O
`
`Unlted States Patent [19]
`Hsiung et al.
`
`[111
`[45]
`
`4,391,286
`Jul. 5, 1983
`
`[54] HAIR CONDITIONING AND COMPOSITION
`
`4,038,995 8/1977 Edelberg ............................... .. 132/7
`
`THEREFOR
`
`[75] Inventors: Du Y. Hsiung, Park Forest; Chester
`A. Davis, Berwyn; Harold J.
`Nicholson, Roselle, all of I11.
`[73] Assignee: Helene Curtis Industries, Chicago,
`111-
`[21] Appl‘ No" 236,127
`[22] Filed;
`Feb, 19, 1981
`7
`
`.......
`($3 ................................
`[2;]
`E58} Fi'elh o1;
`"""""""""""""
`"""""""""""
`References Cited
`U.S. PATENT DOCUMENTS
`
`[56]
`
`/7_ 42’4/70_72
`’
`
`3,693,633 9/1972 Kalopissi ............................... ..132/7
`3,760,819 9/1973 Vogt
`. 132/7
`3,957,065 5/1976 Busch ............................... ..,'.'..'.132/7
`
`4,197,865 4/1980 Jacquet . . . . . .
`. . . . .. 132/7
`4,214,596 7/1980 Kaplan .................................. .. 132/7
`
`Primary Examiner—A. J. Heinz
`Attorney, Agent, or Firm—Dress1cr, Goldsmith, Shore,
`Sutker & Mllnamow
`[57]
`ABSTRACT
`A hair conditioning composition particularly useful in
`conjunction with hair waving having a pH value of
`about 4-9 and containing water having dissolved
`therein about 0_05_5 weight percent quaternary nitro_
`gen-containing conditioning polymer having a molecu
`lar weight of about 10,000-10,000,000, and about 05-10
`weight percent of a water-soluble disul?de-containing
`polycarboxylic acid or salt thereof, as well as methods
`for its use and preparation are disclosed.
`
`16 Claims, N0 Drawings
`
`1
`
`

`

`1
`
`HAIR CONDITIONING AND COMPOSITION
`THEREFOR
`
`10
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`DESCRIPTION
`1. Technical Field
`This invention relates to conditioning hair, and par
`ticularly to compositions and processes for selectively
`conditioning hair whose con?guration is to be altered.
`2. Background Art
`Permanent hair waving is usually carried out by sub
`jecting the hair to reagents containing a free —SH
`group or thiol. These materials are also called mercap
`tans. In this treatment, the hair is usually ?rst wound on
`rollers and then saturated with the thiol. The thiol wav
`ing agent acts to break the disul?de bonds within the
`hair ?ber forming thiol groups in the hair protein and
`disul?de bondsbetween two thiol waving agent mole
`cules. When a suf?cient number of hair disul?de bonds
`have been broken, the hair is realigned to pair previ—
`ously ‘unpaired hair protein thiol groups opposite each
`other. At this point, the .hair is rinsed, removing the
`unreacted thiol waving agent and disul?de ’ reaction
`product formed from it, and then saturated with an
`oxidizing agent, or neutralizer, such as hydrogen perox
`ide'or a bromate salt, to reform disul?de bonds between
`the newly paired hair protein thiols and to give the hair
`a con?guration or wave. This process may be used to
`add curl or straighten the hair.
`'
`Salts of thioglycolic acid, such as ammonium thiogly
`colate, and thioglycolic acid esters, such as glycerol
`thioglycolate, are typically utilized as the thiol waving
`agent. Other thiol-containing reagents'such as thiolactic
`acid,
`beta-mercaptopropionic acid, beta-mercap
`tobutyric acid, mercaptosuccinic acid and the like are
`also known in the art to be effective.
`As the above waving process is usually carried out,
`the hair is wet with water or a disul?de bond breaking
`agent prior to its being wrapped on the rollers. In some
`instances, the thiol-containing waving lotion is used as
`the wetting agent, or prewrap, as it is known in the art.
