記 錄 12831 編 號 狀 G0499396022 態 助 教 建檔完成 查 核 索 書 查核完成 號 學 校 輔仁大學 名 稱 系 所 食品科學系 名 稱 舊 系 所 名 稱 學 499396022 號 研 究 林承萱 生( 中) 研 究 Lin Cheng-hsuan 生( 英) 論 金屬爪蓋墊片鄰苯二甲酸酯轉移之影響因子探討 文 名 稱( 中) 論 文 名 Study on parameters affecting phthalates migrating from metal cap gasket 稱( 英) 其 他 題 名 指 導 教 陳政雄 授( 中) 指 導 教 授( 英) 校 內 全 文 2017.9.7 開 放 日 期 校 外 全 文 2017.9.7 開 放 日 期 全 文 不 開 放 理 由 電 子 全 文 同意 送 交 國 圖. 國 圖 全 文 2017.9.7 開 放 日 期. 檔 案 論文全文 說 明 電 子 01 全 文 學 位 碩士 類 別 畢 業 100 學 年 度 出 版 101 年 語 文 中文 別 關 鍵 鄰苯二甲酸酯類 塑化劑 金屬瓶蓋墊片 聚氯乙烯 迴歸分析 字( 中) 關 鍵 phthalates plasticizer metal cap gasket PVC regression analysis 字( 英) 鄰苯二甲酸酯類為一種內分泌干擾化學物質,具致突變及致癌性,常用於一些塑膠 材質,但從食品包材轉移至食品時,則會造成人體危害。本研究目的主要探討影響 金屬爪蓋內墊片於儲藏期間之鄰苯二甲酸酯類塑化劑轉移的因素。研究藉由水性 ( 三種酸鹼值) 與油性 (橄欖油模擬液) 接觸金屬爪蓋墊片,於冷藏、室溫及模擬運輸 之高溫進行儲藏試驗三個月,模擬液經溶劑萃取鄰苯二甲酸酯再以固相萃取純化, 並利用 HPLC 鑑定與定量。另以 FTIR-ATR 分析金屬爪蓋塗層及墊片材質。結果顯 摘 示以HPLC分析11種鄰苯二甲酸酯類化合物的偵測極限範圍為 0.1-0.5 ppm。水性模 要( 擬液經儲藏12週皆無鄰苯二甲酸酯之檢出,顯示酸鹼值及溫度不影響水模擬液中鄰 中) 苯二甲酸酯類釋出。油性模擬液與墊片於高溫及長時間接觸會造成其中鄰苯二甲酸 酯轉移,以鄰苯二甲酸二-[2-乙基己基]酯 (Di-2-ethylhexyl phthalate) 及鄰苯二甲酸 二異壬酯 (Diisononyl phthalate) 為主要檢出化合物。FTIR-ATR 分析發現金屬爪蓋 塗層無 -C=O 官能基,而聚氯乙烯材質之墊片則有此官能基,推測為鄰苯二甲酸酯 來源。利用迴歸分析鄰苯二甲酸酯之轉移方程式,食品極性、儲藏溫度及時間為主 要影響因子使鄰苯二甲酸酯從聚氯乙烯墊片轉移至食品中。藉由控制包材中鄰苯二 甲酸酯含量、溫度及儲藏時間可降低塑化劑之轉移程度。 Phthalates are characterized as endocrine disruptors, and show mutagenic and carcinogenic activities. Those compounds are widelyused in polymer production, and regarded as a contamination once migrating into food products. The aim of this study was 摘 to investigate factors influencing the extent of phthalates leaching from metal cap gasket 要( into food. Simulant models including water (in three pH values) and olive oil were 英) employed to contact metal cap, and refrigeration and ambient temperature, as well as high temperature which is used to simulate transportation situation were accomplished up to 3 months. Solvent extraction of phthalates from simulants was conducted, and then the extract was purified using SPE cartridge. Identification and quantification of 11 targeted phthalates in simulants was achieved using an HPLC installed UV-Vis detector. Additionally, coating materials and gasket used in metal cap were analyzed by FTIRATR. The results showed the LOD of targeted phthalates were ranging 0.1-0.5 ppm in the present study. No phthalates in water models were found up to 12 weeks, this indicated neither acidity (pH 3-7) nor temperature showing any effectiveness on the leaching of phthalates from gasket. Phthalates migrated from gasket into olive oil model was found in associated with higher temperature and longer