JP2011149031A - Transmission lubricating composition with improved performance, containing acid-polyamine condensation product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide compositions with improved friction resistance, improved anti-shudder properties, and the appropriate friction properties, and compositions suitable for use in a variety of automatic transmission fluids. <P>SOLUTION: The lubricating composition comprises: (a) hydrocarbyl phosphite; (b) the condensation product of at least one fatty acid with a polyamine; (c) a boric acid ester; (d) a borate dispersant; and (e) an oil of lubricating viscosity. The composition has improved anti-shudder properties and the appropriate friction properties. Furthermore, the composition is suitable for use in a variety of automatic transmission fluids. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

(Field of Invention)
The present invention relates to an oil of lubricating viscosity containing a condensation product of a polyamine and an acid, hydrocarbyl phosphite and a boron-containing compound. This composition has improved wear performance. This composition can be used in automatic transmission fluids.

(Background of the Invention)
Various additives to oils with lubricating viscosity for automatic transmission fluid (hereinafter referred to as ATF) to improve wear resistance, to reduce shudder resistance and to provide suitable friction properties It is known to add. The friction characteristics of the ATF must be balanced to provide high dynamic torque for efficient clutch engagement performance and high static friction for good clutch retention. The ATF must also provide a positive friction versus speed curve for good shudder resistance. These competing requirements are difficult to balance. In addition, the wear resistance must be sufficient for the durability of the gear.

  In an attempt to overcome these challenges, automakers have defined specifications; for example, The Ford Motor Company has a MER-CON® V specification. These specifications highlight a number of tests that ATF and other lubricating oil compositions should meet. Important tests include “Ford / Greening Low Speed Friction Test”, “Timken Abrasion Test” and “Ford Clutch Friction Durability Test” in order for ATF to meet wear requirements, reduce shudder resistance and have suitable friction properties. ". Many known lubricating oil compositions for ATF systems pass one or two of the tests specified above. In view of the future prospects of automakers, it is desirable to have a composition that can pass all three of the tests specified above.

  U.S. Pat. No. 6,482,777 discloses a lubricating composition for a transmission package, which includes at least one saturated fatty phosphate ester or salt, and optionally at least one. Either a fatty acid imidazoline or a reaction product of a fatty acid and a polyalkylene polyamine and / or a borate dispersant, wherein the lubricating composition is free of saturated fat phosphite. This composition has improved friction properties and, if necessary, improved thermal stability.

  US Pat. No. 5,759,965 discloses the formulation of boron-containing overbased materials, borate epoxides, borate dispersants, various phosphorus-containing acid esters and their derivatives with oils of lubricating viscosity. ing.

  US Pat. No. 6,528,458 describes the formulation of 2,5-dimercapto-1,3,4-thiadiazole, imidazoline, borate epoxides and short chain phosphites (and borate dispersants in different examples). Disclosure.

US Pat. No. 6,103,673 describes at least 0.1% by weight of overbased metal salt (which contributes to a total base number (TBN) of 0.5-10 of the composition), at least 0. Formulation of 1 wt% phosphorus-containing compound, 0.1-0.25 wt% friction modifier (this is a zinc salt of a fatty acid having at least 10 carbon atoms, at least 12 carbons in its hydrocarbyl group A composition containing a hydrocarbyl imidazoline containing an atom and a borate epoxide is disclosed.
US Patent Application No. 2002/0151441 discloses an automatic transmission fluid containing at least 0.1% by weight of a metal detergent, a dispersant, a mixture of at least two friction modifiers and a base oil. This composition exhibits anti-shudder properties and friction durability.

US Pat. No. 6,482,777 US Pat. No. 5,759,965 US Pat. No. 6,528,458 US Pat. No. 6,103,673

  It would be desirable to have a composition with improved rub resistance. The present invention further provides compositions having anti-shudder properties and suitable friction properties. The present invention further provides compositions suitable for use in various automatic transmission fluids.

(Summary of the Invention)
The present invention provides a composition comprising:
(A) hydrocarbyl phosphite;
(B) a condensation product of a fatty acid and a polyamine;
(C) boric acid ester;
(D) a borate dispersant; and (e) an oil of lubricating viscosity.

The present invention further provides a method of preparing a composition, the method comprising mixing the following:
(A) hydrocarbyl phosphite;
(B) a condensation product of a fatty acid and a polyamine;
(C) boric acid ester;
(D) a borate dispersant; and (e) an oil of lubricating viscosity.

により表わされ、
ここで、Ｒ ^１ およびＲ ^２ の少なくとも一方は、ヒドロカルビル基であり、そしてＲ ^１ およびＲ ^２ の他方は、水素またはヒドロカルビル基であり得、ここで、該亜リン酸ヒドロカルビルは、少なくとも１２個の炭素原子を有するヒドロカルビル基を含有する、
組成物。
（項目３）
項目１に記載の組成物であって、前記脂肪酸とポリアミンとの縮合生成物が、（ａ）式：

により表わされるヒドロカルビルイミダゾリンまたは（ｂ）式：

により現れるヒドロカルビルアミド、またはそれらの混合物を含有し、
（ａ）において、Ｒ ^７ は、１０個またはそれ以上の炭素原子を含有するヒドロカルビル基であり；そしてＲ ^８ は、水素、ヒドロカルビル基または置換ヒドロカルビル基であり；
（ｂ）において、Ｒ ^９ は、１０個またはそれ以上の炭素原子を含有するヒドロカルビル基であり、そしてＲ ^１０ は、水素、ヒドロカルビル基または置換ヒドロカルビル基である、組成物。
（項目４）
前記ホウ酸エステルが、ホウ素化合物と、エポキシ化合物、アルコールおよびそれらの混合物から選択される少なくとも１種の化合物とを反応させることより調製される、項目１に記載の組成物。
（項目５）
項目４に記載の組成物であって、該組成物はさらに、式：

により表わされる任意のホウ酸エステルを含有し、
ここで、Ｒ ^１１ 、Ｒ ^１２ およびＲ ^１３ は、全て、１個〜８個の炭素原子を含有するヒドロカルビル基であるが、但し、Ｒ ^１１ 、Ｒ ^１２ およびＲ ^１３ 中の全炭素原子数は、４個またはそれ以上であり、さらに、但し、該任意のホウ酸エステルは、成分（ｃ）のホウ酸エステルよりも少なくとも２個少ない炭素原子を含有する、
組成物。
（項目６）
前記ホウ酸塩分散剤が、Ｎ−置換長鎖アルケニルスクシンイミドから誘導される、項目１に記載の組成物。
（項目７）
前記潤滑粘性のあるオイルが、ＡＰＩ 第ＩＩ族、第ＩＩＩ族、第ＩＶ族のオイルおよびそれらの混合物からなる群から選択される、項目１に記載の組成物。
（項目８）
項目１に記載の組成物であって、（ａ）前記亜リン酸ヒドロカルビルが、該組成物の０．０１重量％〜５重量％で存在しており；（ｂ）前記脂肪酸とポリアミンとの縮合生成物が、該組成物の０．０１重量％〜３重量％で存在しており；（ｃ）前記ホウ酸エステルが、該組成物の０．０１重量％〜３重量％で存在しており；（ｄ）前記ホウ酸塩分散剤が、該組成物の０．０３重量％〜６重量％で存在しており；そして（ｅ）前記潤滑粘性のあるオイルが、該組成物の７８重量％〜９９．９重量％で存在している、組成物。
（項目９）
前記潤滑粘性のあるオイルが、濃縮物を形成するために、５０重量％未満の量で存在している、項目１に記載の組成物。
（項目１０）
組成物を調製するための方法であって、該方法は、以下：
（ａ）亜リン酸ヒドロカルビル；
（ｂ）脂肪酸とポリアミンとの縮合生成物；
（ｃ）ホウ酸エステル；
（ｄ）ホウ酸塩分散剤；および
（ｅ）潤滑粘性のあるオイル
を混合する工程を包含する、方法。
（項目１１）
伝動装置を潤滑させるための方法であって、該伝動装置に、項目１に記載の組成物を含有する潤滑剤を供給する工程を包含する、方法。 The present invention further provides a composition having suitable friction durability with improved wear resistance and anti-shudder properties. The present invention further provides compositions (particularly automatic transmission fluids) that are suitable for use in various transmissions.
For example, the present invention provides the following items:
(Item 1)
Less than:
(A) hydrocarbyl phosphite, wherein the hydrocarbyl group contains at least 8 carbon atoms;
(B) a condensation product of a fatty acid and a polyamine;
(C) boric acid ester;
(D) a borate dispersant; and
(E) Oil with lubricating viscosity
A composition comprising:
(Item 2)
The composition of item 1, wherein the hydrocarbyl phosphite is of the formula:

