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한국산업위생학회지, 제 23 권제 2 호 (2013) Journal of Korean Society of Occupational and Environmental Hygiene, 2013: 23(2): 95-102 시료채취방법에따른작업공정별 Toluene diisocyanates 포집농도비교 김성호 1 원종욱 1,2,3 김치년 1,3 정우진 1,2,3 노재훈 1,2,3 * 1 연세대학교보건대학원 2 연세대학교의과대학예방의학교실 3 연세대학교산업보건연구소 Comparison of Toluene Diisocyanate Concentrations Collected with Different Sampling Methods by Work Process Sung Ho Kim 1 Jong Uk Won 1,2,3 Chi Nyon Kim 1,3 Woo Jin Jung 1,2,3 Jaehoon Roh 1,2,3 * 1 Graduate School of Public Health, Yonsei University 2 Department of Preventive Medicine, Yonsei University 3 Institute for Occupational Health, Yonsei University ABSTRACT Objectives: The aim of this study is to present an appropriate sampling method for individual exposure assessment based on a comparison of toluene diisocyanate (TDI) concentrations collected through different sampling methods by work process type. Methods: Two plants handling TDIs in the Incheon area were selected. The samplings were taken during respective processes of spray painting, drying, grinding, and foaming, in which the production of TDIs took on different forms. For the sampling methods for airborne TDIs, open-face cassette holder, modified 2-piece cassette holder, and impinger were used, and the sampling was performed simultaneously at the same locations. Results: The comparison of TDI collection concentrations by each process depending on the sampling method showed high concentrations in the order of the impinger, modified 2-piece cassette holder, and open-face cassette holder for spray painting and foaming. In all processes with the exception of drying, TDI collection concentrations were higher for sampling done with the modified 2-piece cassette holder than with the open-face cassette holder. Conclusions: Based on these results, the modified 2-piece cassette holder was found to be a more appropriate sampling method than the open-face cassette holder when taking individual samples of TDIs from spray painting, grinding, and foaming processes. In particular, for individual exposure assessment of the spray painting process, which features comparatively high collection concentrations compared to the other processes, the use of a modified 2-piece cassette holder is considered appropriate. Key words : 2,4-TDI, 2,6-TDI, open-face cassette, modified 2-piece cassette, impinger I. 