U.S. patent number 3,634,022 [Application Number 04/829,116] was granted by the patent office on 1972-01-11 for form-setting keratin substrates by a chemical treatment involving a vinyl monomer.
This patent grant is currently assigned to Colgate-Palmolive Company. Invention is credited to Seymour Grey, Clarence R. Robbins, George V. Scott.
United States Patent |
3,634,022 |
Robbins , et al. |
January 11, 1972 |
FORM-SETTING KERATIN SUBSTRATES BY A CHEMICAL TREATMENT INVOLVING A
VINYL MONOMER
Abstract
A process for form setting into a desired physical configuration
as keratinous substrate such as hair, wool and the like which as
been modified by a chemical treatment involving the use of
olefinically unsaturated compounds comprising wetting the
substrate, placing it into the desired physical configuration, and
then drying it while in said configuration. This form-setting
procedure may be repeated many times on the treated substrate.
Inventors: |
Robbins; Clarence R.
(Piscataway, NJ), Grey; Seymour (Piscataway, NJ), Scott;
George V. (Scotch Plains, NJ) |
Assignee: |
Colgate-Palmolive Company (New
York, NY)
|
Family
ID: |
25253570 |
Appl.
No.: |
04/829,116 |
Filed: |
May 29, 1969 |
Current U.S.
Class: |
8/127.51;
8/DIG.18; 8/127.5; 8/127.6; 8/128.1; 132/203; 424/70.5;
424/70.6 |
Current CPC
Class: |
A61Q
5/04 (20130101); A61K 8/8147 (20130101); D06M
14/06 (20130101); A61K 8/8152 (20130101); A61K
2800/94 (20130101); Y10S 8/18 (20130101) |
Current International
Class: |
D06M
14/06 (20060101); D06M 14/00 (20060101); A61k
007/10 () |
Field of
Search: |
;424/7D,71,72
;8/127.5,127.51,127.6,128A,128R ;132/7 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Meyers; Albert T.
Assistant Examiner: Clarke; Vera C.
Claims
We claim:
1. A method for producing hair in a desired physical configuration
which comprises reducing, with a chemical reducing agent, said hair
to convert at least some of the disulfide bonds present therein to
mercaptan form, removing said reducing agent, thereafter treating
said hair with an effective amount of an olefinically unsaturated
polymerizable monomer and an effective amount of a peroxide
initiator capable of liberating free radical species in the
presence of mercaptan groups, rinsing said hair to remove unreacted
monomer and initiator and then setting said hair while wet into the
desired physical configuration and drying said hair in such
physical configuration whereby a high-degree of form retention
stability of the said hair is obtained, said hair being further
characterized by substantially complete loss of form retention
stability when thoroughly wetted and further characterized by being
capable of resetting repeatedly in the same or different physical
configuration each time the hair is wetted and dried.
2. A method as defined in claim 1 wherein said monomer is itaconic
acid.
3. A method as defined in claim 1 wherein said monomer is methyl
methacrylate.
4. A method as defined in claim 1 wherein said initiator is cumene
hydroperoxide.
5. A method as defined in claim 1 wherein said reducing agent is
ammonium thioglycollate.
6. A method as defined in claim 1 wherein said reducing agent is
ammonium thioglycollate, the monomer is itaconic acid and the
initiator is cumene hydroperoxide.
7. A method as defined in claim 1 including treating said hair with
a multivalent Group IIA cation after removal of unreacted monomer
and initiator.
8. A method as defined in claim 1 including the further step of
treating said form stable hair with a relaxing agent selected from
the group consisting of salts of citric acid,
ethylenediaminetetraacetic acid, nitrilotriacetic acid, phytic
acid, ethane-1-hydroxy-1,1-diphosphonic acid, ethylene diphosphonic
acid, polymers of itaconic acid, aconitic acid, maleic acid,
methylene malonic acid, merconic acid and citraconic acid with a
water-solubilizing cation.
9. A method as defined in claim 8 wherein said relaxing agent is a
water-soluble citrate.
10. A method as defined in claim 8 wherein said water-solubilizing
cation is sodium or potassium.
11. A method as defined in claim 1 wherein said treating with
olefinically unsaturated polymerizable monomer and peroxide
initiator is carried out for a period of about 30 minutes to 2
hours.
12. A method as defined in claim 1 wherein the mole ratio of
catalyst to monomer is from about 0.001 to 1 to about 5:1.
13. A method as defined in claim 1 wherein said monomer and
initiator are dissolved in a solvent medium.
14. A method as defined in claim 13 wherein said solvent medium is
water.
15. A method as defined in claim 13 wherein said solvent medium
consists of from about 10 to about 90 percent by weight water, the
remainder comprising water-miscible organic solvent.
16. A method as defined in claim 15 wherein said water-miscible
organic solvent is a lower alkanol or acetone.
17. A method as defined in claim 1 wherein the step of treating
said hair with olefinically unsaturated polymerizable monomer and
peroxide initiator is carried out in the presence of a water
soluble halide salt of lithium, sodium, potassium or ammonium.
18. A method as defined in claim 17 wherein said halide salt is
lithium bromide, lithium chloride, sodium bromide, sodium chloride,
potassium bromide, potassium chloride, ammonium bromide or ammonium
chloride.
19. A method as defined in claim 18 wherein said halide salt is
lithium bromide.
20. A method as defined in claim 17 wherein the concentration of
halide salt is from about 0.025 to about 40 mols/mol. of monomer.
Description
The present invention relates in general to the treatment of
keratin-containing substrates and in particular to the provision of
a novel process to produce a desired physical configuration to the
hair.
Processes for the modification of keratin-containing substances
such as those associated with the treatment of human hair for
purposes of permanent waving, conditioning, etc., as well as the
treatment of keratinous fibrous materials for purposes of modifying
one or more properties of such material in accordance with
predetermined requirements are well known in the art, being
extensively described in the published literature, both patent and
otherwise. Thus, and with reference to the permanent waving of
human hair, conventional processing invariably involves an initial
impregnation treatment of the hair with a suitable reducing agent,
chemical and/or physical modification of the hair being thereafter
realized by the use of an appropriate oxidizing agent. The various
materials and processing solutions necessary to the implementation
of such techniques are well known in the art, being available
commercially in a wide variety of forms. Although enjoying rather
widespread commercial acceptance, hair-conditioning methods of the
aforedescribed type have nevertheless been found in practice to be
intolerably deficient in one or more important aspects. Perhaps the
primary objection relates to the failure of such processing to
provide a final hair set having the requisite form retention
stability as well as other desirable properties such as proper
level of hygroscopicity, in order to preserve hair flexibility
while preventing excess brittleness, hardness, etc. In addition,
many of the hair-treating processes heretofore promulgated
invariably yield a hair product deficient in the desirable level of
body, thickness, lustre, etc. Moreover, the compositions prescribed
for use in such processing in many instances yield film deposits
lacking in adhesion and exhibiting a highly objectionable tendency
to flake off, dry to a hard deposit and/or discolor the hair,
thereby vitiating any possibility of imparting the desired lustrous
appearance.
Other disadvantages found to characterize hair-conditioning
compositions currently available commercially relate to their
tendency to disrupt or otherwise deleteriously affect the
structural integrity of the hair fiber per se, e.g., elastic
properties, tensile properties, etc. This is quite obviously a
matter of extreme importance since damage of this nature, whether
irreparable or not, is invariably manifested in this form of dull,
lifeless hair, highly difficult to manage. In other instances, it
has been ascertained that the dyeability, i.e., dyereceptivity or
affinity characteristics of the hair fibers, is adversely affected
by a given hair conditioning treatment.
With specific reference to permanent waving of hair or the
converse, i.e., straightening of hair, the currently available
compositions and techniques require that the hair be treated while
in the desired physical configuration. Thus, for example, the use
of curlers during chemical treatment steps of the hair is
necessitated by the fact that the chemical treatment fixes the
physical configuration. Once the configuration of the hair is fixed
it is relatively form stable and any desire to change the physical
configuration requires a complete new chemical treatment, i.e.,
complete permanent wave.
As will thus be manifestly clear, the particular requirements of a
given hair-conditioning treatment may vary considerable, i.e., from
treatments primarily adapted to impart curl, wave, etc., to the
hair, to treatments designed solely to effect changes in one or
more of such properties as tensile strength, elasticity, dye
receptivity, thickness, etc.
As a result of the foregoing situation, considerable industrial
activity has centered around the research and development of
methods as well as compositions for use therein particularly and
beneficially adapted for use in connection with the purposive
modification of not only hair fibers, but in addition,
keratin-containing substrates of varying descriptions, including,
for example, wool.
In accordance with the discovery forming the basis of the present
invention, it has been ascertained that one or more properties of
keratinous substrates such as wool, hair, and the like may be
modified in accordance with predetermined requirements, via a
process involving a particular sequence of operations with
specified compositions.
Thus, the primary object of the present invention resides in the
provision of a process for the treatment of keratinous substances,
said process providing effective means whereby to permit selective
and repetitive variations in one or more of a wide variety of
properties of said keratinous material.
