DE69001462T2 - LUBRICATING OIL COMPOSITION. - Google Patents

LUBRICATING OIL COMPOSITION.

Info

Publication number
DE69001462T2
DE69001462T2 DE90113167T DE69001462T DE69001462T2 DE 69001462 T2 DE69001462 T2 DE 69001462T2 DE 90113167 T DE90113167 T DE 90113167T DE 69001462 T DE69001462 T DE 69001462T DE 69001462 T2 DE69001462 T2 DE 69001462T2
Authority
DE
Germany
Prior art keywords
lubricating oil
zinc
oil composition
composition according
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 - Fee Related
Application number
DE90113167T
Other languages
German (de)
Other versions
DE69001462D1 (en
Inventor
Hitoshi Hata
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Idemitsu Kosan Co Ltd
Original Assignee
Idemitsu Kosan Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Idemitsu Kosan Co Ltd filed Critical Idemitsu Kosan Co Ltd
Application granted granted Critical
Publication of DE69001462D1 publication Critical patent/DE69001462D1/en
Publication of DE69001462T2 publication Critical patent/DE69001462T2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • C10M129/04—Hydroxy compounds
    • C10M129/06—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • 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
    • 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
    • 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
    • C10M137/08—Ammonium or amine salts
    • 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
    • C10M137/10—Thio derivatives
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M141/10—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 at least one of them being an organic phosphorus-containing compound
    • 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
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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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    • C10M155/00—Lubricating compositions characterised by the additive being a macromolecular compound containing atoms of elements not provided for in groups C10M143/00 - C10M153/00
    • C10M155/02—Monomer containing silicon
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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
    • C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
    • C—CHEMISTRY; METALLURGY
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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
    • C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
    • C—CHEMISTRY; METALLURGY
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    • C10M167/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound, a non-macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/02—Well-defined aliphatic compounds
    • C—CHEMISTRY; METALLURGY
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    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/02—Well-defined aliphatic compounds
    • C10M2203/022—Well-defined aliphatic compounds saturated
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    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/02—Well-defined aliphatic compounds
    • C10M2203/024—Well-defined aliphatic compounds unsaturated
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    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/04—Well-defined cycloaliphatic compounds
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    • 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
    • C10M2205/022—Ethene
    • C10M2205/0225—Ethene used as base material
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    • C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
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    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased salts thereof
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    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
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    • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
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    • C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
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    • C10M2207/286—Esters of polymerised unsaturated acids
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    • C10M2207/289—Partial esters containing free hydroxy groups
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    • C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
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    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/089—Overbased salts
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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)

Description

(a) Gebiet der Erfindung(a) Field of the invention

Die vorliegende Erfindung betrifft eine Schmierölzusammensetzung, die sich für die Verwendung als Hydraulikflüssigkeit, Reibgetriebeöl, Lageröl, Getriebeöl, Maschinenöl usw. eignet.The present invention relates to a lubricating oil composition suitable for use as a hydraulic fluid, friction gear oil, bearing oil, gear oil, machine oil, etc.

(b) Beschreibung der verwandten Technik(b) Description of the related art

Zinkdithiophosphate werden in Schmierölen, an die Anforderungen in Richtung auf die Verbesserung der Verschleißfestigkeit und der Belastbarkeit, der Thermostabilität und der Oxidationsstabilität gestellt werden, in großem Umfang verwendet.Zinc dithiophosphates are widely used in lubricating oils where requirements are placed on improving wear resistance and resilience, thermal stability and oxidation stability.

Da sich in neuerer Zeit die Beanspruchungsbedingungen dieser Schmieröle verschärft haben, hat die Nachfrage insbesondere nach Schmierölen mit einer derart hohen Thermostabilität und Oxidationsstabilität, daß sie der Verwendung bei hoher Temperatur standhalten, zugenommen.Since the stress conditions of these lubricating oils have become more severe in recent times, the demand has increased, particularly for lubricating oils with such high thermal stability and oxidation stability that they can withstand use at high temperatures.

Als Maßnahme zur Verbesserung der Thermostabilität und der Oxidationsstabilität ist in der japanischen Patentanmeldung Kokai Koho (offengelegt) No. 60-248796 vorgeschlagen worden, Grundschmierölen Zinkdithiophosphate zusammen mit anderen Additiven, einschließlich stickstoffhaltigen Copolymeren, metallhaltigen Detergens-Dispergiermitteln, aschefreien Detergens- Dispergiermitteln usw., zuzusetzen. Solche Additive setzen jedoch die Belastbarkeit und die Verschleißfestigkeit herab und erbringen nicht die ausreichende Erhöhung der Thermostabilität und der Oxidationsstabilität, und deshalb können bei dem erhaltenen Schmieröl die Ausbildung von Schlamm und die Anfärbung und Entfärbung nicht verhindert werden.As a measure for improving thermal stability and oxidation stability, it has been proposed in Japanese Patent Application Kokai Koho (Laid-Open) No. 60-248796 to add zinc dithiophosphates to lubricating base oils together with other additives including nitrogen-containing copolymers, metal-containing detergent dispersants, ashless detergent dispersants, etc. However, such additives reduce the load-bearing capacity and wear resistance and do not bring about a sufficient increase in thermal stability and oxidation stability, and therefore the resulting lubricating oil cannot be prevented from forming sludge and from coloring and discoloration.

EP-A-0 280 260 offenbart eine Schmierölzusammensetzung, enthaltend (A) ein Mineralöl mit einer spezifischen Viskosität und einem spezifischen Viskositätsindex, (B) 0,5 bis 20 Gew.-% eines Ethylen-α-Olefin-Copolymeren init einem spezifischen Molekulargewichts-Zahlenmittel, (C) 0,05 bis 20 Gew.-% Polymethacrylat mit einem spezifischen Molekulargewichts-Zahlenmittel oder ein Gemisch aus dem Polymethacrylat und einem Olefincopolymer, und entweder (D-I) 1 bis 20 Gew.-% eines Detergens- Dispergiermittels und/oder eines Antioxidationsmittels, oder (D-II) 0,5 bis 20 Gew.-% mindestens eines Mitglieds, ausgewählt aus der aus einem Hochdruckmittel, einem Antiverschleißmittel und einem Schmierfähigkeitsmittel bestehenden Gruppe. Als geeignetes Antioxidationsmittel ist unter anderen Zinkdithiophosphat und als geeignetes Schmierfähigkeitsmittel unter anderen Oleylalkohol offenbart. Zinkdithiophospht ist neben anderen auch als Hochdruckmittel erwähnt. Die obige Schmierölzusammensetzung ist als Mehrbereichs-Schmierölzusammensetzung, die eine ausgezeichnete Scherfestigkeit aufweist, verwendbar.EP-A-0 280 260 discloses a lubricating oil composition containing (A) a mineral oil having a specific viscosity and viscosity index, (B) 0.5 to 20 wt% of an ethylene-α-olefin copolymer having a specific number average molecular weight, (C) 0.05 to 20 wt% of a polymethacrylate having a specific number average molecular weight or a mixture of the polymethacrylate and an olefin copolymer, and either (D-I) 1 to 20 wt% of a detergent-dispersant and/or an antioxidant, or (D-II) 0.5 to 20 wt% of at least one member selected from the group consisting of an extreme pressure agent, an antiwear agent and a lubricity agent. Zinc dithiophosphate is disclosed as a suitable antioxidant, among others, and oleyl alcohol is disclosed as a suitable lubricity agent, among others. Zinc dithiophosphate is also mentioned as an extreme pressure agent, among others. The above lubricating oil composition is usable as a multigrade lubricating oil composition having excellent shear strength.

