US3280029A - Lubricant compositions - Google Patents

Description

United States Patent 3,28%,029 LUBRICANT COMPGSITIONS Hans F. Waldmann, Glassboro, NJ, assignor to Mobil Oil Corporation, a corporation of New York No Drawing. Filed June 18, 1964, Ser. No. 376,249 21 Claims. (Cl. 252-495) The present invention is directed to lubricant compositions possessing improved characteristics. More particularly, it is directed to improved lubricating oils and waterin-oil emulsions.

The vapor phase corrosion or rusting of metal parts is often an acute problem in machines or systems which contain water. Such corrosion most frequently occurs at the metal surfaces enclosing vapor spaces, and is a particular problem in systems which employ water-in-oil emulsions such as hydraulic fluids as functional fluids for transmitting mechanical energy. Indeed, .although water-in-oil emulsions are widely used today as lubricants and functional fluids, this problem of vapor phase corrosion is a major drawback to their more widespread use particularly as functional fluids for power transmission and the like.

Due to the more rigorous demands of modern technology, increasing attention is being given to the problem of fatigue in metal components vvhich are subject to repeated stress. Such metal fatigue is also a particular problem in systems employing water-in-oil emulsions as functional fluids. The metal components in such systems frequently tend to be subject to early fatigue failures. For example, due to the fatigue failure of bearings, the useful life of gear pumps employing water-in-oil emulsions is often only about one-fifth as great as that of gear pumps which employ other types of functional fluids.

In accordance with the present invention, I have found that by incorporating a specific type of compound into lubricant compositions, it is possible to provide compositions which are capable of imparting effective and longlasting vapor phase corrosion resistance, improved antifatigue qualities and other desirable characteristics.

It is therefore an object of the present invention to provide improved lubricants. A further object is to provide a method for improving the characteristics of such lubricants. Another object is a method for enhancing the vapor phase corrosion resistance and anti-fatigue characteristics of metals which are subject to conditions which promote vapor phase corrosion and metal fatigue. A further object is to provide effective additives for 1u bricants. A particular object of the present invention is to provide water-in-oil emulsions exhibiting superior characteristics especially vapor phase corrosion resistance and anti-fatigue characteristics. Other objects of the invention as well as some additional advantages thereof will become apparent hereinafter.

The foregoing and other objects are achieved by incorporating into the lubricants certain alkyl amino monoalkanols possessing the general formula:

where R represents an alkyl group; R represents an alkyl group the same or different from R, or a hydrogen atom; R and R are selected so that 3,280,029 Patented Oct. 18, 1966 "ice sum of the groups represented by R-l-R does not exceed 10 carbon atoms;

X is an alkylene group having from 2 to about 4 carbon atoms; and

n is 1 or 2.

The alkyl groups present in these amine compounds may be either straight or branched-chain; primary, secondary or tertiary alkyls so long as the combined total of carbon atoms does not exceed ten. Similarly, the alkylen groups represented by X may be straight or branched-chain and can be derived from either primary, secondary or tertiary alkyls.

It will be seen from the above general formula that the compounds encompassed thereby may be characterized as monoalkyl or dialkyl amino mono-alkanols or alkoxy mono-alkanols. Some examples of such compounds include: monomethyl amino ethanol, dimethyl amino ethanol, monoethyl amino ethanol, monoethyl amino ethoxy ethanol, diethyl amino ethanol, diethyl amino ethoxy ethanol, diisopropyl amino ethanol, dibutyl amino ethanol, dibutyl amino ethoxy ethanol, n-butyl amino ethanol, dimethylamino-2-propanol, diisopropyl amino 2- propanol, n-butyl amino 2-propanol, isobutyl amino 2- propanol, dimethyl amino Z-butanol, dimethyl amino 1- butanol, etc.

The alkyl amino mono-alkanol compounds described herein may be advantageously employed in a variety of liquid lubricant compositions. They are particularly effective in liquid lubricant compositions which contain water as a component or impurity, or in liquid lubricants employed in machines, apparatus or systems which are subject to conditions which promote vapor phase corrosion and/or metal fatigue either in the presence or absence of water.

