背景：職業性皮膚病是門診常見的皮膚病之一；美髮業又屬職業性皮膚病之好發族群；台灣的研究發現，皮膚科門診之接觸性皮膚炎案例中，職業性皮膚炎約佔五分之一；職業性皮膚病致病原因中又以因接觸化學品而造成皮膚刺激或過敏的現象，為常見的致病原因，而對於美髮從業人員如何選用正確的防護手套以減低工作中手部暴露於各項藥劑的研究並不完備，因此針對相關藥劑對防護手套的滲透研究實有持續進行之必要。
　　目的：本研究以ASTM F739-07標準滲透測試方法測定燙髮劑之主要成分-硫醇基乙酸(Thioglycolic acid)及溴酸鈉(Sodium bromate)-對美髮業常使用之天然乳膠(Natural rubber latex, NRL)手套、黑色天然乳膠(Black natural rubber latex, BNRL)手套、聚氯乙烯(Polyvinylchloride, PVC)手套及丁腈橡膠(Nitrile rubber, NR)手套等4種手套之滲透模式並提出使用建議。
　　材料與方法：硫醇基乙酸以高效液相層析儀(HPLC-UV)定量，溴酸鈉則以紫外線/可見光分光光度計(UV-Vis Spectrometer)測定，滲透試驗中挑戰溶液之濃度分別為：硫醇基乙酸11%(w/v)及溴酸鈉11.5%(w/v)；測試溫度為27°C，每15分鐘採樣1次，測試時間為4小時。每單一測試皆進行3重複。
　　結果：硫醇基乙酸偵測極限為1.5 μg/mL，溴酸鈉為0.35 μg/mL；滲透測試結果顯示，硫醇基乙酸溶液挑戰天然乳膠手套於試驗時間4小時內皆無破出，黑色天然乳膠手套破出時間(Breakthrough time, BT)為80±8.66 (75-90)分鐘，聚氯乙烯手套為25±8.66 (15-30)分鐘，丁腈橡膠手套為175±17.32 (165-195)分鐘，各手套穩定滲透速率(Steady-state permeation rate, SSPR)分別為，黑色天然乳膠手套0.85±0.07 μg/cm2/min，聚氯乙烯手套1.14±0.39 μg/cm2/min，丁腈橡膠手套0.56±0.15 μg/cm2/min。天然乳膠手套對硫醇基乙酸溶液有良好的防護效果，而黑色天然乳膠手套及聚氯乙烯手套破出時間較短，顯示對於硫醇基乙酸溶液防護效果有限；另外溴酸鈉溶液挑戰本研究之四種手套於試驗時間4小時內皆無破出，顯示此四種測試手套對於溴酸鈉溶液具有良好的防護效果。
　　結論：建議美髮業者如使用天然乳膠(NRL)手套處理燙髮劑時， 4小時內是可提供足夠的保護，而聚氯乙烯手套的平均破出時間為25±8.66 (15-30)分鐘，不建議使用於處理燙髮劑產品，另外如使用黑色天然乳膠(BNRL)手套及丁腈橡膠(NR)手套時，則須經常更換，才可提供有效的防護效果。總而言之，使用防護手套應需經常性更換，避免長時間重複使用同一雙手套進行連續性的工作，才能對美髮師的手部有最好的防護效果。

