Abstract:
New, effective and non-toxic compounded henna based hair dyes that are non-toxic, natural and hypoallergenic that provide an alternative to conventional hair color. The products are made using 100% Green Chemistry and do not utilize encapsulation.

Description:
CROSS REFERENCE TO RELATED APPLICATIONS 
     The present application claims the benefit of U.S. Patent Application No. 61/187,062, filed Jun. 15, 2009, the contents of which are incorporated herein by reference. 
    
    
     BACKGROUND OF THE INVENTION 
     For centuries the use of hair coloring was restricted to the fashion needs of a privileged few and was dictated by necessity to hide gray hair. Today a lot of people, both women and man, use hair coloring to change their appearance. There are several reasons for this: to hide white hair, to lighten hair color and add additional highlights, to remove the yellow look from grey hair, enhance natural color, etc. 
     From a technical standpoint, extensive laboratory and research work is essential because of the diverse problems to be solved. The indiscriminate use of certain colorants may have dermatological and toxicological side effects. It is well known that hair dyes are subject for large studies in the field of allergology. Specific classes of dyes like direct and oxidative dyes, also known as Paraphenilene Diamine dyes, are known allergens and suspected carcinogens and genotoxins. (Charles Zviak, The Science of Hair Care, Marcel Dekker, 1986, p.235-240). 
     Although hair coloring using natural dyes is mentioned in most ancient documents, the development of new natural plant based hypoallergenic hair coloring systems remains a scientific and technological challenge. Most common are hair dye compositions based on henna. According to Zviak, henna is a natural product and generally does not have any side effects. The henna leaves are dried and crushed into powder and applied as a paste with hot water. Henna is typically produces auburn and brown-orange colors. However, henna does have a number of major drawbacks, such as complicated preparation and application, unleveled shades, incompatibility with other hair dyes and treatments, etc. Therefore, henna was almost completely replaced with synthetic hair dyes. 
     Recently henna has been regarded as a “back to nature” alternative for home use and by many hairdressers. 
     As early as 1907 improvements in henna dyes were attempted and were based on hair lacquers using phenol compounds such as pyrogallol and nickel, iron, copper, cobalt, or lead salts in the presence of reducing salt and a medium containing henna. These compounds produced full range of colors. 
     However, the disadvantages of hair dyes containing metallic salts are numerous. Most of them are toxic to some extent, and their use is strictly regulated. They nearly always create a dull, leaden color with a flat metallic appearance. Moreover, the metal fixed on the hair shaft acts as a catalyst, causing an abrupt breakdown of the hydrogen peroxide in bleaching products or permanent wave fixers resulting in significant hair damage 
     (C. Zviak, p. 241). Compounded henna remains the only natural alternative to conventional hair color. 
     Therefore, development of new non-toxic natural hypoallergenic alternatives to conventional hair color remains a scientific and technological challenge. Discovery of mild, non-toxic ingredients for compounded henna compositions can theoretically solve problems of color appearance, toxicity, application, and compatibility with other treatments. 
     The patent literature describes the enhancement of conventional oxidative dye composition with henna (or enhancement of so-called black henna). In U.S. Pat. No. 6,139,853, the solid hair colorant composition described comprises a 10-35% p-phenilenediamine based oxidative formula also containing non-oxidative dyes like HC Blue 2 and HC Yellow 12 and 25-70% neutral henna. While the disclosed colorant contains henna and is more convenient to use in comparison to regular henna, it still contains p-phenilenediamine that is not suitable for people with allergic reactions to p-phenilenediamine. 
     A similar composition, described in US 20060010618, discloses Myristine Africana plant parts used in an oxidative (p-phenilenediamine) based formula. 
     DE4402203 describes hair dyeing compositions containing ginseng and plant based dye as a temporary color. 
     JP4013611 A2 describes a hair coloring composition based on freeze-dried plants such as Acacia Shikouka and mordanting metals like Fe, Cr, Mn, or Sn. 
     JP2872385 B2 describes combination of oxidative dyeing agent, vegetable dyeing agent and quaternary ammonium salt. 
     A similar composition is described in U.S. Pat. No. 4,183,366 where 75-95% henna powder is mixed with non-ionic surfactant and 0.5-5.0 of a quaternary salt. Both patents describe a more convenient application procedure. However, there is no mention of durability and/or coloring palette improvement. 
     DE4201749 A1 describes compositions utilizing Alkanna root but only for graphite gray color. 
     DE19600225 A1 describes hair dyeing compositions based on utilization of oils and liquid waxes in a mixture of natural and synthetic dyes. 
     WO2007130777 A3 describes a composition of Acid Blue 74 and Mordant Red11 and combination of encapsulated mordant and natural dye extract. This composition does not seem to be practical due to low core payload possible because of the encapsulation technique. 
     US20030145395 describes hairdressing compositions of henna, tannin, catechin, gardenia, lac, annatto, brazilin and turmeric based pigments providing wide range of colors. However, the mordants described in this patent, like white lead and antimony white, can possess toxicological risks. Also, the scalp staining is the probable cause of using titanium and zinc oxides to inhibit the coloring process. 
     U.S. Pat. No. 7,186,279 describes a black dye comprising of Juglas Regia, Indigofera Tinktoria, Acacia Accocina, Lawsonia Interims, and hair coloring mordant based on natural tannins. While the composition is described as nontoxic and safe, it results in only one color—black, which is not practical for the modern hair coloring industry. 
     The use of mordants is well known in the leather and textile industry and has been employed for centuries as a vegetable dye coloring method. However, the use of mordants has been limited in recent years because of their generally high toxicity. The most common mordants are salts of chromium and are still used in the leather industry, although rarely. Other mordants include salts of aluminum and copper which also possess both toxicological and environmental concern (Joseph Rivlin, The Dyeing of Textile Fibers, PCT&amp;S, Philadelphia, 1992, p. 30-52, H.S. Freeman &amp; A.T. Peters, Colorants for Non-Textile Applications, Elsevier, 2000, pp. 382-449) but are still in use in some textile and leather applications. 
     The mordant&#39;s function is to form a complex between a polyvalent metal salt and a dye. The application of a mordant traditionally requires at least two steps and often includes a pre- or post treatment as well. The reaction between mordants and dyes is virtually instantaneous, making it necessary to apply them separately. This is a significant disadvantage of the mordanting technique because scalp staining can occur due to the fast reaction between mordant and dye. 
     A desirable quality to incorporate into a mordant-dye system for coloring human hair would be to provide time delay in this reaction for several reasons. First, to decrease scalp staining which occurs during the instantaneous reaction between dye and mordant on both scalp and hair. Second, to make the system more convenient and give stylist or home user an opportunity to adjust the color and its depth. Third, to save time and make this application as convenient as a regular hair coloring process. 
     Copper sulfate has been known as a mordant for centuries. Its limitations of application in industries like textiles are limited due to harmful ecological effects (Rivlin p. 108-109) and toxicity. For the same reasons, copper sulfate did not find applicable use in hair coloring applications. However, copper based or mordanted dye compositions applied on textiles exhibit valuable qualities like broad range of colors, light and weather fastness and durability of color (Rivlin p. 108-109). 
     However, some copper salts such as lactic, acetic, tartaric, succinic and gluconic acids, in particular ones made from renewable plant based sources, are not only considered to be non-toxic but are also used as a dietary and food supplements. Copper is involved in numerous biochemical reactions in human cells and is a component of multiple enzymes, is involved with the regulation of gene expression, mitochondrial function/cellular metabolism, connective tissue formation, as well as the absorption, storage, and metabolism of iron. 
     Copper levels are tightly regulated in the body. Copper deficiency can occur in infants fed only cow-milk formulas (which are relatively low in copper content), premature/low-birth weight infants and in adults causing cystic fibrosis. Medicinal use of copper compounds dates to Hippocrates in 400 B.C. Bacterial growth is inhibited on copper&#39;s surface, and hospitals historically installed copper-alloy doorknobs and push-panels as a measure to prevent transmission of infectious disease. (Paul Coates et al., Encyclopedia of Dietary Supplements, 2005, Marcel Decker, pp.133-141). 
     The direct application of copper salts of lactic, acetic, tartaric, maleic, glycinic, succinic and gluconic acids in natural henna based compounding is not found in the art. 
     U.S. Pat. No. 7,087,255 discloses copper salts application in chewing gums as a dietary supplement, in particular copper gluconates and lactates. Copper Gluconate is disclosed as a suntan accelerator and skin protectant during sun tanning (U.S. Pat. No. 5,075,102). Similar application is described in U.S. Pat. No. 5,698,184. Copper Gluconate was proposed to increase melagenesis (darkening of skin and hair) as a part of sun tanning composition as an alternative to DHA (U.S. Pat. No. 6,696,417). U.S. Pat. No. 6,428,580 describes use of Copper Gluconate as a part of oxidizing system for perms. 
     Hair dyes known as dry henna (compounded henna) contain metallic salts in order to provide a right color. Most salts are heavy metals. Most of them are toxic to some extent, and their use is strictly regulated. Compounded henna nearly always creates a dull, leaden color with a flat metallic appearance. Despite all the detriments, compounded henna remains to be the only natural alternative to conventional hair color. 
     U.S. Pat. No. 7,550,014 entitles “Composition for dyeing keratin fibers and a method of dyeing hair using same” is limited to encapsulation and one part system only. 
     Copper Gluconate is mentioned but it is known that encapsulation of water soluble salts is very difficult and in many cases impractical. The maximum theoretical payload of encapsulated material can be no more than 10%. 
     Active copper content in Copper Gluconate can not be more than 12.4% based on molecular weight. In order to achieve concentrations mentioned in this patent (0.01-5%) the disclosed formula has to contain 620% of Copper Gluconate encapsulated to obtain 5% of active copper. It is impossible since maximum concentration of ingredients in formula can be only 100%. At 50% of encapsulate in formula there is 0.4% of active copper and there is not enough room for other ingredients, i.e. water as it is known that aqueous dyes can not produce color without sufficient water. 
     At 5% of encapsulate in the formula of this patents composition, the composition can deliver only 0.04% of active copper. At this concentration, color can not be developed due to very low concentration of mordant, i.e. Copper Gluconate. Practical concentrations around 0.5-5% of active copper cannot be achieved by encapsulation techniques. 
     Therefore, development of a non-toxic natural hypoallergenic alternative to conventional hair color which does not exhibit these detrimental effects remains a scientific and technological challenge and it is an object of this invention to provide a hypoallergenic alternative to conventional hair color which does not exhibit these detrimental effects. 
     Therefore, it is an object of this disclosure to provide final products that can be made using 100% Green Chemistry. 
     It is an object of this disclosure to provide final products that do not utilize encapsulation. 
     It is an object of this disclosure to provide new, effective and non-toxic compounded henna based hair dyes. 
     SUMMARY OF THE INVENTION 
     One advantage of this invention is that the final products can be made using 100% Green Chemistry. 
     Another advantage is that is that encapsulation is not utilized. 
     This invention relates to new, effective and non-toxic compounded henna based hair dyes. 
     A new mechanism using 100% Green Chemistry for swelling of keratin fiber using 100% natural and completely renewable and sustainable dye composition at pH 4.5 and lower than isoelectric point of keratin was discovered. Using all natural ingredients such as Natural Benzyl Alcohol, Benzylaldehyde as dye carrier and Natural Propanol as a solvent, and salts of natural assets it was possible to create a mechanism of ligand binding of human hair with natural dye. Natural Benzyl Alcohol in combination with Natural Propanol and acid causes human hair internal swelling and shifting of micro fibrils mostly in cortex area. This swelled fiber at pH lower than isoelectric point (pH 4.5) has high free volume and abundance of active groups. The ligand binded polynucleous complexes with hair keratin enabled the creation of all natural hair dye compositions that possess very unique qualities of these technologies that could previously be achieved only by using synthetic and/or oxidative dyes. 
     The invention is based on specific properties of copper like salts to promote ligand interaction with the polymeric matrix and other ligand donors like dyes. It was determined that copper complexes can be distributed as particles in the fibrous material. It was elucidated that most of the copper particles are capable of forming poly-nucleus complexes with fibrous materials. The type of copper based complex highly depends on type of fiber, polymeric matrix and conditions of particular treatment. These poly-nucleus complexes form a stable structure with polymeric matrix with compensated spin and can disassociate to smaller formations and react with other ligands. 
     Compounded henna concentrate can be made by mixing and/or heating its compounded ingredients with acid and natural co-solvent such as vegetable Glycerin, Propanediol (from corn), and other natural glycols and poly-alcohols. This process enables compounded henna to act as a dye concentrate. This dye concentrate, when added to conventional formulations such as gels, emulsions, suspensions, sprays at pH lower than 4.5 (isoelectric point of keratin) and/or mixed together with all natural binding system at pH 4.5 and lower will produce permanent coloring with necessary delay. This dye concentrate at pH 4.5 and lower can be added to conventional formulations such as gels, emulsions, suspensions, sprays at pH lower than 4.5 (isoelectric point of keratin) and act as a direct dye coloring system for human hair even in the absence of mordant. 
     This combination of all natural ligand binding system and all natural henna at pH lower than 4.5 can be formulated with dietary salts of copper and other dietary salts. This composition is based on ligand binding of self chelating salts of copper, such as Copper Gluconate and other copper salts with hair keratin. This ligand based complex forming system is employed to carry high payload of color delivering ingredients such as Henna. The color delivering ingredients, i.e. natural dyes and color containing actives such as antioxidants, antimicrobials and other phyto-therapeuticals; vitamins and co-enzymes; bioflavonoids, flavonoids, isoflavonoids, neoflavonoids can also have coloring properties. 
     The self chelating properties of some copper salts provide necessary inhibition and/or short delay in the reaction that makes application convenient and extremely practical. Color deposition does not occur on the scalp, only on hair and can be applied at home and/or salon. 
     It is the first time that Natural Benzyl Alcohol from Cashew oil or oil of Bitter Almond is applied to hair coloring formulations. Natural Benzyl Alcohol is one of the major dye carriers without which the performance of hair color is very limited. 
     In experiments it was also determined that Benzaldehyde that can be made from oil of Bitter Almond that commonly used as a flavor or fragrance ingredient and never before was used as a hair coloring carrier, can be used as a carrier of dyes in natural formulations. 
     Other ingredients that can be used such as Natural Propanol and gluconic salts can be made from corn and completely renewable and never had before been used in hair colorings compositions. 
     With these elements of green chemistry, a new mechanism was discovered for swelling of keratin fiber using 100% natural and completely renewable and sustainable dye composition. Using all natural ingredients such as Natural Benzyl Alcohol, Benzylaldehyde as dye carriers and Natural Propanol as a solvent, and salts of natural acids it was possible to create a mechanism of ligand binding of human hair with natural dye. 
     Natural Benzyl Alcohol in combination with Natural Propanol and natural acid and it salts causes human hair internal swelling and shifting of micro fibrils mostly in cortex area. This swelled fiber at pH lower than isoelectric point (pH 4.5) has high free volume and abundance of active groups. 
     The ligand binded polynucleous complexes with hair keratin enabled the creation of all natural hair dye compositions that possess very unique qualities of these technologies that could previously be achieved only by using synthetic and/or oxidative dyes. 
     These qualities are mixable shades, high resistance of product to environmental conditions and cumulative effects. This same mechanism also enables the control of a diffusion of dye which also resulted in extended gray coverage, reduced scalp staining and possibility of applying hair color without hair damage and using conventional application tools. 
     This specification discloses compositions of all natural non-toxic, non-allergenic henna based dyes. It can be formulated with dietary salts of copper and other dietary salts. This composition is based on ligand binding of self chelating salts of copper, such as Copper Gluconate and other copper salts with hair keratin. This ligand based complex forming system is employed to carry high payload of color delivering ingredients such as Henna. The color delivering ingredients, i.e. natural dyes and color containing actives such as antioxidants, antimicrobials and other phyto-therapeuticals; vitamins and co-enzymes; bioflavonoids, flavonoids, isoflavonoids, neoflavonoids can also have coloring properties. 
     The self chelating properties of some copper salts provide necessary inhibition and/or short delay in the reaction that makes application convenient and extremely practical. Color deposition does not occur on the scalp, only on hair and can be applied at home and/or salon. 
     Along with these properties, some other advantages of these compositions are described, such as: stability enhancement, in particular of iron salts that are also responsible for color development, better color deposition on human hair, less scalp staining, better durability, etc. 
     Some copper salts, in particular those derived from renewable plant based sources like lactic, acetic, tartaric, succinic and gluconic acids, are not just considered to be non-toxic but are also used as dietary and food supplements. Copper is involved in numerous biochemical reactions in human cells. 
     A key success factor for natural, alternative, nontoxic, hypoallergenic and high performance hair coloring composition is to develop new compounds of henna with non-toxic complexes to create a broad dye coloring palette. 
     An all natural non-toxic non-allergenic henna based compound is formulated with the dietary salts that can be used as a non toxic mordants or complex forming agents for ligand copper binded plant based henna based hair dye compositions containing at least one copper ligand donor, other mineral salts, natural dyes and color contained actives such as antioxidants, antimicrobials and other phyto-therapeuticals, vitamins and co-enzymes, bioflavonoids, flavonoids, isoflavonoids, neoflavonoids. 
    
