United States Patent [191
`Cseh
`
`[11] Patent Number:
`[45] Date of Patent:
`
`4,676,978
`Jun.30, 1987
`
`[54] SHAMPOO
`[75]
`Inventor: Edomer G. Cseh, Koge, Denmark
`[73] Assignee: Colgate-Palmolive Company, New
`York, N.Y.
`[21] Appl. No.: 822,445
`[22] Filed:
`Jan. 27, 1986
`
`[51)
`
`Related U.S. Application Data
`[63) Continuation of Ser. No. 542,630, Oct. 17, 1983, aban(cid:173)
`doned.
`Int. CJ.4 ....................... A61K 7/06; A61K 31/74;
`CllD 3/48; CIID 9/50
`[52] u.s. Cl ....................................... 424170; 252/106;
`252/107; 424/DIG. 4; 424/78
`[58] Field of Search .......................................... 424170
`[56]
`References Cited
`U.S. PATENT DOCUMENTS
`3,816,616 6/1974 Angiullo et al ................ oooooo . 424/70
`3,849,548 11/1974 Grand oooo o oooooooo oo oo.ooooooooooooooooo 424/70
`3,987,162 10/1976 Scheuermann oooo . . . . oo oo00 oooo . . . . . 424/70
`4,292,212 9/ 1981 Melby et al. 00000000000000 00000000 00 00 424/70
`4,315,912 2/ 1982 Kalopissis et al. ooo oooooooooo oooo ·oo 424/70
`4,364,837 12/ 1982 Pader oooo oooooooooo oooooOo OO OOOO OO ooooooo 424/ 70
`4,397,322 8/1983 Arbaczawski oooo-oo.oooooo . . oooooo., 424/ 70
`
`FOREIGN PATENT DOCUMENTS
`0027730 4/1981 European Pat. Off. 000000000000 00 424170
`0024799 3/1981 Fed. Rep. of Germany 000000 00 424/70
`3032216 4/1982 Fed. Rep. of Germany 0000 00 00 424/70
`0072095 6/ 1981 Japan 000000000 000000000 00000000000000 0000' 424/ 70
`1333475 10/1 973 United Kingdom 000000000000 000000 424170
`2091102 7/1 982 United Kingdom ... oooooooooooooo, 424/ 70
`
`OTHER PUBLICATIONS
`Garlen, Cosmetics & Toiletries, 3/1979, pp. 66 to 68.
`Primary Examiner-Dale R . Ore
`Attorney, Agent, or Firm- Richard N. Miller; Richard J.
`Ancel; Herbert S. Sylvester
`[57]
`ABSTRACT
`A hair-conditioning shampoo based on anionic wash(cid:173)
`ing-active substances and containing from 0.1 to 4% by
`weight of a polycationic guar derivative, from 0.5% to
`5% by weight of a hardenable cationic polycondensa(cid:173)
`tion product, from 1 to 4% by weight of a hydrophilic
`fatty acid ester and from 0.1 to 1.0% by weight of a
`polyvinyl pyrrolidone gives particularly good wet(cid:173)
`combability values and improves the hair-cosmetic
`properties of hair after drying.
`
`8 Claims, No Drawings
`
`1
`
`

`

`4,676,978
`
`1
`
`SHAMPOO
`
`5
`
`25
`
`This is a continuation of application Ser. No. 542,630
`filed Oct. 17, 1983, now abandoned.
`This invention relates to hair-conditioning shampoos
`and body-washing preparations.
`After washing with shampoos, shower and bath prep(cid:173)
`arations based on synthetic anionic surfactants, the hair
`often is in a cosmetically unsatisfactory state. When 10
`wet, it is difficult to comb and feels dull. After drying,
`the washed hair tends to develop a static charge, result(cid:173)
`ing 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 condition- 15
`ing 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 con- 20
`ditioning 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 of
`the type described in DE-OS No. 21 50 899, polyca(cid:173)
`tionic cellulose derivatives of the type described in U.S.
`Pat. No. 3,816,616 or polycationic guar derivatives of
`the type described in U.S. Pat. No. 4,292,212. Many
`other water-soluble polymers containing cationic or 30
`quaternary ammonium groups have been proposed for
`this purpose.