`This latter treatment begins the hair disul?de‘ bond
`breaking‘process, and hastens the overall process. How
`ever, as the hair is dif?cult to wrap while wearing the
`gloves normally used with thiol waving agents, beauti
`45
`cians frequently use their bare ?ngers for this step, and
`continual contact of the skin with thiol-containing rea
`gents may cause skin irritation to some individuals.
`The problems of using bare ?ngers to wrap hair on
`rollers after treatment with a disul?de bond-breaking
`reagent was largely solved by the invention of the' co
`assigned U.S. Pat. No. 4,214,596 to Kaplan et al. That
`patent describes the use of a bisul?te ion-containing
`composition in a prewrap which is mild to skin and
`non-irritating.
`’
`One problem which U.S. Pat. No. 4,214,596 did not
`solve was the under waving and over waving (under
`and over processing) which may occur during waving
`on different parts of a single hair ?ber or in different
`areas of the hair mass due to the physical and chemical
`condition of the hair itself. For example, hair which has
`been waved, bleached, or bleached and waved is more
`porous than is 'hair which has not undergone these
`chemical treatments, such as portions of the hair ?ber
`near the root which has grown out since the last bleach
`ing or waving. Similarly, even hair having no previous
`history of bleaching or waving is more porous near the
`tip end than near the root end simply because hair near
`
`4,391,286‘
`2
`the tip has been brushed more, or has been subjected to
`more weathering.
`.
`As a'consequence of these porosity differences, the
`hair tends to take-up more waving agent in some areas,
`and less waving agent in others. Over waving or pro
`cessing tends to occur in the more porous portions of
`the hair while under waving or processing tends to
`occur in the less porous areas. These trends are exactly
`the inverse of what is desired since the hair which usu
`ally needs the waving treatment the most gets the least
`waving, and vice versa.
`Aside from changes in porosity, hair which has been
`bleached and/or waved is also believed to have a differ
`ent chemical make-up than does virgin, unchemically
`treated, hair. In addition, older hair which has been
`brushed more often tends to have a rougher cuticle or
`outer layer than does hair which is newer, closer to the
`scalp, and therefore brushed fewer times. This observed
`roughness is believed to be due to several factors includ
`ing: (1) the physical abrasion of portions of the cuticle
`caused simply by repeated contact with hair brush bris
`tles; and (2) the physical damage done to the tip ends
`when a brush or comb is pulled through the tips at the
`end ‘of the brushing or combing stroke.
`.
`Conditioning agents for hair have been known in the
`art for several years. Typically, these conditioning
`agents are relatively small molecules having a single
`quaternary nitrogen atom bonded to at least one 8-20
`carbon atom chain with the remaining nitrogen bonds
`being taken up by ethyl, methyl or benzyl groups. These
`conditioners are used after a shampoo as put-on, rinse
`out compositions; put-on, leave-on compositions also
`being known. At least one commercial waving prepara
`tion is said to use a relatively small molecule quaternary
`conditioning agent in the prewrap composition.
`A disadvantage of the relatively small molecule qua
`ternary conditioning agents is that they are substantially
`washed out of the hair after a single shampoo and there
`fore do not provide a lasting effect. In addition, the
`relatively small molecule quaternary conditioners pro
`vide little, if any, set control to the hair, and tend to
`leave the hair limp, with little body.
`U.S. Pat. No. 3,912,808 to Sokol teaches the use of a
`polymeric quaternary nitrogen-containing polymer in a
`composition used for changing the con?guration of
`hair; i.e., a waving lotion. When such polymeric quater
`nary nitrogen compounds are used as the conditioning
`agents, it is known that the hair will remain conditioned
`through several shampoos. However, use of this condi
`tioning agent in a prewrap can lead to hair which is too
`slippery to wind on rollers. The smaller quaternary _
`' molecule conditioning agents also produce some slip
`periness on the hair, but not so much slipperiness as to
`interfere with manipulating the hair, as during rolling of
`the hair in a waving process.
