CLEAN TECHNOLOGY, Vol. 17, No. 2, June 2011, pp. 124~133 청정소재제품기술 국내전기전자제품에함유된신규 RoHS II 물질검출사례연구 송문환, 손승환, 조영달, 최은경 * 한국생산기술연구원국제환경규제대응기술지원단유해물질분석실 426-910 경기도안산시상록구사 3 동 1271-18 (2011 년 5 월 27 일접수 ; 2011 년 6 월 20 일수정본접수 ; 2011 년 6 월 22 일채택 ) Case Study on Determination of the Level of New RoHS II Substances in Domestic Electronic and Electrical Equipments Moon Hwan Song, Seung-Hwan Son, Young Dal Cho, and Eun Kyung Choe* Products Eco-testing Laboratory, Korea Institute of Industrial Technology, 1271-18 Sa3-dong, Sangrok-gu, Ansan 426-910, Korea (Received for review May 27, 2011; Revision received June 20, 2011; Accepted June 22, 2011) 요 2006 년시행되어온 RoHS 규제에유해물질을추가하여더강화된 RoHS II 의공표에대비하여본연구에서는 RoHS II 의최우선규제물질이면서 2010 년발표된 REACH SVHC 후보목록에도포함된물질인 Hexabromocyclododecane (HBCDD) 및 3 종프탈레이트, Dibutyl phthalate (DBP), Butyl benzyl phthalate (BBP), Diethylhexyl phthalate (DEHP) 의국내전기전자제품내의함유여부를사전검토해보려는목적으로사례연구를진행하였다. 이에고분자소재로구성된세탁기, 냉장고, 혹은전자렌지의부품 20 개를 12 개전기전자부품생산회사로부터수거하여 4 종규제물질을기체크로마토그래피질량분석법으로분석하여그함유량을측정한결과 Nitrile Butadine Rubber (NBR), Polypropylene (PP), Polybutylene Terephthalate (PBT), Ethylene Propylene Rubber (EPDM), Polyvinyl Chloride (PVC) 등의소재로된부품중 HBCDD 는 NBR 소재로된 3 종부품에서 42~381 mg/kg 범위로검출되어규제값 0.1 wt% (1,000 mg/kg) 보다는적지만주의를요한다. DBP 및 BBP 는 20 개부품모두에서검출되지않고있어이두물질은전지전자제품용플라스틱소재에서넓게사용되지않고있을가능성을시사하고있다. 그러나 DEHP 는 40~59,400 mg/kg 범위로 NBR, PP, PBT, EPDM 및 PVC 로이루어진부품에서모두검출되어광범위하게사용되고있음을알수있었고특히 NBR 및 PVC 로이루어진 8 개부품에서예상규제치인 0.1 wt% (1,000 mg/kg) 을훨씬능가한 0.45~5.94 w% 로검출되고있어이에대한대비가필요함을알수있었다. 추가로 REACH SVHC( 고위험성물질 ) 에속하는 Diarsenic pentaoxide, Diarsenic trioxide, Lead hydrogen arsenate, Triethyl arsenate 의 4 종물질의함유여부를 ICP 에의한비소 (Arsenic) 분석으로스크리닝해본결과 NBR, PBT 소재의 4 개부품에서 15~700 mg/kg 으로검출되었고이중 PBT 소재의부품인 Thermistor 에서는규제되는비소화합물이규제값 (0.1 wt%, 1,000 mg/kg) 을초과할가능성이매우높다. 주제어 : 전기전자제품, 유해물질검출, 난연제, 프탈레이트, 비소, 기체크로마토그래피질량분석법 약 Abstract : In addition to six substances regulated in EU RoHS including lead, mercury, cadmium, hexavalent chromium, polybrominated biphenyls (PBB) and polybrominated diphenyl ethers (PBDE), priority substances are identified in new RoHS II as hexabromocyclododecane (HBCDD), dibutyl phthalate (DBP), butyl benzyl phthalate (BBP) and diethylhexyl phthalate (DEHP). In this study, 20 plastic samples were collected from 12 domestic electrotechnical companies and levels of four restricted substances were determined by gas chromatography-mass spectrometry. Among 20 parts that compose washer, refrigerator or microwave oven, HBCDD was detected in three samples of NBR material with the amount of 42~381 mg/kg while DBP and BBP was not detected in any samples collected respectively, implying that these substance may not be used widely in plastic materials for EEE. However, DEHP was detected in all samples of NBR, PP, PBT, EPDM and PVC materials with the amount of 42 up to 59,400 mg/kg that exceeds the limit value of 0.1 wt% (1,000 mg/kg). Presence of a restricted substance in polymer material makes a great negative influence on a number of final product. To cope with coming RoHS II as well as REACH, action not to use DEHP in plastic material or the relevant notification in case of REACH seems to be needed. Screening test of Arsenic compounds such as diarsenic pentaoxide, diarsenic trioxide, lead hydrogen arsenate, triethyl arsenate that are included in REACH SVHC was done by ICP measurement. Arsenium was detected in four samples made of NBR and PBT materials in the level of 15~700 mg/kg. By considering the screening method used in this study, the amount of arsenium compounds in the thermistor made of PBT material has a high chance of exceeding the regulated limit value. Keywords : Electronic and electrical equipments, RoHS II, Phthalate, HBCDD, Arsenic compound, GC-Mass, ICP * To whom correspondence should be addressed. E-mail: ekchoe@kitech.re.kr 124
