WO2012176806A1 - 難燃化された脂環式ポリイミド樹脂組成物およびその薄肉成型体 - Google Patents
難燃化された脂環式ポリイミド樹脂組成物およびその薄肉成型体 Download PDFInfo
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- WO2012176806A1 WO2012176806A1 PCT/JP2012/065752 JP2012065752W WO2012176806A1 WO 2012176806 A1 WO2012176806 A1 WO 2012176806A1 JP 2012065752 W JP2012065752 W JP 2012065752W WO 2012176806 A1 WO2012176806 A1 WO 2012176806A1
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- WO
- WIPO (PCT)
- Prior art keywords
- polyimide resin
- alicyclic
- resin composition
- alicyclic polyimide
- mass
- Prior art date
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 156
- 239000009719 polyimide resin Substances 0.000 title claims abstract description 154
- 125000002723 alicyclic group Chemical group 0.000 title claims abstract description 133
- 239000000203 mixture Substances 0.000 title claims abstract description 76
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000005266 casting Methods 0.000 claims abstract description 6
- -1 4-cyanophenoxy group Chemical group 0.000 claims description 50
- 239000003960 organic solvent Substances 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- 125000001931 aliphatic group Chemical group 0.000 claims description 11
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 abstract description 38
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 34
- 229910052736 halogen Inorganic materials 0.000 abstract description 7
- 150000002367 halogens Chemical class 0.000 abstract description 7
- 229910019142 PO4 Inorganic materials 0.000 abstract description 5
- 229910052787 antimony Inorganic materials 0.000 abstract description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 4
- 239000010452 phosphate Substances 0.000 abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 238000004519 manufacturing process Methods 0.000 description 25
- 230000009477 glass transition Effects 0.000 description 24
- 238000002834 transmittance Methods 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000007787 solid Substances 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
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- 239000003054 catalyst Substances 0.000 description 15
- 150000004985 diamines Chemical class 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 239000000758 substrate Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 14
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 12
- LJMPOXUWPWEILS-UHFFFAOYSA-N 3a,4,4a,7a,8,8a-hexahydrofuro[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1C2C(=O)OC(=O)C2CC2C(=O)OC(=O)C21 LJMPOXUWPWEILS-UHFFFAOYSA-N 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
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- 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 9
- 150000004984 aromatic diamines Chemical class 0.000 description 9
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- 239000000047 product Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000009413 insulation Methods 0.000 description 7
- 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 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000006358 imidation reaction Methods 0.000 description 5
- 230000001771 impaired effect Effects 0.000 description 5
- 229920005575 poly(amic acid) Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000003566 sealing material Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 5
- AWYVETCHVQGXMB-UHFFFAOYSA-N (3-hydroxyphenyl) diphenyl phosphate Chemical compound OC1=CC=CC(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)=C1 AWYVETCHVQGXMB-UHFFFAOYSA-N 0.000 description 4
- HESXPOICBNWMPI-UHFFFAOYSA-N 4-[2-[4-[2-(4-aminophenyl)propan-2-yl]phenyl]propan-2-yl]aniline Chemical compound C=1C=C(C(C)(C)C=2C=CC(N)=CC=2)C=CC=1C(C)(C)C1=CC=C(N)C=C1 HESXPOICBNWMPI-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000009102 absorption Effects 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 229910000410 antimony oxide Inorganic materials 0.000 description 4
- 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 4
- 239000011248 coating agent Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 150000002366 halogen compounds Chemical class 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 125000005462 imide group Chemical group 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000011810 insulating material Substances 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 3
- 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 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- ZPAKUZKMGJJMAA-UHFFFAOYSA-N Cyclohexane-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)CC1C(O)=O ZPAKUZKMGJJMAA-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001334 alicyclic compounds Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- KRPRVQWGKLEFKN-UHFFFAOYSA-N 3-(3-aminopropoxy)propan-1-amine Chemical compound NCCCOCCCN KRPRVQWGKLEFKN-UHFFFAOYSA-N 0.000 description 2
- YJOAIOIVLVUPST-UHFFFAOYSA-N 4-(4-amino-2-methoxyphenyl)-3-methoxyaniline Chemical group COC1=CC(N)=CC=C1C1=CC=C(N)C=C1OC YJOAIOIVLVUPST-UHFFFAOYSA-N 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- 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 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- VAYBSUUSYTWKBX-UHFFFAOYSA-N bicyclo[2.2.1]heptane-2,3,3,4-tetracarboxylic acid Chemical compound C1CC2(C(O)=O)C(C(O)=O)(C(O)=O)C(C(=O)O)C1C2 VAYBSUUSYTWKBX-UHFFFAOYSA-N 0.000 description 2
- XQBSPQLKNWMPMG-UHFFFAOYSA-N bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic acid Chemical compound C1CC2C(C(O)=O)C(C(=O)O)C1C(C(O)=O)C2C(O)=O XQBSPQLKNWMPMG-UHFFFAOYSA-N 0.000 description 2
- 235000013877 carbamide Nutrition 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- 150000003997 cyclic ketones Chemical class 0.000 description 2
- WOSVXXBNNCUXMT-UHFFFAOYSA-N cyclopentane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)C1C(O)=O WOSVXXBNNCUXMT-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 229920006015 heat resistant resin Polymers 0.000 description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 2
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical group [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 239000003495 polar organic solvent Substances 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000013557 residual solvent Substances 0.000 description 2
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- 238000003860 storage Methods 0.000 description 2
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 125000000101 thioether group Chemical group 0.000 description 2
- 150000003672 ureas Chemical class 0.000 description 2
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- 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
- KWLBPQBIJQBPJC-UHFFFAOYSA-N 2,3,5-tris(methoxycarbonyl)bicyclo[2.2.2]octane-6-carboxylic acid Chemical compound C1CC2C(C(O)=O)C(C(=O)OC)C1C(C(=O)OC)C2C(=O)OC KWLBPQBIJQBPJC-UHFFFAOYSA-N 0.000 description 1
- PIQCSNVSJNBSSH-UHFFFAOYSA-N 2,3-bis(methoxycarbonyl)bicyclo[2.2.2]oct-7-ene-5,6-dicarboxylic acid Chemical compound C1=CC2C(C(O)=O)C(C(O)=O)C1C(C(=O)OC)C2C(=O)OC PIQCSNVSJNBSSH-UHFFFAOYSA-N 0.000 description 1
- OHEMJALWWFTURW-UHFFFAOYSA-N 2,3-bis(methoxycarbonyl)bicyclo[2.2.2]octane-5,6-dicarboxylic acid Chemical compound C1CC2C(C(O)=O)C(C(O)=O)C1C(C(=O)OC)C2C(=O)OC OHEMJALWWFTURW-UHFFFAOYSA-N 0.000 description 1
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- ABONQFBBGFQJRT-UHFFFAOYSA-N 2,4,5-tris(methoxycarbonyl)cyclohexane-1-carboxylic acid Chemical compound COC(=O)C1CC(C(=O)OC)C(C(=O)OC)CC1C(O)=O ABONQFBBGFQJRT-UHFFFAOYSA-N 0.000 description 1
- MXSKJYLPNPYQHH-UHFFFAOYSA-N 2,4-dimethyl-6-(1-methylcyclohexyl)phenol Chemical compound CC1=CC(C)=C(O)C(C2(C)CCCCC2)=C1 MXSKJYLPNPYQHH-UHFFFAOYSA-N 0.000 description 1
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- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical group C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- FQNLFSYKGJVORV-UHFFFAOYSA-N 3,3,4-tris(methoxycarbonyl)bicyclo[2.2.1]heptane-2-carboxylic acid Chemical compound C1CC2C(C(O)=O)C(C(=O)OC)(C(=O)OC)C1(C(=O)OC)C2 FQNLFSYKGJVORV-UHFFFAOYSA-N 0.000 description 1
- CGFQSHBACNBBDF-UHFFFAOYSA-N 3,4-bis(methoxycarbonyl)bicyclo[2.2.1]heptane-2,3-dicarboxylic acid Chemical compound C1CC2C(C(O)=O)C(C(=O)OC)(C(O)=O)C1(C(=O)OC)C2 CGFQSHBACNBBDF-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
- C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
- C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
- C08G79/025—Polyphosphazenes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
- C08L85/02—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing phosphorus
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
Definitions
- the present invention relates to a polyimide resin composition and a thin molded body thereof.
- a polyimide resin is a heat-resistant resin obtained by ring-closing reaction of a polyamic acid synthesized from an aromatic tetracarboxylic acid anhydride and an aromatic diamine as raw materials.
- Such wholly aromatic polyimide resins have excellent resistance to thermal decomposition due to molecular chain rigidity, resonance stabilization, and strong chemical bonding, and are highly resistant to chemical changes such as oxidation or hydrolysis. Excellent mechanical and electrical characteristics.
- wholly aromatic polyimide resins are flexible and are widely used as films, coating agents, molded parts and insulating materials in fields such as the electrical, electronic, automotive and aerospace industries. However, since the wholly aromatic polyimide resin is colored from pale yellow to reddish brown, it is unsuitable as an alternative material for glass and ceramic used for substrates of computers and mobile phone devices.
- an alicyclic polyimide resin containing tetravalent alicyclic tetracarboxylic acid and its derivative and divalent diamine as constituents or tetravalent
- An alicyclic polyimide resin having a tetracarboxylic acid and a derivative thereof and a divalent alicyclic diamine as constituent components has been reported.
- a method for producing a transparent and less colored film at a glass transition temperature of 300 ° C. or higher from a polyimide resin solution prepared from 1,2,4,5-cyclohexanetetracarboxylic dianhydride and a diamine having a specific structure is disclosed. (See Patent Document 3).