Some examples of such liquid lubricants include mineral oil or synthetic oil-based lubricating oil compositions suitable for use as automotive lubricants such as motor oils, gear oils and the like; aviation lubricants including jet engine oils; marine lubricants such as marine diesel oils; industrial lubes as exemplified by metal working oils, gear oils; and the like. Also included are the single phase lubricating compositions or functional fluids containing water and a synthetic base oil such as the glycol fluids containing water, glycols and polyglycols.

Further examples of liquid lubricants which may be improved in accordance with the invention include waterin-oil emulsions such as those employed as metal working fluids, oven chain lubricants, as well as those used as functional fluids such as hydraulic fluids, transmission fluids etc. Indeed, the use of the aforedescribed monoalkanol compounds with water-in-oil emulsions is a particular aspect of the present invention. It has been found that the instant mono-alkanol compounds because of their alkaline character are compatible with and particularly effective in water-in-oil emulsions which possess an alkaline or in some cases neutral environment. This is in contrast to behavior of heretofore known acidic inhibitors which tend to precipitate out of the alkaline emulsions. By employing the instant alkyl amino mono-alkanols it has been found that it is possible to impart to the emulsions not only vapor phase corrosion resistance and anti fatigue properties, but also improved anti-wear characteristics and increased periods of useful life.

The above-described liquid lubricants, both lubricating oils and water-in-oil emulsions, may contain base oils of lubricating oil viscosity having widely varying origin and characteristics. Some examples of base oils include mineral oils from different crudes, i.e., naphthenic, paraflinic, etc.; which have ben solvent and acid refined, hydrocracked etc.; and synthetic oils such as olefin polymers, hydrogenated olefin polymers, alkylene oxide polymers,

dicarboxylic acid esters, liquid esters of phosphorus, monomeric and polymeric silicones, esters of polyhydroxy alcohols and the like.

In the case of water-in-oil emulsions the base oil and water may be employed in various relative proportions, the water being present generally in the range from about to 70% by weight of the emulsion. Water-in-oil emulsions containing hydrocarbon base oils of from about 50- 400 S.U.V. at 100 F. are of particular interest.

The use of the particular alkyl amino mono-alkanol compounds defined hereinabove is necessary in order to achieve the desired vapor phase rust resistance, antifatigue properties and other desirable characteristics. The structure and characteristics of these specific mon0- alkanol compounds is important for it has been found, as will be shown hereinafter, that similar compounds including alkyl amines and certain di-alkanol compounds are not as effective in lubricant compositions. It should also be noted that the instant alkyl amino mono-alkanols must be present in the lubricant in an effective state. The mono-alk-anol compound should be free to act in the lubricant composition. This invention therefore should be distinguished from the use of reaction products, complexes or the like of the mono-alkanol compounds with other components wherein the mono-alkanols would be tied up or otherwise have their effectiveness diminished or destroyed.

The superiority of the lubricant compositions of the present invention containing the aforedescribed alkyl amino mono-alkanol compounds will be seen from the following series of comparative tests.

Vapor phase anti-rust test This test measures the eflectivenes of various amino compounds as vapor phase rust inhibitors in lubricants. According to the test procedure, a 16 ounce tallform widemouth glass jar is half filled with the fluid to be tested. A sandblasted and solvent-cleaned steel test panel is attached to the inside of a tin lid with a magnet and the lid then screwed loosely onto the glass jar to allow some breathing. The jar is then immersed overnight up to the fluid level in a water bath maintained at 175 F. and during the day removed and stored at room temperature for 8 hours. The vapor phase anti-rust capability of the fluid is determined by measuring the percent of test panel surface rusted after various periods of exposure. The smaller percent of rusting the more eifective is the inhibitor.

The results obtained with a water-in-oil emulsion after 7 days of exposure to test conditions is reported in Table 1, while the test results obtained after test periods of 27, 38 and 70 days is reported in Table 2.

The isopropyl amino ethanol employed in the following tests is, unless otherwise indicated, a commercial product containing about 60% of isopropyl amino ethanol.

TABLE 1.VAPOR PHASE ANTI-RUST TEST 1 Commercial hydraulic fluid containing 52 wt. percent of a naphthcnic oil having a S.U.V. of 100 at 100 F., and 40 wt. percent water.

TABLE 2.VAPOR PHASE ANTI-RUST TEST Percent Panel Stuiace Test Inhibitor Weight Rusted Alter- No. Percent 27days 38days 70days 1 Isopropylamino ethanol... 0.2 1 l 1 2 do 0.3 0 0 0 0.1 5 30 70 0.2 3 25 60 1 In commercial hydraulic fluid described in Table 1.

