JP4940623B2 - Fluorine-containing polymerizable monomer and polymer compound using the same - Google Patents
Fluorine-containing polymerizable monomer and polymer compound using the same Download PDFInfo
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- JP4940623B2 JP4940623B2 JP2005303786A JP2005303786A JP4940623B2 JP 4940623 B2 JP4940623 B2 JP 4940623B2 JP 2005303786 A JP2005303786 A JP 2005303786A JP 2005303786 A JP2005303786 A JP 2005303786A JP 4940623 B2 JP4940623 B2 JP 4940623B2
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- general formula
- fluorine
- acid
- represented
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- 229920000642 polymer Polymers 0.000 title claims description 54
- 239000000178 monomer Substances 0.000 title claims description 46
- 229910052731 fluorine Inorganic materials 0.000 title claims description 42
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 41
- 239000011737 fluorine Substances 0.000 title claims description 41
- 150000001875 compounds Chemical class 0.000 title claims description 37
- -1 2-hydroxyhexafluoro-2-propyl group Chemical group 0.000 claims description 36
- 238000006116 polymerization reaction Methods 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- YGMPWNORVSXQHO-UHFFFAOYSA-N 2-(2,5-diaminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound NC1=CC=C(N)C(C(O)(C(F)(F)F)C(F)(F)F)=C1 YGMPWNORVSXQHO-UHFFFAOYSA-N 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 9
- 125000002723 alicyclic group Chemical group 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 7
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 7
- 125000000962 organic group Chemical group 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 36
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 18
- 150000004985 diamines Chemical class 0.000 description 18
- 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 17
- 239000002904 solvent Substances 0.000 description 17
- 239000002253 acid Substances 0.000 description 16
- VBZWSGALLODQNC-UHFFFAOYSA-N hexafluoroacetone Chemical compound FC(F)(F)C(=O)C(F)(F)F VBZWSGALLODQNC-UHFFFAOYSA-N 0.000 description 16
- SNZAEUWCEHDROX-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-one;trihydrate Chemical compound O.O.O.FC(F)(F)C(=O)C(F)(F)F SNZAEUWCEHDROX-UHFFFAOYSA-N 0.000 description 13
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 229920001721 polyimide Polymers 0.000 description 12
- 239000004642 Polyimide Substances 0.000 description 11
- 150000001412 amines Chemical class 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 150000001991 dicarboxylic acids Chemical class 0.000 description 7
- 125000000524 functional group Chemical group 0.000 description 7
- 238000007363 ring formation reaction Methods 0.000 description 7
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 229920005575 poly(amic acid) Polymers 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 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 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 4
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 4
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 3
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 206010034972 Photosensitivity reaction Diseases 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000370 acceptor Substances 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 150000002466 imines Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000036211 photosensitivity Effects 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229920006122 polyamide resin Polymers 0.000 description 3
- 229920002577 polybenzoxazole Polymers 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 0 CCC(C)(C)c1ccc(*(C(*2C(*(C(C)(C)C)C(*)=O)=O)=C3CC3)C2=O)cc1 Chemical compound CCC(C)(C)c1ccc(*(C(*2C(*(C(C)(C)C)C(*)=O)=O)=C3CC3)C2=O)cc1 0.000 description 2
- QGLBZNZGBLRJGS-UHFFFAOYSA-N Dihydro-3-methyl-2(3H)-furanone Chemical compound CC1CCOC1=O QGLBZNZGBLRJGS-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- AMEDKBHURXXSQO-UHFFFAOYSA-N azonous acid Chemical compound ONO AMEDKBHURXXSQO-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 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
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 150000004682 monohydrates Chemical class 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 125000006239 protecting group Chemical group 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
- 230000035484 reaction time Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
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- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical group FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- YEDDVXZFXSHDIB-UHFFFAOYSA-N 1,1,2,2,3,3-hexafluoropropan-1-ol Chemical group OC(F)(F)C(F)(F)C(F)F YEDDVXZFXSHDIB-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- YQTCQNIPQMJNTI-UHFFFAOYSA-N 2,2-dimethylpropan-1-one Chemical group CC(C)(C)[C]=O YQTCQNIPQMJNTI-UHFFFAOYSA-N 0.000 description 1
- DKDZUCBUEMQGIC-UHFFFAOYSA-N 2,3,5,6-tetrafluoro-4-(2,3,4,5-tetrafluorophenoxy)aniline Chemical compound FC1=C(F)C(N)=C(F)C(F)=C1OC1=CC(F)=C(F)C(F)=C1F DKDZUCBUEMQGIC-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- 229940075142 2,5-diaminotoluene Drugs 0.000 description 1
- ZQQOGBKIFPCFMJ-UHFFFAOYSA-N 2-(trifluoromethyl)benzene-1,4-diamine Chemical compound NC1=CC=C(N)C(C(F)(F)F)=C1 ZQQOGBKIFPCFMJ-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- OBCSAIDCZQSFQH-UHFFFAOYSA-N 2-methyl-1,4-phenylenediamine Chemical compound CC1=CC(N)=CC=C1N OBCSAIDCZQSFQH-UHFFFAOYSA-N 0.000 description 1
- BDSPLIQKGRTNCG-UHFFFAOYSA-N 3,4-dimethylcyclohexa-1,5-diene-1,3-diamine Chemical group CC1C=CC(N)=CC1(C)N BDSPLIQKGRTNCG-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 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
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- 125000000268 heptanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003104 hexanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000006358 imidation reaction Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- MGJXBDMLVWIYOQ-UHFFFAOYSA-N methylazanide Chemical compound [NH-]C MGJXBDMLVWIYOQ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 150000007965 phenolic acids Chemical group 0.000 description 1
- 150000004986 phenylenediamines Chemical group 0.000 description 1
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZDYVRSLAEXCVBX-UHFFFAOYSA-N pyridinium p-toluenesulfonate Chemical compound C1=CC=[NH+]C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 ZDYVRSLAEXCVBX-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Description
本発明は、新規な含フッ素重合性単量体およびそれを用いた新規な高分子化合物に関する。 The present invention relates to a novel fluorine-containing polymerizable monomer and a novel polymer compound using the same.
高度の耐熱性を有する有機高分子の代表としてポリアミドやポリイミドが開発され、電子デバイス分野、自動車や航空宇宙用途などのエンジニアリングプラスチック分野、燃料電池分野、医療材料分野、光学材料分野などにおいて大きな市場を形成している。それらの中心は、ナイロン、ケブラーなどに代表されるポリアミド、耐熱高分子の代名詞とも言えるポリアミド酸やポリイミド、それらの複合体であるポリアミドイミド、さらにポリベンズオキサゾール、ポリベンズチアゾール、ポリベンズイミダゾールなどの多種多様な高分子が数多く、実用化されている。特に最近では鉛フリーのハンダ工程に耐える材料としてポリイミドが改めて注目されている。 Polyamides and polyimides have been developed as representatives of highly heat-resistant organic polymers, and have a large market in the fields of electronic devices, engineering plastics such as automobiles and aerospace applications, fuel cells, medical materials, and optical materials. Forming. Their centers are polyamides such as nylon and Kevlar, polyamic acids and polyimides that are synonymous with heat-resistant polymers, polyamideimides that are composites of them, and polybenzoxazole, polybenzthiazole, polybenzimidazole, etc. Many different types of polymers have been put into practical use. In particular, polyimide has recently attracted attention as a material that can withstand a lead-free soldering process.
これらの耐熱性高分子の多くは２官能、３官能の反応性基を分子内に有した単量体を複数種用いて、重付加、重縮合などの反応を連鎖的に起こすことで高分子化されている。 Many of these heat-resistant polymers use a plurality of types of monomers having bifunctional and trifunctional reactive groups in the molecule to cause reactions such as polyaddition and polycondensation in a chain. It has become.
重合における単量体の組み合わせは、ポリアミドの場合、ジアミン型単量体を、ジカルボン酸、酸クロリドまたはエステルなどのジカルボン酸誘導体と縮合させる方法、ポリアミド酸又はポリイミドの場合はジアミンと酸二無水物の重付加による方法などが知られている。一般に使用されているジアミンとしては、脂肪族ジアミン、脂環式ジアミン、芳香族ジアミンが報告されているが、重合性や耐熱性の観点からは、ベンゼン環単環、ビフェニル型、または複数のベンゼン環が直接または間接に結合した多環構造を支持骨格とし、その分子内に複数のアミンが含まれたアニリン系単量体が好適に採用されている。一方、ポリベンゾオキサゾール、ポリベンズチアゾールの場合には、ベンゼン環のオルト位にアミンとヒドロキシ基、アミンとチオール基を有した単量体が使用されている。 In the case of polyamide, the combination of monomers in the polymerization is a method of condensing a diamine type monomer with a dicarboxylic acid derivative such as dicarboxylic acid, acid chloride or ester, and in the case of polyamic acid or polyimide, diamine and acid dianhydride. A method using polyaddition is known. As diamines that are generally used, aliphatic diamines, alicyclic diamines, and aromatic diamines have been reported. From the viewpoint of polymerizability and heat resistance, benzene ring monocyclic, biphenyl type, or multiple benzenes are reported. An aniline monomer in which a polycyclic structure in which rings are directly or indirectly bonded is used as a supporting skeleton and a plurality of amines are contained in the molecule is suitably employed. On the other hand, in the case of polybenzoxazole and polybenzthiazole, monomers having an amine and a hydroxy group and an amine and a thiol group at the ortho position of the benzene ring are used.
