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Publication numberUS3215605 A
Publication typeGrant
Publication dateNov 2, 1965
Filing dateApr 25, 1962
Priority dateApr 25, 1962
Publication numberUS 3215605 A, US 3215605A, US-A-3215605, US3215605 A, US3215605A
InventorsSoloway Saul
Original AssigneeRevlon
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Method for coloring hair and other keratinaceous fibers with metal salts
US 3215605 A
Abstract  available in
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Description  (OCR text may contain errors)

United States Patent 3,215,605 METHOD FOR COLORHWG HAIR AND OTHER KERATINACEOUS FIBERS WITH METAL SALTS Saul Soloway, New Rochelle, N.Y., assignor to Revlon, Inc., New York, N.Y. N0 Drawing. Filed Apr. 25, 1962, Ser. No. 189,987 1 Claim. (Cl. 16788) This invention relates to the coloring or dyeing of hair, fur, and similar keratinaceous substances or fibers and, more particularly, to effecting such coloring by means of metallic salt complexes applied directly to the material to be colored or as chemically combined or linked to a pretreating agent previously applied to the hair or reacted with substances therein and/or with or without additional color modification by a subsequently applied reactant. I

As well known, of course, the dyeing or coloring or tinting of hair or fur has for years been carried out with a wide variety of dyes and other coloring materials, although the dyeing or coloring of such materials, particularly to obtain a permanent and lasting effect, presents a variety of well recognized problems distinct from other natural or synthetic fibers. Especially in the dyeing or coloring of growing human hair (to which this invention is particularly adapted and which will be utilized in the following discussion as illustrative of the techniques and objects to which this invention relates), certain particularly exacting complications or problems may be encountered.

For example, although various metallic salt dyes and organic dyestuffs of both natural and synthetic varieties have been extensively used for years in the dyeing of hair with more or less degrees of satisfaction, a number of well recognized deficiencies and disadvantages obtain with such attempts, particularly with growing human hair. The difficulty of obtaining natural appearing colors or shades or hues with metallic salt dyes is well recognized, particularly in instances where it is desired that the dyed product appear completely natural and not dyed. Organic dyestuffs, such as the widely used paraphenylenediamine-type of materials, are highly toxic to many individuals and produce frequent adverse physiological effects so that, although satisfactorily used in the dyeing of animal fur, widespread use in human hair dyeing is tolerated primarily because of the general lack of anything better. The shortcomings of other natural materials such as the henna-type dyes is well understood, despite the fact that such materials have been used for dyeing human hair for literally thousands of years. Even with such materials, however, difiiculty may be experienced in achieving a desirably natural-appearing shade or color, and especially in situations where the particular shade or color desired or dictated by the precepts of a current fashion may be chemical dyeing reaction of conventional dyestuffs with the various protein or amino acid materials which form the keratinaceous hair fiber.

Even if it is possible to obtain a particularly desired hue or shade with a blending of a variety of materials which might be described as dyestuffs, still other disadvantages may be experienced, particularly with human hair, such as ancillary complications involving the necessity of maintaining a harshly alkaline pH for the dyeing reaction or unhealthful concomitants of necessary oxidation of the dye into the protein-affinity form, etc. Similar complexities may be experienced with hair coloring techniques involving the production in situ of melanin as the physiologically natural hair coloring material, particularly if it is desired to obtain a coloration in the reddish area and apart from the brown or black hues naturally produced by melanin and/or of a reddish or other variety of color or shade which is either completely synthetic or outside the spectrum of natural colors produced by physiological pigments other than melanin.

Especially as applied to the treatment of growing human hair (and as distinct from the greater operational latitude permissible in the coloring or dyeing of other animal fur, hair, or Wool fibers or other keratinaceous substances), substantial difiiculty may be experienced in achieving a desired hue or shade of coloration, whether by chemical fiber dyeing or other coloring techniques, within the permissible area of physiologically innocuous chemical reactions While still obtaining the ultimate visual effect to approximate satisfaction in the user. Such visual satisfaction, as will be well understood, may be dictated by non-technological considerations which superimpose upon the dyeing or coloring technology virtually insuperable chemical problems involving not only the ultimate shade or hue of coloration achieved, but also the lustre and texture and tractability of the hair being treated, as well as such considerations as the necessity for repeated and frequent treatments of the same hair in order to accommodate the growth thereof and constant exposure of new lengths of untreated hair adjacent the skin from which the hair is growing.