서론이소시아네이트는기도자극, 감작, 폐기능감소그리고과민성폐렴을일으키며직업성천식의원인이되는화학물질이다 (Baur et al., 1994; Ott et al., 2003; Tsai et al., 2006). 이소시아네이트는폴리우레탄, 가구, 고무합성, 스프레이도장공장등에서많이쓰이고있으며, 그중방향족이소시아네이트인 Toluene diisocyanates(tdis) 는달콤한과일향의자극성을가지고있는무색또는옅은노란색의액체로서 Toluene 2,4- diisocyanate(2,4-tdi) 와 Toluene 2,6-diisocyanate(2,6-TDI) 의두가지이성질체로존재한다. TDIs는접착제, 도장제, 광택제, 단열제등에사용되는폴리우레탄의구성성분으로이소시아네이트산업의 90% 를차지하고있다 (Nordqvist et al., 2003). TDIs에의한건강장해는 1951년에처음으로보고 *Corresponding author: Jaehoon Roh, Tel: 02-2228-1867, E-mail: jhroh@yuhs.ac 421 General classroom building, #50 Yonsei-ro, Seodaemun-ku, Seoul Received: March 9, 2013, Revised: June 17, 2013, Accepted: June 18, 2013 95

96 김성호, 원종욱, 김치년, 정우진, 노재훈 되었으며 (Fuchs & Valade, 1951), 우리나라에서는 1978 년에처음으로보고되었다 (Gang, 1978). 이소시아네이트에의한질환으로고농도노출시수분내기관지염, 기관지경련, 폐부종, 천식등이유발될수있다. 국내에서도 TDIs는직업성천식의대표적인원인물질이며, 기존연구에서 TDIs에의한직업성천식의유병률은 0.58~21.6% 이었다 (Kim et al., 2005; Kim et al., 2004; Choi & Kim., 2000; Park et al., 2003). TDIs에대한노출기준은미국산업위생전문가협의회 (American Conference of Governmental Industrial Hygienists, ACGIH) 에서시간가중평균치 (8-hr Time-Weighted Average, TWA) 로 0.005 ppm, 단시간노출기준 (Short-Term Exposure Limit, STEL) 을 0.02 ppm으로권고하였고 (ACGIH, 2013), 미국산업안전보건청 (Occupational Safety and Health Administration, OSHA) 에서는 2,4-TDI를 C0.02ppm 으로허용기준 (Permissible Exposure Limit, PEL) 을설정하였지만 2,6-TDI에대한기준은없다. 우리나라의노출기준은 TWA 0.005 ppm, STEL 0.02 ppm으로설정하고 2,4-TDI는허용기준대상물질로선정하여매우엄격하게관리하고있다 (MoEL, 2012). 고용노동부의연구에서 TDIs 노출사업장을대상으로공정별 2,4-TDI를측정한결과 TWA와 STEL 모두도장공정에서 2,4-TDI에가장많이노출되었다 (MoEL, 2005). 그러나 TDIs는저농도라도장기간노출될경우호흡곤란, 흉부압박감, 폐기능저하, 기관지염, 천식등이일어나며 (Woolish et al., 1990), 눈, 코점막, 기도에도질병이유발될수있다 (Littorin et al., 2007). TDIs의측정과분석방법은일반적으로이차아민의유도체화시약과반응시켜유도체물질을 HPLC(High Performance Liquid Chromatography) 로분석하며 (Sang & Zimerson, 1980), 작업환경중 TDIs 평가방법으로 OSHA Method 42와 NIOSH Method 5522를주로사용하고있다. 현재우리나라의 TDIs 측정은고용노동부고시제2011-25호의작업환경측정및정도관리규정에의해 1-(2-pryridyl)piperazine( 이하 1-2PP) 가코팅된 37 mm 유리섬유여과지를사용한다 (MOEL, 2011). 이방법은 OSHA Method 42와유사하다. 또다른 TDIs 채취방법의하나로 NIOSH에서는 Dimethyl sulfoxide(dmso) 에 Tryptamine(TRYP) 을녹인흡수액을임핀저에담아사용하는 Method 5522 제시하였다 (NIOSH, 1998). 