JP5779376B2 - Lubricating oil composition - Google Patents

Lubricating oil composition Download PDF

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JP5779376B2
JP5779376B2 JP2011072464A JP2011072464A JP5779376B2 JP 5779376 B2 JP5779376 B2 JP 5779376B2 JP 2011072464 A JP2011072464 A JP 2011072464A JP 2011072464 A JP2011072464 A JP 2011072464A JP 5779376 B2 JP5779376 B2 JP 5779376B2
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JP2012207083A (en
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靖之 大沼田
靖之 大沼田
紀子 阿部
紀子 阿部
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Eneos Corp
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JXTG Nippon Oil and Energy Corp
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Priority to EP11862708.2A priority patent/EP2692841A4/en
Priority to CN201180069358.4A priority patent/CN103443256B/en
Priority to US14/007,120 priority patent/US20140018271A1/en
Priority to PCT/JP2011/070814 priority patent/WO2012132055A1/en
Priority to CA2820519A priority patent/CA2820519A1/en
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    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
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    • C10M141/00Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/10Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
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    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10Petroleum or coal fractions, e.g. tars, solvents, bitumen
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    • C10M2223/043Ammonium or amine salts thereof
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    • C10M2223/02Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
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    • C10M2223/049Phosphite
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    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00Metal present as such or in compounds
    • C10N2010/04Groups 2 or 12
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    • C10N2020/00Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01Physico-chemical properties
    • C10N2020/02Viscosity; Viscosity index
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    • 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
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/04Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/14Electric or magnetic purposes
    • C10N2040/16Dielectric; Insulating oil or insulators

Description

本発明は、絶縁性及び潤滑性に優れる潤滑油組成物に関する。   The present invention relates to a lubricating oil composition having excellent insulating properties and lubricity.

自動車用装置は、さまざまな電子制御装置が使用されている。潤滑油の中で使用される場合もあり、潤滑油の絶縁性も重要になってきている。なかでも燃料電池自動車、電気自動車又はハイブリッド自動車に搭載される変速機用潤滑油、変速機・電動モータ兼用油、又は変速機と電動モータの潤滑システムが共有化された装置用変速機は、使用される電圧が高いところから、これらに使用される潤滑油の絶縁性はさらに高いものが求められている。さらに、近年の省燃費性能向上のため、動力伝達効率の向上や小型軽量化が求められており、変速機には、さらに高い負荷がかかるようになっている。このため絶縁性と同時に高い耐摩耗性や耐焼付性も求められるようになってきている。   Various electronic control devices are used for automobile devices. In some cases, it is used in lubricating oil, and the insulating properties of the lubricating oil are becoming important. In particular, transmission lubricating oil mounted on fuel cell vehicles, electric vehicles, or hybrid vehicles, transmission / electric motor combined oil, or transmissions for devices that share a transmission and electric motor lubrication system are used. Since the applied voltage is high, the insulating properties of the lubricating oil used in these are required to be higher. Furthermore, in order to improve fuel economy performance in recent years, improvement in power transmission efficiency and reduction in size and weight have been demanded, and a higher load is applied to the transmission. For this reason, high wear resistance and seizure resistance as well as insulation have been demanded.

また変速機用潤滑油には、上述した性能のほか、クラッチの特性に合致した摩擦特性や、適正な油圧制御ができるように、低温から高温までの粘度特性、すなわち、できるだけ温度に左右されない粘度維持や、制御装置が適正に作動するように、装置内がきれいに保てるよう、酸化安定性や清浄分散性が求められる。さらにこれらの性能は一般には装置の寿命の間維持される必要がある。このため、変速機用潤滑油にはさまざまな添加剤が使用される。   In addition to the above-mentioned performance, the lubricating oil for transmissions has a friction characteristic that matches the characteristics of the clutch, and a viscosity characteristic from low temperature to high temperature, that is, a viscosity that is not affected by temperature as much as possible, so that proper hydraulic pressure control is possible. Oxidation stability and clean dispersibility are required so that the inside of the apparatus can be kept clean so that the maintenance and control apparatus can operate properly. Furthermore, these performances generally need to be maintained over the lifetime of the device. For this reason, various additives are used in transmission lubricating oil.

これまで、このような変速機用潤滑油として、鉱油、合成油、及びこれらの混合物からなる群より選択される基油と、組成物全量基準で0.1〜1 5.0質量%の、炭化水素基含有ジチオリン酸亜鉛、トリアリールホスフェート、トリアリールチオホスフェート及びこれらの混合物からなる群より選択されるリン化合物とを含有し、かつ、80℃における体積抵抗率が1×10Ω・m 以上であることを特徴とする自動車用変速機油組成物(特許文献1)や、鉱油、ポリ−α−オレフィン、ポリ−α−オレフィンの水素化物、アルキルベンゼン、エステル系化合物、及びこれらの混合物からなる群より選択され、80℃における動粘度が1.5〜4.0mm/sである基油と、組成物全体量基準で0.1〜4.0質量%の、炭化水素基含有ジチオリン酸亜鉛、トリアリールチオホスフェート及びこれらの混合物からなる群より選択されるリン化合物と、無灰分散剤とを含有し、かつ、80℃における体積抵抗率が1×10Ω・m以上であることを特徴とする変速機油組成物(特許文献2)が報告されている。 So far, as such a lubricating oil for transmission, a base oil selected from the group consisting of mineral oil, synthetic oil, and mixtures thereof, and 0.1 to 15.0 mass% on the basis of the total amount of the composition, And a phosphorus compound selected from the group consisting of hydrocarbon group-containing zinc dithiophosphate, triaryl phosphate, triaryl thiophosphate, and mixtures thereof, and has a volume resistivity of 1 × 10 7 Ω · m at 80 ° C. It consists of a transmission oil composition for automobiles (Patent Document 1), mineral oil, poly-α-olefin, poly-α-olefin hydride, alkylbenzene, ester compounds, and mixtures thereof. is selected from the group, kinematic viscosity at 80 ° C. and a base oil is 1.5 to 4.0 mm 2 / s, the 0.1 to 4.0 mass% in total basis composition, a hydrocarbon group-containing Zinc dithiophosphate contains a phosphorus compound selected from the group consisting of triaryl thiophosphate, and mixtures thereof, and ashless dispersants, and the volume resistivity at 80 ° C. is at 1 × 10 8 Ω · m or more A transmission oil composition (Patent Document 2) characterized by this is reported.

国際公開第2002/097017号International Publication No. 2002/097017 特開2008−285682号公報JP 2008-285682 A

前述したように変速機にはさまざまな添加剤が使用されるが、これらの添加剤は単独で、あるいは組み合わせで、絶縁性や耐摩耗性、耐焼付性を低下させたりする。本発明は変速機に必要な性能を維持しながら、従来技術より、さらに優れた絶縁性能や耐摩耗性、耐焼付性を向上させた潤滑油組成物を提供することにある。   As described above, various additives are used in the transmission, but these additives may be used alone or in combination to reduce insulation, wear resistance, and seizure resistance. An object of the present invention is to provide a lubricating oil composition with improved insulation performance, wear resistance, and seizure resistance, which is superior to the prior art, while maintaining the performance required for the transmission.

