NZ205951A - A hair conditioning shampoo - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number £05951 205951 Priority Date(s): J. f?.. I.Q.$3 Complete Specification Filed: Class: Publication Date: J986 r ° Journal. No: Patents Form No. 5 (P. OCT 1983 _ Vfcr--'" Number PATENTS ACT 1953 Dated COMPLETE SPECIFICATION SHAMPOO tfWe 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 if'we pray that a Patent may be granted to rax/us. and the method by which it is to be perfonned. to be particularly described in and by the following statement: 1 205951 2 This invention relates to hair-conditioning shampoos and body-washing preparations.

After washing with shampoos, shower and bath preparations based on synthetic anionic surfactants, the hair often is in a cosmetically unsatisfactory state. When wet, it is difficult to comb and feels dull. After drying, the washed hair tends to develop a static charge, resulting in the well-known "flying away" of freshly washed hair. In addition, freshly washed hair often appears lustreless. For these reasons, it is known that conditioning preparations may be applied to hair after washing or shampooing. The preparations in question are mostly rinses or cream-like lotions containing cation-active surfactants. It is also known that certain substances may be added to ordinary shampoos to obtain a certain conditioning effect when the hair is washed. Substances of the type in question include, for example, water-soluble proteins or protein degradation products, polycationic polymers, for example amino polycarbamide resins, polycationic cellulose derivatives of the type described in US-PS No. 3,816,616 or polycationic guar derivatives of the type described in US-PS No. 4,292,212. Many other water-soluble polymers containing cationic or quaternary ammonium groups have been proposed for this purpose.

One disadvantage common to all known hair-conditioning additives lies in their at least partly reduced effect when used in anion-active hair washing preparations. Products having a particularly strong effect often show excessive adsorption to the hair and, as a reisult, reduce the elasticity, body and set of the dried hair.

Accordingly, the object of the present invention is to provide a shampoo formulation based on the well-known, heavily foaming anionic washing-active substances which, through the presence of suitable hair-reviving additives, enables the hair to be readily combed when wet and also 205951 3 leaves the dry hair with satisfactory cosmetic properties, including in particular elasticity, body, .sheen and set.

It has now been found that the hair-care properties of a shampoo based on anionic washing-active substances may be improved particularly effectively by adding to the shampoo a combination of a polycationic guar derivative, a hardenable cationic polycondensation product, a hydrophilic fatty acid ester and a water-soluble polyvinyl pyrrolidone.

Accordingly, the present invention relates to a hair-conditioning shampoo based on an aqueous solution of anionic washing-active substances and standard set-up agents which is characterised by a content of from 0.1 to 4% by weight of 3-(trimethylamino)-2-hydroxy propyl guar chloride, from 0.5 to 5% by weight of a readily water-soluble, hardenable polycondensation product of water-soluble polyamines containing reactive amino groups and polyalkylene oxide radicals with epichlorohydrin or compounds containing more than one epoxide group and/or halohydrin group in the molecule, from 1 to 4% by weight of an esterification product of ethylene oxide adducts of glycerol and 4 to 20 moles of ethylene oxide with 1 to 2 moles of a C8~Cx8 -fatty acid, from 0.1 to 1% by weight of a polyvinyl pyrrolidone (PVP) having an average molecular weight of at least 10,000.

The 3-(trimethylamino)-2-hydroxy propyl guar chloride is a cationic guar derivative known from US-PS No. 3,589,978. The products described therein contain as their basic unit two mannose units attached by a glucosidic bond and one galactose unit attached to one of the hydroxyl groups of the mannose units. on average, each of the hexose rings carries three free hydroxyl groups. These free hydroxyl groups are reacted with reactive quaternary ammonium 2Q59f 4 compounds to give the cationic polymers. The cationic polymer used in the shampoo according to the invention is commercially available under the name "Cosmedia (R*-Guar C 261".

The readily water-soluble, hardenable polycondensation products of water-soluble polyamines containing reactive amino groups and polyalkylene oxide radicals with epichlorohydrin or compounds containing more than one epoxide and/or halohydrin group in the molecule are known from DE-PS No. 2,363,871 (copy available on request). As set forth in said West German patent, to prepare the hardenable polycondensation products to be employed in the compositions of the present invention, it is necessary to proceed from polyamines with a content of polyalkylene oxide radicals, which are obtained via known procedure by reacting polyamines, especially polyalkylene polyamines with mono-and/or polyfunctional derivatives of polyalkylene oxides. These mono- and/or polyfunctional derivatives of polyalkylene oxides can contain, as reactable groups, chlorohydrin radicals, glycidyl radicals, halogen or other radicals capable of anion formation such as, for example, sulfuric acid radicals, alkylsulfonic acid radicals and so forth. The polyalkylene oxide groups present in the polyalkylene oxide derivatives can have varying molecule sizes, in which case the starting material is generally so chosen that approximately from 3 to 70 alkylene oxide radicals are available. As an alkylene oxide, ethylene oxide is the first to come under consideration; but other cyclic oxides, such as, for example, propylene oxide, as well as corresponding mixtures, are also usable. The polyalkylene oxide chains can also be interrupted, for example via the insertion of a dicarboxylic acid or diisocyanate radical.

