JP2021161291A - Lubricant composition - Google Patents

Lubricant composition Download PDF

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JP2021161291A
JP2021161291A JP2020065360A JP2020065360A JP2021161291A JP 2021161291 A JP2021161291 A JP 2021161291A JP 2020065360 A JP2020065360 A JP 2020065360A JP 2020065360 A JP2020065360 A JP 2020065360A JP 2021161291 A JP2021161291 A JP 2021161291A
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lubricating oil
oil composition
mass
sodium
mass ppm
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JP7493373B2 (en
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元気 奥山
Genki Okuyama
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Idemitsu Kosan Co Ltd
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Idemitsu Kosan Co Ltd
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Priority to JP2020065360A priority Critical patent/JP7493373B2/en
Priority claimed from JP2020065360A external-priority patent/JP7493373B2/en
Priority to US17/907,327 priority patent/US20230112787A1/en
Priority to CN202180024788.8A priority patent/CN115279871A/en
Priority to PCT/JP2021/013231 priority patent/WO2021200799A1/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/045—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution and non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
    • C10M135/10—Sulfonic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C10M137/10—Thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating 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
    • C10M141/10—Lubricating 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/003—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/52—Base number [TBN]
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/12—Gas-turbines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/30—Refrigerators lubricants or compressors lubricants

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

Abstract

To provide a lubricant composition, the hue of which is deteriorated less quickly over time, the lubricant composition comprising a zinc dialkyldithiophosphate.SOLUTION: A lubricant composition comprises a base oil (A), a zinc dialkyldithiophosphate (B), and a sodium-based cleaning agent (C), wherein: a zinc atom content is 100 mass ppm to 2,000 mass ppm based on the total amount of the lubricant composition; and a sodium atom content is 5 mass ppm to 1,000 mass ppm based on the total amount of the lubricant composition.SELECTED DRAWING: None

Description

本発明は、潤滑油組成物に関する。 The present invention relates to a lubricating oil composition.

潤滑油組成物には、酸化防止能及び摩耗防止能等を付与する観点から、ジアルキルジチオリン酸亜鉛が、広く使用されている。
ジアルキルジチオリン酸亜鉛は、上記のように、潤滑油組成物に酸化防止能及び摩耗防止能等を付与できる点で優れている一方で、熱酸化等によりスラッジ発生の要因となりやすい側面も有する、そこで、ジアルキルジチオリン酸亜鉛に由来するスラッジを抑制する手法が各種採用されている。 Zinc dialkyldithiophosphate is widely used in the lubricating oil composition from the viewpoint of imparting antioxidant ability, anti-wear ability and the like.
As described above, zinc dialkyldithiophosphate is excellent in that it can impart antioxidant ability and anti-wear ability to the lubricating oil composition, but also has an aspect that easily causes sludge generation due to thermal oxidation and the like. , Various methods for suppressing sludge derived from zinc dialkyldithiophosphate have been adopted.

例えば、特許文献１には、工業用油圧作動油組成物において、ジアルキルジチオリン酸亜鉛に由来するスラッジを抑制するために、過塩基性金属サリチレートを配合することが記載されている。また、当該過塩基性金属サリチレートを構成する金属成分が、カルシウム及びマグネシウム等のアルカリ土類金属であり、好ましくはカルシウムであることも記載されている。 For example, Patent Document 1 describes that a hyperbasic metal salicylate is blended in an industrial hydraulic fluid composition in order to suppress sludge derived from zinc dialkyldithiophosphate. It is also described that the metal component constituting the hyperbasic metal salicylate is an alkaline earth metal such as calcium and magnesium, preferably calcium.

特開２０１６−０８９０４３号公報Japanese Unexamined Patent Publication No. 2016-089043

ところで、潤滑油組成物は、使用時間とともに徐々に劣化して色相が悪化（濃色化）する傾向がある。そこで、潤滑油組成物の劣化状況を簡便に把握するために、潤滑油組成物の色相の変化を利用した劣化判定手法が、潤滑油組成物を用いた機械及び設備等の管理において広く用いられている。
しかし、ジアルキルジチオリン酸亜鉛を配合した潤滑油組成物は、色相が悪化しやすい傾向が見られる一方で、色相が悪化した後も潤滑油組成物としての性能は維持されていることがある。そのため、色相の変化だけでは一概に劣化の状況が判定できないという問題がある。 By the way, the lubricating oil composition tends to gradually deteriorate with time of use and the hue tends to deteriorate (darken). Therefore, in order to easily grasp the deterioration status of the lubricating oil composition, a deterioration determination method using a change in the hue of the lubricating oil composition is widely used in the management of machines and equipment using the lubricating oil composition. ing.
However, while the lubricating oil composition containing zinc dialkyldithiophosphate tends to have a tendency to deteriorate in hue, the performance as a lubricating oil composition may be maintained even after the hue has deteriorated. Therefore, there is a problem that the state of deterioration cannot be unconditionally determined only by the change in hue.

また、潤滑油組成物を用いた機械及び設備等の管理においては、汚染の状況及び沈殿物の発生状況等を目視で確認することが多い。しかし、潤滑油組成物の色相の悪化が早期に発生してしまうと、潤滑油組成物の汚染の状況及び沈殿物の発生状況等の視認性が悪化し、汚染の状況及び沈殿物の発生状況等を目視で捉えきれなくなる。その結果、機械及び設備等の停止につながる恐れがある。 Further, in the management of machines and equipment using the lubricating oil composition, it is often the case that the state of contamination and the state of generation of precipitates are visually confirmed. However, if the hue of the lubricating oil composition deteriorates at an early stage, the visibility of the contamination status of the lubricating oil composition and the generation status of the precipitate deteriorates, and the contamination status and the generation status of the precipitate deteriorate. Etc. cannot be visually grasped. As a result, there is a risk of stopping machines and equipment.

そこで、本発明者は、ジアルキルジチオリン酸亜鉛を配合した潤滑油組成物の時間の経過に伴う色相の悪化を緩やかにすることを考えた。これにより、潤滑油組成物の汚染の状況及び沈殿物の発生状況等を目視で適切に観察できる期間を延ばすことができ、汚染の状況及び沈殿物の発生状況等を目視で捉えきれないことによる機械及び設備等の停止リスクを軽減できると考えられる。また、潤滑油組成物の色相の悪化を緩やかにすることは、少なくとも潤滑油組成物の酸化劣化を抑制しているともいえるため、潤滑油組成物に対する望ましい対策であるといえる。 Therefore, the present inventor has considered to moderate the deterioration of hue with the passage of time in the lubricating oil composition containing zinc dialkyldithiophosphate. As a result, it is possible to extend the period during which the state of contamination of the lubricating oil composition and the state of generation of precipitates can be visually observed appropriately, and the state of contamination and the state of generation of precipitates cannot be visually grasped. It is thought that the risk of stopping machines and equipment can be reduced. Further, it can be said that slowing down the deterioration of the hue of the lubricating oil composition is at least suppressing the oxidative deterioration of the lubricating oil composition, and thus it can be said that it is a desirable measure for the lubricating oil composition.

本発明は、ジアルキルジチオリン酸亜鉛を含有する潤滑油組成物であって、時間の経過に伴う色相の悪化が緩やかである潤滑油組成物を提供することを課題とする。 An object of the present invention is to provide a lubricating oil composition containing zinc dialkyldithiophosphate, wherein the deterioration of the hue with the passage of time is gradual.

本発明者は、上記課題を解決すべく鋭意検討を重ね、以下の発明を完成するに至った。
すなわち、本発明は、下記［１］〜［６］に関する。
［１］ 基油（Ａ）と、ジアルキルジチオリン酸亜鉛（Ｂ）と、ナトリウム系清浄剤（Ｃ）とを含有する潤滑油組成物であり、
亜鉛原子含有量が、前記潤滑油組成物の全量基準で、１００質量ｐｐｍ〜２，０００質量ｐｐｍであり、
ナトリウム原子含有量が、前記潤滑油組成物の全量基準で、５質量ｐｐｍ〜１，０００質量ｐｐｍである、潤滑油組成物。
［２］ 前記潤滑油組成物中の亜鉛原子（Ｚｎ）と前記潤滑油組成物中のナトリウム原子（Ｎａ）との含有比率［（Ｚｎ）／（Ｎａ）］が、質量比で、０．０５０〜５０である、［１］に記載の潤滑油組成物。
［３］ マグネシウム原子の含有量が、前記潤滑油組成物の全量基準で、３０質量ｐｐｍ未満である、［１］又は［２］に記載の潤滑油組成物。
［４］ カルシウム原子の含有量が、前記潤滑油組成物の全量基準で、３０質量ｐｐｍ未満である、［１］〜［３］いずれかに記載の潤滑油組成物。
［５］ 触媒として銅片と鉄片を入れ、ＪＩＳ Ｋ ２５１４−１：２０１３に準拠するＩＳＯＴ試験を、１５０℃で１６８時間行った後のＡＳＴＭ色が、１．０以下である、［１］〜［４］いずれかに記載の潤滑油組成物。
［６］ 基油（Ａ）の４０℃における動粘度が、９．００ｍｍ２／ｓ〜１６５ｍｍ２／ｓである、［１］〜［５］いずれかに記載の潤滑油組成物。 The present inventor has made extensive studies to solve the above problems and has completed the following invention.
That is, the present invention relates to the following [1] to [6].
[1] A lubricating oil composition containing a base oil (A), zinc dialkyldithiophosphate (B), and a sodium-based cleaning agent (C).
The zinc atom content is 100 mass ppm to 2,000 mass ppm based on the total amount of the lubricating oil composition.
A lubricating oil composition having a sodium atom content of 5 mass ppm to 1,000 mass ppm based on the total amount of the lubricating oil composition.
[2] The content ratio [(Zn) / (Na)] of the zinc atom (Zn) in the lubricating oil composition and the sodium atom (Na) in the lubricating oil composition is 0.050 by mass ratio. The lubricating oil composition according to [1], which is ~ 50.
[3] The lubricating oil composition according to [1] or [2], wherein the content of magnesium atoms is less than 30 mass ppm based on the total amount of the lubricating oil composition.
[4] The lubricating oil composition according to any one of [1] to [3], wherein the content of calcium atoms is less than 30 mass ppm based on the total amount of the lubricating oil composition.
[5] An ASTM color of 1.0 or less after conducting an ISOT test conforming to JIS K 2514-1: 2013 at 150 ° C. for 168 hours with a copper piece and an iron piece as a catalyst, [1] to [4] The lubricating oil composition according to any one.
[6] The kinematic viscosity at 40 ° C. of the base oil (A) is 9.00mm 2 / s~165mm 2 / s, [1] ~ [5] The lubricating oil composition according to any one.

