定される。
本発明の潤滑油組成物は、さらに（Ｃ）成分として、酸化防止剤、清浄分散剤及び粘度指数向上剤の中から選ばれる少なくとも一種を含むことが好ましい。
【００２４】
前記酸化防止剤としては、例えば、アルキル化ジフェニルアミン、フェニル−α−ナフチルアミン、アルキル化−ナフチルアミンなどのアミン系酸化防止剤、２，６−ジ−ｔ−ブチル−ｐ−クレゾール、４，４’−メチレンビス（２，６−ジ−ｔ−ブチルフェノール）などのフェノール系酸化防止剤などを挙げることができる。また、清浄分散剤には、無灰系分散剤及び金属系清浄剤があり、無灰系分散剤としては、例えばコハク酸イミド類、ホウ素含有コハク酸イミド類、ベンジルアミン類、ホウ素含有ベンジルアミン類、コハク酸エステル類、脂肪酸あるいはコハク酸で代表される一価又は二価のカルボン酸のアミド類などが挙げられ、金属系清浄剤としては、例えば中性金属スルホネート、中性金属フェネート、中性金属サリチレート、中性金属ホスホネート、塩基性スルホネート、塩基性フェネート、塩基性サリチレート、塩基性ホスホネート、過塩基性スルホネート、過塩基性フェネート、過塩基性サリチレート、過塩基性ホスホネートなどが挙げられる。さらに、粘度指数向上剤としては、例えば、ポリメタクリレート、分散型ポリメタクリレート、オレフィン系共重合体（例えば、エチレン−プロピレン共重合体など）、分散型オレフィン系共重合体、スチレン系共重合体（例えば、スチレン−ジエン水素化共重合体など）などが挙げられる。
【００２５】
本発明の潤滑油組成物においては、使用目的に応じ、その他の各種添加剤、例えば他の摩擦調整剤（油性剤、他の極圧添加剤）や耐摩耗剤、流動点降下剤、防錆剤、金属腐食防止剤、消泡剤、界面活性剤などを適宜含有させることができる。
他の摩擦調整剤や耐摩耗剤としては、例えば硫化オレフィン、ジアルキルポリスルフィド、ジアリールアルキルポリスルフィド、ジアリールポリスルフィドなどの硫黄系化合物、リン酸エステル、チオリン酸エステル、亜リン酸エステル、アルキルハイドロゲンホスファイト、リン酸エステルアミン塩、亜リン酸エステルアミン塩などのリン系化合物、塩素化油脂、塩素化パラフィン、塩素化脂肪酸エステル、塩素化脂肪酸などの塩素系化合物、アルキル若しくはアルケニルマレイン酸エステル、アルキル若しくはアルケニルコハク酸エステルなどのエステル系化合物、アルキル若しくはアルケニルマレイン酸、アルキル若しくはアルケニルコハク酸などの有機酸系化合物、ナフテン酸塩、ジチオリン酸亜鉛（ＺｎＤＴＰ）、ジチオカルバミン酸亜鉛（ＺｎＤＴＣ）、硫化オキシモリブデンオルガノホスホロジチオエート（ＭｏＤＴＰ）、硫化オキシモリブデンジチオカルバメート（ＭｏＤＴＣ）などの有機金属系化合物などが挙げられる。
流動点降下剤としては、例えばポリメタクリレートなどが、防錆剤としては、例えば、アルケニルコハク酸やその部分エステルなどが、金属腐食防止剤としては、例えば、ベンゾトリアゾール系、ベンズイミダゾール系、ベンゾチアゾール系、チアジアゾール系などが、消泡剤としては、例えば、ジメチルポリシロキサン、ポリアクリレートなどが、界面活性剤としては、例えば、ポリオキシエチレンアルキルフェニルエーテルなどが用いられる。
【００２６】
本発明の潤滑油組成物は、例えば内燃機関や、自動変速機、緩衝器、パワーステアリングなどの駆動系機器、ギヤなどに用いられる自動車用潤滑油、切削加工、研削加工、塑性加工などの金属加工に用いられる金属加工油、油圧機器や装置などの油圧システムにおける動力伝達、力の制御、緩衝などの作動に用いる動力伝達流体である作動油などとして用いられる。
一方、本発明の燃料油組成物は、（Ｘ）燃料油と、（Ｙ）前述のエーテル基含有２，２’，２’’−ニトリロトリエチルボレートを含む燃料油用添加剤を含有するものである。
【００２７】
本発明の燃料油組成物において、（Ｘ）成分である燃料油としては、高度に水素化精製された燃料油、例えば高性能タービン燃料油などが好ましく用いられる。
本発明の燃料油組成物における（Ｙ）成分の燃料油用添加剤の含有量は、通常０．０１〜１，０００ｐｐｍ、好ましくは０．０１〜１００ｐｐｍの範囲である。
