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Publication numberUS3718609 A
Publication typeGrant
Publication dateFeb 27, 1973
Filing dateApr 5, 1971
Priority dateApr 5, 1971
Publication numberUS 3718609 A, US 3718609A, US-A-3718609, US3718609 A, US3718609A
InventorsWeimer D
Original AssigneeContinental Oil Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Liquid detergent compositions
US 3718609 A
Abstract
A liquid detergent composition is provided having an aqueous layer and a layer of a liquid water-immiscible oily material, which composition when shaken, forms a temporary oil-in-water emulsion. The aqueous layer contains a foam-producing water-soluble organic detergent, a non-emulsifying foam stabilizer, and water.
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Description  (OCR text may contain errors)

United States Patent Weimer 1 Feb. 27, 1973 LIQUID DETERGENT COMPOSITIONS OTHER PUBLICATIONS Inventor: Dean Weimer, Ponca y. OkIa- Chemical Abstracts, Vol. 47, Col. 3553, vol. 49, Col. [73] Assignee: Continental Oil Company, Ponca 1407" 1038b- City, Okla. ,1 til 1 Primary ExaminerJohn D. Welsh [22] F1 AP 197 Attorney.loseph C. Kotarski, Henry H. Huth, Robert [21] Appl. No.: 131,461 B. Coleman, Jr. and Glen M. Burdick 521 US. Cl. .252/545, 252/153, 252/307, [57] ABSTRACT 252/160 A liquid detergent composition is provided having an [51] Int. Cl ..Cl Id l/02 aqueous layer and a layer of a liquid Water-immiscible oily material, which composition when shaken, forms [58] Field of Search 252/307 225 6 a temporary oil-in-water emulsion. The aqueous layer contains a foam-producing water-soluble organic de- [56] References Cited tergent, a non-emulsifying foam stabilizer, and water.

7 Claims, No Drawings LIQUID DETERGENT COMPOSITIONS BACKGROUND OF THE INVENTION material phase, which composition when shaken forms a temporary oil-in-water emulsion.

2. Brief Description of the Prior Art In the liquid detergent field, such as shampoos, the present trend is to produce a multi-phase product which, when shaken, forms a temporary emulsion. In such formulations, the lower phase is an aqueous phase which contains the necessary cleaning ingredients, and the upper phase is an oil material which conditions the hair. Further, similar compositions are employed as bubble bath/bath oil compositions, the basic distinction between the shampoo formulations and the bubble bath/bath oil compositions being in the proportion of oil in the upper phase.

The multi-layer physical state of the composition referred to above is essential so that the compositions will produce foam in a product designed to have good skin and hair cleansing properties, and yet, in the case of the bubble bath/bath oil compositions leave an oily film upon the skin of the bather and, in the case of the shampoo formulation, leave a suitable amount of oil on the hair so that the hair will be manageable for grooming. A problem encountered in manufacturing such a product has been that the conventional active-foam booster ingredients normally used in shampoos and the like emulsify the oil so that a clean phase split does not occur between the aqueous phase and the oily material phase. In an effort to overcome these problems, deemulsifiers have been used to prevent emulsification of the aqueous phase and oily material phase. However, such de-emulsifiers are not always effective and often inhibit the desirable properties of the product. For example, many of the de-emulsifiers employed in prior art liquid detergent compositions having a multi-phase product have inhibited the effectiveness of the foam booster incorporated in the composition resulting in a product not possessing desired foam properties. Thus,

new formulations are constantly being sought wherein a liquid detergent formulation can be employed to produce a two-phase product, and yet at the same time, remove the need for the incorporation of ingredients such as de-emulsifiers which inhibit the effectiveness of the resulting products.

OBJECTS OF THE INVENTION An object of the present invention is to provide an improved liquid detergent composition. Another object of the present invention is to provide an improved multi-phase liquid detergent composition which possesses effective cleaning properties as well as conditioning properties without suffering from the deficiencies of the prior art multi-phase liquid detergent compositions. Another object of the present invention is to provide a novel multi-phase liquid detergent composition which possesses a clean phase split between the aqueous and oily material phase without inhibiting the desired cleaning and conditioning properties of the liquid detergent composition. These and other objects,

advantages and features of the present invention will become apparent to those skilled in the art from a reading of the following detailed description.

