JP6778377B2 - A method for producing an aromatic polyketone having an alkylene group in the main chain, an aromatic polyketone varnish, an aromatic polyketone film, and an aromatic polyketone. - Google Patents
A method for producing an aromatic polyketone having an alkylene group in the main chain, an aromatic polyketone varnish, an aromatic polyketone film, and an aromatic polyketone. Download PDFInfo
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- JP6778377B2 JP6778377B2 JP2016014441A JP2016014441A JP6778377B2 JP 6778377 B2 JP6778377 B2 JP 6778377B2 JP 2016014441 A JP2016014441 A JP 2016014441A JP 2016014441 A JP2016014441 A JP 2016014441A JP 6778377 B2 JP6778377 B2 JP 6778377B2
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- substituent
- polyketone
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- 229920001470 polyketone Polymers 0.000 title claims description 148
- 125000003118 aryl group Chemical group 0.000 title claims description 103
- 239000002966 varnish Substances 0.000 title claims description 35
- 125000002947 alkylene group Chemical group 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 67
- 125000001424 substituent group Chemical group 0.000 claims description 56
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 24
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 20
- 125000002723 alicyclic group Chemical group 0.000 claims description 14
- 238000006482 condensation reaction Methods 0.000 claims description 14
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 7
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 15
- 150000002430 hydrocarbons Chemical group 0.000 description 47
- 238000000034 method Methods 0.000 description 20
- 239000000758 substrate Substances 0.000 description 15
- -1 n-octyl group Chemical group 0.000 description 13
- 239000000463 material Substances 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- PAVQGHWQOQZQEH-UHFFFAOYSA-N adamantane-1,3-dicarboxylic acid Chemical compound C1C(C2)CC3CC1(C(=O)O)CC2(C(O)=O)C3 PAVQGHWQOQZQEH-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- VGMKUVCDINAAFC-UHFFFAOYSA-N 1-methoxy-2-(2-methoxyphenyl)benzene Chemical group COC1=CC=CC=C1C1=CC=CC=C1OC VGMKUVCDINAAFC-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000002252 acyl group Chemical group 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LLNAMUJRIZIXHF-CLFYSBASSA-N (z)-2-methyl-3-phenylprop-2-en-1-ol Chemical compound OCC(/C)=C\C1=CC=CC=C1 LLNAMUJRIZIXHF-CLFYSBASSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- LTEQMZWBSYACLV-UHFFFAOYSA-N Hexylbenzene Chemical compound CCCCCCC1=CC=CC=C1 LTEQMZWBSYACLV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical group C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229960002255 azelaic acid Drugs 0.000 description 2
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 210000002858 crystal cell Anatomy 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- 230000000474 nursing effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920001643 poly(ether ketone) Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-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
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- GVSTYPOYHNVKHY-UHFFFAOYSA-N 2-methoxybutanoic acid Chemical compound CCC(OC)C(O)=O GVSTYPOYHNVKHY-UHFFFAOYSA-N 0.000 description 1
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical group CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- LDMRLRNXHLPZJN-UHFFFAOYSA-N 3-propoxypropan-1-ol Chemical compound CCCOCCCO LDMRLRNXHLPZJN-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
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- 229940081735 acetylcellulose Drugs 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 229940007550 benzyl acetate Drugs 0.000 description 1
- XTHLMMQPSUSPPS-UHFFFAOYSA-N bicyclo[2.2.1]heptane-1,4-dicarboxylic acid Chemical compound C1CC2(C(O)=O)CCC1(C(=O)O)C2 XTHLMMQPSUSPPS-UHFFFAOYSA-N 0.000 description 1
- IVVOCRBADNIWDM-UHFFFAOYSA-N bicyclo[2.2.1]heptane-2,3-dicarboxylic acid Chemical compound C1CC2C(C(O)=O)C(C(=O)O)C1C2 IVVOCRBADNIWDM-UHFFFAOYSA-N 0.000 description 1
- TYOIRTKMCCIKFR-UHFFFAOYSA-N bicyclo[2.2.1]heptane-2,4-dicarboxylic acid Chemical compound C1CC2C(C(=O)O)CC1(C(O)=O)C2 TYOIRTKMCCIKFR-UHFFFAOYSA-N 0.000 description 1
- GPRLTFBKWDERLU-UHFFFAOYSA-N bicyclo[2.2.2]octane Chemical group C1CC2CCC1CC2 GPRLTFBKWDERLU-UHFFFAOYSA-N 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
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- 239000007795 chemical reaction product Substances 0.000 description 1
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- 239000011248 coating agent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- TXWRERCHRDBNLG-UHFFFAOYSA-N cubane Chemical group C12C3C4C1C1C4C3C12 TXWRERCHRDBNLG-UHFFFAOYSA-N 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical group CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZICQBHNGXDOVJF-UHFFFAOYSA-N diamantane Chemical group C1C2C3CC(C4)CC2C2C4C3CC1C2 ZICQBHNGXDOVJF-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
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- 239000012153 distilled water Substances 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- UHKJHMOIRYZSTH-UHFFFAOYSA-N ethyl 2-ethoxypropanoate Chemical compound CCOC(C)C(=O)OCC UHKJHMOIRYZSTH-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011416 infrared curing Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([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
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000011415 microwave curing Methods 0.000 description 1
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical group C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- 238000007339 nucleophilic aromatic substitution reaction Methods 0.000 description 1
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- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
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- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
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- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical group C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
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Landscapes
- Polyethers (AREA)
- Optical Elements Other Than Lenses (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、芳香族ポリケトン、芳香族ポリケトンワニス、芳香族ポリケトン膜及び芳香族ポリケトンの製造方法に関する。 The present invention relates to an aromatic polyketone, an aromatic polyketone varnish, an aromatic polyketone film, and a method for producing an aromatic polyketone.
主鎖に芳香環とカルボニル基を有する芳香族ポリケトンは、優れた耐熱性と機械特性を有しており、エンジニアリングプラスチックとして利用されている。芳香族ポリケトンに属する高分子のほとんどは、求核芳香族置換反応を利用して重合された芳香族ポリエーテルケトンであり、主鎖にエーテル結合も有している。これに対し、主鎖にエーテル結合を有していない芳香族ポリケトンは、芳香族ポリエーテルケトンよりも更に優れた耐熱性及び耐薬品性を発揮しうる（例えば、特許文献１及び特許文献２参照）。 Aromatic polyketones having an aromatic ring and a carbonyl group in the main chain have excellent heat resistance and mechanical properties, and are used as engineering plastics. Most of the polymers belonging to the aromatic polyketone are aromatic polyetherketones polymerized by utilizing the nucleophilic aromatic substitution reaction, and also have an ether bond in the main chain. On the other hand, an aromatic polyketone having no ether bond in the main chain can exhibit more excellent heat resistance and chemical resistance than the aromatic polyetherketone (see, for example, Patent Document 1 and Patent Document 2). ).
近年、脂環式ジカルボン酸と２，２’−ジアルコキシビフェニル化合物をＦｒｉｅｄｅｌ−Ｃｒａｆｔｓアシル化により直接重合することで、高い透明性と耐熱性とを両立した芳香族ポリケトンを得ることができることが報告され、光学部品への応用が期待されている（例えば、特許文献３参照）。 In recent years, it has been reported that an aromatic polyketone having both high transparency and heat resistance can be obtained by directly polymerizing an alicyclic dicarboxylic acid and a 2,2'-dialkoxybiphenyl compound by Friedel-Crafts acylation. It is expected to be applied to optical components (see, for example, Patent Document 3).
樹脂材料を光学部品に応用する場合には、無機材料では得られない特性が期待され、そのような特性としては、例えば、軽量性及び柔軟性が挙げられる。軽量性を活かした適用例としては、ポータブルデバイスのガラス代替材及びコート材が挙げられ、柔軟さを活かした適用例としては、フレキシブルディスプレイ等が挙げられる。なかでも、フレキシブルディスプレイへの樹脂材料の適用は、近年特に注目されている。 When a resin material is applied to an optical component, properties that cannot be obtained with an inorganic material are expected, and such properties include, for example, light weight and flexibility. Examples of applications that utilize lightness include glass substitutes and coating materials for portable devices, and examples of applications that utilize flexibility include flexible displays and the like. In particular, the application of resin materials to flexible displays has attracted particular attention in recent years.
しかし、特許文献３に記載の脂環式ジカルボン酸と２，２’−ジアルコキシビフェニル化合物から重合される芳香族ポリケトンは、優れた耐熱性と透明性を有する一方で、成形品が硬くなりやすい。このことにより、折り曲げ可能な柔軟な膜を得ることが難しい。 However, the aromatic polyketone polymerized from the alicyclic dicarboxylic acid and the 2,2'-dialkoxybiphenyl compound described in Patent Document 3 has excellent heat resistance and transparency, but the molded product tends to be hard. .. This makes it difficult to obtain a foldable and flexible film.
本発明は上記状況に鑑みなされたものであり、優れた耐熱性と透明性を有し、柔軟な膜を形成可能な芳香族ポリケトン、芳香族ポリケトンワニス及び芳香族ポリケトンの製造方法、並びに優れた耐熱性と透明性と柔軟性とを有する芳香族ポリケトン膜を提供する。 The present invention has been made in view of the above circumstances, and has excellent heat resistance and transparency, a method for producing an aromatic polyketone, an aromatic polyketone varnish and an aromatic polyketone capable of forming a flexible film, and an excellent method. Provided is an aromatic polyketone film having heat resistance, transparency and flexibility.
本発明は、下記＜１＞〜＜７＞の態様を含む。 The present invention includes the following aspects <1> to <7>.
