Formulation Studies and Properties Evaluation of Natural Semi-permanent Hair Dye Made from Gromwell Root and Sappan Wood

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1 Transaction Formulation Studies and Properties Evaluation of Natural Semi-permanent Hair Dye Made from Gromwell Root and Sappan Wood Hanchieh Wang 1 and Chonyu Chen 2 1 Department of Cosmetic Applications & Management, Yuh-Ing Junior College Of Health Care & Management, No. 15, Lane 420, Dachang 2nd Road, Sanmin District, Kaohsiung City 807, Taiwan (R.O.C) 2 Department of Fashion Design, Shu-Te University, No. 59, Hun Shan Road, Yen Chau, Kaohsiung 824, Taiwan (R.O.C) Abstract : Gromwell Root and Sappan Wood were extracted to prepare 8 different semi-permanent hair dye formulations under ph 3, 4, 5, 6 and 7, 8, 9, 10, respectively. One commercialized hair dye was tested as the standard. Hair, after 8 shampoo washes with the Gromwell Root with ph 5 and Sappan Wood with ph 7, showed the best color differences, DE* 5.8 and 4.9, respectively, which were better than the DE* from the commercialized fruit acid semi-permanent hair dye. By using a confocal microscope, the dyed hair after 8 shampoo washes still showed hair dye fluorescence below hair cuticle mm. (Received 11 May, 2009 ; Accepted 27 June, 2009) 1. Introduction Nowadays, plant hair dye is not very popular. Most commercialized plant hair dyes use henna powder as a major component. Henna dye is obtained from the dried leaves of henna. It can be prepared by adding water, coffee or black tea to form a thicker liquid for directly dyeing hair. However some commercialized henna dyes add para-phenylenediamine (PPDA) or heavy metal to improve dyeing properties [1]. These formulations can cause allergic and heavy metal toxicity problems. At the present time, many papers have been written about the allergy and cancer-inducing problems of oxidation hair dyes [2-4]. The market, however, still uses a lot of oxidation hair dyes like PPDA and aminophenol because it is still hard to find better substitutes [5]. So, determining how to make a nontoxic and low allergy plant hair dye remains a very interesting research topic. Semi-permanent hair dye usually defines dyed hair as that which can last through 6-8 shampoo washes. It can be classified into three categories : acid dyes, basic dyes and disperse dyes. In 1997 Nil [6] mentioned that the semi-permanent acid hair dye had better color fastness compared to the other semi-permanent hair dye. It also proved that ethanol can increase dyeing affinity to hair. In other fields, Ma [3] used Gromwell Root, Sappan Wood and Safflower to dye wool and silk and showed a dry washing fastness rating of 4-5. The objective of this paper is to select natural plant dyes of Gromwell Root and Sappan Wood as hair dyes to develop semi-permanent hair dye formulations. Gromwell Root, its scientific name is Lithospermum Erythrorhizon, belongs to boraginaceae and is also called Arnebia Root. Ki [4] discovered that colorant extracted from Gromwell Root showed a reddish purple color shade with acetic acid, and a bluish purple color shade with sodium carbonate. The major extracting colorant of Gromwell Root is called shikonin (C16H16O5) (Fig. 1) that slightly dissolves in water. Shikonin normally dissolves in alcohol with evaporation and color migration property. In 1996 Chen [7] stated that the light stability of shikonin can be improved by adding Vit-E and p- Aminobenzoic acid (ultraviolet absorber). An antioxidative test was conducted for Lithospermum Erythrorhizon s extracts, such as isobutylshikonin, shikonin, 8-dihydroxy-2- (1-methoxy-4-methyl-3- pentenyl)-1, 4-naphthalenedione and the result proves that Fig. 1 Structures of Gromwell Root colorant components : shikonin, acetylshikoni.

