IE45066B1 - Process for dyeing hair - Google Patents

Abstract

Some people want the colour of their hair to change gradually over the course of a few weeks rather than abruptly. To this end, the procedure involves a series of successive dyeings giving an increasingly intense coloration. Oxidation dyes are used, the amount of dye solution being the same for all the dyeings but the amount of oxidising agent, which is limited to the stoichiometric amount for the first dyeing, being gradually increased in the successive dyeings until the desired final hue is obtained, the latter then being maintained by repeating the final treatment as required.

Description

Field of the Invention The invention relates to an improved process for dyeing human hair, involving the production of progressively deeper colorations with, succeeding treatments for attaining a target shade, and the maintenance thereof by further treatments at »? appropriate intervals thereafter. The Prior Art Dyeing of human hair has been effected heretofore by application of water-soluble heavy metal compounds - e.g. of Ni or Pb - together with reagents yielding a dark-colored water-insolublej i. metal derivative with· the metal compound - e.g. pyrogallol or sulfur compounds.

A more versatile dyeing process - with which the present invention is concerned - involves application to hair of arid .liable, primary aromatis amines (especially diamines) and substitution products thereof, usually together with aminophenols, in admixture· with an oxidising agent - especially or aerivatives ,. such as urea peroxide, perborates,·percarbonates, persulfates,, perphosphates, periodates or the like - whereby socalled oxida.tion dyes or colors are formed in situ on the hair. In the color-forming reaction, the aromatic primary amino groups and phenolic hydroxyl groups' are oxidized in situ to form imino groups and CO groups, and coupling occurs to jform polyimino compounds in ' which the aromatic, nuclei assume a quinonoid configuration - e.g.

It is customary also to include in the colorant mixture, - la 6e coupling compounds such as a polyhydric phenol - e.g. resorcinol, pyrogallol or the like. Atmospheric oxygen can be relied upon as the sole oxidant in hair dyeing, but the use of H^O^ or its derivatives is generally preferred, since the reaction proceeds more rapidly with the latter oxidants and can be more readily controlled. Compositions yielding oxidation colors are conventionally combined with surfactants (detergents, wetting agents) and thickeners, such as are usual in shampoos, so as to facilitate removal of excess reagents by rinsing.

Women generally prefer a dyeing process in which the target color is attained in a single treatment. Men, however, are usually reluctant to dye their hair in such a way that the complete color change occurs in a single treatment, since they find this embarrassing. A number of preparations have been marketed for men which gradually change or darken the color by repeated applications cf the dyeing composition at selected intervals, and maintenance of the final desired coloration is effected by further applications at less frequent intervals. Such coloring compositions usually employ a heavy metal compound and a reagent adapted to form a dark colored sulfide of the metal. However, as compared with oxidation dyes, these compositions lack versatility in the hue of the available colorations.

It was known heretofore to produce gradual darkening of hair by repeated application of an oxidation color mixture at successive intervals. It was also known to modify the depth of shade by varying the concentration of the colorant. Depth of shade has also been controlled by increasing the duration of the treatment. Using a trihydric phenol as the colorant with an iodate, periodate or persulfate as an oxidant therefor, it was -2. known to increase the depth of shade of the coloration produced by increasing the oxidant concentration - the oxidant and colorant being applied in the same or separate solutions.

Processes heretofore known using aromatic primary amineU» 5 and aminophenols as oxidation colorants for hair do not suggest varying the.proportion or concentration of the oxidant as a means for controlling depth of shade.

Objects of the Invention It is an object of the invention to provide a process 10 for dyeing hair·with oxidation dyes in which successive applications at selected intervals first produce a predetermined light coloration, and then successively predetermined deeper shades, until a target, or desired coloration is produced which can be maintained by further applications of the last applied composition at less frequent intervals.

It is a further object to provide a process as above in which the successive hair dyeing treatments can be conveniently performed by the person whose hair is to be dyed and in a short time period, in the order of five (5) minutes.

