JP3955841B2 - Organic-inorganic hybrid film material and method for producing the same - Google Patents
Organic-inorganic hybrid film material and method for producing the same Download PDFInfo
- Publication number
- JP3955841B2 JP3955841B2 JP2003341118A JP2003341118A JP3955841B2 JP 3955841 B2 JP3955841 B2 JP 3955841B2 JP 2003341118 A JP2003341118 A JP 2003341118A JP 2003341118 A JP2003341118 A JP 2003341118A JP 3955841 B2 JP3955841 B2 JP 3955841B2
- Authority
- JP
- Japan
- Prior art keywords
- dianhydride
- group
- polyamic acid
- acid
- tetracarboxylic
- 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.)
- Expired - Lifetime
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- 239000000463 material Substances 0.000 title claims description 61
- 238000004519 manufacturing process Methods 0.000 title claims description 32
- 229920005575 poly(amic acid) Polymers 0.000 claims description 63
- 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 claims description 59
- 238000005859 coupling reaction Methods 0.000 claims description 31
- 230000008878 coupling Effects 0.000 claims description 30
- 238000010168 coupling process Methods 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 27
- 239000003153 chemical reaction reagent Substances 0.000 claims description 25
- 239000004642 Polyimide Substances 0.000 claims description 20
- 229920001721 polyimide Polymers 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- -1 m-phenyldiamine Chemical compound 0.000 claims description 16
- 125000003277 amino group Chemical group 0.000 claims description 14
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- 150000004984 aromatic diamines Chemical class 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 7
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 150000004985 diamines Chemical class 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 5
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 5
- WECDUOXQLAIPQW-UHFFFAOYSA-N 4,4'-Methylene bis(2-methylaniline) Chemical compound C1=C(N)C(C)=CC(CC=2C=C(C)C(N)=CC=2)=C1 WECDUOXQLAIPQW-UHFFFAOYSA-N 0.000 claims description 4
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims description 4
- 239000003377 acid catalyst Substances 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 4
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 4
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- CDVZKYLSVNAIHH-UHFFFAOYSA-N 3,6-bis(trifluoromethyl)benzene-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(F)(F)F)=C(C(O)=O)C(C(O)=O)=C1C(F)(F)F CDVZKYLSVNAIHH-UHFFFAOYSA-N 0.000 claims description 3
- YOABZRCMJMKPFF-UHFFFAOYSA-N 3-triethoxysilylaniline Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC(N)=C1 YOABZRCMJMKPFF-UHFFFAOYSA-N 0.000 claims description 3
- YMTRNELCZAZKRB-UHFFFAOYSA-N 3-trimethoxysilylaniline Chemical compound CO[Si](OC)(OC)C1=CC=CC(N)=C1 YMTRNELCZAZKRB-UHFFFAOYSA-N 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 3
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 3
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims description 3
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 3
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- CGSKOGYKWHUSLC-UHFFFAOYSA-N 1-(4-aminophenyl)-1,3,3-trimethyl-2h-inden-5-amine Chemical compound C12=CC=C(N)C=C2C(C)(C)CC1(C)C1=CC=C(N)C=C1 CGSKOGYKWHUSLC-UHFFFAOYSA-N 0.000 claims description 2
- KQFSLCDYZSPVLX-UHFFFAOYSA-N 2-amino-3-(3-carboxyphenyl)benzoic acid Chemical compound NC1=C(C(O)=O)C=CC=C1C1=CC=CC(C(O)=O)=C1 KQFSLCDYZSPVLX-UHFFFAOYSA-N 0.000 claims description 2
- FFXSDAGPJYALFE-UHFFFAOYSA-N 2-amino-5-(4-amino-3-hydroxyphenoxy)phenol Chemical compound C1=C(O)C(N)=CC=C1OC1=CC=C(N)C(O)=C1 FFXSDAGPJYALFE-UHFFFAOYSA-N 0.000 claims description 2
- KHAFBBNQUOEYHB-UHFFFAOYSA-N 2-amino-5-(4-amino-3-hydroxyphenyl)sulfonylphenol Chemical compound C1=C(O)C(N)=CC=C1S(=O)(=O)C1=CC=C(N)C(O)=C1 KHAFBBNQUOEYHB-UHFFFAOYSA-N 0.000 claims description 2
- WOEURTKUUWKJKH-UHFFFAOYSA-N 2-methoxy-6-(3-methoxyphenyl)aniline Chemical compound COC=1C(=C(C=CC1)C1=CC(=CC=C1)OC)N WOEURTKUUWKJKH-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 claims description 2
- GDGWSSXWLLHGGV-UHFFFAOYSA-N 3-(4-aminophenyl)-1,1,3-trimethyl-2h-inden-5-amine Chemical compound C12=CC(N)=CC=C2C(C)(C)CC1(C)C1=CC=C(N)C=C1 GDGWSSXWLLHGGV-UHFFFAOYSA-N 0.000 claims description 2
- NJCOLSAFYMXOGO-UHFFFAOYSA-N 3-(trifluoromethyl)benzene-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C(C(F)(F)F)=C1C(O)=O NJCOLSAFYMXOGO-UHFFFAOYSA-N 0.000 claims description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 2
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 claims description 2
- JIYCXGLGOPBQSU-UHFFFAOYSA-N 4-(4-amino-3-chlorophenyl)sulfonyl-2-chloroaniline Chemical compound C1=C(Cl)C(N)=CC=C1S(=O)(=O)C1=CC=C(N)C(Cl)=C1 JIYCXGLGOPBQSU-UHFFFAOYSA-N 0.000 claims description 2
- MQMUKCHPSDDMII-UHFFFAOYSA-N 4-(4-amino-3-ethoxyphenyl)sulfonyl-2-ethoxyaniline Chemical compound C1=C(N)C(OCC)=CC(S(=O)(=O)C=2C=C(OCC)C(N)=CC=2)=C1 MQMUKCHPSDDMII-UHFFFAOYSA-N 0.000 claims description 2
- HGPTYGHIMKRTRN-UHFFFAOYSA-N 4-(4-amino-3-methoxyphenoxy)-2-methoxyaniline Chemical compound C1=C(N)C(OC)=CC(OC=2C=C(OC)C(N)=CC=2)=C1 HGPTYGHIMKRTRN-UHFFFAOYSA-N 0.000 claims description 2
- JYBYGQRODBVTDZ-UHFFFAOYSA-N 4-(4-amino-3-methylphenyl)sulfonyl-2-methylaniline Chemical compound C1=C(N)C(C)=CC(S(=O)(=O)C=2C=C(C)C(N)=CC=2)=C1 JYBYGQRODBVTDZ-UHFFFAOYSA-N 0.000 claims description 2
- OSGFBINRYVUILV-UHFFFAOYSA-N 4-[(4-aminophenyl)-diethylsilyl]aniline Chemical compound C=1C=C(N)C=CC=1[Si](CC)(CC)C1=CC=C(N)C=C1 OSGFBINRYVUILV-UHFFFAOYSA-N 0.000 claims description 2
- BLMSGSGJGUHKFW-UHFFFAOYSA-N 4-[(4-aminophenyl)-diphenylsilyl]aniline Chemical compound C1=CC(N)=CC=C1[Si](C=1C=CC(N)=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BLMSGSGJGUHKFW-UHFFFAOYSA-N 0.000 claims description 2
- NMLVVZNIIWJNTI-UHFFFAOYSA-N 4-[(4-aminophenyl)-ethylphosphoryl]aniline Chemical compound C=1C=C(N)C=CC=1P(=O)(CC)C1=CC=C(N)C=C1 NMLVVZNIIWJNTI-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- ZHBXLZQQVCDGPA-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)sulfonyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(S(=O)(=O)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 ZHBXLZQQVCDGPA-UHFFFAOYSA-N 0.000 claims description 2
- VFALDCWSTKEUED-UHFFFAOYSA-N 5-chloro-4-methylbenzene-1,3-diamine Chemical compound CC1=C(N)C=C(N)C=C1Cl VFALDCWSTKEUED-UHFFFAOYSA-N 0.000 claims description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 150000001413 amino acids Chemical class 0.000 claims description 2
- GCAIEATUVJFSMC-UHFFFAOYSA-N benzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 claims description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims description 2
- BKKDOKZWVFDQMM-UHFFFAOYSA-N bis(4-amino-3-chlorophenyl)methanone Chemical compound C1=C(Cl)C(N)=CC=C1C(=O)C1=CC=C(N)C(Cl)=C1 BKKDOKZWVFDQMM-UHFFFAOYSA-N 0.000 claims description 2
- WVGKWPSLUCXKHL-UHFFFAOYSA-N bis(4-amino-3-methoxyphenyl)methanone Chemical compound C1=C(N)C(OC)=CC(C(=O)C=2C=C(OC)C(N)=CC=2)=C1 WVGKWPSLUCXKHL-UHFFFAOYSA-N 0.000 claims description 2
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 238000002454 metastable transfer emission spectrometry Methods 0.000 claims description 2
- 239000005055 methyl trichlorosilane Substances 0.000 claims description 2
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims description 2
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 claims description 2
- VMPITZXILSNTON-UHFFFAOYSA-N o-anisidine Chemical compound COC1=CC=CC=C1N VMPITZXILSNTON-UHFFFAOYSA-N 0.000 claims description 2
- JGGWKXMPICYBKC-UHFFFAOYSA-N phenanthrene-1,8,9,10-tetracarboxylic acid Chemical compound C1=CC=C(C(O)=O)C2=C(C(O)=O)C(C(O)=O)=C3C(C(=O)O)=CC=CC3=C21 JGGWKXMPICYBKC-UHFFFAOYSA-N 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000005054 phenyltrichlorosilane Substances 0.000 claims description 2
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 claims description 2
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005052 trichlorosilane Substances 0.000 claims description 2
- OSOUNOBYRMOXQQ-UHFFFAOYSA-N 1-chloro-3-methylbenzene Chemical compound CC1=CC=CC(Cl)=C1 OSOUNOBYRMOXQQ-UHFFFAOYSA-N 0.000 claims 1
- 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 claims 1
- RCYNJDVUURMJOZ-UHFFFAOYSA-N 2-amino-5-[(4-amino-3-hydroxyphenyl)methyl]phenol Chemical compound C1=C(O)C(N)=CC=C1CC1=CC=C(N)C(O)=C1 RCYNJDVUURMJOZ-UHFFFAOYSA-N 0.000 claims 1
- IVVWBIJMWBNKFV-UHFFFAOYSA-N 3,3'-Dichloro-4,4'-diaminodiphenyl ether Chemical compound C1=C(Cl)C(N)=CC=C1OC1=CC=C(N)C(Cl)=C1 IVVWBIJMWBNKFV-UHFFFAOYSA-N 0.000 claims 1
- LKHVCEWNPKEPBT-UHFFFAOYSA-N 4-[(4-amino-3-methoxyphenyl)methyl]-2-methoxyaniline Chemical compound C1=C(N)C(OC)=CC(CC=2C=C(OC)C(N)=CC=2)=C1 LKHVCEWNPKEPBT-UHFFFAOYSA-N 0.000 claims 1
- 239000005046 Chlorosilane Substances 0.000 claims 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims 1
- 239000012965 benzophenone Substances 0.000 claims 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims 1
- 125000006159 dianhydride group Chemical group 0.000 claims 1
- 239000000243 solution Substances 0.000 description 27
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 17
- 238000010586 diagram Methods 0.000 description 15
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 239000010703 silicon Substances 0.000 description 12
- 229910052710 silicon Inorganic materials 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000000576 coating method Methods 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000005191 phase separation Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 229910010272 inorganic material Inorganic materials 0.000 description 6
- 239000011147 inorganic material Substances 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 238000004528 spin coating Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920003217 poly(methylsilsesquioxane) Polymers 0.000 description 3
- 229920000642 polymer Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-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
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Images
Description
本発明は、有機−無機ハイブリッドフィルム材料およびその製造方法に関するものであり、本発明の製法により、フィルム特性、例えば、屈折率、複屈折率、誘電率、平坦度などがコントロール可能となり、さらに得られるフィルム材料は、耐熱性が優れているため、耐高温性が要求されるIC製造工程の分野に特に有用である。 The present invention relates to an organic-inorganic hybrid film material and a method for producing the same, and the production method of the present invention makes it possible to control film properties such as refractive index, birefringence, dielectric constant, flatness, and the like. The resulting film material has excellent heat resistance and is particularly useful in the field of IC manufacturing processes that require high temperature resistance.
