JP2009108157A - Lubricant composition for internal combustion engine - Google Patents
Lubricant composition for internal combustion engine Download PDFInfo
- Publication number
- JP2009108157A JP2009108157A JP2007280403A JP2007280403A JP2009108157A JP 2009108157 A JP2009108157 A JP 2009108157A JP 2007280403 A JP2007280403 A JP 2007280403A JP 2007280403 A JP2007280403 A JP 2007280403A JP 2009108157 A JP2009108157 A JP 2009108157A
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- Japan
- Prior art keywords
- mass
- content
- acid
- boron
- molybdenum
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 65
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 12
- 239000000314 lubricant Substances 0.000 title abstract 5
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims abstract description 51
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 28
- 239000011593 sulfur Substances 0.000 claims abstract description 28
- 229960002317 succinimide Drugs 0.000 claims abstract description 20
- 239000002199 base oil Substances 0.000 claims abstract description 18
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 11
- 150000002148 esters Chemical class 0.000 claims abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 11
- 239000011574 phosphorus Substances 0.000 claims abstract description 11
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052796 boron Inorganic materials 0.000 claims abstract description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 10
- 239000011733 molybdenum Substances 0.000 claims abstract description 10
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 10
- 150000001412 amines Chemical class 0.000 claims abstract description 9
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 9
- 150000007519 polyprotic acids Polymers 0.000 claims abstract description 6
- 239000010687 lubricating oil Substances 0.000 claims description 36
- 239000003921 oil Substances 0.000 claims description 23
- 239000002480 mineral oil Substances 0.000 claims description 15
- 235000010446 mineral oil Nutrition 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 239000005078 molybdenum compound Substances 0.000 claims description 10
- 150000002752 molybdenum compounds Chemical class 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical class OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims 1
- 239000002956 ash Substances 0.000 abstract description 13
- 230000003647 oxidation Effects 0.000 abstract description 13
- 238000007254 oxidation reaction Methods 0.000 abstract description 13
- 239000003112 inhibitor Substances 0.000 abstract description 7
- 239000010705 motor oil Substances 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011701 zinc Substances 0.000 abstract description 2
- 229910052725 zinc Inorganic materials 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 2
- 230000003405 preventing effect Effects 0.000 abstract 1
- -1 diesel engines Substances 0.000 description 29
- 238000012360 testing method Methods 0.000 description 17
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 239000002253 acid Substances 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- 230000003749 cleanliness Effects 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 125000003342 alkenyl group Chemical group 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- BRESEFMHKFGSDY-UHFFFAOYSA-N molybdenum;pyrrolidine-2,5-dione Chemical compound [Mo].O=C1CCC(=O)N1 BRESEFMHKFGSDY-UHFFFAOYSA-N 0.000 description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 235000011187 glycerol Nutrition 0.000 description 6
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 6
- 235000013772 propylene glycol Nutrition 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000003607 modifier Substances 0.000 description 5
- 150000002978 peroxides Chemical class 0.000 description 5
- 229920000768 polyamine Polymers 0.000 description 5
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 description 4
- BTVWZWFKMIUSGS-UHFFFAOYSA-N 2-methylpropane-1,2-diol Chemical compound CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 4
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 229960002645 boric acid Drugs 0.000 description 4
- 235000010338 boric acid Nutrition 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 150000002751 molybdenum Chemical class 0.000 description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 239000002530 phenolic antioxidant Substances 0.000 description 4
- 230000002265 prevention Effects 0.000 description 4
- 239000000600 sorbitol Substances 0.000 description 4
- 229960005137 succinic acid Drugs 0.000 description 4
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 4
- 239000001993 wax Substances 0.000 description 4
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 3
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000010710 diesel engine oil Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000006078 metal deactivator Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 239000001384 succinic acid Substances 0.000 description 3
- 229940014800 succinic anhydride Drugs 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- LMMTVYUCEFJZLC-UHFFFAOYSA-N 1,3,5-pentanetriol Chemical compound OCCC(O)CCO LMMTVYUCEFJZLC-UHFFFAOYSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 229940035437 1,3-propanediol Drugs 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- BVUXDWXKPROUDO-UHFFFAOYSA-N 2,6-di-tert-butyl-4-ethylphenol Chemical compound CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BVUXDWXKPROUDO-UHFFFAOYSA-N 0.000 description 2
- SZSSMFVYZRQGIM-UHFFFAOYSA-N 2-(hydroxymethyl)-2-propylpropane-1,3-diol Chemical compound CCCC(CO)(CO)CO SZSSMFVYZRQGIM-UHFFFAOYSA-N 0.000 description 2
- SZAQZZKNQILGPU-UHFFFAOYSA-N 2-[1-(2-hydroxy-3,5-dimethylphenyl)-2-methylpropyl]-4,6-dimethylphenol Chemical compound C=1C(C)=CC(C)=C(O)C=1C(C(C)C)C1=CC(C)=CC(C)=C1O SZAQZZKNQILGPU-UHFFFAOYSA-N 0.000 description 2
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 2
- HEBKCHPVOIAQTA-QWWZWVQMSA-N D-arabinitol Chemical compound OC[C@@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-QWWZWVQMSA-N 0.000 description 2
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 206010016717 Fistula Diseases 0.000 description 2
- QCNWZROVPSVEJA-UHFFFAOYSA-N Heptadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCC(O)=O QCNWZROVPSVEJA-UHFFFAOYSA-N 0.000 description 2
- 229930195725 Mannitol Natural products 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001565 benzotriazoles Chemical class 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
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- 229940105990 diglycerin Drugs 0.000 description 2
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- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
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- 238000004519 manufacturing process Methods 0.000 description 2
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- KHYKFSXXGRUKRE-UHFFFAOYSA-J molybdenum(4+) tetracarbamodithioate Chemical compound C(N)([S-])=S.[Mo+4].C(N)([S-])=S.C(N)([S-])=S.C(N)([S-])=S KHYKFSXXGRUKRE-UHFFFAOYSA-J 0.000 description 2
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- 239000002904 solvent Substances 0.000 description 2
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- XQESJWNDTICJHW-UHFFFAOYSA-N 2-[(2-hydroxy-5-methyl-3-nonylphenyl)methyl]-4-methyl-6-nonylphenol Chemical compound CCCCCCCCCC1=CC(C)=CC(CC=2C(=C(CCCCCCCCC)C=C(C)C=2)O)=C1O XQESJWNDTICJHW-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Lubricants (AREA)
Abstract
Description
本発明は、内燃機関用潤滑油組成物に関し、詳しくは特定の添加剤を基油に所定量配合した、優れた高温清浄性および摩耗防止性を有する内燃機関用潤滑油組成物に関する。 The present invention relates to a lubricating oil composition for an internal combustion engine, and more particularly to a lubricating oil composition for an internal combustion engine having a specific additive added to a base oil in a predetermined amount and having excellent high-temperature cleanability and wear resistance.
従来のエンジン油には、摩耗防止剤、金属系清浄剤、無灰分散剤、酸化防止剤などの種々の添加剤が配合されている。近年、自動車には排出ガス後処理装置である酸化触媒、ＮＯｘ還元触媒、ディーゼルパティキュレートフィルタ(DPF)が装着されるようになった。そして、これら触媒やフィルタの寿命延長のために、エンジン油中の硫酸灰分量、リン、硫黄(SAPSと略す：Sulfated Ash, Phosphorus and Sulfurの頭文字からなる用語)の低減が求められ、低リン低硫黄低灰油(Low SAPS油)が開発されるようになった(特許文献１又は２)。しかしながら、SAPSフリーのエンジン油に関しては、摩耗防止性、清浄性、酸化安定性等の低下が懸念され、実用に適さないと考えられてきた。
本発明の課題は、摩耗防止剤であるジアルキルジチオリン酸亜鉛(ZDTP)および金属系清浄剤を含有しなくても、エンジン油として要求される酸化安定性、摩耗防止性、清浄性を有するSAPSが低減された内燃機関用潤滑油組成物を提供することにある。
本発明の別の課題は、リン、金属あるいは硫黄のいずれか又は全部を低減又は実質的に含有させなくても高温清浄性に極めて優れ、その特性維持を更に向上させた内燃機関用潤滑油組成物を提供することにある。
The subject of the present invention is that SAPS having oxidation stability, antiwear properties, and cleanliness required as engine oils without containing zinc antialkyl dialkyldithiophosphate (ZDTP) and metallic detergents. An object of the present invention is to provide a reduced lubricating oil composition for an internal combustion engine.
Another object of the present invention is to provide a lubricating oil composition for an internal combustion engine that is extremely excellent in high-temperature cleanliness and further improves the maintenance of its properties even if it does not contain or substantially contain any or all of phosphorus, metal, or sulfur. To provide things.
