JP2005534782A - Engine oil containing lead corrosion inhibitor - Google Patents

Abstract

Engine oil containing a lead corrosion inhibitor United States Patent Application 20070227735 Kind Code: A1 A blended engine oil containing a certain 1,2,4-triazole metal deactivator is used for lead engine parts such as bearings. Especially non-aggressive. The inclusion of certain 1,2,4-triazole compounds allows the combined use of corrosive additives such as sulfur containing additives and vegetable oil derived friction modifiers while meeting ASTM D4485 standards.

Description

  The present invention relates to engine oil (engine fluid) compositions that are non-aggressive to lead.

Patent document 1 is disclosing the metal deactivator with respect to a functional liquid.
Patent Document 2 discloses a composition useful for preventing precipitation of lead paint in a lubricant.

  Engine oil standards are becoming more stringent as performance requirements, and new formulations are under development to meet these new standards. Engine oil standards are defined in ASTM D 4485.

  New engine oil formulations under development consist of certain additive chemicals. Many of these additive chemicals are corrosive to lead. While meeting certain current engine oil specifications by using certain advantageous additives, it is difficult for formulators to meet the standards for lead corrosion.

Since 1994, all diesel oils are defined in ASTM D 4485 and lead levels measured according to either ASTM D 5968 (performed at 125 ° C) or ASTM D 6594 (performed at 135 ° C). It is required to meet corrosion standards. The ASTM D 4485 Standard for Performance of Engine Oils for engine oil performance is 60 ppm for API categories CF-4 and CG-4 according to ASTM D 5968, and according to ASTM D 6594. -4 shows a maximum allowable lead corrosion level of 120 ppm.
US Pat. No. 4,734,209 US Pat. No. 4,491,527

  For example, certain components of formulated engine oils that cause lead corrosion include certain surfactants, antiwear agents, friction modifiers and antioxidants. Many such desirable additive chemicals are disqualified for use because engine oil formulations do not meet industry standards for lead corrosion.

  For example, desirable additive chemicals that are aggressive to lead and otherwise disqualified for use in engine oils include sulfur-containing additives and certain vegetable oil derived friction modifiers.

It has surprisingly been found that certain 1,2,4-triazole metal deactivators are particularly non-aggressive against lead, eg, lead engine parts such as bearings. The engine oil described in this invention meets the corrosion prevention performance requirements of the diesel lubricant standard as defined in ASTM D 4485.
This lead corrosion problem is generally not a problem with other types of lubricants, such as turbine oil and hydraulic fluid.

  The engine oils of the present invention are diesel oil and universal oil. Universal oils include both diesel and passenger car oils. Engine oil is used, for example, in internal combustion engines, for example in motor vehicles fitted with Otto, diesel, 2-stroke, Wankel or track engines.

で表される少なくとも１種の化合物、及び
ｃ）鉛に対して攻撃的であり、及び抗酸化剤、耐磨耗剤、分散剤、界面活性剤、消泡剤、粘度指数向上剤、銅不動態化剤、防錆剤、流動点降下剤、乳化破壊剤及び摩擦改善剤からなる群より選択された少なくとも１種のオイル添加剤を含み、
式中、Ｒ₁及びＲ₂は同じであるか又は異なり、及び炭素原子数１ないし２０のアルキル基、炭素原子数３ないし２０のアルケニル基、炭素原子数５ないし１２のシクロアルキル基、炭素原子数７ないし１３のアラルキル基又は炭素原子数６ないし１０のアリール基を表すか、又はＲ₁及びＲ₂は各々の結合する窒素原子と一緒に５−、６−又は７−員環ヘテロ環残基を表し、又はＲ₁及びＲ₂は式

Ｒ₃Ｘ［（−Ｒ₄−）Ｏ］_n（−Ｒ₄）−

（式中、
ＸはＯ、Ｓ又はＮを表し、
Ｒ₃は水素原子又は炭素原子数１ないし２０のアルキル基を表し、
Ｒ₄は炭素原子数１ないし１２のアルキレン基を表し、
ｎは０であるか又は１ないし６の整数である。）
で表される基を表すか、
又はＲ₁及びＲ₂の一方は式

で表される基を表し、
又はＲ₂が式（ＩＩ）で表される基を表し、そしてＲ₁が式

−［Ｒ₄］_n−Ｎ（Ｒ₅）−Ａ−［Ｎ（Ｒ₅）₂］_m

（式中、
ｍは０又は１であり、及びｍが０である場合にはＡは式（ＩＩ）で表される基を表し、及びｍが１である場合にはＡはアルキレン基又は炭素原子数６ないし１０のアリーレン基を表し、そしてＲ₅は式（ＩＩ）で表される基を表す。）で表される基を表し、
成分（ｂ）を含まない場合は、前記エンジンオイル組成物はＡＳＴＭ Ｄ ６５９４試験にしたがって測定して鉛がおよそ１００ｐｐｍを超えている
ところの組成物に関する。 Specifically, the present invention is an engine oil composition that is non-aggressive to lead, the composition comprising:
a) Base fluid b) Formula (I)