According to this invention, by contrast, there is provided a system or technique and compositions for achieving on hair or fur or other keratinaceous substances a variety of effects of coloration or dyeing for avoiding disadvantages heretofore encountered in connection with prior or conventional attempts to produce natural-appearing dyed effects with either metallic salt or organic types of dyestuffs on such materials or fibers with conventional dyeing or pigment-forming or mordanting techniques; and, in accordance with this invention, the desired coloring effects are produced bya variety of metallic salt or oxide complexes, principally chemically combined or linked with polypeptide components in the hair directly or with organic pretreatment agents applied to and/ or reacted with components in the hair for accepting the metallic complexes, which complexes as so linked or reacted with such materials either produce the desired degree and intensity of coloration or present for further reaction a potentially colorific group or materials susceptible to engendering the desired color by subsequent chemical treatment. As more specifically stated features of novelty, the teachings in accordance herewith include the activation of or chemical combination with certain amino acid materials in the hair by a pretreating agent to or with which complex salts of certain metals, particularly the transition metals of Group VIII of the Periodic Table, form colored compounds or complexes and may combine, either to produce the finally desired ultimate color or to present a new chemical arrangement in or on the hair fibers which is susceptible to colorific modification by aftertreatment with a variety of subsequent modifying or complexing agents.

With the foregoing and other objects in view, this invention will now be more particularly described, and other objects and advantages thereof will be apparent from the following description and the appended claims.

As will be understood, of course, certain inorganic metallic salts may be considered as inherently possessing certain colored or coloring qualities in water solution or otherwise, and some of them to some extent may be considered as having true dyeing propensities. Generally, however, the techniques and compositions in accordance with this invention are to be distinguished from such inherent qualities or propensities of simple inorganic metal salts. That is, the simple treatment of hair with aqueous solutions of metallic salts (no matter how colorific they may be inherently) does not produce a dyeing or coloring elTect of the stability or intensity 'or controllability desired here for the particular coloring of human hair. For example, a variety of more or less impermanent colors or tints (in the sense that they can be more or less readily washed out by shampooing) may be imparted to human hair by applying thereto a variety of aqueous solutions of many colored metallic inorganic compounds. Indeed, there are even some instances where the mere application to reasonably blond or bleached hair of some simple aqueous solution of metal salts provides a distinct coloration of a more or less permanent nature--e.g., AuCl alone imparts a bright yellow color to bleached human hair, while aqueous solutions of cupric salts impart a more or less permanent light green color. Nevertheless, such effects are to be distinguished from the most preferred advantages obtainable in accordance herewith.

This invention relates primarily to the achieving of the desired coloring or tinting effect utilizing a variety of metallic salts or complexes, particularly of the socalled transition metals, which can be caused to bind or link, one way or another, permanently to the hair materials to impart thereto colored elfects, whether or not the particular shade or color is that normally associated as characteristic of the particular metal salt involved. Furthermore, treatments in accordance herewith achieve the desired effects even with metallic salt materials which inherently have no particular afiinity for any of the materials of which the hair is composed, and preferred results are attained in accordance herewith by the prior treatment of the hair and/or certain materials therein with a pretreating chemical agent or reactant so as to make available reactive valences or combining linkages for the reaction or addition of the colorific metallic complex to achieve the desired permanency, shade 'or hue, and texture.

For example, certain metallic salt materials with which satisfactory results are obtained in accordance herewith have been found not to have a particular colorific or propensity with previously untreated human hair. Nevertheless, if the hair is first chemically treated as disclosed with a variety of preliminary treating agents, a preliminary situation is created wherein a variety 'of metal salt solutions form chemically combined arrangements or complexes permanently with the hair. Among such activating or preliminary treatments may be noted, particularly conventional alkaline peroxide bleaching techniques, which are particular adapted for use in accordance herewith because a person desiring to color hair frequently also wants to bleach the natural color out of the hair as a preliminary step to achieving the ultimate shade or color desired.