Represented by
Wherein at least one of R ¹ and R ² is a hydrocarbyl group and the other of R ¹ and R ² can be hydrogen or a hydrocarbyl group, wherein the hydrocarbyl phosphite comprises at least 12 Containing a hydrocarbyl group having carbon atoms,
Composition.
(Item 3)
Item 2. The composition according to Item 1, wherein the condensation product of the fatty acid and the polyamine is represented by the formula (a):

Or a hydrocarbyl imidazoline represented by formula (b):

Containing hydrocarbyl amide, or a mixture thereof,
In (a), R ⁷ is a hydrocarbyl group containing 10 or more carbon atoms; and R ⁸ is hydrogen, a hydrocarbyl group or a substituted hydrocarbyl group;
In (b), a composition wherein R ⁹ is a hydrocarbyl group containing 10 or more carbon atoms and R ¹⁰ is hydrogen, a hydrocarbyl group or a substituted hydrocarbyl group.
(Item 4)
Item 2. The composition according to Item 1, wherein the borate ester is prepared by reacting a boron compound with at least one compound selected from an epoxy compound, an alcohol, and a mixture thereof.
(Item 5)
Item 5. The composition of item 4, wherein the composition further comprises a formula:

Containing any borate ester represented by
Here, R ¹¹ , R ¹² and R ¹³ are all hydrocarbyl groups containing 1 to 8 carbon atoms, provided that the total number of carbon atoms in R ¹¹ , R ¹² and R ¹³ is 4 or more, provided that the optional borate ester contains at least 2 fewer carbon atoms than the borate ester of component (c),
Composition.
(Item 6)
The composition of claim 1, wherein the borate dispersant is derived from an N-substituted long chain alkenyl succinimide.
(Item 7)
Item 2. The composition of item 1, wherein the oil of lubricating viscosity is selected from the group consisting of API Group II, Group III, Group IV oils and mixtures thereof.
(Item 8)
2. The composition of item 1, wherein (a) the hydrocarbyl phosphite is present at 0.01% to 5% by weight of the composition; (b) condensation of the fatty acid with a polyamine. The product is present at 0.01% to 3% by weight of the composition; (c) the borate ester is present at 0.01% to 3% by weight of the composition (D) the borate dispersant is present at 0.03% to 6% by weight of the composition; and (e) the oil of lubricating viscosity is from 78% to A composition, present at 99.9% by weight.
(Item 9)
A composition according to item 1, wherein the oil of lubricating viscosity is present in an amount of less than 50% by weight to form a concentrate.
(Item 10)
A method for preparing a composition comprising the following:
(A) hydrocarbyl phosphite;
(B) a condensation product of a fatty acid and a polyamine;
(C) boric acid ester;
(D) a borate dispersant; and
(E) Oil with lubricating viscosity
A process comprising:
(Item 11)
A method for lubricating a transmission device, comprising the step of supplying the transmission device with a lubricant containing the composition according to item 1.

(Detailed description of the invention)
As used herein, the term “hydrocarbyl substituent” or “hydrocarbyl group” is used in its ordinary sense, which is well known to those skilled in the art. Specifically, it means a group having a carbon atom bonded directly to the rest of the molecule and having predominantly hydrocarbon character. Examples of hydrocarbyl groups include the following:
Hydrocarbon substituents, ie aliphatic substituents (eg alkyl or alkenyl), alicyclic substituents (eg cycloalkyl, cycloalkenyl), and aromatic substituted aromatic substituents, aliphatic substituted Not only aromatic substituents and alicyclic substituted aromatic substituents, but also cyclic substituents. Here, the ring is completed by other parts of the molecule (eg, two substituents together form a ring);
Substituted hydrocarbon substituents, ie, substituents containing non-hydrocarbon groups. This non-hydrocarbon group does not change the predominantly hydrocarbon nature of the substituent in the context of the present invention (eg, halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkyl mercapto, nitro, nitroso, And sulfoxy);
Hetero substituents, ie, substitutions that have non-carbon atoms present in the ring or chain while remaining predominantly hydrocarbon in nature, but otherwise consist of carbon atoms Group. Heteroatoms include sulfur, oxygen, nitrogen and include substituents such as pyridyl, furyl, thienyl and imidazolyl. Generally, in this hydrocarbyl group, there are no more than 2 non-hydrocarbon substituents, preferably no more than 1 non-hydrocarbon substituent, for each 10 carbon atoms. Typically, there are no such non-hydrocarbon substituents in the hydrocarbyl group.

The present invention provides a composition comprising:
(A) hydrocarbyl phosphite;
(B) a condensation product of at least one fatty acid and a polyamine;
(C) boric acid ester;
(D) a borate dispersant; and (e) an oil of lubricating viscosity.

(Hydrocarbyl phosphite)
The hydrocarbyl phosphite of the present invention can be represented by the following formula:

ここで、Ｒ^１およびＲ^２の少なくとも一方は、少なくとも８個の炭素原子を含有するヒドロカルビル基であり、そして他方は、水素またはヒドロカルビル基であり得る；好ましくは、Ｒ^１およびＲ^２の両方は、ヒドロカルビル基である。このヒドロカルビル基は、アルキル、シクロアルキル、アリール、非環式またはそれらの混合物であり得る。このヒドロカルビル基は、８個〜４０個、好ましくは、１０個〜約３５個、さらに好ましくは、１２個〜３０個、さらにより好ましくは、１３個〜２５個、さらにより好ましくは、１４個〜２０個の炭素原子を有するアルキルであり得る。

Wherein at least one of R ¹ and R ² is a hydrocarbyl group containing at least 8 carbon atoms, and the other can be hydrogen or a hydrocarbyl group; preferably, both R ¹ and R ² are , A hydrocarbyl group. The hydrocarbyl group can be alkyl, cycloalkyl, aryl, acyclic or mixtures thereof. The hydrocarbyl group has from 8 to 40, preferably from 10 to about 35, more preferably from 12 to 30, even more preferably from 13 to 25, even more preferably from 14 to It can be an alkyl having 20 carbon atoms.

The alkyl group can be linear or branched, preferably linear, and can be saturated or unsaturated, preferably saturated. Suitable alkyl groups for R ¹ and R ² include octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, octadecenyl, nonodedecyl, eicosyl or their Mixing is mentioned. In one embodiment, R ¹ and R ² each have 16 to 18 carbon atoms.

  The hydrocarbyl phosphite is typically 0.01-5% by weight of the lubricating oil composition, preferably 0.03-1% by weight, more preferably 0.05-0.7% by weight. Even more preferably, it is present at 0.1-0.4% by weight.

(Condensation product of fatty acid and polyamine)
The condensation of the fatty acids of the present invention with polyamines typically forms at least one compound selected from hydrocarbyl amides, hydrocarbyl imidazolines and mixtures thereof. In one embodiment, these condensation products are hydrocarbyl imidazolines. In one embodiment, these condensation products are hydrocarbyl amides. In one embodiment, these condensation products are a mixture of hydrocarbyl imidazoline and hydrocarbyl amide. Preferably, these condensation products are a mixture of hydrocarbyl imidazoline and hydrocarbyl amide.

  The fatty acids of the present invention can be derived from hydrocarbyl carboxylic acids. The hydrocarbyl group can be alkyl, cycloalkyl or aryl, but alkyl is preferred, and these hydrocarbyl groups can be linear or branched. Typically, the fatty acid has 8 or more, preferably 10 or more, more preferably 13 or more, and even more preferably 14 or more carbon atoms (its carboxy Containing the carbon of the group). Typically, the fatty acid contains 8 to 30, preferably 12 to 24, and even more preferably 16 to 18 carbon atoms. Other suitable carboxylic acids may include polycarboxylic acids or carboxylic acids or anhydrides having 2 to 4 carbonyl groups, preferably 2 carbonyl groups. This polycarboxylic acid includes succinic acid and its anhydride, and Diels of unsaturated monocarboxylic acid and unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid) Mention may be made of Alder reaction products. Preferably, the fatty carboxylic acid is a fatty monocarboxylic acid containing 8 to 30, preferably 10 to 26, and even more preferably 12 to 24 carbon atoms.

