JP2001049283A - Lubricating oil composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a lubricating oil composition which exhibits good rust prevention and wet filterability by compounding a base oil with a neutral rust preventive, a rust preventive system containing a specific compound, and an ashless dispersant. SOLUTION: The rust preventive system contains a compound represented by formula I or II [wherein Z is R1R2CH- (wherein R1 and R2 are each 34C or lower hydrocarbyl provided the total number of carbon atoms of them is 11 to 35)]. A hydrocarbyl ester represented by the formula: R(COOR')n (wherein R and R' are each about 40C or lower hydrocarbyl or hydroxyhydrocarbyl; and n is 1 to 4) is suitable as the neutral rust preventive. Each ingredient is added directly or in the form of a concentrate to the base oil. Irrespective of the form of ingredients, the wt. ratio of the neutral rust preventive to the rust preventive system is usually (3:1)-(8:1). The wt. ratio of (the neutral rust preventive + the rust preventive system) to the ashless dispersant is usually (7.5:1). Moreover, a 20C or higher aliphatic carboxylic acid or carboxylic anhydride is compounded.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a lubricating composition exhibiting good rust prevention and wet filterability and its use.

[0002] Fluids / lubric for turbine ("R &O"), hydraulic and industrial applications
ant) must meet a variety of performance characteristics, but this tends to be achieved by blending the additive / additive pack with the base oil. Such additives / additive packs provide the base oil with the desired properties so that it is suitable for use in the intended application.

[0003] Rust prevention is a frequently desired property, especially in hydraulic fluids and turbine oils, and many types of additives have been used to achieve it. In this regard,
Recently, acidic rust inhibitors such as the reaction products of carboxylic acids, polyalkylene polyamines and alkenyl succinic anhydrides,
Attention has been paid to reaction products such as those described in US Pat. No. 4,101,429. Unfortunately,
Such acidic rust inhibitors can provide the desired level of rust inhibition, but in the presence of water, they can also form metals (which are deliberately in the form of other functional additive components, such as metal-containing detergents). Or may be present as contaminants). Such interactions result in the formation of degradation products, thereby forming sediments as particulates and / or precipitates. Degradation products are particularly problematic in hydraulic fluids, because the hydraulic fluid must be carefully and neatly maintained to maintain good power transmission and prevent damage to the hydraulic equipment in which they are used. This is because it is necessary to avoid contamination. Very fine filters are used to ensure that such fluids are substantially free of contaminants. However, the resulting type of degradation products can lead to filter clogging, or blocking.

[0004] Turbine oil is used as lubricating oil (R
& O oil) is another important situation (pr
It is a representative of an actual situation.
In order to maintain effective operating conditions and to prevent damage to the equipment in which they are used, the turbine oil must be carefully kept clean and free of contaminants. Again, fine filters have been used to minimize the amount of contaminants.

The present invention provides a rust performance comparable to compositions based on acidic rust inhibitors of the type described above.
a lubricating oil composition that exhibits good wet filterability, especially without water (e.g., even in the presence of water) and the metal (s) present in the formulated lubricating oil. To provide. Also, a rust inhibitor system showing good solubility in various oil basestocks (rust inhibitor system).
It would also be desirable if the system could provide a "stem". The present invention also satisfies such criteria.

Accordingly, the present invention provides a base oil, (A) at least one neutral rust inhibitor and (B) a compound represented by the formula:

[0007]

Embedded image

Wherein Z is a group R ₁ R ₂ CH—, wherein R ₁ and R ₂ are each independently a hydrocarbyl group containing up to 34 carbon atoms, The total number of carbon atoms in the radicals R ₁ and R ₂ is from 11 to 35], and (C) said rust inhibitor which is an ashless dispersant Solubilizing system
(a) lubricating oil composition comprising:

As used herein, the term “neutral rust inhibitor”
-Means a rust inhibitor substantially free of COOH functional groups.

The at least one neutral rust inhibitor is preferably of the formula R (COOR ') _{n wherein} R and R' are each independently a number of up to about 40 carbon atoms. A hydrocarbyl or hydroxyhydrocarbyl group comprising
And n is from 1 to 4].

