WO2024004763A1 - Viscosity index improver composition and lubricating oil composition - Google Patents

Viscosity index improver composition and lubricating oil composition Download PDF

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WO2024004763A1
WO2024004763A1 PCT/JP2023/022777 JP2023022777W WO2024004763A1 WO 2024004763 A1 WO2024004763 A1 WO 2024004763A1 JP 2023022777 W JP2023022777 W JP 2023022777W WO 2024004763 A1 WO2024004763 A1 WO 2024004763A1
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meth
viscosity index
group
lubricating oil
carbon atoms
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PCT/JP2023/022777
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French (fr)
Japanese (ja)
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展洋 内藤
真之介 木口
直弘 鳥居
和樹 尾形
義光 杉山
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三洋化成工業株式会社
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Publication of WO2024004763A1 publication Critical patent/WO2024004763A1/en

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/74—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing phosphorus
    • 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
    • C10M129/04—Hydroxy compounds
    • C10M129/06—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10—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
    • C10M145/12—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 monocarboxylic
    • C10M145/14—Acrylate; Methacrylate
    • 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
    • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
    • C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M149/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group

Definitions

  • the present invention relates to a viscosity index improver composition and a lubricating oil composition.
  • Hydraulic oils used as power transmission media in hydraulic equipment include synthetic hydraulic oils, water-containing hydraulic oils, and mineral oil-based hydraulic oils, but when used in environments with high-temperature heat sources, , flame-retardant synthetic hydraulic oil or water-containing hydraulic fluid is used.
  • phosphate ester hydraulic fluid which is a synthetic hydraulic fluid, has excellent fire resistance, lubricity, oxidation stability, and low compressibility, so it has excellent responsiveness to actuators, etc., so it is used in power plants, aircraft, etc. Used in hydraulic systems. In particular, hydraulic fluids used in aircraft need to have good hydrolytic stability and low-temperature fluidity.
  • Patent Document 1 Since it is used in a wide temperature range, it needs to have a low low-temperature viscosity, but it must also maintain a certain level of acceptable viscosity even at high temperatures, and a high viscosity index is required (Patent Document 1). It is known to use a viscosity index improver (Patent Document 2) in order to obtain a high viscosity index, and for example, lubricating oil compositions using polybutyl methacrylate, polyhexyl methacrylate (Patent Document 3), etc. are known. It is being However, the above-mentioned lubricating oil composition has a problem in that the effect of improving the viscosity index is not yet sufficient.
  • phosphate ester hydraulic fluids are highly hydrophilic and easily decompose into acids and alcohols in the presence of moisture, which are known to corrode metals. Substances can also corrode metals.
  • the products generated as a result of deterioration of the hydraulic oil due to moisture cause poor control due to damage to machines and equipment, and cause problems such as further acceleration of deterioration of the hydraulic oil (Patent Document 4).
  • Patent Document 5 it is widely known to use an alicyclic epoxy ester compound as an acid scavenger
  • Non-Patent Document 1 alicyclic epoxy ester-based acid scavengers have the problem of being hydrolyzed themselves (Patent Document 5), and alicyclic epoxy compounds have higher reactivity with acids and cations than epoxy compounds.
  • Non-Patent Document 1 since the alicyclic epoxy ester acid scavenger is used as an epoxy curing agent (Non-Patent Document 1), it is difficult to react with the acid generated by hydrolysis of phosphoric acid ester or alicyclic epoxy ester.
  • the curing reaction does not end with a simple 1:1 reaction and a high molecular weight epoxy resin is produced. This poses a problem in that the viscosity characteristics of the lubricating oil deteriorate and sludge is generated as an insoluble substance, resulting in deterioration in lubricity.
  • An object of the present invention is to obtain a lubricating oil composition that has an excellent effect of improving the viscosity index, an excellent effect of suppressing hydrolysis of phosphate ester, and is free from precipitates even at low temperatures (-60°C) and has a low viscosity at low temperatures. It is an object of the present invention to provide a viscosity index improver composition capable of improving the viscosity index.
  • the present invention provides a viscosity index improver composition for a lubricating oil composition containing a phosphoric acid ester (C), which essentially comprises a monomer (a) represented by the following general formula (1).
  • R 1 is a hydrogen atom or a methyl group
  • -X 1 - is a group represented by -O- or -NH-
  • R 2 is an alkylene group having 2 to 4 carbon atoms
  • R 3 is a straight group having 1 to 17 carbon atoms
  • p is an integer of 0 to 20, and when p is 2 or more, R 2 may be the same or different.
  • the viscosity index improver composition of the present invention has an excellent effect of improving the viscosity index, an excellent effect of suppressing the hydrolysis of phosphate ester, and is free from precipitates even at low temperatures (-60°C), making it a lubricating oil with low viscosity at low temperatures. This has the effect that a composition can be obtained.
  • the viscosity index improver composition of the present invention is a viscosity index improver composition for lubricating oil compositions containing a phosphoric acid ester (C), and includes a monomer ( The (co)polymer (A) containing a) as an essential constituent monomer and a chain aliphatic alcohol (B) having an HLB value of 2.5 to 7.0, This is a viscosity index improver composition in which the solubility parameter of aggregate (A) is 9.00 to 9.80 (cal/cm 3 ) 1/2 .
  • “(co)polymer” means “homopolymer and/or copolymer”.
  • monomer (a) may be used alone or in combination of two or more.
  • (meth)acrylate means acrylate or methacrylate
  • (meth)acrylamide means acrylamide or methacrylamide
  • (meth)acrylic acid means acrylic acid or methacrylic acid.
  • R 1 is a hydrogen atom or a methyl group
  • -X 1 - is a group represented by -O- or -NH-
  • R 2 is an alkylene group having 2 to 4 carbon atoms
  • R 3 is a straight group having 1 to 17 carbon atoms
  • p is an integer of 0 to 20, and when p is 2 or more, R 2 may be the same or different.
  • R 1 is a hydrogen atom or a methyl group, and is preferably a methyl group from the viewpoint of improving the viscosity index.
  • the viscosity index improver composition of the present invention contains a (co)polymer (A) having the monomer (a) represented by the general formula (1) as an essential constituent monomer.
  • -X 1 - is a group represented by -O- or -NH-, and from the viewpoint of improving the viscosity index, it is preferably a group represented by -O-.
  • R 2 is an alkylene group having 2 to 4 carbon atoms, such as an ethylene group, a propylene group, a butylene group, and the like. Among these, from the viewpoint of improving the viscosity index, ethylene groups are preferred.
  • p is an integer of 0 to 20, and when p is 2 or more, R 2 may be the same or different, and from the viewpoint of improving the viscosity index, it is preferably 0 to 4. , more preferably 0 to 2.
  • R 3 is a straight chain or branched alkyl group having 1 to 17 carbon atoms, such as a methyl group, an ethyl group, a straight chain alkyl group ⁇ for example, an n-propyl group, an n-butyl group , n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group , n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, etc. ⁇ , branched alkyl group ⁇ for example, isopropyl group, isobutyl group, sec-butyl group, tert-buty
  • straight chain or branched alkyl groups having 1 to 15 carbon atoms are preferred, and straight chain or branched alkyl groups having 1 to 13 carbon atoms are more preferred.
  • straight chain or branched alkyl groups having 1 to 13 carbon atoms are more preferred.
  • a combination of one having a straight chain or branched alkyl group having 1 to 3 carbon atoms and one having a straight chain or branched alkyl group having 4 to 17 carbon atoms is preferred, and more preferably.
  • an alkyl (meth)acrylate having a straight chain or branched alkyl group having 1 to 17 carbon atoms [for example, an alkyl (meth)acrylate (a1) having a straight chain or branched alkyl group having 1 to 3 carbon atoms ⁇ for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, etc. ⁇ , alkyl (meth)acrylate (a2) having a straight chain or branched alkyl group having 4 to 17 carbon atoms ⁇
  • N-alkyl (meth)acrylamide having a straight chain or branched alkyl group having 1 to 17 carbon atoms ⁇ for example, methyl (meth)acrylamide, ethyl (meth)acrylamide, n-propyl (meth)acrylamide, n-butyl ( meth)acrylamide, n-pentyl(meth)acrylamide, n-hexyl(meth)acrylamide, n-heptyl(meth)acrylamide, n-octyl(meth)acrylamide, n-nonyl(meth)acrylamide, n-decyl(meth)acrylamide ) acrylamide, n-undecyl (meth)acrylamide, n-dodecyl (meth)acrylamide, n-tridecyl (meth)acrylamide, n-tetradecyl (meth)acrylamide, n-p
  • the monomer (a) is preferably one in which -X 1 - in general formula (1) is -O-, and more preferably a linear or branched alkyl having 1 to 17 carbon atoms.
  • alkyl (meth)acrylate having a chain or branched alkyl group and particularly preferably a combination of an alkyl (meth)acrylate (a1) having a straight chain or branched alkyl group having 1 to 3 carbon atoms and an alkyl (meth)acrylate having 6 to 13 carbon atoms. It is a combination with an alkyl (meth)acrylate having a straight chain or branched alkyl group.
  • Neodol (registered trademark) 23 mixture of linear and branched alkyl alcohols having 12 to 13 carbon atoms, manufactured by SHELL
  • Neodol (registered trademark) 45 straight chain and branched alkyl alcohols having 14 to 15 carbon atoms
  • (Meth)acrylic acid esters of mixtures of alkyl alcohols, such as mixtures of chain and branched alkyl alcohols (SHELL) may also be used.
  • the (co)polymer (A) includes, in addition to the monomer (a), a hydroxyl group-containing monomer (e) and a nitrogen atom-containing monomer (f) (excluding monomer (a)).
  • ) may be a copolymer whose constituent monomer is one or more selected from the group consisting of:
  • hydroxyl group-containing monomer (e) include the following. Hydroxyl group-containing aromatic monomer (p-hydroxystyrene, etc.), hydroxyalkyl (2-6 carbon atoms) (meth)acrylate [2-hydroxyethyl (meth)acrylate, and 2- or 3-hydroxypropyl (meth)acrylate etc.], mono- or di-hydroxyalkyl (1 to 4 carbon atoms) substituted (meth)acrylamides [N,N-dihydroxymethyl (meth)acrylamide, N,N-dihydroxypropyl (meth)acrylamide, N,N-dihydroxypropyl (meth)acrylamide, -2-hydroxybutyl (meth)acrylamide, etc.], vinyl alcohol, alkenol having 3 to 12 carbon atoms [(meth)allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1-octenol and 1-undecenol, etc.], carbon number 4 to 12 alkene monools or alk
  • Examples of the nitrogen atom-containing monomer (f) include the following monomers (f1) to (f4).
  • Acrylamide [two alkyl groups having 1 to 4 carbon atoms bonded to a nitrogen atom; for example, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-diisopropyl(meth) acrylamide and N,N-di-n-butyl (meth)acrylamide, etc.], dialkylaminoalkyl (meth)acrylamide [aminoalkyl group in which two alkyl groups having 1 to 4 carbon atoms are bonded to a nitrogen atom (2 to 4 carbon atoms) 6); for example, N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide and N,N-di-n- butylaminobutyl (meth)acrylamide, etc.], N-vinylcar
  • Nitro group-containing monomer (f2) examples include 4-nitrostyrene.
  • tertiary amino group-containing monomer (f3) Vinyl monomers containing primary amino groups ⁇ alkenylamines having 3 to 6 carbon atoms [(meth)allylamine, crotylamine, etc.], aminoalkyl (meth)acrylates (having 2 to 6 carbon atoms) [aminoethyl (meth)acrylate, etc.] ⁇ ; Secondary amino group-containing vinyl monomer ⁇ monoalkylaminoalkyl (meth)acrylate [those having an aminoalkyl group (having 2 to 6 carbon atoms) in which one alkyl group having 1 to 6 carbon atoms is bonded to the nitrogen atom ; For example, t-butylaminoethyl (meth)acrylate and methylaminoethyl (meth)acrylate, etc.], dialkenylamine having 6 to 12 carbon atoms [di(meth)allylamine, etc.]; Tertiary amino group-containing vinyl monomer
  • Nitrile group-containing monomer (f4) examples include (meth)acrylonitrile.
  • amide group-containing monomers (f1) preferred are amide group-containing monomers (f1) and monomers containing primary to tertiary amino groups from the viewpoint of copolymerizability with other monomers.
  • (f3) and more preferred are N,N-diphenylaminoethyl (meth)acrylamide, dimethylaminoethyl (meth)acrylamide, diethylaminoethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate.
  • the polymer (A) may include the following monomers (g) to (n) as constituent monomers.
  • Alicyclic hydrocarbon monomer (h) examples include cyclohexene, (di)cyclopentadiene, pinene, limonene, vinylcyclohexene and ethylidenebicycloheptene.
  • Vinyl esters, vinyl ethers, vinyl ketones (j): Vinyl esters of saturated fatty acids with 2 to 12 carbon atoms (vinyl acetate, vinyl propionate, vinyl butyrate, vinyl octoate, etc.), alkyl, aryl or alkoxyalkyl vinyl ethers with 1 to 12 carbon atoms (methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether) , butyl vinyl ether, 2-ethylhexyl vinyl ether, phenyl vinyl ether, vinyl-2-methoxyethyl ether, vinyl-2-butoxyethyl ether, etc.) and alkyl or aryl vinyl ketones having 1 to 8 carbon atoms (methyl vinyl ketone, ethyl vinyl ketone, phenyl vinyl ketone, etc.).
  • Epoxy group-containing monomer (k) examples include glycidyl (meth)acrylate and glycidyl (meth)allyl ether.
  • Halogen element-containing monomer (l) examples include vinyl chloride, vinyl bromide, vinylidene chloride, (meth)allyl chloride, and halogenated styrene (dichlorostyrene, etc.).
  • Esters of unsaturated polycarboxylic acids (m): Alkyl, cycloalkyl or aralkyl esters of unsaturated polycarboxylic acids [alkyl diesters having 1 to 8 carbon atoms of unsaturated dicarboxylic acids (maleic acid, fumaric acid, itaconic acid, etc.) (dimethyl maleate, dimethyl fumarate, diethyl maleate) and dioctyl maleate)].
  • the proportion of monomer (a) constituting the (co)polymer (A) is determined from the viewpoint of improving the viscosity index and solubility at low temperature (-60°C). Preferably it is 70 to 100% by weight, more preferably 78 to 100% by weight, particularly preferably 85 to 100% by weight, based on the total weight of the monomers.
  • the ratio of the alkyl (meth)acrylate (a1) having a straight chain or branched alkyl group having 1 to 3 carbon atoms constituting the (co)polymer (A) is determined by the viscosity index improvement effect and low temperature (-60°C) From the viewpoint of solubility, it is preferably 10 to 70% by weight, more preferably 15 to 60% by weight, and particularly preferably It is 20 to 55% by weight.
  • the proportion of the alkyl (meth)acrylate (a2) having a linear or branched alkyl group having 4 to 17 carbon atoms constituting the (co)polymer (A) is determined by the viscosity index improvement effect and low temperature (-60°C) From the viewpoint of solubility, it is preferably 10 to 90% by weight, more preferably 20 to 85% by weight, and particularly preferably It is 30 to 80% by weight.
  • the total proportion of monomers (e) to (f) constituting the (co)polymer (A) is determined by the total weight of the monomers constituting the (co)polymer (A) from the viewpoint of improving the viscosity index.
  • the total proportion of monomers (g) to (n) constituting the (co)polymer (A) is determined based on the composition of the (co)polymer (A) from the viewpoint of solubility at low temperature (-60°C). It is preferably at most 10% by weight, more preferably at most 7% by weight, particularly preferably at most 5% by weight, based on the total weight of the monomers.
  • the solubility parameter (hereinafter abbreviated as SP value) of the (co)polymer (A) is 9.00 to 9.0 from the viewpoint of low temperature viscosity, solubility at low temperature (-60°C), and viscosity index improvement effect. .80 (cal/cm 3 ) 1/2 , preferably 9.00 to 9.50 (cal/cm 3 ) 1/2 , more preferably 9.10 to 9.40 (cal/cm 3 ) ) 1/2 , more preferably 9.20 to 9.40 (cal/cm 3 ) 1/2 , particularly preferably 9.25 to 9.40 (cal/cm 3 ) 1/2 .
  • the SP value of the (co)polymer (A) is 9.00 (cal/cm 3 ) 1/2 or more, the low-temperature viscosity is low and it is difficult to precipitate at low temperatures, and it is 9.80 (cal/cm 3 ) 1/ When it is 2 or less, the viscosity index improving effect is good.
  • the SP value in the present invention is determined by the numerical value (atom or functional group (heat of vaporization and molar volume at 25° C.), it means the value calculated by formula (28) on page 153 of the same.
  • the constituent units derived from methyl methacrylate are 2 CH 3 , 1 CH 2 , 1 C, and 1 CO 2 as atomic groups.
  • the SP value of the structural unit derived from methyl methacrylate is 9.933 (cal/cm 3 ) 1/2 .
  • Similar calculations show that the SP value of the structural unit derived from dodecyl methacrylate is 9.017 (cal/cm 3 ) 1/2 .
  • the SP value of the polymer is as follows: It is calculated by arithmetic averaging based on the weight fraction of the SP value.
  • the SP value of the (co)polymer (A) can be adjusted to a desired range by appropriately adjusting the monomers and weight fractions used. Specifically, the SP value can be reduced by using many monomers with a long alkyl group carbon number, and the SP value can be increased by using many monomers with a short alkyl group carbon number. can do.
  • the weight fraction is calculated based on the SP value of each (co)polymer (A), and the arithmetic average value is the above SP value. It is preferable to satisfy the following.
  • the weight average molecular weight (Mw) of the (co)polymer (A) is preferably 5,000 to 300,000, more preferably 10,000 to 250, from the viewpoint of improving the viscosity index and shear stability. 000, particularly preferably from 30,000 to 200,000, particularly preferably from 50,000 to 150,000.
  • the (co)polymer (A) can be obtained by a known production method, specifically a method of solution polymerizing the above-mentioned monomers in a solvent in the presence of a polymerization catalyst.
  • the solvent include toluene, xylene, alkylbenzene having 9 to 10 carbon atoms, methyl ethyl ketone, ethyl acetate, 2-propanol, and phosphoric acid ester (C).
  • polymerization catalysts examples include azo catalysts (azobisisobutyronitrile and azobisvaleronitrile, etc.), peroxide catalysts (benzoyl peroxide, cumyl peroxide, lauryl peroxide, etc.), and redox catalysts (benzoyl peroxide, etc.). and tertiary amine). Furthermore, if necessary, a known chain transfer agent (such as an alkyl mercaptan having 2 to 20 carbon atoms) may be used.
  • the polymerization temperature is preferably 25 to 140°C, more preferably 50 to 120°C.
  • the (co)polymer (A) can be obtained by bulk polymerization, emulsion polymerization, or suspension polymerization.
  • the polymerization form may be either a random addition polymer or an alternating copolymer, or a graft copolymer or a block copolymer. .
  • the viscosity index improver composition of the present invention contains a chain aliphatic alcohol (B) having an HLB value of 2.5 to 7.0.
  • HLB value 2.5 or more
  • precipitates are less likely to be generated at low temperatures (-60° C.), and when it is 7.0 or less, the effect of suppressing the hydrolysis of phosphate ester is excellent.
  • HLB of (B) is 7.0 or less
  • micelles can be formed against the water mixed in the lubricating oil and hydrolysis of the phosphate ester can be suppressed, and when the HLB is 2.5 or more.
  • the HLB value of the chain aliphatic alcohol (B) is preferably 3.0 to 6.0, more preferably 4.0 to 5.0.
  • the HLB value is an index indicating the balance between hydrophilicity and lipophilicity, and is described, for example, in "Introduction to Surfactants” [published by Sanyo Chemical Industries, Ltd., 2007, written by Takehiko Fujimoto], page 212. This is known as the value calculated by the Oda method, and not the value calculated by the Griffin method.
  • the organic value and inorganic value for deriving HLB are determined as 20 per carbon atom as the organic value, and the inorganic value is determined as Calculated using the values in the table described on page 213 of "Introduction to Drugs".
  • chain aliphatic alcohol (B) from the viewpoint of improving the stability of the lubricating oil composition over time (suppressing hydrolysis of phosphate ester), a straight chain or branched aliphatic alcohol having 8 to 17 carbon atoms is used.
  • straight-chain or branched aliphatic alcohols having 9 to 16 carbon atoms are preferred, and straight-chain or branched aliphatic alcohols having 10 to 15 carbon atoms are particularly preferred.
  • the SP value of the chain aliphatic alcohol (B) is preferably 9.00 to 10.20 (cal/cm 3 ) 1/2 , more preferably 9.50 to 1/2, from the viewpoint of improving the stability of the lubricating oil over time. 10.00 (cal/cm 3 ) 1/2 . Further, when a plurality of chain aliphatic alcohols (B) having different SP values are contained, it is preferable that the arithmetic average value based on the weight fraction is within the above range.
  • the viscosity index improver composition of the present invention has an excellent effect of improving the viscosity index, an excellent effect of suppressing hydrolysis of phosphate ester, and is free from precipitates even at low temperatures (-60°C), and has a good viscosity at low temperatures for lubricating. Since an oil composition can be obtained, it can be used as a viscosity index improver composition for lubricating oil compositions containing phosphate ester (C).
  • Examples of the phosphoric acid ester (C) include those represented by the following general formula (2).
  • R 4 OP(O)-(OR 4 ) 2 (2) [In general formula (2), R 4 each independently represents a hydrocarbon group having 1 to 10 carbon atoms. ]
  • the hydrocarbon group having 1 to 10 carbon atoms includes an alkyl group having 1 to 10 carbon atoms ⁇ for example, a straight chain alkyl group (for example, a methyl group, an ethyl group, an n-propyl group, an n- butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, etc.), branched alkyl group (e.g.
  • the hydrocarbon group having 1 to 10 carbon atoms is preferably a hydrocarbon group having 1 to 6 carbon atoms, and more preferably a hydrocarbon group having 2 to 4 carbon atoms.
  • Examples of the phosphate ester (C) include tri(isopropyl) phosphate, tri(n-butyl) phosphate, tri(isobutyl) phosphate, tri(sec-butyl) phosphate, and tert-butyl phosphate.
  • n-butyldiisobutyl phosphate di-n-butylisobutyl phosphate, diisobutylpentyl phosphate, tri(n-pentyl) phosphate, tri(isopentyl) phosphate, tri(2-ethylhexyl) phosphate, phosphoric acid
  • examples include n-butyldiphenyl, isobutyldiphenyl phosphate, triphenyl phosphate, tri(isopropylphenyl) phosphate, and tri(isobutylphenyl) phosphate.
  • tri(n-butyl) phosphate, tri(isobutyl) phosphate, tri(sec-butyl) phosphate, tri(tert-butyl) phosphate, tri(t-butyl) phosphate, Phenyl and tri(isopropylphenyl) phosphate are preferred, and tri(n-butyl) phosphate and tri(isobutyl) phosphate are more preferred.
  • the kinematic viscosity (measured according to ASTM D 445) at 100°C of the phosphoric acid ester (C) is preferably 1 to 5 mm 2 /s, more preferably 1 to 4 mm 2 /s from the viewpoint of low-temperature viscosity. , particularly preferably 1 to 3.5 mm 2 /s.
  • the kinematic viscosity (measured according to ASTM D 445) at 40°C of the phosphoric acid ester (C) is preferably 1 to 40 mm 2 /s, more preferably 1 to 25 mm 2 /s from the viewpoint of low-temperature viscosity. , particularly preferably 1 to 20 mm 2 /s.
  • the viscosity index improver composition of the present invention is a viscosity index improver composition containing the (co)polymer (A) and the chain aliphatic alcohol (B).
  • the viscosity index improver composition of the present invention can improve the viscosity index of the lubricating oil composition when added to a lubricating oil composition containing the phosphate ester (C).
  • the improvement effect is high, and by containing the chain aliphatic alcohol (B), the effect of suppressing the hydrolysis of the phosphoric acid ester (C) is excellent.
  • the chain aliphatic alcohol (B) tends to precipitate in the phosphoric ester (C) especially at low temperatures (-60°C), and the (co)polymer (A) and the chain aliphatic alcohol (B) tend to precipitate in the phosphate ester (C). ) can be made to be difficult to precipitate in the phosphoric ester (C). Therefore, the viscosity index improver composition of the present invention improves the viscosity index of the lubricating oil composition by containing the (co)polymer (A) and the chain aliphatic alcohol (B). It is possible to suppress deterioration of lubricity due to hydrolysis of ester (C) and suppress precipitation at low temperatures.
  • the weight ratio (A/B) of the above-mentioned (co)polymer (A) and the above-mentioned chain aliphatic alcohol (B) in the viscosity index improver composition has the effect of improving the stability over time and improving the viscosity index of the lubricating oil. From this point of view, it is preferably 10 to 5,000, more preferably 10 to 3,000, particularly preferably 10 to 500.
  • the absolute value of the difference between the SP value of the (co)polymer (A) and the SP value of the chain aliphatic alcohol (B) is 0.10 to 1.00 ( It is preferably 0.20 to 0.90 (cal/cm 3 ) 1/2 , more preferably 0.20 to 0.90 (cal/cm 3 ) 1/2 .
  • the absolute value of the difference in arithmetic average values based on the respective weight fractions should be within the above range. It is preferable that there be.
  • the viscosity index improver composition of the present invention only needs to contain the above-mentioned (co)polymer (A) and the above-mentioned chain aliphatic alcohol (B). ) may also be included.
  • the content of the (co)polymer (A) in the viscosity index improver composition is 10 to 70% by weight based on the weight of the viscosity index improver composition, from the viewpoint of ease of handling the viscosity index improver composition. %, more preferably 20 to 60% by weight.
  • the content of the chain aliphatic alcohol (B) in the viscosity index improver composition is based on the weight of the viscosity index improver composition, from the viewpoint of stability over time when producing a lubricating oil composition.
  • the content of the phosphoric acid ester (C) in the viscosity index improver composition is preferably 25 to 89% by weight, more preferably 35% by weight, based on the weight of the viscosity index improver composition. It is 5 to 79% by weight.
  • the viscosity index improver composition of the present invention has an excellent viscosity index improvement effect and a phosphate ester hydrolysis inhibiting effect, and furthermore, there is no precipitate even at low temperatures (-60°C), and the viscosity at low temperatures is good for lubricants.
  • the oil composition can be obtained, it can be used as a viscosity index improver for lubricating oil compositions containing phosphoric ester (C), and further containing phosphoric ester (C) as a base oil. It is particularly useful as a viscosity index improver for aircraft hydraulic fluids that may be used in the sky (under low-temperature environments).
  • the lubricating oil composition of the present invention contains the viscosity index improver composition and a phosphoric acid ester (C).
  • the content of the (co)polymer (A) in the lubricating oil composition is preferably 1 to 15% by weight based on the weight of the lubricating oil composition from the viewpoint of low-temperature viscosity and kinematic viscosity at 100 ° C. More preferably, it is 2 to 10% by weight.
  • the content of the chain aliphatic alcohol (B) in the lubricating oil composition is from 0.01 to 0.6% by weight based on the weight of the lubricating oil composition from the viewpoint of stability over time of the lubricating oil.
  • the content of phosphate ester (C) in the lubricating oil composition is preferably 75% by weight or more, more preferably 75 to 98.99% by weight, based on the weight of the lubricating oil composition, from the viewpoint of low-temperature viscosity. , more preferably 80 to 97.95% by weight.
  • the weight ratio (A/B) of the (co)polymer (A) and the chain aliphatic alcohol (B) in the lubricating oil composition is preferably 10 to 5,000 from the viewpoint of improving the viscosity index, and It is preferably 10 to 3,000, particularly preferably 10 to 500.
  • the phosphoric ester (C) contained in the lubricating oil composition may be the phosphoric ester (C) contained in the viscosity index improver composition, or may be the phosphoric ester (C) that is derived from a source other than the viscosity index improver composition. It may also be an acid ester (C).
  • the phosphoric ester (C) contained in the lubricating oil composition is the phosphoric ester (C) derived from a source other than the phosphoric ester (C) contained in the viscosity index improver composition and the viscosity index improver composition. ) may be a mixture.
  • the phosphoric ester (C) contained in the lubricating oil composition the above-mentioned phosphoric ester (C) can be used.
  • the phosphoric acid ester (C) derived from a source other than the viscosity index improver composition tri(n-butyl) phosphate is preferred, and a mixture of tri(isopropylphenyl) phosphate and triphenyl phosphate is also preferred. It is preferable that the phosphoric acid ester (C) contained in the lubricating oil composition has a kinematic viscosity at 40° C. of 1 to 40 mm 2 /s.
  • ⁇ Method for measuring the content of chain aliphatic alcohol (B) in the viscosity index improver composition and lubricating oil composition Using a Soxhlet extractor, 1 g of the viscosity index improver composition or lubricating oil composition of the present invention is separated and extracted into the (co)polymer (A) component and other components soluble in the hexane solvent using 300 ml of hexane solvent. Since the chain aliphatic alcohol (B) is dissolved in hexane, it is included in the other extracted components. The hexane solvent in the solution containing the extracted other components is distilled off under reduced pressure using an evaporator.
  • the content of chain aliphatic alcohol (B) in the composition can be calculated from the amount of the viscosity index improver composition or lubricating oil composition used, the amount X of other component extracts, and the peak area ratio.
  • GC-MS measurement conditions Equipment: "GC-2010" [manufactured by Shimadzu Corporation] Column: “ZB-5 (column length: 30 m, column inner diameter: 0.25 mm, film thickness: 0.25 ⁇ m)” [manufactured by Shimadzu GLC Co., Ltd.] Vaporization chamber temperature: 250°C Pressure: 1000kPa Split ratio: 50 Temperature raising conditions: Hold at 40°C for 5 minutes, raise temperature to 300°C (10°C/min), hold at 300°C for 10 minutes. (MS measurement conditions) Equipment: "GCMS QP-2010 Plus” [manufactured by Shimadzu Corporation] Ion source: CI Ion source temperature: 170°C Interface temperature: 250°C Introduced reagent gas: I
  • the lubricating oil composition of the present invention contains, in addition to the viscosity index improver composition and the phosphate ester (C), other additives ⁇ an antioxidant, a friction modifier, an antifoaming agent, a rust preventive, and a corrosion preventive agent. at least one kind of additive selected from the group consisting of various additives such as additives.
  • Antioxidant For example, 2,6-di-tert-butylphenol (hereinafter, tert-butyl is abbreviated as t-butyl), 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-Butyl-4-ethylphenol, 2,4-dimethyl-6-t-butylphenol, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-bis(2,6-di- t-butylphenol), 4,4'-bis(2-methyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4- ethyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 4,4'-isopropylidenebis(2,6-di-t-butylphenol), 2,2 '-Methylenebis
  • Friction modifier For example, higher alcohols such as oleyl alcohol, stearyl alcohol, and lauryl alcohol; fatty acids such as oleic acid, stearic acid, and lauric acid; glyceryl oleate, glyceryl stearate, glyceryl laurate, alkyl glyceryl ester, alkenyl glyceryl ester, alkynyl Esters such as glyceryl ester, ethylene glycol oleate, ethylene glycol stearate, ethylene glycol laurate, propylene glycol oleate, propylene glycol stearate, and propylene glycol laurate; oleylamide, stearylamide, lauryl Amides such as amides, alkylamides, alkenylamides and alkynylamides; oleylamine, stearylamine, laurylamine, alkylamine, alkenylamine, alkynyl
  • Antifoaming agent examples include polydimethyl silicone, dimethyl silicone oil, trifluoropropyl methyl silicone, colloidal silica, polyalkyl acrylate, polyalkyl methacrylate, alcohol ethoxy/propoxylate, fatty acid ethoxy/propoxylate, and sorbitan partial fatty acid ester.
  • Rust inhibitor For example, sodium nitrite, oxidized paraffin wax calcium salt, oxidized paraffin wax magnesium salt, tallow fatty acid alkali metal salt, alkaline earth metal salt, alkaline earth amine salt, alkenyl succinic acid, alkenyl succinic acid half ester (molecular weight of alkenyl group (about 100 to 300), sorbitan monoester, nonylphenol ethoxylate, and lanolin fatty acid calcium salt.
  • Corrosion inhibitor For example, 2-ethylhexyl 7-oxabicyclo[4.1.0]heptane-3-carboxylic acid, 7-oxabicyclo[4.1.0]heptane as the alicyclic epoxide as disclosed in Patent Document 2 2-Hydroxy-N-(1H-1,2,4-triazole- 3-yl)benzamide, N,N-bis(2-ethylhexyl)-[(1,2,4-triazol-1-yl)methyl]amine, N,N-bis(2-ethylhexyl)-[(1, 2,4-triazol-1-yl)methyl]amine and 2,2'-[[(4 or 5 or 1)-(2-ethylhexyl)-methyl-1H-benzotriazol-1-methyl]imino]bisethanol
  • Other examples include bis(poly-2-carboxyethyl)phosphinic acid, hydroxyphosphonoacetic acid, tetraalky
  • additives may include one type, two or more types may be used in combination, and a package additive containing multiple types may be used as the additive.
  • the content of other additives is preferably 1 to 15% by weight, more preferably 2 to 10% by weight, based on the weight of the lubricating oil composition.
  • the viscosity index (measured according to ASTM D 445) of the lubricating oil composition is preferably 300 or more, more preferably 320 or more, and particularly preferably 330 or more.
  • the low-temperature viscosity of the lubricating oil composition is preferably 1200 mPa ⁇ s or less, more preferably 1100 mPa ⁇ s or less. , particularly preferably 1050 mPa ⁇ s or less.
  • the lubricating oil composition of the present invention has a high viscosity index, suppresses the hydrolysis of phosphoric acid ester, and has no precipitates even at low temperatures (-60°C), and has good viscosity at low temperatures. It is useful as an aircraft hydraulic fluid that is sometimes used in low-temperature environments.
  • the present disclosure (1) is a viscosity index improver composition for a lubricating oil composition containing a phosphate ester (C), A (co)polymer (A) having monomer (a) represented by the following general formula (1) as an essential constituent monomer, and a chain aliphatic compound having an HLB value of 2.5 to 7.0.
  • the present invention is a viscosity index improver composition containing alcohol (B) and in which the (co)polymer (A) has a solubility parameter of 9.00 to 9.80 (cal/cm 3 ) 1/2 .
  • R 1 is a hydrogen atom or a methyl group
  • -X 1 - is a group represented by -O- or -NH-
  • R 2 is an alkylene group having 2 to 4 carbon atoms
  • R 3 is a straight group having 1 to 17 carbon atoms
  • p is an integer of 0 to 20, and when p is 2 or more, R 2 may be the same or different.
  • the present disclosure (2) is the viscosity index improver composition according to the present disclosure (1), wherein the (co)polymer (A) has a weight average molecular weight of 5,000 to 300,000.
  • the present disclosure (3) provides the present disclosure (1) or (2), wherein the weight ratio (A/B) of the (co)polymer (A) and the chain aliphatic alcohol (B) is 10 to 5000.
  • the present disclosure (4) relates to any one of the present disclosure (1) to (3), wherein the chain aliphatic alcohol (B) is a linear or branched aliphatic alcohol having 8 to 17 carbon atoms.
  • the present disclosure (5) is the viscosity index improver composition according to any one of the present disclosure (1) to (4), which further contains a phosphoric acid ester (C).
  • the present disclosure (6) is a lubricating oil composition containing the viscosity index improver composition according to any one of the present disclosures (1) to (5) and a phosphoric acid ester (C).
  • the present disclosure (7) is the lubricating oil composition according to the present disclosure (6), wherein the content of the phosphate ester (C) in the lubricating oil composition is 75% by weight or more.
  • the present disclosure (8) is the lubricating oil composition according to the present disclosure (6) or (7), wherein the phosphoric acid ester (C) has a kinematic viscosity of 1 to 40 mm 2 /s at 40° C.
  • the present disclosure (9) is the lubricating oil composition according to any one of the present disclosure (6) to (8), which is used as an aircraft hydraulic fluid.
  • Examples 1 to 14, Comparative Examples 1 to 5> In a reaction vessel equipped with a stirring device, a heating and cooling device, a thermometer, a dropping funnel, a nitrogen introduction pipe, and a pressure reducing device, add 100 weight phosphoric acid esters (C) of the types and amounts listed in Tables 2-1 to 2-3. Into another glass beaker, add chain aliphatic alcohol (B) or comparative compound (B') of the types and amounts listed in Tables 2-1 to 2-3, and polymer ( The constituent monomers of A), a chain transfer agent, and a polymerization initiator were added, stirred and mixed at 20°C to prepare a monomer solution, and the solution was added to a dropping funnel.
  • C phosphoric acid esters
  • the monomer solution was converted into phosphate ester (C) over a period of 3 hours while keeping the system temperature at 70 to 80°C under closed conditions. was added dropwise to the reaction vessel containing the solution. At this time, each raw material was charged so that the liquid level of the reaction solution was 70% of the capacity of the reaction container. After aging at 90°C for 2 hours from the end of dropping, the temperature was raised to 120°C, and at the same temperature, the degree of vacuum was reduced to 0.027 to 0.040 MPa until the liquid level reached 90% of the capacity of the reaction vessel. The pressure was gradually reduced so as not to exceed the pressure, and then unreacted monomers were removed until the generation of bubbles completely disappeared.
  • gas phase oxygen concentration 100 ppm
  • viscosity index improver compositions (R1) to (R14), (S1) containing the (co)polymer (A) and the chain aliphatic alcohol (B) or the comparative compound (B') were prepared. ⁇ (S5) was obtained.
  • the Mw of the copolymers (A1) to (A11) and (A'1) to (A'2) and the content of the chain aliphatic alcohol (B) in the obtained viscosity index improver composition were determined as above. The results measured by this method are shown in Tables 2-1 to 2-3. In addition, the appearance at low temperatures and hydrolytic stability of the viscosity index improver composition were measured by the following methods, and the results are shown in Tables 2-1 to 2-3.
  • Monomer (a), monomer (e), monomer (f), chain transfer agent, polymerization initiator, chain aliphatic alcohol ( B), comparative compound (B'), phosphoric acid ester (C), and additive (antifoaming agent) were as follows.
  • ⁇ Method for measuring hydrolytic stability of viscosity index improver composition The acid value of the viscosity index improver composition was measured according to JIS K0070. Further, 1% by weight of water was added to the prepared viscosity index improver composition, and the mixture was heated at 100° C. for 100 hours. The acid value after heating was measured according to JIS K0070. The difference between the acid value before heating and the acid value after heating is listed as the degree of change in acid value in Tables 2-1 to 2-3.
  • Examples 15 to 28 and Comparative Examples 6 to 10 evaluation of lubricating oil composition
  • a stainless steel container equipped with a stirring device add the viscosity index improver composition in the amount listed in Table 3 to prepare a lubricating oil composition so that the kinematic viscosity at 100° C. is 3.50 mm 2 /s. did.
  • the obtained lubricating oil composition was evaluated for its kinematic viscosity at 100°C, kinematic viscosity at 40°C, viscosity index, shear stability, low temperature viscosity (-54°C), appearance at low temperature (-60°C), and hydrolytic stability as follows. It was measured by the method. The results are shown in Table 3.
  • ⁇ Method for measuring low-temperature viscosity (-54°C) of lubricating oil composition The viscosity of the sample after cooling at -54°C for 3 hours was measured using a Brookfield viscometer according to JPI-5S-26-99. The smaller the number, the lower the low-temperature viscosity and the higher the low-temperature properties.
  • ⁇ Method for measuring hydrolytic stability of lubricating oil composition The acid value of the lubricating oil composition was measured according to JIS K0070. Further, 1% by weight of water was added to the prepared lubricating oil composition, and the mixture was heated at 100° C. for 100 hours. The acid value after heating was measured according to JIS K0070. The difference between the acid value before heating and the acid value after heating is shown in Table 3 as the degree of change in acid value.
  • the lubricating oil composition containing the viscosity index improver of the present invention has an excellent viscosity index, no precipitates even at low temperatures, low viscosity at low temperatures, and excellent viscosity due to aging. It can be seen that hydrolysis of the acid ester is small and the properties are excellent.
  • the viscosity index improver composition of the present invention has an excellent viscosity index improvement effect and a phosphate ester hydrolysis inhibiting effect, and furthermore, there is no precipitate even at low temperatures (-60°C), and the viscosity at low temperatures is good for lubricants. Since the lubricating oil composition containing the viscosity index improver composition of the present invention has a low viscosity index and phosphoric acid ester hydrolysis, it also has no precipitates even at low temperatures (-60°C). Since it has a good viscosity at low temperatures, it is particularly useful as an aircraft hydraulic fluid that may be used in the sky (in a low-temperature environment).