近年、材料科学の分野において、金属、セラミック、高分子化合物と電子素材が四大主流となっている。それぞれの材料にはその特殊性があり、例えば、高分子化合物は、加工のしやすさ、強靭、弾性、耐腐腐蝕性、絶縁性や低コストなどの優れた点を示すが耐熱性と機械特性に欠ける。セラミックは、硬さ、低活性、耐熱安定性などの優れた点を示すが、重くて、割れやすい欠点がある。これら諸材料の優れた点を持ちあわせ、欠点を補うことのできる、有機−無機ハイブリッド材料（hybrid material）の研究が注目されている。 In recent years, metals, ceramics, polymer compounds and electronic materials have become mainstream in the field of material science. Each material has its special characteristics. For example, polymer compounds show excellent points such as ease of processing, toughness, elasticity, corrosion resistance, insulation and low cost, but heat resistance and machine Lack of characteristics. Ceramic exhibits excellent points such as hardness, low activity, and heat stability, but it is heavy and has the disadvantage of being easily cracked. Research on organic-inorganic hybrid materials, which have the excellent points of these materials and can compensate for the drawbacks, has attracted attention.
従来の複合材料（composite）における範囲あるいは領域（ドメイン、domain）は、通
常ミクロン〜ミリの範囲にあり、これら材料における有機や無機成分は、主に構造や機能を変化させる役割を果たしており、その製造方法としては、主に物理的な混合（blend）
による方法が用いられている。それに対して、ハイブリッド材料の製造方法としては、主にゾルーゲル法（sol-gel）や自己アッセンブリ法（self-assembly）などにより有機と無機の混合が行なわれ、その欠点を補っている。例えば、有機材料を無機の主体中に導入して、無機材料の壊れやすさを改善し、多色性を与えたりしている。逆に、無機材料を有機の主体中に導入して、その強度や耐熱性を高めたり、吸湿性を改善するなど、材料の分子構造を新しくデザインすることで、新規な特性を有する材料が開発されている。
The range or domain (domain) in conventional composite materials (domains) is usually in the micron to millimeter range, and the organic and inorganic components in these materials mainly play a role in changing the structure and function. The manufacturing method is mainly physical blend (blend)
The method by is used. On the other hand, as a method for producing a hybrid material, organic and inorganic mixing is performed mainly by a sol-gel method or a self-assembly method to compensate for the drawbacks. For example, an organic material is introduced into an inorganic main body to improve the fragility of the inorganic material and to give polychromaticity. Conversely, by introducing an inorganic material into the organic main body to enhance its strength and heat resistance, and improving hygroscopicity, a material with new characteristics has been developed by newly designing the molecular structure of the material. Has been.
通常、有機−無機材料においては、十分な架橋構造をつくり、系内に存在する水分や溶剤を除去するのに高温加熱を必要とするのに対して、ゾル−ゲル法で製造したシリカ−ポリイミドハイブリッド材料は、優れた耐熱性を有するが故に、注目を浴びて多くの研究が行なわれ、そのような耐熱性は通常高温を必要とするIC製造工程において、特に重要な課題である。この種の材料（シリカ−ポリイミドハイブリッド材料）の開発は、物理的ハイブリッドによるポリアミド酸溶液とテトラエチル オルトシリケート（TEOSと略称す）の二種類の溶液の物理的混合工程、自旋塗り工程（スピンコーティング）、次いで、その後に加熱し固化してフィルムを形成する工程からなっている。しかし、このような反応系内では明らかに相分離が観察される。そこで相分離を解決する方法として、カップリング剤を導入する重要な技術が検討された。カップリング剤は、互いに相容れない二つの物質の間に化学結合を与えることができるからである。従来のポリイミド／シリカハイブリッド材料に対して、その分析は主にそれらの光学的特性、有機無機の比率による効果と吸湿性などについて行なわれてきた。又、シリカとポリイミドとの新規なハイブリッド材料には、例えば、水溶性ハイブリッド材料、剛硬性ハイブリッド材料、感光性を示すハイブリッド材料などの、それぞれ特別な異なった用途が見られる。 Usually, in organic-inorganic materials, silica-polyimide produced by the sol-gel method is required to form a sufficient cross-linked structure and to require high-temperature heating to remove moisture and solvent present in the system. Since hybrid materials have excellent heat resistance, much research has been conducted with attention, and such heat resistance is a particularly important issue in IC manufacturing processes that usually require high temperatures. The development of this kind of material (silica-polyimide hybrid material) is based on the physical mixing process of polyamic acid solution and tetraethyl orthosilicate (TEOS) by physical hybrid, self-coating process (spin coating) ), And then a step of heating and solidifying to form a film. However, phase separation is clearly observed in such a reaction system. Therefore, an important technique for introducing a coupling agent was studied as a method for solving phase separation. This is because the coupling agent can provide a chemical bond between two materials that are incompatible with each other. For conventional polyimide / silica hybrid materials, the analysis has mainly been conducted on their optical properties, the effect of organic / inorganic ratio and hygroscopicity. In addition, the novel hybrid material of silica and polyimide has special and different uses such as a water-soluble hybrid material, a rigid hybrid material, and a hybrid material exhibiting photosensitivity.
シリカとポリイミドとのハイブリッド材料の研究成熟に伴い、シリコン元素を主体としたその他の研究開発が次々に進められてきた。その中で、ポリセスキシロキサンを用いた材料は誘電率の低いことで注目される。電子素子（積層回路基板）における回線間の幅が次第に小さくなる傾向下で、信号の伝送の遅延問題が浮上し、このようなRC遅延[Resistance Capacitor (RC) delay]の影響を軽減する目的で、まず、銅線製造工程による電気抵
抗を下げる方法が考えられ、次に誘電率の低い絶縁層を用いることで二本の導線の間に形
成される電気容量を下げる方法が用いられている。そこで、近年では、誘電率の低い材料（即ち、law K material）が材料科学の主な研究分野として注目を浴びている。そのような中にあって、ポリセスキシロキサン［poly(silsesquioxane)、ポリシルセスキオキサン］の誘電率は2.6〜2.9範囲内にあり、シリカの誘電率4.0に比べると非常に低く、しか
もシリカのもつ耐熱性と機械的強度を有するので、次第にシリカに替って絶縁層として利用されつつある。
With the research and maturation of hybrid materials of silica and polyimide, other research and development mainly based on silicon element has been advanced one after another. Among them, a material using polysesquisiloxane is noted for its low dielectric constant. In the trend of decreasing the width between lines in electronic elements (multilayer circuit boards), the problem of signal transmission delay has emerged, and the purpose of reducing the effect of such RC delay (Resistance Capacitor (RC) delay) First, a method of lowering the electric resistance by the copper wire manufacturing process is conceivable. Next, a method of lowering the electric capacity formed between two conductors by using an insulating layer having a low dielectric constant is used. Therefore, in recent years, materials having a low dielectric constant (that is, law K material) have attracted attention as the main research field of material science. Under such circumstances, the dielectric constant of polysesquisiloxane (poly (silsesquioxane), polysilsesquioxane) is in the range of 2.6 to 2.9, which is very low compared to the dielectric constant of silica 4.0. Because of its heat resistance and mechanical strength, it is gradually being used as an insulating layer instead of silica.
通常、ポリセスキシロキサンは、三官能基のシラン単体の加水分解と縮合反応により製造される。上記の官能基としては、クロール（Cl）、メトキシ基やエトキシ基などが挙げられる。生成物の分子量、構造と末端官能基の数は、合成の際の反応条件に大きく支配される。例えば、単体の特性、反応温度、触媒と溶媒の種類などに非常に影響される。特に知られているポリセスキシロキサンとしては、ポリメチルセスキシロキサン［poly(methyl silsesquioxane) 、PMSQと略称す。］が挙げられ、誘電率が僅か2.7で、吸湿性が低く
、且つ耐熱性と機械的強度に優れていることで、近年、PMSQは優れた低誘電率材料として脚光を浴びているが、シリコンウェハーに対す付着性が悪く、しかもこわれ易いという性質を有するので、その利用に制限があり、有機の高分子をさらに導入することで欠点を改善することが望まれている。
Usually, polysesquisiloxane is produced by hydrolysis and condensation reaction of trifunctional silane alone. Examples of the functional group include chlor (Cl), methoxy group, and ethoxy group. The molecular weight, structure and number of terminal functional groups of the product are largely governed by the reaction conditions during the synthesis. For example, it is greatly influenced by the characteristics of the single substance, the reaction temperature, the type of catalyst and solvent, and the like. A particularly known polysesquisiloxane is abbreviated as poly (methyl silsesquioxane) or PMSQ. In recent years, PMSQ has been in the spotlight as an excellent low dielectric constant material because it has a dielectric constant of only 2.7, low hygroscopicity, and excellent heat resistance and mechanical strength. Since it has the property of being poorly adherent to a wafer and easily broken, there is a limit to its use, and it is desired to improve the defects by further introducing an organic polymer.
現在、ポリセスキシロキサン／ポリイミドハイブリッド材料を用いて低誘電率のフィルムを製造する方法としては、下記の文献が知られている。 Currently, the following documents are known as methods for producing a low dielectric constant film using a polysesquisiloxane / polyimide hybrid material.
（１）先に、ジアミンと二酸無水物（ジ酸無水物）を用いてポリアミド酸を合成し、次に、ポリセスキシロキサンと単体であるメチルトリメトキシシラン（MTMSと略称す）とカップリング試薬とをポリアミド酸溶液中に加え、ポリアミド酸の酸性によりMTMSの加水分解縮合反応を引きおこし、最後に生成溶液を基材に塗布し、固化させてフィルムを製造する方法である。この方法ではカップリング試薬により有機と無機との化学結合を提供しているが、なお、相分離の問題が明らかに存在している。これは、MTMSの反応条件を十分に正確に支配できないため、最終時点でのＳi-OH基含量を左右できずに生じるもので、最終的にはフィルムの相分離により物性が低下し、しかも副産物のメタノールが反応系内に残存するという問題が残っている。 (1) First, polyamic acid is synthesized using diamine and dianhydride (diacid anhydride), and then coupled with polysesquisiloxane and methyltrimethoxysilane (abbreviated as MTMS). In this method, a reagent is added to a polyamic acid solution, a hydrolysis condensation reaction of MTMS is caused by the acidity of the polyamic acid, and finally the resulting solution is applied to a substrate and solidified to produce a film. In this method, a coupling reagent provides a chemical bond between organic and inorganic, but there is clearly a phase separation problem. This occurs because the MTMS reaction conditions cannot be controlled sufficiently accurately, so that the Si-OH group content at the final point cannot be influenced. Finally, the physical properties deteriorate due to phase separation of the film, and by-products are produced. There remains a problem that the methanol remains in the reaction system.