すなわち、本発明によれば、(A)潤滑油基油に、(B)一般式(1)または一般式(2)で表される少なくともひとつの水酸基を持ち、かつ炭化水素基の炭素数が16以下であるリン化合物、およびそれらのアミン塩から選ばれる少なくとも1種類のリン化合物を組成物全量基準でリン元素換算量として0.03質量%以上0.1質量%以下配合し(ただし、中性リン系化合物は配合しない)、(C)窒素を含む官能基を分散基とする無灰分散剤を組成物全量基準で窒素量が0.001質量%未満含有するか、あるいはまったく含有せず、80℃における体積抵抗率が5×10Ω・m以上である、変速機油、燃料電池自動車、電気自動車又はハイブリッド自動車に搭載される電動モータ用潤滑油、変速機・電動モータ兼用油、又は変速機と電動モータの潤滑システムが共有化された装置用変速機油の用途に使用される潤滑油組成物を提供する。

Figure 0005779376
(一般式(1)において、X、X及びXは、それぞれ個別に酸素原子を示し、R、R及びRは、少なくともひとつが水素原子であり、他は炭素数1〜16の炭化水素基を示す。)
Figure 0005779376
(一般式(2)において、X、X、X及びXは、それぞれ個別に酸素原子(X、X及びXの1つ又は2つが単結合又は(ポリ)オキシアルキレン基でもよい。)を示し、R、R及びRは、少なくともひとつが水素原子であり、他は炭素数1〜16の炭化水素基を示す。) That is, according to the present invention, (A) the lubricating base oil has (B) at least one hydroxyl group represented by general formula (1) or general formula (2), and the hydrocarbon group has a carbon number of A phosphorus compound that is 16 or less, and at least one phosphorus compound selected from amine salts thereof are blended in an amount of 0.03 % by mass or more and 0.1% by mass or less in terms of phosphorus element based on the total amount of the composition. (C) an ashless dispersant having a functional group containing nitrogen as a dispersing group is contained in an amount of nitrogen of less than 0.001% by mass based on the total amount of the composition, or not contained at all, Transmission oil having a volume resistivity at 80 ° C. of 5 × 10 8 Ω · m or more, lubricating oil for an electric motor mounted on a fuel cell vehicle, an electric vehicle, or a hybrid vehicle, a transmission / electric motor combined oil, or a shift Machine It provides a lubricating oil composition lubrication system of the electric motor is used in applications shared by the device for transmission fluid.
Figure 0005779376
(In General Formula (1), X 1 , X 2, and X 3 each independently represent an oxygen atom, R 1 , R 2, and R 3 each have at least one hydrogen atom; 16 hydrocarbon groups are shown.)
Figure 0005779376
(In General Formula (2), X 4 , X 5 , X 6 and X 7 are each independently an oxygen atom (one or two of X 4 , X 5 and X 6 are a single bond or a (poly) oxyalkylene group) And at least one of R 4 , R 5 and R 6 represents a hydrogen atom, and the other represents a hydrocarbon group having 1 to 16 carbon atoms.)

本発明の潤滑油組成物は、変速機やその他の機器の潤滑に必要な性能を維持しながら、従来技術より、さらに優れた絶縁性能や耐摩耗性、耐焼付性を向上させることができる。   The lubricating oil composition of the present invention can improve insulation performance, wear resistance, and seizure resistance, which are further superior to those of the prior art, while maintaining the performance necessary for lubricating transmissions and other devices.

以下、本発明を詳細に述べる。   The present invention will be described in detail below.

本発明における(A)潤滑油基油としては、鉱油系基油および/または合成油系基油が使用でき、また2種類以上の鉱油系基油同志あるいは合成油系基油同志の混合物であっても差し支えなく、鉱油系基油と合成油系基油と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。   As the (A) lubricating base oil in the present invention, a mineral base oil and / or a synthetic base oil can be used, and two or more mineral base oils or a mixture of synthetic oil base oils can be used. However, it may be a mixture of a mineral base oil and a synthetic base oil. And the mixing ratio of 2 or more types of base oil in the said mixture can be chosen arbitrarily.

鉱油系潤滑油基油としては、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を単独又は二つ以上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、イソパラフィン等が挙げられる。なお、これらの基油は単独でも、2種以上任意の割合で組み合わせて使用してもよい。   As a mineral oil base oil, a lubricating oil fraction obtained by subjecting crude oil to atmospheric distillation and vacuum distillation is subjected to solvent removal, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining. In addition, paraffinic and naphthenic mineral oil base oils, normal paraffins, isoparaffins, and the like, which are refined alone or in appropriate combination of two or more purification treatments such as sulfuric acid washing and clay treatment, can be mentioned. These base oils may be used alone or in combination of two or more at any ratio.

好ましい鉱油系潤滑油基油としては以下の基油を挙げることができる。
(1) パラフィン基系原油および/または混合基系原油の常圧蒸留による留出油;
(2) パラフィン基系原油および/または混合基系原油の常圧蒸留残渣油の減圧蒸留留
出油(WVGO);
(3) 潤滑油脱ろう工程により得られるワックスおよび/またはGTLプロセス等によ
り製造されるフィッシャートロプシュワックス;
(4) (1)〜(3)の中から選ばれる1種または2種以上の混合油のマイルドハイドロクラ
ッキング処理油(MHC);
(5) (1)〜(4)の中から選ばれる2種以上の油の混合油;
(6) (1)、(2)、(3)、(4)または(5)の脱れき油(DAO);
(7) (6)のマイルドハイドロクラッキング処理油(MHC);
(8) (1)〜(7)の中から選ばれる2種以上の油の混合油などを原料油とし、この原料油
および/またはこの原料油から回収された潤滑油留分を、通常の精製方法によって精製し、潤滑油留分を回収することによって得られる潤滑油。
Preferred mineral oil base oils include the following base oils.
(1) Distilled oil obtained by atmospheric distillation of paraffin-based crude oil and / or mixed-base crude oil;
(2) Vacuum distillation distillate (WVGO) of paraffin-based crude oil and / or mixed-base crude oil at atmospheric distillation residue;
(3) Wax obtained by a lubricant dewaxing step and / or a Fischer-Tropsch wax produced by a GTL process or the like;
(4) Mild hydrocracking treatment oil (MHC) of one or two or more mixed oils selected from (1) to (3);
(5) A mixed oil of two or more oils selected from (1) to (4);
(6) Dried oil (DAO) of (1), (2), (3), (4) or (5);
(7) Mild hydrocracking treatment oil (MHC) of (6);
(8) A mixed oil of two or more kinds of oils selected from (1) to (7) is used as a feedstock oil, and this feedstock oil and / or a lubricating oil fraction recovered from this feedstock oil is used as a normal oil fraction. A lubricating oil obtained by refining by a refining method and collecting a lubricating oil fraction.

ここでいう通常の精製方法は特に制限されるものではなく、潤滑油基油製造の際に用いられる精製方法を任意に採用することができる。通常の精製方法としては、例えば、(ア)水素化分解、水素化仕上げなどの水素化精製、(イ)フルフラール溶剤抽出などの溶剤精製、(ウ)溶剤脱ろうや接触脱ろうなどの脱ろう、(エ)酸性白土や活性白土などによる白土精製、(オ)硫酸洗浄、苛性ソーダ洗浄などの薬品(酸またはアルカリ)精製などが挙げられる。本発明ではこれらの1つまたは2つ以上を任意の組み合わせおよび任意の順序で採用することができる。   The normal refining method here is not particularly limited, and a refining method used in the production of the lubricating base oil can be arbitrarily employed. Examples of conventional purification methods include (a) hydrorefining such as hydrocracking and hydrofinishing, (b) solvent purification such as furfural solvent extraction, and (c) dewaxing such as solvent dewaxing and catalytic dewaxing. And (d) white clay refining with acid clay and activated clay, and (e) chemical (acid or alkali) purification such as sulfuric acid washing and caustic soda washing. In the present invention, one or more of these can be used in any combination and in any order.