EP-A-0 291 006 offenbart eine Schmierölzusammensetzung, enthaltend (A) ein Grundöl mit spezifischer Viskosität, spezifischem Stockpunkt und spezifischem Viskositätsindex, (B) ein Ethylen- α-Olefin-Copolymer mit spezifischem Molekulargewichts-Zahlenmittel und (C) mindestens ein Additiv, ausgewählt unter einem Hochdruckmittel, einem Antiverschleißmittel, einem Schmierfähigkeitsmittel und einem Detergens-Dispergiermittel. Unter anderen geeigneten Verbindungen ist Oleylalkohol als geeignetes Schmierfähigkeitsmittel erwähnt. Außerdem ist Zinkdithiophosphat neben zahlreichen anderen Verbindungen als geeignetes Hochdruckmittel oder als weiteres Additiv für die Oxidationsverhinderung erwähnt.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-α-olefin copolymer having a specific number average molecular weight and (C) at least one additive selected from an extreme pressure agent, an antiwear agent, a lubricity agent and a detergent-dispersant. Among other suitable compounds, oleyl alcohol is mentioned as a suitable lubricity agent. Furthermore, zinc dithiophosphate is mentioned as a suitable extreme pressure agent or as another additive for oxidation prevention, among numerous other compounds.

Diese Ölzusammensetzung weist einen hohen Viskositätsindex und gute Temperatureigenschaften, insbesondere bei niedrigen Temperaturen, auf und ist außerdem ausgezeichnet bezüglich Scherfestigkeit und anderen Eigenschaften, wie Verschleißfestigkeit und Detergiereigenschaften.This oil composition has a high viscosity index and good temperature properties, especially at low temperatures, and is also excellent in terms of shear strength and other properties such as wear resistance and detergent properties.

Die vorliegende Erfindung kam aufgrund der vorstehend erläuterten Umstände zustande, und somit ist es Aufgabe der vorliegenden Erfindung, eine Schmierölzusammensetzung anzugeben, die nicht nur eine ausgezeichnete Wirkung hinsichtlich der Verbesserung der Belastbarkeit und der Verschleißfestigkeit hat, sondern auch eine ausgezeichnete Thermostabilität und Oxidationsstabilität aufweist, wodurch die Bildung von Schlamm und die Anfärbung und Entfärbung unterdrückt und Wärme- und Oxidationsabbau verzögert werden können.The present invention has been accomplished due to the above-mentioned circumstances, and thus an object of the present invention is to provide a lubricating oil composition which not only has an excellent effect of improving the load-bearing capacity and wear resistance, but also has excellent thermal stability and oxidation stability, whereby the formation of sludge and the coloring and discoloration can be suppressed and heat and oxidation degradation can be delayed.

Zur Lösung der obigen Probleme wurden sorgfältige Untersuchungen durchgeführt, wobei gefunden wurde, daß eine Schmierölzusammensetzung, die den vorstehend beschriebenen Anforderungen genügt, durch Einmischen von ungesättigten aliphatischen Alkoholen zusammen mit 16 bis 24 Kohlenstoffatomen mit Zinkdithiophosphaten in Grundschmieröle in einem spezifischen Verhältnis erhältlich ist, und auf der Grundlage dieser Erkenntnis wurde die vorliegende Erfindung konzipiert.In order to solve the above problems, careful studies were conducted and it was found that a lubricating oil composition satisfying the above-described requirements was obtainable by mixing unsaturated aliphatic alcohols together with 16 to 24 carbon atoms with zinc dithiophosphates into base lubricating oils at a specific ratio, and on the basis of this finding, the present invention was conceived.

Dies bedeutet, daß sich die vorliegende Erfindung auf eine Schmierölzusammensetzung bezieht, enthaltend:This means that the present invention relates to a lubricating oil composition containing:

(A) einen Hauptanteil mindestens eines Grundschmieröls,(A) a major proportion of at least one base lubricating oil,

(B) 0,05 bis 5 Gew.-% mindestens eines Zinkdithiophosphats einer Struktur, die durch die folgende allgemeine Formel (1) dargestellt ist (B) 0.05 to 5 wt.% of at least one zinc dithiophosphate having a structure represented by the following general formula (1)

in der jeder der Reste R¹, R², R³ und R&sup4; 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, undin which each of R¹, R², R³ and R⁴ independently represents a primary alkyl group having 2 to 30 carbon atoms, a secondary alkyl group having 3 to 30 carbon atoms, a cycloalkyl group having 6 to 30 carbon atoms, an aryl group having 6 to 14 carbon atoms or an alkylaryl group having 7 to 30 carbon atoms, and

(C) 0,01 bis 10 Gew.-% mindestens eines ungesättigten aliphatischen Alkohols mit 16 bis 24 Kohlenstoffatomen,(C) 0.01 to 10% by weight of at least one unsaturated aliphatic alcohol having 16 to 24 carbon atoms,

wobei das Gewichtsverhältnis des ungesättigten aliphatischen Alkohols zu dem Zinkdithiophosphat (C)/(B) 0,1 bis 10 beträgt.wherein the weight ratio of the unsaturated aliphatic alcohol to the zinc dithiophosphate (C)/(B) is 0.1 to 10.