本発明によれば、フェノール系及びアミン系から選ばれる少なくとも１種の無灰酸化防止剤(A)(以下、(A)成分ということがある)１〜１２質量%と、ビスタイプコハク酸イミド系無灰分散剤(B)(以下、(B)成分ということがある)１〜１０質量%と、ホウ素変性コハク酸イミド系無灰分散剤(C)(以下、(C)成分ということがある)２〜１０質量%とを含み、鉱油及び／又は合成油からなる基油により全量を１００質量％とした潤滑油組成物であって、硫酸灰分量が０．２質量%以下、リン含量が０．０１質量％未満、硫黄含量が０．１質量%以下、ホウ素含量が０．０５〜０．０８質量%である内燃機関用潤滑油組成物が提供される。
また本発明によれば、(A)成分１〜１２質量%と、(B)成分１〜１０質量%と、(C)成分２〜１０質量%と、多価アルコール及び多塩基酸の反応により得られたエステル(D)(以下、(D)成分ということがある)０．１〜５質量%及び／又は有機モリブデン化合物(E)（以下(E)成分ということがある）をモリブデン換算で０．００５〜０．０８質量％とを含み、鉱油及び／又は合成油からなる基油により全量を１００質量％とした潤滑油組成物であって、硫酸灰分量が０．２質量%以下、リン含量が０．０１質量％未満、硫黄含量が０．１質量%以下、ホウ素含量が０．０５〜０．０８質量%である内燃機関用潤滑油組成物が提供される。
According to the present invention, 1 to 12% by mass of at least one ashless antioxidant (A) (hereinafter sometimes referred to as component (A)) selected from phenol and amine, and bis-type succinimide Ashless dispersant (B) (hereinafter sometimes referred to as component (B)) 1 to 10% by mass, boron-modified succinimide-based ashless dispersant (C) (hereinafter sometimes referred to as component (C)) A lubricating oil composition containing 2 to 10% by mass and made up to 100% by mass with a base oil composed of mineral oil and / or synthetic oil, the sulfated ash content is 0.2% by mass or less, and the phosphorus content is 0 Provided is a lubricating oil composition for an internal combustion engine that is less than 0.01 mass%, has a sulfur content of 0.1 mass% or less, and has a boron content of 0.05 to 0.08 mass%.
Moreover, according to this invention, (A) component 1-12 mass%, (B) component 1-10 mass%, (C) component 2-10 mass%, and reaction of a polyhydric alcohol and a polybasic acid are used. The obtained ester (D) (hereinafter sometimes referred to as component (D)) 0.1 to 5% by mass and / or organic molybdenum compound (E) (hereinafter sometimes referred to as component (E)) in terms of molybdenum A lubricating oil composition comprising 0.005 to 0.08 mass% and a base oil composed of mineral oil and / or synthetic oil and having a total amount of 100 mass%, wherein the sulfated ash content is 0.2 mass% or less, Provided is a lubricating oil composition for an internal combustion engine having a phosphorus content of less than 0.01 mass%, a sulfur content of 0.1 mass% or less, and a boron content of 0.05 to 0.08 mass%.
本発明の内燃機関用潤滑油組成物は、高温清浄性および摩耗防止性に優れるだけでなく、リン、金属、硫黄による排出ガス後処理装置への影響懸念を低減又は払拭することができ、二輪車及び四輪車用ガソリンエンジン、ディーゼルエンジン、ガスエンジン等の排出ガス後処理装置を装着したエンジン用に好適に用いることができる。また、酸化安定性にも優れ、長期の使用にも耐えうるので、排出ガス後処理装置である酸化触媒やＮＯｘ還元触媒の被毒を防止し、かつDPFにおける灰分堆積を防止することが可能である。
従って、本発明の組成物は、例えば、自動又は手動変速機油、湿式ブレーキ油、油圧作動油、タービン油、圧縮機油、軸受油、冷凍機油等の各種潤滑油への適用も可能である。
The lubricating oil composition for an internal combustion engine of the present invention is not only excellent in high-temperature cleanability and wear resistance, but also can reduce or eliminate the concern about the influence on exhaust gas aftertreatment devices caused by phosphorus, metal, and sulfur. And it can be used suitably for engines equipped with exhaust gas aftertreatment devices such as gasoline engines for four-wheeled vehicles, diesel engines, and gas engines. In addition, because it has excellent oxidation stability and can withstand long-term use, it is possible to prevent poisoning of oxidation catalysts and NOx reduction catalysts that are exhaust gas aftertreatment devices, and to prevent ash accumulation in DPF. is there.
Therefore, the composition of the present invention can be applied to various lubricating oils such as automatic or manual transmission oil, wet brake oil, hydraulic hydraulic oil, turbine oil, compressor oil, bearing oil, and refrigeration oil.
以下、本発明を更に詳細に説明する。
本発明に用いる基油は、通常の潤滑油に使用される鉱油及び／又は合成油が使用できる。
鉱油としては、具体的には、原油を常圧蒸留して得られる常圧残油を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、水素化精製等の処理を１つ以上行って精製したもの、あるいはワックス異性化鉱油、フィッシャートロプシュプロセス等により製造されるGTL WAX(ガストゥリキッドワックス)を異性化する手法で製造される潤滑油基油が例示できる。
Hereinafter, the present invention will be described in more detail.
As the base oil used in the present invention, mineral oils and / or synthetic oils used for ordinary lubricating oils can be used.
Specifically, as mineral oil, a lubricating oil fraction obtained by distillation under reduced pressure of atmospheric residual oil obtained by atmospheric distillation of crude oil can be desolvated, solvent extracted, hydrocracked, and solvent dewaxed. Lubricating oil produced by isomerizing GTL WAX (Gas Liquid Liquid) produced by one or more processes such as hydrorefining, wax isomerized mineral oil, Fischer-Tropsch process, etc. A base oil can be illustrated.
鉱油において全芳香族含有量は、特に制限はないが、好ましくは３０質量％以下、より好ましくは１５質量％以下、さらに好ましくは１０質量％以下、特に好ましくは５質量％以下である。鉱油の全芳香族含有量が３０質量％を越える場合は、酸化安定性が劣る恐れがある。
鉱油中の硫黄分量は、好ましくは０．１質量％以下、さらに好ましくは０．０５質量％以下、特に好ましくは０．００５質量％以下である。鉱油の硫黄分を低減することで、より高温清浄性に優れる組成物が得られる。
In the mineral oil, the total aromatic content is not particularly limited, but is preferably 30% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, and particularly preferably 5% by mass or less. When the total aromatic content of the mineral oil exceeds 30% by mass, the oxidation stability may be inferior.
The sulfur content in the mineral oil is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, and particularly preferably 0.005% by mass or less. By reducing the sulfur content of the mineral oil, a composition having better high-temperature cleanability can be obtained.
合成油としては、ポリブテン又はその水素化物；１−オクテンオリゴマー、１−デセンオリゴマー等のポリα−オレフィン又はその水素化物；ジトリデシルグルタレート、ジ−２−エチルヘキシルアジペート、ジイソデシルアジペート、ジトリデシルアジペート、又はジ−２−エチルヘキシルセバケート等のジエステル；トリメチロールプロパンカプリレート、トリメチロールプロパンペラルゴネート、ペンタエリスリトール−２−エチルヘキサノエート、又はペンタエリスリトールペラルゴネート等のポリオールエステル；マレイン酸ジブチル等のジカルボン酸類と炭素数２〜３０のα−オレフィンとの共重合体、アルキルナフタレン、アルキルベンゼン、又は芳香族エステル等の芳香族系合成油又はこれら２種以上の混合物が例示できる。 Synthetic oils include polybutene or hydrides thereof; poly α-olefins such as 1-octene oligomers and 1-decene oligomers or hydrides thereof; ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, Or a diester such as di-2-ethylhexyl sebacate; a polyol ester such as trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol-2-ethylhexanoate, or pentaerythritol pelargonate; a dicarboxylic such as dibutyl maleate Examples thereof include a copolymer of an acid and an α-olefin having 2 to 30 carbon atoms, an aromatic synthetic oil such as an alkylnaphthalene, an alkylbenzene, or an aromatic ester, or a mixture of two or more of these.
本発明に用いる基油としては、鉱油、合成油又はこれらの中から選ばれる２種以上の基油の任意混合物が使用できる。例えば、１種以上の鉱油、１種以上の合成油、１種以上の鉱油と１種以上の合成油との混合油が挙げられる。
基油の動粘度は特に制限はないが、その１００℃での動粘度は、１mm2／s以上、２０mm2／s以下が好ましく、２mm2／s以上、１０mm2／s以下がより好ましい。基油の１００℃での動粘度が２０mm2／ｓを越える場合は、低温粘度特性が悪化する恐れがあり、一方、その動粘度が１mm2／ｓ未満の場合は、潤滑箇所での油膜形成が不十分であるため潤滑性に劣り、また基油の蒸発損失が大きくなる恐れがある。
As the base oil used in the present invention, mineral oil, synthetic oil, or any mixture of two or more base oils selected from these can be used. For example, 1 or more types of mineral oil, 1 or more types of synthetic oil, the mixed oil of 1 or more types of mineral oil and 1 or more types of synthetic oil is mentioned.