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Abstract

This viscosity index improver composition for a lubricating oil composition containing a phosphate ester (C), the viscosity index improver composition containing: a (co)polymer (A) having a monomer (a) represented by general formula (1) as an essential constituent monomer; and a chain aliphatic alcohol (B) having an HLB value of 2.5 to 7.0, wherein the (co)polymer (A) has a solubility parameter of 9.00 to 9.80 (cal/cm3)1/2. (R1 is a hydrogen atom or a methyl group; –X1– is a group represented by –O– or –NH–; R2 is a C2-4 alkylene group; R3 is a C1-17 linear or branched alkyl group; p is an integer of 0–20; and when p is 2 or greater, R2 may be the same or different.)

Description

粘度指数向上剤組成物及び潤滑油組成物Viscosity index improver composition and lubricating oil composition
　本発明は粘度指数向上剤組成物及び潤滑油組成物に関する。 The present invention relates to a viscosity index improver composition and a lubricating oil composition.
　油圧装置の中で動力伝達媒体として使用される作動油には、合成系作動油、含水系作動油、鉱油系作動油等が公知であるが、高温熱源のある環境で使用される場合には、難燃性の合成系作動油もしくは含水系作動液が使用される。
　例えば、合成系作動油であるリン酸エステル系作動油は耐火性に優れ、潤滑性、酸化安定性、圧縮率の小ささからアクチュエータなどに対する応答性に優れているため、発電所や航空機などの油圧システムに利用されている。
　特に、航空機に使用される油圧作動油では加水分解安定性と低温流動性が良好である必要がある。さらに、幅広い温度域で使用されることから、低い低温粘度が必要でありながらも高温でも一定程度の許容できる粘度を維持しなければならず、高い粘度指数が必要である（特許文献１）。高い粘度指数を得るために粘度指数向上剤（特許文献２）を使用することが知られており、例えば、ポリブチルメタクリレートやポリヘキシルメタクリレート（特許文献３）等を用いた潤滑油組成物が知られている。しかしながら、上記の潤滑油組成物は、粘度指数向上効果が未だ十分でないという問題がある。 Hydraulic oils used as power transmission media in hydraulic equipment include synthetic hydraulic oils, water-containing hydraulic oils, and mineral oil-based hydraulic oils, but when used in environments with high-temperature heat sources, , flame-retardant synthetic hydraulic oil or water-containing hydraulic fluid is used.
For example, phosphate ester hydraulic fluid, which is a synthetic hydraulic fluid, has excellent fire resistance, lubricity, oxidation stability, and low compressibility, so it has excellent responsiveness to actuators, etc., so it is used in power plants, aircraft, etc. Used in hydraulic systems.
In particular, hydraulic fluids used in aircraft need to have good hydrolytic stability and low-temperature fluidity. Furthermore, since it is used in a wide temperature range, it needs to have a low low-temperature viscosity, but it must also maintain a certain level of acceptable viscosity even at high temperatures, and a high viscosity index is required (Patent Document 1). It is known to use a viscosity index improver (Patent Document 2) in order to obtain a high viscosity index, and for example, lubricating oil compositions using polybutyl methacrylate, polyhexyl methacrylate (Patent Document 3), etc. are known. It is being However, the above-mentioned lubricating oil composition has a problem in that the effect of improving the viscosity index is not yet sufficient.
　また、リン酸エステル系作動油は親水性が高く、水分の存在で容易に酸およびアルコールに分解し、これらが金属を腐食させることが知られており、さらに作動油の熱分解で生成する酸性物質も金属を腐食させる虞がある。このように水分によって作動油が劣化した結果生成した生成物は、機械や設備破損による制御不良を引き起こし、更なる作動油の劣化促進等の不都合の発生原因となる（特許文献４）。この問題に対しては脂環式エポキシエステル系化合物を酸捕捉剤（特許文献５）として使用することが広く知られている。しかしながら、脂環式エポキシエステル系酸捕捉剤はそれ自身も加水分解されるという問題（特許文献５）と、エポキシ化合物よりも脂環式エポキシ化合物の方が酸やカチオンとの反応性が高く、また脂環式エポキシエステル系酸捕捉剤はエポキシ硬化剤として使用される（非特許文献１）ものであることから、リン酸エステルや脂環式エポキシエステルの加水分解により発生した酸との反応において、単純な１：１の反応で終わらずに、硬化反応により高分子量エポキシ樹脂が生成してしまう問題がある。これより潤滑油の粘度特性の悪化や不溶物質としてスラッジが生成することで潤滑性が悪化する問題がある。 In addition, phosphate ester hydraulic fluids are highly hydrophilic and easily decompose into acids and alcohols in the presence of moisture, which are known to corrode metals. Substances can also corrode metals. The products generated as a result of deterioration of the hydraulic oil due to moisture cause poor control due to damage to machines and equipment, and cause problems such as further acceleration of deterioration of the hydraulic oil (Patent Document 4). To solve this problem, it is widely known to use an alicyclic epoxy ester compound as an acid scavenger (Patent Document 5). However, alicyclic epoxy ester-based acid scavengers have the problem of being hydrolyzed themselves (Patent Document 5), and alicyclic epoxy compounds have higher reactivity with acids and cations than epoxy compounds. In addition, since the alicyclic epoxy ester acid scavenger is used as an epoxy curing agent (Non-Patent Document 1), it is difficult to react with the acid generated by hydrolysis of phosphoric acid ester or alicyclic epoxy ester. However, there is a problem in that the curing reaction does not end with a simple 1:1 reaction and a high molecular weight epoxy resin is produced. This poses a problem in that the viscosity characteristics of the lubricating oil deteriorate and sludge is generated as an insoluble substance, resulting in deterioration in lubricity.
特許第５２０９３１８号公報Patent No. 5209318 特表２００２－５２９５７７号公報Special Publication No. 2002-529577 米国特許第３７１８５９６号公報US Patent No. 3,718,596 特許第４３８１１２３号公報Patent No. 4381123 特表２００９－５０３１４２号公報Special Publication No. 2009-503142
　本発明の目的は、粘度指数向上効果に優れ、リン酸エステルの加水分解抑制効果に優れ、さらに低温（－６０℃）でも析出物が無く、低温での粘度が低い潤滑油組成物を得ることができる粘度指数向上剤組成物を提供することである。 An object of the present invention is to obtain a lubricating oil composition that has an excellent effect of improving the viscosity index, an excellent effect of suppressing hydrolysis of phosphate ester, and is free from precipitates even at low temperatures (-60°C) and has a low viscosity at low temperatures. It is an object of the present invention to provide a viscosity index improver composition capable of improving the viscosity index.
　本発明者らは、上記の目的を達成するべく検討を行った結果、本発明に到達した。
　すなわち、本発明は、リン酸エステル（Ｃ）を含有する潤滑油組成物用の粘度指数向上剤組成物であって、下記一般式（１）で表される単量体（ａ）を必須構成単量体とする（共）重合体（Ａ）と、ＨＬＢ値が２．５～７．０である鎖状脂肪族アルコール（Ｂ）とを含有し、前記（共）重合体（Ａ）の溶解性パラメータが９．００～９．８０（ｃａｌ／ｃｍ３）１／２である粘度指数向上剤組成物；前記粘度指数向上剤組成物とリン酸エステル（Ｃ）を含有する潤滑油組成物である。
Figure JPOXMLDOC01-appb-C000002
 ［Ｒ１は水素原子又はメチル基；－Ｘ１－は－Ｏ－又は－ＮＨ－で表される基；Ｒ２は炭素数２～４のアルキレン基；Ｒ３は炭素数１～１７の直鎖又は分岐アルキル基；ｐは０～２０の整数であり、ｐが２以上の場合のＲ２は同一でも異なっていてもよい。］ The present inventors conducted studies to achieve the above object, and as a result, they arrived at the present invention.
That is, the present invention provides a viscosity index improver composition for a lubricating oil composition containing a phosphoric acid ester (C), which essentially comprises a monomer (a) represented by the following general formula (1). Containing a (co)polymer (A) as a monomer and a chain aliphatic alcohol (B) having an HLB value of 2.5 to 7.0, the (co)polymer (A) A viscosity index improver composition having a solubility parameter of 9.00 to 9.80 (cal/cm 3 ) 1/2 ; a lubricating oil composition containing the viscosity index improver composition and a phosphate ester (C) It is.
Figure JPOXMLDOC01-appb-C000002
 [R 1 is a hydrogen atom or a methyl group; -X 1 - is a group represented by -O- or -NH-; R 2 is an alkylene group having 2 to 4 carbon atoms; R 3 is a straight group having 1 to 17 carbon atoms; Chain or branched alkyl group; p is an integer of 0 to 20, and when p is 2 or more, R 2 may be the same or different. ]
　本発明の粘度指数向上剤組成物は、粘度指数向上効果に優れ、リン酸エステルの加水分解抑制効果に優れ、さらに低温（－６０℃）でも析出物が無く、低温での粘度が低い潤滑油組成物を得ることができるという効果を奏する。 The viscosity index improver composition of the present invention has an excellent effect of improving the viscosity index, an excellent effect of suppressing the hydrolysis of phosphate ester, and is free from precipitates even at low temperatures (-60°C), making it a lubricating oil with low viscosity at low temperatures. This has the effect that a composition can be obtained.
　本発明の粘度指数向上剤組成物は、リン酸エステル（Ｃ）を含有する潤滑油組成物用の粘度指数向上剤組成物であって、下記一般式（１）で表される単量体（ａ）を必須構成単量体とする（共）重合体（Ａ）と、ＨＬＢ値が２．５～７．０である鎖状脂肪族アルコール（Ｂ）とを含有し、前記（共）重合体（Ａ）の溶解性パラメータが９．００～９．８０（ｃａｌ／ｃｍ３）１／２である粘度指数向上剤組成物である。
　なお、本発明において「（共）重合体」とは「単独重合体及び／又は共重合体」を意味する。また、単量体（ａ）は１種を用いてもよく、２種以上を併用してもよい。
　また、本明細書において（メタ）アクリレートは、アクリレート又はメタクリレートを意味し、（メタ）アクリルアミドは、アクリルアミド又はメタクリルアミドを意味し、（メタ）アクリル酸は、アクリル酸又はメタクリル酸を意味する。
Figure JPOXMLDOC01-appb-C000003
 ［Ｒ１は水素原子又はメチル基；－Ｘ１－は－Ｏ－又は－ＮＨ－で表される基；Ｒ２は炭素数２～４のアルキレン基；Ｒ３は炭素数１～１７の直鎖又は分岐アルキル基；ｐは０～２０の整数であり、ｐが２以上の場合のＲ２は同一でも異なっていてもよい。］ The viscosity index improver composition of the present invention is a viscosity index improver composition for lubricating oil compositions containing a phosphoric acid ester (C), and includes a monomer ( The (co)polymer (A) containing a) as an essential constituent monomer and a chain aliphatic alcohol (B) having an HLB value of 2.5 to 7.0, This is a viscosity index improver composition in which the solubility parameter of aggregate (A) is 9.00 to 9.80 (cal/cm 3 ) 1/2 .
In addition, in the present invention, "(co)polymer" means "homopolymer and/or copolymer". Further, monomer (a) may be used alone or in combination of two or more.
Moreover, in this specification, (meth)acrylate means acrylate or methacrylate, (meth)acrylamide means acrylamide or methacrylamide, and (meth)acrylic acid means acrylic acid or methacrylic acid.
Figure JPOXMLDOC01-appb-C000003
 [R 1 is a hydrogen atom or a methyl group; -X 1 - is a group represented by -O- or -NH-; R 2 is an alkylene group having 2 to 4 carbon atoms; R 3 is a straight group having 1 to 17 carbon atoms; Chain or branched alkyl group; p is an integer of 0 to 20, and when p is 2 or more, R 2 may be the same or different. ]
　一般式（１）において、Ｒ１は水素原子又はメチル基であり、粘度指数向上効果の観点から、好ましくはメチル基である。 In general formula (1), R 1 is a hydrogen atom or a methyl group, and is preferably a methyl group from the viewpoint of improving the viscosity index.
＜（共）重合体（Ａ）＞
　本発明の粘度指数向上剤組成物は、一般式（１）で表される単量体（ａ）を必須構成単量体とする（共）重合体（Ａ）を含有する。
　一般式（１）において、－Ｘ１－は－Ｏ－又は－ＮＨ－で表される基であり、粘度指数向上効果の観点から、好ましくは－Ｏ－で表される基である。 <(Co)polymer (A)>
The viscosity index improver composition of the present invention contains a (co)polymer (A) having the monomer (a) represented by the general formula (1) as an essential constituent monomer.
In the general formula (1), -X 1 - is a group represented by -O- or -NH-, and from the viewpoint of improving the viscosity index, it is preferably a group represented by -O-.
　一般式（１）において、Ｒ２は炭素数２～４のアルキレン基であり、例えば、エチレン基、プロピレン基、ブチレン基等が挙げられる。これらのうち、粘度指数向上効果の観点から、好ましくはエチレン基である。 In the general formula (1), R 2 is an alkylene group having 2 to 4 carbon atoms, such as an ethylene group, a propylene group, a butylene group, and the like. Among these, from the viewpoint of improving the viscosity index, ethylene groups are preferred.
　一般式（１）において、ｐは０～２０の整数であり、ｐが２以上の場合のＲ２は同一でも異なっていてもよく、粘度指数向上効果の観点から、好ましくは０～４であり、さらに好ましくは０～２である。 In the general formula (1), p is an integer of 0 to 20, and when p is 2 or more, R 2 may be the same or different, and from the viewpoint of improving the viscosity index, it is preferably 0 to 4. , more preferably 0 to 2.
　一般式（１）において、Ｒ３は炭素数１～１７の直鎖又は分岐アルキル基であり、例えば、メチル基、エチル基、直鎖状アルキル基｛例えば、ｎ－プロピル基、ｎ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基、ｎ－ノニル基、ｎ－デシル基、ｎ－ウンデシル基、ｎ－ドデシル基、ｎ－トリデシル基、ｎ－テトラデシル基、ｎ－ペンタデシル基、ｎ－ヘキサデシル基、ｎ－ヘプタデシル基等｝、分岐鎖状アルキル基｛例えば、イソプロピル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、イソペンチル基、ネオペンチル基、イソヘキシル基、２－エチルヘキシル基、イソオクチル基、イソノニル基、イソデシル基、イソドデシル基等｝等が挙げられる。
　これらのうち、低温（－６０℃）での溶解性の観点から、炭素数１～１５の直鎖又は分岐アルキル基が好ましく、さらに好ましくは炭素数１～１３の直鎖又は分岐アルキル基である。また、粘度指数向上効果の観点から、炭素数１～３の直鎖又は分岐アルキル基を有するものと炭素数４～１７の直鎖又は分岐アルキル基を有するものとの組み合わせが好ましく、更に好ましくは炭素数１～３の直鎖又は分岐アルキル基を有するものと炭素数４～１５の直鎖又は分岐アルキル基を有するものとの組み合わせであり、さらに好ましくは炭素数１～３の直鎖又は分岐アルキル基を有するものと炭素数６～１３の直鎖又は分岐アルキル基を有するものとの組み合わせである。 In the general formula (1), R 3 is a straight chain or branched alkyl group having 1 to 17 carbon atoms, such as a methyl group, an ethyl group, a straight chain alkyl group {for example, an n-propyl group, an n-butyl group , n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group , n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, etc.}, branched alkyl group {for example, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, isohexyl group , 2-ethylhexyl group, isooctyl group, isononyl group, isodecyl group, isododecyl group, etc.}.
Among these, from the viewpoint of solubility at low temperatures (-60°C), straight chain or branched alkyl groups having 1 to 15 carbon atoms are preferred, and straight chain or branched alkyl groups having 1 to 13 carbon atoms are more preferred. . In addition, from the viewpoint of improving the viscosity index, a combination of one having a straight chain or branched alkyl group having 1 to 3 carbon atoms and one having a straight chain or branched alkyl group having 4 to 17 carbon atoms is preferred, and more preferably. A combination of a straight chain or branched alkyl group having 1 to 3 carbon atoms and a straight chain or branched alkyl group having 4 to 15 carbon atoms, more preferably a straight chain or branched alkyl group having 1 to 3 carbon atoms. It is a combination of one having an alkyl group and one having a straight chain or branched alkyl group having 6 to 13 carbon atoms.
　単量体（ａ）としては、例えば、－Ｘ１－が－Ｏ－のもの；
　例えば、炭素数１～１７の直鎖又は分岐アルキル基を有するアルキル（メタ）アクリレート［例えば、炭素数１～３の直鎖又は分岐アルキル基を有するアルキル（メタ）アクリレート（ａ１）｛例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート等｝、炭素数４～１７の直鎖又は分岐アルキル基を有するアルキル（メタ）アクリレート（ａ２）｛例えば、ｎ－ブチル（メタ）アクリレート、ｎ－ペンチル（メタ）アクリレート、ｎ－ヘキシル（メタ）アクリレート、ｎ－へプチル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、ｎ－ノニル（メタ）アクリレート、ｎ－デシル（メタ）アクリレート、ｎ－ウンデシル（メタ）アクリレート、ｎ－ドデシル（メタ）アクリレート、ｎ－トリデシル（メタ）アクリレート、ｎ－テトラデシル（メタ）アクリレート、ｎ－ペンタデシル（メタ）アクリレート、ｎ－ヘキサデシル（メタ）アクリレート、ｎ－ヘプタデシル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｓｅｃ－ブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、イソペンチル（メタ）アクリレート、ネオペンチル（メタ）アクリレート、イソヘキシル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、イソオクチル（メタ）アクリレート、イソノニル（メタ）アクリレート等｝等］、炭素数１～１７の鎖状脂肪族アルコールの炭素数２～４のアルキレンオキサイド付加物（付加モル数１～２０モル）と（メタ）アクリル酸とのエステル化物等が挙げられる。 As the monomer (a), for example, -X 1 - is -O-;
For example, an alkyl (meth)acrylate having a straight chain or branched alkyl group having 1 to 17 carbon atoms [for example, an alkyl (meth)acrylate (a1) having a straight chain or branched alkyl group having 1 to 3 carbon atoms {for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, etc.}, alkyl (meth)acrylate (a2) having a straight chain or branched alkyl group having 4 to 17 carbon atoms { For example, n-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate , n-decyl (meth)acrylate, n-undecyl (meth)acrylate, n-dodecyl (meth)acrylate, n-tridecyl (meth)acrylate, n-tetradecyl (meth)acrylate, n-pentadecyl (meth)acrylate, n -Hexadecyl (meth)acrylate, n-heptadecyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, isopentyl (meth)acrylate, neopentyl (meth)acrylate, isohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, etc.], addition of alkylene oxide having 2 to 4 carbon atoms to chain aliphatic alcohol having 1 to 17 carbon atoms Examples include esterification products of (meth)acrylic acid (additional mole number: 1 to 20 moles).
　－Ｘ１－が－ＮＨ－のもの；
　例えば、炭素数１～１７の直鎖又は分岐アルキル基を有するＮ－アルキル（メタ）アクリルアミド｛例えば、メチル（メタ）アクリルアミド、エチル（メタ）アクリルアミド、ｎ－プロピル（メタ）アクリルアミド、ｎ－ブチル（メタ）アクリルアミド、ｎ－ペンチル（メタ）アクリルアミド、ｎ－ヘキシル（メタ）アクリルアミド、ｎ－へプチル（メタ）アクリルアミド、ｎ－オクチル（メタ）アクリルアミド、ｎ－ノニル（メタ）アクリルアミド、ｎ－デシル（メタ）アクリルアミド、ｎ－ウンデシル（メタ）アクリルアミド、ｎ－ドデシル（メタ）アクリルアミド、ｎ－トリデシル（メタ）アクリルアミド、ｎ－テトラデシル（メタ）アクリルアミド、ｎ－ペンタデシル（メタ）アクリルアミド、ｎ－ヘキサデシル（メタ）アクリルアミド、ｎ－ヘプタデシル（メタ）アクリルアミド、イソプロピル（メタ）アクリルアミド、イソブチル（メタ）アクリルアミド、ｓｅｃ－ブチル（メタ）アクリルアミド、ｔｅｒｔ－ブチル（メタ）アクリルアミド、イソペンチル（メタ）アクリルアミド、ネオペンチル（メタ）アクリルアミド、イソヘキシル（メタ）アクリルアミド、２－エチルヘキシル（メタ）アクリルアミド、イソオクチル（メタ）アクリルアミド、イソノニル（メタ）アクリルアミド等｝等が挙げられる。 -X 1 - is -NH-;
For example, N-alkyl (meth)acrylamide having a straight chain or branched alkyl group having 1 to 17 carbon atoms {for example, methyl (meth)acrylamide, ethyl (meth)acrylamide, n-propyl (meth)acrylamide, n-butyl ( meth)acrylamide, n-pentyl(meth)acrylamide, n-hexyl(meth)acrylamide, n-heptyl(meth)acrylamide, n-octyl(meth)acrylamide, n-nonyl(meth)acrylamide, n-decyl(meth)acrylamide ) acrylamide, n-undecyl (meth)acrylamide, n-dodecyl (meth)acrylamide, n-tridecyl (meth)acrylamide, n-tetradecyl (meth)acrylamide, n-pentadecyl (meth)acrylamide, n-hexadecyl (meth)acrylamide , n-heptadecyl (meth)acrylamide, isopropyl (meth)acrylamide, isobutyl (meth)acrylamide, sec-butyl (meth)acrylamide, tert-butyl (meth)acrylamide, isopentyl (meth)acrylamide, neopentyl (meth)acrylamide, isohexyl (meth)acrylamide, 2-ethylhexyl (meth)acrylamide, isooctyl (meth)acrylamide, isononyl (meth)acrylamide, etc.}.
　単量体（ａ）としては、粘度指数向上効果の観点から、一般式（１）における－Ｘ１－が－Ｏ－のものが好ましく、さらに好ましくは炭素数１～１７の直鎖又は分岐アルキル基を有するアルキル（メタ）アクリレートであり、次にさらに好ましくは炭素数１～３の直鎖又は分岐アルキル基を有するアルキル（メタ）アクリレート（ａ１）と炭素数４～１７の直鎖又は分岐アルキル基を有するアルキル（メタ）アクリレート（ａ２）との組み合わせであり、より好ましくは炭素数１～３の直鎖又は分岐アルキル基を有するアルキル（メタ）アクリレート（ａ１）と炭素数４～１５の直鎖又は分岐アルキル基を有するアルキル（メタ）アクリレートとの組み合わせであり、特に好ましくは炭素数１～３の直鎖又は分岐アルキル基を有するアルキル（メタ）アクリレート（ａ１）と炭素数６～１３の直鎖又は分岐アルキル基を有するアルキル（メタ）アクリレートとの組み合わせである。 From the viewpoint of improving the viscosity index, the monomer (a) is preferably one in which -X 1 - in general formula (1) is -O-, and more preferably a linear or branched alkyl having 1 to 17 carbon atoms. an alkyl (meth)acrylate (a1) having a straight chain or branched alkyl group having 1 to 3 carbon atoms, and more preferably an alkyl (meth)acrylate (a1) having a straight chain or branched alkyl group having 1 to 3 carbon atoms; It is a combination with an alkyl (meth)acrylate (a2) having a group, more preferably an alkyl (meth)acrylate (a1) having a straight chain or branched alkyl group having 1 to 3 carbon atoms and a straight chain having 4 to 15 carbon atoms. It is a combination with an alkyl (meth)acrylate having a chain or branched alkyl group, and particularly preferably a combination of an alkyl (meth)acrylate (a1) having a straight chain or branched alkyl group having 1 to 3 carbon atoms and an alkyl (meth)acrylate having 6 to 13 carbon atoms. It is a combination with an alkyl (meth)acrylate having a straight chain or branched alkyl group.
　単量体（ａ）としては、Ｎｅｏｄｏｌ（登録商標）２３（炭素数１２～１３の直鎖及び分岐アルキルアルコールの混合物、ＳＨＥＬＬ社製）、Ｎｅｏｄｏｌ（登録商標）４５（炭素数１４～１５の直鎖及び分岐アルキルアルコールの混合物、ＳＨＥＬＬ社製）等のアルキルアルコールの混合物の（メタ）アクリル酸エステルを用いてもよい。 As the monomer (a), Neodol (registered trademark) 23 (mixture of linear and branched alkyl alcohols having 12 to 13 carbon atoms, manufactured by SHELL), Neodol (registered trademark) 45 (straight chain and branched alkyl alcohols having 14 to 15 carbon atoms), (Meth)acrylic acid esters of mixtures of alkyl alcohols, such as mixtures of chain and branched alkyl alcohols (SHELL) may also be used.
　本発明において、（共）重合体（Ａ）は、前記単量体（ａ）以外に水酸基含有単量体（ｅ）、窒素原子含有単量体（ｆ）（単量体（ａ）を除く）からなる群から選ばれる１種以上を構成単量体とする共重合体であってもよい。 In the present invention, the (co)polymer (A) includes, in addition to the monomer (a), a hydroxyl group-containing monomer (e) and a nitrogen atom-containing monomer (f) (excluding monomer (a)). ) may be a copolymer whose constituent monomer is one or more selected from the group consisting of:
　水酸基含有単量体（ｅ）としては、具体的には以下のものが挙げられる。
　水酸基含有芳香族単量体（ｐ－ヒドロキシスチレン等）、ヒドロキシアルキル（炭素数２～６）（メタ）アクリレート［２－ヒドロキシエチル（メタ）アクリレート、及び２－又は３－ヒドロキシプロピル（メタ）アクリレート等］、モノ－又はジ－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）アクリルアミド等］、ビニルアルコール、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－オクテノール及び１－ウンデセノール等］、炭素数４～１２のアルケンモノオール又はアルケンジオール［１－ブテン－３－オール、２－ブテン－１－オール及び２－ブテン－１，４－ジオール等］、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等）、多価（３～８価）アルコール（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、糖類及び蔗糖等）のアルケニル（炭素数３～１０）エーテル又は（メタ）アクリレート［蔗糖（メタ）アリルエーテル等］等；が挙げられる。これらの内、他の単量体との共重合性の観点から、ヒドロキシアルキル（炭素数２～６）（メタ）アクリレートが好ましく、更に好ましくはヒドロキシエチル（メタ）アクリレートである。 Specific examples of the hydroxyl group-containing monomer (e) include the following.
Hydroxyl group-containing aromatic monomer (p-hydroxystyrene, etc.), hydroxyalkyl (2-6 carbon atoms) (meth)acrylate [2-hydroxyethyl (meth)acrylate, and 2- or 3-hydroxypropyl (meth)acrylate etc.], mono- or di-hydroxyalkyl (1 to 4 carbon atoms) substituted (meth)acrylamides [N,N-dihydroxymethyl (meth)acrylamide, N,N-dihydroxypropyl (meth)acrylamide, N,N-dihydroxypropyl (meth)acrylamide, -2-hydroxybutyl (meth)acrylamide, etc.], vinyl alcohol, alkenol having 3 to 12 carbon atoms [(meth)allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1-octenol and 1-undecenol, etc.], carbon number 4 to 12 alkene monools or alkenediols [1-buten-3-ol, 2-buten-1-ol, 2-buten-1,4-diol, etc.], hydroxyalkyl (1 to 6 carbon atoms) alkenyl ( Alkenyls (3 to 10 carbon atoms) of ethers (2-hydroxyethylpropenyl ether, etc.), polyhydric (3 to 8-valent) alcohols (glycerin, pentaerythritol, sorbitol, sorbitan, diglycerin, sugars, sucrose, etc.) ~10) Ethers or (meth)acrylates [sucrose (meth)allyl ether, etc.]; and the like. Among these, from the viewpoint of copolymerizability with other monomers, hydroxyalkyl (2 to 6 carbon atoms) (meth)acrylate is preferred, and hydroxyethyl (meth)acrylate is more preferred.
　窒素原子含有単量体（ｆ）［単量体（ａ）を除く］としては、以下の単量体（ｆ１）～（ｆ４）が挙げられる。
　アミド基含有単量体（ｆ１）：
　（メタ）アクリルアミド、モノアルキルアミノアルキル（メタ）アクリルアミド［窒素原子に炭素数１～４のアルキル基が１つ結合したアミノアルキル基（炭素数２～６）を有するもの；例えばＮ－メチルアミノエチル（メタ）アクリルアミド、Ｎ－エチルアミノエチル（メタ）アクリルアミド、Ｎ－イソプロピルアミノ－ｎ－ブチル（メタ）アクリルアミド及びＮ－ｎ－又はイソブチルアミノ－ｎ－ブチル（メタ）アクリルアミド等］、ジアルキルアミノ（メタ）アクリルアミド［窒素原子に炭素数１～４のアルキル基が２つ結合したもの；例えばＮ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチル（メタ）アクリルアミド、Ｎ，Ｎ－ジイソプロピル（メタ）アクリルアミド及びＮ，Ｎ－ジ－ｎ－ブチル（メタ）アクリルアミド等］、ジアルキルアミノアルキル（メタ）アクリルアミド［窒素原子に炭素数１～４のアルキル基が２つ結合したアミノアルキル基（炭素数２～６）を有するもの；例えばＮ，Ｎ－ジメチルアミノエチル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチルアミノエチル（メタ）アクリルアミド、Ｎ，Ｎ－ジメチルアミノプロピル（メタ）アクリルアミド及びＮ，Ｎ－ジ－ｎ－ブチルアミノブチル（メタ）アクリルアミド等］、Ｎ－ビニルカルボン酸アミド［Ｎ－ビニルホルムアミド、Ｎ－ビニルアセトアミド、Ｎ－ビニル－ｎ－又はイソプロピオニルアミド及びＮ－ビニルヒドロキシアセトアミド等］等のアミド基のみに窒素原子を有するものが挙げられる。 Examples of the nitrogen atom-containing monomer (f) [excluding monomer (a)] include the following monomers (f1) to (f4).
Amide group-containing monomer (f1):
(Meth)acrylamide, monoalkylaminoalkyl (meth)acrylamide [having an aminoalkyl group (2 to 6 carbon atoms) in which one alkyl group of 1 to 4 carbon atoms is bonded to a nitrogen atom; for example, N-methylaminoethyl (meth)acrylamide, N-ethylaminoethyl (meth)acrylamide, N-isopropylamino-n-butyl (meth)acrylamide and Nn- or isobutylamino-n-butyl (meth)acrylamide, etc.], dialkylamino (meth)acrylamide, etc. ) Acrylamide [two alkyl groups having 1 to 4 carbon atoms bonded to a nitrogen atom; for example, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-diisopropyl(meth) acrylamide and N,N-di-n-butyl (meth)acrylamide, etc.], dialkylaminoalkyl (meth)acrylamide [aminoalkyl group in which two alkyl groups having 1 to 4 carbon atoms are bonded to a nitrogen atom (2 to 4 carbon atoms) 6); for example, N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide and N,N-di-n- butylaminobutyl (meth)acrylamide, etc.], N-vinylcarboxylic acid amide [N-vinylformamide, N-vinylacetamide, N-vinyl-n- or isopropionylamide, and N-vinylhydroxyacetamide, etc.] Examples include those having a nitrogen atom.
　ニトロ基含有単量体（ｆ２）：
　４－ニトロスチレン等が挙げられる。 Nitro group-containing monomer (f2):
Examples include 4-nitrostyrene.
　１～３級アミノ基含有単量体（ｆ３）：
　１級アミノ基含有ビニル単量体｛炭素数３～６のアルケニルアミン［（メタ）アリルアミン及びクロチルアミン等］、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）アクリレート等］｝；２級アミノ基含有ビニル単量体｛モノアルキルアミノアルキル（メタ）アクリレート［窒素原子に炭素数１～６のアルキル基が１つ結合したアミノアルキル基（炭素数２～６）を有するもの；例えばｔ－ブチルアミノエチル（メタ）アクリレート及びメチルアミノエチル（メタ）アクリレート等］、炭素数６～１２のジアルケニルアミン［ジ（メタ）アリルアミン等］｝；３級アミノ基含有ビニル単量体｛ジアルキルアミノアルキル（メタ）アクリレート［窒素原子に炭素数１～６のアルキル基が２つ結合したアミノアルキル基（炭素数２～６）を有するもの；例えばジメチルアミノエチル（メタ）アクリレート及びジエチルアミノエチル（メタ）アクリレート等］、窒素原子を有する脂環式（メタ）アクリレート［モルホリノエチル（メタ）アクリレート等］、芳香族ビニル系単量体［Ｎ，Ｎ－ジフェニルアミノエチル（メタ）アクリルアミド、Ｎ，Ｎ－ジメチルアミノスチレン、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－ビニルピロリドン及びＮ－ビニルチオピロリドン等］｝、及びこれらの塩酸塩、硫酸塩、リン酸塩又は低級アルキル（炭素数１～８）モノカルボン酸（酢酸及びプロピオン酸等）塩等が挙げられる。 Primary to tertiary amino group-containing monomer (f3):
Vinyl monomers containing primary amino groups {alkenylamines having 3 to 6 carbon atoms [(meth)allylamine, crotylamine, etc.], aminoalkyl (meth)acrylates (having 2 to 6 carbon atoms) [aminoethyl (meth)acrylate, etc.] }; Secondary amino group-containing vinyl monomer {monoalkylaminoalkyl (meth)acrylate [those having an aminoalkyl group (having 2 to 6 carbon atoms) in which one alkyl group having 1 to 6 carbon atoms is bonded to the nitrogen atom ; For example, t-butylaminoethyl (meth)acrylate and methylaminoethyl (meth)acrylate, etc.], dialkenylamine having 6 to 12 carbon atoms [di(meth)allylamine, etc.]; Tertiary amino group-containing vinyl monomer {Dialkylaminoalkyl (meth)acrylate [having an aminoalkyl group (2 to 6 carbon atoms) in which two alkyl groups of 1 to 6 carbon atoms are bonded to a nitrogen atom; for example, dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate, etc.], alicyclic (meth)acrylates having a nitrogen atom [morpholinoethyl (meth)acrylate, etc.], aromatic vinyl monomers [N,N-diphenylaminoethyl (meth)acrylamide, N, N-dimethylaminostyrene, 4-vinylpyridine, 2-vinylpyridine, N-vinylpyrrole, N-vinylpyrrolidone, N-vinylthiopyrrolidone, etc.], and their hydrochlorides, sulfates, phosphates, or lower alkyls (C1-8) monocarboxylic acid (acetic acid, propionic acid, etc.) salts, and the like.
　ニトリル基含有単量体（ｆ４）：
　（メタ）アクリロニトリル等が挙げられる。 Nitrile group-containing monomer (f4):
Examples include (meth)acrylonitrile.
　窒素原子含有ビニル単量体（ｆ）のうち、他の単量体との共重合性の観点から、好ましいのは、アミド基含有単量体（ｆ１）及び１～３級アミノ基含有単量体（ｆ３）であり、更に好ましいのは、Ｎ，Ｎ－ジフェニルアミノエチル（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、ジメチルアミノエチル（メタ）アクリレート及びジエチルアミノエチル（メタ）アクリレートである。 Among the nitrogen atom-containing vinyl monomers (f), preferred are amide group-containing monomers (f1) and monomers containing primary to tertiary amino groups from the viewpoint of copolymerizability with other monomers. (f3), and more preferred are N,N-diphenylaminoethyl (meth)acrylamide, dimethylaminoethyl (meth)acrylamide, diethylaminoethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate.
　重合体（Ａ）は、以下の単量体（ｇ）～（ｎ）を構成単量体としてもよい。 The polymer (A) may include the following monomers (g) to (n) as constituent monomers.
　脂肪族炭化水素単量体（ｇ）：
　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、ドデセン及びオクタデセン等）及び炭素数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－ヘプタジエン及び１，７－オクタジエン等）等が挙げられる。 Aliphatic hydrocarbon monomer (g):
Alkenes having 2 to 20 carbon atoms (ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, etc.) and alkadienes having 4 to 12 carbon atoms (butadiene, isoprene, 1,4-pentadiene, 1 , 6-heptadiene, 1,7-octadiene, etc.).
　脂環式炭化水素単量体（ｈ）：
　シクロヘキセン、（ジ）シクロペンタジエン、ピネン、リモネン、ビニルシクロヘキセン及びエチリデンビシクロヘプテン等が挙げられる。 Alicyclic hydrocarbon monomer (h):
Examples include cyclohexene, (di)cyclopentadiene, pinene, limonene, vinylcyclohexene and ethylidenebicycloheptene.
　芳香族炭化水素系単量体（ｉ）：
　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、インデン、４－クロチルベンゼン及び２－ビニルナフタレン等が挙げられる。 Aromatic hydrocarbon monomer (i):
Styrene, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, 4-ethylstyrene, 4-isopropylstyrene, 4-butylstyrene, 4-phenylstyrene, 4-cyclohexylstyrene, 4-benzylstyrene, indene, 4 -crotylbenzene and 2-vinylnaphthalene.
　ビニルエステル、ビニルエーテル、ビニルケトン類（ｊ）：
　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、酪酸ビニル及びオクタン酸ビニル等）、炭素数１～１２のアルキル、アリール又はアルコキシアルキルビニルエーテル（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及びビニル－２－ブトキシエチルエーテル等）及び炭素数１～８のアルキル又はアリールビニルケトン（メチルビニルケトン、エチルビニルケトン及びフェニルビニルケトン等）等が挙げられる。 Vinyl esters, vinyl ethers, vinyl ketones (j):
Vinyl esters of saturated fatty acids with 2 to 12 carbon atoms (vinyl acetate, vinyl propionate, vinyl butyrate, vinyl octoate, etc.), alkyl, aryl or alkoxyalkyl vinyl ethers with 1 to 12 carbon atoms (methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether) , butyl vinyl ether, 2-ethylhexyl vinyl ether, phenyl vinyl ether, vinyl-2-methoxyethyl ether, vinyl-2-butoxyethyl ether, etc.) and alkyl or aryl vinyl ketones having 1 to 8 carbon atoms (methyl vinyl ketone, ethyl vinyl ketone, phenyl vinyl ketone, etc.).
　エポキシ基含有単量体（ｋ）：
　グリシジル（メタ）アクリレート及びグリシジル（メタ）アリルエーテル等が挙げられる。 Epoxy group-containing monomer (k):
Examples include glycidyl (meth)acrylate and glycidyl (meth)allyl ether.
　ハロゲン元素含有単量体（ｌ）：
　塩化ビニル、臭化ビニル、塩化ビニリデン、塩化（メタ）アリル及びハロゲン化スチレン（ジクロロスチレン等）等が挙げられる。 Halogen element-containing monomer (l):
Examples include vinyl chloride, vinyl bromide, vinylidene chloride, (meth)allyl chloride, and halogenated styrene (dichlorostyrene, etc.).
　不飽和ポリカルボン酸のエステル（ｍ）：
　不飽和ポリカルボン酸のアルキル、シクロアルキル又はアラルキルエステル［不飽和ジカルボン酸（マレイン酸、フマール酸及びイタコン酸等）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及びジオクチルマレエート）］等が挙げられる。 Esters of unsaturated polycarboxylic acids (m):
Alkyl, cycloalkyl or aralkyl esters of unsaturated polycarboxylic acids [alkyl diesters having 1 to 8 carbon atoms of unsaturated dicarboxylic acids (maleic acid, fumaric acid, itaconic acid, etc.) (dimethyl maleate, dimethyl fumarate, diethyl maleate) and dioctyl maleate)].
　アルコキシアルキルエーテル単量体（ｎ）；
　メトキシエチル（メタ）アクリレート、メトキシプロピル（メタ）アクリレート、メトキシブチル（メタ）アクリレート、メトキシヘプチル（メタ）アクリレート、メトキシヘキシル（メタ）アクリレート、メトキシペンチル（メタ）アクリレート、メトキシオクチル（メタ）アクリレート、エトキシエチル（メタ）アクリレート、エトキシプロピル（メタ）アクリレート、エトキシブチル（メタ）アクリレート、エトキシヘプチル（メタ）アクリレート、エトキシヘキシル（メタ）アクリレート、エトキシペンチル（メタ）アクリレート、エトキシオクチル（メタ）アクリレート、プロポキシメチル（メタ）アクリレート、プロポキシエチル（メタ）アクリレート、プロポキシプロピル（メタ）アクリレート、プロポキシブチル（メタ）アクリレート、プロポキシヘプチル（メタ）アクリレート、プロポキシヘキシル（メタ）アクリレート、プロポキシペンチル（メタ）アクリレート、プロポキシオクチル（メタ）アクリレート、ブトキシメチル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、ブトキシプロピル（メタ）アクリレート、ブトキシブチル（メタ）アクリレート、ブトキシヘプチル（メタ）アクリレート、ブトキシヘキシル（メタ）アクリレート、ブトキシペンチル（メタ）アクリレート、ブトキシオクチル（メタ）アクリレート、等が挙げられる。
　単量体（ｎ）のうち、好ましいのは、メトキシエチル（メタ）アクリレート、エトキシエチル（メタ）アクリレート、ブトキシエチル（メタ）アクリレートである。 Alkoxyalkyl ether monomer (n);
Methoxyethyl (meth)acrylate, methoxypropyl (meth)acrylate, methoxybutyl (meth)acrylate, methoxyheptyl (meth)acrylate, methoxyhexyl (meth)acrylate, methoxypentyl (meth)acrylate, methoxyoctyl (meth)acrylate, ethoxy Ethyl (meth)acrylate, ethoxypropyl (meth)acrylate, ethoxybutyl (meth)acrylate, ethoxyheptyl (meth)acrylate, ethoxyhexyl (meth)acrylate, ethoxypentyl (meth)acrylate, ethoxyoctyl (meth)acrylate, propoxymethyl (meth)acrylate, propoxyethyl (meth)acrylate, propoxypropyl (meth)acrylate, propoxybutyl (meth)acrylate, propoxyheptyl (meth)acrylate, propoxyhexyl (meth)acrylate, propoxypentyl (meth)acrylate, propoxyoctyl ( meth)acrylate, butoxymethyl(meth)acrylate, butoxyethyl(meth)acrylate, butoxypropyl(meth)acrylate, butoxybutyl(meth)acrylate, butoxyheptyl(meth)acrylate, butoxyhexyl(meth)acrylate, butoxypentyl(meth)acrylate ) acrylate, butoxyoctyl (meth)acrylate, and the like.
Among the monomers (n), preferred are methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, and butoxyethyl (meth)acrylate.
　（共）重合体（Ａ）を構成する単量体（ａ）の割合は、粘度指数向上効果及び低温（－６０℃）での溶解性の観点から、（共）重合体（Ａ）の構成単量体の合計重量に基づいて、好ましくは７０～１００重量％であり、より好ましくは７８～１００重量％であり、特に好ましくは８５～１００重量％である。
　（共）重合体（Ａ）を構成する炭素数１～３の直鎖又は分岐アルキル基を有するアルキル（メタ）アクリレート（ａ１）の割合は、粘度指数向上効果及び低温（－６０℃）での溶解性の観点から、（共）重合体（Ａ）の構成単量体の合計重量に基づいて、好ましくは１０～７０重量％であり、より好ましくは１５～６０重量％であり、特に好ましくは２０～５５重量％である。
　（共）重合体（Ａ）を構成する炭素数４～１７の直鎖又は分岐アルキル基を有するアルキル（メタ）アクリレート（ａ２）の割合は、粘度指数向上効果及び低温（－６０℃）での溶解性の観点から、（共）重合体（Ａ）の構成単量体の合計重量に基づいて、好ましくは１０～９０重量％であり、より好ましくは２０～８５重量％であり、特に好ましくは３０～８０重量％である。
　（共）重合体（Ａ）を構成する単量体（ｅ）～（ｆ）の合計割合は、粘度指数向上効果の観点から、（共）重合体（Ａ）の構成単量体の合計重量に基づいて、好ましくは２０重量％以下であり、更に好ましくは１５重量％以下、特に好ましくは１０重量％以下である。
　（共）重合体（Ａ）を構成する単量体（ｇ）～（ｎ）の合計割合は、低温（－６０℃）での溶解性の観点から、（共）重合体（Ａ）の構成単量体の合計重量に基づいて、好ましくは１０重量％以下であり、更に好ましくは７重量％以下、特に好ましくは５重量％以下である。 The proportion of monomer (a) constituting the (co)polymer (A) is determined from the viewpoint of improving the viscosity index and solubility at low temperature (-60°C). Preferably it is 70 to 100% by weight, more preferably 78 to 100% by weight, particularly preferably 85 to 100% by weight, based on the total weight of the monomers.
The ratio of the alkyl (meth)acrylate (a1) having a straight chain or branched alkyl group having 1 to 3 carbon atoms constituting the (co)polymer (A) is determined by the viscosity index improvement effect and low temperature (-60°C) From the viewpoint of solubility, it is preferably 10 to 70% by weight, more preferably 15 to 60% by weight, and particularly preferably It is 20 to 55% by weight.
The proportion of the alkyl (meth)acrylate (a2) having a linear or branched alkyl group having 4 to 17 carbon atoms constituting the (co)polymer (A) is determined by the viscosity index improvement effect and low temperature (-60°C) From the viewpoint of solubility, it is preferably 10 to 90% by weight, more preferably 20 to 85% by weight, and particularly preferably It is 30 to 80% by weight.
The total proportion of monomers (e) to (f) constituting the (co)polymer (A) is determined by the total weight of the monomers constituting the (co)polymer (A) from the viewpoint of improving the viscosity index. Based on , it is preferably 20% by weight or less, more preferably 15% by weight or less, particularly preferably 10% by weight or less.
The total proportion of monomers (g) to (n) constituting the (co)polymer (A) is determined based on the composition of the (co)polymer (A) from the viewpoint of solubility at low temperature (-60°C). It is preferably at most 10% by weight, more preferably at most 7% by weight, particularly preferably at most 5% by weight, based on the total weight of the monomers.
　（共）重合体（Ａ）の溶解性パラメータ（以下においてＳＰ値と略記する）は、低温粘度、低温（－６０℃）での溶解性及び粘度指数向上効果の観点から、９．００～９．８０（ｃａｌ／ｃｍ３）１／２であり、好ましくは９．００～９．５０（ｃａｌ／ｃｍ３）１／２であり、より好ましくは９．１０～９．４０（ｃａｌ／ｃｍ３）１／２、更に好ましくは９．２０～９．４０（ｃａｌ／ｃｍ３）１／２であり、特に好ましくは９．２５～９．４０（ｃａｌ／ｃｍ３）１／２である。
　（共）重合体（Ａ）のＳＰ値が９．００（ｃａｌ／ｃｍ３）１／２以上であると低温粘度が低く、低温で析出しにくく、９．８０（ｃａｌ／ｃｍ３）１／２以下であると粘度指数向上効果が良好である。
　なお、本発明におけるＳＰ値は、Ｆｅｄｏｒｓ法（Ｐｏｌｙｍｅｒ　Ｅｎｇｉｎｅｅｒｉｎｇ　ａｎｄ　Ｓｃｉｅｎｃｅ，Ｆｅｂｒｕａｒｙ，１９７４，Ｖｏｌ．１４、Ｎｏ．２、Ｐ１４７～１５４）の１５２頁（Ｔａｂｌｅ．５）に記載の数値（原子又は官能基の２５℃における蒸発熱及びモル体積）を用いて、同１５３頁の数式（２８）により算出される値を意味する。具体的には、Ｆｅｄｏｒｓ法のパラメータである下記表１に記載のΔｅｉ及びｖｉの数値から、分子構造内の原子及び原子団の種類に対応した数値を用いて、下記数式に当てはめることで算出することができる。
ＳＰ値＝（ΣΔｅｉ／Σｖｉ）１／２
Figure JPOXMLDOC01-appb-T000004
  