`Water-soluble dithiopolycarboxylic acids and their
`salts, such as diammonium dithiodiglycolalte, are
`known to be useful in waving lotion of hair waving
`preparations to effect some protection from over wav
`ing. However, these disul?des are not known to be
`useful in prewrap preparations. It is known to use a less
`soluble ester of such disul?des in a prewrap composi
`tion in conjunction with a relatively small molecule,
`quaternary nitrogen conditioning agent. However, the
`conditioning effect, if any, of the relatively small mole
`cule quaternary nitrogen compound when used with the
`
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`4,391,286
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`less-soluble disul?de ester is, as stated above, substan
`cause the compositions of this invention are not irritat~
`tially lost after shampooing.
`ing to the hands.
`It would therefore be bene?cial if the over waving
`Yet another bene?t of the present invention is that the
`protection provided by water-soluble disul?des could
`compositions may be used as a put-on, leave-on product
`be combined with the long lasting conditioning proper? »
`or as a put-'on, rinse-out product and in either use add a
`ties of a polymeric quaternary nitrogen-containing con
`long term conditioning bene?t to the hair.
`ditioning agent without the hair slipperiness which is
`An additional bene?t of this invention is that the
`associated with such polymers. Such a composition
`tensile strength of waved hair treated with its composi
`tions tends to be greater than that for hair which has
`could be used as a prewrap and allow the proper wind
`ing of the hair on rollers, while imparting its condition
`only been waved, and not treated with the compositions
`ing effect through several shampoos and protecting the
`disclosed herein.
`Still other bene?ts and advantages of the instant in
`hair from over waving.
`'
`-
`The dif?culties associated with manipulation of slip
`vention will be apparent to those skilled in the art from
`the disclosure which follows.
`pery hair when the configuration of the hair is to be
`changed are not unique to hair waving. Rather, the
`DETAILED DESCRIPTION OF THE
`provision of a lasting conditioning effect to hair without
`undue slipperiness is general to hair con?gurational
`change processes, such as water setting, where wet or
`damp hair is manipulated subsequent to the application
`of the conditioning composition.
`SUMMARY OF THE INVENTION
`According to the present invention, a unique hair
`conditioning composition is prepared. This composition
`contains water having dissolved therein about 0.05 to
`about 5 weight percent of a quaternary nitrogen-con
`taining polymer having a molecular weight between
`about 10,000 and about 10,000,000, and about 0.5 to
`about 10 weight percent of a water-soluble disul?de
`containing polycarboxylic acid or salt thereof. The
`composition of this invention has a pH value between
`about 4 and about 9 measured at 80° F. (26.7” C.).
`In addition, a process for treating hair whose con?gu
`ration is to be changed subsequent to the application of
`a conditioning composition of this invention is dis
`35
`closed. According to this process, a composition of this
`invention is applied to the hair, distributed substantially
`evenly therethrough, and the con?guration of the hair
`thereafter altered while the hair is at least partially
`damp.
`The compositions and processes of this invention
`possess many advantages and bene?ts.
`'
`One advantage of the compositions and processes of
`this invention is that the hair is selectively conditioned
`by absorbing more conditioning agent at porous areas
`needing conditioning the most, and less conditioner at
`portions of the hair requiring less conditioning.
`Another bene?t of the instant compositions and pro
`cesses when used in waving is that the amount of wav
`ing tends to be leveled along the hair shaft by protecting
`porous areas from over processing while permitting
`enough waving of less porous portions of the ?ber. This
`allows the beautician or home user added leeway in
`choice of product strength and treatment duration for
`hair which is between the porosity extremes of virgin
`hair and bleached and waved hair.
`Yet another advantage of the compositions and pro
`cesses disclosed herein is ‘that their conditioning and
`over-waving protection lasts through several shampoo
`treatments, and thus the compositions may be applied
`days before waving is performed.
