6-受损头发表面永久性的18-MEA层的再生

?????????? 18-MEA???? ???? 1, ???? 2 ?1??????????? Beauty ???????????? 2-1-3????131-8501 2????????????????????????????? 1334??????640-0112? ?????????? 18-MEA???????????????????? 18-MEA ???? ?????????????? ?????18-MEA????????????????????? ???18-MEA?????????????SPDA?????????????????????? ??????????????????????????? AFM? AR-XPS?????18-MEA/SPDA ????????????????????18-MEA/SPDA???????????????18-MEA ???????????? 25?? ???????????????????SPDA?AFM?AR-XPS ?? 18-MEA ???????????????????????????????????????? ??????18-MEA??????????????????????????[5-8]??? 18-MEA?? ??????????????????????????????????????????? ????????[9, 10]?18-MEA?????????????????????????????? ??????????[7]? ????????????????? 18-MEA ??????????????????? 18-MEA ?????????????????????? 18-MEA ?????????????? ???????????????????????? 18-MEA???????????????? ?????????????? 18-MEA????????????? 18-MEA????????? ?????????? ?? ?? ???? ????? ? ? 30?????????????????? 20????????????? ????????????????? ????????? ??????????? ?????? 360???????????????????? 90? ???????? ? ??? ? ?????????????? ? ??????????????? ??????????????????????????????????????????? Cl ick to bu y N OW ! PD F-XChange w ww.docu-track .co m C lic k t o b uy N OW ! PD F-XChange w ww.docu-track .co m ??????? 10%??????????????????? pH? ?????????? ???? ?? ?????????? pH9.0? 3.5%????? ???????????? 0.5????????? ??????????????? 30?????? 30??0.5??? ?????? ? ????????????? 30???? ? ??????? 30???????? ??????? ???? 18-MEA? SPDA????????????????? ???? ????????? ??????? Wilhelmy?? K100MK2?Kruss??????????20????65%???? ?? ??????????? KEF-SE(KATO TECH. CO., LTD)?????????20 ????65% ?????? 18-MEA????? 18-MEA?????????????????LC-MS??LC-MS, Agilent Technologies, Palo Alto, CA, USA???? ?????? ?? Nanoscope IIIa Multi? AFM(Veeco Instruments, Santa Barbara, CA)? ?????? ??????????????????????? AFM ?????????????????? ???? AFM????????? ???? ?????????ARXPS? ???? ????????(ULVAC PHI, Tokyo)????????????????????? ??????? Quantera SXM ???? 15 Kv?25 W???? Al K ?X-?????? ?? 18-MEA??????? ? 18-MEA????????????????????? ????? 1%? 18-MEA????? ???????????????? 90???????? ??????????????????? ?????????? 18-MEA??????????????????????????? ???? ??????????????????? 18-MEA???????????????? Cl ick to bu y N OW ! PD F-XChange w ww.docu-track .co m C lic k t o b uy N OW ! PD F-XChange w ww.docu-track .co m C on ta ct A ng le ( º) 100 80 70 90 50 60 (a) (b) (c) (d) ? 1 ? 18-MEA????????????????????????? ??????? ?????????????????????? 18-MEA????????????????1%? 18-MEA ?????????? 18-MEA??????????????????????? 18-MEA????????? ?????????????????????????????????????? ? ?? 18-MEA???????????????????????????????????????? ?????????????????? ? ?????????? ? ???? 18-MEA? SPDA?? ??????? ????????????????????? 90?????????????? ???????? 18-MEA/SPDA ????????? ???????????????????? ?????????????????????????????????? 18-MEA/SPDA ??? ?????? ????????????????????????????????????? ???????? C on ta ct A ng le ( º) 100 80 70 90 50 60 (a) (b) (c) (d) (e) (f) p<0.01 ? 2 ? 18-MEA?????????????????????????????? ???????? ??????? ?????????????????????????18-MEA/SPDA?????? ??? ?????????18-MEA/DAPS?????? ????????????18-MEA/STAC?????? ?? ?????????????????? ?? O N H N O N H NO NO N N + Cl-N + Cl- (a) (b) (c) ? 3 ???????? ????????????SPDA?????3-?????????????? ??????????????STAC? Cl ick to bu y N OW ! PD F-XChange w ww.docu-track .co m C lic k t o b uy N OW ! PD F-XChange w ww.docu-track .co m ? 1 ??????? ? ?? 1 ?? 2 ?? 3 ?? ????? SPDA 2 - - 2 DAPS - 2 - - STAC - - 2 - ??? 0.5 0.5 0.5 0.5 ??? 3 3 3 3 18-MEA 1 1 1 - ?? 0.3 0.3 - 0.3 ? 93.2 93.2 93.5 93.2 ? 18-MEA/SPDA ?????????????????????????????????? ?????????????????????? 18-MEA/SPDA????????? ??????? ????????????????????????????? 18-MEA/SPDA ???????? ?????????????????????? 