NOVEL NAPHTHALIMIDE SULFONATE DERIVATIVE, AND PHOTOACID GENERATOR AND PHOTORESIST COMPOSITION WHICH COMPRISE SAME
20230331680 · 2023-10-19
Assignee
Inventors
- Chun Rim OH (Seoul, KR)
- Dae Hyuk CHOI (Seoul, KR)
- Min Jung Kim (Daejeon, KR)
- Deuk Rak LEE (Daejeon, KR)
- Won Jung LEE (Daejeon, KR)
- Yu Na CHOI (Daejeon, KR)
- Ji Eun CHOI (Seongnam-si, KR)
Cpc classification
International classification
Abstract
The present invention relates to a naphthalimide sulfonate derivative, and a photoacid generator and a photoresist composition which comprise same, and, more specifically, to a naphthalimide sulfonate derivative compound, and a photoacid generator and a photoresist composition which comprise same, the compound having an excellent absorbance of light with an i-line wavelength (365 nm), having a high solubility in an organic solvent, having excellent thermal stability, and exhibiting a good acid generation rate.
Claims
1. A naphthalimide sulfonic acid derivative compound represented by the following Formula I or II: ##STR00038## wherein, in Formula I, R.sub.1 is a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, or a substituted or unsubstituted alkylaryl group; R.sub.2 is hydrogen atom or t-butyl group; m is an integer of 1 to 4; n is an integer of 0 to 2; ##STR00039## wherein, in Formula II, R.sub.1, m and n are the same as defined in Formula I, and R.sub.2 is hydrogen atom.
2. The naphthalimide sulfonic acid derivative compound of claim 1, wherein R.sub.1 is a C.sub.1-C.sub.12 linear alkyl group or C.sub.3-C.sub.12 branched alkyl group that is unsubstituted or substituted with one or more halogen atoms or alicyclic hydrocarbon group; a C.sub.3-C.sub.12 alicyclic hydrocarbon group that is unsubstituted or substituted with one or more halogen atoms; a C.sub.6-C.sub.20 aryl group that is unsubstituted or substituted with one or more halogen atoms; a C.sub.7-C.sub.20 arylalkyl group that is unsubstituted or substituted with one or more halogen atoms or C.sub.1-C.sub.12 alkylthio group; or a C.sub.7-C.sub.20 alkylaryl group that is unsubstituted or substituted with one or more halogen atoms.
3. The naphthalimide sulfonic acid derivative compound of claim 1, wherein R.sub.1 is methyl group, ethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, nonafluorobutyl group or tosyl group.
4. The naphthalimide sulfonic acid derivative compound of claim 1, which is selected from the following compounds: ##STR00040## ##STR00041## ##STR00042##
5. A photoacid generator comprising a naphthalimide sulfonic acid derivative compound of claim 1.
6. A photoresist composition comprising a naphthalimide sulfonic acid derivative compound of claim 1; and a binder resin.
7. An acenaphthene derivative compound represented by the following Formula III or IV: ##STR00043## wherein, in Formula III, R.sub.2 is hydrogen atom or t-butyl group; m is an integer of 1 to 4; n is an integer of 0 to 2; ##STR00044## wherein, in Formula IV, R.sub.2 is hydrogen atom; and m and n are the same as defined in Formula III.
8. A method for preparing an acenaphthene derivative compound represented by Formula III or IV of claim 7, the method comprising a step of reducing a compound represented by the following Formula III′ or IV′, respectively: ##STR00045## wherein, in Formulas III′ and IV′, R.sub.2, m and n are the same as defined in Formulas III and IV′ of claim 7, respectively.
