WO2011125679A1 - 難燃性能を有する生分解性潤滑油組成物 - Google Patents
難燃性能を有する生分解性潤滑油組成物 Download PDFInfo
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- WO2011125679A1 WO2011125679A1 PCT/JP2011/057904 JP2011057904W WO2011125679A1 WO 2011125679 A1 WO2011125679 A1 WO 2011125679A1 JP 2011057904 W JP2011057904 W JP 2011057904W WO 2011125679 A1 WO2011125679 A1 WO 2011125679A1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/041—Mixtures of base-materials and additives the additives being macromolecular compounds only
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy compounds
- C10M2207/2835—Esters of polyhydroxy compounds used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/287—Partial esters
- C10M2207/289—Partial esters containing free hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/287—Partial esters
- C10M2207/289—Partial esters containing free hydroxy groups
- C10M2207/2895—Partial esters containing free hydroxy groups used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/40—Fatty vegetable or animal oils
- C10M2207/401—Fatty vegetable or animal oils used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/04—Molecular weight; Molecular weight distribution
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/08—Resistance to extreme temperature
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/64—Environmental friendly compositions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/08—Hydraulic fluids, e.g. brake-fluids
Definitions
- the present invention relates to a biodegradable lubricating oil composition having flame retardancy.
- the present invention relates to a biodegradable lubricating oil composition having excellent flame retardancy and high biodegradability used as a lubricating oil such as hydraulic fluid and door closer oil.
- each of Patent Documents 1 to 4 includes a self-digesting hydraulic oil (Patent Document 1) containing a compound obtained by condensation reaction of hexachlorophosphazene with perfluoroalkyl alcohol, etc., and a polyol and a polyol partial ester as main components.
- Patent Document 1 a self-digesting hydraulic oil containing a compound obtained by condensation reaction of hexachlorophosphazene with perfluoroalkyl alcohol, etc., and a polyol and a polyol partial ester as main components.
- Patent Document 2 Flame retardant hydraulic fluid containing a high molecular compound
- Patent Document 3 a flame retardant hydraulic fluid obtained by blending a high molecular polymer and a low molecular polymer in a base oil composed of a fatty acid ester or a phosphate ester
- Patent Document 4 A hydraulic fluid composition (Patent Document 4) containing a polyalkylene glycol base fluid and an alkylene-vinyl ester copolymer as an anti-mist additive soluble in the fluid is proposed to obtain excellent flame retardancy. Is described.
- a lubricating oil such as hydraulic fluid or door closer oil
- an oil agent may be ejected from the device pinhole during a fire to promote a fire.
- lubricating oil such as hydraulic fluid and door closer oil that exhibits flame retardancy even in a high-pressure spray state or oil leakage.
- a lubricating oil composition that has further flame retardancy and further biodegradability for reducing environmental impact in order to improve safety.
- an object of the present invention is to provide a lubricating oil composition that achieves both excellent flame retardancy and biodegradability.
- the present invention [1] (A) (a) 60% by mass or more of plant-derived oil, and (b) a base oil containing 40% by mass or less of a polyol ester, and (B) a mass average molecular weight of 20,000 to 300,000.
- a biodegradable lubricating oil composition comprising 0.1 to 5% by weight of polymethacrylate, [2] The biodegradable lubricating oil composition according to the above [1], wherein the plant-derived oil is a rapeseed oil having an oleic acid content of 60% by mass or more, [3] The biodegradable lubricating oil composition according to [1] or [2], wherein the polyol ester is a polyol partial ester having a hydroxyl value of 30 mg KOH / g or more and a flash point of 300 ° C. or more.
- the door closer oil which consists of a basic lubricating oil composition.
- the biodegradable lubricating oil composition of the present invention comprises (A) (a) a plant-derived oil of 60% by mass or more, and (b) a base oil containing 40% by mass or less of a polyol ester, and (B) a mass average. It is blended with 0.1 to 5% by mass of polymethacrylate having a molecular weight of 20,000 to 300,000.
