CA1073817A - Process for dyeing hair in which the depth of shade is gradually increased in successive treatments - Google Patents
Process for dyeing hair in which the depth of shade is gradually increased in successive treatmentsInfo
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- CA1073817A CA1073817A CA277,720A CA277720A CA1073817A CA 1073817 A CA1073817 A CA 1073817A CA 277720 A CA277720 A CA 277720A CA 1073817 A CA1073817 A CA 1073817A
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- 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
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/41—Amines
- A61K8/411—Aromatic amines, i.e. where the amino group is directly linked to the aromatic nucleus
-
- 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
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/41—Amines
- A61K8/415—Aminophenols
-
- 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
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Abstract
PROCESS FOR DYEING HAIR IN WHICH THE DEPTH OF SHADE
IS GRADUALLY INCREASED IN SUCCESSIVE TREATMENTS
A B S T R A C T
A process for dyeing hair by application of a mixture of colorant solution of primary aromatic amines and aminophenols and an oxident containing H2O2 or a peroxy der-ivative for a predetermined time period followed by a rinse removal of the residual mixture. The improvement comprises (a) applying said colorant-oxident mixture in successive applications to gradually get rid of the undesirable 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, (ii) the quantity of colorant solution is predetermined and constant through all applications, (iii) the quantity of oxident in the mixture in the first application is of an initial predetermined amount of oxident approximating stoichiometric and successive applications having predetermined increased qualities of oxident above said initial predetermined quantity; (b) each mixture having the ability to produce a 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 with the mixture of colorant and oxident last used.
IS GRADUALLY INCREASED IN SUCCESSIVE TREATMENTS
A B S T R A C T
A process for dyeing hair by application of a mixture of colorant solution of primary aromatic amines and aminophenols and an oxident containing H2O2 or a peroxy der-ivative for a predetermined time period followed by a rinse removal of the residual mixture. The improvement comprises (a) applying said colorant-oxident mixture in successive applications to gradually get rid of the undesirable 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, (ii) the quantity of colorant solution is predetermined and constant through all applications, (iii) the quantity of oxident in the mixture in the first application is of an initial predetermined amount of oxident approximating stoichiometric and successive applications having predetermined increased qualities of oxident above said initial predetermined quantity; (b) each mixture having the ability to produce a 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 with the mixture of colorant and oxident last used.
Description
)'7~'7 TITLE: PROCESS FOR DYEING HAIR IN WHICH THE DEPTH OF SHADE
IS GRADUALLY INCREASED IN SUCCESSIVE TREAT~TS
INVENTORS: HERBERT LAPIDUS, RIDGEFIEL~, CONNECTICUT
ALBERT SHANSKY, NORWALK, CONNECTICUT
Field of the Inventi_ 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 main-tenance thereof by further treatments at appropriate intervals there-after.
The Prior Art ~yeing 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-insoluble 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 oxidizable primary aromatic amines (especially diamines) and substitution products thereof, usually together with aminophenols, in admixture with an oxidiz-ing agent - especially H2O2 or its derivatives, such as urea peroxide, perborates, percarbonates, persulfates, perphosphates, periodates or the like - whereby socalled oxidation 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 form polyimino compounds in which the aromatic nuclei assume a guinonoid configuration - e.g.
A
. It is customary also to include in the colorant mixture, I ~?
~07381 7 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 H202 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 conven-; tionally combined with surfactants (detergents, wetting agents) and thickeners, such as are usual in shampoos, so as to facilitateremoval 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 of the dyeing composition at selected in-tervals, and maintenance of the final desired coloration is ef-. . . .
fected by further applications at less frequent intervals. Suchcoloring 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, perio te or persulfate a= an oxidant therefor, it was .
IS GRADUALLY INCREASED IN SUCCESSIVE TREAT~TS
INVENTORS: HERBERT LAPIDUS, RIDGEFIEL~, CONNECTICUT
ALBERT SHANSKY, NORWALK, CONNECTICUT
Field of the Inventi_ 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 main-tenance thereof by further treatments at appropriate intervals there-after.
The Prior Art ~yeing 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-insoluble 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 oxidizable primary aromatic amines (especially diamines) and substitution products thereof, usually together with aminophenols, in admixture with an oxidiz-ing agent - especially H2O2 or its derivatives, such as urea peroxide, perborates, percarbonates, persulfates, perphosphates, periodates or the like - whereby socalled oxidation 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 form polyimino compounds in which the aromatic nuclei assume a guinonoid configuration - e.g.
