US2749276A

US2749276A - Dextran compound fatty acid ester lipstick

Info

Publication number: US2749276A
Application number: US373924A
Authority: US
Inventors: Leo J Novak; Joseph T Tyree
Original assignee: Commonwealth Engineering Company of Ohio
Current assignee: Commonwealth Engineering Company of Ohio
Priority date: 1953-08-12
Filing date: 1953-08-12
Publication date: 1956-06-05
Anticipated expiration: 1973-06-05

Description

United States Patent '0 I COMPOUND ACID ESTER;

- LIPSTICK Leo J. Noval'r and Joseph T. Tyree, Dayton, Ohio, as-

signors-to- The- Commonwealth Engineering Company of: Ohio, Dayton, Ohio', a corporation of' Ohio No Drawing; ApplicationAugustlZ, v 1953,

Serial No. 373,924-

7 Claims. (Cl. 167-85) This invention relates to cosmetiopreparations. More specifically, the invention relates tocosmetic sticksor. pencils-,,such as lipsticks, perfume. sticks, eyebrow pencils; etc., and. to. creams, shampoosand suchother cosmetic preparations; as-include a wax-like base.

Tor-be entirely. satisfactory lipsticks. and cosmetic sticks generally must be resistant to summer heat and winter cold whileremaining of essentially the same hardness and retaining essentially the same rubbing quality through seasonal temperature changes, and, more especially in the case. of lipsticks, they must be resistantto removaLby aqueous liquids, induce no allergic reactions and exhibit noin'itating effectson thesensitiveskin of the lips.

Conventionally, cosmetic sticks are made: of mixtures of, waxes,, fats, emollients,, and. oils. which form. the. base of-ithe preparations. For lipsticks, specific colo'ring matter israddedto the basic mixture;jfor perfumesticksessentia'l perfume oils; are: added; For other. specialuses, the appropriate ingredients are incorporated with the base mixture;

lttisywell. known that considerable research;has been performed. in an eflort. to: compound a non-irritating, liquid resistantbase, hinder or carrier for the" coloring matter of; lipsticks and having adequate staying;power in all. weather. It isalso. known that the. conventionallipstickscomposed of oil-soluble dyes distributed in anatural waiccontaining, castor oil as solvent for the coloringmatter are not satisfactory.

When. applied, such, lipsticksleave a layer. of a colored mixture of 'the. wax and oil and the color effect. from their applicationlasts only about as long as the fatty layer remains. Since such bases are readily washed off'or removed'by fluids'or 'f'oods' asiwell asmechanically byjmov ing the lips-'orjtouchingithem, thecolon'ngefiect soondis= appears: Such products also have the disadvantage ofbeing readilysmeared andbecoming unsightly. To overcome' thi's d'ifiicultyit has been proposed-to'incorporateiin' incorporated'in a water-repellent, firm'lyadherent, nonsmearing; liarmless base or carrier.

Theseand other objects of the invention are accom plishedbynew compositions comprising the cosmetic materials distributed in a base comprising or consisting'of an ester of a dextran i with 'afatty acid containing from 8 to 18 carbon atoms and havingi an average. D. S. (degreeof substitution or: the. average number of fatty. acid radicals per anhydroglucopyranosidic unit of the dextran) of .from less than 1.0 to 3.0.

'lihedextransarehigh molecular weight, branchedpolysaccharides. containing anhydroglucopyranosidic. units. linked. together by molecular structural repeating linkages some. of. which. are alpha-1,6. linkages, others are non-- alpha-1,6. linkages. and at least 50%. of, these linkages being,,app.arently,- alpha-1,6:linkages. The dex-trans vary with. respect. totheir molecular. structural: repeating;- alpha-l,6 to non-alpha.-l,6. linkages ratios, theextentof branching (the. distribution and=length of side groups. orchains), theirv molecular weight, and their sensitivity} to. moisture The pure. or substantiallypure. dextransv are. bland,.nontoxiq, non-irritating substances, which. are more or: less liydrophilie. Inaccordance with. the. present invention'it' is. found thatwhile-esters. of the dextran with the:fattyacids offrom 8'ito. 1 Scarbon-e atoms differ from. the. parent dextrans in being; more: or less water-resistant, they are. like the. dex-trans in. being bland, non-irritating harmlesssubstancesideally adapted to use as the base for-various. types of cosmetic preparations.

