United States Patent (19) 11) 3,919,430 Siegel (45) Nov

United States Patent (19) 11) 3,919,430 Siegel (45) Nov. 11, 1975

54 WATER ABSORPTION BASE sion, (1965), pp. 448-499, 668, 786, 787 & 789. 75) inventor: Frederick P. Siegel, Lincolnwood, Primary Examiner-Donald B. Moyer Ill. Attorney, Agent, or Firin-Francis W. Young; Philip 73 Assignee: Akzona Incorporated, Asheville, M. Pippenger N.C. 22 Filed: Jan. 28, 1974 (57) ABSTRACT (2 Appl. No.: 437,418 Compositions useful in cosmetic and pharmaceutical formulations comprising at least about 75% petrola tum and a combination of minor amounts each of four 52 U.S. C...... 424/365; 424/170; 424/308; emulsifiers in certain proportions: 1) 1.5 - 10% by 424/358; 252/.351; 252/DIG. 5; 424/238 weight of either sorbitan monooleate or ethoxylated 5 Int. Cl...... A61 K 7/48; A61 K 47/OO (3 moles ethylene oxide) oleic acid; 2) 0.6 - 3% by 58 Field of Search...... 424/365, 358, 170 weight of either glycerol monooleate or glycerol monolaurate; 3) 0.45 - 1.5% cetyl alcohol; and, 4) (56) References Cited 0.45 - 1.5% by weight stearyl alcohol. The composi UNITED STATES PATENTS tions are superior to lanolin or lanolin derivative per 2. l l 449() 4f 1938 Harris...... 424/365 se or water absorption bases containing either in that 2,372.807 4, 1945 Brown...... 424/365 they are stable water-in-oil emulsions having Water OTHER PUBLICATIONS Numbers in excess of 400, are not allergenic, and are DeNavarre, "The Chemistry & Manufacture of Cos not as subject to oxidative attack during shelf life that metics," 2nd Ed. Vol. II, Cosmetic Materials, -ppf 84, can cause discoloration and odor formation. 85, 89, 97, 98, 99 & 100 (1962). 3 Claims, No Drawings The Pharmacopeia of the U.S.A., Seventeenth Revi 3,919,430 1 2 least 400 which remains stable for a minimum of 48 WATER ABSORPTION BASE hours at 100F. Most particularly, it has been found that petrolatum BACKGROUND OF THE INVENTION can be emulsified with certain combinations of four of This invention relates to water absorption bases the following materials to obtain compositions having which are used in the preparation of cosmetic and the above mentioned properties: (1) sorbitan monoole pharmaceutical compositions. ate or ethoxylated (3 moles ethylene oxide) cleic acid: Cosmetic and pharmaceutical formulations utilizing (2) glycerol monooleate or glycerol monolaurate; (3) some of the constituents of the present invention are cetyl alcohol; and (4) stearyl alcohol in specific pro well known and can be represented by some of the fol () portions. In particular, the water absorption base com lowing U.S. Pats. Reissue Patent Nos. Re 27,253 and position comprises at least 75% by weight of petrola Re 20,36; Pat. Nos. 1,958,700; 2,322,820: 2,372,807; tum and minor amounts of each of an emulsifier from 2,583,576; 2.854,378; 2,942,008; 2.987,446 and each of the four groups just mentioned and may con 3,536,86. tain small amounts of a bacterial control agent, such as The best known and almost universally used water propyl p-hydroxybenzoate (propyl paraben). While absorption bases for cosmetic and pharmaceutical for some petrolatums give better results than other petrola mulations contained significant amounts of lanolin and tums, and are preferred, all petrolatums are found to be lanolin derivatives. Lanolin, however, has poor color useful in the invention. Water absorption bases within and color stability, develops odors, imparts stickiness the following ranges are found to exhibit Water Num to formulations, is susceptible to oxidative attack and is 2) bers of at least 400 and are stable water-in-oil emul reported to be allergenic. Furthermore, lanolin has sions, i.e. do not separate, when heated at 1 OF for a shortcomings in terms of its ability to absorb water (the minimum of 48 hours: petrolatum 85 - 95%: sorbitan primary qualification of a water absorption base). The monooleate 1.5 - 10%; glycerol monooleate ().6 - 3% , parameter used to measure the performance of a water cetyl alcohol ().45 - 1.5%; and stearyl alcohol ().45 – absorption base is its “Water Number." Water Number 1.5%. Oleic acid ethoxylated with about 3 moles ethyl was originally defined by Casparis and Meyer (Pharn. ene oxide can be used in place of sorbitan monooleate. Acta. Hell'..., Vol. 10, p. 163, 1935) as the maximum and glycerol monolaurate can be substituted for glyc number of grams of water that will form a stable water erol monooleate in the above ranges. in-oil emulsion with 100 grams of the water absorption Compositions within the following ranges have Water base. For example, a Water Number of 400 means that Numbers in excess of 800 and are stable at this Water 100 parts of the base will combine with 400 parts of wa Number for at least 48 hours at l l OF and, hence, are ter. This test has been expanded to give a measure of preferred: about 90% petrolatum: about 0.65% each of extended packaging or shelflift by examining the water cetyl alcohol and stearyl alcohol; 5 - 7% sorbitan absorption base at the designated Water Number after monooleate and 1 - 2% glycerol monooleate. 