アミンおよびそれ以外の官能基を同時に分子内に持たせる目的としては次のように説明される。すなわち、重合部位としてはジアミンを用い、同時に分子内縮合環化用の官能基として、ヒドロキシ基、チオール基を用い、さらにまたこれらのアルカリ可溶性基などの感光性機能性基として、フェノール性の酸性基を持たせた設計を行っている。しかしながら複数種の官能基をジアミンとともに含有させる試みは限られた前述のような組み合わせしか報告されていない。 The purpose of simultaneously providing an amine and other functional group in the molecule is explained as follows. In other words, diamine is used as the polymerization site, and at the same time, a hydroxyl group or a thiol group is used as a functional group for intramolecular condensed cyclization, and a phenolic acid group is used as a photosensitive functional group such as an alkali-soluble group. We are designing with a group. However, only a limited number of the aforementioned combinations have been reported for attempts to contain multiple types of functional groups together with diamines.
一方、フッ素系化合物は、フッ素の持つ撥水性、撥油性、低吸水性、耐熱性、耐候性、耐腐食性、透明性、感光性、低屈折率性、低誘電性などの特徴から先端材料分野を中心としてポリオレフィンや縮合性高分子などの幅広い材料分野で開発または実用化されている。縮合性高分子分野では、ジアミン単量体中にフッ素を導入する試みがなされ、ベンゼン環の水素をフッ素原子やトリフルオロメチル基に置換したジアミン単量体、２つの芳香環の間にヘキサフルオロイソプロペニル基を導入したジアミン単量体、さらにはベンゼン環を水素還元した含フッ素ジアミン単量体などが報告されている。また、ヘキサフルオロイソプロペニル基を中心原子団とし、その両サイドに芳香族ヒドロキシアミンを有したビスヒドロキシアミン単量体も実用化されている。この場合、ポリベンゾオキサゾールやヒドロキシ基含有ポリイミドとして応用されている。例えば、非特許文献１などに含フッ素ポリベンゾアゾール類として説明されている。 Fluorine compounds, on the other hand, are advanced materials due to the characteristics of fluorine such as water repellency, oil repellency, low water absorption, heat resistance, weather resistance, corrosion resistance, transparency, photosensitivity, low refractive index, and low dielectric properties. It has been developed or put into practical use in a wide range of materials such as polyolefins and condensable polymers. In the field of condensable polymers, attempts have been made to introduce fluorine into a diamine monomer. A diamine monomer in which the hydrogen of the benzene ring is substituted with a fluorine atom or a trifluoromethyl group, and hexafluoro between the two aromatic rings. A diamine monomer into which an isopropenyl group is introduced and a fluorine-containing diamine monomer in which a benzene ring is reduced with hydrogen have been reported. A bishydroxyamine monomer having a hexafluoroisopropenyl group as a central atomic group and having an aromatic hydroxyamine on both sides has also been put into practical use. In this case, it is applied as polybenzoxazole or a hydroxy group-containing polyimide. For example, it is described as non-patent documents 1 as fluorine-containing polybenzoazoles.
さらに一方、最近になってフッ素系化合物の紫外線領域、特に、真空紫外波長域での透明性を応用したフォトレジスト材料など活発な研究開発が行われている。フッ素を導入することで各使用波長での透明性を実現しつつ、基板への密着性、高いガラス転移点、フルオロカルビノール基の酸性による感光性、アルカリ現像性などを実現させようとする試みである。特に、フルオロカルビノールの中でもヘキサフルオロイソプロピル基がその溶解挙動、非膨潤性、高コントラストなどから注目され数多くの研究開発が行われている。 On the other hand, recently, active research and development has been conducted on photoresist materials applying transparency in the ultraviolet region of fluorine-based compounds, particularly in the vacuum ultraviolet wavelength region. Attempts to achieve transparency at various wavelengths by introducing fluorine, while achieving adhesion to the substrate, high glass transition point, photosensitivity due to the acidity of the fluorocarbinol group, alkali developability, etc. It is. In particular, among fluorocarbinols, the hexafluoroisopropyl group has attracted attention because of its dissolution behavior, non-swelling property, high contrast, etc., and many researches and developments have been conducted.
フォトレジストの開発例からも推察されるように酸性アルコールであるヘキサフルオロイソプロピル基は少ない膨潤性を維持したまま、すみやかで均一なアルカリ可溶性を発現し得る可能性を有しているが、同様なコンセプトを利用した耐熱性高分子、すなわちヘキサフルオロイソプロピル基を酸性アルコールとして含有した耐熱性高分子の開発例はほとんど報告されていない。また一般的な酸性基としてはカルボキシル基を挙げることができるが、アミンとの反応性の高さから同一分子内にカルボキシル基を有したアミンを安定に存在させることは難しいとされている。
すなわち本発明では、含フッ素材料としての表面特性（撥水性、撥油性等）、耐性（耐熱性、耐候性、耐腐食性等）、その他の特性（透明性、低屈折率性、低誘電性等）とアルカリ可溶性、感光性、有機溶媒溶解性などを併せ持つ重合可能な新規な高分子材料用単量体を見出し、かつそれを用いた新規な高分子化合物を提供することを課題とする。 That is, in the present invention, surface characteristics (water repellency, oil repellency, etc.), resistance (heat resistance, weather resistance, corrosion resistance, etc.), and other characteristics (transparency, low refractive index, low dielectric properties) as a fluorine-containing material Etc.) and alkali-soluble, photosensitive, organic solvent-soluble, and the like, and a novel polymerizable polymer material monomer, and a novel polymer compound using the same.
本発明者らは、前記の課題を解決するために鋭意検討を重ねた結果、フェニレンジアミン骨格を有し、そのフェニレンジアミン上の少なくとも１つの水素原子がヘキサフルオロイソプロピル基に置換した新規なフェニレンジアミン系化合物を見出した。またアミンのオルト位にヘキサフルオロイソプロピル基を有した特定の単量体の場合、環化反応を伴い、低誘電性、耐熱性、耐溶剤性などの多くの特徴を有する新規な高分子化合物となることを見出し、本発明を完成した。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have a novel phenylenediamine having a phenylenediamine skeleton and having at least one hydrogen atom on the phenylenediamine substituted with a hexafluoroisopropyl group. A compound was found. In addition, in the case of a specific monomer having a hexafluoroisopropyl group at the ortho position of the amine, a novel polymer compound having many characteristics such as low dielectric properties, heat resistance, and solvent resistance is accompanied by a cyclization reaction. The present invention was completed.
すなわち、本発明は、
「１」 一般式［１］
That is, the present invention
“1” General formula [1]
「２」 一般式［２］
“2” General formula [2]
「３」 一般式［３］
“3” General formula [3]
「４」 一般式［４］
"4" General formula [4]
「５」 上記「１」〜「４」のいずれか１つに記載の含フッ素重合性単量体を用いて重合した高分子化合物。 [5] A polymer compound polymerized using the fluorine-containing polymerizable monomer described in any one of [1] to [4].
「６」 一般式［５］ "6" General formula [5]
「７」 上記「６」記載の高分子化合物であって、ａ＝１で且つアミノ基のα位に２−ヒドロキシヘキサフルオロ−２−プロピル基を有する化合物を環化縮合してなる一般式［６］で表される高分子化合物。（一般式［６］中、Ｂおよびｎは一般式［５］と同じ）
“7” A polymer compound according to the above “6”, wherein a = 1 and a compound having a 2-hydroxyhexafluoro-2-propyl group at the α-position of the amino group is cyclized and condensed [ 6]. (In general formula [6], B and n are the same as in general formula [5])
「９」 一般式［７］記載の高分子化合物を環化縮合してなる一般式［８］で表される高分子化合物。
[9] A polymer compound represented by the general formula [8] obtained by cyclization condensation of the polymer compound described in the general formula [7].
なお、一般式［５］〜［８］におけるｎ（重合度）とは、重合の程度に依存する繰り返し単位の数（正の整数）を意味し、５〜１００００が好ましく、１０〜１０００がさらに好ましい。また、本発明の重合体は、重合度に一定の幅のある重合体の混合物であるが、重合体重量平均分子量でいうと、概ね１０００〜５００００００が好ましく、２０００〜２０００００の範囲が特に好ましい。重合度、分子量は、後述の重合方法の条件を適宜調節することによって、所望の値に設定することができる。 In addition, n (degree of polymerization) in the general formulas [5] to [8] means the number of repeating units (a positive integer) depending on the degree of polymerization, preferably 5 to 10000, and more preferably 10 to 1000. preferable. In addition, the polymer of the present invention is a mixture of polymers having a certain degree of polymerization degree, but in terms of the weight average molecular weight of the polymer, generally 1000 to 5000000 is preferable, and 2000 to 200000 is particularly preferable. The degree of polymerization and molecular weight can be set to desired values by appropriately adjusting the conditions of the polymerization method described later.
ジアミンとヘキサフルオロイソプロピル基を同時に含有させることで、フルオロカルビノール性酸性基を有した新規なフェニレンジアミン型含フッ素重合性単量体及びそれを用いた新規な高分子化合物を提供できる。 By containing a diamine and a hexafluoroisopropyl group at the same time, a novel phenylenediamine-type fluorine-containing polymerizable monomer having a fluorocarbinol acidic group and a novel polymer compound using the same can be provided.