A
. It is customary also to include in the colorant mixture, I ~?
~07381 7 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 H202 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 conven-; tionally combined with surfactants (detergents, wetting agents) and thickeners, such as are usual in shampoos, so as to facilitateremoval 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 of the dyeing composition at selected in-tervals, and maintenance of the final desired coloration is ef-. . . .
fected by further applications at less frequent intervals. Suchcoloring 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, perio te or persulfate a= an oxidant therefor, it was .
-2-.. : .', .. ..
1{~731~317 known to increase the depth of shade of the coloration produced by increasing the oxidant concentration - the oxidant and color-ant being applied in the same or separate solutions.
Processes heretofore known using aromatic primary aminesand 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 for dyeing hair with oxidation dyes in which successive applica-tions at selected intervals first produce a predetermined lightcoloration, 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 ; 40 in which the depth of shade produced in successive treatments following the initial treatment is controlled by increasing the - 45 quantity of oxidant added starting with an amount approximately stoichiometric for the initial application and added to a sub-stantially constant amount of colorant employed in each treatment.
Description of the Invention and the Preferred Embodiments 7 - In accordance with the invention, a colorant solution is provided containing a mixture of oxidation colorants, in-cluding, for example, p-phenylenediamine, p-tolylenediamine, .
1{~731~317 known to increase the depth of shade of the coloration produced by increasing the oxidant concentration - the oxidant and color-ant being applied in the same or separate solutions.
Processes heretofore known using aromatic primary aminesand 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 for dyeing hair with oxidation dyes in which successive applica-tions at selected intervals first produce a predetermined lightcoloration, 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 ; 40 in which the depth of shade produced in successive treatments following the initial treatment is controlled by increasing the - 45 quantity of oxidant added starting with an amount approximately stoichiometric for the initial application and added to a sub-stantially constant amount of colorant employed in each treatment.
Description of the Invention and the Preferred Embodiments 7 - In accordance with the invention, a colorant solution is provided containing a mixture of oxidation colorants, in-cluding, for example, p-phenylenediamine, p-tolylenediamine, .
-3-- , , ': . - ~
¦ p-aminophenol, 2,4-diaminoanisole, and p-methylaminophenol ~
¦ usually with a coupler such as resorcinol - combined with an 5 ¦ aqueous vehicle containing, in solution, surfactants convention-¦ ally employed in shampoos, such as Na lauryl sulfate, Na-lauryl-¦ polyethyleneglycol ether sulfate, N-lauroyl diethanolamine and 10 ¦ 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 con-¦ centration of the colorant mixture (including a coupler such as ¦ resorcinol) is advantageously from 0.5 to 8% 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%
¦ H202 - or equivalent solutions of H202 derivatives such as urea ¦ peroxide, perborate or percarbonate, persulfate or periodate.
For dyeing hair - first, in a predetermined light shade 30 ¦ and then in successively deeper predetermined shades, a sub-¦ stantially constant amount of the colorant solution (suitable for ¦moistening a head of hair uniformly) is mixed in successive treat-ments with a quantity of the oxidant solution which is increased I in each successive treatment (e.g. 3 treatments in all) - the 40 1 final treatment yielding the target or desired shade. In each ¦ case, after applying the mixture of colorant and oxidant to the ¦ hair, development of the coloration is permitted to occur over a I ¦ specified period which is the same for each treatment (e.g. 5, ¦ 10 or 15 minutes). The composition is then rinsed from the hair 1 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.
.
~ 1~)7;~
¦ The process of the invention is convenient for use ¦ without professional assistance, since the user - in ~ach treat-5 ¦ ment - has only to measure a specified constant quantity of ¦ colorant solution, mix it with a similarly measured quantity of l oxidant solution - the quantities in successive treatments after 10 ¦ the first being advantageously simple multiples of the amount l 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.