Thehig-her. fatty acid radicalsv may be introduced.- into. the dextran. molecule in any suitable. way. as by the. methods. disclosed in.thev pending application of, L. J.. Novalcandl. T. Tyree, .Serial No. 351,743, filed'April 28,.- 1953. Thus; thetselecteddextran may be reactedtwithan esterifiyingderivative-ofthehigher fatty acid, and'preferaablyahalidesuclr asthe chloride thereof, inthe presence. oi. an. acid: acceptororrbinding agent. such: as. an. organic base,.. as..f.on instance; a tertiary heterocyclic amine of the: type .ofquinoline, pyridine, N-methylmorpholine, etc.- and. in.-the presence ot'ta. substance. in which. the reaction-prod net. is at. least. partially solvated, that is. dissolved. or. swollen; as..it iseformedduringthe. reaction, which results. in. the.reaction-..mass' being maintained.- in a highly. swollenor" dissolvedstate: and thus. insures. substantially uniform, homogeneousreaction.between the. dextran and theesterh fyingagent. Substanceswhich'dissolve or swellthe-ester. as it is formed are, for example, xylene, toluene, dioxane,. etc. In-general, the. reaction-iscarried out at temperatures betvveen.10.0.-. C..and 155. C. for timeperiods varying; inversely with the. temperature. between a half hour and three hours, both. the. temperature and the reaction-time dependingpnithe boiling p oi-nt of the mixture of. acid ace ceptor. andsolvating agent used. Thus,. if. a mixture of. quinol-ineand xyleneais used, the reaction may beetfected. by heating the mass at from C. to- C. for from 0ne.-hal. hour. to-an.hour,. whereas. when amixture of pyridine. and toluenehav-ing, a relatively lowboiling point. is.-employed.-the reaetionais-preferably-run at temperatures.- of.-.1.00. Cite-1 15f C.,.for:from.oneto three hours. The: dextra-nrmay; betrecoveredfrom the crude reaction mix; in.,which it; is. at.- least partially dissolved, by. washing the; mixture. with. water. to remove the hydrochloride of the. organic. base, removing the: aqueouslayer, adding a sol vent; for the. ester to.-the. residual mass, and pouringthe: solution. thus obtained into. anon-solvent for. the ester,, such asa'loweraliphatic alcohol, .e.. g., methanol, ethanol,. isopropanol, etc., and filtering, the. ester, which may be further. purified. hy re-precipitation, and' dried.

Introduction: of. the high fatty acid radicals into the. d'extran molecule may be effected, also, by reacting the dextranwith' the selected. acid, in the presence of an int-- peilerwhich may be a monoha'logenated' monobasie or--' ganic acid anhydride and an esterification' catalyst such" as magnesium perchlorate at temperatures at which the reaction 1 mixture remains inthe liquid state and, depend iirgonthe: acid and3dextran used; generall'yin tin-range;- between--50? C,. andzlOO? C; and fona timevaryingzins' versely with the temperature between one-half hour and two hours. The ester is isolated from the crude reaction mass by cooling the mass, dissolving it in a solvent therefor, and precipitating it into a non-solvent for the ester in which the chloracetic acid (formed by addition of byproduct water to the anhydride impeller") remains in solution, and filtering to remove the ester. The latter may be dried in any suitable manner.

The higher fatty acids which may be used in the free acid condition or in the form of their chlorides are those containing from 8 to 18 carbon atoms and including caprylic, pelargonic, capric, undecyclic, lauric, tridecyclic, myristic, pentadecyclic, palmitic, margaric and stearic acids and the corresponding chlorides. The esters used in the cosmetic preparations of the invention may be mixed esters such as mixed dextran stearate-palmitate resulting from the reaction of a dextran with commercial stearic acid, known to be a mixture of stearic and palmitic acids.

These esters are water-resistant to a degree depending on the kind and number of acid radicals combined therein.