- the alicyclic polyimide resin can impart solvent solubility by introducing an alicyclic component or an aliphatic component into the polyimide resin, but has a drawback that it easily burns. From the viewpoint of safety, its use as a sealing material, protective film material, insulating material, etc. for electric / electronic parts has been restricted. In addition, flame retardancy has been demanded even when used as a display substrate for computers and mobile phone devices, or a substrate for solar cells.
- a halogen flame retardant, an antimony flame retardant, and a flame retardant containing no halogen and antimony are generally used.
- Halogen-based flame retardants cause problems in the halogen compounds, such as degradation of the weather resistance and electrical properties of the resin composition due to the liberated halogen, and thermal decomposition when the resin is exposed to high temperatures, generating hydrogen halide and polluting the environment.
- a typical example of an antimony flame retardant is antimony oxide. Carcinogenicity has been pointed out against antimony oxide that is usually added as a flame retardant aid, and safety to the human body is a problem.
- flame retardant resin compositions that do not use halogen compounds and antimony compounds.
- the flame retardant containing no halogen include inorganic metal hydrates such as magnesium hydroxide and aluminum hydroxide, and phosphates such as ammonium polyphosphate.
- these flame retardants need to be added in a large amount in order to obtain a sufficient flame retardant effect, which may cause a decrease in transparency.
- it is difficult to uniformly combine these flame retardants with the resin which may cause deterioration of mechanical properties.
- these contain an ionic component the favorable insulation characteristic which a polyimide resin has may be impaired.
- Patent Document 4 As a method for imparting flame retardancy to a polyimide resin containing a solvent solubility-imparting component selected from at least one of an aliphatic compound component, an alicyclic compound component, or an alkylene oxide adduct component of a bisphenol compound, a cyclic phenoxyphos There has been reported a method of complexing a phazene compound (see Patent Document 4).
- Patent Document 4 in order to impart flame retardancy corresponding to UL94 standard V-0 only by adding a phosphazene compound, 30 parts by mass of a phosphazene compound is added to 100 parts by mass of a polyimide resin.
- a flame retardant aid such as Aerogel is blended.
- a flame retardant aid such as Aerogel is blended.
- Such an increase in the amount of phosphazene compound added or the incorporation of a flame retardant aid may impair the properties such as colorless transparency, heat resistance, and electrical insulation, and is inferior in practicality.
- the present invention provides a flame retardant that does not contain a flame retardant such as a halogen flame retardant, an antimony flame retardant, an inorganic metal hydrate, or a phosphate, and has excellent transparency, heat resistance, and insulating properties.
- a flame retardant such as a halogen flame retardant, an antimony flame retardant, an inorganic metal hydrate, or a phosphate
- An object is to provide a cyclic polyimide resin composition and a thin molded body thereof.
- the present inventors have compounded 1 to 13 parts by mass of a cyano-modified cyclic phenoxyphosphazene compound with 100 parts by mass of an alicyclic polyimide resin having a specific structure. It has been found that an alicyclic polyimide resin composition excellent in transparency, heat resistance and insulation properties and flame-retarded can be obtained. Furthermore, it is a thin molded article made of the alicyclic polyimide resin composition, and after casting a solution obtained by dissolving the alicyclic polyimide resin composition in an organic solvent, the whole light is obtained by heating. It has been found that a thin molded article having a high transmittance and a low haze value can be obtained, and the present invention has been completed.
- the present invention provides a cyano-modified cyclic phenoxyphosphate represented by the following general formula (2) with respect to 100 parts by mass of the alicyclic polyimide resin (A) having a structural unit represented by the following general formula (1).
- R 1 is a tetravalent alicyclic hydrocarbon group having 4 to 16 carbon atoms
- R 2 is a divalent aliphatic hydrocarbon group having 2 to 28 carbon atoms, and 6 carbon atoms.
- n is an integer of 3 or 4.
- X is independently a phenoxy group or a 4-cyanophenoxy group, and 25% or more of a plurality of Xs are 4-cyanophenoxy groups. All Xs may be 4-cyanophenoxy groups.
- a polyimide resin composition and a thin molded body thereof can be provided.
- the alicyclic polyimide resin (A) of the present invention has a repeating unit represented by the following general formula (1).
- R 1 is a tetravalent alicyclic hydrocarbon group having 4 to 16 carbon atoms.
- R 2 is at least one group selected from a divalent aliphatic hydrocarbon group having 2 to 28 carbon atoms and a divalent aromatic hydrocarbon group having 6 to 27 carbon atoms.
- R 2 may include a sulfide group, a sulfonyl group, a sulfinyl group, a carbonyl group, a methoxy group, an ester group, an ether group, a fluoro group, and the like.
- the divalent aliphatic hydrocarbon group having 2 to 28 carbon atoms may be an aliphatic hydrocarbon group linked via an arylene group.
- a tetravalent alicyclic hydrocarbon group having 6 to 12 carbon atoms is preferable.
- An alicyclic hydrocarbon group derived from a carboxylic acid or a derivative thereof is more preferable, and a group derived from cyclohexane contained in a structural unit represented by the following general formula (3) is more preferable.
- R 2 is the same as described above.
- the divalent aliphatic hydrocarbon group having 2 to 28 carbon atoms in R 2 of the general formulas (1) and (3) is a group obtained by removing two amino groups from an aliphatic diamine specifically exemplified later. Is mentioned.
- examples of the divalent aromatic hydrocarbon group having 6 to 27 carbon atoms in R 2 include groups obtained by removing two amino groups from an aromatic diamine specifically exemplified later.
- the R 2 in the general formula (1) and (3), a divalent aromatic hydrocarbon group having 6 to 27 carbon, nitrogen atom attached to R 2 is directly linked to the aromatic ring of R 2 It preferably has a structure.
- the alicyclic polyimide resin (A) includes an alicyclic tetracarboxylic acid having a tetravalent alicyclic hydrocarbon group having 4 to 16 carbon atoms or a derivative thereof, and a divalent aliphatic carbonization having 2 to 28 carbon atoms. Reaction with an aliphatic diamine having a hydrogen group and at least one diamine selected from an aromatic diamine having a divalent aromatic hydrocarbon group having 6 to 27 carbon atoms in an organic solvent in the presence of an imidization catalyst. Is synthesized.
- alicyclic tetracarboxylic acid or derivatives thereof examples include alicyclic tetracarboxylic acid, alicyclic tetracarboxylic acid esters, alicyclic tetracarboxylic dianhydride and the like. Of these, alicyclic tetracarboxylic dianhydrides are preferred.
- Examples of the alicyclic tetracarboxylic dianhydride having a tetravalent alicyclic hydrocarbon group having 4 to 16 carbon atoms include 1,2,4,5-cyclopentanetetracarboxylic dianhydride, 1, 2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo [2.2.1] heptanetetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5 6-tetracarboxylic dianhydride, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic dianhydride, 3,3 ′, 4,4′-dicyclohexyltetracarboxylic dianhydride Such as things.
- 1,2,4,5-cyclohexanetetracarboxylic dianhydride is preferred.
- These alicyclic tetracarboxylic dianhydrides can be used singly or in combination of two or more, but 1,2,4,5-cyclohexanetetracarboxylic dianhydride can be used alone. preferable.
- tetracarboxylic acid having a tetravalent alicyclic hydrocarbon group having 4 to 16 carbon atoms examples include 1,2,4,5-cyclopentanetetracarboxylic acid and 1,2,4,5-cyclohexanetetracarboxylic acid.
- tetracarboxylic acid esters having a tetravalent alicyclic hydrocarbon group having 4 to 16 carbon atoms include 1,2,4,5-cyclohexanetetracarboxylic acid methyl ester, 1,2,4,5- Cyclohexanetetracarboxylic acid dimethyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid trimethyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid tetramethyl ester, bicyclo [2.2.2] oct-7- En-2,3,5,6-tetracarboxylic acid methyl ester, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid dimethyl ester, bicyclo [2.2.
- the aliphatic diamine and the aromatic diamine are represented by the following general formula (4).
- R 2 is the same as described above. That is, the aliphatic diamine has a structure in which two amino groups are directly bonded to a divalent aliphatic hydrocarbon group having 2 to 28 carbon atoms.
- the divalent aliphatic hydrocarbon group having 2 to 28 carbon atoms may be an aliphatic hydrocarbon group linked via an arylene group.
- the aromatic diamine has a structure in which two amino groups are bonded directly to a divalent aromatic hydrocarbon group having 6 to 27 carbon atoms.
- the aliphatic diamine and the aromatic diamine may each include a sulfide group, a sulfonyl group, a sulfinyl group, a carbonyl group, a methoxy group, an ester group, an ether group, and a fluoro group in the skeleton.
- the aliphatic diamine is not particularly limited, but may be a linear or branched aliphatic diamine or an aliphatic diamine containing an alicyclic structure.
- linear or branched aliphatic diamine include ethylenediamine, tetramethylenediamine, paraxylylenediamine, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, polyethylene glycol bis (3- Aminopropyl) ether, polypropylene glycol bis (3-aminopropyl) ether, metaxylylenediamine, siloxane diamine, and the like.
- Examples of the aliphatic diamine having an alicyclic structure include 4,4-diaminodicyclohexylmethane, isophoronediamine, norbornanediamine, 1,3-bis (aminomethyl) cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, Bicyclohexyl diamine etc. are mentioned. These diamines can be used alone or in combination of two or more.