＜１＞ 下記一般式（１）、下記一般式（２）及び下記一般式（４）からなる群より選択される少なくとも１種の構造単位と、下記一般式（５−１）で表される少なくとも１種の構造単位と、下記一般式（５−２）で表される少なくとも１種の構造単位と、を有する芳香族ポリケトン。 <1> Represented by at least one structural unit selected from the group consisting of the following general formula (1), the following general formula (2), and the following general formula (4), and the following general formula (5-1). An aromatic polyketone having at least one structural unit and at least one structural unit represented by the following general formula (5-2).
一般式（１）中、Ｒ１はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を示し、Ｒ２はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を示す。 In the general formula (1), R 1 independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a hydrogen atom or a substituent, and R 2 is an independent hydrogen atom or a substituent. Indicates a hydrocarbon group having 1 to 30 carbon atoms which may have.
一般式（２）中、Ｒ１はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を示し、Ｘは酸素原子又は下記一般式（３）で表される２価の基を示す。 In the general formula (2), R 1 independently represents a hydrocarbon atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and X is an oxygen atom or the following general formula (3). The divalent group represented is shown.
一般式（３）中、Ｒ３及びＲ４はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を示す。 In the general formula (3), R 3 and R 4 each independently represent a hydrocarbon group having 1 to 30 carbon atoms which may have a hydrogen atom or a substituent.
一般式（４）中、Ｒ５はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を示す。 In the general formula (4), R 5 independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a hydrogen atom or a substituent.
一般式（５−１）中、Ｙ１は、置換基を有していてもよい炭素数３〜３０の２価の脂環式炭化水素基を示す。一般式（５−２）中、Ｙ２は、置換基を有していてもよい炭素数１〜３０の直鎖状又は分岐鎖状アルキレン基を示す。 In the general formula (5-1), Y 1 represents a divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms which may have a substituent. In the general formula (5-2), Y 2 represents a linear or branched chain alkylene group having 1 to 30 carbon atoms which may have a substituent.
＜２＞ 下記一般式（１’）、下記一般式（２’）及び下記一般式（４’）からなる群より選択される少なくとも１種の芳香族モノマと、下記一般式（５−１’）で表される少なくとも１種のジカルボン酸モノマと、下記一般式（５−２’）で表される少なくとも１種のジカルボン酸モノマとを、酸性媒体中で縮合反応させることで得た芳香族ポリケトン。 <2> At least one aromatic monomer selected from the group consisting of the following general formula (1'), the following general formula (2') and the following general formula (4'), and the following general formula (5-1'). ) And at least one dicarboxylic acid monomer represented by the following general formula (5-2') are condensed in an acidic medium to obtain an aromatic acid. Polyketone.
一般式（１’）中、Ｒ１はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を示し、Ｒ２はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を示す。 In the general formula (1'), R 1 independently represents a hydrocarbon atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R 2 is an independent hydrogen atom or a substituent. A hydrocarbon group having 1 to 30 carbon atoms which may have a group is shown.
一般式（２’）中、Ｒ１はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を示し、Ｘは酸素原子又は下記一般式（３’）で表される２価の基を示す。 In the general formula (2'), R 1 independently represents a hydrocarbon atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and X is an oxygen atom or the following general formula (3'). ) Indicates a divalent group.
一般式（３’）中、Ｒ３及びＲ４はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を示す。 In the general formula (3'), R 3 and R 4 each independently represent a hydrocarbon group having 1 to 30 carbon atoms which may have a hydrogen atom or a substituent.
一般式（４’）中、Ｒ５はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を示す。 In the general formula (4'), R 5 independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a hydrogen atom or a substituent.
一般式（５−１’）中、Ｙ１は、置換基を有していてもよい炭素数３〜３０の２価の脂環式炭化水素基を示す。一般式（５−２’）中、Ｙ２は、置換基を有していてもよい炭素数１〜３０の直鎖状又は分岐鎖状アルキレン基を示す。 In the general formula (5-1'), Y 1 represents a divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms which may have a substituent. In the general formula (5-2'), Y 2 represents a linear or branched chain alkylene group having 1 to 30 carbon atoms which may have a substituent.
＜３＞ 前記Ｙ１とＹ２のモル比（Ｙ１：Ｙ２）が、９：１〜３：７である、＜１＞又は＜２＞に記載の芳香族ポリケトン。 <3> The aromatic polyketone according to <1> or <2>, wherein the molar ratio of Y 1 to Y 2 (Y 1 : Y 2 ) is 9: 1 to 3: 7.
＜４＞ ＜１＞〜＜３＞のいずれか１項に記載の芳香族ポリケトンと、溶媒と、を含有する、芳香族ポリケトンワニス。 <4> An aromatic polyketone varnish containing the aromatic polyketone according to any one of <1> to <3> and a solvent.
＜５＞ ＜１＞〜＜３＞のいずれか１項に記載の芳香族ポリケトンを含有する芳香族ポリケトン膜。 <5> An aromatic polyketone film containing the aromatic polyketone according to any one of <1> to <3>.
＜６＞ ＜５＞に記載の芳香族ポリケトン膜を有する表示素子。 <6> A display device having the aromatic polyketone film according to <5>.
＜７＞ 下記一般式（１’）、下記一般式（２’）及び下記一般式（４’）からなる群より選択される少なくとも１種の芳香族モノマと、下記一般式（５−１’）で表される少なくとも１種のジカルボン酸モノマと、下記一般式（５−２）で表される少なくとも１種のジカルボン酸モノマとを、酸性媒体中で縮合反応させる、芳香族ポリケトンの製造方法。 <7> At least one aromatic monomer selected from the group consisting of the following general formula (1'), the following general formula (2') and the following general formula (4'), and the following general formula (5-1'). ) And at least one dicarboxylic acid monomer represented by the following general formula (5-2) are condensed in an acidic medium to produce an aromatic polyketone. ..
一般式（１’）中、Ｒ１はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を示し、Ｒ２はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を示す。 In the general formula (1'), R 1 independently represents a hydrocarbon atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R 2 is an independent hydrogen atom or a substituent. A hydrocarbon group having 1 to 30 carbon atoms which may have a group is shown.
一般式（２’）中、Ｒ１はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を示し、Ｘは酸素原子又は下記一般式（３’）で表される２価の基を示す。 In the general formula (2'), R 1 independently represents a hydrocarbon atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and X is an oxygen atom or the following general formula (3'). ) Indicates a divalent group.
一般式（３’）中、Ｒ３及びＲ４はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を示す。 In the general formula (3'), R 3 and R 4 each independently represent a hydrocarbon group having 1 to 30 carbon atoms which may have a hydrogen atom or a substituent.
一般式（４’）中、Ｒ５はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を示す。 In the general formula (4'), R 5 independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a hydrogen atom or a substituent.
一般式（５−１’）中、Ｙ１は、置換基を有していてもよい炭素数３〜３０の２価の脂環式炭化水素基を示す。一般式（５−２’）中、Ｙ２は、置換基を有していてもよい炭素数１〜３０の直鎖状又は分岐鎖状アルキレン基を示す。 In the general formula (5-1'), Y 1 represents a divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms which may have a substituent. In the general formula (5-2'), Y 2 represents a linear or branched chain alkylene group having 1 to 30 carbon atoms which may have a substituent.
本発明によれば、優れた耐熱性と透明性を有し、柔軟な膜を形成可能な芳香族ポリケトン、芳香族ポリケトンワニス及び芳香族ポリケトンの製造方法、並びに優れた耐熱性と透明性と柔軟性とを有する芳香族ポリケトン膜を提供することができる。 According to the present invention, a method for producing an aromatic polyketone, an aromatic polyketone varnish and an aromatic polyketone having excellent heat resistance and transparency and capable of forming a flexible film, and excellent heat resistance, transparency and flexibility. It is possible to provide an aromatic polyketone film having sex.
以下、本発明について詳細に説明する。ただし、本発明は以下の実施形態に限定されるものではない。
本明細書において「〜」を用いて示された数値範囲は、「〜」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。
本明細書において「膜」とは、平面図として観察したときに、全面に形成されている形状の構成に加え、一部に形成されている形状の構成も包含される。
本明細書において「工程」とは、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、本用語に含まれる。
本明細書において「透明性」とは、可視光の透過性、少なくとも波長４００ｎｍの可視光の透過性が８０％以上（膜厚１μｍ換算）であることを意味する。
本明細書において「耐熱性」とは、芳香族ポリケトンを含有する部材において、加熱によるクラックの発生が抑制されていることを意味する。
本明細書において「柔軟性」とは、芳香族ポリケトン膜についてマンドレル試験を行なったときに、心棒の直径を小さくした場合にクラックの発生が抑制されていることを意味する。
Hereinafter, the present invention will be described in detail. However, the present invention is not limited to the following embodiments.
The numerical range indicated by using "~" in the present specification indicates a range including the numerical values before and after "~" as the minimum value and the maximum value, respectively.
In the present specification, the term "film" includes not only a shape structure formed on the entire surface but also a shape structure formed on a part thereof when observed as a plan view.
In the present specification, the term "process" is included in this term not only as an independent process but also as long as the desired action of the process is achieved even if it cannot be clearly distinguished from other processes.
As used herein, the term "transparency" means that the transparency of visible light, that is, the transparency of visible light having a wavelength of at least 400 nm is 80% or more (converted to a film thickness of 1 μm).
As used herein, the term "heat resistance" means that the generation of cracks due to heating is suppressed in a member containing an aromatic polyketone.
As used herein, the term "flexibility" means that cracks are suppressed when the diameter of the mandrel is reduced when a mandrel test is performed on an aromatic polyketone membrane.