  Examples of suitable fatty acids can include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, eicosic acid and tall oil acid, which can be used alone or in others. It can be used in combination with fatty acids.

  The polyamines of the present invention can be acyclic or cyclic, preferably acyclic; they can also be linear or branched, preferably linear.

  In one embodiment, the polyamine can be an alkylene polyamine, which is selected from the group consisting of ethylene polyamine, propylene polyamine, butylene polyamine, and mixtures thereof. Examples of propylene polyamines include propylene diamine and dipropylene triamine.

  Particularly preferred ethylenepolyamines are ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N- (2-aminoethyl) -N ′-[2-[(2-aminoethyl) amino] ethyl]- It is selected from the group consisting of 1,2-ethanediamine, polyamine still bottoms and mixtures thereof.

  In one embodiment, the polyamine can be an α, β-diaminoalkane. Suitable α, β-diaminoalkanes can include diaminopropane, diaminobutane or mixtures thereof. Specific diaminoalkanes include N- (2-aminoethyl) -1,3-propanediamine, 3,3′-diamino-N-methyldipropylamine, tris (2-aminoethyl) amine, N, N-bis. It is selected from the group consisting of (3-aminopropyl) -1,3-propanediamine, N, N′-1,2-ethanediylbis- (1,3-propanediamine) and mixtures thereof.

  In one embodiment, other polyamines can include di- (trimethylene) triamine, piperazine, diaminocyclohexane, and mixtures thereof.

  In one embodiment, the polyamine can be cyclic, which can include, but is not limited to, compounds represented by the following formula:

ここで、Ｒ^３は、結合して単核環または多核環を形成する原子を含有する炭素環基または複素環基を表わす；そして該原子は、炭素、酸素、窒素、リンおよびそれらの混合からなる群から選択される。好ましくは、Ｒ^３は、炭素、酸素、窒素およびそれらの混合からなる群から選択される原子であり得る。

Wherein R ³ represents a carbocyclic or heterocyclic group containing atoms that combine to form a mononuclear or polynuclear ring; and the atoms are from carbon, oxygen, nitrogen, phosphorus and mixtures thereof Selected from the group consisting of Preferably, R ³ can be an atom selected from the group consisting of carbon, oxygen, nitrogen and mixtures thereof.

This mononuclear ring structure typically contains 5 to 8, preferably 6 to 7 atoms. This polynuclear cyclic structure contains 8 to 16, preferably 10 to 12 atoms. In formula (II), R ³ can contain 4 to 15, preferably 5 to 11, more preferably 5 to 8 atoms. The cyclic ring can be aromatic, non-aromatic or a mixture thereof, but non-aromatic is preferred.

R ⁴ can be a hydrocarbyl group, typically an alkyl or alkenyl group containing 1-8, preferably 1-6, and even more preferably 2-5 carbon atoms. It can be. The alkyl or alkenyl group can be substituted, unsubstituted, branched, unbranched alkylaryl, cycloalkyl, or a mixture thereof. Suitable examples of R ⁴ can include ethyl, propyl, butyl, and pentyl. Preferably R ⁴ is ethyl, propyl or mixtures thereof.

R ⁵ and R ⁶ can be hydrogen or hydrocarbyl; preferably at least one of R ⁵ and R ⁶ , and even more preferably, both are hydrogen. When R ⁵ and ^{R 6} are hydrocarbyl, the number of carbon atoms present in each of ^{R 5} and ^{R 6,} independently, one to eight, preferably in the range from 1 to five range, further More preferably, it is in the range of 1 to 3. Suitable examples of hydrocarbyl groups include methyl, ethyl, propyl, butyl and pentyl.

  Examples of suitable cyclic polyamines include 4- (3-aminopropyl) morpholine, 4- (3-aminoethyl) morpholine or mixtures thereof. Preferably, the cyclic amine is 4- (3-aminopropyl) morpholine, which can be used alone or in combination with other polyamines.

  Typically, the hydrocarbyl imidazoline formed from the condensation product of a fatty acid and a polyamine can be represented by the following formula:

ここで、Ｒ^７は、ヒドロカルビル基、好ましくは、直鎖または分枝アルキル基、好ましくは、直鎖であり得る；また、このヒドロカルビル基は、飽和または不飽和、好ましくは、飽和であり得る。典型的には、ヒドロカルビル基Ｒ^７は、８個またはそれ以上、好ましくは、１１個またはそれ以上、好ましくは、１４個またはそれ以上、さらに好ましくは、１６個またはそれ以上の炭素原子を含有できる。例えば、このヒドロカルビル基は、１０個〜３０個、好ましくは、１２個〜２４個、さらに好ましくは、１６個〜１８個の炭素原子を含有できる。１実施態様では、このヒドロカルビル基は、１７個の炭素原子を含有する。Ｒ^８は、ヒドロカルビル基または置換ヒドロカルビル基であり得る。１実施態様では、Ｒ^８は、上述のアルキレンポリアミンから誘導される。

Here, R ⁷ can be a hydrocarbyl group, preferably a linear or branched alkyl group, preferably a straight chain; and the hydrocarbyl group can be saturated or unsaturated, preferably saturated. Typically, the hydrocarbyl group R ⁷ may contain 8 or more, preferably 11 or more, preferably 14 or more, more preferably 16 or more carbon atoms. . For example, the hydrocarbyl group can contain 10 to 30, preferably 12 to 24, and more preferably 16 to 18 carbon atoms. In one embodiment, the hydrocarbyl group contains 17 carbon atoms. R ⁸ can be a hydrocarbyl group or a substituted hydrocarbyl group. In one embodiment, R ⁸ is derived from an alkylene polyamine as described above.

  Typically, the hydrocarbyl amide formed from the condensation product of a fatty acid and a polyamine can be represented by the following formula:

ここで、Ｒ^９は、上記Ｒ^７について定義した形式のヒドロカルビル基であり得る。Ｒ^１０は、水素、ヒドロカルビル基または置換ヒドロカルビル基であり得る。１実施態様では、Ｒ^１０は、上述のアルキレンポリアミンから誘導される。

Here, R ⁹ can be a hydrocarbyl group of the type defined for R ⁷ above. R ¹⁰ can be hydrogen, a hydrocarbyl group or a substituted hydrocarbyl group. In one embodiment, R ¹⁰ is derived from an alkylene polyamine as described above.

  The condensation product of the fatty acid and polyamine is typically 0.01 to 3% by weight of the lubricating oil composition, preferably 0.03 to 1% by weight, more preferably 0.05 to 0%. .6% by weight, even more preferably 0.07-0.3% by weight.

(Borate ester)
The present invention further contains a borate ester. The borate ester can be prepared by reacting a boron compound with at least one compound selected from an epoxy compound, a halohydrin compound, an epihalohydrin compound, an alcohol, and a mixture thereof. Typically, these alcohols include monohydric alcohols, dihydric alcohols, trihydric alcohols or higher alcohols. Hereinafter, when referring to “at least one compound selected from epoxy compounds, halohydrin compounds, epihalohydrin compounds, alcohols and mixtures thereof”, “epoxy compounds or equivalents” are used.

Boron compounds suitable for preparing this borate ester include various forms, which include boric acid (metaboric acid HBO ₂ , orthoboric acid H ₃ BO ₃ and tetraboric acid H ₂ B ₄ O ₇ . Selected from the group consisting of boron oxide, boron trioxide and alkyl borate. The borate ester can also be prepared from a boron halide.

