JP3995296B2 - Thermosetting composition - Google Patents
Thermosetting composition Download PDFInfo
- Publication number
- JP3995296B2 JP3995296B2 JP02415697A JP2415697A JP3995296B2 JP 3995296 B2 JP3995296 B2 JP 3995296B2 JP 02415697 A JP02415697 A JP 02415697A JP 2415697 A JP2415697 A JP 2415697A JP 3995296 B2 JP3995296 B2 JP 3995296B2
- Authority
- JP
- Japan
- Prior art keywords
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- liquid crystalline
- carboxylic acid
- liquid crystal
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title claims description 16
- 229920001187 thermosetting polymer Polymers 0.000 title claims description 14
- 239000000178 monomer Substances 0.000 claims description 40
- 239000004973 liquid crystal related substance Substances 0.000 claims description 26
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 21
- 229920000106 Liquid crystal polymer Polymers 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 18
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 claims description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 description 13
- -1 methoxyethyl Chemical group 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- HMOZDINWBHMBSQ-UHFFFAOYSA-N 2-[3-(4,5-dihydro-1,3-oxazol-2-yl)phenyl]-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=CC=CC(C=2OCCN=2)=C1 HMOZDINWBHMBSQ-UHFFFAOYSA-N 0.000 description 2
- KAGIRXVDTGQWKF-UHFFFAOYSA-N 4-[6-(2-methylprop-2-enoyloxy)hexoxy]benzoic acid Chemical compound CC(=C)C(=O)OCCCCCCOC1=CC=C(C(O)=O)C=C1 KAGIRXVDTGQWKF-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 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
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- DJKGDNKYTKCJKD-BPOCMEKLSA-N (1s,4r,5s,6r)-1,2,3,4,7,7-hexachlorobicyclo[2.2.1]hept-2-ene-5,6-dicarboxylic acid Chemical compound ClC1=C(Cl)[C@]2(Cl)[C@H](C(=O)O)[C@H](C(O)=O)[C@@]1(Cl)C2(Cl)Cl DJKGDNKYTKCJKD-BPOCMEKLSA-N 0.000 description 1
- MJYFYGVCLHNRKB-UHFFFAOYSA-N 1,1,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)CF MJYFYGVCLHNRKB-UHFFFAOYSA-N 0.000 description 1
