EP3950904B1 - Schmierölzusammensetzung - Google Patents

Schmierölzusammensetzung Download PDF

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Publication number
EP3950904B1
EP3950904B1 EP20781970.7A EP20781970A EP3950904B1 EP 3950904 B1 EP3950904 B1 EP 3950904B1 EP 20781970 A EP20781970 A EP 20781970A EP 3950904 B1 EP3950904 B1 EP 3950904B1
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EP
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Prior art keywords
lubricating oil
mass
oil composition
component
content
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EP20781970.7A
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English (en)
French (fr)
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EP3950904A4 (de
EP3950904A1 (de
Inventor
Tatsuya Kusumoto
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Idemitsu Kosan Co Ltd
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Idemitsu Kosan Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/48—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring
    • C10M129/54—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/38—Heterocyclic nitrogen compounds
    • C10M133/44—Five-membered ring containing nitrogen and carbon only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C10M137/10—Thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M139/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/12—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic compound containing atoms of elements not provided for in groups C10M141/02 - C10M141/10
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/003—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
    • C10M2215/30—Heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbased sulfonic acid salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • C10M2227/061—Esters derived from boron
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines

Definitions

  • the present invention relates to a lubricating oil composition.
  • a gas engine heat pump system and a gas engine cogeneration system have been put into practical use for air conditioning of houses and buildings.
  • a gas engine using natural gas, liquefied petroleum gas (LPG) or the like as a fuel is generally used.
  • Patent Literature 1 describes a lubricating oil composition for a gas engine, comprising a lubricating base oil, an anti-wear agent containing phosphorus as a constituent element and not containing sulfur, an organomolybdenum-based friction modifier, a calcium salicylate-based detergent, and a magnesium salicylate-based detergent, wherein an element content ratio between magnesium and calcium is adjusted in a prescribed range, and a sulfated ash content is set to 0.6 mass% or less.
  • Patent Literature 2 describes a method for preventing or reducing low speed pre-ignition in an engine lubricated with a lubricating oil by using as the lubricating oil a formulated oil.
  • the formulated oil has a composition including a lubricating oil base stock as a major component, and at least one detergent, as a minor component.
  • the detergent includes at least one alkaline earth metal salt of an organic acid, and the at least one alkaline earth metal salt of an organic acid comprises at least one magnesium salt of an organic acid.
  • a lubricating engine oil having a composition including a lubricating oil base stock as a major component; and at least one detergent, as a minor component.
  • the lubricating oils of the disclosure of Patent Literature 2 may be used as passenger vehicle engine oil (PVEO) products.
  • the present invention provides a lubricating oil composition for a gas engine, comprising a base oil, a calcium-based detergent, and an alkenyl succinimide comprising a non-boron-modified alkenyl bis-succinimide, wherein contents of calcium atoms and boron atoms are adjusted to specific ranges.
  • the present invention provides, for example, a lubricating oil composition, a gas engine, and use of a lubricating oil composition according to claim 1.
  • a lubricating oil composition for example, a lubricating oil composition, a gas engine, and use of a lubricating oil composition according to claim 1.
  • the following embodiments may be useful to understanding the invention.
  • the present invention relates to a lubricating oil composition for a gas engine, comprising a base oil (A), a calcium-based detergent (B), and an alkenyl succinimide (C), wherein a content of the component (B) in terms of calcium atoms is 0.09 to 0.17 mass% based on the total amount of the lubricating oil composition, the component (C) comprises a non-boron-modified alkenyl bis-succinimide (C1) and a boron-modified alkenyl succinimide (C2), a content of boron atoms derived from the component (C) is less than 0.02 mass% based on the total amount of the lubricating oil composition, a content of magnesium atoms is less than 0.01 mass% based on the total amount of the lubricating oil composition, and a content of molybdenum atoms is less than 0.001 mass% based on the total amount of the lubricating oil composition.
  • the lubricating oil composition has a content ratio [N/Ca] by mass of nitrogen atoms derived from the component (C) to calcium atoms derived from the component (B) which is 0.90 or less.
