JP2018203952A - Lubricating oil composition for gas engine and method reducing an amount of fuel consumption and abnormal combustion - Google Patents
Lubricating oil composition for gas engine and method reducing an amount of fuel consumption and abnormal combustion Download PDFInfo
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- JP2018203952A JP2018203952A JP2017113738A JP2017113738A JP2018203952A JP 2018203952 A JP2018203952 A JP 2018203952A JP 2017113738 A JP2017113738 A JP 2017113738A JP 2017113738 A JP2017113738 A JP 2017113738A JP 2018203952 A JP2018203952 A JP 2018203952A
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- lubricating oil
- composition
- oil composition
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- 239000000203 mixture Substances 0.000 title claims abstract description 120
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 103
- 230000002159 abnormal effect Effects 0.000 title claims abstract description 22
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 22
- 239000000446 fuel Substances 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims description 20
- 239000011777 magnesium Substances 0.000 claims abstract description 40
- 239000003599 detergent Substances 0.000 claims abstract description 35
- 239000002199 base oil Substances 0.000 claims abstract description 28
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 26
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 25
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000011574 phosphorus Substances 0.000 claims abstract description 23
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 23
- AVVIDTZRJBSXML-UHFFFAOYSA-L calcium;2-carboxyphenolate;dihydrate Chemical compound O.O.[Ca+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O AVVIDTZRJBSXML-UHFFFAOYSA-L 0.000 claims abstract description 22
- MQHWFIOJQSCFNM-UHFFFAOYSA-L Magnesium salicylate Chemical compound [Mg+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O MQHWFIOJQSCFNM-UHFFFAOYSA-L 0.000 claims abstract description 20
- 229940072082 magnesium salicylate Drugs 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011593 sulfur Substances 0.000 claims abstract description 16
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 16
- 230000001050 lubricating effect Effects 0.000 claims abstract description 14
- 239000003607 modifier Substances 0.000 claims abstract description 14
- 239000000470 constituent Substances 0.000 claims abstract description 13
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 13
- 239000011733 molybdenum Substances 0.000 claims abstract description 13
- 239000011575 calcium Substances 0.000 claims description 16
- 239000003963 antioxidant agent Substances 0.000 claims description 13
- 239000002270 dispersing agent Substances 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 238000005461 lubrication Methods 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 abstract description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 27
- 239000002585 base Substances 0.000 description 18
- -1 polyol ester Chemical class 0.000 description 17
- 239000000654 additive Substances 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 12
- 238000000921 elemental analysis Methods 0.000 description 11
- 230000000996 additive effect Effects 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
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- 230000003078 antioxidant effect Effects 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002480 mineral oil Substances 0.000 description 5
- 235000010446 mineral oil Nutrition 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 239000006078 metal deactivator Substances 0.000 description 2
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- 150000002751 molybdenum Chemical class 0.000 description 2
- 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
- 150000002894 organic compounds Chemical class 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical compound OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 2
- SXYOAESUCSYJNZ-UHFFFAOYSA-L zinc;bis(6-methylheptoxy)-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].CC(C)CCCCCOP([S-])(=S)OCCCCCC(C)C.CC(C)CCCCCOP([S-])(=S)OCCCCCC(C)C SXYOAESUCSYJNZ-UHFFFAOYSA-L 0.000 description 2
- GSOYMOAPJZYXTB-UHFFFAOYSA-N 2,6-ditert-butyl-4-(3,5-ditert-butyl-4-hydroxyphenyl)phenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(C=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 GSOYMOAPJZYXTB-UHFFFAOYSA-N 0.000 description 1
- FMNZBNCPTJEVDS-KVVVOXFISA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;(z)-octadec-9-enoic acid Chemical compound CCC(CO)(CO)CO.CCCCCCCC\C=C/CCCCCCCC(O)=O FMNZBNCPTJEVDS-KVVVOXFISA-N 0.000 description 1
- LLEFDCACDRGBKD-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;nonanoic acid Chemical compound CCC(CO)(CO)CO.CCCCCCCCC(O)=O LLEFDCACDRGBKD-UHFFFAOYSA-N 0.000 description 1
- ALKCLFLTXBBMMP-UHFFFAOYSA-N 3,7-dimethylocta-1,6-dien-3-yl hexanoate Chemical compound CCCCCC(=O)OC(C)(C=C)CCC=C(C)C ALKCLFLTXBBMMP-UHFFFAOYSA-N 0.000 description 1
- MDWVSAYEQPLWMX-UHFFFAOYSA-N 4,4'-Methylenebis(2,6-di-tert-butylphenol) Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 MDWVSAYEQPLWMX-UHFFFAOYSA-N 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、ガスエンジン用潤滑油組成物、及び燃料消費量の改善方法又は異常燃焼の低減方法に関する。 The present invention relates to a lubricating oil composition for a gas engine, and a method for improving fuel consumption or a method for reducing abnormal combustion.
ガスエンジンコージェネレーションシステムは、ガスエンジンによって発電し、排熱をエネルギーとして利用するシステムである。このようなシステムで用いられるガスエンジンは、運転条件が高負荷の連続となるため、ガスエンジン用潤滑油は徐々に酸化劣化し、定期的な交換が必要となる。その交換回数を少なくするために、ガスエンジン用潤滑油には、長寿命化が求められている。 The gas engine cogeneration system is a system that generates power by a gas engine and uses exhaust heat as energy. Since the gas engine used in such a system has a continuous high operating condition, the lubricating oil for the gas engine gradually deteriorates due to oxidation and requires periodic replacement. In order to reduce the number of times of replacement, the service life of the lubricating oil for gas engines is required.
近年、ガスエンジンコージェネレーションシステムの高効率化が急務となっており、エンジンのコンパクト化及びエンジンフリクションの低減による省燃費化が検討されている。しかし、エンジンの高出力化に伴うエンジン内での異常燃焼（過早着火：プレイグニッション）の発生が問題視されている。そのため、ガスエンジン用潤滑油には、長寿命化に加えて、異常燃焼を抑制することが求められている。 In recent years, there has been an urgent need to improve the efficiency of gas engine cogeneration systems, and fuel efficiency has been studied by making the engine more compact and reducing engine friction. However, the occurrence of abnormal combustion (premature ignition: pre-ignition) in the engine accompanying the increase in engine output is regarded as a problem. Therefore, in addition to extending the life, gas engine lubricating oils are required to suppress abnormal combustion.
ガスエンジン用潤滑油は、一般的に、潤滑油基油と、上記のような要求特性に応じて選択される添加剤とを含有する。例えば、特許文献１〜５には、摩耗防止性、塩基価維持性及び高温清浄性の観点から、リン系添加剤、金属清浄剤等を含有する潤滑油組成物が開示されている。 A gas engine lubricating oil generally contains a lubricating base oil and an additive selected according to the required characteristics as described above. For example, Patent Documents 1 to 5 disclose lubricating oil compositions containing a phosphorus-based additive, a metal detergent, and the like from the viewpoints of wear prevention, base number maintenance, and high-temperature cleanability.
しかしながら、従来の潤滑油組成物においても、特に異常燃焼の抑制についてはさらなる改善の余地がある。そこで、本発明は、寿命特性及び省燃費性に優れ、さらに異常燃焼を抑制することが可能なガスエンジン用潤滑油組成物を提供することを主な目的とする。 However, even in the conventional lubricating oil composition, there is room for further improvement, particularly regarding the suppression of abnormal combustion. Accordingly, the main object of the present invention is to provide a lubricating oil composition for a gas engine that is excellent in life characteristics and fuel economy, and that can suppress abnormal combustion.
上記課題を解決するために、本発明は、下記［１］〜［４］に示す潤滑油組成物、下記［５］に示す燃料消費量の改善方法又は異常燃焼の低減方法、下記［６］に示す組成物の使用（応用）、及び下記［７］に示す組成物の製造のための使用（応用）を提供する。 In order to solve the above problems, the present invention provides a lubricating oil composition shown in the following [1] to [4], a fuel consumption improving method or abnormal combustion reducing method shown in the following [5], and the following [6]. The use (application) of the composition shown in the following and the use (application) for the production of the composition shown in [7] below are provided.
［１］潤滑油基油と、構成元素としてリンを含み、かつ硫黄を含まない摩耗防止剤と、有機モリブデン系摩擦調整剤と、カルシウムサリシレート系清浄剤と、マグネシウムサリシレート系清浄剤と、を含有し、組成物中のマグネシウム元素含有量に対する組成物中のカルシウム元素含有量の比が１．５０〜１．８０であり、ＪＩＳ Ｋ２２７２に準拠して測定される硫酸灰分量が０．６質量％以下である、ガスエンジン用潤滑油組成物。
［２］組成物中のマグネシウムサリシレート系清浄剤のマグネシウム元素換算の含有量に対する、組成物中のカルシウムサリシレート系清浄剤のカルシウム元素換算の含有量の比が１．５０〜１．８０である、［１］に記載のガスエンジン用潤滑油組成物。
［３］１００℃における動粘度が１０〜１２ｍｍ２／ｓである、［１］又は［２］に記載のガスエンジン用潤滑油組成物。
［４］酸化防止剤及び無灰分散剤からなる群より選ばれる少なくとも１種をさらに含有する、［１］〜［３］のいずれかに記載のガスエンジン用潤滑油組成物。
［５］［１］〜［４］のいずれかに記載のガスエンジン用潤滑油組成物を用いて潤滑を行う、燃料消費量の改善方法又は異常燃焼の低減方法。
［６］組成物のガスエンジン用潤滑油としての使用であって、組成物が、潤滑油基油と、構成元素としてリンを含み、かつ硫黄を含まない摩耗防止剤と、有機モリブデン系摩擦調整剤と、カルシウムサリシレート系清浄剤と、マグネシウムサリシレート系清浄剤と、を含有し、組成物中のマグネシウム元素含有量に対する組成物中のカルシウム元素含有量の比が１．５０〜１．８０であり、ＪＩＳ Ｋ２２７２に準拠して測定される硫酸灰分量が０．６質量％以下である、使用。
［７］組成物のガスエンジン用潤滑油の製造のための使用であって、組成物が、潤滑油基油と、構成元素としてリンを含み、かつ硫黄を含まない摩耗防止剤と、有機モリブデン系摩擦調整剤と、カルシウムサリシレート系清浄剤と、マグネシウムサリシレート系清浄剤と、を含有し、組成物中のマグネシウム元素含有量に対する組成物中のカルシウム元素含有量の比が１．５０〜１．８０であり、ＪＩＳ Ｋ２２７２に準拠して測定される硫酸灰分量が０．６質量％以下である、使用。
[1] Contains a lubricant base oil, an antiwear agent containing phosphorus as a constituent element and not containing sulfur, an organic molybdenum friction modifier, a calcium salicylate detergent, and a magnesium salicylate detergent. The ratio of the calcium element content in the composition to the magnesium element content in the composition is 1.50 to 1.80, and the sulfated ash content measured according to JIS K2272 is 0.6% by mass. The lubricating oil composition for gas engines which is the following.
