JP2022034459A - Siloxane diacid anhydride and polyimide resin - Google Patents
Siloxane diacid anhydride and polyimide resin Download PDFInfo
- Publication number
- JP2022034459A JP2022034459A JP2020138252A JP2020138252A JP2022034459A JP 2022034459 A JP2022034459 A JP 2022034459A JP 2020138252 A JP2020138252 A JP 2020138252A JP 2020138252 A JP2020138252 A JP 2020138252A JP 2022034459 A JP2022034459 A JP 2022034459A
- Authority
- JP
- Japan
- Prior art keywords
- siloxane
- compound
- acid anhydride
- polyimide resin
- group
- 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.)
- Pending
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 28
- 239000009719 polyimide resin Substances 0.000 title claims abstract description 27
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 150000008064 anhydrides Chemical class 0.000 title claims abstract description 10
- -1 diamine compound Chemical class 0.000 claims abstract description 35
- 125000004018 acid anhydride group Chemical group 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 5
- 150000008065 acid anhydrides Chemical class 0.000 claims description 11
- 125000000962 organic group Chemical group 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000006459 hydrosilylation reaction Methods 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 46
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 28
- 239000000203 mixture Substances 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 16
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 15
- 229910052697 platinum Inorganic materials 0.000 description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 6
- 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 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 239000002253 acid Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000008096 xylene Substances 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 3
- WUMMIJWEUDHZCL-UHFFFAOYSA-N 3-prop-2-enyloxolane-2,5-dione Chemical compound C=CCC1CC(=O)OC1=O WUMMIJWEUDHZCL-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 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
- 230000009257 reactivity Effects 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
- 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 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 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
- 229920001296 polysiloxane Polymers 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
- 239000002904 solvent Substances 0.000 description 2
- 239000000758 substrate Substances 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
- 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
- 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
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-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
- 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
- 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
- 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
- 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
- NRLUQVLHGAVXQB-UHFFFAOYSA-N 4-(4-amino-2-chloro-5-methoxyphenyl)-5-chloro-2-methoxyaniline Chemical group C1=C(N)C(OC)=CC(C=2C(=CC(N)=C(OC)C=2)Cl)=C1Cl NRLUQVLHGAVXQB-UHFFFAOYSA-N 0.000 description 1
- WYHSHHJLHFEEFE-UHFFFAOYSA-N 4-(4-aminophenyl)-6,6-dimethylcyclohexa-1,3-dien-1-amine Chemical group C1=C(N)C(C)(C)CC(C=2C=CC(N)=CC=2)=C1 WYHSHHJLHFEEFE-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- NHLGDELWVDRKBL-UHFFFAOYSA-N 4-[4-(1,1,1,3,3,3-hexafluoropropan-2-yl)phenoxy]-3-(trifluoromethyl)aniline Chemical compound NC1=CC(=C(OC2=CC=C(C=C2)C(C(F)(F)F)C(F)(F)F)C=C1)C(F)(F)F NHLGDELWVDRKBL-UHFFFAOYSA-N 0.000 description 1
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 1
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 1
- HYDATEKARGDBKU-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]phenoxy]aniline Chemical group C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 HYDATEKARGDBKU-UHFFFAOYSA-N 0.000 description 1
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical group FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 1
- KIFDSGGWDIVQGN-UHFFFAOYSA-N 4-[9-(4-aminophenyl)fluoren-9-yl]aniline Chemical compound C1=CC(N)=CC=C1C1(C=2C=CC(N)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 KIFDSGGWDIVQGN-UHFFFAOYSA-N 0.000 description 1
- XPAQFJJCWGSXGJ-UHFFFAOYSA-N 4-amino-n-(4-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1NC(=O)C1=CC=C(N)C=C1 XPAQFJJCWGSXGJ-UHFFFAOYSA-N 0.000 description 1
- SNCJAJRILVFXAE-UHFFFAOYSA-N 9h-fluorene-2,7-diamine Chemical compound NC1=CC=C2C3=CC=C(N)C=C3CC2=C1 SNCJAJRILVFXAE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920003354 Modic® Polymers 0.000 description 1
- UIEXFJVOIMVETD-UHFFFAOYSA-N P([O-])([O-])[O-].[Pt+3] Chemical compound P([O-])([O-])[O-].[Pt+3] UIEXFJVOIMVETD-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- LDKSTCHEYCNPDS-UHFFFAOYSA-L carbon monoxide;dichloroplatinum Chemical compound O=C=[Pt](Cl)(Cl)=C=O LDKSTCHEYCNPDS-UHFFFAOYSA-L 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- 238000009429 electrical wiring Methods 0.000 description 1
- 239000008393 encapsulating agent Substances 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
- 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
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-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
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002994 raw material 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
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
本発明は、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 siloxane diic acid 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、樹脂へ柔軟性を付与させる目的で、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. There is. 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、ナジック酸無水物はヒドロシリル化反応性に非常に乏しく、高純度で両末端に酸無水物基を有する化合物を得る事が難しいため、低分子量のポリイミド樹脂しか得られず、密着性に欠け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, nadic acid anhydride has very poor hydrosilylation reactivity, and it is difficult to obtain a compound having an acid anhydride group at both ends with high purity. Therefore, only a low molecular weight polyimide resin can be obtained, and adhesion is lacking. I have a problem.
