ES2227234T3 - COMBINATION OF FRICTION MODIFY ADDITIVES. - Google Patents

Abstract

This invention relates to a friction modifier additive combination comprising (a) an oil-soluble fatty amine compound and (b) an oil-soluble fatty amide compound. Automatic transmission fluids comprising the above additives achieved a green shudder of 0 hour and a shudder resistance time of 110 hours or above.

Description

Combination of additives modifying the friction.

This invention relates to a combination of additives that provides friction modifying benefits to lubricants and functional liquids, especially liquids of power transmission such as gear oils, fluids automatic transmission and transmission fluids continuously variable

Power transmissions for vehicles cars, for example automatic transmissions, are continually developing to improve its efficiency. Exists a new generation of automatic transmissions manufactured currently they are equipped with a converter clutch electronically controlled (hereinafter "ec3"). He design provides a more compact automatic transmission and more light weight that allows fuel saving together with ec3 up to 10% and exhibits superior exchange comfort.

The new automatic transmission designs set higher demands on the automatic transmission fluid (hereinafter referred to as "ATF"). All ATFs must have high oxidation stability, viscosimetric properties and a satisfactory low temperature, and corrosion protection, antifoaming properties and air separation properties satisfactory Additionally, the friction properties, measured by the coefficients of friction displayed on a graph, They are essential to provide satisfactory efficiency. The friction property of the ATF must be compensated, in such a way so that there is sufficient friction to provide a adequate power transmission while minimizing the vibration both in the engine start-up (the so-called "cold vibration") and throughout the life of the ATF. A excessive vibration causes driver discomfort and results in a unacceptable noise level.

For newly developed automatic transmissions equipped with an electronically controlled converter clutch, these friction requirements are even more demanding. Typically, the Original Equipment Manufacturer (hereinafter referred to as "OEM") specifies a minimum friction coefficient of 0.123 for a plate slip speed of 5 rpm in order to provide the necessary power transmission to the shaft, along with the requirement that the coefficient of friction does not decrease with the increasing sliding speed of the plate, that is to say that the gradient of the curve in the friction coefficient graph versus increasing sliding speed is positive or zero; It must not be negative. The last requirement is to minimize cold vibration to an acceptable period of time not exceeding 0.2 hours (12 minutes). Additionally, it is preferred that the ATF operates without appreciable vibration (once any cold vibration has ceased) for at least 150,000 kilometers of automobile transmission operation. The minimum hours according to the Za3radfarbik Friedrichschafen ec3 test (hereinafter "ZF") as defined are located in the region of> 100 hours.

The ATFs used so far that contain friction modifiers ("FM") conventional, such as fatty acids, fatty amines and alcohols fatty, do not meet these requirements. For example, ETHOMEEN® T-12, a tallow amine supplied by AKZO Chemicals, when incorporated into an ATF formulation at a level treatment of 0.15% by weight, does not always satisfy the friction coefficient requirement versus speed of slip (0.123 at 5 rpm) and never reaches durability greater than 100 hours.

The document EP-A-0 713 908 published with above describes a transmission fluid composition of oil-based power, especially ATFs it contains, between other things, at least one soluble friction modifier in oil that can be selected from aliphatic amines, amides of aliphatic fatty acids, aliphatic carboxylic acids, esters aliphatic carboxylic acids, aliphatic carboxylic ester amides, aliphatic phosphonates, aliphatic phosphates, aliphatic thiophosphates and aliphatic thiophosphates, etc. in which the aliphatic group It contains more than 8 carbon atoms to make the compound conveniently soluble in oil. It is said that the compositions of this invention have the ability to exhibit a positive slope in the graph of coefficient of friction versus velocity of sliding in the SAE No. 2 Friction Test at low speed when performed according to the Materials Specification Ford WSP-M2CZAA-A technicians. Also, the clutch friction durability tests performed using the method indicated above involving 20,000 cycles, the following results were achieved: in the range of 0.130-0.170; µs values (at 0.25 seconds) in the range of 0,110-0,155; values dynamic friction at low speed in the range of 0,130-0,170; S1 / D values in the range of 0.90-1.16; and stop times, in seconds, in the 0.70-1.0 range. It would be obvious to Experts in the art that this SAE test cannot be applied to European OEMs, and therefore not suitable for design European because it is a laboratory test equipment that did not produce the specific results initially and, for this reason, he had to leave.