本発明によれば、ジアルキルジチオリン酸亜鉛を含有する潤滑油組成物であって、時間の経過に伴う色相の悪化が緩やかであ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, it is possible to provide a lubricating oil composition containing zinc dialkyldithiophosphate, wherein the deterioration of hue with the passage of time is gradual.

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」とすることができる。
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。
また、本明細書において、「Ａ〜Ｂ」と記載されている数値範囲は、特にことわりのない限り、「Ａ以上Ｂ以下」であることを意味する。 In the present specification, the lower limit value and the upper limit value described stepwise for a preferable numerical range (for example, a range such as content) can be independently combined. 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". be able to.
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.
Further, in the present specification, the numerical range described as "A to B" means "A or more and B 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、基油（Ａ）と、ジアルキルジチオリン酸亜鉛（Ｂ）と、ナトリウム系清浄剤（Ｃ）とを含有する潤滑油組成物であり、
亜鉛原子含有量が、前記潤滑油組成物の全量基準で、１００質量ｐｐｍ〜２，０００質量ｐｐｍであり、
ナトリウム原子含有量が、前記潤滑油組成物の全量基準で、５質量ｐｐｍ〜１，０００質量ｐｐｍである、潤滑油組成物である。 [Aspects of Lubricating Oil Composition of the Present Invention]
The lubricating oil composition of the present invention is a lubricating oil composition containing a base oil (A), zinc dialkyldithiophosphate (B), and a sodium-based cleaning agent (C).
The zinc atom content is 100 mass ppm to 2,000 mass ppm based on the total amount of the lubricating oil composition.
A lubricating oil composition having a sodium atom content of 5 mass ppm to 1,000 mass ppm based on the total amount of the lubricating oil composition.

本発明者は、ジアルキルジチオリン酸亜鉛（以下、「ＺｎＤＴＰ」ともいう）を含有する潤滑油組成物について、時間の経過に伴う色相の悪化を緩やかにすべく、鋭意検討を行った。その結果、ＺｎＤＴＰとナトリウム系清浄剤とを組み合わせて用い、且つ亜鉛原子含有量とナトリウム原子含有量とを、各々特定の範囲に調整した潤滑油組成物が、時間の経過に伴う色相の悪化を緩やかにできることを見出した。
なお、本発明者の検討によると、ＺｎＤＴＰとナトリウム系清浄剤とを組み合わせることなく、それぞれ単独で潤滑油組成物に配合した場合、時間の経過に伴う色相の悪化が早期に生じやすいことがわかった。特に、ナトリウム系清浄剤を単独で配合した場合には、時間の経過に伴う色相の悪化が顕著であった。
ところが、ＺｎＤＴＰとナトリウム系清浄剤とを組み合わせて潤滑油組成物に配合した場合、意外なことに、時間の経過に伴う色相の悪化が極めて緩やかになることが分かった。
この現象の詳細なメカニズムについては明らかではないが、少なくとも、ＺｎＤＴＰの影響による潤滑油組成物の色相の悪化がナトリウム系清浄剤により抑制されると共に、ナトリウム系清浄剤の影響による色相の悪化がＺｎＤＴＰにより抑制されることによるものと考えられる。換言すれば、ＺｎＤＴＰとナトリウム系清浄剤との相互作用によって、ＺｎＤＴＰ及びナトリウム系清浄剤をそれぞれ単独で潤滑油組成物に配合した場合に生じる色相の早期悪化を抑制することができ、本発明の効果が発揮されているものと推察される。
なお、本発明の効果は、ナトリウム系清浄剤を、カルシウム系清浄剤に代えた場合や、マグネシウム系清浄剤に代えた場合には、奏されない効果である。 The present inventor has diligently studied a lubricating oil composition containing zinc dialkyldithiophosphate (hereinafter, also referred to as “ZnDTP”) in order to moderate the deterioration of hue over time. As a result, the lubricating oil composition in which ZnDTP and a sodium-based detergent are used in combination and the zinc atom content and the sodium atom content are each adjusted to a specific range causes deterioration of the hue over time. I found that I could do it slowly.
According to the study by the present inventor, it has been found that when ZnDTP and a sodium-based detergent are individually blended in the lubricating oil composition without being combined, the hue tends to deteriorate at an early stage with the passage of time. rice field. In particular, when the sodium-based cleaning agent was blended alone, the deterioration of hue with the passage of time was remarkable.
However, when ZnDTP and a sodium-based detergent were combined and blended in the lubricating oil composition, it was surprisingly found that the deterioration of the hue with the passage of time became extremely slow.
Although the detailed mechanism of this phenomenon is not clear, at least the deterioration of the hue of the lubricating oil composition due to the influence of ZnDTP is suppressed by the sodium-based cleaning agent, and the deterioration of the hue due to the influence of the sodium-based cleaning agent is ZnDTP. It is considered that this is due to being suppressed by. In other words, the interaction between ZnDTP and the sodium-based cleaning agent can suppress the early deterioration of the hue that occurs when ZnDTP and the sodium-based cleaning agent are individually blended in the lubricating oil composition. It is presumed that the effect is being exhibited.
The effect of the present invention is an effect that is not exhibited when the sodium-based cleaning agent is replaced with a calcium-based cleaning agent or a magnesium-based cleaning agent.

なお、以降の説明では、「基油（Ａ）」、「ＺｎＤＴＰ（Ｂ）」、及び「ナトリウム系清浄剤（Ｃ）」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うことのない範囲で、「成分（Ａ）」、「成分（Ｂ）」、及び「成分（Ｃ）」以外の他の成分を含有していてもよい。
本発明の一態様において、成分（Ａ）、成分（Ｂ）、及び成分（Ｃ）の合計含有量は、本発明の効果をより発揮させやすくする観点から、潤滑油組成物の全量基準で、好ましくは７０．０質量％〜１００質量％、より好ましくは８０．０質量％〜１００質量％、更に好ましくは９０．０質量％〜１００質量％、より更に好ましくは９５．０質量％〜１００質量％である。 In the following description, "base oil (A)", "ZnDTP (B)", and "sodium-based cleaning agent (C)" are referred to as "component (A)", "component (B)", and "component (B)", respectively. Also referred to as "ingredient (C)".
The lubricating oil composition of one aspect of the present invention may be composed of only "component (A)", "component (B)", and "component (C)", but impairs the effect of the present invention. It may contain other components other than "component (A)", "component (B)", and "component (C)" as long as there is no such substance.
In one aspect of the present invention, the total content of the component (A), the component (B), and the component (C) is based on the total mass of the lubricating oil composition from the viewpoint of facilitating the effect of the present invention. It is preferably 70.0% by mass to 100% by mass, more preferably 80.0% by mass to 100% by mass, still more preferably 90.0% by mass to 100% by mass, and even more preferably 95.0% by mass to 100% by mass. %.

以下、基油（Ａ）、ＺｎＤＴＰ（Ｂ）、及びナトリウム系清浄剤（Ｃ）、並びに他の添加剤について、詳細に説明する。 Hereinafter, the base oil (A), ZnDTP (B), the sodium-based cleaning agent (C), and other additives will be described in detail.

＜基油（Ａ）＞
本発明の潤滑油組成物は、基油（Ａ）を含有する。
基油（Ａ）としては、従来、潤滑油の基油として用いられている鉱油及び合成油から選択される１種以上を、特に制限なく使用することができる。 <Base oil (A)>
The lubricating oil composition of the present invention contains a base oil (A).
As the base oil (A), one or more selected from mineral oils and synthetic oils conventionally used as base oils for lubricating oils can be used without particular limitation.

鉱油としては、例えば、パラフィン系原油、中間基系原油、又はナフテン系原油等の原油を常圧蒸留して得られる常圧残油；これらの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、水素化分解、溶剤脱ろう、接触脱ろう、及び水素化精製等の精製処理を１つ以上施して得られる鉱油；等が挙げられる。 As the mineral oil, for example, atmospheric residual oil obtained by atmospheric distillation of crude oil such as paraffin crude oil, intermediate base crude oil, or naphthenic crude oil; distillate obtained by vacuum distillation of these atmospheric residual oils. Oil; Mineral oil obtained by subjecting the distillate oil to one or more refining treatments such as solvent desorption, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, and hydrorefining; and the like.

合成油としては、例えば、α−オレフィン単独重合体及びα−オレフィン共重合体（例えば、エチレン−α−オレフィン共重合体等の炭素数８〜１４のα−オレフィン共重合体）等のポリα−オレフィン；イソパラフィン；ポリオールエステル及び二塩基酸エステル等の各種エステル；ポリフェニルエーテル等の各種エーテル；ポリアルキレングリコール；アルキルベンゼン；アルキルナフタレン；天然ガスからフィッシャー・トロプシュ法等により製造されるワックス（ガストゥリキッド（ＧＴＬ）ワックス）を異性化することで得られるＧＴＬ基油等が挙げられる。 Examples of the synthetic oil include polyα such as an α-olefin homopolymer and an α-olefin copolymer (for example, an α-olefin copolymer having 8 to 14 carbon atoms such as an ethylene-α-olefin copolymer). -Olefin; isoparaffin; various esters such as polyol ester and dibasic acid ester; various ethers such as polyphenyl ether; polyalkylene glycol; alkylbenzene; alkylnaphthalene; wax produced from natural gas by Fischer-Tropsch method, etc. Examples thereof include GTL base oil obtained by isomerizing liquid (GTL) wax).