  • the component (B) comprises calcium salicylate (B1).
  • the component (C1) is a non-boron-modified alkenyl bis-succinimide at least having a polybutenyl group or a polyisobutenyl group having a weight-average molecular weight of 500 to 3000.
  • the lubricating oil has a content ratio [B/N] by mass of boron atoms derived from the component (C2) to nitrogen atoms derived from the component (C) which is 0.01 to 0.35.
  • a content of the component (C) in terms of nitrogen atoms is 0.005 to 0.15 mass% based on the total amount of the lubricating oil composition.
  • the lubricating oil composition further comprises zinc dithiophosphate (D).
  • a content of magnesium atoms is less than 0.001 mass% based on the total amount of the lubricating oil composition.
  • the present invention relates to a use of the lubricating oil composition, wherein the lubricating oil composition according to any one of the claims is applied to a gas engine.
  • the lubricating oil composition of one preferred embodiment of the present invention is excellent in at least one of various characteristics required for lubrication of a gas engine, and in a more preferred embodiment, the lubricating oil composition is excellent in preignition suppression effect even when it is used for a long time. These lubricating oil compositions having such characteristics can be preferably used for lubrication of a gas engine.
  • a kinematic viscosity and a viscosity index mean values measured and calculated in accordance with JIS K2283:2000.
  • the contents of calcium atoms, phosphorus atoms, boron atoms, zinc atoms, and molybdenum atoms mean values measured in accordance with JP1-5S-38-92.
  • the content of nitrogen atoms means a value measured in accordance with JIS K2609:1998.
  • the lubricating oil composition of the present invention is a lubricating oil composition for a gas engine according to claim 1, comprising a base oil (A), a calcium-based detergent (B), and an alkenyl succinimide (C), wherein a content of the component (B) in terms of calcium atoms is 0.09 to 0.17 mass% based on the total amount of the lubricating oil composition, the component (C) comprises a non-boron-modified alkenyl bis-succinimide (C1) and a boron-modified alkenyl succinimide (C2), a content of boron atoms derived from the component (C) is less than 0.02 mass% based on the total amount of the lubricating oil composition, a content of magnesium atoms is less than 0.01 mass% based on the total amount of the lubricating oil composition, and a content of molybdenum atoms is less than 0.001 mass% based on the total amount of the lubricating
  • a lubricating oil composition in which a non-boron-modified alkenyl bis-succinimide (C1) was used as the alkenyl succinimide (C) and the content of the calcium-based detergent (B) in terms of calcium atoms and the content of boron atoms derived from the component (C) were adjusted in prescribed ranges was prepared, and when high-pressure DSC measurement of an ash content of the lubricating oil composition was carried out, the result was that the peak calorific value was suppressed, and it has been shown that the occurrence frequency of preignition is decreased.
  • C1 non-boron-modified alkenyl bis-succinimide
  • B calcium-based detergent
  • the lubricating oil composition of the present invention can effectively suppress occurrence of preignition even when it is used for a long time.
  • the lubricating oil composition of one embodiment of the present invention preferably further contains zinc dithiophosphate (D).
  • the lubricating oil composition of one embodiment of the present invention may further contain lubricating oil additives other than the components (B) to (D) when needed as long as the effects of the present invention are not impaired.
  • the total content of the components (A), (B) and (C) is preferably 60 mass% or more, more preferably 65 mass% or more, still more preferably 70 mass% or more, still much more preferably 75 mass% or more, and particularly preferably 80 mass% or more, based on the total amount (100 mass%) of the lubricating oil composition.
  • base oil (A) used in one embodiment of the present invention one or more selected from mineral oils and synthetic oils can be mentioned.
  • the synthetic oils include poly- ⁇ -olefins, such as an ⁇ -olefin homopolymer and an ⁇ -olefin copolymer (for example, an ⁇ -olefin copolymer having 8 to 14 carbon atoms such as an ethylene- ⁇ -olefin copolymer); isoparaffin; polyalkylene glycol; ester oils, such as polyol ester, dibasic acid ester, and phosphoric acid ester; ether oils, such as polyphenyl ether; alkylbenzene; alkylnaphthalene; and synthetic oil (GTL) obtained by isomerizing wax (GTL WAX (Gas To Liquids WAX)) produced from natural gas through Fischer-Tropsch process or the like.
