JP2021138881A - Lubricant composition and method for using lubricant composition - Google Patents

Lubricant composition and method for using lubricant composition Download PDF

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JP2021138881A
JP2021138881A JP2020039404A JP2020039404A JP2021138881A JP 2021138881 A JP2021138881 A JP 2021138881A JP 2020039404 A JP2020039404 A JP 2020039404A JP 2020039404 A JP2020039404 A JP 2020039404A JP 2021138881 A JP2021138881 A JP 2021138881A
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mass
lubricating oil
oil composition
compound
antioxidant
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JP7444644B2 (en
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徳栄 佐藤
Tokuei Sato
徳栄 佐藤
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Idemitsu Kosan Co Ltd
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Idemitsu Kosan Co Ltd
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Priority to EP21763829.5A priority patent/EP4116395A4/en
Priority to US17/905,465 priority patent/US20230107633A1/en
Priority to PCT/JP2021/008644 priority patent/WO2021177441A1/en
Priority to CN202180018513.3A priority patent/CN115175976A/en
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    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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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    • C10M129/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
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    • C10M129/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
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    • C10M133/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/12Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to a carbon atom of a six-membered aromatic ring
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    • C10M137/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
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    • C10M137/04Phosphate esters
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    • C10M169/00Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
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    • C10M2205/02Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
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    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
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Abstract

To provide a lubricant composition that has excellent oxidative stability as evaluated by a RPVOT value, despite of use of a base oil containing a certain amount or more of tertiary carbon, and can maintain oxidative stability for a long period of time by suppressing increase in acid value in an initial stage.SOLUTION: The lubricant composition comprises: a base oil (X) having a tertiary carbon content of 8.0 at% or more based on a total carbon content of hydrocarbons; and an antioxidant (Y) containing an amine-based antioxidant (A), a phenol-based antioxidant (B), and a phosphorus-based antioxidant (C). The amine-based antioxidant (A) contains a diphenylamine compound (A1) having a specific structure. The phenol-based antioxidant (B) contains a hindered phenolic compound (B1) having an ester structure. A total content [(A1) + (B1) + (C)] of the diphenylamine compound (A1), the hindered phenolic compound (B1) having the ester structure and the phosphorus-based antioxidant (C) is from more than 1.0 mass% to at most 2.0 mass% based on a total amount of the lubricant composition.SELECTED DRAWING: None

Description

本発明は、潤滑油組成物、及び潤滑油組成物の使用方法に関する。 The present invention relates to a lubricating oil composition and a method of using the lubricating oil composition.

蒸気タービン及びガスタービン等のタービン、圧縮機、並びに油圧機器等の機器に使用される潤滑油組成物は、高温環境下の系内を循環しながら使用される。そのため、酸化劣化が生じやすい。かかる事情から、当該潤滑油組成物について、高温環境下における長期間の使用に対しても酸化安定性を良好に維持するための様々な研究開発が行われている。 Lubricating oil compositions used in turbines such as steam turbines and gas turbines, compressors, and equipment such as hydraulic equipment are used while circulating in a system in a high temperature environment. Therefore, oxidative deterioration is likely to occur. Under such circumstances, various researches and developments have been carried out on the lubricating oil composition in order to maintain good oxidative stability even after long-term use in a high temperature environment.

例えば、特許文献1には、粘度指数120以上の潤滑油基油と、フェニル−α−ナフチルアミン又はその誘導体と、p,p’−ジアルキルジフェニルアミン又はその誘導体と、粘度指数向上剤とを含有する、回転式ガス圧縮機用潤滑油組成物が開示されている。
特許文献1によれば、当該回転式ガス圧縮機用潤滑油組成物は、高温下で使用された場合であっても、熱・酸化安定性と抗スラッジ性の双方を高水準で達成すると同時に、省エネルギー効果にも優れるとされている。
For example, Patent Document 1 contains a lubricating oil base oil having a viscosity index of 120 or more, phenyl-α-naphthylamine or a derivative thereof, p, p'-dialkyldiphenylamine or a derivative thereof, and a viscosity index improver. Lubricating oil compositions for rotary gas compressors are disclosed.
According to Patent Document 1, the lubricating oil composition for a rotary gas compressor achieves both thermal / oxidation stability and anti-sludge properties at a high level even when used at a high temperature. , It is said that it is also excellent in energy saving effect.

特開2011−162629号公報Japanese Unexamined Patent Publication No. 2011-162629

本発明者は、原料調達の多様化等を踏まえ、タービン、ガス圧縮機、及び油圧機器等の機器に使用される潤滑油組成物について、基油として様々な基油を用い、鋭意検討を行った。その結果、基油として3級炭素を一定量以上含有する基油を用いた場合、ポリαオレフィン及びPAG等の合成油や鉱油等、従来用いられていた基油に対する酸化防止剤の配合では、酸化安定性を長期に亘り維持できないことがわかった。
一方、潤滑油組成物の酸化安定性を示す指標として、JIS K 2514−3:2013又はASTM D 2272で規定されたRPVOT値(回転ボンベ式酸化安定度試験)が主に用いられ、酸化防止剤の性能低下から、使用油の残存寿命の評価を行うのが一般的である。特許文献1においても、RPVOT値(RBOT値)を用いた評価が行われている。
しかしながら、実機での使用環境下においては、潤滑油組成物が装置内を循環して用いられる際に吐出される圧縮空気に同伴して油が系外に飛び出すため、規定量の潤滑油組成物を実機内に維持するために、潤滑油組成物を適宜充填しながら使用されることが多い。そのため、密閉条件下で行われるRPVOT値での評価結果だけでは酸化安定性を正確に評価できていないという課題もあった。なお、酸価の上昇速度が速いとRPVOT値も短くなる傾向にあるため、初期段階の酸価上昇を抑制することは、結果的に、酸化安定性を長期に亘り維持することにも繋がる。
そこで、従来用いられていた基油に対する酸化防止剤の配合では酸化安定性を長期に亘り維持できなかった、3級炭素を一定量以上含有する基油について、酸化安定性を正確に評価するという観点から、RPVOT値により評価される酸化安定性を優れたものとするだけでなく、初期段階の酸価上昇(酸価上昇速度)を抑制することも考慮して、酸化安定性を長期に亘り維持することが望まれる。
Based on the diversification of raw material procurement, the present inventor has conducted a diligent study on lubricating oil compositions used in equipment such as turbines, gas compressors, and hydraulic equipment, using various base oils as base oils. rice field. As a result, when a base oil containing a certain amount or more of tertiary carbon is used as the base oil, the compounding of the antioxidant with respect to the conventionally used base oil such as synthetic oils such as polyαolefin and PAG and mineral oils It was found that oxidative stability could not be maintained for a long period of time.
On the other hand, as an index showing the oxidative stability of the lubricating oil composition, the RPVOT value (rotary cylinder type oxidative stability test) specified by JIS K 2514-3: 2013 or ASTM D 2272 is mainly used, and is an antioxidant. It is common to evaluate the remaining life of the oil used due to the deterioration of the performance of the oil. Also in Patent Document 1, evaluation using the RPVOT value (RBOT value) is performed.
However, under the environment of use in an actual machine, the lubricating oil composition is circulated in the apparatus and the oil is ejected to the outside of the system along with the compressed air discharged when the lubricating oil composition is used. Is often used while being appropriately filled with a lubricating oil composition in order to maintain the above in the actual machine. Therefore, there is also a problem that the oxidative stability cannot be accurately evaluated only by the evaluation result by the RPVOT value performed under the closed condition. Since the RPVOT value tends to be shorter when the acid value rises faster, suppressing the acid value rise in the initial stage eventually leads to maintaining the oxidative stability for a long period of time.
Therefore, it is said that the oxidative stability of a base oil containing a certain amount or more of tertiary carbon, which could not be maintained for a long period of time by blending an antioxidant with the base oil conventionally used, is accurately evaluated. From the viewpoint, not only the oxidative stability evaluated by the RPVOT value is excellent, but also the oxidative stability is maintained for a long period of time in consideration of suppressing the acid value increase (acid value increase rate) in the initial stage. It is desirable to maintain.

そこで、本発明は、3級炭素を一定量以上含有する基油を用いながらも、RPVOT値により評価される酸化安定性を優れたものとすることのみならず、初期段階の酸価上昇(酸価上昇速度)を抑制することで、酸化安定性を長期に亘り維持することができる潤滑油組成物を提供することを課題とする。 Therefore, the present invention not only makes the oxidative stability evaluated by the RPVOT value excellent while using a base oil containing a certain amount or more of tertiary carbon, but also increases the acid value in the initial stage (acid). It is an object of the present invention to provide a lubricating oil composition capable of maintaining oxidative stability for a long period of time by suppressing the rate of increase in value).

本発明者は、鋭意検討を重ねた結果、特定の酸化防止剤の組み合わせと、これら特定の酸化防止剤の合計含有量の調整とによって、上記課題を解決し得ることを見出し、本発明を完成するに至った。 As a result of diligent studies, the present inventor has found that the above problems can be solved by combining specific antioxidants and adjusting the total content of these specific antioxidants, and completed the present invention. I came to do it.

すなわち、本発明は、下記[1]〜[10]に関する。
[1] 3級炭素の含有量が、炭化水素の全炭素基準で、8.0at%以上である基油(X)と、
アミン系酸化防止剤(A)、フェノール系酸化防止剤(B)、及びリン系酸化防止剤(C)を含む酸化防止剤(Y)と、
を含有する潤滑油組成物であって、
前記アミン系酸化防止剤(A)は、下記一般式(a1)で表されるジフェニルアミン化合物(A1)を含み、

Figure 2021138881

[上記一般式(a1)中、Ra1及びRa2は、各々独立に、炭素数1〜30のアルキル基である。na1及びna2は、各々独立に、1〜5の整数である。na1が2以上である場合、複数のRa1は、同一であってもよく、互いに異なっていてもよい。na2が2以上である場合、複数のRa2は、同一であってもよく、互いに異なっていてもよい。]
前記フェノール系酸化防止剤(B)は、エステル構造を有するヒンダードフェノール化合物(B1)を含み、
前記ジフェニルアミン化合物(A1)、前記エステル構造を有するヒンダードフェノール化合物(B1)、及び前記リン系酸化防止剤(C)の合計含有量[(A1)+(B1)+(C)]が、前記潤滑油組成物の全量基準で、1.0質量%超2.0質量%以下である、潤滑油組成物。
[2] 前記ジフェニルアミン化合物(A1)及び前記エステル構造を有するヒンダードフェノール化合物(B1)の合計含有量[(A1)+(B1)]が、前記潤滑油組成物の全量基準で、0.9質量%以上である、上記[1]に記載の潤滑油組成物。
[3] 前記ジフェニルアミン化合物(A1)が、前記潤滑油組成物の全量基準で、0.30質量%〜1.8質量%である、上記[1]又は[2]に記載の潤滑油組成物。
[4] 前記アミン系酸化防止剤(A)が、更に、下記一般式(a2)で表されるナフチルアミン化合物(A2)を含む、上記[1]〜[3]のいずれかに記載の潤滑油組成物。
Figure 2021138881

[上記一般式(a2)中、Ra3は、炭素数1〜30のアルキル基である。na3は、1〜5の整数である。na3が2以上である場合、複数のRa3は、同一であってもよく、互いに異なっていてもよい。]
[5] 前記ジフェニルアミン(A1)と前記ナフチルアミン(A2)の合計含有量[(A1)+(A2)]が、前記潤滑油組成物の全量基準で、0.80質量%以上2.0質量%未満である、上記[4]に記載の潤滑油組成物。
[6] 前記エステル構造を有するヒンダードフェノール化合物(B1)が、下記一般式(b1−1)で表される化合物(B1−1)及び下記一般式(b1−2)で表される化合物(B1−2)からなる群から選択される1種以上である、上記[1]〜[5]のいずれかに記載の潤滑油組成物。
Figure 2021138881

[上記式(b1−1)中、Rb1は、炭素数1〜5のアルキレン基である。Rb2は、炭素数1〜25のアルキル基である。]
Figure 2021138881

[上記式(b1−2)中、Rb3及びRb4は、各々独立に、炭素数1〜5のアルキレン基である。mは、2〜4の整数である。]
[7] 前記リン系酸化防止剤(C)が、下記一般式(c1)で表される、フェノール構造を有するリン原子含有化合物(C1)を含む、上記[1]〜[6]いずれかに記載の潤滑油組成物。
Figure 2021138881

[上記一般式(c1)中、Rc1、Rc2、Rc3、及びRc4は、各々独立に、水素原子又は炭素数1〜30のアルキル基である。]
[8] 更に、極圧剤、清浄分散剤、流動点降下剤、粘度指数向上剤、防錆剤、金属不活性化剤、消泡剤、及び摩擦調整剤からなる群から選択される1種以上の潤滑油用添加剤を含有する、上記[1]〜[7]のいずれかに記載の潤滑油組成物。
[9] 前記基油(X)が、前記潤滑油組成物の全量基準で、90.0質量%以上である、上記[1]〜[8]のいずれかに記載の潤滑油組成物。
[10] タービン、圧縮機、及び油圧機器からなる群から選択される1種以上の機器に用いられる、上記[1]〜[9]のいずれかに記載の潤滑油組成物。
[11] 上記[1]〜[9]のいずれかに記載の潤滑油組成物を、タービン、圧縮機、及び油圧機器からなる群から選択される1種以上の機器に使用する、使用方法。 That is, the present invention relates to the following [1] to [10].
[1] A base oil (X) having a tertiary carbon content of 8.0 at% or more based on the total carbon of hydrocarbons.
An antioxidant (Y) containing an amine-based antioxidant (A), a phenol-based antioxidant (B), and a phosphorus-based antioxidant (C),
A lubricating oil composition containing
The amine-based antioxidant (A) contains a diphenylamine compound (A1) represented by the following general formula (a1), and contains the diphenylamine compound (A1).
Figure 2021138881

[In the above general formula (a1), Ra1 and Ra2 are independently alkyl groups having 1 to 30 carbon atoms. na1 and na2 are each independently an integer of 1-5. If na1 is 2 or more, plural R a1 may be the same or different from each other. If na2 is 2 or more, plural R a2 may be the same or different from each other. ]
The phenolic antioxidant (B) contains a hindered phenol compound (B1) having an ester structure.
The total content of the diphenylamine compound (A1), the hindered phenol compound (B1) having the ester structure, and the phosphorus-based antioxidant (C) [(A1) + (B1) + (C)] is the above. A lubricating oil composition that is more than 1.0% by mass and 2.0% by mass or less based on the total amount of the lubricating oil composition.
[2] The total content [(A1) + (B1)] of the diphenylamine compound (A1) and the hindered phenol compound (B1) having an ester structure is 0.9 based on the total amount of the lubricating oil composition. The lubricating oil composition according to the above [1], which is by mass% or more.
[3] The lubricating oil composition according to the above [1] or [2], wherein the diphenylamine compound (A1) is 0.30% by mass to 1.8% by mass based on the total amount of the lubricating oil composition. ..
[4] The lubricating oil according to any one of [1] to [3] above, wherein the amine-based antioxidant (A) further contains a naphthylamine compound (A2) represented by the following general formula (a2). Composition.
Figure 2021138881