국내전기전자제품에함유된신규 RoHS II 물질검출사례연구 125 1. 서론 RoHS (Restriction of the use of certain Hazardous Substances in electrical and electronic equipment) 는전기및전자장비내특정유해물질의사용에대한제한지침으로유럽의회및유럽연합심의회에서제안하여 2006년 7월부터시행되어왔다 [1]. RoHS의시행으로납 (Pb), 수은 (Hg), 카드뮴 (Cd), 6가크로뮴 (Cr(Vl)) 및두가지유형의브로민계난연제인폴리브로민화바이페닐 (PBB) 과폴리브로민화다이페닐에테르류 (PBDEs) 의 6종물질 (substance) 이허용농도 0.01 wt%( 카드뮴 ) 및 0.1 wt%( 기타물질 ) 로규제되어왔고, 관련회사들의적극적인품질관리대응으로시행초기와는달리더이상전기및전자제품에서검출되지않고안정화되어있는현황이며, 그시험법도국제표준인 IEC 62321 및이의 KS 표준에규정되어있다 [2,3]. 그러나 RoHS 지침서 (Directive) 제6조의유해물질추가검토에대한명시와함께할로겐난연제대체를완료한 Acer, HP, Dell, Sony, Ericsson 등일부글로벌기업들과 Chemsec (The International Chemical Secretariat)[4] 및 Greenpeace[5] 등의지속적인추가물질에대한사용제한요구등으로규제물질의확대및강화는불가피하게진행되어왔다 [6,7]. 2008년 Oeko-Institut에서 RoHS 지침서에서규제되고있지않는전기전자제품함유유해물질에관한연구를실시하였고전기전자제품의생산자및공급자들이제공한자기선언 (Declaration) 과 XRF 분석등의정보에기초하여 46종후보물질목록 (Inventory) 이작성되었다 [8,9]. 2008년 EU집행위에서규제대상물질을추가하여더강화된 RoHS II 초안문 (RoHS 개정안 ) 이제안된이래 [10], 이에대한수정안이 2009년, 2010년두차례제안되고검토되는과정을거치며최종발표및시행을앞두고있다. RoHS 개정의진행과정에서언급되고있는고려대상물질 ( 부속서 III) 은비소계화합물, 베릴륨과그화합물, 삼산화안티몬, Dinickeltrioxide, 비스페놀 A, 브롬계난연제를제외한유기브롬 (Organobromines), 염소계난연제또는가소제를제외한유기염소 (Organochlorines) 의 7종이며, 새로운제한물질 ( 부속서 IV) 은브롬계난연제 (Brominated flame retardants), 염소계난연제 (Chlorinated flame retardants), PVC (Polyvinylchloride), 염소계가소제Chlorinated plasticizers), DEHP, BBP, DBP이며 7종새로운제한물질의규제값은 0.1 wt% 이다 [6,7]. EU에서 2007년 6월시행된 EU 新화학물질관리규정인 REACH (Registration, Evaluation, Authorization, and Restriction of CHemicals) 법령에서는 CMR (Carcinogenic, Mutagenic or Toxic for Reproduction), PBT (Persistent, Bioaccumulative and Toxic) 및 vpvb (very Persistent and very Bioaccumulative) 물질을고위험성물질 (SVHC, Substances of Very High Concerns) 로정의하고 [11] 유럽화학물질청 (ECHA, European Chemicals Agency) 에서 2008년 10월및 2010년 1월두번에걸쳐 REACH SVHC 허가후보목록 ( 총 30종 ) 을발표한바있다 Table 1. Summarized information of phthalates and HBCDD prohibited on use Substance/ Abbreviation CAS No./ EC No. Chemical structure Hazard information[12] Related regulations Usage [14-17] Dibutyl phthalate DBP 84-74-2 201-557-4 Toxic to reproduction Cat.2 REACH RoHS II - as a plasticizer in resins and polymers such as PVC - printing inks, adhesives, sealants/grouting agents, nitrocellulose paints, film coatings and glass fibres - cosmetics Di-(2-ethylhexyl) phthalate DEHP 117-81-7 204-211-0 Toxic to reproduction Cat.2 REACH RoHS II - widely used as a plasticizer in polymer products, mainly PVC : building material such as flooring, cables, profiles and roofs, as well as medical products like blood bags, dialysis equipment etc. - used in other non-polymer formulation Benzyl butyl phthalate BBP 85-68-7 201-622-7 Toxic to reproduction Cat.2 REACH RoHS II - > 90%, goes to plasticising of PVC or other polymers. flooring, sealants, and paints - food wrap or food package - baby equipment, children toys (impurity level) Hexabromo cyclododecane HBCDD 25637-99-4 247-148-4 Persistent, Bioaccumulative, and Toxic REACH RoHS II - as flame retardant in polystyrene (PS) : rigid thermal insulation panels/boards for buildings and for road and railway constructions to prevent frost heaves and provide a lightweight load-spreading construction material. - as flame retardant in High Impact PS (HIPS) : electronic and electrical equipment. - flameretard textiles (for furniture, automobile interiors etc)
