US 3902507 A
This invention relates to methods for improving curl retention and mechanical properties of human hair. More particularly, it contemplates compositions and methods to beautify hair by the application of hair dressing compositions containing at least one bisbisulfite salt of an aliphatic diol in a cosmetic carrier. Hair treated with such compositions have unexpectedly been found to impart improved curl retention and strength to hair fibers.
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Description (OCR text may contain errors)
United States Patent [191 Kinney et al. 1 Sept. 2, 1975  METHODS FOR IMPROVING CURL 2,671,800 3 1954 Copenhaver 260/513 B RETENTION AND MECHANICAL 2,820,818 1/1958 Sexton et al. 260/513 B PROPERTIES OF HAIR FIBERS BY 3,149,152 9/1964 Boehme 260/513 B ALKANEDIOL BISBISULFITE SALTS 3,459,198 8/1969 Zemlin et a1 424/71 X  inventors: i Tjs g sgrgzigi fii Primary Examiner-Albert T. Meyers N Y Jose h P Ciaudelli Ramse Assistant Examiner-Vera C. Clarke p Attorney, Agent, or Firm-Pennie & Edmonds  Assignee: Avon Products, Inc., New York,
57 ABSTRACT  Ffled: 1972 This invention relates to methods for improving curl  Appl. No.: 301,800 retention and mechanical properties of human hair. More particularly, it contemplates compositions and  Us Cl 132/7 8/10 2, 8/127 51. methods to beautify hair by the application of hair 424/117. 4/ 4 dressing compositions containing at least one bisbisul-  Int Cl A45d i 7/06 fite salt of an aliphatic diol in a cosmetic carrier. Hair  Fieid "260/513 B,424/71 treated with such compositions have unexpectedly been found to impart improved curl retention and strength to hair fibers.
 References Cited v 9 Cl N D UNITED STATES PATENTS raw'ngs 2,506,492 5/1950 De Mytt et al. 424/71 IMPROVEMENT IN CURL RETENTION AND MECHANICAL PROPERTIES OF HAIR FIBERS BY .ALKANEDIOL BISBISULFITE SALTS BACKGROUND oF THE INVENTION Hair. dressing compositions of various types have been used to alter the appearance and physical proper ties of'human hair. Several compositions have been proposed and are commercially available which are directed to increasing the curl retentivity. strength and other mechanical properties which are commonly desired in the beautification of human hair.
In the desire to style hair it has been found desirable to both increase the mechanical properties of the hair as well as allow the hair to retain a memory for the curl styling to which it has been subjected. Hair that has been processeda number of times by various harsh chemicals which have penetrated the hair follicles, such as those used in tinting, straightening, bleaching and the like, tends to become damaged bysuch treatment and will no longer take and hold a style. The hair just hangsand gives an unaesthctic appearance.
Many so called conditioners have been proposed but few of them improve boththe propertiesof'curl retention as well as the mechanical strength of the hair fibers. In general; commercial conditioners function by putting a coating on the hair and give the hair an appearance of being well set. Nevertheless, hair fibers themselves, even when treated with such conditioners, lack the desirable curl memory and mechanical properties.
Among the hair dressing conditioners are those which contain polymeric materials which are deposited 'on the surface of the hair fibers. These products give only temporary benefit as they are generally soluble in water and, therefore,'are easily removed from the hair through the action of rain, bathing or washing of the hair. In addition, various aldehydes andketones, such as glyoxal and the like, have been proposed for cosmetic treatment of the hair to increase the mechanical properties. Such materials are, when used on human hair, objectionable due to their tendency to form brassy tones to dyed hair.
SUMMARY OF THE INVENTION DETAILED DESCRIPTION OF THE INVENTION The active components of the composition to which this invention is directed is a bisbisulfite alkanediol which may be represented by the general formula:
in which at least two of the R, R R, or R groups must be a metal bisulfitc radical, at least an additional two are hydroxy radicals, and any remaining R groups are hydrogen. The symbol n is any whole integer from 'l to H -which, thereby, allows the above general formula to represent compounds having alkanc chains of ethane to dodecane. It is also understood that the alkane chain may be branched as well as being linear in structure. The metal cation of the bisulfite may be any alkali metal or alkaline earth metal, such as sodium, po-
tassium, calcium, and the like, of which sodium is pre- 7 ferred because of its solubility and reactivity properties.
The bisbisulfite alkanediol salts of this invention are generally commercially available or are readily formed by those skilled in the art and the method of making such compounds forms no part of the instant invention. Ethanediol bisbisulfatejthe simplest form of the compounds found'useful in this invention, is also known as sodium bisbisulfite-glyoxal which is formed by the stochiometric reaction of solutions of glyoxal and sodium pyrosulfite. Additional examples of compounds found useful in this invention are disodium salt of 2,3- dihydroxy-l,4-butane disulfonate, disodium, 2,5-dihydroxy-1,6-hexane disulfonatc, disodium 2,l l-dihydroxy-1,l2-dodecane disulfonate and the like.
