US 3592581 A
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United States Patent Oflice Patented July 13, 1971 DYEING OF HUMAN HAIR WITH INSOLUBLE PHTHALOCYANINE DYESTUFFS IN A CATIONIC DISPERSION Albert Shansky, Norwalk, Conn., and Alan Gary Schuster, Amityville, N.Y., assignors to Del Laboratories, Inc., Farmingdale, N.Y. N Drawing. Filed Aug. 8, 1968, Ser. No. 751,075
Int. Cl. A61k 7/12 US. Cl. 8-101 3 Claims ABSTRACT OF THE DISCLOSURE A system for semi-permanently dyeing human hair by plating out a water insoluble phthalocyanine dyestuif onto a cationic layer ensheathing hair strands and acting as a dye coupler for the dyestutf. The cationic layer is applied to the hair strands from an aqueous medium in which the cationic material and water insoluble phthalocyanine dyestuff constitute a single composite mixture with the cationic compound as an ingredient in intimate contact with the dyestuff and acting as a dispersant so as to obtain uniform distribution of the dyestuff in the aqueous medium and leveling of the dyestuff as a waterfast dye on the hair substrate.
BACKGROUND OF THE INVENTION (1) Field of the invention A dyeing system for human hair wherein an insoluble phthalocyanine dyestuff dispersed in an aqueous medium by a cationic dispersant is plated out as a waterfast dye onto a hair substrate that is coated with the cationic dispersant now acting as a dye coupler present as a layer on the hair shafts.
(2) Description of the prior art One of the present methods of dyeing human hair is referred to as temporary dyeing since the color is easily removed by shampooing. In this method, dyes such as nigrosine, resorcine brown, amarinth yellow, methylene blue, and gentian violet are coupled to hair strands. However, a major defect of such temporary dyeing products is their inherently light pastel colors. These light colors often have an artificial appearance and many of them are substantially or even completely removed when the hair is wetted with water. Temporary dyeing is practiced on hair on the human head; however, it also can be practiced on human hair not on the head, for example, wigs, switches, falls and wiglets. It is customary and, indeed, as a practical matter, almost imperative, for temporary dyeing to be practiced on light-colored hair, such, for example, as white hair, gray hair and stripped hair, that is to say that hair which is essentially uncolored.
SUMMARY OF THE INVENTION The present invention is concerned with an improved system of temporary dyeing of human hair, the new system, like the previous system, being applicable both to hair on the human head and to human hair off the head in the many forms in which it is available. Similarly, the present invention finds its principal advantage in the dyeing of non-colored hair, which is to say, white,
gray and stripped hair. It is to be noted that the stripped hair need not be completely stripped. The present invention will work Well with hair that has been partially stripped providing that the applied dyestuff is somewhat darker than the undyed hair. The stripping only has to be sufiicient to be a shade lighter than the ultimate color to be applied to the hair by the present invention.
It is an object of the invention to provide a system of the character described in which the dyeing of the hair, although temporary in a sense, is permanent to the extent that the dyestutt will not be removed when the dyed hair is wetted with water, i.e. the applied dye is waterfast; that is to say it is an object of the invention to provide such a system in which the dyestuff is water insoluble, although removable by shampooing, and in which the dyestuff is coupled to the hair by a water insoluble bond.
It is another object of the present invention to provide a method of dyeing human hair in which the resulting color will be as deep in shade, if desired, as a natural hair color.
It is another object of the invention to provide a system of the character described pursuant to which the dyeing of hair is accomplished more conveniently than it was heretofore by a permanent dye method.
It is another object of the invention to provide a system of the character described which will readily and fully satisfy the capricious nature of female patrons.
It is another object of the invention to provide a product which permits dyestuffs that are insoluble in water to be used in aqueous media for the dyeing of human hair.
It is another object of the invention to provide hair dyeing compositions which will fulfill the objects set forth above.