`Still another advantage of the present invention is
`that when a composition is applied prior to changing
`the hair con?guration, the hair is easily wrapped on
`rollers without the usual slippery feel associated with
`polymeric quaternary nitrogen conditioning agents. In
`addition, when used as a permanent wave prewrap, the
`beautician need not wear gloves during wrapping be
`
`' INVENTION
`The compositions of the present invention are
`broadly useful for conditioning human hair. These com
`positions are particularly useful for conditioning hair
`whose con?guration is to be changed subsequent to the
`application of the conditioning composition since con
`?guration changes typically require manipulation of the
`hair, and use of the compositions of this invention .pro
`vides hair which is conditioned but not too slippery to
`manipulate.
`As used herein, changing or altering the con?gura
`tion of hair is meant to include both straightening and
`curling processes which are carried out while the hair is
`wet, or at least damp. Illustrations of hair con?guration
`changing processes include, but are not limited to, hair
`waving using a thiol-containing reagent and water set
`ting.
`Since the problems associated with hair waving typi
`cally include those found in other hair con?gurational
`change processes, as well as those intrinsic to waving,
`the discussion hereinbelow will be primarily centered
`upon the application of the instant invention to-hair
`waving. It should be understood however, that use of
`the compositions of the present invention is not limited
`to hair waving processes, and includes use on tinted
`hair, on bleached and/or previously waved hair, or as a
`pre-treatment prior to oxidative color or bleaching
`treatments, or whenever conditioning is desired.
`The unique compositions of this invention are pre
`pared by dissolving both a water-soluble, disul?de-con
`taining polycarboxylic acid or salt thereof and a quater
`nary nitrogen-containing polymer in water. The words
`“dissolving” and “solution” in their various grammatif
`cal forms, are meant herein to include the formation of
`true solutions as well as the formation of substantially
`clear, non-settling dispersions. High molecular weight
`polymers rarely form true solutions in water and tend,
`at best to form non-settling, substantially clear disper
`sions. Some lower molecular weight polymers may
`form true solutions.
`The preferred water-soluble disul?de-containing
`polycarboxylic acids, also called dithiopolycarboxylic
`acids, useful herein are typically symmetrical in struc
`ture on either side of the disul?de bond, although asym
`metrical compounds may also be used. These disul?des
`are typically formed by the oxidation of two molecules
`of mercapto-monocarboxylic acid. The preferred disul
`?de-containing polycarboxylic acids of this invention
`are illustrated by dithiodiglycolic acid, 3,3'~dithiodipro
`pionic acid, cystine, dithiodilactic acid, dithiodisuccinic
`acid and the like; dithiodiglycolic acid being especially
`preferred.
`'
`
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`

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`4,391,286
`5
`6
`Another preferred quaternary nitrogen-containing
`The disul?de-containing polycarboxylic acids may be
`present in the compositions of this invention at about 0.5
`polymer useful herein is a cationic guar. This material
`to about 10 weight percent of the total composition
`has 3-trimethyl-ammonium~2-hydroxypropyl groups
`when it is put on the head. In preferred practice, the
`bonded to the mannopyranosyl and galactopyranosyl,
`water-soluble disul?de-containing polycarboxylic acid
`units which make up the guar chains; chloride ion being
`the anion usually associated with the polymer. The
`is present at about 1 to about 5 weight percent of the
`name adopted by the Cosmetics, Toiletries and Fra
`total composition.
`.
`The dithiopolycarboxylic acids may be added to the
`gances Association for this material, although not ap
`pearing in the above C T FA Dictionary, is Guar Hydrox
`water as the free acids and the pH value of the resulting
`ypropyltrimonium Chloride. A suitable cationic guar is
`solution thereafter adjusted, if necessary, as discussed
`hereinafter. Preferably, however, the dithiopolycar
`supplied under the designation COSMEDIA GUAR C
`boxylic acids are used as their water-soluble salts; the
`261 by Henkel, Inc., while a similar material is sold
`preferred cations being alkali metal ions such as sodium
`under the designation JAGUAR C-l3-S by Stein, Hall
`& Company, Inc.
`or potassium, or more preferably the ammonium ion.