48 hours, both at 77°F and at 100°F. If the particular 35 A preservative such as methyl p-hydroxybenzoate water emulsion (Water Number) does not separate (methyl paraben) or propyl p-hydroxybenzoate (propyl within 48 hours at both temperatures, it is judged to be paraben) may be incorporated in the above formula stable under normal conditions. This criterion is per tion in an amount sufficient to control bacteriological haps the most important test of whether a water ab growth in the water absorption base, usually around 0.1 sorption base having a certain Water Number is suit 4) - 0.2%. able for use in cosmetics and pharmaceutical formula tions because of the requirement of long shelf life with DETALED DESCRIPTION OF THE INVENTION out separation of the product. It has been observed that petrolatums of various fiber While lanolin has a Water Number of 475 when lengths (short, medium, long) made from Pennsylvania freshly prepared, on aging, even while refrigerated, this 45 crude oils give the highest Water Numbers and are the value drops to <190. It has been suggested that the lat most stable as determined by the elevated temperature ter value should be considered a more nearly true value storage tests described hereinafter and thus are pre (Chemistry and Manufacture of Cosmetics by M. G. ferred. However, a short fiber petrolatum from a mid deNavarre, D. Van Nostrand, 1941, page 66). continent crude oil (Amojel Snow White) gave satis Numerous attempts have been made over the years factory results but not as good as the Pennsylvania to overcome the above mentioned drawbacks, but none Crudes. Petrolatums derived from Pennsylvania crude have been completely successful. Such attempts have oils that have been used with good effect include: mostly centered on modifying lanolin chemically to re Protopet l-S regular (short fiber petrolatum marketed duce one or more of the disadvantages enumerated by Witco); Protopet l-S (long fiber); Protopet 2-L above; none of the derivatives produced, however, 55 (long fiber); Amojel long fiber (Amoco) Penreco have eliminated all the disadvantages and their cost is short, medium and long fibers (Penreco). The only fac considerably higher than lanolin. The compositions of tor that appears critical is that a large proportion of the present invention overcome the disadvantages petrolatum be used in relation to the total amount of mentioned, exhibits a Water Number of 400 or greater emulsifiers used in the base formulation. For the pur which remain constant with age, and in addition, are 6) poses of this invention at least 75% petrolatum is used lower in cost than lanolin derivatives. and preferably, 85 - 95%. Four emulsifiers are selected from the following: sor SUMMARY OF THE INVENTION bitan monooleate; glycerol monooleate; glycerol The invention is directed to compositions which ex monolaurate, oleic acid ethoxylated with 3 moles of hibit to a very high degree the ability to absorb water 65 ethylene oxides; cetyl alcohol and stearyl alcohol. A and which thus find utility as a water absorption base in first emulsifier either sorbitan monooleate or oleic acid cosmetic and pharmaceutical formulations. The com ethoxylated with 3 moles of ethylene oxide may be in positions of the invention have a Water Number of at corporated in amounts ranging from 1.5 to 10% by 3,919,430 3 4 weight of the water absorption base although amounts from 5 - 7% by weight are preferred. A second emulsi EXAMPLES fier selected from the group consisting of glycerol The invention will be illustrated with a number of ex monooleate and glycerol monolaurate is added in amples setting forth various compositions which are amounts from about 0.6% to about 3% by weight. 5 stable at Water Numbers of 400 or more as shown by Two specific emulsifiers, which additionally function the heat (aging) stability test described above. Each of as emollients, cetyl alcohol and stearyl alcohol, are the compositions was formulated in the proportions, by added in small amounts in the range of 0.45 - 0.9% by weight percentage, stated below in the tables by thor weight each and preferably, in equal quantities. oughly mixing the ingredients in any order desired, in a While the materials utilized in my water absorption () blender. The Water Number is then determined by base are well known and commonly used in cosmetic adding hot (140°F) water in 100 gm. units to 100gm. and pharmaceutical preparations, I have found. unex of the water absorption base with further blending then pectedly, a composition, that, in the proportions dis cooling the mixture to 100°F to determine the maxi closed herein, has water absorption properties com mum units of water which will not separate on standing bined with other properties and a degree of heat stabil S at room temperature for 48 hours. One-ounce samples ity not found in other materials heretofor used for this of the water absorption base at each level of Water purpose. Number up to the maximum at which the base remains The most commonly used water absorption base, lan completely emulsifed after 48 hours are placed in vials olin, has a Water Number of over 400, when freshly and heated in an oven set at 110F. The samples are prepared, which rapidly drops to below 200. The Water again observed after 48 hours. If the emulsion has sepa Number is a direct measure of how much water can be rated during that time, the base is rejected for lack of absorbed by a base material and is an essential criteria aging stability at that Water Number. In the tables be of the suitability of the material for cosmetic and phar low, the figure in the best stability now represents the maceutical preparations. Further, to be useful, the level highest Water Number (in 100 unit steps) for which the of the Water Number must remain high and not dimin h 5 base will not separate under the specified temperature ish with age. A simple test to determine the stability of conditions. The compositions of the invention are illus a water absorption base comprises heating a sample trated in the following examples, 1 - 23 in Table I. Su combined with a given amount of water (i.e., at a spe perior compositions are shown by Examples Nos. 10, cific Water Number) in an oven at OF for 48 hours. 1 and 17 and represent the compositions referred to To be considered stable at the designated Water Num- 30 above. TABLE I Material Example No. l 3. - s 7 8 9 Protope t i-S Reg. 927) 97) 9.7} 97 () 9.7) 94.7() 95.}() 93.7( 9() ()() 92() 87.7() 89.7) Protopet i-S Long Fiher ------m - Protopet 2-L. i.ong Fiber ------Amoje Snow White - - - w------Amojel Long Fiher ------