Preferably, R and R 'in said hydrocarbyl ester (A) are each independently a hydrocarbyl or hydroxyhydrocarbyl group containing from 8 to 20 carbon atoms, and n is from 1 to 4. .

It will be understood that the maximum number of groups COOR 'present on said hydrocarbyl or hydroxyhydrocarbyl group R will vary depending on the number of carbon atoms in R. For example, the maximum possible value of n would be 4 where R is a hydrocarbyl group containing only one carbon atom. The maximum value for n when R is a hydroxyhydrocarbyl group containing one carbon atom will be 3.

The preparation of the hydrocarbyl esters can be carried out by a conventional esterification procedure using a suitable alcohol and acid, acid halide, acid anhydride or a mixture thereof. It is also possible to produce the esters of the invention using conventional transesterification methods. "Essentially free" means that the starting acid, acid halide, acid anhydride or mixture thereof used in the preparation of such hydrocarbyl esters is in an amount sufficient to theoretically convert all of the -COOH groups to esters. Means to react with alcohol. The TAN of such an ester will typically be less than 10 mg KOH / g. Suitable esters include, but are not limited to, octyl oleyl malate, dioleyl malate, monooleate of pentaerythritol and monooleate of glycerol. Among these, it is more preferable to use pentaerythritol monooleate.

[0014] Another class of suitable neutral rust inhibitors include 1-
Aspartic acid diesters of (2-hydroxyethyl-2-heptadecenyl) -imidazoline are included. Such imidazolines are predominantly diester mixtures of imidazoline and L-aspartic acid based on the reaction between oleic acid and ethanolamine. Esters of this type are available from Mona Industries, Inc. From Mon
Commercially available as acor ™ 39.

The group Z in the compound (B) is, for example, 1-
Methylpentadecyl, 1-propyltridecenyl, 1-
It may be pentyltridecenyl, 1-tridecenylpentadecenyl or 1-tetradecyleicosenyl. The total number of carbon atoms in the radicals R ₁ and R ₂ is preferably 16 to 28, more usually 18 to 24. It is particularly preferred that the total number of carbon atoms in the radicals R ₁ and R ₂ is about 20 to 22. Preferred compounds (B) are 3- _{C18-24alkenyl-} 2,5-pyrrolidinedione, i.e. compounds having an average number of carbon atoms in the alkenyl group of 18 to 24.

In one aspect of the invention, compound (B) has a titratable acid number (TAN) of about 80 to about 140 mg KOH / g, preferably about 110 m / g.
g KOH. This TAN is transferred to ASTM D 664
Measure according to

Such compounds (B) are commercially available or can be prepared by the application or adaptation of known techniques (eg EP-A-0 389 237).
No.).

Component (C) is an ashless dispersant. Many types are known and any of them are considered useful in the practice of the present invention. Accordingly, such ashless dispersants are hydrocarbyl succinimides, ie, polyamines such as polyalkylene polyamines and hydrocarbyl succinic acylating agents.
It may be a reaction product of a rating agent. The term "succinimide" is intended to include compounds which may also have amide, amidine and / or salt bonds in addition to the imide bond resulting from the described reaction. Preferred compounds among such succinimides are those in which one of the reactants is an aliphatic hydrocarbyl-substituted succinic acylating agent, the hydrocarbyl moiety containing at least 40 carbon atoms. Such hydrocarbyl moieties are typically derived from polyalkenes. Useful polyalkenes generally have a number average molecular weight of about 500 to about 10,000, for example, about 950 to about 50.
00. Such polyalkenes themselves can be derived from ethylenically unsaturated monomers such as ethylene, propylene, 1-butene, isobutene and 1-octene, or polyolefinic monomers such as 1,3-butadiene or isoprene. Such a polyalkene is preferably a polyisobutene.

The succinic group of the acylating agent is usually a group derived from maleic acid, maleic anhydride or fumaric acid. Thus, in one embodiment of the invention, the acylating agent is polyisobutenyl succinic acid or polyisobutenyl succinic anhydride.