Compounds usable as a second reaction component include those containing in the molecule more than one epoxide and/or halogen hydrin group, such as epichlorohydrin, 205951 ■JfF"1 dichlorohydrins or bifunctional reaction products of these compounds with glycolB, diglycols, polyalkylene oxides, glycerin, dicarboxylic acids, polycarboxylic acids, multivalent phenols, etc.

The preparation of certain hardenable polycondensation products to be employed in the inventive compositions can be effected via an especially simple procedure by reacting a polyalkylene glycol, e.g., a polyoxyethylene glycol having a molecular weight of 1000 or 600, with epichlorohydrin to form a bis chlorohydrin ether and by then further reacting this product with sufficient polyamine, e.g., dipropylene triamine, diethylene triamine or triethylene tetraamine, to produce in the reaction mixture a ratio of available chlorine atoms to available amino hydrocarbon atoms in the range of from 4:5 to 7:5. In this production process, the intermediately formed polyglycol polyamine is not isolated, but is immediately reacted with additional polyglycol bis chlorohydrin ether to form the desired polycondensation product. The reaction of the polyamines, which contain polyalkylene oxide radicals, with those compounds containing in the molecule more than one epoxide and/or halogen hydrin group, can be carried out in the presence of organic solvents or, preferably, water. To speed up the reaction, appropriate acid-binding substances, such as caustic alkali, sodium carbonate, magnesium carbonate or triethanol amine can also be included.

The reaction is carried out at temperatures between 50 and 100°C for a period of time sufficiently long to produce a clear increase in the viscosity of the reaction product. The reaction is terminated as soon as the desired degree of polycondensation—at which point the reaction product is still readily soluble—has been achieved, if necessary by means of adjusting the pH to <6.

Of the cationic polycondensation products described in said yiest German patent, the polycondensate produced as p. r-'TT'' 20595 s product F of the above-mentioned patent is particularly suitable for use in the production of the hair-conditioning shampoos according to the invention. One product of this type is commercially available for example under the name of Polyquart .

For ease of understanding the present invention, the following is an English translation of the method disclosed in said West German patent for preparing Product F; "Placed into a beatable and coolable agitator vessel, equipped with a reflux cooler and a thermometer, are 180 kg of liquid polyglycol 600. At a temperature of approximately 30°C and with agitation, 2.7 kg of tin tetrachloride are slowly added to the same. After raising the heat to 68°-70°, 56 kg of epichlorohydrin are added with steady stirring and possible cooling so quickly that the temperature of the mixture remains between 68-70°.

Agitation is continued for an hour at temperatures of approximately 70°. The total quantity of the obtained crude polyglycol-bis-chlorohydrin ether amounts to 239 kg. "80 kg of the obtained crude chlorohydrin ether are placed in a second agitator vessel with a capacity of approximately 600 liters, capable of heating and cooling and equipped with a thermometer and reflux cooler, and combined in the presence of agitation with 13.2 kg of dipropylene triamine, 50 kg of water and 28 kg of caustic soda solution.

The vessel is then heated for 45 minutes to the boiling point, with reflux cooling. The quantity of crude chlorohydrin ether of the polyglycol 600 remaining in the first vessel is then added with the application of agitation and kept at boiling for an additional 20-30 minutes after the addition of a further 30 kg of water. ■ The pH of the viscous reaction product is reduced during this time to about 7.2. Vigorous cooling is then applied. The pH is adjusted during cooling to 5.5-6 via the addition of approximately 38 kg of 10% aqueous hydrochloric acid - : • r- D L i i'L U i /uO 20595 7 solution. The yield is about 400 kg of a slightly yellowish, slightly opaque and highly viscpus liquid." The esterification products of ethylene oxide adducts of glycerol and 4 to 20 moles of ethylene oxide with 1 to 2 moles of a C8-Cig-fatty acid used in the compositions of the present invention are known from British Patent No. 1,333 ,475. Of the ester ification products mentioned therein, a partial ester obtained by the addition of 7.4 molea of ethylene oxide with 1 mole of glycerol, followed by the esterification of 1 mole of the resulting adduct with 1 mole of Cg-CiB coconut oil fatty acid, is particularly suitable for use in the hair-conditioning shampoos according to the invention. A product having this composition is commercially available for example under the name of Cetiol HE Polyvinyl pyrrolidones have an average molecular weight in the range of 10,000 to 70,000 are commercially available for example under the names of Kollidon (R) and Luviskol (R). Polyvinyl pyrrolidones having an average molecular weight of approximately 40,000, corresponding to a K-value of approximately 30, are particularly suitable for the production of hair-conditioning shampoos according to the invention.

