US3634022A - Form-setting keratin substrates by a chemical treatment involving a vinyl monomer - Google Patents

Form-setting keratin substrates by a chemical treatment involving a vinyl monomer Download PDF

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US3634022A
US3634022A US829116A US3634022DA US3634022A US 3634022 A US3634022 A US 3634022A US 829116 A US829116 A US 829116A US 3634022D A US3634022D A US 3634022DA US 3634022 A US3634022 A US 3634022A
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hair
monomer
acid
water
percent
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Clarence R Robbins
Seymour Grey
George V Scott
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Colgate Palmolive Co
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Colgate Palmolive Co
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    • 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
    • A61Q5/04—Preparations for permanent waving or straightening 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
    • A61K8/72—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
    • A61K8/8147—Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/94—Involves covalent bonding to the substrate
    • 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 keratincontaining substrates and in particular to the provision ofa novel process to produce a desired physical configuration to the hair.
  • hair-conditioning methods of the aforedescribed type have nevertheless been found in practice to be intolerably deficient in one or more im portant 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.
  • compositions and techniques require that the hair be treated while in the desired physical configuration.
  • the use of curlers during chemical treatment steps of the hair is necessitated by the fact that the chemical treatment fixes the physical configuration.
  • 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.
  • the particular requirements ofa 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.
  • 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.
  • 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 ofsaid 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.
  • 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 sulficient 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 initiation as well as propagation is confined to the reduction sites present in the keratinous substrate.
  • 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.
  • the keratin substrate remains substantially unaffected at least in a chemical sense by the reducing solution, the keratin serving primarily as a carrier.
  • the catalysbcontaining 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 contain ing 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.
  • 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 pro vided herein will be made readily manifest by reference to the following discussion.
  • the reducing agents 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.
  • reducing agent buildup in such areas will. of course, depend upon several factors including the quantity of reducing solution employed, the conditions ofthc treatment, e.g.. time, temperature, etc.. condition ofthe keratin substrate. i.e.. degree of porosity, etc.
  • the polymer-forming reaction 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 ofthe 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.
  • 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 ofthe more active type.
  • High-strength reducing agents are preferred being more con ducive 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 sub strate reduction.
  • the aforedescribed process 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 may be carried out under reduced temperature conditions, i.e..
  • 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.
  • 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.
  • preliminary oxidation comprises a preferred embodiment.
  • the keratinous substrate in inert 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.
  • one of the processes of the sub ject 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.
  • I 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.
  • 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 bisultites, 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.
  • 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.; other glycols, e.g,, ethylene glycol monomethyl ether, etc.
  • water miscible organic solvents such as mono and polyhydroxy alcohols, e.g., methanol, ethanol, propanol, isopropanol, nbutanol, 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.
  • the lower alkanols such as typified by ethyl alcohol provide particular advantage for use in the present invention.
  • optimum realization of the ad' vantages 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 percent to about 45 percent being particularly preferred.
  • the reducing solution utilized be substantially saturated with reducing agent, experimental evidence establishing the obtention ofgreater 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 nine
  • Solutions ofthe 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 ofthe 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 red uction treatment be sufficient to yield the desired degree of disullide 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 extent at the boundary between the keratinous substrate and reducing solution whereby to promote penetration ofthe 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 ofthe entire treatment depends critically thereupon.
  • 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.
  • 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 ofthe 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.
  • 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., CODR
  • 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 l carbon atoms, e.g,, allyl, 3,4-butenyl, 2,3-butenyl, 5,6-hexenyl, 2,3-hexenyl, etc.; hydroxyalkyl containing from two to ID carbon atoms, e.g., Z-hydroxypropyl, 3-hydroxypropyl, Z-hydroxybutyl, 2,3- dihydroxypropyl, 2,4dihydroxybutyl,
  • R and R represent hydrogen, alkyl and preferably lower alkyl or alternatively may represent the atoms necessary to complete a polyunsaturated molecule such as:
  • R 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 CN, (f) alkenyl aryl, said alkenyl containing from one to four carbon atoms to, lower alkenyl e.g., o,m and p CII CH: etc,
  • the aforementioned monomer materials may also be provided in the form of their salified derivatives, e.g., salts with water solubilizing cations.
  • the monomer material prior to use may be converted to a suitable salified form such as typified by calcium acrylate, i.e., (CH -CHCOO ),Ca, sodium acrylate, potassium acrylate, calcium methacrylate, and the like,
  • 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.
  • 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 oforganic hydroperoxides, alkali metal salts of per-acids, such as peracetic acid, perbenzoic acid, persulfuric acid, etc.
