Polymer Bulletin

, Volume 72, Issue 3, pp 523–533 | Cite as

Synthesis of novel branched UV-curable methacrylate copolymer and its application in negative photoresist

  • Jingcheng Liu
  • Xiangfei Zheng
  • Hu Li
  • Ren Liu
  • Qidao Mu
  • Xiaoya LiuEmail author
Original Paper


A series of novel branched methacrylate copolymers (BPMBMV) were synthesized via the mercapto chain transfer polymerization using methacrylic acid, maleic anhydride, benzyl methacrylate, and 4-vinyl benzyl thiol. Then, BPMBMV reacted with hydroxyethyl acrylate to obtain branched UV-curable copolymer H-BPMBMV, which were characterized by fourier transfer infrared spectra and proton nuclear magnetic resonance spectra. The molecular weights and glass transition temperature (T g ) of the polymers decreased with the addition of VBT. The results of photo-differential scanning calorimetry (Photo-DSC) tests showed that photo-polymerization ability of H-BPMBMV increased with the increased content of VBT. With an optimized formulation, a negative-type photoresist was prepared. The resolution of the circuit could reach as high as 20 μm, and the film of photoresist showed good acid resistance.


Branched copolymer UV curable Photoresist Resolution 



We acknowledge financial support from the National Nature Science Foundation of Jiangsu Province (No. BK20140160) and Suzhou Rui Hong Electronic Chemicals Co., Ltd.