18-MEA/SPDA ????????? ?????? ???????????????????????????????????? ? ????? LC-MS??????????? 18-MEA?????????????????? ????????18-MEA ?? SPDA ??????????????????????????? ??????????? A m ou nt o f S or pt io n of 1 8- M EA (? g/ g- H ai r ) 0 20 5 25 10 15 (a) (b) (c) ? 4 LC/MS?? 18-MEA??????????????18-MEA??????????????? ????????????? ????????????18-MEA/SPDA?????? ??????18-MEA/DAPS ?????? ??????18-MEA/STAC?????? ?? Cl ick to bu y N OW ! PD F-XChange w ww.docu-track .co m C lic k t o b uy N OW ! PD F-XChange w ww.docu-track .co m ?? ????????????? 18-MEA? SPDA????????????????????? AFM ????????????????????????????????????????? ????????????????????? 18-MEA/SPDA ???????????????? ???? AFM????????????????????? AFM?????????????? ???????????????? ? ??????????????? 18-MEA/SPDA? 18-MEA/DAPS?????????????? AFM????????? 1000nm × 1000nm?????????? ????? AFM??????? ????????????????????????????????????????????? ????????????????????????????????????? 18-MEA/SPDA? ????????????????????????????18-MEA/SPDA????????? 1 ??? 5 x 5 ?m (a) 5 x 5 ?m (b) 5 x 5 ?m (c) Mica Sorbed layer ? 5 ????????? AFM????????????????????????????? ??????????????? AFM???????????? 1000nm x1000nm??????? ??????18-MEA/SPDA ???18-MEA/DAPS (c) 18-MEA/STAC ? ??? ARXPS?????????????????????18-MEA?????????? ?????????????????????????????SPDA???????????? ?????????????18-MEA ????? SPDA ??????????????????? ???????????????????????? 18-MEA/SPDA??????? ? ????? 18-MEA????? 2.39????? 18-MEA/SPDA?????? 25?????? ???????? ??18-MEA/SPDA???? 1nm?18-MEA? SPDA?????????????????????? ????????????????? 25?? Cl ick to bu y N OW ! PD F-XChange w ww.docu-track .co m C lic k t o b uy N OW ! PD F-XChange w ww.docu-track .co m (b) 0 0.02 0.04 0.06 0.08 0.1 0 0.02 0.04 0.06 0.08 0.1 0 2 4 6 80 2 4 6 8 1/sin? Pe ak a re a ra tio (N /C ) (a) 0 0.04 0.08 0.12 0.16 Pe ak a re a ra tio (C O O /C -C ) 0 2 4 6 80 2 4 6 8 1/sin? ? 6 ARXPS???? 18-MEA/SPDA?????????? ??? SPDA?????????? ??? 18-MEA????????????? SO3 - SO3SO3 - Cuticle 18-MEA SPDA O HN+ O O- O HN+ O HN+ O O- O O O O- O HN+ O HN+ SO3 - SO3SO3 - O HN+ O HN+ O HN+ O O- O HN+ O HN+ O O- O O O O- ? 7 ? 18-MEA/SPDA???????????????????? 18-MEA/SPDA??????? ?????? 25??????????????????? ????? 18-MEA??????????????????? ? ? 18-MEA???????? ????????????????????18-MEA???20??????????????18-MEA ????????[11]???????? Ward et al.? XPS????????????? 0.9??[13]? ???? 18-MEA????????????????????? 18-MEA/SPDA????????? ?????? 18-MEA?????????????????????????????????? ??? ? ????????????????????????????????????? 18-MEA/SPDA????????????????????? Cl ick to bu y N OW ! PD F-XChange w ww.docu-track .co m C lic k t o b uy N OW ! PD F-XChange w ww.docu-track .co m ?? ???????????18-MEA? SPDA???????????????? ??AFM? ARXPS?????18-MEA/SPDA??????????????????????? ???????? 25?????????? ??18-MEA/SPDA ????????????? 18-MEA ????????????????? ???????????????? ? ?????????????????????????? ????? ????: [1] A. P. Negri, H. J. Cornell, D. E. Rivett, The nature of covalently bound fatty acids in wool fibers, Aust. J. Agric. Res., 42, 1285-1292(1991) [2] A. P. Negri, H. J. Cornell, D. E. Rivett, Effects of proceeding on the bound and free fatty acid levels in wool, Text. Res. J., 62, 381-387(1992) [3] S. Naito, M. Ooshika, N. Yorimoto, Y. Kuroda, The structure of bound lipids of human hair fibers and its physical properties, Proc. 9th Int. Wool Text. Res. Conf. II, Biella, Italy, 367-374(1996) [4] D. J. Evans, M. Lanczki, Textile Res. J., 67, 435-444(1997) [5] U. Kalkbrenner, H. Koener, H. Hoecker, D. E. Rivett, Proc. 8th Int. Wool Text. Res. Conf. I, Christchurch, New Zealand, 398(1990) [6] C. M. Carr, I. H. Leaver, A. E. Hughes, Textile Res. J., 56, 457(1986) [7] S. Breakspear, J. R. Smith, G. Luengo, J. Struct. Biol., 149, 235-242 (2005) [8] C. A. Torre, B. Bhusham, J-Z. Yang, P. M. Torgerson, J. Cosmet. Sci., 57, 37-56(2006) [9] M. Yasuda, Journal of Hair Science, 95, 7-12(2004) [10] M. L. Tate, Y. K. Kamath, S. B. Ruetsch, H.