JP2021195474A - Modified siloxane diacid anhydride and polyimide resin - Google Patents
Modified siloxane diacid anhydride and polyimide resin Download PDFInfo
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- JP2021195474A JP2021195474A JP2020103831A JP2020103831A JP2021195474A JP 2021195474 A JP2021195474 A JP 2021195474A JP 2020103831 A JP2020103831 A JP 2020103831A JP 2020103831 A JP2020103831 A JP 2020103831A JP 2021195474 A JP2021195474 A JP 2021195474A
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- modified siloxane
- compound
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- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229920001721 polyimide Polymers 0.000 title claims abstract description 32
- 239000009719 polyimide resin Substances 0.000 title claims abstract description 31
- 150000008064 anhydrides Chemical class 0.000 title claims abstract description 17
- 125000004018 acid anhydride group Chemical group 0.000 claims abstract description 20
- 125000000962 organic group Chemical group 0.000 claims abstract description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 10
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 9
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 8
- 125000005843 halogen group Chemical group 0.000 claims abstract description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- -1 diamine compound Chemical class 0.000 claims description 54
- 150000001875 compounds Chemical class 0.000 claims description 20
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 13
- 150000008065 acid anhydrides Chemical class 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 7
- 150000003377 silicon compounds Chemical class 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 125000004429 atom Chemical group 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 108
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 99
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 66
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 43
- 239000000203 mixture Substances 0.000 description 41
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 31
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 22
- 229910052697 platinum Inorganic materials 0.000 description 22
- 239000002244 precipitate Substances 0.000 description 22
- 239000000243 solution Substances 0.000 description 22
- 238000005160 1H NMR spectroscopy Methods 0.000 description 18
- 239000011259 mixed solution Substances 0.000 description 18
- WUMMIJWEUDHZCL-UHFFFAOYSA-N 3-prop-2-enyloxolane-2,5-dione Chemical compound C=CCC1CC(=O)OC1=O WUMMIJWEUDHZCL-UHFFFAOYSA-N 0.000 description 16
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 13
- 239000002904 solvent Substances 0.000 description 12
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 11
- BEKFRNOZJSYWKZ-UHFFFAOYSA-N 4-[2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(N)C=C1 BEKFRNOZJSYWKZ-UHFFFAOYSA-N 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 239000012299 nitrogen atmosphere Substances 0.000 description 11
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 9
- BSXVSQHDSNEHCJ-UHFFFAOYSA-N [(dimethyl-$l^{3}-silanyl)oxy-diphenylsilyl]oxy-dimethylsilicon Chemical compound C=1C=CC=CC=1[Si](O[Si](C)C)(O[Si](C)C)C1=CC=CC=C1 BSXVSQHDSNEHCJ-UHFFFAOYSA-N 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 9
- 239000008096 xylene Substances 0.000 description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- 125000005336 allyloxy group Chemical group 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 238000006459 hydrosilylation reaction Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 4
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 4
- 125000002723 alicyclic group Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002210 silicon-based material Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 description 2
- 0 *N(C(N(CC=C)C(N1CC=C)=O)=O)C1=O Chemical compound *N(C(N(CC=C)C(N1CC=C)=O)=O)C1=O 0.000 description 2
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- KNDQHSIWLOJIGP-XPLVVLGFSA-N O=C([C@H]1C2C3C=CC1C3)OC2=O Chemical compound O=C([C@H]1C2C3C=CC1C3)OC2=O KNDQHSIWLOJIGP-XPLVVLGFSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- OOGRAMOPTBMVKO-UHFFFAOYSA-N bis[[ethenyl(dimethyl)silyl]oxy]-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](O[Si](C)(C)C=C)(O[Si](C)(C)C=C)C1=CC=CC=C1 OOGRAMOPTBMVKO-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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- VLNRSEGRGSDKLS-UHFFFAOYSA-N ethenyl-[4-[ethenyl(dimethyl)silyl]phenyl]-dimethylsilane Chemical compound C=C[Si](C)(C)C1=CC=C([Si](C)(C)C=C)C=C1 VLNRSEGRGSDKLS-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- UHXCHUWSQRLZJS-UHFFFAOYSA-N (4-dimethylsilylidenecyclohexa-2,5-dien-1-ylidene)-dimethylsilane Chemical compound C[Si](C)C1=CC=C([Si](C)C)C=C1 UHXCHUWSQRLZJS-UHFFFAOYSA-N 0.000 description 1
- WJPCIELTJWREGF-UHFFFAOYSA-N (4-diphenylsilylphenyl)-diphenylsilane Chemical compound C1=CC=CC=C1[SiH](C=1C=CC(=CC=1)[SiH](C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 WJPCIELTJWREGF-UHFFFAOYSA-N 0.000 description 1
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 1
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- WTBVSWPUNJVDHW-UHFFFAOYSA-N 1,1-bis(ethenoxy)nonane Chemical compound CCCCCCCCC(OC=C)OC=C WTBVSWPUNJVDHW-UHFFFAOYSA-N 0.000 description 1
- LERDAFCBKALCKT-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-(2,3,4-trifluorophenyl)benzene Chemical group FC1=C(F)C(F)=CC=C1C1=C(F)C(F)=C(F)C(F)=C1F LERDAFCBKALCKT-UHFFFAOYSA-N 0.000 description 1
- CYIGRWUIQAVBFG-UHFFFAOYSA-N 1,2-bis(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOCCOC=C CYIGRWUIQAVBFG-UHFFFAOYSA-N 0.000 description 1
- OGYKDKNLZIEALI-UHFFFAOYSA-N 1,3-bis(ethenoxy)adamantane Chemical compound C1C(C2)CC3CC1(OC=C)CC2(OC=C)C3 OGYKDKNLZIEALI-UHFFFAOYSA-N 0.000 description 1
- IBVPVTPPYGGAEL-UHFFFAOYSA-N 1,3-bis(prop-1-en-2-yl)benzene Chemical compound CC(=C)C1=CC=CC(C(C)=C)=C1 IBVPVTPPYGGAEL-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- MWZJGRDWJVHRDV-UHFFFAOYSA-N 1,4-bis(ethenoxy)butane Chemical compound C=COCCCCOC=C MWZJGRDWJVHRDV-UHFFFAOYSA-N 0.000 description 1
- ZENYUPUKNXGVDY-UHFFFAOYSA-N 1,4-bis(prop-1-en-2-yl)benzene Chemical compound CC(=C)C1=CC=C(C(C)=C)C=C1 ZENYUPUKNXGVDY-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- IYSVFZBXZVPIFA-UHFFFAOYSA-N 1-ethenyl-4-(4-ethenylphenyl)benzene Chemical group C1=CC(C=C)=CC=C1C1=CC=C(C=C)C=C1 IYSVFZBXZVPIFA-UHFFFAOYSA-N 0.000 description 1
- SDRZFSPCVYEJTP-UHFFFAOYSA-N 1-ethenylcyclohexene Chemical compound C=CC1=CCCCC1 SDRZFSPCVYEJTP-UHFFFAOYSA-N 0.000 description 1
- SCZZNWQQCGSWSZ-UHFFFAOYSA-N 1-prop-2-enoxy-4-[2-(4-prop-2-enoxyphenyl)propan-2-yl]benzene Chemical compound C=1C=C(OCC=C)C=CC=1C(C)(C)C1=CC=C(OCC=C)C=C1 SCZZNWQQCGSWSZ-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- UXOXUHMFQZEAFR-UHFFFAOYSA-N 2,2',5,5'-Tetrachlorobenzidine Chemical group C1=C(Cl)C(N)=CC(Cl)=C1C1=CC(Cl)=C(N)C=C1Cl UXOXUHMFQZEAFR-UHFFFAOYSA-N 0.000 description 1
- WVXLLHWEQSZBLW-UHFFFAOYSA-N 2-(4-acetyl-2-methoxyphenoxy)acetic acid Chemical compound COC1=CC(C(C)=O)=CC=C1OCC(O)=O WVXLLHWEQSZBLW-UHFFFAOYSA-N 0.000 description 1
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical group C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 1
- BASOBOGLLJSNNB-UHFFFAOYSA-N 3,5-diamino-n-[3-(trifluoromethyl)phenyl]benzamide Chemical compound NC1=CC(N)=CC(C(=O)NC=2C=C(C=CC=2)C(F)(F)F)=C1 BASOBOGLLJSNNB-UHFFFAOYSA-N 0.000 description 1
- JCPLPXHXAQONRQ-UHFFFAOYSA-N 3,5-diamino-n-[4-(trifluoromethyl)phenyl]benzamide Chemical compound NC1=CC(N)=CC(C(=O)NC=2C=CC(=CC=2)C(F)(F)F)=C1 JCPLPXHXAQONRQ-UHFFFAOYSA-N 0.000 description 1
- OOXMQACSWCZQLX-UHFFFAOYSA-N 3,9-bis(ethenyl)-2,4,8,10-tetraoxaspiro[5.5]undecane Chemical compound C1OC(C=C)OCC21COC(C=C)OC2 OOXMQACSWCZQLX-UHFFFAOYSA-N 0.000 description 1
- MVFJHAFRIJSPFI-UHFFFAOYSA-N 3-(3,4,5-triphenylthiophen-2-yl)benzene-1,2-diamine Chemical compound NC=1C(=C(C=CC=1)C=1SC(=C(C=1C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1)N MVFJHAFRIJSPFI-UHFFFAOYSA-N 0.000 description 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- DKKYOQYISDAQER-UHFFFAOYSA-N 3-[3-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)=C1 DKKYOQYISDAQER-UHFFFAOYSA-N 0.000 description 1
- LBPVOEHZEWAJKQ-UHFFFAOYSA-N 3-[4-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 LBPVOEHZEWAJKQ-UHFFFAOYSA-N 0.000 description 1
- NYRFBMFAUFUULG-UHFFFAOYSA-N 3-[4-[2-[4-(3-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=C(N)C=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=CC(N)=C1 NYRFBMFAUFUULG-UHFFFAOYSA-N 0.000 description 1
- LOYDTBZMMPQJNI-UHFFFAOYSA-N 3a-methyl-5,6-dihydro-4h-2-benzofuran-1,3-dione Chemical compound C1CCC=C2C(=O)OC(=O)C21C LOYDTBZMMPQJNI-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 1
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- 238000009429 electrical wiring Methods 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- OAOUCIAPXRFNKQ-UHFFFAOYSA-N ethenyl-[2-[ethenyl(diphenyl)silyl]ethyl]-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(C=C)CC[Si](C=C)(C=1C=CC=CC=1)C1=CC=CC=C1 OAOUCIAPXRFNKQ-UHFFFAOYSA-N 0.000 description 1
- JCDJGBUVIXYPDE-UHFFFAOYSA-N ethenyl-[3-[ethenyl(dimethyl)silyl]phenyl]-dimethylsilane Chemical compound C=C[Si](C)(C)C1=CC=CC([Si](C)(C)C=C)=C1 JCDJGBUVIXYPDE-UHFFFAOYSA-N 0.000 description 1
- SBOJWTKWEIHBKC-UHFFFAOYSA-N ethenyl-[3-[ethenyl(dimethyl)silyl]propyl]-dimethylsilane Chemical compound C=C[Si](C)(C)CCC[Si](C)(C)C=C SBOJWTKWEIHBKC-UHFFFAOYSA-N 0.000 description 1
- XNLPWCXWJIJUPW-UHFFFAOYSA-N ethenyl-[3-[ethenyl(diphenyl)silyl]phenyl]-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](C=1C=C(C=CC=1)[Si](C=C)(C=1C=CC=CC=1)C=1C=CC=CC=1)(C=C)C1=CC=CC=C1 XNLPWCXWJIJUPW-UHFFFAOYSA-N 0.000 description 1
- KGVOOQYVJDIBGI-UHFFFAOYSA-N ethenyl-[4-[ethenyl(dimethyl)silyl]butyl]-dimethylsilane Chemical compound C=C[Si](C)(C)CCCC[Si](C)(C)C=C KGVOOQYVJDIBGI-UHFFFAOYSA-N 0.000 description 1
- VHOHSCJSHRIPGX-UHFFFAOYSA-N ethenyl-[5-[ethenyl(dimethyl)silyl]pentyl]-dimethylsilane Chemical compound C[Si](CCCCC[Si](C=C)(C)C)(C=C)C VHOHSCJSHRIPGX-UHFFFAOYSA-N 0.000 description 1
- KSVRFYAAMRUWPZ-UHFFFAOYSA-N ethenyl-[[ethenyl(dimethyl)silyl]methyl]-dimethylsilane Chemical compound C=C[Si](C)(C)C[Si](C)(C)C=C KSVRFYAAMRUWPZ-UHFFFAOYSA-N 0.000 description 1
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- SSXMPWKNMJXRDH-UHFFFAOYSA-N heptane-1,4,4,7-tetramine Chemical compound NCCCC(N)(N)CCCN SSXMPWKNMJXRDH-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- FSCVJWOCZOPLET-UHFFFAOYSA-N methyl-[4-[methyl(phenyl)silyl]phenyl]-phenylsilane Chemical compound C=1C=C([SiH](C)C=2C=CC=CC=2)C=CC=1[SiH](C)C1=CC=CC=C1 FSCVJWOCZOPLET-UHFFFAOYSA-N 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- LZPMSYKYCRTNKV-UHFFFAOYSA-N penta-1,4-dien-3-yl-(4-penta-1,4-dien-3-ylsilylphenyl)silane Chemical compound C(=C)C(C=C)[SiH2]C1=CC=C(C=C1)[SiH2]C(C=C)C=C LZPMSYKYCRTNKV-UHFFFAOYSA-N 0.000 description 1
- PKELYQZIUROQSI-UHFFFAOYSA-N phosphane;platinum Chemical compound P.[Pt] PKELYQZIUROQSI-UHFFFAOYSA-N 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Silicon Polymers (AREA)
Abstract
Description
本発明は、変性シロキサン二酸無水物およびポリイミド樹脂に関する発明である。 The present invention relates to a modified siloxane diic anhydride and a polyimide resin.