Another object of the present invention resides in the provision of
a process for the treatment of a keratinous substrate, said process
being beneficially and advantageously adapted for implementation in
connection with the setting and waving of human hair whereby to
provide a conditioned hair product having excellent properties as
regards form retention, stability, thickness, body, luster, and the
like.
A further object of the present invention resides in the provision
of a process for the treatment of keratinous substrates, whereby to
enhance or otherwise augment the affinity of same for one or more
dyestuff materials.
Other objects and advantages of the present invention will become
more apparent hereinafter as the description proceeds.
The attainment of the foregoing and related objects is made
possible in accordance with the present invention which in its
broader aspects includes the provision of a process for modifying
the keratinous substrate by association with certain monomer
compounds and thereafter setting said substrate in the desired
physical configuration. A more specific embodiment comprises (1)
treating a keratin-containing substrate with a reducing agent
capable of reducing disulfide to sulfhydryl, i.e., mercapto, said
treatment being carried out for a time sufficient to effect
reduction of said substrate, (2) removing residual reducing agent
from said substrate, and (3) thereafter treating said reduced
substrate with an oxidizing solution comprising (a) a peroxide
catalyst material i.e., initiator capable of liberating free
radical species in the presence of mercaptan said free radical
species being capable of initiating the polymerization of vinyl
monomer and (b) a vinyl monomer compound containing at least one
grouping of the formula:
and capable of undergoing polymerization in the presence of said
peroxide initiator and thereafter setting the hair in any desired
physical shape by thoroughly wetting and drying in the desired
shape.
Experimental evidence indicates that a polymerization reaction
occurs as a result of the mutual and intimate contacting of
peroxide, initiator, vinyl monomer and reduced keratin the latter
providing a high-population density of "active" sites in the form
of reduced disulfide, i.e., mercapto or sulfhydryl groups. As will
be appreciated, the disulfide linkages present in the
keratin-containing substances are represented by hair, wool, etc.,
comprise reducible groups, being capable of conversion to
sulfhydryl in the presence of relatively strong reducing agents
such as thioglycolic acid. The sulfhydryl groups thus provided as a
result of the reduction treatment exhibit a pronounced tendency to
interreact with peroxide initiator compounds with the concomitant
in situ generation of free radical species, the latter providing
effective means for initiating the polymerization of vinyl-type
monomers. Thus, the predominant portion of vinyl monomer
polymerization initiation as well as propagation is confined to the
reduction sites present in the keratinous substrate. In this
manner, the resultant polymer, which is attached to the hair or
wool fiber, in whatever manner it occurs, is actually integral,
both in a chemical and a physical sense, with such fiber.
It is recognized of course, that it has previously been proposed to
treat keratinous substrates such as wool with a monomer solution in
the presence of a redox catalyst system capable of liberating free
radicals under the conditions of the treatment, such treatment
purportedly functioning to impart to the substrate one or more
desirable properties. However, the subject invention differs
critically over the prior art methodology in several vital
aspects.
Thus, efficacious practice of the aforedescribed techniques
required as a critical imperative that the reduction treatment be
sufficient to accomplish substantial reduction of the keratin
substrate, i.e., that the extent of conversion of disulfide
linkages to mercaptan groups be such as to permit the desired
modification of the keratin substrate upon subsequent treatment
with oxidizing solution. The foregoing is to be distinguished from
those treatments conventional in the art and which provide for
simple impregnation of the hair fiber with the reducing agent.
According to the latter methods, nothing in the way of chemical
reduction of the keratin substrate obtains, such treatment being
designed solely for purposes of depositing upon the said substrate
sufficient of the reducing agent to react with subsequently applied
oxidizing solution. Accordingly, the keratin substrate remains
substantially unaffected at least in a chemical sense by the
reducing solution, the keratin serving primarily as a carrier.
Thus, when proceeding according to such methods, the
catalyst-containing monomer solution introduced at a later stage in
the processing reacts with the reducing agent per se as to be
distinguished from the keratinous substance, the
oxidation-reduction reaction being confined to those portions of
the substrate containing the previously deposited reducing
solution. In contradistinction, the initial reduction treatment
provided for by the present invention results in chemical
modification of the keratinous substrate i.e., reduction of
disulfide to mercaptan. Thus, the substrate itself whether hair,
wool, etc., serves as the reducing agent component of the free
radical liberating, redox catalyst system, the catalyst system
being activated upon subsequent addition of oxidizing solution. In
order to insure such a condition, it is imperative when proceeding
according to the method described above that a rinsing step be
interposed between the reduction and oxidation steps in order to
minimize any possibility of reducing agent remaining, as such, in
the substrate being treated. The significance of the rinsing
operation as a critical step in the processing sequence provided
herein will be made readily manifest by reference to the following
discussion. As will be recognized, the reducing agents when applied
will tend to permeate the total volume occupied by the keratin
substrate. Thus, with reference to hair, the reducing solution will
deposit to a great extent in the free space or interstices among
the individual hair fibers present in said substrate and, more
particularly, at or near the surface of the fiber. The extent of
reducing agent buildup in such areas will, of course, depend upon
several factors including the quantity of reducing solution
employed, the conditions of the treatment, e.g., time, temperature,
etc., condition of the keratin substrate, i.e., degree of porosity,
etc. As will be readily recognized, upon contacting of the
initiator monomer solution with the keratinous substrate under
conditions promotive of vinyl monomer polymerization, the
polymer-forming reaction will in no wise be limited to the
immediate environs of the hair fibers but, of course, will proceed
unabated in the aforedescribed free space areas in view of the
availability of copious amounts of reducing agent thereat. This
leads to the highly undesireable condition "solution
polymerization" leading to substrate interbinding; thus, in the
case of hair, solution polymerization could give rise to an
uncontrolled intertwining of the hair fibers resulting in the
formation of knots, snags, and other irregularities, the latter
being highly inimical to expeditious hair management. The latter
disadvantages are, of course, completely eliminated when proceeding
according to the particular sequence of operations comprising the
process contemplated in the present invention. Thus, the mandatory
employment of an intermediate rinsing operation whereby to
completely remove reducing agent from the keratinous substrate
being treated insures against the occurrence of solution
polymerization to an appreciable extent, polymerization being
confined substantially exclusively to the keratinous material,
i.e., hair fiber. This result necessarily obtains since each single
reduced hair fiber provides a locus for the in situ generation of
polymerization initiating, free radical species and this
polymerization proceeds "within" as opposed to "without" the hair
fiber.
Although any of the reducing agents compounds conventionally
employed in the art for the treatment of keratinous substrates may
be employed to advantage in performing the process under the
present invention, particularly beneficial results are noted to
obtain with those of the more active type. High-strength reducing
agents are preferred being more conducive to economically feasible
practice as well as quality control. Thus, the use of stronger
reducing agents obviates any necessity for the use of protracted
periods of reducing agent treatment while enabling the attainment
of substantial substrate reduction.
In addition to eliminating any possibility of substantial solution
polymerization, the aforedescribed process makes further possible
the realization of increased polymer takeup when compared to prior
art methods. Thus, when proceeding according to the instant
teachings, manifold increases in the amount of polymer which can be
grafted to the keratinous substrate in reduced periods of time can
be readily obtained. More specifically, the instant process of
graft polymerizing is eminently capable of yielding on the order of
at least a tenfold increase in amount of polymer grafted when
compared to prior art techniques carried out under analogous
circumstances. Of primary importance, and perhaps the salient
feature characterizing the said process, is the fact that the
keratin treatment may be carried out under reduced temperature
conditions, i.e., temperature approximating only
65.degree.-75.degree. F. By way of comparison, efficacious practice
of the methods described in the prior art invariably requires the
use of extremely high-temperature values, i.e., those approximating
at least 140.degree. F.; in fact, the high-temperature requirement
apparently constitutes a limitation on the operability of such
processes since attempts to effectuate such processing but
employing temperatures substantially lower than 140.degree. F. are
vitiated by the failure of the polymer-forming reaction to occur to
an extent consonant with feasible practice.
As will be self-evident, the sequence of operations comprising the
aforedescribed process involves necessarily the employment of the
reduction step as the initial expedient. This particular chronology
is necessary since the keratinous substrate must function as the
reducing agent during the oxidation or polymerization phase. In
contradistinction, the methods heretofore provided allow for
significant variation in the process sequence to the extent that
the oxidation step may be carried out prior to reduction without in
any way defeating or otherwise impeding the objectives of the
treatment. In fact in some instances preliminary oxidation
comprises a preferred embodiment. This situation serves to
underscore the relative unimportance of the function served by the
keratinous substrate in such prior art methods; as will be readily
obvious, the keratinous substrate in inert and merely serves as a
carrier for the reducing or alternatively oxidizing solution and in
no way participates functionally in the redox reaction giving rise
to the generation of free radical species. The substrate merely
provides the material to be acted upon by the redox treatment. By
way of contrast, the keratin substrate in the process of the
present invention provides a twofold function, viz, (1) the
reducing agent and (2) the material to be modified.
As previously mentioned, one of the processes of the subject
invention consists of essentially three basic operations performed
successively which can be characterized as (1) reduction, (2)
rinsing and (3) oxidation. In order to expedite comprehension of
these vital aspects of such a process each will now be discussed in
greater detail.