`Cosmetically acceptable substituted ammonium ions
`A copolymer prepared from about 80 weight percent
`N-vinyl pyrrolidone and about 20 weight percent N,N
`such as the alkanolammonium ions, illustrated by the
`dimethyl-aminoethyl methacrylate, quaternized with
`monoethanolammonium, di-isopropanolammonium and
`dimethyl sulfate is also preferred herein. This material is
`triethanolammonium ions, are also useful cations. The
`above described amounts of dithiopolycarboxylic acid
`named Quaternium-23 in the CT FA Dictionary.
`Quaternium-23 is available from GAF Corporation
`in the compositions of this invention are calculated as
`under the designation GAFQUAT-755 and GAF
`the acid, rather than as a salt thereof.
`QUAT-734. The polymer designated GAFQUAT-734,
`A wide variety of water-soluble quaternary nitrogen
`containing polymers are useful herein. Broadly, such
`has an average molecular weight of less than about
`polymers are useful in the range of about 0.05 to about
`100,000, while that designated GAFQUAT-755 has a
`5 weight percent of the compositions. Preferably, these
`molecular weight of greater than 1,000,000.
`Yet another preferred polymer useful herein is a co
`polymers are present in the range of about 0.1 to about
`polymer prepared from acrylamide and N,N-dime
`2 weight percent, and more preferably these polymers
`thylaminoethyl methacrylate, quaternized with di
`are useful in the range of about 0.1 to about 1 weight
`percent. The molecular weights of the polymers useful
`methyl sulfate. Viscosities of 1 weight percent aqueous
`solutions of these polymers typically have Brook?eld
`herein are broadly between about 10,000 and about
`10,000,000, and preferably between about 100,000 and
`Viscosities of about 35 to about 1200 cps.
`,
`These copolymers are named in the CTFA Dictionary
`about 4,000,000, with various useful polymers having a
`generally more narrow molecular weight range.
`as Quaternium-39, and are available under the designa
`The preferred polymeric cationic polymers include
`tion RETEN from Hercules, Inc. Commercially avail
`those prepared from polydiallyldimethylammonium
`able polymers include those designated RETEN SPX
`1104, SPX 1105 and SPX 1106.
`salts as is described in US. Pat. No. 3,288,770 and No.
`3,412,091. These polymers may be prepared by poly
`The copolymers designated RETEN SPX 1104, SPX
`merizing diallyldimethylammonium chloride or bro
`1105 and SPX 1106 are stated by their manufacturer as
`being highly cationic, and are reported to have Brook
`mide, or other suitable diallyldimethylammonium salts,
`using a free radical generating polymerization catalyst,
`?eld Viscosities of 35-50 cps, 100-400 cps and 600-800
`cps, respectively, for 1 percent by weight solutions in
`such as a peroxide or hydroperoxide, then employing a
`suitable anion exchange resin. The resulting polymers
`water at 25° C. RETEN SPX 1104 is most preferred of
`this type of polymer for use herein. Copolymers desig
`are polydiallyldimethylammonium salts, such as poly
`diallyldimethylammonium chloride. The homopolymer
`nated RETEN 210 and 220 having Viscosities in the
`range of about 600 to about 1200 cps, under the above
`so produced has been given the name Quaternium-40 in
`45
`the C TFA Cosmetic Ingredient Dictionary (CTFA Dictio
`conditions, are also suitable.
`nary), 2nd ed., 1977, published by the Cosmetic Toiletry
`The most preferred water-soluble polymer for use
`herein is a quaternary nitrogen-containing hydroxy
`and Fragance Association, Inc.
`ethyl cellulose having a backbone chain of anhydro
`The copolymer formed using acrylamide and a dial
`glucose units with pendant substituent groups bearing a
`lyldimethylammonium salt is also useful herein. The
`full positive charge spaced along the anhydroglucose
`C TFA Dictionary name for the diallyldimethylam
`monium salt copolymerized with acrylamide is Quater
`backbone. The pendant substituent group are spaced
`about the anhydroglucose units along the chain, thereby
`nium-4l.