The present invention is based on the discovery that a certain type of water insoluble dyestuff dispersed in an aqueous medium will plate out on human hair, either on the head or off the head, the strands of which are coated with a cationic surfactant compound in the form of a layer that acts as a dye coupler binding the water insoluble dyestuff to the hair strands in a fashion such that the ensuing dye is waterfast but removable by shampooing.
Prior to application to the hair, the cationic surfactant compound even in the presence of the aforesaid special type dyestuff will not act as a dye coupler. This is an important achievement of the invention since it enables the cationic surfactant compound and the dyestuff to be applied to the hair from an aqueous medium in which the two, to wit the cationic surfactant compound and the special type of dyestuff, are present in a single composite aqueous mixture (composition) with the cationic surfactant compound in intimate contact with the dyestuff.
The dyestutf will be transferred from the aqueous medium to hair from the single composite aqueous composition, the cationic surfactant compound depositing as a layer on the hair shafts prior to deposition of the special dyestuff thereon. It has been observed that upon transference of the dyestuif to the human hair substrate a dye leveling is accomplished by the cationic surfactant compound which also acts as a dispersant prior to the application of the dyeing mixture to the hair strands, that is to say, as a dispersant for the water insoluble special dyestutf. Thereby, which is to say, by the dye leveling function, the cationic surfactant compound prevents an over build-up of the special dyestuff on the hair strands.
By the use of this dyestutf dispersing system, it has become possible to use dyestuffs for the dyeing of human hair which heretofore have been unsuitable for this purpose owing to their water insoluble character. However, in the system of the present invention, such water insolubility, instead of being a drawback, becomes an advantage because it prevents the loss of color which heretofore took place when the hair was wetted after having been dyed.
Nevertheless, the water insoluble dyestuif because of the special method of coupling the same to human strands through the use of a cationic dispersant can be removed with ease merely by shampooing. Hence the hair is, in effect, permanently dyed" for ordinary usage; but the dyestuff can be taken olf any time it is desired to change the same simply by resorting to shampooing so that a woman is not limited to the permanent presence of a given color water insoluble dyestuff on her hair and can have the same removed and a new color substituted with great case.
In the current vogue where fashion demands, or various occasions may call for, changes in hair color, it is not necessary for a woman patron to subject her hair to stringent dye stripping operations for the removal of ordinary permanent dyes since her new semi-permanent dyeing of the present invention can be removed and replaced without harsh treatment of her hair.
The dyestulfs of the present invention are phthalocyanine derivatives. The cationic compound is a cationic surfactant which is adsorbed by human hair from an aqueous medium to leave a coating layer thereof on the surface of the hair on to which the dyestuffs will plate and be coupled. 'Ihe cationic surfactant also acts as a dispersant in water for the water insoluble phthalocyanine dyestuff.
It is also useful to incorporate a non-ionic dispersant along with the cationic dispersant to improve dye dispersion as well as to enhance dye leveling. Furthermore to increase stability over a long-term shelf life, it is useful to employ a non-ionic thickener. The particulation of the dyestutf in the aqueous medium may be improved (made smaller in size) by use of a stabilizing agent that is a liquid wherein the dyestuff is initially soluble.
DESCRIPTION OF THE PREFERRED EMBODIMENTS The special type of dyestuffs which are critical to the proper functioning of the present invention must have the following properties:
( 1) They must be water insoluble.
(2) They must be phthalocyanine derivatives having the general formula:
Fe is a phthalocyanine radical which is either metal free or, more advantageously, metal-containing, in particular, heavy metal-containing, and, principally, coppercontaining;
x,, is a radical of a polyalkylene polyamine containing at least one lipophilic radical and at least 3 basic nitrogen atoms, which polyalkylene polyamine is bound at a terminal N atom to the S group;
x is the ammonium cation of such a polyalkylene polyamine; and
n and m are positive integers, m+m being equal to 2 to 4, m being at least 1 and n being 0, 1, 2, or 3.
.r and x are polyalkylene polyamine radicals of the general formula:
it being observed that an H of either R or R condenses with an OH of the suphonic acid group to link thereto.