ポリイミド樹脂はエレクトロニクス分野において広く利用されている材料であり、樹脂へ柔軟性付与させる目的で、特許文献１に記載されているように、分子中にシロキサン構造を有するポリイミド樹脂も多く提案されている。しかし、合成時に用いるシロキサンジアミン化合物は純度が低く、高温時に低分子シロキサンが揮発することで電気配線での接合不良を起こす問題や、各種基材との密着性に欠けるなどの問題を有している。 Polyimide resin is a material widely used in the field of electronics, and as described in Patent Document 1, many polyimide resins having a siloxane structure in the molecule have been proposed for the purpose of imparting flexibility to the resin. .. However, the siloxane diamine compound used during synthesis has low purity and has problems such as poor bonding in electrical wiring due to volatilization of small molecule siloxane at high temperature and lack of adhesion to various substrates. There is.
一方、特許文献２にはシロキサン構造を有する二酸無水物を用いてポリイミド樹脂を得る技術も提案されている。ただし上記と同様、密着性に欠けるポリイミド樹脂となる課題を有している。 On the other hand, Patent Document 2 also proposes a technique for obtaining a polyimide resin using a diacid anhydride having a siloxane structure. However, as described above, there is a problem that the polyimide resin lacks adhesion.
本発明は、有機変性したシロキサン二酸無水物およびそれを用いて得られる密着性に優れるポリイミド樹脂を提供する事を目的とする。 An object of the present invention is to provide an organically modified siloxane diic anhydride and a polyimide resin obtained by using the same and having excellent adhesion.
上記課題を達成の為に検討を重ねた結果、有機変性したシロキサン二酸無水物およびそれを用いて得られるポリイミド樹脂が、柔軟性を有し、かつ、優れた密着性を有する事を見出すに至った。本発明は、以下からなるものである。 As a result of repeated studies to achieve the above problems, it was found that the organically modified siloxane diic anhydride and the polyimide resin obtained by using the organically modified siloxane diic anhydride have flexibility and excellent adhesion. I arrived. The present invention comprises the following.
〔１〕．末端に酸無水物基を有する以下構造で表される変性シロキサン二酸無水物。 [1]. A modified siloxane diacid anhydride having an acid anhydride group at the terminal and represented by the following structure.
（上記化学式において、Ｇは主鎖の炭素数が１から５０であって、Ｈ原子、Ｏ原子、Ｎ原子、ハロゲン原子、Ｓ原子のいずれかの原子を一種、又は、２種以上含む有機基で表され、Ｘは酸無水物基を構造中に有する有機基、Ｒは炭素数１から２０で表される有機基を示し、ｎは０〜５０、ｍは１〜５０の整数である） (In the above chemical formula, G is an organic group having 1 to 50 carbon atoms in the main chain and containing one or more of H atom, O atom, N atom, halogen atom and S atom. , X is an organic group having an acid anhydride group in the structure, R is an organic group represented by 1 to 20 carbon atoms, n is an integer of 0 to 50, and m is an integer of 1 to 50).
〔２〕．（Ａ）１分子中に炭素−炭素二重結合を２個有する化合物、（Ｂ）１分子中にＳｉＨ基を２個有するケイ素化合物、（Ｃ）１分子中に炭素−炭素二重結合および酸無水物基を１個ずつ有する化合物、を反応させることで得られる〔１〕に記載の変性シロキサン二酸無水物。 [2]. (A) A compound having two carbon-carbon double bonds in one molecule, (B) a silicon compound having two SiH groups in one molecule, (C) a carbon-carbon double bond and an acid in one molecule. The modified siloxane diic acid anhydride according to [1], which is obtained by reacting a compound having one anhydride group at a time.
〔３〕．成分（Ｃ）が以下に記載される化合物より選ばれる事を特徴とする〔２〕に記載の変性シロキサン二酸無水物。 [3]. The modified siloxane diic acid anhydride according to [2], wherein the component (C) is selected from the compounds described below.
〔４〕．成分（Ａ）がＮ原子又はＳ原子を有することを特徴とする〔２〕又は〔３〕に記載の変性シロキサン二酸無水物。 [4]. The modified siloxane diacid anhydride according to [2] or [3], wherein the component (A) has an N atom or an S atom.
〔５〕．成分（Ａ）が以下一般式（ｃ）で表される化合物である事を特徴とする〔４〕に記載の変性シロキサン二酸無水物。 [5]. The modified siloxane diic acid anhydride according to [4], wherein the component (A) is a compound represented by the following general formula (c).
（式中Ｒは水素原子又は炭素数１〜５０の一価の有機基を示す）
〔６〕．〔１〕〜〔５〕に記載の変性シロキサン二酸無水物とジアミン化合物又はジイソシアネート化合物とを反応させる事により得られるポリイミド樹脂。
(R in the formula indicates a hydrogen atom or a monovalent organic group having 1 to 50 carbon atoms)
[6]. A polyimide resin obtained by reacting the modified siloxane diic anhydride according to [1] to [5] with a diamine compound or a diisocyanate compound.
本発明によれば有機変性したシロキサン二酸無水物およびそれを用いて得られる密着性に優れるポリイミド樹脂を提供することができる。 According to the present invention, it is possible to provide an organically modified siloxane diic anhydride and a polyimide resin having excellent adhesion obtained by using the same.
（変性シロキサン二酸無水物）
上記、変性シロキサン二酸無水物は、末端に酸無水物基を有する以下構造で表される変性シロキサン二酸無水物。
(Modified siloxane diic acid anhydride)
The above-mentioned modified siloxane diichydride is a modified siloxane dianohydride having an acid anhydride group at the terminal and represented by the following structure.
（上記化学式において、Ｇは主鎖の炭素数が１から５０であって、Ｈ原子、Ｏ原子、Ｎ原子、ハロゲン原子、Ｓ原子のいずれかの原子を一種、又は、２種以上含む有機基で表され、Ｘは酸無水物基を構造中に有する有機基、Ｒは炭素数１から２０で表される有機基を示し、ｎは０〜５０、ｍは１〜５０の整数である） (In the above chemical formula, G is an organic group having 1 to 50 carbon atoms in the main chain and containing one or more of H atom, O atom, N atom, halogen atom and S atom. , X is an organic group having an acid anhydride group in the structure, R is an organic group represented by 1 to 20 carbon atoms, n is an integer of 0 to 50, and m is an integer of 1 to 50).
ここで言う構造Ｇとは、主鎖の炭素数が１から５０であって、Ｈ原子、Ｏ原子、Ｎ原子、ハロゲン原子、Ｓ原子のいずれかの原子を一種、又は、２種以上含む有機基で表され、特に限定されるものではない。当発明で得られるポリイミド樹脂では、構造Ｇを有さないシロキサン分子を有する樹脂と比較して基材との密着性・樹脂強度を向上させるために有効であり、かつ、ポリイミド樹脂の特長である耐熱性を損なう事無く導入する観点から、下記に示すヒドロシリル化反応を用いて導入する方法が好ましい。 The structure G referred to here is an organic having 1 to 50 carbon atoms in the main chain and containing one or more of H atom, O atom, N atom, halogen atom and S atom. It is expressed as a group and is not particularly limited. The polyimide resin obtained by the present invention is effective for improving the adhesion to the substrate and the resin strength as compared with the resin having a siloxane molecule having no structure G, and is a feature of the polyimide resin. From the viewpoint of introduction without impairing the heat resistance, the method of introduction using the hydrosilylation reaction shown below is preferable.
以下、ヒドロシリル化反応を用いて変性シロキサン二酸無水物を得るための各必須成分について説明する。 Hereinafter, each essential component for obtaining a modified siloxane diic acid anhydride using a hydrosilylation reaction will be described.
（成分（Ａ）：１分子中に炭素−炭素二重結合を２個有する化合物）
上記、変性シロキサン二酸無水物は、成分（Ａ）の１分子中に炭素−炭素二重結合を２個有する化合物と、後述の成分（Ｂ）および（Ｃ）と反応させることによって得ることが出来る。本件発明中の（Ａ）成分である１分子中に炭素−炭素二重結合を２個含有する化合物であれば特に限定されない。
(Component (A): A compound having two carbon-carbon double bonds in one molecule)
The above-mentioned modified siloxane anhydride can be obtained by reacting a compound having two carbon-carbon double bonds in one molecule of the component (A) with the components (B) and (C) described later. I can. The compound is not particularly limited as long as it is a compound containing two carbon-carbon double bonds in one molecule which is the component (A) in the present invention.
成分（Ａ）の炭素−炭素二重結合としては特に限定されないが、下記一般式（ａ） The carbon-carbon double bond of the component (A) is not particularly limited, but the following general formula (a)
（式中Ｒ4は水素原子あるいはメチル基を表す。）で示される基が反応性の点から好適である。また、原料の入手の容易さからは、 The group represented by (R 4 in the formula represents a hydrogen atom or a methyl group) is suitable from the viewpoint of reactivity. Also, due to the availability of raw materials,
で示される基が特に好ましい。 The groups indicated by are particularly preferred.
成分（Ａ）の炭素−炭素二重結合としては、下記一般式（ｂ）で表される部分構造を環内に有する脂環式の基が硬化物の耐熱性が高いという点から好適である。 As the carbon-carbon double bond of the component (A), an alicyclic group having a partial structure represented by the following general formula (b) in the ring is suitable from the viewpoint of high heat resistance of the cured product. ..
（式中Ｒ5は水素原子あるいはメチル基を表す。）また、原料の入手の容易さからは、下記式で表される部分構造を環内に有する脂環式の基が好適である。 (R 5 in the formula represents a hydrogen atom or a methyl group.) Further, from the viewpoint of easy availability of raw materials, an alicyclic group having a partial structure represented by the following formula in the ring is preferable.