The kinematic viscosity of the base oil is not particularly limited, but the kinematic viscosity at 100 ° C. is preferably 1 mm 2 / s or more and 20 mm 2 / s or less, more preferably 2 mm 2 / s or more and 10 mm 2 / s or less. If the base oil has a kinematic viscosity at 100 ° C. of more than 20 mm 2 / s, the low-temperature viscosity characteristics may be deteriorated. On the other hand, if the kinematic viscosity is less than 1 mm 2 / s, an oil film is formed at the lubrication point. Is insufficient, the lubricity is poor and the evaporation loss of the base oil may increase.
基油の粘度指数は特に制限はないが、低温から高温まで優れた粘度特性が得られるようにその値は８０以上が好ましく、１００以上が更に好ましく、１２０以上が最も好ましい。粘度指数の上限については特に制限はなく、ノルマルパラフィン、スラックワックスやGTLワックス等、あるいはこれらを異性化したイソパラフィン系鉱油のような１３５〜１８０程度のものやコンプレックスエステル系基油のような１５０〜２５０程度のものも使用することができる。基油の粘度指数が８０未満では、低温粘度特性が悪化する恐れがある。 The viscosity index of the base oil is not particularly limited, but the value is preferably 80 or more, more preferably 100 or more, and most preferably 120 or more so that excellent viscosity characteristics from low temperature to high temperature can be obtained. There is no particular limitation on the upper limit of the viscosity index, normal paraffin, slack wax, GTL wax or the like, or those of about 135 to 180 such as isoparaffinic mineral oil obtained by isomerizing these, or 150 to about 150 to the complex ester base oil. A thing of about 250 can also be used. If the viscosity index of the base oil is less than 80, the low temperature viscosity characteristics may be deteriorated.
本発明に用いる無灰酸化防止剤(A)としては、フェノール系酸化防止剤(A-1)、アミン系酸化防止剤(A-2)から選ばれる少なくとも１種が挙げられる。該(A)成分を後述する(B)及び(C)成分と併用し、後述する(B)〜(E)成分と併用することで相乗的に組成物の高温清浄性を高めることができる。
フェノール系酸化防止剤(A-1)としては、例えば、４，４'−メチレンビス(２，６−ジ−tert−ブチルフェノール)、４，４'−ビス(２，６−ジ−tert−ブチルフェノール)、４，４'−ビス(２−メチル−６−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)、２，２'−メチレンビス(４−メチル−６−tert−ブチルフェノール)、４，４'−ブチリデンビス(３−メチル−６−tert−ブチルフェノール)、４，４'−イソプロピリデンビス(２，６−ジ−tert−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−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、２，４−ジメチル−６−tert−ブチルフェノール、２，６−ジ−tert−α−ジメチルアミノ−ｐ−クレゾール、２，６−ジ−tert−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−tert−ブチルフェノール)、４，４'−チオビス(３−メチル−６−tert−ブチルフェノール)、２，２'−チオビス(４−メチル−６−tert−ブチルフェノール)、ビス(３−メチル−４−ヒドロキシ−５−tert−ブチルベンジル)スルフィド、ビス(３，５−ジ−tert−ブチル−４−ヒドロキシベンジル)スルフィド、２，２'−チオ−ジエチレンビス［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］、トリデシル−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、ペンタエリスリチル−テトラキス［３−(３，５−ジ−tert−ブチル−４−ヒドロキシフェニル)プロピオネート］、オクチル−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、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、オクチル−３−(３−メチル−５−ジ−tert−ブチル−４−ヒドロキシフェニル)プロピオネートが好ましく挙げられる。これらは二種以上を混合して使用してもよい。
Examples of the ashless antioxidant (A) used in the present invention include at least one selected from a phenolic antioxidant (A-1) and an amine antioxidant (A-2). By using the component (A) in combination with the components (B) and (C) described later and in combination with the components (B) to (E) described later, the high temperature cleanliness of the composition can be synergistically improved.
Examples of the phenolic antioxidant (A-1) include 4,4′-methylenebis (2,6-di-tert-butylphenol) and 4,4′-bis (2,6-di-tert-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′-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- tert-butyl-4-methylpheno 2,6-di-tert-butyl-4-ethylphenol, 2,4-dimethyl-6-tert-butylphenol, 2,6-di-tert-α-dimethylamino-p-cresol, 2,6 -Di-tert-butyl-4- (N, N'-dimethylaminomethylphenol), 4,4'-thiobis (2-methyl-6-tert-butylphenol), 4,4'-thiobis (3-methyl- 6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), bis (3-methyl-4-hydroxy-5-tert-butylbenzyl) sulfide, bis (3,5- Di-tert-butyl-4-hydroxybenzyl) sulfide, 2,2′-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tridecyl-3- (3 , 5-Di-tert-butyl-4- Droxyphenyl) propionate, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octyl-3- (3,5-di-tert-butyl-4- Hydroxyphenyl) propionate, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, octyl-3- (3-methyl-5-di-tert-butyl-4-hydroxyphenyl) propionate Is preferred. You may use these in mixture of 2 or more types.
アミン系酸化防止剤(A-2)としては、例えば、芳香族アミン化合物、アルキルジフェニルアミン、アルキルナフチルアミン、フェニル−α−ナフチルアミン、アルキルフェニル−α−ナフチルアミン等の潤滑油用として一般に使用されている公知のアミン系酸化防止剤が挙げられる。ここで、アルキル基とは炭素数１〜３０、好ましくは３〜２０、特に好ましくは４〜１０のアルキル基を示す。
(A)成分としては、上記フェノール系酸化防止剤(A-1)とアミン系酸化防止剤(A-2)とを組合せて配合することが好ましい。
As the amine-based antioxidant (A-2), for example, it is generally used for lubricating oils such as aromatic amine compounds, alkyldiphenylamines, alkylnaphthylamines, phenyl-α-naphthylamines, alkylphenyl-α-naphthylamines and the like. These amine-based antioxidants. Here, the alkyl group means an alkyl group having 1 to 30 carbon atoms, preferably 3 to 20 carbon atoms, particularly preferably 4 to 10 carbon atoms.
As the component (A), it is preferable to combine the phenolic antioxidant (A-1) and the amine antioxidant (A-2) in combination.
本発明において(A)成分の含有量は、組成物全量基準で１〜１２質量％、好ましくは３〜８質量％、特に好ましくは４〜６質量％である。その含有量が１２質量％を超える場合は、配合量に見合った十分な高温清浄性が得られない恐れがある。またその含有量が１質量％未満の場合は、十分な高温清浄性が得られないおそれがある。
(A)成分として、フェノール系酸化防止剤(A-1)とアミン系酸化防止剤(A-2)との混合物を配合する場合のそれぞれの含有量は、組成物全量基準で通常フェノール系酸化防止剤(A-1)０．５〜６質量%、好ましくは２〜５質量％、更に好ましくは２．５〜３．５質量％、アミン系酸化防止剤(A-2)０．５〜６質量%、好ましくは１〜３質量％、更に好ましくは１．５〜２．５質量％である。
In the present invention, the content of the component (A) is 1 to 12% by mass, preferably 3 to 8% by mass, particularly preferably 4 to 6% by mass based on the total amount of the composition. When the content exceeds 12% by mass, sufficient high temperature cleanliness corresponding to the blending amount may not be obtained. Moreover, when the content is less than 1 mass%, there exists a possibility that sufficient high temperature detergency may not be obtained.
As a component (A), when blending a mixture of a phenolic antioxidant (A-1) and an amine antioxidant (A-2), each content is usually phenolic oxidation based on the total amount of the composition. Inhibitor (A-1) 0.5-6% by mass, preferably 2-5% by mass, more preferably 2.5-3.5% by mass, amine-based antioxidant (A-2) 0.5- It is 6 mass%, Preferably it is 1-3 mass%, More preferably, it is 1.5-2.5 mass%.
本発明に用いるホウ素を含まないビスタイプコハク酸イミド系無灰分散剤(B)としては、イミド化に際してポリアミンの両端に無水コハク酸が付加した式(2)で表されるビスタイプコハク酸イミドが挙げられる。また、本発明に用いるホウ素変性コハク酸イミド系無灰分散剤(C)としては、イミド化に際してポリアミンの一端に無水コハク酸が付加した式(1)で示されるモノタイプコハク酸イミド及び／又はポリアミンの両端に無水コハク酸が付加した式(2)で表されるビスタイプコハク酸イミドを、ホウ素変性させたコハク酸イミドが挙げられる。 As the bis-type succinimide-based ashless dispersant (B) containing no boron used in the present invention, there is a bis-type succinimide represented by the formula (2) in which succinic anhydride is added to both ends of a polyamine during imidization. Can be mentioned. The boron-modified succinimide-based ashless dispersant (C) used in the present invention is a monotype succinimide and / or polyamine represented by the formula (1) in which succinic anhydride is added to one end of a polyamine during imidization. And succinimide obtained by boron-modifying a bis-type succinimide represented by the formula (2) in which succinic anhydride is added to both ends.