- the base oil (A) of the biodegradable lubricating oil composition of the present invention contains (a) 60% by mass or more of a plant-derived oil and (b) 40% by mass or less of a polyol ester.
- (A) Plant-derived oil As the plant-derived oil used in the base oil (a), rapeseed oil, sunflower oil, soybean oil, corn oil, canola oil and the like can be used, and in particular, from the viewpoint of biodegradation performance, heat stability performance, etc., sunflower oil And rapeseed oil are preferred.
- plant-derived oils have a total degree of unsaturation exceeding 0.3, but the total degree of unsaturation can be reduced by a treatment such as hydrogenation in the refining process.
- vegetable oils having a low total unsaturation can be easily produced by gene recombination techniques.
- a plant-derived oil containing oleic acid in a high proportion is preferably used from the viewpoint of biodegradation performance, heat stability performance, etc., for example, those containing 60% by mass or more of oleic acid are preferred, more preferably. Contains 70% by mass or more.
- plant-derived oils containing a high proportion of oleic acid high oleic canola oil, high oleic rapeseed oil, high oleic sunflower oil, high oleic soybean oil and the like can be preferably exemplified.
- Oleic rapeseed oil can be particularly preferably used.
- the vegetable oil-derived oil is contained in the base oil in an amount of 60% by mass or more, preferably 70% by mass or more from the viewpoint of biodegradation performance, and more preferably 75 to 99 from the viewpoint of biodegradation performance and thermal stability performance. % By mass.
- Base oil contains (b) polyol ester from a viewpoint of biodegradation performance and a flame-retardant performance improvement.
- polyol ester there is no restriction
- esterification rate is obtained by dividing the number of esterified hydroxyl groups from the total number of hydroxyl groups in the polyol ester including esterified hydroxyl groups, and was calculated from the following formula.
- Esterification rate (%) ⁇ (SV ⁇ AV) ⁇ 100 ⁇ / (OHV + SV ⁇ AV) (SV: saponification value, AV: acid value, OHV: hydroxyl value)
- the polyol for producing the polyol ester is, for example, a polyol having a total carbon number of 3 to 12 and a total number of hydroxyl groups of 3 to 6, specifically, glycerin, trimethylolethane, trimethylolpropane.
- Trihydric alcohols such as trimethylol nonane
- polyhydric alcohols such as pentaerythritol, ditrimethylolpropane, dipentaerythritol, sorbitol, and mannitol.
- trimethylolpropane, pentaerythritol, and glycerin are preferably used. It is done.
- These polyols may be used alone or in combination of two or more.
- chain monocarboxylic acid to be used for the production of the polyol ester examples include chain monocarboxylic acids having a total carbon number of 6 to 22, specifically, caproic acid, enanthic acid, caprylic acid. , Pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid and other linear saturated fatty acids, undecenoic acid, olein Linear unsaturated fatty acids such as acid, elaidic acid, celetic acid, erucic acid, brassic acid, isomyristic acid, isopalmitic acid, isostearic acid, 2,2-dimethylbutanoic acid, 2,2-dimethylpentanoic acid, 2, 2-dimethyloctanoic acid, 2-ethyl-2
- the desired polyol ester can be obtained by adjusting the respective feed ratios, and the light component is sufficiently light so that the flash point is not lowered. It is desirable to cut. And when using the obtained polyol ester for base oil, an esterification reaction product may be used as it is, or each reaction product may be blended and used so that a desired viscosity may be obtained.
- the polyol ester used for the base oil has a hydroxyl value of preferably 30 mgKOH / g or more, more preferably 35 mgKOH / g or more. If the hydroxyl value is too low, the complete ester portion is increased, and continuous combustion may easily occur as in the conventional product.
- the flash point is preferably 300 ° C. or higher. This is because if the flash point is too low, ignition is easy.
- the polyol ester used in the present invention has a number average molecular weight of preferably 600 to 1,500, more preferably 600 to 1,000, and still more preferably 650 to 950. If this molecular weight is too low, the viscosity and flash point will be low, and it will be easy to burn. Moreover, when too high, a viscosity will become high too much and transmission efficiency may worsen.
