JP2010518205A - Multi-metal corrosion inhibitor - Google Patents

Abstract

A multi-metal corrosion inhibitor is provided.
The object of the present invention is to
a) lubricating oil;
b) a triazole metal deactivator;
A lubricating oil composition comprising c) a boric acid ester; and optionally d) an amine phosphate.
The present invention enables the creation of engine lubricants that can protect copper, lead, iron and zinc from corrosion during the life of the lubricant.
[Selection figure] None

Description

  An object of the present invention is to suppress corrosion of lead, copper, iron and zinc in a lubricating oil. The lubricating oil is, for example, low ash, low phosphorus engine oil (engine fluid) or industrial oil.

  Protection of the metal parts of an ignition engine has been provided by the combination of a neutral to overbased detergent, zinc dithiophosphate (ZnDTP).

  Exhaust gas aftertreatment systems for automobiles are currently required to comply with exhaust gas laws, especially new Japanese or European laws. The efficiency of these systems can be compromised by lubricating ash derived from metal, sulfur and phosphorus containing additives. Therefore, the amount of ash-containing detergents and phosphorus and ash-containing ZnDTP has been reduced in oils made recently to meet current and pressing standards. This can result in reduced corrosion protection of metal parts in the engine.

  U.S. Pat. No. 4,734,209 discloses a copper passivating agent for functional fluids.

  U.S. Pat. Nos. 5,171,463 and 5,032,300 teach benzotriazole-based copper passivating agents.

  US Pat. No. 6,410,490 teaches benzotriazole additives for lubricating oils.

  U.S. Pat. Nos. 6,008,165 and 6,010,986 teach borate as a means for inhibiting lead corrosion.

  Surprisingly, it has been found that certain metal deactivators, borate esters, and optionally amine phosphate combinations, when added to lubricating oils, maintain a high level of protection for bearings and other parts in the engine. It was.

  The present invention enables the creation of engine lubricants that can protect copper, lead, iron and zinc from corrosion during the life of the lubricant. Overbased detergents are known to those skilled in the art and are, for example, phenates, sulfonates or salicylates. The contents of ZnDTP and cleaning agent are suppressed by SAPS restrictions (sulfate ash, phosphorus and sulfur). The ZnDTP content is mainly controlled by the maximum limit set for the% -P content in various engine oil standards. ILSAC and API gradually reduced the P content for passenger car oil as follows.

Maximum allowed% -P
ILSAC GF-1 / API SH 0.12
(1992)
ILSAC GF-2 and 3 / API SJ and SL 0.10
(1996-2001)
ILSAC GF-4 / API SM 0.08
(2004)

  The next classification, GF-5 (scheduled for 2009), requires P-levels by using a catalytic converter toxicology test. If the test is not available, the P limit is further reduced to either a maximum of 0.06 or 0.05% P.

  In Europe, the ACEA 2004 standard for gasoline and diesel engines with aftertreatment devices also requires a reduction in phosphorus content.

Permissible% -P
C1 ≦ 0.05
C2 0.070-0.090
C3 0.070-0.090

  The new ACEA E6 high horsepower diesel engine standard has a maximum limit of 0.08% for phosphorus. The total ash limit is also lowered. This affects the detergent and ZnDTP content.

  Because the sulfur limit limits the contribution that ZnDTP and sulfonate detergents (and sulfurized phenolate detergents) can make, it is also part of the averaging.

  The reduction in these materials results in reduced capacity in protecting the lubricant from copper and lead corrosion in the engine. Furthermore, the economic demands for fuels necessitate the further use of friction modifiers such as glycerol monooleate and certain molybdenum compounds. These materials can be corrosive to copper or lead or both. U.S. Pat. No. 2,898,299 teaches the erodibility of glycerol monooleate on copper-lead bearing alloys. U.S. Pat. No. 5,631,213, European Patent Application Publication No. 1,382,659 and D.C. T.A. Jane, J.A. R. Shanklin, and C.I. F. Statue, “Corrosion Inhibition of Copper Alloys in Engine Oil Production: Abrasion Resistance, Friction Modifier, Dispersant Synergistic Effect”, SAE Paper 2002-01-2767, is a specific molybdenum compound for copper and copper alloys. Teaching corrosiveness. In addition, certain industrial oils erode zinc.