Of the symbols R R R R and R at least one R represents a lipophilic radical. The lipophilic radical preferably is a saturated branched chain aliphatic group, advantageously containing 8 to 16 and, preferably, 8 to 12, carbon atoms, for example, the octyl, iso-octyl, decyl or dodecyl group. However, it is within the scope of the invention for the lipophilic radical to be an araliphatic group, for example, the benzyl group, which con contain saturated aliphatic substituents, eg a tertiary butyl, tertiary amyl, octyl, iso-octyl, decyl or dodecyl group. Also, if desired, the lipophilic radical can be a cycloaliphatic group, for example, a cyclohexyl group. The remaining Rs advantageously constitute hydrogen. However, they can also constitute a lower aliphatic group of one to two carbon atoms, for example, a methyl or ethyl group. In that part of the amine of Formula II, corresponding to x,,, however, at least one R must be hydrogen.
Each of Q and Q constitutes a lower alkylene radical, advantageously an o e-alkylene radical such as, for example, the l,2-propylene radical and, preferably, the 1,2- ethylene radical. However, each of Q and Q can also be an urn-alkylene radical such as, e.g., the 1,3-butylene radical and preferably the 1,3-propylene radical. Preferably Q and Q are the same. p represents a positive integer, preferably l, 2 or 3.
The dyestuffs of the general Formula I are well-known dyestuff; however, for the purpose of further identification it may be mentioned they can be obtained by reacting one mole of a phthalocyanine compound of the general Formula III with m-l-n moles of a polyalkylene polyamine which contains at least one lipophilic radical and at least 3 basic nitrogen atoms. The reaction time typically is about hours at atmospheric pressure at a temperature of between about 20 to about C. The formula for the phthalocyanine compound is:
[SOiCll sotZ] wherein:
Fe, m and n have the definitions given above and wherein Z is hydrogen, an alkali metal or an ammonium ion.
The aforesaid reaction is advantageously performed in an aqueous suspension and with the addition of inert organic solvents which are miscible with water and of acid combining agents, all as is well-known in the art.
The dyestulfs of Formula I, i.e. the dyestulfs constituting phthalocyanine derivatives as specified, are powders of various colors most of which are blue-black and yield various colors as will be specified hereinafter when applied to the hair in accordance with the invention and also in diluted aqueous dispersions.
The dyestuffs are insoluble in water and are difliculty soluble in lower alkanols, such as, e.g. methanol or ethanol, as well as in lower ketones such as acetone. On the other hand said phthalocyanine derivative dyestuffs are easily soluble in several higher alcohols, such as, e.g. benzyl alcohol, or in several ether alcohols, such as e.g. diethylene glycol monoalkyl ethers, e.g. in diethylene glycol monomethyl ether.
The present invention provides hair dyeing compositions which essentially comprise an aqueous liquor, i.e. medium, containing a colored substance selected from the group consisting of one or more of the aforementioned water insoluble phthalocyanine derivative dyestuffs in an amount of between about 0.15% to about 0.25% by weight based on the total weight of the composition, and a cationic surfactant (dispersant) which is dispersible in water, rises to a maximum and then decreases again as the which is adsorbed by human hair from the hair dyeing amount of cationic dispersant present is further increased. composition, leaving a layer thereof on the surface of the Although the method and system will not work without hair, and which is a dispersant in water for the said water this cationic dispersant, a concentration in excess of the insoluble dyestuif at room temperatures. The said water maximum figure of 1.5% by weight only improves dye insoluble dyestuif is adsorbed by human hair coated with dispersion with a simultaneous reduction of color rendithe cationic surfactant from the water based dispersion at tion. For this reason a non-ionic dispersant may be inroom temperatures. The cationic dispersant in this coated cluded in addition to the cationic dispersant in order to form serves as a dye coupler for the aforementioned improve the dye dispersion without reducing color