SUMMARY OF THE INVENTION According to the present invention there is provided a liquid detergent composition having an aqueous phase and a liquid, water'immiscible oily material phase, which composition, when shaken, forms a temporary oil-in-water emulsion. The aqueous phase consists of a foam-producing water-soluble organic detergent, a non-emulsifying foam stabilizer, and water.

Further, according to the invention, there is provided a liquid detergent composition having an aqueous phase and a liquid, water-immiscible oily material phase wherein the non-emulsifying foam stabilizer incorporated into the aqueous phase in a water-soluble salt of an acrylic acid polymer.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The liquid detergent compositions of the present invention include compositions which provide detergency and simultaneously provide for the deposition of a certain amount of oily material on the subject being cleaned. As previously stated, typical examples of such liquid detergent compositions are bubble bath/bath oil compositions and shampoo compositions. The duality of properties possessed by such a multi-phase liquid detergent composition is due to the fact that the compositions contain an oily phase and an aqueous phase which form temporary oil-in-water emulsions when shaken. The aqueous phase contains a foam-producing watersoluble liquid detergent, a non-emulsifying foam stabilizer and water. The oily phase, as the name implies, furnishes oily material which serves as a hair conditioning aid, in the case of shampoo formulations, and as a skin softener, in the case of the bubble bath/bath oil composition.

Although the liquid detergent compositions of the invention exist in the form of separate phases or layers that are shaken prior to use whereupon they form oilin-water emulsions which are only temporary. However, this emulsion state enables the user to measure out the required amount of the composite compositions each time the liquid detergent compositions are used. The actual time required for the detergent composition to return to the layered or multi-phase state will be dependent on the actual formulation, but generally such phase splitting will occur within about 12 hours.

In order that the multi-phase liquid detergent compositions have the desired properties described above, it is essential that they contain four ingredients, namely, a water-immiscible oily material, a foam-producing water-soluble organic detergent, a non-emulsifying foam stabilizer, and water. As is evident, the foamproducing water-soluble organic detergent, the nonemulsifying foam stabilizer and the water constituents form the aqueous phase and the water-immiscible oily material forms the oily phase. The amounts of the various ingredients can vary widely and will be dependent upon the nature of the particular ingredients present, as well as upon the nature or use of the composition.

The multi-phase liquid detergent compositions preferably contain at least 5 percent by weight of one or more water-immiscible oily materials. Although in certain cases amounts up to 50 percent may be used, the amount of oily material usually will not be more than 50 percent. In the composite shampoo/hair conditioning compositions the amount of oily material is desirably from 5 to 20 percent by weight, while in the composite bubble bath/bath oil compositions the amount of oily material will usually be at least about 20 percent by weight. The oily material serves as a skin softener or emollient and as a hair conditioner or hair grooming aid.

Typical suitable oily materials which can be employed to form the oily phase of the compositions of the present invention include light to heavy mineral or hydrocarbon oils, such as the light mineral oils having a Saybolt viscosity of 65-75 cps. 38 C and a specific gravity of 0.835 to 0.845 at 15.5 C animal and vegetable oils, such as linseed oil, castor oil, olive oil, cotton seed oil, safflower oil, almond oil, peanut oil, coconut oil, coconut oil fractions, cornoil, sesame oil, and brominated vegetable oils; synthetic oils which are fatty acid alkyl esters containing a total of from 16 to 22 carbon atoms, such as isopropyl myristate, isopropyl palmitate and isopropyl stearate; and lanolin compounds, such as the well-known lanolin esters and lanolin alcohols. Desirable results are obtained wherein the oily material is mineral or hydrocarbon oil, because of the sharpness of the interface which occurs between the oil phase and the aqueous phase. In addition, the oily phase should be liquid at room temperature, and preferably also at C.

As previously mentioned, the aqueous phase of the multi-phase liquid detergent composition contains a foam-producing water-soluble organic detergent, a non-emulsifying foam stabilizer, and water. The amount of foam-producing water-soluble organic detergent employed can vary widely depending upon the particular formulation desired and its use. Generally, however, the foam-producing water-soluble organic detergent will be present in an amount within the range of from about to 40 percent by weight, based on the total weight of the aqueous phase.