흡수액을사용하는임핀저는유도체시약이안정적이라는장점으로미스트 (mist) 나에어로졸형태의이소 시아네이트가주로발생되는스프레이도장작업의경우에는임핀저를사용한시료채취방법을권고하고있다 (OSHA, 1989). Bello et al.(2002) 의연구결과스프레이도장공정의경우임핀저를사용한시료채취방법이 1-2PP를코팅한유리섬유여과지보다포집농도가더높았다. 그러나지역시료채취만가능한임핀저의시료채취방법은현행작업환경측정시정상적인개인노출평가로적용하기어렵다. 한편, 1-2PP를코팅한유리섬유여과지를사용한시료채취방법의특징은코팅된유도체시약이불안정하고큰에어로졸 (aerosol) 이나프리폴리머 (prepolymers) 의이소시아네이트의경우충분히유도체화반응이일어나지못해이소시아네이트가과소평가될수있다 (Czamecki, 1992). 또한 3단카세트홀더의상단부분을제거한개방형카세트홀더는 TDIs의발생형태가먼지또는증기형태에따라정전기에의해벽면부착등에의해유실이있을수있으며, 유입된 TDIs가 bottom filter에맞고튀겨나갈가능성이나벽면에부착되는등의시료손실이단점이다 (Mao et al., 2000). 따라서주변환경으로부터필터를보호하고벽면에부착하거나홀더밖으로튕겨져나가는공기중 TDIs의농도가일정하지못할수있다는문제를해결하기위해변형 2단카세트홀더를이용하여 TDIs 생산공장의공기중 TDIs 시료를채취하는실험을하였으며, 연구결과변형 2단카세트홀더가개방형카세트홀더보다공기중 TDIs의포집농도가더높았다 (Mao et al., 2000). 국내연구에서는 TDIs 생산공장이아닌 TDIs 사용공장에서변형 2단카세트홀더를사용한공기중 TDIs 시료를채취한실험결과도유사하였다 (Park et al., 2003). 그러나 TDIs 사용공장에서의실험은폴리우레탄도장공정만을대상으로한측정결과이므로 TDIs를취급하는다른공정에서도위연구와마친가지로 TDIs 포집농도가높은결과를보이는지검토할필요가있다. 따라서본연구의목적은실험결과를바탕으로공정별농도분포와노출실태를파악하고, 시료채취방법에따른공정별 TDIs 포집농도를비교하여개인노출평가시적합한시료채취방법을제시하는것이다. II. 연구방법 1. 공기중시료포집공기중 2,4-TDI 와 2,6-TDI 는인천지역소재악기 http://www.kiha.kr Journal of Korean Society of Occupational and Environmental Hygiene, 2013: 23(2): 95-102

시료채취방법에따른작업공정별 Toluene diisocyanates 포집농도비교 97 제조공장의스프레이도장공정, 건조공정, 연마공정과자동차시트제조공장의발포공정에서오전과오후로나누어개방형카세트홀더와변형 2단카세트홀더, 임핀저를사용하여각각의방법에따라 66개의지역시료를채취하였다. 개방형카세트홀더와, 변형 2단카세트홀더에사용되는시료포집여과지는 OSHA Method 42에의하여 methylene chloride에 1-2PP를 0.2 mg/ml가되도록조제한후유리섬유여과지에 0.5mL를도포한뒤건조하여사용하였으며, 임핀저를사용한시료채취방법은 NIOSH Method 5522에의하여 DMSO에 TRYP을 450 μg /ml 농도로제조한흡수액 20 ml을사용하였다. 시료채취는오전과오후각각 3시간동안개인시료채취기를사용하여포집하였고, 유량보정기를사용하여펌프의유량을 1 L/min이되도록보정하였다. 개방형카세트홀더를이용한측정은 3단카세트홀더의상단부분을제거하여여과지와외부공기가직접맞닿을수있도록제작되었고. 변형 2단카세트홀더는개방형카세트홀더의중간부분을제거하고상단홀더의윗면과중간을감싸는여과지를만들어부착하여제작하였다. 개방형카세트홀더와변형 2단카세트홀더를비교한단면도는 Figure 1과같다. 개방형카세트홀더와변형 2단카세트홀더는시료채취종료후플라스틱마개로시료의앞과뒤를막고분석전까지냉동보관하였으며, 임핀저를사용한시료는분석전까지 20 ml cap vial에담아알루미늄호일에싸서햇빛을차단하였으며분석전까지상온에서보관하였다. 2. 시료분석개방형카세트홀더와변형 2 단카세트홀더로포 Table 1. Operating condition of HPLC used for analysis Descrip tions Detector Column Injection volume Mobile phase Flow rate Conditions Condition for open-face and modified 2-piece cassette UV/VIS 254 nm Alltima, C18 5 μm particle size, 15 cm x 4.6 mm Condition for impinger Fluorescence: ex 275 mm; em 320 mm 3.9-mm ID 150mm stainless steel packed with 10-μm u-bondapak C18 25 μl 25 μl 0.01 M ammonium acetate ACN (50%)/ 0.6% sodium in 37.5/62.5 ACN/water acetate buffer (50%) adjusted to ph 6.2 1 L/min 1 L/min 집한시료의분석은자외선- 가시광선검출기 (UV/VIS detector) 가장착된 HPLC( 모델명, 제조사, 제조국 ) 를사용하였다. 