JP2007514040A - Lubricating composition containing succinimide dispersant - Google Patents

Abstract

The present invention provides a composition (a) a detergent package comprising: (i) a metal salixarate; and (ii) optionally a detergent other than component (a)(i); (b) a dispersant package comprising: (i) a dispersant with a carbonyl to nitrogen ratio of 1 or higher ; and (ii) a dispersant with a carbonyl to nitrogen ratio of less than 1; (c) an antioxidant package comprising: (i) a hindered phenol; and (d) an oil of lubricating viscosity, wherein the composition has a phosphorus content of less than or equal to 800 ppm; and wherein the sulphated ash content is less than or equal to 1.1 weight percent of the composition. The invention further provides a process for preparing the composition and its use.

Description

(Field of Invention)
The present invention relates to a lubricating oil composition containing a dispersant package, a detergent package and an antioxidant package. This composition has improved engine cleanliness, detergency, and low sludge formation and wear.

(Background of the Invention)
It is well known that lubricating oils contain a number of additives to protect the engine from wear, sludge accumulation and filter blockage. Common additives for engine lubricants include zinc alkyldithiophosphate (ZDDP) as an antiwear additive, and overbased calcium sulfonate detergents. ZDDP antiwear additives are believed to protect the engine by forming a protective film on the metal surface. A typical throughput of ZDDP is in the range of 1-2% by weight, based on the total weight of the lubricant. Detergents such as overbased calcium sulfonate help keep engine parts clean from soot and other deposits and provide an alkalinity reserve. Typical throughputs for overbased calcium sulfonate detergents range from 0.05 to 10% by weight, based on the total weight of the lubricant.

In recent years, phosphates and sulfonates derived from engine lubricants have been shown to be responsible in part for particulate emissions. Moreover, sulfur and phosphorus tend to harm the NO _x catalyst for use in catalytic converters, resulting in the performance of the catalyst is lowered. Decreased catalytic converter performance tends to lead to an increase in the amount of contaminants (eg, nitric oxide and / or sulfur oxide). However, reducing the amount of ZDDP increases the amount of wear on the engine. Also, reducing the amount of detergent reduces engine cleanliness and increases soot deposits.

  Patent Document 1 (Cressey et al.) Discloses an additive for a lubricant containing a linear compound containing a phenol unit and a salicylic acid unit in the form of an oligomer or a polymer. These linear compounds can be salted with calcium and optionally co-salt with boric acid. These additives have cleaning properties and / or wear resistance properties. Examples of lubricants contain an ashless dispersant and zinc dithiophosphate.

  Patent Document 2 (Moreton) discloses a compound containing a phenol unit and a salicylic acid unit in a lubricating composition. These compounds can be salted with calcium. Examples of lubricating compositions contain phenolic units having dodecylalkyl groups. The compounds of the present invention can be used as detergents in gasoline fuels or diesel fuels. They also make the gasoline or diesel composition stable to pyrolysis.

  Patent Document 3 (Taylor) discloses a fuel composition containing kerosene and a compound containing a phenol unit and a salicylic acid unit. These compounds can be salted with calcium. Examples of lubricating compositions contain phenolic units having dodecylalkyl groups.

  Patent Document 4 (Taylor et al.) Discloses a cyclic compound containing a phenol unit and a salicylic acid unit. The salicylic acid unit can be salted with a metal or ammonium cation.

U.S. Patent No. 6,057,028 (Kocsis et al) relates to the use of saligenin derivatives in lubricating compositions. These formulations contain borate or non-borate magnesium saligenin derivatives. These compositions exhibit improved seal compatibility and low copper and lead corrosion.
International Publication No. 03/18728 Pamphlet US Pat. No. 6,200,936 International Publication No. 99/25793 Pamphlet International Publication No. 01/56968 Pamphlet US Pat. No. 6,310,009

  Currently, it has been discovered that the compositions of the present invention provide engine cleanliness, detergency and antioxidant performance to oils of lubricating viscosity often used in engine oils.

(Summary of the Invention)
The present invention provides a composition containing the following (a), (b), (c) and (d):
(A) Detergent package containing:
(I) metal salixarate; and (ii) a detergent other than component (a) (i), as appropriate;
(B) Dispersant package containing:
(I) a dispersant having one or more carbonyl: nitrogen ratios; and (ii) a dispersant having a carbonyl: nitrogen ratio of less than one;
(C) Antioxidant package containing:
(I) hindered phenol; and (d) oil of lubricating viscosity;
Here, the composition has a phosphorus content equal to or less than 800 ppm; and wherein the sulfate ash content is equal to or less than 1.1 weight percent of the composition.

The present invention further provides a method of preparing a composition, the method comprising the steps of mixing the following (a), (b), (c) and (d):
(A) Detergent package containing:
(I) metal salixarate; and (ii) a detergent other than component (a) (i), as appropriate;
(B) Dispersant package containing:
(I) a dispersant having one or more carbonyl: nitrogen ratios; and (ii) a dispersant having a carbonyl: nitrogen ratio of less than one;
(C) Antioxidant package containing:
(I) hindered phenol; and (d) oil of lubricating viscosity;
Here, the composition has a phosphorus content equal to or less than 800 ppm; and wherein the sulfate ash content is equal to or less than 1.1 weight percent of the composition.

  Using the composition of the present invention, at least one or more of improved engine cleanliness, improved detergency, reduced sludge formation, reduced wear, reduced bore polishing, and reduced oil consumption. Can be given.

(Detailed description of the invention)
The present invention provides the above composition. Often the composition is less than 0.5 wt% in one aspect, less than 0.3 wt% in another aspect, 0.2 wt% or less in yet another aspect, and 0.1 wt% in yet another aspect. Below, it has a total sulfur content. Often, the main source of sulfur in the compositions of the present invention is derived from diluent oil.

  Often, the composition is less than or equal to 800 ppm of the composition, in other aspects, less than or equal to 700 ppm, in yet other aspects, less than or equal to 600 ppm, and in still other aspects, 550 ppm. In yet another aspect, the total phosphorus content is less than or equal to 500 ppm. In one embodiment of the invention, the phosphorus is also present at 200 ppm or 300 ppm to 475 ppm or 580 ppm, or 780 ppm.

  Often, the composition is less than 1.5 wt% of the composition, in one aspect, equal to or less than 1.1 wt%, in other aspects, equal to or less than 1.0 wt%, yet another aspect Has a total ash content (measured by ASTM D-874) equal to or less than 0.8 wt%, and in yet another aspect, equal to or less than 0.5 wt%. In one embodiment, the total ash content is present at 0.1 wt% or 0.2 wt% to 0.6 wt% or 0.7 wt%.