[2] The ratio of the content in terms of calcium of the calcium salicylate detergent in the composition to the content in terms of magnesium element of the magnesium salicylate detergent in the composition is 1.50 to 1.80. [1] The lubricating oil composition for gas engines according to [1].
[3] The lubricating oil composition for gas engines according to [1] or [2], wherein the kinematic viscosity at 100 ° C. is 10 to 12 mm 2 / s.
[4] The lubricating oil composition for a gas engine according to any one of [1] to [3], further containing at least one selected from the group consisting of an antioxidant and an ashless dispersant.
[5] A method for improving fuel consumption or a method for reducing abnormal combustion, wherein lubrication is performed using the lubricating oil composition for gas engines according to any one of [1] to [4].
[6] Use of the composition as a lubricating oil for a gas engine, the composition comprising a lubricating base oil, an anti-wear agent containing phosphorus as a constituent element and not containing sulfur, and an organic molybdenum friction adjustment A calcium salicylate detergent and a magnesium salicylate detergent, and the ratio of the calcium element content in the composition to the magnesium element content in the composition is 1.50 to 1.80 Use, wherein the sulfated ash content measured in accordance with JIS K2272 is 0.6% by mass or less.
[7] Use of the composition for the production of a lubricating oil for gas engines, the composition comprising a lubricating base oil, an anti-wear agent containing phosphorus as a constituent element and not containing sulfur, and organic molybdenum A system friction modifier, a calcium salicylate detergent, and a magnesium salicylate detergent, wherein the ratio of the content of calcium element in the composition to the content of magnesium element in the composition is 1.50-1. Use that is 80 and the sulfated ash content measured according to JIS K2272 is 0.6% by mass or less.
本発明によれば、寿命特性及び省燃費性に優れ、さらに異常燃焼を抑制することが可能なガスエンジン用潤滑油組成物が提供される。また、本発明によれば、ガスエンジン用潤滑油組成物を用いて潤滑を行う、燃料消費量の改善方法又は異常燃焼の低減方法が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the lubricating oil composition for gas engines which is excellent in a lifetime characteristic and fuel-saving property, and can suppress abnormal combustion is provided. Moreover, according to this invention, the improvement method of the fuel consumption or the reduction method of abnormal combustion which lubricates using the lubricating oil composition for gas engines is provided.
以下、本発明の実施形態について詳細に説明する。ただし、本発明は以下の実施形態に限定されるものではない。 Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.
一実施形態のガスエンジン用潤滑油組成物は、潤滑油基油と、構成元素としてリンを含み、かつ硫黄を含まない摩耗防止剤と、有機モリブデン系摩擦調整剤と、カルシウムサリシレート系清浄剤と、マグネシウムサリシレート系清浄剤と、を含有する。 A lubricating oil composition for a gas engine according to an embodiment includes a lubricating oil base oil, an antiwear agent containing phosphorus as a constituent element and not containing sulfur, an organic molybdenum friction modifier, and a calcium salicylate detergent. And a magnesium salicylate detergent.
［潤滑油基油］
潤滑油基油は、通常の潤滑油分野で使用される潤滑油基油を用いることができる。ここで、潤滑油基油としては、具体的には、鉱油系基油、合成系基油、又は両者の混合物が挙げられる。
[Lubricant base oil]
As the lubricating base oil, a lubricating base oil used in the ordinary lubricating oil field can be used. Here, specific examples of the lubricating base oil include a mineral base oil, a synthetic base oil, or a mixture of both.
鉱油系基油としては、例えば、パラフィン系、ナフテン系、又は芳香族系の原油の蒸留により得られる灯油留分；灯油留分からの抽出操作等により得られるノルマルパラフィン；及びパラフィン系、ナフテン系、又は芳香族系の原油の蒸留により得られる潤滑油留分、あるいは潤滑油脱ろう工程により得られる、スラックワックス等のワックス及び／又はガストゥリキッド（ＧＴＬ）プロセス等により得られる、フィッシャートロプシュワックス、ＧＴＬワックス等の合成ワックスを原料とし、溶剤脱れき、溶剤抽出、水素化分解、水素化異性化、溶剤脱ろう、接触脱ろう、水素化精製、硫酸洗浄、白土処理等の精製処理を１つ又は２つ以上適宜組み合わせて精製したパラフィン系鉱油、ナフテン系鉱油、ノルマルパラフィン系基油、イソパラフィン系基油、芳香族系基油等が挙げられる。これらの鉱油系基油は単独で使用してもよく、２種以上を任意の割合で組み合わせて使用してもよい。 Mineral oil base oils include, for example, kerosene fractions obtained by distillation of paraffinic, naphthenic, or aromatic crude oils; normal paraffins obtained by extraction operations from kerosene fractions; and paraffinic, naphthenic, Or a Fischer-Tropsch wax obtained by a lubricating oil fraction obtained by distillation of an aromatic crude oil, or a wax such as slack wax obtained by a lubricating oil dewaxing process and / or a gas-to-liquid (GTL) process, etc. Synthetic wax such as GTL wax is used as a raw material, and solvent purification, solvent extraction, hydrocracking, hydroisomerization, solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid washing, clay treatment, etc. Or, paraffinic mineral oil, naphthenic mineral oil, normal paraffinic base oil, isopa which has been refined by appropriately combining two or more Fin-based base oils, aromatic base oils and the like. These mineral oil base oils may be used alone or in combination of two or more at any ratio.
合成系基油としては、例えば、ポリα−オレフィン又はその水素化物；プロピレンオリゴマー、イソブチレンオリゴマー、ポリブテン、１−オクテンオリゴマー、１−デセンオリゴマー、エチレン−プロピレンオリゴマー等のオレフィンオリゴマー又はその水素化物；アルキルベンゼン；アルキルナフタレン；ジエステル（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−２−エチルヘキシルアゼレート、ジイソデシルアジペート、ジトリデシルアジペート、ジ−２−エチルヘキシルセバケート等）；ポリオールエステル（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、トリメチロールプロパンオレート、ペンタエリスリトール２−エチルヘキサノエート、ペンタエリスリトールペラルゴネート等）；ポリオキシアルキレングリコール、ジアルキルジフェニルエーテル、ポリフェニルエーテル等が挙げられる。これらの合成系基油は単独で使用してもよく、２種以上を任意の割合で組み合わせて使用してもよい。 Synthetic base oils include, for example, poly α-olefins or hydrides thereof; olefin oligomers such as propylene oligomers, isobutylene oligomers, polybutenes, 1-octene oligomers, 1-decene oligomers, ethylene-propylene oligomers or hydrides thereof; alkylbenzenes Alkyl naphthalene; diester (ditridecyl glutarate, di-2-ethylhexyl adipate, di-2-ethylhexyl azelate, diisodecyl adipate, ditridecyl adipate, di-2-ethylhexyl sebacate, etc.); polyol ester (trimethylolpropane capri) Rate, trimethylolpropane pelargonate, trimethylolpropane oleate, pentaerythritol 2-ethylhexanoate, pentaerythritol pera Goneto etc.); polyoxyalkylene glycols, dialkyl ethers, polyphenyl ether, and the like. These synthetic base oils may be used alone or in combination of two or more at any ratio.
潤滑油基油の１００℃における動粘度は、特に制限されないが、好ましくは６．０ｍｍ２／ｓ以上、より好ましくは６．２ｍｍ２／ｓ以上、さらに好ましくは６．３ｍｍ２／ｓ以上である。１００℃における動粘度が６．０ｍｍ２／ｓ以上であると、油膜形成及び製品の蒸発性能により優れる傾向にあり、さらに耐摩耗性能を向上させ、燃料消費を抑えることが可能となり得る。また、潤滑油基油の１００℃における動粘度は、好ましくは７．０ｍｍ２／ｓ以下、より好ましくは６．８ｍｍ２／ｓ以下、さらに好ましくは６．７ｍｍ２／ｓ以下である。１００℃における動粘度が７．０ｍｍ２／ｓ以下であると、粘度指数向上剤の添加による充分な高効率（省燃費）効果がより一層得られる傾向にある。 The kinematic viscosity at 100 ° C. of the lubricating base oil is not particularly limited, but is preferably 6.0 mm 2 / s or more, more preferably 6.2 mm 2 / s or more, and even more preferably 6.3 mm 2 / s or more. . When the kinematic viscosity at 100 ° C. is 6.0 mm 2 / s or more, it tends to be more excellent in oil film formation and product evaporation performance, and it may be possible to improve wear resistance and suppress fuel consumption. The kinematic viscosity at 100 ° C. of the lubricating base oil is preferably 7.0 mm 2 / s or less, more preferably 6.8 mm 2 / s or less, and further preferably 6.7 mm 2 / s or less. When the kinematic viscosity at 100 ° C. is 7.0 mm 2 / s or less, sufficient high efficiency (fuel saving) effect due to the addition of the viscosity index improver tends to be further obtained.
