JP5463108B2 - Lubricating oil composition - Google Patents
Lubricating oil composition Download PDFInfo
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- JP5463108B2 JP5463108B2 JP2009213646A JP2009213646A JP5463108B2 JP 5463108 B2 JP5463108 B2 JP 5463108B2 JP 2009213646 A JP2009213646 A JP 2009213646A JP 2009213646 A JP2009213646 A JP 2009213646A JP 5463108 B2 JP5463108 B2 JP 5463108B2
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- lubricating oil
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- oil composition
- alkaline earth
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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
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- C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
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- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
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- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
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- C10M105/38—Esters of polyhydroxy compounds
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- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
- C10M105/42—Complex esters, i.e. compounds containing at least three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compound: monohydroxy compounds, polyhydroxy compounds, monocarboxylic acids, polycarboxylic acids and hydroxy carboxylic acids
- C10M105/46—Complex esters, i.e. compounds containing at least three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compound: monohydroxy compounds, polyhydroxy compounds, monocarboxylic acids, polycarboxylic acids and hydroxy carboxylic acids derived from the combination of monohydroxy compounds, dihydroxy compounds and dicarboxylic acids only and having no free hydroxy or carboxyl groups
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- C10M105/50—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing halogen
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- C10M105/56—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing nitrogen
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- C10M105/76—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing silicon
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- C10M159/12—Reaction products
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
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- 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
- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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- C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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Description
本発明は潤滑油組成物に関し、さらに詳しくは、ジチオリン酸亜鉛を含有しながらも、低摩擦摺動材料用の潤滑油として用いた際に低い摩擦係数を示す潤滑油組成物に関する。 The present invention relates to a lubricating oil composition, and more particularly to a lubricating oil composition that contains zinc dithiophosphate but exhibits a low coefficient of friction when used as a lubricating oil for low friction sliding materials.
近年、様々な分野において環境問題への対応が重要になっており、省エネルギー化や二酸化炭素の排出量の低減化に関する技術開発が進められている。例えば、自動車に関しては燃費の向上が課題の一つであり、潤滑油や摺動材料の技術開発が重要になっている。 In recent years, it has become important to respond to environmental problems in various fields, and technological development relating to energy saving and reduction of carbon dioxide emission has been promoted. For example, improvement of fuel efficiency is one of the issues for automobiles, and technical development of lubricating oil and sliding materials is important.
潤滑油に関しては、これまでに各種性能向上を目的として、種々の基油や添加剤が開発されている。例えば、エンジン油に要求される性能としては、適切な粘度特性、酸化安定性、清浄分散性、摩耗防止性、あわ立ち防止性等があり、種々の基油及び添加剤の組み合わせによりこれらの性能向上が図られている。特に、ジチオリン酸亜鉛(ZnDTP)は耐摩耗添加剤として優れることから、エンジン油の添加剤としてよく使用されている。 Regarding the lubricating oil, various base oils and additives have been developed so far for the purpose of improving various performances. For example, the performance required for engine oil includes appropriate viscosity characteristics, oxidation stability, clean dispersibility, antiwear, antifogging, etc., and these performances can be improved by combining various base oils and additives. Is planned. In particular, zinc dithiophosphate (ZnDTP) is often used as an engine oil additive because it is excellent as an antiwear additive.
一方、摺動材料に関しては、摩擦摩耗環境が苛酷な部位(例えば、エンジンの摺動部位)用の材料として、耐摩耗性向上等に寄与するTiN皮膜やCrN皮膜等の硬質皮膜を有する材料が知られている。さらに、ダイヤモンドライクカーボン(DLC)皮膜を利用することで、空気中、潤滑油非存在下において摩擦係数を低下できることが知られ、DLC皮膜を有する材料(以下、DLC材料と称する。)が低摩擦摺動材料として期待されている。 On the other hand, with regard to the sliding material, as a material for a part having a severe frictional wear environment (for example, a sliding part of an engine), there is a material having a hard film such as a TiN film or a CrN film that contributes to an improvement in wear resistance. Are known. Furthermore, it is known that a friction coefficient can be lowered in the air and in the absence of lubricating oil by using a diamond-like carbon (DLC) film, and a material having a DLC film (hereinafter referred to as a DLC material) has a low friction. Expected to be a sliding material.
しかしながら、DLC材料は、潤滑油の存在下においてはその摩擦低減効果が小さいことがあり、この場合省燃費効果は得られにくい。このため、これまでにDLC材料等の低摩擦摺動材料用の潤滑油組成物の開発が行われている。
例えば、特許文献1にはエーテル系無灰摩擦低減剤を含む、低摩擦摺動部材に用いられる潤滑油組成物が開示されている。特許文献2、3には、DLC部材と鉄基部材との摺動面やDLC部材とアルミニウム合金部材との摺動面に、脂肪酸エステル系無灰摩擦調整剤や脂肪族アミン系無灰摩擦調整剤を含有する潤滑油組成物を用いる技術が開示されている。特許文献4には、DLCコーティング摺動部材を有する低摩擦摺動機構において、含酸素有機化合物や脂肪族アミン系化合物を含有する低摩擦剤組成物を用いる技術が開示されている。
このように低摩擦摺動材料用の潤滑油組成物が開発されているが、これらの技術を応用した場合であっても、耐摩耗性等の更なる向上を求めてZnDTPを配合すると摩擦係数が大きくなるという傾向があった。したがって、種々の性能に優れ、バランスの良い潤滑油を得ることを目的にすると、ZnDTPを含有しながらも、低摩擦摺動材料用の潤滑油として用いた際に低い摩擦係数を示す潤滑油組成物が求められている。
However, the DLC material may have a small friction reducing effect in the presence of lubricating oil, and in this case, it is difficult to obtain a fuel saving effect. For this reason, a lubricating oil composition for a low friction sliding material such as a DLC material has been developed so far.
For example, Patent Document 1 discloses a lubricating oil composition used for a low friction sliding member containing an ether-based ashless friction reducing agent. Patent Documents 2 and 3 include a fatty acid ester-based ashless friction modifier and an aliphatic amine-based ashless friction adjustment on the sliding surface between the DLC member and the iron base member and the sliding surface between the DLC member and the aluminum alloy member. A technique using a lubricating oil composition containing an agent is disclosed. Patent Document 4 discloses a technique using a low friction agent composition containing an oxygen-containing organic compound or an aliphatic amine compound in a low friction sliding mechanism having a DLC coating sliding member.
Lubricating oil compositions for low-friction sliding materials have been developed in this way, but even when these technologies are applied, the friction coefficient can be increased by adding ZnDTP to further improve wear resistance. Tended to be larger. Therefore, for the purpose of obtaining a lubricating oil having various performance and good balance, a lubricating oil composition containing ZnDTP but having a low friction coefficient when used as a lubricating oil for a low friction sliding material. Things are sought.
