Classifications

• • 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
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
  • A61K8/34—Alcohols
  • A61K8/347—Phenols
• • 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
  • A61Q5/10—Preparations for permanently dyeing the hair

Definitions

• ABSTRACT OF THE DISCLOSURE A process for preventing or retarding the damage to hair during coloring operations (e.g., bleaching or dyeing with oxidation dyes) by simultaneously polymerizing in said hair a polymerizable monomer; the polymerization being brought about by the oxidizing agent used in the bleaching or dyeing operation and the further insolubilization of the polymer formed being caused by a bridging agent, which bridges the polymeric chains.
• This invention relates to processes for preventing or retarding the damage to hair during the coloring of the same and to compositions useful in effecting this purpose. It has application to those processes wherein the hair is merely lightened by the action of a bleaching agent, as Well as those processes which utilize a dye that requires an oxidizing agent to develop the color of the dye. It also has application to those combined hair coloring procedures which employ a bleaching agent to lighten the hair, followed by dyes or toners that do or do not require an oxidizing agent for their development.
• Hair coloring takes several forms which utilize an oxidizing agent that has a tendency to damage hair and make it more porous.
• hair is bleached by simply subjecting it to the action of a bleaching agent.
• Common agents used for this purpose are ammoniacal peroxide, alkali peroxide, or one of the above mixed with ammonium or potassium persulfate, etc.
• the hair may be colored by the application of an oxidation dye composition.
• This dye composition usually contains one or more dyes whose colors are developed by an oxidizing agent.
• This oxidizing agent usually takes the form of hydrogen peroxide.
• the coloring operation usually takes place in two steps.
• the hair is lightened through the use of an oxidizing agent, most usually a composition containing hydrogen peroxide and a persulfate compound.
• the hair is then toned by the application of the so-called toners which are oxidation dye compositions that require an oxidizing agent for their development.
• the dyeing is effected through the use of non-oxidation dyes.
• retouching i.e., making the regrowth area the same color as the rest of the hair
• retouching involves applying as a lightening mixture, an alkaline, peroxidepersulfate mixture to the root ends of the hair while attempting to minimize contact of the previously lightened hair with the fresh lightening mixture.
• the lightening mixture is pulled down over the remainder of the hair shaft by means of a comb or the like. This latter treatment generally lasts for about 5 minutes and is used to remove faded toner left in the hair by a previous coloring treatment.
• All of the hair coloring procedures described above exemplify those processes in the hair coloring art which require the use of an oxidizing agent and which tend to damage hair and make it more porous.
• the hair is subjected to multiple treatments with compositions containing oxidizing agents and the damage may be compounded. This is illustrated by the so-called retouching procedure.
• a measure of remedy suggested for these problems involves applying pastes of oils, waxes, and protein hydrolyzates to retard the action of the lightener on the porous areas of the hair. Also the problem of very weak tonertake on excessively porous hair may be partially overcome by application of additional coloring materials to the porous areas. Essentially, however, these measures are of a nonperrnanent nature as the increased body imparted to the hair by the conditioning agents currently in use is lost when the hair is shampooed.
• the damage to hair attending the coloring thereof as defined above may be prevented or retarded by treating said hair during the coloring thereof with a water soluble polymerizable vinylic monomer containing an acid forming group or a salt thereof and polymerizing said monomer in situ with the aid of an oxidizing agent.
• the oxidizing agent used in the coloring operation may serve ths purpose.
• the polymeric chains of vinylic mononier formed in the procedure of this invention are preferably bridged by bridging agents which reduce the water solubility of said polymer.
• the processes of the present invention involve the treatment of hair with a polymerizable vinylic monomer during the coloring thereof. It is contemplated by this invention that the polymerization and coloring of the hair may be effected at the same time or may be accomplished sequentially. In some aspects of this invention when they are carried on sequentially, it is also within the purview of this invention that these steps can be carried out in any order, i.e., the polymerization can be brought about before or after the lightening operation.
• the processes of the present invention lend themselves to a good deal of variation.
• the hair is pre-treated with an aqueous solution containing the polymerizable vinylic monomer and bridging agent.
• a second solution containing the bleaching agent (which is an oxidizing agent) is then applied. This procedure may be applied to hair which is unbleached or hair that has been given .a previous bleaching treatment.