潤滑油基油の４０℃における動粘度は、特に制限されないが、好ましくは３０ｍｍ２／ｓ以上、より好ましくは３２ｍｍ２／ｓ以上、さらに好ましくは３５ｍｍ２／ｓ以上である。４０℃における動粘度が３０ｍｍ２／ｓ以上であると、油膜形成及び製品の蒸発性能により優れる傾向にあり、さらに耐摩耗性能を向上させ、燃料消費を抑えることが可能となり得る。また、潤滑油基油の４０℃における動粘度は、好ましくは４５ｍｍ２／ｓ以下、より好ましくは４０ｍｍ２／ｓ以下、さらに好ましくは３８ｍｍ２／ｓ以下である。４０℃における動粘度が４５ｍｍ２／ｓ以下であると、粘度指数向上剤の添加による充分な高効率（省燃費）効果がより一層得られる傾向にある。 The kinematic viscosity at 40 ° C. of the lubricating base oil is not particularly limited, but is preferably 30 mm 2 / s or more, more preferably 32 mm 2 / s or more, and further preferably 35 mm 2 / s or more. If the kinematic viscosity at 40 ° C. is 30 mm 2 / s or more, it tends to be more excellent in oil film formation and product evaporation performance, and it may be possible to improve wear resistance and suppress fuel consumption. The kinematic viscosity at 40 ° C. of the lubricating base oil is preferably 45 mm 2 / s or less, more preferably 40 mm 2 / s or less, and still more preferably 38 mm 2 / s or less. When the kinematic viscosity at 40 ° C. is 45 mm 2 / s or less, sufficient high efficiency (fuel saving) effect due to the addition of the viscosity index improver tends to be further obtained.
潤滑油基油の粘度指数は、特に制限されないが、好ましくは１００以上、より好ましくは１１０以上、さらに好ましくは１２０以上である。粘度指数が上記の範囲内であると、外部の温度に対して粘度の安定性が確保されるため、使用時における外部の温度変化に対しても安定的に油膜を形成できる傾向にある。 The viscosity index of the lubricating base oil is not particularly limited, but is preferably 100 or more, more preferably 110 or more, and still more preferably 120 or more. When the viscosity index is within the above range, the stability of the viscosity with respect to the external temperature is ensured, so that the oil film tends to be stably formed even with respect to the external temperature change during use.
本明細書における４０℃及び１００℃における動粘度並びに粘度指数は、それぞれＪＩＳ Ｋ２２８３「原油及び石油製品−動粘度試験方法及び粘度指数算出方法」に準拠して測定される値を意味する。 The kinematic viscosity and viscosity index at 40 ° C. and 100 ° C. in this specification mean values measured in accordance with JIS K2283 “Crude oil and petroleum products—Kinematic viscosity test method and viscosity index calculation method”, respectively.
［摩耗防止剤］
潤滑油組成物は、構成元素としてリンを含み、かつ硫黄を含まない摩耗防止剤を含有する。このような摩耗防止剤を用いることによって、寿命特性を改善することができる。
[Antiwear agent]
The lubricating oil composition contains an antiwear agent that contains phosphorus as a constituent element and does not contain sulfur. By using such an antiwear agent, the life characteristics can be improved.
摩耗防止剤としては、上記条件を満たすものであれば、特に制限されないが、例えば、亜リン酸エステル類（ホスファイト）、リン酸エステル類（ホスフェート）、これらのアミン塩、これらの金属塩、これらの誘導体等が挙げられる。これらの摩耗防止剤は単独で使用してもよく、２種以上を任意の割合で組み合わせて使用してもよい。 The antiwear agent is not particularly limited as long as it satisfies the above conditions. For example, phosphites (phosphites), phosphates (phosphates), amine salts thereof, metal salts thereof, These derivatives are mentioned. These antiwear agents may be used alone or in combination of two or more at any ratio.
これらの中で、摩耗防止剤は、ジアルキルリン酸亜鉛（ＺＰ）、すなわち、下記一般式（Ａ）で表される化合物であることが好ましい。 Among these, the antiwear agent is preferably a zinc dialkyl phosphate (ZP), that is, a compound represented by the following general formula (A).
式（Ｄ）中、Ｒ２１〜Ｒ２４は、それぞれ独立に、炭素数１〜２４の直鎖状又は分枝状のアルキル基を示す。 In formula (D), R 21 to R 24 each independently represent a linear or branched alkyl group having 1 to 24 carbon atoms.
摩耗防止剤の含有量（Ｃ（Ｐ））は、組成物全量を基準として、リン元素換算で、１００〜１０００質量ｐｐｍであってもよい。Ｃ（Ｐ）は、好ましくは１００質量ｐｐｍ以上、より好ましくは２００質量ｐｐｍ以上、さらに好ましくは３００質量ｐｐｍ以上である。Ｃ（Ｐ）が１００質量ｐｐｍ以上であると、潤滑油組成物において、より充分な摩耗防止性能が得られる傾向にある。Ｃ（Ｐ）は、好ましくは１０００質量ｐｐｍ以下、より好ましくは８００質量ｐｐｍ以下、さらに好ましくは６００質量ｐｐｍ以下である。Ｃ（Ｐ）が１０００質量ｐｐｍ以下であると、潤滑油組成物において、灰分量の増加に伴う堆積物の増加及び排ガス後処理触媒の被毒をより抑制できる傾向にある。 The content (C (P)) of the antiwear agent may be 100 to 1000 ppm by mass in terms of phosphorus element based on the total amount of the composition. C (P) is preferably 100 mass ppm or more, more preferably 200 mass ppm or more, and even more preferably 300 mass ppm or more. When C (P) is 100 ppm by mass or more, in the lubricating oil composition, more sufficient wear prevention performance tends to be obtained. C (P) is preferably 1000 ppm by mass or less, more preferably 800 ppm by mass or less, and still more preferably 600 ppm by mass or less. When the C (P) is 1000 ppm by mass or less, in the lubricating oil composition, there is a tendency that the increase in deposits accompanying the increase in the ash content and the poisoning of the exhaust gas aftertreatment catalyst can be further suppressed.
上記Ｃ（Ｐ）は、摩耗防止剤のリン元素含有量を予めＩＣＰ元素分析等によって分析し、その分析値と仕込み量との積から求めることができる。 C (P) can be obtained from the product of the analysis value and the charged amount by analyzing the phosphorus element content of the antiwear agent in advance by ICP elemental analysis or the like.
［摩擦調整剤］
潤滑油組成物は、有機モリブデン系摩擦調整剤を含有する。
[Friction modifier]
The lubricating oil composition contains an organomolybdenum friction modifier.
有機モリブデン系摩擦調整剤としては、例えば、構成元素として硫黄を含む有機モリブデン化合物、構成元素として硫黄を含まない有機モリブデン化合物等が挙げられる。 Examples of the organic molybdenum friction modifier include organic molybdenum compounds containing sulfur as a constituent element, and organic molybdenum compounds not containing sulfur as a constituent element.
構成元素として硫黄を含む有機モリブデン化合物としては、例えば、モリブデンジチオカーバメート（ＭｏＤＴＣ）、モリブデンジチオホスフェート等の硫黄含有有機モリブデン化合物、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等）と、硫黄含有有機化合物（例えば、アルキル（チオ）キサンテート、チアジアゾール、メルカプトチアジアゾール、チオカーボネート、テトラハイドロカルビルチウラムジスルフィド、ビス（ジ（チオ）ハイドロカルビルジチオホスホネート）ジスルフィド、有機（ポリ）サルファイド、硫化エステル等）又はその他の有機化合物との錯体などが挙げられる。これらの有機モリブデン化合物は単独で使用してもよく、２種以上を任意の割合で組み合わせて使用してもよい。 Examples of the organic molybdenum compound containing sulfur as a constituent element include sulfur-containing organic molybdenum compounds such as molybdenum dithiocarbamate (MoDTC) and molybdenum dithiophosphate, molybdenum compounds (for example, molybdenum oxide such as molybdenum dioxide and molybdenum trioxide, and ortho molybdenum). Acid, paramolybdic acid, molybdic acid such as (poly) sulfurized molybdic acid, metal salts of these molybdic acids, molybdate such as ammonium salts, etc.) and sulfur-containing organic compounds (for example, alkyl (thio) xanthate, thiadiazole, Mercaptothiadiazole, thiocarbonate, tetrahydrocarbyl thiuram disulfide, bis (di (thio) hydrocarbyl dithiophosphonate) disulfide, organic (poly) sulfide, sulfide ester, etc.) It is like complexes with other organic compounds. These organic molybdenum compounds may be used alone or in combination of two or more at any ratio.