本発明は上記事情に鑑みなされたもので、耐摩耗剤としてZnDTPを含有しながらも、低摩擦摺動材料用の潤滑油として用いた際に低い摩擦係数を示す潤滑油組成物、すなわち、耐摩耗性と低摩擦性を両立する低摩擦摺動材料用潤滑油組成物を提供することを目的とするものである。 The present invention has been made in view of the above circumstances, and contains a lubricating oil composition that exhibits a low coefficient of friction when used as a lubricating oil for low friction sliding materials while containing ZnDTP as an antiwear agent. An object of the present invention is to provide a lubricating oil composition for a low friction sliding material that has both wear and low friction properties.
本発明者らは、鋭意研究を重ねた結果、特定の添加剤を特定量配合することで、前記課題が解決することを見出した。本発明はかかる知見に基づいて完成したものである。
すなわち本発明は、
1. 潤滑油基油に、(A)アルカリ土類金属サリシレート系および/またはアルカリ土類金属スルフォネート系清浄剤、(B)数平均分子量500〜4000のアルケニル基またはアルキル基を有する、ホウ素未含有コハク酸イミド系無灰分散剤、(C)ジアルキルジチオリン酸亜鉛および(D)ポリスルフィド化合物、硫化油脂、硫化オレフィン、チオリン酸エステル、チオ亜リン酸エステル及びこれらのエステルのアミン塩から選ばれる硫黄系化合物を配合してなる潤滑油組成物であって、組成物全量基準の配合量が、(A)成分がアルカリ土類金属濃度換算で、0.05〜0.25質量%、(B)成分が窒素濃度換算で、0.03〜0.50質量%、(C)成分がリン濃度換算で0.01〜0.12質量%、(D)成分が硫黄濃度換算で0.02〜2.0質量%であって、アルカリ土類金属フェネート系清浄剤がアルカリ土類金属濃度換算で0.10質量%以下、ホウ素含有コハク酸イミドが窒素濃度換算で、0.04質量%以下である、低摩擦摺動材料に用いられる潤滑油組成物、
2. ジアルキルジチオリン酸亜鉛の配合量が、リン濃度換算で0.03〜0.10質量%である上記1に記載の潤滑油組成物、
3. 数平均分子量500〜4000のアルケニル基またはアルキル基を有する、ホウ素未含有コハク酸イミド系無灰分散剤の配合量が、窒素濃度換算で0.05〜0.30質量%である上記1または2に記載の潤滑油組成物、
4. 硫黄系化合物が、一般式(I)
R1−Sn−R2 (I)
(式中、nは1〜4から選ばれる整数を表し、R1及びR2は、それぞれ独立にアルキル基またはアラルキル基を表す。)
で示される化合物である上記1〜3のいずれかに記載の潤滑油組成物、
5. 一般式(I)中のnが2または3である上記4に記載の潤滑油組成物、
6. 低摩擦摺動材料がダイヤモンドライクカーボン(DLC)皮膜を有する材料である上記1〜5のいずれかに記載の潤滑油組成物、
を提供するものである。
As a result of intensive studies, the present inventors have found that the above problem can be solved by blending a specific amount of a specific additive. The present invention has been completed based on such findings.
That is, the present invention
1. Boron-free succinic acid having (A) alkaline earth metal salicylate and / or alkaline earth metal sulfonate detergent, (B) alkenyl group or alkyl group having a number average molecular weight of 500 to 4000 Formulated with imide-based ashless dispersant, (C) zinc dialkyldithiophosphate and (D) polysulfide compound, sulfurized oil, sulfurized olefin, thiophosphate, thiophosphite, and amine salts of these esters The blending amount based on the total amount of the composition is 0.05 to 0.25% by mass in terms of the alkaline earth metal concentration, and the component (B) is the nitrogen concentration. 0.03-0.50 mass% in terms of conversion, (C) component is 0.01-0.12 mass% in terms of phosphorus concentration, and (D) component is 0 in terms of sulfur concentration. 02 to 2.0% by mass, the alkaline earth metal phenate detergent is 0.10% by mass or less in terms of alkaline earth metal concentration, and the boron-containing succinimide is 0.04% by mass in terms of nitrogen concentration A lubricating oil composition used for a low friction sliding material,
2. The lubricating oil composition according to 1 above, wherein the amount of zinc dialkyldithiophosphate is 0.03 to 0.10% by mass in terms of phosphorus concentration,
3. In 1 or 2 above, the amount of boron-free succinimide-based ashless dispersant having an alkenyl group or alkyl group having a number average molecular weight of 500 to 4000 is 0.05 to 0.30% by mass in terms of nitrogen concentration The lubricating oil composition as described,
4). Sulfur compounds are represented by the general formula (I)
R 1 -S n -R 2 (I)
(In the formula, n represents an integer selected from 1 to 4, and R 1 and R 2 each independently represents an alkyl group or an aralkyl group.)
The lubricating oil composition according to any one of 1 to 3, which is a compound represented by:
5. The lubricating oil composition according to 4 above, wherein n in the general formula (I) is 2 or 3,
6). The lubricating oil composition according to any one of the above 1 to 5, wherein the low friction sliding material is a material having a diamond-like carbon (DLC) film,
Is to provide.
本発明によれば、耐摩耗剤としてZnDTPを含有しながらも、低摩擦摺動材料用の潤滑油として用いた際に低い摩擦係数を示す潤滑油組成物が提供される。 According to the present invention, there is provided a lubricating oil composition that contains ZnDTP as an antiwear agent and exhibits a low friction coefficient when used as a lubricating oil for a low friction sliding material.
本発明の潤滑油組成物は、潤滑油基油に、必須の添加剤として(A)アルカリ土類金属サリシレート系および/またはアルカリ土類金属スルフォネート系清浄剤、(B)数平均分子量500〜4000のアルケニル基またはアルキル基を有する、ホウ素未含有コハク酸イミド系無灰分散剤、(C)ジアルキルジチオリン酸亜鉛および(D)ポリスルフィド化合物、硫化油脂、硫化オレフィン、チオリン酸エステル、チオ亜リン酸エステル及びこれらのエステルのアミン塩から選ばれる硫黄系化合物を特定量配合してなるものであって、低摩擦摺動材料の潤滑油として用いられる。 The lubricating oil composition of the present invention contains (A) an alkaline earth metal salicylate and / or alkaline earth metal sulfonate detergent as an essential additive in the lubricating base oil, and (B) a number average molecular weight of 500 to 4000. Boron-free succinimide-based ashless dispersant, having (C) zinc dialkyldithiophosphate and (D) polysulfide compound, sulfurized oil, sulfurized olefin, thiophosphate, thiophosphite and A sulfur compound selected from the amine salts of these esters is blended in a specific amount, and is used as a lubricating oil for low friction sliding materials.
本発明で用いる潤滑油基油に特に制限はなく、従来使用されている公知の鉱物系基油及び合成系基油の中から適宜選択して用いることができる。
ここで、鉱油としては、例えばパラフィン基系原油、中間基系原油あるいはナフテン基系原油を常圧蒸留するか、又は常圧蒸留の残渣油を減圧蒸留して得られる留出油、あるいはこれを常法に従って精製することによって得られる精製油、例えば溶剤精製油、水添精製油、脱ろう処理油、白土処理油などを挙げることができる。
一方、合成油としては、例えば炭素数8〜14のα−オレフィンオリゴマーであるポリ(α−オレフィン)、ポリブテン、ポリオールエステル、アルキルベンゼンなどを挙げることができる。
本発明においては、基油として、上記鉱油を一種用いてもよく、二種以上を組み合わせて用いてもよい。また、上記合成油を一種用いてもよく、二種以上を組み合わせて用いてもよい。さらには、鉱油一種以上と合成油一種以上とを組み合わせて用いてもよい。
There is no restriction | limiting in particular in the lubricating base oil used by this invention, It can select suitably from well-known mineral base oil and synthetic base oil used conventionally.
