JP2007302635A - Acid anhydride having silsesquioxane skeleton and polymer - Google Patents
Acid anhydride having silsesquioxane skeleton and polymer Download PDFInfo
- Publication number
- JP2007302635A JP2007302635A JP2006134628A JP2006134628A JP2007302635A JP 2007302635 A JP2007302635 A JP 2007302635A JP 2006134628 A JP2006134628 A JP 2006134628A JP 2006134628 A JP2006134628 A JP 2006134628A JP 2007302635 A JP2007302635 A JP 2007302635A
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- JP
- Japan
- Prior art keywords
- carbon atoms
- alkyl
- phenyl
- replaced
- carbons
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 150000008065 acid anhydrides Chemical class 0.000 title claims abstract description 47
- 229920000642 polymer Polymers 0.000 title claims description 31
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 72
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 18
- 125000003118 aryl group Chemical group 0.000 claims abstract description 15
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 9
- 125000004018 acid anhydride group Chemical group 0.000 claims abstract description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 7
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 69
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 49
- 239000010408 film Substances 0.000 claims description 48
- 229910052739 hydrogen Inorganic materials 0.000 claims description 39
- 239000001257 hydrogen Substances 0.000 claims description 39
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 38
- 125000002947 alkylene group Chemical group 0.000 claims description 29
- 230000003287 optical effect Effects 0.000 claims description 26
- 239000010409 thin film Substances 0.000 claims description 19
- 239000004973 liquid crystal related substance Substances 0.000 claims description 18
- 125000003884 phenylalkyl group Chemical group 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 16
- 229920001721 polyimide Polymers 0.000 claims description 16
- 239000004642 Polyimide Substances 0.000 claims description 15
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 229910052736 halogen Inorganic materials 0.000 claims description 12
- 150000002367 halogens Chemical group 0.000 claims description 12
- 239000003822 epoxy resin Substances 0.000 claims description 10
- 229920000647 polyepoxide Polymers 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 230000001681 protective effect Effects 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 239000011737 fluorine Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 150000004985 diamines Chemical class 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000001153 fluoro group Chemical group F* 0.000 claims description 5
- 238000006068 polycondensation reaction Methods 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 4
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 6
- 230000009477 glass transition Effects 0.000 abstract description 6
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 description 25
- -1 methacryloyl group Chemical group 0.000 description 24
- 238000000034 method Methods 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 11
- 239000000758 substrate Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000004427 diamine group Chemical group 0.000 description 4
- 230000005693 optoelectronics Effects 0.000 description 4
- 238000012643 polycondensation polymerization Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical class Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- MXPYJVUYLVNEBB-UHFFFAOYSA-N 2-[2-(2-carboxybenzoyl)oxycarbonylbenzoyl]oxycarbonylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1C(O)=O MXPYJVUYLVNEBB-UHFFFAOYSA-N 0.000 description 2
- AVCOFPOLGHKJQB-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)sulfonylphthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1S(=O)(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 AVCOFPOLGHKJQB-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- PCJJZUQUVMVZGQ-UHFFFAOYSA-N 4-[(4,4-dicarboxycyclohexyl)methyl]cyclohexane-1,1-dicarboxylic acid Chemical compound C1CC(C(=O)O)(C(O)=O)CCC1CC1CCC(C(O)=O)(C(O)=O)CC1 PCJJZUQUVMVZGQ-UHFFFAOYSA-N 0.000 description 2
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 description 2
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 2
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000005452 alkenyloxyalkyl group Chemical group 0.000 description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- GWHLJVMSZRKEAQ-UHFFFAOYSA-N 3-(2,3-dicarboxyphenyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O GWHLJVMSZRKEAQ-UHFFFAOYSA-N 0.000 description 1
- TYKLCAKICHXQNE-UHFFFAOYSA-N 3-[(2,3-dicarboxyphenyl)methyl]phthalic acid Chemical compound OC(=O)C1=CC=CC(CC=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O TYKLCAKICHXQNE-UHFFFAOYSA-N 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- MFKRHJVUCZRDTF-UHFFFAOYSA-N 3-methoxy-3-methylbutan-1-ol Chemical compound COC(C)(C)CCO MFKRHJVUCZRDTF-UHFFFAOYSA-N 0.000 description 1
- IFRZFIUBFCZXKK-UHFFFAOYSA-N 3-triethoxysilylpropan-1-amine;n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCN.CO[Si](OC)(OC)CCCNCCN IFRZFIUBFCZXKK-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- FYYYKXFEKMGYLZ-UHFFFAOYSA-N 4-(1,3-dioxo-2-benzofuran-5-yl)-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1C1=CC=CC2=C1C(=O)OC2=O FYYYKXFEKMGYLZ-UHFFFAOYSA-N 0.000 description 1
- UMRMNHAITOCJKK-UHFFFAOYSA-N 4-(4,4-dicarboxycyclohexyl)oxycyclohexane-1,1-dicarboxylic acid Chemical compound C(=O)(O)C1(CCC(CC1)OC1CCC(CC1)(C(=O)O)C(=O)O)C(=O)O UMRMNHAITOCJKK-UHFFFAOYSA-N 0.000 description 1
- IMWZFQNEZIDIRD-UHFFFAOYSA-N 4-(4,4-dicarboxycyclohexyl)sulfonylcyclohexane-1,1-dicarboxylic acid Chemical compound C(=O)(O)C1(CCC(CC1)S(=O)(=O)C1CCC(CC1)(C(=O)O)C(=O)O)C(=O)O IMWZFQNEZIDIRD-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 1
- 125000004860 4-ethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- WMBSTFRTTUVWHC-UHFFFAOYSA-N C[Si+](C(CC(C1)C2C(O3)=O)C1C2C3=O)(O[Si+](c1ccccc1)(O[Si+](c1ccccc1)(O1)O[Si+](c2ccccc2)(O2)O3)O4)O[Si+]2(c2ccccc2)O[Si+]2(c5ccccc5)O[Si+]4(c4ccccc4)O[Si+]1(c1ccccc1)O[Si+](C)(C(CC(C1)C4C(O5)=O)C1C4C5=O)O[Si+]3(c1ccccc1)O2 Chemical compound C[Si+](C(CC(C1)C2C(O3)=O)C1C2C3=O)(O[Si+](c1ccccc1)(O[Si+](c1ccccc1)(O1)O[Si+](c2ccccc2)(O2)O3)O4)O[Si+]2(c2ccccc2)O[Si+]2(c5ccccc5)O[Si+]4(c4ccccc4)O[Si+]1(c1ccccc1)O[Si+](C)(C(CC(C1)C4C(O5)=O)C1C4C5=O)O[Si+]3(c1ccccc1)O2 WMBSTFRTTUVWHC-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000004450 alkenylene group Chemical group 0.000 description 1
- 125000003302 alkenyloxy group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005082 alkoxyalkenyl group Chemical group 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical group CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- RZIPTXDCNDIINL-UHFFFAOYSA-N cyclohexane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCCC1(C(O)=O)C(O)=O RZIPTXDCNDIINL-UHFFFAOYSA-N 0.000 description 1
- WVIIMZNLDWSIRH-UHFFFAOYSA-N cyclohexylcyclohexane Chemical compound C1CCCCC1C1CCCCC1 WVIIMZNLDWSIRH-UHFFFAOYSA-N 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- STZIXLPVKZUAMV-UHFFFAOYSA-N cyclopentane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCC1(C(O)=O)C(O)=O STZIXLPVKZUAMV-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- FAEBHRCELNWPNI-UHFFFAOYSA-N ethane-1,2-diol;phenyl acetate Chemical compound OCCO.CC(=O)OC1=CC=CC=C1 FAEBHRCELNWPNI-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- OBKARQMATMRWQZ-UHFFFAOYSA-N naphthalene-1,2,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 OBKARQMATMRWQZ-UHFFFAOYSA-N 0.000 description 1
- DOBFTMLCEYUAQC-UHFFFAOYSA-N naphthalene-2,3,6,7-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 DOBFTMLCEYUAQC-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical class Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Liquid Crystal (AREA)
- Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Epoxy Resins (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Silicon Polymers (AREA)
- Optical Integrated Circuits (AREA)
Abstract
Description
本発明は、かご型シルセスキオキサン骨格を有する酸無水物、およびこれを主原料として用いて得られる、主鎖にかご型シルセスキオキサン骨格を有する新規な重合体に関する。本発明のポリマーは、電子材料、光学材料および光エレクトロニクスの分野において、絶縁膜、保護膜、液晶配向膜、光導波路などに用いられる。なお、「シルセスキオキサン」は、各ケイ素原子が３個の酸素原子と結合し、各酸素原子が２個のケイ素原子と結合している化合物を示す類名であるが、本発明においてはその一部が変形したシルセスキオキサン類似構造の化合物も含めてシルセスキオキサンとする。シルセスキオキサン構造およびその一部が変形したシルセスキオキサン類似構造の総称として、「シルセスキオキサン骨格」を用いる。以下の説明では、用語「シルセスキオキサン」を記号「ＰＳＱ」を用いて表記することがある。 The present invention relates to an acid anhydride having a cage silsesquioxane skeleton, and a novel polymer having a cage silsesquioxane skeleton in the main chain obtained by using the acid anhydride as a main raw material. The polymer of the present invention is used for insulating films, protective films, liquid crystal alignment films, optical waveguides and the like in the fields of electronic materials, optical materials and optoelectronics. “Silsesquioxane” is a class name indicating a compound in which each silicon atom is bonded to three oxygen atoms, and each oxygen atom is bonded to two silicon atoms. Silsesquioxane including a compound having a silsesquioxane-like structure in which a part thereof is deformed is used. A “silsesquioxane skeleton” is used as a generic term for silsesquioxane structures and silsesquioxane-like structures in which a part thereof is deformed. In the following description, the term “silsesquioxane” may be expressed using the symbol “PSQ”.
