GB1559823A - Shampoo compositions - Google Patents

Description

PATENT SPECIFICATION

Application No 28303/75 ( 22) Filed 4 July 1975 Patent of addition to No 1443426 dated 16 Oct 1973 Complete Specification filed 2 July 1976 ( 44) Complete Specification published 30 Jan 1980 ( 51) INT CL 3 C ID 10/02 (Cl ID 10/02 1/29 1/62 3/37) ( 52) Index at acceptance C 5 D 6 B I IC 6 B 12 A 6 B 12 B 1 6 B 12 B 2 6 B 12 B 3 6 812 F 1 6 812 F 2 6 812 L 6 B 13 6 B 2 6 B 4 6 B 5 6 C 8 ( 72) Inventors ROBERT VICTOR COOK and MICHAEL WILLIAM STEED ( 54) SHAMPOO COMPOSITIONS ( 71) We, RECKITT & COLMAN PRODUCTS LIMITED, a British Company, of P.O Box 26, 1/17 Burlington Lane, London W 4 2 RW, 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 particularly described in and by the following statement:-

The present invention relates to shampoo compositions and in particular to shampoo compositions containing conditioning agents.

Various combinations of detergents and conditioning agents have been proposed in attempts to produce a liquid shampoo composition which will both cleanse and condition the human hair.

Hitherto however, such compositions have not met with success due at least in part to the difficulty in meeting the many requirements of a satisfactory liquid shampoo composition.

The properties, which are generally considered to be desirable in a liquid composition, are that it should clean the hair, produce a foam which is persistent in the presence of grease but which be removed by rinsing the hair with water, leave the hair lustrous and pleasant to touch, impart a conditioning effect to the hair and possess an adequate shelf-life.

By the term "conditioning effect" as used herein is meant an improvement in the manageability of the hair which may be signified by one or more of the following results being obtained: an improvement in the ease of combing of "wet" and "dry" rinsed hair; an increase in the softness of the hair to the touch; a reduction in the tendency of the hair to tangle; a reduction in the tendency of the hair to acquire a charge of static electricity which produces "fly-away" characteristics; an increase in gloss.

Our British Patent Specification No.

1,443,426 describes how certain cationic conditioners can be solubilised in shampoo compositions by using in the compositions a par-

Claims (23)

