JP2000017283A - Lubricating oil additive and lubricating oil composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a lubricating oil additive excellent in lubricity by using a specific glycol compd. SOLUTION: This additive is a compd. of formula I [wherein R1 is a 3C or higher hydrocarbon group; R2 is H or a hydrocarbon group; R3 is a hydrocarbon group; (a) is 1 or higher; (n) is 0, 1, or higher; and B is H or a group of formula II (wherein X is a residue formed by removing hydroxyl groups from a polyol; R4 is a hydrocarbon group; (b) is 1 or higher; and (m) is 0, 1, or higher) provided when B is H, then (a) is 1 and when B is the group of formula II, then a+b is the number of hydroxyl groups of the polyol], is pref. compd. of formula I wherein R1 is 5-24C alkyl; R2 is H; R3 and R4 are each 2-4C alkyl; B is a group of formula II; and X is a residue derived from compds. selected from among ethylene glycol, propylene glycol, butylene glycol, glycerin, sorbitol, or dehydration-condensation products thereof, is compounded pref. in an amt. of 0.01-20 wt.% of a base lube oil, and is pref. used jointly with a phenolic or aminic antioxidant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a lubricating oil additive and a lubricating oil composition using the same.

[0002]

2. Description of the Related Art In recent years, lubricating devices have been increased in speed, output,
There is a demand for miniaturization and maintenance-free. Along with this, various problems have also occurred in lubricating oil. For example, a reduction in the size of a lubricating device has led to a decrease in the amount of lubricating oil, so that the lubricating oil temperature is higher than before. In addition, since three-way catalysts have become widespread in order to suppress the generation of nitrogen oxides (NO _X ) in exhaust gas, the amount of NO _X gas leaking into the crankcase increases, which accelerates deterioration of lubricating oil. ing. In addition, from the requirement of maintenance-free, lubricating oils are required to have a long life, that is, a long drain property. As described above, the demand for lubricating oils to have high stability under severe conditions is increasing year by year.

[0003] On the other hand, lubricating oils are subject to physical shearing during use or exposed to oxidizing atmosphere at high temperature and high pressure.
Degrades over time. The same applies to various additives that are added to lubricating oils, when they undergo oxidative deterioration before exhibiting their original performance and decompose to fail to exhibit their performance, or adversely affect the lubricating oil. There is also.

[0004] In recent years, attempts have been made to improve the temperature-viscosity characteristics of lubricating base oils themselves in order to improve the problem of seizure at high temperatures and the problem of energy loss at low temperatures of engines. That is, the use of a refined base oil obtained by highly refining a mineral oil obtained from crude oil as a base oil or a synthetic base oil synthesized by chemical means is increasing. For this reason, components having antioxidant performance, such as sulfur compounds and nitrogen compounds, which are impurities originally contained in mineral oil, have been eliminated, and the problem that the thermal stability of the lubricating base oil alone is reduced. Has occurred.

[0005] Because of these problems, a variety of additives have been added to the base oil to obtain desired performance. One of the additives includes glycerin monoesters. Glycerin monoester is inexpensive and has an excellent friction adjusting effect, and is therefore used by being added to lubricating oils in a wide range of fields including engine oils. However, it is disadvantageous that glycerin monoester causes hydrolysis in the presence of water. Glycerin monoethers are known as additives that have solved this disadvantage.

[0006]

Glycerin ethers have hitherto been known to be effective as friction modifiers. For example, JP-A-59-25890 discloses that zinc dithiophosphate (ZDTP) and glycerin ethers such as batyl alcohol, chimyl alcohol, and seraky alcohol are added to a mineral oil base oil to have excellent friction adjusting ability. It is described. JP-A-9-1576
No. 76 describes that an ether-based additive such as glycerin monooleyl ether (ceracyl alcohol) exhibits excellent effects, particularly when added to lubricating oil for refrigerators.

However, glycerin ethers represented by the above-mentioned glycerin monooleyl ether and the like are excellent in hydrolytic stability, but may not be satisfactory in terms of lubricity in some cases. Accordingly, the present inventors have studied diligently and have developed a lubricating oil additive having excellent lubricity.