（２）ポリセスキシロキサンとポリアミド酸アルキルエステルをそれぞれ調製し、次に両者を混合し、カップリング試薬を加えてハイブリッド反応を行ない、最後に生成したポリセスキシロキサンとポリイミドとのハイブリッド材料を基材に塗布し固化することでフィルム成形する。この方法では、ポリイミドの前躯体として通常用いられているポリアミド酸を使用せず、ポリアミド酸アルキルエステルが用いられ、多くの溶剤に溶解する利点を有るが、有機と無機との混合比率は限定され、ポリイミドの比率は最高で30％となり、ポリイミドを主体としたハイブリッド材料は得られないという問題がある。 (2) Polysesquisiloxane and polyamic acid alkyl ester are prepared, then both are mixed, a coupling reagent is added to carry out a hybrid reaction, and the last produced polysesquisiloxane and polyimide hybrid material is used as a base material. It is formed into a film by applying and solidifying. This method does not use the polyamic acid that is usually used as a precursor of polyimide, but uses polyamic acid alkyl ester, which has the advantage of being dissolved in many solvents, but the mixing ratio of organic and inorganic is limited. The ratio of polyimide is 30% at the maximum, and there is a problem that a hybrid material mainly composed of polyimide cannot be obtained.
上記の文献より、ポリセスキシロキサンとポリイミドハイブリッド材料より誘電率の低いフィルムと光導波路材料を製造する場合、下記の課題があることが分る。 From the above literature, it can be seen that there are the following problems when producing a film and an optical waveguide material having a dielectric constant lower than that of polysesquisiloxane and polyimide hybrid material.
（１）有機と無機との間の分散が悪く、相分離の現象が生じること；（２）有機と無機との間の比率が限定され、その中の一種を主体にしなければならないこと。 (1) The dispersion between organic and inorganic is poor and the phenomenon of phase separation occurs; (2) The ratio between organic and inorganic is limited and one of them must be the main component.
上記の課題を解決するため、本発明者らは鋭意検討の結果、下記の方法が有効であることを見出し、本発明を完成するに至った。 In order to solve the above problems, the present inventors have intensively studied and found that the following method is effective, and have completed the present invention.
すなわち、本発明の第一の目的は、ポリイミド／ポリセスキシロキサンからなる有機−無機ハイブリッドフィルム材料を提供することにある。 That is, the first object of the present invention is to provide an organic-inorganic hybrid film material composed of polyimide / polysesquisiloxane.
又、本発明の第二の目的は、ポリアミド酸／ポリセスキシロキサンより有機−無機ハイブリッドフィルム材料を製造する方法を提供することにある。 A second object of the present invention is to provide a method for producing an organic-inorganic hybrid film material from polyamic acid / polysesquisiloxane.
本発明は、下記の工程を含む、有機−無機ハイブリッド材料の製造方法に関する：
（ａ）芳香族ジアミンと芳香族二酸無水物とを、室温〜50℃範囲内の温度下で反応し、ポリアミド酸を得る工程（但し、上記の芳香族ジアミンと芳香族二酸無水物との当量比（equivalent ratio：芳香族二酸無水物の酸無水物当量数／芳香族ジアミンのアミン当量数）は２以下である。）；
（ｂ）一般式「ＮＨ2−Ｒ1−Ｓｉ（Ｒ2）3」（式中、Ｒ1はＣ1〜6アルキレン基あるいは
フェニレン基を示し、Ｒ2はそれぞれ同じでも異なっていてもよく、Ｃ1〜6アルコキシ基
を示す。）で示されるアミノ基を含有するカップリング試薬を用いて、上記工程（ａ）で調製したポリアミド酸とのカップリングを行ない、末端が、アミノ基含有カップリング試薬で封じられたポリアミド酸を得る工程（但し、上記のカップリング試薬は、該試薬のアミン当量数が、ジアミンのアミン当量数よりも少ない量で用いる。）；
（ｃ）一般式「Ｒ3−Ｓｉ（Ｒ4）3」（式中、Ｒ3は水素原子、Ｃ1〜6アルキル基、Ｃ2〜6アルケニル基、あるいはフェニル基を示し、Ｒ4はそれぞれ独立してハロゲン原子、Ｃ1〜6アルコキシ基、Ｃ2〜6アルケニルオキシ基、あるいはフェノキシ基を示す。）で示され
る単体を使用し、酸触媒と溶剤の存在下、室温〜100℃の温度範囲内で、ゾル−ゲル反応
を行ない、ポリセスキシロキサン［poly(silsesquioxane)］を調製する工程（但し、酸触媒の用量は、反応系をPh1〜4に保持する範囲で使用される。）；
（ｄ）上記の工程（ｂ）で得られた末端がアミノ基含有カップリング試薬で封じられたポリアミド酸を、脱イオン水の存在下、加水分解を行なうことで、上記工程（ｃ）で得られたポリセスキシロキサンとカップリングして、ポリアミド酸とポリセスキシロキサンとの複合材料スラリーを得る工程（但し、カップリングからポリアミド酸のアミノ基含有カップリング試薬の加水分解に使用される脱イオン水の用量は、アミノ基含有カップリング試薬で末端を封じたポリアミド酸の末端アルコキシ基量と同様なモル数（等量〜やや過剰モル量）が使用される。）；
（ｅ）上記工程（ｄ）で得られた複合材料スラリーを基材に塗布し、温度を上げて固化することで、ポリイミド／ポリセスキシロキサンの有機−無機ハイブリッドフィルム材料を得る工程。
The present invention relates to a method for producing an organic-inorganic hybrid material comprising the following steps:
(A) a step of reacting an aromatic diamine and an aromatic dianhydride at a temperature in the range of room temperature to 50 ° C. to obtain a polyamic acid (provided that the above aromatic diamine and aromatic dianhydride Equivalent ratio (number of acid anhydride equivalents of aromatic dianhydride / number of amine equivalents of aromatic diamine ) is 2 or less);
(B) the formula "NH 2 -R 1 -Si (R 2 ) 3 " (wherein, R 1 represents a C 1 ~ 6 alkylene group or a phenylene group, R 2 may be the same or different and each using a coupling reagent containing an amino group represented by.) showing a C 1 ~ 6 alkoxy group, performs coupling of the polyamic acid prepared in the above step (a), the terminal amino group-containing coupling A step of obtaining a polyamic acid sealed with a reagent (however, the coupling reagent is used in such an amount that the number of amine equivalents of the reagent is less than the number of amine equivalents of diamine );
(C) the formula "R 3 -Si (R 4) 3" (wherein, R 3 represents a hydrogen atom, C 1 ~ 6 alkyl group, C 2 ~ 6 alkenyl group or a phenyl group,, R 4 are each independently a halogen atom, C 1 ~ 6 alkoxy group, using a simple substance represented by.) showing a C 2 ~ 6 alkenyloxy group or a phenoxy group, in the presence of an acid catalyst and a solvent, the temperature of room temperature to 100 ° C. Within the range, a sol-gel reaction is performed to prepare poly (silsesquioxane) (however, the amount of the acid catalyst is used in a range that keeps the reaction system at Ph1 to 4);
(D) The polyamic acid whose end obtained in the above step (b) is sealed with an amino group-containing coupling reagent is hydrolyzed in the presence of deionized water to obtain in the above step (c). To obtain a composite slurry of polyamic acid and polysesquisiloxane by coupling with the obtained polysesquisiloxane (however, deionized water used for hydrolysis of an amino group-containing coupling reagent of polyamic acid from the coupling) The same number of moles as the amount of terminal alkoxy groups of the polyamic acid capped with an amino group-containing coupling reagent (equal amount to slightly excess molar amount) are used .
(E) A step of obtaining a polyimide / polysesquisiloxane organic-inorganic hybrid film material by applying the composite material slurry obtained in the step (d) to a base material and raising the temperature to solidify.
さらに、本発明は下記の工程を含む、有機−無機ハイブリッドフィルム材料の別な製造方法にも関する：
（ａ１）芳香族ジアミンと芳香族二酸無水物とを、室温〜50℃範囲内の温度下で反応し、ポリアミド酸を得る工程（但し、上記の芳香族ジアミンと芳香族二酸無水物との当量比（equivalent ratio）は2以下である。）；
（ｂ１）一般式「ＮＨ2−Ｒ1−Ｓｉ（Ｒ2）3」（式中、Ｒ1はＣ1〜6アルキレン基、あ
るいはフェニレン基を示し、Ｒ2は、それぞれ同じでも異なっていても良い、Ｃ1〜6アル
コキシ基を示す。）で示されるアミノ基含有カップリング試薬を用いて、上記工程（ａ１）で調製されたポリアミド酸とのカップリングを行ない、末端をアミノ基含有カップリング試薬で封じたポリアミド酸を得る工程（但し、カップリング試薬の添加量は、ジアミンの用量より少なめに用いる。）；
（ｄ１）上記の工程（ｂ１）で得られた、末端がアミノ基含有カップリング試薬で封じられたポリアミド酸を、脱イオン水の存在下、加水分解すると共に（好ましくは、加水分解し、次いで）シリコン アルコキサイドを加えてカップリングを行ない、ポリアミド酸とシリコン アルコキサイドとの複合材料スラリーを得る工程（但し、カップリングからポリアミド酸のアミノ基含有カップリング試薬の加水分解で使用される脱イオン水の量は
、アミノ基含有カップリング試薬で末端を封じたポリアミド酸の末端アルコキシ基量と同様のモル数（等量〜やや過剰モル量）が使用される。）；
（ｅ１） 上記工程（ｄ１）で得られた複合材料スラリーを基材に塗布し、温度を上げて固化した後、ポリアミド／シリコン アルコキサイドの有機−無機ハイブリッドフィルム材料を得る工程。
The present invention further relates to another method for producing an organic-inorganic hybrid film material comprising the following steps:
(A1) A step of reacting an aromatic diamine and an aromatic dianhydride at a temperature in the range of room temperature to 50 ° C. to obtain a polyamic acid (provided that the above aromatic diamine and aromatic dianhydride Equivalent ratio of 2 or less.);
(B1) In the general formula "NH 2 -R 1 -Si (R 2 ) 3 " (wherein, R 1 represents a C 1 ~ 6 alkylene group or a phenylene group,, R 2 is also the same as or different from each other good, with an amino group-containing coupling reagent represented by.) showing a C 1 ~ 6 alkoxy group, performs coupling of the polyamic acid prepared in the above step (a1), amino group-containing coupling end A step of obtaining a polyamic acid sealed with a reagent (however, the amount of coupling reagent used is less than the amount of diamine);
(D1) The polyamic acid obtained in the above step (b1) and having a terminal sealed with an amino group-containing coupling reagent is hydrolyzed in the presence of deionized water (preferably hydrolyzed, ) Adding silicon alkoxide to perform coupling to obtain a composite slurry of polyamic acid and silicon alkoxide (however, deionized water used in the hydrolysis of the amino acid-containing coupling reagent of polyamic acid from the coupling) The amount is the same number of moles (equal amount to slightly excess molar amount) as the amount of terminal alkoxy group of the polyamic acid end-capped with an amino group-containing coupling reagent.);
(E1) A step of obtaining a polyamide / silicon alkoxide organic-inorganic hybrid film material after applying the composite material slurry obtained in the above step (d1) to a substrate and raising the temperature to solidify.
