29si nmr spectroscopy

Example 6

Synthesis of Resin 6

A 3-L flask equipped with a stirrer, thermometer, nitrogen purge line and reflux condenser was charged with 39.2 g (0.10 mol) of Compound (S-1), 26.5 g (0.10 mol) of Compound (S-2), 27.1 g (0.05 mol) of Compound (S-3c), 9.3 g (0.05 mol) of Compound (S-4), and 86.0 g (0.20 mol) of Compound (S-7), further with 2,000 g of toluene, and heated at 70° C. Thereafter, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5 wt %) was added, and 58.2 g (0.30 mol) of Compound (S-5) and 317.0 g (0.20 mol) of Compound (S-6) wherein y¹=20 (Shin-Etsu Chemical Co., Ltd.) were added dropwise over 1 hour. The molar ratio of the total amount of hydrosilyl groups to the total amount of alkenyl groups was 1/1. At the end of dropwise addition, the reaction solution was heated at 100° C. and aged for 6 hours. Toluene was distilled off in vacuum from the reaction solution, yielding Resin 6. On ¹H—NMR and ²⁹Si—NMR spectroscopy (Bruker Corp.), Resin 6 was identified to contain recurring units having formulae (a1) to (a5) and (b1) to (b5). On GPC analysis, it was confirmed that the peaks assigned to the reactants had disappeared, proving that a polymer corresponding to the charge ratio was synthesized. Resin 6 had a Mw of 44,000 and a silicone content of 56.3 wt %.

Example 2

Synthesis of Resin 2

A 3-L flask equipped with a stirrer, thermometer, nitrogen purge line and reflux condenser was charged with 26.5 g (0.10 mol) of Compound (S-2), 57.0 g (0.10 mol) of Compound (S-3), 18.6 g (0.10 mol) of Compound (S-4), and 86.0 g (0.20 mol) of Compound (S-7), further with 2,000 g of toluene, and heated at 70° C. Thereafter, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5 wt %) was added, and 58.2 g (0.30 mol) of Compound (S-5) and 317 g (0.20 mol) of Compound (S-6) wherein y¹=40 (Shin-Etsu Chemical Co., Ltd.) were added dropwise over 1 hour. The molar ratio of the total amount of hydrosilyl groups to the total amount of alkenyl groups was 1/1. At the end of dropwise addition, the reaction solution was heated at 100° C. and aged for 6 hours. Toluene was distilled off in vacuum from the reaction solution, yielding Resin 2. On ¹H-NMR and ²⁹Si-NMR spectroscopy (Bruker Corp.), Resin 2 was identified to contain recurring units having formulae (a1) to (a5) and (b1) to (b5). On GPC analysis, it was confirmed that the peaks assigned to the reactants had disappeared, proving that a polymer corresponding to the charge ratio was synthesized. Resin 2 had a Mw of 40,000 and a silicone content of 56.3 wt %.

Example 4

Synthesis of Resin 4

A 3-L flask equipped with a stirrer, thermometer, nitrogen purge line and reflux condenser was charged with 39.2 g (0.10 mol) of Compound (S-1), 26.5 g (0.10 mol) of Compound (S-2), 32.5 g (0.05 mol) of Compound (S-3a), 9.3 g (0.05 mol) of Compound (S-4), and 86.0 g (0.20 mol) of Compound (S-7), further with 2,000 g of toluene, and heated at 70° C. Thereafter, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5 wt %) was added, and 58.2 g (0.30 mol) of Compound (S-5) and 317.0 g (0.20 mol) of Compound (S-6) wherein y¹=20 (Shin-Etsu Chemical Co., Ltd.) were added dropwise over 1 hour. The molar ratio of the total amount of hydrosilyl groups to the total amount of alkenyl groups was 1/1. At the end of dropwise addition, the reaction solution was heated at 100° C. and aged for 6 hours. Toluene was distilled off in vacuum from the reaction solution, yielding Resin 4. On ¹H—NMR and ²⁹Si—NMR spectroscopy (Bruker Corp.), Resin 4 was identified to contain recurring units having formulae (a1) to (a5) and (b1) to (b5). On GPC analysis, it was confirmed that the peaks assigned to the reactants had disappeared, proving that a polymer corresponding to the charge ratio was synthesized. Resin 4 had a Mw of 43,000 and a silicone content of 55.7 wt %.