In the composite bubble bath/bath oil compositions the amount of the foaming organic detergent is preferably from 5 to 25 percent by weight, while in the composite shampoo/hair conditioning compositions the amount of the foaming organic detergent is preferably from to 30 percent by weight.

The foam-producing organic detergent compositions which can be employed comprises one or more watersoluble non-cationic surface-active agents, ie an anionic, or amphoteric surfactant, or a mixture thereof, which produces acceptable foam. Preferred anionic detergents are sulfonated and sulfated anionic detergents and in particular the sodium, magnesium, ammonium, mono, diand triethanolamine salts of sulfated fatty alcohols as well as these salts of the sulfonated alkylaryl compounds, all of which have a total of from 12 to 21 carbon atoms. Typical anionic detergents include sodium lauryl sulfate, sodium oleyl succinate, ammonium lauryl sulfosuccinate, sodium lauryl ether sulfate, ammonium lauryl sulfate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, sodium dodecylbenzene sulfonate, triethanolamine dodecylbenzene sulfonate and sodium N-lauroyl sarcosinate. Other anionic detergents include triethanolamine aluratemyristate and triethanolamine oleate.

Amphoteric or ampholytic detergents include N-lauryl-N'-carboxymethyl-N-(2-hydroxyethyl)ethylenediamine, coco-beta-alanine, and the Miranol compounds described in US. Pat. Nos. 2,528,378 and 2,781,354.

The second essential ingredient of the composition which is present in the aqueous layer is the non-emulsifying foam stabilizer. The amount of the non-emulsifying foam stabilizer can vary widely but is generally present in an amount of from about 2 to about 10 percent by weight based upon the total weight of the aqueous phase of the composition. Desirable results have been obtained wherein the non-emulsifying foam stabilizer is present in the amount of about 3 to 5 weight percent. The non-emulsifying foam stabilizers which can be employed in the composition of the present invention are the water-soluble salts of acrylic acid polymers. This acrylic acid polymers can be represented by the structural formula wherein x is an integer from about 550 to about 2,250. The polymers are neutralized to form a salt and the cation constituent of the salt is selected from the group consisting of sodium, magnesium, ammonium, mono-, di-, and triethanolamine. Especially desirable results have been obtained wherein the salt is the sodium salt or the triethanolamine salt and the molecular weight of the resulting acrylate is from about 50,000 to about 150,000 with the lower molecular weight polymer being the most desired.

The third essential ingredient in the aqueous phase is water and the amount will vary depending upon the amount of the foam producing organic detergent and non-emulsifying foam stabilizer employed. In addition, the amount of water in the total composition will vary depending upon the amount of oily material present in the total composition.

While the compositions of the invention contained the above-mentioned ingredients, other compatible adjuvants can also be included therein. Thus the composition may, for example, contain one or more of the following: a perfume or essential oil, an oil-soluble or water-soluble dye, a germicide, a protein hydrolysate, and the like.

The compositions of the invention can be prepared merely by blending together the various ingredients. Usually the ingredients required to form the aqueous phase component of the composition will be blended together separately, and then admixed with the ingredients employed to produce the oily phase of the composition.

In order to more fully describe the invention the following examples are presented. However, it is to be understood that the examples are for illustrative purposes only and any enumeration or details contained therein are not to be interpreted as a limitation on the invention except as indicated in the appended claims. All parts and percentages of constituents referred to in the following examples are by weight unless otherwise indicated.

6 EXAMPLE Conc. Hard Water (Ml) Shampoo (Grams in Beaker) A series of experiments were conducted on the novel 10% 90 10.0 multi-phase liquid detergent composition to determine 25% 75 250 its foam producing properties, the stability of the foam 5 6' After adding the required amount of hard water, generated, and the compos tions ability to form a clean add a magnetic Stirring bar and place Sample on the phase 5pm between the Olly mammal Phase and P Thermolyne Stir Plate. Set glass thermometer into samaqueous Phase In each expenmem meth?m1amme ple. Stir at full speed with heater on thereby allowing lauryl sulfate was used as the foam-producing f the temperature to reach 100F in 4 to 5 minutes.