he following examples, wherein parts and percentages 20 ¦ are by weight, illustrate the process of the invention:
l Example 1 25 ¦ An aqueous vehicle containing surfactants commonly ¦ employed in shampoos and pH adjusting agents is prepared having 30 ¦ 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 diethanolamine35 parts Ma-laurylpolyethyleneglycol ether sulfate 60% 100 parts Na lauryl sulfate 30%200 parts Two colorant solutions are prepared having the following compo-sitions - the first (A) providing light brown as the target shade, and the second (B) yielding a medium brown as the target shade:
10'7381'7 ¦ ~esorcinol 2.5 parts2.5 parts ¦ p-phenylenediamine 6.0 parts8.0 parts 5 ¦ p-tolylenediamine sulfate 2.0 parts5.0 parts ¦ p-aminophenol 3.o parts6.0 parts ¦ 2,4-diaminoanisole sulfate 0.25 parts 2.5 parts 10 ¦ p-methylaminophenol sulfate 1.0 parts0.0 parts l Perfume (Lavender) 5.0 parts5.0 parts 15 ¦ De-ionized water 302.0 parts30~.0 parts Vehicle as above 693.0 parts693.0 parts I Totals 1014.75 parts1024.0 parts 20 ¦ The resulting colorant solutions have a pH of 9.5, which promotes ¦ decomposition of H202 and its peroxy derivatives.
25 1 As the oxidant for use with the foregoing colorant so-¦ lution, 6% (i.e. 20-volume) H202 is used, or an aqueous solu-¦ tion of an equivalent quantity of urea peroxide, Na perborate 30 ¦ or Na percarbonate can be used - replacing - if desired - part ¦ of the water with propylene glycol to facilitate dissolution.
35 1 In use, 30 cc. of colorant solution A is mixed for the ¦ first treatment with 2.5 cc. of oxidant solution. The mixture l is applied to the hair and allowed to develop for 5 minutes, a 40 ¦ 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 ~ 1073817 ¦ 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 ¦ ~hree 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 (E), a light brown:
C D E
¦ 1. De-ionized water 56.864~ 57.410% 59.51%
30 ¦ 2. Trisodium ethylenediamine-¦ tetracetic acid 0.488 0.493 0.49 3. Sodium sulfite 0.684 0.690 0.68 35 ¦ 4. Borax 1.465 1.478 1.46 ¦ 5. Morpholine 1.953 1.970 1.94 l 6. Sodium lauryl-polyethylene-40 ¦ glycol ether sulfate (60%) 9.766 9.854 9.71 l 7. Sodium lauryl sulfate (30%) lg.531 19.709 19.42 45 ¦ 8. N-lauroyl-diethanolamide 6.418 6.449 4.85 9. Resorcin 0.244 0.246 0.24 l 10. Paraphenylenediamine0.781 0.591 0.58 50 ¦ 11. Para-aminophenol 0.586 0.296 0.29 O-~8~
¦ 12. Paratolylenediamine sulfate 6.118 0.197 0.29 55 ¦ 13. 2,4-diaminoanisole sulfate 0.244 0.25 0.05 13a. Paramethylaminophenol sulfate _ 0.099 -l 14. Perfume (lavender) 0.488 0.493 0.49 60 1 100.--% 100.~ 100.--%
¦ To prepare the foregoing colorant solutions, the ¦ water (1) is heated in a mixing kettle to 80 degr. C. 2, 3, 4 and 5 ¦ 5 are added successively, each being completely dissolved before ¦ addition of the next. 6 and 7 are then added at the same temper-¦ ature. 8 and 9 are then successively added at a temperature of 10 ¦ 70 degr. C. 10, 11, 12 and 13 (and 13a in composition D) are ¦ added, and agitation continued for lS minutes. The mixture is 15 ¦ cooled to 40 degr. C. and 14 is then added.
¦ Example 3 20 ¦ Two colorant solutions are prepared having the following compositions - the first (F) yielding a light brown as the target l shade - and the second (G), a medium dark brown:
25 ~ 1. De-ionized water 56.84% ~-L~r~
l 2. Trisodium ethylenediamine-30 ¦ tetracetic acid0.48 0.47 ¦ 3. Sodium sulfite 0.67 0.66 ¦ 4. Borax 1.44 1.41 5. Monoethanolamine1.92 ~,t~
6. Sodium lauryl-polyethyl-eneylycol ether sulfate (60~) 9.59 13.39 7. Sodium lauryl sulfate (30%) 19.18 20.78 8. N-lauroyl-diethanolamide 5.36 7.29 9. 4-chloro-resorcinol0.515 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,S-diaminoanisole O-SO
sulfate ~,o~r 14. Perfume (lavender)0~48 0.47 ~ 1073817 ¦ Colorant solutions F and G are prepared in su~stantially ¦ 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 l.
¦ The quantity of oxidant employed in the first treat-¦ ment 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 l 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 l.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 advantageous-ly ranges from lO to 25%, that of the pH ad~usting components from 2 to 10%, and that of the aromatic primary aromatic amino group compounds and aminophenols Iwith the coupler or couplers), from 0.5 to 8%.