[0008]

That is, the present invention provides the following general formula (1):

Embedded image [Wherein, R ¹ represents a hydrocarbon group having 4 or more carbon atoms;
² represents a hydrogen atom or a hydrocarbon group, R ³ represents a hydrocarbon group, a represents a number of 1 or more, n represents a number of 0 or 1 or more, and B represents a hydrogen atom or the following general formula ( 2)

Embedded image (In the formula, X represents a residue obtained by removing a hydroxyl group from a polyol, R ⁴ represents a hydrocarbon group, b represents a number of 1 or more, and m represents 0 or a number of 1 or more.) A represents 1 when B is a hydrogen atom, and a + b represents the number of hydroxyl groups of the polyol when B is a group represented by the general formula (2). And a lubricating oil composition comprising the compound and a phenolic or amine antioxidant.

[0009]

DETAILED DESCRIPTION OF THE INVENTION The lubricating oil additive of the present invention comprises a glycol compound represented by the general formula (1):

Embedded image In the general formula (1), R ¹ represents a hydrocarbon group having 3 or more carbon atoms. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, and a cycloalkenyl group.

Examples of the alkyl group include propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, isopentyl, and secondary pentyl.
Neopentyl, tertiary pentyl, hexyl, secondary hexyl, heptyl, secondary heptyl, octyl, 2-ethylhexyl, secondary octyl, nonyl, secondary nonyl, decyl, secondary decyl, undecyl, secondary undecyl, dodecyl, secondary Dodecyl, tridecyl, isotridecyl, secondary tridecyl, tetradecyl, secondary tetradecyl, hexadecyl, secondary hexadecyl, stearyl, icosyl, docosyl, tetracosyl, triacontyl, 2-butyloctyl, 2-butyldecyl, 2-hexyloctyl, 2
-Hexyldecyl, 2-octyldecyl, 2-hexyldecyl, 2-octyldodecyl, 2-decyltetradecyl, 2-dodecylhexadecyl, 2-hexadecyloctadecyl, 2-tetradecyloctadecyl, monomethyl-branched-isostearyl and the like Is mentioned.

Examples of the alkenyl group include butenyl,
Isobutenyl, pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, oleyl and the like.

Examples of the aryl group include phenyl, toluyl, xylyl, cumenyl, mesityl, benzyl, phenethyl, styryl, cinnamyl, benzhydryl, trityl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octyl. Phenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl,
Examples include phenylphenyl, benzylphenyl, styrenated phenyl, p-cumylphenyl, α-naphthyl and β-naphthyl groups.

Examples of the cycloalkyl group and the cycloalkenyl group include, for example, cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl, methylcycloheptyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, methylcyclopentenyl, methylcyclohexenyl, methylcyclohepenyl And a thenyl group.

Of these, too long hydrocarbon groups may lower the solubility in lubricating base oils, while too short hydrocarbon groups may lower the lubricity. Therefore, a hydrocarbon group having 3 to 36 carbon atoms is preferable, an alkyl group, an alkenyl group or an aryl group having 4 to 24 carbon atoms is preferable, and an alkyl group having 5 to 24 carbon atoms is most preferable.

R ² is a hydrocarbon group, examples of which are the same as R ¹ , but are preferably hydrogen atoms from the viewpoint of obtaining raw materials.

R ³ represents a hydrocarbon group having 2 to 2 carbon atoms.
It is preferably an alkylene group of 4. General formula (1)
(R ³ —O) _n can be obtained by addition polymerization of ethylene oxide, propylene oxide, butylene oxide, α-olefin oxide, alkylene oxide such as styrene oxide, and the like.
By adding an alkylene oxide or the like, (R ³
When forming a portion of the -O) _n is, R ³ is determined by the alkylene oxide or the like to be added. The polymerization form of the alkylene oxide or the like to be added is not particularly limited.
It may be homopolymerization of two kinds of alkylene oxides or the like, random copolymerization of two or more kinds of alkylene oxides or the like, block copolymerization, random / block copolymerization, or the like.
R ³ is most preferably an ethylene group or a propylene group, and when R ³ is two or more groups, one is preferably an ethylene group. The polymerization degree n is 0 or a number of 1 or more, preferably 1 to 20, more preferably 1 to 10,
More preferably, it is 1 to 5.