1. REDUCTION
Reduction of the keratinous substrate may be carried out utilizing
any of the reducing agents recognized in the art as being
conventional for such purposes. Such materials are, of course, well
known and thus a highly particularized listing of suitable
representatives would not be required. Suffice to say that the
particular reducing agent selected for use must be employed under
such conditions as to insure substantial reduction of the
keratinous substrate being treated. Thus, suitable materials
include water soluble salts, e.g., alkali metal salts and ammonium
salts of thioglycollic acid, e.g., sodium thioglycollate, ammonium
thioglycollate, etc.; alkali metal bisulfites, e.g., sodium
bisulfite, potassium bisulfite, ammonium bisulfite, etc.; water
soluble salts of thioglycerol; trihydroxymethyl phosphine, the
latter material can also be generated in situ form
tetra-kis-hydroxymethyl phosphonium chloride and the like. As
indicated previously, strong reducing agents are preferred.
However, such preference is based essentially upon operational
consideration, e.g., reduction of processing time. Thus, weaker
reducing agents may be employed; however, the use of such materials
entails correspondingly longer periods of treatment whereby to
accomplish the desired degree of keratin substrate reduction. The
reducing agent may be provided in the form of a simple aqueous
solution or alternatively in a mixed solvent system with water
miscible organic solvents such as mono and polyhydroxy alcohols,
e.g., methanol, ethanol, propanol, isopropanol, n-butanol, ethylene
glycol, 1, 2-propylene glycol, etc.; other-glycols, e.g., ethylene
glycol monomethyl ether, etc. The selection of a particular solvent
system will be influenced somewhat by the nature of the reducing
agent employed.
Thus, and with respect to the reducing agent substances previously
enumerated, it is usually found beneficial to employ mixed solvent
systems with, for example, bisulfite compounds, whereas simple
aqueous solutions suffice for the thioglycollate derivatives. The
proportions of organic, water-miscible solvent employed are not
particularly critical apart from the requirement that such
substance be employed in amounts sufficient to promote monomer
and/or catalyst solubility in the reaction medium. However, excess
organic solvent in the case of water-insoluble, organo-soluble
monomers should be avoided in order to minimize problems associated
with monomer-keratin initiator contacting. Although highly useful
in the practice of the present invention, the concentrations of
such materials employed should be maintained below about 75 percent
as a condition to optimum performance and not to operability. In
general, increased concentrations of organic solvent lead to
reduced rates of polymer takeup by the keratinous substrate upon
treatment with the oxidizing, monomer-containing solution. This may
be due to one or several factors. As will be understood, some
amount of the solvent employed in the reduction treatment remains
in the substrate despite the use of an intermediate rinsing step.
Thus, the employment of "reduction" solvent systems in which the
subsequently introduced monomer component exhibits relatively
unlimited solubility may serve to effectively reduce the rate of
polymer takeup by the keratin substrate since the affinity of the
monomer for the solvent exceeds its affinity for the keratin
substrate. With respect to the solvent materials previously
enumerated, it is found that the lower alkanols such as typified by
ethyl alcohol provide particular advantage for use in the present
invention. In any event, optimum realization of the advantages made
possible by the present invention can be obtained by the use of the
water-miscible organic solvent in concentrations ranging up to
about 50 percent by weight of solution, with the balance water,
i.e., from 0 to 50 percent by weight, with a range of about 20
percent to about 45 percent being particularly preferred. It is
further recommended that the reducing solution utilized be
substantially saturated with reducing agent, experimental evidence
establishing the obtention of greater rates of polymer takeup with
increased concentrations of reducing agent, with optimum
performance characteristics attending the use of saturated
solutions. The amount of reducing agent necessary to provide a
saturated solution will, of course, depend primarily upon its
solubility in the solvent system employed. Such limiting solubility
data can be readily deduced in a particular circumstance by rather
routine laboratory investigation.
The concentration of reducing agent employed may vary within
relatively wide limits depending inter alia upon the reducing power
of such material. For example, water soluble salts of thioglycollic
acid, e.g., ammonium thioglycollate, may be effectively employed in
concentrations approximating 6 percent by weight of solution
whereby to yield a pH of approximately nine Solutions of the
thioglycollate derivative may be readily and conveniently prepared
by diluting, for example, 98 percent thioglycollic acid with water
and thereafter increasing the pH by way of addition of concentrated
ammonium hydroxide. Sodium bisulfite comprises a somewhat weaker
reducing agent and thus effective use of such material requires its
employment in somewhat greater concentrations. In any event, it is
found in general that beneficial results are attainable with the
use of reducing agent in concentrations ranging from about 1
percent to 20 percent by weight of solution with a range of from 3
percent to 20 percent preferred. When using bisulfite it is usually
preferred to maintain a slightly acidic solution pH, i.e., excess
acidity should be avoided.
As previously indicated, the duration of the reduction treatments
will vary depending upon a variety of factors including the
concentration of reducing solution, the nature and extent of the
keratinous substrate being treated, and the like. In any event, it
is found that the use of reduction periods approximating 30 minutes
in duration are eminently suitable for the purposes described
herein. It is implicit, of course, that the reduction treatment be
sufficient to yield the desired degree of disulfide reduction in
the keratinous substrate.
The reducing solution may also contain varying quantities of one or
more added ingredients of an optional nature for purposes of
augmenting or otherwise enhancing the overall proficiency of the
reducing solution. Thus, for example, wetting agents may be
incorporated for purposes of reducing the surface tension extent at
the boundary between the keratinous substrate and reducing solution
whereby to promote penetration of the reducing solution into the
physical mass comprising said substrate. Surfactant materials
preferred for such purposes comprise nonionics, i.e., those of the
polyoxyalkylated type although it is found that certain anionic
materials, e.g., sulfonates, may likewise be employed to
advantage.
The total volume of reducing solution employed for the treatment
will likewise vary depending again upon such factors as solution
concentration and activity, the nature of the keratinous substrate,
etc. In any event, optimum quantities of reducing solution may be
readily determined in a particular circumstance by routine
investigation.
2. Rinse
Upon completion of the aforedescribed reduction procedure, the
keratinous substrate under treatment is next rinsed thoroughly so
as to insure the substantially complete removal of residual,
unreacted reducing agent. This may be effectively accomplished by a
simple water laving operation. No particular difficulty is
encountered as regards implementation of this step since the
reducing agents, being water soluble, are readily removed by the
water-rinsing treatment. It should be emphasized again, however,
that the rinsing operation, although simple of implementation,
nevertheless comprises a highly critical and important phase in the
process described herein since the efficacy of the entire treatment
depends critically thereupon. As previously described, the primary
purpose of the rinsing treatment is to eliminate or minimize any
possibility of polymerization occuring to any substantial extent
within the interstices or void volume of the keratinous substrate.
In this manner the difficulties associated with undesired
interbinding, snagging, knotting, etc., of keratinous mass are
avoided.
3. Oxidation
The third step in the sequence of operations prescribed in
accordance with one of the processes of the present invention
comprises oxidation. The essential ingredients of the oxidation
solution employed in the treatment of the keratinous substrate
comprise monomer and free radical liberating peroxide initiator.
The nature of the monomer material employed is not critical and may
be selected from a relatively wide range of materials and, in
general, encompassing vinyl compounds capable of undergoing
polymerization in the presence of a free radical liberating
catalyst. In general the monomer materials preferred for use herein
comprise those containing at least one grouping of the formula:
Accordingly, both mono- and poly-ethylenically unsaturated
compounds are contemplated for use herein. Such monomer materials
may also be represented for convenience according to the following
structural formula:
wherein R represents hydrogen, lower alkyl of one to four carbon
atoms, e.g., methyl, ethyl, propyl, butyl, isobutyl, etc., and
R.sub.1 represents (a) carbalkoxy, i.e., --COOR.sub.2 wherein
R.sub.2 represents hydrogen, alkyl containing from one to 20 carbon
atoms, e.g., methyl, ethyl, n-pentyl, octyl, lauryl, stearyl and
the like; alkenyl containing from three to 10 carbon atoms, e.g.,
allyl, 3,4-butenyl, 2,3-butenyl, 5,6-hexenyl, 2,3-hexenyl, etc.;
hydroxyalkyl containing from two to 10 carbon atoms, e.g.,
2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl,
2,3-dihydroxypropyl, 2,4 -dihydroxybutyl, 4,6-dihydroxyhexyl, etc.,
alkyl and dialkylaminoalkyl said alkyl each preferably containing
from one to four carbon atoms e.g., 2-N-methylaminoethyl,
2-N,N-dimethylaminoethyl, t-butylaminoethyl,
2-N,N-dimethylaminoethyl, 3-N-N-diisobutylaminopropyl etc.;
haloalkyl containing from one to 10 carbon atoms, e.g.,
hexafluoroisopropyl, perfluoroethyl, perfluoropropyl, 2-difluoro,
3-trifluoropropyl, 2-chloroethyl, 2-chloropropyl,
1,1,9-trihydroperfluorononyl methacrylate etc.; vicinal epoxyalkyl
containing from three to six carbon atoms, e.g., glycidyl,
3,4-epoxybutyl, 4,5-epoxypentyl, 2,3-epoxybutyl, etc., (b) amide,
including both substituted and unsubstituted forms, such group
corresponding to the following structural formula:
wherein R.sub.3 and R.sub.4 represent hydrogen, alkyl and
preferably lower alkyl or alternatively may represent the atoms
necessary to complete a polyunsaturated molecule such as:
wherein R.sub.5 represents an alkylene bridge containing preferably
from one to four carbon atoms such as methylene, ethylene,
propylene and butylene, (c) halogen such as chlorine, bromine,
etc., (d) alkoxy, e.g., methoxy, ethoxy, cyclohexoxy, (e) cyano,
i.e., the grouping --C N, (f) alkenyl aryl, said alkenyl containing
from one to four carbon atoms i.e., lower alkenyl e.g., o,m and
p
The aforementioned monomer materials may also be provided in the
form of their salified derivatives, e.g., salts with water
solubilizing cations. Thus, in the case of acrylic acid,
methacrylic acid, etc., the monomer material prior to use may be
converted to a suitable salified form such as typified by calcium
acrylate, i.e., (CH.sub.2 CH-COO.sup.-).sub.2 Ca.sup.+.sup.+,
sodium acrylate, potassium acrylate, calcium methacrylate, and the
like.
