United States Patent
`Drakoff
`
`[191
`
`[54] LUSTERIZING SHAMPOO CONTAINING A
`POLYSILOXANE AND A HAIR-BODYING
`AGENT
`Inventor: Raymond Drakoff, New York, N.Y.
`[75]
`[73] Assignee: Lever Brothers Company, New
`York, N.Y.
`June 18, 1975
`[22] Filed:
`[21] Appl. No.: 588,120
`Related U.S. Application Data
`Continuation of Ser. No. 428,288, Dec. 26, 1973,
`abandoned.
`
`[63]
`
`U.S. CI. ................... , ........... 132/7; 252/DIG. 2;
`252/DIG. 3; 252/DIG. 13; 252/542; 252/550;
`252/551; 424/DIG. 2; 424/70; 424/78;
`424/81; 424/180; 424/362
`Int. CI.2
`............................................ A61K 7/06
`Field of Search ....... 132/7; 424/70, 71, DIG. 2;
`252/DIG. 2, DIG. 3, DIG. 13, 542, 550, 551
`
`[52]
`
`[51]
`[58]
`
`[56]
`
`References Cited
`UNITED STATES PATENTS
`8/1965 Cook eta!. ......................... 252/389
`
`3,198,747
`
`3,964,500
`[II]
`[45] June 22, 1976
`
`3,208,911
`9/1965 Oppliger ............................... 424!70
`3,392,040
`7/1968 Kass ...................................... 424!70
`2/1971 Bailey et al... ...................... 252/137
`3,562,786
`3,580,853
`5/1971
`Parran .............................. 424/70 X
`FOREIGN PATENTS OR APPLICATIONS
`1 ,362,179
`4/1964 France .................................. 424/70
`8,757
`8/1906 Netherlands .......................... 424/70
`
`Primary Examiner-V. D. Turner
`Assistant Examiner-Vera C. Clarke
`Attorney, Agent, or Firm-Kenneth F. Dusyn; Arnold
`Grant
`
`[57]
`ABSTRACT
`Undesirable effects, such as heaviness, oiliness and
`stringiness, accompanying the deposition of lusteriz~ng
`amount:; of polydimethylsiloxane on the hair durmg
`shampooing are reduced or overcome without sub(cid:173)
`stantially affecting luster by the presence in the sham(cid:173)
`poo composition of a polymeric hair bodying agent.
`The polymeric hair bodying agent also posse.sses the
`property of increasing the amount of polydimethyl(cid:173)
`siloxane deposited on the hair.
`
`16 Claims, No Drawings
`
`1
`
`

`

`1
`
`3;964,500
`
`LUSTERIZING SHAMPOO CONTAINING A
`POLYSILOXANE AND A HAIR-BODYING AGENT
`This is a continuation of application Ser. No.
`428,288, filed Dec. 26, 1973, now abandoned.
`
`2
`Accordingly in itS broadest aspect, the invention
`provides a foaming shampoo composition which con(cid:173)
`tains a water-insoluble polydimethylsiloxane lusterizing
`agent and a polymeric hair bodying agent, which, in
`5 addition to its known function of providing body to the
`hair greatly reduces the aforesaid oiliness, heaviness
`and stringiness imparted to the hair by the polydimeth-
`ylsiloxane and additionally co-acts to increase the
`amount ofthe polysiloxane deposited on the hair.
`In a broad embodiment of the invention there is pro-
`vided a shampoo composition comprising:
`i. an anionic or amphoteric foaming detergent surfac-
`tant,
`ii. a water-insoluble polydimethylsiloxane having
`hair-lusterizing properties and having a viscosity of
`about I ,000 to about 2,500,000 centistokes mea-
`sured at 25°C, and mixtures thereof,
`iii. a hair bodying agent, which is a polymeric resin-
`ous substance, and
`iv. water, which may contain up to about its own
`weight of ethanol.
`
`IS
`
`BACKGROUND OF THE INVENTION
`1. Field of the Invention
`The present invention relates to a hair lusterizing
`shampoo containing an anionic or amphoteric surfac- 10
`tant foaming agent, a lusterizing agent which is a poly-
`dimethylsiloxane, and a hair bodying polymeric resin
`which is soluble in water or solubilized in the aqueous
`shampoo product.
