Analytical Science and Technology (분석과학)

The Korean Society of Analytical Sciences (한국분석과학회)
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Study on verification of various national standards regarding phthalate testing in industrial products

공산품 중 프탈레이트류 함유량 분석법에 관한 국내외 표준의 검증 연구

  • Song, Moon-Hwan (Product Eco-testing Laboratory, Korea Institute of Industrial Technology) ;
  • Cho, Young-Dal (Product Eco-testing Laboratory, Korea Institute of Industrial Technology) ;
  • Choe, Eun-Kyung (Product Eco-testing Laboratory, Korea Institute of Industrial Technology) ;
  • Myoung, Young-Chan (Korean Agency for Technology and Standards)
  • 송문환 (한국생산기술연구원 국제환경규제대응기술지원단 유해물질분석실) ;
  • 조영달 (한국생산기술연구원 국제환경규제대응기술지원단 유해물질분석실) ;
  • 최은경 (한국생산기술연구원 국제환경규제대응기술지원단 유해물질분석실) ;
  • 명영찬 (기술표준원)
  • Received : 2012.03.23
  • Accepted : 2012.06.06
  • Published : 2012.06.25
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Abstract

As phthalates classified as toxic to reproduction category 2 and endocrine disrupting chemicals were more strictly regulated as Substances of Very High Concern (SVHC) for authorization in under EU REACH and considered as priority substances in RoHS II, standardization of phthalate testing method is now being proposed in IEC 62321 of IEC TC 111 and the 2nd revision of KS M 1991 is also finished. In order to assist standardization activities related to phthalating testing, solvent extraction part of existing national standards were compared and verified. Recovery of DEHP (diethylhexyl phthalate) from PVC (polyvinyl chloride) by Soxhlet extraction increased in the order of methanol, toluene, dichloromethane and hexane from 46.9% to 95.3% as measured by GC-MS. Optimum extraction time was verified to be 6 hours using hexane. Recovery of DBP (dibutyl phthalate), BBP (butylbenzyl phthalate), and DEHP from different matrixes such as PVC, nitro cellulose, ABS (acrylonitrile butadiene styrene). and EPDM(ethylene propylene diene monomer) rubber were evaluated to be more than 90% up to 99%. The detection limits of phthalates in solvent extraction followed by GC-MS analysis were 0.08~0.3 ${\mu}g/mL$ in solution and 8~30 mg/Kg in polymeric samples. GC-MS analyses of phthalates were carried out using different solvent extraction based on the EN 14372, ASTM D 7083, Japanese test method (MHLW 0906-4) and KS M 1991, proving that equivalent recoveries ranging from 98%~99% were obtained. DBP and DEHP were detected in three consumer products such as a child toy, a power cable and manicure with the amount of 22~1,910 mg/kg.

생식독성 및 내분비계 장애물질로 분류되는 프탈레이트가 근자에 유럽 신화학물질관리제도(REACH)의 허가대상 고위험성 물질(SVHC) 목록 및 유럽의 전기전자제품에 함유된 유해물질 규제인 RoHS II의 최우선 고려 물질 등으로 규제가 강화되면서 IEC TC 111에서 분석법 표준화가 진행되고 있으며 KS 개정도 이루어지고 있다. 본 고에서는 프탈레이트 분석법의 KS 개정 및 한국 NC에서 제안하여 진행되고 있는 IEC 62321에 프탈레이트 분석법을 추가함에 있어 기술적 자료로 사용될 수 있도록 현존하는 국가별 표준의 용매 추출 전처리를 비교 및 검증해 보았다. PVC (polyvinyl chloride)에서의 DEHP (diethylhexyl phthalate)의 추출 효율은 메탄올, 톨루엔, 디클로로메테인. 헥세인 순으로 46.9%에서 95.3%까지 증가하였다. DBP (dibutyl phthalate), BBP (butylbenzyl phthalate) 및 DEHP의 속슬렛을 사용한 추출 시간은 6시간이 최적임이 입증되었고, PVC, nitro cellulose, ABS (acrylonitrile butadiene styrene), and EPDM (ethylene propylene diene monomer) rubber 등의 매트리스로부터의 추출 효율도 90%~99%로 측정되었다. 용매추출에 이은 GC-MS 분석법의 검출한계는 용액 및 고분자 샘플에서 각각 0.08 ~0.3 ${\mu}g/mL$ 및 8~30 mg/kg으로 산출되었다. 공산품에서 프탈레이트를 분석하는 국가표준에서 용매 추출 전처리를 사용하는 EN 14372, ASTM D 7083, 일본 후생노동성 시험법(MHLW 0906-4) 및 KS M 1991을 비교한 결과 4개 국가별 표준 모두 98%~99%의 추출효율을 가짐이 검증되었다. 또한, 국내에서 유통되는 어린이 장난감, 전기 코드, 매니큐어의 공산품 3종에서 프탈레이트 함유 여부를 분석한 결과 DBP 및 DEHP가 22~1,910 mg/kg 범위로 검출되었다.

Keywords

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