It will be noted from Table 1 that water-in-oil emulsions containing the instant alkyl amino alkanols (tests 2, 6 and 10) possessed excellent vapor phase anti-rust capabilities as evidenced by the low percent panel rusting. By contrast, the same Water-in-oil emulsions containing a well known vapor phase rust inhibitor morpholine (test 3) and monoethanol amine (test 5) which is structurally similar to the instant inhibitors, exhibited poor anti-rust characteristics.

Similarly, it is seen from Table 2 that emulsions containing the instant vapor phase rust inhibitors (tests 1 and 2) exhibited long term anti-rust characteristics as shown by the absence of any increase in panel surface rusting with increasing test periods. On the other hand, the same emulsions containing butylamine (tests 3 and 4) exhibited drastically increased rusting as the test period was extended from 27 to 70 days.

That the use of the instant alkyl amino monoalkanols is critical in order to obtain water-in-oil emulsions possessing the desired superior characteristics is demonstrated by the results reported in the following Table 3 where the emulsions of this invention were compared with similar emulsions containing certain dialkanol amines. In this particular test the fluid was continuously exposed to temperatures of 240 F. for periods of 1, 2 and 7 days.

TABLE 3.VAPOR PHASE ANTI-RUST TEST Percent oi Panel Surface Rusted After Contin- Test Weight nous Exposure at No. Inhibitor Percent 240 F. for

1 day 2 days 7 days None. Diisopropylaminoethanol. 0. 3 Butylaminoethanol- 0.3 Diethylarnlnoethoxyetha nol 0.3 Dibutylaminoethanol. 0. 3 Methylaminodiothanol. 0. 3 Ethylarninodiethanol. 0. 3 IsopropylaminodiethanoL 0. 3 Butylaminodiethanol. 0. 3

1 In the commercial hydraulic fluid described in Table 1.

It is seen from Table 3 that while the emulsions of the invention containing the instant alkyl amino monoalkanols (tests 2-5) exhibit superior and prolonged antirust properties, the emulsions containing the dialkanol compounds (tests 6-9) showed poor anti-rust capabilities and the test panels exposed to these latter emulsions were highly rusted after only one day of exposure.

Vapor phase anti-rust tests were conducted for more extended periods of time (up to days) on several types of water-in-oil emulsions and lubricating oils as reported in Table 4. In this series of tests, water was added to each of the lubricating oil compositions and to the premium hydraulic fluid in the amounts shown in the table. The test procedure employed described above was used but the jar was immersed in a water bath maintained at 180 F. instead of at F.

It will be seen from the results reported in the following Table 4 that the addition of the alkyl amino monomeasuring the characteristics of such emulsions, is conducted by circulating the emulsion to be tested in a Vickers vane type pump, Model V-111-E10 (rated at 2 gallons per minute). This is a positive displacement vane-type hydraulic pump. The rotor has 12 steel vanes in contact with a steel ring and turns at about 1200 rpm.