關鍵字：防護手套、滲透、燙髮劑、硫醇基乙酸、溴酸鈉、美髮師

Background: Occupational skin disorder is one of the common occupational diseases. Hairdressers are prone to be the high risk population of occupational skin disorders. Researches found occupational dermatitis accounted for about 20% of the contact dermatitis cases of dermatological clinics in Taiwan. Most of the occupational skin diosrders were skin irritations or allergies, usually due to exposure to chemicals. Researches in how to select the appropriate protective gloves to minimize hand skin exposure to chemicals for the hairdressers are limited. Therefore, it is necessary to continue the glove permeation investigations for the chemicals being used in hair styling.
Aim: The ASTM F739-07 standard permeation test method was applied to investigate permeation behaviors of the major ingredients (thioglycolic acid and sodium bromate) in the permanent-waving solutions (PWS) while challenged four glove materials, natural rubber latex (NRL), black natural rubber latex (BNRL), polyvinylchloride (PVC) and nitrile rubber (NR). Meanwhile, the glove selection suggestions were proposed accoding to the results.
Material and Method: The thioglycolic acid was quantified by high performance liquid chromatography with UV-Vis detector (HPLC-UV). The UV/visible spectrophotometer was applied to measure the sodium bromate. The concentrations of challenge solutions of the permeation tests were thioglycolic acid 11% (w/v) and sodium bromate 11.5% (w/v). The test temperature was 27C. The permeation sample was collected every 15 minutes. The test duration was 4 hours. Each identical permeation test was performed triplicate.
Results: The detection limit of thioglycolic acid is 1.5 μg/mL and the detection limit of sodium bromate is 0.35 μg/mL. No breakthrough was detected for thioglycolic acid challenged the NRL gloves for the 4-hr tests. The average breakthrough times (BTs) of thioglycolic acid were 80.0±8.66 (75-90) minutes for BNRL, 25.0±8.66 (15-30) minutes for PVC and 175±17.32 (165-195) minutes for NR. The average steady-state permeation rates of triplicated tests were 0.85±0.07 μg/cm2/min for BNRL, 1.14±0.39 μg/cm2/min for PVC and 0.56±0.15 μg/cm2/min for NR. NRL for thioglycolic acid demonstrated sufficienct protection as no breakthrough of thioglycolic acid within 4 hours. The BTs of BNRL and PVC for hioglycolic acid were shorther, which indicated limited skin protection. None of the tested gloves can be permeated by sodium bromate within 4 hours.
Conclusions: NRL gloves provided the best protection among four tested gloves. PVC gloves were not recommended to the hairdressers as the short BTs (15-30 minutes) of thioglycolic acid. BNRL and NR gloves might provide appropriate hand protection only if hairdressers changed the gloves frequently, such as, changing glove per customer. Reusing these tested gloves should be cautious. The gloves should be changed more frequently to avoid prolonged reuse the same pair of disposable gloves for continuing tasks.

Keywords: protective glove, permeation, permanent-waving solution, thioglycolic acid, sodium bromate, hairdresser

摘要 I
Abstract III
誌謝 V
目錄 VII
表目錄 X
圖目錄 XI
第一章　前言 1
第一節　研究背景 1
第二節　研究目的 3
第二章　文獻回顧 4
第一節　美髮業之職業健康危害因子與疾病 4
第二節　燙髮劑種類及特性 6
第三節　燙髮劑相關法規規範 10
第四節　燙髮劑之健康效應及危害 11
2.4.1皮膚暴露評估及毒性試驗方式 11
2.4.2硫醇基乙酸之動物及人體毒理研究 15
2.4.3溴酸鈉之動物及人體毒理研究 19
第五節　燙髮劑分析方法 21
2.5.1硫醇基乙酸之分析方法 21
2.5.2溴酸鈉之分析方法 23
第六節　化學防護手套滲透試驗方式 25
2.6.1手套滲透試驗方式 25
2.6.2化學防護手套之滲透相關研究 30
第三章　材料與方法 33
第一節　藥品與試劑 33
第二節　儀器與設備 33
第三節　滲透試驗測試手套 36
第四節　檢量線藥品製備與製作 38
3.4.1硫醇基乙酸檢量線藥品製備 38
3.4.2硫醇基乙酸檢量線製作 38
3.4.3硫醇基乙酸檢量線高效液相層析儀檢測條件及檢量線繪製 38
3.4.4硫醇基乙酸偵測極限測定 39
3.4.5 溴酸鈉檢量線藥品製備 39
3.4.6 溴酸鈉檢量線製作 40
3.4.7溴酸鈉檢量線紫外線/可見光分光光度計檢測條件及檢量線繪製 40
3.4.8溴酸鈉偵測極限測定 41
第五節　手套滲透試驗實驗設計 42
3.5.1滲透試驗之手套處理 42
3.5.2 滲透試驗流程 42
第六節　數據整理及參數計算方式 45
3.6.1 名詞解釋 45
3.6.2 燙髮劑之滲透試驗物質可偵測破出濃度 46
3.6.3 累積滲透量計算 47
3.6.4 統計分析 48
第四章　結果 49
第一節　硫醇基乙酸及溴酸鈉檢量線 49
4.1.1硫醇基乙酸檢量線 49
4.1.2溴酸鈉檢量線 51
第二節　手套物理特性變化 53
4.2.1硫醇基乙酸手套滲透試驗手套厚度及重量變化 53
4.2.2溴酸鈉手套滲透試驗手套厚度及重量變化 63
第三節　手套滲透參數 73
4.3.1硫醇基乙酸手套滲透參數 73
4.3.2溴酸鈉手套滲透參數 89
第五章　討論 90
第一節　手套滲透試驗物理參數探討 90
5.1.1防護手套厚度及重量差異之探討 90
5.1.2防護手套厚度及重量差異與滲透行為探討 92
第二節　滲透行為對美髮師手部傷害探討 93
第三節　挑戰溶液物理特性差異與滲透行為探討 95
第四節　美髮師使用手套防護各種物質之探討 96
第六章　結論與建議 99
第一節　結論 99
第二節　建議 101
第三節　限制 102
英文參考文獻 103
中文參考文獻 106
日文參考文獻 109