Here, as the mineral oil, for example, a distillate obtained by atmospheric distillation of paraffinic crude oil, intermediate crude oil or naphthenic crude oil, or vacuum distillation residual oil, or The refined oil obtained by refine | purifying in accordance with a conventional method, for example, solvent refined oil, hydrogenated refined oil, dewaxing process oil, clay-treated oil, etc. can be mentioned.
On the other hand, examples of the synthetic oil include poly (α-olefin) which is an α-olefin oligomer having 8 to 14 carbon atoms, polybutene, polyol ester, and alkylbenzene.
In the present invention, as the base oil, one kind of the above mineral oil may be used, or two or more kinds may be used in combination. Moreover, the said synthetic oil may be used 1 type and may be used in combination of 2 or more type. Further, one or more mineral oils and one or more synthetic oils may be used in combination.
前記基油としては、100℃における動粘度が、通常2〜50mm2/s、好ましくは3〜30mm2/s、特に好ましくは3〜15mm2/sであるものが有利である。100℃における動粘度が2mm2/s以上であると蒸発損失が少なく、また50mm2/s以下であると、粘性抵抗による動力損失が抑制され、燃費改善効果が良好に発揮される。
また、この基油は、粘度指数が60以上、さらには70以上、特に80以上のものが好ましい。粘度指数が60以上であると、基油の温度による粘度変化が小さく、安定した潤滑性能を発揮する。
As the base oil, those having a kinematic viscosity at 100 ° C. of usually 2 to 50 mm 2 / s, preferably 3 to 30 mm 2 / s, particularly preferably 3 to 15 mm 2 / s are advantageous. When the kinematic viscosity at 100 ° C. is 2 mm 2 / s or more, the evaporation loss is small, and when it is 50 mm 2 / s or less, the power loss due to the viscous resistance is suppressed, and the fuel efficiency improvement effect is exhibited well.
The base oil preferably has a viscosity index of 60 or more, more preferably 70 or more, and particularly preferably 80 or more. When the viscosity index is 60 or more, the viscosity change due to the temperature of the base oil is small, and stable lubricating performance is exhibited.
前記(A)成分の清浄剤として用いられる、アルカリ土類金属サリシレートおよびアルカリ土類金属スルフォネートとしては、アルキル基を有する化合物等、清浄剤として従来公知の化合物を使用することができる。アルカリ土類金属としてはカルシウムやマグネシウム等が挙げられ、特にカルシウムが好ましい。
また、これらの清浄剤としては、中性塩、塩基性塩、過塩基性塩のいずれも使用することができ、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 alkaline earth metal salicylate and alkaline earth metal sulfonate used as the detergent for the component (A), conventionally known compounds such as compounds having an alkyl group can be used. Examples of the alkaline earth metal include calcium and magnesium, and calcium is particularly preferable.
Further, as these detergents, any of neutral salts, basic salts and overbased salts can be used, and one kind may be used alone, or two or more kinds may be used in combination. .
上記清浄剤の全塩基価は、要求される潤滑油組成物の性能に応じて任意に選択できる。通常は、過塩素酸法で0〜500mgKOH/g、好ましくは50〜400mgKOH/gである。組成物全量基準の上記清浄剤の配合量は、アルカリ土類金属濃度換算で0.05〜0.25質量%であり、好ましくは、0.06〜0.25質量%、より好ましくは0.1〜0.22質量%である。アルカリ土類金属濃度が0.25質量%を超えると、摩擦係数の低減化が困難になる。 The total base number of the detergent can be arbitrarily selected according to the required performance of the lubricating oil composition. Usually, it is 0-500 mgKOH / g by the perchloric acid method, Preferably it is 50-400 mgKOH / g. The blending amount of the detergent based on the total amount of the composition is 0.05 to 0.25% by mass in terms of alkaline earth metal concentration, preferably 0.06 to 0.25% by mass, more preferably 0.00. It is 1-0.22 mass%. If the alkaline earth metal concentration exceeds 0.25% by mass, it is difficult to reduce the friction coefficient.
アルカリ土類金属含有清浄剤としては、前記(A)成分以外の化合物も公知であり、例えば、アルカリ土類金属フェネート系清浄剤が挙げられる。しかしながら、アルカリ土類金属フェネート系清浄剤を配合すると摩擦係数の低減化が困難になるため、本発明においては、その使用を制限する必要がある。その組成物全量基準の含有量は、アルカリ土類金属濃度換算で、0.1質量%以下、好ましくは0.05質量%以下であり、全く含有しないことが特に好ましい。 As alkaline earth metal-containing detergents, compounds other than the component (A) are also known, and examples thereof include alkaline earth metal phenate detergents. However, when an alkaline earth metal phenate detergent is blended, it is difficult to reduce the friction coefficient. Therefore, in the present invention, it is necessary to limit its use. The content based on the total amount of the composition is 0.1% by mass or less, preferably 0.05% by mass or less, particularly preferably not contained at all, in terms of alkaline earth metal concentration.
本発明においては前記(B)成分の無灰分散剤として、数平均分子量500〜4000のアルケニル基またはアルキル基を有する、ホウ素未含有コハク酸イミド化合物(以下、当該コハク酸イミド化合物を「本発明のコハク酸イミド化合物」ということがある。)が配合される。アルケニル基またはアルキル基の数平均分子量が、500以上であれば良好な清浄性効果が発揮され、4000以下であれば低温流動性が良好である。
本発明のコハク酸イミド化合物としては、例えば、以下の一般式(II)または一般式(III)
In the present invention, as the ashless dispersant of the component (B), a boron-free succinimide compound having an alkenyl group or alkyl group having a number average molecular weight of 500 to 4000 (hereinafter, the succinimide compound is referred to as “the present invention”). Succinimide compound "). When the number average molecular weight of the alkenyl group or alkyl group is 500 or more, a good cleansing effect is exhibited, and when it is 4000 or less, the low temperature fluidity is good.
Examples of the succinimide compound of the present invention include the following general formula (II) or general formula (III):
で表される化合物が挙げられる。一般式(II)及び(III)におけるR3〜R5は、それぞれ独立に、数平均分子量500〜4000のアルケニル基又はアルキル基を表し、mは、1〜5の整数を表す。mが1〜5の整数であることで清浄性が向上し、2〜4の整数がより好ましい。 The compound represented by these is mentioned. R 3 to R 5 in the general formulas (II) and (III) each independently represent an alkenyl group or an alkyl group having a number average molecular weight of 500 to 4000, and m represents an integer of 1 to 5. Cleanliness is improved when m is an integer of 1 to 5, and an integer of 2 to 4 is more preferable.