本発明の燃料油組成物においては、必要に応じて、各種の添加剤を適宜配合することができる。このような添加剤としては、例えば、フェニレンジアミン系、ジフェニルアミン系、アルキルフェノール系、アミノフェノール系などの酸化防止剤、ポリエーテルアミン、ポリアルキルアミンなどの清浄剤、シッフ型化合物やチオアミド型化合物などの金属不活性剤、有機リン系化合物などの表面着火防止剤、多価アルコールやエーテルなどの氷結防止剤、有機酸のアルカリ金属塩やアルカリ土類金属塩、高級アルコールの硫酸エステルなどの助燃剤、アニオン性界面活性剤、カチオン性界面活性剤、両性界面活性剤などの帯電防止剤、アルケニルコハク酸のエステルなどの錆止剤、キニザリン、クマリンなどの識別剤、天然精油、合成香料などの着臭剤、アゾ染料などの着色剤など公知の燃料油添加剤が挙げられる。
【００２８】
【実施例】
次に、本発明を実施例により、さらに詳細に説明するが、本発明は、これらの例によってなんら限定されるものではない。
なお、潤滑油組成物の摩擦係数、摩耗痕径及び腐食性は、以下に示す方法に従って求めた。
（１）耐焼付き性
ＡＳＴＭ Ｄ３２３３−９３Ａ法に準拠しファレックス試験によって焼付き荷重（Ｎ）を求めた。測定条件は回転数２９０ｒｐｍ、油度８０℃である。
（２）耐荷重性試験
ＡＳＴＭ Ｄ２７８３に準拠して、回転数１，８００ｒｐｍ、室温の条件で行った。最大非焼付荷重（ＬＮＬ）と融着荷重（ＷＬ）から荷重摩耗指数（ＬＷＩ）を求めた。この値が大きいほど耐荷重性が良好である。
（３）耐摩耗性試験
ＡＳＴＭ Ｄ２７８３に準拠して、荷重３９２Ｎ、回転数１，２００ｒｐｍ、油温７５℃、試験時間６０分の条件で行った。１／２インチ球３個の摩耗痕径を平均して平均摩耗痕径を算出した。
（４）摩擦係数試験
ＡＳＴＭ Ｄ２７１４に準拠して、荷重１１２８Ｎで回転数を変化させて測定した。なお、各回転数に設定した５分後の摩擦係数を測定して摩擦係数とした。
製造例１ ２，２’，２’’−ニトリロトリ−１−（２−エチルヘキソキシメチル）エタノール
【００２９】
攪拌器のついたガラス製フラスコに２−エチルヘキシルグリシジルエーテル４５５．５ｇ、エタノール５００ｍＬ、２８質量％アンモニア水４９．５ｇを加え、室温で３時間攪拌した。一夜静置後、反応液をガスクロマトグラフィーで分析した。原料の２−エチルヘキシルグリシジルエーテルの残存が認められた。フラスコを５０℃の水浴で加温し、２８質量％アンモニア水を約２ｍＬ加え、加温、攪拌した。反応液をガスクロマトグラフィーで分析し、２−エチルヘキシルグリシジルエーテルの残存が認められなくなるまで、アンモニア水の添加、加温、攪拌をくり返した。減圧下にエタノール、水を留去し、２，２’，２’’−ニトリロトリ−１−（２−エチルヘキソキシメチル）エタノール４１７．５ｇを得た。製造例２ ２，２’，２’’−ニトリロトリ−１−（２−エチルヘキソキシメチル）エチルボレート
ガラス製フラスコに製造例１で得られた２，２’，２’’−ニトリロトリ−１−（２−エチルヘキソキシメチル）エタノール４０３．４ｇ、ホウ酸４３．３ｇ、トルエン１．５Ｌを加え、フラスコにディーン・スターク脱水器、その上部に還流冷却器を取り付け、４時間加熱、還流した。水の留出は３７．３ｇであった。反応液を濾過し、減圧下にトルエンを留去して、２，２’，２’’−ニトリロトリ−１−（２−エチルヘキソキシメチル）エチルボレート４３４．１ｇを得た。
【００３０】
実施例１〜８
製造例２で得られた２，２’，２’’−ニトリロトリ−１−（２−エチルヘキソキシメチル）エチルボレートを第１表に示すように配合して、潤滑油組成物を調製し、性能を評価した。結果を第３表に示す。
実施例９
製造例２で得られた２，２’，２’’−ニトリロトリ−１−（２−エチルヘキソキシメチル）エチルボレートを第２表に示すように配合して、潤滑油組成物を調製し、性能を評価した。結果を第３表に示す。
また、この組成物の動粘度は３４．２７ｍｍ^２／ｓ（４０℃）、７．５８９ｍｍ^２／ｓ（１００℃）であった。組成物の摩擦係数を測定し、結果を第４表に示す。
比較例１、２、参考例１
第１表に示すように配合して、潤滑油組成物を調製し、性能を評価した。結果を第３表に示す。
比較例３
市販のベルト式無段変速機用潤滑油を用いて摩擦係数を評価した。動粘度は３７．８１ｍｍ^２／ｓ（４０℃）、７．１９２ｍｍ^２／ｓ（１００℃）であった。結果を第４表に示す。
【００３１】
【表１】