Another, perhaps supplementary preliminary treatment material with which satisfactory results are achieved in accordance herewith is illustrated by a substance such as ammonium thioglycolate (hereinafter referred to for brevity as ATG), which material is particularly adapted as a pretreatment agent for application to previously bleached hair and as being representative of those materials which exhibit a ready reactivity for one or more of the chemical linkages naturally occurring in human hair so as to form, in addition to the desired color-reactive potential linkage, a material which also provides a certain amount of conditioning or softening or manageability to the hair being treated at least sufficient to olfset any contrary characteristics produced by the coloring treatment.

Thus, considering merely as illustrative of the treatments in accordance herewith, the pretreatment results of utilizing ATG in hair coloring techniques in accordance with this invention, one may note that a substantial portion (perhaps 20%) of human hair is formed of material such as cystine compounds having an RSSR- linkage, with the R being an amino acid radical. Reaction with ATG, with or without previous reaction in an alkaline peroxide bleaching step, breaks the RSSR linkage in the hair to produce ionizable or reactive -SH and RS and/or a different and ionizable ammonium RSSR compound, some or all of which are readily available to acquire and/ or combine with a metallic complex, particularly in alkaline solution, to an extent far greater than woud be the case with merely attempting to react a metallic compound with the natural and stable cystine material. Such preliminary reactions, then, make possible the integration or combining or complexing of a variety of colorific metallic salt solutions directly or permanently with the hair materials for producing a coloration thereon or, at least, a reactive outer surface compound susceptible to color engendering or changing upon further chemical reaction. As will be apparent, such results are obtained in a mechanism which, generally, may be considered somewhat different than any conventional dyeing technique and/or direct coloring techniques in which solutions of simple inorganic metallic colored salts may be utilized.

As illustrative of such a sequential or complex reaction and the advantages or results thereof, one may note the situation where a material such as a bivalent nickel salt in 5% water solution produces substantially no discernible color change when applied to the hair alone or to bleached hair, but the same solution of the metallic salt produces a quite discernible and brownish color when applied to hair which has been previously bleached and treated with ATG, and a somewhat similar situation occurs with cobalt compounds. Similarly, the gold chloride mentioned above, while producing a bright yellow color when applied initially to bleached hair, produces a usable and satisfactorily natural appearing golden or auburn coloration when applied to such hair previously treated with ATG in accordance herewith.

Also, it should be emphasized that the treatment of hair with AT G alone does not appear to produce any appreciab le change in coloration, any more than is observed with the above noted nickel or cobalt solutions alone, so the effect of coloring is achieved with a combination of preliminary chemical treatment and subsequent metallic complex and with demonstrably true synergism. Furthermore, the preliminary reaction of a complexing or pretreating agent such as ATG with the metal salts by mixing prior to the application of either to the hair fails to produce the coloring effect desired when applied to the hair, apparently because such preliminary reaction complexes the metal ions with the ATG and all available valences thereof so as to leave few if any available reactive linkage points for interaction or combining with the hair materials to produce the permanent coloring effect desired.

As further illustrative of suitable materials with which techniques embodying this invention may achieve satisfactory results, it may be noted that the metallic coloring agent involved (here referred to as metallic complexes) may be produced particularly from the so-called transition metals of the Periodic Table, in aqueous or ammoniacal or organic complexing environments. Thus, as noted above, merely a 5% aqueous solution of trivalent gold chloride produces the desired synergistic reaction with ATG-treated bleached hair, as do aqueous solutions of a variety of other nickel, cobalt, cadmium, ferrous, ferric, cupric, etc., salts. Some of such materials also perform adequately or differently, and in some cases more advantageously, when utilized in ammoniacal solution, instead of merely aqueous solution, to form the desired metal complex for application to the previously treated hair. In many such cases a different color or a different intensity or shade of color is provided when the metallic salt is applied in ammonia solution instead of plain water, and different anions may give different effects for the same metal ion, especially as between anions of different valences. As noted below, in most if not all of such situations, the color or shade or intensity thereof can be further enhanced or changed or even removed by subsequently applying an additional complexing agent after the metallic material is applied to or linked on the hair and, in some cases, whether or not a preliminary complexing agent such at ATG was also utilized.

