[논문]프탈레이트의 유해성과 대체재 현황: 소고

김웅; 계명찬

doi:10.11626/kjeb.2017.35.1.021

프탈레이트의 유해성과 대체재 현황: 소고
Maleficent Effects of Phthalates and Current States of Their Alternatives: A Review 원문보기

환경생물 = Korean journal of environmental biology, v.35 no.1, 2017년, pp.21 - 36

초록
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대표적인 내분비계 교란물질인 프탈레이트의 이용실태, 위해성, 규제현황 및 이를 대체하여 사용되는 대체가소제 및 대체플라스틱소재들의 특성을 정리하였다. 프탈레이트는 대표적인 내분비계 장애물질 중 하나로 경구 또는 호흡과 피부를 통해 체내에 침투해 여성호르몬 및 남성호르몬과 갑상선호르몬이 작용을 교란하는 것으로 알려졌다. 특히, 태아의 발달 저하, 성체의 생식능력 저하, 암 유발 이외에도 신경발달 저하 및 정신질환까지도 프탈레이트 노출과 연관이 있음이 보고되었다. 각종 플라스틱 제품, 안료, 화장품 등 일상생활 곳곳에 광범위하게 사용되던 프탈레이트는 규제가 이뤄짐에 따라 여러 종류의 대체가소제들이 사용되고 있으며 가소제를 사용하지 않는 플라스틱 대체소재들이 개발되고 있다. 이들 대체가소제 및 대체소재들의 내분비 교란 및 위해성이 새로이 제기되고 있으며, 프탈레이트 만큼 구체적으로 안전성 평가가 이뤄지지 않았으므로 결코 안전하다고 할 수 없다. 또한 대체가소제 및 대체소재들의 물성적 한계와 낮은 가격경쟁력은 재고되어야 한다. 본 소고에서는 in vitro, in vivo 및 in silico 시험을 통해 알려진 프탈레이트 대체가소제 및 대체소재들의 안전성 자료들을 정리하여 안전성에 대한 의문을 제기함과 동시에 바람직한 대체재 발굴을 위한 가이드라인를 제시하고자 하였다.

Abstract ▼ AI-Helper

Phthalates, known as typical endocrine disruptors, are plasticizers used to soften plastics such as polyvinyl chloride (PVC). Because of their material properties, phthalates are used extensively in the production of toys, flooring, wood processing, detergents, and even cosmetics as lubricants and perfume solvents. Due to their endocrine disrupting effect and other adverse health effects published, recently, phthalates have been regulated in many countries. Besides, in an effort to replace phthalates, several chemical plasticizers such as trioctyltrimellitate (TOTM) and dioctylterephthalate (DIOP) have been used instead of the existing harmful phthalates, and novel alternatives are continuously being developed. Nonetheless, phthalates are still being detected in several plastic products, and the safety of alternatives that are considered safe is being questioned. In this review, we describe the adverse health effects of phthalates, their regulation and the current status of their alternatives.

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문제 정의

2013). 본 소고에서는 프탈레이트의 유해성과 함께 국내외 규제 및 대체재의 개발 및 이용, 그리고 대체재들의 독성 정보 및 내분비 교란 효과에 관한 최근까지 연구결과들을 정리하였다.