本発明による製造工程は、第1図に示す反応工程図に詳細に示されている。 The production process according to the present invention is shown in detail in the reaction process diagram shown in FIG.
本発明において使用される「ポリアミド酸」とは、ジアミンとジ酸無水物（二酸無水物）との反応よりなる官能基として、−ＮＨ−ＣＯ−と−ＣＯＯＨとを有する化合物であり、「ポリイミド」とは、上記のポリアミド酸を昇温固化した後、ポリアミド酸の官能基の−ＮＨ−ＣＯ−と官能基のカルボキシル基（−ＣＯＯＨ）とを環化して得られる生成物である。そこで、まだ昇温固化しない場合は「ポリアミド酸」であり、固化した後、該ポリアミド酸は環化してポリイミドに変化する。 The “polyamic acid” used in the present invention is a compound having —NH—CO— and —COOH as a functional group formed by a reaction between a diamine and a diacid anhydride (dioic anhydride). “Polyimide” is a product obtained by solidifying the above polyamic acid at elevated temperature and then cyclizing the functional group —NH—CO— and the functional carboxyl group (—COOH) of the polyamic acid. Therefore, when it is not yet solidified at elevated temperature, it is “polyamic acid”. After solidifying, the polyamic acid cyclizes and changes to polyimide.
本発明において、上記「Ｃ1〜6アルキル基」とは、炭素数１〜６の直鎖状又は側鎖状アルキル基を示し、具体例としては、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓ−ブチル基、ｔ−ブチル基、ｎ−ペンチル基、ネオペンチル基、ヘキシル基などが挙げられる。 In the present invention, the “C 1-6 alkyl group” means a linear or side chain alkyl group having 1 to 6 carbon atoms. Specific examples thereof include, for example, a methyl group, an ethyl group, and n-propyl group. Group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, neopentyl group, hexyl group and the like.
本発明において、上記の「Ｃ2〜6アルケニル基」とは、炭素数２〜６で少なくとも一つの炭素−炭素二重結合を有する直鎖状又は側鎖状のアルケニル基を示す。その具体例としては、例えば、エチレン基、アクリル基、プロプレン基、ブチレン基、ペンチレン基、ヘキシレン基などが挙げられる。 In the present invention, the “C 2-6 alkenyl group” refers to a linear or side chain alkenyl group having 2 to 6 carbon atoms and having at least one carbon-carbon double bond. Specific examples thereof include an ethylene group, an acrylic group, a propylene group, a butylene group, a pentylene group, and a hexylene group.
本発明においては用いられる「ハロゲン原子」とは、フッ素（Ｆ）、塩素（Ｃｌ）、臭素（Ｂｒ）又はヨウ素（Ｉ）を示し、好ましくは塩素（Ｃｌ）である。 The “halogen atom” used in the present invention represents fluorine (F), chlorine (Cl), bromine (Br) or iodine (I), preferably chlorine (Cl).
本発明において用いられる「C1〜6アルコキシ基」とは、酸素原子と結合した上記のア
ルキル基を示し、例えば、メトキシ基、エトキシ、ｎ−プロポキシ基、イソプロキシ基、ｎ−ブトキシ基、ｓ−ブトキシ基、ｔ−ブトキシ基、ｎ−ペントキシ基、ネオペントキシ基、ヘキシルオキシ基などが挙げられる。
And "C 1 ~ 6 alkoxy group" used in the present invention exhibits the above-described alkyl groups linked to an oxygen atom, for example, methoxy, ethoxy, n- propoxy, iso proxy group, n- butoxy group, s -Butoxy group, t-butoxy group, n-pentoxy group, neopentoxy group, hexyloxy group and the like can be mentioned.
本発明において用いられる「C2〜6アルケニルオキシ基」とは、酸素原子と結合した上
記のアルケニル基を示し、例えば、エチレンオキシ基、プロピレンオキシ基、ブチレンオキシ基、ペンチレンオキシ基、ヘキシレンオキシ基などが挙げられる。
The "C 2 ~ 6 alkenyloxy group" used in the present invention, shows the aforementioned alkenyl groups bonded to an oxygen atom, for example, ethylene group, propylene group, butylene group, pentylene group, hexylene An oxy group etc. are mentioned.
本発明において、有機−無機ハイブリッドフィルム材料を製造する際に用いられる芳香族二酸無水物として具体例としては、例えば、ピロメリト酸二無水物（ＰＭＤＡと略称す）、４，４−ビスフタル酸二無水物（ＢＰＤＡと略称す）、４，４−ヘキサフルオロイソプロピレン−ビスフタル酸二無水物（６ＦＤＡと略称す）、１−（トリフルオロメチル）−ベンゼン−２，３，５，６−テトラカルボン酸二無水物（Ｐ３ＦＤＡと略称す）、１，４−ジ（トリフルオロメチル）−ベンゼン−２，３，５，６−テトラカルボン酸二無水物（Ｐ６ＧＤＡと略称す）、１−（３’，４’−ジカルボキシフェニル）−１，３，３−トリメチルインダニル−５，６−ジカルボン酸二無水物、１−（３’，４’−ジカルボキシフェニル）−１，３，３−トリメチルインダニル−６，７−ジカルボン酸二無水物、１−（３’，４’−ジカルボキシフェニル）−３−メチルインダニル−５，６−ジカルボン酸二無水物、１−（３’，４’−ジカルボキシフェニル）−３−メチルインダニル−６，７−ジカルボン酸二無水物、ジアセナフチルベンゼン−２，３，９，１０−テトラカルボン酸二無水物、ナフチル−１，４，５，８−テトラカルボン酸二無水物、２，６−ジクロロ
ナフチル−１，４，５，８−テトラカルボン酸二無水物、２，７−ジクロロナフチル−１，４，５，８−テトラカルボン酸二無水物、２，３，６，７−テトラクロロナフチル−２，４，５，８−テトラカルボン酸二無水物、フェナントレン−１，８，９，１０−テトラカルボン酸二無水物、ベンゾフェノン−３，３’，４，４'−テトラカルボン酸二無水物
、ベンゾフェノン−１，２'，３，３'−テトラカルボン酸二無水物、ビフェニル−３，３'，４，４'−テトラカルボン酸二無水物、ベンゾフェノン−３，３'，４，４'−テトラカルボン酸二無水物、ビフェニル−２，２'，３，３'−テトラカルボン酸二無水物、４，４'−イソプロピレン−ジフタル酸二無水物、３，３'−イソプロピレン−ジフタル酸二無水物、４，４'−オキソジフタル酸二無水物、４，４'−スルホニルジフタル酸二無水物、３，３'−オキソジフタル酸二無水物、４，４'−メチレン−ジフタル酸二無水物、４，４'
−スルファニルジフタル酸二無水物、４，４'−エチレン−ジフタル酸二無水物、ナフチ
ル−２，３，６，７−テトラカルボン酸二無水物、ナフチル−１，２，４，５−テトラカルボン酸二無水物、ナフチル−１，２，５，６−テトラカルボン酸二無水物、ベンゼン−１，２，３，４−テトラカルボン酸二無水物、ピラジニル−２，３，５，６−テトラカルボン酸二無水物などが挙げられるが、これらに限定されるものではない。その内、特にピロメリト酸二無水物（ＰＭＤＡ）、４，４−ジフタル酸二無水物（ＢＰＤＡ）、４，４−ヘキサフルオロイソプロピレン−ジフタル酸二無水物（６ＦＤＡ）、１−（トリフルオロメチル）−ベンゼン−２，３，５，６−テトラカルボン酸二無水物（Ｐ３ＦＤＡ）、１，４−ジ（トリフルオロメチル）−ベンゼン−２，３，５，６−テトラカルボン酸二無水物（Ｐ６ＧＤＡ）が好ましく用いられる。
In the present invention, specific examples of the aromatic dianhydride used in producing the organic-inorganic hybrid film material include pyromellitic dianhydride (abbreviated as PMDA), 4,4-bisphthalic acid dianhydride. Anhydride (abbreviated as BPDA), 4,4-hexafluoroisopropylene-bisphthalic dianhydride (abbreviated as 6FDA), 1- (trifluoromethyl) -benzene-2,3,5,6-tetracarboxylic Acid dianhydride (abbreviated as P3FDA), 1,4-di (trifluoromethyl) -benzene-2,3,5,6-tetracarboxylic dianhydride (abbreviated as P6GDA), 1- (3 ′ , 4′-Dicarboxyphenyl) -1,3,3-trimethylindanyl-5,6-dicarboxylic dianhydride, 1- (3 ′, 4′-dicarboxyphenyl) -1,3,3-trimethyl Indanyl-6,7-dicarboxylic dianhydride, 1- (3 ′, 4′-dicarboxyphenyl) -3-methylindanyl-5,6-dicarboxylic dianhydride, 1- (3 ′, 4 ′ -Dicarboxyphenyl) -3-methylindanyl-6,7-dicarboxylic dianhydride, diacenaphthylbenzene-2,3,9,10-tetracarboxylic dianhydride, naphthyl-1,4,5, 8-tetracarboxylic dianhydride, 2,6-dichloronaphthyl-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthyl-1,4,5,8-tetracarboxylic acid dianhydride Anhydride, 2,3,6,7-tetrachloronaphthyl-2,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, benzophenone-3 , 3 ', 4,4'-tetracarbo Acid dianhydride, benzophenone-1,2 ′, 3,3′-tetracarboxylic dianhydride, biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, benzophenone-3,3 ′, 4,4′-tetracarboxylic dianhydride, biphenyl-2,2 ′, 3,3′-tetracarboxylic dianhydride, 4,4′-isopropylene-diphthalic dianhydride, 3,3′- Isopropylene-diphthalic dianhydride, 4,4′-oxodiphthalic dianhydride, 4,4′-sulfonyldiphthalic dianhydride, 3,3′-oxodiphthalic dianhydride, 4,4′-methylene -Diphthalic dianhydride, 4,4 '
-Sulfanyl diphthalic dianhydride, 4,4'-ethylene-diphthalic dianhydride, naphthyl-2,3,6,7-tetracarboxylic dianhydride, naphthyl-1,2,4,5-tetra Carboxylic dianhydride, naphthyl-1,2,5,6-tetracarboxylic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, pyrazinyl-2,3,5,6- Although tetracarboxylic dianhydride etc. are mentioned, it is not limited to these. Among them, pyromellitic dianhydride (PMDA), 4,4-diphthalic dianhydride (BPDA), 4,4-hexafluoroisopropylene-diphthalic dianhydride (6FDA), 1- (trifluoromethyl) ) -Benzene-2,3,5,6-tetracarboxylic dianhydride (P3FDA), 1,4-di (trifluoromethyl) -benzene-2,3,5,6-tetracarboxylic dianhydride ( P6GDA) is preferably used.
