WO2010079744A1 - Lubricant composition - Google Patents
Lubricant composition Download PDFInfo
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- WO2010079744A1 WO2010079744A1 PCT/JP2010/000041 JP2010000041W WO2010079744A1 WO 2010079744 A1 WO2010079744 A1 WO 2010079744A1 JP 2010000041 W JP2010000041 W JP 2010000041W WO 2010079744 A1 WO2010079744 A1 WO 2010079744A1
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- WIPO (PCT)
- Prior art keywords
- oil
- lubricating
- lubricating oil
- trihydroxybenzoic acid
- ester
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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
- 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
- C10M129/76—Esters containing free hydroxy or carboxyl 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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
- C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms 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
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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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
- C10M2207/284—Esters of aromatic monocarboxylic acids
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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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
- C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
- C10M2219/066—Thiocarbamic type compounds
- C10M2219/068—Thiocarbamate metal salts
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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
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/041—Triaryl phosphates
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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
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
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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
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/02—Viscosity; 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
- C10N2030/12—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
- 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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- 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
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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
- C10N2040/25—Internal-combustion engines
Definitions
- the present invention relates to a lubricating oil composition, in particular, a lubricating oil composition used as a lubricating oil for internal combustion engines, a drive system lubricating oil or a working oil.
- Patent Document 1 a lubricating oil for internal combustion engines in which dimer acid diamide and molybdenum dithiocarbamate (MoDTC) are blended.
- the pressure energy of hydraulic pumps is converted into kinetic energy (work energy) for systems that require large work energy such as injection molding machines, machine tools, press machines, and forging press machines.
- the hydraulic system that can be used is widely used. Even in this hydraulic system, energy saving needs are increasing, and energy saving measures are also required for hydraulic fluid that is the pressure medium of the hydraulic system, and low viscosity and high viscosity index are being achieved. As a result of lowering the viscosity, there has been a problem of reduced wear resistance and seizure of the sliding portion. In recent years, the load on the sliding portion has increased due to the downsizing, speeding up, and fuel and energy savings of mechanical systems, and there has been a demand for lubricating oils that are more excellent in lubricity such as wear resistance.
- the ideal characteristic of the lubricating oil is that there is little friction loss at high speeds and low speeds, and there is little wear such as fretting wear. That is, the lubricating oil is required to reduce friction loss and reduce wear. Therefore, it is desired that the friction loss is small and the wear is small even when the contact surface speed is high, such as when rotating at high speed, or when high torque is applied at low speed.
- To reduce the friction loss at high speed it is necessary to reduce the viscosity of the lubricating base oil itself.
- the viscosity of the base oil is lowered, it becomes weak against wear such as fretting, that is, contact between base materials such as sliding metals may occur and wear or seizure may occur.
- 3,4,5-trihydroxybenzoic acid ester is (1) having a function of reducing friction coefficient and suppressing wear; (2) Because hematite, which is iron red rust, is reduced to hard and strong black rust (magnetite), it has a high anti-rust effect. (3)
- the 3,4,5-trihydroxybenzoic acid compound itself has low solubility in mineral-based lubricating base oils, so it does not exhibit the above effect as it is, but it can exhibit its effect when used with a cleaning dispersant. , As a result, they have come up with the present invention.
- the present invention solves various problems in the sliding part which is more severe by the above-mentioned miniaturization, high speed, fuel saving and energy saving, and the problem to be solved by the present invention is to greatly reduce wear. And providing a lubricating oil composition having a low friction coefficient and having a high rust prevention property in lubrication of iron-based sliding parts.
- the present invention is as follows. (1) To the lubricating base oil, 3,4,5-trihydroxybenzoic acid ester, 0.01 to 10% by mass on the basis of the total amount of the lubricating oil composition, and the detergent dispersant based on the total amount of the lubricating oil composition A lubricating oil composition characterized by adding 0.1 to 20% by mass. (2) 3,4,5-Trihydroxybenzoate is synthesized from 3,4,5-trihydroxybenzoic acid and a linear or branched alcohol having 3 to 12 carbon atoms.
- the lubricating oil composition according to the above (1) which is an alkyl benzoate.
- the lubricating oil composition of the present invention comprises a lubricating base oil containing an ester of 3,4,5-trihydroxybenzoic acid and a detergent dispersant, thereby significantly reducing wear and having a low coefficient of friction and stability.
- the iron-based sliding part has a high antirust effect. Therefore, the lubricating oil composition of the present invention is suitable for long-term use and has a remarkable effect on energy saving due to the low and stable friction coefficient characteristics.
- the lubricating oil composition of the present invention comprises a lubricating base oil containing 0.01 to 10% by mass of 3,4,5-trihydroxybenzoic acid ester and 0.1 to 20% by mass of a detergent dispersant. is there. Since 3,4,5-trihydroxybenzoic acid ester has low solubility in hydrocarbon base oils other than mineral base oils and base oils having polar groups such as esters and ethers, it itself has lubricating properties. Although it cannot be added to such a concentration that the improvement can be exerted, it can be used at a concentration at which the lubricity is improved by using it together with a cleaning dispersant.
- a lubricating base oil such as mineral oil, synthetic oil, animal or vegetable oil can be used. Further, two or more of these lubricating base oils can be mixed and used.
- the physical properties of the lubricating base oil used in the present invention are not particularly limited, but those having a kinematic viscosity of 5 to 1000 mm 2 / s at 40 ° C. are preferred, and energy saving can be achieved by lowering the viscosity. It is about 500 mm 2 / s, more preferably 5 to 100 mm 2 / s. However, it is preferable to use a high viscosity base oil for high load applications.
- the viscosity index is preferably 90 or more, more preferably 100 to 250.
- the pour point which is a low temperature characteristic, is preferably ⁇ 10 ° C. or lower, more preferably ⁇ 15 ° C. or lower.
- the flash point is preferably 70 ° C. or higher, and more preferably 150 ° C. or higher.
- the lubricating base oil is preferably blended in an amount of 70 to 99 mass%, more preferably 80 to 98 mass%, based on the total amount of the lubricating oil composition.