- 125000004955 1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C1([H])[*:2] 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- PMUPSYZVABJEKC-UHFFFAOYSA-N 1-methylcyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)CCCCC1C(O)=O PMUPSYZVABJEKC-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- QFPKSTNFHFEHJL-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)benzoic acid Chemical compound CC(=C)C(=O)OC1=CC=CC=C1C(O)=O QFPKSTNFHFEHJL-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- KFNAHVKJFHDCSK-UHFFFAOYSA-N 2-[2-(4,5-dihydro-1,3-oxazol-2-yl)ethyl]-4,5-dihydro-1,3-oxazole Chemical compound N=1CCOC=1CCC1=NCCO1 KFNAHVKJFHDCSK-UHFFFAOYSA-N 0.000 description 1
- VOGDKZZTBPDRBD-UHFFFAOYSA-N 2-[2-(4,5-dihydro-1,3-oxazol-2-yl)phenyl]-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=CC=CC=C1C1=NCCO1 VOGDKZZTBPDRBD-UHFFFAOYSA-N 0.000 description 1
- GZQKJQLFIGBEIE-UHFFFAOYSA-N 2-[4-(4,5-dihydro-1,3-oxazol-2-yl)butyl]-4,5-dihydro-1,3-oxazole Chemical compound N=1CCOC=1CCCCC1=NCCO1 GZQKJQLFIGBEIE-UHFFFAOYSA-N 0.000 description 1
- PVBLPTHPHFCENZ-UHFFFAOYSA-N 2-[4-(4,5-dihydro-1,3-oxazol-2-yl)cyclohexyl]-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1CCC(C=2OCCN=2)CC1 PVBLPTHPHFCENZ-UHFFFAOYSA-N 0.000 description 1
- ZDNUPMSZKVCETJ-UHFFFAOYSA-N 2-[4-(4,5-dihydro-1,3-oxazol-2-yl)phenyl]-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=CC=C(C=2OCCN=2)C=C1 ZDNUPMSZKVCETJ-UHFFFAOYSA-N 0.000 description 1
- LDXQWLJXDIZULP-UHFFFAOYSA-N 2-[6-(4,5-dihydro-1,3-oxazol-2-yl)hexyl]-4,5-dihydro-1,3-oxazole Chemical compound N=1CCOC=1CCCCCCC1=NCCO1 LDXQWLJXDIZULP-UHFFFAOYSA-N 0.000 description 1
- 125000004278 2-oxazolin-2-yl group Chemical group [H]C1([H])OC(*)=NC1([H])[H] 0.000 description 1
- ZKFOEDSYSPDTEB-UHFFFAOYSA-N 2-prop-2-enoyloxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1OC(=O)C=C ZKFOEDSYSPDTEB-UHFFFAOYSA-N 0.000 description 1
- DNCFPDURLPJGKX-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)benzoic acid Chemical compound CC(=C)C(=O)OC1=CC=C(C(O)=O)C=C1 DNCFPDURLPJGKX-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- IRQWEODKXLDORP-UHFFFAOYSA-N 4-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=C)C=C1 IRQWEODKXLDORP-UHFFFAOYSA-N 0.000 description 1
- IFIUFEBEPGGBIJ-UHFFFAOYSA-N 4-methyl-4,5-dihydro-1,3-oxazole Chemical compound CC1COC=N1 IFIUFEBEPGGBIJ-UHFFFAOYSA-N 0.000 description 1
- RZZZQPNSNIVWAU-UHFFFAOYSA-N 4-prop-2-enoyloxybenzoic acid Chemical compound OC(=O)C1=CC=C(OC(=O)C=C)C=C1 RZZZQPNSNIVWAU-UHFFFAOYSA-N 0.000 description 1
- ZXJMMQWZOFQDFC-UHFFFAOYSA-N 5-methyl-2-[3-(5-methyl-4,5-dihydro-1,3-oxazol-2-yl)phenyl]-4,5-dihydro-1,3-oxazole Chemical compound O1C(C)CN=C1C1=CC=CC(C=2OC(C)CN=2)=C1 ZXJMMQWZOFQDFC-UHFFFAOYSA-N 0.000 description 1
