NZ234190A

NZ234190A - Fibre conditioning composition containing an aminosilicone polymer

Info

Publication number: NZ234190A
Application number: NZ234190A
Authority: NZ
Inventors: Clarence R Robbins; Amrit M Patel
Original assignee: Colgate Palmolive Co
Priority date: 1989-11-07
Filing date: 1990-06-21
Publication date: 1994-08-26
Also published as: BR9002930A; ZA904840B; PT94420A; GR1000696B; GR900100467A; HU210123B; HU903926D0; AU635749B2; NO902745D0; NO902745L; AU5755990A; FI903128A0; PL285681A1; DD295307A5; TR26421A; JPH03153620A; KR910010004A; CN1051599A; HUT57574A

Description

<div class="application article clearfix" id="description"> New Zealand Paient Spedficaiion for Paient Number £34190 23 4 190 FYiCr;;;y C?LC;:;): > V?.5^ "2-** <* Cui iifrj} ^ ^ w Jv -: : ^ • . J ■ . ••••••"■ ri«„. Cv^O^b^ .^fe\VAWn.$,\. -. 1 jpQbmfJMtz* i n ~\ • .3. . HO THUMP* ~ Patents Form No. 5 Number j PATENTS ACT 1953 Dated COMPLETE SPECIFICATION FIBER CONDITIONING COMPOSITIONS CONTAINING AMINOSILICONE CONDITIONING AGENT We, COLGATE-PALMOLIVE COMPANY of 300 Park Avenue, New York, New York 10022, United States of America, a corporation organised under the laws of the State of Delaware, United States of America, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be described in and by the following statement: - 1 (followed by page la) 234190 This invention relates to fiber conditioning compositions. More particularly, it relates to such composition which are shampoos that include certain aminosilicones which, together with cationic surfactant fiber conditioning agents, such as quaternary ammonium salts, improve fiber conditioning significantly and, especially in the case of anionic synthetic organic detergent shampoos, result in excellent conditioning of human hair while it is being cleaned. conditioning detergent compositions an<l non-detergent conditioning compositions, for treating washed fibrous materials, which condition washed fabrics by making them softer and less likely to hold static charges after being dried in an automatic laundry dryer, have been marketed, and have contained cationic conditioning agents, such as quaternary ammonium salts, and such quaternary ammonium compounds have also been included in hair rinses. Aminosilicones.-and amodimethicones Fiber conditioning compositions, such as fabric 234 190 have been suggested as hair conditioning components of shampoos and so have various hydrocarbons, such as petrolatum and mineral oils. Anionic synthetic organic detergents# such as higher fatty alcohol sulfates and higher fatty alcohol polyethoxy sulfates, have been employed in shampoos, sometimes in conjun-tion with quaternary ammonium halides. Also, in a patent application filed by the present inventors on the same day as the present application, which application is entitled Fiber Conditioning Composition Containing Solubilized Poly-Lower Alkylene, shampoos are described which contain anionic detergent, cationic fiber conditioning surface active agent, polyethylene and solubilizing liquid hydrocarbon (mineral oil), in which the combination of polyethylene and mineral oil improves the hair conditioning action of the shampoo. However, it is applicants' belief that prior to their present invention their conditioning shampoos based on anionic synthetic organic detergent (s) and cationic hair conditioning surfactant, and that the unexpectedly improved conditioning effects resulting from such combination had not been previously noted or obtained by others. The closest prior art known to applicants appears to be U.S. patents: 4,559,227; 4,563,347; 4,601,902; 4,704,272; 4,710,314; and 4,747,732. U.S. patent 4,559,227 discloses aminosilicone polymers of structure similar to that of those of the present invention (see Example 7 of the patent, for example), and U.S. patent 4,710,314 describes hair conditioning 2341 shampoos that contain amodimethicone (an aminosilicone) and cationic surfactant conditioner. However, neither describes applicants' preferred aminosilicones and neither would lead one to believe that applicants' compositions, which contain such an aminosilicone, would be significantly better hair conditioning shampoos than similar compositions based on aminosilicones of similar structure (but different). In accordance with the present invention a fiber conditioning composition, which is of improved fiber conditioning characteristics, comprises an aminosilicone of the formula R1 CH3 CH3 R5 i I I i R2 - Si - 0 - (Si -0)x - (Si - 0)y - Si - R6 Il»« ch3 wherein Rl, R2, R3, R5, R6 and R7 are alkyls of 1 to 6 carbon atoms, and most preferably of 1 carbon atom each, R4 is - R8 - NH - CH2CH2 - NH2, R8 is alkylene of 3 to 6 carbon atoms, and most preferably is an isobutyl group, x is an average number in the range of 200 to 10,000, and more preferably above 500 and less than 10,000, and most preferably 750-800, and y is an average number in the range of 1 to 10, and more preferably less than 5, and most preferably 1, which is of an amine equivalent in the range of 4,000 to 60,000, and a carrier forr^minosilicone. 234180 By amine equivalent is meant the molecular weight of the aminosilicone that contains 14 grams (or a gram-atom) of nitrogen. Thus when the aminosilicone contains two amino groups, as in the formula above, with y being 1, an amine equivalent of 30,000 would mean that the polymer had a molecular weight of 60,000. The amine equivalent is invesely proportional to the weight of amine nitrogen present per weight of polymer. The carrier is normally liquid and is often a detergent composition, preferably a shampoo, and when it is a shampoo it preferably includes a cationic fiber conditioning agent, such as a quaternary 234 i ammonium salt. The presence of the quaternary ammonium salt appears to assist in the emulsification of the aminosilicone into the aqueous system, thereby helping to stabilize the shampoo, and also helps to make the aminosilicone more effective 5 in its hair conditioning function, despite the presence sf anionic synthetic organic detergent, which is usually present in such shampoo in much greater proportion than the conditioning agents. The aminosilicones of this invention (see the chemical 10 formula above) are preferably of amine equivalents in the range of 4,000 to 60,000 and more preferably such amine equivalent is of 10,000 or 20,000 to 40,000, with average x's in the range of 200 to 10,000 and more preferably above 500 and less than 10,000, and most preferably between 750-800, and with average 15 y's in the range of 1 to 10 and more preferably less than 5, and most preferably 1. They may also contain up to 25% cyclomethi-cone, which is used as a processing aid in their manufacture, but they may, desirably, contain less than this amount since cyclomethicone is not desirable in the formulations of this 20 invention. The amine equivalent is numerically equal to the weight in grains of polymer that contains 14 grams of amine nitrogen. In the preferred compositions of the present invention the aminosilicone polymer will be one obtained from Dow-corning Corporation, which is designated as aminosilicone B 25 in Table 2 below. Such aminosilicone is of a low charge density and amine content, with the amine equivalent being 30,000. In this polymer, the structure of which is illustrated above, R\ Ra, R3, R3, Re, and R"7 are all methyl groups, and RB is an isobutyl group. The viscosity of this material is 7500 + 1000 30 cps. Another such aminosilicone, designated herein as Dow- Corning aminosilicone A in Table 2 below is also useful but is not as effective as aminosilicone B, which is of a higher molecular weight and a lower charge density. Other aminosilicones made by Dow-Corning, identified as Silicones 7 . ^041 C, D and E in