以下、本発明を詳細に説明する。本発明は一般式［１］ Hereinafter, the present invention will be described in detail. The present invention relates to the general formula [1]
上記一般式［１］の重合性単量体を具体的に例示するならば、次の一般式［４］、［９ａ］、［９ｂ］、［９ｃ］および一般式［１０］〜［２７］などが挙げられる。 Specific examples of the polymerizable monomer represented by the general formula [1] include the following general formulas [4], [9a], [9b], [9c], and general formulas [10] to [27]. Etc.
この単量体は、１，４−フェニレンジアミンとヘキサフルオロアセトンもしくはヘキサフルオロアセトン・３水和物を反応させることによって得られる。 This monomer can be obtained by reacting 1,4-phenylenediamine with hexafluoroacetone or hexafluoroacetone trihydrate.
ヘキサフルオロアセトンを使用する場合、反応は、原料である１，４−フェニレンジアミンの中へヘキサフルオロアセトンを導入することによって行われる。ヘキサフルオロアセトンの沸点が低い（−２８℃）ことから、ヘキサフルオロアセトンの反応系外への流出を防ぐための装置（冷却装置もしくは密封反応器）を使用することが好ましく、装置としては密封反応器が特に好ましい。 When hexafluoroacetone is used, the reaction is performed by introducing hexafluoroacetone into 1,4-phenylenediamine as a raw material. Since the boiling point of hexafluoroacetone is low (−28 ° C.), it is preferable to use a device (cooling device or sealed reactor) for preventing the hexafluoroacetone from flowing out of the reaction system. A vessel is particularly preferred.
また、ヘキサフルオロアセトン・３水和物を使用する場合、反応は、原料である１，４−フェニレンジアミンとヘキサフルオロアセトン・３水和物を同時に混合することによって開始することができる。また、ヘキサフルオロアセトン・３水和物の沸点が比較的高い（１０５℃）ことから、ヘキサフルオロアセトン（沸点：−２８℃）と比較して取扱いが容易である。この場合、反応装置としては、密封容器を使用することもできるが、通常の還流冷却管に上水（室温）を通じる程度でも十分にヘキサフルオロアセトン・３水和物の反応系外への流出を防ぐことができる。 Further, when hexafluoroacetone trihydrate is used, the reaction can be started by simultaneously mixing the raw materials 1,4-phenylenediamine and hexafluoroacetone trihydrate. In addition, since the boiling point of hexafluoroacetone trihydrate is relatively high (105 ° C.), it is easier to handle than hexafluoroacetone (boiling point: −28 ° C.). In this case, a sealed vessel can be used as the reaction apparatus, but hexafluoroacetone trihydrate can be sufficiently discharged out of the reaction system even by passing clean water (room temperature) through a normal reflux condenser. Can be prevented.
また、ヘキサフルオロアセトンはヘキサフルオロアセトン・３水和物に比較して反応性が高く、反応条件によってはヘキサフルオロアセトンがアニリン骨格上のアミノ基と反応して、次の一般式［２８］〜［３０］ Hexafluoroacetone is more reactive than hexafluoroacetone trihydrate. Depending on the reaction conditions, hexafluoroacetone reacts with an amino group on the aniline skeleton, and the following general formula [28] to [30]
このように、取扱いの容易さ、装置の簡便さ、そして生成物選択性の高さの観点から、１−（２−ヒドロキシヘキサフルオロ−２−プロピル）−２，５−フェニレンジアミンの製造に当たっては、ヘキサフルオロアセトン・３水和物を使用することが特に好ましい。 Thus, in view of ease of handling, ease of equipment, and high product selectivity, in the production of 1- (2-hydroxyhexafluoro-2-propyl) -2,5-phenylenediamine, It is particularly preferable to use hexafluoroacetone trihydrate.
本反応に使用するヘキサフルオロアセトンもしくはヘキサフルオロアセトン・３水和物の量は、１，４−フェニレンジアミンに対して、１当量〜１０当量が好ましく、さらに好ましくは１．５当量〜５当量である。これ以上使用しても反応は問題なく進行するが、経済性の面から好ましくない。 The amount of hexafluoroacetone or hexafluoroacetone trihydrate used in this reaction is preferably 1 equivalent to 10 equivalents, more preferably 1.5 equivalents to 5 equivalents with respect to 1,4-phenylenediamine. is there. Although the reaction proceeds without problems even if it is used more than this, it is not preferable from the viewpoint of economy.
本反応は、通常、室温〜１８０℃の温度範囲で行われるが、５０℃〜１５０℃が好ましく、９０℃〜１３０℃が特に好ましい。１８０℃を超える温度では副反応が進行するので好ましくない。 This reaction is usually performed in a temperature range of room temperature to 180 ° C, preferably 50 ° C to 150 ° C, particularly preferably 90 ° C to 130 ° C. A temperature exceeding 180 ° C. is not preferable because side reaction proceeds.
本反応は、触媒を使用しなくても行うことができるが、酸触媒を使用することで反応を促進させることができる。使用される酸触媒としては、塩化アルミニウム、塩化鉄（ＩＩＩ）、フッ化硼素等のルイス酸、ベンゼンスルホン酸、カンファースルホン酸（ＣＳＡ）、メタンスルホン酸、ｐ−トルエンスルホン酸（ｐＴｓＯＨ）、ｐ−トルエンスルホン酸（ｐＴｓＯＨ）・一水和物、ピリジニウムｐ−トルエンスルホン酸（ＰＰＴＳ）などの有機スルホン酸が好ましいが、これらの中でも、塩化アルミニウム、塩化鉄（ＩＩＩ）、メタンスルホン酸、ｐ−トルエンスルホン酸（ｐＴｓＯＨ）・一水和物が特に好ましい。使用される触媒の量は、１，４−フェニレンジアミン１モルに対して、０．５モル％〜１０モル％が好ましく、１モル％から５モル％が特に好ましい。これ以上使用しても反応は問題なく進行するが、経済性の面から好ましくない。 Although this reaction can be performed without using a catalyst, the reaction can be promoted by using an acid catalyst. Examples of the acid catalyst used include Lewis acid such as aluminum chloride, iron (III) chloride, boron fluoride, benzenesulfonic acid, camphorsulfonic acid (CSA), methanesulfonic acid, p-toluenesulfonic acid (pTsOH), p -Organic sulfonic acids such as toluenesulfonic acid (pTsOH) monohydrate and pyridinium p-toluenesulfonic acid (PPTS) are preferable. Among these, aluminum chloride, iron (III) chloride, methanesulfonic acid, p- Toluenesulfonic acid (pTsOH) monohydrate is particularly preferred. The amount of the catalyst used is preferably 0.5 mol% to 10 mol%, particularly preferably 1 mol% to 5 mol%, relative to 1 mol of 1,4-phenylenediamine. Although the reaction proceeds without problems even if it is used more than this, it is not preferable from the viewpoint of economy.
本反応は溶媒を使用せずに行うことができるが、溶媒を使用することもできる。使用される溶媒としては、反応に関与しないものなら特に制限は無いが、キシレン等の芳香族炭化水素類または水が好ましい。使用する溶媒の量には特に制限が無いが、多量に使用することは容積あたりの収量が減少するので好ましくない。 Although this reaction can be carried out without using a solvent, a solvent can also be used. The solvent to be used is not particularly limited as long as it does not participate in the reaction, but aromatic hydrocarbons such as xylene or water is preferable. The amount of the solvent to be used is not particularly limited, but it is not preferable to use a large amount because the yield per volume decreases.
本反応を密封反応器（オートクレーブ）を使用して行う場合には、ヘキサフルオロアセトンとヘキサフルオロアセトン・３水和物のいずれか用いるかによって様態が異なる。ヘキサフルオロアセトンを用いる場合には最初に１，４−フェニレンジアミンと、必要に応じて触媒および／または溶媒を反応器内に仕込む。次いで、反応器内圧が０．５ＭＰａを越えないように、温度を上げつつ、ヘキサフルオロアセトンを逐次導入していくことが好ましい。ヘキサフルオロアセトン・３水和物を用いる場合には、最初に１，４−フェニレンジアミンと必要量のヘキサフルオロアセトン・３水和物を仕込むことが可能であり、さらに必要に応じて触媒および／または溶媒を反応器内に仕込んで反応を行うことができる。 When this reaction is carried out using a sealed reactor (autoclave), the mode differs depending on whether hexafluoroacetone or hexafluoroacetone trihydrate is used. When hexafluoroacetone is used, first, 1,4-phenylenediamine and optionally a catalyst and / or solvent are charged into the reactor. Subsequently, it is preferable to introduce hexafluoroacetone successively while raising the temperature so that the internal pressure of the reactor does not exceed 0.5 MPa. When hexafluoroacetone trihydrate is used, 1,4-phenylenediamine and the required amount of hexafluoroacetone trihydrate can be initially charged, and if necessary, a catalyst and / or Alternatively, the reaction can be carried out by charging a solvent into the reactor.