The D. S. may be from less than 1.0 to about 3.0, resulting from use of the estcrifying agent in amounts between less than 1.0, say 0.5, to 10.0 parts thereof per part of dextran.

The ester may be selected for the particular type of cosmetic of which it is to comprise the base, alone or in admixture with other adjuvants including inert fillers and conventional waxes and oils. Thus, those esters having a D. S. from about 2.5 to 3.0 and derived from fatty acids containing from 14 to 18 carbon atoms are water-repellent substances of wax-like consistency. These water-repellent esters are particularly suited to use as the base of compositions for use as cheek rouge or molding into lipsticks. They are remarkably adherent to the skin. For instance if a film of a dextran palmitate or of a dextran stearate containing an average of 2.9 palmitoyl or stearoyl radicals per anhydroglucopyranosidic unit forms on the hands during handling of dispersions or solutions of those esters, the film is not removed by vigorous scrubbing with soap and water. Used as the base or binder for cosmetic preparations, these water-repellent, wax-like dextran fatty acid esters, yield products which have excellent hardness at normal temperature extremes, rub off readily when applied to the skin, and exhibit good staying power on the skin. These esters may also be used as the base for socalled solid perfumes such as perfume sticks comprising essential perfume oils.

On the other hand, the dextran esters of lower D. S., i. e., those containing an average of from less than 1.0 up to about 2.0 of the fatty acid radicals per anhydroglucopyranosidic unit, are preferred for use as base component for other types of cosmetic products such as creams, shampoos, and similar products and in which the dextran ester functions as a base or binder and may also serve as a suspending agent.

The low-substituted esters are more resistant to water than the parent dextrans, their water-sensitivity being a function of the number of free hydroxyl groups present in the ester. Since this in controllable by adjustment of the conditions for producing the esters, including the relative proportions of dextran and esterifying agent, the ester may be selected for the particular use for which it is intended. The more water-sensitive esters are very suitable for use when a gradual and regulated release of volatile constituents of the composition is desired. An example is perfume blocks or sticks comprising essential perfume oils. These oils may be incorporated in a base comprising or consisting of a water-sensitive dextran higher acyl ester having some free hydroxyl groups so that when, in the presence of body moisture, the dextran swells and may gradually dissolve, the oils are released at a gradual, more or less regulated rate.

Whatever the precise form of the cosmetic, whether it is a lipstick, or a cream, paste, etc. the dextran fatty acid ester will usually comprise at least in most cases, at least 50% of the base. In many instances the base will 4 consist of the dextran ester. However, small amounts of wax such as ozokerite, beeswax, carnauba wax, and spermaceti may be mixed with the ester. The base may also contain, in addition to the dextran ester, small amounts of such substances as cocoa butter, butyl stearate and lanolin. Oil-soluble coloring materials may be dissolved in an oil, such as castor oil, and the solution may be mixed with the base comprising dextran palmitate or the like.

It is also within the scope of the invention to include in the cosmetic preparation a finely divided inert filler, these finely divided filler materials being held together by the dextran ester binder and serving, in the case of sticks or the like, as a structure or body material for imparting additional strength to the stick. The filler also functions as a diluent for the coloring material and assists in effectively dispersing the same through the base. For the structure or body material there may be used such materials as talc, kaolin, clay, bentonite and other similar particulate inerts.

The coloring material may be any of the oil-soluble certified DC colors or lake colors for lipsticks, cheek rouge, etc., and which are known in the art as drug and cosmetic colors. Such colors are preferably dissolved in castor oil and mixed in the dissolved condition with the base. Or compositions may include, as coloring material, a stain, for instance a water-soluble cosmetic dye which is insoluble in waxes or fats and suspended or dispersed in the base composing the dextran palmitate or the like. Compositions according to the invention, in-' cluding a stain, have the advantage that the stain, when combined with the dextran ester base, shows less tendency to induce chapping or cracking of sensitive skins than they commonly exhibit when applied to the lips or skin in conventional bases comprising natural waxes. The dyes to be used depend on the intensity or shade required. Suitable dyes include ponceau 3R, amaranth, purified eosine y, tartarzine, yellow ochre, etc., or any of the dyes used in indelible lipsticks. Various dyes may be used together in selected proportions to give desired shades.

