JPH06179887A - Improvement of friction of synthesized gear oil - Google Patents

Abstract

PURPOSE: To produce a gear oil lubricant suitable to be used for a transmission equipped with a synchronizer.

CONSTITUTION: This lubricant has 4 to 32 mm² sec^-1 (cSt) kinematic viscosity at 100°C and contains (a) a base oil, (b) a gear oil additive package and (c) at least one kind of alkali and alkaline earth metal salts of oil-soluble sulfonic acids. The base oil contains at least 25 wt.% (i) hydrogenated poly-α-olefin oligomer oil or (ii) synthetic ester oil or (iii) combination of (i) and (ii). The gear oil additive package is used in such an amt. or larger that the gear oil lubricant satisfies the specifications concerning API-GL4 service. The alkali or alkaline earth metal salt of oil-soluble sulfonic acid (c) is used in an enough amt. to improve the frictional characteristics of the lubricant used for a manual transmission, especially a synchronizer-type manual transmission, and by 0.01 to 2 wt.% range based on the whole weight of the lubricant.

COPYRIGHT: (C)1994,JPO

Description

Detailed Description of the Invention

The present invention relates to improving the friction properties of gear oils in which the base oil is a synthetic oil, such as a poly-alpha-olefin oil (PAO) or a synthetic ester oil or which contains significant amounts thereof.

Modern large commercial vehicles equipped with manual transmissions of the synchronizer type are typically operated with conventional mineral oil-based transmission lubricants. Such lubricants contain additives for wear protection and corrosion protection, as well as other advantageous property-improving additives. The level and type of additive used depends on the oil performance requirements including low temperature properties or wear protection. The performance display used is API-G.
L4 and API-GL5 are included. More recently, PG1, PG2 and API-GL7 have been defined. Furthermore, the degree of demulsification may be suitable. Conventional crankcase mineral oil lubricants containing zinc dialkyldithiophosphate, sulfonates or ashless dispersants at normal levels can be used to meet API-GL4 and lower performance specifications. Mineral oil lubricants that meet all of the above levels are based on essentially ashless P / S formulations but contain significant levels of alkali metal borate and metal sulfonate. P / S formulation (eg OLOA
9750 additive) satisfied levels at least up to API-GL5. As those in the field will recognize,
"P / S" refers to a gear oil additive package in which an antiwear and / or extreme pressure additive system containing phosphorus and sulfur is used.

However, at more extreme temperatures, and at other extremes encountered by many modern vehicles, formulating these transmission fluids with fluids other than the more classical mineral oils provides significant advantages. There is a possibility that These synthetic fluids, which are often referred to as such, can be used with mineral oils or on their own. Synthetic oils / fluids of major interest in this connection include poly-α-olefin oils (PAO) and synthetic ester oils, as they exhibit thermal stability. It also has a desired viscosity characteristic.

Unfortunately, unlike classical mineral oil-based transmission fluids, many synthetic fluids based on essentially ashless P / S additive systems are based on synchronizers. In the transmission to
It provides inadequately low friction properties and thus worsens the gear change synchronization. The negative point that gear oils based on such synthesis have is Zahnradfabrik Friedrichshafen.
It can be conveniently observed as a low friction and noisy gear change in the AG Synchronizer test (hereinafter described as "ZF Synchronizer test" and referred to by its name). To solve this problem, it is usually necessary to appropriately increase the frictional properties of synthetic oil-based finishing lubricants. However, in order to do so, it is important that it does not substantially interfere with other performance qualities of this finished gear oil.

Finishing gears based on synthetic oils, such as PAO and synthetic ester oils and blends thereof, by using small amounts of additives that do not substantially affect the other properties of this finishing lubricant. It has now been found that it is possible to advantageously increase the friction exhibited by a lubricant. For example, the use of suitable additives in the oil in low amounts, such as 0.1% by weight, allowed the finish lubricant to pass the ZF synchronizer test conducted in the manner described below. .

The additives used according to the invention are alkali or alkaline earth metal salts of oil-soluble sulphonic acids, for example petroleum sulphonic acids, preferably alkylaryl sulphonic acids, more preferably alkylbenzene sulphonic acids. The salt metal preferably has low toxicity and
Metals that pose little or no concern from an environmental point of view: lithium, sodium, potassium, magnesium and calcium. However, if desired,
Barium sulphonate and strontium can also be used.

To the best of our knowledge, the APIs actually used, which obviously contain a metal sulfonate component.
There are only two GL5 gear oil compositions. The first is SPIRAX MB 90 (trademark of Shell Oil Companies), a gear oil based on regular mineral oils, which is considered to be the form of barium sulfonate corrosion inhibitor in Germany. A small amount is included.

Another class is based on the use of gear oil additive packages containing high levels of potassium borate dispersants which act as antiwear / extreme pressure agents.
These packages are believed to contain low levels of calcium, presumably in the form of sulfonate. These packages are obviously primarily (if not exclusively) used predominantly (if not exclusively) in normal mineral oil stocks when producing finished gear oils. And in any case, the level of potassium borate used in this finished oil (e.g. 1-2 wt%) is so high as to severely worsen the results obtainable in the practice of the invention, and thus It is outside the permissible concentration of the present invention.

For more information on such dispersed potassium borate additive systems, see CG Sal entitled "New Gear Lubrication Technology Using Solid Lubricant Dispersion."
Entine, SAE Technical Paper 880609 (1988), and entitled "Durability Testing of Low Viscosity Borate Gear Lubricants."
SAE Technical Paper83 by GE Callis and GY Suh
It can be found in 1731 (1983). Also, U.S. Pat.No. 3,313,727; 3,565,802; 3,819,521; 3,846,313; 3,85
3,772; 3,912,639; 3,912,644; 3,929,650; 3,997,454;
See 4,089,790; and 4,163,729.

Thus, according to one embodiment of the present invention, the kinematic viscosity at 100 ° C. is from 4 to 32 mm ² · sec ^-1.
(CSt), preferably 8 to 20 mm ² · sec ^-1 (cS
t) and a) (i) hydrogenated poly-alpha-olefin oligomer oil or (ii) synthetic ester oil or (ii)
i) a base oil containing at least 25% by weight, preferably at least 50% by weight, more preferably at least 75% by weight, most preferably 100% by weight, a combination of (i) and (ii); b) this gear oil Gear oil additive package in an amount such that the lubricant meets or exceeds specifications for GL4 service; and c) Improves friction characteristics of lubricants used in manual transmissions, especially synchronizer type manual transmissions. At least one alkali or alkaline earth metal salt of an oil-soluble sulfonic acid, in an amount ranging from 0.01 to 2% by weight, based on the total weight of the lubricant; Here, it is essentially free of any metal additive components (ie, one or more additive components other than the above metal salts). The metal, which is included in,
At most 100 ppm, preferably less than 50 ppm), and the boron content, if included, is less than 1,000 ppm, preferably 300 ppm by weight.
Gear oil lubricants are provided which are below ppm, most preferably below 25 ppm.

In the ZF synchronizer test, the advantageous increase in friction exhibited by the finished gear lubricant of the present invention is, in and of itself, dependent on the number of cycles that the test can be performed without compromising the gear change synchronization. It should be noted that it is showing that the price will rise. For example, finishing gear oils based on synthetic oils without metal sulfonate additives are 10,000
Or within 15,000 cycles, a substantial failure may be encountered. On the other hand, the finished lubricants of the invention based on synthetic oils containing metal sulphonate components are able to successfully achieve at least 50,000, usually at least 100,000 cycles of operation in this test operation. it can.