炭素−炭素二重結合は成分（Ａ）の骨格部分に直接結合していてもよく、２価以上の置換基を介して共有結合していても良い。２価以上の置換基としては炭素数０〜１０の置換基であれば特に限定されないが、構成元素としてＣ、Ｈ、Ｎ、Ｏ、Ｓ、およびハロゲンのみを含むものが好ましい。これらの置換基の例としては、 The carbon-carbon double bond may be directly bonded to the skeleton portion of the component (A), or may be covalently bonded via a divalent or higher substituent. The divalent or higher substituent is not particularly limited as long as it is a substituent having 0 to 10 carbon atoms, but those containing only C, H, N, O, S and halogen as constituent elements are preferable. Examples of these substituents are
で表される基等が挙げられる。また、これらの２価以上の置換基の２つ以上が共有結合によりつながって１つの２価以上の置換基を構成していてもよい。 Examples include the group represented by. Further, two or more of these divalent or higher substituents may be connected by a covalent bond to form one divalent or higher substituent.
以上のような骨格部分に共有結合する基の例としては、ビニル基、アリル基、メタリル基、アクリル基、メタクリル基、２−ヒドロキシ−３−（アリルオキシ）プロピル基、２−アリルフェニル基、３−アリルフェニル基、４−アリルフェニル基、２−（アリルオキシ）フェニル基、３−（アリルオキシ）フェニル基、４−（アリルオキシ）フェニル基、２−（アリルオキシ）エチル基、２、２−ビス（アリルオキシメチル）ブチル基、３−アリルオキシ−２、２−ビス（アリルオキシメチル）プロピル基、ビニルエーテル基、等が挙げられる。 Examples of the group covalently bonded to the skeleton portion as described above include a vinyl group, an allyl group, a metallicyl group, an acrylic group, a methacryl group, a 2-hydroxy-3- (allyloxy) propyl group, and a 2-allylphenyl group, 3. -Allylphenyl group, 4-allylphenyl group, 2- (allyloxy) phenyl group, 3- (allyloxy) phenyl group, 4- (allyloxy) phenyl group, 2- (allyloxy) ethyl group, 2,2-bis (allyl) Examples thereof include an oxymethyl) butyl group, a 3-allyloxy-2, a 2-bis (allyloxymethyl) propyl group, a vinyl ether group, and the like.
成分（Ａ）の具体的な例としては、ジアリルフタレート、ジエチレングリコールビスアリルカーボネート、トリメチロールプロパンジアリルエーテル、ジアリリデンペンタエリスリット、ジアリルモノメチルイソシアヌレート。ジアリルモノプロピルイソシアヌレート、ジアリルモノグリシジルイソシアヌレート、ジアリルモノベンジルイソシアヌレート、ジアリルジメチルグリコールウリル、１，４−ブタンジオールジビニルエーテル、ノナンジオールジビニルエーテル、１，４−シクロへキサンジメタノールジビニルエーテル、トリエチレングリコールジビニルエーテル、ビスフェノールＳのジアリルエーテル、ジビニルベンゼン、ジビニルビフェニル、１，３−ジイソプロペニルベンゼン、１，４−ジイソプロペニルベンゼン、１，３−ビス（アリルオキシ）アダマンタン、１，３−ビス（ビニルオキシ）アダマンタン、ジシクロペンタジエン、ビニルシクロへキセン、１，５−ヘキサジエン、１，９−デカジエン、ジアリルエーテル、ビスフェノールＡジアリルエーテル、テトラアリルビスフェノールＡ、２，５−ジアリルフェノールアリルエーテル Specific examples of the component (A) include diallyl phthalate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, diallylidene pentaerythritol, and diallyl monomethylisocyanurate. Dialyl monopropyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl monobenzyl isocyanurate, diallyl dimethyl glycol uryl, 1,4-butanediol divinyl ether, nonanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, tri Ethylene glycol divinyl ether, bisphenol S diallyl ether, divinylbenzene, divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, 1,3-bis (allyloxy) adamantan, 1,3-bis (Vinyloxy) adamantan, dicyclopentadiene, vinylcyclohexene, 1,5-hexadiene, 1,9-decadien, diallyl ether, bisphenol A diallyl ether, tetraallyl bisphenol A, 2,5-diallylphenol allyl ether
等が挙げられる。 And so on.
成分（Ａ）としては、基材との接着性に優れるという観点からは、成分（Ａ）が極性の高いＮ原子又はＳ原子を有することが好ましい。具体的な例としては、ジアリルモノメチルイソシアヌレート。ジアリルモノプロピルイソシアヌレート、ジアリルモノグリシジルイソシアヌレート、ジアリルモノベンジルイソシアヌレート、ジアリルジメチルグリコールウリル、ビスフェノールＳのジアリルエーテル、などが挙げられる。 As the component (A), it is preferable that the component (A) has a highly polar N atom or an S atom from the viewpoint of excellent adhesiveness to the base material. As a specific example, diallyl monomethyl isocyanurate. Examples thereof include diallyl monopropyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl monobenzyl isocyanurate, diallyl dimethyl glycol uryl, and bisphenol S diallyl ether.
その中でも特に、耐熱性、耐光性が高いという観点から下記一般式（ｃ）で表されるジアリルモノメチルイソシアヌレート。ジアリルモノプロピルイソシアヌレート、及びその誘導体が特に好ましい。 Among them, diallyl monomethylisocyanurate represented by the following general formula (c) from the viewpoint of high heat resistance and light resistance. Dialyl monopropyl isocyanurate and its derivatives are particularly preferred.
（式中Ｒは水素原子又は炭素数１〜５０の一価の有機基を示す）
で表される化合物が好ましい。
(R in the formula indicates a hydrogen atom or a monovalent organic group having 1 to 50 carbon atoms)
The compound represented by is preferable.
また、炭素−炭素二重結合を２個有するケイ素系化合物も用いる事も出来る。最も一般的に入手し易いものとして、ビニル基末端直鎖状ポリシロキサンが挙げられるが、ジメチルシロキサン単位、ジフェニルシロキサン単位、メチルフェニルシロキサン単位の単一重合体、および、それぞれのシロキサン単位の共重合体についてジメチルビニルシリル基で末端が封鎖されたポリオルガノシロキサン重合体であれば特に限定されない。具体的には、例えば、１，１，３，３−テトラメチルジビニルジシロキサン、１，１，３，３，５，５，―ヘキサメチルジビニルトリシロキサン、１，１，５，５−テトラメチルジビニル−３，３−ジフェニルトリシロキサンなどが、好ましい例として例示される。また、ビニル基末端のポリシロキサン化合物以外のケイ素系化合物も用いる事ができ、例えば、１，４−ビス（ジメチルビニルシリル）ベンゼン、１，４−ビス（ジフェニルビニルシリル）ベンゼン、１，４−ビス（メチルフェニルビニルシリル）ベンゼン、ジビニルジメチルシラン、ジビニルシクロヘキシルメチルシラン、ジビニルフェニルメチルシラン、ジビニルジシクロヘキシルシラン、ジビニルジフェニルシラン、ビス（ビニルジメチルシリル）メタン、ビス（ビニルフェニルメチルシリル）メタン、ビス（ビニルシクロヘキシルメチルシリル）メタン、ビス（ビニルジフェニルシリル）メタン、（ビニルジメチルシリル）（ジビニルメチルシリル）メタン、（ビニルフェニルメチルシリル）（ジビニルメチルシリル）メタン、１，２−ビス（ビニルジメチルシリル）エタン、１，２−ビス（ビニルジフェニルシリル）エタン、１，２−ビス（ジビニルメチルシリル）エタン、１，２−ビス（ジビニルフェニルシリル）エタン、１，３−ビス（ビニルジメチルシリル）プロパン、１，３−ビス（ビニルジフェニルシリル）プロパン、１，４−ビス（ビニルジメチルシリル）ブタン、１，４−ビス（ビニルジフェニルシリル）ブタン、１，５−ビス（ビニルジメチルシリル）ペンタン、１，５−ビス（ビニルジフェニルシリル）ペンタン、１，４−ビス（ビニルジメチルシリル）シクロヘキサン、１，４−ビス（ビニルフェニルメチルシリル）シクロヘキサン、１，４−ビス（ビニルシクロヘキシルメチルシリル）シクロヘキサン、１，４−ビス（ビニルジフェニルシリル）シクロヘキサン、１，３−ビス（ビニルフェニルメチルシリル）シクロヘキサン、１，３−ビス（ビニルシクロヘキシルメチルシリル）シクロヘキサン、１，３−ビス（ビニルジフェニルシリル）シクロヘキサン、１，４−ビス（ビニルジメチルシリル）ベンゼン、１，４−ビス（ビニルフェニルメチルシリル）ベンゼン、１，４−ビス（ビニルシクロヘキシルメチルシリル）ベンゼン、１，４−ビス（ビニルジフェニルシリル）ベンゼン、１，４−ビス（ジビニルメチルシリル）ベンゼン、１，３−ビス（ビニルジメチルシリル）ベンゼン、１，３−ビス（ビニルフェニルメチルシリル）ベンゼン、１，３−ビス（ビニルシクロヘキシルメチルシリル）ベンゼン、１，３−ビス（ビニルジフェニルシリル）ベンゼン、２，６−ビス（ビニルジメチルシリル）ナフタレン、２，６−ビス（ビニルフェニルメチルシリル）ナフタレン、２，６−ビス（ビニルシクロヘキシルメチルシリル）ナフタレン、２，６−ビス（ビニルジフェニルシリル）ナフタレン、２，７−ビス（ビニルジメチルシリル）ナフタレン、２，７−ビス（ビニルフェニルメチルシリル）ナフタレン、２，７−ビス（ビニルシクロヘキシルメチルシリル）ナフタレン、２，７−ビス（ビニルジフェニルシリル）ナフタレン、２，７−ビス（ビニルジメチルシリル）アントラセン、２，７−ビス（ビニルフェニルメチルシリル）アントラセン、２，７−ビス（ビニルシクロヘキシルメチルシリル）アントラセン、２，７−ビス（ビニルジフェニルシリル）アントラセン、２，８−ビス（ビニルジメチルシリル）アントラセン、２，８−ビス（ビニルフェニルメチルシリル）アントラセン、２，８−ビス（ビニルシクロヘキシルメチルシリル）アントラセン、２，８−ビス（ビニルジフェニルシリル）アントラセン、等が挙げられる。 Further, a silicon-based compound having two carbon-carbon double bonds can also be used. The most commonly available one is a vinyl group-terminated linear polysiloxane, which is a monopolymer of dimethylsiloxane unit, diphenylsiloxane unit, methylphenylsiloxane unit, and a copolymer of each siloxane unit. The above is not particularly limited as long as it is a polyorganosiloxane polymer whose end is closed with a dimethylvinylsilyl group. Specifically, for example, 1,1,3,3-tetramethyldivinyldisiloxane, 1,1,3,3,5,5,-hexamethyldivinyltrisiloxane, 1,1,5,5-tetramethyl Divinyl-3,3-diphenyltrisiloxane and the like are exemplified as preferable examples. Further, silicon-based compounds other than the polysiloxane compound at the terminal of the vinyl group can also be used, for example, 1,4-bis (dimethylvinylsilyl) benzene, 1,4-bis (diphenylvinylsilyl) benzene, 1,4-. Bis (methylphenylvinylsilyl) benzene, divinyldimethylsilane, divinylcyclohexylmethylsilane, divinylphenylmethylsilane, divinyldicyclohexylsilane, divinyldiphenylsilane, bis (vinyldimethylsilyl) methane, bis (vinylphenylmethylsilyl) methane, bis ( Vinyl Cyclohexylmethylsilyl) methane, bis (vinyldiphenylsilyl) methane, (vinyldimethylsilyl) (divinylmethylsilyl) methane, (vinylphenylmethylsilyl) (divinylmethylsilyl) methane, 1,2-bis (vinyldimethylsilyl) Etan, 1,2-bis (vinyldiphenylsilyl) ethane, 1,2-bis (divinylmethylsilyl) ethane, 1,2-bis (divinylphenylsilyl) ethane, 1,3-bis (vinyldimethylsilyl) propane, 1,3-Bis (vinyldiphenylsilyl) propane, 1,4-bis (vinyldimethylsilyl) butane, 1,4-bis (vinyldiphenylsilyl) butane, 1,5-bis (vinyldimethylsilyl) pentane, 1, 5-bis (vinyldiphenylsilyl) pentane, 1,4-bis (vinyldimethylsilyl) cyclohexane, 1,4-bis (vinylphenylmethylsilyl) cyclohexane, 1,4-bis (vinylcyclohexylmethylsilyl) cyclohexane, 1, 4-Bis (vinyldiphenylsilyl) cyclohexane, 1,3-bis (vinylphenylmethylsilyl) cyclohexane, 1,3-bis (vinylcyclohexylmethylsilyl) cyclohexane, 1,3-bis (vinyldiphenylsilyl) cyclohexane, 1, 4-Bis (vinyldimethylsilyl) benzene, 1,4-bis (vinylphenylmethylsilyl) benzene, 1,4-bis (vinylcyclohexylmethylsilyl) benzene, 1,4-bis (vinyldiphenylsilyl) benzene, 1, 4-Bis (divinylmethylsilyl) benzene, 1,3-bis (vinyldimethylsilyl) benzene, 1,3-bis (vinylphenylmethylsilyl) benzene, 1,3-bis (vinylcyclohexylmethylsilyl) benzene, 1, 3-Bis (vinyl diphenylsilyl) benzene, 2,6-bis (vinyl di) Methylsilyl) naphthalene, 2,6-bis (vinylphenylmethylsilyl) naphthalene, 2,6-bis (vinylcyclohexylmethylsilyl) naphthalene, 2,6-bis (vinyldiphenylsilyl) naphthalene, 2,7-bis (vinyldimethyl) Cyril) naphthalene, 2,7-bis (vinylphenylmethylsilyl) naphthalene, 2,7-bis (vinylcyclohexylmethylsilyl) naphthalene, 2,7-bis (vinyldiphenylsilyl) naphthalene, 2,7-bis (vinyldimethyl) Cyril) Naphthalene, 2,7-bis (vinylphenylmethylsilyl) anthracene, 2,7-bis (vinylcyclohexylmethylsilyl) anthracene, 2,7-bis (vinyldiphenylsilyl) anthracene, 2,8-bis (vinyldimethyl) Examples thereof include silyl) anthracene, 2,8-bis (vinylphenylmethylsilyl) anthracene, 2,8-bis (vinylcyclohexylmethylsilyl) anthracene, and 2,8-bis (vinyldiphenylsilyl) anthracene.
