WO2011161908A1 - 軸受用潤滑油組成物 - Google Patents
軸受用潤滑油組成物 Download PDFInfo
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- WO2011161908A1 WO2011161908A1 PCT/JP2011/003425 JP2011003425W WO2011161908A1 WO 2011161908 A1 WO2011161908 A1 WO 2011161908A1 JP 2011003425 W JP2011003425 W JP 2011003425W WO 2011161908 A1 WO2011161908 A1 WO 2011161908A1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/041—Mixtures of base-materials and additives the additives being macromolecular compounds only
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
- F16C33/00—Parts of bearings; Special methods for making bearings or parts thereof
- F16C33/02—Parts of sliding-contact bearings
- F16C33/04—Brasses; Bushes; Linings
- F16C33/06—Sliding surface mainly made of metal
- F16C33/10—Construction relative to lubrication
- F16C33/1025—Construction relative to lubrication with liquid, e.g. oil, as lubricant
- F16C33/109—Lubricant compositions or properties, e.g. viscosity
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
- F16C33/00—Parts of bearings; Special methods for making bearings or parts thereof
- F16C33/30—Parts of ball or roller bearings
- F16C33/66—Special parts or details in view of lubrication
- F16C33/6637—Special parts or details in view of lubrication with liquid lubricant
- F16C33/6688—Lubricant compositions or properties, e.g. viscosity
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
- C10M2207/2825—Esters of (cyclo)aliphatic oolycarboxylic acids used as base material
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy compounds
- C10M2207/2835—Esters of polyhydroxy compounds 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
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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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/109—Polyethers, i.e. containing di- or higher polyoxyalkylene groups esterified
- C10M2209/1095—Polyethers, i.e. containing di- or higher polyoxyalkylene groups esterified used as base material
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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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/081—Thiols; Sulfides; Polysulfides; Mercaptals 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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/085—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing carboxyl groups; Derivatives thereof
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- 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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/02—Bearings
Definitions
- the present invention relates to a lubricating oil composition for bearings. More specifically, the present invention relates to a lubricating oil composition for bearings having a high viscosity index that has a low viscosity over a wide temperature range.
- ester-based lubricating oils containing a viscosity index improver have been proposed (for example, Patent Documents 2 to 5). Further, a lubricating oil in which a viscosity index improver is added to a mixed base oil of an olefin such as an ester and poly- ⁇ -olefin (for example, Patent Document 6), and a viscosity index improver is added to a mixed base oil of an ester and a mineral oil.
- An ester-based lubricating oil for example, Patent Document 8 containing a lubricating oil (for example, Patent Document 7), a viscosity index improver, and an antiwear agent has been proposed.
- the lubricating oil used in conventional spindle motors has a large viscosity change with temperature and has a low viscosity under a high temperature environment, but a high viscosity under a low temperature environment. There was a problem of becoming higher.
- the ester-based lubricating oil containing the conventional viscosity index improver described in Patent Documents 2 to 5 the lubricating oil has a high viscosity, so the friction loss of the equipment is high, and poly- ⁇ -olefin or
- the lubricating oil described in Patent Documents 6 and 7 containing mineral oil as a lubricating base oil the effect of improving the viscosity index is low, and poly- ⁇ -olefin and mineral oil are contained in a high temperature environment.
- the amount of evaporation loss of the lubricating oil increases because the low-molecular components easily volatilize.
- the lubricating oil described in Patent Document 8 containing an antiwear agent there is a problem that evaporation loss due to the decomposition product of the antiwear agent occurs in a high temperature environment.
- the object of the present invention is that the viscosity in a low temperature environment is lower than that of a conventional lubricating oil, and a constant viscosity is maintained in a high temperature environment so that liquid leakage and seizure does not occur as in the case of a conventional lubricating oil, and the lubricating oil
- An object of the present invention is to provide a lubricating oil composition for bearings that has a low evaporation loss.
- the present invention relates to a diester (A1) represented by the following general formula (1), a diester (A2) represented by the following general formula (2), and a diester (A3) represented by the following general formula (3).
- the bearing lubricating oil composition (K) has a total weight ratio of (A) and (B) of 81% by weight or more based on the weight of the bearing lubricating oil composition.
- R 1 to R 6 are the same or different and each represents an alkyl group having 1 to 18 carbon atoms
- R 7 to R 8 are the same or different and each represents an alkylene group having 1 to 8 carbon atoms.
- X represents an alkylene group having 1 to 16 carbon atoms
- a 1 is the same or different and represents an alkylene group having 2 to 4 carbon atoms
- n represents an integer of 1 to 10.
- the bearing lubricating oil composition (K) of the present invention has a high viscosity index, a constant viscosity in a high temperature environment, a low viscosity in a low temperature environment, a low viscosity in a wide temperature range, and a high temperature environment.
- the amount of evaporation loss of lubricating oil is small even under.
- the diester (A) in the present invention is represented by the diester (A1) represented by the following general formula (1), the diester (A2) represented by the following general formula (2), and the following general formula (3). It is at least one selected from the group consisting of diesters (A3).
- the diester (A1) is represented by the following general formula (1).
- R 1 and R 2 are the same or different and each represents an alkyl group having 1 to 18 carbon atoms, and X represents an alkylene group having 1 to 16 carbon atoms.
- alkyl group having 1 to 18 carbon atoms of R 1 to R 2 include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, amyl group, isoamyl group, hexyl group, cyclohexyl group, Methylhexyl group, heptyl group, methylheptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, isononyl group, 3,5,5-trimethylhexyl group, decyl group, isodecyl group, lauryl group, tridecyl group, Examples include myristyl group, isomyristyl group, cetyl group, stearyl group, and isostearyl group. Among these, from the viewpoint of the viscosity of the lubricating oil composition, R 1 to R 2 preferably
- alkylene group having 1 to 16 carbon atoms of X include methylene, ethylene, 1,2-propylene, 1,3-propylene, tetramethylene, 2-methylpropylene, pentamethylene, 2,2-dimethylpropylene, Hexamethylene, 3-methylpentamethylene, heptamethylene, octamethylene, nonamethylene, 2,4-diethylpentamethylene, decamethylene, undecamethylene, dodecamethylene, tridecamethylene, tetradecamethylene, pentadecamethylene, hexadecamethylene, etc. Is mentioned.
- the number of carbon atoms is preferably 1 to 12, particularly preferably the sum of R 1 , R 2 and X is 12 to 38, more preferably 18 to 30. .
- Preferred examples of the diester (A1) include neopentyl glycol di n-pentanoate (molecular weight: 272), neopentyl glycol di n-hexanoate (molecular weight: 300), neopentyl glycol di n-heptanoate (molecular weight: 329), neopentyl.
- Glycol di n-octanoate (molecular weight: 357), neopentyl glycol di n-nonanoate (molecular weight: 385), neopentyl glycol di n-decanoate (molecular weight: 413), 3-methyl-1,5-pentanediol di n- Pentanoate (molecular weight: 286), 3-methyl-1,5-pentanediol di n-hexanoate (molecular weight: 314), 3-methyl-1,5-pentanediol di n-heptanoate (molecular weight: 343), 3-methyl -1,5-pentanediol n-octanoate (molecular weight: 371), 3-methyl-1,5-pentanediol di-n-nonanoate (molecular weight: 399), 3-methyl-1,5-pentanediol di n-
- the diester (A2) is represented by the following general formula (2).
- R 3 to R 4 are the same or different and each represents an alkyl group having 1 to 18 carbon atoms
- a 1 is the same or different and represents an alkylene group having 2 to 4 carbon atoms
- n is Represents an integer of 1 to 10.
- R 3 to R 4 preferably have 1 to 14 carbon atoms, and more preferably 1 to 12 carbon atoms.
- Preferred examples of the diester (A2) include diethylene glycol di n-pentanoate (molecular weight: 274), diethylene glycol di n-heptanoate (molecular weight: 331), diethylene glycol di n-octanoate (molecular weight: 356), diethylene glycol di n-nonanoate (molecular weight: 387), diethylene glycol di n-decanoate (molecular weight: 415), triethylene glycol di n-hexanoate (molecular weight: 346), triethylene glycol di n-heptanoate (molecular weight: 374), triethylene glycol di n-octanoate (molecular weight: 403), triethylene glycol di n-nonanoate (molecular weight: 430), triethylene glycol di n-decanoate (molecular weight: 459), tetraethylene glycol di n- Tertanoate (molecular weight: 36
- the diester (A3) is represented by the following general formula (3).
- R 5 to R 6 are the same or different and each represents an alkyl group having 1 to 18 carbon atoms
- R 7 to R 8 are the same or different and each represents an alkylene group having 1 to 8 carbon atoms.
- the same or different alkylene group having 1 to 8 carbon atoms of R 7 to R 8 include methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene and the like.
- the number of carbon atoms is preferably 1 to 6 from the viewpoint of the viscosity of the lubricating composition.
- the sum of the carbon numbers of R 5 , R 6 , R 7 and R 8 is 10 to 36, and more preferably 14 to 28.
- the diester (A2) is preferable from the viewpoint of the evaporation loss amount of the lubricating oil composition.
- the diester (A2) is a general formula (2) in which R 3 to R 4 are the same or different alkyl groups having 4 to 10 carbon atoms, A 1 is an ethylene group and / or a propylene group, and n is 2 A case of ⁇ 6 is preferable.
- the molecular weight of the diester (A) in the present invention is 250 or more, preferably 300 or more, more preferably 350 or more, from the viewpoint of evaporation loss, and 600 or less, preferably 500 or less, more preferably from the viewpoint of reducing friction loss. Is 450 or less.
- the molecular weight of (A) is less than 250, the vapor pressure is high and the amount of evaporation loss in a high temperature environment is large.
- the molecular weight of (A) exceeds 600, the viscosity of the lubricating oil composition increases and the friction loss of the bearing becomes higher.
- the diester (A) of the present invention comprises an aliphatic dihydric alcohol and a monocarboxylic acid, a polyalkylene glycol and a monocarboxylic acid, or a thiodicarboxylic acid and a monohydric alcohol according to a conventional method, preferably an inert gas atmosphere such as nitrogen. It can be prepared by esterification with heating and stirring in the presence or absence of an esterification catalyst at medium, normal or reduced pressure.
- the total acid value of the diester (A) of the present invention is preferably 0.5 mgKOH / g or less, more preferably 0.001 to 0.1 mgKOH, from the viewpoint of corrosion prevention, wear resistance, and stability. / G.