(Cleaner package)
The detergent package contains a metal salixate and optionally at least one detergent other than the metal salixate. Other detergent compounds are well known in the art and are often selected from the group consisting of sulfonates, phenates, sulfurized phenates, carboxylates, phosphates, saligenin and alkyl salicylates. The chemical action of saligenin is described in more detail in US Pat. No. 6,310,009. The chemistry of phenates, alkyl salicylates and phosphonates is described in “Chemistry and Technology of Lubricants” Edited by R. M.M. Mortier and S.M. T.A. ^{Orszulik, 2 nd Edition, Chapter 3} , section 3.2.2, page 82~85, disclosed Copyright 1997. The chemistry of sulfonates is described in “Chemistry and Technology of Lubricants” Edited by R. M.M. Mortier and S.M. T.A. ^{Orszulik, 2 nd Edition, Chapter 3} , section 3.2.1, page 77~82, disclosed Copyright 1997.

  Often the compound can be in the form of a metal salt. In one aspect of the invention, the metal is selected from alkali metals or alkaline earth metals (eg, magnesium, calcium, potassium or sodium, or mixtures thereof). Suitable examples of metal detergents include magnesium saligenin, calcium saligenin, calcium alkyl salicylate, magnesium alkyl salicylate, calcium sulfonate, magnesium sulfonate, or mixtures thereof. In one embodiment, the other detergent compound is magnesium saligenin.

  This detergent package is often 50 ppm to 1200 ppm, in one aspect 75 ppm to 1000 ppm, in other aspects 120 ppm to 800 ppm, and in still other aspects 150 ppm to 700 ppm, such as about 225 ppm, about 275 ppm, about 325 ppm, Contains no more than about 400 ppm, or about 550 ppm of the metal salt present.

  The detergent package is often 0.01 to 20 weight percent of the composition, 0.05 to 15 weight percent in one aspect, 0.1 to 12 weight in other aspects, on an oil-free basis. Percent, in other aspects, from 0.15 to 8 weight percent, and in yet other aspects, from 0.25 to 4 weight percent. In one aspect, the detergent is 10 wt% or less of the detergent package, in another aspect, 20 wt% or less of the detergent package, and in another aspect, 30 wt% or less of the detergent package. Containing. In one aspect, the metal salixarate is present at 0.25-4 weight percent of the composition.

(Salixate salt detergent)
The metal salixarate substrates of the present invention are often represented by substantially linear compounds comprising at least one unit of formula (I) or (II):

または

Or

該化合物の各末端は、式（ＩＩＩ）または（ＩＶ）の末端基を有する：

Each end of the compound has a terminal group of formula (III) or (IV):

このような基は、多価架橋基により連結され、該多価架橋基は、各連鎖に対して、同一または異なり得る；ここで、式（Ｉ）〜（ＩＶ）では、ｆは、１局面では、１、２または３であり、他の局面では、１または２である；Ｕは、−ＯＨ、−ＮＨ_２、−ＮＨＲ^１、−Ｎ（Ｒ^１）_２、またはそれらの混合物であり、Ｒ^１は、１個〜５個の炭素原子を含有するヒドロカルビル基である；Ｒ^３は、水素またはヒドロカルビル基である；Ｒ^４は、ヒドロカルビル基または置換ヒドロカルビル基である；ｇは、１、２または３であるが、但し、少なくとも１個のＲ^４基は、８個またそれ以上の炭素原子を含有する；そして、ここで、該分子は、平均して、該組成物中の（Ｉ）または（ＩＩＩ）単位の少なくとも１個および（ＩＩ）または（ＩＶ）単位の少なくとも１個を含み、（Ｉ）および（ＩＩＩ）単位の全数と（ＩＩ）および（ＩＶ）単位の全数との比は、０．１：１〜２：１である。

Such groups are linked by a polyvalent bridging group, which can be the same or different for each linkage; where in formulas (I)-(IV), f is one aspect In other aspects, it is 1 or 2; U is —OH, —NH ₂ , —NHR ¹ , —N (R ¹ ) ₂ , or a mixture thereof; R ¹ is a hydrocarbyl group containing 1 to 5 carbon atoms; R ³ is hydrogen or a hydrocarbyl group; R ⁴ is a hydrocarbyl group or a substituted hydrocarbyl group; Or 3, provided that at least one R ⁴ group contains 8 or more carbon atoms; and wherein, on average, the molecule comprises (I) in the composition Or (III) at least one unit and (II) or (IV At least one comprises, (I) and (III) the ratio of the total number of units of the total number and (II) and (IV) units units, 0.1: 1 to 2: 1.

The U group of formulas (i) and (iii) may be located at one or more positions of ortho, meta or para with respect to the —COOR ³ group. In one embodiment of the invention, the U group is located ortho to the -COOR ³ group. When the U group is an -OH group, the formulas (i) and (iii) can be converted to 2-hydroxybenzoic acid (which is often referred to as salicylic acid), 3-hydroxybenzoic acid, 4-hydroxybenzoic acid Or a mixture thereof. When U is a —NH ₂ group, formulas (i) and (iii) can be converted to 2-aminobenzoic acid (which is often referred to as anthranilic acid), 3-aminobenzoic acid, 4-aminobenzoic acid Derived from acids, or mixtures thereof.

The divalent bridging groups (which may be the same or different in each occurrence) include —CH ₂ — (methylene bridge) and —CH ₂ OCH ₂ — (ether bridge), any of which is It may be derived from formaldehyde or formaldehyde equivalents (eg paraform, formalin), ethanal or propanal.

  The metal of the metal salixarate is often monovalent, divalent or a mixture thereof. In one aspect of the invention, the metal is selected from alkali metals or alkaline earth metals (eg, magnesium, calcium, potassium or sodium, or mixtures thereof).

  It is believed that an important part of the salixarate molecule (before neutralization), on average, can be expressed as:

ここで、各Ｒ^５は、同一または異なり得、そして水素またはアルキル基であるが、但し、少なくとも１個のＲ^５は、アルキルである。１実施態様では、Ｒ^５は、ポリイソブチレン基（特に、２００〜１，０００、または５５０の分子量を有するもの）である。式（ＩＩＩ）のサリチル酸末端基を含む相当な量の二核種または三核種もまた、存在し得る。このサリキサレート清浄剤は、単独で、または他の清浄剤と併用して、使用され得る。

Here, each R ⁵ may be the same or different and is hydrogen or an alkyl group, provided that at least one R ⁵ is alkyl. In one embodiment, R ⁵ is a polyisobutylene group (particularly one having a molecular weight of 200 to 1,000, or 550). A considerable amount of di- or tri-nuclide containing a salicylic acid end group of formula (III) may also be present. The salixarate detergent can be used alone or in combination with other detergents.