[In the above general formula (a2), Ra3 is an alkyl group having 1 to 30 carbon atoms. na3 is an integer of 1-5. If na3 is 2 or more, plural R a3 may be the same or different from each other. ]
[5] The total content [(A1) + (A2)] of the diphenylamine (A1) and the naphthylamine (A2) is 0.80% by mass or more and 2.0% by mass based on the total amount of the lubricating oil composition. The lubricating oil composition according to the above [4], which is less than or equal to.
[6] The hindered phenol compound (B1) having the ester structure is represented by the compound represented by the following general formula (b1-1) (B1-1) and the compound represented by the following general formula (b1-2) ( The lubricating oil composition according to any one of the above [1] to [5], which is one or more selected from the group consisting of B1-2).
Figure 2021138881

[In the above formula (b1-1), R b1 is an alkylene group having 1 to 5 carbon atoms. R b2 is an alkyl group having 1 to 25 carbon atoms. ]
Figure 2021138881

[In the above formula (b1-2), R b3 and R b4 are independently alkylene groups having 1 to 5 carbon atoms. m is an integer of 2-4. ]
[7] In any of the above [1] to [6], the phosphorus-based antioxidant (C) contains a phosphorus atom-containing compound (C1) having a phenol structure represented by the following general formula (c1). The lubricating oil composition described.
Figure 2021138881

[In the above general formula (c1), R c1 , R c2 , R c3 , and R c4 are each independently a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. ]
[8] Further, one selected from the group consisting of extreme pressure agents, cleaning dispersants, flow point lowering agents, viscosity index improvers, rust preventives, metal deactivators, defoamers, and friction modifiers. The lubricating oil composition according to any one of the above [1] to [7], which contains the above additive for lubricating oil.
[9] The lubricating oil composition according to any one of [1] to [8] above, wherein the base oil (X) is 90.0% by mass or more based on the total amount of the lubricating oil composition.
[10] The lubricating oil composition according to any one of the above [1] to [9], which is used for one or more kinds of equipment selected from the group consisting of a turbine, a compressor, and a hydraulic equipment.
[11] A method of use, wherein the lubricating oil composition according to any one of [1] to [9] above is used for one or more kinds of equipment selected from the group consisting of turbines, compressors, and hydraulic equipment.

本発明によれば、3級炭素を一定量以上含有する基油を用いながらも、RPVOT値により評価される酸化安定性を優れたものにすることのみならず、初期段階の酸価上昇を抑制することで、酸化安定性を長期に亘り維持することができる潤滑油組成物を提供することが可能となる。 According to the present invention, while using a base oil containing a certain amount or more of tertiary carbon, not only the oxidative stability evaluated by the RPVOT value is excellent, but also the increase in acid value in the initial stage is suppressed. By doing so, it becomes possible to provide a lubricating oil composition capable of maintaining oxidative stability for a long period of time.

本明細書において、好ましい数値範囲(例えば、含有量等の範囲)について、段階的に記載された下限値及び上限値は、それぞれ独立して組み合わせることができる。例えば、「好ましくは10〜90、より好ましくは30〜60」という記載から、「好ましい下限値(10)」と「より好ましい上限値(60)」とを組み合わせて、「10〜60」とすることもできる。
また、本明細書において、実施例の数値は、上限値又は下限値として用いられ得る数値である。
本明細書において、「AA〜BB」と表現された数値範囲は、特にことわりのない限り、「AA以上BB以下」を意味する。
In the present specification, with respect to a preferable numerical range (for example, a range such as content), the lower limit value and the upper limit value described stepwise can be combined independently. For example, from the description of "preferably 10 to 90, more preferably 30 to 60", the "preferable lower limit value (10)" and the "more preferable upper limit value (60)" are combined to obtain "10 to 60". You can also do it.
Further, in the present specification, the numerical values of Examples are numerical values that can be used as an upper limit value or a lower limit value.
In the present specification, the numerical range expressed as "AA to BB" means "AA or more and BB or less" unless otherwise specified.

[本発明の潤滑油組成物の態様]
本発明の潤滑油組成物は、3級炭素の含有量が、炭化水素の全炭素基準で、8.0at%以上である基油(X)と、アミン系酸化防止剤(A)、フェノール系酸化防止剤(B)、及びリン系酸化防止剤(C)を含む酸化防止剤(Y)と、を含有する潤滑油組成物である。
アミン系酸化防止剤(A)は、下記一般式(a1)で表されるジフェニルアミン化合物(A1)を含む。

Figure 2021138881

[上記一般式(a1)中、Ra1及びRa2は、各々独立に、炭素数1〜30のアルキル基である。na1及びna2は、各々独立に、1〜5の整数である。na1が2以上である場合、複数のRa1は、同一であってもよく、互いに異なっていてもよい。na2が2以上である場合、複数のRa2は、同一であってもよく、互いに異なっていてもよい。]
フェノール系酸化防止剤(B)は、エステル構造を有するヒンダードフェノール化合物(B1)を含む。
そして、ジフェニルアミン化合物(A1)、エステル構造を有するヒンダードフェノール化合物(B1)、及びリン系酸化防止剤(C)の合計含有量[(A1)+(B1)+(C)]は、潤滑油組成物の全量基準で、1.0質量%超2.0質量%以下である。 [Aspects of Lubricating Oil Composition of the Present Invention]
The lubricating oil composition of the present invention contains a base oil (X) having a tertiary carbon content of 8.0 at% or more based on the total carbon content of hydrocarbons, an amine-based antioxidant (A), and a phenol-based oil. It is a lubricating oil composition containing an antioxidant (B) and an antioxidant (Y) containing a phosphorus-based antioxidant (C).
The amine-based antioxidant (A) contains a diphenylamine compound (A1) represented by the following general formula (a1).
Figure 2021138881

[In the above general formula (a1), Ra1 and Ra2 are independently alkyl groups having 1 to 30 carbon atoms. na1 and na2 are each independently an integer of 1-5. If na1 is 2 or more, plural R a1 may be the same or different from each other. If na2 is 2 or more, plural R a2 may be the same or different from each other. ]
The phenolic antioxidant (B) contains a hindered phenol compound (B1) having an ester structure.
The total content [(A1) + (B1) + (C)] of the diphenylamine compound (A1), the hindered phenol compound (B1) having an ester structure, and the phosphorus-based antioxidant (C) is a lubricating oil. It is more than 1.0% by mass and 2.0% by mass or less based on the total amount of the composition.

本発明者は、3級炭素を一定量以上含有する基油を用いながらも、RPVOT値により評価される酸化安定性を優れたものとすることのみならず、初期段階の酸価上昇を抑制することで、酸化安定性を長期に亘り維持することができる潤滑油組成物を提供することを課題として、鋭意検討を行った。
まず、3級炭素を一定量以上含有する基油を用いた場合に、ポリαオレフィン及びPAG等の合成油や鉱油等、従来用いられていた基油に対する酸化防止剤の配合では、酸化防止剤が効きにくい理由について検討した。その結果、3級炭素のラジカルは、3級炭素よりも低級炭素のラジカルと比較して安定であるため、3級炭素を一定量以上含有する基油は、酸素原子を捕捉し得るラジカルがより多く存在し、酸化劣化が起こりやすくなることが要因の一つとして考えられた。そして、このことから、3級炭素を一定量以上含有する基油を用いる場合、酸化防止剤の配合の調整が従来よりも困難であると考えられた。実際、3級炭素を一定量以上含有する基油に、従来と同様に酸化防止剤を配合しても酸化防止剤が効きにくく、上記課題を解決する潤滑油組成物の調整は困難を極めた。
かかる状況の下、本発明者は、酸化防止剤の配合について種々検討を重ね、上記課題を解決し得る酸化防止剤の配合を見出し、本発明を完成するに至った。
Although the present inventor uses a base oil containing a certain amount or more of tertiary carbon, it not only enhances the oxidative stability evaluated by the RPVOT value, but also suppresses an increase in acid value in the initial stage. Therefore, an earnest study was conducted with the task of providing a lubricating oil composition capable of maintaining oxidative stability for a long period of time.
First, when a base oil containing a certain amount or more of tertiary carbon is used, the antioxidant is added to the conventionally used base oil such as synthetic oils such as polyα-olefins and PAGs and mineral oils. I examined the reason why it is difficult to work. As a result, the radical of the tertiary carbon is more stable than the radical of the lower carbon than the tertiary carbon, so that the base oil containing a certain amount or more of the tertiary carbon has more radicals capable of capturing oxygen atoms. It was considered that one of the factors was that there were many of them and oxidative deterioration was likely to occur. From this, it was considered that when a base oil containing a certain amount or more of tertiary carbon is used, it is more difficult to adjust the composition of the antioxidant than before. In fact, even if an antioxidant is added to a base oil containing a certain amount or more of tertiary carbon as in the conventional case, the antioxidant is difficult to work, and it is extremely difficult to prepare a lubricating oil composition that solves the above problems. ..
Under such circumstances, the present inventor has repeated various studies on the formulation of an antioxidant, found a formulation of an antioxidant that can solve the above problems, and completed the present invention.

なお、以降の説明では、「基油(X)」及び「酸化防止剤(Y)」を、それぞれ「成分(X)」及び「成分(Y)」ともいう。
本発明の一態様の潤滑油組成物は、成分(X)及び成分(Y)のみから構成されていてもよいが、本発明の効果を損なわない範囲で、成分(X)及び成分(Y)以外の他の成分を含有していてもよい。
本発明の一態様の潤滑油組成物において、成分(X)及び成分(Y)の合計含有量は、潤滑油組成物の全量基準で、好ましくは80質量%以上、より好ましくは85質量%以上、更に好ましくは90質量%以上、より更に好ましくは95質量%以上、更になお好ましくは97質量%以上である。また、好ましくは、99.9質量%以下である。
In the following description, the "base oil (X)" and the "antioxidant (Y)" are also referred to as "component (X)" and "component (Y)", respectively.
The lubricating oil composition of one aspect of the present invention may be composed of only the component (X) and the component (Y), but the component (X) and the component (Y) are used as long as the effects of the present invention are not impaired. It may contain other components other than.
In the lubricating oil composition of one aspect of the present invention, the total content of the component (X) and the component (Y) is preferably 80% by mass or more, more preferably 85% by mass or more, based on the total amount of the lubricating oil composition. , More preferably 90% by mass or more, even more preferably 95% by mass or more, and even more preferably 97% by mass or more. Further, it is preferably 99.9% by mass or less.

以下、本発明の潤滑油組成物が含有する各成分について、詳細に説明する。 Hereinafter, each component contained in the lubricating oil composition of the present invention will be described in detail.

<基油(X)>
本発明の潤滑油組成物は、基油(X)を含有する。
基油(X)は、3級炭素の含有量が、基油(X)中の炭化水素の全炭素基準で、8.0at%以上である。
本発明者の検討によると、基油(X)の3級炭素の含有量が、基油(X)中の炭化水素の全炭素基準で、8.0at%以上である場合、酸化劣化が起こりやすく、酸化防止剤の配合の調整が従来よりも困難であることがわかっている。本発明では、後述する酸化防止剤の配合の調整によって、酸化安定性を長期に亘り維持しつつ、酸価の上昇を抑制するようにしている。
なお、本発明の一態様では、基油(X)の3級炭素の含有量は、8.5at%以上であってもよく、9.0at%以上であってもよく、9.5at%以上であってもよく、10.0at%以上であってもよい。なお、基油(X)の3級炭素の含有量の上限値は、通常、20.0at%以下である。
なお、基油(X)中の炭化水素の全炭素基準での3級炭素の含有量は、13C−NMRにより測定される、全炭素の積分強度の合計に対する3級炭素に起因する積分強度の合計の割合を意味するが、同等の結果が得られるのであればその他の方法を用いてもよい。なお、13C−NMR測定にあたっては、サンプルとして測定対象試料0.5gに3gの重クロロホルムを加えて希釈したものを使用し、測定温度は室温、共鳴周波数は100MHzとし、測定法はゲート付デカップリング法を使用する方法が挙げられる。上記分析により、後述するように(a)と(b)をそれぞれ測定し、(a)を100%とした時の(b)の割合(%)を算出する。(b)の割合は基油(X)を構成する全炭素原子に対する全3級炭素原子の割合を示す。
(a)化学シフト約10−50ppmの積分強度の合計(炭化水素の全炭素に起因する積分強度の合計)
(b)化学シフト約27.9−28.1ppm、28.4−28.6ppm、32.6−33.2ppm、34.4−34.6ppm、37.4−37.6ppm、38.8−39.1ppm、及び、40.4−40.6ppmの積分強度の合計(メチル基、エチル基、及びその他分岐基がついた3級炭素及びナフテン3級炭素に起因する積分強度の合計)
なお、基油(X)が混合基油の場合には、当該混合基油の3級炭素の含有量を上述の方法で測定した値を示す。
<Base oil (X)>
The lubricating oil composition of the present invention contains a base oil (X).
The base oil (X) has a tertiary carbon content of 8.0 at% or more based on the total carbon of hydrocarbons in the base oil (X).
According to the study by the present inventor, when the content of tertiary carbon in the base oil (X) is 8.0 at% or more based on the total carbon content of the hydrocarbon in the base oil (X), oxidative deterioration occurs. It is easy and it is known that it is more difficult to adjust the composition of the antioxidant than before. In the present invention, by adjusting the composition of the antioxidant described later, the increase in acid value is suppressed while maintaining the oxidative stability for a long period of time.
In one aspect of the present invention, the content of the tertiary carbon of the base oil (X) may be 8.5 at% or more, 9.0 at% or more, or 9.5 at% or more. It may be 10.0 at% or more. The upper limit of the tertiary carbon content of the base oil (X) is usually 20.0 at% or less.
The content of tertiary carbon in the base oil (X) based on the total carbon is the integrated strength due to the tertiary carbon with respect to the total integrated carbon strength measured by 13 C-NMR. It means the ratio of the total of, but other methods may be used as long as the same result can be obtained. For 13 C-NMR measurement, 0.5 g of the sample to be measured was diluted with 3 g of deuterated chloroform, the measurement temperature was room temperature, the resonance frequency was 100 MHz, and the measurement method was decup with a gate. A method using the ring method can be mentioned. By the above analysis, (a) and (b) are measured as described later, and the ratio (%) of (b) when (a) is 100% is calculated. The ratio of (b) indicates the ratio of all tertiary carbon atoms to all carbon atoms constituting the base oil (X).
(A) Total integrated intensity of chemical shift of about 10-50 ppm (total integrated intensity due to total carbon of hydrocarbon)
(B) Chemical shift Approximately 27.9-28.1 ppm, 28.4-28.6 ppm, 32.6-33.2 ppm, 34.4-34.6 ppm, 37.4-37.6 ppm, 38.8- Total integrated intensities of 39.1 ppm and 40.4-40.6 ppm (total integrated intensities due to tertiary and naphthenic tertiary carbons with methyl, ethyl, and other branched groups)
When the base oil (X) is a mixed base oil, the value obtained by measuring the tertiary carbon content of the mixed base oil by the above method is shown.