- Poly (meth) acrylate viscosity index improver (B) is a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms and a (meth) acrylic acid ester having a hydroxyalkyl group having 1 to 4 carbon atoms
- a copolymer containing (meth) acrylic acid alkyl ester (b3) having an essential constituent monomer is preferred.
- the essential constituent monomers (b1) to (b3) of (B) will be described below.
- (B1) is a group consisting of (meth) acrylic acid alkyl ester (b11) having an alkyl group having 1 to 4 carbon atoms and (meth) acrylic acid ester (b12) having a hydroxyalkyl group having 1 to 4 carbon atoms.
- One or more selected (meth) acrylic acid esters are selected.
- Examples of (b11) include methyl (meth) acrylate, ethyl (meth) acrylate, n- or iso-propyl (meth) acrylate, n-, (meth) acrylate, iso- or sec-butyl.
- Preferred are methyl methacrylate and n-butyl methacrylate, and more preferred is methyl methacrylate from the viewpoint of improving the viscosity index.
- (B12) is preferably a (meth) acrylic acid ester having a hydroxyalkyl group having 2 to 3 carbon atoms, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2 or 3-hydroxypropyl (meth) acrylate, etc. Is mentioned.
- Examples of (b2) include n-undecyl (meth) acrylate, n-dodecyl (meth) acrylate, 2-methylundecyl (meth) acrylate, n-tridecyl (meth) acrylate, and (meth) acrylic.
- Examples of (b3) include n-hexadecyl acrylate, n-hexadecyl methacrylate (hereinafter abbreviated as HMA), n-octadecyl acrylate, n-octadecyl methacrylate (hereinafter abbreviated as OMA), and (meth) acrylate n- Eicosyl, n-docosyl (meth) acrylate, 2-methylpentadecyl (meth) acrylate, 2-hexyldecyl (meth) acrylate, 2-methylhexadecyl (meth) acrylate, 2- (meth) acrylic acid 2- Octyldecyl, 2-methydecyl (meth) acrylate, 2-methylheptadecyl (meth) acrylate, 2-methyloctadecyl (meth) acrylate, 2-octyldodecyl (meth) acryl
- Preferred ranges of the respective weight percentages of (b1) to (b3) based on the total weight of (b1) to (b3) of the viscosity index improver (B) are as follows. The following% represents weight%.
- the proportion of (b1) is preferably 30 to 99.9%, more preferably 40 to 99.9%, from the viewpoint of viscosity index and solubility.
- the proportion of (b2) is preferably 0.01 to 39.9%, more preferably 0.01 to 35%, from the viewpoint of viscosity index and solubility.
- the proportion of (b3) is preferably 0.01 to 60%, more preferably 0.01 to 50% from the viewpoints of the viscosity index and the low temperature viscosity.
- (b ′) As the monomer constituting the viscosity index improver (B) in the present invention, in addition to (b1) to (b3), another monomer (b ′) can be used as a constituent monomer.
- Examples of (b ′) include (b1 ′) to (b9 ′).
- a hydroxyl group-containing aromatic vinyl monomer such as p-hydroxystyrene
- mono- or di-hydroxyalkyl (C 1-4) substituted (meth) acrylamide [N, N-dihydroxymethyl (meth) acrylamide, N, N-dihydroxypropyl (meth) acrylamide, N, N-di-2-hydroxybutyl (meth) acrylamide, etc.]
- vinyl alcohol formed by hydrolysis of vinyl acetate units
- alkenol having 3 to 12 carbon atoms [(Meth) allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1-octenol, 1-undecenol, etc.]
- alkenediol having 4 to 12 carbon atoms [1-buten-3-ol, 2-buten-1-ol , 2-butene-1,4-diol, etc.]
- Primary amino group-containing vinyl monomers such as alkenylamines having 3 to 6 carbon atoms [(meth) allylamine, crotylamine, etc.], aminoalkyl (2 to 6 carbon atoms) (meth) acrylates [aminoethyl (meth) acrylates Etc.]
- Secondary amino group-containing vinyl monomer for example, alkyl (carbon number 1-6) aminoalkyl (carbon number 2-6) (meth) acrylate [t-butylaminoethyl methacrylate, methylaminoethyl (meth) Acrylates, etc.], diphenylamine (meth) acrylamide [4-diphenylamine (meth) acrylamide, 2-diphenylamine (meth) acrylamide, etc.], dialkenylamine having 6 to 12 carbon atoms [di
- a quaternizing agent alkyl chloride having 1 to 12 carbon atoms, dialkyl sulfuric acid, dialkyl carbonate, benzyl chloride, etc.
- (B3 ′) Hydrocarbon vinyl monomer (B31 ′) Aliphatic hydrocarbon vinyl monomer
- alkene having 2 to 20 carbon atoms [ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, etc.]
- 4 carbon atoms To 12 alkadienes [butadiene, isoprene, 1,4-pentadiene, 1,6-heptadiene, 1,7-octadiene, etc.].
- Aromatic hydrocarbon vinyl monomer For example, styrene, ⁇ -methylstyrene, vinyltoluene, 2,4-dimethylstyrene, 4-ethylstyrene, 4-isopropylstyrene, 4-butylstyrene, 4-phenylstyrene, 4-cyclohexylstyrene, 4-benzylstyrene, 4 -Crotylbenzene, 2-vinylnaphthalene and the like.
- aryl vinyl ketones [methyl vinyl ketone, ethyl vinyl ketone, phenyl vinyl ketone, etc.] can be used.
- (B5 ′) an epoxy group-containing vinyl monomer examples thereof include glycidyl (meth) acrylate and glycidyl (meth) allyl ether.
- (B6 ′) a halogen element-containing vinyl monomer For example, vinyl chloride, vinyl bromide, vinylidene chloride, (meth) allyl chloride, halogenated styrene (dichlorostyrene and the like) and the like can be mentioned.
- (B7 ′) an ester of an unsaturated polycarboxylic acid For example, an alkyl, cycloalkyl or aralkyl ester of an unsaturated polycarboxylic acid may be mentioned. Among them, an alkyl diester having 1 to 8 carbon atoms [dimethyl maleate, unsaturated dicarboxylic acid [maleic acid, fumaric acid, itaconic acid, etc.] Dimethyl fumarate, diethyl maleate, dioctyl maleate] and the like.
- (B8 ′) a polyoxyalkylene chain-containing vinyl monomer For example, polyoxyalkylene glycol (alkylene group having 2 to 4 carbon atoms, degree of polymerization 2 to 50) or polyoxyalkylene polyol [polyoxyalkylene ether of the above tri- to 8-valent alcohol (alkyl group having 2 to 4 carbon atoms, Degree of polymerization 2 to 100)] or mono (meth) acrylates thereof (polyethylene glycol (molecular weight 100 to 300) mono (meth) acrylate, polypropylene glycol (molecular weight 130 to 500) mono of their alkyl (1 to 4 carbon atoms) ether (Meth) acrylate, methoxypolyethylene glycol (molecular weight 110 to 310) (meth) acrylate, lauryl alcohol ethylene oxide adduct (2 to 30 mol) (meth) acrylate, mono (meth) acrylic acid polyoxyethylene (molecular weight 150 to 230) Rubitan] and the like
- Monocarboxyl group-containing vinyl monomers such as unsaturated monocarboxylic acids [(meth) acrylic acid, ⁇ -methyl (meth) acrylic acid, crotonic acid, cinnamic acid, etc.], monoalkyls of unsaturated dicarboxylic acids (carbon number) 1-8) esters [maleic acid monoalkyl esters, fumaric acid monoalkyl esters, itaconic acid monoalkyl esters, etc.]; vinyl monomers containing two or more carboxyl groups, such as maleic acid, fumaric acid, itaconic acid And citraconic acid.
- (B ′) may be a combination of two or more, but the total of (b ′) based on the total weight of (b1) to (b3) is preferably 40% or less from the viewpoint of the effect of improving the viscosity index. is there.
- the weight average molecular weight of the poly (meth) acrylate viscosity index improver (B) is preferably 5,000 to 1,000,000, more preferably 30,000 to 1,000, from the viewpoint of the effect of improving the viscosity index. , 000.
- the solubility parameter ( ⁇ ) of the poly (meth) acrylate viscosity index improver (B) is preferably 9.0 to 11.0, more preferably 9.10, from the viewpoint of solubility in the diester (A). 2 to 10.5.
- the solubility parameter can be calculated from the structure of the monomer used and its molar ratio by the method by Fedors “Polym. Eng. Sci. 14 (2) 152, (1974)”.
- the poly (meth) acrylate viscosity index improver (B) of the present invention is preferably diluted with a diester (A) from the viewpoint of handling, and may be diluted with another lubricating base oil (D).
- lubricating base oils (D) include mineral oil, poly- ⁇ -olefin, alkylbenzene, animal and vegetable oils, esters other than diester (A), polyalkylene glycol, polyvinyl ether, polyphenyl ether, silicone oil, and the like. It is done.
- the other lubricating base oil (D) preferably has a kinematic viscosity at 100 ° C. of 2 to 10 mm 2 / s from the viewpoint of the viscosity of the lubricating oil composition.
- Mineral oil includes solvent refined mineral oil, hydrorefined mineral oil, and wax isomerized oil.
- poly- ⁇ -olefins examples include ⁇ -olefins having 2 to 16 carbon atoms (for example, ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, etc. ) Or a copolymer thereof.
- alkyl benzene examples include monoalkyl benzene, dialkyl benzene, trialkyl benzene, and tetraalkyl benzene substituted with an alkyl group having 1 to 40 carbon atoms.
- Animal and vegetable oils include beef tallow, lard, palm oil, coconut oil, rapeseed oil, castor oil, sunflower oil and the like.
- esters other than the diester (A) include diesters of dicarboxylic acids and monohydric alcohols, triesters, tetraesters, and complex esters.
- polyalkylene glycol examples include a ring-opening polymer of alcohol and alkylene oxide having 2 to 4 carbon atoms.
- alkylene oxide examples include ethylene oxide, propylene oxide, and butylene oxide, and a polymer using one of these or a copolymer using two or more types can be used.
- Polyvinyl ether is a compound obtained by polymerization of vinyl ether monomers, and monomers include methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, sec-butyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether. N-hexyl vinyl ether, 2-methoxyethyl vinyl ether, 2-ethoxyethyl vinyl ether and the like.