- Mineral oil-based lubricating base oils include hydrocracking, solvent extraction, hydrorefining, and solvent removal of lubricating oil fractions obtained by atmospheric distillation of crude oil or vacuum distillation of atmospheric distillation residues.
- a refined lubricating base oil obtained by appropriately combining lubricating oil refining means such as wax, hydrodewaxing, and clay treatment can be suitably used.
- Mineral-based lubricating base oils made from such a relatively high boiling fraction of petroleum are generally inexpensive and are widely used in various lubricating oils and greases. Therefore, in the present invention, it is economical and preferable to use this mineral oil base oil alone.
- examples of the synthetic oil base oil include poly- ⁇ -olefin (PAO), alkylbenzene, alkylnaphthalene, ester, ether, glycol, silicone oil, and fluorinated oil. Of these, PAO and esters are preferably used. PAO is chemically inert, has excellent viscosity characteristics, and is commercially available with a wide range of viscosities.
- Esters are also commercially available as compounds with various molecular structures, each having unique characteristics and higher flash point than hydrocarbon base oils of the same viscosity.
- the ester can be obtained by a dehydration condensation polymerization reaction between an alcohol and a fatty acid. Esters are suitable as lubricating base oils.
- Animal and vegetable oil-based lubricating base oils include milk fat, beef tallow, lard (pig tallow), sheep fat, beef leg oil, whale oil coconut oil, bonito oil, herring oil, coconut oil, and soybean oil, rapeseed oil, Sunflower oil, safflower oil, peanut oil, corn oil, cottonseed oil, rice bran oil, kapok oil, sesame oil, olive oil, linseed oil, castor oil, cacao butter, sha fat, palm oil, palm kernel oil, coconut oil, hemp seed oil, Rice oil and tea seed oil are preferred, but not limited thereto.
- these base oils such as mineral oils, synthetic oils and animal and vegetable oils can be appropriately combined and blended at an appropriate ratio so as to satisfy various performances required for each application.
- a plurality of lubricating base oils of mineral oil type, synthetic oil type and animal and vegetable oil type may be used.
- 3,4,5-trihydroxybenzoic acid ester has high solubility in lubricating base oils having polar groups such as synthetic esters, ethers, or animal and plant systems, when these base oils are used, The amount of the cleaning dispersant added can be reduced.
- the lubricating base oils having these polar groups generally have low hydrolysis resistance, and from the economical aspect, the lubricating base oils having polar groups with respect to 100 parts by weight of the mineral-based lubricating base oil
- the mixing ratio is preferably 50 parts by mass or less, more preferably 5 to 30 parts by mass, based on the lubricating base oil.
- 3,4,5-trihydroxybenzoic acid ester In the present invention, 3,4,5-trihydroxybenzoic acid ester is added.
- the ester is synthesized from 3,4,5-trihydroxybenzoic acid and a linear or branched alcohol having 3 to 12 carbon atoms.
- the 3,4,5-trihydroxybenzoic acid alkyl esters are preferred.
- the alkyl esters of 3,4,5-trihydroxybenzoic acid propyl ester, butyl ester, hexyl ester, octyl ester, decyl ester and dodecyl ester are preferable, and propyl ester of 3,4,5-trihydroxybenzoic acid is particularly preferable.
- 3,4,5-Trihydroxybenzoic acid octyl ester is preferred from the standpoint of the balance between solubility in base oil and improvement in lubricity.
- the alkyl group may be linear or branched.
- the 3,4,5-trihydroxybenzoic acid ester is added in an amount of 0.01 to 10% by mass, preferably 0.1 to 5% by mass, based on the total amount of the lubricating oil composition. If the amount is less than 0.01% by mass, the reduction in wear, the reduction in the friction coefficient, and the rust prevention effect cannot be sufficiently achieved. Can not be expected, it is not economical.
- detergent dispersant examples include metal detergents such as alkaline earth metal sulfonates, alkaline earth metal phenates, and alkaline earth metal salicylates, or polyalkenyl succinimides, polyalkenyl succinates and their respective boric acid modifications. And phosphonate types, or ashless dispersants such as benzylamines, boron-containing benzylamines, monovalent or divalent carboxylic acid amides represented by fatty acids or succinic acid are suitable.
- metal detergents such as alkaline earth metal sulfonates, alkaline earth metal phenates, and alkaline earth metal salicylates
- polyalkenyl succinimides polyalkenyl succinates and their respective boric acid modifications.
- phosphonate types, or ashless dispersants such as benzylamines, boron-containing benzylamines, monovalent or divalent carboxylic acid amides represented by fatty acids or succinic acid are
- Alkaline earth metal sulfonate is an alkaline earth metal salt of a product obtained by sulfonating an alkyl aromatic compound using fuming sulfuric acid or sulfuric acid
- alkaline earth metal phenate is alkylphenol sulfide or alkylphenol sulfide and formaldehyde.
- the alkaline earth metal salt of the Mannich reaction product of alkylphenol obtained by the reaction, and the alkaline earth metal salicylate are alkaline earth metal salts of alkylsalicylic acid. Examples of the alkaline earth metal that forms a salt include calcium, barium, and magnesium, with calcium being particularly preferred.
- an ashless detergent obtained by the reaction of polybutenyl succinate polyamine by maleating a polybutene having a molecular weight of 1,000 to several thousand is particularly suitable.
- the detergent dispersant is added in an amount of 0.1 to 20% by mass based on the total amount of the lubricating oil composition, and it is particularly preferable to add 1 to 10% by mass. If the amount is less than 0.1% by mass, the effect cannot be sufficiently exerted, and even if it is added in excess of 20% by mass, the effect cannot be expected for an increase in the amount added, and this is not economical.
- Friction modifiers include organic molybdenum compounds such as molybdenum dithiocarbamate and molybdenum dithiophosphate, and nitrogenous compounds such as aliphatic amines, aliphatic amides, aliphatic imides and alcohols, esters, phosphate ester amine salts, and phosphite amines.