  A borate ester formed by reaction of a boron compound with an epoxy compound or equivalent can be represented by at least one selected from:

ここで、Ｒ^１１、Ｒ^１２およびＲ^１３は、水素またはヒドロカルビル基であり得るが、但し、Ｒ^１１、Ｒ^１２およびＲ^１３の少なくとも１個、好ましくは、少なくとも２個は、ヒドロカルビル基である。１実施態様では、Ｒ^１１は、ヒドロカルビル基である；そしてＲ^１２およびＲ^１３は、水素である。１実施態様では、Ｒ^１１およびＲ^１２は、ヒドロカルビル基であり、そしてＲ^１３は、水素である。１実施態様では、Ｒ^１１、Ｒ^１２およびＲ^１３は、全て、ヒドロカルビル基である。これらのヒドロカルビル基は、任意の２個の隣接するＲ基が環内で連結されているとき、アルキル、アリールまたはシクロアルキルであり得る。アルキルのとき、この基は、飽和または不飽和であり得、不飽和が好ましい。１実施態様では、このヒドロカルビル基は、環式である。１実施態様では、これらのヒドロカルビル基は、アルキルおよびシクロアルキルの混合である。

Here, R ¹¹ , R ¹² and R ¹³ may be hydrogen or a hydrocarbyl group provided that at least one, preferably at least two of R ¹¹ , R ¹² and R ¹³ are hydrocarbyl groups. In one embodiment, R ¹¹ is a hydrocarbyl group; and R ¹² and R ¹³ are hydrogen. In one embodiment, R ¹¹ and R ¹² are hydrocarbyl groups and R ¹³ is hydrogen. In one embodiment, R ¹¹ , R ¹² and R ¹³ are all hydrocarbyl groups. These hydrocarbyl groups can be alkyl, aryl or cycloalkyl when any two adjacent R groups are linked in the ring. When alkyl, the group can be saturated or unsaturated, with unsaturation being preferred. In one embodiment, the hydrocarbyl group is cyclic. In one embodiment, these hydrocarbyl groups are a mixture of alkyl and cycloalkyl.

Typically, there is no upper limit on the number of carbon atoms, but a practical limit is 500, preferably 400, more preferably 200, even more preferably 100 or 60. It is a piece. For example, the number of carbon atoms present in R ¹¹ , R ¹² and R ¹³ is 1 to 60, preferably 1 to 40, more preferably 1 to 30 carbon atoms. Provided that the total number of carbon atoms in R ¹¹ , R ¹² and R ¹³ is 9 or more, preferably 10 or more, more preferably 12 or more, or 14 or more. It is.

In one embodiment, R ¹¹ , R ¹² and R ¹³ are all hydrocarbyl groups containing 1 to 30 carbon atoms, provided that the total number of carbon atoms in R ¹¹ , R ¹² and R ¹³ is , 9 or more.

R ^{14 to} R ²⁰ (including them) can be hydrogen or a hydrocarbyl group, provided that at least one of R ^{14 to} R ¹⁷ and / or R ^{18 to} R ²⁰ is a hydrocarbyl group. R ^{21 to} R ²⁶ (including them) are hydrocarbyl groups or hydrogen, but are preferably hydrocarbyl groups; and R ²⁷ can be hydrogen or hydrocarbyl groups, but hydrogen is preferred. The definition of the hydrocarbyl group for R ^{14 to} R ²⁷ (including them) is the same as the definition shown for R ¹¹ , R ¹² and R ¹³ .

Examples of suitable groups for R ^{11 to} R ²⁷ (including them) include isopropyl, n-butyl, isobutyl, amyl, 2-pentenyl, 4-methyl-2-pentyl, 2-ethyl-1-hexyl, Examples include 2-ethylhexyl, heptyl, isooctyl, nonyl, decyl, undecyl, dodecenyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl groups.

  Epoxy compounds useful for preparing the borate esters of the present invention can be represented by the following formula:

ここで、Ｒ^２８は、８個〜３０個、好ましくは、１０個〜２６個、さらにより好ましくは、１２個〜２２個の炭素原子を含有するアルキル鎖であり得る；Ｒ^２９は、水素、または１個〜４個、好ましくは、１個〜２個の炭素原子を含有するアルキル鎖であり得、さらにより好ましくは、Ｒ^２９は、水素である；そしてＴは、水素またはハロゲン、すなわち、塩素、臭素、ヨウ素またはフッ素、またはそれらの混合物であり得るが、塩素が好ましい。さらにより好ましくは、Ｔは、水素である。Ｔがハロゲンであるとき、本発明のエポキシ化合物は、エピクロロヒドリン化合物である。

Wherein R ²⁸ may be an alkyl chain containing 8 to 30, preferably 10 to 26, and even more preferably 12 to 22 carbon atoms; R ²⁹ is hydrogen, Or may be an alkyl chain containing 1 to 4, preferably 1 to 2 carbon atoms, even more preferably R ²⁹ is hydrogen; and T is hydrogen or halogen, ie Although it can be chlorine, bromine, iodine or fluorine, or a mixture thereof, chlorine is preferred. Even more preferably, T is hydrogen. When T is halogen, the epoxy compound of the present invention is an epichlorohydrin compound.

In one embodiment, the epoxy compounds of the present invention include C ₁₄ -C ₁₆ epoxides or commercial mixtures of C ₁₄ -C ₁₈ epoxides. In one embodiment, the epoxy compound of the present invention is purified. Examples of suitable purified epoxy compounds include 1,2-epoxydecane, 1,2-epoxyundecane, 1,2-epoxydodecane, 1,2-epoxytridecane, 1,2-epoxybutadecane, 1,2, Mention may be made of epoxypentadecane, 1,2-epoxyhexadecane, 1,2-epoxyheptadecane, 1,2-epoxyoctadecane, 1,2-epoxynonadecane and 1,2-epoxyicosane. Preferably, the purified epoxy compound includes 1,2-epoxytetradecane, 1,2-epoxypentadecane, 1,2-epoxyhexadecane, 1,2-epoxyheptadecane, 1,2-epoxyoctadecane; Is 1,2-epoxy-hexadecane.

  Another group of compounds described in “epoxy compounds or equivalents” are alcohols, which include monohydric alcohols, dihydric alcohols, trihydric alcohols, higher alcohols (ie, 4 or Alcohols containing more hydroxyl groups) and mixtures thereof, and monohydric alcohols are preferred. Typically, these alcohol compounds contain 2 to 30, more preferably 4 to 26, and even more preferably 6 to 20 carbon atoms. These alcohol compounds can include glycerol compounds (eg, glycerol monooleate).

  These borate esters can be obtained by mixing the boron compound with an epoxy compound or equivalent and bringing them to an appropriate temperature (typically 80 ° C. to 250 ° C., more preferably until the desired reaction occurs). , 90 ° C to 240 ° C or 100 ° C to 230 ° C). The molar ratio of the boron compound to the epoxy compound or equivalent is typically 4: 1 to 1: 4, preferably 1: 1 to 1: 3, more preferably about 1: 2. In carrying out this reaction, an inert liquid can be used. This liquid can be, for example, toluene, xylene, chlorobenzene, dimethylformamide and mixtures thereof. Water is formed and is typically distilled off during the reaction. Alkaline reagents can be used to catalyze this reaction.

  The boric acid ester is typically 0.01 to 3% by weight of the lubricating oil composition, preferably 0.03 to 1% by weight, more preferably 0.05 to 0.6% by weight, Even more preferably, it is present at 0.07 to 0.3% by weight.

In one embodiment, any borate ester may be present in the present invention in addition to the borate ester. The optional borate ester is such that R ¹¹ , R ¹² and R ¹³ all contain from 1 to 8, preferably from 2 to 7, even more preferably from 3 to 6 carbon atoms. Is derived from formula (V) except that the total number of carbon atoms of R ¹¹ , R ¹² and R ¹³ is 4 or more, preferably 6 or more, Even more preferably, there are 8 or more, provided that this optional borate ester is at least 2 fewer carbon atoms, preferably at least 3 less than the borate ester of component (c) It contains carbon atoms, more preferably at least 4 fewer carbon atoms, even more preferably at least 5 fewer carbon atoms.

  Suitable examples of this optional borate ester include tripropyl borate, tributyl borate, tripentyl borate, trihexyl borate, triheptyl borate, trioctyl borate, trinonyl borate and tridecyl borate.

  In one embodiment, the optional borate ester is selected from the group consisting of tributyl borate, tri-2-ethylhexyl borate, and mixtures thereof. In one embodiment, the optional borate ester is tributyl borate. In one embodiment, the optional borate ester is tri-2-ethylhexyl borate.