- the aromatic diamine is not particularly limited, but 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 1,3-phenylenediamine, 1,4-phenylenediamine, 4 , 4'-diamino-3,3'-dimethylbiphenyl, 4,4'-diamino-2,2'-dimethylbiphenyl, 4,4'-diamino-2,2'-dimethoxybiphenyl, 4,4'-diamino -2,2'-bis (trifluoromethyl) biphenyl, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminobenzophenone, 9,9-bis (4-aminophenyl) ) Fluorene, 1,1-
- the aromatic diamine is preferable in that a polyimide having high heat resistance can be obtained.
- the aromatic diamines 1,4-bis (4-amino- ⁇ , ⁇ -dimethylbenzyl) benzene, 4,4′-bis (4- Aminophenoxy) biphenyl, 9,9-bis (4-aminophenyl) fluorene, 4,4′-diaminodiphenyl ether, 4,4′-diamino-2,2′-dimethoxybiphenyl, 4,4′-diamino-2, 2'-bis (trifluoromethyl) biphenyl is preferred.
- the organic solvent used in the production of the alicyclic polyimide resin (A) of the present invention is preferably a solvent containing at least one structure selected from the group consisting of cyclic ethers, cyclic ketones, cyclic esters, amides, and ureas.
- ⁇ -butyrolactone N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, hexamethylphosphoramide, cyclopentanone, cyclohexanone
- aprotic polar organic solvents such as 1,3-dioxolane, 1,4-dioxane, tetramethylurea, and tetrahydrofuran.
- at least one selected from ⁇ -butyrolactone, N, N-dimethylacetamide, N, N-dimethylformamide and N-methyl-2-pyrrolidone is more preferable.
- Examples of the imidization catalyst used in the production of the alicyclic polyimide resin (A) include triethylamine, tripropylamine, tributylamine, pyridine, quinoline, isoquinoline, ⁇ -picoline, ⁇ -picoline, N, N-dimethylaniline, N Tertiary amines such as N, diethylaniline, or acids such as crotonic acid, benzoic acid, methylbenzoic acid, oxybenzoic acid, benzenesulfonic acid, paratoluenesulfonic acid can be used. It is preferable to do this.
- a manufacturing method is not limited to the following.
- a solution obtained by dissolving diamine in an organic solvent at a temperature of 30 ° C. or less and an aliphatic tetracarboxylic acid or a derivative thereof are mixed and reacted at a temperature of 4 to 30 ° C. to obtain a polyamic acid solution.
- An imidation catalyst is added to the polyamic acid solution, and a dehydration imidation reaction is performed while distilling the generated water out of the system to obtain a solution of the alicyclic polyimide resin (A).
- the molar ratio of diamine to alicyclic tetracarboxylic acid or derivative thereof is preferably in the range of 0.95 to 1.05, particularly 0.99 to 1.01. The range of is preferable. If the molar ratio of the diamine to the alicyclic tetracarboxylic acid or derivative thereof is 0.95 or more, or 1.05 or less, the high molecular weight can be sufficiently advanced to prevent the thin molded article from becoming brittle. it can.
- the proper molar ratio of imidization catalyst and diamine is preferably in the range of 0.01 to 1.0, more preferably in the range of 0.05 to 0.5. If the molar ratio of the imidization catalyst to the diamine is 0.01 or more, the imidization reaction proceeds sufficiently by the catalytic action of the imidization catalyst, and if it is 1.0 or less, the imidization catalyst itself is removed. Is easy and can prevent coloring of a thin molded article made of the alicyclic polyimide resin composition described later, and can prevent the solubility of the alicyclic polyimide resin from being lowered.
- reaction temperature is usually in the range of 160 to 200 ° C, preferably in the range of 170 to 190 ° C, more preferably in the range of 180 to 190 ° C. If it is 160 ° C. or higher, imidization and high molecular weight advance sufficiently, and if it is 200 ° C. or lower, problems such as the scorching of the resin on the wall of the reaction vessel occur when the solution viscosity increases significantly. Can be prevented.
- an azeotropic dehydrating agent such as toluene or xylene may be used.
- the reaction pressure is usually atmospheric pressure, but the reaction can also be carried out under pressure as necessary.
- the holding time for the reaction temperature is at least 1 hour, more preferably 3 hours or more. If it is less than 1 hour, imidization and high molecular weight may not proceed sufficiently. There is no particular upper limit for the reaction time, but it is usually in the range of 3 to 10 hours.
- the solid content concentration of the alicyclic polyimide resin with respect to the total mass part including the organic solvent in the above step is preferably 20% by mass or more and 50% by mass or less, more preferably 30% by mass or more and 40% by mass or less.
- the content is 20% by mass or more, the intrinsic viscosity of the polyimide resin is appropriately increased and the molecular weight is sufficiently increased, so that the thin molded article can be prevented from becoming brittle.
- it if it is 50 mass% or less, it can suppress that the viscosity of a polyimide resin solution rises excessively with the raise of the intrinsic viscosity of a polyimide resin, and since it can stir uniformly, resin scorching occurs. Can be prevented.
- the temperature for dissolving in the organic solvent is desirably at least 20 ° C. or higher, and preferably in the temperature range of 30 ° C. to 100 ° C. If it is 20 degreeC or more, since it has moderate solution viscosity, a handleability will improve.
- the excess alicyclic polyimide resin solution is mixed with excess methanol and stirred to obtain a precipitate of the alicyclic polyimide resin. After filtering the said deposit, it heats under vacuum and white powdery alicyclic polyimide resin (A) is obtained.
- the imidization catalyst may be added before adding the alicyclic tetracarboxylic acid or its derivative. In that case, heating can be started immediately and dehydration imidation can be carried out without having to keep the temperature at or near room temperature, which is generally a reaction condition for forming polyamic acid.
- the cyano-modified cyclic phenoxyphosphazene compound (B) used in the present invention is a cyanophenol-substituted cyclic phosphazene or a cyanophenol-phenol mixed-substituted cyclic phosphazene represented by the following general formula (2).
- n is an integer of 3 or 4.
- X is independently a phenoxy group or a 4-cyanophenoxy group, and 25% or more of a plurality of Xs are 4-cyanophenoxy groups. All Xs may be 4-cyanophenoxy groups.
- the above-mentioned cyano-modified cyclic phenoxyphosphazene compound has high solubility in an organic solvent described later and exhibits good compatibility with an alicyclic polyimide resin (A), so that sufficient transparency is imparted to a thin molded article. can do. Further, by having a cyano-modified substituent, the mass loss at high temperature is small and excellent in high temperature reliability as compared with the conventional cyclic phenoxyphosphazene compound, and the dielectric properties of the resin molded body are hardly impaired. In addition, since the nitrogen content ratio per unit mass is high, excellent flame retardancy is exhibited even when added in a small amount.
- the alicyclic polyimide resin composition obtained by combining the cyano-modified cyclic phenoxyphosphazene compound and the thin-walled molded product thereof are excellent in transparency, and further, heat resistance and mechanical strength are not easily lowered.
- the ratio of 4-cyanophenoxy group in all X bonded to the phosphorus atom in the general formula (2) is 25 to 100%, more preferably 35 to 75%, and more preferably 45 to 55 % Is more preferable.
- cyano-modified cyclic phenoxyphosphazene compound a synthesized product or a commercially available product may be used. Examples of commercially available products include Ravitor FP-300 (above, Fushimi Pharmaceutical Co., Ltd., trade name).
- a cyano modified cyclic phenoxyphosphazene compound may be used individually by 1 type, and may use 2 or more types together.
- the compounding amount of the cyano-modified cyclic phenoxyphosphazene compound in the alicyclic polyimide resin composition of the present invention must be 1 to 13 parts by mass with respect to 100 parts by mass of the alicyclic polyimide resin. It is preferably ⁇ 10 parts by mass.
- the compounding amount of the cyano-modified cyclic phenoxyphosphazene compound exceeds 13 parts by mass, the glass transition temperature is lowered and the heat resistance is impaired in a thin molded article made of the alicyclic polyimide resin composition described later.
- the fall of a total light transmittance and the raise of a haze value are caused, and transparency falls.
- the mechanical strength may decrease.
- the amount is less than 1 part by mass, the flame retardancy is impaired, which is not practical.
- the alicyclic polyimide resin composition may contain a condensed phosphate having a high molecular weight, a cyclic organic phosphorus compound, or the like as long as the effects of the present invention are not impaired.
- condensed phosphate esters and cyclic organophosphorus compounds include resorcinol bis (phenyl) phosphate, resorcinol bis (2,6-dixylenyl) phosphate, bisphenol A bis (diphenyl) phosphate, bisphenol A bis. Examples include (dicresyl) phosphate and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (Sanko Co., Ltd., trade name: HCA), but are not limited thereto. .
- the alicyclic polyimide resin composition includes known additives such as 2,6-di-t-butyl-4-methylphenol, 2- (1-methylcyclohexyl) -4,6-dimethylphenol, 2 , 2-methylenebis- (4-ethyl-6-t-methylphenol), 4,4′-thiobis- (6-t-butyl-3-methylphenol), 2,2′-dihydroxy- UV absorbers such as 4-methoxybenzophenone, 2- (2′-hydroxy-4′-n-octoxyphenyl) benzotriazole, pt-butylphenyl salicylate, calcium carbonate, clay, silica, glass fiber, carbon fiber Etc. and various surfactants may be included within a range that maintains transparency, if necessary.