rendiphthalocyanine water insoluble dyestuffs; although it does 10 tion, as well as to alTord an improved dye leveling effect not couple to the said dyestuffs in said water dispersion on the fiber through surface detergency. The preferred prior to coating on hair strands. The cationic dispersant non-ionic dispersant is a nonyl phenoxy poly(ethyleneis one selected from the class of compounds constituting oxy)ethanol (4 moles ethylene oxide) selected from the higher alkyl (C is equal to 14 to 22) dimethyl benzyl class, of which others are usable, constituting nonyl pheammonium chlorides. The said dyestuffs will plate onto 15 noxy poly(ethyleneoxy) ethanols with from 4 to 7 moles such coated hair strands. of ethylene oxide. The preferred range for the non-ionic In general, for any given dye of the general class of dispersant of the class mentioned is from about 0.1% to phthalocyanine derivative dyestuffs as above defined, there about 2.5% by weight based on the total weight of the will be one or more cationic dispersants which possess the w t based dyeing composition. Properties listed above, to Wii hair Strand a g, ye Since the hair dyeing composition used in the process p ng. ye l l ng and aqueous i p r i n f h y and system of the present invention is a dispersion, it is Sillif, Which Tender it Useful for the method and system prudent to further include a thickener in order to main- Of the Present il'lvbniioh- Similariy, y given Cationic tain stability and uniformity of the dispersion over a long dispersant as above defined, there will be a number of the term h lf lif F thi purpose, there preferably is emaforesaid phthalocyanine derivative dyestuffs WhiCh are ployed a non-ionic compound in rder to prevent ancillary dispersibib y Said dispersant in all aqueous medium and reactions with the cationic dispersant of the water based which ca be used fiiiificiiveiy in the meihOd and system dyeing composition of the present invention. A thickener 0f the Pfesfiht invention for y g human hail Oii and 011 found to function excellently in this connection is a nonihe human head, which hair Preferably is While, g y 0f ionic hydroxy ethyl ether cellulose which preferably, when stripped to a color level lower than the ultimate color l d, i d i a range f from b t 1 0% t b t level to be Obtained by the dyeing method and y 2.0% by weight based on the total weight of the com- T m u t f the Said Cationic dispersant Contained in position. The thickener is also useful, upon suitable octhe water based hair dyeing composition varies accordi t prevent in f th o ition when ing to the specific aforementioned phthalocyanine derivali d t a mass f human h i tive dyestufi' employed and to the amount of dyestulf used Th f ll i constitutes a li of i l h min the aforesaid range. cyanine derivative dyestuffs useful in the practice of the For a given concentration of dyestutl' in the aforesaid present i i range, there is an optimum value in the range of from about 0.25% to about 1.5 by weight based on the total PHTHALOCYANINE DERIVATIVE DYESTUFF A weight of the composition for the amount of cationic dis- 40 (COPPER-CONTAINING) F -SOz-N-CHz-NCHZ-NCCH CCH3 I /2 /z (IIHa )1 CH3 J SO.'| NCH N-CHN-C-CH;CCH;
/a /2 \clH: 2 CH5 This dyestuff is a blue-black powder and when diluted and used in the range aforementioned and in the example concentration of phthalocyanine derivative dyestuff in the i fg h g figgig E g a smoke color to white gray aforesaid range of 0.15% to 0.25% by weight based on a nppe the total weight of the composition, as the amount of PHTHALOCYANINE DERIVATIVE DYESTUFF B cationic dispersant is increased, the efficiency of dyeing (COPPER-CONTAINING) H H SO N- CH N CH persant which should be used, at which value maximum efficiency of the dyeing operation is achieved. For a given 8 This dyestutf is a blue powder and when diluted and used This dyestuif is a blue-green powder and when mixed in the range aforementioned and in the example given with an equal amount of dyestufi C and used in the range hereafter will impart a slate color to white, gray and stripped human hair. PHTHALOCYANINE DERIVATIVE DYESTUFF C 5 (COPPER-CONTAINING) This dyestuff is a purple-black powder and when diluted aforementioned and in the example given hereafter will and used in the range aforementioned and in the exam- 30 dye hair black at maximum dilution.