Table 2 below, while of similar formulas, are of 5 different charge densities (charge density is inversely related to amine equivalent), are less effective, and unacceptable as hair conditioning agents in applicants' compositions. The carrier for the aminosilicone may be any suitable carrier, preferably liquid and aqueous, and often will include a 10 surface active material (surfactant) or a detergent, which will help maintain the aminosilicone emulsified, dispersed or suspended in the aqueous medium, and will help to prevent phase separations and settling out of the aminosilicone and other components of the composition. Very preferably, the carrier 15 will be a shampoo and such shampoo will be useful to wash the hair and condition it so that after washing (and removal of hair oils) the hair will not be difficult to manage, which is often observed after shampooing, due to the shampooing removing from the hair substances that have conditioning properties. Instead 20 of shampoos serving as carriers for the aminosilicones other compositions may also be employed, including solvents, gels, pastes, crernes, lotions, emulsions, sprays, etc., and the aminosilicones may be applied to fibrous materials and to the hair in any normal manners. Because bases for such various 25 forms of cosmetic materials are well known they will not be specifically recited here, which is considered to be unnecessary because those skilled in the art will readily be awaxe of their compositions or can obtain formulas thereof from any of various 5 234190 texts in the field of cosmetics^ such as Modern Cosmeticoloqy. The cationic surface active fiber conditioning agents, which may be considered to be secondary conditioning agents in the invented fiber conditioning compositions, are preferably quaternary ammonium salts, although other surface active compounds with fiber conditioning properties may also be employed, at least in part. Thus, imidazolinium salts and betaines, and such cationic materials as are described in U.S. patent 4,000,077 may be substituted for at least some of the quaternary ammonium salt, as may be complexes of cationic and anionic surfactants, such as have been described in New Zealand patent specification 221541 and in New Zealand patent specifications 221580 and 221581. formula r9 R^O r12 n+ X~, wherein at least one of the R groups is lower alkyl and at least one is higher alkyl, with the others being higher and/or lower alkyl. Preferably R9 is higher alkyIs of 10 to 40 carbon atoms, R1^ is such a higher alkyl or lower alkyl, and X" is a salt-forming anion, such as halide, lower alkosulfate or lower carboxylic acid radical, e.g., chloride, bromide, methosulfate, ethosulfate, citrate or acetate. The lower alkyl will preferably be of 1 to 3 carbon atoms, more preferably being of 1 or 2 carbon atoms, and most preferably , in most cases, will be methyl, and the higher alkyl will preferably be of 10 to 22 carbon atoms, more preferably 12 to 18 or 20 carbon atoms, most The preferred quaternary ammonium salts are of the lower alkyl, such as of 1 to 4 carbon atoms, R^-® and R^ are - 6 2 3 4 1 9 carbon atoms, e.g., 16 or about "*t6 carbon atoms. The anion is preferably a halogen, such as chlorine, bromine or iodine, with chlorine and bromine being preferred and with chlorine being more preferred. The number of lower alkyls on the quaternary nitrogen will preferably be 1 or 2 and the number of higher alkyls will usually be 2 or 3. It has been found to be desirable to have at least 30 carbon atoms in the quaternary ammonium salt and preferably at least 34. The most preferred higher alkyl is cetyl, the most preferred lower alkyl is methyl, and the most preferred quaternary ammonium halide is tricetyl methyl ammonium chloride. Nevertheless, it is within the invention to employ other quaternary ammonium halides, such as distearyl dimethyl ammonium chloride, dilauryl dimethyl ammonium bromide, stearyl cetyl dimethyl ammonium chloride, trimyristyl ethyl ammonium bromide and trilauryl ethyl ammonium chloride, and other fiber and hair conditioning cationic surfactants as at least part of the fiber and/or hair conditioning cationic surfactant (surfactant is short for surface active agent) content of the present compositions. As was indicated previously, the fiber conditioning compositions of the invention may be in various suitable forms, although they are preferably in aqueous liquid form. The compositions may be used directly or may be dissolved and/or dispersed in water or other aqueous medium. Preferred compositions are shampoos, which will usually include a synthetic 2341^0 anionic organic detergent and water, but the preferred amino-silicones may also be included in non-detersive formulations with suitable carriers, such as in thickened aqueous media, emulsions, microemulsions and stable dispersions, preferably with cationic conditioning agent, too. Optionally, amphoteric, ampholytic, zwitterionic and nonionic detergents and surfactants may be utilized in the mentioned shampoos instead of or with the anionic detergent (s). Various suitable such detergents and surfactants are listed and described in McCutcheon's Detergents and Emulsifiers, North American Edition, 1983. The preferred anionic detergents, which are also described in the McCutcheon book, may be designated as "sulf(on)ated". Such are water soluble lipophilic sulfates and/or sulfonates of 8 to 22 carbon atoms, preferably of 10 to 20 carbon atoms, more preferably of 10 to 16 or 18 carbon atoms, and most preferably of 12 to 16 or 18 carbon atoms. Among such anionic detergents there may be mentioned, as exemplary thereof, higher alky1 sulfates, higher paraffin sulfonates, higher olefin sulfonates, higher fatty acid monoglyceride sulfates, higher fatty alcohol lower alkoxy (and polyoxy) sulfates, linear higher alkyl benzene sulfonates, and dialkyl sulfosuccinates. The most preferred of these anionic detergents for the present shampoos are the higher alkyl sulfates of 12 to 234 190 16 to 18 carbon atoms (preferably with the higher alkyl thereof being lauryl and with 2 or 3 ethoxy groups per mole). However, such alkyls may be of 12 to 16 carbon atoms and the alkoxy content may be of 1 to 20 per mole, such as 2 to 6 ethoxies per mole. A most preferred higher fatty alcohol sulfate is lauryl sulfate and a particularly preferred higher fatty alcohol poly-lower alkoxy sulfate is di- or triethoxylated lauryl alcohol sulfate. Most preferably the anionic detergent will be a mixture of higher alkyl sulfate and higher alkyl ether sulfate, with either being present in greater or equal proportion, and with the ratio of amounts of such components being in the range of 10:1 to 1:10 or 7:1 to 1:7, e.g., 1:5 to 5:1, when both such anionic detergents are present. The anionic detergents will be employed in the forms of their water soluble salts, which will usually be salts of alkali metals (sodium, potassium), ammonium, amines (such as dimethylamine and trimethylamine) or lower alkanolamines (such as triethanolamine, diethanolaxnine and monoethanolamine). Exemplary of useful detergents are ammonium lauryl sulfate, sodium lauryl diethoxy sulfate, ammonium lauryl triethoxy sulfate, sodium alpha C^g olefin sulfonate, sodium paraffin sulfonate, sodium coco monoglyceride sulfate, triethanolamine cetyl sulfate and dimethylamine myristyl sulfate. However, for best results it is preferred to utilize higher alkyl sulfate, higher alkyl poly-lower alkoxy sulfate or a mixture of such 234190 higher alkyl sulfate and such higher alkyl ether sulfate, such as lauryl sulfate and lauryl diethoxy sulfate or lauryl tri-ethoxy sulfate, often with the higher alkyl sulfate being present in greater proportion and in ammonium, triethanolamine 5 and/or sodium salt form. The water employed in the aqueous compositions of the invention, including the preferred shampoos, will preferably be deionized water of a hardness content less than 10 parts per million, as CaCO^, but other waters may also be utilized when 10 circumstances require. So as to ensure that the invented compositions are free of microorganisms it is preferred to use irradiated deionized water, and the various mixing vessels, tanks, piping andcontainers employed will be maintained in clean condition. 