Description
EXAMPLES
Example 1: Preparation of 4-cyclopropanemethyl-naphthalimide trifluoromethane sulfonate (1)
[0043] Reaction 1. Synthesis of 5-cyclopropanecarbonyl acenaphthene
[0044] 5.0 g (32.4 mmol) of acenaphthene was added to dichloromethane, and cooled to 10° C. or lower. 4.55 g (34.0 mmol) of aluminum chloride was added thereto and stirred for 30 minutes, and then 3.39 g (32.4 mmol) of cyclopropanecarbonyl chloride diluted in dichloromethane was slowly added thereto, and the reaction mixture was stirred for 1 hour at 5° C. or less. Next, distilled water was added to the reaction product, and after stirring for 30 minutes, the organic layer was separated. The separated organic layer was washed twice with distilled water, and the collected organic layer was dried with anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The concentrated residue was purified by silica gel column chromatography (developing solvent; ethyl acetate:n-heptane=1:4) to obtain 6.03 g (83.7%) of 5-cyclopropanecarbonyl acenaphthene.
[0045] .sup.1H NMR (δ.sub.ppm; CDCl.sub.3): 1.08-1.02(2H, m), 1.31-1.35(2H, m), 2.63-2.74(1H, m)), 3.40(4H, m), 7.31-7.36(2H, m), 7.51-7.56(1H, dd), 8.10-8.12(1H, d), 8.42-8.44(1H, d)
[0046] MS (m/z): 222
Reaction 2. Synthesis of 5-cyclopropylmethyl acenaphthene
[0047] 5.75 g (25.9 mmol) of 5-cyclopropanecarbonyl acenaphthene, 3.50 g (38.8 mmol) of methyl carbazate, and 4.66 g (77.6 mmol) of acetic acid were dissolved in ethanol, and the reaction mixture was heated to reflux. The reaction mixture was then cooled to room temperature and ethanol was removed under reduced pressure. Ethyl acetate and distilled water were added to the concentrated residue, and after stirring, the organic layer was separated. The separated organic layer was washed twice with distilled water, and the collected organic layer was dried with anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The concentrated residue was added to 7.27 g (129.5 mmol) of potassium hydroxide and triethylene glycol, heated to 140° C., stirred, cooled to room temperature, and stirred with n-heptane and distilled water, and then the organic layer was separated. The separated organic layer was washed twice with distilled water, and the collected organic layer was dried with anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The product obtained by distilling the organic layer under reduced pressure was purified by silica gel column chromatography (developing solvent: n-heptane alone) to obtain 4.24 g (65.4%) of solid 5-cyclopropylmethyl acenaphthene.
[0048] .sup.1H NMR (δ.sub.ppm; CDCl.sub.3): 0.23-0.27(2H, m) 0.52-0.56(2H, m), 1.12-1.20(1H, m), 2.93-2.94(2H, d) 3.35-3.42(4H, m), 7.21-7.24(1H, d) 7.27-7.28(1H, d), 7.37-7.39(1H, d), 7.44-7.47(1H, dd), 7.71-7.73(1H, d)
[0049] MS(m/z): 208
Reaction 3. Synthesis of 4-cyclopropylmethyl naphthylic anhydride
[0050] 15.0 g (72.0 mmol) of 5-cyclopropylmethyl acenaphthene was added to acetic acid, 107.3 g (360.1 mmol) of sodium dichromate dihydrate was added thereto, and the mixture was stirred at room temperature and heated to reflux. Then, after cooling to room temperature, the reaction mixture was poured into ice water. The generated solid was filtered and washed sequentially with distilled water and ethanol. The resulting solid was dried to obtain 13.70 g (75.4%) of 4-cyclopropylmethyl naphthylic anhydride.
[0051] 1H NMR (δ.sub.ppm; CDCl.sub.3): 0.31-0.36(2H, m), 0.64-0.70(2H, m), 1.14-1.23(1H, m), 3.14-3.16(2H, d), 7.82-7.86(2H, m), 8.51-8.54(1H, dd), 8.58-8.60(1H, d), 8.63-8.65(1H, dd)
[0052] MS(m/z): 252
Reaction 4. Synthesis of N-hydroxy-4-cyclopropylmethyl naphthalimide
[0053] 13.40 g (53.1 mmol) of 4-cyclopropylmethyl naphthylic anhydride was added to ethanol, 5.54 g (79.7 mmol) of hydroxylamine hydrochloride salt and 6.30 g (79.7 mmol) of pyridine were added thereto, and the mixture was heated to reflux. Ethanol was removed under reduced pressure to obtain 13.30 g (crude yield: 93.7%) of crude N-hydroxy-4-cyclopropylmethyl naphthalimide, which was used in the next reaction without further purification.