WO 99/02628 describes modifiers of friction including alkoxylated amines and a compound polyamide which is the reaction product of a poly-amine containing from 2 to 60 carbon atoms totals and 3 to 15 nitrogen atoms, at least being present one of the nitrogen atoms in the form of an amine group primary and at least two of the atoms of nitrogen remaining in the form of primary or secondary amine group and a carboxylic anhydride.

EP 0748862 refers to a lubrication composition, which can be used as a fluid for automatic or manual transmissions, comprising a quantity main of an oil of lubricating viscosity and at least one ester of metal-free thiophosphorus acid, at least one amine salt of the thiophosphorus acid ester, or a mixture thereof, in the which the metal-free thiophosphorus acid ester contains the least one hydrocarbyl-terminated oxyalkylene group, at least one hydrocarbyl terminated polyoxyalkylene group, or a mixture of the same.

EP 812900 describes a composition of lubricating oil for automatic transmission comprising a Sulfur-containing antioxidant or an amine-type antioxidant, a phosphate or its amine salt and a reaction product of an acid carboxylic and an amine in which the amine antioxidant is select from alkylamines. WO 97/04049 describes a  friction modifier that includes an alkoxylated amine and a polyamide which is the reaction product of an acid or anhydride carboxylic with a polyamine containing from 2 to 60 atoms of total carbon and 3 to 15 nitrogen atoms, being present at least one of the nitrogen atoms in the form of a group primary amine and at least two of the atoms of nitrogen remaining in the form of primary amine groups or secondary.

The present invention provides a combination of friction modifying additives comprising (a) a oil-soluble fatty amine compound and (b) a compound of oil soluble fat amide.

It has been found that by combination of an amine fat with a fatty amide, the friction properties of a Lubricant or functional fluid containing them are improved. For example, by formulation of an ATF that uses the combination of amine / amide friction modifiers of the present invention  it is possible to achieve a friction coefficient at 5 rpm of at least 0.123 along with a positive or zero gradient on the graph of coefficient of friction versus sliding speed. After the end of the cold vibration, where appropriate, the ATF can operate for 150 hours or more before the appearance of vibration.

The fatty amine compound is a compound of tertiary amine, of the following formula (I):

one

in the which:

R is an alkyl group containing from 8 to 24 carbon atoms or any aryl group containing one or more alkyl substituents containing from 8 to 24 atoms of carbon;

R1 and R2 are each independently an alkylene group containing from 1 to 8 carbon atoms; y x e y are each independently 0 or an integer from 1 to 5.

The substituent group R is conveniently a alkyl group containing from 10 to 18 carbon atoms, preferably from 12 to 14 carbon atoms. The substituent group R is conveniently derived from a fatty acid that is usually a naturally existing substance and therefore can contain a mixture of carbon chain lengths, in which case the average chain length of the substituent group R is more preferably comprised within the ranges of atoms Carbon specified above.

The substituent groups R1 and R2 are each independently an alkylene group as set forth above, and these groups conveniently have 1 to 4 atoms carbon, most preferably 2 carbon atoms, such as e.g. a grouping -CH_ {2} -CH_ {2} -. The groupings -R 1 O- and -R 2 O- are preferably groups oxy-ethylene and, correspondingly, -R 1 OH and -R 2 OH are ethylene hydroxy groups.

The number of oxyalkylene groups represented by x and y are each independently conveniently 0, 1 or 2 and they are preferably 0.

Specific examples of fatty amine compounds suitable include a coco-bis (2-hydroxyethyl) amine, a polyoxyethylene (5) coco-amine, a tallow-bis (2-hydroxyethyl) -amine, a polyoxyethylene (5) sebum amine, a tallow / oleyl-bis (2-hydroxyethyl) amine and one oleyl-bis- (2-hydroxy-ethyl) amine. Such compounds are commercially available from, e.g., AKZO Chemicals Compounds such as e.g. the coco-bis (2-hydroxyethyl) amine (ETOMEEN® C / 12) containing a mixture of C 8 to alkyl groups C 18 in which C 12 groups predominate, sold by Akzo Chemicals

The fatty amide compound is an amide tertiary of the formula (II)

2

in which R, R 1, R 2, x e and are each independently as defined above for formula (I), both with respect to general embodiments as to realizations preferred.