- the kinematic viscosity may be in a range that can be used depending on the application such as hydraulic oil, but is usually a kinematic viscosity at a temperature of 40 ° C., preferably 20 to 200 mm, from the viewpoint of pump efficiency and viscosity resistance of piping.
- the polyol ester in the viscosity range as described above a diester of trimethylolpropane, in which the fatty acid is a mixture of oleic acid and isostearic acid is preferably used.
- the polyol ester is contained in the base oil in an amount of 40% by mass or less based on the total amount of the base oil, and is preferably 30% by mass or less, more preferably 25% by mass from the viewpoints of flame retardancy, biodegradability, thermal stability, and the like. Hereinafter, it is more preferably 1 to 25% by mass.
- (B) polymethacrylate is used for the purpose of making the base oil difficult to mist, and includes not only a homopolymer of methacrylate but also a copolymer.
- the molecular weight of the polymethacrylate is 20,000 to 300,000 in terms of mass average molecular weight, preferably 30,000 to 300,000, more preferably 35,000 to 200,000.
- the weight average molecular weight is less than 20,000, the above effect is hardly expected.
- the weight average molecular weight is more than 300,000, it is deteriorated by shearing during use, and the effect is also reduced, and the viscosity is further lowered. It is not preferable.
- a mass average molecular weight can be measured by the mass average molecular weight of polystyrene conversion by GPC (gel permeation chromatography).
- the component (B) is preferably 0.1 to 4% by mass, more preferably 0.2 to 3.5% by mass, and still more preferably 0.3 to 3.3% by mass in the lubricating oil composition. % Blended.
- the base oil (A) used for the biodegradable lubricating oil composition of the present invention contains the above-mentioned (a) plant-derived oil and the above-mentioned (b) polyol ester. And a polyol ester, and (B) the optimal compound of the polymethacrylate of the component were discovered, and the lubricating oil composition which was able to provide more outstanding flame retardance performance and biodegradability performance was able to be provided.
- the biodegradable lubricating oil composition of the present invention is optionally used as an antioxidant, a dispersant, a rust inhibitor, a metal deactivator, an oily agent, and an extreme pressure agent that are usually used as lubricating oil additives. It is preferable to blend at least one selected from a demulsifier, a fluidity improver, and an antifoaming agent.
- the antioxidant used here include 2,6-di-t-butyl-4-methylphenol, 4,4′-methylenebis (2,6-di-t-butyl-4-methylphenol), and the like.
- Phenolic antioxidants such as N-phenyl- ⁇ -naphthylamine, N-phenyl- ⁇ -naphthylamine, phenothiazine, monooctyldiphenylamine, or sulfur-based antioxidants such as alkyl disulfides and benzothiazoles, Examples include zinc dialkyldithiophosphate.
- an ashless dispersant and / or a metal detergent can be used as the dispersant.
- the ashless dispersant include succinimides, boron-containing succinimides, benzylamines, and boron-containing benzylamines.
- metal detergents include neutral, basic or overbased metal sulfonates, metal phenates, metal salicylates, and metal phosphonates.
- the metal constituting the metal sulfonate, metal phenate, metal salicylate, or metal phosphonate is preferably an alkaline earth metal such as Ca or Mg.
- Examples of the antirust agent include alkenyl succinic acid, sorbitan monooleate, pentaerythritol monooleate, and amine phosphate.
- Examples of the metal deactivator include benzotriazole, benzothiazole, triazole, and dithiol. Examples thereof include carbamate, imidazole, and derivatives thereof.
- Examples of oily agents include alcohols, fatty acids and fatty acid esters.
- Examples of the fatty acid esters include esters composed of an aliphatic carboxylic acid having 6 to 22 carbon atoms and an aliphatic alcohol having 1 to 18 carbon atoms.
- Preferred examples of the alcohols include monovalent aliphatic saturated or unsaturated alcohols having 8 to 18 carbon atoms.
