US2338745A - Dyeing of hair - Google Patents

Description

Patented Jan. 11, 1944 UNITED STATES PATENT OFFICE and Warren John Zinck, Woodstown, N. J.

signors to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Application March 15, 1940, Serial No. 324,084

7 Claims. (Cl. 167-88) This invention relates to dyeing hair and to new compositions and processes for such purposes, and especially to the dyeing of human hair such as hair on living persons.

Heretofore numerous substances having atiinity for hair have been proposed as dyes for the hair, among which are the metal dyes which produce unnatural effects, the vegetable dyes which often produce weak dyeings or give dyeings only in a small number of shades, combinations of metal and vegetable dyes which have one or all the defects of their several constituents and the oxidation dyes which are amino derivatives of aromatic compounds and develop color upon applying oxidizing agents after they are applied to the hair. Use of the latter compounds generally requires preliminary tests which are made on concealed hairy parts of each individual to determine the probable effect of the compound on his hair since the reaction of hairs of all persons is not the same toward these compounds. Another disadvantage of the oxidation dyes arises from the fact that considerable time, say a day or so, is required after the dyeing has been made to determine whether the ultimate shade and effect of the compounds on the hair will be satisfactory or similar to the aproximation indicated by the preliminary test. The most of the oxidation hair dyes are toxic to living persons and the least toxic among them are generally harmful to some individuals. It is therefor desirable to, provide hair dyes, especially dyes for the hair of living persons which will preserve the natural appearance of hair, will produce a large variety of shades and can be operated easily and 'conveniently to produce final results in a very short space of time.

It is among the objects of the present invention to provide new compositions and processes for dyeing hair. Another object is to provide compositions which will produce colored hair having a natural appearance and in a large variety of shades. Another object of the invention is to provide such compositions and processes which will give final results rapidly and satisfactorily at relatively low temperatures. Another object is to provide rapidly acting hair dyes with good fastness properties without deleteriously affecting the natural appearance of the hair. Still other objects of the invention will be apparent from the following more detailed description.

The objects of the invention are attained in general'by applying a mildly heated solution of a suitable inorganic salt to premordant the hair and then applying a mildly heated water solution of a suitable soluble synthetic organic dye or of a mixture of such dyes.

The invention will be more fully set forth in the following more detailed description which includes examples that are given as illustrative embodiments of the invention and not as limitations thereof. Parts are expressed in parts by weight unless otherwise noted.

Example I Medium brown human hair which had been bleached was wet with a one-half percent solution of ferrous sulfate to premordant the hair. The temperature of the solution was about F. After about ten minutes and while the hair was still moist the hair was again wet with the following acidified mixture which had been heated to about the same temperature.

The solution was applied with cotton.

fiubic centimeters Pontachrome Fast Yellow R (C. I. 343) (A% solution) 50 Du Pont Alizarine Blue Black B (C. I. 1085) solution) 5 3% solution of acetic acid (glacial) 2 Water 43 By a similar treatment of bleached human hair as that described in Example I and using the following acidified developing mixture instead of the mixture recited in Example I, a satisfactory dyeing in a golden brown shade was produced Cubic centimeters Pontachrome Fast Yellow R (/2 solution) 50 Du Pont Allzarine Blue Black solution) 12 3% solution of acetic acid (glacial) 2 Water 35% lowing dye mixture.

Example 111 By a similar treatment as that described in Example I and using the following dye solution instead of the mixture recited therein, a dyeing in a light warm brown shade was produced.

Cubic centimeters Pontachrome Fast Yellow R (1% solution)- 18% Brown dye A (1% solution) 37 10 Du Pont Alizarine Blue Black (1% solution) 12% 3% solution of acetic acid (glacial) -2 Water 31% Brown dye A is a water soluble disazo dye which in its acid form is represented by the formula 4- nitro-Z-amino phenolresorcim-naphthylamine- 5-sulfonic acid (Laurents acid) and is described in U. 8. Patent 2,117,707.

A satisfactory dyeing in a somewhat similar shade was produced in like manner .by the fol- Cubic centimeters Pontachrome Brown G (C. I. 238) (1% solution) 25 Du Pont Alizarine Blue Black B 1% solution)- 73 3% solution of acetic acid (glacial) 2 Dyeings in other shades of brown and reddish brown were similarly produced by the following Du Pont Alizarine Blue Black B 2% solution) 3% solution of aceticacid (glacial) 2 Example IV By following generally the procedure of Example I and using the following dye mixture instead of the mixture described in Example I, the hair was dyed satisfactorily in an auburn shade.