- known additives such as 2,6-di-t-butyl-4-methylphenol, 2- (1-methylcyclohexyl) -4,6-dimethylphenol, 2 , 2-methylenebis- (4-ethyl-6-t
- the alicyclic polyimide resin composition may contain an organic solvent containing at least one structure selected from the group consisting of cyclic ethers, cyclic ketones, cyclic esters, amides, and ureas. Specific examples include, but are not limited to, ⁇ -butyrolactone, N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, hexamethylphosphoramide, cyclopentanone, cyclohexanone , 1,3-dioxolane, 1,4-dioxane, tetramethylurea, tetrahydrofuran and the like, and at least one selected from aprotic polar organic solvents. Among these, at least one selected from ⁇ -butyrolactone, N, N-dimethylacetamide, N, N-dimethylformamide and N-methyl-2-pyrrolidone is more preferable.
- a thin molded article comprising the alicyclic polyimide resin composition of the present invention is produced by the following method.
- Step (1) An alicyclic polyimide resin composition solution containing three components of an alicyclic polyimide resin (A), a cyano-modified cyclic phenoxyphosphazene compound (B), and an organic solvent is prepared.
- Step (2) After extruding or coating the solution on the support in the form of a film, the solution is heated and the organic solvent is volatilized to produce a thin molded article made of the alicyclic polyimide resin composition.
- an alicyclic A method of mixing an alicyclic polyimide resin solution (A ′) prepared by dissolving a polyimide resin (A) in an organic solvent and a cyano-modified cyclic phenoxyphosphazene compound (B), or a cyano-modified cyclic phenoxyphosphazene Any of the methods of mixing the solution (A ′) with the compound (B ′) previously dissolved or swollen in an organic solvent capable of uniformly mixing the compound (B) with the alicyclic polyimide resin (A) may be used.
- the temperature at the time of mixing in the step (1) is preferably 20 to 90 ° C. In any case, it is important to stir under mechanical shearing with a knea
- the solid content concentration in the alicyclic polyimide resin composition solution obtained in the step (1) is preferably 10 to 50% by mass, more preferably 20 to 40% by mass. If it is 10% by mass or more, it is possible to prevent the occurrence of problems that it is difficult to maintain the thickness of the thin molded body and that it takes a long time to remove the organic solvent. Moreover, if it is 50 mass% or less, it can prevent the malfunction that formation of a thin molded object becomes difficult by the fluidity
- the material of the support in the step (2) is not particularly limited, an organic polymer film such as polyethylene terephthalate or polyethylene naphthalate can be used in addition to the glass substrate and the stainless steel substrate.
- step (2) a known method can be used as a method for forming a coating layer by extruding or coating the support on a film.
- a known method can be used as a method for forming a coating layer by extruding or coating the support on a film. Examples thereof include a casting method using die extrusion, a method using an applicator, a coater, and the like.
- the coating layer is heated at a temperature of 120 ° C. or lower for about 30 to 60 minutes until it has self-supporting property, and the organic solvent is volatilized. Subsequently, this is peeled off from a support body, and an edge part is fixed with a metal clip or a tenter. Then, in a nitrogen stream or under reduced pressure, the temperature is raised to at least the boiling point of the organic solvent so as not to cause a sudden boiling of the remaining organic solvent while limiting the contraction of the film, and preferably at least 5 to 10 ° C. higher than the boiling point of the organic solvent The temperature is raised to a temperature, and the residual solvent is removed by drying and annealing at that temperature to obtain a thin molded article.
- the content of the organic solvent contained in the thin molded body is preferably less than 1% by mass.
- the content of the organic solvent is less than 1% by mass, the glass transition temperature of the thin-walled molded product can be prevented from being lowered due to plasticizing action, thereby preventing problems such as thermal deformation. Coloring due to oxidative decomposition of the solvent or the like can be prevented.
- the thickness of the thin molded body is preferably 1 ⁇ m to 1 mm, more preferably 10 to 500 ⁇ m, and even more preferably 30 to 300 ⁇ m.
- the thin molded article preferably has a total light transmittance of 88% or more at a film thickness of 100 ⁇ m, more preferably 89% or more.
- the total light transmittance is 88% or more, the transparency is sufficient when used as a substrate for a display substrate such as a computer or a cellular phone device or a substrate for a solar cell.
- the thin molded article preferably has a haze value of 1.3 or less, more preferably 1.0 or less at a film thickness of 100 ⁇ m. If the haze value is 1.3 or less, the transparency is sufficient when used as a display substrate for computers and mobile phone devices, or a substrate for solar cells.
- the glass transition temperature which is a heat resistance index of the thin molded article, is preferably 240 ° C. or higher. If the glass transition temperature of the thin molded article is 240 ° C. or higher, sufficient heat resistance is ensured.
- a heat treatment process at 250 ° C. or higher is required in order to lower the insulation resistance of the conductive layer and increase the electron mobility.
- the glass transition temperature of the thin molded article is preferably 250 ° C. or higher, more preferably 270 ° C. or higher. If the glass transition temperature of the thin-walled molded product is 250 ° C. or higher, it is possible to prevent problems from occurring during the soldering process.
- the thin molded article comprising the alicyclic polyimide resin composition of the present invention utilizes the excellent transparency, heat resistance, insulation characteristics and flame retardancy, sealing materials for optical and electronic / electronic parts, protective films Suitable as material and insulating material. Moreover, after apply
- a fluorescent material or the like may be mixed with the sealing resin for light emitting diodes for the purpose of converting the emission wavelength into the visible region. Since the alicyclic polyimide resin of the present invention is excellent in mixing property, dispersibility, and stability when mixed with various fluorescent materials, it is preferable as a sealing material for a light emitting diode.
- the present invention will be specifically described by way of examples. However, the present invention is not limited to these examples.
- the physical properties of the thin molded article comprising the alicyclic polyimide resin (A) obtained in each production example and the alicyclic polyimide resin composition obtained in each example and comparative example were measured by the following methods.
- ⁇ Glass transition temperature> The heat resistance of the alicyclic polyimide resin composition was raised to 400 ° C. at 10 ° C./min in a nitrogen atmosphere using a differential thermal analyzer (model number DSC-6220) manufactured by SII NanoTechnology. The glass transition temperature was measured.
- Total light transmittance and haze value As an index for evaluating colorlessness and transparency according to “JIS K7105 Transparency Test Method” using a thin molded product of an alicyclic polyimide resin composition, a color difference / turbidity measuring instrument (manufactured by Nippon Denshoku Industries Co., Ltd.) The total light transmittance and haze value were determined using model number COH-400).
- Insulation characteristics of thin-walled molded products of alicyclic polyimide resin compositions were measured for surface resistivity using a microammeter (model number R-8340) manufactured by Advantest Co., Ltd. in an environment of 23 ° C / 50% RH. It was evaluated by doing.
- ⁇ Flame retardance evaluation> A thin molded product having a thickness of about 0.1 mm made of an alicyclic polyimide resin composition is cut into 50 mm ⁇ 200 mm, rounded into a cylindrical shape with a diameter of 12.7 mm and a length of 200 mm, and a test piece compliant with the UL94VTM standard is prepared. A vertical combustion test was performed.
- the hydrogen gas in the reaction vessel was replaced with nitrogen gas, the reaction solution was extracted from the autoclave, and the reaction solution was filtered to separate the catalyst.
- the filtrate was concentrated by removing water with a rotary evaporator under reduced pressure to precipitate crystals.
- the precipitated crystals were separated into solid and liquid at room temperature, dried and dried to 481 g of 1,2,4,5-cyclohexanetetracarboxylic acid (yield). 85.0%).
- 481 g of the obtained 1,2,4,5-cyclohexanetetracarboxylic acid and 4000 g of acetic anhydride were charged into a 5-liter glass separable flask, and the inside of the reaction vessel was replaced with nitrogen gas while stirring. .
- the temperature was raised to the reflux temperature of the solvent under a nitrogen gas atmosphere, and the solvent was refluxed for 10 minutes. While stirring, the mixture was cooled to room temperature to precipitate crystals. The precipitated crystals were separated into solid and liquid and dried to obtain primary crystals. Further, the separated mother liquor was concentrated under reduced pressure using a rotary evaporator to precipitate crystals. The crystals were separated into solid and liquid and dried to obtain secondary crystals. The primary crystal and the secondary crystal were combined to obtain 375 g of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (anhydrous yield of 96.6%).
- tetracarboxylic dianhydride and diamine used in the production examples and the flame retardants used in the examples and comparative examples are as follows.
- BisAP 1,4-bis (4-amino- ⁇ , ⁇ -dimethylbenzyl) benzene
- BAPB 4,4′-bis (4-aminophenoxy) biphenyl
- BAFL 9,9-bis (4-aminophenyl) fluorene
- DCHM 4,4-Diaminodicyclohexylmethane
- B1 Cyano-modified cyclic phenoxyphosphazene compound [manufactured by Fushimi Pharmaceutical Co., Ltd., trade name Ravitor FP-300 (in the general formula (2), n is a mixture of 3 and 4; 4- The proportion of cyanophen
- the temperature was raised to 180 ° C., refluxed for 5 hours while distilling off the distillate as needed, the reaction was terminated, air-cooled until the internal temperature reached 120 ° C., and N, N-dimethylacetamide as the diluent 143.7g was added and it cooled, stirring, and obtained the alicyclic polyimide resin solution (A1 ') of solid content concentration 20 mass%.
- a portion of the above solution is poured into 1 L of methanol to precipitate a polymer, which is filtered and washed with methanol, and then dried in a vacuum dryer at 100 ° C. for 24 hours to obtain a white powder (alicyclic polyimide resin A1). Obtained.
- the IR spectrum of this powder was measured, absorptions of 1704 and 1770 cm ⁇ 1 peculiar to the imide group were observed.