-D. Weigmann, Quantification and prevention [11] A. P. Negri, H. J. Cornell, D. E. Rivett, A model for the surface of keratin fibers, Textile Res. J., 63,109-1158(1993) [12] H. Zahn, H. Messinger, H. Hoecker, Covalently linked fatty acids at the surface of wool: part of the ”cuticle cell envelope”, Text. Res. J., 64, 554-555(1994) [13] R. J. Ward, H. A. Willis, G. A. George, G. B. Guise, R. J. Denning, D. J. Evans, R. D. Short, Surface analysis of wool by X-ray photoelectron spectroscopy and static secondary ion mass spectroscopy, Text. Res. J., 63, 362-368(1993) Cl ick to bu y N OW ! PD F-XChange w ww.docu-track .co m C lic k t o b uy N OW ! PD F-XChange w ww.docu-track .co m Regeneration of Persistent 18-MEA layer on Damaged Hair Surface HIROTO TANAMACHI1, SHIGETO INOUE2 ?1 BeautyResearch Center, Kao Corporation, 2-1-3, Bunka, Sumida-ku, Tokyo 131-8501, Japan ? 2 Analytical Science Research Laboratories, Kao Corporation, 1334 Minato, Wakayama-shi, Wakayama, 640-0112, Japan? Abstract: A technology for the regeneration of a persistent hydrophobicity to damaged hair surfaces using 18-MEA (18-Methyleicosanoic acid) is presented. Two approaches were examined in order to make 18-MEA bind tightly to damaged hair surface. One was to apply 18-MEA as an acid form and the other was to apply 18-MEA as a salt or complex. It was found that the combination of 18-MEA with a specific cationic surfactant (Stearoxypropyldimethylamine: SPDA) makes damaged hair surface hydrophobic, and maintains its hydrophobicity even after shampooing. Characterization of adsorbed layers of 18-MEA/SPDA on mica surface, as a hydrophilic surface model, was performed using Atomic Force Microscopy (AFM) and Angle-resolved X-ray Photoelectron Spectroscopy (AR-XPS). The results revealed that 18-MEA/SPDA formed a layer with high wear resistance, with an alkyl chain, the hydrophobic moiety, oriented at an angle of around 25°to the air interface. INTRODUCTION 18-MEA is thought to be covalently bound, probably via a thioester or ester linkage, to the outer surface of the cuticle (1-4) and locates specifically in the cuticle, not cortex (3). It is also known that 18-MEA makes the surface hydrophobic and acts as a boundary lubricant to decrease friction resistance (5-8). Since 18-MEA is covalently bound to the cuticle surface via thioester linkage, it can be easily removed under alkaline conditions, such as hair coloring or permanent waving, and the surface becomes hydrophilic and friction increases (9, 10). The absence of 18-MEA is considered as one of the reasons for an increase in friction on the surface of the cuticle and it may have an influence on the sensory perception of hair, such as dried out feeling and being hard to finger/comb through (7). Although it is expected that a damaged hair surface should be repaired if 18-MEA layer could be repaired, restoration of 18-MEA on damaged hair surface has not been reported so far. The objective of this study is to develop a regeneration method of 18-MEA on a damaged hair surface and provide persistent hydrophobicity and low friction to the damaged hair surface. It is well known that it is impossible to regenerate covalently bound 18-MEA to the damaged hair surface. Therefore, two approaches were Cl ick to bu y N OW ! PD F-XChange w ww.docu-track .co m C lic k t o b uy N OW ! PD F-XChange w ww.docu-track .co m examined in this study in order to make 18-MEA bind tightly to the damaged hair surface. One was to apply 18-MEA as an acid form and the other was to apply 18-MEA as a salt or complex. EXPERIMENTAL MATERIALS Hair samples Hair fibers were kindly provided by a Japanese female aged 30. The fibers were cut at a distance of approximately 20 cm from the root end on the back of her head. The hair had never been treated with any chemical agents, such as bleaching, coloring or permanent waving. Preparation of alkaline-colored