    
     DETAILED DESCRIPTION 
     The copper compound may be selected from, for example, Copper Lactate, Copper Gluconate, Copper Acetate, Copper Glycinate, Copper Acetate, Copper Lysine, Copper Tartrate, Copper Salicylate, Copper Succinate. 
     Other mineral salts selected from but not limited to the following group are also useful in the present invention: Ferrous Lactate, Ferrous Gluconate, Ferrous Fumarate, Ferrous Citrate, Ferric Ammonia Citrate, Zinc Lactate, Zinc Citrate, Zinc Picolinate, Zinc Tartarate, Potassium Gluconate, Potassium Citrate, Potassium Lactate, Potassium Citrate, Potassium Succinate, Potassium Chloride, Calcium Maleate, Magnesium Citrate, Magnesium Carbonate, Magnesium Oxide, Calcium Gluconate, Calcium Citrate, Calcium Carbonate, Manganese Gluconate, Manganese Glycinate, Selenium Selenomethionine. 
     Copper salts that are listed above are typically do not have a stability problems. As matter of fact an application of copper salts is one of the best ways to increase light stability but in comparison with iron salt on the compositional mordanting it is very difficult to get dark shades like dark brown and black using a copper salts as a mordant alone (Rivlin, p. 108-109). 
     Natural Dyes and Color Contained Actives (antioxidants, antimicrobials and other phyto-therapeuticals) may be selected from Henna, Acacia Dealbata Flower/Stem Extract, Annatto, Anthocyanins, Astaxanthin, Betanin, Capsanthin/Capsorubin, Carotenoids, Chlorophyll, Coptis Japonica Rhizome Extract, Crocus Sativus Flower Extract, Curcuma Longa, Turmeric Extract, Dunaliella Bardawil Powder, Gardenia Florida Fruit Extract, Gardenia Jasminoides Fruit Extract, Guaiazulene, Carthamin, Rosa Hybrid Flower Extract, Rubia Cordifolia Root Extract, Rubia Tinctorum Root Extract, Purpuroxanthin, Morindanigrin, Morindadiol, Rhubarb Extract, Purpurin, Pseudupururin, Morindone, Emodin, Crocin, Crocetin, Canthaxanthin, Sorghum Vulgare Seed/Skin/Stalk Extract, Vitis Vinifera (Grape) Fruit Powder, Vitis Vinifera (Grape) Skin Extract, Wine Extract, Deoxysantalin, Atromentin, Humin, Berberine. 
     Vitamins and Co-enzymes may be selected from Beta Carotene, D-Alpha Tocopherols, Co Enzyme Q-10, D-Biotin, Folic Acid, Niacin, Niacinamid, Riboflavin, Tocopherol, Vitamin A, B1, B2, B5, B6, B12, D3. 
     Bioflavonoids, flavonoids, isoflavonoids, neoflavonoids may be selected from Flavone, Luteolin, Apigenin, Baicalein, Rutin , Acacetin, Fisetin, Kaempferol, Myricetin, Quercetin, Naringenin, Hesperidin, Taxifolin, Genistein, Genistin, Daidzein, BiochaninA, Doxorubicin, Quercetin, Kaempferol, Myricetin, Fisetin, Isorhamnetin, Pachypodol, Rhamnazin, Eriodictyol, Homoeriodictyol, Tangeritin, Dihydrokaempferol, Glycitein, Catechins, Epicatechins, Morin, Brazelin, Brazilein, Haematein, Haematoxylon, Atrocappanon, Fukugetin, Datiscetin, Rhamnocitrin, Rhamnetin, Xanthorhamnin, Gossypetin. 
     The above salts are used as nutrition supplements, vitamin complexes and for fortification of food. In many cases compatibility and stability of their ligand complexes in particularly in aqueous media is in question. 
     As an example, most of the iron supplements with high bioavailability are susceptible to oxidation and reaction with other ingredients during storage. During oxidation, the ferrous form Fe (2+) is converted to ferric form Fe (3+) that can cause precipitation. (U.S. Pat. No. 7,087,255; R. Hurrel, How to ensure Adequate Iron Absorption from Iron-fortified Food, Nutrition Reviews, Vol.60,7 pp 7-13 and Miller DD et all., An in vitro method for estimation of iron availability from meals, The American Journal of Clinical Nutrition, 43(10),pp2248-2256). Thus, it makes application of any liquid composition of ferrous salt in personal care products difficult due to stability requirements. In particular, the development of liquid hair coloring composition containing just Ferrous Gluconate would be impractical due to the stability concern. The typical required shelf life of hair coloring product should be at least 12 month. Attempt to stabilize ferrous salt is described in WO 2007/130777A3 by means of encapsulation. While encapsulated Ferrous Gluconate can make it more stable, the payload of encapsulate is typically low. The shell material and encapsulation process itself is expensive, elaborate and time consuming. This makes the technology of hair coloring product very expensive and impractical. 
     Several hydrocolloid based acidic formulations were made using both copper salts and iron salts and its compositions. All compositions were subjected to the long term standard ambient and light stability protocol as well as accelerated stability (Table 1). Hydrocolloids containing 10% of Copper and Iron Gluconates were prepared and mixed proportionally from 0-10%. 
     
