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研究生： 蔡曜輝
Tsai, Yao-Hui
論文名稱： 雷射切割塑膠製程之環境荷爾蒙排放特徵及其勞工健康風險評估
Characterization of Endocrine Disruptors from Laser Cutting Process of Plastics and Health-Risk Assessment for Workers
指導教授： 林達昌
Lin, Ta-Chang
學位類別： 碩士
Master
系所名稱： 工學院 - 環境工程學系
Department of Environmental Engineering
論文出版年： 2014
畢業學年度： 102
語文別： 中文
論文頁數： 204
中文關鍵詞： 雷射切割 、懸浮微粒 、鄰苯二甲酸酯類 、多環芳香烴 、健康風險評估
外文關鍵詞： Laser cutting process, Particulate Matter, Phthalate Esters, Polycyclic Aromatic Hydrocarbons, Health-Risk Assessment
相關次數： 點閱：131  下載：3 
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    • 由於過去雷射切割塑膠製程在工業上並不常見，因此鮮少有相關研究係針對雷射切割塑膠排放之污染物進行調查與評估；但隨著工業科技之進步，雷射切割技術愈來愈盛行。雷射製程會產生大量懸浮微粒(Particulate Matter, PM)，而這些微粒能夠沉降於人體呼吸系統上造成健康危害；此外，雷射切割機制牽涉到高溫燃燒、汽化及熱分解，係具有潛力產生複雜且對人體有害之有機污染物，因此對於雷射製程中作業人員之危害風險評估係有其必要性。過去研究指出塑膠製程所排放空氣物染物中內分泌干擾物質最為常見，其中以鄰苯二甲酸酯類(Phthalate Esters, PAEs)與多環芳香烴化合物(Polycyclic Aromatic Hydrocarbons, PAHs)為主。PAEs與PAHs皆具有生殖毒性，長期暴露可能導致生殖系統受損；此外，PAHs亦具有致癌性，對人體健康影響甚大，因此本研究將針對這兩類內分泌干擾物質進行研究。
    實驗結果顯示雷射切割塑膠所產生懸浮微粒主要分佈於粒徑小於1μm以下(即PM1)。不同雷射功率之污染物排放部分，燻煙中PM質量濃度與PAHs濃度皆會隨著雷射功率提升而增加；但DEHP由於係來自於塑膠本身之添加，因此總DEHP排放濃度並不隨著雷射能量提升而增加。污染物之氣相與粒相分佈情形，DEHP易因高溫而揮發至氣相中。分子量低之PAHs會因揮發性高而主要分佈於氣相中；相對的，高分子量PAHs則主要存在於粒相。比較各暴露組之污染物暴露濃度，距離雷射機台1公尺之高暴露組明顯高於距離3公尺與7公尺之中、低暴露組，主要係受污染物距離傳輸之影響。
    DEHP慢性非致癌性風險而言，各暴露組之危害指數皆符合容許範圍；但值得注意的是雷射切割聚碳酸酯製程之男性雷射機台操作人員，其每日攝入量高於男性長期暴露導致生育力損害之建議值，即表示男性雷射機台操作人員可能會有不孕、精子活動力下降等生殖能力受損之危害。PAHs致癌性風險評估而言，粒相之BaPeq毒性濃度高於氣相之BaPeq毒性濃度。各暴露組之致癌風險度皆高於10-6，表示作業人員所暴露BaPeq毒性當量濃度具有高致癌性風險。
    綜合以上結論可知雷射切割塑膠製程之作業人員處於高危害風險作業環境中，因此應給予作業人員適當的防護具與建立良好通風系統，以減少作業人員之危害物暴露量。

    In the past decades, laser cutting of plastics was not common in industry, so there has been very limited information for the reference in terms of laser-generated air contaminants (LGACs), plastic material especially. Nowadays, Laser cutting is more and more popular with the improvement of industry. Therefore, health-risk assessment for workers is very necessary. First of all, gaseous and particulate contaminants are sampled respectively under various laser powers and distances; second qualitative and quantitative analyses of phthalate esters (PAEs) and polycyclic aromatic hydrocarbons (PAHs) are measured. And third, evaluate the human health risk assessment of personal exposure to PAEs and PAHs. The results of this study show: (1) PM1 is found mainly at laser cutting of plastics; (2) the concentrations of particulate matter (PM) and PAHs increase as the laser power increase; (3) because of transmission distance, the concentrations in the high-exposure group are obviously higher than the middle-and low-exposure group; (4) The daily intake of DEHP for male’s laser operator is higher than the threshold value, that is to say male’s reproductive system might be at risk; (5) for carcinogenic risk, the estimated average lifetime lung cancer risk due to PAH exposure is higher than values recommended. According to the aforementioned, the workers at laser cutting of plastics are under the highest danger and risk workplace, so employers need to provide workers with personal protective equipments and improve the ventilation system at workplace.