In addition to the aforementioned vinyl compounds, it has also been
found that other olefinically unsaturated compounds lead to
substantially similar properties in the keratin substrate, although
the mechanism may or may not be one of polymerization or
graft-copolymerization but rather a modification of the keratin
(i.e., polyamide) chain involving the attachment, randomwise or
otherwise of units of said olefinic compound to the keratin chain.
Such compounds are exemplifications of compounds of the more
general formula:
wherein each of the R groups is independently hydrogen, halogen,
alkyl, alkoxy, aryl, acyl, carboxy, carbalkoxy, carboxamido and the
like. The preferred nonvinylic-type monomers are the .alpha.,.beta.
-unsaturated dicarboxylic acids and anhydrides such as maleic,
itaconic, citraconic, etc.
As example of monomer materials falling within the ambit of the
foregoing definition and description there may be mentioned in
particular and without necessary limitation the following:
methyl methacrylate
ethyl acrylate
butyl methacrylate
isobutyl methacrylate
t-butyl methacrylate
n-pentyl methacrylate
n-hexyl methacrylate
isooctyl methacrylate
t-octyl methacrylate
allyl methacrylate
glycidyl methacrylate
3,4-epoxybutyl acrylate
2,3-epoxybutyl methacrylate
4,5-epoxypentyl methacrylate
methyl acrylate
butyl acrylate
allyl acrylate
3,4-butenyl acrylate
4,5-pentenyl methacrylate
5,6-hexeny acrylate
lauryl methacrylate
tridecyl methacrylate
tetradecyl methacrylate
cetyl methacrylate
octadecyl methacrylate
eicosyl methacrylate
2-hydroxypropyl methacrylate
3-hydroxypropyl acrylate
2,4-dihydroxybutyl methacrylate
2-t-butylaminoethyl acrylate
2-t-butylaminoethyl methacrylate
2-N,N-dimethylaminoethyl methacrylate
2-N,N-dimethylaminoethyl acrylate
ethylene glycol monomethacrylate
hexafluoroisopropyl acrylate
hexafluoroisopropyl methacrylate
perfluoroethyl acrylate
2,2-difluoropropyl methacrylate
perfluoroisobutyl acrylate
2-fluoroethyl methacrylate
methacrylic acid
acrylic acid
2-dimethylaminoethyl methacrylate
2-(2-diethylamino)ethyl methacrylate
methacrylamide
acrylamide
1,2-propylene chloride
vinyl chloride
vinyl bromide
vinyl fluoride
N-tertiary-butyl methacrylamide
N,n-diethyl methacrylamide
N,n-dipropyl acrylamide
N,n.sup.1 -methylene-bis-acrylamide
N,n.sup.1 -ethylene-bis-(N,N.sup.1 -diethyl)acrylamide
N,n.sup.1 -propylene-bis-(N,N.sup.1 -diisopropyl)methacrylamide
acrylonitrile
methyl vinyl ether
propyl vinyl ether
isobutyl vinyl ether
methyl isopropenyl ether
divinyl benzene ...
maleic anhydride or acid
itaconic anhydride or acid
citraconic anhydride or acid
In the case of polyfunctional monomeric materials typified by allyl
methacrylate, divinyl benzene and the like, it will be understood
that considerable cross-linking can occur in addition to the
predominant graft copolymerization reaction during oxidizing
treatment of the keratinous substrate. This result obtains since
monomer materials of this type possess more than one group capable
of undergoing polymerization under the reaction conditions
employed. It will in addition be understood that the monomer
materials contemplated for use herein may be employed singly or in
admixture comprising two or more. Selection of specific monomer
systems will depend primarily upon the requirements of the
processor having reference to the nature of the keratin material
under treatment, the specific properties desired in the ultimate
product, monomer reactivity, etc.
The oxidizing solution as mentioned above further contains as a
free radical liberating peroxide initiator material capable of
initiating the polymerization of vinyl monomer in the presence of
reducing agent, i.e., mercaptan. Initiator materials suitable for
such purposes are well known in the art being extensively described
in the published literature and include both the organic and
inorganic peroxides, hydroperoxides, peracids etc. Specific
examples of suitable initiators include without necessary
limitation, cumene hydroperoxide hydrogen peroxide, barium
peroxide, benzoyl peroxide, acetyl peroxide, tertiary-butyl
hydroperoxide, alkali metal salts of organic hydroperoxides, alkali
metal salts of per-acids, such as peracetic acid, perbenzoic acid,
persulfuric acid, etc. In general, it is found that particularly
beneficial results as regards the rate of monomer takeup are
obtainable with the use of organo-soluble initiator compounds such
as typified by cumene hydroperoxide for example, this compound
being of course water-insoluble: although somewhat inferior results
typify procedures involving the use of the water-soluble peroxygen
compounds vis a vis organo-soluble materials, such procedures are
nevertheless found to be highly satisfactory.
The initiator and monomer materials may be formulated utilizing
simple aqueous solutions alternatively mixed solvent systems, the
nature and proportion of the solvent materials employed depending
upon the solubility characteristics typifying the monomer and
catalyst components. In general, the solvent madium employed should
comprise from about 10 to about 90 percent by weight water with the
remainder comprising a water miscible organic solvent such as a
lower alkanol, e.g., ethanol, n-propanol, isopropanol, n-butanol,
etc., acetone and the like. Within the aforestated range, the
selection of particular amounts of organic solvent will depend,
inter alia, upon the relative hydrophobicity of the monomer
component. Thus, the use of substantially hydrophobic monomer
materials whether singly or in admixture may dictate the use of
increased quantities of organic solvent in order to facilitate the
obtention of a uniform and homogeneous dispersion of the involved
monomer and catalyst ingredients. By the same taken, the use of
hydrophilic monomer component dictates correspondingly the use of
increased quantities of water.
Regardless of the nature of the monomer material employed, a
further and vital consideration must be taken into account in
formulating the oxidizing, monomer solution. As will be recognized,
the efficacy of the entire process depends critically upon the
achievement of efficient contacting as between the ingredients
present in the oxidizing solution and the mass comprising the
reduced keratin substance. Thus, conditions promotive of such
contacting should be observed during processing in order to assure
optimum results. Accordingly, the relative proportions of solvent
employed in formulating the oxidizing solution should be selected
so as to provide a medium in which the monomer material exhibits a
ready capability of reaction with the keratin substrate under the
conditions employed in the treatment. Thus, it is usually
recommended practice to employ as organic solvents, one or more of
the lower alkanols of the type hereinbefore specified, solvents of
this type having been ascertained to assure optimum results. By way
of contrast, solvents of the ether and particularly, the ether
glycol-type, e.g., ethylene, glycol monomethyl ether, are somewhat
inferior, leading to reduced rates of monomer takeup. However, this
situation should not be construed as necessarily prescribing the
use of the latter solvent materials in accordance with the present
invention since particular circumstances may dictate the
feasibility of somewhat reduced grafting rates. Again, such matters
lie largely within the discretion of the processor.
The oxidizing solution may likewise be provided in the form of a
suitable dispersion, suspension, emulsion, or the like depending
upon the solubility characteristics of the monomer employed. This
can be readily achieved by the use of suitable suspending agents,
emulsifying agents, etc., the particular adjuvants effective for
such purposes being well known in the art. Actually, the form in
which the monomer is provided is of secondary importance, i.e.,
emulsion, solution, etc., the primary requirement being that such
material be available for reaction with the reduced keratin
substrate. To this end the monomer may be provided in a variety of
forms so long as such conditions be conducive to efficient
monomer-substrate contacting.
