JP6472262B2 - 内燃機関用潤滑油組成物 - Google Patents
内燃機関用潤滑油組成物 Download PDFInfo
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- JP6472262B2 JP6472262B2 JP2015026905A JP2015026905A JP6472262B2 JP 6472262 B2 JP6472262 B2 JP 6472262B2 JP 2015026905 A JP2015026905 A JP 2015026905A JP 2015026905 A JP2015026905 A JP 2015026905A JP 6472262 B2 JP6472262 B2 JP 6472262B2
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- 239000010687 lubricating oil Substances 0.000 title claims description 61
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- 229910052751 metal Inorganic materials 0.000 claims description 44
- 239000002184 metal Substances 0.000 claims description 44
- 125000000217 alkyl group Chemical group 0.000 claims description 41
- 125000004432 carbon atom Chemical group C* 0.000 claims description 37
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- 125000003342 alkenyl group Chemical group 0.000 claims description 23
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 21
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- 238000001704 evaporation Methods 0.000 claims description 16
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 9
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- DIOYAVUHUXAUPX-KHPPLWFESA-N Oleoyl sarcosine Chemical group CCCCCCCC\C=C/CCCCCCCC(=O)N(C)CC(O)=O DIOYAVUHUXAUPX-KHPPLWFESA-N 0.000 description 3
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- XYRMLECORMNZEY-UHFFFAOYSA-B [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S Chemical compound [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S XYRMLECORMNZEY-UHFFFAOYSA-B 0.000 description 3
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 3
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- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 3
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- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 3
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 description 3
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- ZRNBEAAEJJLWTJ-KHPPLWFESA-N 3-[methyl-[(z)-octadec-9-enoyl]amino]propanoic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)N(C)CCC(O)=O ZRNBEAAEJJLWTJ-KHPPLWFESA-N 0.000 description 2
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- 125000000755 henicosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- AEIJTFQOBWATKX-UHFFFAOYSA-N octane-1,2-diol Chemical compound CCCCCCC(O)CO AEIJTFQOBWATKX-UHFFFAOYSA-N 0.000 description 1