American Society for Testing and Materials(ASTM). (2007). Standard Test Method for Permeation of Liquids and Gases through Protective Clothing Materials under Conditions of Continuous Contact. ASTM Method F739-07.

Andreasson, H., Boman, A., Johnsson, S., Karlsson, S., Barregard, L. (2003). On permeability of methyl methacrylate, 2-hydroxyethyl methacrylate and triethyleneglycol dimethacrylate through protective gloves in dentistry. [Comparative Study Research Support, Non-U.S. Gov't]. Eur J Oral Sci, 111(6), 529-535.

Bullock, W. H., Ignacio, J. S. (2006). A strategy for assessing and managing occupational exposures. Fairfax, VA: AIHA Press, American Industrial Hygiene Association.

European Union. (2009) REGULATION (EC) No 1223/2009 OF THE EUROPEAN PARLIAMENT AND OF THE COUNCIL of 30 November 2009 on cosmetic products. Available at http://eur-lex.europa.eu/LexUriServ/LexUriServ.do?uri=OJ:L:2009:342:0059:0209:en:PDF access September 18 2012.

Gan, H. F., Meng, X. S., Song, C. H., Li, B. X. (2003). A survey on health effects in a human population exposed to permanent-waving solution containing thioglycolic acid. [Comparative Study]. J Occup Health, 45(6), 400-404.

Glatt, H., Protic-Sablji, C. M., Oesch, F. (1983). Mutagenicity of glutathione and cysteine in the Ames test. [Research Support, Non-U.S. Gov't]. Science, 220(4600), 961-963.

Glatt, H., Oesch, F. (1985). Mutagenicity of cysteine and penicillamine and its enantiomeric selectivity. [Research Support, Non-U.S. Gov't]. Biochem Pharmacol, 34(20), 3725-3728.

Guo, Y. L., Wang, B. J., Lee, J. Y., Chou, S. Y. (1994). Occupational hand dermatoses of hairdressers in Tainan City. Occup Environ Med, 51(10), 689-692.

Guo, T. L., McCay, J. A., Karrow, N. A., et al. (2001). Immunotoxicity of sodium bromate in female B6C3F1 mice: a 28-day drinking water study. [Research Support, U.S. Gov't, Non-P.H.S. Research Support, U.S. Gov't, P.H.S.]. Drug Chem Toxicol, 24(2), 129-149. doi: 10.1081/DCT-100102606

Lee, H. S., Lin, Y. W. (2009). Permeation of hair dye ingredients, p-phenylenediamine and aminophenol isomers, through protective gloves. [Comparative Study Research Support, Non-U.S. Gov't]. Ann Occup Hyg, 53(3), 289-296. doi: 10.1093/annhyg/mep009


Lewis, R. J., Sax, N. I. (2000). Sax's dangerous properties of industrial materials. New York: Wiley.

