CN101280240B - Gear oil composition - Google Patents
Gear oil composition Download PDFInfo
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- CN101280240B CN101280240B CN2008100897026A CN200810089702A CN101280240B CN 101280240 B CN101280240 B CN 101280240B CN 2008100897026 A CN2008100897026 A CN 2008100897026A CN 200810089702 A CN200810089702 A CN 200810089702A CN 101280240 B CN101280240 B CN 101280240B
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M127/00—Lubricating compositions characterised by the additive being a non- macromolecular hydrocarbon
- C10M127/02—Lubricating compositions characterised by the additive being a non- macromolecular hydrocarbon well-defined aliphatic
-
- 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
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Lubricants (AREA)
Abstract
The present invention provides a gear oil composition, which is high level with low-temperature fluidity and shearing stabilizing ability, having moderate extreme pressure property, and having excellent corrosion resistance and oxygenize stabilizing ability.The gear oil composition is characterized in that: lubricating oil basic oil (A) with viscosity index greater or equal 110 containing : at least one phosphorus series extreme pressure agent (B) selecting from families composed by phosphite ester and phosphoric acid esters with phosphorus element 0.05-0.5 wt%, azote series anticorrosion agent (C-1) with 0.005-0.2wt%, azote sulphur series anticorrosion agent (C-2) with 0.005-0.2 wt%, ethylene -alpha -olefin copolymer (D) as viscosity index improver with 1-10wt%, and 0.02-0.2wt% zinc element zinc dialkyl dithiophosphate (E) with sulphur ingredient less than or equal to 1.4wt%.
Description
Technical field
The present invention relates to a kind of gear oil composition, particularly relate to a kind of gear oil composition that under high speed, high loading environment, uses.
Background technology
At present, friction, the wearing and tearing of contact surface in various industrial fields, are being used various lubricating oil when touching slip each other indirectly in order to alleviate metal.Among said lubricating oil, for gear oil,, also require to have excellent extreme pressure property, oxidation stability, wearability, shear stability etc. except requiring to have the oilness under the working conditions.In order to satisfy these performances, previous gear oil is to make through in the base oil that comprises MO and/or synthetic oil, allocating various additives such as extreme pressure agent, corrosion inhibitor, inhibitor, viscosity index improver.
For example; Open in 2002-371291 number (patent documentation 1) in Japanese Patent Laid and to have disclosed a kind of lubricating oil composition, this lubricating oil composition has been allocated thiadiazoles derivative with ad hoc structure and the P contained compound with ad hoc structure in the base oil that comprises MO and/or synthetic oil.Oxidation stability and the excellent in wear resistance of this lubricating oil composition under high oil temperature improves fatigue lifetime through preventing pitching (pithcing), is suitable as gear oil, automobile is used gear box oil.
Because the defective that above-mentioned existing lubricant compsn exists; The inventor is based on being engaged in this type of product design manufacturing abundant for many years practical experience and expertise; And cooperate the utilization of studying the science, actively study innovation, in the hope of founding a kind of gear oil composition of novel texture; Can improve general existing lubricant compsn, make it have more practicality.Through constantly research, design, and, found out the present invention of true tool practical value finally through after studying sample and improvement repeatedly.
Summary of the invention
But when the device machine start, the whole temperature of device can be identical with outside temperature basically.Therefore, when cold district using appts machine, in order the time not cause the clamping stagnation of gear or move badly that in starting not only employed lubricating oil has the performance under the usual conditions in the claimed apparatus machine, and requires lubricating oil to have low-temperature fluidity.Yet, under the situation of keeping the performance under the usual conditions, improve aspect the low-temperature fluidity, there is variety of issue.
For example, using when being used as in the lubricating oil composition employed base oil as the synthetic oil of representative,, having the problem that causes cost to increase substantially though solve easily in the said problem about the part of performance with poly-alpha-olefin (PAO).On the other hand; Using MO to make viscosity degradation as base oil; And use when improving viscosity index as the viscosity index improver of representative with Rohm tech inc (PMA); Though can guarantee low-temperature fluidity, have the problem that fully to guarantee very important shear stability for gear oil.
And, in a part of guaranteeing the extreme pressure agent that extreme pressure property is required, also can there be the material that low-temperature fluidity is worsened.In addition, because extreme pressure agent must select to have reactive compound of the environment for use that is suitable for gear oil, so, so also have corrosion of metal, or the situation that the oxidation stability of gear oil is descended of causing if too pay attention to extreme pressure property.Therefore; When under low temperature environment, using gear oil; Gear oil must be selected to have the required extreme pressure property of environment for use, can not make low-temperature fluidity worsen and can obviously not reduce the compound of the erosion resistance and the oxidation stability of gear oil with the extreme pressure agent that is added in the compsn, and must add extreme pressure agent with suitable addition.