• a simple extension of the procedure described above involves the application of a toner to the hair after the final treatment with the bleaching agent.
• This usually comprises mixing an oxidation dye composition with an oxidizing agent which will develop the color of the oxidation dyes and then applying this mixture to the hair. It is also possible in this case to substitute a non-oxidation dye system for the oxidative dye system.
• hair which may or may not have been previously bleached, is first treated with an oxidation dye composition to which has been added oxidizing agent and polymerizable vinylic monomer. After a period of time the hair is then treated with an aqueous solution of the bridging agent.
• hair (which may or may not have been bleached) is wettecl with an aqueous solution containing the polymerizable monomer and the bridging agent. After the elapse of a period of time, the hair is dyed out with an oxidation dye composition to which has been added the oxidizing agent.
• An alternative procedure for coloring the hair by bleaching in accordance with this invention involves wetting the hair with an aqueous solution containing the polymerizable vinylic monomer and the oxidizing agent. This solution is permitted to act on the hair for a period of time and then the bridging agent, preferably in the form of an aqueous solution, is applied to the hair.
• the present invention also has utility in retouching previously bleached hair and particularly pre-bleached hair which has been made overporous or has been otherwise damaged.
• the entire head is first saturated with an alkaline aqueous solution of a watersoluble monomeric vinylic compound, as described above.
• the solution contains a bridging agent, such as water soluble polyvalent cations or long-chain, watersoluble monovalent organic cations.
• this solution After the application of this solution, it is combed through the hair.
• the oxidizing agent mixture is then applied in the usual retouch fashion to the virgin roots of the hair (regrowth area). After the roots have been in contact With the oxidizing agent mixture for the desired period of time, this mixture on the roots is smoothed over the entire head of hair. Five minutes or less after this last step, the hair is shampooed and towel dried, ready for the toner application if desired.
• the vinylic monomer used in this invention because of the relatively small size of its molecules, enters into the interior of the hair structure. Inside the hair structure, it polymerizes to relatively long chain molecules under the influence of the oxidizing agent. These molecules, because of their size cannot readily leave the interior of the hair structure. Furthermore, the action of the bridging agent in bridging adjacent polymeric chains further insolubilizes the polymers and locks them within hair structure. This action serves to strengthen the hair treated and minimize any damage caused by the oxidizing agent.
• the agent most commonly used in lightening hair is essentially hydrogen peroxide in an alkaline solution With varying amounts of compounds, such as persulfate salts, to accelerate the action of the agent.
• the strongest of the agents which are currently used for lightening are sold as powders which are mixed with commercially available (20 volume) hydrogen peroxide. These are the socalled powder bleaches.
• these agents are very fast acting compared to the liquid lighteners, they are not generally used for retouch applications because their potent action tends to damage the hair excessivly when applied a second time to previously lightened hair.
• the materials employed in practicing the present invention may be used in any convenient form. Thus, they may be applied as aqueous solutions or suspensions, gels, pastes, creams, etc. in a manner well-known to those skilled in this art.
• acid forming groups are important for the purposes of the present invention in that they provide sites at which neighboring polymer chains may be bridged by means of bridging agent utilized in this invention to render the polymer less water soluble.
• acid forming groups is intended to encompass the acid groups per se, as well as groups which will be converted into acid groups under the conditions of use of the present invention.
• polymerizable vinylic compounds that may be used in accordance with the present invention are water-soluble compounds described by the general formula: 1
• RzC C- wherein R R and R are selected from the group consisting of hydrogen, alkyl, aryl and halide, and X is selected from the group consisting of acid groups and salts thereof (e.g., -COOH, SO H).
• X is selected from the group consisting of acid groups and salts thereof (e.g., -COOH, SO H).
• acrylic acids sodium acrylate, potassium acrylate, monoethanolamine acrylate, potassium acrylate, calcium acrylate, methacrylic acid, sodium methacrylate, monoethanolamine methacrylate, potassium methacrylate, calcium methacrylate, itaconic acid and salts of itaconic acid.
• the bridging agents used in accordance with the present invention to further insolubilize the polymerized vinylic compound formed can be of a variety of types.
