永久性染髮劑的配方改良和分析方法探討

在現今社會中，染髮已經成為一件相當普遍的事情，而在染髮中所使用的染髮劑，其中有一個常用的成分中間體，名為對苯二胺(PPD，p-Phenylenediamine)，此成分有過敏或致癌的爭議；因此現今市售染髮劑改用對胺基苯酚(PAP；p-Aminophenol)及2,5-二胺基甲苯(TDS；Toluene-2,5-diamine sulfate)來取代PPD，也使用間胺基苯酚(MAP；m-Aminophenol)為耦合劑，此染髮劑最終可將頭髮染成深色，本研究根據黃婉雯碩士論文”永久染髮的配方開發及分析方法建立”將其染髮劑配方進行改良，使用PAP、TDS、MAP這三種成分當作自製永久性染髮劑的主要成分，並建立出一個簡單快速且準確的HPLC方法來分析這三種成分。本研究所建立的HPLC分析方法，層析管柱：HYPERSIL ODS-C18（5μm，4.6 mm × 250 mm），移動相為三乙胺：水：乙晴 (5：85：10，v/v)並以稀磷酸調整pH至7.5，波長設定為 245 nm，流速：1.0 ml∕min，注入量為10 μL，此分析條件同時分析這3種染髮劑成分，並且在7分鐘內完成。在安定性試驗方面，測試自製的永久型染髮劑(含10%的抗氧化劑Na2SO3)，在25℃的室溫下存放一個月，PAP、TDS及MAP含量分別衰退為87.75%、94.53%及88.23%。分析方法確效方面，PAP的相對標準偏差(RDS%)介於0.12%~0.67%，而回收率為98.82%，線性迴歸R2＝0.9966，偵測極限為2.3 ppm，定量極限為7.6 ppm；TDS的相對標準偏差(RDS%)介於0.15%~0.99%，而回收率為97.92%，線性迴歸R2＝0.9981，偵測極限為2.1 ppm，定量極限為7 ppm；MAP的相對標準偏差(RDS%)介於0.13%~0.78%，而回收率為97.14%，線性迴歸R2＝0.9948，偵測極限為3.5 ppm，定量極限為12.4 ppm。在虐待實驗方面，經加熱破壞後PAP、TDS及MAP含量皆在80.24%以上，經加酸破壞後PAP、TDS及MAP含量皆在82.44%以上，經加鹼破壞後，除PAP含量剩下61.75%衰退比較多外，TDS和MAP含量皆在83.01%以上，經氧化破壞後PAP、TDS及MAP含量皆在89.58%以上，經照射UV破壞後PAP、TDS及MAP含量皆在91.61%以上。

關鍵字

2,5-二胺基甲苯；對胺基苯酚；高效能液相層析儀；永久染髮；間胺基苯酚

並列摘要

In today society, hair dyes become very common. Nevertheless, in hair dye intermediates, PPD(p-Phenylenediamine) is now recognized as a controversial ingredient due to stimulus and carcinogen. At present, PAP(p-Aminophenol) and TDS(Toluene-2,5-diamine sulfate) are commercially available in hair dye used to replace PPD component. This research was based on Huang’ thesis” The Development of Formula and Analytical Method for Permanent Hair Dye”. Besides, the ingredients of PAP and TDS were used in the improved hair dye formula and the more stable ingredient of MAP(m-Aminophenol) was included to obtain the dark hair dye. A simple, fast and accurate HPLC method was established to analyze these three ingredients. The developed HPLC method was performed with the conditions: column (Hypersil ODS-C18; 5μm; 4.6 mm × 250 mm), mobile phase(triethylamine: water: acetonitrile = 5：85：10, v/v, adjusted pH to 7.5 with diluted phosphoric acid), detection wavelength 245 nm, flow rate 1.0 ml/min, injection amount 10 μL, and the run time was within 7 minutes to simultaneously analyze three ingredients of hair dyes. In the stability tests, 10% of antioxidant Na2SO3 was added to the formula of our self-made permanent hair dyes. This formula showed the satisfied results with the 87.75% contents of PAP, 94.53% contents of TDS and 88.23% contents of MAP in one month of 25℃room temperature condition. In the results of validation experiment, the relative standard deviation (RSD) of PAP is ranged from 0.12% to 0.67%, the average recovery was 98.82%, the linear regression coefficient (R2) was 0.9966, and the limits of detection (LOD) and quantification (LOQ) were 2.3 ppm and 7.6 ppm, respectively. The relative standard deviation of TDS is ranged from 0.15% to 0.99%, the average recovery was 97.92%, the linear regression coefficient was 0.9981, and the limits of detection and quantification were 2.1 ppm and 7 ppm, respectively. The relative standard deviation of MAP is ranged from 0.13% to 0.78%, the average recovery was 97.14%, the linear regression coefficient was 0.9948, and the limits of detection and quantification were 3.5 ppm and 12.4 ppm, respectively. In the stress experiments of method validation, the contents of PAP, TDS and MAP were remained more than 80.24% during the test of heating, the contents of PAP, TDS and MAP were remained more than 82.44% during the test of adding strong acid, the contents of TDS and MAP were remained more than 83.01% but the content of PAP only 61.75% remained during the test of adding strong base, the contents of PAP, TDS and MAP were remained more than 89.58% during the test of adding strong oxidants, and the contents of PAP, TDS and MAP were remained more than 91.61% during the test of illuminating UV light.