US2983569A - Deformation of keratinous fibers with sulfite-borohydride composition - Google Patents

Description

used at clearly defined pH- values.

'aforesaaaimaiaa: 1

. Pr p. 1 Tier-ably, I

' {-the" rediicuig 'agentsemployed being such that th'e'concentiation-ofactive h drogen theoretically available is not more 'than Z-gi'ains' P'e too-cc. of the aqueous' reducing' DEFORMATION F KERATINOUS FIBERS WITH SULFITE-BOROHYDRIDE COMPOSITION Roger Charla, Soisy-sous-Montmorency, and Gregoire Kalopissis,.Paris, France, assign-ors to Societe Anonyme (lite: Societe Monsavon-lOreal, Paris, France, a corporation of France N0 Drawing. Filed May 19, 1958,8613 735,968

priority, application France May 20, 19:57

Claims. (Cl. 8-127-5) This invention relates to the deformation of keratinous fibers and moreespecially live human hair. The curling or dekinking of hair is eflected by means of compositions,v

effectiveness of which depends primarily upon the nature of the reducingsubstances contained therein. More especially, inorganic or organic'sulphites, if desired inassociation with bisu-lphites, are usually employed. =Thiols or mercaptansmay also be used, generally in the form of alkali metal'salts or anunonium salts.

Difficulties are encountered in applying the aforesaid reducing agents, and more especially since they must be of mercaptans' isfsomewhat unpleasant and they may produce allergic reactions in persons with whom they come into contactj It has therefore previously been proposed to use, for splitting the cystine linkages of the keratin of the' hair, hydrogen-generating reactants consisting of alkali metal borohydrides, preferably as a powder. uni- Moreover, the odor forrnly embedded ina water-miscible, inert carrier as described in copending application,'Serial No. 573,618, filed March 26, l956'j(now abandoned). I i I i Such a process of permanently waving hair by means of an'aqueoussolution of an alkaline borohydride is described 'in copending 'applicatiori; Serial No. 593,364, filed June 25, 1956;(now abandoned), Althoughitobviates the disadvantages inherent in the use of sulphites-or mercaptans, its application nevertheless requires ;a fairly strict control of the pH value' of the medium employed,

as the basicity ofthe aqueous borohydride solutions increases along with hydrolysis; this conitrol'however is the the nature "1 the composition to be used ffcdpeiiaijng agpliandn er1aljI-Io. '573,618, how abandolled, and ap'plic a Saar N6.""5 93;3'64, new a andonefd, "were conrlnnedin a continuation-in-part applicat'idn andjissuedafPatent No. 25 961405.

i "It is object, of Hej'resent invention to provide anew process forhthefpermaiient" deformation of keratinous fib rs a mare al 'q'ffh e h s; i 1 perature, in asimpleandfrl able manner and withini 'a and fafv t b j'm ie as ..A ,d iis, .t a saai y fi fl e af 1 or tlrel'ideforii la 'tion'of keratinous fibers,"

hair orother 'fibers to a desiredi c'onfiguration an composition, owingjs composition toiacton the hair for {at least ts Patented May 9,1961

ice

which shows that the reducing power of one mole of an alkali metal borohydride MeBH (wherein Me is the alkali metal) is theoretically four times that of onemole of an alkali metal sulphite Me SO when the reducing power is calculated in gram-atoms of active hydrogen. Whilstthe inventionis not to be regarded as restricted to any theoretical explanationof reduction ,of the disulphide bridges of keratin or, more generally, with regard to the softening action exerted on the hair by such mix- 'tures of sulphite and borohydride, it is believed possible 7 that thesulphite, in the presence of the keratin of the hair,

- the borohydride and probable by-products of the reaction,

constitutes a redox system, that is to say functions as an intermediate between the borohydride and the keratin. In this way the waste of. borohydrides as a result of the evolution of nascent hydrogen and the'rapid elimination of the latter by conversion into molecular hydrogen, such as occurs when a borohydride is used; as a sole reducing agent, is avoided. Due .to the presence of sulphite, the whole of the'reducing. power of. the composition is as it were conveyed to the hair through the non volatile compounds such as the sulphite and other :related reducing agents which derive thereof and which contain sulphur in a vicinal oxidation stage. In an intentionally simplified example, it may beiassumednthatta quantity of sulphite reducesv the keratin withconcomitantconversion into sulphate and that this sulphate is ..instantaneously reduced back to sulphite by the nascent'hydrogen .of-the borohydride, and so on. What actually happens is PIObably more complex, especially in view of the many oxidation stageswheresulphur vmaybe, at leastjtheoretica'lly (sulwhenused alone. The eflect obtained is all the more sur prising in that it isisuperior to the sumpr'the eiiects' of these jtwo reducing agents used separately. In particular, itha sbeen found that the reducing action ofthe mixture o f'sulphite an'd borohydride manifests itselffimrriediatelyj onapplication, whereas with an aqueous solution contain ing only a borohydride, eveniif this solution. s adjusted to a' favourable pHyaluef (9' to '10) for a steadydecomposition, there is an initial, latentperiod during 'whi ch' the reducing action is negligible; I