The objective of the invention is to solve said problem, and a kind of gear oil composition is provided, this gear oil composition has low-temperature fluidity and shear stability concurrently with high level, and not only has the extreme pressure property of appropriateness, and also excellence of erosion resistance and oxidation stability.
People such as present inventor carry out active research in order to realize said purpose; The result finds a kind of gear oil composition; This gear oil composition is through adding the ethene-alpha-olefin copolymer as viscosity index improver in viscosity index in more than or equal to 110 lubricant base, and realizes having low-temperature fluidity and shear stability concurrently with high level, and is that extreme pressure agent, nitrogen are that corrosion inhibitor, nitrogen sulphur are corrosion inhibitor through adding phosphorus; And add zinc dialkyl dithiophosphate (ZnDTP) as inhibitor; And make this gear oil composition have the extreme pressure property of appropriateness, and have excellent erosion resistance and oxidation stability, thus accomplish the present invention.
That is, gear oil composition of the present invention is characterised in that:
It is to make viscosity index more than or equal to containing in 110 the lubricant base (A):
At least a phosphorus of from the group that phosphorous acid ester and SULPHOSUCCINIC ACID ESTER are formed, selecting of counting 0.05～0.5 quality % with the phosphoric quality be extreme pressure agent (B),
0.005 the nitrogen of～0.2 quality % be corrosion inhibitor (C-1),
0.005 the nitrogen sulphur of～0.2 quality % be corrosion inhibitor (C-2),
The ethene-alpha-olefin copolymer of 1～10 quality % (D) as viscosity index improver and
Count the zinc dialkyl dithiophosphate (E) of 0.02～0.2 quality % and form with the zinc element quality,
And the sulphur composition is smaller or equal to 1.4 quality %.In addition, in the gear oil composition of the present invention, sulphur composition/phosphorus composition is preferably smaller or equal to 6.5, and Bu Shi (BF) viscosity under-40 ℃ is preferably smaller or equal to 100.000mPas.
The present invention compared with prior art has tangible advantage and beneficial effect.By technique scheme, gear oil composition of the present invention has advantage and beneficial effect at least:
Gear oil composition of the present invention; Through add the ethene-alpha-olefin copolymer as viscosity index improver (D) of specified quantitative in more than or equal to 110 lubricant base (A) in viscosity index, can realize having low-temperature fluidity and shear stability concurrently with high level.And; Through in said lubricant base (A); The phosphorus that adds specified quantitative is that extreme pressure agent (B), nitrogen are that corrosion inhibitor (C-1), nitrogen sulphur are corrosion inhibitor (C-2); And add the zinc dialkyl dithiophosphate as inhibitor (E) of specified quantitative, can give the extreme pressure property of gear oil composition, and can improve erosion resistance and oxidation stability significantly with appropriateness.Therefore, according to the present invention, a kind of gear oil composition can be provided, this gear oil composition has low-temperature fluidity and shear stability concurrently with high level, and not only has the extreme pressure property of appropriateness, and also excellence of erosion resistance and oxidation stability.
Above-mentioned explanation only is the general introduction of technical scheme of the present invention; Understand technique means of the present invention in order can more to know; And can implement according to the content of specification sheets, and for let of the present invention above-mentioned with other purposes, feature and advantage can be more obviously understandable, below special act preferred embodiment; And conjunction with figs., specify as follows.
Description of drawings
(nothing)
Embodiment
Reach technique means and the effect that predetermined goal of the invention is taked for further setting forth the present invention; Below in conjunction with accompanying drawing and preferred embodiment; To the gear oil composition that proposes according to the present invention, its embodiment, structure, characteristic and effect thereof, specify as after.
Employed base oil is a viscosity index more than or equal to 110 lubricant base (A) in the gear oil composition of the present invention.This lubricant base (A) both can be the MO of lubricating oil distillate, also can be synthetic oil, the lubricant base that can use previous conduct to use as the base oil of the various lubricating oil of representative with gear oil.In addition, this lubricant base (A) requires viscosity index more than or equal to 110, is preferably greater than to equal 120.When using viscosity index smaller or equal to 110 lubricant base, Bu Shi (BF) viscosity under-40 ℃ obviously rises, and can't fully guarantee low-temperature fluidity.And when using viscosity index more than or equal to 120 lubricant base, low-temperature fluidity is especially good.In addition, the viscosity index of common lubricant base (A) is smaller or equal to 180.