本反応の反応時間に特別な制限はないが、温度や、用いる触媒の量等に依存して最適の反応時間は異なる。従って、ガスクロマトグラフィー等、汎用の分析手段により、反応の進行状況を測定しつつ反応を実施し、原料が十分消費されたことを確認した後、本工程を終了することが好ましい。反応終了後、抽出、蒸留、晶析等の通常の手段により、１−（２−ヒドロキシヘキサフルオロ−２−プロピル）−２，５−フェニレンジアミンを得ることができる。また、必要によりカラムクロマトグラフィーあるいは再結晶等により精製することもできる。 The reaction time of this reaction is not particularly limited, but the optimum reaction time varies depending on the temperature, the amount of catalyst used, and the like. Therefore, it is preferable to carry out the reaction while measuring the progress of the reaction by a general-purpose analysis means such as gas chromatography and confirm that the raw materials are sufficiently consumed, and then terminate this step. After completion of the reaction, 1- (2-hydroxyhexafluoro-2-propyl) -2,5-phenylenediamine can be obtained by ordinary means such as extraction, distillation, and crystallization. If necessary, it can be purified by column chromatography or recrystallization.
その他の一般式［１］で表される含フッ素重合性単量体を製造するにあたっては、使用するヘキサフルオロアセトンもしくはヘキサフルオロアセトン・３水和物の量を制御する以外は、上述した、１−（２−ヒドロキシヘキサフルオロ−２−プロピル）−２，５−フェニレンジアミンの合成方法に準拠して行うことができる。 In producing other fluorine-containing polymerizable monomers represented by the general formula [1], the above-described 1 is used except that the amount of hexafluoroacetone or hexafluoroacetone trihydrate used is controlled. It can be performed according to the synthesis method of-(2-hydroxyhexafluoro-2-propyl) -2,5-phenylenediamine.
次に、本発明による含フッ素重合性単量体の使用方法例を説明する。本発明の含フッ素重合性単量体は、ジアミンであり、ヘキサフルオロイソプロピル基を一つ以上有する化合物であり、少なくとも分子内に３つ以上の官能基を同時に有している。高分子を製造する場合、これらの３つ以上の官能基を有効に利用することになるが、具体的にはジアミンを使用することが好ましい。 Next, an example of how to use the fluorine-containing polymerizable monomer according to the present invention will be described. The fluorine-containing polymerizable monomer of the present invention is a diamine, a compound having one or more hexafluoroisopropyl groups, and having at least three functional groups in the molecule at the same time. In the case of producing a polymer, these three or more functional groups are effectively used. Specifically, it is preferable to use a diamine.
本発明の含フッ素重合性単量体であるジアミンの相手方としてジカルボン酸単量体を使用でき、生成する高分子としてポリアミド樹脂が合成される。この場合、ジカルボン酸はもとより、その誘導体、例えば、ジカルボン酸ジハライド（ハロゲンは、塩素、臭素、フッ素、ヨウ素）、ジカルボン酸モノエステル、ジカルボン酸ジエステルを用いることができる。 A dicarboxylic acid monomer can be used as the diamine counterpart of the fluorinated polymerizable monomer of the present invention, and a polyamide resin is synthesized as a polymer to be produced. In this case, not only dicarboxylic acids but also derivatives thereof such as dicarboxylic acid dihalides (halogens are chlorine, bromine, fluorine, iodine), dicarboxylic acid monoesters, and dicarboxylic acid diesters can be used.
本発明の含フッ素重合性単量体の相手となる重合性単量体を例示するならば、一般式［３１］で示されるジカルボン酸およびそのエステル誘導体および一般式［３２］で示されるジカルボン酸ハライドが挙げられる。 If the polymerizable monomer which becomes the partner of the fluorine-containing polymerizable monomer of the present invention is exemplified, the dicarboxylic acid represented by the general formula [31] and its ester derivative and the dicarboxylic acid represented by the general formula [32] A halide is mentioned.
本発明で使用できるジカルボン酸をジカルボン酸の形で例示すると、例えばシュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸等の脂肪族ジカルボン酸、フタル酸、イソフタル酸、テレフタル酸、３，３’−ジカルボキシルジフェニルエーテル、３，４’−ジカルボキシルジフェニルエーテル、４，４’−ジカルボキシルジフェニルエーテル、３，３’−ジカルボキシルジフェニルメタン、３，４’−ジカルボキシルジフェニルメタン、４，４’−ジカルボキシルジフェニルメタン、３，３’−ジカルボキシルジフェニルジフルオロメタン、３，４’−ジカルボキシルジフェニルジフルオロメタン、４，４’−ジカルボキシルジフェニルジフルオロメタン、３，３’−ジカルボキシルジフェニルスルホン、３，４’−ジカルボキシルジフェニルスルホン、４，４’−ジカルボキシルジフェニルスルホン、３，３’−ジカルボキシルジフェニルスルフィド、３，４’−ジカルボキシルジフェニルスルフィド、４，４’−ジカルボキシルジフェニルスルフィド、３，３’−ジカルボキシルジフェニルケトン、３，４’−ジカルボキシルジフェニルケトン、４，４’−ジカルボキシルジフェニルケトン、２，２−ビス（３−カルボキシフェニル）プロパン、２，２−ビス（３，４’−ジカルボキシフェニル）プロパン、２，２−ビス（４−カルボキシフェニル）プロパン、２，２−ビス（３−カルボキシフェニル）ヘキサフルオロプロパン、２，２−ビス（３，４’−ジカルボキシフェニル）ヘキサフルオロプロパン、２，２−ビス（４−カルボキシフェニル）ヘキサフルオロプロパン、１，３−ビス（３−カルボキシフェノキシ）ベンゼン、１，４−ビス（３−カルボキシフェノキシ）ベンゼン、１，４−ビス（４−カルボキシフェノキシ）ベンゼン、３，３’−（１，４−フェニレンビス（１−メチルエチリデン））ビス安息香酸、３，４’−（１，４−フェニレンビス（１−メチルエチリデン））ビス安息香酸、４，４’−（１，４−フェニレンビス（１−メチルエチリデン））ビス安息香酸、２，２−ビス（４−（３−カルボキシフェノキシ）フェニル）プロパン、２，２−ビス（４−（４−カルボキシフェノキシ）フェニル）プロパン、２，２−ビス（４−（３−カルボキシフェノキシ）フェニル）ヘキサフルオロプロパン、２，２−ビス（４−（４−カルボキシフェノキシ）フェニル）ヘキサフルオロプロパン、ビス（４−（３−カルボキシフェノキシ）フェニル）スルフィド、ビス（４−（４−カルボキシフェノキシ）フェニル）スルフィド、ビス（４−（３−カルボキシフェノキシ）フェニル）スルホン、ビス（４−（４−カルボキシフェノキシ）フェニル）スルホン、５−（パーフルオロノネニルオキシ）イソフタル酸、４−（パーフルオロノネニルオキシ）フタル酸、２−（パーフルオロノネニルオキシ）テレフタル酸、４−メトキシ−５−（パーフルオロノネニルオキシ）イソフタル酸などのパーフルオロノネニルオキシ基含有のジカルボン酸、５−（パーフルオロヘキセニルオキシ）イソフタル酸、４−（パーフルオロヘキセニルオキシ）フタル酸、２−（パーフルオロヘキセニルオキシ）テレフタル酸、４−メトキシ−５−（パーフルオロヘキセニルオキシ）イソフタル酸などのパーフルオロヘキセニルオキシ基含有のジカルボン酸、等の芳香族ジカルボン酸が例示できる。 Examples of the dicarboxylic acid that can be used in the present invention include dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. Phthalic acid, isophthalic acid, terephthalic acid, 3,3′-dicarboxyldiphenyl ether, 3,4′-dicarboxyldiphenyl ether, 4,4′-dicarboxyldiphenyl ether, 3,3′-dicarboxyldiphenylmethane, 3,4′- Dicarboxyl diphenylmethane, 4,4′-dicarboxyldiphenylmethane, 3,3′-dicarboxyldiphenyldifluoromethane, 3,4′-dicarboxyldiphenyldifluoromethane, 4,4′-dicarboxyldiphenyldifluoromethane, 3,3 ′ -Dikarboki Rudiphenyl sulfone, 3,4′-dicarboxyl diphenyl sulfone, 4,4′-dicarboxyl diphenyl sulfone, 3,3′-dicarboxyl diphenyl sulfide, 3,4′-dicarboxyl diphenyl sulfide, 4,4′-di Carboxyl diphenyl sulfide, 3,3′-dicarboxyl diphenyl ketone, 3,4′-dicarboxyl diphenyl ketone, 4,4′-dicarboxyl diphenyl ketone, 2,2-bis (3-carboxyphenyl) propane, 2,2 -Bis (3,4'-dicarboxyphenyl) propane, 2,2-bis (4-carboxyphenyl) propane, 2,2-bis (3-carboxyphenyl) hexafluoropropane, 2,2-bis (3 4'-dicarboxyphenyl) hexafluoropropane, 2,2 Bis (4-carboxyphenyl) hexafluoropropane, 1,3-bis (3-carboxyphenoxy) benzene, 1,4-bis (3-carboxyphenoxy) benzene, 1,4-bis (4-carboxyphenoxy) benzene, 3,3 ′-(1,4-phenylenebis (1-methylethylidene)) bisbenzoic acid, 3,4 ′-(1,4-phenylenebis (1-methylethylidene)) bisbenzoic acid, 4,4 ′ -(1,4-phenylenebis (1-methylethylidene)) bisbenzoic acid, 2,2-bis (4- (3-carboxyphenoxy) phenyl) propane, 2,2-bis (4- (4-carboxyphenoxy) ) Phenyl) propane, 2,2-bis (4- (3-carboxyphenoxy) phenyl) hexafluoropropane, 2,2-bis (4- (4-cal Boxyphenoxy) phenyl) hexafluoropropane, bis (4- (3-carboxyphenoxy) phenyl) sulfide, bis (4- (4-carboxyphenoxy) phenyl) sulfide, bis (4- (3-carboxyphenoxy) phenyl) Sulfone, bis (4- (4-carboxyphenoxy) phenyl) sulfone, 5- (perfluorononenyloxy) isophthalic acid, 4- (perfluorononenyloxy) phthalic acid, 2- (perfluorononenyloxy) terephthalate Acids, perfluorononenyloxy-containing dicarboxylic acids such as 4-methoxy-5- (perfluorononenyloxy) isophthalic acid, 5- (perfluorohexenyloxy) isophthalic acid, 4- (perfluorohexenyloxy) phthalate Acid, 2- (perfluorohexenyl Carboxymethyl) terephthalic acid, 4-methoxy-5- (perfluoroalkyl hexenyloxy) perfluoroalkyl hexenyl group-containing dicarboxylic acids such as isophthalic acid, aromatic dicarboxylic acids and the like can be exemplified.