A further object is to provide a hair dyeing process in which the depth of shade produced in successive treatments following the initial treatment is controlled by increasing the quantity of oxidant added starting with an amount approximately stoichiometric for the initial application and added to a sub25 stantially constant amount of colorant employed in each treatment. Description of the Invention and the Preferred Embodiments In accordance with the invention, a colorant solution is provided containing a mixture of oxidation colorants, including, for example, p-phenylenediamine, p-tolylenediamine, -3p-aminophenol, 2,4-diaminoanisole, and p-methylaminophenol usually with a coupler such as resorcinol - combined with an aqueous vehicle containing, in solution, surfactants conventionally employed in shampoos, such as Na lauryl sulfate, Na-laurylpolyethyleneglycol ether sulfate, N-lauroyl diethanolamine and ethylenediaminetetracetic acid Na salt, and alkaline reagents such as borax, morpholine and Na sulfite, which adjust the pH of the composition. A perfume can also be included. The concentration of the colorant mixture (including a coupler such as resorcinol) is advantageously from 0.5 to 8¾ by weight. The pH is preferably adjusted from 8 to 10. For use with such a colorant solution, there is provided an oxidant solution - especially 6-5 H^Og - or equivalent solutions of derivatives such as urea peroxide, perborate or percarbonate, persulfate or periodate.

For dyeing hair - first, in a predetermined light shade and then in successively deeper predetermined shades, a substantially constant amount of the colorant solution (suitable for moistening a head of hair uniformly; is mixed in successive treatments with a quantity of the oxidant solution which is increased in each successive treatment (e.g. 3 treatments in all) - the final treatment yielding the target or desired shade. Xn each case, after applying the mixture of colorant and oxidant to the hair, development of the coloration is permitted to occur over a specified period which is the same for each treatment (e.g. 5, or 15 minutes). The composition is then rinsed from the hair with water. After the target shade is attained, it is maintained by re-applying the mixture used in the last treatment of the darkening series at such intervals as to color the new growth of hair in the target shade. a 0 θ β The process of the invention is convenient for use without professional assistance, since the user - in each treatment - has only to measure a specified constant quantity of colorant solution, mix it with a similarly measured quantity of oxidant solution - the quantities in successive treatments after the first being advantageously simple multiples of the amount used in the first application - applying the resulting mixture of colorant and oxidant to the hair, waiting a specified period e.g. 5 minutes - and rinsing the residual mixture from the hair.

. The following examples, wherein parts and percentages are by weight, illustrate the process of the invention: Example 1 An aqueous vehicle containing surfactants commonly employed in shampoos and pH adjusting agents is prepared having the following composition: De-ionized water 311 parts Na sulfite 7 parts Borax 15 parts Morpholine 20 parts Ethylenediaminetetracetic acid tri-Na salt 5 parts N-lauroyl diethanolamine 35 parts ' _N a-laurylpolyethyleneglycol ether sulfate 60¾ 100 parts Na lauryl sulfate 30% 200 parts Two colorant solutions are prepared having the following compositions - the first (A) providing light brown as the target shade, and the second (B) yielding a medium brown as the target shade: -5ίο A B Resorcinol 2.5 parts 2.5 parts p-phenylenediamine 6.0 parts 8.0 parts p-tolylenediamine sulfate 2.0 parts 5.0 parts p-aminophenol 3.0 parts 6.0 parts 2,4-diaminoanisole sulfate 0.25 parts 2.5 parts p-methylaminophenol sulfate 1.0 pGi.2? ts 0.0 parts Perfume (Lavender) 5.0 parts 5.0 parts De-ionised water 302.0 parts 302.0 parts Vehicle as above 693.0 parts 693.0 parts Totals 1 014.75 parts 1024.0 parts The resulting colorant solutions have a pH of 9.5, which promotes decomposition of H2O2 and its peroxy derivatives.

As the oxidant for use with the foregoing colorant solution, 6% (i.e. 20-volume) use^'' or an aqueous solution of an equivalent quantity of urea peroxide, Na perborate or Na percarbonare can be used - replacing - if desired - part cf the water wich propylene glycol to facilitate dissolution.

In use, 30 cc. of colorant solution A is mixed for the first treatment with 2.5 cc. of oxidant solution. The mixture is applied to the hair and allowed to develop for 5 minutes, a very short time period by conventional dyeing standards. The hair is then rinsed. The treatment yields a barely perceptible brownish coloration. After a desired interval, determined by the user (e.g. one week), a second treatment is carried out, using in this case, 5 cc. of oxidant solution with 30 cc. of colorant solution. After development for 5 minutes, the hair is rinsed, yielding an intermediate light brown shade. Again, after a desired interval of a week or so, a third application is made, using 10 cc. of oxidant solution and 30 cc. of colorant solution. Five minutes' development, followed by rinsing, yields the final light brown target shade. This can be maintained by -62 ίϊ 0 g θ repeating the third treatment at such intervals (e.g. about once every 2 to 8 weeks) so as to color new growth of hair in the target shade.