       
         
               
             
               
               
             
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 Stability assessment of Iron and Copper Gluconates combinations: 
               
             
          
           
               
                   
                 Copper vs. Iron Gluconate % proportion 
               
             
          
           
               
                   
                 0:10 
                 2:8 
                 4:6 
                 5:5 
                 6:4 
                 8:2 
                 10:0 
               
               
                   
                   
               
             
          
           
               
                 Stability 1 month 
                 failed 
                 stable 
                 stable 
                 stable 
                 stable 
                 stable 
                 stable 
               
               
                 Stability 2 month 
                 failed 
                 stable 
                 stable 
                 stable 
                 stable 
                 stable 
                 stable 
               
               
                 Stability 6 month 
                 failed 
                 stable 
                 stable 
                 stable 
                 stable 
                 stable 
                 stable 
               
               
                 Stability 8 month 
                 failed 
                 stable 
                 stable 
                 stable 
                 stable 
                 stable 
                 stable 
               
               
                 Accelerated 
                 stable 
                 stable 
                 stable 
                 stable 
                 stable 
                 stable 
                 stable 
               
               
                 Stability 1 week 
               
               
                 Accelerated 
                 failed 
                 stable 
                 stable 
                 stable 
                 stable 
                 stable 
                 stable 
               
               
                 Stability 30 days 
               
               
                 Accelerated 
                 failed 
                 stable 
                 stable 
                 stable 
                 stable 
                 stable 
                 stable 
               
               
                 Stability 60 days 
               
               
                   
               
             
          
         
       
     
     Combinations of Ferrous Lactate and Copper Gluconate show similar pattern although Ferrous Lactate compositions are less stable and require more Copper Gluconate to stabilize them. 
     Table 1 discloses the following unexpected results. All of the Ferrous Gluconate and Ferrous Lactate compositions showed precipitation and typical Fe (3+) dark brown water like face separation on the top. The addition of as little as 2.0% copper dietary salt (Copper Gluconate) kept this composition stable for at least 8 months under normal conditions and for 60 days at accelerated conditions. 
     Another unexpected result occurred when color and mordanting compositions were mixed together and left still for 30 minutes (typical time of application of hair color). The dark brown compounded henna (“Dark Brown Henna”) was made with one of the ingredients from classes of ingredients described in the Scope of Invention. 
     Preparation is similar to that described in US20030145395. Precipitation occurred almost instantaneously in the compositions containing Ferrous Gluconate and Ferrous Lactate alone (without Copper salt addition). The samples mixed with equal amounts of Copper salts even as low as 10% have showed no precipitation on the course of 30 min and more as set forth in Table 2. 
     
       
         
               
             
               
               
             
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                 Precipitation of Copper and Iron Gluconate hydrogels 
               
               
                 with “Dark Brown Henna”-30 minute test. 
               
             
          
           
               
                   
                 Copper vs. Iron Gluconate % (of 100% total) proportion 
               
             
          
           
               
                   
                 0:100 
                 10:90 
                 30:70 
                 50:50 
                 70:30 
                 90:10 
                 100:0 
               
               
                   
                   
               
             
          
           
               
                 Precipitation 
                 Yes 
                 No 
                 No 
                 No 
                 No 
                 No 
                 No 
               
               
                   
               
             
          
         
       
     
     Color was applied on DeMeo Brother&#39;s Natural White Hair Swatches and on volunteers as a comparative ¼ head scalp surface test. A portion of the swatches was subjected to outdoor weather and a durability test for 45 days. All samples were evaluated for color in comparison with initial colored swatches using the same conditions. 
     
       
         
               
             
               
               
             
               
               
               
               
               
               
               
               
             
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 3 
               
               
                   
               
               
                 “Dark Brown Henna” using ligand 
               
               
                 binded Copper at 45 C. for 45 min. 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 Copper Gluconate vs. Iron Gluconate 
               
               
                   
                 % (of 100% total) proportion 
               
             
          
           
               
                   
                 0:100 
                 10:90 
                 30:70 
                 50:50 
                 70:30 
                 90:10 
                 100:0 
               
               
                   
               
               
                 Deposition 
                 Poor 
                 Fair 
                 Good 
                 Good 
                 Good 
                 Good 
                 Fair 
               
               
                   
               
             
          
           
               
                   
                 Copper Lactate vs. Iron Gluconate 
               
               
                   
                 % (of 100% total) proportion 
               
             
          
           
               
                   
                 0:100 
                 10:90 
                 20:80 
                 50:50 
                 60:40 
                 80:20 
                 100:0 
               
               
                   
               
               
                 Deposition 
                 Poor 
                 Fair 
                 Good 
                 Good 
                 Good 
                 Fair 
                 Fair 
               
               
                   
               
             
          
         
       
     
     As demonstrated by the results set forth in Table 3, best results on color deposition can be achieved within presence of copper salts like Copper Gluconate and Copper Lactate. Iron Gluconate was noted to exhibit poor deposition. Best results were achieved in proportion 30:70 parts of Copper salt. 
     
       
         
               
             
               
               
             
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 4 
               
             
             
               
                   
               
               
                 Scalp staining. Comparative evaluation 
               
             
          
           
               
                   
                 Copper vs. Iron Gluconate % (of 100% total) proportion 
               
             
          
           
               
                   
                 0:100 
                 10:90 
                 30:70 
                 50:50 
                 70:30 
                 90:10 
                 100:0 
               
               
                   
                   
               
             
          
           
               
                 Staining 
                 Heavy 
                 Moderate 
                 Mild to 
                 Mild 
                 Mild 
                 Very 
                 Very 
               
               
                   
                   
                   
                 Moderate 
                   
                   
                 Mild 
                 Mild 
               
               
                   
               
             
          
         
       
     
     As a shown in Table 4 some salts exhibit heavy scalp staining This staining can be eliminated by small addition of a copper salt. Significant improvement was observed from adding as low as 10 parts of copper salt. 
     