At least one compound represented by: c) aggressive to lead, and antioxidants, antiwear agents, dispersants, surfactants, antifoaming agents, viscosity index improvers, copper Including at least one oil additive selected from the group consisting of a mobilizing agent, a rust inhibitor, a pour point depressant, an emulsion breaker and a friction improver,
Wherein R ₁ and R ₂ are the same or different and are an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 3 to 20 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a carbon atom Represents an aralkyl group having 7 to 13 carbon atoms or an aryl group having 6 to 10 carbon atoms, or R ₁ and R ₂ together with the nitrogen atom to which each is bonded, a 5-, 6- or 7-membered heterocyclic residue Represents a group, or R ₁ and R ₂ are of the formula

R ₃ X [(— R ₄ —) O] _n (—R ₄ ) —

(Where
X represents O, S or N;
R ₃ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
R ₄ represents an alkylene group having 1 to 12 carbon atoms,
n is 0 or an integer of 1 to 6. )
Or a group represented by
Or _one of R ₁ and R ₂ is the formula

Represents a group represented by
Or R ₂ represents a group represented by the formula (II), and R ₁ represents the formula

_{- [R 4] n -N (} R 5) -A- [N (R 5) 2] m

(Where
m is 0 or 1, and when m is 0, A represents a group represented by the formula (II), and when m is 1, A represents an alkylene group or 6 to 6 carbon atoms. 10 represents an arylene group, and R ₅ represents a group represented by the formula (II). ) Represents a group represented by
In the absence of component (b), the engine oil composition relates to a composition in which lead exceeds approximately 100 ppm as measured according to ASTM D 6594 test.

R ₄ is, for example, an alkylene group having 1 to 6 carbon atoms, such as an alkylene group having 2 or 3 carbon atoms.
The number n is, for example, 0, 1, 2, 3, 4, 5 or 6.
The alkyl group is linear or branched and includes, for example, methyl group, ethyl group, n-proyl group, isopropyl group, n-butyl group, sec-butyl group, n-pentyl group, n- Hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl or n- Eicosyl group.
Alkenyl groups are linear or branched and include, for example, prop-2-enyl, but-2-enyl, 2-methyl-prop-2-enyl, pent-2-enyl groups , A hexa-2,4-dienyl group, a dec-10-enyl group or an eicos-2-enyl group.
The cycloalkyl group is, for example, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclodecyl group, an adamantyl group or a cyclododecyl group.
The aralkyl group is, for example, a benzyl group, a 2-phenylethyl group, a benzhydryl group, or a naphthylmethyl group.
The aryl group is, for example, a phenyl group or a naphthyl group.
R ₁ and R ₂ together with the nitrogen atom to which they are attached form a heterocyclic group, which is, for example, a morpholine ring group, a pyrrolidine ring group, a piperidine ring group or a perhydroazepine ring group.
Examples of the alkylene group include a methylene group, an ethylene group, a 1: 2- or 1: 3-propylene group, a 1: 4-butylene group, a 1: 6-hexylene group, a 1: 8-octylene group, and a 1: 10-decylene group. And 1: 12-dodecylene group.
Arylene groups include, for example, phenylene groups and naphthylene groups.

Specific compounds represented by the formula (I) are: 1- (or 4)-(dimethylaminomethyl) triazole, 1- (or 4)-(diethylaminomethyl) triazole, 1- (or 4)-( Di-isopropylaminomethyl) triazole, 1- (or 4)-(di-n-butylaminomethyl) triazole, 1- (or 4)-(di-n-hexylaminomethyl) triazole, 1- (or 4) -(Di-isooctylaminomethyl) triazole, 1- (or 4)-(di- (2-ethylhexyl) aminomethyl) triazole, 1- (or 4)-(di-n-octylaminomethyl) triazole, 1 -(Or 4)-(di-n-decylaminomethyl) triazole, 1- (or 4)-(di-n-dodecylaminomethyl) triazole, 1- (or 4)-( -N-octadecylaminomethyl) triazole, 1- (or 4)-(di-n-eicosylaminomethyl) triazole, 1- (or 4)-[di- (prop-2'-enyl) aminomethyl] triazole 1- (or 4)-[di- (but-2′-enyl) aminomethyl] triazole, 1- (or 4)-[di- (eicose-2′-enyl) aminomethyl] triazole, 1- (Or 4)-(di-cyclohexylaminomethyl) triazole, 1- (or 4)-(di-benzylaminomethyl) triazole, 1- (or 4)-(di-phenylaminomethyl) triazole, 1- (or 4)-(4′-morpholinomethyl) triazole, 1- (or 4)-(1′-pyrrolidinomethyl) triazole, 1- (or 4)-(1′-piperidinomethyl) tria 1- (or 4)-(1′-perhydroazepinomethyl) triazole, 1- (or 4)-[(2 ′, 2 ″ -dihydroxyethyl) aminomethyl] triazole, 1- (or 4 )-(Dibutoxypropyl-aminomethyl) triazole, 1- (or 4)-(dibutylthiopropyl-aminomethyl) triazole, 1- (or 4)-(di-butylaminopropyl-aminomethyl) triazole, N, N-bis- (1- or 4-triazolylmethyl) laurylamine, N, N-bis- (1- or 4-triazolylmethyl) oleylamine, N, N-bis- (1- or 4-tria Zolylmethyl) ethanolamine and N, N, N ′, N′-tetra (1- or 4-triazolylmethyl) ethylenediamine.
A representative compound represented by the formula (I) is, for example, 1- (di-isooctylaminomethyl) triazole, that is, 1- (di-isooctylaminomethyl) -1,2,4-triazole. Or 1- (di- (2-ethylhexyl) aminomethyl) 1,2,4-triazole.