Similar treatments using colorant solution B yields, first, a light brown shade, then an intermediate darker brown shade, and finally a medium brown target shade. Maintenance of the final coloration is effected in the same manner as in the case of colorant solution A.

Example 2 Three colorant solutions are prepared having the fol- lowing compositions - the first (C) yielding < a medium dark brown as the target shade - the second (D) , a light medium brown - and the third.(Ε), a light brown: 1. De-ionized water C 56.864% D 57.410% E 59.51% 2» Trisodium ethylenediaminetetracetic acid 0.488 0.493 0.49 3. Sodium sulfite 0.584 0.690 0,68 4. Borax 1.465 1.478 1.46 5. Morpholine 1.953 1.970 1.94 6. Sodium lauryl-polyethyleneglycol ether sulfate (50%) 9.766 9.854 9.71 7. Sodium lauryl sulfate (30%) 19.531 19.709 19.42 S. N-lauroyl-diethanolamide 6.418 6.449 4.85 9. Resorcin 0.244 0.246 0.24 10. Paraphenylenediamine 0.781 0.591 0.58 11. Para-aminopheno1 0.586 0.296 0.29 12. Paratolylenediamine sulfate 0.488 0.197 0.29 13. 2,4-diaminoanisole sulfate 0.244 0.25 0,05 13a. Paramethylaminophenol sulfate 0.099 - 14. Perfume (lavender) 0.488 100.—% 0.493 10.0.-% 0.49 100.—% -7•4·> To prepare the foregoing colorant solutions, the water (1) is heated in a mixing kettle to 80 degr. C. 2, are added successively, each being completely dissolved before addition of the next. 6 and 7 are then added at the same temperature. 8 and 9 are then successively added at a temperature of 70 degr. C. 10, 11, 12 and 13 (and 13a in composition D) are added, and agitation continued for 15 minutes. The mixture is cooled to 40 degr. C. and 14 is then added.

Example 3 Two colorant solutions are prepared having the following 3, 4 and compositions - the first (F) yielding a light brown as the shade - and the second (G), a medium dark brown: P G L De-ionized water 56.84¾ 45.32% 2. Trisodium ethvlenediamine- tetracetir acid 0.48 0.47 3 * Sodium sulfite 0.67 0.66 A ‘S · Borax 1,44 1.41 5. Mcnoethanolamins 1.92 2.57 6. Sodium lauryl-poiyethyleneglvcol ether sulfate (60¾) 9.59 13.39 7. Sodium lauryl sulfate (30%) 19.18 20.78 8. N-lauroyl-diethanolamide 5.36 7.29 9. 4-chioro-resorcinol 0.515 0.515 10. Paratolylenediamine sulfate 2.130 2.130 11. Meta-aminophenol sulfate 0.745 0.745 12. Para-aminodiphenylamine sulfate 0.650 0.650 13. 2,5-diaminoanisole sulfate 0.50 14. Perfume (lavender) 0.48 0.47 -84 » OS 6 Colorant solutions F and G are prepared in substantially the same manner as described in Example 2.

For coloring hair, the colorant solutions of Examples 2 and 3 are applied in essentially the same manner as described in Example 1.

The quantity of oxidant employed in the first treatment as illustrated in the foregoing examples should provide 0.5 to 2 times the amount required to oxidize the aromatic primary amino groups and aminophenols contained in the components of the colorant solution. , The amount of oxidant has been termed herein as approximately stoichiometric to dramatize and characterize the amount as being very small in contrast to the prior art. The quantity of oxidant used in the second treatment as illustrated in the examples should provide 1.0 to 4 times the amount required of oxygen to oxidize the primary aromatic amino groups and aminophenols contained in the colorant solution. In the third and subsequent maintenance treatments illustrated in the examples, the quantity of oxidant should provide 2 to 10 times the amount of oxygen required to oxidize the aromatic primary amino groups and aminophenols contained in the colorant solution employed.

In the colorant solutions illustrated in the foregoing examples, the concentration of surfactant components advantageously ranges from 10 to 25%, that of the pH adjusting components from 2 to 10%, and that of the aromatic primary aromatic amino group compounds and aminophenols (with the coupler or couplers), from 0.5 to 8%.

