Cosmetic compositions
Kalopissis et a1.  
 COSMETIC COMPOSITIONS Inventors: Gregoire Kalopissis, 64, Rue  
 Vauvenargues, Paris; Guy Vanlerberghe, Rue des Ecoles, Montjay-La-Tour, Villevaude par Clay-Souilly 77, both of France Filed: Mar. 16, 1973 Appl. No.: 341,853  
 Related US. Application Data Division of Ser. No. 186,524, Oct. 4, 1971, which is a continuation-in-part of Ser. No. 846,929, Aug. 1,  
 1969, Pat. No. 3,666,671, which is a continuation-in-part of Ser. No. 780,300, Nov. 29, 1968, Pat. No. 3,578,719, which is a continuation-in-part of Ser. No. 544,095, April 21, 1966, abandoned.  
 Foreign Application Priority Data Apr. 23, 1965 Luxembourg 48458 Nov. 22, 1965 Luxembourg 49902 Apr. 6, 1966 Luxembourg 50850 Dec. 1, 1967 France 67.13071 U.S. CI 106/266; 106/308 F; 106/308 Q; 106/285&#39;, 424/63; 424/64 Int. Cl C08h 17/04 Field of Search 106/266, 308 F, 308 0, 106/285 References Cited UNITED STATES PATENTS 1/1922 Rodebush 260/636 Apr. 15, 1975 2,089,569 8/1937 Orthner et al 260/615 B UX 2,096,036 10/1937 Hansley 260/638 2,131,142 9/1938 Orthner et al 260/613 13 UX 2,260,753 10/1941 Marple et al. 260/612 2,986,570 5/1961 Monroe et al..... 260/615 B X 3,190,926 6/1965 Edwards 260/613 B FOREIGN PATENTS OR APPLICATIONS 1,022,878 3/1966 United Kingdom 260/613 B OTHER PUBLICATIONS Groggins: Unit Processes in Organic Synthesis (1952), pp. 616-620.  
 Primary Examiner-Allan Lieberman Assistant Examiner-E. Suzanne Parr Attorney, Agent, or Firm-Cushman, Darby &amp; Cushman [57] ABSTRACT 8 Claims, No Drawings COSMETIC COMPOSITIONS This is a division of application Ser. No. 186.524 filed Oct. 4. 1971. which is a continuation-in-part of our application Ser. No. 846.929. filed Aug. 1. I969 now US. Pat. No. 3.666.671. which is a continuation-in-part of our application Scr. No. 780.300. filed Nov. 29. 1968 now U.S. Pat. No. 3.578.719. which in turn is a continuation-in-part of our application Ser. No. 544.095. filed Apr. 21. 1966. now abandoned.  
  There are quite a number of known non-ionic surface active agents the compositions and properties of which are quite varied.  
  Nevertheless the known products made from the conventional raw materials do not have simultaneously all the characteristics which are desired for certain cosmetic purposes.  
  For instance. the best detergents and foaming agents among those monoethers of polyethylene glycol which comprise a lipophile chain having at least eight carbon atoms are generally the most irritating to the mucous membranes. Moreover. when mixed with cationic surface active agents the degree of irritation increases synergistically.  
  On the other hand. the derivatives of the polyols and the sugars. especially their esters. have been considered most useful because they are not irritating. They have. however. certain disadvantages which result from their composition. In particular. the non-selective character of the reactions used in their preparation results in the formation of a mixture of constituents having one or more lipophile chains per molecule. When these products are to be used for applications for which solubility in water is a prerequisite. they must therefore be painstakingly purified.  
  The hydrosolubility of these compounds may be improved by adding hydrophile substituents on the carbon chain or by adding ethylene oxide to the free hydroxyl groups. However. such compounds are not usually very good foaming agents. even when they comprise a medium length hydrocarbon chain. They are consequently used mainly as emulsifiers.  
  The object of the invention is to produce. from conventional commercial raw materials. new non-ionic surface-active agents which are stable. very hydrophile. non-irritating. non-toxic and which may be used as emulsifiers. foaming agents. detergents. or wetting agents.  
  Another object of the present invention is to provide a method of preparing preferred new non-ionic surface-active compounds having the formula:  
 in which R represents a lipophile group that is a linear or branched alkyl or alkenyl. which has eight to 22 carbon atoms or an alkyl aryl group which has eight to 22 carbon atoms and has a linear or branched alkyl chain which has l] 8 carbon atoms. and in which n has a statistical average value greater than I and less than l0 or equal to 10. essentially characterized by the fact that :1 molecules of the glycerol epihalohydrin repeating group are linearly polyadded to a hydroxylated compound having the formula ROH. in which R has the significance indicated above, and that the resulting product is hydroxylated with a carboxylic acid salt.  
  A further object of the present invention is to provide the new article of manufacture which consists of nonionic&#39;surface-active agents according to formula I made by the foregoing process.  
  Another object of the present invention is to provide as new articles of manufacture. the intermediate products obtained while carrying out the above-mentioned process. after the polyaddition has taken place but before the hydroxylation. said intermediates having the formula:  
 in which R has the significance indicated above. it has a statistical average value greater than 2 and less than 10 or equalto l0 and X represents a halogen.  
  Broadly. the present application covers the class of non-ionic surface-active agents described above and those which may be prepared from natural or synthetic aliphatic or alicyclic alcohols. The term natural alcohols&#34; is intended to include those derived. for example. from lanolin, natural waxes (e.g. beeswax). hydroabi etic alcohols derived from resinous acids. and alcohols obtained by reducing cyclic fatty acids.  
  It is known that lanolin alcohols. for example. comprise up to 30 carbon atoms. and that they consist of a mixture of straight or branched chain iso and anteiso derivatives. which are members of the aliphatic series. and of alicyclic alcohols (sterols and triterpenic alcohols). The alcohols are found in lanolin. essentially in the form of esters of fatty acids. Hydrogenation yields a mixture comprising both the alcohols of the unsaponifiable material and those derived from the fatty acids of lanolin.  
  The preparation of lanoline alcohols by hydrogenation was described by Stickdorn. E. Konig and Birk in the Tcnside review. 3. No. 2 (1966) p. 45.  
  Elrolan sold by VEB Deutsches Hydrierwerk and Hydrolan R sold by Occo International. Division of Millmaster Onyx Corporation. Jersey City. New Jersey U.S.A. are examples of alcohols of lanoline prepared by hydrogenation.  
  High molecular weight alcohols may be obtained in like manner from natural waxes. (beeswax. for example) and from resinous acids.  
  It is another object of the present application to provide new non-ionic surface-active agents having the formula:  
 in which n has a statistical average value greater than 1 and less than 10 or equal to 10 and R represents a hydrocarbon radical derived from aliphatic or alicyclic alcohols. of either natural or synthetic origin. which may comprise from eight to 30 carbon atoms and a process of making these compounds. This process is essentially characterized by the fact that n molecules of glycerol epihalohydrin are polycondensed on an alcohol having the formula R OH. in which R, has the significance hereinbefore indicated, the resulting product is then hydroxylated by means of carboxylic acid salt. and the ester thus formed is hydrolized or alcoholizcd.  
 It is a further object of the present invention to provide. as new compositions of matter. the non-ionic surface-active agents responding to formula (1) and (111) produced by the above process.  
  it is a still further object of the present invention to provide, as new compositions of matter. the intermediates which are obtained in the course of the above process. after completion of the polycondensation step and before hydroxylation, which intermediates respond to the general formula:  
 in which R has the significance hereinbefore indicated. it has a statistical average value greater than 2 and less than or equal to 10. and X represents a halogen.  
