WO2017038734A1 - 共重合体および潤滑油組成物 - Google Patents
共重合体および潤滑油組成物 Download PDFInfo
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- WO2017038734A1 WO2017038734A1 PCT/JP2016/075129 JP2016075129W WO2017038734A1 WO 2017038734 A1 WO2017038734 A1 WO 2017038734A1 JP 2016075129 W JP2016075129 W JP 2016075129W WO 2017038734 A1 WO2017038734 A1 WO 2017038734A1
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- C—CHEMISTRY; METALLURGY
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- 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
- C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/22—Polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
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- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
- C10M105/36—Esters of polycarboxylic acids
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- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
- C10M105/38—Esters of polyhydroxy compounds
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- 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
- C10M129/68—Esters
- C10M129/78—Complex esters, i.e. compounds containing at least three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compound: monohydroxy compounds, polyhydroxy compounds, monocarboxylic acids, polycarboxylic acids, hydroxy carboxylic acids
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/041—Mixtures of base-materials and additives the additives being macromolecular compounds only
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
- C10M2207/2825—Esters of (cyclo)aliphatic oolycarboxylic acids used as base material
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy compounds
- C10M2207/2835—Esters of polyhydroxy compounds used as base material
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/284—Esters of aromatic monocarboxylic acids
- C10M2207/2845—Esters of aromatic monocarboxylic acids used as base material
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/285—Esters of aromatic polycarboxylic acids
- C10M2207/2855—Esters of aromatic polycarboxylic acids used as base material
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
- C10M2207/301—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids used as base material
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
- C10M2207/302—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids derived from the combination of monocarboxylic acids, dicarboxylic acids and dihydroxy compounds only and having no free hydroxy or carboxyl groups
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/40—Fatty vegetable or animal oils
- C10M2207/401—Fatty vegetable or animal oils used as base material
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/102—Polyesters
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/08—Resistance to extreme temperature
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/20—Colour, e.g. dyes
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/58—Elastohydrodynamic lubrication, e.g. for high compressibility layers
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/68—Shear stability
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/08—Hydraulic fluids, e.g. brake-fluids
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- C10N2040/20—Metal working
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- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/10—Semi-solids; greasy
Definitions
- the present invention relates to a copolymer that satisfies specific requirements, a lubricating oil composition containing a specific amount of the copolymer, and uses thereof.
- Petroleum products generally have a so-called viscosity temperature dependency in which the viscosity changes greatly when the temperature changes.
- the lubricating oil also has a temperature dependency of the viscosity, and it is preferable that the temperature dependency of the viscosity is small.
- a polymer soluble in a lubricating base oil is used as a viscosity index improver.
- a typical viscosity modifier a mineral oil solution of an olefin copolymer or a polymer of polymethacrylate (hereinafter referred to as PMA) is known.
- lubricating oil compositions for grease and engine oil containing vegetable oils such as soybean oil and rapeseed oil as base oils and synthetic esters such as polyols have been proposed (for example, see Non-Patent Document 1).
- the lubricating oil composition containing vegetable oil as the base oil has a problem in storage characteristics and stability at low temperatures.
- a viscosity modifier such as an OCP (olefin copolymer) viscosity modifier
- the viscosity modifier is poorly soluble in vegetable oil and difficult to apply.
- the solubility of the viscosity modifier in the base oil is improved by selecting a PMA (polymethacrylate) viscosity modifier as the viscosity modifier of the lubricating oil composition based on vegetable oil or synthetic ester.
- PMA polymethacrylate
- the PMA-based viscosity modifier contains 50% by mass or more of mineral oil having a low biodegradation rate as a diluent oil, the biodegradation rate of the lubricating oil composition was significantly reduced.
- Patent Document 1 discloses an attempt to use a ricinoleic acid polymer as a viscosity modifier to be blended in a lubricating oil composition.
- the ricinoleic acid polymer used in Patent Document 1 is a polymer obtained by homopolymerizing only a ricinoleic acid ester derivative or copolymerizing a ricinoleic acid ester derivative and a hydroxycarboxylic acid ester derivative.
- Patent document 1 by employ
- the biodegradability is remarkably excellent.
- the lubricating oil composition is required to be difficult to discolor even when heated, and it is desirable that the lubricating oil composition has a high adhesive strength in order to maintain adhesion to the sliding portion and to prevent scattering and sagging.
- a lubricating oil composition having excellent heat resistance (inhibition of discoloration during heating) and adhesiveness while maintaining the excellent biodegradability and viscosity characteristics of the lubricating oil composition using a ricinoleic acid polymer. Is an issue. Further, it is possible to provide such a lubricating oil composition, and further provide a polymer that can be used as a viscosity modifier excellent in handling property and solubility in base oil when producing the lubricating oil composition. This is a problem.
- the present invention relates to the following [1] to [16].
- the base oil (A) and the copolymer (B) described in [1] above, and the mass ratio of the base oil (A) and the copolymer (B) (mass of (A) / (B) mass) is a lubricating oil composition of 60/40 to 99.5 / 0.5.
- At least one additive (C) selected from the group consisting of antioxidants, extreme pressure agents, rust inhibitors, metal deactivators, antiwear additives, antifoaming agents, cleaning dispersants and pour point depressants.
- a gear oil comprising the lubricating oil composition according to any one of [2] to [11].
- a hydraulic oil comprising the lubricating oil composition according to any one of [2] to [11].
- Engine oil comprising the lubricating oil composition according to any one of [2] to [11].
- a grease comprising the lubricating oil composition according to any one of [2] to [11].
- a machining oil comprising the lubricating oil composition according to any one of [2] to [11].
- a copolymer having excellent workability (handling properties, solubility) and biodegradability can be provided as a viscosity modifier for a lubricating oil composition. Furthermore, it is possible to provide a lubricating oil composition having both shear stability, low-temperature fluidity, heat resistance (inhibition of discoloration during heating) and adhesiveness using the copolymer.
- the lubricating oil composition according to the present invention contains a base oil (A).
- examples of the base oil (A) include vegetable oils, synthetic esters, low molecular weight poly ⁇ -olefins, and the like. Of these, vegetable oils and synthetic esters are preferred.
- the base oil (A) may be a vegetable oil, a synthetic ester, or a combination thereof.
- the synthetic ester used as the base oil (A) is different from the copolymer (B) described later. That is, in the present invention, an ester that can correspond to both the synthetic ester that can be used as the base oil (A) and the copolymer (B) described later is handled as a copolymer that corresponds to the copolymer (B) described later. .
- preferred examples of the vegetable oil include rapeseed oil, soybean oil, castor oil, palm oil, sunflower oil, safflower oil, corn oil, meadow foam oil, rice bran oil, olive oil, jojoba oil, etc.
- rapeseed oil, soybean oil, castor oil, and palm oil are more preferable.
- preferred examples of the synthetic ester include diesters and polyol esters. Adopting these as the base oil (A) is preferable because the resulting lubricating oil composition can be used under a wide range of temperature conditions.
- diesters and polyol esters preferred examples include aliphatic diesters such as di-2-ethylhexyl sebacate, dioctyl adipate, dioctyl decanedioate, diisodecyl adipate, dioctyl sebacate, and the like.
- diesters include aliphatic diesters such as di-2-ethylhexyl sebacate, dioctyl adipate, dioctyl decanedioate, diisodecyl adipate, dioctyl sebacate, and the like.
- the lubricating oil composition can be used under a wide range of temperature conditions from a low temperature range (below room temperature) to a high temperature range (50 ° C. to 100 ° C.). This is preferable because it can be used.
- These synthetic esters may be used alone or in combination of two or more.
- base oil (A) one or more kinds of vegetable oils and one or more kinds of synthetic esters may be mixed and used.
- the base oil (A) should have a kinematic viscosity at 40 ° C. (according to ASTM 445 kinematic viscosity test method) of 10 to 80 mm 2 / s. Is more preferable, and 14 to 60 mm 2 / s is more preferable.
- the pour point of the base oil (A) (according to the measurement method of JIS K2269) should be 0 to -50 ° C. Is preferred.
- the lubricating oil composition according to the present invention contains a copolymer (B) as a viscosity modifier.