  The compounds of formula (I) are prepared by known methods, for example as disclosed in US Pat. No. 4,734,209, the disclosure of which is hereby incorporated by reference. .

  Base fluids for this invention include mineral oil based fluids (API groups I, II and III), poly-α-olefin-PAOs (API group IV), esters (API group V), other synthetic fluids, origins Utilizes natural oils, which are animals or plants, and mixtures thereof. The base fluid is of a suitable viscosity for use in engine oil applications.

  The present compounds of formula (I) are used at a concentration of about 0.01 to about 1.0% by weight, based on the weight of the blended engine oil. For example, the compound of formula (I) is about 0.02 to about 0.5% by weight; for example, about 0.03 to about 0.3% by weight; for example, about 0.01 to about 0.5 or about 0.01 To about 0.3% by weight; for example, about 0.02 to about 1.0 or about 0.02 to about 0.3% by weight; for example, about 0.03 to about 1.0, or about 0.03 to about 0. .5% by weight.

Suitable antioxidants for component (c) are:
1) alkylated monophenols such as 2,6-di-tert-butyl-4-methylphenol, 2-butyl-4,6-di-methylphenol, 2,6-di-tert-butyl-4-ethyl Phenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-iso-butylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (α -Methylcyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tri-cyclohexylphenol, 2,6-di-tert-butyl-4-methoxy Methylphenol, linear or branched nonylphenol such as 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6- (1′-methylun) Ci-1'-yl) phenol, 2,4-dimethyl-6- (1'-methylheptadecy-1'-yl) phenol, 2,4-dimethyl-6- (1'-methyltridec-1'-yl) phenol And mixtures thereof 2) Alkylthiomethylphenols, for example 2,4-di-octylthiomethyl-6-tert-butylphenol, 2,4-di-octylthiomethyl-6-methylphenol, 2,4-di-octyl Thiomethyl-6-ethylphenol or 2,6-di-dodecylthiomethyl-4-nonylphenol 3) hydroquinone and alkylated hydroquinone such as 2,6-di-tert-butyl-4-methoxyphenol, 2,5- Di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenone 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tertiary Butyl-4-hydroxyphenyl stearate or bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate 4) Tocopherols, for example α-, β-, γ- or δ-tocopherol or mixtures thereof ( Vitamin E)
5) hydroxylated thiodiphenyl ethers such as 2,2′-thiobis (6-tert-butyl-4-methylphenol), 2,2′-thiobis (4-octylphenol), 4,4′-thiobis (6- Tributyl-3-methylphenol), 4,4′-thiobis (6-tert-butyl-2-methylphenol), 4,4′-thiobis (3,6-di-secondary amylphenol) or 4,4 '-Bis (2,6-di-methyl-4-hydroxyphenyl) disulfide 6) alkylidene bisphenols such as 2,2'-methylene bis (6-tert-butyl-4-methylphenol), 2,2'-methylene bis (6-tert-butyl-4-ethylphenol), 2,2′-methylenebis (4-methyl-6- (α-methylcyclohexyl) -phenol), 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (6-nonyl-4-methylphenol), 2,2'-methylenebis (4,6-di-tert-butylphenol), 2,2 ' -Ethylidenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis (6- (α-methylbenzyl) -4-nonylphenol), 2,2'-methylene-bis (6- (α, α-dimethylbenzyl) -4-nonylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 4 , 4′-methylenebis (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-tert three Til-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis (5- Tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecylmercaptobutane, ethylene glycol bis (3,3-bis (3′-tert-butyl-4′-hydroxyphenyl) butyrate), bis ( 3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclo-pentadiene, bis (2- (3′-tert-butyl-2′-hydroxy-5′-methylbenzyl) -6-tert-butyl-4 -Methylphenyl) terephthalate, 1,1-bis- (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3,5-di-tert-butyl-4-hydroxyphene) Propane, 2,2-bis- (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane or 1,1,5,5-tetra (5-tert-butyl- 4-hydroxy-2-methylphenyl) pentane 7) O-, N- and S-benzyl compounds such as 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether Octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris (3,5-di-tert-butyl) amine, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) Fido or isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate 8) Hydroxybenzylated malonate such as dioctadecyl 2,2-bis (3,5-di-tert-butyl-2-hydroxy Benzyl) malonate, di-octadecyl 2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) -malonate, di-dodecyl mercaptoethyl-2,2-bis (3,5-di-tert-butyl- 4-hydroxybenzyl) -malonate or di (4- (1,1,3,3-tetramethylbutyl) phenyl) -2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate 9) Aromatic hydroxybenzyl compounds such as 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2 , 4,6-trimethylbenzene, 1,4-bis (3,5-di-tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene or 2,4,6-tris ( 3,5-di-tert-butyl-4-hydroxybenzyl) phenol 10) triazine compounds such as 2,4-bisoctyl mercapto-6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octyl mercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octyl mercapto- 4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4- Hydroxyphenoxy) -1,2,3- Triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6 -Dimethylbenzyl) isocyanurate, 2,4,6-tris- (3,5-di-tert-butyl-4-hydroxyphenylethyl) -1,3,5-triazine, 1,3,5-tris (3 , 5-Di-tert-butyl-4-hydroxyphenylpropionyl) hexahydro-1,3,5-triazine or 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate 11) Benzylphosphonate For example, dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzyl Phosphonate, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzyl phosphonate, dioctadecyl 5-tert-butyl-4-hydroxy-3-methylbenzyl phosphonate or 3,5-di-tert-butyl-4- Calcium salt of monoethyl ester of hydroxybenzylphosphonic acid 12) Acylaminophenol, for example 4-hydroxylauranilide, 4-hydroxystearanilide or octyl N- (3,5-di-tert-butyl-4-hydroxy Phenyl) carbamate 13) β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid, β- ( 3,5-dicyclohexyl-4-hydroxyphenyl) -propionic acid, 3,5-di-tert-butyl 4-hydroxyphenylacetic acid or β- (5-tert-butyl-4-hydroxyphenyl) -3-thiabutyric acid and mono- or polyhydric alcohols such as methanol, ethanol, n-octanol, i-octanol, Octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyan Nurate, N, N′-bis (hydroxyethyl) oxalsamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7 -Esterification of trioxabicyclo (2.2.2) octane, glycerol or transesterification products based on natural triglycerides of eg coconut oil, rapeseed oil, sunflower oil or colza oil 14) Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, such as N, N′-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylene Diamine, N, N′-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamine or N, N′-bis (3,5-di-tert-butyl-4-hydroxyphenyl) Propionyl) hydrazine 15) Ascorbic acid (vitamin C)
16) Amine-type antioxidants such as N, N′-diisopropyl-p-phenylenediamine, N, N′-di-secondarybutyl-p-phenylenediamine, N, N′-bis (1,4-dimethyl) Pentyl) -p-phenylenediamine, N, N′-bis (1-ethyl-3-methyl-pentyl) -p-phenylenediamine, N, N′-bis (1-methyl-heptyl) -p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-di (naphth-2-yl) -p-phenylenediamine, N-isopropyl-N'- Phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine, N- (1-methylheptyl) N′-phenyl-p-phenyle Diamine, N-cyclohexyl-N′-phenyl-p-phenylenediamine, 4- (p-toluenesulfonamido) diphenylamine, N, N′-dimethyl-N, N′-di-secondary butyl-p-phenylenediamine, Diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine such as p , P'-di-tert-octyldiphenyl-amine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, Di- (4-methoxyphenyl) Amine, 2,6-di-tert-butyl-4-dimethylamino-methyl-phenol, 2,4′-diaminodiphenylmethane, 4,4′-diamino-diphenylmethane, N, N, N ′, N′-tetramethyl -4,4'-diamino-diphenylmethane, 1,2-di ((2-methylphenyl) amino) ethane, 1,2-di- (phenylamino) propane, (o-tolyl) biguanide, di (4- ( 1 ', 3'-dimethylbutyl) -phenyl) amine, tertiary octylated N-phenyl-1-naphthylamine, mono- and dialkylated tertiary butyl / tertiary octyl diphenylamine mixtures, mono- and dialkylated nonyl diphenylamines Mixtures, mixtures of mono- and dialkylated dodecyldiphenylamine, mono- and dialkylated isopropyl / isohexyl diph Mixtures of nilamines, mixtures of mono- and dialkylated tert-butyldiphenylamine, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mono- and dialkylated tert-butyl / tertiary octyl A mixture of phenothiazines, a mixture of mono- and dialkylated tertiary octylphenothiazines, N-allylphenothiazine, N, N, N ′, N′-tetraphenyl-1,4-diaminobut-2-ene, N, N-bis ( 2,2,6,6-tetramethylpiperidin-4-yl) hexamethylenediamine, bis (2,2,6,6-tetramethyl-piperidin-4-yl) sebacate, 2,2,6,6- Tetramethylpiperidino-4-one or 2,2,6,6-tetramethylpiperidino-4-ol, and 17) aliphatic or aromatic Phosphites, esters of thiodipropionic acid or thiodiacetic acid, or salts of dithiocarbamic acid or dithiophosphoric acid, 2,2,12,12-tetramethyl-5,9-dihydroxy-3,7,1-trithiatri It is selected from decane or 2,2,15,15-tetramethyl-5,12-dihydroxy-3,7,10,14-tetrathiahexadecane.