The compositions may take the form of solid or semisolid cosmetic products, creams, pastes, cream shampoos, deodorants, etc. and may be modified as desired by the addition of oils to give them emollient or lubricating properties. Solid or semi-solid products, e. g., sticks, useful as long-lasting perfumes may be made by incorporating in the base suitable essential perfume oils.

The low-substituted esters having some free hydroxyl groups and more or less sensitivity to water, are, as has been mentioned above, useful as the base substance when release of the active cosmetic at regulated, controlled rate is desirable. Those esters tend to swell and may eventually dissolve in the presence of moisture. Their use is indicated in perfumes, deodorants and the like. In such applications, when the composition comprises a homogeneous mixture of concentrated perfume oils and a partial dextran higher fatty acid ester, as the ester is swollen in contact with the moisture of the skin, the perfume oils combined therewith are released at more or less regulated rate and thus it is possible to prolong the effect thereof. The same is true of homogeneous mixtures of the partial dextran esters and active deodorizing ingredients.

The dextran which is reacted with the higher fatty acid or its chloride to produce the esters to be used as bases or binders in the practice of this invention may be obtained in any suitable way. It may be produced microbiologically, for instance by inoculating a nutrient medium containing sucrose, particular nitrogenous compounds, and certain inorganic salts with an appropriate bacterium such as those of the Leuconostoc mesenteroides and L. dextranicum types and incubating the culture at the temperature most favorable to the growth of the particular bacterium.

In one method of obtaining a dextran by bacterial ac-i aus ere? tion, there is first" prepared" an aqueous nutrient. medium which may have the following composition."

This :medium-isadjustedxto apI-It.ofi'betweenabout 6.5; and about 7.5, preferably 7.2, and then sterilized: The material: is. cooledv to; room: temperature and. inoculated with at culture: of the. dextran-producing bacteria;, for; example,. Leucanostac: mesen-tenoid'es. B:-512; (Northern Regional Research Laboratory. classification). and. incubatedzatr toz (optimumy25f C.) until a maximum yields. of dextrarrhas: been: attained;. normally. a period: of between 12: and: 48 hours: will be.- satisfactoryv fon'this procedure: The fermentedproduct contains: approximately -85 of waterand isva-thick turbid liquid;

Upon? completion of thefermentatiom which process rendersthe;materiahsomewhat acid, that is, toa pH of 3.5-5.5.- (average. 4.2), calcium chloride is added to: the fermenttto bring-,thespH thereof to. about.7.0-to.8.0.. This aids in the precipitationof phosphates- Thereafter, ace.- tone or alcohol, which may be a. water-misciblealiphatic, suchasmethyl, ethyl. or isopropyl, is.added insuflicient quantity-to precipitate the. dextran and this bringsv down, with the dextran, occluded and adsorbed bacteria,,and. nitrogenous and inorganicelements. Tov occasion. complete. precipitation of. the. dcxtranv it. may be desirable. to allow. themix. to standfor a.relatively long period,' such as about 6 hours. The precipitated dextran may be dried in any suitable manner, for example by drum drying to obtaina flaky product. Thereafter, it may, be reduced to powdered condition, if desired.

A purer dextran may be obtainedhy adding an aliphatic alcohol to the fermented culture. at a pH between about 2.5 and. 4.5. The precipitate thus-obtained-may be furtherpurified by again precipitatingit with the alcohol. Several. precipitations may be performed.