As illustrated in the examples, the quantities of oxidant used in the successive treatments after the first are simple multiples of the amount used in the first treatment - especially multiples constituting a geometric series (1, 2, 4) - or simple multiples (1, 2, 3,4). A geometric series of multiples is preferred, since it yields a substantially linear darkening of the -9hair in attaining the target shade. In each case, the development time for each treatment of the series is substantially constant - e.g. 5, 10 or 15 minutes.

Oxidizable aromatic primary amines and aminophenols which can be used in the colorant solutions as such, or in the form of their water-soluble salts, such as sulfates, hydrochlorides or acetates - may be selected from the following: ο-, p— and m-phenylenediamine p-amincdiphenyfamine p-aminodiphenylamine sulfonic acid 2-aminO“4-nitrophenol 4-amino-2-nitrophenol p-aminophenol m-aminophenol o-aminophenol ο-, m- and p-methylaminophenol 2-aminotjhe.iOl-4-sulfonic acid 4-aminopheno1-2-su1fon ic ac id o-anisidine 2,4 -diaminoanisole 2,5-diaminoanisole p,p'-diaminodiphenylamine ρ,ρ'-diaminodiphenylamine sulfonic acid ρ,p‘-diaminod iphenylmethane 1,8-diaminonaphthalene 2, 4-diarainophenol 2.4- diaminophenetole 2.5- diaminophenol-4-sulfonic acid N,N'-dimethyl-p-phenylenediamine 4.6- dinitro-2-aminophenol N-(p-hydroxyphenyl)-glycine -1013-{2-hydroxy-5-nitrophenyl)-glycine ‘ p-methylaminophenol 4-nitro-o-phenylenediamine m- and p-tolylenedfamine >2,4,6-trinitroaniline Couplers which can be used in the colorant solution are, for example, polyhydric phenols such as resorcinol, chlororesorcinols, pyrocatechol, pyrogallol and hydroquinone.

Surfactants suitable for inclusion in the colorant 'solution or in the oxidant solution combined therewith are, for example,' higher fatty acid soaps? higher fatty alcohol sulfuric ester salts of alkali metals, ammonium or aliphatic amines; higher fatty acid alkylolamides; polyalkyleneglycols; and ethylenediamine-tetracetic acid alkali metal or ammonium salts.

Compounds suitable for adjusting the pH which can be included in the colorant solutions illustrated in the examples include alkylolamines, such as mono-, di- and triethanolamine, water-soluble alicyclic amines such as morpholine, and alkali metal salts of weak inorganic acids such as borax, alkali metal sulfites and alkali metal carbonates.

The oxidants used in the oxidant solution of the example can be derivatives of such as urea peroxide, alkali metal perborates, -percarbonates, -perphosphates, -persulfates or -periodates, as well as H202 itself.

Other variations and modifications which will be obvious to those skilled in the art can be made in the foregoing examples and the above outlined modifications thereof without departing from the spirit or scope of the invention.

Claims (15)

WE CLAIM: 1.

1. A process for dyeing hair by application of a mixture of colorant solution of primary aromatic amines and aminophenols and an oxidant containing or a peroxy derivative

2. A process-as defined in Claim 1 wherein the quantity of oxidant admixed ,with the colorant solution in the first treatment is 0.5 to 2 times the amount required to oxidize all of the aroma,tic primary amines and the aminophenols contained in the * · I

3. A prqcess as defined in Claim 2 wherein the quantity qf oxidant admixed with fhe colorant solution in each treatment of the series after the first is a simple multiple of the quantity '10 ’employed in the first treatment.

4. A process as defined in Claim 3 wherein the multiples! of the quantity of oxidant employed in the successive treatments following the first constitute a geometric progression with the amount employed in the first treatment. 15

5. A process as defined in Claim 4 wherein the quantities of oxidant employed in the successive treatments of the serief are substantially in the ratio of 1, 2, and 4. 5 colorant solution, and ranges up to 10 times said amount in the last treatment of the series yielding a target shade. 5 }for predetermined time period followed by a rinse removal of the residual mixture; the improvement to the aforesaid process comprising: (a) applying said colorant-c-xidant mixture in succesive applications to gradually get rid of the undesirable

6. A process as defined in Claim 1, wherein the colorant solution includes, as a coupler, a polyhydric phenol. 20

7. A process as defined in Claim 1, wherein the colorant solution comprises a surfactant.

8. A process as defined in Claim 1, wherein the oxidant is selected from the group consisting of H 2 Q 2 , urea P srost ~ ide, and per-salt derivatives of H 2 0 2 25 1

9. A process as defined in Claim 1, wherein the quantity of oxidizable aromatic primary amines and aminophenols contained in the colorant solution, together with any coupler contained therein, ranges from 0.5 to 8% by weight of the solution.