The proportions of monomer and catalyst employed in preparing the
oxidizing solution are not critical factors in the practice of the
present invention. Thus, it is only necessary that the monomer
material be employed in amounts sufficient to permit realization of
the desired degree of reaction with the keratin substrate;
correlatively, the concentration of catalyst material need only be
that sufficient to impart the desired reaction rate. Thus, the
monomer concentration would be increased in those instances wherein
a substantial extent of reduction is desired; conversely monomer
requirements may be reduced where lesser degrees of reduction are
desired. It will be understood that in those instances wherein the
monomer material is provided in liquid form e.g., methyl
methacrylate, the oxidizing solution may comprise simply the
monomer and catalyst. Thus, the monomer material may be employed in
concentrations ranging from as little as 1 percent to as high as
about 99 percent and preferably from about 5 to about 30 percent by
weight of total oxidizing solution. The amount of catalyst material
may likewise vary within wide limits, within a mole ratio range of
catalyst to monomer of from about 0.001 to 1 to about 5:1 with a
range 1:8 to 1:2 being preferred. Within the foregoing range the
particular amount selected will depend upon numerous factors
including, for example, the reactivity of the monomer material, the
concentration of the latter, the extent of thiol conversion
desired, and the like. In any event, determination of optimum
parameters in this regard can be readily determined in a particular
circumstance by routine investigation.
In general, the duration of the oxidizing solution treatment may
range from up to about 30 minutes up to about 2 hours whereby to
achieve substantial modification of the keratin material. In any
event, it is found in the vast majority of instances that oxidizing
periods on the order of 30 minutes suffice to permit the desired
reaction. Again, the optimum reaction time in a particular
circumstance will depend upon the reactivity of the monomer
component, the degree of modification desired in the keratinous
substrate, etc. However, one of the important aspects of the
aforedescribed process resides in the fact that beneficial results
may be obtained when carrying the oxidizing treatment out under
room temperature conditions. In contradistinction, prior art
methods heretofore promulgated in the treatment of keratinous
substrates invariably require the employment of relatively extreme
temperature, i.e., on the order of at least 60.degree. C., in order
to obtain the desired degree of substrate modification within
treatment intervals consonant with efficacious commercial practice.
Thus, one of the truly surprising aspects of this process attached
to the discovery that effective modification of the keratin
material under treatment may be obtained despite the use of
exceptionally mild temperature conditions, i.e., room temperature,
and treatment intervals on the order of only 30 minutes in
duration. The significance of this particular aspect becomes
abundantly clear when it is realized that the possibility of damage
to the keratinous substrate increases considerably as the treatment
conditions become more severe and particularly as the temperature
is increased. Thus, in the case of garments constituted in whole or
in part of keratinous substances, one or more properties of the
garment material may be deleteriously affected in the event of
subjection to prolonged treatment under the conditions prescribed
according to prior art methods. In contradistinction, the
relatively mild temperatures characterizing the process described
herein involves little or no risk of damage to the keratinous
material selected for treatment.
Another suitable process is a one-step process which involves
treating the keratin substrate with a composition comprising
1. a free radical liberating peroxide initiator material capable of
initiating the polymerization of ethylenically unsaturated vinyl
monomer compounds, said initiator being selected from the group
consisting of persulfuric acid and salified derivatives thereof
including salts with water solubilizing cations, e.g., alkali metal
such as sodium, potassium, etc., ammonium, substituted ammonium,
i.e., wherein one or more hydrogen atoms is replaced by alkyl,
hydroxyalkyl, etc., and
2. a vinyl monomer containing at least one grouping of the
formula:
said monomer being capable of undergoing polymerization in the
presence of said persulfate catalyst.
The vinyl monomers which may be used are similar to those
enumerated above for the multistep technique.
The initiator materials prescribed for use in accordance with the
one-step method comprise those selected from a relatively specific
and delimited class of materials, namely, persulfuric acid and its
salts with water solubilizing cations. As specific examples of
compounds found to function to exceptional advantage in the
practice of the present invention there may be mentioned,
persulfuric acid, disodium persulfate, dipotassium persulfate and
ammonium persulfate. The concentration of initiator employed is not
particularly critical and need only be employed in small but
effective amounts i.e., amounts sufficient to enable the attainment
of efficacious polymerization rates. Accordingly, suitable
concentrations of initiator may vary within relatively wide limits.
In any event, it is generally found that optimum results can be
assured by the employment of the initiator material in
concentrations ranging from about 0.02 to about 5 moles/mole of
monomer with a range of 0.1 to 2 being particularly preferred. It
will be understood that the selection of a particular concentration
value within the aforestated ranges will depend primarily upon the
reactivity of the monomer materials, the temperature employed in
the treatment, etc. It will further be understood that departures
from the ranges given may be dictated in a particular circumstance
depending upon the requirements of the processor. The persulfuric
catalyst compounds contemplated for use herein are uniquely typical
in that they exhibit a pronounced tendency to react with the
disulfide linkages present in the keratinous mass, such reaction
leading ultimately to the formation of free radicals. Thus, any
necessity for the use of particular reagents whereby to accomplish
preliminary reduction and thus conversion of disulfide to mercapto
is completely obviated. In contradistinction, an initial reduction
step is mandatory utilizing keratin-modification treatments
heretofore promulgated and involving the employment of other though
related peroxygen compounds. Thus, one of the truly surprising
aspects of this technique resides in the discovery that a rather
specific group of peroxygen initiators namely, the persulfuric
compounds of the type more fully described hereinbefore, enable the
accomplishment of keratin modification via the use of but a single
processing step.
The concentrations of monomer and catalyst and the use of organic
solvents generally conform to specification set forth in the
description of the multistep process but it is preferred to employ
solutions which are saturated with respect to the components
present.
To obtain optimum results utilizing the one-step method it is
advantageous to effect treatment of the keratin substrate within
the range of 90.degree. to 140.degree. F. and preferably from about
100.degree. to 110.degree. F. The pH of the reaction may vary from
about 1 to about 11 with a range of 3.5 to 9.0 being particularly
preferred. The usual acids and bases can be used for pH selection
e.g., sodium hydroxide, hydrochloric acid, sulfuric acid etc.
The modification processes of the present invention may be
effectively applied to a relatively wide variety of keratinous
materials including, for example, various types of hair, e.g.,
camel hair, mohair, horse hair, cattle hair, human hair, etc. Other
materials found to be suitable for treatment in accordance with the
present invention include wool, synthetic keratin fibers, chicken
feathers, turkey feathers, and the like.
It has further been found that in the aforedescribed processes, it
may be advantageous to incorporate into the monomer solution a
water-soluble halide salt. The nature of the water-solubilizing
cation is not particularly critical the salient requirement with
respect thereto being that such cation be devoid of any tendency to
deleteriously affect the keratin substrate or its immediate
environs. As particular example of water-soluble halide found to be
eminently suitable for use herein they may be mentioned, for
example, lithium bromide, lithium chloride, sodium bromide, sodium
chloride, potassium bromide, potassium chloride, ammonium bromide,
and ammonium chloride etc. The aforementioned bromides and
chlorides are uniquely characterized in their exceptional capacity
to augment to a considerable extent the graft copolymerization rate
obtainable. Thus, the use of the halide salt in relatively minor
amounts nevertheless permits the attainment of manifold increases
in the polymerization reaction rate thereby enabling the grafting
of increased quantities of polymer for a given period of treatment.
The concentration of halide employed may likewise vary within
relatively wide limits. In any event, it will usually be found that
beyond certain concentration values incremental increases in the
amount of halide employed fail to give rise to corresponding
increases in graft polymerization rate, i.e., the quantum
efficiency of the halide compound tends to diminish with the use of
increased concentrations thereof. In any event, significant
enhancement in polymer grafting rate can be obtained by the use of
the halide salt in concentrations ranging from about 0.025 to about
40 moles/mole of monomer with a range of 4 to 10 found to be
particularly beneficial. Apparently, the halide ion contributes
effectively to the reaction mechanism giving rise to the formation
and proliferation of free radicals. Thus, the halide salt, e.g.,
lithium bromide, appears to react with the peroxide catalyst
materials, e.g., potassium persulfate, resulting in the liberation
of free radical species according to the following sequence of
reactions,
Br.sup.-+S.sub.2 O.sub.8 .sup.-.sup.- Br.sup..
+SO.sub.4.sup.-.sup.. +SO.sub.4 .sup.-.sup.-
So.sub.4.sup.- +n.sub.2 o hso.sub.4 .sup.-+oh.sup..
br.sup.. +Br.sup.. Br.sub.2
In the presence of reduced keratin fibers, e.g., wool, chain
transfer can take place, the reaction involved being represented as
follows:
Wool-SH+SO.sub.4 .sup.-. HSO.sub.4 .sup.-+Wool-S.sup..
Wool-SH+ OH.sup.. H.sub.2.+ Wool-S.sup..
Experimental evidence likewise suggests that the exceptional
improvement in graft copolymerization rate cannot be explained
solely by reference to the foregoing. Apparently, the presence of
the halide compound promotes swelling of the keratin mass, e.g.,
fibers, while favoring the absorption of peroxide catalyst and
monomer according to concentration effects.
The keratin substrate, and particularly hair, when treated and
modified in accordance with the aforedescribed techniques is, in
order to achieve the ends and objects of this invention then
thoroughly wetted with water and "set" to any desired shape while
wet. It is then permitted to dry in the "set" form. The result is a
most unique and unexpected degree of form retention stability even
under conditions of relatively high humidity e.g., 85 percent R.H.