Cubic centimeters Brown dye A (1% solution) 22% Pontachrome Fast Yellow R (1% solution). 67% 3% solution of acetic acid (glacial) 10 By varying the proportions of the dyes used in this example and adding various small amounts of logwood, dyeings in various other shades of brown can be made as follows.

Example V Bleached hair was premordanted as described in Example I. While still moist, the hair was treated with the following dye solution in the manner described in Example I.

Cubic centimeters Pontachrome Fast Yellow R. (1% solution) 48 Brown dye A (1% solution) 48 Logwood crystals (1% .solution) 2 3% solution of acetic acid (glacia1).... 2

Thechair was dyed a fast light brown shade having a natural appearance.

Example v1 By varying the proportions of the yellow and brown dyestuffs in the dye composition of Example V and tinting with logwood, darker brown to black shades can be made on bleached hair by premordanting with iron sulfate and applying the dye solution in a manner similar to that described in Example I.

The following is illustrative of a dye composition suitable for producing a dark brown.

Cubic centimeters Pontachrome Fast Yellow R 1% solution) 46 Brown dyeA (1% solution) 47 Logwood crystals (C. I. 1246) (1% solution) 5 3% solution of acetic acid (glacial) 2 A still darker brown can be made by increasing the relative proportion of the brown dye in the above composition and decreasing the proportion of yellow dye.

Example VII A deep black dyeing of excellent fastness and appearance was produced, by using the following acidified dye composition and applying the premordanting and dye solutions similarly to that described in Example I.

. Cubic centimeters Brown dye A (1% solution) 38 Pontachrome Fast Yellow R (1% solution) 30 Logwood crystals (1% solution) 30 3% solution of acetic acid (glacial) 2 Example VIII By using on premordanted hair in a manner similar to that described in Example I, a dye composition consisting of 7 Cubic centimeters Pontachrome Fast Yellow R (1% solution)--- 97 1 Logwood crystals (1% solution) 3% acetic acid solution (glacial) 2 a fast and satisfactory ash blond dyeing was produced.

A light ash brown dyeing resulted from the use of the following composition.

I Cubic centimeters Pontachrome Fast Yellow R (1% solution) 96 Logwood crystals 1% solution) 2 3% acetic acid solution (glacial) 2 Etample IX Bleached hair was mordanted with iron sulfate solution as described in Example I and while moist the following dye composition was applied as described in Example I.

Cubic centi-' meters Brown dye A (1% solution) 68 Logwood crystals (1% solution) 30 3% solution of acetic acid (glacial) 2 The dyeing was a pleasing black shade'which had good light and washing fastness.

Example X A medium brown hair was prebleached to a golden brown with ammoniacal hydrogen peroxide in the manner well known in the art. A onehalf percent solution of ferrous sulfate was then heated to 110 F. and applied to the dry hair by brushing on the solution with a cotton swab.

After the application of the ferrous sulfa e: 6luance.

Example XI Prebleached hair was mordanted with a solution of ferrous sulfate as described in Example I. A one-half percent solution of Pontachrome Fast Red E (C. I. 652) in a 0.1% glacial acetic acid water solution was made and heated to 110 F. The solution was brushed on the premordanted hair by means of a cotton applicator. Final color developed within ten minutes after application of the dye. The hair was then thoroughly washed. An excellent fast re'd dyeing of a henna shade resembling natural hair in lustre, depth of shade and other appearance was produced.

By using Pontrachrome' Fast Yellow R instead of Pontachrome Fast Red E, yellow shades were produced.

By using Du Pont Alizarine Blue Black B indead of Pontachrome Fast Red E a fast bluish black shade of excellent natural lustre and appearance was produced.

Premordanting can be done with solutions of various water soluble lake forming metal salts such as copper, aluminum, chromium and iron. The iron salts, such as the chlorides, sulfates and acetate and of these the water soluble sulfates of ferrous iron are preferred, such as ferrous sulfate and ferrous ammonium sulfate. The iron salts work more rapidly at moderately low tempera tures than chromium salts, they produce shades which are more like the natural shades of hair than copper salts and they producesomewhat faster dyeings as a general rule than the aluminum salts. In the premordanting operation various concentrations of these solutions can be used from about 0.25% to about As the developing or dye solution, a solution of any of the various water soluble synthetic organic dyes from the classes of chrome, acid, direct, diazo or basic dyes can be used. When the 'hair is vpremordanted as described these dyes operate rapidly and produce a great variety of fast shades which can be varied in a number of ways as by using mixtures of the dyes. For dyeing human hair the dyes classifiable as water soluble chrome dyes are preferred and among such dyes the ones which are devoid of amine groups are preferred.

