US2871193A - Shampoo compositions - Google Patents

Shampoo compositions Download PDF

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Publication number
US2871193A
US2871193A US532732A US53273255A US2871193A US 2871193 A US2871193 A US 2871193A US 532732 A US532732 A US 532732A US 53273255 A US53273255 A US 53273255A US 2871193 A US2871193 A US 2871193A
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Prior art keywords
detergent
shampoo
water
methyl cellulose
hydroxypropyl methyl
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US532732A
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Henkin Hyman
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Colgate Palmolive Co
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Colgate Palmolive Co
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/02Preparations for cleaning the hair
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/46Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
    • A61K8/463Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfuric acid derivatives, e.g. sodium lauryl sulfate
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73Polysaccharides
    • A61K8/731Cellulose; Quaternized cellulose derivatives
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/54Polymers characterized by specific structures/properties
    • A61K2800/542Polymers characterized by specific structures/properties characterized by the charge
    • A61K2800/5422Polymers characterized by specific structures/properties characterized by the charge nonionic

Definitions

  • the present invention relates to new improved shampoo compositions having, as an active or detersive component,
  • a water soluble higher fatty acid monoglyceride monosulfate detergent More particularly it is of such compositions containing hydroxypropyl methyl cellulose.
  • Shampoo compositions of many types have been forv ,mulated and various such products are on the market.
  • soap was an essential component of shampoos but'in recent years it has been largely displaced by synthetic compounds, especially organic sulfates and sulfonates, because, among other reasons, they clean the hair more thoroughly and do not form dul'ling lime soaps when used in hard water.
  • liquid shampoo compositions consisting essentially of .water soluble higher fatty acid monoglyceride monosulfate detergent and a minor proportion of water soluble hydroxypropyl methyl cellulose in an aqueous medium.
  • compositions are of a desirable viscosity; they can easily be poured but still are thick enough so that they do not flow readily through the fingers of a closed hand or drip from the hairwhen applied thereto in normal quantities; They possess a high degree of foaming power and cleanse the hair thoroughly. They do not either damage it or dry it excessively and after shampooing with these compositions the hair is still manageable.
  • the essential principal detersive ingredient is a water soluble higher fatty acid monoglyceride 'monosulfate detergent. This detergent is unique in harmlessto the hair.
  • said sulfated detergents are well-known and may be 'prethe art; it is an excellent foamer' Patented, Jan. 27, 1959 pared in any suitable manner.
  • glycerine and oleum are reacted and the mix is added to a fatty oil.
  • the resulting product, the monosulfuric acid ester of higher fatty acid monoglyceride may beneutralized with any suitable base to .form the desired water soluble detergent salt. 1 r
  • acyl group As sources of the higher fatty acyl group one may use the normal soap-making fats or mixtures thereof. Generally thosefatswill be employed whose constituent acyl groups are almost entirely within the 8 to 18 carbon atom range. Of these coconut oil is preferred, especially where a transparent shampoo is desired. 1
  • the various water soluble salts of the monosulfuric acid esterof higher fatty acid monoglyceride may be used in the invented compositions.
  • the salt forming radicals and ions the most desirableare the ammonium, alkali metal (e. g., sodium,-potassium), and lower alkylolamine containing'up to about 9 carbon atoms (e. g., mono-, diand triethanolamine).
  • the ammonium detergent salt is the preferred detersive active ingredient where clear or transparent shampoos are desired while the sodium salt is preferred for making opaque liquid shampoos such as lotion or cream shampoos.
  • compositions desirably contain a minimum of inorganic salts
  • the presence of some such salts in thereaction product is inevitable because an excess of sulfating agent must be employed which must later be neutralized.
  • this amount will constitute more than 50% of the detergent or detergent solids in the neutralized product, the terms detergent solids and detergent including active detergent, inorganic salt, and ether solubles.
  • the percentage of inorganic salt present with the active ingredient is dependent onthe amount of sulfating agent employed and the molecular weight of the neutralizing agent and valence of its salt-forming radical.
  • the inorganic salt present will have asits cation the same cation as present in the neutralized detergent but this is not necessarily the case.
  • ammonium higher fatty acid monoglyceride monosulfate-is-made by treating the corresponding sodium detergent with ammonium sulfate the inorganic salt'mixture will contain sodium sulfate too.
  • the monoglyceride monosulfate liquid'shampoo contain less than about 15% inorganic salt on a detergent solids basis the neutralized detergent will usually be freed of most of its salt content.- This may be effected by any suitable process but solvent extraction is preferred. Commercially it has been found both practicable and desirable to reduce the salt content to about 5 to 10% of the detergent solids which may often be done by a single extraction with ethanol or isopropanol.
  • the ether solubles referred to earlier comprise unreacted fat, and fatty acids obtained therefrom and from the detergent acid during the sulfation and neutralization steps in the manufacture of the monoglyceride monsulfate detergent.
  • the essential hydroxypropyl methyl cellulose component of the invented shampoos must be of the Water soluble type.
  • the methoxyl content should be between 25 and 32% and is preferably between 28 and 31%.
  • the hydroxypropyl contenbshoul d be between 2 and preferably between 2 an' l7%, and most desirably between 6 and 7%. Outside theselimitsthe hydroxypropyl methyl cellulose is either insufiiciently water soluble or else does not yield stable shampoos with the higher fatty acid monoglyceride monosulfate detergent.
  • hydroxypropyl methyl cellulose described above is known and it may be made by the usual methods of manufacturing compounds of this type. It is normally a White solid, soluble in water but insoluble in most organic solvents and more soluble in coldwater than in hot water.
  • the pH of an aqueous solution is 7 and hydroxypropyl methyl cellulose solutions are stable over a wide pH range.
  • methyl cellulose By controlling thechain length of the methyl cellulose one can secure compounds capable of producing water solutions covering a range of viscosities. Thus 2% solutions in water of suitable hydroxypropyl methyl celluloses will have viscosities ranging from averages of about 10 to 5,000 centipoises at C.
  • the hydroxypropyl methyl cellulose employed in making the shampoos of the present invention is that having an average viscosity in 2% aqueous solution (hereafter referred to only as viscosity) between 10 and 5,000 centipoises, preferably between 50 and 4,000 centipoises.
  • the resulting shampoo composition possesses many desirable properties.
  • the specific cellulose derivative inhibits excessive drying of the hair by the detergent, leaving it more easily manageable after the shampoo.
  • the viscosity or consistency of the shampoo may be varied widely by adjusting the proportions of detersive agent, the cellulose derivative and aqueous medium or by using a cellulose ether of different viscosity.
  • a thick-but flowing product of syrupy consistency can be made, or, as is more-often desired, a thinner freerflowing, but still non-spilling shampoo can be obtained by proper formulation.
  • the clear shampoos thus made are stable for prolonged periods of time, shelf lives of over 16 months at room temperature having been noted.
  • This high degree of stability is unexpected since almost all gums or gum-like materials are incompatible with the detersive agent or do not appreciably alter the viscosity V f or consistency of an aqueous solution thereof.