TABLE 4.--VAPOR PHASE ANTI-RUST TEST Percent Panel Surface Rusted After (Days) Test No. Lubricant Wt. Percent Inhibitor Motor Oil 1 plus 5% H 0 100 .do 1 0.2 isopropylamiuoethanol 3 3 3 3 3 3 3 do 0.2 cyclohexylamine 50 70 90 Motor Oil 1 plus 40% E20 0.2 isopropylaminoethanol 4 6 6 10 10 10 15 Hydraulic Fluid 2 100 do. 0.2 diethylaminoethanol 0 0 0 0 0 0 5 0.2 diisopropylaminoethanol 4 4 6 8 15 18 35 0.2 dimethylaminoethanol 4 4 4 4 6 7 7 0.2 ethlaminoethanol 4 4 5 6 8 8 8 0.2 isopropylaminodiethanoL. 70 80 100 0.2 n-butylaminoethanol 5 5 5 5 5 5 8 0.2 butylarninodiethanol 70 80 100 0.2 methylarninoethanol 5 5 6 6 6 8 8 0.2 methylaminodiethanoh 100 0.2 ethylaminodiethanol. 0.2 isopropylaminoethancl 8g 8 8 8 8 8 8 0.3 isopropylaminoethanol 0 0.3 diethylaminoethanol 0 0.3 dimethylaminoethanol 0 .(10. 0,3 ethylqminnethannl 0 4 Premium Motor Oil 4 plus 5% H O 100 4a do. 0.3 isopropylaminoethanol 4 4 4b do. 0.3 diethylaminoethanol .4 4 5 5 Premium Hydraulic Oil 5 plus 5% added H 0... 30 50 5a do. 0 0 0 5b. 0 0 0 5e 0 0 0 5ddo. 0 0 0 6 SAE 30 Base Oil plus 15% E 0. 100 6a. do. 0 0 0 0 0 0 1 6b- 0 0 0 0 0 0 0 6c- 0 0 0 0 0 0 0 6d- 12 12 12 12 12 12 12 6e. 0 0 0 0 0 0 0 6i- 0 0 0 0 0 0 0 6g 1 1 1 1 l 2 2 6h. (1 0 0 0 0 5 8 8 7 Diesel Engine Oil 7 plus 15% E10 3 100 7a do. 6 (i 6 6 6 6 7b. 1 1 2 2 2 2 7c 4 4 5 5 5 5 7d- 12 20 20 20 20 30 7e- 0 0 0 0 0 0 7L 5 5 5 6 6 6 7g 25 25 25 25 25 25 7h- 3 6 6 6 6 6 Commercial product containing cross-graded base oil of 20% S.U.S. (100 F.) neutral stock, 20% solvent refined 200 S.U.S. (100 F.) neutral, 60% 100 S.U.S. (100 F.) naphthenic stock.

2 Commercial hydraulic fluid of about 52% 100 S.U.S. (100 F.) naphthenic stock, about 40% water.

5 Solvent refined neutral stock of 8.13.8. (100 F.).

4 Commercial product, base oil contains about 80% solvent refined neutral stock of 130 S.U.S. (100 F.), 20% solvent refined naphthenic stock M100 S.U.S. (100 F.).

Vickers pump test In order to determine the anti-wear properties and fluid life of the water-in-oil emulsions in addition to their vapor phase anti-rust characteristics, the emulsions were subjected to a Vickers pump test.

The Vickers pump test, which is a recognized test for 5 Commercial hydraulic oil containing 150 S.U.S. (100 F.) solventrefined neutral paraifinie mineral oil and about 40% water.

6 Oil blend consisting of 64% paraflinic solvent-refined neutral mineral oil of 200 S.U.S. (100 F.) and 36% bright stock of 2,650 S.U.S. (100 F.).

7 Commercial diesel engine lubricant containing about 50% 3,300 S.U.S. (100 F.) solvent-refined coastal bright stock and 40% 520 8.11.8. (100 F.) naphthenic stock.

8 90% of panel surface rusted within 4 hours.

The results Of the tests are reported in Table 5. TABLE 6 FOUR BALL FATIGUE TEST Test No. Egogrs to a L118 TABLE 5.EFFECI OF VAPOR PHASE INHIBITORS IN VICKERS PUMP TESTS AT 1,000 P.S.I., 175 F., 2 GAL/MIN.

is s s as Wt. Hours Percent Total g fi fih pus sopmpy Test Inhibitor Perof ofSuriace Wear, N0. cent Oper- Rusted mg.

M1011 1 Commercial hydraulic fluid containing about 52% 100 S.U.V. (100 1 0 F.) naphthenic stock, 40% water. 1 None 71 32 As can be seen from the above, the addition of isoigg propylamino ethanol to the hydraulic fluid increased the 514 so time period to failure from 19.9 to 50 hours thereby in- 1, 36% $3; dicating the increased anti-fatigue qualities imparted to 2 Isopropyl amino ethanoL..- 0.2 09 l the emuls on,

33% i 66 Gear pump test 557 1 "e 724 1 i The 1m roved anti-fatigue characteristics and the rep p u 822 l 3% sultm-g increased pump life achieved by the use of the 11130 2 104 water-in-oil emulsions of the invention is further demong strated by the data obtained from gear pump runs using 1:446 100 132 a Commercial Shearing Model D-2 inch gear pump. i gg 188 The gear pump was run to failure under 1500 psi. 3 Butylamine 0.05 s s pressure at 1200 r.p.m. at 150 F. The failure was de- Zgg $8 23 25 tected by an overload device when the amperage exceeded 605 70 34s a preset level. The results are given in the following 4 do 0 07 g 8% Table 7 where it is seen that the addition of the iso- 340 2 20 164 propylamino ethanol lengthened the time period to failure 980 100 200 5 lsoprppylamme plus hewb Q1 g from 165 hours (test 1) to 279 hours (test 2).