`making the substituent groups themselves pendant and
`Both Quaternium-40 and Quaternium-41 are commer
`spaced along the chain. These hydroxyethyl cellulose
`cially available under the respective designations MER
`derivatives contain a plurality of quaternary nitrogen
`QUAT-lOO and MERQUAT-SSO from Merck & Com
`containing groups with each anhydroglucose unit hav
`pany, Inc. The polymer of the product designated
`ing from zero to three quaternary nitrogen-containing
`MERQUAT-IOO is said by the manufacturer to have a
`groups. These materials are typically prepared by react
`molecular weight of about 100,000 to about 1,000,000,
`ing hydroxyethyl cellulose with epichlorohydrin fol
`while the polymer, of the product designated MER
`lowed by reaction with a tertiary amine; the preferred
`QUAT-550 is said by the manufacturer to have a molec
`tertiary amine being trimethylamine. The preparation of
`ular weight of about 1,000,000 to about 10,000,000.
`these quaternary nitrogen-containing polymers is de
`MERQUAT-IOO is sold as a 40 weight percent aqueous
`solution of the polymer, and has a Brook?eld viscosity
`scribed in US. Pat. No. 3,472,840.
`These cationic, hydroxyethyl cellulose derivatives
`at 25° C. in the range of about 8,000~l2,000 centipoises
`are named Quaternium-19 in the CTFA Dictionary, and
`(cps). MERQUAT-SSO is sold as an 8 weight percent
`are commercially available under the designation POL
`aqueous solution of polymer, and‘ has‘a Brook?eld vis
`YMER JR from the Union Carbide Corporation. The
`cosity at 25° C. in the range of about 7,500-15,000 cps.
`
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`

`4,391,286
`8
`7
`presently available materials include POLYMER JR
`effectively on rollers. However, it has now been found
`l25, POLYMER JR-400 and POLYMER JR-30M. The
`1 that when quaternary nitrogen-containing polymers are
`molecular weights of these polymers are reported to be
`combined with the dithiopolycarboxylic acid or its
`between about 300,000 and about 1,000,000, with poly
`salts, as taught herein, the wet or damp hair is still con
`mers of a given designation having narrower average
`ditioned, but it is not so slippery that it will not wind
`molecular weights. For instance, POLYMER JR-30M
`properly on rollers. The conditioning effect is also
`is reported to have an average molecular weight be
`found- to last through several shampoo treatments. Ad
`tween about 700,000 and 1,000,000, while POLYMER
`ditionally, hair treated with the compositions of this
`J R-l25 is reported to have an average molecular weight
`invention has more body than hair treated with either
`between about 300,000 and about 400,000, and nearer to
`an equal amount of the quaternary polymer or the dithi
`300,000 than to 400,000. A two percent by weight aque
`opolycarboxylic acid alone. This is shown in Example
`ous solution of POLYMER JR-125 is reported to have
`3, hereinafter.
`a Brook?eld viscosity at a 30 rpm. spindle speed of
`75-175 cps (No. 1 spindle), while a one percent solution
`In addition to the water, dithiopolycarboxylic acid or
`salts thereof and quaternary nitrogen-containing poly
`of POLYMER J R-30M is reported to have a Brook?eld
`viscosity of l,000-2,500 cps (No. 3 spindle) under the
`mer, additional ingredients may also be present in the
`same measurement conditions.
`compositions of this invention. These additional ingre
`Of these polymers, POLYMER JR-400 is most pre
`dients may be selected from preservatives, perfume, one
`ferred. A two weight percent aqueous solution of POL
`or more surfactants, nonionic surfactants being pre
`YMER JR-400 at 25° C. reportedly has a Brookfield
`ferred, colorants, and additional conditioning agents,
`viscosity of 300-500 cps (No. 2 spindle), again at 30
`such as benzalkonium chloride.
`.