- DEXHGMUVBNTXIN-UHFFFAOYSA-N 5-methyl-2-[4-(5-methyl-4,5-dihydro-1,3-oxazol-2-yl)phenyl]-4,5-dihydro-1,3-oxazole Chemical compound O1C(C)CN=C1C1=CC=C(C=2OC(C)CN=2)C=C1 DEXHGMUVBNTXIN-UHFFFAOYSA-N 0.000 description 1
- CIIILUMBZOGKDF-UHFFFAOYSA-N 5-methyl-4,5-dihydro-1,3-oxazole Chemical compound CC1CN=CO1 CIIILUMBZOGKDF-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005264 High molar mass liquid crystal Substances 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- KZHATIZLAHNHSV-UHFFFAOYSA-N OC(=O)C1=CC=CC=C1OCC1=CC=C(C=C)C=C1 Chemical compound OC(=O)C1=CC=CC=C1OCC1=CC=C(C=C)C=C1 KZHATIZLAHNHSV-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 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
- 230000007812 deficiency Effects 0.000 description 1
- 125000005716 dioxanylene group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 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
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005551 pyridylene group Chemical group 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 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
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
Landscapes
- Liquid Crystal Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、硬化後に液晶相を示す熱硬化性組成物に関し、詳細には、液晶相を示す重合性単量体およびカルボン酸基を有する重合性単量体からなる共重合物と、分子中にオキサゾリン基を２個以上有する化合物とからなる熱硬化性組成物に関する。
【０００２】
【従来の技術及び発明が解決しようとする課題】
近年、液晶物質はＴＮ型やＳＴＮ型に代表されるディスプレイ素子等の液晶分子の可逆的運動を利用した表示媒体への応用以外にも、その配向性と屈折率、誘電率、磁化率等の物理的性質の異方性を利用して、位相差板、偏光板、光偏光プリズム、各種光フィルター等の光学異方体への応用が検討されている。
【０００３】
このように液晶物質を構成材料とする光学異方体には、安定で均一な光学特性を得るために、液晶状態における液晶分子の均一な配向状態を半永久的に固定化して、機械的にも熱的にも安定なガラス転移温度（以下、「Ｔｇ」ともいう）の高い、配向性に優れた重合物とすることが必須である。
【０００４】
液晶状態における液晶分子の均一な配向状態を半永久的に固定化する手段としては、例えば、重合性官能基を有する液晶性化合物又はこのような化合物を含有する重合性液晶組成物を、液晶状態で均一に配向させた後、液晶状態を保持したまま紫外線等のエネルギー線を照射することによって光重合させて、均一な配向状態を半永久的に固定化する方法が既に知られている。
【０００５】
しかしながら、この方法では光重合を行なう為に高価な光重合開始剤が不可欠であり、また、低分子量体などにより機械的強度が不足したり、イミド樹脂などと積層した際に液晶性が失われるなどの問題を有していた。
【０００６】
また、基材上に塗布した後に重合した場合の欠点を克服する方法としては、重合性液晶組成物を光又は熱により重合した後に、溶液として基材上に塗布して乾燥後、等方性液体となるまで加熱し、徐冷して液晶状態を固定化する方法が知られている。
【０００７】
しかしながら、この方法を用いるには溶媒への溶解性に優れた液晶性重合体であることが必要である。しかも、近年はハロゲン系の有機溶剤の使用が制限されていることからハロゲンを含まない有機溶剤への溶解性に優れた液晶重合体が求められている。これまで具体的に検討されてきた液晶性単量体の重合物は溶解性に乏しいか、溶解性が高過ぎて、イミド樹脂などと積層した際に液晶性が失われるなどの問題を有していた。