本発明において有機−無機ハイブリッドフィルム材料の製造方法で用いる芳香族ジアミンの具体例としては、例えば、４，４’−オキソジアニリン（ＯＤＡと略称す）、５−アミノ−１−（４’−アミノフェニル）−１，３，３−トリメチルインダン、６−アミノ−１−（４’−アミノフェニル）−１，３，３−トリメチルインダン、４，４’−メチレンジ（０−クロロアニリン）、３，３’−ジクロロジアニリン、３，３'−スルホニルジア
ニリン、４，４'−ジアミノベンゾフェノン、１，５−ジアミノナフタレン、ジ（４−ア
ミノフェニル）ジエチルシラン、ジ（４−アミノフェニル）ジフェニルシラン、ジ（４−アミノフェニル）エチルホスフィン オキサイド、Ｎ−（ジ（４−アミノフェニル））−Ｎ−メチルアミン、Ｎ−（ジ（４−アミノフェニル））−Ｎ−フェニルアミン、４，４'
−メチレンジ（２−メチルアニリン）、４，４'−メチレンジ（２−メトキシアニリン）
、５，５'−メチレンジ（２−アミノフェノール）、４，４'−メチレンジ（２−メチルアニリン）、４，４'−オキソジ（２−メトキシアニリン）、４，４'−オキソジ（２−クロロアニリン）、２，２'−ジ（４−アミノフェノール）、５，５'−オキソジ（２−アミノフェノール）、４，４'−スルファニルジ（２−メチルアニリン）、４，４'−スルファニルジ（２−メトキシアニリン）、４，４'−スルファニルジ（２−クロロアニリン）、４
，４'−スルホニルジ（２−メチルアニリン）、４，４'−スルホニルジ（２−エトキシアニリン）、４，４'−スルホニルジ（２−クロロアニリン）、５，５'−スルホニルジ（２−アミノフェノール）、３，３'−ジメチル−４，４'−ジアミノベンゾフェノン、３，３'−シ゛メトキシ−４，４'−ジアミノベンゾフェノン、３，３'−ジクロロ−４，４'−ジアミノベンゾフェノン、４，４'−ジアミノビフェニル、ｍ−フェニルジアミン、ｐ−フ
ェニルジアミン、４，４'−メチレンジアニリン、４，４'−スルファニルジアニリン、４，４'−スルホニルジアニリン、４，４'−イソプロピレンジアニリン、３，３'−ジメチ
ルビフェニリルアミン、３，３'−ジメトキシビフェニリルアミン、３，３'−ジカルボキシビフェニリルアミン、２，４−トリルジアミン、２，５−トリルジアミン、２，６−トリルジアミン、ｍ−キシリルジアミン、２，４−ジアミノ−５−クロロトルエン、２，４−ジアミノ−６−クロロトルエンなどが挙げられるが、これらに限定されるものではない。その内、特に４，４'−オキソジアニリン（ＯＤＡ）が好ましい。
Specific examples of the aromatic diamine used in the method for producing an organic-inorganic hybrid film material in the present invention include, for example, 4,4′-oxodianiline (abbreviated as ODA), 5-amino-1- (4′- Aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4′-aminophenyl) -1,3,3-trimethylindane, 4,4′-methylenedi (0-chloroaniline), 3 , 3′-dichlorodianiline, 3,3′-sulfonyldianiline, 4,4′-diaminobenzophenone, 1,5-diaminonaphthalene, di (4-aminophenyl) diethylsilane, di (4-aminophenyl) diphenyl Silane, di (4-aminophenyl) ethylphosphine oxide, N- (di (4-aminophenyl))-N-methylamine, N- (di (4-amino Eniru)) - N-phenylamine, 4,4 '
-Methylenedi (2-methylaniline), 4,4'-methylenedi (2-methoxyaniline)
5,5′-methylenedi (2-aminophenol), 4,4′-methylenedi (2-methylaniline), 4,4′-oxodi (2-methoxyaniline), 4,4′-oxodi (2-chloro) Aniline), 2,2′-di (4-aminophenol), 5,5′-oxodi (2-aminophenol), 4,4′-sulfanyldi (2-methylaniline), 4,4′-sulfanyldi (2-methoxyaniline), 4,4′-sulfanyldi (2-chloroaniline), 4
, 4′-sulfonyldi (2-methylaniline), 4,4′-sulfonyldi (2-ethoxyaniline), 4,4′-sulfonyldi (2-chloroaniline), 5,5′-sulfonyldi (2 -Aminophenol), 3,3'-dimethyl-4,4'-diaminobenzophenone, 3,3'-dimethoxy-4,4'-diaminobenzophenone, 3,3'-dichloro-4,4'-diaminobenzophenone, 4,4′-diaminobiphenyl, m-phenyldiamine, p-phenyldiamine, 4,4′-methylenedianiline, 4,4′-sulfanyldianiline, 4,4′-sulfonyldianiline, 4,4′- Isopropylene dianiline, 3,3′-dimethylbiphenylylamine, 3,3′-dimethoxybiphenylylamine, 3,3′-dicarboxybiphenylylamine, 2,4-tri Examples include diamine, 2,5-tolyldiamine, 2,6-tolyldiamine, m-xylyldiamine, 2,4-diamino-5-chlorotoluene, and 2,4-diamino-6-chlorotoluene. It is not limited to. Of these, 4,4′-oxodianiline (ODA) is particularly preferable.
本発明において用いられるシリコン アルコキサイドの具体例としては、例えば、テト
ラメトキシシラン、テトラエトキシシランなどが挙げられるが、これらに限定されるものではない。
Specific examples of the silicon alkoxide used in the present invention include, but are not limited to, tetramethoxysilane and tetraethoxysilane.
本発明において、製造工程の（ａ）と（ａ１）における反応は、溶剤の存在下で行なわれるのが好ましく、反応に対して不活性の溶剤であれば特に制限はない。その具体例としては、例えば、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡｃと略称す）、１−メチルピロリドン（ＮＭＰと略称す）、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦと略称す）、テトラヒドロフラン（ＴＨＦと略称す）、ジオキサン、メチルエチルケトン（ＭＥＫと略称す）、クロロホルム、ジクロロメタンなどが挙げられるが、これらに限定されるものではない。その内、特にＮ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）が好ましい。 In the present invention, the reactions in the production steps (a) and (a1) are preferably carried out in the presence of a solvent, and are not particularly limited as long as they are inert to the reaction. Specific examples thereof include N, N-dimethylacetamide (abbreviated as DMAc), 1-methylpyrrolidone (abbreviated as NMP), N, N-dimethylformamide (abbreviated as DMF), and tetrahydrofuran (abbreviated as THF). ), Dioxane, methyl ethyl ketone (abbreviated as MEK), chloroform, dichloromethane and the like, but are not limited thereto. Of these, N, N-dimethylacetamide (DMAc) is particularly preferable.
本発明の製造工程（ｂ）と（ｂ１）において、一般式「ＮＨ2−Ｒ1−Ｓｉ（Ｒ2）3」(
定義は上記に同じ。)で示されるアミノカップリング試薬の具体例としては、例えば、３
−アミノプロピルトリメトキシシラン（ＡＰｒＴＭＳと略称す）、３−アミノプロピルトリエトキシシラン（ＡＰ〜ＴＥＳと略称す）、３−アミノフェニルトリメトキシシラン（ＡＰＴＭＳと略称す）、３−アミノフェニルトリエトキシシラン（ＡＰＴＥＳと略称す）などが挙げられるが、これらに限定されるものではない。
In the production steps (b) and (b1) of the present invention, the general formula “NH 2 —R 1 —Si (R 2 ) 3 ” (
The definition is the same as above. Specific examples of amino coupling reagents represented by
-Aminopropyltrimethoxysilane (abbreviated as APrTMS), 3-aminopropyltriethoxysilane (abbreviated as AP-TES), 3-aminophenyltrimethoxysilane (abbreviated as APTMS), 3-aminophenyltriethoxysilane (Abbreviated as APTES) and the like, but are not limited thereto.
本発明の製造工程（ｃ）において、ポリセスキシロキサンを調製の際に用いられる一般式「Ｒ3−Ｓｉ（Ｒ4）3」(定義は上記に同じ。)で示される単体としては、例えば、メチ
ルトリメトキシシラン（ＭＴＭＳと略称す）、トリメトキシシラン（ＴＭＳと略称す）、トリエトキシシラン（ＴＥＳと略称す）、メチルトリエトキシシラン（ＭＴＥＳと略称す）、フェニルトリメトキシシラン（ＰＴＭＳと略称す）、フェニルトリエトキシシラン（ＰＴＥＳと略称す）、ビニルトリメトキシシラン（ＶＴＭＳと略称す）、ビニルトリエトキシシラン（ＶＴＥＳと略称す）、トリクロロシラン、メチルトリクロロシラン、フェニルトリクロロシラン、ビニルトリクロロシランなどが挙げられるが、これらに限定されるものではない。
In the production step (c) of the present invention, the simple substance represented by the general formula “R 3 —Si (R 4 ) 3 ” (defined above is the same) used when preparing polysesquisiloxane is, for example, Methyltrimethoxysilane (abbreviated as MTMS), trimethoxysilane (abbreviated as TMS), triethoxysilane (abbreviated as TES), methyltriethoxysilane (abbreviated as MTES), phenyltrimethoxysilane (abbreviated as PTMS) ), Phenyltriethoxysilane (abbreviated as PTES), vinyltrimethoxysilane (abbreviated as VTMS), vinyltriethoxysilane (abbreviated as VTES), trichlorosilane, methyltrichlorosilane, phenyltrichlorosilane, vinyltrichlorosilane However, it is not limited to these.
本発明の製造工程（ｃ）において用いられる触媒としては、有機酸又は無機酸が用いられる。その具体例としては、例えば、塩酸、硫酸、硝酸、燐酸などの無機酸；ギ酸、酢酸、プロピオン酸、シュウ酸、マロン酸、グルタル酸、グリコール酸、酒石酸などの有機酸などが挙げられるが、これらに限定されるものではない。 As the catalyst used in the production process (c) of the present invention, an organic acid or an inorganic acid is used. Specific examples thereof include, for example, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, glutaric acid, glycolic acid, and tartaric acid. It is not limited to these.
本発明において、製造工程（ｃ）で用いられる溶剤としては、特に制限はなく、本発明の反応に不活性なものであれば良く、その具体例としては、例えば、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）、１−メチルピロリドン（ＮＭＰ）、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、テトラヒドロフラン（ＴＨＦ）、ジオキサン、メチルエチルケトン（ＭＥＫ）、クロロホルム、ジクロロメタンなどが挙げられるが、それらに限定されるものではない。その内、Ｎ，Ｎ−ジメチルアセトアミドが好ましく用いられる。 In the present invention, the solvent used in the production step (c) is not particularly limited as long as it is inert to the reaction of the present invention. Specific examples thereof include, for example, N, N-dimethylacetamide ( DMAc), 1-methylpyrrolidone (NMP), N, N-dimethylformamide (DMF), tetrahydrofuran (THF), dioxane, methyl ethyl ketone (MEK), chloroform, dichloromethane and the like, but are not limited thereto. . Of these, N, N-dimethylacetamide is preferably used.