- polyphenyl ether examples include compounds having a structure in which meta positions of two or more aromatic rings are connected by an ether bond or a thioether bond. Specifically, bis (m-phenoxyphenyl) ether, m-bis ( m-phenoxyphenoxy) benzene, and thioethers (commonly referred to as C-ethers) in which one or more of these oxygens are substituted with sulfur.
- silicone oil examples include dimethyl silicone and methylphenyl silicone, and modified silicones such as long-chain alkyl silicone and fluorosilicone.
- the content of the other lubricating base oil (D) is preferably 19% by weight or less, and more preferably 15% by weight or less, based on the weight of the bearing lubricating oil composition (K).
- the poly (meth) acrylate viscosity index improver (B) can be obtained by a known production method. For example, it can be obtained by radical polymerization of the above monomer in a solvent in the presence of a polymerization catalyst.
- diester (A) is preferable, and other lubricating base oil (D) can also be used.
- an azo catalyst for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethyl
- Valeronitrile dimethyl 2,2-azobisisobutyrate and the like
- peroxides eg t-butyl peroxypivalate, t-hexyl peroxypivalate, t-butyl peroxyneoheptanoate, t-butylperoxyneodecanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-amylperoxy-2-ethylhexanoate, 1,1,3,3 -Tetramethylbutylperoxy 2-ethylhexanoate, dibutylperoxytrimethyladipate, benzoyl peroxide, cumyl peroxide Lau
- a chain transfer agent may be used in combination, and examples thereof include thiocarboxylic acids (n-lauryl mercaptan (hereinafter abbreviated as DM), mercaptoethanol, mercaptopropanol, etc.), thiolic acids (thioglycolic acid). , Thiomalic acid, etc.), amines (dibutylamine, etc.) and the like.
- the amount of the chain transfer agent is preferably 0.001 to 5%, more preferably 0.05, based on the weight of the monomer. ⁇ 3%.
- the reaction temperature is 50 to 140 ° C, preferably 70 to 120 ° C. In addition to the above solution polymerization, it can also be obtained by bulk polymerization, emulsion polymerization or suspension polymerization.
- the polymerization mode of the viscosity index improver (B) may be either random addition polymerization or alternating copolymerization, and may be either graft copolymerization or block copolymerization.
- the weight average molecular weight of (B) can be adjusted by the polymerization temperature, monomer concentration (solvent concentration), catalyst amount, chain transfer agent amount, and the like.
- the difference between the solubility parameter ( ⁇ ) of the diester (A) and the solubility parameter ( ⁇ ) of the viscosity index improver (B) satisfies the following general formula (1) from the viewpoint of the viscosity index improving effect and solubility.
- is 0.3 or more
- the bearing lubricating oil composition (K) of the present invention contains a diester (A) and a viscosity index improver (B), and the content of (B) is preferably 0.1 based on the weight of (K). -30% by weight, more preferably 0.1-20% by weight, still more preferably 0.3-5% by weight.
- the lubricating oil composition for bearings (K) of the present invention may contain other components in addition to the diester (A) and the poly (meth) acrylate viscosity index improver (B). Based on the weight of (A), the ratio of the total weight of (A) and (B) is 81% by weight or more, preferably 85% by weight or more. When the ratio of the total weight of (A) and (B) is less than 81% by weight based on the weight of (K), the effect of improving the viscosity index is lowered.
- other components include the other lubricating base oils (D) and the following additives (E).
- the additive (E) that can be contained in the bearing lubricating oil composition (K) of the present invention includes pour point depressant, detergent, dispersant, oiliness improver, antiwear agent (C), pole Examples thereof include a pressure agent, an antifoaming agent, a demulsifier, a corrosion inhibitor, a rust inhibitor, a hydrolysis inhibitor, and an antioxidant.
- the total amount added is preferably 15% by weight or less, and more preferably 10% by weight or less, based on the weight of the lubricating composition for bearing (K).
- the antiwear agent (C) does not contain (C) from the viewpoint of heat resistance, or may contain 0.09% by weight or less based on the weight of (K). preferable.
- antiwear agent (C) examples include neutral phosphate esters (for example, tricresyl phosphate, trixylenyl phosphate, trioctyl phosphate) and neutral phosphite esters (for example, trioleyl phosphate). , Trixylenyl phosphite, trioctyl phosphite, etc.), acidic phosphate esters (eg, oleyl acid phosphate, 2-ethylhexyl acid phosphate, etc.) and acidic phosphites (eg, dilauryl hydrogen phosphite, Rail hydrogen phosphite).
- neutral phosphate esters for example, tricresyl phosphate, trixylenyl phosphate, trioctyl phosphate
- neutral phosphite esters for example, trioleyl phosphate
- acidic phosphate esters eg, oleyl acid phosphate, 2-
- the kinematic viscosity at 100 ° C., 40 ° C. and 0 ° C. of the lubricating oil composition for bearings (K) of the present invention is preferably in the following range.
- the kinematic viscosity at 100 ° C. is preferably 2.0 mm 2 / s or more, more preferably 2.5 mm 2 / s or more, from the viewpoint of preventing liquid leakage or seizure, and preferably 5.8 mm from the viewpoint of reducing friction loss. 2 / s or less, more preferably 5.5 mm 2 / s or less.
- the kinematic viscosity at 0 ° C. is preferably 10 to 85 mm 2 / s, more preferably 10 to 70 mm 2 / s from the viewpoint of reducing friction loss in a low temperature environment, and the kinematic viscosity at ⁇ 20 ° C. is preferably 10 It is ⁇ 250 mm 2 / s, more preferably 10 to 220 mm 2 / s.
- the viscosity index of (K) is preferably 160 to 550, more preferably 180 to 550.
- the kinematic viscosity ratio (100 ° C. kinematic viscosity / ⁇ 20 ° C. kinematic viscosity) of (K) is preferably 5 to 55, more preferably 5 to 50.
- the bearing lubricating oil composition (K) of the present invention contains a diester (A) and a viscosity index improver (B), but the kinematic viscosity of (K) increases as the content ratio of (B) increases.
- the kinematic viscosity of (K) increases as the weight average molecular weight of (B) increases.
- the specific viscosity index improver (B) which is a coalescence the specific viscosity index improver (B) which is a coalescence, the bearing lubricating oil composition (K) of the present invention having low viscosity in a wide temperature range and low evaporation loss in a high temperature environment is obtained. Obtainable.
- viscosity index improver in addition to the poly (meth) acrylate viscosity index improver (B), an olefin copolymer system (solubility parameter: about 8.2), a polyisobutylene system (solubility parameter: about 7.6), etc.
- solubility parameter is low, the solubility with the diester (A) is poor, and the effect of improving the viscosity index is low.
- the bearing lubricating oil composition (K) of the present invention is particularly preferably used as a fluid bearing lubricating oil composition.
- a fluid bearing is a bearing supported by a thin liquid film. Specifically, it is used for a fan motor, a DC motor, and a spindle motor for a magnetic disk device, an optical disk device, a magneto-optical disk device, a polygon mirror driving device, etc. Bearing.
- Production Example 1 Production of diester (A1-1) A reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a water fractionator with a cooling tube was charged with 255.0 parts of neopentyl glycol, 701.3 parts of heptanoic acid, xylene 48 parts were charged and heated to 200 ° C. in a nitrogen atmosphere. The esterification reaction was carried out for about 10 hours while removing the produced water distilled off with the moisture fraction receiver with the theoretical amount of produced water (88 g) as the target. After completion of the reaction, excess acid and xylene were removed by distillation to obtain an esterified crude product.
- the middle distillate was collected by removing 15% by volume of the first fraction and the latter fraction by vacuum distillation.
- the middle distillate was diester (A1-1): neopentylglycol di n-heptanoate (molecular weight 328), and the total acid value of (A1-1) was 0.01 mgKOH / g.
- the diester (A1-2) was prepared in the same manner as in Production Example 1, except that the preparation of the diester (A1-2) was changed to 277.5 parts of 3-methyl-1,5-pentanediol, 672.6 parts of heptanoic acid, and 48 parts of xylene.
- the total acid value of (A1-2) was 0.01 mgKOH / g.
- the diester (A1-3) was prepared in the same manner as in Production Example 1, except that the preparation of the diester (A1-3) was changed to 255.1 parts of 3-methyl-1,5-pentanediol, 684.9 parts of octanoic acid, and 47 parts of toluene.
- the total acid value of (A1-3) was 0.01 mgKOH / g.
- Production Example 4 Same as Production Example 1, except that the preparation of diester (A1-4) was changed to 305.9 parts neopentyl glycol, 659.9 parts pentanoic acid and 48 parts xylene, and distillation was carried out at 200 ° C. under reduced pressure.
- the total acid value of (A1-4) was 0.01 mgKOH / g.
- the diester (A2-1) triester was prepared in the same manner as in Production Example 1, except that the preparation of the diester (A2-1) was changed to 322.5 parts of triethylene glycol, 615.1 parts of heptanoic acid, and 47 parts of xylene. Ethylene glycol di n-heptanoate (molecular weight 375) was obtained. The total acid value of (A2-1) was 0.01 mgKOH / g.
- the total acid value of (A2-2) was 0.01 mgKOH / g.
- Diester (A2-3) tetraester was prepared in the same manner as in Production Example 1, except that the preparation of diester (A2-3) was changed to 398.0 parts of tetraethylene glycol, 523.5 parts of hexanoic acid, and 46 parts of xylene. Ethylene glycol di n-hexanoate (molecular weight 391) was obtained. The total acid value of (A2-3) was 0.01 mgKOH / g.
- Production Example 8 Production of diester (A2-4)
- a reaction vessel equipped with a stirrer, thermometer, nitrogen introduction tube, and moisture fractionator with a cooling tube 276.7 parts of tripropylene glycol, 633.0 parts of dodecanoic acid, xylene 45 parts were charged and the temperature was raised to 220 ° C. in a nitrogen atmosphere.
- the esterification reaction was carried out for about 15 hours while removing the produced water distilled off with the moisture fraction receiver with the theoretical amount of produced water (52 g) as the target. After completion of the reaction, excess acid and xylene were removed by distillation to obtain an esterified crude product.
- the activated carbon process was performed.
- the activated carbon is removed by filtration, the water in the esterified crude product is removed by distillation, and diester (A2-4): tripropylene glycol di-n-dodecanoate (molecular weight: 557), and the total acid of (A2-4) The value was 0.02 mg KOH / g.