       
         
               
             
               
               
             
               
               
               
               
               
               
               
               
             
               
               
             
               
               
               
               
               
               
               
               
             
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 5 
               
               
                   
               
               
                 Combined weather and durability test: length 45 days, temperature 45-70 
               
               
                 F., medium sun. Hair was shampooed with a mild shampoo every other day. 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 Copper Gluconate vs. Iron Gluconate % (of 100% total) proportion 
               
             
          
           
               
                   
                 0:100 
                 10:90 
                 30:70 
                 50:50 
                 70:30 
                 90:10 
                 100:0 
               
               
                   
               
               
                 Discoloration 
                 Heavy 
                 Moderate 
                 Mild 
                 Very 
                 Very 
                 Very 
                 Very 
               
               
                   
                   
                   
                   
                 Mild 
                 Mild 
                 Mild 
                 Mild 
               
               
                   
               
             
          
           
               
                   
                 Copper Lactate vs. Iron Gluconate % (of 100% total) proportion 
               
             
          
           
               
                   
                 0:100 
                 10:90 
                 30:70 
                 50:50 
                 70:30 
                 90:10 
                 100:0 
               
               
                   
               
               
                 Discoloration 
                 Heavy 
                 Moderate 
                 Mild to 
                 Mild 
                 Very 
                 Very 
                 Mild 
               
               
                   
                   
                   
                 Moderate 
                   
                 Mild 
                 Mild 
               
               
                   
               
             
          
           
               
                   
                 Copper Acetate vs. Iron Gluconate % (of 100% total) proportion 
               
             
          
           
               
                   
                 0:100 
                 10:90 
                 30:70 
                 50:50 
                 70:30 
                 90:10 
                 100:0 
               
               
                   
               
               
                 Discoloration 
                 Heavy 
                 Moderate 
                 Moderate 
                 Mild 
                 Very 
                 Very 
                 Mild 
               
               
                   
                   
                   
                   
                   
                 Mild 
                 Mild 
               
               
                   
               
             
          
         
       
     
     In all cases heavy discoloration was observed buy using an iron salt. Addition of copper significantly improved weather resistance and durability of color. 
     Self Chelating Properties of Copper Gluconate. 
     The above described properties of copper gluconates, lactates, and succinates act as natural chelating agents. Some of the chelating properties of D-gluconic acid were described in publication on removal of heavy metals (K. Fisher at. all Removal of Heavy Metals from Soil Components and Soils by Natural Chelating Agents., Water, Air and Soil Pollution 138, 271, 2002). These properties of gluconates, lactates, and succinates and poly-nucleus complexes that disassociate to smaller formations and react with other ligand can possibly explain anomaly in behavior of copper salts in henna based compounding formulations. 
     To illustrate this fact the following experiment was performed. Copper salts of other acids—Copper Sulfate, Copper Chloride and Copper Acetate, were used in preparation of mordanting solution. Also, two commonly used chelating agents were used—Turpinal SL (Solutia)-Etidronic Acid and Versenol 120—EDTA (Dow Chemical). These chelating agents were used at a concentrations range of 0.09-2.0% to the gel based formula of mordant which than was applied on hair with the same “Dark Brown Henna” dye composition. The surprise was that there was no color deposition in any of the cases using chelating agents, even at low concentration of 0.09%. See Table 6. 
     
       
         
               
             
               
               
             
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 6 
               
             
             
               
                   
               
               
                 Influence of different copper salts and chelating agents on color deposition 
               
             
          
           
               
                   
                 Copper salt &amp; Chelating agent, % 
               
             
          
           
               
                   
                   
                 Copper 
                 Copper 
                 Copper 
                 Copper 
                 Copper 
                 Copper 
               
               
                   
                   
                 Sulfate 
                 Chloride 
                 Acetate 
                 Sulfate 
                 Sulfate 
                 Sulfate 
               
               
                   
                 Copper 
                 0.09-2.0%% 
                 0.09-2.0%% 
                 0.09-2.0%% 
                 0.09-2.0%% 
                 0.09-2.0%% 
                 0.09-2.0%% 
               
               
                   
                 Gluconate 
                 Versenol 
                 Versenol 
                 Versenol 
                 Turpinal 
                 Turpinal 
                 Turpinal 
               
               
                   
                   
               
             
          
           
               
                 Color 
                 YES 
                 NO 
                 NO 
                 NO 
                 NO 
                 NO 
                 NO 
               
               
                 Deposition 
               
               
                   
               
             
          
         
       
     
     Influence of Acid Type. 
     One of the surprising aspects of these findings was selectivity of the process involving “Dark Brown Henna” to a specific acid or acid type. 
     In most of the cases the use of acid is limited to pH adjustment. The most unexpected result was received on several experiments with different acids added to “Dark Brown Henna” formulas. The following acids were tested: Citric, Glycolic, Lactic and Acetic. The results are listed in Table 7. Surprisingly we found that similar acid types can have different influence on color deposition. 
     
       
         
               
             
               
               
               
               
               
             
           
               
                 TABLE 7 
               
             
             
               
                   
               
               
                 Influence of acids on color deposition 
               
             
          
           
               
                   
                 Lactic 
                 Glycolic 
                 Acetic 
                 Citric 
               
               
                 Acid, % 
                 0.5-5.0% 
                 0.5-5.0% 
                 0.5-5.0% 
                 0.5-5.0% 
               
               
                   
               
               
                 Color Deposition 
                 Good 
                 Good 
                 Moderate 
                 Very Low 
               
               
                   
               
             
          
         
       
     
     As shown in Table 7, the strongest color can be achieved by using Lactic and Glycolic acids. Acetic Acid produced a weaker color. Citric Acid showed an extremely weak color deposition. It was also completely unexpected that solution of Citric Acid can be used to remove stains from skin. 
     Citric and Lactic Acids were used in comparison with a typical mix of 10% nonionic surfactant, 25% of alcohol, 5% of acetone, and 60% water, that is used for cleaning color stains from skin. According to the results, Citric Acid is more effective in removing stains of henna based colorant from skin than Lactic Acid or typical stain removal mix. 
     Citric acid can be used in concentration of 0.5-10% as a stain remover as shown in Table 8. 
     
       
         
               
             
               
               
             
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                 TABLE 8 
               
             
             
               
                   
               
               
                 Removing stains using different acids 
               
               
                 and solvent-surfactant system 
               
             
          
           
               
                   
                 Type of stain remover vs. concentration 
               
             
          
           
               
                   
                   
                 Lactic 
                 Acetic 
                 Citric 
               
               
                   
                 Surfactant- 
                 Acid 
                 Acid 
                 Acid 
               
               
                   
                 solvent mix 
                 0.5-5.0% 
                 0.5-5.0% 
                 0.5-5.0% 
               
               
                   
                   
               
             
          
           
               
                 Stain Dark 
                 Not 
                 Partially 
                 Partially 
                 Completely 
               
               
                 Brown 
                 removed 
                 removed 
                 removed 
                 removed at 3.0% 
               
               
                 Stain Red 
                 Not 
                 Partially 
                 Partially 
                 Completely 
               
               
                 Brown 
                 removed 
                 removed 
                 removed 
                 removed at 5.0% 
               
               
                 Stain Yellow 
                 Not 
                 Partially 
                 Partially 
                 Completely 
               
               
                 Brown 
                 removed 
                 removed 
                 removed 
                 removed at 5.0% 
               
               
                   
               
             
          
         
       
     
     Influence of Combination of Acid and Alcohol. 
     Alcohols as solvents are employed in some hair coloring applications with and without mordant or salt. For example, in US 2001/0042276 A1, an application of dye, metal salt, and alcohol is described. In this particular case, the use of alcohol with synthetic CI Acid Dyes resulted in slowing rate of reaction between dye and protein (hair and scalp/skin). CI Acid Dyes are designed to dye keratin fibers at low pH. This reaction is extremely fast in acidic conditions and therefore scalp and skin stains can occur. A slow down reaction is generally recommended for leveling of color. While most vegetable dyes and henna are generally have no affinity to hair, the use of alcohol and acid combination has a purpose to increase color deposition on human hair. In US20030145395, the pH range from 2.0 to 6.0 is implied with henna compounding. However, there is no mention of use of alcohol of any kind and/or ligand binded cooper as a complex forming system. 
     Color deposition was measured on DeMeo Brothers Natural White hair. “Dark Brown Henna” color was prepared using the following solvents (some of them can be natural and made from the renewable sources): 
     Methanol, Ethanol, Propanol, Isopropanol, Butanol, Amyl Alcohol 
     These alcohols were used with following acids: Lactic, Glycolic, Citric, and Acetic. Dye and Cupper Gluconate based mordant were shaken together and applied on hair. The results are in Table 9. 
     
       
         
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE 9 
               
             
             
               
                   
               
               
                 Influence of alcohol type and acid on color deposition. 
               
             
          
           
               
                 Composition 
                   
                   
                   
                   
                   
                   
               
               
                 of acid type 
                   
                   
                   
                 Amyl 
                 Iso- 
               
               
                 vs. type of 
                 Meth- 
                 Ethanol 
                 Propanol 
                 Alcohol 
                 propyl 
                 Butanol 
               
               
                 alcohol 
                 anol 
                 Natural 
                 Natural 
                 Natural 
                 Alcohol 
                 Natural 
               
               
                   
               
               
                 Dye + 
                 Light 
                 Light 
                 Dark 
                 Light 
                 Dark 
                 Dark 
               
               
                 Lactic 
                 Brown 
                 Brown 
                 Brown 
                 Brown 
                 Brown 
                 Brown 
               
               
                 Dye + 
                 Light 
                 Light 
                 Dark 
                 Light 
                 Dark 
                 Light 
               
               
                 Glycolic 
                 Brown 
                 Brown 
                 Brown 
                 Brown 
                 Brown 
                 Brown 
               
               
                 Dye + 
                 Low to 
                 Low to 
                 Low to 
                 Low to 
                 Low to 
                 Low to 
               
               
                 Citric 
                 none 
                 none 
                 none 
                 none 
                 none 
                 none 
               
               
                 Dye + 
                 Low to 
                 Low to 
                 Light 
                 Low to 
                 Light 
                 Low to 
               
               
                 Acetic 
                 none 
                 none 
                 Brown 
                 none 
                 Brown 
                 none 
               
               
                   
               
             
          
         
       
     
     As shown in Table 9, the influence of alcohol on color deposition is selective and the best performance is (in descending order): Propanol, Butanol, Isopropyl Alcohol, Amyl, Ethanol and Methanol. 
     Influence of Solvent and Co-Solvent. 
     Co-solvents are an important part of hair coloring formulation. Typical co-solvents are Glycerin, Propylene Glycol, Butylene Glycol (A. Hunting, Encyclopedia of Shampoo Ingredients, Micelle Press, 1983, pp 240-243; 319-323). Another co-solvent for hair coloring applications is Propanediol from corn by DuPont. 
     Table 10 shows the results of co-solvent influence on hair color deposition of henna based formulations in different color shades. 
     
       
         
               
             
               
               
               
               
               
               
             
           
               
                 TABLE 10 
               
             
             
               
                   
               
               
                 Influence of co-solvent type and acid on color deposition. 
               