• One class of bridging agent comprises water-soluble compounds (e.g., salts, oxides, hydroxides) of elements of Group II or III of the Periodic Table capable of yielding multivalent cations (divalent, trivalent, etc.). These are believed to function as bridging agents through the formation of a salt-like structure involving the acid groups of neighboring polymeric chains and the cations of the bridging agent.
• These bridges can be visualized in the case wherein the polymerizable vinylic compound is a carboxy acid and the bridging agent is a calcium salt or compound as follows:
• A is a polymeric chain.
• A is a polymeric chain.
• the following compounds can serve as bridging agents which will supply the cationic type bridge: Cacl ZnCl,, Bacl AI,(SO.), and difunctionai quaternary ammonium compounds, such as N Tallow, N-N-dlmethyl-N'-N'-N'-trimethyl-l,3-propylene-dlammonium chloride (Aliquat 726): N-Tallow'lJ- propylene-diaminedioleate (Diam 26 Dioleate).
• Another class of bridging agent that may be used in accordance with the present invention may be described as agents capable of providing long-chain organic monovalent cations.
• the mechanism by which these long chain cations work to provide a bridge between neighboring polymer chains is not quite clear. However, it is believed that this probably involves chain entanglement.
• this class of bridging agent may be exemplitied by the following: cetyl pyridinium chloride; cetyl trimethylammonium chloride; stearyl amine.
• an oxidizing agent capable of polymerizing the vinylic monomer is used in accordance with the present invention.
• this oxidizing agent will also be instrumental in coloring the hair.
• the term oxidizing agent is used in its broad sense and is intended to encompass a single oxidizing agent, as well as a combination of oxidizing agents. Moreover, it is also intended to cover complex compositions which include other components which may or may not be active ingredients.
• the term oxidizing agent is intended to apply to compositions which contain, in addition to the active oxidizing agent, such things as thicheners, carriers, surfaces active agents, basic materials, etc.
• the term oxidizing agent is also intended to extend to oxidation dye compositions which contain suiiicient oxidizing agent to function in polymerizing the vinylic monomer.
• the oxidizing agent used in this invention can vary considerably. By way of illustration the following may be mentioned: H 0, ammonium persulfate, sodium persulfate, potassium persulfate, pastes made from a combination of aqueous H 0, and said persulfates, etc.
• oxidation dye compositions that can be employed in accordance with the present invention are also quite varied. Any of the compositions of this character which are well known to those skilled in this art are utilizable. Thus, for example, the oxidation dye formulas shown on page 508 of Cosmetics, Science and Technology by Edward Sagarin (i957) lnterscience Publishers, inc., New York, are suitable for the present purposes.
• a swelling agent in the treating compositions.
• These materials are generally basic in nature and give the treating solutions a relatively high H.
• a pH between 8 and 9 or 10 is particularly sultsble For this purpose.
• a pH between about 7 to ll can be used.
• any of a number of bases both organic and inorganic may be used to obtain the suitable pH.
• bases organic and inorganic may be used to obtain the suitable pH.
• -the following may be mentioned: .monoethanolamine, NaOi-i, KOH, Ni-b, Ca(0H),, etc.
• concentration of vinylic monomer, bridging agent and oxidizing agent and time of treatment that is utilized in accordance with the present invention is interrelated and may be varied considerably. Any combination of these parameters which result in the incorporation into the hair structure of a polymer of high enough molecular weight to reinforce the hair strength will serve the purposes of this invention. This will be made clearer by a discussion of the mechanism of the polymerization reaction believed to be operating in the present invention.
• the rate of conversion of monomer to polymer is made up of three steps: initiation, propagation, and termination.
• the initiation step consist of forming monomer free radicals, either by direct activation, or by forming other free radicals which then add to monomer.
• the rate of formation of monomer radicals (iinitiation) will be proportional to the monomer concentration and also the concentration of initiating radicals (which will in turn be proportional to initiator concentrations, i.e., the concentration of oxidizing agent).
• the propagation step will be primarily dependent on monomer concentration. This is the step which, relative to the initiation and termination steps, determines the molecular weight of the polymer formed (i.e., if propagation is fast compared to the termination and initation steps, the molecular weight of the polymer formed will be high).
• the rate of the termination step is proportional to the total concentration of all radicals; initiator, monomer, and growing chain species. (See, for example, P. i. Flory, Principles of Polymer Chemistry, Cornell University Press, 1953, chapter 4.)