In the general formula (1), B is a hydrogen atom or a group represented by the general formula (2):

Embedded image In the general formula (2), X is a residue obtained by removing a hydroxyl group from a polyol. Examples of the polyol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,2-butanediol, neopentyl glycol, 1,6-hexanediol, 1,2-octanediol, 1,8-octanediol, Diols such as isoprene glycol, 3-methyl-1,5-pentanediol, sorbite, catechol, resorcin, hydroquinone, bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F, dimer diol; glycerin, trioxyisobutane, 1,2,3
-Butanetriol, 1,2,3-pentanetriol, 2-methyl-1,2,3-propanetriol, 2
-Methyl-2,3,4-butanetriol, 2-ethyl-1,2,3-butanetriol, 2,3,4-pentanetriol, 2,3,4-hexanetriol, 4-
Propyl-3,4,5-heptanetriol, 2,4-
Trihydric alcohols such as dimethyl-2,3,4-pentanetriol, pentamethylglycerin, pentaglycerin, 1,2,4-butanetriol, 1,2,4-pentanetriol, trimethylolethane, and trimethylolpropane; Erythritol, erythritol,
1,2,3,4-pentane tetrol, 2,3,4,5
Tetrahydric alcohols such as hexane tetrol, 1,2,4,5-pentane tetrol, 1,3,4,5-hexane tetrol, diglycerin and sorbitan; 5 such as adonitol, arabitol, xylitol and triglycerin And polyhydric alcohols; hexahydric alcohols such as dipentaerythritol, sorbitol, mannitol, iditol, inositol, darcitol, talose, and allose; octahydric alcohols such as sucrose, polyglycerin, and dehydration condensates thereof. Among these, ethylene glycol, propylene glycol, butylene glycol, glycerin, sorbitol, or a dehydrated condensate thereof are preferred from the viewpoints of lubricity and oil solubility.

However, if B is a hydrogen atom, the fluidity of the compound represented by the general formula (1) itself deteriorates, and the compoundability and stability when compounded in a lubricating base oil are poor. Is preferably a group represented by the general formula (2).

R ⁴ is the same as R ³ and is preferably an alkylene group having 2 to 4 carbon atoms. m is 0 or a number of 1 or more, preferably 1 to 20, more preferably 1 to
10, more preferably 1 to 5.

A represents a number of 1 or more, and b represents a number of 1 or more. A is 1 when B is a hydrogen atom, and a + b when B is a group represented by the general formula (2).
Is a number corresponding to the number of hydroxyl groups of the polyol.

As the compound represented by the general formula (1), an adjacent long-chain alkanediol such as a so-called 1,2-alkanediol and a condensate thereof and a polyol are applicable. The method for producing the compound of the general formula (1) is not particularly limited. Usually, a method of adding an alkylene oxide such as ethylene oxide to a long-chain 1,2-alkanediol or the like, and a method of reacting a polyol such as ethylene glycol or glycerin with an olefin oxide such as a long-chain α-olefin oxide are exemplified.

The lubricating oil additive of the present invention improves lubricity. Moreover, since it is an ether type compound, it does not hydrolyze. Accordingly, unlike ester-based lubricants such as glycerin monooleate, even when water is mixed in the lubricating oil, the lubricating oil does not deteriorate, so that there is no change in lubricity.

The lubricating oil additive of the present invention is used by being blended with a lubricating base oil. The compounding amount is not particularly limited, but if the amount is too small, the effect of improving lubricity is not sufficiently exhibited, and if the amount is too large, sludge is caused. Therefore, the preferable amount is 0.01 to 20% by weight based on the lubricating base oil, More preferably, it is 0.05 to 15% by weight.