             
          
           
               
                 Composition 
                   
                   
                   
                   
                   
               
               
                 of acid type 
                 Pro- 
                   
                 Pro- 
                 Glycerin/ 
                 Butyl- 
               
               
                 vs. type of 
                 pylene 
                 Glycerin 
                 panediol 
                 Propanediol 
                 ene 
               
               
                 co-solvent 
                 Glycol 
                 Vegetable 
                 From Corn 
                 50:50 
                 Glycol 
               
               
                   
               
               
                 Dye + 
                 Light 
                 Dark 
                 Light 
                 Dark 
                 Dark 
               
               
                 Lactic 
                 Brown 
                 Brown 
                 Brown 
                 Brown 
                 Brown 
               
               
                 Dye + 
                 Light 
                 Dark 
                 Light 
                 Dark 
                 Light 
               
               
                 Glycolic 
                 Brown 
                 Brown 
                 Brown 
                 Brown 
                 Brown 
               
               
                 Dye + 
                 Low to 
                 Low to 
                 Low to 
                 Low to 
                 Low to 
               
               
                 Citric 
                 none 
                 none 
                 none 
                 none 
                 none 
               
               
                 Dye + 
                 Low to 
                 Light 
                 Low to 
                 Light 
                 Low to 
               
               
                 Acetic 
                 none 
                 Brown 
                 none 
                 Brown 
                 none 
               
               
                   
               
             
          
         
       
     
     As shown in Table 10, best results can be achieved by using Glycerin and Propanediol or its mixture with Lactic or Glycolic Acids. 
     Dye Concentrates 
     A totally unexpected result was obtained by mixing and heating compounded henna with acid and co-solvent as shown by the results recorded in Table 11. This process enables compounded henna to act as a dye concentrate for permanent and semi-permanent natural hair coloring products. These dye concentrates, when dispersed in water and/or water based formulations such as gels, emulsions, suspensions, shampoos and conditioners. An example of compounded henna dye concentrate is illustrated in Table 11. 
     
       
         
               
             
               
               
               
               
               
               
             
           
               
                 TABLE 11 
               
             
             
               
                   
               
               
                 Color deposition of compounded henna dye concentrate 
               
               
                 on human hair in shampoo (pH 4.5-3.0). 
               
             
          
           
               
                   
                   
                   
                   
                 Glycerin/ 
                   
               
               
                 Type of 
                 Propylene 
                   
                 Pro- 
                 Propanediol 
                 Butilene 
               
               
                 co-solvent 
                 Glycol 
                 Glycerin 
                 panediol 
                 50:50 
                 Glycol 
               
               
                   
               
               
                 Dye + 
                 Light 
                 Dark 
                 Light 
                 Dark 
                 Dark 
               
               
                 Lactic 
                 Yellow 
                 Yellow 
                 Yellow 
                 Yellow 
                 Yellow 
               
               
                 0.1-5.0% 
               
               
                 Dye + 
                 Light 
                 Dark 
                 Light 
                 Dark 
                 Light 
               
               
                 Glycolic 
                 Yellow 
                 Yellow 
                 Yellow 
                 Yellow 
                 Yellow 
               
               
                 0.1-5.0% 
               
               
                 Dye + 
                 Low to 
                 Light 
                 Light 
                 Light 
                 Low to 
               
               
                 Acetic 
                 none 
                 Yellow 
                 Yellow 
                 Yellow 
                 none 
               
               
                 0.1-5.0% 
               
               
                   
               
             
          
         
       
     
     As it follows from Table 11,in the presence of co-solvent, such as Glycerin and Propanediol, golden, golden-orange, and dark golden shades can be obtained by heating compounded henna dye concentrate at low pH (4.5 and lower). 
     Most importantly, the co-solvent can be natural and made from renewable sources (Glycerin and corn based Propanediol). 
     Most surprising and unexpected was a significant color deposition from formulations prepared with this concentrate type even without presence of ligand binding complexes. 
     More Detailed Description of Preparation and Application of Natural Dye Concentrates in all Natural Permanent and Semi-Permanent Hair Dying Formulations 
     Using dye concentrates oppose to mixing dry powders has significant technological advantages. 
     First, using dye concentrates in comparison with addition of compounded henna powders makes entire technological process more flexible. For example, same dye concentrate can be used for several formulation types, i.e. gels, emulsions, suspensions, shampoos and conditioners. 
     Second, it is known that some of the commonly used natural hair colorants like henna are not water soluble. In fact, main disadvantages of regular dry henna is required mixing of dry henna powder with boiling water to produce henna paste for application and application of heat for several hours. 
     Third, it is known that plant based extracts are inconsistent in concentration of their dyeing substances due to cultivar and environmental differences. Therefore, there are many challenges in shade consistency from batch to batch and variability of natural coloring formulations. 
     These problems can be worked out by using dye concentrates prepared as slurry of plant extracts in glycerin and/or glycol at low pH (4.0-2.5) and used for many formulations of permanent and semi-permanent color, emulsions, suspensions, shampoos and conditioners and stored for long periods of time without risk of running bacterial growth. This will also enable the greater technological flexibility and time saving in color adjusting. 
     Preparation of Dye Concentrates 
     Dye concentrates can be prepared using natural dye co-solvents, natural dye carriers, natural acids, henna, natural dyes and color contained actives, vitamins, co-enzymes, bioflavonoids, flavonoids, isoflavonoids, neoflavonoids. 
     Natural dye co-solvents can be selected from Glycerin and/or corn based Propanediol at concentration 5.0-50%. 
     Natural dye carriers can be selected from natural Benzyl Alcohol, natural Benzaldehyde and/or natural Benzyl Acetate at concentration 0.1-10%. 
     Natural acids can be selected from Lactic, Glycolic, Acetic or Citric acids at concentration 0.1-10.0%. 
     Henna can be used at concentration 0.1-30.0%. 
     Natural Dyes and Color Contained Actives (antioxidants, antimicrobials and other phyto-therapeuticals) can be used at concentration 0.5-15.0% and selected from: Acacia Dealbata Flower/Stem Extract, Annatto, Anthocyanins, Astaxanthin, Betanin, Capsanthin/Capsorubin, Carotenoids, Chlorophyll, Coptis Japonica Rhizome Extract, Crocus Sativus Flower Extract, Curcuma Longa, Turmeric Extract, Dunaliella Bardawil Powder, Gardenia Florida Fruit Extract, Gardenia Jasminoides Fruit Extract, Guaiazulene, Carthamin, Rosa Hybrid Flower Extract, Rubia Cordifolia Root Extract, Rubia Tinctorum Root Extract, Purpuroxanthin, Morindanigrin, Morindadiol, Rhubarb Extract, Purpurin, Pseudupururin, Morindone, Emodin, Crocin, Crocetin, Canthaxanthin, Sorghum Vulgare Seed/Skin/Stalk Extract, Vitis Vinifera (Grape) Fruit Powder, Vitis Vinifera (Grape) Skin Extract, Wine Extract, Deoxysantalin, Atromentin, Humin, Berberine. 
     Vitamins and Co-enzymes can be used at concentration 0.5-15.0% and selected from: Beta Carotene, D-Alpha Tocopherols, Co Enzyme Q-10, D-Biotin, Folic Acid, Niacin, Niacinamid, Riboflavin, Tocopherol, Vitamin A, B1, B2, B5, B6, B12, D3. 
     Bioflavonoids, flavonoids, isoflavonoids, neoflavonoids can be used at concentration 0.5-15.0% and selected from: Flavone, Luteolin, Apigenin, Baicalein, Rutin, Acacetin, Fisetin, Kaempferol, Myricetin, Quercetin, Naringenin, Hesperidin, Taxifolin, Genistein, Genistin, Daidzein, BiochaninA, Doxorubicin, Quercetin, Kaempferol, Myricetin, Fisetin, Isorhamnetin, Pachypodol, Rhamnazin, Eriodictyol, Homoeriodictyol, Tangeritin, Dihydrokaempferol, Glycitein, Catechins, Epicatechins, Morin, Brazelin, Brazilein, Haematein, Haematoxylon, Atrocappanon, Fukugetin, Datiscetin, Rhamnocitrin, Rhamnetin, Xanthorhamnin, Gossypetin. 
     Depending upon stability ingredients can be added together and heated up to 75 C or added after slurry cools down. 
     Total pH of dye concentrate should be 4.5 and lower. 
     Influence of Carriers. 
     A well known dye carrier is Benzyl Alcohol. Benzyl Alcohol, Benzaldehyde and Benzyl Acetate can be derived from sustainable sources like Jasmine, Ylang-Ylang, Cashew oil or oil of Bitter Almond. Other carriers from this category are Benzyl Benzoate or Ethyl Benzoate. 
     