（式中、Ｒ及びＲ’は独立して炭素原子数１ないし２０のアルキル基、炭素原子数３ないし２０のアルケニル基、炭素原子数５ないし１２のシクロアルキル基、炭素原子数７ないし１３のアラルキル基又は炭素原子数６ないし１０のアリール基を表し、例えばＲ及びＲ’は独立して炭素原子数１ないし１２のアルキル基を表す。）
として表され、
及び
２）硫化オレフィン及び植物油、トリトリルホスフェート、トリクレシルホスフェート、塩素化パラフィン、アルキル及びアリールジ−及びトリスルフィド、モノ−及びジアルキルホスフェートのアミン塩、メチルホスホン酸のアミン塩、ジエタノールアミノメチルトリルトリアゾール、ジ（２−エチル−ヘキシル）−アミノメチルトリルトリアゾール、２，５−ジメルカプト−１，３，４−チアジアゾールの誘導体、エチル（（ビスイソプロピルオキシホスフィノチオイル）チオ）プロピオネート、トリフェニルチオホスフェート（トリフェニルホスホロチオエート）、トリス（アルキルフェニル）ホスホロチオエート及びそれらの混合物（例えばトリス（イソノニルフェニル）ホスホロチオエート）、ジフェニルモノノニルフェニルホスホロチオエート、イソブチルフェニルジフェニルホスホロチオエート、３−ヒドロキシ−１，３−チアホスフェタン３−オキシドのドデシルアミン塩、トリチオホスホン酸５，５，５−トリス（イソオクチル２−アセテート）、１−（Ｎ，Ｎ−ビス（２−エチルヘキシル）アミノメチル）−２−メルカプト−１Ｈ−１，３−ベンゾチアゾールのような２−メルカプトベンゾチアゾールの誘導体又はエトキシカルボニル５−オクチルジチオカルバメートのような硫黄原子−及び／又はリン原子−及び／又はハロゲン原子−含有化合物
より選択される。 Suitable antiwear agents for component (c) are:
1) Dihydrocarbyl dithiophosphate metal salts where the metal is aluminum, lead, tin, manganese, cobalt, nickel, zinc or copper, but most often zinc. Zinc salt (dialkyldithiophosphate zinc)

Wherein R and R ′ are independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 3 to 20 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or 7 to 13 carbon atoms. Represents an aralkyl group or an aryl group having 6 to 10 carbon atoms, for example, R and R ′ independently represent an alkyl group having 1 to 12 carbon atoms.)
Represented as
And 2) sulfurized olefins and vegetable oils, tolylyl phosphate, tricresyl phosphate, chlorinated paraffin, alkyl and aryl di- and trisulfides, amine salts of mono- and dialkyl phosphates, amine salts of methylphosphonic acid, diethanolaminomethyltolyltriazole, Di (2-ethyl-hexyl) -aminomethyltolyltriazole, a derivative of 2,5-dimercapto-1,3,4-thiadiazole, ethyl ((bisisopropyloxyphosphinothioyl) thio) propionate, triphenylthiophosphate ( Triphenylphosphorothioate), tris (alkylphenyl) phosphorothioate and mixtures thereof (eg tris (isononylphenyl) phosphorothioate), diphenylmonononylphenyl Phosphorothioate, isobutylphenyl diphenyl phosphorothioate, dodecylamine salt of 3-hydroxy-1,3-thiaphosphetane 3-oxide, trithiophosphonic acid 5,5,5-tris (isooctyl 2-acetate), 1- (N, N-bis Derivatives of 2-mercaptobenzothiazole such as (2-ethylhexyl) aminomethyl) -2-mercapto-1H-1,3-benzothiazole or sulfur atoms and / or phosphorus atoms such as ethoxycarbonyl 5-octyldithiocarbamate -And / or a halogen atom-containing compound.

Suitable dispersants for component (c) are:
1) Mannich base which is a condensation reaction product of aldehyde such as high molecular weight phenol, alkylene polyamine and formaldehyde 2) Olefin polymer and succinic acylating agent (acid, anhydrous) further reacted with organic hydroxy compound and / or amine Succinic acid-based dispersants, which are the reaction products of products, esters or halides) and 3) high molecular weight amides and hydrocarbyl acylating agents and polyhydric aliphatic alcohols (such as glycerol, pentaerythritol or sorbitol) Selected from esters such as reaction products.