- the copolymer (B) satisfies the following requirements (B1) to (B3).
- Requirement (B1) a structural unit (a) derived from ricinoleic acid, A structural unit (b) derived from an aliphatic dicarboxylic acid; And a structural unit (c) derived from a diol having 2 to 10 carbon atoms.
- the structural unit (a) derived from ricinoleic acid in the present invention (hereinafter sometimes simply referred to as “structural unit (a)”) is ricinoleic acid (12-hydroxy-cis-9-octadecenoic acid) or ricinol It is a structural unit derived from an acid derivative.
- structural unit (a) is ricinoleic acid (12-hydroxy-cis-9-octadecenoic acid) or ricinol It is a structural unit derived from an acid derivative.
- the copolymer (B) contains such a structural unit (a)
- the resulting lubricating oil composition is excellent in viscosity characteristics and storage stability, and high biodegradability can be expected.
- Examples of derivatives of ricinoleic acid include condensates of ricinoleic acid, esterified products of ricinoleic acid and carboxylic acid, esterified products of ricinoleic acid and alcohols (for example, ricinoleic acid methyl ester), and reaction products of ricinoleic acid and an epoxy compound.
- Examples thereof include various compounds that give the derived structural unit (a).
- the monomer component corresponding to the structural unit (a), that is, the ricinoleic acid and the derivative of ricinoleic acid may be referred to as “monomer component (a ′)”.
- the total ratio of the units is not particularly limited, and is the sum of the structural units (a) derived from ricinoleic acid (that is, the structural unit represented by the above formula (1) and the structural unit represented by the above formula (2)) ) Is 100 mol%, it is optional in the range of 0 to 100 mol%.
- the structural unit (a) derived from ricinoleic acid is represented by the above formula (1).
- the above ratio is preferably 0 to 80 mol%, and more preferably 0 to 60 mol%.
- the ratio is excellent in terms of fluidity at a low temperature and dispersibility in a base oil (particularly vegetable oil).
- the ratio does not necessarily have to be in the preferred range. It does not exclude that the structural unit (a) derived from ricinoleic acid consists only of the structural unit represented by the above formula (2).
- the structural unit (b) derived from an aliphatic dicarboxylic acid (hereinafter sometimes simply referred to as “structural unit (b)”) is derived from an aliphatic dicarboxylic acid or an aliphatic dicarboxylic acid ester.
- structural unit (b) referred to in the present invention is a structural unit having a structure in which —OH is excluded from two carboxyl groups contained in the aliphatic dicarboxylic acid.
- the aliphatic dicarboxylic acid leading to the structural unit (b) is aliphatic in order not to lower the biodegradability and solubility in the base oil of the obtained copolymer.
- the aliphatic dicarboxylic acid is not particularly limited as long as it has no other functional group having reactivity in the system in which the ester polymerization reaction is performed, for example, a hydroxyl group, and may be used alone or in combination of two or more.
- malonic acid (3 carbon atoms), dimethyl malonic acid (5 carbon atoms), succinic acid (4 carbon atoms), glutaric acid (5 carbon atoms), adipic acid (6 carbon atoms) 2-methyladipic acid (7 carbon atoms), trimethyladipic acid (9 carbon atoms), pimelic acid (7 carbon atoms), 2,2-dimethylglutaric acid (7 carbon atoms), 3,3- Examples include diethyl succinic acid (8 carbon atoms), suberic acid (8 carbon atoms), azelaic acid (9 carbon atoms), sebacic acid (10 carbon atoms), and the like.
- examples of the aliphatic dicarboxylic acid ester include various esters of the above aliphatic dicarboxylic acid.
- aliphatic dicarboxylic acids having 6 to 12 carbon atoms are preferred, and sebacic acid is particularly preferred.
- the monomer component corresponding to the structural unit (b), that is, the aliphatic dicarboxylic acid and the aliphatic dicarboxylic acid ester may be referred to as “aliphatic dicarboxylic acid component (b ′)”.
- structural unit (c) derived from diol having 2 to 10 carbon atoms
- structural unit (c) has a formally having 2 to 10 carbon atoms. Is a structural unit having a structure obtained by removing —H from two hydroxyl groups contained in the diol.
- the diol having 2 to 10 carbon atoms for leading the structural unit (c) one kind may be used alone, or two or more kinds may be used in combination. Specific examples include the following compounds.
- Examples of the diol having 2 to 10 carbon atoms include aliphatic diols having 2 to 10 carbon atoms.
- Examples of such aliphatic diols include 1,2-ethanediol (ethylene glycol: 2 carbon atoms), 1,3-propanediol (trimethylene glycol: 3 carbon atoms), 1,2-propanediol ( Propylene glycol: 3 carbon atoms, 1,4-butanediol (tetramethylene glycol: 4 carbon atoms), 2,2-dimethylpropane-1,3-diol (neopentyl glycol: 5 carbon atoms), 1 , 6-hexanediol (hexamethylene glycol: 6 carbon atoms), 1,8-octanediol (octamethylene glycol: 8 carbon atoms), 1,9-nonanediol (nonamethylene glycol: 9 carbon atoms), etc. Is mentioned.
- side chain alkyl group-containing glycols include 2-methyl-1,3-propanediol, 2-ethyl-1,3-propanediol, 2-hexyl-1,3-propanediol, 2-hexyl-1,6-propanediol, neopentyl glycol, 2-ethyl-2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-n -Butyl-1,3-propanediol, 1,3-nonanediol, 2-methyl-1,8-octanediol, and the like.
- 1,4-butanediol is particularly preferable.
- the monomer component corresponding to the structural unit (c), that is, the diol having 2 to 10 carbon atoms may be referred to as “diol component (c ′)”.
- the copolymer (B) used in the present invention includes the structural units (b) and (c) in addition to the structural unit (a).
- copolymer (B) also contains said structural unit (b) and (c)
- the heat resistance and handling property in the obtained lubricating oil composition and more strictly, the following Example mentioned later As shown by, it is excellent in heat resistance and adhesiveness. The reason why such an effect is obtained will be described later in “Characteristics of Copolymer (B)”.
- the copolymer (B) used in the present invention is preferably composed of only the structural units (a) to (c). However, as long as the effects of the present invention are not impaired, the structural unit (a) A structural unit that does not fall under any of (c) (hereinafter referred to as “other structural unit”) may be further included.
- furandicarboxylic acid such as 2,5-furandicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, alicyclic dicarboxylic acid such as 1,3-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid
- 2 A structural unit derived from various dicarboxylic acids and carboxylic esters not corresponding to the aliphatic dicarboxylic acid component (b ′), such as aromatic dicarboxylic acids such as methyl terephthalic acid and naphthalenedicarboxylic acid, and having 11 or more carbon atoms
- the above aliphatic diols, aromatic diols, trivalent or higher polyhydric alcohols, trivalent or higher polyvalent carboxylic acids and oxydicarboxylic acids may be referred to as “other monomer components”.
- Requirement (B2) When the total of the structural units (a), (b) and (c) is 100 mol%, the content of the structural unit (a) is 20 to 90 mol%, and the structural unit (b) The content of the structural unit (c) is 5 to 40 mol%.
- the lower limit of the content of the structural unit (a) is 20 mol%, more preferably 30 mol%, still more preferably 40 mol%, and particularly preferably 50 mol%. It is preferable that the content of the structural unit (a) is 20 mol% or more in terms of imparting appropriate stickiness. When it is 30 mol% or more, it is more preferable in terms of improving the viscosity characteristics of the resulting composition and the storage stability, that is, the turbidity (haze) of the base oil. Storage stability is particularly preferable when it is 40 mol% or more. Also, shear stability is preferred. On the other hand, the upper limit of the content of the structural unit (a) is 90 mol%, but 85 mol% is more preferable.
- the content of the structural unit (a) is 90 mol% or less from the viewpoint of heat resistance and tackiness of the resulting composition.
- the content of the structural unit (a) is preferably 40 to 90 mol%, more preferably 45 to 85 mol%.
- the molar ratio ((b) / (c)) between the structural unit (b) and the structural unit (c) is preferably 0.9 to 1.1.