The term chrome dyes refers to the synthetic.

organic dyes which are generally applied on animal fibers with sodium or potassium bichromate or a neutral chromate by any one of three methods, i. e., -by premordanting with a chrome salt, by after chroming with a chrome salt, or by dyeing with dye and a chrome salt simultaneously and in the same bath. The term acid dyes refers to the synthetic organic dyes which are applied on animal fibers in a neutral or acid bath. The term direct dyes refers to the synthetic organic dyes which are generally applied on vegetable or cellulose fibers and which vary in their animal fiber dyeing properties. The term diazo dyes refers to those synthetic organic dyes which are generally applied on vegetable or cellulose fibers and which vary in their animal fiber dyeing properties. They can be dyed direct or coupled with beta naphthol, phenyl methyl pyrazolone, meta toluylene diamine or other coupling components of similar properties. The term basic dyes refers to those synthetic organic dyes which can be applied on animal fibers in a neutral or acid bath or on vegetable fibers "premordanted with a metallic salt or a tannin-bearing organic compound.

The dyes must be capable of being applied in the form of solutions and the term water soluble dye in the specification and claims refers to dyes which are readily soluble in water as well as to those which are more diflicultly soluble, such as those which can be more conveniently and rapidly put into solution .by first dissolving in a water soluble organic solvent, such as alcohol and then'diluting with water to the desired strength for use.

As other/illustrations of the many synthetic dyes which produce the described results and can be used alone orin mixtures of dyes similarly to those specifically recited, the following are mentioned as listed by color index number in C01- or Index edited by F. M. Rowe and published by the Society of Dyers and Colorists (England), namely, Color Index Numbers 10, 21, 101, 109, 151, 179, 203, 216, 234, 235, 246, 332, 420, 430, 561, 620, 640, 652, 655, 662, 696, 720, 749, 788, 789, 802, 814, 833, 841, 864, 865, 883, 909, 922, 1034, 1035, 1088 and 1091. Others to which Color Index numbers have not been assigned are anthranilic acid- 1 (o-chlor-m-sulfo-phenyl), 3 methyl- 5 pyrazalone, para phenylene diamine- 1z6 Cleves acid 1:6 Cleves acid-*F acid, Z-amino naphthalene-6 8-disulphonic acid-+meta toluidine- 1 :6 Cleves acidmeta toluidine-para amine benzoilated as described in U. S. P. 1,735,924, para nitro anilineaniline, para nitro anilineethyl, hydroxy ethyl aniline, 1-amino-2-methyl anthraquinone, 1-amino-4-hydroxy anthraquinone, diortho toluyl guanidine salt of C. I. 208 (U. S. P. 1,674,128), di-ortho' toluyl guanidine salt of amino G resorcin -amino G acid (U. S. P. 1,674,- 128) and 4-nitro-2-amino-phenol mixture of 4 partsv of meta-phenylene diamine and 1 part meta-toluene diamine -Laurents acid.

The developing or dye solution is preferably but not necessarily acidified. Any amount of any organic acid which is not deleterious to the substance being dyed or to the dye solution can be used. A deleterious acid is one which reacts on the dye or hair to cause undue deterioration thereof, such as an oxidizing acid. In general a sufficient acidity is about 0.04% to about 0.5% of glacial acetic acid or its equivalent. Small amounts of acid such as concentrations of or equivalent to about 0.06% to about 0.1% are usually desirable and such low concentrations, especially of acetic acid are preferred in dyeing the hair of living persons.

Both the premordanting solution and the developing or dye solution may be applied at a temperature not less than about-40 F., but the preferred temperature range for dyeing human hair is about 70 F. to about F. since the action of the dye is faster, better quality dyeings are produced at these temperatures and temtions of the synthetic dyes of the kinds described can be operated rapidly and at relatively low temperatures to dye hair in a variety of shades, provided the hair is also premordanted at low temperatures. The lower concentrations are usually satisfactory, but any acidified solution up to saturated solutions can be used. In such a procedure the dyeings are accomplished with surprising rapidity and they have satisfactory fastness properties.