0.1 551 5 182 TABLE 7. GEAR PUMP TEST 724 200 11 365 2 235 Test N0. Composition Hours to failure 1 Commercial hydraulic fluid described in Table 1. 2 Reservoir badly rusted. Hydraulic flujdl Hydraulic fluid plus 0.2% isopropyl- 279 amino ethanol. Hydraulic fluid plus 0.6% lsopropyl- 203 It will be noted from Table 5 that the emulsion (test ammo ethanol 2) containing the instant alkyl amino mono-alkanol compound possesses superior vapor phase anti-rust characteristics, as well as low wear rates and prolonged emulsion life. By contrast, it is seen from tests 3-5 that at the end of about 1000 test hours, emulsions containing butylamine or isopropylamine and hexylarnine mixtures completely lost their useful vapor phase rustprotection so that not only was the test panel badly rusted but the reservoir of the pump was also rusted. In addition, it is seen that the emulsions of these tests 3-5 possessed decidedly inferior anti-wear properties as evidenced by their high total wear values. Thus, for example, after about 1000 hours, the emulsions of tests 3 and 4 had total wear values of 468 and 200 mg. respectively, compared to 102 mg. total wear obtained with the emulsion of test 2.

F our-ball fatigue test As indicated hereinabove a major drawback to the wider use of water-in-oil hydraulic fluids is their poor antifatigue properties. A particular advantage of the water in-oil emulsions of this invention, however, is their improved anti-fatigue life. This is shown by the Four-Ball Fatigue Test.

According to this test three lower steel balls are allowed to spin freely in a conforming race driven by a fourth steel ball which is held firmly in the chuck of the spindle of the four-ball fatigue tester. The load employed is 294 pounds and the speed 5200 r.p.m. The test is terminated when one of the balls shows a fatigue pit which is indicated by excessive noise and vibration. This vibration actuates a vibration switch in the drivemotor electrical circuit which turns off the tester.

The longer the time period to failure the greater is the anti-fatigue qualities of the fluid tested. The results are reported in the following Table 6.

1 Commercial water-in-oil emulsion containing about 52% 100 S.U.V. (100 F.) naphthenic stock, 40% water.

The alkyl amino mono-alkanol compounds of the invention may be employed in the form of relatively pure compounds or as mixtures of dilferent alkyl amino monoalkanols. The amount of alkyl alkanol amines which should be used in the lubricant compositions will vary depending on such factors as the nature of the lubricant, its intended use, the presence or absence of other additives, etc. In general, from about 0.05 to about 5 weight percent, preferably from about 0.1 to about 1.0 weight percent are suitable. The use of larger amounts may in some instances be suitable depending on economic considerations.

The lubricant compositions of the invention may also contain other ingredients normally used with such compositions such as antioxidants, detergents, V.I. improvcrs, inhibitors, E.P. agents, pour point improvers, and in the case of water-in-oil emulsions, emulsifiers, stabilizing agents, anti-freeze agents etc.

It will, of course, be appreciated that many variations and modifications may be practiced without departing from the scope and spirit of the present invention.

Having described the invention, what I desire to secure and claim by Letters Patent is:

1. A liquid lubricant composition containing an effective amount sufficient to provide corrosion resistance thereto of a mono-alkanol compound of the formula:

where R represents an alkyl group; R is selected from the class consisting of alkyl groups and hydrogen atoms;

the sum of R+R' is equal to from 1 to about 10 carbon atoms; X is an alkylene group having from 2 to about 4 carbon atoms; and n represents an integer selected from the class consisting of l and 2.