126 청정기술, 제 17 권제 2 호, 2011 년 6 월 Table 2. Application areas of arsenic compounds in candidate list of REACH SVHC Substance CAS No./ EC No. Hazard information[12] Usage [9,18-20] Diarsenic pentaoxide Diarsenic trioxide 1303-28-2 215-116-9 1327-53-3 215-481-4 Carcinogenic Carcinogenic in the dying industry, in metallurgy, for manufacturing special glass in wood preservatives Lead hydrogen arsenate 7784-40-9 232-064-2 Carcinogenic and toxic for reproduction insectides in fruit trees, pesticides, wood preservatives (in the process of being phase-out) Plastic/PVC products (including garden articles, travel/leisure time articles, construction materials and wallpapers), Lead accumulators electrical and electronic equipment (EEE) grouts, textiles. cosmetics,hip-bottom paint, mineral fertilizer, glass goods, glass beads for road markings Triethyl arsenate 15606-95-8 427-700-2 Carcinogenic as above, in the fabrication of integrated circuits [12]. 이를반영하여 2010년 EU의회의환경위원회에서 RoHS II 고려대상물질목록에 REACH SVHC 30종을추가로제안하여, 현재확대되어있다 [7]. RoHS 개정안을보면신규규제물질의추가는 REACH에서수립된방법론을이용하여검토하도록되어있어 [7,10] 향후에도 REACH SVHC 후보물질과밀접한영향이있을전망이다. RoHS II의최우선규제물질 (priority substances) 은 Hexabromocyclododecane (HBCDD) 및 Dibutyl phthalate (DBP), BBP (Butyl benzyl phthalate), DEHP (Diethylhexyl phthalate) 3종프탈레이트이며 [13] 이물질들은유럽화학물질청 (ECHA, European Chemicals Agency) 에서 2008년발표한 15종 SVHC 후보목록에도포함된물질이다 [12]. HBCDD의주요용도는폴리스타이렌고분자용난연제이며, 3종프탈레이트는 PVC 등의고분자에가소제로사용되며각물질의규제사유가되는유해성 (Hazard) 및용도는 Table 1과같다 [9,14-17,18-20]. RoHS II의최종입법까지는아직적지않은절차와시간이소요될예정이지만국내기업의대비가필요한시점이다. 이에본연구에서는국내전기전자제품내에 RoHS II 규제물질인 HBCDD 및 3종프탈레이트, DBP, BBP, DEHP의함유여부를사전검토해보려는목적으로국내전기전자부품기업의생산품을대상으로사례연구를진행하였다. 추가로비소화합물 (Arsenic Compounds, Table 2) 의함유여부도비소 (Arsenic) 측정에의하여스크리닝 (Screeing) 해보았다. 2. 실험 2.1. 대상부품수집세탁기, 냉장고및전자레인지등의대표적가전제품을구성하는부품중에서난연제및가소제를함유할가능성이있는플라스틱재질로구성된부품을수집하도록계획하였고최종완제품생산기업의도움을받아이들부품을생산하여납품하는협력업체를통하여수집하는방식으로진행하였다. 12개회사의 20개부품 (7종) 을수집하면서이들부품의용도및재질을함께조사하였다 (Table 3). 2.2. 시약, 장비및기기 2.2.1. 시약톨루엔과헥산은 GC급을사용하였고, 헬륨과아르곤은순도 99.999 vol%, 99.9999 vol% 을사용하였다. HBCDD와 3종프탈레이트는각 Sigma-Aldrich사및 Supelco사에서시약급 ( 표준시약 ) 으로구입하여정제없이사용하였다. 비소 (As) 표준시약은 MERCK사에서구입하여사용하였고 ( 농도 1,000 mg/l), 질산 (nitric acid, HNO 3), 불산 (hydrofluoric acid, HF) 및과산화수소 (hydrogen peroxide, H 2O 2) 는각 65 vol%, 40 vol% 및 30 vol% 농도의시약급이었다. 증류수는 RO (Reverse Osmosis) Filter로처리후전기전도도측정값이 18.2 Ω인 2차증류수를사용하였다. 2.2.2. 장비및사용기기시료분쇄에는 Centrifugal mill (Pulverisette 14, Germany), 그리고프탈레이트및 HBCDD 분석을위한시료추출에는 250 ml 용량의속스레장치가사용되었다. 비소 (As) 분석을위한시료용해에는 microwave digestion system (Milestone, Ethos Touch Control, Italy) 이사용되었다. HBCDD 및프탈레이트의정량분석에는 GC-Mass (Gas Chromatography-Mass Spectometry) (Agilent, HP 6890, HBCDD 검출은 MS (5975i)/ 프탈레이트검출은 MS (5973N)) 을사용하였고비소 (As) 의정량분석에는 ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometer) (Jovin-Yvon, Ultima II, Horiba) 를사용하였다. 국제및 KS 표준분석법에서권장하는데로 [2,3] 반복성 (Repeatability) 을위하여자동시료채취장치 (autosampler) 를사용하였다 (GC-Mass 7683 series injector, Agilent). 2.3. 시료샘플링수집된세탁기, 냉장고및전자레인지의구성부품 20개 (7 종 ) 에서플라스틱재질로된부분을물리적으로분리하여 Centrifugal mill을사용하여추출전에균일하게 500 µm의체를통과할수있도록분쇄한다. 액체질소로냉각시키는저온분쇄가권장된다 [2,3].