US Pat. No. 4,734,209 US Pat. No. 5,171,463 US Pat. No. 5,032,300 US Pat. No. 6,410,490 US Pat. No. 6,008,165 US Pat. No. 6,010,986 US Pat. No. 2,898,299 US Pat. No. 5,631,213 European Patent Publication No. 1,382,659

D. T.A. Jane, J.A. R. Shanklin, and C.I. F. Statue, “Copper alloy corrosion inhibition in engine oil preparation: wear resistance, friction modifier, dispersant synergistic effect”, SAE Paper 2002-01-2767.

The subject of the present invention is
a) lubricating oil;
b) a triazole metal deactivator;
A lubricating oil composition comprising c) a boric acid ester; and optionally d) an amine phosphate.

  Components b), c) and d) present in the lubricating oil composition of the present invention are specified below.

A further object of the present invention is a method for inhibiting corrosion of lead, copper, iron and zinc in a lubricating oil, wherein b) a triazole metal deactivator;
c) boric acid ester; and optionally d) a method comprising formulating an amine phosphate.

  The engine oils of the present invention utilize either natural or synthetic base fluids such as vegetable oils, minerals, for example. Usually API I, II and III, mineral and synthetic oils, IV, poly-α-olefins, V, such as esters are utilized. Synthetic oils can also be obtained from the Fischer-Tropsch gas liquor synthesis procedure. These products can often be hydroisomerized. A mixture of two or more of the above base fluids can be used. The finished fluid is used, for example, in an internal combustion engine engine, for example in an automobile with an Otto, Diesel, 2-cycle Wankel or orbital engine bonded.

  The engine oil of the present invention contains, for example, less than about 1.1% by mass of ash. For example, the engine oil contains less than about 0.9% by weight ash or less than about 0.8% by weight ash. The engine oil contains less than about 0.1% by weight phosphorus. For example, the engine oil of the present invention contains less than about 0.08%, less than about 0.07% or less than about 0.06% by weight phosphorus. The engine oil of the present invention has, for example, less than about 0.5% by weight sulfur, for example, less than about 0.4% by weight sulfur.

  Ash content is determined by the sulfate ashing technique, ASTM D874.

  Industrial lubricating oils are, for example, polyalkylene glycols and are used, for example, in windmills.

  The present triazole metal deactivators are those of 1,2,4-triazoles or benzotriazoles.

  Metal deactivators for 1,2,4-triazoles are disclosed, for example, in US Pat. No. 4,734,209.

｛式中、Ｒ₁及びＲ₂は同一又は相違し、そして炭素原子数１乃至２０のアルキル基、炭素原子数３乃至２０のアルケニル基、炭素原子数５乃至１２のシクロアルキル基、炭素原子数７乃至１３のアラルキル基又は炭素原子数６乃至１０のアリール基を表し、又はＲ₁と
Ｒ₂は、それぞれが結合している窒素原子と一緒になって、５、６又は７員の複素環を形
成しても良く、又はＲ₁及びＲ₂は部分式

（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乃至２０のアルキル基を表し、
Ｒ₄は、炭素原子数１乃至１２のアルキレン基を表し、
ｎは、０又は１乃至６の整数を表す。）で表される基を表し、
又はＲ₁とＲ₂の一方は部分式

で表される基を表すか、
又はＲ₂は部分式（ＩＩ）で表される基を表し、そしてＲ₁は部分式

（式中、
ｍは、０又は１を表し、ｍが０の場合は、Ａは式（ＩＩ）で表される基を表し、ｍが１の場合は、Ａはアルキレン基又は炭素原子数６乃至１０アリーレン基を表し、及びＲ₅は
式（ＩＩ）で表される基を表す。）で表される基を表す。｝で表されるものである。
Ｒ₄は、例えば、炭素原子数１乃至６のアルキレン基、例として、炭素原子数２乃至３
のアルキレン基を表す。指数ｎは、例として、０、１、２、３、４、５又は６を表す。 1,2,4-triazole metal deactivators include, for example:
formula

{Wherein, R ₁ and R ₂ are the same or different, and the alkyl group having 1 to 20 carbon atoms, an alkenyl group having a carbon number of 3 to 20, a cycloalkyl group having a carbon number of 5 to 12 carbon atoms 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 ring Or R ₁ and R ₂ are partial formulas

(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 represents 0 or an integer of 1 to 6. ) Represents a group represented by
Or _one of R ₁ and R ₂ is a partial formula

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

(Where
m represents 0 or 1, and when m is 0, A represents a group represented by the formula (II). When m is 1, A represents an alkylene group or an arylene group having 6 to 10 carbon atoms. And R ₅ represents a group represented by the formula (II). ) Represents a group represented by }.
R ₄ is, for example, an alkylene group having 1 to 6 carbon atoms, such as 2 to 3 carbon atoms.
Represents an alkylene group. The index n represents 0, 1, 2, 3, 4, 5 or 6 as an example.