（成分（Ｂ）：１分子中にＳｉＨ基を２個有するケイ素化合物）
成分（Ｂ）としては、ＳｉＨ基を２個有するケイ素化合物、つまり、Ｓｉ原子を分子中に有するＳｉＨ基を２個有する化合物であれば特に限定せず使用できる。最も一般的に入手し易いものとして、ＳｉＨ基末端直鎖状ポリシロキサンが挙げられるが、ジメチルシロキサン単位、ジフェニルシロキサン単位、メチルフェニルシロキサン単位の単一重合体、および、それぞれのシロキサン単位の共重合体についてジメチルハイドロジェンシリル基で末端が封鎖されたポリオルガノシロキサン重合体であれば特に限定されない。具体的には、例えば、１，１，３，３−テトラメチルジシロキサン、１，１，３，３，５，５，―ヘキサメチルトリシロキサン、１，１，５，５−テトラメチル−３，３−ジフェニルトリシロキサンなどが、好ましい例として例示される。また、ＳｉＨ基末端のポリシロキサン化合物以外のケイ素系化合物も用いる事ができ、例えば、１，４−ビス（ジメチルシリル）ベンゼン、１，４−ビス（ジフェニルシリル）ベンゼン、１，４−ビス（メチルフェニルシリル）ベンゼン、などが具体的に挙げられる。
(Component (B): Silicon compound having two SiH groups in one molecule)
The component (B) can be used without particular limitation as long as it is a silicon compound having two SiH groups, that is, a compound having two SiH groups in the molecule. The most commonly available one is a SiH group-terminated linear polysiloxane, which is a single polymer of dimethylsiloxane unit, diphenylsiloxane unit, methylphenylsiloxane unit, and a copolymer of each siloxane unit. The above is not particularly limited as long as it is a polyorganosiloxane polymer whose end is closed with a dimethylhydrogensilyl group. Specifically, for example, 1,1,3,3-tetramethyldisiloxane, 1,1,3,3,5,5,-hexamethyltrisiloxane, 1,1,5,5-tetramethyl-3. , 3-Diphenyltrisiloxane and the like are exemplified as preferable examples. Further, silicon-based compounds other than the polysiloxane compound at the end of the SiH group can also be used, and for example, 1,4-bis (dimethylsilyl) benzene, 1,4-bis (diphenylsilyl) benzene, and 1,4-bis ( Methylphenylsilyl) benzene, etc. are specifically mentioned.
（成分（Ｃ）：１分子中に炭素−炭素二重結合および酸無水物基を１個ずつ有する化合物）
成分（Ｃ）としては、１分子中に炭素−炭素二重結合および酸無水物基を１個ずつ有する化合物であれば特に限定せず使用する事ができる。具体的な例としては、無水マレイン酸、シトラコン酸無水物、イタコン酸無水物、アリルコハク酸無水物、ナジック酸無水物、メチルナジック酸無水物、テトラヒドロ無水フタル酸、テトラヒドロメチル無水フタル酸、テトラメチルフェニル無水フタル酸が挙げられる。反応性の観点より、ナジック酸無水物、メチルナジック酸無水物、アリルコハク酸無水物が好ましい。
(Component (C): A compound having one carbon-carbon double bond and one acid anhydride group in one molecule)
As the component (C), any compound having one carbon-carbon double bond and one acid anhydride group in one molecule can be used without particular limitation. Specific examples include maleic anhydride, citraconic anhydride, itaconic acid anhydride, allylsuccinic anhydride, nadic acid anhydride, methylnagic acid anhydride, tetrahydrophthalic anhydride, tetrahydromethylphthalic anhydride, and tetramethyl. Phthalic anhydride is mentioned. From the viewpoint of reactivity, nadic acid anhydride, methyl nagic acid anhydride, and allyl succinic acid anhydride are preferable.
（成分（Ａ）、（Ｂ）、（Ｃ）の反応）
成分（Ａ）、（Ｂ）、（Ｃ）を反応させ変性シロキサン二酸無水物を得る方法としては、ヒドロシリル化反応を用いる。この場合、スムーズに反応を進行させる目的で触媒を用いても良い。
(Reaction of components (A), (B), (C))
A hydrosilylation reaction is used as a method for obtaining a modified siloxane diic acid anhydride by reacting the components (A), (B) and (C). In this case, a catalyst may be used for the purpose of allowing the reaction to proceed smoothly.
ヒドロシリル化反応の触媒としては、例えば次のようなものを用いることができる。白金の単体、アルミナ、シリカ、カーボンブラック等の担体に固体白金を担持させたもの、塩化白金酸、塩化白金酸とアルコール、アルデヒド、ケトン等との錯体、白金−オレフィン錯体（例えば、Ｐｔ（ＣＨ2＝ＣＨ2）2（ＰＰｈ3）2、Ｐｔ（ＣＨ2＝ＣＨ2）2Ｃｌ2）、白金−ビニルシロキサン錯体（例えば、Ｐｔ（ＶｉＭｅ2ＳｉＯＳｉＭｅ2Ｖｉ）n、Ｐｔ［（ＭｅＶｉＳｉＯ）4］m）、白金−ホスフィン錯体（例えば、Ｐｔ（ＰＰｈ3）4、Ｐｔ（ＰＢｕ3）4）、白金−ホスファイト錯体（例えば、Ｐｔ［Ｐ（ＯＰｈ）3］4、Ｐｔ［Ｐ（ＯＢｕ）3］4）（式中、Ｍｅはメチル基、Ｂｕはブチル基、Ｖｉはビニル基、Ｐｈはフェニル基を表し、ｎ、ｍは、整数を示す。）、ジカルボニルジクロロ白金、カールシュテト（Ｋａｒｓｔｅｄｔ）触媒、また、アシュビー（Ａｓｈｂｙ）の米国特許第３１５９６０１号及び３１５９６６２号明細書中に記載された白金−炭化水素複合体、ならびにラモロー（Ｌａｍｏｒｅａｕｘ）の米国特許第３２２０９７２号明細書中に記載された白金アルコラート触媒が挙げられる。更に、モディック（Ｍｏｄｉｃ）の米国特許第３５１６９４６号明細書中に記載された塩化白金−オレフィン複合体も本発明において有用である。 As the catalyst for the hydrosilylation reaction, for example, the following can be used. Platinum alone, a carrier such as alumina, silica, carbon black, etc. on which solid platinum is supported, platinum chloride acid, a complex of platinum chloride acid with alcohol, aldehyde, ketone, etc., a platinum-olefin complex (for example, Pt (CH) 2 = CH 2 ) 2 (PPh 3 ) 2 , Pt (CH 2 = CH 2 ) 2 Cl 2 ), Platinum-vinylsiloxane complex (for example, Pt (ViMe 2 SiOSiMe 2 Vi) n , Pt [(MeViSiO) 4 ] m ), platinum-phosphine complex (eg Pt (PPh 3 ) 4 , Pt (PBu 3 ) 4 ), platinum-phosphite complex (eg Pt [P (OPh) 3 ] 4 , Pt [P (OBu) 3). 4 ) (In the formula, Me is a methyl group, Bu is a butyl group, Vi is a vinyl group, Ph is a phenyl group, and n and m are integers.), Dicarbonyldichloroplatinum, Karstedt catalyst. Also, the platinum-hydrogen complex described in Ashby's US Pat. Nos. 3,159,601 and 3159662, and the platinum alcoholate described in Lamoreoux's US Pat. No. 3220972. Examples include catalysts. Further, the platinum chloride-olefin complex described in Modic's US Pat. No. 3,516,946 is also useful in the present invention.
また、白金化合物以外の触媒の例としては、ＲｈＣｌ（ＰＰｈ）3、ＲｈＣｌ3、ＲｈＡｌ2Ｏ3、ＲｕＣｌ3、ＩｒＣｌ3、ＦｅＣｌ3、ＡｌＣｌ3、ＰｄＣｌ2・２Ｈ2Ｏ、ＮｉＣｌ2、ＴｉＣｌ4、等が挙げられる。 Further, examples of catalysts other than platinum compounds, RhCl (PPh) 3, RhCl 3, RhAl 2 O 3, RuCl 3, IrCl 3, FeCl 3, AlCl 3, PdCl 2 · 2H 2 O, NiCl 2, TiCl 4 , Etc. can be mentioned.
これらの中では、触媒活性の点から塩化白金酸、白金−オレフィン錯体、白金−ビニルシロキサン錯体等が好ましい。また、これらの触媒は単独で使用してもよく、２種以上併用してもよい。 Among these, platinum chloride acid, platinum-olefin complex, platinum-vinylsiloxane complex and the like are preferable from the viewpoint of catalytic activity. Further, these catalysts may be used alone or in combination of two or more.
成分（Ａ）、（Ｂ）、（Ｃ）の反応させる順序については、まず成分（Ａ）と（Ｂ）とをＳｉＨ基量を多くした条件でヒドロシリル化により反応させ、次に成分（Ｃ）を逐次で反応させ、末端に酸無水物基を導入する事によって、変性シロキサン二酸無水物を得る事ができる。 Regarding the reaction order of the components (A), (B), and (C), first, the components (A) and (B) are reacted by hydrosilylation under the condition that the amount of SiH group is increased, and then the component (C) is reacted. A modified siloxane diichydride can be obtained by sequentially reacting with and introducing an acid anhydride group at the terminal.