  The optional borate ester, when present, is typically 0-5% by weight of the lubricating oil composition, preferably 0.01-3%, more preferably 0.05- It is present at 1.5% by weight, even more preferably from 0.1 to 0.7% by weight.

  The total amount of boric acid ester and any boric acid ester is typically 0.01-8% by weight of the lubricating oil composition, preferably 0.04-4%, more preferably 0.1 to 2.1% by weight, even more preferably 0.17 to 1% by weight.

(Borate dispersant)
The present invention further contains a borate dispersant, which is typically derived from an N-substituted long chain alkenyl succinimide. These N-substituted long chain alkenyl succinimides have various chemical structures and two exemplary formulas include the following:

ここで、各Ｒ^３０は、別個に、アルキル基、頻繁には、３５０〜５０００、好ましくは、５００〜３０００の分子量を有するポリイソブチル基であり、そしてＲ^３１は、アルキレン基、通例、エチレン（Ｃ_２Ｈ_４）基である。各Ｒ^３０はまた、追加スクシンイミド官能基で置換でき、そして種々の連鎖により、そのスクシンイミド構造に結合できる。繰り返し単位数「ｘ」は、１〜２０、好ましくは、１〜１５、さらにより好ましくは、１〜１０であり得る。

Wherein each R ³⁰ is independently an alkyl group, frequently a polyisobutyl group having a molecular weight of 350 to 5000, preferably 500 to 3000, and R ³¹ is an alkylene group, typically ethylene ( C ₂ H ₄ ) group. Each R ³⁰ can also be substituted with an additional succinimide functional group and can be attached to its succinimide structure by various linkages. The number of repeating units “x” may be 1-20, preferably 1-15, and even more preferably 1-10.

The N-substituted long chain alkenyl succinimides are borated using various reagents, which are prepared in various forms of boric acid (metaboric acid HBO ₂ , orthoboric acid H ₃ BO ₃ and tetraboric acid H ₂ B _4. including O _7), boron oxide is selected from the group consisting of boron trioxide and boric acid alkyl. These reagents are described in more detail above. In one embodiment, the boration reagent is boric acid, which can be used alone or in combination with other boration reagents.

  The borate dispersant is prepared by mixing the boron compound with an N-substituted long chain alkenyl succinimide and bringing them to a suitable temperature (typically 80 ° C. to 250 ° C., and further until the desired reaction occurs. Preferably, it can be prepared by heating at 90 ° C to 230 ° C, and still more preferably 100 ° C to 210 ° C. The molar ratio of the boron compound to the N-substituted long chain alkenyl succinimide is typically 10: 1 to 1: 4, preferably 4: 1 to 1: 3, and even more preferably 1: 2. is there. In carrying out this reaction, an inert liquid can be used. This liquid can include, but is not limited to, toluene, xylene, chlorobenzene, dimethylformamide, and mixtures thereof.

  The borate dispersant is typically 0.03 to 6% by weight of the lubricating oil composition, preferably 0.06 to 3%, more preferably 0.15 to 2%, More preferably, it is present at 0.3-1.5% by weight.

(Oil with lubricating viscosity)
The lubricating oil composition of the present invention can be added to oil having lubricating viscosity. The oils include natural and synthetic oils, hydrocracked, hydrogenated, hydrofinished oils, unrefined oils, refined oils and rerefined oils, or mixtures thereof.

  Unrefined oil is oil that is obtained directly from natural or synthetic raw materials, generally without further purification (or almost no purification).

  Refined oils are similar to unrefined oils, except that they have been further processed in one or more purification stages to improve one or more properties. Purification techniques are known in the art and include solvent extraction, secondary distillation, acid or base extraction, filtration, permeation and the like.

  Rerefined oils are also known as reclaimed oils or reprocessed oils, and are produced by a process similar to that used to obtain refined oils, and consumed additives and cracking of oils It is often further processed by the method instructed to remove the object.

  Natural oils useful in producing the lubricants of the present invention include animal and vegetable oils (eg, castor oil, lard oil), mineral lubricating oils (eg, liquid petroleum oils, and paraffinic, naphthenic or Mixed paraffin-naphthenic type and solvent-treated mineral or acid-treated mineral lubricants, oils derived from coal or shale or mixtures thereof).

  Synthetic lubricating oils are useful, including hydrocarbon oils such as polymerized olefins and interpolymerized olefins (eg, polybutylene, polypropylene, propylene-isobutylene copolymers); poly (1- Hexene), poly (1-octene), poly (1-decene) and mixtures thereof; alkylbenzenes (eg, dodecylbenzene, tetradecylbenzene, dinonylbenzene, di- (2-ethylhexyl) -benzene, etc.); polyphenyl (Eg, biphenyl, terphenyl, alkylated polyphenyl); alkylated diphenyl ethers and alkylated diphenyl sulfides, and derivatives, analogs and homologues thereof, or mixtures thereof.

  Other synthetic lubricating oils include, but are not limited to, liquid esters of phosphorus-containing acids (eg, tricresyl phosphate, trioctyl phosphate and diethyl ester of decanophosphonic acid), polymerized tetrahydrofuran, and the like. Synthetic oils can be produced by a Fischer-Tropsch reaction and typically can be hydroisomerized Fischer-Tropsch hydrocarbons or waxes.

  Oils of lubricating viscosity can also be defined as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. The five base oil groups are as follows: Group I (sulfur content> 0.03% by weight, and / or <90% by weight saturates, viscosity index 80-120); Group II (sulfur content) ≦ 0.03% by weight, and ≧ 90% by weight saturates, viscosity index 80-120); Group III (sulfur content ≦ 0.03% by weight, and ≧ 90% by weight saturates, viscosity index ≧ 120) Group IV (all polyalphaolefins (PAOs)); and Group V (all others not included in Groups I, II, III, or IV). The oil of lubricating viscosity is selected from the group consisting of API Group I, Group II, Group III, Group IV, Group V and mixtures thereof. Preferably the oil of lubricating viscosity is API Group II, Group III, Group IV or mixtures thereof.

  The oil of lubricating viscosity is from 78 to 99.9%, preferably from 89% to 99.8%, more preferably from 93.6 to 99.7% by weight of the lubricating oil composition, More preferably, it is present in the range of 96.3 to 99.3% by weight.

(Performance additive)
This lubricating oil composition can contain other performance additives, which are metal deactivators, detergents, dispersants, antioxidants, antiwear agents, corrosion inhibitors, scuffing agents, extreme pressure agents. Selected from the group consisting of antifoaming agents, demulsifiers, friction modifiers, viscosity modifiers, pour point depressants and seal swell agents. Typically, a well-formulated lubricating oil will contain one or more of these additives.

  The total amount of any additives present is 0-10% by weight of the lubricating oil composition, preferably 0.1-7% by weight, more preferably 0.2-5% by weight, More preferably, it may be 1 to 5% by weight.

(Metal deactivator)
Metal deactivators can be used to neutralize the catalytic effects of metals that promote oxidation in lubricating oils. Examples of metal deactivators include benzotriazole, benzimidazole, 2-alkyldithiobenzoimidazole, 2-alkyldithiobenzotriazole, 2- (N, N-dialkyl-dithiocarbamoyl) benzotriazole, 2,5-bis Listed are derivatives of (alkyl-dithio) -1,3,4-thiadiazole, 2,5-bis (N, N-dialkyldithiocarbamoyl) -1,3,4-thiadiazole and 2-alkyldithio-5-mercaptothiadiazole be able to.

  Preferably, the metal deactivator is a hydrocarbyl substituted benzotriazole compound. Benzotriazole compounds having a hydrocarbyl substituent include at least one of the following ring positions: 1- or 2- or 4- or 5- or 6- or 7-. The hydrocarbyl group contains 1 to 30, preferably 1 to 15, more preferably 1 to 7 carbon atoms, even more preferably the metal deactivator is 5 -Methylbenzotriazole (tolyltriazole).