  It is clear that in the course of the polycondensation which constitutes the first step of the process according to the invention. a mixture of compounds responding to general formula (IV) is formed, but in these compounds the number of glycerol epihalohydrin molecules attached may be greater or less than the statistical average value of the number of molecules of glycerol epihalohydrin supplied per molecule of alcohol. Consequently, the process according to the invention makes it possible to obtain a mixture of compounds having hydrophilic chains the size of which is dependent on the value of the number n in formula (IV), the group of values ofn being statistically distributed about an average value corresponding to the number of molecules of glycerol epihalohydrin provided per molecule of alcohol.  
  But the important point. which represents one of the essential advantages of the process according to the invention, is that it leads to the formation of compounds having a single lipophile group for each hydrophile chain.  
  Moreover. it should be pointed out that the process according to the invention makes it possible to regulate the lipophile property of the resulting product by varying the value of the number n of glycerol epihalohydrin molecules provided for each molecule of alcohol.  
 When n is at least equal to one-third of the number of carbon atoms in the lipophile chain, the products are detergents which are soluble in water. Moreover. the derivatives in which the lipophile chain contains 10-14 carbon atoms make good foaming agents. while those in which the lipophile chain contains more than 14 carbon atoms are emulsifiers.  
  When n is more than 10 the condensation becomes difficult because beyond this value, we obtain the phenomenum described in the JACS Vol. 82 Jan. 60 No. 1 (Pages 120-124) Latremouille, Merrall and Eastham, that is to say. the depolymerization of our products by formation of dioxane and rupture of chain links.  
  In a preferred embodiment of the invention the glycerol epihalohydrin is polycondensed in the presence of a Lewis acid catalyst such as boron trifluoride, stannic chloride. or antimony pentachloride. at a temperature between and 160C.  
  When boron trifluoride is used, this is introduced in the proportion of 1 to 2% of the total reaction mass and the reaction is preferably carried out at between 60 and 120C.  
  The hydroxylation which constitutes the second step of the process makes it possible to avoid the disadvantages inherent in those reactions in which hydroxyl groups are directly substituted for halogens. It is well known that the preparation of hydroxylated compounds by hydrolysis of halogen derivatives is, in general, quite difficult, that the substitution is often incomplete, and that the presence of the mineral halides has an adverse effect on the solubility and makes it laborious to separate the desired end product. The hydroxylation step which is preferred to use in the practice of the present invention consists in reacting the halogen derivative of formula (IV) with an alkaline salt of carboxylic acid, preferably within a solvent which insures both the miscibility of the reagents and the easy separation of the halide formed. In this method, the selected solvents participate by progressive alcoholysis of the esters formed in an intermediate stage. Among the solvents having the required properties are propylene glycol. dipropylene glycol, diethylene glycol, ethylene glycol, hexylene glycol, 2-butoxy-ethanol, 1,3-butanedio1 and ethers of diethylene glycol, such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether. diethylene glycol diethylether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, the boiling points of which are sufficiently high to make it unnecessary to use an autoclave. In general, it has been found that the amount of solvent to be used should equal at least 50% by weight of the amount of polyhalogenated ether which is to be hydroxylated, and preferably from to 400% by weight.  
  The hydroxylation reaction is carried out at a temperature high enough for the speed of the reaction to be convenient and low enough so that there is no degradation of the products formed. A temperature between and 200C, and preferably between 180 and C is suitable. The percentage of hydroxylation resulting under these conditions is always greater than 90%.  
  The alkaline salt of carboxylic acid used in the hydroxylation step is advantageously an acetate in stoichiometric proportions or in slight excess, 10 to 15% at the maximum) with respect to the halogenated compounds participating in the reaction. it has been found that the results remain equally satisfactory when the acetates are added all at once at the beginning of the hydroxylation step, or in successive fractions in the course of this reaction. It is possible to regenerate the acetates in situ from the esters formed during the reaction, for example, by adding an aqueous solution of an alkaline hydroxide and instantaneously evaporating the water.  
 Finally, in order to avoid coloring the products obtained during the hydroxylation, it has been found that it suffices to add reducing agents such as sodium hypophosphite or alkaline borohydrides.  
  The products according to formula (111) are very valuable because of their emulsifying properties and their compatability with ionic surface-active agents. This compatability makes it possible to introduce them into aqueous or hydroalcoholic solutions in association with ionic surface-active agents.  
  It is a further object of the present invention to provide cosmetic compositions, and particularly hair dye compositions, which are essentially characterized by the fact that they contain at least one product responding to formula ([11) or to formula (I) in amountsranging from 1 to 60% by weight of said composition and a conventional hair dye in amounts effective to color said hair.  
  These hair dye compositions may in addition contain other surface active agents and/or carriers. thickening agents such as hydroxycthylcellulose. carboxymethylcellulose etc.  
  It is another object of the present invention to provide an effective peptizing agent comprising said surface-active agents for dispersing solid pulvcrulent material in non-aqueous liquid media. and particularly in oils.  
  Still another object of the present application is to provide a dispersion of solid pulverulent material in non-aqueous liquid media. and particularly in oils. said dispersion being characterized by the fact that it contains as a peptizing agent at least one compound according to formula (III). Preferably R in this formula (III) represents a radical derived from alcohols and sterols obtained by hydrogenation of lanoline. R may also represent a radical derived from alcohols obtained by reduction of cyclic fatty acids.  
  A solid pulvcrulent material such as a pigment which is ground up in oil is frequently used in the cosmetic field. These pigments are often obtained by precipita- .ion. and are dried. After drying they re-agglomerate, so that they must be ground before being mixed with the oil. This grinding is not too fine because it is limited by the mechanical means available. It has been suggested that the precipitated product be dried in the presence of oil. However. experience has shown that. even though insoluble in water. a large part of the pigment is not emulsified by the oil and re-agglomerates on drying. It has now been found that drying of such pigments in the presence ofa peptizing agent according to the invention comprising a compound according to the formula (III) redisperses the pigments in the oil while retaining their original degree of fineness. Representative oils employed include. for instance. paraffin oil. vegetable oils. animal oils. modified animal oils such as perhydrosqualene or fatty acid esters such as isopropyl myristate.  
  Generally. the amount of oil employed ranges between about 50 to 99% based on the total weight of the dispersion and the amount of peptizing agent can vary between about 1 to based on the weight of the pulvcrulent material.  
  Moreover. it should be emphasized that the compounds of formula I in a 5% aqueous solution are completely harmless and freely tolerated by the mucous membrane of the eye. This property has been clearly established by tests carried out on the dyes of a group of rabbits using the methods described by J. H. Draize. G. Woodard and H. O. Calvery in the Journal of Phar&#39; macology&#34; 1944. Vol. 82. pages 377-389 and by .I. H. Draize and E. A. Kelly in &#34;Proceedings of Scientific Section&#34;, 17. l-4. (1952). No lesions of any nature appeared in the mucous membranes of the eyes of rabbits after such tests. Moreover. these compounds. when associated with cationic surface-active agents. cause no synergistic irritation. On the contrary. they decrease the irritation caused by certain quaternary ammonium halides.  
  The cosmetic compositions according to the invention may be stock solutions, i.e. concentrates to be diluted before use and compositions ready for use.  
  The concentrates may contain up to 75% of the compounds of formulas I and III. The compositions ready for use are preferably aqueous solutions comprising about l-25% and advantageously 5-207( of the compounds of formulas I and III.  
  The above cosmetic compounds may contain other ionic or non-ionic surface-active agents and the percentages indicated above include all the surface-active agents.  
  Other conventional additives such as thickening agents may be added to these compositions. When the hair is washed with these solutions it becomes shiny. soft and non-electric.  
  It has moreover been found that the compounds according to formula I may be used in cosmetic compounds as carriers for hair dyes. In general, such hair dye compositions have a pH of 3 to 9.  
  In order that the invention may be clearly illustrated, examples which show the general method of preparation and use of compounds of this invention will now be described.  