The various bisbisulfite alkanediols which have been herein found to be effective as curl retention and mechanical enhancing agents may contain alkane chains which are straight or branched and which can contain from I to 12 carbon atoms. The contemplated compositions will contain at least one bisbisulfite alkanediol and may, alternately, contain mixtures of said compounds. The lower derivatives, such as disodium bisbisulfite C C alkanediols are preferred due to their high reactivity perunit weight,
Small amounts of the subject compound or combinations of compounds may be applied to the human hair to obtain the desired end results. It has been found that concentrations ranging from about 1 part to about 10 parts of a metal salt of a bisbisulfite alkanediol per one hundred parts of composition yields satisfactory results. The preferred range of concentration being from about 4 parts to about 6 parts of such material per one hundred parts of composition. It is well realized that higher concentrations of the subject compounds will be necessary where higher homologs of the active compounds are used in as much as these compounds are less reactive per unit weight than their correspondingly lower homologs.
The bisbisulfite alkanediol is combined with a suitable cosmetic carrier base. These carrier bases are well known to those skilled in the art and include aqueous solutions, aqueous-alcoholic solutions, alcoholic solutions wherein the alcohol may be a C C alcohol, oil in-water emulsions, creams and various commercially available conditioner and shampoo compositions. The cosmetic carrier base substantially forms the remaining part of the hair dressing composition of this invention. These compositions are obtained by simply mixing the bisbisulfite alkanediols with'the cosmetic carrier vehicle. In some instances, wherein the active ingredient is not completely soluble in the cosmetic carrier, additional solvent for the active ingredient, such as water or alcohol, may be combined with the remainder of the cosmetic carrier and, if necessary, an emulsifying agent may be added to cause a homogenous mixture to be formed and thereby allow even distribution of the active material on the hair The basic body building composition described herein may have a pH range from about 1 to about 12.
Therefore, the bisbisulfite alkanediols have been found to be active both in alkaline and acid compositions. They have been found to'be most active in compositionshaving a pH of from about 4 to about 1 1.
It has been found that solutions containing bisbisulfite alkanediols upon long standing may become somewhat unstable. Such instability may be readily alleviated by buffering the solution with any known buffering agent to a pH of from about 5 to 8. The exact pH which stabilized the particular bisbisulfite solution can be readily ascertained by routine procedures. Excellent stability of ethanediol bisbisulfite is attained when solutions of it are buffered at a pH of 5.6. A 4 percent aqueous solution of ethanediol bisbisulfate has such a pH.
The cosmetically active compounds of this invention have been found to have enhanced activity in the presence of various metal ions in addition to those needed to form the salt material. These metal ions are normally transition metals which form metal ion complexes, such as cuprous, cupric, ferrous, ferric, nickel, zinc and the like. The addition of small quantities of these ions, such as from about 0.1 parts to about 2 parts per one hundred parts of composition have been found to further enhance the'activity of the bisbisulfite alkanediols in forming a body building and curl retention composition.
If desired, additional compounds which are conventionally used in hair preparations may be incorporated in the hair dressing composition of this invention. The addition of these compounds will depend upon the specific mode of application, texture of hair and the like and such additional compounds may include colorants, perfumes, fillers, dyestuffs, thickening agents and the like.
Hair dressing compositions containing the active material, as described hereinabove, may be applied to the hair in any known hair dressing manner, such as applying the composition onto the hair from a spray bottle or by an aerosol container. Alternately, the composition may be applied to the hair by hand until the hair is saturated with the composition. Such application can be safely done as the active ingredients herein disclosed are nontoxic.
As mentioned in the above background of the invention, various body building agents, such as glyoxal, have been previously used on the hair. During such use a hair dye complexing reaction is normally observed with a result in a shifting of color of the hair from an ash to a brassy tone with certain hair dye systems. Although the exact mechanism of such complexing is not known, it is believed that the mechanism which is operative in this color alteration results from a Schiff base formation between such aldehydes and free amine group present in the dye. Thisreaction produces a new chromophoric amine double bond group which shifts the hair dye color to a more brassy shade. The active compounds of this invention do not form the carbonamine double bond described above and, therefore, avoid the formation of the new chromophoric group.
After application of the composition of this invention in sufficient quantity to thoroughly saturate the hair, the composition is allowed to remain on the hair.
The active ingredients of this invention can be preferably promoted by applying mild heat ,to the treated hair. The degree of heat needed to allow the bisbisulfite alkanediols to be activated need not be such as would cause harm or pain to the user. Suitable amounts of heat to initiate such activation are readily attained through the use of hair dryers, hot combs, hot curlers and the like.'The resultant hair fiber willshow good curl retention and mechanical properties and will have substantially no noticeable colorshifting.
