DOI QR코드

DOI QR Code

Analysis of dried Asian lacquer by pyrolysis/GC/MS

열분해/GC/MS에 의한 한국산 건조 옻 분석

  • Park, Jongseo (Cultural Heritage Conservation Science Center, National Research Institute of Cultural Heritage) ;
  • Ahn, Sun Ah (Restoration Technology Division, National Research Institute of Cultural Heritage)
  • 박종서 (국립문화재연구소 문화재보존과학센터) ;
  • 안선아 (국립문화재연구소 복원기술연구실)
  • Received : 2017.12.21
  • Accepted : 2018.02.08
  • Published : 2018.04.25

Abstract

Asian lacquer has been used as an adhesive and coating material in Asian countries, such as China, Japan, and Korea, and other southeast Asian countries. In this study, the changes in the chemical structure of lacquer with drying was analyzed using pyrolysis/GC/MS (which is useful in analyzing polymeric material) to understand its drying procedures. Upon increasing temperature, the dried lacquer was fully pyrolyzed above the pyrolysis temperature of $500^{\circ}C$. The repeatability was good at the pyrolysis temperature of $500^{\circ}C$ (rsd = 2.6-22.3 %); however, there were differences in the pyrogram patterns when the difference in sample quantity was large. The characteristic peaks of Asian lacquer components, such as those corresponding to 1,2-benzenediol and 3-methyl-1,2-benzenediol, were detected and the compound of each peak was assigned according to the mass library. As the lacquer dried, the composition of pyrolysis products with urushiol derivatives bearing 3 C=C bonds was severely reduced compared with the ones with no C=C bonds, indicating that the polymerization is related to C=C bonds. These results can be applied to confirm the presence of lacquer in excavated relics and to monitor the changes in the composition of raw lacquer with drying.

옻은 우리나라를 포함하여 중국, 일본, 동남아시아 등에서 접착제와 도료로 사용되어 왔다. 옻의 경화 특성을 이해하기 위해서는 경화에 따른 화학구조 변화를 파악해야 하며 이를 위해 본 연구에서는 불용성 고분자 분석에 유용한 열분해/GC/MS 방법을 이용하였다. 우선, 건조시킨 옻 도막을 온도를 변화시키면서 열분해했을 때 $500^{\circ}C$ 이상에서 대부분 물질의 열분해가 일어났다. $500^{\circ}C$에서 열분해했을 때 반복성은 2.6~22.3 %로 양호하였으나, 시료량에 따른 열분해 산물 패턴에 차이가 있었다. 열분해 크로마토그램에서 1,2-benzenediol, 3-methyl-1,2-benzenediol 등 우루시올에서 기인하는 옻의 특징적인 성분을 확인하였다. 건조가 진행됨에 따라 열분해산물 중 탄소이중결합 3개를 갖는 우루시올이 포화 우루시올에 비해 크게 감소하여 고분자화가 이중결합과 관련됨을 알 수 있었다. 연구결과에 의해 설정된 분석조건은 출토유물에서 옻을 확인하거나 건조에 따른 옻의 성분 변화를 파악하는데 활용될 수 있을 것으로 보인다.

Keywords

References

  1. Y.-H. Chung, 'Chil-Jang (The Master of Korean Traditional Lacquer Craft)', p12, National Research Institute of Culutural Heritage, Daejeon, 2006.
  2. S.-C. Kim, 'Analysis and Conservation of Lacquer Wares from Archaeological Sites in Korea' Ph. D. Dissertation, Chungbuk National University, Cheongju, Korea, 2007.
  3. R. Lu and T. Miyakoshi, 'Lacquer Chemistry and Applications', Elsevier, Amsterdam, 2015.
  4. J. Kumanotani, Prog. Org. Coat., 34(1-4), 135-146 (1998). https://doi.org/10.1016/S0300-9440(97)00115-X
  5. N. Niimura, T. Miyakoshi, J. Onodera, and T. Higuchi, Archaeometry, 41(1), 137-149 (1999). https://doi.org/10.1111/j.1475-4754.1999.tb00856.x
  6. A.-S. Le Ho, M. Regert, O. Marescot, C. Duhamel, J. Langlois, T. Miyakoshi, C. Genty, and M. Sablier, Anal. Chim. Acta, 710, 9-16 (2012). https://doi.org/10.1016/j.aca.2011.10.024
  7. N. Niimura and T. Miyakoshi, Talanta, 70(1), 146-152 (2006). https://doi.org/10.1016/j.talanta.2005.12.039
  8. E. Kim and S. Kwon, J. Orient. Academia, 3(1), 52-62 (2010).
  9. J. Kim, Korean J. Food and Nutrition, 19(3), 267-270 (2006).
  10. Y. Cho, Y.-K. Jung, J. Kim, J. Lee, and K.-J. Paeng, Anal. Sci. Technol., 22(1), 65-74 (2009).
  11. J.-K. Roh and Y.-G. Kim, J. Korea Furnit. Soc., 19(5), 307-318 (2008).
  12. R. Lu, T. Yoshida, and T. Miyakoshi, Polym. Rev., 53(2), 153-191 (2013). https://doi.org/10.1080/15583724.2013.776585
  13. N.-C. Cho, S.-C. Kim, W.-H. Kim, and Y.-S. Shin, J. Conserv. Sci., 26(4), 371-376 (2010).
  14. N. Niimura and T. Miyakoshi, J. Mass Spectrom. Soc. Jpn., 51(4), 439-457 (2003). https://doi.org/10.5702/massspec.51.439
  15. Y. Kamiya, Y. Niimura, and T. Miyakoshi, Bull. Chem. Soc. Jpn., 73(11), 2621-2626 (2000). https://doi.org/10.1246/bcsj.73.2621
  16. R. Lu, Y. Kamiya, Y.-Y. Wan, T. Honda, and T. Miyakoshi, J. Anal. Appl. Pyrol., 78(1), 117-124 (2007). https://doi.org/10.1016/j.jaap.2006.05.002