本発明で用いる鉱油系潤滑油基油としては、上記(1)〜(8)から選ばれる基油をさらに以下の処理を行って得られる基油が特に好ましい。
すなわち、上記(1)〜(8)から選ばれる基油をそのまま、またはこの基油から回収された潤滑油留分を、水素化分解あるいはワックス異性化し、当該生成物をそのまま、もしくはこれから潤滑油留分を回収し、次に溶剤脱ろうや接触脱ろうなどの脱ろう処理を行い、その後、溶剤精製処理するか、または、溶剤精製処理した後、溶剤脱ろうや接触脱ろうなどの脱ろう処理を行って製造される水素化分解鉱油及び/又はワックス異性化イソパラフィン系基油が好ましく用いられる。この水素化分解鉱油及び/又はワックス異性化イソパラフィン系基油は、基油全量基準で好ましくは30質量%以上、より好ましくは50質量%以上、特に好ましくは70質量%以上使用することが望ましい。
The mineral oil base oil used in the present invention is particularly preferably a base oil obtained by further subjecting the base oil selected from the above (1) to (8) to the following treatment.
That is, the base oil selected from the above (1) to (8) is used as it is, or the lubricating oil fraction recovered from this base oil is hydrocracked or wax isomerized, and the product is used as it is or from now on. Collect the fraction, and then perform dewaxing treatment such as solvent dewaxing or contact dewaxing, and then solvent refining treatment, or after solvent refining treatment, dewaxing such as solvent dewaxing or contact dewaxing Hydrocracked mineral oil and / or wax isomerized isoparaffinic base oil produced by treatment is preferably used. The hydrocracked mineral oil and / or wax isomerized isoparaffin base oil is preferably used in an amount of 30% by mass or more, more preferably 50% by mass or more, and particularly preferably 70% by mass or more based on the total amount of the base oil.

本発明の潤滑油組成物における(A)潤滑油基油は、100℃における動粘度が1.5〜4.5mm/sに調整してなる潤滑油基油であることが好ましい。
(A)成分としては、具体的には以下の(A−a)〜(A−c)から選ばれる1種又は2種以上を混合して用いることが好ましい。
(A−a)100℃における動粘度が1.5〜3.5mm/s未満、好ましくは1.9〜3.2mm/sの鉱油系基油
(A−b)100℃における動粘度が3.5〜7mm/s未満、好ましくは3.6〜4.5mm/sの鉱油系基油
(A−c)100℃における動粘度が1.5〜7mm/s未満、好ましくは3.8〜4.5mm/sの合成油系基油
The (A) lubricating base oil in the lubricating oil composition of the present invention is preferably a lubricating base oil whose kinematic viscosity at 100 ° C. is adjusted to 1.5 to 4.5 mm 2 / s.
Specifically, as the component (A), it is preferable to use a mixture of one or more selected from the following (Aa) to (Ac).
(Aa) Mineral oil base oil having a kinematic viscosity at 100 ° C. of less than 1.5 to 3.5 mm 2 / s, preferably 1.9 to 3.2 mm 2 / s (Ab) Kinematic viscosity at 100 ° C. Is less than 3.5 to 7 mm 2 / s, preferably 3.6 to 4.5 mm 2 / s mineral oil base oil (Ac) The kinematic viscosity at 100 ° C. is less than 1.5 to 7 mm 2 / s, preferably Is 3.8 to 4.5 mm 2 / s synthetic oil base oil

ここで、(A−a)〜(A−b)の鉱油系基油の%Cは2以下であることが好ましく、さらに1以下であることが好ましく、0.5以下であることがさらに好ましく、実質的に0であることが特に好ましい。(A−c)の%Cは実質的に0である。(A)潤滑油基油の%Cを2以下とすることでより酸化安定性に優れる潤滑油組成物を得ることができる。
なお、本発明において%Cとは、ASTM D 3238−85に準拠した方法により求められる芳香族炭素数の全炭素数に対する百分率を示す。
Here, (A-a) ~ it is preferred that the% C A of the mineral base oil (A-b) is 2 or less, preferably further 1 or less, further not more than 0.5 It is particularly preferable that it is substantially 0. (A-c)% C A of substantially zero. (A) a% C A of the lubricating base oil can be obtained more lubricating oil composition excellent in oxidative stability by 2 or less.
Note that the% C A in the present invention, showing the percentage of aromatic carbon atoms in total number of carbon obtained by a method in accordance with ASTM D 3238-85.

また、(A−a)〜(A−c)の潤滑油基油は、その粘度指数に格別の限定はないが、粘度指数は80以上が好ましく、より好ましくは100以上、特に好ましくは120以上であり、通常200以下、好ましくは160以下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、低温から高温にわたり良好な粘度特性を示す組成物を得ることができる。また粘度指数が高すぎると組成的にノルマルパラフィン量が増えすぎ、低温流動性が悪化する。   The lubricating base oils (Aa) to (Ac) are not particularly limited in the viscosity index, but the viscosity index is preferably 80 or more, more preferably 100 or more, and particularly preferably 120 or more. It is usually 200 or less, preferably 160 or less. By setting the viscosity index to 80 or more, it is possible to obtain a composition exhibiting good viscosity characteristics from a low temperature to a high temperature. On the other hand, if the viscosity index is too high, the amount of normal paraffin increases in composition and the low temperature fluidity deteriorates.

また、本発明における(A−a)〜(A−b)の鉱油系基油は、その硫黄含有量に格別の限定はないが、0.05質量%以下であることが好ましく、0.02質量%以下であることがさらに好ましく、0.005質量%以下であることが特に好ましい。(A−c)の硫黄含有量は実質的に0%である。(A)成分の硫黄含有量を低減することで組成物の酸化安定性により優れた組成物を得ることができる。   Further, the mineral base oils (Aa) to (Ab) in the present invention are not particularly limited in the sulfur content, but are preferably 0.05% by mass or less, and 0.02 The content is more preferably no more than mass%, and particularly preferably no more than 0.005 mass%. The sulfur content of (Ac) is substantially 0%. By reducing the sulfur content of the component (A), it is possible to obtain a composition that is more excellent in oxidative stability of the composition.

本発明においては、上記(A−a)〜(A−c)をそれぞれ単独でも使用することができるが、任意に混合使用することができる。中でも、(A−a)と、(A−b)及び/又は(A−c)を併用することが好ましい。なお、(A−a)成分及び/又は(A−b)成分と(A−c)成分を併用する場合の(A−c)成分の含有量は、基油全量基準で、好ましくは1〜50質量%、より好ましくは3〜20質量%、さらに好ましくは3〜10質量%である。(A−c)成分を配合することで、安価かつ効果的に、疲労寿命、低温特性、酸化安定性に優れた効果を発現することができる。   In the present invention, each of the above (Aa) to (Ac) can be used alone, but can be arbitrarily mixed and used. Especially, it is preferable to use (Aa) and (Ab) and / or (Ac) together. In addition, the content of the component (Ac) when the component (Aa) and / or the component (Ab) and the component (Ac) are used in combination is preferably 1 to 4 on a base oil total basis. 50 mass%, More preferably, it is 3-20 mass%, More preferably, it is 3-10 mass%. By blending the component (Ac), an effect excellent in fatigue life, low temperature characteristics, and oxidation stability can be expressed inexpensively and effectively.