- Production Example 9 Production of diester (A3-1) In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a moisture fractionator with a cooling tube, 431.1 parts of n-butanol and 493.6 parts of thiodipropionic acid Then, 46 parts of xylene were charged, and the temperature was raised to 180 ° C. in a nitrogen atmosphere. The esterification reaction was carried out for about 12 hours while removing the produced water distilled off with the moisture fraction receiver with the theoretical amount of produced water (100 g) as the target. After completion of the reaction, excess alcohol and xylene were removed by distillation to obtain an esterified crude product.
- the middle distillate was collected by removing 15% by volume of the first fraction and the latter fraction by vacuum distillation.
- the middle distillate was diester (A3-1): di-n-butyl thiodipropionate (molecular weight 290), and the total acid value of (A3-1) was 0.01 mgKOH / g.
- the diester (A3-2) was prepared in the same manner as in Production Example 9 except that the preparation of the diester (A3-2) was changed to 546.0 parts of 2-heptanol, 380.7 parts of thiodipropionic acid, and 46 parts of xylene. : Di-2-heptyl thiodipropionate (molecular weight 375) was obtained. The total acid value of (A3-2) was 0.01 mgKOH / g.
- the low boiling point component was distilled off to obtain a (D-1) solution of a viscosity index improver (B-1) as a copolymer. 250 parts of (D-1) was added so that the concentration of the obtained viscosity index improver (B-1) was 20% by weight, and the (D-1) solution of the viscosity index improver (B-1) (BA -1) was obtained.
- the resulting viscosity index improver had a weight average molecular weight of 3840,000.
- Production Example 12 Production of viscosity index improver (B-2) 20 parts of 3-methyl-1,5-pentanediol (A1-3) as a polymerization solvent, 50 parts of methyl methacrylate as a monomer, 17 parts of N23, N45 17 parts, 12 parts of HMA, 4 parts of OMA, and the same procedure as in Production Example 11 except that the monomer diluent was changed to 130 parts (A1-3).
- a solution (B1-3) (A1-3) was obtained. 250 parts of (A1-3) was added so that the concentration of the obtained viscosity index improver (B-2) was 20% by weight, and the (A1-3) solution of the viscosity index improver (B-2) (BA -2) was obtained.
- the resulting viscosity index improver had a weight average molecular weight of 381,000.
- the obtained viscosity index improver had a weight average molecular weight of 292,000.
- Production Example 15 Production of viscosity index improver (B-5) 20 parts of dipropylene glycol di n-octanoate (A2-2) as a polymerization solvent, 50 parts of methyl methacrylate as a monomer, 17 parts of N23, 17 parts of N45, Viscosity index improver (B-5), which is a copolymer, was prepared in the same manner as in Production Example 11 except that 12 parts of HMA, 4 parts of OMA, and 130 parts of monomer diluent (A2-2) were changed. ) Solution (A2-2) was obtained.
- Production of viscosity index improver (B-6) 33 parts of tetraethylene glycol di-n-hexanoate (A2-3) as a polymerization solvent, 99.7 parts of methyl methacrylate as a monomer, 0.1 part of N23, N45
- the copolymer was prepared in the same manner as in Production Example 11 except that 0.1 part of HMA, 0.08 part of HMA, 0.02 part of OMA, and 45 parts of (A2-3) were used as the monomer diluent.
- a solution (A2-3) of the viscosity index improver (B-6) was obtained.
- the viscosity index improver obtained had a weight average molecular weight of 155,000.
- Production of viscosity index improver (B-7) 33 parts neopentylglycol di-n-pentanoate (A1-4) as polymerization solvent, 75.5 parts methyl methacrylate as monomer, 0.1 part N23, N45 Was changed to 8.4 parts, HMA 12 parts, OMA 4 parts, and (A1-4) 45 parts as the monomer diluent, and the viscosity index of the copolymer was changed to Production Example 11. A solution (A1-4) of the improver (B-7) was obtained.
- the viscosity index improver obtained had a weight average molecular weight of 32,000.
- Production Example 18 Production of viscosity index improver (B-8) 20 parts of tripropylene glycol di-n-dodecanoate (A2-4) as a polymerization solvent, 50 parts of methyl methacrylate as a monomer, 17 parts of N23, 17 parts of N45, Viscosity index improver (B-8), which is a copolymer, was prepared in the same manner as in Production Example 11 except that 12 parts of HMA, 4 parts of OMA, and 130 parts of (A2-4) were used as the monomer diluent. ) Solution (A2-4) was obtained.
- the resulting viscosity index improver had a weight average molecular weight of 391,000.
- the viscosity index improver obtained had a weight average molecular weight of 30 million.
- Example 1 Production of Lubricating Oil Composition (K-1) 4 parts of viscosity index improver solution (BA-1) was dissolved in 96 parts of diester (A1-1) to obtain lubricating oil composition (K-1).
- Example 2 Production of Lubricating Oil Composition (K-2) 3.6 parts of viscosity index improver solution (BA-1) was dissolved in 96.4 parts of diester (A1-2) to obtain lubricating oil composition (K-2). Got.
- Example 4 Production of Lubricating Oil Composition (K-4) 2.5 parts of viscosity index improver solution (BA-3) was dissolved in 97.5 parts of diester (A2-1) to obtain lubricating oil composition (K-4). Got.
- Example 5 Production of Lubricating Oil Composition (K-5) 3.5 parts of viscosity index improver solution (BA-4) was dissolved in 96.5 parts of diester (A2-1) to obtain lubricating oil composition (K-5). Got.
- Example 6 Production of Lubricating Oil Composition (K-6) 2.5 parts of viscosity index improver solution (BA-5) was dissolved in 97.5 parts of diester (A2-2) to obtain lubricating oil composition (K-6). Got.
- Example 7 Production of Lubricating Oil Composition (K-7) 3.4 parts of viscosity index improver solution (BA-6) was dissolved in 96.6 parts of diester (A2-3) to obtain lubricating oil composition (K-7). Got.
- Example 8 Production of Lubricating Oil Composition (K-8) 7.7 parts of viscosity index improver solution (BA-7) were dissolved in 92.3 parts of diester (A1-4) to obtain lubricating oil composition (K-8). Got.
- Example 9 Production of Lubricating Oil Composition (K-9) 4.5 parts of viscosity index improver solution (BA-8) was dissolved in 95.5 parts of diester (A2-4) to obtain lubricating oil composition (K-9). Got.
- Example 10 Production of Lubricating Oil Composition (K-10) 2.5 parts of viscosity index improver solution (BA-9) was dissolved in 97.5 parts of diester (A2-1) to obtain lubricating oil composition (K-10). Got.
- Example 12 Manufacture of lubricating oil composition (K-12) 2.6 parts of viscosity index improver solution (BA-3) and 0.1 part of antiwear agent (trixylenyl phosphite) (C-1) are diester (A2-1) Dissolved in 97.4 parts to obtain a lubricating oil composition (K-12).
- Example 13 Production of Lubricating Oil Composition (K-13) 4.0 parts of viscosity index improver solution (BA-1) was dissolved in 96.0 parts of diester (A3-1) to obtain lubricating oil composition (K-13). Got.
- Example 14 Production of Lubricating Oil Composition (K-14) 7.0 parts of viscosity index improver solution (BA-1) was dissolved in 93.0 parts of diester (A3-1) to obtain lubricating oil composition (K-14). Got.
- Example 15 Production of Lubricating Oil Composition (K-15) 2.3 parts of viscosity index improver solution (BA-10) was dissolved in 97.7 parts of diester (A3-2) to obtain lubricating oil composition (K-15). Got.
- Comparative production example 1 Production of other lubricating base oil (D-3)
- a reaction vessel equipped with a stirrer, thermometer, nitrogen inlet tube, and moisture fractionator with cooling tube 533.0 parts of 2-ethylhexanol, azelaic acid 366.9 parts and 46 parts of xylene were charged, and the temperature was raised to 200 ° C. in a nitrogen atmosphere.
- the esterification reaction was carried out for about 5 hours while removing the produced water distilled off with the water fraction receiver with the theoretical amount of produced water (70 g) as the target. Excess alcohol and xylene were removed by distillation to obtain an esterified crude.
- the middle distillate was collected by removing 15% by volume of the first fraction and the latter fraction by vacuum distillation.
- the middle distillate was another lubricating base oil (D-3): di-2-ethylhexyl azelate (molecular weight: 413), and the total acid value of (D-3) was 0.01 mgKOH / g.
- Comparative production example 2 Production of comparative diester (A2-5 ′)
- a reaction vessel equipped with a stirrer, thermometer, nitrogen introduction tube, and moisture fractionator with a cooling tube diethylene glycol 343.7 parts, butanoic acid 628.6 parts, xylene 49 parts were charged and the temperature was raised to 180 ° C. in a nitrogen atmosphere.
- the esterification reaction was carried out for about 15 hours while removing the produced water distilled off with the moisture fraction receiver with the theoretical amount of produced water (117 g) as the target. After completion of the reaction, excess acid and xylene were removed by distillation to obtain an esterified crude product.
- the middle distillate was collected by removing 15% by volume of the first fraction and the latter fraction by vacuum distillation.
- the middle distillate was comparative diester (A2-5 ′): diethylene glycol di-n-butanoate (molecular weight: 247), and the total acid value of (A2-5 ′) was 0.01 mgKOH / g.
- Comparative production example 3 Production of comparative diester (A2-6 ′) In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a moisture fractionator with a cooling tube, 250.8 parts of tripropylene glycol and 655.9 parts of tetradecanoic acid Then, 45 parts of xylene was charged and heated to 220 ° C. in a nitrogen atmosphere. The esterification reaction was carried out for about 15 hours while removing the produced water distilled off with the moisture fraction receiver with the theoretical amount of produced water (47 g) as the target. After completion of the reaction, excess acid and xylene were removed by distillation to obtain an esterified crude product.
- Comparative diester (A2-6 ′): tripropylene glycol di-n-tetradecanoate (molecular weight: 613), (A2- The total acid value of 6 ′) was 0.02 mg KOH / g.
- Comparative Example 1 As a comparative bearing lubricating oil composition (K′-1), azelaic acid di-2-ethylhexyl (D-3) was used.
- Comparative Example 2 8.9 parts of the viscosity index improver solution (BA-11 ′) was dissolved in 91.1 parts of the diester (A2-5 ′) to obtain a comparative lubricating oil composition (K′-2).
- Comparative Example 3 2.0 parts of the viscosity index improver solution (BA-12 ′) was dissolved in 98.0 parts of diester (A2-6 ′) to obtain a comparative lubricating oil composition (K′-3).