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- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
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- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 1
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- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
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- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
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- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
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- 108700004121 sarkosyl Proteins 0.000 description 1
- CDAISMWEOUEBRE-UHFFFAOYSA-N scyllo-inosotol Natural products OC1C(O)C(O)C(O)C(O)C1O CDAISMWEOUEBRE-UHFFFAOYSA-N 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
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- 239000010802 sludge Substances 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
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- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 125000002469 tricosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
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Classifications
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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
-
- 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
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic 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
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M133/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
-
- 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
- C10M139/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00
-
- 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
- C10M141/12—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 compound containing atoms of elements not provided for in groups C10M141/02 - C10M141/10
-
- 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
- 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
-
- 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
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
- C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
-
- 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
- C10M2203/1025—Aliphatic fractions used as base material
-
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Description
これらの中で、低燃費エンジン油の使用は、費用対効果に優れていることから、市場においても一般的になりつつある。エンジン油による低燃費対策としてはピストン系や軸受部などの流体潤滑条件下における摩擦損失の低減を意図した低粘度化が検討されており、また、動弁系などの混合潤滑下および境界潤滑下における摩擦損失の低減を意図した有機モリブデン化合物のような摩擦低減剤の添加が提案されている。
このような省燃費エンジン油としては、例えば、特許文献1には、100℃での動粘度が2〜8mm2/sで、芳香族含有量が15質量%の基油に特定の添加剤(アルカリ土類金属サリシレート系清浄剤、モリブデンジチオカーバメート系摩擦低減剤等)を特定量含有するエンジン油組成物が、また、特許文献2には、100℃での動粘度が3〜8mm2/sのエステル系潤滑油基油を含有する潤滑油基油に、モリブデン系摩擦調整剤またはエステル系やアミン系の無灰系摩擦調整剤と過塩基性Caサリシレートを配合した内燃機関用潤滑油組成物が、さらに、特許文献3には、硫化オキシモリブデンジチオカーバメートと酸アミド化合物及び脂肪族部分エステル化合物及び/または脂肪族アミン化合物などの無灰系摩擦調整剤を組み合わせて配合した内燃機関用潤滑油組成物が提案されている。
一方、サルコシンやアスパラギン酸誘導体は無灰系摩擦調整剤として知られているが(例えば、特許文献4〜6)、内燃機関用潤滑油組成物に配合することも、モリブデン系摩擦調整剤と併用することにより摩擦低減の相乗効果を奏することも知られておらず、当業者がこの作用効果を予測できるものではなかった。
[1](A)100℃における動粘度が2.0〜5.0mm2/sの潤滑油基油に、(B)モリブデン系摩擦調整剤を組成物全量基準でモリブデン量として0.005〜0.2質量%、(C)サリシレート系金属系清浄剤を組成物全量基準で金属量として0.01〜1質量%および(D)炭素数15〜24のアルキル基又はアルケニル基又はアシル基を有するアミノ酸及び/又はその誘導体から選ばれる1種類以上の化合物を0.01〜10質量%含有する内燃機関用潤滑油組成物。
[2]前記(C)サリシレート系金属系清浄剤が、ホウ素を含有するサリシレート系金属系清浄剤である上記[1]に記載の内燃機関用潤滑油組成物。
[3]150℃におけるHTHS粘度が1.9〜2.7mPa/sである上記[1]又は[2]に記載の内燃機関用潤滑油組成物。
[4]150℃におけるHTHS粘度が1.9〜2.4mPa/sである上記[1]〜[3]のいずれか1項に記載の内燃機関用潤滑油組成物。
[5]NOACK蒸発量が15質量%以下である上記[1]〜[4]のいずれか1項に記載の内燃機関用潤滑油組成物。
[6](E)ジアルキルジチオリン酸亜鉛摩耗防止剤を組成物全量基準で、リン量として、0.02〜0.20質量%含有する上記[1]〜[5]のいずれか1項に記載の内燃機関用潤滑油組成物。
本発明における潤滑油基油は、100℃における動粘度が2.0〜5.0mm2/sの潤滑油基油であれば、特に限定されるものではなく、通常の内燃機関用潤滑油組成物の潤滑油基油として用いられているものであれば、鉱油、合成油を問わず使用することができる。
この潤滑油基油の100℃での動粘度は、2.5mm2/s以上、より好ましくは3.0mm2/s以上、さらに好ましくは3.5mm2/s以上、特に好ましくは3.8mm2/s以上、最も好ましくは4.0mm2/s以上である。また、4.5mm2/s以下であることが好ましく、4.3mm2/s以下であることがさらに好ましい。
100℃における動粘度が2.0mm2/s未満の場合、潤滑箇所での油膜形成が不十分となるため潤滑性に劣り、また潤滑油基油の蒸発損失が大きくなる。一方、5.0mm2/sを超えると省燃費効果が小さくなり、また低温粘度特性が悪化する。
なお、本発明において、100℃での動粘度とは、ASTM D−445に規定される100℃での動粘度である。
鉱油系基油としては、原油を常圧蒸留及び減圧蒸留して得られた潤滑油留分を、溶剤脱れき、溶剤抽出、水素化分解、溶剤脱ろう、接触脱ろう、水素化精製、硫酸洗浄及び白土処理等の精製処理等を適宜組み合わせて精製したパラフィン系、ナフテン系等の潤滑油基油等が例示できる。
また、この基油は、API(米国石油学会)による基油分類に基づく分類でグループIII以上に分類されるもの、およびワックスを異性化した基油などが好ましい。
この基油の製造方法については、特に制限はないが、原油を常圧蒸留して得られる常圧残油を、脱硫、水素化分解し、設定された粘度グレードに分留、あるいはその残油を溶剤脱ろう、あるいは接触脱ろうし、必要であればさらに、溶剤抽出、水素化し、基油としたものが好ましい。なかでも接触脱ろうして得られる基油が好ましい。
なお、上記%CAは、ASTM D3238−85に準拠した方法(n−d−M環分析)で測定した値を意味する。
硫黄分の測定法に特に制限はないが、JIS K2541−1996等が一般に使用される。