(基油(X)の含有量)
本発明の一態様の潤滑油組成物において、基油(X)の含有量は、潤滑油組成物の全量基準で、好ましくは90.0質量%以上、より好ましくは93.0質量%以上、更に好ましくは95.0質量%以上である。また、好ましくは99.0質量%未満、より好ましくは98.5質量%以下、更に好ましくは98.0質量%以下である。
(Content of base oil (X))
In the lubricating oil composition of one aspect of the present invention, the content of the base oil (X) is preferably 90.0% by mass or more, more preferably 93.0% by mass or more, based on the total amount of the lubricating oil composition. More preferably, it is 95.0% by mass or more. Further, it is preferably less than 99.0% by mass, more preferably 98.5% by mass or less, and further preferably 98.0% by mass or less.

(基油(X)の種類)
基油(X)としては、3級炭素の含有量が、基油(X)中の炭化水素の全炭素基準で、8.0at%以上である基油を、特に制限なく用いることができる。以下、「3級炭素の含有量が、基油(X)中の炭化水素の全炭素基準で、8.0at%以上である基油」を、「3級炭素高含有基油」ともいう。
3級炭素高含有基油の代表例としては、例えば、パラフィン系鉱油、中間系鉱油、ナフテン系鉱油等の原油を常圧蒸留して得られる常圧残油;当該常圧残油を減圧蒸留して得られる留出油;当該留出油を、溶剤脱れき、溶剤抽出、水素化仕上げ、溶剤脱ろう、接触脱ろう、異性化脱ろう、減圧蒸留等の精製処理の一つ以上の処理を施した鉱油又はワックス(スラックワックス、GTLワックス等)や、イソパラフィン重合体等が挙げられる。
これらの基油(X)は、1種からなるものであってもよく、2種以上を組み合わせた混合油であってもよい。
(Type of base oil (X))
As the base oil (X), a base oil having a tertiary carbon content of 8.0 at% or more based on the total carbon content of hydrocarbons in the base oil (X) can be used without particular limitation. Hereinafter, "a base oil having a tertiary carbon content of 8.0 at% or more based on the total carbon content of hydrocarbons in the base oil (X)" is also referred to as a "classical carbon high content base oil".
Typical examples of tertiary carbon-rich base oils are atmospheric residual oils obtained by atmospheric distillation of crude oils such as paraffin mineral oils, intermediate mineral oils, and naphthenic mineral oils; atmospheric distillation of the atmospheric residual oils under reduced pressure. Distillate oil obtained by Examples thereof include mineral oils or waxes (slack wax, GTL wax, etc.) and isoparaffin polymers.
These base oils (X) may be composed of one kind or may be a mixed oil in which two or more kinds are combined.

なお、基油(X)は、3級炭素の含有量が、基油(X)の全量基準で、8.0at%以上であることを満たす範囲内で、3級炭素の含有量が8.0at%未満である基油、例えば、合成油や植物油等を1種または2種以上組み合わせて含有していてもよい。 The base oil (X) has a tertiary carbon content of 8. within a range satisfying that the tertiary carbon content is 8.0 at% or more based on the total amount of the base oil (X). A base oil having a content of less than 0 at%, for example, a synthetic oil, a vegetable oil, or the like may be contained in one or a combination of two or more.

但し、本発明の効果をより発揮させやすくするという観点から、基油(X)は、基油の全量基準で、50質量%〜100質量%含むことが好ましく、60質量%〜100質量%含むことがより好ましく、70質量%〜100質量%含むことが更に好ましく、80質量%〜100質量%含むことがより更に好ましく、90質量%〜100質量%含むことが更になお好ましい。 However, from the viewpoint of making it easier to exert the effect of the present invention, the base oil (X) preferably contains 50% by mass to 100% by mass, and contains 60% by mass to 100% by mass, based on the total amount of the base oil. More preferably, it further preferably contains 70% by mass to 100% by mass, further preferably 80% by mass to 100% by mass, and even more preferably 90% by mass to 100% by mass.

(基油(X)の40℃における動粘度、粘度指数)
基油(X)の40℃における動粘度(以下、「40℃動粘度」ともいう)は、好ましくは10mm/s〜100mm/s、より好ましくは30mm/s〜60mm/s、更に好ましくは35mm/s〜55mm/s、より更に好ましくは40mm/s〜50mm/sである。
また、基油(X)の粘度指数は、好ましくは100以上、より好ましくは125以上、更に好ましくは130以上である。また、通常150以下である。
本明細書において、基油(X)の40℃動粘度及び粘度指数は、JIS K 2283:2000に準拠して測定及び算出した値である。
(Kinematic viscosity and viscosity index of base oil (X) at 40 ° C)
Kinematic viscosity (hereinafter also referred to as "40 ° C. kinematic viscosity") at 40 ° C. of the base oil (X) is preferably from 10mm 2 / s~100mm 2 / s, more preferably 30mm 2 / s~60mm 2 / s, more preferably 35mm 2 / s~55mm 2 / s, even more preferably 40mm 2 / s~50mm 2 / s.
The viscosity index of the base oil (X) is preferably 100 or more, more preferably 125 or more, and further preferably 130 or more. Moreover, it is usually 150 or less.
In the present specification, the 40 ° C. kinematic viscosity and viscosity index of the base oil (X) are values measured and calculated in accordance with JIS K 2283: 2000.

<酸化防止剤(Y)>
本発明の潤滑油組成物は、酸化防止剤(Y)を含有する。
潤滑油組成物が酸化防止剤(Y)を含有しない場合、本発明の効果が奏されない。
本発明の潤滑油組成物が含有する酸化防止剤(Y)は、アミン系酸化防止剤(A)、フェノール系酸化防止剤(B)、及びリン系酸化防止剤(C)を含む。以降の説明では、これらをそれぞれ「成分(A)」、「成分(B)」、及び「成分(C)」ともいう。
本発明の一態様の潤滑油組成物において、酸化防止剤(Y)は、成分(A)、成分(B)、及び成分(C)のみから構成されていてもよいが、本発明の効果を損なわない範囲で、成分(A)、成分(B)、及び成分(C)以外の他の酸化防止剤を含有していてもよい。
本発明の一態様の潤滑油組成物において、成分(A)、成分(B)、及び成分(C)の合計含有量は、本発明の効果を発揮させやすくするという観点から、酸化防止剤(Y)の全量基準で、好ましくは60質量%〜100質量%、より好ましくは70質量%〜100質量%、更に好ましくは80質量%〜100質量%、より更に好ましくは90質量%〜100質量%、更になお好ましくは95質量%〜100質量%である。
以下、アミン系酸化防止剤(A)、フェノール系酸化防止剤(B)、及びリン系酸化防止剤(C)について、詳細に説明する。
<Antioxidant (Y)>
The lubricating oil composition of the present invention contains an antioxidant (Y).
If the lubricating oil composition does not contain the antioxidant (Y), the effects of the present invention will not be achieved.
The antioxidant (Y) contained in the lubricating oil composition of the present invention includes an amine-based antioxidant (A), a phenol-based antioxidant (B), and a phosphorus-based antioxidant (C). In the following description, these are also referred to as "component (A)", "component (B)", and "component (C)", respectively.
In the lubricating oil composition of one aspect of the present invention, the antioxidant (Y) may be composed of only the component (A), the component (B), and the component (C), but the effect of the present invention can be obtained. An antioxidant other than the component (A), the component (B), and the component (C) may be contained as long as the component (A), the component (B), and the component (C) are not impaired.
In the lubricating oil composition of one aspect of the present invention, the total content of the component (A), the component (B), and the component (C) is an antioxidant (from the viewpoint of facilitating the effect of the present invention. Based on the total amount of Y), preferably 60% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, still more preferably 80% by mass to 100% by mass, still more preferably 90% by mass to 100% by mass. Even more preferably, it is 95% by mass to 100% by mass.
Hereinafter, the amine-based antioxidant (A), the phenol-based antioxidant (B), and the phosphorus-based antioxidant (C) will be described in detail.

<アミン系酸化防止剤(A)>
本発明の潤滑油組成物は、酸化防止剤(Y)として、アミン系酸化防止剤(A)を含有する。
アミン系酸化防止剤(A)は、酸化防止性能を有し、アミノ基を含有する化合物である。
以下、本発明の潤滑油組成物において用いられる、アミン系酸化防止剤(A)について、詳細に説明する
<Amine-based antioxidant (A)>
The lubricating oil composition of the present invention contains an amine-based antioxidant (A) as an antioxidant (Y).
The amine-based antioxidant (A) is a compound having an antioxidant performance and containing an amino group.
Hereinafter, the amine-based antioxidant (A) used in the lubricating oil composition of the present invention will be described in detail.

(ジフェニルアミン化合物(A1))
本発明の潤滑油組成物において、アミン系酸化防止剤(A)は、下記一般式(a1)で表されるジフェニルアミン化合物(A1)を含む。

Figure 2021138881

[上記一般式(a1)中、Ra1及びRa2は、各々独立に、炭素数1〜30のアルキル基である。na1及びna2は、各々独立に、1〜5の整数である。na1が2以上である場合、複数のRa1は、同一であってもよく、互いに異なっていてもよい。na2が2以上である場合、複数のRa2は、同一であってもよく、互いに異なっていてもよい。]
本発明者の検討によると、ジフェニルアミン化合物(A1)は、リン系酸化防止剤(C)と併用することで、RPVOT値で評価される酸化安定性を良好にする性能を有する。一方で、ジフェニルアミン化合物(A1)は、初期段階で酸価を上昇させてしまう傾向にある。そこで、本発明では、初期段階の酸化上昇を抑制することで、酸化安定性を長期に亘り維持するために、ジフェニルアミン化合物(A1)、エステル構造を有するヒンダードフェノール化合物(B1)、及びリン系酸化防止剤(C)の合計含有量[(A1)+(B1)+(C)]を一定範囲に規定している。なお、潤滑油組成物がジフェニルアミン化合物(A1)を含有しない場合、本発明の効果が奏されない。 (Diphenylamine compound (A1))
In the lubricating oil composition of the present invention, the amine-based antioxidant (A) contains a diphenylamine compound (A1) represented by the following general formula (a1).
Figure 2021138881

[In the above general formula (a1), Ra1 and Ra2 are independently alkyl groups having 1 to 30 carbon atoms. na1 and na2 are each independently an integer of 1-5. If na1 is 2 or more, plural R a1 may be the same or different from each other. If na2 is 2 or more, plural R a2 may be the same or different from each other. ]
According to the study of the present inventor, the diphenylamine compound (A1) has a performance of improving the oxidative stability evaluated by the RPVOT value when used in combination with the phosphorus-based antioxidant (C). On the other hand, the diphenylamine compound (A1) tends to increase the acid value in the initial stage. Therefore, in the present invention, in order to maintain the oxidative stability for a long period of time by suppressing the increase in oxidation at the initial stage, a diphenylamine compound (A1), a hindered phenol compound having an ester structure (B1), and a phosphorus-based compound are used. The total content of the antioxidant (C) [(A1) + (B1) + (C)] is specified within a certain range. If the lubricating oil composition does not contain the diphenylamine compound (A1), the effect of the present invention will not be exhibited.

上記一般式(a1)中、Ra1及びRa2として選択し得るアルキル基の炭素数は、本発明の効果を発揮させやすくするという観点から、各々独立に、好ましくは1〜20、より好ましくは4〜16、更に好ましくは4〜14である。
a1及びRa2として選択し得るアルキル基の具体例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、イコシル基、ヘンイコシル基、ドコシル基、トリコシル基、テトラコシル基、ペンタコシル基、ヘキサコシル基、ヘプタコシル基、オクタコシル基、ノナコシル基、トリアコンチル基等が挙げられる。
これらのアルキル基は、直鎖状であっても分岐鎖状であってもよいが、本発明の効果を発揮させやすくするという観点から、直鎖状であることが好ましい。
In the above general formula (a1), the carbon number of the alkyl group that can be selected as Ra1 and Ra2 is independently, preferably 1 to 20, more preferably 1 to 20 from the viewpoint of facilitating the effect of the present invention. It is 4 to 16, more preferably 4 to 14.
Specific examples of the alkyl group that can be selected as R a1 and R a2 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group and an undecyl group. Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecil group, icosyl group, henicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group. , Nonacosyl group, Triacontyl group and the like.
These alkyl groups may be linear or branched, but are preferably linear from the viewpoint of facilitating the effects of the present invention.

上記一般式(a1)中、na1及びna2は、本発明の効果を発揮させやすくするという観点から、各々独立に、好ましくは1〜3、より好ましくは1〜2、更に好ましくは1である。 In the general formula (a1), na1 and na2 are independently preferably 1-3, more preferably 1-2, and even more preferably 1 independently from the viewpoint of facilitating the effect of the present invention.

ジフェニルアミン化合物(A1)は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。 As the diphenylamine compound (A1), one type may be used alone, or two or more types may be used in combination.

ジフェニルアミン化合物(A1)の含有量は、潤滑油組成物の全量基準で、好ましくは0.30質量%〜1.8質量%、より好ましくは0.30質量%〜1.2質量%、更に好ましくは0.40質量%〜1.1質量%である。
ジフェニルアミン化合物(A1)の含有量が上記範囲であることにより、RPVOT値で評価される潤滑油組成物の酸化安定性を良好なものとしつつ、潤滑油組成物の初期段階の酸価の上昇を抑制しやすい。
The content of the diphenylamine compound (A1) is preferably 0.30% by mass to 1.8% by mass, more preferably 0.30% by mass to 1.2% by mass, still more preferably, based on the total amount of the lubricating oil composition. Is 0.40% by mass to 1.1% by mass.
When the content of the diphenylamine compound (A1) is in the above range, the oxidation stability of the lubricating oil composition evaluated by the RPVOT value is improved, and the acid value of the lubricating oil composition is increased in the initial stage. Easy to suppress.

(ナフチルアミン化合物(A2))
本発明の一態様の潤滑油組成物において、本発明の効果をより発揮させやすくするという観点から、アミン系酸化防止剤(A)は、下記一般式(a2)で表されるナフチルアミン化合物(A2)を含むことが好ましい。

Figure 2021138881

[上記一般式(a2)中、Ra3は、炭素数1〜30のアルキル基である。na3は、1〜5の整数である。na3が2以上である場合、複数のRa3は、同一であってもよく、互いに異なっていてもよい。] (Naphthylamine compound (A2))
From the viewpoint of making it easier to exert the effects of the present invention in the lubricating oil composition of one aspect of the present invention, the amine-based antioxidant (A) is a naphthylamine compound (A2) represented by the following general formula (a2). ) Is preferably included.
Figure 2021138881

[In the above general formula (a2), Ra3 is an alkyl group having 1 to 30 carbon atoms. na3 is an integer of 1-5. If na3 is 2 or more, plural R a3 may be the same or different from each other. ]

上記一般式(a2)中、Ra3として選択し得るアルキル基の炭素数は、本発明の効果を発揮させやすくするという観点から、好ましくは1〜20、より好ましくは4〜16、更に好ましくは6〜14である。
a3として選択し得るアルキル基の具体例としては、Ra1及びRa2として選択し得るアルキル基として例示したものが挙げられる。
これらのアルキル基は、直鎖状であっても分岐鎖状であってもよいが、本発明の効果を発揮させやすくするという観点から、直鎖状であることが好ましい。
In the general formula (a2), the carbon number of the alkyl group may be selected as R a3, from the viewpoint of easy to exhibit the effects of the present invention, preferably 1 to 20, more preferably 4 to 16, more preferably 6 to 14.
Specific examples of the alkyl group that can be selected as R a3 include those exemplified as the alkyl group that can be selected as R a1 and R a2.
These alkyl groups may be linear or branched, but are preferably linear from the viewpoint of facilitating the effects of the present invention.