hair The hair was exposed to alkaline-coloring treatment 4 times with model weathering 360 times, where 90 times model weathering were done between every interval of alkaline-coloring, resulting in a total of alkaline-coloring combined with daily weathering for 1 year, if the hair is alkaline-colored every 3 months. The model weathering consists of a series of hair care procedures in daily life; shampooing, conditioning, drying with a hot drier and brushing. Plain shampoo (10wt% of sodium polyoxyethylene lauryl ether sulfate solution adjusted to pH7 with phosphoric acid), plain conditioner (formulation No.4 listed in Table 1) and alkaline-color solution, including 3.5% H2O2 at pH 9.0, were used for the preparation of alkaline-colored hair. Procedure of shampoo and conditioner treatment Shampoo (0.5ml) was applied to the wet hair tress (5g) and was massaged by hand for 30 seconds. The hair tress was then rinsed for 30seconds under running water. Conditioner (0.5ml) was applied to the wet hair tress and distributed manually for 30 seconds, then left on for 1 minute. The hair tress was rinsed for 30seconds under running water. The hair tress was towel dried and dried using a hot dryer. Chemicals 18-MEA and Stearoxypropyldimethylamine (SPDA) were obtained by chemical synthesis. Other chemicals were commercially available. METHODS Measurement of surface properties of hair Dynamic contact angles of hair were measured by the Wilhelmy method using a K100MK2 (Kruss). The measurements were done at 20 ? C , 65% relative humidity (RH). Friction forces on the cuticle surface of hair were measured using KEF-SE (KATO TECH. CO., LTD). The test was conducted at a temperature of 20 ? C and relative humidity of 65%. Cl ick to bu y N OW ! PD F-XChange w ww.docu-track .co m C lic k t o b uy N OW ! PD F-XChange w ww.docu-track .co m Quantitative analysis of 18-MEA The amount of 18-MEA adsorbed to the hair fiber was measured using Liquid Chromatography / Mass Spectrometry (LC-MS, Agilent Technologies, Palo Alto, CA, USA). Atomic Force Microscopy AFM images of adsorbed layer on mica surface were obtained using a Nanoscope IIIa Multi Mode AFM (Veeco Instruments, Santa Barbara, CA) with E-Scanner. Tapping mode imaging was used to obtain the topography images of adsorbed membrane layer. Mechanical property of adsorbed membrane was analyzed by AFM scratching method. Angle Resolved X-ray Photoelectron Spectroscopy (ARXPS) ARXPS is a nondestructive method to obtain elemental and chemical-state information as a function of depth. ARXPS data was obtained using a Quantera SXM spectrometer (ULVAC PHI, Tokyo) with a monochromatized Al K alpha X-ray source at 15 kV and 25 W. RESULTS Application of 18-MEA as an acid form Contact angles of alkaline-colored hair treated with 18-MEA as acid type are shown in Figure 1. When the alkaline-colored hair was treated with 1wt% of 18-MEA in chloroform, the contact angle became 90 º, corresponding to that of normal hair (Figure 1(c)). That means the surface of the alkaline-colored hair recovers hydrophobicity just after 18-MEA application. The contact angle decreased after shampooing (Figure 1(d)), however, meaning the surface reverts to being hydrophilic. This is because 18-MEA as an acid form doesn't have shampoo resistance with this procedure. C on ta ct A ng le ( º) 100 80 70 90 50 60 (a) (b) (c) (d) Figure 1. Contact angle of alkaline-colored hair treated with 18-MEA as an acid form. The bars represent means for n=5, the whiskers represent the standard deviations. (a) normal hair (b) alkaline-colored hair (c) alkaline-colored hair treated with 18-MEA as acid type (1wt% of 18-MEA in chloroform was applied.) (d) alkaline-colored hair treated with 18-MEA as an acid form and shampooed Cl ick to bu y N OW ! PD F-XChange w ww.docu-track .co m C lic k t o b uy N OW ! PD F-XChange