 EXAMPLE 1 Preparation of the compound:  
 CI2H25O+C2H3O(CH2OH &#39;17- H in which n has a statistical average value of about 4. First step-polycondensation:  
  I86 g of lauryl alcohol and 1.5 ml of an acetic compound of boron fluoride containing 3671 BF are introduced into a flask adapted to hold a liter and provided with stirring means, a thermometer and a cooling coil.  
  The mixture is heated to C and 389 g of glycerol cpichlorohydrin are added drop by drop. The reaction is exothermic. and the temperature stays between 75 and C. The operation lasts 75 minutes. after which the reaction mixture is permitted to return to room temperature.  
  The resulting polyoxychloropropylenated lauryl alcohol is a clear yellow oil which is insoluble in water. The epoxide function is measured to verify that the epichlorohydrin has completely reacted.  
 Second stcp-hydroxylation:  
  144 g of potassium acetate are dissolved in 360 g of dipropylene glycol. This solution is heated to 180C under a nitrogen atmosphere.  
  181 g of the product obtained in the first step are added while stirring. This takes 30 minutes. The mixture is then heated for 2 /2 hours at between 180 and I90C. After cooling it to room temperature. the potassium chloride formed is separated by filtration. with a yield of about 96% of the quantity which should theoretically have been formed.  
  The partially acetylatcd dipropylene glycol is evaporated under vacuum from the filtrate and a sirupy product soluble in water is thus isolated.  
  The index of saponification determined for both the end product and the recovered solvent. shows that the polyhydroxylated polyether is de-acetylated.  
  The product is then dissolved in 500 ml of absolute ethyl alcohol. This solution is colored with vegetable black and 300 mg of sodium ethylate dissolved in 10 ml of absolute ethyl alcohol are added. The resulting mixture is left at room temperature for 6 hours. which permits de-acetylation of the product. After evaporation of the ethyl acetate and the ethyl alcohol. 147 g of an end product having the following characteristics are recovered:  
 Saponification index Hydroxyl index 546 Iodine index I Percentage of potassium acetate 7% This compound is in the form of a sirupy liquid which is readily soluble in water. 1t has excellent foaming characteristics and is perfectly tolerated by the mucous membranes of the eye.  
 EXAMPLE 2 Preparation of the compound having the formula:  
 C, H ,-,O-[-C H O (CH OH) -1 H in which n has a statistical average value of about 4.  
  In a first step the glycerol epichlorohydrin is polycondensed on the lauryl alcohol in the manner described in Example 1.  
  1n the second step, hydroxylation is effected in the following manner:  
  0.84 mols of crystallized sodium acetate in the form of the trihydrate and 0.11 g of sodium hypophosphite are dissolved in l g of diethylene glycol. The solution is heated under a nitrogen atmosphere. When the ternperature reaches 120C the water begins to distill away. At l40-145C gelification may be seen.  
  1 15 g of polyoxychloropropylene lauryl alcohol are then added within minutes. while stirring and maintaining the temperature between 140 and 145C. The reaction mixture again becomes fluid. and is heated at 180C to complete the evaporation of the water.  
  The reaction is then continued at 180-185C for three hours. Under these conditions from 95.5 to 96% of the sodium acetate involved is consumed. After cooling to 80C. the solution is filtered and the sodium chloride washed with 29 g of diethylene glycol at 80C. The diethylene glycol is evaporated from the filtrate under vacuum and while heating to 180C. 107 g of a product having a saponification index of 64 and 150 g of partially acetylated diethylene glycol having a saponification index of 244 are recovered.  
 The de-acetylation of the polyhydroxypolyether is terminated by saponification with aqueous 13% sodium hydroxide at a temperature of 40-45C. This step takes an hour and a half.  
 EXAMPLE 3 Preparation of the compound:  
 RO+C H O (CH OH) 4 H (in which R represents a linear aliphatic chain having 12 to 14 carbon atoms derived from copra and n has a statistical average value of 4).  
 First step-polycondensation:  
  Proceeding as in Example 1, 370 g of glycerol epichlorohydrin are reacted with 200 g of a mixture of fatty alcohols of copra consisting essentially of dodecanol and tetradecanol in the proportion of about 70% of the first to 30% of the second. This produces a polychlorinated polyether.  
 Second step-hydroxylation:  
  1 14 g of the compound thus obtained are dissolved in 200 g of dipropylene glycol. The solution is heated to 180C and 80 g of potassium acetate are added little by little. After 4 hours and 30 minutes of reaction at 180C. 96 to 97% of the acetate introduced has been consumed. The potassium chloride thus formed is separated. the solvent is evaporated. and an indicated in Example l. the product is dissolved in ethyl alcohol. The ethyl acetate and the ethyl alcohol are then eliminated and 100.5 g of a sirupy product are recovered. This product is soluble in water and responds to the formula given at the beginning of this example.  
 EXAMPLE 4 Preparation of the compound having the formula:  
 (in which R represents a linear aliphatic chain having 12 to 14 carbon atoms, and n has a statistical average value of about 5.5.)  
 First step-polycondensation:  
  In the same way described in Example 1. 509 g of glycerol epichlorohydrin are reacted with 194 g of a mixture of fatty alcohols containing about of dodecanol and 30% of tetradecanol in the presence of 1.5 ml of an acetic compound of boron fluoride comprising 36% BF This yields a chlorinated polyether.  
 Second step-hydroxylation:  
  70 g of the polychlorinated polyether obtained in the first step hereinbefore described are dissolved in 735 g of Z-butoxy ethanol. The solution is heated to C. and 55 g of anhydrous potassium acetate are then introduced little by little, over a period of 40 minutes.  
  After reacting for 7 hours at 170C. the reaction mixture is permitted to return to ambient temperature. 94% of the quantity of potassium chloride which should theoretically have been formed is separated by filtration. After evaporation of the solvent 67.5 g of a product are recovered, which is then de-acetylated with ethanol. in the presence of potassium hydroxide which acts as a catalyst. The ethyl alcohol and ethyl acetate are then eliminated.  
  The resulting polyhydroxyl ether is soluble in water and is a good foaming detergent.  
 EXAMPLE 5 Preparation of the compound:  
 RO-{-C H;,O (CH OH) H (in which R is an alkyl radical having 16 to 18 carbon atoms and n has a statistical average value of 6.) First step-polycondensation:  
 The method of operation is essentially that of Example l. 416 g of glycerol epichlorohydrin are reacted at a temperature between 70 and 80C and 188 g of a mixture of cetyl alcohol and stearyl alcohol in the presence of 0.87% of boron fluoride, yielding a polychlorinated polyether.  
 Second step-hydroxylation:  
  156 g of the compound thus obtained are mixed with 144.5 g of potassium acetate dissolved in hexylene glycol at a temperature between and C. The temperature is maintained for 3 hours. Then it is cooled to 25C and the potassium chloride formed is separated by filtration. The hexylene glycol is then evaporated under a pressure of 15-20 mm of mercury while progressively increasing the temperature to 180C. The product is de-acetylated by ethanolysis with sodium cthylate as the catalyst. The ethyl acetate and the alcohol are eliminated. and 132 g of a pasty product which dissolves in water at 75C are recovered.  
 EXAMPLE 6 Preparation of the compound:  
 C H O-[-C H O (CH- H l-,-, H  
 in which n has a statistical average value of 10. First step-polyeondensation:  
  [n the same general way as in Example 1. 462.5 g of glycerol cpichlorohydrin are reacted with 143.5 g of stearyl alcohol in the presence of 1.1% boron fluoride. The reaction mixture is kept for four hours at a temperature between 60 and 65C and then heated to 120C for 5 minutes. It is then stirred while being permitted to return to ambient temperature.  
 The result is a polychlorinated polyether.  