Generally in accordance herewith, a variety of metals have been found satisfactorily to react or combine with bleached hair, either directly or after pretreatment thereof with a complexing material such as ATG, although some of the metals so reacted did not inherently produce a noticeable color change in hair. Nevertheless, the bonding or linking of a metal ion or complex directly to the hair or to an intermediate treatment compound combined therewith provides a situation where the color of the metallized hair may be subsequently modified to provide the complete advantages hereof whether or not a desirable color was obtained by the metallizing treatment alone. The fact of reaction on the hair is readily demonstrable (even when no discernible color change occurs), particularly with metals applied in the form of a salt which is colored in aqueous solution, by noting the reduction in intensity of the color of the solution as the reaction of the metal occurs with hair dipped into the color solution, as well as by a visual metallic effect appearing in the hair surface.

Among the metals which reacted for complexing or binding to the hair in accordance herewith, in aqueous or ammoniacal solution and with or without an initial or unaided color change, may be noted a variety of metallic ions including such metals as lithium, cesium, as well as copper, silver, gold, magnesium, calcium, barium, zinc, cadmium, and mercury from the first two groups of the Periodic Table. Particularly of interest, however, are the transition metal elements or those which have incomplete orbitals and a plurality of oxidation states such as those of Group VIII as well as such metals as lathamum and the lanthanide series of rare earths, the actinide series such as thorium, tin, and lead. Vanadium, bismuth, chromium, manganese, molybdenum, and uranium salts also were capable of complexing or binding results.

It was primarily the metals of Group VIII of the Periodic Table, however, which were found to produce the greatest or most useful color change in reaction with either the hair alone or with hair previously treated with a complexing agent such as ATG, and, particularly, iron, cobalt, nickel, palladium, and platinum. Although other Group VIII metals achieved the desired reaction, the extreme rarity or expensiveness of rhenium and iridium and the extreme toxicity of osmium salts indicate that these materials are not preferred, especially in the treatment of growinghuman hair. As previously noted, of course, copper and gold salts give direct and useful color effects, although these metals are not in Group VIII of the Periodic Table, but the metals of this latter group are essentially those with which preferred results are achieved in accordance herewith when a primary color change is desired upon initial application of either an aqueous or ammoniacal complex of the metal to the treated or untreated hair.

As previously noted, after application of the metal complex to the hair and the desired chemical bonding or linking thereto, some further modification of the color effect may then be achieved by a subsequent treatment of the metallized hair by an additional complexing or treating agent. As illustrative of such materials with which satisfactory results are achieved herewith may be noted such materials as an amidoxime of cyanoethylcellulose polymers (referred to here for brevity as ADC) and/ or thioamide materials or derivatives such as dithiooxamide (referred to as DTOA), etc. Although both the aforementioned materials or types of materials do produce color variations or modifications as indicated in more detail in the following data, the complexing or other mechanisms by which they each react on or affect the metallic materials linked to the hair may vary considerably, as will be understood.

enerally, as to visual effect, the subsequent application of additional complexing agents or reactants to the metallized hair had the effect of deepening or darkening the color originally produced by the metal salt, although in some cases the actual color Was changed, rather than merely deepening the original shade. In other cases (e.g., ferric salts) the original color was actually lightened by subsequent application of a material uch as AOC. In other cases, the application of one or the other of such materials as AOC or DTOA appeared to prevent or remove a color change obtained with the metal salt and only on activating pretreatment.

From the standpoint of the chemical reactions involved, it is essentially desired that the subsequent complexing agent react with the metal ion previously linked to the hair to form therewith a metallic complex of the desired color, which color will be different from that originally produced by the reaction of the metallic salt with either the hair or a pretreating agent such as ATG thereon. With resin or polymer types of subsequent complexing agents such as the AOC mentioned, a variety of tautomeric possibilities occur having different reactive or terminal groups available for complexing reaction with the previously applied metal ion. That is, such materials are derived from cyanoethylcellulose in known manner by, for example, reacting it with hydroxylamine to form, instead of the terminal CN group, either tautomeric amidoxime group, which may react with various metal complexes on the hair to give a variety of different organo-metallic complexes having different colors and under different conditions.