本発明における(A)潤滑油基油の100℃における動粘度は1.5〜4.5mm/sであることが好ましく、さらに好ましくは2.8〜4.0mm/s、特に好ましくは3.6〜3.9mm/sである。100℃における動粘度を4.5mm/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箇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り、低温粘度に優れた組成物(例えば、−40℃におけるブルックフィールド粘度が2万mPa・s以下)とすることができる。また、100℃における動粘度を1.5mm/s以上とすることによって、油膜形成が十分となり、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。 Preferably the kinematic viscosity at 100 ° C. of (A) a lubricating base oil in the present invention is 1.5 to 4.5 mm 2 / s, more preferably 2.8~4.0mm 2 / s, particularly preferably 3.6 to 3.9 mm 2 / s. By setting the kinematic viscosity at 100 ° C. to 4.5 mm 2 / s or less, it is possible to obtain a lubricating oil composition having a lower frictional resistance at a lubricating location because the fluid resistance becomes smaller, and a composition having excellent low-temperature viscosity. (For example, the Brookfield viscosity at −40 ° C. is 20,000 mPa · s or less). Further, by setting the kinematic viscosity at 100 ° C. to 1.5 mm 2 / s or more, the oil film formation is sufficient, the lubricity is excellent, and the lubricating oil composition has a smaller evaporation loss of the base oil under high temperature conditions. Can be obtained.

(A−c)成分の合成油としては、ポリ−α−オレフィン(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、アルキルジフェニルエタン、モノイソプロピルビフェニル、ジメチルシリコーン、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、並びにポリフェニルエーテル等の合成系潤滑油及びこれらの混合油等が使用できる。これらのうち、ポリ−α−オレフィン及びその水素化物、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、アルキルジフェニルエタン、モノイソプロピルビフェニル、ジメチルシリコーン等は80℃における体積抵抗率が1×1013Ω・m以上であり潤滑油組成物の絶縁性能を高めるために好ましく用いることができる。また、エステル系化合物は一般に80℃における体積抵抗率が1×10〜1×1013Ω・m程度であり、残存水分や不純物を十分除去したものが好ましい。
なお、本明細書において80℃における体積抵抗率とは、JIS C 2101の24.(体積抵抗率試験)に準拠して測定されたものを示す。
Synthetic oils for component (Ac) include poly-α-olefins (1-octene oligomers, 1-decene oligomers, ethylene-propylene oligomers, etc.) and their hydrides, isobutene oligomers and their hydrides, isoparaffins, alkylbenzenes, Alkylnaphthalene, alkyldiphenylethane, monoisopropylbiphenyl, dimethylsilicone, diester (ditridecyl glutarate, di2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di-2-ethylhexyl sebacate, etc.), polyol ester (trimethylolpropane capri) Rate, trimethylolpropane pelargonate, pentaerythritol 2-ethylhexanoate, pentaerythritol pelargonate, etc.), polyoxyal Glycol, dialkyl ethers, as well as synthetic lubricating oils and mixtures oils of these polyphenyl ether and the like can be used. Among these, poly-α-olefin and its hydride, isobutene oligomer and its hydride, isoparaffin, alkylbenzene, alkylnaphthalene, alkyldiphenylethane, monoisopropylbiphenyl, dimethylsilicone, etc. have a volume resistivity of 1 × 10 at 80 ° C. It is 13 Ω · m or more, and can be preferably used for enhancing the insulating performance of the lubricating oil composition. The ester compound generally has a volume resistivity of about 1 × 10 9 to 1 × 10 13 Ω · m at 80 ° C., and preferably has a remaining water and impurities sufficiently removed.
In addition, in this specification, the volume resistivity at 80 ° C. means 24. JIS C 2101. What was measured based on (volume resistivity test) is shown.

本発明における合成油としては、上記合成油のうち、ポリ−α−オレフィン、ポリ−α−オレフィンの水素化物、アルキルベンゼン、エステル系化合物及びこれらの混合物からなる群より選択されるものが好ましい。この場合には、使用条件下で低温流動性と低揮発性とをバランス良く維持することができる。   The synthetic oil in the present invention is preferably selected from the group consisting of poly-α-olefins, poly-α-olefin hydrides, alkylbenzenes, ester compounds, and mixtures thereof among the above synthetic oils. In this case, low temperature fluidity and low volatility can be maintained in a well-balanced condition under use conditions.

ポリα−オレフィンとしては、典型的には、炭素数2〜32、好ましくは6〜16のα−オレフィンのオリゴマーまたはコオリゴマー(例えば、1−オクテンオリゴマー、1−デセンオリゴマー、エチレン−プロピレンコオリゴマー等)及びその水素化物が挙げられる。   The poly α-olefin is typically an α-olefin oligomer or co-oligomer having 2 to 32 carbon atoms, preferably 6 to 16 (eg, 1-octene oligomer, 1-decene oligomer, ethylene-propylene co-oligomer). And hydrides thereof.

これらの合成油は単独で使用されても良い。粘度の制限は特にないが、好ましくは100℃における動粘度が1.5〜4.5mm/sに調整してなるように、異なる粘度のものを組み合わせても良い。これは粘度の高いものと低いものを組み合わせることにより、より高い基油粘度指数を得ることができるためである。 These synthetic oils may be used alone. Although there is no restriction | limiting in particular in a viscosity, You may combine a thing with a different viscosity so that the kinematic viscosity in 100 degreeC may adjust to 1.5-4.5 mm < 2 > / s preferably. This is because a higher base oil viscosity index can be obtained by combining a high viscosity and a low viscosity.

本発明における(A)潤滑油基油は前述の通りであるが、潤滑油組成物としての疲労寿命に問題がある場合は、この基油に動粘度20mm/s〜50mm/sの溶剤精製基油を混合して使用することが好ましい。さらに(A)%Cが2以下であり、100℃における動粘度が1.5〜4.5mm/sに調整してなる範囲で混合して使用すること好ましい。 While (A) the lubricant base oil in the present invention is as described above, if there is a problem in fatigue life of the lubricating oil composition, solvent kinematic viscosity 20mm 2 / s~50mm 2 / s in the base oil It is preferable to use a mixture of refined base oils. Further (A)% C A is 2 or less, it preferably kinematic viscosity at 100 ° C. is used as a mixture in a range comprised adjusted to 1.5 to 4.5 mm 2 / s.

本発明における(B)リン化合物として挙げられる例は、一般式(1)で表されるリン化合物、または一般式(2)で表されるリン化合物、それらのアミン塩からなる群より選ばれる少なくとも1種の化合物である。 Examples which may be mentioned as (B) the phosphorus compound in the present invention, the phosphorus compound represented by the general formula (1), or phosphorus compounds represented by the general formula (2) is selected from amine salts thereof or Ranaru group At least one compound.

Figure 0005779376
Figure 0005779376

一般式(1)において、X、X及びXは、それぞれ個別に酸素原子を示し、、R及びRは、少なくともひとつが水素原子であり、他は炭素数1〜16の炭化水素基を示す。 In the general formula (1), X 1 , X 2 and X 3 each independently represent an oxygen atom , R 1 , R 2 and R 3 each have at least one hydrogen atom, and the others have 1 to 16 carbon atoms. Represents a hydrocarbon group.

Figure 0005779376
Figure 0005779376

一般式(2)において、X、X、X及びXは、それぞれ個別に酸素原子(、X及びXの1つ又は2つが単結合又は(ポリ)オキシアルキレン基でもよい。)を示し、R 、R及びRは、少なくともひとつが水素原子であり、他は炭素数1〜16の炭化水素基を示す。 In the general formula (2), X 4, X 5, X 6 and X 7, one or two single bonds or (poly) oxyalkylene groups each oxygen atom individually (X 4, X 5 and X 6 R 4 , R 5 and R 6 each represents at least one hydrogen atom, and the other represents a hydrocarbon group having 1 to 16 carbon atoms.