- the lubricating oil compositions for bearings (K-1) to (K-15) obtained in Examples 1 to 15 and the lubricating compositions for bearings (K′-1) to (K′ ⁇ ) of Comparative Examples 1 to 4 were used.
- the total acid value was measured according to JIS K 2501 (2003).
- the kinematic viscosity and viscosity index were measured according to JIS K 2283 (2000).
- the bearing lubricating oil composition of the present invention has a high viscosity index, maintains a constant viscosity under a high temperature environment, has a low viscosity under a low temperature environment, and has a small amount of evaporation loss of the lubricating oil even under a high temperature environment.
- the diesters (A) is preferable, and the diester (A2-1) (molecular weight 375) has the same molecular weight (A1-3) (molecular weight 371), (A3-2) (molecular weight 375). It was found that the amount of evaporation loss was small compared to.
- the lubricating oil composition for bearings of the present invention does not need to contain the antiwear agent (C), but rather the evaporation loss increases when the antiwear agent (C) is contained. . This is clear when the evaporation loss amounts of (K-12) and (K-4) obtained by adding (C) to (K-4) are compared.
- the bearing lubricating oil composition of the present invention can be suitably used for fan motors, DC motors, and spindle motors such as magnetic disk devices, optical disk devices, magneto-optical disk devices, and polygon mirror driving devices.
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Abstract
Description
また、特許文献2~5に記載の従来の粘度指数向上剤を含有するエステル系潤滑油を使用した場合は、潤滑油が高粘度であるため機器の摩擦損失が高く、ポリ-α-オレフィンや鉱物油を潤滑油基油として含有する特許文献6,7に記載の潤滑油を使用した場合は、粘度指数向上効果が低く、さらに高温環境下では、ポリ-α-オレフィンや鉱物油の含有する低分子成分が揮発しやすいため、潤滑油の蒸発損失量が多くなるという問題があった。また、耐磨耗剤を含有する特許文献8に記載の潤滑油を使用した場合は、高温環境下で耐磨耗剤の分解物に由来する蒸発損失が発生するという問題があった。
[ジエステル]
本発明におけるジエステル(A)は、下記一般式(1)で表されるジエステル(A1)、下記一般式(2)で表されるジエステル(A2)、及び下記一般式(3)で表されるジエステル(A3)からなる群より選ばれる少なくとも1種である。
ジエステル(A2)は、一般式(2)において、R3~R4が同一または相異なる炭素数4~10のアルキル基であり、A1がエチレン基及び/又はプロピレン基であり、nが2~6である場合が好ましい。
ポリ(メタ)アクリレート系粘度指数向上剤(B)は、炭素数1~4のアルキル基を有する(メタ)アクリル酸アルキルエステルおよび炭素数1~4のヒドロキシアルキル基を有する(メタ)アクリル酸エステルからなる群から選ばれる1種以上の(メタ)アクリル酸エステル(b1)、炭素数11~15のアルキル基を有する(メタ)アクリル酸アルキルエステル(b2)、並びに炭素数16~24のアルキル基を有する(メタ)アクリル酸アルキルエステル(b3)を必須構成単量体とする共重合体が好ましい。
(B)の必須構成単量体(b1)~(b3)について以下に説明する。
(b2)のうち、好ましくは炭素数12~15の直鎖状または分岐鎖状アルキル基を有する(メタ)アクリル酸アルキルエステルである。
(b3)のうちで好ましいのは低温特性の観点から、炭素数16~18の直鎖状アルキル基を有する(メタ)アクリル酸アルキルエステルおよび炭素数24の分岐状アルキル基を有する(メタ)アクリル酸アルキルエステルである。
(b2)の割合は、粘度指数と溶解性の観点から、好ましくは0.01~39.9%、さらに好ましくは0.01~35%である。
(b3)の割合は、粘度指数と低温粘度の観点から、好ましくは0.01~60%、さらに好ましくは0.01~50%である。
例えば、ヒドロキシル基含有芳香族ビニル単量体[p-ヒドロキシスチレンなど]、モノ-またはジ-ヒドロキシアルキル(炭素数1~4)置換(メタ)アクリルアミド[N,N-ジヒドロキシメチル(メタ)アクリルアミド、N,N-ジヒドロキシプロピル(メタ)アクリルアミド、N,N-ジ-2-ヒドロキシブチル(メタ)アクリルアミドなど]、ビニルアルコール(酢酸ビニル単位の加水分解により形成される)、炭素数3~12のアルケノール[(メタ)アリルアルコール、クロチルアルコール、イソクロチルアルコール、1-オクテノール、1-ウンデセノールなど]、炭素数4~12のアルケンジオール[1-ブテン-3-オール、2-ブテン-1-オール、2-ブテン-1,4-ジオールなど]、ヒドロキシアルキル(炭素数1~6)アルケニル(炭素数3~10)エーテル[2-ヒドロキシエチルプロペニルエーテルなど]、多価(3~8価)アルコール(アルカンポリオール、その分子内もしくは分子間脱水物、糖類、例えばグリセリン、ペンタエリスリトール、ソルビトール、ソルビタン、ジグリセリン、蔗糖)のアルケニル(炭素数3~10)エーテルまたは(メタ)アクリレートなど[蔗糖(メタ)アリルエーテル]などが挙げられる。
(b21’)1~3級アミノ基含有ビニル単量体:
1級アミノ基含有ビニル単量体、例えば、炭素数3~6のアルケニルアミン[(メタ)アリルアミン、クロチルアミンなど]、アミノアルキル(炭素数2~6)(メタ)アクリレート[アミノエチル(メタ)アクリレートなど]、2級アミノ基含有ビニル単量体、例えば、アルキル(炭素数1~6)アミノアルキル(炭素数2~6)(メタ)アクリレート[t-ブチルアミノエチルメタクリレート、メチルアミノエチル(メタ)アクリレートなど]、ジフェニルアミン(メタ)アクリルアミド[4-ジフェニルアミン(メタ)アクリルアミド、2-ジフェニルアミン(メタ)アクリルアミドなど]、炭素数6~12のジアルケニルアミン[ジ(メタ)アリルアミンなど]、3級アミノ基含有ビニル単量体、例えば、ジアルキル(炭素数1~4)アミノアルキル(炭素数2~6)(メタ)アクリレート[ジメチルアミノエチル(メタ)アクリレート、ジエチルアミノエチル(メタ)アクリレートなど、ジアルキル(炭素数1~4)アミノアルキル(炭素数2~6)(メタ)アクリルアミド[ジメチルアミノエチル(メタ)アクリルアミド、ジエチルアミノエチル(メタ)アクリルアミド、ジメチルアミノプロピル(メタ)アクリルアミドなど]、3級アミノ基含有芳香族ビニル系単量体[N,N-ジメチルアミノスチレン、など]、含窒素複素環含有ビニル系単量体[モルホリノエチル(メタ)アクリレート、4-ビニルピリジン、2-ビニルピリジン、N-ビニルピロール、N-ビニルピロリドン、N-ビニルチオピロリドンなど]などが挙げられる。
例えば、前述の3級アミノ基含有ビニル単量体を、4級化剤(炭素数1~12のアルキルクロライド、ジアルキル硫酸、ジアルキルカーボネート、およびベンジルクロライド等)を用いて4級化したものなどが挙げられる。
(b23’)ニトリル基含有ビニル単量体
(メタ)アクリロニトリルなどが挙げられる。
(b31’)脂肪族炭化水素系ビニル単量体
例えば、炭素数2~20のアルケン[エチレン、プロピレン、ブテン、イソブチレン、ペンテン、ヘプテン、ジイソブチレン、オクテン、ドデセン、オクタデセンなど]、および炭素数4~12のアルカジエン[ブタジエン、イソプレン、1,4-ペンタジエン、1,6ヘプタジエン、1,7-オクタジエンなど]などが挙げられる。
(b32’)脂環式炭化水素系ビニル単量体:
例えば、シクロヘキセン、(ジ)シクロペンタジエン、ピネン、リモネン、インデン、ビニルシクロヘキセン、およびエチリデンビシクロヘプテンなどが挙げられる。
(b33’)芳香族炭化水素系ビニル単量体:
例えば、スチレン、α-メチルスチレン、ビニルトルエン、2,4-ジメチルスチレン、4-エチルスチレン、4-イソプロピルスチレン、4-ブチルスチレン、4-フェニルスチレン、4-シクロヘキシルスチレン、4-ベンジルスチレン、4-クロチルベンゼン、および2-ビニルナフタレンなどが挙げられる。
例えば、炭素数2~12の飽和脂肪酸のビニルエステル[酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、オクタン酸ビニルなど]、炭素数1~12のアルキル、アリールもしくはアルコキシアルキルのビニルエーテル[メチルビニルエーテル、エチルビニルエーテル、プロピルビニルエーテル、ブチルビニルエーテル、2-エチルヘキシルビニルエーテル、フェニルビニルエーテル、ビニル2-メトキシエチルエーテル、ビニル2-ブトキシエチルエーテルなど]、および炭素数1~8のアルキルもしくはアリールのビニルケトン[メチルビニルケトン、エチルビニルケトン、フェニルビニルケトンなど]などが挙げられる。