＜芳香族ポリケトン＞
芳香族ポリケトンは、下記一般式（１）、下記一般式（２）及び下記一般式（４）からなる群より選択される少なくとも１種の構造単位と、下記一般式（５−１）で表される少なくとも１種の構造単位と、下記一般式（５−２）で表される少なくとも１種の構造単位と、を有する。この芳香族ポリケトンを、「特定芳香族ポリケトン」とも称する。
<Aromatic polyketone>
Aromatic polyketone is represented by at least one structural unit selected from the group consisting of the following general formula (1), the following general formula (2) and the following general formula (4), and the following general formula (5-1). It has at least one structural unit to be formed and at least one structural unit represented by the following general formula (5-2). This aromatic polyketone is also referred to as "specific aromatic polyketone".
特定芳香族ポリケトンが、芳香族モノマに由来する構造単位として、一般式（１）、（２）及び（４）からなる群より選択される少なくとも１種の構造単位を有し、且つジカルボン酸モノマに由来する構造単位として一般式（５−１）で表される少なくとも１種の構造単位と下記一般式（５−２）で表される少なくとも１種の構造単位の両方を有することで、耐熱性、透明性及び柔軟性に優れる芳香族ポリケトン膜を形成することができる。この理由は明らかではないが、以下のように考えることができる。 The specific aromatic polyketone has at least one structural unit selected from the group consisting of the general formulas (1), (2) and (4) as a structural unit derived from the aromatic monoma, and the dicarboxylic acid monoma. By having at least one structural unit represented by the general formula (5-1) and at least one structural unit represented by the following general formula (5-2) as the structural unit derived from, heat resistance It is possible to form an aromatic polyketone film having excellent properties, transparency and flexibility. The reason for this is not clear, but it can be thought of as follows.
特定芳香族ポリケトンがＹ１で表される脂環式炭化水素基を有することで、優れた耐熱性と透明性が奏される。また、特定芳香族ポリケトンがＹ２で表されるアルキレン基を有することで、膜としたときに優れた柔軟性が奏される。 Since the specific aromatic polyketone has an alicyclic hydrocarbon group represented by Y 1 , excellent heat resistance and transparency are exhibited. Further, since the specific aromatic polyketone has an alkylene group represented by Y 2 , excellent flexibility is exhibited when it is formed into a film.
一般式（１）中、Ｒ１はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を示し、Ｒ２はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を示す。尚、波線を付した部分は、結合手を意味する。以降、化学式中の波線については同様である。 In the general formula (1), R 1 independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a hydrogen atom or a substituent, and R 2 is an independent hydrogen atom or a substituent. Indicates a hydrocarbon group having 1 to 30 carbon atoms which may have. The wavy line means a bond. Hereinafter, the same applies to the wavy lines in the chemical formula.
耐熱性の観点から、Ｒ１はそれぞれ独立に、炭素数１〜１０の炭化水素基であることが好ましく、反応制御の観点から、炭素数１〜５の炭化水素基であることがより好ましい。 From the viewpoint of heat resistance, each of R 1 is preferably a hydrocarbon group having 1 to 10 carbon atoms independently, and more preferably a hydrocarbon group having 1 to 5 carbon atoms from the viewpoint of reaction control.
Ｒ１における置換基としては、ハロゲン原子、炭素数１〜５のアルコキシ基、炭素数２〜５のアシル基等が挙げられる。尚、炭化水素基が置換基を有する場合、炭化水素基の炭素数には、置換基の炭素数を含めないものとする。以降、同様である。 Examples of the substituent in R 1 include a halogen atom, an alkoxy group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms. When the hydrocarbon group has a substituent, the carbon number of the hydrocarbon group does not include the carbon number of the substituent. The same applies thereafter.
Ｒ１で示される炭化水素基としては、飽和脂肪族炭化水素基、不飽和脂肪族炭化水素基、脂環式炭化水素基等が挙げられる。また、これらの炭化水素基を組み合わせたものでもよい。 Examples of the hydrocarbon group represented by R 1 include a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, and an alicyclic hydrocarbon group. Further, a combination of these hydrocarbon groups may be used.
Ｒ１で示される飽和脂肪族炭化水素基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔ−ブチル基、ｎ−ペンチル基、イソペンチル基、ｓｅｃ−ペンチル基、ｎｅｏ−ペンチル基、ｔ−ペンチル基、ｎ−ヘキシル基、ｎ−ヘプチル基、ｎ−オクチル基、ｎ−ノニル基、ｎ−デシル基、ｎ−イコサニル基、ｎ−トリアコンタニル基等が挙げられる。 The saturated aliphatic hydrocarbon group represented by R 1 includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group and an n-pentyl group. , Isopentyl group, sec-pentyl group, neo-pentyl group, t-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-icosanyl group, n -Examples include a triacanthanyl group.
Ｒ１で示される不飽和脂肪族炭化水素基としては、ビニル基、アリル基等のアルケニル基、エチニル基等のアルキニル基などが挙げられる。 Examples of the unsaturated aliphatic hydrocarbon group represented by R 1 include an alkenyl group such as a vinyl group and an allyl group, and an alkynyl group such as an ethynyl group.
Ｒ１で示される脂環式炭化水素基としては、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、ノルボルニル基等のシクロアルキル基、シクロヘキセニル基等のシクロアルケニル基などが挙げられる。 Examples of the alicyclic hydrocarbon group represented by R 1 include a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and a norbornyl group, and a cycloalkenyl group such as a cyclohexenyl group. Group etc. can be mentioned.
一般式（１）中、Ｒ２はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を示す。耐熱性の観点から、Ｒ２としては、水素原子又は炭素数１〜５の炭化水素基が好ましい。このような炭化水素基としては、Ｒ１で例示したものと同様のものが挙げられる。また、置換基としては、ハロゲン原子、炭素数１〜５のアルコキシ基、炭素数２〜５のアシル基等が挙げられる。 In the general formula (1), R 2 independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a hydrogen atom or a substituent. From the viewpoint of heat resistance, R 2 is preferably a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. Examples of such hydrocarbon groups include the same ones as exemplified for R 1. Examples of the substituent include a halogen atom, an alkoxy group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms.
一般式（２）中、Ｒ１はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を示す。一般式（２）中のＲ１の詳細は、一般式（１）中のＲ１と同様である。 In the general formula (2), R 1 independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a hydrogen atom or a substituent. The general formula (2) R 1 in detail, is the same as R 1 in general formula (1).
一般式（２）中、Ｘは、酸素原子又は下記一般式（３）で表される２価の基を示す。 In the general formula (2), X represents an oxygen atom or a divalent group represented by the following general formula (3).
一般式（３）中、Ｒ３及びＲ４はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を示す。耐熱性の観点から、Ｒ３及びＲ４としては、それぞれ独立に、炭素数１〜１０の炭化水素基であることが好ましく、炭素数１〜５の炭化水素基であることがより好ましい。このような炭化水素基としては、一般式（１）中のＲ１で例示したものと同様のものが挙げられる。また、置換基としては、ハロゲン原子、炭素数１〜５のアルコキシ基、炭素数２〜５のアシル基等が挙げられる。 In the general formula (3), R 3 and R 4 each independently represent a hydrocarbon group having 1 to 30 carbon atoms which may have a hydrogen atom or a substituent. From the viewpoint of heat resistance, R 3 and R 4 are preferably hydrocarbon groups having 1 to 10 carbon atoms independently, and more preferably hydrocarbon groups having 1 to 5 carbon atoms. Examples of such hydrocarbon groups include the same ones as exemplified for R 1 of the general formula (1). Examples of the substituent include a halogen atom, an alkoxy group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms.
一般式（４）中、Ｒ５はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を示す。耐熱性の観点から、Ｒ５としては、それぞれ独立に、炭素数１〜１０の炭化水素基であることが好ましく、炭素数１〜５の炭化水素基であることがより好ましい。このような炭化水素基としては、一般式（１）中のＲ１で例示したものと同様のものが挙げられる。また、置換基としては、ハロゲン原子、炭素数１〜５のアルコキシ基、炭素数２〜５のアシル基等が挙げられる。 In the general formula (4), R 5 independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a hydrogen atom or a substituent. From the viewpoint of heat resistance, the R 5, each independently, preferably a hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrocarbon group having 1 to 5 carbon atoms. Examples of such hydrocarbon groups include the same ones as exemplified for R 1 of the general formula (1). Examples of the substituent include a halogen atom, an alkoxy group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms.
一般式（５−１）中、Ｙ１は、置換基を有していてもよい炭素数３〜３０の２価の脂環式炭化水素基を示す。一般式（５−２）中、Ｙ２は、置換基を有していてもよい炭素数１〜３０の直鎖状又は分岐鎖状アルキレン基を示す。 In the general formula (5-1), Y 1 represents a divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms which may have a substituent. In the general formula (5-2), Y 2 represents a linear or branched chain alkylene group having 1 to 30 carbon atoms which may have a substituent.
Ｙ１で示される脂環式炭化水素基の炭素数は、３〜３０であり、耐熱性の観点から、５〜２０であることが好ましい。 Y carbon atoms in the alicyclic hydrocarbon group represented by 1, 3 to 30, from the viewpoint of heat resistance, it is preferably from 5 to 20.