Specific compounds of 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)-(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) triazole, 1- (or 4)-(1
'-Perhydroazepinomethyl) triazole, 1- (or 4)-[(2', 2 ''-dihydroxyethylaminomethyl)] 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-triazolylmethyl) ethanolamine and N, N, N ′, N′-tetra- (1- or 4-triazoly Rumethyl) ethylenediamine.

  In a preferred embodiment, 1,2,4-triazole (I) is 1- (di-isooctylaminomethyl) -1,2,4-triazole and 1- (di- (2-ethylhexyl) aminomethyl) -1 , 2,4-triazole. The present invention relates to a lubricating oil composition selected from the group consisting of 2,4-triazole.

  Benzotriazole metal deactivators are those disclosed, for example, in US Pat. Nos. 5,032,300 and 5,171,463.

（式中、
Ｒ₆は、炭素原子数１乃至１２のアルキル基を表し、
Ｒ₇は、炭素原子数１乃至１２のアルキル基、１個以上のＯ原子によって中断された炭
素原子数１乃至１２のアルキル基又は炭素原子数５乃至１２のシクロアルキル基を表し及び
Ｒ₈及びＲ₉は、水素原子又はメチル基を表す。）で表されるものである。 Benzotriazole metal deactivators include, for example:
formula

(Where
R ₆ represents an alkyl group having 1 to 12 carbon atoms,
R ₇ represents an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms interrupted by one or more O atoms, or a cycloalkyl group having 5 to 12 carbon atoms, and R ₈ and R ₉ represents a hydrogen atom or a methyl group. ).

Specific examples of the compound represented by the formula (III) include 1- (2-methoxyprop-2-yl) tolyltriazole, 1- (1-methoxyethyl) tolyltriazole, 1- (1-methoxypropyl) Tolyltriazole, 1- (1-isobutoxybutyl) tolyltriazole, 1- (1-tert-butoxybutyl) tolyltriazole, 1- (1-hexyloxybutyl) tolyltriazole, 1- (1-octyloxybutyl) tolyl Triazole, 1- (1-butoxy-2-methylpropyl) tolyltriazole, 1- (1-dodecyloxybutyl) tolyltriazole, 1- (1-isopropyloxyethyl) tolyltriazole, 1- (1-isopropyloxypropyl) Tolyltriazole, 1- (1-isopropyloxybutyl) tolyl Riazole, 1- (1-cyclohexyloxypropyl) tolyltriazole, 1- (1-cyclohexyloxyheptyl) tolyltriazole, 1- (1-cyclohexyloxybutyl) tolyltriazole, 1- [1- (2-methoxyethoxy) butyl ] Tolyltriazole and 1- [1- (2-ethoxyethoxy) butyl] tolyltriazole.

  In a preferred embodiment, benzotriazole (III) is 1- (2-methoxyprop-2-yl) tolyltriazole, 1- (1-cyclohexyloxypropyl) tolyltriazole, 1- (1-cyclohexyloxyheptyl) tolyltriazole And a lubricating oil composition selected from the group consisting of 1- (1-cyclohexyloxybutyl) tolyltriazole.

である。 (1- (2-methoxyprop-2-yl) tolyltriazole is

It is.

である。 1- (1-cyclohexyloxyheptyl) tolyltriazole is

It is.

  Benzotriazole metal deactivators are those disclosed, for example, in US Pat. No. 6,410,490.

｛式中、
Ｒ₁₀は、水素原子又は炭素原子数１乃至１２のアルキル基を表し、及び
Ｒ₁₁及びＲ₁₂は同一又は相違し、そして炭素原子数１乃至２０のアルキル基、
炭素原子数３乃至２０のアルケニル基、炭素原子数５乃至１２のシクロアルキル基、炭素原子数７乃至１３のアラルキル基又は炭素原子数６乃至１０のアリール基を表し、又はＲ₁₁とＲ₁₂は、それぞれが結合している窒素原子と一緒になって、５、６又は７員の複素環を形成しても良く、又はＲ₁₁とＲ₁₂は部分式

