Skip to main content
Log in

Effect of isocyanate crosslinkers blocked with amine derivatives on rheological and crosslinking characteristics of automotive clearcoats

  • Short Communication
  • Published:
Korea-Australia Rheology Journal Aims and scope Submit manuscript

Abstract

Isocyanate crosslinkers with blocking agents based on various amine derivatives were newly synthesized for automotive clearcoat applications. Amine-based blocking agents were prepared by varying the alkyl substituent attached on both sides of the main nitrogen atom (named DEA, DiPA, NtBEA, and NtBiA) to modify their deblocking feature in blocked isocyanates (BIs) and curing reaction under thermal curing conditions. Curing properties of clearcoats containing amine-based BIs were characterized at the normal curing temperature of 150°C and were compared with those by the commercialized BI, Desmodur® PL350. The dissociation ability of the amine-based BIs was interpreted using the density functional theory (DFT) simulation under their optimized geometric configurations. The urethane reaction between isocyanate group in BIs and hydroxyl group in a hydroxyl-functionalized polyol binder within clearcoats was confirmed from the OH stretching absorbance data via Fourier-transform infrared (FT-IR) spectrometer. The real-time cross-linking dynamics of various clearcoats with amine-based BIs were comprehensively investigated using rotational rheometer and rigid-body pendulum tester. The surface mechanical properties of fully-cured clearcoat films were measured by nano-indentation and nano-scratch testers to address the crosslinked network formation caused by amine-based BIs. It is demonstrated that the amine-based BIs could be favorably applied to thermal curing process of clearcoats, based on their reactivity and curing performance.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

References

  • Adamsons, K., G. Blackman, B. Gregorovich, L. Lin, and R. Matheson, 1998, Oligomers in the evolution of automotive clearcoats: mechanical performance testing as a function of exposure, Prog. Org. Coat. 34, 64–74.

    Article  CAS  Google Scholar 

  • Bossion, A., G.O. Jones, D. Taton, D. Mecerreyes, J.L. Hedrick, Z.Y. Ong, Y.Y. Yang, and H. Sardon, 2017, Non-isocyanate polyurethane soft nanoparticles obtained by surfactant-assisted interfacial polymerization, Langmuir 33, 1959–1968.

    Article  CAS  Google Scholar 

  • Chiu, H.-T., and J.-O. Cheng, 2008, Thermal imidization behavior of aromatic polyimides by rigid-body pendulum rheometer, J. Appl. Polym. Sci. 108, 3973–3981.

    Article  CAS  Google Scholar 

  • Delebecq, E., J.P. Pascault, B. Boutevin, and F. Ganachaud, 2013, On the versatility of urethane/urea bonds: reversibility, blocked isocyanate, and non-isocyanate polyurethane, Chem. Rev. 113, 80–118.

    Article  CAS  Google Scholar 

  • Gregorovich, B.V., and I. Hazan, 1994, Environmental etch performance, and scratch and mar of automotive clearcoats, Prog. Org. Coat. 24, 131–146.

    Article  CAS  Google Scholar 

  • He, Z.A., and W.J. Blank, 1999, Crosslinking with malonate blocked isocyanates and with melamine resins, J. Coat. Technol. 71, 85–90.

    Article  CAS  Google Scholar 

  • Hwang, J.W., K.N. Kim, G.S. Lee, J.H. Nam, S.M. Noh, and H.W. Jung, 2013, Rheology and curing characteristics of dual-curable automotive clearcoats using thermal radical initiator derived from O-imino-isourea and photo-initiator, Prog. Org. Coat. 76, 1666–1673.

    Article  CAS  Google Scholar 

  • Jung, K.I., B. Kim, D.G. Lee, T.H. Lee, S.Y. Choi, J.C. Kim, S.M. Noh, Y.I. Park, and H.W. Jung, 2018, Characteristics of dual-curable blocked isocyanate with thermal radical initiator for low-temperature curing of automotive coatings, Prog. Org. Coat. 125, 160–166.

    Article  CAS  Google Scholar 

  • Lee, D.G., S. Sung, D.G. Oh, Y.I. Park, S.-H. Lee, J.C. Kim, S.M. Noh, and H.W. Jung, 2020, Application of polycarbonate diol containing hindered urea to polyurethane-based clearcoats for tuning of scratch-healing properties, J. Coat. Technol. Res. 17, 1–14.