Regarding meeting or exceeding the specifications for API-GL4 service, the gear oil additive package used as component b) is actually API-
Other performance specifications such as GL5 [including not yet implemented (or envisioned) specifications, eg PG1, PG2 and API-GL7], or specifications of other countries, eg comparable JIS gear oil standards. Can satisfy the requirements for Briefly, the API-GL4 specification shall be considered to be the minimum performance level for the package. For example, if the requirements of the API-GL7 specification are, for the most part, more stringent than the so-called API-GL4, then it is necessary for the additive package to meet the requirements of the API-GL7 in this package.
Whether or not a performance test was actually performed, it would essentially meet the minimum performance requirements for use in practicing the present invention.

According to another embodiment of the present invention, (1) an oil soluble phosphorus and sulfur containing antiwear and / or extreme pressure additive supplement, and (2) at least one alkali or alkali of an oil soluble sulfonic acid. A gear oil additive package comprising an earth metal salt, the gear oil additive package further having a kinematic viscosity at 100 ° C. in the range of 4 to 32 cSt and (i) hydrogenated poly-alpha- Olefin oligomer oil or (i
i) synthetic ester oil or (iii) (i) and (i
Blending the combination of i) with a base oil containing at least 25 wt.
Characterized in that it produces a lubricant containing from 1 to 2% by weight, and said gear oil additive package: A) meets or exceeds the specifications for API-GL4 service; Also, the content of the metal different from the metal of the above metal salt is 100 ppm at most, preferably 50 pp
m or less; and C) has a boron content of 1,000 p, even if included.
pm or less, preferably 300 ppm or less, most preferably 2
5 ppm or less; gives a lubricant composition.

Yet another aspect of the present invention is that the lubricant composition is satisfactory for use in manual transmissions, especially synchronizer type manual transmissions, while meeting or exceeding the specifications for API-GL4 service. A method of advantageously modifying the friction properties of a low friction synthetic lubricant composition that includes a gear oil additive package that does not exhibit friction properties. This method provides 0.01 to 2% by weight, based on the total weight of the lubricant, so as to improve the frictional properties of the lubricant so that it is suitable for use in manual transmissions, especially synchronizer type manual transmissions. Including a range of amounts of at least one metal salt of an oil soluble sulfonic acid in the lubricant composition.

In each of the above embodiments, the metal of the sulfonate is preferably lithium, sodium, potassium, magnesium or calcium, or a combination of two or more of the above metals. However, barium and / or strontium sulfonates may also be used if desired.

In each of the embodiments of the present invention, the metal sulfonate is used as an independent component (eg, a "top-treat" to the base oil blended or blended with the additive package). As) or
Alternatively, it can be used as a component of the additive package itself. Similarly, it is preferred to use an additive package, either by blending the metal sulfonate and the individual components of the additive package separately into the base oil, or
Alternatively, it is possible to blend in various subcombinations showing compatibility.

As noted above, these base oils are partially or wholly comprised of low friction fluids such as PAO base oils and / or synthetic ester lubricating oils. These PAO fluids are usually prepared by oligomerizing or co-oligomerizing 1-alkene hydrocarbons having 6 to 20, preferably 8 to 16 carbon atoms in the molecule and then hydrogenating the resulting oligomer. It is made by doing. Hydrogenated oligomers made from 1-decene are particularly suitable. Methods for producing such liquid oligomeric 1-alkene hydrocarbons are known and reported in the literature. See, for example, U.S. Patent Nos. 3,763,244; 3,780,128; 4,172,855; 4,218,330; and 4,950,822. In addition, suitable hydrogenated 1-alkene oligomers of this type are for example the Ethyl Corporat
It is available commercially from ion and its branch offices under the trademark ETHYLFLO.

Synthetic ester oils are also well known and widely available on the market. Typical synthetic ester oils include dicarboxylic acids (eg phthalic acid, succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer) and various alcohols ( Materials such as esters with butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol) are included. Specific examples of these esters include dibutyl adipate, di (1-dipic acid adipate.
Ethylpropyl), di (1,3-dimethylbutyl) adipate, di (2-ethylhexyl) adipate, didodecyl adipate, di (tridecyl) adipate, di (2-ethylhexyl) sebacate, dilauryl sebacate, fumar Acid di-n-hexyl, dioctyl sebacate, di (1-methylpropyl) azelate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, mixed C ₉ and C
₁₁ dialkyl phthalates, dibutyl sebacate, di (1-ethylpropyl) sebacate, di (eicosyl) sebacate, 2-ethylhexyl diester of linoleic acid dimer, and 1 mol sebacic acid and 2 mol tetra Included are complex esters formed by reacting ethylene glycol with 2 moles of octylic acid.
Other synthetic esters which may be used as synthetic oils, C ₃ -C ₁₂ monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylol propane, those obtained from pentaerythritol and dipentaerythritol Is also included. Examples include trimethylolpropane tripelargonate and pentaerythritol tetracaproate.

Suitable commercial products include Emkarate 911P (ICI,
plc.) and KETJENLUBE synthetic oil (Akzo Chemicals)
Is included.

These base oils contain up to 75% by weight of mineral oil or other suitable oily liquid having a lubricating viscosity,
It may preferably comprise up to 50% by weight, more preferably up to 25% by weight, provided that this total base lubricant meets or exceeds the specifications for API-GL4 service. Provided that it is suitable for producing an agent, and further that the resulting finish oil remains subject to the friction modification according to the present invention. It is understood that most gear oil packages contain a diluent oil or solvent for the particular active material or ingredient. However, since the diluent oil or solvent has been added to the base oil either with the additive package, or independently or with one or more additive components blended individually, Such diluent oils or solvents should be excluded from consideration when assessing the composition of the base oil that the composition of the present invention has. Thus, the finish gear oil lubricant may contain up to 75% by weight of mineral oil or the like, plus any additional amount of diluent oil or solvent emerging from the additive or additive package used in formulating the finish lubricant. May be included.

The metal sulfonate used in the present invention is preferably an overbased metal sulfonate, but so-called neutral metal sulfonates can also be used if desired. It is particularly preferred to use the calcium salt of the oil-soluble alkylbenzene sulfonate, especially the overbased calcium alkylbenzene sulfonate. Methods for producing metal sulfonates are described, for example, in U.S. Pat.No. 2,865,956;
2,956,018; 2,671,430; 3,779,920; 3,907,691; 4,137,
184; 4,261,840; 4,326,972; 4,328,111; 5,089,155; and 5,112,506. Petroleum sulfonates are usually purified by sulfonation of a suitable petroleum fraction, followed by removal of acidic sludge, followed by neutralization with a suitable basic metal compound (eg oxide or hydroxide). Manufactured by. EP publication number 275,395 (July 27, 1988
Petroleum oxydates (ox
idates) and the like can also be used for the purpose of generating an overbased sulfonate. Alkylaryl sulfonates are typically prepared by sulfonation of alkylated benzene or benzene analogs (toluene, naphthalene, phenothiazine, diphenyl oxide, or diphenyl sulfide) followed by treatment and neutralization. Suitable alkylbenzenes for making these sulfonates can be generated, for example, by alkylating benzene with an oligomer or polymer such as tetrapropylene in the presence of Friedel-Crafts catalysts. Many highly suitable metal sulfonates are commercially available.