이동상용매는 ACN(Acetonitrile) 과탈이온수를 37.5 : 62.5로혼합한것을사용하였으며, 초산을첨가해 ph 6.2로맞추어사용하였다. 임핀저로포집한시료의분석은형광검출기 (fluorescence) 가장착된 HPLC를사용하였다. 이동상용매는아세트산나트륨 10.2 g을탈이온수 1 L에놓인후빙초산을첨가해 ph 5.5를맞춘후이를 ACN과 5:5로혼합하여사용하였다. 분석방법에따른기기조건은 Table 1과같다. 3. 통계분석개방형카세트홀더와변형 2단카세트홀더, 임핀저의공정별포집효율을비교하기위해분산분석을실시하였고, 시료채취방법에따른 2,4-TDI와 2,6-TDI의농도를비교하기위해 t-test를실시하였다. 통계분석은통계프로그램 SAS v9.2(ibm, USA) 을활용하였다. III. 연구결과 Figure 1. Cross-sections of the open-face and modified 2-piece cassette holder 1. 공정에따른 2,4-TDI, 2,6-TDI의농도비교 2,4-TDI 농도는스프레이도장공정에서임핀저 0.896 ppb, 변형 2단카세트홀더 0.341 ppb, 개방형카세트홀더 0.225 ppb 순으로통계학적유의한차이가있었으며 (p<0.0001), 발포공정에서공기중 2,4-TDI 농도는임핀저 0.381 ppb, 변형 2단카세트홀더 0.266 ppb, 개방형카세트홀더 0.247 ppb 순으로통계학적으로유의한차이가있었다 (p=0.025). 건조공정과연 Journal of Korean Society of Occupational and Environmental Hygiene, 2013: 23(2): 95-102 http://www.kiha.kr/

98 김성호, 원종욱, 김치년, 정우진, 노재훈 마공정의공기중 2,4-TDI 농도는모두통계학적유의한차이를보이지않았다. 공기중 2,6-TDI 농도는모든공정의측정값에서임핀저, 변형 2단카세트홀더, 개방형카세트홀더순이었고, 스프레이도장공정 (p< 0.0001), 연마공정 (p=0.023), 발포공정 (p<0.0001) 로통계학적으로유의한차이가있었다 (Table 2). 2,4-TDI, 2.6-TDI 모두에서스프레이도장공정의임핀저방법이가장높은농도를보였으며, 높은농도에서시료채취방법에따른더큰차이가있었다 (Figure 2). 2. 시료채취방법에따른 2,4-TDI, 2,6-TDI의농도비교개방형카세트홀더, 변형 2단카세트홀더, 임핀저방법에따른 2,4-TDI와 2,6-TDI의농도는통계학 적으로유의한차이를보였으며모든측정자료에서 2,4-TDI 보다 2,6-TDI의농도가높은수준을보였다 (Table 3). IV. 고찰이소시아네이트가사용되는산업은현재까지급격히확장되고있는추세이며, 이로인해 TDIs 사용량또한계속증가하고있다. 직업성천식의원인이되는 TDIs는기도자극, 감작과폐기능감소및과민성폐렴을일으킨다. TDIs에의한천식발병에있어서유도기간은매우다양하다. TDIs에의해직업성천식이유발한작업자들의 50% 가초기노출로부터 2 년정도가경과한시점이었다. 전형적으로직업성천 Table 2. Comparison of collection concentrations of 2,4-TDI, 2,6-TDI by the process No. of Mean(ppb) ± S.D. Substances Manufacturing types Process p-value samples Method 1 * Method 2 Method 3 spray painting 16 0.225 ± 0.119 0.341 ± 0.158 0.896 ± 0.566 <0.0001 Musical drying 16 0.110 ± 0.067 0.094 ± 0.069 0.094 ± 0.062 0.735 2,4-TDI instrument grinding 18 0.180 ± 0.126 0.214 ± 0.134 0.213 ± 0.125 0.666 Car seat foaming 16 0.247 ± 0.114 0.266 ± 0.106 0.381 ± 0.156 0.025 spray