2 the anti-oxidative effect does exist.furthermore, the antioxidative effect is enhanced when adding vitamin E to shikonin [8,9]. The scientific name of Sappan Wood is Sappan Lignum that belongs to leguminosae and is also called Red Wood and Brazil Wood. The research of Ma [3] showed that silk and wool dyed with Sappan Wood with chromium, copper and iron mordant turned purple, grey and a black color, respectively. Owing to the fact that the structure of Sappan Wood comes with several OH functional groups, it is easy to dissolve in water. The aqueous colorant extraction of Sappan Wood illustrated in Fig. 2, shows an orangish yellow color shade when ph<6, and a reddish purple color shade when ph>6 [3,10,11]. Sappan Wood, which was treated with Microwave Plasma when dyeing cotton fabric, can inhibit bacteria and achieve excellent dyeing fastness properties [12]. 2. Materials and methods 2.1 Plant and Colorant extraction The peeled and dry heartwood of Sappan Wood and dry Gromwell Root were purchased in Kaohsiung City, Taiwan. Colorant extraction from the Sappan Wood was repeated 4 times using a total of 490 g Sappan Wood and ml of de-ionized water. Every extraction process was maintained at 95 o C for 50 min. All extracted solutions were filtered three times using Whatman (42 ash-less, 11 cm) filter paper. The filtered solution was then concentrated by using a rotary evaporator (EYELA N-1000s). Using 2700 ml ethanol and 54 ml of 3% acetic acid, 450 g of Gromwell Root were soaked for 30 hr. This extracted solution was also filtered three times using Whatman (42 ash-less, 11 cm) filter paper. The filtered solution was then concentrated using a rotary evaporator [13]. 2.2 Bleaching hair and shampoo washes Real human hair purchased from a beauty shop was Fig. 2 Structures of Sappan Wood colorant components : Brasilin, Brasilein. Table 1 Test condition of shampoo wash bleached by 9% hydrogen peroxide (L Oreal s Platifiz Precision) three times for 30 min each time. The dyed hair shampoo washes was tested with a shaking bath (FIRSTEK B630D). The sample test condition is listed in Table 1. Each hair sample was put into a 500 ml erlenmeyer flask with 400 ml of de-ionized water and 5 g ph 7.5 hair shampoo (L Oreal Vitamino Color Shampoo). Every sample was tested for 7 min with the shaking bath at less than 200 rpm. After the shampoo washes, each sample hair was rinsed twice with 400 ml of de-ionized water in the shaking bath at 200 rpm for three minutes each time. Finally, each rinsed dyed hair was soaked with 0.01% (w/w) hair conditioner (L Oreal Vitamino Color conditioner) for10 sec and then dried with a hair dryer. 2.3 Hair dye formulation In this experiment, a buffer solution was used to prepare different ph hair dye formulations. Gromwell Root hair dye was formulated with ph 3, 4, 5, 6 and Sappan Wood hair dye with ph 7, 8, 9, 10. The buffer solution was prepared with disodium hydrogen phosphate-citric acid for ph 3, 4, 5, 6, 7, 8 and glycinesodium hydroxide for ph 9, Thin Layer Chromatography (TLC) We used a 3x9 cm TLC plate (Merck, silica gel 60) with developing solvent system of n-hexane, ethyl acetate, methyl alcohol mixture to calculate the Rf value of the components of Sappan Wood colorant and Gromwell Root. It also analyzed the components fluorescence response under UV light for the following experiment of confocal scanning probe microscopy. 2.5 SEM and confocal scanning probe microscopy Scanning electron microscopy (A JEOL 6330 TF Field Emission Electron Microscope) was used to observe the hair scale change after dyeing and the shampoo washes. Confocal scanning probe microscopy (CSPM, Leica TCS SP2) was used to analyze the hair dye sustained condition in the hair cortex after shampoo washes. 2.6 Color difference DE* and CIELAB measurement CIELAB color space is a popular tool for measuring the color property of reflective objects. The dyed hair