15 In addition to the required components of the invented conditioning compositions, including the shampoos which are preferred embodiments therof, there may also be present in such compositions various adjuvants which are known in the art to impart desirable properties or which have been determined 20 by the present inventors or their fellow researchers to have desirable effects when incorporated in the invented compositions. Among such adjuvants may be mentioned: paraffins, petrolatums, microcrystalline waxes, isoparaffins mineral oils and poly-ethylenes, all of which have been described in published Australian patent 25 application 57558/90 and in our simultaneously filed """" - 10 - 23 4190 patent specifications, previously noted herein, and which are useful to further improve the conditioning effects of the basic compositions of the present invention. Such materials, although not required components of the basic compositions of this invention, 5 are very useful adjuvants and significantly improve the conditioning activities of the invented compositions. When the polyethylene is being used it will be accompanied by a solubilizing hydrocarbon, such as mineral oil, although other liquid or near liquid hydrocarbons can also be employed for that purpose. 10 Other useful adjuvants or non-required components of the conditioning compositions and shampoos include higher fatty acid esters of lower alcohols, lower fatty acid esters of higher alcohols, and higher fatty acid esters of higher fatty alcohols, and mixtures thereof, as described in Australian patent application 15 57558/90; thickeners, such as lower alkyl celluloses and hydroxy-lower alkyl celluloses, e.g., methyl cellulose and hydroxypropyl methyl cellulose, and gums, such as xanthan gum, which may also act as stabilizers for the aqueous compositions; foam modifiers and improvers, such as betaines, higher fatty 20 acid triglycerides, and higher fatty acid alkanolamides, e.g., coco amidopropyl betaine, C^g_3g acids triglycerides and lauric monoethanolamide; pearlescing agents, such as ethylene glycol mono- and distearates; anti-dandruff agents, such as zinc pyrithione; viscosity control agents, such as propylene glycol 25 and sodium chloride; preservatives and anti.p^^|i^^ antifreezes, /v c 7 / A ff>\. .rs L 0 ^ j y {) ■ — such as ethylene glycol; sequeslhrants, such as EDTA; pH adjusters such as citric acid and citrates; colorants (dyes and water dispersible pigments); and solvents, such as ethanol and iso-propanol. 5 The proportions of the various components of the invented compositions are -such as to produce the desired fiber conditioning effects and increases in such effects. Such improve ments are obtained when the proportion of cationic fiber conditioning surfactant is sufficient to add conditioning to the condi 10 tioning effect of the aminosilicone, and also is enough to improve the dispersion of the aminosilicone so as to stabilize it in the aqueous medium. The proportion of anionic detergent is such as to clean the hair or other fiber thoroughly but also is such that the aminosilicone and cationic conditioning 15 surfactant can deposit on the fiber or hair from the comparatively strong aqueous detergent medium. The proportion of hydrocarbon materials is such that it improves the conditioning effects of the aminosilicone and cationic conditioning agent. Finally, such proportions are those whichwill allow the composi-20 tion to be stable on storage, non-settling and non-separating, and the water content will be sufficient to form such a stable continuous aqueous medium in which the other components will be contained in stable form. For non-shampoo conditioning compositions the propor-25 tions of aminosilicone, cationic surfactant and water will - 12 - 234190 normally be in the ranges of 0.1 to 10%, 0.1 to 10% and 50 to 99%, respectively, with any difference being of adjuvant(s) and surfactant, if present. When the surfactant is present in such compositions it will be in a proportion in the range of 0.5 to 20*4. For shampoos and other cleaning compositions that are desirably fiber conditioning the proportion of aminosilicone will usually be in the range of 0.3 to 5%, preferably 0.5 to 5%, more preferably 1 to 3%, e.g., about 1, 1.5, 2 or 3%. The percentage ranges for the cationic surfactant conditioner will usually be 0.1 to 5%, preferably 0.1 to 3%, more preferably 0.2 to 2% and most preferably 0.3 to 1%, e.g., 0.5%. The percentage of anionic detergent is normally 5 to 30%, preferably 8 to 25%, more preferably 10 to 20% and most preferably 12 to 18%, e.g., 15%. When mixed alkyl sulfate and alkyl ethoxy sulfate anionic detergents are present the proportions will normally be 10 to 15% of the alkyl sulfate and 2 to 5% of the alkyl ether sulfate, although the proportions can slso be reversed, in some circumstances. The water content will normally be in the range of 50 to 95 %, preferably 60 to 90% and more preferably 65 to 80%, e.g., about 70, 73 or 75%. The adjuvant content will normally be 0.1 to 30%, preferably 0.5 to 30%, preferably 0.5 to 20% and more preferably 3 to 15%, e.g., about 8 or 9%. When a supplementing hydrocarbon conditioning agent is present the percentage thereof will be in the range of 0.5 to 20%, # 234 190 preferably 1 to 10% and more preferably 1.5 to 5%. Preferred hydrocarbon component contents are 0.1 to 5% of microcrystalline wax with 0.1 to 3% of paraffin, more preferably 0.5 to 3% and 0.5 to 2%, respectively. When polyethylene and mineral oil are r 5 present to add their supplementing conditioning effect the proportions will normally be in the ranges of 0.2 to 5% of the polyethylene and 0.1 to 10% of mineral oil, preferably 0.2 to 2%, and 0.2 to 8%, respectively and more preferably 0.3 to 1% and 0.5 to 5%, respectively. 10 For non-aqueous compositions the required, optional and adjuvant components will normally be in the same ranges of proportions as in ;the aqueous compositions, with the water removed. The aqueous medium may be omitted or replaced, in whole or in part, by another solvent or liquid medium, e.g., 15 ethanol or isopropanol. As had been indicated previously, although the fiber conditioning and hair conditioning compositions of this invention may be in various physical forms preferably they are in liquid form and a preferred embodiment of the invention is a hair 20 conditioning shampoo. Such compositions should be stable chemically and physically to be acceptable in the marketplace. They should not deteriorate to an unacceptable extent on storage, and will not have components settle out or phases separating during storage. Also, the shampoos will be of desirable 25 viscosities, so as to be pourable and yet will not be so thin - 14 - 234 190 that they run uncontrollably. The desired viscosity range is 1,000 to 15,000 centipoises at room temperature (25°C.), preferably 3,000 to 6,000 centipoises, and more preferably the viscosity will be of about 3,500 or 4,000 centipoises at room temperature. The invented shampoos are non-settling and non-separating, and do not chemically- deteriorate on storage, as has been established by accelerated aging tests at elevated temperatures. The shampoo viscosity may change slightly on storage but such an increase