ＰＳＱに関しては、これまで数多くの研究が行われてきた。例えば非特許文献１に記載されている総説によれば、ラダー構造、完全縮合型構造、および不完全縮合型構造のほか、一定の構造を示さない不定形構造などのＰＳＱの存在が確認されている。完全縮合型構造とは、複数の環状構造からなり、閉じた空間を形成する構造であり、その閉じた空間の形状は限定されていない。不完全縮合型構造は、完全縮合型構造の少なくとも１箇所以上が塞がれておらず、空間が閉じていない構造である。 Many studies have been conducted on PSQ. For example, according to the review described in Non-Patent Document 1, the presence of PSQ such as an amorphous structure that does not show a certain structure in addition to a ladder structure, a fully condensed structure, and an incompletely condensed structure has been confirmed. Yes. The fully condensed structure is a structure formed of a plurality of annular structures and forming a closed space, and the shape of the closed space is not limited. The incompletely condensed structure is a structure in which at least one part of the completely condensed structure is not closed and the space is not closed.
完全縮合型構造または不完全縮合型構造を有するＰＳＱのうち、容易に合成され単離されている化合物の種類は限定されている。その中で市販されている化合物の数はさらに限定されている。最近では、完全縮合型構造または不完全縮合型構造を有するＰＳＱに、種々の官能基が導入されたＰＳＱ誘導体が、ハイブリッドプラスチック社より市販されており、多くの用途が提案されている。 Among PSQs having a fully condensed structure or an incompletely condensed structure, the types of compounds that are easily synthesized and isolated are limited. Among them, the number of commercially available compounds is further limited. Recently, PSQ derivatives in which various functional groups are introduced into PSQ having a fully condensed structure or an incompletely condensed structure are commercially available from Hybrid Plastics and many uses have been proposed.
しかしながら、これら市販されているＰＳＱ誘導体は完全縮合型（いわゆるＴ８構造）が主流であり、また不完全縮合型もカゴが１箇所だけ閉じていない（Ｔ７構造）がほとんどであった。従って、これらのＰＳＱ誘導体を用いるには、完全縮合型誘導体を添加剤として樹脂中にブレンドする例が多い。しかし、既存のＰＳＱ誘導体には、樹脂との相溶性が悪く、そのために均一に混合できなかったり、塗膜にした場合に白化したり、塗膜からブリードアウトするなどの問題点があるので、その添加量に限界があった。そして、ＰＳＱが本来有する特性（難燃性、耐熱性、耐候性、耐光性、電気絶縁性、表面特性、硬度、力学的強度、耐薬品性など）を十分に付与できない例も少なくなかった。 However, most of these commercially available PSQ derivatives are completely condensed type (so-called T8 structure), and most of the incompletely condensed type is not closed at one place (T7 structure). Therefore, in order to use these PSQ derivatives, there are many examples in which a fully condensed derivative is blended into a resin as an additive. However, the existing PSQ derivatives have poor compatibility with the resin, so that they cannot be uniformly mixed, whitening when formed into a coating film, or bleeding out from the coating film, There was a limit to the amount of addition. In addition, there are many examples in which the characteristics inherent to PSQ (flame resistance, heat resistance, weather resistance, light resistance, electrical insulation, surface characteristics, hardness, mechanical strength, chemical resistance, etc.) cannot be sufficiently provided.
一方、不完全縮合型ＰＳＱ骨格を、ブレンド以外の形で樹脂中に導入した例がいくつか見受けられる。非特許文献２には側鎖にメタクリロイル基を有するかご型のＰＳＱが開示されている。この化合物を重合させて得られたポリマーは、高い機械強度と酸素透過性を有する。さらに、非特許文献３ではＴ７構造の非縮合部をトリクロロシラン誘導体で閉環した後ジアミンを合成し、ＰＳＱ骨格を側鎖に有するポリイミドを合成している。しかし、これらはいずれもＰＳＱを側鎖にしか導入できないという、Ｔ７骨格に由来する構造化学的な問題があった。 On the other hand, there are some examples in which the incompletely condensed PSQ skeleton is introduced into the resin in a form other than the blend. Non-Patent Document 2 discloses a cage-type PSQ having a methacryloyl group in the side chain. A polymer obtained by polymerizing this compound has high mechanical strength and oxygen permeability. Further, in Non-Patent Document 3, a diamine is synthesized after the non-condensed portion of the T7 structure is closed with a trichlorosilane derivative, and a polyimide having a PSQ skeleton in the side chain is synthesized. However, all of these have a structural chemical problem derived from the T7 skeleton that PSQ can be introduced only into the side chain.
近年、非縮合部位を２箇所有する新規なＰＳＱ骨格（以下、ダブルデッカー骨格と略記することがある。）が見出された。この化合物は各種ジクロロシラン類とのエンドキャッピング反応により閉環し、完全縮合型ＰＳＱと類似のかご型ケイ素化合物となることが明らかとなっている。この手法を用いて合成された、式（ａ）で示される酸無水物が特許文献１に開示されている。
そこで、本発明者らは耐熱性を改善するために、式（ｂ）で示される、フタル酸無水物が直結したタイプの剛直な酸無水物を発明した（特許文献３）。
この酸無水物を用いたポリイミドは、２００℃以上のガラス転移温度と、約５００℃の熱分解温度を示し、耐熱性の改善には極めて有効な化合物である。しかし、芳香族酸無水物に起因するポリマーの着色により透明性と耐光性が劣化し、優れた光学特性が要求される光電子材料に用いるには若干問題があった。
In order to improve the heat resistance, the present inventors have invented a rigid acid anhydride of the type directly bonded to phthalic anhydride represented by the formula (b) (Patent Document 3).
A polyimide using this acid anhydride exhibits a glass transition temperature of 200 ° C. or higher and a thermal decomposition temperature of about 500 ° C., and is an extremely effective compound for improving heat resistance. However, transparency and light resistance are deteriorated due to the coloring of the polymer due to the aromatic acid anhydride, and there are some problems when used for optoelectronic materials that require excellent optical properties.
本発明の目的は、主鎖中にダブルデッカー骨格を有する新規な重合体、およびその原料となる脂環式酸無水物基を有するＰＳＱを提供することである。特に、分子鎖を極力剛直にすることにより耐熱性や機械強度を維持しつつ、光エレクトロニクス用材料に応々にして要求される透明・耐光性を併せ持つポリイミド、またはエポキシ樹脂を提供することである。具体的には、例えば、低誘電率の絶縁膜、耐光性、透明性などに優れた液晶配向膜や発光ダイオード封止材、または低伝送損失の光導波路材料を提供することである。 An object of the present invention is to provide a novel polymer having a double-decker skeleton in the main chain, and a PSQ having an alicyclic acid anhydride group as a raw material. In particular, it is to provide a polyimide or epoxy resin that has both transparency and light resistance required for optoelectronic materials while maintaining heat resistance and mechanical strength by making the molecular chain as rigid as possible. . Specifically, for example, a low dielectric constant insulating film, a liquid crystal alignment film excellent in light resistance and transparency, a light emitting diode sealing material, or a low transmission loss optical waveguide material is provided.