`One disadvantage common to all known hair-condi(cid:173)
`tioning additives lies in their at least partly reduced
`effect when used in anion-active hair washing prepara- 35
`tions. Products having a particularly strong effect often
`show excessive adsorption to the hair and, as a result,
`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- 40
`known, heavily foaming anionic washing-active sub(cid:173)
`stances which, through the presence of suitable hair(cid:173)
`reviving additives, enables the hair to be readily
`combed when wet and also leaves the dry hair with
`satisfactory cosmetic properties, including in particular 45
`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 quar de- 50
`rivative, a hardenable cationic polycondensation prod(cid:173)
`uct, a hydrophilic fatty acid ester and a water-soluble
`polyvinyl pyrrolidone. Accordingly, the present inven(cid:173)
`tion relates to a hair-conditioning shampoo based on an
`aqueous solution of anionic washing-active substances 55
`and standard set-up agents which is characterized 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, 60
`hardenable polycondensation product of water-sol(cid:173)
`uble polyamines containing reactive amino groups
`and polyalkylene oxide radicals with epichlorohy(cid:173)
`drin or compounds containing more than one epox(cid:173)
`ide group and/or halohydrin group in the mole- 65
`cule,
`from I to 4% by weight of an esterification product
`of ethylene oxide adducts of glycerol and 4 to 20
`
`2
`moles of ethylene oxide with I to 2 moles of a
`Cs-C1s fatty acid,
`from 0.1 to 1% by weight of a polyvinyl pyrrolidone
`having an average molecular weight of at least
`10,000.
`The 3-(trimethylamino)-2-hydroxy propyl guar chlo(cid:173)
`ride is a cationic guar derivative known from U.S. Pat.
`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 aver(cid:173)
`age, each of the hexose rings carries three free hydroxyl
`groups. These free hydroxyl groups are reacted with
`reactive quaternary ammonium compounds to give the
`cationic polymers. The cationic polymer used in the
`shampoo according to the invention is commercially
`available under the name "Cosmedia ® Guar C 261."
`The readily water-soluble, hardenable, polyconden(cid:173)
`sation 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 mole(cid:173)
`cule are known from DE-PS No. 2,363,871. As set forth
`in said patent, to prepare the hardenable polycondensa(cid:173)
`tion products to be employed in the invented composi(cid:173)
`tions, it is necessary to proceed from polyamines with a
`content of polyalkylene oxide radicals, which are ob(cid:173)
`tained via known procedure by reacting polyamines,
`especially polyalkylene polyamines with mono- and/or
`polyfunctional derivatives of polya1kylene oxides.
`These mono- and/or polyfunctional derivatives of poly(cid:173)
`alkylene oxides can contain, as reactable groups, chlo(cid:173)
`rohydrin radicals, glycidyl radicals, halogen or other
`radicals capable of anion formation such as, for exam(cid:173)
`ple, sulfuric acid radicals, alkylsulfuric acid radicals,
`alkylsulfonic acid radicals and so forth. The polyalkyl(cid:173)
`ene oxide groups present in the polyalkylene oxide de(cid:173)
`rivatives can have varying molecule sizes, in which case
`the starting material is generally so chosen that approxi(cid:173)
`mately from 3 to 70 alkylene oxide radicals are avail(cid:173)
`able. 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 correspond(cid:173)
`ing 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 epichlo(cid:173)
`rohydrin, dichlorohydrins or bifunctional reaction
`products of these compounds with glycols, diglycols,
`polyalkylene oxides, glycerin, dicarboxylic acids, multi(cid:173)
`valent phenols, etc.
`The preparation of certain hardenable polycondensa(cid:173)
`tion products to be employed in the inventive composi(cid:173)
`tions can be effected via an especially simple procedure
`by reacting a polyalkylene glycol, e.g., a poly-oxyethy(cid:173)
`lene 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 triam(cid:173)
`ine 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 polycondensa-
`
`2
`
`

`

`3
`tion product. The reaction of the polyamines, which
`contain polyalkylene oxide radicals, with those com(cid:173)
`pounds containing in the molecule more than one epox(cid:173)
`ide and/or halogen hydrin group, can be carried out in
`the presence of organic solvents or, preferably, of wa(cid:173)
`ter. To speed up the reaction, appropriate acid-binding
`substances, such as caustic alkali, sodium carbonate,
`magnesium carbonate or triethanolamine can also be
`included.
`The reaction is carried out at temperatures between 10
`so· and 1 oo· 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 de(cid:173)
`sired degree of polycondensation-at which point the
`reaction product is still readily soluble-has been 15
`achieved, if necessary by means of adjusting the pH to
`<6.
`Of the cationic polycondensation products described
`in German DE OS No. 2,363,871 the polycondensate
`produced as product F of the above-mentioned patent is 20
`particularly suitable for use in the production of the
`hair-conditioning shampoos according to the invention.