- the copolymer (B) according to the present invention is preferably composed of only the structural units (a) to (c) as described above, but includes other structural units as long as the effects of the invention are not impaired. You may go out.
- the content of the other structural units in the copolymer (B) is the sum of the above structural units (a) to (c) and other structural units.
- the mol% is preferably 20 mol% or less, more preferably 10 mol% or less, and particularly preferably 5 mol% or less.
- the contents of the structural units (a) to (c) and “other structural units” in the copolymer (B) can be determined by an appropriate method such as NMR.
- Intrinsic viscosity [IV] is in the range of 0.1 to 2.0 dl / g. Preferably 0.1 to 1.5 dl / g, more preferably 0.2 to 1.5 dl / g, still more preferably 0.2 to 1.0 dl / g, particularly preferably 0.2 to 0.6 dl / g. It is. It exists in the workability
- the measurement conditions for the intrinsic viscosity [IV] are as described in the Examples section.
- the copolymer (B) having an intrinsic viscosity [IV] in such a range the resulting lubricating oil composition can be imparted with excellent thickening and viscosity index improving effects.
- the said base oil (A) is a vegetable oil
- favorable low-temperature storage stability can be provided to the obtained lubricating oil composition.
- Intrinsic viscosity [IV] can be adjusted to the said range by adjusting the molecular weight of a copolymer (B).
- the copolymer (B) used by this invention is a copolymer containing the structural unit represented by the said Formula (1) as said structural unit (a) among the copolymers (B) as needed.
- B0) may be subjected to a treatment such as hydrogenation.
- the copolymer (B) of the present invention has fewer ester bonds derived from secondary hydroxyl groups (12-position hydroxyl groups) than the homopolymer of ricinoleic acid derivatives, and the length between adjacent ester groups (carbon chain carbon). (Length represented by a number) includes a relatively short structure. This means that there are few thermally unstable bonds in the copolymer (B), which is considered to contribute to heat resistance stability. Further, the high ester group density is likely to have a compact structure due to intermolecular interaction, which is considered to contribute to workability (handling properties and solubility).
- the copolymer (B) of the present invention has more primary hydroxyl groups in the monomer component than the homopolymer of the ricinoleic acid derivative, the ester polymerization reaction can proceed more stably. It is considered that the effect of excellent heat stability is obtained by suppressing dehydration in the coalescence and suppressing the double bond amount of the copolymer obtained.
- the copolymer (B) of the present invention has a relatively low ratio of ricinoleic acid derivatives having a long side chain as compared with a homopolymer of ricinoleic acid derivative, and thus in the resulting lubricating oil composition. It is considered that excellent shear stability can be obtained.
- the copolymer (B) is a compound that leads to the structural units (a), (b), and (c), that is, the monomer component (a ′) and the aliphatic dicarboxylic acid component (b ′). And obtained by performing an ester polymerization reaction on the diol component (c ′).
- the ricinoleic acid or ricinoleic acid derivative described above in the section “Structural unit derived from ricinoleic acid (a)” and the aliphatic dicarboxylic acid described above in the “structural unit derived from aliphatic dicarboxylic acid (b)” It is obtained by subjecting an aliphatic dicarboxylic acid ester and a diol having 2 to 10 carbon atoms described above in the section “Structural unit (c) derived from diol having 2 to 10 carbon atoms” to ester polymerization reaction with each other.
- This ester polymerization reaction is carried out by using various dicarboxylic acids, carboxylic acid esters, aliphatic diols having 11 or more carbon atoms, aromatic diols, trihydric or higher polyhydric alcohols, trivalent or higher.
- dicarboxylic acids carboxylic acid esters
- aliphatic diols having 11 or more carbon atoms
- aromatic diols trihydric or higher polyhydric alcohols, trivalent or higher.
- other structural units A copolymer (B) containing also can be obtained.
- the monomer component (a ′), the aliphatic dicarboxylic acid component (b ′), the diol component (c ′), and the optional “other monomer component” are mixed in a conventional manner.
- a copolymer can be obtained by direct condensation polymerization.
- the diol (the diol component (c ′) and the various diols described in the section “Other structural units” above) is heated under pressure, and the condensed water produced is removed from the reaction system while removing the condensed water from the reaction system. Then, the reaction system is depressurized in the presence of a polycondensation catalyst such as a titanium compound, a germanium compound, or an antimony compound, and the diol is distilled out of the system.
- a polycondensation catalyst such as a titanium compound, a germanium compound, or an antimony compound
- the polyester resin can be manufactured.
- the monomer component (a ′), the dicarboxylic acid component and the diol are reacted is mentioned.
- the “other monomer component” a trihydric or higher polyhydric alcohol and / or Or when trivalent or more polyvalent carboxylic acid coexists, it can carry out similarly.
- a corresponding dialkyl ester of dicarboxylic acid may be used as a starting material.
- a corresponding dialkyl ester is employed as the aliphatic dicarboxylic acid component (b ′), the monomer component (a ′), the diol component (c ′), and the optional “other unit”.
- a copolymer can be obtained by carrying out direct polycondensation with a monomer component "by a conventional method.
- various dicarboxylic acids described in the above-mentioned monomer component (a ′) and / or the above-mentioned “other structural unit” may also be used in the form of the corresponding alkyl ester.
- the monomer component (a ′), A dialkyl ester of a dicarboxylic acid (the aliphatic dicarboxylic acid component (b ′) and various dicarboxylic acids described above in the section “Other structural units”);
- the diol (the diol component (c ′) and the various diols described above in the section “Other structural units”) is heated at normal pressure, and the low molecular weight condensation is performed while removing the generated alkyl alcohol from the reaction system. Then, the reaction system is depressurized in the presence of a polycondensation catalyst such as a titanium compound, a germanium compound, or an antimony compound, and the diol is distilled out of the system.
- a polycondensation catalyst such as a titanium compound, a germanium compound, or an antimony compound
- a high molecular weight polyester resin can be manufactured.
- the monomer component (a ′) is reacted with a dialkyl ester of a dicarboxylic acid and a diol is described.
- the “other monomer component” a trihydric or higher polyhydric alcohol is used. It can also be carried out in the same manner when a trivalent or higher polyvalent carboxylic acid coexists.
- the esterification reaction in the direct esterification method and transesterification method proceeds even without a catalyst, but it is preferable to use a polycondensation catalyst as exemplified above.
- the copolymer polyester resin obtained by melt polymerization can be subjected to solid phase polymerization to increase the molecular weight.
- the copolymer (B) of the present invention can also be produced by an ester polymerization reaction with lipase.
- the monomer component (a ′), the aliphatic dicarboxylic acid component (b ′), the diol component (c ′) and the optional “other monomer component” are added in the presence of lipase.
- a copolymer can be obtained by condensation polymerization.
- the lipase is preferably an immobilized lipase derived from Burkholderia cepacia (eg, Lipase PS-C Amano II (trade name), PS-D Amano I (trade name), etc., manufactured by Wako Chemical Co., Ltd.).
- the reaction temperature can be increased to 90 ° C.
- the reaction conditions are preferably a batch method using a reactor equipped with a stirrer under bulk conditions.
- the reaction time is usually 4 to 7 days, although it varies depending on conditions such as catalyst concentration and polymerization temperature.
- the ester polymerization reaction is a reversible reaction, and it is preferable to sequentially remove the generated alcohol and water in order to advance an efficient polymerization reaction. Specifically, maintaining the pressure state in the reaction system in a reduced pressure state, or performing a synthesis reaction after placing a hygroscopic agent such as synthetic zeolite (for example, molecular sieve 4A) in the reaction system in a non-contact manner. Is mentioned. By carrying out the polymerization reaction under such conditions, the polymerization reaction can be advanced simply and easily, and the copolymer (B) can be synthesized efficiently.
- a hygroscopic agent such as synthetic zeolite (for example, molecular sieve 4A)
- the monomer component (a ′), the aliphatic dicarboxylic acid component (b ′), the diol component (c ′), and the optional “other monomer component” in each ester polymerization reaction can be adjusted as appropriate according to the contents of the structural units (a), (b), (c) and “other structural units” to be achieved in the copolymer (B). .