    Article  CAS  Google Scholar 

  • Lee, K.C., S.B. Jeong, D.Y. Kim, T.H. Lee, S.C. Kim, J.C. Kim, S.-H. Lee, S.M. Noh, and Y.I. Park, 2018, Synthesis and radical polymerization properties of thermal radical initiators based on o-imino-isourea: The effect of the alkyl side chain on the radical initiation temperature, J. Polym. Sci. Pol. Chem. 56, 1749–1756.

    Article  CAS  Google Scholar 

  • Mühlebach, A., 1994, Pyrazoles-a novel class of blocking agents for isocyanates, J. Polym. Sci. Pol. Chem. 32, 753–765.

    Article  Google Scholar 

  • Noh, S.M., J.W. Lee, J.H. Nam, J.M. Park, and H.W. Jung, 2012a, Analysis of scratch characteristics of automotive clear-coats containing silane modified blocked isocyanates via car-wash and nano-scratch tests, Prog. Org. Coat. 74, 192–203.

    Article  CAS  Google Scholar 

  • Noh, S.M., J.W. Lee, J.H. Nam, K.H. Byun, J.M. Park, and H.W. Jung, 2012b, Dual-curing behavior and scratch characteristics of hydroxyl functionalized urethane methacrylate oligomer for automotive clearcoats, Prog. Org. Coat. 74, 257–269.

    Article  CAS  Google Scholar 

  • Oliver, W.C., and G.M. Pharr, 1992, An improved technique for determining hardness and elastic modulus using load and displacement sensing indentation experiments, J. Mater. Res. 7, 1564–1583.

    Article  CAS  Google Scholar 

  • Petit, H., N. Henry, A. Krebs, G. Uytterhoeven, and F. de Jong, 2001, Ambient cure high solids acrylic resins for automotive refinish clear coat applications, Prog. Org. Coat. 43, 41–49.

    Article  CAS  Google Scholar 

  • Ramezanzadeh, B., S. Moradian, A. Kohsravi, and N. Tahmassebi, 2012, Effect of polysiloxane additives on the scratch resistance of an acrylic melamine automotive clearcoat, J. Coat. Technol. Res. 9, 203–214.

    Article  CAS  Google Scholar 

  • Slinckx, M., N. Henry, A. Krebs, and G. Uytterhoeven, 2000, High-solids automotive coatings, Prog. Org. Coat. 38, 163–173.

    Article  CAS  Google Scholar 

  • Subramani, S., A. Sultan Nasar, T. Philip Gnanarajan, N. Padmanabha Iyer, and G. Radhakrishnan, 2000, Structure-property relationship of blocked diisocyanates: synthesis of polyimides using imidazole-blocked isocyanates, Polym. Int. 49, 546–550.

    Article  CAS  Google Scholar 

  • Tassel, X., D. Barbry, and L. Tighzert, 2000, A new blocking agent of isocyanates, Eur. Polym. J. 36, 1745–1751.

    Article  CAS  Google Scholar 

  • Wernståhl, K.M., and B. Carlsson, 1997, Durability assessment of automotive coatings-design and evaluation of accelerated tests, J. Coat. Technol. 69, 69–75.

    Article  Google Scholar 

  • Wicks, D.A., and Z.W. Wicks Jr., 1999, Blocked isocyanates III: Part A. Mechanisms and chemistry, Prog. Org. Coat. 36, 148–172.

    Article  CAS  Google Scholar 

  • Wicks, D.A., and Z.W. Wicks Jr., 2001, Blocked isocyanates III: Part B: Uses and applications of blocked isocyanates, Prog. Org. Coat. 41, 1–83.

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This study was supported by the Ministry of Trade, Industry & Energy (MOTIE, Korea) under Industrial Technology Innovation Programs (No. 10067706 and No. 20004044).

Author information

Authors and Affiliations

Authors

Corresponding authors

Correspondence to Seung Man Noh or Hyun Wook Jung.

Additional information

Publisher’s Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

June, YG., Jung, K.I., Lee, T.H. et al. Effect of isocyanate crosslinkers blocked with amine derivatives on rheological and crosslinking characteristics of automotive clearcoats. Korea-Aust. Rheol. J. 33, 37–43 (2021). https://doi.org/10.1007/s13367-021-0004-2

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s13367-021-0004-2

Keywords

Navigation