Die Oxidationsstabilität der Schmierölzusammensetzung nach der vorliegenden Erfindung kann durch Zusatz von Detergens-Dispergiermitteln weiter verbessert werden. Dies bedeutet, daß die vorliegende Erfindung auch eine Schmierölzusammensetzung betrifft, enthaltend:The oxidation stability of the lubricating oil composition according to the present invention can be further improved by adding detergent dispersants. This means that the present invention also relates to a lubricating oil composition containing:

(A) einen Hauptanteil mindestens eines Grundschmieröls,(A) a major proportion of at least one base lubricating oil,

(B) 0,05 bis 5 Gew.-% mindestens eines Zinkdithiophosphats einer Struktur, die durch die folgende allgemeine Formel (1) dargestellt ist (B) 0.05 to 5 wt.% of at least one zinc dithiophosphate having a structure represented by the following general formula (1)

in der jeder der Reste R¹, R², R³ und R&sup4; die vorstehend angegebene Bedeutung hat,in which each of the radicals R¹, R², R³ and R⁴ has the meaning given above,

(C) 0,01 bis 10 Gew.-% mindestens eines ungesättigten aliphatischen Alkohols mit 16 bis 24 Kohlenstoffatomen und(C) 0.01 to 10% by weight of at least one unsaturated aliphatic alcohol having 16 to 24 carbon atoms and

(D) 0,01 bis 5 Gew.-% mindestens eines Detergens-Dispergiermittels,(D) 0.01 to 5% by weight of at least one detergent-dispersant,

wobei das Gewichtsverhältnis des ungesättigten aliphatischen Alkohols zu Zinkdithiophosphat (C)/(B) 0,1 bis 10 beträgt.wherein the weight ratio of the unsaturated aliphatic alcohol to zinc dithiophosphate (C)/(B) is 0.1 to 10.

Die Schmierölzusammensetzung nach der vorliegenden Erfindung kann vorteilhaft als Hydraulikflüssigkeit, Reibgetriebeflüssigkeit, Lageröl, Getriebeöl, Maschinenöl usw. selbst unter verschärften Bedingungen verwendet werden, bei denen die Einwirkung von hohen Temperaturen unvermeidlich ist.The lubricating oil composition according to the present invention can be advantageously used as a hydraulic fluid, friction gear fluid, bearing oil, gear oil, machine oil, etc. even under severe conditions where exposure to high temperatures is unavoidable.

Die Komponente (A), d.h. das bei der Schmierölzusammensetzung nach der vorliegenden Erfindung zu verwendende Grundschmieröl, kann von der Art sein, wie sie im allgemeinen bei Schmierölen eingesetzt wird, und ist nicht besonders eingeschränkt. Im allgemeinen kann ein Mineralöl oder ein synthetisches Öl mit jeweils einer kinematischen Viskosität von 5 bis 10 000 mm²/s (cSt), gemessen bei 40ºC, verwendet werden.The component (A), i.e., the lubricating base oil to be used in the lubricating oil composition of the present invention, may be of the type generally used in lubricating oils and is not particularly limited. In general, a mineral oil or a synthetic oil each having a kinematic viscosity of 5 to 10,000 mm²/s (cSt) measured at 40°C may be used.

Für die Mineralöle bestehen keine besonderen Einschränkungen, so lange sie den vorstehend genannten Bedingungen genügen, und einige Beispiele umfassen die, die durch Raffination der Schmierölfraktion von Erdöl mittels der Solventraffination, der Hydroraffination, der Bleicherdebehandlung oder einer Kombination daraus erhalten werden, und hocharomatische Fraktionen, die durch Solventraffination von Schmierölen erhalten werden, oder die Hydrierungsprodukte von hocharomatischen Fraktionen. Einige Beispiele für synthetische Öle umfassen alkylsubstituierte aromatische Verbindungen, Poly-α-olefin-Öle, Esteröle, Diesteröle, gehinderte Esteröle, synthetische Naphthenöle, Polyglykolöle und Gemische aus diesen.There are no particular restrictions on the mineral oils, as long as they satisfy the above conditions, and some examples include those obtained by refining the lubricating oil fraction of petroleum by means of solvent refining, hydrorefining, bleaching earth treatment or a combination thereof, and highly aromatic fractions obtained by solvent refining of lubricating oils, or the hydrogenation products of highly aromatic fractions. Some examples of synthetic oils include alkyl-substituted aromatic compounds, poly-α-olefin oils, ester oils, diester oils, hindered ester oils, synthetic naphthenic oils, polyglycol oils and mixtures of these.

Das als Komponente (B) in der Schmierölzusammensetzung nach der vorliegenden Erfindung zu verwendende Zinkdithiophosphat (ZnDTP) ist eine Verbindung, die durch die folgende allgemeine Formel (1) dargestellt ist The zinc dithiophosphate (ZnDTP) to be used as component (B) in the lubricating oil composition according to the present invention is a compound represented by the following general formula (1)

in der jeder der Reste R¹, R², R³ und R&sup4; unabhängig eine primäre Alkylgruppe mit 2 bis 30 Kohlenstoffatomen, vorzugsweise 3 bis 12 Kohlenstoffatomen, eine sekundäre Alkylgruppe mit 3 bis 30 Kohlenstoffatomen, vorzugsweise 3 bis 12 Kohlenstoffatomen, eine Cycloalkylgruppe mit 6 bis 30 Kohlenstoffatomen, eine Arylgruppe mit 6 bis 14 Kohlenstoffatomen oder eine Alkylarylgruppe mit 7 bis 30 Kohlenstoffatomen, vorzugsweise 9 bis 24 Kohlenstoffatomen, bedeutet.in which each of R¹, R², R³ and R⁴ independently represents a primary alkyl group having 2 to 30 carbon atoms, preferably 3 to 12 carbon atoms, a secondary alkyl group having 3 to 30 carbon atoms, preferably 3 to 12 carbon atoms, a cycloalkyl group having 6 to 30 carbon atoms, an aryl group having 6 to 14 carbon atoms or an alkylaryl group having 7 to 30 carbon atoms, preferably 9 to 24 carbon atoms.

Einige Beispiele für Zinkdithiophosphate umfassen Zinkdialkyldithiophosphate, wieSome examples of zinc dithiophosphates include zinc dialkyldithiophosphates, such as

Zink-di-n-propyldithiophosphat,Zinc di-n-propyldithiophosphate,

Zink-diisopropyldithiophosphat,Zinc diisopropyldithiophosphate,

Zink-di-n-butyldithiophosphat,Zinc di-n-butyldithiophosphate,

Zink-diisobutyldithiophosphat,Zinc diisobutyldithiophosphate,

Zink-di-sec.-butyldithiophosphat,Zinc di-sec.-butyldithiophosphate,

Zink-di-n-amyldithiophosphat,Zinc di-n-amyldithiophosphate,

Zink-diisoamyldithiophosphat,Zinc diisoamyldithiophosphate,

Zink-di-n-hexyldithiophosphat,Zinc di-n-hexyldithiophosphate,

Zink-di-sec.-hexyldithiophosphat,Zinc di-sec.-hexyldithiophosphate,

Zink-bis(2-ethylhexyl)-dithiophosphat undZinc bis(2-ethylhexyl) dithiophosphate and

Zink-didecyldithiophosphat,Zinc didecyldithiophosphate,

Zink-diaryldithiophosphate, wieZinc diaryldithiophosphates, such as

Zink-diphenyldithiophosphat, undZinc diphenyldithiophosphate, and

Zink-bis(alkylaryl)-dithiophosphate, wieZinc bis(alkylaryl) dithiophosphates, such as

Zink-bis(octylphenyl)-dithiophosphate,Zinc bis(octylphenyl)dithiophosphate,

Zink-bis(nonylphenyl)-dithiophosphate undZinc bis(nonylphenyl) dithiophosphates and

Zink-bis(dodecylphenyl)-dithiophosphate.Zinc bis(dodecylphenyl)dithiophosphate.