（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乃至２０のアルキル基を表し、
Ｒ₄は、炭素原子数１乃至１２のアルキレン基を表し、
ｎは、０又は１乃至６の整数を表す。）で表される基を表し、
又はＲ₁₁及びＲ₁₂の一方は部分式

で表される基を表すか、
又はＲ₁₂は式（ＩＩ）で表される基を表し、そしてＲ₁₁は部分式

（式中、
ｍは、０又は１を表し、ｍが０の場合、Ａは式（ＩＩ）で表される基を表し、そしてｍが１の場合、Ａはアルキレン基又は炭素原子数６乃至１０アリーレン基を表し、及びＲ₅
は式（ＩＩ）で表される基を表す。）で表される基を表す。｝で表されるものである。
Ｒ₄は、例えば、炭素原子数１乃至６のアルキレン基、例として、炭素原子数２乃至３
のアルキレン基を表す。指数ｎは、例として、０、１、２、３、４、５又は６を表す。 Benzotriazole metal deactivators include, for example:
formula

{Where,
R ₁₀ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and R ₁₁ and R ₁₂ are the same or different, and the alkyl group of 1 to 20 carbon atoms,
Represents an alkenyl group having 3 to 20 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, or an aryl group having 6 to 10 carbon atoms, or R ₁₁ and R ₁₂ are , Together with the nitrogen atom to which they are attached, may form a 5, 6 or 7 membered heterocycle, or R ₁₁ and R ₁₂ may be a partial formula

(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 represents 0 or an integer of 1 to 6. ) Represents a group represented by
Or one of R ₁₁ and R ₁₂ is a partial formula

Or a group represented by
Or R ₁₂ represents a group represented by formula (II), and R ₁₁ represents a partial formula

(Where
m represents 0 or 1, when m is 0, A represents a group represented by the formula (II), and when m is 1, A represents an alkylene group or an arylene group having 6 to 10 carbon atoms. And R ₅
Represents a group represented by the formula (II). ) Represents a group represented by }.
R ₄ is, for example, an alkylene group having 1 to 6 carbon atoms, as an example, a carbon atom number of 2 to 3
Represents an alkylene group. The index n represents 0, 1, 2, 3, 4, 5 or 6 as an example.

The benzotriazole metal deactivator of formula (IV) is, for example, as described in US Pat. No. 4,701,273, which reacts benzotriazole with formaldehyde and amines. Prepared by known methods. Preferably, R ₁₀ is a hydrogen atom or a methyl group.

A preferred embodiment relates to a lubricating oil composition wherein the benzotriazole (IV) is 1- [bis- (2-ethylhexyl) aminomethyl-4-methyl] benzotriazole.

  The triazole metal deactivator is present from about 0.01 to about 0.03%, based on the weight of the lubricating oil. By way of example, the triazole is present from about 0.02 to about 0.2 weight percent or from about 0.03 to about 0.1 weight percent, based on the weight of the lubricating oil.

  The boric acid ester compound is disclosed in, for example, US Pat. Nos. 6,008,165 and 6,010,986.

（式中、
Ｒ₁₅は、独立して水素原子、炭素原子数１乃至２０のアルキル基、炭素原子数３乃至２０のアルケニル基、炭素原子数５乃至１２のシクロアルキル基、炭素原子数７乃至１３のアラルキル基または炭素原子数６乃至１９のアリール基を表す、但し、少なくとも１つのＲ₁₅基は水素原子ではない。）で表されるものである。 The borate ester is, for example, the formula (R ₁₅ O) ₃ B or

(Where
R ₁₅ is independently a hydrogen atom, 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 an aralkyl group having 7 to 13 carbon atoms. Or an aryl group having 6 to 19 carbon atoms, provided that at least one R ₁₅ group is not a hydrogen atom. ).

R ₁₅ represents, for example, an alkyl group having 4 to 16 carbon atoms. By way of example, all three R ₁₅ groups represent alkyl groups.

  In a preferred embodiment, the borate ester is triethyl borate, tripropyl borate, triisopropyl borate, tributyl borate, triphenyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate, triiso-borate. The present invention relates to a lubricating oil composition selected from the group consisting of octyl, tridecyl borate, triborate (alkyl having 8 to 10 carbon atoms), triborate (alkyl having 12 to 15 carbon atoms) and oleyl borate. .

  The borate ester is present from about 0.02 to about 1.0 weight percent, based on the weight of the lubricating oil. By way of example, the borate ester may be from about 0.03 to about 0.9%, from about 0.04 to about 0.7%, or from about 0.05 to about 0.5, based on the weight of the lubricating oil. Mass% present.