[0054] 1H NMR (δ.sub.ppm; CDCl.sub.3): 0.30-0.34(2H, m), 0.64-0.69(2H, m), 1.12-1.21(1H, m), 3.14-3.16(2H, d), 7.79-7.84(2H, m), 8.49-8.51(1H, d), 8.61-8.63(1H, d) 8.67-8.69(1H, d), 8.72(1H, b)
[0055] MS(m/z): 267
Reaction 5. Synthesis of 4-cyclopropanemethyl-naphthalimide trifluoromethane sulfonate (1) 13.75 g (51.4 mmol) of N-hydroxy-5-cyclopropylmethyl naphthalimide was added to dichloromethane, and 10.41 g (102.9 mmol) of triethylamine was added thereto, and the mixture was stirred for 30 minutes and cooled to 5° C. or lower. After adding 8.67 g (51.4 mmol) of trifluoromethane sulfonyl chloride, the mixture was stirred at room temperature. Then, after adding thereto distilled water and stirring, the organic layer was separated. The separated organic layer was washed twice with distilled water, and the collected organic layer was dried with anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The product obtained by distilling the organic layer under reduced pressure was purified by silica gel column chromatography (developing solvent: ethyl acetate:n-heptane=1:4) to obtain 16.24 g (79.1%) of 4-cyclopropanemethyl-naphthalimide trifluoromethane sulfonate (1).
[0056] 1H NMR (δ.sub.ppm; CDCl.sub.3): 0.31-0.35(2H, m), 0.65-0.70(2H, m), 1.13-1.21(1H, m), 3.15-3.16(2H, d), 7.83-7.87(2H, m), 8.54-8.56(1H, dd), 8.62-8.64(1H, d), 8.67-8.69(1H, dd)
[0057] MS(m/z): 399
[0058] The following compounds were prepared in the same manner as in Example 1.
TABLE-US-00001 Compound MS No. Structure 1H-NMR (m/z) 1
Example 2: Preparation of 2,5-dicyclopropanemethyl-naphthalimide trifluoromethane sulfonate (9)
[0059] Reaction 1. Synthesis of 3,6-cyclohexanecarbonyl acenaphthene
[0060] 6.0 g (38.9 mmol) of acenaphthene was added to dichloromethane, and cooled to 10° C. or lower. 10.89 g (81.7 mmol) of aluminum chloride was added thereto and stirred for 30 minutes, and then 12.55 g (85.6 mmol) of cyclohexane chloride diluted in dichloromethane was slowly added thereto, and the reaction mixture was stirred for 1 hour at 5° C. or less. Next, distilled water was added to the reaction product, and after stirring for 30 minutes, the organic layer was separated. The separated organic layer was washed twice with distilled water, and the collected organic layer was dried with anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The concentrated residue was purified by silica gel column chromatography (developing solvent; ethyl acetate:n-heptane=1:4) to obtain 10.30 g (70. 7%)of 3,6-dicyclohexanecarbonyl acenaphthene.