Specific examples of fatty amide compounds suitable include the compound polyoxyethylene (5) oleamide sold under the name ETHOMID® 0/15 (from Akzo Chemicals) containing a mixture of C 12 to C 18 alkyl groups in which the C 18 groups; and an acid-derived fatty acid amide lauric, sold as COMPERLAN® LD (from Henkel).

In a preferred embodiment, the combination of friction modifying additives in accordance with the present invention comprises a mixture of (a) a bis (hydroxyethyl) fatty amine in which the fatty group it comprises an alkyl group having 12 to 14 carbon atoms and (b) a bis (hydroxyethyl) fatty amide in which the fatty group comprises an alkyl group having 12 to 18 atoms of carbon.

In another embodiment, the present invention provides a lubricant or functional fluid formulation that comprises a main amount of viscosity base oil lubricant and a smaller amount of a combination of additives friction modifiers as defined above. He lubricant or functional fluid can be conveniently used as a power transmission fluid, preferably as a automatic transmission fluid (ATF). To illustrate the invention, the description that follows will focus on formulations ATF, although it will be understood that the compositions herein invention is not limited to such fluids, but encompasses within its reach other lubricating and functional fluids.

ATFs typically have a viscosity kinematics at 100 ° C (KV 100) between 2 and 15 mm 2 / s, preferably between 4 and 10 mm 2 / s, and more preferably between 5 and 8 mm 2 / s, measured according to the procedure of ASTM D-446 standard test. Brookfield viscosity at -40 ° C it is conveniently less than 50,000 mPa s, preferably from 4,000 to 20,000 mPa s, and more preferably 5,000 to 18,000 mPa s measured according to the standard test procedure ASTM D-2983. The viscosity index is conveniently in the range of 100 to 200, preferably between 150 and 200 measured according to the ASTM D-2270 standard test procedure.

Generally, the amount of base oil contained in the ATF is between 50% by weight and 99.9%, conveniently between 60 and 95% by weight, and preferably between 70 and 90% by weight, based on the total weight of the ATF formulation.

The amount of additive combination friction modifiers present in the ATF formulation (it is say the total amount of fatty amine and fatty amide) is generally in the range of 0.05-1.2% by weight. Within this interval, the specific amount used will depend not only on the properties of desired friction but also, at least to some extent, of the Automatic transmission design. Thus, the amount of combination of friction modifier additives used is comprised conveniently in the range of 0.1-1% by weight, preferably between 0.2 and 0.8% by weight and more preferably between 0.3 and 0.6% by weight.

The amount of fatty amine compound in this combination of friction modifying additives is conveniently in the range of 0.03-1.0% by weight, preferably between 0.05 and 0.8% by weight and more preferably between 0.1 and 0.6% by weight. He fatty amide compound in the additive combination is conveniently between 0.05 and 0.8% by weight, preferably between 0.05 and 0.5% by weight, and more preferably between 0.08 and 0.3% by weight.

The weight ratio of the fatty amine to the amide grease in the combination of additives is comprised conveniently in the range of 0.5: 1 to 10: 1, preferably between 1: 1 and 8: 1, and more preferably between 2: 1 and 6: 1.

The amounts of fatty amine and fatty amide in the combination of additives they are expressed with respect to active ingredients in such compounds. The compounds above specified are generally liquid at room temperature and within conventional handling and mixing temperatures of the lubricant additives, and are supplied and used by consequently usually in pure form, with 100% ingredient active. However, if desired, they can be diluted with a solvent, such as e.g. mineral oil, which is inert in such conditions, especially with respect to the efficiency of lubricant.