本発明におけるモリブデン系摩擦調整剤としては、例えば、ジチオカルバミン酸モリブデン(MoDTC)およびジチオリン酸モリブデン(MoDTP)等の硫黄を含有する有機モリブデン系摩擦調整剤を挙げることができる。ジチオカルバミン酸モリブデンとしては、具体的には下記の一般式(1)で表される化合物を例示することができる。また、ジチオリン酸モリブデンとしては、具体的には下記の一般式(2)で表される化合物を例示することができる。
本発明でいうサリシレート系金属系清浄剤としては、潤滑油に通常用いられる任意の化合物が使用可能であり、例えば、直鎖状もしくは分岐鎖状の炭化水素基を有し、さらにOH基および/またはカルボニル基を有する油溶性金属塩の過塩基性化合物を用いることができる。また、アルカリ土類金属サリシレートの過塩基性金属塩、アルカリ土類金属水酸化物または酸化物、必要によりホウ酸または無水ホウ酸を反応させることによって得ることができる過塩基性金属塩を用いることができる。サリシレート系金属系清浄剤としては、ホウ素を含有するサリシレート系金属系清浄剤が特に好ましい。アルカリ土類金属としては、マグネシウム、カルシウム、バリウムなどがあげられるが、カルシウムが好ましい。過塩基性金属塩としては、アルカリ土類金属ホウ酸塩またはアルカリ土類金属炭酸塩で過塩基化されたOH基および/またはカルボニル基を含有する化合物の油溶性金属塩を用いることがより好ましい。特に、省燃費性に優れる点から、アルカリ土類金属サリシレートを用いることが好ましく、アルカリ土類金属ホウ酸塩で過塩基化されたアルカリ土類金属サリシレートを用いることがより好ましい。
なお、本発明にいう金属比とは、金属系清浄剤における金属元素の価数×金属元素含有量(mol%)/せっけん基含有量(mol%)で表され、金属元素とは、カルシウム、マグネシウム等、せっけん基とはスルホン酸基やフェノール基、サリチル酸基等を意味する。
本発明においては、無灰系摩擦調整剤として、炭素数15〜24のアルキル基又はアルケニル基又はアシル基を有するアミノ酸及び/又はその誘導体を少なくとも1種類以上含有させるが、例えば、この化合物としては、次の一般式(3)に示す化合物を挙げることができる。
R11のアルキル基は直鎖状又は分岐鎖状又は環状構造を含むものでもよく、炭素原子はヘテロ原子で置換されていてもよく、水酸基、カルボキシル基、アミノ基などの官能基で修飾されていてもよい。摩擦低減効果や基油への溶解性などの観点から、炭素数2以下のアルキル基がより好ましく、炭素数1以下がさらに好ましく、水素が特に好ましい。
R12は、貯蔵安定性などの点から、炭素数4以下のアルキル基がより好ましく、炭素数3以下がさらに好ましく、炭素数2以下が特に好ましく、最も好ましくは水素である。
活性水素を有する官能基である水酸基を有する炭化水素としては、具体的には、例えば、エチレングリコール、プロピレングリコール、1,4‐ブタンジオール、1,2‐ブタンジオール、ネオペンチルグリコール、1,6‐ヘキサンジオール、1,2‐オクタンジオール、1,8‐オクタンジオール、イソプレングリコール、3‐メチル‐1,5‐ペンタンジオール、ソルバイト、カテコール、レゾルシン、ヒドロキノン、ビスフェノールA、ビスフェノールF、水添ビスフェノールA、水添ビスフェノールF、ダイマージオール等の2価のアルコール;グリセリン、2‐(ヒドロキシメチル)‐1,3‐プロパンジオール、1,2,3‐ブタントリオール、1,2,3‐ペンタントリオール、2‐メチル‐1,2,3‐プロパントリオール、2‐メチル‐2,3,4‐ブタントリオール、2‐エチル‐1,2,3‐ブタントリオール、2,3,4‐ペンタントリオール、2,3,4‐ヘキサントリオール、4‐プロピル‐3,4,5‐ヘプタントリオール、2,4‐ジメチル‐2,3,4‐ペンタントリオール、1,2,4‐ブタントリオール、1,2,4‐ペンタントリオール、トリメチロールエタン、トリメチロールプロパン等の3価アルコール;ペンタエリスリトール、エリスリトール、1,2,3,4‐ペンタンテトロール、2,3,4,5‐ヘキサンテトロール、1,2,4,5‐ペンタンテトロール、1,3,4,5‐ヘキサンテトロール、ジグリセリン、ソルビタン等の4価アルコール;アドニトール、アラビトール、キシリトール、トリグリセリン等の5価アルコール;ジペンタエリスリトール、ソルビトール、マンニトール、イジトール、イノシトール、ダルシトール、タロース、アロース等の6価アルコール;ポリグリセリン又はこれらの脱水縮合物等が挙げられる。
金属塩としては一般式(3)のなかでも一般式(3)の−COXがカルボキシ基構造のカルボン酸塩が好ましい。
なお、一般式(3)で表される化合物の好適な例として、N‐アシルサルコシン、なかでもR9が炭素数18のアシル基、R10がメチル基、R11が水素、Xが水酸基、nが0であるN‐オレオイルサルコシンや、R9が炭素数18のアシル基、R10がメチル基、R11が水素、R12が水素、Xが水酸基、nが1であるN‐オレオイル‐N‐メチル‐β‐アラニンが挙げられる。
本発明の内燃機関用潤滑油組成物には、上記添加剤以外にさらに、摩耗防止剤としてジアルキルジチオリン酸亜鉛(ZnDTP)を添加することが好ましいが、例えば、この化合物としては、次の一般式(4)に示す化合物を挙げることができる。
本発明においては、これらのジアルキルジチオリン酸亜鉛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が、第1級アルキル基を有するジチオリン酸亜鉛(プライマリーZnDTP)又は第2級アルキル基を含有するジチオリン酸亜鉛(セカンダリーZnDTP)が好ましく、特には、第2級のアルキル基のジチオリン酸亜鉛を主成分とするものが、耐摩耗性を高めるため好ましい。
