Hair setting composition and method

This invention deals with compositions for and a method of imparting temporary set to human hair involving the application of an aqueous composition containing a dialdehyde polysaccharide and a hydroxyaromatic compound in which two hydroxyl groups are meta to each other. After application of the composition, the tress is wrapped and heated using a conventional heated rod or brush type curling iron, heated roller, or salon or handheld hot air blower hair dryer to cause the polysaccharide and hydroxyaromatic compound to react with one another.

BACKGROUND 
This invention deals with compositions for and a method of imparting 
temporary set to human hair involving the application of an aqueous 
composition containing a dialdehyde polysaccharide and a hydroxyaromatic 
compound in which two hydroxyl groups are meta to each other. After 
application of the composition to the hair, the tress is wrapped and 
heated using a conventional heated rod or brush type curling iron, heated 
roller, or salon or hand-held hot air blower hair dryer to cause the 
polysaccharide and hydroxyaromatic compound to react with one another. 
Since time immemorial, man has exhibited a desire to control the 
configuration of the hair of the head, exemplified most basically by the 
daily ritual of combing, which is almost universally practiced. As part of 
the ritual of hair styling, man has not only come to cut and arrange the 
hair in styles influenced by the views of society, but has had a 
continuing desire to be able to either permanently or temporarily alter 
the hair type genetically bestowed by changing the natural curvature of 
his hair. 
The type of hair configuration bestowed by nature, be it straight, curly, 
or somewhere in between, is a function of the structure of the hair 
keratin in which both covalent disulfide bonds and secondary bonds 
including hydrogen bonds and salt linkages act to maintain the natural 
fiber configuration. 
One way of permanently overcoming the effects of these bonds is to break 
them by the application of an aqueous reducing agent after which the 
fibers are arranged in an altered configuration and the disulfide linkages 
are rebuilt at new sites within the fiber. The end result is a molecular 
structure in which the covalent bonds serve to maintain a modified hair 
style. This chemical approach to the problem is the basis for the various 
"permanent waving" processes and products available for self-application 
or as beauty shop treatments. 
While reductive processes do indeed provide a more or less permanent change 
in the natural hair configuration, their very permanence tends to render 
them undesirable in the views of many people. Such people, while wishing 
to be able to change the natural hair configuration, prefer a means of 
being able to do so only temporarily and without the bother of subjecting 
their hair to reductive chemical reaction. 
The simplest and probably the oldest method of temporarily altering the 
natural configuration of hair on the human head is to wet it with water, 
arrange the fibers in an altered configuration, allow the hair to dry, and 
then comb it into a desired final style. The temporary nature of water 
setting is due to the fact that while the secondary bonds, especially the 
hydrogen bonds, are broken and reformed in the presence of water, the 
covalent bonds are not. A disadvantage of water setting is that in the 
presence of a moist atmosphere, as on a humid day or as the result of 
scalp perspiration, a water-set hair fiber will tend to return to its 
original configuration by virtue of the influence of the covalent bonds in 
the keratin. 
While the origins of the practice are lost in history, attempts have long 
been made to use mechanical means to reduce the tendency of hair to revert 
to its natural form in humid circumstances. While such materials as mud 
and various naturally occuring gums and resins were used in ancient times 
to reinforce artificially constructed hair styles, modern man usually 
applies a solution of oils, waxes, and/or synthetic polymers which serve 
to mechanically fix the fiber array by partially coating the fiber 
surfaces and forming interfiber bridges. Since products of this type do 
not react chemically with the hair keratin to which they are applied, they 
may be used as often as desired without causing damage. 
Inspired by advances in polymer chemistry, investigators have proposed that 
fibers, including hair, be treated with compositions containing a variety 
of polymerizable monomeric species under conditions such that 
polymerization of the species will take place at the surface of or within 
the hair fiber resulting in the formation of a hair setting polymer film 
or deposit. Such films and deposits have a degree of semi-permanence not 
only because they resist water removal, but also because of limited 
chemical interaction with the fiber surface itself. In spite of this, they 
can sometimes be removed by conventional shampooing procedures and hence 
should be considered as improved "temporary" setting agents rather than 
"permanent" setting agents. 
As mentioned above, the practice of this invention involves the use of 
aqueous compositions containing polymerizable dialdehyde polysaccharides 
and meta-hydroxyaromatic compounds. A number of investigators have 
attempted to exploit dialdehyde polysaccharides and a variety of 
condensation systems in the treatment of natural fibers. This technology 
is exemplified in the following patents. 
U.S. Pat. No. 2,552,130 describes the treatment of wool and animal hair by 
immersion at room temperature in dilute aqueous solutions of specified 
polyhydric phenols and nonpolymeric aldehydes to form condensation 
products on the surface of the fibers to improve body and luster. 
