Title Page
Contents
LIST OF ABBREVIATIONS 14
ABSTRACT 15
Ⅰ. INTRODUCTION 17
Ⅱ. BACKGROUND 23
1. Radical polymerization with thiol 23
2. Sol-gel process 25
3. Epoxy-amine curing reaction 27
Ⅲ. EXPERIMENTAL SECTION 29
1. Materials 29
2. Synthesis of hybrid nanocluster polymer 30
2.1. Synthesis of silane acrylate oligomer (SA) 30
2.2. Sol-gel process of SA and metal alkoxide 30
3. Synthesis of acrylate polymer 34
4. Preparation of coatings 34
4.1. Preparation of hybrid nanocluster polymer coatings 34
4.2. Preparation of acrylate polymer/ hybrid polymer bilayer coatings 34
5. Characterization 36
5.1. Nuclear Magnetic Resonance (NMR) 36
5.2. Differential Scanning Calorimetry (DSC) 36
5.3. Fourier Transform Intrared Spectroscopy (FT-IR) 36
5.4. X-ray Photoelectron Spectroscopy (XPS) 36
5.5. Field emission scanning electron microscope (FE-SEM) 37
5.6. Particle size analysis 37
5.7. Pencil Hardness 37
5.8. Surface Force 37
5.9. Contact Angle Measurement 38
5.10. Transmittance 38
5.11. Cross-cut Adhesion Test 38
Ⅳ. RESULTS AND DISCUSSION 39
1. Synthesis of SA 39
2. Synthesis of hybrid nanocluster polymer 41
3. Preparation of hybrid nanocluster polymer coating film 51
3.1. Curing reaction 51
3.2. Hybrid nanocluster polymer coating film properties 54
4. Preparation of bilayer coating films 62
4.1. Synthesis of acrylate coating 62
4.2. Microstructure of bilayer coating films 63
4.3. bilayer coating film properties 67
5. Thermoforming test 73
Ⅴ. CONCLUSION 75
Ⅵ. REFERENCE 76
ABSTRACT IN KOREAN 82
Table 1. Reaction ratio for synthesis of hybrid nanocluster polymer. 33
Table 2. Molar ratio of functional groups in SA calculated by ¹H NMR analysis. 40
Table 3. Atomic % of hybrid nanocluster polymer coating analyzed by XPS spectroscopy. 46
Table 4. Average cluster size and the polydispersity index (PDI) in hybrid nanocluster polymers. 50
Table 5. Surface free energy of hybrid nanocluster polymer coating films. 59
Figure 1. IML process steps. 20
Figure 2. PC/PMMA bilayer film using in automotive display. 21
Figure 3. Concept of organic/Inorganic hybrid polymer coating. 22
Figure 4. Structure of SA by radical polymerization. 32
Figure 5. Preparation route of hybrid nanocluster polymer coating (a) GPS-SA and (b) GPS-SA-Zr. 35
Figure 6. ¹H NMR analysis of SA. 40
Figure 7. FT-IR analysis of hybrid nanocluster polymer. 45
Figure 8. High-resolution spectra of (a) C 1s, (b) O 1s, (c) Si 2p, and (d) Zr 3d of the hybrid nanocluster polymer coating films: (i) GPS10-SA0, (ii) GPS8-SA2, (iii) GPS7-SA3, and... 47
Figure 9. Overlapped high-resolution spectra of (a) O 1s and (c) Si 2p from the hybrid nanocluster polymer coating films. 48
Figure 10. SEM images of hybrid nanocluster coating films : (a) GPS10-SA0, (b) GPS8-SA2, (c) GPS7-SA3, (d) GPS-SA-Zr. 49
Figure 11. Cluster size distribution curve of hybrid nanocluster polymers. 50
Figure 12. DSC curve of mixture of hybrid nanocluster polymer and DDM. 52
Figure 13. FT-IR spectra of uncured (grey line) and cured (color line) hybrid nanocluster polymers. 53
Figure 14. (a) Pencil hardness values and (b) OM images after pencil hardness test of hybrid nanocluster polymer coating films. 57
Figure 15. Surface force of hybrid nanocluster polymer coating films measured with Sclerometer. 58
Figure 16. Water contact angle of hybrid nanocluster polymer coating films. 59
Figure 17. (a) Transmittance and (b) images of hybrid nanocluster polymer coating films. 60
Figure 18. Cross-cut test of hybrid nanocluster coating films : (a) GPS10-SA0, (b) GPS8-SA2, (c) GPS7-SA3, (d) GPS-SA-Zr. 61
Figure 19. FT-IR spectra of uncured and cured acrylate polymer. 64
Figure 20. Coating process of acrylate/hybrid polymer bilayer coating film. 65
Figure 21. FE-SEM images of polymer coatings on PC/PMMA films : (a) Acylate polymer, (b) acrylate polymer/GPS8-SA2, (c) acrylate polymer/GPS7-SA3, and (d) acrylate... 66
Figure 22. (a) Pencil hardness values and (b) OM images after pencil hardness test of bilayer coating films. 69
Figure 23. Surface force of bilayer coating films measured with Sclerometer. 70
Figure 24. (a) Transmittance and (b) images of bilayer coating films. 71
Figure 25. Cross-cut test of bilayer coating films : (a) Acylate polymer, (b) acrylate polymer/GPS8-SA2, (c) acrylate polymer/GPS7-SA3 and (d) acrylate polymer/GPS-SA-... 72
Figure 26. Thermoforming test method. 74
Figure 27. Images of coated PC/PMMA films after thermoforming test : (a) hybrid polymer coating films and (b) bilayer coating films. 74
Scheme 1. Mechanism of radical polymerization with thiol. 24
Scheme 2. Sol-gel process mechanism. 26
Scheme 3. Epoxy-amine reaction mechanism. 28