  • the initiator and monomer materials may be formulated utilizing simple aqueous solutions alternatively mixed solvent :vstems, ti. nature and proportion of the solvent materials I t rye-l depending upon the solubility characteristics typify- .lg the monomer and catalyst components.
  • the sol- Vctll madium employed should comprise from about 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.
  • the selection of particular amounts oforganic solvent will depend, inter alia, upon the relative hydrophobicity of the monomer component.
  • 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 ofsolvent 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 oxidizing solution may likewise be provided in the form of a suitable dispersion, suspension, emulsion, or the like de pending upon the solubility characteristics of the monomer employed.
  • a suitable dispersion, suspension, emulsion, or the like de pending upon the solubility characteristics of the monomer employed.
  • suitable suspending agents, emulsifying agents, etc. the particular adjuvants effective for such purposes being well known in the art.
  • 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.
  • 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.
  • 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 0.00l to l to about 5:] with a range 1:8 to l: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.
  • 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 aforedescribed process 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.
  • Another suitable process is a one-step process which involves treating the keratin substrate with a composition comprising 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
  • said monomer being capable of undergoing polymerization in the presence ofsaid 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.
  • persulfuric acid As specific examples of compounds found to function to exceptional ad vantage in the practice of the present invention there may be mentioned, persulfuric acid, disodium persulfate, dipotassium persulfate and ammonium persulfate.
  • 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.
  • 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.
  • 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.
  • the pH of the reaction may vary from about 1 to about ll 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 BIC.
  • 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.
  • the aforementioned bromides and chlorides are uniquely characterized in their exceptional capacity to augment to a considerable extent the graft copolymerization rate obtainable.
  • 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.
  • the reduction treatment is effected utilizing a 6 percent solution of ammonium thioglycollate having a pH of 9, the period oftreatment being l0 minutes.
  • the keratinous substrate selected for treatment comprises samples of human hair.
  • 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 30 minutes employing 20 ml. of oxidizing solution per gram of hair sample. The results obtained are itemized in table 2,
  • 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.
  • 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.
  • the solvent employed for the experimental runs comprises ethyl alcohol with the balance water.
  • suitable relaxing agents which have been found use ful 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-l-hydroxy l,ldispl
  • 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.
  • Ml./ ML/ cumene Tresses 3 to 6 are treated for l hour and 7 and 8 for 30 minutes, all at 75 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.
  • a sample of human hair is treated for a period of one hour at l06 F. with a solution of the following composition:
  • 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.
  • the amount of polymethyl methacrylate grafter to the hair sample is calculated by difference of 10.78 percent.
  • 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:
  • hydrochloride acid 25 parts hydrochloric acid 5 parts methyl methacrylate 5 parts methyl alcohol 45 parts water parts
  • the amount of polymetbyl methacrylate grafted is calcu- 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.
  • EXAM PLE 43 The eight tresses of example 33 are resoaked in water to remove the wave and then rewaved on glass rods at 60 percent RiH. The percent wave retention at 85 percent RF]. is as follows:
  • Tresses Alter lhoursl l and 2 3 and 4 5 and b 7 and it EXAMPLE 44
  • the eight tresses of example 43 are shampooed with l 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 RH. for 24 hours and
  • 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 RH. They are then exposed for 24 hours to 85 percent RH. and the percent wave retention measured.
  • the figures appear in the table below.
  • 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.
  • 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.
  • the polymer grafting rates would appear to be attributable to the increased porosity characterizing predamaged hair.
  • 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 ofabout 9.
  • Examples 46 to 59 follow the general, multistep process of examples 1 to lband the like.
  • 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.
  • 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 l1-0.003 is used. In each instance the hair sample is subjected to a reduction treatment for a period of IS 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 ofone hour at a temperature of I 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 l2 hours over calcium chloride in a dry box. The results obtained are summarized in table 8.
  • the initiator material selected for use may be any of those conventionally employed in the free radical-induced polymerization of vinyltype 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,
  • EXAMPLE 66 This examples illustrates the use ofammonium persulfate in the multistep treating procedure.
  • 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 physi cal configuration each time the hair is wetted and dried.
  • a method as defined in claim 1 wherein said monomer is methyl methacrylatev 4.
  • a method as defined in claim 1 wherein said initiator is cumene hydroperoxide.
  • a method as defined in claim 1 including treating said hair with a multivalent Group "A cation after removal of unreacted monomer and initiator.
  • 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-l-hydroxy-l,l-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.
  • a relaxing agent selected from the group consisting of salts of citric acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, phytic acid, ethane-l-hydroxy-l,l-diphosphonic acid, ethylene diphosphonic acid, polymers of itaconic acid, aconitic acid, maleic acid, methylene malonic acid, merconic acid and citraconic acid with a
  • agent is a water-soluble citrate.