（ポリイミド樹脂について）
本発明の変性シロキサン二酸無水物を用いて得られるポリイミド樹脂は、一般にジアミン化合物又はジイソシアネート化合物との反応により得られ、特に限定されるものではない。
(About polyimide resin)
The polyimide resin obtained by using the modified siloxane diacid anhydride of the present invention is generally obtained by reaction with a diamine compound or a diisocyanate compound, and is not particularly limited.
本発明のポリイミド合成のために用いるジアミンとしては、例えば、［ビス（４−アミノ−３−カルボキシ）フェニル］メタン、ｐ−フェニレンジアミン、ｍ−フェニレンジアミン、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノフェニルエタン、４，４’−ジアミノフェニルエーテル、４，４’−ジジアミノフェニルスルフィド、４，４’−ジジアミノフェニルスルホン、１，５−ジアミノナフタレン、３，３−ジメチル−４，４’−ジアミノビフェニル、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’−ジアミノベンズアニリド、３，５−ジアミノ−３’−トリフルオロメチルベンズアニリド、３，５−ジアミノ−４’−トリフルオロメチルベンズアニリド、３，４’−ジアミノジフェニルエーテル、２，７−ジアミノフルオレン、２，２−ビス（４−アミノフェニル）ヘキサフルオロプロパン、４，４’−メチレン−ビス（２−クロロアニリン）、２，２’，５，５’−テトラクロロ−４，４’−ジアミノビフェニル、２，２’−ジクロロ−４，４’−ジアミノ−５，５’−ジメトキシビフェニル、３，３’−ジメトキシ−４，４’−ジアミノビフェニル、４，４’−ジアミノ−２，２’−ビス（トリフルオロメチル）ビフェニル、２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン、２，２−ビス［４−（３−アミノフェノキシ）フェニル］プロパン、２，２−ビス［４−（４−アミノフェノキシ）フェニル］スルホン、２，２−ビス［４−（３−アミノフェノキシ）フェニル］スルホン、２，２−ビス［４−（４−アミノフェノキシ）フェニル］ヘキサフルオロプロパン、１，４−ビス（４−アミノフェノキシ）ベンゼン、１，４−ビス（３−アミノフェノキシ）ベンゼン、４，４’−ビス（４−アミノフェノキシ）−ビフェニル、１，３’−ビス（４−アミノフェノキシ）ベンゼン、１，３’−ビス（３−アミノフェノキシ）ベンゼン、９，９−ビス（４−アミノフェニル）フルオレン、４，４’−（ｐ−フェニレンイソプロピリデン）ビスアニリン、４，４’−（ｍ−フェニレンイソプロピリデン）ビスアニリン、２，２’−ビス［４−（４−アミノ−２−トリフルオロメチルフェノキシ）フェニル］ヘキサフルオロプロパン、４，４’−ビス［４−（４−アミノ−２−トリフルオロメチル）フェノキシ］−オクタフルオロビフェニル等の芳香族ジアミン；ジアミノテトラフェニルチオフェン等の芳香環に結合された２個のアミノ基と当該アミノ基の窒素原子以外のヘテロ原子を有する芳香族ジアミン；１，１−メタキシリレンジアミン、１，３−プロパンジアミン、テトラメチレンジアミン、ペンタメチレンジアミン、オクタメチレンジアミン、ノナメチレンジアミン、４，４−ジアミノヘプタメチレンジアミン、１，４−ジアミノシクロヘキサン、イソフォロンジアミン、テトラヒドロジシクロペンタジエニレンジアミン、ヘキサヒドロ−４，７−メタノインダニレンジメチレンジアミン、トリシクロ［６，２，１，０２．７］−ウンデシレンジメチルジアミン、４，４’−メチレンビス（シクロヘキシルアミン）等の脂肪族ジアミンおよび脂環式ジアミン等及びそれらの誘導体などが挙げられ、これらを単独で、又は任意の割合で混合した混合物を好ましく用いることができる。 Examples of the diamine used for the polyimide synthesis of the present invention include [bis (4-amino-3-carboxy) phenyl] methane, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4, 4'-Diaminophenyl ethane, 4,4'-diaminophenyl ether, 4,4'-didiaminophenyl sulfide, 4,4'-didiaminophenyl sulfone, 1,5-diaminonaphthalene, 3,3-dimethyl-4 , 4'-Diaminobiphenyl, 5-amino-1- (4'-aminophenyl) -1,3,3-trimethylindan, 6-amino-1- (4'-aminophenyl) -1,3,3- Trimethylindan, 4,4'-diaminobenzanilide, 3,5-diamino-3'-trifluoromethylbenzanilide, 3,5-diamino-4'-trifluoromethylbenzanilide, 3,4'-diaminodiphenyl ether, 2,7-Diaminofluorene, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4'-methylene-bis (2-chloroaniline), 2,2', 5,5'-tetrachloro- 4,4'-Diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'- Diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane , 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] ) Phenyl] Hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) -biphenyl, 1, 3'-bis (4-aminophenoxy) benzene, 1,3'-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 4,4'-(p-phenylene isopropylidene) ) Bisaniline, 4,4'-(m-phenyleneisopropylidene) bisaniline, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-bis [4-( 4-Amino-2-trifluoromethyl) phenoxy] -aromatic diamines such as octafluorobiphenyl; two amino groups bonded to an aromatic ring such as diaminotetraphenylthiophene and heteroatoms other than the nitrogen atom of the amino groups. Aromatic diamines with; 1,1-methoxylylene diamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1,4 -Diaminocyclohexane, Isophorondiamine, Tetrahydrodicyclopentadiene diamine, Hexahydro-4,7-Metanoindanylenedimethylenediamine, Tricyclo [6,2,1,02.7] -Undecylendimethyldiamine, 4,4 Examples thereof include aliphatic diamines such as'-methylenebis (cyclohexylamine), alicyclic diamines and derivatives thereof, and a mixture thereof alone or in any ratio can be preferably used.
さらに、樹脂の溶剤への溶解性を向上させ塗布性を確保する目的で、上記、ポリイミド樹脂のポリマー分子中に脂環式構造又はスルホン基を有している事が好ましい。脂環式構造のポリマー分子への導入方法は限定されないが、原料のジアミン、又は、テトラカルボン酸化合物にこれら構造を有しているものを用いる事で簡便に導入する事ができる。ジアミン化合物について記載したが、ジアミン化合物のアミノ基をイソシアネート基に置き換えたジイソシアネート化合物も、ジアミン化合物と同様に用いることができる。 Further, for the purpose of improving the solubility of the resin in the solvent and ensuring the coatability, it is preferable that the above-mentioned polyimide resin has an alicyclic structure or a sulfone group in the polymer molecule. The method for introducing the alicyclic structure into the polymer molecule is not limited, but it can be easily introduced by using a diamine as a raw material or a tetracarboxylic dian compound having these structures. Although the diamine compound has been described, a diisocyanate compound in which the amino group of the diamine compound is replaced with an isocyanate group can also be used in the same manner as the diamine compound.
以下、実施例に基づいて本発明をより詳細に説明するが、本発明は以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to the following examples.
（密着性評価）
実施例および比較例で得られたポリイミド樹脂溶液をＣｕ製膜ウェハ基板上に膜厚５μｍでスピンコーティングした後２５０℃１時間ホットプレートで加熱する事で、ポリイミド樹脂膜を形成した。次にＪＩＳ Ｋ５６００−Ｖ−ＶＩ(ＩＳＯ２４０９)に準じてクロ
スカット試験を行い、Ｃｕ薄膜への密着性評価を行った。
(Adhesion evaluation)
The polyimide resin solutions obtained in Examples and Comparative Examples were spin-coated on a Cu film-forming wafer substrate with a film thickness of 5 μm and then heated on a hot plate at 250 ° C. for 1 hour to form a polyimide resin film. Next, a cross-cut test was performed according to JIS K5600-V-VI (ISO2409) to evaluate the adhesion to the Cu thin film.
●評価指標
０：剥離無し １：１〜１０％剥離 ２：２０〜３０％剥離
３：５０％剥離 ４：７０〜８０％剥離 ５：９０％以上剥離
● Evaluation index 0: No peeling 1: 1-10% peeling 2: 20-30% peeling 3: 50% peeling 4: 70-80% peeling 5: 90% or more peeling
（耐熱性評価）
熱重量測定装置（ＴＧＡ、島津製作所製）を用いて、室温から５００℃まで１０℃／分で昇温させ、１％重量減少温度を指標として評価を行った。
(Heat resistance evaluation)
Using a thermogravimetric measuring device (TGA, manufactured by Shimadzu Corporation), the temperature was raised from room temperature to 500 ° C. at 10 ° C./min, and evaluation was performed using the 1% weight loss temperature as an index.
（実施例１）
５００ｍＬ四つ口フラスコにトルエン１００ｇ、１，１，５，５−テトラメチル−３，３−ジフェニルトリシロキサン１５ｇを入れ、気相部を窒素置換した後、内温１０５℃で加熱、攪拌した。ジアリルモノメチルイソシアヌレート９ｇ、トルエン１０ｇ、白金ビニルシロキサン錯体のキシレン溶液（白金として３ｗｔ％含有）０.０１６３ｇの混合液を３０分かけて滴下した。滴下終了から３時間後に1Ｈ−ＮＭＲでアリル基の反応率が１００％であることを確認し、６０℃冷却した。その後、アリルコハク酸無水物１．５ｇとトルエン３ｇの混合溶液を滴下した。滴下終了から５時間後に1Ｈ−ＮＭＲでアリルコハク酸無水物の二重結合の反応率が１００％であることを確認し、冷却した反応を終了した。トルエンを減圧留去し、酸無水物基を末端に有する変性シロキサン化合物Ａを得た。
(Example 1)
Toluene (100 g) and 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane (15 g) were placed in a 500 mL four-necked flask, the gas phase portion was replaced with nitrogen, and the mixture was heated and stirred at an internal temperature of 105 ° C. A mixed solution of 9 g of diallyl monomethylisocyanurate, 10 g of toluene, and 0.0163 g of a xylene solution of a platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise over 30 minutes. Three hours after the completion of the dropping , it was confirmed by 1 H-NMR that the reaction rate of the allyl group was 100%, and the mixture was cooled at 60 ° C. Then, a mixed solution of 1.5 g of allyl succinic anhydride and 3 g of toluene was added dropwise. Five hours after the completion of the dropping, 1 H-NMR confirmed that the reaction rate of the double bond of the allyl succinic anhydride was 100%, and the cooling reaction was completed. Toluene was distilled off under reduced pressure to obtain a modified siloxane compound A having an acid anhydride group at the end.
次に、２００ｍＬのフラスコ中に、溶剤としてＮ，Ｎ−ジメチルホルムアミド２０ｇ、上記で得た変性シロキサン化合物Ａを２．５ｇ、２，２−ビス（４−アミノフェニル）ヘキサフルオロプロパン１．５ｇを投入し、室温、窒素雰囲気下で３０分間撹拌した。さらにＮ，Ｎ−ジメチルホルムアミド５ｇ、ピリジン０．８ｇ、無水酢酸１．５ｇを順次フラスコに投入し、９０℃に加熱しながら３時間撹拌した。常温に戻ってから、フラスコに５００ｍＬのイソプロピルアルコールを投入し、析出物を回収した。更に５００ｍＬのイソプロピルアルコールで洗浄を３回行い、得られた析出物を８０℃で６時間減圧乾燥し、その後、Ｎ，Ｎ−ジメチルホルムアミドで５０％に希釈してポリイミド樹脂溶液Ａを得た。 Next, in a 200 mL flask, 20 g of N, N-dimethylformamide, 2.5 g of the modified siloxane compound A obtained above, and 1.5 g of 2,2-bis (4-aminophenyl) hexafluoropropane were added as a solvent. The mixture was charged and stirred at room temperature and a nitrogen atmosphere for 30 minutes. Further, 5 g of N, N-dimethylformamide, 0.8 g of pyridine and 1.5 g of acetic anhydride were sequentially put into a flask, and the mixture was stirred for 3 hours while heating at 90 ° C. After returning to room temperature, 500 mL of isopropyl alcohol was put into the flask, and the precipitate was collected. Further, washing with 500 mL of isopropyl alcohol was performed three times, and the obtained precipitate was dried under reduced pressure at 80 ° C. for 6 hours, and then diluted to 50% with N, N-dimethylformamide to obtain a polyimide resin solution A.