 Second step-hydroxylation:  
  242.5 g of the compound obtained in the first step are heated with 200 g of potassium acetate, using 300 g of dipropylene glycol as the solvent. The reaction is continued for 3 hours at a temperature between 185 and 190C. The chloride ion and the potassium acetate are then measured to determine the percentage of transformation. which is found to be between 97 and 98%. The resulting product is isolated and ethanolyzed as in Example l. After the ethyl alcohol and ethyl acetate have becn evaporated. the process yields 177 g of a solid product which. in aqueous solution. is slightly opalescent at 25C and limpid at 60C.  
 EXAMPLE 7 Preparation of the compound:  
 (in which n has statistical average value of 5 and R is a branched chain alkyl radical containing 1 l to 16 carbon atoms in the branch chain derived from an alcohol obtained by &#34;Oxo&#34; synthesis). First step-polycondensation:  
  Using the method of Example 1. 231.2 g of glycerol cpichlorohydrin are reacted with 105.5 g of a mixture of fatty alcohols obtained by Oxo synthesis. the branched hydrocarbon chain of which contains 11 to 16 carbon atoms. This reaction is carried out in the presence of 0.75 ml of an acetic compound of boron fluoride.  
  This yields a polyoxychloropropylenated alcohol which is insoluble in water and a deep brown in color. Second step-hydroxylation:  
  134.7 g of the compound thus obtained are dissolved in 876 g of dipropylene glycol, and l g of potassium borohydride is added to this solution. The mixture is heated while stirring and loses color rapidly. 100 g of potassium acetate are then added. followed by 50 g of dipropylene glycol. After 3 hours of reaction at 175-l80C. 93.5% of the potassium acetate supplied has been consumed.  
  The potassium chloride is separated by filtration. after which the solvent is evaporated by progressively raising the temperature to 180C under a reduced pressure to 20 mm of mercury). The resulting product is then subjected to ethanolysis in the presence of alcoholic potassium hydroxide.  
  The ethyl acetate and alcohol are then eliminated and 135.5 g ofa sirupy liquid are recovered. This liquid dissolves easily in water and may be used as a foaming detergent.  
 EXAMPLE 8 First step-polycondensation:  
  Glycerol cpichlorohydrin is reacted with commercial oleyl alcohol having a hydroxyl index of 207 and an iodine index of 88.  
  This yields polychlorinated mono-alkyl-ethers having the formula:  
 1 Ro+c a o (ur ent H in which R designates the radical derived from the oleyl alcohol raw material and n has the value 2, 4, 5 or 6.  
  This reaction is carreid out at about C. using. as a catalyst. an acetic compound of boron fluoride in the ratio of about 0.25 ml per g of reaction mass. Second step-hydroxylation:  
  The polychlorinated ether obtained in the first step of the present example is treated with a stoichiometric quantity of potassium acetate at a temperature of about l80-185C. for 5 hours. The solvent used in this reaction is dipropylene glycol. The quantity of solvent is equal in weight to that of the chlorinated ether and the potassium acetate combined.  
  The products obtained at the end of the hydroxylation step have properties which are summarized in the following table:  
 Value Appearance Solubility of n 2 Yellow oil Dispersible in water 4 Yellowish paste Soluble in water with turbidity 5 Clear brown paste Soluble in a hydroalcoholic 1 medium containing 10&#39;&#39;;  
 I alcohol 6 Clear brown paste Soluble in water EXAM PLE 9 First step-polycondensation:  
  343 g of Hexadecylie&#39; alcohol. sold commercially by Esso. are reacted with g of glycerol cpichlorohydrin in the presence of 1.25 ml of an acetic compound of boron fluoride. yielding a polychlorinated ether having the formula:  
  /CH-CH+ C2H3O (ca oakj a C8H17 in which n has a statistical average value of 1.5 and is an almost colorless oil which is dispersible in water.  
 The product can advantageously replace the olcic dem rivative having the same hydrophilic chain. Because it contains no double bond. it does not turn rancid.  
 EXAMPLE 10 First step-polycondensation:  
  372 g of lauryl alcohol (i.e.. the product sold under the trademark Alfol-12) are reacted at -90C with 278.5 g of glycerol epichlorohydrin in the presence of 1.65 ml of an acetic compound of boron fluoride.  
 The result is a lauryl ether having the formula:  
  has first been heated to 70C.  
 Third step-preparation of a sulfated derivative:  
  74 g of polyhydroxylated ether prepared in the first step are mixed with 6 g of urea and heated to C. 25 g of sulfamic acid are then added. The mixture is vigorously mixed using a turbo-mixer and heated on an oil bath to C. The reaction is then strongly exothermic and. while heating is discontinued, the temperature rises to C.  
  The resulting sulfate dissolves readily in water and is a good foaming detergent.  
 EXAMPLE 11 Preparation of the compound:  
 in which n has a statistical average value of about 6. First step-p0lycondensation:  
  2.5 ml of a phenolic boron fluoride compound containing 2671 BF are added to 167 grams of melted octylphenol.  
  416 grams of glycerol epichlorohydrin are then added. drop by drop. while stirring. The reaction begins at 95C. after which the temperature is lowered to 75-80C when the mixture will remain liquid at the latter temperature.  
  The epichlorohydrin is added over a period of 60 minutes. 0.5 ml of the phenolic boron fluoride compound is then added and the reaction terminated while continuing to stir the mixture.  
  No loss of weight due to evaporation of volatile products occurs while the mixture is being heated in a water-bath under a vacuum produced by a water-jet pump. The polychlorinated ether thus obtained is in the form of a viscous oil.  
 Second step-hydroxylation:  
  300 g of potassium acetate are dissolved in 700 g of dipropyleneglycol and the resulting solution heated to 180C under a nitrogen atmosphere.  
  398 g of the product obtained in the first step are then added while stirring the mixture for 170 minutes, after which is it heated for 100 minutes at a temperature between C and C. It is then cooled to room temperature and the potassium chloride formed therein is filtered out.  
  The partially acetylated dipropylene glycol is evaporated under vacuum from the filtrate.  
  The product thus obtained is dissolved in 750 ml of absolute ethyl alcohol; the solution is colored with vegetable black. and 30 ml of alcoholic potassium hydroxide at half normal strength are added. The resulting mixture is left at room temperature for 4 hours and 30 minutes. thus de-acetylating the product. After evaporation of the ethyl acetate and the alcohol 335 g of a product responding to the formula at the beginning of this example are obtained in the form ofa viscous substance which is soluble in water. This substance has good foaming power and does not irritate the mucous membrane of the eye.  
 EXAMPLE 1?.  
 Preparation of the compound:  
 c a o+c H o ca oa) in which n has a statistical average value of 6. First step-polycondensation:  
  Following the method described in Example 1, 416 g of glycerol epichlorohydrin are reacted with 172 g of commercial nonyl-phenol. A polychlorinated polyether is thus obtained.  
 Second step-hydroxylation:  
  300 g of potassium acetate are dissolved in 700 g of dipropylene glycol. The solution is heated to 180C and 392 g of the product obtained in the first step are added, little by little. After reacting for 4 hours at 180C. about 95% of the theoretical quantity of potassium chloride has been formed and should then be separated out. The solvent is then evaporated and the ethyl acetate and alcohol eliminated. to yield 345 g of a viscous product which is soluble in water and responds to the formula given at the beginning of this example.  
 EXAMPLE 13 Preparation of the product represented by the formula:  
 RO+C H.-;O(CH OH H in which R is a hydrocarbon derived from lanolin alcohol obtained by catalytic hydrogenation of lanolin and sold under the trademark ELROLAN by the VEB DEUTSCHES HYDRlERWERK. and n has a statistical average value of 4.  
 First step-polycondensation:  
  0.7 ml of an acetic complex of boron fluoride is added to 103 g of the molecularly equivalent amount of alcohol) in the form of the above ELRO- LAN which has been melted.  