10. A process as defined in Claim 1, wherein the oxi30 ; dant is employed in a solution of which the concentration is equivalent in oxidizing potential to that of a solution of H 2 0 2 of about 6% concentration. 10 hair color, i.e. gray, wherein (i) the time period of application of the mixture being short, in the order of five (5) minutes and of a predetermined length for each subsequent application, lg (ii) the gxc.ntity of colorant solution is predetermined and constant through all applications, (iii; ths quantity of oxida.it in the mixture in the first application is of an initial predetermined amount of oxidant approximating 20 stoichiometric and successive applications having predetermined increased quanities of oxidant above said initial predetermined quantity; (b) each mixture having the ability to produce a 25 predetermined oxidation color on ordinary human hair; and (c) each such color being a deeper shade than the preceding application, whereby the user can stop the coloration process at any desirable color attainment and thereafter maintain such color level by repeating the application 30 with the mixture of colorant and oxident last used.

11. A process as defined in Claim 1, wherein the quantity of colorant solution employed in each treatment is about 30 cc. and the quantities of oxidant solution employed in three successive treatments are respectively 2.5, 5 and 10 cc.

12. A process as defined in Claim 1, wherein the pH of the mixture applied in each of the successive treatments is within the range of 8 to 10. - 12 So e β

13. A process as defined in Claim 1, wherein the colorant solution contains 2.5 parts resorcinol, 6-8 parts p-phenylenediamine, 2-5 parts p-tolylenediamine sulfate, 3-6 parts paminophenol, 0.25-2.5 parts 2,4-diaminoanisole sulfate, up to 1 part p-methylaminophenol sulfate, 5 parts perfume, 7 parts Na sulfite, 15 parts borax, 20 parts morpholine, 35 parts N-lauroyl diethanolamine, 5 parts ethylenediaminetetracetic acid trisodium salt, 60 parts Ha-laurylpolyethylenegiycol ether sulfate, 60 parts Na lauryl sulfate, and aboyt 793 parts water, and the oxidizing solution is 61 3,0,. 14. A process as defined in Claim 1 wherein the colorant solution contains 0.24 - 0.246 parts resorcinol, 0.58 - 0.781 parts caraphenyjenediamine, 0.29 - 0.586 parts para-aminophenol, 0.197 - 0.438 parts paratolylenediamine sulfate, 0.05 - 0.25 parts 2j4->3iaainoanisole sulfate, up to 0.099 parts p-methylaminophenol sulfate, 0.488 - 0.493 parts perfume, 0.68 - 0.69 parts sodium sulfite, 1.46 - 1.478 parts borax, 1.94 - 1.97 parts morpholine. 0.488 - 0.493 parts ethylenediaminetetracetic acid tri-sodium salt, 9.71 - 9.854 parts sodium lauryl-polyethyleneglycol-ether sulfate (60%), 19.42 - 19.709 parts sodium lauryl sulfate (30¾), 4.85 - 6.449 parts N-lauroyl-diethanolamide and 56.864 - 59.51 parts water. - 13 6 5

14. - 14 4 0 0 6 6 < .

15. A process as defined in Claim 1 v/herein the colorant solution contains 0.515 parts 4-chlororssorcinol, 2.13 parts paratolylenediamine sulfate, 0.745 parts meta-aminophenol sulfate, . 0.50 0.65 parts para-aminodiphenylamine sulfate, up to /parts 2,55 diaminoanisole sulfate, 0.47 -0.48 parts perfume, 0.66 - 0.67 parts sodium sulfite, 1.41 - 1.44 parts borax, 1.92-2.67 parts monoethanolamine, 0.47 - 0.48 parts ethylenediamine-tetracetic acid trisodium salt, 9.59 - 13.39 parts sodium lauryl-polyethylene!· glycol ether sulfate (60S), 19.18 - 20.78 parts sodium lauryl TO sulfate (30%), 5.36 - 7.29 parts N-lauryl-diethanolamide and 48.32-·’ 56.84 parts water. IS. A process as defined in Claim 1 in which the time period of each application of the mixture is constant.