`Polydimethylsiloxanes having relatively low viscosi-
`ties, for example about 25 centistokes or less, have
`poor adhesiveness on the hair when applied to the hair
`from a shampoo composition and have substantially no
`hair-grooming properties. On the other hand, the
`polydimethylsiloxanes useful in the practice of the pre- 20
`sent invention, i.e., those having viscosities of about
`1 ,000 to about 2,500,000 centistokes, are effective
`hair-grooming agents when heavily deposited on the
`hair, but introduce problems of heaviness, oiliness, and
`stringiness. When an excessive amount of a siloxane 25
`has been deposited on the hair, many hair styles be(cid:173)
`come difficult to achieve. Overconditionec,l hair tends
`to lie ·flat and to be slick.
`The aforementioned resin not only performs the
`function of a hair-bodying agent, but cooperates with
`the polydimethylsiloxane to reduce the oiliness, heavi(cid:173)
`ness and stringiness of the hair imparted by the siloxane
`and to increase the amount thereof deposited on the
`··
`·
`·
`hair.
`2. The Prior Art
`Shampoo comp(>sitions containing water"insoluble
`polydimethylsiloxane are well known in the art, as illus(cid:173)
`trated by the disclosures in U.S. Pat. No. 2,826,551'
`assigned to the Simoniz Company.
`As a further illustration of the use of polysiloxanes in
`hair care products reference may be made to an article
`by Charles W. Todd and Steven Hayes in "Americn
`Perfumer and Cosmetics", Volume 86, pages 112-114,
`October, 1971. In this article the authors disclose the
`use of silicones to relieve the stickiness of the resins in
`a hair spray.
`U.S. Pat. No. 3,215,603 discloses the use _in hair(cid:173)
`grooming compositions of a copolymer of a low molec(cid:173)
`ular weight olefin and maleic anhydride cross linked
`with vinyl crotonate.
`U.S. Pat. No. 2,415,389 describes a method for the
`preparation of alkoxy end-blocked polysiloxanes.
`
`DETAILED DESCRIPTION OF THE INVENTION
`The surfactant, which is a compound capable of pro(cid:173)
`ducing a desired level of foam and of having a good
`detergent action on the hair when used as a shampoo,
`may be present in the composition in proportions of
`about 5% to about 25%, whole composition basis. The
`surfactants within the meaning employed in the instant
`30 specification are free of silicon in their molecular struc(cid:173)
`ture.
`The polydimethylsiloxane may be present in the com(cid:173)
`position in proportions of about 3% to about 60%, and
`the hair-bodying agent in proportions of about 1% to
`35 about 25%, whole composition basis.
`The solvent will comprise about 30% to about 91% of
`the composition by weight, and may comprise 0% to
`about 50% ethanol by weight of the solvent, the bal(cid:173)
`ance, about 50% to 100%, being water.
`40 The shampoo compositions of the invention impart
`good groom and brilliantine effects to the hair, and
`eliminate or greatly reduce comb resistance. The poly(cid:173)
`dimethylsiloxane component is chemically stable in the
`shampoo medium, is safe for external use, has very
`45 little adverse effect on lather volume, and does not
`affect hair dyeing or cold waving.
`By the term "bodying" as applied to the hair is meant
`· the conferring thereupon of a feeling of thickness or
`substance manifested by improved control during
`so combing, shaping, or teasing. The consumer may pre(cid:173)
`ceive this as an increase in combing resistance or drag
`on the hair either in the wet or dry state. Physically, the
`interfiber friction of hair has been increased.
`SUMMARY OF THE INVENTION
`To achieve a desired level of gloss or luster on the
`It has now been discovered that the oiliness, heavi- 55 hair, the shampoo may contain relatively large amounts
`of a low viscosity polydimethylsiloxane or a relatively
`ness, and stringiness imparted to hair shampooed with
`a.· foaming composition containing a water-insoluble
`small amount of a high viscosity polydimethylsiloxane.
`polydimethylsiloxane lusterizing agent is greatly re-
`For example, no luster improvement is obtained in
`duced or overcome by the presence in the composition
`vitro with a shampoo containing up to 50% of its weight
`of a polymeric hair-bodying agent. Additionally the 60 of a polydimethylsiloxane having a viscosity of 100
`polymeric hair-bodying agent increases the amount of
`centistokes although an improvement in luster is noted
`polydimethylsiloxane deposited on the hair.
`at a level of 50% when the polydimethylsiloxane has a
`It is an object of the present .invention to formulate a
`viscosity of 5,000 centistokes. Also, an improvement is
`shampoo having a lusterizing effect on. the hair without
`noted when the shampoo contains only 10% of a poly-
`65 dimethylsiloxane having a viscosity of 30,000 centi-
`any attendant oiliness, ·heaviness,.and stringiness.