"In accordance: with further feature oft eirivention,

'larly'livejhun an'fhair,"which comprises applying wine I 7 hair or s reamers, hernia and/ or after constraining-the ,permanent deformation of 'hair isl'ih'u's definitely more" etfectiveathan the known processes, in which ionly sullphites :or borohydrides are'employed. vApart from *the i art c lar y 'tn ked esu s :Qb inedA nJR Q t Qs"th sw ur, 'periorityjhas-been verified "by;.taking;asa basis of 'comp nrth pe c n e of e systin ag be r p i asca function-mike duration of cori c -v Thispercentage a ,70" mirlute'sand thereafter rins ng, fix ng and J {penetrating and/ on swelling agents, kno'wnfper se for proving the effectivenessof the conventionalpreparations for permanent waving, are added to thecomposition. V

.thisiway an even more completeband jefiective utilizat on of the reducingproperties of the,sulphite borohydrideassociation is obtained Theimprovement thus afforded'is rmuch. .greatefirgthafn that resulting :troin theadditiGnQOf these same penetration and/ or ,swe'llin'g agents to a composition containing lsolely sulphites .or solely, borohydrides. The process according to the invention foreifectingthe 3. was determined photo colorimetrically by the method of Folin et a1. by means of phospho-tungstic acid (J. Biol. Chem vol. 112 1935), p. 683,, and Bulletin de lInstitut Textile 'de France; vol. 30 (1952), pp. 255-271): The tests were carried out on hairs of medium textu'r'etaken from a same subject, shampooed, rinsed anddried. Each test consists of treating one tress weighing 1.25 g. with cc. of reducing solution at a temperature of 20 C. for 20 minutes. The compositions of the solutions employed in each of these tests, in which the proportions are expressed ingrarnsper 100 cc. of solution, are as follows:

It willl be noted that iefau these tests, involving we same sulphite and the' same borohydride merely with" ja view to facilitating the compan'sb'ii, the same "r 'e'actafnt sw n .i nt isr Pr ms centage ,oflcystinelinkagesbeing split bythe twor'educing 1 1.2". a Reduction, Percent... 13 a 9 1 d 9 3 (Extreme .values me m-e V 10. 3- 1:2 Penetratln and swel- 1-. 1 t a Pg mmnfs 15%ethanol and i .1. t i 12%lurea..

table clearlyshows that mixtures of the two reducing agents-{tests Candi exert a much greater reducingaction than the su'mdf their rediibing 'actions when a som TestA: V 1 G. Sodium sulphite 2 Glycine. 2 Water to make .100 cc.

TestB:. t

.Sodium borohydride .2 Glycine 2 Water to make 100 cc. I

Test CL. e a H Sodium sulphite 2 Sodium borohydride 2 d Glycine a 2 Water to make 100 cc. l I

Test D: a 1

' Sodium sulphite Y 2 Glycine 2 Urea 12 Ethanol i v 15 Water to make 100 0c. t t t y TestE: j

a Sodium borohydride 2 a Water to make 100 cc. f.

Test Fa, w a M Glycine 3 W J2 Urea a A a .12 Ethanol i i 1 i t 1 15 Water to make 100 cc. 1 1 t i tory results under the}aforesaidfionditions,

w 19 p ese v nt n was T e pro according qt etinve ta l o nQQth s k ha d. 9 1 a sflm t- :after they are wound. Ihes olutionh act for: a period of time necessary or tliesofiteningof the ham generally, 15am 45.: minutesm nd 11h? h 'zti values (9.0 to 9.3, i.e. moderately alkaline as-compared with the usual methods of cold-waving), the addition of penetrating and swelling agents, such as ethanol and urea, does not substantially improve the action of the sulphite or borohydride when used separately as reducing agents (compare the reduction percentages in columns D andE of the table with those in columns A and-B), but does very substantially increase the efiicac'y of the mixture of the two reducing agents (comparef the reduction percentage in column F of the table with that inicolumn C).