上記一般式(a2)中、na3は、本発明の効果を発揮させやすくするという観点から、好ましくは1〜3、より好ましくは1〜2、更に好ましくは1である。 In the general formula (a2), na3 is preferably 1 to 3, more preferably 1 to 2, and even more preferably 1 from the viewpoint of facilitating the effect of the present invention.

ナフチルアミン化合物(A2)は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。 As the naphthylamine compound (A2), one type may be used alone, or two or more types may be used in combination.

ナフチルアミン化合物(A2)の含有量は、本発明の効果をより発揮させやすくするという観点から、潤滑油組成物の全量基準で、好ましくは0.50質量%〜0.80質量%、より好ましくは0.55質量%〜0.75質量%、更に好ましくは0.60質量%〜0.70質量%である。 The content of the naphthylamine compound (A2) is preferably 0.50% by mass to 0.80% by mass, more preferably 0.50% by mass, based on the total amount of the lubricating oil composition, from the viewpoint of facilitating the effect of the present invention. It is 0.55% by mass to 0.75% by mass, more preferably 0.60% by mass to 0.70% by mass.

(アミン系酸化防止剤(A)中の各種アミン化合物の含有量、含有比率)
本発明の一態様の潤滑油組成物において、ジフェニルアミン化合物(A1)の含有量は、本発明の効果を発揮させやすくするという観点から、アミン系酸化防止剤(A)の全量基準で、好ましくは30質量%〜100質量%、より好ましくは、35質量%〜100質量%、更に好ましくは40質量%〜100質量%である。
また、本発明の一態様の潤滑油組成物において、アミン系酸化防止剤(A)がナフチルアミン化合物(A2)を含む場合、ジフェニルアミン化合物(A1)及びナフチルアミン化合物(A2)の合計含有量は、本発明の効果をより発揮させやすくするという観点から、アミン系酸化防止剤(A)の全量基準で、好ましくは80質量%〜100質量%、より好ましくは90質量%〜100質量%、更に好ましくは95質量%〜100質量%、より更に好ましくは98質量%〜100質量%、更になお好ましくは99質量%〜100質量%である。
なお、本発明の一態様の潤滑油組成物において、本発明の効果を発揮させやすくするという観点から、ジフェニルアミン化合物(A1)及びナフチルアミン化合物(A2)以外の他のアミン系酸化防止剤(A’)の含有量は少ないことが好ましい。当該他のアミン系酸化防止剤(A’)の含有量は、アミン系酸化防止剤(A)の全量基準で、好ましくは5質量%未満、より好ましくは1質量%未満、更に好ましくは0.1質量%未満、より更に好ましくは0.01質量%未満、更になお好ましくは当該他のアミン系酸化防止剤(A’)を含まないことである。
当該他のアミン系酸化防止剤(A’)としては、例えば、ジフェニルアミン化合物(A1)には該当しない、アラルキル化ジフェニルアミン等が挙げられる。
(Contents and ratios of various amine compounds in the amine-based antioxidant (A))
In the lubricating oil composition of one aspect of the present invention, the content of the diphenylamine compound (A1) is preferably based on the total amount of the amine-based antioxidant (A) from the viewpoint of facilitating the effect of the present invention. It is 30% by mass to 100% by mass, more preferably 35% by mass to 100% by mass, and further preferably 40% by mass to 100% by mass.
When the amine-based antioxidant (A) contains the naphthylamine compound (A2) in the lubricating oil composition of one aspect of the present invention, the total content of the diphenylamine compound (A1) and the naphthylamine compound (A2) is the present. From the viewpoint of making it easier to exert the effects of the present invention, it is preferably 80% by mass to 100% by mass, more preferably 90% by mass to 100% by mass, still more preferably, based on the total amount of the amine-based antioxidant (A). It is 95% by mass to 100% by mass, more preferably 98% by mass to 100% by mass, and even more preferably 99% by mass to 100% by mass.
In addition, in the lubricating oil composition of one aspect of the present invention, from the viewpoint of facilitating the effect of the present invention, other amine-based antioxidants (A') other than the diphenylamine compound (A1) and the naphthylamine compound (A2). ) Is preferably low. The content of the other amine-based antioxidant (A') is preferably less than 5% by mass, more preferably less than 1% by mass, and further preferably 0. It is less than 1% by mass, more preferably less than 0.01% by mass, and even more preferably free of the other amine-based antioxidant (A').
Examples of the other amine-based antioxidant (A') include aralkylated diphenylamine, which does not correspond to the diphenylamine compound (A1).

(ジフェニルアミン化合物(A1)及びナフチルアミン化合物(A2)の合計含有量、含有比率)
本発明の一態様の潤滑油組成物において、アミン系酸化防止剤(A)がナフチルアミン化合物(A2)を含む場合、ジフェニルアミン化合物(A1)及びナフチルアミン化合物(A2)の合計含有量[(A1)+(A2)]は、本発明の効果をより発揮させやすくするという観点から、潤滑油組成物の全量基準で、好ましくは0.80質量%以上2.0質量%未満、より好ましくは0.90質量%〜1.9質量%、更に好ましくは1.0質量%〜1.7質量%である。
また、本発明の一態様の潤滑油組成物において、アミン系酸化防止剤(A)がナフチルアミン化合物(A2)を含む場合、本発明の効果を発揮させやすくするという観点から、ジフェニルアミン化合物(A1)とナフチルアミン化合物(A2)との含有比率[(A1)/(A2)]は、質量比で、好ましくは0.5〜2.0、より好ましくは0.6〜1.8、更に好ましくは0.7〜1.7である。
(Total content and content ratio of diphenylamine compound (A1) and naphthylamine compound (A2))
In the lubricating oil composition of one aspect of the present invention, when the amine-based antioxidant (A) contains the naphthylamine compound (A2), the total content of the diphenylamine compound (A1) and the naphthylamine compound (A2) [(A1) + (A2)] is based on the total amount of the lubricating oil composition, preferably 0.80% by mass or more and less than 2.0% by mass, more preferably 0.90, from the viewpoint of making it easier to exert the effect of the present invention. It is from mass% to 1.9% by mass, more preferably 1.0% by mass to 1.7% by mass.
Further, in the lubricating oil composition of one aspect of the present invention, when the amine-based antioxidant (A) contains the naphthylamine compound (A2), the diphenylamine compound (A1) can easily exert the effects of the present invention. The content ratio [(A1) / (A2)] of the naphthylamine compound (A2) to the naphthylamine compound (A2) is preferably 0.5 to 2.0, more preferably 0.6 to 1.8, and further preferably 0 in terms of mass ratio. It is .7 to 1.7.

<フェノール系酸化防止剤(B)>
本発明の潤滑油組成物は、酸化防止剤(Y)として、フェノール系酸化防止剤(B)を含有する。
フェノール系酸化防止剤(B)は、酸化防止性能を有し、フェノール構造を有する化合物である。但し、このような化合物のうち、リン原子を含有する化合物は、リン系酸化防止剤(C)に包含されるものとする。
以下、本発明の潤滑油組成物において用いられる、フェノール系酸化防止剤(B)について、詳細に説明する。
<Phenolic antioxidant (B)>
The lubricating oil composition of the present invention contains a phenolic antioxidant (B) as an antioxidant (Y).
The phenolic antioxidant (B) is a compound having an antioxidant performance and a phenolic structure. However, among such compounds, the compound containing a phosphorus atom shall be included in the phosphorus-based antioxidant (C).
Hereinafter, the phenolic antioxidant (B) used in the lubricating oil composition of the present invention will be described in detail.

(エステル構造を有するヒンダードフェノール化合物(B1))
本発明の潤滑油組成物において、フェノール系酸化防止剤(B)は、エステル構造を有するヒンダードフェノール化合物(B1)を含む。
本発明者の検討によると、エステル構造を有するヒンダードフェノール化合物(B1)は、3級炭素高含有基油で生じ易い初期段階の酸化劣化を抑制する性能を有する。但し、当該ヒンダードフェノール化合物(B1)のエステル構造部位が、3級炭素高含有基油に含まれ得る微量の水分と加水分解し、初期段階の酸価を上昇させ易い。そのため、本発明では、ジフェニルアミン化合物(A1)、エステル構造を有するヒンダードフェノール化合物(B1)、及びリン系酸化防止剤(C)の合計含有量[(A1)+(B1)+(C)]を一定範囲に規定している。
潤滑油組成物がエステル構造を有するヒンダードフェノール化合物(B1)を含有しない場合、本発明の効果が奏されない。
なお、ヒンダードフェノール化合物とは、フェノール芳香環上の水素原子がtert−ブチル基等の嵩高い置換基により置換された化合物である。
エステル構造を有するヒンダードフェノール化合物(B1)としては、例えば、下記一般式(b1−1)で表される化合物(B1−1)及び下記一般式(b1−2)で表される化合物(B1−2)からなる群から選択される1種以上が挙げられる。なお、以降の説明では、エステル構造を有するヒンダードフェノール化合物(B1)を、単に「ヒンダードフェノール化合物(B1)」ともいう。

Figure 2021138881

[上記式(b1−1)中、Rb1は、炭素数1〜5のアルキレン基である。Rb2は、炭素数1〜25のアルキル基である。]
Figure 2021138881

[上記式(b1−2)中、Rb3及びRb4は、各々独立に、炭素数1〜5のアルキレン基である。mは、2〜4の整数である。] (Hindered phenol compound having an ester structure (B1))
In the lubricating oil composition of the present invention, the phenolic antioxidant (B) contains a hindered phenol compound (B1) having an ester structure.
According to the study by the present inventor, the hindered phenol compound (B1) having an ester structure has an ability to suppress oxidative deterioration in the initial stage, which is likely to occur in a tertiary carbon-rich base oil. However, the ester structure portion of the hindered phenol compound (B1) is easily hydrolyzed with a trace amount of water that can be contained in the tertiary carbon high-containing base oil, and the acid value in the initial stage is easily increased. Therefore, in the present invention, the total content of the diphenylamine compound (A1), the hindered phenol compound having an ester structure (B1), and the phosphorus-based antioxidant (C) [(A1) + (B1) + (C)]. Is specified in a certain range.
When the lubricating oil composition does not contain the hindered phenol compound (B1) having an ester structure, the effect of the present invention is not exhibited.
The hindered phenol compound is a compound in which a hydrogen atom on the phenolic aromatic ring is substituted with a bulky substituent such as a tert-butyl group.
Examples of the hindered phenol compound (B1) having an ester structure include a compound represented by the following general formula (b1-1) (B1-1) and a compound represented by the following general formula (b1-2) (B1). -2) One or more species selected from the group consisting of 2) can be mentioned. In the following description, the hindered phenol compound (B1) having an ester structure is also simply referred to as "hindered phenol compound (B1)".
Figure 2021138881

[In the above formula (b1-1), R b1 is an alkylene group having 1 to 5 carbon atoms. R b2 is an alkyl group having 1 to 25 carbon atoms. ]
Figure 2021138881

[In the above formula (b1-2), R b3 and R b4 are independently alkylene groups having 1 to 5 carbon atoms. m is an integer of 2-4. ]

上記一般式(b1−1)中、Rb1として選択し得るアルキレン基の炭素数は、本発明の効果を発揮させやすくするという観点から、好ましくは1〜4、より好ましくは1〜3、更に好ましくは1〜2である。
b1として選択し得るアルキレン基の具体例としては、メチレン基、エチレン基、n−プロピレン基、n−ブチレン基、n−ペンチレン基等の直鎖状のアルキレン基;イソプロピレン基、イソブチレン基、sec−ブチレン、tert−ブチレン基、イソペンチレン基、ネオペンチレン基などの分枝鎖状アルキレン基等が挙げられる。
上記一般式(b1−1)中、Rb2として選択し得るアルキル基の炭素数は、本発明の効果を発揮させやすくするという観点から、好ましくは2〜20、より好ましくは4〜15、更に好ましくは6〜10である。
b2として選択し得るアルキル基の具体例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、イコシル基、ヘンイコシル基、ドコシル基、トリコシル基、テトラコシル基、ペンタコシル基等が挙げられる。これらは、直鎖状であっても分岐鎖状であってもよい。
上記一般式(b1−1)で表される化合物(B1−1)を例示すると、ベンゼンプロパン酸3,5−ビス(1,1−ジメチルエチル)−4−ヒドロキシアルキルエステル等が挙げられる。
上記一般式(b1−1)で表される化合物(B1−1)は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
In the above general formula (b1-1), the number of carbon atoms of the alkylene group that can be selected as R b1 is preferably 1 to 4, more preferably 1 to 3, and further, from the viewpoint of facilitating the effect of the present invention. It is preferably 1 to 2.
Specific examples of the alkylene group that can be selected as R b1 include a linear alkylene group such as a methylene group, an ethylene group, an n-propylene group, an n-butylene group, and an n-pentylene group; an isopropylene group, an isobutylene group, and the like. Examples thereof include branched alkylene groups such as sec-butylene, tert-butylene group, isopentylene group and neopentylene group.
In the above general formula (b1-1), the number of carbon atoms of the alkyl group that can be selected as R b2 is preferably 2 to 20, more preferably 4 to 15, and further, from the viewpoint of facilitating the effect of the present invention. It is preferably 6 to 10.
Specific examples of the alkyl group that can be selected as R b2 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group and a dodecyl group. Examples thereof include a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecil group, an icosyl group, a henicosyl group, a docosyl group, a tricosyl group, a tetracosyl group and a pentacosyl group. These may be linear or branched chain.
Examples of the compound (B1-1) represented by the above general formula (b1-1) include benzenepropanoic acid 3,5-bis (1,1-dimethylethyl) -4-hydroxyalkyl ester.
As the compound (B1-1) represented by the above general formula (b1-1), one type may be used alone, or two or more types may be used in combination.

上記一般式(b1−2)中、Rb3及びRb4として選択し得るアルキレン基の炭素数は、本発明の効果を発揮させやすくするという観点から、好ましくは1〜4、より好ましくは1〜3、更に好ましくは1〜2である。
b3及びRb4として選択し得るアルキレン基の具体例としては、Rb2として挙げた基と同様の基が挙げられる。
上記一般式(b1−2)で表される化合物(B1−2)を例示すると、ペンタエリスリトール テトラキス[3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオナート]等が挙げられる。
上記一般式(b1−2)で表される化合物(B1−2)は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
In the above general formula (b1-2), the carbon number of the alkylene group that can be selected as R b3 and R b4 is preferably 1 to 4, more preferably 1 to 4 from the viewpoint of facilitating the effect of the present invention. 3, more preferably 1-2.
Specific examples of the alkylene group that can be selected as R b3 and R b4 include a group similar to the group mentioned as R b2.
Examples of the compound (B1-2) represented by the above general formula (b1-2) include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and the like. ..
As the compound (B1-2) represented by the general formula (b1-2), one type may be used alone, or two or more types may be used in combination.