ATF base oil or other lubricant or fluid Functional according to the invention can be a mineral oil, a synthetic oil or mixtures thereof. The base oils are conveniently select from refined mineral oils, by for example, oils refined with solvents and / or hydrotreated, oils derived from coal tar or shale, oils vegetables, animal oils, hydrocracked oils, oils hydro-isomerized, poly-alphaolefins (PAO), esters, alkylbenzenes, polyglycols, alkylene oxide polymers, oils silicone, etc.

In cases where the base oil comprises a mineral oil, it is conveniently a refined oil with solvents and / or hydrotreated. Examples of suitable oils of this type include among others, mineral oils refined with solvents in the range of 50N to 150N, preferably 80N at 130N Such mineral oils are available, for example, from Esso under the trade name Esso Solvent Neutral.

In cases where the base oil is an oil strongly refined mineral such as e.g. white oil, these they can be one of the varieties supplied by Esso under the trade names MARCOL® 52 and 172, PRIMOL® 352, PLASTOL® 135 and 352 and BAYOL® 52. The base oils used can also be hydrocracked or hydroisomerized oils such as e.g. a hydroisomerized paraffin.

In cases where the base oil is an oil synthetic, it is preferably a PAO produced by the oligomerization of 1-alkenes containing conveniently 6-20 carbon atoms, preferably 8-14 carbon atoms. Be particularly prefer PAOs produced from 1-dean. The KV_ {100} of the selected PAO is usually determined by the desired viscosity in the formulation final lubricant and is conveniently included in the range of 2 to 8 mm 2 / s, preferably 4 to 6 mm 2 / s. Such PAOs are commercially available e.g. from ExxonMobil.

In a preferred embodiment, the base oil is a mixture of mineral oils and synthetic oils, e.g. a mixing one or more mineral oils refined with solvents with PAOs; or a mixture of mineral oil refined with solvents with white oil, a hydrocracked oil or an oil hydroisomerized as set forth above. In a particularly preferred embodiment, the base oil is a mixture of solvent-refined mineral oil, a PAO and oil White.

The functional fluid formulations of the The present invention may also contain other additives optional depending on the proposed use of the functional fluid. Such additives include, among others, index improvers. viscosity, pour point depressants, antioxidants, agents anti-wear, extreme pressure additives, dispersants, detergents, corrosion inhibitors, inhibitors of erosion, anti-foaming agents, agents seal gasket swelling conditioners (sealing fasteners), anti-sting agents and analogues Such additives are available all of them commercially, depending on the choice of one or more of these and the used amounts of each of the proposed end use of the fluid  functional. Thus, e.g., a viscosity index improver is would typically include in functional fluids at a level of 2-15% weight based ingredient treatment active (i.e. excluding solvent and vehicle fluids, in if applicable), preferably 2 to 10% by weight, and the other additives would typically be included in functional fluids at the level of 0.01-5% weight based ingredient treatment active.

The optional additives listed above may can be added individually to the base oil, or they can pre-mix two or more of them with a fluid vehicle such as e.g. a mineral oil, to form a additive concentrate and can then be mixed with the oil base. The combination of friction modifying additives from according to the invention it can also be premixed with or without others additives to give a concentrate of additives.

Of the optional additives indicated previously:

the dispersants they are conveniently dispersed without ashes such as e.g. poly (alkenyl succinic anhydrides), poly (alkenyl succinimides) and derivatives of the same in which the polyalkenyl group is derived from a long chain polyolefin such as e.g. polyisobutylene;

the additives of extreme pressure are conveniently based on phosphorus or zinc;

the Antioxidants are conveniently of the amine type and / or phenolic;

the reinforcer against pitting ("pitting booster") is conveniently a  sulphurous fatty oil, e.g. Sulperm® 307 (from Ferro Corporation);

the agents Defoamers are conveniently based on silicon; Y

the improver of viscosity index is conveniently acrylic based such as e.g. a poly (methyl methacrylate).

The combination of modifier additives friction and lubricating oil formulations produced at from it are particularly effective when used in automatic transmission fluids, especially for automatic transmissions equipped with a converter clutch electronically controlled

The present invention is further illustrated. with reference to the following examples.