2. The composition of claim 1 which contains a lubricating oil.

16. The composition of claim 4 wherein said vapor phase anti-corrosion agent is butylamino ethanol.

17. The composition of claim 4 wherein said vapor phase anti-corrosion agent is dimethylamino ethanol.

3. The composition of claim 1 which contains a water- 5 18. A process for lubricating moving metal surfaces in-oil emulsion. normally subject to vapor phase corrosion and metal 4. A liquid lubricating composition containing a minor fatigue wherein the said metal surfaces enclose vapor amount of a vapor phase anti-corrosion agent of the forspaces in which water is present which comprises the steps mula: of (1) incorporating into a liquid lubricating composition R an effective amount suflicient to provide vapor phase corrosion resistance and anti-fatigue characteristics thereto NAXTOMH of a compound of the formula R R where R represents an alkyl group; R is selected from N(X O)H the class consisting of alkyl groups and hydrogen atoms; the 511m of -iis equal to from 1 to about 10 Carbon where R represents an alkyl group: R is selected from atoms; X is an alkylene group having from 2 to about the class consisting of alkyl groups and hydrogen atoms; 4 carbon atoms; and n represents an integer selected the sum of R and R is equal to from 1 t b t 10 from the class consisting of 1 and 2. bon atoms; X is an alkylene group having from 2 to about 5. The composition of claim 4 which contains water. 4 carbon atoms; and n represents an integer selected from 6. The composition of claim 4 which contains a mineral the class consisting of 1 and 2, and (2) introducing said lubricating oil. liquid lubricating composition into a moving lubrication 7. The composition of claim 4 which contains a synsystem operating under conditions normally conductive to thetic lubricating oil. the formation of water vapor whereby the said moving 8. The composition of claim 4 which contains a watermetal surfaces are contacted therewith. in-oil emulsion. 19. The process of claim 18 wherein the said com- 9. The composition of claim 8 wherein said water-in-oil pound is isopropylamino ethanol. emulsion contains from about 10 to about 70% by weight 20. The process of claim 18 wherein said additive is of water. employed in an amount from about 0.05 to about 5 weight 10. The composition of claim 4 wherein said vapor percent. phase anti-corrosion agent is present in an amount from 21. The process of claim 18 wherein said liquid lubabout 0.05 to about 5 weight percent. ricating composition is a water-in-oil emulsion.

11. The composition of claim 4 wherein said vapor phase anti-corrosion agent is isopropylamino ethanol. References Cited y the Examiner 12. The composition of claim 4 wherein said vapor UNITED STATES PATENTS i? 95 2 855 .agent diethylammc p 2 512,949 1950 Li 252 39z X position of clalm 4 wherem said vapor 2 56 88 10/1960 D 252 3 X phase anti-corrosion agent is diisopropylamino ethanol. 9 enman 92 14. A hydraulic fluid containing from about 10 to about by weight of water, a hydrocarbon oil having OTHER REFERENCES a Saybolt Universal viscosity at F. from about 50 Aliphatic Nitrogen p Carbide & Carbon to about 400 seconds, and an elfective amount sufiicient Chemicals 1952, P- to provide corrosion resistance thereto of a mono-alkanol 45 s Rohm and Haas 1959, all P compound of the formula shown in claim 4. g 15. The composition of claim 4 wherein said vapor DANIEL WYMANPNmary Exammer' phase anti-corrosion agent is ethylamino ethanol. C. F. DEES, Assistant Examiner.

Disclaimer 3,280,029.Hms F. Waldmcmn, Glassboro, NJ. LUBRICANT COMPOSI- TIONS. Patent dated Oct. 18, 1966. Disclaimer filed June 10, 1969, by the assignee, Mobil Oil Corporation. Hereby enters this disclaimer to claims 1, 2, 4, 6, 7, 10 and 12 of said patent.

[Ofiioial Gazette October 14, 1.969.]

Disclaimer 3,280,029.J](ms F. Waldmann, Glassboro, NJ. LUBRICANT COMPOSI- TIONS. Patent dated Oct. 18, 1966. Disclaimer filed June 10, 1969, by the assignee,1l[obil Oil Corporation.

Hereby enters this disclaimer to claims 1, 2, 4, 6, 7, 10 and 12 of said patent.

[Ofiicial Gazette October 14, 1.969.]

Claims (2)

1. A LIQUID LUBRICANT COMPOSITION CONTAINING AN EFFECTIVE AMOUNT SUFFICIENT TO PROVIDE CORROSION RESISTANCE THERETO OF A MONO-ALKANOL COMPOUND OF THE FORMULA:

3. THE COMPOSITION OF CLAIM 1 WHICH CONTAINS A WATERIN-OIL EMULSION.