上記R〜Rで表される炭素数1〜16の炭化水素基としては、具体的には、アルキル基、シクロアルキル基、アルケニル基、アルキル置換シクロアルキル基、アリール基、アルキル置換アリール基、及びアリールアルキル基を挙げることができ、炭素数1〜16のアルキル基又は炭素数6〜16のアリール基であることが好ましく、さらに好ましくは炭素数3〜16、さらに好ましくは炭素数4〜12のアルキル基である。 Specific examples of the hydrocarbon group having 1 to 16 carbon atoms represented by R 1 to R 6 include an alkyl group, a cycloalkyl group, an alkenyl group, an alkyl-substituted cycloalkyl group, an aryl group, and an alkyl-substituted aryl group. And an arylalkyl group, preferably an alkyl group having 1 to 16 carbon atoms or an aryl group having 6 to 16 carbon atoms, more preferably 3 to 16 carbon atoms, and still more preferably 4 to carbon atoms. 12 alkyl groups.

一般式(1)で表されるリン化合物としては、例えば、以下のリン化合物を挙げることができる。
亜リン酸、モノチオ亜リン酸、ジチオ亜リン酸;上記炭素数1〜16の炭化水素基を1つ有する亜リン酸モノエステル、モノチオ亜リン酸モノエステル、ジチオ亜リン酸モノエステル、トリチオ亜リン酸モノエステル;上記炭素数1〜16の炭化水素基を2つ有する亜リン酸ジエステル、モノチオ亜リン酸ジエステル、ジチオ亜リン酸ジエステル、トリチオ亜リン酸ジエステル;及びこれらの混合物。
As a phosphorus compound represented by General formula (1), the following phosphorus compounds can be mentioned, for example.
Phosphorous acid, monothiophosphorous acid, dithiophosphorous acid; phosphorous acid monoester, monothiophosphorous acid monoester, dithiophosphorous acid monoester, trithiophosphite having one hydrocarbon group having 1 to 16 carbon atoms. Phosphoric acid monoesters; phosphorous acid diesters, monothiophosphorous acid diesters, dithiophosphorous diesters, trithiophosphorous acid diesters having two hydrocarbon groups having 1 to 16 carbon atoms; and mixtures thereof.

本発明においては、高温清浄性や酸化安定性などの性能をより高めるために、一般式(1)のX〜X はそれらの全てが酸素原子であることが特に好ましい。
In the present invention, in order to enhance the performance of such high temperature detergency and oxidation stability, it is particularly preferred that all of X 1 to X 3 Waso those of the general formula (1) is an oxygen atom.

一般式(2)で表されるリン化合物としては、例えば、以下のリン化合物を挙げることができる。
リン酸、モノチオリン酸、ジチオリン酸、トリチオリン酸、テトラチオリン酸;上記炭素数1〜16の炭化水素基を1つ有するリン酸モノエステル、モノチオリン酸モノエステル、ジチオリン酸モノエステル、トリチオリン酸モノエステル、テトラチオリン酸モノエステル;上記炭素数1〜16の炭化水素基を2つ有するリン酸ジエステル、モノチオリン酸ジエステル、ジチオリン酸ジエステル、トリチオリン酸ジエステル、テトラチオリン酸ジエステル;上記炭素数1〜16の炭化水素基を1〜2つ有するホスホン酸、ホスホン酸モノエステル、ホスホン酸ジエステル;炭素数1〜4の(ポリ)オキシアルキレン基を有する上記リン化合物;β−ジチオホスホリル化プロピオン酸やジチオリン酸とオレフィンシクロペンタジエン又は(メチル)メタクリル酸との反応物等の上記リン化合物の誘導体;及びこれらの混合物。
As a phosphorus compound represented by General formula (2), the following phosphorus compounds can be mentioned, for example.
Phosphoric acid, monothiophosphoric acid, dithiophosphoric acid, trithiophosphoric acid, tetrathiophosphoric acid; phosphoric acid monoester having one hydrocarbon group having 1 to 16 carbon atoms, monothiophosphoric acid monoester, dithiophosphoric acid monoester, trithiophosphoric acid monoester, Tetrathiophosphoric acid monoester; phosphoric acid diester having two hydrocarbon groups having 1 to 16 carbon atoms, monothiophosphoric acid diester, dithiophosphoric acid diester, trithiophosphoric acid diester, tetrathiophosphoric acid diester; hydrocarbon having 1 to 16 carbon atoms Phosphonic acid having 1 to 2 groups, phosphonic acid monoester, phosphonic acid diester; phosphorus compound having a (poly) oxyalkylene group having 1 to 4 carbon atoms; β-dithiophosphorylated propionic acid, dithiophosphoric acid and olefinic cyclo Pentadiene or (Me Derivatives of the phosphorus compounds of the reaction product with Le) methacrylic acid; and mixtures thereof.

本発明においては、高温清浄性や酸化安定性などの性能をより高めるために、一般式(2)のX〜X、それらの全てが酸素原子であることが特に好ましい。なお、これらX、X及びXの1つ又は2つが単結合又は(ポリ)オキシアルキレン基でもよい。 In the present invention, in order to enhance the performance of such high temperature detergency and oxidation stability, X 4 to X 7 of the general formula (2) is its It is particularly preferred that all of these is an oxygen atom. One or two of X 4 , X 5 and X 6 may be a single bond or a (poly) oxyalkylene group.

一般式(1)又は(2)で表されるリン化合物の塩としては、リン化合物にアンモニア、炭素数1〜16の炭化水素基又はヒドロキシル基含有炭化水素基のみを分子中に有するアミン化合物等の窒素化合物を作用させて、残存する酸性水素の一部又は全部を中和した塩を挙げることができる。
上記窒素化合物としては、具体的には、アンモニア、モノアミン、ジアミン、ポリアミンが挙げられる。より具体的には、デシルアミン、ドデシルアミン、ジメチルドデシルアミン、トリデシルアミン等の炭素数10〜16のアルキル基又はアルケニル基を有する脂肪族アミン(これらは直鎖状でも分枝状でもよい)が好ましい例として挙げることができる。
Examples of the salt of the phosphorus compound represented by the general formula (1) or (2) include an amine compound having only ammonia, a hydrocarbon group having 1 to 16 carbon atoms, or a hydroxyl group-containing hydrocarbon group in the molecule. The salt which neutralized one part or all part of the remaining acidic hydrogen by making this nitrogen compound act can be mentioned.
Specific examples of the nitrogen compound include ammonia, monoamine, diamine, and polyamine. More specifically, decylamine, dodecylamine, dimethyldodecylamine, aliphatic amines having an alkyl or alkenyl group of carbon number 10 to 16, such as Torideshiruami emissions (These may be and straight-chain or branched) are preferred As an example.

(B)リン化合物としては、一般式(1)におけるX、X及びXが全て酸素原子であるリン化合物のアミン塩及び一般式(2)におけるX、X、X及びXが全て酸素原子(X、X及びXの1つ又は2つが単結合又は(ポリ)オキシアルキレン基でもよい)であるリン化合物のアミン塩からなる群より選ばれる少なくとも1種の化合物であることが、酸化安定性に優れる点で好ましい。 (B) As the phosphorus compound, an amine salt of a phosphorus compound in which X 1 , X 2 and X 3 in the general formula (1) are all oxygen atoms, and X 4 , X 5 , X 6 and X in the general formula (2) At least one compound selected from the group consisting of amine salts of phosphorus compounds in which 7 is an oxygen atom (one or two of X 4 , X 5 and X 6 may be a single bond or a (poly) oxyalkylene group) It is preferable that it is excellent in oxidation stability.