The polyalkylene polyamine has the formula H ₂
N (CH ₂ ) _n (NH (CH ₂ ) _n ) _m NH _{2 wherein} n is from 2 to about 10 (preferably 2 to 4, most preferably 2) and m is 0 to 10, It is preferably about 1 to 6.]. Examples include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, spermine, pentaethylenehexamine, propylenediamine, butylenediamine, hexamethylenediamine and decamethylenediamine. Mixtures of amines can also be used. Preference is given to using tetraethylenepentamine or an amine mixture whose overall composition is close to tetraethylenepentamine. Another useful class of polyamines are those comprising a mixture of acyclic hydrocarbyl polyamines and cyclic hydrocarbyl polyamines. The use of such amines, as well as the use of such amines, is specifically disclosed in EP-A-0460309. This latter describes useful ashless dispersants of the type described above and their preparation. Useful dispersants are also commercially available.

Instead of reacting the acylating agent with an amine, the acylating agent may be replaced with an organic hydroxy compound,
For example, it is possible to produce a useful dispersant by reacting with phenols and alcohols and / or basic inorganic materials. Also, such dispersants are well known in the art (eg, US Pat. No. 4,466,894).

In a possible embodiment, the ashless dispersant can be a so-called "Mannich dispersant". These are the reaction products of an alkylphenol (the alkyl group typically containing at least about 30 carbon atoms) and an aldehyde, especially formaldehyde, and an amine, such as a polyalkylene polyamine. Such dispersants are also well known in the art (eg, US Pat. No. 3,41,41).
No. 3,347, U.S. Pat. No. 3,697,574, U.S. Pat. No. 3,725,277, U.S. Pat. No. 3,725,480.
And U.S. Pat. No. 3,726,882).

In another embodiment, the ashless dispersant can be the reaction product of a high molecular weight hydrocarbyl halide and an amine. Such dispersants are known in the art and are disclosed in U.S. Pat. No. 3,454,555 and U.S. Pat.
No. 65,804.

Any of the above dispersants can also be used in post-treated form, that is, in a state where they have subsequently been reacted with one or more conventional post-treating agents. Examples of suitable post-treating agents include boron compounds, phosphorus compounds, and acylating agents such as dibasic acylating agents. Suitable post-treatments are discussed in more detail, for example, in EP-A-0460309.

Yet another class of ashless dispersants that can be used are those made from oil-soluble monomers such as decyl methacrylate, vinyl decyl ether and high molecular weight olefins and monomers containing polar substituents. Can be mentioned. They are also known in the art (eg, US Pat. No. 3,687,849 and US Pat.
02, 300).

In one embodiment of the present invention, the composition further comprises, as component (D), an aliphatic carboxylic acid or carboxylic anhydride whose aliphatic group contains at least 20 carbon atoms. Such groups typically contain no more than about 500 carbon atoms, preferably contain about 10 to about 300 carbon atoms, and often contain about 10 to about 150 carbon atoms. For example, component (D) contains about 20 carbon atoms in the fatty substituent.
From about 500, preferably from about 30 to about 30 carbon atoms.
It may be a fatty substituted succinic acid or anhydride containing zero, often from about 50 to about 150 carbon atoms.
Patents describing useful aliphatic carboxylic acids or anhydrides and methods for their preparation include U.S. Patent Nos. 3,215,707, 3,219,666, 3,231,58.
7,3,912,764,4,110,349 and 4,2
34,435 and GB 1,440,219.

Component (D) in one embodiment of the present invention
Is an alkenyl carboxylic acid or carboxylic anhydride in which the alkenyl group contains 10 to 75 carbon atoms, preferably alkenyl succinic anhydride in which the alkenyl group contains 10 to 65 carbon atoms. Component (D) in such embodiments comprises a polyisobutenyl moiety of from about 300 to about 9
It may be a polyisobutenyl succinic anhydride having a number average molecular weight of 50. It has been found that the use of component (D) provides further advantages in terms of the solubility of the component.

The number average molecular weight shown in the present specification is the number average molecular weight measured by mass spectrometry.

Unless otherwise specified, all hydrocarbyl groups and moieties can be straight or branched.

