| What accelerates the CTP (computer to plate) including free-process plates and the ultraviolet (405nm) plates is the emergence of superpower ultraviolet laser and infrared laser, so that the systems of PAGs (photo acid generation) and SRs (acid-sensitive polymer) are more and more regarded as the imaging materials systems with potential high amplification mechanism. Therefore, it is of much significance to explore thoroughly the mechanism of photolysis, to research the RSPs (relationship of structure-performance) of the related systems and to solve the problems on innovation of materials. Moreover, the related systems of PAGs have widely used in domains consisting of biotic slugs, combination chemistry, photochemical synthesis, owing to the related results.The chief problem solved is aimed at the methods for quantitive evaluation of the efficiency of acid-generation and analysis of the RSPs including the influencing factors, on the basis of the research on the series of PAGs and APGs(acid proliferation generation) and application of various instruments and methods, including UV, FT-IR, RF, DSC, TLC and profile meter, etc.The structures of PAGs tested are sulfonium series (3 kinds), triazine series (6 kinds), calixarenes series (5 kinds), moreover, the APGs are various esters (4 kinds) of para-toluenesulfonate with cyclohexanediol or with para-nitro calyx-4, in addition, the two series of SRs, presented as following.(1) Establishment of determination method of the acidity of systemsDue to the isomerization and color-change, the so-called CCA (calibration curves for acidity) for the acid-generation system on studying the relation between theconcentration of the acid and the absorbance value of acid-sensitive peak of RB (Rhodamine B) is available. On the basis of non-aqueous titration and the RB-photometry, different CCAs have been made to be used in the related solution systems combination from variant acids and variant solvents, e.g., one from TfOH(trifluoromethylsulfonic acid) , HCl(hydrochloride), TsOH (paratoluenesulfonate) ,the other from THF, ACN(acetonitrile), EE(2-ethoxyethanol) systems. Moreover, the quantitive evaluation of acid-generation dose in film tested can be researched through the so-called solving-resin method.(2) The study on the RSPs of acid-generator, concluding PAGs and APGs, and the related influence factors.The RSPs of PAGs can be given by the CCAs as well as the poly-spectrum dynamics assay. A series of results have been obtained as followed. One, the concentration effect of PAGs and intensity one of light-source on the quantum efficiencies of decomposition and acid-generation can be ignored in the domain. Two, solvent effect shows significant influence on the quantum efficiencies, cause PAGs more apt to photolysis, not only strong polar solvents to the sulfonium-type PAGs, but also nucleophilic solvents to the triazine-type PAGs, except for the red or violet shift of major peak in UV spectrum;Moreover, the anthracene-base sulfonium-type PAG, i.e. , PAG C36, show more intense fluorescence in the blending solvent of the THF and ACN, in equal volume, than in ACN;In addition, it is so marked difference of solubility between the materials fore and after exposure, that can been separated easily. Three, substituent effect had been explored, and the conclusion presented that the triazine-type PAGs with tertiary amine-base, concluding PAG C17,PAG C25,PAG C23,are high-efficiency ones, due to their structures with good synergistic conjugate and nucleophilicity;while, PAG C36 with high efficiency, should be modified in conjugate structure. Four, the results on photolysis efficiency on basis of UV spectrum dynamics assays between in solutions and in films, are in conformity. Moreover, the characteristic peaks, such as the bond between carbon and sulfur, sulfoacid, the bond between carbon and chlorine, had been monitored in the related frequencies, such as— 13400,1641,1183,1197,696 cm , respectively, the quantum efficiencies derived from which concordance with the UV spectrum dynamics results mentioned above.The results from the study on RSPs of APGs present in three aspects. One, the thermo-decomposition temperature of APG C20 is about 130°C in the free-acid conditions, while 90 °C when adding acid previously, monitored by DSC under the constant temperature manipulation. Two, the changes of IR spectrum peaks derivation from the sulfoacid group, whose frequency values are around 1163, 1343cm"1, are remarkable in 130°C after 5 min, while there is no obvious signal in 100°C, in despite of the same heating time. Three, the two sulphonic ester type with para-nitro calixarenes-base or 1,4-cyclohexanediol group, can used as high-efficiency APGs;and that the latter shows better thermal stability whether in solutions or in film of Voly200,while the proliferation rate approaches 50% when blending with para-toluenesulfonate in equal mol ratio, both controlled in the heating condition of 130°C and monitored by the dynamics method for UV spectrum. There are good conformities among these results.(3) Research on the relationship among the PAG materials systems, processes and performances of imaging in CTP analogsBy the so-called solving-resin trials, the two kinds of feasibility formulas (proportion of ingredient), used in cross-linking or degradation systems, had been achieved during the optimization research trials in pre-process of plates, film technique, developing solution, contrast dyes, light cover, etc. The former formula is the system containing 16%( g/ml) phenolic resin solution of EE, 1.8% (w/w) HC1 (ratio to the resin weigh),and the latter is 50% (mg/1) P(t-BuMMA)/( 1:1THF/H2O), 180 (w/w) HC1 (ratio to the resin weigh).On the basis of the achievements mentioned above, the CTP analogues of thermo-sensitive to 830nm and photosensitive to 300nm-upward had been obtained and established by the film thickness measuring, when previously adding high efficiency PAG, e.g., PAG C17, PAG C23, whose weight ratio to the phenolic resin only 0.8%.In addition, the achieves of APG C20 in thermo-sensitive plate mentioned in the paper.In one word, the two kinds of plates are in preliminary application stage.
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