Specifically; MO can use: to paraffin (paraffin) is that the air distillation residue of former wet goods carries out underpressure distillation and the cut that obtains; SX, hydrofinishing through utilizing furfural etc., utilize methyl ethyl ketone (methyl ethyl ketone, MEK)/treatment processs such as solvent dewaxing of toluene etc. handle the gained cut and the lubricant base that obtains; The residue of said underpressure distillation is carried out diasphaltene (deasphalting) and obtains deasphalted oil, utilize said suitable treatment process to gained deasphalted oil handle and the lubricant base that obtains; Slack wax (slackwax) or Fischer-Tropsch synthetic (FT is synthetic) paraffin etc. is carried out hydroisomerization handle the refining base oil of the height that is obtained; Heavy oil is decomposed and the suitable cut that obtains carries out the dewaxing of MEK/ toluene solvant or the refining base oil of height that hydrodewaxed obtained and the mixture of these base oils through hydrogenation.
In addition, synthetic oil can use: the oligomer of terminal olefin; By diprotic acid and monohydroxy-alcohol synthetic diester such as hexanodioic acids; Or by polyvalent alcohol and monoprotic acid synthetic polyol esters such as NSC 6366, TriMethylolPropane(TMP), tetramethylolmethanes; Korenyl; Polyether polyols; And their mixture.
Consider from the cost aspect, in these base oils, preferred MO, more preferably the MO of gained is decomposed in hydrogenation.
Said lubricant base (A) preferred movement viscosity (100 ℃) is 4～20mm
2/ s.If the kinematic viscosity of lubricant base (A) (100 ℃) is low excessively; Must increase the viscosity index improver that adds in order to ensure suitable product viscosity so; So may cause shear stability to descend, perhaps oil film thickness decline the causing wearing and tearing owing to sliding part increase.On the other hand, if the kinematic viscosity of lubricant base (A) (100 ℃) is too high, might fully guarantee low-temperature fluidity so.
Said lubricant base (A) optimization aromatic composition is smaller or equal to 5 quality %.If the aromatic component in the lubricant base (A) smaller or equal to 5 quality %, can further improve the stability to heat or oxidation so.In addition, the aromatic component in the lubricant base (A) can utilize the n-d-M ring analysis of regulation among the ASTMD 3238 and try to achieve.
The preferred sulphur composition of said lubricant base (A) is smaller or equal to 0.01 quality %.If the sulphur composition in the lubricant base (A) smaller or equal to 0.01 quality %, can fully suppress the caused corrosion of sulphur composition so.
It is extreme pressure agent (B) that gear oil composition of the present invention contains at least a phosphorus of from the group that phosphorous acid ester and SULPHOSUCCINIC ACID ESTER are formed, selecting of counting 0.05～0.5 quality % with the phosphoric quality, and preferably contains (B) of 0.05～0.1 quality %.And, gear oil composition of the present invention preferably contain simultaneously phosphorous acid ester and SULPHOSUCCINIC ACID ESTER the two.Phosphorus be extreme pressure agent (B) if content in the phosphoric quality less than 0.05 quality %; Extreme pressure property and oxidation stability can be insufficient so, on the other hand, if surpass 0.5 quality % in the phosphoric quality; Might cause corrosion or chemical abrasion so, perhaps oxidation stability descends.In addition, through being that the content of extreme pressure agent (B) is made as in the phosphoric quality smaller or equal to 0.1 quality % with phosphorus, can guarantee erosion resistance and oxidation stability well.
Said phosphorous acid ester (B-1) is with the one or more hydroxyl of the phosphorous acid compound that forms of esterification in addition, both can be three esters, also can be diester, also can be monoesters, preferred diester.In addition, said phosphorous acid ester (B-1), dialkyl phosphites such as preferred specifically phosphorous acid two-2-ethylhexyl, phosphorous acid two lauryls, wherein, preferred phosphorous acid two lauryls etc. have the dialkyl phosphite that carbon number is 8～18 alkyl especially.
Said SULPHOSUCCINIC ACID ESTER (B-2) is with the one or more hydroxyl of the phosphoric acid compound that forms of esterification in addition, both can be three esters, also can be diester, also can be monoesters, preferred three esters.In addition; Said SULPHOSUCCINIC ACID ESTER (B-2); Tri aromatic ester of phosphic acid such as preferably phosphoric acid triphenylmethyl methacrylate, Tritolyl Phosphate, tricresyl phosphate ethyl phenyl ester, tricresyl phosphate propyl group phenyl ester, tricresyl phosphate butyl phenyl ester, tricresyl phosphate base diphenyl ester, phosphoric acid ethylphenyl diphenyl ester, phosphoric acid propyl group phenyl diphenyl ester, phosphoric acid butyl phenyl diphenyl ester, di(2-ethylhexyl)phosphate tolyl phenyl ester, di(2-ethylhexyl)phosphate ethyl phenyl phenyl ester, di(2-ethylhexyl)phosphate propyl group phenyl phenyl ester, di(2-ethylhexyl)phosphate butyl phenyl ester specifically; Wherein, special preferably phosphoric acid front three phenyl ester etc. has the tri aromatic ester of phosphic acid that carbon number is 6～12 aryl.