　（共）重合体（Ａ）のＳＰ値は、前記ＳＰ値の算出方法を用いて（共）重合体（Ａ）を構成する各単量体に由来する構成単位（重合性炭素－炭素二重結合が重合反応により単結合となった構造）のＳＰ値を算出し、仕込み時の各構成単量体の重量分率に基づいて相加平均した値を意味する。例えば、単量体がメタクリル酸メチルの場合、メタクリル酸メチルに由来する構成単位は、原子団として、ＣＨ３が２個、ＣＨ２が１個、Ｃが１個、ＣＯ２が１個なので、下記数式により、メタクリル酸メチルに由来する構成単位のＳＰ値は９．９３３（ｃａｌ／ｃｍ３）１／２であることが分かる。同様に計算して、メタクリル酸ドデシルに由来する構成単位のＳＰ値は９．０１７（ｃａｌ／ｃｍ３）１／２であることがわかる。
ΣΔｅｉ＝１１２５×２＋１１８０＋３５０＋４３００＝８０８０
Σｖｉ＝３３．５×２＋１６．１－１９．２＋１８．０＝８１．９
δ＝（８０８０／８１．９）１／２＝９．９３３（ｃａｌ／ｃｍ３）１／２
　（共）重合体（Ａ）がメタクリル酸メチル２０重量％とメタクリル酸ドデシル８０重量％との重合物である場合、重合体のＳＰ値は、下記の通り各単量体に由来する構成単位のＳＰ値の重量分率に基づいて相加平均することにより算出される。
重合体のＳＰ値＝（９．９３３×２０＋９．０１７×８０）／１００＝９．２０
　（共）重合体（Ａ）のＳＰ値は、使用する単量体、重量分率を適宜調整することにより所望の範囲にすることができる。具体的には、アルキル基の炭素数の長い単量体を多く使用することでＳＰ値を小さくすることができ、アルキル基の炭素数の短い単量体を多く使用することでＳＰ値を大きくすることができる。 The solubility parameter (hereinafter abbreviated as SP value) of the (co)polymer (A) is 9.00 to 9.0 from the viewpoint of low temperature viscosity, solubility at low temperature (-60°C), and viscosity index improvement effect. .80 (cal/cm 3 ) 1/2 , preferably 9.00 to 9.50 (cal/cm 3 ) 1/2 , more preferably 9.10 to 9.40 (cal/cm 3 ) ) 1/2 , more preferably 9.20 to 9.40 (cal/cm 3 ) 1/2 , particularly preferably 9.25 to 9.40 (cal/cm 3 ) 1/2 .
When the SP value of the (co)polymer (A) is 9.00 (cal/cm 3 ) 1/2 or more, the low-temperature viscosity is low and it is difficult to precipitate at low temperatures, and it is 9.80 (cal/cm 3 ) 1/ When it is 2 or less, the viscosity index improving effect is good.
In addition, the SP value in the present invention is determined by the numerical value (atom or functional group (heat of vaporization and molar volume at 25° C.), it means the value calculated by formula (28) on page 153 of the same. Specifically, from the values of Δe i and v i listed in Table 1 below, which are the parameters of the Fedors method, by applying them to the following formula using values corresponding to the types of atoms and atomic groups in the molecular structure. It can be calculated.
SP value = (ΣΔe i /Σv i ) 1/2
Figure JPOXMLDOC01-appb-T000004
The SP value of the (co)polymer (A) is calculated using the above SP value calculation method. The SP value of the structure (in which the bond becomes a single bond due to a polymerization reaction) is calculated, and it means the arithmetic average value based on the weight fraction of each constituent monomer at the time of preparation. For example, when the monomer is methyl methacrylate, the constituent units derived from methyl methacrylate are 2 CH 3 , 1 CH 2 , 1 C, and 1 CO 2 as atomic groups. According to the following formula, it can be seen that the SP value of the structural unit derived from methyl methacrylate is 9.933 (cal/cm 3 ) 1/2 . Similar calculations show that the SP value of the structural unit derived from dodecyl methacrylate is 9.017 (cal/cm 3 ) 1/2 .
ΣΔe i =1125×2+1180+350+4300=8080
Σv i =33.5×2+16.1-19.2+18.0=81.9
δ=(8080/81.9) 1/2 =9.933(cal/cm 3 ) 1/2
When the (co)polymer (A) is a polymer of 20% by weight of methyl methacrylate and 80% by weight of dodecyl methacrylate, the SP value of the polymer is as follows: It is calculated by arithmetic averaging based on the weight fraction of the SP value.
SP value of polymer = (9.933×20+9.017×80)/100=9.20
The SP value of the (co)polymer (A) can be adjusted to a desired range by appropriately adjusting the monomers and weight fractions used. Specifically, the SP value can be reduced by using many monomers with a long alkyl group carbon number, and the SP value can be increased by using many monomers with a short alkyl group carbon number. can do.
　また、（共）重合体（Ａ）を２種以上用いる場合は、それぞれの（共）重合体（Ａ）のＳＰ値を基に重量分率を計算し、相加平均した値が上記ＳＰ値を満たすことが好ましい。 In addition, when using two or more types of (co)polymers (A), the weight fraction is calculated based on the SP value of each (co)polymer (A), and the arithmetic average value is the above SP value. It is preferable to satisfy the following.
　（共）重合体（Ａ）の重量平均分子量（Ｍｗ）は、粘度指数向上効果及びせん断安定性の観点から、好ましくは５，０００～３００，０００であり、更に好ましくは１０，０００～２５０，０００であり、特に好ましくは３０，０００～２００，０００であり、特に好ましくは５０，０００～１５０，０００である。 The weight average molecular weight (Mw) of the (co)polymer (A) is preferably 5,000 to 300,000, more preferably 10,000 to 250, from the viewpoint of improving the viscosity index and shear stability. 000, particularly preferably from 30,000 to 200,000, particularly preferably from 50,000 to 150,000.
　＜（共）重合体（Ａ）のＧＰＣによるＭｗ、Ｍｎの測定条件＞
装置　　：「ＨＬＣ－８３２０ＧＰＣ」［東ソー（株）製］
カラム　：「ＴＳＫｇｅｌｇｕａｒｄｃｏｌｕｍｎＳｕｐｅｒＨＺＭ－Ｍ」
　［東ソー（株）製］　
「ＴＳＫｇｅｌ　ＳｕｐｅｒＨＺＭ－Ｍ」　３本　
　［東ソー（株）製］　
測定温度　：４０℃
試料溶液　：０．２５重量％のテトラヒドロフラン溶液　
溶液注入量：１０．０μｌ
検出装置　：屈折率検出器
基準物質　：標準ポリスチレン（ＴＳ　基準物質　：標準ポリスチレン（ＴＳＫｓｔａｎｄａｒｄ　ＰＯＬＹＳＴＹＲＥＮＥ））
１２点（分子量：５８９、１，０５０、２，６３０、９，１００、１９，５００、３７，９００、９６，４００、１９０，０００、３５５，０００、１，０９０，０００、２，１１０，０００、４，４８０，０００）［東ソー（株）製］ <Measurement conditions of Mw and Mn by GPC of (co)polymer (A)>
Equipment: “HLC-8320GPC” [manufactured by Tosoh Corporation]
Column: "TSKgelguardcolumnSuperHZM-M"
[Manufactured by Tosoh Corporation]
"TSKgel SuperHZM-M" 3 bottles
[Manufactured by Tosoh Corporation]
Measurement temperature: 40℃
Sample solution: 0.25% by weight tetrahydrofuran solution
Solution injection amount: 10.0μl
Detection device: Refractive index detector Reference material: Standard polystyrene (TS Reference material: Standard polystyrene (TSK standard POLYSTYRENE))
12 points (molecular weight: 589, 1,050, 2,630, 9,100, 19,500, 37,900, 96,400, 190,000, 355,000, 1,090,000, 2,110,000 , 4,480,000) [manufactured by Tosoh Corporation]
　（共）重合体（Ａ）は、公知の製造方法によって得ることができ、具体的には前記の単量体を溶剤中で重合触媒存在下に溶液重合することにより得る方法が挙げられる。
　溶剤としては、トルエン、キシレン、炭素数９～１０のアルキルベンゼン、メチルエチルケトン、酢酸エチル、２－プロパノール及びリン酸エステル（Ｃ）等が挙げられる。
　重合触媒としては、アゾ系触媒（アゾビスイソブチロニトリル及びアゾビスバレロニトリル等）、過酸化物系触媒（ベンゾイルパーオキサイド、クミルパーオキサイド及びラウリルパーオキサイド等）及びレドックス系触媒（ベンゾイルパーオキサイドと３級アミンの混合物等）が挙げられる。更に必要により、公知の連鎖移動剤（炭素数２～２０のアルキルメルカプタン等）を使用することもできる。
　重合温度は、好ましくは２５～１４０℃であり、更に好ましくは５０～１２０℃である。また、上記の溶液重合の他に、塊状重合、乳化重合又は懸濁重合により（共）重合体（Ａ）を得ることができる。
　（共）重合体（Ａ）が共重合体である場合の重合形態としては、ランダム付加重合体又は交互共重合体のいずれでもよく、また、グラフト共重合体又はブロック共重合体のいずれでもよい。 The (co)polymer (A) can be obtained by a known production method, specifically a method of solution polymerizing the above-mentioned monomers in a solvent in the presence of a polymerization catalyst.
Examples of the solvent include toluene, xylene, alkylbenzene having 9 to 10 carbon atoms, methyl ethyl ketone, ethyl acetate, 2-propanol, and phosphoric acid ester (C).
Examples of polymerization catalysts include azo catalysts (azobisisobutyronitrile and azobisvaleronitrile, etc.), peroxide catalysts (benzoyl peroxide, cumyl peroxide, lauryl peroxide, etc.), and redox catalysts (benzoyl peroxide, etc.). and tertiary amine). Furthermore, if necessary, a known chain transfer agent (such as an alkyl mercaptan having 2 to 20 carbon atoms) may be used.
The polymerization temperature is preferably 25 to 140°C, more preferably 50 to 120°C. In addition to the solution polymerization described above, the (co)polymer (A) can be obtained by bulk polymerization, emulsion polymerization, or suspension polymerization.
When the (co)polymer (A) is a copolymer, the polymerization form may be either a random addition polymer or an alternating copolymer, or a graft copolymer or a block copolymer. .
＜鎖状脂肪族アルコール（Ｂ）＞
　本発明の粘度指数向上剤組成物は、ＨＬＢ値が２．５～７．０である鎖状脂肪族アルコール（Ｂ）を含有する。ＨＬＢ値が２．５以上であると、低温（－６０℃）で析出物が発生しにくく、７．０以下であるとリン酸エステルの加水分解抑制効果に優れる。（Ｂ）のＨＬＢが７．０以下であると潤滑油中に混入した水に対してミセルを形成し、リン酸エステルの加水分解を抑制することができると推察され、２．５以上であると（共）重合体（Ａ）との相溶性が高く低温（－６０℃）でも基油中に溶解することができると推察される。
　鎖状脂肪族アルコール（Ｂ）のＨＬＢ値は、３．０～６．０が好ましく、更に好ましくは４．０～５．０である。
　本発明において、ＨＬＢ値とは、親水性と親油性のバランスを示す指標であって、例えば「界面活性剤入門」〔２００７年三洋化成工業株式会社発行、藤本武彦著〕２１２頁に記載されている小田法による計算値として知られているものであり、グリフィン法による計算値ではない。
　ＨＬＢ値は有機化合物の有機性の値と無機性の値との比率から計算することができる。
ＨＬＢ＝１０×無機性／有機性
　ＨＬＢを導き出すための有機性の値及び無機性の値については有機性の数値として、炭素原子１個あたり２０と定め、無機性の数値としては前記「界面活性剤入門」２１３頁に記載の表の値を用いて算出する。算出例として、「－ＣＨ３基：有機性値２０、無機性値０」、「－ＣＨ２－基：有機性値２０、無機性値０」、「＝ＣＨ２基（二重結合）：有機性値２０、無機性値２」、「＝ＣＨ－基（二重結合）：有機性値２０、無機性値２」、「ｉｓｏ分岐炭素：有機性値１０、無機性値０」、「ｔｅｒｔ分岐炭素：有機性値０、無機性値０」、「－Ｏ－基：有機性値０、無機性値２０」、「－ＯＨ基：有機性値０、無機性値１００」等が挙げられる。
　例えば、ドデカノール｛ＣＨ３（ＣＨ２）１１ＯＨ｝の場合は、下記となる。
ＨＬＢ値＝１０×（１００）／（２０×１１＋２０）＝４．１７
　また、ＨＬＢ値が異なる鎖状脂肪族アルコール（Ｂ）を複数含有する場合は、重量分率に基づく相加平均値が上記範囲であることが好ましい。 <Chained aliphatic alcohol (B)>
The viscosity index improver composition of the present invention contains a chain aliphatic alcohol (B) having an HLB value of 2.5 to 7.0. When the HLB value is 2.5 or more, precipitates are less likely to be generated at low temperatures (-60° C.), and when it is 7.0 or less, the effect of suppressing the hydrolysis of phosphate ester is excellent. It is presumed that when the HLB of (B) is 7.0 or less, micelles can be formed against the water mixed in the lubricating oil and hydrolysis of the phosphate ester can be suppressed, and when the HLB is 2.5 or more. It is presumed that the compatibility between the (co)polymer (A) and (co)polymer (A) is high and that it can be dissolved in the base oil even at low temperatures (-60°C).
The HLB value of the chain aliphatic alcohol (B) is preferably 3.0 to 6.0, more preferably 4.0 to 5.0.
In the present invention, the HLB value is an index indicating the balance between hydrophilicity and lipophilicity, and is described, for example, in "Introduction to Surfactants" [published by Sanyo Chemical Industries, Ltd., 2007, written by Takehiko Fujimoto], page 212. This is known as the value calculated by the Oda method, and not the value calculated by the Griffin method.
The HLB value can be calculated from the ratio of the organic value and the inorganic value of an organic compound.
HLB=10×Inorganic/Organic The organic value and inorganic value for deriving HLB are determined as 20 per carbon atom as the organic value, and the inorganic value is determined as Calculated using the values in the table described on page 213 of "Introduction to Drugs". As calculation examples, "-CH 3 group: organic value 20, inorganic value 0", "-CH 2 - group: organic value 20, inorganic value 0", "=CH 2 group (double bond): Organic value 20, inorganic value 2", "=CH- group (double bond): organic value 20, inorganic value 2", "iso branched carbon: organic value 10, inorganic value 0", " tert-branched carbon: organic value 0, inorganic value 0", "-O- group: organic value 0, inorganic value 20", "-OH group: organic value 0, inorganic value 100", etc. It will be done.
For example, in the case of dodecanol {CH 3 (CH 2 ) 11 OH}, it is as follows.
HLB value = 10 x (100) / (20 x 11 + 20) = 4.17
Furthermore, when a plurality of chain aliphatic alcohols (B) having different HLB values are contained, it is preferable that the arithmetic average value based on the weight fraction is within the above range.
　鎖状脂肪族アルコール（Ｂ）としては、炭素数８～１７のものが含まれ、例えば、直鎖状飽和脂肪族アルコール｛例えば、１－デカノール（ＨＬＢ値＝５．００）、１－ドデカノール（ＨＬＢ値＝４．１７）、１－トリデカノール（ＨＬＢ＝３．８５）、１－テトラデカノール（ＨＬＢ＝３．５７）、１－ペンタデカノール（ＨＬＢ＝３．３３）、１－ヘキサデカノール（ＨＬＢ＝３．１３）、１－ヘプタデカノール（ＨＬＢ＝２．９４）等｝、分岐鎖状飽和脂肪族アルコール｛例えば、２－エチルヘキサノール（ＨＬＢ値＝６．６７）、イソデカノール（ＨＬＢ値＝５．２６）、２－メチル－１－ウンデカノール（ＨＬＢ＝４．３５）、２－メチル－１－ドデカノール（ＨＬＢ＝４．００）、２－メチル－１－トリデカノール（ＨＬＢ＝３．７０）、２－メチル－１－テトラデカノール（ＨＬＢ＝３．４５）等｝等が挙げられる。 The chain aliphatic alcohol (B) includes those having 8 to 17 carbon atoms, such as linear saturated aliphatic alcohols {for example, 1-decanol (HLB value = 5.00), 1-dodecanol ( HLB value = 4.17), 1-tridecanol (HLB = 3.85), 1-tetradecanol (HLB = 3.57), 1-pentadecanol (HLB = 3.33), 1-hexadecanol (HLB=3.13), 1-heptadecanol (HLB=2.94), etc.}, branched saturated aliphatic alcohols {for example, 2-ethylhexanol (HLB value=6.67), isodecanol (HLB value = 5.26), 2-methyl-1-undecanol (HLB = 4.35), 2-methyl-1-dodecanol (HLB = 4.00), 2-methyl-1-tridecanol (HLB = 3.70) , 2-methyl-1-tetradecanol (HLB=3.45), etc.}.
　鎖状脂肪族アルコール（Ｂ）としては、潤滑油組成物の経時安定性向上（リン酸エステルの加水分解抑制効果）の観点から、炭素数８～１７の直鎖又は分岐鎖状脂肪族アルコールが好ましく、さらに好ましくは炭素数９～１６の直鎖又は分岐鎖状脂肪族アルコールであり、特に好ましくは炭素数１０～１５の直鎖又は分岐鎖状脂肪族アルコールである。 As the chain aliphatic alcohol (B), from the viewpoint of improving the stability of the lubricating oil composition over time (suppressing hydrolysis of phosphate ester), a straight chain or branched aliphatic alcohol having 8 to 17 carbon atoms is used. Preferably, straight-chain or branched aliphatic alcohols having 9 to 16 carbon atoms are preferred, and straight-chain or branched aliphatic alcohols having 10 to 15 carbon atoms are particularly preferred.
　鎖状脂肪族アルコール（Ｂ）のＳＰ値は、潤滑油の経時安定性向上の観点から、９．００～１０．２０（ｃａｌ／ｃｍ３）１／２が好ましく、更に好ましくは９．５０～１０．００（ｃａｌ／ｃｍ３）１／２である。
　また、ＳＰ値が異なる鎖状脂肪族アルコール（Ｂ）を複数含有する場合は、重量分率に基づく相加平均値が上記範囲であることが好ましい。 The SP value of the chain aliphatic alcohol (B) is preferably 9.00 to 10.20 (cal/cm 3 ) 1/2 , more preferably 9.50 to 1/2, from the viewpoint of improving the stability of the lubricating oil over time. 10.00 (cal/cm 3 ) 1/2 .
Further, when a plurality of chain aliphatic alcohols (B) having different SP values are contained, it is preferable that the arithmetic average value based on the weight fraction is within the above range.
＜リン酸エステル（Ｃ）＞
　本発明の粘度指数向上剤組成物は、粘度指数向上効果に優れ、リン酸エステルの加水分解抑制効果に優れ、さらに低温（－６０℃）でも析出物が無く、低温での粘度が良好な潤滑油組成物を得ることができるので、リン酸エステル（Ｃ）を含有する潤滑油組成物用の粘度指数向上剤組成物として用いることができる。
　リン酸エステル（Ｃ）としては、例えば、下記一般式（２）で表されるものが挙げられる。
Ｒ４Ｏ－Ｐ（Ｏ）－（ＯＲ４）２　　（２）
［一般式（２）中、Ｒ４はそれぞれ独立に炭素数１～１０の炭化水素基を表す。］ <Phosphoric acid ester (C)>
The viscosity index improver composition of the present invention has an excellent effect of improving the viscosity index, an excellent effect of suppressing hydrolysis of phosphate ester, and is free from precipitates even at low temperatures (-60°C), and has a good viscosity at low temperatures for lubricating. Since an oil composition can be obtained, it can be used as a viscosity index improver composition for lubricating oil compositions containing phosphate ester (C).
Examples of the phosphoric acid ester (C) include those represented by the following general formula (2).
R 4 OP(O)-(OR 4 ) 2 (2)
[In general formula (2), R 4 each independently represents a hydrocarbon group having 1 to 10 carbon atoms. ]
　一般式（２）において、炭素数１～１０の炭化水素基としては、炭素数１～１０のアルキル基｛例えば、直鎖アルキル基（例えば、メチル基、エチル基、ｎ－プロピル基、ｎ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基等）、分岐鎖アルキル基（例えば、イソプロピル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、イソペンチル基、ネオペンチル基、イソヘキシル基、２－エチルヘキシル基等）｝、炭素数６～１０のアリール基｛例えば、フェニル基、アルキル置換アリール基（例えば、トリル基、キシリル基、ｎ－プロピルフェニル基、イソプロピルフェニル基、ｎ－ブチルフェニル基、イソブチルフェニル基等）等｝等が挙げられる。
　炭素数１～１０の炭化水素基としては、低温粘度と引火点の観点から、炭素数１～６の炭化水素基が好ましく、さらに好ましくは炭素数２～４の炭化水素基である。 In general formula (2), the hydrocarbon group having 1 to 10 carbon atoms includes an alkyl group having 1 to 10 carbon atoms {for example, a straight chain alkyl group (for example, a methyl group, an ethyl group, an n-propyl group, an n- butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, etc.), branched alkyl group (e.g. isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group) , neopentyl group, isohexyl group, 2-ethylhexyl group)}, aryl group having 6 to 10 carbon atoms {for example, phenyl group, alkyl-substituted aryl group (for example, tolyl group, xylyl group, n-propylphenyl group, isopropylphenyl group) group, n-butylphenyl group, isobutylphenyl group, etc.).
From the viewpoint of low-temperature viscosity and flash point, the hydrocarbon group having 1 to 10 carbon atoms is preferably a hydrocarbon group having 1 to 6 carbon atoms, and more preferably a hydrocarbon group having 2 to 4 carbon atoms.
　リン酸エステル（Ｃ）としては、例えば、リン酸トリ（イソプロピル）、リン酸トリ（ｎ－ブチル）、リン酸トリ（イソブチル）、リン酸トリ（ｓｅｃ－ブチル）、リン酸トリ（ｔｅｒｔ－ブチル）、リン酸ｎ－ブチルジイソブチル、リン酸ジ－ｎ－ブチルイソブチル、リン酸ジイソブチルペンチル、リン酸トリ（ｎ－ペンチル）、リン酸トリ（イソペンチル）、リン酸トリ（２－エチルヘキシル）、リン酸ｎ－ブチルジフェニル、リン酸イソブチルジフェニル、リン酸トリフェニル、リン酸トリ（イソプロピルフェニル）、リン酸トリ（イソブチルフェニル）等が挙げられる。