Pentec Short Fiher ------

Penreco Nielium Filher ------

Penreco Long Fiher ------Stearyl Alcohol (),65 ().5 ().65 ().65 ().5 ().5 ().5 ().65 (8) ().65 65 ().5 Cetyl Alcohol (). h5 (.65 ().6S (),65 ().f5 ().65 (.45 ().65 (1.89 ().65 (.65 (). S Sorlitan Monocleate 5()() - S()() S()() 5.) 3()() 3.42 3.()() 6.85 6.()() 7() 8) Ethoxylated Oleic Acid (3 moles ethylene oxide) - 5}} ------Glycerol Monchlete }() ()() -- () 3.) l (2.68 (){ 37 5() () () Glycerol Monolaurate - - 1() - - - - - v- - - Water N.--48 hrs. at 77F 6th() -4)() -()() S() 8)} -()} 6() 8(){} 9}() 9) 8) ()() Heat Stability (Water No.- 48 hrs. it (F) {y}} 4)() () U} f() ()() 4}() ...}) f()() 8}) 8}) ().) 3. I-4 15 f 7 18 19 () 3.

Protopet 1-S Reg. 9.)} 85.()() ------9 ()() ------96() Protopet 1-S Long Fiber ------m Protopet 2-L Long Fiber - --- 9,7() -- n 9.7() -- -- Amojel Snow White - - - 9.() - - - - - m Amoje Long Fiher - - - -- 92.7) ------Penreco. Short Fiher ------9.7) ------Penrecy Melium Fiber ------97) - Penreco long Fiber ------97 () --- Stearyl Alcohol 1.() 1.33 U.65 (),65 (),65 5 ().65 (),65 (.65 ().65 65 Cetyl Alcohol }() 33 ().65 (),65. ().65 5 ().65 ().65 (.65 O.65 6S Sorhitan Monocleiate 5}() ().28 5()() 5.}} S}() S()) 5(){ 5.()() 5(() 5()() 5}() Ethoxylated Oleic Acid (3 moles ethylene oxide) ------m Glycerol Monooleate ()() 2.06 }() ()() (){} ()( 1 (U (){ ()() () () (J() Propylparaben ------(). Water No.--48 hrs, it 77°F f)) ()() (JC () 8) (){ 6) 6(){} 4)() 4() -()) Heat Stability (Water No.- 48 hrs at 1 °F) ()) 6()() -- )() 4()() 8()} ()) }() f() () (}() -(j)

In Table II below, each of the Examples 24 - 32 are directed to a composition in which one or more of the ber, the emulsion must not separate during the 48 hour essential ingredients have been omitted, substituted by period. another material or reduced below the level of the op