  Ashless (metal-free) polymeric materials that typically contain an oil-soluble high molecular weight skeleton bonded to polar functional groups associated with the dispersed particles are typically used as dispersants. Widely used hydrocarbon backbones are olefin polymers and copolymers, ie -ethylene, propylene, butylene, isobutylene, styrene; with or without other functional groups incorporated into the polymer backbone. Polar materials such as amines, alcohols, amides or esters are attached to the backbone via bridges.

Suitable dispersants for component (c) are: selected from calcium, magnesium, barium, sodium or lithium salts of organic acids such as sulfonates, alkyl phenates, sulfurized alkyl phenates, carboxylates, salicylates, phosphonates, thiophosphonates and phosphinates. Is done.
The salt may be neutral or may be alkaline, for example with a metal hydroxide or carbonate.

  Suitable antifoaming agents for component (c) are selected from: silicone oil, polysiloxane and polyethylene glycol ether.

Suitable viscosity index improvers for component (c) are: polyisobutylene, copolymers of ethylene and propylene, polyacrylates, polymethacrylates, vinyl pyrrolidone / methacrylate copolymers, polyvinyl pyrrolidone, polybutenes, olefin copolymers, styrene / acrylate copolymers, styrene / isoprene. Selected from copolymers, styrene / isobutadiene copolymers, isoprene / butadiene copolymers and polyethers.

Suitable copper passivating agents for component (c) are:
1) Benzotriazole and derivatives thereof, for example 4- or 5-alkylbenzotriazole (for example toltriazole) and derivatives thereof, 4,5,6,7-tetrahydrobenzotriazole, 5,5′-methylenebisbenzotriazole; -Mannich bases of benzotriazoles or toltriazoles such as-(di (2-ethylhexyl) aminomethyl) toltriazole and 1- (di- (2-ethylhexyl) aminomethyl) -benzotriazole; 1- (nonyloxymethyl)- Alkoxyalkylbenzotriazoles such as benzotriazole, 1- (1-butoxyethyl) -benzotriazole or 1- (1-cyclohexyloxybutyl) -toltriazole 2) Imidazole derivatives such as 4,4′-methylenebis (2- Ndecyl-5-methyl-imidazole), bis ((N-methyl) imidazol-2-yl) carbinol octyl ether 3) Sulfur-containing heterocyclic compounds such as 2-mercaptobenzothiaazole, 2,5-dimercapto- 1,3,4-thiadiazole, 2,5-dimercaptobenzothiadiazole and derivatives thereof, or 3,5-bis (di (2-ethylhexyl) aminomethyl) -1,3,4-thiadiazolin-2-one, and 4) selected from amino compounds such as salicylidenepropylenediamine, salicylaminoguanidine or salts thereof.

Suitable rust inhibitors for component (c) are:
1) Nonionic polyoxyalkylene polyols and their esters, polyoxyalkylene phenols, organic acids, their esters, metal salts, amine salts and anhydrides such as alkyl- and alkenyl succinic acids and their alcohols, diols or hydroxycarboxylic acids 4-esteryl phenoxyacetic acid, alkoxy- and alkoxyethoxycarboxylic acids, such as partial esters with acids, partial amides of alkyl- and alkenyl succinic acids, dodecyloxyacetic acid, dodecyloxy (ethoxy) acetic acid and their amine salts, or N-oleoyl sarcosine, sorbitan monooleate, lead naphthenate and alkenyl succinic anhydrides such as dodecenyl succinic anhydride, 2- (2-carboxyethyl) -1-dodecyl-3-methylglycerol and its E.g. sodium and triethanolamine salts 2) i) primary, secondary or tertiary aliphatic or cycloaliphatic amines and amine salts of organic or inorganic acids such as oil soluble alkyl ammonium carboxylates, and also 1- (N , N-bis (2-hydroxyethyl) amino) -3- (4-nonylphenoxy) propano-2-ol, or ii) heterocyclic compounds such as: substituted imidazolines or oxazolines such as 2-heptadecenyl- Compounds containing nitrogen atoms selected from 1- (2-hydroxyethyl) -imidazoline 3) Phosphorus-containing compounds such as phosphoric acid, phosphoric acid partial esters or amine salts of phosphonic acid partial esters or zinc dialkyldithiophosphates 4) Sulfur-containing compounds such as dinonylnaphthalene-barium sulfonate, petro Calcium sulfonates, alkylthio-substituted aliphatic carboxylic acids, esters of aliphatic 2-sulfocarboxylic acids or their salts, and 5) glycerol derivatives such as glycerol monooleate, 1- (alkylphenoxy) -3- (2 -Hydroxyethyl) glycerol, 1- (alkylphenoxy) -3- (2,3-dihydroxypropyl) glycerol or 2-carboxyalkyl-1,3-
Selected from dialkylglycerols.

  Suitable pour point depressants for component (c) are selected from polymethacrylates and alkylated naphthalene derivatives.

  Suitable demulsifiers for component (c) are selected from polyether polyols and dinonyl naphthalene sulfonates.