例えば、グリシジル(メタ)アクリレート、グリシジル(メタ)アリルエーテルなどが挙げられる。
例えば、塩化ビニル、臭化ビニル、塩化ビニリデン、塩化(メタ)アリル、ハロゲン化スチレン(ジクロルスチレンなど)などが挙げられる。
例えば、不飽和ポリカルボン酸のアルキル、シクロアルキルもしくはアラルキルエステルが挙げられ、このうち不飽和ジカルボン酸[マレイン酸、フマル酸、イタコン酸など]の炭素数1~8のアルキルジエステル[ジメチルマレエート、ジメチルフマレート、ジエチルマレエート、ジオクチルマレエート]などが挙げられる。
例えば、ポリオキシアルキレングリコール(アルキレン基の炭素数2~4、重合度2~50)もしくはポリオキシアルキレンポリオール[上記3~8価のアルコールのポリオキシアルキレンエーテル(アルキル基の炭素数2~4、重合度2~100)]、またはそれらのアルキル(炭素数1~4)エーテルのモノ(メタ)アクリレート[ポリエチレングリコール(分子量100~300)モノ(メタ)アクリレート、ポリプロピレングリコール(分子量130~500)モノ(メタ)アクリレート、メトキシポリエチレングリコール(分子量110~310)(メタ)アクリレート、ラウリルアルコールエチレンオキシド付加物(2~30モル)(メタ)アクリレート、モノ(メタ)アクリル酸ポリオキシエチレン(分子量150~230)ソルビタン]などが挙げられる。
モノカルボキシル基含有ビニル単量体、例えば、不飽和モノカルボン酸[(メタ)アクリル酸、α-メチル(メタ)アクリル酸、クロトン酸、桂皮酸など]、不飽和ジカルボン酸のモノアルキル(炭素数1~8)エステル[マレイン酸モノアルキルエステル、フマル酸モノアルキルエステル、イタコン酸モノアルキルエステルなど];2個以上のカルボキシル基を含有するビニル単量体、例えば、マレイン酸、フマル酸、イタコン酸、シトラコン酸などが挙げられる。
溶解性パラメーターは、Fedorsによる方法「Polym.Eng.Sci.14(2)152,(1974)」によって、使用した単量体の構造とそのモル比から計算できる。
重合時の温度、単量体濃度(溶媒濃度)、触媒量、連鎖移動剤量などにより(B)の重量平均分子量を調整できる。
0.2≦|(α)-(β)|≦1.6 (1)
(K)の重量に基づいて(A)と(B)の合計重量の割合が81重量%未満であると粘度指数向上効果が低下する。
他の成分としては、上記の他の潤滑油基油(D)、下記の添加剤(E)等が挙げられる。
100℃における動粘度は、液漏れや焼き付き防止の観点から、好ましくは2.0mm2/s以上、さらに好ましくは2.5mm2/s以上であり、摩擦損失低減の観点から好ましくは5.8mm2/s以下、さらに好ましくは5.5mm2/s以下である。
40℃における動粘度は、摩擦損失低減の観点から好ましくは4~20mm2/s、さらに好ましくは4~15mm2/sである。
0℃における動粘度は、低温環境下での摩擦損失低減の観点から好ましくは10~85mm2/s、さらに好ましくは10~70mm2/sであり、-20℃における動粘度は、好ましくは10~250mm2/s、さらに好ましくは10~220mm2/sである。
(K)の粘度指数は、好ましくは160~550、さらに好ましくは180~550である。
(K)の動粘度比(100℃動粘度/-20℃動粘度)は、好ましくは5~55、さらに好ましくは5~50である。
粘度指数向上剤としては、ポリ(メタ)アクリレート系粘度指数向上剤(B)以外にオレフィンコポリマー系(溶解性パラメーター:約8.2)やポリイソブチレン系(溶解性パラメーター:約7.6)等が知られているが、溶解性パラメーターが低いため、ジエステル(A)との溶解性が悪く、粘度指数向上効果が低い。
ジエステル(A1-1)の製造
撹拌装置、温度計、窒素導入管、および冷却管付き水分分留受器を備えた反応容器に、ネオペンチルグリコール255.0部、ヘプタン酸701.3部、キシレン48部を仕込み、窒素雰囲気下、200℃まで昇温した。理論生成水量(88g)を目処にして留出してくる生成水を水分分留受器で除去しながらエステル化反応を約10時間行った。反応終了後、過剰の酸およびキシレンを蒸留により除去してエステル化粗物を得た。次いで、得られたエステル化粗物をヴィグリュー分留管を備えたナス型フラスコに移し、減圧下、220℃で蒸留を行った。減圧蒸留により初留分、後留分を各15体積%除き、中留を採取した。中留はジエステル(A1-1):ネオペンチルグリコールジn-ヘプタノエート(分子量328)であり、(A1-1)の全酸価は0.01mgKOH/gであった。
ジエステル(A1-2)の製造
仕込みを3-メチル-1,5-ペンタンジオール277.5部、ヘプタン酸672.6部、キシレン48部に変更した以外は、製造例1と同様に行い、ジエステル(A1-2):3-メチル-1,5-ペンタンジオールジn-ヘプタノエート(分子量342)を得た。(A1-2)の全酸価は0.01mgKOH/gであった。
ジエステル(A1-3)の製造
仕込みを3-メチル-1,5-ペンタンジオール255.1部、オクタン酸684.9部、トルエン47部に変更した以外は、製造例1と同様に行い、ジエステル(A1-3):3-メチル-1,5-ペンタンジオールジn-オクタノエート(分子量371)を得た。(A1-3)の全酸価は0.01mgKOH/gであった。
ジエステル(A1-4)の製造
仕込みをネオペンチルグリコール305.9部、ペンタン酸659.9部、キシレン48部に変更し、蒸留を減圧下、200℃で行った以外は、製造例1と同様に行い、ジエステル(A1-4):ネオペンチルグリコールジn-ペンタノエート(分子量272)を得た。(A1-4)の全酸価は0.01mgKOH/gであった。
ジエステル(A2-1)の製造
仕込みをトリエチレングリコール322.5部、ヘプタン酸615.1部、キシレン47部に変更した以外は、製造例1と同様に行い、ジエステル(A2-1):トリエチレングリコールジn-ヘプタノエート(分子量375)を得た。(A2-1)の全酸価は0.01mgKOH/gであった。
ジエステル(A2-2)の製造
仕込みをジプロピレングリコール279.2部、オクタン酸600.1部、キシレン47部に変更した以外は、製造例1と同様に行い、ジエステル(A2-2):ジプロピレングリコールジn-オクタノエート(分子量387)を得た。(A2-2)の全酸価は0.01mgKOH/gであった。
ジエステル(A2-3)の製造
仕込みをテトラエチレングリコール398.0部、ヘキサン酸523.5部、キシレン46部に変更した以外は、製造例1と同様に行い、ジエステル(A2-3):テトラエチレングリコールジn-ヘキサノエート(分子量391)を得た。(A2-3)の全酸価は0.01mgKOH/gであった。
ジエステル(A2-4)の製造
撹拌装置、温度計、窒素導入管、および冷却管付き水分分留受器を備えた反応容器に、トリプロピレングリコール276.7部、ドデカン酸633.0部、キシレン45部を仕込み、窒素雰囲気下、220℃まで昇温した。理論生成水量(52g)を目処にして留出してくる生成水を水分分留受器で除去しながらエステル化反応を約15時間行った。反応終了後、過剰の酸およびキシレンを蒸留により除去してエステル化粗物を得た。次いで、得られたエステル化粗物の全酸価に対して過剰の水酸化ナトリウム水溶液で中和し、中性になるまで水洗を行った後、活性炭処理を行った。次いで、濾過により活性炭を取り除き、エステル化粗物中の水分を蒸留により除去しジエステル(A2-4):トリプロピレングリコールジn-ドデカノエート(分子量:557)であり、(A2-4)の全酸価は0.02mgKOH/gであった。
ジエステル(A3-1)の製造
撹拌装置、温度計、窒素導入管、および冷却管付き水分分留受器を備えた反応容器に、n-ブタノール431.1部、チオジプロピオン酸493.6部、キシレン46部を仕込み、窒素雰囲気下、180℃まで昇温した。理論生成水量(100g)を目処にして留出してくる生成水を水分分留受器で除去しながらエステル化反応を約12時間行った。反応終了後、過剰のアルコールおよびキシレンを蒸留により除去してエステル化粗物を得た。次いで、得られたエステル化粗物をヴィグリュー分留管を備えたナス型フラスコに移し、減圧下、200℃で蒸留を行った。減圧蒸留により初留分、後留分を各15体積%除き、中留を採取した。中留はジエステル(A3-1):チオジプロピオン酸ジn-ブチル(分子量290)であり、(A3-1)の全酸価は0.01mgKOH/gであった。
ジエステル(A3-2)の製造
仕込みを2-ヘプタノール546.0部、チオジプロピオン酸380.7部、キシレン46部に変更した以外は、製造例9と同様に行い、ジエステル(A3-2):チオジプロピオン酸ジ2-ヘプチル(分子量375)を得た。(A3-2)の全酸価は0.01mgKOH/gであった。
粘度指数向上剤(B-1)の製造
撹拌装置、加熱冷却装置、温度計、窒素導入管、および滴下ロートを備えた反応容器に、重合溶剤としてセバシン酸ジ-2エチルヘキシル(商品名「サンソサイザー DOS」、新日本理化(株)社製) (D-1)20部を仕込み、ガラス製ビーカーに、単量体としてメタクリル酸メチルを50部、N23を17部、N45を17部、HMAを12部、OMAを4部、単量体の希釈剤として(D-1)130部、重合触媒として2,2’-アゾビス(2,4-ジメチルバレロニトリル)0.04部、および2,2’-アゾビス(2-メチルブチロニトリル)0.18部を仕込み、20℃で撹拌、混合して単量体-重合触媒の希釈剤溶液を調整し、滴下ロートに仕込んだ。反応容器の気相部の窒素置換を行い、気相酸素濃度を500~1,000ppmとした。密閉下に、75℃にて2時間かけて単量体-重合触媒の希釈剤溶液を滴下し、滴下終了から4時間、同温度で熟成した後、130℃、減圧度4kPa以下で2時間かけて低沸点成分を留去し、共重合体である粘度指数向上剤(B-1)の(D-1)溶液を得た。得られた粘度指数向上剤(B-1)の濃度が20重量%となるように(D-1)を250部加え、粘度指数向上剤(B-1)の(D-1)溶液(BA-1)を得た。得られた粘度指数向上剤の重量平均分子量は38.4万であった。
粘度指数向上剤(B-2)の製造
重合溶剤として3-メチル-1,5-ペンタンジオール(A1-3)20部、単量体としてメタクリル酸メチルを50部、N23を17部、N45を17部、HMAを12部、OMAを4部、単量体の希釈剤として(A1-3)130部に変更した以外は製造例11と同様に行い、共重合体である粘度指数向上剤(B-2)の(A1-3)溶液を得た。得られた粘度指数向上剤(B-2)の濃度が20重量%となるように(A1-3)を250部加え、粘度指数向上剤(B-2)の(A1-3)溶液(BA-2)を得た。得られた粘度指数向上剤の重量平均分子量は38.1万であった。
粘度指数向上剤(B-3)の製造