~5 illustrated in the examples, the quantities of oxi-;~ ~ dant 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 (l, 2, 4) - or simple multiples (l, 2~ 3, 4). A geometric series of multiples is pre-ferred, since it yields a substan~ially linear darkening of the . ..... :. . . . . .: .. , :
10'73817 ¦ hair in attaining the target shade. In each case, the develop-¦ ment 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 I form of their water-soluble salts, such as sulfates, hydrochlor-¦ ides or acetates - may be selected from the following:
15 ¦ o-, p- and m-phenylenediamine ¦ p-aminodiphenylamine ¦ p-aminodiphenylamine sulfonic acid 20 ¦ 2-amino-4-nitrophenol ¦ 4-amino-2-nitrophenol 25 ¦ p-aminophenol m-aminophenol o-aminophenol 30 ¦ o-, m- and p-methylaminophenol 2-aminophenol-4-sulfonic acid ~35 ¦ 4-aminophenol-2-sulfonic acid ; I ¦ o-anisidine ~ 2,4-diaminoanisole I
40 ¦ . 2,5~diaminoanisole ¦ p,p'-diaminodiphenylamine p,p'-diaminodiphenylamine sulfonic acid : 45 l p,p'-diaminodiphenylmethane ::~ 1,8-diaminonaphthalene 2,4-diaminophenol -2,4-diaminophenetole : 50 2,5-diaminophenol-4-sulfonic acid N,N'-dimethyl-p-phenylenediamine
¦ p-aminophenol, 2,4-diaminoanisole, and p-methylaminophenol ~
¦ usually with a coupler such as resorcinol - combined with an 5 ¦ aqueous vehicle containing, in solution, surfactants convention-¦ ally employed in shampoos, such as Na lauryl sulfate, Na-lauryl-¦ polyethyleneglycol ether sulfate, N-lauroyl diethanolamine and 10 ¦ 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 con-¦ centration of the colorant mixture (including a coupler such as ¦ resorcinol) is advantageously from 0.5 to 8% 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%
¦ H202 - or equivalent solutions of H202 derivatives such as urea ¦ peroxide, perborate or percarbonate, persulfate or periodate.
For dyeing hair - first, in a predetermined light shade 30 ¦ and then in successively deeper predetermined shades, a sub-¦ stantially constant amount of the colorant solution (suitable for ¦moistening a head of hair uniformly) is mixed in successive treat-ments with a quantity of the oxidant solution which is increased I in each successive treatment (e.g. 3 treatments in all) - the 40 1 final treatment yielding the target or desired shade. In each ¦ case, after applying the mixture of colorant and oxidant to the ¦ hair, development of the coloration is permitted to occur over a I ¦ specified period which is the same for each treatment (e.g. 5, ¦ 10 or 15 minutes). The composition is then rinsed from the hair 1 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.
.
~ 1~)7;~
¦ The process of the invention is convenient for use ¦ without professional assistance, since the user - in ~ach treat-5 ¦ ment - has only to measure a specified constant quantity of ¦ colorant solution, mix it with a similarly measured quantity of l oxidant solution - the quantities in successive treatments after 10 ¦ the first being advantageously simple multiples of the amount l 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.
he following examples, wherein parts and percentages 20 ¦ are by weight, illustrate the process of the invention:
l Example 1 25 ¦ An aqueous vehicle containing surfactants commonly ¦ employed in shampoos and pH adjusting agents is prepared having 30 ¦ 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 diethanolamine35 parts Ma-laurylpolyethyleneglycol ether sulfate 60% 100 parts Na lauryl sulfate 30%200 parts Two colorant solutions are prepared having the following compo-sitions - the first (A) providing light brown as the target shade, and the second (B) yielding a medium brown as the target shade:
10'7381'7 ¦ ~esorcinol 2.5 parts2.5 parts ¦ p-phenylenediamine 6.0 parts8.0 parts 5 ¦ p-tolylenediamine sulfate 2.0 parts5.0 parts ¦ p-aminophenol 3.o parts6.0 parts ¦ 2,4-diaminoanisole sulfate 0.25 parts 2.5 parts 10 ¦ p-methylaminophenol sulfate 1.0 parts0.0 parts l Perfume (Lavender) 5.0 parts5.0 parts 15 ¦ De-ionized water 302.0 parts30~.0 parts Vehicle as above 693.0 parts693.0 parts I Totals 1014.75 parts1024.0 parts 20 ¦ The resulting colorant solutions have a pH of 9.5, which promotes ¦ decomposition of H202 and its peroxy derivatives.