Suclia native"high molecular weight dextran. (the molecular weight is calculated to be in the millions) may be used in practicingthis' invention. In the alternative,. and for. some purposes, preferably, a-dextramhaving, initially, a high molecular weight is hydrolyzed to a product of lower molecular weight for esterification with the higher fatty acid or esterifying derivative thereof. For instance, the native dextran obtained as described above may be hydrolyzed to a product having a lower molecular weight or lower average molecular weight, for instance and average molecular Weight in the range between 20,000

and 200,000 and this hydrolyzed product, if desired or necessary may be fractionated by available methods to obtain a fraction of pre-selected uniform or more nearly uniform molecular weight in the stated range, such as a fraction having a molecular weight or average molecular weight in the range 70,000 to 85,000. The fraction of pre-selected molecular weight may be, if desired, treated by known methods for the removal of pyrogens and coloring materials, prior to the esterification. The dextran used in preparing the higher fatty acid esters may be a so-called clinical dextran. In general, the dextran may have a molecular Weight between 5,000 and x10 as determined by light scattering measurements.

The dextran to be esterified may be obtained by inoculating the culture medium with microorganisms bearing the following NRRL classifications: Leuconostoc mesenteroides B-119, B-l146, B-1190; or it may be a water-insoluble or substantially water-insoluble dextran obtained by inoculating the nutrient medium with the microorganisms Leuconostoc mesenteroides B-742, B-1191, B-l196, 13-1208, B-1216, 8-1120, 3-1144 or B-523, Streptobacterium dextranicum 13-1254, or Betabacterium vermiforme B-1139.

'color coating to the lips.

duced under any particular set of conditions or using:any'

particularmicroorganism. The dextran maybe produced enzymatically, in the substantial absence of bacteria, by cultivating an appropriate microorganism, such as Leuconoszoc mesenteroidsB -5-l2 to obtain a dextran-pro ducingenzyme, separating the enzyme from the medium in'which it is produced; and introducing the enzyme into a medium in which dextran is produced by the actionjof the enzyme. Also, the dextran' may be. obtained by bacterial conversion of 1,4 linkages of dextrin to 1,6 linkages of dextran, orin any other suitable manner; The following formulations, in which the parts are given in percentages by weight; are'illustrativeof specific embodiments of the invention. The colorsused in Formulae I-V' are certified DC colors or lake colors for lipsticks' and known as-di'ug and cosmetic colors:

Colors- 26.0 (H). Dextran'palmitate.asinFormulaI 69.5 Castor. O 5.5 Colors 25.0 (HI) Dextranpalmitate. asdn-Formula I 52.5 Lanolin: 12.0 Castor oil.- 5.5. Colors 30.0

(1V), Dextran. stearatefrom clinical dextran; average D..S. 2.9 stearoylgroups 6510- Ozokerite 2.0 Carnauba w 4.0 Spermaceti. 2.0 Cocoa butter 1.5. Lanolin 2.5. Colors 23.0 (V Dextran palinitateas. in Formula I.. 60.0 Bentonite 20L0 Colors, 20.0v (VI) Dextran palmi'tate as inFormula I 40.0 Bentonite 27.5 Poinceau 3 R 9.5 Certifiedf amaranth 5.5 Yellow ochre 1 0.5 Petrol'atum 7.0

The ingredients of these respective formulae are compounded by heating the dextran ester to convert it to a fluid or plastic state, and then distributing the coloring matter or dye through the fluid or plastic mass. If inerts such as talc, bentonite, etc. are to be included these may be ball milled with the coloring matter or dye before being mixed with the fluid dextran ester, at a temperature at which the ester remains readily workable. A heated, water-jacketed mixer or a heat-jacketed paint mill can be used to insure intimate commingling of the ingredients. The mass, while plastic, is given the desired shape. These compositions may take the form of cakes, blocks, balls, pencils, sticks, creams or liquids of emulsion or suspension type. The plastic moldable compositions may be compressed or extruded through dies of appropriate shape to obtain continuous rods of corresponding crosssection and the rods may be cut into lengths to obtain discs or cakes, or the lengths may be beveled and mounted in lipstick holders.

The final product may have a consistency such that it can be taken up by the fingers or a cosmeticians brush and spread on the skin or lips, or sticks may be applied directly to the skin. In the use of a lipstick in accordance with the invention, the stick is manipulated to apply a Since the dextran fatty acid esters employed as base or binder for the color and inerts, if the latter are present, are water-repellent, the ester is not readily smeared or dissolved by liquids, hot or cold, and thus the coloring matter intimately associated with the dextran ester film, tends to remain on the lips "7 for a long time, even when the coloring matter is not a stain.