(B)成分および(C)成分は、摩耗防止性の向上の面で、そのアルキル基又はアルケニル基の数平均分子量は５００〜５６００が好ましく、８００〜４９００がより好ましい。このために、上記式(1)及び(2)中のＲ1、Ｒ2及びＲ3のアルキル基又はアルケニル基は、その炭素数が上記重量平均分子量の範囲になるように選定することが好ましい。
上記コハク酸イミドの製法は特に制限はなく、例えば、炭素数４０〜４００のアルキル基又はアルケニル基を有する化合物を、無水マレイン酸と１００〜２００℃で反応させて得たアルキルコハク酸又はアルケニルコハク酸をポリアミンと反応させることにより得られる。
ポリアミンとしては、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、ペンタエチレンヘキサミンが例示できる。
Component (B) and component (C) are preferably an alkyl group or an alkenyl group having a number average molecular weight of 500 to 5600, more preferably 800 to 4900, from the viewpoint of improving wear resistance. For this reason, the alkyl group or alkenyl group of R 1 , R 2 and R 3 in the above formulas (1) and (2) is preferably selected so that the number of carbon atoms is in the range of the weight average molecular weight. .
The method for producing the succinimide is not particularly limited. For example, an alkyl succinic acid or alkenyl succinic acid obtained by reacting a compound having an alkyl group or alkenyl group having 40 to 400 carbon atoms with maleic anhydride at 100 to 200 ° C. It is obtained by reacting an acid with a polyamine.
Examples of polyamines include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.
(C)成分は、式(1)及び式(2)で示されるコハク酸イミドに、ホウ酸、ホウ酸塩又はホウ酸エステル等のホウ素化合物を作用させることにより得ることができる。
ホウ酸としては、例えば、オルトホウ酸、メタホウ酸又はテトラホウ酸が挙げられる。
The component (C) can be obtained by allowing a boron compound such as boric acid, borate or boric acid ester to act on the succinimide represented by the formulas (1) and (2).
Examples of boric acid include orthoboric acid, metaboric acid, and tetraboric acid.
(C)成分は、窒素／ホウ素(Ｎ／Ｂ)質量比２〜４のホウ素変成コハク酸イミド(C-1)と、Ｎ／Ｂ質量比０．５〜１．５のホウ素変成コハク酸イミド(C-2)との混合物が好ましい。このような混合物として配合する場合のホウ素変成コハク酸イミド(C-1)の含有割合は、組成物全量基準で０．５〜４質量%が好ましい。一方、ホウ素変成コハク酸イミド(C-2)の含有割合は、組成物全量基準で０．５〜６質量%が好ましい。 Component (C) is a boron-modified succinimide (C-1) having a nitrogen / boron (N / B) mass ratio of 2 to 4 and a boron-modified succinimide having an N / B mass ratio of 0.5 to 1.5. A mixture with (C-2) is preferred. The content of boron-modified succinimide (C-1) when blended as such a mixture is preferably 0.5 to 4% by mass based on the total amount of the composition. On the other hand, the content of the boron-modified succinimide (C-2) is preferably 0.5 to 6% by mass based on the total amount of the composition.
本発明において、(B)成分の含有割合は、摩耗防止性を向上させるために、組成物全量基準で１〜１０質量％、好ましくは２〜５質量％、より好ましくは１〜３質量％であり、さらに詳しくは、窒素含有量基準での（B）成分の含有割合は、０．０１〜０．２質量％、好ましくは０．０２〜０．１質量％、より好ましくは０．０３〜０．０６質量％である。
本発明において、(C)成分の含有割合は、摩耗防止性を向上させるために、組成物全量基準で２〜１０質量％、好ましくは３〜８質量％、より好ましくは４〜７質量％であり、さらに詳しくは、窒素含有量基準での（C）成分の含有割合は、０．０３〜０．１５質量％、好ましくは０．０５〜０．１２質量％、より好ましくは０．０７〜０．１１質量％である。
In the present invention, the content ratio of the component (B) is 1 to 10% by mass, preferably 2 to 5% by mass, more preferably 1 to 3% by mass on the basis of the total amount of the composition in order to improve the antiwear property. More specifically, the content ratio of the component (B) based on the nitrogen content is 0.01 to 0.2% by mass, preferably 0.02 to 0.1% by mass, more preferably 0.03 to 0.03% by mass. 0.06% by mass.
In the present invention, the content ratio of the component (C) is 2 to 10% by mass, preferably 3 to 8% by mass, more preferably 4 to 7% by mass on the basis of the total amount of the composition in order to improve the antiwear property. More specifically, the content ratio of the component (C) on the basis of the nitrogen content is 0.03 to 0.15% by mass, preferably 0.05 to 0.12% by mass, more preferably 0.07 to 0.11% by mass.
本発明においては、上記(A)、(B)及び(C)成分を併用することで、２９０℃のような高温での清浄性に優れた組成物が得られ、これら３成分を主成分とする添加剤を含有させることにより、リン、硫黄、金属のいずれか１〜３種を低減又は実質的に含有しない内燃機関用潤滑油組成物とすることができる。 In the present invention, by using the components (A), (B) and (C) in combination, a composition having excellent cleanliness at a high temperature such as 290 ° C. can be obtained. By containing the additive which makes it, it can be set as the lubricating oil composition for internal combustion engines which reduces or does not contain substantially any 1-3 types of phosphorus, sulfur, and a metal.
本発明の潤滑油組成物は、上記(A)〜(C)成分に加えて、摩耗防止性を更に向上させるために、多価アルコールと多塩基酸との反応により得られたエステル(D)及び／又は酸化安定性を向上させるために有機モリブデン化合物(E)を配合することができる。
上記(D)成分における多価アルコールとしては、通常２〜１０価、好ましくは２〜６価のものが用いられる。２〜１０価の多価アルコールとしては、例えば、エチレングリコール、ジエチレングリコール、エチレングリコールの３〜１５量体からなるポリエチレングリコール、プロピレングリコール、ジプロピレングリコール、プロピレングリコールの３〜１５量体からなるポリプロピレングリコール、１，３−プロパンジオール、１，２−プロパンジオール、１，３−ブタンジオール、１，４−ブタンジオール、２−メチル−１，２−プロパンジオール、２−メチル−１，３−プロパンジオール、１，２−ペンタンジオール、１，３−ペンタンジオール、１，４−ペンタンジオール、１，５−ペンタンジオール、ネオペンチルグリコール等の２価アルコール；グリセリン；ジグリセリン、トリグリセリン、テトラグリセリン等のグリセリンの２〜８量体からなるポリグリセリン；トリメチロールエタン、トリメチロールプロパン、トリメチロールブタン等トリメチロールアルカン及びこれらの２〜８量体；ペンタエリスリトール及びこれらの２〜４量体；１，２，４−ブタントリオール、１，３，５−ペンタントリオール、１，２，６−ヘキサントリオール、１，２，３，４−ブタンテトロール、ソルビトール、ソルビタン、ソルビトールグリセリン縮合物、アドニトール、アラビトール、キシリトール、マンニトールが挙げられる。
In addition to the above components (A) to (C), the lubricating oil composition of the present invention is an ester (D) obtained by reacting a polyhydric alcohol with a polybasic acid in order to further improve the wear resistance. And / or an organic molybdenum compound (E) can be mix | blended in order to improve oxidation stability.
As the polyhydric alcohol in the component (D), those having 2 to 10 valences, preferably 2 to 6 valences are usually used. Examples of the divalent to 10-valent polyhydric alcohol include, for example, polyethylene glycol consisting of ethylene glycol, diethylene glycol, and 3-15 mer of ethylene glycol, polypropylene glycol consisting of 3 to 15 mer of propylene glycol, dipropylene glycol, and propylene glycol. 1,3-propanediol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,2-propanediol, 2-methyl-1,3-propanediol , 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, neopentyl glycol and other dihydric alcohols; glycerin; diglycerin, triglycerin, tetraglycerin, etc. 2-8 of glycerin Polyglycerin consisting of trimethylolethane, trimethylolpropane, trimethylolbutane and the like trimethylolalkanes and 2- to 8-mers thereof; pentaerythritol and their 2-tetramers; 1,2,4-butanetriol; 1,3,5-pentanetriol, 1,2,6-hexanetriol, 1,2,3,4-butanetetrol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol, mannitol.