- the logarithmic viscosity of the alicyclic polyimide resin (A1) was measured and found to be 1.05.
- 1,2,4,5-cyclohexanetetracarboxylic dianhydride 22.45 (0.1 mol) and 0.51 g (0.005 mol) of triethylamine as an imidization catalyst were added all at once. .
- the temperature was raised to 180 ° C., refluxed for 5 hours while distilling off the distillate as needed, the reaction was terminated, air-cooled until the internal temperature reached 120 ° C., and N, N-dimethylacetamide as the diluent 134.7g was added and it cooled, stirring, and obtained the alicyclic polyimide resin solution (A2 ') of solid content concentration 20 mass%.
- the mass of the solution was 278.26 g, and the total distillate mass was 3.66 g.
- a portion of the above solution is poured into 1 L of methanol to precipitate a polymer, which is filtered and washed with methanol, and then dried in a vacuum dryer at 100 ° C. for 24 hours to obtain a white powder (alicyclic polyimide resin (A2)).
- alicyclic polyimide resin (A2) alicyclic polyimide resin
- the mass of the above solution was 270.26 g, and the total mass of the distillate was 4.35 g.
- a part of the above solution is poured into 1 L of methanol to precipitate a polymer, filtered, washed with methanol, dried in a vacuum dryer at 100 ° C. for 24 hours, and then white powder (alicyclic polyimide resin (A3)).
- white powder alicyclic polyimide resin (A3)
- Example 1 The alicyclic polyimide resin solution (A1 ′) obtained in Production Example 1 contains 3 parts by mass of a cyano-modified cyclic phenoxyphosphazene compound (B1) as a flame retardant with respect to 100 parts by mass of the polyimide resin solid content. Then, the mixture was stirred and mixed at 70 ° C. for 2 hours to obtain an alicyclic polyimide resin composition solution. The concentration of the solution was 20.48% by mass. The obtained alicyclic polyimide resin composition solution was cast on a glass substrate on which a plastic release agent (pericoat) was uniformly applied using a 1000 ⁇ m doctor blade. This was kept on a hot plate at 100 ° C.
- a plastic release agent peripheral component
- Example 2 The alicyclic polyimide resin solution (A2 ′) obtained in Production Example 2 contains 5 parts by mass of a cyano-modified cyclic phenoxyphosphazene compound (B1) as a flame retardant with respect to 100 parts by mass of the polyimide resin solid content. Then, the mixture was stirred and mixed at 70 ° C. for 2 hours to obtain an alicyclic polyimide resin composition solution. The concentration of the solution was 20.79% by mass. Next, a thin molded article made of a transparent alicyclic polyimide resin composition having a thickness of 101 ⁇ m was prepared in the same manner as in Example 1 except that the alicyclic polyimide resin composition solution obtained above was used. Got. These total light transmittances and haze values were determined, and the glass transition temperature and surface resistivity were measured. Further, as a result of conducting a flammability test, it corresponded to UL standard VTM-0. The results are shown in Table 1.
- Example 3 The alicyclic polyimide resin solution (A3 ′) obtained in Production Example 3 contains 3 parts by mass of a cyano-modified cyclic phenoxyphosphazene compound (B1) as a flame retardant with respect to 100 parts by mass of the polyimide resin solid content. Then, the mixture was stirred and mixed at 70 ° C. for 2 hours to obtain an alicyclic polyimide resin composition solution. The concentration of the solution was 20.48% by mass. Next, a thin molded article made of a transparent alicyclic polyimide resin composition having a film thickness of 100 ⁇ m was prepared in the same manner as in Example 1 except that the alicyclic polyimide resin composition solution obtained above was used. Got. These total light transmittances and haze values were determined, and the glass transition temperature and surface resistivity were measured. Further, as a result of conducting a flammability test, it corresponded to UL standard VTM-0. The results are shown in Table 1.
- Example 4 The content of the cyano-modified cyclic phenoxyphosphazene compound (B1) as a flame retardant in the polyimide resin solution (A4 ′) obtained in Production Example 4 is 10 parts by mass with respect to 100 parts by mass of the polyimide resin solid content. The mixture was stirred and mixed at 70 ° C. for 2 hours to obtain an alicyclic polyimide resin composition solution. The concentration of the solution was 21.57% by mass. Next, a thin molded article made of a transparent alicyclic polyimide resin composition having a thickness of 102 ⁇ m was prepared in the same manner as in Example 1 except that the alicyclic polyimide resin composition solution obtained above was used. Got. These total light transmittances and haze values were determined, and the glass transition temperature and surface resistivity were measured. Further, as a result of conducting a flammability test, it corresponded to UL standard VTM-0. The results are shown in Table 1.
- the alicyclic polyimide resin solution (A1 ′) obtained in Production Example 1 contains 10 parts by mass of a cyano-modified cyclic phenoxyphosphazene compound (B1) as a flame retardant with respect to 100 parts by mass of polyimide resin solids. Then, the mixture was stirred and mixed at 70 ° C. for 2 hours to obtain an alicyclic polyimide resin composition solution. The concentration of the solution was 21.57% by mass. Next, a thin-walled molding made of a colorless and transparent alicyclic polyimide resin composition having a thickness of 105 ⁇ m was performed in the same manner as in Example 1 except that the alicyclic polyimide resin composition solution obtained above was used. Got the body. These total light transmittances and haze values were determined, and the glass transition temperature and surface resistivity were measured. Further, as a result of conducting a flammability test, it corresponded to UL standard VTM-0. The results are shown in Table 1.
- Example 6 The content of the cyano-modified cyclic phenoxyphosphazene compound (B1) as a flame retardant in the polyimide resin solution (A4 ′) obtained in Production Example 4 is 5 parts by mass with respect to 100 parts by mass of the polyimide resin solid content. The mixture was stirred and mixed at 70 ° C. for 2 hours to obtain an alicyclic polyimide resin composition solution. The concentration of the solution was 20.79% by mass. Next, a thin molded article made of a transparent alicyclic polyimide resin composition having a thickness of 104 ⁇ m was prepared in the same manner as in Example 1 except that the alicyclic polyimide resin composition solution obtained above was used. Got. These total light transmittances and haze values were determined, and the glass transition temperature and surface resistivity were measured. Further, as a result of conducting a flammability test, it corresponded to UL standard VTM-0. The results are shown in Table 1.
- Triphenyl phosphate (B2) is added as a flame retardant to the alicyclic polyimide resin solution (A1 ′) obtained in Production Example 1 so that the content with respect to 100 parts by mass of the polyimide resin solid content is 3 parts by mass.
- a thin molded article made of a transparent alicyclic polyimide resin composition having a film thickness of 118 ⁇ m was obtained in the same manner as in Example 1 except that. These total light transmittances and haze values were determined, and the glass transition temperature and surface resistivity were measured. In addition, as a result of conducting the flammability test, it was completely burned and corresponded to a non-UL standard. The results are shown in Table 2.
- Triphenyl phosphate (B2) is added as a flame retardant to the alicyclic polyimide resin solution (A1 ′) obtained in Production Example 1 so that the content with respect to 100 parts by mass of the polyimide resin solid content is 20 parts by mass.
- a thin molded article made of an alicyclic polyimide resin composition having a film thickness of 103 ⁇ m was obtained in the same manner as in Example 1 except that.
- the total light transmittance was decreased as compared with Example 1, and the haze value was greatly increased. Further, as a result of conducting a flammability test, it corresponded to UL standard VTM-1. The results are shown in Table 2.
- Phenoxyphosphazene (B4) as a flame retardant in the alicyclic polyimide resin solution (A1 ′) obtained in Production Example 1 is 3 parts by mass with respect to 100 parts by mass of polyimide resin solid content.
- a thin molded article made of a transparent alicyclic polyimide resin composition having a film thickness of 105 ⁇ m was obtained in the same manner as in Example 1 except that it was added. These total light transmittances and haze values were determined, and the glass transition temperature and surface resistivity were measured. Further, as a result of conducting a flammability test, it corresponded to UL standard VTM-1. The results are shown in Table 2.
- the alicyclic polyimide resin solution (A1 ′) obtained in Production Example 1 contains 20 parts by mass of the phenoxyphosphazene compound (B4) as a flame retardant with respect to 100 parts by mass of the polyimide resin solid content.
- a thin molded article made of an alicyclic polyimide resin composition having a film thickness of 109 ⁇ m was obtained in the same manner as in Example 1 except that it was added. These total light transmittances and haze values were determined, and the glass transition temperature and surface resistivity were measured.
- the alicyclic polyimide resin solution (A1 ′) obtained in Production Example 1 contains 20 parts by mass of a cyano-modified cyclic phenoxyphosphazene compound (B1) as a flame retardant with respect to 100 parts by mass of polyimide resin solids.
- a thin molded article made of a transparent alicyclic polyimide resin composition having a film thickness of 111 ⁇ m was obtained in the same manner as in Example 1 except that it was added so as to be. These total light transmittances and haze values were determined, and the glass transition temperature and surface resistivity were measured.
- it corresponded to UL standard VTM-0 but the glass transition temperature was significantly lowered as compared with Example 1.
- the results are shown in Table 2.
- an alicyclic compound excellent in flame retardancy, transparency, heat resistance, and insulation characteristics without using a flame retardant such as a halogen compound or an antimony oxide compound which may be affected by the human body and the environment.
- a polyimide resin composition and a thin molded body thereof are provided, and are used as sealing materials, protective film materials, and insulating materials for various electric / electronic parts that require transparency and flame retardancy.