When the lubricating oil additive of the present invention is used in combination with a phenol-based or amine-based antioxidant, it is possible to exhibit lubricity over a long period of time. As the phenolic antioxidant, a hindered phenolic antioxidant having a tertiary butyl group or a tertiary pentyl group in the molecule is particularly preferable. For example, 2,6-di-ter
t-butylphenol, 2,6-di-tert.-butyl-p-cresol, 2,6-di-tert.-butyl-4-methylphenol, 2,6-di-tert.-butyl-4-ethyl Phenol, 2,4-dimethyl-6-
tert.-butylphenol, 4,4′-methylenebis (2,6-di-tert.-butylphenol),
4,4'-bis (2,6-di-tert.-butylphenol), 4,4'-bis (2-methyl-6-ter
-butylphenol), 2,2'-methylenebis (4-methyl-6-tert.-butylphenol),
2,2'-methylenebis (4-ethyl-6-tert.
-Butylphenol), 4,4′-butylidenebis (3
-Methyl-6-tert.-butylphenol), 4,
4'-isopropylidenebis (2,6-di-tert.
-Butylphenol), 2,2'-methylenebis (4-
Methyl-6-cyclohexylphenol), 2,2′-
Methylene bis (4-methyl-6-nonylphenol),
2,2′-isobutylidenebis (4,6-dimethylphenol), 2,6-bis (2′-hydroxy-3′-t
tert.-butyl-5'-methylbenzyl) 4-methylphenol, 3-tert.-butyl-4-hydroxyanisole, 2-tert.-butyl-4-hydroxyanisole, 4,4'-thiobis (3-methyl -6-t
ert. -Butylphenol), 4,4′-thiobis (2-methyl-6-tert.-butylphenol),
2,2′-thiobis (4-methyl-6-tert.-butylphenol), 2,6-di-tert. -Butyl-
α-dimethylamino-p-cresol, 2,6-di-t
ert. -Butyl-4 (N, N'-dimethylaminomethylphenol), bis (3,5-di-tert.-butyl-4-hydroxybenzyl) sulfide, tris {(3,5-di-tert.-butyl) 4-hydroxyphenyl) propionyl-oxyethyl diisocyanurate, tris (3,5-di-tert.-butyl-4-)
(Hydroxyphenyl) isocyanurate, 1,3,5-
Tris (3 ′, 5′-di-tert.-butyl-butyl-4-hydroxybenzoyl) isocyanurate, bis {2-methyl-4- (3-n-alkylthiopropionyloxy) -5-tert. -Butylphenyl disulfide, 1,3,5-tris (4-di-tert.-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, tetraphthaloyl-di (2,6-dimethyl-4) -Tert.-butyl-3-hydroxybenzyl sulfide), 6- (4-hydroxy-3,5-di-tert.-butylanilino) -2,4-bis (octylthio) -1,3,5-triazine, , 2-thio-
{Diethyl-bis-3- (3,5-di-tert.-butyl-4-hydroxyphenyl)} propionate,
N, N'-hexamethylenebis (3,5-di-ter
t. -Butyl-4-hydroxy-hydrocinamide),
3,5-di-tert. -Butyl-4-hydroxy-benzyl-phosphoric acid diester, bis (3-methyl-4-hydroxy-5-tert.-butylbenzyl) sulfide, bisphenol A, alkylated bisphenol A, polyalkylated bisphenol A, etc.

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Embedded image (In the formula, Me represents a methyl group, t-Bu is ter
t. Represents a -butyl group, R represents a monovalent hydrocarbon group, and R 'represents a divalent hydrocarbon group. ) And the like.

As the amine antioxidant, an aromatic amine antioxidant is particularly preferable. For example, naphthylamine antioxidants such as 1-naphthylamine, phenyl-1-naphthylamine, p-octylphenyl-1-naphthylamine, p-nonylphenyl-1-naphthylamine, p-dodecylphenyl-1-naphthylamine and phenyl-2-naphthylamine Agent; N, N'-diisopropyl-
p-phenylenediamine, N, N'-diisobutyl-p
-Phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-di-β-naphthyl-p-
Phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N-cyclohexyl-
N'-phenyl-p-phenylenediamine, N-1,3
Phenylenediamine antioxidants such as -dimethylbutyl-N'-phenyl-p-phenylenediamine, dioctyl-p-phenylenediamine, phenylhexyl-p-phenylenediamine, phenyloctyl-p-phenylenediamine; dipyridylamine, diphenylamine,
p, p'-di-n-butyldiphenylamine, p, p '
-Di-tert. -Butyldiphenylamine, p, p '
-Di-tert. -Pentyldiphenylamine, p,
p'-dinonyldiphenylamine, p, p'-didecyldiphenylamine, p, p'-didodecyldiphenylamine, p, p'-distyryldiphenylamine, p,
Examples thereof include diphenylamine-based antioxidants such as p′-dimethoxydiphenylamine, 4,4′-bis (4-α, α-dimethylbenzoyl) diphenylamine, and p-isopropoxydiphenylamine.