`lt is another object :of .the invention to .enhance the
`stokes.
`deposition ofa polydimethylsiloxanelusterizipg agent
`Viscosities of the polydimethylsiloxanes useful in the
`on the. hair during a ~hampoo operation,.,; , ·
`practice of the present invention are within the range of
`
`2
`
`

`

`3,964,500
`
`q.s.
`
`3
`4
`of the hair grooming agent, i.e., promote even distribu-
`about 1,000 to about 2,500,000 centistokes, preferably
`about 5,000 to about 60,000 centistokes, measured at
`tion throughout the hair. Examples of suitable materi-
`als are hydroxylpropylmethyl cellulose, proteins, gela-
`250C. Average molecular weights range broadly from
`tin, methyl cellulose, fumed silicas and polyoxyethy-
`about 17,000 to about 180,000, preferably from about
`5 Iene.
`30,000 to about 52,000.
`Additionally, these thickeners are used to stabilize
`The presence of a bodying agent counteracts the
`gel and liquid preparations of the invention by virtue of
`lubricity of the hair imparted by the polydimethylsilox-
`the viscosity they impart to the system. Thus, dimethyl-
`ane, but ordinarily does not significantly decrease the
`luster, and the combination thereby imparts visual Ius-
`polysiloxanes are dispersed throughout the preparation
`ter with substantially no tactile feel of oiliness.
`10 and maintained in suspensions and dispersion by virtue
`The reason for the enhancing effect of the hair-body-
`of the viscosity imparted to the external phase by these
`hydrophilic materials. These systems are thereby stabi-
`ing resin on the lusterizing and deposition characteris-
`lized and the separation of the dimethylpolysiloxane
`tics of the polydimethylsiloxane is not known. While
`into a clear layer is prevented. This is of value to the
`not wishing to be held to any theory, it is believed that
`the hair-bodying resin precipitates upon dilution of the 15 consumer who may prefer this form of product.
`shampoo composition and application to the hair,
`Other water-soluble salts may also be used as hydro-
`whereupon the resin coacervates with the siloxane and
`philic thickeners.
`the coacervate deposits on the hair strands.
`Also useful as hydrophilic thickeners are watersolu-
`In use, the hair is washed with a shampoo composi-
`ble salts which are electrolytes well known for this
`tion within the instant invention, the washing being 20 purpose in the art. Exemplary of such electrolytes, to
`which however the compositions of the invention are
`carried out by simple shampoo procedures, usually
`with a diluted product, generating a foam on the hair,
`not limited, are the alkali-metal halides such as sodium
`preferably by movement of the hands and fingers, then
`chloride and potassium chloride, the ammonium and
`rinsed with water to remove substantially all foaming
`substituted ammonium halides, such as ammonium
`components from the hair. By these steps, and provided 25 chloride, monoethanolammonium
`chloride, die-
`thanolammonium chloride, and triethanolammonium
`that the shampoo contains at least one of the polydime-
`thylsiloxanes and one of the hair-bodying agents de-
`chloride, the alkali-metal sulfates, phosphates, citrates
`scribed hereinafter, the polydimethylsiloxane is depos-
`and lactates.
`ited on the hair in an amount at least sufficient to im-
`The shampoo composition may of course also in-
`p~~ visual luster with substantially no tactile feel of 30 elude, if desired such further adju~ants as perfumes or
`mhness.
`. .
`.
`.
`.
`essential oils, dyes and the like to enhance and improve
`The compos1t10~s <?ft:J:le mvent10n may be m the form
`the commercial acceptability of the product. The re-
`of pourable: t~rbtd h':lmds, or rna~ be gel~, or may be
`mainder of the composition usually comprises water.
`two-phase hqmds havmg the polysdoxane m the upper
`Suitable lusterizing shampoo compositions may con-
`35 tain the following components in the broad and pre-
`lay~r. .
`.
`.
`Ltqutd forms of the product of the mventton may
`ferred proportions set forth below:
`contain about 5% to about 25% surfactant, about 3% to
`about 50% polysiloxane having a viscosity of about
`Percent By Weight,
`1 ,000 to about 2,500,000 centistokes at 25°C, and
`Whole composition Basis
`about 1% to about 10% of a polymeric resinous hair- 40 ___ ___________ B_ro_a_d ___ Pr_e_re_rr_ed_
`bodying substance.