重合反応の一例として、例えば、本発明の一般式［１］で示される含フッ素重合性単量体と上記のジカルボン酸単量体（一般式［３１］または一般式［３２］）を反応させると、一般式［５］で示される高分子化合物（ポリアミド樹脂）が得られる。 As an example of the polymerization reaction, for example, the fluorine-containing polymerizable monomer represented by the general formula [1] of the present invention and the above dicarboxylic acid monomer (general formula [31] or general formula [32]) are reacted. Then, a polymer compound (polyamide resin) represented by the general formula [5] is obtained.
この重合反応の方法、条件については特に制限されない。例えば、前記ジアミン成分と前記ジカルボン酸のアミド形成性誘導体を１５０℃以上で相互に溶解（溶融）させて無溶媒で反応させる方法、また有機溶媒中高温（好ましくは１５０℃以上）で反応させる方法、−２０〜８０℃の温度で有機溶媒中にて反応する方法があげられる。 The method and conditions for this polymerization reaction are not particularly limited. For example, a method in which the diamine component and the amide-forming derivative of the dicarboxylic acid are mutually dissolved (melted) at 150 ° C. or higher and reacted in a solvent-free manner, or a method of reacting at a high temperature in an organic solvent (preferably 150 ° C. or higher). , A method of reacting in an organic solvent at a temperature of -20 to 80 ° C.
使用できる有機溶媒としては原料の両成分が溶解すれば特に限定されないが、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチルホルムアミド、ヘキサメチルリン酸トリアミド、Ｎ−メチル−２−ピロリドン等のアミド系溶媒、ベンゼン、アニソール、ジフェニルエーテル、ニトロベンゼン、ベンゾニトリル等の芳香族系溶媒、クロロホルム、ジクロロメタン、１，２−ジクロロエタン、１，１，２，２−テトラクロロエタン等のハロゲン系溶媒、γ−ブチロラクトン、γ−バレロラクトン、δ−バレロラクトン、γ−カプロラクトン、ε−カプロラクトン、α−メチル−γ−ブチロラクトン等のラクトン類などを例示することができる。このような有機溶媒とともに、酸受容体、例えば、ピリジン、トリエチルアミンなどを共存させて反応を行うことが効果的である。特に上記のアミド系溶媒を用いるとこれらの溶媒自身が酸受容体となり高重合度のポリアミド樹脂を得ることができる。 The organic solvent that can be used is not particularly limited as long as both components of the raw material dissolve, but N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformamide, hexamethylphosphoric triamide, N-methyl-2- Amido solvents such as pyrrolidone, aromatic solvents such as benzene, anisole, diphenyl ether, nitrobenzene, benzonitrile, halogen solvents such as chloroform, dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, Examples include lactones such as γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, and α-methyl-γ-butyrolactone. It is effective to carry out the reaction in the presence of an acid acceptor such as pyridine or triethylamine together with such an organic solvent. In particular, when the above amide solvents are used, these solvents themselves become acid acceptors, and a polyamide resin having a high degree of polymerization can be obtained.
本発明の含フッ素重合性単量体は、他のジアミン、ジヒドロキシアミンなどと併用した共重合体とすることも可能である。併用できるジアミン化合物としては、３，５−ジアミノベンゾトリフルオリド、２，５−ジアミノベンゾトリフルオリド、３，３’−ビストリフルオロメチル−４，４’−ジアミノビフェニル、３，３’−ビストリフルオロメチル−５，５’−ジアミノビフェニル、ビス（トリフルオロメチル）−４，４’−ジアミノジフェニル、ビス（フッ素化アルキル）−４，４’−ジアミノジフェニル、ジクロロ−４，４’−ジアミノジフェニル、ジブロモ−４，４’−ジアミノジフェニル、ビス（フッ素化アルコキシ）−４，４’−ジアミノジフェニル、ジフェニル−４，４’−ジアミノジフェニル、４，４’−ビス（４−アミノテトラフルオロフェノキシ）テトラフルオロベンゼン、４，４’−ビス（４−アミノテトラフルオロフェノキシ）オクタフルオロビフェニル、４，４’−ビナフチルアミン、ｏ−、ｍ−、ｐ−フェニレンジアミン、２，４−ジアミノトルエン、２，５−ジアミノトルエン、２，４−ジアミノキシレン、２，４−ジアミノジュレン、ジメチル−４，４’−ジアミノジフェニル、ジアルキル−４，４’−ジアミノジフェニル、ジメトキシ−４，４’−ジアミノジフェニル、ジエトキシ−４，４’−ジアミノジフェニル、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルエーテル、３，４’−ジアミノジフェニルエーテル、４，４’−ジアミノジフェニルスルホン、３，３’−ジアミノジフェニルスルホン、４，４’−ジアミノベンゾフェノン、３，３’−ジアミノベンゾフェノン、１，３−ビス（３−アミノフェノキシ）ベンゼン、１，３−ビス（４−アミノフェノキシ）ベンゼン、１，４−ビス（４−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、ビス（４−（３−アミノフェノキシ）フェニル）スルホン、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−（４−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）ヘキサフルオロプロパン、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−（３−アミノフェノキシ）フェニル）ヘキサフルオロプロパン、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、２，２−ビス（４−（３−アミノ−５−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、２，２−ビス（４−アミノフェニル）ヘキサフルオロプロパン、２，２−ビス（３−アミノフェニル）ヘキサフルオロプロパン、２，２−ビス（３−アミノ−４−ヒドロキシフェニル）ヘキサフルオロプロパン、２，２−ビス（３−アミノ−４−メチルフェニル）ヘキサフルオロプロパン、４，４’−ビス（４−アミノフェノキシ）オクタフルオロビフェニル、４，４’−ジアミノベンズアニリド等が例示できる。これらを２種以上併用することもできる。 The fluorine-containing polymerizable monomer of the present invention can be a copolymer used in combination with other diamine, dihydroxyamine and the like. Examples of diamine compounds that can be used in combination include 3,5-diaminobenzotrifluoride, 2,5-diaminobenzotrifluoride, 3,3′-bistrifluoromethyl-4,4′-diaminobiphenyl, and 3,3′-bistrifluoromethyl. -5,5'-diaminobiphenyl, bis (trifluoromethyl) -4,4'-diaminodiphenyl, bis (fluorinated alkyl) -4,4'-diaminodiphenyl, dichloro-4,4'-diaminodiphenyl, dibromo -4,4'-diaminodiphenyl, bis (fluorinated alkoxy) -4,4'-diaminodiphenyl, diphenyl-4,4'-diaminodiphenyl, 4,4'-bis (4-aminotetrafluorophenoxy) tetrafluoro Benzene, 4,4'-bis (4-aminotetrafluorophenoxy) octa Ruorobiphenyl, 4,4'-binaphthylamine, o-, m-, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,4-diaminoxylene, 2,4-diaminoju Len, dimethyl-4,4′-diaminodiphenyl, dialkyl-4,4′-diaminodiphenyl, dimethoxy-4,4′-diaminodiphenyl, diethoxy-4,4′-diaminodiphenyl, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone, 1,3-bis (3-aminophenoxy) benzene, 1,3-bi (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, bis (4- (3-aminophenoxy) phenyl) sulfone, bis (4- (4-aminophenoxy) phenyl) sulfone, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane 2,2-bis (4- (3-aminophenoxy) phenyl) propane, 2,2-bis (4- (3-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4- (4- Amino-2-trifluoromethylphenoxy) phenyl) hexafluoropropane, 2,2-bis (4- (3-amino-5-trifluoromethyl) Ruphenoxy) phenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2-bis (3-amino-4) -Hydroxyphenyl) hexafluoropropane, 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane, 4,4'-bis (4-aminophenoxy) octafluorobiphenyl, 4,4'-diaminobenz Examples include anilide. Two or more of these may be used in combination.