  Alkyl groups are straight or branched chains, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, n-pentyl, n-hexyl. Group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group or n-eicosyl group It is a group.

  An alkenyl group is a straight chain or branched chain, for example, a prop-2-enyl group, a but-2-enyl group, a 2-methyl-prop-2-enyl group, a pent-2-enyl group , A hexa-2,4-dienyl group, a dodece-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.

When R ₁ and R ₂ are combined with the nitrogen atom to form a heterocyclic group, the heterocyclic group is, for example, a morpholine, pyrrolidine, piperidine or perhydroazepine ring.

The alkylene moiety is, for example, a methylene group, an ethylene group, 1: 2- or 1: 3-propylene group, 1: 4-butylene group, 1: 6-hexylene group, 1: 8-octylene group, 1: 10-
Includes a decylene group and a 1: 12-dodecylene group.

  The arylene moiety includes, for example, a phenylene group or a naphthylene group.

（式中、
Ｒ₂₇は、水素原子、未置換の又は１個以上の炭素原子数１乃至６のアルコキシ基により置換された炭素原子数１乃至２５の直鎖状の又は枝分れ鎖状のアルキル基、飽和の非環式基又は脂環式基、又はアリール基を表す；Ｒ₂₈は、未置換の又は１個以上の炭素原子数１乃至６のアルコキシ基により置換された炭素原子数１乃至２５の直鎖状の又は枝分れ鎖状のアルキル基、飽和の非環式基又は脂環式基、又はアリール基を表す；
Ｒ₂₉は、水素原子、炭素原子数１乃至２５の直鎖状の又は枝分れ鎖状のアルキル基、飽和の又は不飽和の非環式基又は脂環式基、又はアリール基を表す；及び
Ｒ₃₀及びＲ₃₁は、それぞれ他とは独立に、炭素原子数１乃至２５の直鎖状の又は枝分れ鎖状のアルキル基、飽和の又は不飽和の非環式基又は脂環式基、又はアリール基を表す。） Component d) amine phosphates are, by way of example, salts containing amines and mixed mono- and diacid phosphates. Mono- and diacid phosphates have the following structural formula:

(Where
R ₂₇ represents a hydrogen atom, a linear or branched alkyl group having 1 to 25 carbon atoms which is unsubstituted or substituted by one or more alkoxy groups having 1 to 6 carbon atoms, saturated Represents an acyclic group, an alicyclic group, or an aryl group; R ₂₈ is a straight chain having 1 to 25 carbon atoms that is unsubstituted or substituted by one or more alkoxy groups having 1 to 6 carbon atoms; Represents a chain or branched chain alkyl group, a saturated acyclic or alicyclic group, or an aryl group;
R ₂₉ represents a hydrogen atom, a linear or branched alkyl group having 1 to 25 carbon atoms, a saturated or unsaturated acyclic or alicyclic group, or an aryl group; And R ₃₀ and R ₃₁ are each independently a linear or branched alkyl group having 1 to 25 carbon atoms, a saturated or unsaturated acyclic group or alicyclic group. Represents a group or an aryl group. )

In a preferred embodiment, R ₂₇ and R ₂₈ represent a linear or branched alkyl group having 1 to 12 carbon atoms; and R ₂₉ , R ₃₀ and R ₃₁ represent a linear or branched carbon atom number. The present invention relates to a lubricating oil composition representing 1 to 18 alkyl groups.

（式中、
Ｒ₃₃はｎ−ヘキシル基を表し、Ｒ₃₄は炭素原子数１１乃至１４の枝分かれしたアルキル基を表し、そしてｘ＝１の場合、ｙ＝２であり；ｘ＝２の場合、ｙ＝１である。）で表されるものであるところの潤滑油組成物に関する。 In a further preferred embodiment, the amine phosphate is
formula

(Where
R ₃₃ represents an n-hexyl group, R ₃₄ represents a branched alkyl group having 11 to 14 carbon atoms, and when x = 1, y = 2; when x = 2, y = 1 is there. It is related with the lubricating oil composition which is what is represented by this.

  The amine phosphate is present from about 0.02 to about 0.50% by weight, based on the weight of the lubricating oil. For example, the amine phosphate is present from about 0.03 to about 0.4 weight percent based on the weight of the lubricating oil.