- Examples of the extreme pressure agent include zinc dialkyldithiophosphate, dialkyl polysulfide, triaryl phosphate, trialkyl phosphate and the like.
- Examples of the demulsifier include polyoxyalkylene glycol, polyoxyalkylene alkyl ether, polyoxyalkylene alkylamide, polyoxyalkylene fatty acid ester and the like.
- Examples of the fluidity improver include polyalkyl acrylates, alkyl aromatic compounds, and ethylene-vinyl acetate copolymers.
- examples of the antifoaming agent include dimethylpolysiloxane, diethyl silicate, and ester polymers.
- the amount of these additives can be determined depending on the purpose, but the total amount is preferably 5.0% by mass or less, more preferably 3.0% by mass per lubricating oil composition. % Or less, more preferably 0.5 to 2.5% by mass.
- the biodegradable lubricating oil composition of the present invention comprises (A) (a) a base oil containing 60% by mass or more of a plant-derived oil and (b) 40% by mass or less of a polyol ester, and (B) a mass average molecular weight of 20 , 1,000 to 300,000, and 0.1 to 5% by mass of polymethacrylate.
- A (a) a base oil containing 60% by mass or more of a plant-derived oil and (b) 40% by mass or less of a polyol ester, and (B) a mass average molecular weight of 20 , 1,000 to 300,000, and 0.1 to 5% by mass of polymethacrylate.
- the details of each component and the amount of the components are as described above.
- the biodegradation rate is 60% or more in the degradation test of chemical substances by microorganisms according to the OECD test guideline 301C method.
- it is 70% or more, More preferably, it is 80% or more, and it has the outstanding biodegradation performance.
- the 96-hour LC 50 value is usually 100 mg / L or more, and there is little influence on the living body.
- the lubricating oil composition is a very environmentally friendly lubricating oil.
- the kinematic viscosity at 40 ° C. of the biodegradable lubricating oil composition of the present invention is preferably 120 mm 2 / s or less, more preferably 20 to 80 mm 2 / s from the viewpoint of pump efficiency, piping resistance, and the like. It is.
- the viscosity index is preferably 130 or more, more preferably 140 or more, from the viewpoint of preventing increase in viscosity at low temperatures.
- the pour point is usually ⁇ 20 ° C. or lower, preferably from ⁇ 30 ° C. or lower, more preferably ⁇ 35 ° C. or lower, from the viewpoint of low temperature fluidity.
- the flash point is usually 250 ° C. or higher, and preferably 260 ° C.
- the lubricating oil composition has a low pour point as described above, when used as a hydraulic fluid, door closer oil, or sliding surface oil, the startability of the machine at low temperature is good and high Since it has a flash point, flame retardancy is high, and VG32 or higher is classified as a flammable liquid under the Japanese Fire Service Act and is excellent in safety.
- the biodegradable lubricating oil composition of the present invention is excellent in biodegradability, has little impact on ecology, and is excellent in flame retardancy.
- the lubricating oil composition is attached to and opened on a hydraulic fluid, which is a power transmission fluid used for operation of power transmission, force control, buffering, etc., in hydraulic systems such as hydraulic equipment and devices, and doors (open doors). It is suitable as a door closer oil used for a door closer which is a device that automatically closes a door, a sliding face oil used for various sliding surfaces and imparting lubricity.
- kinematic viscosity 6.00 mm 2 / s potentiometric acid value 0.04 mg KOH / g, hydroxyl value 2.0 mg KOH / g, density (15 °C) 0.961g / cm 3 , flash point (Cleveland open type) 280 °C TMP triolate: 40 ° C. kinematic viscosity 49.45 mm 2 / s, 100 ° C. kinematic viscosity 9.81 mm 2 / s, potentiometric acid value 0.99 mg KOH / g, hydroxyl value 3.0 mg KOH / g, density (15 ° C. ) 0.918g / cm 3 , flash point (Cleveland open type) 320 ° C
- PMA (1) acrylic copolymer, 100 ° C. kinematic viscosity 835 mm 2 / s, acid value by indicator method 0.05 mg KOH / g, density (15 ° C.) 0.915 g / cm 3 , mass average molecular weight (Mw) 140,000
- PMA (2) acrylic copolymer, 100 ° C. kinematic viscosity 852 mm 2 / s, acid value by indicator method 0.05 mg KOH / g, density (15 ° C.) 0.941 g / cm 3 , Mw 37,000
- PMA (3) Dispersed acrylic copolymer, 100 ° C.