これらの多価アルコールの中でも、エチレングリコール、ジエチレングリコール、エチレングリコールの３〜１０量体からなるポリエチレングリコール、プロピレングリコール、ジプロピレングリコール、プロピレングリコールの３〜１０量体からなるポリプロピレングリコール、１，３−プロパンジオール、２−メチル−１，２−プロパンジオール、２−メチル−１，３−プロパンジオール、ネオペンチルグリコール、グリセリン、ジグリセリン、トリグリセリン、トリメチロールエタン、トリメチロールプロパン、トリメチロールブタン等のトリメチロールアルカン及びこれらの２〜４量体、ペンタエリスリトール、ジペンタエリスリトール、１，２，４−ブタントリオール、１，３，５−ペンタントリオール、１，２，６−ヘキサントリオール、１，２，３，４−ブタンテトロール、ソルビトール、ソルビタン、ソルビトールグリセリン縮合物、アドニトール、アラビトール、キシリトール、マンニトール等の２〜６価の多価アルコール及びこれらの混合物が好ましい。更に好ましくは、エチレングリコール、プロピレングリコール、ネオペンチルグリコール、グリセリン、トリメチロールエタン、トリメチロールプロパン、ペンタエリスリトール、ソルビタン、及びこれらの混合物が挙げられる。これらの中でも、より高い熱・酸化安定性が得られることから、ネオペンチルグリコール、トリメチロールエタン、トリメチロールプロパン、ペンタエリスリトール、及びこれらの混合物が最も好ましい。 Among these polyhydric alcohols, ethylene glycol, diethylene glycol, polyethylene glycol composed of 3 to 10 mer of ethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol composed of 3 to 10 mer of propylene glycol, 1,3- Propanediol, 2-methyl-1,2-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, glycerin, diglycerin, triglycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, etc. Trimethylol alkanes and their dimers and tetramers, pentaerythritol, dipentaerythritol, 1,2,4-butanetriol, 1,3,5-pentanetriol, 1,2,6-hexaneto Ol, 1,2,3,4 butane tetrol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol, divalent to hexavalent polyhydric alcohols and mixtures thereof, such as mannitol are preferred. More preferably, ethylene glycol, propylene glycol, neopentyl glycol, glycerin, trimethylol ethane, trimethylol propane, pentaerythritol, sorbitan, and a mixture thereof can be used. Among these, neopentyl glycol, trimethylol ethane, trimethylol propane, pentaerythritol, and a mixture thereof are most preferable because higher thermal and oxidation stability can be obtained.
上記(D)成分における多塩基酸としては、例えば、炭素数２〜１６の二塩基酸及びトリメリット酸が挙げられる。炭素数２〜１６の二塩基酸は、直鎖のものでも分岐のものでもよく、また飽和のものでも不飽和のものでもよい。具体的には例えば、エタン二酸、プロパン二酸、ブタン二酸、ペンタン二酸、ヘキサン二酸、ヘプタン二酸、オクタン二酸、ノナン二酸(アゼライン酸)、デカン二酸(セバシン酸)、ウンデカン二酸、ドデカン二酸、トリデカン二酸、テトラデカン二酸、ヘプタデカン二酸、ヘキサデカン二酸、ヘキセン二酸、ヘプテン二酸、オクテン二酸、ノネン二酸、デセン二酸、ウンデセン二酸、ドデセン二酸、トリデセン二酸、テトラデセン二酸、ヘプタデセン二酸、ヘキサデセン二酸又はこれらの２種以上の混合物が挙げられる。 Examples of the polybasic acid in the component (D) include a dibasic acid having 2 to 16 carbon atoms and trimellitic acid. The dibasic acid having 2 to 16 carbon atoms may be linear or branched, and may be saturated or unsaturated. Specifically, for example, ethanedioic acid, propanedioic acid, butanedioic acid, pentanedioic acid, hexanedioic acid, heptanedioic acid, octanedioic acid, nonanedioic acid (azelaic acid), decanedioic acid (sebacic acid), Undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, heptadecanedioic acid, hexadecanedioic acid, hexenedioic acid, heptenedioic acid, octenedioic acid, nonenedioic acid, decenedioic acid, undecenedioic acid, dodecenedioic acid Examples include acids, tridecenedioic acid, tetradecenedioic acid, heptacenedioic acid, hexadecenedioic acid, or a mixture of two or more thereof.
上記(D)成分は、多価アルコール中の水酸基又は多塩基酸のカルボキシル基の全てがエステル化された完全エステルでもよく、水酸基又はカルボキシル基の一部がエステル化されず水酸基又はカルボキシル基のまま残存する部分エステルでもよいが、低温性能の点から、完全エステルであることが好ましい。
上記(D)成分の重量平均分子量は、潤滑性の点から、好ましくは３,０００〜５０,０００、より好ましくは５,０００〜４０,０００、更に好ましくは１０,０００〜３０,０００である。重量平均分子量が３,０００未満の場合は十分な摩耗防止効果が得られないおそれがあり、５０,０００を超える場合には組成物製造時の作業性が悪くなるおそれがある。
本発明の潤滑油組成物に上記(D)成分を含有させる場合の含有割合は、組成物全量基準で、通常０．１〜５質量％、好ましくは０．２〜４質量％、より好ましくは０．３〜３質量％である。エステルの含有量が０．１質量％未満の場合は十分な摩耗防止効果が得られないおそれがあり、エステルの含有量が５質量％以上の場合は添加量に見合った効果が得られないおそれがある。
The component (D) may be a complete ester in which all of the hydroxyl groups or polybasic acid carboxyl groups in the polyhydric alcohol are esterified, and the hydroxyl groups or part of the carboxyl groups are not esterified and remain as hydroxyl groups or carboxyl groups. The remaining partial ester may be used, but a complete ester is preferable from the viewpoint of low-temperature performance.
The weight average molecular weight of the component (D) is preferably 3,000 to 50,000, more preferably 5,000 to 40,000, and still more preferably 10,000 to 30,000 from the viewpoint of lubricity. . When the weight average molecular weight is less than 3,000, there is a possibility that a sufficient anti-wearing effect may not be obtained, and when it exceeds 50,000, workability during production of the composition may be deteriorated.
The content ratio when the component (D) is contained in the lubricating oil composition of the present invention is usually 0.1 to 5% by mass, preferably 0.2 to 4% by mass, more preferably based on the total amount of the composition. It is 0.3-3 mass%. If the ester content is less than 0.1% by mass, a sufficient anti-wear effect may not be obtained, and if the ester content is 5% by mass or more, the effect corresponding to the addition amount may not be obtained. There is.
本発明における(Ｅ)成分は有機モリブデン化合物であり、より厳しい酸化劣化条件においても、過酸化物を分解し、酸化安定性向上や粘度増加抑制等による組成物の長寿命化のために配合することができる。
本発明における(Ｅ)成分としては、例えば、モリブデンジチオカーバメート、モリブデン−アミン錯体、モリブデン−コハク酸イミド錯体、アルコールのモリブデン塩、有機酸のモリブデン塩が挙げられ、過酸化物分解効果と低硫黄化の観点から、モリブデン−アミン錯体、モリブデン−コハク酸イミド錯体が好ましく使用される。
ここでいうモリブデン−アミン錯体、モリブデン−コハク酸イミド錯体、アルコールのモリブデン塩、有機酸のモリブデン塩とは、モリブデン化合物(例えば、二酸化モリブデン、三酸化モリブデン等の酸化モリブデン、オルトモリブデン酸、パラモリブデン酸、(ポリ)硫化モリブデン酸等のモリブデン酸、これらモリブデン酸の金属塩、アンモニウム塩等のモリブデン酸塩、二硫化モリブデン、三硫化モリブデン、五硫化モリブデン、ポリ硫化モリブデン等の硫化モリブデン、硫化モリブデン酸、硫化モリブデン酸の金属塩又はアミン塩、塩化モリブデン等のハロゲン化モリブデン等)と、アミン化合物、コハク酸イミド化合物、アルコール、有機酸から選ばれる１種の有機化合物と、必要に応じて元素硫黄等の硫黄源とを反応させて得られる、モリブデン−アミン錯体、モリブデン−コハク酸イミド錯体、アルコールのモリブデン塩、有機酸のモリブデン塩を示す。
The component (E) in the present invention is an organomolybdenum compound, and is blended to extend the life of the composition by decomposing peroxide and improving the oxidative stability and suppressing the increase in viscosity even under more severe oxidative deterioration conditions. be able to.
Examples of the component (E) in the present invention include molybdenum dithiocarbamate, molybdenum-amine complex, molybdenum-succinimide complex, alcohol molybdenum salt, and organic acid molybdenum salt. From the viewpoint of conversion, molybdenum-amine complexes and molybdenum-succinimide complexes are preferably used.
Molybdenum-amine complex, molybdenum-succinimide complex, molybdenum salt of alcohol, and molybdenum salt of organic acid are molybdenum compounds (for example, molybdenum dioxide, molybdenum oxide such as molybdenum trioxide, orthomolybdic acid, para-molybdenum). Acid, molybdic acid such as (poly) sulfurized molybdate, metal salts of these molybdates, molybdate such as ammonium salt, molybdenum disulfide, molybdenum trisulfide, molybdenum pentasulfide, molybdenum sulfide such as polysulfide molybdenum, molybdenum sulfide Acid, metal salts of sulfurized molybdic acid or amine halides, molybdenum halides such as molybdenum chloride, etc.), one organic compound selected from amine compounds, succinimide compounds, alcohols, organic acids, and elements as required Obtained by reacting with sulfur sources such as sulfur , Molybdenum-amine complex, molybdenum-succinimide complex, molybdenum salt of alcohol, and molybdenum salt of organic acid.