The concentration of the above mentioned mixture of essential conditioning agents in the final shampoo may range from 1.7-14% by weight, and a range from 2-8% by weight is preferred.

The ratio of the various essential conditioning agents mentioned above may vary. Generally, the ratio will be about 1 part of the guar derivative to 0.5-4 parts hardenable condensation product (e.g. Polyquart h(r^) to 0.5-4 parts of the esterif ication product of C8~C;l8 fatty acid and ethoxylated glycerol (e.g. Cetiol HE(r*) to 0.15-0.5 parts of PVP. #» 205951 s The hair-conditioning shampoos according to the invention preferably contain as water-soluble anionic washing-active substances alkali metal, magnesium, ammonium and/or C2-C3 alkanolammonium salts of alkyl sulfuric acid semiesters containing from 8 to 18 and preferably from 12 to 16 carbon atoms in the alkyl radical or of alkyl polyglycol ether sulfuric acid semiesters containing from 8 to 18 and preferably from 12 to 16 carbon atoms in the alkyl radical and from 1 to 6 glycol ether groups in the molecule. Other suitable anionic washing-active substances are primary and secondary linear alkane sulfonates containing from 10 to 18 carbon atoms, alkene sulfonates and hydroxy alkane sulfonates of the type obtained in the sulfonation of olefins containing from 10 to 18 carbon atoms, Cs-Cis fatty acid alkylol amide polyglycol ether sulfates, C8-C18 fatty acid monoglyceride sulfates, sulfosuccinic acid monoalkyl esters containing from 8 to 18 carbon atoms in the alkyl group or dialkyl esters containing from 6 to 10 carbon atoms in the alkyl groups, alkyl polyglycol ether carboxylates containing from 8 to 18 carbon atoms in the alkyl group and 2 to 6 polyglycol ether groups in the molecule and acyl sarcosinea, acyl taurides and acyl isethionates containing from 8 to 18 carbon atoms in the acyl group. Mixtures of these components may also be used.

In general, the concentration of anionic surfactants in the shampoo may range from about 5 to 50% by weight; a preferred range is about 8 to about 30% by weight. 9 20595 A preferred anionic surfactant comprises a mixture of sodium lauryl polygljcol ether sulfate and fatty alcohol sulfate in a ratio of about 2 :1 to 1:1 by weight. The fatty, alcohol sulfate preferably contains an alcohol moiety with about 10 -5 1 •) C-atoms, preferably 12 - 11 C-atoms. The ratio of the total amount of anionic surfactants present to the mixture of essential conditioning agents may vary from about 10 : 1 to 1 : 1, preferably from 2-5 : 1 to 1,5: 1.

In addition, the hair-conditioning shampoos according to the 10 invention may contain standard additives and set-up agents, such as for example thickeners of the fatty acid alkylolaniide type, opacifiers, for example of the ethylene glycol distearate type, pH-stabilisers, > ** i such as alkali or ammonium phospates or citrates, preservatives, such as formaldehyde or p-hydroxy benzoic acid esters, dyes, 15 fragrances and known hair-cosmetic active substances, such as anti-dandruff agents or sebostatics.

The hair-conditioning shampoos having the composition according to the invention are distinguished by an unexpectedly marked improvement in the hair-conditioning properties of hair washed with 20 them. For example, the so-called wet combability of the hair condition ing shampoos according to the invention is considerably improved in relation to shampoos-containing only one of the conditioning components, (R) e. g. Cosmedia Guar C 2G1. This is the more surprising as the other essential ingredients have little or no influence on wet-rcombability 2r themselves. Similar surprising synergistic effects can be observed if the parameters sheen, feel, and antistatic properties, the so-called "conditioning effect", are investigated.

Also the feel (elasticity) and sheen of the dry hair are improved by the shampoos accoi'ding to the invention to a greater extent ' than with conventional shampoos containing for example only one of the components required in accordance with the invention. Finally, the tendency of the hair to develop an electrostatic charge after drying is i 1 0 considerably reduced by using the conditioning shampoo according to the invention. The hair tends less to "fly-away", can be combed more easily and retains its shape for longer periods.

