US3567355A - Mercaptans for boosting the dyeing of human hair with direct dyes - Google Patents

Mercaptans for boosting the dyeing of human hair with direct dyes Download PDF

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US3567355A
US3567355A US3567355DA US3567355A US 3567355 A US3567355 A US 3567355A US 3567355D A US3567355D A US 3567355DA US 3567355 A US3567355 A US 3567355A
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thioglycolic acid
ester
acid
dyeing
hair
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Karl-Josef Boosen
Gunter Reese
Peter Berth
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THERACHEMIE CHEM THERAPEUT
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THERACHEMIE CHEM THERAPEUT
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/30Cosmetics or similar toilet preparations characterised by the composition containing organic compounds
    • A61K8/46Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing sulfur
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILET PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/06Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A61Q5/065Preparations for temporary colouring the hair, e.g. direct dyes
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/42Colour properties
    • A61K2800/43Pigments; Dyes
    • A61K2800/432Direct dyes

Abstract

A PROCESS IS DISCLOSED FOR IMPROVING THE COLORING OF HUMAN HAIR, ESPECIALLY LIVING HUMAN HAIR, WITH DIRECT DYES BY THE USE OF MERCAPTANS WHICH ARE INSOLUBLE OR DIFFICULTLY SOLUBLE IN WATER. THE MERCAPTANS ARE MERCAPTOCARBOXYLIC ACID ESTERS AND AMIDES. EMULSIONS OR DISPERSIONS OF THE MERCAPTANS CAN BE USED TO TREAT THE HAIR PRIOR TO DYEING OR THEY CAN BE COMBINED WITH THE DYEING COMPOSITION.

Description

United States Patent Office 3,567,355 Patented Mar. 2, 1971 Int. Cl. A61k 7/12 US. Cl. 810.1 24 Claims ABSTRACT OF THE DISCLOSURE A process is disclosed for improving the coloring of human hair, especially living human hair, with direct dyes by the use of mercaptans which are insoluble or difficultly soluble in water. The mercaptans are mercaptocarboxylic acid esters and amides. Emulsions or dispersions of the mercaptans can be used to treat the hair prior to dyeing or they can be combined with the dyeing composition.

The invention relates to substances which boost the activity of dyeing agents for human hair, and more particularly to so-called direct dyes, applied to living human hair.

It has previously been proposed to improve the action of direct dyes on human hair, by treating the hair, prior to dyeing, with readily water-soluble mercapto compounds, such as thioglycolic acid or its alkali or ammonia salts. However, in practice the production of uniform and reproducible coloring had met with diflieulties because discoloration of the hair occurs. It therefore has also been suggested to carry out an ensuing treatment with oxidizing agents, such as hydrogen peroxide. However, this is an involved procedure and eliminates the advantages of the use of direct dyes which, by themselves, do not require the addition of oxidizers. Another considerable drawback upon the use of the known water-soluble mercapto compounds, e.g., thioglycolic acid or its alkali or ammonium salts, consists in the lack of storability of mixtures thereof with direct dyes.

The object of the invention is to present a process and agents for its accomplishment which facilitate coloring of human hair with direct dyes while avoiding the abovenamed disadvantages. This can be attained by treating the hair with aqueous dispersions or emulsions of mercaptans which are insoluble or difficultly soluble in water.

Mercaptans of this kind which lend themselves to the purpose are particularly mercaptocarboxylic acid esters, preferably alphaand beta-mercaptocarboxylic acids, and/ or mercaptocarboxylic acid amides.

To be considered therefore are such compounds as thioglycolic acid esters, thiolactic acid esters and beta-mercaptopropionic acid esters of primary, secondary and tertiary monoand bivalent alcohols, such as methyl-, dodecyl-, citronellyl-, tertiary heptyl alcohol, ethylene glycol monoethyl ether, diethylene glycol, cyclohexanol and phenol; furthermore, thioglycolic acid diethanolamide, thioglycolic acid bis (beta-hydroxyethoxyethyl)-amide and thioglycolic acid formamide.

In many instances the esters of thioglycolic acids, of thiolactic acid and of mercaptopropionic acid with alcohols such as ethyl-, propyl-, butyl-, isobutyl-, hexyl-, isoheptyl-, isooctyl-, octyland tetrafurfuryl alcohol and with diethyleneglycol monoethyl ether have proved especially applicable.