  • GTL WAX Gas To Liquids WAX
  • the base oil (A) used in one embodiment of the present invention is preferably one or more selected from mineral oils classified in Group II and Group III of API (American Petroleum Institute) base oil categories, and synthetic oils.
  • the kinematic viscosity of the base oil (A) used in one embodiment of the present invention at 40°C is preferably 10 to 130 mm 2 /s, more preferably 20 to 120 mm 2 /s, still more preferably 30 to 110 mm 2 /s, and still much more preferably 40 to 100 mm 2 /s.
  • the viscosity index of the base oil (A) used in one embodiment of the present invention is preferably 70 or more, more preferably 80 or more, still more preferably 90 or more, still much more preferably 100 or more, and particularly preferably 105 or more.
  • the kinematic viscosity and the viscosity index of the mixed oil are preferably in the above ranges.
  • the content of the component (A) is preferably 50 to 99.5 mass%, more preferably 60 to 99.0 mass%, still more preferably 65 to 97.0 mass%, and still much more preferably 70 to 95.0 mass%, based on the total amount (100 mass%) of the lubricating oil composition.
  • the lubricating oil composition of the present invention contains a calcium-based detergent (B).
  • the calcium-based detergent (B) is contained, a lubricating oil composition capable of effectively suppressing occurrence of preignition even when it is used for a long time can be obtained. Moreover, this component contributes to extension of a life of the lubricating oil composition, such as suppression of occurrence of sludge that is produced when the lubricating oil composition is used in a high-temperature high-load environment in a gas engine.
  • the component (B) may be used singly, or may be used in combination of two or more.
  • the content of the component (B) in terms of calcium atoms in the lubricating oil composition of the present invention is 0.09 to 0.17 mass% based on the total amount (100 mass%) of the lubricating oil composition, but it is preferably 0.10 to 0.16 mass%, more preferably 0.11 to 0.15 mass%, still more preferably 0.115 to 0.14 mass%, and still much more preferably 0.118 to 0.135 mass%.
  • the calcium-based detergent (B) used in one embodiment of the present invention is preferably one or more selected from calcium salicylate (B1), calcium sulfonate (B2), and calcium phenate (B3), and more preferably, it contains at least calcium salicylate (B1).
  • the content ratio of the calcium salicylate (B1) in the component (B) is preferably 50 to 100 mass%, more preferably 60 to 100 mass%, still more preferably 70 to 100 mass%, still much more preferably 80 to 100 mass%, and particularly preferably 90 to 100 mass%, based on the total amount (100 mass%) of the component (B).
  • the calcium salicylate (B1) is preferably a compound represented by the following general formula (b-1)
  • the calcium sulfonate (B2) is preferably a compound represented by the following general formula (b-2)
  • the calcium phenate (B3) is preferably a compound represented by the following general formula (b-3).
  • R is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.
  • hydrocarbon groups capable of being selected as R include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 ring-forming carbon atoms, an aryl group having 6 to 18 ring-forming carbon atoms, an alkylaryl group having 7 to 18 carbon atoms, and an arylalkyl group having 7 to 18 carbon atoms.
  • Y is an integer of 0 or more, and preferably an integer of 0 to 3.
  • the base number of the component (B) used in one embodiment of the present invention is preferably 0 to 600 mgKOH/g.
  • the component (B) contain an overbased calcium-based detergent having a base number of 100 mgKOH/g or more.
  • the base number of the overbased calcium-based detergent is 100 mgKOH/g or more, but it is preferably 150 to 500 mgKOH/g, and more preferably 200 to 400 mgKOH/g.
  • the "base number" of the component (B) means a base number measured by hydrochloric acid method in accordance with JIS K2501 "Petroleum products and lubricants - Determination of neutralization number", 7.