  The mixture is heated to 75-80C. and 92.5 g of glycerol epichlorohydrin are introduced. \vhile stirring. This addition is so regulated as to keep the temperature substantially constant. as a result of the exothermic character of the reaction.  
  This operation takes 40 minutes. The reaction mixture is then heated in a water bath for 15 minutes.  
  The result is a polychlorinated ether in the form of a viscous oil.  
 Second step-hydroxylation:  
  156.6 g of polychlorinated ether are dissolved in 160 g of dipropyleneglycol. The mixture is heated to 145C. 260 g of a aqueous solution of potassium acetate are then introduced. In the course of this operation the temperature is progressively increased so as to eliminate water from the reaction mixture. This is then maintained at l80-185C under a nitrogen atmosphere for three hours.  
 After cooling. the potassium chloride is separated by filtration. The precipitated salt is washed with hot dipropylene glycol. The solvent is evaporated from the filtrate at first under a reduced pressure of l5-20 mm of mercury. and then under a pressure of 1 mm.  
  The product is then introduced into 225 ml of absolute ethyl alcohol and subjected to ethanolysis. For this purpose sodium methylate is used as a catalyst in the proportion of 0.275 g per 100 g of product to be treated.  
  The mixture is kept first at C so as to obtain a homogeneous mixture. and then left at room temperature overnight. After evaporation of the ethyl acetate and ethyl alcohol. a yellow-brown paste is recovered which can be dispersed in water. The composition of this paste is represented by the formula given at the beginning of the example. and it has the following characteristlcsz Hydroxyl index 372 Saponilication index 9 EXAMPLE 14 Preparation of the product represented by the formula:  
 RO+C H O (CH OH H in which n has a statistical average value of 7.6 and R represents the alkyl radical of the mixture of hydrogenated lanolin alcohols sold commercially under the trademark &#34;ELROLAN.&#34; First step-polycondensation of epichlorohydrin:  
  In this process 41.3 g of the mixture of lanolin alcohols. 74 g of glycerol epichlorohydrin and 0.4 ml of an acetic complex of boron fluoride are reacted together. the acetic complex of boron fluoride being introduced into the reaction mixture in three fractions:  
 0.2 ml at the beginning of the reaction;  
 0.1 ml before the end of the addition of the first half of the epichlorohydrin used: and  
 0.1 ml while the second half of the epichlorohydrin is being introduced. The temperature is kept at 8085C.  
  Under these conditions 93% of the epoxide introduced is consumed. i.e.. 7.6 mols per molar equivalent of alcohol.  
  After evaporation of the glycerol epichlorohydrin the result is a polychlorinated ether represented by the formula:  
 in which R and n have the significance hereinbefore assigned thereto. Second step-hydroxylation:  
  This step is carried out at 180185C in a propylene glycol bath. utilizing potassium acetate in stoichiometric proportions with respect to the chlorine.  
  After 4 hours of heating at l-l85C, the percentage of substitution is of the order of 96%.  
  After separating the potassium chloride by filtration. the dipropylene glycol is evaporated under subatmosphere pressure.  
  As in Example 1. the de-acetylation is terminated by ethanolysis.  
  The resulting product is dissolved in water. The solution thus produced exhibits a turbidity which does not increase when the temperature is raised to 100C.  
 EXAMPLE 15 Preparation of the product represented by the formula:  
  i- E 30 (CH OH)-]r H in which R represents the alkyl radical of the hydrogenated lanolin alcohols sold commercially under the trademark &#34;HYDROLAN&#34; by OCCO INTERNA- TIONAL (DIVISION OF MlLLMASTER ONYX CORPORATION). This raw material has a hydroxyl index of 154.  
  The polycondensation of epichlorohydrin and the hydroxylation reaction are carried out under conditions indentieal to those described in Example 13. The product thus obtained is in the form ofa soft water insoluble wax.  
 EXAMPLE 16 Preparation of the product represented by the formula:  
 in which R represents the alkyl of the lanolin alcohols sold under the trademark HYDROLAN The polycondensation of the epichlorohydrin is carried out at 80-90C in the presence of boron fluoride as a catalyst and in the proportion of O. l 5% of the total weight of the reaction mixture. Hydroxylation is brought about by heating at C for 4 hours and a half.  
  The polyhydroxyl polyether represented by the above formula takes the form of a yellow-brown paste.  
 It is dispersible in water.  
 EXAMPLE 17 Preparation of the product represented by the formula:  
  d- E 30 (Gl-LOHH H in which R represents a hydrocarbon derived from alcohols obtained from the isostearic acid sold commercially by the Emery Company. the preparation of which is described in U.S. Pat. No. 2.812.342.  
  The mixture of fatty alcohols obtained by catalytic hydrogenation and distillation has a hydroxyl index of 193.  
 First step-polycondensation of epichlorohydrin:  
  By reacting 245 g of isostearylic acid at 80C with 148 g of epichlorohydrin. in the presence of 1.2 ml of an acetic complex of BF a polychlorinated ether is obtained which responds to the formula:  
  &#39;l Z aO (CHgCll&#39;l&#39;E H Second step-hydroxylation:  
  385 g of the polychlorinated ether obtained in the first step are dissolved in 580 g of propylene glycol. The mixture is heated to l40C and 420 g of an aqueous 40.4% solution of potassium acetate are introduced by progressively increasing the temperature to 165C so as to eliminate the water from the reaction mixture.  
  After 4 /2 hours at l80l90C, the percentage of substitution. calculated from the acetate consumption, is 9971.  
  The potassium chloride is then separated and the dipropylene glycol evaporated under vacuum. The dcacetylation of the product is then terminated by ethanolysis. using 0.25% sodium methylate as the catalyst.  
  After evaporation of the ethyl acetate and ethyl alcohol. a polyhydroxyl polyether is recovered in the form of a sirupy light yellow liquid.  
  This product is purified by washing it twice in boiling water. using I liter of water in the first washing and L5 liters in the second.  
  The products represented by the following formula are successively prepared in like manner.  
 RO-[-C- HsO (CH2OH)-]T| H In this formula R represents a hydrocarbon derived from alcohols obtained by the catalytic hydrogenation of commercial isostearic acid. The properties of these derivatives are summarized in the following table:  
  Although the example set forth above can use R groups obtained by reacting commercially available fatty alcohol mixtures, similar results are obtained by using a single fatty alcohol. aliphatic alcohol or alicyclic alcohol. When a single or pure ROH reactant is used the R portion of the compounds formed all have that R group.  
  The following alcohols further illustrate the type alcohols that can be substituted in the above examples to produce the compounds of this invention which have the corresponding R and R groups present in the specific alcohol reactant:  
 u. Saturated linear alcohols such as:  
 l-octanol l-decanol l-undecanol l-dodecanol l-tridecanol l-tetradecanol l-pcntadecanol l-hexadecanol l-heptadecanol l -octadecanol l-eicosanol l-docosanol h. Unsaturated linear alcohols such as:  
 Oleyl alcohols (cis-9-octadecenel -ol) Elaidyl alcohol (trans-9-octadecene- 1 -01) Erucylic alcohol (cis-l3-docosenc-l-ol) c. Branched chain alcohols such as:  
 Z-ethyll -hexanol Z-methyl-l decanol Z-methylldodecanol 2-methyll -tridecanol Z-methyll-tetradecanol 3, 7. l l. lS-tetramethyl-l-hexadecanol 2, 3. 5. 7-tetramethyl-l-nonanol 2. 4. 7-trimethyl-l-nonanol 2-octyll -dodecanol Z-hexyll -decanol 2-methyl-alkanols d. Fatty alcohols derived from animal and vegetable oils and fats. such as:  
 Copra Tallow. etc.  
  e. Mixed industrial alcohols such as those derived from the ALFOL&#39; process. the OXO&#34; process. etc. These compositions contain a variety of isomers and homologs which vary with the olefin feed that is being converted to the alcohol mixture.  
  f. Fatty alcohols prepared using the GUERBET reaction.  
  g. Fatty alcohols prepared using the method described in US. Pat. No. 2.812.342.  
 h. Phenol alkyls. such as:  
 p-tert-octyl-phenol p-sec-octyl-phenol p-isononyl-phenol p-tert-dodecyl-phenol p-isododecyl-phenol and in general those alcohols which are obtained by alkylation of phenols with olcfins such as dodecine. tripropylene, tetrapropylene and diisobutylene.  
 i. Aliphatic alcohols. such as:  
 ceryl alcohol melissyl alcohol cholesterol lanesterol or dihydrolanesterol mixtures obtained by catalytic hydrogenation of Ian-.  
 olin or resinic fatty acids.  