Lind, M. L., Boman, A., Sollenberg, J., Johnsson, S., Hagelthorn, G., Meding, B. (2005). Occupational dermal exposure to permanent hair dyes among hairdressers. [Multicenter Study Research Support, Non-U.S. Gov't]. Ann Occup Hyg, 49(6), 473-480. doi: 10.1093/annhyg/mei030

Lind, M. L., Johnsson, S., Meding, B., Boman, A. (2007). Permeability of hair dye compounds p-phenylenediamine, toluene-2,5-diaminesulfate and resorcinol through protective gloves in hairdressing. [Research Support, Non-U.S. Gov't]. Ann Occup Hyg, 51(5), 479-485. doi: 10.1093/annhyg/mem028

Lysdal, S. H., Johansen, J. D., Flyvholm, M. A., Sosted, H. (2012). A quantification of occupational skin exposures and the use of protective gloves among hairdressers in Denmark. [Research Support, Non-U.S. Gov't]. Contact Dermatitis, 66(6), 323-334. doi: 10.1111/j.1600-0536.2012.02050.x

Monticello, M. V., Gaber, D. J. (1999). Glove resistance to permeation by a 7.5% hydrogen peroxide sterilizing and disinfecting solution. [Comparative Study]. Am J Infect Control, 27(4), 364-366.

Nielsen, J. B., Sorensen, J. A. (2012). Glove material, reservoir formation, and dose affect glove permeation and subsequent skin penetration. [Comparative Study In Vitro]. Sci Total Environ, 417-418, 87-91. doi: 10.1016/j.scitotenv.2011.12.037

O'Connell, R. L., White, I. R., Mc Fadden, J. P., White, J. M. (2010). Hairdressers with dermatitis should always be patch tested regardless of atopy status. Contact Dermatitis, 62(3), 177-181. doi: 10.1111/j.1600-0536.2009.01696.x

Royal Society of Chemistry(RSC). ChemSpider. CAS:52-90-4. Available at http://www.chemspider.com/Chemical-Structure.574.html access August 28 2012.

Uchida, H. A., Sugiyama, H., Kanehisa, S., et al. (2006). An elderly patient with severe acute renal failure due to sodium bromate intoxication. [Case Reports]. Intern Med, 45(3), 151-154.

U.S. National Library of Medicine(NLM). Hazardous Substances Data Bank(HSDB). CAS:68-11-1. Available at http://toxnet.nlm.nih.gov/cgi-bin/sis/search/r?dbs+hsdb:@term+@rn+@rel+68-11-1 access August 28 2012.

U.S. National Library of Medicine(NLM). Hazardous Substances Data Bank(HSDB). CAS:52-90-4. Available at http://toxnet.nlm.nih.gov/cgi-bin/sis/search/f?./temp/~1DTEhH:1 access August 28 2012.

U.S. National Library of Medicine(NLM). Hazardous Substances Data Bank(HSDB). CAS:7789-38-0. Available at http://toxnet.nlm.nih.gov/cgi-bin/sis/search/f?./temp/~7Doux2:1 access August 28 2012.
Wang, V., Lin, K. P., Tsai, C. P., Kao, K. P. (1995). Bromate intoxication with polyneuropathy. [Case Reports Letter]. J Neurol Neurosurg Psychiatry, 58(4), 516-517.

Wang, Z., Ren, X., Wang, D., Guan, Y., Xia, L. (2011). Effects of thioglycolic acid on parthenogenetic activation of Xenopus oocytes. [Research Support, Non-U.S. Gov't]. PLoS One, 6(1), e16220. doi: 10.1371/journal.pone.0016220

White, R. D., Wilson, D. M., Glosson, J. A., Madsen, D. C., Rowe, W. B., Goldberg, D. I. (1993). Toxicity evaluations of L-cysteine and Procysteine, a cysteine prodrug, given once intravenously to neonatal rats. [Comparative Study]. Toxicol Lett, 69(1), 15-24.
 