Suitable water-soluble sulphites Having an alkaline reaction for use in the process of the presentinvention' are, for example, sodium sulphite, potassium sulphite and the sulphites of nitrogenous organic bases, such as triethanolamine sulphite, morpholine sulphite land guam'dine sul- P t a 1 r 1.

In effecting control of the pH-value of the solutions, it was found preferable to restort to buffers or compounds, such as weak acids, which, are capable under theconditions in which they are employed of fo'rm'ing buffered systems. These include, for example. boric acidalone or mixedwith calcium chloride, tartaric acid, citric acid, lactic acid, di-hydrogen ortho-sodium phosphate, glycine", sarcosine and taurine. It has also beenfoimd that itjmay be advantageous to start the treatment in the presence of a small quantity of the weak acid 'and toadd a further quantity of the same acid in the course of thetreatrr ient, by spraying or by any other: suitableimeans'. f Y

The agents promoting the penetr mnet nereactants into the hair, and the use'of which naqsrmgeaaawmage; ous for carrying out the process" according 'to the invention, include those already'proposed for permanent w v ing by means of sulphites, especiallyflower nconbrmuch as ethanol and isopropanol, the 'glycbls others or etheresters of glycols, such'as ethylene-glycol," diethyl ene g'lyco L the monoethyl and monobutylkthersipfjethyleh" glycol, the acetate of ethylenglycol. mbdetnyt etheif," 'nfil larly advantageousmethod ofcarrying'outthep entlin;

vention conslsts in preparing the-aqueouscomposition by dissolutionof a mixture obtained'in'accordance with the process described ini application"Ser NOZ 573,618 and wherein the binder orcarrier ,for thejborohydride powder also acts as a penetratingfagenti "Aneiample of swa a bin r i a l q d n a l f th ls re-awn 11,5149. a.

sition suitable .for* carrying out l k ellpijoce s to invention, hi s m sitiqn c t ris n m fi l mixturepf a,water-soluble em hases alii'i re sodium and/or potassium borohydxide weak acid, all uniformly embedded h s o i solidafu s a We -w g $4? t em l e t 14 2 9Fm fl9i i 9 n t ti ss .and use, said;oomposition.containjngone, mole of .p ta p lr mo s tp et z b v, i-f4i l f' hydride Such a compositipnlcan M ample, according to the processdesc d" ,SerytNo. 573,618.21

.thidurea, formamide andacetam A q y ui t s s i a y ths n u tqhsi q sf v g, t e hair es csaflQWQ tLfiMQtlI sui abl .shape gand d1mens1ons.,; Th etresses e itnptgegpated with the, reducing 'solutionjimrnediatel betorey and/or Al en allowed.

under, substantially the same conditions of initial =pH- 75, then rinsed and fixed in the usual manner forieaample-by sodium hq phyfl idem A ydrous. d llfill p i i :1' G ci e, Et anol--- Urea jjThehair is immediately woundon eurlers; A fter a period of: contactfofr 1 minutes; a solution of -1 .5 g. of

glycine in 20 cc. of water is sprayed onto the hair. After r a further minutes, the hair isrinsed with water, fixed with a 2% hydrogen peroxide solution and dried. A tight anddurable' curl is obltain'ed; I t I What we claim is: :2 p u a 1. A method of permanently reshapmg human hair andother. keratinous ,.fibers..whicl1 .cOinpi'iss holding the fibers in desired shape .whileithey are wettedawith a hair, Softening -.so1utiont..adjusted to 7a.. pH-value N within the range of about .9.0--to-10.0.tanddcontainingflat least one hydride of a molecular weight higher-than 35Iin a ratio of one mole of sulphit e to 1 moles of borohydride, the total quantity oftbothfrea'ctants being such a s to amount to a concentration of active Hydrogen theoretically avail able of not more than#2=;grams per 100 of the hairsoftening solution, allowing said solution toremain in contact with'th' fibers rb'rat least 1 5ii1inutes'; and thereafter rinsing, 's'ettiiig' by tfeat'ing with an oxidizing a ent, releasing and drying the fibers. I Y t ,1 2; method-of permanently. reshafiin and-otherkeratinous fibers according to*clairn l', yvhe I the -water=solublesulphitrandthe alkali metal bo hy 'dride are "used" in a ratio' 'of "one' mole of *sulphite t moles -of"borohydrider 3. Amethod of permanently reshapin' g hair and a other keratinous fibers which compriseshjoldin'g? thetttfib'ers in desiredishap'e while they are'wett'ed withla hair-soften"- ing solution; buffered to a pH-value within the range :of about 9.0 to 10.0 and containing atleast one Iwate'r-s'oluble sulphite and at least-toner allgali metal borohydride of a molecular weight higher than in a ratio 01:: one mole of *sulphite to l- 20 moles of borohydi'i de, the total' 'quan .tity of both reactants, being suchas,to amoi1i1f to a"con centration of active hydrogen theoretically available of Shot more than- 2 gramspen 100 00. of the "hai'r soft'ening solution, allowing-said solution-to ren'iain' in contact with the fibers for: at least-15 minutes, and thereafter rinsing, setting by treating with an oxidizing-agent;releasing and d fih sq jw e fir fit imi h ir h estua e th d nath 'q a sali l tisn." '1 Y, s ws d qia PE lue the swfiaebs tz stQJ Q-aiQ'Q/and ssm in 'sat one water-soluble sulphite and at least orie alkali metal water-solublemsulphite-and-vat least "one alkalitmetal borodrying the fibers.