[0061] .sup.1H NMR (δ.sub.ppm; CDCl.sub.3): 1.08-1.02(2H, m), 1.31-1.35(2H, m), 2.63-2.74(1H, m)), 3.41-3.48(2H, t), 3.78-3.85(2H, t) 7.36-7.41(2H, m), 8.13-8.15(1H, d), 8.45-8.47(1H, d)
[0062] MS(m/z): 290
Reaction 2. Synthesis of 3,6-dicyclohexylmethyl acenaphthene
[0063] 10.75 g (28.0 mmol) of 3,6-dicyclohexanecarbonyl acenaphthene, 7.58 g (84.1 mmol) of methyl carbazate, and 10.10 g (168.2 mmol) of acetic acid were dissolved in ethanol, and the reaction mixture was heated to reflux. The reaction mixture was then cooled to room temperature and ethanol was removed under reduced pressure. Ethyl acetate and distilled water were added to the concentrated residue, and after stirring, the organic layer was separated. The separated organic layer was washed twice with distilled water, and the collected organic layer was dried with anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The concentrated residue was added to 15.71 g (280.0 mmol) of potassium hydroxide and triethylene glycol, heated to 140° C., stirred, cooled to room temperature, and stirred with n-heptane and distilled water, and then the organic layer was separated. The separated organic layer was washed twice with distilled water, and the collected organic layer was dried with anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The product obtained by distilling the organic layer under reduced pressure was purified by silica gel column chromatography (developing solvent: ethyl acetate:n-heptane=1:4) to obtain 4.27 g (58.2%) of 3,6-dicyclohexylmethyl acenaphthene.
[0064] .sup.1H NMR (δ.sub.ppm; CDCl.sub.3): 0.23-0.27(4H, m) 0.52-0.56(4H, m), 1.12-1.20(2H, m), 2.87-2.88(2H, d), 2.90-2.91(2H, d) 3.35-3.42(2H, t), 3.42-3.69(2H, t), 7.25-7.29(1H, d) 7.31-7.32(1H, d), 7.47-7.50(1H, d), 7.73-7.75(1H, d)
[0065] MS(m/z): 262
Reaction 3. Synthesis of 2,5-dicyclopropylmethyl naphthylic anhydride
[0066] 2.35 g (6.8 mmol) of 3,6-dicyclohexylmethyl acenaphthene was added to acetic acid, 10.10 g (33.9 mmol) of sodium dichromate dihydrate was added thereto, and the mixture was stirred at room temperature and heated to reflux. Then, after cooling to room temperature, the reaction mixture was poured into ice water, and after adding ethyl acetate thereto and stirring, the organic layer was separated. The separated organic layer was washed twice with distilled water, and the collected organic layer was dried with anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The product obtained by distilling the organic layer under reduced pressure was purified by silica gel column chromatography (developing solvent: ethyl acetate:n-heptane=1:4) to obtain 1.78 g (67.2%) of 2,5-dicyclopropylmethyl naphthylic anhydride.
[0067] 1H NMR (δ.sub.ppm; CDCl.sub.3): 0.31-0.36(4H, m), 0.64-0.70(4H, m), 1.14-1.23(2H, m), 3.14-3.16(2H, d), 3.17-3.19(2H, d), 7.82-7.86(2H, m), 8.58-8.60(1H, d), 8.63-8.65(1H, d)
[0068] MS(m/z): 306
Reaction 4. Synthesis of N-hydroxy-2,5-dicyclopropylmethyl naphthalimide
[0069] 5.24 g (13.4 mmol) of 2,5-dicyclopropylmethyl naphthylic anhydride was added to ethanol, 1.40 g (20.1 mmol) of hydroxylamine hydrochloride salt and 1.59 g (20.1 mmol) of pyridine were added thereto, and the mixture was heated to reflux. Ethanol was removed under reduced pressure to obtain 3.54 g (crude yield: 65.1%) of crude N-hydroxy-2,5-dicyclopropylmethyl naphthalimide.
[0070] 1H NMR (δ.sub.ppm; CDCl.sub.3): 0.30-0.34(4H, m), 0.64-0.69(4H, m), 1.12-1.21(2H, m), 3.14-3.16(2H, d), 3.17-3.19(2H, d), 7.81-7.86(2H, m), 8.62-8.64(1H, d), 8.67-8.69(1H, d), 8.71(1H, b)
[0071] MS(m/z): 321
Reaction 5. Synthesis of 2,5-dicyclopropanemethyl-naphthalimide trifluoromethane sulfonate (9)
[0072] 4.08 g (10.1 mmol) of N-hydroxy-2,5-dicyclopropylmethyl naphthalimide was added to dichloromethane, and 2.04 g (20.1 mmol) of triethylamine was added thereto, and the mixture was stirred for 30 minutes and cooled to 5° C. or lower. After adding 1.70 g (10.1 mmol) of trifluoromethane sulfonyl chloride, the mixture was stirred at room temperature. Then, after adding thereto distilled water and stirring, the organic layer was separated. The separated organic layer was washed twice with distilled water, and the collected organic layer was dried with anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The product obtained by distilling the organic layer under reduced pressure was purified by silica gel column chromatography (developing solvent: ethyl acetate:n-heptane=1:4) to obtain 3.52 g (65.1%) of 2,5-dicyclopropanemethyl-naphthalimide trifluoromethane sulfonate (9).