- the copolymer obtained by such ester polymerization reaction may be used as it is as the copolymer (B), but further, a hydrogenation reaction is carried out using a conventionally known appropriate method. Thus, hydrogenation may be carried out on some or all of the double bonds contained in the structural unit (a).
- a copolymer (B0) containing the structural unit represented by the above formula (1) as the structural unit (a) in the copolymer (B) is prepared by an ester polymerization reaction.
- the copolymer (B0) may be partially or completely hydrogenated, and a product obtained by such hydrogenation may be employed as the copolymer (B).
- the mass ratio of the base oil (A) to the copolymer (B) is 60/40 to 99.5 / 0.5, preferably 75/25 to 99/1, and more preferably 80/20 to 97/3.
- the base oil (A) and the copolymer (B) are contained in the lubricating oil composition, good compatibility between the base oil (A) and the copolymer (B). And a thickening effect is imparted to the lubricating oil composition.
- the lubricating oil composition can exhibit an appropriate viscosity index, and therefore has good fluidity. Furthermore, when the base oil (A) is a vegetable oil, the low temperature storage stability of the lubricating oil composition can be improved.
- the kinematic viscosity (based on ASTM D445) at 40 ° C. of the lubricating oil composition according to the present invention is 50 preferably to ⁇ 700mm 2 / s, and even more preferably from 80 ⁇ 600mm 2 / s.
- the kinematic viscosity at 100 ° C. (according to ASTM D445) of the lubricating oil composition according to the present invention is: It is preferably 10 to 100 mm 2 / s, more preferably 15 to 70 mm 2 / s.
- the viscosity index (based on ASTM D2270) of the lubricating oil composition according to the present invention is 180. Is preferably from 250 to 250, and more preferably from 200 to 250.
- the lubricating oil composition of the present invention can be expected to have high biodegradability due to its composition.
- the lubricating oil composition is naturally scattered (leakage)
- the biodegradation rate based on “OECD301C” is preferably 40% or more, and more preferably 60% or more.
- the lubricating oil composition according to the present invention is added depending on the purposes such as oxidation stability, rust prevention, extreme pressure, and defoaming. It is preferable that an agent (C) is included.
- Such additives (C) include from the group consisting of antioxidants, extreme pressure agents, rust inhibitors, metal deactivators, antiwear additives, antifoaming agents, detergent dispersants and pour point depressants. One or more selected are preferable.
- the total amount of additive (C) can be appropriately blended within a range not impairing the object of the present invention, but is 0.05 to 25% by mass with respect to 100% by mass of the lubricating oil composition. It is preferable.
- antioxidants As the antioxidant used in the lubricating oil composition of the present invention, known antioxidants can be used. Specifically, di (alkylphenyl) amine (alkyl group has 4 to 20 carbon atoms), phenyl- ⁇ -Naphthylamine, alkyldiphenylamine (alkyl group has 4 to 20 carbon atoms), N-nitrosodiphenylamine, phenothiazine, N, N'-dinaphthyl-p-phenylenediamine, acridine, N-methylphenothiazine, N-ethylphenothiazine, dipyridylamine, Amine antioxidants such as diphenylamine, phenolamine, 2,6-di-t-butyl- ⁇ -dimethylaminoparacresol, 2,6-di-t-butylparacresol, 4,4′-methylenebis (2, 6-di-t-butylphenol), 2,6-di-di-
- Extreme pressure agent As the extreme pressure agent used in the lubricating oil composition of the present invention, known extreme pressure additives can be used. Specifically, chlorine compounds such as chlorinated paraffin, chlorinated diphenyl, and chlorinated fatty acid; Sulfur compounds such as fatty acid, sulfurized fatty acid ester, sulfurized animal oil, sulfurized vegetable oil, dibenzyl disulfide, synthetic polysulfide, amine salt or alkali metal salt of alkylthiopropionic acid, and amine salt or alkali metal salt of alkylthioglycolic acid; phosphoric acid Esters, acidic phosphate esters, amine salts of acidic phosphate esters, and phosphorus compounds such as chlorinated phosphate esters and phosphite esters, zinc dialkyldithiophosphates or zinc diallyldithiophosphates, organomolybdenum compounds, naphthenic acids Metal soap such as lead, organic borate Le and metal salts
- One or two or more extreme pressure agents can be added to the lubricating oil composition of the present invention, and the combination of extreme pressure additives used when adding two or more types has the desired characteristics of the resulting lubricating oil composition. It can be arbitrarily combined so that it can have.
- the content of the extreme pressure agent in the lubricating oil composition is preferably 0.5 to 10 parts by mass, and preferably 2 to 8 parts by mass with respect to 100 parts by mass of the base oil (A). Further preferred.
- rust inhibitor used in the lubricating oil composition of the present invention include petroleum sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, alkenyl succinic acid ester, and polyhydric alcohol ester.
- Metal deactivator examples of the metal deactivator used in the lubricating oil composition of the present invention include benzotriazole and its derivatives, and thiazole compounds.
- Anti-wear additive examples include phosphorus compounds, organic molybdenum compounds, fatty acid ester compounds, and aliphatic amine compounds.
- antiwear additives for phosphorus compounds include zinc alkyldithiophosphates, phosphoric acid, phosphorous acid, phosphoric acid monoesters, phosphoric acid diesters, phosphoric acid triesters, phosphorous acid monoesters, Examples thereof include phosphoric acid diesters, phosphite triesters, salts of (phosphite) esters, and thiophosphoric acid, thiophosphorous acid or esters thereof, and mixtures thereof.
- zinc alkyldithiophosphate is preferably used, and usually contains a hydrocarbon group having 2 to 30 carbon atoms, preferably 3 to 20 carbon atoms.
- hydrocarbon group having 2 to 30 carbon atoms examples include an alkyl group, a cycloalkyl group, an alkylcycloalkyl group, an alkenyl group, an aryl group, an alkylaryl group, and an arylalkyl group.
- organic molybdenum compound as the antiwear additive examples include molybdenum dithiocarbamate, molybdenum dithiophosphate, and molybdate amine salt, and molybdenum dithiocarbamate is particularly preferable.
- antifoaming agent used in the lubricating oil composition of the present invention known antifoaming agents can be used.
- silicon-based antifoaming agents such as dimethylsiloxane and silica gel dispersion
- alcohols and ester-based antifoaming agents can be mentioned.
- detergent dispersant used in the lubricating oil composition of the present invention
- known detergent dispersants can be used.
- metal sulfonates such as calcium sulfonate, magnesium sulfonate, barium sulfonate, thiophosphonate, phenate, salicylate, succinimide , Benzylamine, succinic acid ester and the like.
- Pour point depressants include alkylated naphthalenes, alkyl methacrylate (co) polymers, alkyl acrylate (co) polymers, copolymers of alkyl fumarate and vinyl acetate, ⁇ -olefin polymers, ⁇ -olefins And styrene copolymer.
- alkyl methacrylate (co) polymer, an alkyl acrylate (co) polymer, and the like can be given.
- the lubricating oil composition of the present invention is obtained by mixing and kneading a base oil (A), a predetermined copolymer (B), and, if necessary, an additive (C) at a predetermined ratio.
- a mixing / kneading means a known mixing / kneading apparatus such as a tank blend method or an auto blender method can be used.
- the mixing / kneading may be performed at room temperature, but in order to improve the uniformity of each component in the lubricating oil composition, the components are mixed after heating to 60 to 80 ° C. or while heating. -It is preferable to knead.
- the lubricating oil composition according to the present invention is very useful as a lubricating oil composition for each application because it has good viscosity characteristics and friction characteristics and is excellent in biodegradability.
- Specific applications include, for example, gear oil, hydraulic oil, engine oil, grease, machining oil, sliding surface oil, electrical insulating oil, turbine oil, gear oil, air compressor oil, compressor oil, vacuum pump oil, Bearing oil, heat medium oil, mist oil, refrigerator oil, and rock drill oil are preferred.
- examples of the engine oil include two-cycle engine oil, gasoline engine oil, and diesel engine oil.
- examples of the machining oil include cutting oil, grinding oil, punching oil, drawing oil, press oil, drawing oil, rolling oil, forging oil, and the like.