ヒンダードフェノール化合物(B1)は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。 As the hindered phenol compound (B1), one type may be used alone, or two or more types may be used in combination.

ヒンダードフェノール化合物(B1)の含有量は、潤滑油組成物の全量基準で、好ましくは0.50質量%〜0.80質量%、より好ましくは0.55質量%〜0.70質量%、更に好ましくは0.55質量%〜0.65質量%である。
ヒンダードフェノール化合物(B1)の含有量が上記範囲であることにより、潤滑油組成物の初期段階の酸価上昇を抑制することができると共に、3級炭素高含有基油に含まれ得る微量な水分との反応により生成される加水分解物に起因する酸価の上昇を抑制させ得る。
The content of the hindered phenol compound (B1) is preferably 0.50% by mass to 0.80% by mass, more preferably 0.55% by mass to 0.70% by mass, based on the total amount of the lubricating oil composition. More preferably, it is 0.55% by mass to 0.65% by mass.
When the content of the hindered phenol compound (B1) is in the above range, it is possible to suppress an increase in the acid value at the initial stage of the lubricating oil composition, and a small amount that can be contained in the tertiary carbon high content base oil. The increase in acid value caused by the hydrolyzate produced by the reaction with water can be suppressed.

(フェノール系酸化防止剤(B)中のヒンダードフェノール化合物(B1)の含有量)
本発明の一態様の潤滑油組成物において、ヒンダードフェノール化合物(B1)の含有量は、本発明の効果を発揮させやすくするという観点から、フェノール系酸化防止剤(B)の全量基準で、好ましくは80質量%〜100質量%、より好ましくは90質量%〜100質量%、更に好ましくは95質量%〜100質量%、より更に好ましくは98質量%〜100質量%、更になお好ましくいは99質量%〜100質量%である。
なお、本発明の一態様の潤滑油組成物において、本発明の効果を発揮させやすくするという観点から、ヒンダードフェノール化合物(B1)以外の他のフェノール系酸化防止剤(B’)の含有量は少ないことが好ましい。当該他のフェノール系酸化防止剤(B’)の含有量は、フェノール系酸化防止剤(B)の全量基準で、好ましくは5質量%未満、より好ましくは1質量%未満、更に好ましくは0.1質量%未満、より更に好ましくは0.01質量%未満、更になお好ましくは当該他のフェノール系酸化防止剤(B’)を含まないことである。
当該他のフェノール系酸化防止剤(B’)としては、例えば、ヒンダードフェノール化合物(B1)には該当しない、2,6−ジ−tert−ブチル−p−クレゾール(DBPC)等が挙げられる。
(Content of hindered phenol compound (B1) in phenolic antioxidant (B))
In the lubricating oil composition of one aspect of the present invention, the content of the hindered phenol compound (B1) is based on the total amount of the phenolic antioxidant (B) from the viewpoint of facilitating the effect of the present invention. It is preferably 80% by mass to 100% by mass, more preferably 90% by mass to 100% by mass, still more preferably 95% by mass to 100% by mass, still more preferably 98% by mass to 100% by mass, and even more preferably 99. It is from mass% to 100% by mass.
The content of the phenolic antioxidant (B') other than the hindered phenol compound (B1) in the lubricating oil composition of one aspect of the present invention from the viewpoint of facilitating the exertion of the effects of the present invention. Is preferably small. The content of the other phenolic antioxidant (B') is preferably less than 5% by mass, more preferably less than 1% by mass, still more preferably 0.%, Based on the total amount of the phenolic antioxidant (B). It is less than 1% by mass, more preferably less than 0.01% by mass, and even more preferably free of the other phenolic antioxidant (B').
Examples of the other phenolic antioxidant (B') include 2,6-di-tert-butyl-p-cresol (DBPC), which does not correspond to the hindered phenol compound (B1).

<リン系酸化防止剤(C)>
本発明の潤滑油組成物は、酸化防止剤(Y)として、リン系酸化防止剤(C)を含有する。
リン系酸化防止剤(C)は、リン原子を含有する化合物であり、アミン系酸化防止剤(A)と併用することで、RPVOT値で評価される酸化安定性を良好なものとして、酸化安定性を長期に亘り維持する性能を有する。
潤滑油組成物がリン系酸化防止剤(C)を含有しない場合、RPVOT値で評価される酸化安定性を優れたものとすることができず、酸化安定性を長期に亘り維持することができない。
以下、本発明の潤滑油組成物において用いられる、リン系酸化防止剤(C)について、詳細に説明する
<Phosphorus-based antioxidant (C)>
The lubricating oil composition of the present invention contains a phosphorus-based antioxidant (C) as an antioxidant (Y).
The phosphorus-based antioxidant (C) is a compound containing a phosphorus atom, and when used in combination with the amine-based antioxidant (A), the oxidation stability evaluated by the RPVOT value is made good, and the oxidation stability is achieved. It has the ability to maintain its properties for a long period of time.
When the lubricating oil composition does not contain the phosphorus-based antioxidant (C), the oxidative stability evaluated by the RPVOT value cannot be made excellent, and the oxidative stability cannot be maintained for a long period of time. ..
Hereinafter, the phosphorus-based antioxidant (C) used in the lubricating oil composition of the present invention will be described in detail.

(フェノール構造を有するリン原子含有化合物(C1))
本発明の一態様の潤滑油組成物において、リン系酸化防止剤(C)は、下記一般式(c1)で表される、フェノール構造を有するリン原子含有化合物(C1)を含むことが好ましい。

Figure 2021138881

[上記一般式(c1)中、Rc1、Rc2、Rc3、及びRc4は、各々独立に、水素原子又は炭素数1〜30のアルキル基である。] (Phosphorus atom-containing compound having a phenol structure (C1))
In the lubricating oil composition of one aspect of the present invention, the phosphorus-based antioxidant (C) preferably contains a phosphorus atom-containing compound (C1) having a phenol structure represented by the following general formula (c1).
Figure 2021138881

[In the above general formula (c1), R c1 , R c2 , R c3 , and R c4 are each independently a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. ]

c1、Rc2、Rc3、及びRc4として選択し得るアルキル基としては、上述のRa1及びRa2として選択し得るアルキル基と同じものが挙げられる。
但し、Rc1、Rc2、Rc3、及びRc4として選択し得るアルキル基の炭素数としては、それぞれ独立に、好ましくは1〜20、より好ましくは1〜10、更に好ましくは1〜6である。
ここで、フェノール構造を有するリン原子含有化合物(C1)は、本発明の効果を発揮させやすくするという観点から、ヒンダードフェノール骨格を有することが好ましい。したがって、Rc1及びRc2として選択し得るアルキル基は、分岐鎖アルキル基であることが好ましく、炭素数1〜6の分岐鎖アルキル基であることがより好ましく、tert−ブチル基であることが更に好ましい。
Examples of the alkyl group that can be selected as R c1 , R c2 , R c3 , and R c4 include the same alkyl groups that can be selected as R a1 and R a2 described above.
However, the number of carbon atoms of the alkyl groups that can be selected as R c1 , R c2 , R c3 , and R c4 is independently, preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6. be.
Here, the phosphorus atom-containing compound (C1) having a phenol structure preferably has a hindered phenol skeleton from the viewpoint of facilitating the exertion of the effects of the present invention. Therefore, the alkyl group that can be selected as R c1 and R c2 is preferably a branched alkyl group, more preferably a branched alkyl group having 1 to 6 carbon atoms, and preferably a tert-butyl group. More preferred.

フェノール構造を有するリン原子含有化合物(C1)の含有量は、潤滑油組成物の全量基準で、好ましくは0.05質量%〜0.30質量%、より好ましくは0.07質量%〜0.20質量%、更に好ましくは0.09質量%〜0.15質量%である。
フェノール構造を有するリン原子含有化合物(C1)の含有量が上記範囲であることにより、ジフェニルアミン(A1)とヒンダードフェノール化合物(B1)の配合量を抑えながらも、酸化安定性を長期に亘り安定に維持し得る。
The content of the phosphorus atom-containing compound (C1) having a phenol structure is preferably 0.05% by mass to 0.30% by mass, more preferably 0.07% by mass to 0.% by mass based on the total amount of the lubricating oil composition. It is 20% by mass, more preferably 0.09% by mass to 0.15% by mass.
By keeping the content of the phosphorus atom-containing compound (C1) having a phenol structure in the above range, the oxidative stability is stable for a long period of time while suppressing the blending amount of the diphenylamine (A1) and the hindered phenol compound (B1). Can be maintained at.

(リン系酸化防止剤(C)中のフェノール構造を有するリン原子含有化合物(C1)の含有量)
本発明の一態様の潤滑油組成物において、フェノール構造を有するリン原子含有化合物(C1)の含有量は、本発明の効果を発揮させやすくするという観点から、リン系酸化防止剤(C)の全量基準で、好ましくは80質量%〜100質量%、より好ましくは90質量%〜100質量%、更に好ましくは95質量%〜100質量%、より更に好ましくは98質量%〜100質量%、更になお好ましくいは99質量%〜100質量%である。
なお、本発明の一態様の潤滑油組成物において、本発明の効果を発揮させやすくするという観点から、フェノール構造を有するリン原子含有化合物(C1)以外の他のリン系酸化防止剤(C’)の含有量は少ないことが好ましい。当該他のリン系酸化防止剤(C’)の含有量は、リン系酸化防止剤(C)の全量基準で、好ましくは5質量%未満、より好ましくは1質量%未満、更に好ましくは0.1質量%未満、より更に好ましくは0.01質量%未満、更になお好ましくは当該他のリン系酸化防止剤(C’)を含まないことである。
当該他のリン系酸化防止剤(C’)としては、例えば、フェノール構造を有するリン原子含有化合物(C1)には該当しない、リン原子を含有する金属系酸化防止剤、例えばジアルキルジチオリン酸亜鉛等が挙げられる。
(Content of phosphorus atom-containing compound (C1) having a phenol structure in phosphorus-based antioxidant (C))
In the lubricating oil composition of one aspect of the present invention, the content of the phosphorus atom-containing compound (C1) having a phenol structure is the phosphorus-based antioxidant (C) from the viewpoint of facilitating the effect of the present invention. Based on the total amount, preferably 80% by mass to 100% by mass, more preferably 90% by mass to 100% by mass, still more preferably 95% by mass to 100% by mass, still more preferably 98% by mass to 100% by mass, still more. It is preferably 99% by mass to 100% by mass.
In addition, in the lubricating oil composition of one aspect of the present invention, from the viewpoint of facilitating the effect of the present invention, other phosphorus-based antioxidants (C') other than the phosphorus atom-containing compound (C1) having a phenol structure. ) Is preferably low. The content of the other phosphorus-based antioxidant (C') is preferably less than 5% by mass, more preferably less than 1% by mass, and further preferably 0. It is less than 1% by mass, more preferably less than 0.01% by mass, and even more preferably free of the other phosphorus-based antioxidant (C').
Examples of the other phosphorus-based antioxidant (C') include a phosphorus atom-containing metal-based antioxidant that does not correspond to the phosphorus atom-containing compound (C1) having a phenol structure, for example, zinc dialkyldithiophosphate and the like. Can be mentioned.

<他の酸化防止剤(Y’)>
本発明の一態様の潤滑油組成物において、本発明の効果を発揮させやすくするという観点から、アミン系酸化防止剤(A)、フェノール系酸化防止剤(B)、及びリン系酸化防止剤(C)以外の他の酸化防止剤(Y’)の含有量は少ないことが好ましい。当該他の酸化防止剤(Y’)の含有量は、酸化防止剤(Y)の全量基準で、好ましくは5質量%未満、より好ましくは1質量%未満、更に好ましくは0.1質量%未満、より更に好ましくは0.01質量%未満、更になお好ましくは当該他の酸化防止剤(Y’)を含まないことである。
他の酸化防止剤(Y’)としては、例えば硫黄系酸化防止剤、金属系酸化防止剤等が挙げられる。
<Other antioxidants (Y')>
From the viewpoint of facilitating the effect of the present invention in the lubricating oil composition of one aspect of the present invention, an amine-based antioxidant (A), a phenol-based antioxidant (B), and a phosphorus-based antioxidant ( It is preferable that the content of the antioxidant (Y') other than C) is small. The content of the other antioxidant (Y') is preferably less than 5% by mass, more preferably less than 1% by mass, still more preferably less than 0.1% by mass, based on the total amount of the antioxidant (Y). , More preferably less than 0.01% by mass, and even more preferably free of the other antioxidant (Y').
Examples of other antioxidants (Y') include sulfur-based antioxidants, metal-based antioxidants, and the like.

<各酸化防止剤の合計含有量、含有比率>
以下、ジフェニルアミン化合物(A1)、エステル構造を有するヒンダードフェノール化合物(B1)、及びリン系酸化防止剤(C)に関し、合計含有量、含有比率について詳細に説明する。
<Total content and ratio of each antioxidant>
Hereinafter, the total content and content ratio of the diphenylamine compound (A1), the hindered phenol compound having an ester structure (B1), and the phosphorus-based antioxidant (C) will be described in detail.

([(A1)+(B1)+(C)])
本発明の潤滑油組成物において、ジフェニルアミン化合物(A1)、エステル構造を有するヒンダードフェノール化合物(B1)、及びリン系酸化防止剤(C)の合計含有量[(A1)+(B1)+(C)]は、1.0質量%超2.0質量%以下であることを要する。
[(A1)+(B1)+(C)]が1.0質量%以下であると、RPVOT値で評価される酸化安定性を優れたものとすることができず、酸化安定性を長期に亘って維持することができない。
また、[(A1)+(B1)+(C)]が2.0質量%超であると、初期段階で酸価が上昇しやすい潤滑油組成物となる。
ここで、本発明の効果をより発揮させやすくするという観点から、[(A1)+(B1)+(C)]は、1.1質量%〜1.9質量%であることが好ましく、1.1質量%〜1.8質量%であることがより好ましく、1.2質量%〜1.7質量%であることが更に好ましい。
([(A1) + (B1) + (C)])
In the lubricating oil composition of the present invention, the total content of the diphenylamine compound (A1), the hindered phenol compound having an ester structure (B1), and the phosphorus-based antioxidant (C) [(A1) + (B1) + ( C)] is required to be more than 1.0% by mass and 2.0% by mass or less.
If [(A1) + (B1) + (C)] is 1.0% by mass or less, the oxidative stability evaluated by the RPVOT value cannot be made excellent, and the oxidative stability can be maintained for a long period of time. Cannot be maintained over.
Further, when [(A1) + (B1) + (C)] is more than 2.0% by mass, the lubricating oil composition tends to increase the acid value in the initial stage.
Here, from the viewpoint of making it easier to exert the effect of the present invention, [(A1) + (B1) + (C)] is preferably 1.1% by mass to 1.9% by mass, 1 It is more preferably .1% by mass to 1.8% by mass, and further preferably 1.2% by mass to 1.7% by mass.

