3,193,464 United States Patent Office Patented July 6, 1965 2 produces an exothermic chemical reaction. This heat 3,193,464 intensifies the sensitivity of the scalp to the peroxide HYDROGEN PEROXDE HAR BLEACHING free alkali, etc. COMPOSITION AND METHOD Hair color consists of granular coloring such as black, Walter W. Edman, Port Washington, and Anne T. Sulli 5 which is easily bleached out, and diffused red coloring van, Hollis, N.Y., assignors to Sales Affilites, Inc., New which is more resistant to bleaching. Because of its re York, N.Y., a corporation of New York sistance, red tones are found in all but the higher stages No Drawing. Filed May 31, 1961, Ser. No. 113,605 of bleached hair. The shades and intensity of red in 5 Claims. (C. 167-88) the hair vary from individual to individual and even O on the same head. As the principal purpose of bleaching This invention relates to a novel hair bleaching com is to arrive at a blonde shade, these red tones produce position and particularly to a hair bleaching composi an undesirable color effect. They confer a highly arti tion that produces a more effective, more versatile and ficial-looking color to hair and impart a brassy tone to more comfortable bleaching action on the hair. blonde shades. Any red hue remaining in the hair inter Any process relating to the treatment of hair must take 5 feres with the color imparted by the hair toner, producing into account a tremendous number of variables; the an off-color. The presently marketed bleaches eliminate bleaching process is no exception. Hairs differ from the interfering red coloration by bleaching the hair fur head to head and even on the same head in natural ther. Thus the hair is bleached in excess, that is, to a color, texture, resistance to treatment, size (diameter), lighter blonde shade than that necessary for a particular condition, porosity, etc. 20 toner, just to remove a concomitant, interfering color. Bleaching, basically, is a process of removing the nat All bleaching damages the hair. Bleaches not only ural color from hair. Because of the virtually unlimited affect the color of the hair but also the hair fibre itself. variations of hair colors, bleaching per se, does not It is therefore preferable to limit the level of bleaching usually produce a uniform or aesthetically pleasing color to that which is necessary to achieve the desired end-color. in hair, nor will it produce a color tone other than that 25 Applicants' invention overcomes the disadvantages of inherent in the hair. For these reasons hair that has formation of off-color, uncomfortable bleaching, separate been bleached is subsequently treated with a hair "toner,' bleaches for particular degrees of bleaching, etc. a composition containing a hair dye which imparts the An object of applicants' invention is to provide a novel desired end-color to the bleached hair. method of bleaching hair and a novel hair bleach com The degree to which the natural color must be bleached 30 position that bleaches or strips the color from hair with from the hair is primarily determined by the desired end a maximum of comfort to the patron. color. The toners do not lighten the shade of hair to Another object is to provide a novel hair bleach corth any great extent; they impart their tone coloration to position that bleaches or strips the color from hair at hair pre-bleached to the basic blonde shade desired, e.g. lower temeprature than heretofore possible. pastel blonde color tone is achieved in hair pre-bleached 35 A further object is to provide a novel hair bleach to pale blonde not in hair pre-bleached only to a light composition that is more versatile than many presently brown. used bleach compositions. The hair colors desired by patrons vary from the mere A still further object is to provide a novel hair bleach highlighting of hair through to the palest blonde shade. composition that bleaches hair lighter than other bleach The bleaching compositions therefore must be capable 40 compositions. of producing mild bleaching, high bleaching and all de Another object is to provide a novel hair bleach com grees of bleaching in between. position that bleaches hair at a more rapid rate than other Some heads have virgin or untreated hair; others have bleaches. bleached and/or dyed hair. If the patron desires to alter A further object is to provide a novel hair bleach the color of her pre-treated hair, the dye color is usually 45 composition that eliminates the red tones in bleached hair stripped from the hair by a strong bleaching composi more efficiently and effectively with less hair damage than tion. Many problems relating to bleaching virgin hair heretofore possible. also apply to this type of bleaching or stripping of hair, Other objects and advantages will be set forth herein therefore both hair conditions are treated as one, unless or will be obvious herefrom or may be learned by prac otherwise stated herein. 