U.S. Pat. No. 3,117,105 discloses reaction products of dialdehyde 
polysaccharides and phenols including meta and para substituted phenols 
and employing a condensation catalyst to yield polymeric products useful 
is resins and adhesives formulations. 
U.S. Pat. No. 3,479,128 discloses a process for increasing the tensile 
strength of wool and silk fibers by contact with an aqueous dispersion of 
a dialdehyde polysaccharide at 20.degree.-40.degree. C. 
U.S. Pat. No. 3,584,992 describes a process for modifying wool by reacting 
it with an anhydrous mixture of cresol and paraformaldehyde at 
60.degree.-180.degree. C. 
U.S. Pat. No. 3,479,427 discloses hair setting compositions containing 
hydrated dialdehyde starches. 
U.S. Pat. No. 4,278,659 describes hair treatments employing mixtures of 
glyceraldehyde, resorcinol, and precondensates thereof. 
DETAILED DESCRIPTION OF THE INVENTION 
In practicing the present invention, human hair is contacted with an 
aqueous dispersion of a dialdehyde polysaccharide and a 
meta-hydroxyaromatic compound followed by the application of heat to form 
a fiber-dialdehyde polysaccharidehydroxyaromatic reaction product. 
Dialdehyde polysaccharides are readily obtained by oxidation of 
polysaccharides such as corn, wheat, or other starches, celluloses, 
dextrins, dextrans, and the like with periodic acid. This is a well known 
method for the preparation of dialdehyde polysaccharides and may be 
illustrated by means of the following equation. 
##STR1## 
where .chi. represents the number of repeating polymer units. More 
recently electrolytic procedures have been used such as those exemplified 
by U.S. Pat. No. 2,648,629 to William Drench and Charles L. Mehltretter 
and U.S. Pat. No. 2,713,553, 2,770,589 and 2,830,941 to Charles L. 
Mehltretter. Such oxidized polymers for use in this invention may have 
molecular weights of from about 10,000 to about 500,000. 
The preferred dialdehyde polysaccharide for use in the practice of this 
invention is a dialdehyde starch derived from cornstarch in which from 
80-100% of the original anhydrogelucose units have been converted to the 
dialdehyde form. 
Dialdehyde polysaccharides as prepared by the above oxidation techniques 
must first be hydrated to convert them to a form usable in the practice of 
this invention. The technique of hydrating natural polysaccharides such as 
starch is well known in the art and is adapted as well to the hydration of 
dialdehyde polysaccharides. Hydration is effected by heating an aqueous 
dispersion of the material to at least 60.degree. C. for a sufficient time 
to attain a substantially clear solution. The end point is readily 
determined by visual observation since the dispersion during the heat 
treating step proceeds to thicken and then becomes substantially thinner 
at about the time the clarification occurs. For best results and for the 
purpose of reducing the time required for hydration, it is desirable to 
add an alkaline material such as sodium bicarbonate or borax at a 
concentration of about 5 to 15% by weight of the dialdehyde 
polysaccharide. In such case, hydration will usually take place within 10 
to 20 minutes. 
As mentioned above, dialdehyde polysaccharides including dialdehyde 
starches have in the past been reacted with phenolic compounds of various 
types to produce condensation products which are useful in a number of 
applications including the treatment of various natural fibers. The art 
does not disclose, however, that dialdehyde starch and 
meta-hydroxyaromatic compounds may be caused to condense on and react with 
the hair fibers to produce a cosmetically useful hair setting effect. 
The hydroxyaromatic compounds which we have found to be useful in the 
practice of this invention are the benzene and naphthalene derivatives 
having two hydroxyl groups which are meta(1,3) to each other. Examples of 
such materials are gallic acid; 3,5-dihydroxybenzoic acid; orcinol; 
1,3-dihydroxynpahthalene and, our preferred material, resorcinol. 
In preparing the compositions of this invention, we have found that ratios 
of dialdehyde polysaccharide to hydroxyaromatic compound may range from 
1:0.75 to 1:2.0 by weight, preferably 1:1 to 1:1.5. While a wide range of 
concentrations of mixtures containing the two active materials in water 
may be used in effectively setting the hair, we have found that from 2-8% 
by weight of combined dialdehyde polysaccharide and hydroxyaromatic 
compound may be used for favorable cosmetic hair attributes. We prefer to 
use 3.5% to 5.0%. 
The compositions of this invention may be applied to the hair in a variety 
of ways prior to the application of the heat necessary to bring about the 
condensation polymerization referred to hereinbefore. 