Example 3

Synthesis of Resin 3

A 3-L flask equipped with a stirrer, thermometer, nitrogen purge line and reflux condenser was charged with 66.3 g (0.25 mol) of Compound (S-2), 9.3 g (0.05 mol) of Compound (S-4), and 86.0 g (0.20 mol) of Compound (S-7), further with 2,000 g of toluene, and heated at 70° C. Thereafter, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5 wt %) was added, and 58.2 g (0.30 mol) of Compound (S-5) and 604.0 g (0.20 mol) of Compound (S-6) wherein y¹=40 (Shin-Etsu Chemical Co., Ltd.) were added dropwise over 1 hour. The molar ratio of the total amount of hydrosilyl groups to the total amount of alkenyl groups was 1/1. At the end of dropwise addition, the reaction solution was heated at 100° C. and aged for 6 hours. Toluene was distilled off in vacuum from the reaction solution, yielding Resin 3. On ¹H-NMR and ²⁹Si-NMR spectroscopy (Bruker Corp.), Resin 3 was identified to contain recurring units having formulae (a1) to (a5) and (b1) to (b5). On GPC analysis, it was confirmed that the peaks assigned to the reactants had disappeared, proving that a polymer corresponding to the charge ratio was synthesized. Resin 3 had a Mw of 46,000 and a silicone content of 73.3 wt %.

Example 6

Synthesis of Resin C-6

A 3-L flask equipped with a stirrer, thermometer, nitrogen purge line, and reflux condenser was charged with 55.8 g (0.30 mol) of Compound (S-3), 117.6 g (0.30 mol) of Compound (S-4), and 106.0 g (0.40 mol) of Compound (S-5), then with 2,000 g of toluene, and heated at 70° C. Thereafter, 1.0 g of a chloroplatinic acid toluene solution (Pt concentration 0.5 wt %) was added, and 135.8 g (0.70 mol) of Compound (S-1) and 475.5 g (0.30 mol) of Compound (S-2) (y¹=20, by Shin-Etsu Chemical Co., Ltd.) were added dropwise over 1 hour (total hydrosilyl groups/total alkenyl groups=1/1 in molar ratio). After the completion of dropwise addition, the solution was heated at 100° C. and aged for 6 hours. From the reaction solution, the toluene was distilled off in vacuum, yielding Resin C-6. Resin C-6 was analyzed for structure by ¹H-NMR and ²⁹Si-NMR spectroscopy (Bruker Corp.) and GPC. Resin C-6 had a Mw of 31,000 and a silicone content of 59.6 wt %.

[2] Preparation and Evaluation of Photosensitive Resin Compositions

Example 1

Synthesis of Resin C-1

A 3-L flask equipped with a stirrer, thermometer, nitrogen purge line, and reflux condenser was charged with 265.0 g (1.00 mol) of Compound (S-5), then with 2,000 g of toluene, and heated at 70° C. Thereafter, 1.0 g of a chloroplatinic acid toluene solution (Pt concentration 0.5 wt %) was added, and 164.9 g (0.85 mol) of Compound (S-1) and 453.0 g (0.15 mol) of Compound (S-2) (y¹=40, by Shin-Etsu Chemical Co., Ltd.) were added dropwise over 1 hour (total hydrosilyl groups/total alkenyl groups=1/1 in molar ratio). After the completion of dropwise addition, the solution was heated at 100° C. and aged for 6 hours. From the reaction solution, the toluene was distilled off in vacuum, yielding Resin C-1. Resin C-1 was analyzed for structure by ¹H-NMR and ²⁹Si-NMR spectroscopy (Bruker Corp.) and GPC. Resin C-1 had a Mw of 65,000 and a silicone content of 51.3 wt %.

Example 5

Synthesis of Resin 5

A 3-L flask equipped with a stirrer, thermometer, nitrogen purge line and reflux condenser was charged with 39.2 g (0.10 mol) of Compound (S-1), 26.5 g (0.10 mol) of Compound (S-2), 26.6 g (0.05 mol) of Compound (S-3b), 9.3 g (0.05 mol) of Compound (S-4), and 86.0 g (0.20 mol) of Compound (S-7), further with 2,000 g of toluene, and heated at 70° C. Thereafter, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5 wt %) was added, and 58.2 g (0.30 mol) of Compound (S-5) and 317.0 g (0.20 mol) of Compound (S-6) wherein y¹=20 (Shin-Etsu Chemical Co., Ltd.) were added dropwise over 1 hour. The molar ratio of the total amount of hydrosilyl groups to the total amount of alkenyl groups was 1/1. At the end of dropwise addition, the reaction solution was heated at 100° C. and aged for 6 hours. Toluene was distilled off in vacuum from the reaction solution, yielding Resin 5. On ¹H—NMR and ²⁹Si—NMR spectroscopy (Bruker Corp.), Resin 5 was identified to contain recurring units having formulae (a1) to (a5) and (b1) to (b5). On GPC analysis, it was confirmed that the peaks assigned to the reactants had disappeared, proving that a polymer corresponding to the charge ratio was synthesized. Resin 5 had a Mw of 45,000 and a silicone content of 56.3 wt %.