3 samples were measured by a spectrophotometer (X-Rite Sphere Spectrophotometer SP60) to see the DE* and CIELAB value change under different shampoo washing tests. Each sample was measured at three different places (upper, middle, and lower). The mean value was then calculated. The DE* is defined as : Table 2 Thin layer chromatography of Gromwell root and Sappan wood DE* = (DL * 2-DL * 1) 2 +(Da * 2-Da * 1) 2 +(Db * 2-Db * 1) 2 1/2 (1) DL * : lightness ; Da * : red/green axis ; Db * : yellow/ blue axis 2.7 Safety evaluation In past times, heavy metal was used in the hair dye to increase the dye s hair covering property. But it may be absorbed through the scalp into the body. Nowadays, most countries have regulations about using heavy metal in hair dye formulations. In this experiment, Sappan Wood hair dye with ph 10 and Gromwell Root hair dye with ph 3 were selected to measure the heavy metal quantity, by using inductively coupled plasma mass spectrometry (PE-SCIEX ELAN 6100 DRC). 3. Results and discussion 3.1 Thin layer chromatography of Gromwell root and Sappan wood Thin layer chromatography (TLC) was used to analyze the colorant components of Gromwell root and Sappan wood, detected via a 365 nm UV lamp (Entela UVGL-25). The best developing solvent system was ethyl acetate : n-hexane = 1 : 5 (V/V) for Gromwell root and ethyl acetate : n-hexane = 2 : 1 (V/V) for Sappan wood. As shown in Table 2, the TLC plate of both Gromwell root and Sappan wood colorants can be separated into 5 and 7 major components. Each component exhibits different color and may have different affinity with hair. That also explains why the color shade will change after different shampoo washes. 3.2 Concentration analysis of Gromwell Root and Sappan Wood colorant Since a reagent grade of Gromwell Root and Sappan Wood colorant is not available in the market, our lab prepared the standard colorants of Gromwell Root and Sappan Wood. By UV/VIS spectrometer, the maximum absorption peak nm (95% ethanol solution) of Gromwell Root and nm (water solution) of Sappan Wood were selected for a standard calibration curve. Samples of Gromwell Root with concentration 0.01% (w/w) to 0.04% (w/w) and Sappan Wood with concentration 0.1% (w/w) to 0.4% (w/w) were prepared to build a standard calibration curve for the following colorant quantity calculation. The calibration curve R 2 of Gromwell Root and Sappan Wood is and , respectively. 3.3 Preliminary experiment of hair dye formulation To investigate the best hair dye formulation, three different Sappan Wood colorant amounts : 6% (w/w), 8% (w/w), and 10% (w/w) and three different Gromwell Root amounts of 0.6% (w/w), 1% (w/w), and 1.4% (w/w) were prepared to dye six bleached hair samples. A Beehive dryer (KT-3020) was then used to warm the sample hair for 20 min, at 40. Afterwards, the sample was cooled down to room temperature (25 ) for 20 min and then shampoo washed and dried. This test was repeated 8 times and each shampoo washing sample was compared to the original bleached hair sample to calculate the DE* value. The higher DE* value means the better the hair dyeing effect on the hair sample. The experimental results are listed in Table 3, which can be a reference for the formulation study for the following experiments. According to the results, after 8 shampoo washes, the DE* of Sappan Wood 10% is 16.1, which is close to the DE* of Sappan Wood 8%, Considering the economic effect, Sappan Wood 8% formulation is the best choice. The DE* of 8 shampoo washes with Gromwell Root 1.4% is This is the best of the three formulations and will be selected as the best Gromwell root hair dye formulation. In formulation preparation, ethanol was replaced by isopropanol which is more stable and more popularly used in hair dye solvent.