([(A1)+(B1)])
本発明の一態様の潤滑油組成物において、ジフェニルアミン化合物(A1)及びエステル構造を有するヒンダードフェノール化合物(B1)の合計含有量[(A1)+(B1)]は、本発明の効果をより発揮させやすくするという観点から、好ましくは0.9質量%以上、より好ましくは1.0質量%以上、更に好ましくは1.1質量%以上である。また、好ましくは1.9質量%以下、より好ましくは1.8質量%以下、更に好ましくは1.7質量%以下、より更に好ましくは1.6質量%以下である。
([(A1) + (B1)])
In the lubricating oil composition of one aspect of the present invention, the total content [(A1) + (B1)] of the diphenylamine compound (A1) and the hindered phenol compound (B1) having an ester structure makes the effect of the present invention more effective. From the viewpoint of facilitating the exertion, it is preferably 0.9% by mass or more, more preferably 1.0% by mass or more, and further preferably 1.1% by mass or more. Further, it is preferably 1.9% by mass or less, more preferably 1.8% by mass or less, still more preferably 1.7% by mass or less, still more preferably 1.6% by mass or less.

([(A1)/(B1)])
本発明の一態様の潤滑油組成物において、ジフェニルアミン化合物(A1)と、エステル構造を有するヒンダードフェノール化合物(B1)との含有比率[(A1)/(B1)]は、本発明の効果をより発揮させやすくするという観点から、質量比で、好ましくは0.5〜2.0、より好ましくは0.6〜1.9、更に好ましくは0.7〜1.8、より更に好ましくは0.8〜1.7である。
([(A1) / (B1)])
In the lubricating oil composition of one aspect of the present invention, the content ratio [(A1) / (B1)] of the diphenylamine compound (A1) and the hindered phenol compound (B1) having an ester structure has the effect of the present invention. From the viewpoint of making it easier to exert, the mass ratio is preferably 0.5 to 2.0, more preferably 0.6 to 1.9, still more preferably 0.7 to 1.8, still more preferably 0. It is .8 to 1.7.

([(A1)/(C)])
本発明の一態様の潤滑油組成物において、ジフェニルアミン化合物(A1)と、リン系酸化防止剤(C)との含有比率[(A1)/(C)]は、本発明の効果をより発揮させやすくするという観点から、質量比で、好ましくは3.0〜15.0、より好ましくは3.5〜13.0、更に好ましくは4.0〜12.0、より更に好ましくは4.5〜11.0、更になお好ましくは5.0〜10.0である。
([(A1) / (C)])
In the lubricating oil composition of one aspect of the present invention, the content ratio [(A1) / (C)] of the diphenylamine compound (A1) and the phosphorus-based antioxidant (C) further exerts the effect of the present invention. From the viewpoint of facilitation, the mass ratio is preferably 3.0 to 15.0, more preferably 3.5 to 13.0, still more preferably 4.0 to 12.0, still more preferably 4.5 to 1. It is 11.0, and even more preferably 5.0 to 10.0.

([(B1)/(C)])
本発明の一態様の潤滑油組成物において、エステル構造を有するヒンダードフェノール化合物(B1)と、リン系酸化防止剤(C)との含有比率[(B1)/(C)]は、本発明の効果をより発揮させやすくするという観点から、質量比で、好ましくは4.0〜10.0、より好ましくは4.5〜9.0、更に好ましくは5.0〜8.0、より更に好ましくは5.5〜7.0、更になお好ましくは5.5〜6.5である。
([(B1) / (C)])
In the lubricating oil composition of one aspect of the present invention, the content ratio [(B1) / (C)] of the hindered phenol compound (B1) having an ester structure and the phosphorus-based antioxidant (C) is the present invention. From the viewpoint of making it easier to exert the effect of, the mass ratio is preferably 4.0 to 10.0, more preferably 4.5 to 9.0, still more preferably 5.0 to 8.0, and further. It is preferably 5.5 to 7.0, and even more preferably 5.5 to 6.5.

<潤滑油用添加剤>
本発明の一態様の潤滑油組成物は、本発明の効果を損なわない範囲で、酸化防止剤(Y)以外の潤滑油用添加剤を含有してもよい。
当該潤滑油用添加剤としては、例えば、極圧剤、清浄分散剤、流動点降下剤、粘度指数向上剤、防錆剤、金属不活性化剤、消泡剤、及び摩擦調整剤等が挙げられる。
これらの潤滑油用添加剤は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
<Additives for lubricating oil>
The lubricating oil composition of one aspect of the present invention may contain an additive for lubricating oil other than the antioxidant (Y) as long as the effects of the present invention are not impaired.
Examples of the additive for lubricating oil include extreme pressure agents, cleaning dispersants, pour point lowering agents, viscosity index improvers, rust preventives, metal inactivating agents, defoaming agents, friction modifiers and the like. Be done.
These lubricant additives may be used alone or in combination of two or more.

なお、本明細書において、粘度指数向上剤や消泡剤等の添加剤は、ハンドリング性や鉱油系基油(A)への溶解性を考慮し、希釈油に溶解した溶液の形態で、他の成分と配合される場合がある。このような場合、本明細書においては、消泡剤や粘度指数向上剤等の添加剤の含有量は、希釈油を除いた有効成分換算(樹脂分換算)での含有量である。
以下、上記の各潤滑油用添加剤の詳細について説明する。
In the present specification, the additives such as the viscosity index improver and the defoaming agent are in the form of a solution dissolved in a diluted oil in consideration of handleability and solubility in the mineral oil-based base oil (A). May be mixed with the ingredients of. In such a case, in the present specification, the content of the additive such as the defoaming agent and the viscosity index improver is the content in terms of the active ingredient (converted to the resin content) excluding the diluted oil.
The details of each of the above-mentioned additives for lubricating oil will be described below.

(極圧剤)
極圧剤としては、例えば、リン酸エステル類、亜リン酸エステル類、酸性リン酸エステル類、酸性亜リン酸エステル類、ジチオリン酸等のリン系極圧剤;モノチオリン酸エステル類、ジチオリン酸エステル類等の硫黄−リン系極圧剤;塩素化炭化水素等のハロゲン系極圧剤;有機金属系極圧剤;等が挙げられる。
なお、これらの極圧剤は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
本発明の一態様の潤滑油組成物が極圧剤を含有する場合、極圧剤の含有量は、当該潤滑油組成物の全量基準で、好ましくは0.01〜10質量%、より好ましくは0.03〜5質量%、更に好ましくは0.05〜1.0質量%である。
(Extreme pressure agent)
Examples of extreme pressure agents include phosphorus-based extreme pressure agents such as phosphoric acid esters, phosphite esters, acidic phosphoric acid esters, acidic phosphite esters, and dithiophosphates; monothiophosphates, dithiophosphates. Examples thereof include sulfur-phosphorus extreme pressure agents; halogen-based extreme pressure agents such as chlorinated hydrocarbons; organic metal-based extreme pressure agents; and the like.
In addition, these extreme pressure agents may be used individually by 1 type and may use 2 or more types in combination.
When the lubricating oil composition of one aspect of the present invention contains an extreme pressure agent, the content of the extreme pressure agent is preferably 0.01 to 10% by mass, more preferably 0.01 to 10% by mass, based on the total amount of the lubricating oil composition. It is 0.03 to 5% by mass, more preferably 0.05 to 1.0% by mass.

(清浄分散剤)
清浄分散剤としては、例えば、金属スルホネート、金属サリチレート、金属フェネート、有機亜リン酸エステル、有機リン酸エステル、有機リン酸金属塩、コハク酸イミド、ベンジルアミン、コハク酸エステル、多価アルコールエステル等が挙げられる。
金属スルホネート等の金属塩を構成する金属としては、アルカリ金属及びアルカリ土類金属が好ましく、ナトリウム、カルシウム、マグネシウム、及びバリウムがより好ましく、カルシウムが更に好ましい。なお、コハク酸イミド、ベンジルアミン、及びコハク酸エステルは、ホウ素変性物であってもよい。
本発明の一態様の潤滑油組成物が清浄分散剤を含有する場合、清浄分散剤の含有量は、当該潤滑油組成物の全量基準で、好ましくは0.01〜10質量%、より好ましくは0.02〜7質量%、更に好ましくは0.03〜5質量%である。
(Cleaning dispersant)
Examples of the cleaning dispersant include metal sulfonate, metal salicylate, metal phenate, organic phosphite ester, organic phosphate ester, organic phosphate metal salt, succinateimide, benzylamine, succinate ester, polyhydric alcohol ester and the like. Can be mentioned.
As the metal constituting the metal salt such as metal sulfonate, alkali metal and alkaline earth metal are preferable, sodium, calcium, magnesium and barium are more preferable, and calcium is further preferable. The succinimide, benzylamine, and succinate ester may be boron-modified products.
When the lubricating oil composition of one aspect of the present invention contains a cleaning dispersant, the content of the cleaning dispersant is preferably 0.01 to 10% by mass, more preferably 0.01 to 10% by mass, based on the total amount of the lubricating oil composition. It is 0.02 to 7% by mass, more preferably 0.03 to 5% by mass.

(流動点降下剤)
流動点降下剤としては、例えば、重量平均分子量が5万〜15万程度のポリメタクリレート等が挙げられる。本発明の一態様の潤滑油組成物が流動点降下剤を含有する場合、流動点降下剤の含有量は、当該潤滑油組成物の全量基準で、好ましくは0.01〜5質量%、より好ましくは0.02〜2質量%である。
(粘度指数向上剤)
粘度指数向上剤としては、例えば、非分散型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等)、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−ジエン共重合体、スチレン−イソプレン共重合体等)等の重合体が挙げられる。
本発明の一態様の潤滑油組成物が粘度指数向上剤を含有する場合、粘度指数向上剤の樹脂分換算での含有量は、当該潤滑油組成物の全量基準で、好ましくは0.01〜10質量%、より好ましくは0.02〜7質量%、更に好ましくは0.03〜5質量%である。
(Pour point depressant)
Examples of the pour point lowering agent include polymethacrylate having a weight average molecular weight of about 50,000 to 150,000. When the lubricating oil composition of one aspect of the present invention contains a pour point depressant, the content of the pour point depressant is preferably 0.01 to 5% by mass, based on the total amount of the lubricating oil composition. It is preferably 0.02 to 2% by mass.
(Viscosity index improver)
Examples of the viscosity index improver include non-dispersible polymethacrylate, dispersed polymethacrylate, olefin-based copolymer (for example, ethylene-propylene copolymer, etc.), dispersed-type olefin-based copolymer, and styrene-based copolymer. (For example, a styrene-diene copolymer, a styrene-isoprene copolymer, etc.) and the like can be mentioned.
When the lubricating oil composition of one aspect of the present invention contains a viscosity index improver, the content of the viscosity index improver in terms of resin content is preferably 0.01 to 0.01 based on the total amount of the lubricating oil composition. It is 10% by mass, more preferably 0.02 to 7% by mass, and even more preferably 0.03 to 5% by mass.

(防錆剤)
防錆剤としては、例えば、金属スルホネート、アルキルベンゼンスルフォネート、ジノニルナフタレンスルフォネート、有機亜リン酸エステル、有機リン酸エステル、有機スルフォン酸金属塩、有機リン酸金属塩、アルケニルコハク酸エステル、アルケニルコハク酸多価アルコールエステル等が挙げられる。
本発明の一態様の潤滑油組成物が防錆剤を含有する場合、防錆剤の含有量は、当該潤滑油組成物の全量基準で、好ましくは0.01〜10.0質量%、より好ましくは0.03〜5.0質量%である。
(anti-rust)
Examples of the rust preventive agent include metal sulfonate, alkylbenzene sulphonate, dinonylnaphthalen sulphonate, organic phosphite ester, organic phosphoric acid ester, organic sulphonic acid metal salt, organic phosphoric acid metal salt, and alkenyl succinic acid ester. , Alkenyl succinic acid polyhydric alcohol ester and the like.
When the lubricating oil composition of one aspect of the present invention contains a rust preventive, the content of the rust preventive is preferably 0.01 to 10.0% by mass, based on the total amount of the lubricating oil composition. It is preferably 0.03 to 5.0% by mass.

(金属不活性化剤)
金属不活性化剤としては、ベンゾトリアゾール系化合物、トリルトリアゾール系化合物、チアジアゾール系化合物、イミダゾール系化合物、ピリミジン系化合物等が挙げられる。
本発明の一態様の潤滑油組成物が金属不活性化剤を含有する場合、金属不活性化剤の含有量は、当該潤滑油組成物の全量基準で、好ましくは0.01〜5.0質量%、より好ましくは0.03〜3.0質量%である。
(Metal inactivating agent)
Examples of the metal inactivating agent include benzotriazole-based compounds, tolyltriazole-based compounds, thiadiazole-based compounds, imidazole-based compounds, pyrimidine-based compounds and the like.
When the lubricating oil composition of one aspect of the present invention contains a metal inactivating agent, the content of the metal inactivating agent is preferably 0.01 to 5.0 based on the total amount of the lubricating oil composition. It is by mass, more preferably 0.03 to 3.0% by mass.

(消泡剤)
消泡剤としては、例えば、シリコーン系消泡剤、フルオロシリコーン油及びフルオロアルキルエーテル等のフッ素系消泡剤、ポリアクリレート系消泡剤等が挙げられる。
本発明の一態様の潤滑油組成物が消泡剤を含有する場合、消泡剤の樹脂分換算での含有量は、当該潤滑油組成物の全量基準で、好ましくは0.0001〜0.20質量%、より好ましくは0.0005〜0.10質量%である。
(Defoamer)
Examples of the defoaming agent include silicone-based defoaming agents, fluorine-based defoaming agents such as fluorosilicone oil and fluoroalkyl ether, and polyacrylate-based defoaming agents.
When the lubricating oil composition of one aspect of the present invention contains a defoaming agent, the content of the defoaming agent in terms of resin content is preferably 0.0001 to 0. It is 20% by mass, more preferably 0.0005 to 0.10% by mass.