Ｙ１で示される脂環式炭化水素基としては、シクロプロパン骨格、シクロブタン骨格、シクロペンタン骨格、シクロヘキサン骨格、シクロヘプタン骨格、シクロオクタン骨格、キュバン骨格、ノルボルナン骨格、トリシクロ［５．２．１．０］デカン骨格、アダマンタン骨格、ジアダマンタン骨格、ビシクロ［２．２．２］オクタン骨格等を有する２価の基が挙げられる。溶解性の観点から、アダマンタン骨格を有する２価の基が好ましい。 Examples of the alicyclic hydrocarbon group represented by Y 1 include cyclopropane skeleton, cyclobutane skeleton, cyclopentane skeleton, cyclohexane skeleton, cycloheptane skeleton, cyclooctane skeleton, cubane skeleton, norbornane skeleton, and tricyclo [5.2.1. 0] Examples thereof include divalent groups having a decane skeleton, an adamantane skeleton, a diadamantane skeleton, a bicyclo [2.2.2] octane skeleton and the like. From the viewpoint of solubility, a divalent group having an adamantane skeleton is preferable.
Ｙ2で示されるアルキレン基の炭素数は、１〜３０であり、耐熱性及び透明性の観点から、３〜３０であることが好ましい。 The alkylene group represented by Y 2 has 1 to 30 carbon atoms, and is preferably 3 to 30 from the viewpoint of heat resistance and transparency.
Ｙ2で示されるアルキレン基としては、メチレン基、エチレン基、トリメチレン基、メチルエチレン基、テトラメチレン基、ｎ−メチルトリメチレン基、エチルエチレン基、ジメチルエチレン基、ペンチレン基、ｎ−メチルテトラメチレン基、ｎ−エチルトリメチレン基、ｎ，ｎ−ジメチルトリメチレン基、プロピルエチレン基、エチルメチルエチレン基、ヘキシレン基、ｎ−メチルペンチレン基、ｎ−エチルテトラメチレン基、ｎ−プロピルトリメチレン基、ブチルエチレン基、ｎ，ｎ−ジメチルテトラメチレン基、トリメチルトリメチレン基、ｎ，ｎ−エチルメチルトリメチレン基、ヘプチレン基、オクチレン基、ノニレン基、デシレン基、イコサニレン基、トリアコンタニレン基等が挙げられる。 Examples of the alkylene group represented by Y 2 include a methylene group, an ethylene group, a trimethylene group, a methylethylene group, a tetramethylene group, an n-methyltrimethylene group, an ethylethylene group, a dimethylethylene group, a pentylene group and an n-methyltetramethylene group. Group, n-ethyltrimethylene group, n, n-dimethyltrimethylene group, propylethylene group, ethylmethylethylene group, hexylene group, n-methylpentylene group, n-ethyltetramethylene group, n-propyltrimethylene group , Butylethylene group, n, n-dimethyltetramethylene group, trimethyltrimethylene group, n, n-ethylmethyltrimethylene group, heptylene group, octylene group, nonylene group, decylene group, icosanylene group, triactanylene group, etc. Can be mentioned.
Ｙ１とＹ２のモル比は、求める物性に応じて調整することができる。耐熱性と柔軟性の観点から、Ｙ１とＹ２のモル比は、Ｙ１：Ｙ２＝９：１〜３：７であることが好ましく、Ｙ１：Ｙ２＝８：２〜３：７であることが更に好ましい。 The molar ratio of Y 1 and Y 2 can be adjusted according to the desired physical properties. From the viewpoint of heat resistance and flexibility, the molar ratio of Y 1 to Y 2 is preferably Y 1 : Y 2 = 9: 1 to 3: 7, and Y 1 : Y 2 = 8: 2 to 3: 7. It is more preferably 7.
耐熱性の観点からは、芳香族ポリケトンの重量平均分子量（Ｍｗ）は、１００００以上であることが好ましく、２００００以上であることがより好ましい。また、数平均分子量（Ｍｎ）は１０００以上であることが好ましく、２０００以上であることがより好ましい。
溶解性の観点からは、芳香族ポリケトンの重量平均分子量（Ｍｗ）は、３５００００以下であることが好ましく、３０００００以下であることがより好ましい。また、数平均分子量（Ｍｎ）は、２０００００以下であることが好ましく、１０００００以下であることがより好ましい。
From the viewpoint of heat resistance, the weight average molecular weight (Mw) of the aromatic polyketone is preferably 10,000 or more, and more preferably 20,000 or more. The number average molecular weight (Mn) is preferably 1000 or more, and more preferably 2000 or more.
From the viewpoint of solubility, the weight average molecular weight (Mw) of the aromatic polyketone is preferably 350,000 or less, and more preferably 300,000 or less. The number average molecular weight (Mn) is preferably 200,000 or less, and more preferably 100,000 or less.
＜芳香族ポリケトンの製造方法＞
特定芳香族ポリケトンは、上記一般式（１）、（２）及び（４）からなる群より選択される少なくとも１種の構造単位と、上記一般式（５−１）で表される少なくとも１種の構造単位と、上記一般式（５−２）で表される少なくとも１種の構造単位と、を有してさえいれば、製造方法は特に限定されない。例えば、下記一般式（１’）、（２’）及び（４’）からなる群より選択される少なくとも１種の芳香族モノマと、下記一般式（５−１’）で表される少なくとも１種のジカルボン酸モノマと、下記一般式（５−２’）で表される少なくとも１種のジカルボン酸モノマとを、酸性媒体中で縮合反応させて得ることができる。
<Manufacturing method of aromatic polyketone>
The specific aromatic polyketone is at least one structural unit selected from the group consisting of the general formulas (1), (2) and (4) and at least one represented by the general formula (5-1). The production method is not particularly limited as long as it has the structural unit of the above and at least one structural unit represented by the above general formula (5-2). For example, at least one aromatic monoma selected from the group consisting of the following general formulas (1'), (2') and (4'), and at least 1 represented by the following general formula (5-1'). A seed dicarboxylic acid monoma and at least one dicarboxylic acid monoma represented by the following general formula (5-2') can be obtained by condensation reaction in an acidic medium.
一般式（１’）中、Ｒ１はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を示し、Ｒ２はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を示す。一般式（１’）中のＲ１及びＲ２の詳細は、一般式（１）中のＲ１及びＲ２とそれぞれ同様である。 In the general formula (1'), R 1 independently represents a hydrocarbon atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R 2 is an independent hydrogen atom or a substituent. A hydrocarbon group having 1 to 30 carbon atoms which may have a group is shown. The general formula (1 ') of R 1 and R 2 in detail, is the general formula (1) and R 1 and R 2 in the same respectively.
一般式（２’）中、Ｒ１はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を示し、Ｘは酸素原子又は下記一般式（３’）で表される２価の基を示す。一般式（２’）中のＲ１の詳細は、一般式（２）中のＲ１と同様である。 In the general formula (2'), R 1 independently represents a hydrocarbon atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and X is an oxygen atom or the following general formula (3'). ) Indicates a divalent group. The general formula (2 ') of R 1 in detail, the same as R 1 in the general formula (2).
一般式（３’）中、Ｒ３及びＲ４はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を示す。一般式（３’）中のＲ３又はＲ４の詳細は、一般式（３）中のＲ３又はＲ４とそれぞれ同様である。 In the general formula (3'), R 3 and R 4 each independently represent a hydrocarbon group having 1 to 30 carbon atoms which may have a hydrogen atom or a substituent. The more general formula (3 ') in R 3 or R 4, are each similar to the general formula (3) R 3 or R 4 in.
一般式（４’）中、Ｒ５はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を示す。一般式（４’）中のＲ５の詳細は、一般式（４）中のＲ５と同様である。 In the general formula (4'), R 5 independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a hydrogen atom or a substituent. Details of the general formula (4 ') in R 5, is the same as R 5 in the general formula (4).
一般式（５−１’）中、Ｙ１は、置換基を有していてもよい炭素数３〜３０の２価の脂環式炭化水素基を示す。一般式（５−２’）中、Ｙ２は、置換基を有していてもよい炭素数１〜３０の直鎖状又は分岐鎖状アルキレン基を示す。一般式（５−１’）中のＹ１の詳細は、一般式（５−１）中のＹ１と同様である。一般式（５−２’）中のＹ２の詳細は、一般式（５−２）中のＹ２と同様である。 In the general formula (5-1'), Y 1 represents a divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms which may have a substituent. In the general formula (5-2'), Y 2 represents a linear or branched chain alkylene group having 1 to 30 carbon atoms which may have a substituent. The general formula (5-1 ') of Y 1 in detail, the same as Y 1 in the general formula (5-1). The general formula (5-2 ') of Y 2 in detail, the same as Y 2 in the general formula (5-2) in.
一般式（５−１’）で表されるジカルボン酸モノマとしては、１，３−アダマンタンジカルボン酸、１，３−シクロへキサンジカルボン酸、１，４−シクロヘキサンジカルボン酸、２，３−シクロヘキサンジカルボン酸、１，３−ノルボルナンジカルボン酸、１，４−ノルボルナンジカルボン酸、２，３−ノルボルナンジカルボン酸、１，４−デカヒドロナフタレンジカルボン酸、２，３−デカヒドロナフタレンジカルボン酸等が挙げられる。反応性の観点からは、１，３−位、又は２，３−位でカルボキシル基と結合した脂環式カルボン酸が好ましい。
一般式（５−２’）で表されるジカルボン酸モノマとしては、ドデカン二酸、ウンデカン二酸、デカン二酸、ノナン二酸、オクタン二酸、ヘプタン二酸、ノナン二酸、アジピン酸、グルタル酸、コハク酸、マロン酸等が挙げられる。
Examples of the dicarboxylic acid monoma represented by the general formula (5-1') include 1,3-adamantandicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and 2,3-cyclohexanedicarboxylic acid. Examples thereof include acids, 1,3-norbornandicarboxylic acid, 1,4-norbornandicarboxylic acid, 2,3-norbornandicarboxylic acid, 1,4-decahydronaphthalenedicarboxylic acid, and 2,3-decahydronaphthalenedicarboxylic acid. From the viewpoint of reactivity, an alicyclic carboxylic acid bonded to a carboxyl group at the 1,3-position or the 2,3-position is preferable.