Of the mercaptocarboxylic acid amides, thioglycolic acid cyclohexylamide and N,-N-bis-(mercaptoacetyl)-1,6-hexamethylenediamine are especially to be mentioned.

The process can be carried out in such a manner that the hair first is treated with an emulsion or dispersion of the insoluble or difiicultly soluble substituted mercaptans named, followed by rinsing of the hair and dyeing with the direct dyes in the conventional manner.

Direct dyes suitable for the purpose are nonionic compounds based upon anthraquinone or aminoanthraquinone or azo dyes. Particularly, those dyestuffs named in British Pat. 957,119 can be employed or those sold under the name Celliton (registered trademark).

Anionic direct dyes also are applicable, especially those based on acid azo dyes and triarylmethane dyes and also corresponding anthraquinone and aminoanthraquin'one dyes.

Finally, cationic dyestuffs which dye directly also can be employed.

The dyes are employed in the conventional quantities of 0.1 to 5 weight percent, preferably 0.5 to 3 percent. However, when the effect of increased color intensity is not desired, the booster agents according to the invention facilitate a substantial decrease in the amount of dyestuif required, in some cases down to the amount otherwise used.

The booster liquids in the form of emulsions or dispersions containing the water-insoluble or difficultly soluble substituted mercaptans also can be applied as the last rinse after shampooing of the hair to be dyed. The concentration of the active ingredients in all instances is approximately 0.1 to 10 weight percent, and preferably 1 to 5 percent.

If desired, the booster treatment can also be combined with the dyeing process. The booster agents, in this case, are incorporated in the dyeing compounds either upon their manufacture or shortly before application. It goes without saying that chemical compatibilities of the booster with the other materials present must be considered. It is feasible not to use just one of the water-insoluble or difiicultly soluble substituted mercaptans, but a mixture of several such compounds.

The pH value of the dispersions or emulsions containing these boosters can be adapted to the prevailing conditions. Equally good results are obtained when the pretreatment liquid or the last rinse after shampooing is not alkaline, but neutral or acid.

The agents can be mixed with any desired wetting agents, detergents and Washing agents, especially those which are anionic or nonionic. Suitable wetting agents, detergents and washing agents are especially alkylbenzene sulfonates, fatty alcohol sulfates, alkylsulfonates, fatty acid ethanolamides, addition products of ethylene oxide on fatty acids and fatty alcohols.

Furthermore, thickeners, e.g., methylcellulose, starch, higher fatty alcohols, Vaseline, paraffin oil and fatty acids can be admixed, also perfumes, i.e., essential oils, or hair grooming agents such as pantothenic acid and cholesterol.

These admixtures are employed in the quantities customary for the purpose. Wetting agents and detergents particularly are employed at 0.5 to 30 weight percent, thickeners in amounts of 0.1 to 25 weight percent, calculated on the total composition. The concentration of the direct dyes depending upon the purpose amounts to up to 5 weight percent, preferably however to 0.1 to 2 weight percent, also calculated on the total composition.

The advantage of the novel process according to the invention reside in the feasibility of considerably reducing the amount of dye to be used without materially detracting from the color intensity; or, when using the customary amounts of dyestuif, to increase the intensity considerably. Other advantages are that not only the action of the dye on the human hair is improved, but that resistance to abrasion and rubbing ensues. The singular effects named to a certain extent depend upon the boosting agent used and especially on the kind of dyestuif employed. W 1

Finally, a particularly great advantage is found in the fact that mixtures of direct dyes with 'the water-insoluble or difficultly soluble substituted mercaptans named are storable for great lengths of time. These mixtures adv'alntageously are used in practice in the form of creams or pastes; Hair dyes containing water-soluble merca pto compounds cannot be stored for any length of time (see, e.g., Example 7 below). The invention now will be further expiained by the following examples. However, it should be understood that these are given merely by way of illustration and not of limitation, and that numerous changes may be made in the. details without departing from the spirit and the scope of the invention as hereinatferclaimedj 1 EXAMPLE 1 A strand of naturally greyed human hair was saturated with a 1 weight percent aqueous solution of a dyestuif having Formula 1 O 7 NH, I 1

t The solution had been adjusted to a pH of 9.5 with aqueous ammonia and was allowed to act on the hair for 20 minutes at room temperature. This was followed by shampooing and rinsing. The 'hair thus treated 'had a light red color. Y a

When the dyeing solution was fortified with 1 weight percent thioglycolic acid isobutylester, dispersed therein, a briliiant deep red color was attained.