국내전기전자제품에함유된신규 RoHS II 물질검출사례연구 127 Table 3. Information of electrical and electronic parts collected from 12 companies for the case study Sample/Company Name of part Picture Usage in end products : washer, refrigerator and microwave oven No.1 / Comp. A Bellow Assembly as valve drain assy. of washer No.2 / Comp. B Bobbin as drain motor assy. of washer No.3 / Comp. C Thermistor as temperature control assy. of refrigerator No.4 / Comp. D Gasket as door assy. of refrigerator No.5 / Comp. E Absorber Pipe as cooling assy. of refrigerator No.6 / Comp. F Absorber Compression Rubber as cabinet assy. of refrigerator No.7 / Comp. G Absorber Compression Rubber as cabinet assy. of refrigerator No.8 / Comp. H as power cord assy. of washer No.9 / Comp. I No.10 / Comp. I as power cord assy. of refrigerator No.11 / Comp. I No.12 / Comp. I No.13 / Comp. I No.14 / Comp. I No.15 / Comp. I No.16 / Comp. I No.17 / Comp. I No.18 / Comp. J as power cord assy. of microwave oven No.19 / Comp. K No.20 / Comp. L 2.4. 대상부품에서프탈레이트및 HBCDD 분석 2.4.1. 시료추출 2.3에따라균질하게분쇄된시료는전자저울을이용하여 2 g을측정한후셀룰로오스재질인원통형추출심블 (thimble) 에담아, 프탈레이트분석을위해서는헥산약 90 ml, HBCDD 분석의경우톨루엔약 90 ml을이용하여 1시간당용매순환속도가 4~8회가되도록온도를맞추고 8시간이상추출을하였다. 속슬렛장치로추출된용액은 0.45 µm 실린지필터로여과한후 100 ml 부피플라스크에담아추출시사용했던동일용매로표시부분까지부피를맞춘후 GC 자동시료채취장치용 2 ml vial에옮겨졌다.
128 청정기술, 제 17 권제 2 호, 2011 년 6 월 2.4.2. 표준용액의제조 GC-Mass 검량곡선작성을위하여 3종프탈레이트와 HBCDD 에대한표준용액을제조하였다. EPA phthalate esters 혼합용액 ( 각 2,000 ug/ml, hexane) 을이용하여 0.3125, 0.625, 1.25, 2.50, 5.00, 10.00 ug/ml 농도의프탈레이트 3종 (DBP, BBP, DEHP) 표준용액을제조하였고, 톨루엔으로 1,000 ug/ml 농도의 HBCDD 용액을제조한후, 0.625, 1.25, 2.50, 5.00 ug/ml 농도의 HBCDD 표준용액을제조하였다. 2.4.3. GC-Mass 분석속슬렛추출에의해분석대상물질을추출한후기체크로마토그래피와질량분석법으로프탈레이트와 HBCDD를 1개의시료에대하여 2회반복 ( 전처리부터 2회 ) 분석하였으며, 총이온전류질량분석방법 ( 전주사법 ) 으로물질을확인한후, 선택이온모니터링 (SIM) 을이용해정량되었고이에사용된컬럼및기기분석조건등은 Table 4에정리하였다. 3종의 Phthalates의경우 0.3125~10 ug/ml 범위에서제조된 6개표준용액을 3회반복측정하여검량곡선을작성하였고, HBCDD 또한 0.625~5 ug/ml 범위에서제조된 4개표준용액을이용하여 3회반복측정하여검량곡선을작성하였다. 시료에함유된프탈레이트및 HBCDD의농도는외부표준물 (ESTD, External Standard) 로작성된검량곡선 (Calibration Curve) 에의하여계산하였고동일시료에대하여시료추출부터 2회반복측정하여평균값을구하였다. 2.5. 대상부품에서비소 (As) 분석 2.5.1. 시료전처리 2.3에따라균질하게분쇄된시료를전자저울에 0.5 g을측정하여 microwave용 teflon vessel에담아질산 (65 vol%) 10 ml, 불산 (40 vol%) 1 ml 및과산화수소수 (30 vol%) 1 ml를첨가후시료를장착시킨다음 210, 1,000 W에서 90분간용해하였다. 시료가담긴 teflon vessel을분리하여 -25 냉장고에서 60분간냉각한후 50 ml 부피플라스크에담아부피를맞춘후 ICP 분석을진행하였다. 2.5.2. 표준용액의제조 2차증류수를이용하여 3 vol% 질산을제조한후교정이완료된피펫과부피플라스크를사용하여비소 (As) 표준용액 (1,000 ug/ml, MERCK) 으로부터 0.10, 0.50, 1.00 ug/ml 농도로검량곡선작성을위한표준용액을제조하였다. Table 4. Details on (a) pretreatment, (b) GC-Mass analysis, and (c) ICP analysis (a) Pretreatment Grinding homogenized using a centrifugal mill with particle size less than 500 µm Extraction for GC-Mass analysis of phthalates Soxhlet extraction using hexane for 8 hrs with 4~8 cycle/hr Extraction for GC-Mass analysis of HBCDD Soxhlet extraction using toluene for 8 hrs with 4~8 cycle/hr Decomposition for ICP analysis of Arsenic decomposed in microwave digestion system using HNO 3 (65 vol%), HF (40 vol%) and H 2O 2 (30 vol%), for 90 min at 210 (b) GC-Mass analysis phthalates HBCDD Column HP-5MS (30 m 0.25 mm 0.25 um) HP-5MS (10 m 0.25 mm 0.25 um) Carrier gas Helium Helium Oven 90 (3 min) 200 (0 