Metal sulfonates can be used in amounts ranging from as low as 0.01% by weight to as high as 2% by weight or more, based on the total weight of the finish lubricant. Generally, the amounts used do not significantly exceed those required to obtain the desired friction performance for the particular finish gear oil lubricant in question. Therefore, this amount is often less than 1% by weight and in some cases less than 0.5% by weight. In the case of the friction modifying additive package of the present invention, this amount is such that when the package is blended with the base oil at the recommended or desired concentration, the resulting finish oil is from 0.01% to 2% by weight or more, preferably The proportion is such that it contains less than about 1% by weight, and in some cases less than about 0.5% by weight metal sulfonate. Such ratios of metal sulphonate are based on the active material and, therefore, when calculating the concentration of metal sulphonate in this finishing oil or friction modifying additive package, the metal sulphonate at the time of use. It is noted that the weight of any solvent or diluent associated with the acid salt should be subtracted from the weight of the additive. However, the total weight of the finish oil or finished additive package includes the weight of the solvent or diluent.

The specifications for API-GL4 and API-GL5 services are entitled "Laboratory Performance Tests for Automotive Gear Lubricants".
for Automotive Gear Lubricants) ASTM publishing ST
Published in P-512A (March 1987).

A number of gear oil additive packages (concentrates) are available on the market that provide API-GL4 or API-GL5 performance. These are generally at least sulfur-phosphorus antiwear or extreme pressure additive systems,
It contains one or more antioxidants, one or more corrosion inhibitors, and antifoam additives, and may and preferably contains dispersant additives.

According to another embodiment of the invention: a) at least one oil-soluble ashless dispersant, preferably succinimide ashless dispersant and / or succinate-
Amide ashless dispersants, more preferably Mannich base ashless dispersants; b) at least one oil-soluble metal-free sulfur-containing antiwear and / or extreme pressure agent; c) at least one oil-soluble metal-free phosphorus-containing antiwear. And / or an extreme pressure agent; and d) at least one alkali or alkaline earth metal salt of an oil soluble sulfonic acid having a kinematic viscosity at 100 ° C. in the range of 4 to 32 cSt and (i) hydrogenated poly-
Alpha-olefin oligomer oil or (ii)
Synthetic ester oil or (iii) (i) and (ii)
0.01 to 2 wt% of the above metal salt by blending this additive package into a base oil containing at least 25 wt%, preferably at least 50 wt%, most preferably at least 75 wt% of the combination of % Lubricant composition obtained by forming a lubricant containing: A) meets or exceeds the specifications for API-GL4 service; B) contains a metal of the above metal salt, if any. Has a high content of different metals of at most 100 ppm, preferably 50 pp
m or less; and C) has a boron content of 1,000 p, even if included.
pm or less, preferably 300 ppm or less, most preferably 2
A gear oil lubricant package (concentrate) containing 5 ppm or less; Preferably,
The metal of the salt is lithium, sodium, potassium, magnesium or calcium, or a combination of two or more of the above metals.

Finishing lubricant compositions containing at least the above-mentioned components a), b), c) and d) form a further embodiment of the invention. The finish lubricant is A
It meets or exceeds the specifications for PI-GL4 services, and preferably meets or exceeds the specifications for API-GL5 services. Component a) of the above additive package and finish lubricant composition
Is most preferably Mannich base, which comprises or alternatively consists of a boronated Mannich base ashless dispersant.

Yet another embodiment of the present invention uses a Mannich base dispersant as component a) and replaces said components a) and b) in said additive package or finish lubricant composition with said Mannich base. The mass ratio (weight / weight) of nitrogen in the dispersant to sulfur in the sulfur-containing antiwear and / or extreme pressure agent is in the range of 0.0005: 1 to 0.5: 1,
It is preferably accompanied by a ratio in the range of 0.003: 1 to 0.2: 1.

In an even further embodiment, a Mannich base dispersant is used as component a) and the above components a) and c) in the additive package or finish lubricant composition are used in the Mannich base dispersant. Of nitrogen and the anti-wear and / or phosphorus in the metal-free phosphorus-containing antiwear and / or extreme pressure agent have a weight ratio (weight / weight) in the range of 0.005: 1 to 5: 1, preferably 0.01: 1. To a ratio of 2: 1.

In additional embodiments, at least one of the additive concentrates and finish lubricant compositions described above is present.
Further included are oil soluble demulsifiers of the species.

In yet another embodiment, any of the above additive concentrates and finish lubricant compositions further comprises at least one oil-soluble amine salt of hydrocarbyl phosphate that is free of sulfur.

Preferably, the halogen content of the lubricant composition of the present invention, if included, is by weight,
It is 100 ppm or less, and more preferably 30 ppm or less.

Another specific example of the present invention is shown below.

As is well known in the art, the ZF Synchronizer test is based on oil conditions in commercial synchromesh equipment under durable conditions where the bulk lubricant temperature is adjusted to relatively high levels. It is designed for performance evaluation. While it is important to simulate fairly close to the actual conditions encountered during operation, it must be considered that it is necessary to obtain test results during the acceptance period. Briefly, the two halves of the transmission synchromesh device are repeatedly brought together under known force and velocity differential conditions until they fail. Fail may be defined in terms of synchromesh performance or overall wear. The test rig used in this operation is titled "Manual Transmission Synchronizer" (Manu
al Transmission Synchronizers) Socin and Walter
s, SAE Paper Number 680008; titled “Proposed Synchromesh Test Method Using Synchronized Test Rig”
(Synchromesh Test MethodWith Proposed Synchro Tes
Rig), Fano, CEC TLPG4 Chairman's Final Repor
t, 1985; and the title "Einfluss Des Schmierstoffes.
Br from Zahnradfabrik Friedrichshafen AG in the paper "auf die Schaltelemente Von Fahrzeuggetrieben"
Designed by considering the work done by ugen, Thies and Naurian. These two synchromesh devices are assembled in a gearbox forming an oil reservoir and facilitating splash lubrication of the components. The drive may be transmitted along the main axis or through a countershaft gear that provides an increased ratio. A DC drive control system and large flywheel simulated vehicle inertia are used to keep the input speed constant. When the gear is changed, the output shaft accelerates and decelerates a small flywheel that simulates clutch inertia. A pivot connection, which is connected to the pneumatic cylinder, provides the actuation force, which is applied to the load ring strain gauge.
strain gauge). A small heater is used to control the oil temperature.

By measuring the torque transmitted through the output shaft, the synchronizing cone
An indication of the coefficient of friction between g cones) can be obtained. The synchromesh device used is a standard commercial steel device in which the inner surface of the outer synchro ring is coated with a molybdenum-based plasma spray. Prior to performing each test, these synchromesh devices are refreshed. Typically, the friction coefficient for satisfactory synchronizer performance in this test is at least 0.06 when measured at relatively high torque points during gear changes.
It is 5.

Another performance criterion that may be used when performing tests for quality evaluation is the excessive vibration exhibited by the gearbox casing in the axial plane, ie the condition indicating poor gear change. For this purpose, the rig is controlled and monitored in cooperation with the process controller. During the test consisting of 10 ⁵ cycles, record the number of poor exchanges. If this number becomes unacceptable, the study will be terminated early.

Perthometer Stylus device
vice) can be used to evaluate the test components by examining the friction surface of the internal synchronizer cone both before and after the test. When this metal surface is polished or decomposed glaze of lubricant or additive is deposited,
An unacceptably smooth surface finish results. this is,
On the contrary, it lowers the friction value during the gear change, and this results in sleeves and gear clutch teeth.
h) can result in destruction. Wear measurements on these test components are also made.

Planning with Zahnradfabrik Friedrichshafen A.G., as known to those skilled in the art, to allow the company to carry out ZF synchronizer tests on test formulations submitted by an organization. It is also possible. It is understood that a summary report of this test result will be given to the test formulation submitter.

The following examples, numbered 1 to 35, illustrate inter alia the preferred additive concentrates and oil compositions of the present invention. These examples are not intended to limit the invention and should not be considered limiting. In all of these examples, all percentages are by weight.