  • 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.
  • a method as defined in claim medium is water.
  • said solvent medium consists of from about [0 to about percent by weight water, the remainder comprising water-miscible or ganic solvent.
  • a method as defined in claim I 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 oflithium, sodium, potassium or ammonium.
  • halide salt is lithium bromide, lithium chloride, sodium bromide, sodium chloride, potassium bromide, potassium chloride, ammonium bromide or ammonium chloride.
  • a method as defined in claim is lithium bromide.

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US4901389A (en) * 1987-04-14 1990-02-20 Institut Textile De France Grafting process, ensuring waterproofing, of a polymeric material by a fluorinated monomer and material obtained thereby
US5362486A (en) * 1992-04-10 1994-11-08 Helene Curtis, Inc. In-situ polymerization of oligomers onto hair
FR2833489A1 (fr) * 2001-12-18 2003-06-20 Oreal Utilisation pour le traitement des cheveux de monomeres electrophiles
US20040156800A1 (en) * 2002-11-07 2004-08-12 Gaelle Brun Cosmetic composition comprising at least one cyclic carbonate
US20060078523A1 (en) * 2004-10-13 2006-04-13 Gabin Vic Composition comprising at least one electrophilic monomer and at least one acid in a cosmetically acceptable anhydrous medium, and use thereof for cosmetic treatment of the hair
US20060078522A1 (en) * 2004-10-13 2006-04-13 Gabin Vic Composition for treating keratin materials comprising at least one electrophilic monomer and at least one salt
FR2876282A1 (fr) * 2004-10-13 2006-04-14 Oreal Composition oxydante comprenant un monomere electrophile et un agent oxydant autre que la benzoquinone
EP1647308A1 (fr) * 2004-10-13 2006-04-19 L'oreal Utilisation d'une composition à base de monomères électrophiles et de micro- ou nanoparticules
EP1647261A1 (fr) * 2004-10-13 2006-04-19 L'oreal Composition pour le traitement des matières kératiniques à base de monomères électrophiles et de sels
EP1647263A1 (fr) * 2004-10-13 2006-04-19 L'oreal Dispositif aérosol à deux compartiments comprenant des monomères électrophiles et utilisation pour le traitement cosmétique des cheveux
EP1647265A1 (fr) * 2004-10-13 2006-04-19 L'oreal Utilisation pour le traitement cosmétique des matières kératiniques de compositions non collantes à base de monomères électrophiles et de polymères non siliconés
US20060083762A1 (en) * 2004-10-13 2006-04-20 Gaelle Brun Uses of compositions comprising electrophilic monomers and micro-particles or nanoparticles
US20060085922A1 (en) * 2004-10-13 2006-04-27 Gregory Plos Oxidizing composition comprising at least one electrophilic monomer and at least one non-benzoquinone oxidant
US20060088493A1 (en) * 2004-10-13 2006-04-27 Gabin Vic Composition and process for the cosmetic treatment of keratin materials based on electrophilic monomers and non-silicone polymers
EP1707241A1 (fr) * 2005-03-31 2006-10-04 L'oreal Composition comprenant un monomère électrophile et un acide aminé différent de la cystéine et traitement cosmétique
US20060233731A1 (en) * 2004-10-13 2006-10-19 Gabin Vic Use, for the cosmetic treatment of keratin materials, of a film-forming composition comprising an electrophilic monomer and a non-silicone polymer, conferring a soft coating
US20060263315A1 (en) * 2005-03-31 2006-11-23 Gregory Plos Composition comprising an electrophilic monomer and an amino acid other than cysteine, and cosmetic treatment processes
EP1844755A1 (fr) * 2006-04-13 2007-10-17 L'Oréal Composition cosmétique comprenant au moins un monomère dielectrophile et un amorceur radicalaire
FR2899812A1 (fr) * 2006-04-13 2007-10-19 Oreal Composition comprenant un monomere cyanoacrylate, un compose glucidique et un solvant organique liquide et procedes de traitement cosmetique
US20070253927A1 (en) * 2006-04-13 2007-11-01 Gwenaelle Jegou Cosmetic compositions comprising at least one dielectrophile monomer and at least one radical initiator
US20080066773A1 (en) * 2006-04-21 2008-03-20 Anderson Daniel G In situ polymerization for hair treatment
US20080187506A1 (en) * 2007-02-05 2008-08-07 Jose Antonio Carballada Hair care composition