【００３２】
（注）
＊１：パラフィン系鉱油（１５０ニュートラル、イオウ分１０ｐｐｍ以下）
＊２：製造例２で得られたボレート
＊３：ポリブテニルコハク酸モノイミド（Ｎ分２．１質量％）
＊４：カルシウムスルホネート（塩基価２０ｍｇＫＯＨ／ｇ）
＊５：アミン系
＊６：ジアルキルジチオリン酸亜鉛（Ｃ４〜Ｃ８の第１級アルキル型）
【００３３】
【表２】

【００３４】
（注）
＊７：パラフィン系鉱油（１００ニュートラル）
＊８：ポリメタクリル酸エステル系
＊９：ポリメタクリル酸エステル系
＊１０：フェノール系
＊１１：トリアゾール系
＊２〜＊６は第１表の脚注と同じである。
【００３５】
【表３】

【００３６】
【表４】

【００３７】
上記実施例、比較例、及び参考例から明らかなように、本発明の添加剤を用いた潤滑油組成物は耐焼付き荷重、最大焼付き荷重が増加し、摩耗痕径が減少しており、耐焼付き性能、耐荷重性能及び耐摩耗性能が高いことが分かる（実施例１、２と比較例１を対比。実施例５、６と比較例２を対比）。また、本発明の添加剤に酸化防止剤を添加することで、耐荷重性能及び耐摩耗性能が更に向上している（実施例３、４と実施例１、２を対比）。更に、本発明の添加剤を市販極圧剤に添加することで耐焼付き性能を高めることができる（実施例７、８と参考例１を対比）。実施例９はベルト式無段変速機用途を想定した潤滑油組成物であり、優れた耐焼付き性能、耐荷重性能及び耐摩耗性能を示しており（実施例９）、市販ベルト式無段変速機油と比較して、摩擦係数が高いことから、変速機の動力の伝達能力が大きい（実施例９と比較例３を対比）。
【００３８】
【発明の効果】
本発明によれば、優れた耐焼付き性能、耐荷重性能、耐摩耗性を有する上、ベルト式無段変速機の動力伝達性能を高めることができ、潤滑油用として、あるいは燃料油用として用いられる極圧添加剤、並びに該添加剤を含む潤滑油組成物及び燃料油組成物を提供することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to additives for lubricating oils and fuel oils, as well as lubricating oil compositions and fuel oil compositions, and more particularly to specific agents having excellent functions as friction modifiers, especially extreme pressure additives and antiwear agents. The present invention relates to a lubricating oil and fuel oil additive having a structure of nitrilotriethyl borate as a main component, and a lubricating oil composition and a fuel oil composition each containing the additive.
[0002]
[Prior art]
Conventionally, drive system equipment such as internal combustion engines, automatic transmissions, shock absorbers, and power steering use lubricating oil to facilitate their operation. It is well known that the performance is insufficient, the lubricated surface is rubbed and worn, and finally seizure occurs. Therefore, lubricating oils containing an extreme pressure additive, an antiwear agent and the like are used. However, conventional extreme pressure additives are not always satisfactory because they do not exhibit sufficient seizure prevention effects, corrode metals, or have poor abrasion resistance due to interaction with other additives. It wasn't good.
Metal working oils used for metal working such as cutting, grinding or plastic working include mineral oils and synthetic hydrocarbon oils, and oily agents such as alcohols, fatty acid esters, and fatty acids, and extreme pressure additives. It is prepared by blending and attempts have been made to improve processability.
[0003]
However, for such a metal working oil, a new working oil capable of further improving the workability is demanded from the viewpoint of improving productivity and saving energy. At the same time, chlorine-based extreme pressure additives, which have been widely used as extreme pressure additives in the past, cause rash on the human body and cause rust on the target metal, causing deterioration of the working environment. , Tend to refrain from using it.
As a metalworking oil that meets the above demand, an oil agent obtained by adding a sulfurized olefin containing active sulfur and an overbased sulfonate to a base oil is commercially available.
[0004]
The above-mentioned commercially available metal working oil has good welding resistance and has a performance capable of preventing abnormal wear (for example, chipping) of a tool and peeling of a machined surface. However, in processing in which relatively low-load friction is repeated, corrosion and wear of the tool due to active sulfur progresses, and the time required for tool replacement or re-polishing is shortened, often hindering production efficiency. Conversely, metal processing in which abnormal wear does not pose a problem from the beginning often causes a reduction in production efficiency.
Next, the hydraulic oil is a power transmission fluid used for operations such as power transmission, force control, and buffering in a hydraulic system such as a hydraulic device or device, and also functions to lubricate sliding parts.
[0005]
In such a hydraulic oil, it is essential to have an excellent anti-seizure property under load and abrasion resistance in particular. Therefore, extreme pressure additives and anti-wear agents are added to base oils such as mineral oil and synthetic oil. , The above-mentioned performance is imparted. However, conventional extreme pressure additives have not always been fully satisfactory, such as having insufficient load seizure prevention effects, insufficient wear resistance, and causing corrosion wear. .
In addition, gear oils, especially gear oils for automobiles, have recently suffered from increased wear capacity, harsh operating conditions such as long-distance transportation due to the development of the expressway network, and the extension of oil renewal intervals. Improving oxidation stability is urgently needed.
Until now, it has been practiced to blend mainly extreme pressure additives or anti-wear additives such as sulfurized fats and oils, sulfurized olefins, phosphoric and thiophosphoric compounds, and zinc dithiophosphate with lubricating base oils. Further, further reduction in wear resistance, oxidation stability and wear coefficient ratio (low speed / high speed) is required.
[0006]
On the other hand, it is known that the lubricating performance of fuel oil becomes insufficient as it is highly hydrogenated, and it has been pointed out that a fuel pump using a highly purified fuel wears. Therefore, recent high-performance turbine fuels are required to have high lubrication performance, and are adsorbed on the metal surface of fuel system equipment to form an extreme pressure film, thereby improving lubricity and reducing wear. Fuel oil additives are desired.
Conventionally, sulfur-based extreme pressure additives have been often used as extreme pressure additives for lubricating oils. This sulfur-based extreme-pressure additive has a sulfur atom in the molecule and is dissolved or uniformly dispersed in a base oil to exhibit an extreme-pressure effect. Sulfurized olefins, thiocarbamates, thioterpenes, dialkylthiodipropionates and the like are known. However, these sulfur-based extreme pressure additives corrode metals, do not exhibit sufficient seizure prevention effects due to interaction with other additives, or have insufficient abrasion resistance. However, it was not always satisfactory.
[0007]
The applicant has previously applied for a patent for a lubricating oil additive and a fuel oil additive containing hydrocarbon-substituted 2,2 ′, 2 ″ -nitrilotriethyl borate as a main component (Patent Document 1). This additive exerts excellent effects on load resistance, abrasion resistance and friction reduction when added in a small amount, but sometimes has insufficient solubility and is difficult to use at a high concentration, and its improvement has been desired. .
[0008]
[Patent Document 1]
JP 2001-131567 A
[Problems to be solved by the invention]
The present invention has been made in such a situation, and has excellent load resistance and abrasion resistance without containing harmful phosphorus or heavy metal, and dissolves in lubricating base oil or fuel oil. It is an object of the present invention to provide an additive which has good properties and is suitably used for lubricating oil and fuel oil, and a lubricating oil composition and a fuel oil composition containing the additive.
[0010]
[Means for Solving the Problems]
Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a lubricating oil and a fuel mainly containing an ether bond-containing 2,2 ′, 2 ″ -nitrilotriethyl borate having a specific structure are used as main components. It has been found that the purpose can be achieved by the additive for oil. The present invention has been completed based on such findings.
That is, the present invention
(1) General formula (I)
[0011]
Embedded image