[0039]

EXAMPLE A 38.0 parts of sulfurized isobutylene, dicyclopentadiene and dithiophosphoric acid-0,0-dialkyl ester (wherein 4 parts of these alkyl groups based on moles) were placed in a reaction vessel.
0% is isopropyl, 40% is isobutyl, and 20% is 2-ethylhexyl) 14.0 parts product, 4.76 parts dibutyl hydrogen phosphite, and 2-ethylhexyl acid. Charge 1.75 parts of phosphate. Throughout this addition,
The ingredients of the reaction vessel are stirred and maintained at 30 ° C for 10 minutes. To this mixture was added 6.0 parts of Primene ^R 81-R amine (a mixture of tertiary alkyl primary amines in the C ₁₂ -C ₁₄ range; Rohm & Haas), and the mixture was allowed to heat for 20 minutes. Stir. Then another 4.9 parts of the tertiary alkyl monoamine product is added and the contents of the reaction vessel are maintained at 50 ° C. for 1 hour with continued stirring. While cooling the contents of this container to 40 ° C, 4.3
1 part oleic acid and 0.58 part M530 antifoam (Mons
anto Company antifoam concentrate). Then, without heating in the final stage, 1.8 parts of 2-t-dodecyldithio-5-mercapto-1,3, were added to the contents of the reaction vessel.
4-thiadiazole, 12.3 parts Amoco 9250 additive (48% oil concentrate of borated Mannich based ashless dispersant containing about 1.1% nitrogen and about 0.2% boron). Possible, patented product of Amoco Corporation), 0.77 parts of Pluronic L-121 demulsifier (BASF)
Corporation ethylene oxide-propylene oxide block copolymer) and 10.83 parts of processing oil. The resulting additive concentrate is stirred for 60 minutes.

Example B A reactor was charged with 38.3 parts of isobutylene sulphide, 14.3 parts of di-t-nonyl polysulphide, 5.7 parts of dibutyl hydrogen phosphite, 0.1 part of tolyltriazole and 29 parts of amyl acid phosphate. Prepare. Stir the ingredients of the reaction vessel throughout the addition and
Hold for 10 minutes. To this mixture 3.7 parts of Primen
e ^R 81-R amine, 3.7 parts of C ₁₆ and C ₁₈ primary amines, 1.0 part of octyl amine, and 3.2 parts of processing oil were added and the mixture was stirred for 20 minutes while 50 minutes for 1 hour with continuous stirring of the contents of this reaction vessel
Keep at ℃. Then, while cooling the contents to 40 ° C., 0.6 parts of C ₃₆ dimer acid, 0.6 parts of caprylic acid,
Add 1.0 part M530 defoamer, and 3.2 parts processing oil. Thereafter, without heating, the contents of the reaction vessel were charged with 2.7 parts of 2-t-dodecyldithio-5-mercapto-1,3,4-thiadiazole, 12.2 parts of Amoc.
o 9250 additive, 0.5 parts Pluronic L-101 demulsifier (BA
SF Corporation of ethylene oxide - block copolymer concentrate of propylene oxide), 2.9 parts of phenolic antioxidant (ETHYL ^R antioxidant 733) and 3.4
Part of processing oil is added. 60% of the resulting additive concentrate
Stir for minutes.

Example C A reaction vessel was charged with 35.8 parts of sulfurized isobutylene, 3.6 parts of dibutyl hydrogen phosphite, dicyclopentadiene and dithiophosphoric acid-0,0-dialkyl ester (wherein these were based on moles). 40% of the alkyl groups of is isopropyl, 40% is isobutyl, and 20% is 2-ethylhexyl).
Charge 8.9 parts and 1.7 parts of 2-ethylhexyl acid phosphate. The ingredients of the reaction vessel are stirred and maintained at 30 ° C. for 10 minutes throughout the addition. To this mixture was added 3.9 parts C ₁₆ and C ₁₈ primary amines, 0.7 parts octylamine, and 9.1 parts processing oil, and the mixture was stirred for 20 minutes while the reaction vessel was stirred. 1 hour 50 while continuously stirring the contents of
Keep at ℃. Then while cooling the contents to 40 ° C., 0.7 parts of caprylic acid, 0.7 parts of M544 antifoam (Monsanto Company acrylate copolymer concentrate), and 5.8 parts of processing oil are added. Add. Then, without heating, the contents of this reaction vessel were charged with 12.0 parts of Am.
oco 9250 additive, 1.5 parts of 2-t-dodecyldithio-
5-mercapto-1,3,4-thiadiazole, 0.8
Parts of Chemax HCO-5 (hydrogenated castor oil ethoxylate concentrate from Chemax, Inc.), and 4.8 parts of processing oil are added.
The resulting additive concentrate is stirred for 60 minutes.

Example D In a reaction vessel, 35.1 parts of sulfurized isobutylene, 3.8 parts of dibutyl hydrogen phosphite, dicyclopentadiene and dithiophosphoric acid-0,0-dialkyl ester (wherein, based on moles, these 40% of the alkyl groups of is isopropyl, 40% is isobutyl, and 20% is 2-ethylhexyl).
Charge 6.6 parts and 1.0 part of 2-ethylhexyl acid phosphate. The ingredients of the reaction vessel are stirred and maintained at 30 ° C. for 10 minutes throughout the addition. After adding 3.3 parts of C ₁₆ and C ₁₈ primary amines and 8.3 parts of processing oil to the mixture, the mixture is stirred for 20 minutes while the contents of the reaction vessel are continuously stirred. While maintaining at 50 ° C for 1 hour. Then, while cooling the contents to 40 ° C., 0.6 parts of caprylic acid,
Add 0.6 parts M544 defoamer, and 8.3 parts processing oil. Thereafter, without heating, the contents of this reaction vessel were charged with 12.8 parts of Amoco 9250 additive, 1.3 parts of 2-
Add t-dodecyldithio-5-mercapto-1,3,4-thiadiazole, and 8.3 parts processing oil. The resulting additive concentrate is stirred for 60 minutes.

Examples 1-4 Using the above individual Examples AD, gear lubricants are formulated as follows.

Additive Package 6.5 wt% Amoco 421 Magnesium Sulfonate 0.35 wt% Diisodecyl Adipate 25 wt% ETHYLFLO 174 PAO 58.15 wt% ETHYLFLO 168 PAO 10.0 wt% Examples 5-8 Above Examples Using the individual additive packages A-D,
The alternative lubricants of the present invention are formulated as follows.

The additive package 3.2 wt% HiTEC ^R 614 Calcium sulfonate 0.1 wt% ETHYLFLO 170 PAO 80.7 wt% ETHYLFLO 174 PAO 6.0% by weight diisodecyl adipate 10.0% by weight Example 9 below A lubricating oil composition based on the synthetic oil of the present invention is made by blending the components together in the amounts shown.

0.3%, HiTEC ^R 611 calcium sulfonate; [0046] of 6.5%, Example A, B, additive package C or D of 39.9% ETHYLFLO 168 poly -α- olefin oligomers Oil (8cSt base oil)
(ETHYLFLO is a trademark of Ethyl Corporation); 4
3.3%, low chlorine version of ETHYLFLO 174 poly-α-olefin oligomer oil (40 cSt base oil);
And 10.0% of KETJENLUBE synthetic oil (KETJENLUBE
BE is a trademark of Akzo Chemicals).