  Salixarate derivatives and methods for their preparation are described in further detail in US Pat. No. 6,200,936 and PCT publications WO 01/56968 and WO 03/18728.

(Dispersant package)
The dispersants of the present invention are often derived from N-substituted long chain alkenyl succinimides. The present invention requires at least two dispersants, one having a high total base number and one having a high total acid number. In general, dispersants with high TAN numbers have a carbonyl: nitrogen ratio of 1 or higher, in one aspect, a carbonyl: nitrogen ratio of 1.2 or higher, in other aspects, a carbonyl of 1.4 or higher. : Nitrogen ratio, and in yet other aspects, has a carbonyl: nitrogen ratio of 1.45 or higher, eg, a carbonyl: nitrogen ratio of 1.5. Generally, dispersants with high TBN numbers have a carbonyl: nitrogen ratio of less than 1, in one aspect, a carbonyl: nitrogen ratio of 0.94 or lower, in other aspects, a carbonyl: nitrogen of 0.88 or lower. The ratio, in other aspects, has a carbonyl: nitrogen ratio of 0.8 or lower, eg, a carbonyl: nitrogen ratio of 0.77. The carbonyl: nitrogen ratio is calculated on a molar basis, ie, the ratio of the number of moles of carbonyl functionality (eg, —C (O) O—) to the number of moles of nitrogen functionality (eg, amine nitrogen). .

  The dispersant package is often 0.01 to 30 weight percent of the composition, 0.5 to 25 weight percent in one aspect, 1.5 to 20 weight in another aspect, on an oil-free basis. Present in percent, and in yet other aspects, from 3 to 15 percent by weight. Often, dispersants having a high total base number are present at a lower concentration than dispersants having a high total acid number. Alternatively, the amount of dispersant having a high total acid number is equal to the amount of dispersant having a high total base number. In yet another option, dispersants having a high total acid number are often present at lower concentrations than dispersants having a high total base number. Often, the dispersant present in large amounts is greater than 50% of the amount of dispersant present in the package, and in one aspect 55% of the amount of dispersant present in the package. More, in yet other aspects, more than 60% of the amount of dispersant present in the package is present. For example, dispersants that are present in large amounts are present in 61% to 95% of the dispersant, in one aspect 62% to 90% of the dispersant, and in yet another aspect in the package. 63% to 85% of the dispersant present. In one aspect, the ratio of high TAN dispersant to high TBN dispersant is 1: 1 to 15: 1, in other aspects 2: 1 to 10: 1, in other aspects 3: 1 to 6: 1. In certain embodiments, the mixture of dispersants has a TAN of at least 15% or at least 20% of the TBN of the dispersant mixture, for example, 15-30% of the TBN. In a particular embodiment, the dispersant mixture has a TBN / TAN ratio of 3: 1 to 7: 1.

  The N-substituted long chain alkenyl succinimide has various chemical structures and includes mono-succinimide and / or di-succinimide. Often, the long chain alkenyl group has a number average molecular weight of 350 to 10,000, in one aspect 400 to 7000, in another aspect 500 to 5000, and in yet another aspect 500 to 4000. In one embodiment, the long chain alkenyl group is a polyisobutylene group having a number average molecular weight of 800-1600, in another embodiment 1600-3000. The succinimide is often a hydrocarbyl-substituted acylating agent (eg, hydrocarbyl-substituted succinic anhydride) and a polyamine or amino alcohol (often a polyalkylene polyamine or poly (ethylene amine) such as triethylenetetramine, tetraethylenepentamine. , Pentaethylenehexamine, or, in one embodiment, polyamine still bottoms).

  N-substituted long chain alkenyl succinimide dispersant additives and their preparation are disclosed, for example, in US Pat. Nos. 3,361,673, 3,401,118 and 4,234,435. .

  Other dispersants may also be present. Other types of suitable dispersants include Mannich bases, which are alkyl (wherein the alkyl group typically contains at least 30 carbon atoms) and aldehydes (in particular, Formaldehyde) and amines (especially polyalkylene polyamines) and are described in more detail in US Pat. No. 3,634,515.

  Another type of ashless dispersant is a high molecular weight ester. These materials are similar to the succinimides described above except that they may appear to have been prepared by reaction of a hydrocarbyl acylating agent with a polyhydric aliphatic alcohol (eg, glycerol, pentaerythritol or sorbitol). Such materials are described in further detail in US Pat. No. 3,381,022.

  Other dispersants include polymeric dispersant additives, which are generally hydrocarbon-based polymers that contain polar functionality that imparts dispersion properties to the polymer.

  The dispersant can also be worked up by reacting with any of a variety of reagents. These include urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds and phosphorus compounds. References detailing such treatment are listed in US Pat. No. 4,654,403. (The carbonyl: nitrogen ratio in that document is calculated before any such post-treatment).

There are two commonly used methods of making N-substituted long chain alkenyl succinimide dispersants. These are the methods by which polyalkylene (typically polyisobutylene but also copolymers, including ethylene copolymers) substituents are prepared and whether it is a monoacid or diacid or anhydride moiety (in particular, In that it is anchored to the succinic anhydride moiety or reactive equivalent thereof. In the usual method (a), isobutylene is polymerized in the presence of AlCl ₃ to produce a polymer containing primarily tri-substituted olefins and tetra-substituted olefin end groups, with very small amounts of chains (eg, Only less than 20 percent) contain terminal vinylidene groups. Alternatively, in “chlorine-free” or “thermal” method (b), isobutylene is polymerized in the presence of BF ₃ catalyst to predominantly (eg, at least 70 percent) contain terminal vinylidene groups. This produces a mixture of polymers, with a small amount of tetrasubstituted end groups and other structures. These materials are sometimes referred to as “high vinylidene PIB” and are described in US Pat. No. 6,165,235. In general, dispersants having a carbonyl nitrogen ratio of 1 or higher; or dispersants having a carbonyl nitrogen ratio of less than 1 can be prepared using any method.

  Amines that can be used in preparing the dispersant include those having at least one reactive NH group. Suitable examples of amines include amine compounds containing only one reactive amino group per molecule; (ii) polyamines; (iii) a amino alcohol; (iv) cyclic amines; and (v) (i)-( iv) selected from the group consisting of mixtures.

  In one embodiment, the polyamine is an alkylene polyamine selected from the group consisting of ethylene polyamine, propylene polyamine, butylene polyamine, and mixtures thereof. Examples of propylene polyamines include propylene diamine, dipropylene triamine, or mixtures thereof. A particularly useful class of amines is derived from ethylene polyamines and is selected from the group consisting of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyamine still bottoms and mixtures thereof.

