EP0407977B1 - Schmierölzusammensetzung - Google Patents

Schmierölzusammensetzung Download PDF

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Publication number
EP0407977B1
EP0407977B1 EP90113167A EP90113167A EP0407977B1 EP 0407977 B1 EP0407977 B1 EP 0407977B1 EP 90113167 A EP90113167 A EP 90113167A EP 90113167 A EP90113167 A EP 90113167A EP 0407977 B1 EP0407977 B1 EP 0407977B1
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EP
European Patent Office
Prior art keywords
oil composition
zinc
lubricating oil
lubricating
carbon atoms
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP90113167A
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English (en)
French (fr)
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EP0407977A1 (de
Inventor
Hitoshi C/O Idemitsu Kosan Co. Ltd. Hata
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Idemitsu Kosan Co Ltd
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Idemitsu Kosan Co Ltd
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Publication of EP0407977A1 publication Critical patent/EP0407977A1/de
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
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    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
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    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
    • C10M107/04—Polyethene
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    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/04—Hydroxy compounds
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    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
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    • C10M137/04—Phosphate esters
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    • C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
    • C10M145/12—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
    • C10M145/14—Acrylate; Methacrylate
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    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
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    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
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    • C10M2203/02—Well-defined aliphatic compounds
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Definitions

  • the present invention relates to a lubricating oil composition which can be suitably used as hydraulic fluid, traction fluid, bearing oil, gear oil, engine oil, etc.
  • Zinc dithiophosphates have been widely used in lubricating oils having requirements for the function of improving wear resistance and load carrying capacity, thermostability, and oxidation stability.
  • thermostability and oxidation stability As a means of improving thermostability and oxidation stability, it is proposed in Japanese Patent Application Kokai Koho (Laid-open) No. 60-248796 to add zinc dithiophosphates into lubricating base oils together with other additives including nitrogen-containing copolymers, metallic detergent-dispersants, ashless detergent-dispersants, etc.
  • additives decrease load carrying capacity and wear resistance and cannot bring about sufficient increase in thermostability and oxidation stability, and therefore, the obtained lubricating oil cannot be prevented sufficiently from formation of sludge and coloration and discoloration.
  • EP-A-0 280 260 discloses a lubricating oil composition
  • a lubricating oil composition comprising (A) a mineral oil having a specific viscosity and viscosity index, (B) 0.5 to 20 % by weight of an ethylene-a-olefin copolymer having a specific number average molecular weight, (C) 0.05 to 20 % by weight of polymethacrylate having a specific number average molecular weight or a mixture of said polymethacrylate and an olefin copolymer, and either (D-I) 1 to 20 % by weight of a detergent-dispersant and/or an antioxidant, or (D-II) 0.5 to 20 % by weight of at least one member selected from the group consisting of an extreme pressure agent, an anti-wear agent and an oiliness agent.
  • zinc dithiophosphate As one suitable antioxidant, among others, zinc dithiophosphate, and as one suitable oiliness agent, among others, oleyl alcohol are disclosed. Zinc dithiophosphate is also mentioned, besides others, as extreme pressure agent.
  • the above lubricating oil composition is useful as a multi grade lubricating oil composition which is excellent in shear stability.
  • EP-A-0 291 006 discloses a lubricating oil composition containing (A) a base oil having a specific viscosity, pour point and viscosity index, (B) an ethylene- ⁇ -olefin copolymer having a specific number average molecular weight, and (C) at least one additive selected from an extreme pressure agent, an anti-wear agent, an oiliness agent and a detergent dispersant.
  • a base oil having a specific viscosity, pour point and viscosity index
  • B an ethylene- ⁇ -olefin copolymer having a specific number average molecular weight
  • C at least one additive selected from an extreme pressure agent, an anti-wear agent, an oiliness agent and a detergent dispersant.
  • oleyl alcohol is mentioned as being suited as oiliness agent.
  • zinc dithiophosphate is mentioned besides numerous other compounds as compound suited as extreme pressure agent, or as a further additive for preventing oxidation.
  • This oil composition exhibits a high viscosity index and good temperature characteristics, particularly at low temperatures and is further excellent in shear stability and other properties, such as wear resistance and detergency.
  • the present invention has been made under the above-described circumstances, and the object of the present invention is to provide a lubricating oil composition which has not only excellent effect in improving load carrying capacity and wear resistance but also excellent thermostability and oxidation stability whereby formation of sludge and coloration and discoloration are inhibited and heat degradation and oxidation degradation can be retarded.
  • a lubricating oil composition satisfying the above-described object is obtainable by blending unsaturated aliphatic alcohols of from 16 to 24 carbon atoms together with zinc dithiophosphates into lubricating base oils in a specific ratio, and on the basis of the finding, we have eventually completed the present invention.
  • the oxidation stability of the lubricating oil composition of the present invention can be further improved by adding detergent-dispersants. That is, the present invention also provides a lubricating oil composition, comprising:
  • the lubricating oil composition of the present invention can be suitably used as hydraulic fluid, traction fluid, bearing oil, gear oil, engine oil, etc. even in severe circumstances where exposure to high temperature is inevitable.
  • the component (A), i.e. the lubricating base oil to be used in the lubricating oil composition of the present invention may be any one generally used in lubricating oils and is not particularly limited. Generally, a mineral oil or a synthetic detail each having a kinematic viscosity of from 5 to 10,000 mm2 s (cSt) as measured at 40 °C may be used