In one embodiment of the present invention, the composition comprises an acidic rust inhibitor and / or a metal detergent.
substantially no tergents). For the purposes of the present invention, the term “substantially free” means that neither acidic rust inhibitors nor metals (eg, as metal-containing detergents) are intentionally added to the finished oil (either due to contamination or as some impurities). It is possible).

Lubricating oils intended for use in the present invention include natural lubricating oils, synthetic lubricating oils and mixtures thereof. Suitable lubricating oils also undergo hydrocracking (as opposed to solvent extraction) to aromatic and polar components contained in crude oils, as well as to base stocks obtained from isomerization of synthetic and slack waxes. Includes base stocks produced through the making. The kinematic viscosity of each such lubricating oil at 100 ° C., for both natural and synthetic, is generally about 1 × 10 ⁻⁶ m
² / sec to about 40 × 10 ⁻⁶ m ² / sec (about 1 to about 40 cS
t), but for typical applications each oil is 100 ° C
From about 2 × 10 ⁻⁶ m ² / sec to about 8 × 10 ⁻⁶ m ² / sec (about 2 × 10 ⁻⁶ m ² / sec.
From about 8 cSt) to about 8 cSt).

[0032] Natural base oils include animal oils, vegetable oils (eg, castor oil and lard oil), petroleum, mineral oil, and oils derived from coal or shale. A preferred natural base oil is mineral oil.

Mineral oils useful in the present invention include all conventional mineral oil base stocks. It includes oils of naphthenic or paraffinic chemical structure. They may be acids, alkalis, and oils that have been purified using conventional methods with clay or other agents, such as aluminum chloride, or solvents such as phenol, sulfur dioxide, furfural, dichlorodiethyl ether, and the like. It may be an extracted oil produced by solvent extraction using a solvent. It is also possible to subject them to a hydrotreatment or hydrorefining, cooling or dewaxing using a catalytic dewaxing treatment. Such mineral oils may be oils made from pristine sources or may be composed of isomerized wax materials or other refining process residues.

The kinematic viscosity of such a mineral oil at 100 ° C. will typically be from 2 × 10 ⁻⁶ m ² / sec to 12 × 10 ⁻⁶ m ² / sec ( ² cSt to 12 cSt). One suitable mineral oil
The kinematic viscosity at 00 ° C. is from 3 × 10 ⁻⁶ m ² / sec to 10 × 1
0 ^-6 m ² / sec (3 to 10 cSt), 5 × 10 ^-6
mineral oil exhibits a viscosity of m from ² / sec 9 × 10 ^-6 m ² / s (9 cSt 5) is most preferred.

[0035] Synthetic lubricating oils useful in the present invention include hydrocarbon oils and halo-substituted hydrocarbon oils, such as olefin oligomers, polymers and copolymers [eg polybutylenes, polypropylenes, propylene , Isobutylene copolymer, chlorinated polylactenes, poly (1-hexene) s, poly (1-hexene)
Octenes) and their mixtures]; alkylbenzenes [eg dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes and di (2-ethylhexyl) benzenes]; polyphenyls [eg biphenyls, terphenyls, alkyls] Substituted polyphenyls] and alkyl-substituted diphenyl ethers, alkyl-substituted diphenyl sulfides as well as their derivatives,
Analogs and homologs are included. Suitable synthetic oils are
Oligomers of α-olefins, especially oligomers of 1-decene (also polyalphaolefins or PAOs)
Also known as a kind).

The synthetic lubricating oils also include alkylene oxide polymers, copolymers, copolymers and derivatives thereof (terminal hydroxyl groups modified by esterification or etherification). Synthetic oils of this type include polyoxyalkylene polymers formed by the polymerization of ethylene oxide or propylene oxide: alkyl and aryl ethers of such polyoxyalkylene polymers (eg, methyl-polyisopropylene glycol ether having an average molecular weight of 1000). , Molecular weight 1
And mono- and poly-carboxylic esters thereof (eg, acetate esters of tetraethylene glycol, mixed C ₃ -C ₈ fatty acid esters and C _12).
Oxo acid diester).

