Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
  • A61K8/463—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfuric acid derivatives, e.g. sodium lauryl sulfate
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
  • D06M14/02—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin
  • D06M14/06—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin of animal origin, e.g. wool or silk
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
  • D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
  • D06M14/20—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of natural origin
  • D06M14/24—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of natural origin of animal origin, e.g. wool or silk
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
  • Y10S8/18—Grafting textile fibers

Definitions

• the present invention relates in general to the treatment of keratin-containing substrates and in particular to the provision of a novel process whereby to effectively modify the properties of keratinous material such as typified by wool, hair and the like.
• 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.
• many of the hair-treating processes heretofore promulgated invariably yield a hair product deficient in the desirable level of body, thickness, lustre, etc.
• 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.
• the particular requirements of a given hair-conditioning treatment may vary considerably, 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, dyereceptivity, thickness, etc.
• keratinous substrates such as wool, hair, and the like may be synergistically modified in accordance with predetermined requirements, via a process involving a particular chronology of operations as well as the employment of relatively specific compositions in conjunction therewith.
• the primary object of the present invention resides in the provision of a process for the treatment of keratinous substances, said process providing effective mcans whereby to permit selective 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 sub strates, whereby to enhance or otherwise augment the affinity of same for one or more dyestuff materials.
• a still further object of the present invention resides in the provision of a process for the modification of keratin-containing substrates, said process having exceptional utility in connection with the treatment of fibrous materials constituted wholly or partly of wool, whereby to render same more resistant against the debilitating and degradative effects attributable to such influences as moisture, heat, soil, etc.
• a process for the modification of a keratinous substrate comprising l treating a keratin-containing substrate with a reducing agent capable of reducing disulfide to sulfliydryl, 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:
• 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.
• 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.
• the predominant portion of vinyl monomer polymerization initia tion as well as propagation is confined to the reduction sites present in the keratinous substrate. in this manner, the resultant polymer, which is grafted to the hair or wool fiber, whatever the case may be, is actually integral, both in a chemical and a physical sense, with such fiber.
• the keratin substrate remains substantially unaffected at least in a chemical sense by the reducing solution, the keratin serving primarily as a carrier.
• 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.
• 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.
• 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.
• 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.
• the reducing agent when applied will tend to permeate the total volume occupied by the keratin substrate.
• 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.
• any of the reducing agents compounds conventionally employed in the art for the treatment of keratinous substrates may be employed to advantage in 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.
• 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.
• the subject invention makes further possible the realization of increased polymer takeup when compared to prior art methods.
• manifold increases in the amount of polymer which can be grafted to the keratinous substrate in reduced periods of time can be readily obtained.
• 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.
• the keratin treatment process may be carried out under reduced temperature conditions, ie, temperatures approximating only 6575 F.
• the sequence of operations comprising the instant 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.
• 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.
• the keratinous substrate is 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.
• the keratin substrate in the process of the present invention provides a twofold function, viz. (l) the reducing agent and (2) the material to be modified.
• the process of the subject invention consists of essentially three basic operations performed successively which can be characterized as l reduction, (2) rinsing and (3) oxidation. ln order to expedite comprehension of these vital aspects of the subject invention each will now be discussed in greater detaii.
• REDUCTlON 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.
• 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 bisulflte, ammonium bisulftte, etc.; water soluble salts of thioglycerol; trihydroxymethyl phosphinethe latter material can also be generated in situ from tetra-kis-hydroxymethyl phosphonium chloride and the like. As indicated previously, strong reducing agents are preferred.
• 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, nbutanol, ethylene glycol, 1, 2-propylene glycol, etc.; etherglycols, 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.
• the lower alkanols such as typified by ethyl alcohol provide particular advantage for use in the present invention.
• 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 to about 45 percent being particularly preferred.
• 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.
• water soluble salts of thioglycollic acid e.g., ammonium thioglycollate
• concentrations approximating 6 percent by weight of solution whereby to yield a pH of approximately 9.
• 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.
• the duration of the reduction treatment 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.
• wetting agents may be incorporated for purposes of reducing the surface tension extant 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.
• 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.
• 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.
• the primary purpose of the rinsing treatment is to eliminate or minimize any possibility of polymerization occurring 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.
• the third step in the sequence of operations prescribed in accordance with 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 particularly critical apart from the obvious requirement that the polymeric material yielded thereby be innocuous towards the total environment comprising the keratin substrate having reference to, for example, human skin as would be the case with onscalp applications to human hair, fabrics, in the case of wool, etc.