- Deactivate metals such as salts, phosphate esters and zinc dialkyldithiophosphates as antiwear agents, sulfurized olefins and sulfurized fats and oils as extreme pressure agents, amine and phenolic antioxidants as antioxidants
- the agent include benzotriazole
- examples of the rust inhibitor include alkenyl succinic acid ester and partial ester
- examples of the antifoaming agent include a silicone compound and an ester-based antifoaming agent.
- a lubricating oil for an internal combustion engine, a drive system lubricating oil, and a working oil are suitable.
- A 3,4,5-trihydroxybenzoic acid ester
- A1 3,4,5-trihydroxybenzoic acid propyl (n-propyl) ester [manufactured by Iwate Chemical Co., Ltd.]
- A2) 3,4,5-Trihydroxybenzoic acid octyl (n-octyl) ester [Wako Pure Chemical Industries, Ltd.]
- B Lubricating base oil (B1) Paraffinic mineral oil (40 ° C. kinematic viscosity: 32 mm 2 / s, viscosity index: 106, pour point: ⁇ 15 ° C., flash point: 230 ° C.) (B2) Polyol ester oil (40 ° C. kinematic viscosity: 10 mm 2 / s, viscosity index: 95, pour point: ⁇ 50 ° C., flash point: 190 ° C.) (B3) Polyalphaolefin (PAO, 40 ° C. kinematic viscosity: 400 mm 2 / s, viscosity index: 150, pour point: ⁇ 35 ° C., flash point: 280 ° C.)
- Paraffinic mineral oil 40 ° C. kinematic viscosity: 32 mm 2 / s, viscosity index: 106, pour point: ⁇ 15 ° C., flash point: 230 ° C
- C detergent dispersant (C1) neutral calcium sulfonate (C2) polybutenyl succinimide (D) other additives (D1) antioxidant: di-t.-butyl-p.-cresol ( DBPC) (D2) Antiwear agent: tricresyl phosphate (TCP) (D3) Friction modifier: Molybdenum dithiocarbamate (MoDTC)
- Each of the lubricant compositions of Examples 1 to 7 and Comparative Examples 1 to 4 thus obtained was evaluated for appearance and lubrication performance (friction coefficient, wear depth) as a general lubricant composition.
- the measurement and evaluation were performed by the following method. ⁇ appearance ⁇ After blending at the blending ratio shown in Table 1 and cooling to room temperature, the finished composition was visually observed. The case where a precipitate or a precipitate was generated was rejected, and the case where a uniform liquid was obtained was determined as acceptable.
- Abrasion resistance test The wear resistance of the lubricating oil compositions of Examples 1 to 7 and Comparative Examples 1 to 4 was measured using a ball / disk type reciprocating friction tester.
- the test conditions were such that the oil film was not easily formed and the sliding speed was low (1 cm / s), high load (2200 gf), the amplitude was 20 mm, and the test was started at room temperature, so that the strict lubrication conditions were achieved. Friction was performed. Incidentally, bearing carbon steel (SUJ-2) was used as a test piece for the ball and the disk. The friction coefficient after 2 hours and the disc wear depth after the test were measured with a stylus type surface roughness meter.
- SUJ-2 bearing carbon steel
- the lubricating oil compositions of Examples 1 to 7 all became uniform liquids.
- the friction coefficient in the friction test of these examples is 0.05 to 0.07 and is low and stable. Further, the disc wear depth after the friction test is 0.04 to 0.06 ⁇ m, which is a level with almost no wear.
- Comparative Example 1 in which propyl 3,4,5-trihydroxybenzoate was added but no detergent dispersant was added, the composition was turbid and propyl 3,4,5-trihydroxybenzoate was It can be seen that it is not uniformly dissolved or dispersed. For this reason, the friction coefficient is high and the disk wear depth is also large.
- the lubricating oil composition of the present invention has a characteristic that the wear is remarkably reduced and the coefficient of friction is low and stable, and also has a high rust prevention effect in the iron-based sliding part. It is useful as a lubricating oil for some parts, particularly as a lubricating oil for internal combustion engines, a drive system lubricating oil or a working oil.
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Abstract
Description
例えば、自動車においては、燃費を向上させ、CO2の排出を抑制するため、ガソリンエンジンにおいてリーンバーン化や直噴化の技術が採用されるなど、エンジンの効率化が図られる一方、エンジンの摩擦を低減するため、摺動部品への低摩擦材料の使用や省燃費型内燃機関用潤滑油や駆動系潤滑油の採用が図られている。ところで、エンジンには排気ガスを浄化するために三元触媒が装着されており、この三元触媒はリン分によって被毒されて使用と共に排気ガスの浄化率が低下していくため、潤滑油中のリン分の低減が求められていた。しかし、潤滑油中のリン分の低下は耐摩耗性の低下や焼付きなどを引き起こすという問題があったため、本出願人はダイマー酸ジアミドおよびモリブデンジチオカーバメイト(MoDTC)を配合した内燃機関用潤滑油を提案した(特許文献1)。 In recent years, various fields have been required to cope with environmental load reduction. In particular, the reduction of carbon dioxide is an urgent issue, and energy saving has been achieved in various domestic industrial fields, transportation fields including automobiles, and general consumer life.
For example, in automobiles, in order to improve fuel efficiency and suppress CO 2 emissions, the engine engine efficiency is improved by adopting lean burn and direct injection technologies in gasoline engines. In order to reduce this, use of a low-friction material for sliding parts, fuel-saving internal combustion engine lubricants, and drive system lubricants are being adopted. By the way, the engine is equipped with a three-way catalyst for purifying the exhaust gas, and this three-way catalyst is poisoned by phosphorus, and the purification rate of exhaust gas decreases with use. There has been a demand for reduction of phosphorus content. However, since the decrease in the phosphorus content in the lubricating oil has a problem of causing a decrease in wear resistance and seizure, the present applicant has obtained a lubricating oil for internal combustion engines in which dimer acid diamide and molybdenum dithiocarbamate (MoDTC) are blended. (Patent Document 1).