  In one embodiment, the polyamine includes an α, β-diaminoalkane, or a mixture thereof. Suitable examples of α, β-diaminoalkanes include diaminopropane, diaminobutane, or mixtures thereof. Particularly useful examples of aminoalkanes include N- (2-aminoethyl) -1,3-propanediamine, 3,3′-diamine-N-methyldipropylamine, tris (2-aminoethyl) amine, N , N-bis (3-aminopropyl) -1,3-propanediamine, N, N′-1,2-ethanediylbis- (1,3-propanediamine), and mixtures thereof Is mentioned.

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

  Suitable aminoalcohols for the present invention are 1 to 6 hydroxyl groups, 1 to 3 hydroxyl groups and 1 to 8 amine groups in one aspect, 1 to 2 amine groups in one aspect. Containing. When the amine is an aminoalcohol, the insomnia is often ethanolamine, isopropanolamine, diethanolamine, triethanolamine, diethylethanolamine, dimethylethanolamine, dibutylethanolamine, 3-amino-1,2-propanediol; 2-amino-2-methyl-1,3-propanediol; tris (hydroxymethyl) -aminomethane; 1-amino-1-deoxy-D-sorbitol; diethanolamine; diisopropanolamine; N-methyl-N, N-diethanolamine; triethanolamine; N, N, N ′, N′-tetrakis (2-hydroxypropyl) -ethylenediamine, 2-amino-2-methyl-1-propanol, 2-dimethylamino-methyl-1 Selected from the group consisting of propanediol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, 2-amino-1-butanol and mixtures thereof The

(Antioxidant package)
Hindered phenol antioxidants suitable for the present invention are often represented by the following formula:

ここで、Ｒ^６およびＲ^７は、別個に、１局面では、１個〜２４個、他の局面では、４個〜１８個、さらに他の局面では、４個〜１２個の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、ヒドロカルビル基、第二芳香族基に連結する架橋基、エステル含有基、またはそれらの混合物である。

Here, R ⁶ and R ⁷ separately contain 1 to 24 carbon atoms in one aspect, 4 to 18 in another aspect, and 4 to 12 carbon atoms in yet another aspect. And E is hydrogen, a hydrocarbyl group, a bridging group linked to a second aromatic group, an ester-containing group, or a mixture thereof.

R ⁶ and R ⁷ can be either linear or branched, and suitable examples include secondary butyl and tertiary butyl.

  In one embodiment, the hindered phenol of formula (VI) suitable for the present invention is an ester or acid represented by the following formula:

ここで、Ｒ^６およびＲ^７は、上で定義したとおりであり、そしてＲ^８は、水素、ヒドロカルビル基、またはそれらの混合物である。Ｒ^８がヒドロカルビル基であるとき、Ｒ^８は、しばしば、ブチル、ｓｅｃ−ブチル、イソブチル、ｔｅｒｔ−ブチル、ペンチル、ｎ−ヘキシル、ｓｅｃ−ヘキシル、ｎ−オクチル、２−エチルヘキシル、ノニル、デシル、ウンデシル、ドデシル、およびそれらの混合物からなる群から選択される。

Where R ⁶ and R ⁷ are as defined above and R ⁸ is hydrogen, a hydrocarbyl group, or a mixture thereof. When R ⁸ is a hydrocarbyl group, R ⁸ is often butyl, sec-butyl, isobutyl, tert-butyl, pentyl, n-hexyl, sec-hexyl, n-octyl, 2-ethylhexyl, nonyl, decyl, undecyl. , Dodecyl, and mixtures thereof.

In one embodiment, the hindered phenol of formula (VI) suitable for the present invention contains a crosslinking group. Examples of suitable bridging groups include alkylene bridges or ether bridges, which are from 1 to 8, in one aspect from 1 to 6, in other aspects from 1 to 4, and others In this aspect, it contains 1 to 2 carbon atoms. Examples of suitable bridging _{groups, -CH 2 -, - CH 2} CH 2 -, - CH 2 OCH 2 - and _{-CH 2 CH 2 OCH 2 CH 2} - and the like.

  When present, hindered phenols with bridging groups are often represented by the following formula:

ここで、Ｒ^６およびＲ^７は、上で定義されており、そしてＹは、架橋基である。メチレン架橋ヒンダードフェノールの例には、４，４’メチレン−ビス−（６−第三級ブチル−ｏ−クレゾール）、４，４’メチレン−ビス−（２−第三級アミル−ｏ−クレゾール）および４，４’メチレン−ビス−（２，６−ジ−第三級ブチルフェノール）が挙げられる。

Where R ⁶ and R ⁷ are defined above and Y is a bridging group. Examples of methylene bridged hindered phenols include 4,4'methylene-bis- (6-tertiarybutyl-o-cresol), 4,4'methylene-bis- (2-tertiary amyl-o-cresol) ) And 4,4 ′ methylene-bis- (2,6-di-tert-butylphenol).

  The hindered phenols of the present invention also include compounds represented by the following formula:

ここで、Ｒ^６およびＲ^７、ＥおよびＹは、上で定義されている。式（ＶＩＩ）の適当なメチレン架橋ヒンダードフェノールの例には、２，２’−メチレン−ビス−（４−メチル−６−第三級ブチルフェノール）、および２，２’−メチレン−ビス−（４−エチル−６−第三級ブチルフェノール）、２，２’−メチレン−ビス−（４−プロピル−６−第三級ブチルフェノール）が挙げられる。

Here, R ⁶ and R ⁷ , E and Y are defined above. Examples of suitable methylene bridged hindered phenols of formula (VII) include 2,2'-methylene-bis- (4-methyl-6-tert-butylphenol), and 2,2'-methylene-bis- ( 4-ethyl-6-tert-butylphenol), 2,2'-methylene-bis- (4-propyl-6-tert-butylphenol).

  The antioxidant package is often 0.01 to 20 weight percent of the composition, 0.1 to 15 weight percent in one aspect, 0.5 to 10 in other aspects, on an oil-free basis. It is present in weight percent, and in yet other aspects, from 1 to 5 weight percent. In one aspect, at least 50 wt% of the antioxidant package is hindered phenol. In one aspect, the hindered phenol is 0.2 to 3 weight percent of the composition, alternatively 0.01 to 15 weight percent or 0.05 to 10 weight percent or 0.1 to 5 weight percent or 0.1. It is present at 5-4 weight percent.

(Oil with lubricating viscosity)
The lubricating oil composition of the present invention can be added to oils with 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 obtained directly from natural or synthetic raw materials without further purification treatment (or almost no purification treatment).

  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 often further processed by methods directed to remove spent additives and oil breakdown products.

  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.); polyphenyls (eg, , Biphenyl, terphenyl, alkylated polyphenyl); alkylated diphenyl ethers and alkylated diphenyl sulfides, and their derivatives, analogs and homologues, or mixtures thereof.