Die vorstehend genannte Komponente (B), d.h. das Zinkdithiophosphat, ist in der Schmierölzusammensetzung nach der vorliegenden Erfindung in einer Konzentration von 0,05 bis 5,0 Gew.- %, vorzugsweise von 0,1 bis 3,0 Gew.-%, anwesend. Wenn der Prozentsatz an Komponente (B) in der Schmierölzusammensetzung kleiner ist als 0,05 Gew.-%, ist der Effekt der Verbesserung der Verschleißfestigkeit und der Belastbarkeit gering. Selbst wenn andererseits der Prozentsatz an Komponente (B) in der Schmierölzusammensetzung 5,0 Gew.-% überschreitet, kann kein größerer Effekt mehr erwartet werden.The above-mentioned component (B), ie the zinc dithiophosphate, is present in the lubricating oil composition according to the present invention in a concentration of from 0.05 to 5.0% by weight, preferably from 0.1 to 3.0% by weight. When the percentage of component (B) in the lubricating oil composition is less than 0.05 wt.%, the effect of improving wear resistance and load capacity is small. On the other hand, even if the percentage of component (B) in the lubricating oil composition exceeds 5.0 wt.%, no greater effect can be expected.

Der ungesättigte aliphatische Alkohol mit 16 bis 24 Kohlenstoffatomen, der in der Schmierölzusammensetzung nach der vorliegenden Erfindung als Komponente (C) verwendet wird, kann jeder beliebige Alkohol mit der vorstehend genannten Anzahl von Kohlenstoffatomen und mindestens einer Doppelbindung je Molekül sein. Bevorzugt sind Alkohole mit einer Iodzahl von nicht weniger als etwa 50. Einige Beispiele für bevorzugte ungesättigte aliphatische Alkohole umfassen cis-11-Hexadecen-1-ol (C&sub1;&sub6;H&sub3;&sub2;O), cis-9-Octadecen-1-ol (Oleylalkohol, C&sub1;&sub8;H&sub3;&sub6;O), 3,7,11,15-Tetramethyl-2-hexadecen-1-ol (C&sub2;&sub0;H&sub4;&sub0;O), 9-Eicosen-1-ol (C&sub2;&sub0;H&sub4;&sub0;O), 11-Docosen-1-ol (C&sub2;&sub2;H&sub4;&sub4;O), 13-Docosen-1-ol (C&sub2;&sub2;H&sub4;&sub4;O), 12-Tetracosen-1-ol (C&sub2;&sub4;H&sub4;&sub8;O) und 13-Tetracosen-1-ol (C&sub2;&sub4;H&sub4;&sub8;O).The unsaturated aliphatic alcohol having 16 to 24 carbon atoms used as component (C) in the lubricating oil composition of the present invention may be any alcohol having the above-mentioned number of carbon atoms and at least one double bond per molecule. Preferred are alcohols having an iodine value of not less than about 50. Some examples of preferred unsaturated aliphatic alcohols include cis-11-hexadecen-1-ol (C₁₆H₃₂O), cis-9-octadecen-1-ol (oleyl alcohol, C₁₈H₃₆O), 3,7,11,15-tetramethyl-2-hexadecen-1-ol (C₂₀H₄₀O), 9-eicosen-1-ol (C₂₀H₄₀O), 11-docosen-1-ol (C₂₂H₄₄O), 13-docosen-1-ol (C₂₂H₄₄O), 12-tetracosen-1-ol (C₂₄H₄₈O) and 13-tetracosen-1-ol (C₂₄H₄₈O).

Von diesen umfassen besonders bevorzugte Beispiele 11-Docosen- 1-ol, 13-Docosen-1-ol, 9-Eicosen-1-ol und cis-9-Octadecen-1-ol (Oleylalkohol).Of these, particularly preferred examples include 11-docosen- 1-ol, 13-docosen-1-ol, 9-eicosen-1-ol and cis-9-octadecen-1-ol (oleyl alcohol).

Die vorstehend beschriebene Komponente (C), d.h. der ungesättigte aliphatische Alkohol, ist in der Schmierölzusammensetzung nach der vorliegenden Erfindung in einer Konzentration von 0,01 bis 10 Gew.-%, vorzugsweise von 0,05 bis 6,0 Gew.-%, anwesend, und das Gewichtsverhältnis des ungesättigten aliphatischen Alkohols zu dem Zinkdithiophosphat (C)/(B) beträgt 0,1 bis 10, vorzugsweise 0,2 bis 3,0. Wenn der Prozentsatz an Komponente (C) in der Schmierölzusammensetzung weniger als 0,01 Gew.-% beträgt oder (C)/(B) kleiner als 0,1 ist, wird durch die Komponente (C) kein nennenswerter Effekt der Unterdrückung der Schlammbildung erzeugt. Selbst wenn andererseits der Prozentsatz an Komponente (C) 10 Gew.-% überschreitet oder (C)/(B) größer als 3,0 ist, kann kein größerer Effekt mehr erwartet werden.The above-described component (C), i.e., the unsaturated aliphatic alcohol, is present in the lubricating oil composition according to the present invention in a concentration of 0.01 to 10% by weight, preferably 0.05 to 6.0% by weight, and the weight ratio of the unsaturated aliphatic alcohol to the zinc dithiophosphate (C)/(B) is 0.1 to 10, preferably 0.2 to 3.0. When the percentage of component (C) in the lubricating oil composition is less than 0.01% by weight or (C)/(B) is less than 0.1, no appreciable effect of suppressing sludge formation is produced by the component (C). On the other hand, even if the percentage of component (C) exceeds 10% by weight or (C)/(B) is greater than 3.0, no greater effect can be expected.

Die Oxidationsstabilität der Schmierölzusammensetzung nach der vorliegenden Erfindung, enthaltend das vorstehend genannte Grundschmieröl (A), die Komponente (B) und die Komponente (C), kann durch Zusetzen einer relativ geringen Menge an mindestens einem Detergens-Dispergiermittel (Komponente D) weiter verbessert werden.The oxidation stability of the lubricating oil composition according to the present invention containing the above-mentioned lubricating base oil (A), component (B) and component (C) can be further improved by adding a relatively small amount of at least one detergent dispersant (component D).