• the time of treatment cannot be unduly long. This must be taken into consideration in determining the concentration of the components of the compositions utilized in this invention, since the time interval during which a proper degree of polymerization taltcs place is dependent on the concentra tion of the various components of the composition.
• the concentration of vinylic monomer and oxidizing agent is therefore so arranged so that a suificient degree of polymerization will take place so as to reinforce the hair within a time period generally used in the beauty trade for treating hair on the human head.
• the concentration of vinylic monomer present in the solution used either serially with the bridging agent and/or simultaneously with the bridging agent will be in the range of a .05 M. to 2.5 M.
• the bridging agent is generally used in the concentration range of .05 M. to 2.5 M., the divalent bridging agent usually being employed in the range of .05 M. to 1.25 M. and the monovalent agent in the range of .l M. to 2.5 M.
• the concentration of oxidizing agent in the compositions applied to the hair will vary with the particular type of application involved, as well as other factors. Where the oxidizing agent serves as a bleach, its concentration will be very high and may approach saturated solutions. In the case where the oxidizing agent scrvcs as the agent by developing the color for an oxidation dye, the values will be much lower. in this case it may vary from about .596 to about 15% by weight.
• the time during which the vinylic polymerization is allowed to proceed will also vary. in general, however, this will be between 5 to 60 minutes.
• the bridging agent When used simultaneously with the vinylic monomer, it, obviously, will be allowed to act over the same period of time as the vinylic monomer. However, where the 7 bridging agent is applied after the application of the vinylic monomer, it is permitted to remain in contact with the hair over a period of l to 10 minutes and ideally for minutes.
• the oxidation dye composition mentioned in some of the examples set out below has the following formula:
• EXAMPLE 1 A sample of normal brown hair was treated with a bleach mixture containing l5 grams of ammonium persulfate and 40 ml. of 6% H O, for lVs hours at 30' C. This sample was then divided into three parts: (a) control, not treated further, (b) control treated again as above, and (c) treated as (b), except before the second bleach the sample was wet with a pretreating solution of 2.2 grams potassium acrylate, 1.5 grams CaCl, (anhydrous), 20 ml. H,O (solution pH 7.5). The relative tensile modulus values (measured in water) of the samples were found to be 5.3, 3.9, and 7.4 for (a), (b), and
• EXAMPLE 2 Starting hair was treated for two successive 2-hour treatments with the bleach mixture described in Example i. The hair was then separated into two samples: (a) control, given 5 cycles of a two-step blonding, representing the treatment given to all but the hair roots during successive retouches. The cycle was: 5-minute treatment with the said bleach mixture, shampoo, 30-minute treatment with Composition A +20 volume 50,, light shampoo, then dried. (b) 5 cycles as in (it), except each cycle was preceded by a wetting with the pretreating solution as described in Example i (e). After the wetting, the hair was allowed to sit for 45 minutes (representing the root bleaeh-out time) before applying the bleach mixture.
• samples (a) and (b) were made on the basis of dye-take, swelling on immersion in water (as measured microscopically), and relative tensile modulus values (as measured in water).
• the dye-takes were equivalent in shade but the control sample (a) was somewhat deeper in intensity.
• the transverse swelling for (a) was twice as much (on an area basis and also on a volume basic because the longitudinal swellings were essentlaliy equal) as for (b).
• the tensile modulus values were 0.9 and 3.2 for (a) and (b), respectively.