  The preparation of lanolin alcohols by hydrogenation was described by K. Stickdorn E. Konig and Birk in the TENSIDE review. 3. No. 2 (1966) p. 45.  
 j. Saturated cyclic fatty alcohols such as:  
  These cyclic alcohols have been described by Bellfriedrich Gast and Cowan in JAOCS review. 42. October 1965, on page 876.  
  Moreover. the compounds of the invention can be transformed by a known process. into ionic surfaceactive agents by introducing ionic groups into the compound strueture. such as sulfonate ions. carboxylate ions. phosphate ions. etc.  
 EXAMPLE 18 The following composition is prepared:  
 in which R is an ole \&#39;l radical 20 g Z-hutoxy ethanol 15 g 20% ammonia 13 cm Ethylene diamine tetracetic acid 0.3 g Sodium bisulfite 0.6 g Paratoltn&#39;lene diamine 0.4 cm&#34; Metadiamino-anisol 0.04 g Resorcinc 0.2 g Meta-untinophenol 0. l g Pura-uminophcnol 0.25 g Water. q.s.p. 100 g This solution is mixed with an equal volume of hydrogen peroxide at 20 volumes. thus producing a beautiful transparent gel. This gel is applied to very gray hair for 25 minutes. After shampooing. a chestnut shade results.  
 When dried. the hair is especially soft and lustrous.  
 EXAMPLE 19 The following composition is prepared in which R is an ole \l radical 25 g RO-[-( H ()(CH OH) 1 H in which R is an ole \&#39;l radical l g Olein 6 g 509i dicetvldimethyl ammonium chloride in isopropanol l 2-hutox ethanol 1 Ethyl alcohol ammonia l Paratoluylene diamine 0 Rcsnrcine 0 Meta-aminophenol (l. Para-aminophenol 0 Methyl para-aminophenol 0 Meta-diaminoanisol I Ethylene diamine tetracetic acid 0. Sodium bisulfite 0. Water. q.s.p. N  
  This solution is mixed with its own volume of hydrogen peroxide at 20 volumes. When applied to very gray hair for to minutes, the result. after shampooing. is a golden chestnut shade.  
  The hair. after treatment. is very soft and easy to manage.  
 -Continued ltletudiamino-anisol 0.02 g Resorcine (H5 g Meta-aminophenol 0.3 g Para-aminophenol 0.2 g Sodium bisulfite 0.6 g Water q.s.p. I00 g This solution is mixed with its own volume of hydrogen peroxide at&#39; 20 volumes. When applied to very gray hair for 25 to 30 minutes. the result. after shampooing. is a dark blond shade.  
 The hair. after treatment. is very soft and easy to manage.  
 EXAMPLE 20 A The same composition is prepared as in example 20 except that The same good results are obtained as in example 20.  
 EXAMPLE Zl The following composition is prepared:  
 Laurylether sodium sulfate ox \&#39;eth vlenated with 2 moles of ethylene oxide 5 g Eth \&#39;l alcohol 15 g 200? ammonia l4 em Ethylene-diamine tetraeetic acid 0.3 g Para-toluylene-diamine. 0.1 g Resorcine 0.] g Meta-aminophenol 0.05 g Para-aminophenol 0.l5 g Sodium hisulfite 0.6 g Water q.s.p. I00 g This solution is mixed with its own volume of hydrogen peroxide at 20 volumes. When applied to very gray hair for 25 to 30 minutes. the result. after shampooing. is a fair blond shade.  
  The hair. after treatment. is very soft and easy to manage.  
 EXAMPLE 21 A The same com-position is prepared as in example 21 except that is used instead of R0 [-C H -,O(CH-,OH)-l1- H 20 g R oleyl The same good results are obtained as in example 2l.  
 EXAMPLES 21 B 2] E i EXAMPLE 22 B i a The same composition is prepared as in example 22 The Same composmo&#34; prcparcd &#39;&#34;F except that the two first components are replaced by except that I 5 RO [C H O(CH OH)-h H C H O [C H;,O(CH- ,OH h H s L g s R linear aliphatic chain having 12 to 14 carbon 18 replaced by the same weight of: atoms derived f copra RO -[-C H;,O(CH ,OH)-] H m and (31 B) R [-C H O(CH OH)-]- H in which R represents a linear aliphatic chain having l2 25 g to 14 carbon atoms derived from copra. R isostearyl R0 H ()(CH OH) H H The same good results are obtained as in example 22.  
 2 a 2 &#39;l s.s  
  (1] 0 EXAMPLE 23 in which R represents a linear aliphatic chain having 12 The following composition is prepared: to 14 carbon atoms derived from copra. Dye? v 1,S-bis-y-aminopropylamino anthraquinone 0.15 g. RO -[-C H;,O( CH OH) H 20 l-diethylarnino ethylamino 2-nitr0 4-NN-dihydroxyethyl- 0.6 g.  
  amino benzene dihydro-ehloride. (H D) 4-N-methylamino-3nitr0-l-N-B-aminoethylamino benzene. 0.25 g. [l-hydroigy 4-(y-methy1morpholinium) propylamino an- 0.1g. in which R IS a branched chain alkyl radical containing q o el e y u a e Z-B-ammoethylamtno anthraqumone 0.2 g. l l l0 l6 Cill&#39;bOfl llIOlTlS. 1,5-di-(B-aminopropylamino) anthraquinone 0.3 g. l-dimleltliylaming 3-aminoethylamino 4-ntiltlro benzene g. 1 l-met yamino -amino-propy amino an raquinone g. R0 cH&#39;loH H l-amino-propylamino anthraquinone 0.15 g.  
  1,4-diamino S-aminopropylamino anthraquinone 0.4 g. 21 E) l -Intro 45-aminoethylamino anisole monohydrochloride... 0.2 g. in which R is a radical derived from oleyl alcohol. ii acid L00 g, ]I)iethanola1ilnide of 1cfopra. &#34;.51. 1 t..d..RHEHFTHY. g. 77 aury so um su ate oxye yena e wi moes o g EXAMPLE u) ethylene oxide. The following composition is prepared: R NH CH COONa 1mg CH2CON(CH2)3N R-()-IC H;.O (CH OH1|,H l5 g (HITCH: 2 6 T O CH H N g 2; (R=pHydrocarbon radical derived from fatty acids of 2 a 2 2- (50 r R Oleyl Eth \&#39;l alcohol 20 g 20% ammonia 11 cm&#34; R&#34;-0 [C2H3O (CH2OH)IH Eth vlene-diamine tetracetic acid 0.3 g Para&#39;toluylene-diamine 5 g (R=Nonylphenyl) Mela-diaminozmisol 0.05 g R rcin .2 g 40 figg fi g gg 8% 5&#39; g H drox eth lcellulbidby&#39;ifriifichfidEinti aiiidxf 15 g. pilrll&#39;ilmlllllllhemll 2 under the trademark Cellosize W.P. 3&#34;. Sodium hisulfitc 0.6 g Water, g.s.p 100 g. Water q.s.p. l()() g This composition is applied for minutes to chest- This solution is mixed with its own volume of hydro- 45 nut hair containing 30% to 70% gray hair. After shamgcn peroxide at 20 volumes. When applied to very gr pooing adark chestnut shade is obtained masking the hair for to minutes, the result. after shampooing. gray hair. is a chestnut shade.  