Example 10 The materials listed below were premixed in the relative proportions indicated and 6
After heating at 0 ° C. for 1.5 hours, the resulting mixture was
10.0% Ketjenlube 115 (Akzo Chemicals), 4
3.3% ETHYLFLO 174 PAO and 41.0% ETHYLF
With LO 168 PAO in the SAE 80W-90 synthetic fluids containing a HiTEC ^R 611 calcium sulfate 0.2w / w%, 5.5
Mix at w / w% concentration.

Isobutyl Sulfide 3.9 Octylamine 0.6 Oleylamine 0.163 Caprylic Acid 0.5 2-Ethylhexyl-Acid Phosphate 0.196 Copper Deactivator 0.07 Defoamer 0.06 Example 11 Isobutylene Sulfide , A trihydrocarbyl ester of dithiophosphoric acid, octylamine, bis-2-ethylhexyl phosphate, oleylamine, an alkyl acid phosphite, a friction modifier, and a succinimide type dispersant, by heating at 50 ° C. for 1 hour, Produces a gear oil additive concentrate of the present invention. In the second stage of this operation, oleic acid, defoamer and processing oil are added to the hot mixture produced in the first stage. The resulting concentrate is then cooled to about 35 ° C, at which point the metal deactivator and calcium sulfonate are added. The resulting concentrate (other than the amine bound to phosphoric acid) contains about 21 mole% sulfur per mole amino nitrogen and about 0.56 chemical equivalents weak acid per mole of amino nitrogen (oleic acid).
Is included. As in Example 10 above, blending the additive concentrate into the SAE 80W-90 synthetic fluid at a level of 6.5 w / w% produces gear oil (2.27 wt% isobutylene sulfide). Corresponding to the concentration of).

Example 12 Approximately 11.7: 2.8: 0.7: 5.5: 1: 1 respectively.
To give a mixture of sulfurized isobutylene, oleylamine, caprylic acid, trihydrocarbyl dithiophosphate, succinimide dispersant and friction modifier in a weight ratio of The mixture is heated at 60 ° C. for 1 hour. To this hot mixture, in the second stage, about 0.2: 0.4: 3.
Add octylamine, bis-2-ethylhexyl phosphate, amine salt of dihydrocarbyl thiophosphate and defoamer in a weight ratio of 3: 0.2. Thereafter, the resulting concentrate is about 35% initial sulfurized isobutylene and about 1%.
Add mineral oil and metal deactivator to contain 8.3% mineral oil diluent. Except for the amine bound phosphoric acid, this additive concentrate contains about 1 mole of amino nitrogen per mole.
It contains 8 mol% sulfur and about 0.6 equivalents of weak acid per equivalent of amino nitrogen. Together with 0.3% of HiTEC ^R 611 Calcium sulfonate, 3.25 percent of the additive package, 15% di (tridecyl) adipate, 25%
ETHYLFLO 168 PAO and 56.45% mineral oil (Shel
Dissolve in a semi-synthetic fluid containing HVI 650b).

Example 13 Example 1 of making the additive concentrate using the following modifications:
Repeat operation 2 above. In the first stage, bis-2-ethylhexyl phosphate, octylamine and defoamer are included, and into the reaction mixture of the second stage oleylamine, dispersant and friction modifier are introduced, and in this second stage The reaction mixture is held at 50 ° C for 30 minutes. 0.5
% With Amoco 421 Magnesium Sulfonate, 6.
Dissolving 5% of the above additive package in a fluid containing a mixture of ETHYLFLO 168 PAO and mineral oil (Shell HVI 650b) gives a gear lubricant with SAE 80W-90 viscosity grade.

Example 14 The procedure of Example 13 is repeated except that the first stage reaction mixture is heated to 50 ° C. for 20 minutes and the second stage reaction mixture is held at 50 ° C. for 1 hour. 0.25% HiTEC ^R
With 631 barium sulphonate, 6.5% of the above additive package was added to di (tridecyl) adipate (30
%) And 63.25% mineral oil to give a SAE 80W-90 semi-synthetic gear lubricant.

Example 15 Octylamine was added in the first stage reaction, caprylic acid was added into the second stage reaction mixture, the first stage reaction mixture was held at 50 ° C. for 1 hour and the final In stages,
The procedure of Example 12 of making the additive concentrate is repeated except that the amine salt of dihydrocarbyl thiophosphate is added along with the mineral oil and metal deactivator. After added with stirring 3.0% HiTEC ^R 611 overbased sulfonate in the additive package and used to synthesis and suitable for use in automotive manual transmissions synchronization system is used Formulate a semi-synthetic lubricant.

Example 16 Example 1 of making the additive concentrate with the following modifications.
Repeat operation 2 above. Octylamine and trihydrocarbyl dithiophosphate are introduced into the first stage reaction mixture and caprylic acid is introduced into the second stage reaction mixture. 5.0% of the above additive package with 0.2% Lubrizol 6477 overbased sulfonate, 25% poly-alpha-olefin made from dodecene, poly-alpha-olefin made from decene (ETHYLF
LO 168 PAO) is 44.8% and di (tridecyl) adipate is 25% dissolved in a synthetic fluid containing mixture.

Example 17 A lubricating fluid having SAE 90 grade viscosity characteristics was added to a commercial additive package (HiTEC ^R 2375 additive: Ethyl Petrole).
um Additives, Ltd .; Ethyl Petroleum Additives, In
c .; Ethyl SA; Ethyl Canada Limited), this oil is a mixture of sulfurized isobutylene (2.27 w / w%) and alkyl amine / alkyl phosphate / alkyl phosphite / alkyl thiophosphate (0.56).
(w / w%). The oil also contains caprylic acid in a ratio such that about 136 moles of sulfur are present per mole of caprylic acid. The sulfurized isobutylene is itself HiTEC ^R 309 additive. The alkylamine is totally neutralized with the phosphoric acid present. Together with 0.2% of HiTEC ^R 631 barium sulfonate, with 3.75% of the additive package, 15
% Di (isodecyl) adipate, 30% ETHYLFLO 1
68 PAO and 56.05% Shell mineral oil (HVI 650b)
Formulating a semi-synthetic lubricant containing

Example 18 Step 1-In a reaction vessel, 43.4% isobutylene sulfide is added.
Part, dibutyl hydrogen phosphite 4.44 parts, C ₁₂ -C ₁₄
Tertiary alkyl primary amines (Primene 81R; Rohm & Haas
Chemical Comopany) 4.99 parts, 2-ethylhexyl acid phosphate 1.16 parts and processing oil 2.56.
Prepare the department. The reaction vessel components are stirred throughout the above additions in which the sulfurized isobutylene, phosphite, and amines are added in the order listed. When the sulfurized isobutylene, phosphite and amines are brought into contact with each other, an exothermic reaction occurs, so the addition rate is adjusted so that this temperature does not exceed 60 ° C. At the same time, maintaining the pressure in the reaction vessel slightly negative removes any volatiles generated during the exothermic reaction. Stirring is continued while maintaining the temperature of the reaction vessel at 55-60 ° C for 60 minutes.
Then the mixture is cooled to 40 ° C.

Stage 2-0.69 in a separate reactor
Part of M-544 defoamer (Monsanto Chemical Company), 0.
73 parts of caprylic acid, 0.50 parts of a mixture of C ₁₂ and C ₁₄ tertiary alkyl primary monoamines (Primene 81R) and 2.87 parts of processing oil are stirred together for 15 minutes. The solution thus obtained is added to the product of step 1.
At the same time, dicyclopentadiene and dithiophosphoric acid-0,0-
Dialkyl esters (wherein, on a mole basis, 40% of these alkyl groups are isopropyl and 40%
Is isobutyl and 20% is 2-ethylhexyl), and 19.63 parts of the product resulting from the reaction are added. Stirring is continued for 15 minutes and this temperature is brought to 30-4.
Keep at 0 ° C. The pH of the resulting solution is about 6.9.