• Composition A -..oz- 2 20 Vol. H 0, --oz-- 2 Sodium acrylate ..g... 10
• a process for dyeing hair in an aqueous medium with an oxidation dye composition which comprises subjecting said hair to a preliminary bleaching treatment, subsequently wetting said hair with a mixture of a watersoluble polymerizable monomeric vinyl compound in the concentration range of .05 M to 2.5 M selected from the group consisting of vinyl compounds having acid forming groups and salts thereof and a bridging agent in the concentration range of .05 M to 2.5 M and subsequently dyeing said hair with an oxidation dye composition containing an oxidizing agent in the concentration range of .5% to 15% by weight; said monomeric vinyl compound being selected from the group consisting of acrylic acid, sodium acrylate, potassium acrylate, monocthanolamine acrylate, calcium acrylate, methacrylic acid, sodium methacrylate, monocthanolamine methacrylate, potassium methacrylate, calcium methacrylate and itaconic acid; and said bridging agent being selected from the group consisting of CaCl ZnCl,, BaCI Al,(SO N)
• a process for dyeing hair in an aqueous maximt with an oxidation dye composition which eomprisr treating said hair with a composition containing an ox dation dye, an oxidizing agent in the concentration rang of .596 to 15% by weight and a water-soluble polymeriz able monomeric vinyl compound in the concentratic range of .05 M to 2.5 M having an acid forming grou or salts thereof and subsequently treating said hair with a composition containing a bridging agent in the concentratlon range of .05 M to 2.5 M; said monomeric vinyl compound being selected from the group consisting of acrylic acid, sodium acrylate, potassium acrylate, monoethanolamine acrylate, calcium acryinte, methncryllc acid, sodium methacrylate, monocthanolamine methacrylate, potassium methacrylate, calcium mcthacrylate and itaconic acid; and said bridging agent being selected from the group consisting of CaCl,, ZnCI 9 BaCl Al (SO
• a process for dyeing hair in an aqueous medium with an oxidation dye composition which comprises treating said hair with a composition containing a watersoluble monomeric vinyl compound in the concentration range of .05 M to 2.5 M having an acid forming group or salts thereof and a bridging agent in the concentration range of .05 M to 2.5 M, and subsequently treating said hair with an oxidation dye composition containing an oxidizing agent in the concentration range of .5% to 15% by weight; said monomeric vinyl compound being selected from the group consisting of acrylic acid, sodium acrylate, potassium acrylate, monoethanolamine acrylate, calcium acrylate, methacrylic acid, sodium methacrylate, monoethanolamine methacrylate, potassium methacrylate, calcium methacrylate and itaconic acid; and said bridging agent being selected from the group consisting of CaCl ZnCl BaCl Al (SO N- Tallow, N-N-dimethyl-N-NN-trimethyl-1, 3-propylenediammonium chloride; N-Tallow
• a process for simultaneously lightening and protecting hair in an aqueous medium which comprises subjecting said hair to the action of a composition comprising a bleaching agent in the concentration range of .5 to 15% by weight and a water-soluble monomeric vinyl compound in the concentration range of .05 M to 2.5 M having acid forming groups or salts thereof and subsequently treating said hair with a bridging agent in the concentration range of .05 M to 2.5 M;
• said monomeric vinyl compound being selected from the group consisting of acrylic acid, sodium acrylate, potassium acrylate, monoethanolamine acrylate, calcium acrylate, methacrylic acid, sodium methacrylate, monoethanolamine methacrylate, potassium methacrylate, calcium methacrylate and itaconic acid; and said bridging agent being selected from the group consisting of CaCl ZnCl BaCl Al (SO N-Tallow, N-N-dimethyl-N'-N-N'- trimethyl 1,3 propylene-diammonium chloride; N-Tall-ow
• a process for retouching, previously bleached hair having new hair growth, in an aqueous medium which comprises applying to said new growth an aqueous composition containing a water-soluble polymerizable monomeric vinyl compound in the concentration range of .05 M to 2.5 M containing acid groups or salts thereof and a bridging agent in the concentration range of .05 M to 2.5 M capable of rendering polymeric chains of said vinyl compounds less soluble in water and then applying to said new growth an aqueous composition containing an oxidizing agent in the concentration range of .5 to 15 by weight capable of promoting the polymerization of said monomeric compound and lightening said hair;
• said monomeric vinyl compound being selected from the group consisting of acrylic acid, sodium acrylate, potassium acrylate, monoethanolamine acrylate, calcium acrylate, methacrylic acid, sodium methacrylate, monoethanolamine methacrylate, potassium methacrylate, calcium methacrylate and itaconic acid; and said bridging agent being selected from the group consisting of CaCl

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• 1965
  • 1965-09-27 US US490729A patent/US3472604A/en not_active Expired - Lifetime
• 1966
  • 1966-08-12 GB GB36286/66A patent/GB1151188A/en not_active Expired
  • 1966-09-19 DE DE19661617378 patent/DE1617378A1/de active Pending
  • 1966-09-20 CH CH1350266A patent/CH490085A/de not_active IP Right Cessation

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