25 1 As the oxidant for use with the foregoing colorant so-¦ lution, 6% (i.e. 20-volume) H202 is used, or an aqueous solu-¦ tion of an equivalent quantity of urea peroxide, Na perborate 30 ¦ or Na percarbonate can be used - replacing - if desired - part ¦ of the water with propylene glycol to facilitate dissolution.
35 1 In use, 30 cc. of colorant solution A is mixed for the ¦ first treatment with 2.5 cc. of oxidant solution. The mixture l is applied to the hair and allowed to develop for 5 minutes, a 40 ¦ 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 ~ 1073817 ¦ 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 ¦ ~hree 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 (E), a light brown:
C D E
¦ 1. De-ionized water 56.864~ 57.410% 59.51%
30 ¦ 2. Trisodium ethylenediamine-¦ tetracetic acid 0.488 0.493 0.49 3. Sodium sulfite 0.684 0.690 0.68 35 ¦ 4. Borax 1.465 1.478 1.46 ¦ 5. Morpholine 1.953 1.970 1.94 l 6. Sodium lauryl-polyethylene-40 ¦ glycol ether sulfate (60%) 9.766 9.854 9.71 l 7. Sodium lauryl sulfate (30%) lg.531 19.709 19.42 45 ¦ 8. N-lauroyl-diethanolamide 6.418 6.449 4.85 9. Resorcin 0.244 0.246 0.24 l 10. Paraphenylenediamine0.781 0.591 0.58 50 ¦ 11. Para-aminophenol 0.586 0.296 0.29 O-~8~
¦ 12. Paratolylenediamine sulfate 6.118 0.197 0.29 55 ¦ 13. 2,4-diaminoanisole sulfate 0.244 0.25 0.05 13a. Paramethylaminophenol sulfate _ 0.099 -l 14. Perfume (lavender) 0.488 0.493 0.49 60 1 100.--% 100.~ 100.--%
¦ To prepare the foregoing colorant solutions, the ¦ water (1) is heated in a mixing kettle to 80 degr. C. 2, 3, 4 and 5 ¦ 5 are added successively, each being completely dissolved before ¦ addition of the next. 6 and 7 are then added at the same temper-¦ ature. 8 and 9 are then successively added at a temperature of 10 ¦ 70 degr. C. 10, 11, 12 and 13 (and 13a in composition D) are ¦ added, and agitation continued for lS minutes. The mixture is 15 ¦ cooled to 40 degr. C. and 14 is then added.
¦ Example 3 20 ¦ Two colorant solutions are prepared having the following compositions - the first (F) yielding a light brown as the target l shade - and the second (G), a medium dark brown:
25 ~ 1. De-ionized water 56.84% ~-L~r~
l 2. Trisodium ethylenediamine-30 ¦ tetracetic acid0.48 0.47 ¦ 3. Sodium sulfite 0.67 0.66 ¦ 4. Borax 1.44 1.41 5. Monoethanolamine1.92 ~,t~
6. Sodium lauryl-polyethyl-eneylycol ether sulfate (60~) 9.59 13.39 7. Sodium lauryl sulfate (30%) 19.18 20.78 8. N-lauroyl-diethanolamide 5.36 7.29 9. 4-chloro-resorcinol0.515 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,S-diaminoanisole O-SO
sulfate ~,o~r 14. Perfume (lavender)0~48 0.47 ~ 1073817 ¦ Colorant solutions F and G are prepared in su~stantially ¦ 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 l.
¦ The quantity of oxidant employed in the first treat-¦ ment 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 l 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 l.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 advantageous-ly ranges from lO to 25%, that of the pH ad~usting components from 2 to 10%, and that of the aromatic primary aromatic amino group compounds and aminophenols Iwith the coupler or couplers), from 0.5 to 8%.
