the compounds known as vat dyes are well known . they have been used for thousands of years , examples being the naturally occurring indigo and tyrian purple . in modem times , dyes of this type have been made synthetically , and are widely used in the textile industry for dyeing of cloth , both natural and synthetic ( see joseph rivlin , the dyeing of textile fibers , theory and practice , chapter 10 , 1992 , incorporated herein by reference ). these dyes are aromatic compounds containing two or more carbonyl groups that are joined by conjugated double bonds . unlike their permanent dye precursors , the vat dyes already contain their chromophore , and therefore do not require the presence of an oxidative agent to generate the chromophore on the hair . the soluble vat dyes are actually a group of dyes by themselves . they are vat dyes already in the reduced soluble form , and have the unique feature that they will not oxidize by merely exposing them to the air . the soluble vat dyes are esters of the leuco vat dyes . in presence of the acid and at the proper temperature , the ester will hydrolyze to yield the leuco acid of the vat dye , which can then be oxidized even by air , as are regular leuco vats , to its insoluble form . solubilized vat dyes were originally used for textiles . this is because they offer many advantages : 1 . the reduction step is eliminated and there is no need for careful control of the dye - bath during application . 2 . the application is easier to follow since there are not large amounts of electrolytes in the dye - bath that may cause a fast - strike . 3 . the solubilized vat dyes can be used in a significantly lowered ph and in diverse applications . soluble vat dyes have previously been disclosed for use in dyeing hair , but only in combination with a standard peroxidation system ( u . s . pat . no . 5 , 364 , 415 ). however , to the best of applicants &# 39 ; knowledge , solubilized vat dyes have never been used alone for the coloring of hair . surprisingly , it was found that solubilized vat dyes out - perform other classes of dyes in the semi - permanent dye formula . for example , basic and direct dyes normally used in semi - permanent hair colors wash out after a few shampoos . solubilized vat dyes , however , can last up to 45 shampoos . in application , the solublized vat dye is easily penetrated into the hair and is then oxidized back to its insoluble form by simple exposure to the air . this oxidation thereby causes the dye to be retained by the hair and thus coloring the hair . the solublized vat dyes of the invention can be any of the solublized vat dyes that are cosmetically acceptable . vat dyes as well as solublized vat dyes encompass two chemical classes , namely the indigoids and the anthraquinone derivatives , with a preference for the anthraquinones because of their color fastness . examples of useful solublized vat dyes include , but are not limited to , ci solublized vat brown 5 ( ci 73411 ), ci solublized vat black 1 ( ci 73671 ), ci solublized vat red 1 ( ci 73361 ), ci solublized vat green 2 ( ci 59831 ), ci solublized vat violet 8 ( ci 73601 ), ci solublized vat yellow 4 ( ci 59101 ), ci solublized vat brown 1 ( ci 70801 ), ci solublized vat red 3 . the vat dyes are capable of being used alone , as the sole source of color in a dyeing composition , or in combination with another solublized vat dye . the amount of dye used is dependent upon the final shade desired , and is not particularly critical . however , the dyes are ordinarily used in an amount of about 0 . 5 to about 10 % by weight of the composition , and preferably in a range of about 1 to about 5 %. it was discovered that the dye solution penetrates the hair very quickly , sometimes in a matter of seconds , and the color change on the hair can be observed almost immediately . oxidation of the dyes back to their insoluble , colored , form is achieved in the absence of harsh oxidizing agents , such as hydrogen peroxide . instead , sufficient oxidation can occur simply by exposure to air ; ordinarily , however , it will be desirable to assist the dyeing procedure by exposing the hair to a hair dryer , preferably a blow dryer on a warm setting , for about 10 minutes . although the dyeing composition and application may