ticular class of detergents Claim 1 of Speci- fication No 1,443,426 reads "A cosmetical shampoo composition which comprises at least one detergent which is a sulphated fatty amine, fatty acid amide or fatty acid alkanolamide or a sulphated ethoxylated fatty amine, fatty acid amide or fatty acid alkanolamide having a mean ethoxy group content of up to 15 ethoxy groups per mole and wherein the hydrocarbon chains in the fatty or fatty acid moiety each contain from 8 to 18 carbon atoms, or a salt thereof, and at least one cationic conditioner (as hereinbefore defined) dispersed in an aqueous medium, the p H of the composition being in the range of from 4 to 7 " We have now found that certain of the detergents which are structurally related to the detergents used in Specification No 1,443,426 may also be used to prepare clear, homogeneous shampoos containing conditioners. Accordingly the present invention provides a clear, homogeneous shampoo composition which comprises a cationic conditioner and at least one detergent of (Y)8 (CHZCH 20)x SO 3 X R-N A where R is an alkyl or an alkenyl group containing from 8 to 18 carbon atoms, Y is a straight chain or branched chain alkoxy group containing 2 or more carbon atoms, A is a hydrogen atom or the radical -(Y)b(CH 2 CH 20)y Z, a, b are 0 or 1 providing that when A is a hydrogen atom a= 1, and Y is not a group of the formula (CH 2 CH 20), x, y are in the range 1 to 15 X is a hydrogen ion, ammonium or quarternary ammonium ion or the ion of an alkali metal or alkaline earth metal and Z is a hydrogen atom or the group Soax The preferred detergents may be represented by the formula R-NH-(Y)H(CH 2 CH 2 00)SO 3 X ( 21) ( 61) ( 23) ( 11) 1559823 2 1,5982 where R, Y, X are as defined above and u lies in the range 1 to 3 or by the formula (Y)a(CH 2 CH 20)v 50 a X R-N \(Y)b(CI-a CH 2 IO)2 z where R, Y, X, Z, a and b are as defined above and the sum of v and W lies in the range 2 to 6. The chain length of the group R of the detergent is preferably that found in nature in coconut oil or palm kernel oil, that is chiefly a chain length of 12 carbon atoms, but may also be of synthetic origin. The preferred mean or average ethoxylate chain length may be obtained by blending two or more detergents having different ethoxylate chain lengths. The preferred detergents may be prepared by the reaction of ethylene oxide with a compound of formula RNHCH 2 CH 2,OH or of formula CH 2 CH 20 H / RN CH 2 CH 2 OH followed by the introduction of a sulphate group onto the ethylene oxide condensation product either by a sulphamation reaction using sulphamic acid or an alkyl sulphamic acid or by a sulphation reaction using sulphur trioxide or chlorosulphonic acid. The total level of detergent in the shampoo compositions of the present invention may be varied in accordance with the degree of foaming and cleansing desred It will generally be in the range of from 5 to 35 %, preferably from to 30 % by weight of the total composition. Other additional detergents may be present in the compositions The additional detergents which may be used include amphoteric detergents, for example, alkyl betaines, such as lauryl betaines, amine oxides such as alkyl dimethyl amrnine oxide and imidazolines, or anionic detergens such as sodium lauryl ether sulphate. The cationic conditioner used in the shampoo compositions of the present invention is substantive to the human hair, an effect believed to be due to electrostatic attraction During use of the compositions of the invention it is believed that the conditioner is deposited as a thin continuous film over the hair to provide a conditioning effect on the hair The deposition of the cationic conditioner by this mechanism achieves a total or almost total coverage of each hair with a thin film of the conditioner The film of conditioner may be as thin as one monolayer and still exert a conditioning effect on the hair. Suitable cationic conditioners for use in the compositions of the present invention include nitrogen-containing compounds having one or more cationic charges per molecule and imine polymers. Examples of nitrogen-containing compounds having one cationic charge (hereinafter referred to as monocationic compounds) which may be used in the compositions of the invention are: alkyl trimethyl ammonium halides N alkyl pyridinium halides N alkyl isoquinolinium halides di alkyl dimethyl ammonium halides alkyl aryl dimethyl ammonium halides fatty acid aminoalkyl amides for example those sold under the trade name Sapamines (Trade Mark) and alkyl benzyl hydroxy ethyl imidazolinium chloride. Mixtures of such monocationic compounds may also be used. In order to improve the solubility of such compounds the nitrogen groups may be ethoxylated A suitable ethoxylated compound is stearyl penta ethoxy ammonium chloride (sold under the trade name Genamin KS 5 by Hoechst) Ethoxylation is particularly advantageous in the case of dialkyl quaternary ammonium salts whose solubility in an aqueous medium is low. Examples of nitrogen-containing compounds having more than one cationic charge (hereinafter referred to as polycationic compounds) which may be used in the compositions of the invention are: high molecular weight aminoethyl acrylate/ phosphate/acrylate copolymer sold under the trade name Catrex (formerly known as Resyn 78-3510) National Adhesives Limited, quaternised vinyl pyrollidone copolymers sold under the trade name Gafquat e g Gafquat 734, 755, 750 or 759 by G A F. Limited, the low molecular weight condensation product of adipic acid, diethylene triamine polyamide and epichlorhydrin sold under the trade name Delsette e g Delsette 101 or 201 by Hercules Limited and, the quaternary nitrogen containing cellulose ether sold under the trade name Polymer JR by Union Carbide Corporation Mixtures of such compounds may also be used (Resyn, Catrex Gafquat, Delsette and Polymer JR are Trade Marks). The cationic conditioner may comprise a mixture of at least one mono cationic compound and at least one polycationic compound.

1,559,823 1,559,823 Monocationic ad polycationic conditioners such as those described above may be present in an amount from 0 1 to 10 % by weight of the total composition, for example from 0 5 to

2 5 % by weight.

Imine polymers may be prepared by the polymerisation of imines of the formula:

R, R 2 1 2 H C -C H H N H where R 1, R, each represent H atoms or an alkyl group having 1 to 6 carbon atoms Imine polymers suitable for use in the compositions of the present invention may contain an average of 3 to 1502 imine groups per mole preferable 7 to 102 imine groups per mole Such polymers have been reported (J Soc Cos.