PHTHALOCYANINE DERIVATIVE DYE/STUFF E (METAL FREE) H N N N TI IIN 1 QJLL 9J so; N \CH N CH N c n,
ple given hereafter will impart a pearl color to white, This dyestuff is a greenish-blue powder and when diluted gray and stripped human hair. 55 and used in the range aforementioned and in the exam- PHTHALOCYANINE DERIVATIVE DYESTUFF I) (COPPER-CONTAINING) Z' 1 S0 N-CH-NCH NCH HCH OH L"\*/ \77 \7."
N N K 0* N ple given hereafter will impart a gray-blue color to white, The aqueous base dyeing composition of the present gray and stripped human hair. invention is advantageously repared by adding the thick- PHTHALOCYANINE DERIVATIVE DYESTUFF F ener (the non-ionic hy xy ethyl ether cellulose) to (IRONCONTAINED) 75% of the final water/volume and mixing the same. Then I" J -S()Q*N--CIIQN CH N- C H *0 H N J R This dyestuff is a red powder and when diluted and used 20 the cationic dispm-Sam (the alkyl dimethyl benzyl in [he afiolememioned and in the e xample given monium chloride) is added to and mixed with the above hefeafter lmpflrt a red Color to White gray and thickener solution before swelling of the thickener is compp human halrpleted, for example before about one hour.
H ALOC AN DERIVATIVE DYESTUFF G A previously made hot, e.g., about 150 F., mixture of (CHROMIUgLCONTAINED the dyestufl solvent (the benzyl alcohol), the non-ionic F "f 1 so NOH N0H -NCH 0H L /i\ /i\/ 1i N l LN N This dyestufi" is a yellow powder and when diluted and dispersant, e.g., the nonyl phenoxy poly(ethylene0xy) used in the range aforementioned and in the example ethanol and the water insoluble phthalocyanine derivative given hereafter will impart a yellow color to white, gray dyestutf is added, with stirring, to the solution of the thickand stripped human hair. ener and cationic dispersant until dispersion of the dye- It is also desirable to incorporate in the aqueous liquor r stuff is atfected. Now, if perfume is desired, the same is composition a stabilizing agent for the water insoluble added. Finally, the balance of the Water is added, Wheredyestuff. Benzyl alcohol is excellent for this purpose. Its upon the water base liquid dyestuff composition is ready function is to provide a vehicle through the incorporafor use. tion of a soluble form of the dyestuif (the dyestuff is solu- The water based dyeing composition is applied to the ble in benzyl alcohol) in the dispersion so as to cause a hair in a conventional fashion. As noted previously, the
smaller initial particulation of the dyestulf in water (when 50 hair must be human hair either on or off the head and the the benzyl alcohol dissolved dyestuif is added to the hair preferably is white, gray or stripped, either fully or water) than can be realized by mechanical means such, partially. A typical series of steps for dyeing hair of the for instance, as ball milling. Where benzyl alcohol is aforesaid character is first to shampoo and towel dry the employed, it is present in the amount of from about 1% hair. Then enough of the aqueous dyeing composition, e.g. to about 4% by Weight based on the total weight of the about 1 02., is applied to and combed thoroughly through composition. the hair. The excess product is rinsed out with lukewarm The following is an example of a water based hair water. dyeing composition embodying the present invention: It Will be found that the dyeslulf Will be Plawd 011 to the hair coated with the cationic dispersant. It will be Ingredlents: Percentage by Welght permanent to the extent that the dye color imparted to the Water insoluble phthalocyanine derivative dyestuffs 0.2 hair is Waterfast- However, it y can be readily Benzyl alcohol (dyestufl ol 5 rem ved simply by shampooing the hair with any standard Stearyl dimethyl benzyl ammonium chloride (catsoap. Moreover, it will be observed that the ensuing colors i i dispersant) 1 P will range, depending upon the particular dyestuffs or com- Nonyl phenoxy poly(ethyleneoxy)ethanol (4 moles blnations thereof employed and their dilution, from light to ethylene Oxide) (nomiomc f t t) 0 dark tones, and can be as deep in shade as desired, even Non-ionic hydroxy ethyl ether cellulose (thickener) 1.5 F P as natural hair COIOFS Such as dark brown and Water (to make up balance) 92.8 mack- H It thus will be seen that there are provided a system and Typical alternative cationic dlspersants which can be dyeing compositions which achieve the various objects of Substituted in the foregoing example for the yl dithe invention and which are well adapted to meet the conmethyl benzyl ammonium chloride are: myristyl dimethyl ditions of practical use.