The hair-cosmetic effects obtained with a hair conditioning shampoo according to the invention are shown in the following examples by comparison with conventional shampoos.

EXAMPLE Shampoo formulations according to the invention (Nos. 1 to 3) are comparatively tested with analogous shampoo formulations containing none (No. 10) or only part (Nos. 4 to 9) of the necessary components of the shampoos according to the invention.

The performance-tested shampoo formulations are set out in Table 1. EXAMPLE 1 Determination of wet-combability was determined by measuring the resistance to combing, i.e., the force required to draw a comb through a tuft of hair. A modified tensile testing machine (type 1402 as manufactured by the Zwick Company of Einsingen uber Ulm/Danube) was used. The test arrangement is described in "Reichstoffe, Aromen, Kosmetika, No. 12/1977", page 325, columns 2 and 3.

Standardized strands of hair which had been predamaged by bleaching and permanent-waving under defined conditions were used. They were washed with the shampoos set out in Table 1 in hand-warm water and rinsed with clear water.

In order to minimize error, the resistance to combing was determined 15 times with each of the shampoos to be tested and the average values calculated. The average combing resistance values are quoted in percent of the blank value. The blank value was determined after shampooing with an acqueous solution containing 10% by weight of sodium lauryl ether diethenoxy sulfate and rinsing with clear water. in CP lO Fatty alcohol 'Cj_2/14)-poly (2E0)glycol qvj ether sulfate, sodium salt Fatty alcohol Jsulfats, monoethanol a'UTonium salt Ethylene glycol distearate (20% dispersion in alkyl ether sulfate solution) .5 4.5 3.0 3.0 .5 4.5 3.0 ,5 4.5 3.0 .5 4.5 3.0 .5 4.5 3.0 .5 4.5 3.0 I9 .5 4.5 3.0 .5 4.5 3.0 .5 4.5 3.0 Cosmedia guar C 261* Polyquart H 81^' ** '(R) •£** (R) * Cetiol HE Luviskol K 30 (R) *-***- 2.0 1.0 1.5 0.6 2.0 3.0 1.0 0.6 0.8 2.5 2.5 0.4 1.5 2.5 1.5 0.5 1.2 2.0 0. i - 2.0 0.5 Perfume oil Preservative (Bronidox L5 Citric acid Water (R) 0.8 C.4 0.2 78.5 0.8 0.4 0.2 79.0 Resistance to wet combing in % of the value obtained after washing with a sodium lauryl ether sulfate solution 26% % 0.8 0.4" 0.2 79.4 0.8 0.4 0.2 83.6 0.8 0.4 0.2 83.6 0.8 0.4 0.2 84.4 0.8 0.4 0.2 85.Q 27% 95% 70^ % 110% 0.8 0.4 0.2 91.8 C .8 G.4 0.2 0.8 ! G. 4 i „ 0 • 'j. 2 81.0 ; 85.6 31% 75% 100% * Guar-hydroxypropyl-trinethylammonium chloride (CTFA name is Guar Hydroxypropyl trimmonium chloride) ** Polyglycol polyamine condensation resin *** Polyethylene glycol (7.5) glyceryl nionococate **** Polyvinyl pyrrolidone having an average molecular weight of 40,000 12- 205951 1 EXAMPLE 2 Testing of hair-cosmetic properties (salon test).

The testing and assessment of the hair-cosmetic properties were carried out on 10 test subjects differing from one another in the 5 quality of their hair using the so-called half-side test. The test was carried out by a trained hairdresser. The half-side test is used for the comparative testing of two hair treatment preparations or one hair treatment preparation and one standard on test subjects. In the present tests, hair shanpoo No. 1 according to the invention was used as the 10 standard. The canparison marks given in Table 2 are a measure of the extent to which hair shampoos Nos. 4 to 10 differ from the assessment of shampoo No. 1.

Procedure and evaluation The hair of the test subjects was wetted and parted in the middle. 15 The standard shampoo was applied to the left-hand half of the heads of 5 of the test subjects and the comparison shampoo to the right-hand half in equal quantities of 5 g in each case (pre-washed). In the case of the other 5 test subjects, the other half of their heads was treated with the same product. Both sides were shanpooed in the same way and rinsed with 20 water. For the main wash, the shampoos were applied once again to the same half of the head in quantities of 2.5 g, rubbed in to form a lather and thoroughly rinsed out with clear water.