  • the shampoos of superior aging characteristics at room temperature but they also are more stable at elevated temperatures. Even under a'rigoro-us testing at 110 F., a temperature to which they will be subjected in some localities or under certain transportation or storage conditions, they are still stable, showing no separation, even afte'r-as long as a year. Based on past experience with fatty acid monoglyceride monosulfate detergent shampoos this higher temperature aging test indicates that the compositions will be stable at average room temperatures for over 4 years. i
  • the monolyceride monosulfate detergent andhydroxypropyl methyl cellulose should both be employed within certain ranges of concentrations and proportions. There is no problem in making the specific detergent solutions of optimum viscosity when less than 5% detergent is employed. However solution concentrations of that level are deficient in cleansing power. They are not satisfactory When compared to shampoos of greater detergent content and are considered commercially unacceptable. Detergent solutions' having over 35% higher fatty acid monoglyceride monosulfate detergent will often gel, becoming unpourable and unsalable. Even when the detergent used does not gel at such high concentrations it tends to become cloudy and often a flocculent material separates out, adversely affecting the appearance of the shampoo. In general, therefore, the shampoo compositions of the present invention should contain about 5 to 35%, usually 10 to 35% and preferably 10 to 25% by Weight of detergent for optimum elfectiveness.
  • the quantity of hydroxypropyl methyl cellulose used will be between 0.1 and 5%, preferably between 0.2 and 2% by weight. Below 0.1% no appreciable viscosity regulating or increasing of hair manageability are noted. Above 5% the shampoos tend to become gummy and gel, thus destroying the essential character of the product as a smooth, homogeneous, pourable liquid.
  • the amount of hydroxypropyl methyl cellulose in the present composition should be chosen relative to the concentration of detergent and to the viscosity of the cellulose derivative employed, as well as with respect to the desired viscosity or thickness of the shampoo to be made. Thus if a high viscosity hydroxypropyl methyl cellulose is used less will be required to produce a shampoo of iven viscosity than will be needed of a corresponding low viscosity cellulose compound. Other factors must also be considered. While it is possible to make a thick shampoo having as much as 5% hydroxypropyl methyl cellulose of 10 centipoise viscosity, 5% of 4,000 centipoise material would not dissolve completely and would make a gelled, rather than a liquid shampoo.
  • the inorganic salt present with the detergent also exerts an insolubilizing effect on the cellulose compound and consequently the less salt present the more cellulose compound may be added. It has been noted that the high viscosity hydroxypropyl methyl celluloses are-less soluble in the presence of inorganic salts than are the lower viscosity compounds.
  • ionizable salts do tend to decrease the stability of the present shampoos the effect thereof is much less than is the case when similar useful cellulose derivatives, e. g., methyl cellulose, are employed.
  • Shampoos made according to the present invention, but in which methyl cellulose replaces hydroxypropyl methyl cellulose are stable at ordinary temperatures but when subjected to high temperature storage (at F.) these shampoos separate.
  • Novel clear shampoos of this invention do not separate or break down at 110 F, even after more than a years aging. Greater stability of the product contain hydroxypropyl methyl cellulose products is most significant when the shampoo compositions contain from about 1.0 to 2.5% inorganic salt, e. g., ammonium sulfate, sodium sulfate.
  • urea in a preferred embodiment of the present invention between 1% and 5% urea is added to the aforementioned essential ingredients.
  • the urea has been found to stabilize the present shampoo compositions, increasing the shelf life, raising the permissible upper storage temperature and improving the tolerance of the shampoo for inorganic salts.
  • the urea maintains the pH of the composition between 5 and 7.5 preferably on the acid side and thereby inhibits hydrolytic decomposition of the detersive ingredient.
  • from 0.1 to 10%, preferably from 1 to 10%, of higher fatty acid dialkylolamide may be used in admixture with the organic detergent and hydroxypropyl methyl cellulose to further improve the hair manageability properties of the shampoo and increase its viscosity or consistency.
  • the higher fatty acyl group should contain about 10 to 18 carbon atoms and the alkylol groups should have no more than about 5 carbon atoms each.
  • the preferred compounds are those wherein the fatty acyl radical has 12 to 14 carbon atoms and each alkylol group has 2 to 3 carbon atoms.
  • dialkylolamide compounds find greatest utility in liquid cream shampoos or lotion shampoos because on aging they tend to cloud clear liquid shampoos, thereby detracting somewhat from their appearance.
  • Various adjuvant materials may be present in the present shampoo compositions and these should be selected so as to be compatible with the shampoo.
  • perfume and coloring material, wetting agents, hair conditioners or superfatting agents such as lanolin, fatty alcohols, fatty acids, fatty amides, etc.
  • perfume and coloring material, wetting agents, hair conditioners or superfatting agents such as lanolin, fatty alcohols, fatty acids, fatty amides, etc.
  • Minor amounts of watersolublephosphates such as disodium phosphate, sodium tripolyphosphate, or other compounds such as the water soluble salts of ethylene diamine tetra-acetic acid may be added for their sequestering activity.
  • Preservatives might ,be needed to inhibit mold, fungus and bacterial growth.
  • Solvents such as ethanol and isopropanol may be employed to help solubilize dyes, perfumes, etc.
  • the invented shampoo compositions may be made in any suitable liquid state pourable at room temperature. Generally the thinner of these liquids will have a viscosity of about 50 centipoises at 80 F.
  • the flow time which is by definition the time in seconds that it takes a volume of shampoo to flow by gravity out of .a certain cylindrical container under a certain liquid head through a standard tube is a more accurate measure than viscosity of the flow characteristics of a shampoo of importance to the consumer because it measures all flow resisting forces, not just the resistance of the liquid to shear.
  • the flow time is determined in the following manner.
  • a graduated glass 100 milliliter cylinder with the bottom removed, of 24 centimeters length and 2.5 cm. internal diameter is held vertically. Both ends of the cylinder are open.
  • a No. 2 rubber stopper is used to close off the lower opening; the stopper is bored axially and in the hole is inserted a metal tube of 14 cm. length and 4 millimeters inside diameter, leading from a point near the bottom of the cylinder to the atmosphere.
  • the cylinder is filled to the 100 ml. mark with shampoo, the metal tube also being filled, and being closed off at its outlet.
  • the outlet is opened and the time is recorded when ml. shampoo have flowed out the cylinder.
  • the time is again recorded when 60 ml. have been drained.
  • the difference is the flow time.
  • the liquid at the 10 ml. height is 15.8 cm. above the tube top and at the 60 ml. height is only 6.3 cm. above that point.
  • Water at 80 F. has a flow time of 3 seconds while the present shampoos will flow in about 15 to 700 seconds, preferably from 15 to 200 seconds at the same temperature.
  • Either clear, i. e., transparent liquid shampoos or liquid cream shampoos may be made.
  • the hydroxypropyl methyl cellulose should preferably first be dispersed in hot water and then be dissolved by cooling the water or by adding a sufficient amount of cold water.