does not significantly affect the shampoo's properties. Also, the desired use viscosity can be planned and the shampoo can be designed to have the desired viscosity when it is normally expected to be used by the consumer. The improved hair conditioning obtained by use of the invented compositions, compared to controls, from which any of the aminosilicone, cationic conditioner, or hydrocarbon conditioner has been omitted, is quite noticeable to the casual user of the shampoo or other invented conditioning composition, and is measurable in standard tests that are used to evaluate conditioning and its components, including ease of wet combing, ease of dry combing, manageability, static charge retention and flyaway. The casual shampooer will note that the hair is easire to comb after shampooing, in both wet and dry states, compared to control hair washed with a shampoo that is not under the invention (with one or more components missing from it). Scientific tests also I 234190 prove that the force needed to move a comb through a standard hair tress after treatment (shampooing) of the hair with an invented shampoo, and rinsing, is measurably less than that when such control is employed in the same manner. Such results are confirmed by panel tests, in which several experienced evaluators, using both the experimental and control products in blind tests, evaluate them for such combing ease, manageability and static characteristics and effects. Uses of the invented compositions, including shampoos, are not required to be different from normal uses of hair conditioning shampoos and other conditioning compositions. Conditioning agents may be applied at room temperature or at somewhat elevated temperatures in normal quantities and may be left on the hair for different lengths of time, depending on the extent of conditioning desired. Usually the conditioning agent and the hair will be at a temperature in the range of 15 to 50°C., preferably 20 to 40°C., and the conditioning composition will be in contact with the hair for from 30. seconds to ten minutes, preferably one to five minutes. Thei amount of composition applied will normally be in the range of 0.1 to 25 grams, often being 0.2 to 10 g. or 0.5 to 2 or 5 g., on the basis of the non-aqueous and non-solvent components of the compositions. On the basis of the shampoo which may be employed such application raltes may be in the range of 0.5 to 50 grams, often 2 to 15 or 20 grams and frequently five or ten grams per use. The applied composition may be brushed and/Q£ combed through the hair and may be subsequently washed out, may be allowed to remain on the hair or may be partially removed, as by towelling. When the shampoo is employed to wash and condition the hair it will be rinsed off with water after remaining on thehair as an aqueous foam for a sufficient length of time, usually 1 to 5 minutes, to satisfactorily condition the hair, and may then be wet combed, dried, as by blow drying, and dry combed or brushed to the desired style. To manufacture the present compositions, including shampoos, no complex procedures have to be followed, but to obtain best stability and greatest conditioning activity, after storage of the invented compositions, it will be desirable to form a dispersion of the water s-luble lipophile sulfate and/or sulfonate and adjuvants in water, at an elevated temperature, such as 70 to 90°C., dissolve and/or disperse cationic conditioning agent, such as quaternary ammonium salt, with any lipophilic materials, such as hydrocarbons, including polyethylene, mineral oil, microcrystalline wax, petrolatum, paraffin and isoparaffin as a melt or liquid mix at elevated temperature, and admix the two pre-mixes, at such elevated temperature, after which the heated aminosilicone may be admixed with the resulting mix, with the various mixings taking place with the portions to be mixed at approximately the same temperatures. It is important that the aminosilicone be mixed in after the main pre-mixing; otherwise it may separate out or form an unstable composition. When adjuvants are present those whi^fc are water soluble and/or disperslble may be mixed in with the aqueous phase materials and those which are not water soluble or dispersible in the aqueous medium, may be blended in with the lipophilic materials, such as the hydrocarbons, or in some instances may be added to the mixture of the hydrophilic and lipophilic materials either before or after cooling to room temperature. Normally perfume will be added to the other mixed components after cooling to room temperature and the aminosilicone will be added at elevated temperature and before such cooling. The perfume is added to the cooled composition to avoid losses thereof due to volatilizations of components and to prevent and heat degradation. When the procedure described is not followed, as when the various components of the compositions are blended indiscriminately, unstable products may result, which can separate or settle out on storage, and such unstable compositions tend to have poorer conditioning properties than the stable conditioning compositions and shampoos that are made according to the invented procedure. The following examples illustrate but do not limit the invention. Unless otherwise indicated all parts are by weight and all temperatures are in degrees Centigrade. Component example 1 Part 1 A B Deionized water 75. 89 75. 64 Natrosol™ 250 HHR 0. ,45 0. 45 Natrosol 330 CS 0. ,15 0. 15 Ammonium lauryl sulfate 12. .50 12. 50 Sodium lauryl diethoxy sulfate 2. ,50 2. 50 10 H* \0 15 Part 2 *** Cib-36 acid triglyceride Ethylene glycol distearate Stearyl stearate Propylene glycol, U.S.P. Laurie monoethanolamide 0.75 0.75 0.35 0.50 3.50 Tricetyl methyl ammonium chlor'ide 0.50 Others **** preservative (Gemaben II) Dye (1% aqueous solution) + Sodium chloride 20 ++ Citric acid Dow-Corning™ Silicone "B" Perfume 0.50 0.10 0.30 0.01 0.75 0.50 160.00 0.75 0.75 0.35 0.50 3.50 0.50 0.50 0.10 0.30 0.01 1.00 0.50 100.00 Percent (by weight) 1 ! C D E 75.14 74.54 73.64 0.45 0.45 0.45 0.15 0.15 0.15 12.50 12.50 12.50 2.50 2.50 2.50 0.75 0.75 0.35 0.50 3.50 0.50 0.75 0.75 0.35 0.50 3.50 0.50 0.75 0.75 0.35 0.50 3.50 0.50 r 0.50 0.10 0.30 0.01 1.50 0.50 0.10 0.30 0.01 2.00 0.50 0.10 0.30 0.01 3.00 PO vo o 0.50 100.00 0.50 100.00 0.50 100.00 # ' Z >54 1 9Q * * hydroxyethyl cellulose (Hercuies-^Coip.) ** Hydroxyethyl cellulose (Hercules Corp.) *** Syncrowax^ HGC-L (mf'd. by Croda Corp.) **** Mf'd. by Sutton Laboratories, Inc. 5 + Sodium chloride (viscosity regulator, can be employed up to 0.5%, to increase shampoo viscosity). ++ pH adjuster, can be employed, up to 0.1%, to lower pH, or sodium citrate can be employed, up to 0.1%, to raise pH. The shampoo of the invention is made by charging the 10 formula amount of water to a primary mixing vessel, starting mixing, and slowly sprinkling in the formula amounts of the Natrosols. Mixing is continued until the Natrosols are dissolved, while the medium is being heated to about 50°C. Heating is continued until the temperature is in the range of 80 to 85°C., 15 after which the heat is turned down and the mixing is continued. The formula amounts of ammonium lauryl sulfate and sodium lauryl diethoxy sulfate are then added. During the time that the Part 1 components are being prepared the Part 2 components, including Cis-36 acid triglyceride, ethylene glycol distearate, stearyl 20 stearate, propylene glycol, lauric monoethanolamide and tricetyl ammonium chloride, are either added separately or together to a separate container and are heated, with mixing, in such container until a uniform melt or solution is obtained at a temperature in the 80 to 85°C. range. With both Parts 1 and 2 at about the 23 4 1 9 * "* same elevated temperature, Part 2 is added to Part 1 in the main 5 mixing vessel, with care being taken to avoid foam formation during admixing. After the admixing is completed the heat is turned off and mixing is continued for another ten minutes, after which the aminosilicone (Dow-Corning Silicone "B") is mixed in and mixing is continued for another ten minutes. When 10 the mix is cooled to 39°C, the formula amounts of perfume, preservative and dye solution are added, with mixing, and sodium . chloride and citric acid (or sodium citrate) are added in such amounts as are sufficient to bring the viscosity to about 4,000 centipoises at 25°C, and sodium chloride and citric acid (or 15 sodium citrate) are then added if the viscosity is too low, outside the 4,000 to 6,000 centipoise range (measured on a Brookfield RVTD viscometer, with spindle No. 4, rotating at 20 r.p.m), and if the pH is off specification (although in some circumstances the pH may be as low as 5 or as high as 8). 