本発明の製造方法において、製造工程（ｃ）の後に、ポリセスキシロキサンについて減圧蒸留を施し副生成物のメタノールを留去する工程を加えることができる。その際、蒸留温度を４０〜４５℃の範囲内に保つ必要がある。蒸留温度が高すぎると反応は続行し、低すぎるとメタノールを十分に留去することが難しい。蒸留後、反応の際に用いた溶剤を留出混合物に加え、総固形物含量を１０〜２０％範囲内に調整する。 In the production method of the present invention, after the production step (c), a step of subjecting polysesquisiloxane to distillation under reduced pressure to distill off methanol as a by-product can be added. In that case, it is necessary to keep distillation temperature in the range of 40-45 degreeC. If the distillation temperature is too high, the reaction continues, and if it is too low, it is difficult to sufficiently distill off methanol. After distillation, the solvent used in the reaction is added to the distillate mixture to adjust the total solids content within the 10-20% range.
製造工程（ｃ）の後に蒸留により副生成物のメタノールを留去しない場合、ポリセスキシロキサン含量は、僅か３０重量％までしか利用できず、そうでない場合、ポリアミド酸が析出するという問題が発生する。 If the by-product methanol is not distilled off by distillation after the production step (c), the polysesquisiloxane content can only be used up to 30% by weight, otherwise the problem of precipitation of polyamic acid occurs. .
本発明の製造工程（ｄ）と（ｄ１）において、ポリセスキシロキサン（又はシリコン アルコキサイド）と、ポリアミド酸との混合は任意の比率でもよく、沈殿や混濁が生じる恐れは全くない。 In the production steps (d) and (d1) of the present invention, the polysesquisiloxane (or silicon alkoxide) and the polyamic acid may be mixed at an arbitrary ratio, and there is no possibility of causing precipitation or turbidity.
本発明の製造工程（ｅ）と（ｅ１）において、基材上に塗布する方法としては、例えば、ロール コート法、流し塗り法、浸し塗り法、吹付け塗り法（スプレー）、自旋塗り法（スピンコート）、カーテン塗り法などが挙げられるが、均一なフィルムを得る立場から、自旋塗り法が特に好ましく用いられる。 In the production steps (e) and (e1) of the present invention, examples of the method of coating on the substrate include a roll coating method, a flow coating method, a dip coating method, a spray coating method (spray), and a self-rotating coating method. (Spin coating), curtain coating method and the like can be mentioned. From the standpoint of obtaining a uniform film, the self-rotating coating method is particularly preferably used.
本発明の製造工程（ｅ）と（ｅ１）において、塗布後のフィルムを昇温固化する方法としては、ベーキング法が使用され、多段式昇温ベーキング法を用いるのが好ましく、これにより溶剤をゆっくりと蒸散することで、フィルムの亀裂を防止することができる。多段式ベーキング法としては、例えば、先に５０〜７０℃で１５〜２５分ベーキングし、次に９０〜１１０℃で１５〜２５分、さらに１４０〜１６０℃で１５〜２５分ベーキングした後、高温炉に移し窒素ガス流通下に２９０〜３１０℃で数時間固化し、最後は、３９０〜４２０℃で数時間固化するが、これらに限定されるものではない。
［実施例］
以下、実施例を用いて本発明をより具体的に説明する。但し、本発明は以下の実施例に限定されない。
In the production steps (e) and (e1) of the present invention, a baking method is used as a method for heating and solidifying the coated film, and it is preferable to use a multistage heating baking method. The film can be prevented from cracking by evaporating. As the multi-stage baking method, for example, first baking is performed at 50 to 70 ° C. for 15 to 25 minutes, then baking at 90 to 110 ° C. for 15 to 25 minutes, further baking at 140 to 160 ° C. for 15 to 25 minutes, and then high temperature. It is transferred to a furnace and solidified at 290 to 310 ° C. for several hours under a nitrogen gas flow, and finally solidified at 390 to 420 ° C. for several hours, but is not limited thereto.
[Example]
Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
＜理論分子量５０００ｇ／モルのポリアミド酸の製造＞
４，４'−オキソジアニリン（ＯＤＡ、０．６８６ｇ）をＮ，Ｎ−ジメチルアセトアミ
ド（ＤＡＭｃ、８．５ｇ）に溶解し、２０分攪拌した後、ピロメリト酸二無水物（ＰＭＤＡ、０．８１４ｇ）をゆっくりと添加し、室温下で４時間攪拌した後、さらに３−アミノプロピルトリメトキシシラン（ＡＰｒＴＭＳ、０．１０７ｇ）を加えた。反応系中、ＰＭＤＡ：ＯＤＡ：ＡＰｒＴＭＳのモル比は１２．４：１１．４：２であった。ＡＰｒＴＭＳの添加後、２０分反応させた後、ポリアミド酸溶液（Ａ）を得た。
<Production of polyamic acid having a theoretical molecular weight of 5000 g / mol>
4,4′-oxodianiline (ODA, 0.686 g) was dissolved in N, N-dimethylacetamide (DAMc, 8.5 g), stirred for 20 minutes, and then pyromellitic dianhydride (PMDA, 0.814 g). ) Was slowly added and stirred at room temperature for 4 hours, and further 3-aminopropyltrimethoxysilane (APrTMS, 0.107 g) was added. In the reaction system, the molar ratio of PMDA: ODA: APrTMS was 12.4: 11.4: 2. After the addition of APrTMS, the mixture was reacted for 20 minutes to obtain a polyamic acid solution (A).
＜ポリメチルセスキシロキサン溶液の調製＞
三つロフラスコにメチルトリメトキシシラン（ＭＴＭＳ，１０．１７ｇ）単体を入れ、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ，３０ｇ）を加え、シリコンオイルバス中、６０℃に加熱し、窒素ガスを通じ、冷却管により還流しながら反応させた。これとは別に、恒圧下に、漏斗（ロート）にＤＭＡｃ（７．１４ｇ）、脱イオン水（２，６８７ｇ）と塩酸（０．０５５ｇ）を入れた後、３０分かけてゆっくりと還流中の三つロフラスコにロートを通して滴下し、３時間反応を続けた。反応溶液を真空ロータリエバポレター中、４０℃下で減圧濃縮して、メタノールと一部分の溶剤を留去し、総固形物含量が３０％になるまで続け、最後に溶剤としてＤＭＡｃを加え１５％に希釈し、ポリセスキシロキサン溶液（Ｃ）を得た。
<Preparation of polymethylsesquisiloxane solution>
Place methyltrimethoxysilane (MTMS, 10.17 g) alone in a three-flask, add N, N-dimethylacetamide (DMAc, 30 g), heat to 60 ° C. in a silicone oil bath, and pass nitrogen gas through cooling tube The reaction was carried out at reflux. Separately, DMAc (7.14 g), deionized water (2,687 g) and hydrochloric acid (0.055 g) were placed in a funnel under constant pressure, and then slowly refluxed over 30 minutes. A funnel was added dropwise to the three-rottle flask, and the reaction was continued for 3 hours. The reaction solution was concentrated under reduced pressure at 40 ° C. in a vacuum rotary evaporator, methanol and a part of the solvent were distilled off, and continued until the total solid content was 30%, and finally DMAc was added as a solvent to 15%. Dilution was performed to obtain a polysesquisiloxane solution (C).
＜ポリセスキシロキサン溶液とポリアミド酸溶液とのゾル−ゲル反応＞
ポリセスキシロキサン溶液（Ｃ；１ｇ）とポリアミド酸溶液（Ａ；９ｇ）との混合物中に脱イオン水（０．０３９ｇ）を加え、ポリアミド酸の末端アルコキシシラン基を加水分解し、室温下で１時間攪拌して、ポリセスキシロキサン−ポリアミド酸のハイブリッド溶液（ポリセスキシロキサン含量は１０重量％）を得た。
<Sol-gel reaction between polysesquisiloxane solution and polyamic acid solution>
Deionized water (0.039 g) is added to a mixture of the polysesquisiloxane solution (C; 1 g) and the polyamic acid solution (A; 9 g) to hydrolyze the terminal alkoxysilane group of the polyamic acid, and 1 at room temperature. The mixture was stirred for a time to obtain a polysesquisiloxane-polyamic acid hybrid solution (polysesquisiloxane content of 10% by weight).
上記で得た溶液を自旋塗り法（スピンコート）により３０００ｒｐｍの回転速度で４インチのシリコン ウエハー上に６０秒塗布し、次に、ヒートプレート上下記の順序でベーキングした。 The solution obtained above was coated on a 4-inch silicon wafer for 60 seconds at a rotational speed of 3000 rpm by a self-rotating coating method (spin coating), and then baked in the following order on a heat plate.
すなわち、６０℃で２０分、１００℃で２０分、１５０℃で２０分それぞれベーキングし、その後、高温炉に移し、窒素ガスを通じながら、３００℃で１時間固化し、最後に４００℃で１時間固化して、ポリメチルセスキシロキサン−ポリアミド酸ハイブリッドフィルムを得た。
［実施例２〜８］
That is, baking was performed at 60 ° C. for 20 minutes, 100 ° C. for 20 minutes, and 150 ° C. for 20 minutes, then transferred to a high temperature furnace and solidified at 300 ° C. for 1 hour while passing nitrogen gas, and finally at 400 ° C. for 1 hour. Solidifying to obtain a polymethylsesquisiloxane-polyamic acid hybrid film.
[ Examples 2 to 8]
実施例２〜８は、実施例１と同じ工程により操作した。ただし、実施例２〜８では、実施例１において、セスキシロキサンの比率をハイブリッド溶液中、それぞれ０％、２０％、４０％、６０％、８０％、１００％と１００％に変更した。又、実施例８において得たフィルムは、乾燥しただけで、高温炉内での固化工程を行わなかった。
[実施例９]
Examples 2-8 were operated by the same process as Example 1. However, in Examples 2 to 8, the ratio of sesquisiloxane in Example 1 was changed to 0%, 20%, 40%, 60%, 80%, 100%, and 100% in the hybrid solution, respectively. Moreover, the film obtained in Example 8 was only dried and was not subjected to a solidification step in a high temperature furnace.
[Example 9]
＜理論分子量１０００ｇ／モルのポリアミド酸の製造＞
４，４’−オキソジアニリン（ＯＤＡ，０．５６９ｇ）をＮ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ，８．５ｇ）に溶解し、２０分攪拌した後、ピロメリト酸二無水物（ＰＭＤＡ，０．９３１ｇ）をゆっくり加え、室温下で４時間攪拌した後、さらに、３−アミノプロピルトリメトキシシラン（ＡＰｒＴＭＳ，０．５０９ｇ）を加える。反応系中ＰＭＤＡ：ＯＤＡ：ＡＰｒＴＭＳのモル比は３：２：２であり、２０分反応した後、ポリアミド酸溶液（Ｂ）を得た。
<Production of polyamic acid having a theoretical molecular weight of 1000 g / mol>
4,4′-oxodianiline (ODA, 0.569 g) was dissolved in N, N-dimethylacetamide (DMAc, 8.5 g), stirred for 20 minutes, and then pyromellitic dianhydride (PMDA, 0.931 g). ) Is slowly added and stirred at room temperature for 4 hours, and further 3-aminopropyltrimethoxysilane (APrTMS, 0.509 g) is added. The molar ratio of PMDA: ODA: APrTMS in the reaction system was 3: 2: 2, and after reacting for 20 minutes, a polyamic acid solution (B) was obtained.