昨今、機械システムの小型化、高速化、省燃費・省エネルギ-化により摺動部における負荷が高まり、より耐摩耗性等の潤滑性に優れる潤滑油が求められている。 Also, in industrial equipment machines, the pressure energy of hydraulic pumps is converted into kinetic energy (work energy) for systems that require large work energy such as injection molding machines, machine tools, press machines, and forging press machines. The hydraulic system that can be used is widely used. Even in this hydraulic system, energy saving needs are increasing, and energy saving measures are also required for hydraulic fluid that is the pressure medium of the hydraulic system, and low viscosity and high viscosity index are being achieved. As a result of lowering the viscosity, there has been a problem of reduced wear resistance and seizure of the sliding portion.
In recent years, the load on the sliding portion has increased due to the downsizing, speeding up, and fuel and energy savings of mechanical systems, and there has been a demand for lubricating oils that are more excellent in lubricity such as wear resistance.
高速下における摩擦損失の低減には、潤滑油基油自体の粘度を下げて対応する必要がある。しかし、基油の粘度を下げると、フレッティング等の摩耗に対して弱くなり、すなわち、摺動する金属同士等の母材間の接触が発生して摩耗や焼付けを生じる恐れがある。 The ideal characteristic of the lubricating oil is that there is little friction loss at high speeds and low speeds, and there is little wear such as fretting wear. That is, the lubricating oil is required to reduce friction loss and reduce wear. Therefore, it is desired that the friction loss is small and the wear is small even when the contact surface speed is high, such as when rotating at high speed, or when high torque is applied at low speed.
To reduce the friction loss at high speed, it is necessary to reduce the viscosity of the lubricating base oil itself. However, when the viscosity of the base oil is lowered, it becomes weak against wear such as fretting, that is, contact between base materials such as sliding metals may occur and wear or seizure may occur.
(1)摩擦係数を下げ、摩耗を抑制できる機能を有すること、
(2)鉄の赤錆であるヘマタイトを硬くて強度のある黒錆(マグネタイト)に還元するため、高い防錆効果を有すること、
(3)3,4,5‐トリヒドロキシ安息香酸化合物自体は、鉱油系潤滑油基油に対する溶解度が低いため、そのままでは上記の効果を発揮しないが、清浄分散剤とともに用いるとその効果が発揮できること、
などの驚くべき知見を得、本発明に想到した。
本発明は、上記の小型化、高速化、省燃費・省エネルギー化によって、よりシビアとなっている摺動部における諸問題を解決するもので、本発明が解決しようとする課題は、摩耗を大幅に低減し、かつ低い摩擦係数を安定して示すとともに、鉄系摺動部の潤滑において高い防錆性を有する潤滑油組成物を提供することである。 The inventors of the present invention have made extensive studies in order to achieve such problems, and as a result, 3,4,5-trihydroxybenzoic acid ester is
(1) having a function of reducing friction coefficient and suppressing wear;
(2) Because hematite, which is iron red rust, is reduced to hard and strong black rust (magnetite), it has a high anti-rust effect.
(3) The 3,4,5-trihydroxybenzoic acid compound itself has low solubility in mineral-based lubricating base oils, so it does not exhibit the above effect as it is, but it can exhibit its effect when used with a cleaning dispersant. ,
As a result, they have come up with the present invention.
The present invention solves various problems in the sliding part which is more severe by the above-mentioned miniaturization, high speed, fuel saving and energy saving, and the problem to be solved by the present invention is to greatly reduce wear. And providing a lubricating oil composition having a low friction coefficient and having a high rust prevention property in lubrication of iron-based sliding parts.
(1)潤滑油基油に、3,4,5‐トリヒドロキシ安息香酸エステルを、潤滑油組成物全量基準で0.01~10質量%、および清浄分散剤を、潤滑油組成物全量基準で0.1~20質量%添加することを特徴とする潤滑油組成物。
(2)3,4,5‐トリヒドロキシ安息香酸エステルが3,4,5‐トリヒドロキシ安息香酸と炭素数3~12の直鎖あるいは分岐鎖アルコールで合成される3,4,5‐トリヒドロキシ安息香酸アルキルエステルである上記(1)に記載の潤滑油組成物。
(3)潤滑油基油の40℃における動粘度が5~1000mm2/sである上記(1)または(2)に記載の潤滑剤組成物。
(4)上記(1)~(3)の潤滑油組成物からなる内燃機関用潤滑油、駆動系潤滑油あるいは作動油。 That is, the present invention is as follows.
(1) To the lubricating base oil, 3,4,5-trihydroxybenzoic acid ester, 0.01 to 10% by mass on the basis of the total amount of the lubricating oil composition, and the detergent dispersant based on the total amount of the lubricating oil composition A lubricating oil composition characterized by adding 0.1 to 20% by mass.
(2) 3,4,5-Trihydroxybenzoate is synthesized from 3,4,5-trihydroxybenzoic acid and a linear or branched alcohol having 3 to 12 carbon atoms. The lubricating oil composition according to the above (1), which is an alkyl benzoate.
(3) The lubricant composition according to the above (1) or (2), wherein the lubricant base oil has a kinematic viscosity at 40 ° C. of 5 to 1000 mm 2 / s.
(4) A lubricating oil for an internal combustion engine, a drive system lubricating oil or a hydraulic oil comprising the lubricating oil composition according to the above (1) to (3).
本発明において、潤滑油基油としては、鉱油系、合成油系、動植物油系などの潤滑油基油を用いることができる。さらに、これらの潤滑油基油を2種以上混合して用いることもできる。
本発明に用いられる潤滑油基油の物性は特に限定するものではないが、40℃における動粘度が5~1000mm2/sのものが好ましく、低粘度化により省エネルギーが図れることから、好ましくは5~500mm2/s、より好ましくは5~100mm2/sのものである。ただし、高負荷の用途には高粘度の基油を使うことが好ましい。
粘度指数としては90以上が好ましく、より好ましくは100~250である。また、低温特性である流動点は-10℃以下が好ましく、-15℃以下がより好ましい。さらには、安全面から引火点が70℃以上であることが好ましく、150℃以上がより好ましい。
なお、この潤滑油基油は、潤滑油組成物全量基準で、70~99質量%配合することが好ましく、80~98質量%がより好ましい。 [Lubricant base oil]
In the present invention, as the lubricating base oil, a lubricating base oil such as mineral oil, synthetic oil, animal or vegetable oil can be used. Further, two or more of these lubricating base oils can be mixed and used.