50 tice with the invention. An entire head of hair may be bleached or only por Applicants' invention consists of a novel bleaching tions thereof, i.e. new growth of hair, streaking or tipping composition containing a novel bleach and a novel bleach tresses of hair. accelerator or booster. Applicants' novel bleaching com In the present art of hair bleaching, there are some position contains a drabbing agent and a coolant. A bleaches formulated solely for mild bleaching, others 55 "drabbing agent' is one that eliminates undesirable warm only for high bleaching and some products offered for tones which occur during the bleaching of hair. A the accomplishment of the entire range of bleaching. "coolant' is an agent that produces a lower solution Each type has certain disadvantages. temperature in the bleach. The limitations of a mild bleaching agent are obvious, The bleach is a combination of bleach base and hydro namely, that it is incapable of producing a high degree 60 gen peroxide in the ratio of about 2 parts of peroxide of bleach within a reasonable length of time. The high to each part of base. The peroxide, usually 20 volume, bleach products "burn' the scalp. In the high bleaching bleaches hair most effectively in an alkaline medium. Many alkaline materials have been used, but ammonia products the high concentration of active ingredients in is the most effective reagent for activating the peroxide. contact with the scalp causes considerable discomfort to Applicants' bleach base is comprised of the combination the patron, in some cases, a biting, stinging, burning of liquid soaps, such as ammonium oleate, laurate and sensation which may be so intolerable that the patron's Stearate; hair conditioners, such as propylene glycol, hair must be bleached in several sittings rather than at glycerine, etc.; soap solubilizers, such as the lower alco one time. This is undesirable from the standpoint of the hols; and thickening agents, such as fatty acid amides and patron and the operator. The more versatile bleaches 70 amines; NH4OH in quantity sufficient to neutralize the on the market also encouter the irritation problem from fatty acid and to provide an excess of free ammonia from high bleaching action. The combination of the reagents about 2% to about 1.2% to activate the bleaching ac 3,193,464 3 4. tions and to adjust the pH to a range of from about pH agents and as a humectant in the bleach composition to 9 to about pH 9.7; a heavy metal sequestering agent such prevent undesirable drying during the bleaching process. as, salts of ethylenediamine tetraacetic acid and poly Upon the addition of applicants' booster to their bleach, phosphates; and a metal complex azo dye drabbing agent. there is an immediate drop in temperature; the resulting Upon the addition of the peroxide to applicants' bleach temperature of the bleaching composition is below room base, the viscosity of the liquid base is substantially in temperature. As a consequence the active ingredients of creased, virtually to the point of a gel. the composition are in contact with the scalp at a lower While the bleaching action is independent of the con temperature, which abates the occasion of irritation. One sistency of the composition, it is difficult, in practice, for would expect a bleaching composition at a lower temper an operator to control the application of water-thin bleach, O ature to react at a slower rate, however, surprisingly ap particularly when only portions of the hair are to be plicants' novel composition has a faster bleaching action. lightened. The preferred consistency is one sufficient to The following examples are given to illustrate appli maintain its applied locale without running, dripping or cants' bleach base and bleach booster. creeping. Bleach base Metal-complex azo dyes are well known. Basically, 5 they are polyvalent metal containing azo dyes in which Percent two molecules of dye are complexed with one metal atom NH4OH (28% conc.) ------9 (2:1 complexes). These type of dyes have been de Propylene glycol ------15 scribed in various patents and articles, for example U.S. Oleic acid ------40 Patents Nos. 2551,056, 2,730,522, 2,817,655 and G. Shet 20 Stearyl amine ------20 ty's article in J. Soc. Dyers Col. 71, 705-724, 1955. Isopropanol ------15 Presently there are several such dye products marketed by Iragalan Grey BL ------0.1 various companies, e.g. Du Pont's Capracyl, Ciba's Sodium ethylenediamine tetraacetate ------0.55 Cibalan, Geigy's Irgalan, etc. Bleach booster Applicants have found that the presence of the blue 25 shades of such dyes will produce the desired drab on the Ammonium persulfate ------14 hair; however, the duller blue shades produce optimum Sodium metasilicate ------14 drabbing coloration. This result is highly unexpected in Potassium persulfate ------30 view of the fact that these dyes are suitable for dyeing Sodium ethylenediamine tetraacetate ------0.1 in an acid to neutral pH range whereas in applicants' 30 SiO2 ------1. bleach the pH is in the alkaline range; also the dye does Cetyl alcohol ------3.4 not interfere with nor is affected by the strong oxidizing Urea ------37.5 medium. - When the materials are combined the oxidation process The blue dye is present in relatively low concentration. begins, therefore the bleach base, peroxide and bleach Slightly lesser or greater amounts (0.05 to 2.0%) may 35 booster are