~5 illustrated in the examples, the quantities of oxi-;~ ~ dant 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 (l, 2, 4) - or simple multiples (l, 2~ 3, 4). A geometric series of multiples is pre-ferred, since it yields a substan~ially linear darkening of the . ..... :. . . . . .: .. , :
10'73817 ¦ hair in attaining the target shade. In each case, the develop-¦ ment 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 I form of their water-soluble salts, such as sulfates, hydrochlor-¦ ides or acetates - may be selected from the following:
15 ¦ o-, p- and m-phenylenediamine ¦ p-aminodiphenylamine ¦ p-aminodiphenylamine sulfonic acid 20 ¦ 2-amino-4-nitrophenol ¦ 4-amino-2-nitrophenol 25 ¦ p-aminophenol m-aminophenol o-aminophenol 30 ¦ o-, m- and p-methylaminophenol 2-aminophenol-4-sulfonic acid ~35 ¦ 4-aminophenol-2-sulfonic acid ; I ¦ o-anisidine ~ 2,4-diaminoanisole I
40 ¦ . 2,5~diaminoanisole ¦ p,p'-diaminodiphenylamine p,p'-diaminodiphenylamine sulfonic acid : 45 l p,p'-diaminodiphenylmethane ::~ 1,8-diaminonaphthalene 2,4-diaminophenol -2,4-diaminophenetole : 50 2,5-diaminophenol-4-sulfonic acid N,N'-dimethyl-p-phenylenediamine
4,6-dinitro-2-aminophenol N-(p-hydroxyphenyl)-glycine :107;~817 N-(2-hydroxy-5-nitrophenyl)-glycine p-methylaminophenol 4-nitro-o-phenylenediamine m- and p-tolylenediamine l 2,4,6-trinitroaniline 10 ¦ Couplers which can be used in the colorant solution l are, for example, polyhydric phenols such as resorcinol, chloro-
5 ¦ resorcinols, pyrocatechol, pyrogallol and hydroquinone.
Surfactants suitable for inclusion in the colorant l 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;
~5 ¦ higher fatty acid alkylolamides; polyalkyleneglycols; and ethylenediamine-tetracetic acid alkali metal or ammonium salts.
l 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, l 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 H202 such as urea peroxide, alkali metal perborates, -percarbonates, -perphosphates, -persulfates or -periodates, as well as H202 itself.
Other variations and modificatisns 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.
Surfactants suitable for inclusion in the colorant l 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;
~5 ¦ higher fatty acid alkylolamides; polyalkyleneglycols; and ethylenediamine-tetracetic acid alkali metal or ammonium salts.
l 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, l 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 H202 such as urea peroxide, alkali metal perborates, -percarbonates, -perphosphates, -persulfates or -periodates, as well as H202 itself.
Other variations and modificatisns 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 (16)
1. A process for dyeing hair by application of a mixture of colorant solution of primary aromatic amines and aminophenols and an oxidant containing H202 or a peroxy derivative for a time period yielding color development followed by a rinse removal of the residual mixture;
the improvement to the aforesaid process comprising;
(a) applying said colorant-oxidant mixture in successive applications to gradually get rid of the undesirable hair color, wherein (i) the time period of application of the mixture being short, on the order of five (5) to fifteen (15) minutes and of substantially the same length for each subsequent application, (ii) the quanitity of colorant solution is suitable for moistening a head of hair uniformly, and substantially constant through all applications, (iii) the quantity of oxidant in the mixture in the first application is 0.5 to 2 times the amount required to oxidize the primary aromatic amines and aminophenols contained in the colorant solution, and successive applications having increased quantities of oxidant above said initial quantity, ranging up to 10 times the amount required for the aforesaid oxidation;
(b) each mixture having the ability to produce an 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 with the mixture of colorant and oxidant last used.
the improvement to the aforesaid process comprising;
(a) applying said colorant-oxidant mixture in successive applications to gradually get rid of the undesirable hair color, wherein (i) the time period of application of the mixture being short, on the order of five (5) to fifteen (15) minutes and of substantially the same length for each subsequent application, (ii) the quanitity of colorant solution is suitable for moistening a head of hair uniformly, and substantially constant through all applications, (iii) the quantity of oxidant in the mixture in the first application is 0.5 to 2 times the amount required to oxidize the primary aromatic amines and aminophenols contained in the colorant solution, and successive applications having increased quantities of oxidant above said initial quantity, ranging up to 10 times the amount required for the aforesaid oxidation;
(b) each mixture having the ability to produce an 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 with the mixture of colorant and oxidant last used.
2. A process as defined in Claim 1 wherein the quantity of oxidant admixed with the colorant solution in the first treat-ment is 0.5 to 2 times the amount required to oxidize all of the aromatic primary amines and the aminophenols contained in the colorant solution, and ranges up to 10 times said amount in the last treatment of the series yielding a target shade.