本発明における有機モリブデン化合物としては、これらのうち、過酸化物分解効果と高温清浄性に特に優れる点で、モリブデン−コハク酸イミド錯体を使用することが最も好ましく、硫黄を含有するモリブデン−コハク酸イミド錯体が最も好ましい。なお、硫黄を含有するモリブデン−コハク酸イミド錯体としては、上述したモリブデン化合物のうち硫黄を含有するモリブデン化合物と、コハク酸イミド化合物と、必要に応じて元素硫黄等の硫黄源との反応生成物、あるいは上述したモリブデン化合物のうち硫黄を含有しないモリブデン化合物と、コハク酸イミド化合物と、元素硫黄等の硫黄源との反応生成物が好ましい例として挙げられる。
なお、ここでいうコハク酸イミド化合物としては、コハク酸イミド、炭素数１〜３９の炭化水素基を有するコハク酸イミド、及び前述した(Ｃ)成分の項で説明した、式(１)で示される炭素数４０〜４００のアルキル基又はアルケニル基を有するモノタイプコハク酸イミド、式(２)で示される炭素数４０〜４００のアルキル基又はアルケニル基を有するビスタイプコハク酸イミド、及びこれらの混合物を例示することができる。これらの中でも、スラッジ分散性の観点から炭素数４０〜４００のアルキル基又はアルケニル基を有するモノタイプ又はビスタイプのコハク酸イミド及びその混合物が特に好ましい。
本発明における有機モリブデン化合物としては、その硫黄とモリブデンとの含有比率に特に制限はないが、硫黄／モリブデン比率(質量比)は、好ましくは１．２以下、より好ましくは０．５以下であり、過酸化物分解効果と低硫黄化の観点から、さらに好ましくは０．２５以下であり、硫黄／モリブデン比率(質量比)は、０でも良いが、摩耗防止性を向上できる点から、好ましくは０．１以上、より好ましくは０．１５以上である。
Among these, as the organic molybdenum compound in the present invention, it is most preferable to use a molybdenum-succinimide complex because it is particularly excellent in peroxide decomposition effect and high-temperature cleanliness, and molybdenum-succinic acid containing sulfur. Most preferred are imide complexes. In addition, as a molybdenum-succinimide complex containing sulfur, a reaction product of a molybdenum compound containing sulfur among the above-described molybdenum compounds, a succinimide compound, and a sulfur source such as elemental sulfur as necessary. A preferable example is a reaction product of a molybdenum compound that does not contain sulfur among the above-described molybdenum compounds, a succinimide compound, and a sulfur source such as elemental sulfur.
In addition, as a succinimide compound here, succinimide, a succinimide which has a C1-C39 hydrocarbon group, and the formula (1) demonstrated by the term of the (C) component mentioned above are shown. Mono-type succinimide having an alkyl group or alkenyl group having 40 to 400 carbon atoms, bis-type succinimide having an alkyl group or alkenyl group having 40 to 400 carbon atoms represented by formula (2), and a mixture thereof Can be illustrated. Among these, from the viewpoint of sludge dispersibility, monotype or bistype succinimide having an alkyl group or alkenyl group having 40 to 400 carbon atoms and a mixture thereof are particularly preferable.
The organic molybdenum compound in the present invention is not particularly limited in the content ratio of sulfur and molybdenum, but the sulfur / molybdenum ratio (mass ratio) is preferably 1.2 or less, more preferably 0.5 or less. Further, from the viewpoint of the peroxide decomposition effect and low sulfurization, it is more preferably 0.25 or less, and the sulfur / molybdenum ratio (mass ratio) may be 0, but preferably from the viewpoint of improving the wear resistance. It is 0.1 or more, more preferably 0.15 or more.
本発明の潤滑油組成物に上記(Ｅ)成分を含有させる場合の含有割合は、組成物全量基準で、モリブデン元素換算量として０．００５〜０．０８質量％、好ましくは０．０１〜０．０６質量％、硫酸灰分の増加抑制と過酸化物分解効果とのバランスで、さらに好ましくは０．０２〜０．０４質量％である。モリブデン元素換算量としての含有量が０．０８質量％を超える場合、硫酸灰分を増加させるため好ましくなく、該含有量が０．００５質量％未満では、期待される過酸化物分解効果が得られないため好ましくない。 When the lubricating oil composition of the present invention contains the component (E), the content is 0.005 to 0.08% by mass, preferably 0.01 to 0, in terms of molybdenum element, based on the total amount of the composition. 0.06% by mass, more preferably 0.02 to 0.04% by mass in terms of the balance between suppression of increase in sulfated ash and the effect of peroxide decomposition. When the content in terms of molybdenum element is more than 0.08% by mass, it is not preferable because the sulfated ash content is increased. When the content is less than 0.005% by mass, the expected peroxide decomposition effect is obtained. Since it is not, it is not preferable.
本発明の潤滑油組成物には、更に金属に対する腐食防止性を付与するために、腐食防止剤(Ｆ)を配合することができる。（Ｆ）成分としては、例えば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、又はイミダゾール系化合物が挙げられ、チアジアゾール系化合物が特に好ましく用いられる。腐食防止剤の組成物全量基準での配合量は、０．００５〜５質量％であり、好ましくは０．０１〜２質量％である。 The lubricating oil composition of the present invention may further contain a corrosion inhibitor (F) in order to impart corrosion resistance to metals. Examples of the component (F) include benzotriazole compounds, tolyltriazole compounds, thiadiazole compounds, and imidazole compounds, and thiadiazole compounds are particularly preferably used. The compounding quantity of the corrosion inhibitor based on the total composition is 0.005 to 5% by mass, preferably 0.01 to 2% by mass.
本発明の潤滑油組成物には、本発明の効果をより高めるため、あるいは要求される性能上、必要に応じて、本発明の効果を著しく阻害しない範囲で各種の他の潤滑油添加剤を配合することができる。他の潤滑油添加剤としては、例えば、摩擦調整剤、粘度指数向上剤、防錆剤、抗乳化剤、金属不活性化剤、消泡剤、又は着色剤が挙げられる。
摩擦調整剤としては、例えば、脂肪酸エステル系、脂肪族アミン系、脂肪酸アミド系等の無灰摩擦調整剤、モリブデンジチオカーバメート、モリブデンジチオホスフェート等の金属系摩擦調整剤等が挙げられる。
粘度指数向上剤としては、例えば、ポリメタクリレート系粘度指数向上剤、オレフィン共重合体系粘度指数向上剤、スチレン−ジエン共重合体系粘度指数向上剤、スチレン−無水マレイン酸エステル共重合体系粘度指数向上剤又はポリアルキルスチレン系粘度指数向上剤が挙げられる。これらの粘度指数向上剤の重量平均分子量は、通常８００〜１,０００,０００、好ましくは１００,０００〜９００,０００である。
In the lubricating oil composition of the present invention, various other lubricating oil additives are added within the range that does not significantly impair the effects of the present invention, if necessary, in order to further enhance the effects of the present invention or in the required performance. Can be blended. Examples of other lubricating oil additives include friction modifiers, viscosity index improvers, rust inhibitors, demulsifiers, metal deactivators, antifoaming agents, and colorants.
Examples of the friction modifier include ashless friction modifiers such as fatty acid esters, aliphatic amines, and fatty acid amides, and metal friction modifiers such as molybdenum dithiocarbamate and molybdenum dithiophosphate.
Examples of the viscosity index improver include, for example, a polymethacrylate viscosity index improver, an olefin copolymer viscosity index improver, a styrene-diene copolymer viscosity index improver, and a styrene-maleic anhydride copolymer viscosity index improver. Or a polyalkyl styrene type viscosity index improver is mentioned. The weight average molecular weight of these viscosity index improvers is usually 800 to 1,000,000, preferably 100,000 to 900,000.
防錆剤としては、例えば、石油スルホネート、アルキルベンゼンスルホネート、ジノニルナフタレンスルホネート、アルケニルコハク酸エステル、又は多価アルコールエステルが挙げられる。
抗乳化剤としては、例えば、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、又はポリオキシエチレンアルキルナフチルエーテル等のポリアルキレングリコール系非イオン系界面活性剤が挙げられる。
金属不活性化剤としては、例えば、イミダゾリン、ピリミジン誘導体、アルキルチアジアゾール、メルカプトベンゾチアゾール、ベンゾトリアゾール又はその誘導体、１，３，４−チアジアゾールポリスルフィド、１，３，４−チアジアゾリル−２，５−ビスジアルキルジチオカーバメート、２−(アルキルジチオ)ベンゾイミダゾール、又はβ−(ｏ−カルボキシベンジルチオ)プロピオンニトリルが挙げられる。
消泡剤としては、例えば、シリコーン、フルオロシリコール、又はフルオロアルキルエーテルが挙げられる。
Examples of the rust inhibitor include petroleum sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, alkenyl succinic acid ester, and polyhydric alcohol ester.