  • the compounding amount (content) of the component (B) is appropriately adjusted in such a manner that the content of calcium atoms in the lubricating oil composition is in the aforesaid range, but it is preferably 0.10 to 10.0 mass%, more preferably 0.20 to 7.5 mass%, still more preferably 0.30 to 5.0 mass%, and still much more preferably 0.50 to 2.5 mass%, based on the total amount (100 mass%) of the lubricating oil composition.
  • the lubricating oil composition of one embodiment of the present invention may contain a metal-based detergent other than the component (B) as long as the effects of the present invention are not impaired.
  • the metal-based detergent other than the component (B) is one or more selected from a metal salicylate, a metal phenate, and a metal sulfonate each of which contains an alkali metal atom or an alkaline earth metal atom other than a calcium atom.
  • the content of a magnesium-based detergent is preferably smaller.
  • metal salicylate, metal phenate and metal sulfonate are preferably those having structures represented by the aforesaid general formulae (b-1), (b-2) and (b-3), respectively.
  • the lubricating oil composition of the present invention contains an alkenyl succinimide (C).
  • the component (C) may be used in combination of two or more.
  • the component (C) has a function of homogenously dispersing additives including the component (B).
  • a modified alkenyl succinimide may be used as the alkenyl succinimide (C).
  • a boron-modified alkenyl succinimide that is a boron-modified product is excellent in that it homogeneously disperses an additive such as the component (B) to allow the additive to effectively exhibit its function.
  • the boron-modified alkenyl succinimide is contained in a deposit that has occurred with long time use, it tends to become a factor for the occurrence of preignition.
  • the content of boron atoms derived from the component (C) is less than 0.02 mass% based on the total amount (100 mass%) of the lubricating oil composition.
  • the content of boron atoms derived from the component (C) in the lubricating oil composition of one embodiment of the present invention is preferably 0.018 mass% or less, more preferably 0.015 mass% or less, still more preferably 0.012 mass% or less, and still much more preferably 0.011 mass% or less, based on the total amount (100 mass%) of the lubricating oil composition.
  • Examples of the components (C) used in one embodiment of the present invention include an alkenyl bis-succinimide represented by the following general formula (c-1) and an alkenyl monosuccinimide represented by the following general formula (c-2).
  • R A1 , R A2 and R A3 are each independently an alkenyl group having a weight-average molecular weight (Mw) of 500 to 3000 (preferably 900 to 2500).
  • alkenyl groups capable of being selected as R A1 , R A2 and R A3 include a polybutenyl group, a polyisobutenyl group and an ethylene-propylene copolymer, and among these, a polybutenyl group or a polyisobutenyl group is preferable.
  • R B1 , R B2 and R B3 are each independently an alkylene group having 2 to 5 carbon atoms.
  • x1 is an integer of 0 to 10, preferably an integer of 1 to 4, and more preferably 2 or 3.
  • x2 is an integer of 1 to 10, preferably an integer of 2 to 5, and more preferably 3 or 4.
  • a modified alkenyl succinimide obtained by reacting a compound represented by the aforesaid general formula (c-1) or (c-2) with one or more selected from a boron compound, an alcohol, an aldehyde, a ketone, an alkylphenol, a cyclic carbonate, an epoxy compound and an organic acid is also contained.
  • the component (C) contains a non-boron-modified alkenyl bis-succinimide (C1).
  • the component (C1) is presumed to have a high effect of homogeneously dispersing the component (B), and it is thought that the component (C) can sustain the preignition suppression effect possessed by the component (B) even in long time use.
  • the lubricating oil composition containing a non-boron-modified alkenyl bis-succinimide (C1) as the component (C) together with the component (B) can effectively suppress occurrence of preignition even when it is used for a long time.
  • the component (C1) is a non-boron-modified alkenyl bis-succinimide, but is preferably a non-modified alkenyl bis-succinimide.
  • the content of the component (C1) in terms of nitrogen atoms in the lubricating oil composition of one embodiment of the present invention is preferably 0.001 to 0.15 mass%, more preferably 0.005 to 0.10 mass%, still more preferably 0.01 to 0.09 mass%, and still much more preferably 0.03 to 0.07 mass%, based on the total amount (100 mass%) of the lubricating oil composition.