- Rapeseed oil MP Biomedical
- A-2 DIDA (diisodecyl adipate): Daihachi Chemical Industries
- A-3 H-334R (neopentyl polyol fatty acid ester): NOF Corporation
- An ECA500 type nuclear magnetic resonance apparatus manufactured by JEOL Ltd. was used, and deuterated chloroform was used as a solvent.
- the sample concentration was 35 mg / 0.5 mL, and the measurement temperature was 50 ° C.
- the observation nucleus is 1H (500 MHz), the sequence is a single pulse, the pulse width is 6.3 ⁇ s (45 ° pulse), the repetition time is 8.5 seconds, the integration number is 394 times, and the hydrogen signal of tetramethylsilane is chemically shifted. Measured as a reference value.
- Each peak was assigned by a conventional method.
- Intrinsic Viscosity (IV) is obtained by dissolving 0.5 g of a sample (polyester resin) using 100 ml of a 1,1,2,2-tetrachloroethane / phenol mixed solution (50% by mass / 50% by mass), The mixed solution is heated and dissolved at 135 ° C. for 40 minutes, then cooled with water at 25 ° C., and the solution viscosity at 25 ° C. is measured and calculated using an Ubbelohde viscometer.
- the intrinsic viscosity is a value calculated by the following formula.
- ⁇ SP (t ⁇ t0) / t0 t: Number of seconds that the sample solution flows (seconds) t0: The number of seconds that the solvent flows (seconds) [Melting point (Tm), glass transition temperature (Tg)]
- Tm melting point
- Tm melting point
- DSC220C type manufactured by Seiko Instruments Inc.
- the second heating was performed to 150 ° C. at 10 ° C./min.
- the peak temperature (° C.) at the second heating was defined as the melting point (Tm) of the copolymer, and the displacement point corresponding to the glass transition was defined as the glass transition temperature (Tg).
- ⁇ Can be taken out by tilting the container at 23 ° C.
- ⁇ Can be taken out using a spatula at 23 °C.
- ⁇ Can be taken out by heating to 50 °C.
- Example 1-1 (Production of copolymer B-1) 40.0 parts by mass of ricinoleic acid, 5.8 parts by mass of sebacic acid, and 5.2 parts by mass of 1,4-butanediol were heated from room temperature to 210 ° C. over 30 minutes. After reaching 210 ° C., 0.20 parts by mass of titanium tetrabutoxide and 0.03 parts by mass of a 20 wt% aqueous solution of ethylammonium hydroxide were added and held at 210 ° C. for 5 hours to carry out an esterification reaction.
- Example 1-2 (Production of copolymer B-2) 40.0 parts by mass of ricinoleic acid, 10.2 parts by mass of adipic acid, and 9.7 parts by mass of 1,4-butanediol were heated from room temperature to 210 ° C. over 30 minutes. Thereafter, a polyester was obtained in the same manner as in Example 1-1.
- Example 1-3 (Production of copolymer B-3) 40.0 parts by mass of ricinoleic acid, 13.6 parts by mass of sebacic acid, and 9.7 parts by mass of 1,4-butanediol were heated from room temperature to 210 ° C. over 30 minutes. Thereafter, a polyester was obtained in the same manner as in Example 1-1.
- Example 1-4 (Production of copolymer B-4) 20.0 parts by mass of ricinoleic acid, 19.6 parts by mass of 12-hydroxystearic acid, 13.6 parts by mass of sebacic acid, and 9.7 parts by mass of 1,4-butanediol were raised from room temperature to 210 ° C. over 30 minutes. Warm up. Thereafter, a polyester was obtained in the same manner as in Example 1-1.
- Example 1-5 (Production of copolymer B-5) 30.5 parts by mass of ricinoleic acid, 20.6 parts by mass of sebacic acid, and 13.3 parts by mass of 1,4-butanediol were heated from room temperature to 210 ° C. over 30 minutes. Thereafter, a polyester was obtained in the same manner as in Example 1-3.
- Examples 1-6 to 1-9 (Production of copolymers B-6 to B-9) A polyester was obtained in the same manner as in Example 1-3, except that the polycondensation reaction was terminated when the stirring torque reached a predetermined range. That is, Examples 1-6 to 1-9 are examples in which the polycondensation reaction performed in Example 1-3 was performed by changing the magnitude of the stirring torque as a reference for terminating the reaction. This corresponds to an embodiment performed by changing
- Example 1-10 (Production of copolymer B-10) 39.2 parts by mass of 12-hydroxystearic acid, 13.6 parts by mass of sebacic acid, and 9.7 parts by mass of 1,4-butanediol were heated from room temperature to 210 ° C. over 30 minutes. Thereafter, a polyester was obtained in the same manner as in Example 1-1.
- compositions and physical properties of the (co) polymers obtained in the form of polyester in each production example are shown in Table 2-1 and Table 2-2 below.
- the compound name described in the column of each structural unit represents the compound used for the formation of the structural unit.
- Table 2-1 shows that the copolymer (B-1) contains 70 mol% of the structural unit obtained from ricinoleic acid as the structural unit (a). It represents that the structural unit obtained from sebacic acid as the structural unit (b) is 15 mol% and the structural unit obtained from 1,4-butanediol as the structural unit (c) is 15 mol%. .
- ⁇ Each component of the lubricating oil composition is uniformly dispersed and not separated.
- Viscosity characteristics Viscosity index: The viscosity index was determined based on ASTM D2270.
- Shear stability is a measure of kinematic viscosity loss due to shearing of the copolymer component in the lubricating oil at the metal sliding portion and breaking of the molecular chain.
- V Low temperature fluidity (-10 ° C, -40 ° C viscosity)
- ⁇ 40 ° C. viscosity was measured with a Brookfield viscometer at ⁇ 10 ° C. and ⁇ 40 ° C.
- Adhesiveness stringiness, adhesive strength
- the tackiness of the lubricating oil was evaluated as follows.
- the stringing property was evaluated by observing and evaluating the presence or absence of stringing when one drop of the sample was sandwiched between the thumb and index finger at room temperature and both fingers were released or touched.
- the adhesive strength was determined by immersing a metal rod with a spiral groove attached to a stirrer in a sample at room temperature and rotating the sample at 300 rpm. The sample pulled up along the groove of the metal rod (from the liquid surface) (Height / mm) was observed and evaluated.
- the adhesiveness of the lubricating oil was comprehensively evaluated based on the stringiness and adhesive strength, and the evaluation result was judged according to the following score.
- Grade 5 Sufficient stringiness and high adhesive strength (5 mm or more) Grade 4; Has stringiness and high adhesion strength (5 mm or more) Score 3; Has stringiness Shows stickiness (1-5mm) Rating 2; Slight stringing is observed and stickiness is shown (1-5mm) Grade 1; stringiness is not seen and adhesiveness is low (0 mm) (Vii)
- the heat resistance test of a heat- resistant lubricating oil is usually performed by adding an additive such as an antioxidant.
- a lubricating oil composition for heat resistance evaluation was prepared by adding and dissolving 0.5% by weight of 2,6-di-tert-butyl-p-cresol to each lubricating oil composition of Examples or Comparative Examples.
- Examples 2-2 to 2-8, Comparative Examples 2-1 to 2-4 A lubricating oil composition was prepared by mixing according to Tables 3-1 and 3-2 below. The evaluation results are shown in Tables 3-1 and 3-2.
- Rapeseed oil (A-1), copolymer (B-3) and copolymer (B-10) were mixed at a mass ratio of 90/5/5 to prepare a lubricating oil composition.
- the evaluation results are also shown in Table 3-2.
- a synthetic polyol ester (A-3) was used and mixed at a ratio according to Table 3-2 to prepare a lubricating oil composition.
- the evaluation results are also shown in Table 3-1.
- Table 3-3 shows examples and comparative examples in which a synthetic ester (A-2) was used as a base oil and a (co) polymer was blended so that the kinematic viscosity (40 ° C.) was about 100 mm 2 / s. Is contrasted. From Table 3-3, it can be seen that each of the examples is superior in shear stability to the composition of Comparative Example 2-5 using the ricinoleic acid homopolymer. Furthermore, it can be seen that the lower the intrinsic viscosity of the copolymer (B) used, the better the shear stability. Furthermore, it turns out that the Example using the copolymer which contains many structural units (a) derived from ricinoleic acid (70 mol%) is excellent in shear stability.