성능/효과

22종의 프탈레이트를 대상으로 내분비계 교란 가능성을 조사한 결과 알킬기 곁사슬(alkyl chain)의 길이가 C3~C6인 프탈레이트 중 BBeP, DcHP, DiHP, DiBP, DBP, DPeP, DHP, DEHP, DiHepP는 에스트로젠 수용체알파(human estrogen receptor α, hERα)를 활성화시키며, DcHP, BBeP, DPeP, DiHP, DHP, DEHP, DiHepP는 에스트로젠 수용체 베타(human estrogen receptor β, hERβ)의 길항제로 작용한다.
50℃의 n-hexane에 2시간 노출시킨 뒤 무게 감소를 비교하여 내이행성(migration resistance)을 확인한 결과 DEHP를 사용한 PVC의 무게 감소율 10%에 비해 ε-caprolactone을 사용한 PVC의 무게 감소율이 0.6% 이하로 나타나 높은 내이행성을 보였다.
TOTM에 이어 각광받는 프탈레이트 대체제로 dioctylterephthalate (DOTP)와 di(2-ethylhexyl)terephthalate(DEHT)가 있다. DOTP는 프탈레이트나 기존의 대체가소제들이 갖는 내분비계 교란 효과와 유해성이 없으면서 프탈레이트 대비 80~90% 수준의 가소효율을 보이므로 DEHP나 DNIP를 대체할 수 있는 친환경 가소제로 인식되었다. DOPT는 대체가소제로서 높은 효율성을 보이며 독성을 나타내지 않아 국내에서는 LG화학에서 GL300 및 GL500이라는 제품으로 물성을 개선하여 생산 및 판매되고 있다(Kim et al.
또 다른 연구에서는 최대 19 μg kg^-1 day^-1까지 노출될 수 있음이 보고되었다(Meek and Chan 1994). 두 연구에서 공통적으로 연령이 어릴수록 그 노출량이 증가하는 것으로 나타났다. 가스의 형태로 흡입되거나 피부로 흡수되는 것이 주된 흡수경로로 추측되며 영·유아의 경우 먼지를 흡입하게 되어 그 노출량이 높은 것으로 보인다(Heudorf et al.
Di(2-ethylhexyl)terephthalate(DEHT)는 만성적으로 노출되면 눈과 코에 이상을 초래하고, Di-(iso-nonyl)-cyclohexane1,2-dicarboxylate(DINCH)는 백서 실험에서 갑상선과 신장에 독성이 있다. 반복투여에 따른 DINCH의 NOAEL은40 mg kg^-1 bw day^-1로 DEHT, DINA, ATBC에 비해 낮으며, 아동완구 등에 사용되는 2,2,4-trimetyl-1,3-pentanedioldiisobutyrate (TXIB)는 반복투여에 따른 NOAEL이 30 mgkg-1 bw day-1로 DEHT, DINA, ATBC에 비해 낮으며 개와 백서에서 간 및 신장독성이 나타났다. 백서에서 고농도의TXIB는 생식 및 발생독성을 보였다(Hirata-Koizumi et al.
2014; LGchem 2014). 웹기반 데이터베이스(EDMON v1.2: Inverse Screening: NR_HUMAN)를 통해 DOTP와 핵수용체(nuclear hormone receptors)에 결합할 가능성을 확인한 결과 주요 호르몬수용체들(ER, AR,RXR, PRGR, PPAR)과 결합하지 않아 기존의 프탈레이트 및 대체가소제에 비해 상대적으로 안전한 것으로 평가되었다. 그러나 최근 DOTP와 SHBG 간의 결합 가능성이 보고되어 in vitro 및 in vivo 실험연구를 통한 안전성 검증이 필요한 상태이다(Sheikh et al.

후속연구

2013). 그러나 내분비계 교란 특성 및 다양한 독성 종말점에 대한 정보가 충분치 않으므로 이에 대한 in vivo 및 in vitro 연구가 필요하다. 백서에서 ATBC는 간 독성이 있고 고농도의 ATBC는 생식 및 발생독성을 보였다(Hirata-Koizumi et al.
최근 송사리 바이오마커 실험에서 CHDM은 에스트로젠에 의해 유도되는 바이오마커인 vtg2 mRNA를 유도하였고, TPA는 성호르몬생성 효소 유전자인 cyp19b, star, cyp17, cyp19a 발현을 증가시켰으며, 사람의 부신피질암세포(H295R) in vitro실험에서 고농도에서 성호르몬의 생성을 변화시켰다(Jangand Ji 2015). 따라서 TritanTM의 제조에 사용되는 단량체들이 BPA보다 여성호르몬성이 낮은 것은 사실이지만 더 정확한 내분비 교란 특성의 유무 및 기타 장기에 미치는 다양한 독성 효과에 대해서 추가적인 연구가 필요하다. 열 안정성이 200℃ 이상으로 좋아 멸균처리에 유리한 경화성플라스틱 소재로 polyethersulfone(PES), polyphenylsulfone(PPSU) 등이 유아용 젖병 및 의료기구에 이용되고 있다.

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