- Corrosion resistance According to JIS K 2513 “Petroleum product copper plate corrosion test method”, the test temperature is 100 ° C., the test time is 3 hours, and the test tube method is used. The state was observed and the corrosivity was evaluated by subdivision symbols 1a to 4c. In addition, corrosivity becomes small so that the number of a subdivision symbol is small, and corrosivity becomes large sequentially alphabetically.
- Rust prevention test In accordance with JIS K 2510, while stirring the sample and water, keep it at 60 ° C, immerse the steel round bar specimen in it, and check the specimen for rust after 24 hours. It was.
- Load bearing test Based on ASTM D2783, it carried out on condition of rotation speed 1,800rpm and room temperature.
- the load wear index (LWI) was determined from the maximum non-seizure load (LNL) and the fusion load (WL). The larger this value, the better the load resistance.
- Biodegradability test The biodegradation rate is measured according to the modified MITI test method “OECD301C”. In addition, according to the Eco Mark certification standard revised in July 1998, the biodegradation rate is required to be 60% or more.
- Biodegradability / toxicity test In accordance with JIS K 0102, Himedaka is used as a test fish, and the half-lethal concentration LC 50 value after 96 hours is measured. The Eco Mark certification standard revised in July 1998 requires the LC 50 value to be 100 mg / L or more.
- biodegradable lubricating oil composition of the present invention has both excellent flame retardancy and biodegradation performance, power used for power transmission, force control, buffering, etc. in hydraulic systems such as hydraulic equipment and devices It can be suitably used as hydraulic fluid as a transmission fluid, door closer oil used in door closers, and the like.
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Abstract
Description
一方、油圧作動油やドアクローザー油などの潤滑油を使用する機器においては、火災時に機器ピンホールから油剤が噴出して、火災を助長することがある。このため、高圧噴霧状態や油漏れにおいても難燃性能を示す油圧作動油やドアクローザー油などの潤滑油が求められている。また、安全性向上のため、更なる難燃性能と環境負荷低減のため更なる生分解性能を有する潤滑油組成物が求められている。