  Other synthetic lubricating oils include, but are not limited to, polyol esters, 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 API Group I, Group II, Group III, Group IV, Group V oil, and mixtures thereof; in one aspect, API Group II, Group III, Group IV Group or Group V oils, and mixtures thereof; in yet other aspects, selected from the group consisting of API Group III, Group IV, Group V oils, and mixtures thereof. If this oil of lubricating viscosity is an API Group II, Group III, Group IV or Group V oil, up to 20 wt%, in one aspect, up to 10 wt%, other In aspects, there may be up to 5 wt% of lubricating oil (API Group I oil) up to 1.5 wt% in yet other aspects.

  Examples of suitable API Group III oils include Nexbase (TM) 3050, Nexbase (TM) 3043, Nexbase (TM) 3060, PAO-6, Priolube (TM) 1976, Yubase (TM) 4, Yubase (TM) 6 and Shell ™ XHVI 5.2.

  The oil of lubricating viscosity is often up to 99.97 weight percent of the composition, in one aspect, up to 99.69 weight percent, in other aspects, up to 97.75 weight percent, and in yet other aspects, Present up to 95.5 weight percent. This composition is often classified as an SAE XW-Y lubricating oil, where X is 0 or 5; and Y is 20, 30, 40 or 50.

  If the present invention is in the form of a concentrate (which can be mixed with additional oil to form, in whole or in part, the final lubricant), each of the other components as well as the dispersant The ratio of oil to diluent oil is often 80:20 to 10:90 on a weight basis.

(Other performance additives)
The composition of the present invention further contains other performance additives as required. These other performance additives include antioxidants other than component (c), corrosion inhibitors, antiwear agents, friction modifiers, viscosity modifiers, scuffing agents, antifoaming agents, demulsifiers, pour point depressants. , A seal swell agent, and mixtures thereof.

  The total amount of other performance additives present is often 0 to 25 weight percent of this composition, 0.01 to 20 weight percent in one aspect, and 0.01 to 20 weight percent in other aspects, on an oil-free basis. 0.05 to 15 weight percent, and in yet another aspect 0.1 to 10 weight percent. Although one or more of these other performance additives may be present, these other performance additives are typically present in different amounts relative to each other.

(Friction modifier)
The friction modifier, when present in the present invention, can be a monoester of a polyol and an aliphatic carboxylic acid (often an acid containing 12 to 24 carbon atoms). Often, the monoester of a polyol and an aliphatic carboxylic acid is in the form of a mixture with sunflower oil or the like, and the sunflower oil or the like is 5 to 95 weight percent of the mixture in the friction modifier mixture, 1 In aspects, it may be present at 10 to 90 weight percent, in other aspects 20 to 85 weight percent, and in still other aspects 20 to 80 weight percent.

  Polyols include diols, triols, and alcohols having a high number of alcoholic OH groups. Polyhydric alcohols include ethylene glycol (including di-, tri- and tetraethylene glycol); propylene glycol (including di-, tri- and tetrapropylene glycol); glycerol; butanediol; hexanediol; sorbitol; Arabitol; mannitol; sucrose; fructose; glucose; cyclohexanediol; erythritol; and pentaerythritol (including di- and tripentaerythritol). Often the polyol is diethylene glycol, triethylene glycol, glycerol, sorbitol, pentaerythritol or dipentaerythritol.

  The aliphatic carboxylic acids that form these esters are those containing 12 to 24 carbon atoms. Acids containing straight chain hydrocarbyl groups containing 12 to 24 carbon atoms (e.g., 14 to 20 or 16 to 18 carbon atoms) are often used. Such acids can be used in combination with acids having more or fewer carbon atoms as well. Examples of carboxylic acids include dodecanoic acid, stearic acid, lauric acid, behenic acid and oleic acid.

  The esters present in the present invention are in particular monoesters of such polyols with such carboxylic acids. Often this ester is glycerol monooleate. Glycerol monooleate is a mixture containing substances such as glycerol, oleic acid, other long chain acids, glycerol dioleate and glycerol trioleate in its commercial grade, as is the case with other such substances. You should be able to understand that. This commercial material is believed to contain 60 ± 5 weight percent of the species “glycerol monooleate” along with 35 ± 5 weight percent glycerol dioleate and less than 5 weight percent trioleate and oleic acid. The amount of these monoesters (below) is calculated based on the actual corrected amount of polyol monoester present in any such mixture.

  Other friction modifiers suitable for the present invention include fatty amines, fatty phosphites, fatty acid amides, fatty epoxides, alkoxylated fatty amines, fatty acid metal salts, sulfurized olefins, fatty imidazoles, carboxylic acids and polyalkylene-polyamines. And an amine salt of alkyl phosphoric acid.

(Other antioxidants)
Optionally, the present invention contains antioxidants other than hindered phenols (eg, diphenylamine antioxidants, molybdenum dithiocarbamates, sulfurized olefins, or mixtures thereof). Diphenylamine antioxidant additives often have 6 or fewer hydrocarbyl groups in one aspect, 4 or fewer hydrocarbyl groups in another aspect, and 3 or fewer hydrocarbyls in yet another aspect. Contains groups (eg 1 or 2). Each hydrocarbyl group often contains 1 to 24 carbon atoms in one aspect, 2 to 18 carbon atoms in another aspect, and 4 to 12 carbon atoms in yet another aspect. To do. In one embodiment of the invention, the composition contains a diphenylamine antioxidant.

  Examples of suitable diphenylamine antioxidants include octyl diphenylamine, nonyl diphenylamine, bis-octyl diphenylamine and bis-nonyl diphenylamine.

(Viscosity modifier)
As needed, this invention contains a viscosity modifier. Viscosity modifiers are known and include polymeric materials, which include hydrogenated styrene-butadiene rubbers, olefin copolymers, hydrogenated styrene-isoprene polymers, polymethacrylates, polyacrylates, polyacrylates. Examples include alkyl styrene, alkenyl aryl conjugated diene copolymers, polyalkyl methacrylates, esters of maleic anhydride-styrene copolymers or mixtures thereof.

Often, the polymethacrylate viscosity modifiers include the following (a), (b) and, optionally, a copolymer of (c): (a) contains 9-30 carbons in the ester group (B) a methacrylic acid ester containing 7 to 12 carbons in the ester group, wherein the ester group is a 2- (C _1-4 alkyl) -substituent. And (c) a methacrylic acid ester containing 2 to 8 carbon atoms in the ester group, and the methacrylic acid ester used in the above (a) and (b) Is different. A more detailed description of polymethacrylate viscosity modifiers is disclosed in US Pat. No. 6,124,249.

