화학공학소재연구정보센터
Polymer(Korea), Vol.22, No.3, 424-434, May, 1998
폴리이미드 필름의 경화, 건조과정 중 필름의 두께변화 측정 및 해석
Measurement and Analysis of Thickness Change in the Curing and Drying Processes of Polyimide Films
초록
Pyromellitic dianhydride-4,4'-oxydianiline (PMDA-ODA)형 폴리이미드 필름의 경화, 건조과정 중 두께변화를 레이저 간섭계를 이용하여 측정하고, 승온속도와 pre-baking시간이 두께 변화에 미치는 영향을 분석하였다. 승온속도에 따른 경화과정 중 이미드화 정도의 변화를 적외선 분광기를 이용하여 조사하였다. Pre-baking시간이 증가함에 따라 경화과정 초기의 필름의 두께변화는 크게 감소하였다. 숭온속도가 상승함에 따라 필름두께와 이미드화 정도의 변화가 시작되는 온도와 종결되는 온도는 상승하였다. 경화과정 중 같은 온도에서 필름의 두께는 승온속도가 증가함에 따라 크게 나타났다. 경화된 폴리이미드 필름의 열팽창계수를 온도에 따른 필름의 두께변화를 측정함으로서 결정하였다. 팽윤된 폴리이미드 필름의 건조과정 중 온도에 따른 용매의 확산계수를 이론적으로 얻어진 필름내의 용매 질량 잔유분율을 여러 온도에서 얻은 실험결과에 fitting시킴으로써 구하였으며, 이로부터 활성화에너지를 구할 수 있었다.
The thickness change of semirigid polyimide, pyromellitic dianhydride-4.4'- oxydianiline (PMDA-ODA), films during the curing and drying processes was monitored using laser interferometer system and the effects of scanning rate and pre-baking time on it were analyzed. The variation of imidization extent in the curing process for different temperature scanning rates was investigated using Fourier transform-infrared spectroscopy. As the pre-baking time increased, the initial film thickness in the curing process decreased significantly. As the temperature scanning rate increased, the temperatures at which the variation of film thickness and imidization extent started and completed increased. The values of film thickness were higher for higher scanning rates at the same temperatures in the curing process. The thermal expansion coefficient of cured polyimide film was determined from measurement of the temperature dependence of film thickness. In the drying process of swelled polyimide films, the temperature dependence of solvent diffusion coefficient was determined from the curve fitting of the theoretical time dependent fractional solvent mass residue in the film to the experimental results obtained at varying temperatures, with the extraction of the activation energy from it.
  1. Satou H, Makino D, "Polyimides for Electric Applications," Hitachi Chemical Co., Ltd. Ibaraki, Japan (1993)
  2. Coburn JC, Pottiger MT, "Thermal Curing in Polyimide Films and Coatings," "Polyimides: Fundamentals and Applications," M.K. Ghosh and K.L. Mittal, eds., p. 207, Marcel Dekker, Inc., New York (1996)
  3. Sato K, Mukai K, Harada S, Saeki A, Kimura T, Okubo T, Ishi I, Shimizu I, IEEE Trans. Hybrid Packag., PHP-9, 173 (1973)
  4. Chao CC, Scholz KD, Proceedings of 38th Electronic Component Conf., 276 (1988)
  5. Larsen RA, IBM J. Res. Dev., 26, 268 (1980)
  6. Sroog CE, J. Polym. Sci. Macromol. Rev., 11, 161 (1976) 
  7. Saenger KL, Tong HM, "Laser Interferormetry: A Measurement Tool for Thin Film Polymer Properties and Processing Characteristics," "New Cahracterization Techniques for Thin Polymer Films," H.M. Tong and N.T. Nguyen, Eds., p. 95, John Wiley & Sons, Inc. (1990)
  8. Hecht E, "Optics," 2nd eds., p. 333, Addison Wesley Publishing Company, Massachusetts (1987)
  9. Saenger KL, Tong HM, J. Appl. Polym. Sci., 33, 1777 (1987) 
  10. Krasicky PD, Groele RJ, Jubinsky JA, Rodriguez F, Namaste YMN, Obendorf SK, Polym. Eng. Sci., 27, 282 (1987) 
  11. Durning CJ, Hassan MM, Tong HM, Lee KW, Macromolecules, 28(12), 4234 (1995) 
  12. Kong BS, Kwon YS, Kim D, Polym. J., 29, 722 (1997) 
  13. Ginsburg R, Susko JR, "Polyimide Curing Determination," "Polyimides: Systhesis, Characterization, and Application," K.L. Mittal, Ed., p. 237, Plenum, New York (1984)
  14. Numata S, Fujisaki K, Kinjo N, "Studies on Thermal Cyclization of Polyamic Acids," "Polyimides: Systhesis, Characterization, and Application," K.L. Mittal, ed., p. 259, Plenum, New York (1984)
  15. Jou JH, Huang PT, Macromolecules, 24, 3796 (1991) 
  16. Snyder RW, "In Situ FT-IR Analysis of Polyimide Curing," "Polyimides: Materials, Chemistry and Characterization," C. Feger, M.M. Khojasteh, and J.E. McGrath, eds., p. 363, Elsevier Science Publishers, B.V. Amsterdam (1989)
  17. Gattiglia E, Russell TP, J. Polym. Sci. B: Polym. Phys., 27, 2131 (1989) 
  18. Tong HM, Saenger KL, J. Polym. Sci. B: Polym. Phys., 27, 689 (1989) 
  19. Jou JH, Chang YL, Liu CH, Macromolecules, 25, 5186 (1992) 
  20. "Handbook of Chemistry and Physics," CRC. 64th ed. (1983)
  21. Jou JH, Huang PT, Chen HC, Liao CN, Polymer, 33, 967 (1992)