すなわち、本発明の課題は、より優れた難燃性能と生分解性能を両立する潤滑油組成物を提供することにある。
[1](A)(a)植物由来の油を60質量%以上、及び(b)ポリオールエステルを40質量%以下含有する基油、及び
(B)質量平均分子量20,000~300,000のポリメタアクリレート0.1~5質量%、を配合してなる生分解性潤滑油組成物、
[2]前記植物由来の油が、オレイン酸含有量が60質量%以上である菜種油である、上記[1]記載の生分解性潤滑油組成物、
[3]前記ポリオールエステルが、水酸基価30mgKOH/g以上、かつ引火点が300℃以上であるポリオール部分エステルである、前記[1]又は[2]に記載の生分解性潤滑油組成物、
[5]油圧作動油、ドアクローザー油、または摺動面油に用いられる、前記[1]~[4]のいずれかに記載の生分解性潤滑油組成物、
[6]前記[1]~[4]のいずれかに記載の生分解性潤滑油組成物からなる油圧作動油、及び
[7]前記[1]~[4]のいずれかに記載の生分解性潤滑油組成物からなるドアクローザー油、に関する。
本発明の生分解性潤滑油組成物は、(A)(a)植物由来の油を60質量%以上、及び(b)ポリオールエステルを40質量%以下含有する基油、及び(B)質量平均分子量20,000~300,000のポリメタアクリレート0.1~5質量%を配合してなる。
本発明の生分解性潤滑油組成物の基油(A)は、(a)植物由来の油を60質量%以上、及び(b)ポリオールエステルを40質量%以下含有する。
((a)植物由来の油)
基油に用いられる(a)植物由来の油としては、菜種油、ひまわり油、大豆油、トウモロコシ油、キャノーラ油等を用いることができ、中でも生分解性能、熱安定性能等の観点から、ひまわり油及び菜種油が好ましい。
上記植物油由来の油は、基油中に60質量%以上含有され、生分解性能の観点から、好ましくは70質量%以上含有され、生分解性能および熱安定性能の観点からより好ましくは75~99質量%である。
(A)基油は、生分解性能及び難燃性能向上の観点から、(b)ポリオールエステルを含有する。ポリオールエステルとしては特に制限はないが、上記観点から、ポリオールと鎖状モノカルボン酸とを、それぞれを単独で、あるいは二種以上を組み合わせて通常のエステル化反応によって生成するポリオール部分エステルを主成分とするものであることが好ましい。ポリオール部分エステルとしては、ポリオールの少なくとも一部がエステル化したものであり、そのエステル化率が、70~90%であるものが難燃性能の点で好ましい。ここで「エステル化率」とは、エステル化された水酸基を含む、ポリオールエステル中の全水酸基数からエステル化された水酸基数を除したものであり、次式より算出した。
エステル化率(%)={(SV-AV)×100}/(OHV+SV-AV)
(SV:ケン化価、AV:酸価、OHV:水酸基価を表す。)
上記ポリオールエステルは、基油中に基油全量に対し40質量%以下含有され、難燃性能、生分解性能、熱安定性能等の観点から、好ましくは30質量%以下、より好ましくは25質量%以下、さらに好ましくは1~25質量%である。
本発明において、(B)ポリメタアクリレートは、基油をミスト化しにくくするという目的で使用されるものであり、メタアクリレートの単独重合体のみならず、共重合体も含む。このような観点から、ポリメタアクリレートの分子量は質量平均分子量で20,000~300,000であり、好ましくは30,000~300,000、より好ましくは35,000~200,000である。質量平均分子量が20,000より小さい場合は上記の効果がほとんど期待されず、また300,000より大きい場合は使用中に剪断による劣化を受け、その効果も薄れ、更に粘度低下を引き起こしてしまうこととなり好ましくない。なお、質量平均分子量は、GPC(ゲルパーミエーションクロマトグラフィー)によるポリスチレン換算の質量平均分子量により測定できる。
本発明の生分解性潤滑油組成物は、その他必要に応じて、潤滑油添加剤として通常使用される酸化防止剤、分散剤、防錆剤、金属不活性化剤、油性剤、極圧剤、抗乳化剤、流動性向上剤、及び消泡剤から選ばれる少なくとも一種を配合することが好ましい。
ここで用いられる酸化防止剤としては、例えば、2,6-ジ-t-ブチル-4-メチルフェノール,4,4'-メチレンビス(2,6 -ジ-t-ブチル-4-メチルフェノール)等のフェノール系酸化防止剤、N-フェニル-α-ナフチルアミン,N-フェニル-β-ナフチルアミン,フェノチアジン,モノオクチルジフェニルアミン等のアミン系酸化防止剤あるいはアルキルジスルフィド,ベンゾチアゾール等の硫黄系の酸化防止剤、ジアルキルジチオリン酸亜鉛などが挙げられる。