`10-20
`5-25
`Surfactant
`Gel forms may contain about 5% to about 25% sur(cid:173)
`10-40
`3-60
`Polydimethylsiloxane
`1-25
`3-15
`Hair·bodying resinous substance
`factant, about 3% to about 25% polysiloxane having a
`0-5
`2-3
`Hydrophilic thickener
`viscosity of about 1 ,000 to about 2,500,000 centistokes
`0-5
`1-3
`Suds booster
`10-25
`0-40
`at 25°C, and about 1% to about 25% of a hair-bodying 45
`Ethanol
`20-50
`20-80
`Water
`substance.
`Perfume, colorant, preservative,
`Two-phase liquid forms of the product may contain
`opacifier, U. V. absorber
`about 5% to about 25% surfactant, about 10% to about
`60% polysiloxane having a viscosity of about 1 ,000 to
`about 2,500,000 centistokes at 25°C, and about 1% to 50
`about 25% of hair-bodying substance.
`When the product is a two-phase liquid system, the
`aqueous phase may comprise one or more of the com(cid:173)
`positions described in U.S. Pat. No. 3,533,955, the
`disclosures of which are incorporated herein by refer- 55
`ence. In this embodiment the siloxane constitutes the
`upper oily layer and the hair-bodying agent is incorpo(cid:173)
`rated into the aqueous layer. The siloxanes form less
`stable emulsions in shampoo systems than do the oily
`components in the compositions of the aforementioned 60
`U.S. Pat. No. 3,533,955, and consequently the liquid
`phases may separate sufficiently soon after using to
`make the presence of an emulsion destabilizer less
`important than in the compositions of U.S. Pat. No.
`3,533,955.
`Optionally, the shampoo composition may further
`contain from about 0. 1 to about 10 weight percent of a
`hydrophilic thickener to prevent localized deposition
`
`The surfactant system comprises one or more water(cid:173)
`soluble surface-active agents, i.e., an anionic surfac(cid:173)
`tant, an amphoteric surfactant, a soap, or a mixture
`thereof which produces acceptable foam or whose
`foam is supplemented by a suds improver. Useful an(cid:173)
`ionic detergents are sulfonated and sulfated anionic
`detergents and in particular the sodium, magnesium,
`potassium, ammonium and substituted ammonium salts
`of sulfated fatty alcohols as well as these salts of the
`sulfonated alkylaryl compounds, and the acyl isethion(cid:173)
`ates, and mixtures thereof.
`Amphoteric or ampholytic detergents include N-lau(cid:173)
`ryl-N '-carboxymethyl-N '-(2-hydroxyethyl)e(cid:173)
`thylenediamine, coco-beta-alanine, the alkali-metal
`salts of protein-coconut fatty acid condensates, the
`aminopropionates such as alkyl beta-imin6dipropion(cid:173)
`ate represented by RN(CH2CH2C00Mh, and alkyl
`beta-iminopropionate
`represented
`by
`RNHCH 2CH2COOM wherein R is an aliphatic hydro-
`
`65
`
`3
`
`

`

`3,964,500
`
`6
`lauric" oils, that is, oils or fats wherein at least 50% of
`the total fatty acids are composed of lauric or myristic
`acids or mixtures thereof. These oils are generally ex(cid:173)
`emplified by the tropical nut oils of the coconut oil
`5 class, such as palm kernel oil, babassu oil, ouricuri oil,
`tucum oil, cohune nut oil, murumuru oil, jaboty kernel
`oil, khakan kernel oil, dika nut oil, and for present
`purposes ucuhuba butter, a vegetable triglyceride high
`in myristic acid esters.
`10 A preferred soap is a mixture of about 15% to about
`25% coconut oil and about 75% to about 85% tallow.
`These mixtures contain about 95-96% fatty acids hav(cid:173)
`ing about 12 to about 18 carbon atoms. The soap may
`be prepared from coconut oil, in which case the fatty
`15 acid content is about 84% of C12-C18 chain length.
`The soaps may contain unsaturation in accordance
`with the commercially acceptable standards. Excessive
`unsaturation is normally avoided.
`The soaps may be made by the well-known kettle
`boiling process from natural fats and oils such as tallow
`or coconut oil or their equivalents, by boiling with an
`alkali-metal hydroxide, using procedures well known to
`those skilled in the art. Alternatively the soaps may be
`25 made by neutralizing fatty acids, such as lauric (C 12),
`myristic (C 14 ), palmitic (C16), or stearic (C18) acids
`with an alkali-metal hydroxide or carbonate.
`The amphoteric detergents may include any of the
`high-foaming quaternary cycle compounds disclosed in
`30 the aforementioned U.S. Pat. Nos. 2,528,378 and
`2,781 ,354. Of special interest are the quaternary cy(cid:173)
`cloimidates having the general structure.