Another remarkable characteristic of the modified hair is its
ability to be put into any physical form, repeatedly, if first
wetted out and then dried in the selected physical
configuration.
In the examples which follow all parts and percentages given are by
volume unless otherwise indicated. It will be understood that such
examples are given for purposes of illustration only and should not
be considered as necessarily constituting a limitation on the
preset invention.
EXAMPLE 1-16
As previously mentioned, a number of factors exhibit considerably
influence upon the efficacy of the reducing solution treatment,
i.e., in terms of effect upon the capacity of the keratinous mass
thus treated to take up monomer in the oxidizing step. This
situation is illustrated by the present examples wherein the
keratinous mass subjected to treatment comprises human hair. In
each case, the reducing treatment is carried out at room
temperature for a period of up to 30 minutes utilizing
approximately 20 ml. of reducing solution per gram of hair. Upon
completion of the reduction treatment, the hair sample is rinsed
thoroughly so as to completely remove residual reducing solution.
The oxidizing treatment is thereupon carried out utilizing a
solution consisting of methyl methacrylate monomer (12.0 percent),
cumene hydroperoxide catalyst (5.0 percent), and ethyl alcohol
(41.0 percent), with the balance water. In each instance the hair
sample selected for treatment is weighed both before and after
treatment with the increase in weight, i.e., extent of polymer
grafting, calculated by difference. ##SPC1## ##SPC2##
In general, increasing the period of oxidizing solution treatment
effects corresponding incremental increases in the amount of
polymer grafted. This situation is illustrated by reference to the
following example which summarize the results obtained in
connection with the treatment with methyl methacrylate.
In each of the examples the reduction treatment is effected
utilizing a 6 percent solution of ammonium thioglycollate having a
pH of 9, the period of treatment being 10 minutes. The keratinous
substrate selected for treatment comprises samples of human hair.
Moreover, in each instance the reducing solution is employed in
volumes approximating 20 ml. per gram of hair sample being treated.
Upon completion of the reduction treatment, the hair sample is
thoroughly rinsed in order to completely remove residual reducing
solution. For each of the experimental runs, oxidizing solution
treatment is carried out at room temperature for a period of 30
minutes employing 20 ml. of oxidizing solution per gram of hair
sample. The results obtained are itemized in table 2. ##SPC3##
As will be readily evident, significant amounts of polymer are
effectively grafted to the hair sample under treatment despite the
employment of moderate, room temperature conditions. It will also
be understood that the amount of polymer grafted as a function of
time will also be influenced to a great extent by the population
density of reduction sites available in the keratinous mass. Thus,
as the number of available reducing sites decreases appreciably,
the rate of polymer grafting will correspondingly decrease. This is
further evidenced from the results itemized in connection with the
oxidizing solution treatments ranging from 5 to 20 minutes; this,
with respect to the initial incremental increase in time of from 5
to 10 minutes an approximate threefold increase in percent grafting
is obtained. By way of contrast, increasing the period of oxidizing
solution treatment from 10 to 15 minutes brings about a
corresponding twofold increase in percent grafted. However, as the
data makes manifestly clear, the rate of percent grafting tends to
decrease rather markedly as the period of treatment is increased
thereafter.
Cumene hydroperoxide comprises highly effective catalyst means and
is preferred for use being capable of storage for extended periods
of time in the absence of decomposition or other degradation. In
any event, contacting of the catalyst material with reducing agent
prior to actual use should be avoided in order to eliminate or at
least minimize any possibility of inadvertent catalyst loss.
In general, increased polymerization grafting rates are attainable
with the use of the catalyst material in increased amounts within
the ranges hereinafter stated. This situation is illustrated by
reference to the following data which summarizes the results
obtained in connection with the treatment of human hair samples
with methyl methacrylate. In each instance reduction is carried out
for a period of 10 minutes utilizing a 6 percent, aqueous, ammonium
thioglycollate solution having a pH of 9. The reducing solution is
employed in quantities of 20 ml. per gram of hair sample. Treatment
with oxidizing solution is effected in the manner explained in
connection with example 17-21. The results obtained are itemized in
the following table: ##SPC4##
As will be noted, highly favorable percent grafting figures are
obtainable despite the use of reduction treatment periods on the
order of only 10 minutes. As will be further observed, relatively
slight increases in the amount of catalyst employed serve to
augment considerably the grafting polymerization rate. Accordingly,
increasing the concentration of cumene hydroperoxide from 1 to 4
ml. per 100 ml. of solution enables the attainment of a
corresponding increase in percent grafting from 4.96 to 17.5 an
almost fourfold increase. Such figures must be regarded as being
highly significant in view of the curtailed reducing treatment
intervals. Quite clearly, the polymerization grafting rate is
highly sensitive and response to the amount of catalyst employed.
Again, it is of the first order of significance that such highly
beneficial rates of polymer takeup are available under room
temperature conditions.
As illustrated in examples 1-16, the nature of the solvent employed
in the reducing solution is of vital importance and affects
significantly the graft polymerization rate obtainable in the final
oxidizing step. As the following examples make readily apparent,
the identical situation exists as regards the nature of the solvent
material employing in the monomer containing oxidizing solution.
This situation is illustrated by the following examples which
summarize the results obtained in connection with the treatment of
human hair samples with methyl methacrylate. The reducing and
oxidizing treatments are identical to those described in the
previous examples. As will be noted, the solvent employed for the
experimental runs comprises ethyl alcohol with the balance water.
##SPC5##
As the foregoing results make manifestly clear, the employment of
organic solvent in increased quantities leads to the obtention of
decreased polymerization rates. It will further be understood that
the relationship extant between concentration of organic solvent
and corresponding polymerization rate depends critically upon the
nature of the monomer materials employed. Thus, a given monomer
component may tolerate copious quantities of organic solvent in the
absence of deleterious effects upon polymerization grafting rate.
In general, decreased polymerization rates can be expected in those
instances wherein the monomer material exhibits ready and
relatively unlimited solubility in the organic solvent selected. In
any event, such parameters can be readily ascertained in a
particular circumstance. Thus, should decreased grafting rates be
desirable, the use of increased amounts of organic solvent may well
be dictated as a particular means to accomplish same.
EXAMPLE 30
A 22.0 g. sample of DM-36 hair is reduced for 5 minutes with 440
ml. aqueous solution of 6 percent ammonium thioglycollate at pH 9.
The hair is rinsed thoroughly with water and then treated for 1
hour at 75.degree. F. with 440 ml. of the following solution.
40g itaconic acid
20 ml. cumene hydroperoxide
200 ml. ethanol
dilute to 500 ml. with water
The hair is then rinsed and dried in a random fashion. The hair
contains 22.4 percent itaconic acid. The hair is made into tresses
and then thoroughly wetted out and hung straight, with weight until
dry. The hair is very straight. Again, it is wetted thoroughly and
wrapped around glass rods and dried in this form. An extremely
tight curl results, substantially in the form as wrapped on the
glass rods. The curled hair is then conditioned at 85 percent R.H.
and shows the following percent wave retention after the indicated
times.
After (Hrs.) % Wave Retention
__________________________________________________________________________
0.5 99.3 1.0 98.8 2.0 97.8 4.0 96.7 6.0 96.0 24.0 93.0 48.0 92.5
__________________________________________________________________________
The hair is then put through four series of cycles each comprising
wetting, straightening, drying, wetting, curling and drying.
In all cases the hair maintains its "set" form after drying and
retains this form even after severe and prolonged exposure to high
humidity (60-90 percent R.H.).
Untreated DM-36 hair when subject to a thorough wetting and
curling, initially does not show the same degree of physical
conformation to the glass rods as the treated hair, but even more
significantly, after exposure to high humidity (85 percent) the
wave retention properties are as follows:
After (Hrs.) % Wave Retention
__________________________________________________________________________
0.5 57 1.0 42 2.0 36 4.0 34 6.0 32 24.0 28
__________________________________________________________________________
An additional remarkable characteristic of the treated hair lies in
the fact that straightened hair remains substantially unchanged
under high-humidity conditions while untreated hair "kinks up."
EXAMPLE 30A
Example 30 is repeated employing the indicated monomers and amounts
in lieu of 40 g. itaconic acid.
1. 10 g. itaconic acid
2. 40 g. itaconic acid
3. 15 g. methylene malonic acid
4. 50 g. citraconic acid
5. 30 g. maleic acid
6. 12 ml./100 ml. ethyl acrylate
7. 6 ml./100 ml. vinyl chloride
8. 25 g. lauryl methacrylate
Excellent results are obtained comparable to Example 30.
EXAMPLE 30B
Example 30 is again repeated modifying Example 30 as indicated:
1. 200 ml. ethanol replaced by 100 ml. acetone
2. peroxide replaced by equal weight of di-t-butyl peroxide
3. peroxide replaced by equal weight of potassium persulfate
EXAMPLE 31
A 20.8635 g. sample of DM-36 hair is reduced with 400 ml. of a 6
percent aqueous solution of ammonium thioglycollate (pH = 9) for 5
minutes. The hair is thoroughly rinsed with water to remove the
thioglycollate and treated with the following solution at about
75.degree. F.