3. A process as defined in Claim 2 wherein the quantity of oxidant admixed with the colorant solution in each treatment of the series after the first is a simple multiple of the quantity 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.
5. A process as defined in Claim 4 wherein the quanti-ties of oxidant employed in the successive treatments of the series are substantially in the ratio of 1, 2, and 4.
6. A process as defined in Claim 1, wherein the color-ant solution includes, as a coupler, a polyhydric phenol.
7. A process as defined in Claim 1, wherein the color-ant solution comprises a surfactant.
8. A process as defined in Claim 1, wherein the oxi-dant is selected from the group consisting of H202, urea perox-ide, and per-salt derivatives of H202.
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 oxi-dant is employed in a solution of which the concentration is equivalent in oxidizing potential to that of a solution of H202 of about 6% concentration.
11. A process as defined in Claim 1, wherein the quan-tity 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.
of the mixture applied in each of the successive treatments is within the range of 8 to 10.
13. A process as defined in Claim 1, wherein the color-ant solution contains 2.5 parts resorcinol, 6-8 parts p-phenyl-enediamine, 2-5 parts p-tolylenediamine sulfate, 3-6 parts p-aminophenol, 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 Na-laurylpolyethyleneglycol ether sulfate, 60 parts Na lauryl sulfate, and about 793 parts water, and the oxi-dizing solution is 6% H202.
14. A process as defined in Claim 1 wherein the color-ant solution contains 0.24 - 0.246 parts resorcinol, 0.58 - 0.781 parts paraphenylenediamine, 0.29 - 0.586 parts para-aminophenol, 0.197 - 0.488 parts paratolylenediamine sulfate, 0.05 - 0.25 parts 2,4-diaminoanisole sulfate, up to 0.099 parts p-methylamino phenol 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-polyethylene-glycol-ether sulfate (60%), 19.42 - 19.709 parts sodium lauryl sulfate (30%), 4.85 - 6.449 parts N-lauroyl-diethanolamide and 56.864 - 59.51 parts water.
15. A process as defined in Claim 1 wherein the colorant solution contains 0.515 parts 4-chlororesorcinol, 2.13 parts paratolylenediamine sulfate, 0.745 parts meta-aminophenol sulfate, 0.65 parts para-aminodiphenylamine sulfate, up to 0.50 parts 2.5-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 monoethanolamine, 0.47 - 0.48 parts ethylenediamine-tetracetic acid trisodium salt, 9.59 - 13.39 parts sodium lauryl-polyethylene-glycol ether sulfate (60%), 19.18 - 20.78 parts sodium lauryl sulfate (30%), 5.36 - 7.29 parts N-lauryl-diethanolamide and 48.32 - 56.84 parts water.
16. A process as defined in Claim 1 in which the time period of each application of the mixture is constant.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US69088576A | 1976-05-28 | 1976-05-28 | |
| US05/789,076 US4104021A (en) | 1976-05-28 | 1977-04-20 | Process for dyeing hair in which the depth of shade is gradually increased in successive treatments |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1073817A true CA1073817A (en) | 1980-03-18 |
Family
ID=27104696
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA277,720A Expired CA1073817A (en) | 1976-05-28 | 1977-05-05 | Process for dyeing hair in which the depth of shade is gradually increased in successive treatments |
Country Status (20)
| Country | Link |
|---|---|
| JP (1) | JPS52148634A (en) |
| AT (1) | AT372276B (en) |
| AU (1) | AU507404B2 (en) |
| BR (1) | BR7703464A (en) |
| CA (1) | CA1073817A (en) |
| CH (1) | CH623741A5 (en) |
| DE (1) | DE2722979A1 (en) |
| DK (1) | DK235077A (en) |
| FI (1) | FI65908C (en) |
| FR (1) | FR2352542A1 (en) |