       
         
               
             
               
               
               
               
               
               
             
           
               
                 TABLE 12 
               
             
             
               
                   
               
               
                 comparative properties of potential dye 
               
               
                 carriers on “Dark Brown Henna” 
               
             
          
           
               
                 Acid 
                 Benzyl 
                 Benzyl Alcohol 
                   
                 Benzal- 
                   
               
               
                 type vs. 
                 Acetate 
                 Natural/ 
                 Ethyl 
                 dehyde 
                 Benzyl 
               
               
                 carrier 
                 Natural 
                 Synthetic 
                 Benzoate 
                 Natural 
                 Benzoate 
               
               
                   
               
               
                 Lactic 
                 Light 
                 Dark 
                 Light 
                 Dark 
                 Light 
               
               
                   
                 Brown 
                 Brown 
                 Brown 
                 Brown 
                 Brown 
               
               
                 Glycolic 
                 Light 
                 Dark 
                 Light 
                 Dark 
                 Light 
               
               
                   
                 Brown 
                 Brown 
                 Brown 
                 Brown 
                 Brown 
               
               
                 Acetic 
                 Light 
                 Medium 
                 Low to 
                 Medium 
                 Low to 
               
               
                   
                 Brown 
                 Brown 
                 none 
                 Brown 
                 none 
               
               
                   
               
             
          
         
       
     
     As shown in Table 12 both natural and synthetic dye carriers perform adequately well in this dye system. In fact, Benzyl Alcohol was unexpectedly found to be a superior dye carrier. 
     Distribution of Copper in the Hair Fiber and Cumulative Effect of Color. 
     It was noted that hair colorant prepared with copper based compounded henna formulations have a cumulative effect. This effect is probably due to particle distribution of copper ligand binded complexes in human hair. These poly-nucleus complexes form a stable structure with polymeric matrix with compensated spin and can disassociate to smaller formations and react with other ligands. Therefore, these complexes can act as a depot of ligands redistributing complex forming systems within an addition of more dye. 
     The best deposition of color was observed when an entire system was applied couple consecutive times without using durability of color. No “wash off” color has been observed. Therefore, it can be concluded that most of colorants had been cumulatively binded to the hair. 
     Hair Coloring Kits 
     An encapsulate free two part all plant based hair coloring kit with controlled color deposition due to delay in reaction between salt and dye was prepared. This product enables one to observe, control and adjust color development and deposition during the coloring process. 
     The product may be formulated as a kit which contains a cleaning solution that may preferably contain Citric Acid. The kit can contain customizable coloring tinctures, color adjusters, and root pretreatment solution for coverage of resistant gray. 
     Due to poly-nucleus copper complexes formations and reactions with other ligands, a cumulative effect of product can be achieved, even on the same day of application. 
     EXAMPLES 
     Example 1 
     Two Part Hair Coloring Kit 
     Two parts of Hair Coloring Kit and/or customizable coloring tinctures and/or root pretreatment solution for coverage of resistant gray 
     Concentrations of ingredients will vary depending upon the type of the product (tincture, color, or solution for coverage of resistant gray). Same formula type makes these products highly versatile and compatible with each other. All percentages are by volume. 
     Part 1 
     
       
         
               
               
               
               
             
           
               
                   
               
               
                 Component 
                 Broad 
                 Preferred 
                 Most Preferred 
               
               
                   
               
             
             
               
                 DI Water to make 100% 
                 100% 
                   
                   
               
               
                 Thickener (natural or synthetic) 
                 0.1 to 5.0% 
                 0.1 to 2.0% 
                 0.1 to 1.0% 
               
               
                 Solvent (natural or synthetic) 
                 1.0 to 40.0% 
                 2 to 25.0% 
                 5 to 15.0% 
               
               
                 Co-Solvent (natural or synthetic) 
                 0.1 to 20.0% 
                 1 to 15.0% 
                 3 to 10.0% 
               
               
                 Surfactant 
                 0.1 to 10.0% 
                 1 to 10.0% 
                 2 to 5.0% 
               
               
                 Carrier (natural or synthetic) 
                 0.1 to 10.0% 
                 1 to 10.0% 
                 2 to 5.0% 
               
               
                 Acid (natural or synthetic) 
                 0.1 to 10.0% 
                 1 to 7.0% 
                 1 to 3.0% 
               
               
                 Poly-nucleus copper based mineral 
                 0.1 to 20.0% 
                 1 to 15.0% 
                 2 to 10.0% 
               
               
                 complex (added to make part 1) - 
               
               
                   
               
             
          
         
       
     
     Part 2 
     Compounded henna made with at least one of the ingredients from classes of ingredients described in the Scope of Invention (added to make part 2)—0.5 to 20.0% 
     Example 2 
     Two Part Hair Coloring Kit for Resistant Gray 
     All Natural two part Hair Coloring Kit and/or customizable coloring tinctures and/or root pretreatment solution for coverage of resistant gray formulation: 
     
       
         
               
               
               
               
               
             
               
               
               
               
               
             
               
               
             
           
               
                   
                   
               
               
                   
                 Component 
                 Broad Range 
                 Preferred 
                 Most Preferred 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                 1 
                 DI Water to make 100% 
                   
                   
                   
               
               
                 2 
                 Natural Thickener (selected from one or more 
                 0.1 to 5.0% 
                 0.1 to 2.0% 
                 0.1 to 1.0% 
               
               
                   
                 of Guar Gum, Xanthan Gum, 
               
               
                   
                 Hydroxyethylcellulose, Cellulose Gum) 
               
               
                 3 
                 Natural Solvent (selected from one or more of 
                 1.0 to 40.0% 
                 2 to 25.0% 
                 5 to 15.0% 
               
               
                   
                 Natural Propanol, Natural Organic Ethanol, 
               
               
                   
                 Natural Amyl Alcohol, Natural Butanol) 
               
               
                 4 
                 Natural Co-solvent (selected from one or more 
                 0.1 to 20.0% 
                 1 to 15.0% 
                 3 to 10.0% 
               
               
                   
                 of Vegetable glycerin, Propanediol from corn) - 
               
               
                 5 
                 Natural Surfactant (selected from one or more 
                 0.1 to 10.0% 
                 1 to 10.0% 
                 2 to 5.0% 
               
               
                   
                 of Decyl Glucoside, Coco Glucoside etc) 
               
               
                 6 
                 Natural Carrier (selected from one or more of 
                 0.1 to 10.0% 
                 1 to 10.0% 
                 2 to 5.0% 
               
               
                   
                 Benzaldehyde from oil of Bitter Almond, 
               
               
                   
                 Benzyl Acetate and Benzyl Alcohol from 
               
               
                   
                 Jasmine or Ylang Ylang) 
               
               
                 7 
                 Natural Acid (selected from one or more of 
                 0.1 to 10.0% 
                 1 to 7.0% 
                 1 to 3.0% 
               
               
                   
                 lactic, glycolic, acetic) to pH 4.5 and lower 
               
               
                 8 
                 Poly-nucleus copper based mineral complex 
                 0.1 to 20.0% 
                 1 to 15.0% 
                 2 to 10.0% 
               
               
                   
                 (one part of salt is made from plant) - for 
               
               
                   
                 part 1 at pH 4.5 and lower 
               
             
          
           
               
                 All Natural henna based vegetable dye composition - 
                 0.5 to 20.0% 
               
               
                 for part2 
               
               
                   
               
             
          
         
       
     
     Examples of the above hair coloring kit with controlled color deposition due to delay in reaction between salt and dye applications: 
     In a separate two part all natural hair coloring kit embodiment of the invention, one part is applied on top of the other. When second part is applied, it is possible to observe, control, and adjust the development of color due to delay in reaction between salt and dye. 
     Optionally, the kit can be equipped with customizable coloring tinctures of tonal colors and sprays for resistant gray. Optionally, the kit can be applied few times on the same day to achieve cumulative properties. 
     In a mixable two part all natural hair coloring kit embodiment, parts can be mixed using conventional bowl and brush. When mixed parts are applied, it is possible to observe, control, and adjust the development of color due to delay in reaction between salt and dye. Optionally, the kit can be equipped with customizable coloring tinctures of tonal colors and sprays for resistant gray. Optionally, the kit can be applied few times on the same day to achieve cumulative properties. 
     In a shakable two part all natural hair coloring kit with applicator for home use embodiment, the parts can be mixed using conventional bowl and brush. When mixed parts are applied, it is possible to observe, control, and adjust the development of color due to delay in reaction between salt and dye. Optionally, the kit can be equipped with customizable coloring tinctures of tonal colors and sprays for resistant gray. Optionally, the kit can be applied few times on the same day to achieve cumulative properties. 
     One Part Dual Chamber Bottle Two Part All Natural Hair Coloring Kit. 
     Parts are mixed upon release. The kit can optionally contain customizable coloring tinctures of tonal colors mixable and/or as a part of one of the chambers of Dual Chamber bottle. Optionally, the kit can be equipped with customizable coloring spray for resistant gray. Optionally, the kit can be applied few times on the same day to achieve cumulative properties. 
     All Natural Kit for Blending Gray. 
     All Natural Kits for Blending Gray can be comprised of shampoo, conditioner, styling aid and color fixative spray and/or other delivery combination containing at least two of the above. This system is encapsulate free. Due to poly-nucleus copper complexes formations and reactions with other ligand, the cumulative effect of product can be achieved, even on the same day of application. 
     The color and grey coverage can be adjusted to desirable tone. At least one part will contain poly-nucleus copper based mineral complex. Another part contains compounded henna complex. 
     Formulation: 
     Shampoo 
     DI Water 
     Primary surfactant 
     Secondary surfactant 
     Tertiary Surfactant 
     Thickener 
     Solvent 
     Co-Solvent 
     Acid 
     Dye Carrier 
     Conditioning agents 
     Poly-nucleus copper based mineral complex or compounded henna complex 
     Conditioner 
     DI Water 
     Primary emulsifiers 
     Co-emulsifier 
     Thickeners 
     Oils 
     Solvent 
     Co-Solvent 
     Poly-nucleus copper based mineral complex or compounded henna complex 
     Conditioning agents 
     Acid 
     Spray 
     DI Water 
     Solvent 
     Co-solvent 
     Hair fixative resin 
     Poly-nucleus copper based mineral complex or compounded henna complex 
     Conditioning agents 
     Acid 
     Optionally may also contain: 
     Primary emulsifiers 
     Co-emulsifier 
     Thickeners 
     Formulation of All Natural Kit for Blending Grey. 
     Natural Shampoo 
     
       
         
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                   
                   
                   
                 Most 
               
               
                   
                 Component 
                 Broad Range 
                 Preferred 
                 Preferred 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                  1 
                 DI Water to 
                 100% 
                 Add to 
                 Add to 
               
               
                   
                   
                   
                 100% 
                 100% 
               
               
                  2 
                 Natural Thickener- Guar Gum 
                 0.1 to 5.0%  
                 0.1 to 2.0%   
                 0.1 to 1.0%   
               
               
                  3 
                 Natural solvent- Natural Propyl Alcohol 
                 0.1 to 10.0% 
                 1 to 8.0%  
                 2 to 5.0% 
               
               
                  4 
                 Natural co-solvent- Propanediol (from corn) 
                 0.1 to 10.0% 
                 1 to 8.0%  
                 2 to 5.0% 
               
               
                  5 
                 Natural Primary surfactant - selected from one 
                 1.0 to 20.0% 
                 2 to 18.0% 
                 12 to 15.0% 
               