• the monomer component 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.
• the monomer materials preferred for use herein comprise those containing at least one grouping of the formula:
• R represents hydrogen, lower alkyl of one to four carbon atoms, e.g., methyl, ethyl, propyl, butyl, isobutyl, etc.
• R represents (a) carbalkoxy, i.e., COOR
• R 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- dihydroxy propyl, 2,4,dihydroxybutyl, 4,6-
• R and R represent hydrogen, alkyl and preferably lower alkyl or alternatively may represent the atoms necessary to complete a polyunsaturated molecule such as:
• the aforementioned monomer materials may also be provided in the form of their salified derivatives, e.g., salts with water-solubilizing cations.
• the oxidizing solution of the present invention further contains as a critical ingredient a free radical liberating peroxide initiator material capable of initiating the polymerization of vinyl monomer in the presence of reducing agent, i.e., mercaptan.
• 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.
• 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 peracids, such as peracetic acid, perbenzoic acid, persulfuric acid, etc.
• 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 watersoluble 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 or alternatively, mixed solvent systems, the nature and proportion of the solvent materials employed depending upon the solubility characteristics typifying the monomer and catalyst components.
• the solvent medium 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.
• a water miscible organic solvent such as a lower alkanol, e.g., ethanol, n-propanol, isopropanol, n-butanol, etc., acetone and the like.
• substantially hydrophobic monomer materials 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.
• hydrophilic monomer component dictates correspondingly the use of increased quantities of water.
• 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.
• the proportions of monomer and catalyst employed in preparing the oxidizing solution are not critical factors in the.
• 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 polymerization reaction rate.
• 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.
• the oxidizing solution may comprise simply the monomer and catalyst.
• the monomer material may be employed in concentrations ranging from as little as l 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 of 1:8 to 1:2
• 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.
• 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.
• one of the important aspects of the present invention resides in the fact that beneficial results may be obtained when carrying the oxidizing treatment out under room temperature conditions.
• 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.
• the relatively mild temperatures characterizing the process described herein involves little or no risk of damage to the keratinous material selected for treatment.
• the process 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.
• keratin substrates are characterized among the proteins as containing copious quantities of chemically combined sulfur, the latter being present in the protein molecule in disulfide form also referred to as cystine linkages.
• the keratin molecule contains amino acids linked through amide groups to form long chain structures known as polypeptides, the latter in turn being mutually interconnected through disultide linkages.
• treatment of such material with reducing agent results in the conversion of the disulfide linkage, i.e., the SS bond into two thiol groups each attached to a polypeptide chain.
• Ksh+RO-O-H R +K-S +H O wherein K represents polypeptide chains and R represents an organic moiety, which may be aryl or aliphatic, e.g., tertiary butyl.
• grafting is induced by free radical species formed in situ with the keratinous mass.
• the polymer formed by the action of RO' radicals may also be grafted by termination reactions onto the functional groups present in the keratin substance.
• the polymerization of vinyl monomers can, of course, be effected by means of an addition reaction through the double bond present in the monomer molecule.
• Polymerization initiation can be readily achieved by merely adding effective amounts of a suitable initiator, i.e., polymerization catalyst, the latter being capable of liberating polymerization-initiating species under the conditions extant in the reaction medium.
• a suitable initiator i.e., polymerization catalyst
• R represents a free radical fragment formed by decomposition of the initiator
• M represents the vinyl monomer material
• Mn represents a polymeric chain carrying a live" or reactive end portion.
• the macroradical formed can be chilled, i.e., rendered nonreactive, by combination with another polymeric radical this mechanism being commonly referred to as combination-termination"; by oxido-reduction with a radical leading to the formation of a double bond at the end of the chain, this mechanism being referred to as disproportionation termination; by reaction with a solvent molecule (transfer to the monomer); by reaction with a solvent molecule (transfer to the solvent) or by reaction with another added substance which contains labile hydrogen atoms, e.g., amines, mercaptans, alcohols, etc., the latter materials being well known as chain regulators.
• the peroxide catalyst material in the presence of mercaptan and under the conditions of treatment liberates polymerization-initiating, free radical species on the keratinous mass, e.g., fiber, the free radicals thus generated in situ in turn reacting with monomer thereby initiating the polymer-forming reaction.
• Preferential internal polymerization occurs since initiator and monomer are consumed as soon as they penetrate the keratinous mass.