The physical properties of the lubricating base oil used in the present invention are not particularly limited, but those having a kinematic viscosity of 5 to 1000 mm 2 / s at 40 ° C. are preferred, and energy saving can be achieved by lowering the viscosity. It is about 500 mm 2 / s, more preferably 5 to 100 mm 2 / s. However, it is preferable to use a high viscosity base oil for high load applications.
The viscosity index is preferably 90 or more, more preferably 100 to 250. The pour point, which is a low temperature characteristic, is preferably −10 ° C. or lower, more preferably −15 ° C. or lower. Furthermore, from the viewpoint of safety, the flash point is preferably 70 ° C. or higher, and more preferably 150 ° C. or higher.
The lubricating base oil is preferably blended in an amount of 70 to 99 mass%, more preferably 80 to 98 mass%, based on the total amount of the lubricating oil composition.
なお、3,4,5‐トリヒドロキシ安息香酸エステルは、合成系のエステルやエーテルあるいは動植物系などの極性基を有する潤滑油基油に対する溶解性が高いので、これらの基油を用いる場合は、清浄分散剤の添加量を低減できる。しかし、これらの極性基を有する潤滑油基油は、一般に、耐加水分解安定性が低く、また、経済性の面から、鉱油系潤滑油基油100質量部に対する極性基を有する潤滑油基油の混合割合は、潤滑油基油基準で、50質量部以下が好ましく、5~30質量部がより好ましい。 Usually, these base oils such as mineral oils, synthetic oils and animal and vegetable oils can be appropriately combined and blended at an appropriate ratio so as to satisfy various performances required for each application. At this time, a plurality of lubricating base oils of mineral oil type, synthetic oil type and animal and vegetable oil type may be used.
In addition, since 3,4,5-trihydroxybenzoic acid ester has high solubility in lubricating base oils having polar groups such as synthetic esters, ethers, or animal and plant systems, when these base oils are used, The amount of the cleaning dispersant added can be reduced. However, the lubricating base oils having these polar groups generally have low hydrolysis resistance, and from the economical aspect, the lubricating base oils having polar groups with respect to 100 parts by weight of the mineral-based lubricating base oil The mixing ratio is preferably 50 parts by mass or less, more preferably 5 to 30 parts by mass, based on the lubricating base oil.
本発明では3,4,5‐トリヒドロキシ安息香酸エステルを添加するが、そのエステルとしては、3,4,5‐トリヒドロキシ安息香酸と炭素数3~12の直鎖あるいは分岐鎖アルコールで合成される3,4,5‐トリヒドロキシ安息香酸アルキルエステルが好適である。3,4,5‐トリヒドロキシ安息香酸アルキルエステルのなかでも、プロピルエステル、ブチルエステル、ヘキシルエステル、オクチルエステル、デシルエステル、ドデシルエステルが好ましく、特には3,4,5‐トリヒドロキシ安息香酸プロピルエステル、3,4,5‐トリヒドロキシ安息香酸オクチルエステルが、基油への溶解性と潤滑性向上効果のバランスの面から好ましい。アルキル基については、直鎖でも分岐鎖でも良い。
3,4,5‐トリヒドロキシ安息香酸エステルについては、潤滑油組成物全量基準で、0.01~10質量%添加するが、0.1~5質量%が好ましい。0.01質量%未満では、摩耗の低減、摩擦係数の低下および防錆効果が十分に達成できず、また、10質量%を超えて添加しても、添加量の増加の割にはその効果の向上が期待できず、経済的でない。 [3,4,5-trihydroxybenzoic acid ester]
In the present invention, 3,4,5-trihydroxybenzoic acid ester is added. The ester is synthesized from 3,4,5-trihydroxybenzoic acid and a linear or branched alcohol having 3 to 12 carbon atoms. The 3,4,5-trihydroxybenzoic acid alkyl esters are preferred. Among the alkyl esters of 3,4,5-trihydroxybenzoic acid, propyl ester, butyl ester, hexyl ester, octyl ester, decyl ester and dodecyl ester are preferable, and propyl ester of 3,4,5-trihydroxybenzoic acid is particularly preferable. 3,4,5-Trihydroxybenzoic acid octyl ester is preferred from the standpoint of the balance between solubility in base oil and improvement in lubricity. The alkyl group may be linear or branched.
The 3,4,5-trihydroxybenzoic acid ester is added in an amount of 0.01 to 10% by mass, preferably 0.1 to 5% by mass, based on the total amount of the lubricating oil composition. If the amount is less than 0.01% by mass, the reduction in wear, the reduction in the friction coefficient, and the rust prevention effect cannot be sufficiently achieved. Can not be expected, it is not economical.
清浄分散剤としては、例えば、アルカリ土類金属スルホネート、アルカリ土類金属フェネート、アルカリ土類金属サリシレートなどの金属系清浄剤、またはポリアルケニルコハク酸イミド、ポリアルケニルコハク酸エステルおよびそれぞれのホウ酸変性物やホスホネートタイプ、あるいはベンジルアミン類、ホウ素含有ベンジルアミン類、脂肪酸あるいはコハク酸で代表される一価又は二価カルボン酸アミド類などの無灰系分散剤が好適である。
アルカリ土類金属スルホネートは、アルキル芳香族化合物を発煙硫酸や硫酸を用いてスルホン化することによって得られる生成物のアルカリ土類金属塩、アルカリ土類金属フェネートは、アルキルフェノールサルファイドまたはこのアルキルフェノールとホルムアルデヒドを反応させて得られるアルキルフェノールのマンニッヒ反応生成物のアルカリ土類金属塩、また、アルカリ土類金属サリシレートは、アルキルサルチル酸のアルカリ土類金属塩である。塩を形成するアルカリ土類金属としては、カルシウム、バリウム、マグネシウムなどが挙げられ、特にはカルシウムが好ましい。なお、中性塩だけではなく、さらにアルカリ土類金属塩を付加した過塩基性金属塩もあり、どちらでも良い。
ポリアルケニルコハク酸イミドとしては、特に、分子量千~数千のポリブテンのマレイン化によるポリブテニルコハク酸ポリアミンの反応によって得られる無灰分清浄剤が、好適である。 [Cleaning dispersant]
Examples of the detergent dispersant include metal detergents such as alkaline earth metal sulfonates, alkaline earth metal phenates, and alkaline earth metal salicylates, or polyalkenyl succinimides, polyalkenyl succinates and their respective boric acid modifications. And phosphonate types, or ashless dispersants such as benzylamines, boron-containing benzylamines, monovalent or divalent carboxylic acid amides represented by fatty acids or succinic acid are suitable.