- it is suitably used for applications such as display substrates for computers and mobile phone devices, insulating substrates such as solar cells, and sealing materials for light emitting diodes.
Abstract
Description
一方、フィルム成形に高温処理を必要としない溶媒可溶性の透明ポリイミド樹脂として、4価の脂環式テトラカルボン酸およびその誘導体と2価のジアミンを構成成分とする脂環式ポリイミド樹脂、または4価のテトラカルボン酸およびその誘導体と2価の脂環式ジアミンを構成成分とする脂環式ポリイミド樹脂が報告されている。例えば、1,2,4,5-シクロヘキサンテトラカルボン酸二無水物と特定の構造を有するジアミンから調整したポリイミド樹脂溶液からガラス転移温度300℃以上で透明で着色の少ないフィルムを作製する方法について開示されている(特許文献3参照)。
樹脂に難燃性を付与させるために複合化される難燃剤としては、一般的にハロゲン系難燃剤、アンチモン系難燃剤、ハロゲンおよびアンチモンを含まない難燃剤が使用される。
アンチモン系難燃剤の代表例として、酸化アンチモンがあげられる。通常難燃助剤として添加される酸化アンチモンに対しては、発ガン性が指摘されており、人体に対する安全性が問題とされている。
ハロゲンを含まない難燃剤としては、水酸化マグネシウムや水酸化アルミニウムなどの無機金属水和物、ポリリン酸アンモニウムなどのリン酸塩類などが挙げられる。しかしながら、これらの難燃剤は十分な難燃効果を得るために大量に添加する必要があり、透明性の低下を招く恐れがある。またこれらの難燃剤を樹脂に対して均一に複合化させることが難しく、機械特性の低下を招く恐れがある。
またこれらはイオン成分を含有することから、ポリイミド樹脂が有している良好な絶縁特性が損なわれる場合がある。
前記一般式(1)および(3)のR2における炭素数2~28の2価の脂肪族炭化水素基としては、後で具体的に例示する脂肪族ジアミンから2つのアミノ基を除いた基が挙げられる。同様に、R2における炭素数6~27の2価の芳香族炭化水素基としては、後で具体的に例示する芳香族ジアミンから2つのアミノ基を除いた基が挙げられる。
前記一般式(1)および(3)のR2としては、炭素数6~27の2価の芳香族炭化水素基であって、R2に結合する窒素原子がR2の芳香環に直結する構造を有していることが好ましい。
H2N-R2-NH2 (4)
式(4)中、R2は前記と同じである。すなわち、前記脂肪族ジアミンは、炭素数2~28の2価の脂肪族炭化水素基に直接2つのアミノ基が結合した構造を有している。炭素数2~28の2価の脂肪族炭化水素基としては、アリーレン基を介して連結した脂肪族炭化水素基でもよい。
前記芳香族ジアミンは、炭素数6~27の2価の芳香族炭化水素基に直接2つのアミノ基が結合した構造を有している。
前記脂肪族ジアミンおよび前記芳香族ジアミンは、それぞれ骨格の中にスルフィド基、スルホニル基、スルフィニル基、カルボニル基、メトキシ基、エステル基、エーテル基、フルオロ基を含んでもよい。
30℃以下の温度においてジアミンを有機溶媒に溶解させた溶液と脂肪族テトラカルボン酸またはその誘導体を混合し、4~30℃の温度において反応させ、ポリアミド酸溶液を得る。上記ポリアミド酸溶液にイミド化触媒を添加して、生成水を系外に留出しつつ脱水イミド化反応を行い、脂環式ポリイミド樹脂(A)の溶液を得る。
工程(1):脂環式ポリイミド樹脂(A)とシアノ変性環状フェノキシフォスファゼン化合物(B)と有機溶媒の3成分を含む脂環式ポリイミド樹脂組成物溶液を調製する。
工程(2):該溶液を支持体上に膜状に押し出しまたは塗布した後、該溶液を加熱し、有機溶媒を揮発させることにより脂環式ポリイミド樹脂組成物から成る薄肉成型体を製造する。
各製造例で得られた脂環式ポリイミド樹脂(A)および各実施例および比較例で得られた脂環式ポリイミド樹脂組成物から成る薄肉成型体の物性は、以下に示す方法で測定した。
製造例1~4において得られた脂環式ポリイミド樹脂溶液を無水メタノールに投入し、固体を析出させて未反応単量体を除去した後、濾過してから80℃で12時間真空乾燥して得られたポリイミド樹脂0.1gをN-メチル-2-ピロリドン20mLに溶解させ、キャノンフェンスケ粘度計を使用して30℃における対数粘度を測定した。対数粘度(μ)は下記式により求められた。
μ=ln(ts/t0)/C
t0:溶媒の流れる時間
ts:希薄高分子溶液の流れる時間
C:0.5g/dL
脂環式ポリイミド樹脂組成物の耐熱性はエス・アイ・アイ・ナノテクノロジー(株)製示差熱分析装置(型番DSC-6220)により、窒素雰囲気下において10℃/分で400℃まで昇温し、ガラス転移温度を測定した。
脂環式ポリイミド樹脂組成物の薄肉成型品を用いて、「JIS K7105透明度試験法」に準ずる無色性、透明性を評価する指標として、日本電色工業(株)製色差・濁度測定器(型番COH-400)を用いて全光線透過率およびヘイズ値を求めた。
脂環式ポリイミド樹脂組成物の薄肉成型品の絶縁特性は、23℃/50%RH環境下においてアドバンテスト(株)製の微小電流計(型番R-8340)を使用して、表面抵抗率を測定することにより評価した。
脂環式ポリイミド樹脂組成物からなる厚み約0.1mmの薄肉成型品を50mm×200mmに切り、直径12.7mm、長さ200mmの筒状になるように丸め、UL94VTM規格に準拠した試験片を作製し、垂直燃焼試験を実施した。
<1,2,4,5-シクロヘキサンテトラカルボン酸二無水物の合成>
内容積5リットルのハステロイ製(HC22)オートクレーブにピロメリット酸552g、活性炭にロジウム(Rh)を担持させた触媒(エヌ・イーケムキャット(株)製)200g、水1656gを仕込み、撹拌をしながら反応容器内を置換し、反応器の水素圧を5.0MPaとして60℃まで昇温した。水素圧を5.0MPaに保ちながら2時間反応させた。反応容器内の水素ガスを窒素ガスで置換し、反応液をオートクレーブから抜き出し、この反応液を濾過して触媒を分離した。濾過液をロータリーエバポレーターで減圧下で水を飛ばして濃縮し、結晶を析出させた析出した結晶を室温で固液分離し、乾燥して1,2,4,5-シクロヘキサンテトラカルボン酸481g(収率85.0%)を得た。続いて、得られた1,2,4,5-シクロヘキサンテトラカルボン酸481gと無水酢酸4000gとを、5リットルのガラス製セパラブルフラスコに仕込み、撹拌をしながら反応容器内を窒素ガスで置換した。窒素ガス雰囲気下に溶媒の還流温度まで昇温し、10分間溶媒を還流させた。撹拌しながら室温まで冷却し、結晶を析出させた。析出した結晶を固液分離し、乾燥して一次結晶を得た。さらに分離母液をロータリーエバポレーターにて減圧下に濃縮し、結晶を析出させた。この結晶を固液分離し、乾燥して二次結晶を得た。一次結晶、二次結晶を合わせて1,2,4,5-シクロヘキサンテトラカルボン酸二無水物375gが得られた(無水化の収率96.6%)。
<テトラカルボン酸二無水物>
H-PMDA: 1,2,4,5-シクロヘキサンテトラカルボン酸二無水物
<ジアミン>
BisAP: 1,4-ビス(4-アミノ-α,α-ジメチルベンジル)ベンゼン
BAPB: 4,4’-ビス(4-アミノフェノキシ)ビフェニル
BAFL: 9,9-ビス(4-アミノフェニル)フルオレン
DCHM: 4,4-ジアミノジシクロヘキシルメタン
<難燃剤>
B1:シアノ変性環状フェノキシフォスファゼン化合物〔(株)伏見製薬所製、商品名ラビトルFP-300(前記一般式(2)においてnが3及び4の混合物であり、すべてのXのうち4-シアノフェノキシ基である割合が50%である。)〕
B2:トリフェニルホスフェート(大八化学工業(株)製、商品名TPP)
B3:レゾルシノールビス(フェニル)フォスフェート(大八化学工業(株)製、商品名CR-733S)
B4:フェノキシフォスファゼン化合物(大塚化学(株)製、商品名SPS-100)
<脂環式ポリイミド樹脂(A1)の合成>
温度計、撹拌器、窒素導入環、分留器付き冷却管を備えた500mLの5つ口フラスコに、1,4-ビス(4-アミノ-α,α-ジメチルベンジル)ベンゼン24.18g(0.07モル)および4,4’-ビス(4-アミノフェノキシ)ビフェニル11.07g(0.03モル)溶剤としてSP値12.6のγ-ブチロラクトン68.19g及び、SP値10.8のN,N-ジメチルアセトアミド17.25gを仕込んで溶解させ、氷水バスを用いて5℃に冷却した。同温に保ちながら、1,2,4,5-シクロヘキサンテトラカルボン酸二無水物22.45(0.1モル)およびイミド化触媒としてトリエチルアミン0.51g(0.005モル)を一括で添加した。滴下終了後、180℃に昇温し、随時留出液を留去させながら5時間還流を行い反応終了とし、内温が120℃になるまで空冷した後、希釈溶剤としてN,N-ジメチルアセトアミド143.7gを加え、撹拌しながら冷却し、固形分濃度20質量%の脂環式ポリイミド樹脂溶液(A1’)を得た。上記溶液の一部を1Lのメタノールに注ぎ入れてポリマーを沈殿させ、ろ過、メタノール洗浄を行った後、100℃の真空乾燥機中24時間乾燥させ、白色粉末(脂環式ポリイミド樹脂A1)を得た。この粉末のIRスペクトルを測定したところ、イミド基に特有の1704、1770cm-1の吸収が見られた。脂環式ポリイミド樹脂(A1)の対数粘度を測定したところ、1.05であった。
<脂環式ポリイミド樹脂(A2)の合成>