＜ポリセスキシロキサン溶液とポリアミド酸溶液とのゾル−ゲル反応＞
ポリセスキシロキサン溶液（Ｃ，１ｇ）とポリアミド酸溶液（Ｂ，８ｇ）の混合物中に、脱イオン水（０．１６４ｇ）を加えて、ポリアミド酸の末端アルコキシシラン基の加水分解を行ない、同時に室温下で１時間攪拌し、ポリセスキシロキサン−ポリアミド酸 ハイブリッド溶液（ポリセスキシロキサン含量は２０重量％）を得た。
<Sol-gel reaction between polysesquisiloxane solution and polyamic acid solution>
To the mixture of the polysesquisiloxane solution (C, 1 g) and the polyamic acid solution (B, 8 g), deionized water (0.164 g) is added to hydrolyze the terminal alkoxysilane group of the polyamic acid, and at the same time at room temperature. The mixture was stirred for 1 hour to obtain a polysesquisiloxane-polyamic acid hybrid solution (polysesquisiloxane content of 20% by weight).
上記により得た溶液を自旋塗り法（スピンコート）を用い、３０００ｒｐｍの回転速度で４インチのシリコンウエハー上に６０秒かけて塗布し、次に下記の工程順序によりヒートプレートでベーキングした。 The solution obtained as described above was applied on a 4-inch silicon wafer at a rotation speed of 3000 rpm for 60 seconds using a self-rotating coating method (spin coating), and then baked on a heat plate according to the following process sequence.
すなわち、６０℃で２０分、１００℃で２０分、１５０℃で２０分間それぞれベーキングし、次に高温炉に移し、窒素ガスを通じて３００℃下で１時間固化し、最後に、４００℃下で１時間固化して、ポリメチルセスキシロキサン−ポリアミド酸ハイブリッドフィルムを得た。
[実施例１０]
That is, baking was performed at 60 ° C. for 20 minutes, 100 ° C. for 20 minutes, and 150 ° C. for 20 minutes, then transferred to a high temperature furnace, solidified through nitrogen gas at 300 ° C. for 1 hour, and finally at 400 ° C. for 1 hour. Solidifying for a time, a polymethylsesquisiloxane-polyamic acid hybrid film was obtained.
[Example 10 ]
＜理論分子量１０００ｇ／モルのポリアミド酸の製造＞
４，４’−オキソジアニリン（ＯＤＡ，４．１０ｇ）をＮ，Ｎ’−ジメチルアセトアミド（ＤＭＡｃ，６２．２ｇ）に溶解し、２０分攪拌した後、４，４−ジフタル酸二無水物（ＢＰＤＡ，９．１２ｇ）をゆっくり加え、室温下で４時間攪拌した後、さらに３−アミノプロピルトリメトキシシラン（ＡＰｒＴＭＳ、３．６８ｇ）を加える。反応系中ＢＰＤＡ：ＯＤＡ：ＡＰｒＴＭＳのモル比は３：２：２であり、２０分反応した後、ポリアミド酸（１３．６ｇ）を含むＮ，Ｎ−ジメチルアセトアミド溶液（Ｄ，６２．２ｇ）を得た。
<Production of polyamic acid having a theoretical molecular weight of 1000 g / mol>
4,4′-oxodianiline (ODA, 4.10 g) was dissolved in N, N′-dimethylacetamide (DMAc, 62.2 g), stirred for 20 minutes, and then 4,4-diphthalic dianhydride ( BPDA, 9.12 g) is slowly added and stirred at room temperature for 4 hours, followed by further addition of 3-aminopropyltrimethoxysilane (APrTMS, 3.68 g). The molar ratio of BPDA: ODA: APrTMS in the reaction system was 3: 2: 2, and after reaction for 20 minutes, an N, N-dimethylacetamide solution (D, 62.2 g) containing polyamic acid (13.6 g) was added. Obtained.
＜シリコン アルコキサイド溶液とポリアミド酸溶液とのゾル−ゲル反応＞
上記で得たポリアミド酸（１３．６ｇ）を含むＮ，Ｎ−ジメチルアセトアミド溶液（Ｄ，６２．２ｇ）中、テトラメトキシシラン（ＴＭＯＳ，１５．６ｇ）を加え、さらに脱イオン水（８．３ｇ）を添加して、ポリアミド酸末端のアルコキシシラン基を加水分解し、同時に室温下で１時間攪拌して、ポリシロキサン−ポリアミド酸ハイブリッド溶液を得た。
<Sol-gel reaction between silicon alkoxide solution and polyamic acid solution>
Tetramethoxysilane (TMOS, 15.6 g) is added to the N, N-dimethylacetamide solution (D, 62.2 g) containing the polyamic acid (13.6 g) obtained above, and deionized water (8.3 g) is added. ) To hydrolyze the polyamic acid-terminated alkoxysilane group and simultaneously stirred at room temperature for 1 hour to obtain a polysiloxane-polyamic acid hybrid solution.
上記で得た溶液を自旋塗り法（スピンコート）を用い、３０００ｒｐｍの回転速度で４インチ シリコン ウエハーに６０秒塗布し、次にヒートプレートを用い下記の工程順序で操作した。 The solution obtained above was applied to a 4 inch silicon wafer for 60 seconds at a rotation speed of 3000 rpm using a self-rotating coating method (spin coating), and then operated in the following process sequence using a heat plate.
すなわち、６０℃で２０分、１００℃で２０分、１５０℃で２０分間それぞれベーキングし、その後高温炉に移し、窒素ガスを通じ、３００℃下で１時間固化し、最後に４００℃で１時間固形して、シリコン アルコキサイド−ポリイミド ハイブリッドフィルムを得た。 That is, baking was performed at 60 ° C. for 20 minutes, 100 ° C. for 20 minutes, and 150 ° C. for 20 minutes, then transferred to a high-temperature furnace, solidified at 300 ° C. for 1 hour through nitrogen gas, and finally solid at 400 ° C. for 1 hour. Thus, a silicon alkoxide-polyimide hybrid film was obtained.
上記の実施例により得られたフィルム材料を用い、例えば、ＦＴ−ＩＲ、ＡＦＭ［(Atomic Force Microscopic) spectrum］、ＳＥＭ、粗度、屈折率、複屈折率、近赤外分光吸
光度、誘電率、ＴＧＡ、熱分解温度と熱分析などのフィルム特性を測定し、その結果を第２〜１２図中にそれぞれ示した。
Using the film material obtained by the above examples, for example, FT-IR, AFM [(Atomic Force Microscopic) spectrum], SEM, roughness, refractive index, birefringence, near infrared spectral absorbance, dielectric constant, Film characteristics such as TGA, thermal decomposition temperature and thermal analysis were measured, and the results are shown in FIGS.
第２図のＦＴ−ＩＲより、ポリメチルセスキシロキサン（又はシリコン アルコキシド）又はポリアミド酸の反応は完全に終了したことが明らかに示され、かつそれぞれのピーク面積は成分の比率により変化していることが分る。又、第３図のＡＦＭ図より低分子量のポリイミドが比較して良好な表面平坦度を有することが明らかである。第４図より組成分の異なるフィルムの粗度については、低分子量のポリアミド酸から製造したハイブリッドフィルムの粗度がすべて１ｎｍ以下であることが分かり、カップリング試薬を加えていないフィルムの粗度が最も大きい値を示していることが明らかにされた。さらに、第５図のＳＥＭ図より高分子量のポリアミド酸より製造されたハイブリッドフィルムにおいて、ポリセスキシロキサン含量がより多い場合、明らかに相分離の現象を生じ、架橋密度を高めることで確かに相分離を軽減する効果があることを立証している。又、第６図の結果より、屈折率はポリアミド酸とポリセスキシロキサンの比率を左右することで変えられることが明らかにされた。なお第７図により、複屈折率は無機材料の添加により高分子の排列がこわれ、低くなることが明らかとなり、複屈折率は無機材料の増加にともないやや低くなることが判る。第８図は、本発明のハイブリッドフィルム材料における近赤外線フォトグラフを示すものであるが、通常の光導波領域では吸収がなく、光導波路材料として用いることができる。第９図より誘電率は吸湿性と膜の厚さにより、非リニアー性の変化を呈し、又無機材料の加入にともない低下する。第１０図より無機成分はフィルム全体の耐熱性を明らかに高め、しかも低分子量のポリアミド酸に比べて高分子量のポリアミド酸を用いて製造したフィルムが、より耐熱性を示すことが分かる。第１１図より熱分解温度はすべて５４５℃以上であり、本発明のハイブリッドフィルム全部が極めて優れた耐熱性を有することが明らかにされた。ＤＳＣの結果からもガラス転移温度が発見されなかった。第１２図の熱応力図より無機成分を加えることは、その安定性を高めることが明らかにされた。 The FT-IR in FIG. 2 clearly shows that the reaction of polymethylsesquisiloxane (or silicon alkoxide) or polyamic acid has been completely completed, and that each peak area varies depending on the ratio of components. I understand. In addition, it is clear from the AFM diagram of FIG. 3 that the low molecular weight polyimide has a better surface flatness than the polyimide. From FIG. 4, it can be seen that the roughness of the films having different compositions is about 1 nm or less for all of the hybrid films produced from the low molecular weight polyamic acid. It was revealed that it showed the largest value. Furthermore, in the hybrid film produced from the high molecular weight polyamic acid from the SEM diagram of FIG. 5, when the polysesquisiloxane content is higher, the phase separation phenomenon clearly occurs, and the cross-linking density is surely increased. It has been proved that there is an effect to reduce. Also, from the results of FIG. 6, it was clarified that the refractive index can be changed by controlling the ratio of polyamic acid and polysesquisiloxane. From FIG. 7, it is clear that the birefringence is reduced by the addition of the inorganic material, resulting in the lowering of the polymer, and the birefringence becomes slightly lower as the inorganic material increases. FIG. 8 shows a near-infrared photograph in the hybrid film material of the present invention, but there is no absorption in a normal optical waveguide region, and it can be used as an optical waveguide material. According to FIG. 9, the dielectric constant exhibits a non-linear change depending on the hygroscopicity and the film thickness, and decreases with the addition of the inorganic material. From FIG. 10, it can be seen that the inorganic component clearly increases the heat resistance of the whole film, and that the film produced using the high molecular weight polyamic acid as compared with the low molecular weight polyamic acid exhibits more heat resistance. From FIG. 11, all the thermal decomposition temperatures were 545 ° C. or more, and it was revealed that all the hybrid films of the present invention have extremely excellent heat resistance. The glass transition temperature was not found from the DSC results. From the thermal stress diagram of FIG. 12, it has been clarified that adding an inorganic component increases its stability.
以上に述べたことから、本発明のハイブリッドフィルム材料は優れた耐熱性と光学性質を有し、通常のハイブリッドフィルムに見られる相分離現象がなく、耐高温性を必要とする光学材料や低誘電率材料に有用であることが判る。
As described above, the hybrid film material of the present invention has excellent heat resistance and optical properties, does not have the phase separation phenomenon found in ordinary hybrid films, and requires optical materials and low dielectrics that require high temperature resistance. It is found to be useful for rate materials.