  • the content ratio of the non-boron-modified alkenyl bis-succinimide (C1) in the component (C) is preferably 30 mass% or more, more preferably 50 mass% or more, still more preferably 60 mass% or more, still much more preferably 70 mass% or more, and particularly preferably 80 mass% or more, based on the total amount (100 mass%) of the component (C).
  • the component (C1) is preferably an alkenyl bis-succinimide represented by the aforesaid general formula (c-1), and is more preferably a non-boron-modified alkenyl bis-succinimide at least having a polybutenyl group or a polyisobutenyl group having a weight-average molecular weight of 500 to 3000 (preferably 900 to 2500).
  • the component (C) further contains a boron-modified alkenyl succinimide (C2) together with the component (C1).
  • the boron-modified alkenyl succinimide (C2) in the component (C) tends to be a factor for the occurrence of preignition if it is contained in a deposit occurring with long time use, as previously described.
  • the content of the component (C2) needs to be adjusted in such a manner that the content of boron atoms in the lubricating oil composition is in the aforesaid range.
  • Examples of the components (C2) include a boron-modified product of the alkenyl bis-succinimide represented by the aforesaid general formula (c-1) and a boron-modified product of the alkenyl monosuccinimide represented by the aforesaid general formula (c-2), but preferable is a boron-modified product of the alkenyl monosuccinimide represented by the aforesaid general formula (c-2).
  • polystyrene resins examples include polymers obtained by polymerizing one or two or more selected from ⁇ -olefins having 2 to 8 carbon atoms, but preferable is a copolymer of isobutene and 1-butene.
  • polyamines examples include single diamines, such as ethylenediamine, propylenediamine, butylenediamine and pentylenediamine, polyalkylene polyamines, such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, di(methylethylene)triamine, dibutylenetriamine, tributylenetetramine and pentapentylenehexamine; and piperazine derivatives, such as aminoethylpiperazine.
  • single diamines such as ethylenediamine, propylenediamine, butylenediamine and pentylenediamine
  • polyalkylene polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, di(methylethylene)triamine, dibutylenetriamine, tributylenetetramine and pentapentylenehexamine
  • piperazine derivatives such as aminoethylpipe
  • boron compounds include boron oxide, boron halide, boric acid, boric anhydride, boric acid ester, and ammonium salt of boric acid.
  • the ratio [B/N] of boron atoms to nitrogen atoms, both the atoms constituting the component (C2) is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, and still much more preferably 0.5 or more.
  • the content ratio [N/Ca] by mass of nitrogen atoms derived from the component (C) to calcium atoms derived from the component (B) in the lubricating oil composition of one embodiment of the present invention is preferably 0.90 or less, more preferably 0.80 or less, still more preferably 0.70 or less, still much more preferably 0.60 or less, particularly preferably 0.55 or less, and is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.10 or more, still much more preferably 0.15 or more, particularly preferably 0.20 or more.
  • the content ratio [B/N] by mass of boron atoms derived from the component (C2) to nitrogen atoms derived from the component (C) is preferably 0.01 to 0.35, more preferably 0.03 to 0.25, still more preferably 0.05 to 0.22, still much more preferably 0.10 to 0.20, and particularly preferably 0.12 to 0.18.
  • the content of the component (C) in terms of nitrogen atoms is preferably 0.005 to 0.15 mass%, more preferably 0.01 to 0.10 mass%, still more preferably 0.02 to 0.09 mass%, and still much more preferably 0.04 to 0.07 mass%, based on the total amount (100 mass%) of the lubricating oil composition.
  • the compounding amount (content) of the component (C) is appropriately adjusted in such a manner that the content of nitrogen atoms derived from the component (C) is in the aforesaid range, but it is preferably 0.10 to 15.0 mass%, more preferably 0.50 to 12.0 mass%, still more preferably 1.0 to 10.0 mass%, and still much more preferably 2.5 to 8.0 mass%, based on the total amount (100 mass%) of the lubricating oil composition.