また、(B)リン化合物が、一般式(2)におけるX、X、X及びXの全てが酸素原子(X、X及びXの1つ又は2つが単結合又は(ポリ)オキシアルキレン基でもよい)であり、R、R及びRが少なくともひとつが水素であり、他がそれぞれ個別に炭素数1〜16の炭化水素基であるリン化合物であることが、酸化安定性で好ましい。 In addition, (B) the phosphorus compound is such that all of X 4 , X 5 , X 6 and X 7 in the general formula (2) are oxygen atoms (one or two of X 4 , X 5 and X 6 are single bonds or ( Poly) oxyalkylene group), and at least one of R 4 , R 5, and R 6 is hydrogen, and the other is a phosphorus compound in which each is individually a hydrocarbon group having 1 to 16 carbon atoms, Preferred for oxidation stability.

また(B)リン化合物の炭化水素基の炭素数は16以下が好ましい。これは表1に示すように体積抵抗率は炭素数が少ないほど高くなるという事実に基づく。   (B) The hydrocarbon group of the phosphorus compound preferably has 16 or less carbon atoms. This is based on the fact that the volume resistivity increases as the number of carbon atoms decreases as shown in Table 1.

Figure 0005779376
Figure 0005779376

表1において、体積抵抗率は、JIS C 2101の24.(体積抵抗率試験)に準拠し、油温80℃にて測定された値を示す。測定例についてはいずれも鉱油系基油に、リン元素量で100質量ppmとなるよう添加し溶解させている。   In Table 1, the volume resistivity is JIS C 2101 24. The value measured at an oil temperature of 80 ° C. in accordance with (Volume Resistivity Test) is shown. About the measurement example, all are added and dissolved in mineral oil base oil so that it may become 100 mass ppm in phosphorus element amount.

本発明の潤滑油組成物において上記(B)リン化合物の含有量は、特に制限はないが、組成物全量基準でリン元素換算量として0.03質量%以上であり、一方、その含有量は、好ましくは0.1質量%以下、さらに好ましくは0.08質量%以下、特に好ましくは0.05質量%以下である。(B)リン化合物の含有量が、リン元素として0.03質量%未満の場合は、摩耗防止性に対して効果が不足する。一方、その含有量が、リン元素として0.1質量%を超える場合では、絶縁性能に劣り、酸化安定性が低下し、またシール材への攻撃性が高まる。 The content of the (B) phosphorus compound in the lubricating oil composition of the present invention is not particularly limited, and the terms of phosphorus amount in the total amount of the composition 0. On the other hand, the content is preferably 0.1% by mass or less, more preferably 0.08% by mass or less, and particularly preferably 0.05% by mass or less. (B) When content of a phosphorus compound is less than 0.03 mass% as a phosphorus element, an effect is insufficient with respect to wear prevention property. On the other hand, when the content exceeds 0.1% by mass as the phosphorus element, the insulating performance is inferior, the oxidation stability is lowered, and the aggressiveness to the sealing material is increased.

本発明の潤滑油組成物は、(C)窒素を含む官能基を分散基とする無灰分散剤を組成物全量基準で窒素量が0.001質量%未満含有するか、あるいはまったく含まないことを特徴とする。   The lubricating oil composition of the present invention contains (C) an ashless dispersant having a functional group containing nitrogen as a dispersing group and a nitrogen content of less than 0.001% by mass based on the total amount of the composition, or not at all. Features.

前述のように本発明の潤滑油組成物は、(B)少なくともひとつの水酸基及び/又はチオール基を持つリン化合物から選ばれる少なくとも1種類のリン化合物を含有する。これを含むことにより組成物の耐摩耗性や耐焼付性が大幅に向上する。ところがこのタイプのリン系化合物は水酸基及び/又はチオール基を持たないリン化合物に比べ(C)窒素を含む官能基を分散基とする無灰分散剤が共存すると、体積低効率が大幅に低下する。このため、窒素を含む官能基を分散基とする無灰分散剤を組成物全量基準で窒素量が0.001質量%未満含有するか、あるいはまったく含まないことが、耐摩耗性や耐焼付性の向上と体積抵抗率の向上に必須である。   As described above, the lubricating oil composition of the present invention contains (B) at least one phosphorus compound selected from phosphorus compounds having at least one hydroxyl group and / or thiol group. By including this, the abrasion resistance and seizure resistance of the composition are greatly improved. However, when this type of phosphorus compound coexists with (C) an ashless dispersant having a functional group containing nitrogen as a dispersing group in comparison with a phosphorus compound having no hydroxyl group and / or thiol group, the volumetric efficiency is greatly reduced. Therefore, an ashless dispersant having a functional group containing nitrogen as a dispersing group may contain less than 0.001% by mass of nitrogen based on the total amount of the composition or may contain no ash. Essential for improvement and volume resistivity.

(C)窒素を含む官能基を分散基とする無灰分散剤としては、炭素数40〜400の炭化水素基を有する、コハク酸イミド、ベンジルアミン、ポリアミン等が挙げられる。
ただし、これらの化合物でも、窒素が(B)成分のリン化合物と塩構造を取れない構造に変性されているものは含まない。例えばアミノ基がアシル化されていたり、またホウ素化合物や、硫黄系化合物で変性されいるもので、(B)成分のリン化合物と塩構造を取れない構造のものは含まれない。
また窒素を含む官能基を分散基とする無灰分散剤を組成物全量基準で窒素量が0.001質量%未満含有するとは、(B)成分のリン化合物と塩構造が取れるアミノ基が残されているものでも、その添加量のレベルは組成物として、80℃における体積抵抗率が5×10Ω・m以上である潤滑油組成物となる、構造ないし量であり、具体的には組成物全量基準で窒素量が0.001質量%未満であるものである。より好ましくは組成物全量基準で窒素量が0.0008質量%未満である。
(C) Examples of the ashless dispersant having a functional group containing nitrogen as a dispersing group include succinimide, benzylamine, and polyamine having a hydrocarbon group having 40 to 400 carbon atoms.
However, these compounds do not include those in which nitrogen is modified to a structure that cannot take a salt structure with the phosphorus compound of component (B). For example, an amino group is acylated or modified with a boron compound or a sulfur compound, and does not include a structure that cannot take a salt structure with the phosphorus compound of component (B).
In addition, when an ashless dispersant having a functional group containing nitrogen as a dispersing group contains less than 0.001% by mass of nitrogen based on the total amount of the composition, the phosphorus compound of component (B) and an amino group capable of taking a salt structure remain. However, the level of the added amount is a structure or amount that gives a lubricating oil composition having a volume resistivity of 5 × 10 8 Ω · m or more at 80 ° C. as a composition. The amount of nitrogen is less than 0.001% by mass based on the total amount of matter. More preferably, the nitrogen content is less than 0.0008% by mass based on the total amount of the composition.

なお、同じ窒素を含む化合物である、アミン系酸化防止剤や腐食防止剤であるチアジアゾールやトリアゾール等の構造の化合物は、その添加量が1質量%以下である限り影響は無視できるため、その使用に制限はない。   In addition, as long as the amount of addition is 1% by mass or less, compounds having the same structure containing nitrogen, such as amine antioxidants and corrosion inhibitors such as thiadiazole and triazole, can be ignored. There is no limit.