本発明は、柔軟性および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 a polyimide resin having excellent flexibility and adhesion.
上記課題を達成の為に検討を重ねた結果、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 has been found that the siloxane diic acid anhydride and the polyimide resin obtained by using the siloxane diacid anhydride have flexibility and excellent adhesion. The present invention comprises the following.
〔1〕.(A)1分子中にSiH基を2個有するケイ素化合物と、(B)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、とをヒドロシリル化することにより得られる以下で示されるシロキサン二酸無水物であり、 [1]. Obtained by hydrosilylating (A) a silicon compound having two SiH groups in one molecule and (B) a compound having one carbon-carbon double bond and one acid anhydride group in one molecule. Is a siloxane diic acid anhydride shown below,
(上記化学式において、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の整数である)
かつ、成分(B)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シロキサン二酸無水物。
(In the above chemical formula, 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, and n is an integer of 0 to 50).
Moreover, the siloxane diic acid anhydride is characterized in that the component (B) is selected from the compounds described below.
〔2〕.〔1〕に記載のシロキサン二酸無水物とジアミン化合物また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。 [2]. A polyimide resin obtained by reacting the siloxane diic anhydride according to [1] with a diamine compound or a diisocyanate compound.
本発明によればシロキサン二酸無水物を高効率で得ることができる。また、それを用いることにより、柔軟性および密着性に優れるポリイミド樹脂を得ることができる。 According to the present invention, siloxane diic acid anhydride can be obtained with high efficiency. Further, by using it, a polyimide resin having excellent flexibility and adhesion can be obtained.
(シロキサン二酸無水物)
上記、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シロキサン二酸無水物である。
(Siloxane acid anhydride)
The above-mentioned siloxane diic anhydride is a 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、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の整数である)
また、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、Xの酸無水物基は、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。
(In the above chemical formula, 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, and n is an integer of 0 to 50).
Further, from the viewpoint of introducing the polyimide resin without impairing the heat resistance, which is a feature of the polyimide resin, the method of introducing the acid anhydride group of X by using the hydrosilylation reaction shown below is preferable.
以下、ヒドロシリル化反応を用いて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 siloxane diic acid anhydride using a hydrosilylation reaction will be described.
(成分(A):1分子中にSiH基を2個有するケイ素化合物)
成分(A)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 (A): Silicon compound having two SiH groups in one molecule)
The component (A) 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 compounds other than the polysiloxane compound at the end of the SiH group can also be used, for example, 1,4-bis (dimethylsilyl) benzene, 1,4-bis (diphenylsilyl) benzene, 1,4-bis (1,4-bis). Methylphenylsilyl) benzene, etc. are specifically mentioned.
(成分(B):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(B)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る。成分(B)としては、SiH基との反応性に優れ、高収率で両末端に酸無水物基を導入することができる化合物が好ましい。一方で、特に、ナジック酸無水物やマレイン酸化合物などの化合物は、分子構造上ヒドロシリル化反応性に乏しく、高収率で両末端に酸無水物基を導入したシロキサン二酸無水物を得ることが難しいため、これら化合物を用いたポリイミド樹脂は低分子量となり、密着性、強度に欠けるため好ましくない。
(Component (B): A compound having one carbon-carbon double bond and one acid anhydride group in one molecule)
The component (B) is a compound having one carbon-carbon double bond and one acid anhydride group in one molecule. As the component (B), a compound having excellent reactivity with a SiH group and capable of introducing an acid anhydride group at both ends in a high yield is preferable. On the other hand, in particular, compounds such as nadic acid anhydride and maleic acid compound have poor hydrosilylation reactivity due to their molecular structure, and a siloxane diic acid anhydride having an acid anhydride group introduced at both ends can be obtained in high yield. Therefore, a polyimide resin using these compounds has a low molecular weight and lacks adhesion and strength, which is not preferable.