一般式(II)及び(III)におけるR3〜R5としては、例えば、高純度イソブテン又は1−ブテンとイソブテンの混合物をフッ化ホウ素系触媒又は塩化アルミニウム系触媒で重合させて得られるポリブテン等に由来するアルケニル基又はアルキル基が挙げられる。 Examples of R 3 to R 5 in the general formulas (II) and (III) include polybutene obtained by polymerizing a high-purity isobutene or a mixture of 1-butene and isobutene with a boron fluoride catalyst or an aluminum chloride catalyst. An alkenyl group or an alkyl group derived from the above.
本発明のコハク酸イミド化合物の製造方法としては特に限定はないが、例えば、ポリブテンやポリブテンの塩素化物と無水マレイン酸とを100〜200℃程度で反応させて得られるブテニルコハク酸を、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン及びペンタエチレンヘキサミン等のポリアミンと反応させることにより得ることができる。なお、アルケニル基又はアルキル基の前駆体となる上記ポリブテン等は、製造過程の触媒に起因して残留する微量のフッ素分や塩素分を、吸着法や十分な水洗等の適切な方法により、通常50質量ppm以下、好ましくは10質量ppm以下、特に好ましくは1質量ppm以下まで除去してから用いることが有利である。 The method for producing the succinimide compound of the present invention is not particularly limited. For example, butenyl succinic acid obtained by reacting polybutene or a chlorinated product of polybutene and maleic anhydride at about 100 to 200 ° C. is converted into diethylenetriamine, triethylene. It can be obtained by reacting with polyamines such as ethylenetetramine, tetraethylenepentamine and pentaethylenehexamine. The polybutene or the like that is a precursor of an alkenyl group or an alkyl group is usually removed by an appropriate method such as an adsorption method or sufficient washing with water by removing a trace amount of fluorine and chlorine remaining due to a catalyst in the production process. It is advantageous to use after removing to 50 mass ppm or less, preferably 10 mass ppm or less, particularly preferably 1 mass ppm or less.
本発明においては、上記のようにホウ素未含有のコハク酸イミド化合物が用いられる。このホウ素未含有とは、ホウ素化合物で処理したコハク酸イミド化合物は、本願(B)成分から除外されることを意味する。すなわち、無灰分散剤として、ポリブテニルコハク酸イミド化合物にホウ酸、ホウ酸塩及びホウ酸エステル等のホウ素化合物を作用させて、残存するアミノ基及び/又はイミノ基の一部又は全部を中和したホウ素含有ポリブテニルコハク酸イミド化合物が知られているが、このようなホウ素含有ポリブテニルコハク酸イミドを配合すると、低摩擦摺動材料の潤滑油として用いた際に摩擦の低減化が困難になる。 In the present invention, a boron-free succinimide compound is used as described above. This boron-free means that the succinimide compound treated with the boron compound is excluded from the component (B). That is, as an ashless dispersant, a boron compound such as boric acid, borate, and boric acid ester is allowed to act on a polybutenyl succinimide compound so that a part or all of the remaining amino groups and / or imino groups can be added. A boron-containing polybutenyl succinimide compound is known, but when such a boron-containing polybutenyl succinimide compound is blended, friction is reduced when used as a lubricant for low friction sliding materials. Becomes difficult.
本発明の潤滑油組成物においては、本発明のコハク酸イミド化合物を、一種配合してもよく、二種以上を組み合わせて配合しても良い。本発明のコハク酸イミド化合物の、組成物全量基準の配合量は、窒素濃度換算で0.03〜0.50質量%であり、好ましくは、0.05〜0.30質量%である。窒素濃度が上記範囲内にあると、清浄性、抗乳化性及び経済性のバランスなどの面で好ましい効果が得られる。 In the lubricating oil composition of the present invention, the succinimide compound of the present invention may be blended in one kind or in combination of two or more kinds. The blending amount of the succinimide compound of the present invention based on the total amount of the composition is 0.03 to 0.50% by mass, preferably 0.05 to 0.30% by mass in terms of nitrogen concentration. When the nitrogen concentration is within the above range, favorable effects can be obtained in terms of the balance of cleanliness, demulsibility and economic efficiency.
上記のように、ホウ素含有コハク酸イミド化合物を配合すると摩擦係数の低減化が困難になるため、本発明においては、その使用を制限する必要がある。その組成物全量基準の含有量は、窒素濃度換算で、0.04質量%以下、好ましくは0.02質量%であり、全く含有しないことが特に好ましい。 As described above, when a boron-containing succinimide compound is blended, it is difficult to reduce the friction coefficient. Therefore, in the present invention, it is necessary to limit its use. The content based on the total amount of the composition is 0.04% by mass or less, preferably 0.02% by mass in terms of nitrogen concentration, and it is particularly preferable that no content is contained at all.
前記(C)成分のジアルキルジチオリン酸亜鉛としては、例えば、一般式(IV) Examples of the component (C) zinc dialkyldithiophosphate include, for example, the general formula (IV)
で表される化合物が挙げられる。
一般式(IV)において、R6〜R9は、それぞれ独立にアルキル基を示し、好ましくは炭素数1〜24のアルキル基が用いられる。
The compound represented by these is mentioned.
In general formula (IV), R < 6 > -R < 9 > shows an alkyl group each independently, Preferably a C1-C24 alkyl group is used.
炭素数1〜24のアルキル基は直鎖状、分岐鎖状、環状のいずれであってもよく、具体的にはメチル基、エチル基を始め、それぞれ異性体を含む各種のプロピル基、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、トリコシル基及びテトラコシル基、あるいはシクロペンチル基、シクロヘキシル基、シクロヘプチル基及びこれらのアルキル置換体などが挙げられる。 The alkyl group having 1 to 24 carbon atoms may be linear, branched or cyclic, and specifically includes various propyl groups and butyl groups each including isomers including a methyl group and an ethyl group. , Pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, heicosyl Group, docosyl group, tricosyl group and tetracosyl group, or cyclopentyl group, cyclohexyl group, cycloheptyl group, and alkyl substituted products thereof.
一般式(IV)で表されるジアルキルジチオリン酸亜鉛の具体例としては、例えばジイソプロピルジチオリン酸亜鉛、ジイソブチルジチオリン酸亜鉛、ジ−sec−ブチルジチオリン酸亜鉛、ジ−sec−ペンチルジチオリン酸亜鉛、ジ−n−ヘキシルジチオリン酸亜鉛、ジ−sec−ヘキシルジチオリン酸亜鉛、ジ−オクチルジチオリン酸亜鉛、ジ−2−エチルヘキシルジチオリン酸亜鉛、ジ−n−デシルジチオリン酸亜鉛、ジ−n−ドデシルジチオリン酸亜鉛、ジイソトリデシルジチオリン酸亜鉛などが挙げられる。これらの中で、耐摩耗性の向上効果の面からは、第二級アルキル基のジアルキルジチオリン酸亜鉛が好適である。 Specific examples of the zinc dialkyldithiophosphate represented by the general formula (IV) include, for example, zinc diisopropyldithiophosphate, zinc diisobutyldithiophosphate, zinc di-sec-butyldithiophosphate, zinc di-sec-pentyldithiophosphate, di- zinc n-hexyldithiophosphate, zinc di-sec-hexyldithiophosphate, zinc di-octyldithiophosphate, zinc di-2-ethylhexyldithiophosphate, zinc di-n-decyldithiophosphate, zinc di-n-dodecyldithiophosphate, Examples include zinc diisotridecyl dithiophosphate. Among these, zinc dialkyldithiophosphate having a secondary alkyl group is preferable from the viewpoint of the effect of improving wear resistance.