3,919,430 S 6 erative range and it will be noted that the Water Num ber is below 400 or the composition is not stable as in TABLE IV-continued dicated by the aging test. From Example No. 29, it will Material Example No. be observed that petrolatum alone has a Water Number 33 3. 35 36 less than b:O and is therefore not useful as a water ab- 5 CarnationArmilk CompanyMineral Oil 1. () 5. ( 7.)..) f Sorption base. TABLE I Base of Example 23 3. 3. 3. 3. Materia Example No. 4 s 2 27 28 9. 3. 3. 3. Protopet 1-S Reg. 92.7) 97) 92.7 94.()() 98.7) ()(). Protopet 2-L Long Fiber 99. 6.. 977) Steary Alcohol 1.65 }.65 (.65 (.65 area n- (.5 65 Cetyl Alcohol 5 (.65 - 65 - - ().h5 (.65 Sorbitan Monolete Y- s 5)) w - S() Sorbitan Monoaurate - 5. m - GlycerolDiethylene Montroleate Glycol () () - () () () PolyethyleneMonosteurate Glycol 51() a- s - Monoclete - 5. Water No. - 48 hrs. it 77°F () g (); () 2}() c 2} () Heat Stability (Water No. - 48 hits, at (°F) (} <() (a)) < () () 2) <)

Steary Alcohol S() - ( Methyl Paraben . (). t (). Propyl Parahen (). ().5 3. t}, Glycerin S.) 3) - S} 5 Polavax (Croul: ) ...) - - In Table III below the Water Numbers of lanolin and Cetyl Alcohol () af numberb off modifieddified lilanolins li now generallytly availableavailabl Stearici S-55 Acic (Armak (Nec-Fat Company ) - - on the market have been determined in the same man- Triethnolanine - - 5 let described about to provide ay direct comparisony ri to CetyKessco Palmitate X-65 Arnik the compositions of the invention. Although it will be 30 Stiply noted that some of the modified lanolins exhibit ele- Deionized Witter 68.3 8.85 733 79S vated temperature stability, Water Numbers greater than 400, they are more costly than the compositions P described herein. Furthermore, while the modified lan- What is claimed is: -- tirelyolins areeliminate less allergenic the reported than allergeniclanolin, they reactions. do not Theen- metic1. A formulations, water absorption Sonsisting base for essentially cream and of lotion cos lanolin odor that is often objectionable in pharmaceuti- a from 1.5 to 10% by weight of a member of the cal and cosmetic preparations is still evident in many group consisting of sorbitan monooleate and oleic modified lanolin products, but is totally absent from the id ethoxylated with about 3 moles of ethylene ox composition of the invention. Cle, w p 0 b. from 0.6 to 3.0% by weight of a member of the TABLE II group consisting of glyceroled monooleate and glyc Product Maximum Water erol monolaurate; Little c. from 0.45 to 1.5% by weight of stearyl alcohol; at CF d. from 0.45 to 1.5% by weight of cetyl alcohol; and Example () >8) 5 e. balance at least 75% by weight of a fiber petrola Aisi (croda) tum; said water absorption base having a capability Hist E. s.S. 8 of forming a stable water-in-oil emulsion in a ratio modified linolinanchlin (Americhol(Forlin- CAB-CP)) c)<()() of 100 parts of base to at least 400 parts of water,w modified:nolin (Americhel H-9 - CPE) <6)) by weight, said emulsion showing no separation modified anolin (Americhol 4)() - CPI) a)) SO when held both at 77 of and 1 10°F for al minimum midified anolin (Lanalan-lanatex) 3)() modified lunulin (Llanatex L-5 - Llanatex K) period of 48 hours. E. R {REk BRITA) s: 2. The water absorption base of claim 1 wherein the EEE nate K2) amount of petrolatum is from 85 to 90% by weight of the composition. S5 3. A water absorption base for cream for lotion cos Using the composition of Example 23, a hand creme metic formulations, consisting essentially of (Example 33), a creme lotion (Example 34), a night a. 6% by weight of sorbitan monooleate; creme (Example 35), and a hand and body lotion (Ex- b. 1.5% by weight of glycerol monooleate; ample 36), respectively were prepared by blending the c. 0.6% by weight of cetyl alcohol; ingredients indicated in Table IV in the proportions by d. 0.6% by weight of stearyl alcohol; and weight indicated. e. balance about 90% by weight of a fiber petrolatum; TABLE IV said water absorption base having a capability of forming a stable water-in-oil emulsion in a ratio Materia Example No. of 100 parts of base to 800 parts of water, by 33 3. 35 36 65 weight, said emulsion showing no separation Promulgen D (Robinson- when held both at 77F and l l OF for a minimum Wagner } 3.5 m Glycero Monos tearate period of 48 hours. Kessco GMS SE k sk k k