　これらのうち、低温粘度と引火点の観点から、リン酸トリ（ｎ－ブチル）、リン酸トリ（イソブチル）、リン酸トリ（ｓｅｃ－ブチル）、リン酸トリ（ｔｅｒｔ－ブチル）、リン酸トリフェニル、リン酸トリ（イソプロピルフェニル）が好ましく、さらに好ましくはリン酸トリ（ｎ－ブチル）、リン酸トリ（イソブチル）である。 Examples of the phosphate ester (C) include tri(isopropyl) phosphate, tri(n-butyl) phosphate, tri(isobutyl) phosphate, tri(sec-butyl) phosphate, and tert-butyl phosphate. ), n-butyldiisobutyl phosphate, di-n-butylisobutyl phosphate, diisobutylpentyl phosphate, tri(n-pentyl) phosphate, tri(isopentyl) phosphate, tri(2-ethylhexyl) phosphate, phosphoric acid Examples include n-butyldiphenyl, isobutyldiphenyl phosphate, triphenyl phosphate, tri(isopropylphenyl) phosphate, and tri(isobutylphenyl) phosphate.
Among these, from the viewpoint of low-temperature viscosity and flash point, tri(n-butyl) phosphate, tri(isobutyl) phosphate, tri(sec-butyl) phosphate, tri(tert-butyl) phosphate, tri(t-butyl) phosphate, Phenyl and tri(isopropylphenyl) phosphate are preferred, and tri(n-butyl) phosphate and tri(isobutyl) phosphate are more preferred.
　リン酸エステル（Ｃ）の１００℃における動粘度（ＡＳＴＭ　Ｄ　４４５に準拠して測定したもの）は、低温粘度の観点から、１～５ｍｍ２／ｓが好ましく、更に好ましくは１～４ｍｍ２／ｓ、特に好ましくは１～３．５ｍｍ２／ｓである。
　リン酸エステル（Ｃ）の４０℃における動粘度（ＡＳＴＭ　Ｄ　４４５に準拠して測定したもの）は、低温粘度の観点から、１～４０ｍｍ２／ｓが好ましく、更に好ましくは１～２５ｍｍ２／ｓ、特に好ましくは１～２０ｍｍ２／ｓである。 The kinematic viscosity (measured according to ASTM D 445) at 100°C of the phosphoric acid ester (C) is preferably 1 to 5 mm 2 /s, more preferably 1 to 4 mm 2 /s from the viewpoint of low-temperature viscosity. , particularly preferably 1 to 3.5 mm 2 /s.
The kinematic viscosity (measured according to ASTM D 445) at 40°C of the phosphoric acid ester (C) is preferably 1 to 40 mm 2 /s, more preferably 1 to 25 mm 2 /s from the viewpoint of low-temperature viscosity. , particularly preferably 1 to 20 mm 2 /s.
＜粘度指数向上剤組成物＞
　本発明の粘度指数向上剤組成物は、前記（共）重合体（Ａ）と、前記鎖状脂肪族アルコール（Ｂ）とを含有する粘度指数向上剤組成物である。
　本発明の粘度指数向上剤組成物は、前記（共）重合体（Ａ）を含有することで、リン酸エステル（Ｃ）を含む潤滑油組成物に添加した際の潤滑油組成物の粘度指数向上効果が高く、前記鎖状脂肪族アルコール（Ｂ）を含有することでリン酸エステル（Ｃ）の加水分解を抑制する効果に優れる。また、前記鎖状脂肪族アルコール（Ｂ）は特に低温（－６０℃）でリン酸エステル（Ｃ）中で析出しやすいところ、（共）重合体（Ａ）と前記鎖状脂肪族アルコール（Ｂ）とを同時に含有することで、リン酸エステル（Ｃ）中で析出しにくいものとすることができる。したがって、本発明の粘度指数向上剤組成物は、前記（共）重合体（Ａ）と前記鎖状脂肪族アルコール（Ｂ）とを含有することにより、潤滑油組成物の粘度指数向上、リン酸エステル（Ｃ）の加水分解による潤滑性の悪化の抑制、低温での析出を抑制のすべてを達成することができるものである。 <Viscosity index improver composition>
The viscosity index improver composition of the present invention is a viscosity index improver composition containing the (co)polymer (A) and the chain aliphatic alcohol (B).
By containing the above-mentioned (co)polymer (A), the viscosity index improver composition of the present invention can improve the viscosity index of the lubricating oil composition when added to a lubricating oil composition containing the phosphate ester (C). The improvement effect is high, and by containing the chain aliphatic alcohol (B), the effect of suppressing the hydrolysis of the phosphoric acid ester (C) is excellent. In addition, the chain aliphatic alcohol (B) tends to precipitate in the phosphoric ester (C) especially at low temperatures (-60°C), and the (co)polymer (A) and the chain aliphatic alcohol (B) tend to precipitate in the phosphate ester (C). ) can be made to be difficult to precipitate in the phosphoric ester (C). Therefore, the viscosity index improver composition of the present invention improves the viscosity index of the lubricating oil composition by containing the (co)polymer (A) and the chain aliphatic alcohol (B). It is possible to suppress deterioration of lubricity due to hydrolysis of ester (C) and suppress precipitation at low temperatures.
　粘度指数向上剤組成物中の前記（共）重合体（Ａ）と前記鎖状脂肪族アルコール（Ｂ）の重量比率（Ａ／Ｂ）は、潤滑油の経時安定性向上及び粘度指数向上効果の観点から、１０～５０００が好ましく、更に好ましくは１０～３０００であり、特に好ましくは１０～５００である。 The weight ratio (A/B) of the above-mentioned (co)polymer (A) and the above-mentioned chain aliphatic alcohol (B) in the viscosity index improver composition has the effect of improving the stability over time and improving the viscosity index of the lubricating oil. From this point of view, it is preferably 10 to 5,000, more preferably 10 to 3,000, particularly preferably 10 to 500.
　（共）重合体（Ａ）のＳＰ値と鎖状脂肪族アルコール（Ｂ）のＳＰ値との差の絶対値は、潤滑油の経時安定性向上の観点から、０．１０～１．００（ｃａｌ／ｃｍ３）１／２が好ましく、更に好ましくは０．２０～０．９０（ｃａｌ／ｃｍ３）１／２である。
　また、ＳＰ値が異なる（共）重合体（Ａ）及び鎖状脂肪族アルコール（Ｂ）をそれぞれ複数含有する場合は、それぞれ重量分率に基づく相加平均値の差の絶対値が上記範囲であることが好ましい。 The absolute value of the difference between the SP value of the (co)polymer (A) and the SP value of the chain aliphatic alcohol (B) is 0.10 to 1.00 ( It is preferably 0.20 to 0.90 (cal/cm 3 ) 1/2 , more preferably 0.20 to 0.90 (cal/cm 3 ) 1/2 .
In addition, if a plurality of (co)polymers (A) and chain aliphatic alcohols (B) each having different SP values are contained, the absolute value of the difference in arithmetic average values based on the respective weight fractions should be within the above range. It is preferable that there be.
　本発明の粘度指数向上剤組成物は、前記（共）重合体（Ａ）と前記鎖状脂肪族アルコール（Ｂ）とを含有していればよく、取り扱い性の観点から、リン酸エステル（Ｃ）を含有していてもよい。
　粘度指数向上剤組成物中の（共）重合体（Ａ）の含有量は、粘度指数向上剤組成物の取り扱い性の観点から、粘度指数向上剤組成物の重量を基準として、１０～７０重量％が好ましく、更に好ましくは２０～６０重量％である。
　粘度指数向上剤組成物中の鎖状脂肪族アルコール（Ｂ）の含有量は、潤滑油組成物を製造した際の経変安定性の観点から、粘度指数向上剤組成物の重量を基準として、０．０１～５．００重量％が好ましく、更に好ましくは０．１～４．５０重量％である。
　粘度指数向上剤組成物中のリン酸エステル（Ｃ）の含有量は、低温粘度の観点から、粘度指数向上剤組成物の重量を基準として、２５～８９重量％が好ましく、更に好ましくは３５．５～７９重量％である。 The viscosity index improver composition of the present invention only needs to contain the above-mentioned (co)polymer (A) and the above-mentioned chain aliphatic alcohol (B). ) may also be included.
The content of the (co)polymer (A) in the viscosity index improver composition is 10 to 70% by weight based on the weight of the viscosity index improver composition, from the viewpoint of ease of handling the viscosity index improver composition. %, more preferably 20 to 60% by weight.
The content of the chain aliphatic alcohol (B) in the viscosity index improver composition is based on the weight of the viscosity index improver composition, from the viewpoint of stability over time when producing a lubricating oil composition. It is preferably 0.01 to 5.00% by weight, more preferably 0.1 to 4.50% by weight.
From the viewpoint of low-temperature viscosity, the content of the phosphoric acid ester (C) in the viscosity index improver composition is preferably 25 to 89% by weight, more preferably 35% by weight, based on the weight of the viscosity index improver composition. It is 5 to 79% by weight.
　本発明の粘度指数向上剤組成物を用いれば、粘度指数向上効果及びリン酸エステルの加水分解抑制効果に優れ、さらに低温（－６０℃）でも析出物がなく、低温での粘度が良好な潤滑油組成物を得ることができるので、リン酸エステル（Ｃ）を含む潤滑油組成物用の粘度指数向上剤として用いることができ、さらにリン酸エステル（Ｃ）を基油として含む潤滑油組成物の粘度指数向上剤として好ましく用いることができ、特に上空（低温環境下）で用いられることのある航空機用油圧作動油用の粘度指数向上剤として有用である。 If the viscosity index improver composition of the present invention is used, the viscosity index improver composition has an excellent viscosity index improvement effect and a phosphate ester hydrolysis inhibiting effect, and furthermore, there is no precipitate even at low temperatures (-60°C), and the viscosity at low temperatures is good for lubricants. Since the oil composition can be obtained, it can be used as a viscosity index improver for lubricating oil compositions containing phosphoric ester (C), and further containing phosphoric ester (C) as a base oil. It is particularly useful as a viscosity index improver for aircraft hydraulic fluids that may be used in the sky (under low-temperature environments).
＜潤滑油組成物＞
　本発明の潤滑油組成物は、前記粘度指数向上剤組成物とリン酸エステル（Ｃ）とを含有する。
　潤滑油組成物中の（共）重合体（Ａ）の含有量は、低温粘度と１００℃での動粘度の観点から、潤滑油組成物の重量を基準として、１～１５重量％が好ましく、更に好ましくは２～１０重量％である。
　潤滑油組成物中の鎖状脂肪族アルコール（Ｂ）の含有量は、潤滑油の経変安定性の観点から、潤滑油組成物の重量を基準として、０．０１～０．６重量％が好ましく、更に好ましくは０．０５～０．５５重量％である。
　潤滑油組成物中のリン酸エステル（Ｃ）の含有量は、低温粘度の観点から、潤滑油組成物の重量を基準として、７５重量％以上が好ましく、より好ましくは７５～９８．９９重量％、更に好ましくは８０～９７．９５重量％である。
　潤滑油組成物中の前記（共）重合体（Ａ）と前記鎖状脂肪族アルコール（Ｂ）の重量比率（Ａ／Ｂ）は、粘度指数向上効果の観点から、１０～５０００が好ましく、更に好ましくは１０～３０００であり、特に好ましくは１０～５００である。 <Lubricating oil composition>
The lubricating oil composition of the present invention contains the viscosity index improver composition and a phosphoric acid ester (C).
The content of the (co)polymer (A) in the lubricating oil composition is preferably 1 to 15% by weight based on the weight of the lubricating oil composition from the viewpoint of low-temperature viscosity and kinematic viscosity at 100 ° C. More preferably, it is 2 to 10% by weight.
The content of the chain aliphatic alcohol (B) in the lubricating oil composition is from 0.01 to 0.6% by weight based on the weight of the lubricating oil composition from the viewpoint of stability over time of the lubricating oil. It is preferably 0.05 to 0.55% by weight, and more preferably 0.05 to 0.55% by weight.
The content of phosphate ester (C) in the lubricating oil composition is preferably 75% by weight or more, more preferably 75 to 98.99% by weight, based on the weight of the lubricating oil composition, from the viewpoint of low-temperature viscosity. , more preferably 80 to 97.95% by weight.
The weight ratio (A/B) of the (co)polymer (A) and the chain aliphatic alcohol (B) in the lubricating oil composition is preferably 10 to 5,000 from the viewpoint of improving the viscosity index, and It is preferably 10 to 3,000, particularly preferably 10 to 500.
　潤滑油組成物に含まれるリン酸エステル（Ｃ）は、粘度指数向上剤組成物に含まれていたリン酸エステル（Ｃ）であってもよいし、粘度指数向上剤組成物以外に由来するリン酸エステル（Ｃ）であってもよい。また、潤滑油組成物に含まれるリン酸エステル（Ｃ）は、粘度指数向上剤組成物に含まれていたリン酸エステル（Ｃ）と粘度指数向上剤組成物以外に由来するリン酸エステル（Ｃ）の混合物であってもよい。 The phosphoric ester (C) contained in the lubricating oil composition may be the phosphoric ester (C) contained in the viscosity index improver composition, or may be the phosphoric ester (C) that is derived from a source other than the viscosity index improver composition. It may also be an acid ester (C). In addition, the phosphoric ester (C) contained in the lubricating oil composition is the phosphoric ester (C) derived from a source other than the phosphoric ester (C) contained in the viscosity index improver composition and the viscosity index improver composition. ) may be a mixture.
　潤滑油組成物に含まれるリン酸エステル（Ｃ）としては、上述したリン酸エステル（Ｃ）を用いることができる。粘度指数向上剤組成物以外に由来するリン酸エステル（Ｃ）としては、リン酸トリ（ｎ－ブチル）が好ましく、リン酸トリ（イソプロピルフェニル）とリン酸トリフェニルの混合物も好ましい。
　潤滑油組成物に含まれるリン酸エステル（Ｃ）の４０℃における動粘度が、１～４０ｍｍ２／ｓであることが好ましい。 As the phosphoric ester (C) contained in the lubricating oil composition, the above-mentioned phosphoric ester (C) can be used. As the phosphoric acid ester (C) derived from a source other than the viscosity index improver composition, tri(n-butyl) phosphate is preferred, and a mixture of tri(isopropylphenyl) phosphate and triphenyl phosphate is also preferred.
It is preferable that the phosphoric acid ester (C) contained in the lubricating oil composition has a kinematic viscosity at 40° C. of 1 to 40 mm 2 /s.
＜粘度指数向上剤組成物及び潤滑油組成物中の鎖状脂肪族アルコール（Ｂ）の含有量の測定方法＞
　本発明の粘度指数向上剤組成物又は潤滑油組成物１ｇを、ソックスレー抽出器を用いて、ヘキサン溶剤３００ｍｌにより（共）重合体（Ａ）成分とヘキサン溶剤に溶解するその他成分に分離抽出する。鎖状脂肪族アルコール（Ｂ）はヘキサンに溶解するので、抽出されたその他成分中に含まれる。抽出したその他成分を含む溶液中のヘキサン溶剤をエバポレーターにより減圧留去する。
　留去せずに残ったその他成分抽出物の量Ｘ（ｍｇ）のうち１０ｍｇを精秤し、そこにシリル化試薬（ＢＳＴＦＡ－ＴＭＣＳ（９９：１）東京化成工業（株）製）を４０ｍｇ加え、７０℃で３時間反応させる。反応後の溶液をガスクロマトグラフ質量分析計（ＧＣＭＳ）により分析する。例えば炭素数２４の鎖状脂肪族アルコール（分子量：３５５、シリル化後の分子量：４２８）の場合、ＭＳ分析による分子量４２７のピークがガスクロマトグラフにて保持時間が２９．５分あたりに認められるので、用いた粘度指数向上剤組成物又は潤滑油組成物の量、その他成分抽出物の量Ｘ及びピーク面積比率から、組成物中の鎖状脂肪族アルコール（Ｂ）の含有量を算出することができる。
＜ＧＣ－ＭＳ測定条件＞
（ＧＣ測定条件）
装置　　　　：「ＧＣ－２０１０」［（株）島津製作所製］
カラム　　　：「ＺＢ－５（カラム長：３０ｍ、カラム内径：０．２５ｍｍ、膜厚：０．２５μｍ）」［島津ジーエルシー（株）製］　
気化室温度　：２５０℃
圧力　　　　：１０００ｋＰａ
スプリット比：５０
昇温条件　　：４０℃で５分保持、３００℃まで昇温（１０℃／分）、３００℃で１０分保持。
（ＭＳ測定条件）
装置　　　　　　　　：「ＧＣＭＳ　ＱＰ－２０１０　Ｐｌｕｓ」［（株）島津製作所製］
イオン源　　　　　　：ＣＩ
イオン源温度　　　　：１７０℃
インターフェース温度：２５０℃
導入試薬ガス　　　　：イソブタン <Method for measuring the content of chain aliphatic alcohol (B) in the viscosity index improver composition and lubricating oil composition>
Using a Soxhlet extractor, 1 g of the viscosity index improver composition or lubricating oil composition of the present invention is separated and extracted into the (co)polymer (A) component and other components soluble in the hexane solvent using 300 ml of hexane solvent. Since the chain aliphatic alcohol (B) is dissolved in hexane, it is included in the other extracted components. The hexane solvent in the solution containing the extracted other components is distilled off under reduced pressure using an evaporator.
Accurately weigh 10 mg of the amount X (mg) of other component extracts that remained without distillation, and add 40 mg of silylation reagent (BSTFA-TMCS (99:1) manufactured by Tokyo Kasei Kogyo Co., Ltd.) thereto. , react at 70°C for 3 hours. The solution after the reaction is analyzed using a gas chromatograph mass spectrometer (GCMS). For example, in the case of a chain aliphatic alcohol with 24 carbon atoms (molecular weight: 355, molecular weight after silylation: 428), a peak with a molecular weight of 427 is observed in a gas chromatograph at a retention time of 29.5 minutes by MS analysis. The content of chain aliphatic alcohol (B) in the composition can be calculated from the amount of the viscosity index improver composition or lubricating oil composition used, the amount X of other component extracts, and the peak area ratio. can.
<GC-MS measurement conditions>
(GC measurement conditions)
Equipment: "GC-2010" [manufactured by Shimadzu Corporation]
Column: “ZB-5 (column length: 30 m, column inner diameter: 0.25 mm, film thickness: 0.25 μm)” [manufactured by Shimadzu GLC Co., Ltd.]
Vaporization chamber temperature: 250℃
Pressure: 1000kPa
Split ratio: 50
Temperature raising conditions: Hold at 40°C for 5 minutes, raise temperature to 300°C (10°C/min), hold at 300°C for 10 minutes.
(MS measurement conditions)
Equipment: "GCMS QP-2010 Plus" [manufactured by Shimadzu Corporation]
Ion source: CI
Ion source temperature: 170℃
Interface temperature: 250℃
Introduced reagent gas: Isobutane
　本発明の潤滑油組成物は、前記粘度指数向上剤組成物と前記リン酸エステル（Ｃ）以外に、その他の添加剤｛酸化防止剤、摩擦調整剤、消泡剤、防錆剤、腐食防止剤などの種々添加剤からなる群から選ばれる少なくとも１種の添加剤｝を含有してもよい。 The lubricating oil composition of the present invention contains, in addition to the viscosity index improver composition and the phosphate ester (C), other additives {an antioxidant, a friction modifier, an antifoaming agent, a rust preventive, and a corrosion preventive agent. at least one kind of additive selected from the group consisting of various additives such as additives.
（１）酸化防止剤：
　例えば、２，６－ジ－ｔｅｒｔ－ブチルフェノール（以下、ｔｅｒｔ－ブチルをｔ－ブチルと略記する。）、２，６－ジ－ｔ－ブチル－４－メチルフェノール、２，６－ジ－ｔ－ブチル－４ －エチルフェノール、２，４－ジメチル－６－ｔ－ブチルフェノール、４，４’－メチレンビス（２，６－ジ－ｔ－ブチルフェノール）、４，４’－ビス（２，６－ジ－ｔ－ブチルフェノール）、４，４’－ビス（２－ メチル－６－ｔ－ブチルフェノール）、２，２’－メチレンビス（４－メチル－６－ｔ－ブチルフェノール）、２，２’－メチレンビス（４－エチル－６－ｔ－ブチルフェノール）、４，４’－ブチリデンビス（３－メチル－６－ｔ－ブチルフェノール）、４，４’－イソプロピリデンビス（２，６－ジ－ｔ－ブチルフェノール）、２，２’－メチレンビス（４－メチル－６－シクロヘキシルフェノール）、２，２’－メチレンビス（４－メチル－６－ノニルフェノール）、２，２’－イソブチリデンビス（４，６－ジメチルフェノール）、２，６－ビス（２’－ヒドロキシ－３’－ｔ－ブチル－５’－メチルベンジル）－４－メチルフェノール、３－ｔ－ブチル－４－ヒドロキシアニソール、２－ｔ－ブチル－４－ヒドロキシアニソール、３－（４－ヒドロキシ－３，５－ジ－ｔ－ブチルフェニル）プロピオン酸ステアリル、３－（４－ヒドロキシ－３，５－ジ－ｔ－ブチルフェニル）プロピオン酸オレイル、３－（４－ヒドロキシ－３，５－ジ－ｔ－ブチルフェニル）プロピオン酸ドデシル、３－（４－ヒドロキシ－３，５－ジ－ｔ－ブチルフェニル）プロピオン酸デシル、３－（４－ヒドロキシ－３，５－ジ－ｔ－ブチルフェニル）プロピオン酸オクチル、テトラキス｛３－（４－ヒドロキシ－３， ５－ジ－ｔ－ブチルフェニル）プロピオニルオキシメチル｝メタン、３－（４－ヒドロキシ－３，５－ジ－ｔ－ブチルフェニル）プロピオン酸グリセリンモノエステル、３－（４－ヒドロキシ－３，５－ジ－ｔ－ブチルフェニル）プロピオン酸とグリセリンモノオレイルエーテルとのエステル、３－（４－ヒドロキシ－３，５－ ジ－ｔ－ブチルフェニル）プロピオン酸ブチレングリコールジエステル、３－（４－ヒドロキシ－３，５－ジ－ｔ－ブチルフェニル）プロピオン酸チオジグリコールジエステル、４，４’－チオビス（３－メチル－６－ ｔ－ブチルフェノール）、４，４’－チオビス（２－メチル－６－ｔ－ブチルフェノール）、２，２’－チオビス（４－メチル－６－ｔ－ブチルフェノール）、２，６－ジ－ｔ－ブチル－α－ジメチルアミノ－ｐ－クレゾール、４，６－ビス（オクチルチオメチル）－ｏ－クレゾール、４，６－ビス（ドデシルチオメチル）－ｏ－クレゾール、２，６－ジ－ｔ－ブチル－４－（Ｎ，Ｎ’－ジメチルアミノメチルフェノール）、ビス（３， ５－ジ－ｔ－ブチル－４－ヒドロキシベンジル）サルファイド、トリス｛（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオニル－オキシエチル｝イソシアヌレート、トリス（３，５－ジ－ｔ－ブチル－４ －ヒドロキシフェニル）イソシアヌレート、１，３，５－トリス（３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジル）イソシアヌレート、ビス｛２－メチル－４－（３－ｎ－アルキルチオプロピオニルオキシ）－５－ｔ－ブチルフェニル｝サルファイド、１，３，５－トリス（４－ｔ－ブチル－３－ヒドロキシ－２，６－ジメチルベンジル）イソシアヌレート、テトラフタロイル－ジ（２，６－ジメチル－４－ｔ－ブチル－３－ヒドロキシベンジルサルファイド）、６－（４－ヒドロキシ－３，５－ジ－ｔ－ ブチルアニリノ）－２，４－ビス（オクチルチオ）－１，３，５－トリアジン、２，２’－チオ－ジエチレンビス［３－ （３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、トリデシル－３－（３，５－ジ－ｔ－ブチル－４－ ヒドロキシフェニル）プロピオネート、ペンタエリスリチル－テトラキス［３－（３，５－ジ－ｔ－ ブチル－４－ヒドロキシフェニル）プロピオネート］、オクタデシル－３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、オクチル－３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、ヘプチル－３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、オクチル－３－（３－メチル－５－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、ノニル－３－（３－メチル－５－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、ヘキサメチレンビス［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、［３，５－ビス（１，１－ジメチル－エチル）－４－ヒドロキシ］ベンゼンプロピオン酸Ｃ７－Ｃ９側鎖アルキルエステル、２，４，８－テトラオキサスピロ［５，５］ウンデカン－３，９－ジイルビス（２－メチルプロパン－２，１－ジイル）ビス［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、３，５－ジ－ｔ－ブチル－４－ヒドロキシ－ベンジル－リン酸ジエステル、ビス（３－メチル－４－ヒドロキシ－５－ｔ－ブチルベンジル）サルファイド、３，９－ビス〔１，１－ジメチル－２－｛β－（３－ｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオニルオキシ｝エチル〕－２，４，８，１０－テトラオキサスピロ［５，５］ウンデカン、１，１，３－トリス（２ －メチル－４－ヒドロキシ－５－ｔ－ブチルフェニル）ブタン、１，１－ビス（２－メチル－４－ヒドロキシ－５－ｔ－ブチルフェニル）ブタン、１，３，５－トリメチル－２，４，６－トリス（３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジル）ベンゼン、２，４，６－トリス（３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジル）メシチレン、３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジルアルキルエステル及びビス｛３，３’－ビス－（４’－ヒドロキシ－３’－ｔ－ブチルフェニル）ブチリックアシッド｝グリコールエステル等のフェノール系酸化防止剤； (1) Antioxidant:
For example, 2,6-di-tert-butylphenol (hereinafter, tert-butyl is abbreviated as t-butyl), 2,6-di-t-butyl-4-methylphenol, 2,6-di-t- Butyl-4-ethylphenol, 2,4-dimethyl-6-t-butylphenol, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-bis(2,6-di- t-butylphenol), 4,4'-bis(2-methyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4- ethyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 4,4'-isopropylidenebis(2,6-di-t-butylphenol), 2,2 '-Methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(4-methyl-6-nonylphenol), 2,2'-isobutylidenebis(4,6-dimethylphenol), 2, 6-bis(2'-hydroxy-3'-t-butyl-5'-methylbenzyl)-4-methylphenol, 3-t-butyl-4-hydroxyanisole, 2-t-butyl-4-hydroxyanisole, Stearyl 3-(4-hydroxy-3,5-di-t-butylphenyl)propionate, oleyl 3-(4-hydroxy-3,5-di-t-butylphenyl)propionate, 3-(4-hydroxy) Dodecyl -3,5-di-t-butylphenyl)propionate, Decyl 3-(4-hydroxy-3,5-di-t-butylphenyl)propionate, 3-(4-hydroxy-3,5-didecyl) -t-butylphenyl)octyl propionate, tetrakis {3-(4-hydroxy-3,5-di-t-butylphenyl)propionyloxymethyl}methane, 3-(4-hydroxy-3,5-di-t) -butylphenyl)propionic acid glycerin monoester, ester of 3-(4-hydroxy-3,5-di-t-butylphenyl)propionic acid and glycerin monooleyl ether, 3-(4-hydroxy-3,5- Di-t-butylphenyl)propionate butylene glycol diester, 3-(4-hydroxy-3,5-di-t-butylphenyl)propionate thiodiglycol diester, 4,4'-thiobis(3-methyl-6 - t-butylphenol), 4,4'-thiobis(2-methyl-6-t-butylphenol), 2,2'-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t- Butyl-α-dimethylamino-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, 4,6-bis(dodecylthiomethyl)-o-cresol, 2,6-di-t-butyl -4-(N,N'-dimethylaminomethylphenol), bis(3,5-di-t-butyl-4-hydroxybenzyl)sulfide, tris{(3,5-di-t-butyl-4-hydroxy phenyl)propionyl-oxyethyl}isocyanurate, tris(3,5-di-t-butyl-4-hydroxyphenyl)isocyanurate, 1,3,5-tris(3,5-di-t-butyl-4-hydroxy) benzyl) isocyanurate, bis{2-methyl-4-(3-n-alkylthiopropionyloxy)-5-t-butylphenyl} sulfide, 1,3,5-tris(4-t-butyl-3-hydroxy- 2,6-dimethylbenzyl)isocyanurate, tetraphthaloyl-di(2,6-dimethyl-4-t-butyl-3-hydroxybenzyl sulfide), 6-(4-hydroxy-3,5-di-t- butylanilino)-2,4-bis(octylthio)-1,3,5-triazine, 2,2'-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] , tridecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, pentaerythrityl-tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], Octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, Octyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, Heptyl-3-(3 ,5-di-t-butyl-4-hydroxyphenyl)propionate, octyl-3-(3-methyl-5-t-butyl-4-hydroxyphenyl)propionate, nonyl-3-(3-methyl-5-t) -butyl-4-hydroxyphenyl)propionate, hexamethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], [3,5-bis(1,1-dimethyl-ethyl)] -4-Hydroxy]benzenepropionic acid C7-C9 side chain alkyl ester, 2,4,8-tetraoxaspiro[5,5]undecane-3,9-diylbis(2-methylpropane-2,1-diyl)bis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3,5-di-t-butyl-4-hydroxy-benzyl-phosphoric acid diester, bis(3-methyl-4- Hydroxy-5-t-butylbenzyl) sulfide, 3,9-bis[1,1-dimethyl-2-{β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]- 2,4,8,10-tetraoxaspiro[5,5]undecane, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,1-bis(2 -Methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 2 , 4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)mesitylene, 3,5-di-t-butyl-4-hydroxybenzyl alkyl ester and bis{3,3'-bis- Phenolic antioxidants such as (4'-hydroxy-3'-t-butylphenyl) butyric acid} glycol ester;
　１－ナフチルアミン、フェニル－１－ナフチルアミン、Ｎ－ナフチル－（１，１，３，３－テトラメチルブチルフェニル）－１－アミン、アルキルフェニル－１－ナフチルアミン、ｐ－オクチルフェニル－１－ナフチルアミン、ｐ－ノニルフェニル－１－ナフチルアミン、ｐ－ドデシルフェニル－１－ナフチルアミン及びフェニル－２－ナフチルアミン等のナフチルアミン系酸化防止剤；Ｎ，Ｎ’－ジイソプロピル－ ｐ－フェニレンジアミン、Ｎ，Ｎ’－ジイソブチル－ｐ－フェニレンジアミン、Ｎ，Ｎ’－ジフェニル－ｐ－ フェニレンジアミン、Ｎ，Ｎ’－ジ－β－ナフチル－ｐ－フェニレンジアミン、Ｎ－フェニル－Ｎ’－イソプロピル－ｐ－フェニレンジアミン、Ｎ－シクロヘキシル－Ｎ’－フェニル－ｐ－フェニレンジアミン、Ｎ－１，３－ジメチルブチル－Ｎ’－フェニル－ｐ－フェニレンジアミン、ジオクチル－ｐ－フェニレンジアミン、フェニルヘキシル－ｐ－フェニレンジアミン及びフェニルオクチル－ｐ－フェニレンジアミン等のフェニレンジアミン系酸化防止剤；ジピリジルアミン、ジフェニルアミン、ジアルキルフェニルアミン、ビス（４－ｎ－ブチルフェニル）アミン、ビス（４－ｔ－ブチルフェニル）アミン、ビス（４－ｎ－ペンチルフェニル）アミン、ビス（４－ｔ－ペンチルフェニル）アミン、ビス（４－ｎ－オクチルフェニル）アミン、ビス（４－（２－エチルヘキシル）フェニル）アミン、ビス（４－ノニルフェニル）アミン、ビス（４－デシルフェニル）アミン、ビス（４－ドデシルフェニル）アミン、ビス（４－スチリルフェニル）アミン、ビス（４－メトキシフェニル）アミン、４，４’－ビス（４－α，α－ジメチルベンゾイル）ジフェニルアミン、ｐ－イソプロポキシジフェニルアミン、ジピリジルアミン及びＮ－フェニルベンゼンアミンと２，２，４－トリメチルペンテンの反応生成物等のジフェニルアミン系酸化防止剤；フェノチアジン、Ｎ－メチルフェノチアジン、Ｎ－エチルフェノチアジン、３，７－ジオクチルフェノチアジン、フェノチアジンカルボン酸エステル及びフェノセレナジン等のフェノチアジン系酸化防止剤等が挙げられる。 1-naphthylamine, phenyl-1-naphthylamine, N-naphthyl-(1,1,3,3-tetramethylbutylphenyl)-1-amine, alkylphenyl-1-naphthylamine, p-octylphenyl-1-naphthylamine, p - Naphthylamine antioxidants such as nonylphenyl-1-naphthylamine, p-dodecylphenyl-1-naphthylamine and phenyl-2-naphthylamine; N,N'-diisopropyl-p-phenylenediamine, N,N'-diisobutyl-p -phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-di-β-naphthyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N-cyclohexyl- N'-phenyl-p-phenylenediamine, N-1,3-dimethylbutyl-N'-phenyl-p-phenylenediamine, dioctyl-p-phenylenediamine, phenylhexyl-p-phenylenediamine and phenyloctyl-p-phenylene Phenylenediamine antioxidants such as diamine; dipyridylamine, diphenylamine, dialkylphenylamine, bis(4-n-butylphenyl)amine, bis(4-t-butylphenyl)amine, bis(4-n-pentylphenyl) Amine, bis(4-t-pentylphenyl)amine, bis(4-n-octylphenyl)amine, bis(4-(2-ethylhexyl)phenyl)amine, bis(4-nonylphenyl)amine, bis(4- decylphenyl)amine, bis(4-dodecylphenyl)amine, bis(4-styrylphenyl)amine, bis(4-methoxyphenyl)amine, 4,4'-bis(4-α,α-dimethylbenzoyl)diphenylamine, Diphenylamine antioxidants such as p-isopropoxydiphenylamine, dipyridylamine, and reaction products of N-phenylbenzenamine and 2,2,4-trimethylpentene; phenothiazine, N-methylphenothiazine, N-ethylphenothiazine, 3,7 - Phenothiazine antioxidants such as dioctylphenothiazine, phenothiazine carboxylic acid ester, and phenoselenazine.
（２）摩擦調整剤：
　例えば、オレイルアルコール、ステアリルアルコール及びラウリルアルコール等の高級アルコール類；オレイン酸、ステアリン酸及びラウリン酸等の脂肪酸類；オレイン酸グリセリル、ステアリン酸グリセリル、ラウリン酸グリセリル、アルキルグリセリルエステル、アルケニルグリセリルエステル、アルキニルグリセリルエステル、エチレングリコールオレイン酸エステル、エチレングリコールステアリン酸エステル、エチレングリコールラウリン酸エステル、プロピレングリコールオレイン酸エステル、プロピレングリコールステアリン酸エステル及びプロピレングリコールラウリン酸エステル等のエステル類；オレイルアミド、ステアリルアミド、ラウリルアミド、アルキルアミド、アルケニルアミド及びアルキニルアミド等のアミド類；オレイルアミン、ステアリルアミン、ラウリルアミン、アルキルアミン、アルケニルアミン、アルキニルアミン、ココビス（２－ヒドロキシエチル）アミン、牛脂ビス（２－ヒドロキシエチル）アミン、Ｎ－（２－ヒドロキシヘキサデシル）ジエタノールアミン及びジメチル牛脂三級アミン等のアミン類；オレイルグリセリルエーテル、ステアリルグリセリルエーテル、ラウリルグリセリルエーテル、アルキルグリセリルエーテル、アルケニルグリセリルエーテル及びアルキニルグリセリルエーテル等のエーテル類が挙げられる。 (2) Friction modifier:
For example, higher alcohols such as oleyl alcohol, stearyl alcohol, and lauryl alcohol; fatty acids such as oleic acid, stearic acid, and lauric acid; glyceryl oleate, glyceryl stearate, glyceryl laurate, alkyl glyceryl ester, alkenyl glyceryl ester, alkynyl Esters such as glyceryl ester, ethylene glycol oleate, ethylene glycol stearate, ethylene glycol laurate, propylene glycol oleate, propylene glycol stearate, and propylene glycol laurate; oleylamide, stearylamide, lauryl Amides such as amides, alkylamides, alkenylamides and alkynylamides; oleylamine, stearylamine, laurylamine, alkylamine, alkenylamine, alkynylamine, cocobis(2-hydroxyethyl)amine, tallow bis(2-hydroxyethyl)amine , N-(2-hydroxyhexadecyl) diethanolamine and dimethyl tallow tertiary amine; ethers such as oleyl glyceryl ether, stearyl glyceryl ether, lauryl glyceryl ether, alkyl glyceryl ether, alkenyl glyceryl ether and alkynyl glyceryl ether; Can be mentioned.
（３）消泡剤：
　例えば、ポリジメチルシリコーン、ジメチルシリコーンオイル、トリフルオロプロピルメチルシリコーン、コロイダルシリカ、ポリアルキルアクリレート、ポリアルキルメタクリレート、アルコールエトキシ／プロポキシレート、脂肪酸エトキシ／プロポキシレート及びソルビタン部分脂肪酸エステル等が挙げられる。 (3) Antifoaming agent:
Examples include polydimethyl silicone, dimethyl silicone oil, trifluoropropyl methyl silicone, colloidal silica, polyalkyl acrylate, polyalkyl methacrylate, alcohol ethoxy/propoxylate, fatty acid ethoxy/propoxylate, and sorbitan partial fatty acid ester.
（４）防錆剤：
　例えば、亜硝酸ナトリウム、酸化パラフィンワックスカルシウム塩、酸化パラフィンワックスマグネシウム塩、牛脂脂肪酸アルカリ金属塩、アルカリ土類金属塩、アルカリ土類アミン塩、アルケニルコハク酸、アルケニルコハク酸ハーフエステル（アルケニル基の分子量は１００～３００程度）、ソルビタンモノエステル、ノニルフェノールエトキシレート及びラノリン脂肪酸カルシウム塩等が挙げられる。 (4) Rust inhibitor:
For example, sodium nitrite, oxidized paraffin wax calcium salt, oxidized paraffin wax magnesium salt, tallow fatty acid alkali metal salt, alkaline earth metal salt, alkaline earth amine salt, alkenyl succinic acid, alkenyl succinic acid half ester (molecular weight of alkenyl group (about 100 to 300), sorbitan monoester, nonylphenol ethoxylate, and lanolin fatty acid calcium salt.
（５）腐食防止剤：
　例えば、特許文献２に開示されているような脂環式エポキシドとして２－エチルヘキシル７－オキサビシクロ［４．１．０］ヘプタン－３－カルボン酸、７－オキサビシクロ［４．１．０］ヘプタン－３，４－カルボン酸等やトリアゾール、トリルトリアゾール、ベンゾトリアゾール、ベンゾイミダゾール、ベンゾチアゾール、ベンゾチアジアゾール又はこれら化合物の誘導体である、２－ヒドロキシ－Ｎ－（１Ｈ－１，２，４－トリアゾール－３－イル）ベンズアミド、Ｎ，Ｎ－ビス（２－エチルヘキシル）－［（１，２，４－トリアゾール－１－イル）メチル］アミン、Ｎ，Ｎ－ビス（２－エチルヘキシル）－［（１，２，４－トリアゾール－１－イル）メチル］アミン及び２，２’－［［（４又は５又は１）－（２－エチルヘキシル）－メチル－１Ｈ－ベンゾトリアゾール－１－メチル］イミノ］ビスエタノール等が挙げられ、他にもビス（ポリ－２－カルボキシエチル）ホスフィン酸、ヒドロキシホスホノ酢酸、テトラアルキルチウラムジサルファイド、Ｎ’１，Ｎ’１２－ビス（２－ヒドロキシベンゾイル）ドデカンジハイドラジド、３－（３，５－ジ－ｔ－ブチル－ヒドロキシフェニル）－Ｎ’－（３－（３，５－ジ－ｔｅｒｔ－ブチル－ヒドロキシフェニル）プロパノイル）プロパンハイドラジド、テトラプロぺニルコハク酸と１，２－プロパンジオールのエステル化物、ジソディウムセバケート、（４－ノニルフェノキシ）酢酸、モノ及びジヘキシルフォスフェートのアルキルアミン塩、トリルトリアゾールのナトリウム塩及び（Ｚ）－Ｎ－メチルＮ－（１－オキソ９－オクタデセニル）グリシン等が挙げられる。 (5) Corrosion inhibitor:
For example, 2-ethylhexyl 7-oxabicyclo[4.1.0]heptane-3-carboxylic acid, 7-oxabicyclo[4.1.0]heptane as the alicyclic epoxide as disclosed in Patent Document 2 2-Hydroxy-N-(1H-1,2,4-triazole- 3-yl)benzamide, N,N-bis(2-ethylhexyl)-[(1,2,4-triazol-1-yl)methyl]amine, N,N-bis(2-ethylhexyl)-[(1, 2,4-triazol-1-yl)methyl]amine and 2,2'-[[(4 or 5 or 1)-(2-ethylhexyl)-methyl-1H-benzotriazol-1-methyl]imino]bisethanol Other examples include bis(poly-2-carboxyethyl)phosphinic acid, hydroxyphosphonoacetic acid, tetraalkylthiuram disulfide, and N'1,N'12-bis(2-hydroxybenzoyl)dodecane dihydrazide. , 3-(3,5-di-tert-butyl-hydroxyphenyl)-N'-(3-(3,5-di-tert-butyl-hydroxyphenyl)propanoyl)propane hydrazide, tetrapropenylsuccinic acid and 1 , esterified products of 2-propanediol, disodium sebacate, (4-nonylphenoxy)acetic acid, alkylamine salts of mono- and dihexyl phosphate, sodium salt of tolyltriazole and (Z)-N-methyl N-(1- Examples include oxo-9-octadecenyl)glycine.
　その他の添加剤は、１種を含んでいてもよく、２種以上を併用してもよく、添加剤として複数種類を含んだパッケージ添加剤を用いてもよい。その他の添加剤の含有量は、潤滑油組成物の重量を基準として、好ましくは１～１５重量％であり、更に好ましくは２～１０重量％である。 Other additives may include one type, two or more types may be used in combination, and a package additive containing multiple types may be used as the additive. The content of other additives is preferably 1 to 15% by weight, more preferably 2 to 10% by weight, based on the weight of the lubricating oil composition.
　潤滑油組成物の粘度指数（ＡＳＴＭ　Ｄ　４４５に準拠して測定した値）は、３００以上が好ましく、さらに好ましくは３２０以上であり、特に好ましくは３３０以上である。 The viscosity index (measured according to ASTM D 445) of the lubricating oil composition is preferably 300 or more, more preferably 320 or more, and particularly preferably 330 or more.
　潤滑油組成物の低温粘度（－５４℃、ＪＰＩ－５Ｓ－２６－９９に準じてブルックフィールド型粘度計で測定した値）は、１２００ｍＰａ・ｓ以下が好ましく、さらに好ましくは１１００ｍＰａ・ｓ以下であり、特に好ましくは１０５０ｍＰａ・ｓ以下である。 The low-temperature viscosity of the lubricating oil composition (value measured at -54°C with a Brookfield viscometer according to JPI-5S-26-99) is preferably 1200 mPa·s or less, more preferably 1100 mPa·s or less. , particularly preferably 1050 mPa·s or less.
　本発明の潤滑油組成物は、粘度指数が高く、リン酸エステルの加水分解が抑制されており、さらに低温（－６０℃）でも析出物がなく、低温での粘度が良好なので、特に上空（低温環境下）で用いられることのある航空機用油圧作動油として有用である。 The lubricating oil composition of the present invention has a high viscosity index, suppresses the hydrolysis of phosphoric acid ester, and has no precipitates even at low temperatures (-60°C), and has good viscosity at low temperatures. It is useful as an aircraft hydraulic fluid that is sometimes used in low-temperature environments.
　本明細書には、以下の事項が開示されている。 The following matters are disclosed in this specification.
　本開示（１）は、リン酸エステル（Ｃ）を含有する潤滑油組成物用の粘度指数向上剤組成物であって、
　下記一般式（１）で表される単量体（ａ）を必須構成単量体とする（共）重合体（Ａ）と、ＨＬＢ値が２．５～７．０である鎖状脂肪族アルコール（Ｂ）とを含有し、前記（共）重合体（Ａ）の溶解性パラメータが９．００～９．８０（ｃａｌ／ｃｍ３）１／２である粘度指数向上剤組成物である。
Figure JPOXMLDOC01-appb-C000005
 ［Ｒ１は水素原子又はメチル基；－Ｘ１－は－Ｏ－又は－ＮＨ－で表される基；Ｒ２は炭素数２～４のアルキレン基；Ｒ３は炭素数１～１７の直鎖又は分岐アルキル基；ｐは０～２０の整数であり、ｐが２以上の場合のＲ２は同一でも異なっていてもよい。］ The present disclosure (1) is a viscosity index improver composition for a lubricating oil composition containing a phosphate ester (C),
A (co)polymer (A) having monomer (a) represented by the following general formula (1) as an essential constituent monomer, and a chain aliphatic compound having an HLB value of 2.5 to 7.0. The present invention is a viscosity index improver composition containing alcohol (B) and in which the (co)polymer (A) has a solubility parameter of 9.00 to 9.80 (cal/cm 3 ) 1/2 .
Figure JPOXMLDOC01-appb-C000005
 [R 1 is a hydrogen atom or a methyl group; -X 1 - is a group represented by -O- or -NH-; R 2 is an alkylene group having 2 to 4 carbon atoms; R 3 is a straight group having 1 to 17 carbon atoms; Chain or branched alkyl group; p is an integer of 0 to 20, and when p is 2 or more, R 2 may be the same or different. ]
　本開示（２）は、前記（共）重合体（Ａ）の重量平均分子量が５，０００～３００，０００である本開示（１）に記載の粘度指数向上剤組成物である。 The present disclosure (2) is the viscosity index improver composition according to the present disclosure (1), wherein the (co)polymer (A) has a weight average molecular weight of 5,000 to 300,000.
　本開示（３）は、前記（共）重合体（Ａ）と前記鎖状脂肪族アルコール（Ｂ）の重量比率（Ａ／Ｂ）が１０～５０００である本開示（１）又は（２）に記載の粘度指数向上剤組成物である。 The present disclosure (3) provides the present disclosure (1) or (2), wherein the weight ratio (A/B) of the (co)polymer (A) and the chain aliphatic alcohol (B) is 10 to 5000. The viscosity index improver composition described above.
　本開示（４）は、前記鎖状脂肪族アルコール（Ｂ）が、炭素数８～１７の直鎖又は分岐鎖状脂肪族アルコールである本開示（１）～（３）のいずれか１項に記載の粘度指数向上剤組成物である。 The present disclosure (4) relates to any one of the present disclosure (1) to (3), wherein the chain aliphatic alcohol (B) is a linear or branched aliphatic alcohol having 8 to 17 carbon atoms. The viscosity index improver composition described above.
　本開示（５）は、さらにリン酸エステル（Ｃ）を含有してなる本開示（１）～（４）のいずれか１項に記載の粘度指数向上剤組成物である。 The present disclosure (5) is the viscosity index improver composition according to any one of the present disclosure (1) to (4), which further contains a phosphoric acid ester (C).
　本開示（６）は、本開示（１）～（５）のいずれか１項に記載の粘度指数向上剤組成物とリン酸エステル（Ｃ）を含有する潤滑油組成物である。 The present disclosure (6) is a lubricating oil composition containing the viscosity index improver composition according to any one of the present disclosures (1) to (5) and a phosphoric acid ester (C).
　本開示（７）は、前記潤滑油組成物中の前記リン酸エステル（Ｃ）の含有量が７５重量％以上である本開示（６）に記載の潤滑油組成物である。 The present disclosure (7) is the lubricating oil composition according to the present disclosure (6), wherein the content of the phosphate ester (C) in the lubricating oil composition is 75% by weight or more.