【０００８】
従って、本発明の目的は、基材上への塗布時には溶剤への溶解性に優れ、使用時には耐溶剤性に優れる液晶性重合体を提供することにある。
【０００９】
【課題を解決するための手段】
本発明者等は、鋭意検討を重ねた結果、重合性の液晶性単量体およびカルボン酸基を有する重合性単量体の共重合物と、分子中に２個以上のオキサゾリン基を有する化合物とからなる熱硬化性組成物が、上記目的を達成し得ることの知見をした。
【００１０】
本発明は、上記知見に基づきなされたもので、下記（Ａ）および（Ｂ）成分からなり、該（Ａ）成分が有するカルボン酸基と、該（Ｂ）成分が有するオキサゾリン基とのモル比（前者／後者）が０．８〜１．２の範囲内である熱硬化性組成物を提供するものである。
（Ａ）；カルボン酸基を有していない重合性液晶性単量体（ａ）、カルボン酸基を有している重合性液晶性単量体（ｂ）およびカルボン酸基を有している非液晶性の重合性単量体（ｃ）からなる群より選ばれる少なくとも２種の単量体を共重合して得られる、カルボン酸基を有する液晶性重合体であって、上記重合性液晶性単量体（ａ）および（ｂ）が、下記〔化１〕の一般式（Ｉ）で表される化合物（但し、（ａ）の場合はＲ2がカルボキシル基以外の基、（ｂ）の場合はＲ2がカルボキシル基）であり、かつ、該重合性液晶性単量体（ａ）および／または（ｂ）からなる構成単位部分の含有量の合計が、該（Ａ）成分である液晶性重合体中５０重量％以上である液晶性重合体。
（Ｂ）；分子中に２個以上のオキサゾリン基を有する化合物。
【化１】
【発明の実施の形態】
以下、本発明の熱硬化性組成物について詳細に説明する。
本発明に使用される（Ａ）成分である、カルボン酸基を有する液晶性重合体において、カルボン酸基を有していない重合性液晶性単量体（ａ）またはカルボン酸基を有している重合性液晶性単量体（ｂ）は、下記〔化２〕（前記〔化１〕と同じ）の一般式（Ｉ）で表される化合物（但し、（ａ）の場合はＲ2 がカルボキシル基以外の基、（ｂ）の場合はＲ2 がカルボキシル基）である。
【００１２】
【化２】
ここで、上記一般式（Ｉ）中、環Ａ、Ｂ、ＣおよびＤで表される炭化水素６員環または複素６員環で構成される基としては、１，４−フェニレン、１，４−シクロヘキシレン、１，４−シクロヘキセニレン、ジオキサニレン、ピリジレン、ピリミジレン等が挙げられ、縮合環としてはナフチレン等が挙げられる。
【００１４】
また、R2で表されるアルキル基としては、メチル、エチル、プロピル、ブチル、イソブチル、ペンチル、ヘキシル、ヘプチル、オクチルが挙げられ、アルコキシ基としては、上記アルキル基に対応するアルコキシ基が挙げられ、アルコキシアルキル基としては、メトキシメチル、メトキシエチル、メトキシプロピル、エトキシメチル、エトキシエチルなどが挙げられ、フルオロアルキル基としては、トリフルオロメチル、ペンタフルオロエチルなどの上記アルキル基に対応するフルオロアルキル基が挙げられる。
【００１５】
また、R2、X1およびX2で表されるハロゲン原子としては、例えば、フッ素、塩素、臭素が挙げられ、得られる化合物が安定性に優れることからフッ素が好ましい。
【００１６】
また、ｌは、０〜１４を表し、ｌが１４より大きいと、液晶性単量体を重合して得られる液晶性重合体の配向状態の安定性が低下する。
【００１７】
また、ｎ、ｐ、ｑおよびｒは各々独立に０または１を示し、２≦ｎ＋ｐ＋ｑ＋ｒ≦４であり、これらの和が１では得られる重合物の液晶性が乏しくなることがあり、４より大きいと、得られる重合物が剛直になり配向性に乏しくなることがある。
【００１８】
従って、上記カルボン酸基を有していない重合性液晶性単量体（ａ）、および上記カルボン酸基を有する重合性液晶性単量体（ｂ）としては、より具体的には、前者としては、下記〔化３〕〜〔化１９〕の化合物Ｎｏ．１〜１７等が挙げられ、後者としては、下記〔化２０〕〜〔化２２〕の化合物Ｎｏ．１８〜２０が挙げられる。ただし、本発明に係る上記重合性液晶性単量体（ａ）および上記重合性液晶性単量体（ｂ）は以下に示す化合物により制限を受けるものではない。
【００１９】
【化３】
【化４】
【化５】
【化６】
【化７】
【化８】
【化９】
【化１０】
【化１１】
【化１２】
【化１３】
【化１４】
【化１５】
【化１６】
【化１７】
【化１８】
【化１９】
【化２０】
【化２１】
【化２２】
上記重合性液晶性単量体（ａ）および（ｂ）は、各々単独または２種以上を組み合わせて用いることができ、該重合性液晶性単量体（ａ）および／または（ｂ）からなる構成単位部分の含有量の合計が、得られる液晶性重合体〔（Ａ）成分〕中５０重量％以上となる量で用いる。該含有量の合計が３０重量％未満では、得られる重合体が液晶性を示さないか、示しても液晶相を示す温度範囲が狭くなることがある。
【００４０】
また、上記カルボン酸基を有している非液晶性の重合性単量体（ｃ）としては、例えば、下記〔化２３〕の一般式（II）で表される化合物等が用いられる。
【００４１】
【化２３】
上記一般式（II）で表される化合物の具体例としては、例えば、アクリル酸、メタクリル酸、アクリロイルオキシ安息香酸、メタクリロイルオキシ安息香酸、４−アクリロイルオキシ安息香酸、４−メタクリロイルオキシ安息香酸、４−（２−アクリロイルオキシエチルオキシ）安息香酸、４−（６−メタクリロイルオキシヘキシルオキシ）安息香酸、４−カルボキシスチレン、４−（２−カルボキシフェノキシメチル）スチレンなどが挙げられる。