  • the mineral oil is not particularly limited so far as it satisfies the above-described condition, and some examples include those obtained by refining lubricating oil fraction of petroleum by means of solvent refining, hydrorefining, clay treatment, or a combination thereof and highly aromatic fractions obtained by solvent refining of lubricating oils, or hydrogenation products of the highly aromatic fractions.
  • Some examples of the synthetic oil include alkyl-substituted aromatic compounds, poly- ⁇ -olefin oils, ester oils, diester oils, hindered ester oils, synthetic naphthene oils, polyglycol oils, and mixtures thereof.
  • zinc dithiophosphate examples include zinc dialkyldithiophosphates, such as zinc di-n-propyldithiophosphate, zinc diisopropyldithiophosphate, zinc di-n-butyldithiophosphate, zinc diisobutyldithiophosphate, zinc di-sec-butyldithiophosphate, zinc di-n-amyldithiophosphate, zinc diisoamyldithiophosphate, zinc di-n-hexyldithiophosphate, zinc di-sec-hexyldithiophosphate, zinc bis(2-ethylhexyl)dithiophosphate, and zinc didecyldithiophosphate, zinc diaryldithiophosphates, such as zinc diphenyldithiophosphate, and zinc bis(alkylaryl)dithiophosphates, such as zinc bis(octylphenyl)dithiophosphate
  • the above-described component (B) i.e. the zinc dithiophosphate is present in the lubricating oil composition of the present invention at a concentration of from 0.05 to 5.0 % by weight, preferably from 0.1 to 3.0 % by weight. If the percentage of the component (B) is less than 0.05 % by weight of the lubricating oil composition, the effect of improving wear resistance and load carrying capacity will be small. On the other hand, even if the percentage of the component (B) exceeds 5.0 % by weight of the lubricating oil composition, larger effect cannot be expected.
  • the unsaturated aliphatic alcohol of from 16 to 24 carbon atoms which is to be used as the component (C) in the lubricating oil composition of the present invention may be any alcohol having the above-described number of carbon atoms and at least one double bond in each molecule.
  • the preferred are alcohols having an iodine number of about not less than 50.
  • Some examples of the preferred unsaturated aliphatic alcohols include cis-11-hexadecene-1-ol (C16H32O), cis-9-octadecene-1-ol (oleyl alcohol, C18H36O), 3,7,11,15-tetramethyl-2-hexadecene-1-ol (C20H40O), 9-eicosene-1-ol (C20H40O), 11-docosene-1-ol (C22H44O), 13-docosene-1-ol (C22H44O), 12-tetracosene-1-ol (C24H48O), and 13-tetracosene-1-ol (C24H48O).
  • the particularly preferred examples include 11-docosene-1-ol, 13-docosene-1-ol, 9-eicosene-1-ol, and cis-9-octadecene-1-ol (oleyl alcohol).
  • the detergent-dispersant to be used in the present invention may be any known detergent-dispersant, and some examples include metallic detergent-dispersants such as petroleum sulfonates, phosphonates, and phenates, and ashless detergent-dispersants, such as succinic acid derivatives and amine-type detergent-dispersants. Some typical examples of the detergent-dispersants which may be suitably used are Ca sulfonate and Ca phenate.
  • the component (D), i.e. the detergent-dispersant is present in the lubricating oil composition of the present invention at a concentration of from 0.01 to 5.0 % by weight, preferably from 0.1 to 1.5 % by weight, more preferably from 0.2 to 1.0 % by weight.
  • the above-described lubricating oil composition of the present invention comprising the lubricating base oil (A), component (B), and component (C) or the lubricating base oil (A), component (B) component (C) and component (D) may further contain a relatively small amount of at least one additive compound (component E) selected from the group consisting of phosphoric esters, phosphorous esters, amine salts of phosphoric esters, and amine salts of phosphorous esters.
  • component E additive compound selected from the group consisting of phosphoric esters, phosphorous esters, amine salts of phosphoric esters, and amine salts of phosphorous esters.
  • phosphoric esters and the phosphorous esters which may be suitably used are the compounds represented by the following general formulas (II) and (III) respectively: wherein each of R5, R6, R7, R8, R9, and R10 is, for example, independently a hydrogen atom, an alkyl group of from 4 to 30 carbon atoms, an aryl group of from 6 to 30 carbon atoms, or an alkylaryl group of from 7 to 30 carbon atoms, and two or more of them may be identical with each other or they may be different from each other.
  • phosphoric esters and the phosphorous esters include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris(isopropylphenyl)phosphate, butyl acid phosphate, 2-ethylhexyl acid phosphate, lauryl acid phosphate, oleyl acid phosphate, stearyl acid phosphate, dibutyl hydrogen phosphite, dioctyl hydrogen phosphite, dioleyl hydrogen phosphite, and distearyl hydrogen phosphite.
  • amine salts of phosphoric esters and the amine esters of phosphorous esters include lauryl amine salt, oleyl amine salt, coconut amine salt, and beef tallow amine salt
  • the component (E), i.e. the additive compound is present in the lubricating oil composition of the present invention at a concentration of from 0.01 to 5.0 % by weight, preferably from 0.1 to 1.5 % by weight, more preferably from 0.2 to 1.0 % by weight. Addition of the component (E) improves wear resistance still more.
  • Table 1 shows the composition and the test results of the lubricating oil compositions of the Examples and Comparative Examples.
  • Evaluation of the coloration and discoloration (1) was carried out by removing the sample used every 24 hour to observe the color of the sample (ASTM JIS K 2580) and is shown as the time (h) required of the color to exceed the ASTM color grade 4. Evaluation of the property of inhibiting formation of sludge was carried out by observing the above-described sample and was shown as the time (h) required of the deposition of separated material to be observed.
  • Oxidation stability was examined according to JIS K 2514, paragraph 3.1, Method of Testing the Oxidation Stability of Lubricating Oils for Internal Combustion Engines (so called ISOT).
  • Example 2 and Comparative Example 1 were @165.5 °C ⁇ 24 h, and the condition for the sample from Example 12 was @150 °C ⁇ 96 h.
  • Table 1 shows that the addition of the component (C) such as 13-docosene-1-ol and oleyl alcohol, i.e., in particular, unsaturated aliphatic alcohols of from 18 to 22 carbon atoms improved thermostability and oxidation stability, and particularly, the properties of inhibiting coloration, discoloration, and formation of sludge were remarkably improved.
  • the compounds other than the components of the present invention could not produce the directed effects.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Claims (11)