US20090022681A1 (en) * 2007-02-05 2009-01-22 Jose Antonio Carballada Hair Care Composition
US20090104136A1 (en) * 2007-10-22 2009-04-23 Daniel Griffith Anderson Hair care compositions and methods of treating hair using same
US20090193595A1 (en) * 2004-10-13 2009-08-06 L'oreal S.A. Coloring composition comprising at least one pigment and at least one electrophilic cyanoacrylate monomer
US20100028279A1 (en) * 2008-07-31 2010-02-04 Jose Antonio Carballada Method and Composition for Maintaining Hair Dye Color
US20100028286A1 (en) * 2008-07-31 2010-02-04 Jose Antonio Carballada Method and Composition for Stabilizing Hair Moisture Levels
US20100120871A1 (en) * 2008-11-10 2010-05-13 Dawson Jr Thomas Larry Hair care compositions, methods, and articles of commerce that can increase the appearance of thicker and fuller hair
US20100278769A1 (en) * 2007-10-22 2010-11-04 Living Proof, Inc. Hair care compositions and methods of treating hair
EP2295029A1 (en) * 2009-09-14 2011-03-16 The Procter & Gamble Company Method of chemically modifying the internal region of a hair shaft
EP2772246A1 (en) * 2013-03-01 2014-09-03 The Procter and Gamble Company Acidic composition for modifying the internal region of a hair shaft
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WO2016075498A1 (en) * 2015-02-27 2016-05-19 Revolymer (U.K.) Limited Polymers of itaconic acid and uses thereof as a film forming agent in a cosmetic or personal care product
US9358197B2 (en) 2012-06-15 2016-06-07 The Procter & Gamble Company Method employing polyols when chemically modifying the internal region of a hair shaft
WO2016177344A1 (zh) * 2015-05-07 2016-11-10 知识产权全资有限公司 含有单体的染发混合物
US9986809B2 (en) 2013-06-28 2018-06-05 The Procter & Gamble Company Aerosol hairspray product comprising a spraying device
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US10251826B2 (en) * 2016-11-24 2019-04-09 Henkel Ag & Co. Kgaa Alkaline agent for lightening hair containing oxidants and special carboxylic acid esters
JP2021503469A (ja) * 2017-11-17 2021-02-12 リビング プルーフ インコーポレイテッド ケラチン含有物質の共有結合処理
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US12128118B2 (en) 2021-07-29 2024-10-29 The Procter & Gamble Company Aerosol dispenser containing a hairspray composition and a nitrogen propellant

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US3972336A (en) * 1974-03-14 1976-08-03 National Starch And Chemical Corporation Hair fixatives based on sulfonated styrene polymers
US4166473A (en) * 1974-06-10 1979-09-04 L'oreal Method and apparatus for setting hair
US4369037A (en) * 1980-11-19 1983-01-18 Kao Soap Co., Ltd. Hair treatment cosmetics containing cationic keratin derivatives
US4861583A (en) * 1986-09-04 1989-08-29 S. C. Johnson & Son, Inc. Hot curling hair treatment
US4901389A (en) * 1987-04-14 1990-02-20 Institut Textile De France Grafting process, ensuring waterproofing, of a polymeric material by a fluorinated monomer and material obtained thereby
US5362486A (en) * 1992-04-10 1994-11-08 Helene Curtis, Inc. In-situ polymerization of oligomers onto hair
FR2833489A1 (fr) * 2001-12-18 2003-06-20 Oreal Utilisation pour le traitement des cheveux de monomeres electrophiles
US20030175229A1 (en) * 2001-12-18 2003-09-18 L'oreal Electrophilic monomers for treating the hair
WO2003053380A3 (fr) * 2001-12-18 2004-01-22 Oreal Utilisation pour le traitement des cheveux de monomeres electrophiles
US7357921B2 (en) 2001-12-18 2008-04-15 L'oreal Electrophilic monomers for treating the hair
US20040156800A1 (en) * 2002-11-07 2004-08-12 Gaelle Brun Cosmetic composition comprising at least one cyclic carbonate
JP2006518330A (ja) * 2002-11-07 2006-08-10 ロレアル 重合されてもよい少なくとも１種の特定の環状カーボネートを含む化粧品組成物
US20060085922A1 (en) * 2004-10-13 2006-04-27 Gregory Plos Oxidizing composition comprising at least one electrophilic monomer and at least one non-benzoquinone oxidant
EP1647308A1 (fr) * 2004-10-13 2006-04-19 L'oreal Utilisation d'une composition à base de monomères électrophiles et de micro- ou nanoparticules
EP1647261A1 (fr) * 2004-10-13 2006-04-19 L'oreal Composition pour le traitement des matières kératiniques à base de monomères électrophiles et de sels