The nitrogen that gear oil composition of the present invention contains 0.005～0.2 quality % be corrosion inhibitor (C-1) as corrosion inhibitor (C), preferably contain (C-1) of 0.01～0.1 quality %.When nitrogen is that the content of corrosion inhibitor (C-1) is during less than 0.005 quality %; Erosion resistance and/or oxidation stability are insufficient, on the other hand, even add the amount that surpasses 0.2 quality %; The effect of oxidation stability and/or corrosion stability can not significantly improve yet; If add superfluously, can cause the oily tackify behind the oxidative degradation so, so preferably in said scope, add.In addition; Through being that the content of corrosion inhibitor (C-1) is made as more than or equal to 0.01 quality % with nitrogen; The erosion resistance and the oxidation stability of gear oil composition are increased substantially; On the other hand, through being that the content of corrosion inhibitor (C-1) is made as smaller or equal to 0.1 quality % with nitrogen, can under the situation of tackify not, give the oxidation stability and corrosion stability of appropriateness.
Among the present invention, nitrogen is that corrosion inhibitor (C-1) is meant the corrosion inhibitor that contains nitrogen, intramolecularly do not contain aspect the sulphur with after the nitrogen sulphur stated be that corrosion inhibitor (C-2) is distinguished to some extent.This nitrogen is that corrosion inhibitor (C-1) is that ring contains 3 or 3 above N, and the intramolecularly heterogeneous ring compounds such as triazole derivative of sulfur-bearing not; Or has a not heterogeneous ring compound such as imidazolidine derivatives, pyrimidine derivatives of sulfur-bearing of N-C-N key and intramolecularly; And have＞NH, and further has the heterogeneous ring compound of 1 or 1 above nitrogen-atoms; Preferred especially intramolecularly is the compound of sulfur-bearing not.In addition, specifically, nitrogen is that corrosion inhibitor (C-1) can be enumerated N, two (2-ethylhexyl)-(4 or the 5)-methyl isophthalic acid H-benzotriazoles of N--OR 10154 such as 1-methylamine.
The nitrogen sulphur that gear oil composition of the present invention contains 0.005～0.2 quality % be corrosion inhibitor (C-2) as corrosion inhibitor (C), preferably contain (C-2) of 0.01～0.1 quality %.When nitrogen sulphur is that the content of corrosion inhibitor (C-2) is during less than 0.005 quality %; Erosion resistance and/or oxidation stability are insufficient, on the other hand, even add the amount that surpasses 0.2 quality %; The effect of oxidation stability and/or corrosion stability can not show yet and improving; If add superfluously, can cause the oily tackify behind the oxidative degradation so, so preferably in said scope, add.In addition; Through being that the content of corrosion inhibitor (C-2) is made as more than or equal to 0.01 quality % with nitrogen sulphur; The erosion resistance and the oxidation stability of gear oil composition are increased substantially; On the other hand, through being that the content of corrosion inhibitor (C-2) is made as smaller or equal to 0.1 quality % with nitrogen sulphur, can be in the oxidation stability and corrosion stability of also not giving appropriateness behind the oxidative degradation under the situation of tackify.
Among the present invention, nitrogen sulphur is that corrosion inhibitor (C-2) is meant the corrosion inhibitor that contains nitrogen and sulphur, and containing aspect the sulphur with said nitrogen at intramolecularly is that corrosion inhibitor (C-1) is distinguished to some extent.This nitrogen sulphur is the compound that corrosion inhibitor (C-2) preferably contains the N-C-S key, wherein, especially preferably have-N=C (X)-change of S-S-R structure (in the formula, X is NH, O or S, and R is an alkyl) contains thing.And specifically, nitrogen sulphur is that corrosion inhibitor (C-2) can be enumerated thiadiazoles derivative, special preferred alkylization 2, and 5-dimercapto-1,3,4-thiadiazoles etc. has the thiadiazoles derivative of polysulfide structure.