油性剤としては、例えばアルコール類、脂肪酸類及び脂肪酸エステル類などを挙げることができる。脂肪酸エステル類としては、炭素数6~22の脂肪族カルボン酸と炭素数1~18の脂肪族アルコールとからなるエステルを挙げることができる。アルコール類としては、炭素数8~18の一価の脂肪族飽和若しくは不飽和アルコールを好ましく挙げることができる。
抗乳化剤としては、例えば、ポリオキシアルキレングリコール,ポリオキシアルキレンアルキルエーテル,ポリオキシアルキレンアルキルアミド,ポリオキシアルキレン脂肪酸エステル等が挙げられる。
流動性向上剤としては、ポリアルキルアクリレート、アルキル芳香族化合物、エチレン-酢酸ビニル共重合体等が挙げられる。さらに、消泡剤としては、例えば、ジメチルポリシロキサンやジエチルシリケート、エステル系ポリマー等が挙げられる。
本発明の生分解性潤滑油組成物は、(A)(a)植物由来の油を60質量%以上及び(b)ポリオールエステルを40質量%以下含有する基油、(B)質量平均分子量20,000~300,000のポリメタアクリレート0.1~5質量%を配合してなるものであり、各成分の詳細及びその配合量等については、前述の通りである。
当該潤滑油組成物は、前記のように低流動点を有するので、油圧作動油、ドアクローザー油、摺動面油として用いた場合、低温での機械の始動性が良好であり、また、高引火点を有するので難燃性能が高く、VG32以上は日本の消防法の可燃性液体に分類され、安全性に優れる。
実施例1~7及び比較例1,2
表1に示すような量で植物由来の油とポリオールエステルを混合して基油を調製した後、これに表1に示すようにポリメタアクリレート及びその他の添加剤を添加して得られた潤滑油組成物の各々について、下記に示すようにして、一般性状、潤滑性能、燃焼性能及び生分解性能を評価した。その結果を第1表に示す。なお、使用した植物由来の油、ポリオールエステル及びポリメタアクリレートの詳細については以下に示す。
高オレイン酸含有菜種油:オレイン酸含有量 73質量%、炭素数16以下の脂肪酸含有量 4質量%、炭素数18の脂肪酸(オレイン酸除く)含有量 22質量%
(ポリオールエステル)
・TMP(トリメチロールプロパン)イソステアリン酸(オレイン酸)部分エステル:40℃動粘度 60.0mm2/s,100℃動粘度 10.0mm2/s,指示薬法による酸価 0.20mgKOH/g,水酸基価 40.0mgKOH/g,密度(15℃) 0.925g/cm3,引火点(クリーブランド開放式) 306℃
・PE飽和脂肪酸エステル:40℃動粘度 33.5mm2/s,100℃動粘度6.00mm2/s,電位差法による酸価 0.04mgKOH/g,水酸基価 2.0mgKOH/g,密度(15℃) 0.961g/cm3,引火点(クリーブランド開放式) 280℃
・TMPトリオレート:40℃動粘度 49.45mm2/s,100℃動粘度 9.81mm2/s,電位差法による酸価 0.99mgKOH/g,水酸基価 3.0mgKOH/g,密度(15℃) 0.918g/cm3,引火点(クリーブランド開放式) 320℃
・PMA(1):アクリル系共重合物,100℃動粘度 835mm2/s,指示薬法による酸価 0.05mgKOH/g,密度(15℃) 0.915g/cm3、質量平均分子量(Mw) 140,000
・PMA(2):アクリル系共重合物,100℃動粘度 852mm2/s,指示薬法による酸価 0.05mgKOH/g,密度(15℃) 0.941g/cm3、Mw 37,000
・PMA(3):分散型アクリル系共重合物,100℃動粘度 1190mm2/s,指示薬法による酸価 0.26mgKOH/g,密度(15℃) 0.906g/cm3、Mw 79,000
・PMA(4):アルキルメタクリレート系共重合物,100℃動粘度 1500mm2/s,密度(15℃) 0.933g/cm3、Mw 35,000
・流動点向上剤:ポリアルキルメタクリレート,100℃動粘度 364.3mm2/s,指示薬法による酸価 0.04mgKOH/g,密度(15℃) 0.911g/cm3
(1)動粘度
JIS K 2283に準拠して測定した。
(2)酸価
JIS K 2501に規定される「潤滑油中和試験方法」に準拠し、電位差法により測定した。
(3)水酸基価
JIS K 0070に準拠し、ピリジン-塩化アセチル化法により測定する。
(4)引火点
JIS K 2274に準拠し、クリーブランド開放式(COC)試験器によ り測定した。
JIS K 2513「石油製品銅板腐食試験方法」に従って、試験温度100℃、試験時間3時間、及び試験管法により腐食性の試験を行い、「銅板腐食標準」に従って銅板の変色状態を観察し細分記号1a~4cで腐食性を評価した。なお、細分記号の数字の小さいほど腐食性が小さく、アルファベット順に腐食性が順次大きくなる。
