Carbon black photo-resist (CB PR), containing CB, CB dispersant, photo-curable resins, adhesion promoter, photo-initiator, and solvent, was developed for production of high resolution of black matrix (BM) which is an important light-shielding element on the color filter in liquid crystal display (LCD) industry. This work was divided into two parts: (1) the synthesis and function of each ingredient in CB PR and (2) the kinetic behaviors of photo-polymerization and TEMPO-mediated polymerization related to the compounds synthesized in the first part. In the first part, CB was first treated by CB dispersant in order to prepare a high loading of CB dispersion in an organic solvent (propylene glycol monomethyl ether acetate, PGMEA) up to 10 wt%. Three different kinds of dispersants were taken separately to disperse CB, a commercialized dispersant and two newly synthesized dispersants. These three CB dispersants were effectively adsorbed onto CB by the interaction between amino-containing anchoring groups of dispersant and carboxylic acid group on CB surface. They had a moderate chain length to provide a steric repulsion for CB. In addition, the influences of amount and structure of these dispersants on the stability and light-shielding property of CB were discussed. Among these dispersants, one of the newly synthesized dispersants having (meth)acrylate group is an UV-curable CB dispersant, which was synthesized by a two-step process. First, a styrene-(meth)acrylate living copolymer was synthesized as a CB dispersant by TEMPO-mediated living polymerization. In the second step, to render the UV-curable property, additional (meth)acrylate groups were grafted onto the prepared CB dispersant by an urethane linkage reaction. The other newly synthesized CB dispersant was also interesting because it exhibited both UV-curable and alkali-soluble properties, which was capable of forming micro-patterns through an UV-lithographic process. This dispersant was also synthesized by a two-step process. First, UV-curable and alkali-soluble resins were synthesized by the reaction of bisphenol-A epoxy diacrylate with benzophenone tetracarboxylic dianhydride at different molar ratios. Second, to be able to disperse CB particles, these resins were further reacted with an isocyanate-containing methacrylate monomer to produce effective dispersants. Afterwards, CB PRs were prepared by adding photo-initiator and with or without photo-curable resins into the above CB dispersions. However, it was not easy to prepare a BM with both a high opacity and a good resolution upon a low irradiation energy of UV light. This is because CB is a strong light-shielding material which would reduce the photo-sensitivity of CB PR. Besides, the developability of CB PR was strongly retarded by CB since CB can not be soluble in any solvent. In view of this, the selections of photo-initiator and photo-curable resins are critical because they affect the lithographic performance of CB PR. Several photo-initiators were evaluated with respect to their light absorbance and the rate of photo-polymerization in the presence of CB. In addition, several new photo-curable resins were synthesized in this work. UV-curable and alkali-soluble resins were tailored because they can form patterns by an environmental-friendly alkali developer. The influences of photo-sensitivities and concentration of carboxylic acid groups of these resins on the appearance of BM patterns and the energy consumption of UV light were discussed. Finally, a BM with both a high optical density of 4μm-1 and resolution of 10 μm in size upon irradiation of 50-200 mJ/cm2 was successfully produced by using the aforementioned CB PRs through an UV-lithographic process. In addition, the adhesion strength between BM and glass substrate was studied. In the manufacturing process of color filter, the adhesion strength between the BM and glass substrate largely decreased after the ITO sputtering process. To overcome this problem, in this work, a newly synthesized UV-curable silane coupling agent as an adhesion promoter was added into a CB PR. This adhesion promoter was synthesized by the reaction between the hydroxyl group of bisphenol A epoxy diacrylate and the isocyanate group of 3-(isocyanatopropyl)-triethoxysilane. This adhesion promoter containing both acrylate and triethoxysilane groups can be cured upon UV irradiation and form a strong covalent bond with the glass substrate at high temperature, respectively. The influence of this adhesion promoter on the adhesion strength between BM and glass substrate before and after ITO sputtering process was discussed. In the second part, the kinetic behaviors of photo-polymerization of UV-curable resins with carboxylic acid and amino functional groups were investigated. The rate of polymerization and extent of reaction were monitored by using a photo differential scanning calorimeter. A new method combining dark polymerization with pseudo steady state assumption of growing radicals was presented in order to calculate the kinetic constants for propagation, bimolecular termination, monomolecular termination, and the concentration of growing radicals of each resin as a function of extent of reaction. According to the experimental results, it was found that the photo-polymerization was strongly influenced by both functional groups of resins and photo-initiators. The influences of functional groups on the kinetic rate constants and initiator efficiency were discussed in depth. For the CB dispersant synthesized by TEMPO-mediated copolymerization of styrene and (meth)acrylate monomers, the successful living character was observed only at high styrene molar fraction in feed. In view of this, a new kinetic model was established in order to explain the retardant mechanism of the living polymerization of (meth)acrylate. Besides, it was found that TEMPO-mediated polymerization of acrylate could be improved by adding a small amount of polar solvent, DMF (N,N-dimethylformamide) as a rate-enhancement agent. Finally, by using this kinetic model and experimental results, the kinetic rate constants in the TEMPO-mediated polymerization were then calculated and discussed.
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