[0073] 1H NMR (δ.sub.ppm; CDCl.sub.3): 0.31-0.35(4H, m), 0.65-0.70(4H, m), 1.13-1.21(2H, m), 3.15-3.16(2H, d), 3.20-3.21(2H, d), 7.83-7.87(2H, d), 8.62-8.64(1H, d), 8.67-8.69(1H, d)
[0074] MS(m/z): 453
[0075] The following compounds were prepared in the same manner as in Example 2.
TABLE-US-00002 Compound MS No. Structure 1H-NMR (m/z) 11
Example 3: Preparation of 4-t-butyl acenaphthene (16)
[0076] 15.00 g (97.3 mmol) of acenaphthene was added to dichloromethane and cooled to 10° C. or lower. 0.65 g (4.9 mmol) of aluminum chloride was added thereto and stirred for 30 minutes, and then 13.33 g (97.3 mmol) of t-butyl bromide was slowly added thereto, and the reaction mixture was heated to reflux and stirred. Next, distilled water was added to the reaction product, and after stirring for 30 minutes, the organic layer was separated. The separated organic layer was washed twice with distilled water, and the collected organic layer was dried with anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The concentrated residue was purified by silica gel column chromatography (developing solvent; ethyl acetate:n-heptane=1:4) to obtain 12.03 g (58.8%) of 4-t-butyl acenaphthene (16).
[0077] .sup.1H NMR (δ.sub.ppm; CDCl.sub.3): 1.44(9H, s), 3.32-3.41(4H, m), 7.11-7.12(1H, d), 7.29-7.38(2H, m), 7.76-7.81(2H, m)
[0078] MS(m/z): 210
Example 4: Preparation of 3-t-butyl-5-cyclopropylmethyl-naphthalimide trifluoromethane sulfonate (17)
[0079] Reaction 1. Synthesis of 4-t-butyl-6-cyclopropanecarbonyl acenaphthene
[0080] 5.0 g (23.8 mmol) of 4-t-butyl acenaphthene (16) was added to dichloromethane, and cooled to 10° C. or lower. 3.33 g (25.0 mmol) of aluminum chloride was added thereto and stirred for 30 minutes, and then 2.49 g (23.8 mmol) of cyclopropanecarbonyl chloride diluted in dichloromethane was slowly added thereto, and the reaction mixture was stirred for 1 hour at 5° C. or less. Next, distilled water was added to the reaction product, and after stirring for 30 minutes, the organic layer was separated. The separated organic layer was washed twice with distilled water, and the collected organic layer was dried with anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The concentrated residue was purified by silica gel column chromatography (developing solvent; ethyl acetate:n-heptane=1:4) to obtain 4.56 g (68.9%)of 4-t-butyl-6-cyclopropanecarbonyl acenaphthene.