基油（Ａ）は、鉱油を単独で又は複数種組み合わせて用いてもよいし、合成油を単独で又は複数種組み合わせて用いてもよい。また、１種以上の鉱油と１種以上の合成油とを組み合わせて用いてもよい。 As the base oil (A), mineral oil may be used alone or in combination of a plurality of types, and synthetic oil may be used alone or in combination of a plurality of types. Further, one or more kinds of mineral oil and one or more kinds of synthetic oil may be used in combination.

基油（Ａ）は、潤滑油組成物の酸化安定性をより向上させる観点から、米国石油協会（ＡＰＩ）の基油カテゴリーにおけるグループＩＩ、ＩＩＩ、及びＩＶに分類される基油から選択される１種以上が好ましく、グループＩＩ及びＩＩＩに分類される基油から選択される１種以上がより好ましい。 The base oil (A) is selected from the base oils classified into groups II, III, and IV in the base oil category of the American Petroleum Institute (API) from the viewpoint of further improving the oxidative stability of the lubricating oil composition. One or more are preferable, and one or more selected from the base oils classified into groups II and III are more preferable.

基油（Ａ）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８．００ｍｍ２／ｓ〜１５０ｍｍ２／ｓ、より好ましくは１０．０ｍｍ２／ｓ〜１２０ｍｍ２／ｓ、更に好ましくは１５．０ｍｍ２／ｓ〜１００ｍｍ２／ｓである。
基油（Ａ）の４０℃動粘度が８．００ｍｍ２／ｓ以上であると、引火点が高く、潤滑性能に優れる潤滑油組成物としやすい。
また、基油（Ａ）の４０℃動粘度が１５０ｍｍ２／ｓ以下であると、低温時の粘性抵抗がそれほど大きくなることもなく、機械の作動を良好なものとしやすい。 Kinematic viscosity (hereinafter also referred to as "40 ° C. kinematic viscosity") at 40 ° C. of the base oil (A) is preferably 8.00mm 2 / s~150mm 2 / s, more preferably 10.0mm 2 / s~120mm 2 / s, more preferably from 15.0mm 2 / s~100mm 2 / s.
When the kinematic viscosity of the base oil (A) at 40 ° C. is 8.00 mm 2 / s or more, it is easy to obtain a lubricating oil composition having a high flash point and excellent lubricating performance.
Further, when the 40 ° C. kinematic viscosity of the base oil (A) is 150 mm 2 / s or less, the viscous resistance at low temperature does not increase so much, and it is easy to improve the operation of the machine.

基油（Ａ）の粘度指数は、好ましくは８０以上、より好ましくは９０以上、更に好ましくは１００以上である。基油（Ａ）の粘度指数が上記範囲であると、温度変化による粘度変化を抑えて高温時に油膜を形成させやすくすることができ、耐摩耗性を向上させやすい。 The viscosity index of the base oil (A) is preferably 80 or more, more preferably 90 or more, still more preferably 100 or more. When the viscosity index of the base oil (A) is in the above range, it is possible to suppress the change in viscosity due to the temperature change and facilitate the formation of an oil film at a high temperature, and it is easy to improve the wear resistance.

なお、基油（Ａ）が２種以上の基油を含有する混合基油である場合、当該混合基油の４０℃動粘度及び粘度指数が上記範囲内であることが好ましい。 When the base oil (A) is a mixed base oil containing two or more kinds of base oils, it is preferable that the 40 ° C. kinematic viscosity and the viscosity index of the mixed base oil are within the above ranges.

本明細書において、４０℃動粘度及び粘度指数は、ＪＩＳ Ｋ ２２８３：２０００に準拠して測定又は算出される値を意味する。 As used herein, the 40 ° C. kinematic viscosity and viscosity index mean values measured or calculated in accordance with JIS K 2283: 2000.

本発明の一態様の潤滑油組成物において、基油（Ａ）の含有量は、本発明の効果をより発揮させやすくする観点から、潤滑油組成物の全量基準で、好ましくは８０．０質量％〜９９．８４質量％、より好ましくは８５．０質量％〜〜９９．８０質量％、更に好ましくは９０．０質量％〜９９．５０質量％である。 In the lubricating oil composition of one aspect of the present invention, the content of the base oil (A) is preferably 80.0% by mass based on the total amount of the lubricating oil composition from the viewpoint of making it easier to exert the effect of the present invention. % To 99.84% by mass, more preferably 85.0% by mass to ~ 99.80% by mass, still more preferably 90.0% by mass to 99.50% by mass.

＜ＺｎＤＴＰ（Ｂ）＞
本発明の潤滑油組成物は、ＺｎＤＴＰ（Ｂ）を含有する。
潤滑油組成物がＺｎＤＴＰ（Ｂ）を含有することで、潤滑油組成物に酸化防止能及び摩耗防止能等が付与される。
なお、潤滑油組成物がＺｎＤＴＰ（Ｂ）を含有しない場合、ＺｎＤＴＰ（Ｂ）とナトリウム系清浄剤（Ｃ）との組み合わせることによる本発明の効果が発揮されない。 <ZnDTP (B)>
The lubricating oil composition of the present invention contains ZnDTP (B).
When the lubricating oil composition contains ZnDTP (B), the lubricating oil composition is imparted with antioxidant ability, anti-wear ability and the like.
When the lubricating oil composition does not contain ZnDTP (B), the effect of the present invention cannot be exhibited by combining ZnDTP (B) with the sodium-based cleaning agent (C).

本発明の一態様の潤滑油組成物に用いられるＺｎＤＴＰ（Ｂ）としては、例えば、下記一般式（ｂ１）で表されるものが好ましく挙げられる。 As the ZnDTP (B) used in the lubricating oil composition of one aspect of the present invention, for example, those represented by the following general formula (b1) are preferably mentioned.

Figure 2021161291
Figure 2021161291

上記一般式（ｂ１）中、Ｒ１１〜Ｒ１４は、各々独立に、炭素数３〜２２の第１級もしくは第２級アルキル基、又は炭素数３〜１８のアルキル基で置換されたアルキルアリール基である。 In the above general formula (b1), R 11 to R 14 are each independently substituted with a primary or secondary alkyl group having 3 to 22 carbon atoms or an alkyl group having 3 to 18 carbon atoms. Is the basis.

Ｒ１１〜Ｒ１４として選択され得る、炭素数３〜２２の第１級もしくは第２級アルキル基としては、第１級もしくは第２級のプロピル基、ブチル基、ペンチル基、ヘキシル基、へプチル基、オクチル基、ノニル基、デシル基、ドデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基、イコシル基、エチルヘキシル基等が挙げられる。
また、Ｒ１１〜Ｒ１４として選択され得る、炭素数３〜１８のアルキル基で置換されたアルキルアリール基としては、例えばプロピルフェニル基、ペンチルフェニル基、オクチルフェニル基、ノニルフェニル基、ドデシルフェニル基等が挙げられる。 The primary or secondary alkyl group having 3 to 22 carbon atoms, which can be selected as R 11 to R 14 , includes a primary or secondary propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl. Examples thereof include a group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, an icosyl group and an ethylhexyl group.
Examples of the alkylaryl group substituted with an alkyl group having 3 to 18 carbon atoms, which can be selected as R 11 to R 14, include a propylphenyl group, a pentylphenyl group, an octylphenyl group, a nonylphenyl group, and a dodecylphenyl group. And so on.

ＺｎＤＴＰ（Ｂ）として、上記一般式（ｂ１）で表される化合物を用いる場合、当該化合物は、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。
ここで、本発明の一態様の潤滑油組成物において、ＺｎＤＴＰ（Ｂ）として、上記一般式（ｂ１）で表される化合物を用いる場合には、少なくとも第１級アルキル基を有する第１級ジアルキルジチオリン酸亜鉛（第１級アルキルＺｎＤＴＰ）を用いることが好ましく、第１級アルキルＺｎＤＴＰを単独で用いることがより好ましい。
第１級アルキルＺｎＤＴＰと第２級アルキル基を有する第２級ジアルキルジチオリン酸亜鉛（第２級アルキルＺｎＤＴＰ）とを組み合わせて用いる場合、第１級アルキルＺｎＤＴＰと第２級アルキルＺｎＤＴＰとの含有比率［（第１級アルキルＺｎＤＴＰ）／（第２級アルキルＺｎＤＴＰ）］は、質量比で、好ましくは５０／５０〜９９／１、より好ましくは６０／４０〜９５／５、更に好ましくは７０／３０〜９０／１０である。 When a compound represented by the above general formula (b1) is used as ZnDTP (B), one type of the compound may be used alone, or two or more types may be used in combination.
Here, in the lubricating oil composition of one aspect of the present invention, when a compound represented by the above general formula (b1) is used as ZnDTP (B), a primary dialkyl having at least a primary alkyl group is used. It is preferable to use zinc dithiophosphate (primary alkyl ZnDTP), and it is more preferable to use the primary alkyl ZnDTP alone.
When a primary alkyl ZnDTP and a secondary zinc dialkyl dithiophosphate having a secondary alkyl group (secondary alkyl ZnDTP) are used in combination, the content ratio of the primary alkyl ZnDTP and the secondary alkyl ZnDTP [ (Primary alkyl ZnDTP) / (secondary alkyl ZnDTP)] is preferably 50/50 to 99/1, more preferably 60/40 to 95/5, and even more preferably 70/30 to mass ratio. It is 90/10.

本発明の一態様の潤滑油組成物において、ＺｎＤＴＰ（Ｂ）由来の亜鉛原子の含有量は、本発明の効果をより発揮させやすくする観点から、潤滑油組成物の全量基準で、好ましくは１００質量ｐｐｍ〜２，０００質量ｐｐｍ、より好ましくは１１０質量ｐｐｍ〜１，９００質量ｐｐｍ、更に好ましくは１２０質量ｐｐｍ〜１，８００質量ｐｐｍである。 In the lubricating oil composition of one aspect of the present invention, the content of zinc atoms derived from ZnDTP (B) is preferably 100 based on the total amount of the lubricating oil composition from the viewpoint of facilitating the effect of the present invention. It is mass ppm to 2,000 mass ppm, more preferably 110 mass ppm to 1,900 mass ppm, still more preferably 120 mass ppm to 1,800 mass ppm.