[0012]
[Wherein, R ¹ represents a —CH ₂ —O—CR ₃ group (provided that R is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different, and R This hydrocarbon group may contain an oxygen atom, a sulfur atom or a nitrogen atom.), And R ^{2 to} R ¹² each independently represent a hydrogen atom, a C 1-20 carbon atom. Represents a hydrogen group or R ¹ . ]
An additive for a lubricating oil containing, as a main component, an ether group-containing 2,2 ′, 2 ″ -nitrilotriethyl borate represented by:
(2) an additive for a fuel oil containing, as a main component, an ether group-containing 2,2 ′, 2 ″ -nitrilotriethyl borate represented by the general formula (I),
(3) A lubricating oil composition comprising (A) a lubricating base oil and (B) the lubricating oil additive of (1) above.
(4) The lubricating oil composition of (3), which further comprises (C) at least one selected from an antioxidant, a detergent / dispersant, and a viscosity index improver, and (5) (X) a fuel oil. , (Y) a fuel oil composition comprising the fuel oil additive of (2) above,
Is provided.
[0013]
BEST MODE FOR CARRYING OUT THE INVENTION
The compound represented by the general formula (I) used in the lubricating oil and fuel oil additives of the present invention has the following structure:
Embedded image

[0015]
2,2 ′, 2 ″ -nitrilotriethyl borate containing an ether group.
In the general formula (I), R ¹ represents a —CH ₂ —O—CR ₃ group. Here, R is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different, and R may combine with each other to form a ring. The hydrocarbon group may contain an oxygen, sulfur or nitrogen atom.
The CR ₃ is preferably a hydrocarbon group having 1 to 12 carbon atoms, and more preferably a hydrocarbon group having 3 to 8 carbon atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. Here, the alkyl group having 1 to 20 carbon atoms may be linear, branched, or cyclic. Specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, Examples include various pentyl groups, various hexyl groups, various octyl groups, various decyl groups, various dodecyl groups, cyclopentyl groups, cyclohexyl groups, methylcyclohexyl groups, and the like. Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a tolyl group, a xylyl group, a butylphenyl group, and a naphthyl group. Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group, a phenethyl group, And a naphthylmethyl group.
[0016]
On the other hand, R ^{2 to} R ¹² each represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or R ¹ . Here, examples of the hydrocarbon group having 1 to 20 carbon atoms include the groups exemplified above as the hydrocarbon group having 1 to 20 carbon atoms. R ^{2 to} R ¹² may be the same or different from each other. However, for manufacturing reasons, (1) all of R ^{2 to} R ¹² are hydrogen atoms, and (2) R ⁵ = R ⁹ = R ¹ , and the others are preferably a hydrogen atom or a methyl group, (3) R ⁵ = R ¹ , and the others are preferably a hydrogen atom or a methyl group.
Representative examples of the ether group-containing 2,2 ′, 2 ″ -nitrilotriethyl borate represented by the general formula (1) of the present invention include 2,2 ′, 2 ″ -nitrilo-1-alkoxymethyltriethyl borate, 2,2 ′, 2 ″ -Nitrilo-1,1′-dialkoxymethyltriethyl borate, 2,2 ′, 2 ″ -Nitrilo-1,1 ′, 1 ″ -trialkoxymethyltriethyl borate and the like. Can be
[0017]
The ether group-containing 2,2 ′, 2 ″ -nitrilotriethyl borate represented by the general formula (I) of the present invention can be produced by various methods, and usually, the ether group-containing 2,2 ′, 2 ′. After obtaining '-nitrilotriethanol, it can be produced by esterifying it with boric acid or the like.
The starting material containing ether group-containing 2,2 ′, 2 ″ -nitrilotriethanol can be prepared, for example, by the following reaction formulas (a), (b) and (c).
[0018]
Embedded image