構成元素として硫黄を含まない有機モリブデン化合物としては、例えば、モリブデン−アミン錯体、モリブデン−コハク酸イミド錯体、有機酸のモリブデン塩、アルコールのモリブデン塩などが挙げられる。これらの有機モリブデン化合物は単独で使用してもよく、２種以上を任意の割合で組み合わせて使用してもよい。モリブデン−アミン錯体を構成するモリブデン化合物としては、三酸化モリブデン又はその水和物（ＭｏＯ３・ｎＨ２Ｏ）、モリブデン酸（Ｈ２ＭｏＯ４）、モリブデン酸アルカリ金属塩（Ｍ２ＭｏＯ４；Ｍはアルカリ金属を示す）、モリブデン酸アンモニウム（（ＮＨ４）２ＭｏＯ４又は（ＮＨ４）６［Ｍｏ７Ｏ２４］・４Ｈ２Ｏ）、ＭｏＣｌ５、ＭｏＯＣｌ４、ＭｏＯ２Ｃｌ２、ＭｏＯ２Ｂｒ２、Ｍｏ２Ｏ３Ｃｌ６等の硫黄を含まないモリブデン化合物が挙げられる。 Examples of the organic molybdenum compound that does not contain sulfur as a constituent element include molybdenum-amine complexes, molybdenum-succinimide complexes, molybdenum salts of organic acids, molybdenum salts of alcohols, and the like. These organic molybdenum compounds may be used alone or in combination of two or more at any ratio. As the molybdenum compound constituting the molybdenum-amine complex, molybdenum trioxide or a hydrate thereof (MoO 3 .nH 2 O), molybdic acid (H 2 MoO 4 ), molybdate alkali metal salt (M 2 MoO 4 ; M Represents an alkali metal), ammonium molybdate ((NH 4 ) 2 MoO 4 or (NH 4 ) 6 [Mo 7 O 24 ] · 4H 2 O), MoCl 5 , MoOCl 4 , MoO 2 Cl 2 , MoO 2 Br 2 , molybdenum compounds not containing sulfur such as Mo 2 O 3 Cl 6 .
摩擦調整剤の含有量（Ｃ（Ｍｏ））は、組成物全量を基準として、モリブデン元素換算で、１００〜１０００質量ｐｐｍであってもよい。Ｃ（Ｍｏ）は、好ましくは１００質量ｐｐｍ以上、より好ましくは１２０質量ｐｐｍ以上、さらに好ましくは１５０質量ｐｐｍ以上である。Ｃ（Ｍｏ）が１００質量ｐｐｍ以上であると、潤滑油組成物において、より充分なフリクション低減性能が得られる傾向にある。Ｃ（Ｍｏ）は、好ましくは１０００質量ｐｐｍ以下、より好ましくは５００質量ｐｐｍ以下、さらに好ましくは３００質量ｐｐｍ以下である。Ｃ（Ｍｏ）が１０００質量ｐｐｍ以下であると、潤滑油組成物において、製品貯蔵時の沈殿生成及びエンジン内での体積物の増加をより抑制できる傾向にある。 The content of the friction modifier (C (Mo)) may be 100 to 1000 ppm by mass in terms of molybdenum based on the total amount of the composition. C (Mo) is preferably 100 mass ppm or more, more preferably 120 mass ppm or more, and further preferably 150 mass ppm or more. When C (Mo) is 100 mass ppm or more, in the lubricating oil composition, more sufficient friction reduction performance tends to be obtained. C (Mo) is preferably 1000 ppm by mass or less, more preferably 500 ppm by mass or less, and still more preferably 300 ppm by mass or less. When C (Mo) is 1000 ppm by mass or less, in the lubricating oil composition, it tends to be possible to further suppress precipitation formation during product storage and increase in volume in the engine.
上記Ｃ（Ｍｏ）は、摩擦調整剤のモリブデン元素含有量を予めＩＣＰ元素分析等によって分析し、その分析値と仕込み量との積から求めることができる。 The C (Mo) can be obtained from the product of the analysis value and the charged amount by analyzing the molybdenum element content of the friction modifier in advance by ICP elemental analysis or the like.
［金属系清浄剤］
潤滑油組成物は、カルシウムサリシレート系清浄剤と、マグネシウムサリシレート系清浄剤と、を含有する。
[Metal-based detergent]
The lubricating oil composition contains a calcium salicylate detergent and a magnesium salicylate detergent.
カルシウムサリシレート系清浄剤は、下記一般式（Ｂ）で表される化合物（カルシウムサリシレート）である。 The calcium salicylate detergent is a compound (calcium salicylate) represented by the following general formula (B).
式（Ｂ）中、Ｒｂは炭素数１４〜２８の直鎖状又は分岐状のアルキル基を示す。Ｒｂの炭素数は、好ましくは１４〜２０である。ｎｂはＲｂの置換数を示し、１又は２である。ｎｂが２のとき、Ｒｂは互いに同一であっても異なっていてもよい。 In the formula (B), R b represents a linear or branched alkyl group having 14 to 28 carbon atoms. The number of carbon atoms in R b is preferably 14-20. nb represents the number of substitutions of R b and is 1 or 2. When nb is 2, R b may be the same as or different from each other.
カルシウムサリシレートの製造方法としては、特に制限されないが、例えば、アルキルサリシレートに、カルシウム酸化物、カルシウム水酸化物等の金属塩基を反応させる方法、一度ナトリウム塩、カリウム塩等のアルカリ金属塩としてからカルシウム塩と置換させる方法が挙げられる。 The method for producing calcium salicylate is not particularly limited. For example, calcium salicylate is reacted with a metal base such as calcium oxide or calcium hydroxide, and once alkali metal salt such as sodium salt or potassium salt is used. The method of substituting with a salt is mentioned.
カルシウムサリシレートは、上述の方法によって得られた中性塩だけではなく、これら中性塩と過剰のアルカリ金属又はアルカリ土類金属塩、アルカリ金属又はアルカリ土類金属塩基（アルカリ金属又はアルカリ土類金属の水酸化物、酸化物等）などを水の存在下で加熱することによって得られる塩基性塩、炭酸ガス又はホウ酸若しくはホウ酸塩の存在下で中性塩をアルカリ金属又はアルカリ土類金属の水酸化物等の塩基と反応させることにより得られる過塩基性塩であってもよい。 Calcium salicylate is not only a neutral salt obtained by the above-mentioned method, but also these neutral salts and excess alkali metal or alkaline earth metal salt, alkali metal or alkaline earth metal base (alkali metal or alkaline earth metal). A basic salt, carbon dioxide gas, or neutral salt in the presence of boric acid or borate obtained by heating in the presence of water. An overbased salt obtained by reacting with a base such as hydroxide may be used.
マグネシウムサリシレート系清浄剤は、下記一般式（Ｃ）で表される化合物（マグネシウムサリシレート）である。 The magnesium salicylate detergent is a compound (magnesium salicylate) represented by the following general formula (C).
式（Ｃ）中、Ｒｃは炭素数１４〜２８の直鎖状又は分岐状のアルキル基を示す。Ｒｃの炭素数は、好ましくは１４〜２５である。ｎｃはＲｃの置換数を示し、１又は２である。ｎｃが２のとき、Ｒｃは互いに同一であっても異なっていてもよい。 In formula (C), R c represents a linear or branched alkyl group having 14 to 28 carbon atoms. The carbon number of R c is preferably 14 to 25. nc represents the number of substitutions of R c and is 1 or 2. When nc is 2, R c may be the same as or different from each other.
マグネシウムサリシレートは、上述のカルシウムサリシレートの製造方法と同様の製造方法で得ることができる。 Magnesium salicylate can be obtained by a production method similar to the above-described production method of calcium salicylate.
マグネシウムサリシレートは、上述のカルシウムサリシレートと同様に、中性塩、塩基性塩又は過塩基性塩であってもよい。 Magnesium salicylate may be a neutral salt, a basic salt or an overbased salt, similar to the calcium salicylate described above.
組成物中のマグネシウムサリシレート系清浄剤のマグネシウム換算の含有量をＣ（Ｍｇ）、組成物中のカルシウムサリシレート系清浄剤のカルシウム元素換算の含有量をＣ（Ｃａ）としたとき、Ｃ（Ｍｇ）に対するＣ（Ｃａ）の比（Ｃ（Ｃａ）／Ｃ（Ｍｇ））は、１．５０〜１．８０であってもよい。Ｃ（Ｃａ）／Ｃ（Ｍｇ）は、好ましくは１．５０以上、より好ましくは１．５３以上、さらに好ましくは１．５５以上である。Ｃ（Ｃａ）／Ｃ（Ｍｇ）が１．５０以上であると、潤滑油組成物の寿命がより長くなる傾向にある。Ｃ（Ｃａ）／Ｃ（Ｍｇ）は、好ましくは１．８０以下、より好ましくは１．７０以下、さらに好ましくは１．６０以下である。Ｃ（Ｃａ）／Ｃ（Ｍｇ）が１．８０以下であると、潤滑油組成物の異常燃焼がより抑制される傾向にある。 When the magnesium equivalent content of the magnesium salicylate detergent in the composition is C (Mg) and the calcium element equivalent content of the calcium salicylate detergent in the composition is C (Ca), C (Mg) The ratio of C (Ca) to C (Ca) / C (Mg) may be 1.50 to 1.80. C (Ca) / C (Mg) is preferably 1.50 or more, more preferably 1.53 or more, and further preferably 1.55 or more. When C (Ca) / C (Mg) is 1.50 or more, the life of the lubricating oil composition tends to be longer. C (Ca) / C (Mg) is preferably 1.80 or less, more preferably 1.70 or less, and still more preferably 1.60 or less. When C (Ca) / C (Mg) is 1.80 or less, abnormal combustion of the lubricating oil composition tends to be further suppressed.
上記Ｃ（Ｃａ）は、カルシウムサリシレート系清浄剤のカルシウム元素含有量を予めＩＣＰ元素分析等によって分析し、その分析値と仕込み量との積から求めることができる。同様に、上記Ｃ（Ｍｇ）は、マグネシウムサリシレート系清浄剤のマグネシウム元素含有量を予めＩＣＰ元素分析等によって分析し、その分析値と仕込み量との積から求めることができる。 The C (Ca) can be obtained from the product of the analytical value and the charged amount by previously analyzing the calcium element content of the calcium salicylate detergent by ICP elemental analysis or the like. Similarly, the C (Mg) can be obtained from the product of the analytical value and the charged amount by analyzing the magnesium element content of the magnesium salicylate detergent in advance by ICP elemental analysis or the like.