  • the various additives desired may be dispersed or dissolved in the aqueous detergent base (which may contain both water and alcohol) and finally the hydroxypropyl methyl cellulose solution may be added to the solution of the detergent base.
  • shampoos made from ingredients unadulterated with cloud-forming impurities are clear and sparkling. If a filtration step is considered desirable to remove insoluble impurities which sometimes might be in the various ingredients the shampoo will be found filterable and the resulting shampoos will be transparent.
  • an opaque emulsion of the oil-in-water type is usually formed although other well-known methods may be used to secure opacity- Since the detersive agent and the hydrox'y propyl methyl cellulose will be in the water phase it is desirable to have present an oil-like material to form the oil phase.
  • a recognized opacifying agent e. g., behenic acid or other such agent selected for its compatibility with the monoglyceride monosulfate detergent is utilized in conjunction with a stabilizing agent, e. g. hydrogenated castor oil having a melting point above F.
  • the liquid cream shampoos are made by dissolving or dispersing the detergent and other water soluble adjuvant material in Water, mixing that solution with the hydroxypropyl methyl cellulose solution, heating, melting the oil soluble additives together and admixing the fluid oil soluble materials with the detergent-cellulose derivative solution, after which the shampoo is perfumed.
  • long chain fatty and other acids in the compositions may be partially neutralized by addition of small amounts of alkali, preferably an alkylomaine such as mono-, diand triethanolamine, monoisopropanolamine, etc., but alkali metal hydroxides such as sodium and potassium hydroxide may also be employed.
  • The' shampoo pH may be adjusted by addition of an appropriate agent, e. g. citric acid, phosphates, and urea may also be present.
  • the hydroxypropyl methyl cellulose in the liquid cream shampoos stabilizes the emulsion and so helps prevent the unattractive separation of oily and aqueous layers.
  • the filling of containers with lotion shampoos containing hydroxypropyl methyl cellulose is easier because that product does not splash and entrap air in filling while a similar product without hydroxypropyl methyl cellulose does, causing the shampoo to be heterogeneous and less attractive.
  • the total amount of water will usually be above 50% and preferably over 60% for optimum results.
  • Example I The following composition is a clear shampoo:
  • Ammonium salt of coconut oil fatty acids monoglyceride monosulfate detergent contains about 10% ammonium sulfate and about 10% ether soluble material due to the method of manufacture.
  • This compound contains from 2 to 4% hydroxypropoxy groups and about 30% methoxy groups and has a viscosity of 4,000 centipoises.
  • the detergent, ethanol and some of the water are obtained from alcoholic extraction of detergent product as a solution or concentrate comprising 40% detergent solids, 17.7% ethanol and 42.3% water.
  • the urea is dissolved in 52.6 parts of this concentrate and the perfume is also added thereto.
  • the hydroxypropyl methyl cellulose is dispersed in 44.6 parts of water at 180 F. and then the dispersion is cooled to room temperature at which the cellulose derivative dissolves.
  • the detergent, urea and perfume mixture is then admixed with the hydroxypropyl methyl cellulose solution to form a substantially clear shampoo solution.
  • the shampoo is filtered to remove insoluble materials found in the perfume, water, and other ingredients. product resulting is sparkling clear. It is stable at room Such filtration 'is effected easily and thetemperature for over 16 months and even can be kept at temperatures as high as 110 F. for as long as a year without clouding or separating.
  • the above shampoo is more stable, has a superior desired consistency (23 seconds flow time corresponding to about 70 centipoises at 20 C.) and leaves the hair more easily manageable than a similar shampoo without hydroxypropyl methyl cellulose.
  • a liquid shampoo is prepared by the same method and of the same formula except that 1.0% hydroxypropyl methyl cellulose containing 6 to 7% hydroxypropoxy groups and about 29% methoxy groups and having a viscosity of 50 centipoises is substituted for the hydroxypropyl methyl cellulose of Example I, the amount of Water being correspondingly decreased.
  • This shampoo is clear, of desirable consistency (2 seconds how time which corresponds to about 70 centipoises viscosity), filterable, stable and leaves the hair manageable.
  • Another stable clear liquid shampoo may be made according to the above method and formula except that 0.5% of hydroxypropyl methyl cellulose containing about 6 to 7% hydroxypropoxy groups and about 29% methoxy groups and having a viscosity of 3,000 centipoises is used in place of the foregoing hydroxypropyl methyl celluloses and the formula amount of water is adjusted accordingly.
  • the shampoo prepared is characterized by a desirable consistency (49 seconds fiow time) and good hair manageability properties.
  • Example II A clear thickened shampoo of desirable consistency may be made of the following formula:
  • the dry sodium salt of coconut oil fatty acids monoglycll'ldQ monosull'ate detergent containing about 10% sodium sulfate and about 10% other soluble mat in 'Tllit; compound contains from 2 to 4 hydroxyprn x3 groups and about 30% inethoxy groups Lid has a, viscosity of -l,000 ccutipouss.
  • the hydroxypropyl methyl cellulose is dispersed in about /3 of the water at about 170 F. and the dispersion is cooled to room temperature to promote solution of the cellulose derivative.
  • the detergent is dissolved in the remainder of the water and the solutions are admixed.
  • Example III A liquid cream (lotion) shampoo is made according to the formula:
  • This compound contains from 2 to 4% hydroxypropoxy groups and about 30% niethoxy groups and has a viscosity of 1.000 ccnl'looises.
  • the dry sodium salt of coconut oil fatty acids monoglycorido monosulfate detergent containing about 10% sodium sulfate and about 10% ether soluble material.
  • the hydroxypropyl methyl cellulose solution A is made by dispersing the cellulose compound in about 73 of the water at about 190 F, cooling the dispersion to about room temperature by adding the remaining water as ice and stirring until dissolved.
  • detergent solution B The components of detergent solution B are mixed together and added to solution A, after which AB is heated to 180 F. at which temperature it is a solution.
  • the citric acid of group C is dissolved in the water and the triethanolamine is added to the solution, generating heat, after which C is added to AB.
  • Group D comprises oil soluble materials. These are melted and heated to 200 F. and then the melt is added carefully to the solution of combined groups A, B andC. After cooling the emulsion to about F. perfume is added and stirred in.
  • the resulting product is of a desirable consistency, having a how time of 128 seconds.
  • the shampoo has an attractive pearly sheen. It is an excellent free-flowing shampoo product having very good detersive properties while still leaving the washed hair manageable.
  • a similar shampoo containing 0.5% of the same hydroxypropyl methyl cellulose and prepared in the same manner has a flow time of 662 seconds while the flow time of a control shampoo with no cellulose derivative added is only 16.5 seconds.
  • the term consisting essentially of as used in the definition of the ingredients present in the claimed composition is intended to exclude the presence of other materials in such amounts as will interfere substantially with the properties and characteristics possessed by the composition as set forth but to permit the presence of other materials in such amounts as will not substantially affect adversely such properties and characteristics.