（実施例２）
５００ｍＬ四つ口フラスコにトルエン１００ｇ、１，１，５，５−テトラメチル−３，３−ジフェニルトリシロキサン１５ｇを入れ、気相部を窒素置換した後、内温１０５℃で加熱、攪拌した。ジアリルモノプロピルイソシアヌレート８ｇ、トルエン１０ｇ、白金ビニルシロキサン錯体のキシレン溶液（白金として３ｗｔ％含有）０.０１６３ｇの混合液を３０分かけて滴下した。滴下終了から３時間後に1Ｈ−ＮＭＲでアリル基の反応率が１００％であることを確認し、６０℃冷却した。その後、アリルコハク酸無水物１．５ｇとトルエン３ｇの混合溶液を滴下した。滴下終了から５時間後に1Ｈ−ＮＭＲでアリルコハク酸無水物の二重結合の反応率が１００％であることを確認し、冷却した反応を終了した。トルエンを減圧留去し、酸無水物基を末端に有する変性シロキサン化合物Ｂを得た。
(Example 2)
Toluene (100 g) and 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane (15 g) were placed in a 500 mL four-necked flask, the gas phase portion was replaced with nitrogen, and the mixture was heated and stirred at an internal temperature of 105 ° C. A mixed solution of 8 g of diallyl monopropyl isocyanurate, 10 g of toluene, and 0.0163 g of a xylene solution of a platinum vinyl siloxane complex (containing 3 wt% as platinum) was added dropwise over 30 minutes. Three hours after the completion of the dropping , it was confirmed by 1 H-NMR that the reaction rate of the allyl group was 100%, and the mixture was cooled at 60 ° C. Then, a mixed solution of 1.5 g of allyl succinic anhydride and 3 g of toluene was added dropwise. Five hours after the completion of the dropping, 1 H-NMR confirmed that the reaction rate of the double bond of the allyl succinic anhydride was 100%, and the cooling reaction was completed. Toluene was distilled off under reduced pressure to obtain a modified siloxane compound B having an acid anhydride group at the end.
次に、２００ｍＬのフラスコ中に、溶剤としてＮ，Ｎ−ジメチルホルムアミド２０ｇ、上記で得た変性シロキサン化合物Ｂを２．５ｇ、２，２−ビス（４−アミノフェニル）ヘキサフルオロプロパン１．５ｇを投入し、室温、窒素雰囲気下で３０分間撹拌した。さらにＮ，Ｎ−ジメチルホルムアミド５ｇ、ピリジン０．８ｇ、無水酢酸１．５ｇを順次フラスコに投入し、９０℃に加熱しながら３時間撹拌した。常温に戻ってから、フラスコに５００ｍＬのイソプロピルアルコールを投入し、析出物を回収した。更に５００ｍＬのイソプロピルアルコールで洗浄を３回行い、得られた析出物を８０℃で６時間減圧乾燥し、その後、Ｎ，Ｎ−ジメチルホルムアミドで５０％に希釈してポリイミド樹脂溶液Ｂを得た。 Next, in a 200 mL flask, 20 g of N, N-dimethylformamide, 2.5 g of the modified siloxane compound B obtained above, and 1.5 g of 2,2-bis (4-aminophenyl) hexafluoropropane were added as a solvent. The mixture was charged and stirred at room temperature and a nitrogen atmosphere for 30 minutes. Further, 5 g of N, N-dimethylformamide, 0.8 g of pyridine and 1.5 g of acetic anhydride were sequentially put into a flask, and the mixture was stirred for 3 hours while heating at 90 ° C. After returning to room temperature, 500 mL of isopropyl alcohol was put into the flask, and the precipitate was collected. Further, washing with 500 mL of isopropyl alcohol was carried out three times, and the obtained precipitate was dried under reduced pressure at 80 ° C. for 6 hours, and then diluted to 50% with N, N-dimethylformamide to obtain a polyimide resin solution B.
（実施例３）
５００ｍＬ四つ口フラスコにトルエン１００ｇ、１，１，５，５−テトラメチル−３，３−ジフェニルトリシロキサン１５ｇを入れ、気相部を窒素置換した後、内温１０５℃で加熱、攪拌した。ビス（ｐ−アリルオキシフェニル）スルホン１２ｇ、トルエン１０ｇ、白金ビニルシロキサン錯体のキシレン溶液（白金として３ｗｔ％含有）０.０１６３ｇの混合液を３０分かけて滴下した。滴下終了から３時間後に1Ｈ−ＮＭＲでアリル基の反応率が１００％であることを確認し、６０℃冷却した。その後、アリルコハク酸無水物１．５ｇとトルエン３ｇの混合溶液を滴下した。滴下終了から５時間後に1Ｈ−ＮＭＲでアリルコハク酸無水物の二重結合の反応率が１００％であることを確認し、冷却した反応を終了した。トルエンを減圧留去し、酸無水物基を末端に有する変性シロキサン化合物Ｃを得た。
(Example 3)
Toluene (100 g) and 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane (15 g) were placed in a 500 mL four-necked flask, the gas phase portion was replaced with nitrogen, and the mixture was heated and stirred at an internal temperature of 105 ° C. A mixed solution of 12 g of bis (p-allyloxyphenyl) sulfone, 10 g of toluene, and 0.0163 g of a xylene solution of a platinum vinyl siloxane complex (containing 3 wt% as platinum) was added dropwise over 30 minutes. Three hours after the completion of the dropping , it was confirmed by 1 H-NMR that the reaction rate of the allyl group was 100%, and the mixture was cooled at 60 ° C. Then, a mixed solution of 1.5 g of allyl succinic anhydride and 3 g of toluene was added dropwise. Five hours after the completion of the dropping, 1 H-NMR confirmed that the reaction rate of the double bond of the allyl succinic anhydride was 100%, and the cooling reaction was completed. Toluene was distilled off under reduced pressure to obtain a modified siloxane compound C having an acid anhydride group at the end.
次に、２００ｍＬのフラスコ中に、溶剤としてＮ，Ｎ−ジメチルホルムアミド２０ｇ、上記で得た変性シロキサン化合物Ｃを２．５ｇ、２，２−ビス（４−アミノフェニル）ヘキサフルオロプロパン１．５ｇを投入し、室温、窒素雰囲気下で３０分間撹拌した。さらにＮ，Ｎ−ジメチルホルムアミド５ｇ、ピリジン０．８ｇ、無水酢酸１．５ｇを順次フラスコに投入し、９０℃に加熱しながら３時間撹拌した。常温に戻ってから、フラスコに５００ｍＬのイソプロピルアルコールを投入し、析出物を回収した。更に５００ｍＬのイソプロピルアルコールで洗浄を３回行い、得られた析出物を８０℃で６時間減圧乾燥し、その後、Ｎ，Ｎ−ジメチルホルムアミドで５０％に希釈してポリイミド樹脂溶液Ｃを得た。 Next, in a 200 mL flask, 20 g of N, N-dimethylformamide, 2.5 g of the modified siloxane compound C obtained above, and 1.5 g of 2,2-bis (4-aminophenyl) hexafluoropropane were placed as a solvent. The mixture was charged and stirred at room temperature and a nitrogen atmosphere for 30 minutes. Further, 5 g of N, N-dimethylformamide, 0.8 g of pyridine and 1.5 g of acetic anhydride were sequentially put into a flask, and the mixture was stirred for 3 hours while heating at 90 ° C. After returning to room temperature, 500 mL of isopropyl alcohol was put into the flask, and the precipitate was collected. Further, washing with 500 mL of isopropyl alcohol was performed three times, and the obtained precipitate was dried under reduced pressure at 80 ° C. for 6 hours, and then diluted to 50% with N, N-dimethylformamide to obtain a polyimide resin solution C.
（実施例４）
５００ｍＬ四つ口フラスコにトルエン１００ｇ、１，１，５，５−テトラメチル−３，３−ジフェニルトリシロキサン１５ｇを入れ、気相部を窒素置換した後、内温１０５℃で加熱、攪拌した。ジビニルベンゼン４ｇ、トルエン１０ｇ、白金ビニルシロキサン錯体のキシレン溶液（白金として３ｗｔ％含有）０.０１６３ｇの混合液を３０分かけて滴下した。滴下終了から３時間後に1Ｈ−ＮＭＲでアリル基の反応率が１００％であることを確認し、６０℃冷却した。その後、アリルコハク酸無水物１．５ｇとトルエン３ｇの混合溶液を滴下した。滴下終了から５時間後に1Ｈ−ＮＭＲでアリルコハク酸無水物の二重結合の反応率が１００％であることを確認し、冷却した反応を終了した。トルエンを減圧留去し、酸無水物基を末端に有する変性シロキサン化合物Ｄを得た。
(Example 4)
Toluene (100 g) and 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane (15 g) were placed in a 500 mL four-necked flask, the gas phase portion was replaced with nitrogen, and the mixture was heated and stirred at an internal temperature of 105 ° C. A mixed solution of 4 g of divinylbenzene, 10 g of toluene, and 0.0163 g of a xylene solution of a platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise over 30 minutes. Three hours after the completion of the dropping , it was confirmed by 1 H-NMR that the reaction rate of the allyl group was 100%, and the mixture was cooled at 60 ° C. Then, a mixed solution of 1.5 g of allyl succinic anhydride and 3 g of toluene was added dropwise. Five hours after the completion of the dropping, 1 H-NMR confirmed that the reaction rate of the double bond of the allyl succinic anhydride was 100%, and the cooling reaction was completed. Toluene was distilled off under reduced pressure to obtain a modified siloxane compound D having an acid anhydride group at the end.
次に、２００ｍＬのフラスコ中に、溶剤としてＮ，Ｎ−ジメチルホルムアミド２０ｇ、上記で得た変性シロキサン化合物Ｄを２．５ｇ、２，２−ビス（４−アミノフェニル）ヘキサフルオロプロパン１．５ｇを投入し、室温、窒素雰囲気下で３０分間撹拌した。さらにＮ，Ｎ−ジメチルホルムアミド５ｇ、ピリジン０．８ｇ、無水酢酸１．５ｇを順次フラスコに投入し、９０℃に加熱しながら３時間撹拌した。常温に戻ってから、フラスコに５００ｍＬのイソプロピルアルコールを投入し、析出物を回収した。更に５００ｍＬリットルのイソプロピルアルコールで洗浄を３回行い、得られた析出物を８０℃で６時間減圧乾燥し、その後、Ｎ，Ｎ−ジメチルホルムアミドで５０％に希釈してポリイミド樹脂溶液Ｄを得た。 Next, in a 200 mL flask, 20 g of N, N-dimethylformamide, 2.5 g of the modified siloxane compound D obtained above, and 1.5 g of 2,2-bis (4-aminophenyl) hexafluoropropane were placed as a solvent. The mixture was charged and stirred at room temperature and a nitrogen atmosphere for 30 minutes. Further, 5 g of N, N-dimethylformamide, 0.8 g of pyridine and 1.5 g of acetic anhydride were sequentially put into a flask, and the mixture was stirred for 3 hours while heating at 90 ° C. After returning to room temperature, 500 mL of isopropyl alcohol was put into the flask, and the precipitate was collected. Further washing with 500 mL liter of isopropyl alcohol was performed three times, and the obtained precipitate was dried under reduced pressure at 80 ° C. for 6 hours, and then diluted to 50% with N, N-dimethylformamide to obtain a polyimide resin solution D. ..