Das bei der vorliegenden Erfindung zu verwendende Detergens- Dispergiermittel kann jedes beliebige bekannte Detergens- Dispergiermittel sein, und einige Beispiele umfassen metallhaltige Detergens-Dispergiermittel, wie Petroleumsulfonate, -phosphonate und -phenate, und aschefreie Detergens-Dispergiermittel, wie Bernsteinsäurederivate und Detergens-Dispergiermittel vom Amintyp. Einige typische Beispiele für Detergens- Dispergiermittel, die vorteilhaft verwendet werden können, sind Ca-sulfonat und Ca-phenat. Die Komponente (D), d.h. das Detergens-Dispergiermittel, ist in der Schmierölzusammensetzung nach der vorliegenden Erfindung in einer Konzentration von 0,01 bis 5,0 Gew.-%, vorzugsweise von 0,1 bis 1,5 Gew.-%, noch besser von 0,2 bis 1,0 Gew.-%, anwesend.The detergent dispersant to be used in the present invention may be any known detergent dispersant, and some examples include metal-containing 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 detergent dispersants that can be advantageously 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 0.01 to 5.0 wt%, preferably 0.1 to 1.5 wt%, more preferably 0.2 to 1.0 wt%.

Die vorstehend erläuterte Schmierölzusammensetzung nach der vorliegenden Erfindung, enthaltend das Grundschmieröl (A), die Komponente (B) und die Komponente (C) oder das Grundschmieröl (A), die Komponente (B), die Komponente (C) und die Komponente (D), kann weiterhin eine relativ kleine Menge mindestens einer Additiv-Verbindung (Komponente E), ausgewählt aus der aus Phosphorsäureestern, Estern der phosphorigen Säure, Aminsalzen von Phosphorsäureestern und Aminsalzen von Estern der phosphorigen Säure bestehenden Gruppe, enthalten.The above-described lubricating oil composition according to the present invention containing the lubricating base oil (A), the component (B) and the component (C) or the lubricating base oil (A), the component (B), the component (C) and the component (D) may further contain a relatively small amount of at least one additive compound (component E) selected from the group consisting of phosphoric acid esters, phosphorous acid esters, amine salts of phosphorous acid esters and amine salts of phosphorous acid esters.

Einige Beispiele für Phosphorsäureester und Ester der phosphorigen Säure, die vorteilhaft verwendet werden können, sind die Verbindungen, die durch die folgenden allgemeinen Formeln (II) bzw. (III) dargestellt sind: Some examples of phosphoric acid esters and phosphorous acid esters that can be used advantageously are Compounds represented by the following general formulas (II) or (III):

wobei jeder der Reste R&sup5;, R&sup6;, R&sup7;, R&sup8;, R&sup9; und R¹&sup0; beispielsweise unabhängig ein Wasserstoffatom, eine Alkylgruppe mit 4 bis 30 Kohlenstoffatomen, eine Arylgruppe mit 6 bis 30 Kohlenstoffatomen oder eine Alkylarylgruppe mit 7 bis 30 Kohlenstoffatomen bedeutet oder wobei zwei oder mehrere von ihnen miteinander identisch sein oder sich voneinander unterscheiden können.wherein each of R⁵, R⁶, R⁷, R⁸, R⁸, R⁹⁰ represents, for example, independently a hydrogen atom, an alkyl group having 4 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or an alkylaryl group having 7 to 30 carbon atoms, or two or more of them may be identical or different from each other.

Einige typische Beispiele für Phosphorsäureester und Ester der phosphorigen Säure umfassen Triphenylphosphat, Tricresylphosphat, Trixylenylphosphat, Tris(isopropylphenyl)-phosphat, Buttersäurephosphat, 2-Ethylhexylsäurephosphat, Laurylsäurephosphat, Oleylsäurephosphat, Stearylsäurephosphat, Dibutylhydrogenphosphit, Dioctylhydrogenphosphit, Dioleylhydrogenphosphit und Distearylhydrogenphosphit.Some typical examples of phosphoric acid esters and esters of phosphorous acid include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris(isopropylphenyl) phosphate, butyric acid phosphate, 2-ethylhexylic acid phosphate, lauric acid phosphate, oleic acid phosphate, stearylic acid phosphate, dibutyl hydrogen phosphite, dioctyl hydrogen phosphite, dioleyl hydrogen phosphite, and distearyl hydrogen phosphite.

Einige Beispiele für Aminsalze von Phosphorsäureestern und Aminsalze von Estern der phosphorigen Säure umfassen Laurylaminsalz, Oleylaminsalz, Kokosaminsalz und Rindertalgaminsalz.Some examples of amine salts of phosphoric acid esters and amine salts of esters of phosphorous acid include laurylamine salt, oleylamine salt, coconut amine salt and beef tallow amine salt.

Die Komponente (E), d.h. die Additiv-Verbindung, ist in der Schmierölzusammensetzung nach der vorliegenden Erfindung in einer Konzentration von 0,01 bis 5,0 Gew.-%, vorzugsweise von 0,1 bis 1,5 Gew.-%, noch besser von 0,2 bis 1,0 Gew.-%, anwesend. Der Zusatz an Komponente (E) verbessert die Verschleißfestigkeit noch weiter.The component (E), i.e. the additive compound, is present in the lubricating oil composition according to the present invention in a concentration of 0.01 to 5.0 wt.%, preferably 0.1 to 1.5 wt.%, more preferably 0.2 to 1.0 wt.%. The addition of component (E) further improves the wear resistance.

Weiterhin kann die Schmierölzusammensetzung nach der vorliegenden Erfindung andere Additive enthalten, die üblicherweise zu Schmierölen zugesetzt werden, beispielsweise Antioxidationsmittel, den Viskositätsindex verbessernde Mittel, Korrosionsschutzmittel, Rostschutzmittel, Metalldesaktivatoren oder Antischaummittel.Furthermore, the lubricating oil composition according to the present invention may contain other additives which are usually added to lubricating oils, for example antioxidants, viscosity index improvers, corrosion inhibitors, rust inhibitors, metal deactivators or antifoam agents.

Die folgenden Beispiele erläutern die vorliegende Erfindung mehr im einzelnen. Der Bereich der Erfindung wird jedoch durch die spezifischen Einzelheiten dieser Beispiele in keiner Weise eingeschränkt.The following examples illustrate the present invention in more detail. However, the scope of the invention is in no way limited by the specific details of these examples.

BEISPIELE 1 bis 14 und VERGLEICHSBEISPIELE 1 bis 5EXAMPLES 1 to 14 and COMPARATIVE EXAMPLES 1 to 5

Tabelle 1 zeigt die Zusammensetzung und die Testergebnisse von Schmierölzusammensetzungen nach den Beispielen und den Vergleichsbeispielen.Table 1 shows the composition and test results of lubricating oil compositions according to the examples and the comparative examples.