また、本発明の一態様の潤滑油組成物において、ＺｎＤＴＰ（Ｂ）の含有量は、ＺｎＤＴＰ（Ｂ）由来の亜鉛原子の含有量が、上記範囲を充足するように調整すればよい。ＺｎＤＴＰ（Ｂ）の含有量は、潤滑油組成物の全量基準で、好ましくは０．１１質量％〜２．３質量％、より好ましくは０．１３質量％〜２．２質量％、更に好ましくは０．１４質量％〜２．１質量％である。 Further, in the lubricating oil composition of one aspect of the present invention, the content of ZnDTP (B) may be adjusted so that the content of zinc atoms derived from ZnDTP (B) satisfies the above range. The content of ZnDTP (B) is preferably 0.11% by mass to 2.3% by mass, more preferably 0.13% by mass to 2.2% by mass, still more preferably 0.11% by mass to 2.3% by mass, based on the total amount of the lubricating oil composition. It is 0.14% by mass to 2.1% by mass.

＜ナトリウム系清浄剤（Ｃ）＞
本発明の潤滑油組成物は、ナトリウム系清浄剤（Ｃ）を含有する。
潤滑油組成物がナトリウム系清浄剤（Ｃ）を含有することで、清浄性等が潤滑油組成物に付与される。
潤滑油組成物がナトリウム系清浄剤（Ｃ）を含有しない場合、ＺｎＤＴＰ（Ｂ）とナトリウム系清浄剤（Ｃ）との組み合わせることによる本発明の効果が発揮されない。 <Sodium-based cleaning agent (C)>
The lubricating oil composition of the present invention contains a sodium-based cleaning agent (C).
When the lubricating oil composition contains the sodium-based cleaning agent (C), cleanliness and the like are imparted to the lubricating oil composition.
When the lubricating oil composition does not contain the sodium-based cleaning agent (C), the effect of the present invention by combining ZnDTP (B) and the sodium-based cleaning agent (C) cannot be exhibited.

ナトリウム系清浄剤（Ｃ）としては、例えば、ナトリウムスルホネート、ナトリウムフェネート、及びナトリウムサリチレート等のナトリウム塩が挙げられる。
これらの中でも、本発明の効果をより発揮させやすくする観点から、ナトリウムスルホネートが好ましい。 Examples of the sodium-based cleaning agent (C) include sodium salts such as sodium sulfonate, sodium phenate, and sodium salicylate.
Among these, sodium sulfonate is preferable from the viewpoint of making it easier to exert the effect of the present invention.

ナトリウムスルホネートとしては、下記一般式（ｃ１）で表される化合物が好ましい。
ナトリウムフェネートとしては、下記一般式（ｃ２）で表される化合物が好ましい。
ナトリウムサリチレートとしては、下記一般式（ｃ３）で表される化合物が好ましい。
ナトリウム系清浄剤（Ｃ）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 sodium sulfonate, a compound represented by the following general formula (c1) is preferable.
As the sodium phenate, a compound represented by the following general formula (c2) is preferable.
As the sodium salicylate, a compound represented by the following general formula (c3) is preferable.
As the sodium-based cleaning agent (C), one type may be used alone, or two or more types may be used in combination.

Figure 2021161291
Figure 2021161291

なお、上記一般式（ｃ１）〜（ｃ３）中、Ｒは、水素原子又は炭素数１〜１８の炭化水素基である。また、上記一般式（ｃ２）中、ｑは、０以上の整数であり、好ましくは０〜３の整数である。
Ｒとして選択し得る炭化水素基としては、例えば、炭素数１〜１８のアルキル基、炭素数１〜１８のアルケニル基、環形成炭素数３〜１８のシクロアルキル基、環形成炭素数６〜１８のアリール基、炭素数７〜１８のアルキルアリール基、炭素数７〜１８のアリールアルキル基等が挙げられる。 In the general formulas (c1) to (c3), R is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. Further, in the above general formula (c2), q is an integer of 0 or more, preferably an integer of 0 to 3.
Examples of the hydrocarbon group that can be selected as R include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 ring-forming carbon atoms, and 6 to 18 ring-forming carbon atoms. Examples thereof include an aryl group of 7 to 18, an alkylaryl group having 7 to 18 carbon atoms, and an arylalkyl group having 7 to 18 carbon atoms.

ナトリウム系清浄剤（Ｃ）は、中性、塩基性、又は過塩基性のいずれであってもよいが、潤滑油組成物の塩基価維持性をより向上させやすくする観点から、塩基性又は過塩基性のものが好ましく、過塩基性のものがより好ましい。
なお、本明細書において、塩基性又は過塩基性金属系清浄剤とは、金属と酸性有機化合物とを反応させてなり、該金属と該酸性有機化合物との中和に必要な化学量論量よりも過剰の金属を含有するものを意味する。すなわち、金属と酸性有機化合物との中和に必要な化学量論量に従って反応させて得られる金属塩（中性塩）中の金属の化学当量に対する、金属系清浄剤中の金属の総化学当量を「金属比」としたときに、塩基性又は過塩基性金属系清浄剤の金属比は１より大きくなる。本実施形態に用いられる塩基性又は過塩基性金属系清浄剤の金属比は、好ましくは１．３超、より好ましくは５〜３０、更に好ましくは７〜２２である。
なお、本明細書において、ＪＩＳ Ｋ ２５０１：２００３に準拠して、過塩素酸法により測定される塩基価が５０ｍｇＫＯＨ／ｇ未満のものを「中性」、５０ｍｇＫＯＨ／ｇ以上１５０ｍｇＫＯＨ／ｇ未満のものを「塩基性」、１５０ｍｇＫＯＨ／ｇ以上のものを「過塩基性」と定義する。 The sodium-based cleaning agent (C) may be neutral, basic, or hyperbasic, but is basic or excessive from the viewpoint of facilitating the improvement of the basic value sustainability of the lubricating oil composition. Basic ones are preferable, and hyperbasic ones are more preferable.
In the present specification, the basic or hyperbasic metal-based cleaning agent is a stoichiometric amount required for neutralizing the metal and the acidic organic compound by reacting the metal with the acidic organic compound. Means one containing an excess of metal. That is, the total chemical equivalent of the metal in the metal-based cleaning agent to the chemical equivalent of the metal in the metal salt (neutral salt) obtained by reacting the metal according to the stoichiometric amount required for neutralization of the acidic organic compound. When is "metal ratio", the metal ratio of the basic or hyperbasic metal-based cleaning agent is larger than 1. The metal ratio of the basic or hyperbasic metal-based cleaning agent used in the present embodiment is preferably more than 1.3, more preferably 5 to 30, and even more preferably 7 to 22.
In the present specification, those having a base value of less than 50 mgKOH / g measured by the perchloric acid method are "neutral", and those having a base value of 50 mgKOH / g or more and less than 150 mgKOH / g, in accordance with JIS K 2501: 2003. Is defined as "basic", and those of 150 mgKOH / g or more are defined as "hyperbasic".

ナトリウム系清浄剤（Ｃ）の塩基価は、好ましくは５ｍｇＫＯＨ／ｇ以上、より好ましくは１００ｍｇＫＯＨ／ｇ以上、更に好ましくは２００ｍｇＫＯＨ／ｇ以上、より更に好ましくは３００ｍｇＫＯＨ／ｇ以上、更になお好ましくは３５０ｍｇＫＯＨ／ｇ以上、一層好ましくは４００ｍｇＫＯＨ／ｇ以上であり、そして、好ましくは６００ｍｇＫＯＨ／ｇ以下、より好ましくは５５０ｍｇＫＯＨ／ｇ以下、更に好ましくは５００ｍｇＫＯＨ／ｇ以下である。 The base value of the sodium-based cleaning agent (C) is preferably 5 mgKOH / g or more, more preferably 100 mgKOH / g or more, still more preferably 200 mgKOH / g or more, still more preferably 300 mgKOH / g or more, still more preferably 350 mgKOH / g. It is g or more, more preferably 400 mgKOH / g or more, and preferably 600 mgKOH / g or less, more preferably 550 mgKOH / g or less, still more preferably 500 mgKOH / g or less.

本発明の一態様の潤滑油組成物において、ナトリウム系清浄剤（Ｃ）に由来するナトリウム原子の含有量は、本発明の効果をより発揮させやすくする観点から、潤滑油組成物の全量基準で、好ましくは５質量ｐｐｍ〜１，０００質量ｐｐｍ、より好ましくは１０質量ｐｐｍ〜９８０質量ｐｐｍ、更に好ましくは１５質量ｐｐｍ〜９７０質量ｐｐｍである。 In the lubricating oil composition of one aspect of the present invention, the content of the sodium atom derived from the sodium-based cleaning agent (C) is based on the total amount of the lubricating oil composition from the viewpoint of facilitating the effect of the present invention. It is preferably 5 mass ppm to 1,000 mass ppm, more preferably 10 mass ppm to 980 mass ppm, and further preferably 15 mass ppm to 970 mass ppm.

本発明の一態様の潤滑油組成物において、ナトリウム系清浄剤（Ｃ）の含有量は、ナトリウム系清浄剤（Ｃ）由来のナトリウム原子の含有量が、上記範囲を充足するように調整すればよい。ナトリウム系清浄剤（Ｃ）の含有量は、潤滑油組成物の全量基準で、好ましくは０．０１質量％〜０．５３質量％、より好ましく０．０１質量％〜０．５２質量％、更に好ましくは０．０１質量％〜０．５１質量％である。 In the lubricating oil composition of one aspect of the present invention, the content of the sodium-based cleaning agent (C) is adjusted so that the content of sodium atoms derived from the sodium-based cleaning agent (C) satisfies the above range. good. The content of the sodium-based cleaning agent (C) is preferably 0.01% by mass to 0.53% by mass, more preferably 0.01% by mass to 0.52% by mass, and further, based on the total amount of the lubricating oil composition. It is preferably 0.01% by mass to 0.51% by mass.