【００４３】
また、上記（Ａ）成分を得るに際し、得られる液晶性重合体のＴｇなどの機械特性を調整するために、（ａ），（ｂ）および（ｃ）の単量体以外に必要に応じて他の単量体を使用することができる。該他の単量体は、上記（ａ）および／または（ｂ）の単量体が前記含有量の範囲を逸脱しない範囲で用いられることが好ましい。該他の単量体としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレートテトラヒドロフルフリル（メタ）アクリレート、第三ブチル（メタ）アクリレート、グリシジル（メタ）アクリレート、トリフルオロエチル（メタ）アクリレート、テトラフルオロプロピル（メタ）アクリレート等の（メタ）アクリル酸エステル、ジアセトンアクリルアミド、スチレン、ビニルトルエン等が挙げられる。
【００４４】
また、上記（Ａ）成分を得るに際し、カルボン酸基を有している単量体〔（ａ）および（ｂ）〕の使用量は、得られる液晶性重合体のカルボン酸当量が５００〜５００００、特に１０００〜１００００となる範囲の量が好ましい。該カルボン酸当量が５００未満では、本発明の組成物を硬化した後にできる硬化膜が液晶性を保持できないことがあり、５００００より大きいと、十分な熱硬化性が得られないことがある。
【００４５】
また、上記重合性液晶性単量体（ａ）、上記重合性液晶性単量体（ｂ）および上記非液晶性の重合性単量体（ｃ）からなる群より選ばれる少なくとも２種の単量体を共重合する方法は特に限定されるものではなく、例えば、ラジカル開始剤を用いた熱重合や光開始剤を用いた光重合により得られる方法などがあげられる。
【００４６】
上記（Ａ）成分である液晶性重合体は、その数平均分子量が３０００〜５０００００であることが好ましく、５０００〜３０００００であることが特に好ましい。該数平均分子量が３０００より小さいと、得られる硬化膜の機械強度が不足して実用的でなく、５０００００より大きいと有機溶剤への溶解性が低下して溶液として基材に塗布することが困難になる。
【００４７】
本発明に使用される（Ｂ）成分である分子中に２個以上のオキサゾリン基を有する化合物（以下、「オキサゾリン化合物」ともいう）としては、特に限定されるものではないが、例えば、2,2'- ビス(2- オキサゾリン) 、2,2'- ビス(4- メチル-2- オキサゾリン) 、2,2'- ビス(5- メチル-2- オキサゾリン) 、2,2'- ビス(5,5'-ジメチルオキサゾリン) 、2,2'- ビス(4,4,4',4'- テトラメチル-2- オキサゾリン) 、1,2-ビス(2- オキサゾリン-2- イル) エタン、1,4-ビス(2- オキサゾリン-2- イル) ブタン、1,6-ビス(2- オキサゾリン-2- イル) ヘキサン、1,8-ビス(2- オキサゾリン-2- イル) 、1,4-ビス(2- オキサゾリン-2- イル) シクロヘキサン、1,2-ビス(2- オキサゾリン-2- イル) ベンセン、1,3-ビス(2- オキサゾリン-2- イル) ベンゼン、1,4-ビス(2- オキサゾリン-2- イル) ベンゼン、1,2-ビス(5- メチル-2- オキサゾリン-2- イル) ベンゼン、1,3-ビス(5- メチル-2- オキサゾリン-2- イル) ベンゼン、1,4-ビス(5- メチル-2- オキサゾリン-2- イル) ベンゼン、1,4-ビス(4,4'-ジメチル-2- オキサゾリン-2- イル) ベンゼン等のビスオキサゾリン化合物、および、該ビスオキサゾリン化合物のオキサゾリン基２化学当量と多塩基性カルボン酸（例えばマレイン酸、琥珀酸、イタコン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、メチルヘキサヒドロフタル酸、クロレンド酸、トリメリット酸、ピロメリット酸、ベンゾフェノンテトラカルボン酸等）のカルボキシル基１化学当量とを反応させて得られる末端オキサゾリン基を有する化合物等を挙げることができる。
【００４８】
上記オキサゾリン化合物〔（Ｂ）成分〕の前記液晶性重合体〔（Ａ）成分〕に対する使用量の比率（モル比）は、本発明においては、該液晶性重合体〔（Ａ）成分〕が有するカルボン酸基と、オキサゾリン化合物〔（Ｂ）成分〕が有するオキサゾリン基とが反応して硬化することにより、液晶性重合体に耐溶剤性を付与するなどの改質を行うものであるため、カルボン酸基／オキサゾリン基が０．８〜１．２となるように使用する。上記オキサゾリン化合物の量が大過剰（上記範囲の下限未満）になると、得られる硬化膜は未反応のオキサゾリン化合物を多量に含有するため耐溶剤性が低下することがあり、また上記オキサゾリン化合物の量が著しく不足する場合（上記範囲の上限超）は、硬化が十分行われず、得られる硬化膜の耐溶剤性が低下したり、未反応のカルボン酸基が多量に残存して硬化膜の電気的特性などに悪影響を及ぼすことがある。
【００４９】
本発明の熱硬化性組成物を用いて硬化膜を得る際の硬化方法としては、通常公知の方法が挙げられ、例えば、前記（Ａ）成分と前記（Ｂ）成分とを溶剤に溶解して塗布液を得、得られた塗布液を、スピンコーター等によりガラス基板等の基材上に塗布した後、所望の温度および時間で加熱して硬化する方法等が挙げられる。
【００５０】
本発明の熱硬化性組成物から得られる硬化膜は、ディスプレイ素子等の表示媒体や、位相差板、偏光板、光偏光プリズム、各種光フィルター等の光学異方体等、種々の液晶物質としての用途に使用される。