`
`20
`
`5
`carbon radical having about 8 to about 18 carbon
`atoms and M is a water-solubilizing cation, betaines,
`sultaines, and the Miranol compounds described in
`U.S. Pat. Nos. 2;528,378 and 2,781 ,354, incorporated
`herein by reference.
`Other examples, well known to the art, may be found
`in the literature such as "Surface Active Agents" by
`Schwartz and Perry and "Surface Active Agents and
`Detergents" by Schwartz, Perry and Berch, both Inter(cid:173)
`science Publishers, New York, New York, the disclo(cid:173)
`sures of which are incorporated herein by reference.
`The most preferred detergents are the anionics.
`Preferred anionics are the alkyl sulfates wherein the
`alkyl group may be straight or branched, saturated or
`unsaturated, and have six to 24 carbon atoms, prefer(cid:173)
`ably about 12 to about 18 carbon atoms. Particularly
`preferred are
`the monoethanolammonium, die(cid:173)
`thanolammonium and triethanolammonium alkyl sul(cid:173)
`fates wherein the alkyl group is a member selected
`from the group consisting. of dodecyl and tetradecyl
`and mixtures thereof. Also preferred is .. the trie(cid:173)
`thanolammonium salt of the sulfated condensate of
`dodecyl - or tetradecyl alcohol or mixtures thereof and
`about 2 to about 5 molar proportions of ethylene oxide.
`Sodium acyl isethionate may be prepared by methods
`well known to those skilled in the art. Suitable prepara(cid:173)
`tory procedures may be found in U.S. Pat. Nos.
`3,320,292,
`3,376,229,
`3,151,136,
`3,383,396,
`3,420,857 and 3,420,858.
`The alkylbenzenesulfonates useful in the present
`invention may have a branched alkyl group of about 9
`to about 15 carbon atoms such as may be derived from
`polypropyleneas described in U.S. Pat. Nos. 2,477,382
`and 2,477,383. Preferably the alkyl group is a straight
`chain having about 11 to about 15 carbon atoms and 35
`the sulfonated phenyl group is randomly positioned
`along the alkyl chain. Also useful are the alkylbenzene(cid:173)
`sulfonates described in U.S. Pat. Nos. 2,390,295/
`3,320,174 and in Nos. 2,712,530 and 2,723,240.
`The term "soap" is used herein in its popular mean- 40
`ing, i.e., the alkali metal salts of aliphatic alkane- or
`alkenemonocarboxylic acids. The soaps useful herein
`are the well-known alkali-metal salts of natural or syn(cid:173)
`thetic fatty (alkanoic or alkenoic) acids having about
`12 to about 20 carbon atoms, preferably about 12 to 45
`about 18 carbon atoms, and may be described as alkali(cid:173)
`metal carboxylates of acyclic hydrocarbons. having
`about 12 to about 20 carbon atoms.
`Soaps having the fatty acid distribution of coconut oil
`may provide the lower end of the broad molecular 50
`weight range, while soaps having the fatty acid distribu(cid:173)
`tion of peanut or rapeseed oil, or their hydrogenated
`derivatives, may provide the upper end of the broad
`molecular weight range. It is preferred to use the soaps
`having the fatty acid distribution of coconut oil or tal- 55
`low, or mixtures thereof, since these are among the
`more readily available fats. The proportion of fatty
`acids having at least 12 carbon atoms in coconut oil
`soap is about 84%. This proportion will be greater
`when mixtures of coconut oil and fats such as tallow, 60
`palm oil, or non-tropical nut oils or fats are used,
`wherein the principal chain lengths are C 16 and higher.
`The preferred soap for use in the present invention
`then has at least 84% fatty acids having about 12-18
`carbon atoms.