本発明の含フッ素重合性単量体は、ヘキサフルオロプロピル基を保護して、酸により脱離する保護基（酸不安定基）を導入することも可能である。使用できる酸不安定基の例としては、光酸発生剤や加水分解などの効果で脱離が起きる基であれば制限なく使用できる。具体的な例を挙げるとするならば、ｔｅｒｔ−ブトキシカルボニル基、ｔｅｒｔ−アミルオキシカルボニル基、メトキシカルボニル基、エトキシカルボニル基等のアルキコキシカルボニル基、メトキシメチル基、エトキシエチル基、ブトキシエチル基、シクロヘキシルオキシエチル基、ベンジルオキシエチル基等のアセタール基、トリメチルシリル基、エチルジメチルシリル基、メチルジエチルシリル基、トリエチルシリル基のシリル基、アセチル基、プロピオニル基、ブチリル基、ヘプタノイル基、ヘキサノイル基、バレリル基、ピバロイル基等のアシル基等を挙げることができる。 In the fluorine-containing polymerizable monomer of the present invention, a hexafluoropropyl group can be protected and a protecting group (acid labile group) that is eliminated by an acid can be introduced. Examples of the acid labile group that can be used can be used without limitation as long as they are groups that undergo elimination due to effects such as a photoacid generator or hydrolysis. Specific examples include tert-butoxycarbonyl group, tert-amyloxycarbonyl group, alkoxycarbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, methoxymethyl group, ethoxyethyl group, butoxyethyl group. Acetal group such as cyclohexyloxyethyl group, benzyloxyethyl group, trimethylsilyl group, ethyldimethylsilyl group, methyldiethylsilyl group, silyl group of triethylsilyl group, acetyl group, propionyl group, butyryl group, heptanoyl group, hexanoyl group, Examples include acyl groups such as valeryl group and pivaloyl group.
酸脱離基を導入することにより、本発明の含フッ素重合性単量体を用いて重合した高分子化合物をレジスト材料として使用することが可能である。すなわち、分子内のヘキサフルオロイソプロパノール基を酸不安定性の保護基で保護した後に光酸発生剤と混合してレジスト化し、これを露光することによって酸不安定基がはずれ、ヘキサフルオロプロパノール基が生成し、その結果アルカリ現像可能となるので、ポジ型のレジストや感光性材料として有用である。 By introducing an acid leaving group, a polymer compound polymerized using the fluorine-containing polymerizable monomer of the present invention can be used as a resist material. That is, the hexafluoroisopropanol group in the molecule is protected with an acid labile protecting group, then mixed with a photoacid generator to form a resist, and this is exposed to light to release the acid labile group, producing a hexafluoropropanol group. As a result, alkali development becomes possible, which is useful as a positive resist or a photosensitive material.
また、本発明の含フッ素重合性単量体は、他の官能基を付与して使用することも可能である。例えば、不飽和結合を付与することにより架橋部位を導入できる。例えば、本発明の含フッ素重合性単量体と無水マレイン酸を反応させると、ビスマレイミド化して二重結合を導入することができる。この化合物は架橋剤として有用である。 The fluorine-containing polymerizable monomer of the present invention can be used with other functional groups. For example, a crosslinking site can be introduced by imparting an unsaturated bond. For example, when the fluorine-containing polymerizable monomer of the present invention is reacted with maleic anhydride, a double bond can be introduced by bismaleimide formation. This compound is useful as a crosslinking agent.
本発明の一般式［５］で表される高分子化合物を脱水することにより、環化させることができる。一例を示すと、一般式［５］で示される高分子化合物であって、ａ＝１で且つアミノ基のα位に２−ヒドロキシヘキサフルオロ−２−プロピル基を有する化合物（例えば下記式［５−１］）を環化させることにより、一般式［６］で示される高分子化合物が得られる。下記式中、Ｂは脂環、芳香環、アルキレン基から選ばれた一種以上を含有した２価の有機基であり、フッ素、塩素、酸素、硫黄、窒素などを含有してもよく、さらには水素の一部がアルキル基、フルオロアルキル基、カルボキシル基、ヒドロキシ基、シアノ基などで置換されてもよい。ｎは重合度を表す。 The polymer compound represented by the general formula [5] of the present invention can be cyclized by dehydration. As an example, a polymer compound represented by the general formula [5], which has a = 1 and a 2-hydroxyhexafluoro-2-propyl group at the α-position of the amino group (for example, the following formula [5 -1]) is cyclized to give a polymer compound represented by the general formula [6]. In the following formula, B is a divalent organic group containing one or more selected from an alicyclic ring, an aromatic ring, and an alkylene group, and may contain fluorine, chlorine, oxygen, sulfur, nitrogen, etc. A part of hydrogen may be substituted with an alkyl group, a fluoroalkyl group, a carboxyl group, a hydroxy group, a cyano group, or the like. n represents the degree of polymerization.
環化させた場合、耐熱性の向上、溶解性変化、屈折率や誘電率の低下、撥水撥油性の発現など、大きな物性面の変化を伴う樹脂変性を行うことができる。特に本発明の一般式［６］で表される含フッ素高分子化合物は、分子内に環状構造を有することから耐熱性がさらに向上する。
さらに本発明の含フッ素重合性単量体であるジアミンの相手方としてテトラカルボン酸系の誘導体、例えば、一般式［３３］
In the case of cyclization, it is possible to perform resin modification accompanied by a large change in physical properties such as improvement in heat resistance, change in solubility, reduction in refractive index and dielectric constant, and expression of water and oil repellency. In particular, since the fluorine-containing polymer compound represented by the general formula [6] of the present invention has a cyclic structure in the molecule, the heat resistance is further improved.
Furthermore, tetracarboxylic acid derivatives such as the general formula [33] as a counterpart of the diamine which is the fluorine-containing polymerizable monomer of the present invention.
かかるテトラカルボン酸二無水物としては、その構造は特に限定されないが、例えば、ベンゼンテトラカルボン酸二無水物（ピロメリット酸二無水物；ＰＭＤＡ）、トリフルオロメチルベンゼンテトラカルボン酸二無水物、ビストリフルオロメチルベンゼンテトラカルボン酸二無水物、ジフルオロベンゼンテトラカルボン酸二無水物、ナフタレンテトラカルボン酸二無水化物、ビフェニルテトラカルボン酸二無水物、ターフェニルテトラカルボン酸二無水物、ヘキサフルオロイソプロピリデンジフタル酸二無水物、オキシジフタル酸二無水物、ビシクロ（２，２，２）オクト−７−エン−２，３，５，６−テトラカルボン酸二無水物、２，２−ビス（３，４−ジカルボキシフェニル）フェキサフルオロプロパン酸二無水物（６ＦＤＡ）、２，３，４，５−チオフェンテトラカルボン酸二無水化物、２,５,６,２',５',６'- ヘキサフルオロ- ３，３’，４，４’−ビフェニルテトラカルボン酸二無水化物、ビス（３，４−ジカルボキシフェニル）スルホン酸二無水化物、３，４，９，１０−ペリレンテトラカルボン酸二無水化物等を挙げることができなどが挙げられるが、ピロメリット酸、６ＦＤＡが特に好ましい。
これらのテトラカルボン酸二無水物は単独で用いてもよいし、２種以上混合して用いてもよい。本発明において、上記テトラカルボン酸二無水物とアミン成分との使用割合は、テトラカルボン酸二無水物１モルに対して０．９〜１．１モル用いられ、好ましくは０．９５〜１．０５モル、更に好ましくは０．９８〜１．０３モル用いられる。この範囲を外れると、モル比のバランスがくずれ特性が低下するため好ましくない。
重合反応の一例として、例えば、本発明の一般式［１］で示される含フッ素重合性単量体と上記のテトラカルボン酸無水物を反応させると、一般式［７］で示される高分子化合物（ポリアミド酸）が得られる。重合反応の方法、条件については、ジカルボン酸類との反応と同様な重合方法、重合条件を適応することができる。使用できる溶媒も原料の両成分が溶解すれば特に限定されず、ジカルボン酸類との反応と同様な溶媒を用いることができるが、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチルホルムアミド、ヘキサメチルリン酸トリアミド、Ｎ−メチル−２−ピロリドン等のアミド系溶媒、ベンゼン、アニソール、ジフェニルエーテル、ニトロベンゼン、ベンゾニトリル等の芳香族系溶媒、クロロホルム、ジクロロメタン、１，２−ジクロロエタン、１，１，２，２−テトラクロロエタン等のハロゲン系溶媒、γ−ブチロラクトン、γ−バレロラクトン、δ−バレロラクトン、γ−カプロラクトン、ε−カプロラクトン、α−メチル−γ−ブチロラクトン等のラクトン類などを例示することができる。このような有機溶媒とともに、酸受容体、例えば、ピリジン、トリエチルアミンなどを共存させて反応を行うことも同様に効果的である。
The structure of the tetracarboxylic dianhydride is not particularly limited. For example, benzenetetracarboxylic dianhydride (pyromellitic dianhydride; PMDA), trifluoromethylbenzenetetracarboxylic dianhydride, bistri Fluoromethylbenzenetetracarboxylic dianhydride, difluorobenzenetetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, terphenyltetracarboxylic dianhydride, hexafluoroisopropylidenediphthalate Acid dianhydride, oxydiphthalic dianhydride, bicyclo (2,2,2) oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,2-bis (3,4 Dicarboxyphenyl) fexafluoropropanoic acid dianhydride (6FDA), 2, , 4,5-thiophenetetracarboxylic dianhydride, 2,5,6,2 ′, 5 ′, 6′-hexafluoro-3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) sulfonic acid dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride can be mentioned, and pyromellitic acid and 6FDA are particularly preferable. .