Alkaline earth metal sulfonate is an alkaline earth metal salt of a product obtained by sulfonating an alkyl aromatic compound using fuming sulfuric acid or sulfuric acid, and alkaline earth metal phenate is alkylphenol sulfide or alkylphenol sulfide and formaldehyde. The alkaline earth metal salt of the Mannich reaction product of alkylphenol obtained by the reaction, and the alkaline earth metal salicylate are alkaline earth metal salts of alkylsalicylic acid. Examples of the alkaline earth metal that forms a salt include calcium, barium, and magnesium, with calcium being particularly preferred. In addition, there is not only a neutral salt but also an overbased metal salt to which an alkaline earth metal salt is further added, either of which may be used.
As the polyalkenyl succinimide, an ashless detergent obtained by the reaction of polybutenyl succinate polyamine by maleating a polybutene having a molecular weight of 1,000 to several thousand is particularly suitable.
この清浄分散剤は、潤滑油組成物全量基準で0.1~20質量%添加するが、特には、1~10質量%添加することが好ましい。0.1質量%未満では、効果が十分に発揮できず、また、20質量%を超えて添加しても、添加量の増加の割にはその効果の向上が期待できず、経済的でない。 Although it is difficult to accurately consider the action of the detergent and dispersant, in the case of the present invention, 3,4,5-trihydroxybenzoic acid ester having low solubility in hydrocarbon oil is dissolved in the base oil. , Presumed to play a role of dispersion.
The detergent dispersant is added in an amount of 0.1 to 20% by mass based on the total amount of the lubricating oil composition, and it is particularly preferable to add 1 to 10% by mass. If the amount is less than 0.1% by mass, the effect cannot be sufficiently exerted, and even if it is added in excess of 20% by mass, the effect cannot be expected for an increase in the amount added, and this is not economical.
本発明の潤滑油組成物には、本発明の目的が損なわれない範囲で、従来から潤滑油やグリースなどに用いられている、摩擦調整剤、摩耗防止剤、極圧剤、酸化防止剤、防錆剤、金属不活性化剤、消泡剤などの添加剤を、より性能を向上させるために添加することができる。
摩擦調整剤としては有機モリブデン化合物であるモリブデンジチオカーバメートやモリブデンジチオフォスフェート、含窒素化合物である脂肪族アミン、脂肪族アミド、脂肪族イミドやアルコール、エステル、リン酸エステルアミン塩、亜リン酸エステルアミン塩など、摩耗防止剤としてはリン酸エステル、ジアルキルジチオリン酸亜鉛など、極圧剤としては硫化オレフィン、硫化油脂など、酸化防止剤としてはアミン系、フェノール系の酸化防止剤など、金属不活性化剤としてはベンゾトリアゾールなど、防錆剤としてはアルケニルコハク酸エステルまたは部分エステルなど、消泡剤としてはシリコーン化合物、エステル系消泡剤などがそれぞれ挙げられる。
本発明の潤滑油組成物の用途としては、内燃機関用潤滑油、駆動系潤滑油、作動油が適している。 [Other additives]
In the lubricating oil composition of the present invention, friction modifiers, antiwear agents, extreme pressure agents, antioxidants, which are conventionally used in lubricating oils and greases, etc., as long as the object of the present invention is not impaired. Additives such as rust inhibitors, metal deactivators, and antifoaming agents can be added to further improve performance.
Friction modifiers include organic molybdenum compounds such as molybdenum dithiocarbamate and molybdenum dithiophosphate, and nitrogenous compounds such as aliphatic amines, aliphatic amides, aliphatic imides and alcohols, esters, phosphate ester amine salts, and phosphite amines. Deactivate metals, such as salts, phosphate esters and zinc dialkyldithiophosphates as antiwear agents, sulfurized olefins and sulfurized fats and oils as extreme pressure agents, amine and phenolic antioxidants as antioxidants Examples of the agent include benzotriazole, examples of the rust inhibitor include alkenyl succinic acid ester and partial ester, and examples of the antifoaming agent include a silicone compound and an ester-based antifoaming agent.
As the use of the lubricating oil composition of the present invention, a lubricating oil for an internal combustion engine, a drive system lubricating oil, and a working oil are suitable.
次に示す3,4,5‐トリヒドロキシ安息香酸エステル、潤滑油基油、清浄分散剤、その他の添加剤を用いて、表1に示す配合割合(添加量は組成物全量基準での質量%)でブレンドして、実施例および比較例の潤滑油組成物を調製した。なお、基油及び実施例、比較例の潤滑油の性状について、粘度、粘度指数はJIS K2283、流動点はJIS K2269、引火点はJIS K2265-4に規定の方法により測定した。 (Preparation of lubricating oil composition)
Using the following 3,4,5-trihydroxybenzoate ester, lubricating base oil, detergent dispersant, and other additives, the blending ratio shown in Table 1 (addition amount is mass% based on the total amount of the composition) The lubricating oil compositions of Examples and Comparative Examples were prepared. The properties of the base oil and the lubricating oils of the examples and comparative examples were measured by the methods prescribed in JIS K2283, the pour point, JIS K2269, and the flash point in JIS K2265-4.
(A1)3,4,5‐トリヒドロキシ安息香酸プロピル(n‐プロピル)エステル[岩手ケミカル社製]
(A2)3,4,5‐トリヒドロキシ安息香酸オクチル(n‐オクチル)エステル[和光純薬工業社製] (A) 3,4,5-trihydroxybenzoic acid ester (A1) 3,4,5-trihydroxybenzoic acid propyl (n-propyl) ester [manufactured by Iwate Chemical Co., Ltd.]