Another class of suitable synthetic lubricating oils include dicarboxylic acids such as phthalic acid, succinic acid, alkylsuccinic and alkenylsuccinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipine. acid,
From linoleic acid dimer, malonic acid, alkylmalonic acid and alkenylmalonic acid) and various alcohols (such as butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, monoethers of diethylene glycol and propylene glycol) Includes made esters. Specific examples of such esters include dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl isophthalate, didecyl phthalate, Includes diicosyl sebacate, 2-ethylhexyl diester of linoleic acid dimer, and complex esters formed by reacting 1 mole of sebacic acid with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid . Suitable types of oil belong to this class of synthetic oils are adipates of C ₁₂ alcohol from C _4.

Esters useful as synthetic lubricating oils also include C ₅ to C ₁₂ monocarboxylic acids and polyols and polyol ethers, such as neopentyl glycol, trimethylolpropane, pentaerythritol,
Includes esters made from dipentaerythritol and tripentaerythritol and the like.

Silicon-based oils (eg, polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxy-siloxane oils and silicate oils) constitute another useful class of synthetic lubricating oils. Such oils include tetra-ethyl silicate, tetraisopropyl silicate, tetra- (2-ethylhexyl) silicate, tetra- (4-methyl-2-ethylhexyl) silicate, tetra-silicate (pt- Butylphenyl), hexa- (4-methyl-2-pentoxy) -disiloxane, poly (dimethyl) -siloxanes and poly (methylphenyl) siloxanes. Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (eg, tricresyl phosphate, trioctyl phosphate, and diethyl ester of decylphosphonic acid), polymers of tetrahydrofuran, and poly-α-olefins.

Such lubricating base oils can be derived from refined, rerefined oils or mixtures thereof. Unrefined oils are obtained directly from a natural or synthetic source (eg, coal, shale, or tar sands bitumen) without further purification or treatment. Examples of unrefined oils include shale oil obtained directly from a retort operation, petroleum oil obtained directly from distillation, or ester oil obtained directly from an esterification step, each of which is subsequently used without further processing. Refined oil is 1
Same as the unrefined oil except it undergoes one or more purification steps to improve one or more properties. Suitable purification techniques include distillation, hydrotreating, dewaxing, solvent extraction, acid or base extraction, filtration and percolation, all of which are known to those skilled in the art. Rerefined oils are obtained by treating used oils using a treatment similar to that used to obtain the refined oils. Such rerefined oils are also known as reclaimed or reprocessed oils, which are often subjected to additional treatment using techniques to remove spent additives and oil breakdown products. It is also possible to use white oils as taught in US Pat. No. 5,736,490 as base oil, especially in turbine applications.

Another aspect of the present invention relates to the fact that the active ingredients of the lubricating oil composition can be dissolved in various types of base oils. In fact, the aromaticity (a
(there is a decrease in solubility)
It is believed that the reason that the rust inhibitor system exhibited improved solubility in the prepared base stock was the presence of the ashless dispersant (C) and compound (D) (if present). One consequence of increasing the solubility of the additive is that the filterability is improved. The present invention also provides the use of an ashless dispersant (C) and optionally a compound (D) for the purpose of improving the aesthetic appearance of the base oil comprising said rust inhibitor system when water is mixed therein. I do.

[0042] Original equipment manufacturers are constantly striving to improve the performance of lubricating oils, even though lubricating oil formulations are under pressure due to environmental constraints. As a result, one significant change facing the industrial lubricating oil industry is that base oils that have been subjected to hydrocracking and catalytic dewaxing to suit turbine, hydraulic and industrial oil applications are increasingly used. It must have been. Such hydrogenation and dewaxing operations can result in base oils having significantly lower aromatics and sulfur levels, thereby resulting in lubricating additives (lub) used in such base oils.
solubility and thus performance may be affected. The additive components (A) and (B), when they are used together with component (C) and when they are used together with (D), a range of base oils, more particularly group I , Group II, Group III and Group IV basestocks exhibit good solubility and thus provide advantages in terms of formulation flexibility.