Chem 23, 593-603 l 1972 l) to have a structure which may be represented as:

Trade Name PEI 6 PEI 12 PEI 18 PEI 600 PEI 600 E When an imine polymer is used conditioner in the compositions of t invention it may be present in an am 0.05 to 2 5 % by weight of the tota tion, for example from 0 1 to 1 0 % 50; The preferred imine polymers are po imines having molecular weights in 600 to 1800.

In addition to its conditioning e ethyleneimine shows strong anti action against several organisms In it has been shown that polyethylene a powerful inhibitory action ag organism P ovale which is repor associated with dandruff.

Polyethyleneimine has a strong action and will form complexes v compounds containing metal ions si heavy metal salts of 2 pyridinet oxide (pyrithione) For example, the of pyrithione is sparingly soluble in a complex of zinc pyrithione with of polyethyleneimine (MW 600) foron aqueous solution which is soluble in poo compositions of the present in give a clear shampoo The prefer metal salt of pyrithione in the zinc the shampoo compositions of the p vention may contain up to 0 5 % of the salt Other suitable heavy met dcude the cobalt, manganese, and nic The preferred p H of the compo R C CHR H RNH CHCH H CH NH 2 R 2 H where m is an integer from 1 to 1500 preferably 5 to 100 and R 1 and Ro are as defined above In practice a considerable amount of branching occurs in the polymerisation of imines and primary, secondary and tertiary nitrogen atoms will be present in the molecule.

The imine polymers may be alkoxylated by reaction with an, alkylene oxide.

The number of cationic charges of the imine polymer increases as the p H of any composition in which they are present is decreased.

In the above-mentioned paper it is reported that at p H 8 0, p H 6 0 and p H 4 0 the percentage of nitrogen atoms in polyethyleneimine having a positive charge is 25 %, 33 % and 50 % O respectively.

Examples of ethyleneimine polymers which are produced by the Dow Chemical Co (Midland Mich 48680), are as follows:

Chemical Description Polyethyleneimine M W 600 Polyethyleneimine M W 1200 Polyethyleneimine M W 1800 Polyethyleneimine M W 60,000 Polyethyleneimine M W 60,000 reacted with ethylene oxide in ratio 1:0 75 as cationic the invention will depend on the particular the present formulation and is conveniently in the range nount from of 3 5 to 10 The p H of the composition may 1 composi be adjusted to the required value by the addiby weight tion of acid, the preferred acids being phoslyethylene phoric acid, hydrochloric acid, acetic acid, the range tartaric acid and citric acid, or by the addition of a base such as sodium hydroxide or triffect poly ethanol amine.

i-microbial The shampoo compositions of the present inparticular vention may contain additives which are comeimine has mon in contemporary shampoo preparations, gainst the providing that such additives do not interfere ted to be to any significant extent with the mechansm of deposition of the cationic conditioner onto the chelating hair.

with some Foam stabilizers typically used in shampoo uch as the preparations may be incorporated into the hiol 1 shampoo compositions of the present invention.

e zinc salt Typical examples of foam stabilizers are amine water but oxides, such as coco dimethyl amine oxide, an excess alkyl betaines such as coco dimethyl betaine, ms a clear alkanolamides such as coco fatty acids monothe sham ethanolamide, coco fatty acids diethanolamide, vention to coco fatty acids isopropanolamide and ethoxylred heavy ated alkanolamides such as ethoxylated coco c salt and fatty acids monoethanolamide The foam stabil)resent in izers may be incorporated in the compositions by weight of the present invention in an amount of from al salts in 1 to 5 % by weight based on the weight of the ckel salts total composition.

ositions of Thickeners, such as simple salts, ethoxylated 1,559,823 fatty acids or cellulosic derivatives, or thinners, such as glycols, or polyalkylene glycols may be incorporated into the compositions of the invention.

If desired medicaments such as antimicrobial agents may be incorporated into the compositions Typical examples of antimicrobial agents suitable for inclusion in shampoo compositions of the present invention are 2,4,4 'trichloro 2 hydroxy diphenyl ether (Irgasan DP 300-Ciba-Geigy, Irgasan is a Registered Trade Mark), trichlorocarbanilide, cetyltrimethyl ammonium chloride, benzalkonium chloride, heavy metal salts of 2 pyridinethiol 1 oxide and colloidal sulphur.