• initiation step is an exothermic reaction graft polymerization can be readily achieved at or below room temperature.
• reducing agent an initiating agency, i.e., reducing agent, polymerization occurs within rather than without the keratinous mass.
• the oxidizing treatment is thereupon carried out utilizing a solution consisting of methyl methacrylate monomer (12.0 percent), cumene hydroperoxide catalyst (50 percent), and ethyl alcohol (4L0 percent) with the balance water.
• a solution consisting of methyl methacrylate monomer (12.0 percent), cumene hydroperoxide catalyst (50 percent), and ethyl alcohol (4L0 percent) with the balance water.
• 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.
• a reducing solution comprising 5 percent sodium bisulfite in an ethylene glycol monomethyl ether (69 percent)water mixture suffers considerably by comparison.
• the discrepancy in effectiveness is probably due to the fact that the ethylene glycol monomethyl ether comprises an inferior precipitant.
• the solution employed in this particular instance is not saturated. Accordingly, as the foregoing data suggests, more favorable grafting rates attend the use of reducing solutions wherein the concentration of reducing agent approximates the saturation point while employing solvent materials which function as satisfactory precipitants.
• the data summarized in connection with the ammonium thioglycollate reducing solution makes abundantly clear that increased grafting rates are obtainable with the use of reducing agents of the high-strength type.
• the thioglycollates possess a relatively highreducing power as compared to bisulfite materials.
• manifold increases in polymer grafting rates may be obtained simply by judicious selection of reducing agent. More specifically, for a reducing period of 10 minutes with an ammonium thioglycollate solution, 22.26 percent by weight of polymer is grafted to the hair sample as compared to polymer-grafting values of 5.0 percent and 3.47 percent respectively in the case of t ea rqi rtwit k s
• increasing the period of oxidizing solution treatment gives rise to corresponding incremental increases in the amount of polymer grafted. This situation is illustrated by reference to the following examples which summarize the results obtained in connection with the treatment of human hair with methyl methacrylate.
• the reduction treatment is carried out employing a 6 percent solution of ammonium thioglycollate having a pH of 9, the period of treatment being 10 minutes.
• the reducing solution is employed in volumes approximating 20 ml. per gram of hair sample being treated.
• the hair sample is thoroughly rinsed in order to completely remove residual reducing solution.
• oxidizing solution treatment is carried out at room temperature for a period of minutes employing 20 ml. of oxidizing solution per gram of hair sample. The results obtained are itemized in table 2.
• a sixfold increase in time of grafting i.e., from 5 to 30 minutes leads to an approximate eightfold increase in amount of polymer grafted.
• significant amounts of polymer are effectively grafted to the hair sample under treatment despite the employment of moderate, room temperature conditions.
• 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.
• the rate of polymer grafting will correspondingly decrease.
• 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.
• the solvent employed for the experimental runs comprises ethyl alcohol with the balance waterv TABLE 5 Examples 3 l-34
• the relationship extant between concentration of organic solvent and corresponding polymerization rate depends critically upon the nature of the monomer material employed.
• a given monomer component may tolerate copious quantities of organic solvent in the absence of deleterious effects upon polymerization grafting rate.
• 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.
• the use of increased amounts of organic solvent may well be dictated as a particular means to accomplish same.
• keratinous materials 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.
• the term damaged within the context of the present invention would connote, for example, bleached hair, permanently waved hair, etc.
• the adaptability of a given hair sample to the process of the present invention 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.
• Both the cationic and anionic sorption properties of keratinous substrates can likewise be regulated in accordance with predetermined requirements by means of the present invention.
• suitable choice of monomer, controlling the amount of polymer grafted, etc. it is found that the selective sorption of keratinous substrates for either cationic or anionic reagents, e.g., dyestuffs, can be significantly modified.
• experimental studies relating to the sorption of hexadecyl pyridinium chloride (HDPC) at acidic, neutral and basic pH s have shown that it is possible to increase the amount of sorbed cationic by grafting, for example, polymethacrylic acid to the keratinous material.
• HDPC hexadecyl pyridinium chloride
• the hydrophobic polymer has the effect of retarding the penetration of cationics.
• the cationic sorption properties of the keratinous mass selected for treatment can be varied practically at will.
• the subject invention likewise described herein.
• the affinity for Orange 11 as well as the rate of uptake of this dyestuffs by grafted hair are much greater than that obtained with ungrafted hair, with the differences therebetween becoming less evident as the pH is increased.