  • a liquid shampoo composition consisting essentially of about 5 to 35 of a Water soluble higher fatty acid monoglyceride monosulfate detergent and about 0.1 to 5% of a water soluble hydroxypropyl methyl cellulose in an aqueous medium therefor, the said cellulose derivative having a methoxy content of 25 to 32% and an hydr0xypropoxy content of 2 to 10% and having a viscosity between 10 and 5,000 centipoises as determined at 2% solution in Water at 20 C.
  • a liquid cream shampoo composition consisting essentially of about 10 to 35% of a sodium higher fatty acid monoglyceride monosulfate detergent, about 0.5 to 10% opacifying agent and about 0.1 to 5% of a water soluble hydroxypropyl methyl cellulose in an aqueous medium therefor, the said cellulose derivative having a methoxy content of 25 to 32% and an hydroxypropoxy content of 2 to 10% and having a viscosity between 10 and 5,000 centipoises as determined at 2% solution in Water at 20 C.
  • a clear liquid shampoo composition consisting essentially of about 10 to 35% of an ammonium higher fatty acid monoglyceride monosulfate detergent and about 0.1 to of a water soluble hydroxypropyl methyl cellulose in an aqueous medium therefor, the said cellulose derivative having a methoxy content of 25 to 32% and an hydroxypropoxy content of 2 to and having a viscosity between 10 and 5,000 centipoises as determined at 2% solution in water at C.
  • a clear liquid shampoo consisting essentially of about 10 to of an ammonium higher fatty acid monoglyceride monosulfate detergent and about 0.2 to 2% of a water soluble hydroxypropyl methyl cellulose in an aqueous medium therefor, the said cellulose derivative having a methoxy content of 28 to 31% and an hydroxypropoxy content of 2 to 7% and having a viscosity between 50 and 4,000 centipoises as determined at 2% solution in water at 20 C.
  • a clear liquid shampoo composition consisting essentially of about 10 to 35% of an ammonium higher fatty acid monoglyceride monosulfate detergent, from about 1 to 2.5% inorganic salt and from 0.1 to 5% of a water soluble hydroxypropyl methyl cellulose in an aqueous medium therefor, the said cellulose derivative having a methoxy content of 25 to 32% and an hydroxypropoxy content of 2 to 10% and having a viscosity between 50 and 4,000 centipoises as determined at 2% solution in water at 20 C.
  • a liquid shampoo composition consisting essentially of about 10 to 35% of a higher fatty acid monoglyceride monosulfate detergent, about 1 to 5% of urea, and about 0.1 to 5% of a water soluble hydroxypropyl methyl cellulose in an aqueous medium therefor, the said cellulose derivative having a methoxy content of 25 to 32% and an hydroxypropoxy content of 2 to 10% and having a viscosity between 10 and 5,000 centipoises as determined at 2% solution in water at 20 C.
  • a liquid cream shampoo composition consisting essentially of about 10 to 35% of a sodium higher fatty acid monoglyceride monosuliate detergent, about 0.5 to 10% opacifying agent, about 0.1 to 10% of a higher fatty acyl di-lower alkylolamide having about 12 to 14 carbon atoms in the fatty acyl group thereof and about 0.1 to 5% of a water soluble hydroxypropyl methyl cellulose in an aqueous medium therefor, the said cellulose derivative having a methoxy content of 25 to 32% and an hydroxy-- propoxy content of 2 to 10% and having a viscosity between 10 and 5,000 centipoises as determined at 2% solution in water at 20 C.
  • a clear liquid shampoo composition consisting essentially of about 10 to 25 of an ammonium higher fatty acid monoglyceride monosulfate detergent, about 1 to 5% of urea and about 0.2 to 2% of a water soluble hydroxypropyl methyl cellulose in an aqueous medium therefor, the said cellulose derivative having a methoxy content of 28 to 31% and a hydroxypropoxy content of 2 to 7% and having a viscosity between and 4,000 centipoises as determined at 2% solution in water at 20 C.

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Description

- and cleanser'while still being United States Patent 1 2,871,193 SHAMPOO COMPOSITIONS Hyman Henkin, Bayside, N. Y., assignor to Colgate-Palmolive Company, Jersey City, N. J., acorporation of Delaware No. Drawing. Application September 6, 1955 Serial N 0. 532,732
8 Claims. or. 252-152 The present invention relates to new improved shampoo compositions having, as an active or detersive component,
a water soluble higher fatty acid monoglyceride monosulfate detergent. More particularly it is of such compositions containing hydroxypropyl methyl cellulose.
Shampoo compositions of many types have been forv ,mulated and various such products are on the market.
Originally soap was an essential component of shampoos but'in recent years it has been largely displaced by synthetic compounds, especially organic sulfates and sulfonates, because, among other reasons, they clean the hair more thoroughly and do not form dul'ling lime soaps when used in hard water.
The different chemical nature of the synthetic detergents, the very cause of these compounds being shampoo ingredients superior to soap, also often results in shampoos made therefrom having certain undesirable properties not with agents to improve hair manageability, thickeners,
and the'like. Sometimes these additives react with the other shampoo ingredients yielding precipitates or causing cloudiness (in clear shampoos). Because they are quite different chemically from each other, as well as from the soaps, itis clear that each shampoo active detergent ingredient and each specific formulation involves problems peculiar to itself. Consequently improvements in formulas are not necessarily considered in the art to be generally applicable but, rather, to a large extent are specific to the particular formulation and detergent employed.
In accordance with the present invention there are provided liquid shampoo compositions consisting essentially of .water soluble higher fatty acid monoglyceride monosulfate detergent and a minor proportion of water soluble hydroxypropyl methyl cellulose in an aqueous medium.
Such compositions are of a desirable viscosity; they can easily be poured but still are thick enough so that they do not flow readily through the fingers of a closed hand or drip from the hairwhen applied thereto in normal quantities; They possess a high degree of foaming power and cleanse the hair thoroughly. They do not either damage it or dry it excessively and after shampooing with these compositions the hair is still manageable. In the novel compositionsof this invention-the essential principal detersive ingredient is a water soluble higher fatty acid monoglyceride 'monosulfate detergent. This detergent is unique in harmlessto the hair. The
said sulfated detergents are well-known and may be 'prethe art; it is an excellent foamer' Patented, Jan. 27, 1959 pared in any suitable manner. According to one method glycerine and oleum are reacted and the mix is added to a fatty oil. The resulting product, the monosulfuric acid ester of higher fatty acid monoglyceride may beneutralized with any suitable base to .form the desired water soluble detergent salt. 1 r
As sources of the higher fatty acyl group one may use the normal soap-making fats or mixtures thereof. Generally thosefatswill be employed whose constituent acyl groups are almost entirely within the 8 to 18 carbon atom range. Of these coconut oil is preferred, especially where a transparent shampoo is desired. 1
The various water soluble salts of the monosulfuric acid esterof higher fatty acid monoglyceride may be used in the invented compositions. Among the salt forming radicals and ions the most desirableare the ammonium, alkali metal (e. g., sodium,-potassium), and lower alkylolamine containing'up to about 9 carbon atoms (e. g., mono-, diand triethanolamine). The ammonium detergent salt is the preferred detersive active ingredient where clear or transparent shampoos are desired while the sodium salt is preferred for making opaque liquid shampoos such as lotion or cream shampoos.
