J. Soc. CosmeticChemists,20, 595-602 (Sept. 16, 1969)

ShampooHair Coloring Compositions for Direct Dyeing of Human

Hair FULVIO

SARDO, Ph.D.*

Presented December 3, 1968, New I'ork City

Synopsis--A discussionis presented concerning direct dyeing of hair with nonionic disperse dyes such as nitro arylamines, azo dyes, and anthraquinones. Semipermanent shampoo hair color preparations are also illustrated.

INTRODUCTION

A direct dye is a dye which penetratesinto the hair shaft and gives color to the hair without simultaneousor subsequentmanipulation such asreactionwith peroxides. Accordingto Giles (1), a dye is taken up by the fiber (absorbed) becausethe two combineto form a chemicalcompound. This compound may not be a well-definedsubstance,but it is a compoundnevertheless. In the caseof direct dyeing, the reaction between fiber and dye is reversible and the compoundcan be made to break up into its constituents; that is, dye and fiber can be separatedand restoredto their original state unchanged. This processbecomesvery apparent when a dyed fiber is washedwith a surfactantat relativelyhigh temperature. * Present address: Viale Italia 97, 98100 Messina, Italy. 595

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For effectivedirect dyeing to occur (1), the combiningpower of fiber and dye must overcomethe attraction which the water has for the dye. This can happen only if the dye molecule has certain arrangementsof groupsof atoms which give it specialattraction (affinity) for the fiber, causingthe formation of firm bonds.

DIRECT

DYEINC

WITH NONIONIC

DYES

The use of various typesof nonionic dyes in the direct dyeing of hair has been long known. Representativeof thesenonionicdyesare the socalled "dispersedyes" which were originally developedfor useon cellulose acetate but which are now usedon a wide variety of the newer synthetic fibers. These dyes fall into three clearly defined chemical classes: the nonionicnitro arylamine dyes, the nonionicazo dyes (1), and the nonionic anthraquinone dyes. Substantially, all these dyes contain amino groupsbut no solubilizinggroupssuchassulfonicor carboxylicradicals. Some processespreviously proposedfor dyeing hair with such "disperse dyes" have generally involved the use of elevated temperature heating caps which, of course, greatly reduce the desirability of such compositions. Other attemptsto use "dispersedyes" in the coloringof human hair have involved the use of suchdyes in combinationwith anionic surfactantsof varioustypes. Shampoosare particularly desirablevehiclesfor applying hair coloring compositions. Numerousattemptshave been made to producecompositionswhich can be usedto cleanseand color human hair satisfactorilyand simultaneously. The shampoo-coloringcompositionsbased on direct dyes produced sofar, however,have all fallen short of the desireddegreeof effectiveness, either in their failure to achievesignificantcleansingof the hair or in their failure to give satisfactorycoloringeffects.

DIRECT DYEINC

WITH

BASIC DYES

Shampoohair coloringcompositionscomprisingbasicdyes and basic quaternizeddyes(2, 3) havetwo main deficiencies: (a) Hair, unlike a syntheticfiber, is not uniform. Becauseof the action of sunlight, or previouschemical treatments(4), it has undergone irreversible chemical reactions. Different sections(roots, shafts, ends, etc.) leavedifferent chemicalan,d physicalcompositions. For thisreason,

SHAMPOO

HAIR

COLORING

COMPOSITIONS

597

when hair coloringcompositionscomprisingbasicand basicquaternized dyes are applied to the hair, the color deposit is very heavy at the ends and light at the root area. Consequently, an undesirable, over-all, uneveneffectisproduced.

(b) Many basicand basicquaternizeddyes in aqueousvehiclesat acid and alkaline pH are chemically unstable and consequentlyhave a very short shelf-life. The following dyes were evaluated by the author at

a concentrationof 0.2% in aqueoussolutionscontainingvarioustypesof surfactantsat pH of 4, 6, and 8. Basic Violet

1

Basic Yellow

11

Basic Violet

16

C.I.

42535

C.I.

48055

C.I.

48013

Basic Blue 7

C.I.

42595

Meldola

C.I.

51175

Basic Blue 1

C.I.

42025

Basic Blue 26

C.I.

44045

C.I.

42120

Blue

Basic Blue 5 Basic Yellow Bismarck

Safranine Rhodamine

1

C.I.

49005

Brown

C.I.

21010

C.I.

50240

C.I.