The amount of these phenolic or amine-based antioxidants to be added is not particularly limited. However, if the amount is too small, the antioxidant effect is not sufficient, and if the amount is too large, there is no effect corresponding to the added amount and there is a technical meaning. , Preferably 0.01 to 5% by weight, more preferably 0.05 to 3% by weight, based on the base oil.

The lubricating base oil which can be used in the present invention may be any one of a mineral oil, a synthetic oil and a mixture thereof. The kinematic viscosity of the lubricating base oil is not particularly limited, but is preferably 1 to 50 cSt at 100 ° C, and 10 to 1 at 40 ° C.
000 cSt, and the viscosity index (VI) is preferably 70
The number is more preferably 100 or more.

Mineral oil is separated from natural crude oil, and is produced by appropriately distilling, refining, and the like.
Main component of mineral oil is hydrocarbon (mostly paraffins)
And further contains a naphthene component, an aromatic component, and the like. Base oils which have been subjected to hydrorefining, solvent dewaxing, solvent extraction, solvent dewaxing, hydrogen dewaxing, catalytic dewaxing, hydrocracking, alkali distillation, sulfuric acid washing, clay treatment, etc. are also preferably used. be able to. These purification means are appropriately combined, and it is effective to repeat the same treatment in a plurality of stages. For example, (A) a method in which a distillate is subjected to a solvent extraction treatment or a solvent extraction treatment followed by a hydrogenation treatment and then a sulfuric acid washing, (B) a method in which a distillate oil is subjected to a hydrogenation treatment and then a dewaxing treatment, (C) a method of subjecting a distillate to solvent extraction and then hydrotreating, (D) a method of subjecting a distillate to solvent extraction and a clay treatment, and (E) a distillate of two or more stages of hydrogen. (F) Hydrotreating distillate oil, or alkali distilling or sulfuric acid washing treatment after hydrogenation treatment, or these treatments A method of mixing oil is effective.

By performing these treatments, it is possible to remove aromatic components, sulfur components, nitrogen components, and the like. With the current technology, these impurities can be removed to a trace amount or less, but aromatics have an effect of making the lubricating oil additive easy to dissolve, so that about 3 to 5% by weight remains. There is also. For example, the sulfur content and the nitrogen content in the currently used highly refined mineral oil are 0.01% by weight or less, and in some cases 0.005% by weight or less. On the other hand, the aromatic content is 1% by weight or less, and in some cases, 0.05% by weight or less, and about 3% by weight remains.

The synthetic oil is a chemically synthesized lubricating oil such as poly-α-olefin, polyisobutylene (polybutene), diester, polyol ester, phosphate ester, silicate ester, polyalkylene. Glycols, polyphenyl ethers, silicones, fluorinated compounds, alkylbenzenes and the like can be mentioned. Among them, poly-α-olefin, polyisobutylene (polybutene), diester, polyol ester, polyalkylene glycol, and the like can be used for general purposes, and can be preferably used for internal combustion engine oil, processing oil, and the like.