"Hume a ey ar wetted with a,hair

r 1" borohydride of a moleemasweigm higher than 35 in a sk ds. 9 Wa t. uagt tya iflqth ,e a :l eing such s p t to amount to a concentration of active hydrogen theoreti- I cally available of not more than 2 grams per cc of f the "hairasoftening solution; "allOWlllglSQald 1 solution inain irr-contact'with the fibers'ifor at"least' 15' farnbient "temperature 'while'the "pH' is maintain'e :d'esiredwalue""by'addition-ofa"'compoundselected ro theclass consisting'ofboric'acid; tartaric acidglacti citric acid, glycine, sarcosine and? rinsing,zsetting by-tieating ingEand dr ing tHe fibers. i t t; 5.:A imethod bf permanently -reshapinghiimmhairand other keratinous fibers iwhich -coniprises holding the fibers trogenou's organic bases and at leasftoneg metal bojrohy dride of ;a. molecular weight higher; 'in a ratio of lane mole of, "sulphite to, 11-20, moles er horohyi dride, the total quantity of qboth type's of reactants being such as to amounttto a concentration of active, hydrogen theoretically available 'of not more-than) g'rams per 10 0 cc. of the hair-softening solution, allowingtsaid solution to remain in contact with thefibers for ,at least 1; minutes at, ambient temperature, and, thereafterrinsing, setting by treating with an oxidizing agent, releasing and 6. A method for permanentlyireshaping human hair and otheri-keratinous fiberswvhich comprises holdingithe fibers laureates-snaps while they arewetted with a hair'- softening solution adjusted to a pH-value within the range of about..9..0 to 10.0 .containing at least one ,water soluble. sulphite, ,at least "one alkali, metal. borohydride of aimolecular; weight n higher than t .35 ,in a "ratio. of. :one mole of sulphite to 1-20 moles ofaborohydride; and a penetrationagent selected-from the class; consisting of lower v t'atty'ia lcrbliols; 'glycols; glycol] etheis; glycol ether estersfcyclic ethers'anfd ethylene oxide polycondnsates', the total quantity ofthi reducing agents'beingsucli 'as to amount to a concentration of active hydrogen theoretisa x v il blelpfi mt mvrs 11 1;; :sx m r str msof th mh inqits ms s t nsel nst at .=s9lv iontq reinain in contact with the fibers for at least liminutes at ambient temperature, and thereafter rinsing, setting by t atmentstqsidisi zsa e asin and-d y n h fibers.

theoretically available of not more than 2 grams 365 100 gtthe hair-softening solution, allowinggsaid solution one mole of sulphite tol 1-fl20. moles of borohydride, the 5917-1 gantit rot h Mus n agents b i amount 'to" a "conntratidn 6f grams per 1 giis'soliltron 'of a we'a'li organie' acid, tt g posfi'r' waiameninfifi m 9. In a mth'od'of permanently reshaping human hair and othri kei atinous fibers by holding the' fiBIrQ "desird s'hape wliile they afe watt ed'with an aqlieoiiihair softening solution adjusted to a pH-value within the range of about 9.0 to 10.0 containing at least one Watersoluble sulphite, at least one alkali metal borohydride of a molecular weight higher than 35 in a ratio of one mole of sulphite to 1-20 moles of borohydride and an acid compound selected from the class consisting of boric acid, tartaric acid, lactic acid, .citric acid, glycine, sarcosine and taurine, the total quantity of the reducing agents being such as to amount to a concentration of active hydrogen theoretically available of not more than 2 grams per 100 cc. of the hair-softening solution and the time allowed for said solution to remain in contact with the fibers being of at least 15 minutes at ambient temperature, the step which comprises keeping apart substantially half the amount of said acid compound and applying it to the fiber about minutes later.