(6)防錆試験
JIS K 2510に準拠し、試料と水をかき混ぜながら、60℃に保ち、その中へ鋼製丸棒の試験片を浸し、24時間後の試験片の錆の有無を見た。
ASTM D 2783に準拠して、回転数1,800rpm,室温の条件で行った。最大非焼付荷重(LNL)と融着荷重(WL)から荷重摩耗指数(LWI)を求めた。この値が大きいほど耐荷重性が良好である。
高圧により噴霧された試料油にバーナーで着火し、10秒間予備燃焼させた後、バーナーの火を取り去り、その後の継続燃焼時間を測定し、難燃性能の指標とした。なお、30秒以上継続燃焼したものについては、その時点で試験を打ち切り、「継続燃焼性有り」と判定した。試験条件噴霧圧力:70kg/cm2 G(窒素加圧)試料油温:60℃, ノズル :Monarch 60°PL2.25(ホロウコーンタイプ),ノズルバーナー間:10cm,予備燃焼時間:10秒,オートクレーブ容量:1リットル
修正MITI試験法「OECD301C」に準拠し、生分解率を測定する。なお、1998年7月に改訂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。
(10)生分解性・毒性試験
JIS K 0102に準拠し、試験魚としてヒメダカを用い、96時間後の半数致死濃度LC50値を測定する。なお、1998年7月に改訂されたエコマーク認定基準では、上記LC50値が100mg/L以上であることが要求される。
Claims (7)
- (A)(a)植物由来の油を60質量%以上、及び(b)ポリオールエステルを40質量%以下含有する基油、及び
(B)質量平均分子量20,000~300,000のポリメタアクリレート0.1~5質量%、を配合してなる生分解性潤滑油組成物。 - 前記植物由来の油が、オレイン酸含有量が60質量%以上である菜種油である、請求項1記載の生分解性潤滑油組成物。
- 前記ポリオールエステルが、水酸基価30mgKOH/g以上、かつ引火点が300℃以上であるポリオール部分エステルである、請求項1又は2に記載の生分解性潤滑油組成物。
- 組成物全体の40℃における動粘度が120mm2/s以下である、請求項1~3のいずれか1項に記載の生分解性潤滑油組成物。
- 油圧作動油、ドアクローザー油、または摺動面油に用いられる、請求項1~4のいずれか1項に記載の生分解性潤滑油組成物。
- 請求項1~4のいずれか1項に記載の生分解性潤滑油組成物からなる油圧作動油。
- 請求項1~4のいずれか1項に記載の生分解性潤滑油組成物からなるドアクローザー油。
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- 2011-03-29 WO PCT/JP2011/057904 patent/WO2011125679A1/ja active Application Filing
- 2011-03-29 EP EP11765579.5A patent/EP2554646B1/en active Active
- 2011-03-29 CN CN2011800145217A patent/CN102812114A/zh active Pending
- 2011-03-29 US US13/637,659 patent/US20130017984A1/en not_active Abandoned
- 2011-03-30 TW TW100111031A patent/TWI510611B/zh active
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WO2024004900A1 (ja) * | 2022-06-29 | 2024-01-04 | 出光興産株式会社 | 潤滑油組成物並びにその使用方法及び製造方法 |
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EP2554646A4 (en) | 2013-11-06 |
JP2011213920A (ja) | 2011-10-27 |
EP2554646B1 (en) | 2019-06-12 |
CN102812114A (zh) | 2012-12-05 |
TW201142011A (en) | 2011-12-01 |
EP2554646A1 (en) | 2013-02-06 |
US20130017984A1 (en) | 2013-01-17 |
JP5764298B2 (ja) | 2015-08-19 |
TWI510611B (zh) | 2015-12-01 |
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