  The lubricating oil may further contain a viscosity index improver. Examples of suitable viscosity index improvers are polyacrylates, polymethacrylates, vinyl pyrrolidone / methacrylate copolymers, polyvinyl pyrrolidone, polybutenes, olefin copolymers, styrene / acrylate copolymers and polyethers. .

The lubricating oil may further comprise any of an ashless dispersant, a cleaning agent and / or an antiwear system, a ZnDTP, an ashless phosphorus compound, or an antiwear additive in which no phosphorus is used.

（式中、
Ｒ及びＲ’は独立して炭素原子数１乃至２０のアルキル基、炭素原子数３乃至２０のアルケニル基、炭素原子数５乃至１２のシクロアルキル基、炭素原子数７乃至１３のアラルキル基又は炭素原子数６乃至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乃至１２のアルキル基を表す。）として表される；及び
２）硫化オレフィンや植物油、リン酸トリトリル、リン酸トリクレシル、塩素化パラフィン、アルキル及びアリールジ及びトリ硫化物、リン酸モノ及びジアルキルのアミン塩、メチルホスホン酸アミン塩、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］プロピオン酸塩、トリフェニルチオリン酸塩（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のような硫黄及び／又はリン及び／又はハロゲン原子を含む化合物、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−オキサイドのドデシルアミン塩、トリチオリン酸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−ベンゾチアゾール又は５−オクチルジチオカルバミン酸エトキシカルボニルのような２−メルカプトベンゾチアゾール誘導体
から成る群から選ばれる。 Antiwear additives are
1) Metal salt of dihydrocarbyl dithiophosphate (metal is aluminum, lead, tin, manganese, cobalt, nickel or copper, but in most cases zinc). Zinc salt (zinc dialkyldithiophosphate)

(Where
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, an aralkyl group having 7 to 13 carbon atoms, or carbon. Represents an aryl group having 6 to 10 atoms, for example, R and R ′ independently represent an alkyl group having 1 to 12 carbon atoms; And 2) sulfurized olefins and vegetable oils, tolyl phosphate, tricresyl phosphate, chlorinated paraffins, alkyl and aryl di and trisulfides, mono and dialkyl phosphates, methylphosphonates, diethanolamino Methyltolyltriazole, di (2-ethyl-hexyl) -aminomethyltolyltriazole, 2,5-dimercapto-1,3,4-thiadiazole derivative, ethyl [(bisisopropyloxyphosphinothioyl) thio] propionate, Compounds containing sulfur and / or phosphorus and / or halogen atoms such as triphenylthiophosphate (triphenylphosphorothioate), tris (alkylphenyl) phosphorothioate and mixtures thereof, for example tris (isononylphenyl) phospho Thioate, diphenylmonononylphenyl phosphorothioate, isobutylphenyl diphenyl phosphorothioate, 3-hydroxy-1,3-thiaphosphetane 3-oxide dodecylamine salt, trithiophosphate 5,5,5-tris (isooctyl 2-acetate), 1- (N , N-bis (2-ethylhexyl) aminomethyl) -2-mercapto-1H-1,3-benzothiazole or a 2-mercaptobenzothiazole derivative such as ethoxycarbonyl 5-octyldithiocarbamate.

Suitable dispersants are
1) Mannich base, which is the condensation reaction product of aldehydes such as high molecular weight phenols, alkylene polyamides and formaldehyde;
2) A succinic acid-based dispersant which is a reaction product of an olefin polymer and a succinic acylating agent (acid, anhydride, ester or halide), further reacted with an organic hydroxy compound and / or an amine. And 3) selected from the group consisting of reaction products of high molecular weight amides and esters, such as hydrocarbyl acylating agents, and polyhydric aliphatic alcohols such as glycerol, pentaerythritol or sorbitol.

Ashless (metal-free) polymeric materials that usually contain an oil-soluble high molecular weight backbone combined with polar functional groups associated with the particles to be dispersed are typically used as dispersants. In general, the hydrocarbon backbone materials used are olefin polymers and copolymers, in particular ethylene, propylene, butylene, isobutylene, styrene; with or without further functional groups incorporated into the polymer backbone. Polar materials such as amines, alcohols, amides or esters are
It is bound to the skeleton via a bridge.

  Detergents are calcium, magnesium, barium, sodium, or lithium salts of organic acids such as sulfonates, alkylphenates, sulfurized alkylphenolates, carboxylates, salicylates, phosphonates, thiophosphonates and phosphinic acids Selected from the group consisting of salt. The salt may be neutral or may be overbased with, for example, a metal hydroxide or carbonate.