45160

CG 6 CG

Storageconditionswere at 40ø C and at ambient temperature. The dyes were unstable at both conditions. The instability is seen in the color depositedon white hair and sometimesin the color of the dye solution.

Spectrophotometric readings of these solutionsfour weeks later between 400 and 800 m/• indicated a considerableshift of the absorption curvesascomparedto the control.

DIRECT

DYEING

WITH

ANIONIC DYES

Effective coloring shampoocompositionsbased upon anionic acid dyes which satisfactorilycleanse and dye the hair cannot be achieved, since these dyes do not deposit any color on the fiber in presenceof the considerableamount of surfactant required to formulate an effective shampoo.

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SHAMPOO HAIR

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COLORING COMPOSITIONS

The nonionic 'Cdispersedyes" which have been previously described can be used in the formulation of hair coloring shampoos. Such a compositioncan be used to shampoothe hair effectively with the formation of a rich lather while achieving adequate cleansingof the hair and simultaneouslyand rapidly imparting a uniform color deposition. The following are formulas for semipermanent shampoo hair colors which, when applied to hair treated with double-process permanent

colors*(toners),are able to restorethe colorwhich hasfaded throughthe action of detergents,light, and other atmosphericconditions. These types of shampoohave the dual function of washing the hair and, at the same time, depositingon the hair the color which has faded. The deposit of color on the hair is instantaneousand can be removed only through severalwashingswith a detergent. Example

Disperse Violet 4 Disperse Black 3 Disperse Violet 1 Pluronic L 64• Miranol SM coned. SFI: Atomonyx LO õ Stearic

acid diethanolamide

2% 8

0 0 11 33

o

11

o

1 o

2 o

Hydrochloric acid to pH5 Water q.s. to 100 ApplicationProcedure

One ounce of the undiluted shampoo described in Example 1 was applied to strongly bleached hair uniformly on the roots and on the ends and

was worked

out

until

a foam

was obtained

and

then

was rinsed

thoroughly and dried. The hair appeared cleansedand was left with a uniform

ash blonde

color.

* Double-processpermanent hair color is defined as a hair color which requires two steps: bleachingfor one to two hours with a strong peroxide bleach followed by applying hair coloring for one-half

hour.

t Wyandotte Chemical Co., Wyandotte, Mich. 1:The Miranol Chemical Co., 277 Coit St., Irvington, N.J. õ Onyx Chemical Co., 190 Warren St., Jersey City, N.J.

SIIAMPOO

HAIR

COLORING

COMPOSiTiONS

599

Example2 Disperse Violet 1 Disperse Violet 4 Disperse Black 3 Pluronic

L 64

o6% O9 06 10 0

Cocodimethyl betainc (30%)

3O 0

Ammonyx LO

10 0

Arquad 2HT 100'

O5

Lauric

2O

acid diethanolamide

Hydrochloric acid to pH5 Water q.s. to 100 Application of the shampoodescribedin Example 2, according to the application proceduredescribedin Example 1, to strongly bleached hair produceda lather and left the hair with a soft,warm beige color.

Example3

The repeated use of mild bleach compositionsoften producesbrassy red tonesin the hair. The followingcoloringshampoocompositionwas effectivelyusedto correctand subduesuchbrassytones. DisperseViolet 4 Disperse Blue 1 Phenylglycolether

1.1 t•o 0.2

3.0

Polyoxyethylene(100) hydroabietyl alcohol

10.0

Miranol

SM concd. SF

25.0

Aromox

DMCD*

10.0

SuperamideGRt Hydrochloric acid to pH5 Water q.s. to 100

2.0

This shampooapplied on the hair accordingto the applicationprocedure described in Example 1 left the hair well cleansed and it removed the brassyred huespresentin the hair beforeshampooing.

* Armour Chemieal Co., Box 1805, Chicago, Ill. t Onyx Chemical Co., 190 Warren Street, Jersey City, N.J.

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Example4

Permanent hair color compositionsbased upon p-phenylenediamine or p-toluylenediaminein combination with hydroxyphenolsand amino and nitro phenols have shown considerabledisadvantages. Thus, for example, the light fastnessis insufficient. Furthermore, after a time a marked visible shift towards red hues occurs. The following coloring shampoo composition was effectively used to correct and subdue red hueson an originally dark ashbrown shade.