　本開示（８）は、前記リン酸エステル（Ｃ）の４０℃における動粘度が１～４０ｍｍ２／ｓである本開示（６）又は（７）に記載の潤滑油組成物である。 The present disclosure (8) is the lubricating oil composition according to the present disclosure (6) or (7), wherein the phosphoric acid ester (C) has a kinematic viscosity of 1 to 40 mm 2 /s at 40° C.
　本開示（９）は、航空機用油圧作動油として用いられる本開示（６）～（８）のいずれか１項に記載の潤滑油組成物である。 The present disclosure (9) is the lubricating oil composition according to any one of the present disclosure (6) to (8), which is used as an aircraft hydraulic fluid.
　以下、実施例により本発明を詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited thereto.
＜実施例１～１４、比較例１～５＞
　撹拌装置、加熱冷却装置、温度計、滴下ロート、窒素導入管及び減圧装置を備えた反応容器に、表２－１～表２－３に記載の種類及び量のリン酸エステル（Ｃ）１００重量部を投入し、別のガラス製ビーカーに、表２－１～表２－３に記載の種類及び量の鎖状脂肪族アルコール（Ｂ）又は比較用の化合物（Ｂ’）、並びに重合体（Ａ）の構成単量体、連鎖移動剤、及び重合開始剤を投入し、２０℃で撹拌、混合して単量体溶液を調製し、滴下ロートに投入した。反応容器の気相部の窒素置換（気相酸素濃度１００ｐｐｍ）を行った後、密閉下系内温度を７０～８０℃に保ちながら、３時間かけて単量体溶液をリン酸エステル（Ｃ）が投入された反応容器に滴下した。この時、反応溶液の液面の高さが反応容器の容量の７０％になるように各原料を仕込んだ。滴下終了から２時間、９０℃で熟成した後、１２０℃に昇温後、同温度で減圧度を０．０２７～０．０４０ＭＰａになるまで、液面高さが反応容器の容量の９０％を超えないように徐々に減圧し、その後、気泡の発生が完全に消失するまで未反応の単量体を除去した。
　上記手順により、（共）重合体（Ａ）及び鎖状脂肪族アルコール（Ｂ）又は比較用の化合物（Ｂ’）を含有する粘度指数向上剤組成物（Ｒ１）～（Ｒ１４）、（Ｓ１）～（Ｓ５）を得た。得られた粘度指数向上剤組成物中の共重合体（Ａ１）～（Ａ１１）及び（Ａ’１）～（Ａ’２）のＭｗ、鎖状脂肪族アルコール（Ｂ）の含有量を上記の方法で測定した結果を表２－１～表２－３に示す。また、粘度指数向上剤組成物の低温での外観、加水分解安定性を下記の方法で測定した結果を表２－１～表２－３に示す。 <Examples 1 to 14, Comparative Examples 1 to 5>
In a reaction vessel equipped with a stirring device, a heating and cooling device, a thermometer, a dropping funnel, a nitrogen introduction pipe, and a pressure reducing device, add 100 weight phosphoric acid esters (C) of the types and amounts listed in Tables 2-1 to 2-3. Into another glass beaker, add chain aliphatic alcohol (B) or comparative compound (B') of the types and amounts listed in Tables 2-1 to 2-3, and polymer ( The constituent monomers of A), a chain transfer agent, and a polymerization initiator were added, stirred and mixed at 20°C to prepare a monomer solution, and the solution was added to a dropping funnel. After replacing the gas phase of the reaction vessel with nitrogen (gas phase oxygen concentration: 100 ppm), the monomer solution was converted into phosphate ester (C) over a period of 3 hours while keeping the system temperature at 70 to 80°C under closed conditions. was added dropwise to the reaction vessel containing the solution. At this time, each raw material was charged so that the liquid level of the reaction solution was 70% of the capacity of the reaction container. After aging at 90°C for 2 hours from the end of dropping, the temperature was raised to 120°C, and at the same temperature, the degree of vacuum was reduced to 0.027 to 0.040 MPa until the liquid level reached 90% of the capacity of the reaction vessel. The pressure was gradually reduced so as not to exceed the pressure, and then unreacted monomers were removed until the generation of bubbles completely disappeared.
By the above procedure, viscosity index improver compositions (R1) to (R14), (S1) containing the (co)polymer (A) and the chain aliphatic alcohol (B) or the comparative compound (B') were prepared. ~(S5) was obtained. The Mw of the copolymers (A1) to (A11) and (A'1) to (A'2) and the content of the chain aliphatic alcohol (B) in the obtained viscosity index improver composition were determined as above. The results measured by this method are shown in Tables 2-1 to 2-3. In addition, the appearance at low temperatures and hydrolytic stability of the viscosity index improver composition were measured by the following methods, and the results are shown in Tables 2-1 to 2-3.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
　表２－１～表２－３及び表３に記載の単量体（ａ）、単量体（ｅ）、単量体（ｆ）、連鎖移動剤、重合開始剤、鎖状脂肪族アルコール（Ｂ）、比較用の化合物（Ｂ’）、リン酸エステル（Ｃ）及び添加剤（消泡剤）は下記のものを用いた。
（ａ－１）：メタクリル酸メチル（Ｒ３の炭素数１）
（ａ－２）：メタクリル酸エチル（Ｒ３の炭素数２）
（ａ－３）：メタクリル酸プロピル（Ｒ３の炭素数３）
（ａ－４）：メタクリル酸ブチル（Ｒ３の炭素数４）
（ａ－５）：メタクリル酸２－エチルヘキシル（Ｒ３の炭素数８）
（ａ－６）：メタクリル酸ｎ－テトラデシル（Ｒ３の炭素数１４）
（ａ－７）：Ｒ３の炭素数１２～１３の直鎖及び分岐アルキルメタクリレート混合物（Ｎｅｏｄｏｌ２３（ＳＨＥＬＬ社製）とメタクリル酸とのエステル化物）（炭素数１２～１３）（重量比＝直鎖Ｃ１２：分岐Ｃ１２：直鎖Ｃ１３：分岐Ｃ１３＝４０：１０：４０：１０）
（ａ－８）：Ｒ３の炭素数１４～１５の直鎖及び分岐アルキルメタクリレート混合物（Ｎｅｏｄｏｌ４５（ＳＨＥＬＬ社製）とメタクリル酸とのエステル化物）（炭素数１４～１５）（重量比＝直鎖Ｃ１４：分岐Ｃ１４：直鎖Ｃ１５：分岐Ｃ１５＝４０：１０：４０：１０）
（ａ－９）：メタクリル酸ｎ－ヘキサデシル（Ｒ３の炭素数１６）
（ｅ－１）：メタクリル酸２－ヒドロキシエチル
（ｆ－１）：Ｎ，Ｎ－ジメチルアミノエチルメタクリルアミド
（ｆ－２）：Ｎ，Ｎ－ジエチルアミノエチルメタクリルアミド
連鎖移動剤：Ｘ－１：ドデシルメルカプタン
重合開始剤：Ｚ－１：２，２’－アゾビス（２－メチルブチロニトリル）
（Ｂ１）：２－エチルヘキサノール（炭素数８）、ＨＬＢ値＝６．６７、ＳＰ値＝１０．１４
（Ｂ２）：１－ドデカノール（炭素数１２）、ＨＬＢ値＝４．１７、ＳＰ値＝９．８１
（Ｂ３）：２－メチル－１－ウンデカノール（炭素数１２）、ＨＬＢ値＝４．３５、ＳＰ値＝９．７１
（Ｂ４）：１－トリデカノール（炭素数１３）、ＨＬＢ値＝３．８５、ＳＰ値＝９．７３
（Ｂ５）：２－メチル１－ドデカノール（炭素数１３）、ＨＬＢ値＝４．００、ＳＰ値＝９．６３
（Ｂ６）：１－テトラデカノール（炭素数１４）、ＨＬＢ値＝３．５７、ＳＰ値＝９．６６
（Ｂ７）：２－メチル１－トリデカノール（炭素数１４）、ＨＬＢ値＝３．７０、ＳＰ値＝９．５７
（Ｂ８）：１－ペンタデカノール（炭素数１５）、ＨＬＢ値＝３．３３、ＳＰ値＝９．６０
（Ｂ９）：２－メチル－１－テトラデカノール（炭素数１５）、ＨＬＢ値＝３．４５、ＳＰ値＝９．５１
（Ｂ１０）：１－ヘキサデカノール（炭素数１６）、ＨＬＢ値＝３．１３、ＳＰ値＝９．５４
（Ｂ１１）：１－ヘプタデカノール（炭素数１７）、ＨＬＢ値＝２．９４、ＳＰ値＝９．４９
（Ｂ’１）：１－ヘプタノール（炭素数１７）、ＨＬＢ値＝７．６９、ＳＰ値＝１０．３０
（Ｂ’２）：２－デシル－１－テトラデカノール（炭素数２４）、ＨＬＢ値＝２．０４、ＳＰ値＝９．１７
（Ｃ－１）：東京化成工業株式会社製「リン酸トリｎ－ブチル」、１００℃の動粘度＝１．１ｍｍ２／ｓ、４０℃の動粘度＝２．６ｍｍ２／ｓ
（Ｃ－２）：ｓｉｇｍａ－ａｌｄｒｉｃｈ製「リン酸トリイソブチル」、１００℃の動粘度＝１．１ｍｍ２／ｓ、４０℃の動粘度＝３．０ｍｍ２／ｓ
（Ｃ－３）：リン酸トリイソプロピルフェニルとリン酸トリフェニルの混合物（重量比８０／２０）、１００℃の動粘度＝３．８ｍｍ２／ｓ、４０℃動粘度＝３４．２ｍｍ２／ｓ
消泡剤：ポリジメチルシリコーン Monomer (a), monomer (e), monomer (f), chain transfer agent, polymerization initiator, chain aliphatic alcohol ( B), comparative compound (B'), phosphoric acid ester (C), and additive (antifoaming agent) were as follows.
(a-1): Methyl methacrylate (R 3 has 1 carbon number)
(a-2): Ethyl methacrylate (R 3 has 2 carbon atoms)
(a-3): Propyl methacrylate (R 3 has 3 carbon atoms)
(a-4): Butyl methacrylate (R 3 has 4 carbon atoms)
(a-5): 2-ethylhexyl methacrylate (R 3 has 8 carbon atoms)
(a-6): n-tetradecyl methacrylate (R 3 has 14 carbon atoms)
(a-7): Linear and branched alkyl methacrylate mixture with R 3 having 12 to 13 carbon atoms (esterified product of Neodol 23 (manufactured by SHELL) and methacrylic acid) (12 to 13 carbon atoms) (weight ratio = linear C12: branched C12: straight chain C13: branched C13 = 40:10:40:10)
(a-8): R 3 linear and branched alkyl methacrylate mixture with 14 to 15 carbon atoms (esterified product of Neodol 45 (manufactured by SHELL) and methacrylic acid) (14 to 15 carbon atoms) (weight ratio = linear C14: Branched C14: Straight chain C15: Branched C15 = 40:10:40:10)
(a-9): n-hexadecyl methacrylate (R 3 has 16 carbon atoms)
(e-1): 2-hydroxyethyl methacrylate (f-1): N,N-dimethylaminoethyl methacrylamide (f-2): N,N-diethylaminoethyl methacrylamide Chain transfer agent: X-1: Dodecyl Mercaptan polymerization initiator: Z-1: 2,2'-azobis(2-methylbutyronitrile)
(B1): 2-ethylhexanol (8 carbon atoms), HLB value = 6.67, SP value = 10.14
(B2): 1-dodecanol (12 carbon atoms), HLB value = 4.17, SP value = 9.81
(B3): 2-methyl-1-undecanol (12 carbon atoms), HLB value = 4.35, SP value = 9.71
(B4): 1-tridecanol (13 carbon atoms), HLB value = 3.85, SP value = 9.73
(B5): 2-methyl 1-dodecanol (13 carbon atoms), HLB value = 4.00, SP value = 9.63
(B6): 1-tetradecanol (14 carbon atoms), HLB value = 3.57, SP value = 9.66
(B7): 2-methyl 1-tridecanol (14 carbon atoms), HLB value = 3.70, SP value = 9.57
(B8): 1-pentadecanol (15 carbon atoms), HLB value = 3.33, SP value = 9.60
(B9): 2-methyl-1-tetradecanol (15 carbon atoms), HLB value = 3.45, SP value = 9.51
(B10): 1-hexadecanol (16 carbon atoms), HLB value = 3.13, SP value = 9.54
(B11): 1-heptadecanol (17 carbon atoms), HLB value = 2.94, SP value = 9.49
(B'1): 1-heptanol (17 carbon atoms), HLB value = 7.69, SP value = 10.30
(B'2): 2-decyl-1-tetradecanol (24 carbon atoms), HLB value = 2.04, SP value = 9.17
(C-1): "Tri-n-butyl phosphate" manufactured by Tokyo Chemical Industry Co., Ltd., kinematic viscosity at 100°C = 1.1 mm 2 /s, kinematic viscosity at 40°C = 2.6 mm 2 /s
(C-2): "Triisobutyl phosphate" manufactured by Sigma-Aldrich, kinematic viscosity at 100°C = 1.1 mm 2 /s, kinematic viscosity at 40°C = 3.0 mm 2 /s
(C-3): Mixture of triisopropylphenyl phosphate and triphenyl phosphate (weight ratio 80/20), kinematic viscosity at 100°C = 3.8 mm 2 /s, kinematic viscosity at 40°C = 34.2 mm 2 /s
Antifoaming agent: polydimethyl silicone
（ａ－７）に由来する構成単位のＳＰ値の計算
直鎖Ｃ１２
ΣΔｅｉ＝６９５５＋１１８０×１１＋１１２５＝２１０６０
Σｖｉ＝４８．４＋１６．１×１１＋３３．５＝２５９
ＳＰ値＝（ΣΔｅｉ／Σｖｉ）１／２＝（２１０６０／２５９）１／２＝９．０１７
分岐Ｃ１２
ΣΔｅｉ＝６９５５＋１１８０×９＋１１２５×２＋８２０＝２０６４５
Σｖｉ＝４８．４＋１６．１×９＋３３．５×２-１．０＝２５９．３
ＳＰ値＝（ΣΔｅｉ／Σｖｉ）１／２＝（２０６４５／２５９．３）１／２＝８．９２３
直鎖Ｃ１３
ΣΔｅｉ＝６９５５＋１１８０×１２＋１１２５＝２２２４０
Σｖｉ＝４８．４＋１６．１×１２＋３３．５＝２７５．１
ＳＰ値＝（ΣΔｅｉ／Σｖｉ）１／２＝（２２２４０／２７５．１）１／２＝８．９９１
分岐Ｃ１３
ΣΔｅｉ＝６９５５＋１１８０×１０＋１１２５×２＋８２０＝２１８２５
Σｖｉ＝４８．４＋１６．１×１０＋３３．５×２-１．０＝２７５．４
ＳＰ値＝（ΣΔｅｉ／Σｖｉ）１／２＝（２１８２５／２７５．４）１／２＝８．９０２
（ａ－１）に由来する構成単位のＳＰ値＝（９．０１７×４０＋８．９２３×１０＋８．９９１×４０＋８．９０２×１０）／１００＝８．９８６
（共重合体（Ａ）のＳＰ値の計算には８．９９として使用した） Calculation of SP value of structural unit derived from (a-7) Linear C12
ΣΔe i =6955+1180×11+1125=21060
Σv i =48.4+16.1×11+33.5=259
SP value = (ΣΔe i /Σv i ) 1/2 = (21060/259) 1/2 = 9.017
Branch C12
ΣΔe i =6955+1180×9+1125×2+820=20645
Σv i =48.4+16.1×9+33.5×2-1.0=259.3
SP value = (ΣΔe i /Σv i ) 1/2 = (20645/259.3) 1/2 = 8.923
Straight chain C13
ΣΔe i =6955+1180×12+1125=22240
Σv i =48.4+16.1×12+33.5=275.1
SP value = (ΣΔe i /Σv i ) 1/2 = (22240/275.1) 1/2 = 8.991
Branch C13
ΣΔe i =6955+1180×10+1125×2+820=21825
Σv i =48.4+16.1×10+33.5×2-1.0=275.4
SP value = (ΣΔe i /Σv i ) 1/2 = (21825/275.4) 1/2 = 8.902
SP value of structural unit derived from (a-1) = (9.017×40+8.923×10+8.991×40+8.902×10)/100=8.986
(8.99 was used to calculate the SP value of copolymer (A))
（ａ－８）に由来する構成単位のＳＰ値の計算
直鎖Ｃ１４
ΣΔｅｉ＝６９５５＋１１８０×１３＋１１２５＝２３４２０
Σｖｉ＝４８．４＋１６．１×１３＋３３．５＝２９１．２
ＳＰ値＝（ΣΔｅｉ／Σｖｉ）１／２＝（２３４２０／２９１．２）１／２＝８．９６８
分岐Ｃ１４
ΣΔｅｉ＝６９５５＋１１８０×１１＋１１２５×２＋８２０＝２３００５
Σｖｉ＝４８．４＋１６．１×１１＋３３．５×２－１．０＝２９１．５
ＳＰ値＝（ΣΔｅｉ／Σｖｉ）１／２＝（２３００５／２９１．５）１／２＝８．８８４
直鎖Ｃ１５
ΣΔｅｉ＝６９５５＋１１８０×１４＋１１２５＝２４６００
Σｖｉ＝４８．４＋１６．１×１４＋３３．５＝３０７．３
ＳＰ値＝（ΣΔｅｉ／Σｖｉ）１／２＝（２４６００／３０７．３）１／２＝８．９４７
分岐Ｃ１５
ΣΔｅｉ＝６９５５＋１１８０×１２＋１１２５×２＋８２０＝２４１８５
Σｖｉ＝４８．４＋１６．１×１２＋３３．５×２－１．０＝３０７．６
ＳＰ値＝（ΣΔｅｉ／Σｖｉ）１／２＝（２４１８５／３０７．６）１／２＝８．８６７
（ａ－８）に由来する構成単位のＳＰ値＝（８．９６８×４０＋８．８８４×１０＋８．９４７×４０＋８．８６７×１０）／１００＝８．９４１
（共重合体（Ａ）のＳＰ値の計算には８．９４として使用した） Calculation of SP value of structural unit derived from (a-8) Linear C14
ΣΔe i =6955+1180×13+1125=23420
Σv i =48.4+16.1×13+33.5=291.2
SP value = (ΣΔe i /Σv i ) 1/2 = (23420/291.2) 1/2 = 8.968
Branch C14
ΣΔe i =6955+1180×11+1125×2+820=23005
Σv i =48.4+16.1×11+33.5×2-1.0=291.5
SP value = (ΣΔe i /Σv i ) 1/2 = (23005/291.5) 1/2 = 8.884
Straight chain C15
ΣΔe i =6955+1180×14+1125=24600
Σv i =48.4+16.1×14+33.5=307.3
SP value = (ΣΔe i /Σv i ) 1/2 = (24600/307.3) 1/2 = 8.947
Branch C15
ΣΔe i =6955+1180×12+1125×2+820=24185
Σv i =48.4+16.1×12+33.5×2-1.0=307.6
SP value = (ΣΔe i /Σv i ) 1/2 = (24185/307.6) 1/2 = 8.867
SP value of structural unit derived from (a-8) = (8.968 x 40 + 8.884 x 10 + 8.947 x 40 + 8.867 x 10) / 100 = 8.941
(8.94 was used to calculate the SP value of copolymer (A))
＜粘度指数向上剤組成物の低温（－６０℃）外観の測定方法＞
　粘度指数向上剤組成物を－６０℃で３時間静置して外観の白濁の有無を確認した。下記基準で評価した結果を表２－１～表２－３に示す。
〇：白濁していないもの
×：白濁しているもの <Method for measuring low temperature (-60°C) appearance of viscosity index improver composition>
The viscosity index improver composition was allowed to stand at -60°C for 3 hours, and the presence or absence of cloudy appearance was checked. The results of evaluation based on the following criteria are shown in Tables 2-1 to 2-3.
〇: Not cloudy ×: Cloudy
＜粘度指数向上剤組成物の加水分解安定性の測定方法＞
　粘度指数向上剤組成物の酸価をＪＩＳ　Ｋ００７０に従って測定した。
　また、作製した粘度指数向上剤組成物に対して１重量％の水を加え、１００℃で１００時間加熱した。加熱後の酸価をＪＩＳ　Ｋ００７０に従って測定した。加熱前の酸価と加熱後の酸価の差を酸価変化度として表２－１～表２－３に記載した。 <Method for measuring hydrolytic stability of viscosity index improver composition>
The acid value of the viscosity index improver composition was measured according to JIS K0070.
Further, 1% by weight of water was added to the prepared viscosity index improver composition, and the mixture was heated at 100° C. for 100 hours. The acid value after heating was measured according to JIS K0070. The difference between the acid value before heating and the acid value after heating is listed as the degree of change in acid value in Tables 2-1 to 2-3.
＜実施例１５～２８及び比較例６～１０（潤滑油組成物の評価）＞
撹拌装置を備えたステンレス製容器において、表３に記載の配合量で粘度指数向上剤組成物を添加して、１００℃動粘度が３．５０ｍｍ２／ｓになるように潤滑油組成物を調製した。
　得られた潤滑油組成物の１００℃動粘度、４０℃動粘度、粘度指数、せん断安定性、低温粘度（－５４℃）、低温（－６０℃）での外観、加水分解安定性を以下の方法で測定した。結果を表３に示す。 <Examples 15 to 28 and Comparative Examples 6 to 10 (evaluation of lubricating oil composition)>
In a stainless steel container equipped with a stirring device, add the viscosity index improver composition in the amount listed in Table 3 to prepare a lubricating oil composition so that the kinematic viscosity at 100° C. is 3.50 mm 2 /s. did.
The obtained lubricating oil composition was evaluated for its kinematic viscosity at 100°C, kinematic viscosity at 40°C, viscosity index, shear stability, low temperature viscosity (-54°C), appearance at low temperature (-60°C), and hydrolytic stability as follows. It was measured by the method. The results are shown in Table 3.
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
＜潤滑油組成物の粘度指数の計算方法＞
　ＡＳＴＭ　Ｄ　４４５の方法で４０℃と１００℃における動粘度を測定し、ＡＳＴＭ　Ｄ　４４５の方法で計算した。数値が大きいほど粘度指数向上効果が高いことを意味する。 <Method for calculating viscosity index of lubricating oil composition>
Kinematic viscosity at 40°C and 100°C was measured using the ASTM D 445 method and calculated using the ASTM D 445 method. The larger the value, the higher the effect of improving the viscosity index.
＜潤滑油組成物のせん断安定性（Ｓｏｎｉｃ　ＳＳ）の測定方法及び計算方法＞
　ＡＳＴＭ　Ｄ２６０３の超音波法に準拠して試験を行った。数値が小さいほどせん断安定性が高いことを意味する。 <Measurement method and calculation method of shear stability (Sonic SS) of lubricating oil composition>
Testing was conducted in accordance with the ultrasound method of ASTM D2603. The smaller the number, the higher the shear stability.
＜潤滑油組成物の低温粘度（－５４℃）の測定方法＞
　－５４℃で３時間サンプルを冷却した時の粘度をＪＰＩ－５Ｓ－２６－９９に準じてブルックフィールド型粘度計で測定した。数値が小さいほど低温粘度が低く、低温特性が高いことを意味する。 <Method for measuring low-temperature viscosity (-54°C) of lubricating oil composition>
The viscosity of the sample after cooling at -54°C for 3 hours was measured using a Brookfield viscometer according to JPI-5S-26-99. The smaller the number, the lower the low-temperature viscosity and the higher the low-temperature properties.
＜潤滑油組成物の低温（－６０℃）外観の測定方法＞
　潤滑油組成物を－６０℃で３時間静置して外観の白濁の有無を確認した。下記基準で評価した結果を表３に示す。
〇：白濁していないもの
×：白濁しているもの <Method for measuring low temperature (-60°C) appearance of lubricating oil composition>
The lubricating oil composition was allowed to stand at -60°C for 3 hours, and the presence or absence of cloudy appearance was checked. Table 3 shows the results of evaluation based on the following criteria.
〇: Not cloudy ×: Cloudy
＜潤滑油組成物の加水分解安定性の測定方法＞
　潤滑油組成物の酸価をＪＩＳ　Ｋ００７０に従って測定した。
　また、作製した潤滑油組成物に対して１重量％の水を加え、１００℃で１００時間加熱した。加熱後の酸価をＪＩＳ　Ｋ００７０に従って測定した。加熱前の酸価と加熱後の酸価の差を酸価変化度として表３に記載した。 <Method for measuring hydrolytic stability of lubricating oil composition>
The acid value of the lubricating oil composition was measured according to JIS K0070.
Further, 1% by weight of water was added to the prepared lubricating oil composition, and the mixture was heated at 100° C. for 100 hours. The acid value after heating was measured according to JIS K0070. The difference between the acid value before heating and the acid value after heating is shown in Table 3 as the degree of change in acid value.
　表３の結果から、本発明の粘度指数向上剤を含有する潤滑油組成物は、粘度指数が優れており、低温でも析出物がなく、低温での粘度が低く優れており、経時変化によるリン酸エステルの加水分解が少なく、特性が優れていることが分かる。 From the results in Table 3, the lubricating oil composition containing the viscosity index improver of the present invention has an excellent viscosity index, no precipitates even at low temperatures, low viscosity at low temperatures, and excellent viscosity due to aging. It can be seen that hydrolysis of the acid ester is small and the properties are excellent.
　本発明の粘度指数向上剤組成物を用いれば、粘度指数向上効果及びリン酸エステルの加水分解抑制効果に優れ、さらに低温（－６０℃）でも析出物がなく、低温での粘度が良好な潤滑油組成物を得ることができるので、本発明の粘度指数向上剤組成物を含む潤滑油組成物は、粘度指数及びリン酸エステルの加水分解が少なく、さらに低温（－６０℃）でも析出物がなく、低温での粘度が良好なので、特に上空（低温環境下）で用いられることのある航空機用油圧作動油として有用である。