(A2) 3,4,5-Trihydroxybenzoic acid octyl (n-octyl) ester [Wako Pure Chemical Industries, Ltd.]
(B1)パラフィン系鉱物油(40℃動粘度:32mm2/s、粘度指数:106、流動点:-15℃、引火点:230℃)
(B2)ポリオールエステル油(40℃動粘度:10mm2/s、粘度指数:95、流動点:-50℃、引火点:190℃)
(B3)ポリアルファオレフィン(PAO,40℃動粘度:400mm2/s、粘度指数:150、流動点:-35℃、引火点:280℃) (B) Lubricating base oil (B1) Paraffinic mineral oil (40 ° C. kinematic viscosity: 32 mm 2 / s, viscosity index: 106, pour point: −15 ° C., flash point: 230 ° C.)
(B2) Polyol ester oil (40 ° C. kinematic viscosity: 10 mm 2 / s, viscosity index: 95, pour point: −50 ° C., flash point: 190 ° C.)
(B3) Polyalphaolefin (PAO, 40 ° C. kinematic viscosity: 400 mm 2 / s, viscosity index: 150, pour point: −35 ° C., flash point: 280 ° C.)
(C1)中性カルシウムスルホネート
(C2)ポリブテニルコハク酸イミド
(D)その他の添加剤
(D1)酸化防止剤:ジ‐t.‐ブチル‐p.‐クレゾ-ル(DBPC)
(D2)摩耗防止剤:トリクレジルフォスフェート(TCP)
(D3)摩擦調整剤:モリブデンジチオカーバメート(MoDTC) (C) detergent dispersant (C1) neutral calcium sulfonate (C2) polybutenyl succinimide (D) other additives (D1) antioxidant: di-t.-butyl-p.-cresol ( DBPC)
(D2) Antiwear agent: tricresyl phosphate (TCP)
(D3) Friction modifier: Molybdenum dithiocarbamate (MoDTC)
〔測定・評価方法〕
前記の測定および評価は、次の方法にて行った。
〔外観〕
表1の配合割合で調合し、室温まで冷却した後、組成物の出来上がりを外観目視により観察した。析出物や沈殿物が発生した場合を不合格とし、均一液体が得られた場合を合格とした。
〔耐摩耗性試験〕
ボール/ディスクタイプの往復摩擦試験機を用いて、実施例1~7および比較例1~4の潤滑油組成物の耐摩耗性を測定した。
試験条件は、より油膜ができにくく、厳しい潤滑条件となるように、しゅう動速度が低速(1cm/s)、高荷重(2200g f)とし、振幅20mm、室温で試験を開始し、2時間往復摩擦を実施した。なお、ボ-ルとディスクの試験片は、軸受炭素鋼(SUJ-2)を用いた。2時間経過時の摩擦係数および試験後のディスク摩耗深さを触針式表面粗さ計で計測した。 Each of the lubricant compositions of Examples 1 to 7 and Comparative Examples 1 to 4 thus obtained was evaluated for appearance and lubrication performance (friction coefficient, wear depth) as a general lubricant composition.
[Measurement and evaluation method]
The measurement and evaluation were performed by the following method.
〔appearance〕
After blending at the blending ratio shown in Table 1 and cooling to room temperature, the finished composition was visually observed. The case where a precipitate or a precipitate was generated was rejected, and the case where a uniform liquid was obtained was determined as acceptable.
[Abrasion resistance test]
The wear resistance of the lubricating oil compositions of Examples 1 to 7 and Comparative Examples 1 to 4 was measured using a ball / disk type reciprocating friction tester.
The test conditions were such that the oil film was not easily formed and the sliding speed was low (1 cm / s), high load (2200 gf), the amplitude was 20 mm, and the test was started at room temperature, so that the strict lubrication conditions were achieved. Friction was performed. Incidentally, bearing carbon steel (SUJ-2) was used as a test piece for the ball and the disk. The friction coefficient after 2 hours and the disc wear depth after the test were measured with a stylus type surface roughness meter.
〔内燃機関用潤滑油としての評価〕
内燃機関用潤滑油としての評価はシリンダー/ディスクタイプのSRV摩擦試験機を用い、温度を100℃と高温に設定し、ディスク摩耗痕径及び摩擦係数を測定した。
条件は、荷重:200N、周波数:300Hz、振幅:1.0mm、試験時間:1時間で、シリンダーでディスクに往復動摩擦を加えて、ディスクに生じた摩耗痕径を顕微鏡で測定した。摩擦係数は、摩擦試験機にあらかじめ備えられている歪み計により測定した。 Next, characteristics as lubricating oils for internal combustion engines, drive system lubricating oils, and hydraulic oils were evaluated using the lubricating oil compositions of Examples 1 to 7, and compared with Comparative Examples 1 to 4.
[Evaluation as lubricating oil for internal combustion engines]
For evaluation as a lubricating oil for an internal combustion engine, a cylinder / disk type SRV friction tester was used, the temperature was set at a high temperature of 100 ° C., and the disk wear scar diameter and the friction coefficient were measured.
The conditions were load: 200 N, frequency: 300 Hz, amplitude: 1.0 mm, test time: 1 hour, the disc was subjected to reciprocating friction with the cylinder, and the wear scar diameter generated on the disc was measured with a microscope. The coefficient of friction was measured with a strain gauge provided in advance in the friction tester.
駆動系潤滑油としての評価はFZGピッチング試験で行った。試験はDIN51354に準拠し、TYPE PT-C歯車を用い、荷重:9ステ-ジ、油温:120℃、回転数:1440回/分 で実施した。疲労寿命判定方法は、試験装置を停止し、歯面の定期観察を行い、1mm2のピッチングが発生した時点の時間(hr)とした。観察間隔は最初の24時間は8時間毎、以降は2~4時間毎とした。 [Evaluation as driveline lubricant]
Evaluation as a drive system lubricant was performed by the FZG pitching test. The test was conducted in accordance with DIN 51354, using a TYPE PT-C gear, with a load of 9 stages, an oil temperature of 120 ° C., and a rotational speed of 1440 times / minute. The fatigue life determination method was performed by stopping the test apparatus, periodically observing the tooth surface, and setting the time (hr) when 1 mm 2 pitching occurred. The observation interval was every 8 hours for the first 24 hours and every 2-4 hours thereafter.