w ww.docu-track .co m Application of 18-MEA as a complex The objective for this study is to regenerate 18-MEA on alkaline-colored hair and provide persistent hydrophobicity and low friction on alkaline-colored hair surface. In this section, contact angles after shampooing were measured in order to make sure that damaged surface maintains its hydrophobicity even after shampooing. Contact angles of alkaline-colored hair treated with 18-MEA and long-chain tertiary amine or quaternary cationic surfactant complex in conditioner, after shampooing are shown in Figure 2. Chemical structures of these surfactants are shown in Figure 3 and the conditioner formulations are listed in Table 1. When alkaline-colored hair was treated with 18-MEA/SPDA complex (conditioner 1), the contact angle became nearly 90 º, corresponding to that of normal hair. To further investigate, analysis of variance (ANOVA) was conducted. It demonstrated that there were significant differences in the contact angle between the hair treated with 18-MEA/SPDA complex (conditioner 1) and alkaline-colored hair, and there were not significant differences in the contact angle between the hair treated with 18-MEA/SPDA complex (conditioner 1) and normal hair. That means the surface of alkaline-colored hair treated with 18-MEA/SPDA complex (conditioner 1) could maintain its hydrophobicity even after shampooing, while the hair treated with other complexes could not. C on ta ct A ng le ( º) 100 80 70 90 50 60 (a) (b) (c) (d) (e) (f) p<0.01 Figure 2. Contact angle of alkaline-colored hair treated with18-MEA complexes after shampooing. The bars represent means for n=7, the whiskers represent the standard deviations. p-value was obtained from ANOVA analysis. (a) normal hair (b) alkaline-colored hair (c) 18-MEA/SPDA (conditioner 1) (d) 18-MEA/DAPS (conditioner 2) (e) 18-MEA/STAC (conditioner 3) (f) control (conditioner 4) Cl ick to bu y N OW ! PD F-XChange w ww.docu-track .co m C lic k t o b uy N OW ! PD F-XChange w ww.docu-track .co m O N H N O N H NO NO N N + Cl-N + Cl- (a) (b) (c) Figure 3. Chemical structures of surfactants (a) Stearoxypropyldimethylamine (SPDA) (b) Dimethylaminopropylstearamide (DAPS) (c) Stearyltrimethylammonium chloride (STAC) Table 1. Formulation of conditioners Balance 31 2 4(control) Dimethylaminopropylstearamide -- 2 - Water Stearyl alcohol 33 3 3 Stearoxypropyldimethylamine -2 - 2 18-MEA 11 1 - Lactic Acid -0.3 0.3 0.3 Stearyltrimethylammonium chloride 2- - - Benzyl alcohol 0.50.5 0.5 0.5 The dynamic friction coefficient of alkaline-colored hair treated with 18-MEA/SPDA was the nearest to that of normal hair, and it was much lower than that of hair treated with other complexes. The results of ANOVA showed that there was a significant difference in the dynamic friction coefficient between the hair treated with 18-MEA/SPDA complex (conditioner 1) and alkaline-colored hair, and there were no significant differences in the dynamic friction coefficient between the hair treated with 18-MEA/SPDA complex (conditioner 1) and normal hair. That means the surface of alkaline-colored hair treated with 18-MEA/SPDA complex (conditioner 1) could maintain its low friction even after shampooing, while the hair treated with other complexes could not. Figure 4 shows the amount of sorption of 18-MEA of alkaline-colored hair treated with 18-MEA/SPDA, 18-MEA/DAPS and 18-MEA/STAC complex measured by LC-MS. As we expect from the results of the contact angle and surface friction, the amount of 18-MEA absorbed on the surface of alkaline-colored hair treated with 18-MEA/SPDA complex was much higher than that of hair treated with other complexes. Cl ick to bu y N OW ! PD F-XChange w ww.docu-track .co m C lic k t o b uy N OW ! PD F-XChange w ww.docu-track .co m A m ou nt o f S or pt io n of 1 8- M EA (? g/ g- H ai r ) 0 20 5