(Dispersant)
Dispersants other than the borate dispersants of the present invention can also be added. These are often ashless because they do not contain ash-forming metals prior to mixing with the lubricating oil composition and do not contribute to any ash-forming metals when added to lubricants and polymeric dispersants. Known as a dispersant. Ashless type dispersants are characterized by polar groups attached to relatively high molecular weight hydrocarbon chains. Typical ashless dispersants include N-substituted long chain alkenyl succinimides. Examples of N-substituted long chain alkenyl succinimides include polyisobutylene succinimide having a number average molecular weight of 350 to 5000, preferably 500 to 3000. Succinimide dispersants and their preparation are disclosed, for example, in US Pat. No. 4,234,435. This polyisobutylene succinimide can be used alone or in combination with other dispersants.

  In one embodiment, the present invention further contains at least one dispersant derived from polyisobutylene, an amine and zinc oxide to form a polyisobutylene succinimide complex with zinc. This polyisobutylene succinimide complex with zinc can be used alone or in combination with other dispersants.

  Another type of ashless dispersant is Mannich base. Mannich dispersants are reaction products of alkylphenols whose alkyl groups contain at least 30 carbon atoms with aldehydes (especially formaldehyde) and amines (especially polyalkylene polyamines).

  The dispersant can also be worked up in the usual way by reaction with various optional reagents. These include urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehyde, ketone, carboxylic acid, hydrocarbon-substituted succinic anhydride, maleic anhydride, nitrile, epoxide, boron compounds and phosphorus compounds.

(Cleaning agent)
Detergents are known and include alkali metals, alkaline earth metals and transition metals and one or more hydrocarbyl sulfonic acids, carboxylic acids, phosphorus-containing acids, mono- and / or di-thiophosphoric acids. And neutral or overbased Newtonian or non-Newtonian basic salts with alkylphenols, sulfur-coupled alkylphenol compounds, salixarates, saligenin or mixtures thereof. Commonly used metals include sodium, potassium, calcium, magnesium, lithium or mixtures thereof. The most commonly used metals include sodium, magnesium and calcium. Detergents, particularly overbased detergents and their preparation are disclosed in US Pat. No. 3,629,109.

(Antiwear agent)
The lubricating oil composition may further contain an antiwear agent. Useful antiwear agents include zinc hydrocarbyl dithiophosphates, phosphate esters or salts thereof; phosphites; and phosphorus-containing carboxylic esters, ethers and amides, or mixtures thereof. Examples of suitable hydrocarbyl dithiophosphate zinc compounds include zinc isopropylmethylamyl dithiophosphate, zinc isopropyl isooctyl dithiophosphate, barium di (nonyl) -dithiophosphate, zinc di (cyclohexyl) dithiophosphate, calcium di (hexyl) dithiophosphate, Mention may be made of zinc isobutylisoamyldithiophosphate, zinc isopropyl n-butyldithiophosphate, primary amyl isobutyldithiophosphate, methylamyl dithiophosphate and isopropyl 2-ethylhexyl dithiophosphate.

(Antioxidant)
Antioxidants are known materials, including diphenylamine, hindered phenol, molybdenum dithiocarbamate and sulfurized olefins.

  The diphenylamine antioxidant can be represented by the following formula:

ここで、Ｒ^３２およびＲ^３３は、ヒドロカルビル基、好ましくは、アリールアルキルまたはアルキル基である。これらのアリールアルキル基は、６個〜２０個、好ましくは、６個〜１０個の炭素原子を含有する。このアルキル基は、直鎖または分枝であり得、好ましくは、直鎖であり得る；このアルキル基は、１個〜２４個、好ましくは、２個〜１８個、さらにより好ましくは、４個〜１２個の炭素原子を含有する；そしてｚは、別個に、０、１、２または３であるが、但し、少なくとも１個の芳香環は、ヒドロカルビル基を含有する。好ましいアルキル化ジフェニルアミンには、オクチルジフェニルアミン、ノニルジフェニルアミン、ビス−オクチルジフェニルアミンおよびビス−ノニルジフェニルアミンを挙げることができる。

Here, R ³² and R ³³ are hydrocarbyl groups, preferably arylalkyl or alkyl groups. These arylalkyl groups contain 6 to 20, preferably 6 to 10 carbon atoms. The alkyl group can be linear or branched, preferably linear; the alkyl group is 1-24, preferably 2-18, and even more preferably 4 Contains ˜12 carbon atoms; and z is independently 0, 1, 2, or 3, provided that at least one aromatic ring contains a hydrocarbyl group. Preferred alkylated diphenylamines include octyl diphenylamine, nonyl diphenylamine, bis-octyl diphenylamine and bis-nonyl diphenylamine.

  Sterically hindered phenols can be represented by the following formula:

ここで、Ｒ^３４およびＲ^３５は、別個に、１個〜２４個、好ましくは、４個〜１８個、さらにより好ましくは、４個〜１２の個炭素原子を含有する分枝または直鎖アルキル基である；そしてＥは、水素、ヒドロカルビル、第二芳香族基に連結している架橋基、またはそれらの混合である。

Wherein R ³⁴ and R ³⁵ are independently branched or straight chain alkyl containing 1 to 24, preferably 4 to 18, and even more preferably 4 to 12 carbon atoms. And E is hydrogen, hydrocarbyl, a bridging group linked to a second aromatic group, or a mixture thereof.

R ³⁴ and R ³⁵ can be either linear or branched; branched is preferred. Preferably, the phenol is substituted with butyl and contains two t-butyls. When the t-butyl group occupies the 2,6-position, the phenol is sterically hindered. Examples of suitable hydrocarbyl groups include 2-ethylhexyl, n-butyl and dodecyl groups. Examples of suitable bridging groups, -CH ₂ - (methylene bridge) and _{-CH 2} OCH 2 - (ether bridge) and the like.

  When present, sterically hindered cross-linked phenols other than component (a) can be represented by the following formula:

ここで、Ｒ^３６、Ｒ^３７、Ｒ^３８、Ｒ^３９、Ｒ^４０、Ｒ^４１は、直鎖または分枝のいずれかであり、そして４個〜１８個、好ましくは、４個〜１２個の炭素原子を含有する。好ましくは、このフェノールは、ブチルで置換されている。Ｒ^４２およびＲ^４３は、別個に、水素またはヒドロカルビルである；好ましくは、Ｒ^４２およびＲ^４３は、アリールアルキルまたはアルキル基である。Ｒ^４２およびＲ^４３のアルキル基は、直鎖または分枝であり得、直鎖が好ましい。Ｒ^４２およびＲ^４３は、好ましくは、パラ位置にある。これらのアリールアルキルまたはアルキル基は、典型的には、１個〜１５個、好ましくは、１個〜１０個、さらに好ましくは、１個〜５個の炭素原子を含有する。架橋基Ｙには、−ＣＨ_２−（メチレン架橋）または−ＣＨ_２ＯＣＨ_２−（エーテル架橋）を挙げることができる。

Where R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴¹ are either linear or branched and are 4-18, preferably 4-12 carbons. Contains atoms. Preferably, the phenol is substituted with butyl. R ⁴² and R ⁴³ are independently hydrogen or hydrocarbyl; preferably R ⁴² and R ⁴³ are an arylalkyl or an alkyl group. The alkyl groups of R ⁴² and R ⁴³ can be straight or branched, with straight chains being preferred. R ⁴² and R ⁴³ are preferably in the para position. These arylalkyl or alkyl groups typically contain 1 to 15, preferably 1 to 10, more preferably 1 to 5 carbon atoms. Examples of the bridging group Y include —CH ₂ — (methylene bridge) or —CH ₂ OCH ₂ — (ether bridge).

  Examples of methylene bridged sterically hindered phenols include 4,4'-methylenebis (6-tertiarybutyl o-cresol), 4,4'-methylenebis (2-tertiary amyl-o-cresol) ), 2,2′-methylenebis (4-methyl-6-tert-butylphenol) and 4,4′-methylene-bis (2,6-di-tert-butylphenol). In one embodiment, a sterically hindered phenol suitable for the present invention is a hindered ester represented by the formula:

ここで、Ｒ^４４およびＲ^４５は、３個〜２２個、好ましくは、３個〜１８個、さらに好ましくは、４個〜１２個の炭素原子を含有する直鎖または分枝アルキル基（これらは、置換または非置換であり得る）である。アルキル基の具体例には、ジ−第二級ブチルおよびトリ−第三級ブチルが挙げられる。Ｒ^４６は、ヒドロカルビルであり得る。適当な例には、２−エチルヘキシルまたはｎ−ブチルエステル、ドデシル、−ＣＨ_２ＣＨ_２ＣＯＯＨおよびそれらの混合物が挙げられる。

Here, R ⁴⁴ and R ⁴⁵ are straight or branched alkyl groups containing 3 to 22, preferably 3 to 18, more preferably 4 to 12 carbon atoms (these are Can be substituted or unsubstituted). Specific examples of alkyl groups include di-secondary butyl and tri-tertiary butyl. R ⁴⁶ can be hydrocarbyl. Suitable examples include 2-ethylhexyl or n-butyl ester, dodecyl, —CH ₂ CH ₂ COOH and mixtures thereof.