The subject of the present invention is also a lubricating oil additive composition, the composition comprising b) a triazole metal deactivator;
c) a borate ester; and a dispersant.

  Suitable dispersants are those known for use in lubricating oils, such as polyisobutenyl succinimide, polybutenyl phosphonic acid derivatives, or copolymers of vinyl acetate and fumarate esters.

  For example, a suitable dispersant is an amine or alcohol product of a succinic acylating agent substituted with a hydrocarbyl group. The dispersant is in particular polyisobutenyl succinimide. For example, as disclosed in US Pat. Nos. 5,112,507, 6,440,905, 5,587,432, and references cited therein. Dispersant.

  The weight to mass ratio of triazole metal deactivator to borate is from about 1:10 to about 10: 1, for example, from about 1: 7 to about 7: 1, from about 1: 5 to about 5: 1. About 1: 3 to about 3: 1. For example, the mass: mass ratio of triazole metal deactivator to borate ester is from about 1: 2 to about 1: 5 or from about 1: 2 to about 1: 4.

  The weight of dispersant used in the additive composition is from about 1% to about 50% based on the total weight of the triazole metal deactivator and borate ester. By way of example, the weight of dispersant in the additive composition may be about 2% to about 30%, about 3% to about 25%, or about 4 based on the total weight of triazole metal deactivator and borate ester. % To about 20%.

  By way of example, a typical additive composition is about 5% dispersant, about 25% triazole metal deactivator and about 70% borate ester each by weight.

For corrosion bench tests: C.I. M Cusano and J.M. C. One, corrosion of diesel and copper containing lead by diesel lubricant, Soc. Tribologists and
See Lubrication Engineers, 51 (1) 89-95, 1994; and ASTM D 5968 and D 6594. This test is commonly used in engine oil standards to demonstrate the ability of lubricants to protect against copper and lead corrosion.

<Example 1>
The following formulations were prepared in a 5W-30 SM type passenger car motor oil containing 0.05% phosphorus and friction modifier in API Group II base oil. Ingredients were specified in mass% based on the total formulation.

The borate ester is (R ₁₅ O) ₃ B, where R ₁₅ is 5 to 1 carbon atoms mixed.
Represents an alkyl group of 3; Borate is used at 60 ppm and 120 ppm B treatment levels. Triazole metal deactivator A is 1- (di- (2-ethylhexyl) -aminomethyl) -1,2,4-triazole. Triazole metal deactivator B is methyl-1- (di- (2-ethylhexyl) -aminomethyl) -benzotriazole.

  The hot corrosion bench test was performed according to ASTM D 6594 (135 ° C. for 168 hours). The corrosion results are as follows in ppm increase by mass.

<Example 2>
The additive mixture was mixed with 5 wt% succinimide dispersant, HITEC 646, 25 wt% 1- (di-2-ethylhexyl) aminomethyl) -1,2,4-triazole and 70 wt% borate ester (R ₁₅ O) ₃ B (wherein R ₁₅ represents 5 to 13 carbon atoms mixed)
Represents an alkyl group. ) Together. The mixture was blended into a polyalkylene glycol industrial oil.

  The following results are shown below for zinc corrosion in polyalkylene glycol (PAG). The corrosion result is ppm of Zn obtained after 30 minutes at 125 ° C.

Claims (10)

a) lubricating oil;
b) a triazole metal deactivator;
c) boric acid esters; and optionally d) amine phosphates;
A lubricating oil composition comprising:
The triazole metal deactivator has the formula

{Wherein R ₁ and R ₂ are the same or different, and 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, and the number of carbon atoms 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 ring; Or R ₁ and R ₂ may be partial formulas

(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 represents 0 or an integer of 1 to 6. ) Represents a group represented by
Or _one of R ₁ and R ₂ is a partial formula

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

(Where
m represents 0 or 1, when m is 0, A represents a group represented by the formula (II), and when m is 1, A represents an alkylene group or an arylene group having 6 to 10 carbon atoms. And R ₅
Represents a group represented by the formula (II). ) Represents a group represented by }, Or the triazole metal deactivator is represented by the formula (III)

(Where
R ₆ represents an alkyl group having 1 to 12 carbon atoms,
R ₇ represents an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms interrupted by one or more O atoms, or a cycloalkyl group having 5 to 12 carbon atoms, and R ₈ and R ₉ represents a hydrogen atom or a methyl group. Benzotriazole represented by:
Or the triazole metal deactivator has the formula (IV)