本発明の潤滑油組成物の80℃における体積抵抗率は、5×10Ω・m以上であることが好ましく、6×10Ω・m以上であることがより好ましく、10×10Ω・m以上であることが特に好ましい。組成物の80℃における体積抵抗率を5×10Ω・m以上とすることで、新油時だけでなく劣化時においても絶縁性能をより高く維持することが可能となり、長期に渡って電動モータがショートする等のトラブルを回避することができる。 The volume resistivity at 80 ° C. of the lubricating oil composition of the present invention is preferably 5 × 10 8 Ω · m or more, more preferably 6 × 10 8 Ω · m or more, 10 × 10 8 Ω. -It is especially preferable that it is m or more. By setting the volume resistivity of the composition at 80 ° C. to 5 × 10 8 Ω · m or more, it becomes possible to maintain a higher insulation performance not only during the new oil but also during the deterioration, and it is electrically operated over a long period of time. Troubles such as a short circuit of the motor can be avoided.

本発明の潤滑油組成物には、その性能をさらに向上させる目的で、必要な性能を付与するために、必要に応じて、粘度指数向上剤、極圧剤、上述した化合物を除く分散剤、金属系清浄剤、摩擦調整剤、酸化防止剤、腐食防止剤、防錆剤、抗乳化剤、金属不活性化剤、流動点降下剤、シール膨潤剤、消泡剤、着色剤等の各種添加剤を単独で又は数種類組み合わせて配合しても良い。   For the purpose of further improving the performance of the lubricating oil composition of the present invention, a viscosity index improver, an extreme pressure agent, a dispersant other than the above-described compounds, as necessary, in order to impart necessary performance, Various additives such as metal detergents, friction modifiers, antioxidants, corrosion inhibitors, rust inhibitors, anti-emulsifiers, metal deactivators, pour point depressants, seal swelling agents, antifoaming agents, and colorants May be blended alone or in combination.

粘度指数向上剤としては、非分散型または分散型ポリ(メタ)アクリレートのほか、非分散型または分散型エチレン−α−オレフィン共重合体またはその水素化物、ポリイソブチレンまたはその水素化物、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、ポリアルキルスチレンおよび構造式(1)で表される(メタ)アクリレートモノマーとエチレン/プロピレン/スチレン/無水マレイン酸のような不飽和モノマーとの共重合体等の粘度指数向上剤をさらに用いることができる。   Viscosity index improvers include non-dispersed or dispersed poly (meth) acrylates, non-dispersed or dispersed ethylene-α-olefin copolymers or hydrides thereof, polyisobutylene or hydrides thereof, and styrene-dienes. Hydrogenated copolymers, styrene-maleic anhydride copolymers, polyalkylstyrenes and (meth) acrylate monomers represented by structural formula (1) and unsaturated monomers such as ethylene / propylene / styrene / maleic anhydride And a viscosity index improver such as a copolymer can be further used.

本発明の潤滑油組成物における粘度指数向上剤の配合量は、組成物の100℃における動粘度が5〜10mm/s、好ましくは6〜9mm/s、かつ、組成物の粘度指数が120〜270、好ましくは150〜250、より好ましくは170〜220となるような量であり、より具体的には、その配合量は、組成物全量基準で15質量%以下、好ましくは10質量%以下、さらに好ましくは8質量%以下であり、2質量%以上、好ましくは4質量%以上、さらに好ましくは5質量%以上である。15質量%を超えると粘度が高くなりすぎ、2質量%未満で十分な組成物粘度を確保できない。 The blending amount of the viscosity index improver in the lubricating oil composition of the present invention is such that the kinematic viscosity at 100 ° C. of the composition is 5 to 10 mm 2 / s, preferably 6 to 9 mm 2 / s, and the viscosity index of the composition is The amount is 120 to 270, preferably 150 to 250, more preferably 170 to 220, and more specifically, the blending amount is 15% by mass or less, preferably 10% by mass based on the total amount of the composition. Hereinafter, it is more preferably 8% by mass or less, 2% by mass or more, preferably 4% by mass or more, and more preferably 5% by mass or more. If it exceeds 15% by mass, the viscosity becomes too high, and if it is less than 2% by mass, a sufficient composition viscosity cannot be ensured.

金属系清浄剤としては、アルカリ土類金属スルホネート、アルカリ土類金属フェネート、アルカリ土類金属サリシレート等の金属系清浄剤が挙げられる。
本発明においては、上記金属系清浄剤の中から任意に選ばれる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、組成物全量基準で0.01〜10質量%、好ましくは0.1〜5質量%である。
Examples of the metal detergent include metal detergents such as alkaline earth metal sulfonate, alkaline earth metal phenate, and alkaline earth metal salicylate.
In the present invention, one or two or more compounds arbitrarily selected from the above metal-based detergents can be contained in any amount, but the content is usually 0 based on the total amount of the composition. 0.01 to 10% by mass, preferably 0.1 to 5% by mass.

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、イミド化合物、脂肪酸エステル、脂肪酸アミド、脂肪酸金属塩等が好ましく用いられる。
本発明においては、上記摩擦調整剤の中から任意に選ばれる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、組成物全量基準で0.01〜5.0質量%、好ましくは0.03〜3.0質量%である。
As the friction modifier, any compound 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, particularly a linear alkyl group having 6 to 30 carbon atoms. Alternatively, amine compounds, imide compounds, fatty acid esters, fatty acid amides, fatty acid metal salts, and the like having at least one linear alkenyl group in the molecule are preferably used.
In the present invention, one kind or two or more kinds of compounds arbitrarily selected from the above friction modifiers can be contained in any amount, but the content is usually 0.00 on the basis of the total amount of the composition. It is 01-5.0 mass%, Preferably it is 0.03-3.0 mass%.

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。
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)脂肪酸(プロピオン酸等)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。
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質量%、好ましくは0.1〜3質量%であるのが望ましい。
As the antioxidant, any phenolic compound or amine compound that is generally used in lubricating oils can be used.
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) fatty acid ( Propionic acid etc.) or (3-methyl-5-tertbutyl-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.
One or two or more compounds arbitrarily selected from these can be contained in any amount, but usually the content is 0.01 to 5 mass based on the total amount of the lubricating oil composition. %, Preferably 0.1 to 3% by mass.

腐食防止剤としては、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、及びイミダゾール系化合物等が挙げられる。   Examples of the corrosion inhibitor include benzotriazole, tolyltriazole, thiadiazole, and imidazole compounds.

防錆剤としては、例えば、石油スルホネート、アルキルベンゼンスルホネート、ジノニルナフタレンスルホネート、アルケニルコハク酸エステル、及び多価アルコールエステル等が挙げられる。   Examples of the rust inhibitor include petroleum sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, alkenyl succinic acid ester, and polyhydric alcohol ester.

抗乳化剤としては、例えば、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、及びポリオキシエチレンアルキルナフチルエーテル等のポリアルキレングリコール系非イオン系界面活性剤等が挙げられる。   Examples of the demulsifier include polyalkylene glycol nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, and polyoxyethylene alkyl naphthyl ether.

金属不活性化剤としては、例えば、イミダゾリン、ピリミジン誘導体、アルキルチアジアゾール、メルカプトベンゾチアゾール、ベンゾトリアゾール又はその誘導体、1,3,4−チアジアゾールポリスルフィド、1,3,4−チアジアゾリル−2,5−ビスジアルキルジチオカーバメート、2−(アルキルジチオ)ベンゾイミダゾール、及びβ−(o−カルボキシベンジルチオ)プロピオンニトリル等が挙げられる。   Examples of metal deactivators include imidazoline, pyrimidine derivatives, alkylthiadiazoles, mercaptobenzothiazoles, benzotriazoles or derivatives thereof, 1,3,4-thiadiazole polysulfide, 1,3,4-thiadiazolyl-2,5-bis. Examples include dialkyldithiocarbamate, 2- (alkyldithio) benzimidazole, and β- (o-carboxybenzylthio) propiononitrile.