EXAMPLE 2 A dyeing cream was prepared from 8 weight parts cetylstearyl alcohol, 2 weight parts fatty alcohol C C 9 weight parts fatty alcohol .sulfate C C by heating these components to 80 C., adding 0.2 weight part 2,2}- diaminoazobenzene, 0.4 weight part 4,4'-diaminoazobenzene, 0.4 weight part l,4diamino-5-(1',4,7-trioxanonyl) anthraquinone, and 2 weight parts thioglycolic aeid isopropylester, and emulsified at this temperature with 70 parts water of like temperature. After cooling to 40 C., the pH was adjusted to 9.5, and the emulsion made up to 100 parts with water. The dyeing cream thus obtained colored'living human grey hair to a beautiful dark brown.

Withthe same dyeing process, but without theaddition of the thioglycolic acid isopropylester, a brown color also was obtained which, however, had a much weaker hue.

EXAMPLE 3 Aqueous solutions or dispersions, respectively, were produced containing as dyestufi 1,4-diamino-2-chloro-3- (l',4 ',7'trioxanonyl-anthraquinone and. as a booster 5 weight percent of one of the compounds listed in Table 1. The pH of these dispersions ,was adjusted to 9.5 with ammonia. Grey hair was treated with these coloring baths for-20 minutes at room temperature, rinsed with wate and shampooed.

In all instances the color obtained" was a distinct improvementpver the light red color which was produced in the like process *but without the boosters named.

Corresponding results were obtained when, in lieu of the dyestuif named, a dye was used as listed in Table 2.

4 7 EXAMPLE 4 0 l rH t (2) which had been adjusted to a pH of 9.5 with ammonia. The dye was allowed to act for 20 minutes at room temperature, and the hair was then'shampooed. A light red color was obtained. H i

An intensively brilliant red' color ensued when, at otherwise like working conditions, the hair was treated, prior to dyeing, with an aqueous-ammoniacal emulsion of 5 weight percent thioglycolic acid tertiary-butyl ester of zi pH of 9.5 for 20 minutes at room temperature.

Similar results were obtained when the pretreatment with the thioglycolic acid tertiary-butyl ester emulsion was carried out when this emulsion had a pH of 2 or of 7.

EXAMPLE 5 i Aqueous dispersions were produced containing as a cationic dyestulf 0.3 weight percent crystal violet and as booster one of the compounds named in Table 3 in the amounts named therein. The dispersions were adjusted to a pH'of 9.5 with ammonia. Living grey human hair was treated with these dispersions for 20 minutes at room II I . temperature. After completed dyeing the hair was shampooed and dried.

having a pH of 9.5. After dyeing, the hair was shampooed,

.rinsed and dried. It had a brilliant red color. Changes in the time of action of the pretreatment to between 10 seconds and 30 minutes effected corresponding differences in the shading of the coloring obtained.

Without the .boosting: action of the thioglycolic acid tetrahydrofurfuryl ester, the red coloring was considerably weaker in all instances.

A brilliant red color also was obtained whenthe pretreatment batlr had a pH of 2 or of 7.

EXAMPLE 7 Naturally grey living human hair was treated for 20 minutes at room temperature with a solution containing 1 weight percent of a dyestuif having Eormula 4 e e 1 in s Oz--CH3 EXAMPLE 8 Grey hair was treated with an aqueous solution containing 1 weight percent of a dye having Formula 3 (see also Example 6) adjusted to a pH of 2.5, for 20' minutes at room temperature. The hair assumed a weak red color.

A strong red color was obtained when, at other-wise like treatment, the dyeing solution contained 5 weight percent thioglycolic acid hexyl ester.

TABLE 1 No. Material 1- Thioglycolic acid methyl ester. 2 Thioglycolic acid ethyl ester. 3- Thioglycolic acid propyl ester. 4 Thioglycolic acid butyl ester.

5 Thioglycolic acid hcxyl ester.-

6- Thioglycolic acid octyl ester.