During and after washing, the criteria set out in Table 2 below were separately assessed by -the hairdresser for each of the two sides. Assessment 25 was carried out by the awarding of marks (1 = excellent, 2 = good, 3 = moderate, 4 = poor). From the marks awarded for the 10 test subjects, the average values were calculated for the same product. The average values for the standard product were subtracted fran the average values for the N.Z. PATOCT OW»5T* •J -xp o vy? i I I » is J 1. 205051 13 ci r i :'on product. The p.iir ili f fcrencc . f.him obtained in the ;!vi'i.Mgo values of- the eisucsruonts of 10 test ;;ubjocts is r.hown in Table 2 below.

Result: The comparison shampoos were all juayed t_o be poorer in their hair-cosmetic properties than the standard shampoo (shampoo No. 1 according to the invention).

T A B L E 2 Comparison with shampoo No. 1 (pair difference) Salon tests 1 4 6 7 8 9 Wet hair Combabi1i ty 4- 0 -1 . 2 -0.6 -0 . A -1 . 0 -0. 4 -0.6 -1 . 2 Fee 1 ± 0 1 o UD -0.8 ro O 1 00 1 0 1 1 -0.5 -0.8 CO 1 o I Dry hair Antistati c ± 0 -0.5 -0.3 -0.5 -0.6- -0.1 1 o -0.6 Feel - 0 -0.5 -0.4 -0.6 -0.3 -0.5 -0.3 -0.6 (elasticity) Sheen 1+ o -0 . 5 -0.3 -0.2 -0.5 -0.4 + 0 -0.5 14 205951

Claims (6)

WHAT WE CLAIM IS:

1. 1 A hair conditioning shampoo comprising 5% to 50% by weight of a water-soluble anionic alkali metal, magnesium, ammonium or C2-C3 alkanolammonium detergent salt selected from the group consisting of C8~Cib alkyl sulfates, C8~Ci8 alkyl polyglycol ether sulfates having 1 to 6 glycol ether groups in the molecule, C10-C19 alkane sulfonates, Cio~c18 olefin sulfonates, Cs-Cis fatty acid alkylolamide polyglycol ether sulfates, C8_C]_8 fatty acid monoglyceride sulfates, c8~c18 alkylsulfosuccinates, Cg-Cio dialkylsulfosuccinates, c8~c18 alkyl polyglycol ether carboxylates having 2 to 6 polyglycol ether groups in the molecule, C8-C3.8 acyl sarcosinates, acyl taurides, Cs-Cis acyl isethionates and mixtures thereof and an effective amount of a conditioning agent selected from the group consisting of (a) 0.1% to 4% by weight of 3-(trimethylamino)-2-hydroxypropyl guar chloride, (b) 0.5% to 5% by weight of a readily water-soluble, hardenable polycondensation product formed by reacting a water-soluble polyamine containing reactive amino groups and having from 4 to 6 carbon atoms with an ether of poly C2-C3 alkylene glycol having terminal halohydrin or hydroxyl groups followed by reaction with either epichlorohydrin or additional reaction product of said polyamine and said ether, fc) 1% to 4% by weight of an esterification product formed by reacting from 1 to 2 moles of C8-Ci8 fatty acid with the adduct obtained by reacting 4 to 20 moles of ethylene oxide with 1 mole of glycerol and (d) 0.1% to 1% by weight of a polyvinylpyrrolidone having an average molecular weight of 10,000 to 70,000 in an amount in an aqueous medium characterized in that said conditioning agent is a mixture of (a), (b), (c), and (d) in a weight ratio of (a):(b):(c):(d) of 1:0.5-4:0.5-4:0.15-0.5, said conditioning mixture being present in an amount of 1.7% to 14% by weight and the weight ratio of said anionic detergent to said mixture is from 10:1 to 1:1.

2. A shampoo according to Claim 1 wherein 2% to 8% by 15 205951 weight of said conditioning mixture is present.

3. A shampoo according to Claim 2 wherein said anionic detergent is present in an amount of 8% to 30% by weight.

4. A shampoo according to Claim 3 wherein the weight ratio of said detergent to said mixture is from 2.5:1 to 1.5:1.

5. A shampoo according to any one of Claims 1 to 4 wherein said anionic detergent is a mixture of said Cg-C^s alkyl polyglycol ether sulfate and C3-C18 alkyl sulfate in a ratio of 2:1 to 1:1 by weight.

6. A hair conditioning shampoo as claimed in Claim 1 substantially as hereinbefore described, with reference to Examples 1(1), 1(2) and 1(3). 3T-WALKER, McCABE per ATTORNEY, THE .APPLICANT