soluble organic detergent constituent, sodium in while the Sample is warming, rinse out a 500 ml polyacrylate, having a molecular weight ranging from 50,000 to about 150,000, was employed as the nonemulsifying foam stabilizer and the oily material constituent was light mineral oil or a blend of about onethird olive oil and two-thirds light mineral oil. The materials were then admixed to form a liquid detergent formulation having an 87 percent aqueous phase and a 13 percent oily material phase. The aqueous phase of the liquid detergent contained about 21 percent triethanolamine-lauryl sulfate. The amount of sodium polyacrylate was varied, as shown in the following table to determine concentration variables for same. Tests were then run by the standard shampoo test which measures the foam generation ability by the milliliters of foam and the stability of the foam as the time required for 75 milliliters of the liquid to draw from the foam. Therefore, the higher values of the foam generated and the longer the time required for the drainage are desirable and indicate a product having the desired foam and foam stability properties.

The standard shampoo test referred to above and utilized to test the novel liquid detergent formulation is as set forth hereinbelow. The amount of the ingredients was varied as shown in Table 1.

TEST PROCEDURE 1. Weight 10.0 and 25.0 grams of test shampoo into separate 150 ml Griffin low form glass beakers.

2. Mix synthetic sebum which has been allowed to return to room temperature with a metal spatula. The sebum is a synthetic soil to simulate actual conditions.

3. Distribute 3.0 grams of sebum around the sides of the 150 ml beaker taking care not to allow it to come into contact with the shampoo nor to come up so high in the beaker to be above the water level when it is introduced.

4. Premeasure 90, 85, 80 and 75 ml of water of the desired hardness (50 and/or 250 ppm) in four separate 100 ml cylinders.

5. Add the hard water to the following manner to result in the following concentrations of shampoo:

glass cylinder and prewarm with 100 F tap water. Cylinder should contain the capped plastic tube filled with water.

8. Drain the 500 ml glass cylinder when sample temperature reaches 98 F.

9. Pour sample into 500 ml cylinder when temperature reaches 100 degrees F being careful not to allow the magnetic stirring bar to drop into the cylinder.

10. Attach the 500 milliliter cylinder to the rotator assembly to keep the cylinder in the perpendicular plane when rotating.

1 1. Rotate the cylinder a total of 20 complete circles (40 half circles) to generate foam. The rate at which the cylinder is rotated is critical. Consistent results are obtained if the rotations are completed within 35-45 seconds. It is also important to rotate at a constant speed. If difficulties are encountered, a Metronome should be used.

12. Start the stopwatch immediately upon completion of the rotations.

13. Remove the stopper and read the total foam volume (including liquid). Record this as the volume of foam generated.

14. Remove the 500 ml graduated cylinder from the rotator assembly gently and set it on the table top.

15. Stop the stopwatch when the liquid level reaches the 100 ml mark. (Actually, ml have drained since the plastic cylinder displaces 25 ml of liquid). Record the time interval from the completion of the rotations to the point at which ml of apparent liquid has drained as the drainage time.

16. The test results are recorded as ml of foam/drainage time in seconds.

Results of the test on the novel liquid detergent composition of the present invention are tabulated in Table I. The date clearly illustrate the utility of the novel detergent composition as a two-phase shampoo wherein sodium polyacrylate is employed as a non-emulsifying foam stabilizer. Further, the data illustrate the effectiveness of the sodium polyacrylate in giving a clean phase split between the oily material phase and the aqueous phase.

TABLE I.POLYACRYLATE CONCENTRATION Formulation:

21% triethanolamine lauryl sulfate; Polyacrylatc as shown in tablc87% Foam/drainage time, ml./sec.

Polyacrylatn olive oil, lt. mineral oil Lt. mineral oil Molecu- Run No lar Wtv Cation Percent 10% 25% 10% 25% Phase split l) 5 3-layer, middle layer ref. to as cuff- 50, 000 N a 0 /11 275/91 Oil phase not homogeneous. 200/20 280/73 Good.

50,000 N 1 250/35 320/138 D0. 200/5? 360/16 D0. 50, 000 Na t 275/45 330/153 Do. 300/65 375/111. Du.