Examples of the dicarboxylic acid monoma represented by the general formula (5-2') include dodecanedioic acid, undecanedioic acid, decanedioic acid, nonanedioic acid, octanedioic acid, heptanedioic acid, nonanedioic acid, adipic acid, and glutaric acid. Examples thereof include acid, succinic acid and malonic acid.
一般式（５−１’）で表されるジカルボン酸モノマと一般式（５−２’）で表されるジカルボン酸モノマの仕込む割合を変えることで、縮合反応によって得られる特定芳香族ポリケトン中のＹ１とＹ２の比率を調整することができる。 By changing the ratio of the dicarboxylic acid monomer represented by the general formula (5-1') and the dicarboxylic acid monoma represented by the general formula (5-2'), the specific aromatic polyketone obtained by the condensation reaction can be charged. The ratio of Y 1 and Y 2 can be adjusted.
縮合反応は酸性媒体中で行う。酸性媒体は特に限定されず、塩化アルミニウムの有機溶媒溶液、トリフルオロアルカンスルホン酸の有機溶媒溶液、ポリリン酸、五酸化二リンと有機スルホン酸との混合物等を用いることができる。反応性と取り扱い性の観点から、酸性媒体としては、五酸化二リンと有機スルホン酸との混合物を用いることが好ましく、更に、有機スルホン酸としてはメタンスルホン酸が好ましい。 The condensation reaction is carried out in an acidic medium. The acidic medium is not particularly limited, and an organic solvent solution of aluminum chloride, an organic solvent solution of trifluoroalkane sulfonic acid, polyphosphoric acid, a mixture of diphosphorus pentoxide and organic sulfonic acid and the like can be used. From the viewpoint of reactivity and handleability, it is preferable to use a mixture of diphosphorus pentoxide and organic sulfonic acid as the acidic medium, and further, methanesulfonic acid is preferable as the organic sulfonic acid.
五酸化二リンと有機スルホン酸との混合物中で、五酸化二リンが少なすぎると、反応性に劣る傾向にある。五酸化二リンと有機スルホン酸との混合比は、反応の制御性及び促進性の観点から、質量比で五酸化二リン：有機スルホン酸＝１：５〜１：２０であることが好ましく、１：５〜１：１０であることがより好ましい。 If the amount of diphosphorus pentoxide is too small in the mixture of diphosphorus pentoxide and organic sulfonic acid, the reactivity tends to be poor. The mixing ratio of diphosphorus pentoxide and organic sulfonic acid is preferably diphosphorus pentoxide: organic sulfonic acid = 1: 5 to 1:20 in terms of mass ratio from the viewpoint of reaction controllability and facilitation. It is more preferably 1: 5 to 1:10.
縮合反応における五酸化二リンと有機スルホン酸の使用量は、芳香族モノマとジカルボン酸モノマとを溶解し得る量であれば特に限定されず、いわゆる触媒量から溶媒量までの範囲で用いることができる。反応性と扱いやすさの観点から、ジカルボン酸モノマ１質量部に対して、五酸化二リンと有機スルホン酸との混合物を５０質量部〜１００質量部の範囲で使用することが好ましい。 The amount of diphosphorus pentoxide and organic sulfonic acid used in the condensation reaction is not particularly limited as long as it can dissolve the aromatic monoma and the dicarboxylic acid monoma, and may be used in the range from the so-called catalytic amount to the solvent amount. it can. From the viewpoint of reactivity and ease of handling, it is preferable to use a mixture of diphosphorus pentoxide and organic sulfonic acid in the range of 50 parts by mass to 100 parts by mass with respect to 1 part by mass of monoma dicarboxylic acid.
縮合反応の温度は、反応生成物の着色及び副反応を防ぐ観点からは、１０℃〜１００℃に設定することが好ましく、反応速度を上げて生産性を向上させる観点からは、２０℃〜１００℃に設定することがより好ましい。 The temperature of the condensation reaction is preferably set to 10 ° C. to 100 ° C. from the viewpoint of preventing coloring of the reaction product and side reactions, and 20 ° C. to 100 ° C. from the viewpoint of increasing the reaction rate and improving productivity. It is more preferable to set it to ° C.
縮合反応の雰囲気は特に限定されず、開放系で行うこともできる。しかし、水分の存在により酸性媒体の反応性が低下するため、乾燥空気、窒素、アルゴン等の雰囲気下で行なうことが好ましい。想定外の副反応を防ぐ観点からは、窒素又はアルゴンの雰囲気下で行なうことが更に好ましい。 The atmosphere of the condensation reaction is not particularly limited, and the condensation reaction can be carried out in an open system. However, since the reactivity of the acidic medium decreases due to the presence of water, it is preferable to carry out the operation in an atmosphere of dry air, nitrogen, argon or the like. From the viewpoint of preventing unexpected side reactions, it is more preferable to carry out in an atmosphere of nitrogen or argon.
反応液を撹拌することで、縮合反応を促進することができる。撹拌方法は特に限定されず、マグネチックスターラ、メカニカルスターラ等を用いることができる。 The condensation reaction can be promoted by stirring the reaction solution. The stirring method is not particularly limited, and a magnetic stirrer, a mechanical stirrer, or the like can be used.
縮合反応の反応時間は、反応温度、目標とする特定芳香族ポリケトンの分子量、反応に用いるモノマの種類等によって適宜設定することが好ましい。十分に分子量の高いポリケトンを得る観点からは、反応時間は１時間〜１２０時間とすることが好ましく、生産性の観点からは、１時間〜７２時間とすることがより好ましい。 The reaction time of the condensation reaction is preferably set appropriately according to the reaction temperature, the target molecular weight of the specific aromatic polyketone, the type of monomer used in the reaction, and the like. From the viewpoint of obtaining a polyketone having a sufficiently high molecular weight, the reaction time is preferably 1 hour to 120 hours, and more preferably 1 hour to 72 hours from the viewpoint of productivity.
縮合反応での反応系の圧力は特に限定されず、常圧下、加圧下、又は減圧下のいずれで行ってもよい。コストの観点から、常圧下で縮合反応を行うことが好ましい。 The pressure of the reaction system in the condensation reaction is not particularly limited, and may be carried out under normal pressure, pressure, or reduced pressure. From the viewpoint of cost, it is preferable to carry out the condensation reaction under normal pressure.
芳香族モノマとジカルボン酸モノマとの縮合反応を終えた後、特定芳香族ポリケトンを含有する液（例えば、縮合反応液、又は特定芳香族ポリケトンを溶解した溶液）と貧溶媒とを接触させて特定芳香族ポリケトンを析出させ、不純物を貧溶媒層に抽出し、析出した特定芳香族ポリケトンを濾過、デカンテーション、遠心分離等の方法で液体から分離する。更にこの後、分離した特定芳香族ポリケトンを再度、良溶媒に溶解させ、再び貧溶媒と接触させて特定芳香族ポリケトンを析出させ、不純物を貧溶媒層に抽出し、析出した特定芳香族ポリケトンを濾過、デカンテーション、遠心分離等の方法で液体から分離してもよい。この操作を繰り返すことで、特定芳香族ポリケトンから不純物をより十分に取り除くことができる。 After completing the condensation reaction between the aromatic monoma and the dicarboxylic acid monoma, a solution containing the specific aromatic polyketone (for example, a condensation reaction solution or a solution in which the specific aromatic polyketone is dissolved) is brought into contact with a poor solvent for identification. Aromatic polyketone is precipitated, impurities are extracted into a poor solvent layer, and the precipitated specific aromatic polyketone is separated from the liquid by a method such as filtration, decantation, or centrifugation. Further, after this, the separated specific aromatic polyketone is dissolved again in a good solvent, contacted with a poor solvent again to precipitate the specific aromatic polyketone, impurities are extracted into the poor solvent layer, and the precipitated specific aromatic polyketone is obtained. It may be separated from the liquid by a method such as filtration, decantation, or centrifugation. By repeating this operation, impurities can be more sufficiently removed from the specific aromatic polyketone.
本明細書において「貧溶媒」とは、芳香族ポリケトンに対して貧溶媒であることを意味し、具体的には、溶媒１００ｇ中に芳香族ポリケトンが０．０１ｇ以下しか溶解しない溶媒を意味する。そして、「良溶媒」とは、芳香族ポリケトンに対して良溶媒であることを意味し、具体的には、溶媒１００ｇ中に芳香族ポリケトンが１ｇ以上溶解する溶媒を意味する。 As used herein, the term "poor solvent" means that the solvent is poor with respect to the aromatic polyketone, and specifically, it means a solvent in which only 0.01 g or less of the aromatic polyketone is dissolved in 100 g of the solvent. .. The "good solvent" means that the solvent is a good solvent for the aromatic polyketone, and specifically, it means a solvent in which 1 g or more of the aromatic polyketone is dissolved in 100 g of the solvent.
特定芳香族ポリケトンは、透明性、耐熱性及び柔軟性に優れる芳香族ポリケトン膜を得ることができ、フレキシブルな透明耐熱材として用いることができる。 As the specific aromatic polyketone, an aromatic polyketone film having excellent transparency, heat resistance and flexibility can be obtained, and it can be used as a flexible transparent heat resistant material.