indeed be as simple as described above , ordinarily the composition and methodology will employ additional features to optimize the process and produce an improved color intensity and / or color fastness . for example , a useful additive to the dye solution is one or more antioxidants . the presence of the antioxidant ( s ) in the formulation aids in solublization of the dye , reducing precipitation of the dye , and ensuring that the dye is in optimum form for penetration and dyeing of the hair . examples of useful antioxidants are erythorbic acid , sodium sulfite , sodium metabisulfite , and sodium hydrosulfite . when used , the antioxidant will be present in amount of from about 0 . 5 - 5 % by weight of the composition . a preferred combination is of sodium metabisulfite and erythorbic acid , particularly preferred in a ratio of about 2 : 1 . an additional factor that may aid in performance is the use of an alcohol in the formulation , namely benzyl alcohol . the alcohol may constitute up to about 90 %, or even more , of the composition , taking into account the other necessary components of the product . however , in most cases , the amount of benzyl alcohol used will be about 0 . 5 to about 5 % by weight . because the solublized vat dyes are very versatile and applicable , it is possible to combine the vat dyes with other types of semi - permanent hair dyes . the semi - permanent dye systems of the present invention have many advantages over comparable existing dyes systems . first , the use of the solublized vat dyes avoids the use of harsh oxidants such as hydrogen peroxide , and thus reduces the possibility of hair damage due to the dyeing process so common with other dyes . the colors are also very bright , and easy to match because of its defined chromophore system . the dyes have a great affinity for the hair , and maintain an exceptional level of color - fastness even after many shampoos . the application of the dye system is also very simple , achievable in a simple rinse - off formula , with color development completed by air exposure , preferably coupled with a hair dryer at a moderate heat setting . the invention will be further understood by reference to the following non - limiting examples . a number of experiments were carried out to determine the effect of different variables on the development of color and color fastness . the following variables were tested for their effect on the formulation and on the dyeing process : dye name color index number ci solubilized vat brown 5 73411 ci solubilized vat black 1 73671 ci solubilized vat red 1 73361 ci solubilized vat green 2 59831 ci solubilized vat violet 8 73601 ci solubilized vat yellow 4 59101 ci solubilized vat brown 1 70801 ci solubilized vat red 3 not published the aqueous solution containing vat dye was heated with agitation to about 50 ° c . the dye and antioxidant ( if used ) was then added at 60 ° c . following approximately 5 minutes of cooling , the ph was adjusted ( if applicable ). hair swatches of 50 % gray , natural blond and yak ( international hair importers & amp ; products inc ., ny ) were fully saturated with the dye solution and incubated at 40 ° c . for 20 minutes . the hair was then rinsed with tepid tap water , towel dried and blown dry at a medium setting . if hair swatches were washed , the hair was saturated with tepid tap water and shampooed using rosemary mint shampoo ( aveda ). the hair was then rinsed thoroughly , combed and blown dry on medium setting . in preparing the solution , the violet dye appeared to go into solution at constant rate , regardless of an antioxidant being added to the dye , or the ph of the solution . when sodium hydrosulfite was used , it did not go into aqueous solution when used in conjunction with erythorbic acid . the ph was adjusted to around 10 using various bases ( ammonium hydroxide , amp and naoh ). it is important to note that the solubilized vat dyes also work well in acidic conditions , and can therefore be used in a variety of formulas . when the dye was applied to dry hair , it appeared to absorb the dye solution very quickly and even “ wicked ” its way up to the base of the hair swatch . an odor was emitted once dye was added to the hair . because some precipitation occurred , tests were conducted