(摩擦調整剤)
摩擦調整剤としては、例えば、ジチオカルバミン酸モリブデン(MoDTC)、ジチオリン酸モリブデン(MoDTP)等のモリブデン系摩擦調整剤;炭素数6〜30のアルキル基又はアルケニル基を分子中に少なくとも1個有する、脂肪族アミン、脂肪酸エステル、脂肪酸、脂肪族アルコール、脂肪族エーテル等の無灰摩擦調整剤;等が挙げられる。
なお、高温環境下で長期間の使用に伴い発生するスラッジの析出を抑制するという観点から、MoDTCやMoDTP等の硫黄原子含有摩擦調整剤の含有量は少ないことが好ましい。具体的には、硫黄原子含有摩擦調整剤の含有量は、潤滑油組成物の全量基準で、好ましくは1質量%未満、より好ましくは0.5質量%未満、更に好ましくは0.1質量%未満、より更に好ましくは0.05質量%未満、更になお好ましくは0.01質量%未満、一層好ましくは硫黄原子含有摩擦調整剤を含まないことである。
(Friction modifier)
Examples of the friction modifier include molybdenum-based friction modifiers such as molybdenum dithiocarbamate (MoDTC) and molybdenum dithiophosphate (MoDTP); fatty acids having at least one alkyl group or alkenyl group having 6 to 30 carbon atoms in the molecule. Ash-free friction modifiers such as group amines, fatty acid esters, fatty acids, aliphatic alcohols, and aliphatic ethers; and the like.
From the viewpoint of suppressing the precipitation of sludge generated by long-term use in a high temperature environment, it is preferable that the content of the sulfur atom-containing friction modifier such as MoDTC and MoDTP is small. Specifically, the content of the sulfur atom-containing friction modifier is preferably less than 1% by mass, more preferably less than 0.5% by mass, still more preferably 0.1% by mass, based on the total amount of the lubricating oil composition. Less than, more preferably less than 0.05% by mass, even more preferably less than 0.01% by mass, still more preferably free of sulfur atom-containing friction modifiers.

[潤滑油組成物の各種物性]
<潤滑油組成物の40℃動粘度>
本発明の一態様の潤滑油組成物の40℃動粘度は、好ましくは10mm/s〜100mm/s、より好ましくは30mm/s〜60mm/s、更に好ましくは35mm/s〜55mm/s、より更に好ましくは40mm/s〜50mm/sである。
本明細書において、潤滑油組成物の40℃動粘度は、JIS K 2283:2000に準拠して測定した値である。
[Various physical properties of lubricating oil composition]
<40 ° C kinematic viscosity of lubricating oil composition>
40 ° C. The kinematic viscosity of one embodiment of the lubricating oil composition of the present invention is preferably 10mm 2 / s~100mm 2 / s, more preferably from 30mm 2 / s~60mm 2 / s, more preferably 35 mm 2 / s to 55 mm 2 / s, even more preferably from 40mm 2 / s~50mm 2 / s.
In the present specification, the 40 ° C. kinematic viscosity of the lubricating oil composition is a value measured according to JIS K 2283: 2000.

<酸化安定性>
(酸価の増加量)
本発明の一態様の潤滑油組成物において、後述する実施例に記載の方法で行われる、ASTM D2440に準拠した酸化安定性試験による試験前後の酸価の増加量Δ酸価(試験後酸価と試験前酸価との差)は、好ましくは0.10mgKOH/g未満、より好ましくは0.08mgKOH/g以下、更に好ましくは0.06mgKOH/g以下、より更に好ましくは0.05mgKOH/g以下、更になお好ましくは0.04mgKOH/g以下である。
本明細書において、酸価は、JIS K2501:2003の5(指示薬滴定法)に準拠して測定される値である。
<Oxidation stability>
(Increase in acid value)
In the lubricating oil composition of one aspect of the present invention, the amount of increase in acid value before and after the test by the oxidation stability test based on ASTM D2440 performed by the method described in Examples described later Δ Acid value (acid value after test) The difference between the acid value before the test and the acid value before the test) is preferably less than 0.10 mgKOH / g, more preferably 0.08 mgKOH / g or less, still more preferably 0.06 mgKOH / g or less, still more preferably 0.05 mgKOH / g or less. Even more preferably, it is 0.04 mgKOH / g or less.
In the present specification, the acid value is a value measured according to JIS K2501: 2003-5 (indicator titration method).

(RPVOT値)
本発明の一態様の潤滑油組成物において、ASTM D2440に準拠して酸化安定性試験を行った後に、ASTM D2272に準拠して試験温度150℃で測定される、RPVOT値は、好ましくは600min以上、より好ましくは650min以上、更に好ましくは700min以上、より更に好ましくは750min以上である。
(RPVOT value)
In the lubricating oil composition of one aspect of the present invention, after performing an oxidation stability test according to ASTM D2440, the RPVOT value measured at a test temperature of 150 ° C. according to ASTM D2272 is preferably 600 min or more. , More preferably 650 min or more, still more preferably 700 min or more, still more preferably 750 min or more.

[潤滑油組成物の製造方法]
本発明の潤滑油組成物の製造方法は、特に制限されない。
例えば、本発明の一態様の潤滑油組成物の製造方法は、3級炭素の含有量が、炭化水素の全炭素基準で、8.0at%以上である基油(X)と、アミン系酸化防止剤(A)、フェノール系酸化防止剤(B)、及びリン系酸化防止剤(C)を含む酸化防止剤(Y)と、を含有する潤滑油組成物の製造方法であって、基油(X)と酸化防止剤(Y)とを混合する工程を含み、
アミン系酸化防止剤(A)は、下記一般式(a1)で表されるジフェニルアミン化合物(A1)を含み、

Figure 2021138881

[上記一般式(a1)中、Ra1及びRa2は、各々独立に、炭素数1〜30のアルキル基である。na1及びna2は、各々独立に、1〜5の整数である。na1が2以上である場合、複数のRa1は、同一であってもよく、互いに異なっていてもよい。na2が2以上である場合、複数のRa2は、同一であってもよく、互いに異なっていてもよい。]
フェノール系酸化防止剤(B)は、エステル構造を有するヒンダードフェノール化合物(B1)を含み、
ジフェニルアミン化合物(A1)、エステル構造を有するヒンダードフェノール化合物(B1)、及びリン系酸化防止剤(C)の含有量[(A1)+(B1)+(C)]は、潤滑油組成物の全量基準で、1.0質量%超2.0質量%以下に調整される、潤滑油組成物の製造方法である。
上記各成分を混合する方法としては、特に制限はないが、例えば、基油(A)に、酸化防止剤(Y)を配合する工程を有する方法が挙げられる。アミン系酸化防止剤(A)、フェノール系酸化防止剤(B)、及びリン系酸化防止剤(C)は、基油(A)に同時に配合してもよいし、別々に配合してもよい。酸化防止剤(Y)以外の他の成分(潤滑油用添加剤)の配合についても同様である。なお、各成分は、希釈油等を加えて溶液(分散体)の形態とした上で配合してもよい。各成分を配合した後、公知の方法により、撹拌して均一に分散させることが好ましい。 [Manufacturing method of lubricating oil composition]
The method for producing the lubricating oil composition of the present invention is not particularly limited.
For example, in the method for producing a lubricating oil composition according to one aspect of the present invention, a base oil (X) having a tertiary carbon content of 8.0 at% or more based on the total carbon content of the hydrocarbon and an amine-based oxidation A method for producing a lubricating oil composition containing an antioxidant (A), a phenolic antioxidant (B), and an antioxidant (Y) containing a phosphorus-based antioxidant (C), which is a base oil. Including the step of mixing (X) and the antioxidant (Y),
The amine-based antioxidant (A) contains a diphenylamine compound (A1) represented by the following general formula (a1), and contains the diphenylamine compound (A1).
Figure 2021138881

[In the above general formula (a1), Ra1 and Ra2 are independently alkyl groups having 1 to 30 carbon atoms. na1 and na2 are each independently an integer of 1-5. If na1 is 2 or more, plural R a1 may be the same or different from each other. If na2 is 2 or more, plural R a2 may be the same or different from each other. ]
The phenolic antioxidant (B) contains a hindered phenol compound (B1) having an ester structure and contains.
The contents of the diphenylamine compound (A1), the hindered phenol compound (B1) having an ester structure, and the phosphorus-based antioxidant (C) [(A1) + (B1) + (C)] are the lubricating oil compositions. It is a method for producing a lubricating oil composition, which is adjusted to more than 1.0% by mass and 2.0% by mass or less on a total amount basis.
The method for mixing each of the above components is not particularly limited, and examples thereof include a method having a step of blending the antioxidant (Y) with the base oil (A). The amine-based antioxidant (A), the phenol-based antioxidant (B), and the phosphorus-based antioxidant (C) may be blended in the base oil (A) at the same time or separately. .. The same applies to the formulation of components (additives for lubricating oil) other than the antioxidant (Y). In addition, each component may be blended after adding a diluting oil or the like to form a solution (dispersion). After blending each component, it is preferable to stir and uniformly disperse by a known method.

[潤滑油組成物の用途]
本発明の一態様の潤滑油組成物は、蒸気タービン、原子力タービン、ガスタービン、水力発電用タービン等の各種タービンの潤滑に用いられるタービン油;送風機、ガス圧縮機等の各種ターボ機械の潤滑に用いられる軸受油、ギヤ油、制御系作動油;さらには油圧作動油等として使用し得る。
つまり、本発明の潤滑油組成物は、タービン、ガス圧縮機、及び油圧機器からなる群から選択される1種以上の機器等の潤滑用途に使用することが好ましい。
したがって、本発明の潤滑油組成物によれば、当該潤滑油組成物を、タービン、ガス圧縮機、及び油圧機器からなる群から選択される1種以上の機器に使用する、使用方法が提供される。
[Use of lubricating oil composition]
The lubricating oil composition of one aspect of the present invention is a turbine oil used for lubricating various turbines such as steam turbines, nuclear turbines, gas turbines, and turbines for hydraulic power generation; for lubrication of various turbo machines such as blowers and gas compressors. It can be used as bearing oil, gear oil, control system hydraulic oil; and further, hydraulic hydraulic oil and the like.
That is, the lubricating oil composition of the present invention is preferably used for lubricating applications such as one or more types of equipment selected from the group consisting of turbines, gas compressors, and hydraulic equipment.
Therefore, according to the lubricating oil composition of the present invention, there is provided a method of use in which the lubricating oil composition is used for one or more kinds of equipment selected from the group consisting of a turbine, a gas compressor, and a hydraulic equipment. NS.

本発明について、以下の実施例により具体的に説明するが、本発明は以下の実施例に限定されるものではない。 The present invention will be specifically described with reference to the following examples, but the present invention is not limited to the following examples.

[各種物性値の測定方法]
各実施例及び各比較例で用いた各原料並びに各実施例及び各比較例の潤滑油組成物の各性状の測定は、以下に示す要領に従って行ったものである。
(1)動粘度及び粘度指数
JIS K2283:2000に準拠して測定及び算出した。
(2)酸価
JIS K2501:2003の5(指示薬滴定法)に準拠して測定した。
(3)3級炭素の含有量
基油の3級炭素の含有量(炭化水素の全炭素基準)は、13C−NMRを用いて上述した方法にて測定した。
[Measurement method of various physical property values]
The measurement of each property of each raw material used in each Example and each Comparative Example and each property of the lubricating oil composition of each Example and each Comparative Example was carried out according to the procedure shown below.
(1) Kinematic viscosity and viscosity index Measured and calculated according to JIS K2283: 2000.
(2) Acid value Measured according to JIS K2501: 2003-5 (indicator titration method).
(3) Content of tertiary carbon The content of tertiary carbon in the base oil (based on the total carbon of hydrocarbons) was measured by the method described above using 13 C-NMR.

[実施例1〜3及び比較例1〜8]
以下に示す基油及び各種添加剤を、表1に示す配合量(質量%)で十分に混合し、潤滑油組成物をそれぞれ調製した。
実施例1〜3及び比較例1〜8で用いた基油及び各種添加剤の詳細は、以下に示すとおりである。
[Examples 1 to 3 and Comparative Examples 1 to 8]
The base oils and various additives shown below were sufficiently mixed in the blending amounts (mass%) shown in Table 1 to prepare lubricating oil compositions.
Details of the base oil and various additives used in Examples 1 to 3 and Comparative Examples 1 to 8 are as shown below.

<基油(X)>
・基油(X1)
石油由来のワックスを含む原料油を、水素化異性化脱ろう処理を施した後に、水素化仕上げ処理を施し得られた、API分類でグループIIIに属する基油
3級炭素の含有量:10.0at%(基油全量基準)、40℃動粘度:43.75mm/s、粘度指数:143
・基油(X2)
イソパラフィン重合体からなる基油
3級炭素の含有量:9.2at%(基油中の炭化水素の全炭素基準)、40℃動粘度:45.87mm/s、粘度指数:107
・基油(X3)
下記(1)及び(2)の基油を2種類混合し、3級炭素の含有量が5.0at%(基油全量基準)とした混合基油
(1)API分類でグループIIに属する基油、3級炭素の含有量:5.0at%(基油中の炭化水素の全炭素基準)、40℃動粘度:30.60mm/s、粘度指数:104
(2)API分類でグループIIに属する基油、3級炭素の含有量:5.0at%(基油中の炭化水素の全炭素基準)、40℃動粘度:90.51mm/s、粘度指数:107
※(1)と(2)の含有比率は、質量比で、(1):(2)=67.90:30.00である。
・基油(X4)
ポリ−α−オレフィンからなる基油
3級炭素の含有量:5.0at%(基油中の炭化水素の全炭素基準)、40℃動粘度:46.74mm/s、粘度指数:137
<Base oil (X)>
・ Base oil (X1)
Raw material oil containing petroleum-derived wax is subjected to hydrogenation isomerization dewaxing treatment and then hydrogenation finishing treatment. Content of tertiary carbon of base oil belonging to Group III according to API classification: 10. 0 at% (based on total amount of base oil), 40 ° C. kinematic viscosity: 43.75 mm 2 / s, viscosity index: 143
・ Base oil (X2)
Base oil made of isoparaffin polymer Tertiary carbon content: 9.2 at% (based on total carbon of hydrocarbons in base oil), 40 ° C kinematic viscosity: 45.87 mm 2 / s, viscosity index: 107
・ Base oil (X3)
Mixed base oils in which two types of base oils (1) and (2) below are mixed and the content of tertiary carbon is 5.0 at% (based on the total amount of base oil) (1) Groups belonging to Group II in the API classification Oil, tertiary carbon content: 5.0 at% (based on total carbon of hydrocarbons in base oil), 40 ° C kinematic viscosity: 30.60 mm 2 / s, viscosity index: 104
(2) Base oil belonging to Group II according to API classification: Content of tertiary carbon: 5.0 at% (based on total carbon of hydrocarbons in base oil), 40 ° C kinematic viscosity: 90.51 mm 2 / s, viscosity Index: 107
* The content ratio of (1) and (2) is (1) :( 2) = 67.90: 30.00 in terms of mass ratio.
・ Base oil (X4)
Base oil consisting of poly-α-olefin Content of tertiary carbon: 5.0 at% (based on total carbon of hydrocarbons in base oil), 40 ° C kinematic viscosity: 46.74 mm 2 / s, viscosity index 137

<アミン系酸化防止剤(A)>
・ジフェニルアミン(A1):ジ(オクチルフェニル)アミン
前記一般式(a1)中、Ra1及びRa2がオクチル基であり、na1=na2=1である化合物である。
・ナフチルアミン(A2):オクチルフェニル−α−ナフチルアミン
前記一般式(a2)中、Ra3がオクチル基であり、na3=1である化合物である。
<Amine-based antioxidant (A)>
-Diphenylamine (A1): Di (octylphenyl) amine In the general formula (a1), R a1 and R a2 are octyl groups, and na1 = na2 = 1.
- naphthylamine (A2): in octylphenyl -α- naphthylamine Formula (a2), R a3 is octyl, compounds which are na3 = 1.