本発明の潤滑油組成物においては、前記ジアルキルジチオリン酸亜鉛を、一種配合してもよく、二種以上を組み合わせて配合しても良い。ジアルキルジチオリン酸亜鉛の、組成物全量基準の配合量は、リン濃度換算で、0.01〜0.12質量%であり、好ましくは、0.03〜0.10質量%である。ジアルキルジチオリン酸亜鉛の配合により、耐摩耗性や高温清浄性が向上するが、リン濃度換算で0.12質量%を超えると、摩擦係数の低減化が困難になる。 In the lubricating oil composition of the present invention, the zinc dialkyldithiophosphate may be blended in one kind or in combination of two or more kinds. The amount of zinc dialkyldithiophosphate based on the total amount of the composition is 0.01 to 0.12% by mass, preferably 0.03 to 0.10% by mass in terms of phosphorus concentration. Although the wear resistance and the high-temperature cleanability are improved by blending the zinc dialkyldithiophosphate, if it exceeds 0.12% by mass in terms of phosphorus concentration, it is difficult to reduce the friction coefficient.
前記(D)成分の硫黄系化合物は、ポリスルフィド化合物、硫化油脂、硫化オレフィン、チオリン酸エステル、チオ亜リン酸エステル及びこれらのエステルのアミン塩から選ばれる化合物である。この中で、ポリスルフィド化合物が好ましく、特に、一般式(I)
R1−Sn−R2 (I)
で示される化合物が好ましい。(I)式中、nは1〜4から選ばれる整数を表し、特にnが2または3が好ましい。R1及びR2は、それぞれ独立にアルキル基またはアラルキル基を表す。R1およびR2は、好ましくは炭素数4〜24の基であり、より好ましくは炭素数8〜18の基である。
The sulfur compound of the component (D) is a compound selected from polysulfide compounds, sulfurized fats and oils, sulfurized olefins, thiophosphate esters, thiophosphite esters, and amine salts of these esters. Of these, polysulfide compounds are preferred, and in particular, the general formula (I)
R 1 -S n -R 2 (I)
The compound shown by these is preferable. In formula (I), n represents an integer selected from 1 to 4, and n is particularly preferably 2 or 3. R 1 and R 2 each independently represents an alkyl group or an aralkyl group. R 1 and R 2 are preferably a group having 4 to 24 carbon atoms, more preferably a group having 8 to 18 carbon atoms.
本発明においては、前記硫黄系化合物は、一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。硫黄系化合物の、組成物全量基準の配合量は、硫黄濃度換算で0.02〜2.0質量%であり、好ましくは、0.02〜1.0質量%である。0.02質量%を下回る場合においても、2.0質量%を超える場合であっても、摩擦係数の低減化が困難になる。 In this invention, the said sulfur type compound may be used individually by 1 type, and may be used in combination of 2 or more type. The amount of the sulfur-based compound based on the total amount of the composition is 0.02 to 2.0 mass%, preferably 0.02 to 1.0 mass%, in terms of sulfur concentration. Even when the amount is less than 0.02% by mass or more than 2.0% by mass, it is difficult to reduce the friction coefficient.
本発明の潤滑油組成物は本発明の効果を損なわない限りにおいて、従来公知の添加剤を配合しても良く、例えば、摩擦低減剤、粘度指数向上剤、流動点降下剤、酸化防止剤、防錆剤等が挙げられる。
摩擦低減剤としては、脂肪酸エステル系、脂肪族アミン系、高級アルコール系などの無灰摩擦低減剤が挙げられる。粘度指数向上剤としては、具体的には、各種メタクリル酸エステル又はこれらの任意の組合せに係る共重合体やその水添物等のいわゆる非分散型粘度指数向上剤、及び更に窒素化合物を含む各種メタクリル酸エステルを共重合させたいわゆる分散型粘度指数向上剤等が例示できる。また、非分散型又は分散型エチレン−α−オレフィン共重合体(α−オレフィンとしては、例えばプロピレン、1−ブテン、1−ペンテン等)及びその水素化物、ポリイソブチレン及びその水添物、スチレン−ジエン水素化共重合体、スチレン−無水マレイン酸エステル共重合体、並びにポリアルキルスチレン等も例示できる。これら粘度指数向上剤の分子量は、せん断安定性を考慮して選定することが必要である。具体的には、粘度指数向上剤の数平均分子量は、例えば分散型及び非分散型ポリメタクリレートでは5000〜1000000、好ましくは100000〜800000がよく、ポリイソブチレン又はその水素化物では800〜5000、エチレン−α−オレフィン共重合体及びその水素化物では800〜300000、好ましくは10000〜200000がよい。また、かかる粘度指数向上剤は、単独で又は複数種を任意に組合せて含有させることができるが、通常その含有量は、潤滑油組成物全量に基づき0.1〜40.0質量%程度である。流動点降下剤としては、例えばポリメタクリレートなどが挙げられる。
The lubricating oil composition of the present invention may be blended with conventionally known additives as long as the effects of the present invention are not impaired, for example, friction reducers, viscosity index improvers, pour point depressants, antioxidants, An antirust agent etc. are mentioned.
Examples of the friction reducing agent include ashless friction reducing agents such as fatty acid esters, aliphatic amines, and higher alcohols. Specific examples of the viscosity index improver include so-called non-dispersion type viscosity index improvers such as various methacrylate esters or copolymers and hydrogenated products thereof, and various nitrogen compounds. Examples thereof include a so-called dispersed viscosity index improver obtained by copolymerizing a methacrylic acid ester. Further, non-dispersed or dispersed ethylene-α-olefin copolymers (for example, propylene, 1-butene, 1-pentene, etc.) and hydrides thereof, polyisobutylene and hydrogenated products thereof, styrene- Examples thereof include diene hydrogenated copolymers, styrene-maleic anhydride copolymers, and polyalkylstyrenes. The molecular weight of these viscosity index improvers needs to be selected in consideration of shear stability. Specifically, the number average molecular weight of the viscosity index improver is, for example, 5,000 to 1,000,000, preferably 100,000 to 800,000 for dispersed and non-dispersed polymethacrylates, 800 to 5,000 for polyisobutylene or a hydride thereof, ethylene- The α-olefin copolymer and its hydride have a value of 800 to 300,000, preferably 10,000 to 200,000. Further, the viscosity index improver can be contained alone or in any combination of plural kinds, but the content is usually about 0.1 to 40.0% by mass based on the total amount of the lubricating oil composition. is there. Examples of the pour point depressant include polymethacrylate.