20 After the manufacturing of products 1/A, 1/B, 1/C, 1/D and 1/E, they are evaluated for hair conditioning properties, using standard dry combing and wet combing evaluation techniques, such as are described in our co-filed application entitled Fiber Conditioning Compositions Containing Solubilized Poly-25 Lower Alkylene. The results of such tests are shown in Table 1. 21 2 3 4 10 15 TABLE 1 Test 1/A 1/B 1/C 1/D 1/E *** Evaluation for ease 4-5 6-7 7-8 8-9 10-11 of wet combing *** Evaluation for ease 3-4 5-6 5-6 6-7 7-8 of dry combing *** Evaluations are on a scale of 1-10, with 1 being minimum conditioning (maximum resistance to combings) and 10 being maximum conditioning (minimum resistance to combings). 20 The rating of 11 for Composition 1/E indicates conditioning and ease of wet combing that are better than what had theretofore been considered to be obtainable. A control shampoo is made of the same formula as those of this example, with the exception that the aminosilicone is 25 omitted and is replaced by water. Both wet combing and dry combing ratings for such control shampoo are 1-2, which illustrate the great improvement in conditioning effect obtained and its dependence on the presence of the particular described aminosilicone. When other aminosilicones, such as 30 Dow-Corning Silicones "C" and "D" of similar general formula but of higher charge density, and in some cases lower molecular weight, are substituted for the Silicone "B" significantly lower values in conditioning evaluations result. Also, when 22 i 23 4 1 the formulas are modified by additions of microcrystalline wax (m.p. = 82°C.) and petrolatum, using 0.2 to 1% of micro-crystalline wax, such as 0.5%, and 0.2 to 1.5% of petrolatum, such as 0.7%, with water contents being decreased to compensate, dry combing ratings are increased significantly for such modifications of Compositions 1/C, 1/D and 1/E« More importantly, significantly less flyaway hair is observed for all of these hydrocarbon containing compositions. 23 4 1 EXAMPLE2 Component Percent (by weight) A B C Irradiated deionized water 73.73 73.93 73.23 Natrosol 250 HHR 0.37 0.45 0.45 Natrosol 330 CS 0.13 0.45 0.15 Ammonium lauryl sulfate 12.50 12.50 12.50 Sodium lauryl diethoxy sulfate 2.50 2.50 2.50 Microcrystalline wax (m.p. = 82°C.) 1.00 0.20 0.20 c18-36 acid triglyceride 0.75 0.75 0.75 Snow white petrolatum 1.00 0.20 0.20 Tricetyl methyl ammonium chloride 0.50 0.50 0.50 Ethylene glycol distearate 0.75 0.75 0.75 Propylene glycol, U.S.P. 0.50 0.50 0.50 Laurie monoethanolamide 3.50 3.50 3.50 Stearyl stearate . 0.35 0.35 0.35 Others • Dow-Corning Silicone "B" 1.00 2.00 3.00 Sodium chloride , 0.10 0.10 0.10 Preservative 0.50 0.50 0.50 Citric acid 0.01 0.01 0.01 Dye solution (0.5% aqueous solution) 0.31 0.31 0.31 Perfume 0.50 100.00 0.50 100.00 0.50 100.00 2 7 ,, ~ „ ^ ^ 1 9 (j Compositions 2/A, 2/B and 2/C are made according to the procedures described in Example 1 and are tested according to the procedures also described therein. The products are stable shampoos, which can last a year or more under normal conditions 5 without deteriorating or losing conditioning powers, and without separating or settling out of component materials. The three shampoos are each adjusted to be of a viscosity in the range of 3,500 to 4,000 centipoises at 25°C., with such adjustment being made by addition of sodium chloride to thicken the shampoo . to. the 10 desired viscosity. Also, pH's thereof are in the range of 6 to 7, normally being about 6.5, with pH adjustment being effected by addition of citric acid and/or sodium citrate, as appropriate. When the shampoos are employed to wash and simultaneously 15 condition human .hair, evaluations of such hair after washing and rinsing (and drying when appropriate) show that the products made are excellent conditioning shampoos. The ratings (on the same bases as described in Example 1) for wet combing and dry combing for both 2/A and 2/B are 9-10 and wet combing and drying combing 20 ratings for 2/C are both 10-11. Thus, these examples illustrate that when more of the special aminosilicones of this invention is utilized conditioning will be improved. Additionally, it is shown that when microcrystalline wax and petrolatum are present, a lesser proportion of the aminosilicone may be employed, and 25 conditioning corresponding to that obtained from the composition 25 234180 containing more aminosilicone agd less microcrystalline wax and petrolatum is achievable. Thus, it would be expected that even better conditioning than 10-11 would be obtained by further increasing the microcrystalline wax and petrolatum contents of Formula 2/C, but care should be taken to avoid any excessive waxy feel of the conditioned hair. Another advantage of the present invention is that the invented shampoos, although containing significant proportions of very effective anionic detergent(s), do not prevent the deposition of the contained conditioning agents onto the hair or other fibers to be conditioned. Also, although the conditioning agents are substantive to the hair and are not removed from it by the anionic detergent(s) during shampooing, they do not tend to build up excessive deposits on the hair due to repeated shampooings of the hair with the conditioning shampoos, and do not thereby tend to make the hair objectionably greasy. In summary, the conditioning agents, particularly the amino-silicones, sufficiently adhere to the hair from aqueous solutions of the present shampoo components during shampooing but do not objectionably build up deposits on the hair that would tend to make it greasy or would otherwise adversely affect its physical properties. EXAMPLE 3 Component A B Water (irradiated, deionized) 73.13 68.13 5 Natrosol 250 HHR 0.37 0.37 Natrosol 330 CS 0.13 0.13 Ammonium lauryl sulfate 15.00 ° Ammonium laurethoxy sulfate - 20.00 Sodium laurethoxy (2 EtO) sulfate - -10 Sodium alpha C12-i6 °lefin sulfonate - Cocoamidopropyl betaine - - Sodivun decethoxy (3 EtO) sulfate - - Microcrystalline wax (m.p. = 82°C.) 1.00 1.00 c18-36 acid triglyceride 0.75 0.75 15 Petrolatum (Snow white) 0.75 0.75 Tricetyl methyl ammonium chloride 0.50 0.50 Ethylene glycol distearate 0.75 0.75 Propylene glycol, U.S.P. 0.50 0.50 Laurie monoethanolamide 3.50 3.50. 20 Stearyl stearate 0.35 0.35 - 27 Percent (by weight) c D E F G H 68.13 70.63 73.13 73.13 69.13 71.13 0.37 0.37 0.37 0.37 0.37 0.37 0.13 0.13 0.13 0.13 0.13 0.13 - 2.50 - - 12.50 12.50 - - - 7.50 - - - - - 7.50 2.50 2.50 - - 15.00 - - - - - - - 3.50 1 20.00 I 15.00 - - r - 1.00 1.00 1.00 1.00 1.00 1.00 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.50 0.50 0.50 0.50 0.50 0.50 0.75 0.75 0.75 0.75 0.75 0.75 f\3> 0.50 0.50 0.50 0.50 0.50 0.50 Ck| 3.50 3.50 3.50 3.50 3.50 3.50 0.35 0.35 0.35 0.35 0.35 0.35 Component Aminosilicone (Dow-Corning "B") 00 climbazole 000 piroctone olamine 009 Zinc pyrithione Sodium chloride Preservative (Germaben II) Sodium citrate Aqueous dye solution (1% concentration) Perfume EXAMPLE 3 (cont'd.) 0.75 Percent (by weight) 0.75 0.75 0.75 0.75 0.75 0 of 1-3 ethoxies, e.g., 2 EtO *°° anti-dandruff agent, mf'd. by Bayer ®°° anti-dandruff agent, mf'd. by Hoechst, as Octopirox ®.