DisperseViolet 4

1.1%

Black

0.5

A

DisperseViolet 1

0.2

Polyoxyethylene(20) oleyl ammonium chloride

2.0

Polyoxyethylene(100) hydroabietyl alcohol Benzyl alcohol Miranol

SM

concd.

SF

Atomonyx LO Hydrochloric acid to pH5 Water q.s. to 100

8.0 4.0 30.0

10.0

Example5

The following coloring shampoocompositionwas effectivelyused to impart a brilliant platinumcolorto virginyellow-greyhair.

DisperseViolet 4

1.

Benzyl alcohol

4.0

Polyoxyethylene(20) oleyl ammonium chloride Polyoxyethylene(100)

2.0

hydroabietyl alcohol 1,3-Dimethyl thiourea

8.0 4.0

Miranol

SM

concd.

SF

Atomonyx LO Stearic

acid diethanolamide

Hydrochloric acid to pH5 Water q.s. to 100

30.0

10.0 2.0

SHAMPOO

HAIR

COLORING

COMPOSITIONS

601

HAIR COLORING COMPOSITION WITH SOME CLEANSING AND FOAMING PROPERTIES

The uptake of "dispersedyes" by the hair can be increased to achieve shadesof considerabledepth by using vehicleswhich are much lesseffective in their cleansingand foaming properties. Such compositions,which cannot be considered shampoosin the traditional sense, have, however, some cleansing properties due to the presenceof a solvent as well as a surfactant. Moreover, they do produce somefoaming, due mainly to the large amount of product which must be applied on the hair to achieve the desiredtinctorial effect (80 to 100 g as comparedto 15 to 30 g usedfor a normalshampoo). Example6 Celliton

Black

Celliron

Red

BTNA

Celliron

Brown

Violet

2.25% RNA

3 RA

0 069

0 30 0 15

CalcosynDiazo Black NSHS SarcosylO*

4 O0

Butyl alcohol

8 O0

'•-"--:--

1 O0

QP 15000•

Ammonia 28•o to pH 9.5 Water q.s. to 100 ApplicationProcedure

One hundred gramsof the productwasuniformlyapplied to dry grey hair and was worked up until some foam was produced. The product was then left for 20 to 45 minutes depending on the intensity of the shade desired. After cleansingand drying, the hair appeared fairly clean and was left with a dark brown to black color deposit. Example7

A dark brown uniformshadewasobtainedwhen the followingformula was applied to grey hair using the same application procedure as in Example 6.

* Geigy Chemical Co., Saw Mill River Road, Ardsley, N.Y. t Union Carbide Chemical Co., 270 Park Avenue, N.Y., N.Y. 10017

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Celliton

Black BTNA

Celliton

Red Violet

Celliton

Brown

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9% RNA

0 23

3 RA

0 45 25

CalcosynDiazo Black NSHS SarcosylL

0 4

n-Butanol

8 00

CellosizeQP 15000 Ammonia 28% to pH 9.5 Water q.s. to 100

00 CO

CONCLUSION

Shampoo compositionsfor direct dyeing of human hair based upon nonionic"dispersedyes,"suchasnitro arylamines,azo dyes,and anthraquirtones,can be producedwhen thesedyesare dispersedin a suitable vehicle. Suchcompositions can be usedto shampoothe hair effectively with the formation of a rich lather, while achievingadequate cleansing, and simultaneouslyand rapidly imparting a uniform color deposition. The uptake of "dispersedyes" by the hair can be increasedby using vehicles which are much less effective in their cleansing and foaming properties.

(ReceivedDecember20, 1968) REFERENCES

(1) Giles, C. H., Notesfor a LaboratoryCoursein Dyeing, Societyof Dyers and Colourists. Yorkshire, England, 1957, p. 80.

(:2) Stead,C. V., Recentdevelopmentin the chemistryof hair dyes,Am. PerfumerCosmetics, 79, 31 (Feb., 1964). (3) Warner Lambert PharmaceuticalCo., Morris Plains, N.J., Hair coloringcompositions comprisinga basic dye, a glycol and an amphoteric surfactant, U.S. Patent 3,194,735 (July 13, 1965).

(4) Chesebrough-Pond's, Inc., New York, N.Y.,

Hair coloring shampoo, U.S. Patent

986,712 (March 28, 1963). ($) Zahn, Helmut, Bleachingof wool and human hair with hydrogenperoxideand peracids, J. Soc. CosmeticChemists,17, 687 (1966).