7 Thioglycolic acid dodecyl ester.

. Thioglycolic acid tetrahydrofuriuryl ester.

Thioglycolic acid citronellyl ester.

. Thioglycolic acid isopropyl ester.

Thioglycolic acid isobutyl ester.

12 Thioglycolic acid isoheptyl ester.

13 Thioglycolic acid isooctyl ester.

14. Thioglycolic acid tertiary-butyl ester.

15 Thioglycolic acid tertiary-heptyl ester.

16. 'Ihioglycolic acid ethylene glycol monoethyl ether ester. 17..-- Thioglycolic acid diethylene glycol ester.

18. Thioglycolic acid diethylene glycol monoethyl ether ester. 19...- Thioglycolic acid phenyl ester.

Thiolactic acid ethyl ester.

Beta-mercaptopropionic acid butyl ester.

2 Thioglycolicacid cyclohexamide.

23. N,N'-bis-(mercaptoacetyl) -1,6-hexamethylenediamine.

TABLE 2 Name of dye Color Index No. Supracene Red G 17045 Supracene Red B 17070 Supracene Violet 4 BF 620 Supracene Blue GE Acid Blue 66 Isolane Grey BRLS Acid Black 140 TABLE 3 Weight No. Material percent 1 Thioglycolic acid diethanolamide 3 2 Thioglyoolic acid hydro'xyethoxyethylamide 1 3 Thioglycolic acid-di-(hydroxyethoxyethyl)amide- 2 TABLE 4 Weight No. Material percent 1 Thioglycolic acid ethyl ester 3 2 Thioglycolic acid hexyl ester 3 3 'Ihioglyeolic acid tetrahydroiurfuryl ester 3 g Thioglycolic acid isopropyl ester g 3 3 i Thioglycolic acid diethanolaznide 5 N,N-bis-(mercaptoacetyl)-1,6-hexamethylenediamine 5 6 EXAMPLE 9' Coloring baths :were produced containing 1 weight percent of an anionic dyestulf having Formula 3 (see Examand further containing as booster one of the compounds listed in Table 4 in the quantities named therein. The dyeing liquid was adjusted to a pH of 9.5 with aqueous ammonia.

Living human hair was dyed by treating it with these liquids for 20 minutes at room temperature. After dyeing, the hair was shampooed and dried. In all instances, the coloration was a considerable improvement over the weak red color obtained under the same conditions but without the presence of the booster in the dyeing liquid.

What is claimed is:

1. A process for boosting the action of a directdye on human hair which comprises treating said hair substantially at room temperature with a dispersion of substantially 0.1 to 10 weight percent of compounds selected from the group consisting of water-insoluble or difiicultly soluble esters of thioglycolic acid, thiolactic acid, beta mercaptopropionic acid with primary, secondary and tertiary mono and divalent alcohols; thioglycolic acid diethanolamide, thioglycolic acid mono and dihydroxyethyl amide, thioglycolic acid formamide, thioglycolic acid cyclohexamide, N,N -bis- (mercaptoacetyl) -1,6-hexarnethylene diamine, and mixtures thereof and thereafter applying said dye.

2. A process according to claim '1 wherein said alcohols are citronellyl alcohol, mono and diethylene glycol monoethyl ether, diethylene glycol, cyclohexanol, phenol, tetrafurfuryl alcohol, or mixtures thereof.

3. A process according to claim 1, in which said com pound is thioglycolic acid ethyl ester.

4. A process according to claim 1, in which said compound is thioglycolic acid butyl ester.

5. A process according to claim 1, in which said compound is thioglycolic acid dodecyl ester.

6. A process according to claim. 1, in which said compound is thioglycolic acid isopropyl ester.

7. A process according to claim 1, in which said compound is thioglycolic acid isobutyl ester.

8. A process according to claim 1, in which said compound is thioglycolic acid isooctyl ester.

9. A process according to claim 1, in which said compound is thioglycolic acid tertiary-butyl ester.

10. A process according to claim 1, in which said compound is thioglycolic acid tertiary-heptyl ester.

11. A process according to claim 1, in which said compound is thiolactic acid ethyl ester.

:12. -A process according to claim 1, in which said compound is beta-mercaptopropionic acid butyl ester.