Rondney Boyer, 王姿文, 汪文忠, 林美惠, 施美份, 程中玉. (2003). 生物化學. 臺北縣新店市: 學銘圖書。

王來好, P. Bore. (1995). 化粧品分析. 臺北市: 高立圖書。

友和貿易股份有限公司. (2012). 物質安全資料表MSDS. CAS：52-90-4。

光井武夫, 陳韋達, 陳莉螢. (2004). 新化粧品學. 臺北市: 合記。

行政院衛生福利部食品藥物管理署. (2013). 包裝飲用水及盛裝飲用水中溴酸鹽之檢驗方法。Available at
http://www.fda.gov.tw/upload/133/Content/2013091116085382693.pdf access November 17 2013.

行政院衛生福利部食品藥物管理署. (2009). 燙髮劑中硫醇基乙酸成分之鑑別及含量測定。Available at
http://www.fda.gov.tw/upload/133/Content/%e7%87%99%e9%ab%ae%e5%8a 8%e6%88%90%e5%88%86%e4%b9%8b%e9%91%91%e5%88%a5%e5%8f%8a%e5%90%ab%e9%87%8f%e6%b8%ac%e5%ae%9a.doc access November 17 2013.

行政院衛生福利部食品藥物管理署. (2009). 燙髮劑中硫醇基乙酸及半胱胺酸之鑑別及含量測定方法。Available at
http://www.fda.gov.tw/upload/133/Content/%e7%87%99%e9%ab%ae%e5%8a%91%e4%b8%ad%e7%a1%ab%e9%86%87%e5%9f%ba%e4%b9%99%e9%85%b8%e5%8f%8a%e5%8d%8a%e8%83%b1%e8%83%ba%e9%85%b8%e4%b9%8b%e9%91%91%e5%88%a5%e5%8f%8a%e5%90%ab%e9%87%8f%e6%b8%ac%e5%ae%9a%e6%96%b9%e6%b3%95.doc access November 17 2013.

行政院衛生福利部食品藥物管理署. (2009). 燙髮劑中溴酸鈉成分之鑑別及含量測定。Available at
http://www.fda.gov.tw/upload/133/Content/%e7%87%99%e9%ab%ae%e5%8a%91%e4%b8%ad%e6%ba%b4%e9%85%b8%e9%88%89%e6%88%90%e5%88%86%e4%b9%8b%e9%91%91%e5%88%a5%e5%8f%8a%e5%90%ab%e9%87%8f%e6%b8%ac%e5%ae%9a.doc access November 17 2013.

 
行政院衛生福利部食品藥物管理署. (2012). 化粧品含有醫療或毒劇藥品基準(含藥化粧品基準)。Available at
http://www.fda.gov.tw/TC/includes/GetFile.ashx?id=1420&chk=84569111-af3b-4087-8db8-aa48c5b922a7&mid=46&name=fdContent access November 17 2013.

行政院勞工委員會安全衛生技術中心GHS化學品全球調和制度 CAS：68-11-1。Available at http://ghs.cla.gov.tw/CHT/intro/MSDS.aspx?casno=68-11-1 access August 28 2012.

行政院勞工委員會安全衛生技術中心GHS化學品全球調和制度 CAS：7789-38-0。Available at http://ghs.cla.gov.tw/CHT/intro/MSDS.aspx?casno=7789-38-0 access August 28 2012.

行政院經濟部標準檢驗局. 中華民國國家標準CNS總號：1953。Available at http://www.cnsonline.com.tw/previewJPG.jsp?general_no=0195300&language=C&pagecount=1 access August 28 2012.

行政院經濟部標準檢驗局. 中華民國國家標準CNS總號：2016。Available at http://www.cnsonline.com.tw/previewJPG.jsp?general_no=0201600&language=C&pagecount=1 access August 28 2012.

行政院經濟部標準檢驗局. 中華民國國家標準CNS總號：14384-3。Available at http://www.cnsonline.com.tw/previewJPG.jsp?general_no=1438403&language=C&pagecount=6 access November 23 2012.