Also, as will be understood, similar variations in conditions or colors, due to tautomerism or otherwise, may also be satisfactorily utilized with the materials such as DTOA or thiourea or other thioamides wherein the shifting double bond linkages with either N or S in the terminal or reactant groupings provide for additional varieties of reactions and formation of metallic complexes of different colors with the metal ions previously applied to the hair and/or by complexing the originally applied metal salts with regard to the cystine linkages in the hair itself and/or the thioglycolate reaction therewith after pretreatment with ATG.

In any event, as will be apparent from the foregoing, the final color effects in accordance with this reaction may be achieved in almost infinite variety and with a similar variety of different complexing mechanisms for producing colored metallic salt complexes chemically linked in one way or another to the substances in the hair. Especially with the use of a preliminary treatment of thio-glycolate (for reaction with the --RSSR group in the cystine in the hair) and the subsequent utilization of thio-amine materials readily tautomerized in varione solution media and at various pH ranges, -a large number of different possible permutations and combinations for the formation of differently colored metallic complexes is provided by the profusion of reactive S and N groups and double bonds involved in the several noted types of compounds.

Indeed, the actual color effects obtained by the various different complexing reactions possible may not be with certainty predicted in every case, whether or not the chemistry is predictable, although the color effect have been found to be completely reproducible. That is, the particular effects are readily discernible empirically for any given combination of chemical substances, and the selected effects are thereafter completely reproducible in accordance herewith, whether one desires to rely merely on the color change affected by the initial reaction of an aqueous or ammonia metallic complex with the hair or a pretreatment complexing agent thereon or Whether it is desired to modify this initial color condition further with a subsequent treatment of an additional complexing agent as noted. Although the thio-types of subsequent complexing agents apparently produce a wider variety of different shades and color hues, it may actuaally be preferred to use one of the polymer types of complexing agents, such as AOC, because such materials have an independent advantageous effect on the hair as softening or conditioning agents, in addition to whatever effect they may have in the coloring reactions, and are desirable additives to the coloring technique for the purpose of aiding the later manageability of the hair, etc.

Merely as illustrative of some of the different coloring effects achieved with various metallic salts and different complexing agents in accordance herewith, the following Tables I and II collate the general results of a number of different treatment of essentially the same initially bleached human hair. In each instance the data is given with respect to a variety of treatments with various metallic ions in aqueous or ammonia solution, with ATG being indicated as the preliminary complexing agent applied to the bleached hair prior to the metallic salt and with AOC and DTOA being shown as representative of subsequently applied types of organic complexing agents.

Although data is given for instances Where no visibly appreciable color change was obtained, it is to be understood that additional or different subsequent complexing agents may be utilized, as will be understood from this disclosure, to produce other colored complexes with the applied metallic salt in a variety of different colors or shades. In all instances the texture and sheen or appearance of the hair was satisfactory, indeed usually to a greater extent than is normally experienced with conventional hair dyeing treatments, and the colors achieved were the desirably natural appearing hair colors, with the possible exception of the several instances noted in the greenish spectrum. Even these, however, were found to be further modified to more natural hues by subsequent additions of various complexing agents.

In both Tables I and II, reading across, the 2; marks denote whether or not a preliminary hair treatment with ATG and/ or subsequent complexing treatments with AOC and DTOA were utilized with each of the noted metallic salt complexes to provide the results noted. Table I sets forth illustrative data obtained using ammonia solution of the various salts noted, while the data of TABLE II relate to application of the metallic materials in aqueous solution, with a 5% concentration of salt in each case.

Table I Metal Salt in N HiOH Green.

Olive Green.

Black with greenish tinge. Dark reddish brown.

Lighter reddish brown.

Dark reddish brown.

Dark brown, slightly reddish. Darker brown.

Still darker brown.

Very dark brown.

Darllger brown (almost black). x o.

Table 11 A00 DTOA Color Results Dark yellow to auburn. Green'brown.