Step 3-To the stirring solution of Step 2 3.0 parts of 2-t-dodecyldithio-1,3,4-
Add thiadiazole, and 16.03 parts of processing oil. Stirring is continued for 15 minutes while maintaining the temperature at 30-40 ° C. The finished product typically has a sulfur content of about 23.7% (by weight) and a phosphorus content of about 2.35%.
It is a bright, transparent, tan liquid that is (by weight).

Example 19 Step 1-34.97 parts of sulfurized isobutylene, 3.00 parts of dibutyl hydrogen phosphite, 5.60 parts of C _16-18 alkylmonoamine and 0.01 of n-octylamine.
Part, 0.9% 2-ethylhexyl acid phosphate
The procedure of Step 1 of Example 18 is repeated using 8 parts and 2.65 parts of processing oil.

Step 2-The Step 1 product is cooled to 40 ° C. with continued stirring. After the temperature reached 40 ° C., the product was added to dicyclopentadiene and dithiophosphoric acid-0,0-dialkyl ester, where 40% of these alkyl groups are isopropyl, on a molar basis, 40% is isobutyl and 20% is 2
The product resulting from the reaction with
Add 6.61 parts.

Step 3-0.58 in a separate reactor
Part of M-544 defoamer (Monsanto Chemical Company), 0.
62 parts of caprylic acid, 0.62 parts of C ₃₆ dicarboxylic acid (caused by the dimerization of oleic acid) and 2.65 parts of processing oil are stirred together for 15 minutes. This resulting solution is
Add to stage 2 product. Stirring is continued for 15 minutes.

Step 4-To the stirring mixture of Step 3 2.6 parts of 2-t-dodecyldithio-1,3,4-
Add thiadiazole, and 2.65 parts of processing oil.
After adding these two ingredients, add 0.75 to the mixture.
Parts of dibutyl hydrogen phosphite are added. Stirring is continued for 15 minutes.

Step 5--To the stirring mixture of Step 4 was added 55% (by weight) of borated succinimide (HiTEC ^R 6
48 Additives: Ethyl Petroleum Additives, Inc .; Ethyl P
etroleum Additives, Ltd .; Ethyl SA; Ethyl Canada
Limited) and 45% (by weight) of processing oil, at 23.07 parts, followed by another 2.65 parts of processing oil. Stirring is continued for 15 minutes to ensure a perfect blend of these ingredients. The finished product is pumped through the filter. The product is typically about 19.3% sulfur, about 2.0% phosphorus, by weight.
It is a light clear tan liquid containing about 0.62% nitrogen and about 0.16% boron. This concentrate is dissolved in the synthesis fluid with 3.5%, 0.1% Amoco 421 magnesium sulfonate. In this case, the synthetic fluid is 25% synthetic dibasic ester di (tridecyl) adipate and 10 cSt (10 mm ² ·.
ETHYLFLO 170 PAO, which is a poly-α-olefin of sec- ¹ )
Is included.

Example 20 Step 1-31.26 parts of sulfurized isobutylene, 2.44 parts of dibutyl hydrogen phosphite, 3.18 parts of C _16-18 alkylmonoamine and 0.63 of n-octylamine.
0.8 parts of 2-ethylhexyl acid phosphate
The procedure of Step 1 of Example 18 is repeated using 0 part and 5.19 parts of processing oil. The pH of the resulting mixture is about 7.0.

Step 2-0.47 in a separate reactor
Part of M-544 defoamer (Monsanto Chemical Company), 0.
51 parts of caprylic acid, 0.51 part of C ₃₆ dicarboxylic acid (caused by the dimerization of oleic acid) and 5.19 parts of processing oil are stirred together for 15 minutes. This resulting solution is
Add to stage 1 product. At the same time, dicyclopentadiene and dithiophosphoric acid-0,0-dialkyl esters (wherein, on a molar basis, 40% of these alkyl groups are isopropyl, 40% are isobutyl and 20% are 2- 10.66 parts of the product resulting from the reaction with ethylhexyl) is added. Stirring is continued for 60 minutes and this temperature is maintained at 40 ° C.

Step 3-To the stirring solution of Step 2 2.14 parts of 2,5-dimethylthio-1,3,4-
Add thiadiazole and 5.19 parts of processing oil.
Then 0.61 part of dibutyl hydrogen phosphite is added to this mixture. Stirring is continued for 15 minutes.

Step 4--To the stirring solution of Step 3 was added 55% (by weight) of borated succinimide (HiTEC ^R 6
48 Additives: Ethyl Petroleum Additives, Inc .; Ethyl P
etroleum Additives, Ltd .; Ethyl SA; Ethyl Canada
Ltd.) and 45% (by weight) of processing oil in a mixture of 1
After the addition of 0.32 part, 6.24 parts of alkenylsuccinimide (isomerized 1-olefin mixture containing 49% C ₂₀ , 42% C ₂₂ and 8% C ₂₄ 1-olefins). Alkenyl succinic anhydride prepared from a mixture of olefins obtained by oxidization and ammonia), and an additional 14.66 parts of processing oil.
Stirring is continued for 15 minutes to ensure a perfect blend of these ingredients. The finished product is pumped through the filter. The product is a light clear tan liquid that typically contains about 17.5% sulfur and about 16% phosphorus by weight. This product
0.5% calcium sulfonate (HiTEC ^R 611 additive), 27% Lubrizol 3174 shear stability viscosity index improver, 40% of a synthetic ester di (isodecyl) adipate and 32.5% of ETHYLFLO 168 PAO Dissolve in the fluid it contains.

Example E An additive concentrate is prepared as follows.

14 parts by weight of trihydrocarbyl dithiophosphate [wherein two of the substituents are a mixture of isopropyl, n-butyl and 2-ethylhexyl (4
Ratio of 0:40:20) and the third substituent is derived from dicyclopentadiene], 38 parts of isobutylene sulfide, 1.75 parts of 2-ethylhexyl acid phosphate, and 4.76 parts. Stir with dibutyl hydrogen phosphite of about 30 ° C.

Primary alkyl tertiary amine (PRIMENE 81
6 parts of R) are added and reacted. After about 30 minutes, 2.42 parts by weight of a polyisobutylene-substituted succinimide dispersant and an additional 4.9 parts of PRIMENE 81R were added, and the resulting mixture was stirred at about 55 ° C for 1 hour.

To this mixture was added 0.57 parts of a polyalkyl acrylate defoamer, 4.31 parts of oleic acid and 5.63 parts of mineral oil with stirring and then cooled to below 40 ° C. .

Next, after adding thiadiazole 1.8 parts This mixture (HiTEC ^R 314 additive), cooled to room temperature.

[0072] Among the additive concentrate produced in the same manner as in Example 21 above Example E, with stirring, the addition of 3.15 parts of HiTEC ^R 611 Calcium sulfonate and 11.85 parts of mineral oil of This gives an additive package suitable for formulating gear oils.

[0073] Among the additive concentrate produced in the same manner as in Example 22 above Example E, with stirring, the addition of HiTEC ^R 614 Calcium sulfonate 15 parts, the additive concentrate can be obtained.

Example 23 3.0 parts of Amoco 421 magnesium sulphonate and 12.0 parts of mineral oil are added, with stirring, to an additive concentrate prepared as in Example E above.

[0075] Among the additive concentrate produced in the same manner as in Example 24 above Example E, 1.0 parts of sodium alkylbenzene sulfonate, HiTEC ^R 611 Calcium sulfonate 2.0 parts of 1
Blend 2.0 parts mineral oil.