  Suitable examples of molybdenum dithiocarbamate include commercially available materials sold under the trade names such as: Vanlube 822 ™ and Molly-van ™ A (RT Vanderbilt Co., Ltd. And Adeka Sakura-Lube (TM) S-100 and S-165 and S-600 (Asahi Denka Kogyo Co., Ltd.).

  Examples of suitable olefins that can be sulfurized include propylene, isobutylene, pentene, hexane, heptene, octane, nonene, decene, undecene, dodecene, undecyl, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, octadecenene, nonodecene. (Nondecene), eicosene or mixtures thereof. In one embodiment, hexadecene, heptadecene, octadecene, octadecenene, nonodecene, eicosene or mixtures thereof, and their dimers, trimers and tetramers are particularly preferred olefins. Alternatively, the olefin can be a Diels-Alder adduct of a diene (eg, 1,3-butadiene) and an unsaturated ester (eg, butyl (meth) acrylate).

  Other types of sulfurized olefins include fatty acids and their esters. These fatty acids are often obtained from vegetable or animal oils; and typically contain from 4 to 22 carbon atoms. Examples of suitable fatty acids and their esters include triglycerides, oleic acid, linoleic acid, palmitoleic acid or mixtures thereof. Often these fatty acids are obtained from lard oil, tall oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil or mixtures thereof. In one embodiment, these fatty acids are mixed with olefins.

(Corrosion inhibitor)
Corrosion inhibitors include amine salts of carboxylic acids (eg octylamine octoate), dodecenyl succinic acid or anhydride and fatty acids (eg oleic acid) and polyamines (eg polyalkylene polyamines (eg triethylenetetramine)) And alkenyl succinic acid (wherein the alkenyl group contains 8 to 24 carbon atoms) and a half ester of an alcohol (eg, polyglycol).

(Anti-scuffing agent)
The lubricant may also contain an anti-scuffing agent. Anti-scuffing agents that reduce adhesive wear are often sulfur-containing compounds. Typically, these sulfur-containing compounds include organic sulfides and polysulfides such as benzyl disulfide, bis- (chlorobenzyl) disulfide, dibutyl tetrasulfide, di-tertiary butyl polysulfide, sulfurized sperm whale oil, oleic acid. Sulfurized methyl ester, sulfurized alkylphenol, sulfurized diterpene, sulfurized terpene, sulfurized Diels-Alder adduct, alkylsulfenyl N'N-dialkyldithiocarbamate), reaction product of polyamine and polybasic acid ester, 2,3-dibromopropoxy Chlorobutyl ester of isobutyric acid, acetoxymethyl ester of dialkyldithiocarbamic acid and acyloxyalkyl ether of xanthogenic acid and mixtures thereof.

(Extreme pressure agent)
Extreme pressure (EP) agents that are soluble in the oil include sulfur and chlorosulfur containing EP agents, chlorinated hydrocarbon EP agents, phosphorus EP agents and mixtures thereof. Examples of such EP agents include chlorinated waxes; organic sulfides and polysulfides (eg, benzyl disulfide, bis- (chlorobenzyl) disulfide, dibutyl tetrasulfide, sulfurized sperm oil, sulfurized methyl ester of oleic acid, sulfurized alkylphenol, Sulfurized diterpenes, sulfurized terpenes, sulfurized Diels-Alder adducts); phosphosulfurized hydrocarbons (eg, reaction products of phosphorous sulfide with turpentine oil or methyl oleate; phosphorous esters (eg, dihydrophosphite and phosphorous acid) Trihydrocarbons such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentyl phenyl phosphite; dipentyl phenyl phosphite, tridecyl phosphite, distearyl phosphite and phosphite polypropylene substitution Enols)), metal thiocarbamates (eg zinc dioctyldithiocarbamate) and barium heptylphenol diacid; zinc salts of phosphorodithioic acids; amine salts of alkyl and dialkylphosphoric acids (eg reaction of dialkyldithiophosphoric acids with flopylene oxide) Including the amine salt of the product); and mixtures thereof.

(Anti-foaming agent)
Anti-foaming agents are known and can include organic silicones such as polyacetates, dimethyl silicones, polysiloxanes, polyacrylates or mixtures thereof. Examples of antifoaming agents include ethyl polyacrylate, 2-ethylhexyl polyacrylate, and polyvinyl acetate.

(Demulsifier)
Demulsifiers are known and include propylene oxide, ethylene oxide, polyoxyalkylene alcohols, alkyl amines, amino alcohols, diamines and derivatives of polyamines, which in turn react with ethylene oxide or substituted ethylene oxide. It is done. Examples of the demulsifier include trialkyl phosphate, polyethylene glycol, polyethylene oxide, polypropylene oxide, and (ethylene oxide-propylene oxide) polymer.

(Pour point depressant)
Pour point depressants are known and include maleic anhydride-styrene copolymer esters, polymethacrylates; polyacrylates; polyacrylamides; condensation products of haloparaffin waxes and aromatic compounds; vinyl carboxylates. Polymers; and terpolymers of dialkyl fumarate, vinyl esters of fatty acids, ethylene-vinyl acetate copolymers, alkylphenol formaldehyde condensation resins, alkyl vinyl ethers and mixtures thereof.

(Friction modifier)
Friction modifiers are known and include fatty amines, esters (especially glycerol esters (eg glycerol monooleate, borated glycerol esters)), fatty phosphites, fatty acid amides, fatty epoxides, boric acid. Mention of chlorinated fatty epoxides, alkoxylated fatty amines, borated alkoxylated fatty amines, metal salts of fatty acids, sulfurized olefins, fatty imidazolines, condensation products of carboxylic acids with polyalkylene-polyamines, amine salts of alkyl phosphoric acids Can do.

(Viscosity modifier)
Viscosity modifiers are known and are typically polymeric materials, including styrene-butadiene rubber, ethylene-propylene copolymer, polyisobutylene, hydrogenated styrene-isoprene polymer, hydrogenated radicals. Examples include isoprene polymers, polymethacrylic acid esters, polyacrylic acid esters, polyalkylstyrenes, alkenylaryl conjugated diene copolymers, polyolefins, polyalkylmethacrylates, maleic anhydride-styrene copolymer esters, and mixtures thereof. .

  Some polymers can also be described as dispersant-viscosity modifiers (which are often referred to as DVMs) because they also exhibit dispersant properties. Typically, this type of polymer includes a polyolefin (eg, an ethylene-propylene copolymer functionalized with the reaction product of maleic anhydride and an amine). Another class of polymers is polymethacrylates functionalized with amines.

(Seal swelling agent)
Seal swelling agents are known and are typically esters, or low viscosity mineral oils having a high naphthalene or aromatic content. Esters can be derived from monobasic or polybasic acids and monoalcohols, or can be esters of polyols and monobasic esters. Typically these alcohols contain 8 to 13 carbon atoms. Suitable examples of mineral oil seal swelling agents include adipate, azelate and sebacate. Examples of suitable mineral oil seal swell agents include Exxon Necton-37 ™ (FN 1380) and Exxon Mineral Seal Oil ™ (FN 3200).

(Flow regulator)
Flow control agents are known and include Hydrocal-38 (a product identified as refined naphthenic oil), 40 Neutral naphthenic oil and low molecular weight poly-α-olefins (Ethylflo ™). 162).

(Method)
The present invention further provides a method of preparing a composition, the method comprising mixing the following:
(A) hydrocarbyl phosphite;
(B) a condensation product of at least one fatty acid and a polyamine;
(C) boric acid ester;
(D) a borate dispersant; and (e) an oil of lubricating viscosity.