酸化防止剤としては、フェノール系酸化防止剤やアミン系酸化防止剤が挙げられる。フェノール系酸化防止剤としては、例えば4,4'−メチレンビス(2,6−ジ−t−ブチルフェノール);4,4'−ビス(2,6−ジ−t−ブチルフェノール);4,4'−ビス(2−メチル−6−t−ブチルフェノール);2,2'−メチレンビス(4−エチル−6−t−ブチルフェノール);2,2'−メチレンビス(4−メチル−6−t−ブチルフェノール);4,4'−ブチリデンビス(3−メチル−6−t−ブチルフェノール);4,4'−イソプロピリデンビス(2,6−ジ−t−ブチルフェノール);2,2'−メチレンビス(4−メチル−6−ノニルフェノール);2,2'−イソブチリデンビス(4,6−ジメチルフェノール);2,2'−メチレンビス(4−メチル−6−シクロヘキシルフェノール);2,6−ジ−t−ブチル−4−メチルフェノール;2,6−ジ−t−ブチル−4−エチルフェノール;2,4−ジメチル−6−t−ブチルフェノール;2,6−ジ−t−アミル−p−クレゾール;2,6−ジ−t−ブチル−4−(N,N'−ジメチルアミノメチルフェノール);4,4'−チオビス(2−メチル−6−t−ブチルフェノール);4,4'−チオビス(3−メチル−6−t−ブチルフェノール);2,2'−チオビス(4−メチル−6−t−ブチルフェノール);ビス(3−メチル−4−ヒドロキシ−5−t−ブチルベンジル)スルフィド;ビス(3,5−ジ−t−ブチル−4−ヒドロキシベンジル)スルフィド;n−オクタデシル−3−(4−ヒドロキシ−3,5−ジ−t−ブチルフェニル)プロピオネート;2,2'−チオ[ジエチル−ビス−3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート]などが挙げられる。これらの中で、特にビスフェノール系及びエステル基含有フェノール系のものが好適である。 Examples of the antioxidant include phenolic antioxidants and amine antioxidants. Examples of the phenolic antioxidant include 4,4′-methylenebis (2,6-di-t-butylphenol); 4,4′-bis (2,6-di-t-butylphenol); 4,4′- Bis (2-methyl-6-tert-butylphenol); 2,2′-methylenebis (4-ethyl-6-tert-butylphenol); 2,2′-methylenebis (4-methyl-6-tert-butylphenol); 4 4,4′-butylidenebis (3-methyl-6-tert-butylphenol); 4,4′-isopropylidenebis (2,6-di-tert-butylphenol); 2,2′-methylenebis (4-methyl-6- Nonylphenol); 2,2′-isobutylidenebis (4,6-dimethylphenol); 2,2′-methylenebis (4-methyl-6-cyclohexylphenol); 2,6-di-t-butyl- 2,6-di-t-butyl-4-ethylphenol; 2,4-dimethyl-6-t-butylphenol; 2,6-di-t-amyl-p-cresol; Di-t-butyl-4- (N, N′-dimethylaminomethylphenol); 4,4′-thiobis (2-methyl-6-tert-butylphenol); 4,4′-thiobis (3-methyl-6) -T-butylphenol); 2,2'-thiobis (4-methyl-6-t-butylphenol); bis (3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide; bis (3,5-di-) -T-butyl-4-hydroxybenzyl) sulfide; n-octadecyl-3- (4-hydroxy-3,5-di-t-butylphenyl) propionate; 2,2'-thio [diethyl-bis-3- ( 3, - di -t- butyl-4-hydroxyphenyl) propionate] and the like. Among these, bisphenol-based and ester group-containing phenol-based ones are particularly preferable.
また、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などのモノアルキルジフェニルアミン系、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などのジアルキルジフェニルアミン系、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、及びナフチルアミン系のもの、具体的にはα−ナフチルアミン;フェニル−α−ナフチルアミン;さらにはブチルフェニル−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アルキル置換フェニル−α−ナフチルアミンなどが挙げられる。これらの中でジアルキルジフェニルアミン系及びナフチルアミン系のものが好適である。
防錆剤としては、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、アルケニルコハク酸エステル、多価アルコールエステル等が挙げられる。
Examples of the amine antioxidant include monooctyl diphenylamine; monoalkyl diphenylamines such as monononyl diphenylamine; 4,4′-dibutyldiphenylamine; 4,4′-dipentyldiphenylamine; 4,4′-dihexyldiphenylamine; 4,4′-diheptyldiphenylamine; 4,4′-dioctyldiphenylamine; dialkyldiphenylamines such as 4,4′-dinonyldiphenylamine; tetrabutyldiphenylamine; tetrahexyldiphenylamine; tetraoctyldiphenylamine; polyalkyldiphenylamine such as tetranonyldiphenylamine And naphthylamine type, specifically α-naphthylamine; phenyl-α-naphthylamine; and butylphenyl-α-naphthyl Min; pentylphenyl -α- naphthylamine; hexylphenyl -α- naphthylamine; heptylphenyl -α- naphthylamine; octylphenyl -α- naphthylamine; and alkyl-substituted phenyl -α- naphthylamine, such as nonylphenyl -α- naphthylamine. Of these, dialkyldiphenylamine type and naphthylamine type are preferable.
Examples of the rust inhibitor include alkyl benzene sulfonate, dinonyl naphthalene sulfonate, alkenyl succinate, polyhydric alcohol ester and the like.
本発明の潤滑油組成物は、低摩擦摺動材料を有する摺動面に適用され、優れた低摩擦特性を付与することができ、特に内燃機関に適用した場合には、省燃費効果を付与することができる。
前記の低摩擦摺動材料を有する摺動面としては、一方の側に低摩擦摺動材料としてDLC材料を有するものが特に好ましい。この場合、相手の材料については特に制限はなく、例えば該DLC材料と鉄基材料との摺動面あるいはDLC材料とアルミニウム合金材料との摺動面などを挙げることができる。
ここで、上記DLC材料は、表面にDLC膜を有し、該膜を構成するDLC材は、炭素元素を主として構成された非晶質であり、炭素同士の結合形態がダイヤモンド構造(SP3結合)とグラファイト結合(SP2結合)の両方から成る。具体的には、炭素元素だけから成るa−C(アモルファスカーボン)、水素を含有するa−C:H(水素アモルファスカーボン)、及びチタン(Ti)やモリブデン(Mo)等の金属元素を一部に含むMeCが挙げられる。
The lubricating oil composition of the present invention is applied to a sliding surface having a low-friction sliding material and can impart excellent low-friction characteristics, and particularly when applied to an internal combustion engine, provides a fuel-saving effect. can do.
As the sliding surface having the low friction sliding material, one having a DLC material as a low friction sliding material on one side is particularly preferable. In this case, the mating material is not particularly limited, and examples thereof include a sliding surface between the DLC material and the iron-based material or a sliding surface between the DLC material and the aluminum alloy material.