本発明者らは、様々な有機ポリマー主鎖中にダブルデッカー骨格を導入し、構造制御されたかご型構造を含む有機−無機ハイブリッド材料を創製するという観点から鋭意研究した。その結果、従来知られている脂環式ポリイミドの透明性に着目し、脂環式酸無水物残基がダブルデッカー骨格に直結した新規酸無水物を合成した。さらに、この酸無水物とジアミン類との縮重合によって主鎖中にかご型ケイ素骨格が導入されたポリイミドが得られた。この酸無水物と種々のエポキシドとの架橋反応によってエポキシ樹脂を得ることにも成功した。そして、これらの重合体が、例えば、誘電特性、透明性、耐光性、耐熱性等に優れ、絶縁膜、液晶配向膜、発光ダイオードの封止剤、光導波路等の光電子材料に有用であることを見出し、本発明の完成に至った。 The present inventors have intensively studied from the viewpoint of introducing a double-decker skeleton into various organic polymer main chains and creating an organic-inorganic hybrid material including a cage-controlled structure. As a result, focusing on the transparency of the conventionally known alicyclic polyimide, a novel acid anhydride in which the alicyclic acid anhydride residue was directly linked to the double-decker skeleton was synthesized. Furthermore, a polyimide having a cage silicon skeleton introduced into the main chain was obtained by condensation polymerization of the acid anhydride and diamines. We have also succeeded in obtaining epoxy resins by cross-linking reaction between this acid anhydride and various epoxides. These polymers are excellent in dielectric properties, transparency, light resistance, heat resistance, etc., and are useful for optoelectronic materials such as insulating films, liquid crystal alignment films, light-emitting diode sealants, and optical waveguides. As a result, the present invention has been completed.
本発明の酸無水物は次の［１］項に示される。
［１］ 式（１）で示される酸無水物：
[1] An acid anhydride represented by the formula (1):
本発明の酸無水物を用いて得られる重合体は、主鎖に機械強度や耐熱性に優れた、剛直なかご型骨格を有する。しかも、ダブルデッカー骨格と酸無水物残基が直結しているので、耐熱性を低下させない。また、酸無水物に起因するポリイミドの透明性も芳香族系より優れている。さらに、ポリマー全体に占める有機ケイ素成分の含有量が多いので、有機残基だけで構成された同種のポリマーに比べて耐光性にも優れている。従って、従来の有機重合体に比べ、過酷な条件下で使用される層間絶縁膜やポリマー光導波路等の電子材料として有用である。 The polymer obtained using the acid anhydride of the present invention has a rigid cage skeleton excellent in mechanical strength and heat resistance in the main chain. Moreover, since the double decker skeleton and the acid anhydride residue are directly connected, the heat resistance is not lowered. Moreover, the transparency of the polyimide resulting from the acid anhydride is also superior to the aromatic type. Furthermore, since the content of the organosilicon component in the entire polymer is large, it is excellent in light resistance as compared with the same kind of polymer composed only of organic residues. Therefore, it is useful as an electronic material such as an interlayer insulating film and a polymer optical waveguide used under severe conditions as compared with conventional organic polymers.
最初に、本発明で用いる用語について説明する。「任意の」は、位置だけでなく個数についても任意に選択できることを意味する。任意の−ＣＨ２−が−Ｏ−で置き換えられてもよいと記述するときには、連続する複数の−ＣＨ２−が−Ｏ−で置き換えられる場合を含まない。任意のＡがＢまたはＣで置き換えられてもよいという表現は、任意のＡがＢで置き換えられる場合および任意のＡがＣで置き換えられる場合に加えて、任意のＡがＢで置き換えられると同時に、残りのＡのうちの任意のＡがＣで置き換えらる場合をも含むことを意味する。例えば、任意の−ＣＨ２−が−Ｏ−または−ＣＨ＝ＣＨ−で置き換えられてもよいアルキルには、アルキル、アルコキシ、アルコキシアルキル、アルケニル、アルケニルオキシ、アルコキシアルケニル、アルケニルオキシアルキル、およびアルケニルオキシアルケニルが含まれる。アルキル、アルケニル、アルキレンおよびアルケニレンは、いずれも直鎖の基であってよいし、分岐された基であってもよい。シクロアルキルは架橋環構造の基であってもよいし、そうでなくてもよい。式（１）で示される化合物を化合物（１）と略称することがある。他の式で示される化合物についても同じ簡略化法により表記することがある。実施例においては、電子天秤の表示データを質量単位であるｇ（グラム）を用いて示した。重量％や重量比はこのような数値に基づくデータである。 First, terms used in the present invention will be described. “Arbitrary” means that not only the position but also the number can be arbitrarily selected. The description that any —CH 2 — may be replaced by —O— does not include the case where a plurality of consecutive —CH 2 — are replaced by —O—. The expression that any A may be replaced by B or C means that any A is replaced by B in addition to any A being replaced by B and any A being replaced by C. , It means that any A in the remaining A is replaced by C. For example, alkyl in which any —CH 2 — may be replaced by —O— or —CH═CH— includes alkyl, alkoxy, alkoxyalkyl, alkenyl, alkenyloxy, alkoxyalkenyl, alkenyloxyalkyl, and alkenyloxy Alkenyl is included. Alkyl, alkenyl, alkylene and alkenylene may all be straight-chain groups or branched groups. Cycloalkyl may or may not be a bridged ring group. A compound represented by the formula (1) may be abbreviated as a compound (1). The compounds represented by other formulas may be represented by the same simplification method. In the examples, the display data of the electronic balance is shown using g (gram) which is a mass unit. Weight% and weight ratio are data based on such numerical values.
本発明は、前記の［１］項と下記の［２］〜［２３］項とで構成される。
［２］ Ｘのそれぞれが任意の水素が炭素数１〜４のアルキルで置き換えられてもよいフェニル、シクロヘキシル、および任意の水素が炭素数１〜４のアルキルで置き換えられてもよいフェニルと炭素数１〜５のアルキレンとで構成されるフェニルアルキルから独立して選択される基であり；Ｙが炭素数１〜８のアルキル、炭素数１〜８のフッ素化アルキル、炭素数５〜８のシクロアルキル、任意の水素が炭素数１〜４のアルキルで置き換えられてもよいフェニル、または任意の水素が炭素数１〜４のアルキルで置き換えられてもよいフェニルと炭素数１〜５のアルキレンとで構成されるフェニルアルキルであり；そして、炭素数１〜５のアルキレンにおいて、任意の−ＣＨ２−は−Ｏ−で置き換えられてもよい、［１］項に記載の酸無水物。
The present invention includes the above item [1] and the following items [2] to [23].
[2] Each of X is phenyl in which arbitrary hydrogen may be replaced with alkyl having 1 to 4 carbons, cyclohexyl, and phenyl in which arbitrary hydrogen may be replaced with alkyl having 1 to 4 carbons and carbon number A group independently selected from phenylalkyl composed of 1 to 5 alkylene; Y is alkyl having 1 to 8 carbon atoms, fluorinated alkyl having 1 to 8 carbon atoms, cyclohexane having 5 to 8 carbon atoms Alkyl, phenyl in which arbitrary hydrogen may be replaced by alkyl having 1 to 4 carbons, or phenyl in which arbitrary hydrogen may be replaced by alkyl having 1 to 4 carbons and alkylene having 1 to 5 carbons it is constituted phenylalkyl; and, in the alkylene having 1 to 5 carbon atoms, arbitrary -CH 2 - may be replaced by -O-, [1] acid anhydride according to claim
［３］ Ｘが任意の水素が炭素数１〜４のアルキルで置き換えられてもよいフェニル、シクロヘキシル、またはフェニルと炭素数１〜５のアルキレンとで構成されるフェニルアルキルであり；Ｙが炭素数１〜８のアルキル、炭素数１〜８のフッ素化アルキル、炭素数５〜８のシクロアルキル、任意の水素が炭素数１〜４のアルキルで置き換えられてもよいフェニル、またはフェニルと炭素数１〜５のアルキレンとで構成されるフェニルアルキルであり；そして、炭素数１〜５のアルキレンにおいて、任意の−ＣＨ２−は−Ｏ−で置き換えられてもよい、［１］項に記載の酸無水物。 [3] X is phenyl, cyclohexyl, or phenylalkyl composed of phenyl and alkylene having 1 to 5 carbons in which arbitrary hydrogen may be replaced by alkyl having 1 to 4 carbons; Y is carbon number 1 to 8 alkyl, fluorinated alkyl having 1 to 8 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, phenyl in which any hydrogen may be replaced by alkyl having 1 to 4 carbon atoms, or phenyl and 1 carbon atom An acid according to item [1], which is phenylalkyl composed of ˜5 alkylene; and in the alkylene having 1 to 5 carbon atoms, arbitrary —CH 2 — may be replaced by —O—. Anhydride.
［４］ Ｘがフェニル、シクロヘキシル、またはフェニルと炭素数１〜３のアルキレンとで構成されるフェニルアルキルであり；Ｙが炭素数１〜８のアルキル、炭素数１〜８のフッ素化アルキル、炭素数５〜８のシクロアルキル、任意の水素が炭素数１〜４のアルキルで置き換えられてもよいフェニル、またはフェニルと炭素数１〜３のアルキレンとで構成されるフェニルアルキルである、［１］項に記載の酸無水物。 [4] X is phenyl, cyclohexyl, or phenylalkyl composed of phenyl and alkylene having 1 to 3 carbon atoms; Y is alkyl having 1 to 8 carbon atoms, fluorinated alkyl having 1 to 8 carbon atoms, carbon A cycloalkyl having 5 to 8 carbon atoms, phenyl in which arbitrary hydrogen may be replaced by alkyl having 1 to 4 carbon atoms, or phenylalkyl composed of phenyl and alkylene having 1 to 3 carbon atoms, [1] The acid anhydride according to item.