4 Table 3 Different shampoo wash DE* of Gromwell Root with formulations 0.6%, 1%, 1.4% and Sappan Wood dyed hair with formulations 6%, 8%, 10% (compared to bleached hair without dyeing) Table 4 Hair dye formulation of Gromwell Root1.4% and Sappan Wood 8%(w/w) Table 5 Hair swatch of all formulation dyed hair with different shampoo washes 3.4 Hair dye formulation and preparation On the basis of Table 3, the final selected hair dye quantity for the following experiments are Gromwell Root, 1.4% (w/w) and Sappan Wood 8% (w/w), respectively. The real weight of extracting colorant is the one according to the calculation of UV/VIS standard calculation curve. The hair dye formulation total weight is based on 100 g. The hair dye formulations are listed in Table 4. These calculations are compulsory every time because the purity of extracting colorant of Sappan Wood and Gromwell Root won t be the same every time. We designed the experimental hair dye formulations, including one commercialized product (CP) as standard and four Gromwell Root 8% (w/w) with ph 3 to ph 6 and four Sappan Wood 4% (w/w) with ph 7 to ph 10 for comparison, and samples were named as GR3 to GR6 and SW7toSW10. In these formulations, vitamin E was purchased from Roche ; K-400 preservative was purchased from Schulke & Mayr ; glycerin was purchased from Cognis Deutschland ; isopropyl alcohol was purchased from Shimakyu s pure chemicals ; sodium phosphate, dibasic, 12- hydrate were purchased from Nihon Shiyaku Industries and Xanthan gum was purchased from National Starch & Chemical. The preparation method was done according to Table 4 by fully mixing the A components and fully mixing B components separately, then pouring A into B by using a Homomixer to mix both components thoroughly. 3.5 Color shade and washfastness of dyed hair All dyed hair samples treated with one to eight shampoo washes are listed in Table 1. The hair sample swatch is shown in Table 5 and the DE* value is calculated by comparing the dyed hair (without shampoo washes) with different hair samples that were shampoo washed (Table 6). Among these 9 hair dye formulations, Gromwell Root with ph 5 and Sappan Wood with ph 7 revealed the best washfastness conditions. After 8 shampoo washes, the DE* values of GR5 and SW7 were 5.8 and 4.9 respectively, which were much smaller than the 15.5 of the commercialized hair formulation. By calculating the linear regression of DE* change versus the different sample shampoo washing times of these nine formulations, we found the commercialized formulation with y = x , R 2 = , GR5 with y = x , R 2 = and SW7 with y = x , R 2 = It concluded that the slope of the equation for the commercialized formulation is higher, which means faster color shampoo washes fading. The R 2 value of these two lab formulations also showed better regression linearity than did the commercialized formulation.

5 Table 6 DE* value loss by comparing dyeing hair sample (without washes) with hair dye sample after 1 to 8 shampoo washes 3.6 Color shade analysis of dyed hair According to Fig. 3, the hair dyed sample GR3 and GR4 before shampoo washes, showed deeper reddish color shade compared to GR5 and GR6. After 8 shampoo washes, four formulations exhibited similar Da * value but the GR5 and GR6 had higher Db * value compared to GR3 and GR4, meaning that GR5 and GR6 reveal deeper yellowish color shade after 8 shampoo washes. Generally speaking, after 8 shampoo washes, all Gromwell root hair dye formulations showed similar color shade. All Da * Db * values of Sappan wood hair dye formulation are shown in Fig. 4. The higher ph sample showed higher Da * value with deeper reddish color shade and smaller Db * value with less yellowish color shade. After 8 shampoo washes, all Sappan wood hair dye formulations exhibited almost the same color shade. That means even different ph formulations showed different component affinity to hair before shampoo washes but after 8 shampoo washes only components with strong affinity remained inside the hair. 3.7 SEM and Confocal Scanning Probe