Examples of the demulsifier include polyalkylene glycol nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, and polyoxyethylene alkyl naphthyl ether.
Examples of metal deactivators include imidazoline, pyrimidine derivatives, alkylthiadiazoles, mercaptobenzothiazoles, benzotriazoles or derivatives thereof, 1,3,4-thiadiazole polysulfide, 1,3,4-thiadiazolyl-2,5-bis. Examples include dialkyldithiocarbamate, 2- (alkyldithio) benzimidazole, or β- (o-carboxybenzylthio) propiononitrile.
Examples of the antifoaming agent include silicone, fluorosilicol, or fluoroalkyl ether.
他の潤滑油添加剤を本発明の組成物に含有させる場合には、その含有量は組成物全量基準で、摩擦調整剤では０．０１〜２質量％、粘度指数向上剤では０．１〜２０質量％、防錆剤、抗乳化剤ではそれぞれ０．００５〜５質量％、金属不活性化剤では０．００５〜１質量％、消泡剤では０．０００５〜１質量％の範囲が好ましい。 When other lubricating oil additives are included in the composition of the present invention, the content is 0.01 to 2% by mass for the friction modifier and 0.1 to 0.1 for the viscosity index improver based on the total amount of the composition. 20 mass%, rust inhibitor and demulsifier are each preferably 0.005 to 5 mass%, metal deactivator is 0.005 to 1 mass%, and antifoaming agent is 0.0005 to 1 mass%.
本発明の油用潤滑油組成物は、(A)成分、(B)成分及び(C)成分を含む添加剤を必須とし、必要に応じて、(D)成分及び／又は(E)成分、上記その他の潤滑油添加剤の少なくとも１種を、上述の基油に配合することにより得ることができる。
従って、基油は残部となり、本発明の潤滑油組成物は基油により全量を１００質量％とすることができる。
なお、本発明の潤滑油組成物の１００℃における動粘度は、特に制限はないが、好ましくは３．８〜２１．９ｍｍ2／ｓ、より好ましくは４．１〜１６．３ｍｍ2／ｓ、特に好ましくは５．６〜１２．５ｍｍ2／ｓである。ここでいう１００℃における動粘度とは、ＡＳＴＭ Ｄ−４４５に規定される１００℃での動粘度を示す。
本発明の潤滑油組成物は、優れた摩耗防止性、高温清浄性及び酸化安定性を発揮すると共に、内燃機関に使用される酸化触媒、ＮＯｘ還元触媒やＤＰＦの寿命を延長するために、SAPS量が低減されている。即ち、本発明の潤滑油組成物の硫酸灰分量は０．２質量%以下、好ましくは０．１５質量％以下、リン含量は０．０１質量％未満、好ましくは０、硫黄含量は０．１質量%以下、好ましくは０．０５質量％以下、ホウ素含量は０．０５〜０．０８質量%、好ましくは０．０５〜０．０６質量％である。
ここで、上記硫酸灰分量とは、JIS K２２７２の５．「硫酸灰分の試験方法」に規定される方法により測定される値を示し、主として金属含有添加剤および分散剤中のホウ素に起因する値である。
The lubricating oil composition for oil of the present invention essentially comprises an additive comprising the component (A), the component (B) and the component (C), and if necessary, the component (D) and / or the component (E), It can be obtained by blending at least one of the other lubricating oil additives with the base oil described above.
Accordingly, the base oil becomes the balance, and the total amount of the lubricating oil composition of the present invention can be 100% by mass with the base oil.
The kinematic viscosity at 100 ° C. of the lubricating oil composition of the present invention is not particularly limited, but is preferably 3.8 to 21.9 mm 2 / s, more preferably 4.1 to 16.3 mm 2 / s, Particularly preferably, it is 5.6 to 12.5 mm 2 / s. The kinematic viscosity at 100 ° C. here refers to the kinematic viscosity at 100 ° C. as defined in ASTM D-445.
The lubricating oil composition of the present invention exhibits excellent anti-wear properties, high-temperature cleanliness and oxidation stability, and also extends the life of oxidation catalysts, NOx reduction catalysts and DPFs used in internal combustion engines. The amount is reduced. That is, the amount of sulfated ash in the lubricating oil composition of the present invention is 0.2% by mass or less, preferably 0.15% by mass or less, the phosphorus content is less than 0.01% by mass, preferably 0, and the sulfur content is 0.1 The content of boron is 0.05% by mass or less, preferably 0.05% by mass or less, and the boron content is 0.05-0.08% by mass, preferably 0.05-0.06% by mass.
Here, the amount of sulfated ash is JIS K2272 5. The value measured by the method prescribed in “Testing method for sulfated ash” is a value mainly attributable to boron in the metal-containing additive and dispersant.
以下に本発明を実施例及び比較例によってさらに具体的に説明するが、本発明はこれらの例に限定されない。
実施例１〜１０及び比較例１〜７
表１及び表２に示される組成の潤滑油組成物につき、実験室での高温清浄性及び摩耗防止性の評価と、エンジンを用いた動弁系摩耗及びエンジン清浄性の評価とを以下の方法で行った。結果を表１及び表２に示す。
尚、粘度グレードはすべて１０Ｗ−３０とした(１００℃動粘度約１０．７ｍｍ2／ｓ)。
The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.
Examples 1-10 and Comparative Examples 1-7
For the lubricating oil compositions having the compositions shown in Tables 1 and 2, the following methods were used to evaluate the high temperature cleanliness and wear resistance in the laboratory, and the evaluation of valve system wear and engine cleanliness using the engine. I went there. The results are shown in Tables 1 and 2.
The viscosity grades were all 10W-30 (100 ° C. kinematic viscosity about 10.7 mm 2 / s).
（高温清浄性の評価）
ディーゼルエンジン油の高温堆積物防止性評価のために、JASOディーゼルエンジン油規格試験JASO M355:2005におけるJPI-5S-55-99(ホットチューブ試験)を利用して行った。このホットチューブ試験において、２８０℃、１６時間後の評点が７．０以上であることがディーゼルエンジン油の品質に求められている。本発明では高温堆積物防止性評価のために、２８０℃および温度条件をより厳しくした２９０℃で試験を行った。
（摩耗防止性の評価）
摩耗防止性の評価にＨＦＲＲ(High Frequency Reciprocating Rig)を用いた。ボール直径が６ｍｍで、振動数５０Ｈｚ、振幅１ｍｍ、すべり速度０．１ｍ／ｓ、荷重３００ｇ(平均ヘルツ圧力０．９５６ＧＰａ)、試験片温度１００℃、試験時間６０分間の試験条件とした。ディスクの摩耗痕径の摩耗幅を測定し、ｍｍで表示した。ディスク摩耗痕径０．３０ｍｍ以下であることが目標である。
（腐食防止性の評価）
金属腐食防止性は高温腐食酸化安定度試験により評価した。試験油１００ｍLに銅片（０．８ｍｍ×２５．４ｍｍ×２５．４ｍｍ×６ｍｍФ孔）および鉛片（１ｍｍ×２５．４ｍｍ×２５．４ｍｍ×６ｍｍФ孔）を浸漬し、温度１３５℃、空気吹き込み量５Ｌ／時間の条件で１６８時間行った。試験油中の鉛量と銅量を分析し、鉛量が１２０質量ｐｐｍ以下、銅量が２０質量ｐｐｍ以下であれば合格とした。
（JASO M328-95動弁系摩耗試験(KA24Eガソリンエンジン)）
JASO標準油GV1と同等以上で、JASO標準油GV2より優れた成績であれば合格とした。目安として、カムノーズ摩耗１６．５μｍ以下であれば合格とした。
（JASO M 354:2005動弁系摩耗試験(4D34T4ディーゼルエンジン)）
カム径減少量(平均)９５μｍ以下、カム径減少量(最大)２１０μｍ以下、ピッチングなし、であれば合格とした。
（JASO M 336:1998清浄性試験）
トップリング溝カーボン詰まり６０ｖｏｌ％以下、ピストンリング膠着なし、であれば合格とした。
(Evaluation of high temperature cleanliness)
JPI-5S-55-99 (hot tube test) in JASO Diesel Engine Oil Standard Test JASO M355: 2005 was used to evaluate high temperature deposit prevention of diesel engine oil. In this hot tube test, the quality of diesel engine oil is required to be 7.0 or more after 16 hours at 280 ° C. In the present invention, the test was conducted at 280 ° C. and 290 ° C. with more severe temperature conditions in order to evaluate high-temperature deposit prevention.
