清潔類化粧品中 5-bromo-5-nitro-1,3-dioxane及甲醛之檢驗方法開發

Development of analytical method for determination of 5-bromo-5-nitro-1,3-dioxane and formaldehyde in rinse-off cosmetics

鄭淑晶(Shu-Ching Cheng)

指導教授 ： 許秀蘊

臺北醫學大學/藥學院/藥學系(碩博士班)/碩士(2014年)

摘要

為了預防化粧品在長時間的使用過程中受到微生物汙染(例如：黴菌和酵母菌)，保障產品安全性，添加適量防腐劑是有其必要性。甲醛和5-bromo-5-nitro-1,3-dioxane被用在清潔類(或洗去型)化粧品中當作抗菌和防腐作用，特別是在洗面乳、洗髮精和沐浴乳中。甲醛於2006年被世界衛生組織WHO的國際癌症研究中心 ( International Agency for Research on Cancer)分類為第一類人類致癌物，5-bromo-5- nitro-1,3-dioxane (BND)則是一種含溴的抗菌化合物，國際上化粧品法規對其有不同的限量規定。因此，同時檢測化粧品中甲醛及5-bromo-5-nitro-1,3-dioxane的含量是有其必要性。本研究超高液相層析法可同時運用在不同清潔類化粧品中甲醛及5-bromo-5-nitro-1,3-dioxane的檢測，本方法僅將檢體經過簡單萃取並與乙醯丙酮衍生，不須經淨化或濃縮步驟便可以分析，檢驗方法確效以線性、準確度、精密度、定量極限及檢測極限來確保方法的性能，在最適化條件下，甲醛濃度在0.1到20 ppm之間，5-bromo-5-nitro-1,3-dioxane濃度在2到200 ppm之間，吸收光譜強度與濃度均呈線性關係，判定係數 (r2) 分別為1.0及0.9996，全部回收率均大於82 %，精密度之變異係數均小於8.2%，定量極限分別為0.1 ppm及2 ppm，檢測極限分別為0.02 ppm及0.8 ppm。本研究開發之方法具有寬的線性範圍，高選擇性和靈敏度，定量極限分別遠低於國際化粧品的規範，因此，本分析方法適用於市售清潔類化粧品中5-Bromo-5-nitro- 1,3-dioxane及甲醛的常規品質監測。

關鍵字

清潔類化粧品 ； 洗去型 ； 甲醛 ； 甲醛供體 ； 超高效液相層析法

並列摘要

The addition of preservatives is absolutely essential to ensure that cosmetics are safe to use for a long time, since these compounds protect formulations from contamination by microorganisms such as bacteria and yeasts. 5-bromo-5-nitro-1,3-dioxane and formaldehyde are used in rinse-off cosmetics, particularly facial cleanser, shampoos and body wash, as antibacterial agent and preservatives. In 2006, International Agency for Research on Cancer (IARC) classified formaldehyde as carcinogen to humans. 5-Bromo - 5 - nitro-1 , 3 - dioxane is a bromine -containing preservative which also subjected to several restrictions according to the international cosmetic regulation. Thus, as a part of a quality control procedure, analytical methods for the determination of two compounds in different types of cosmetics are required. In this paper that ultra performance liquid chromatography has been simultaneously applied for the determination of formaldehyde and 5-bromo-5-nitro-1,3-dioxane in a variety of rinse off cosmetic products. After simple extraction, and derived with acetylacetone, it was analyzed without any further cleanup or concentration step. Linearity, accuracy, precision, limit of quantitation, and limit of detection were evaluated to assess the performance of the proposed method. Under optimal conditions, the spectrophotometry intensity increased linearly with the concentration of formaldehyde ranging from 0.1 to 20 ppm with a correlation coefficient of 1.0, and 5-bromo-5-nitro-1,3-dioxane ranging from 2 to 200 ppm with a correlation coefficient of 0.9996. The recovery studies on rinse-off cosmetics gave satisfactory values ( > 82 % for two analytes), and coefficient of variance of precision were all below 8.2 %. The quantitation limit of formaldehyde was 0.1 ppm, and 5-bromo-5-nitro-1,3-dioxane was 2 ppm. The detection limit of formaldehyde was 0.02 ppm, and 5-bromo-5-nitro-1,3-dioxane was 0.8 ppm. The proposed method has a wide linear range, high selectivity and sensitivity. The quantification limits were far below those set by the international cosmetic regulations, making this analytical method suitable for routine control.

並列關鍵字

rinse-off cosmetics ； formaldehyde ； 5-bromo-5-nitro-1,3-dioxane ； ultra performance liquid chromatography

參考文獻

1. Lang I., Bruckner T., Triebig G. Formaldehyde and chemosensory irritation in humans: A controlled human exposure study. Regulatory Toxicology and Pharmacology. 2008;50(1):23-36.

2. Anton C., et al. Formaldehyde-releasers:relationship to formaldehyde contact allergy. Contact allergy to formaldehyde and inventory of formaldehyde-releasers. Contact Dermatitis. 2009;61:63-85.

3. Anton C., De G., Mari-Ann F., et al. Formaldehyde-releasers in cosmetics relationship to formaldehyde contact allergy. Contact Dermatitis. 2010;62:2-17.

4. Thyssen J.P.J., Jeanne D., Menne T., Contact allergy epidemics and their controls. Contact Dermatitis. 2006;56:185-95.

5. Kehoe K.J. Formaldehyde. Encyclopedia of Toxicology (Second Edition). New York: Elsevier; 2005. p. 375-6.