Microscopy According to the SEM picture of GR3 and SW10 in Fig. 5, the hair cuticle was covered with a lot of hair dye after the dyeing process, but after 8 shampoo washes most of the dye was washed out of the hair cuticle. From the picture (Fig. 6) of confocal scanning probe microscopy, the same samples above were measured in the deeper area 0.02 mm beneath the hair cuticle surface. This cross section area shows a lot of hair dye before shampoo washes. After 8 shampoo washes, only a small portion of dye still remained in this area. 3.8 Safety evaluation An inductive coupled plasma-mass spectrometer was used to analyze the heavy metal component of randomly selected formulations of GR6 and SW10. The major heavy mental test results are listed in Table 7 and all fall (Solid dot before shampoo washes ; Hollow dot after 8 shampoo washes) Fig. 3 Color Distribution of L * a * b * Values for the Hair dyed sample by Gromwell Root (Solid dot before shampoo washes ; Hollow dot after 8 shampoo washes) Fig. 4 Color Distribution of L * a * b * Values for the Hair dyed sample by Sappan Wood inside the safety limits required by the Department of Health in Taiwan. 4. Conclusions In this paper, colorant extractions from Gromwell root and Sappan wood were used to formulate semipermanent hair dye. With different ph conditions, seven lab hair dye formulations and one commercialized hair dye formulation were evaluated under several physical and chemical tests. The results can be concluded as

6 Fig. 5 Cuticle of GR3 BSW10 dyed hair and after 8 shampoo washes. Gromwell root and Sappan wood have many varieties. Different ph formulations of each component show different affinity to virgin hair and express different dyed hair hue. But after 8 shampoo washes, Gromwell root and Sappan wood hair dye formulations will reach a very similar final hue. It can be explained that only the long lasting washfastness components can be retained in the hair after many shampoo washes. 4. The SEM and Confocal Scanning Probe Microscopy experiments show that part of the hair dye will stick on the hair scale before washing. After 8 shampoo washes, the hair dye will lose a lot but will also be distributed more homogeneously inside the hair. 5. Comparing different experimental results in this paper, the Gromwell root and Sappan wood are two kinds of natural plant that are worthwhile developing as semi-permanent hair dyes. References Fig. 6 follows : CSPM image of GR3 and SW10 dyed hair and dyed hair after 8 shampoo washes. 1. The hair dye hue of Gromwell root is close to light brown-grey, which is deeper at lower ph 3 formulation. The hair dye hue of Sappan wood is close to light brown-red, which is deeper at lower ph 10 formulation. 2. After 8 shampoo washes, the formulations of GR5 and SW7 show better washfastness (by DE*) than does the commercialized product. 3. From TLC analysis, the colorant components of Table 7 The Taiwan government safety limit and experimental results of major heavy metal contents in formulation GR6 and SW10 1. M. H. Lee, I. J. Kang, H. H. Park, J. Am. Acad. Dermatol., 52,79 (2005). 2. J. Kawase, T. Yoshihara, Fragrance Journal, 22, 18 (1994). 3. F. M. Ma, National Taiwan Craft Research Institute, 56, 56 (1995). 4. M. Kimura, Dyeing & Finishing, 163, 27 (1998). 5. G. J. Nohynek, R. Fautz, F. B. Kieffer, H. Toutain, Food Chem. Toxicol., 42, 517 (2004). 6. Nil, Manufacturing Chemist, Jan, 1997, p F. A. Chen, Ph. D. Thesis, Studies on the stability and formulation of alkannin/shikonin enantiomers, Taipei Medical University Taiwan ; J. Han, X. C. Weng, K. S. Bi, Food Chemistry, 106, 2 (2008). 9. X. C. Weng, G. Q. Xiang, A. L. Jiang, Y. P. Liu, L. L. Wu, X. W. Dong, S. Duan, Food Chemistry, 69, 143 (2000). 10. R. H. Guo, M. L. Liu, H. B. Fu, Journal of Chengdu Textile College, 22, 11 (2005). 11. H. M. Li, Journal of Xi an University of Engineering Science and Technology, 20, 378 (2006). 12. C.Y.Chen,L.M.Fan,H.C.Wang,Sen i Gakkaishi, 63, 252 (2007). 13. Dyeing and Finishing Consulting Center, Dyeing & Finishing, 181, (1999).