Formulation:

21% triethanolamine Q.s. water Oil (type shown)i3% Test conditions:

250 p.p.m. Hardness 3 grams Seburn and 25% shampoo lauryl sulfate; Polyacrylate as shown in table--h7};

Foam/drainage time, ml./see.

Polyacrylate olive oil,

325/254 V. large top layer.

230/82 Oil rl hase not homogeneous. V e e )0.

Good. 7 Do. Do.

Oil phase not homogeneous.

Triethanolamine.

In addition to the above, experiments were conducted in which other types of water-soluble polymers 25 were employed as the non-emulsifying foam stabilizer. These other types of water-soluble polymers were guar gum and ethylene maleic anhydride polymers. The formulation containing the guar gum was a thick gummy mixture showed no signs of splitting into two phases. The formulations containing the ethylene maleic anhydride copolymers produced three phase products at concentrations of both 2 and 5 weight percent.

Therefore, the above data clearly indicate that a multi-phase liquid detergent composition in which the aqueous phase contains a foam-producing, water-soluble organic detergent and a water-soluble salt of a polyacrylate possesses the desired foam and foam stability properties, as well as the desired phase splitting properties.

Having thus described the invention, I claim:

1. A liquid detergent composition having an aqueous phase and a liquid water-immiscible oily material phase which composition, when shaken, forms a temporary oil-in-water emulsion, said aqueous phase consisting essentially of a foam producing water-soluble, non-cationic organic detergent, a water-soluble neutralized salt of a polyacrylate having a molecular weight in the range of from about 50,000 to about 150,000 and water.

2. The composition of claim 1 wherein the poly portion of said water-soluble neutralized salt of a polyacry late is represented by the formula ll: ll

3. The composition of claim 2 wherein said cation constituent is selected from sodium and triethanolamine.

4. The composition of claim 2 wherein said composition contains from about 5 to about 50 percent by weight of said water-immiscible oily material and from about to 50 percent by weight said aqueous phase, said aqueous phase containing from about 5 to about 40 percent by weight of said foam-producing watersoluble organic detergent and from about 2 to about 10 percent by weight said water-soluble neutralized salt of said polyacrylate.

5. The composition of claim 4 wherein said water-immiscible oily material is present in an amount of at least 20 percent, said oily material being selected from the group consisting of mineral oils, and blends of mineral oils and vegetable oils, and said aqueous phase contains from about 5 to 25 percent of said foam-producing, water-soluble detergent and from about 3 to 5 percent of said water-soluble neutralized salt of said polyacrylate.

6. The composition in claim 4 wherein said water-immiscible oily material is present in an amount of about 5 to 20 percent, said oily material being selected from the group consisting of mineral oils, and blends of mineral oils and vegetable oils, and said aqueous phase contains from about 10 to 30 percent of said foamproducing, water-soluble detergent and from about 3 to 5 percent by weight of said water-soluble neutralized salts of said polyacrylate.