[0019]
(In the formula, R ¹³ is the same as CR ₃ , and R ^{14 to} R ²⁴ are the same as R ^{2 to} R ^12. )
As shown in the above, a method of reacting glycidyl ethers (II) with ammonia to produce 2,2 ′, 2 ″ -nitrilotriethanol (III) [reaction formula (a)], glycidyl ethers (II) ) And monoethanolamines (IV) to produce 2,2 ′, 2 ″ -nitrilotriethanol (V) [reaction formula (b)], glycidyl ethers (II) and diethanolamines ( VI) to produce 2,2 ′, 2 ″ -nitrilotritanol (VII) [reaction formula (c)].
Examples of the glycidyl ethers (II) include methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, tert-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, 2-methyloctyl glycidyl ether, phenyl glycidyl ether, and sec-butyl. Examples include phenyl glycidyl ether and benzyl glycidyl ether. This glycidyl ether can be produced, for example, from epichlorohydrin and alcohol by a known method. Glycidyl ethers having a branched alkyl group are preferred, and 2-ethylhexyl glycidyl ether is particularly preferred. Examples of the monoethanolamines (IV) include ethanolamine, 1-amino-2-propanol, 2-amino-1-propanol, 1-amino-2-butanol, and 2-amino-2-methyl-1. -Propanol, 2-amino-1-phenylethanol, phenylalaninol and the like. The monoethanolamines can be produced, for example, by a known method of reacting an epoxy compound with ammonia. Examples of the diethanolamines (VI) include diethanolamine, dipropanolamine, and 2,2′-iminodi (1-phenylethanol). The diethanolamines can be produced, for example, by a known method of reacting an epoxy compound with ammonia or ethanolamines.
[0020]
The ether containing 2,2 ′, 2 ″ -nitrilotriethanol obtained by the above method is reacted with a boron compound such as boric acid, metaboric acid, boric acid triester and the like, and the ether group containing 2,2 ′, 2 ′ is obtained. '-Nitrilotriethyl borate can be obtained. Water and alcohol generated during the reaction are removed by distillation or the like. The target substance is purified by a method such as recrystallization if necessary.
Specific examples of the ether group-containing 2,2 ′, 2 ″ -nitrilotriethyl borate represented by the general formula (I) include 3-methoxymethyl-2,8,9-trioxa-5-aza-1- Borabicyclo [3.3.3] undecane, 3,7-dimethoxymethyl-2,8,9-trioxa-5-aza-1-borabicyclo [3.3.3] undecane, 2,2 ′, 2 ″- Nitrilotri-1-methoxymethylethyl borate, 3-ethoxymethyl-2,8,9-trioxa-5-aza-1-borabicyclo [3.3.3] undecane, 3,7-diethoxymethyl-2,8, 9-trioxa-5-aza-1-borabicyclo [3.3.3] undecane, 2,2 ′, 2 ″ -nitrilotri-1-ethoxymethylethyl borate, 3-butoxymethyl-2,8,9-trioxa −5- The-1-borabicyclo [3.3.3] undecane, 3,7-dibutoxymethyl-2,8,9-trioxa-5-aza-1-borabicyclo [3.3.3] undecane, 2,2 ′ , 2 ''-Nitrilotri-1-butoxymethylethyl borate, 3- (2-ethylhexoxymethyl) -2,8,9-trioxa-5-aza-1-borabicyclo [3.3.3] undecane, 3 , 7-Di (2-ethylhexoxymethyl) -2,8,9-trioxa-5-aza-1-borabicyclo [3.3.3] undecane, 2,2 ′, 2 ″ -nitrilotri-1- (2-ethylhexoxymethyl) ethyl borate, 3-phenoxymethyl-2,8,9-trioxa-5-aza-1-borabicyclo [3.3.3] undecane, 3,7-diphenoxymethyl-2, 8,9-trioki -5-aza-1-borabicyclo [3.3.3] undecane, 2,2 ′, 2 ″ -nitrilotri-1-phenoxymethylporate, 3,7-dimethyl-10- (2-ethylhexoxymethyl) -2,8,9-Trioxa-5-aza-1-borabicyclo [3.3.3] undecane, 3,7-di-2-ethylhexoxymethyl-10-methyl-2,8-9-trioxa- 5-aza-1-borabicyclo [3.3.3] undecane, 3,7-di-2-ethylhexoxymethyl-10-phenyl-2,8,9-trioxa-5-aza-1-borabicyclo [3 .3.3] undecane and the like.
[0021]
These ether group-containing 2,2 ′, 2 ″ -nitrilotriethyl borate is an extreme pressure additive that does not contain harmful phosphorus or heavy metals, and has excellent load carrying capacity and wear resistance, and is used for lubricating oils and fuels. Used as an additive for
The additive for lubricating oil and fuel oil of the present invention may contain one kind of the ether group-containing 2,2 ′, 2 ″ -nitrilotriethyl borate represented by the general formula (I), The above may be included.
Next, the lubricating oil composition of the present invention contains (A) a lubricating oil base oil and (B) a lubricating oil additive containing the aforementioned ether group-containing 2,2 ′, 2 ″ -nitrilotriethyl borate. Is what you do. The lubricating oil composition according to the present invention includes an automotive engine lubricating oil used for an internal combustion engine, a drive system device such as an automatic transmission, a shock absorber, a power steering, a gear, a cutting process, a grinding process, and a plastic working process. Metal working oils used for metal working such as, for example, hydraulic oils used in hydraulic systems such as hydraulic equipment and devices for power transmission, force control, and shock absorbers are also used as hydraulic fluids.
[0022]
In the lubricating oil composition of the present invention, the lubricating base oil used as the component (A) is not particularly limited, and is appropriately selected from mineral oil and synthetic oil according to the purpose of use and use conditions of the composition. . Here, as the mineral oil, for example, a paraffin-based crude oil, an intermediate-based crude oil or a naphthene-based crude oil is subjected to atmospheric distillation, or a distillate obtained by vacuum-distilling the residual oil of atmospheric distillation, or a distillate obtained therefrom. Refined oils obtained by refining according to a conventional method, specifically, solvent refined oils, hydrogenated refined oils, dewaxed oils, clay treated oils and the like can be mentioned.