＜芳香族ポリケトンワニス＞
芳香族ポリケトンワニスは、特定芳香族ポリケトンと、溶媒と、を含有する。芳香族ポリケトンワニスは、特定芳香族ポリケトンを溶媒に溶解させる等により得ることができる。特定芳香族ポリケトンを溶媒に溶解させる方法は特に限定されず、当該技術分野で既知の方法を用いることができる。また、必要に応じて、溶解後に、不溶成分を濾別してもよい。
<Aromatic polyketone varnish>
The aromatic polyketone varnish contains a specific aromatic polyketone and a solvent. The aromatic polyketone varnish can be obtained by dissolving a specific aromatic polyketone in a solvent or the like. The method for dissolving the specific aromatic polyketone in the solvent is not particularly limited, and a method known in the art can be used. Further, if necessary, the insoluble component may be filtered off after dissolution.
ワニスに含有される溶媒は、特定芳香族ポリケトンを溶解するものであれば特に制限されない。溶媒の例としては、γ−ブチロラクトン、乳酸エチル、プロピレングリコールモノメチルエーテルアセテート、酢酸ブチル、酢酸ベンジル、エトキシエチルプロピオネート、３−メチルメトキシプロピオネート、Ｎ−メチル−２−ピロリドン、Ｎ−シクロヘキシル−２−ピロリドン、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、ジメチルスルホキシド、ヘキサメチルホスホリルアミド、テトラメチレンスルホン、ジエチルケトン、ジイソブチルケトン、メチルアミルケトン、シクロヘキサノン、プロピレングリコールモノメチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテル、キシレン、メシチレン、エチルベンゼン、プロピルベンゼン、クメン、ジイソプロピルベンゼン、ヘキシルベンゼン、アニソール、ジグライム、ジメチルスルホキシド、クロロホルム、ジクロロメタン、ジクロロエタン、クロロベンゼン、テトラヒドロフラン等が挙げられる。これらの溶媒は１種単独で又は２種以上を組み合わせて用いることができる。 The solvent contained in the varnish is not particularly limited as long as it dissolves a specific aromatic polyketone. Examples of solvents include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, butyl acetate, benzyl acetate, ethoxyethyl propionate, 3-methylmethoxypropionate, N-methyl-2-pyrrolidone, N-cyclohexyl. -2-Pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphorylamide, tetramethylenesulfone, diethylketone, diisobutylketone, methylamylketone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol Monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, xylene, mesitylene, ethylbenzene, propylbenzene, cumene, diisopropylbenzene, hexylbenzene, anisole, diglime, dimethyl sulfoxide, chloroform, dichloromethane, dichloroethane, chlorobenzene, tetrahydrofuran, etc. Can be mentioned. These solvents can be used alone or in combination of two or more.
芳香族ポリケトンワニスは、特定芳香族ポリケトン及び溶媒以外に、添加剤等を更に含んでいてもよい。添加剤としては、接着助剤、界面活性剤、レベリング剤、酸化防止剤、紫外線劣化防止剤等が挙げられる。 The aromatic polyketone varnish may further contain additives and the like in addition to the specific aromatic polyketone and the solvent. Examples of the additive include an adhesive aid, a surfactant, a leveling agent, an antioxidant, an ultraviolet deterioration inhibitor and the like.
＜芳香族ポリケトン膜＞
芳香族ポリケトン膜は、特定芳香族ポリケトンを含有する。芳香族ポリケトン膜は、芳香族ポリケトンワニスを用いて形成することができる。芳香族ポリケトン膜は、原料として脂環式ジカルボン酸及び２，２’−ジアルコキシビフェニル化合物以外のものを用いずに重合される従来の芳香族ポリケトンを含有する芳香族ポリケトン膜よりも柔軟である。
<Aromatic polyketone membrane>
The aromatic polyketone membrane contains a specific aromatic polyketone. The aromatic polyketone film can be formed by using an aromatic polyketone varnish. Aromatic polyketone films are more flexible than conventional aromatic polyketone films containing polyketones that are polymerized without using anything other than alicyclic dicarboxylic acids and 2,2'-dialkoxybiphenyl compounds as raw materials. ..
特定芳香族ポリケトン膜の製造方法は、特に限定されない。例えば、以下の方法によって得ることができる。
本実施形態の芳香族ポリケトンワニスを基材の表面の少なくとも一部に付与してワニス層を形成する。ワニスを付与する方法としては、ワニス層を基材上の任意の場所に任意の形状で形成可能な手法であれば特に限定されない。例えば、付与方法としては、浸漬塗布法、スプレー塗布法、スクリーン印刷法、回転塗布法等が好適に用いられる。
The method for producing the specific aromatic polyketone film is not particularly limited. For example, it can be obtained by the following method.
The aromatic polyketone varnish of the present embodiment is applied to at least a part of the surface of the base material to form a varnish layer. The method of applying the varnish is not particularly limited as long as the varnish layer can be formed at an arbitrary location on the substrate in an arbitrary shape. For example, as the applying method, a dipping coating method, a spray coating method, a screen printing method, a rotary coating method and the like are preferably used.
芳香族ポリケトンワニスを付与する基材は特に限定されず、ガラス基材、半導体基材、金属酸化物絶縁体基材（例えば、酸化チタン基材及び酸化ケイ素基材）、窒化ケイ素基材、トリアセチルセルロース、透明ポリイミド、ポリカーボネート、アクリル系ポリマー、シクロオレフィン樹脂等の透明樹脂基材などを例示することができる。基板の形状は特に限定されず、板状又はフィルム状であってもよい。 The base material to which the aromatic polyketone varnish is applied is not particularly limited, and is a glass base material, a semiconductor base material, a metal oxide insulator base material (for example, a titanium oxide base material and a silicon oxide base material), a silicon nitride base material, and a bird. Examples thereof include transparent resin substrates such as acetyl cellulose, transparent polyimide, polycarbonate, acrylic polymer, and cycloolefin resin. The shape of the substrate is not particularly limited, and may be a plate shape or a film shape.
ワニス層を形成した後、乾燥工程においてワニス層を乾燥させる。乾燥する方法は特に限定されず、例えば、ホットプレート、オーブン等を用いた加熱により乾燥することができる。必要に応じて、乾燥した芳香族ポリケトン膜を、基板から剥がして用いることもできる。 After forming the varnish layer, the varnish layer is dried in the drying step. The method of drying is not particularly limited, and for example, it can be dried by heating using a hot plate, an oven, or the like. If necessary, the dried aromatic polyketone film can be peeled off from the substrate and used.
また、必要に応じて、乾燥した芳香族ポリケトン膜を更に熱処理してもよい。熱処理の方法は特に限定されず、例えば、箱型乾燥機、熱風式コンベアー型乾燥機、石英チューブ炉、ホットプレート、ラピッドサーマルアニール、縦型拡散炉、赤外線硬化炉、マイクロ波硬化炉等のオーブンを用いて行なうことができる。また、熱処理工程における雰囲気条件としては、大気、又は窒素等の不活性ガスのいずれであってもよい。 Further, if necessary, the dried aromatic polyketone membrane may be further heat-treated. The method of heat treatment is not particularly limited, and for example, an oven such as a box type dryer, a hot air type conveyor type dryer, a quartz tube furnace, a hot plate, a rapid thermal annealing, a vertical diffusion furnace, an infrared curing furnace, a microwave curing furnace, etc. Can be done using. The atmospheric conditions in the heat treatment step may be either the atmosphere or an inert gas such as nitrogen.
＜表示素子＞
表示素子は、本実施形態の芳香族ポリケトン膜を有する。
表示装置は、例えば、芳香族ポリケトン膜を、粘着剤、接着剤等を介してＬＣＤ（液晶ディスプレイ）、ＥＬＤ（エレクトロルミネッセンスディスプレイ）等の構成部材に貼り合せて、得ることができる。芳香族ポリケトン膜を貼り付ける構成部材としては、偏光板等の各種光学素子等が挙げられる。
<Display element>
The display element has the aromatic polyketone film of the present embodiment.
The display device can be obtained by, for example, attaching an aromatic polyketone film to a constituent member such as an LCD (liquid crystal display) or an ELD (electroluminescence display) via an adhesive, an adhesive or the like. Examples of the constituent member to which the aromatic polyketone film is attached include various optical elements such as a polarizing plate.
本実施形態の表示装置は、芳香族ポリケトン膜を有すること以外は、従来の表示装置と同様の構成であってもよい。例えば、表示装置が液晶表示装置である場合は、液晶セル、偏光板等の光学素子、及び必要に応じ照明システム（バックライト等）などの各構成部材を常法により組み立てて、駆動回路を組み込むこと等により製造できる。液晶セルとしては、特に制限されず、ＴＮ型、ＳＴＮ型、π型等の様々なタイプを使用できる。 The display device of the present embodiment may have the same configuration as the conventional display device except that it has an aromatic polyketone film. For example, when the display device is a liquid crystal display device, each component such as a liquid crystal cell, an optical element such as a polarizing plate, and a lighting system (backlight, etc.) is assembled by a conventional method, and a drive circuit is incorporated. It can be manufactured by such things. The liquid crystal cell is not particularly limited, and various types such as TN type, STN type, and π type can be used.
表示装置は、任意の適切な用途に使用される。その用途は、例えば、デスクトップパソコン、ノートパソコン、コピー機等のＯＡ機器、携帯電話、時計、デジタルカメラ、携帯情報端末（ＰＤＡ）、携帯ゲーム機等の携帯機器、ビデオカメラ、テレビ、電子レンジ等の家庭用電気機器、バックモニター、カーナビゲーションシステム用モニター、カーオーディオ等の車載用機器、商業店舗用インフォメーション用モニター等の展示機器、監視用モニター等の警備機器、介護用モニター等の介護機器、医療用モニター等の医療機器などが挙げられる。 The display device is used for any suitable application. Applications include, for example, OA devices such as desktop personal computers, laptop computers, and copy machines, mobile phones, watches, digital cameras, mobile information terminals (PDAs), portable devices such as portable game machines, video cameras, televisions, microwave ovens, etc. Household electrical equipment, back monitors, car navigation system monitors, in-vehicle equipment such as car audio, exhibition equipment such as information monitors for commercial stores, security equipment such as monitoring monitors, nursing equipment such as nursing monitors, Examples include medical devices such as medical monitors.