  Often, the viscosity modifier derived from the olefin copolymer backbone contains 2 to 4 species in one aspect, 2 to 3 in another aspect, and 2 different olefin monomers in yet another aspect. . These olefin monomers often have 2 to 20 carbon atoms in one aspect, 2 to 10 carbon atoms in another aspect, 2 to 6 carbon atoms in yet another aspect, In yet another aspect, it contains 2 to 4 carbon atoms.

The olefin copolymer is often derived from an ethylene monomer and at least one other comonomer (which is derived from an alpha-olefin having the formula H ₂ C═CHR ⁸ , where R ⁸ is a hydrocarbyl group, In aspects, 1 to 18 carbon atoms, in one aspect, 1 to 10 carbon atoms, in other aspects, 1 to 6 carbon atoms, and in other aspects, 1 to 3 carbon atoms An alkyl radical containing a carbon atom of The hydrocarbyl group contains an alkyl radical having a straight chain, a branched chain, or a mixture thereof. Examples of suitable comonomers include propylene, 1-butene, 1-hexene, 1-octene, 4-methylpentene-1,1-decene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, -Hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, or mixtures thereof. Examples of this olefin copolymer include ethylene-propylene copolymer, ethylene-butene-1 copolymer, and mixtures thereof.

In one embodiment of the invention, the optional viscosity modifier is a mixture of copolymers containing two or more olefins. For example, a mixture of two copolymers derived from the following (A) and (B): (A) a copolymer comprising 45 to 85% by weight of units derived from ethylene, , _M w, of less than 3 _M w / _{M n,} and has a melting point of 0 ° C. to 60 ° C. for 000～300,000; block copolymers comprising a and (B) a vinyl aromatic comonomer moiety and second comonomer moiety.

  Copolymer (A) is often prepared by copolymerizing ethylene and other monomers (usually propylene).

  Among the monomers that can be used to prepare the (B) copolymer of the present invention, 1,3-butadiene, 1,2-pentadiene, 1,3-pentadiene, isoprene, 1,5-hexadiene and 2-chloro -1,3-butadiene, and aromatic olefins such as styrene, α-methyl styrene, ortho-methyl styrene, meta-methyl styrene, para-methyl styrene and para-t-butyl styrene, and mixtures thereof . The mixture and polymer can contain other comonomers, which do not substantially change the properties of the resulting polymer.

Suitable styrene / isoprene hydrogenated copolymers are Infineum ™ SV140 (formerly Shellvis ™ 40) ( _Mw about 200,000), Infineum ™ SF150 ( _Mw about 150,000) and Infineum ( (Trademark) SV160 ( _Mw about 150,000), not only commercially available from Infineum, but also Septon (TM) 1020 ( _Mw about 150,000) and Septon (TM) 1001 ( _Mw about 200) , 000) under the trade name of Septon Company of America (Kuraray Group). A suitable styrene / 1,3-butadiene hydrogenated random block copolymer is available from BASF under the trade name Glissoviscal ™ ( _Mw about 160,000-220,000). A more detailed description of some of these polymers can be found in US Pat. No. 5,747,433 (see column 3, lines 56-8, line 62). A more detailed description of copolymers containing two or more olefins is given in US patent application 0/458666 (currently PCT application WO 04/0887849).

  Optionally, this viscosity modifier copolymer is further grafted with an unsaturated dicarboxylic anhydride or derivative thereof and an amine to form a dispersant viscosity modifier (often referred to as DVM, The properties are also shown, so they are named).

(Antiwear agent)
The present invention optionally contains an antiwear agent such as a metal hydrocarbyl dithiophosphate, which is often represented by the following formula:

ここで、Ｒ^９およびＲ^１０は、別個に、水素、ヒドロカルビル基、またはそれらの混合物であるが、但し、Ｒ^９およびＲ^１０の少なくとも１個は、ヒドロカルビル基であり、これは、しばしば、１局面では、１個〜３０個の炭素原子、他の局面では、２個〜２０個の炭素原子、さらに他の局面では、２個〜１５個の炭素原子を含有する。

Where R ⁹ and R ¹⁰ are independently hydrogen, hydrocarbyl groups, or mixtures thereof, provided that at least one of R ⁹ and R ¹⁰ is a hydrocarbyl group, which is often 1 In aspects, it contains 1 to 30 carbon atoms, in other aspects it contains 2 to 20 carbon atoms, and in yet other aspects it contains 2 to 15 carbon atoms.

  M 'is a metal and n is an integer equal to the available valence of M'. M 'is monovalent, divalent or trivalent; in one aspect, M' is divalent and in another aspect is a divalent transition metal. In one embodiment, M 'is zinc. In one embodiment, M 'is calcium. In one embodiment, M 'is barium. Examples of hydrocarbyl dithiophosphate metals include zinc dihydrocarbyl dithiophosphate, which is often referred to as ZDDP, ZDP or ZDTP.

  If necessary, the present invention further contains a borate ester antiwear agent. The borate ester is prepared by reacting a boron compound with at least one compound selected from the following: epoxy compounds, halohydrin compounds, epihalohydrin compounds, alcohols, and mixtures thereof. Often these alcohols include monohydric alcohols, dihydric alcohols, trihydric alcohols or higher alcohols.

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.

  The borate ester formed by the reaction of a boron compound and an epoxy compound can be represented by at least one compound derived from the following formula:

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、１局面では、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、アルキル、アリールまたはシクロアルキル（任意の２個の隣接したＲ基が環で結合するとき）であり得る。

Here, R ¹¹ , R ¹² and R ¹³ can be hydrogen or a hydrocarbyl group, provided that at least one of R ¹¹ , R ¹² and R ¹³ , in one aspect, at least two 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 joined by a ring).

Often, in this hydrocarbyl group, there is no upper limit on the number of carbon atoms, but practical limits are 500, in one aspect, 400, in other aspects, 200, and in other aspects. , 100 or 60. For example, the number of carbon atoms present in R ¹¹ , R ¹² and R ¹³ can be 1 to 60, or 1 to 40, or 1 to 30 carbon atoms provided that R ¹¹ , R ¹² and R ¹³ have 9 or more carbon atoms, 10 or more in one aspect, 12 or more in other aspects, 14 or 14 in other aspects, More than that.

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 hydrogen or hydrocarbyl groups, but it is common for at least one of R ^{21 to} R ²⁶ to be a hydrocarbyl group; and R ²⁷ is hydrogen or hydrocarbyl. Although it may be a group, it is common for R ^{27 to} be hydrogen. 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.

  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. Boric acid ester compounds are described in more detail in European Patent 976814.