Examples of the poly-α-olefin include 1
-Hexene, 1-octene, 1-nonene, 1-decene,
Examples thereof include those obtained by polymerizing or oligomerizing 1-dodecene, 1-tetradecene, and the like, and those obtained by hydrogenating them. Examples of the diester include glutaric acid,
Examples include dibasic acids such as adipic acid, azelaic acid, sebacic acid and dodecane diacid, and diesters of alcohols such as 2-ethylhexanol, octanol, decanol, dodecanol and tridecanol. Examples of the polyol ester include neopentyl glycol, trimethylolethane, trimethylolpropane, glycerin, pentaerythritol, sorbitol, dipentaerythritol, tripentaerythritol, or a polyol such as an alkylene oxide adduct thereof, butyric acid, isobutyric acid, Esters with fatty acids such as valeric acid, isovaleric acid, pivalic acid, capric acid, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and oleic acid. Examples of the polyalkylene glycol include polyethylene glycol, polypropylene glycol, polyethylene glycol monomethyl ether, mono- or dimethyl ether of a block or random copolymer of ethylene oxide / propylene oxide, and the like.

Since these synthetic oils are each chemically synthesized, they are single substances or mixtures of homologues. Therefore, for example, synthetic oils such as poly-α-olefin, polyisobutylene (polybutene), diester, polyol ester, and polyalkylene glycol are used as impurities contained in mineral oil such as benzene, polycyclic condensed aromatic components, and thiophene. Of sulfur, nitrogen such as indole and carbazole are not included.

The lubricating oil additive of the present invention can be used in combination with other lubricating oil additives as required. Representative lubricating oil additives include oil agents, friction modifiers, extreme pressure agents, other antioxidants, detergents, dispersants, viscosity index improvers, defoamers, rust inhibitors, pour point depressants And the like.

Examples of the oil agent include fatty acids such as capric acid, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, linoleic acid and linolenic acid, lauryl alcohol, myristyl alcohol , Palmityl alcohol, stearyl alcohol, alcohols such as oleyl alcohol, laurylamine, myristylamine, palmitylamine, stearylamine, amines such as oleylamine,
Examples include amides such as laurylamide, myristylamide, palmitylamide, stearylamine, and oleylamine.

Examples of the friction modifier include capric acid (mono, di, tri) glyceride and caproic acid (mono, di, tri).
Di, tri) glyceride, caprylic acid (mono, di, tri)
Glyceride, lauric acid (mono, di, tri) glyceride, myristic acid (mono, di, tri) glyceride, palmitic acid (mono, di, tri) glyceride, stearic acid (mono, di, tri) glyceride, oleic acid (mono) ,
Esters such as di- and tri-glycerides; metal salts such as oxymolybdenum dialkyl dithiocarbamate and oxymolybdenum dialkyl dithiophosphate; polyol ethers such as glycerin monooleyl ether; and polyethers.

Examples of extreme pressure agents include sulfurized olefins,
Sulfurized paraffin, Sulfurized polyolefin, Sulfurized lard, Sulfurized fish oil, Sulfurized whale oil, Sulfurized soybean oil, Sulfurized pinene oil, Sulfurized phenol, Sulfurized alkylphenol, Sulfurized fatty acid, Dialkyl polysulfide, Dibenzyl disulfide, Diphenyl disulfide, Polyphenylene sulfide, Alkyl mercaptan, Alkylsulfone Acid, dithiocarbamate, 1,3,4-thiadiazole derivative,
Thiuram disulfide, butyl (thio, dithio) phosphate, hexyl (thio, dithio) phosphate, octyl (thio, dithio) phosphate, 2-ethylhexyl (thio, dithio) phosphate, nonyl (thio, dithio) phosphate, decyl (thio, dithio) ) Phosphate, lauryl (thio, dithio) phosphate, myristyl (thio, dithio) phosphate, palmityl (thio,
Dithio) phosphate, stearyl (thio, dithio) phosphate, oleyl (thio, dithio) phosphate,
(Thio, dithio) phosphates such as phenyl (thio, dithio) phosphate and cresyl (thio, dithio) phosphate.

Examples of the sulfur-based antioxidants include dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, lauryl stearyl thiodipropionate, dimyristyl thiodipropionate, and distearyl- β, β′-thiodibutyrate, 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, 2-benzimidazole disulfide, dilauryl sulfide, amylthioglycolate and the like.