以下、実施例を挙げて本発明を更に具体的に説明する。ただし、本発明は、その要旨を逸脱しない限り、これら実施例に限定されるものではない。尚、特に断りのない限り、「部」及び「％」は質量基準である。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples as long as it does not deviate from the gist thereof. Unless otherwise specified, "parts" and "%" are based on mass.
（実施例１）ポリケトンＰＫ１の合成
モノマとして、２，２’−ジメトキシビフェニル１０ｍｍｏｌと１，３−アダマンタンジカルボン酸５ｍｍｏｌとドデカン二酸５ｍｍｏｌが入ったフラスコに、五酸化二リンとメタンスルホン酸の混合液物（質量比１：１０）を３０ｍｌ加え、窒素風船をつけて６０℃で４０時間撹拌した。反応後、反応液をメタノール５００ｍｌ中に投じ、生成した析出物を濾取した。得られた固体を蒸留水とメタノールで洗浄した後、乾燥し、ポリケトンＰＫ１を得た。得られたポリケトンＰＫ１の１３Ｃ−ＮＭＲスペクトルを図１に示す。また、重量平均分子量は３０，０００、数平均分子量は５，０００であった。
(Example 1) Synthesis of polyketone PK1 As a monoma, diphosphorus pentoxide and methanesulfonic acid are mixed in a flask containing 10 mmol of 2,2'-dimethoxybiphenyl, 5 mmol of 1,3-adamantandicarboxylic acid, and 5 mmol of dodecanedioic acid. 30 ml of a liquid (mass ratio 1:10) was added, and a nitrogen balloon was attached to stir at 60 ° C. for 40 hours. After the reaction, the reaction solution was poured into 500 ml of methanol, and the formed precipitate was collected by filtration. The obtained solid was washed with distilled water and methanol and then dried to obtain a polyketone PK1. The 13 C-NMR spectrum of the obtained polyketone PK1 is shown in FIG. The weight average molecular weight was 30,000 and the number average molecular weight was 5,000.
（実施例２）ポリケトンＰＫ２の合成
モノマとして、２，２’−ジメトキシビフェニル１０ｍｍｏｌと１，３−アダマンタンジカルボン酸７．５ｍｍｏｌとドデカン二酸２．５ｍｍｏｌを用いた以外は実施例１と同様にして、ポリケトンＰＫ２を得た。得られたポリケトンＰＫ２の１３Ｃ−ＮＭＲを図２に示す。また、重量平均分子量は１８０，０００、数平均分子量は３，０００であった。
(Example 2) Synthesis of polyketone PK2 Same as in Example 1 except that 10 mmol of 2,2'-dimethoxybiphenyl, 7.5 mmol of 1,3-adamantandicarboxylic acid and 2.5 mmol of dodecanedioic acid were used as monomas. , Polyketone PK2 was obtained. The 13 C-NMR of the obtained polyketone PK2 is shown in FIG. The weight average molecular weight was 180,000 and the number average molecular weight was 3,000.
（実施例３）ポリケトンＰＫ３の合成
モノマとして、２，２’−ジメトキシビフェニル１０ｍｍｏｌと１，３−アダマンタンジカルボン酸９．０ｍｍｏｌとドデカン二酸１．０ｍｍｏｌを用いた以外は実施例１と同様にして、ポリケトンＰＫ３を得た。得られたポリケトンＰＫ３の１３Ｃ−ＮＭＲを図３に示す。また、重量平均分子量は２５０，０００、数平均分子量は５，０００であった。
(Example 3) Synthesis of polyketone PK3 Same as in Example 1 except that 10 mmol of 2,2'-dimethoxybiphenyl, 9.0 mmol of 1,3-adamantandicarboxylic acid and 1.0 mmol of dodecanedioic acid were used as monomas. , Polyketone PK3 was obtained. The 13 C-NMR of the obtained polyketone PK3 is shown in FIG. The weight average molecular weight was 250,000 and the number average molecular weight was 5,000.
（実施例４）ポリケトンＰＫ１を含有するワニス
実施例１で得たポリケトンＰＫ１を、Ｎ−メチル−２−ピロリドン（ＮＭＰ）に濃度が２０％となるように溶解し、ポリテトラフルオロエチレン製のメンブレンフィルター（孔径５μｍ）で濾過して、ポリケトンＰＫ１のワニスを得た。
(Example 4) Varnish containing polyketone PK1 The polyketone PK1 obtained in Example 1 was dissolved in N-methyl-2-pyrrolidone (NMP) so as to have a concentration of 20%, and a membrane made of polytetrafluoroethylene was dissolved. A varnish of polyketone PK1 was obtained by filtering with a filter (pore diameter 5 μm).
（実施例５）ポリケトンＰＫ２を含有するワニス
ポリケトンＰＫ１の代わりにポリケトンＰＫ２を用いた以外は実施例４と同様にして、ポリケトンＰＫ２のワニスを得た。
(Example 5) Varnish containing polyketone PK2 A varnish of polyketone PK2 was obtained in the same manner as in Example 4 except that polyketone PK2 was used instead of polyketone PK1.
（実施例６）ポリケトンＰＫ３を含有するワニス
ポリケトンＰＫ１の代わりにポリケトンＰＫ３を用いた以外は実施例４と同様にして、ポリケトンＰＫ３のワニスを得た。
(Example 6) Varnish containing polyketone PK3 A varnish of polyketone PK3 was obtained in the same manner as in Example 4 except that polyketone PK3 was used instead of polyketone PK1.
（実施例７）ポリケトンＰＫ１を含有する膜
実施例４で得られたポリケトンＰＫ１のワニスを、バーコート法によりガラス基板上及びカプトンフィルム上にそれぞれ塗布し、１２０℃に加熱したホットプレート上で３分間乾燥して、ポリケトンＰＫ１の膜付きガラス基板及びポリケトンＰＫ１の膜付きカプトンフィルム（以降、これらを総称して「膜付き基板」ともいう）を得た。得られた膜付き基板について、透明性、耐熱性、及び柔軟性（耐屈曲性）を、後述の手法で評価した。
(Example 7) Film containing polyketone PK1 The varnish of polyketone PK1 obtained in Example 4 was applied onto a glass substrate and a Kapton film by the bar coating method, respectively, and 3 on a hot plate heated to 120 ° C. After drying for a minute, a glass substrate with a film of Polyketone PK1 and a Kapton film with a film of Polyketone PK1 (hereinafter, these are collectively referred to as a “film-coated substrate”) were obtained. The transparency, heat resistance, and flexibility (flexibility) of the obtained substrate with a film were evaluated by the method described later.
（実施例８）ポリケトンＰＫ２を含有する膜
ポリケトンＰＫ１のワニスの代わりに、実施例５で得られたポリケトンＰＫ２のワニスを用いた以外は実施例７と同様にして、ポリケトンＰＫ２の膜付き基板を得て、評価を行った。
(Example 8) Film containing polyketone PK2 A substrate with a film of polyketone PK2 was used in the same manner as in Example 7 except that the varnish of polyketone PK2 obtained in Example 5 was used instead of the varnish of polyketone PK1. Obtained and evaluated.
（実施例９）ポリケトンＰＫ３を含有する膜
ポリケトンＰＫ１のワニスの代わりに、実施例６で得られたポリケトンＰＫ３のワニスを用いた以外は実施例７と同様にして、ポリケトンＰＫ３の膜付き基板を得て、評価を行った。
(Example 9) Film containing polyketone PK3 A substrate with a film of polyketone PK3 was prepared in the same manner as in Example 7 except that the varnish of polyketone PK3 obtained in Example 6 was used instead of the varnish of polyketone PK1. Obtained and evaluated.
（比較合成例）ポリケトンＰＫ４の合成
モノマとして、２，２’−ジメトキシビフェニル１０ｍｍｏｌと１，３−アダマンタンジカルボン酸１０ｍｍｏｌを用いるように変更した以外は実施例１と同様にして、ポリケトンＰＫ４を得た。得られたポリケトンＰＫ４の重量平均分子量は６０，０００、数平均分子量は４，０００であった。
(Comparative Synthesis Example) Synthesis of polyketone PK4 Polyketone PK4 was obtained in the same manner as in Example 1 except that 10 mmol of 2,2'-dimethoxybiphenyl and 10 mmol of 1,3-adamantandicarboxylic acid were used as monomas. .. The obtained polyketone PK4 had a weight average molecular weight of 60,000 and a number average molecular weight of 4,000.
（比較製造例）ポリケトンＰＫ４を用いたワニス
ポリケトンＰＫ１の代わりにポリケトンＰＫ４を用いた以外は実施例４と同様にして、ポリケトンＰＫ４を含有するワニスを得た。
(Comparative Production Example) Varnish Using Polyketone PK4 A varnish containing polyketone PK4 was obtained in the same manner as in Example 4 except that polyketone PK4 was used instead of polyketone PK1.