7. The composition of claim 6 wherein said oily material is present in an amount of about 13 percent, said aqueous phase is present in an amount of about 87 percent and the detergent constituent is triethanolamine lauryl sulfate and is present in an amount of about 21 percent.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2580713 *Feb 26, 1947Jan 1, 1952Procter & GamblePlastic detergents and method of making same
Non-Patent Citations
Reference
1 *Chemical Abstracts, Vol. 47, Col. 3553, Vol. 49, Col. 1407i, Vol. 55, Col. 1038b.
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4006703 *Nov 10, 1975Feb 8, 1977Smith Judson LFoamed wax apparatus
US4442018 *Nov 1, 1982Apr 10, 1984The United States Of America As Represented By The United States Department Of EnergyStabilized aqueous foam systems and concentrate and method for making them
US4775489 *May 16, 1986Oct 4, 1988Union Oil Company Of CaliforniaSeparation into liquid phases; removal from well
US5344643 *Aug 27, 1993Sep 6, 1994Dowbrands L.P.Carboxyvinyl polymer, anionic surfactant
US5597793 *Nov 15, 1994Jan 28, 1997Ecolab Inc.Contains foam stabilizing acrylic polymers, alkalinity source and animicrobial agent; vertical and horizontal surfaces
US5686024 *Dec 18, 1995Nov 11, 1997Rhone-Poulenc Surfactants & Specialties, L.P.Diallyldialkylammonium salt, unsaturated amide, oxyalkylated acrylate
US6022727 *Jan 12, 1998Feb 8, 2000Board Of Trustees Operating Michigan State UniversityForming gas containing microbubbles in a liquid; providing emulsifier and surfactant mixtures which are hydrophobic, amphipathic or hydrophilic, forming gas microbubbles, changing conditions of solution so microbubbles coalesce
US6180587 *Sep 28, 1999Jan 30, 2001Colgate Palmolive CompanyMultiple phase compositions
US6429177Aug 22, 2000Aug 6, 2002Unilever Home & Personal Care Usa, Division Of Conopco, Inc.Separating multi-phase personal wash composition in a transparent or translucent package
US6521584Mar 9, 1999Feb 18, 2003Henkel Kommanditgesellschaft Auf AktienChlorofluorocarbon free; can be temporarily transformed into an emulsion by shaking; cleaning glass and ceramics
US6565838 *Oct 24, 2002May 20, 2003Carroll Thomas EMixture of surfactants
US6720300Oct 20, 1998Apr 13, 2004Reckitt Benckiser N.V.Surfactants and electrolytes
US6727209Aug 14, 2002Apr 27, 2004Unilever Home & Personal Care, Usa, Division Of Conopco, Inc.Use of sucrose widens the window of polydextrose which can be used and lowers the levels of polydextrose necessary to achieve biphasic effect
US6750191 *May 20, 2003Jun 15, 2004Procter & Gamble CompanyMethod of sequentially dispensing a consumable layered liquid composition and product containing the same
US6787511Aug 14, 2002Sep 7, 2004Unilever Home & Personal Care Usa Division Of Conopco, Inc.Biphasic composition induced by polydextrose
US6797685Apr 26, 2002Sep 28, 2004Unilever Home & Personal Care Usa, Division Of Conopco, Inc.Liquid laundry detergent with emulsion layer
US6884766Jun 19, 2001Apr 26, 2005The Procter & Gamble CompanyMulti-phase fabric care composition for delivering multiple fabric care benefits
US7220713Apr 13, 2005May 22, 2007Unilever Home & Personal Care Usa, Division Of Conopco, Inc.To obtain viscosity levels more suitable for, for example, shampoos, body liquids, polymer is included without destroying the ability of dual phase compositions to form after product is left standing
US7273840Jul 14, 2005Sep 25, 2007Conopco, Inc.Preparing formulation which comprises:surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, amphoteric/zwitterionic surfactants, cationic surfactants and mixtures thereof; polydextrose or mixture of polydextrose and water; diluting biphasic liquid with water
US8006336Jul 3, 2003Aug 30, 2011The Procter & Gamble CompanyFabric article treating method and apparatus
WO1996014046A1 *Nov 7, 1995May 17, 1996Melvyn RosenbergMethod and compositions for hair treatment
WO1999047634A1 *Mar 9, 1999Sep 23, 1999Benoit MarcLiquid multiphase detergents
WO2000024852A2 *Oct 20, 1999May 4, 2000Benckiser NvLiquid cleaning agent or detergent composition
WO2001021751A1 *Sep 21, 1999Mar 29, 2001Henkel KgaaLiquid multi-phase cleaning agent
WO2001023514A1 *Sep 27, 2000Apr 5, 2001Colgate Palmolive CoMultilayered liquid composition
WO2003102294A1 *May 23, 2003Dec 11, 2003Procter & GambleMethod of sequentially dispensing a consumable layered liquid composition and product containing the same
Classifications
U.S. Classification510/417, 510/432, 516/19, 510/426, 510/135, 510/505, 516/59, 516/14, 510/476, 510/127, 510/461
International ClassificationC11D3/37, C11D17/00
Cooperative ClassificationC11D3/3765, C11D17/0017
European ClassificationC11D17/00B3, C11D3/37C6F
Legal Events
DateCodeEventDescription
Oct 1, 1984ASAssignment
Owner name: VISTA CHEMICAL COMPANY, 15990 NORTH BARKERS LANDIN
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST. SUBJECT TO TERMS OF AGREEMENT DATED JUNE 26,1984;ASSIGNOR:CONOCO INC.;REEL/FRAME:004349/0285
Effective date: 19840720