mixed immediately prior to performing the be used, depending upon the desired drabbing effect, but bleaching action. It is most convenient to combine the about 0.1% produces a satisfactory effect. composition in an applicator bottle, which is usually made The dye combines with the hair to overcome the con of plastic. comitant red tones in the bleached hair. The brassy and Add 4 oz. of peroxide followed by 46 grams of the similar harsh tones are thus eliminated, which permits the 40 booster and lastly 2 oz. of the bleach base. If the hair is toner to impart its coloration without off-color inter highly resistant and a high bleaching is required, an addi ference from such residual color in the air. The drab ef tional 23 grams of booster may be added; if lesser bleach fect is also important in those cases where a hair toner ing is necessary and the hair is easily bleached, 23 grams treatment is not given to the hair. In such cases, the off of booster may be used instead of the 46 grams. The color from red tones would be even more obvious, and combined materials should be shaken to assure that they the drab effect permits the hair to assume the developed 45 are all in solution and/or homogeneous dispersion. blonde tones in true color. In general, it is best not to shampoo the hair immedi The boosters, in essence, are an additional source of ately prior to the bleaching treatment as the scalp may oxygen added to the bleach immediately prior to use on become sensitive. the hair. If the hair is very easy to bleach, or if the natural hair Applicants' bleach booster contains an additional source 50 is very light in color, and an extremely light or mild of bleach, i.e. a mixture of ammonium persulfate and bleaching action, such as "highlighting” the hair, is de potassium perSulfate, sodium metasilicate; peroxide stabi sired, the bleach may be used alone. However, in the lizer, such as a heavy metal sequestrant; anti-caking agent, vast majority of cases the bleach accelerator or booster Such as a silica; thickening agents, such as cetyl, or lauryl is vital to the bleaching action. Normal or resistant hair alcohol; and urea. 55 does not bleach even a few shades lighter, within a reason While the proportions by weight between the ammonium able length of time, without the booster; high bleaching persulfate and sodium metasilicate may be 2 parts of the necessitates the presence of the booster. Applicants' novel former to each part of the latter, it has been found that a bleaching composition will produce the entire range of greater amount of free NH3 is obtained, unexpectedly, bleaching from a mild bleaching effect to the highest when the ratio is 1:1. 60 degree of bleaching. However, with the very mildest of The urea produces the coolant effect in the bleach com bleaching on easy-to-bleach or light colored hair, the time position. The greater the concentration of urea, the lower of application becomes an important factor. Assuming the temperature of the composition, e.g. when the urea con it takes the operator fifteen minutes to apply the composi stitutes about 35-40% by weight of 23 grams of booster, tion, if the bleaching composition produces the desired the temperature is 9-10 F. lower than room temper 65 color in ten minutes, the operator must apply the bleach ature. to only sections of the hair at one time, wait for color In addition to the coolant effect produced by the urea development, rinse the bleach from the hair and repeat in the solution, applicants find that the presence of urea the procedure until the entire head is bleached. Such unexpectedly stabilizes the pH of the bleach which in 70 a procedure, while feasible, is troublesome and time con creases the bleaching action of the composition so that suming. As the occasion of irritation during this very hair may be bleached to a higher degree than other mild bleaching is so slight, there is little advantage to bleaches in an equivalent length of time. The bleaching using the combination of applicants' bleach and booster is affected with a maximum of comfort. In addition to as weighed against the use of the bleach alone. This this the urea functions as a carrier for the thickening 75 type of bleaching is so infrequent compared to the vast 3,193,464 5 6 majority of bleaching processes that the consideration agent, a bleach booster and a coolant; said bleach base of using a bleach without booster is virtually academic. being a carrier, containing ammonium hydroxide in an As regarded herein, applicants' novel bleaching composi amount to provide /2 to 1.2% free ammonia; said bleach tion comprises the combination of bleach and booster. ing agent being hydrogen peroxide; said bleach booster Applicants have found that the metal complex azo dye consisting essentially of at least one water soluble per may be present in the booster in lieu of the bleach, but as Sulfate in combination with sodium metasilicate; and, the booster and bleach are combined to form the bleach Said coolant being urea in an amount to produce a coolant ing composition, it is immaterial, from the standpoint of effect on the head in the use of said bleaching com its activity, in which