min) with 20 /min 310 (5 min) with 10 /min 110 (5 min) 200 (5 min) with 40 /min 325 (5 min) with 10 /min Inlet Temp. and mode 300 / Splitless 320 / Splitless Injection Volume 1 ul 2 ul Acquisition mode SIM SIM Reference masses for the quantification Detector / Pump Torch / Temp. Carrier gas Gas flow rate Injection Volume DBP : 149, 205, 223 BBP : 149, 91, 206 DEHP : 149, 167, 251 (c) ICP-AES analysis PMT / Peristaltic Pump Vertical Type / 10,000 K Argon 12 L / min / 0.1 L / min (Cooling gas / Sheath gas) 10 ml/min 319, 401. 561
국내전기전자제품에함유된신규 RoHS II 물질검출사례연구 129 2.5.3. ICP 분석 2.5.1의전처리를통해완전용해된시료를고주파유도코일에의하여형성된플라즈마에도입하여, 10,000 K에서여기된원자가낮은에너지준위로떨어지면서방출하는빛을회절장치를이용하여순차적으로분산 (Dispersion) 시켜비소 (As) 에해당하는 193.696 nm 발광선의흡광도를측정하였다. 바탕값을확인하고, 제조된 0.10~1.00 ug/ml 농도범위의표준용액을 3회반복측정하여그평균값으로검량곡선을작성하였다. 임의의시료도 3번반복측정하여그평균값으로비소 (As) 를정량하였다. 3. 결과및고찰 3.1. 규제유해물질이함유된부품의재질세탁기, 냉장고, 전자레인지등의대표적인가전제품에플라스틱재질의부품을조사한결과, thermostat, bearing inner, bellow assembly, bobbin, power cord, gasket, absorber pipe, absorber compression rubber, switch bimtl assembly, switch def timer, switch timer 등의부품이있으며, 구성재질은 PVC, PBT, PP, NBR, EPDM, POM (Polyoxymethylene), Nylon 66, PPS(Polyphenylene Sulfide) 이었다. 세탁기, 냉장고, 전자레인지의파워코드부품대부분은 PVC로구성되고, 극소부분 PBT로도구성되며, 냉장고의 thermostat는 Nylon 66나 PBT로구성됨이조사되었다. PVC로구성된다른부품으로는냉장고도어부품내의틈막이 (gasket) 가있었고, 냉장고의 bellow assembly, absorber compression rubber가 NBR로구성되었다. 재질이조사된부품중실제분석을한부품으로는 Table 3의 7종부품 20개로써, 세탁기부품으로는 valve drain assembly 안에들어있는 bellow assembly, tub assembly 내에들어있는 bearing inner, 배수용모터내의전기줄감개 (bobbin), 전기코드등을수집하였고냉장고부품으로는온도조절장치내의 thermistor, 전기코드, 도어부품내의틈막이 (gasket), 냉각기부품내의 absorber pipe, 캐비넷우레탄부품내의 absorber compression rubber, 전기코드등을수집하였으며, 전자레인지부품으로는전기코드를수집하여규제유해물질함유여부를분석하였고이들을구성하는각재질은 Table 5와같다. 이중 PVC 소재는 Greenpeace의활동 [5] 이나 RoHS II의새로운제한물질항목에들어가있어대체물질에대한대비가필요하다고볼수있다. Table 5. Amounts of phthalates, HBCDD and Arsenic detected in electrical and electronic components collected from 12 companies and their constituent materials Amounts measured (mg/kg) Samples Company Name of part Material* Phthalates DBP DEHP BBP HBCDD Arsenic No.1-W A Bellow Assembly NBR ND 20,200 ND 381 150 No.2-W B Bobbin PP ND 300 ND ND ND No.3-R C Thermistor PBT ND 50 ND ND 700 No.4-R D Gasket PVC ND 59,385 ND ND ND No.5-R E Absorber Pipe EPDM ND 117 ND ND ND No.6-R F Absorber Comp. Rubber NBR ND 55,641 ND 360 25 No.7-R G Absorber Comp. Rubber NBR ND 158 ND 42 15 No.8-W H PVC ND 117 ND ND ND No.9-R I PVC ND 105 ND ND ND No.10-R I PVC ND 52,818 ND ND ND No.11-R I PVC ND 43,704 ND ND ND No.12-R I PVC ND 510 ND ND ND No.13-R I PVC ND 4,506 ND ND ND No.14-R I PVC ND 115 ND ND ND No.15-R I PVC ND 40,777 ND ND ND No.16-R I PVC ND 233 ND ND ND No.17-R I PVC ND 82 ND ND ND No.18-M J PVC ND 44,463 ND ND ND No.19-M K PVC ND 748 ND ND ND N0.20-M L PVC ND 42 ND ND ND * NBR: Nitrile Butadien Rubber, PP: Polypropylene, PBT: Polybutylene Terephthalate, EPDM : Ethylene Propylene Rubber, PVC; Polyvinyl Chloride
130 청정기술, 제 17 권제 2 호, 2011 년 6 월 (a) Figure 1. GC-Mass SIM chromatograms of (a) phthalates and (b) hexabromocyclododecane. (b) (a) DBP (b) BBP (c) DEHP (d) HBCDD Figure 2. Figure 2. Mass spectral patterns of (a) DBP, (b) BBP, (c) DEHP and (d) hexabromocyclododecane.