               
                   
                 or more of Sodium Cocoyl Isethionate, Sodium 
               
               
                   
                 Lauroamphoacetate, Sodium Methyl Cocoyl 
               
               
                   
                 Taurate, Methylisothiazolione 
               
               
                  5a 
                 Natural Secondary surfactant- Decyl Glucoside 
                 1.0 to 15.%  
                 2 to 12.0% 
                  5 to 10.0% 
               
               
                  5b 
                 Natural Tertiary surfactant - Cocamidopropyl 
                 1.0 to 5.0%  
                 2 to 12.0% 
                  5 to 10.0% 
               
               
                   
                 Betaine 
               
               
                  6 
                 Natural dye carrier- natural benzaldehyde 
                 0.1 to 15.0% 
                 2 to 12.0% 
                 3 to 8.0% 
               
               
                  7 
                 Natural Citric Acid to pH 4.5 and lower 
                 0.1 to 10.0% 
                 0.2 to 5.0%   
                 0.5 to 3.0%   
               
               
                  8 
                 Poly-nucleus copper based mineral complex or 
                 0.1 to 20.0% 
                 1 to 15.0% 
                  2 to 10.0% 
               
               
                   
                 compounded henna complex at pH 4.5 and 
               
               
                   
                 lower 
               
               
                 40 
                 Natural conditioning agents- selected from one 
                 0.1 to 5.0%  
                 0.5 to 5.0%   
                 1 to 3.0% 
               
               
                   
                 or more of Hydroxypropyl Guar &amp; Chitosan 
               
               
                   
                 Succinamide 
               
               
                   
               
             
          
         
       
     
     Natural Conditioner 
     
       
         
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                   
                   
                   
                 Most 
               
               
                   
                 Component 
                 Broad Range 
                 Preferred 
                 Preferred 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                 1 
                 DI Water to make 100% 
                   
                 Add to 
                 Add to 
               
               
                   
                   
                   
                 100% 
                 100% 
               
               
                 2 
                 Thickeners- selected from one or more of Guar 
                 0.1 to 5.0%  
                 0.1 to 2.0% 
                 0.1 to 1.0% 
               
               
                   
                 gum, Xanthan gum, Hydroxyethyl Cellulose, 
               
               
                   
                 Cellulose Gum 
               
               
                 3 
                 Solvent- Organic Grain Ethanol 
                 0.1 to 10.0% 
                   1 to 8.0% 
                   2 to 5.0% 
               
               
                 4 
                 Co-Solvent- Vegetable Glycerin 
                 0.1 to 10.0% 
                   1 to 8.0% 
                   2 to 5.0% 
               
               
                 7 
                 Natural Acid- Natural Citric Acid to pH 4.5 and 
                 0.1 to 10.0% 
                 0.2 to 5.0% 
                 0.5 to 2.0% 
               
               
                   
                 lower 
                   
                   
                   
               
               
                 8 
                 Poly-nucleus copper based mineral complex or 
                 0.1 to 20.0% 
                   1 to 15.0% 
                   2 to 10.0% 
               
               
                   
                 compounded henna complex at pH 4.5 and 
               
               
                   
                 lower 
               
               
                 17 
                 Oils-: selected from one or more of  Persea   
                 1.0 to 25.0% 
                  2.0 to 15.0% 
                  7.0 to 10.0% 
               
               
                   
                   Gratissima  (Avocado) Oil;  Glycine Soja  Protein 
               
               
                   
                 (Soybean);  Simmondsia Chinensis  (Jojoba) 
               
               
                   
                 Seed Oil 
               
               
                 30 
                 Natural Primary emulsifiers- selected from one 
                 0.5 to 10.0% 
                 1.0 to 8.0% 
                 2.0 to 7.0% 
               
               
                   
                 or more of Cetearyl Alcohol and Behenyl 
               
               
                   
                 Alcohol 
               
               
                 31 
                 Co-emulsifier- selected from one or more of 
                 0.5 to 10.0% 
                 1.0 to 8.0% 
                 2.0 to 7.0% 
               
               
                   
                 Arachidyl Glucoside, Coco Glucoside and 
               
               
                   
                 Coconut Alcohol 
               
               
                 40 
                 Natural Conditioning agents- selected from one 
                 1.0 to 15.0% 
                 0.5 to 5.0% 
                   1 to 3.0% 
               
               
                   
                 or more of Beta-Glucan, Hydroxypropyl Guar, 
               
               
                   
                 Chitosan Succinamide,  Triticum Vulgare   
               
               
                   
                 (Hydrolyzed Wheat) Protein 
               
               
                   
               
             
          
         
       
     
     Natural Spray/Natural Styling Aid (Gel or Mousse) 
                                                                                       Most           Component   Broad Range   Preferred   Preferred                                    1   DI Water to make 100%       Add to   Add to                   100%   100%       3   Solvents- selected from one or more of Organic   0.1 to 45.0%   5 to 30.0%   5 to 15.0%           Grain Ethanol and Natural Propyl Alcohol       4   Co-solvents- Vegetable glycerin and   0.1 to 15.0%   1 to 12.0%   2 to 5.0%            Propanediol (from corn)       7   Natural Acid- Natural Citric acid to pH 4.5 and   0.1 to 10.0%   0.2 to 5.0%     0.5 to 3.0%             lower       8   Poly-nucleus copper based mineral complex or   0.1 to 20.0%   1 to 15.0%   2 to 10.0%           compounded henna complex at pH 4.5 and           lower       10   Conditioning agents- selected from one or more   0.1 to 15.0%   0.5 to 5.0%     1 to 3.0%            of Hydroxypropyl Guar &amp; Chitosan           Succinamide       21   Hair fixative resins- selected from one or more   0.1 to 5.0%    0.1 to 2.0%     0.1 to 1.0%             of Guar Gum, Hyrdoxyethyl Cellulose, and           Cellulose Gum                    
where each of the components of the kit may optionally contain:
 
     
       
         
               
               
               
             
           
               
                   
               
             
             
               
                 2 
                 Thickeners- selected from one or more 
                 0.1 to 5.0%  
               
               
                   
                 of Guar gum, Xanthan gum, 
               
               
                   
                 Hydroxyethyl Cellulose, Cellulose Gum 
               
               
                 30 
                 Natural Primary emulsifiers- selected 
                 0.5 to 10.0% 
               
               
                   
                 from one or more of Cetearyl 
               
               
                   
                 Alcohol and Behenyl Alcohol 
               
               
                 31 
                 Co-emulsifier- selected from one or 
                 0.5 to 10.0% 
               
               
                   
                 more of Arachidyl Glucoside, 
               
               
                   
                 Coco Glucoside and Coconut Alcohol 
               
               
                   
               
             
          
         
       
     
     Two part all natural kit for blending gray. At least one part should be conditioner, and another part can be shampoo or spray. On a course of application, it is possible to observe, control, and adjust the development of color due to cumulative effect. Application can be stopped when desirable blending of gray is achieved. After that kit can be continued once a week as maintenance. 
     Three parts all natural kit for blending gray. This system contains shampoo, conditioner, and spray. On a course of application, it is possible to observe, control, and adjust the development of color due to cumulative effect. Application can be stopped when desirable blending of gray is achieved. After that kit can be continued once a weak as maintenance. 
     Four parts all natural kit for blending gray. This system contains shampoo, conditioner, spray, and hair fixative aid. On a course of application, it is possible to observe, control, and adjust the development of color due to cumulative effect. Application can be stopped when desirable blending of gray is achieved. After that kit can be continued once a weak as maintenance. 
     Dual Chamber bottle all natural kit for blending gray. This system contains shampoo, conditioner, spray, and hair fixative aid. Either two or four parts are in Dual Chamber. Therefore, this kit can contain one dual chamber bottle with shampoo and conditioner combined with color fixative spray and hair fixative aid. Another combination is two dual chamber bottles—one contains shampoo and conditioner, and another contains hair fixative liquid and styling aid. On a course of application, it is possible to observe, control, and adjust the development of color due to cumulative effect. Application can be stopped when desirable blending of gray is achieved. After that kit can be continued once a weak as maintenance. 
     All Natural Tonal (Semi-Permanent) Tint Kit. 
     All Natural Tonal(Semi-Permanent) Tint Kits can be comprised of shampoo, conditioner, styling aid and color fixative spray and/or other delivery combinations containing at least two of the above. This product is encapsulate free. This system provides controlled color deposition. This applications enables to observe, control and adjust color development and deposition during the coloring process. 
     Due to poly-nucleus copper complexes formations and reactions with other ligand, a cumulative effect of product can be achieved, even on the same day of application. At least one part will contain poly-nucleus copper based mineral complex. Another part will contain compounded henna complex. 
     Formulation: 
     Shampoo 
     DI Water 
     Primary surfactant 
     Secondary surfactant 
     Tertiary Surfactant 
     Thickener 
     Solvent 
     Co-Solvent 
     Acid 
     Dye Carrier 
     Conditioning agents 
     Poly-nucleus copper based mineral complex or compounded henna complex 
     Conditioner 
     DI Water 
     Primary emulsifiers 
     Co-emulsifier 
     Thickeners 
     Oils 
     Solvent 
     Co-Solvent 
     Poly-nucleus copper based mineral complex or compounded henna complex 
     Conditioning agents 
     Acid 
     Spray 
     DI Water 
     Solvent 
     Co-solvent 
     Hair fixative resin 
     Poly-nucleus copper based mineral complex or compounded henna complex 
     Conditioning agents 
     Acid 
     Can also contain: 
     Primary emulsifiers 
     Co-emulsifier 
     Thickeners 
     Formulation of All Natural Tonal (Semi-Permanent) Tint Kit: 
     Natural Shampoo 
     
       
         
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                   
                   
                   
                 Most 
               
               
                   
                 Component 
                 Broad Range 
                 Preferred 
                 Preferred 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                  1 
                 DI Water to make100% 
                   