While the invented compositions desirably contain a minimum of inorganic salts, in the making of the active detergent ingredient according to the above method the presence of some such salts in thereaction product is inevitable because an excess of sulfating agent must be employed which must later be neutralized. Generally this amount will constitute more than 50% of the detergent or detergent solids in the neutralized product, the terms detergent solids and detergent including active detergent, inorganic salt, and ether solubles. The percentage of inorganic salt present with the active ingredient is dependent onthe amount of sulfating agent employed and the molecular weight of the neutralizing agent and valence of its salt-forming radical. Usually the inorganic salt present will have asits cation the same cation as present in the neutralized detergent but this is not necessarily the case. For instance where ammonium higher fatty acid monoglyceride monosulfate-is-made by treating the corresponding sodium detergent with ammonium sulfate the inorganic salt'mixture will contain sodium sulfate too. Because it is generally desirable that the monoglyceride monosulfate liquid'shampoo contain less than about 15% inorganic salt on a detergent solids basis the neutralized detergent will usually be freed of most of its salt content.- This may be effected by any suitable process but solvent extraction is preferred. Commercially it has been found both practicable and desirable to reduce the salt content to about 5 to 10% of the detergent solids which may often be done by a single extraction with ethanol or isopropanol.
The ether solubles referred to earlier comprise unreacted fat, and fatty acids obtained therefrom and from the detergent acid during the sulfation and neutralization steps in the manufacture of the monoglyceride monsulfate detergent. The ether solubles with the detergent should be less than about 10% of the detergent soilds.- If 'the ether= soluble content of the detergent is appreciably. higher than 10% of the detergent the. stability of the shampoo made will be impaired and its initial cloud point will be high. Afhigher cloud point means that the de-' tergent will become cloudy (from ether solublesseparating) when cooledonly slightly. Thus it will not be, able to withstand cooling without losing clarity. On aging the product will tend to become unduly dark in color and,
if originally a sparkling clear shampoo, will often become cloudy or separate; In addition the higher ether soluble content of the detergent will, together with the necessary oils, fatty, acids and .waxes added as perfumes, opacifier (when I desired) and emollient, diminish the foaming power ofthe shampoo below an acceptable limit.
The essential hydroxypropyl methyl cellulose component of the invented shampoos must be of the Water soluble type. The methoxyl content should be between 25 and 32% and is preferably between 28 and 31%. The hydroxypropyl contenbshoul d be between 2 and preferably between 2 an' l7%, and most desirably between 6 and 7%. Outside theselimitsthe hydroxypropyl methyl cellulose is either insufiiciently water soluble or else does not yield stable shampoos with the higher fatty acid monoglyceride monosulfate detergent.
The hydroxypropyl methyl cellulose described above is known and it may be made by the usual methods of manufacturing compounds of this type. It is normally a White solid, soluble in water but insoluble in most organic solvents and more soluble in coldwater than in hot water. The pH of an aqueous solution is 7 and hydroxypropyl methyl cellulose solutions are stable over a wide pH range.
By controlling thechain length of the methyl cellulose one can secure compounds capable of producing water solutions covering a range of viscosities. Thus 2% solutions in water of suitable hydroxypropyl methyl celluloses will have viscosities ranging from averages of about 10 to 5,000 centipoises at C.
The hydroxypropyl methyl cellulose employed in making the shampoos of the present invention is that having an average viscosity in 2% aqueous solution (hereafter referred to only as viscosity) between 10 and 5,000 centipoises, preferably between 50 and 4,000 centipoises.
When hydroxypropyl methyl cellulose and higher. fatty acid monoglyceride monosulfate detergent are used in combination in the proper proportions in a suitable aqueous medium the resulting shampoo composition possesses many desirable properties. The specific cellulose derivative inhibits excessive drying of the hair by the detergent, leaving it more easily manageable after the shampoo. In addition the viscosity or consistency of the shampoo may be varied widely by adjusting the proportions of detersive agent, the cellulose derivative and aqueous medium or by using a cellulose ether of different viscosity. Thus a thick-but flowing product of syrupy consistency can be made, or, as is more-often desired, a thinner freerflowing, but still non-spilling shampoo can be obtained by proper formulation. The clear shampoos thus made are stable for prolonged periods of time, shelf lives of over 16 months at room temperature having been noted. This high degree of stability is unexpected since almost all gums or gum-like materials are incompatible with the detersive agent or do not appreciably alter the viscosity V f or consistency of an aqueous solution thereof. Not only are the shampoos of superior aging characteristics at room temperature but they also are more stable at elevated temperatures. Even under a'rigoro-us testing at 110 F., a temperature to which they will be subjected in some localities or under certain transportation or storage conditions, they are still stable, showing no separation, even afte'r-as long as a year. Based on past experience with fatty acid monoglyceride monosulfate detergent shampoos this higher temperature aging test indicates that the compositions will be stable at average room temperatures for over 4 years. i
To secure a satisfactory shampoo the monolyceride monosulfate detergent andhydroxypropyl methyl cellulose should both be employed within certain ranges of concentrations and proportions. There is no problem in making the specific detergent solutions of optimum viscosity when less than 5% detergent is employed. However solution concentrations of that level are deficient in cleansing power. They are not satisfactory When compared to shampoos of greater detergent content and are considered commercially unacceptable. Detergent solutions' having over 35% higher fatty acid monoglyceride monosulfate detergent will often gel, becoming unpourable and unsalable. Even when the detergent used does not gel at such high concentrations it tends to become cloudy and often a flocculent material separates out, adversely affecting the appearance of the shampoo. In general, therefore, the shampoo compositions of the present invention should contain about 5 to 35%, usually 10 to 35% and preferably 10 to 25% by Weight of detergent for optimum elfectiveness.
The quantity of hydroxypropyl methyl cellulose used will be between 0.1 and 5%, preferably between 0.2 and 2% by weight. Below 0.1% no appreciable viscosity regulating or increasing of hair manageability are noted. Above 5% the shampoos tend to become gummy and gel, thus destroying the essential character of the product as a smooth, homogeneous, pourable liquid.
The amount of hydroxypropyl methyl cellulose in the present composition should be chosen relative to the concentration of detergent and to the viscosity of the cellulose derivative employed, as well as with respect to the desired viscosity or thickness of the shampoo to be made. Thus if a high viscosity hydroxypropyl methyl cellulose is used less will be required to produce a shampoo of iven viscosity than will be needed of a corresponding low viscosity cellulose compound. Other factors must also be considered. While it is possible to make a thick shampoo having as much as 5% hydroxypropyl methyl cellulose of 10 centipoise viscosity, 5% of 4,000 centipoise material would not dissolve completely and would make a gelled, rather than a liquid shampoo. The inorganic salt present with the detergent also exerts an insolubilizing effect on the cellulose compound and consequently the less salt present the more cellulose compound may be added. It has been noted that the high viscosity hydroxypropyl methyl celluloses are-less soluble in the presence of inorganic salts than are the lower viscosity compounds.