`It will be understood that the coconut oil employed
`for the soap, and for the nonsoap surfactant as well,
`may be substituted in whole or in part by other "high-
`
`CH2
`
`N
`
`CH2
`1/R'-O-A
`
`/ "
`II
`R-C--N I 'R•-cooM
`
`B
`
`wherein
`R is an aliphatic hydrocarbon radical having about 9
`to about 17 carbon atoms,
`R' and R2 are each independently
`a. a divalent alkylene radical having I to 4 carbon
`atoms,
`b. a hydroxy-substituted divalent alkylene radical
`having 2 to 4 carbon atoms,
`c. a divalent alkylene radical having 2-4 carbon
`atoms wherein said alkylene radical contains an
`ether or a keto linkage, and
`d. a hydroxy-substituted divalent alkylene radical
`having 2-4 carbon atoms wherein said alkylene
`radical contains an ether or a keto linkage,
`M is a water-solubilizing cation,
`A is
`a.M,
`b. -CH2COOM
`c. -C2H40CH2COOM or
`d. -C2H4COOM, and
`B is
`a. OH,
`b. C,2H2sOSOa-, or
`c. C,2H2s-CsH4-S03-
`Particularly preferred amphoteric surfactants are the
`substituted quaternary hydroxy cycloimidinic acid a!-
`
`65
`
`4
`
`

`

`7
`kali metal alcoholates described in U.S. Pat. No.
`2,528,378 and which have the generic structure:
`
`3,964,500
`
`/c~
`N
`CH2
`I
`
`II
`
`R -C--N-R'-ONa
`
`\R2C00Na
`
`/
`OH
`
`wherein R is an aliphatic hydrocarbon radical having
`about 9-17 carbon atoms, R' and R2 represent divalent
`alkylene groups having I to 4 carbon atoms, and may 15
`be the same or different.
`The most preferred of the amphoteric surfactants are
`the substituted quaternary hydroxy cycloimidinic acid
`alkali metal alkoxymethyl carboxylates described in
`U.S. Pat. No. 2,781 ,354, and which have the generic 20
`structure:
`
`8
`tioned surfactants may not be suitable for others, as for
`example calcium and magnesium cations, which are
`appropriate for many of the nonsoap surfactants but
`are not suitable as cations in the compositions of the
`5 instant invention when the surfactant is predominantly
`soap.
`Among the cations which may be associated with the
`surfactants, subject to the aforementioned limitation,
`are sodium, potassium, lithium (alkali metals, group I
`10 of the Periodic Table), calcium, magnesium (group II
`of the Periodic Table), ammonium, and substituted
`ammonium ions. Among the substituted ammonium
`ions there may be mentioned the methyl-, dimethyl-,
`trimethyl-, tetramethyl-, ethyl-, diethyl-, triethyl-, tetra(cid:173)
`ethyl-, monoethanol-,
`diethanol-,
`triethanolam(cid:173)
`monium, and morpholinium ions.
`Compatible mixtures of the foregoing types, i.e.,
`anionics, amphoterics, or soap, or mixtures within each
`type, may be used.
`The polydimethylsiloxanes suitable for use in the
`present inventon are the well-known dimethylsiloxane
`polymers which may generally be represented by the
`structure:
`
`/c~
`N
`CH2
`II
`I
`I \
`
`R 2C00Na
`
`OH
`
`R-C--N-R'-O-R3COONa
`
`25
`
`30
`
`wherein R is an aliphatic hydrocarbon radical having
`about 9 to about 17 carbon atoms, R' and R2 are as
`defined above, and R3 is a divalent alkylene group
`having 1 to 2 carbon atoms.
`A useful compound is one having the foregoing struc(cid:173)
`ture wherein R has 11 carbon atoms, R' has 2 carbon
`atoms and R2 and R3 each have 1 carbon atom.
`The betaines may have the structure
`
`wherein R1 is an alkyl group having about 12 to about
`18 carbon atoms or a mixture thereof, R2 and R3 are
`independently lower alkyl groups having 1 to 3 carbon
`atoms, and N is an integer from 1 to 4. Specific betaines
`useful in the products of the invention are for example
`alpha-( tetradecyldimethylammonio) acetate, beta((cid:173)
`hexadecyldiethylammonio )propionate,
`and gamma
`( dodecyldimethylammonio )butyrate.
`The sultaines may have the structure
`
`wherein R" R2 , R3 and x are defined as above. Specific
`useful sultaines are for example 3-(dodecyldime(cid:173)
`thylammonio) propane-1-sulfonate, and 3-(tetradecyl(cid:173)
`dimethylammonio )ethane-1-sulfonate.
`The the term "water-solubilizing cation" is meant
`any cation which, when associated with the detergent
`anion, does not result in an insoluble compound. A
`cation suitable as the cation of some of the aforemen-
`
`wherein x is an integer from about 220 to about 2400,
`35 and A is CH3, CH30,C2H50 or C3H70.
`While the structure of the polydimethylsiloxanes is
`illustrated as having the above molecular configura(cid:173)
`tion, it will be understood that the commercially avail(cid:173)
`able grades may be mixtures of polysiloxanes wherein
`40 the above structure predominates. Moreover, values
`assigned to x in the present application are average
`values.