  1. Schmierölzusammensetzung, enthaltend
    (A) einen Hauptanteil mindestens eines Grundschmieröls,
    (B) 0,05 bis 5 Gew.-% mindestens eines Zinkdithiophosphats einer Struktur, die durch die folgende allgemeine Formel (1) dargestellt ist
    Figure imgb0015
     in der jeder der Reste R¹, R², R³ und R⁴ unabhängig eine primäre Alkylgruppe mit 2 bis 30 Kohlenstoffatomen, eine sekundäre Alkylgruppe mit 3 bis 30 Kohlenstoffatomen, eine Cycloalkylgruppe mit 6 bis 30 Kohlenstoffatomen, eine Arylgruppe mit 6 bis 14 Kohlenstoffatomen oder eine Alkylarylgruppe mit 7 bis 30 Kohlenstoffatomen bedeutet, und
    (C) 0,01 bis 10 Gew.-% mindestens eines ungesättigten aliphatischen Alkohols mit 16 bis 24 Kohlenstoffatomen, wobei das Gewichtsverhältnis des ungesättigten aliphatischen Alkohols zu dem Zinkdithiophosphat (C)/(B) 0,1 bis 10 beträgt.
  2. Schmierölzusammensetzung gemäß Anspruch 1, die zusätzlich
    (D) 0,01 bis 5,0 Gew.-% mindestens eines Detergens-Dispergiermittels enthält.
  3. Schmierölzusammensetzung gemäß Anspruch 1 oder 2, worin das Grundschmieröl ein Mineralöl mit einer kinematischen Viskosität von 5 bis 10 000 mm²/s (cSt), gemessen bei 40°C, oder ein synthetisches Öl mit einer kinematischen Viskosität von 5 bis 10 000 mm²/s (cSt), gemessen bei 40°C, ist.
  4. Schmierölzusammensetzung gemäß einem der Ansprüche 1 bis 3, in der das Zinkdithiophosphat aus der aus Zink-di-primären (C₃-C₁₂)-alkyldithiophosphaten, Zink-di-sekundären (C₃-C₁₂)-alkyldithiophosphaten und Zink-bis-(C₉-C₂₄)-(alkyl-aryl)-dithiophosphaten bestehenden Gruppe ausgewählt ist.
  5. Schmierölzusammensetzung gemäß einem der Ansprüche 1 bis 4, in der der ungesättigte aliphatische Alkohol 11-Docosen -1-ol, 13-Docosen-1-ol, 9-Eicosen-1-ol oder cis-9-Octadecen -1-ol ist.
  6. Schmierölzusammensetzung gemäß Anspruch 1 oder 5, in der der ungesättigte aliphatische Alkohol 13-Docosen-1-ol oder cis-9-Octadecen-1-ol ist.
  7. Schmierölzusammensetzung gemäß Anspruch 1, in der das Grundschmieröl ein Mineralöl ist, das Zinkdithiophosphat ein Gemisch aus Zink-di-prinmären (C₄-C₈)-alkyldithiophospaten ist und der ungesättigte aliphatische Alkohol cis-9-Octadecen -1-ol ist.
  8. Schmierölzusammensetzung gemäß einem der Ansprüche 1 bis 7, die zusätzlich (E) 0,01 bis 5,0 Gew.-% mindestens eines Additivs enthält, das aus der aus Phosphorsäureestern, Phosphorigsäureestern, Aminsalzen von Phosphorsäureestern und Aminsalzen von Phosphorigsäureestern bestehenden Gruppe ausgewählt ist.
  9. Schmierölzusammensetzung gemäß Anspruch 2, in der der ungesättigte aliphatische Alkohol 13-Docosen-1-ol ist.
  10. Schmierölzusammensetzung gemäß Anspruch 2, in der das Grundschmieröl ein Mineralöl ist, das Zinkdithiophosphat ein Gemisch aus Zink-di-primären-(C₄-C₆)-alkyldithiophosphaten ist, der ungesättigte aliphatische Alkohol 13-Docosen-1-ol ist und das Detergens-Dispergiermittel ein Gemisch aus Calciumsulfonat und Calciumphenat ist.
  11. Schmierölzusammensetzung gemäß Anspruch 2, in der das Grundschmieröl ein Mineralöl ist, das Zinkdithiophosphat ein Gemisch aus Zink-di-primären-(C₄-C₆)-alkyldithiophosphaten ist, der ungesättigte aliphatische Alkohol 13-Docosen-1 -ol ist, das Detergens-Dispergiermittel ein Gemisch aus Calciumsulfonat und Calciumphenat ist und das Additiv Tricresylphosphat ist.
EP90113167A 1989-07-13 1990-07-10 Schmierölzusammensetzung Expired - Lifetime EP0407977B1 (de)