  • the lubricating oil composition of one embodiment of the present invention preferably further contains zinc dithiophosphate (ZnDTP) (D) as an anti-wear agent.
  • ZnDTP zinc dithiophosphate
  • the component (D) may be used singly, or may be used in combination of two or more.
  • the zinc dithiophosphate (D) used in one embodiment of the present invention is preferably a compound represented by the following general formula (d-1).
  • R 1 to R 4 each independently represent a hydrocarbon group, and may be the same as one another or may be different from one another.
  • the number of carbon atoms of the hydrocarbon group capable of being selected as R 1 to R 4 is preferably 1 to 20, more preferably 1 to 16, still more preferably 3 to 12, and still much more preferably 3 to 10.
  • hydrocarbon groups capable of being selected as R 1 to R 4 include alkyl groups, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group and an octadecyl group; alkenyl groups, such as an octenyl group, a nonenyl group, a decenyl group, a undecenyl group, a dodecenyl group, a tridecenyl group, a te
  • alkyl groups more preferable are primary or secondary alkyl groups, and still more preferable are secondary alkyl groups, as the hydrocarbon groups capable of being selected as R 1 to R 4
  • the content of the component (D) in terms of zinc atoms is preferably 0.001 to 1.0 mass%, more preferably 0.005 to 0.80 mass%, still more preferably 0.01 to 0.60 mass%, still much more preferably 0.02 to 0.50 mass%, and particularly preferably 0.03 to 0.40 mass%, based on the total amount (100 mass%) of the lubricating oil composition.
  • the content (compounding amount) of the component (D) may be adjusted in such a manner that the content in terms of zinc atoms is in the above range, but it is preferably 0.01 to 15.0 mass%, more preferably 0.05 to 10.0 mass%, still more preferably 0.10 to 8.0 mass%, still much more preferably 0.20 to 5.0 mass%, or may be 1.00 mass% or less, 0.90 mass% or less, 0.85 mass% or less, or 0.80 mass% or less, based on the total amount (100 mass%) of the lubricating oil composition.
  • the lubricating oil composition of one embodiment of the present invention may further contain lubricating oil additives other than the components (B) to (D) when needed as long as the effects of the present invention are not impaired.
  • lubricating oil additives examples include an antioxidant, a pour point depressant, a viscosity index improver, a demulsifier, a friction modifier, a corrosion inhibitor, a metal deactivator, an antistatic agent, and an anti-foaming agent.
  • lubricating oil additives may be each used singly, or may be each used in combination of two or more.
  • the contents of these lubricating oil additives can be each appropriately adjusted as long as the effects of the present invention are not impaired, but the contents of the additives are each independently usually 0.001 to 15 mass%, preferably 0.005 to 10 mass%, and more preferably 0.01 to 5 mass%, based on the total amount (100 mass%) of the lubricating oil composition.
  • the production method for the lubricating oil composition of one embodiment of the present invention is not particularly limited, but from the viewpoint of productivity, preferable is a method having a step of compounding the aforesaid components (B) and (C), and if necessary, the component (D) and other lubricating oil additives with the base oil (A).
  • the compounding amounts of the components (A), (B), (C) and (D), and the lubricating oil additives are as previously described.
  • the kinematic viscosity of the lubricating oil composition of one embodiment of the present invention at 40°C is preferably 10 to 130 mm 2 /s, more preferably 20 to 115 mm 2 /s, still more preferably 30 to 100 mm 2 /s, and still much more preferably 40 to 90 mm 2 /s.
  • the kinematic viscosity of the lubricating oil composition of one embodiment of the present invention at 100°C is preferably 2.5 to 20.0 mm 2 /s, more preferably 4.0 to 16.0 mm 2 /s, still more preferably 5.5 to 14.0 mm 2 /s, and still much more preferably 7.0 to 12.0 mm 2 /s.
  • the viscosity index of the lubricating oil composition of one embodiment of the present invention is preferably 90 or more, more preferably 100 or more, still more preferably 110 or more, and still much more preferably 130 or more.