While ionizable salts do tend to decrease the stability of the present shampoos the effect thereof is much less than is the case when similar useful cellulose derivatives, e. g., methyl cellulose, are employed. Shampoos made according to the present invention, but in which methyl cellulose replaces hydroxypropyl methyl cellulose are stable at ordinary temperatures but when subjected to high temperature storage (at F.) these shampoos separate. Novel clear shampoos of this invention do not separate or break down at 110 F, even after more than a years aging. Greater stability of the product contain ing hydroxypropyl methyl cellulose products is most significant when the shampoo compositions contain from about 1.0 to 2.5% inorganic salt, e. g., ammonium sulfate, sodium sulfate. With the above guiding information in mind it is within the ability of one skilled in the art in light of specific examples to be given subsequently to formulate the smooth, homogeneous pourable liquid shampoos of this invention without difficulty if care is taken that the amount of the cellulose derivative incorporated in the shampoo is sufiiciently soluble.
In a preferred embodiment of the present invention between 1% and 5% urea is added to the aforementioned essential ingredients. The urea has been found to stabilize the present shampoo compositions, increasing the shelf life, raising the permissible upper storage temperature and improving the tolerance of the shampoo for inorganic salts. In addition the urea maintains the pH of the composition between 5 and 7.5 preferably on the acid side and thereby inhibits hydrolytic decomposition of the detersive ingredient.
In another preferred embodiment of the invention from 0.1 to 10%, preferably from 1 to 10%, of higher fatty acid dialkylolamide may be used in admixture with the organic detergent and hydroxypropyl methyl cellulose to further improve the hair manageability properties of the shampoo and increase its viscosity or consistency. The higher fatty acyl group should contain about 10 to 18 carbon atoms and the alkylol groups should have no more than about 5 carbon atoms each. The preferred compounds are those wherein the fatty acyl radical has 12 to 14 carbon atoms and each alkylol group has 2 to 3 carbon atoms. Examples of such suitable materials are lauroyl' diethanolamide, myristoyl diethanolamide, lauroyl myristoyl diethanolamide (a mixture), lauroyl dipropanolamide, lauroyl diglycerylamide, and the like. The dialkylolamide compounds find greatest utility in liquid cream shampoos or lotion shampoos because on aging they tend to cloud clear liquid shampoos, thereby detracting somewhat from their appearance.
Various adjuvant materials may be present in the present shampoo compositions and these should be selected so as to be compatible with the shampoo. Thus perfume and coloring material, wetting agents, hair conditioners or superfatting agents such as lanolin, fatty alcohols, fatty acids, fatty amides, etc., may be used in minor proportions but the total thereof should preferably not exceed about 5%. Minor amounts of watersolublephosphates such as disodium phosphate, sodium tripolyphosphate, or other compounds such as the water soluble salts of ethylene diamine tetra-acetic acid may be added for their sequestering activity. Preservatives might ,be needed to inhibit mold, fungus and bacterial growth. Solvents such as ethanol and isopropanol may be employed to help solubilize dyes, perfumes, etc.
The invented shampoo compositions may be made in any suitable liquid state pourable at room temperature. Generally the thinner of these liquids will have a viscosity of about 50 centipoises at 80 F. The flow time, which is by definition the time in seconds that it takes a volume of shampoo to flow by gravity out of .a certain cylindrical container under a certain liquid head through a standard tube is a more accurate measure than viscosity of the flow characteristics of a shampoo of importance to the consumer because it measures all flow resisting forces, not just the resistance of the liquid to shear.
The flow time is determined in the following manner. A graduated glass 100 milliliter cylinder with the bottom removed, of 24 centimeters length and 2.5 cm. internal diameter is held vertically. Both ends of the cylinder are open. A No. 2 rubber stopper is used to close off the lower opening; the stopper is bored axially and in the hole is inserted a metal tube of 14 cm. length and 4 millimeters inside diameter, leading from a point near the bottom of the cylinder to the atmosphere. The cylinder is filled to the 100 ml. mark with shampoo, the metal tube also being filled, and being closed off at its outlet. The outlet is opened and the time is recorded when ml. shampoo have flowed out the cylinder. The time is again recorded when 60 ml. have been drained. The difference is the flow time. The liquid at the 10 ml. height is 15.8 cm. above the tube top and at the 60 ml. height is only 6.3 cm. above that point.
Water at 80 F. has a flow time of 3 seconds while the present shampoos will flow in about 15 to 700 seconds, preferably from 15 to 200 seconds at the same temperature.
Either clear, i. e., transparent liquid shampoos or liquid cream shampoos may be made. In either case the hydroxypropyl methyl cellulose should preferably first be dispersed in hot water and then be dissolved by cooling the water or by adding a sufficient amount of cold water. When making clearshampoo compositions the various additives desired may be dispersed or dissolved in the aqueous detergent base (which may contain both water and alcohol) and finally the hydroxypropyl methyl cellulose solution may be added to the solution of the detergent base. Shampoos made from ingredients unadulterated with cloud-forming impurities are clear and sparkling. If a filtration step is considered desirable to remove insoluble impurities which sometimes might be in the various ingredients the shampoo will be found filterable and the resulting shampoos will be transparent.
To manufacture liquid cream shampoos an opaque emulsion of the oil-in-water type is usually formed although other well-known methods may be used to secure opacity- Since the detersive agent and the hydrox'y propyl methyl cellulose will be in the water phase it is desirable to have present an oil-like material to form the oil phase. Generally about /2 to 10% of a recognized opacifying agent, e. g., behenic acid or other such agent selected for its compatibility with the monoglyceride monosulfate detergent is utilized in conjunction with a stabilizing agent, e. g. hydrogenated castor oil having a melting point above F.
Normally the liquid cream shampoos are made by dissolving or dispersing the detergent and other water soluble adjuvant material in Water, mixing that solution with the hydroxypropyl methyl cellulose solution, heating, melting the oil soluble additives together and admixing the fluid oil soluble materials with the detergent-cellulose derivative solution, after which the shampoo is perfumed. If desired, long chain fatty and other acids in the compositions may be partially neutralized by addition of small amounts of alkali, preferably an alkylomaine such as mono-, diand triethanolamine, monoisopropanolamine, etc., but alkali metal hydroxides such as sodium and potassium hydroxide may also be employed. The' shampoo pH may be adjusted by addition of an appropriate agent, e. g. citric acid, phosphates, and urea may also be present.
The hydroxypropyl methyl cellulose in the liquid cream shampoos stabilizes the emulsion and so helps prevent the unattractive separation of oily and aqueous layers. In addition the filling of containers with lotion shampoos containing hydroxypropyl methyl cellulose is easier because that product does not splash and entrap air in filling while a similar product without hydroxypropyl methyl cellulose does, causing the shampoo to be heterogeneous and less attractive.