EP1647263A1 (fr) * 2004-10-13 2006-04-19 L'oreal Dispositif aérosol à deux compartiments comprenant des monomères électrophiles et utilisation pour le traitement cosmétique des cheveux
EP1647265A1 (fr) * 2004-10-13 2006-04-19 L'oreal Utilisation pour le traitement cosmétique des matières kératiniques de compositions non collantes à base de monomères électrophiles et de polymères non siliconés
US20060083762A1 (en) * 2004-10-13 2006-04-20 Gaelle Brun Uses of compositions comprising electrophilic monomers and micro-particles or nanoparticles
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US20060088493A1 (en) * 2004-10-13 2006-04-27 Gabin Vic Composition and process for the cosmetic treatment of keratin materials based on electrophilic monomers and non-silicone polymers
US20060078522A1 (en) * 2004-10-13 2006-04-13 Gabin Vic Composition for treating keratin materials comprising at least one electrophilic monomer and at least one salt
US7682405B2 (en) 2004-10-13 2010-03-23 L'oreal S.A. Coloring composition comprising at least one pigment and at least one electrophilic cyanoacrylate monomer
EP1649895A3 (fr) * 2004-10-13 2009-07-01 L'oreal Composition oxydante comprenant un monomere électrophile et un agent oxydant autre que la benzoquinone
US20060233731A1 (en) * 2004-10-13 2006-10-19 Gabin Vic Use, for the cosmetic treatment of keratin materials, of a film-forming composition comprising an electrophilic monomer and a non-silicone polymer, conferring a soft coating
US20090193595A1 (en) * 2004-10-13 2009-08-06 L'oreal S.A. Coloring composition comprising at least one pigment and at least one electrophilic cyanoacrylate monomer
US20060078523A1 (en) * 2004-10-13 2006-04-13 Gabin Vic Composition comprising at least one electrophilic monomer and at least one acid in a cosmetically acceptable anhydrous medium, and use thereof for cosmetic treatment of the hair
US20060263315A1 (en) * 2005-03-31 2006-11-23 Gregory Plos Composition comprising an electrophilic monomer and an amino acid other than cysteine, and cosmetic treatment processes
FR2883742A1 (fr) * 2005-03-31 2006-10-06 Oreal Composition comprenant un monomere electrophyle et un acide amine different de la cysteine et procedes de traitement cosmetique
EP1707241A1 (fr) * 2005-03-31 2006-10-04 L'oreal Composition comprenant un monomère électrophile et un acide aminé différent de la cystéine et traitement cosmétique
EP1844755A1 (fr) * 2006-04-13 2007-10-17 L'Oréal Composition cosmétique comprenant au moins un monomère dielectrophile et un amorceur radicalaire
US20070253927A1 (en) * 2006-04-13 2007-11-01 Gwenaelle Jegou Cosmetic compositions comprising at least one dielectrophile monomer and at least one radical initiator
FR2899808A1 (fr) * 2006-04-13 2007-10-19 Oreal Composition cosmeyique comprenant au moins un monomere dielectrophile et un amorceur radicalaire
EP1847252A3 (fr) * 2006-04-13 2009-12-02 L'Oréal Composition comprenant un monomère cyanoacrylate, un composé glucidique et un solvant organique liquide et procédés de traitement cosmétique
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US20080066773A1 (en) * 2006-04-21 2008-03-20 Anderson Daniel G In situ polymerization for hair treatment
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US9358197B2 (en) 2012-06-15 2016-06-07 The Procter & Gamble Company Method employing polyols when chemically modifying the internal region of a hair shaft
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Also Published As

Publication number Publication date
DE2025452A1 (de) 1971-01-28
ZA702931B (en) 1971-12-29
NL167320B (nl) 1981-07-16
NL167320C (nl) 1981-12-16
DE2025452B2 (de) 1979-03-22
IT1013005B (it) 1977-03-30
PH11259A (en) 1977-11-02
ES379573A1 (es) 1972-10-16
CH547908A (de) 1974-04-11
DK129023B (da) 1974-08-12
FR2043767B1 (enrdf_load_stackoverflow) 1975-09-26
BR7019291D0 (pt) 1973-05-17
GB1321331A (en) 1973-06-27
FR2043767A1 (enrdf_load_stackoverflow) 1971-02-19
NO134184C (enrdf_load_stackoverflow) 1976-09-01
CA958336A (en) 1974-11-26
BE751185A (fr) 1970-11-03
DE2025452C3 (de) 1979-11-08
NO134184B (enrdf_load_stackoverflow) 1976-05-24
NL7007859A (enrdf_load_stackoverflow) 1970-12-01

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