（実施例５）
５００ｍＬ四つ口フラスコにトルエン１００ｇ、１，１，５，５−テトラメチル−３，３−ジフェニルトリシロキサン１５ｇを入れ、気相部を窒素置換した後、内温１０５℃で加熱、攪拌した。ビニルノルボルネン１２．５ｇ、トルエン１０ｇ、白金ビニルシロキサン錯体のキシレン溶液（白金として３ｗｔ％含有）０.０１６３ｇの混合液を３０分かけて滴下した。滴下終了から３時間後に1Ｈ−ＮＭＲでアリル基の反応率が１００％であることを確認し、６０℃冷却した。その後、アリルコハク酸無水物１．５ｇとトルエン３ｇの混合溶液を滴下した。滴下終了から５時間後に1Ｈ−ＮＭＲでアリルコハク酸無水物の二重結合の反応率が１００％であることを確認し、冷却した反応を終了した。トルエンを減圧留去し、酸無水物基を末端に有する変性シロキサン化合物Ｅを得た。
(Example 5)
Toluene (100 g) and 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane (15 g) were placed in a 500 mL four-necked flask, the gas phase portion was replaced with nitrogen, and the mixture was heated and stirred at an internal temperature of 105 ° C. A mixed solution of 12.5 g of vinyl norbornene, 10 g of toluene, and 0.0163 g of a xylene solution of a platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise over 30 minutes. Three hours after the completion of the dropping , it was confirmed by 1 H-NMR that the reaction rate of the allyl group was 100%, and the mixture was cooled at 60 ° C. Then, a mixed solution of 1.5 g of allyl succinic anhydride and 3 g of toluene was added dropwise. Five hours after the completion of the dropping, 1 H-NMR confirmed that the reaction rate of the double bond of the allyl succinic anhydride was 100%, and the cooling reaction was completed. Toluene was distilled off under reduced pressure to obtain a modified siloxane compound E having an acid anhydride group at the end.
次に、２００ｍＬのフラスコ中に、溶剤としてＮ，Ｎ−ジメチルホルムアミド２０ｇ、上記で得た変性シロキサン化合物Ｅを２．５ｇ、２，２−ビス（４−アミノフェニル）ヘキサフルオロプロパン１．５ｇを投入し、室温、窒素雰囲気下で３０分間撹拌した。さらにＮ，Ｎ−ジメチルホルムアミド５ｇ、ピリジン０．８ｇ、無水酢酸１．５ｇを順次フラスコに投入し、９０℃に加熱しながら３時間撹拌した。常温に戻ってから、フラスコに５００ｍＬのイソプロピルアルコールを投入し、析出物を回収した。更に５００ｍＬリットルのイソプロピルアルコールで洗浄を３回行い、得られた析出物を８０℃で６時間減圧乾燥し、その後、Ｎ，Ｎ−ジメチルホルムアミドで５０％に希釈してポリイミド樹脂溶液Ｅを得た。 Next, in a 200 mL flask, 20 g of N, N-dimethylformamide, 2.5 g of the modified siloxane compound E obtained above, and 1.5 g of 2,2-bis (4-aminophenyl) hexafluoropropane were placed as a solvent. The mixture was charged and stirred at room temperature and a nitrogen atmosphere for 30 minutes. Further, 5 g of N, N-dimethylformamide, 0.8 g of pyridine and 1.5 g of acetic anhydride were sequentially put into a flask, and the mixture was stirred for 3 hours while heating at 90 ° C. After returning to room temperature, 500 mL of isopropyl alcohol was put into the flask, and the precipitate was collected. Further, washing with 500 mL liter of isopropyl alcohol was performed three times, and the obtained precipitate was dried under reduced pressure at 80 ° C. for 6 hours, and then diluted to 50% with N, N-dimethylformamide to obtain a polyimide resin solution E. ..
（実施例６）
５００ｍＬ四つ口フラスコにトルエン１００ｇ、１，１，５，５−テトラメチル−３，３−ジフェニルトリシロキサン１５ｇを入れ、気相部を窒素置換した後、内温１０５℃で加熱、攪拌した。２，２−ビス（３−アリル−４−ヒドロキシフェニル）プロパン１１ｇ、トルエン１０ｇ、白金ビニルシロキサン錯体のキシレン溶液（白金として３ｗｔ％含有）０.０１６３ｇの混合液を３０分かけて滴下した。滴下終了から３時間後に1Ｈ−ＮＭＲでアリル基の反応率が１００％であることを確認し、６０℃冷却した。その後、アリルコハク酸無水物１．５ｇとトルエン３ｇの混合溶液を滴下した。滴下終了から５時間後に1Ｈ−ＮＭＲでアリルコハク酸無水物の二重結合の反応率が１００％であることを確認し、冷却した反応を終了した。トルエンを減圧留去し、酸無水物基を末端に有する変性シロキサン化合物Ｆを得た。
(Example 6)
Toluene (100 g) and 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane (15 g) were placed in a 500 mL four-necked flask, the gas phase portion was replaced with nitrogen, and the mixture was heated and stirred at an internal temperature of 105 ° C. A mixed solution of 11 g of 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 10 g of toluene, and 0.0163 g of a xylene solution of a platinum vinyl siloxane complex (containing 3 wt% as platinum) was added dropwise over 30 minutes. Three hours after the completion of the dropping , it was confirmed by 1 H-NMR that the reaction rate of the allyl group was 100%, and the mixture was cooled at 60 ° C. Then, a mixed solution of 1.5 g of allyl succinic anhydride and 3 g of toluene was added dropwise. Five hours after the completion of the dropping, 1 H-NMR confirmed that the reaction rate of the double bond of the allyl succinic anhydride was 100%, and the cooling reaction was completed. Toluene was distilled off under reduced pressure to obtain a modified siloxane compound F having an acid anhydride group at the end.
次に、２００ｍＬのフラスコ中に、溶剤としてＮ，Ｎ−ジメチルホルムアミド２０ｇ、上記で得た変性シロキサン化合物Ｆを２．５ｇ、２，２−ビス（４−アミノフェニル）ヘキサフルオロプロパン１．５ｇを投入し、室温、窒素雰囲気下で３０分間撹拌した。さらにＮ，Ｎ−ジメチルホルムアミド５ｇ、ピリジン０．８ｇ、無水酢酸１．５ｇを順次フラスコに投入し、９０℃に加熱しながら３時間撹拌した。常温に戻ってから、フラスコに５００ｍＬのイソプロピルアルコールを投入し、析出物を回収した。更に５００ｍＬリットルのイソプロピルアルコールで洗浄を３回行い、得られた析出物を８０℃で６時間減圧乾燥し、その後、Ｎ，Ｎ−ジメチルホルムアミドで５０％に希釈してポリイミド樹脂溶液Ｆを得た。 Next, in a 200 mL flask, 20 g of N, N-dimethylformamide, 2.5 g of the modified siloxane compound F obtained above, and 1.5 g of 2,2-bis (4-aminophenyl) hexafluoropropane were placed as a solvent. The mixture was charged and stirred at room temperature and a nitrogen atmosphere for 30 minutes. Further, 5 g of N, N-dimethylformamide, 0.8 g of pyridine and 1.5 g of acetic anhydride were sequentially put into a flask, and the mixture was stirred for 3 hours while heating at 90 ° C. After returning to room temperature, 500 mL of isopropyl alcohol was put into the flask, and the precipitate was collected. Further washing with 500 mL liter of isopropyl alcohol was performed three times, and the obtained precipitate was dried under reduced pressure at 80 ° C. for 6 hours, and then diluted to 50% with N, N-dimethylformamide to obtain a polyimide resin solution F. ..
（実施例７）
５００ｍＬ四つ口フラスコにトルエン１００ｇ、１，１，５，５−テトラメチル−３，３−ジフェニルトリシロキサン１５ｇを入れ、気相部を窒素置換した後、内温１０５℃で加熱、攪拌した。１，１，５，５−テトラメチルジビニル−３，３−ジフェニルトリシロキサン１２ｇ、トルエン１０ｇ、白金ビニルシロキサン錯体のキシレン溶液（白金として３ｗｔ％含有）０.０１６３ｇの混合液を３０分かけて滴下した。滴下終了から３時間後に1Ｈ−ＮＭＲでアリル基の反応率が１００％であることを確認し、６０℃冷却した。その後、アリルコハク酸無水物１．５ｇとトルエン３ｇの混合溶液を滴下した。滴下終了から５時間後に1Ｈ−ＮＭＲでアリルコハク酸無水物の二重結合の反応率が１００％であることを確認し、冷却した反応を終了した。トルエンを減圧留去し、酸無水物基を末端に有する変性シロキサン化合物Ｇを得た。
(Example 7)
Toluene (100 g) and 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane (15 g) were placed in a 500 mL four-necked flask, the gas phase portion was replaced with nitrogen, and the mixture was heated and stirred at an internal temperature of 105 ° C. A mixed solution of 1,1,5,5-tetramethyldivinyl-3,3-diphenyltrisiloxane 12g, toluene 10g, and a xylene solution of a platinum vinylsiloxane complex (containing 3 wt% as platinum) 0.0163g was added dropwise over 30 minutes. did. Three hours after the completion of the dropping , it was confirmed by 1 H-NMR that the reaction rate of the allyl group was 100%, and the mixture was cooled at 60 ° C. Then, a mixed solution of 1.5 g of allyl succinic anhydride and 3 g of toluene was added dropwise. Five hours after the completion of the dropping, 1 H-NMR confirmed that the reaction rate of the double bond of the allyl succinic anhydride was 100%, and the cooling reaction was completed. Toluene was distilled off under reduced pressure to obtain a modified siloxane compound G having an acid anhydride group at the end.
次に、２００ｍＬのフラスコ中に、溶剤としてＮ，Ｎ−ジメチルホルムアミド２０ｇ、上記で得た変性シロキサン化合物Ｇを２．５ｇ、２，２−ビス（４−アミノフェニル）ヘキサフルオロプロパン１．５ｇを投入し、室温、窒素雰囲気下で３０分間撹拌した。さらにＮ，Ｎ−ジメチルホルムアミド５ｇ、ピリジン０．８ｇ、無水酢酸１．５ｇを順次フラスコに投入し、９０℃に加熱しながら３時間撹拌した。常温に戻ってから、フラスコに５００ｍＬのイソプロピルアルコールを投入し、析出物を回収した。更に５００ｍＬリットルのイソプロピルアルコールで洗浄を３回行い、得られた析出物を８０℃で６時間減圧乾燥し、その後、Ｎ，Ｎ−ジメチルホルムアミドで５０％に希釈してポリイミド樹脂溶液Ｈを得た。 Next, in a 200 mL flask, 20 g of N, N-dimethylformamide, 2.5 g of the modified siloxane compound G obtained above, and 1.5 g of 2,2-bis (4-aminophenyl) hexafluoropropane were added as a solvent. The mixture was charged and stirred at room temperature and a nitrogen atmosphere for 30 minutes. Further, 5 g of N, N-dimethylformamide, 0.8 g of pyridine and 1.5 g of acetic anhydride were sequentially put into a flask, and the mixture was stirred for 3 hours while heating at 90 ° C. After returning to room temperature, 500 mL of isopropyl alcohol was put into the flask, and the precipitate was collected. Further, washing with 500 mL liter of isopropyl alcohol was performed three times, and the obtained precipitate was dried under reduced pressure at 80 ° C. for 6 hours, and then diluted to 50% with N, N-dimethylformamide to obtain a polyimide resin solution H. ..