流動点降下剤としては、潤滑油基油に応じて公知の流動点降下剤を任意に選択することができるが、重量平均分子量が好ましくは20,000〜500,000、より好ましくは50,000〜300,000、特に好ましくは80,000〜200,000のポリ(メタ)クリレートが好ましい。   As the pour point depressant, a known pour point depressant can be arbitrarily selected according to the lubricating base oil, but the weight average molecular weight is preferably 20,000 to 500,000, more preferably 50,000. Poly (meth) acrylates of ˜300,000, particularly preferably 80,000 to 200,000 are preferred.

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り、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種類以上の化合物を任意の量で配合することができる。   As the antifoaming agent, any compound usually used as an antifoaming agent for lubricating oil can be used, and examples thereof include silicones such as dimethyl silicone and fluorosilicone. One or two or more compounds arbitrarily selected from these can be blended in any amount.

シール膨潤剤としては、潤滑油用のシール膨潤剤として通常用いられる任意の化合物が使用可能であり、例えば、エステル系、硫黄系、芳香族系等のシール膨潤剤が挙げられる。   As the seal swelling agent, any compound usually used as a seal swelling agent for lubricating oil can be used, and examples thereof include ester-based, sulfur-based and aromatic-based seal swelling agents.

着色剤としては、通常用いられる任意の化合物が使用可能であり、また任意の量を配合することができるが、通常その配合量は、組成物全量基準で0.001〜1.0質量%である。   As the colorant, any compound that is usually used can be used, and any amount can be blended. Usually, the blending amount is 0.001 to 1.0% by mass based on the total amount of the composition. is there.

これらの添加剤を本発明の潤滑油組成物に含有させる場合には、その含有量は組成物全量基準で、腐食防止剤、防錆剤、抗乳化剤ではそれぞれ0.005〜5質量%、流動点降下剤、金属不活性化剤では0.005〜2質量%、シール膨潤剤では0.01〜5質量%、消泡剤では0.0005〜1質量%の範囲で通常選ばれる。   When these additives are contained in the lubricating oil composition of the present invention, the content is based on the total amount of the composition, and 0.005 to 5% by mass for the corrosion inhibitor, the rust inhibitor, and the demulsifier, respectively. The point depressant and the metal deactivator are usually selected in the range of 0.005 to 2% by mass, the seal swelling agent in the range of 0.01 to 5% by mass, and the antifoaming agent in the range of 0.0005 to 1% by mass.

以下、本発明の内容を実施例及び比較例によってさらに具体的に説明するが、本発明はこれらに何ら限定されるものではない。   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 to these.

(実施例1、比較例1〜5)
表2に示す組成に従い、本発明に係る潤滑油組成物(実施例1)および比較のための潤滑油組成物(比較例1〜5)を調製した。これらの組成物につき、以下に示す性能評価試験を行い、その結果も表2に示した。
(Example 1, Comparative Examples 1-5)
According to the composition shown in Table 2, a lubricating oil composition according to the present invention (Example 1) and a comparative lubricating oil composition (Comparative Examples 1 to 5) were prepared. These compositions were subjected to the following performance evaluation tests, and the results are also shown in Table 2.

Figure 0005779376
Figure 0005779376

本発明の潤滑油組成物は、焼付き防止性能に優れ、かつ絶縁性能に優れた組成物であり、電気自動車又はハイブリッド車等の電動モータ装着車における潤滑油、電動モータ油、変速機・電動モータ兼用油、又は変速機と電動モータがパッケージ化された、すなわち、変速機と電動モータの潤滑システムが共有化された装置用油等の用途に使用することができる。
また、本発明は、本発明の潤滑油組成物を含む上記変速機、電動モータ、装置、あるいは本発明の潤滑油組成物を用いることによる、上記変速機、電動モータ、装置の潤滑方法、絶縁方法、冷却方法を提供することができる。
The lubricating oil composition of the present invention is a composition having excellent anti-seizure performance and excellent insulating performance. Lubricating oil, electric motor oil, transmission / electric motor in an electric motor-equipped vehicle such as an electric vehicle or a hybrid vehicle. The oil can be used for a motor oil or a device oil in which a transmission and an electric motor are packaged, that is, a lubrication system for the transmission and the electric motor is shared.
In addition, the present invention provides the above transmission, electric motor, and apparatus including the lubricating oil composition of the present invention, or the above-described transmission, electric motor, apparatus lubrication method, and insulation by using the lubricating oil composition of the present invention. A method and a cooling method can be provided.

Claims (1)

(A)潤滑油基油に、(B)一般式(1)または一般式(2)で表される少なくともひとつの水酸基を持ち、かつ炭化水素基の炭素数が16以下であるリン化合物、およびそれらのアミン塩から選ばれる少なくとも1種類のリン化合物を組成物全量基準でリン元素換算量として0.03質量%以上0.1質量%以下配合し(ただし、中性リン系化合物は配合しない)、(C)窒素を含む官能基を分散基とする無灰分散剤を組成物全量基準で窒素量が0.001質量%未満含有するか、あるいはまったく含有せず、80℃における体積抵抗率が5×10Ω・m以上である、変速機油、燃料電池自動車、電気自動車又はハイブリッド自動車に搭載される電動モータ用潤滑油、変速機・電動モータ兼用油、又は変速機と電動モータの潤滑システムが共有化された装置用変速機油の用途に使用される潤滑油組成物。
Figure 0005779376
(一般式(1)において、X、X及びXは、それぞれ個別に酸素原子を示し、R、R及びRは、少なくともひとつが水素原子であり、他は炭素数1〜16の炭化水素基を示す。)
Figure 0005779376
(一般式(2)において、X、X、X及びXは、それぞれ個別に酸素原子(X、X及びXの1つ又は2つが単結合又は(ポリ)オキシアルキレン基でもよい。)を示し、R、R及びRは、少なくともひとつが水素原子であり、他は炭素数1〜16の炭化水素基を示す。)
(A) a lubricating base oil, (B) a phosphorus compound having at least one hydroxyl group represented by general formula (1) or general formula (2) and having a hydrocarbon group having 16 or less carbon atoms, and At least one phosphorus compound selected from those amine salts is blended in an amount of 0.03 % by mass to 0.1% by mass in terms of phosphorus element based on the total amount of the composition (however, a neutral phosphorus compound is not blended) (C) An ashless dispersant having a functional group containing nitrogen as a dispersing group is contained in an amount of nitrogen of less than 0.001% by mass based on the total amount of the composition or not contained at all, and the volume resistivity at 80 ° C. is 5 × is 10 8 Omega-m or more, transmission oil, fuel cell vehicles, electric vehicles or lubricants electric motor mounted in a hybrid vehicle, the transmission-electric motor combined oil, or transmission and the electric motor lubrication system Lubricating oil compositions used in applications shared by the device for transmission fluid.
Figure 0005779376
(In General Formula (1), X 1 , X 2, and X 3 each independently represent an oxygen atom, R 1 , R 2, and R 3 each have at least one hydrogen atom; 16 hydrocarbon groups are shown.)
Figure 0005779376
(In General Formula (2), X 4 , X 5 , X 6 and X 7 are each independently an oxygen atom (one or two of X 4 , X 5 and X 6 are a single bond or a (poly) oxyalkylene group) And at least one of R 4 , R 5 and R 6 represents a hydrogen atom, and the other represents a hydrocarbon group having 1 to 16 carbon atoms.)
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