• the amount of Orange ll dyestutf sorbed by polydimethylaminoethyl methacrylate grafted hair is approximately double the amount sorbed by untreated hair at pH of 3.5.
• 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.
• the amount of polymer grafted to the hair fibers compares favorably with the values described in the previous example.
• 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.
• results similar to those described above are obtained when the procedure described is repeated but employing in lieu of cumene hydroperoxide, such materials as di-butyl peroxide, tbutyl hydroperoxide, benzoyl peroxide, peracetic acid, and hydrogen peroxide.
• cumene hydroperoxide such materials as di-butyl peroxide, tbutyl hydroperoxide, benzoyl peroxide, peracetic acid, and hydrogen peroxide.
• the use of certain of the aforementioned initiators proves particularly advantageous in view of superior stability, ease of handling, etc.
• 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.
• 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 dye-receptivity, feel, etc.
• one or more of a wide variety of properties of keratinous substrates can be effectively modified by the process described herein.
• 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-grafted hair, e.g., polymethyl methacrylate, is decreased by an amount which is approximately equal to the percent grafted polymer.
• a process for the modification of a keratinous substrate which has just previously been subjected to chemical reduction thereby to convert disulfide to mercaptan and thereafter rinsed to remove reducing agent which comprises treating the same with an effective amount of an oxidizing solution comprising (a) a peroxide initiator capable of liberating free radical species in the presence of mercaptan, said free radical species being capable of initiating the polymerization of vinyl monomers and (b) a vinyl monomer compound containing at least one grouping of the formula said monomer undergoing polymerization in the presence of said peroxide initiator.
• a process for the modification of a keratin material which comprises l treating a keratinous substrate with an effective amount of a chemical reducing agent to reduce disulfide linkages present in said substrate to mercaptan (2) removing residual reducing agent froni said substrate and (3) thereafter treating said reduced substrate with an effective amount of an oxidizing solution comprising (a) a peroxide initiator material capable of liberating free radical species in the presence of mercaptan said free radical specie being capable of initiating the polymerization of vinyl monomer and b) a vinyl monomer compound containing at least one grouping of the formula:
• R is selected form the group consisting of hydrogen and lower alkyl and R is selected from the group consisting of a. carbalkoxy of the formula COOR wherein R, is selected from the group consisting of hydrogen, alkyl containing from one to 20 carbon atoms, alkenyl containing from three to 10 carbon atoms, hydroxy-alkyl containing from two to 10 carbon atoms, halo-alkyl containing from one to 10 carbon atoms, vicinal epoxy-alkyl containing from three to six carbon atoms and alkyl and dialkylaminoalkyl said alkyl containing from one to four carbon atoms and b.
• amido of the following structural formula a CON R4 Hr wherein R and R are independently selected from the group consisting of hydrogen, lower alkyl or together represent the atoms necessary to complete a grouping of the formula wherein R represents lower alkylene c. halogen d. alkoxy e. cyano and f. alkenyl aryl said alkenyl containing from one to four carbon atoms.
• a process according to claim 10 wherein said monomer is methyl methacrylate.
• a process according to claim 10 wherein said monomer is calcium methacrylate.

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• 1969
  • 1969-05-29 US US829097A patent/US3633591A/en not_active Expired - Lifetime
  • 1969-05-29 US US829096A patent/US3676550A/en not_active Expired - Lifetime
• 1970
  • 1970-05-25 DE DE2025454A patent/DE2025454C2/de not_active Expired
  • 1970-05-25 FR FR7018913A patent/FR2043768B1/fr not_active Expired
  • 1970-05-26 GB GB2520570A patent/GB1311902A/en not_active Expired
  • 1970-05-26 GB GB5902772A patent/GB1318170A/en not_active Expired
  • 1970-05-27 CH CH788370A patent/CH546576A/de not_active IP Right Cessation
  • 1970-05-27 ES ES380121A patent/ES380121A1/es not_active Expired
  • 1970-05-28 NO NO2039/70A patent/NO132920C/no unknown
  • 1970-05-29 JP JP45045770A patent/JPS4925334B1/ja active Pending
  • 1970-05-29 CA CA084,162A patent/CA941302A/en not_active Expired
  • 1970-05-29 NL NL7007860.A patent/NL167321C/xx not_active IP Right Cessation
  • 1970-05-29 CA CA084,161A patent/CA941301A/en not_active Expired
  • 1970-05-29 BE BE751183D patent/BE751183A/xx not_active IP Right Cessation

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