 . EXAMPLE 24 The hair. after treatment, is very soft and easy to m-maga The following composition is prepared:  
 EXAMPLE 22 A Dyes r 1&#39; ainlnopropylamino anthraqumone 0.15 g. The same composition is prepared as in example 22 i i; dhydmxyethyl&#39; 4-N-rnethylamino-3nitro l-NB aminoethylamino benzene... 0.25 g. [l-hydroxy 4- (v methylmorpholinium) propylamino an- 0.1 g.  
  thragulnone] methyl sulfate. R0 C H O CH OH 1; H Q-B-arnmoethylamino anthraquinone 1,5- d1-(B-am1nopropylamino) anthraquinone l g l-dimethylamino 3-amino ethylamino 4-nitro benzene. g 1-methy1amino 4-arnino propylamino anthraquinone. R lm ar ahphuuc chum havmg 12 I0 14 carbon l Propylamlpo amhl&#39;aqulnone lA-diamino 5-y-aminopropylammo anthraquinone... atoms ClCl&#39;lVCd from copra C 3 -n1tr0 eB-aminoethylamino anisole monohydrochloridet (,0 amer: and Lautic acid Diethanolamide of copra Lanryl sodium sulfate oxyethylenated with 2 moles of (361111 3 dlethylene oxide.  
 817 (RHd b y rocar on radical d df ftt f The same good results are obtained as in example 22. copra) enve mm a y mas 0 except that the two first are replaced by Continued R-O|: C2H30(CH2OH) 5.00 g.  
 (R Octylphenyl) Butylglycol 6.00 g. Monoethanolamine 0.60 g. Hydroxyethylcellulose, sold by Union Carbide and Carbon 15.00 g.  
  under the trademark Cellosize W.P. 3&#34;. Water, q.s.p 100 g.  
  This composition is applied for minutes to chest nut hair containing 30% to 70% gray hair. After shampooing a dark chestnut shade is obtained masking the gray hair.  
 EXAMPLE 27 The same composition is prepared as in example 24 except that l2 2-5 2 :i z )&#34;lT.T. H  
  1.00 g is used instead of diethanolamide of copra The same good results are obtained as in example 24.  
 EXAMPLE 28 The same composition is prepared as in example except that iz as &#39;ls a i s l H 3.00 g is used instead of diethanolamide of copra 3.00 g The same good results are obtained as in example 25.  
 EXAMPLE 29 The following composition is prepared:  
 Dyes:  
 1,8-bis-y-aminopropylamino anthraquinone 0.15 g. ldiethylamino ethylamino 2-nitro 4-NN-dihydroxyethyl- 0.6 g.  
  amino benzene dihydro-chloride. i-N-mdthYIEIl&#39;llIlO-K-IlillJIO-lN-fl-BJIIiIIOGlZhYISJIIIIlO benzene. 0.25 g. [I-hydroxy 4-( -methylmorpholinium) propylamino 0.1 anthraquinone1methylsuliate. Z-fl-aminoethylamino anthraqninone 1,5-di-(B-aminopropylamino) anthraquinonc l-dimethylamino 3-aminoethylamino 4-n1tro benzene. l-methylamino 4 amino-propylamino anthraquinone... l-amino-propylamino anthraquinone 1,4-diamino 5-aminopropylamino anthraquinone..... 3-nltro 4-fi-aminoethylamino anisole monohydrochlonde... 0. Carrier:  
 Laurie acid Diethanolamide of copra Lauryl sodium sulfate oxyethylenated with 2 moles of 5.  
 ethylene oxide.  
 CHz-CH;  
 (R=Hydrocarbon radical derived from fatty acids of copra) (R =Nony1phenyl) ROCH3O(CH2OH) (R =Hydrocarbon radical derived from lanolin alcohols obtained by catalytic hydrogenation of lanolin) Bntyiglycol 8.00 g.  
 Monoethanolamine Hydroxyethylcellulose sold by Union Carbide and Carbon under the trademark &#34;Cellosize W.P. 3&#34;.  
 Water, q.s.p 1.00 g.  
  This composition is applied for 20 minutes to chestnut hair containing 309: to gray hair. After shampooing a dark chestnut shade is obtained masking the gray hair.  
 EXAMPLE 30 The following composition is prepared:  
 1,8-bisy-aminoprot3ylamin0 anthraquinone 0.  
 l-diethylarnino ethylamino 2-nitro 4-NN dihydroxy- 0.  
 ethylamino benzene dihydrochloride.  
 4-N-methylamino-3 nitro l-N-B aminoethylamino benzene. 0.25 g. [l-hydroxy 4-(-y methylmorphoiinium) propylamino anth- 0.1 g.  
  raquinone] methyl sulfate. 2-fl-aminoethylamino anthraquinone 0.2 g. 1,5 di-(fl-aminopropylamino) anthraquinonc 0.3 g. l-dirnethylarnino E-amino ethylamino 4-nitro benzene 0.3 g. l-methylamino 4-amino propylamino anthraquinone 0.3 g. l-amino propylamino anthraquinone 0.15 g. 1,4-diamino fi-v-aminopropylamino anthraquinone....&#39;.. 0.4 g. Carl31-nitro 4-,8-arninoethylarnino anisole monohydrochloride.. 0.2 g.  
  er: Laurlc acid 1.00 g. Diethanolamide of copra 1.00 g. Lauryl sodium sulfate oxyethylenated with 2 moles of 5.00 g.  
 diethylene oxide.  
 R-NH-OH-C O ONa C Ha-CHa 1.00 g.  
 CHz-C OIII(CH2)3N 10 CHz-CHa (R=Hydrocarbon radical derived from fatty acids of copra) RO CzHaO(OHaOH) 4.6 g. L .l.  
 (R Octylphenyl) R-o o.H.o omoH) 0.4 g.  
 l .lm  
 (R Hydrocarbon radical derived from lanolin alcohols obtained by catalytic hykrogenation of lanolin) Butylglycol 6.00 Monoethanolamine 0.00 g  
 Hydroxyethylcellulose, sold by Union Carbide and Carbon 15.00%.  
  under the trademark &#34;Cellosize W P 3&#34;. Water, q.s.p g.  
  This composition is applied for 20 minutes to chest- Continued nut hair containing 30% to 70% gray hair. After sham- R-NHCHCOONa CII2CH3 1.00 g. pooinhg a dark chestnut shade is obtained masking the g a dl CH2|1CH3 EXAMPLE 3 l (R=H3;dr0carbou radical derived from fatty acids of copra Aminohydroquinone 0.4 g.  
 2,5-dihydroxy monomcthylamirio benzene; 0.7 g. I I  
 fi-hydroxy -methyl 2,4-diaminobenzene 1.5 g. 2 s 20H)-H 5.00 g.  
 4-hydroxy 3-amino-anisole hydrochloride- 1.6 g. L. h  
 2,5-diamino 4-methy1 phenol dihydrobromide 0.5 g.  
 4-NN-diethylamino 2,6-diaminophenoltiichiorhydrate 0.6 g. (R= Hydrocarbon rad cal derived from alcohols 0b- Diethanolamide or copra 3.0 g. tam d y th catalytic hydrogenation of commercial isostearic acid) Butylglycol CHZ .C ONH (CHZ)3 N Monoethanolamine 0.60 g.  
  Hydroxyethylcellulose sold by Union Car on g. GHPGHa under the trademark Cellosize W.P. 3.  
 l 5 Water, q.s.p 100 g. (B -Hydrocarbon derived from the fatty acids of copra) C H 0 FC H O OH O This composition is applied for minutes to chest- *1: 2 i 2 nut hair containing 30% to 70% gray hair. After shamr pooing a dark chestnut shade is obtained masking the R-OLCzH3O(CHzOH) T-H 0.5 g. gray hair.  