マグネシウムサリシレート系清浄剤のマグネシウム元素換算の含有量（Ｃ（Ｍｇ））とカルシウムサリシレート系清浄剤のカルシウム元素換算の含有量（Ｃ（Ｃａ））との総量（Ｃ（Ｃａ）＋Ｃ（Ｍｇ））は、８００〜１５００質量ｐｐｍであってもよい。Ｃ（Ｃａ）＋Ｃ（Ｍｇ）は、好ましくは８００質量ｐｐｍ以上、より好ましくは９００質量ｐｐｍ以上、さらに好ましくは１０００質量ｐｐｍ以上である。Ｃ（Ｃａ）＋Ｃ（Ｍｇ）が８００質量ｐｐｍ以上であると、より充分な清浄性能及び寿命性能が得られる傾向にある。また、Ｃ（Ｃａ）＋Ｃ（Ｍｇ）は、好ましくは１５００質量ｐｐｍ以下、より好ましくは１４００質量ｐｐｍ以下、さらに好ましくは１３００質量ｐｐｍ以下である。Ｃ（Ｃａ）＋Ｃ（Ｍｇ）が１５００質量ｐｐｍ以下であると、異常燃焼をより抑制できる傾向にある。 Total amount (C (Ca) + C (Mg)) of magnesium element equivalent content (C (Mg)) of magnesium salicylate detergent and calcium element equivalent content (C (Ca)) of calcium salicylate detergent 800-1500 mass ppm may be sufficient. C (Ca) + C (Mg) is preferably 800 ppm by mass or more, more preferably 900 ppm by mass or more, and further preferably 1000 ppm by mass or more. When C (Ca) + C (Mg) is 800 mass ppm or more, more sufficient cleaning performance and life performance tend to be obtained. Further, C (Ca) + C (Mg) is preferably 1500 mass ppm or less, more preferably 1400 mass ppm or less, and still more preferably 1300 mass ppm or less. When C (Ca) + C (Mg) is 1500 mass ppm or less, abnormal combustion tends to be further suppressed.
潤滑油組成物は、酸化防止剤及び無灰分散剤からなる群より選ばれる少なくとも１種をさらに含有していてもよい。 The lubricating oil composition may further contain at least one selected from the group consisting of an antioxidant and an ashless dispersant.
酸化防止剤は、特に制限されず、通常の潤滑油分野に使用される酸化防止剤を使用することができる。酸化防止剤としては、例えば、フェノール系、アミン系等の無灰酸化防止剤、銅系、モリブデン系等の金属系酸化防止剤などが挙げられる。具体的には、例えば、フェノール系無灰酸化防止剤としては、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）等が、アミン系無灰酸化防止剤としては、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、ジアルキルジフェニルアミン、ジフェニルアミン等が挙げられる。 The antioxidant is not particularly limited, and an antioxidant used in a normal lubricating oil field can be used. Examples of the antioxidant include ashless antioxidants such as phenols and amines, and metal antioxidants such as copper and molybdenum. Specifically, for example, as a phenol-based ashless antioxidant, 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4′-bis (2,6-di-tert- Butylphenol) and the like are amine-based ashless antioxidants such as phenyl-α-naphthylamine, alkylphenyl-α-naphthylamine, dialkyldiphenylamine, and diphenylamine.
酸化防止剤の含有量は、組成物全量を基準として、０．１〜２．０質量％であってもよい。 The content of the antioxidant may be 0.1 to 2.0% by mass based on the total amount of the composition.
無灰分散剤は、特に制限されず、通常の潤滑油分野に使用される無灰分散剤を使用することができる。無灰分散剤としては、例えば、炭素数４０以上４００以下の直鎖若しくは分枝状のアルキル基又はアルケニル基を分子中に少なくとも１個有するモノ又はビスコハク酸イミド、炭素数４０以上４００以下のアルキル基又はアルケニル基を分子中に少なくとも１個有するベンジルアミン、炭素数４０以上４００以下のアルキル基又はアルケニル基を分子中に少なくとも１個有するポリアミン、これらのホウ素化合物、カルボン酸、リン酸等による変成品などが挙げられる。 The ashless dispersant is not particularly limited, and an ashless dispersant used in a normal lubricating oil field can be used. Examples of the ashless dispersant include mono- or bissuccinimide having at least one linear or branched alkyl group or alkenyl group having 40 to 400 carbon atoms in the molecule, and an alkyl group having 40 to 400 carbon atoms. Alternatively, benzylamine having at least one alkenyl group in the molecule, polyamine having at least one alkyl group or alkenyl group having 40 to 400 carbon atoms in the molecule, modified products of these boron compounds, carboxylic acids, phosphoric acids, etc. Etc.
無灰分散剤の含有量は、組成物全量を基準として、０．１〜１０質量％であってもよい。 The content of the ashless dispersant may be 0.1 to 10% by mass based on the total amount of the composition.
潤滑油組成物は、その目的に応じて、一般的に使用されている任意の潤滑油用添加剤をさらに含有することができる。このような添加剤としては、例えば、流動点降下剤、腐食防止剤、防錆剤、抗乳化剤、金属不活性化剤、消泡剤等が挙げられる。 The lubricating oil composition may further contain any commonly used lubricating oil additive depending on the purpose. Examples of such additives include pour point depressants, corrosion inhibitors, rust inhibitors, demulsifiers, metal deactivators, and antifoaming agents.
流動点降下剤としては、例えば、使用する潤滑油基油に適合するポリメタクリレート系ポリマー等が挙げられる。 Examples of the pour point depressant include polymethacrylate polymers that are compatible with the lubricating base oil used.
腐食防止剤としては、例えば、ベンゾトリアゾール系、トリルトリアゾール系、チアジアゾール系、イミダゾール系化合物等が挙げられる。 Examples of the corrosion inhibitor include benzotriazole, tolyltriazole, thiadiazole, and imidazole compounds.
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、多価アルコールエステル等が挙げられる。 Examples of the rust preventive include petroleum sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, alkenyl succinic acid ester, polyhydric alcohol ester and the like.
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、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などが挙げられる。 Examples of the demulsifier include polyalkylene glycol nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, and polyoxyethylene alkyl naphthyl ether.
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、アゾール誘導体等が挙げられる。 Examples of the metal deactivator include imidazoline, pyrimidine, azole derivatives and the like.
消泡剤としては、例えば、２５℃における動粘度が１００〜１００００００ｍｍ２／ｓのハロゲン化アルキル基を有していてもよいシリコーンオイル、アルケニルコハク酸誘導体、ポリヒドロキシ脂肪族アルコールと長鎖脂肪酸とのエステル、メチルサリチレートとｏ−ヒドロキシベンジルアルコールとのエステル等が挙げられる。 Examples of the antifoaming agent include silicone oils that may have a halogenated alkyl group having a kinematic viscosity of 100 to 1,000,000 mm 2 / s at 25 ° C., alkenyl succinic acid derivatives, polyhydroxy aliphatic alcohols and long chain fatty acids, And esters of methyl salicylate and o-hydroxybenzyl alcohol.
その他の潤滑油用添加剤を用いる場合、それぞれの含有量は、組成物全量を基準として、０．０１〜２０質量％であってもよい。 When other additives for lubricating oil are used, each content may be 0.01 to 20% by mass based on the total amount of the composition.
潤滑油組成物中のリン元素含有量は、組成物全量を基準として、１００〜１０００質量ｐｐｍであってもよい。潤滑油組成物中のリン元素含有量は、主に上述の構成元素としてリンを含み、かつ硫黄を含まない摩耗防止剤のリン元素に由来する。潤滑油組成物中のリン元素含有量は、好ましくは１００質量ｐｐｍ以上、より好ましくは２００質量ｐｐｍ以上、さらに好ましくは３００質量ｐｐｍ以上である。潤滑油組成物中のリン元素含有量が１００質量ｐｐｍ以上であると、より充分な摩耗防止性能が得られる傾向にある。潤滑油組成物中のリン元素含有量は、好ましくは１０００質量ｐｐｍ以下、より好ましくは８００質量ｐｐｍ以下、さらに好ましくは６００質量ｐｐｍ以下である。潤滑油組成物中のリン元素含有量が１０００質量ｐｐｍ以下であると、灰分量の増加に伴う堆積物の増加及び排ガス後処理触媒の被毒をより抑制できる傾向にある。 The phosphorus element content in the lubricating oil composition may be 100 to 1000 ppm by mass based on the total amount of the composition. The phosphorus element content in the lubricating oil composition is mainly derived from the phosphorus element of the antiwear agent containing phosphorus as a constituent element and not containing sulfur. The phosphorus element content in the lubricating oil composition is preferably 100 ppm by mass or more, more preferably 200 ppm by mass or more, and even more preferably 300 ppm by mass or more. When the phosphorus element content in the lubricating oil composition is 100 ppm by mass or more, more sufficient wear prevention performance tends to be obtained. The phosphorus element content in the lubricating oil composition is preferably 1000 ppm by mass or less, more preferably 800 ppm by mass or less, and even more preferably 600 ppm by mass or less. When the phosphorus element content in the lubricating oil composition is 1000 ppm by mass or less, it tends to be possible to further suppress the increase in deposits accompanying the increase in the ash content and the poisoning of the exhaust gas aftertreatment catalyst.
潤滑油組成物中のリン元素含有量は、潤滑油組成物について、ＩＣＰ元素分析等を行うことによって直接的に求めることができる。また、リン元素を含む添加剤のリン元素含有量を予めＩＣＰ元素分析等によって分析し、その分析値と仕込み量との積からも求めることができる。 The phosphorus element content in the lubricating oil composition can be directly determined by performing ICP elemental analysis or the like on the lubricating oil composition. Further, the phosphorus element content of the additive containing phosphorus element can be analyzed in advance by ICP elemental analysis or the like, and it can be obtained from the product of the analysis value and the charged amount.