benzyl ammonium chloride, palmityl dimethyl benzyl am- As various possible embodiments might be made of monium chloride, arachidyl dimethyl benzyl ammonium the above invention, and as various changes might be chloride and behenyl dimethyl benzyl ammonium chloride. 75 made in the embodiments above set forth, it is to be understood that all matter herein described is to be interpreted as illustrative and not in a limiting sense.
Having thus described the invention, there is claimed as new and desired to be secured by Letters Patent:
1. A method of waterfastly dyeing white, gray or stripped human hair, said method comprising, applying to the hair about one ounce of an aqueous dyeing composition composed of an aqueous medium containing a water insoluble phthalocyanine dyestuff dispersed in the aqueous medium by a cationic dispersant, said dispersant being adsorbed by the hair and leaving a layer thereof coated on the hair strands, said layer acting as a dye coupler on which the dispersed water insoluble phthalocyanine dyestufi is plated, said water insoluble phthalocyanine dyestuff having the formula:
l orxelm mea -[Ken wherein Fe is a phthalocyanine radical selected from the class consisting of and n and m are positive integers, m+n being equal to 2 to 4, m being at least 1 and n being 0, 1, 2, or 3; x is a polyalkyleue polyamine radical of the formula:
-QA T IM R2 x is the ammonium cation of such polyalkylene polyamine;
an H of either R or R being condensed with an OH of the sulphonic acid group to link thereto;
at least one R of R R R R and R being a lipophilic radical selected from the class consisting of a saturated branched chain aliphatic group contain ing from 8 to 16 carbon atoms, a benzyl group, a benzyl group with saturated aliphatic substituents selected from the class consisting of tertiary butyl, tertiary amyl, octyl, iso-octyl, decyl and dodecyl groups and a cyclohexyl group, the remaining Rs being selected from the class consisting of hydrogen, methyl and ethyl, at least one R of x being hydrogen;
each of Q and Q being selected from the class consisting of 1,2-propylene, 1,2-ethylene, 1,3-butylene and .1,3-propylene; and p being a positive integer from 1 to 3; wherein the cationic dispersant is a higher alkyl dimethyl benzyl ammonium chloride having from 14 to 22 carbon atoms in the alkyl radical; and
wherein the water insoluble phthalocyanine dyestuff is present in an amount of between about 0.15% to about 0.25% by weight based on the total weight of the composition and the cationic dispersant is present in an amount of between about 0.25% to about 1.5% by weight based on the total weight of the composition.
2. A method as set forth in claim 1 wherein the composition further includes a non-ionic dispersant constituting nonyl phenoxy poly(ethyleneoxy) ethanol with 4 to 7 moles of ethylene oxide in an amount of between about 0.1% to about 2.5% by weight based on the total weight of the composition.
3. A method as set forth in claim 1 wherein the composition further includes a stabilizing agent for the water insoluble phthalocyanine dyestuli, said stabilizing agent being benzyl alcohol in an amount of between about 1% to about 4% by weight based on the total weight of the composition.
References Cited UNITED STATES PATENTS 2,795,585 6/1957 Muehlbauer 8-10X 3,057,873 10/1962 Pugin et al 260-3145 3,062,831 11/ 1962 Freyermuth et a1 810X FOREIGN PATENTS 363,963 10/ 1962 Switzerland.
ALBERT T. MEYERS, Primary Examiner V. C. CLARKE, Assistant Examiner US. Cl. X.R. 810, 85, 93