＜その他添加剤＞
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、成分（Ｂ）及び成分（Ｃ）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、酸化防止剤、粘度指数向上剤、流動点降下剤、防錆剤、金属不活性化剤、消泡剤、極圧剤、耐摩耗剤、油性剤、及びナトリウム系清浄剤（Ｃ）以外の金属系清浄剤（Ｃ’）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。
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、ハンドリング性や基油（Ａ）への溶解性を考慮し、上述の基油（Ａ）の一部に希釈し溶解させた溶液の形態であってもよい。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上述の含有量は、希釈油を除いた有効成分換算（樹脂分換算）での含有量を意味する。 <Other additives>
The lubricating oil composition of one aspect of the present invention may contain additives for lubricating oil other than the component (B) and the component (C) as long as the effects of the present invention are not impaired.
Examples of the lubricant additive include antioxidants, viscosity index improvers, pour point lowering agents, rust preventives, metal deactivators, defoaming agents, extreme pressure agents, abrasion resistant agents, and oil-based agents. And a metal-based cleaning agent (C') other than the sodium-based cleaning agent (C).
These lubricant additives may be used alone or in combination of two or more.
In this specification, additives such as a viscosity index improver and an antifoaming agent are diluted with a part of the above-mentioned base oil (A) in consideration of handleability and solubility in the base oil (A). It may be in the form of a dissolved solution. In such a case, in the present specification, the above-mentioned content of additives such as antifoaming agent and viscosity index improver means the content in terms of active ingredient (converted to resin content) excluding diluted oil. ..

（酸化防止剤）
酸化防止剤としては、例えば、アミン系酸化防止剤及びフェノール系酸化防止剤等が挙げられる。これらは、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。 (Antioxidant)
Examples of the antioxidant include amine-based antioxidants and phenol-based antioxidants. These may be used individually by 1 type, and may be used in combination of 2 or more type.

アミン系酸化防止剤としては、例えば、モノオクチルジフェニルアミン、モノノニルジフェニルアミン等のモノアルキルジフェニルアミン系化合物；４，４’−ジブチルジフェニルアミン、４，４’−ジペンチルジフェニルアミン、４，４’−ジヘキシルジフェニルアミン、４，４’−ジヘプチルジフェニルアミン、４，４’−ジオクチルジフェニルアミン、４，４’−ジノニルジフェニルアミン、モノブチルフェニルモノオクチルフェニルアミン等のジアルキルジフェニルアミン系化合物；テトラブチルジフェニルアミン、テトラヘキシルジフェニルアミン、テトラオクチルジフェニルアミン、テトラノニルジフェニルアミンなどのポリアルキルジフェニルアミン系化合物；α−ナフチルアミン、フェニル−α−ナフチルアミン、ブチルフェニル−α−ナフチルアミン、ペンチルフェニル−α−ナフチルアミン、ヘキシルフェニル−α−ナフチルアミン、ヘプチルフェニル−α−ナフチルアミン、オクチルフェニル−α−ナフチルアミン、ノニルフェニル−α−ナフチルアミンなどのナフチルアミン系化合物等が挙げられる。 Examples of the amine-based antioxidant include monoalkyldiphenylamine-based compounds such as monooctyldiphenylamine and monononyldiphenylamine; 4,4'-dibutyldiphenylamine, 4,4'-dipentyldiphenylamine, 4,4'-dihexyldiphenylamine, 4 , 4'-Diheptyldiphenylamine, 4,4'-dioctyldiphenylamine, 4,4'-dinonyldiphenylamine, monobutylphenylmonooctylphenylamine and other dialkyldiphenylamine compounds; tetrabutyldiphenylamine, tetrahexyldiphenylamine, tetraoctyldiphenylamine , Polyalkyldiphenylamine compounds such as tetranonyldiphenylamine; α-naphthylamine, phenyl-α-naphthylamine, butylphenyl-α-naphthylamine, pentylphenyl-α-naphthylamine, hexylphenyl-α-naphthylamine, heptylphenyl-α-naphthylamine, Examples thereof include naphthylamine-based compounds such as octylphenyl-α-naphthylamine and nonylphenyl-α-naphthylamine.

フェノール系酸化防止剤としては、例えば、２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノール、２，６−ジ−ｔｅｒｔ−ブチル−４−エチルフェノール、オクタデシル３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート等のモノフェノール系化合物；４，４’−メチレンビス（２，６−ジ−ｔｅｒｔ−ブチルフェノール）、２，２’−メチレンビス（４−エチル−６−ｔｅｒｔ−ブチルフェノール）等のジフェノール系化合物が挙げられる。 Examples of the phenolic antioxidant include 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, and octadecyl 3- (3,5-di-). Monophenolic compounds such as tert-butyl-4-hydroxyphenyl) propionate; 4,4'-methylenebis (2,6-di-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert- Examples thereof include diphenol compounds such as butylphenol).

本発明の一態様の潤滑油組成物が酸化防止剤を含有する場合、酸化防止剤の含有量は、酸化安定性を保つのに必要な最低量を加えれば良く、潤滑油組成物の全量基準で、好ましくは０．０１質量％〜１．５質量％、より好ましくは０．１質量％〜１質量％である。 When the lubricating oil composition of one aspect of the present invention contains an antioxidant, the content of the antioxidant may be the minimum amount necessary for maintaining oxidative stability, and is based on the total amount of the lubricating oil composition. It is preferably 0.01% by mass to 1.5% by mass, and more preferably 0.1% by mass to 1% by mass.

（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。これらは、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。 (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. These may be used individually by 1 type, and may be used in combination of 2 or more type.
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.

（流動点降下剤）
流動点降下剤としては、例えば、質量平均分子量が５万〜１５万程度のポリメタクリレート等が挙げられる。これらは、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。 (Pour point depressant)
Examples of the pour point lowering agent include polymethacrylate having a mass average molecular weight of about 50,000 to 150,000. These may be used individually by 1 type, and may be used in combination of 2 or more type.
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.

（防錆剤）
防錆剤としては、例えば、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、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。これらは、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 alkylbenzene sulphonate, dinonylnaphthalen sulphonate, organic phosphite ester, organic phosphoric acid ester, alkenyl succinate ester, alkenyl succinic acid polyhydric alcohol ester and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.
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。これらは、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. These may be used individually by 1 type, and may be used in combination of 2 or more type.
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。これらは、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. These may be used individually by 1 type, and may be used in combination of 2 or more type.
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.

（極圧剤又は耐摩耗剤）
本発明の一態様の潤滑油組成物は、極圧剤及び耐摩耗剤からなる群から選択される１種以上を含んでいてもよいが、本発明の効果を発揮させやすくする観点から、極圧剤及び耐摩耗剤からなる群から選択される１種以上の含有量は少ないことが好ましい。
極圧剤、耐摩耗剤としては、成分（Ｂ）には該当しない、有機金属系化合物、硫黄系化合物、リン系化合物、及び硫黄−リン系化合物が挙げられる。 (Extreme pressure agent or wear resistant agent)
The lubricating oil composition of one aspect of the present invention may contain one or more selected from the group consisting of extreme pressure agents and abrasion resistant agents, but from the viewpoint of facilitating the effect of the present invention, it is extremely It is preferable that the content of one or more selected from the group consisting of a pressure agent and an abrasion resistant agent is small.
Examples of the extreme pressure agent and the abrasion resistant agent include organic metal compounds, sulfur compounds, phosphorus compounds, and sulfur-phosphorus compounds, which do not correspond to the component (B).

有機金属系化合物としては、例えば、ジアルキルジチオカルバミン酸モリブデン（ＭｏＤＴＣ）及びジアルキルジチオリン酸モリブデン（ＭｏＤＴＰ）等の有機モリブデン系化合物、並びにジアルキルジチオカルバミン酸亜鉛（ＺｎＤＴＣ）等の成分（Ｂ）以外の有機亜鉛系化合物が挙げられる。 Examples of the organic metal compound include organic molybdenum compounds such as molybdenum dialkyldithiocarbamate (MoDTC) and molybdenum dialkyldithiophosphate (MoDTP), and zinc organic compounds other than the component (B) such as zinc dialkyldithiocarbamate (ZnDTC). Examples include compounds.

硫黄系化合物としては、例えば、硫化油脂、硫化脂肪酸、硫化エステル、硫化オレフィン、モノサルファイド、ポリサルファイド、ジヒドロカルビルサルファイド、チアジアゾール化合物、アルキルチオカルバモイル化合物、チオカーバメート化合物、チオテルペン化合物、及びジアルキルチオジプロピオネート化合物が挙げられる。 Examples of sulfur-based compounds include sulfide fats and oils, sulfide fatty acids, sulfide esters, sulfide olefins, monosulfides, polysulfides, dihydrocarbyl sulfides, thiadiazole compounds, alkylthiocarbamoyl compounds, thiocarbamate compounds, thioterpene compounds, and dialkylthiodipropionate compounds. Can be mentioned.

リン系化合物としては、例えば、アリールホスフェート、アルキルホスフェート、アルケニルホスフェート、アルキルアリールホスフェート等のリン酸エステル；アリールハイドロゲンホスファイト、アルキルハイドロゲンホスファイト、アリールホスファイト、アルキルホスファイト、アルケニルホスファイト、アリールアルキルホスファイト等の亜リン酸エステル；及びこれらのアミン塩が挙げられる。 Examples of phosphorus-based compounds include phosphate esters such as aryl phosphate, alkyl phosphate, alkenyl phosphate, and alkyl aryl phosphate; aryl hydrogen phosphite, alkyl hydrogen phosphite, aryl phosphite, alkyl phosphite, alkenyl phosphite, and aryl alkyl. Phosphite esters such as phosphite; and amine salts thereof.

硫黄−リン系化合物としては、例えば、モノアルキルチオホスフェート、ジアルキルジチオホスフェート、トリアルキルトリチオホスフェート、及びこれらのアミン塩が挙げられる。 Examples of the sulfur-phosphorus compound include monoalkylthiophosphate, dialkyldithiophosphate, trialkyltrithiophosphate, and amine salts thereof.