`
`PRODUCTF
`Placed into a heatable and coolable agitator vessel, 25
`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 rais(cid:173)
`ing the heat to 68"-78", 56 kg. of epichlorohydrin are 30
`added with steady stirring and possible cooling so
`quickly that the temperature of the mixture remains
`between 68" and 70". Agitation is. continued for an hour
`at temperatures of approximately 70". The total quan(cid:173)
`tity of the obtained crude polyglycol-bis-chlorohydrin 35
`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, 40
`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 45
`600 remaining in the first vessel is then added with the
`application of agitation and kept at boiling for an addi(cid:173)
`tional 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 50
`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 solution. The yield is about
`400 kg. of a slightly yellowish, slightly opaque and
`highly viscous liquid.
`One product of this type is commercially available
`for example under the name of Polyquart H @.
`The esterification products of ethylene oxide adducts
`of glycerol and 4 to 20 moles of ethylene oxide with 1 to
`2 moles of a Cs-C1s fatty acid are known from DE-AS 60
`No. 20 24 051. Of the esterification products mentioned
`therein, a partial ester obtained by the addition of 7.4
`moles of ethylene oxide with 1 mole of glycerol, fol(cid:173)
`lowed by the esterification of I mole of the resulting
`adduct with I mole of Cs-C1s coconut oil fatty acid, is 65
`particularly suitable for use in the hair-conditioning
`shampoos according to the invention. A product having
`this composition is commercially available for example
`
`4,676,978
`
`4
`under the namde of Cetiol HE@. Polyvinyl pyrrol(cid:173)
`idones having an average molecular weight of approxi(cid:173)
`mately 40,000, corresponding to a K-value of approxi(cid:173)
`mately 30, are particularly suitable for the production of
`5 the hair-conditioning shampoos according to the inven(cid:173)
`tion.
`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 I part of the guar derivative to 0,5-4 parts of
`Polyquart @H to 0,5-4 parts ofCetiol @HE to 0,15-0,5
`parts of PVP.
`The hair·conditioning shampoos according to the
`invention preferably contain as water-soluble anionic
`washing-active substances alkali metal, magnesium,
`ammonium and/or Cz-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 semies(cid:173)
`ters 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 sec-
`ondary 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-C1s
`fatty acid alkylol amide polyglycol ether sulfates,
`Cs-C1s 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 18 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 sarcosines, acyl
`tamides and acyl isethionates containing from 8 to 18
`carbon atoms in the acyl group.
`In general, the concentration of anionic surfactants in
`the shampoo may range from about 5 to about 50% by
`weight; a preferred range is about 8 to about 30% by
`weight.
`A preferred anionic surfactant comprises a mixture of
`sodium Iaury! polyglycol ether sulfate and fatty alcohol
`sulfate in a ratio of about 2: I to 1:1 by weight. The fatty
`alcohol sulfate preferably contains an alcohol moiety
`with about 10-14 C-atoms, preferably 12-14 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 accord-
`55 ing to the invention may contain standard additives and
`set-up agents, such as for example thickeners of the
`Cs-C1s fatty acid alkylolamide type, opacifiers, for ex(cid:173)
`ample of the ethylene glycol distearate type, pH-stabi-
`lisers, such as alkali or ammonium phosphates or ci(cid:173)
`trates, preservatives, such as formaldehyde or p(cid:173)
`hydroxy benzoic acid esters, dyes, fragrances and
`known hair-cosmetic active substances, such as anti(cid:173)
`dandruff agents or sebostatics.
`The hair-conditioning shampoos having the composi(cid:173)
`tion according to the invention are distinguished by an
`unexpectedly marked improvement in the hair-condi(cid:173)
`tioning properties of hair washed with them. For exam(cid:173)
`ple, the so-called wet combability of the hair condition-
`
`3
`
`

`

`4,676,978
`
`5
`ing shampoos according to the invention is considerably
`improved in relation to shampoos containing only one
`of
`the conditioning components, e.g. Cosmedia
`Guar @C 261. This is the more surprising as the other
`essential ingredients have little or no influence on wet- 5
`combability 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 !0
`
`6
`shampoos set out in Table I 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 aver(cid:173)
`age combing resistance values are quoted in percent of
`the blank value. The blank value was determined after
`shampooing with an aqueous solution containing 10%
`by weight of sodium Iaury! ether diethenoxy sulfate and
`rinsing with clear water.