［５］ Ｘがフェニルであり；Ｙが炭素数１〜８のアルキル、炭素数１〜８のフッ素化アルキル、シクロペンチル、シクロヘキシル、フェニル、ベンジル、またはフェニルエチルである、［１］項に記載の酸無水物。 [5] The paragraph [1], wherein X is phenyl; Y is alkyl having 1 to 8 carbons, fluorinated alkyl having 1 to 8 carbons, cyclopentyl, cyclohexyl, phenyl, benzyl, or phenylethyl. Acid anhydride.
［６］ ［１］項に記載の式（１）におけるＺが次に示す３価の基のいずれか１つである、［１］〜［５］のいずれか１項に記載の酸無水物：
ここに、環骨格との結合位置が固定されていない結合手は、Ｓｉ原子と結合する遊離原子価を示し、そして環骨格との結合位置が任意であることを示す。
[6] The acid anhydride according to any one of [1] to [5], wherein Z in the formula (1) according to the item [1] is any one of the following trivalent groups: :
Here, the bond in which the bonding position with the ring skeleton is not fixed indicates the free valence bonded to the Si atom, and the bonding position with the ring skeleton is arbitrary.
［７］ 式（１−１）で示される酸無水物：
［８］ ［１］〜［７］のいずれか１項に記載の酸無水物の少なくとも１つを原料として用いる縮重合反応によって得られる重合体。
［９］ ［１］〜［７］のいずれか１項に記載の酸無水物の少なくとも１つとジアミンとの縮重合反応によって得られるポリイミド。
［１０］ ［１］〜［７］のいずれか１項に記載の酸無水物の少なくとも１つを硬化剤として用いる架橋反応によって得られるエポキシ樹脂。
[8] A polymer obtained by a condensation polymerization reaction using at least one of the acid anhydrides according to any one of [1] to [7] as a raw material.
[9] A polyimide obtained by a polycondensation reaction between at least one of the acid anhydrides according to any one of [1] to [7] and a diamine.
[10] An epoxy resin obtained by a crosslinking reaction using at least one of the acid anhydrides according to any one of [1] to [7] as a curing agent.
［１１］ ［１０］項に記載のエポキシ樹脂を用いて得られる封止剤。
［１２］ ［１１］項に記載の封止剤を含有する発光素子。
[11] A sealant obtained using the epoxy resin according to the item [10].
[12] A light emitting device containing the sealing agent according to the item [11].
［１３］ ［９］または［１０］項に記載の重合体を用いて得られる薄膜。
［１４］ ［１３］項に記載の薄膜からなる絶縁膜。
［１５］ ［１３］項に記載の薄膜からなる保護膜。
［１６］ ［１３］項に記載の薄膜からなる液晶配向膜。
［１７］ ［１３］項に記載の薄膜からなる平坦化膜。
［１８］ ［１３］項に記載の薄膜からなる光導波路材料。
[13] A thin film obtained using the polymer described in the item [9] or [10].
[14] An insulating film comprising the thin film according to item [13].
[15] A protective film comprising the thin film according to the item [13].
[16] A liquid crystal alignment film comprising the thin film according to the item [13].
[17] A planarizing film comprising the thin film according to the item [13].
[18] An optical waveguide material comprising the thin film according to the item [13].
［１９］ ［１４］項に記載の絶縁膜を含有する電気的固体装置。
［２０］ ［１５］項に記載の保護膜を含有する電気的固体装置。
［２１］ ［１６］項に記載の液晶配向膜を含有する液晶表示素子。
［２２］ ［１７］項に記載の平坦化膜を含有する液晶表示素子。
［２３］ ［１８］項に記載の光導波路材料を含有する光導波路。
[19] An electrical solid device comprising the insulating film as described in the item [14].
[20] An electrical solid device containing the protective film according to the item [15].
[21] A liquid crystal display device comprising the liquid crystal alignment film according to item [16].
[22] A liquid crystal display device comprising the planarizing film according to the item [17].
[23] An optical waveguide containing the optical waveguide material according to the item [18].
本発明の酸無水物は式（１）で示される。即ち、本発明の酸無水物は、酸無水物基を有する脂環式構造の基または酸無水物基と共に環を構成する飽和脂肪族基がシルセスキオキサン骨格に直結した構造を有する化合物である。
式（１）において、Ｘのそれぞれは炭素数１〜４０のアルキル、炭素数４〜１０のシクロアルキル、任意の水素がハロゲンまたは炭素数１〜２０のアルキルで置き換えられてもよいアリール、および任意の水素がハロゲンまたは炭素数１〜２０のアルキルで置き換えられてもよいアリールと炭素数１〜８のアルキレンとで構成されるアリールアルキルから独立して選択される基である。８個のＸは２つ以上の異なる基で構成されてもよいが、すべてのＸが同一の基であることが好ましい。 In Formula (1), each X is alkyl having 1 to 40 carbon atoms, cycloalkyl having 4 to 10 carbon atoms, aryl in which any hydrogen may be replaced by halogen or alkyl having 1 to 20 carbon atoms, and any Are independently selected from arylalkyl composed of halogen or aryl optionally substituted with alkyl having 1 to 20 carbons and alkylene having 1 to 8 carbons. Eight Xs may be composed of two or more different groups, but it is preferable that all Xs are the same group.
ＸまたはＹが炭素数１〜４０のアルキルであるとき、任意の水素はフッ素で置き換えられてもよく、そして任意の−ＣＨ２−は−Ｏ−または−ＣＨ＝ＣＨ−で置き換えられてもよい。このような基の例は、アルキル、フッ素化アルキル、アルコキシアルキル、アルケニル、アルケニルオキシアルキルなどである。このようなＸの具体例として、メチル、エチル、ｔ−ブチル、オクチル、デシル、３，３，３−トリフルオロプロピル、トリデカフルオロ−１，１，２，２−テトラヒドロオクチル、３−メトキシプロピル、３−ヘプタフルオロイソプロポキシプロピル、エテニル、３−ブテニル、アリルオキシウンデシルなどが挙げられる。 When X or Y is alkyl having 1 to 40 carbon atoms, any hydrogen may be replaced with fluorine, and any —CH 2 — may be replaced with —O— or —CH═CH—. . Examples of such groups are alkyl, fluorinated alkyl, alkoxyalkyl, alkenyl, alkenyloxyalkyl and the like. Specific examples of such X include methyl, ethyl, t-butyl, octyl, decyl, 3,3,3-trifluoropropyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, 3-methoxypropyl. , 3-heptafluoroisopropoxypropyl, ethenyl, 3-butenyl, allyloxyundecyl and the like.
シクロアルキルの例は、シクロブチル、シクロペンチル、シクロヘキシル、シクロヘプチル、シクロオクチルおよびデカリルであり、シクロヘキシルが好ましい。 Examples of cycloalkyl are cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and decalyl, with cyclohexyl being preferred.
ＸまたはＹがアリールであるとき、環の任意の水素はハロゲンまたは炭素数１〜２０のアルキルで置き換えられてもよい。そしてこの炭素数１〜２０のアルキルにおいて、任意の水素はフッ素で置き換えられてもよく、そして任意の−ＣＨ２−は−Ｏ−で置き換えられてもよい。このような基の例は、フェニル、ナフチル、アントニル、フルオレニル、４−フルオロフェニル、４−クロロフェニル、４−ブロモフェニル、４−メチルフェニル、４−エチルフェニル、４−ブチルフェニル、４−オクチルフェニル、４−デシルフェニル、２，４−ジメチルフェニル、４−（１，１−ジメチルエチル）フェニル、４−（２−エチルヘキシル）フェニル、４−メトキシフェニル、４−エトキシフェニル、４−ブトキシフェニル、４−ヘプチルオキシフェニル、およびメトキシエチルフェニルである。 When X or Y is aryl, any hydrogen in the ring may be replaced with halogen or alkyl having 1 to 20 carbons. In the alkyl having 1 to 20 carbon atoms, arbitrary hydrogen may be replaced with fluorine, and arbitrary —CH 2 — may be replaced with —O—. Examples of such groups are phenyl, naphthyl, anthonyl, fluorenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-methylphenyl, 4-ethylphenyl, 4-butylphenyl, 4-octylphenyl, 4-decylphenyl, 2,4-dimethylphenyl, 4- (1,1-dimethylethyl) phenyl, 4- (2-ethylhexyl) phenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 4-butoxyphenyl, 4- Heptyloxyphenyl, and methoxyethylphenyl.