Suitable friction modifiers of component (c) are fatty acids and their derivatives, for example natural esters of fatty acids such as glycerol monooleate, amides, imides and amines such as oleylamine, sulfur-containing organomolybdenum dithiocarbamates, sulfur -Phosphorus-containing organomolybdenum dithiophosphates, sulfur-nitrogen-containing organomolybdenum compounds based on dispersants, molybdenum carboxylate salts, molybdenum-amine complexes, molybdenumamine / alcohol / amide complexes and molybdenum cluster compounds, Teflon And molybdenum disulfide.

  Additives that are aggressive to lead include antioxidants such as sulfur-containing antioxidants, sulfur-containing antiwear agents, sulfur-containing copper passivators or vegetable oil-derived friction modifiers, and anti-wear agents. It is a wear agent, surfactant, copper passivator or friction modifier. For example, a sulfur-containing antioxidant that is aggressive to lead is a phenothiazine antioxidant.

  The additive of component (c) is added in conventional amounts in each case in the range of approximately 0.01 to approximately 10.0% by weight, based on the engine oil composition.

  The compounds of the formula (I) can be introduced into engine oils in a manner known per se. The compound is readily soluble in oil. In order to use the concentrate in the required ratio, it is also possible to prepare so-called additive masterbatches (packages) that can be diluted with the corresponding fluid. The compound of formula (I) may be introduced as part of an additive package.

  Without the compound of formula (I), the engine oil consisting of components (a) and (c) does not meet the lead corrosion standards defined in ASTM D4485 as measured by ASTM D6594. Or just be close to the standard. That is, when the compound represented by the formula (I) is not included, the engine oil composed of the components (a) and (c) is approximately 100 ppm, approximately 120 ppm, approximately 150 ppm, approximately 180 ppm, as measured by ASTM D6594. Or more than about 210 ppm.

  The invention is also (a) base fluid and (c) aggressive to lead, and antioxidants, antiwear agents, dispersants, surfactants, antifoam agents, viscosity index improvers, copper Corrosion of lead parts in the presence of an engine oil composition comprising at least one oil additive selected from the group consisting of passivating agents, rust inhibitors, pour point depressants, demulsifiers and friction modifiers. Which comprises (b) blending at least one compound of formula (I) with the engine oil composition, wherein component (b) is included. In the absence, the engine oil composition also relates to a process wherein lead exceeds approximately 100 ppm as measured according to ASTM D 6594 test.

  The following examples illustrate the invention in more detail. They should not be construed as limiting the invention in any way.

に示す。
ＧＭＯ及びＴＰＳ２７の両方とも、ベース配合物の腐食を増加させ、ベース配合物を使用に不適なものとさせた。各々の場合において、イルガメット３０は、腐食を非常に許容し得る水準にまで有意に低減させた。
Example ASTM D6594 Assessment of Diesel Engine Oil Corrosion at 135 ° C. In this test, four metal specimens of copper, lead, tin and phosphor bronze were immersed in a measured amount of engine oil. The oil was blown with air at 135 ° C. for 168 hours. When the test was complete, the stressed oil was tested to detect corrosion and corrosion products. The presence of copper, lead and tin in the oil used was determined by ICP. Desirably, the result is less than 50 ppm lead in the stressed oil.
As a base formulation for this example, a fully formulated non-corrosive engine oil was used. In order to show the effect of the present invention, a friction improver / corrosion inhibitor glycerol monooleate (GMO) 1.0% by weight and a sulfur-containing antiwear / extreme pressure additive diternonyl tri 0.5% by weight of sulfide (TPS® 27) was added separately to the base formulation. These are compounds represented by formula (I) according to ASTM D6594: 1- (di- (2-ethylhexyl) aminomethyl) 1,2,4-triazole (Irgamet (registered trademark) 30, Ciba Specialty Chemicals) Both with and without 0.2% by weight were tested. The following table shows the results for lead corrosion that occurred during the test:

Shown in
Both GMO and TPS27 increased the corrosion of the base formulation, making it unsuitable for use. In each case, irgamet 30 significantly reduced corrosion to a very tolerable level.

Claims (9)

An engine oil composition that is non-aggressive to lead, said composition comprising:
a) Base fluid b) Formula (I)

At least one compound represented by: c) aggressive to lead, and antioxidants, antiwear agents, dispersants, surfactants, antifoaming agents, viscosity index improvers, copper Including at least one oil additive selected from the group consisting of a mobilizing agent, a rust inhibitor, a pour point depressant, an emulsion breaker and a friction improver,
Wherein R ₁ and R ₂ are the same or different and are an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 3 to 20 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a carbon atom Represents an aralkyl group having 7 to 13 carbon atoms or an aryl group having 6 to 10 carbon atoms, or R ₁ and R ₂ together with the nitrogen atom to which each is bonded, a 5-, 6- or 7-membered heterocyclic residue May form a group, or R ₁ and R ₂ may be of the formula