李仰川, 詹馥妤. (2008). 化妝品學原理. 臺北縣中和市: 新文京開發。

李樹其, 鄭秋真, 施如佳. (1987). 魚肉煉製品中溴酸鉀殘留量之調查研究. [Survey on Residue of Potassium Bromate in Fish Paste Product]. 藥物食品檢驗局調查研究年報(5號), 110-114.

李筱書. (2008). 染髮劑中對苯二胺及胺基苯酚之防護手套滲透研究. 輔仁大學碩士論文。

吳君泰, 孫啟璟. (1999). 接觸性皮膚炎. [Contact Dermatitis]. 臺灣醫學, 3(4), 414-422。

林立. (2012). 建立手套滲透的預測模式. 輔仁大學碩士論文。

郁仁貽. (2005). 最新化粧品學. 臺南市: 復文。

侯紹英, 張岭, 吳坤, 夏蕾. (2007). 巰基乙酸對小鼠MⅠ/MⅡ期卵母細胞進程及結構的影響. [Effect of TGA on Maturing Progress and Structure of MⅠ/MⅡ Stage Oocytes in Mice ]. 中華疾病控制雜誌, 11(3), 263-266。

凌苑珊. (2010). 醫療用手套中鄰苯二甲酸酯類之探討. 輔仁大學碩士論文。

夏蕾, 張嶺, 侯少英, 吳坤. (2007). 巰基乙酸對非洲蟾蜍和小鼠卵母細胞體外減數分裂成熟的影響. [Thioglycolic Acid on the in Vitro Maturation Process of Oocytes in Xenopus and Mouse]. 中華疾病控製雜誌, 11(6), 595-598。
夏蕾, 侯紹英, 張嶺, 趙艷. (2009). 經皮染毒胇基乙酸對昆明小鼠排卵及體內卵母細胞成熟的影響. [Effects of Thioglycolic Acid through Percutaneous Administration to Mouse on Ovulation and Maturation of Oocyte in Vivo]. 癌變‧畸變‧突變, 21(3), 201-205。

張紅梅. (2010). TGA對蟾蜍血清生理指標的影響. [Effect of Thioglycolic Acid on the Physiology Index in Bufo gargarizans]. 四川動物, 29(2), 220-223。

張振平, 李聯雄, 劉立文. (2006). 防護手套之有機溶劑抗滲透性測試探討. [The Study of Organic SolventsPermeation Through Chemical ProtectiveGloves]. 行政院勞工委員會勞工安全衛生研究所. IOSH94-H302。

張慧菁. (2006). 染髮劑對防護手套之滲透評估. 輔仁大學碩士論文。

張麗卿. (1998). 化粧品製造實務. 臺南市: 臺灣復文興業。

張麗卿. (1998). 化妝品檢驗實務. 臺北市: 匯華。

連美華, 陳玉盆, 黃明權, 鄒玫君. (2008). 市售燙髮劑化粧品品質及溴酸鉀成分調查. [Investigation on Quality and Adulteration of Potassium Bromate in Permanent Wave in Taiwan Area]. 藥物食品檢驗局調查研究年報(26號), 30-35。

黃耀興, 葉慶輝, 黃吉田. (2003). 職業性皮膚病. 中華職業醫學雜誌, 10(4), 277-282。

蕭淑銖, 王伯智, 張素貞, 郭育良. (1995). 職校畢業之美髮從業人員皮膚病變及相關致病因子的探討. 勞工安全衛生研究季刊, 3(1), 17-24。

簡珮婷. (2009). 不同除污方式對手套重複是使用之防護效果的影響. 輔仁大學碩士論文。

饒麥玲, 詹芳霖, 李樹其, 周薰修. (1995). 食品中溴酸鉀檢驗方法之探討及其含量之調查. 藥物食品檢驗局調查研究年報(13號), 151-178.
 
厚生労働省. (1994). 都道府県知事の承認に係る医薬部外品。Available at http://wwwhourei.mhlw.go.jp/cgi-bin/t_docframe2.cgi?MODE=hourei&DMODE=SEARCH&SMODE=NORMAL&KEYWORD=%88%e3%96%f2%95%94%8a%4f%95%69&EFSNO=626&FILE=FIRST&POS=0&HITSU=0 access September 18 2012.