温度計、撹拌器、窒素導入環、分留器付き冷却管を備えた500mLの5つ口フラスコに、4,4’-ビス(4-アミノフェノキシ)ビフェニル36.89g(0.1モル)溶剤としてSP値12.6のγ-ブチロラクトン71.18g及び、SP値10.8のN,N-ジメチルアセトアミド17.79gを仕込んで溶解させ、氷水バスを用いて5℃に冷却した。同温に保ちながら、1,2,4,5-シクロヘキサンテトラカルボン酸二無水物22.45(0.1モル)およびイミド化触媒としてトリエチルアミン0.51g(0.005モル)を一括で添加した。滴下終了後、180℃に昇温し、随時留出液を留去させながら5時間還流を行い反応終了とし、内温が120℃になるまで空冷した後、希釈溶剤としてN,N-ジメチルアセトアミド134.7gを加え、撹拌しながら冷却し、固形分濃度20質量%の脂環式ポリイミド樹脂溶液(A2’)を得た。上記溶液の質量は278.26g、また、留出液総質量は3.66gであった。上記溶液の一部を1Lのメタノールに注ぎ入れてポリマーを沈殿させ、ろ過、メタノール洗浄を行った後、100℃の真空乾燥機中24時間乾燥させ、白色粉末(脂環式ポリイミド樹脂(A2))を得た。この粉末のIRスペクトルを測定したところ、イミド基に特有の1705、1768cm-1の吸収が見られた。脂環式ポリイミド樹脂(A2)の対数粘度を測定したところ、1.24であった。
<脂環式ポリイミド樹脂(A3)の合成>
温度計、撹拌器、窒素導入環、分留器付き冷却管を備えた500mLの5つ口フラスコに、9,9-ビス(4-アミノフェニル)フルオレン27.95g(0.08モル)および4,4’-ビス(4-アミノフェノキシ)ビフェニル7.38g(0.02モル)溶剤としてSP値12.6のγ-ブチロラクトン69.31g及び、SP値10.8のN,N-ジメチルアセトアミド17.33gを仕込んで溶解させ、氷水バスを用いて5℃に冷却した。同温に保ちながら、1,2,4,5-シクロヘキサンテトラカルボン酸二無水物22.45(0.1モル)およびイミド化触媒としてトリエチルアミン0.51g(0.005モル)を一括で添加した。滴下終了後、180℃に昇温し、随時留出液を留去させながら5時間還流を行い反応終了とし、内温が120℃になるまで空冷した後、希釈溶剤としてN,N-ジメチルアセトアミド130.7gを加え、撹拌しながら冷却し、固形分濃度20質量%の脂環式ポリイミド樹脂溶液(A3’)を得た。上記溶液の質量は270.26g、また、留出液総質量は4.35gであった。上記溶液の一部を1Lのメタノールに注ぎ入れてポリマーを沈殿させ、ろ過、メタノール洗浄を行った後、100℃の真空乾燥機中24時間乾燥させ、白色粉末(脂環式ポリイミド樹脂(A3))を得た。この粉末のIRスペクトルを測定したところ、イミド基に特有の1704、1771cm-1の吸収が見られた。脂環式ポリイミド樹脂(A3)の対数粘度を測定したところ、1.16であった。
<脂環式ポリイミド樹脂(A4)の合成>
温度計、撹拌器、窒素導入環、分留器付き冷却管を備えた500mLの5つ口フラスコに、4,4-ジアミノジシクロヘキシルメタン21.14g(0.1モル)と有機溶媒としてSP値11.3のN-メチル-2-ピロリドン54.54gおよびSP値10.8のN, N-ジメチルアセトアミド13.60gを仕込んで溶解させ、氷水バスを用いて5℃に冷却した。同温に保ちながら、1,2,4,5-シクロヘキサンテトラカルボン酸二無水物22.62g(0.1モル)およびイミド化触媒としてトリエチルアミン0.50g(0.005モル)を一括で添加した。130℃まで昇温し、30分程撹拌することにより、生成した塊状の塩が均一に溶解した。その後、180℃に昇温し、随時留出液を留去させながら6時間還流を行い反応終了とし、内温が120℃になるまで空冷した後、希釈溶媒としてN,N-ジメチルアセトアミド113.4gを加え、撹拌しながら冷却し、濃度20質量%の脂環式ポリイミド樹脂溶液(A4')を得た。上記溶液の質量は223.82g、また、留出液総質量は3.54gであった。上記溶液の一部を1Lのメタノールに注ぎ入れてポリマーを沈殿させ、ろ過、メタノール洗浄を行った後、100℃の真空乾燥機中24時間乾燥させ、白色粉末(脂環式ポリイミド樹脂(A4))を得た。この粉末のIRスペクトルを測定したところ、イミド基に特有の1691、1764cm-1の吸収が見られた。脂環式ポリイミド樹脂(A4)の対数粘度を測定したところ、0.86であった。
製造例1で得られた脂環式ポリイミド樹脂溶液(A1’)に難燃剤としてシアノ変性環状フェノキシフォスファゼン化合物(B1)をポリイミド樹脂固形分100質量部に対しての含有量が3質量部となるように室温で添加し、70℃の条件で2時間撹拌混合し、脂環式ポリイミド樹脂組成物溶液を得た。溶液の濃度は20.48質量%であった。得られた脂環式ポリイミド樹脂組成物溶液を、1000μmのドクターブレードを用いて、プラスチック離型剤(ペリコート)を均一に塗布したガラス基板上にキャストした。これをホットプレートで100℃、60分間保持し、溶媒を揮発させることで自己支持性を有する無色透明な一次乾燥フィルムを得た。このフィルムをステンレス枠に固定し、200℃で3時間真空乾燥により、残留溶媒の除去を行い、膜厚97μmの透明な脂環式ポリイミド樹脂組成物から成る薄肉成型体を得た。これらの全光線透過率およびヘイズ値を求め、ガラス転移温度、表面抵抗率を測定した。また、燃焼性試験を実施した結果、UL規格VTM-0に相当した。結果を表1に示す。
製造例2で得られた脂環式ポリイミド樹脂溶液(A2’)に難燃剤としてシアノ変性環状フェノキシフォスファゼン化合物(B1)をポリイミド樹脂固形分100質量部に対しての含有量が5質量部となるように室温で添加し、70℃の条件で2時間撹拌混合し、脂環式ポリイミド樹脂組成物溶液を得た。溶液の濃度は20.79質量%であった。
次に、前記で得られた脂環式ポリイミド樹脂組成物溶液を用いたこと以外は、実施例1と同様の方法で、膜厚101μmの透明な脂環式ポリイミド樹脂組成物から成る薄肉成型体を得た。これらの全光線透過率およびヘイズ値を求め、ガラス転移温度、表面抵抗率を測定した。また、燃焼性試験を実施した結果、UL規格VTM-0に相当した。結果を表1に示す。
製造例3で得られた脂環式ポリイミド樹脂溶液(A3’)に難燃剤としてシアノ変性環状フェノキシフォスファゼン化合物(B1)をポリイミド樹脂固形分100質量部に対しての含有量が3質量部となるように室温で添加し、70℃の条件で2時間撹拌混合し、脂環式ポリイミド樹脂組成物溶液を得た。溶液の濃度は20.48質量%であった。
次に、前記で得られた脂環式ポリイミド樹脂組成物溶液を用いたこと以外は、実施例1と同様の方法で、膜厚100μmの透明な脂環式ポリイミド樹脂組成物から成る薄肉成型体を得た。これらの全光線透過率およびヘイズ値を求め、ガラス転移温度、表面抵抗率を測定した。また、燃焼性試験を実施した結果、UL規格VTM-0に相当した。結果を表1に示す。
製造例4で得られたポリイミド樹脂溶液(A4’)に難燃剤としてシアノ変性環状フェノキシフォスファゼン化合物(B1)をポリイミド樹脂固形分100質量部に対しての含有量が10質量部となるように室温で添加し、70℃の条件で2時間撹拌混合し、脂環式ポリイミド樹脂組成物溶液を得た。溶液の濃度は21.57質量%であった。
次に、前記で得られた脂環式ポリイミド樹脂組成物溶液を用いたこと以外は、実施例1と同様の方法で、膜厚102μmの透明な脂環式ポリイミド樹脂組成物から成る薄肉成型体を得た。これらの全光線透過率およびヘイズ値を求め、ガラス転移温度、表面抵抗率を測定した。また、燃焼性試験を実施した結果、UL規格VTM-0に相当した。結果を表1に示す。
製造例1で得られた脂環式ポリイミド樹脂溶液(A1’)に難燃剤としてシアノ変性環状フェノキシフォスファゼン化合物(B1)をポリイミド樹脂固形分100質量部に対しての含有量が10質量部となるように室温で添加し、70℃の条件で2時間撹拌混合し、脂環式ポリイミド樹脂組成物溶液を得た。溶液の濃度は21.57質量%であった。
次に、前記で得られた脂環式ポリイミド樹脂組成物溶液を用いたこと以外は、実施例1と同様の方法で、膜厚105μmの無色透明な脂環式ポリイミド樹脂組成物から成る薄肉成型体を得た。これらの全光線透過率およびヘイズ値を求め、ガラス転移温度、表面抵抗率を測定した。また、燃焼性試験を実施した結果、UL規格VTM-0に相当した。結果を表1に示す。
製造例4で得られたポリイミド樹脂溶液(A4’)に難燃剤としてシアノ変性環状フェノキシフォスファゼン化合物(B1)をポリイミド樹脂固形分100質量部に対しての含有量が5質量部となるように室温で添加し、70℃の条件で2時間撹拌混合し、脂環式ポリイミド樹脂組成物溶液を得た。溶液の濃度は20.79質量%であった。
次に、前記で得られた脂環式ポリイミド樹脂組成物溶液を用いたこと以外は、実施例1と同様の方法で、膜厚104μmの透明な脂環式ポリイミド樹脂組成物から成る薄肉成型体を得た。これらの全光線透過率およびヘイズ値を求め、ガラス転移温度、表面抵抗率を測定した。また、燃焼性試験を実施した結果、UL規格VTM-0に相当した。結果を表1に示す。
製造例1で得られた脂環式ポリイミド樹脂溶液(A1’)に難燃剤としてトリフェニルホスフェート(B2)をポリイミド樹脂固形分100質量部に対しての含有量が3質量部となるように添加した以外は、実施例1と同様の方法で膜厚118μmの透明な脂環式ポリイミド樹脂組成物から成る薄肉成型体を得た。これらの全光線透過率およびヘイズ値を求め、ガラス転移温度、表面抵抗率を測定した。また、燃焼性試験を実施した結果、全焼となり、UL規格外に相当した。結果を表2に示す。