<フェノール系酸化防止剤(B)>
・ヒンダードフェノール化合物(B1):ベンゼンプロパン酸−3,5−ビス(1,1−ジメチルエチル)−4−ヒドロキシアルキルエステル
前記一般式(b1−1)中、Rb1が炭素数2のアルキレン基、Rb2が炭素数8のアルキル基である化合物である。
<Phenolic antioxidant (B)>
-Hindered phenol compound (B1): Benzenepropanoic acid-3,5-bis (1,1-dimethylethyl) -4-hydroxyalkyl ester In the above general formula (b1-1), R b1 is an alkylene having 2 carbon atoms. A compound in which the group R b2 is an alkyl group having 8 carbon atoms.

<リン系酸化防止剤(C)>
・フェノール構造を有するリン原子含有化合物(C1):ジ−tert−ブチル−4−ヒドロキシベンジルホスホン酸ジエチル、
前記一般式(c1)中、Rc1及びRc2がtert−ブチル基、Rc3及びRc4がエチル基である化合物である。
<Phosphorus-based antioxidant (C)>
-Phosphorus atom-containing compound having a phenol structure (C1): Di-tert-butyl-4-hydroxybenzylphosphonate diethyl,
In the general formula (c1), R c1 and R c2 are compounds having a tert-butyl group, and R c3 and R c4 are compounds having an ethyl group.

<潤滑油用添加剤>
・極圧剤:ジチオリン酸
・防錆剤:アルケニルコハク酸多価アルコールエステル、
・金属不活性化剤:N−ジアルキルアミノメチルベンゾトリアゾール
・消泡剤:樹脂分濃度1質量%のシリコーン系消泡剤
<Additives for lubricating oil>
・ Extreme pressure agent: dithiophosphate ・ Rust preventive agent: alkenyl succinic acid polyhydric alcohol ester,
-Metal inactivating agent: N-dialkylaminomethylbenzotriazole-Defoaming agent: Silicone-based defoaming agent with a resin concentration of 1% by mass

実施例1〜3及び比較例1〜8の潤滑油組成物のそれぞれについて、以下の2つの試験を実施した。 The following two tests were carried out for each of the lubricating oil compositions of Examples 1 to 3 and Comparative Examples 1 to 8.

<酸化安定性試験1(試験前後での酸価増加量の評価)>
まず、各潤滑油組成物の試験前の酸価を測定した。次に、ASTM D2440に準拠し、下記条件で酸化安定性試験を実施した。この試験では、試験時間を1週間(168時間)として初期段階での酸価の上昇を確認した。
・試験温度:110℃
・触媒:銅
・試験時間:1週間(168時間)
・酸素吹き込み量:1L/h
試験後、各潤滑油組成物の酸価を測定して試験前の酸価からの上昇量(Δ酸価)を求めた。そして、Δ酸価が0.10mgKOH/g未満であるものを合格とした。
<Oxidation stability test 1 (evaluation of acid value increase before and after the test)>
First, the acid value of each lubricating oil composition before the test was measured. Next, an oxidation stability test was carried out under the following conditions in accordance with ASTM D2440. In this test, the test time was set to 1 week (168 hours), and an increase in acid value at the initial stage was confirmed.
・ Test temperature: 110 ℃
-Catalyst: Copper-Test time: 1 week (168 hours)
・ Oxygen injection amount: 1L / h
After the test, the acid value of each lubricating oil composition was measured to determine the amount of increase (Δ acid value) from the acid value before the test. Then, those having a Δ acid value of less than 0.10 mgKOH / g were regarded as acceptable.

<酸化安定性試験2(試験前後でのRPVOT値の評価)>
まず、各潤滑油組成物のRPVOT値を、ASTM D2272に準拠して試験温度150℃で測定した。次に、ASTM D2440に準拠して酸化安定性試験を行った後の各潤滑油組成物のRPVOT値を同様に測定した。この試験では、酸化防止剤の性能低下から、試験油の残存寿命を確認した。
そして、試験油のRPVOT値が600min以上であるものを合格とした。
<Oxidation stability test 2 (evaluation of RPVOT value before and after the test)>
First, the RPVOT value of each lubricating oil composition was measured at a test temperature of 150 ° C. according to ASTM D2272. Next, the RPVOT value of each lubricating oil composition after the oxidation stability test was performed according to ASTM D2440 was measured in the same manner. In this test, the remaining life of the test oil was confirmed due to the deterioration of the performance of the antioxidant.
Then, the test oil having an RPVOT value of 600 min or more was regarded as acceptable.

結果を表1に示す。 The results are shown in Table 1.

Figure 2021138881
Figure 2021138881

表1より、以下のことがわかる。
実施例1〜3の潤滑油組成物は、Δ酸価及びRPVOT値ともに優れた結果が得られ、初期段階の酸価の上昇を抑制し、酸化安定性を長期に亘り維持することができる潤滑油組成物であることがわかる。
これに対し、比較例1、2、及び4のように、ジフェニルアミン化合物(A1)、ヒンダードフェノール化合物(B1)、及びリン系酸化防止剤(C)の合計含有量[(A1)+(B1)+(C)]が2.0質量%を超える潤滑油組成物は、Δ酸価の値が大きくなり、初期段階で酸価上昇が起こりやすいことがわかる。
また、比較例3、5、及び8のように、ジフェニルアミン化合物(A1)、ヒンダードフェノール化合物(B1)、及びリン系酸化防止剤(C)の合計含有量[(A1)+(B1)+(C)]が1.0質量%以下である潤滑油組成物は、RPVOT値が低下し、酸化安定性を長期に亘って維持できないことがわかる。
さらに、比較例6及び7のように、3級炭素の含有量が8.0at%未満である基油を用いた潤滑油組成物は、Δ酸価の値は小さいことから初期段階での酸価上昇は起こり難いものの、RPVOT値が低下し、酸化安定性を長期に亘って維持できないことがわかる。
From Table 1, the following can be seen.
The lubricating oil compositions of Examples 1 to 3 gave excellent results in both Δ acid value and RPVOT value, suppressed an increase in acid value in the initial stage, and could maintain oxidative stability for a long period of time. It turns out that it is an oil composition.
On the other hand, as in Comparative Examples 1, 2, and 4, the total content of the diphenylamine compound (A1), the hindered phenol compound (B1), and the phosphorus-based antioxidant (C) [(A1) + (B1) ) + (C)] is more than 2.0% by mass, the value of Δ acid value becomes large, and it can be seen that the acid value tends to increase in the initial stage.
Further, as in Comparative Examples 3, 5, and 8, the total content of the diphenylamine compound (A1), the hindered phenol compound (B1), and the phosphorus-based antioxidant (C) [(A1) + (B1) + It can be seen that in the lubricating oil composition in which [(C)] is 1.0% by mass or less, the RPVOT value is lowered and the oxidative stability cannot be maintained for a long period of time.
Further, as in Comparative Examples 6 and 7, the lubricating oil composition using the base oil having a tertiary carbon content of less than 8.0 at% has a small Δ acid value, so that the acid in the initial stage It can be seen that although the price increase is unlikely to occur, the RPVOT value decreases and the oxidative stability cannot be maintained for a long period of time.

Claims (11)

3級炭素の含有量が、炭化水素の全炭素基準で、8.0at%以上である基油(X)と、
アミン系酸化防止剤(A)、フェノール系酸化防止剤(B)、及びリン系酸化防止剤(C)を含む酸化防止剤(Y)と、
を含有する潤滑油組成物であって、
前記アミン系酸化防止剤(A)は、下記一般式(a1)で表されるジフェニルアミン化合物(A1)を含み、
Figure 2021138881

[上記一般式(a1)中、Ra1及びRa2は、各々独立に、炭素数1〜30のアルキル基である。na1及びna2は、各々独立に、1〜5の整数である。na1が2以上である場合、複数のRa1は、同一であってもよく、互いに異なっていてもよい。na2が2以上である場合、複数のRa2は、同一であってもよく、互いに異なっていてもよい。]
前記フェノール系酸化防止剤(B)は、エステル構造を有するヒンダードフェノール化合物(B1)を含み、
前記ジフェニルアミン化合物(A1)、前記エステル構造を有するヒンダードフェノール化合物(B1)、及び前記リン系酸化防止剤(C)の合計含有量[(A1)+(B1)+(C)]が、前記潤滑油組成物の全量基準で、1.0質量%超2.0質量%以下である、潤滑油組成物。
Base oil (X) having a tertiary carbon content of 8.0 at% or more based on the total carbon of hydrocarbons, and
An antioxidant (Y) containing an amine-based antioxidant (A), a phenol-based antioxidant (B), and a phosphorus-based antioxidant (C),
A lubricating oil composition containing
The amine-based antioxidant (A) contains a diphenylamine compound (A1) represented by the following general formula (a1), and contains the diphenylamine compound (A1).
Figure 2021138881

[In the above general formula (a1), Ra1 and Ra2 are independently alkyl groups having 1 to 30 carbon atoms. na1 and na2 are each independently an integer of 1-5. If na1 is 2 or more, plural R a1 may be the same or different from each other. If na2 is 2 or more, plural R a2 may be the same or different from each other. ]
The phenolic antioxidant (B) contains a hindered phenol compound (B1) having an ester structure.
The total content of the diphenylamine compound (A1), the hindered phenol compound (B1) having the ester structure, and the phosphorus-based antioxidant (C) [(A1) + (B1) + (C)] is the above. A lubricating oil composition that is more than 1.0% by mass and 2.0% by mass or less based on the total amount of the lubricating oil composition.
前記ジフェニルアミン化合物(A1)及び前記エステル構造を有するヒンダードフェノール化合物(B1)の合計含有量[(A1)+(B1)]が、前記潤滑油組成物の全量基準で、0.9質量%以上である、請求項1に記載の潤滑油組成物。 The total content [(A1) + (B1)] of the diphenylamine compound (A1) and the hindered phenol compound (B1) having an ester structure is 0.9% by mass or more based on the total amount of the lubricating oil composition. The lubricating oil composition according to claim 1. 前記ジフェニルアミン化合物(A1)が、前記潤滑油組成物の全量基準で、0.3質量%〜1.8質量%である、請求項1又は2に記載の潤滑油組成物。 The lubricating oil composition according to claim 1 or 2, wherein the diphenylamine compound (A1) is 0.3% by mass to 1.8% by mass based on the total amount of the lubricating oil composition. 前記アミン系酸化防止剤(A)が、更に、下記一般式(a2)で表されるナフチルアミン化合物(A2)を含む、請求項1〜3のいずれか1項に記載の潤滑油組成物。
Figure 2021138881

[上記一般式(a2)中、Ra3は、炭素数1〜30のアルキル基である。na3は、1〜5の整数である。na3が2以上である場合、複数のRa3は、同一であってもよく、互いに異なっていてもよい。]
The lubricating oil composition according to any one of claims 1 to 3, wherein the amine-based antioxidant (A) further contains a naphthylamine compound (A2) represented by the following general formula (a2).
Figure 2021138881

[In the above general formula (a2), Ra3 is an alkyl group having 1 to 30 carbon atoms. na3 is an integer of 1-5. If na3 is 2 or more, plural R a3 may be the same or different from each other. ]
前記ジフェニルアミン(A1)と前記ナフチルアミン(A2)の合計含有量[(A1)+(A2)]が、前記潤滑油組成物の全量基準で、0.8質量%以上2.0質量%未満である、請求項4に記載の潤滑油組成物。 The total content [(A1) + (A2)] of the diphenylamine (A1) and the naphthylamine (A2) is 0.8% by mass or more and less than 2.0% by mass based on the total amount of the lubricating oil composition. , The lubricating oil composition according to claim 4. 前記エステル構造を有するヒンダードフェノール化合物(B1)が、下記一般式(b1−1)で表される化合物(B1−1)及び下記一般式(b1−2)で表される化合物(B1−2)からなる群から選択される1種以上である、請求項1〜5のいずれか1項に記載の潤滑油組成物。
Figure 2021138881

[上記式(b1−1)中、Rb1は、炭素数1〜5のアルキレン基である。Rb2は、炭素数1〜25のアルキル基である。]
Figure 2021138881

[上記式(b1−2)中、Rb3及びRb4は、各々独立に、炭素数1〜5のアルキレン基である。mは、2〜4の整数である。]
The hindered phenol compound (B1) having the ester structure is represented by the compound represented by the following general formula (b1-1) (B1-1) and the compound represented by the following general formula (b1-2) (B1-2). The lubricating oil composition according to any one of claims 1 to 5, which is one or more selected from the group consisting of).
Figure 2021138881

[In the above formula (b1-1), R b1 is an alkylene group having 1 to 5 carbon atoms. R b2 is an alkyl group having 1 to 25 carbon atoms. ]
Figure 2021138881

[In the above formula (b1-2), R b3 and R b4 are independently alkylene groups having 1 to 5 carbon atoms. m is an integer of 2-4. ]
前記リン系酸化防止剤(C)が、下記一般式(c1)で表される、フェノール構造を有するリン原子含有化合物(C1)を含む、請求項1〜6のいずれか1項に記載の潤滑油組成物。
Figure 2021138881

[上記一般式(c1)中、Rc1、Rc2、Rc3、及びRc4は、各々独立に、水素原子又は炭素数1〜30のアルキル基である。]
The lubrication according to any one of claims 1 to 6, wherein the phosphorus-based antioxidant (C) contains a phosphorus atom-containing compound (C1) having a phenol structure represented by the following general formula (c1). Oil composition.
Figure 2021138881

[In the above general formula (c1), R c1 , R c2 , R c3 , and R c4 are each independently a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. ]
更に、極圧剤、清浄分散剤、流動点降下剤、粘度指数向上剤、防錆剤、金属不活性化剤、消泡剤、及び摩擦調整剤からなる群から選択される1種以上の潤滑油用添加剤を含有する、請求項1〜7のいずれか1項に記載の潤滑油組成物。 Further, one or more types of lubricants selected from the group consisting of extreme pressure agents, cleaning dispersants, flow point lowering agents, viscosity index improvers, rust preventives, metal deactivators, defoamers, and friction modifiers. The lubricating oil composition according to any one of claims 1 to 7, which contains an additive for oil. 前記基油(X)が、前記潤滑油組成物の全量基準で、90.0質量%以上である、請求項1〜8のいずれか1項に記載の潤滑油組成物。 The lubricating oil composition according to any one of claims 1 to 8, wherein the base oil (X) is 90.0% by mass or more based on the total amount of the lubricating oil composition. タービン、圧縮機、及び油圧機器からなる群から選択される1種以上の機器に用いられる、請求項1〜9のいずれか1項に記載の潤滑油組成物。 The lubricating oil composition according to any one of claims 1 to 9, which is used for one or more kinds of equipment selected from the group consisting of turbines, compressors, and hydraulic equipment. 請求項1〜9のいずれか1項に記載の潤滑油組成物を、タービン、圧縮機、及び油圧機器からなる群から選択される1種以上の機器に使用する、使用方法。 A method of use, wherein the lubricating oil composition according to any one of claims 1 to 9 is used for one or more kinds of equipment selected from the group consisting of a turbine, a compressor, and a hydraulic equipment.
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