ＸまたはＹが環の任意の水素がハロゲンまたは炭素数１〜２０のアルキルで置き換えられてもよいアリールと炭素数１〜８のアルキレンとで構成されるアリールアルキルであるとき、この炭素数１〜２０のアルキルにおいて、任意の水素はフッ素で置き換えられてもよく、そして任意の−ＣＨ２−は−Ｏ−で置き換えられてもよい。このようなアリールの例は前記と同様である。そして、炭素数１〜８のアルキレンにおける任意の−ＣＨ２−は−Ｏ−で置き換えられてもよい。 When X or Y is arylalkyl in which any hydrogen in the ring is halogen or aryl optionally substituted with alkyl having 1 to 20 carbons and alkylene having 1 to 8 carbons, In the 20 alkyls, any hydrogen may be replaced with fluorine and any —CH 2 — may be replaced with —O—. Examples of such aryl are the same as described above. Then, any -CH 2 - in the alkylene having 1 to 8 carbon atoms - may be replaced by -O-.
式（１）における２つのＹは同じ基であるが、Ｙの選択範囲内の異なる基であっても構わない。２つのＹが異なる基である化合物の場合には、製造コストが嵩むという欠点があるだけであり、物性に大きな違いがあるわけではない。 Two Y in the formula (1) are the same group, but they may be different groups within the selection range of Y. In the case of a compound in which two Ys are different groups, there is only a drawback that the production cost increases, and there is no significant difference in physical properties.
式（１）におけるＸとＹに関して好ましい組み合わせは次の通りである。即ち、Ｘのそれぞれが任意の水素が炭素数１〜４のアルキルで置き換えられてもよいフェニル、シクロヘキシル、および任意の水素が炭素数１〜４のアルキルで置き換えられてもよいフェニルと炭素数１〜５のアルキレンとで構成されるフェニルアルキルから独立して選択される基であり、そしてＹは、炭素数１〜８のアルキル、炭素数１〜８のフッ素化アルキル、炭素数５〜８のシクロアルキル、任意の水素が炭素数１〜４のアルキルで置き換えられてもよいフェニル、または任意の水素が炭素数１〜４のアルキルで置き換えられてもよいフェニルと炭素数１〜５のアルキレンとで構成されるフェニルアルキルである。そして、この炭素数１〜５のアルキレンにおける任意の−ＣＨ２−は−Ｏ−で置き換えられてもよい。 Preferred combinations for X and Y in formula (1) are as follows. That is, each of X is phenyl and cyclohexyl in which arbitrary hydrogen may be replaced with alkyl having 1 to 4 carbons, and phenyl and carbon having 1 carbon in which arbitrary hydrogen may be replaced with alkyl having 1 to 4 carbons Is a group independently selected from phenylalkyl composed of ˜5 alkylene, and Y is alkyl having 1 to 8 carbons, fluorinated alkyl having 1 to 8 carbons, 5 to 8 carbons Cycloalkyl, phenyl in which any hydrogen may be replaced with alkyl having 1 to 4 carbons, or phenyl and any hydrogen in which any hydrogen may be replaced with alkyl having 1 to 4 carbons and alkylene having 1 to 5 carbons It is a phenylalkyl composed of Then, any -CH 2 - in the alkylene of 1 to 5 carbon atoms - may be replaced by -O-.
式（１）におけるＸとＹに関してより好ましい組み合わせは次の通りである。即ち、Ｘが任意の水素が炭素数１〜４のアルキルで置き換えられてもよいフェニル、シクロヘキシル、またはフェニルと炭素数１〜５のアルキレンとで構成されるフェニルアルキルであり、そしてＹは、炭素数１〜８のアルキル、炭素数１〜８のフッ素化アルキル、炭素数５〜８のシクロアルキル、任意の水素が炭素数１〜４のアルキルで置き換えられてもよいフェニル、またはフェニルと炭素数１〜５のアルキレンとで構成されるフェニルアルキルである。そして、この炭素数１〜５のアルキレンにおける任意の−ＣＨ２−は−Ｏ−で置き換えられてもよい。このようなフェニルアルキルの例は、ベンジル、フェニルエチル、フェニルプロピル、フェノキシプロピル、およびベンジルオキシプロピルである。 More preferable combinations for X and Y in the formula (1) are as follows. That is, X is phenyl, cyclohexyl, or phenylalkyl composed of phenyl and alkylene having 1 to 5 carbons in which arbitrary hydrogen may be replaced by alkyl having 1 to 4 carbons, and Y is carbon Alkyl having 1 to 8 carbon atoms, fluorinated alkyl having 1 to 8 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, phenyl in which any hydrogen may be replaced by alkyl having 1 to 4 carbon atoms, or phenyl and carbon number It is phenylalkyl composed of 1 to 5 alkylene. Then, any -CH 2 - in the alkylene of 1 to 5 carbon atoms - may be replaced by -O-. Examples of such phenylalkyl are benzyl, phenylethyl, phenylpropyl, phenoxypropyl, and benzyloxypropyl.
式（１）におけるＸとＹに関してさらに好ましい組み合わせは次の通りである。即ち、Ｘがフェニル、シクロヘキシル、またはフェニルと炭素数１〜３のアルキレンとで構成されるフェニルアルキルであり、そしてＹは、炭素数１〜８のアルキル、炭素数１〜８のフッ素化アルキル、炭素数５〜８のシクロアルキル、任意の水素が炭素数１〜４のアルキルで置き換えられてもよいフェニル、またはフェニルと炭素数１〜３のアルキレンとで構成されるフェニルアルキルである。 Further preferred combinations of X and Y in the formula (1) are as follows. That is, X is phenyl, cyclohexyl, or phenylalkyl composed of phenyl and alkylene having 1 to 3 carbon atoms, and Y is alkyl having 1 to 8 carbon atoms, fluorinated alkyl having 1 to 8 carbon atoms, A cycloalkyl having 5 to 8 carbon atoms, phenyl in which arbitrary hydrogen may be replaced by alkyl having 1 to 4 carbon atoms, or phenylalkyl composed of phenyl and alkylene having 1 to 3 carbon atoms.
式（１）におけるＸとＹに関して特に好ましい組み合わせは次の通りである。即ち、Ｘがフェニルであり、そしてＹは、炭素数１〜８のアルキル、炭素数１〜８のフッ素化アルキル、シクロペンチル、シクロヘキシル、フェニル、ベンジル、またはフェニルエチルである。 Particularly preferred combinations for X and Y in formula (1) are as follows. That is, X is phenyl and Y is alkyl having 1 to 8 carbons, fluorinated alkyl having 1 to 8 carbons, cyclopentyl, cyclohexyl, phenyl, benzyl, or phenylethyl.
式（１）におけるＺは、炭素数４〜２０の３価の脂環式基、または酸無水物基と共に環を形成する炭素数２〜１０の３価の飽和脂肪族基である。この脂環式基は架橋構造の環であってもよく、１つの−ＣＨ２−は−Ｏ−で置き換えられてもよい。Ｚの好ましい例を次に示す。
これらの基において、環骨格との結合位置が固定されていない結合手は、Ｓｉ原子と結合する遊離原子価を示す。そしてこの遊離原子価の環骨格における位置は任意である。
Z in Formula (1) is a trivalent alicyclic group having 4 to 20 carbon atoms, or a trivalent saturated aliphatic group having 2 to 10 carbon atoms that forms a ring together with an acid anhydride group. The alicyclic group may be a ring having a crosslinked structure, and one —CH 2 — may be replaced by —O—. Preferred examples of Z are shown below.
In these groups, the bond in which the bonding position with the ring skeleton is not fixed indicates a free valence bonded to the Si atom. And the position in this free valence ring skeleton is arbitrary.
本発明の酸無水物は、通常の有機化学的手法で容易に合成が可能であるが、式（１−０）で示されるダブルデッカー型ＰＳＱと酸無水物基を有するジクロロシラン誘導体との閉環反応（エンドキャッピング反応）によって合成するのが最も一般的である。ダブルデッカー型ＰＳＱは、トリアルコキシシランを水酸化ナトリウム存在下加水分解重縮合することによって得ることができる。式（１）の化合物の一般的合成法を以下に示す。
式（１−０）の化合物を、ケイ素−水素結合を有するジクロロシラン誘導体で一旦閉環した後、環内に不飽和結合を有する酸無水物とヒドロシリル化反応させて合成する方法も有用である。反応例を以下に示す。
このようにして得られる酸無水物の少なくとも１つを原料として用い、縮重合反応または架橋反応を行うことにより本発明の重合体を得ることができる。本発明の重合体の好ましい例は、本発明の酸無水物の少なくとも１つとジアミンとの縮重合反応によって得られるポリイミドである。このとき、得られる重合体の透明性、機械強度、耐熱性などに悪影響を与えない範囲であれば、他のテトラカルボン酸二無水物を併用してもよい。これらの物性に悪影響を与えない範囲であれば、ジカルボン酸無水物、ジカルボン酸ジクロリドなどのジカルボン酸誘導体を併用してポリアミドイミドとしてもよい。なお、ジアミンは２種以上を混合して用いてもよい。 The polymer of the present invention can be obtained by performing a condensation polymerization reaction or a crosslinking reaction using at least one of the acid anhydrides thus obtained as a raw material. A preferred example of the polymer of the present invention is a polyimide obtained by a polycondensation reaction between at least one of the acid anhydride of the present invention and a diamine. At this time, other tetracarboxylic dianhydrides may be used in combination as long as they do not adversely affect the transparency, mechanical strength, heat resistance and the like of the resulting polymer. As long as these properties are not adversely affected, dicarboxylic acid derivatives such as dicarboxylic acid anhydride and dicarboxylic acid dichloride may be used in combination to form polyamideimide. Two or more diamines may be mixed and used.