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Abstract
Description
下記要件(B1)~(B3)を満たす共重合体(B):
(B1)リシノール酸に由来する構成単位(a)と、
脂肪族ジカルボン酸に由来する構成単位(b)と、
炭素原子数2~10のジオールに由来する構成単位(c)と
を含む;
(B2)前記構成単位(a)、(b)および(c)の合計を100モル%としたとき、前記構成単位(a)の含量が20~90モル%、前記構成単位(b)の含量が5~40モル%、前記構成単位(c)の含量が5~40モル%である;
(B3)極限粘度[IV]が0.1~2.0dl/gの範囲にある。
基油(A)と、前記[1]に記載の共重合体(B)と
を含み、かつ、前記基油(A)と前記共重合体(B)との質量比((A)の質量/(B)の質量)が60/40~99.5/0.5である潤滑油組成物。
前記基油(A)が植物油および/又は合成エステルである前記[2]に記載の潤滑油組成物。
前記合成エステルが、ジエステルまたはポリオールエステルである前記[3]に記載の潤滑油組成物。
前記合成エステルが、脂肪族ジエステルまたは脂肪族ポリオールエステルである前記[3]または[4]に記載の潤滑油組成物。
前記要件(B2)において、前記構成単位(b)と前記構成単位(c)とのモル比((b)/(c))が0.9~1.1である、前記[2]~[5]のいずれかに記載の潤滑油組成物。
前記要件(B2)において、前記構成単位(a)が40~90モル%である、前記[2]~[6]のいずれかに記載の潤滑油組成物。
前記要件(B3)において、極限粘度[IV]が0.3~1.5dl/gの範囲にある、前記[2]~[7]のいずれかに記載の潤滑油組成物。
酸化防止剤、極圧剤、防錆剤、金属不活性剤、耐摩耗添加剤、消泡剤、清浄分散剤および流動点降下剤からなる群から選ばれる少なくとも1種の添加剤(C)をさらに含む前記[2]~[8]のいずれかに記載の潤滑油組成物。
前記脂肪族ジカルボン酸がセバシン酸である、前記[2]~[9]のいずれかに記載の潤滑油組成物。
前記炭素原子数2~10のジオールが1,4-ブタンジオールである、前記[2]~[10]のいずれかに記載の潤滑油組成物。
前記[2]~[11]のいずれかに記載の潤滑油組成物からなるギヤー油。
前記[2]~[11]のいずれかに記載の潤滑油組成物からなる作動油。
前記[2]~[11]のいずれかに記載の潤滑油組成物からなるエンジン油。
前記[2]~[11]のいずれかに記載の潤滑油組成物からなるグリース。
前記[2]~[11]のいずれかに記載の潤滑油組成物からなる機械加工油。
本発明に係る潤滑油組成物は、基油(A)を含む。本発明において、基油(A)の種類としては、植物油、合成エステル、低分子量のポリα-オレフィン等を挙げることができる。なかでも植物油、合成エステルが好ましい。この場合、基油(A)は、植物油でもよく、合成エステルでもよく、あるいは、これらの組み合わせであってもよい。
本発明に係る潤滑油組成物は、粘度調整剤として共重合体(B)を含む。本発明において、共重合体(B)は下記要件(B1)~(B3)を満たす。
脂肪族ジカルボン酸に由来する構成単位(b)と、
炭素原子数2~10のジオールに由来する構成単位(c)と
を含む。
本発明におけるリシノール酸に由来する構成単位(a)(以下、単に「構成単位(a)」と呼ぶ場合がある。)とは、リシノール酸(12-ヒドロキシ-cis-9-オクタデセン酸)もしくはリシノール酸誘導体由来の構成単位である。本発明では、共重合体(B)がこのような構成単位(a)を含むことにより、得られる潤滑油組成物が粘度特性と貯蔵安定性に優れ、また、高い生分解性が期待できる。
脂肪族ジカルボン酸に由来する構成単位(b)(以下、単に「構成単位(b)」と呼ぶ場合がある。)は、脂肪族ジカルボン酸または脂肪族ジカルボン酸エステルに由来する。本発明にいう構成単位(b)は、具体的には、形式上、脂肪族ジカルボン酸に含まれる2つのカルボキシル基から-OHを除いてなる構造を有する構成単位である。
炭素原子数2~10のジオールに由来する構成単位(c)(以下、単に「構成単位(c)」と呼ぶ場合がある。)は、具体的には、形式上、炭素原子数2~10のジオールに含まれる2つの水酸基から-Hを除いてなる構造を有する構成単位である。構成単位(c)を導く、炭素原子数2~10のジオールとしては、一種単独でも二種以上を組み合わせてもよく、具体的には以下の化合物が例示できる。
本発明で用いられる共重合体(B)は、上記の構成単位(a)~(c)のみで構成されることが好ましいが、本発明の効果を阻害しない限り、上記の構成単位(a)~(c)のいずれにも該当しない構成単位(以下、「その他の構成単位」)をさらに含んでもよい。その他の構成単位としては、2,5-フランジカルボン酸などのフランジカルボン酸、1,4-シクロヘキサンジカルボン酸、1,3-シクロヘキサンジカルボン酸などの脂環族ジカルボン酸、テレフタル酸、イソフタル酸、2-メチルテレフタル酸、ナフタレンジカルボン酸などの芳香族ジカルボン酸、などの、上記脂肪族ジカルボン酸成分(b')に該当しない各種ジカルボン酸やカルボン酸エステルに由来する構成単位、炭素原子数11以上の脂肪族ジオールに由来する構成単位、芳香族ジオールに由来する構成単位、トリメチロールエタン、グリセリン等の3価以上の多価アルコール、ブタントリカルボン酸、トリメリット酸、などの3価以上の多価カルボン酸、4-ヒドロキシフタル酸などのオキシジカルボン酸等が例示される。
本発明の共重合体(B)は、リシノール酸誘導体の単独重合体に比べて2級水酸基(12位の水酸基)由来のエステル結合が少なく、隣り合うエステル基間の長さ(炭素連鎖の炭素数で表される長さ)が比較的短い構造を含むことを特徴とする。これは共重合体(B)において熱的に不安定な結合が少ないことを意味するため、耐熱安定性に寄与すると考えられる。また、エステル基密度が高いことは、分子間相互作用によりコンパクトな構造を取りやすく、それが作業性(ハンドリング性および溶解性)に寄与すると考えられる。
上記共重合体(B)は、上記の構成単位(a)、(b)および(c)を導く化合物、すなわち、上記単量体成分(a')、上記脂肪族ジカルボン酸成分(b')および上記ジオール成分(c')に対しエステル重合反応を行うことで得られる。すなわち、上記セクション「リシノール酸に由来する構成単位(a)」で上述したリシノール酸もしくはリシノール酸誘導体と、上記「脂肪族ジカルボン酸に由来する構成単位(b)」で上述した脂肪族ジカルボン酸もしくは脂肪族ジカルボン酸エステルと、上記セクション「炭素原子数2~10のジオールに由来する構成単位(c)」で上述した炭素原子数2~10のジオールとを互いにエステル重合反応させることにより得られる。このエステル重合反応を、上記セクション「その他の構成単位」で上述した各種ジカルボン酸、カルボン酸エステル、炭素原子数11以上の脂肪族ジオール、芳香族ジオール、3価以上の多価アルコール、3価以上の多価カルボン酸、オキシジカルボン酸などの共存下で行うと、「その他の構成単位」
をも含む共重合体(B)を得ることができる。
上記単量体成分(a')と、
ジカルボン酸成分(上記脂肪族ジカルボン酸成分(b')、および、上記セクション「その他の構成単位」で上述した各種ジカルボン酸)と、
ジオール(上記ジオール成分(c')、および、上記セクション「その他の構成単位」で上述した各種ジオール)と
を加圧下で昇温し、生成する縮合水を反応系外に除きながら低分子量の縮合物とした後、チタン化合物、ゲルマニウム化合物、アンチモン化合物などの重縮合触媒の存在下に反応系内を減圧してジオールを系外に留去する。これにより、高分子量のポリエステル樹脂を製造することができる。なお、この例では、上記単量体成分(a')とジカルボン酸成分とジオールとを反応させる場合について触れたが、上記「その他の単量体成分」として3価以上の多価アルコールおよび/または3価以上の多価カルボン酸が共存する場合にも同様に行うことができる。