contact duration. Among the detected phthalates, Di-2-ethylhexyl phthalate and Di-isononyl phthalate were predominant. From the results of the use of FTIR-ATR to characterize the materials used in metal cap gasket, no –C=O functional group was observed from the coatings, however, from PVC gasket that indicated the source of phthalates. Leaching of selected phthalates determined from regression analysis showed different patterns with respect to storage temperatures and storage. The present study demonstrate that polarity of food, storage temperature and duration play a key on migration of phthalates from PVC gasket into food. With a control on phthalates load, temperature, and storage length may reduce the extent of phthalate migration. 論 文 目 次 第一章 前言 1 第二章 文獻回顧 4 一、轉移現象(Migration) 4 (一)轉移定義 4 (二)轉移機制 5 (三)影響轉移之因子 11 二、塑化劑(Plasticizer) 13 (一)塑 化劑特性 13 (二)塑化劑之應用性及暴露途徑 17 (三)對人體之危害性及環境影 響 19 (四)法規 22 (五)塑膠包材特性 27 三、鄰苯二甲酸酯類 (Phthalates, PAEs) 32 (一)製造及物化特性 32 (二)分析方法 37 (三)純化處理 44 (四) 萃取純化方法 44 (五)國內追蹤之鄰苯二甲酸酯類化合物 45 第三章 材料與方法 48 一、試驗材料 48 (一)化學藥品 48 (二)氣體 49 (三)試驗儀器與設備 49 二、實驗設計 51 三、試驗方法 52 (一)樣品前處理 52 (二)轉移系統 (migration models) 52 (三)儲藏試驗 55 (四)空白試驗 55 (五)模擬液中鄰苯二甲酸酯類 之溶劑萃取 55 (六)固相萃取純化 55 (七)FTIR-ATR 分析 58 (八)HPLC 分析 65 (九)統計分析 65 第四章 結果與討論 66 一、鄰苯二甲酸酯類標準品分析 66 二 、空白 (Blank) 分析 67 三、食品金屬瓶蓋墊片材質分析 70 四、食品模擬系統中鄰 苯二甲酸酯類轉移分析 73 五、含定量鄰苯二甲酸酯類之PVC轉移模式分析 155 第 五章 結論 164 第六章 參考文獻 165 參 考 文 獻 日本厚生労働省食品衛生法 2011。http://law.egov.go.jp/htmldata/S22/S22HO233.html, accessed on 2011.07.16。 行政院衛生署食品 藥物管理局塑膠食品容器宣導網站 2011。 http://www.pidc.org.tw/PlasticsPackage/Pages/default.aspx, accessed on 2011.06.28。 行 政院環境保護署網站 2012。http://www.epa.gov.tw。 李波平、林勤保、宋欢、李莉 莉。2008。快速溶剂萃取-高效液相色谱测定塑料中邻苯二甲酸酯类化合物。应用 化学。第25卷第1期。中國。 林怡瑩。2006。添加奈米生物顆粒對土壤中鄰苯二甲 酸酯類化合物生物降解之影響。東吳大學微生物學系碩士論文。台北。 吳宜勳。 2004。水中鄰苯二甲酸酯類採樣分析方法之研究。國立清華大學原子科學系碩士論 文。新竹。 邱馨儀。2003。以微透析裝置連結高效能液相層析儀檢測塑膠容器中 飲品之鄰苯二甲酸酯類含量。國立高雄師範大學化學系碩士論文。高雄。 陳佳飛 。2002。食品容器及包裝用塑膠材質之塑化劑溶出研究。國立陽明大學環境衛生研 究所碩士論文。台北。 陳琰。1999。塑膠添加劑。高立圖書有限公司。p97-100。 陳再洁、楊曉燕、王智、李小俠。2010。HPLC同時測定歐盟限用 6 種增塑劑含量 。廣州化工。38(1):151-3。 許順文、葉燦輝、丁文輝。2006。塑膠容器中之塑化劑 (鄰苯二甲酸脂類)危害。崑山科技大學環境工程系專題研究報告。台南。 黃康帆。 2009。市售食品、食品容器及包裝材料所含鄰苯二甲酸酯類化合物之調查及轉移試 驗。國立嘉義大學食品科學研究所碩士論文。嘉義。 楊岸玠。2005。淺談食品包 裝容器–裝東西看仔細。耕讀茶話。第四十八期。第八章。 廖健森。2002。環境荷 爾蒙鄰苯二甲酸酯類化合物於台灣水體環境中含量調查與微生物分解之研究。東吳 大學微生物學系碩士論文。台北。 賴倩因。2000。以近紅外線光譜儀偵測 HI-PS 塑膠容器在不同浸出溶液中釋出物之含量。大葉大學食品工程研究所碩士論文。彰 化。 賴耿陽譯。1993。塑膠大全。臺南巿:臺灣復文興業。p169-170。 盧彥辰。 2006。土壤中鄰苯二甲酸酯類化合物降解影響因子及添加奈米化堆肥之探討。東吳 大學微生物學系碩士論文。台北。 Agarwal DK, Maronpot RR, Lamb JC, and Kluwe WM. 1985. 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