 (R=Hydrocarbon radical derived irom lanolin alcohols EXAMPLE 34 obtained by catalyic hydrogenation of lanolin).  
 The following composition is prepared:  
 NaOH 5 N, q. 5.11. pH 7. Dyes:  
 Water, q.s.p. 100 q 1,8-biS-q aminopropylamino anthraquinone 0.15 g.  
  l-diethylamino ethylamino 2-nitro 4-NN d hydroxy- 0.6 g. ethylamino benzene dihydrochloride. This solution is mixed with its own volume of hydro- 4 N-xnethylamino-3Fmtr0 l-N-B aminoethylammo benzene- 0.25 g.  
  7 l i v [l-hydroxy 4-( methylmorpholinium) propylamino 0.1 g. gen peroxide at -0 volumes. When applied to very gray .antmaquinone methy15u1fate 2-B-aminoethy1amino anthraquinone 0.2 hair for to minutes. the result, after shampooing. l,5 dj (fi anfinopmpylammo) anthmqmnqnmu 03 IS 11 brown shade. l-dimethylamino 3-amino ethylamino 4-mtro be 0.3 g.  
  30 l-methylamino 4-amino propylamino anthraquinon 0.3 g. The hall, iiftCi treatment. IS very soft and 6215) to l-amino propylamino anthraquinone 0.15 g. 1,4-diamino 5 -aminopro ylamino anthraquinone 0.4 g. C rg-nltro 4-fl-aminoethylami no anisole monohydrochloride 0.2 g.  
 2. er: 2 Laurie acid 1.00 g. EXAMPLE 3 Eiethanolarnide oicopra. l l 1 &#34;(THE l --.f g. The following composition is prepared: 3 3 15 333 s lfate xyet yenate t 2 mo es 0 g.  
 . R-NHCHC O ONa CHz-CH: 1.00 g.  
 Celyl-stearyl alcohol 50 g CHz-COIf-(CHQPN Oleyl diethunolamide g CHHMO+CZHHO(CH2OH HImH 6 g CIOHS! GET-CH8 i R=H drocarbon radical derived from fatt acids of ZA-diumino-unisol sulfate 0.048 g 40 y Resorcine g l l Mcia-aminophenol hasc lg Nilro-para-phenylene-diumine 0.085 g RCTOZHQO (CHZOI&#39;DT Para-toluylene-diaminc I 0.004 g Sodium salt of ethylene amine tetracetic acid L000 g (R=Hydmcarbn radical derived f alcohols So wm llfiie L200 8 tained by the catalytic hydrogenation of commercial Water q.s.p. I00 g isostearic acid) Butylglycol 6 00 i;- 30 g of that composition are mixed with hydrogen Monoethanolamine 0:00 g.  
  7 I l Hydroxyethylcellulose, sold by Union Carbide and Carbon 15.00 g. peroxide umes&#39; under the trademark Cellosize W.P. 3&#34;.  
 A smooth dense cream is obtained which is of pleaswater ant USC.  
 when pp to 100% gray for 30 minutes the This composition is applied for 20 minutes to chestresult after shflmpooing and rinsing is a Pleasimt blond nut hair containing 30% to 70% gray hair. After sham-&#39; shade. The hair after treatment is very soft and easy to pooing a dark chestnut Shade is obtained masking the manage. the hair is shining. silky and pleasant to touch. gray hair.  
  XAM 33 EXAMPLE 35 The following composition is Prepared: Pcptization of barium sulfate B.hj5- .am1nopropylgmlno gnthm 1 1 1 0.15 g Barium f is preFipiEated&#39;by pouring 21.2.4 N S0- .iiiiit&#39;tiies iitamhtia iiflfi.tiihl&#34;.lllhi ifiil fnlllfihile firlin ill 4-N-methyiaminee-n1tro-l-N-fl-aminoethylamino benzene. 0.25 g. e preclpl- [il lgyadligolig-ggglggfipggpholinium) propylamino anth- 0.1g. tate is washed by simple decantat on. it is very fine and if r &#39;il lk &#39;litiii?.lii?iii?$kaiia;a:.-.. 813%: lrf ifij&#39; gf &#39;jm A greater i l dimethylamino -amln0et ylomlno 4-nitro hem 0.3 g. g product ls added to the bdnum 1-methylamino 4-amino-propylamino anthraquinon 0.3 g. sulfate liifliififi iiiiiifirtiyl313 1513220555.3135;::... 31.1  
  a jl ni tro 4-B-amin0ethy1amino anisole monohydrochloride. 0.2 g. R IO+C2HSIO(CH2OH) &#39;l&#39;i&#39; H sihiliifilfisiaaxraaeiizi:1::::::::::::::::::::::::::::: lfi: i i dcrivcd. Lauryl sodium sulfate oxyethylenated with 2 moles oi 5:00 g. from the ulcohfils obwmed y hydrogenation of mime lanolin sold under the trademark Elrolan. The other compounds in which n 2. 3 and 7.6 may also be used.  
  The product is carefully dried and is found to be prefectly wetted by oil so that it may be introduced into emulsions.  
  The example of barium sulfate is given purely by way of illustration. Other pigments such as titanium oxide. iron oxide. and Guimet blue may also be peptized.  
 EXAMPLE 36 Composition for use as lip rouge:  
 This example illustrates the use of the product:  
 R1 2 2lO(CHgOH) &#39;17 H for peptizing metallic particles.  
  H) g of *Bentone 38&#34; (trademark of National Lead Co.) which is an organophilic bentonite (as cationic colloidal earth) are dispersed in a liquid consisting of 88 g of paraffin oil and 2 g of the product (Ill) wherein the repeating unit is linear, n has a statistical average value greater than I and equal to or less than 10, R, is a hydrocarbon radical derived from a member selected from the group consisting of aliphatic and alicyclic alcohols having from eight to 30 carbon atoms said compound being present in amounts of 1-25 percent based on the weight of said pulverulent material.  
  2. The composition of claim I wherein R is a radical derived from alcohols and sterols obtained by hydrogenation of lanolin.  
  3. The composition of claim 1 in which R is a radical derived from alcohols obtained by reducing cyclic fatty acids.  
  4. The composition of claim 1 wherein said pulverulent material is a pigment.  
  5. The composition of claim 4 wherein said pigment is barium sulfate.  
  6. The composition of claim 1 including an oily liquid media selected from the group consisting of paraffin oil. vegetable oil. animal oil. modified animal oil and fatty acid esters.  
  7. A method for producing a composition having dispersed therein a solid pulverulent material selected from the group consisting of barium sulfate, titanium oxide. iron oxide. Guimet blue and aluminum particles and a compound of the formula wherein the repeating unit is linear, n has a statistical average value greater than I and equal to or less than H). R is a hydrocarbon radical derived from a member selected from the group consisting of aliphatic and alicyclic alcohols having from eight to 30 carbon atoms. said compound being present in amounts of l-25 percent based on the weight of said pulverulent material, comprising dispersing organophilic bentonite in a mixture of paraffin oil and said compound to produce a first dispersion, dispersing said first dispersion in a lip rouge base to produce a second dispersion and introducing into said second dispersion said solid pulverulent material in amount of l-l5 percent of said composition.  
  8. The method of claim 7 wherein said solid pulverulent material comprises flakes of aluminum paint.  
 Patent No. 3,877,955 Dated April 15, 1975 Inventor s Gregoire and It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:  
 In the Heading Under [30] Foreign Application Priority Data change &#34;67.13071&#34; to 130,713  
 Signed and Scaled this twenty-first D ay Of October 1975 [SEAL] Arrest:  
 RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner ofPaIenls and Trademarks