`r.p.m. The average molecular weight of POLYMER
`An illustration of the use of the conditioning compo
`JR-4OO is said to be between about 300,000 and about
`' sitions of this invention on hair whose con?guration is
`400,000, nearer to 400,000 than 300,000, and above that
`to be changed is as follows. The hair is usually ?rst
`of POLYMER JR-l25.
`25
`shampooed and left wet or damp. It is then treated with
`As used, the compositions of this invention suitably
`a composition of this invention by applying the compo
`' have a pH value of from about 4 to about 9. When used
`sition to the hair and distributing the composition sub
`generally as a conditioner, the compositions preferably
`stantially evenly therethrough. The con?guration of the
`have a pH value of from about 5 to about 8, while when
`30
`used as a prewrap before a waving process, the pH
`hair is thereafter altered while the hair is wet or at least
`value is more preferably from about 6.5 to about 8.
`_ partially damp from the application of the conditioning
`The mechanisms by which the composition and pro
`composition. The con?guration of the hair can be al
`cess of the instant invention provide their unique and
`tered by winding upon rollers, or the like, with no other
`lasting selective conditioning and over waving protec
`treatment, or by further treatment with a waving or
`tion results are not known. While not wishing to be
`straightening agent as is known in the art, and then
`bound by any one set of theories or hypotheses, it is
`dried.
`thought, however, that the composite mode of action of
`Additional steps are carried out when hair is to be
`the compositions of this invention may be as follows.
`waved substantially immediately after treatment with
`First, it is believed that treating hair to be waved with
`the composition of this invention, e.g., while the hair is
`a solution of a dithiopolycarboxylic acid before the
`still at least partially damp after application. In this
`thiol-containing waving lotion is applied can allow
`more of the over-waving protective dithiopolycarboxy
`embodiment, the hair is divided into a plurality of sec
`lic acid, or its salt, to be taken up by the hair than when
`tions and a composition of this invention is applied to a
`the dithiopolycarboxylic acid is used in the waving
`section, distributed substantially evenly therethrough,
`lotion. This is because there can be no competition for
`and the treated section wound on a roller. These steps
`binding sites within the hair ?ber between the dithi
`are then repeated on each of the remaining hair sections
`opolycarboxylic acid and the thiol-containing waving
`until all of the hair to be waved is wound on rollers.
`agent when the former is applied before the latter.
`Because of the mildness of the compositions of this
`Second, as the accompanying Example 4 demon
`invention, no gloves need be worn during the wrapping
`strates, the useful conditioning, quaternary nitrogen
`step. The hair is thereafter waved by conventional tech~
`containing polymer binds more to hair with a previous
`history of bleaching and/or waving than to virgin hair,
`and it is bleached and/or waved hair which is most
`susceptible to over waving. Consequently, a further
`possible mode by which selective protection from over
`waving is afforded by the compositions of this invention
`may be due to the formation of a physical barrier to
`penetration of the hair ?ber by the thiol-containing
`waving agent caused by selective polymer binding to
`those portions of the hair which have a previous history
`of bleaching and/or waving or are otherwise relatively
`porous.
`Third, the dithiopolycarboxylic acid or its salts are
`found to have a synergistic effect on the conditioning
`caused by the quaternary nitrogen-containing polymer.
`Thus, while it is known that the polymers useful herein
`will condition hair, hair treated with the polymer alone
`tends to be too slippery when wet or damp to wind
`
`Water (deionized)
`Quaternary Nitrogen-
`containing Polymer (Note 1)
`Dithiopolycarboxlic acid
`salt (Note 2)
`Surfactant (Note 3)
`Preservative
`Perfume
`Ammonium hydroxide
`(28% NH3)
`
`niques. .