Further additives such as protein hydrolysates, lanolin and derivatives thereof, herbal or balsamic extracts, vitamins, vegetable oils, dyes, perfumes and preservatives, such as formalin or dodecyl guanidine, may be incorporated without impairing the fundamental properties of the compositions.

Pearlising or opacifying agents may also be added, for example ethylene glycol monostearate, ethylene glycol distearate, alkaline earth metal soaps or fatty alcohols.

The following Examples illustrate the present invention Percentages are percentages by weight based on the total weight of the composition unless otherwise stated In these Examples the detergent (designed Detergent M) is a 24 % aqueous solution of the sodium salt of the product of the sulphation of an ethylene oxide condensation product of formula CHCHH,0 (CH 2 CH 2 O) H / R-N CH/CHO (CHZCH 20)y H where R is a group derived from coconut oil and containing mainly C 12 and C 1 carbon chains and the sum of x+y is about 4.

Example 1 The components below were mixed together in a mixing vessel and citric acid was added to a give a p H of 5 8.

Detergent M Alkyl dimethyl betaine ( 30 % solution) Coconut diethanol amide Gafquat 734 M ( 50 % solution in Industrial Methylated Spirit) Perfume, preservative, colour Water % w/w 45.0 3.0 3.0 2.0 qs Balance Example 2 The components below were mixed together in a vessel and the p H of the composition was adjusted to 6 7 by the addition of phosphoric acid.

Detergent M 4.5 mole ethoxylated coco fatty acids monoethanolamide Polyethyleneimine (Mol wt 600) Perfume, preservative, colour Water 50.0 3.5 0.17 q.s.

Balance Example 3 The components below were mixed together in a mixing vessel and the p H of the composition was adjusted to 4 0 by the addition of phosphoric acid.

Sodium lauryl 3 mole ether sulphate ( 27 % solution) Detergent M Coconut diethanolamide Catrex resin Perfume, preservative, colour Water 20.0 25.0 3.0 5.0 q.s.

Balance Example 4 To prepare the clear shampoo composition below a solution of the complex formed from the zinc pyrithione and the poiyethyleneimine was blended with the other components in a simple mixer Sulphuric acid was added to adjust the p H of the composition to 8 6.

Detergent M Alkyl dimethyl betaine ( 30 % solution) Monoisopropanolamine lauryl 2 mole ether sulphate ( 28 % solution) Monoisopropanolamine lauryl sulphate ( 35 % solution) Monoisopropanolamine Perfume, colour Zinc pyrithione Polyethyleneimine (MW= 600) Water % w/w 55.0 12.50 16.50 4.40 3.00 q.s.

0.25 0.44 Balance WHAT WE CLAIM IS:1 A single phase aqueous shampoo composition comprising a cationic conditioner and at least one detergent of the formula (Y)(CH 2 CH 20),SO 3 X / R-N A where R is an alkyl or an alkenyl group containing from 8 to 18 carbon atoms, Y is a straight chain or branched chain alkoxy group containing 2 or more carbon 105 atoms, A is a hydrogen atom or the radical -(Y)b(CH 2 CH 20)FZ, S 1,559,823 5 a, b are 0 or 1 providing that when A is a hydrogen atom a=l, and Y is not a group of the formula CH 2 CHPO x, y are in the range 1 to 15, X is a hydrogen ion, ammonium or quaternary ammonium ion or the ion of an alkali metal or alkaline earth metal and Z is a hydrogen atom or the group SOSX 2 A shampoo composition as claimed in claim 1 wherein the detergent is represented by the formula R-NHI (Y)-(CH 2 CHO)SO 3 X where R is an alkyl or an alkenyl group containing from 8 to 18 carbon atoms, Y is a straight chain or branched chain alkoxy group containing 3 or more carbon atoms, X is a hydrogen ion, ammonium or quaternary ammonium ion or the ion of an alkali metal or alkaline earth metal and u is in the range 1 to 3.

3 A shampoo composition as claimed in claim 1 wherein the detergent is represented by the formula (Y)(CHC Ho 0),50 o X / R-N (Y)b(CH 2 CHO) Z where R is an alkyl or an alkenyl group containing from 8 to 18 carbon atoms, Y is a straight chain or branched chain alkoxy group containing 2 or more carbon atoms a, b are O or 1, X is a hydrogen ion, ammonium or quaternary ammonium ion or the ion of an alkali metal or alkaline earth metal, Z is a hydrogen atom or the group SOX and the sum of v and W is in the range 2 to 6.