Here, the DLC material has a DLC film on the surface, and the DLC material constituting the film is amorphous mainly composed of carbon element, and the bonding form between carbons is a diamond structure (SP 3 bond). ) And graphite bonds (SP 2 bonds). Specifically, aC (amorphous carbon) consisting only of carbon elements, aC: H (hydrogen amorphous carbon) containing hydrogen, and some metal elements such as titanium (Ti) and molybdenum (Mo). MeC included in
一方、鉄基材料としては、例えば浸炭鋼SCM420やSCr420(JIS)などを挙げることができる。アルミニウム合金材料としては、ケイ素を4〜20質量%及び銅を1.0〜5.0質量%を含む亜共晶アルミニウム合金又は過共晶アルミニウム合金を用いることが好ましい。具体的にはAC2A、AC8A、ADC12、ADC14(JIS)などを挙げることができる。
また、前記DLC材料及び鉄基材料、あるいはDLC材料及びアルミニウム合金材料のそれぞれの表面粗さは、算術平均粗さRaで、0.1μm以下であることが摺動の安定性
の面から好適である。0.1μm以下であると局部的なスカッフィングが形成しにくく、摩擦係数の増大を抑制することができる。更に、上記DLC材料は、表面硬さが、マイクロビッカーズ硬さ(98mN荷重)でHv1000〜3500、厚さが0.3〜2.0μmであることが好ましい。
一方、前記鉄基材料は、表面硬さがロックウェル硬さ(Cスケール)でHRC45〜60であることが好ましい。この場合は、カムフォロワー部材のように700MPa程度の高面圧下の摺動条件においても、膜の耐久性を維持できるので有効である。
また、前記アルミニウム合金材料は、表面硬さがブリネル硬さHB80〜130であることが好ましい。
DLC材料の表面硬さ及び厚さが上記範囲にあると摩滅や剥離が抑制される。また、鉄基材料の表面硬さがHRC45以上であると、高面圧下で座屈し剥離するのを抑制することができる。一方、アルミニウム合金材料の表面硬さが上記範囲にあれば、アルミニウム合金の摩耗が抑制される。
On the other hand, examples of the iron base material include carburized steel SCM420 and SCr420 (JIS). As an aluminum alloy material, it is preferable to use a hypoeutectic aluminum alloy or a hypereutectic aluminum alloy containing 4 to 20% by mass of silicon and 1.0 to 5.0% by mass of copper. Specifically, AC2A, AC8A, ADC12, ADC14 (JIS), etc. can be mentioned.
The surface roughness of each of the DLC material and the iron base material, or the DLC material and the aluminum alloy material is preferably an arithmetic average roughness Ra of 0.1 μm or less from the viewpoint of sliding stability. is there. If it is 0.1 μm or less, local scuffing is difficult to form, and an increase in the friction coefficient can be suppressed. Further, the DLC material preferably has a surface hardness of microvickers hardness (98 mN load) of Hv 1000 to 3500 and a thickness of 0.3 to 2.0 μm.
On the other hand, the iron-based material preferably has a surface hardness of HRC45-60 in terms of Rockwell hardness (C scale). This case is effective because the durability of the film can be maintained even under sliding conditions under a high surface pressure of about 700 MPa as in a cam follower member.
The aluminum alloy material preferably has a surface hardness of Brinell hardness HB 80 to 130.
When the surface hardness and thickness of the DLC material are within the above ranges, abrasion and peeling are suppressed. Further, when the surface hardness of the iron-based material is HRC45 or more, it is possible to suppress buckling and peeling under high surface pressure. On the other hand, if the surface hardness of the aluminum alloy material is within the above range, the wear of the aluminum alloy is suppressed.
本発明の潤滑油組成物が適用される摺動部については、二つの金属表面が接触し、かつ少なくとも一方が低摩擦摺動材料を有する表面であればよく、特に制限はないが、例えば内燃機関の摺動部を好ましく挙げることができる。この場合は、従来に比べて極めて優れた低摩擦特性が得られ、省燃費効果が発揮されるので有効である。例えば、DLC部材としては、鉄鋼材料の基板にDLCをコーティングした円板状のシムやリフター冠面などが挙げられ、鉄基部材としては、低合金チルド鋳鉄、浸炭鋼又は調質炭素鋼、及びこれらの任意の組合せに係る材料を用いたカムロブなどが挙げられる。 The sliding part to which the lubricating oil composition of the present invention is applied is not particularly limited as long as two metal surfaces are in contact with each other and at least one of them has a low friction sliding material. The sliding part of an engine can be mentioned preferably. In this case, it is effective because a low friction characteristic which is extremely excellent as compared with the conventional case is obtained and a fuel saving effect is exhibited. For example, as the DLC member, a disk-shaped shim or lifter crown surface coated with DLC on a steel material substrate is exemplified, and as the iron base member, low alloy chilled cast iron, carburized steel or tempered carbon steel, and The cam lobe using the material which concerns on these arbitrary combinations is mentioned.
次に、本発明を実施例により更に詳細に説明するが、本発明はこれらの例によって何ら限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
実施例1〜6及び比較例1〜5
第1表に示す組成を有する潤滑油組成物を調製し、以下に示す摩擦特性試験を行い、摩擦係数を求めた。その結果を第2表に示す。
<摩擦特性試験>
往復動摩擦試験機(オプティマール社製SRV往復動摩擦試験機)を用いて、以下の方法により摩擦係数を測定した。
テストピースとして、DLCコーティングしたディスク(φ24mm×7.9mm)を用い、その上に試料油(潤滑油組成物)を数滴滴下する。SCM420製のシリンダー(φ15mm×22mm)を上記ディスク上部にセットした状態で、荷重400N,振幅1.5mm、周波数50Hz、温度80℃の条件で摩擦係数を求める。
Examples 1-6 and Comparative Examples 1-5
A lubricating oil composition having the composition shown in Table 1 was prepared, and the friction characteristic test shown below was conducted to obtain the friction coefficient. The results are shown in Table 2.
<Frictional property test>
The friction coefficient was measured by the following method using a reciprocating friction tester (SRV reciprocating friction tester manufactured by Optimar).
As a test piece, a DLC-coated disk (φ24 mm × 7.9 mm) is used, and several drops of sample oil (lubricating oil composition) are dropped on the disk. A friction coefficient is obtained under the conditions of a load of 400 N, an amplitude of 1.5 mm, a frequency of 50 Hz, and a temperature of 80 ° C. with an SCM420 cylinder (φ15 mm × 22 mm) set on the top of the disk.