`The polydimethylsiloxane polymers may be made by
`procedures well known by those skilled in the art, and
`45 may be made at varying degrees of polymerization, to
`provide viscosities of from example 0.65 to 2,500,000
`centistokes.
`Suitable preparative methods are found in the text,
`"An Introduction to the Chemistry of Silicones" by E.
`50 G. Rochow, second Edition, 1951, John Wiley & Sons,
`Inc. New York.
`In one method described, for the preparation of
`methyl-blocked silicones, elemental silicon is reacted
`with methyl chloride under the influence of copper
`55 metal catalyst to produce dimethyldichlorosilocane,
`along with certain by-products. The dimethyldi(cid:173)
`chlorosilocane is hydrolyzed and polymerized to form
`the desired polydimethylsiloxane.
`Methods for the preparation of alkoxy end-blocked
`60 polysiloxanes are found in U.S. Pat. No. 2,415,389,
`which is incorporated herein by reference.
`A discussion of silicones in general may be found in
`Kirk-Othmer, "Encyclopedia of Chemical Technol(cid:173)
`ogy", Volume 18, 1969, Interscience Publishers, par-
`65 ticularly at pages 221-248.
`The polydimethylsiloxanes employed in the Exam(cid:173)
`ples herein are members of the Viscasil series. Viscasil
`is a trademark of the General Electric Company.
`
`5
`
`

`

`9
`Mixtures of the aforementioned polysiloxanes having
`different viscosities and chain lengths may be em(cid:173)
`ployed.
`Resinous materials, in general, tend to impart body(cid:173)
`ing or set holding to the hair. Suitable resins for pur- 5
`poses of the present invention would include shellac;
`wood rosins and the cl to c6 esters thereof, the wood
`rosins and esters preferably having a softening point of
`between about 96°C to about 125°C and A Gardner(cid:173)
`Holt viscosity of between about 20 and 40. Preferred I 0
`embodiments of these rosins are their C 1 to C6 esters
`and polymerized and dimerized rosins (softening point
`98°-l06°C, acid number 140 minimum), hydrogenated
`rosin (softening point 69°-80°C, acid number !58 mini(cid:173)
`mum) and hydrogenated methyl ester of rosin (boiling 15
`point 350°-380°C preferably 360°-364°C, acid number
`7 minimum). Other suitable hair-bodying are sucrose
`acetate isobutyrate, polyvinyl ethyl ether resin having a
`molecular weight of from about I 0,000-750,000, alkyl
`resins having a preferred . molecular weight of from
`about I 0,000-50,000, polyketone resins having a pre(cid:173)
`ferred average molecular weight of from about
`500-1,000, most preferably 600-800, vinyl acetate
`resins having an average molecular weight of from
`about 8,000-15,000, acrylic resins having an average 25
`molecular weight of from about 10,000-150,000, and
`mixtures thereof.
`Waxy materials tend to impart bodying and condi(cid:173)
`tioning effects to the hair. Suitable waxy materials
`would include, but are not limited to, cocoamide (pref(cid:173)
`erably having a melting point of 80°-90°C), ethylene(cid:173)
`maleic anhydride resins, ethoxylated lanolin containing
`about 5 to about 25 moles of ethylene oxide, stearyl
`(preferably . having a melting point of
`amide
`95°-ll0°C), ethoxylated higher fatty alcohols, prefer- 35
`ably C14-C30 having 2 to 4 moles of ethylene oxide, and
`the like. Liquid grooming agents such as lanolin alco(cid:173)
`hols (preferably having a saponification value of aboul'
`144-150), mineral oil fractions having a Saybolt viscos-
`ity of about 50 to about 360 sec., and the like, tend to
`
`3,964,500
`
`10
`impart conditioning and ease of combing effects to the
`hair.
`Preferred hair bodying agents are the above defined
`wood rosins, sucrose acetate isobutyrate, a copolymer
`of vinyl acetate and crotonic acid having a molecular
`weight of about 12,000, an ethylene-maleic anhydride
`copolymer cross linked with vinyl crotonate, having a
`viscosity of about 160,000 cps, polyketone and shellac
`used alone or in combinations, such as wood rosins -
`polyketone, and sucrose acetate isobutyrate- polyke(cid:173)
`tone at ratios from about 1:9 to about I: 1, most prefer-
`ably I :5 to 5: I. Combinations of hair grooming agents
`are often desired because of the balance of benefits
`they provide.