Gear oil composition of the present invention contains the ethene-alpha-olefin copolymer (D) of 1～10 quality % as viscosity index improver.This ethene-alpha-olefin copolymer is to utilize coordination anionic polymerization catalyst etc. to make ethene and alpha-olefin copolymer close the multipolymer that forms, and can adjust viscosity through the polymerization degree.When the content of this ethene-alpha-olefin copolymer (D) during less than 1 quality %, can't fully improve viscosity index, on the other hand, when the content of this ethene-alpha-olefin copolymer (D) surpassed 10 quality %, the raising effect of viscosity index can reach capacity.Moreover when using ethene-alpha-olefin copolymer (D) additive in addition as viscosity index improver, the shear stability meeting of gear oil composition worsens.
The number average molecular weight of said ethene-alpha-olefin copolymer (D) is preferred 1,000～30,000, and more preferably 2,000～10,000.If the number average molecular weight of ethene-alpha-olefin copolymer (D) is more than or equal to 1; 000; Can obtain sufficient viscosity index improvement effect so, on the other hand, if the number average molecular weight of ethene-alpha-olefin copolymer (D) is smaller or equal to 30; 000, can guarantee the shear stability that gear oil is required so.In addition, be 2,000～10,000 ethene-alpha-olefin copolymer (D) through the usage quantity molecular-weight average, can make the balance of viscosity index improvement effect and shear stability reach best.
Gear oil composition of the present invention contain count 0.02～0.2 quality % with the zinc element quality zinc dialkyl dithiophosphate (E) as inhibitor, preferably contain (E) of 0.05～0.1 quality %.When the content of zinc dialkyl dithiophosphate (E) in the zinc element quality during less than 0.02 quality %; Oxidation stability can be insufficient; On the other hand, if surpass 0.2 quality % in the zinc element quality, the deterioration thing of this zn cpds also can increase so; This deterioration thing be not scattered in oil in and become greasy filth (sludge), thereby possibly cause device bad.In addition; If the content of zinc dialkyl dithiophosphate (E) in the zinc element quality more than or equal to 0.02 quality %; Oxidation stability is good especially so; On the other hand, if the content of zinc dialkyl dithiophosphate (E) smaller or equal to 0.2 quality %, the deterioration thing can not become the greasy filth that causes device bad so.
Said zinc dialkyl dithiophosphate (E) is represented with formula (I):
[changing 1]
[in the formula, R1 is an alkyl, both can be identical also can be different].Wherein, the preferred secondary alkyl of alkyl (sec-) that R1 is represented, preferred especially Sec-Hexyl.In general, the zinc dithiophosphate with secondary alkyl (sec-) is characterised in that: compare with the zinc dithiophosphate with one-level alkyl (n-), the wearability extreme pressure property is very excellent, but oxidation stability is poor; Zinc dithiophosphate with aryl is characterised in that: compare with the zinc dithiophosphate with one-level alkyl (n-), oxidation stability is very excellent, but the wearability extreme pressure property is poor.And gear oil is relatively paid attention to the wearability extreme pressure property, thus preferably have the zinc dithiophosphate of secondary alkyl (sec-), but also can and with the zinc dithiophosphate of other types.Moreover, the carbon number of alkyl R1 preferred 4～10.
Can further suitably add ashless in the gear oil composition of the present invention be additives such as dispersion agent, pour point depressant, skimmer; More particularly, can be further suitably add the boracic succimide, sulphur is oiliness improver, phosphorodithioic acid amine, organic amide, nonionic acvator etc.Wherein be alkaline components because metal is a sanitising agent, so can be that the acidic components such as phosphorous acid two lauryls of extreme pressure agent (B) react, and generate greasy filth with belonging to said phosphorus, therefore gear oil composition of the present invention preferably not containing metal be sanitising agent.
Gear oil composition of the present invention is characterised in that the sulphur composition smaller or equal to 1.4 quality %, and preferred sulphur composition is 1.0～1.4 quality %.If the sulphur composition of gear oil composition surpasses 1.4 quality %; Oxidation stability or low-temperature fluidity can worsen so; On the other hand, when using universal gear oil compounding agent (gear oil package), the sulphur composition that is difficult to make gear oil composition is less than 1.0 quality %.In addition, the mass ratio of the preferred sulphur composition/phosphorus composition of gear oil composition of the present invention is smaller or equal to 6.5, and more preferably 4.5～6.5.For balance improves oxidation stability, erosion resistance and extreme pressure property well, preferably the mass ratio with sulphur composition/phosphorus composition is adjusted into said scope.
Bu Shi (BF) viscosity under preferred-40 ℃ of the gear oil composition of the present invention is smaller or equal to 100,000mPas.If the brookfield viscosity under-40 ℃ of gear oil composition is smaller or equal to 100,000mPas, low-temperature fluidity is enough high so, even be used in the device that cold district uses, the clamping stagnation of gear or move bad in the time of also can preventing to start.