These tetracarboxylic dianhydrides may be used alone or in combination of two or more. In the present invention, the ratio of the tetracarboxylic dianhydride and the amine component used is 0.9 to 1.1 mol, preferably 0.95 to 1. mol per mol of tetracarboxylic dianhydride. 05 mol, more preferably 0.98 to 1.03 mol is used. Outside this range, the molar ratio balance is lost and the characteristics are deteriorated.
As an example of the polymerization reaction, for example, when a fluorine-containing polymerizable monomer represented by the general formula [1] of the present invention is reacted with the above tetracarboxylic acid anhydride, a polymer compound represented by the general formula [7] (Polyamic acid) is obtained. Regarding the method and conditions for the polymerization reaction, the same polymerization method and polymerization conditions as those for the reaction with dicarboxylic acids can be applied. The solvent that can be used is not particularly limited as long as both components of the raw material dissolve, and a solvent similar to the reaction with dicarboxylic acids can be used. N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl Amide solvents such as formamide, hexamethylphosphoric triamide, N-methyl-2-pyrrolidone, aromatic solvents such as benzene, anisole, diphenyl ether, nitrobenzene, benzonitrile, chloroform, dichloromethane, 1,2-dichloroethane, 1, Examples include halogen solvents such as 1,2,2-tetrachloroethane, lactones such as γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, and α-methyl-γ-butyrolactone. can do. It is also effective to conduct the reaction in the presence of an acid acceptor such as pyridine and triethylamine together with such an organic solvent.
また、ジカルボン酸類との反応と同様に他のジアミン、ジヒドロキシアミンなどと併用した共重合体とすることも可能である。併用できるジアミン化合物としては前記のジアミンを用いることができ、２種以上を併用できることも同様である。
前述した一般式［７］で表されるポリアミド酸は加熱または脱水試薬によってイミド化反応することにより一般式［８］で表される含フッ素脂環式ポリイミドとすることができる。加熱イミド化を行う場合、８０〜４００℃の温度で処理可能であるが、特に１５０〜３５０℃の温度範囲が好ましい。イミド化温度が１５０℃未満の場合はイミド化率が低いためポリイミド膜の膜強度が損なわれるため好ましくなく、３５０℃を超える場合は塗膜が着色したり脆くなるので問題がある。また熱処理に代えて無水酢酸などの脱水試薬と反応させて化学的に行うこともできる。
Moreover, it can also be set as the copolymer used together with other diamine, dihydroxyamine, etc. similarly to reaction with dicarboxylic acids. As the diamine compound that can be used in combination, the above-mentioned diamines can be used, and it is also the same that two or more types can be used in combination.
The above-mentioned polyamic acid represented by the general formula [7] can be converted to a fluorinated alicyclic polyimide represented by the general formula [8] by heating or imidizing with a dehydrating reagent. When heat imidization is performed, the treatment can be performed at a temperature of 80 to 400 ° C, and a temperature range of 150 to 350 ° C is particularly preferable. When the imidization temperature is less than 150 ° C., the imidation rate is low, and thus the film strength of the polyimide film is impaired. Therefore, when it exceeds 350 ° C., there is a problem because the coating film is colored or brittle. Moreover, it can replace with heat processing and can be made to react chemically with dehydrating reagents, such as acetic anhydride.
本発明の含フッ素重合体は有機溶媒に溶解したワニス状態、または粉末状態、フィルム状態、固体状態で使用に供することが可能である。ワニスで使用する場合は、ガラス、シリコンウエーハ、金属、金属酸化物、セラミックス、樹脂などの基材上にスピンコート、スプレーコート、フローコート、含浸コート、ハケ塗りなど通常用いられる方法で塗布することができる。
［実施例］
次に本発明を実施例によりさらに詳細に説明する。
The fluoropolymer of the present invention can be used in a varnish state dissolved in an organic solvent, or in a powder state, a film state, or a solid state. When using in varnish, apply it on a substrate such as glass, silicon wafer, metal, metal oxide, ceramics, resin, etc. by usual methods such as spin coating, spray coating, flow coating, impregnation coating, brush coating. Can do.
[Example]
Next, the present invention will be described in more detail with reference to examples.
１−（２−ヒドロキシヘキサフルオロ−２−プロピル）−２，５−フェニレンジアミンの製造
１００ｍｌのガラス製密封容器（オートクレーブ）内に１、４−フェニレンジアミン １０．０ｇ（９２．５ｍｍｏｌ）、ｐ−トルエンスルホン酸・一水和物 ３５２ｍｇ（１．８５ｍｍｏｌ、２ｍｏｌ％）、およびキシレン２０ｍｌを仕込み、系内を窒素雰囲気にした。次いで昇温を開始し、反応液の内温を１００℃とした後、５０分間かけてヘキサフルオロアセトンを３２．２ｇ（１９４ｍｍｏｌ、２．１当量）導入した。内温１２０℃にて１．５時間反応後、反応液を冷却した。反応液をガスクロマトグラフィー（ＧＣ）で分析したところ、目的化合物である１−（２−ヒドロキシヘキサフルオロ−２−プロピル）−２，５−フェニレンジアミンが４７．６％、ヘキサフルオロアセトンと１、４−フェニレンジアミンのアミン部が反応することにより生じた種々のイミン体が合計２０．７％であった。
Production of 1- (2-hydroxyhexafluoro-2-propyl) -2,5-phenylenediamine In a 100 ml glass sealed container (autoclave), 10.0 g (92.5 mmol) of 1,4-phenylenediamine, p- Toluenesulfonic acid monohydrate 352 mg (1.85 mmol, 2 mol%) and xylene 20 ml were charged, and the inside of the system was put into a nitrogen atmosphere. Next, the temperature was raised and the internal temperature of the reaction solution was set to 100 ° C., and then 32.2 g (194 mmol, 2.1 equivalents) of hexafluoroacetone was introduced over 50 minutes. After reacting at an internal temperature of 120 ° C. for 1.5 hours, the reaction solution was cooled. When the reaction solution was analyzed by gas chromatography (GC), the target compound 1- (2-hydroxyhexafluoro-2-propyl) -2,5-phenylenediamine was 47.6%, hexafluoroacetone and 1, The total of various imines formed by the reaction of the amine part of 4-phenylenediamine was 20.7%.
１−（２−ヒドロキシヘキサフルオロ−２−プロピル）−２，５−フェニレンジアミン（一般式［４］）の製造
１００ｍｌのガラス製密封容器（オートクレーブ）内に１、４−フェニレンジアミン１０．０ｇ（９２．５ｍｍｏｌ）、ｐ−トルエンスルホン酸・一水和物 ７０４ｍｇ（３．７０ｍｍｏｌ、４ｍｏｌ％）、およびヘキサフルオロアセトン・三水和物４０．７ｇ（１８５ｍｍｏｌ、２当量）を仕込み、系内を窒素雰囲気にした。次いで昇温を開始し、反応液の内温を１１０℃とした。２１時間攪拌後、反応液を冷却した。反応液をガスクロマトグラフィー（ＧＣ）で分析したところ、目的化合物である１−（２−ヒドロキシヘキサフルオロ−２−プロピル）−２，５−フェニレンジアミンが７５．５％、１、４−フェニレンジアミンが３．６％、ヘキサフルオロアセトンと１、４−フェニレンジアミンのアミン部が反応することにより生じたイミン体が２０．９％であった。反応液に水２００ｍｌを加え、氷浴にて冷却した。析出した固体を濾過、減圧乾燥して、粗１−（２−ヒドロキシヘキサフルオロ−２−プロピル）−２，５−フェニレンジアミンを２４．７ｇ（収率９７％、純度７８．９％）得た。この粗体をトルエン中で再結晶することにより、目的とする１−（２−ヒドロキシヘキサフルオロ−２−プロピル）−２，５−フェニレンジアミンを１８．６ｇ（収率７３％、純度９９．４％）得た。
Production of 1- (2-hydroxyhexafluoro-2-propyl) -2,5-phenylenediamine (general formula [4]) In a 100 ml sealed glass container (autoclave), 10.0 g of 1,4-phenylenediamine ( 92.5 mmol), 704 mg (3.70 mmol, 4 mol%) of p-toluenesulfonic acid monohydrate, and 40.7 g (185 mmol, 2 equivalents) of hexafluoroacetone trihydrate were charged, and the system was filled with nitrogen. It was an atmosphere. Next, the temperature increase was started, and the internal temperature of the reaction solution was adjusted to 110 ° C. After stirring for 21 hours, the reaction solution was cooled. When the reaction solution was analyzed by gas chromatography (GC), the target compound, 1- (2-hydroxyhexafluoro-2-propyl) -2,5-phenylenediamine, was 75.5% and 1,4-phenylenediamine. Was 3.6%, and the imine form produced by the reaction of hexafluoroacetone with the amine portion of 1,4-phenylenediamine was 20.9%. 200 ml of water was added to the reaction solution and cooled in an ice bath. The precipitated solid was filtered and dried under reduced pressure to obtain 24.7 g (yield 97%, purity 78.9%) of crude 1- (2-hydroxyhexafluoro-2-propyl) -2,5-phenylenediamine. . By recrystallizing this crude product in toluene, 18.6 g (yield 73%, purity 99.4) of the target 1- (2-hydroxyhexafluoro-2-propyl) -2,5-phenylenediamine was obtained. %)Obtained.