本発明の一態様の潤滑油組成物において、極圧剤及び耐摩耗剤からなる群から選択される１種以上の含有量は、潤滑油組成物の全量基準で、通常０．０５〜１０質量％程度であり、好ましくは、０．１〜５質量％である。
但し、酸化安定性の確保、スラッジ生成の抑制、及び色相悪化の抑制等の観点から、リン系化合物の中でも、モノアリールアシッドホスフェート、ジアリールアシッドホスフェート、モノアルキルアシッドホスフェート、ジアルキルアシッドホスフェート、モノアルケニルアシッドホスフェート、ジアルケニルアシッドホスフェート等の酸性リン酸エステル；モノアルキルアシッドホスファイト、ジアルキルアシッドホスファイト、モノアルケニルアシッドホスファイト、ジアルケニルアシッドホスファイト等の酸性亜リン酸エステル；及びこれらのアミン塩の含有量は、少ないことが好ましい。具体的には、潤滑油組成物の全量基準で、好ましくは０．０１質量％未満、より好ましくは０．００１質量％未満、更に好ましくはこれらのリン系化合物を含まないことである。 In the lubricating oil composition of one aspect of the present invention, the content of one or more selected from the group consisting of extreme pressure agents and abrasion resistant agents is usually 0.05 to 10% by mass based on the total amount of the lubricating oil composition. It is about%, preferably 0.1 to 5% by mass.
However, from the viewpoint of ensuring oxidative stability, suppressing sludge formation, suppressing deterioration of hue, etc., among phosphorus-based compounds, monoaryl acid phosphate, diaryl acid phosphate, monoalkyl acid phosphate, dialkyl acid phosphate, monoalkenyl acid Acidic phosphates such as phosphate and dialkenyl acid phosphate; acidic phosphites such as monoalkyl acid phosphite, dialkyl acid phosphite, monoalkenyl acid phosphite, dialkenyl acid phosphite; and inclusion of amine salts thereof. The amount is preferably small. Specifically, based on the total amount of the lubricating oil composition, it is preferably less than 0.01% by mass, more preferably less than 0.001% by mass, and further preferably not containing these phosphorus compounds.

（油性剤）
油性剤としては、脂肪族アルコール；脂肪酸及び脂肪酸金属塩等の脂肪酸化合物；ポリオールエステル、ソルビタンエステル、及びグリセライド等のエステル化合物；脂肪族アミン等のアミン化合物等を挙げることができる。
油性剤の含有量は、添加効果の点から、潤滑油組成物の全量基準で、通常０．１〜１０質量％であり、好ましくは０．５〜５質量％である。 (Oil agent)
Examples of the oily agent include aliphatic alcohols; fatty acid compounds such as fatty acids and fatty acid metal salts; ester compounds such as polyol esters, sorbitan esters, and glycerides; amine compounds such as aliphatic amines.
The content of the oily agent is usually 0.1 to 10% by mass, preferably 0.5 to 5% by mass, based on the total amount of the lubricating oil composition from the viewpoint of the addition effect.

（ナトリウム系清浄剤（Ｃ）以外の金属系清浄剤（Ｃ’））
本発明の一態様の潤滑油組成物は、ナトリウム系清浄剤（Ｃ）以外の金属系清浄剤（Ｃ’）を含んでいてもよいが、本発明の効果を発揮させやすくする観点から、ナトリウム系清浄剤（Ｃ）以外の金属系清浄剤（Ｃ’）の含有量は少ないことが好ましい。
ナトリウム系清浄剤（Ｃ）以外の金属系清浄剤（Ｃ’）としては、例えば、マグネシウム系清浄剤及びカルシウム系清浄剤が挙げられる。 (Metal-based cleaning agents (C') other than sodium-based cleaning agents (C))
The lubricating oil composition of one aspect of the present invention may contain a metal-based cleaning agent (C') other than the sodium-based cleaning agent (C), but from the viewpoint of facilitating the effect of the present invention, sodium is used. It is preferable that the content of the metal-based cleaning agent (C') other than the system-based cleaning agent (C) is small.
Examples of the metal-based cleaning agent (C') other than the sodium-based cleaning agent (C) include magnesium-based cleaning agents and calcium-based cleaning agents.

マグネシウム系清浄剤としては、マグネシウムスルホネート、マグネシウムフェネート、マグネシウムサリチレート等のマグネシウム塩が挙げられる。また、マグネシウム系清浄剤は、中性、塩基性、又は過塩基性のいずれであってもよい。
カルシウム系清浄剤としては、カルシウムスルホネート、カルシウムフェネート、カルシウムサリチレート等のカルシウム塩が挙げられる。また、カルシウム系清浄剤は、中性、塩基性、又は過塩基性のいずれであってもよい。 Examples of the magnesium-based cleaning agent include magnesium salts such as magnesium sulfonate, magnesium phenate, and magnesium salicylate. Further, the magnesium-based cleaning agent may be either neutral, basic, or hyperbasic.
Examples of the calcium-based cleaning agent include calcium salts such as calcium sulfonate, calcium phenate, and calcium salicylate. In addition, the calcium-based cleaning agent may be either neutral, basic, or hyperbasic.

本発明の一態様の潤滑油組成物は、ナトリウム系清浄剤（Ｃ）以外の金属系清浄剤（Ｃ’）に由来する金属原子の含有量が少ないことが好ましく、潤滑油組成物の全量基準で、好ましくは３０質量ｐｐｍ未満、より好ましくは２０質量ｐｐｍ未満、更に好ましくは１０質量ｐｐｍ未満、より更に好ましくは１質量ｐｐｍ未満、更になお好ましくはマグネシウム系清浄剤に由来するマグネシウム原子を含まないことである。
また、本発明の一態様の潤滑油組成物は、マグネシウム系清浄剤に由来するマグネシウム原子の含有量が少ないことが好ましく、潤滑油組成物の全量基準で、好ましくは３０質量ｐｐｍ未満、より好ましくは２０質量ｐｐｍ未満、更に好ましくは１０質量ｐｐｍ未満、より更に好ましくは１質量ｐｐｍ未満、更になお好ましくはマグネシウム系清浄剤に由来するマグネシウム原子を含まないことである。
さらに、本発明の一態様の潤滑油組成物は、カルシウム系清浄剤に由来するカルシウム原子の含有量が少ないことが好ましく、潤滑油組成物の全量基準で、好ましくは３０質量ｐｐｍ未満、より好ましくは２０質量ｐｐｍ未満、更に好ましくは１０質量ｐｐｍ未満、より更に好ましくは１質量ｐｐｍ未満、更になお好ましくはカルシウム系清浄剤に由来するカルシウム原子を含まないことである。 The lubricating oil composition of one aspect of the present invention preferably has a low content of metal atoms derived from a metal-based cleaning agent (C') other than the sodium-based cleaning agent (C), and is based on the total amount of the lubricating oil composition. It is preferably less than 30 mass ppm, more preferably less than 20 mass ppm, further preferably less than 10 mass ppm, even more preferably less than 1 mass ppm, and even more preferably free of magnesium atoms derived from magnesium-based cleaning agents. That is.
Further, the lubricating oil composition according to one aspect of the present invention preferably has a low content of magnesium atoms derived from a magnesium-based cleaning agent, and is preferably less than 30 mass ppm based on the total amount of the lubricating oil composition. Is less than 20 mass ppm, more preferably less than 10 mass ppm, even more preferably less than 1 mass ppm, and even more preferably free of magnesium atoms derived from magnesium-based cleaning agents.
Further, the lubricating oil composition of one aspect of the present invention preferably has a low content of calcium atoms derived from a calcium-based cleaning agent, and is preferably less than 30 parts by mass, more preferably based on the total amount of the lubricating oil composition. Is less than 20 mass ppm, more preferably less than 10 mass ppm, even more preferably less than 1 mass ppm, and even more preferably free of calcium atoms derived from calcium-based cleaning agents.

［潤滑油組成物の物性］
＜４０℃動粘度、粘度指数＞
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９．００ｍｍ２／ｓ〜１６５ｍｍ２／ｓ、より好ましくは２０．０ｍｍ２／ｓ〜１２０ｍｍ２／ｓ、更に好ましくは２５．０ｍｍ２／ｓ〜１００ｍｍ２／ｓである。
潤滑油組成物の４０℃動粘度が９．００ｍｍ２／ｓ以上であると、引火点が高く、潤滑性能に優れる潤滑油組成物としやすい。また、基油（Ａ）の４０℃動粘度が１６５ｍｍ２／ｓ以下であると、低温時の粘性抵抗がそれほど大きくなることもなく、機械の作動を良好なものとしやすい。
また、本発明の一態様の潤滑油組成物の粘度指数は、好ましくは８０以上、より好ましくは９０以上、更に好ましくは１００以上である。
４０℃動粘度及び粘度指数は、ＪＩＳ Ｋ ２２８３：２０００に準拠して測定又は算出される値を意味する。 [Physical characteristics of lubricating oil composition]
<40 ° C kinematic viscosity, viscosity index>
40 ° C. The kinematic viscosity of one embodiment of the lubricating oil composition of the present invention is preferably 9.00mm 2 / s~165mm 2 / s, more preferably 20.0mm 2 / s~120mm 2 / s, more preferably 25 .0mm is a 2 / s~100mm 2 / s.
When the 40 ° C. kinematic viscosity of the lubricating oil composition is 9.00 mm 2 / s or more, it is easy to obtain a lubricating oil composition having a high flash point and excellent lubricating performance. Further, when the 40 ° C. kinematic viscosity of the base oil (A) is 165 mm 2 / s or less, the viscous resistance at low temperature does not increase so much, and it is easy to improve the operation of the machine.
The viscosity index of the lubricating oil composition according to one aspect of the present invention is preferably 80 or more, more preferably 90 or more, still more preferably 100 or more.
40 ° C. kinematic viscosity and viscosity index mean values measured or calculated in accordance with JIS K 2283: 2000.