국내전기전자제품에함유된신규 RoHS II 물질검출사례연구 131 3.2. 부품의프탈레이트함유분석결과프탈레이트측정은 KS 규격 [21] 을근거로하여, 분석법의유효화 (Validation) 과정을거쳐본실험실에구축된시료추출법과 GC-Mass 분석법을이용하였다 [22,23]. 분석하고자하는 3종프탈레이트인 DBP, BBP, DEHP는기체크로마토그램의 11.97분, 15.06분, 16.48분대에각각분리되어나왔고 (Figure 1(a)), Mass Spectrometry 검출에의하여각물질의확인이가능하였다 (Figure 2(a)~(c)). Figure 2는분석물질의 fragmentation으로생성된화학종의 m/z (mass-to-charge ratio) 값을 x 축으로하여그세기 (abundance) 를 y축에나타낸그래프로이세물질의주요 m/z 값은 DBP는 149, 205, 223, BBP는 149, 91, 206, DEHP는 149,167, 251임을보여주었고, 물질의확인은이주요 m/z값및소장된소프트웨어 (Library match) 로이루어졌다. 이중세물질에공통적이고세기가제일큰 m/z 149를정량의타겟이온으로한단일 ( 선택 ) 이온측정 (Single Ion Mode) 으로 DBP, BBP, DEHP의각검량곡선이작성되었고각검량곡선은 Figure 3(a)~(c) 에서보여주듯이좋은직선 성 (Linearity) 을보여주었다. 이상의방법으로세탁기, 냉장고및전자렌지를구성하는폴리머로된부품 20개샘플에서 DBP, BBP, DEHP를측정한결과 (Table 5), DBP 및 BBP는검출되지않은반면 DEHP가 NBR, PP, PBT, EPDM 및 PVC 등의소재로된부품 20개에서모두검출되어광범위하게사용되고있음을알수있었다. 검출된 DEHP 함유량도 42~59,400 mg/kg 범위이며특히 NBR 및 PVC로이루어진 8개부품에서예상규제치인 0.1 wt% (1,000 mg/kg) 을훨씬능가한 0.45~5.94 wt% 로검출되고있어이에대한대비가필요함을알수있었다. PVC 소재로된부품은 Gasket 및 2종으로각 1개및 13개의총 14 개샘플이수거되었는데 5개의각기다른회사에서생산되었음에도불구하고 DEHP가모두검출되었다. 3.3. 부품의 HBCDD 함유분석결과 HBCDD 측정은 KS 규격 [24] 을근거로하여, 분석법의유효화 (Validation) 과정을거쳐본실험실에구축된시료추출법 (a) DBP (b) BBP (c) DEHP Figure 3. Calibration curves for phthalates and hexabromocyclododecane. (d) HBCDD
132 청정기술, 제 17 권제 2 호, 2011 년 6 월 과 GC-Mass 분석법을이용하였다 [22,23]. 분석하고자하는 HBCDD의기체크로마토그램 retention time은 16.11분이었고 (Figure 1(d)), Mass Spectrometry 검출에의하여 HBCDD임을확인하였다 (Figure 2(d)). HBCDD를확인하는주요 m/z 값은 319, 401. 561이며 m/z 319를타겟이온으로정량에이용하였고, 이의세기를기준으로한단일 ( 선택 ) 이온측정 (Single Ion Mode) 에의해작성된 HBCDD의검량곡선은좋은직선성 (Linearity) 을보여주었다 (Figure 3(d)). 이상의방법으로세탁기, 냉장고및전자렌지를구성하는폴리머로된부품 20개샘플에서HBCDD를측정한결과, HBCDD 는 PP, PBT, EPDM 및 PVC 소재로된부품에서는검출되지않았다. 그러나 NBR 소재의 3개샘플에서 42, 360, 381 mg/kg 으로측정되어규제값 (0.1 wt%, 1,000 mg/kg) 보다는적지만주의를요하고있다. HBCDD가난연제로첨가되는주소재는폴리스타이렌으로주요 4개제품군은 Expanded Polystylene ((EPS), Extruded Polystylene (XPS), 고충격폴리스타이렌 (HIPS, High Impact Polystylene), 섬유용폴리머분산제품으로알려져있다 [17]. HBCDD가규제되는근거는 PBT (Persistent, Bioaccumulative, and Toxic) 물질로분류되기때문이며 [12], 전기전자제품뿐만이아니라섬유제품에코라벨에서도난연가공제 (flame retardant finishes) 로서의사용이오래전부터금지되어왔다 [25]. 3.4. 비소화합물 (Arsenic compounds) 함유여부의스크리닝 (Screening) 결과 수거된 20개샘플을 ICP 분석으로비소 (As) 함유량을측정한결과, NBR, PBT 소재의 4개부품에서비소가검출되었다 (Table 6). NBR 소재의부품에서는 15~150 mg/kg의비소가측정되었고 PBT 소재의부품에서는 700 mg/kg의비소가측정되었다. ICP 분석시의산을이용한전처리방법은비소의휘발성을내포하고있어실제함유량보다적은값이측정됨을고려할수있고, 또한어떤비소화합물인지의분석은본연구에서더진행되지는않았지만측정된비소양을비소화합물의양으로환산한다면 PBT 소재의부품 (Thermistor) 에서는규제비소화합물이비소측정값보다더큰값이되어규제값 (0.1 wt%, 1,000 mg/kg) 을초과할가능성이매우높다. RoHS II 고려대상물질로제안되어있는비소화합물 (Arsenic compounds) 은 REACH SVHC 허가후보목록에다음의구체적인네가지물질로발표되어있다 ; Triethyl arsenate, Lead hydrogen arsenate, Diarsenic trioxide, Diarsenic pentaoxide. 이들물질의규제근거는 CMR 물질로분류되기때문이며 [12], 네가지비소화합물의확인된용도혹은미량불순물 (occurrence as impurities) 로함유되어있을가능성이있는분야는잉크, 페인트, 안료, 염료, 난연제, 착색유리, 금속접착제, 살균제, 목재방부제, 전기전자제품, 집적회로등이며 Table 2 에물질별로정리하였다 [9,18-20]. 