好ましい化合物例としては、イタコン酸無水物、アリルコハク酸無水物、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。さらに好ましくは、イタコン酸無水物、アリルコハク酸無水物が好ましい。 Preferred compound examples include itaconic acid anhydride, allylsuccinic anhydride, tetrahydrophthalic anhydride, tetrahydromethylphthalic anhydride, and tetramethylphenylphthalic anhydride. More preferably, itaconic acid anhydride and allyl succinic acid anhydride are preferable.
(成分(A)、(B)の反応)
成分(A)、(B)を反応させ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) and (B))
A hydrosilylation reaction is used as a method for reacting the components (A) and (B) to obtain a siloxane diic acid anhydride. 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-hydrocarbon 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。 Examples of catalysts other than platinum compounds include RhCl (PPh) 3 , RhCl 3 , RhAl 2 O 3 , RuCl 3 , IrCl 3 , FeCl 3 , AlCl 3 , PdCl 2.2H 2 O, NiCl 2 , and 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.
(ポリイミド樹脂について)
本発明の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また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 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、また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-phenylene isopropylidene) 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, Tetrahydrodicyclopentadienylene diamine, Hexahydro-4,7-Metanoindanylenedimethylenediamine, Tricyclo [6,2,1,02.7] -Undecylenedimethyldiamine, 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もしく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、もしくは、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 to 10% peeling 2: 20 to 30% peeling 3: 50% peeling 4: 70 to 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.
(分子量測定)
得られたポリイミド樹脂溶液をそれぞれDMF(ジメチルホルムアミド)で0.5wt%に希釈して、GPC(Gel Permeation Chromatography;ゲル浸透クロマトグラフ)システム(東ソー(株)製、HCL-8420)により分析を行い、標準ポリスチレン換算で、重量平均分子量(Mw)を測定した。
(Measurement of molecular weight)
Each of the obtained polyimide resin solutions was diluted to 0.5 wt% with DMF (dimethylformamide) and analyzed by a GPC (Gel Permeation Chromatography) system (HCL-8420, manufactured by Toso Co., Ltd.). , Weight average molecular weight (Mw) was measured in terms of standard polystyrene.
(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。アリルコハク酸無水物12.85g、トルエン15g、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で二重結合の反応率が100%であることを確認して、冷却し反応を終了した。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 mixture of 12.85 g of allyl succinic anhydride, 15 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 double bond was 100%, and the reaction was cooled to complete the reaction. Toluene was distilled off under reduced pressure to obtain a 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, 20 g of N, N-dimethylformamide, 2.5 g of the siloxane compound A obtained above, and 1.5 g of 2,2-bis (4-aminophenyl) hexafluoropropane were placed in a 200 mL flask. Then, 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 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 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。イタコン酸無水物10.28g、トルエン15g、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で二重結合の反応率が100%であることを確認して、冷却し反応を終了した。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 mixture of 10.28 g of itaconic acid anhydride, 15 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 double bond was 100%, and the reaction was cooled to complete the reaction. Toluene was distilled off under reduced pressure to obtain a 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, 20 g of N, N-dimethylformamide, 2.5 g of the siloxane compound B obtained above, and 1.5 g of 2,2-bis (4-aminophenyl) hexafluoropropane were placed in a 200 mL flask. Then, 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 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 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。テトラヒドロ無水フタル酸13g、トルエン13g、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6時間後に1H-NMRで二重結合の反応率が100%であることを確認して、冷却し反応を終了した。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 mixture of 13 g of tetrahydrophthalic anhydride, 13 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. Six hours after the completion of the dropping, 1 H-NMR was confirmed to confirm that the reaction rate of the double bond was 100%, and the reaction was cooled to complete the reaction. Toluene was distilled off under reduced pressure to obtain a 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, 20 g of N, N-dimethylformamide, 2.5 g of the siloxane compound C obtained above, and 1.5 g of 2,2-bis (4-aminophenyl) hexafluoropropane were placed in a 200 mL flask. Then, 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 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 C.