  If the viscosity index improver composition of the present invention is used, the viscosity index improver composition has an excellent viscosity index improvement effect and a phosphate ester hydrolysis inhibiting effect, and furthermore, there is no precipitate even at low temperatures (-60°C), and the viscosity at low temperatures is good for lubricants. Since the lubricating oil composition containing the viscosity index improver composition of the present invention has a low viscosity index and phosphoric acid ester hydrolysis, it also has no precipitates even at low temperatures (-60°C). Since it has a good viscosity at low temperatures, it is particularly useful as an aircraft hydraulic fluid that may be used in the sky (in a low-temperature environment).

Claims (9)

  1. 　リン酸エステル（Ｃ）を含有する潤滑油組成物用の粘度指数向上剤組成物であって、
    　下記一般式（１）で表される単量体（ａ）を必須構成単量体とする（共）重合体（Ａ）と、ＨＬＢ値が２．５～７．０である鎖状脂肪族アルコール（Ｂ）とを含有し、前記（共）重合体（Ａ）の溶解性パラメータが９．００～９．８０（ｃａｌ／ｃｍ３）１／２である粘度指数向上剤組成物。
    Figure JPOXMLDOC01-appb-C000001
     ［Ｒ１は水素原子又はメチル基；－Ｘ１－は－Ｏ－又は－ＮＨ－で表される基；Ｒ２は炭素数２～４のアルキレン基；Ｒ３は炭素数１～１７の直鎖又は分岐アルキル基；ｐは０～２０の整数であり、ｐが２以上の場合のＲ２は同一でも異なっていてもよい。］     A viscosity index improver composition for a lubricating oil composition containing a phosphoric acid ester (C),
    A (co)polymer (A) having monomer (a) represented by the following general formula (1) as an essential constituent monomer, and a chain aliphatic compound having an HLB value of 2.5 to 7.0. A viscosity index improver composition containing alcohol (B), wherein the (co)polymer (A) has a solubility parameter of 9.00 to 9.80 (cal/cm 3 ) 1/2 .
    Figure JPOXMLDOC01-appb-C000001
     [R 1 is a hydrogen atom or a methyl group; -X 1 - is a group represented by -O- or -NH-; R 2 is an alkylene group having 2 to 4 carbon atoms; R 3 is a straight group having 1 to 17 carbon atoms; Chain or branched alkyl group; p is an integer of 0 to 20, and when p is 2 or more, R 2 may be the same or different. ]
  2. 　前記（共）重合体（Ａ）の重量平均分子量が５，０００～３００，０００である請求項１に記載の粘度指数向上剤組成物。 The viscosity index improver composition according to claim 1, wherein the (co)polymer (A) has a weight average molecular weight of 5,000 to 300,000.
  3. 　前記（共）重合体（Ａ）と前記鎖状脂肪族アルコール（Ｂ）の重量比率（Ａ／Ｂ）が１０～５０００である請求項１に記載の粘度指数向上剤組成物。 The viscosity index improver composition according to claim 1, wherein the weight ratio (A/B) of the (co)polymer (A) and the chain aliphatic alcohol (B) is 10 to 5,000.
  4. 　前記鎖状脂肪族アルコール（Ｂ）が、炭素数８～１７の直鎖又は分岐鎖状脂肪族アルコールである請求項１に記載の粘度指数向上剤組成物。 The viscosity index improver composition according to claim 1, wherein the chain aliphatic alcohol (B) is a straight or branched aliphatic alcohol having 8 to 17 carbon atoms.
  5. 　さらにリン酸エステル（Ｃ）を含有してなる請求項１に記載の粘度指数向上剤組成物。 The viscosity index improver composition according to claim 1, further comprising a phosphoric acid ester (C).
  6. 　請求項１～５のいずれか１項に記載の粘度指数向上剤組成物とリン酸エステル（Ｃ）を含有する潤滑油組成物。 A lubricating oil composition comprising the viscosity index improver composition according to any one of claims 1 to 5 and a phosphoric ester (C).
  7. 前記潤滑油組成物中の前記リン酸エステル（Ｃ）の含有量が７５重量％以上である請求項６に記載の潤滑油組成物。 The lubricating oil composition according to claim 6, wherein the content of the phosphoric ester (C) in the lubricating oil composition is 75% by weight or more.
  8. 　前記リン酸エステル（Ｃ）の４０℃における動粘度が１～４０ｍｍ２／ｓである請求項６に記載の潤滑油組成物。 The lubricating oil composition according to claim 6, wherein the phosphoric acid ester (C) has a kinematic viscosity of 1 to 40 mm 2 /s at 40°C.
  9. 　航空機用油圧作動油として用いられる請求項６に記載の潤滑油組成物。