上記単量体成分(a')と、
ジカルボン酸(上記脂肪族ジカルボン酸成分(b')、および、上記セクション「その他の構成単位」で上述した各種ジカルボン酸)のジアルキルエステルと、
ジオール(上記ジオール成分(c')、および、上記セクション「その他の構成単位」で上述した各種ジオール)と
を常圧で昇温し、生成するアルキルアルコールを反応系外に除きながら低分子量の縮合物とした後、チタン化合物、ゲルマニウム化合物、アンチモン化合物などの重縮合触媒の存在下に反応系内を減圧にしてジオールを系外に留去する。これにより、高分子量のポリエステル樹脂を製造することができる。なお、この例では、上記単量体成分(a')とジカルボン酸のジアルキルエステルとジオールとを反応させる場合について触れたが、上記「その他の単量体成分」として3価以上の多価アルコールおよび/または3価以上の多価カルボン酸が共存する場合にも同様に行うことができる。
本願発明に係る潤滑油組成物において、上記基油(A)と上記共重合体(B)との質量比((A)の質量/(B)の質量)が60/40~99.5/0.5であり、好ましくは75/25~99/1、さらに好ましくは80/20~97/3である。このような範囲で、潤滑油組成物に基油(A)と共重合体(B)とが含まれることにより、基油(A)と共重合体(B)との間に良好な相溶性が得られるとともに、潤滑油組成物に増粘効果が付与される。また、室温条件下であっても、潤滑油組成物が適正な粘度指数を発揮できるために、流動性が良好である。さらに、基油(A)が植物油である場合、潤滑油組成物の低温貯蔵安定性を向上させることができる。
本発明に係る潤滑油組成物は、基油(A)および共重合体(B)の他に、酸化安定性、防錆性、極圧性、消泡性の向上等の目的に応じて、添加剤(C)を含むことが好ましい。
本発明の潤滑油組成物に用いる酸化防止剤としては、公知の酸化防止剤が使用できるが、具体的には、ジ(アルキルフェニル)アミン(アルキル基は炭素数4~20)、フェニル-α-ナフチルアミン、アルキルジフェニルアミン(アルキル基は炭素数4~20)、N-ニトロソジフェニルアミン、フェノチアジン、N,N'-ジナフチル-p-フェニレンジアミン、アクリジン、N-メチルフェノチアジン、N-エチルフェノチアジン、ジピリジルアミン、ジフェニルアミン、フェノールアミン、2,6-ジ-t-ブチル-α-ジメチルアミノパラクレゾール等のアミン系酸化防止剤、2,6-ジ-t-ブチルパラクレゾ-ル、4,4'-メチレンビス(2,6-ジ-t-ブチルフェノ-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、2,6-ジ-t-ブチルフェノ-ル、ジオクチルジフェニルアミン等のフェノ-ル系酸化防止剤、また鉄オクトエート、フェロセン、鉄ナフトエート等の有機鉄塩、セリウムナフトエート、セリウムトルエ-ト等の有機セリウム塩、ジルコニウムオクトエート等の有機ジルコニウム塩等の有機金属化合物系酸化防止剤が挙げられる。また、酸化防止剤は単独で使用してもよいが、二種以上組み合わせて使用することもできる。
本発明の潤滑油組成物に用いる極圧剤としては、公知の極圧添加剤が使用できるが、具体的には、塩素化パラフィン、塩素化ジフェニル、および塩素化脂肪酸等の塩素系化合物;硫化脂肪酸、硫化脂肪酸エステル、硫化動物油、硫化植物油、ジベンジルジサルファイド、合成ポリサルファイド、アルキルチオプロピオン酸のアミン塩またはアルカリ金属塩、およびアルキルチオグリコール酸のアミン塩またはアルカリ金属塩等のイオウ系化合物;リン酸エステル、酸性リン酸エステル、酸性リン酸エステルのアミン塩、ならびに塩素化リン酸エステルおよび亜リン酸エステル等のリン系化合物、ジアルキルジチオリン酸亜鉛化合物またはジアリルジチオリン酸亜鉛化合物、有機モリブデン化合物、ナフテン酸鉛等の金属石鹸、有機ホウ酸エステルおよびその金属塩やアミン塩、有機ホスホン酸およびその金属塩やアミン塩が挙げられる。
本発明の潤滑油組成物に用いる防錆剤としては 、例えば、石油スルホネート、アルキルベンゼンスルホネート、ジノニルナフタレンスルホネート、アルケニルコハク酸エステル、及び多価アルコールエステル等が挙げられる。
本発明の潤滑油組成物に用いる金属不活性剤としては、ベンゾトリアゾールとその誘導体、チアゾール系化合物などを挙げることができる。
耐摩耗添加剤としては 、リン系化合物、有機モリブデン化合物、脂肪酸エステル化合物あるいは脂肪族アミン系化合物が挙げられる。
本発明の潤滑油組成物に用いる消泡剤としては、公知の消泡剤が使用できるが、例えば、ジメチルシロキサン、シリカゲル分散体等のシリコン系消泡剤;アルコール、エステル系消泡剤などが挙げられる。
本発明の潤滑油組成物に用いる清浄分散剤としては、公知の清浄分散剤が使用できるが、例えば、カルシウムスルホネート、マグネシウムスルホネート、バリウムスルホネート等の金属スルホネートやチオホスホネート、フェナート、サリチレート、コハク酸イミド、ベンジルアミン、コハク酸エステルなどが挙げられる。
流動点降下剤としては、アルキル化ナフタレン、メタクリル酸アルキルの(共)重合体、アクリル酸アルキルの(共)重合体、フマル酸アルキルと酢酸ビニルの共重合体、α-オレフィンポリマー、α-オレフィンとスチレンの共重合体などが挙げられる。特に、メタクリル酸アルキルの(共)重合体、アクリル酸アルキルの(共)重合体などが挙げられる。
本発明の潤滑油組成物は、基油(A)および所定の共重合体(B)、必要によっては添加剤(C)等を所定割合で混合・混練して得られる。
本発明に係る潤滑油組成物は、良好な粘度特性および摩擦特性を有するとともに、生分解性に優れているために、各用途の潤滑油組成物として非常に有用である。
本実施例および比較例において使用した下記基油の性状を下記表1に示す。
A-2:DIDA(ジイソデシルアジペート):大八化学工業株式会社製
A-3:H-334R(ネオペンチルポリオール脂肪酸エステル):日油株式会社製
下記の各製造例で得られた(共)重合体を構成する各構成単位の含量は、以下の手順により求めた。
極限粘度(IV:Intrinsic Viscosity)は、試料(ポリエステル樹脂)0.5gを1,1,2,2-テトラクロロエタン/フェノールの混合溶液(50質量%/50質量%)100mlを用いて溶解し、その混合溶液中で、135℃で40分加熱溶解した後に25℃の水で冷却し、ウベローデ粘度計を用いて25℃での溶液粘度を測定し、算出する。
[η]:極限粘度(dl/g)
ηSP:比粘度
C:試料濃度(g/dl)
k:定数(溶液濃度の異なるサンプル(3点以上)の比粘度を測定し、横軸に溶液濃度、縦軸にηSP/Cをプロットして求めた傾き)
ここで、比粘度ηSPは以下の算式に従って求めた。
t:試料溶液の流下秒数(秒)
t0:溶媒の流下秒数(秒)
〔融点(Tm)、ガラス転移温度(Tg)〕
共重合体(B)の融点(Tm)は、測定装置として示差走査熱量計(DSC220C型、セイコーインスツル(株)製)を用いて測定した。具体的には、約5mgの共重合体(B)を測定用アルミニウムパン中に密封し、室温から10℃/minで150℃まで加熱した。150℃で5分間保持し、次いで、10℃/minで-100℃まで冷却した。-100℃で5分間置いた後、10℃/minで150℃まで2度目の加熱を行なった。この2度目の加熱でのピーク温度(℃)を共重合体の融点(Tm)とし、ガラス転移に相当する変位点をガラス転移温度(Tg)とした。
容器に入れた(共)重合体を、基油の入ったビーカーに移液する際の作業性を以下の基準に基づいて評価した。