°° anti-dandruff agent, mf'd. by Olin Industries g". , (" ■ 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 _ — — - 0.50 — — 1 - - - - 0.50 - - - - - - - 1.00 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.01 0.01 0.01 0.01 0.01 0.01 0.01 ' 0.01 0.31 0.31 0.31 0.31 0.31 0.31 0.31 t 0.31 0.75 0.75 100!00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 ro 0*4 GanuSai CO o - 28 - 234190 Compositions A-H of-this example are made by the procedure previously described in Examples 1 and 2. The various compositions made, all of which are within the present invention, all exhibit improved hair conditioning properties, including 5 easier combing, better manageability, less flyaway (which is attributed in part to the presence of the microcrystalline wax and petrolatum in all the formulas), and repeated shampooings of the compositions do not leave objectionable gummy deposits on the hair, such as can result from employing cationic gum 10 conditioners instead of the described aminosilicones. 234 190 EXAMPLE 4 Component Irradiated deionized water Natrosol 250 HHR Natrosol 330 CS Ammonium lauryl sulfate Sodium lauryl diethoxy sulfate Microcrystalline wax (m.p. = 82°C.) c18-36 acid triglyceride Petrolatum (white) Tricetyl methyl ammonium chloride Ethylene glycol distearate Propylene glycol Laurie monoethanolamide Stearyl stearate Dow-Corning Silicone "B" Sodium chloride Preservative (Germaben II) Sodium citrate or citric acid Aqueous dye solution (0.6% conc.) Perfume Percent (by weight) A B C 73.63 73.53 73.13 0.37 0.45 0.45 0.13 0.15 0.15 12.50 12.50 12.50 2.50 2.50 2.50 1.00 - 0.20 0.75 0.75 0.75 1.00 - 0.20 0.50 0.50 0.50 0.75 0.75 0.75 0.50 0.50 0.50 3.50 3.50 3.50 0.35 0.35 0.35 1.00 3.00 3.00 0.20 0.20 0.20 0.50 0.50 0.50 0.01 0.01 0.01 0.31 0.31 0.31 0.50 0.50 0.50 100.00 100.00 100.00 The compositions of'-this example are made according to the method described in the previous examples and are evaluated in similar manner. The three shampoos made are effective conditioning shampoos of desired viscosity (4,000 centipoises at 25°C.) and pH (6.5). They are stable on storage and effectively condition hair that is shampooed with them. Shampoos 4/B and 4/C are more effective in improving ease of wet combing than Shampoo 4/A but Shampoo 4/A, despite the fact that it contains less aminosilicone than the other shampoos, is characterized by improved (excellent) dry combing properties. To make shampoo 4/A even more acceptable to consumers the amount of petrolatum in the formula is decreased to 0.75%, to avoid any trace of greasiness in the shampooed hair, and improved and satisfactory conditioning (including superior dry combing ease) are still obtained. 234190 EXAMPLE 5 Component Percent (by weight) Deionized water 73.94 Natrosol 250 HHR 0.45 • Natrosol 330 AP 0.15 Ammonium lauryl sulfate 12.50 Sodium lauryl diethoxy sulfate 2.50 c18-36 acid triglyceride 0.75 Tricetyl methyl ammonium chloride 0.50 Ethylene glycol distearate 0.75 Propylene glycol 0.50 Laurie monoethanolamide 3.50 Stearyl stearate 0.35 Aqueous color solution (0.6% conc.) 0.31 Germaben II 0.30 Aminosilicone 3.00 Perfume 0.50 100.00 Hydroxyethyl cellulose (Hercules Corp.) Shampoos of the above formula are made by the procedure previously described, using different amino-silicones, which shampoos are identified as A, B, C, D and E, and a basic control formula, F, is also made, containing no silicone (but with 3% more deionized water) 234 1 9 10 15 Table 2 below identifies the aminosilicones in the various formulas, when present, and Table 3 gives wet combing and dry combing evaluation data for such formulations. TABLE 2 20 Formula Identification 5/A 5/B 5/C 5/D 5/E 5/F Aminosilicone Identification A B C D E F Amine Equivalent 4,200 30,000 2,000 2,000 1,800 25 Characteristic 30 Wet combing ease Dry combing ease TABLE 3 Evaluation 5/A 5/B 5/C 5/D 5/E 4.5 8.5 2 1 1 2.5 4.0 8.0 2 2 2 2.0 35 From the above data it is seen that some aminosilicones have an adverse affect on hair conditioning or affect it hardly at all whereas those of the present invention, which are components of the A and B compositions, measurably improve conditioning (as measured by eases of wet and dry combing). 40 Such compositions also improve manageability of the hair. 33 EXAMPLE 6 When, in variations of the formulations of the preceding examples, the various adjuvants are omitted from the formulas so that the shampoos made contain only the required constituents thereof, anionic surfactant(s), cationic surfactant conditioner(s) aminosilicone(s) and water, the preparations made are less viscous than is desirable for commercial shampoos but they are usefully employable, for shampooing and conditioning hair. When hydrocarbon components, such as microcrystalline wax and petrolatum, or polyethylene and mineral oil, with paraffin and/or isoparaffin also being addable, are included in the formulations with the basic required components/ conditioning is further improved, as was previously indicated. % In the various formulations of the examples other materials mentioned in the specification may be substituted in part for those recited in the examples and useful improvements in hair conditioning (and fiber conditioning) will be obtainable. Thus, triethanolamine lauryl sulfate, sodium myristyl sulfate, potassium cetyl sulfate, triethanolamine myristyl diethoxy sulfate, sodium 0^4 paraffin sulfonate, ammonium C^o olefin sulfonate or triethanolamine cocomonoglyceride sulfate, or mixtures thereof, may be employed as the anionic detergent component, and distearyl dimethyl ammonium chloride, trilauryl methyl ammonium chloride, stearyl cetyl dimethyl ammonium chloride or dilauryl diethyl ammonium chloride may be # O 7 / ^9 c \J H substituted for the cationic surfactant conditioning agent, and improved conditioning will also result. Similarly, various 5 aminosilicones of the formula given and of the mentioned molecular weights and amine equivalents, which describe such polymers, may be employed in place of the specific preferred materials recited herein. Normally, however, it will be preferred to employ those wherein R1, R2, R3, R5, R® and R"7 are 10 alkyls in the lower portion of the 1 to 6 carbon atoms range, such as of two carbon atoms or less and most preferably 1 carbon atom, and Ra is an alkyl group having 3 to 6 carbon atoms with isobutyl being the preferred group. An important consideration in selecting the aminosilicone formulation is the feasibility 15 and economy of its manufacture so the R and other alkyl substituents on the silicon atoms will often be identical, except for RA. As to the adjuvants, different thickeners, viscosity controllers, foaming agents, foam modifiers, stabilizers, dispersing agents, preservatives, pH modifiers, 20 etc. may be substituted for those of the examples, as described in the specification, without interfering with the improved conditioning obtainable. Furthermore, the proportions of components of the compositions of the examples may also be changed, by being increased or 25 decreased by 10%, 20%, 30%, so long as such proportions are retained within the ranges recited in the specification, and in which the mentioned improved conditioning effects are obtainable. Finally, instead of the compositions of the examples all being shampoos they may be 30 employed for cleaning and conditioning other fibrous 35 </div>