潤滑油組成物の調製に用いた各成分は以下のとおりである。
潤滑油基油:水素化分解鉱油(100℃動粘度4.47mm2/s)
Caスルフォネート(1):Caスルフォネート(Ca含有量15.2質量%)
Caスルフォネート(2):Caスルフォネート(Ca含有量12.0質量%)
Caサリシレート(1):Caサリシレート(Ca含有量7.8質量%)
Caサリシレート(2):Caサリシレート(Ca含有量2.3質量%)
Caフェネート:Caフェネート(Ca含有量9.25質量%)
ホウ素未含有コハク酸イミド(1):前記(III)式で表されるホウ素未含有ポリブテニルコハク酸イミド(窒素含有量2.1質量%、ポリブテニル基数平均分子量1000)
ホウ素未含有コハク酸イミド(2):前記(II)式で表されるホウ素未含有ポリブテニルコハク酸イミド(窒素含有量0.97質量%、ポリブテニル基数平均分子量1300)
ホウ素含有コハク酸イミド:前記(III)式で表されるホウ素含有ポリブテニルコハク酸イミド(窒素含有量1.23質量%、ポリブテニル基数平均分子量1000)
ジアルキルジチオリン酸亜鉛(1):第2級アルキル型ジアルキルジチオリン酸亜鉛(リン含有量8.2質量%)
ジアルキルジチオリン酸亜鉛(2):第1級アルキル型ジアルキルジチオリン酸亜鉛(リン含有量7.4質量%)
硫黄系化合物:ポリサルファイド混合物(R−Sa−R,Rは炭素数12のアルキル基、aは2または3、硫黄含有量22.0質量%)
粘度指数向上剤:ポリメタクリレート(重量平均分子量 Mw=550,000)
流動点降下剤:ポリメタクリレート(重量平均分子量 Mw=69,000)
酸化防止剤(1):ジアルキルジフェニルアミン(窒素含有量4.62質量%)
酸化防止剤(2):4,4’−メチレンビス(2,6−ジ−Tert−ブチルフェノール)
防錆剤:N−アルキルベンゾトリアゾール
Each component used for the preparation of the lubricating oil composition is as follows.
Lubricating base oil: hydrocracked mineral oil (100 ° C. kinematic viscosity 4.47 mm 2 / s)
Ca sulfonate (1): Ca sulfonate (Ca content 15.2% by mass)
Ca sulfonate (2): Ca sulfonate (Ca content 12.0% by mass)
Ca salicylate (1): Ca salicylate (Ca content 7.8% by mass)
Ca salicylate (2): Ca salicylate (Ca content 2.3 mass%)
Ca phenate: Ca phenate (Ca content: 9.25% by mass)
Boron-free succinimide (1): Boron-free polybutenyl succinimide represented by the formula (III) (nitrogen content 2.1 mass%, polybutenyl group number average molecular weight 1000)
Boron-free succinimide (2): Boron-free polybutenyl succinimide represented by the formula (II) (nitrogen content 0.97 mass%, polybutenyl group number average molecular weight 1300)
Boron-containing succinimide: Boron-containing polybutenyl succinimide represented by the formula (III) (nitrogen content 1.23% by mass, polybutenyl group number average molecular weight 1000)
Zinc dialkyldithiophosphate (1): zinc secondary alkyl type dialkyldithiophosphate (phosphorus content 8.2% by mass)
Zinc dialkyldithiophosphate (2): primary alkyl-type zinc dialkyldithiophosphate (phosphorus content 7.4% by mass)
Sulfur-based compound: polysulfide mixture (R-S a -R, R is an alkyl group having 12 carbon atoms, a is 2 or 3, and sulfur content is 22.0% by mass)
Viscosity index improver: polymethacrylate (weight average molecular weight Mw = 550,000)
Pour point depressant: polymethacrylate (weight average molecular weight Mw = 69,000)
Antioxidant (1): Dialkyldiphenylamine (nitrogen content 4.62% by mass)
Antioxidant (2): 4,4′-methylenebis (2,6-di-tert-butylphenol)
Rust inhibitor: N-alkylbenzotriazole
なお、DLCコーティングしたディスクは以下のもの用いた。
DLC:水素20%含有DLC
DLC W:水素20%含有(タングステン添加)DLC
The following DLC-coated discs were used.
DLC: DLC containing 20% hydrogen
DLC W: 20% hydrogen (tungsten added) DLC
第2表の結果から,本発明の潤滑油組成物である実施例1〜6の組成物は,摩擦係数が低く優れている。一方,比較例1および2は,それぞれ金属系清浄剤,無灰系分散剤として,Caフェネート,硼素含有コハク酸イミドが配合されるため摩擦係数が高い。比較例3は、硫黄系化合物が配合されないため、摩擦係数が高い。比較例4、5は、リン量またはカルシウム量が過剰に存在するため、摩擦係数が高くなっている。 From the results in Table 2, the compositions of Examples 1 to 6, which are the lubricating oil compositions of the present invention, have a low coefficient of friction and are excellent. On the other hand, Comparative Examples 1 and 2 have a high coefficient of friction because Ca phenate and boron-containing succinimide are blended as a metallic detergent and an ashless dispersant, respectively. Since the comparative example 3 does not contain a sulfur compound, the friction coefficient is high. In Comparative Examples 4 and 5, the amount of phosphorus or calcium is excessive, and thus the friction coefficient is high.
本発明の潤滑油組成物は、DLC材料のような低摩擦摺動材料からなる摺動面に適用され、優れた低摩擦特性を付与することができ、特に内燃機関に適用した場合に、省燃費効果を付与することができる。 The lubricating oil composition of the present invention is applied to a sliding surface made of a low-friction sliding material such as a DLC material and can impart excellent low-friction characteristics, particularly when applied to an internal combustion engine. A fuel efficiency effect can be imparted.
Claims (5)
組成物全量基準の配合量が、(A)成分がアルカリ土類金属濃度換算で、0.05〜0.25質量%、(B)成分が窒素濃度換算で、0.03〜0.50質量%、(C)成分がリン濃度換算で0.01〜0.12質量%、(D)成分が硫黄濃度換算で0.02〜2.0質量%であって、
アルカリ土類金属フェネート系清浄剤がアルカリ土類金属濃度換算で0.10質量%以下、ホウ素含有コハク酸イミドが窒素濃度換算で、0.04質量%以下である、低摩擦摺動材料に用いられる潤滑油組成物。
R 1 −Sn−R 2 (I)
(式中、nは1〜4から選ばれる整数を表し、R 1 及びR 2 は、それぞれ独立にアルキル基またはアラルキル基を表す。) Boron-free succinic acid having (A) alkaline earth metal salicylate and / or alkaline earth metal sulfonate detergent, (B) alkenyl group or alkyl group having a number average molecular weight of 500 to 4000 imide type ashless dispersant, a lubricating oil composition prepared by blending a sulfur-based compound represented by (C) zinc dialkyldithiophosphate and (D) the following formula (I),
The blending amount based on the total amount of the composition is 0.05 to 0.25% by mass in terms of alkaline earth metal concentration (A) component, and 0.03 to 0.50 mass in terms of nitrogen concentration in component (B). %, (C) component is 0.01-0.12 mass% in terms of phosphorus concentration, (D) component is 0.02-2.0 mass% in terms of sulfur concentration,
The alkaline earth metal phenate detergent is 0.10% by mass or less in terms of alkaline earth metal concentration, and the boron-containing succinimide is 0.04% by mass or less in terms of nitrogen concentration. Lubricating oil composition.
R 1 —Sn—R 2 (I)
(In the formula, n represents an integer selected from 1 to 4, and R 1 and R 2 each independently represents an alkyl group or an aralkyl group.)
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CN201080041843.6A CN102597194B (en) | 2009-09-15 | 2010-09-03 | Lubricating oil composition |
KR1020127006495A KR20120080173A (en) | 2009-09-15 | 2010-09-03 | Lubricant composition |
PCT/JP2010/065136 WO2011033953A1 (en) | 2009-09-15 | 2010-09-03 | Lubricant composition |
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