In either the clear or opaque liquid shampoos the total amount of water will usually be above 50% and preferably over 60% for optimum results.
The following specific examples are further illustrative of the present invention but the invention is not to be limited thereby. All amounts or percentages throughout this specification and in the claims are by weight unless otherwise indicated.
Example I The following composition is a clear shampoo:
' Percent Detergent 21.0 As detergent Ethanol 9.3 concentrate: Water 22.3 52.6% Hydroxypropyl methyl cellulose 0.4 Urea 2.0 Perfume 0.4 Water 44.6
Ammonium salt of coconut oil fatty acids monoglyceride monosulfate detergent. It contains about 10% ammonium sulfate and about 10% ether soluble material due to the method of manufacture.
This compound contains from 2 to 4% hydroxypropoxy groups and about 30% methoxy groups and has a viscosity of 4,000 centipoises.
The detergent, ethanol and some of the water are obtained from alcoholic extraction of detergent product as a solution or concentrate comprising 40% detergent solids, 17.7% ethanol and 42.3% water. The urea is dissolved in 52.6 parts of this concentrate and the perfume is also added thereto. The hydroxypropyl methyl cellulose is dispersed in 44.6 parts of water at 180 F. and then the dispersion is cooled to room temperature at which the cellulose derivative dissolves. The detergent, urea and perfume mixture is then admixed with the hydroxypropyl methyl cellulose solution to form a substantially clear shampoo solution. The shampoo is filtered to remove insoluble materials found in the perfume, water, and other ingredients. product resulting is sparkling clear. It is stable at room Such filtration 'is effected easily and thetemperature for over 16 months and even can be kept at temperatures as high as 110 F. for as long as a year without clouding or separating.
The above shampoo is more stable, has a superior desired consistency (23 seconds flow time corresponding to about 70 centipoises at 20 C.) and leaves the hair more easily manageable than a similar shampoo without hydroxypropyl methyl cellulose.
A liquid shampoo is prepared by the same method and of the same formula except that 1.0% hydroxypropyl methyl cellulose containing 6 to 7% hydroxypropoxy groups and about 29% methoxy groups and having a viscosity of 50 centipoises is substituted for the hydroxypropyl methyl cellulose of Example I, the amount of Water being correspondingly decreased. This shampoo is clear, of desirable consistency (2 seconds how time which corresponds to about 70 centipoises viscosity), filterable, stable and leaves the hair manageable.
Another stable clear liquid shampoo may be made according to the above method and formula except that 0.5% of hydroxypropyl methyl cellulose containing about 6 to 7% hydroxypropoxy groups and about 29% methoxy groups and having a viscosity of 3,000 centipoises is used in place of the foregoing hydroxypropyl methyl celluloses and the formula amount of water is adjusted accordingly. The shampoo prepared is characterized by a desirable consistency (49 seconds fiow time) and good hair manageability properties.
Example II A clear thickened shampoo of desirable consistency may be made of the following formula:
The dry sodium salt of coconut oil fatty acids monoglycll'ldQ monosull'ate detergent containing about 10% sodium sulfate and about 10% other soluble mat in 'Tllit; compound contains from 2 to 4 hydroxyprn x3 groups and about 30% inethoxy groups Lid has a, viscosity of -l,000 ccutipouss.
The hydroxypropyl methyl cellulose is dispersed in about /3 of the water at about 170 F. and the dispersion is cooled to room temperature to promote solution of the cellulose derivative. The detergent is dissolved in the remainder of the water and the solutions are admixed.
The flow time of this shampoo was 55 seconds. if 1.0% of the same hydroxypropyl methyl cellulose is used a clear shampoo of 16 seconds flow time results. This result when compared with those of Example 1 illustrates that the effective amount of cellulose derivative to be added to obtain a shampoo of desired consistency will vary somewhat, within the .1 to range, depending on the particular detergent salt employed.
Example III A liquid cream (lotion) shampoo is made according to the formula:
A Percent Hydroxypropyl methyl cellulose 0.25 Distilled water 15.0
B Detergent 25.0 Distilled water 46.05 Preservative 0.70
C Distilled water 5.0 Citric acid 0.6
Triethanolamine 3.0
D Behenic acid 3.0 Hydrogenated castor oil 0.5 Lanolin 0.5
Perfume 0.4
This compound contains from 2 to 4% hydroxypropoxy groups and about 30% niethoxy groups and has a viscosity of 1.000 ccnl'looises.
The dry sodium salt of coconut oil fatty acids monoglycorido monosulfate detergent containing about 10% sodium sulfate and about 10% ether soluble material.
The hydroxypropyl methyl cellulose solution A is made by dispersing the cellulose compound in about 73 of the water at about 190 F, cooling the dispersion to about room temperature by adding the remaining water as ice and stirring until dissolved.
The components of detergent solution B are mixed together and added to solution A, after which AB is heated to 180 F. at which temperature it is a solution.
The citric acid of group C is dissolved in the water and the triethanolamine is added to the solution, generating heat, after which C is added to AB.
Group D comprises oil soluble materials. These are melted and heated to 200 F. and then the melt is added carefully to the solution of combined groups A, B andC. After cooling the emulsion to about F. perfume is added and stirred in.
The resulting product is of a desirable consistency, having a how time of 128 seconds. In addition the shampoo has an attractive pearly sheen. It is an excellent free-flowing shampoo product having very good detersive properties while still leaving the washed hair manageable.
A similar shampoo, containing 0.5% of the same hydroxypropyl methyl cellulose and prepared in the same manner has a flow time of 662 seconds while the flow time of a control shampoo with no cellulose derivative added is only 16.5 seconds.
The term consisting essentially of as used in the definition of the ingredients present in the claimed composition is intended to exclude the presence of other materials in such amounts as will interfere substantially with the properties and characteristics possessed by the composition as set forth but to permit the presence of other materials in such amounts as will not substantially affect adversely such properties and characteristics.
Although the present invention has been described with reference to particular embodiments and examples, it will be apparent to those skilled in the art that variations and modifications can be made and substituted therefor without departing from the principles and true spirit of the invention or going outside the scope of the claims.
What is claimed is:
1. A liquid shampoo composition consisting essentially of about 5 to 35 of a Water soluble higher fatty acid monoglyceride monosulfate detergent and about 0.1 to 5% of a water soluble hydroxypropyl methyl cellulose in an aqueous medium therefor, the said cellulose derivative having a methoxy content of 25 to 32% and an hydr0xypropoxy content of 2 to 10% and having a viscosity between 10 and 5,000 centipoises as determined at 2% solution in Water at 20 C.
2. A liquid cream shampoo composition consisting essentially of about 10 to 35% of a sodium higher fatty acid monoglyceride monosulfate detergent, about 0.5 to 10% opacifying agent and about 0.1 to 5% of a water soluble hydroxypropyl methyl cellulose in an aqueous medium therefor, the said cellulose derivative having a methoxy content of 25 to 32% and an hydroxypropoxy content of 2 to 10% and having a viscosity between 10 and 5,000 centipoises as determined at 2% solution in Water at 20 C.