또한비소화합물은 Oeko- Institut의목록 (Inventory) 에의하면전지전자제품 (EEE) 에서난연제 (flame retardant) 로도사용될가능성이있다고한다 [9]. 4. 결론 RoHS II의시행에대비하여국내전기전자제품에서의 RoHS II 최우선항목인 HBCDD 및 DBP, BBP, DEHP 3종프탈레이트의검출여부를조사하기위하여 12개회사에서생산한전기전자부품을수집하여화학분석하는사례연구를진행하였다. 분석대상이된세탁기, 냉장고및전자렌지를구성하는폴리머로된부품 20개의 GC-Mass 분석결과 HBCDD 는규제값 (0.1 wt%, 1,000 mg/kg) 보다는적지만 NBR 소재의 3개샘플에서 42, 360, 381 mg/kg으로측정되어주의를요하며 DBP 및 BBP는검출되지않았다. 그러나 DEHP가 NBR, PP, PBT, EPDM 및 PVC 등의소재로된부품 20개에서모두검출되어광범위하게사용되고있음을알수있었다. 검출된 DEHP 함유량은 42~59,400 mg/kg 범위이며특히 NBR 및 PVC 로이루어진 8개부품에서예상규제치인 0.1 wt% (1,000 mg/ kg) 을훨씬능가한 0.45~5.94% 로검출되고있어이에대한대비가필요함을알수있었다. 이에더하여 ICP에의한비소화합물 (Arsenic compounds) 스크리닝시험 (Screening test) 을시행한결과 NBR, PBT 소재의 4개부품에서 15~700 mg/kg 의비소가검출되었고이중스크리닝방법을고려해보면 PBT 소재의부품 (Thermistor) 에서는규제비소화합물이비소측정값보다더큰값이되어규제값 (0.1 wt%, 1,000 mg/kg) 을초과할가능성이매우높다. 본연구를통하여전지전자제품의유해물질을품질관리함에있어폴리머소재관리가중요함을재확인하였고, 규제하는유해물질이어느폴리머소재에들어있는지의산업계사례일부를파악하였다. 감사본연구는지식경제부 산업원천기술개발사업 ( 청정생산기반분야 ) 으로수행된결과이며연구비지원에감사드립니다. 약어 RoHS : Restrictions of Hazardous Substances in electrical and electronic equipment REACH : Registration, Evaluation, Authorization, and Restriction of CHemicals EEE : Electronic and Electrical Equipments SVHC : Substances of Very High Concerns 고위험성물질 CMR : Carcinogenic( 발암성 ), Mutagenic( 돌연변이유발성 ) or Toxic for Reproduction( 생식독성 ) PBT : Persistent( 잔류성 ), Bioaccumulative( 생물농축성 ), and Toxic( 독성 ) vpvb : Very Persistent and very Bioaccumulative substances IEC : International Electotechnical Commission GC-MS : Gas Chromatography-Mass Spectometry 기체크로마토그래피-질량분석법 ICP-AES : Inductively Coupled Plasma-Atomic Emission Spectrometer 유도결합플라즈마방출분광법
국내전기전자제품에함유된신규 RoHS II 물질검출사례연구 133 SIM : Single Ion Mode 단일 ( 선택 ) 이온측정 m/z : mass-to-charge ratio 질량 / 전하 LOD : Limit of Detection 검출한계 LOQ : Limit of Quantification 정량한계 MDL : Method Detection Limit 방법검출한계 PBB : Polybrominated biphenyls 폴리브로민화바이페닐 PBDE : Polybrominated diphenyl ethers 폴리브로민화다이페닐에테르 DBP : Dibutyl phthalate BBP : Butylbenzyl phthalate DEHP : Diethylhexyl phthalate, Bis(2-ethylhexyl)phthalate HBCDD : Hexabromocyclododecane NBR : Nitrile Butadien Rubber PVC : Polyvinyl Chloride, 폴리비닐클로라이드 PP : Polypropylene, 폴리프로필렌 PBT : Polybutylene Terephthalate EPDM : Ethylene Propylene Rubber 참고문헌 1. Directive 2002/95/EC, Restriction of the use of certain hazardous substances in electrical and electronic equipment, Official Journal of the European Union, L37, the European Parliament and the Council of the European Union, 2003. 2. IEC 62321, Electrotechnical products-determination of levels of six regulated substances (lead, mercury, cadmium, hexavalent chromium, polybrominated biphenyls, polybrominated diphenyl ethers), International Electrotechnical Commission, Geneva, 2008. 