  The compositions of the present invention optionally contain antiwear additives other than hydrocarbyl dithiophosphate metals, including phosphate esters or salts thereof; and phosphorus-containing carboxylic esters, ethers and amides, or A mixture thereof may be mentioned. Often the phosphate ester contains a hydrocarbyl ester group having from 4 to 40 carbon atoms, in one aspect from 4 to 30 carbon atoms, and in other aspects from 6 to 24 carbon atoms. . In one embodiment, the hydrocarbyl ester group is alkyl, and in another embodiment, the hydrocarbyl group is aryl.

  Other optional performance additives include, for example, corrosion inhibitors (octylamine octoate, dodecenyl succinic acid or anhydride and fatty acid (eg, oleic acid) and polyamine condensation products); metal deactivators (including Are benzotriazole, 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzoimidazole or 2-alkyldithiobenzothiazole); antifoaming agents (these are ethyl acrylate and acrylic acid 2- Including copolymers of ethylhexyl and, optionally, vinyl acetate); demulsifiers (including trialkyl phosphates, polyethylene glycol, polyethylene oxide, polypropylene oxide and (ethylene oxide-propylene oxide) polymers). ); Pour point depressant ( These include maleic anhydride-esters of styrene, polymethacrylates, polyacrylates or polyacrylamides); and seal swell agents (including Exxon Necton-37 ™ (FN 1380) and Exxon Mineral Seal Oil. (FN 3200)), which may also be used in the compositions of the present invention.

(Method)
The present invention further provides a method of preparing the composition.

  Components (a)-(d) are often mixed sequentially and separately for the compositions of the present invention, but two or more of these components can also be mixed simultaneously. The mixing conditions are often 15 ° C. to 130 ° C., 1 aspect 20 ° C. to 120 ° C., other aspects 25 ° C. to 110 ° C .; 30 seconds to 48 hours, 1 aspect 2 minutes to 24 hours, In another aspect, the time ranges from 5 minutes to 16 hours, and in yet another aspect, the time ranges from 10 minutes to 5 hours; In another aspect, the pressure is in the range of 95 kPa to 133 kPa (715 mmHg to 1000 mmHg).

  This method includes a step of mixing the other performance additives as necessary. These optional performance additives are often added sequentially, separately or as a concentrate.

(Industrial use)
The compositions of the present invention are useful as lubricants in internal combustion engines (eg, diesel fuel engines, gasoline fuel engines, natural gas fuel engines or mixed gasoline / alcohol fuel engines).

  In one embodiment, the present invention provides a method of lubricating an internal combustion engine, the method comprising supplying a lubricant containing the composition described herein. Use of the composition of the present invention may provide at least one or more of improved engine cleanliness, improved detergency, reduced sludge formation, reduced wear, reduced bore polishing and reduced oil consumption. it can.

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

(Reference Example 1)
Reference Example 1 is a 5W-30 lubricant containing: About 6% succinimide dispersant (more than high TBN dispersant, high TAN dispersant present on an oil-free basis) Containing, on an oil-free basis, about 2.8 wt% hindered phenol antioxidant; and a detergent package (which is an alkyl salicylate (AC60C® available from Infineum); It is present at about 1.1 wt% on an oil free basis). This lubricant has a phosphorus content of 480 ppm and a sulfate ash content of 0.49 wt%.

Example 1
Example 1 describes a detergent package containing an alkyl salicylate as a calcium sulfonate detergent and a calcium salixalate detergent (each commercially available from The Lubrizol Corporation, both on an oil-free basis, approximately 1 This is the same as Reference Example 1 except that it is replaced by 1 wt%.

(Reference Example 2)
Reference Example 2 is the same as Example 1 except that the high TAN dispersant is used alone.

(Reference Example 3)
Reference Example 3 is the same as Reference Example 1 except that the detergent package containing the alkyl salicylate is replaced with calcium sulfonate and calcium phenate.

(Example 2)
Example 2 is the same as Reference Example 1 except that the detergent package containing the alkyl salicylate is replaced with calcium sulfonate, calcium phenate and calcium salixarate.

(Preparation Example A)
A blend is prepared from a 50:50 (by weight) mixture of ethylene-propylene copolymer (Polymer A) and styrene / isoprene hydrogenated copolymer (Polymer B), each of which is a commercially available viscosity modifier. Polymer A is first dissolved in 150N mineral oil, which contains 0.1% butylated hydroxytoluene (BHT) antioxidant. The antioxidant is added to the mineral oil at room temperature. To the oil, slowly add polymer A (which is in the form of pellets) while heating and stir under high agitation. After all the polymer A has been added, the oil continues to be heated to 130 ° C. and is maintained at that temperature until the polymer A pellets are fully dissolved. Polymer B (also in pellet form) is then added to the oil with thorough stirring at 130 ° C. until all of the polymer B is fully dissolved. These blends are maintained at 130 ° C. under strong agitation for an additional 2 hours to ensure that all polymers are sufficiently dissolved.

(Example 3)
Example 3 is a 5W-30 lubricant containing: about 6% succinimide dispersant (which is higher in amount than high TBN dispersant in high TAN dispersant) on an oil-free basis. About 2.8% hindered phenol antioxidant on an oil-free basis; and a detergent package (which includes 1.2 wt.% Calcium salixate and olefin copolymer on an oil-free basis) It contains only viscosity modifiers and is present at about 1 wt% on an oil-free basis). This lubricant has a phosphorus content of 480 ppm and a sulfate ash content of 0.44 wt%.

Example 4
Example 4 is the same as Reference Example 4 except that the viscosity modifier is the product of Preparation Example A.

(Reference Example 4)
Reference Example 4 is the same as Reference Example 3 except that the composition contains an antioxidant package with hindered phenol and diphenylamine. The detergent package is present at about 1.1 wt%. This lubricant has a phosphorus content of 760 ppm and an ash content of 0.76 wt%.

(Example 5)
Example 5 is the same as Reference Example 4 except that the detergent package present at 0.8 wt% contains calcium sulfonate, calcium phenate and calcium salixate instead of alkyl salicylate. is there.

(Reference Example 5)
Reference Example 5 is a 5W-30 lubricant containing: about 6% succinimide dispersant (this is a higher amount of high TAN dispersant than higher TBN dispersant) on an oil-free basis. About 0.65% hindered phenol antioxidant on an oil-free basis; and a detergent package (which contains only magnesium saligenin and 0.9 wt% on an oil-free basis) Is). This lubricant has a magnesium content of 400 ppm, a phosphorus content of 1300 ppm, and an ash content of 1.65 wt%.