32 g. itaconic acid
16 ml. cumene hydroperoxide
160 ml. of ethanol
dilute to 400 ml. with deionized water
The treated hair is rinsed with water and dried. The dry weight is
24.4543 g. indicating a weight gain of 17 percent.
Six tresses are made from the above treated hair of which two are
treated with 0.1 M sodium citrate pH = 9.5 and two are treated with
0.1 M CdSO.sub.4. All six are rinsed with water and waved on rods
as in example 30. The four after-treated tresses
(2-citrate-2-CdSO.sub.4) and the other two itaconic treated tresses
along with two untreated hair tresses are conditioned at 85 percent
R.H. and the percent wave retention noted as previously. The
results are ##SPC6##
The above data demonstrate that the itaconic treated hair has
excellent form stability under high humidity; the cadmium sulfate
after-treated tresses are somewhat more form stable and the
untreated hair has little stability. The citrate after-treated hair
demonstrates a means for causing a relaxation of the curl (form
stability). A further treatment of the citrate relaxed tresses with
cadmium sulfate reestablishes the form retention characteristic
similar to that initially provided by the cadmium sulfate treatment
described above.
Among suitable relaxing agents which have been found useful and
effective mention may be made of the general class of polyacids and
their derivatives and particularly the water soluble salts of
citric acid, ethylenediaminetetraacetic acid, nitrilotriacetic
acid, water-soluble phytates, e.g. sodium and potassium phytate,
water-soluble salts of ethane-1-hydroxy-1,1-disphosphonates,
water-soluble salts of methylene diphosphonic acid (e.g., trisodium
and tripotassium salts), water-soluble salts of polymers and
interpolymers of itaconic acid, aconitic acid, maleic acid,
methylene malonic acid, merconic acid, citraconic acid, etc.
In addition to cadmium sulfate, illustrated above, other
water-soluble multivalent metal salts can be used to "set" the
hair. The preferred salts are the Group IIA metal cations. The
anion is not critical so long as the salt is sufficiently soluble
in the treating bath. The preferred anions are sulfate, nitrate,
halogen and the lower fatty acids e.g., formate, acetate,
propionate, and the like.
The unique form stability of the hair treated in accordance with
the present invention is further vividly demonstrated by the
following:
Example 32
Four tresses are treated with monomer as in example 31. Two of the
tresses are "set" in a straight form by drying with weights
suspended therefrom. The remaining two tresses are treated with
cadmium sulfate as in example 31 and also "set" straight.
Two additional, but untreated tresses are thoroughly wetted out and
also dried in a straight form. Finally a pair of tresses which had
been processed while curled on glass rods with a commercial home
permanent wave was, after fully "set," thoroughly wetted out and
also hung straight with a weight attached. All eight tresses, after
drying in the straight form are conditioned at 85 percent R.H.: the
four tresses treated according to the present invention remained
substantially straight. The untreated hair curled somewhat, while
the permanent waved hair curled even more. This demonstrates the
versatility and form stability of this instant invention.
EXAMPLE 33
Eight 2 g. tresses are prepared from 16 g. of DM-36 hair. Two are
used for control (1 and 2 ) and the other six are reduced with 20
ml. of 6 percent aqueous ammonium thioglycollate at pH9/g. of hair.
They are then thoroughly washed with water and treated with
composition as follows: ##SPC7##
Tresses 3 to 6 are treated for 1 hour and 7 and 8 for 30 minutes,
all at 75.degree. F. The eight tresses are then soaked with water
and waved on glass rods.
The tresses are dried at 60 percent relative humidity (R.H.)
overnight, and then examined at 85 percent R.H. at intervals of
time from one-half hours to 24 hours. The percent wave retention is
averaged for each pair and given below.
Tresses After (Time Hrs.) 1 and 2 3 and 4 5 and 6 7 and 8
__________________________________________________________________________
1/2 68.0 94 90.3 92.4 1 52.0 90 81.5 86.4 2 43.0 87 75.0 81.0 4
36.8 83.8 70.0 75.0 6 34.1 82.0 63.6 73.0 24 31.6 79.0 60.0 68.9
__________________________________________________________________________
The outstanding retention properties are evident from the
above.
EXAMPLE 34
In this and the following examples illustrative techniques of the
one-step treating process are given.
A sample of human hair is treated for a period of one hour at
106.degree. F. with a solution of the following composition:
potassium persulfate 2 parts methyl methacrylate 2 parts acetone 20
parts 0.095N hydrochloric acid 17 parts water 61 parts
Thereafter, the hair sample is rinsed with water and dried over
calcium chloride for 12 hours in a dry box. The difference in dry
weights of the hair sample, i.e., taken before and after treatment
is thereupon tabulated.
The amount of polymethyl methacrylate grafter to the hair sample is
calculated by difference of 10.78 percent.
EXAMPLE 35
Example 34 is repeated except that the solution employed has the
following composition:
potassium persulfate 2 parts methyl methacrylate 2 parts acetone 40
parts 0.095N hydrochloric acid 17 parts water 43 parts
The amount of polymethyl methacrylate grafter to the hair sample in
this instance is calculated at 7.45 percent.
As will be noted, decreasing the amount of acetone relative to the
amount of water present in the system serves to promote the graft
polymerization reaction rate to the extent of making possible an
almost 44 percent increase in amount of polymer grafted for the
same period of treatment.
More favorable graft polymerization rates can likewise be obtained
by increasing the concentration of monomer and/or catalyst
employed. This situation is illustrated by the following
example:
EXAMPLE 36
Example 34 is repeated except that the solution employed has the
following composition:
potassium persulfate (4% solution in 0.09N hydrochloride acid) 25
parts hydrochloric acid 5 parts methyl methacrylate 5 parts methyl
alcohol 45 parts water 30 parts
The amount of polymethyl methacrylate grafted is calculated at
10.96 percent. As will be observed the percent polymer grafting
figure approximates that obtained in example 35 despite the fact
that less catalyst is employed. However, the total amount of
monomer employed is increased from 4 to 5 parts while the solvent
employed comprises methanol.
As illustrated by example 37 and 38, polymer grafting may likewise
be carried out employing monomer admixtures whereby to yield a
keratin product having an interpolymer grafted thereto.
EXAMPLE 37
Example 34 is repeated except that the solution employed has the
following composition:
potassium persulfate (saturated solution in 0.095N hydrochloric
acid) 15 parts methyl methacrylate 2 parts methacrylic acid 2 parts
methyl alcohol 15 parts water 15 parts
The amount of methyl methacrylate-methacrylic acid copolymer
grafted to the hair sample is calculated at 17.82 percent.
EXAMPLE 38
The procedure described in example 34 is repeated except that the
solution employed has the following composition:
potassium persulfate (4% in a buffer solution pH=4.1) 30 parts
methyl alcohol 20 parts methyl methacrylate 2 parts methacrylic
acid 4 parts
The amount of methacrylic acid-methyl methacrylate copolymer
grafted to the hair sample is calculated at 24.56 percent. As will
be noted by comparison with example 37, increasing the total amount
of monomer component as well as catalyst correspondingly increases
the amount of polymer grafted.
EXAMPLE 39
Example 34 is repeated except that the solution employed has the
following composition:
potassium persulfate (4% solution in 0.09N hydrochloric acid) 15
parts methacrylic acid 2 parts methyl alcohol 15 parts water 15
parts
The amount of polymethacrylic acid grafted to the hair sample is
calculated at 13.35 percent.
EXAMPLE 40
Example 34 is repeated except that the solution employed has the
following composition:
potassium persulfate (4% solution pH=2.5) 40 parts ethyl alcohol 16
parts methacrylic acid 2 parts
The amount of polymethacrylic acid grafted to the hair sample is
calculated at 26.81 percent.
As example 40 makes clear, increasing the amount of catalyst
employed gives rise to an approximate 100 percent increase in
amount of polymer grafted as will be noted by comparison with
example 39.
EXAMPLE 41
Example 34 is repeated except that the solution employed has the
following composition:
potassium persulfate (saturated in 0.095N hydrochloric acid) 15
parts methyl alcohol 15 parts methacryamide 2 parts water 15
parts
The amount of polymethacryamide grafted to the hair sample is
calculated at 6.77 percent.