`
`-
`
`Best Modes For Carrying Out The Invention
`Example 1: Prewrap Composition
`
`Components
`
`Weight percent of
`the Composition
`
`15
`
`20
`
`35
`
`40
`
`50
`
`55
`
`65
`
`(1)
`(2)
`
`(3)
`
`(4)
`(5)
`(6)
`(7)
`
`9l.02
`0.25
`
`8.0
`
`0.5
`0.] l5
`0.04
`0.075
`
`5
`
`

`

`10
`,
`was easier to comb through and wrap and had a better
`wet feel; i.e. was smoother than was the half-head
`treated with water alone. When the hair had dried, the
`half-head side treated with the composition of this in
`vention had better body, sheen and manageability, less
`fly-away and a ?rmer set than the hair of the half-head
`side treated with water. In addition, no tackiness, greas
`iness or ?aking was observed on the half-head side
`treated with the composition of this Example.
`Example 3: Comparative Properties
`Aqueous compositions containing the quaternary
`nitrogen-containing polymer and dithiopolycarboxylic
`acid salt of Examples 1 and 2 alone and in combination
`were compared in blind tests against water alone and
`against each other to determine various properties the
`compositions would impart to the hair. Both virgin and
`bleached hair tresses (Example 4) were used.
`In each determination, a composition (2 milliliters)
`was applied to a tress, the tress combed through once,
`wrapped on a roller and air dried. Wet hair properties
`were determined and ranked prior to wrapping, while
`dry hair properties were determined and ranked after
`the rolled hair had dried. A composite ranking of results
`for both virgin and bleached hair is shown below, with
`a ranking of 1 being the best.
`Compositions
`l. 0.25 Weight percent polymer of Example 1 in wa
`ter;
`2. 2.5 Weight percent diammonium dithiodiglycolate;
`3. 0.25 Weight percent polymer of Example 1 plus 2.5
`weight percent diammonium dithiodiglycolate;
`4. 0.25 Weight percent polymer of Example 1 plus
`‘1.25 weight percent diammonium dithiodiglycolate;
`5. 1.5 Weight percent polymer of Example 1;
`6. 2.75 Weight percent polymer of Example 1; and
`7. Water control.
`‘
`
`Rankine of Composition“
`2 .
`3
`4
`5
`6
`
`l
`
`7
`
`Attributes‘
`EXEL.
`Body .
`Combing
`Ease
`v
`Feel
`Appearance
`Overall
`Preference
`
`2
`2
`— -- '
`
`l
`l
`
`— — l
`— — l
`2
`2
`l
`
`l
`l
`
`l
`l
`l
`
`l
`l
`
`— — 3
`3
`3
`2
`
`3
`3
`4
`
`l
`3
`
`3
`3
`4
`
`l
`4
`
`2
`2
`3
`
`2
`—
`
`9
`-continued
`
`4,391,286
`
`Components
`
`Weight percent of
`the Composition
`l00.00
`(Note I) The most preferredkwater-soluble quaternary nitrogen-containing hydrox
`yethyl cellulose derivative designated POLYMER “(400. available from Union
`Carbide Corporation was used. This material has the CTFA Dictionary name
`Quaternium-l9.
`(Note 2) Diammonium dithiodiglycolate was used. This material was 27% active
`expressed as dithiodiglycolic acid. providing the composition with 2.16 weight
`percent active dithiodiglycolic acid or 256 Weight percent diammonium dithiodi
`glycoiate.
`(Note 3) A nonionic surfactant comprised of a mixture of laurate esters of sorbitol
`and sorbitol anhydrides, consisting predominantly of the monoester condensed with
`approximately 20 moles of ethylene oxide was used. This material has a CTFA
`Dictionary designation of Polysorbate-ZO.
`
`The prewrap of this Example was prepared by pre
`mixing Components 5 and 6 in Component 4 until the
`mixture was substantially homogeneous. The substan
`tially homogeneous mixture was then admixed with the
`deionized water (Component 1) which had been heated
`to a temperature of about 80° F. The resulting aqueous
`admixture was then stirred for about 15-20 minutes and
`maintained at a temperature of about v80" F. during the
`remainder of the preparation. The quaternary nitrogen
`containing polymer (Component 2) was then sifted into
`the aqueous admixture and the resulting composition
`stirred until the polymer dissolved. Diammonium dithi
`odiglycolate (Component 3) was thereafter added with
`stirring until a substantiall