[embodiment]
Below, enumerate embodiment and come further explain the present invention, but the present invention does not receive any qualification of following embodiment.
[preparation of gear oil composition]
According to the allotment ratio shown in the top of table 1 and table 2 (addition is to be the quality % of benchmark with the total composition), use following lubricant base and additive, the gear oil composition of preparation embodiment 1 and comparative example 1～13.
< lubricant base >
[A composition: lubricant base]
A-1: MO (100 ℃ kinematic viscosity: 7.6mm
2/ s, viscosity index: 129, aromatic component: 0.0 quality %, sulphur composition: 0.0008 quality %)
A-2: MO (100 ℃ kinematic viscosity: 7.6mm
2/ s, viscosity index: 100, aromatic component: 5.9 quality %, sulphur composition: 0.16 quality %)
< additive >
[B composition: extreme pressure agent]
B-1: phosphorous acid two lauryls
B-2: Tritolyl Phosphate
B-3: olefine sulfide and the mixture that vulcanizes ester
B-4: phosphorodithioate
B-5: sulfuration arctic sperm oil
[C composition: corrosion inhibitor]
C-1:N, two (2-ethylhexyl)-(4 or the 5)-methyl isophthalic acid H-benzotriazoles of N--1-methylamine
C-2: alkylation 2,5-dimercapto-1,3,4-thiadiazoles (alkyl is that carbon number is 9 branched structure)
[D composition: viscosity index improver]
D-1: ethene-alpha-olefin copolymer (number average molecular weight: 5,200)
D-2: Rohm tech inc (put: 20,000) by non-dispersive type, quantity mean molecule
Addition all is adjusted in embodiment and all comparative examples and makes the viscosity of compsn reach 9～11mm
2The amount of/s.
[E composition: inhibitor]
E-1: pentanoic
E-2: hindered phenol (octyl group-3-(3,5-two-tertiary butyl-4-phenylor) propionic ester)
E-3: zinc dialkyl dithiophosphate (alkyl: sec-C6)
[other additives]
Contain boracic succimide, sulphur and be extreme pressure agent, phosphorodithioic acid amine, organic amide, nonionic acvator gear oil compounding agent, ashless be the additive that dispersion agent, pour point depressant, skimmer combine, in embodiment and all comparative examples, be same composition and allotment amount.
< appraisal procedure >
[low-temperature fluidity]
According to ASTM D 2983, Bu Shi (BF) viscosity under measuring-40 ℃.
[shear stability]
According to CEC L-45-T-93, carry out 60 hours KRL shearing tests, the viscosity degradation rate under measuring 100 ℃.
[extreme pressure property]
According to JIS K 2519, carry out Tian Shisi ball rub(bing)test once with 750rpm, measure supporting capacity.
[erosion resistance]
According to JIS K 2513, under 121 ℃, 3 hours condition, carry out copper corrosion test.
[oxidation stability]
Oxidation permanence test according to regulation among the JIS K 2514 is the ISOT method, under 150 ℃, 48 hours condition, and the viscosity increment rate under measuring 100 ℃.