In as much as the active ingredient of this invention appears-to have an activation which'is promoted by heat, it has been found that a one step semi-permanent hair waving process can be also obtained through its use. In such a process one or more of the various well known reducing agents, such as sodium sulfoxylateformaldehyde and the like, or some other means, such as a metal acetate compound, which are known to break the hairs cystine double bonds could be applied to the hair with the bisbisulfite' addition compound present. No attempt to dry the hair would be made for at least 5 minutes after such application. During that time the hairs reduction would take place and once completed, the individual would then apply heat, such as from a hair dryer, for about 10 to about 40 minutes. During the time in which the heat is applied, the bisulfite compound would crosslink available sulfhydryl and amine groups in the desired hair coiffure. Such hair would then have a chemically strong curl retention and physical properties without any detrimental color change.
The following examples herein disclosed are for illustrative purposes only and are not meant to be limiting upon the inventive concept except as set forth in the appended claims. All parts and percentages are by weight unless otherwise indicated.
EXAMPLE 1 Five parts of sodium salt of the bisbisulfite-glyoxal addition product which had been previously prepared by reacting stoichiometric quantities of glyoxal and sodium pyrosulfite, is mixed with 95 parts water, with 95 parts of a :50 mixture of water and ethanol, and with parts of a shampoo concentrate containing 16% triethanolamine stearate, 0.10% propylparaben, 0.15% methylparaben, 11% sodium acetate, 1.8% boric acid and water (adjusted to pH 5.6 with NaOH).
1.5 gram swatches of hair which has been previously washed with a commercial shampoo, rinsed and dried are treated for 2 minutes with each of the above formulations. Similarly, 1.5 gram swatches of prepared hair were treated under the same conditions with the carrier base material. Following these treatments, all of the hair swatches were curled on inch O.D. plastic rollers. To avoid variation in the tension applied during the curling process, a gram weight was attached to the free end of each swatch prior to rolling. After being air dried, the hair samples were'carefully removed from the rollers, hung from the crimped end and photographed. Following this, each of the hair samples were combed and rehung for an additional 8 hours. After rephotographing the swatches, both controls and treated samples were washed with a standard triethanolamine stearate-alkanolamide shampoo. Once thoroughly rinsed, the samples were recurled and dried. These tests were repeated at controlled humidity levels of 30, 50 and 99%. The results of these evaluations showed that the glyoxal bisbisulftie treated swatched were superior in curl retentivity to the control swatches in each case.
EXAMPLE n Compositions containing 5 parts sodium salt of 2.3- di-hydroxy-1,4-butane-disulfonatc and compositions containing 5 parts sodium salt of 2.5-dihydroxy-L6- hexane disulfonate are mixed with 95 parts water, 95 parts shampoo concentrate containing 16% triethanolamine stearate and with 95 parts of a long chain alkyl cationic cream conditioner. Each of the six compositions formed are applied to 1.5 gram swatches of hair that has been previously shampooed, rinsed and dried. The hair samples are tested in the same manner as described in Example 1 above. Each tested sample shows superior curl retention and mechanical properties than the control samples to which it is related.
EXAMPLE II! A cosmetic composition containing 4 parts of the disodium salt of bisbisulfite-glyoxal addition product and 1 part of glyoxal, 1.62 parts of potassium citrate, 1.33 parts borax and 93.05 parts of water. The composition is thoroughly applied by hand to human hair which has been previously shampooed. The solution is allowed to remain on the hair. The hair is then set in the desired configuration of curlers and heat is applied with a commercial dryer. The resultant hair. upon examination. was found to retain the desired curl configuration even after repeated shampooings.
It will be understood that it is the intent to cover all changes and modifications of the disclosure of the invention herein chosen for the purpose of illustration which do not constitute departures from the Spirit and scope of the invention.
What is claimed is:
l. A process for improving the curl retention and mechanical properties of hair which comprises applying thereto in an amount sufficient to saturate the hair a composition comprising an effective amount of an alkanediol bisbisulfite salt having the formula:
wherein two of the R. R R and R groups are metal bisulfite radicals. an additional two of the groups are hydroxy radicals, and any remaining R groups are hydrogcn; wherein the metal ion of the bisulfite radical is selected from the group consisting of an alkali metal and an alkaline earth metal ion and wherein n is a whole integer of l to 11, and a hair cosmetic carrier and allowing the composition to remain on the hair for a time sufficient to allow the alkanediol bisbisulfite to enhance mechanical and curl retention properties to the hair.
2. The process according to claim 1 wherein the promotion of curl retention and mechanical properties is enhanced by applying mild heat to the treated hair.
3. The process according to claim 1 wherein the composition also contains an effective amount 'of a cysteine-cystine reducing agent 4. The process according to claim 2 wherein hair is set in the desired curl configuration prior to applying mild heat.
5. The process according to claim 1 wherein the alkanediol bisbisulfite salt is a C -C alkanediol bisbisulfite metal salt.
6. The process according to claim 1 wherein the al- I kanediol bisbisulfite salt is sodium bisbisulfite glyoxal.
7. The process according to claim 1 wherein the alkanediol bisbisulfite salt is the sodium salt of 2,3-
dihydroxy-l ,4-butane disulfonate.
2 percent of a complexing transition metal ion.