The reasons for the surprising eifect oi" the described premordanting are not fully understood but the premordanting appears to have a specific effect on hair which in the case of premordanted bleached hair gives a satisfactory dyeing even without further treatment. When a different shade is desired besides that produced by iron sulfate alone, the premordanted hair appears to provide an especially suitable composition which has superior aihnity for the class of dyes described. Besides exhausting the dye solutions rapidly, there is a surprisingly complete penetration of dye into hair which'is premordanted at the described temperatures. In the dyeing of living hair the low temperature of application and rapidity of the final results are of the greatest practical importance since both contribute to the comfort and satisfaction of the person whose hair is operated upon and superior dyeings are obtained without delay. The rapid development of the final color with a given application of the color developing solution is also an important advantage in cases where it is desired to vary the dyeing by a second or repeated applications of the developing solution, as for example where new-grown hair is to be dyed to match the previously dyed hair. In such cases the bleaching and premordanting can be confined to the newly treated parts of the hair and the correct shade can be attained rapidly and easily, often by an inexperienced operator.

The preferred conditions for dyeing the hair of living persons is the use of premordanting solutions which may or may not be acidified, dyeing solutions which are acidified, application temperature of about 70 F. to 110 F. and mordant solution and dye solution of about 0.25% to 1%.

70 F. to about 130 F., and while the premordanted hair is still moist applying an acidified aqueous solution containing a non-deleterious acid and a water soluble synthetic organic dye which is heated to a temperature of about 70 F. to about 130 F.

2. The process of dyeing hair which comprises premordanting bleached hair by applying a dilute water solution containing a lake forming metal salt which is heated to a temperature of about 70 to about 130 F., and while the premordanted hair is still moist applying an acidified aqueous solution containing a non-deleterious acid and a water soluble synthetic dye which is heated to a temperature of about 70 F. to about 130 F.

3. The process of dyeing hair which comprises premordanting the hair by applying a dilute water solution of a ferrous salt which is heated to a temperature of about 70 F. to about 130 F., and while the premordanted hair is still moist applying an acidified aqueous solution containing a non-deleterious organic acid and a water soluble synthetic organic dye which is heated to a temperature of about 70 F. to about 130 F.

4. The process of dyeing hair which comprises premordanting the hair by moistening it with a dilute water solution containing a ferrous sulfate which is heated to a temperature of about 70 F. to about 130 F., and while the premordanted hair is still moist applying a solution containing a water soluble synthetic organic dye and a small amount of acetic acid, said solution being heated to about 70 F. to about 110 F. I

5. The process of dyeing hair which comprises premordanting the hair by moistening it with For dyeing hair in shades of blond, henna, brown and black, one or a mixture of two or more dyes which when used alone on premordanted hair, dye it in a shade of yellow, red, brown or black are preferred. To any of these or to mixtures thereof, there may be added a minor proportion of logwood crystals for varying the tint when such a variation is desired. With such solutions and temperatures the full and final fastness and shade effects are produced rapidly and the hair has a natural appearance.

From the foregoing disclosure it will be recognized that the invention is susceptible of modiflcation without departing from the spirit and salt which is heated to a temperature-0f about a dilute water solution containing a ferrous sulfate which is heated to a temperature of about 70 F. to about 130 F., and while the premordanted hair is still'moist applying an aqueous' solution containing a water soluble synthetic organic dye and a small amount of acetic acid which is heated to about 70 F. to about F., said dye being at least one of agroup of chrome dyes which dyes hair that is premordanted with said sulfates in one of the shades yellow, brown, red and black.

6. The process of dyeing hair which comprises premordanting the hair bymoistening it with a dilute water solution containing ferrous ammonium sulfate at a temperature between about 70 F. and F., said solution containing about 0.25% to about 5.0% of said sulfate, and while the premordanted hair is still moist applying an acidified solution containing a water soluble synthetic chrome dye containing about 0.25% to saturation of said dye and about 0.04% to about 0.5% of acetic acid.

7. The process of dyeing hair which comprises mordanting a bleached hair with a water solutiOn containing about 0.25% to about 1.0% of a ferrous sulfate, and then while the hair is moist applying an aqueous solution containing about 0.1% of acetic acid and at least one of the water soluble chrome dyes which dyes hair that is premordanted with said sulfate in one of the shades yellow, brown, red and black; both of said solutions being heated to a temperature between about 70 F. and 110 F.

WILLARD FREDERICK VAN RIPER. WARREN JOHN ZINCK.