製造例1で得られた脂環式ポリイミド樹脂溶液(A1’)に難燃剤としてトリフェニルホスフェート(B2)をポリイミド樹脂固形分100質量部に対しての含有量が20質量部となるように添加した以外は、実施例1と同様の方法で膜厚103μmの脂環式ポリイミド樹脂組成物から成る薄肉成型体を得た。これらの全光線透過率およびヘイズ値を求め、ガラス転移温度、表面抵抗率を測定した結果、実施例1と比較して全光線透過率が低下し、ヘイズ値が大きく上昇していた。また、燃焼性試験を実施した結果、UL規格VTM-1に相当した。結果を表2に示す。
製造例1で得られた脂環式ポリイミド樹脂溶液(A1’)に難燃剤としてレゾルシノールビス(フェニル)フォスフェート(B3)をポリイミド樹脂固形分100質量部に対しての含有量が20質量部となるように添加した以外は、実施例1と同様の方法で膜厚98μmの脂環式ポリイミド樹脂組成物から成る薄肉成型体を得た。これらの全光線透過率およびヘイズ値を求め、ガラス転移温度、表面抵抗率を測定した結果、実施例1と比較して全光線透過率が低下し、ヘイズ値が大きく上昇していた。また、燃焼性試験を実施した結果、UL規格VTM-1に相当した。結果を表2に示す。
製造例1で得られた脂環式ポリイミド樹脂溶液(A1’)に難燃剤としてフェノキシフォスファゼン(B4)をポリイミド樹脂固形分100質量部に対しての含有量が3質量部となるように添加した以外は、実施例1と同様の方法で膜厚105μmの透明な脂環式ポリイミド樹脂組成物から成る薄肉成型体を得た。これらの全光線透過率およびヘイズ値を求め、ガラス転移温度、表面抵抗率を測定した。また、燃焼性試験を実施した結果、UL規格VTM-1に相当した。結果を表2に示す。
製造例1で得られた脂環式ポリイミド樹脂溶液(A1’)に難燃剤としてフェノキシフォスファゼン化合物(B4)をポリイミド樹脂固形分100質量部に対しての含有量が20質量部となるように添加した以外は、実施例1と同様の方法で膜厚109μmの脂環式ポリイミド樹脂組成物から成る薄肉成型体を得た。これらの全光線透過率およびヘイズ値を求め、ガラス転移温度、表面抵抗率を測定した。また、燃焼性試験を実施した結果、UL規格VTM-0に相当したが、実施例1と比較してガラス転移温度が大幅に低下し、全光線透過率が低下し、ヘイズ値が上昇していた。結果を表2に示す。
製造例1で得られた脂環式ポリイミド樹脂溶液(A1’)に難燃剤としてシアノ変性環状フェノキシフォスファゼン化合物(B1)をポリイミド樹脂固形分100質量部に対しての含有量が20質量部となるように添加した以外は、実施例1と同様の方法で膜厚111μmの透明な脂環式ポリイミド樹脂組成物から成る薄肉成型体を得た。これらの全光線透過率およびヘイズ値を求め、ガラス転移温度、表面抵抗率を測定した。また、燃焼性試験を実施した結果、UL規格VTM-0に相当したが、ガラス転移温度が実施例1と比較して大幅に低下していた。結果を表2に示す。
表3に示す、脂環式ポリイミド樹脂組成物から成る薄肉成型体を、難燃剤を添加しなかったこと以外は実施例1と同様の方法で得た。これらの全光線透過率およびヘイズ値を求め、ガラス転移温度、表面抵抗率を測定した。また、燃焼性試験を実施した結果、全焼となり、UL規格外に相当した。結果を表3に示す。
Claims (4)
- 下記一般式(1)で表される構造単位を有する脂環式ポリイミド樹脂(A)100質量部に対して、下記一般式(2)で表されるシアノ変性環状フェノキシフォスファゼン化合物(B)を1~13質量部含む脂環式ポリイミド樹脂組成物。
- 上記式(1)および(3)において、R2が炭素数6~27の2価の芳香族炭化水素基であって、R2に結合する窒素原子がR2の芳香環に直結する、請求項1又は2に記載の脂環式ポリイミド樹脂組成物。
- 請求項1~3のいずれかに記載の脂環式ポリイミド樹脂組成物から成る薄肉成型体であって、該脂環式ポリイミド樹脂組成物を有機溶媒に溶解させてなる脂環式ポリイミド樹脂組成物溶液を流延させた後に加熱して得られる、薄肉成型体。
Priority Applications (5)
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JP2013521599A JP5920349B2 (ja) | 2011-06-21 | 2012-06-20 | 難燃化された脂環式ポリイミド樹脂組成物およびその薄肉成型体 |
CN201280028994.7A CN103608406B (zh) | 2011-06-21 | 2012-06-20 | 阻燃化了的脂环式聚酰亚胺树脂组合物及其薄壁成型体 |
EP12802902.2A EP2725067B1 (en) | 2011-06-21 | 2012-06-20 | Flameproofed alicyclic polyimide resin composition and thin-walled molded body of same |
KR1020137033277A KR101898689B1 (ko) | 2011-06-21 | 2012-06-20 | 난연화된 지환식 폴리이미드 수지 조성물 및 그 박육 성형체 |
US14/124,113 US20140114000A1 (en) | 2011-06-21 | 2012-06-20 | Flameproofed alicyclic polyimide resin composition and thin-walled molded body of same |
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Cited By (2)
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WO2016190105A1 (ja) * | 2015-05-25 | 2016-12-01 | コニカミノルタ株式会社 | ポリイミドフィルム、ポリイミドフィルムの製造方法、フレキシブルプリント基板、フレキシブルディスプレイ用基板、フレキシブルディスプレイ用前面板、led照明装置及び有機エレクトロルミネッセンス表示装置 |
JP2021100822A (ja) * | 2014-11-10 | 2021-07-08 | 住友化学株式会社 | 樹脂フィルム、積層フィルム、光学部材、表示部材、前面板、及び積層フィルムの製造方法 |
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US9790349B2 (en) * | 2014-11-14 | 2017-10-17 | Schill & Seilacher Gmbh | Flame retardant wood plastic composite |
EP3441428B1 (en) * | 2016-04-05 | 2024-03-13 | Mitsubishi Gas Chemical Company, Inc. | Polyimide resin composition, method for producing same, and polyimide film |
CN109575285B (zh) * | 2018-12-11 | 2020-05-05 | 中国地质大学(北京) | 一种利用pi基体树脂制备聚酰亚胺薄膜的方法 |
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- 2012-06-20 CN CN201280028994.7A patent/CN103608406B/zh active Active
- 2012-06-20 JP JP2013521599A patent/JP5920349B2/ja active Active
- 2012-06-20 KR KR1020137033277A patent/KR101898689B1/ko active IP Right Grant
- 2012-06-20 WO PCT/JP2012/065752 patent/WO2012176806A1/ja active Application Filing
- 2012-06-20 EP EP12802902.2A patent/EP2725067B1/en not_active Not-in-force
- 2012-06-20 US US14/124,113 patent/US20140114000A1/en not_active Abandoned
- 2012-06-21 TW TW101122238A patent/TWI544006B/zh active
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Also Published As
Publication number | Publication date |
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CN103608406A (zh) | 2014-02-26 |
EP2725067A4 (en) | 2015-01-14 |
JPWO2012176806A1 (ja) | 2015-02-23 |
EP2725067A1 (en) | 2014-04-30 |
KR20140057492A (ko) | 2014-05-13 |
TW201307438A (zh) | 2013-02-16 |
EP2725067B1 (en) | 2016-02-24 |
CN103608406B (zh) | 2016-02-17 |
US20140114000A1 (en) | 2014-04-24 |
TWI544006B (zh) | 2016-08-01 |
JP5920349B2 (ja) | 2016-05-18 |
KR101898689B1 (ko) | 2018-09-13 |
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