Dark green-brown. Bright yellow.

No color change. Slightly pink.

No (light change.

Slightly tan.

Light brown.

No color change.

Light brown.

Slightly tan.

Light green-brown. Darker green-brown. Black with greenish tinge. No color change.

Do. Black with bluish tinge. Light green-brown. Darker green-brown. Dark red brown. N 0 color change. Slightly tan. Dark red brown. No color change.

Do. Light yellow. Light green.

0. Black with greenish tinge. Liglig green.

As Will be apparent from the foregoing tabulations, the ultimate color effect achieved with a particular metal salt is a truly synergistic function of the presence or absence of one or more pretreatments or after treatments, with the former in one way or another breaking or activating some sulphur (or, perhaps, some nitrogen) valences in the keratinaceous material of the hair for compleXing reactivity or combination with the metallic salt material.

It is to be understood, in considering the foregoing tabulations, that all relate to the treatment of hair which has been previously bleached with conventional alkaline peroxide bleaching techniques, in the course of which some activation of otherwise stable valences or chemical bonding has occurred. For example, although gold chloride or cupric salts produce a desirably permanent color effect (indicating true chemical complexing or combination with the hair) when applied to the bleached hair, a similarly permanent combination or result is not achieved with the same materials applied to hair which has not previously been subjected to some bleaching or chemical pretreatment. Furthermore, a further pretreatment, as with ATG or similar sulphur-reactive agents, in addition to reaction with the bleaching agent, produces still different complexing or color effects with the same metallic salt solutions, just as additional after treatments with different thio-amidic or other sulphur and nitrogen containing materials alters the color efiect achieved and/ or changes or modifies in some manner or other the particular metallic complex achieved with the hair materials. For example, considering the instances in the tabulations where the results are indicated as not producing the color change, such notation is to be understood as indicating merely that the particular metallic complex achieved with the combination of materials noted does not produce an appreciable color on the bleached hair, whereas other different complexes of the same metal achieved With the different combinations of materials to produce a discernible color effect.

As will be apparent from the foregoing, a wide variety of materials are also available for pretreating the hair to receive the desired coloring action by metallic complexes, although, as noted, such materials may fall broadly into the two categories of polymer-type materials and those which actually react chemically with materials in the hair such as the cystine groups mentioned. Although the visible or coloring results achieved in either case may be substantially alike, it is to be understood that the particular mechanism whereby such results are achieved may vary. Thus, a variety of polymer-type materials (in addition to those noted above) may be utilized as a pretreating or aftertreating complex material provided they also contain a multiplicity of functional groups in close proximity for bonding with a metal ione.g., readily chelated materials, and/ or, particularly, those With active or available carboxy, hydroxy, amino, oxime, thio, cyano, etc., groups.

Such functional groups are available for complexing the metallic salts, and, when included in a film forming or polymer-type material, are thus useful in accordance herewith. That is, such pretreatment or complexing agents form a coating or film layer over the hair (whether or not they may also chemically react with the hair) as a basis for binding the colorific metallic salts to form a more or less permanent colored layer bound to the hair. Although, for ease of application, water soluble varieties of such polymer or film forming materials produce satisfactory results in accordance herewith, it is preferred to utilize such materials which tend to be insolubilized by the metallic salt complexing therewith. Also, as will be understood for the particular utility here, absolute insolubility or permanence may not be necessary for satisfactory results in view of the necessity for repeatedly treating the hair from time to time to maintain the artificial color thereof in any event and because the hair continues to grow and produce new areas adjacent the scalp requiring repeated treatment.

With the reactive or non-polymer types of pretreating materials noted (e.g., thio and dithio materials, peroxides, etc.) an actual chemical reaction between such agents and the hair is believed to occur, as noted, to open the -RSSR- linkage in one way or another and thus provide on the hair itself and from the materials therein an active sulphur (or sulfhydryl) group available for complexing the metal salt and/or an active carboxy or hydroxy or other group. That is, the RSSR radical in the hair is considered to react with one of the pretreating agents to produce some active group on the RS of the original cystine hair material, which group is available to bind metallic ions, while the SR group separated from the cystine radical also remains available separately to complex the metallic salts.