［１−（２−ヒドロキシヘキサフルオロ−２−プロピル）−２，５−フェニレンジアミンの物性］
紫色粉末。融点１８４．５−１８５．５℃。1Ｈ−ＮＭＲ（基準物質：ＴＭＳ、溶媒：（ＣＤ3）2ＣＯ）δ（ｐｐｍ）：２．８３（ｂｒ，２Ｈ），４．８０（ｂｒ，２Ｈ），６．７１（ｄｄ，１Ｈ，Ｊ＝２．６，８．５Ｈｚ），６．８８（ｍ，１Ｈ），６．９８（ｄ，１Ｈ，Ｊ＝８．５Ｈｚ）。19Ｆ−ＮＭＲ（基準物質：ＣＣｌ3Ｆ、溶媒：（ＣＤ3）2ＣＯ）δ（ｐｐｍ）：−７５．０（ｓ，６Ｆ）。
[Physical properties of 1- (2-hydroxyhexafluoro-2-propyl) -2,5-phenylenediamine]
Purple powder. Melting point 184.5-185.5 ° C. 1 H-NMR (reference material: TMS, solvent: (CD 3 ) 2 CO) δ (ppm): 2.83 (br, 2H), 4.80 (br, 2H), 6.71 (dd, 1H, J = 2.6, 8.5 Hz), 6.88 (m, 1H), 6.98 (d, 1H, J = 8.5 Hz). 19 F-NMR (reference substance: CCl 3 F, solvent: (CD 3 ) 2 CO) δ (ppm): −75.0 (s, 6F).
実施例２で合成した１−（２−ヒドロキシヘキサフルオロ−２−プロピル）−２，５−フェニレンジアミンを用いて、次に示すジカルボン酸クロリドの化合物（ａ）と重合反応を行った。 Using 1- (2-hydroxyhexafluoro-2-propyl) -2,5-phenylenediamine synthesized in Example 2, a polymerization reaction was performed with the following dicarboxylic acid chloride compound (a).
実施例３の化合物（ａ）の代わりにジカルボン酸ジクロリドとして化合物（ｂ）および化合物（ｃ）を用いて、同様の条件下で１−（２−ヒドロキシヘキサフルオロ−２−プロピル）−２，５−フェニレンジアミンとそれぞれ重合させた。 1- (2-hydroxyhexafluoro-2-propyl) -2,5 under the same conditions using compound (b) and compound (c) as dicarboxylic acid dichloride instead of compound (a) in Example 3 -Polymerized with phenylenediamine, respectively.
実施例３および実施例４で合成した高分子（Ａ）、（Ｂ）、（Ｃ）のγ−ブチロラクトン溶液をガラス基板上に展開し、１２０℃で２時間乾燥したところ、どの場合も透明で強靱なフィルムを得た。 The γ-butyrolactone solutions of the polymers (A), (B), and (C) synthesized in Example 3 and Example 4 were spread on a glass substrate and dried at 120 ° C. for 2 hours. A tough film was obtained.
次いで、得られた高分子（Ａ）のフィルム（４０ミクロン厚み）を２８０℃で２時間熱処理を行ったところ、次に示す高分子（Ｄ）に閉環し、強靱なフィルムを得た。得られたフィルムの熱分解温度を測定したところ４００℃でも安定に保持した。また１ｋＨｚの誘電率は２．８であった（高分子（Ｄ）の重量平均分子量（Ｍｗ）：１００００）。 Subsequently, when the obtained polymer (A) film (thickness: 40 microns) was heat-treated at 280 ° C. for 2 hours, the polymer (D) shown below was closed to obtain a tough film. When the thermal decomposition temperature of the obtained film was measured, it was kept stable even at 400 ° C. The dielectric constant at 1 kHz was 2.8 (weight average molecular weight (Mw) of polymer (D): 10,000).
実施例２で合成した１−（２−ヒドロキシヘキサフルオロ−２−プロピル）−２，５−フェニレンジアミン（一般式［４］）を用いて、次に示すテトラカルボン酸無水物化合物(ｄ)、（ｅ）、（ｆ）との重合反応を行った。 Using 1- (2-hydroxyhexafluoro-2-propyl) -2,5-phenylenediamine (general formula [4]) synthesized in Example 2, the following tetracarboxylic anhydride compound (d), A polymerization reaction with (e) and (f) was performed.
これらの高分子溶液をシリコンウエハー上に塗布したところ、均一性の高い強靭で透明なフィルムが生成した。 When these polymer solutions were applied onto a silicon wafer, a highly uniform tough and transparent film was produced.
実施例６で得られた高分子（Ｅ）、（Ｆ）、（Ｇ）を固形分１０％になるようにγ−ブチロラクトン溶液を調整し、無水酢酸とピリジンを添加し、５０℃で２時間、攪拌混合し、化学反応によるイミド化処理を行った。得られた高分子溶液をメタノールに再沈処理し、清浄なメタノールで３回繰り返し攪拌洗浄を行ったのち、室温で真空乾燥した。得られた高分子固体は、イミド環化が確認されたものの、ジメチルアセトアミドに可溶であり、可溶性ポリイミドで（Ｈ）、（Ｉ）、（Ｊ）あることがわかった。次いで（Ｈ）、（Ｉ）、（Ｊ）を１２％の固形分になるようにそれぞれジメチルアセトアミド溶液を調整し、シリコンウエハー上にスピンコートしたところ、強靭な含フッ素高分子膜が得られた。一方、高分子（Ｅ）、（Ｆ）、（Ｇ）のフィルムを３５０℃で１時間熱処理を行ったところ、同様な脱水反応を起こし、やはりポリイミド（Ｈ）、（Ｉ）、（Ｊ）が生成していた。 A γ-butyrolactone solution was prepared so that the polymers (E), (F), and (G) obtained in Example 6 had a solid content of 10%, acetic anhydride and pyridine were added, and the mixture was added at 50 ° C. for 2 hours. Then, the mixture was stirred and imidized by a chemical reaction. The obtained polymer solution was re-precipitated in methanol, repeatedly stirred and washed three times with clean methanol, and then vacuum dried at room temperature. Although the obtained polymer solid was confirmed to be imide cyclization, it was found to be soluble in dimethylacetamide and (H), (I), (J) as soluble polyimide. Next, when (H), (I), and (J) were each adjusted to a dimethylacetamide solution so as to have a solid content of 12% and spin-coated on a silicon wafer, a tough fluorine-containing polymer film was obtained. . On the other hand, when the polymer (E), (F), and (G) films were heat-treated at 350 ° C. for 1 hour, the same dehydration reaction was caused, and the polyimides (H), (I), and (J) were also converted. It was generated.
次いで、高分子（Ｈ）、（Ｉ）、（Ｊ）の熱分解温度をＤＳＣ（示差熱操作熱量計）にて測定したところ、５％重量減少温度として、それぞれ、４６５℃、４５０℃、４２０℃と高い耐熱性を示し、さらに１ＭＨｚでの誘電率をＬＣＲメーターを用いて測定したところ、それぞれ２．８、２．６、２．４と低い値を示した。 Subsequently, when the thermal decomposition temperature of polymer (H), (I), (J) was measured with DSC (differential heat operation calorimeter), it was set as 465 degreeC, 450 degreeC, 420 as 5% weight loss temperature, respectively. When the dielectric constant at 1 MHz was measured using an LCR meter, it showed a low value of 2.8, 2.6, and 2.4, respectively.
本発明の含フッ素重合性単量体は、分子内に複数の重合性アミンを有し、かつ同時にヘキサフルオロイソプロピル基を有することで、撥水性、撥油性、低吸水性、耐熱性、耐候性、耐腐食性、透明性、感光性、低屈折率性、低誘電性などを発現できる有効な重合性単量体として使用することができ、先端高分子材料分野に供することが可能である。しかもヘキサフルオロイソプロピル基はアルカリ可溶性を有する酸性基であり、低誘電性、高溶解性、高コントラストなどを有した電子デバイス用感光性絶縁膜として使用することも可能にする。
The fluorine-containing polymerizable monomer of the present invention has a plurality of polymerizable amines in the molecule and simultaneously has a hexafluoroisopropyl group, so that it has water repellency, oil repellency, low water absorption, heat resistance, weather resistance. It can be used as an effective polymerizable monomer that can exhibit corrosion resistance, transparency, photosensitivity, low refractive index property, low dielectric property, etc., and can be used in the field of advanced polymer materials. Moreover, the hexafluoroisopropyl group is an acidic group having alkali solubility, and can be used as a photosensitive insulating film for electronic devices having low dielectric properties, high solubility, high contrast, and the like.
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| JP5233457B2 (en) * | 2007-07-17 | 2013-07-10 | セントラル硝子株式会社 | Novel fluorine-containing dicarboxylic acid and novel polymer compound using the same |
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| WO2010053186A1 (en) * | 2008-11-10 | 2010-05-14 | 味の素株式会社 | Siloxane-containing polyimide resin |
| US20100216967A1 (en) * | 2009-02-20 | 2010-08-26 | International Business Machines Corporation | Interfacial polymerization methods for making fluoroalcohol-containing polyamides |
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| WO2015186782A1 (en) * | 2014-06-04 | 2015-12-10 | 宇部興産株式会社 | Method for producing polyimide film |
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