反応例を以下に示す。Ｑはジアミン残基である。
本発明の酸無水物と併用することができるテトラカルボン酸二無水物の例は、シクロブタンテトラカルボン酸二無水物、シクロペンタンテトラカルボン酸二無水物、シクロヘキサンテトラカルボン酸二無水物、ジシクロヘキサンテトラカルボン酸二無水物、ジシクロペンタンテトラカルボン酸二無水物、ビス（ジカルボキシシクロヘキシル）エーテル二無水物、ビス（ジカルボキシシクロヘキシル）スルホン二無水物、ビス（ジカルボキシシクロヘキシル）メタン二無水物、ピロメリット酸二無水物、３，３'，４，４'−ビフェニルテトラカルボン酸二無水物、２、２'，３，３'−ビフェニルテトラカルボン酸二無水物、２，３，３'，４'−ビフェニルテトラカルボン酸二無水物、３，３'，４，４'−ベンゾフェノンテトラカルボン酸二無水物、２，３，３'，４'−ベンゾフェノンテトラカルボン酸二無水物、２，２'，３，３'−ベンゾフェノンテトラカルボン酸二無水物、ビス（３，４−ジカルボキシフェニル）エーテル二無水物、ビス（３，４−ジカルボキシフェニル）スルホン二無水物、１，２，５，６−ナフタレンテトラカルボン酸二無水物、２，３，６，７−ナフタレンテトラカルボン酸二無水物、ビス（ジカルボキシフェニル）メタン二無水物、および４，４'−（ヘキサフルオロイソプロピリデン）ジフタル酸二無水物である。 Examples of tetracarboxylic dianhydrides that can be used in combination with the acid anhydrides of the present invention include cyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane tetracarboxylic dianhydride, dicyclohexane tetra Carboxylic dianhydride, dicyclopentanetetracarboxylic dianhydride, bis (dicarboxycyclohexyl) ether dianhydride, bis (dicarboxycyclohexyl) sulfone dianhydride, bis (dicarboxycyclohexyl) methane dianhydride, pyro Merit acid dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4 '-Biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride Bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, bis ( Dicarboxyphenyl) methane dianhydride and 4,4 ′-(hexafluoroisopropylidene) diphthalic dianhydride.
これらの中の好ましい例は、シクロブタンテトラカルボン酸二無水物、ビス（ジカルボキシシクロヘキシル）メタン二無水物、ピロメリット酸二無水物、３，３'，４，４'−ビフェニルテトラカルボン酸二無水物、３，３'，４，４'−ベンゾフェノンテトラカルボン酸二無水物、ビス（３，４−ジカルボキシフェニル）エーテル二無水物、ビス（３，４−ジカルボキシフェニル）スルホン二無水物、および４，４'−（ヘキサフルオロイソプロピリデン）ジフタル酸二無水物である。これらの化合物には異性体を含むものもあるが、これらの異性体混合物であってもかまわない。これらの２種以上の化合物を併用してもよい。 Preferred examples among these include cyclobutanetetracarboxylic dianhydride, bis (dicarboxycyclohexyl) methane dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, And 4,4 ′-(hexafluoroisopropylidene) diphthalic dianhydride. Some of these compounds include isomers, but a mixture of these isomers may be used. You may use together these 2 or more types of compounds.
本発明のポリイミドを合成する場合において、ジアミンの残基の構造は特に限定されない。ジアミン残基の好ましい例を次に挙げる。なお、下記式中に記載のＸおよびＹの意味は前記の通りである。
上記のジアミン残基の中で特に好ましい例を次に示す。
本発明の重合体において、その主鎖がエポキシ樹脂である重合体は、分子中に式（１）で示される骨格を有する酸無水物と、各種エポキシ化合物との重付加反応で合成することができる。ここで、本発明の酸無水物はエポキシドの硬化剤として作用している。この時、エポキシ樹脂特性の多様性を発揮させるために、具体的にはビスフェノールＡのジグリシジルエーテル系、グリシジルエステル系、グリシジルジアミン系化合物、または環状脂肪族エポキシド等を用いることができる。 In the polymer of the present invention, the polymer whose main chain is an epoxy resin can be synthesized by a polyaddition reaction between an acid anhydride having a skeleton represented by the formula (1) in the molecule and various epoxy compounds. it can. Here, the acid anhydride of the present invention acts as a curing agent for epoxides. At this time, specifically, diglycidyl ether-based, glycidyl ester-based, glycidyldiamine-based compounds, or cyclic aliphatic epoxides of bisphenol A can be used in order to exhibit a variety of epoxy resin characteristics.
本発明の重合体において、重合反応、溶液保存、および薄膜形成時に用いる溶剤は、重合反応を阻害することなく、モノマーとポリマーの溶解性に優れたものであれば特に制限されない。このような溶剤の例は、ベンゼン、トルエン、キシレン、メシチレン、シクロペンタノン、シクロヘキサノン、Ｎ−メチル−２−ピロリドン、ホルムアミド、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルイミダゾリジノン、ジメチルスルホキシド、ヘキサメチルリン酸トリアミド、スルホラン、γ−ブチロラクトン、テトラヒドロフラン、ジオキサン、ジクロロメタン、クロロホルム、１，２−ジクロロエタンが好ましい。さらに好ましくは、シクロヘキサノン、Ｎ−メチル−２−ピロリドン、Ｎ，Ｎ−ジメチルアセトアミド、およびテトラヒドロフランである。これらの溶剤は、単独で用いても複数混合して使用してもよい。 In the polymer of the present invention, the solvent used for the polymerization reaction, solution storage, and thin film formation is not particularly limited as long as it is excellent in solubility of the monomer and the polymer without inhibiting the polymerization reaction. Examples of such solvents are benzene, toluene, xylene, mesitylene, cyclopentanone, cyclohexanone, N-methyl-2-pyrrolidone, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, N, N- Dimethylimidazolidinone, dimethyl sulfoxide, hexamethylphosphoric triamide, sulfolane, γ-butyrolactone, tetrahydrofuran, dioxane, dichloromethane, chloroform, 1,2-dichloroethane are preferred. More preferred are cyclohexanone, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, and tetrahydrofuran. These solvents may be used alone or in combination.
さらに必要により、塗布性改善などの目的で表面張力の低い溶剤を併用してもよい。このような溶剤の例は、乳酸アルキル、３−メチル−３−メトキシブタノール、テトラリン、イソホロン、エチレングリコールモノアルキルエーテル（エチレングリコールモノブチルエーテルなど）、ジエチレングリコールモノアルキルエーテル（ジエチレングリコールモノエチルエーテルなど）、エチレングリコールモノアルキルアセテート、エチレングリコールモノフェニルアセテート、トリエチレングリコールモノアルキルエーテル、プロピレングリコールモノアルキルエーテル（プロピレングリコールモノブチルエーテルなど）、およびマロン酸ジアルキル（マロン酸ジエチルなど）である。これらの溶剤は、先の良溶剤に対して貧溶剤的なものが多い。従って、溶解成分が析出しない程度の量を添加することが好ましい。 Further, if necessary, a solvent having a low surface tension may be used in combination for the purpose of improving coating properties. Examples of such solvents are alkyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monoalkyl ether (such as ethylene glycol monobutyl ether), diethylene glycol monoalkyl ether (such as diethylene glycol monoethyl ether), ethylene Glycol monoalkyl acetate, ethylene glycol monophenyl acetate, triethylene glycol monoalkyl ether, propylene glycol monoalkyl ether (such as propylene glycol monobutyl ether), and dialkyl malonate (such as diethyl malonate). Many of these solvents are poor solvents with respect to the previous good solvent. Therefore, it is preferable to add such an amount that the dissolved component does not precipitate.
さらに、塗布性を改良する等の目的で用いられる界面活性剤や、帯電防止の目的等で用いられる帯電防止剤を添加することも可能である。あるいは、さらに基板との密着性を向上させるために、シランカップリング剤やチタン系のカップリング剤を配合することも可能である。 Furthermore, it is also possible to add a surfactant used for the purpose of improving coating properties and an antistatic agent used for the purpose of antistatic. Alternatively, in order to further improve the adhesion to the substrate, it is possible to add a silane coupling agent or a titanium-based coupling agent.