Examples of the phosphorus-based antioxidant include triphenyl phosphite, trinonyl phenyl phosphite, triisodecyl phosphite, diphenyl isodecyl phosphite, phenyl diisotridecyl phosphite, trioctadecyl phosphite, and tridecyl phosphite. Phyte, diphenylnonylphenylphosphite, trilauryltrithiophosphite, tris (cyclohexylphenyl) phosphite, bis (2-ethylhexyl) phosphite, diisodecylpentaerythritol diphosphite, distearylpentaerythritol diphosphite, tetraphenyldipropylene Glycol diphosphite and the like.

Examples of the metal salt include nickel dithiocarbamate and zinc-2-mercaptobenzimidazole.

Examples of the detergent include calcium sulfonate, calcium phenate, calcium salicylate, magnesium sulfonate, magnesium phenate, magnesium salicylate, barium sulfonate, barium phenate, and barium salicylate. Examples of the dispersant include polyalkenyl succinimide, polyalkenyl succinimide boride, benzylamine and the like. Examples of the viscosity index improver include poly (meth) acrylate, polyisobutylene, polystyrene, ethylene-propylene copolymer, styrene-isobutylene copolymer and the like.

When used as a grease, the lubricating oil additive of the present invention is added to a base grease obtained by adding a thickener to a base oil composed of mineral oil or synthetic oil. Examples of the thickener include organic non-soaps such as soap-based or complex soap-based thickeners, terephthalate-based thickeners, urea-based thickeners, polytetrafluoroethylene, and fluorinated ethylene-propylene copolymers. And a non-soap inorganic thickener. Although the amount of the thickener is not particularly limited, it is usually preferably 3 to 40% by weight, more preferably 5 to 2% by weight based on the base grease comprising the base oil and the thickener.
0% by weight. The consistency of the base grease comprising the base oil and the thickener is not particularly limited, but is usually about 100 to 500.

The lubricating oil additive of the present invention can be used by adding it to lubricating oils for various uses. For example, industrial lubricating oils,
Turbine oil, machine oil, bearing oil, compressor oil, hydraulic oil, hydraulic oil, internal combustion engine oil, refrigeration oil, gear oil, oil for automatic transmission (ATF), oil for continuously variable continuously variable transmission (CVT oil), Transaxle fluids, metalworking oils and the like. or,
Plain bearings, rolling bearings, gears, universal joints, torque limiters, constant velocity joints for automobiles (CV
J), and can be used by adding to various greases such as ball joints, wheel bearings, constant speed gears, and transmission gears. Among them, additives for internal combustion engine oils such as vehicle engines, two-stroke engines, aircraft engines, marine engines, locomotive engines, gear oils, automatic transmission oils, and continuously variable transmission oils. It is suitable as an additive for transmission lubricating oil. Examples of the internal combustion engine include a gasoline engine, a diesel engine, a jet engine, a gas turbine engine, an alcohol engine, and the like.

[0043]

The present invention will be described more specifically with reference to the following examples. In the following examples, “parts” and “%” are based on weight unless otherwise specified. << Base oil >> Mineral oil-based high VI oil obtained by treating a mineral oil obtained from a crude oil by a hydrocracking process method. The kinematic viscosity is 4.1 cSt at 100 ° C., 18.3 cSt at 40 ° C.,
VI = 126.

<< Lubricant Additive of the Present Invention >><Product 1 of the Present Invention> 1,2-Dodecanediol (the following formula)

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<Product 2 of the Invention> 1,2-Dodecanediol EO 1 mol adduct (the following formula)

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<Product 3 of the Invention> 1,2-Dodecanediol EO 2 mol adduct (the following formula)

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<Product 4 of the Invention> 1,2-Dodecanediol PO2 mol adduct (the following formula)

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<Product 5 of the Invention> 1,2-Hexadecanediol EO 2 mol adduct (the following formula)

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<Product 6 of the Invention> 1,2-Tetradecanediol EO 2 mol adduct (the following formula)

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<Product 7 of the Invention> 1,2-octadecanediol EO 2 mol adduct (the following formula)

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<Product 8 of the Invention> 1,2-Dodecanediol glycerin condensate (the following formula)

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<Product 9 of the Present Invention> 1,2-Dodecanediol diglycerin condensate (the following formula)