As will be understood, enhanced results may be achieved by utilizing pretreatment materials which both cling to the hair mechanically as film forming polymers and also chemically react to open up the RSSR radical to make available a plurality of complexing groups for binding the colorific metallic ions. Similarly, the colored effects desired are generally achieved by metallic ions which will remain bound to the hair if combined with sulphur in some oxidation state thereof, and some such metals, upon complexing with a sulphur material, themselves form additional active bonds for further complexing of additional metal ions. Therefore, in addition to purely mechanically bound complexing agents, there are also available generally in accordance herewith a wide variety of materials which include various groups susceptible of nucleophilic displacement generally with dithio radicals. Among the classes of materials, for example, which may combine both of the above mentioned mechanisms may be noted polymer-type esters of thio or cyano acids (e.g., a polyester of polyvinyl alcohol and thioglycolic acid or a reactive polymeric ester of hydroxy ethyl cellulose and thioglycolic acid). Accordingly, there are available for use herewith materials having a plurality of complexing groups for reaction with colorific metallic ions (e.g., hydroxyoxime, dioxime, dithio, thiohydrazide, diphenol, hydroxyamine, etc.) and some means for binding such reactive groups (or other metal-complexing hy droxy, carboxy, thio, cyano, etc., groups) more or less permanently to the hair-whether this last mentioned means includes mechanical binding as with a film forming polymer or chemical binding as by actual reaction with materials in the hair. Additionally, both of the foregoing can readily be combined into a single material and, also, the invention includes the situation where the metal binding agency is wholly produced within the hair itself as by peroxide reaction with a pretreating material which contributes nothing more to the final effect other than opening the RSSR linkage so it will receive and bind colorific metal ions.

Accordingly there is provided in accordance herewith a wide variety of materials and combinations of materials for application to human hair to produce thereon a variety of different colors, shades, tints, or hues, all of a substantially permanent nature and resulting from different metallic salt complexes actually chemically bound to the hair materials. Furthermore, the methods and compositions involved are simply applied to the air in solution, with the particular color effect being controlled primarily by the combination of materials used, rather than being a notable function of reaction time or other delicate control technique which might require extensive manipulative experience on the part of the person applying the coloring material. Similarly, by contrast with conventional hair dyeing techniques and compositions, the materials involved are free of adverse physiological toxic or sensitivity factors, are essentially innocuous in use and effect, with some of them actually imparting to the hair beneficial characteristics in addition to coloring. Prior to application to the hair in the desired sequence, all the various pretreatment and after treatment and metallic salt compositions or components hereof are essentially stable and readily packaged for convenient storage, sale, and handling, and the results achieved (both from the standpoint of permanency and specific color effect) are readily and repeatedly reproducible in a completely safe and certain manner, even by untrained or unskilled users; and the effective reactions involved for the application of the metallic salt materials, after treatment agents, etc., neither involve nor rely upon harsh oxidation or reduction reactions or other chemistry of a nature which must be either critically controlled or considered as damaging to the hair being treated.

While the method and compositions herein described constitute preferred embodiments of the invention, it is to be understood that the invention is not limited to these precise methods and compositions, and that changes may be made therein without departing from the scope of the invention which is defined in the appended claim.

What is claimed is:

The method for coloring human hair and like keratinaceous fibers with colorific metallic salt complexes, which comprises the steps of pretreating said hair with a chem ical pretreating reactant for reaction with -RSSR- groups in cystine materials in said hair to activate reactive complexing valences therein and selected from the group consisting of ammonium thioglycolate, polyesters of polyvinyl alcohol and thioglycolic acid, polyesters of hydroxy ethyl cellulose and thioglycolic acid, and mixtures thereof, applying an equeous solution of a colorific complexing metal salt to said pretreated hair for reaction and complexing combination with said reactive valences thereof for forming a metallic complex chemically bonded to said pretreated hair said complexing metal salts being inorganic salts of metals selected from the group consisting of lithium, caesium, copper, silver, gold, magnesium, calcium, barium, zinc, cadmium, mercury, the transition metals of Group VIII of the Periodic Table, the lanthanide series of rare earth metals, the actinide series of metals, tin, lead, vanadium, bismuth, chromium, manganese, molybdenum, uranium, and mixtures thereof, and thereafter treating said metallic complex on said hair with an additional complexing agent for altering the visible color effect of said metallic complex as bound on said hair, said additional complexing agent being selected from the group consisting of dithiooxamide, amidoxines of cyanoethyl cellulose polymers, polyesters of thioglycolic acid, and mixtures thereof.