painting 16 0.681 ± 0.257 0.989 ± 0.298 1.878 ± 0.716 <0.0001 Musical drying 16 0.203 ± 0.123 0.282 ± 0.183 0.366 ± 0.222 0.074 2,6-TDI instrument grinding 18 0.330 ± 0.187 0.397 ± 0.254 0.565 ± 0.311 0.023 Car seat foaming 16 0.514 ± 0.197 0.678 ± 0.188 0.981 ± 0.302 <0.0001 * method 1: sampled by open-face cassette, method 2: sampled by modified 2-piece cassette, method 3: sampled by Impinger, p-value: calculated by ANOVA test Figure 2. Comparison of TDIs concentrations by each process Process : 1=spray painting, 2=drying, 3=grinding, 4=foaming Conc. : A=Open-face cassette, B=Modified 2-piece cassette, C=impinger http://www.kiha.kr Journal of Korean Society of Occupational and Environmental Hygiene, 2013: 23(2): 95-102

시료채취방법에따른작업공정별 Toluene diisocyanates 포집농도비교 99 Table 3. Comparing of the concentrations of 2,4-TDI, 2,6-TDI by the sampling methods. Sampling methods * No of samples Mean(ppb) ± S.D. 2,4-TDI 2,6-TDI p-value Method 1 66 0.190 ± 0.1190.429 ± 0.263 <0.0001 Method 2 66 0.228 ± 0.1480.581 ± 0.357 <0.0001 Method 3 66 0.390 ± 0.4210.936 ± 0.716 <0.0001 * method 1: sampled by open-face cassette, method 2: sampled by modified 2-piece cassette, method 3: sampled by Impinger, p-value: calculated by t-test test 식은 20 ppb 수준의이소시아네이트에 15분간노출된작업자에서유발된다 (Lemiere et al., 1996). 그러나 O'Brien et al,(1979a; 1979b) 이실시한연구에의하면과거에감작된경험이있는작업자들은 1 ppb 수준의낮은농도에서도천식이발병한다고보고하였다. TDIs에대한공기중시료채취및분석방법은그동안다양하게제시되었으며, 공기중 TDIs 농도는국소배기장치와같은공학적인관리로노출을줄일수있다. 그러나공기중이소시아네이트의농도가매우저농도이거나검출되지않는작업장에서직업성천식이발생되는사례들이조사되었다 (Bello et al., 2007). 현재우리나라에서작업환경측정평가시 TDIs 개인시료채취방법으로사용하는방법은 1-2PP를코팅한유리섬유여과지를사용하여시료를채취하며, OSHA Method 42와유사하다 (MoEL, 2011). 하지만이방법은코팅된유도체시약이불안정하고유도체반응이충분히일어나지못해 TDIs 측정평가에서과소평가가될가능성이있다. Mao et al.(2000) 은공기중 TDIs 채취시개방형카세트홀더의단점을보완하기위해변형 2단카세트홀더를사용한실험결과개방형카세트홀더보다포집농도가 21% 더높은결과로보고하였다. 개방형카세트홀더보다변형 2단카세트홀더의포집농도가더높다는선행연구결과를바탕으로유도체시약이안정적이고이소시아네이트류의포집농도가높다고알려진임핀저시료채취방법과함께현재작업환경측정에서개인노출평가시주로사용되는개방형카세트홀더를이용한시료채취와개방형카세트홀더보다포집농도가높은변형 2단카세트홀더를사용하여 TDIs 발생형태가다른스프레이도장, 건조, 연마, 발포공정에서시료를채집하고그농도를공정별로비교분석하였다. 세가지시료채취방법을이용한측정결과모든시 료에서 2,6-TDI가 2,4-TDI 보다많이포집되었다. 이는 2,4-TDI보다반응성이큰 2,6-TDI가공기중으로더많이증발된다 (Rando et al., 1984) 는기존연구결과와동일하였다. 공정별포집농도의분포에서스프레이도장공정, 발포공정, 연마공정, 건조공정순으로높았다. 