  • the acid value of the lubricating oil composition of one embodiment of the present invention is preferably 0.30 to 2.00 mgKOH/g, more preferably 0.35 to 1.70 mgKOH/g, still more preferably 0.40 to 1.30 mgKOH/g, and still much more preferably 0.45 to 1.00 mgKOH/g.
  • the acid value of the lubricating oil composition means a value measured in accordance with JIS K2501:2003 (indicator method).
  • the base number of the lubricating oil composition of one embodiment of the present invention is preferably 2.0 to 10.0 mgKOH/g, more preferably 2.5 to 8.0 mgKOH/g, still more preferably 3.0 to 6.5 mgKOH/g, and still much more preferably 3.5 to 5.0 mgKOH/g.
  • the base number of the lubricating oil composition means a value measured in accordance with JIS K2501:2003 (hydrochloric acid method).
  • the content of phosphorus atoms is preferably 0.01 to 0.15 mass%, more preferably 0.015 to 0.12 mass%, still more preferably 0.02 to 0.10 mass%, and still much more preferably 0.025 to 0.08 mass%, based on the total amount (100 mass%) of the lubricating oil composition.
  • the content of nitrogen atoms is preferably 0.01 to 0.50 mass%, more preferably 0.02 to 0.30 mass%, still more preferably 0.03 to 0.20 mass%, still much more preferably 0.04 to 0.15 mass%, and particularly preferably 0.045 to 0.10 mass%, based on the total amount (100 mass%) of the lubricating oil composition.
  • the content of magnesium atoms is less than 0.01 mass%, and still much more preferably less than 0.001 mass%, based on the total amount of the lubricating oil composition, from the viewpoint of decreasing a causative substance of a deposit.
  • the content of molybdenum atoms is less than 0.001 mass%, based on the total amount (100 mass%) of the lubricating oil composition, from the viewpoint of preparing a lubricating oil composition capable of effectively suppressing occurrence of preignition even when it is used for a long time.
  • the lubricating oil composition of one preferred embodiment of the present invention is excellent in preignition suppression effect even in the case where it is used for a long time.
  • the lubricating oil composition of one embodiment of the present invention can be applied to various apparatuses in which it can exhibit the above characteristics, but it is preferably applied to lubrication of gas engines.
  • the present invention can also provide the following [1] and [2].
  • the kinematic viscosity and viscosity index were measured and calculated in accordance with JIS K2283:2000.
  • the content was measured in accordance with JIS K2609:1998.
  • the acid value was measured in accordance with JIS K2501:2003 (indicator method).
  • the base number was measured in accordance with JIS K2501:2003 (hydrochloric acid method).
  • a base oil and various additives of types shown in Table 1 and Table 2 were added and mixed in compounding amounts shown in Table 1 and Table 2, thereby preparing each lubricating oil composition.
  • Antioxidant mixture of amine-based antioxidant and phenol-based antioxidant.
  • the lubricating oil composition prepared was placed as a 25 mL sample and subjected to complete combustion over a period of 30 minutes.
  • the temperature of the ash content after combustion was increased up to 600°C from 50°C at a temperature-increasing rate of 10°C/min in an atmosphere of oxygen at high pressure of 3 MPa using a differential scanning calorimeter (manufactured by METTLER TOLEDO, high-pressure DSC), and a peak calorific value (unit: mW) of the ash content was measured.
  • the peak calorific value of the ash content is preferably 22.0 mW or less, more preferably 20.0 mW or less, still more preferably 18.5 mW or less, still much more preferably 15.0 mW or less, and particularly preferably 11.0 mW or less.
  • Example 1 The lubricating oil compositions prepared in Example 1 and Comparative Example 1 were each subjected to the same operation as above as a new oil, and a peak calorific value (unit: mW) of the new oil was measured.