Claims (6)
（ａ）芳香族ジアミンと芳香族二酸無水物とを、室温〜５０℃範囲内の温度で反応させて、ポリアミド酸を得る工程（但し、上記の芳香族ジアミンと芳香族二酸無水物との当量比（equivalent ratio：芳香族二酸無水物の酸無水物当量数／芳香族ジアミンのアミン当量数）は２以下である。）；
（ｂ）一般式「ＮＨ2−Ｒ1−Ｓｉ（Ｒ2）3」（式中、Ｒ1はＣ1〜6アルキレン基、あるい
はフェニレン基を示し、Ｒ2はそれぞれ同じでも異なっていてもよく、Ｃ1〜6アルコキシ
基を示す。）で示されるアミノ基を含有するカップリング試薬を用いて、上記工程（ａ）で調製したポリアミド酸とのカップリング反応を行ない、末端が、アミノ基含有カップリング試薬で封じられたポリアミド酸を得る工程（但し、上記のカップリング試薬は、該試薬のアミン当量数が、ジアミンのアミン当量数よりも少ない量で用いる。）；
（ｃ）一般式「Ｒ3−Ｓｉ（Ｒ4）3」（式中、Ｒ3は水素原子、Ｃ1〜6アルキル基、Ｃ2〜6アルケニル基あるいはフェニル基を示し、Ｒ4はそれぞれ独立してハロゲン原子、Ｃ1〜6
アルコキシ基、Ｃ2〜6アルケニルオキシ基、あるいはフェノキシ基を示す。）で示す単体を使用し、酸触媒と溶剤の存在下、室温〜１００℃範囲の温度下で、ゾル−ゲル反応を行ない、ポリセスキシロキサン［poly(silsesquioxane)］を調製する工程（但し、酸触媒の用量は、反応系をｐＨ１〜４に維持する範囲内で用いられる。）；
（ｄ）上記工程（ｂ）で得られた、末端がアミノ基含有カップリング試薬で封じられたポリアミド酸を用い、脱イオン水の存在下、加水分解することで、上記工程（ｃ）で得られたポリセスキシロキサンとカップリングして、ポリアミド酸とポリセスキシロキサンとの複合材料スラリーを得る工程（但し、カップリングからポリアミド酸のアミノ基含有カップリング試薬の加水分解で使用される脱イオン水の用量は、アミノ基含有カップリング試薬で末端を封じたポリアミド酸の末端アルコキシ基量と同じモル数を用いる。）；
（ｅ）上記工程（ｄ）で得られた複合材料スラリーを基材に塗布し、昇温固化して、ポリイミド／ポリセスキシロキサン有機−無機ハイブリッドフィルム材料を製造する工程。 The manufacturing method of the organic-inorganic hybrid film material characterized by including the following manufacturing processes:
(A) A step of reacting an aromatic diamine and an aromatic dianhydride at a temperature in the range of room temperature to 50 ° C. to obtain a polyamic acid (provided that the above aromatic diamine and aromatic dianhydride (Equivalent ratio : number of acid anhydride equivalents of aromatic dianhydride / number of amine equivalents of aromatic diamine ) is 2 or less);
(B) In the general formula "NH 2 -R 1 -Si (R 2 ) 3 " (wherein, R 1 represents a C 1 ~ 6 alkylene group or a phenylene group, may be R 2 are either the same or different, respectively , using a coupling reagent containing an amino group represented by.) showing a C 1 ~ 6 alkoxy group, subjected to coupling reaction with the polyamic acid prepared in the above step (a), the terminus containing amino groups A step of obtaining a polyamic acid sealed with a coupling reagent (however, the coupling reagent is used in such an amount that the amine equivalent number of the reagent is smaller than the amine equivalent number of the diamine );
(C) the formula "R 3 -Si (R 4) 3" (wherein, R 3 represents a hydrogen atom, C 1 ~ 6 alkyl group, C 2 ~ 6 alkenyl group or a phenyl group, R 4 are each independently a halogen atom, C 1 ~ 6
Alkoxy group, a C 2 ~ 6 alkenyloxy group or a phenoxy group. ) In the presence of an acid catalyst and a solvent in the presence of an acid catalyst and a solvent at a temperature ranging from room temperature to 100 ° C. to prepare polysesquisiloxane [poly (silsesquioxane)] The dosage of the catalyst is used within a range that maintains the reaction system at pH 1 to 4).
(D) Using the polyamic acid obtained in the above step (b), the terminal of which is sealed with an amino group-containing coupling reagent, by hydrolysis in the presence of deionized water, obtained in the above step (c). Coupling with the obtained polysesquisiloxane to obtain a composite slurry of polyamic acid and polysesquisiloxane (however, deionized water used in hydrolysis of the amino acid-containing coupling reagent of polyamic acid from the coupling) The same number of moles as the amount of terminal alkoxy groups of the polyamic acid capped with an amino group-containing coupling reagent is used.);
(E) A step of producing a polyimide / polysesquisiloxane organic-inorganic hybrid film material by applying the composite material slurry obtained in the above step (d) to a substrate and solidifying the mixture at elevated temperature.
水物（ＢＰＤＡ）、４，４−ヘキサフルオロイソプロピレン−ビスフタル酸二無水物（６ＦＤＡ）、１−（トリフルオロメチル）−ベンゼン−２，３，５，６−テトラカルボン酸二無水物（Ｐ３ＦＤＡ）、１，４−ジ（トリフルオロメチル）−ベンゼン−２，３，５，６−テトラカルボン酸二無水物（Ｐ６ＧＤＡ）、１−（３'，４'−ジカルボキシフェニル）−１，３，３−トリメチルインダニル−５，６−ジカルボン酸二無水物、１−（３'，４'−ジカルボキシフェニル）−１，３，３−トリメチルインダニル−６，７−ジカルボン酸二無水物、１−（３'，４'−ジカルボキシフェニル）−３−メチルインダニル−５，６−ジカルボン酸二無水物、１−（３'，４'−ジカルボキシフェニル）−３−メチルインダニル−６，７−ジカルボン酸二無水物、ジアセナフチルベンゼン−２，３，９，１０−テトラカルボン酸二無水物、ナフチル−１，４，５，８−テトラカルボン酸二無水物、２，６−ジクロロナフチル−１，４，５，８−テトラカルボン酸二無水物、２，７−ジクロロナフチル−１，４，５，８−テトラカルボン酸二無水物、２，３，６，７−テトラクロロナフチル−２，４，５，８−テトラカルボン酸二無水物、フェナントレン−１，８，９，１０−テトラカルボン酸二無水物、ベンゾフェノン−３，３'，４，４'−テトラカルボン酸二無水物、ベンゾフェノン−１，２'，３、３'−テトラカルボン酸二無水物、ビフェニル−３，３'，４，４'−テトラカルボン酸二無水物、ベンゾフェノン−３，３'，４，４'−テトラカルボン酸二無水物、ビフェニル−２，２'，３，３'−テトラカルボン酸二無水物、４，４'−イソプロプレン・ジフタル酸二無水物、３，３'−イソプロピレン−ジフタル酸二無水物、４，４'−オキソジフタル酸二無水物、４，４'−スルホニルジフタル酸二無水物、３，３'−オキソジフタル酸二無水物、４，４'−メチレン−ジフタル酸二無水物、４，４'−スルファニルジフタル酸二無水物、４，４'−エチレン−ジフタル酸二無水物、ナフチル−２，３，６７−テトラカルボン酸二無水物、ナフチル−１，２，４，５−テトラカルボン酸二無水物、ナフチル−１，２，５，６−テトラカルボン酸二無水物、ベンゼン−１，２，３，４−テトラカルボン酸二無水物、ピラジニル−２，３，５，６−テトラカルボン酸二無水物からなる群より選ばれる請求項１に記載の方法。 Aromatic dianhydrides are pyromellitic dianhydride (PMDA), 4,4-bisphthalic dianhydride (BPDA), 4,4-hexafluoroisopropylene-bisphthalic dianhydride (6FDA), 1- (Trifluoromethyl) -benzene-2,3,5,6-tetracarboxylic dianhydride (P3FDA), 1,4-di (trifluoromethyl) -benzene-2,3,5,6-tetracarboxylic acid Dianhydride (P6GDA), 1- (3 ′, 4′-dicarboxyphenyl) -1,3,3-trimethylindanyl-5,6-dicarboxylic dianhydride, 1- (3 ′, 4′- Dicarboxyphenyl) -1,3,3-trimethylindanyl-6,7-dicarboxylic dianhydride, 1- (3 ′, 4′-dicarboxyphenyl) -3-methylindanyl-5,6-dicarboxylic Acid dianhydride, 1- ( ', 4'-dicarboxyphenyl) -3-methylindanyl-6,7-dicarboxylic dianhydride, diacenaphthylbenzene-2,3,9,10-tetracarboxylic dianhydride, naphthyl-1, 4,5,8-tetracarboxylic dianhydride, 2,6-dichloronaphthyl-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthyl-1,4,5,8- Tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthyl-2,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride Benzophenone-3,3 ′, 4,4′-tetracarboxylic dianhydride, benzophenone-1,2 ′, 3,3′-tetracarboxylic dianhydride, biphenyl-3,3 ′, 4,4 ′ -Tetracarboxylic dianhydride, benzopheno -3,3 ', 4,4'-tetracarboxylic dianhydride, biphenyl-2,2', 3,3'-tetracarboxylic dianhydride, 4,4'-isoproprene diphthalic dianhydride 3,3′-Isopropylene-diphthalic dianhydride, 4,4′-oxodiphthalic dianhydride, 4,4′-sulfonyldiphthalic dianhydride, 3,3′-oxodiphthalic dianhydride 4,4′-methylene-diphthalic dianhydride, 4,4′-sulfanyl diphthalic dianhydride, 4,4′-ethylene-diphthalic dianhydride, naphthyl-2,3,67-tetracarboxylic Acid dianhydride, naphthyl-1,2,4,5-tetracarboxylic dianhydride, naphthyl-1,2,5,6-tetracarboxylic dianhydride, benzene-1,2,3,4-tetra Carboxylic dianhydride, pyrazinyl-2,3,5,6-tetracarboxylic The method of claim 1 selected from the group consisting of dianhydrides.
シラン（ＭＴＭＳ）、トリメトキシシラン（ＴＭＳ）、トリエトキシシラン（ＴＥＳ）、メチルトリエトキシシラン（ＭＴＥＳ）、フェニルトリメトキシシラン（ＰＴＭＳ）、フェニルトリエトキシシラン（ＰＴＥＳ）、ビニルトリメトキシシラン（ＶＴＭＳ）、ビニルトリエトキシシラン（ＶＴＥＳ）、トリクロロシラン、メチルトリクロロシラン、フェニルトリクロロシラン、ビニルトリクロロシランからなる群から選ばれる請求項１に記載の方法。 The simple substance represented by the general formula “R 3 —Si (R 4 ) 3 ” (same as above) is methyltrimethoxysilane (MTMS), trimethoxysilane (TMS), triethoxysilane (TES), methyltriethoxy. Silane (MTES), phenyltrimethoxysilane (PTMS), phenyltriethoxysilane (PTES), vinyltrimethoxysilane (VTMS), vinyltriethoxysilane (VTES), trichlorosilane, methyltrichlorosilane, phenyltrichlorosilane, vinyltri The method of claim 1 selected from the group consisting of chlorosilanes.
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