작업공정에따른이소시아네이트류포집농도를비교한연구에서타공정에비해상대적으로스프레이도장공정에서이소시아네이트류포집농도가높았다는연구결과와 (Kang & Kim, 1999), TDIs 노출사업장에서 2,4- TDI를측정한결과스프레이도장공장에서 2,4- TDI 에가장많이노출되고있다는 (MoEL, 2005) 기존연구결과와동일하였다. TDIs 농도로공정별노출실태파악을위해상가작용을고려한노출기준초과여부평가결과모든공정과채취방법에서노출기준를초과하는시료는없었다. 현재국내작업환경측정기관에서실시하는 TDIs 평가는 2,4-TDI, 2,6-TDI 각각으로노출기준치를적용하여평가하고있다. 그러나실제작업환경에서이들은혼합물로존재하고인체에대한표적장기가호흡기로서작업환경에대한평가는상가작용을고려하여평가하여야한다. 스프레이도장공정에시료채취방법에따른 TDIs 포집농도의통계검정결과 2,4-TDI, 2,6-TDI 모두임핀저, 변형 2단카세트홀더, 개방형카세트홀더순으로포집농도가통계학적으로유의하게높았으며 (p< 0.0001), 2,4-TDI와 2,6-TDI 모두변형 2단카세트홀더의농도가개방형카세트홀더보다포집농도가더높았다. 기존의연구에서개방형카세트홀더와변형 2 단카세트홀더를이용하여 TDIs 생산공장과 TDIs 사용공장내도장공정에서 TDIs를측정하였을때, 변형 2단카세트홀더가개방형카세트홀더보다포집농도가더높았다는연구결과가보고되었다 (Mao et al., 2000; Park et al., 2003). 또한, IOM(Institute of Occupational Medicine) 채취기를이용한여과지채취방법과흡수액을이용한임핀저방법을사용해자동차스프레이도장공정에서 HDI(hexamethylene di-isocyanate) 를측정하였을때, 임핀저를사용하여포집한 HDI 농도가개방형카세트홀더를사용하여포집한 HDI농도보다높았다는연구결과가있었으며 (Bello et al., 2002), 자동차정비공장의스프레이도장공정에서유도체시약 1-2MP(1-(2-methoxyphenyl) piperazine) 을코팅한여과지를이용한채취방법과흡수액을이용한액체채취방법을이용하여 HDI를측정하였을때, 임핀저 Journal of Korean Society of Occupational and Environmental Hygiene, 2013: 23(2): 95-102 http://www.kiha.kr/

100 김성호, 원종욱, 김치년, 정우진, 노재훈 을이용하여포집한 HDI농도가더높았다는연구결과가있다 (Maitre et al., 1996). 본연구결과와선행연구결과를보았을때, 스프레이도장공정에서세가지측정방법에따른 TDIs 포집농도는기존연구결과와동일하였다. 건조공정과연마공정의경우 2,4-TDI 는세가지시료채취방법간에통계학적으로유의한차이를보이지않았으며, 개방형카세트홀더의농도가가장높거나변형 2단카세트홀더의농도보다더높았다. 하지만, 2,6-TDI는연마공정에서만임핀저, 변형 2단카세트홀더, 개방형카세트홀더순으로포집농도가통계학적으로유의하게높았으며 (p=0.023), 변형 2단카세트홀더의농도가개방형카세트홀더보다포집농도가더높았다. 기존선행연구에서연마작업을하는동안발생하는열로인해이소시아네이트의배출이증가하며, 예로자동차정비공장에서연마와용접작업을하는동안많은양의열이발생하는동안이소시아네이트의배출이많이발생하였다 (Karlsson et al., 2000). 이소시아네이트가발생되는형태는가스와입자형태로발생되며이소시아네이트류를측정하였을때, 임핀저를이용한이소시아네이트의포집농도가더높았다는연구결과가있었다 (Henriks-Eckerman et al., 2002). 또한, 다른연구에따르면온도의변화에따라이소시아네이트가공기중으로이동한다는것이보고되었다 (Boutin et al., 2006). 이번연구결과 2,6-TDI의결과는동일한성향으로선행연구와일치하였으나 2,4-TDI는일치하지않았다. 발포공정의경우시료채취방법에따른 TDIs 농도의통계검정결과 2,4- TDI, 2,6-TDI 모두임핀저, 변형 2단카세트홀더, 개방형카세트홀더순으로포집농도가통계학적으로유의하게높았으며 (p<0.05), 2,4-TDI와 2,6-TDI 모두변형 2단카세트홀더의농도가개방형카세트홀더보다포집농도가더높았다. Dahlin et al.(2008) 의연구결과폴리우레탄의열분해시 TDIs는가스와입자형태사이에분포를보이고있으며, 오랜시간동안공기중에남아있었다. TDIs는열분해초기가스형태또는매우작은입자형태이나몇분후입자형태로나타난다. 응집과응축과정을거쳐입자의성장이이루어지며, 시간이경과됨에따라가스형태의 TDIs는감소했다. 위와같은연구결과로건조, 연마, 발포공정에서도가스나입자형태의유도체결합이안정적인임핀저가가장높은농도이었다. 또한카세트홀더벽면에부 착하거나홀더밖으로튕겨져나가는단점을보완한변형 2단카세트홀더의포집농도가개방형카세트홀더보다높았다. 