                 Add to 
                 Add to 
               
               
                   
                   
                   
                 100% 
                 100% 
               
               
                  2 
                 Natural Thickener- Guar Gum 
                 0.1 to 5.0%  
                 0.1 to 2.0%   
                 0.1 to 1.0%   
               
               
                  3 
                 Natural solvent- Natural Propyl Alcohol 
                 0.1 to 10.0% 
                 1 to 8.0%  
                 2 to 5.0% 
               
               
                  4 
                 Natural co-solvent- Propanediol (from corn) 
                 0.1 to 10.0% 
                 1 to 8.0%  
                 2 to 5.0% 
               
               
                  5 
                 Natural Primary surfactant - selected from one 
                 1.0 to 20.0% 
                 2 to 18.0% 
                 12 to 15.0% 
               
               
                   
                 or more of Sodium Cocoyl Isethionate, Sodium 
               
               
                   
                 Lauroamphoacetate, Sodium Methyl Cocoyl 
               
               
                   
                 Taurate, Methylisothiazolione 
               
               
                  5a 
                 Natural Secondary surfactant- Decyl Glucoside 
                 1.0 to 15.%  
                 2 to 12.0% 
                  5 to 10.0% 
               
               
                  5b 
                 Natural Tertiary surfactant - Cocamidopropyl 
                 1.0 to 5.0%  
                 2 to 5.0%  
                 3 to 5.0% 
               
               
                   
                 Betaine 
               
               
                  6 
                 Natural dye carrier- natural benzaldehyde 
                 0.1 to 15.0% 
                 2 to 12.0% 
                 3 to 8.0% 
               
               
                  7 
                 Natural Citric Acid to pH 4.5 and lower 
                 0.1 to 10.0% 
                 0.2 to 5.0%   
                 0.5 to 3.0%   
               
               
                  8 
                 Poly-nucleus copper based mineral complex or 
                 0.1 to 20.0% 
                 1 to 15.0% 
                  2 to 10.0% 
               
               
                   
                 compounded henna complex at pH 4.5 and 
               
               
                   
                 lower 
               
               
                 10 
                 Natural conditioning agents- selected from one 
                 0.1 to 5.0%  
                 0.5 to 5.0%   
                 1 to 3.0% 
               
               
                   
                 or more of Hydroxypropyl Guar &amp; Chitosan 
               
               
                   
                 Succinamide 
               
               
                   
               
             
          
         
       
     
     Natural Conditioner 
     
       
         
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                   
                 Broad 
                   
                 Most 
               
               
                   
                 Component 
                 Range 
                 Preferred 
                 Preferred 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                 1 
                 DI Water to make 100% 
                   
                   
                   
               
               
                 2 
                 Thickeners- selected from one or more of 
                 0.1-5.0%  
                 0.1 to 2.0% 
                 0.1 to 1.0% 
               
               
                   
                 Guar gum, Xanthan gum, Hydroxyethyl 
               
               
                   
                 Cellulose, Cellulose Gum 
               
               
                 3 
                 Solvent- Organic Grain Ethanol 
                 0.1-10.0% 
                   1 to 8.0% 
                   2 to 5.0% 
               
               
                 4 
                 Co-Solvent- Vegetable Glycerin 
                 0.1-10.0% 
                   1 to 8.0% 
                   2 to 5.0% 
               
               
                 7 
                 Natural Acid- Natural Citric Acid to pH 4.5 
                 0.1 to 10.0% 
                 0.2 to 5.0% 
                 0.5 to 2.0% 
               
               
                   
                 and lower 
               
               
                 8 
                 Poly-nucleus copper based mineral complex 
                 0.1-20.0% 
                   1 to 15.0% 
                   2 to 10.0% 
               
               
                   
                 or compounded henna complex at pH 4.5 
               
               
                   
                 and lower 
               
               
                 10 
                 Natural Conditioning agents- selected from 
                 1.0 to 15.0% 
                 0.5 to 5.0% 
                   1 to 3.0% 
               
               
                   
                 one or more of Beta-Glucan, Hydroxypropyl 
               
               
                   
                 Guar, Chitosan Succinamide,  Triticum   
               
               
                   
                   Vulgare  (Hydrolyzed Wheat) Protein 
               
               
                 13 
                 Natural Primary emulsifiers- selected from 
                 0.5-10.0% 
                 1.0 to 8.0% 
                 2.0 to 7.0% 
               
               
                   
                 one or more of Cetearyl Alcohol and 
               
               
                   
                 Behenyl Alcohol 
               
               
                 14 
                 Co-emulsifier- selected from one or more of 
                 0.5-10.0% 
                 1.0 to 8.0% 
                 2.0 to 7.0% 
               
               
                   
                 Arachidyl Glucoside, Coco Glucoside and 
               
               
                   
                 Coconut Alcohol 
               
               
                 17 
                 Oils- : selected from one or more of  Persea   
                 1.0-25.0% 
                  2.0 to 15.0% 
                  7.0 to 10.0% 
               
               
                   
                   Gratissima  (Avocado) Oil;  Glycine Soja   
               
               
                   
                 Protein (Soybean); 
               
               
                   
                   Simmondsia Chinensis  (Jojoba) Seed Oil 
               
               
                   
               
             
          
         
       
     
     Natural Spray/Natural Styling Aid (Gel or Mousse) 
     
       
         
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                   
                   
                   
                 Most 
               
               
                   
                 Component 
                 Broad Range 
                 Preferred 
                 Preferred 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                 1 
                 DI Water to make 
                 100% 
                 Add to 
                 Add to 
               
               
                   
                   
                   
                 100% 
                 100% 
               
               
                 3 
                 Solvents- selected from one or more of Organic 
                 0.1 to 45.0% 
                   5 to 30.0% 
                   5 to 15.0% 
               
               
                   
                 Grain Ethanol and Natural Propyl Alcohol 
               
               
                 4 
                 Co-solvents- selected from one or more of 
                 0.1 to 15.0% 
                   1 to 12.0% 
                   2 to 5.0% 
               
               
                   
                 Vegetable glycerin and Propanediol (from corn) 
               
               
                   
                 Hair fixative resins- selected from one or more 
                 0.1 to 5.0%  
                 0.2 to 5.0% 
                 0.5 to 3.0% 
               
               
                   
                 of Guar Gum, Hyrdoxyethyl Cellulose, 
               
               
                   
                 Cellulose Gum 
               
               
                   
                 Conditioning agents- selected from one or more 
                 0.1 to 15.0% 
                 0.5 to 5.0% 
                   1 to 3.0% 
               
               
                   
                 of Hydroxypropyl Guar &amp; Chitosan 
               
               
                   
                 Succinamide 
               
               
                 7 
                 Natural Acid- Natural Citric acid to pH 4.5 and 
                 0.1-10.0% 
                 0.2 to 5.0% 
                 0.5 to 3.0% 
               
               
                   
                 lower 
               
               
                 8 
                 Poly-nucleus copper based mineral complex or 
                 0.1-20.0% 
                   1 to 15.0% 
                   2 to 10.0% 
               
               
                   
                 compounded henna complex at pH 4.5 and 
               
               
                   
                 lower 
               
               
                   
               
             
          
         
       
     
     Where each of the above compositions may also optionally contain: 
     
       
         
               
               
               
             
           
               
                   
               
             
             
               
                   
                 Natural Primary emulsifiers - selected 
                 0.5 to 10.0% 
               
               
                   
                 from one or more of Cetearyl Alcohol 
               
               
                   
                 and Behenyl Alcohol 
               
               
                   
                 Co emulsifier - selected from one or 
                 0.5 to 10.0% 
               
               
                   
                 more of Arachidyl Glucoside, Coco 
               
               
                   
                 Glucoside and Coconut Alcohol 
               
               
                 2 
                 Thickeners - selected from one or more 
                 0.1 to 5.0%  
               
               
                   
                 of Guar gum, Xanthan Gum, 
               
               
                   
                 Hydroxyethyl Cellulose, Cellulose Gum 
               
               
                   
               
             
          
         
       
     
     Kit Embodiments: 
     In a preferred embodiment a two part All Natural Tonal (Semi-Permanent) Tint Kit system delivers coloring tone and/or can be applied on its own as a semi-permanent color. At least one part should be conditioner, and another part can be shampoo or spray. Over a course of application, it is possible to observe, control, and adjust the development of color due to the cumulative effect. The application can be stopped when a desirable blending of gray is achieved. After that, the kit can be continued once a week as maintenance. 
     In a preferred embodiment a three part All Natural Tonal (Semi-Permanent)Tint Kit system delivers coloring tone and/or can be applied on its own as a semi-permanent color. This system contains shampoo, conditioner, and spray. Over a course of application, it is possible to observe, control, and adjust the development of color due to the cumulative effect. The application can be stopped when a desirable blending of gray is achieved. After that, the t kit can be continued once a week as maintenance. 
     In a preferred embodiment a four part All Natural Tonal (Semi-Permanent)Tint Kit system delivers coloring tone and/or can be applied on its own as a semi-permanent color. This system contains shampoo, conditioner, spray, and hair fixative aid. Over a course of application, it is possible to observe, control, and adjust the development of color due to the cumulative effect. The application can be stopped when a desirable blending of gray is achieved. After that, the kit can be continued once a week as maintenance. 
     All Natural Tonal (Semi-Permanent)Tint Kit may be comprised of dual chamber bottles that deliver coloring tone and/or can be applied on its own as a semi-permanent color. This system contains shampoo, conditioner, spray, and hair fixative aid. Either two or four parts are in the dual chambers. Therefore, this kit can contain one dual chamber bottle with shampoo and conditioner combined with color fixative spray and hair fixative aid. In another embodiment, the combination is two dual chamber bottles—one contains shampoo and conditioner, and another contains hair fixative liquid and styling aid. Over a course of application, it is possible to observe, control, and adjust the development of color due to the cumulative effect. Application can be stopped when a desirable blending of gray is achieved. After that kit can be continued once a week as maintenance.