潤滑油組成物中のモリブデン元素含有量は、組成物全量を基準として、１００〜１０００質量ｐｐｍであってもよい。潤滑油組成物中のモリブデン元素含有量は、主に上述の有機モリブデン系摩擦調整剤のモリブデン元素に由来する。潤滑油組成物中のモリブデン元素含有量は、好ましくは１００質量ｐｐｍ以上、より好ましくは１２０質量ｐｐｍ以上、さらに好ましくは１５０質量ｐｐｍ以上である。潤滑油組成物中のモリブデン元素含有量が１００質量ｐｐｍ以上であると、より充分なフリクション低減性能が得られる傾向にある。潤滑油組成物中のモリブデン元素含有量は、好ましくは１０００質量ｐｐｍ以下、より好ましくは５００質量ｐｐｍ以下、さらに好ましくは３００質量ｐｐｍ以下である。潤滑油組成物中のモリブデン元素含有量が１０００質量ｐｐｍ以下であると、製品貯蔵時の沈殿生成及びエンジン内での体積物の増加をより抑制できる傾向にある。 The molybdenum element content in the lubricating oil composition may be 100 to 1000 ppm by mass based on the total amount of the composition. The molybdenum element content in the lubricating oil composition is mainly derived from the molybdenum element of the organic molybdenum friction modifier described above. The molybdenum element content in the lubricating oil composition is preferably 100 ppm by mass or more, more preferably 120 ppm by mass or more, and even more preferably 150 ppm by mass or more. When the molybdenum element content in the lubricating oil composition is 100 mass ppm or more, more sufficient friction reduction performance tends to be obtained. The molybdenum element content in the lubricating oil composition is preferably 1000 ppm by mass or less, more preferably 500 ppm by mass or less, and even more preferably 300 ppm by mass or less. When the molybdenum element content in the lubricating oil composition is 1000 ppm by mass or less, precipitation tends to occur during product storage and increase in volume in the engine tends to be further suppressed.
潤滑油組成物中のモリブデン元素含有量は、潤滑油組成物について、ＩＣＰ元素分析等を行うことによって直接的に求めることができる。また、モリブデン元素を含む添加剤のモリブデン元素含有量を予めＩＣＰ元素分析等によって分析し、その分析値と仕込み量との積からも求めることができる。 The molybdenum element content in the lubricating oil composition can be determined directly by performing ICP elemental analysis or the like on the lubricating oil composition. Further, the molybdenum element content of the additive containing molybdenum element can be analyzed in advance by ICP elemental analysis or the like, and can also be obtained from the product of the analysis value and the charged amount.
潤滑油組成物中のマグネシウム元素含有量に対するカルシウム元素含有量の比（カルシウム元素含有量／マグネシウム元素含有量）は、１．５０〜１．８０である。ここで、潤滑油組成物中のカルシウム元素及びマグネシウム元素は、主に上述のカルシウムサリシレート系清浄剤のカルシウム元素及びマグネシウムサリシレート系清浄剤のマグネシウム元素にそれぞれ由来する。マグネシウム元素含有量に対するカルシウム元素含有量の比は、１．５０以上、好ましくは１．５３以上、より好ましくは１．５５以上である。マグネシウム元素含有量に対するカルシウム元素含有量の比が１．５０以上であると、潤滑油組成物寿命が長くなる傾向にある。マグネシウム元素含有量に対するカルシウム元素含有量の比は、１．８０以下、好ましくは１．７０以下、より好ましくは１．６０以下である。マグネシウム元素含有量に対するカルシウム元素含有量の比が１．８０以下であると、潤滑油組成物の異常燃焼が抑制される傾向にある。 The ratio of the calcium element content to the magnesium element content in the lubricating oil composition (calcium element content / magnesium element content) is 1.50 to 1.80. Here, the calcium element and the magnesium element in the lubricating oil composition are mainly derived from the calcium element of the calcium salicylate detergent and the magnesium element of the magnesium salicylate detergent, respectively. The ratio of the calcium element content to the magnesium element content is 1.50 or more, preferably 1.53 or more, more preferably 1.55 or more. When the ratio of the calcium element content to the magnesium element content is 1.50 or more, the lubricating oil composition life tends to be long. The ratio of the calcium element content to the magnesium element content is 1.80 or less, preferably 1.70 or less, more preferably 1.60 or less. When the ratio of the calcium element content to the magnesium element content is 1.80 or less, abnormal combustion of the lubricating oil composition tends to be suppressed.
潤滑油組成物中のカルシウム元素含有量及びマグネシウム元素含有量は、潤滑油組成物について、ＩＣＰ元素分析等を行うことによって直接的に求めることができる。各元素を含む添加剤の各元素含有量を予めＩＣＰ元素分析等によって分析し、その分析値と仕込み量との積からも求めることができる。 The calcium element content and the magnesium element content in the lubricating oil composition can be directly determined by performing ICP elemental analysis or the like on the lubricating oil composition. Each element content of the additive containing each element is analyzed in advance by ICP elemental analysis or the like, and can also be obtained from the product of the analysis value and the charged amount.
潤滑油組成物中のマグネシウム元素含有量とカルシウム元素含有量との総量は、８００〜１５００質量ｐｐｍであってもよい。マグネシウム元素含有量とカルシウム元素含有量との総量は、好ましくは８００質量ｐｐｍ以上、より好ましくは９００質量ｐｐｍ以上、さらに好ましくは１０００質量ｐｐｍ以上である。マグネシウム元素含有量とカルシウム元素含有量との総量が８００質量ｐｐｍ以上であると、より充分な清浄性能及び寿命性能が得られる傾向にある。マグネシウム元素含有量とカルシウム元素含有量との総量は、好ましくは１５００質量ｐｐｍ以下、より好ましくは１４００質量ｐｐｍ以下、さらに好ましくは１３００質量ｐｐｍ以下である。マグネシウム元素含有量とカルシウム元素含有量との総量が１５００質量ｐｐｍ以下であると、異常燃焼をより抑制できる傾向にある。 800-1500 mass ppm may be sufficient as the total amount of magnesium element content and calcium element content in a lubricating oil composition. The total amount of magnesium element content and calcium element content is preferably 800 ppm by mass or more, more preferably 900 ppm by mass or more, and still more preferably 1000 ppm by mass or more. When the total amount of the magnesium element content and the calcium element content is 800 mass ppm or more, more sufficient cleaning performance and life performance tend to be obtained. The total amount of magnesium element content and calcium element content is preferably 1500 ppm by mass or less, more preferably 1400 ppm by mass or less, and even more preferably 1300 ppm by mass or less. When the total amount of the magnesium element content and the calcium element content is 1500 ppm by mass or less, abnormal combustion tends to be further suppressed.
潤滑油組成物の１００℃における動粘度は、好ましくは１０〜１２ｍｍ２／ｓである。１００℃における動粘度は、より好ましくは１０〜１１．５ｍｍ２／ｓ、さらに好ましくは１０〜１１ｍｍ２／ｓである。１００℃における動粘度が１０ｍｍ２／ｓ以上あると、実使用温度域においてより良好な油膜が得られる傾向にある。１００℃における動粘度が１２ｍｍ２／ｓ以下であると、より充分な高効率（省燃費）効果が得られる傾向にある。 The kinematic viscosity at 100 ° C. of the lubricating oil composition is preferably 10 to 12 mm 2 / s. The kinematic viscosity at 100 ° C. is more preferably 10 to 11.5 mm 2 / s, still more preferably 10 to 11 mm 2 / s. When the kinematic viscosity at 100 ° C. is 10 mm 2 / s or more, a better oil film tends to be obtained in the actual use temperature range. When the kinematic viscosity at 100 ° C. is 12 mm 2 / s or less, a more sufficient high efficiency (fuel saving) effect tends to be obtained.
潤滑油組成物の４０℃における動粘度は、特に制限されないが、好ましくは５０ｍｍ２／ｓ以上、より好ましくは５５ｍｍ２／ｓ以上、さらに好ましくは６０ｍｍ２／ｓ以上である。潤滑油組成物の４０℃における動粘度が５０ｍｍ２／ｓ以上であると、実使用温度域においてより良好な油膜が得られる傾向にある。また、潤滑油組成物の４０℃における動粘度は、好ましくは７０ｍｍ２／ｓ以下、より好ましくは６５ｍｍ２／ｓ以下、さらに好ましくは６３ｍｍ２／ｓ以下である。潤滑油組成物の４０℃における動粘度が７０ｍｍ２／ｓ以下であると、より充分な省燃費効果が得られる傾向にある。 The kinematic viscosity at 40 ° C. of the lubricating oil composition is not particularly limited, but is preferably 50 mm 2 / s or more, more preferably 55 mm 2 / s or more, and further preferably 60 mm 2 / s or more. When the kinematic viscosity at 40 ° C. of the lubricating oil composition is 50 mm 2 / s or more, a better oil film tends to be obtained in the actual use temperature range. Further, the kinematic viscosity at 40 ° C. of the lubricating oil composition is preferably 70 mm 2 / s or less, more preferably 65 mm 2 / s or less, and further preferably 63 mm 2 / s or less. When the kinematic viscosity at 40 ° C. of the lubricating oil composition is 70 mm 2 / s or less, more sufficient fuel saving effect tends to be obtained.