The following formulation was tested for its efficiency as an ATF, in which all quantities in columns are expressed in percentage by weight:

TABLE 1

3

       \ dotable {\ tabskip \ tabcolsep # \ hfil \ tabskip0ptplus1fil \ dddarstrut \ cr} {
 * Refers to a package of patented ATF additives, Hitec®
403 but without Ethomeen® T / 12 (from \ cr Ethyl
Corp.). \ Cr}
    

The formulations indicated in the Tests 1-4 earlier passed the clutch tests electronically controlled converter (ECCC) in the Mannesmann Sachs (MS) German für Geregelte Wandlerkupplung (hereafter "GWK"). The formulations indicated above reached a 0 hours cold vibration and a resistance time to the vibration of 110 hours or higher (compared to a time specified at least 100 hours) thus satisfying the demanding requirements GWK of MS and ZF.

Claims (14)

1. A combination of modifier additives the friction that comprises

(to)

a Oil soluble fat amine compound of formula (I):

5

in the which:

R is a group alkyl containing from 8 to 24 carbon atoms or an aryl group containing one or more alkyl substituents containing from 8 to 24 carbon atoms;

R1 and R2 are each independently an alkylene group which contains from 1 to 8 carbon atoms; y x e y are each independently 0 or an integer from 1 to 5, and

(b)

a oil soluble fat amide compound of the formula (II)

6

in which R, R 1 and R 2, x e y are each independently as has been defined above for formula (I), and in which the relationship in Weight of fatty amine to fatty acid amide in combination of additives is in the range of 0.5: 1 to 10: 1

2. A combination according to the claim 1, wherein the substituent groups R1 and R2 are each independently an alkylene group and have 1 to 4 carbon atoms. 3. A combination according to the claim 1 or 2, wherein the number of oxyalkylene groups represented by x and y are each independently conveniently 0, 1 or 2 and are preferably 0. 4. A combination according to any one of claims 1 to 3, wherein the fatty amine is select from the group of coco-bis (2-hydroxyethyl) amine, a polyoxyethylene (5) coco-amine and a oleyl-bis- (2-hydroxy-ethyl) amine, and mixtures thereof. 5. A combination according to any one of claims 1 to 4, comprising a mixture of (a) a bis (hydroxyethyl) fatty amine in which the fatty group it comprises an alkyl group having 12 to 14 carbon atoms and (b) a bis (hydroxyethyl) fatty amide in which the fatty group comprises an alkyl group having 12 to 18 atoms of carbon. 6. A lubricant formulation comprising a main amount of lubricating viscosity base oil and a smaller amount of a combination of additives modifying the friction as defined in any one of the claims 1-5 above. 7. A lubricant formulation according to the claim 6, wherein said formulation is a fluid of automatic transmissions that have a kinematic viscosity at 100 ° C (KV 100) between 2 and 15 mm 2 / s measured by In accordance with the ATM standard test procedure D-446, a Brookfield viscosity at -40 ° C lower than 50,000 mPa s measured according to the test procedure ASTM D-2983 standard and a viscosity index in the  100-200 range measured according to the ASTM D-2270 standard test procedure. 8. A lubricant formulation according to the claim 6 or 7, wherein the total amount of the fatty amine and the fatty acid amide present as the combination of additives friction modifiers is in the range of 0.05-1.2% by weight. 9. A lubricant formulation according to a any one of claims 6 to 8 above, in which the base oil comprises a poly-alpha-olefin (PAO) that has a KV_ {100} value in the range of 2-8 mm2 / s. 10. A lubricant formulation according to a any one of claims 6 to 9 above, in which said formulation comprises a mixture of a mineral oil refined with solvent, a PAO and white oil. 11. A lubricant formulation according to a any of claims 6 to 10 above, in which said formulation comprises a viscosity index improver a a level of 2-15% by weight based on ingredient active. 12. A lubricant formulation according to the claim 11, wherein the viscosity index improver It is a poly (methyl methacrylate). 13. Use of the lubricant formulation according with any one of claims 6 to 12 as the fluid of power transmission. 14. Use of the lubricant formulation according with any one of claims 6 to 12 as the fluid of automatic transmissions (ATF).