作動油としての評価は高圧ベーンポンプ試験で行った。試験はASTM D2882に準拠し、ポンプ試験機中に56.8リットルの油を循環し、圧力:140kg/cm2、ポンプ回転数:1200rpm、入口油温:65.5℃ で試験時間100時間後のベーンとカムリングの総重量減を測定し、摩耗量とした。
得られた測定、評価結果を表1に、まとめて示した。 [Evaluation as hydraulic oil]
The hydraulic oil was evaluated by a high pressure vane pump test. The test conforms to ASTM D2882 and circulates 56.8 liters of oil in the pump tester, pressure: 140 kg / cm 2 , pump speed: 1200 rpm, inlet oil temperature: 65.5 ° C., after 100 hours of test time The total weight loss of vanes and cam rings was measured and used as the amount of wear.
The obtained measurement and evaluation results are summarized in Table 1.
これに対し、3,4,5‐トリヒドロキシ安息香酸プロピルを添加したものの、清浄分散剤を配合していない比較例1では、組成物がにごり、3,4,5‐トリヒドロキシ安息香酸プロピルが均一に溶解・分散されていないことがわかる。このため、摩擦係数が高く、ディスク摩耗深さも大きくなっている。また、3,4,5‐トリヒドロキシ安息香酸エステルが添加されていない、比較例2~4では、摩擦係数が高く、摩耗深さも実施例よりはるかに大きくなっている。
このように、潤滑油基油に3,4,5‐トリヒドロキシ安息香酸エステルと清浄分散剤を配合することにより、潤滑油組成物の潤滑性を大幅に向上させることができる。
また、実施例1~7の潤滑油組成物は、すべて内燃機関用潤滑油、駆動系潤滑油、作動油としての特性に優れていることがわかる。 The lubricating oil compositions of Examples 1 to 7 all became uniform liquids. The friction coefficient in the friction test of these examples is 0.05 to 0.07 and is low and stable. Further, the disc wear depth after the friction test is 0.04 to 0.06 μm, which is a level with almost no wear.
On the other hand, in Comparative Example 1 in which propyl 3,4,5-trihydroxybenzoate was added but no detergent dispersant was added, the composition was turbid and propyl 3,4,5-trihydroxybenzoate was It can be seen that it is not uniformly dissolved or dispersed. For this reason, the friction coefficient is high and the disk wear depth is also large. In Comparative Examples 2 to 4, in which 3,4,5-trihydroxybenzoic acid ester was not added, the friction coefficient was high and the wear depth was much larger than that of the Examples.
Thus, the lubricity of the lubricating oil composition can be significantly improved by blending the lubricating base oil with 3,4,5-trihydroxybenzoic acid ester and a detergent dispersant.
In addition, it can be seen that the lubricating oil compositions of Examples 1 to 7 are all excellent in properties as a lubricating oil for internal combustion engines, a drive system lubricating oil, and a working oil.
Claims (4)
- 潤滑油基油に、3,4,5‐トリヒドロキシ安息香酸エステルを、潤滑油組成物全量基準で0.01~10質量%および清浄分散剤を、潤滑油組成物全量基準で0.1~20質量%添加することを特徴とする潤滑油組成物。 In the lubricating base oil, 3,4,5-trihydroxybenzoic acid ester is added in an amount of 0.01 to 10% by mass based on the total amount of the lubricating oil composition and a detergent-dispersant. A lubricating oil composition characterized by adding 20% by mass.
- 3,4,5‐トリヒドロキシ安息香酸エステルが3,4,5‐トリヒドロキシ安息香酸と炭素数3~12の直鎖あるいは分岐鎖アルコールで合成される3,4,5‐トリヒドロキシ安息香酸アルキルエステルである請求項1に記載の潤滑油組成物。 3,3,4,5-Trihydroxybenzoic acid ester is synthesized with 3,4,5-trihydroxybenzoic acid and a linear or branched alcohol having 3 to 12 carbon atoms, alkyl 3,4,5-trihydroxybenzoic acid The lubricating oil composition according to claim 1, which is an ester.
- 潤滑油基油の40℃における動粘度が5~1000mm2/sである請求項1または2に記載の潤滑剤組成物。 The lubricant composition according to claim 1 or 2, wherein the lubricating base oil has a kinematic viscosity at 40 ° C of 5 to 1000 mm 2 / s.
- 請求項1~3の潤滑油組成物からなる内燃機関用潤滑油、駆動系潤滑油あるいは作動油。 A lubricating oil for internal combustion engines, a drive system lubricating oil or a working oil comprising the lubricating oil composition according to claims 1 to 3.
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JP2010545744A JP5693240B2 (en) | 2009-01-09 | 2010-01-06 | Lubricating oil composition |
US13/143,755 US20110275549A1 (en) | 2009-01-09 | 2010-01-06 | Lubricating oil composition |
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EP2527420A1 (en) * | 2010-01-18 | 2012-11-28 | JX Nippon Oil & Energy Corporation | Lubricating oil composition |
JP2017008229A (en) * | 2015-06-24 | 2017-01-12 | 竹本油脂株式会社 | Lubricant composition for sliding surface |
WO2018186283A1 (en) * | 2017-04-05 | 2018-10-11 | Jxtgエネルギー株式会社 | Hydraulic device and hydraulic oil composition |
EP2721128B1 (en) * | 2011-06-15 | 2019-08-07 | The Lubrizol Corporation | Lubricating composition containing an ester of an aromatic carboxylic acid |
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JP6405216B2 (en) * | 2014-12-09 | 2018-10-17 | シェルルブリカンツジャパン株式会社 | Lubricating oil composition for sliding guide surfaces |
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CN102272276A (en) | 2011-12-07 |
US20110275549A1 (en) | 2011-11-10 |
JPWO2010079744A1 (en) | 2012-06-21 |
JP5693240B2 (en) | 2015-04-01 |
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