(Evaluation of wear prevention)
HFRR (High Frequency Reciprocating Rig) was used for evaluation of wear resistance. The test conditions were a ball diameter of 6 mm, a vibration frequency of 50 Hz, an amplitude of 1 mm, a sliding speed of 0.1 m / s, a load of 300 g (average Hertz pressure of 0.956 GPa), a test piece temperature of 100 ° C., and a test time of 60 minutes. The wear width of the wear scar diameter of the disk was measured and displayed in mm. The target is a disc wear scar diameter of 0.30 mm or less.
(Evaluation of corrosion prevention)
Metal corrosion prevention was evaluated by a high temperature corrosion oxidation stability test. A copper piece (0.8 mm × 25.4 mm × 25.4 mm × 6 mm fistula) and a lead piece (1 mm × 25.4 mm × 25.4 mm × 6 mm fistula) are immersed in 100 mL of the test oil, and the temperature is 135 ° C. and the air blowing amount The test was carried out for 168 hours under the condition of 5 L / hour. The amount of lead and the amount of copper in the test oil were analyzed, and if the amount of lead was 120 mass ppm or less and the amount of copper was 20 mass ppm or less, it was considered acceptable.
(JASO M328-95 valve train wear test (KA24E gasoline engine))
A grade that was equal to or better than JASO Standard Oil GV1 and superior to JASO Standard Oil GV2 was accepted. As a guide, if the cam nose wear was 16.5 μm or less, it was accepted.
(JASO M 354: 2005 valve train wear test (4D34T4 diesel engine))
A cam diameter reduction (average) of 95 μm or less, a cam diameter reduction (maximum) of 210 μm or less, and no pitching were accepted.
(JASO M 336: 1998 Cleanliness test)
If the top ring groove was clogged with carbon of 60 vol% or less and the piston ring was not stuck, it was judged acceptable.
尚、表１及び表２中の1)〜９)は以下のとおりである。
1)水素化精製鉱油(１００℃動粘度：５．７４mm2／s、硫黄分：０．０１質量％未満、粘度指数：１２８)、
2) オクチル−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
3) オクチルジフェニルアミン
4)ポリブテニルコハク酸ビスイミド、ポリブテニル基の数平均分子量１０００、N含有量２．０質量％、
5)ポリブテニルコハク酸イミド、ポリブテニル基の数平均分子量１３００、N含有量１．５質量％、Ｂ含有量０．５質量％、Ｎ／Ｂ比３．０、
6)ポリブテニルコハク酸イミド、ポリブテニル基の数平均分子量１３００、N含有量１．４５質量％、Ｂ含有量１．３質量％、Ｎ／Ｂ比１．１、
7)アゼライン酸／セバシン酸のネオペンチルグリコールエステル、
8) 硫黄含有モリブデン−コハク酸イミド錯体、Ｍｏ含有量２．１質量％
9）１，３，４−チアジアゾール化合物、硫黄分３５質量％、窒素分６．４質量％
In addition, 1) -9) in Table 1 and Table 2 are as follows.
1) Hydrorefined mineral oil (100 ° C. kinematic viscosity: 5.74 mm 2 / s, sulfur content: less than 0.01% by mass, viscosity index: 128),
2) Octyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate
3) Octyl diphenylamine
4) polybutenyl succinic acid bisimide, polybutenyl group number average molecular weight 1000, N content 2.0 mass%,
5) Number average molecular weight of polybutenyl succinimide, polybutenyl group 1300, N content 1.5% by mass, B content 0.5% by mass, N / B ratio 3.0,
6) polybutenyl succinimide, polybutenyl group number average molecular weight 1300, N content 1.45% by mass, B content 1.3% by mass, N / B ratio 1.1,
7) Neopentyl glycol ester of azelaic acid / sebacic acid,
8) Sulfur-containing molybdenum-succinimide complex, Mo content 2.1% by mass
9) 1,3,4-thiadiazole compound, sulfur content 35% by mass, nitrogen content 6.4% by mass
表１及び表２より、(A)成分〜(C)成分のすべてを含有する実施例１〜１０の組成物はホットチューブ試験(ＨＴＴ)及びＨＦＲＲで優れた成績を示し、またエンジン試験にも合格する。追加成分として(D)成分を加えることにより、ＨＦＲＲの成績が向上し、更に(D)成分に加えて(E)成分を併用することにより、エンジン試験を含めた全体的な性能が向上する。また金属腐食性に関しては、実施例７の潤滑油組成物は、鉛量が１１質量ｐｐｍ、銅量が１７質量ｐｐｍと合格範囲内であるが、この組成物にチアジアゾールを添加した実施例８の潤滑油組成物は、鉛量が１質量ｐｐｍ未満、銅量が８質量ｐｐｍであり、さらに良好な結果であった。 From Tables 1 and 2, the compositions of Examples 1 to 10 containing all of the components (A) to (C) showed excellent results in the hot tube test (HTT) and HFRR, and also in the engine test. Pass. By adding the component (D) as an additional component, the performance of the HFRR is improved, and by using the component (E) in addition to the component (D), the overall performance including the engine test is improved. Regarding the metal corrosiveness, the lubricating oil composition of Example 7 has a lead content of 11 mass ppm and a copper content of 17 mass ppm, which are within the acceptable range. In this example, thiadiazole was added to this composition. The lubricating oil composition had a lead content of less than 1 ppm by mass and a copper content of 8 ppm by mass.
Claims (3)
硫酸灰分量が０．２質量%以下、リン含量が０．０１質量％未満、硫黄含量が０．１質量%以下、ホウ素含量が０．０５〜０．０８質量%である内燃機関用潤滑油組成物。 1 to 12% by mass of at least one ashless antioxidant (A) selected from phenols and amines, 1 to 10% by mass of bis-type succinimide ashless dispersant (B), and boron-modified succinic acid A lubricating oil composition comprising 2 to 10% by mass of an imide-based dispersant (C) and having a total amount of 100% by mass with a base oil composed of mineral oil and / or synthetic oil,
Lubricating oil for internal combustion engines having a sulfated ash content of 0.2 mass% or less, a phosphorus content of less than 0.01 mass%, a sulfur content of 0.1 mass% or less, and a boron content of 0.05 to 0.08 mass% Composition.
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| JP2011157530A (en) * | 2010-02-03 | 2011-08-18 | Showa Shell Sekiyu Kk | Lubricating oil composition |
| JP2014148689A (en) * | 2014-05-27 | 2014-08-21 | Idemitsu Kosan Co Ltd | Lubricant composition |
| WO2014189057A1 (en) * | 2013-05-20 | 2014-11-27 | 出光興産株式会社 | Lubricant composition |
| JP2015034205A (en) * | 2013-08-08 | 2015-02-19 | 出光興産株式会社 | Lubricant composition for regeneration processing and manufacturing method of lubricant base oil |
| JP2015071789A (en) * | 2008-12-17 | 2015-04-16 | シェブロン・オロナイト・カンパニー・エルエルシー | Lubricating oil compositions |
| US9790450B2 (en) | 2012-03-21 | 2017-10-17 | Idemitsu Kosan Co., Ltd. | Lubricating oil composition for engine made of aluminum alloy and lubrication method |
| WO2019177125A1 (en) * | 2018-03-14 | 2019-09-19 | 出光興産株式会社 | Lubricating oil composition |
| JP2020164620A (en) * | 2019-03-29 | 2020-10-08 | 出光興産株式会社 | Lubricant composition |
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| JP2015071789A (en) * | 2008-12-17 | 2015-04-16 | シェブロン・オロナイト・カンパニー・エルエルシー | Lubricating oil compositions |
| JP2011157530A (en) * | 2010-02-03 | 2011-08-18 | Showa Shell Sekiyu Kk | Lubricating oil composition |
| US9790450B2 (en) | 2012-03-21 | 2017-10-17 | Idemitsu Kosan Co., Ltd. | Lubricating oil composition for engine made of aluminum alloy and lubrication method |
| WO2014189057A1 (en) * | 2013-05-20 | 2014-11-27 | 出光興産株式会社 | Lubricant composition |
| JPWO2014189057A1 (en) * | 2013-05-20 | 2017-02-23 | 出光興産株式会社 | Lubricating oil composition |
| US9850446B2 (en) | 2013-05-20 | 2017-12-26 | Idemitsu Kosan Co., Ltd. | Lubricant composition |
| JP2015034205A (en) * | 2013-08-08 | 2015-02-19 | 出光興産株式会社 | Lubricant composition for regeneration processing and manufacturing method of lubricant base oil |
| JP2014148689A (en) * | 2014-05-27 | 2014-08-21 | Idemitsu Kosan Co Ltd | Lubricant composition |
| WO2019177125A1 (en) * | 2018-03-14 | 2019-09-19 | 出光興産株式会社 | Lubricating oil composition |
| JPWO2019177125A1 (en) * | 2018-03-14 | 2021-02-25 | 出光興産株式会社 | Lubricating oil composition |
| JP2020164620A (en) * | 2019-03-29 | 2020-10-08 | 出光興産株式会社 | Lubricant composition |
| JP7132880B2 (en) | 2019-03-29 | 2022-09-07 | 出光興産株式会社 | lubricating oil composition |
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