In one mode of application, an appropriate quantity of treating material is 
applied along the length of tresses of dry hair by means of spray 
application after which the tresses are combed from top to bottom to 
distribute the treating composition. Alternatively, tresses of hair may be 
shampooed, rinsed, and towel blotted to remove excess water after which an 
appropriate quantity of a composition is applied along the length of each 
tress from a squeeze-bottle or the like after which the tresses are combed 
through. 
Following application of the treating composition, the hair is dried and 
curled by using a conventional heated rod or bursh curling appliance or 
other conventional heat source with the time of treatment depending upon 
the temperature of the heat source employed. We have found that 
temperature ranges of 40.degree.-150.degree. C., preferably 
50.degree.-120.degree. C. may be employed. When a curling iron having a 
rod surface temperature approaching 100.degree. C. is employed, it will 
only be necessary to apply the heat for about 10 seconds to bring about 
the condensation reaction between the reactive materials. On the other 
hand, when a lower temperature is used as, for example, a hair dryer 
having an air temperature of 40.degree.-50.degree. C., it may be necessary 
to allow the hair to remain in its wrapped condition for up to an hour to 
assure complete drying and reaction. 
Where it is intended to employ the compositions of this invention in 
setting hair which has been bleached or oxidatively colored, it is 
desirable to include a hair conditioning ingredient to enhance ease of 
combing, both during the application of the composition and while styling 
the set hair after heat treatment. Such conditioning agents include 
proteins, surfactants and materials which can be broadly classified as 
oils and waxes. The use of such materials is well known to those skilled 
in the art of formulation of hair treating compositions and is described 
in, for example, the treatise entitled Cosmetics-Science and Technology, 
Second Edition, Vol. 2, pages 345-372, Edited by M. S. Balsam and Edward 
Sagarin. These materials may be incorporated in amounts ranging from 0.05 
to 1.0% by weight of the total composition.

EXAMPLE I 
A solid dialdehyde starch derived from cornstarch and having a degree of 
oxidation of 90-100% (SUMSTAR-190; Hexcel Corp.) is purified by stirring a 
dispersion of 150 grams of the solid starch and 3000 ml of distilled water 
for 3-4 hours and filtering. The process is repeated until the pH of the 
water reaches 5.15, after which the filtered material is vacuum oven-dried 
and bottled for further use. 
The purified starch is hydrated for use in the practice of the invention by 
dispersing 10 grams of the material in 100 ml of distilled water 
containing 1.0 gram sodium tetraborate (borax) which has been heated to 
60.degree. C. The temperature is raised to 80.degree.-85.degree. C. and 
held until a clear liquid dispersion results after approximately 15 
minutes. The dispersion is cooled and bottled for future use. 
An aqueous dispersion of purified, hydrated dialdehyde starch and 
resorcinol having a total solids content of 4.8% by weight and a starch 
dialdehyde:resorcinol molar ratio of 1.0:1.5 is applied to one side of the 
head of a female subject having hair approximately six inches long which 
has been shampooed with a commercially available anionic shampoo, rinsed 
and towel dried. After approximately 20 ml. of the above composition has 
been distributed even through one side of the hair by combing, the entire 
head is partially dried using a home style, hot air blower dryer after 
which the hair on both sides of the head is set using a commercially 
available heated rod curling iron having a rod surface temperature of 
about 100.degree. C. After styling both sides of the head, results are 
compared for body, feel, luster, and combing ease. The composition of this 
invention imparts more body and luster to the treated side than was 
present in the control side. Combing ease on the treated side is rated as 
better than average and reduced fly-away is observed. Twenty-four hours 
after the treatment, the treated side is judged to have better set holding 
and body. 
EXAMPLE II 
A composition as described in Example I is prepared containing, in 
addition, 0.5% by weight of stearyldimethylbenzyl ammonium chloride as a 
hair conditioning agent. 
After application of the composition as described in Example I, the hair is 
set on mesh rollers having a diameter of 1 inch, after which it is dried 
under a salon-style hair dryer having an air flow temperature of about 
45.degree. C. After about 40 minutes, the rollers on both sides of the 
head are removed and the hair styled. Comparative evaluation of the two 
sides produces the same results as described in Example I. 
EXAMPLE III 
A composition as described in Example I is prepared except that 
3,5-dihydroxybenzoic acid is substituted in place of the resorcinol. 
The composition is applied to the head of the subject as described in 
Example I except that the hair of the subject is allowed to dry completely 
before application. After application, excess water from the solution is 
allowed to evaporate under ambient conditions until the hair is nearly dry 
after which it is curled by the use of a conventional heated rod curling 
iron as described in Example I. Comparison of the two sides yields results 
as described in Example I. 
While particular embodiments of the invention have been described, it will 
be apparent to those skilled in the art that variations may be made 
thereto without departing from the spirit of the invention and the scope 
of the appended claims.