＜亜鉛原子含有量＞
本発明の潤滑油組成物は、亜鉛原子含有量が、潤滑油組成物の全量基準で、１００質量ｐｐｍ〜２，０００質量ｐｐｍである。
亜鉛原子含有量が１００質量ｐｐｍ未満であると、酸化防止能及び摩耗防止能に劣ると共に、本発明の効果が発揮され難くなる。また、亜鉛原子含有量が２，０００質量ｐｐｍ超である場合も、本発明の効果が発揮され難くなる。
ここで、本発明の効果をより発揮させやすくする観点、さらには、酸化防止能及び摩耗防止能に優れる潤滑油組成物を調製する観点から、本発明の一態様の潤滑油組成物の亜鉛原子含有量は、潤滑油組成物の全量基準で、好ましくは１１０質量ｐｐｍ〜１，９００質量ｐｐｍ、より好ましくは１２０質量ｐｐｍ〜１，８００質量ｐｐｍである。
なお、本明細書において、潤滑油組成物の亜鉛原子含有量は、ＡＳＴＭ Ｄ４９５１に準拠して測定される値を意味する。 <Zinc atom content>
The lubricating oil composition of the present invention has a zinc atom content of 100 mass ppm to 2,000 mass ppm based on the total amount of the lubricating oil composition.
If the zinc atom content is less than 100 mass ppm, the antioxidant ability and the abrasion preventive ability are inferior, and the effect of the present invention is difficult to be exhibited. Further, when the zinc atom content is more than 2,000 mass ppm, the effect of the present invention is less likely to be exhibited.
Here, from the viewpoint of making it easier to exert the effect of the present invention, and further, from the viewpoint of preparing a lubricating oil composition having excellent antioxidant ability and anti-wear ability, the zinc atom of the lubricating oil composition of one aspect of the present invention. The content is preferably 110 mass ppm to 1,900 mass ppm, more preferably 120 mass ppm to 1,800 mass ppm based on the total amount of the lubricating oil composition.
In this specification, the zinc atom content of the lubricating oil composition means a value measured according to ASTM D4951.

＜ナトリウム原子含有量＞
本発明の潤滑油組成物は、ナトリウム原子含有量が、潤滑油組成物の全量基準で、５質量ｐｐｍ〜１，０００質量ｐｐｍである。
ナトリウム原子含有量が５質量ｐｐｍ未満であると、清浄性に劣る潤滑油組成物になると共に、本発明の効果が発揮され難くなる。また、ナトリウム原子含有量が１，０００質量ｐｐｍ超である場合も、本発明の効果が発揮され難くなる。
ここで、本発明の効果をより発揮させやすくする観点、さらには、清浄性に優れる潤滑油組成物を調製する観点から、本発明の一態様の潤滑油組成物のナトリウム原子含有量は、潤滑油組成物の全量基準で、好ましくは１０質量ｐｐｍ〜９８０質量ｐｐｍ、より好ましくは１５質量ｐｐｍ〜９７０質量ｐｐｍである。
なお、本明細書において、潤滑油組成物のナトリウム原子含有量は、ＡＳＴＭ Ｄ４９５１に準拠して測定される値を意味する。 <Sodium atom content>
The lubricating oil composition of the present invention has a sodium atom content of 5 mass ppm to 1,000 mass ppm based on the total amount of the lubricating oil composition.
If the sodium atom content is less than 5 mass ppm, the lubricating oil composition is inferior in cleanliness, and the effect of the present invention is difficult to be exhibited. Further, when the sodium atom content is more than 1,000 mass ppm, the effect of the present invention is less likely to be exhibited.
Here, from the viewpoint of making it easier to exert the effect of the present invention, and further, from the viewpoint of preparing a lubricating oil composition having excellent cleanliness, the sodium atom content of the lubricating oil composition of one aspect of the present invention is lubricated. Based on the total amount of the oil composition, it is preferably 10 mass ppm to 980 mass ppm, more preferably 15 mass ppm to 970 mass ppm.
In this specification, the sodium atom content of the lubricating oil composition means a value measured according to ASTM D4951.

＜亜鉛原子含有量とナトリウム原子含有量との含有比率＞
本発明の一態様の潤滑油組成物において、亜鉛原子含有量とナトリウム原子含有量との含有比率［（Ｚｎ）／（Ｎａ）］は、本発明の効果をより発揮させやすくする観点から、質量比で、好ましくは０．０５０〜５０、より好ましくは０．０８０〜３０、更に好ましくは０．１０〜２０である。 <Content ratio of zinc atom content and sodium atom content>
In the lubricating oil composition of one aspect of the present invention, the content ratio [(Zn) / (Na)] of the zinc atom content and the sodium atom content is a mass from the viewpoint of making it easier to exert the effect of the present invention. The ratio is preferably 0.050 to 50, more preferably 0.080 to 30, and even more preferably 0.10 to 20.

＜マグネシウム原子含有量＞
本発明の一態様の潤滑油組成物において、マグネシウム原子含有量は、本発明の効果をより発揮させやすくする観点から、潤滑油組成物の全量基準で、好ましくは３０質量ｐｐｍ未満、より好ましくは２０質量ｐｐｍ未満、更に好ましくは１０質量ｐｐｍ未満、より更に好ましくは１質量ｐｐｍ未満、更になお好ましくはマグネシウム原子を含まないことである。
なお、本明細書において、潤滑油組成物のマグネシウム原子含有量は、ＡＳＴＭ Ｄ４９５１に準拠して測定される値を意味する。 <Magnesium atom content>
In the lubricating oil composition of one aspect of the present invention, the magnesium atom content is preferably less than 30 mass ppm, more preferably less than 30 mass ppm, based on the total amount of the lubricating oil composition, from the viewpoint of facilitating the effect of the present invention. It is less than 20 mass ppm, more preferably less than 10 mass ppm, even more preferably less than 1 mass ppm, and even more preferably free of magnesium atoms.
In this specification, the magnesium atom content of the lubricating oil composition means a value measured according to ASTM D4951.

＜カルシウム原子含有量＞
本発明の一態様の潤滑油組成物において、カルシウム原子含有量は、本発明の効果をより発揮させやすくする観点から、潤滑油組成物の全量基準で、好ましくは３０質量ｐｐｍ未満、より好ましくは２０質量ｐｐｍ未満、更に好ましくは１０質量ｐｐｍ未満、より更に好ましくは１質量ｐｐｍ未満、更になお好ましくはカルシウム原子を含まないことである。
なお、本明細書において、潤滑油組成物のカルシウム原子含有量は、ＡＳＴＭ Ｄ４９５１に準拠して測定される値を意味する。 <Calcium atom content>
In the lubricating oil composition of one aspect of the present invention, the calcium atom content is preferably less than 30 mass ppm, more preferably less than 30 mass ppm, based on the total amount of the lubricating oil composition, from the viewpoint of facilitating the effect of the present invention. It is less than 20 mass ppm, more preferably less than 10 mass ppm, even more preferably less than 1 mass ppm, and even more preferably free of calcium atoms.
In this specification, the calcium atom content of the lubricating oil composition means a value measured according to ASTM D4951.

＜ＩＳＯＴ試験後のＡＳＴＭ色＞
本発明の一態様の潤滑油組成物において、触媒として銅片と鉄片を入れ、ＪＩＳ Ｋ ２５１４−１：２０１３に準拠するＩＳＯＴ試験を、１５０℃で１６８時間行った後のＡＳＴＭ色は、好ましくは１．０以下、より好ましくは０．５以下である。 <ASTM color after ISOT test>
In the lubricating oil composition of one aspect of the present invention, the ASTM color after adding a copper piece and an iron piece as a catalyst and performing an ISOT test according to JIS K 2514-1: 2013 at 150 ° C. for 168 hours is preferable. It is 1.0 or less, more preferably 0.5 or less.

［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、基油（Ａ）と、ＺｎＤＴＰ（Ｂ）と、ナトリウム系清浄剤（Ｃ）とを混合する工程を含む、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、成分（Ｂ）と成分（Ｃ）とを配合する工程を有する方法が挙げられる。成分（Ｂ）と成分（Ｃ）とは、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。成分（Ｂ）及び成分（Ｃ）以外の他の成分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, the method for producing a lubricating oil composition according to one aspect of the present invention includes a step of mixing a base oil (A), a ZnDTP (B), and a sodium-based cleaning agent (C). It is a manufacturing method.
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 component (B) and the component (C) with the base oil (A). The component (B) and the component (C) may be blended into the base oil (A) at the same time, or may be blended separately. The same applies to the components other than the component (B) and the component (C). 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］
本発明の潤滑油組成物は、時間の経過に伴う色相の悪化が緩やかであることから、汚染の状況及び沈殿物の発生状況等を目視で確認する手法を採用している機械及び設備等に好適に用いることができる。また、酸化安定性にも優れる。
したがって、例えば、油圧作動油、圧縮機油、ギヤ油、切削油、工作機械油、冷凍機油、タービン油、内燃機油、変速機油等として好適に用いることができ、特に油圧作動油として好適に用いることができる。 [Use of lubricating oil composition]
Since the lubricating oil composition of the present invention gradually deteriorates in hue with the passage of time, it is suitable for machines and equipment that employ a method of visually confirming the state of contamination and the state of generation of precipitates. It can be preferably used. It also has excellent oxidative stability.
Therefore, for example, it can be suitably used as hydraulic hydraulic oil, compressor oil, gear oil, cutting oil, machine tool oil, refrigerating machine oil, turbine oil, internal combustion machine oil, transmission oil, etc., and particularly preferably as hydraulic hydraulic oil. Can be done.

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基油及び潤滑油組成物の物性値の測定は、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
４０℃動粘度及び粘度指数は、ＪＩＳ Ｋ２２８３：２０００に準拠して測定及び算出した。
（２）ナトリウム原子量、亜鉛原子量
潤滑油組成物中のカルシウム原子量、マグネシウム原子量、ナトリウム原子量、及び亜鉛原子量は、ＡＳＴＭ Ｄ４９５１に準拠して測定した。 [Measurement method of various physical property values]
The measurement of the physical characteristic values of the base oil and the lubricating oil composition used in each Example and each Comparative Example was carried out according to the procedure shown below.
(1) Dynamic Viscosity and Viscosity Index The 40 ° C. kinematic viscosity and viscosity index were measured and calculated in accordance with JIS K2283: 2000.
(2) Sodium Atomic Weight, Zinc Atomic Weight The calcium atomic weight, magnesium atomic weight, sodium atomic weight, and zinc atomic weight in the lubricating oil composition were measured according to ASTM D4951.

［実施例１〜１１及び比較例１〜７］
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１〜１１及び比較例１〜７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 11 and Comparative Examples 1 to 7]
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 11 and Comparative Examples 1 to 7 are as shown below.