(共)重合体を基油に投入後、60℃で5分撹拌し、目視で以下の基準に基づいて評価した。
○:8割以上が均一になっている
△:半分程度が均一になっている
〔生分解性〕
修正MITI試験法「OECD301C」に準拠し、生分解率を測定した。なお、1998年7月に改定されたエコマーク認定基準では、上記生分解率は60%以上であることが要求される。
リシノール酸40.0質量部、セバシン酸5.8質量部、1,4-ブタンジオール5.2質量部を30分かけて、常温から210℃まで昇温した。210℃へ到達した後、チタンテトラブトキシドを0.20質量部、エチルアンモニウムヒドロキシドの20wt%水溶液を0.03質量部加え、そのまま210℃で5時間保持して、エステル化反応を行った。
リシノール酸40.0質量部、アジピン酸10.2質量部、1,4-ブタンジオール9.7質量部を30分かけて、常温から210℃まで昇温した。以後、実施例1-1と同様にしてポリエステルを得た。
リシノール酸40.0質量部、セバシン酸13.6質量部、1,4-ブタンジオール9.7質量部を30分かけて、常温から210℃まで昇温した。以後、実施例1-1と同様にしてポリエステルを得た。
リシノール酸20.0質量部、12-ヒドロキシステアリン酸19.6質量部、セバシン酸13.6質量部、1,4-ブタンジオール9.7質量部を30分かけて、常温から210℃まで昇温した。以後、実施例1-1と同様にしてポリエステルを得た。
リシノール酸30.5質量部、セバシン酸20.6質量部、1,4-ブタンジオール13.3質量部を30分かけて、常温から210℃まで昇温した。以後、実施例1-3と同様にしてポリエステルを得た。
それぞれ所定の範囲まで攪拌トルクが到達した時点で重縮合反応を終了した以外は、実施例1-3と同様にしてポリエステルを得た。すなわち、実施例1-6~1-9は、実施例1-3で行った重縮合反応につき、反応を終了させる基準とする攪拌トルクの大きさを変えて行った実施例であり、重合度を変えて行った実施例に相当する。
12-ヒドロキシステアリン酸39.2質量部、セバシン酸13.6質量部、1,4-ブタンジオール9.7質量部を30分かけて、常温から210℃まで昇温した。以後、実施例1-1と同様にしてポリエステルを得た。
リシノール酸60.0質量部を30分かけて、常温から210℃まで昇温した。以後、実施例1と同様にしてポリエステルを得た。
アジピン酸30.0質量部、1,4-ブタンジオール29.2質量部を30分かけて、常温から210℃まで昇温した。以後、実施例1と同様にしてポリエステルを得た。
実施例及び比較例で得られた潤滑油組成物10gを20mlのネジ口ビンに入れ、50℃で30分間加熱し、室温に放置した後、25℃、0℃の温度条件下で貯蔵安定性として相溶性(流動性、結晶化)を以下の基準に基づいて評価した。
動粘度:ASTM D445に基づいて、100℃の動粘度を測定した。
粘度指数:ASTM D2270に基づいて粘度指数を求めた。
日本自動車技術会規格(JASO:Japanese Automotive Standards Organization)に規定される超音波剪断安定性試験法(JASO M347-95)に基づいて超音波を1時間照射し、照射前後の40℃動粘度の低下率(%)を評価した。
ASTM D2983に準拠し、-10℃および-40℃にてブルックフィールド粘度計により-40℃粘度を測定した。
潤滑油の粘着性を、以下のように評価した。
評点4; 糸引き性を有し、高い粘着力(5mm以上)を示す
評点3;糸引き性を有し、粘着性を示す(1~5mm)
評点2; 僅かに糸引きが見られ、粘着性を示す(1~5mm)
評点1;糸引きが見られず、粘着性が低い(0mm)
(vii)耐熱性
潤滑油の耐熱性試験は、通常、酸化防止剤などの添加剤を加えて行われる。
評点4; 若干の色調変化が見られ、淡黄色への色変化が認められる
評点3; 淡黄色への色変化が認められる
評点2; 色調変化が比較的大きく、黄色への色変化が認められる
評点1; 色調変化が大きく、茶褐色への色変化が認められる
[実施例2-1]
ナタネ油(A-1)と共重合体(B-1)とを、質量比が90/10となるように混合して潤滑油組成物を調製した。得られた潤滑油組成物の物性評価結果を下記表3-1に示す。
下記表3-1および3-2に従って混合し、潤滑油組成物を調製した。評価結果を表3-1および3-2に併せて示す。
ナタネ油(A-1)、共重合体(B-3)および共重合体(B-10)を、質量比が90/5/5となるように混合して潤滑油組成物を調製した。評価結果を表3-2に併せて示す
[実施例2-10]
合成ポリオールエステル(A-3)を用い、表3-2に従った比率にて混合し、潤滑油組成物を調製した。評価結果を表3-1に併せて示す。
合成エステル(DIDA)(A-2)を用い、表3-3に従った比率にて混合し、潤滑油組成物を調製した。評価結果を表3-3に併せて示す。
Claims (16)
- 下記要件(B1)~(B3)を満たす共重合体(B):
(B1)リシノール酸に由来する構成単位(a)と、
脂肪族ジカルボン酸に由来する構成単位(b)と、
炭素原子数2~10のジオールに由来する構成単位(c)と
を含む;
(B2)前記構成単位(a)、(b)および(c)の合計を100モル%としたとき、前記構成単位(a)の含量が20~90モル%、前記構成単位(b)の含量が5~40モル%、前記構成単位(c)の含量が5~40モル%である;
(B3)極限粘度[IV]が0.1~2.0dl/gの範囲にある。 - 基油(A)と、請求項1に記載の共重合体(B)とを含み、かつ、前記基油(A)と前記共重合体(B)との質量比((A)の質量/(B)の質量)が60/40~99.5/0.5である潤滑油組成物。
- 前記基油(A)が植物油および/又は合成エステルである請求項2に記載の潤滑油組成物。
- 前記合成エステルが、ジエステルまたはポリオールエステルである請求項3に記載の潤滑油組成物。
- 前記合成エステルが、脂肪族ジエステルまたは脂肪族ポリオールエステルである請求項3または4に記載の潤滑油組成物。
- 前記要件(B2)において、前記構成単位(b)と前記構成単位(c)とのモル比((b)/(c))が0.9~1.1である、請求項2~5のいずれか1項に記載の潤滑油組成物。
- 前記要件(B2)において、前記構成単位(a)が40~90モル%である、請求項2~6のいずれか1項に記載の潤滑油組成物。
- 前記要件(B3)において、極限粘度[IV]が0.3~1.5dl/gの範囲にある、請求項2~7のいずれか1項に記載の潤滑油組成物。
- 酸化防止剤、極圧剤、防錆剤、金属不活性剤、耐摩耗添加剤、消泡剤、清浄分散剤および流動点降下剤からなる群から選ばれる少なくとも1種の添加剤(C)をさらに含む請求項2~8のいずれか1項に記載の潤滑油組成物。
- 前記脂肪族ジカルボン酸がセバシン酸である、請求項2~9のいずれか1項に記載の潤滑油組成物。
- 前記炭素原子数2~10のジオールが1,4-ブタンジオールである、請求項2~10のいずれか1項に記載の潤滑油組成物。
- 請求項2~11の何れか1項に記載の潤滑油組成物からなるギヤー油。
- 請求項2~11の何れか1項に記載の潤滑油組成物からなる作動油。
- 請求項2~11の何れか1項に記載の潤滑油組成物からなるエンジン油。
- 請求項2~11の何れか1項に記載の潤滑油組成物からなるグリース。
- 請求項2~11の何れか1項に記載の潤滑油組成物からなる機械加工油。
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US20180201864A1 (en) | 2018-07-19 |
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