（実施例８）
５００ｍＬ四つ口フラスコにトルエン１００ｇ、１，１，５，５−テトラメチル−３，３−ジフェニルトリシロキサン１５ｇを入れ、気相部を窒素置換した後、内温１０５℃で加熱、攪拌した。ジアリルモノメチルイソシアヌレート９ｇ、トルエン１０ｇ、白金ビニルシロキサン錯体のキシレン溶液（白金として３ｗｔ％含有）０.０１６３ｇの混合液を３０分かけて滴下した。滴下終了から３時間後に1Ｈ−ＮＭＲでアリル基の反応率が１００％であることを確認し、６０℃冷却した。その後、イタコン酸無水物１．３ｇとトルエン３ｇの混合溶液を滴下した。滴下終了から５時間後に1Ｈ−ＮＭＲでイタコン酸無水物の二重結合の反応率が１００％であることを確認し、冷却した反応を終了した。トルエンを減圧留去し、酸無水物基を末端に有する変性シロキサン化合物Ｈを得た。
(Example 8)
Toluene (100 g) and 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane (15 g) were placed in a 500 mL four-necked flask, the gas phase portion was replaced with nitrogen, and the mixture was heated and stirred at an internal temperature of 105 ° C. A mixed solution of 9 g of diallyl monomethylisocyanurate, 10 g of toluene, and 0.0163 g of a xylene solution of a platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise over 30 minutes. Three hours after the completion of the dropping , it was confirmed by 1 H-NMR that the reaction rate of the allyl group was 100%, and the mixture was cooled at 60 ° C. Then, a mixed solution of 1.3 g of itaconic acid anhydride and 3 g of toluene was added dropwise. Five hours after the completion of the dropping , it was confirmed by 1 H-NMR that the reaction rate of the double bond of the itaconic acid anhydride was 100%, and the cooling reaction was completed. Toluene was distilled off under reduced pressure to obtain a modified siloxane compound H having an acid anhydride group at the end.
次に、２００ｍＬのフラスコ中に、溶剤としてＮ，Ｎ−ジメチルホルムアミド２０ｇ、上記で得た変性シロキサン化合物Ｈを２．５ｇ、２，２−ビス（４−アミノフェニル）ヘキサフルオロプロパン１．５ｇを投入し、室温、窒素雰囲気下で３０分間撹拌した。さらにＮ，Ｎ−ジメチルホルムアミド５ｇ、ピリジン０．８ｇ、無水酢酸１．５ｇを順次フラスコに投入し、９０℃に加熱しながら３時間撹拌した。常温に戻ってから、フラスコに５００ｍＬのイソプロピルアルコールを投入し、析出物を回収した。更に５００ｍＬリットルのイソプロピルアルコールで洗浄を３回行い、得られた析出物を８０℃で６時間減圧乾燥し、その後、Ｎ，Ｎ−ジメチルホルムアミドで５０％に希釈してポリイミド樹脂溶液Ｉを得た。 Next, in a 200 mL flask, 20 g of N, N-dimethylformamide, 2.5 g of the modified siloxane compound H obtained above, and 1.5 g of 2,2-bis (4-aminophenyl) hexafluoropropane were placed as a solvent. The mixture was charged and stirred at room temperature and a nitrogen atmosphere for 30 minutes. Further, 5 g of N, N-dimethylformamide, 0.8 g of pyridine and 1.5 g of acetic anhydride were sequentially put into a flask, and the mixture was stirred for 3 hours while heating at 90 ° C. After returning to room temperature, 500 mL of isopropyl alcohol was put into the flask, and the precipitate was collected. Further washing with 500 mL liter of isopropyl alcohol was performed three times, and the obtained precipitate was dried under reduced pressure at 80 ° C. for 6 hours, and then diluted to 50% with N, N-dimethylformamide to obtain a polyimide resin solution I. ..
（実施例９）
５００ｍＬ四つ口フラスコにトルエン１００ｇ、１，１，５，５−テトラメチル−３，３−ジフェニルトリシロキサン１５ｇを入れ、気相部を窒素置換した後、内温１０５℃で加熱、攪拌した。ジアリルモノメチルイソシアヌレート９ｇ、トルエン１０ｇ、白金ビニルシロキサン錯体のキシレン溶液（白金として３ｗｔ％含有）０.０１６３ｇの混合液を３０分かけて滴下した。滴下終了から３時間後に1Ｈ−ＮＭＲでアリル基の反応率が１００％であることを確認し、６０℃冷却した。その後、マレイン酸無水物１．０ｇとトルエン３ｇの混合溶液を滴下した。滴下終了から５時間後に1Ｈ−ＮＭＲでマレイン酸無水物の二重結合の反応率が１００％であることを確認し、冷却した反応を終了した。トルエンを減圧留去し、酸無水物基を末端に有する変性シロキサン化合物Ｉを得た。
(Example 9)
Toluene (100 g) and 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane (15 g) were placed in a 500 mL four-necked flask, the gas phase portion was replaced with nitrogen, and the mixture was heated and stirred at an internal temperature of 105 ° C. A mixed solution of 9 g of diallyl monomethylisocyanurate, 10 g of toluene, and 0.0163 g of a xylene solution of a platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise over 30 minutes. Three hours after the completion of the dropping , it was confirmed by 1 H-NMR that the reaction rate of the allyl group was 100%, and the mixture was cooled at 60 ° C. Then, a mixed solution of 1.0 g of maleic anhydride and 3 g of toluene was added dropwise. Five hours after the completion of the dropping, 1 H-NMR confirmed that the reaction rate of the double bond of maleic anhydride was 100%, and the cooling reaction was completed. Toluene was distilled off under reduced pressure to obtain a modified siloxane compound I having an acid anhydride group at the end.
次に、２００ｍＬのフラスコ中に、溶剤としてＮ，Ｎ−ジメチルホルムアミド２０ｇ、上記で得た変性シロキサン化合物Ｉを２．５ｇ、２，２−ビス（４−アミノフェニル）ヘキサフルオロプロパン１．５ｇを投入し、室温、窒素雰囲気下で３０分間撹拌した。さらにＮ，Ｎ−ジメチルホルムアミド５ｇ、ピリジン０．８ｇ、無水酢酸１．５ｇを順次フラスコに投入し、９０℃に加熱しながら３時間撹拌した。常温に戻ってから、フラスコに５００ｍＬのイソプロピルアルコールを投入し、析出物を回収した。更に５００ｍＬリットルのイソプロピルアルコールで洗浄を３回行い、得られた析出物を８０℃で６時間減圧乾燥し、その後、Ｎ，Ｎ−ジメチルホルムアミドで５０％に希釈してポリイミド樹脂溶液Ｊを得た。 Next, in a 200 mL flask, 20 g of N, N-dimethylformamide, 2.5 g of the modified siloxane compound I obtained above, and 1.5 g of 2,2-bis (4-aminophenyl) hexafluoropropane were added as a solvent. The mixture was charged and stirred at room temperature and a nitrogen atmosphere for 30 minutes. Further, 5 g of N, N-dimethylformamide, 0.8 g of pyridine and 1.5 g of acetic anhydride were sequentially put into a flask, and the mixture was stirred for 3 hours while heating at 90 ° C. After returning to room temperature, 500 mL of isopropyl alcohol was put into the flask, and the precipitate was collected. Further, washing with 500 mL liter of isopropyl alcohol was performed three times, and the obtained precipitate was dried under reduced pressure at 80 ° C. for 6 hours, and then diluted to 50% with N, N-dimethylformamide to obtain a polyimide resin solution J. ..
（比較例１）
２００ｍＬのフラスコ中に、溶剤としてＮ，Ｎ−ジメチルホルムアミド２０ｇ、シロキサンジアミン（商品名：ＫＦ−８０１０、信越化学工業株式会社製）を１．５ｇ、２，２’−ヘキサフルオロプロピリデンジフタル酸二無水物２．５ｇを投入し、室温、窒素雰囲気下で３０分間撹拌した。さらにＮ，Ｎ−ジメチルホルムアミド５ｇ、ピリジン０．８ｇ、無水酢酸１．５ｇを順次フラスコに投入し、９０℃に加熱しながら３時間撹拌した。常温に戻ってから、フラスコに５００ｍＬのイソプロピルアルコールを投入し、析出物を回収した。更に５００ｍＬリットルのイソプロピルアルコールで洗浄を３回行い、得られた析出物を８０℃で６時間減圧乾燥し、その後、Ｎ，Ｎ−ジメチルホルムアミドで５０％に希釈してポリイミド樹脂溶液Ｊを得た。
(Comparative Example 1)
In a 200 mL flask, 20 g of N, N-dimethylformamide and 1.5 g of siloxane diamine (trade name: KF-8010, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) as a solvent, 2,2'-hexafluoropropyridene diphthalic acid. 2.5 g of dianhydride was added, and the mixture was stirred at room temperature and a nitrogen atmosphere for 30 minutes. Further, 5 g of N, N-dimethylformamide, 0.8 g of pyridine and 1.5 g of acetic anhydride were sequentially put into a flask, and the mixture was stirred for 3 hours while heating at 90 ° C. After returning to room temperature, 500 mL of isopropyl alcohol was put into the flask, and the precipitate was collected. Further, washing with 500 mL liter of isopropyl alcohol was performed three times, and the obtained precipitate was dried under reduced pressure at 80 ° C. for 6 hours, and then diluted to 50% with N, N-dimethylformamide to obtain a polyimide resin solution J. ..
（比較例２）
２００ｍＬのフラスコ中に、溶剤としてＮ，Ｎ−ジメチルホルムアミド２０ｇ、２，２−ビス（４−アミノフェニル）ヘキサフルオロプロパン１．５ｇ、２，２’−ヘキサフルオロプロピリデンジフタル酸二無水物２．５ｇを投入し、室温、窒素雰囲気下で３０分間撹拌した。さらにＮ，Ｎ−ジメチルホルムアミド５ｇ、ピリジン０．８ｇ、無水酢酸１．５ｇを順次フラスコに投入し、９０℃に加熱しながら３時間撹拌した。常温に戻ってから、フラスコに５００ｍＬのイソプロピルアルコールを投入し、析出物を回収した。更に５００ｍＬリットルのイソプロピルアルコールで洗浄を３回行い、得られた析出物を８０℃で６時間減圧乾燥し、その後、Ｎ，Ｎ−ジメチルホルムアミドで５０％に希釈してポリイミド樹脂溶液Ｋを得た。
(Comparative Example 2)
In a 200 mL flask, 20 g of N, N-dimethylformamide, 1.5 g of 2,2-bis (4-aminophenyl) hexafluoropropane as a solvent, 2,2'-hexafluoropropyridene diphthalic acid dianhydride 2 .5 g was added, and the mixture was stirred at room temperature and a nitrogen atmosphere for 30 minutes. Further, 5 g of N, N-dimethylformamide, 0.8 g of pyridine and 1.5 g of acetic anhydride were sequentially put into a flask, and the mixture was stirred for 3 hours while heating at 90 ° C. After returning to room temperature, 500 mL of isopropyl alcohol was put into the flask, and the precipitate was collected. Further washing with 500 mL liter of isopropyl alcohol was performed three times, and the obtained precipitate was dried under reduced pressure at 80 ° C. for 6 hours, and then diluted to 50% with N, N-dimethylformamide to obtain a polyimide resin solution K. ..
（結果）
実施例１〜９および比較例１、２で得られたポリイミド樹脂溶液に対し、前述の評価を行った。その結果を表１に示す。
(result)
The polyimide resin solutions obtained in Examples 1 to 9 and Comparative Examples 1 and 2 were evaluated as described above. The results are shown in Table 1.
本発明は、半導体やディスプレイ等のエレクトロニクスデバイス用の絶縁層間膜、接着剤、コーティング剤および封止剤等の様々な分野で利用することができる。 The present invention can be used in various fields such as insulating interlayer films for electronic devices such as semiconductors and displays, adhesives, coating agents and encapsulants.
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