潤滑油組成物の粘度指数は、特に制限されないが、好ましくは１００以上、より好ましくは１１０以上、さらに好ましくは１２０以上である。粘度指数が上記の範囲内であると、外部の温度に対して粘度の安定性が確保されるため、使用時における外部の温度変化に対しても安定的に油膜を形成できる傾向にある。 The viscosity index of the lubricating oil composition is not particularly limited, but is preferably 100 or more, more preferably 110 or more, and still more preferably 120 or more. When the viscosity index is within the above range, the stability of the viscosity with respect to the external temperature is ensured, so that the oil film tends to be stably formed even with respect to the external temperature change during use.
潤滑油組成物の塩酸法による塩基価は、特に制限されないが、３．０〜５．０ｍｇＫＯＨ／ｇであってもよい。塩基価は、好ましくは３．５〜５．０ｍｇＫＯＨ／ｇ、より好ましくは４．０〜５．０ｍｇＫＯＨ／ｇである。塩基価が３．０ｍｇＫＯＨ／ｇ以上であると、より充分な寿命性能が得られる傾向にある。塩基価が５．０ｍｇＫＯＨ／ｇ以下であると、潤滑油組成物中の金属成分が適切な範囲となり、異常燃焼をより抑制できる傾向にある。なお、塩酸法による塩基価は、ＪＩＳ Ｋ２５０１に準拠して測定される値を意味する。 The base number of the lubricating oil composition by the hydrochloric acid method is not particularly limited, but may be 3.0 to 5.0 mgKOH / g. The base number is preferably 3.5 to 5.0 mgKOH / g, more preferably 4.0 to 5.0 mgKOH / g. When the base number is 3.0 mgKOH / g or more, more sufficient life performance tends to be obtained. When the base number is 5.0 mgKOH / g or less, the metal component in the lubricating oil composition is in an appropriate range, and abnormal combustion tends to be further suppressed. The base number by the hydrochloric acid method means a value measured according to JIS K2501.
潤滑油組成物の硫酸灰分量は、０．６質量％以下である。硫酸灰分量が０．６質量％以下であると、ピストンへの灰分堆積による異常摩耗及び異常燃焼を抑制できる傾向にある。硫酸灰分量は、ＪＩＳ Ｋ２２７２に準拠して測定される値を意味する。 The amount of sulfated ash in the lubricating oil composition is 0.6% by mass or less. When the sulfated ash content is 0.6% by mass or less, abnormal wear and abnormal combustion due to ash deposition on the piston tend to be suppressed. The amount of sulfated ash means a value measured according to JIS K2272.
本実施形態のガスエンジン用潤滑油組成物によれば、寿命特性及び省燃費性に優れ、さらに異常燃焼を抑制することが可能となる。そのため、このような潤滑油組成物を用いて潤滑を行う、燃料消費量の改善方法又は異常燃焼の低減方法を提供することができる。 According to the lubricating oil composition for gas engine of this embodiment, it is excellent in a life characteristic and fuel-saving property, and it becomes possible to suppress abnormal combustion. Therefore, it is possible to provide a method for improving fuel consumption or a method for reducing abnormal combustion, in which lubrication is performed using such a lubricating oil composition.
以下、本発明について実施例を挙げてより具体的に説明する。ただし、本発明はこれら実施例に限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
［潤滑油組成物の調製］
（実施例１、２及び比較例１〜４）
表１に示すように、実施例１、２及び比較例１〜４の潤滑油組成物をそれぞれ調製した。なお、潤滑油組成物の調製の際には、その１００℃における動粘度が、１０．２〜１０．４ｍｍ２／ｓの範囲内になるように主に粘度指数向上剤の含有量を調整した。得られた潤滑油組成物について、各種試験を行った。
[Preparation of lubricating oil composition]
(Examples 1 and 2 and Comparative Examples 1 to 4)
As shown in Table 1, the lubricating oil compositions of Examples 1 and 2 and Comparative Examples 1 to 4 were prepared. When preparing the lubricating oil composition, the content of the viscosity index improver was mainly adjusted so that the kinematic viscosity at 100 ° C. was in the range of 10.2 to 10.4 mm 2 / s. . Various tests were performed on the obtained lubricating oil composition.
表１に示した各成分の詳細は以下のとおりである。 Details of each component shown in Table 1 are as follows.
＜潤滑油基油＞
基油Ａ−１：水素化精製鉱油（ＧｐＩＩＩ＋）（ＹＵＢＡＳＥ−６、４０℃動粘度：３６．１ｍｍ２／ｓ、１００℃動粘度：６．４２ｍｍ２／ｓ、粘度指数：１３１）
<Lubricant base oil>
Base oil A-1: Hydrorefined mineral oil (GpIII +) (YUBASE-6, 40 ° C. kinematic viscosity: 36.1 mm 2 / s, 100 ° C. kinematic viscosity: 6.42 mm 2 / s, viscosity index: 131)
＜潤滑油用添加剤＞
摩耗防止剤Ｂ−１：ジアルキルリン酸亜鉛（ＺＰ）（城北化学工業株式会社製、商品名：ＤＢＰ−Ｚｎ−５０Ｌ、アルキル基：ブチル基、リン元素含有量：６．９質量％）
摩耗防止剤ｂ−１：ジアルキルジチオリン酸亜鉛（ＺＤＴＰ）（シェブロンオロナイト社製、ＯＬＯＡ ２６９ＲＪ、アルキル基：ｎ−オクチル基、リン元素含有量：７．１質量％）
摩擦調整剤Ｃ−１：モリブデン酸ジアルキルアミン塩（株式会社ＡＤＥＫＡ製、サクラルーブ ７１０、アルキル基：トリデカニル基、モリブデン元素含有量：１０質量％）
金属系清浄剤Ｄ−１：過塩基性カルシウムサリシレート（オスカ化学株式会社製、商品名：ＯＳＣＡ ４６３、カルシウム元素含有量：６．５質量％）
金属系清浄剤Ｄ−２：中性カルシウムサリシレート（オスカ化学株式会社製、商品名：ＬＢ ６２２、カルシウム元素含有量：１．８質量％）
金族系清浄剤Ｄ−３：マグネシウムサリシレート（オスカ化学株式会社製、マグネシウム元素含有量：２．１質量％）
無灰分散剤Ｅ−１：ポリアルケニルコハク酸イミド（シェブロンオロナイト社製、ＯＬＯＡ ５０９６、重量平均分子量：４０００〜６０００、窒素元素含有量：１．５質量％、ホウ素元素含有量：０．５質量％）
酸化防止剤Ｆ−１：アミン系酸化防止剤（ＢＡＳＦ社製、商品名：ＩＲＧＡＮＯＸ Ｌ５７、モノブチルフェニルモノオクチルフェニルアミン、窒素元素含有量：４．５質量％）０．３質量％（組成物全量基準）及びフェノール系酸化防止剤（ＢＡＳＦ社製、商品名：ＩＲＧＡＮＯＸ Ｌ１３５、ヒンダードフェノール、窒素元素含有量：４．５質量％）０．３質量％（組成物全量基準）
粘度指数向上剤Ｇ−１：ポリメタクリレートとオレフィンコポリマーとの混合ポリマー（エボニックデグサ社製、商品名：ＶＩＳＣＯＰＬＥＸ ２−６０２）
<Additive for lubricating oil>
Antiwear agent B-1: Zinc dialkyl phosphate (ZP) (manufactured by Johoku Chemical Industry Co., Ltd., trade name: DBP-Zn-50L, alkyl group: butyl group, phosphorus element content: 6.9% by mass)
Antiwear agent b-1: zinc dialkyldithiophosphate (ZDTP) (manufactured by Chevron Oronite, OLOA 269RJ, alkyl group: n-octyl group, phosphorus element content: 7.1% by mass)
Friction modifier C-1: dialkylamine salt of molybdate (manufactured by ADEKA, Sakurarubu 710, alkyl group: tridecanyl group, molybdenum element content: 10% by mass)
Metal detergent D-1: Overbased calcium salicylate (manufactured by Oska Chemical Co., Ltd., trade name: OSCA 463, content of calcium element: 6.5% by mass)
Metal detergent D-2: Neutral calcium salicylate (manufactured by Oska Chemical Co., Ltd., trade name: LB 622, calcium element content: 1.8% by mass)
Metallic detergent D-3: Magnesium salicylate (manufactured by Oska Chemical Co., Ltd., magnesium element content: 2.1% by mass)
Ashless dispersant E-1: polyalkenyl succinimide (manufactured by Chevron Oronite, OLOA 5096, weight average molecular weight: 4000 to 6000, nitrogen element content: 1.5 mass%, boron element content: 0.5 mass %)
Antioxidant F-1: Amine-based antioxidant (trade name: IRGANOX L57, monobutylphenyl monooctylphenylamine, nitrogen element content: 4.5 mass%) 0.3 mass% (composition) 0.3% by mass (based on the total amount of the composition) and phenolic antioxidant (made by BASF, trade name: IRGANOX L135, hindered phenol, nitrogen element content: 4.5% by mass)
Viscosity index improver G-1: mixed polymer of polymethacrylate and olefin copolymer (Evonik Degussa, trade name: VISCOPLEX 2-602)
各潤滑油用添加剤の各元素含有量は、ＩＣＰ元素分析法によって求めた。また、表１において、各潤滑油用添加剤の組成物基準としたときの各元素換算の含有量（元素換算値）及び組成物における各元素含有量は、各潤滑油用添加剤の各元素含有量と仕込み量との積から求めた。 Each element content of each additive for lubricating oil was determined by ICP elemental analysis. Further, in Table 1, the content in terms of each element (element-converted value) and the content of each element in the composition based on the composition standard of each additive for lubricating oil are the respective elements in each additive for lubricating oil. It calculated | required from the product of content and preparation amount.