Example 25 The table below shows examples of gear oil formulations containing the individual additive packages described in Examples 21-24 above.

[0077]

[Table 1]

Example F A chemical composition is prepared as follows.

6.26 parts of trihydrocarbyl dithiophosphate [wherein two of the substituents are a mixture of isopropyl, n-butyl and 2-ethylhexyl (4
Ratio of 0:40:20) and the third substituent is derived from dicyclopentadiene], 44 parts isobutylene sulfide, 5.33 parts dibutyl hydrogen phosphite and 1.94 parts 2 -Stir with ethylhexyl acid phosphate for 10 minutes at about 30 <0> C. To this mixture is added 0.6 parts octylamine, followed by a mixture of 6.0 parts PRIMENE 81R amine and 1.2 parts oleylamine. The resulting mixture is then heated at about 55 ° C. for about 1 hour, after which heating is stopped and the acidic mixture shown below is added.

Acid mixture 5 parts mineral oil 2.2 parts oleic acid 0.5 parts polyalkyl acrylate antifoam 0.3 parts caprylic acid 0.116 parts TOLAD 9308 (Petrolite) 0.106 parts Polyethylene / Propylene Block Copolymer 0.777 parts TOLAD 370 (Petrolite) 9.33 parts Am after cooling below 40 ° C. with stirring
Add oco 9250, 1.2 parts thiadiazole (HiTEC 314 additive) and 15.781 parts mineral oil.

Example 26 The composition prepared as described in Example F above was mixed with calcium sulfonate (HiTEC 611 additive) at 50:50 by weight and used to prepare Example 27 below. Prepare a transmission oil as described in.

Example 27

[0083]

[Table 2]

Example 28 3.9% of a mixture in a mixture of 10% diisodecyl adipate, 25% hydrotreated mineral oil (Shell XHVI 5.2), and 60.9% mineral oil (Shell HVI 650b). An
The glamol 99 gear additive package and 0.2% barium sulfonate (HiTEC631 additive) produces the semi-synthetic gear fluid of the present invention.

Example 29 6.5% Anglamol 6004A Gear Additive Package, 0.
5% of HiTEC 614 ^R calcium sulfonate, 10% of diisodecyl adipate, to blend 6.0% of ETHYLFLO 174PAO, and 77% of ETHYLFLO 170 PAO together, SAE 80W fluids of the present invention is obtained.

Example 30 33.2% diisodecyl adipate and 60% ETHYLF
6.6% Mobila with a mixture consisting of LO 174 PAO
Blending 0.25% Amoco 421 Magnesium Sulfonate with the G521T gear additive package provides the gear lubricant of the present invention.

Example 31 8.0% Anglamol 6043U gear additive, 0.2% Hi
TEC 631 Barium Sulfonate, 35% Di (tridecyl) adipate, and 56.8% Mineral Oil (Shell HV
Blending with I 650b) results in the semi-synthetic gear lubricant of the present invention.

Example 32 6.5% Anglamol 99 Gear Additive Low Chlorine Plate, 0.5%
HiTEC 631 Barium Sulfonate, 1.5% HiTEC 623
A pour point depressant, 65% mineral oil (Shell HVI 650b) and 26.5% ETHYLFLO 168 PAO are blended together to provide the semi-synthetic gear lubricant of the present invention.

Example 33 7.0% Anglamol 9000 Gear Additive, 0.1% HiTEC
611 Calcium sulfonate, and 1.0% HiTEC 62
Blending 33% diisodecyl adipate and 58.9% Shell HVI 650b mineral oil with a mixture of three pour point depressants results in the semi-synthetic gear fluid of the present invention.

Example 34 8.0% Anglamol 6043U gear additive, 0.1% potassium alkylbenzene sulfonate, 0.1% HiTEC
611 calcium sulfonate, 35% di (tridecyl)
Blending with adipate and 56.8% mineral oil results in the semi-synthetic gear lubricant of the present invention.

Example 35 6.5% Anglamol 99 Gear Additive Low Chlorine Plate, 0.2%
Of sodium alkylbenzene sulfonate, 0.2%
Amoco 421 Magnesium sulfonate, 0.2% HiTEC 6
14 calcium sulfonate, 1.5% HiTEC 623 pour point depressant, 65% mineral oil (Shell HVI 650b) and 2
Blending 6.5% diisodecyl adipate together provides a lubricant of the present invention suitable for use in certain automotive manual transmissions and final drives.

The three different Anglamol products described above (The
Lubrizol Corporation) and the above Mobilad products (Mobil
Chemical Company) are all phosphorus and sulfur containing antiwear and / or extreme pressure additives
It will, of course, be understood by those skilled in the art that the gear oil additive package is based on the use of onentry).

The results of the various ZF Synchronizer tests performed as described above are illustrative of the performance improvements achieved by the practice of the present invention and are not limiting in any manner. Table I shows the gear additive package (HiTEC ^R 380 additive; Ethyl Petroleum Additives, Lt
d., Bracknell, England) at the API-GL4 dose level in various base oils. In Table I, all percentages are by weight and PAO (I) is ETHYLFLO 170 PAO (Ethy
Corporation), that is, the kinematic viscosity at 100 ° C is about 9.6m
m ² · sec ^-1 (cSt) is a hydrogenated poly-α-olefin; ESTER is diisodecyl adipate; MIN. OIL is Shell HVI 115; and PAO (II) is ETHYLFLO 174 PAO (Ethyl Corporat
ion), that is, the kinematic viscosity at 100 ° C. is about 40 mm ² · sec ^-1 (c
St) hydrogenated poly-α-olefin.

The Shell HVI 115 mineral oil described above is HiTEC ^R 623.
The solvent neutral oil contained 1.0 pour point depressant and had a kinematic viscosity at 100 ° C. of 9 mm ² · sec ^-1 (cSt). Table I
In the first seven trials (i.e., Run Nos. 1-7) in SAE 80W viscosity grade formulations were used. Run Nos. 1-7 are comparative tests because none of these formulations contained a sulfonate additive. However, in Experiment No. 8, 0.5 wt% of HiTEC ^R 611 additive, i.e. from Ethyl Petroleum Additives, Inc. and Eth
A formulation commercially available from yl Petroleum Additives, Ltd. was used containing a nominal TBN of 300 overbased calcium alkylbenzene sulfonate. The HiTEC ^R 611 additive contains approximately 44% diluent oil. The run number 8 formulation is a SAE 90 grade formulation that is effective as an overall driveline fluid suitable for use in final drives such as hypoid differentials and gearboxes.

[0095]

[Table 3]

Fluids containing these synthetic oils failed the above test, while fluids based on mineral oils passed, comparing the results of Experiment Nos. 2-7 with Experiment No. 1. You will understand that. Run No. 8 contains a small amount of a metal sulfonate according to the present invention in a synthetic oil based fluid which improves the frictional properties of this blend to the extent that it passes the above test. ,
It is shown that.

Table II summarizes the results of additional ZF synchronizer tests showing the practice and advantages of the present invention.

Experiment Nos. 11-14 were 2.0, 1.0, 0.2 and 0.1% for these gear oils respectively.
The inclusion of the metal sulfonate (HiTEC® 611 additive) of Example ¹ demonstrates the practice of the present invention. In Experiment No. 15, this gear oil has an EP for comparison purposes.
An alkenyl succinimide friction modifier of the type described in 20,037 was included at 1.0%. The oil of Experiment No. 16 contained polyisobutenylsuccinimide ashless dispersant (HiTEC ^R 646 additive; Ethyl Petroleum Additives, In
c .; Ethyl Petroleum Additives, Ltd. and their branch offices). The above percentages are "as received" (as received basi
s), thus containing solvent oil. Example number 1
The succinimide friction modifier of 5 contained no diluent. As in Table I, all percentages are by weight and also "PAO (I)""PAO(II)"
And "ESTER" have the same meaning as in Table I.