Examples of the synthetic oil include low-molecular-weight polybutene, low-molecular-weight polypropylene, α-olefin oligomers having 8 to 14 carbon atoms and hydrides thereof, and polyol esters (trimethylolpropane fatty acid ester, pentaerythritol fatty acid ester and the like). ), Dibasic acid esters, aromatic polycarboxylic acid esters, phosphoric acid esters, etc., alkylaromatic compounds such as alkylbenzenes and alkylnaphthalenes, polyglycol oils such as polyalkylene glycols, and silicone oils.
[0023]
These base oils may be used alone or in an appropriate combination of two or more.
The content of the lubricating oil additive of the component (B) in the lubricating oil composition of the present invention is appropriately selected depending on the purpose and conditions of use of the composition, but is generally 0.01 to 50% by mass. Range. In the case of lubricating oils for automobiles and hydraulic oils, it is usually in the range of 0.01 to 30% by mass, preferably 0.01 to 10% by mass. In the case of metal working oils, the additives can be used alone. Is usually selected in the range of 0.1 to 60% by mass, preferably 0.1 to 50% by mass.
The lubricating oil composition of the present invention preferably further contains, as the component (C), at least one selected from an antioxidant, a detergent / dispersant, and a viscosity index improver.
[0024]
Examples of the antioxidant include amine antioxidants such as alkylated diphenylamine, phenyl-α-naphthylamine, and alkylated-naphthylamine; 2,6-di-t-butyl-p-cresol; and 4,4′-. Examples include phenolic antioxidants such as methylenebis (2,6-di-t-butylphenol). Further, the detergent and dispersant include ashless dispersants and metal detergents. Examples of the ashless dispersants include succinimides, boron-containing succinimides, benzylamines, and boron-containing benzylamine. , Succinic esters, amides of monovalent or divalent carboxylic acids represented by fatty acids or succinic acids, and the like, and as the metal-based detergent, for example, neutral metal sulfonate, neutral metal phenate, Basic metal salicylates, neutral metal phosphonates, basic sulfonates, basic phenates, basic salicylates, basic phosphonates, overbased sulfonates, overbased phenates, overbased salicylates, overbased phosphonates, and the like. Further, as the viscosity index improver, for example, polymethacrylate, dispersion-type polymethacrylate, olefin-based copolymer (for example, ethylene-propylene copolymer or the like), dispersion-type olefin-based copolymer, styrene-based copolymer ( For example, styrene-diene hydrogenated copolymer and the like can be mentioned.
[0025]
In the lubricating oil composition of the present invention, other various additives, for example, other friction modifiers (oil agents, other extreme pressure additives), antiwear agents, pour point depressants, rust prevention, depending on the purpose of use. Agents, metal corrosion inhibitors, defoamers, surfactants, and the like can be appropriately contained.
As other friction modifiers and antiwear agents, for example, sulfur compounds such as sulfurized olefins, dialkyl polysulfides, diarylalkyl polysulfides, diaryl polysulfides, phosphate esters, thiophosphate esters, phosphite esters, alkyl hydrogen phosphites, phosphorus Phosphorus compounds such as acid ester amine salts and phosphite ester amine salts, chlorinated fats and oils, chlorinated paraffins, chlorinated fatty acid esters, chlorinated fatty acids and other chlorinated compounds, alkyl or alkenyl maleate esters, alkyl and alkenyl succinates Ester compounds such as acid esters, organic acid compounds such as alkyl or alkenyl maleic acid, alkyl or alkenyl succinic acid, naphthenate, zinc dithiophosphate (ZnDTP), dithiocarbamic acid Zinc (ZnDTC), sulfurized oxymolybdenum organo phosphorodithioate (MoDTP), and an organic metal-based compounds such as sulfurized oxymolybdenum dithiocarbamate (MoDTC).
Pour point depressants include, for example, polymethacrylates; rust inhibitors include, for example, alkenyl succinic acids and partial esters thereof; metal corrosion inhibitors include, for example, benzotriazoles, benzimidazoles, benzothiazoles For example, dimethylpolysiloxane and polyacrylate are used as defoaming agents, and polyoxyethylene alkylphenyl ether is used as a surfactant, for example.
[0026]
The lubricating oil composition of the present invention includes, for example, internal combustion engines, automatic transmissions, shock absorbers, drive system equipment such as power steering, automotive lubricating oils used for gears and the like, cutting, grinding, and plastic working. It is used as a metal working oil used for processing, a hydraulic oil as a power transmission fluid used for operations such as power transmission, force control, and buffering in hydraulic systems such as hydraulic equipment and devices.
On the other hand, the fuel oil composition of the present invention comprises (X) a fuel oil and (Y) a fuel oil additive containing the aforementioned ether group-containing 2,2 ′, 2 ″ -nitrilotriethyl borate. is there.
[0027]