`The use of a suds booster is optional. When desired,
`the suds boosters useful in the shampoo compositions
`of the invention may be selected from the compounds
`well known for their general and specific effects. For ·
`example, there may be used the fatty amides, such as
`20 lauric, myristic, and palmitic amides, monoethanola(cid:173)
`mides, diethanolamides,
`and
`isopropanolamides.
`Where 1mitable, the stearic derivatives may be used.
`Mixed lauric and myristic derviatives of the aforemen-
`tioned amides and substituted amides, as well as the
`coconut oil and tallow derivatives are useful. Laury!
`alcohol and myristyl alcohol find utility with the alkyl
`sulfate detergents. Also useful are the sulfoxides, amine
`oxides, and phosphine oxides having one
`long
`(C12-C18 ) alkyl chain, the particular compounds being
`30 well known in the art. It will be understood that the
`suds booster, when desired, will be selected with due
`regard to the detergent species with which it is to be
`associated.
`The invention may be more fully understood by ref(cid:173)
`erence to the following examples, which illustrate, but
`by no means limit the scope of the invention.
`
`EXAMPLE 1
`
`The following compositions are within the invention.
`
`Polydimethylsiloxane, I ,000 centistokes'"'
`Polydimethylsiloxane, 5,000 centistokes'"'
`Polydimethylsiloxane, 10,000 centistokes'"'
`Polydimethylsiloxane, 30,000 centistokes'"'
`Polydimethylsiloxane, 2,500,000 centistokes'"'
`Shellac, bleached, dewaxed
`Sucrose. acetyl isobutyrate•••
`Cationic cellulose•••
`Polymerized rosin•••
`Ethanol
`Methyl cellulose, 60 NG'"
`Triethanolammonium Iaury! sulfate
`Potassium lauryl.E.O. sulfateUl,
`Ammonium alkylbenzenesulfonate'"'
`Lauric diethanolarnide
`N"alkyl-beta-alanine•••
`Alkyl dimethyl amine oxide•••
`Perfume
`Triethanolamine, q.s. to pH 6.2
`Water, q.s. to 100%
`
`<a>Figures are viscosity at .25°C in centistokes.
`' 0'SAIB 90, obtainable from the Eastman Kodak Co .
`.. ;.'Polymer JR ", trademark of the Union Carbide Corp.
`having the structural formula:
`
`A
`
`20.0
`
`4.0
`
`3.0
`
`25.0
`
`Percent By Weight
`c
`D
`B
`
`E
`
`F
`
`15.0
`
`5.0
`
`20.0
`3.0
`
`10.0
`
`5.0
`
`i.o
`
`7.0
`
`30.0
`3.0
`16.0
`
`20.0
`3.0
`10.0
`
`3.0
`
`5.0
`20.0
`3.0
`5.0
`
`10.0
`
`5.0
`
`20.0
`3.0
`
`20.0
`2.0
`
`20.0
`
`0.5
`
`0.5
`
`1.5
`0.5
`
`0.5
`
`0.5
`
`0.5
`
`100
`
`100
`
`100
`
`100
`
`100
`
`100
`
`R R RJ
`I
`I
`I
`0 0 0
`"~~.
`
`y
`
`[
`
`where Rc,11 is the residue of an anhydroglucose unit
`
`6
`
`

`

`3,964,500
`
`11
`-continued
`(C,;H 1u05 ), the R's may be the same or different and
`each R individually represents a substituent group of
`the formula given hereinbelow, andy represents the
`degree of polymerization and is an integer having a value
`of from about 50 to about 20,000, or more, and preferably
`from about 200 to about 5,000.
`In the above structural formula each R individually
`represents a substituent group of the general formula:
`--t-C.,H2.,-0-r-;;;-tCH,-~H-O-r-;;-tC.H2•-0-r-;;-tC.,H2.,-Tq"R'
`
`12
`
`CH2
`I
`R,-N+-R,[Xj-
`1
`I
`V
`R2
`
`wherein:
`a is an integer having a value of from 2 to 3;
`b is an integer having a value of from 2 to 3;
`c is an integer having a value of from I to 3;
`m is an integer having a value of from zero to I 0;
`n is an integer having a value of from zero to 3;
`p is an integer having a value of from zero to I 0;
`q is an integer having a value of from zero to I;
`R' is a member selected from the group consisting of
`0
`0
`0
`0
`II
`II
`II
`II
`-H, -C-OH, -C-O-Na, -C-O-K and -c-O-NH,
`with the proviso that when q is zero then R' is -H;
`·
`R., R2 and R3 , take