[0099]

[Table 4]

The term "oil-soluble" as used in the above description means that the component in question is dissolved in the selected base oil at normal temperature, at a concentration which corresponds at least to the minimum concentration specified here for the use of said component. It is used in the sense that it has a sufficient solubility. However, preferably, the solubility of the component in the selected base oil is above the minimum concentration, but the requirement that the component should be dissolved in the base oil in all proportions is It doesn't exist. As is well known to those skilled in the art, certain effective additives are not completely dissolved in the base oil, but rather are used in the form of stable suspensions or dispersions. There is. It is also possible to use additives of this type in the compositions according to the invention, provided that they do not significantly impair the performance or effectiveness of the compositions in which they are used.

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

1. Kinematic viscosity at 100 ° C is 4 to 3
2 mm ² · sec ^-1 (cSt) and a) (i) hydrogenated poly-alpha-olefin oligomer oil or (ii) synthetic ester oil or (ii)
i) a base oil containing at least 25% by weight of a combination of (i) and (ii); b) an amount of a gear oil additive package such that this gear oil lubricant meets or exceeds specifications for GL4 service; and c) An amount in the range of 0.01 to 2% by weight, based on the total weight of the lubricant, sufficient to improve the frictional properties of the lubricant used in manual transmissions, especially synchronizer type manual transmissions. Of at least one alkali or alkaline earth metal salt of oil-soluble sulfonic acid; wherein the metal contained as one or more metal-containing additive components other than the above metal salt is At most 100 ppm, if included, and the boron content, if included, is 1, based on weight. 00ppm or less, gear oil lubricants.

2. The lubricant composition according to claim 1, wherein the component c) is a calcium salt of an oil-soluble alkylbenzene sulfonic acid.

3. The lubricant composition according to claim 1, wherein the component c) is an overbased salt of the sulfonic acid.

4. The lubricant composition according to claim 1, wherein said component a) is at least 50% by weight of hydrogenated poly-alpha-olefin oligomer oil.

5. a) at least one selected from succinimide ashless dispersants and / or succinic ester-amide ashless dispersants, and Mannich base ashless dispersants
B) at least one oil-soluble metal-free sulfur-containing antiwear and / or extreme pressure agent; c) at least one oil-soluble metal-free phosphorus-containing antiwear and / or extreme pressure agent; And d) at least one alkali or alkaline earth metal salt of an oil-soluble sulfonic acid having a kinematic viscosity at 100 ° C. in the range of 4 to 32 cSt and (i) hydrogenated poly-
Alpha-olefin oligomer oil or (ii)
Synthetic ester oil or (iii) (i) and (ii)
A lubricant composition obtained by blending this additive package into a base oil containing at least 25% by weight of the combination of the above-mentioned combinations to produce a lubricant containing 0.01 to 2% by weight of the above metal salt. A) meets or exceeds the specifications for API-GL4 service; B) contains at most 100 ppm of a metal that is different from the metal of the above metal salt even if included; and C) is included Boron content of 1,000p
Gear oil lubricant package (concentrate) containing pm or less; in an amount to provide a lubricant composition.

6. The gear oil additive package according to claim 5, wherein the metal salt is a calcium salt of an oil-soluble alkylbenzene sulfonic acid.

7. The gear oil additive package according to claim 5, wherein the metal salt is an overbased salt of the sulfonic acid.

8. The gear oil additive package of claim 5, further characterized in that the total halogen content, if included, is 100 ppm or less by weight.

9. The gear oil additive package of claim 8, wherein the total halogen content, if included, is 250 ppm or less based on weight.

10. 0. based on the total weight of this lubricant, so as to improve the frictional properties of the lubricant so that it is suitable for use in synchronizer type manual transmissions.
Including at least one alkali or alkaline earth metal salt of an oil-soluble sulfonic acid in an amount in the range of 01 to 2% by weight in a lubricant composition, (i)
Hydrogenated poly-alpha-olefin oligomer oil or (ii) synthetic ester oil or (iii) (i)
At least 25% by weight of the combination of (ii) and this lubricant composition meets or exceeds specifications for API-GL4 service, but is satisfactory for use in manual transmissions, especially synchronizer type manual transmissions. And a method for advantageously modifying the friction properties of a low friction synthetic lubricant composition containing a gear oil additive package that does not exhibit such friction properties.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C10M 133: 16 137: 02 135: 04 135: 10) C10N 10:02 10:04 20:02 30 : 00 A 8217-4H 30:04 30:06 30:12 40:04

Claims (3)

[Claims] 1. The kinematic viscosity at 100 ° C. is 4 to 32 m.
m ² · sec ⁻¹ (cSt), and a) (i) hydrogenated poly-alpha-olefin oligomer oil or (ii) synthetic ester oil or (ii)
i) a base oil containing at least 25% by weight of a combination of (i) and (ii); b) an amount of a gear oil additive package such that this gear oil lubricant meets or exceeds specifications for GL4 service; and c) An amount in the range of 0.01 to 2% by weight, based on the total weight of the lubricant, sufficient to improve the frictional properties of the lubricant used in manual transmissions, especially synchronizer type manual transmissions. Of at least one alkali or alkaline earth metal salt of oil-soluble sulfonic acid; wherein the metal contained as one or more metal-containing additive components other than the above metal salt is At most 100 ppm, if included, and the boron content, if included, is 1, based on weight. 00ppm or less, gear oil lubricants. 2. At least one oil-soluble ashless dispersant selected from a) succinimide ashless dispersants and / or succinic acid ester-amide ashless dispersants, and Mannich base ashless dispersants; b) at least one oil. Soluble metal-free sulfur-containing antiwear and / or extreme pressure agent; c) at least one oil-soluble metal-free phosphorus-containing antiwear and / or extreme pressure agent; and d) at least one alkali or alkali oil-soluble sulfonic acid. The earth metal salt has a kinematic viscosity at 100 ° C. in the range of 4 to 32 cSt and (i) hydrogenated poly-
Alpha-olefin oligomer oil or (ii)
Synthetic ester oil or (iii) (i) and (ii)
A lubricant composition obtained by blending this additive package into a base oil containing at least 25% by weight of the combination of the above-mentioned combinations to produce a lubricant containing 0.01 to 2% by weight of the above metal salt. A) meets or exceeds the specifications for API-GL4 service; B) contains at most 100 ppm of a metal that is different from the metal of the above metal salt even if included; and C) is included Boron content of 1,000p
Gear oil lubricant package (concentrate) containing pm or less; in an amount to provide a lubricant composition. 3. An amount ranging from 0.01 to 2% by weight, based on the total weight of the lubricant, so as to improve the frictional properties of the lubricant so that it is suitable for use in a synchronizer type manual transmission. (I) hydrogenated poly-alpha-olefin oligomer oil or (i) comprising at least one alkali or alkaline earth metal salt of an oil-soluble sulfonic acid in the lubricant composition.
i) synthetic ester oil or (iii) (i) and (i
The combination of i) is at least 25% by weight and the lubricant composition meets or exceeds the specifications for API-GL4 service, but satisfactory friction for use in manual transmissions, especially synchronizer type manual transmissions. A method of beneficially modifying the friction properties of a low friction synthetic lubricant composition containing a gear oil additive package that does not exhibit properties.