10. A method of permanently reshaping human hair and other keratinous fibers which comprises holding the fibers in desired shape while they are wetted with an aqueous hair-softening solution bufiered to a pH-value within the range of about 9.0 to 10.0 containing at least one Water-soluble sulphite, at least one alkali metal borohydride of a molecular weight higher than 35 in a ratio of one mole of sulphite to 1-20 moles of borohydride, a water miscible penetrating agent selected from the class consisting of lower fatty alcohols, glycols, glycol ethers, glycol ether-esters, cyclic ethers and ethylene oxide polycondensates and a water soluble hair swelling agent selected from the class consisting of urea, thio-urea, formamide, acetamide and carboxylic acid amides of organic heterocyclic nitrogenous bases in an aqueous medium, the total quantity of the reducing agents being such as to amount to a concentration of active hydrogen theoretically available of not more than 2 grams per 100 cc. of the hair-softening solution, allowing said solution to remain in contact with the fibers for at least minutes at ambient temperature, and thereafter rinsing, setting by treating with an oxidizing agent, releasing and drying the fibers.

11. A solid hair waving composition to be used in aqueous solution which comprises a pulverulent mixture of a water-soluble sulphite, an alkali metal borohydride of a molecular weight higher than 35 and a crystalline weak acid, all uniformly embedded as a stable dispersion in a solid, fusible and water-miscible carrier which is chemically inert under normal conditions of storage and use, said composition containing one mole of sulphite to 1-20 moles of borohydride and a suitable amount of the weak acid to ensure a pH-value of 9-10 in the solution ready for use.

12. A solid hair waving composition according to claim 11 wherein the solid, fusible and water-miscible carrier is present in the proportion of at least percent of the composition.

13. A solid hair waving composition to be used in aqueous solution which comprises a pulverulent mixture of a water-soluble sulphite, an alkali metal borohydride of a molecular weight higher than 35 and a crystalline weak acid, all uniformly embedded as a stable dispersion in a waxy polycondensate of ethylene oxide, said composition containing one mole of sulphite to 1-20 moles of borohydride and a suitable amount of the weak acid to ensure a pH-value of 9-10 in the solution ready for use.

14. A solid hair waving composition to be used in aqueous solution which comprises a pulverulent mixture of a Water-soluble sulphite, an alkali metal borohydride selected from the class consisting of sodium borohydride and potassium borohydride and a crystalline weak acid, all uniformly embedded as a stable dispersion in a polycondensate of ethylene oxide of an average molecular weight higher than 1500, said composition containing one mole of sulphite to 2-4 moles of borohydride and a suitable amount of the weak acid to ensure a pH-value of 9-10 in the solution ready for use.

References Cited in the file of this patent UNITED STATES PATENTS 2,351,718 Speakman June 20, 1944 2,464,280 Reed Mar. 15, 1949 2,766,760 Bogaty Oct. 16, 1956 FOREIGN PATENTS 75,921 Netherlands Sept. 15, 1954 OTHER REFERENCES Speakman: J. Soc. Dyers and Colorists, vol. 52, 1936, pp. 335-346.

Claims (1)

1. A METHOD OF PERMANENTLY RESHAPING HUMAN HAIR AND OTHER KERATINOUS FIBERS WHICH COMPRISES HOLDING THE FIBERS IN DESIRED SHAPE WHILE THEY ARE WETTED WITH A HAIRSOFTENING SOLUTION ADJUSTED TO A PH-VALUE WITHIN THE RANGE OF ABOUT 9.0 TO 10.0 AND CONTAINING AT LEAST ONE WATER-SOLUBLE SULPHITE AND AT LEAST ONE ALKALI METAL BOROHYDRIDE OF A MOLECULAR WEIGHT HIGHER THAN 35 IN A RATIO OF ONE MOLE OF SULPHITE TO 1-20 MOLES OF BOROHYDRIDE, THE TOTAL QUANTITY OF BOTH REACTANTS BEING SUCH AS TO AMOUNT TO A CONCENTRATION OF ACTIVE HYDROGEN THEORETICALLY AVAILABLE OF NOT MORE THAN 2 GRAMS PER 100 CC. OF THE HAIRSOFTENING SOLUTION, ALLOWING SAID SOLUTION TO REMAIN IN CONTACT WITH THE FIBERS FOR AT LEAST 15 MINUTES, AND THEREAFTER RINSING, SETTING BY TREATING WITH AN OXIDIZING AGENT, RELEASING AND DRYING THE FIBERS.