          The lubricating oil composition according to claim 6, which is used as an aircraft hydraulic fluid.
PCT/JP2023/022777 2022-06-27 2023-06-20 Viscosity index improver composition and lubricating oil composition WO2024004763A1 (en)

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Citations (7)

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Publication number Priority date Publication date Assignee Title
JPH1077494A (en) * 1996-08-08 1998-03-24 Rohm & Haas Co Hydraulic fluid composition
JP2002529577A (en) * 1998-11-10 2002-09-10 エクソンモービル リサーチ アンド エンジニアリング カンパニー Phosphate ester base oil comprising n-butyl / isobutyl phosphate ester mixture and aircraft hydraulic fluid comprising said base oil
JP2003524673A (en) * 1998-10-23 2003-08-19 エクソンモービル リサーチ アンド エンジニアリング カンパニー Phosphate base oil and hydraulic fluid for aircraft containing the base oil
JP2008546871A (en) * 2005-06-14 2008-12-25 ソリユテイア・インコーポレイテツド High performance phosphate hydraulic fluid
JP2009503142A (en) * 2005-07-19 2009-01-29 エクソンモービル リサーチ アンド エンジニアリング カンパニー Aircraft phosphate functional fluids with enhanced acid capture properties
JP2016017170A (en) * 2014-07-11 2016-02-01 東亞合成株式会社 Additive for lubricating oil and lubricating oil composition
WO2022039266A1 (en) * 2020-08-20 2022-02-24 三洋化成工業株式会社 Viscosity index improver composition and lubricating oil composition

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1077494A (en) * 1996-08-08 1998-03-24 Rohm & Haas Co Hydraulic fluid composition
JP2003524673A (en) * 1998-10-23 2003-08-19 エクソンモービル リサーチ アンド エンジニアリング カンパニー Phosphate base oil and hydraulic fluid for aircraft containing the base oil
JP2002529577A (en) * 1998-11-10 2002-09-10 エクソンモービル リサーチ アンド エンジニアリング カンパニー Phosphate ester base oil comprising n-butyl / isobutyl phosphate ester mixture and aircraft hydraulic fluid comprising said base oil
JP2008546871A (en) * 2005-06-14 2008-12-25 ソリユテイア・インコーポレイテツド High performance phosphate hydraulic fluid
JP2009503142A (en) * 2005-07-19 2009-01-29 エクソンモービル リサーチ アンド エンジニアリング カンパニー Aircraft phosphate functional fluids with enhanced acid capture properties
JP2016017170A (en) * 2014-07-11 2016-02-01 東亞合成株式会社 Additive for lubricating oil and lubricating oil composition
WO2022039266A1 (en) * 2020-08-20 2022-02-24 三洋化成工業株式会社 Viscosity index improver composition and lubricating oil composition

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