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 Formulation of lubricating oil composition
  • Base oil (a-i) mass% 14.31 13.00 13.00 13.00 13.00 13.00 13.00
  • Base oil (a-ii) mass% 75.82 78.16 78.37 79.37 77.27 78.20
  • Ca-based detergent Ca salicylate (b-i) mass% 1.58 1.58 1.58 1.58 1.58 Imide compound
  • Non-modified bis-succinimide (c1-ii) mass% 6.00 3.90 3.90 6.00 4.00
  • Boron-modified monosuccinimide (c2-i) mass% 1.30 Boron-modified monosuccinimide (c2-ii) mass% 0.49 0.49 0.49 0.56
  • Non-modified monosuccinimide (c3) mass% 1.00 1.00
  • Zinc dithiophosphate Pri-ZnDTP mass

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Claims (10)

  1. Schmierölzusammensetzung für einen Gasmotor, umfassend ein Basisöl (A), ein Detergens auf Calciumbasis (B) und ein Alkenylsuccinimid (C), wobei
    ein Gehalt der Komponente (B) in Form von Calciumatomen 0,09 bis 0,17 Masse-%, bezogen auf die Gesamtmenge der Schmierölzusammensetzung, beträgt,
    die Komponente (C) ein nicht-bormodifiziertes Alkenyl-bis-succinimid (C1) und ein bormodifiziertes Alkenylsuccinimid (C2) umfasst,
    ein Gehalt an Boratomen, abgeleitet von der Komponente (C), weniger als 0,02 Masse-%, bezogen auf die Gesamtmenge der Schmierölzusammensetzung, beträgt,
    einen Gehalt an Magnesiumatomen weniger als 0,01 Masse-%, bezogen auf die Gesamtmenge der Schmierölzusammensetzung, beträgt und
    einen Gehalt an Molybdänatomen weniger als 0,001 Masse-%, bezogen auf die Gesamtmenge der Schmierölzusammensetzung, beträgt.
  2. Schmierölzusammensetzung gemäß Anspruch 1, wobei ein Massengehaltsverhältnis [N/Ca] von Stickstoffatomen, abgeleitet von der Komponente (C), zu Calciumatomen, abgeleitet von der Komponente (B), 0,90 oder weniger beträgt.
  3. Schmierölzusammensetzung gemäß Anspruch 1 oder 2, wobei die Komponente (B) Calciumsalicylat (B1) umfasst.
  4. Schmierölzusammensetzung gemäß einem der Ansprüche 1 bis 3, wobei die Komponente (C1) ein nicht-bormodifiziertes Alkenyl-bis-succinimid ist, das mindestens eine Polybutenylgruppe oder eine Polyisobutenylgruppe mit einem gewichtsmittleren Molekulargewicht von 500 bis 3.000 aufweist.
  5. Schmierölzusammensetzung gemäß Anspruch 1-4, wobei ein Massengehaltsverhältnis [B/N] von Boratomen, abgeleitet von der Komponente (C2), zu Stickstoffatomen, abgeleitet von der Komponente (C), 0,01 bis 0,35 beträgt.
  6. Schmierölzusammensetzung gemäß einem der Ansprüche 1 bis 5, wobei ein Gehalt der Komponente (C) in Form von Stickstoffatomen 0,005 bis 0,15 Masse-%, bezogen auf die Gesamtmenge der Schmierölzusammensetzung, beträgt.
  7. Schmierölzusammensetzung gemäß einem der Ansprüche 1 bis 6, ferner umfassend Zinkdithiophosphat (D).
  8. Schmierölzusammensetzung gemäß einem der Ansprüche 1 bis 7, wobei ein Gehalt an Magnesiumatomen weniger als 0,001 Masse-%, bezogen auf die Gesamtmenge der Schmierölzusammensetzung, beträgt.
  9. Schmierölzusammensetzung gemäß einem der Ansprüche 1 bis 8, wobei der Gehalt der Komponente (B) in Form von Calciumatomen 0,118 bis 0,135 Masse-%, bezogen auf die Gesamtmenge der Schmierölzusammensetzung, beträgt.
  10. Verwendung einer Schmierölzusammensetzung, wobei die Schmierölzusammensetzung gemäß einem der Ansprüche 1 bis 9 auf einem Gasmotor angewendet wird.
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WO2020203525A1 (ja) 2020-10-08
FI3950904T3 (fi) 2025-04-25
JPWO2020203525A1 (de) 2020-10-08
EP3950904A1 (de) 2022-02-09

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