In the fuel oil composition of the present invention, a highly hydrorefined fuel oil such as a high-performance turbine fuel oil is preferably used as the fuel oil (X).
The content of the fuel oil additive (Y) in the fuel oil composition of the present invention is generally in the range of 0.01 to 1,000 ppm, preferably 0.01 to 100 ppm.
In the fuel oil composition of the present invention, various additives can be appropriately compounded as needed. Examples of such additives include, for example, phenylenediamine-based, diphenylamine-based, alkylphenol-based, aminophenol-based antioxidants, polyetheramines, detergents such as polyalkylamines, Schiff-type compounds and thioamide-type compounds. Metal deactivators, surface ignition inhibitors such as organophosphorus compounds, anti-icing agents such as polyhydric alcohols and ethers, alkali metal salts and alkaline earth metal salts of organic acids, and auxiliary agents such as sulfates of higher alcohols, Antistatic agents such as anionic surfactants, cationic surfactants and amphoteric surfactants, rust inhibitors such as alkenyl succinic acid esters, discriminating agents such as quinizarin and coumarin, odorants such as natural essential oils and synthetic fragrances And known fuel oil additives such as colorants such as azo dyes.
[0028]
【Example】
Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
The friction coefficient, wear scar diameter, and corrosivity of the lubricating oil composition were determined according to the following methods.
(1) Seizure Resistance Seizure load (N) was determined by a Falex test according to ASTM D3233-93A method. The measurement conditions are a rotation speed of 290 rpm and an oiliness of 80 ° C.
(2) Load resistance test The test was performed at 1,800 rpm and room temperature in accordance with ASTM D2783. The load and wear index (LWI) was determined from the maximum non-seizure load (LNL) and the fusion load (WL). The larger the value, the better the load resistance.
(3) Abrasion resistance test Abrasion resistance test was performed under the conditions of a load of 392 N, a rotation speed of 1,200 rpm, an oil temperature of 75 ° C, and a test time of 60 minutes in accordance with ASTM D2783. The average wear scar diameter was calculated by averaging the wear scar diameters of three 1/2 inch balls.
(4) Friction coefficient test According to ASTM D2714, the friction coefficient was measured at a load of 1128 N while changing the rotation speed. In addition, the friction coefficient after 5 minutes set at each rotation speed was measured and defined as a friction coefficient.
Production Example 1 2,2 ′, 2 ″ -Nitrilotri-1- (2-ethylhexoxymethyl) ethanol
To a glass flask equipped with a stirrer, 455.5 g of 2-ethylhexyl glycidyl ether, 500 mL of ethanol, and 49.5 g of 28% by mass aqueous ammonia were added, and the mixture was stirred at room temperature for 3 hours. After standing overnight, the reaction solution was analyzed by gas chromatography. It was confirmed that 2-ethylhexyl glycidyl ether as a raw material remained. The flask was heated in a 50 ° C. water bath, about 2 mL of 28% by mass aqueous ammonia was added, and the mixture was heated and stirred. The reaction solution was analyzed by gas chromatography, and the addition of ammonia water, heating and stirring were repeated until no remaining 2-ethylhexyl glycidyl ether was observed. Ethanol and water were distilled off under reduced pressure to obtain 417.5 g of 2,2 ′, 2 ″ -nitrilotri-1- (2-ethylhexoxymethyl) ethanol. Production Example 2 2,2 ′, 2 ″ -Nitrilotri-1- obtained in Production Example 1 in a flask made of 2,2 ′, 2 ″ -nitrilotri-1- (2-ethylhexoxymethyl) ethyl borate glass 403.4 g of (2-ethylhexoxymethyl) ethanol, 43.3 g of boric acid and 1.5 L of toluene were added, and a Dean-Stark dehydrator was attached to the flask, and a reflux condenser was attached to the upper part of the flask, and the mixture was heated and refluxed for 4 hours. Distillation of water was 37.3 g. The reaction solution was filtered, and toluene was distilled off under reduced pressure to obtain 434.1 g of 2,2 ′, 2 ″ -nitrilotri-1- (2-ethylhexoxymethyl) ethyl borate.
[0030]
Examples 1 to 8
2,2 ′, 2 ″ -Nitrilotri-1- (2-ethylhexoxymethyl) ethyl borate obtained in Production Example 2 was blended as shown in Table 1 to prepare a lubricating oil composition, The performance was evaluated. The results are shown in Table 3.
Example 9
2,2 ′, 2 ″ -Nitrilotri-1- (2-ethylhexoxymethyl) ethyl borate obtained in Production Example 2 was blended as shown in Table 2 to prepare a lubricating oil composition, The performance was evaluated. The results are shown in Table 3.
Further, the kinematic viscosity of the composition was ^{34.27mm 2 /s(40℃),7.589mm 2 / s (100} ℃). The coefficient of friction of the composition was measured and the results are shown in Table 4.
Comparative Examples 1 and 2, Reference Example 1
The lubricating oil composition was prepared by mixing as shown in Table 1 and the performance was evaluated. The results are shown in Table 3.
Comparative Example 3
The friction coefficient was evaluated using a commercially available lubricating oil for a belt-type continuously variable transmission. The kinematic viscosity was ^{37.81mm 2 /s(40℃),7.192mm 2 / s (100} ℃). The results are shown in Table 4.
[0031]
[Table 1]