（比較例）ポリケトンＰＫ４のワニスを用いた膜
ポリケトンＰＫ１のワニスの代わりにポリケトンＰＫ４のワニスを用いた以外は実施例７と同様にして、ポリケトンＰＫ４の膜付き基板を得て、評価を行った。
(Comparative Example) A film using a varnish of polyketone PK4 A substrate with a film of polyketone PK4 was obtained and evaluated in the same manner as in Example 7 except that a varnish of polyketone PK4 was used instead of the varnish of polyketone PK1. ..
（分子量の測定）
分子量は、溶離液として、硝酸テトラブチルアンモニウム（ＴＢＡ・ＮＯ３）を０．１％溶解させたテトラヒドロフラン（ＴＨＦ）を用いて、ガスパーミエーションクロマトグラフィー（ＧＰＣ）法によって測定し、標準ポリスチレン換算にて求めた。詳細は次のとおりである。
(Measurement of molecular weight)
The molecular weight was measured by the gas permeation chromatography (GPC) method using tetrahydrofuran (THF) in which 0.1% of tetrabutylammonium nitrate (TBA / NO 3 ) was dissolved as an eluent, and converted to standard polystyrene. I asked for it. The details are as follows.
・装置名：ＲＩ−８０２０（検出器）、ＤＰ−８０２０（ポンプ）、ＳＤ−８０２２（デガッサ）（東ソー株式会社）
・カラム：Ｇｅｌｐａｃｋ ＧＬ−Ａ１５０、ＧＬ−Ａ１６０、ＧＬ−Ａ１７０（製品名、日立化成株式会社）
・検出器：ＲＩ検出器
・溶離液：硝酸テトラブチルアンモニウム（ＴＢＡ・ＮＯ３）を０．１質量％溶解させたテトラヒドロフラン（ＴＨＦ）
・流速：１ｍｌ／ｍｉｎ
-Device name: RI-8020 (detector), DP-8020 (pump), SD-8022 (degassa) (Tosoh Corporation)
-Column: Gelpack GL-A150, GL-A160, GL-A170 (Product name, Hitachi Chemical Co., Ltd.)
-Detector: RI detector-Eluent: Tetrahydrofuran (THF) in which 0.1% by mass of tetrabutylammonium nitrate (TBA / NO 3 ) is dissolved.
・ Flow velocity: 1 ml / min
（透明性の評価）
実施例７〜９又は比較例で得たポリケトン膜付きガラス基板の４００ｎｍにおける紫外光の透過率を、紫外可視吸収スペクトル法によって測定した。測定には、紫外可視分光光度計（「Ｕ−３３１０Ｓｐｅｃｔｒｏｐｈｏｔｏｍｅｔｅｒ」日立ハイテク株式会社）を用いた。ポリケトン膜の付いていないガラス基板をリファレンスとして、膜厚１μｍに換算した透過率を表１に示す。
(Evaluation of transparency)
The transmittance of ultraviolet light at 400 nm of the glass substrate with a polyketone film obtained in Examples 7 to 9 or Comparative Example was measured by the ultraviolet-visible absorption spectroscopy. An ultraviolet-visible spectrophotometer (“U-3310 Spectrophotometer”, Hitachi High-Technologies Corporation) was used for the measurement. Table 1 shows the transmittance converted to a film thickness of 1 μm using a glass substrate without a polyketone film as a reference.
（耐熱性の評価）
実施例７〜９又は比較例で得たポリケトン膜付きガラス基板を２００℃のオーブンに２４時間静置して加熱し、４００ｎｍにおける紫外光の透過率を、紫外可視吸収スペクトル法によって測定した。測定には、紫外可視分光光度計（「Ｕ−３３１０Ｓｐｅｃｔｒｏｐｈｏｔｏｍｅｔｅｒ」日立ハイテク株式会社）を用いた。また、加熱後のポリケトン膜のクラックの有無を目視で確認した。ポリケトン膜の付いていないガラス基板をリファレンスとして、膜厚１μｍに換算した透過率と、膜のクラックの有無を表１に示す。
(Evaluation of heat resistance)
The glass substrate with the polyketone film obtained in Examples 7 to 9 or Comparative Example was allowed to stand in an oven at 200 ° C. for 24 hours and heated, and the transmittance of ultraviolet light at 400 nm was measured by the ultraviolet-visible absorption spectrum method. An ultraviolet-visible spectrophotometer (“U-3310 Spectrophotometer”, Hitachi High-Technologies Corporation) was used for the measurement. In addition, the presence or absence of cracks in the polyketone film after heating was visually confirmed. Table 1 shows the transmittance converted to a film thickness of 1 μm and the presence or absence of cracks in the film, using a glass substrate without a polyketone film as a reference.
（柔軟性の評価）
実施例７〜９又は比較例で得たポリケトン膜付きカプトンフィルムを、マンドレル試験（円筒形マンドレル法）により評価した。試験はＪＩＳ Ｋ５６００−５−１：１９９９に従って行った。心棒直径は２５ｍｍから３ｍｍまで変え、クラックの発生有無を目視で確認した。クラックの発生しない心棒の最小直径を表１に示す。
(Evaluation of flexibility)
The Kapton film with a polyketone film obtained in Examples 7 to 9 or Comparative Example was evaluated by a mandrel test (cylindrical mandrel method). The test was carried out according to JIS K5600-5-1: 1999. The mandrel diameter was changed from 25 mm to 3 mm, and the presence or absence of cracks was visually confirmed. Table 1 shows the minimum diameter of the mandrel that does not generate cracks.
表１に示すとおり、特定芳香族ポリケトンは、従来の芳香族ポリケトンと同等の透過率及び耐熱性を発揮し、更に耐屈曲性に優れる。 As shown in Table 1, the specific aromatic polyketone exhibits the same transmittance and heat resistance as the conventional aromatic polyketone, and further has excellent bending resistance.
Claims (5)
（一般式（１）中、Ｒ１はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を示し、Ｒ２はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を示す。）
（一般式（２）中、Ｒ１はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を示し、Ｘは酸素原子又は下記一般式（３）で表される２価の基を示す。）
（一般式（３）中、Ｒ３及びＲ４はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を示す。）
（一般式（４）中、Ｒ５はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を示す。）
（一般式（５−１）中、Ｙ１は、置換基を有していてもよい炭素数３〜３０の２価の脂環式炭化水素基を示す。一般式（５−２）中、Ｙ２は、置換基を有していてもよい炭素数１〜３０の直鎖状又は分岐鎖状アルキレン基を示す。） At least one structural unit selected from the group consisting of the following general formula (1), the following general formula (2), and the following general formula (4), and at least one type represented by the following general formula (5-1). a structural unit, it possesses at least one structural unit represented by the following general formula (5-2), a, and Y 1 in the general formula (5-1), the formula (5-2) the molar ratio of Y 2 in (Y 1: Y 2) is 9: 1 to 3: 7 der Ru aromatic polyketones.
(In the general formula (1), R 1 independently represents a hydrocarbon atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R 2 is an independent hydrogen atom or a substituent. Indicates a hydrocarbon group having 1 to 30 carbon atoms which may have a group.)
(In the general formula (2), R 1 independently represents a hydrocarbon atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and X is an oxygen atom or the following general formula (3). Indicates a divalent group represented by.)
(In the general formula (3), R 3 and R 4 each independently represent a hydrocarbon group having 1 to 30 carbon atoms which may have a hydrogen atom or a substituent.)
(In the general formula (4), R 5 independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a hydrogen atom or a substituent.)
(In the general formula (5-1), Y 1 represents a divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms which may have a substituent. In the general formula (5-2), Y 2 represents a linear or branched alkylene group having 1 to 30 carbon atoms which may have a substituent.)
（一般式（１’）中、Ｒ１はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を示し、Ｒ２はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を示す。）
（一般式（２’）中、Ｒ１はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を示し、Ｘは酸素原子又は下記一般式（３’）で表される２価の基を示す。）
（一般式（３’）中、Ｒ３及びＲ４はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を示す。）
（一般式（４’）中、Ｒ５はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を示す。）
（一般式（５−１’）中、Ｙ１は、置換基を有していてもよい炭素数３〜３０の２価の脂環式炭化水素基を示す。一般式（５−２’）中、Ｙ２は、置換基を有していてもよい炭素数１〜３０の直鎖状又は分岐鎖状アルキレン基を示す。） Table with at least one aromatic monoma selected from the group consisting of the following general formula (1'), the following general formula (2') and the following general formula (4'), and the following general formula (5-1'). At least one dicarboxylic acid monoma to be subjected to condensation reaction with at least one dicarboxylic acid monoma represented by the following general formula (5-2 ' ) in an acidic medium, and the above general formula (5-1'). ) in Y 1 and formula (5-2 ') in the molar ratio of Y 2 (Y 1: Y 2) is 9: 1 to 3: 7 so as to the general formula (5-1' tables in) A method for producing an aromatic polyketone, which is used by adjusting the charging ratio of the dicarboxylic acid monoma to be prepared and the dicarboxylic acid monoma represented by the general formula (5-2') .
(In the general formula (1'), R 1 independently represents a hydrocarbon atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R 2 independently represents a hydrogen atom or a hydrocarbon group. Indicates a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent.)
(In the general formula (2'), R 1 independently represents a hydrocarbon atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and X is an oxygen atom or the following general formula (3). Indicates a divalent group represented by').)
(In the general formula (3'), R 3 and R 4 each independently represent a hydrocarbon group having 1 to 30 carbon atoms which may have a hydrogen atom or a substituent.)
(In the general formula (4'), R 5 independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a hydrogen atom or a substituent.)
(In the general formula (5-1'), Y 1 represents a divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms which may have a substituent. General formula (5-2'). Among them, Y 2 represents a linear or branched alkylene group having 1 to 30 carbon atoms which may have a substituent.)
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