본연구의결과로스프레이도장공정, 연마공정, 발포공정에서 TDIs를측정할경우유도체시약이안정적인흡수액을사용한임핀저를사용한시료채취방법의포집농도가가장높으나현행작업환경측정제도는개인시료채취를원칙으로하고있다. 하지만, 임핀저시료채취방법은 DMSO 노출위험으로인해 NIOSH에서는지역시료채취로제한을두고있어개인노출평가의적용이어렵다. 위결과에따라개인노출평가시개방형카세트홀더보다포집농도가높은변형 2단카세트홀더의사용이적절하다고해석할수있다. 특히, 개방형카세트홀더와변형 2단카세트홀더의농도관계에서타공정에비해상대적으로포집농도가높은스프레이도장공정의시료채취방법은변형 2단카세트홀더를사용한채취방법이바람직하다. 하지만, 본연구의대상공정이 4개공정만을대상으로하였으며, TDIs 발생형태가다른여러공정에서의측정은이루어지지않았다. 또한개방형카세트홀더와변형 2단카세트홀더의시료채취방법이지역시료채취로이루어졌으며, 건조공정의 2,4-TDI의경우변형 2단카세트홀더의포집농도가오히려개방형카세트홀더포집농도보다낮다는한계도발생한다. 향후 TDIs가발생하는타공정에서 2,4 및 2,6-TDI 모두변형 2단카세트홀더가개방형카세트홀더보다포집농도가높다는것을증명한다면움직임이많고다양한오염원이존재하는사업장에서변형 2단카세트홀더의활용이개인시료채취시더욱적합한측정방법임을뒷받침할것이다. 이를위해 TDIs가발생하는더욱다양한공정에서시료채취방법에따른포집농도를비교하고향상시키는연구가추가적으로필요할것이라생각한다. V. 결론본연구는발생형태에따른공정별 TDIs 시료채취방법에의한포집농도를비교평가하였다. 사용한새료채취방법은개방형카세트홀더 (OSHA 42), 2단변형카세트홀더와임핀저 (NIOSH 5522) 를사용하여공기중시료를채취하였으며, 스프레이도장공정, 건조공정, 연마공정, 발포공정 4개소를대상으로세가지시료채취방법을이용하여포집된시료의농도를 http://www.kiha.kr Journal of Korean Society of Occupational and Environmental Hygiene, 2013: 23(2): 95-102

시료채취방법에따른작업공정별 Toluene diisocyanates 포집농도비교 101 비교분석한결과는다음과같다. 1. 대상공정 4개소모든시료에서 2,6-TDI가 2,4- TDI 보다많이포집되었다. 공정별노출실태파악을위해혼합물의노출기준초과여부를평가한결과모든공정에서노출기준을초과하는시료는없었다. 2. 공정별 TDIs 포집농도비교결과스프레이도장공정의경우변형 2단카세트홀더로포집한 2,4 및 2,6-TDI의농도는 0.341, 0.989 ppb로임핀저로포집한 TDIs의농도 0.896, 1.878 ppb의 38% 와 53% 이어개방형카세트홀더로포집한 TDIs의농도 (0.225, 0.681 ppb) 25% 와 36% 보다높았다. 3. 건조공정의경우 2,6-TDI만변형 2단카세트홀더로포집한 2,6-TDI의농도가 0.282 ppb로임펀저로포집한 2,6-TDI의농도 0.353 ppb의 80% 로개방형카세트홀더로포집한 2,6-TDI의농도 (0.203 ppb) 58% 보다높았다. 2,4-TDI의경우개방형카세트홀더로포집한 2,4-TDI의농도가 0.110ppb로임핀저와변형 2단카세트홀더농도 (0.094 ppb) 보다더높았다. 4. 연마공정의경우변형 2단카세트홀더로포집한 2,4 및 2,6-TDI의농도는 0.214, 0.397 ppb로임핀저로포집한 TDIs의농도 0.213, 0.565 ppb의 101% 와 70% 이어개방형카세트홀더로포집한 TDIs의농도 (0.180, 0.330 ppb) 85% 와 58% 보다높았다. 5. 발포공정의경우변형 2단카세트홀더로포집한 2,4 및 2,6-TDI의농도는 0.266, 0.678 ppb로임핀저로포집한 TDIs의농도 0.381, 0.981 ppb의 70% 와 69% 이어개방형카세트홀더로포집한 TDIs의농도 (0.247, 0.514 ppb) 65% 와 52% 보다높았다. 이상의결과로보아세가지시료채취방법중임핀저 (NIOSH Method 5522) 를사용한채취방법의포집농도가가장높았다. 해당시료채취방법은공기중 TDIs 채취시농도의과소평과를막을수있으나, NIOSH 에서는 DMSO의노출위험이있어임핀저채취방법을지역시료채취로제한을두고있다. 건조공정을제외한 3개소의공정에서변형 2단카세트홀더포집농도가개방형카세트홀더보다높았다. 위결과에따라스프레이도장공정, 연마공정, 발포공정의 TDIs 개인시료채취시개방형카세트홀더보다변형 2단카세트홀더를사용한시료채취가더욱적절한측정방법이다. 특히, 타공정에비해상대적으로포집농도가높은스프레이도장공정의개인노출평가시시료채취방법은변형 2단카세트홀더를사용한채취방법 이바람직하다. 