The proportion of dextran higher fatty acid ester in the preparation may vary. It will usually comprise at least 50% by weight of the total composition, but this is not essential and lesser amounts of the ester may be used, especially when the product is a cream containing a high percentage of oils and intended for use as a skin lubricant.

Instead of esters of the higher fatty acids with dextrans, we may use those esters of dextran conversion products which are physiologically harmless such as lower acyl esters of dextran having from 1 to 5 carbon atoms in the acyl groups, alkyl dextrans such as those containing 1-5 carbon atoms in the alkyl radical, carboxyalkyl and hydroxyalkyl dextrans in which the alkyl portion of the carboxyalkyl or hydroxyalkyl group has from 1 to 5 carbons and particularly carboxymethyl dextrans and hydroxyethyl dextrans. The esters of the conversion products may contain an average of from less than 1.0 to 2.9, preferably to 2.5 of the higher fatty acid radicals and from less than 1.0 to 29, preferably to 2.5 of the lower acyl, alkyl, carboxyalkyl, hydroxyalkyl or other groups, per anhydroglucopyranosidic unit. Preferably, the esterified conversion products contain from less than 1.0 to 1.5 of the radicals other than the higher fatty acid radicals and from about 1.5 to 2.5 of the higher fatty acid radicals, the total number of substituent groups per anhydroglucopyranosidic unit of the dextran being not greater than 3.0. The esters of the conversion products may have a controlled moisture pick-up and retention capacity rendering them suitable for combination with agents to be released gradually when the composition is contacted by moisture. Esters of carboxymethyl and hydroxyethyl dextrans are typical esters of that type.

It will be apparent that by selection of the dextran ester (both the dextran and the esterifying acid or chloride, as well as the D. S. being involved and variable), used in the cosmetic preparations, and by incorporating therein other agents including natural waxes and oils, fats, etc., it is possible to vary the hardness of the preparation, its sensitivity to moisture and other physical properties, so that a wide range of cosmetic products are possible.

These selections, variations and modifications may be made without departing from the spirit and scope of the invention and therefore it is to be understood that the invention is not to be limited except as defined by the appended claims.

We claim:

1. A lipstick comprising coloring matter and a base comprising an ester of a dextran with a saturated fatty acid of from 14 to 18 carbon atoms, said ester containing an average of from 2.5 to 3.0 of the fatty acid radicals per anhydroglucopyranosidic unit.

2. A lipstick comprising coloring matter and a base comprising dextran palmitate containing an average of 2.5 to about 3.0 palmitoyl groups per anhydroglucopyranosidic unit.

3. A lipstick comprising coloring matter and a base comprising a palmitate of carboxymethyl dextran containing an average of 2.5 to about 3.0 palmitoyl radicals per anhydroglucopyranosidie unit.

4. A lipstick comprising coloring matter and a base comprising an ester of a dextran with a saturated fatty acid of from 8 to 18 carbon atoms, said ester containing an average of less than 1.0 up to 3.0 of the fatty acid radicals per anhydroglucopyranosidic unit.

5. A lipstick comprising coloring matter and a base comprising an ester of a dextran with a saturated fatty acid of from 14 to 18 carbon atoms, said ester containing an average of less than 1.0 up to 3.0 of the fatty acid radicals per anhydroglucopyranosidic unit.

6. A lipstick comprising coloring matter and a base comprising a dextran palmitate containing an average of less than 1.0 up to 3.0 palmitoyl radicals per anhydroglucopyranosidic unit.

7. A lipstick comprising coloring matter and a base comprising a dextran stearate containing an average of less than 1.0 up to 3.0 stearoyl radicals per anhydroglucopyranosidic unit.

References Cited in the file of this patent UNITED STATES PATENTS 1,958,700 Harris May 15, 1934 2,052,026 Ham's Aug. 25, 1936 2,229,941 Stahly Jan. 28, 1941 2,587,623 Jeanes Mar. 4, 1952 2,609,368 Gaver Sept. 2, 1952 FOREIGN PATENTS 117,452 Sweden Oct. 22, 1946