13. A process for boosting the action of a direct dye on human hair which comprises treating said hair substantially at room temperature with the application of said dye in a dispersion of substantially 0.1 to 10 weight percent of compounds selected from the group consisting of water-insoluble or diflicultly soluble esters of thioglycolic acid, thiolactic acid, beta mercaptopropionic acid with primary, secondary and tertiary mono and divalent alcohols; thioglycolic acid diethanolamide, thioglycolic acid mono and dihydroxyethoxyethyl amide, thioglycolic acid formamide, thioglycolic acid cyclohexamide, N,N bis-(mercaptoacetyl)-16-hexamethylene diamine, and mixtures thereof.

14. A process according to claim 13 wherein said alcohols are citronellyl alcohol mono and diethylene glycol monoethyl ether, diethylene glycol, cyclohexanol, phenol, 24. A process according to claim 13, in which said tetrafurfuryl alcohol or mixtures thereof. compound is beta-mercaptopropionic acid butyl ester.

15. A process according to claim 13 in which said compound is thioglycolic acid ethyl ester. References Cited 16. A process according to claim 13, in which said 5 UNITED STATES PATENTS compound is thiogly-colic acid butyl ester.

17. A process according to claim 13, in which said g::

compound is thioglycolic acid dodecyl ester.

18. A process according to claim 13, in which said compound is thioglycolic acid isopropyl ester. 10 a 19. A process according to claim 13, in which said FOREIGN PAFSEITITS compound is thioglycolic acid isobutyl ester. 833,809- 4/1960 Great i f 16788 20. A process according to claim 13, in which said 906,526 9/1962 Great Bntam 167*88 compound is thioglycolic acid isooctyl ester.

21. A process according to claim 13, in which said 2,615,828 10/1952 Haefele .....16787.1

15 ALBERT T. MYERS, Primary Examiner compound is thioglycolic acid tertiary-butyl ester. V. C. CLARKE, Assistant Examiner 22. A process according to claim .13, in which said compound is thioglycolic acid tertiary-heptyl ester. XR

23. A process according to claim 13, in which said 92 71 72 compound is thiolactic acid ethyl ester. 20

US3567355A 1964-09-02 1965-08-26 Mercaptans for boosting the dyeing of human hair with direct dyes Expired - Lifetime US3567355A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3966397A (en) * 1969-03-28 1976-06-29 Lever Brothers Company Dyeing keratinous fibers
US5161553A (en) * 1986-09-19 1992-11-10 Clairol Incorporated Process for simultaneously waving and coloring hair
US5356439A (en) * 1992-09-14 1994-10-18 Shiseido Co., Ltd. Non-oxidative permanent dye formulation for hair and synthetic fibers
US5942009A (en) * 1997-03-28 1999-08-24 Brg, Ltd. Same-day waving and coloring of hair
WO2012038114A3 (en) * 2010-09-20 2012-10-18 Henkel Ag & Co. Kgaa Colour preservation by means of conditioning agents containing reducing agents
WO2015086269A1 (en) * 2013-12-12 2015-06-18 Henkel Ag & Co. Kgaa Method and kit for straightening and colouring hair with enhanced grey coverage and enhanced wash resistance

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE832593C (en) * 1948-03-11 1952-02-25 Ciba A G A process for dyeing animal fibers
BE553139A (en) * 1955-12-10
BE561572A (en) * 1956-10-13

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3966397A (en) * 1969-03-28 1976-06-29 Lever Brothers Company Dyeing keratinous fibers
US5161553A (en) * 1986-09-19 1992-11-10 Clairol Incorporated Process for simultaneously waving and coloring hair
US5356439A (en) * 1992-09-14 1994-10-18 Shiseido Co., Ltd. Non-oxidative permanent dye formulation for hair and synthetic fibers
US5942009A (en) * 1997-03-28 1999-08-24 Brg, Ltd. Same-day waving and coloring of hair
WO2012038114A3 (en) * 2010-09-20 2012-10-18 Henkel Ag & Co. Kgaa Colour preservation by means of conditioning agents containing reducing agents
WO2015086269A1 (en) * 2013-12-12 2015-06-18 Henkel Ag & Co. Kgaa Method and kit for straightening and colouring hair with enhanced grey coverage and enhanced wash resistance

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