참고문헌 American Conference of Governmental Industrial Hygienists(ACGIH). 2013 Threshold limit values for chemical substances and physical agents & biological exposure indices, Cincinnati. Ohio, ACGIH, 2013 Baur X, Marek W, Ammon J, Czuppon AB, Marczynski B, Raulf-heimsoth M, Roemmelt H, Fruhmann G. Respiratory and other hazards of isocyanates. Int Arch Occup Environ Health 1994;66:141-152 Bello D, Sparer J, Redlich CA, Ibrahim K, Stowe MH, Liu Y. Slow curing of aliphatic polyisocyanate paints in automotive refinishing. J Occup Environ Hyg 2007; 4:406-411 Bello D, Streiche RP, Liu YC, Sparer J, Youngs F, Woskie SR. Field comparison of impingers and treated filters for sampling of total aliphatic isocyanates with the MAP reagent. Am Ind Hyg Assoc J 2002;63:790-796 Boutin M, Dufresne A, Ostiguy C, Lesage J. Determination of airborne isocyanates generated during the thermal degradation of car paint in body repair shops. Ann Occup Hyg 2006;50(4):385-393 Choi JK, Kim KS. Study of occupational Asthma(Ⅱ). Korea occupational safety and health agency, 1999 Czamecki B. Polyisocyanate aerosol sampling using coatedfilter vs. impinger collection system. Poster presented at American Industrial Hygiene Conference and Exposition, Boston, 1992 Dahlin J, Spanne M, Karlsson D, Dalene M, Skarping G. Size-separated sampling and analysis of isocyanates in workplace aerosols-part II: Aging of aerosols from thermal degradation of polyurethane. Ann Occup Hyg 2008;52(5):375-383 Fuchs S, Valade P. Etude clinique et experimentale sur quelques cas d'intoxication par le desmodur T (diisocyanate de toluylene 1-2-4 et 1-2-6). Archives des Maladies Professionnelles 1951;12:19119-6 Gang SY. Occupational asthma cases caused by inhalation of Polyurethane. Korean J Asthma Allergy Clin Immuno Abstracts 1978;8-9 Henriks-Eckerman ML, Välimaa J, Rosenberg C, Peltonen K, Engström K. Exposure to airborne isocyanates and other thermal degradation products at polyurethane-processing workplace. J Environ Monit 2002; 4:717-721 Kang HK, Kim HW. Assessment of total isocyanates by Journal of Korean Society of Occupational and Environmental Hygiene, 2013: 23(2): 95-102 http://www.kiha.kr/

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