R ₃ X [(— R ₄ —) O] _n (—R ₄ ) —

(Where
X represents O, S or N;
R ₃ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
R ₄ represents an alkylene group having 1 to 12 carbon atoms,
n is 0 or an integer of 1 to 6. )
Or a group represented by
Or _one of R ₁ and R ₂ is the formula

Represents a group represented by
Or R ₂ represents a group represented by the formula (II), and R ₁ represents the formula

_{- [R 4] n -N (} R 5) -A- [N (R 5) 2] m

(Where
m is 0 or 1, and when m is 0, A represents a group represented by the formula (II), and when m is 1, A represents an alkylene group or 6 to 6 carbon atoms. 10 represents an arylene group, and R ₅ represents a group represented by the formula (II). ) Represents a group represented by
When component (b) is not included, the engine oil composition is a composition in which lead exceeds approximately 100 ppm as measured according to ASTM D 6594 test. The compound represented by the formula (I) is 1- (or 4)-(dimethylaminomethyl) triazole, 1- (or 4)-(diethylaminomethyl) triazole, 1- (or 4)-(di-isopropyl). Aminomethyl) triazole, 1- (or 4)-(di-n-butylaminomethyl) triazole, 1- (or 4)-(di-n-hexylaminomethyl) triazole, 1- (or 4)-(di -Isooctylaminomethyl) triazole, 1- (or 4)-(di- (2-ethylhexyl) aminomethyl) triazole, 1- (or 4)-(di-n-octylaminomethyl) triazole, 1- (or 4)-(di-n-decylaminomethyl) triazole, 1- (or 4)-(di-n-dodecylaminomethyl) triazole, 1- (or 4)-(di-n Octadecylaminomethyl) triazole, 1- (or 4)-(di-n-eicosylaminomethyl) triazole, 1- (or 4)-[di- (prop-2'-enyl) aminomethyl] triazole, 1- (Or 4)-[di- (but-2'-enyl) aminomethyl] triazole, 1- (or 4)-[di- (eicose-2'-enyl) aminomethyl] triazole, 1- (or 4 )-(Di-cyclohexylaminomethyl) triazole, 1- (or 4)-(di-benzylaminomethyl) triazole, 1- (or 4)-(di-phenylaminomethyl) triazole, 1- (or 4)- (4′-morpholinomethyl) triazole, 1- (or 4)-(1′-pyrrolidinomethyl) triazole, 1- (or 4)-(1′-piperidinomethyl) tri Sol, 1- (or 4)-(1′-perhydroazepinomethyl) triazole, 1- (or 4)-[(2 ′, 2 ″ -dihydroxyethyl) aminomethyl] triazole, 1- (or 4) -(Dibutoxypropyl-aminomethyl) triazole, 1- (or 4)-(dibutylthiopropyl-aminomethyl) triazole, 1- (or 4)-(di-butylaminopropyl-aminomethyl) triazole, N, N -Bis- (1- or 4-triazolylmethyl) laurylamine, N, N-bis- (1- or 4-triazolylmethyl) oleylamine, N, N-bis- (1- or 4-triazolyl) A methyl group selected from the group consisting of (rumethyl) ethanolamine and N, N, N ', N'-tetra (1- or 4-triazolylmethyl) ethylenediamine. Composition. The compound represented by the formula (I) is 1- (di-isooctylaminomethyl) -1,2,4-triazole or 1- (di- (2-ethylhexyl) aminomethyl) -1,2,4. A composition according to claim 1, which is a triazole. The composition of claim 1, wherein component (b) is present from about 0.01 to about 1.0 weight percent based on the weight of the engine oil. The composition of claim 1 wherein component (b) is present from about 0.02 to about 0.5 wt% based on the weight of the engine oil. The composition of claim 1, wherein component (b) is present from about 0.03 to about 0.3 wt% based on the weight of the engine oil. The composition of claim 1 wherein the additive of component (c) is selected from the group consisting of antioxidants, antiwear agents, surfactants, copper passivators and friction modifiers. The additive of component (c) is selected from the group consisting of a sulfur-containing antioxidant, a sulfur-containing antiwear agent, a sulfur-containing copper passivator and a vegetable oil-derived friction improver. The composition as described. The composition of claim 1 wherein the additive of component (c) is selected from the group consisting of phenothiazine antioxidants and vegetable oil derived friction modifiers. (A) base fluid and (c) aggressive to lead, and antioxidants, antiwear agents, dispersants, surfactants, antifoaming agents, viscosity index improvers, copper passivating agents, A method for preventing corrosion of lead parts in the presence of an engine oil composition comprising at least one oil additive selected from the group consisting of a rust inhibitor, a pour point depressant, an emulsion breaker and a friction improver. The method comprises (b) blending at least one compound of formula (I) according to claim 1 into the engine oil composition, wherein the engine oil composition comprises: If the component (b) is not included, the lead exceeds approximately 100 ppm as measured according to the ASTM D 6594 test.