American Petroleum
The Institute classifies such different types of basestocks as follows: Group I contains> 0.03% by weight sulfur and / or saturates (satu).
rates is <90% by volume and the viscosity index is 80-120.
Group II: sulfur ≦ 0.03% by weight, saturates ≧ 90% by volume and viscosity index 80-120; Group III: sulfur ≦ 0.03% by weight and saturates ≧ 9
Viscosity index> 120 at 0% by volume; Group IV is entirely polyalphaolefin. Hydrotreated basestocks and catalytic dewaxed basestocks generally fall into Group II and Group III due to their low sulfur content and low aromatics content. Polyalphaolefins (Group IV basestocks) are synthetic base oils made from various alpha olefins, which are substantially free of sulfur and aromatics.

Formulation of the lubricating oil composition of the present invention can be accomplished by simply blending the various components with a suitable base oil.

In another aspect of the present invention, the additive component used in the practice of the present invention is provided as a concentrate for convenience.
It can be formulated into a lubricating oil composition ready for use. Such concentrates may contain, in addition to the various components, solvents and diluents for fluid components. Both such solvents and diluents should be miscible and / or soluble in the base oil to which such concentrates are to be added. Suitable solvents and diluents are well known. Both such solvents and diluents may themselves be the base oil of the lubricating oil composition. Such a concentrate may suitably include any of the conventional additives used in lubricating oil compositions. The proportion of each component included in this concentrate is controlled by the intended dilution, but the top treatment (to
It is also possible to perform p treatment.

Whether components (A) and (B) are added directly to the base oil or in the form of a concentrate,
The weight ratio of (A) :( B) is usually from 3: 1 to 8: 1, preferably from 4: 1 to 6: 1. The total amount of (A) and (B) present in the finished oil should be from 0.15 to 0.5% by weight, preferably from 0.20 to about 0.4% by weight. [(A) + in the concentrate or finished oil
The weight ratio of (B)] :( C) is usually 7.5: 1.
The total amount of (C) in the finished oil is usually 0.03% by weight. Regardless of whether component (D) is added directly to the base oil or in the form of a concentrate, component (D) is added to the finished oil in an amount of 0.0
It should be present in an amount of 1% by weight. The amount of (A), (B), (C) and (D) (if used) in the concentrate is such that the concentrate is treated at a typical throughput of, for example, 0.3.
Such amounts are achieved in the finished composition when used in an amount of 0% by weight.

Other additives commonly used in lubricating oils / fluids for turbine, hydraulic and industrial applications can be included in the compositions or concentrates of the present invention. They include antiwear agents such as sulfur and / or phosphorus containing compounds, antioxidants, demulsifiers and corrosion inhibitors. If such additives are present, they are used in amounts usually used for such applications. For certain additives, it may be included in the concentrate, and for certain additives,
It may be added as a top treatment to a fully formulated lubricating oil / fluid.

The invention will now be illustrated by the following examples, which are not intended to limit the scope of the invention in any way.

[0049]

EXAMPLE Lubricating fluid (lubricant fluid)
d) The composition was formulated according to the table below. The amounts given for each component are the amounts expressed as weight percent of the components in the additive concentrate. The throughput indicates the level of dilution of the concentrate when formulating the composition.

The compatibility of the additive components contained in the composition was visually evaluated after one month.

The wet filterability of each fluid was determined by Afnor E48
It was evaluated by a −691 (wet) test. In the latter, the fluid treated with water is converted to a certain absolute stopping power (sto
Filter under constant pressure and temperature conditions through a membrane that shows pping power.

The filtration index IF of the fluid is given for a given fluid in the ratio:

[0053]

(Equation 1)

[Where T ₃₀₀ is the time for 300 cm ³ of hydraulic oil to pass through the membrane, T ₂₀₀ is the time for ₂₀₀ cm ³ of hydraulic oil to pass through the membrane, and T ₁₀₀ is 100 cm ^{3 for} 100 cm ³
Is the time of the hydraulic oil passes through the membrane, T ₅₀ is, 50 cm
³ is the time for the hydraulic oil to pass through the membrane].

Thus, the IF ratio consists of comparing the filtration rates during the course of testing the fluid. Not only this ratio but also various segments (segme
nts) represents the ease of filtration of the fluid. An IF value of less than 1 in this test method indicates a fault. The filterability of the fluid is better the closer the IF value is to one. If the membrane becomes clogged during the test, the result is recorded as abort.