また、この粘度指数向上剤は、ディーゼルインジェクター法におけるPSSI(パーマネントシアスタビリティインデックス)が、30以下のものが好ましい。PSSIが30を超える場合にはせん断安定性が悪く、使用後の動粘度やHTHS粘度を一定以上に保つために、初期の省燃費性が悪化するおそれがある。
なお、ここでいう「ディーゼルインジェクター法におけるPSSI」とは、ASTM D6022−01(Standard Practice for Calculation of Permanent Shear Stability Index)に準拠し、ASTM D6278−02(Test Method for Shear Stability of Polymer Containing Fluids Using a European Diesel Injector Apparatus)により測定されたデータに基づき計算された、ポリマーの永久せん断安定性指数(Permanent Shear Stability Index)を意味する。
この清浄分散剤は、モノタイプ又はビスタイプのコハク酸イミドであることが好ましく、ビスタイプのコハク酸イミドがより好ましい。また、ホウ素非含有のビスタイプのコハク酸イミドであることが特に好ましい。
さらに、この清浄分散剤は、分子量1000以上であることが好ましく、より好ましくは5000以上、より好ましくは7000以上、さらに好ましくは9000以上であることが好ましい。また、分子量30000以下であることが好ましく、25000以下であることが好ましく、分子量20000以下であることがより好ましい。分子量1000以下の場合は、清浄性が不十分となるおそれがあり、一方、分子量30000を超える場合は、エンジン油組成物の省燃費性が大幅に悪化するおそれがある。
また、清浄分散剤のN含有量は、0.1以上であることが好ましく、より好ましくは0.3以上、より好ましくは0.4以上、さらに好ましくは0.5以上であることが好ましい。また、2.0以下であることが好ましく、1.0以下であることが好ましく、0.8以下であることがより好ましい。N含有量0.1以下の場合は、清浄性が不十分となるおそれがあり、一方、N含有量2.0を超える場合は、エンジン油組成物の省燃費性が大幅に悪化するおそれがある。
錆止め剤としては、例えば、アルケニルコハク酸、アルケニルコハク酸エステル、多価アルコールエステル、石油スルホネート、ジノニルナフタレンスルホネート等が使用できる。
腐食防止剤としては、例えば、ベンゾトリアゾール系、チアジアゾール系、イミダゾール系の化合物等が使用できる。
また、消泡剤としては、例えば、ジメチルシリコーンやフルオロシリコーン等のシリコーン化合物類が使用できる。
(A)潤滑油基油
表1に示す性状を有する水素化分解潤滑油基油を表2に示す割合で配合して用いた。
ジチオカルバミン酸モリブデン:一般式(1)において、R1〜R4は、炭素数8又は13のアルキル基、a及びbは2、モリブデン元素の濃度は10質量%、硫黄分11質量%
(C)サリシレート系金属系清浄剤
(C−1)過塩基性Caサリシレート:金属比2.3、アルキル基の炭素数14〜18、Ca含有量6.2質量%、塩基価180mgKOH/g
(C−2)過塩基性ホウ酸Caサリシレート:金属比2.5、アルキル基の炭素数14〜18、Ca含有量6.8質量%、B含有量2.7質量%、塩基価190mgKOH/g
(D−1)N−オレオイル‐N‐メチル‐β‐アラニン
(D−2)オレオイルサルコシン
(D−3)N‐ラウロイル‐N‐メチル‐β‐アラニン
(D−4)N‐ラウロイルサルコシン
(E−1)ZnDTP:一級アルキル基、炭素数8、Zn含有量9.0質量%、P含有量7.4質量%、S含有量15質量%
(E−2)ZnDTP:二級アルキル基、炭素数4及び6、Zn含有量8.0質量%、P含有量7.2質量%、S含有量15質量%
(F−1)非分散型PMA系粘度指数向上剤(Mw=400,000,PSSI=7)
(F−2)ポリブテニルコハク酸イミド:分子量9000、N含有量0.7質量%
(F−3)酸化防止剤、消泡剤(ジメチルシリコーン)など
使用エンジン:3L、DOHCエンジン
油温:80℃
回転数:550rpm
Claims (4)
- (A)100℃における動粘度が2.0〜5.0mm2/sの潤滑油基油に、(B)モリブデン系摩擦調整剤を組成物全量基準でモリブデン量として0.03〜0.2質量%、(C)サリシレート系金属系清浄剤を組成物全量基準で金属量として0.01〜1質量%および(D)炭素数15〜24のアルキル基又はアルケニル基又はアシル基を有するアミノ酸及び/又はその誘導体から選ばれる1種類以上の化合物を0.01〜10質量%含有する、150℃におけるHTHS粘度が1.9〜2.4mPa・sである内燃機関用潤滑油組成物。
- 前記(C)サリシレート系金属系清浄剤が、ホウ素を含有するサリシレート系金属系清浄剤である請求項1に記載の内燃機関用潤滑油組成物。
- NOACK蒸発量が15質量%以下である請求項1又は2に記載の内燃機関用潤滑油組成物。
- (E)ジアルキルジチオリン酸亜鉛摩耗防止剤を組成物全量基準で、リン量として、0.02〜0.20質量%含有する請求項1〜3のいずれか1項に記載の内燃機関用潤滑油組成物。
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