References Cited by the Examiner UNITED STATES PATENTS 2,501,184 3/50 Michaels 167-88 12 2,615,782 10/52 Haefele 167-88 XR 2,719,104 9/55 Westerberg 167-88 2,769,748 11/56 Eckardt et al. 167-88 2,934,396 4/60 Charle et a1 167-88 XR 2,948,657 8/60 Siccama et al. 167-88 XR 3,062,609 11/ 62 Abel 8-43 3,063,950 11/62 Schouteden 260-212 XR 3,066,077 11/ 62 De Mytt et al 167-871 3,075,821 1/63 Goldemberg et al. 167-88 XR FOREIGN PATENTS 163,316 6/55 Great Britain.

OTHER REFERENCES Encyclopedia of Chemical Technology, 14: 173-177 (1955).

Goldemberg: Journal of the Society of Cosmetic Chemists, 10: 294, 296, and 301-302 (1959).

Greenfield: Journal of the Society of Cosmetic ChemiSts, 8(4): 200, 201, 205, and 209 (1957).

Rostenberg et al.: Todays Health, vol. 48, No. 8, pp. 14-17 and 68-71, especially pages 16 and 17 (1964).

Wilsmann: American Perfumer and Aromatics, (5), p. 46, May 1960.

JULIAN S. LEVITT, Primary Examiner.

FRANK CACCIAPAGLIA, L. GOTTS, Examiners.

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US3075821 *Aug 18, 1960Jan 29, 1963Shulton IncProcess of dyeing keratinous fibers
GB163316A * Title not available
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3415606 *Apr 23, 1964Dec 10, 1968Randebrock Rudolf EmmanuelMethod of dyeing human hair with reactive dyes
US3838966 *May 25, 1970Oct 1, 1974Mennen CoPermanent but removable hair-coloring system
US3966903 *Apr 22, 1974Jun 29, 1976Shiseido Co., Ltd.Sulfite or bisulfite hair-waving composition containing a wave accelerating agent
US3973574 *Dec 7, 1973Aug 10, 1976Fumio UmezawaWaving and straightening hair by producing metal chelates in the keratin of the hair
US4173453 *Mar 9, 1978Nov 6, 1979CDC Research Inc.Topical hair coloring formulation in the form of suspension, lotion and cream
US4630621 *Sep 27, 1985Dec 23, 1986Susanne PontaniMethod and composition for simultaneously permanently waving and dyeing human hair
US4801302 *May 5, 1987Jan 31, 1989L'orealProcess for dyeing human hair with brazilin or its hydroxyl derivative and compositions employed
US5161553 *Sep 19, 1986Nov 10, 1992Clairol IncorporatedProcess for simultaneously waving and coloring hair
US5173085 *Jan 29, 1991Dec 22, 1992Clairol IncorporatedHair dyeing process and compositons package
US5346509 *Apr 14, 1993Sep 13, 1994Clairol IncorporatedProcess for dyeing hair by the sequential treatment of hair with metal ion-containing composition and with a dye composition containing 5,6-dihydroxyindole-2-carboxylic acid and certain derivatives thereof
US5635168 *Sep 21, 1994Jun 3, 1997Business Resources Group, Inc.Composition for treating hair
US5942009 *Mar 28, 1997Aug 24, 1999Brg, Ltd.Same-day waving and coloring of hair
Classifications
U.S. Classification8/425, 8/432, 424/DIG.200
Cooperative ClassificationA61K8/731, A61Q5/065, A61K2800/57, Y10S424/02, A61K8/19, A61K8/46
European ClassificationA61K8/46, A61K8/19, A61Q5/06D, A61K8/73C