The filtration properties of the oil-based fluids are evaluated using the Shell filtration test with and without calcium and / or water contamination. Each of the as-blended and contaminated fluids was tested twice as follows. Three
After pretreatment of 70 ml of test oil at 70 ° C., 6
1.2 micron Mil using a vacuum of 50 mmHg
Filter through a lipore membrane. No special adjustment of the temperature of the fluid is made, but it should be in the range of 19 to 26 ° C. Record the time (in seconds) required to filter each 100 ml fluid sequentially or the time at which the filtration membrane is shut off. Pass the result of Shell filtration test (this is 300m
l means all of the oil has passed through the filter)
Or failed (meaning the filter was shut off).

The tendency of the fluid to cause rust is determined by ASTM D
Evaluated during the 665B test. In this test, a steel blank is cleaned by rotating it at 1700 rpm while in contact with a 150 grade aluminum oxide fabric and then a 280 grade fabric. A PTFE holder (h
older) and install this assembly (ass
embly) is completely immersed in the test tube containing the fluid under test. First, it was washed with a detergent solution, rinsed with distilled water, and then dried in an oven for about 15 minutes.
Pour 300 ml of test fluid into a 0 ml beaker. Next, the beaker is placed in an oil bath (set at 60 ° C.), and a perspex cover is attached to the oil bath. The stirrer is lowered through a hole in the top of the cover to enter the test fluid and stir the fluid. After about 30 minutes, the steel blank is removed from the test tube and the oil is allowed to drain for a short period of time.
After that, put in the beaker. After another 30 minutes, the test fluid contained in the beaker was mixed with a synthetic seawater solution for 30 minutes.
Add ml. After 24 hours, the steel blank is removed from the test fluid and allowed to run down, rinsed with heptane and then evaluated according to the following rating system: Pass: no rust Light: rust spots each less than 1 mm in diameter No more than 6 Medium: More than 6 spots, but limited to less than 5% of the surface of the blank Bad: Rust covers more than 5% of the surface of the blank .

[0058]

[Table 1]

[0059] Note component (A) was monooleate of pentaerythritol.

Component (B) is 3-C _{18-24 alkenyl-}
2,5-pyrrolidinedione.

The component (C) is composed of anhydrous polyisobutenyl (Mn)
1300) Polyisobutenyl succinimide derived from succinic acid and tetraethylenepentamine.

The component (D) is composed of anhydrous polyisobutenyl (Mn)
950) Succinic acid.

The base stock of Group III is Yub
case 6.

The compatibility results show that the additive components remain completely in solution in the base stock used. No precipitate was observed after one month. This means that the components may have such a group III
Has demonstrated excellent solubility in purified basestocks. It is expected that similar compatibility results will be obtained in less severe Group I and II base stocks.

When experiment 1 was repeated, omitting only component (C), the compatibility grade in the Group III base stock was reduced, ie such an oil solution after one month due to the presence of a precipitate. Cloudy. This demonstrates that component (C) exhibits efficacy in solubilizing such rust inhibitor components.

The Afnor results of Experiments 1 and 2 show that the compositions according to the invention show excellent wet filterability.

The results of the Shell filtration test show the water tolerance of the composition.
Indicates that it is excellent even in the presence of a metal.

The results of both ASTM D665B rust tests passed, indicating that the rust inhibiting properties of the present composition are satisfactory.

The features and embodiments of the present invention are as follows.

1. A lubricating oil composition, comprising a base oil,
(A) at least one neutral rust inhibitor and formula (B):

[0071]

Embedded image

Wherein Z is a group R ₁ R ₂ CH—, wherein R ₁ and R ₂ are each independently a hydrocarbyl group containing up to 34 carbon atoms, The total number of carbon atoms in R ₁ and R ₂ is from 11 to 35], and (C) a solubilizer for the rust inhibitor system, which is an ashless dispersant. A composition comprising:

2. The at least one neutral rust inhibitor (A) has the formula R (COOR ') _n [wherein R and R'
Is independently a hydrocarbyl or hydroxyhydrocarbyl group containing up to about 40 carbon atoms, and n is from 1 to 4]. object.