  1. 1.
    Guo L, DeWeerth SP (2010) High-density stretchable electronics: toward an integrated multilayer composite. Adv Mater 22:4030–4033CrossRefGoogle Scholar
  2. 2.
    Lee CK, Hwang FH, Cheng LP et al (2012) Preparation and characterization of nanosilica-filled color resist. Adv Polym Technol 31(2):163–171CrossRefGoogle Scholar
  3. 3.
    Sakii D, Takahashi A, Oyama T (2012) Development of photosensitive vinyl polymers with imide group based on reaction development patterning. J Photopolym Sci Technol 25:371–374CrossRefGoogle Scholar
  4. 4.
    Eunhye K, Hyungju A, Sungmin P (2013) Directed assembly of high molecular weight block copolymers: highly ordered line patterns of perpendicularly oriented lamellae with large periods. ACS Nano 7(3):1952–1960CrossRefGoogle Scholar
  5. 5.
    Li TS, Xu WJ, Tang CQ (2012) Controllable photopatterning and photochemical properties of novel copolymer containing dianthracene Langmuir–Blodgett films. J Polym Sci Part B Polym Phys 50:139–147CrossRefGoogle Scholar
  6. 6.
    Han WS, Lin BP, Yang H et al (2012) Synthesis and properties of UV-curable hyperbranched polyurethane acrylate oligomers containing carboxyl groups. Polym Bull 68:1009–1022CrossRefGoogle Scholar
  7. 7.
    Lee CK, Don TM, Lin DJ et al (2008) Characterization of acrylic copolymers applied in negative-type photoresist via a ternary composition diagram. J Appl Polym Sci 109:467–474CrossRefGoogle Scholar
  8. 8.
    Shi J, Jim CKW, Mahtab F et al (2010) Ferrocene-functionalized hyperbranched polyphenylenes: synthesis, redox activity, light refraction, transition-metal complexation, and precursors to magnetic ceramics. Macromolecules 43:680–690CrossRefGoogle Scholar
  9. 9.
    Tang Y, Jim CKW, Liu Y, Ye L et al (2010) Synthesis and curing of hyperbranched poly(triazole)s with click polymerization for improved adhesion strength. ACS Appl Mater Interfaces 2:566–574CrossRefGoogle Scholar
  10. 10.
    Go C, Yan D (2004) Hyperbranched polymers: from synthesis to applications. Prog Polym Sci 29:183–275CrossRefGoogle Scholar
  11. 11.
    Liu CW, Zhao XG (2013) Synthesis of soluble and autophotosensitive hyperbranched polyimides with good optical properties and thermal properties. Polym J 45:318–325CrossRefGoogle Scholar
  12. 12.
    Christos L, Georges H (2009) Hyperbranched polymers for photolithographic applications—towards understanding the relationship between chemical structure of polymer resin and lithographic performances. Adv Mater 21:1121–1125CrossRefGoogle Scholar
  13. 13.
    Hae SS, Jong CL (2012) Preparation of acid-cleavable branched polymers for argon fluoride photoresists via reversible addition-fragmentation chain-transfer polymerization. J Appl Polym Sci 125(1):344–352CrossRefGoogle Scholar
  14. 14.
    Saptarshi C SR (2013) A novel photodegradable hyperbranched polymeric photoresist. Chem Commun 49:11041–11043CrossRefGoogle Scholar
  15. 15.
    Isaure F, Cormack PAG, Sherrington DC (2004) Synthesis of branched poly (methyl methacrylate)s: effect of the branching comonomer structure. Macromolecules 37:2096–2105CrossRefGoogle Scholar
  16. 16.
    Graham S, Cormack PAG, Sherrington DC (2005) One-pot synthesis of branched poly(methacrylic acid)s and suppression of the rheological polyelectrolyte effect. Macromolecules 38:86–90CrossRefGoogle Scholar
  17. 17.
    Baudry R, Sherrington DC (2006) Facile synthesis of branched poly(vinyl alcohol)s. Macromolecules 39:5230–5237CrossRefGoogle Scholar
  18. 18.
    Liu J, Wang Y, Fu Q (2008) Branched polymer via free radical polymerization of chain transfer monomer: a theoretical and experimental investigation. J Polym Sci Part A Polym Chem 46:1449–1459CrossRefGoogle Scholar
  19. 19.
    Jiang L, Huang WY, Xue XQ et al (2012) Radical polymerization in the presence of chain transfer monomer: an approach to branched vinyl polymers. Macromolecules 45:4092–4100CrossRefGoogle Scholar
  20. 20.
    Liu JC, Liu XY (2013) One-pot synthesis of branched alternating copolymers P(St-alt-MAn) via free radical polymerization in the presence of chain transfer monomer. Polym Bull 70:1795–1803CrossRefGoogle Scholar
  21. 21.
    Liu JC, Liu R, Yuan Y et al (2013) Preparation of superhydrophobic antistatic coatings from branched alternating copolymers P(St-alt-MAn) and carbon nanotubes based on organic–inorganic hybrid approach. Prog Org Coat 76:1251–1257CrossRefGoogle Scholar
  22. 22.
    Liu JC, Jia XL, Liu R et al (2014) Synthesis of UV-curable hyperbranched polyurethane and its application in the negative-type photoresist. J Wuhan Univ Technol (Mater Sci Ed) 29(1):208–212CrossRefGoogle Scholar
  23. 23.
    Ma R, Ma RM, Feng LL et al (2009) The synthesis of P(MAn-co-St)-b-PS-b-P(MAn-co-St) block copolymers by RAFT polymerization and the nanostructure of their self-assembly aggregates. Colloids Surf A Physicochem Eng Aspects 346:184–194CrossRefGoogle Scholar
  24. 24.
    Carola EC, Giulio M et al (2009) Mariaenrica Frigione UV-curable epoxy systems containing hyperbranched polymers: kinetics investigation by photo-DSC and real-time FT-IR experiments. Polym Test 28:157–164CrossRefGoogle Scholar
  25. 25.
    Yuan Y, Chen N, Liu R et al (2014) A novel acrylic prepolymer/methacrylate modified nano-SiO2 composite used for negative photoresist. Mater Res Bull 50:392–398CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2014

Authors and Affiliations

  • Jingcheng Liu
    • 1
    • 2
  • Xiangfei Zheng
    • 1
    • 2
  • Hu Li
    • 1
    • 2
  • Ren Liu
    • 1
    • 2
  • Qidao Mu
    • 3
  • Xiaoya Liu
    • 1
    • 2
    Email author
  1. 1.The Key Laboratory of Food Colloids and BiotechnologyMinistry of EducationWuxiChina
  2. 2.School of Chemical and Material EngineeringJiangnan UniversityWuxiChina
  3. 3.Suzhou Rui Hong Electronic Chemicals Co., Ltd.,SuzhouChina

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