[table 1]
| (unit is quality %) | Embodiment 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 |
| A-1 MO | Remainder | Remainder | Remainder | Remainder | Remainder | Remainder | Remainder |
| B-1 phosphorous acid two lauryls (in the P amount) B-2 Tritolyl Phosphates (in the P amount) | 0.030 0.037 | 0.030 0.037 | 0.030 0.037 | 0.030 0.037 | 0.030 0.037 | 0.030 0.037 | 0.006 0.037 |
| C-1 benzotriazole cpd C-2 thiadiazole compound | 0.05 0.02 | 0.10 | 0.03 | 0.10 | 0.10 | 0.10 | 0.05 0.02 |
| The D-1 ethene-alpha-olefin | 3.5 | 3.5 | 3.5 | 3.5 | 3.5 | 3.5 | 3.5 |
| E-1 pentanoic e-2 hindered phenol E-3 zinc dialkyl dithiophosphate (in the Zn amount) | 0.08 | 0.08 | 0.08 | 0.50 0.08 | 0.50 0.08 | 0.25 0.25 0.08 | 0.08 |
| Other additives | 7.3 | 7.3 | 7.3 | 7.3 | 7.3 | 7.3 | 7.3 |
| Sulphur composition % | 1.38 | 1.37 | 1.38 | 1.37 | 1.37 | 1.37 | 1.39 |
| Sulphur composition/phosphorus composition | 6.1 | 6.1 | 6.2 | 6.1 | 6.1 | 6.1 | 6.9 |
| Viscosity degradation rate (100 ℃) % Ceng Tiansi ball rub(bing)test supporting capacity MPa copper corrosion test after brookfield viscosity (40 ℃) mPas KRL shears (121 ℃, 3h) ISOT viscosity increment rate (100 ℃) % | 72200 ?3.5 0.50 1b 0.7 | 73600 ?3.5 0.45 2e 4.6 | 72800 ?3.3 0.45 1b 19.6 | 75300 ?3.4 0.45 2c 21.5 | 75000 ?3.7 0.40 2c 22.0 | 74400 ?3.6 0.45 2c 4.2 | 71100 ?3.4 0.40 1a 21.3 |
[table 2]
| (unit is quality %) | Comparative example 7 | Comparative example 8 | Comparative example 9 | Comparative example 10 | Comparative example 11 | Comparative example 12 | Comparative example 13 |
| A-1 MO a-2 MO | Remainder | Remainder | Remainder | Remainder | Remainder | Remainder | Remainder |
| B-1 phosphorous acid two lauryls (in the P amount) B-2 Tritolyl Phosphates (in the P amount) | 0.006 0.037 | 0.006 0.037 | 0.006 0.037 | 0.030 0.037 | 0.030 0.037 | 0.030 0.037 | 0.030 0.037 |
| B-3 mixture of sulfides (in the S amount) b-4 phosphorodithioate (in the S amount) b-5 sulfuration arctic sperm oil (in the S amount) | 0.19 | 0.088 | 0.19 | 0.19 | 0.88 | ||
| C-1 benzotriazole cpd C-2 thiadiazole compound | 0.05 0.02 | 0.05 0.02 | 0.05 0.02 | 0.05 0.02 | 0.05 0.02 | 0.05 0.02 | 0.05 0.02 |
| D-1 ethene-alpha-olefin d-2 Rohm tech inc | 3.5 | 3.5 | 3.5 | 3.5 | 3.5 | 3.5 | 6.0 |
| E-3 zinc dialkyl dithiophosphate (in the Zn amount) | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 |
| Other additives | 7.3 | 7.3 | 7.3 | 7.3 | 7.3 | 7.3 | 7.3 |
| Sulphur composition % | 1.57 | 1.47 | 1.55 | 1.56 | 1.46 | 1.38 | 1.35 |
| Sulphur composition/phosphorus composition | 7.8 | 6.1 | 7.9 | 7.0 | 5.5 | 6.1 | 6.1 |
| Viscosity degradation rate (100 ℃) % Ceng Tiansi ball rub(bing)test supporting capacity MPa copper corrosion test after brookfield viscosity (40 ℃) mPasKRL shears (121 ℃, 3h) ISOT viscosity increment rate (100 ℃) % | ?78300 ?3.1 0.50 ?1a 19.6 | ?79800 ?3.3 0.50 ?1b 13.1 | ?176000 ?3.7 0.50 ?1a -0.9 | ?79000 ?3.2 0.55 ?1a 25.8 | ?80200 ?3.5 0.50 ?1b 22.2 | Can't measure 3.6 0.50 1b 3.4 | ?73000 ?6.2 0.50 ?1b 2.5 |
The result of embodiment can know that gear oil composition of the present invention has following performance: has low-temperature fluidity and shear stability concurrently with high level, and not only has the extreme pressure property of appropriateness, and also excellence of erosion resistance and oxidation stability.
On the other hand, have only at corrosion inhibitor under any one the situation (comparative example 1～5), a kind of poor-performing in erosion resistance or the oxidation-resistance or this two kinds of performances are all relatively poor.In addition, be the total amount of phosphorus of extreme pressure agent during less than 0.05 quality % (comparative example 6) when deriving from phosphorus, extreme pressure property and oxidation stability are relatively poor.In addition, when the sulphur composition in the gear oil composition integral body surpasses 1.4 quality % (comparative example 7～11), though extreme pressure property than more excellent, oxidation stability or low-temperature fluidity are relatively poor.
And when using the lower base oil of viscosity index (comparative example 12), low-temperature fluidity is relatively poor, and when normally used Rohm tech inc is used for viscosity index improver (comparative example 13), shear stability is relatively poor.
As stated; In base oil, the additive one or more are replaced to the gear oil composition of the integrant different with thing of the present invention; Perhaps addition is at specialized range gear oil composition in addition; Also have at a certain aspect of performance compsn more excellent than the present invention thing, but other performances are poor, hence one can see that: the good compsn of excellent performance that gear oil composition is required and balance has only thing of the present invention.