fraction of the bleaching composi position. tion it is originally. However, as the drab effect is desired O 2. A hair bleaching composition as in claim 1 con even in those rare instances where the bleach is used taining a metal complex azo blue dye in an amount without the booster, it is more efficacious to place the from 0.05 to 2.0% by weight of the total composition drab in the bleach. as a drabbing agent. The technique followed in bleaching the hair may vary, 3. A hair bleaching composition as in claim 2, wherein depending upon the viscosity of the bleaching composi 5 the persulfate component is a mixture of ammonium per tion, the location and amount of hair to be bleached, etc. Sulfate and potassium persulfate. An example of a technique, utilizing the plastic applier 4. A hair bleaching composition comprising the com bottle, for bleaching the entire head of hair is as follows: bination of a bleach base, a bleaching agent, a bleach Making 4 inch partings, apply the bleaching composi ing booster and a drabbing agent; said bleach base being tion to hair, making certain that each strand is saturated 20 a carrier containing ammonium hydroxide in an amount along the entire hair shaft, continue partings and applica to provide /2 to 1/2% free ammonia; said bleaching agent tion of bleaching composition until all the hair is treated. being hydrogen peroxide; said bleach booster consisting Clean off a hair tress to check the color at various time essentially of at least one water soluble persulfate in intervals until the desired hair shade is attained, reap combination with sodium metasilicate; and, said drab plying bleach to the checked tress if the hair is not light 25 bing agent being a metal complex azo blue dye in an enough. As soon as the desired color is attained, rinse amount from 0.05 to 2.0% by weight of the total com off the bleaching composition and lightly shampoo the position. hair. Towel dry the hair and apply the toner, following 5. The method of bleaching hair comprising the steps the directions on the toner. of treating hair with a bleaching composition comprising Frequently in bleaching the entire hair, the bleaching 30 the combination of a bleach base, a bleaching agent, a composition is applied to the hair from about an inch away bleach booster and a coolant; said bleach base being a from the scalp down through the ends of the hair. When carrier, containing ammonium hydroxide in an amount a color slightly darker than the desired shade is obtained, to provide /2 to 1/2% free ammonia; said bleaching the bleaching composition is then applied to the scalp end agent being hydrogen peroxide; said bleach booster con of the hair (usually with smaller partings of about /2 35 sisting essentially of at least one water soluble persulfate inch) and the entire head is then allowed to process until in combination with sodium metasilicate; and, said cool the desired shade is attained. At this point the hair is ant being urea in a amount to produce a coolant effect rinsed, etc., as stated above. on the head in the use of said bleaching composition. The length of time the bleaching composition remains in contact with the hair varies with the degree of bleach 40 References Cited by the Examiner desired and the resistant quality of the hair. In general, UNITED STATES PATENTS the color of the hair is checked after 20 minutes and at frequent intervals thereafter; one hour is the average 2,081,327 5/37 Franz ------252-186 X bleaching time. 2,185,467. 1/40 Kritchevsky ------167-88 The invention in its broader aspects is not limited to 45 2,679,483 5/54 Armstrong et al. ------252-186 the specific steps, compositions, etc. described but depar OTHER REFERENCES - ture may be had therefrom within the scope of the ac companying claims without departing from the principles Jannaway: The Perfumery and Essential Oil Record, of the invention and without sacrificing its chief ad June 1938, pp. 220-223. Wantages. 50 Sagarin: Cosmetics, Intersciene Pub., 1957, p. 511. We claim: JULIAN S. LEVITT, Primary Examiner. 1. A hair bleaching composition comprising the com prising the combination of a bleach base, a bleaching MORRIS O. WOLK, Examiner. 7 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 5, 195,464 July 6, 1965 Walter W. Edman et al. It is hereby certified that error appears in the above numbered pat correctedent requiring below. correction and that the said Letters Patent should read as Column 5, line 35, for "1/2" read -- 1/8 - -; line S 52 and 53, strike out 'the comprising'. Signed and sealed this 15th day of February 1966.

(SEAL) Attest: ERNEST W. SWIDER EDWARD.J. BRENNER Attesting Officer Commissioner of Patents UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION tent No. 3, 193, 464 July 6, 1965 Walter W. Edman et al. It is hereby certified that error appears in the above numbered pat it requiring correction and that the said Letters Patent should read as irrected below. Column 5, line 35, for "1/2" read - - 1/8 - - ; lines 52 d 53, strike out 'the comprising'. Signed and sealed this 15th day of February 1966.

AL) st: NEST W. SWIDER EDWARD J. BRENNER sting Officer Commissioner of Patents