Die bei den Beispielen und den Vergleichsbeispielen durchgeführten Tests wurden nach den folgenden Methoden durchgeführt:The tests performed on the examples and comparative examples were carried out using the following methods:

(1) Anfärbung und Entfärbung, (2) Eigenschaft der Unterdrückung der Schlammbildung(1) Coloring and decolorization, (2) property of suppressing sludge formation

Diese Eigenschaften wurden gemäß JIS K 2540, Methode zum Untersuchen der Thermostabilität von Schmierölen, bei einer Testtemperatur (Öltemperatur) von 140ºC durchgeführt. Die verwendeten Katalysatoren waren Kupferdraht, Eisendraht und Aluminiumdraht mit Abmessungen von jeweils φ 1,6 mm x 8 cm.These properties were carried out according to JIS K 2540, Method for Investigating Thermostability of Lubricating Oils, at a test temperature (oil temperature) of 140ºC. The catalysts used were copper wire, iron wire and aluminum wire, each with dimensions of φ 1.6 mm x 8 cm.

Die Auswertung der Anfärbung und Entfärbung (1) wurde so durchgeführt, daß die verwendete Probe alle 24 Stunden entnommen wurde, um die Farbe der Probe zu beobachten (ASTM JIS K 2580), und es ist die Zeit (h) angegeben, die erforderlich ist, daß die Farbe den ASTM-Farbgrad 4 überschreitet. Die Auswertung der Eigenschaft der Unterdrückung der Schlammbildung wurde so durchgeführt, daß die obengenannte Probe beobachtet wurde, und es ist die Zeit (h) angegeben, die erforderlich ist, daß ein Niederschlag von abgeschiedenem Material zu beobachten ist.The evaluation of coloration and decolorization (1) was carried out by taking the sample used every 24 hours to observe the color of the sample (ASTM JIS K 2580), and the time (h) required for the color to exceed ASTM color grade 4 is given. The evaluation of the sludge suppression property was carried out by carried out that the above sample was observed and the time (h) required for a precipitation of deposited material to be observed is given.

(3) Oxidationsstabilität(3) Oxidation stability

Die Oxidationsstabilität wurde gemäß JIS K 2514, Absatz 3.1, Methode zum Prüfen der Oxidationsstabilität von Schmierölen für Verbrennungskraftmaschinen (das sogenannte ISOT) durchgeführt.The oxidation stability was carried out according to JIS K 2514, paragraph 3.1, Method for testing the oxidation stability of lubricating oils for internal combustion engines (the so-called ISOT).

Bedingungen von ISOTConditions of ISOT

Die Bedingungen für die Proben von Beispiel 2 und Vergleichsbeispiel 1 waren @165,5ºC x 24 h, und die Bedingungen für die Probe von Beispiel 12 waren @150ºC x 96 h.The conditions for the samples of Example 2 and Comparative Example 1 were @165.5ºC x 24 h, and the conditions for the sample of Example 12 were @150ºC x 96 h.

(4) Verschleißfestigkeit (Falex-Verschleißfestigkeit)(4) Wear resistance (Falex wear resistance)

Die Prüfung auf Verschleißfestigkeit wurde gemäß ASTM-D 2670 durchgeführt.The wear resistance test was carried out according to ASTM-D 2670.

Materialien: Block SUJ-2 (Rc62)Materials: Block SUJ-2 (Rc62)

Stift SKH-1 (Rc65)Pen SKH-1 (Rc65)

Die in Tabelle 1 angegebenen Kennzeichnungen haben die folgende Bedeutung:The markings given in Table 1 have the following meaning:

*1: 150-Neutralöl (hergestellt von Idemitsu Kosan Co., Ltd.)*1: 150-Neutral oil (manufactured by Idemitsu Kosan Co., Ltd.)

*2: DOA (Handelsname, Dioctyladipat, hergestellt von Nippon Cooper Company)*2: DOA (trade name, dioctyl adipate, manufactured by Nippon Cooper Company)

*3: Fettsäureester von Trimethylolpropan (Handelsname: Unistar H312R, hergestellt von NIPPON OIL & FATS CO., LTD.)*3: Fatty acid ester of trimethylolpropane (trade name: Unistar H312R, manufactured by NIPPON OIL & FATS CO., LTD.)

*4: 1,2-Bis(methylcyclohexyl)-2-methylpropan*4: 1,2-bis(methylcyclohexyl)-2-methylpropane

*5: Zink-di-sec.-hexyldithiophosphat (Handelsname: LZ677A, hergestellt von Lubrizol Corporation)*5: Zinc di-sec-hexyldithiophosphate (trade name: LZ677A, manufactured by Lubrizol Corporation)

*6: Gemisch aus Zink-di-(C&sub4;-C&sub6;)-alkyldithiophosphaten (Handelsname: OLOA267, hergestellt von Chevron Chemical Company)*6: Mixture of zinc di-(C₄-C₆)alkyl dithiophosphates (Trade name: OLOA267, manufactured by Chevron Chemical Company)

*7: Zink-bis(alkylaryl)-dithiophosphat (Handelsname: OLOA260, hergestellt von Chevron Chemical Company)*7: Zinc bis(alkylaryl) dithiophosphate (trade name: OLOA260, manufactured by Chevron Chemical Company)

*8: Oleylalkohol (cis-9-Octadecen-1-ol) (hergestellt von Kyowa Yushi Co., Ltd.)*8: Oleyl alcohol (cis-9-octadecen-1-ol) (manufactured by Kyowa Yushi Co., Ltd.)

*9: 85TBN Ca-sulfonat + 150TBN Ca-phenat (Gewichtsverhältnis 1:1)*9: 85TBN Ca-sulfonate + 150TBN Ca-phenate (weight ratio 1:1)

*10: 300TBN Ca-sulfonat + 150TBN Ca-phenat (Gewichtsverhältnis 1:2)*10: 300TBN Ca-sulfonate + 150TBN Ca-phenate (weight ratio 1:2)

*11: TCP (Tricresylphosphat) (Handelsname, hergestellt von KYOWA HAKKO KOGYO CO., LTD.)*11: TCP (Tricresyl Phosphate) (trade name, manufactured by KYOWA HAKKO KOGYO CO., LTD.)

*12: Polymethacrylat (Molekulargewichts-Zahlenmittel: 60 000) (hergestellt von SANYO CHEMICAL INDUSTRIES, LTD.)*12: Polymethacrylate (number average molecular weight: 60,000) (manufactured by SANYO CHEMICAL INDUSTRIES, LTD.)

*13: Silikonöl*13: Silicone oil

*14: Kalcohol 20 (Handelsname, hergestellt von Kao Corp.)*14: Kalcohol 20 (trade name, manufactured by Kao Corp.)