to determine if the vat dyes were truly in a reduced form . therefore various antioxidants were used and the hair color intensity appeared to be greatest with the addition of sodium metabisulfite and erythorbic acid , 2 : 1 respectively . the addition of these two antioxidants also decreased the amount of precipitate that formed in the solution and the dye appeared to go into the aqueous solution at a faster rate . the addition of electrolyte into the solution did not appear to change the precipitation of dye and appeared to decrease color intensity . the addition of sd alcohol in the original dye solution also did not change the volume of precipitate nor alter the hair color intensity , however addition of benzyl alcohol ( 5 %) increased the hair color intensity greatly as well as decreased fading after washing . different concentrations of dye were used ranging from 1 - 10 % and it appeared that above a 2 % dye solution , the intensity of color did not appear to change significantly . conditioning hair after rinsing appeared to intensify color of yak hair , but this result was not readily observable in the other trial swatches . most fading occurred during the first two shampoos . the color was seen in the shampoo bubbles and was displaced on the towel when dried . fading was reduced with the addition of benzyl alcohol into the solution . in conclusion , the most intense and vibrant color along with greatest wash fastness was seen with a solution containing 5 % benzyl alcohol , 4 % solubilized vat dye , 2 % sodium metabisulfite and 1 % erythorbic acid and ph being adjusted with ammonium hydroxide . on one fading experiment conducted , l , a , and b values were determined with the use of a chromameter ( minolta ) and graphed ( fig1 and 2 ). swatch label “ 1 ” is a reference swatch in which it was dyed and then rinsed with tap water . swatch “ 2 ” was dyed , rinsed and washed 5 times . the solution that the swatches were dyed with was 4 % svd ( violet ), 2 % sodium metabisulfite , 1 % erythorbic acid and water . l , a , and b values before and after 5 shampoo cycles l a b l a b 1 23 . 3 30 . 09 − 10 . 6 1 24 . 26 32 . 58 − 10 . 53 2 23 . 87 28 . 39 − 9 . 53 2 22 . 21 27 . 51 − 8 . 79 3 23 . 85 27 . 92 − 8 . 7 3 22 . 24 28 . 71 − 10 4 23 . 91 27 . 72 − 8 . 84 4 23 . 91 31 . 25 − 10 . 38 5 21 . 87 24 . 02 − 7 . 31 5 26 . 01 35 . 48 − 13 . 6 6 25 . 27 31 . 47 − 10 . 36 6 26 . 23 36 . 41 − 13 . 87 7 25 . 16 31 . 56 − 10 . 06 7 26 . 32 32 . 66 − 11 . 48 8 25 . 22 29 . 17 − 8 . 64 8 25 . 92 30 . 94 − 10 . 64 9 25 . 13 28 . 72 − 8 . 66 9 24 . 06 28 . 58 − 9 . 6 10 22 . 81 26 . 61 − 8 . 03 10 26 . 04 30 . 19 − 10 . 32 averages : 24 . 039 28 . 567 − 9 . 073 24 . 72 31 . 431 − 10 . 921 the solution for the above data consisted of 5 % benzyl alcohol , 5 % solublized vat dye and water . the ph was adjusted to 10 using ammonium hydroxide . solublized vat dyes were incorporated into various formulas to determine applicability of the dyes . some of the formulas are as follows : low voc indigo hair spray ctfa ingredient percent sequence sd alcohol 40 - b 190 proof 51 . 0 1 solublized vat dye ( svd ) 4 . 0 1 erythorbic acid 1 . 5 1 sodium metabisulfite 2 . 5 1 fragrance 1 . 0 - 0 . 4 1 octylacrylamide / acrylates / 0 . 2 3 butylaminoethyl methacrylate va / crotonates / vinyl 4 . 5 3 neodecanoate copolymer panthenol 005 4 lauramide dea 0 . 05 4 tocopherol 0 . 01 4 di water q . s . 4 surfactant 0 . 1 4 amp qs 5 at stp , sequence # 1 ingredients were added and mixed until homogeneous . sequence # 2 ingredient was then added and mixed in thoroughly . at medium to high speed , sequence # 3 ingredients were mixed in . at medium mixing speed , sequence # 4 ingredients were added to the mixture and stirred until all lumps of powder dissolved . finally , the ph was adjusted to 9 with sequence # 5 . the product was applied to 4 yak , 4 natural white and 4 50 % gray hair swatches , incubated for 10 minutes at 40 ° c . and dried . one of each type of hair swatch was kept after dying process , one of each was rinsed with tap water after dyeing process , one of each was washed once with aveda ® rosemary mint shampoo after dyeing process , and one of each was washed 5 times after dyeing process . there was vibrant and level deposition of dye onto the different hair samples . there was not much difference in amount of fading with the “ rinsed ” samples and “ washed one time ” samples . indigo black malva shampoo ctfa ingredient percent sequence di water q . s . 