重合溶剤としてトリエチレングリコールジn-ヘプタノエート(A2-1)33部、単量体としてメタクリル酸メチルを75.5部、N23を0.1部、N45を8.4部、HMAを12部、OMAを4部、単量体の希釈剤として(A2-1)45部に変更した以外は製造例11と同様に行い、共重合体である粘度指数向上剤(B-3)の(A2-1)溶液を得た。得られた粘度指数向上剤(B-3)の濃度が20重量%となるように(A2-1)を322部加え、粘度指数向上剤(B-3)の(A2-1)溶液(BA-3)を得た。得られた粘度指数向上剤の重量平均分子量は30.7万であった。
粘度指数向上剤(B-4)の製造
重合溶剤としてトリエチレングリコールジn-ヘプタノエート(A2-1)33部、単量体としてメタクリル酸メチルを94部、N23を0.1部、N45を0.5部、HMAを4.1部、OMAを1.4部、単量体の希釈剤として(A2-1)45部に変更した以外は製造例11と同様に行い、共重合体である粘度指数向上剤(B-4)の(A2-1)溶液を得た。得られた粘度指数向上剤(B-4)の濃度が20重量%となるように(A2-1)を322部加え、粘度指数向上剤(B-4)の(A2-1)溶液(BA-4)を得た。得られた粘度指数向上剤の重量平均分子量は29.2万であった。
粘度指数向上剤(B-5)の製造
重合溶剤としてジプロピレングリコールジn-オクタノエート(A2-2)20部、単量体としてメタクリル酸メチルを50部、N23を17部、N45を17部、HMAを12部、OMAを4部、単量体の希釈剤として(A2-2)130部に変更した以外は製造例11と同様に行い、共重合体である粘度指数向上剤(B-5)の(A2-2)溶液を得た。得られた粘度指数向上剤(B-5)の濃度が20重量%となるように(A2-2)を250部加え、粘度指数向上剤(B-5)の(A2-2)溶液(BA-5)を得た。得られた粘度指数向上剤の重量平均分子量は38.0万であった。
粘度指数向上剤(B-6)の製造
重合溶剤としてテトラエチレングリコールジn-ヘキサノエート(A2-3)33部、単量体としてメタクリル酸メチルを99.7部、N23を0.1部、N45を0.1部、HMAを0.08部、OMAを0.02部、単量体の希釈剤として(A2-3)45部に変更した以外は製造例11と同様に行い、共重合体である粘度指数向上剤(B-6)の(A2-3)溶液を得た。得られた粘度指数向上剤(B-6)の濃度が20重量%となるように(A2-3)を322部加え、粘度指数向上剤(B-6)の(A2-3)溶液(BA-6)を得た。得られた粘度指数向上剤の重量平均分子量は15.5万であった。
粘度指数向上剤(B-7)の製造
重合溶剤としてネオペンチルグリコールジn-ペンタノエート(A1-4)33部、単量体としてメタクリル酸メチルを75.5部、N23を0.1部、N45を8.4部、HMAを12部、OMAを4部、単量体の希釈剤として(A1-4)45部に変更した以外は製造例11と同様に行い、共重合体である粘度指数向上剤(B-7)の(A1-4)溶液を得た。得られた粘度指数向上剤(B-7)の濃度が20重量%となるように(A1-4)を322部加え、粘度指数向上剤(B-7)の(A1-4)溶液(BA-7)を得た。得られた粘度指数向上剤の重量平均分子量は32.0万であった。
粘度指数向上剤(B-8)の製造
重合溶剤としてトリプロピレングリコールジn-ドデカノエート(A2-4)20部、単量体としてメタクリル酸メチルを50部、N23を17部、N45を17部、HMAを12部、OMAを4部、単量体の希釈剤として(A2-4)130部に変更した以外は製造例11と同様に行い、共重合体である粘度指数向上剤(B-8)の(A2-4)溶液を得た。得られた粘度指数向上剤(B-8)の濃度が20重量%となるように(A2-4)を250部加え、粘度指数向上剤(B-8)の(A2-4)溶液(BA-8)を得た。得られた粘度指数向上剤の重量平均分子量は39.1万であった。
粘度指数向上剤(B-9)の製造
重合溶剤としてアジピン酸ジ-2エチルヘキシル(東京化成工業(株)社製)(D-2)33部、単量体としてメタクリル酸メチルを75.5部、N23を0.1部、N45を8.4部、HMAを12部、OMAを4部、単量体の希釈剤として(D-2)45部に変更した以外は製造例11と同様に行い、共重合体である粘度指数向上剤(B-9)の(D-2)溶液を得た。得られた粘度指数向上剤(B-9)の濃度が20重量%となるように(D-2)を322部加え、粘度指数向上剤(B-8)の(D-2)溶液(BA-9)を得た。得られた粘度指数向上剤の重量平均分子量は31.4万であった。
粘度指数向上剤(B-10)の製造
重合溶剤としてチオジプロピオン酸ジ2-ヘプチル(A3-2)33部を仕込み、ガラス製ビーカーに、単量体としてメタクリル酸メチルを75.5部、N23を0.1部、N45を8.4部、HMAを12部、OMAを4部、単量体の希釈剤として(A3-2)45部に変更した以外は製造例11と同様に行い、共重合体である粘度指数向上剤(B-10)の(A3-2)溶液を得た。得られた粘度指数向上剤(B-10)の濃度が20重量%となるように(A3-2)を322部加え、粘度指数向上剤(B-10)の(A3-2)溶液(BA-10)を得た。得られた粘度指数向上剤の重量平均分子量は30.0万であった。
潤滑油組成物(K-1)の製造
粘度指数向上剤の溶液(BA-1)4部をジエステル(A1-1)96部に溶解し、潤滑油組成物(K-1)を得た。
潤滑油組成物(K-2)の製造
粘度指数向上剤の溶液(BA-1)3.6部をジエステル(A1-2)96.4部に溶解し、潤滑油組成物(K-2)を得た。
潤滑油組成物(K-3)の製造
粘度指数向上剤の溶液(BA-2)3.1部をジエステル(A1-3)96.9部に溶解し、潤滑油組成物(K-3)を得た。
潤滑油組成物(K-4)の製造
粘度指数向上剤の溶液(BA-3)2.5部をジエステル(A2-1)97.5部に溶解し、潤滑油組成物(K-4)を得た。
潤滑油組成物(K-5)の製造
粘度指数向上剤の溶液(BA-4)3.5部をジエステル(A2-1)96.5部に溶解し、潤滑油組成物(K-5)を得た。
潤滑油組成物(K-6)の製造
粘度指数向上剤の溶液(BA-5)2.5部をジエステル(A2-2)97.5部に溶解し、潤滑油組成物(K-6)を得た。
潤滑油組成物(K-7)の製造
粘度指数向上剤の溶液(BA-6)3.4部をジエステル(A2-3)96.6部に溶解し、潤滑油組成物(K-7)を得た。
潤滑油組成物(K-8)の製造
粘度指数向上剤の溶液(BA-7)7.7部をジエステル(A1-4)92.3部に溶解し、潤滑油組成物(K-8)を得た。
潤滑油組成物(K-9)の製造
粘度指数向上剤の溶液(BA-8)4.5部をジエステル(A2-4)95.5部に溶解し、潤滑油組成物(K-9)を得た。
潤滑油組成物(K-10)の製造
粘度指数向上剤の溶液(BA-9)2.5部をジエステル(A2-1)97.5部に溶解し、潤滑油組成物(K-10)を得た。
潤滑油組成物(K-11)の製造
粘度指数向上剤の溶液(BA-1)2.5部をジエステル(A2-2)97.5部に溶解し、潤滑油組成物(K-11)を得た。
潤滑油組成物(K-12)の製造
粘度指数向上剤の溶液(BA-3)2.6部、および耐磨耗剤(トリキシレニルフォスファイト)(C-1)0.1部をジエステル(A2-1)97.4部に溶解し、潤滑油組成物(K-12)を得た。
潤滑油組成物(K-13)の製造
粘度指数向上剤の溶液(BA-1)4.0部をジエステル(A3-1)96.0部に溶解し、潤滑油組成物(K-13)を得た。
潤滑油組成物(K-14)の製造
粘度指数向上剤の溶液(BA-1)7.0部をジエステル(A3-1)93.0部に溶解し、潤滑油組成物(K-14)を得た。
潤滑油組成物(K-15)の製造
粘度指数向上剤の溶液(BA-10)2.3部をジエステル(A3-2)97.7部に溶解し、潤滑油組成物(K-15)を得た。
他の潤滑油基油(D-3)の製造
撹拌装置、温度計、窒素導入管、および冷却管付き水分分留受器を備えた反応容器に、2-エチルヘキサノール533.0部、アゼライン酸366.9部、キシレン46部を仕込み、窒素雰囲気下、200℃まで昇温した。理論生成水量(70g)を目処にして留出してくる生成水を水分分留受器で除去しながらエステル化反応を約5時間行った。過剰のアルコールおよびキシレンを蒸留により除去してエステル化粗物を得た。次いで、得られたエステル化粗物をヴィグリュー分留管を備えたナス型フラスコに移し、減圧下、220℃で蒸留を行った。減圧蒸留により初留分、後留分を各15体積%除き、中留を採取した。中留は他の潤滑油基油(D-3):アゼライン酸ジ2-エチルヘキシル(分子量:413)であり、(D-3)の全酸価は0.01mgKOH/gであった。
比較ジエステル(A2-5’)の製造
撹拌装置、温度計、窒素導入管、および冷却管付き水分分留受器を備えた反応容器に、ジエチレングリコール343.7部、ブタン酸628.6部、キシレン49部を仕込み、窒素雰囲気下、180℃まで昇温した。理論生成水量(117g)を目処にして留出してくる生成水を水分分留受器で除去しながらエステル化反応を約15時間行った。反応終了後、過剰の酸およびキシレンを蒸留により除去してエステル化粗物を得た。次いで、得られたエステル化粗物をヴィグリュー分留管を備えたナス型フラスコに移し、減圧下、200℃で蒸留を行った。減圧蒸留により初留分、後留分を各15体積%除き、中留を採取した。中留は比較ジエステル(A2-5’):ジエチレングリコールジn-ブタノエート(分子量:247)であり、(A2-5’)の全酸価は0.01mgKOH/gであった。
比較ジエステル(A2-6’)の製造
撹拌装置、温度計、窒素導入管、および冷却管付き水分分留受器を備えた反応容器に、トリプロピレングリコール250.8部、テトラデカン酸655.9部、キシレン45部を仕込み、窒素雰囲気下、220℃まで昇温した。理論生成水量(47g)を目処にして留出してくる生成水を水分分留受器で除去しながらエステル化反応を約15時間行った。反応終了後、過剰の酸およびキシレンを蒸留により除去してエステル化粗物を得た。次いで、得られたエステル化粗物の全酸価に対して過剰の水酸化ナトリウム水溶液で中和し、中性になるまで水洗を行った後、活性炭処理を行った。次いで、濾過により活性炭を取り除き、エステル化粗物中の水分を蒸留により除去し比較ジエステル(A2-6’):トリプロピレングリコールジn-テトラデカノエート(分子量:613)であり、(A2-6’)の全酸価は0.02mgKOH/gであった。
粘度指数向上剤(B-11’)の製造
重合溶剤としてジエチレングリコールジn-ブタノエート(A2-5’)33部、単量体としてメタクリル酸メチルを94部、N23を0.1部、N45を0.5部、HMAを4.1部、OMAを1.4部、単量体の希釈剤として(A2-5’)45部に変更した以外は製造例11と同様に行い、共重合体である粘度指数向上剤(B-11’)の(A2-5’)溶液を得た。得られた粘度指数向上剤(B-11’)の濃度が20重量%となるように(A2-5’)を322部加え、粘度指数向上剤(B-11’)の(A2-5’)溶液(BA-11’)を得た。得られた粘度指数向上剤の重量平均分子量は29.0万であった。