好ましいシランカップリング剤として、ビニルトリメトキシシラン、ビニルトリエトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルメチルジメトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、３−アミノプロピルトリメトキシシラン、３−グリシドキシプロピルトリメトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、３−クロロプロピルトリメトキシシラン、３−メタクリロキシプロピルトリメトキシシラン、３−メルカプトプロピルトリメトキシシランを挙げることができる。 As preferred silane coupling agents, vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropyltrimethoxysilane, Examples include 3-methacryloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane.
上述したような溶剤で本発明の重合体を溶解し、これを基板に塗布することによって薄膜を形成することができる。重合体溶液を薄膜を形成させる基板へ塗布する方法としては、通常使用されている方法が使用可能である。例えば、スピンナー法、印刷法、ディッピング法、滴下法などが使用できる。塗布の際、オリゴマー溶液の溶剤組成、濃度は重合時と同一でもよいが、反応溶剤を減圧濃縮等にて一旦除去した後、最適な濃度や溶剤組成に調整してから塗布しても全く問題はない。基板としては、ガラス基板、プラスチック基板、またはフィルム状基板などを用いることができる。 A thin film can be formed by dissolving the polymer of the present invention in a solvent as described above and applying it to a substrate. As a method for applying the polymer solution to a substrate on which a thin film is to be formed, a commonly used method can be used. For example, a spinner method, a printing method, a dipping method, a dropping method, or the like can be used. During application, the solvent composition and concentration of the oligomer solution may be the same as during polymerization, but once the reaction solvent is removed by concentration under reduced pressure, etc., it is completely problematic to apply after adjusting to the optimal concentration and solvent composition. There is no. As the substrate, a glass substrate, a plastic substrate, a film substrate, or the like can be used.
塗布後の溶剤の乾燥のための加熱処理などにおいても、通常の絶縁膜、保護膜、液晶配向膜、光導波路形成で使用している手法と同様な方法で実施することが可能である。例えば、オ−ブン、ホットプレ−ト、赤外炉中などが使用できる。溶液を塗布した後は、比較的低温で溶剤を蒸発させた後、１００〜５００℃程度の温度で、好ましくは１５０〜４５０℃で加熱処理することが好ましい。加熱温度は一定でも段階的に昇温してもよい。加熱時間は重合体の種類によって異なるが、１０〜１８０分程度が好ましく、さらに好ましくは約３０〜９０分である。なお、本加熱処理においては空気中、窒素雰囲気もしくは減圧条件下のいずれで行ってもよい。このようにして形成された薄膜は絶縁膜、保護膜、液晶配向膜、平坦化膜などとして有用である。膜のサイズや厚さは用途に応じて適宜設定することができる。 Also in the heat treatment for drying the solvent after the application, etc., it is possible to carry out by the same method as that used in the usual insulating film, protective film, liquid crystal alignment film, and optical waveguide formation. For example, an oven, a hot plate, or an infrared furnace can be used. After applying the solution, it is preferable to evaporate the solvent at a relatively low temperature and then heat-treat at a temperature of about 100 to 500 ° C, preferably 150 to 450 ° C. The heating temperature may be constant or increased in steps. Although heating time changes with kinds of polymer, about 10 to 180 minutes are preferable, More preferably, it is about 30 to 90 minutes. Note that this heat treatment may be performed in air, in a nitrogen atmosphere, or under reduced pressure. The thin film thus formed is useful as an insulating film, a protective film, a liquid crystal alignment film, a planarizing film, and the like. The size and thickness of the film can be appropriately set according to the application.
絶縁膜は、ＬＳＩ内部の多層配線構造において、電気を通す金属配線とそれらを電気的に絶縁する機能を有する膜などを意味する。保護膜は、ＬＳＩ多層配線構造の最上部に形成され、配線内部を外部からの汚染等から保護する機能を有する膜などを意味する。本発明の絶縁膜及び保護膜は、半導体などの電気的固定装置の製造に好適に用いられる。 The insulating film means a metal wiring that conducts electricity and a film having a function of electrically insulating them in a multilayer wiring structure inside the LSI. The protective film means a film formed on the uppermost part of the LSI multilayer wiring structure and having a function of protecting the inside of the wiring from contamination from the outside. The insulating film and protective film of the present invention are suitably used for manufacturing an electrical fixing device such as a semiconductor.
平坦化膜は、凹凸面を持った物体をコーティングすることにより、その表面を平坦にさせる膜などを意味する。液晶配向膜は、液晶表示素子内部において液晶分子の一軸配向性と、界面におけるプレチルト角を発現させる機能を有する膜などを意味する。本発明の平坦化膜および液晶配向膜は、液晶表示素子の製造に好適に用いられる。 The flattened film means a film that flattens the surface by coating an object having an uneven surface. The liquid crystal alignment film means a film having a function of developing uniaxial alignment properties of liquid crystal molecules and a pretilt angle at the interface inside the liquid crystal display element. The planarization film and the liquid crystal alignment film of the present invention are suitably used for manufacturing a liquid crystal display element.
本発明の重合体を光導波路材料として用いることもできる。光導波路材料は、光ファイバーや光配線等の光機能素子において、光信号を特定の領域に閉じこめて入射端から出射端に導く機能を有する材料などを意味する。 The polymer of the present invention can also be used as an optical waveguide material. The optical waveguide material means a material having a function of guiding an optical signal from an incident end to an output end in an optical functional element such as an optical fiber or an optical wiring.
光導波路は、公知の方法（特開２００５−０１０７７０号公報、特開２００５−０２９６５２号公報、特開２００４−１８２９０９号公報など）に基づいて作製することができる。例えば、以下のような経路で作製される。まず、光学クラッド材用として用いられる重合体を基板上に塗布し、膜を形成した後、光学コア材用の重合体を塗布し、得られた塗布層上にエッチングマスクをマウントし、以下フォトリソグラフィーの手法により導波路パターンに加工する。エッチングマスクの材料としては、有機フォトレジストあるいは金属等が用いられる。次に、エッチングマスク越しに光学コア層を反応性イオンエッチングすることにより、所望の導波路パターンを形成することができる。この方法は、特にシングルモードタイプの光導波路の作製に有効である。特開平９−３２９７２１号公報には、光導波路型縮小イメージセンサーに用いるための光導波路の作製方法が記載されており、本発明の重合体はこのような光導波路の調製にも適している。 The optical waveguide can be manufactured based on a known method (JP 2005-010770 A, JP 2005-029652 A, JP 2004-182909 A, etc.). For example, it is produced by the following route. First, a polymer used for an optical cladding material is coated on a substrate to form a film, then a polymer for an optical core material is coated, an etching mask is mounted on the obtained coating layer, A waveguide pattern is processed by lithography. As a material for the etching mask, an organic photoresist or a metal is used. Next, a desired waveguide pattern can be formed by reactive ion etching of the optical core layer through an etching mask. This method is particularly effective for manufacturing a single mode type optical waveguide. Japanese Patent Application Laid-Open No. 9-329721 describes a method for producing an optical waveguide for use in an optical waveguide reduced image sensor, and the polymer of the present invention is also suitable for the preparation of such an optical waveguide.
以下、実施例により本発明をさらに詳しく説明するが、本発明はこれら実施例によって限定されない。実施例で得られた化合物の物性は以下の方法で測定した。
＜プロトンＮＭＲスペクトル（1Ｈ−ＮＭＲ）＞
日本電子株式会社製ＪＮＭ−ＧＳＸ４００を使用し、４００ＭＨｚで溶剤にクロロホルム−ｄを用い、内部標準物質にテトラメチルシランを用いて室温で測定した。
＜シリコンＮＭＲスペクトル（29Ｓｉ−ＮＭＲ）＞
日本電子株式会社製ＪＮＭ−ＧＳＸ４００を使用し、７９ＭＨｚで溶剤にクロロホルム−ｄを用い、内部標準物質にテトラメチルシランを用いて室温で測定した。
＜熱分解温度＞
セイコー電子工業社製、ＴＧ／ＤＴＡ−２２０型を用い、空気中で毎分１０℃の昇温速度で測定し、５％重量減少を示した点を分解温度とした。
＜ガラス転移温度＞
セイコー電子工業社製ＤＳＣ−２００型を用い毎分５℃の昇温速度で測定した。なお、以下の実施例では、容量を示す単位であるミリリットルを記号ｍＬで表記する。また、電子天秤の表示データを読み取った値を質量単位ｇを用いて示した。
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these Examples. The physical properties of the compounds obtained in the examples were measured by the following methods.
<Proton NMR spectra (1 H-NMR)>
JNM-GSX400 manufactured by JEOL Ltd. was used, and measurement was performed at room temperature using chloroform-d as a solvent at 400 MHz and tetramethylsilane as an internal standard substance.
<Silicon NMR spectra (29 Si-NMR)>
JNM-GSX400 manufactured by JEOL Ltd. was used, and measurement was performed at room temperature using chloroform-d as a solvent at 79 MHz and tetramethylsilane as an internal standard substance.