`TABLE I
`
`F atty alcohol (CJ2/ J4)·poly (2EO)glycol
`ethe r sulfate, sodium salt
`Fatty alcohol (C1 2114lsulfate, monoethanol
`ammonium salt
`Ethylene glycol distearate (20% dispersion
`in alkyl ether sulfate solution)
`Cosmedia guar C 261 ®*
`Polyquart H 81 @**
`Cetiol HE @*••
`Luviskol K 30 ®••••
`Perfume oil
`Preservative (Bronidox L5 @)
`Citric acid
`Water
`Resistanc e to wet combing in % of the
`value obtained after washing with a
`sodium Iaury) ether sulfate solution
`
`4
`
`6
`
`5.5
`
`10
`
`5.5
`
`5.5
`
`5.5
`
`5.5
`
`4.5
`
`4.5
`
`4.5
`
`4.5
`
`4.5
`
`3.0
`
`3.0
`
`3.0
`
`3.0
`
`3.0
`
`3.0
`
`1.5
`
`2.5
`
`1.5
`
`0.8
`2.0
`2.0
`2.5
`3.0
`1.0
`2.5
`1.0
`1.5
`0.4
`0.6
`0.6
`0.8
`0.8
`0.8
`0.8
`0.8
`0.8
`0.4
`0.4
`0.4
`0.4
`0.4
`0.4
`0.2
`0.2
`0.2
`0.2
`0.2
`0.2
`84.4
`83.6
`83.6
`79.4
`79.0
`78.5
`26% 25% 27% 95% 70% 35%
`
`5.5
`
`4.5
`
`3.0
`
`0.5
`0.8
`0.4
`0.2
`85.0
`110%
`
`5.5
`
`5.5
`
`4.5
`
`4.5
`
`3.0
`
`3.0
`
`1.2
`
`2.0
`2.0
`2.0
`0.6
`0.6
`0.8
`0.8
`0.4
`0.4
`0.2
`0.2
`81.0
`81.8
`31 % 75%
`
`10
`
`5.5
`
`4.5
`
`3.0
`
`0.8
`0.4
`0.2
`85.6
`100%
`
`•Guar-hydro"ypropyl-trimethylammon1um c hloride (CTFA name is Guar Hydroxypropyl trimmonium chloride)
`.. Polyglycol polyamine condensation resin
`.. • Polyethylene glycol (7.5) glyceryl monococare
`••••Polyvinyl pyrrolidonc: having an average molecular wejght of 40,000
`
`improved by the shampoos according to the invention
`to a greater extent than with conventional shampoos
`containing for example only one of the components 35
`required in accordance with the invention. Finally, the
`tendency of the hair to develop an electrostatic charge
`after drying is considerably reduced by using the condi(cid:173)
`tioning shampoo according to the invention. The hair
`tends less to "fly away", can be combed more easily and 40
`retains its shape for longer periods.
`The hair-cosmetic effects obtained with a hair condi(cid:173)
`tioning shampoo according to the invention are shown
`in the following examples by comparison with conven(cid:173)
`tional shampoos.
`
`EXAMPLES
`Shampoo formulations according to the invention
`(nos. 1-3) 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 I
`Determination of wet-combability (laboratory test)
`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 60
`machine (type 1402 as manufactured by the Zwick
`Company of Einsingen uber Dim/Danube) was used.
`The test arrangement is described in "Riechstoffe, Aro(cid:173)
`men, Kosmetika, No. 12/1977", page 325, columns 2
`and 3.
`Standardized strands of hair which had been preda(cid:173)
`maged by bleaching and permanent-waving under de(cid:173)
`fined conditions were used. They were washed with the
`
`EXAMPLE2
`Testing of hair-cosmetic properties (salon test)
`The testing and assessment of the hair-cosmetic prop(cid:173)
`erties were carried out on 10 test subjects differing from
`one another in the quality of their hair using the so(cid:173)
`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 shampoo No. 1
`according to the invention was used as the standard.
`The comparison marks given in Table 2 are a measure
`45 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. The standard shampoo was applied to the
`50 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-wash). In the case of
`the other 5 test subjects, the other half of their heads
`was treated with the same product. Both sides were
`55 shampooed in the same way and rinsed with 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 was carried out by
`the awarding of marks (l=excellent, 2=good, 3=mod(cid:173)
`erate, 4=poor). From the marks awarded for the 10 test
`65 subjects, the average values were calculated for the
`same product. The average values for the standard
`product were subtracted from the average values for
`the comparison product. The pair difference thus ob-
`
`4
`
`

`

`4,676,978
`
`7
`tained in the average values of the assessments of I 0 test
`subjects is shown in Table 2 below.