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<Product 10 of the Invention> 1,2-Dodecanediol sorbitol condensate (the following formula)

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<Product 11 of the Present Invention> 1,2-Dodecanediol diethylene glycol condensate (the following formula)

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<< Antioxidant >> <Antioxidant 1>

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<Antioxidant 2>4,4'-methylenebis (2,6-di-tert.-butylphenol) <Antioxidant 3>

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<Antioxidant 4>

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<Antioxidant 5> p, p'-dioctyldiphenylamine <Antioxidant 6> Diphenyl-p-phenylenediamine <Antioxidant 7> Phenyl-1-naphthylamine

<< Comparative product >> <Comparative product 1> Glycerin monooleyl ester <Comparative product 2> Oleic acid amide <Comparative product 3> Glycerin monooleyl ether

The lubricating oil composition obtained from the above components was subjected to a lubricating oil oxidation deterioration test for an internal combustion engine by the following method, and then to a friction coefficient measurement test. <Lubricating oil oxidation stability test for internal combustion engine> The lubricating oil oxidation stability test for internal combustion engine was performed in accordance with JIS-K-2514. In addition, the temperature of the thermostat was set to 165.5 ° C., and the sample stirring rod was stirred at 1,300 revolutions per minute for 24 hours to deteriorate the sample oil. <Friction coefficient measurement test> The friction coefficient was measured using an SRV measurement tester. The test was performed under ball-on-plate line contact conditions. That is, the upper cylinder (φ15 × 22m
m) was set on a plate (φ24 × 6.85 mm), reciprocated under the following conditions, and the friction coefficient was measured after 15 minutes. The material was SUJ-2 for both. Load: 200N Temperature: 80 ° C Measurement time: 15 minutes Amplitude: 1mm Cycle: 50Hz

[0061]

[Table 1]

[0062]

[Table 2]

[0063]

[Table 3]

[0064]

[Table 4]

[0065]

The effect of the present invention is to provide a novel lubricating oil additive and a lubricating oil composition using the same.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Kazuhisa Morita 7-35, Higashiogu, Arakawa-ku, Tokyo Asahi Denka Kako Co., Ltd. (72) Kazuhiro Umehara 7-35, Higashiogu, Arakawa-ku, Tokyo Asahi Denka Kogyo Co., Ltd. F-term (reference) 4H104 BB04C BB05C BB08C BB35C BE07C DA02A EB02 LA03 LA13

Claims (6)

[Claims] 1. The following general formula (1): [Wherein, R ¹ represents a hydrocarbon group having 3 or more carbon atoms;
² represents a hydrogen atom or a hydrocarbon group, R ³ represents a hydrocarbon group, a represents a number of 1 or more, n represents a number of 0 or 1 or more, and B represents a hydrogen atom or the following general formula ( 2) (In the formula, X represents a residue obtained by removing a hydroxyl group from a polyol, R ⁴ represents a hydrocarbon group, b represents a number of 1 or more, and m represents 0 or a number of 1 or more.) A represents 1 when B is a hydrogen atom, and a + b represents the number of hydroxyl groups of the polyol when B is a group represented by the general formula (2). ] A lubricating oil additive comprising a compound represented by the formula: 2. The lubricating oil additive according to claim 1, wherein R ¹ is an alkyl group having 5 to 24 carbon atoms, and R ² is a hydrogen atom. 3. The lubricating oil additive according to claim 1, wherein R ³ and R ⁴ are an alkylene group having 2 to 4 carbon atoms. 4. B is a group represented by the general formula (2), and X is ethylene glycol, propylene glycol,
The lubricating oil additive according to any one of claims 1 to 3, which is butylene glycol, glycerin, sorbitol, or a dehydrated condensate thereof. 5. A lubricating oil composition comprising a lubricating base oil containing the lubricating oil additive according to claim 1 and a phenolic or amine antioxidant. 6. The phenolic antioxidant is a hindered phenolic antioxidant having a tertiary butyl group or a tertiary pentyl group in a molecule, and the amine antioxidant is an aromatic amine antioxidant. Claim 5.
The lubricating oil composition according to the above.