粘度指数向上剤(B-12’)の製造
重合溶剤としてトリプロピレングリコールジn-テトラデカノエート(A2-6’)20部を仕込み、ガラス製ビーカーに、単量体としてメタクリル酸メチルを50部、N23を17部、N45を17部、HMAを12部、OMAを4部、単量体の希釈剤として(A2-6’)130部に変更した以外は製造例11と同様に行い、共重合体である粘度指数向上剤(B-12’)の(A2-6’)溶液を得た。得られた粘度指数向上剤(BA-12’)の濃度が20重量%となるように(A2-6’)を250部加え、粘度指数向上剤(B-12’)の(A2-6’)溶液(BA-12’)を得た。得られた粘度指数向上剤の重量平均分子量は37.4万であった。
アゼライン酸ジ-2エチルヘキシル(D-3)を比較の軸受用潤滑油組成物(K’-1)とした。
粘度指数向上剤の溶液(BA-11’)8.9部をジエステル(A2-5’)91.1部に溶解し、比較の潤滑油組成物(K’-2)を得た。
粘度指数向上剤の溶液(BA-12’)2.0部をジエステル(A2-6’)98.0部に溶解し、比較の潤滑油組成物(K’-3)を得た。
粘度指数向上剤の溶液(BA-2)2.5部をジエステル(A2-1)77.5部に溶解した後、ポリ-α-オレフィン(エクソンモービルケミカル社製SpectraSyn4)(D-4)を20部加え、比較の潤滑油組成物(K’-4)を得た。
JIS K 2501(2003年)に準じて全酸価を測定した。
GPCにより重量平均分子量を測定した。
装置 : 東洋曹達製 HLC-802A
カラム : TSK gel GMH6 2本
測定温度 : 40℃
試料溶液 : 0.5%のTHF溶液
溶液注入量 : 200μl
検出装置 : 屈折率検出器
標準 : ポリスチレン
JIS K 2283(2000年)に準じて測定した。
潤滑油組成物の重量に基づいて酸化防止剤の含有量が0.2重量%となるよう潤滑油組成物3.0gにIRGANOX 1010(BASFジャパン製)を6mg加え溶解させた試料を容器容量9ml(口内径10.0mm、胴径21.0mm、高さ45mm)のガラス製容器に1000.0mg入れ、160℃に温調した乾燥器に静置し、10時間加熱後の蒸発損失量を測定した。蒸発損失量は下記計算式(2)により算出した。
蒸発損失量(重量%)=((G1-G2)/1000)×100 (2)
G1:1000(mg)+容器重量(mg)
G2:10時間加熱後の試料重量(mg)+容器重量(mg)
したがって、本発明の軸受用潤滑油組成物は粘度指数が高く、かつ高温環境下では一定の粘度を保持し低温環境下では粘度が低く、かつ高温環境下でも潤滑油の蒸発損失量が少ないことがわかった。
ジエステル(A)の中でもジエステル(A2)が好ましく、ジエステル(A2-1)(分子量375)は、同程度の分子量である(A1-3)(分子量371)、(A3-2)(分子量375)に比べて、蒸発損失量が少ないことがわかった。
また、本発明の軸受用潤滑油組成物では耐磨耗剤(C)を含有させる必要もなく、むしろ耐磨耗剤(C)を含有させた場合は蒸発損失量が増加することがわかった。このことは(K-4)に(C)を添加した(K-12)と(K-4)の蒸発損失量を比較すれば明らかである。
Claims (12)
- 下記一般式(1)で表されるジエステル(A1)、下記一般式(2)で表されるジエステル(A2)、及び下記一般式(3)で表されるジエステル(A3)からなる群より選ばれる少なくとも1種であって分子量が250~600であるジエステル(A)、及びポリ(メタ)アクリレート系粘度指数向上剤(B)を含有する軸受用潤滑油組成物であって、軸受用潤滑油組成物の重量に基づいて(A)と(B)の合計重量の割合が81重量%以上である軸受用潤滑油組成物(K)。
- さらに耐磨耗剤(C)を含有する軸受用潤滑油組成物(K)であって、(K)の重量に基づいて(C)の重量の割合が0.09重量%以下である請求項1に記載の組成物(K)。
- 100℃における動粘度が2.0~5.8mm2/sである請求項1または2に記載の組成物(K)。
- ジエステル(A)がジエステル(A2)である請求項1~3のいずれか1項に記載の組成物(K)。
- ジエステル(A2)を表す一般式(2)において、R3~R4が同一または相異なる炭素数4~10のアルキル基であり、A1がエチレン基及び/又はプロピレン基であり、nが2~6である請求項4に記載の組成物(K)。
- ポリ(メタ)アクリレート系粘度指数向上剤(B)が、炭素数1~4のアルキル基を有する(メタ)アクリル酸アルキルエステルおよび炭素数1~4のヒドロキシアルキル基を有する(メタ)アクリル酸エステルからなる群から選ばれる1種以上の(メタ)アクリル酸エステル(b1)、炭素数11~15のアルキル基を有する(メタ)アクリル酸アルキルエステル(b2)、並びに炭素数16~24のアルキル基を有する(メタ)アクリル酸アルキルエステル(b3)を必須構成単量体とする共重合体である請求項1~5のいずれか1項に記載の組成物(K)。
- ポリ(メタ)アクリレート系粘度指数向上剤(B)の(メタ)アクリル酸エステル(b1)、(メタ)アクリル酸アルキルエステル(b2)、及び(メタ)アクリル酸アルキルエステル(b3)の合計重量に基づく(b1)の重量の割合が30~99.9%であり、(b2)の重量の割合が0.01~39.9%であり、(b3)の重量の割合が0.01~60%である請求項6に記載の組成物(K)。
- ポリ(メタ)アクリレート系粘度指数向上剤(B)の重量平均分子量が、5,000~1,000,000である請求項6または7に記載の組成物(K)。
- ポリ(メタ)アクリレート系粘度指数向上剤(B)の溶解性パラメーター(β)が9.0~11である請求項6~8のいずれか1項に記載の組成物(K)。
- ジエステル(A)の溶解性パラメーター(α)とポリ(メタ)アクリレート系粘度指数向上剤(B)の溶解性パラメーター(β)の差が下記関係式(1)を満足する請求項9に記載の組成物(K)。
0.2≦|(α)-(β)|≦1.6 (1) - 軸受用潤滑油組成物(K)の重量に基づく粘度指数向上剤(B)の重量割合が0.1~30重量%である請求項1~10のいずれか1項に記載の組成物(K)。
- 流体軸受用である請求項1~11のいずれか1項に記載の組成物(K)。
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JP2013018973A (ja) * | 2011-06-17 | 2013-01-31 | New Japan Chem Co Ltd | 潤滑油 |
JP2013177554A (ja) * | 2012-02-08 | 2013-09-09 | Sanyo Chem Ind Ltd | 粘度指数向上剤及び潤滑油組成物 |
JP2013203913A (ja) * | 2012-03-29 | 2013-10-07 | Sanyo Chem Ind Ltd | 粘度指数向上剤及び潤滑油組成物 |
WO2014076747A1 (ja) * | 2012-11-13 | 2014-05-22 | 新日本理化株式会社 | 潤滑油 |
JP2015013961A (ja) * | 2013-07-05 | 2015-01-22 | Jx日鉱日石エネルギー株式会社 | ポリ(メタ)アクリレート系粘度指数向上剤、並びに該粘度指数向上剤を含有する潤滑油添加剤及び潤滑油組成物 |
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WO2023133514A1 (en) * | 2022-01-06 | 2023-07-13 | Vantage Santolubes Research, Llc | Diesters of polyethylene oxide as lubricant base oils |
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Cited By (9)
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JP2013018973A (ja) * | 2011-06-17 | 2013-01-31 | New Japan Chem Co Ltd | 潤滑油 |
JP2013177554A (ja) * | 2012-02-08 | 2013-09-09 | Sanyo Chem Ind Ltd | 粘度指数向上剤及び潤滑油組成物 |
JP2013203913A (ja) * | 2012-03-29 | 2013-10-07 | Sanyo Chem Ind Ltd | 粘度指数向上剤及び潤滑油組成物 |
US9783757B2 (en) | 2012-07-24 | 2017-10-10 | Jx Nippon Oil & Energy Corporation | Poly(meth)acrylate-based viscosity index improver, lubricant additive and lubricant composition containing viscosity index improver |
WO2014076747A1 (ja) * | 2012-11-13 | 2014-05-22 | 新日本理化株式会社 | 潤滑油 |
JP2015013961A (ja) * | 2013-07-05 | 2015-01-22 | Jx日鉱日石エネルギー株式会社 | ポリ(メタ)アクリレート系粘度指数向上剤、並びに該粘度指数向上剤を含有する潤滑油添加剤及び潤滑油組成物 |
JP2018080246A (ja) * | 2016-11-15 | 2018-05-24 | コスモ石油ルブリカンツ株式会社 | 潤滑油用基油及び潤滑油 |
EP4274877A4 (en) * | 2021-01-06 | 2024-05-15 | Vantage Santolubes Res Llc | PROCESS FOR PRODUCING BASE OILS WITH LOW SHEAR STRENGTH |
WO2023133514A1 (en) * | 2022-01-06 | 2023-07-13 | Vantage Santolubes Research, Llc | Diesters of polyethylene oxide as lubricant base oils |
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