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JPH07109477A (ja) * 1993-10-15 1995-04-25 Oronaito Japan Kk 農業機械もしくは建設機械用の共通潤滑作動油
JP2000001685A (ja) * 1998-06-18 2000-01-07 Cosmo Sogo Kenkyusho:Kk エンジン油組成物
JP4524007B2 (ja) * 1999-06-29 2010-08-11 協同油脂株式会社 等速ジョイント用グリース組成物
US8206035B2 (en) 2003-08-06 2012-06-26 Nissan Motor Co., Ltd. Low-friction sliding mechanism, low-friction agent composition and method of friction reduction
JP4973971B2 (ja) 2003-08-08 2012-07-11 日産自動車株式会社 摺動部材
JP2005054617A (ja) * 2003-08-08 2005-03-03 Nissan Motor Co Ltd 動弁機構
EP1508611B1 (de) 2003-08-22 2019-04-17 Nissan Motor Co., Ltd. Getriebe enthaltend eine getriebeölzusammensetzung
JP7400806B2 (ja) * 2019-03-14 2023-12-19 日油株式会社 潤滑油用添加剤、潤滑油用添加剤組成物およびこれらを含有する潤滑油組成物

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US2418894A (en) * 1944-12-09 1947-04-15 Standard Oil Dev Co Compounded lubricating oil
US2945810A (en) * 1956-12-31 1960-07-19 California Research Corp Lubricating oil compositions containing bi-metal dithiophosphates
GB1287405A (en) * 1968-11-13 1972-08-31 Shell Int Research Non-aqueous lubricant compositions
JPS5140567B2 (de) * 1972-06-21 1976-11-04
JPS59122597A (ja) * 1982-11-30 1984-07-16 Honda Motor Co Ltd 潤滑油組成物
US4634541A (en) * 1985-01-28 1987-01-06 Standard Oil Company Color stabilizers for zinc dithiophosphates
US4776967A (en) * 1987-02-27 1988-10-11 Idemitsu Kosan Company Limited Lubricating oil composition
JP2599383B2 (ja) * 1987-04-11 1997-04-09 出光興産 株式会社 潤滑油組成物
JP2555284B2 (ja) * 1987-05-14 1996-11-20 出光興産株式会社 温度特性改良潤滑油組成物

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JP2795911B2 (ja) 1998-09-10
KR910003081A (ko) 1991-02-26
KR930010530B1 (ko) 1993-10-25
DE69001462D1 (de) 1993-06-03
JPH0345697A (ja) 1991-02-27
DE69001462T2 (de) 1993-11-04

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