Claims

<div class="application article clearfix printTableText" id="claims"> 2 3 4 1 materials, such as cotton, woo-l_and synthetic fibers, and the formulas may be modified by omission of anionic surfactants to produce non-detersive fiber and hair conditioning preparations that are useful for conditioning previously washed fibers (and which may be employed as hair rinses, mousses or gels to condition washed hair). The various patent applications, patents and publications previously referred to in this specification are hereby incorporated herein by reference. The invention has been described with reference to illustrations and examples thereof but is not intended to be limited to these because it is evident that one of skill in the art, with the present specification before him or her, will be able to utilize substitutes and equivalents without departing from the invention. 234190 WHAT WE CLAIM IS:

1. A fiber conditioning composition which comprises an aminosilicone of the formula

R1 CH3 CH3 r5

» » ii

R2 - si - 0 - (Si - 0)x - (Si - 0)y - Si - r6 R3 CH3 R4 R7

wherein R1, R2, R3, Rs, R6 and R7 are each methyl groups, R4 is -R8 - NH - CH2CH2 -NH2, Rs is an isobutylene group, x is an average number in the range of 750 to 800 and y is 1, which is of an amine equivalent in the range of 10,000 to 40,000, and a carrier for the aminosilicone.

2. A fiber conditioning composition according to claim 1 wherein the carrier is an aqueous medium.

3. A fiber conditioning composition according to claim 2 wherein the carrier is a liquid detersive medium in which the aminosilicone is in a dispersed or emulsified state.

4. A fiber conditioning composition according to claim 3 wherein said liquid detersive medium, comprises a detersive proportion of a synthetic organic detergent, a fiber conditioning proportion of the described aminosilicone, a fiber conditioning improving proportion of cationic fiber conditioning surfactant, and water.

5. A fiber conditioning composition according to claim 4 wherein said fiber is hair and the dispersion or emulsion of said aminosilicone in said liquid detersive medium is a hair conditioning shampoo.

y %

- 37 - -V ~;;x f 10 MAR 1994 !

" S E 1v

234 190

6. A hair conditioning shampoo according to claim 5 which comprises by weight, 5 to 30% of a water soluble synthetic organic anionic detergent, 0.3 to 5% of the described aminosilicone, 0.1 to 5% of cationic surfactant hair conditioning agent, 0.1 to 30% of adjuvants for the shampoo and 50 to 94.5% of water.

7. A hair conditioning shampoo according to claim 6 which comprises by weight, 5 to 30% of a water soluble synthetic organic lipophile sulfate and/or sulfonate anionic detergent having 8 to 20 carbon atoms in the lipophile group thereof, 0.3 to 5% of the aminosilicone, 0.1 to 5% of quaternary ammonium salt cationic conditioning agent of the formula R9, R10, R11, R12 N+ X", wherein R9 is lower alkyl of 1 to 4 carbon atoms, R10 and R11 are independently higher alkyls of 10 to 40 caibon atoms, R12 is such a lower alkyl or such a higher alkyl, and X" is a salt forming anion, 0.1 to 30% of adjuvants for the shampoo, and 50 to 94.5% of water.

8. A hair conditioning shampoo according to claim 7 which comprises, by weight, 8 to 25% of the water soluble sulfate and/or sulfonate detergent having 8 to 18 carbon atoms in the lipophile group(s) thereof, 0.5 to 5% of the aminosilicone, 0.1 to 3% of quaternary ammonium halide wherein X in the formula given is a halogen which is chlorine, bromine or iodine or any mixture thereof, and the sum of the numbers of carbon atoms is at least 30, 0.5 to 20% of adjuvants and 60 to 90% of water.

9. A hair conditioning shampoo according to claim 8 which comprises, by weight, 10 to 20% of a water soluble lipophile sulfate , 0.8 to 4% of the described aminosilicone, 0.2 to 2% of quaternary ammonium halide wherein the halogen is chlorine or bromine or a mixture thereof, 3 to 15% of adjuvants and 65 to 80% of water, which shampoo is of a viscosity in the range of 1,500 to 10,000 centipoises at 25°C.