＜基油（Ａ）＞
ＡＰＩカテゴリーでグループＩＩに属する鉱油（４０℃動粘度＝３０．６ｍｍ２／ｓ、粘度指数＝１０４）を用いた。 <Base oil (A)>
Mineral oil belonging to Group II in the API category (40 ° C. kinematic viscosity = 30.6 mm 2 / s, viscosity index = 104) was used.

＜ジアルキルジチオリン酸亜鉛（Ｂ）＞
上記一般式（ｂ１）中、Ｒ１１〜Ｒ１４が２−エチルヘキシル基（第１級アルキル基）である第１級ジアルキルジチオリン酸亜鉛を用いた。
亜鉛原子の含有量：８．９０質量％、リン原子の含有量：７．４０質量％、硫黄原子の含有量：１５．０質量％
なお、表１では、ジアルキルジチオリン酸亜鉛（Ｂ）を、「ＺｎＤＴＰ」と略記する。 <Zinc dialkyldithiophosphate (B)>
In the general formula (b1), using the first zinc dialkyl dithiophosphate R 11 to R 14 is a 2-ethylhexyl group (primary alkyl group).
Zinc atom content: 8.90% by mass, phosphorus atom content: 7.40% by mass, sulfur atom content: 15.0% by mass
In Table 1, zinc dialkyldithiophosphate (B) is abbreviated as "ZnDTP".

＜ナトリウム系清浄剤（Ｃ）、ナトリウム系清浄剤以外の他の金属系清浄剤（Ｃ’）＞
・Ｎａスルホネート（塩基価：４４８ｍｇＫＯＨ／ｇ、ナトリウム原子含有量：１９．５質量％）
・Ｃａスルホネート（塩基価：３０７ｍｇＫＯＨ／ｇ、カルシウム原子含有量：１１．９質量％）
・Ｍｇスルホネート（塩基価：３０８ｍｇＫＯＨ／ｇ、マグネシウム原子含有量：９．４質量％）
なお、ナトリウム系清浄剤（Ｃ）及びナトリウム系清浄剤以外の他の金属系清浄剤（Ｃ’）の塩基価は、ＪＩＳ Ｋ ２５０１−９：２００３に準拠して、過塩素酸法により測定した。 <Sodium-based cleaning agent (C), metal-based cleaning agent other than sodium-based cleaning agent (C')>
-Na sulfonate (base value: 448 mgKOH / g, sodium atom content: 19.5% by mass)
-Ca sulfonate (base value: 307 mgKOH / g, calcium atom content: 11.9% by mass)
-Mg sulfonate (base value: 308 mgKOH / g, magnesium atom content: 9.4% by mass)
The base values of the sodium-based cleaning agent (C) and the metal-based cleaning agent (C') other than the sodium-based cleaning agent were measured by the perchloric acid method in accordance with JIS K 2501-9: 2003. ..

［評価］
＜ＩＳＯＴ試験＞
試験油（潤滑油組成物）に触媒として銅片と鉄片を入れ、ＪＩＳ Ｋ ２５１４−１：２０１３に準拠するＩＳＯＴ試験を実施して、試験油を強制劣化させた。試験温度は１５０℃とし、ＩＳＯＴ試験開始前、ＩＳＯＴ試験開始から７２時間後、及びＩＳＯＴ試験開始から１６８時間後の試験油について、ＡＳＴＭ色（ＪＩＳ Ｋ ２５８０：２００３）を測定した。
そして、ＡＳＴＭ色が１．０以下（Ｌ１．０）であった試料油を「色相悪化無し」と判断し、１．０よりも大きい試料油（Ｌ１．５、Ｌ２．０等）を「色相悪化有り」と判断した。 [evaluation]
<ISOT test>
A copper piece and an iron piece were added to the test oil (lubricating oil composition) as catalysts, and an ISOT test conforming to JIS K 2514-1: 2013 was carried out to forcibly deteriorate the test oil. The test temperature was 150 ° C., and the ASTM color (JIS K 2580: 2003) was measured for the test oil before the start of the ISOT test, 72 hours after the start of the ISOT test, and 168 hours after the start of the ISOT test.
Then, the sample oil having an ASTM color of 1.0 or less (L1.0) is judged to have "no deterioration in hue", and the sample oil having a color greater than 1.0 (L1.5, L2.0, etc.) is "hue". There is deterioration. "

＜塩基価＞
ＩＳＯＴ試験開始前の試験油の塩基価（Ｂ０ｈ）、ＩＳＯＴ試験開始から７２時間後の試験油の塩基価（Ｂ７２ｈ）、及びＩＳＯＴ試験開始から１６８時間後の試験油の塩基価（Ｂ１６８ｈ）を、ＪＩＳ Ｋ ２５０１−８：２００３に準拠して、塩酸法により測定した。
そして、以下の式により、「ＩＳＯＴ試験開始から７２時間後の塩基価維持率Ｓ７２ｈ（％）」と「ＩＳＯＴ試験開始から１６８時間後の塩基価維持率Ｓ１６８ｈ（％）」を計算した。
・Ｓ７２ｈ（％）＝｛（Ｂ７２ｈ）／（Ｂ０ｈ）｝×１００
・Ｓ１６８ｈ（％）＝｛（Ｂ１６８ｈ）／（Ｂ０ｈ）｝×１００ <Base value>
The base value of the test oil before the start of the ISOT test (B 0h ), the base value of the test oil 72 hours after the start of the ISOT test (B 72h ), and the base value of the test oil 168 hours after the start of the ISOT test (B 168h). ) Was measured by the hydrochloric acid method in accordance with JIS K 2501-8: 2003.
Then, "base value maintenance rate S 72h (%) 72 hours after the start of the ISOT test" and "base value maintenance rate S 168h (%) 72 hours after the start of the ISOT test" were calculated by the following formulas.
・ S 72h (%) = {(B 72h ) / (B 0h )} × 100
・ S 168h (%) = {(B 168h ) / (B 0h )} × 100

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

Figure 2021161291
Figure 2021161291

表１より、以下のことがわかる。
実施例１〜１１の潤滑油組成物は、ＩＳＯＴ試験開始から１６８時間経過後も色相悪化が見られなかった。
これに対し、ＺｎＤＴＰを配合し、Ｎａスルホネートを配合していない、比較例１及び２は、ＩＳＯＴ試験開始から７２時間経過後に色相の悪化が見られた。
また、Ｎａスルホネートを配合し、ＺｎＤＴＰを配合していない、比較例３及び４も、ＩＳＯＴ試験開始から７２時間経過後に色相の悪化が見られた。
さらに、Ｎａスルホネートに代えて、Ｃａスルホネートを配合した比較例５及び６、並びに、Ｎａスルホネートに代えて、Ｍｇスルホネートを配合した比較例７も、ＩＳＯＴ試験開始から７２時間経過後に色相の悪化が見られた。 From Table 1, the following can be seen.
No deterioration in hue was observed in the lubricating oil compositions of Examples 1 to 11 even after 168 hours from the start of the ISOT test.
On the other hand, in Comparative Examples 1 and 2 containing ZnDTP and not Nasulfonate, deterioration of hue was observed 72 hours after the start of the ISOT test.
Further, in Comparative Examples 3 and 4 containing Na sulfonate and not ZnDTP, deterioration of hue was observed 72 hours after the start of the ISOT test.
Further, in Comparative Examples 5 and 6 in which Ca sulfonate was added instead of Na sulfonate, and Comparative Example 7 in which Mg sulfonate was added instead of Na sulfonate, deterioration of hue was observed 72 hours after the start of the ISOT test. Was done.

Claims (6)

基油（Ａ）と、ジアルキルジチオリン酸亜鉛（Ｂ）と、ナトリウム系清浄剤（Ｃ）とを含有する潤滑油組成物であり、
亜鉛原子含有量が、前記潤滑油組成物の全量基準で、１００質量ｐｐｍ〜２，０００質量ｐｐｍであり、
ナトリウム原子含有量が、前記潤滑油組成物の全量基準で、５質量ｐｐｍ〜１，０００質量ｐｐｍである、潤滑油組成物。 A lubricating oil composition containing a base oil (A), zinc dialkyldithiophosphate (B), and a sodium-based cleaning agent (C).
The zinc atom content is 100 mass ppm to 2,000 mass ppm based on the total amount of the lubricating oil composition.
A lubricating oil composition having a sodium atom content of 5 mass ppm to 1,000 mass ppm based on the total amount of the lubricating oil composition. 前記潤滑油組成物中の亜鉛原子（Ｚｎ）と前記潤滑油組成物中のナトリウム原子（Ｎａ）との含有比率［（Ｚｎ）／（Ｎａ）］が、質量比で、０．０５０〜５０である、請求項１に記載の潤滑油組成物。 The content ratio [(Zn) / (Na)] of the zinc atom (Zn) in the lubricating oil composition and the sodium atom (Na) in the lubricating oil composition is 0.050 to 50 in terms of mass ratio. The lubricating oil composition according to claim 1. マグネシウム原子の含有量が、前記潤滑油組成物の全量基準で、３０質量ｐｐｍ未満である、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 content of magnesium atoms is less than 30% by mass based on the total amount of the lubricating oil composition. カルシウム原子の含有量が、前記潤滑油組成物の全量基準で、３０質量ｐｐｍ未満である、請求項１〜３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 3, wherein the content of calcium atoms is less than 30% by mass based on the total amount of the lubricating oil composition. 触媒として銅片と鉄片を入れ、ＪＩＳ Ｋ ２５１４−１：２０１３に準拠するＩＳＯＴ試験を、１５０℃で１６８時間行った後のＡＳＴＭ色が、１．０以下である、請求項１〜４のいずれか１項に記載の潤滑油組成物。 Any of claims 1 to 4, wherein an ASTM color of 1.0 or less after conducting an ISOT test conforming to JIS K 2514-1: 2013 at 150 ° C. for 168 hours with a copper piece and an iron piece as a catalyst. The lubricating oil composition according to item 1. 基油（Ａ）の４０℃における動粘度が、９．００ｍｍ２／ｓ〜１６５ｍｍ２／ｓ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。 Kinematic viscosity at 40 ° C. of the base oil (A) is 9.00mm 2 / s~165mm 2 / s, the lubricating oil composition according to any one of claims 1 to 5.
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