`Result: The comparison shampoos were all judged to
`be poorer in their hair-cosmetic properties than the
`standard shampoo (shampoo No. I according to 5
`the invention).
`
`TABLE 2
`Compariso n with shampoo No. I
`(Eair difference)
`5
`6
`
`4
`
`10
`
`-1.2 - 0.6 -0.4 - 1.0 -0.4 - 0.6
`-1.2
`± 0
`± 0 -0.9 - 0.8 -0.3 - 0.8 -0.5 - 0.8 -0.8
`
`±0
`±0
`
`- 0.5 -0.3 - 0.5
`- 0.5 -0.4 -0.6
`
`-0.6 - 0.1 -0.3
`- 0.3 -0.5 -0.3
`
`- 0.6
`- 0.6
`
`±0
`
`-0.5 -0.3 -0.2
`
`-0.5 -0.4 ±0
`
`- 0.5
`
`Salon tests
`
`Wet hair
`Combability
`Feel
`Dry hair
`Antistatic
`Feel
`(elasticity)
`Sheen
`
`10
`
`15
`
`8
`with an ether of poly C2-C3 alkylene glycol having
`terminal halohydrin or hydroxyl groups followed by
`reaction with either epichlorohydrin or the addition
`reaction product of said polyamine and said ether, (3)
`I% to 4% by weight of an esterification product formed
`by reacting I to 2 moles of Cs-CJs fatty acid with the
`adduct obtained by reacting 4 to 20 moles of ethylene
`oxide with I mole of glycerol and (4) 0.1% to 1% by
`weight of a polyvinyl pyrrolidone having an average
`molecular weight of 10,000 to 70,000, the weight ratio
`of (1):(2):(3):(4) being I :0.5-4:0.5-4:0.15-0.5 and the
`weight ratio of said anionic detergent to said condition(cid:173)
`ing mixture being from ID:I to l :I in an aqueous me(cid:173)
`dium.
`2. A shampoo according to claim 1 wherein 2% to
`8% by 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%
`20 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 claim 1 wherein said
`anionic detergent is a mixture of said Cs-Cis alkyl poly(cid:173)
`glycol ether sulfate and Cs-CJs alkyl sulfate in a ratio of
`2: I to I: I by weight.
`6. A shampoo according to claim 2 wherein said
`anionic detergent is a mixture of said Cs-CJs alkyl poly(cid:173)
`glycol ether sulfate and Cs-C!s alkyl sulfate in a ratio of
`2: 1 to 1: I by weight.
`7. A shampoo according to claim 3 wherein said
`anionic detergent is a mixture of said Cs-C1s alkyl poly(cid:173)
`glycol ether sulfate and Cs-C1s alkyl sulfate in a ratio of
`2: I to 1: 1 by weight.
`8. A shampoo according to claim 4 wherein said
`anionic detergent is a mixture of said Cs-C1s alkyl poly(cid:173)
`glycol ether sulfate and Cs-C1s alkyl sulfate in a ratio of
`2: I to I: 1 by weight.
`* • * * *
`
`What is claimed is:
`1. A hair conditioning shampoo consisting essentially
`of 5 to 50% by weight of a water soluble, anionic, alkali
`metal, magnesium, ammonium or C2-C3 alkanol ammo(cid:173)
`nium detergent salt selected from the group consisting
`of C8- C1 s alkyl sulfates, C8-C1s alkyl polyglycol ether 25
`sulfates having 1 to 6 glycol ether groups in the mole(cid:173)
`cule, Cw-C18 alkane sulfonates, Cw-C1s olefin sulfa(cid:173)
`nates, Cg-C1s fatty acid alkylolamide polyglycol ether
`sulfates, Cs-CJs fatty acid monoglyceride sulfates,
`Cs-Cis alkyl sulfosuccinates, C6-CIO dialkylsulfosucci- 30
`nates, Cs-CJs alkyl polyglycol ether carboxylates hav(cid:173)
`ing 2-6 polyglycol ether groups in the molcule, Cs-C1s
`acyl sarcosinates, Cs-CJs acyl taurides and Cs-C1s acyl
`isethionates and 1.7% to 14% by weight of a mixture of
`conditioning agents consisting of (1) 0.1% to 4% by 35
`weight of 3 (trimethylamino)-2-hydroxypropyl guar
`chloride, (2) 0.5% to 5% by weight of a readily water(cid:173)
`soluble, hardenable polycondensation product formed
`by reacting a water-soluble polyamine containing reac(cid:173)
`tive amino groups and having from 4 to 6 carbon atoms 40
`
`45
`
`50
`
`55
`
`60
`
`65
`
`5
`
`