10. A hair conditioning shampoo according to claim 9 which comprises, by weight, 12 to 18% of anionic detergent which is alcohol sulfate of 10 to 18 carbon atoms in the alkyl thereof and/or alcohol ether sulfate of 10 to 18 carbon atoms containing 1 to 3 ethoxy groups in ether portion thereof, with the cations of such salts being alkali metal,

ammonium and/or lower alkanolamijie of 1 to 3 carbon atoms in the alkanoi, 1 to 3% of the aminosilicone, 0.3 to 1% of quaternary ammonium chloride wherein, in the formula, R12 is higher alkyl, 3 to 15% of adjuvants and 65 to 80% of water, which shampoo is of a viscosity in the range of 3,000 to 6,000 centipoises at 25°C., and a pH in the range of 5 to 8.

weight, about 13% ammonium lauryl sulfate, about 3% of sodium lauryl diethoxy sulfate, about 3% of the described aminosilicone, about 0.5 of tricetyl methyl ammonium chloride, about 8% adjuvants and about 72.5% of water, in which the viscosity of the shampoo is in the range of substantially 3,500 to 4,000 centipoises at 25°C. and the pH is in range of 6 to 7.

12. A hair conditioning shampoo according to claim 6 which further includes 0.5 to 20% by weight of a hydrocarbon or a mixture of hydrocarbons selected from the group consisting of normally solid polyethylene, mineral oil, paraffin, isoparaffin, petrolatum and microcrystalline wax.

13. A hair conditioning shampoo according to claim 7 which further includes 0.1 to 3% by weight of microcrystalline wax and 0.1 to 2% by weight of paraffin.

14. A hair conditioning shampoo according to claim 8 which further includes 0.5 to 2% by weight of microcrystalline wax and 0.5 to 1.5% by weight of paraffin.

15. A hair conditioning shampoo according to claim 6 which further includes 0.2 to 5% by weight of a normally solid polyethylene and 0.1 to 10% by weight of a normally liquid mineral oil, which mineral oil makes the polyethylene water dispersible, emulsifiable or soluble, and increases its hair conditioning effects.

16. A hair conditioning shampoo according to claim 7 which further includes 0.2 to 2% by weight of a normally solid polyethylene and 0.2 to 8% by weight of a

11.

A hair conditioning shampoo according to claim 10 which comprises, by normally liquid mineral oil, which mineral oil makes the polyeth;

-39-

23 4 1 9 0

emulsifiable or soluble.

17. A process for conditioning fibers which comprises applying to such fibers a conditioning proportion of a composition according to claim 1 in such manner as to distribute such composition over such fibers.

18. A process for conditioning hair according to claim 17 wherein the conditioning composition comprises a detersive proportion of synthetic organic anionic detergent, a hair conditioning proportion of an aminosilicone of the formula

Rl

CH3 CH3 r5

I

R2 - Si - O -(Si - 0) x - (Si- 0)y - Si - rG

I

' f

R3 CH3 r4 r7

wherein R1, R2, R3, R5, R6 and R7 are each methyl groups, R4 is - R8 - NH - CH2CH2 -NH2, R8 is an isobutylene group, x is an average number in the range of 750 to 800, y is 1, which is of an amine equivalent in the range of 10,000 to 40,000, a conditioning improving proportion of cationic surfactant conditioning agent, and an aqueous shampoo medium which comprises water and shampoo adjuvant, the application to the hair is by shampooing the hair, and the application is followed by rinsing and drying of the shampooed and rinsed hair, and by wet and dry combing thereof.

19. A process according to claim 18 wherein the composition comprises by weight, 5 to 30% by weight of lipophile sulfate and/or sulfonate anionic detergent having 8 to 20 carbon atoms in the lipophile group thereof, 0.3 to 5% of aminosilicone, in which the amine equivalent is in the range of 20,000 to 40,000, 0.1 to 5% of quaternary ammonium salt cationic conditioning agent of the formula R9, R10, Ru, R12 N+ X*, wherein

40-

n.z. tvvfi-^TGfiriSS

10 fvl AY 1994

21 4 i 9 ®

R9 is lower alkyl of 1 to 4 carbon atoms, R10 and Ri: are independently higher alkyls of 10 to 40 carbon atoms, R12 is such a lower alkyl or such a higher alkyl, and X" is a salt forming anion, 0.1 to 30% of adjuvant, and 50 to 95 % of water, the conditioning shampoo is applied to hair on the head at the rate of 2 to 15 grams per shampooing, is maintained in contact with the hair, as an aqueous foam, for from 1 to 15 minutes, and is rinsed off, after which the hair is wet combed, blow dried and dry combed.

20. A process according to claim 18 wherein the conditioning composition includes in addition, 0.5 to 20% by weight of a hydrocarbon or a mixture of hydrocarbons selected from the group consisting of normally solid polyethylene, mineral oil, paraffin, isoparaffin, petrolatum and microcrystalline wax.

21. A process according to claim 19 wherein the conditioning composition further comprises, 0.5 to 2% by weight of microcrystalline wax and 0.5 to 1.5% by weight paraffin.

22. A process for the manufacture of a stable hair conditioning shampoo of the composition of claim 6 which comprises admixing the components, except for the aminosilicone, and heating to an elevated temperature at which the aminosilicone, when heated, will form an emulsion or stable dispersion when admixed with such composition and subsequently cooled, heating the aminosilicone and mixing the aminosilicone and the composition, less aminosilicone, for from one minute to one hour to disperse the aminosilicone in the composition, and cooling the composition to a stable emulsion or dispersion form.

23. A process for the manufacture of a stable hair conditioning shampoo of the composition of claim 16 wherein the polyethylene and mineral oil are heated together to a temperature in the range of 70 to 90°C., to melt and/or dissolve and/or disperse the polyethylene in the mineral oil, the balance of the composition components except for the aminosilicone, is processed to dispersion, emulsion or solution form by mixing together the components thereof and heating to a temperature in the range of 70 to 90°C., the two

23 4 1 9

such pre-mixes are admixed at such elevated temperature and the aminosilicone, at a temperature in the range of 70 to 90°C., is admixed with the combination of pre-mixes, and the mix is cooled to room temperature, to produce a stable hair conditioning shampoo, which does not deteriorate, separate or settle out on storage before use.

24. A process according to claim 19 wherein the amine equivalent of said aminosilicone is 30,000.

25. A fiber conditioning composition according to claim 3 wherein the amine equivalent of said aminosilicone is 30,00Or-

26. A fiber conditioning composition substantially as described herein and with reference to the examples excluding reference to any comparative compositions referred to therein.

27. A process for conditioning fibers substantially as described herein and with reference to the examples excluding reference to any comparative processes referred to therein.

28. A process for the manufacture of a stable hair conditioning shampoo substantially as described herein and with reference to the examples excluding reference to any comparative processes referred to therein.

west-walker; mc'cabb per: —»<-a «

ATTORNEYS FOR THE APPLICANT

42-

:r office

10 MAY 1994

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