（１）粘度特性
ＪＩＳ Ｋ２２８３「原油及び石油製品−動粘度試験方法及び粘度指数算出方法」に準拠して、各潤滑油組成物の４０℃及び１００℃動粘度並びに粘度指数を測定した。
(1) Viscosity characteristics 40 ° C. and 100 ° C. kinematic viscosity and viscosity index of each lubricating oil composition were measured according to JIS K2283 “Crude oil and petroleum products—Kinematic viscosity test method and viscosity index calculation method”.
（２）酸価及び塩基価
ＪＩＳ Ｋ２５０１に準拠して、各潤滑油組成物の酸価及び塩酸法による塩基価を測定した。
(2) Acid number and base number Based on JIS K2501, the acid number of each lubricating oil composition and the base number by the hydrochloric acid method were measured.
（３）硫酸灰分量
ＪＩＳ Ｋ２２７２に準拠して、各潤滑油組成物の硫酸灰分量を測定した。
(3) Amount of sulfated ash The amount of sulfated ash of each lubricating oil composition was measured according to JIS K2272.
（４）ＮＯｘ吹き込み試験（寿命特性）
各潤滑油組成物について、ＮＯｘ吹き込み試験を行った。試験条件を以下に示す。試験後、ＪＩＳ Ｋ２５０１に準拠して、各潤滑油組成物の塩酸法による塩基価を測定し、試験前の塩基価に対する試験後の塩基価（［試験後の塩基価］／［試験前の塩基価］）を「ＮＯｘ試験後塩基価残存率」として算出した。本試験においては、数値が大きい（例えば、１０％以上）ほど、潤滑油組成物の塩基価が維持される、ずなわち、長寿命であることを意味する。
(4) NOx blowing test (life characteristics)
Each lubricating oil composition was subjected to a NOx blowing test. Test conditions are shown below. After the test, the base number by the hydrochloric acid method of each lubricating oil composition was measured according to JIS K2501, and the base number after the test relative to the base number before the test ([base number after test] / [base before test] Value]) was calculated as “base number remaining ratio after NOx test”. In this test, a larger value (for example, 10% or more) means that the base number of the lubricating oil composition is maintained, that is, a longer life.
＜試験条件＞
混合ガス：酸素（８５％）、ＮＯ２（１０００ｐｐｍ）及び窒素（残部）の混合ガス
試験温度：１４０℃
試験時間：９６時間
<Test conditions>
Mixed gas: mixed gas of oxygen (85%), NO 2 (1000 ppm) and nitrogen (remainder) Test temperature: 140 ° C.
Test time: 96 hours
（５）ＳＲＶ試験（省燃費性）
各潤滑油組成物について、シリンダオンディスク式往復動摩擦試験機を用いて、ＳＲＶ試験を行い、金属間摩擦係数を測定した。試験条件を以下に示す。本試験においては、数値が小さい（例えば、０．１５以下）ほど、摩擦特性に優れる、すなわち、省燃費性に優れることを意味する。
(5) SRV test (fuel economy)
Each lubricating oil composition was subjected to an SRV test using a cylinder-on-disk type reciprocating friction tester, and the friction coefficient between metals was measured. Test conditions are shown below. In this test, the smaller the numerical value (for example, 0.15 or less), the better the friction characteristics, that is, the better the fuel economy.
＜試験条件＞
荷重：１７０Ｎ
振動数：５０Ｈｚ
試験温度：８０℃
試験時間：３０分間
<Test conditions>
Load: 170N
Frequency: 50Hz
Test temperature: 80 ° C
Test time: 30 minutes
（６）高圧ＤＳＣ（示唆熱分析）試験（酸化特性）
各潤滑油組成物について、高圧示差走査熱量計（高圧ＤＳＣ）を用いて、熱量変化を測定し、ＤＳＣチャートの立ち上がり温度（ｏｎｓｅｔ）を酸化開始温度として評価した。試験条件を以下に示す。本試験においては、数値が大きい（例えば、２７０℃以上）ほど、酸化（すなわち、自己着火（燃焼）現象）が起こりにくいことを意味する。
(6) High pressure DSC (suggested thermal analysis) test (oxidation characteristics)
About each lubricating oil composition, the calorimetric change was measured using the high-pressure differential scanning calorimeter (high-pressure DSC), and the rising temperature (onset) of the DSC chart was evaluated as the oxidation start temperature. Test conditions are shown below. In this test, a larger value (for example, 270 ° C. or higher) means that oxidation (that is, self-ignition (combustion) phenomenon) hardly occurs.
＜試験条件＞
測定雰囲気：空気雰囲気下
圧力：１．０ＭＰａ（１０ａｔｍ）
昇温条件：５０℃で５分間保持した後、１０℃／分で５００℃まで昇温
<Test conditions>
Measurement atmosphere: Under air atmosphere Pressure: 1.0 MPa (10 atm)
Temperature raising condition: After holding at 50 ° C. for 5 minutes, the temperature is raised to 500 ° C. at 10 ° C./min.
実施例１、２の潤滑油組成物は、高水準で寿命特性、省燃費性及び酸化特性が両立されていた。これに対して、構成元素として硫黄を含む摩耗防止剤を用い、有機モリブデン系摩擦調整剤及びマグネシウムサリシレート系清浄剤を含有しない比較例１の潤滑油組成物は、実施例１、２の潤滑油組成物に比べて、寿命特性、省燃費性及び酸化特性のいずれにおいても充分ではなかった。また、有機モリブデン系摩擦調整剤及びマグネシウムサリシレート系清浄剤を含有しない比較例２の潤滑油組成物は、実施例１、２の潤滑油組成物に比べて、寿命特性に優れているものの、省燃費性及び酸化特性は充分でなかった。一方、組成物におけるマグネシウム元素含有量に対するカルシウム元素含有量の比が特定の範囲にない比較例３及び４の潤滑油組成物においては、寿命特性及び酸化特性が相反関係にあり、これら特性を高い水準で両立できないことが判明した。これらの結果から、本発明のガスエンジン用潤滑油組成物が、寿命特性及び省燃費性に優れ、さらに異常燃焼を抑制することが可能であることが確認された。 The lubricating oil compositions of Examples 1 and 2 were compatible at high levels with life characteristics, fuel economy and oxidation characteristics. On the other hand, the lubricating oil composition of Comparative Example 1 using an antiwear agent containing sulfur as a constituent element and not containing an organic molybdenum friction modifier and a magnesium salicylate detergent is the lubricating oil of Examples 1 and 2. Compared to the composition, none of the life characteristics, fuel economy and oxidation characteristics were satisfactory. In addition, the lubricating oil composition of Comparative Example 2 that does not contain an organic molybdenum friction modifier and a magnesium salicylate detergent is superior to the lubricating oil compositions of Examples 1 and 2 in terms of life characteristics. Fuel economy and oxidation characteristics were not sufficient. On the other hand, in the lubricating oil compositions of Comparative Examples 3 and 4 in which the ratio of the calcium element content to the magnesium element content in the composition is not in a specific range, the life characteristics and the oxidation characteristics are in a reciprocal relationship, and these characteristics are high. It became clear that it was incompatible at the level. From these results, it was confirmed that the lubricating oil composition for a gas engine of the present invention is excellent in life characteristics and fuel economy, and can suppress abnormal combustion.
Claims (5)
構成元素としてリンを含み、かつ硫黄を含まない摩耗防止剤と、
有機モリブデン系摩擦調整剤と、
カルシウムサリシレート系清浄剤と、
マグネシウムサリシレート系清浄剤と、
を含有し、
組成物中のマグネシウム元素含有量に対する組成物中のカルシウム元素含有量の比が１．５０〜１．８０であり、
ＪＩＳ Ｋ２２７２に準拠して測定される硫酸灰分量が０．６質量％以下である、
ガスエンジン用潤滑油組成物。 Lubricating base oil,
An antiwear agent containing phosphorus as a constituent element and not containing sulfur;
An organic molybdenum friction modifier;
A calcium salicylate detergent,
A magnesium salicylate detergent,
Containing
The ratio of the elemental calcium content in the composition to the elemental magnesium content in the composition is 1.50-1.80,
The sulfated ash content measured according to JIS K2272 is 0.6% by mass or less,
Lubricating oil composition for gas engines.
請求項１に記載のガスエンジン用潤滑油組成物。 The ratio of the content in terms of calcium of the calcium salicylate detergent in the composition to the content in terms of magnesium element of the magnesium salicylate detergent in the composition is 1.50 to 1.80.
The lubricating oil composition for gas engines according to claim 1.
請求項１又は２に記載のガスエンジン用潤滑油組成物。 The kinematic viscosity at 100 ° C. is 10 to 12 mm 2 / s,
The lubricating oil composition for gas engines according to claim 1 or 2.
請求項１〜３のいずれか一項に記載のガスエンジン用潤滑油組成物。 Further containing at least one selected from the group consisting of antioxidants and ashless dispersants,
The lubricating oil composition for gas engines as described in any one of Claims 1-3.
燃料消費量の改善方法又は異常燃焼の低減方法。 Lubrication is performed using the lubricating oil composition for a gas engine according to any one of claims 1 to 4.
A method for improving fuel consumption or reducing abnormal combustion.
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| CN201810567795.2A CN109022104A (en) | 2017-06-08 | 2018-06-05 | The reduction method of the ameliorative way or abnormal combustion of gas engine lubricant oil composite and fuel consumption |
| US16/001,988 US20180355274A1 (en) | 2017-06-08 | 2018-06-07 | Gas engine lubricating oil composition, and method for improving fuel consumption and/or for reducing abnormal combustion |
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| WO2020203525A1 (en) | 2019-03-29 | 2020-10-08 | 出光興産株式会社 | Lubricating oil composition |
| WO2022209540A1 (en) | 2021-03-30 | 2022-10-06 | 出光興産株式会社 | Lubricating oil composition |
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| JP7281321B2 (en) | 2019-03-29 | 2023-05-25 | 出光興産株式会社 | lubricating oil composition |
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