<Thermal decomposition temperature>
Using a TG / DTA-220 model manufactured by Seiko Denshi Kogyo Co., Ltd., the temperature was measured in air at a heating rate of 10 ° C. per minute, and the point showing 5% weight loss was defined as the decomposition temperature.
<Glass transition temperature>
The measurement was performed at a rate of temperature increase of 5 ° C. per minute using a DSC-200 type manufactured by Seiko Electronics Industry. In the following examples, milliliter, which is a unit indicating capacity, is expressed by the symbol mL. Moreover, the value which read the display data of the electronic balance was shown using the mass unit g.
＜化合物（１−１）（式（１）において、全てのＸがフェニルであり、Ｙがメチルであり、Ｚがノルボルニルである酸無水物）の合成＞
窒素ライン、冷却管、撹拌磁子、温度計を２００ｍＬ−三ツ口フラスコに備え、特許文献１に記載の方法で合成した化合物（ｃ）を１１．５３ｇ（０．０１ｍｏｌ）、５−ノルボルネン−２，３−ジカルボン酸無水物３．２８ｇ（０．０２ｍｏｌ）をとり、モノクロロベンゼン５０ｍＬに懸濁、撹拌した。窒素気流下、撹拌しながら８０℃に加熱し、市販のＫａｒｓｔｅｄｔ触媒１０滴を一度に加えた。８０℃で１時間撹拌後、温度を１３０〜１４０℃に上げて６時間撹拌後、室温まで冷却した。反応液に活性炭を少量加え、室温で３０分撹拌後セライトろ過し、ろ液を減圧濃縮した。得られた白色ペースト状物質をヘキサン／酢酸エチル混合溶剤中で撹拌し、スラリー状態になったところでろ過器を用いて固体を捕集した。捕集した固体は、減圧乾燥後ＮＭＲで化学構造を確認した。ろ液は再度濃縮してこの固体捕集操作を行い、固体が得られなくなるまでこれらの一連の操作を繰り返した。白色固体の化合物（１−１）を最終的に８．００ｇ（５．４ｍｍｏｌ）得た。収率５４％であった。
1Ｈ−ＮＭＲ（ＣＤＣｌ３）；δ＝０．３０（ｓ，６Ｈ）, ０．８６（ｔ，２Ｈ），１．３３（ｄ，２Ｈ），１．６０（ｔ，４Ｈ），１．７５〜１．８３（ｍ，４Ｈ），２．８０（ｄ，３Ｈ），３．２２〜３．２９（ｍ，３Ｈ），７．２１〜７．５１（ｍ，４０Ｈ）
29Ｓｉ−ＮＭＲ（ＣＤＣｌ３）；δ＝−７９．３１，−７９．１３，−７９．０７，−７８．９８，−７８．２１，−７８．１２，−２２．４３
ＮＭＲ分析の結果、この化合物はダブルデッカー骨格由来のシス−トランス体に加えて、ヒドロシリル化に伴いノルボルネン骨格上に不斉炭素原子が新たに生成するので、立体化学的に複雑な混合物であった。
A nitrogen line, a condenser tube, a stirring magnet, and a thermometer were provided in a 200 mL three-necked flask, and 11.53 g (0.01 mol) of compound (c) synthesized by the method described in Patent Document 1, 5-norbornene-2, 3.28 g (0.02 mol) of 3-dicarboxylic anhydride was taken and suspended in 50 mL of monochlorobenzene and stirred. The mixture was heated to 80 ° C. with stirring under a nitrogen stream, and 10 drops of a commercially available Karstedt catalyst were added all at once. After stirring at 80 ° C. for 1 hour, the temperature was raised to 130 to 140 ° C., stirred for 6 hours, and then cooled to room temperature. A small amount of activated carbon was added to the reaction solution, and the mixture was stirred at room temperature for 30 minutes, filtered through celite, and the filtrate was concentrated under reduced pressure. The obtained white paste-like substance was stirred in a mixed solvent of hexane / ethyl acetate, and when it was in a slurry state, a solid was collected using a filter. The collected solid was confirmed for its chemical structure by NMR after drying under reduced pressure. The filtrate was concentrated again and this solid collection operation was performed. These series of operations were repeated until no solid was obtained. The compound (1-1) of white solid was finally obtained 8.00g (5.4mmol). The yield was 54%.
1 H-NMR (CDCl 3 ); δ = 0.30 (s, 6H), 0.86 (t, 2H), 1.33 (d, 2H), 1.60 (t, 4H), 1.75 ˜1.83 (m, 4H), 2.80 (d, 3H), 3.22 to 3.29 (m, 3H), 7.21 to 7.51 (m, 40H)
29 Si-NMR (CDCl 3 ); δ = −79.31, −79.13, −79.07, −78.98, −78.21, −78.12, −22.43
As a result of NMR analysis, in addition to the cis-trans isomer derived from the double-decker skeleton, this compound was a stereochemically complex mixture because a new asymmetric carbon atom was formed on the norbornene skeleton upon hydrosilylation. .
＜ポリイミドの合成＞
４，４’−ジアミノジフェニルエーテル０．０６７５ｇ（０．３３７ｍｍｏｌ）をＮ−メチル−２−ピロリジノン（ＮＭＰ）２．２０ｇに溶かし室温で撹拌した。この溶液に、実施例１で合成した化合物（１−１）を０．５０００ｇ（０．３３７ｍｍｏｌ）固体のまま添加した。室温で６時間撹拌して得られたワニスを、重合体の濃度が２０重量％になるまでシクロヘキサノンで希釈し、０．５ミクロンのメンブランフィルターでろ過した。この溶液をスピンナー法でガラス基板に塗布し、１００℃のホットプレート上で３分間加熱した。続いて窒素雰囲気下２５０℃のオーブンで１時間焼成したところ淡黄色薄膜が得られた。このポリイミドのガラス転移温度１８７℃、熱分解温度は４０９℃であった。
<Synthesis of polyimide>
0.0675 g (0.337 mmol) of 4,4′-diaminodiphenyl ether was dissolved in 2.20 g of N-methyl-2-pyrrolidinone (NMP) and stirred at room temperature. To this solution, 0.5000 g (0.337 mmol) of the compound (1-1) synthesized in Example 1 was added as a solid. The varnish obtained by stirring at room temperature for 6 hours was diluted with cyclohexanone until the polymer concentration reached 20% by weight, and filtered through a 0.5 micron membrane filter. This solution was applied to a glass substrate by a spinner method and heated on a hot plate at 100 ° C. for 3 minutes. Subsequent baking in an oven at 250 ° C. for 1 hour under a nitrogen atmosphere gave a pale yellow thin film. This polyimide had a glass transition temperature of 187 ° C. and a thermal decomposition temperature of 409 ° C.
＜エポキシ樹脂の硬化＞
市販のエポキシ樹脂（ビスフェノールＡ−ジグリシジルエーテル：分子量９００）５ｇを５０ｍＬのビーカー中で１２０℃に加熱、融解させた。これに、実施例１で合成した酸無水物０．５ｇをかき混ぜながら加えた。均一になったら１２０℃で１時間、次いで１７０℃で１時間加熱したところ、透明な硬化物が得られた。
<Curing of epoxy resin>
5 g of a commercially available epoxy resin (bisphenol A-diglycidyl ether: molecular weight 900) was heated and melted at 120 ° C. in a 50 mL beaker. To this, 0.5 g of the acid anhydride synthesized in Example 1 was added while stirring. When it became uniform, it was heated at 120 ° C. for 1 hour and then at 170 ° C. for 1 hour, and a transparent cured product was obtained.
［比較例１］
酸無水物を、特許文献３記載の化合物（ｂ）０．４８１１ｇ（０．３３７ｍｍｏｌ）に代えた以外は、実施例２と同様に合成してポリイミド薄膜を得た。このポリイミドのガラス転移温度は１８８℃で、本発明の酸無水物を用いた場合と同等の耐熱性を示したが、薄膜の色は暗褐色であった。
[Comparative Example 1]
A polyimide thin film was obtained by synthesizing in the same manner as in Example 2 except that the acid anhydride was replaced with 0.4811 g (0.337 mmol) of the compound (b) described in Patent Document 3. The polyimide had a glass transition temperature of 188 ° C. and exhibited heat resistance equivalent to that when the acid anhydride of the present invention was used, but the color of the thin film was dark brown.
Claims (23)
ここに、環骨格との結合位置が固定されていない結合手は、Ｓｉ原子と結合する遊離原子価を示し、そして環骨格との結合位置が任意であることを示す。 The acid anhydride according to any one of claims 1 to 5, wherein Z in the formula (1) according to claim 1 is any one of the following trivalent groups:
Here, the bond in which the bonding position with the ring skeleton is not fixed indicates the free valence bonded to the Si atom, and the bonding position with the ring skeleton is arbitrary.
An optical waveguide containing the optical waveguide material according to claim 18.
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