[0081] 1H NMR (δ.sub.ppm; CDCl.sub.3): 1.08-1.02(2H, m), 1.31-1.35(2H, m), 1.43(9H, s), 1.50(9H, s), 2.63-2.74(1H, m)), 3.40(4H, m), 7.34-7.36(1H, d), 7.53-7.54(1H, d), 8.11-8.13(1H, d), 8.39-8.40(1H, d)
[0082] MS(m/z): 278
Reaction 2. Synthesis of 4-t-butyl-6-cyclopropylmethyl acenaphthene
[0083] 5.36 g (19.3 mmol) of 4-t-butyl-6-cyclopropanecarbonyl acenaphthene, 2.60 g (28.9 mmol) of methyl carbazate, and 3.47 g (57.8 mmol) of acetic acid were dissolved in ethanol, and the reaction mixture was heated to reflux. The reaction mixture was then cooled to room temperature and ethanol was removed under reduced pressure. Ethyl acetate and distilled water were added to the concentrated residue, and after stirring, the organic layer was separated. The separated organic layer was washed twice with distilled water, and the collected organic layer was dried with anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The product obtained by distilling the organic layer under reduced pressure was added to 5.41 g (96.5 mmol) of potassium hydroxide and triethylene glycol, heated to 140° C., stirred, cooled to room temperature, and stirred with n-heptane and distilled water, and then the organic layer was separated. The separated organic layer was washed twice with distilled water, and the collected organic layer was dried with anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The product obtained by distilling the organic layer under reduced pressure was purified by silica gel column chromatography (developing solvent: ethyl acetate:n-heptane=1:10) to obtain 2.66 g (52.3%) of 4-t-butyl-6-cyclopropylmethyl acenaphthene.
[0084] .sup.1H NMR (δ.sub.ppm; CDCl.sub.3): 0.23-0.27(2H, m) 0.52-0.56(2H, m), 1.12-1.20(1H, m), 1.50(9H, s), 2.93-2.94(2H, d) 3.35-3.42(4H, m), 7.25-7.26(1H, d), 7.32-7.33(1H, d), 7.40-7.41(1H, d), 7.66-7.67(1H, d)
[0085] MS (m/z): 264
Reaction 3. Synthesis of 3-t-butyl-5-cyclopropylmethyl naphthylic anhydride
[0086] 10.05 g (38.0 mmol) of 4-t-butyl-6-cyclopropylmethyl acenaphthene was added to acetic acid, 56.63 g (190.0 mmol) of sodium dichromate dihydrate was added thereto, and the mixture was stirred at room temperature and heated to reflux. Then, after cooling to room temperature, ethanol was removed under reduced pressure, and then ethyl acetate and distilled water were added and stirred, and the organic layer was separated. The separated organic layer was washed twice with distilled water, and the collected organic layer was dried with anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The product obtained by distilling the organic layer under reduced pressure was purified by silica gel column chromatography (developing solvent: ethyl acetate:n-heptane=1:4) to obtain 7.25 g (61.9%) of 3-t-butyl-5-cyclopropylmethyl naphthylic anhydride.
[0087] .sup.1 H NMR (δ.sub.ppm; CDCl.sub.3): 0.31-0.36(2H, m), 0.64-0.70(2H, m), 1.14-1.23(1H, m), 1.50(9H, s), 3.14-3.16(2H, d), 7.79-7.81(1H, d), 8.58-8.60(1H, d), 8.66-8.68(1H, d), 8.71-8.72(1H, d)
[0088] MS(m/z): 308
Reaction 4. Synthesis of N-hydroxy-3-t-butyl-5-cyclopropylmethyl naphthalimide
[0089] 10.80 g (35.0 mmol) of 3-t-butyl-5-cyclopropylmethyl naphthylic anhydride was added to ethanol, 3.65 g (52.5 mmol) of hydroxylamine hydrochloride salt and 4.16 g (52.5 mmol) of pyridine were added thereto, and the mixture was heated to reflux. Ethanol was removed under reduced pressure, and then ethyl acetate and distilled water were added and stirred, and the organic layer was separated. The separated organic layer was washed twice with distilled water, and the collected organic layer was dried with anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The product obtained by distilling the organic layer under reduced pressure was purified by silica gel column chromatography (developing solvent: ethyl acetate:n-heptane=1:4) to obtain 8.23 g (72.7%) of N-hydroxy-3-t-butyl-5-cyclopropylmethyl naphthalimide.