| GB (1) | GB1542034A (en) |
| GR (1) | GR82248B (en) |
| IE (1) | IE45066B1 (en) |
| LU (1) | LU77379A1 (en) |
| MX (1) | MX148039A (en) |
| NL (1) | NL172822C (en) |
| NO (1) | NO145457C (en) |
| PH (1) | PH13324A (en) |
| PT (1) | PT66609B (en) |
| SE (1) | SE7705460L (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2460664A1 (en) * | 1979-07-10 | 1981-01-30 | Oreal | TINCTORIAL HAIR COMPOSITIONS BASED ON PARAPHENYLENEDIAMINE AND ORTHOAMINOPHENOL |
| DE3016905A1 (en) * | 1980-05-02 | 1981-11-05 | Henkel KGaA, 4000 Düsseldorf | HAIR DYE |
| US4535957A (en) * | 1983-07-18 | 1985-08-20 | Goodyear Aerospace Corporation | Safety device for venting aircraft tires |
| DE3510039A1 (en) * | 1985-03-20 | 1986-09-25 | Henkel KGaA, 4000 Düsseldorf | HAIR DYE |
| JPS6335406A (en) * | 1986-07-28 | 1988-02-16 | Hoou Kk | Composition containing hydrogen peroxide |
| JPH0720852B2 (en) * | 1988-06-08 | 1995-03-08 | 花王株式会社 | Keratin fiber dyeing composition |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3649159A (en) * | 1968-06-03 | 1972-03-14 | Fmc Corp | Hair coloring method using a peroxydiphosphate oxidant |
| US3871818A (en) * | 1972-10-30 | 1975-03-18 | Avon Prod Inc | Promoting color change in human hair with a dialdehyde compound and a nitrogen containing compound |
| US3920384A (en) * | 1974-07-17 | 1975-11-18 | Clairol Inc | Autoxidizable hair dye containing preparations |
-
1977
- 1977-05-03 PH PH19771A patent/PH13324A/en unknown
- 1977-05-05 CA CA277,720A patent/CA1073817A/en not_active Expired
- 1977-05-10 SE SE7705460A patent/SE7705460L/en unknown
- 1977-05-13 NO NO771707A patent/NO145457C/en unknown
- 1977-05-17 NL NLAANVRAGE7705458,A patent/NL172822C/en not_active IP Right Cessation
- 1977-05-20 DE DE19772722979 patent/DE2722979A1/en not_active Ceased
- 1977-05-20 LU LU77379A patent/LU77379A1/xx unknown
- 1977-05-23 GR GR53538A patent/GR82248B/el unknown
- 1977-05-25 AT AT0372177A patent/AT372276B/en not_active IP Right Cessation
- 1977-05-26 GB GB7722308A patent/GB1542034A/en not_active Expired
- 1977-05-26 FI FI771683A patent/FI65908C/en not_active IP Right Cessation
- 1977-05-26 IE IE1087/77A patent/IE45066B1/en unknown
- 1977-05-27 DK DK235077A patent/DK235077A/en unknown
- 1977-05-27 CH CH656177A patent/CH623741A5/en not_active IP Right Cessation
- 1977-05-27 JP JP6126877A patent/JPS52148634A/en active Pending
- 1977-05-27 FR FR7716357A patent/FR2352542A1/en active Granted
- 1977-05-27 PT PT66609A patent/PT66609B/en unknown
- 1977-05-27 BR BR7703464A patent/BR7703464A/en unknown
- 1977-05-27 AU AU25578/77A patent/AU507404B2/en not_active Expired
- 1977-05-30 MX MX169228A patent/MX148039A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| FR2352542B1 (en) | 1981-07-31 |
| IE45066L (en) | 1977-11-28 |
| PT66609A (en) | 1977-06-01 |
| GB1542034A (en) | 1979-03-14 |
| NL7705458A (en) | 1977-11-30 |
| FR2352542A1 (en) | 1977-12-23 |
| IE45066B1 (en) | 1982-06-16 |
| FI65908B (en) | 1984-04-30 |
| BR7703464A (en) | 1978-03-14 |
| AU507404B2 (en) | 1980-02-14 |
| NL172822C (en) | 1983-11-01 |
| FI65908C (en) | 1984-08-10 |
| AU2557877A (en) | 1978-11-30 |
| LU77379A1 (en) | 1977-08-29 |
| FI771683A (en) | 1977-11-29 |
| DE2722979A1 (en) | 1977-12-08 |
| NO145457B (en) | 1981-12-21 |
| MX148039A (en) | 1983-03-08 |
| NO145457C (en) | 1982-03-31 |
| CH623741A5 (en) | 1981-06-30 |
| NO771707L (en) | 1977-11-29 |
| SE7705460L (en) | 1977-11-29 |
| ATA372177A (en) | 1983-02-15 |
| GR82248B (en) | 1984-12-13 |
| PT66609B (en) | 1978-10-25 |
| PH13324A (en) | 1980-03-13 |
| DK235077A (en) | 1977-11-29 |
| AT372276B (en) | 1983-09-26 |
| JPS52148634A (en) | 1977-12-10 |
| NL172822B (en) | 1983-06-01 |
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