【００５１】
【実施例】
以下、合成例および実施例により本発明の熱硬化性組成物を更に詳細に説明する。しかしながら、本発明はこれらの合成例および実施例により何ら制限されるものではない。
【００５２】
先ず、実施例および比較例で使用した化合物の具体的な合成例を示す。
〔共重合体No.1〜No.7および比較共重合体の合成〕
重合性液晶性単量体（下記〔表１〕参照）と4-(6- メタアクリロイルオキシヘキシルオキシ) 安息香酸（以下、「ＭＡＨＢＡ」ともいう）とを合計で20g になるようテトラヒドロフラン200ml に溶解し、過酸化ベンゾイルを全単量体に対して3mol% 加え、アルゴン置換後、65℃で8 時間反応させた。反応後、得られた反応液をメタノール2000mlに加え、生成する白色沈澱をろ取した。得られた共重合体の収量、収率、並びに単分散ポリスチレン換算（ＧＰＣ：テトラヒドロフラン）の数平均分子量（Mn）および重量平均分子量／数平均分子量（Mw/Mn)を測定し、それらの結果を下記〔表１〕に示す。また、得られた共重合体の相転移温度を測定し、その結果を下記〔表２〕に示す。
【００５３】
共重合体No.8の合成
ＭＡＨＢＡをメタクリル酸に替えた以外は、共重合体No.3と同様にして共重合体No.8を得た。得られた共重合体の収量、収率、MnおよびMn/Mw を測定し、それらの結果を下記〔表１〕に示す。また、得られた共重合体の相転移温度を測定し、その結果を下記〔表２〕に示す。
【００５４】
【表１】
【表２】
実施例１−１〜１−８および比較例１−１
上記合成例により得られた共重合体３ｇと、該共重合体が有するカルボン酸基と過不足なく反応する量の１，３−フェニレンビスオキサゾリンとを、シクロヘキサノン／メチルエチルケトン＝８／２（ｗｔ／ｗｔ）（以下、「ＣＨ／ＭＥＫ」ともいう）１７ｇに溶解して塗布液を得た。得られた塗布液をスピンコーターでガラス基板に塗布して１５０℃で１時間熱硬化した。得られた硬化膜はいずれも光学特性である複屈折性を保持していた。得られた硬化膜にクロロホルムまたはＣＨ／ＭＥＫを１滴滴下して膜の膨潤などの変化の有無を目視で観察して耐溶剤性を評価した。変化が認められなかったものを○、若干の膨潤を示したものを△、明白に膨潤などの変化を示したものを×として評価した。それらの結果を下記〔表３〕に示す。
【００５７】
比較例１−２
オキサゾリン化合物を含まない以外は、実施例１−１と同様にして膜を得、同様の評価をした。それらの結果を下記〔表３〕に示す。
【００５８】
【表３】
以上の結果より、カルボン酸基を有する特定の液晶性重合体〔前記（Ａ）成分〕および特定のオキサゾリン化合物〔（Ｂ）成分〕からなる本発明の熱硬化性組成物（実施例１−１〜１−８）は、溶剤への溶解性に優れ、また硬化後には優れた硬化膜を提供できることが明らかである。
【００６０】
【発明の効果】
本発明の熱硬化性組成物は、溶剤への溶解性に優れ、また硬化後の硬化膜が耐溶剤性に優れるものである。このため、本発明の熱硬化性組成物によれば、耐溶剤性に優れる高分子液晶膜を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a thermosetting composition exhibiting a liquid crystal phase after curing, and more specifically, a copolymer comprising a polymerizable monomer exhibiting a liquid crystal phase and a polymerizable monomer having a carboxylic acid group, and a molecule. The present invention relates to a thermosetting composition comprising a compound having two or more oxazoline groups.
[0002]
[Prior art and problems to be solved by the invention]
In recent years, liquid crystal materials have a high degree of orientation, refractive index, dielectric constant, magnetic susceptibility, etc., in addition to application to display media using the reversible motion of liquid crystal molecules such as TN type and STN type display elements. Applications to optical anisotropic bodies such as retardation plates, polarizing plates, light polarizing prisms, and various optical filters have been studied using the anisotropy of physical properties.
[0003]