{Where,
R ₁₀ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and R ₁₁ and R ₁₂ are the same or different, and the alkyl group of 1 to 20 carbon atoms,
Represents an alkenyl group having 3 to 20 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, or an aryl group having 6 to 10 carbon atoms, or R ₁₁ and R ₁₂ are , Together with the nitrogen atom to which they are attached, may form a 5, 6 or 7 membered heterocycle, or R ₁₁ and R ₁₂ may be a partial formula

(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 represents 0 or an integer of 1 to 6. ) Represents a group represented by
Or one of R ₁₁ and R ₁₂ is a partial formula

Or a group represented by
Or R ₁₂ represents a group represented by formula (II), and R ₁₁ represents a partial formula

(Where
m represents 0 or 1, when m is 0, A represents a group represented by the formula (II), and when m is 1, A represents an alkylene group or an arylene group having 6 to 10 carbon atoms. And R ₅
Represents a group represented by the formula (II). ) Represents a group represented by } The composition which is a benzotriazole represented by this.   The 1,2,4-triazole (I) includes 1- (di-isooctylaminomethyl) -1,2,4-triazole and 1- (di- (2-ethylhexyl) aminomethyl) -1,2, The lubricating oil composition of claim 1, selected from the group consisting of 4-triazoles.   The benzotriazole (III) includes 1- (2-methoxyprop-2-yl) tolyltriazole, 1- (1-cyclohexyloxypropyl) tolyltriazole, 1- (1-cyclohexyloxyheptyl) tolyltriazole and 1- ( The lubricating oil composition according to claim 1, selected from the group consisting of (1-cyclohexyloxybutyl) tolyltriazole.   The lubricating oil composition according to claim 1, wherein the benzotriazole (IV) is 1- [bis- (2-ethylhexyl) aminomethyl-4-methyl] benzotriazole. The borate ester has the formula (R ₁₅ O) ₃ B or

(Where
R ₁₅ is independently a hydrogen atom, 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 an aralkyl group having 7 to 13 carbon atoms. Or an aryl group having 6 to 19 carbon atoms, provided that at least one R ₁₅ group is not a hydrogen atom. The lubricating oil composition according to claim 1, which is represented by:   The borate ester is triethyl borate, tripropyl borate, triisopropyl borate, tributyl borate, triphenyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate, triisooctyl borate, boric acid 6. A lubricating oil composition according to claim 5, selected from the group consisting of tridecyl, triborate (alkyl of 8 to 10 carbon atoms), triborate (alkyl of 12 to 15 carbon atoms) and oleyl borate. formula

(Where
R ₂₇ represents a hydrogen atom, a linear or branched alkyl group having 1 to 25 carbon atoms which is unsubstituted or substituted by one or more alkoxy groups having 1 to 6 carbon atoms, saturated R ₂₈ represents an unsubstituted or alicyclic group or an aryl group; R ₂₈ is a straight chain having 1 to 25 carbon atoms which is unsubstituted or substituted by one or more alkoxy groups having 1 to 6 carbon atoms; Represents a chain- or branched-chain alkyl group, a saturated acyclic or alicyclic group, or an aryl group;
R ₂₉ represents a hydrogen atom, a linear or branched alkyl group having 1 to 25 carbon atoms, a saturated or unsaturated acyclic or alicyclic group, or an aryl group; And R ₃₀ and R ₃₁ are each independently a linear or branched alkyl group having 1 to 25 carbon atoms, a saturated or unsaturated acyclic group or alicyclic group. Represents a group or an aryl group. The lubricating oil composition according to claim 1, comprising a mono- or diacid phosphate amine represented by R ₂₇ and R ₂₈ represent a linear or branched alkyl group having 1 to 12 carbon atoms, and R ₂₉ , R ₃₀ and R ₃₁ represent a linear or branched alkyl group having 1 to 18 carbon atoms. The lubricating oil composition according to claim 7, which represents a group. The amine phosphate has the formula

(Where
R ₃₃ represents an n-hexyl group, R ₃₄ represents a branched alkyl group having 11 to 14 carbon atoms, and when x = 1, y = 2; when x = 2, y = 1 is there. The lubricating oil composition according to claim 7, which is represented by: A method for inhibiting corrosion of lead, copper, iron and zinc in a lubricating oil, wherein b) a triazole metal deactivator;
c) boric acid ester; and optionally d) formulating a phosphate amine.