(Example 6)
Example 6 is a 5W-40 lubricant containing: About 11.9% succinimide dispersant (which is higher in amount than high TBN dispersant and high TAN dispersion on an oil-free basis) About 3% hindered phenol antioxidant on an oil-free basis; and a detergent package (which contains calcium salixarate and magnesium saligenin, on an oil-free basis, Present at 1.0 wt%). The lubricant has a magnesium content of 100 ppm, a phosphorus content of 500 ppm, and a sulfate ash content of 0.97 wt%.

(Test 1: Cleanliness test)
A piston cleanliness test is performed based on the Coordinating European Council (CEC) test method CEC L-78-T-99. The results are based on merit scores, with high values indicating good piston cleanliness. The results obtained are as follows:

表１の結果は、高ＴＡＮ分散剤と高ＴＢＮ分散剤との組み合わせ（実施例１）が１種の分散剤だけを有する参照例２と比較して、ピストン清浄度が向上したことを示している。

The results in Table 1 show that the combination of high TAN dispersant and high TBN dispersant (Example 1) improved piston cleanliness compared to Reference Example 2 with only one dispersant. Yes.

  Comparing Example 1 with Reference Example 1, (a) a dispersant package with a high TAN dispersant, a high TBN dispersant detergent package (which contains salixarate); and a hindered phenol antioxidant package However, it is clear that it improves piston cleanliness compared to detergent packages that do not contain salixarate. Similarly, comparing Example 2 with Reference Example 3 again reveals the piston cleanliness characteristics of the composition of the present invention.

  Comparison of Example 3 and Reference Example 4 reveals that the composition of the present invention has piston cleanliness properties even in the presence of a viscosity modifier.

(Test 2: Sludge and wear test)
The sludge test M111 ESL is performed based on the Coordinating European Council (CEC) test method CEC-L-53-T-95. The test conditions used are condition E of this test method. From this test, a sludge score and average engine cam wear scar (μm) are obtained. The higher the sludge rating, the less sludge formed in the engine, and a lower wear scar value indicates less engine wear. The results obtained are as follows:

これらの結果は、本発明の組成物がスラッジ形成およびエンジン摩耗を減らすことを示している。

These results show that the composition of the present invention reduces sludge formation and engine wear.

(Test 3: MB OM 441 LA high load diesel cleanliness test)
The high load diesel cleanliness test MB OM 441 LA is performed based on the Coordinating European Council (CEC) test method CEC-L-52-T-97. This test provides engine cleanliness data and data related to engine durability. The results obtained are as follows:

これらの結果は、本発明の組成物が、参照例と比較して、ピストン清浄度を向上させ、ボアポリッシングを減らし、そしてオイル消費を減らしたことを示している。表３の他の測定値は、許容できる限度内である。

These results indicate that the composition of the present invention improved piston cleanliness, reduced bore polishing, and reduced oil consumption compared to the reference example. The other measurements in Table 3 are within acceptable limits.

  Overall, the compositions of the present invention improve engine cleanliness, improve cleanliness, reduce sludge formation, reduce wear, reduce bore polishing, and reduce oil consumption.

  As used herein, the term “hydrocarbyl substituent” or “hydrocarbyl group” as used herein is used in its ordinary sense, which is well known to those skilled in the art. Specifically, it is a group composed primarily of carbon and hydrogen atoms, bonded to the rest of the molecule through the carbon atom, and is sufficient to damage molecules that have predominantly hydrocarbon character. Means a group that does not preclude the presence of other atoms or groups in any proportion. Generally, in this hydrocarbyl group, there are no more than 2 non-hydrocarbon substituents, and in one aspect, no more than 1 non-hydrocarbon substituent for each 10 carbon atoms; typically the hydrocarbyl There are no such non-hydrocarbon substituents in the group. A more detailed description of “hydrocarbyl substituent” or “hydrocarbyl group” is provided in US Pat. No. 6,583,092.

  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, number of carbon atoms, etc. in this description specifying 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 combined 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 (15)

A composition comprising:
(A) A detergent package, which:
A detergent package comprising (i) a metal salixarate; and (ii) a detergent other than component (a) (i), as appropriate;
(B) Dispersant package comprising:
a. A dispersant having a carbonyl to nitrogen ratio of about 1 or more; and b. A dispersant package comprising a dispersant having a carbonyl to nitrogen ratio of less than about 1;
(C) Antioxidant package containing:
a. Hindered phenols; and (d) oils of lubricating viscosity;
Including
Wherein the composition has a phosphorus content less than or equal to about 800 ppm; and wherein the sulfate ash content is less than or equal to about 1.1 weight percent of the composition ,Composition. Furthermore, the composition of Claim 1 containing detergent other than component (a) (i). Furthermore, the composition of Claim 1 containing a viscosity modifier. The viscosity modifier is
(A) a copolymer comprising 45 to 85% by weight of units derived from ethylene, having a M _{w of} 50,000 to 300,000, a M _w / M _{n of} less than 3, and a melting point of 0 ° C. to 60 ° C .; 4. The composition of claim 3 which is a mixture of two copolymers derived from (B) a block copolymer comprising a vinyl aromatic comonomer moiety and a second comonomer moiety. The composition of claim 1, further comprising a diphenylamine antioxidant, molybdenum dithiocarbamate, sulfurized olefin, or mixtures thereof. The composition of claim 1 further comprising a borate ester. The composition of claim 2, wherein the detergent other than component (a) (i) is selected from the group consisting of sulfonate, phenate, sulfurized phenate, carboxylate, phosphate, saligenin and alkyl salicylate. The composition according to claim 7, wherein the detergent other than the components (a) and (i) is in the form of a metal salt. The composition of claim 8, wherein the metal salt is an alkaline earth metal. The composition of claim 9, wherein the metal salt is present at about 550 ppm or less. The composition according to claim 10, wherein the metal salt is calcium or magnesium. The composition according to claim 2, wherein the detergent other than the component (a) (i) is magnesium saligenin, calcium saligenin, magnesium sulfonate, calcium sulfonate, or a mixture thereof. The composition of claim 1 further comprising a metal hydrocarbyl dithiophosphate. 2. The composition of claim 1, wherein the detergent mixture has a TBN / TAN ratio of about 3: 1 to about 7: 1. A process for preparing a composition comprising the following:
(A) A detergent package, which:
a. A metal salixarate; and b. A detergent package comprising a detergent other than component (a) (i), if necessary;
(B) Dispersant package comprising:
a. A dispersant having a carbonyl to nitrogen ratio of about 1 or more; and b. A dispersant package comprising a dispersant having a carbonyl to nitrogen ratio of less than about 1;
(C) Antioxidant package containing:
a. Hindered phenols; and (d) oils of lubricating viscosity;
Including the step of:
Wherein the composition has a phosphorus content less than or equal to about 800 ppm; and wherein the sulfate ash content is less than or equal to about 1.1 weight percent of the composition ,process.