Results similar to those described in the foregoing examples are
obtained when the procedures described therein are repeated but
employing in lieu of the monomer components exemplified the
following:
calcium acrylate
acrylonitrile
butyl acrylate
t-butyl acrylate
hexafluoroisopropyl acrylate
allyl methacrylate
lauryl methacrylate
octadecyl methacrylate
4,5-pentenyl methacrylate
2-hydroxyethyl methacrylate
perfluoroethyl acrylate
glycidyl methacrylate
3,4-epoxybutyl acrylate
dimethylaminoethyl methacrylate
acrylamide
N,n-methylene-bis-acrylamide
itaconic acid
citraconic acid
maleic acid
EXAMPLE 42
To demonstrate still further the outstanding properties of the
treated hair, the tresses of example 32 (in straight form) are
resoaked in water and, again, waved on rods. The percent wave
retention at 85 percent R.H. is recorded below. ##SPC8##
EXAMPLE 43
The eight tresses of example 33 are resoaked in water to remove the
wave and then rewaved on glass rods at 60 percent R.H. The percent
wave retention at 85 percent R.H. is as follows:
Tresses After (hours) 1 and 2 3 and 4 5 and 6 7 and 8
__________________________________________________________________________
1/2 77.8 96.3 91.2 94.8 1 56.3 92.0 80.3 88.0 2 43.2 85.0 70.2 79.3
4 33.7 78.2 65.0 75.0 6 32.6 76.4 61.3 70.8 24 28.1 75.5 54.8 65.0
__________________________________________________________________________
EXAMPLE 44
The eight tresses of example 43 are shampooed with 1 ml. HALO/2g.
of hair, rinsed with water and condition straight (with 50
weight/tress) overnight at 60 percent R.H. The tresses are then
exposed to 85 percent R.H. for 24 hours and the percent contraction
measured. The results are:
Tresses (% of length at 0 hours) After (hours) 1 and 2 3 and 4 5
and 6 7 and 8
__________________________________________________________________________
1/2 98.4 100 100 99.2 1 97.6 100 100 99.0 2 96.4 100 100 99.0 4
95.5 100 100 98.6 6 96.0 100 100 98.2 24 95.2 100 100 99.5
__________________________________________________________________________
EXAMPLE 45
The tresses from example 44 are once again rewaved by first soaking
in water, then waved on glass rods and dried overnight at 60
percent R.H. They are then exposed for 24 hours to 85 percent R.H.
and the percent wave retention measured. The figures appear in the
table below.
Tresses After (hours) 1 and 2 3 and 4 5 and 6 7 and 8
__________________________________________________________________________
1/2 74.4 97.3 92.8 96.6 1 59.1 93.4 84.4 91.1 2 47.3 87.8 75.0 85.8
4 40.0 82.7 68.2 77.8 6 37.2 81.7 65.0 74.7 24 32.7 77.5 60.2 70.0
__________________________________________________________________________
The continued ability of the tresses treated as herein taught to
reproduce the waving effect after repeated treatments of
straightening, shampooing, etc., is vividly demonstrated here.
In general, keratinous material which have been exposed to
environments which tend to be damaging toward same exhibit a
greater tendency to undergo more favorable polymerization
reactions, i.e., more accelerated grafting rates. This situation
can probably be explained by reference to the fact that the damaged
keratin fiber for example is of more porous structure the latter
condition being more conductive to penetration of reagents into the
fiber mass. Thus, with reference to human hair, for example, the
term "damaged" within the context of the present invention would
connote, for example, bleached hair, permanently waved hair, etc.
This, it is invariably found that the adaptability of a given hair
sample to the processes herein described can be enhanced, for
example, by subjecting the sample to one or more preliminary
bleaching treatments with plural treatments usually leading to more
favorable results. This situation is illustrated by reference to
the following examples which summarize results obtained in
connection with the grafting of methyl methacrylate to bleached
hair. In each instance reduction of the hair sample is carried out
for a period of 10 minutes utilizing a reducing solution comprising
5 percent sodium bisulfite in an ethanol (45 percent)-- water mixed
solvent system. The reducing solution is employed in volumes
approximating 10 ml. per gram of hair sample. Oxidizing solution
treatment is carried out for a period of 30 minutes at room
temperature utilizing 20 ml. of oxidizing solution per gram of hair
sample. ##SPC9##
As will be noted, hair subjected to but a single preliminary
bleaching treatment exhibits a 50 percent increase in amount of
polymer grafted as compared to a control, nonbleached hair sample.
Moreover, further improvement in percent grafting values obtain as
the number of preliminary bleaching treatments is increased.
Similar increases in polymer grafting are noted to obtain when the
aforedescribed treatment is repeated employing hair samples which
have been subjected to permanent waving. In examples 51 to 53, the
procedure observed is as follows: In each instance reduction is
carried out employing a 5 percent solution of sodium bisulfite in
an ethanol (45 percent)-- water system, reduction being continued
for a period of 20 minutes. Approximately 10 ml. of reducing
solution are employed per gram of hair sample. After rinsing, the
oxidation step is effected for approximately 30 minutes at room
temperature utilizing 20 ml. of monomer solution per gram of hair.
The results obtained are summarized in the following table:
##SPC10##
As the foregoing data makes abundantly clear, significant increases
in amount of polymer grafting are achieved in connection with the
treatment of permanently waved hair an approximate eight-fold
increase noted in the ease of but a single preliminary bleaching
treatment. As previously pointed out, the polymer grafting rates
would appear to be attributable to the increased porosity
characterizing predamaged hair.
In each of the following examples, human hair is treated with the
composition itemized in the following table the data signifying
parts by weight for 30 minutes at room temperature each of the hair
samples having been previously reduced with 6 percent
thioglycollate solution having a pH of about 9.
---------------------------------------------------------------------------
TABLE 7
Example No. 54 55 56 57 58 59
__________________________________________________________________________
Cumene hydro- peroxide 3 3 3 3 3 3 ethyl alcohol 30 18 26 47 -- 28
acetone -- -- -- -- 60 -- water 42 30 21 73 25 25 calcium acrylate
5 -- -- -- -- -- acrylonitrile -- 5 -- -- -- -- butyl acrylate --
-- 5 -- -- -- 5-butyl acrylamide -- -- -- 5 -- --
hexafluoroisopropyl acrylate -- -- -- -- 5 -- allyl methacrylate --
-- -- -- -- 5 Am't grafted polymer (%) 15.9 11.5 18.4 16.2 11.7
13.3
__________________________________________________________________________
Examples 46 to 59 follow the general, multistep process of examples
1 to 16 and the like.
In each case, the amount of polymer grafted to the hair fibers
compares favorably with the values described in the previous
example. In addition, the results obtained would tend to establish
the relative superiority of the organo-soluble initiators, those of
the water soluble type being somewhat less conducive to highly
accelerated polymer grafting rates.
As previously mentioned, the use of water soluble halide salt in
the monomer solution may be advantageous. This is demonstrated in
the following examples wherein human hair, each sample weighing
1.+-. 0.003 is used. In each instance the hair sample is subjected
to a reduction treatment for a period of 15 minutes utilizing an
aqueous solution of ammonium thioglycollate (6 percent) having a pH
of 9. Upon completion of the reduction treatment, the hair sample
is rinsed thoroughly so as to remove residual reducing agent.
Thereafter, the reduced hair sample is treated with a monomer
solution of specified composition for a period of one hour at a
temperature of 105.degree. F. Approximately 27 ml. of monomer
solution is employed per gram of hair treated. The amount of
grafted polymer is calculated as the percent dry weight increase
after drying for 12 hours over calcium chloride in a dry box. The
results obtained are summarized in table 8. ##SPC11##
Results similar to those described above are obtained when the
procedure described is repeated but employing in lieu of cumene
hydroperoxide, such material as di-butyl peroxide, t-butyl
hydroperoxide, benzoyl peroxide, peracetic acid, and hydrogen
peroxide. As previously mentioned, the use of certain of the
aforementioned initiators proved particularly advantageous in view
of superior stability, ease of handling, etc. In place of potassium
persulfate similar results are forthcoming using sodium persulfate,
ammonium persulfate, and persulfuric acid. In any event, it should
be noted the initiator material selected for use may be any of
those conventionally employed in the free radical-induced
polymerization of vinyl-type monomers. It will be understood, of
course, that specific monomer compounds may well lend themselves to
more effective use with but delimited types of initiator compounds.
In any event, such considerations can be readily resolved by the
practitioner in a particular circumstance whereby to determine
optimum modes of proceeding.
Moreover, the employment of keratin substances other than human
hair leads to similar results and particularly with the use of
wool, synthetic keratin fibers and animal hair. The process of the
present invention proves singularly adaptable for use in connection
with the latter-mentioned materials since a wide variety of
modification treatments are possible whereby to effect changes in
dyereceptivity, feel, etc. Thus, one or more of a wide variety of
properties of keratinous substrates can be effectively modified by
the process described herein. Thus, investigation indicates that
the equilibrium moisture content of the keratin material selected
for treatment can be altered by correspondingly controlling the
amount of polymer grafted thereto. In general, it has been
ascertained that the percent of water vapor taken up by
polymer-grafter hair, e.g., polymethyl methacrylate, is decreased
by an amount which is approximately equal to the percent grafted
polymer.
EXAMPLE 66
This examples illustrates the use of ammonium persulfate in the
multistep treating procedure.
A one gram sample of DM-36 hair is reduced for 3 minutes with 20
ml. of a 6 percent aqueous ammonium thioglycollate solution (pH =
9). The hair is then rinsed thoroughly with water and then treated
with 20 ml. for one hour at 75.degree. F. of a solution which
consists of:
6g. itaconic acid
4g. ammonium persulfate
10 ml. ethanol
to 100 ml. with deionized water
The treated hair exhibits substantially the same properties as
described above in the foregoing examples.
* * * * *