*15: Oleyloleat (hergestellt von Yuka Sangyo) Tabelle 1 Beispiel Komponente (Grundschmieröl) Andere Additive Mineralöl *1 Diesteröl *2 gehindertes Esteröl synthetisches Napthenöl *4 sec.-AlkylZnDTP *5 p-AlkylZnDTP *6 AlkylarylAZnDTP *7 13-Docosen-1-ol Oleylalkohol *8 Detergens-Dispergiermittel Phosphorsäureester *11 Visk.-Index-Verbesserer *12 Antischaummittel *13 Laurylalkohol *14 Oleyloleat *15 (1)Anfärbung u. Entfärbung (h) (2)Eig.d.Unterdrückung d.Schlammbildung (h) (3)Oxidationsstabilität (ISOT) (Frisches Öl/Testöl) Viskosität (cSt 40ºC) Gesamt-Säurewert (mgKOH/g) Farbe (ASTM) Gehalt an in n-Pentan unlösl.Stoffen (Gew.-%) Zn-Gehalt in Schmierölzusammensetzung (ppm) (4)Falex-Abriebfestigkeit (mg) 181,4 kg (400 lbs) x 60 min Block Stift Tabelle 1 (Fortsetzung) Beispiel Komponente (Grundschmieröl) Andere Additive Mineralöl *1 Diesteröl *2 gehindertes Esteröl *3 synthetisches Napthenöl *4 sec.-AlkylZnDTP *5 p-AlkylZnDTP *6 AlkylarylAZnDTP *7 13-Docosen-1-ol Oleylalkohol *8 Detergens-Dispergiermittel Phosphorsäureester *11 Visk.-Index-Verbesserer *12 Antischaummittel *13 Laurylalkohol *14 Oleyloleat *15 (1)Anfärbung u. Entfärbung (h) (2)Eig.d.Unterdrückung d.Schlammbildung (h) (3)Oxidationsstabilität (ISOT) (Frisches Öl/Testöl) Viskosität (cSt 40ºC) Gesamt-Säurewert (mgKOH/g) Farbe (ASTM) Gehalt an in n-Pentan unlösl.Stoffen (Gew.-%) Zn-Gehalt in Schmierölzusammensetzung (ppm) (4)Falex-Abriebfestigkeit (mg) 181,4 kg (400 lbs) x 60 min Block Stift Tabelle 1 (wird fortgesetzt) Vergleichsbeispiel Komponente (Grundschmieröl) Andere Additive Mineralöl *1 Diesteröl *2 gehindertes Esteröl *3 synthetisches Napthenöl *4 sec.-AlkylZnDTP *5 p-AlkylZnDTP *6 AlkylarylAZnDTP *7 13-Docosen-1-ol Oleylalkohol *8 Detergens-Dispergiermittel Phosphorsäureester *11 Visk.-Index-Verbesserer *12 Antischaummittel *13 Laurylalkohol *14 Oleyloleat *15 (1)Anfärbung u. Entfärbung (h) (2)Eig.d.Unterdrückung d.Schlammbildung (h) (3)Oxidationsstabilität (ISOT) (Frisches Öl/Testöl) Viskosität (cSt 40ºC) Gesamt-Säurewert (mgKOH/g) Farbe (ASTM) Gehalt an in n-Pentan unlösl.Stoffen (Gew.-%) Zn-Gehalt in Schmierölzusammensetzung (ppm) (4)Falex-Abriebfestigkeit (mg) 181,4 kg (400 lbs) x 60 min Block Stift*15: Oleyl oleate (manufactured by Yuka Sangyo) Table 1 Example Component (Base oil) Other additives Mineral oil *1 Diester oil *2 Hindered ester oil Synthetic naphthenic oil *4 sec.-AlkylZnDTP *5 p-AlkylZnDTP *6 AlkylarylAZnDTP *7 13-Docosen-1-ol Oleyl alcohol *8 Detergent-dispersant Phosphoric acid ester *11 Viscosity index improver *12 Antifoaming agent *13 Lauryl alcohol *14 Oleyl oleate *15 (1)Coloring and decolorization (h) (2)Sludge suppression ability (h) (3)Oxidation stability (ISOT) (Fresh oil/Test oil) Viscosity (cSt 40ºC) Total acid value (mgKOH/g) Color (ASTM) Content of n-pentane insolubles (wt.%) Zn content in Lubricating Oil Composition (ppm) (4)Falex Abrasion Resistance (mg) 181.4 kg (400 lbs) x 60 min Block Pin Table 1 (continued) Example Component (Base oil) Other additives Mineral oil *1 Diester oil *2 Hindered ester oil *3 Synthetic naphthenic oil *4 sec.-AlkylZnDTP *5 p-AlkylZnDTP *6 AlkylarylAZnDTP *7 13-Docosen-1-ol Oleyl alcohol *8 Detergent-dispersant Phosphoric acid ester *11 Viscosity index improver *12 Antifoaming agent *13 Lauryl alcohol *14 Oleyl oleate *15 (1)Coloration and decolorization (h) (2)Sludge suppression property (h) (3)Oxidation stability (ISOT) (Fresh oil/Test oil) Viscosity (cSt 40ºC) Total acid value (mgKOH/g) Color (ASTM) Content of n-pentane insolubles (wt%) Zn content in lubricating oil composition (ppm) (4)Falex abrasion resistance (mg) 181.4 kg (400 lbs) x 60 min Block Pin Table 1 (continued) Comparative Example Component (Base Oil) Other Additives Mineral Oil *1 Diester Oil *2 Hindered Ester Oil *3 Synthetic Naphthenic Oil *4 sec.-AlkylZnDTP *5 p-AlkylZnDTP *6 AlkylarylAZnDTP *7 13-Docosen-1-ol Oleyl Alcohol *8 Detergent Dispersant Phosphoric Acid Ester *11 Viscosity Index Improver *12 Antifoaming Agent *13 Lauryl Alcohol *14 Oleyl Oleate *15 (1)Coloration and Discoloration (h) (2)Sludge Suppression Property (h) (3)Oxidation Stability (ISOT) (Fresh Oil/Test Oil) Viscosity (cSt 40ºC) Total Acid Value (mgKOH/g) Color (ASTM) Content of n-Pentane Insoluble Matter (wt%) Zn content in lubricating oil composition (ppm) (4)Falex abrasion resistance (mg) 181.4 kg (400 lbs) x 60 min Block Pin

Tabelle 1 zeigt, daß der Zusatz der Komponente (C), wie 13- Docosen-1-ol und Oleylalkohol, d.h. insbesondere von ungesättigten aliphatischen Alkoholen mit 18 bis 22 Kohlenstoffatomen, die Thermostabilität und die Oxidationsstabilität verbessert, und insbesondere die Eigenschaften der Unterdrückung der Anfärbung, der Entfärbung und der Schlammbildung werden erheblich verbessert. Wie aus den Vergleichsbeispielen 4 und 5 ersichtlich ist, können andere Verbindungen als die Komponenten gemäß der vorliegenden Erfindung nicht die vorgeschriebenen Wirkungen erbringen.Table 1 shows that the addition of the component (C) such as 13- docosen-1-ol and oleyl alcohol, i.e., particularly, unsaturated aliphatic alcohols having 18 to 22 carbon atoms, improves the thermostability and the oxidation stability, and in particular, the properties of suppressing coloration, decolorization and sludge formation are remarkably improved. As is apparent from Comparative Examples 4 and 5, compounds other than the components according to the present invention cannot provide the prescribed effects.