  The mixing conditions are typically 15 ° C to 130 ° C, preferably 20 ° C to 120 ° C, even more preferably 25 ° C to 110 ° C; and 30 seconds to 48 hours, preferably 2 minutes to 24 ° C. Time, more preferably 5 minutes to 16 hours, even more preferably time in the range of 10 minutes to 5 hours; and 86 kPa to 266 kPa (650 mmHg to 2000 mmHg), preferably 92 kPa to 200 kPa (690 mmHg to 1500 mmHg), further More preferably, the pressure is 95 kPa to 133 kPa (715 mmHg to 1000 mmHg).

  This method includes a step of mixing the other performance additives as necessary. This optional performance additive can be added sequentially, separately or as a concentrate.

  If the present invention is in the form of a concentrate, the oil of lubricating viscosity is less than 78% by weight, preferably less than 65% by weight, more preferably less than 50% by weight, even more preferably 45% by weight. Present in less than the amount (which can be mixed with the additional oil to form, in whole or in part, the final lubricant), and the ratio of each of the above components to the diluent oil is on a weight basis. Typically, it is 80:20 to 10:90.

(Industrial use)
The compositions of the present invention are useful in transmissions (specifically, mechanical transmissions) and provide a method of lubricating a transmission, wherein the method includes a lubricant containing the composition. A step of supplying These transmissions are selected from the group consisting of automatic transmissions, manual transmissions, transaxles, gears, and tractor transmissions. Suitable gear applications can include both open and closed systems.

  In one embodiment, the compositions of the present invention are particularly useful in transmission oils for automatic transmissions. Use of this lubricating oil composition can improve one or more of wear resistance, anti-shudder properties and friction durability.

  The following examples illustrate the invention. These examples are not exhaustive and are not to be construed as limiting the scope of the invention.

Example 1
90% by weight API Group III Motiva Enterprise ™ 70N oil (3.04 mm ² s ⁻¹ (cSt) at 100 ° C.) and 10% by weight API Group II Neste ™ 120N oil (100 An oil of lubricating viscosity is prepared by blending at 5.0 ° C. with 5.07 mm ² s ⁻¹ (cSt)). To this oil, (a) a reaction product of boric acid and polyisobutylene succinimide 0.33% by weight; (b) a condensation product of a mixture of fatty acids having 16 to 18 carbon atoms and tetraethylenepentamine 0.15% by weight (based on its total composition); (c) 0.2% by weight of a mixture of dialkyl hydrogen phosphite C ₁₆ -C ₁₈ ; and (d) boric acid and 1,2-epoxyhexadecane 0.2% by weight of the reaction product is added. A number of other optional performance additives are added to the resulting mixture: (a) 2.25% by weight non-borate dispersant, (b) 2.2% by weight antioxidant, (c) 0 detergent. 0.03 wt%, (d) 0.04 wt% metal deactivator, (e) 0.3 wt% seal swell, (f) 55 ppm antifoam, and (g) 3.1 wt% diluent oil.

(Example 2)
This experimental procedure is the same as that of Example 1 except that 0.16% by weight of the reaction product of boric acid and polyisobutylene succinimide is added.

(Example 3)
This experimental procedure is the same as the method of Example 1 except that 8.8% by weight dispersant-viscosity modifier, 0.02% by weight pour point depressant and 0.11% by weight dibutyl hydrogen phosphite are added. It is.

Example 4
This experimental procedure is the same as the method of Example 2, except that 0.4% by weight of tributyl borate is added.

(Test 1: Ford / Greening low speed friction test)
Approximately 300 mL of sample is placed in a modified SAE Number 2 device (which has a variable speed drive) and the sample is rotated at approximately 300 rpm for approximately 30 minutes. See Ford Motor Company MERCON® V specification for Automatic Transmission Fluid (January 1, 1999) for a more detailed description of this study. The maximum wear recommended for this test is 0.076 mm. The results obtained are as follows:

（試験２：Ｔｉｍｋｅｎ摩耗試験）
この方法は、Ｔｉｍｋｅｎ（商標） Ｌｕｂｒｉｃａｎｔ Ｔｅｓｔｅｒにより、自動変速機油の耐摩耗特性を決定するのに使用し、これには、試料ホルダーを取り付け、約１８０ｍｌの試験油を充填し、そして８００ｒｐｍで、４．０８ｋｇ（９．０ｌｂ）の負荷で、１５０℃で操作する。このＴｉｍｋｅｎ装置の回転シャフトにＦａｌｅｘ（商標）試験リングを装着する。長方形試験ブロックを、その小試料アダプタ内にしっかりと保持し、そして試験潤滑剤に十分に浸し、次いで、回転しているリングと接触させる。得られた結果は、以下である：

(Test 2: Timken abrasion test)
This method is used by the Timken ™ Lubricant Tester to determine the wear resistance characteristics of an automatic transmission fluid, which is fitted with a sample holder, filled with about 180 ml of test oil, and 4 at 800 rpm. Operate at 150 ° C. with a load of 0.08 kg (9.0 lb). A Falex ™ test ring is mounted on the rotating shaft of the Timken device. The rectangular test block is held firmly in its small sample adapter and is fully immersed in the test lubricant and then brought into contact with the rotating ring. The results obtained are as follows:

（試験３：Ｆｏｒｄクラッチ摩擦耐久性試験）
約３００ｍＬの試料を、改良型ＳＡＥ Ｎｕｍｂｅｒ ２装置（これには、ＳＤ−１７７７摩擦材料クラッチプレートおよびＣ８ＡＰ−７Ｂ４４２−Ａセパレータープレート材料を備え付けている）に入れる。このクラッチプレートおよびセパレータープレートを、２０，０００回にわたって、噛み合わせ、次いで、外す。この試験のさらに詳細な説明は、Ｆｏｒｄ Ｍｏｔｏｒ Ｃｏｍｐａｎｙ ＭＥＲＣＯＮ（登録商標）Ｖ ｓｐｅｃｉｆｉｃａｔｉｏｎ ｆｏｒ Ａｕｔｏｍａｔｉｃ Ｔｒａｎｓｍｉｓｓｉｏｎ Ｆｌｕｉｄ（１９９９年１月１日）を参照せよ。この試験で推奨される最大摩耗は、０．０７６ｍｍである。得られた結果は、以下である：

(Test 3: Ford clutch friction durability test)
Approximately 300 mL of sample is placed in a modified SAE Number 2 device (which is equipped with an SD-1777 friction material clutch plate and a C8AP-7B442-A separator plate material). The clutch plate and separator plate are engaged and then removed 20,000 times. See Ford Motor Company MERCON® V specification for Automatic Transmission Fluid (January 1, 1999) for a more detailed description of this study. The maximum wear recommended for this test is 0.076 mm. The results obtained are as follows:

この分析から、本発明の組成物は、種々の自動変速機油試験に対して良好な結果を生じることが分かる。試験３の実施例２では、値がある程度高い；この値は、ホウ酸塩分散剤の量を増やすことにより、著しく低くできると考えられる。

From this analysis, it can be seen that the compositions of the present invention give good results for various automatic transmission fluid tests. In Example 2 of Test 3, the value is somewhat high; it is believed that this value can be significantly lowered by increasing the amount of borate dispersant.

  The contents of each reference cited above are incorporated herein by reference. Except for the examples, unless otherwise indicated, all numerical quantities, reaction conditions, molecular weights, carbon atom numbers, etc. in this description that specify the amount of a substance are modified by the term “about”. I understand that Unless otherwise indicated, each chemical or composition referred to herein is considered to be present in its isomers, by-products, derivatives, and other such as would normally be found in commercial grade materials. It should be construed as a commercial grade material that can contain such materials. However, the amount of each chemical component is provided except for solvents or diluent oils that may typically be present in commercial grade materials unless otherwise indicated. Similarly, the range and amount of each element of the invention can be used in combination with the range or amount of any other element. It will be appreciated that the upper and lower amounts, ranges and ratios set forth herein may be combined separately. As used herein, the phrase “consisting essentially” may include substances that do not significantly affect the basic and novel properties of the composition in question.

Claims (1)

Invention described in the specification.