[0032]
(note)
* 1: Paraffinic mineral oil (150 neutral, sulfur content 10 ppm or less)
* 2: Borate obtained in Production Example 2 * 3: Polybutenylsuccinic monoimide (N content: 2.1% by mass)
* 4: Calcium sulfonate (base value 20 mgKOH / g)
* 5: Amine type * 6: Zinc dialkyldithiophosphate (C4-C8 primary alkyl type)
[0033]
[Table 2]

[0034]
(note)
* 7: Paraffinic mineral oil (100 neutral)
* 8: Polymethacrylate ester * 9: Polymethacrylate ester * 10: Phenol * 11: Triazole * 2 to * 6 are the same as footnotes in Table 1.
[0035]
[Table 3]

[0036]
[Table 4]

[0037]
As is clear from the above Examples, Comparative Examples, and Reference Examples, the lubricating oil composition using the additive of the present invention has an increased seizure resistance, a maximum seizure load, and a reduced wear scar diameter. It can be seen that the seizure resistance, load resistance and abrasion resistance are high (Examples 1 and 2 are compared with Comparative Example 1; Examples 5 and 6 are compared with Comparative Example 2). Further, by adding the antioxidant to the additive of the present invention, the load resistance and the wear resistance are further improved (Examples 3 and 4 are compared with Examples 1 and 2). Further, the anti-seizure performance can be improved by adding the additive of the present invention to a commercially available extreme pressure agent (Comparing Examples 7 and 8 with Reference Example 1). Example 9 is a lubricating oil composition intended for use in a belt-type continuously variable transmission, and shows excellent seizure resistance, load resistance and wear resistance (Example 9), and a commercially available belt-type continuously variable transmission. Since the friction coefficient is higher than that of the machine oil, the transmission power of the transmission is large (compare Example 9 with Comparative Example 3).
[0038]
【The invention's effect】
According to the present invention, in addition to having excellent seizure resistance, load resistance, and wear resistance, the power transmission performance of a belt-type continuously variable transmission can be enhanced, and it is used for lubricating oil or for fuel oil. , And a lubricating oil composition and a fuel oil composition containing the additive.

Claims (5)

General formula (I)

[Wherein, R ¹ represents a —CH ₂ —O—CR ₃ group (provided that R is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different, and R is a ring This hydrocarbon group may contain an oxygen atom, a sulfur atom or a nitrogen atom.) And R ^{2 to} R ¹² are each independently a hydrogen atom, a hydrocarbon having 1 to 20 carbon atoms. Represents a group or R ¹ . ]
An additive for lubricating oils comprising, as a main component, an ether group-containing 2,2 ′, 2 ″ -nitrilotriethyl borate represented by the formula: General formula (I)

[Wherein, R ¹ represents a —CH ₂ —O—CR ₃ group (provided that R is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different, and R This hydrocarbon group may contain an oxygen atom, a sulfur atom or a nitrogen atom.), And R ^{2 to} R ¹² each independently represent a hydrogen atom, a C 1-20 carbon atom. Represents a hydrogen group or R ¹ . ]
An additive for fuel oils containing ether group-containing 2,2 ′, 2 ″ -nitrilotriethyl borate represented by the following formula: A lubricating oil composition comprising: (A) a lubricating base oil; and (B) the lubricating oil additive according to claim 1. The lubricating oil composition according to claim 3, further comprising (C) at least one selected from an antioxidant, a detergent / dispersant, and a viscosity index improver. A fuel oil composition comprising: (X) a fuel oil; and (Y) the fuel oil additive according to claim 2.