Claims (11)

1. Schmierölzusammensetzung, enthaltend1. Lubricating oil composition containing (A) einen Hauptanteil mindestens eines Grundschmieröls,(A) a major proportion of at least one base lubricating oil, (B) 0,05 bis 5 Gew.-% mindestens eines Zinkdithiophosphats einer Struktur, die durch die folgende allgemeine Formel (1) dargestellt ist (B) 0.05 to 5 wt.% of at least one zinc dithiophosphate having a structure represented by the following general formula (1) in der jeder der Reste R¹, R², R³ und R&sup4; 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, undin which each of R¹, R², R³ and R⁴ independently represents a primary alkyl group having 2 to 30 carbon atoms, a secondary alkyl group having 3 to 30 carbon atoms, a cycloalkyl group having 6 to 30 carbon atoms, an aryl group having 6 to 14 carbon atoms or an alkylaryl group having 7 to 30 carbon atoms, and (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.(C) 0.01 to 10% by weight of at least one unsaturated aliphatic alcohol having 16 to 24 carbon atoms, the weight ratio of the unsaturated aliphatic alcohol to the zinc dithiophosphate (C)/(B) being 0.1 to 10. 2. Schmierölzusammensetzung gemäß Anspruch 1, die zusätzlich2. Lubricating oil composition according to claim 1, which additionally (D) 0,01 bis 5,0 Gew.-% mindestens eines Detergens-Dispergiermittels enthält.(D) 0.01 to 5.0 wt.% of at least one detergent dispersant. 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 40ºC, oder ein synthetisches Öl mit einer kinematischen Viskosität von 5 bis 10 000 mm²/s (cSt), gemessen bei 40ºC, ist.3. A lubricating oil composition according to claim 1 or 2, wherein the base lubricating oil is a mineral oil having a kinematic viscosity of 5 to 10,000 mm²/s (cSt), measured at 40ºC, or a synthetic oil having a kinematic viscosity of 5 to 10,000 mm²/s (cSt), measured at 40ºC. 4. Schmierölzusammensetzung gemäß einem der Ansprüche 1 bis 3, in der das Zinkdithiophosphat aus der aus Zink-diprimären (C&sub3;-C&sub1;&sub2;)-alkyldithiophosphaten, Zink-di-sekundären (C&sub3;-C&sub1;&sub2;)-alkyldithiophosphaten und Zink-bis-(C&sub9;-C&sub2;&sub4;)-(alkylaryl)-dithiophosphaten bestehenden Gruppe ausgewählt ist.4. A lubricating oil composition according to any one of claims 1 to 3, wherein the zinc dithiophosphate is selected from the group consisting of zinc diprimary (C3-C12) alkyl dithiophosphates, zinc di-secondary (C3-C12) alkyl dithiophosphates and zinc bis-(C9-C24) (alkylaryl) dithiophosphates. 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.5. A lubricating oil composition according to any one of claims 1 to 4, wherein the unsaturated aliphatic alcohol is 11- docosen-1-ol, 13-docosen-1-ol, 9-eicosen-1-ol or cis-9- octadecen-1-ol. 6. Schmierölzusammensetzung gemäß Anspruch 1 oder 5, in der der ungesättigte aliphatische Alkohol 13-Docosen-1-ol oder cis-9-Octadecen-1-ol ist.6. A lubricating oil composition according to claim 1 or 5, in which the unsaturated aliphatic alcohol is 13-docosen-1-ol or cis-9-octadecen-1-ol. 7. Schmierölzusammensetzung gemäß Anspruch 1, in der das Grundschmieröl ein Mineralöl ist, das Zinkdithiophosphat ein Gemisch aus Zink-di-prinmären (C&sub4;-C&sub8;)-alkyldithiophospaten ist und der ungesättigte aliphatische Alkohol cis-9- Octadecen-1-ol ist.7. A lubricating oil composition according to claim 1, in which the base lubricating oil is a mineral oil, the zinc dithiophosphate is a mixture of zinc di-primary (C4-C8)alkyl dithiophosphates and the unsaturated aliphatic alcohol is cis-9-octadecen-1-ol. 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.8. Lubricating oil composition according to one of claims 1 to 7, which additionally contains (E) 0.01 to 5.0 wt. % of at least one additive selected from the group consisting of phosphoric acid esters, phosphorous acid esters, amine salts of phosphoric acid esters and amine salts of phosphorous acid esters. 9. Schmierölzusammensetzung gemäß Anspruch 2, in der der ungesättigte aliphatische Alkohol 13-Docosen-1-ol ist.9. A lubricating oil composition according to claim 2, wherein the unsaturated aliphatic alcohol is 13-docosen-1-ol. 10. Schmierölzusammensetzung gemäß Anspruch 2, in der das Grundschmieröl ein Mineralöl ist, das Zinkdithiophosphat ein Gemisch aus Zink-di-primären-(C&sub4;-C&sub6;)-alkyldithiophosphaten ist, der ungesättigte aliphatische Alkohol 13-Docosen-1- ol ist und das Detergens-Dispergiermittel ein Gemisch aus Calciumsulfonat und Calciumphenat ist.10. A lubricating oil composition according to claim 2, wherein the lubricating base oil is a mineral oil, the zinc dithiophosphate is a mixture of zinc di-primary (C4-C6) alkyl dithiophosphates, the unsaturated aliphatic alcohol is 13-docosen-1-ol, and the detergent dispersant is a mixture of calcium sulfonate and calcium phenate. 11. Schmierölzusammensetzung gemäß Anspruch 2, in der das Grundschmieröl ein Mineralöl ist, das Zinkdithiophosphat ein Gemisch aus Zink-di-primären-(C&sub4;-C&sub6;)-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.11. A lubricating oil composition according to claim 2, wherein the base lubricating oil is a mineral oil, the zinc dithiophosphate is a mixture of zinc di-primary (C4-C6) alkyl dithiophosphates, the unsaturated aliphatic alcohol is 13-docosen-1-ol, the detergent-dispersant is a mixture of calcium sulfonate and calcium phenate, and the additive is tricresyl phosphate.
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JP4524007B2 (en) * 1999-06-29 2010-08-11 協同油脂株式会社 Grease composition for constant velocity joints
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
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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
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JPS59122597A (en) * 1982-11-30 1984-07-16 Honda Motor Co Ltd Lubricating oil composition
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
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