3. A clear liquid shampoo composition consisting essentially of about 10 to 35% of an ammonium higher fatty acid monoglyceride monosulfate detergent and about 0.1 to of a water soluble hydroxypropyl methyl cellulose in an aqueous medium therefor, the said cellulose derivative having a methoxy content of 25 to 32% and an hydroxypropoxy content of 2 to and having a viscosity between 10 and 5,000 centipoises as determined at 2% solution in water at C.
4. A clear liquid shampoo consisting essentially of about 10 to of an ammonium higher fatty acid monoglyceride monosulfate detergent and about 0.2 to 2% of a water soluble hydroxypropyl methyl cellulose in an aqueous medium therefor, the said cellulose derivative having a methoxy content of 28 to 31% and an hydroxypropoxy content of 2 to 7% and having a viscosity between 50 and 4,000 centipoises as determined at 2% solution in water at 20 C.
5. A clear liquid shampoo composition consisting essentially of about 10 to 35% of an ammonium higher fatty acid monoglyceride monosulfate detergent, from about 1 to 2.5% inorganic salt and from 0.1 to 5% of a water soluble hydroxypropyl methyl cellulose in an aqueous medium therefor, the said cellulose derivative having a methoxy content of 25 to 32% and an hydroxypropoxy content of 2 to 10% and having a viscosity between 50 and 4,000 centipoises as determined at 2% solution in water at 20 C.
6. A liquid shampoo composition consisting essentially of about 10 to 35% of a higher fatty acid monoglyceride monosulfate detergent, about 1 to 5% of urea, and about 0.1 to 5% of a water soluble hydroxypropyl methyl cellulose in an aqueous medium therefor, the said cellulose derivative having a methoxy content of 25 to 32% and an hydroxypropoxy content of 2 to 10% and having a viscosity between 10 and 5,000 centipoises as determined at 2% solution in water at 20 C.
- 7. A liquid cream shampoo composition consisting essentially of about 10 to 35% of a sodium higher fatty acid monoglyceride monosuliate detergent, about 0.5 to 10% opacifying agent, about 0.1 to 10% of a higher fatty acyl di-lower alkylolamide having about 12 to 14 carbon atoms in the fatty acyl group thereof and about 0.1 to 5% of a water soluble hydroxypropyl methyl cellulose in an aqueous medium therefor, the said cellulose derivative having a methoxy content of 25 to 32% and an hydroxy-- propoxy content of 2 to 10% and having a viscosity between 10 and 5,000 centipoises as determined at 2% solution in water at 20 C.
8. A clear liquid shampoo composition consisting essentially of about 10 to 25 of an ammonium higher fatty acid monoglyceride monosulfate detergent, about 1 to 5% of urea and about 0.2 to 2% of a water soluble hydroxypropyl methyl cellulose in an aqueous medium therefor, the said cellulose derivative having a methoxy content of 28 to 31% and a hydroxypropoxy content of 2 to 7% and having a viscosity between and 4,000 centipoises as determined at 2% solution in water at 20 C.
References Cited in the file of this patent UNITED STATES PATENTS

Claims (1)

1. A LIQUID SHAMPOO COMPOSITION CONSISTING ESSENTIALLY OF ABOUT 5 TO 35% OF A WATER SOLUBLE HIGHER FATTY ACID MONOGLYCERIDE MONOSULFATE DETERGENT AND ABOUT 0.1 TO 5% OF A WATER SOLUBLE HYDROXYPROPYL METHYL CELLULOSE DERIVATIVE AQUEOUS MEDIUM THEREOF, THE SAID CELLULOSE DERIVATIVE HAVING A METHOXY CONTENT OF 25 TO 32% AND AN HYDROXYPROPOXY CONTENT OF 2 TO 10% AND HAVING A VISCOSITY BETWEEN 10 AND 5,000 CENTIPOISES AS DETERMINED AT 2% SOLUTION IN WATER AT 20*C.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3242092A (en) * 1962-06-01 1966-03-22 Colgate Palmolive Co Wax-containing liquid detergent
US3452135A (en) * 1966-04-06 1969-06-24 Medimpex Gyogyszerkullkeresked Allergy diagnostic skin test with carbamide or thiocarbamide and lipophilic adjuvants
US3960782A (en) * 1974-09-27 1976-06-01 The Procter & Gamble Company Shampoo compositions which impart high luster and manageability to hair

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Publication number Priority date Publication date Assignee Title
US2023387A (en) * 1932-10-31 1935-12-03 Benjamin R Harris Wetting agent
US2265913A (en) * 1933-07-17 1941-12-09 Lilienfeld Patents Inc Hydroxy alkyl-alkyl ethers of cellulose
US2538051A (en) * 1949-11-23 1951-01-16 Dow Chemcial Company Aqueous suspension polymerization in the presence of methyl hydroxypropyl cellulose as granulating agent
US2629667A (en) * 1949-12-27 1953-02-24 Phillips Petroleum Co Retarded set cement and slurries thereof
US2635103A (en) * 1950-03-09 1953-04-14 Drew & Co Inc E F Detergent and method of making the same
US2674580A (en) * 1950-07-20 1954-04-06 Colgate Palmolive Co Liquid shampoo
GB730572A (en) * 1952-03-31 1955-05-25 British Celanese Improvements in detergent compositions
US2773835A (en) * 1951-11-16 1956-12-11 Colgate Palmolive Co Liquid shampoo composition

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2023387A (en) * 1932-10-31 1935-12-03 Benjamin R Harris Wetting agent
US2265913A (en) * 1933-07-17 1941-12-09 Lilienfeld Patents Inc Hydroxy alkyl-alkyl ethers of cellulose
US2538051A (en) * 1949-11-23 1951-01-16 Dow Chemcial Company Aqueous suspension polymerization in the presence of methyl hydroxypropyl cellulose as granulating agent
US2629667A (en) * 1949-12-27 1953-02-24 Phillips Petroleum Co Retarded set cement and slurries thereof
US2635103A (en) * 1950-03-09 1953-04-14 Drew & Co Inc E F Detergent and method of making the same
US2674580A (en) * 1950-07-20 1954-04-06 Colgate Palmolive Co Liquid shampoo
US2773835A (en) * 1951-11-16 1956-12-11 Colgate Palmolive Co Liquid shampoo composition
GB730572A (en) * 1952-03-31 1955-05-25 British Celanese Improvements in detergent compositions

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3242092A (en) * 1962-06-01 1966-03-22 Colgate Palmolive Co Wax-containing liquid detergent
US3452135A (en) * 1966-04-06 1969-06-24 Medimpex Gyogyszerkullkeresked Allergy diagnostic skin test with carbamide or thiocarbamide and lipophilic adjuvants
US3960782A (en) * 1974-09-27 1976-06-01 The Procter & Gamble Company Shampoo compositions which impart high luster and manageability to hair

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