1 erythorbic acid 1 . 5 1 sodium metabisulfite 2 . 5 1 wild cherry bark extract 1 . 00 - 0 . 1 2 camellia oleifera extract 1 . 00 - 0 . 1 2 malva rotundafolia flower 1 . 00 - 0 . 1 2 aloe barbadensis leaf extract 1 . 00 - 0 . 1 2 prunus dulcis 1 . 00 - 0 . 1 2 tetrasodium edta 0 . 05 3 solublized vat dye ( svd ) 2 . 0 - 5 . 0 4 ammonium lauryl sulfate 15 . 0 - 30 . 0 5 cocamidopropyl betaine 2 . 0 - 5 . 0 6 cocamidopropyl 2 . 0 - 5 . 0 7 hydroxysultaine wheat amino acids 0 . 1 8 isostearamidopropyl 0 . 5 9 morpholine lactate cocamidopropyl pg - dimonium 1 . 0 10 chloride phosphate panthenol 0 . 1 11 lauramide dea 2 . 0 - 5 . 0 12 fragrance 0 . 5 13 tocopherol 0 . 03 13 citric acid 0 . 05 14 mix thoroughly for 20 minutes sequence # 1 ingredients . place sequence # 2 ingredients into a 5 - micron filter bag , placing the filter bag into the water mixture and circulate for 20 minutes . add sequence # 3 ingredient with slower mixing to avoid foaming . add slowly sequence # 4 to the mixture until homogeneous . sequence # 5 -# 12 ingredients should be added in sequential order , insuring that each component is fully dissolved before adding the next one . premix sequence # 13 ingredients in a separate container and add the mixture slowly to the main container and mix for 30 minutes . finally , sequence # 14 ingredient can be added and mixed for 30 minutes . natural indigo shampoo ctfa ingredient percent sequence deionized water 22 . 75 1 xanthan gum 0 . 75 1 sodium metabisulfite 2 . 5 1 erythorbic acid 1 . 5 1 cocamide dea 6 . 0 2 cocamidopropyl betaine 20 . 0 2 saponins 10 . 0 2 benzyl alcohol 5 . 0 2 rosemary extract 0 . 10 2 comfrey leaf extract 0 . 10 2 horsetail extract 0 . 10 2 matricaria extract 0 . 10 2 decyl polyglucose 15 . 0 2 avocado oil 0 . 10 2 solublized vat dye 5 . 0 3 citric acid q . s . 4 polyquaternium - 10 10 . 0 5 acetamide mea 1 . 0 5 the ingredients of sequence # 1 were combined at 60 degrees celsius under moderate stirring for about 20 minutes or until gum and antioxidants were thoroughly dissolved . the temperature was then brought back down to stp for the remainder of the procedure . slowly , sequence # 2 ingredients were added and mixing continued , making sure the polymer was completely dispersed . sequence # 3 ingredients were then mixed in slowly until homogeneous . sequence # 4 ingredient ( the vat dye ) was then added until mixed thoroughly . the ph was adjusted to 5 . 5 (± 0 . 2 ) with sequence # 5 . sequence # 6 ingredient was slowly added and mixed until homogeneous . sequence # 7 was then mixed in slowly until batch was homogeneous . indigo hair conditioner with tea tree oil ctfa ingredient percent sequence deionized water qs 1 xanthan gum 0 . 75 1 sodium metabisulfite 2 . 5 1 erythorbic acid 1 . 5 1 methylparaben 0 . 2 2 methychloroisothiazolinone and 0 . 1 2 methylisothiazolinone ( mix ) hydrolyzed whole wheat protein 0 . 1 2 dicetyldimonium chloride 1 . 0 3 cetearyl alcohol and ceteareth - 20 2 . 0 4 ( mix ) stearamidopropyl dimethylamine 1 . 35 4 tea tree oil 2 . 0 4 propylparaben 0 . 05 4 benzyl alcohol 5 . 0 4 fragrance 0 . 2 5 solublized vat dye 5 . 0 6 citric acid 0 . 3 6 the ingredients of sequence # 1 were combined at 60 ° celsius under moderate stirring for about 20 minutes or until gum and antioxidants were thoroughly dissolved . the temperature was then raised to 78 ° celsius . sequence # 2 was then added until a clear uniform solution was obtained . sequence # 3 was added , maintaining thorough mixing and temperature . in a separate mixing container , sequence # 4 was mixed and heated to 72 ° celsius . at proper temperature , sequence # 4 was added to the main container , maintaining temperature until emulsification was complete . the temperature was then cooled to 40 ° celsius with slower mixing . at 40 ° c ., sequence # 5 was added , cooling to 30 ° celsius . at 30 ° celsius , sequence # 6 was added and cooled to 25 ° celsius .
the invention relates to a semi - permanent dye system comprising at least one solubilized vat dye , an aqueous carrier , and substantially no chemical oxidant .