[0090] .sup.1H NMR (δ.sub.ppm; CDCl.sub.3): 0.30-0.34(2H, m), 0.64-0.69(2H, m), 1.12-1.21(1H, m), 1.50(9H, s), 3.14-3.16(2H, d), 7.74-7.76(1H, d), 8.57-8.59(1H, d), 8.69-8.71(1H, d) 8.76-8.77(1H, d), 8.79(1H, b)
[0091] MS(m/z): 323
Reaction 5. Synthesis of 3 -t-butyl-5 -cyclopropylmethyl-naphthalimide trifluoromethane sulfonate (17)
[0092] 10.65 g (32.9 mmol) of N-hydroxy-3-t-butyl-5-cyclopropylmethyl naphthalimide was added to dichloromethane, and 6.66 g (65.9 mmol) of triethylamine was added thereto, and the mixture was stirred for 30 minutes and cooled to 5° C. or lower. After adding 5.55 g (32.9 mmol) of trifluoromethane sulfonyl chloride, the mixture was stirred at room temperature. Then, after adding thereto distilled water and stirring, the organic layer was separated. The separated organic layer was washed twice with distilled water, and the collected organic layer was dried with anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The product obtained by distilling the organic layer under reduced pressure was purified by silica gel column chromatography (developing solvent: ethyl acetate:n-heptane=1:4) to obtain 10.55 g (70.3%) of 3-t-butyl-5-cyclopropylmethyl-naphthalimide trifluoromethane sulfonate (17).
[0093] .sup.1H NMR(δ.sub.ppm; CDCl.sub.3): 0.31-0.35(2H, m), 0.65-0.70(2H, m), 1.13-1.21(1H, m), 1.50(9H, s), 3.15-3.16(2H, d), 7.77-7.79(1H, d), 8.61-8.62(1H, d), 8.70-8.72(1H, d), 8.77-8.78(1H, d)
[0094] MS(m/z): 455
[0095] The following compounds were prepared in the same manner as in Example 4.
TABLE-US-00003 Compound MS No. Structure 1H-NMR (m/z) 18
Preparation of Binder Resin
a) Preparation of Binder Resin 1
[0096] 200 ml of propylene glycol monomethyl ether acetate (PGMEA) and 1.5 g of azobisisobutyronitrile (AIBN) were added in a 500 ml polymerization vessel, and acetoxy styrene, styrene, and t-butoxymethacrylate were added with a molar ratio of 50:25:25, respectively, so that the solid content might be 40 weight %, and then polymerized with stirring at 70° C. for 5 hours under nitrogen atmosphere to prepare binder resin 1.
[0097] It was confirmed that the weight average molecular weight of the copolymer prepared as such was 25,000, and the degree of dispersion thereof was 2.0.
b) Preparation of Binder Resin 2
[0098] 200 ml of PGMEA and 1.5 g of AIBN were added in a 500 ml polymerization vessel, and acetoxy styrene, styrene, t-butoxymethacrylate and methyl methacrylate were added with a molar ratio of 40:25:25:10, respectively, so that the solid content might be 40 weight %, and then polymerized with stirring at 70° C. for 5 hours under nitrogen atmosphere to synthesize a copolymer. After adding 0.3 g of N,N-dimethylaniline and 20 molar ratio of glycidyl methacrylate to the reactor, the mixture was stirred at 100° C. for 10 hours to prepare binder resin 2, which was an acrylic polymer having an acrylic unsaturated bond in the side chain. It was confirmed that the weight average molecular weight of the copolymer prepared as such was 20,000, and the degree of dispersion thereof was 2.1.
Measurement of Solubility
[0099] In preparing a photoresist composition, solubility of a photoacid generator is very important. Hence, the solubility in propylene glycol monomethyl ether (PGMEA) and cyclohexane, which are solvents mainly used in photoresist compositions, were compared with those of the compound of the following Formula V, and are shown in Table 1 below.