3. 3. The composition according to claim 2, wherein R and R 'are each independently a hydrocarbyl or hydroxyhydrocarbyl group containing from 8 to 20 carbon atoms.

4. 4. The composition according to claim 3, wherein (A) is a monooleate of pentaerythritol.

5. The composition according to any one of the preceding items, wherein the total number of carbon atoms in the groups R ₁ and R ₂ in (B) is 18 to 24.

6. (B) is 3-C _{18-24 alkenyl-}
6. The composition according to claim 5, which is 2,5-pyrrolidinedione.

7. The composition according to any one of the preceding claims, wherein the ashless dispersant is a Mannich base ashless dispersant.

8. 7. The composition of any one of claims 1 to 6, wherein the ashless dispersant is a reaction product of a polyamine and a hydrocarbyl-substituted succinic acylating agent, wherein the hydrocarbyl group contains at least 40 carbon atoms.

9. 9. The composition according to claim 8, wherein said succinic acylating agent is polyisobutenyl succinic acid or polyisobutenyl succinic anhydride derived from polyisobutene having a number average molecular weight of 700 to 5,000.

10. The polyamine has the formula H ₂ N (CH ₂ )
_{n (NH (CH 2) n} ) m NH 2 [ wherein, n is 2 to 10 and m is from 0 to 10] 8 or 9, wherein composition wherein the alkylene polyamines represented by.

11. 11. The composition according to claim 10, wherein said polyamine is tetraethylenepentamine or a polyamine mixture whose composition is close to tetraethylenepentamine.

12. (D) The composition according to any one of the preceding items, wherein the aliphatic group further comprises an aliphatic carboxylic acid or a carboxylic anhydride containing at least 20 carbon atoms.

13. 13. The composition according to claim 12, wherein (D) is an alkenyl carboxylic acid or carboxylic anhydride in which the alkenyl group contains from 10 to 75 carbon atoms.

14. 14. The composition according to claim 13, wherein (D) is an alkenyl succinic anhydride wherein the alkenyl group contains 10 to 65 carbon atoms.

15. 15. The composition according to claim 14, wherein (D) is a polyisobutenyl succinic anhydride having a number average molecular weight of 300 to 950.

16. The composition according to any one of the preceding claims, wherein the base oil is a Group I, II or III base oil.

17. The base oil is Group II or I
17. The composition according to claim 16, which is a base oil of II.

18. The composition according to any one of the preceding claims, further comprising at least one additive selected from antiwear agents, antioxidants, demulsifiers and corrosion inhibitors.

19. Use of an ashless dispersant (C) as defined in any one of Items 1 and 7 to 11, wherein
Compound (A) as defined in any one of Items 1 to 3
Use of a rust preventive system comprising a compound (B) as defined in any one of paragraphs 1, 5 and 6 for improving the solubility in a base oil.

20. 20. Use according to item 19, wherein said ashless dispersant (C) is used in combination with an aliphatic carboxylic acid or a carboxylic anhydride as defined in any one of items 12 to 15.

21. 21. Use according to claim 19 or 20, wherein the lubricating oil composition contains certain metals.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C10M 133/16 C10M 133/16 133/44 133/44 133/56 133/56 137/02 137/02 139 / 00 139/00 A 145/14 145/14 159/12 159/12 159/16 159/16 // C10N 30:12 40:08 40:12

Claims (2)

[Claims] 1. A lubricating oil composition comprising: a base oil; (A) at least one neutral rust inhibitor; and (B) a compound represented by the formula: Wherein, Z is CH- group R ₁ R _2, wherein, R ₁ and R ₂ are each independently a hydrocarbyl group containing the number of below 34 carbon atoms, the radicals R ₁ And the total number of carbon atoms in R ₂ is from 11 to 35], and (C) a solubilizer for the rust inhibitor system, which is an ashless dispersant. A composition comprising: 2. Use of an ashless dispersant (C) as defined in claim 1, comprising a compound (A) as defined in claim 1 and a compound (B) as defined in claim 1. Use to improve the solubility of the resulting rust inhibitor system in base oils.