Claims (1)
1. gear oil composition; It is characterized in that: it is to make viscosity index more than or equal to containing in 110 the lubricant base (A): at least a phosphorus of from the group that phosphorous acid ester and SULPHOSUCCINIC ACID ESTER are formed, selecting of counting 0.05～0.5 quality % with the phosphoric quality is that the nitrogen of extreme pressure agent (B), 0.005～0.2 quality % is that the nitrogen sulphur of corrosion inhibitor (C-1), 0.005～0.2 quality % is the ethene-alpha-olefin copolymer as viscosity index improver (D) of corrosion inhibitor (C-2), 1～10 quality % and counts the zinc dialkyl dithiophosphate (E) of 0.02～0.2 quality % and form with the zinc element quality; And the sulphur composition is smaller or equal to 1.4 quality %, and above-mentioned nitrogen is not sulfur-bearing of corrosion inhibitor (C-1).
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| Application Number | Priority Date | Filing Date | Title |
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| JP2007-099580 | 2007-04-05 | ||
| JP2007099580A JP2008255239A (en) | 2007-04-05 | 2007-04-05 | Gear oil composition |
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| CN101280240B true CN101280240B (en) | 2012-12-12 |
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| JP (1) | JP2008255239A (en) |
| KR (1) | KR101410177B1 (en) |
| CN (1) | CN101280240B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5502356B2 (en) | 2009-03-27 | 2014-05-28 | 出光興産株式会社 | Gear oil composition |
| CN102115689B (en) * | 2010-12-09 | 2011-12-14 | 高碑店市中煤神海科技发展有限公司 | Mine-used flame retardant gear liquid and preparation method thereof |
| FR2984348B1 (en) | 2011-12-16 | 2015-02-27 | Total Raffinage Marketing | LUBRICATING COMPOSITIONS FOR TRANSMISSIONS |
| SG11201503993WA (en) * | 2012-12-03 | 2015-06-29 | Lubrizol Corp | Industrial gear oils imparting reduced gearbox operating temperatures |
| CN105018189A (en) * | 2014-04-30 | 2015-11-04 | 吉坤日矿日石能源株式会社 | Lubricating oil compound |
| WO2017170868A1 (en) * | 2016-03-30 | 2017-10-05 | 出光興産株式会社 | Rust preventive oil composition |
| CN107474912A (en) * | 2017-06-27 | 2017-12-15 | 山西潞安太行润滑油有限公司 | A kind of high viscous finger, the Industrial gear oil composition of wide temperature range and its application |
| JP7055990B2 (en) * | 2017-10-02 | 2022-04-19 | 出光興産株式会社 | Automotive gear oil composition and lubrication method |
| JP7089899B2 (en) * | 2018-02-23 | 2022-06-23 | 出光興産株式会社 | Lubricating oil composition, manufacturing method of lubricating oil composition and drive system equipment |
| US11732208B2 (en) | 2018-08-06 | 2023-08-22 | The Lubrizol Corporation | Composition and method for lubricating automotive gears, axles and bearings |
| WO2020184570A1 (en) * | 2019-03-14 | 2020-09-17 | 日油株式会社 | Lubricating oil additive, lubricating oil additive composition, and lubricating oil composition containing these |
| CN115537257B (en) * | 2022-08-03 | 2023-12-19 | 上海万生合金材料有限公司 | High-temperature-resistant wire drawing oil and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1371964A (en) * | 2001-02-20 | 2002-10-02 | 乙基公司 | Low phosphorus clenaing-gear oil preparation |
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| JP2555284B2 (en) | 1987-05-14 | 1996-11-20 | 出光興産株式会社 | Lubricant composition with improved temperature characteristics |
| KR100241281B1 (en) * | 1997-08-30 | 2000-02-01 | 정몽규 | Composition of automatic transmission fluid improved in friction property and durability |
| JP3973281B2 (en) * | 1997-12-25 | 2007-09-12 | コスモ石油株式会社 | Gear oil composition |
| US6482778B2 (en) * | 1999-08-11 | 2002-11-19 | Ethyl Corporation | Zinc and phosphorus containing transmission fluids having enhanced performance capabilities |
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| CN1371964A (en) * | 2001-02-20 | 2002-10-02 | 乙基公司 | Low phosphorus clenaing-gear oil preparation |
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| JP特开2003-183686A 2003.07.03 |
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| JP2008255239A (en) | 2008-10-23 |
| CN101280240A (en) | 2008-10-08 |
| KR20080091008A (en) | 2008-10-09 |
| KR101410177B1 (en) | 2014-06-19 |
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