##STR00036##
TABLE-US-00004 TABLE 1 Solubility of photoacid generators Solubility (w/v; %) Compound No. PGMEA Cyclohexane 1 9.2 26.1 5 3.1 7.8 9 6.3 21.3 13 10.2 30.2 19 11.0 31.2 Formula V 1.7 5.8
Measurement of Thermal Stability
[0100] If a photoacid generator is thermally stable in a photoresist preparation process, a very good effect in terms of stability can be expected. Hence, the temperature at which 5% weight loss occurred was measured by using a thermogravimetric analyzer to compare with the compound of Formula V.
TABLE-US-00005 TABLE 2 Thermal stability of photoacid generators Temperature at which 5% Compound No. weight loss occurred (° C.) 1 242 5 252 9 258 13 244 19 236 Formula V 223
Preparation of Photoresist Compositions of Examples
[0101] In a reaction mixing bath equipped with an ultraviolet blocking film and an agitator, according to the components and contents shown in Table 3 below, binder resins 1 and 2; compounds 1, 2, 4, 11 and 18 as photoacid generators; and FC-430 (a leveling agent of 3M, 0.02 weight %) were sequentially added, and the mixture was stirred at room temperature, and then PGMEA as a solvent was added to make 100 weight %, to prepare a photoresist composition.
TABLE-US-00006 TABLE 3 Preparation of photoresist composition Composition Binder resin photoacid generator Additive No. (parts by (parts by (parts by weight) weight) weight) 1 1 (97) Compound 1 (0.4) FC-430 (0.1) 2 1 (97) Compound 2 (0.4) FC-430 (0.1) 3 1 (97) Compound 4 (0.4) FC-430 (0.1) 4 1 (97) Compound 11 (0.4) FC-430 (0.1) 5 1 (97) Compound 18 (0.4) FC-430 (0.1) 6 2 (97) Compound 1 (0.4) FC-430 (0.1) 7 2 (97) Compound 4 (0.4) FC-430 (0.1) 8 2 (97) Compound 11 (0.4) FC-430 (0.1) 9 2 (97) Compound 18 (0.4) FC-430 (0.1) 10 2 (97) Compound 4 (0.4) FC-430 (0.1) 11 1 (60) Compound 1 (0.4) FC-430 (0.1) 2 (37) 12 1 (37) Compound 1 (0.4) FC-430 (0.1) 2 (60)
Preparation of Photoresist Composition of Comparative Example
[0102] A photoresist composition was prepared in the same manner as in the preparation of Composition 1, except that the photoacid generator of Formula V was used instead of Compound 5 as the photoacid generator.
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Evaluation of Photoresist Composition
[0103] Evaluation of the photoresist compositions of Examples and Comparative Example was performed on a glass substrate, and pattern stability and taper angle of the photoresist composition were measured, and the evaluation results are shown in Table 4 below.
1) Pattern Stability
[0104] The photoresist was spin-coated on a silicon wafer substrate, dried on a hot plate at 90° C. for 1 minute, exposed with using a line-space (10 μm-10 μm) step mask, subjected to a post-exposure bake process, and then developed in 2.384% aqueous solution of trimethylammonium hydroxide (TMAH). The width of the pattern in the space portion after the development was measured.
2) Taper Angle
[0105] The photoresist was spin-coated on a silicon wafer substrate, dried on a hot plate at 90° C. for 1 minute, exposed with using a line-space (10 μ-10 μm) step mask, subjected to a post-exposure bake process, and then developed in 2.384% aqueous solution of trimethylammonium hydroxide (TMAH). The taper angle of the space portion after the development was measured, and it was determined as good in case of 85 to 90° , and poor in case of less than 85° or greater than 91°.
TABLE-US-00007 TABLE 4 Size of space Value compared Condition Composition CD pattern withC omparative of No. (μm) Example taper angle 1 12.4 1.07 Good 2 11.4 0.98 Poor 3 12.4 1.07 Good 4 12.5 1.08 Good 5 11.8 1.02 Good 6 12.4 1.07 Good 7 12.3 1.06 Good 8 12.0 1.03 Good 9 12.4 1.07 Good 10 12.3 1.06 Good 11 12.0 1.03 Good 12 12.0 1.03 Good Comparative 11.6 1.00 Poor Example