3. KS C IEC 62321, Electrotechnical products - Determination of levels of six regulated substances (lead, mercury, cadmium, hexavalent chromium, polybrominated biphenyls, polybrominated diphenyl ethers), Korea Agency for Technology and Standards, Gwacheon, 2009. 4. http://www.chemsec.org 5. http://www.greenpeace.org/international/en/news/features/ calling-out-samsung-030310 6. Ju, H. -S., and Hong, S. Y., Comparison between RoHS and RoHS II, COMPASS Analyst Report No. 312-09-020, Korea National Cleaner Production Center, 2009. 7. Ju, H. -S., and Yun, H. R., Revision Trends of EU RoHS (2), COMPASS Analyst Report No. 312-10-030, Korea National Cleaner Production Center, 2010. 8. http://hse-rohs.oeko.info 9. http://echa.europa.eu/doc/consultations/svhc/svhc_axvrep_ norway_cmr_leadas_20083006.pdf 10. COM(2008)0809-C6-0471/2008 2008/0240(COD), Proposal for EU Directive on the restriction of the use of certain hazardous substances in electrical and electronic equipment, the European Parliament, 2009. 11. Regulation (EC) No 1907/2006, Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH), Official Journal of the European Union, L396, the European Parliament and the Council of the European Union, 2006. 12. http://echa.europa.eu/chem_data/authorisation_process/candidate_list_table_en.asp 13. http://www.sgs.com/sgs-rohs-coming-soon-first-reading-ondraft-completed?viewid=641 14. http://echa.europa.eu/doc/consultations/recommendations/ tech_reports/tech_rep_dbp.pdf 15. http://echa.europa.eu/doc/consultations/recommendations/ tech_reports/tech_rep_bbp.pdf 16. http://echa.europa.eu/doc/consultations/recommendations/ tech_reports/tech_rep_dehp.pdf 17. http://echa_2008_2_sr04_hbcdd_report_12_01_2009 18. http://echa.europa.eu/doc/candidate_list/svhc_axrep_norway_cmr_triethylas.pdf 19. http://echa.europa.eu/doc/candidate_list/svhc_supdoc_diarsenic%20pentaoxide_publication.pdf 20. http://echa.europa.eu/doc/candidate_list/svhc_supdoc_diarsenic%20trioxide_publication.pdf 21. KS M 1991:2008, Determination of phthalates contents in polymer materials, Korea Agency for Technology and Standards, Gwacheon, 2008. 22. ICH Q2B Guideline, Validation of analytical procedures methodology, International Conference on Harmonization of Technical Secretariat, Geneva, 2007. 23. Choe, E. K., Technology development of SVHC-testing and exposure scenario and establishment their infrastructure to cope with REACH SVHC, Mid-term report of MKE-funded research, Korea Institute of Industrial Technology, Ansan, 2009. 24. KS M 1072:2008, Determination of TBBPA (Tetrabromobisphenol-A) and HBCD (Hexabromocyclododecan) in polymer materials, Korea Agency for Technology and Standards, Gwacheon, 2008. 25. Oeko-Tex Standard 100, Ed.01/2011, International Association for Resarch and Testing in the Field of Textile Ecology, Ed., Oeko-Tex, Zuerich, 2011.