4 A shampoo composition as claimed in any one of claims 1 to 3 wherein the chain length of the group R of the detergent is that found in nature in coconut oil or palm kernel oil.

A shampoo composition as claimed in any one of the preceding claims wherein the total amount of detergent in the shampoo is from

5 to 35 % by weight of the total composition.

6 A shampoo composition as claimed in claim 5 wherein the total amount of detergent in the shampoo is from 10 to 30 % by weight of the total composition.

7 A shampoo composition as claimed in any one of the preceding claims wherein the cationic conditioner is a nitrogen-containing compound having one or more cationic charges per molecule.

8 A shampoo composition as claimed in claim 7 wherein the cationic conditioner comprises a mono cationic compound which is an alkyl trimethyl ammonium halide, an N alkyl pyridinum halide, and N alkyl isoquinolinium halide, a di alkyl dimethyl ammonium halide, an alkyl aryl dimethyl ammonium halide, a fatty acid aminoalkylamide, an alkyl benzyl hydroxy ethyl imidazolinium chloride, stearyl pentaethoxy ammonium chloride or a mixture of such compounds.

9 A shampoo composition as claimed in claim 7 wherein the cationic conditioner is a polycationic compound as hereinbefore specifically described or a mixture of such compounds.

A shampoo composition as claimed in any one of clams 7 to 9 wherein the cationic conditioner is present in an amount of from 0.1 to

10 % by weight based on the total weight of the composition.

11 A shampoo composition as claimed in claim 10 wherein the cationic conditioner is present in an amount from 0 5 to 2 5 % by weight based on the total weight of the composition.

12 A shampoo composition as claimed in any one of claims 1 to 6 wherein the cationic conditioner is an imine polymer which is the polymerisation product of an imine of formula R 1 R 2 1 2 H C-C-H H H where R& R 2 each represent H atoms or an alkyl group containing 1 to 6 carbon atoms and which contains an average of 3 to 1502 imine groups per mole.

13 A shampoo composition as claimed in 95 claim 12 wherein the imine polymer contains an average of 7 to 102 imine groups per mole.

14 A shampoo composition as claimed in either claim 12 or claim 13 wherein the imine polymer is alkoxylated by reaction with 100 an alkylene oxide.

A shampoo composition as claimed in any one of claims 12 to 14 wherein the imine polymer or its alkoxylated derivative is present in an amount from 0 05 to 2 5 % by 105 weight of the total composition.

16 A shampoo composition as claimed in claim 15 wherein the imine polymer or its alkoxylated derivative is present in an amount from 0 1 to 1 0 % by weight of the total com 110 position.

17 A shampoo composition as claimed in claim 12 wherein the imine polymer is a polyethyleneimine having a molecular weight in the range 600 to 1800 115

18 A shampoo composition as claimed in 1,559,823 1,559,823 any one of claims 12 to 17 wherein a proportion of the imine polymer is present as a complex with a heavy metal salt of 2 pyridinethiol 1 oxide.

19 A shampoo composition as claimed in claim 18 wherein the composition contains up to 0 5 % by weight of the zinc salt of 2 pyridinethiol 1 oxide (calculated as zinc 2 pyridinethiol 1 oxide) complexed with the imine polymer.

A shampoo composition as claimed in any preceding claim which aditionally comprises, as an antimicrobial agent, 2,4,4 ' trichloro 2 hydroxy diphenyl ether, trichlorocarbanilide, cetyltrimethyl ammonium chloride, benzalkonium chloride, or colloidal sulphur.

21 A shampoo composition as claimed in any one of the preceding claims which additionally includes at least one of a foam stabilizer, a preservative, a thickener, a medicament, a perfume, a colourant or a pearlising or opacifying agent.

22 A shampoo composition as claimed in claim 1 substantially as hereinbefore described.

23 A shampoo composition substantially as hereinbefore described with reference to any one of Examples 1 to 4.

BOULT, WADE & TENNANT, Chartered Patent Agents, 34 Cursitor Street, London EC 4 A IPQ.

Printed for Her Majesty's Stationery Office, by the Courier Press, Leamington Spa 1980 Published by The Patent Office, 25 Southampton Buildings, London, WC 2 A l AY, from which copies may be obtained.