    摘要 I Extended Abstract III 誌謝 X 目錄 XII 表目錄 XVIII 圖目錄 XXII 第1章 前言 1 1.1 研究動機 1 1.2 研究目的 3 第2章 文獻回顧 4 2.1 環境荷爾蒙 4 2.1.1 國內外塑膠加工製程之環境荷爾蒙職業暴露研究 5 2.2 雷射切割製程污染研究 7 2.2.1 雷射切割製程機制 7 2.2.2 雷射切割製程之污染物特性 11 2.3 光電面板基材中之塑膠介紹 13 2.3.1 聚碳酸酯(Polycarbonate, PC) 16 2.3.2 聚對苯二甲酸乙二酯(Polyethylene terephthalate, PET) 17 2.4 雷射切割塑膠燻煙中懸浮微粒(Particulate Matter, PM) 20 2.4.1 懸浮微粒之生成與分類 20 2.4.2 懸浮微粒之物化特性 21 2.4.3 懸浮微粒之健康危害 24 2.5 雷射切割塑膠燻煙中環境荷爾蒙 28 2.5.1 鄰苯二甲酸酯類(Phthalate Esters, PAEs) 28 2.5.1.1 鄰苯二甲酸酯類之物化特性與應用 28 2.5.1.2 鄰苯二甲酸酯類之暴露途徑 32 2.5.1.3 鄰苯二甲酸酯類之健康危害與毒性 33 2.5.2 多環芳香烴(Polycyclic Aromatic Hydrocarbons, PAHs) 37 2.5.2.1 多環芳香烴碳氫化合物之形成機制與物化特性 37 2.5.2.2 多環芳香烴碳氫化合物之暴露途徑 43 2.5.2.3 多環芳香烴碳氫化合物之健康危害 44 第3章 實驗方法與設備 49 3.1 實驗架構與流程 49 3.2 實驗藥品與器材 51 3.3 採樣設計與規畫 52 3.3.1 CO2雷射切割機台介紹 52 3.3.2 雷射加工製程之塑膠基材 55 3.3.3 採樣設計 57 3.3.3.1 雷射功率的選擇 57 3.3.3.2 採樣時間 57 3.3.3.3 污染源採樣 58 3.3.3.4 勞工暴露採樣 59 3.4 採樣設備與方法 61 3.4.1 空氣中懸浮微粒採樣 61 3.4.1.1 雷射粒數質量濃度監測儀(DUSTTM check) 61 3.4.1.2 SEM分析 62 3.4.2 採樣前處理 62 3.4.2.1 採樣濾紙製備與調理 62 3.4.2.2 矽膠與無水硫酸鈉之前處理 63 3.4.3 空氣中內分泌干擾物採集設備 63 3.4.3.1 氣相與粒狀之鄰苯二甲酸酯類採集 63 3.4.3.2 氣相與粒相之多環芳香烴化合物採集 64 3.5 樣品分析與方法 66 3.5.1 鄰苯二甲酸酯類之樣品前處理 66 3.5.1.1 粒狀樣品之萃取 66 3.5.1.2 氣相樣品之萃取 66 3.5.2 多環芳香烴化合物之樣品前處理 67 3.5.2.1 粒狀樣品之萃取、濃縮及淨化 67 3.5.2.2 氣相樣品之萃取 68 3.5.3 樣品GC-MS之分析方法 68 3.5.4 塑膠中鄰苯二甲酸酯類之萃取試驗 70 3.6 勞工健康風險評估 71 3.6.1 鄰苯二甲酸酯類之健康風險評估 71 3.6.2 多環芳香烴化合物之健康風險評估 73 3.7 資料處理與統計分析方法 75 第4章 數據分析品質保證與控制 77 4.1 採樣程序之QA/QC 77 4.2 空白試驗 77 4.2.1 採樣程序與氣固相樣本之空白試驗 77 4.2.2 溶劑空白試驗 78 4.3 粒相與氣相之回收率 78 4.4 分析程序之QA/QC 81 4.4.1 標準品之檢量線建立 81 4.4.2 精密度與準確度之建立 81 4.4.3 方法偵測極限 82 4.4.4 滯留時間測試 83 第5章 結果與討論 87 5.1 CO2雷射切割製程產生之燻煙微粒基本特徵 87 5.2 CO2雷射切割塑膠之懸浮微粒排放特徵 91 5.2.1 燻煙中懸浮微粒質量濃度 91 5.2.2 燻煙中PM之質量濃度與粒徑特性分析 99 5.2.2.1 不同雷射功率下PM1與PM10之相關性 99 5.2.2.2 不同雷射功率下PM1-2.5與PM10之相關性 100 5.2.2.3 不同雷射功率下PM2.5-10與PM10之相關性 102 5.3 塑膠原料之鄰苯二甲酸酯類萃取試驗 104 5.4 CO2雷射切割塑膠之環境荷爾蒙排放 108 5.4.1 雷射切割源之空氣污染物逸散特徵 108 5.4.1.1 不同雷射功率切割塑膠之PAEs排放量 108 5.4.1.2 不同雷射功率切割塑膠之PAEs分佈特徵 111 5.4.1.3 不同雷射功率切割塑膠產生之PAHs排放量 119 5.4.1.4 不同雷射功率切割塑膠之PAHs分類探討 129 5.4.2 雷射加工製程之勞工暴露情形 138 5.4.2.1 不同作業之人員PAEs實際暴露量 138 5.4.2.2 不同作業之人員氣相與粒相PAEs分佈特徵 148 5.4.2.3 不同作業之人員PAHs實際暴露量 151 5.4.2.4 不同作業之人員PAHs分類探討 167 5.5 雷射切割製程之健康風險評估 172 5.5.1 勞工暴露DEHP之健康風險評估 172 5.5.1.1 以總DEHP濃度進行風險評估 172 5.5.1.2 DEHP慢性非致癌性風險度評估 173 5.5.2 勞工暴露PAHs之健康風險評估 177 5.5.2.1 以總PAHs濃度進行風險評估 177 5.5.2.2 以BbF+BaP+DBA濃度進行風險評估 178 5.5.2.3 以BaPeq毒性當量濃度進行風險評估 179 5.5.2.4 PAHs致癌風險度評估 185 5.5.3 小結 186 第6章 結論與建議 188 6.1 結論 188 6.2 建議 190 第7章 參考文獻 191

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