(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D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 the dianhydride was added, and the mixture was stirred at room temperature and in 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. ..
(比較例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。ナジック酸無水物15.5g、1,4-ジオキサン15.5g、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24時間後に1H-NMRで二重結合の反応率が90%でそれ以上反応が進行しないことを確認して、冷却し反応を終了した。1,4-ジオキサンを減圧留去し、酸無水物基を末端に有するシロキサン化合物Dを得た。
(Comparative 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 mixture of 15.5 g of nagic acid anhydride, 15.5 g of 1,4-dioxane and 0.0163 g of a xylene solution of a platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise over 30 minutes. Twenty-four hours after the completion of the dropping, it was confirmed by 1 H-NMR that the reaction rate of the double bond was 90% and the reaction did not proceed any further, and the reaction was cooled to complete the reaction. 1,4-Dioxane was distilled off under reduced pressure to obtain a 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, 20 g of N, N-dimethylformamide, 2.5 g of the siloxane compound D obtained above, and 1.5 g of 2,2-bis (4-aminophenyl) hexafluoropropane were placed in a 200 mL flask. Then, 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 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 E.
(結果)
実施例1~3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 3 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.
Claims (2)
かつ、成分(B)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シロキサン二酸無水物。
Moreover, the siloxane diic acid anhydride is characterized in that the component (B) is selected from the compounds described below.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2020138252A JP2022034459A (en) | 2020-08-18 | 2020-08-18 | Siloxane diacid anhydride and polyimide resin |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2020138252A JP2022034459A (en) | 2020-08-18 | 2020-08-18 | Siloxane diacid anhydride and polyimide resin |
Publications (1)
Publication Number | Publication Date |
---|---|
JP2022034459A true JP2022034459A (en) | 2022-03-03 |
Family
ID=80442173
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2020138252A Pending JP2022034459A (en) | 2020-08-18 | 2020-08-18 | Siloxane diacid anhydride and polyimide resin |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2022034459A (en) |
-
2020
- 2020-08-18 JP JP2020138252A patent/JP2022034459A/en active Pending
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JPS63500802A (en) | Flame retardant wire coating composition | |
KR101480587B1 (en) | Novel silphenylene skeleton containing silicone type polymer compound and method for producing the same | |
KR100938043B1 (en) | Imide Silicone Resin and Process for Preparing the Same | |
JP3232123B2 (en) | Curable composition | |
JP4535245B2 (en) | Partially-blocked polyimide-polysiloxane copolymer, process for producing the same, and resin composition containing the copolymer | |
TW200920768A (en) | Thermal curing polyimide silicon resin composition and membrane containing the same | |
US6297341B1 (en) | Silicone-containing polyimide resin, silicon-containing polyamic acid, and methods for manufacture | |
JP4549382B2 (en) | Novel silphenylene compound and process for producing the same | |
JP2799217B2 (en) | Fluorinated diaminobenzene derivatives and polyimides | |
TWI332961B (en) | ||
TW200927795A (en) | Flame-retardant polyimide-silicone resin composition | |
JP2022034459A (en) | Siloxane diacid anhydride and polyimide resin | |
JP2021195474A (en) | Modified siloxane diacid anhydride and polyimide resin | |
JP4377354B2 (en) | Polyimide silicone resin composition | |
US6001942A (en) | Silicon-containing polyimide resin and silicon-containing polyamic acid | |
JP3232124B2 (en) | Curable composition | |
JP2022012362A (en) | Modified siloxane diamine compound and polyimide resin | |
JP3359359B2 (en) | Curable composition | |
JP2022012361A (en) | Modified siloxane diisocyanate compound and polyimide resin | |
JP4041771B2 (en) | Polyimide silicone resin composition | |
JP3279663B2 (en) | Hydrosilyl group-containing imide compound | |
JP4018589B2 (en) | Reactive silyl group-containing bisimide compound and method for producing the same | |
JP3279636B2 (en) | Hydrosilyl group-containing imide compound | |
JP3279662B2 (en) | Hydrosilyl group-containing imide compound | |
JP3359360B2 (en) | Curable composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20230622 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20240521 |