Thus, in order to obtain stable and uniform optical characteristics, an optically anisotropic body composed of a liquid crystal substance has a uniform alignment state of liquid crystal molecules in a liquid crystal state semi-permanently and mechanically. It is essential to provide a polymer having a high glass transition temperature (hereinafter also referred to as “Tg”) which is thermally stable and excellent in orientation.
[0004]
As a means for semi-permanently fixing the uniform alignment state of the liquid crystal molecules in the liquid crystal state, for example, a liquid crystal compound having a polymerizable functional group or a polymerizable liquid crystal composition containing such a compound can be used in the liquid crystal state. A method is known in which a uniform alignment state is semi-permanently fixed by irradiating energy rays such as ultraviolet rays while maintaining a liquid crystal state after the alignment is uniformly performed.
[0005]
However, in this method, an expensive photopolymerization initiator is indispensable for carrying out photopolymerization, and the liquid crystallinity is lost when laminated with an imide resin or the like due to insufficient mechanical strength due to a low molecular weight substance or the like. Had problems such as.
[0006]
In addition, as a method of overcoming the drawbacks of polymerization after coating on a substrate, the polymerizable liquid crystal composition is polymerized by light or heat, then coated on the substrate as a solution, dried, and isotropic. A method for fixing a liquid crystal state by heating to a liquid and gradually cooling is known.
[0007]
However, in order to use this method, it is necessary to be a liquid crystalline polymer having excellent solubility in a solvent. Moreover, in recent years, since the use of halogen-based organic solvents is limited, liquid crystal polymers having excellent solubility in organic solvents containing no halogen are required. The polymer of the liquid crystalline monomer that has been specifically studied so far has poor solubility or too high solubility, causing problems such as loss of liquid crystallinity when laminated with an imide resin. It was.
[0008]
Accordingly, an object of the present invention is to provide a liquid crystalline polymer that is excellent in solubility in a solvent when applied onto a substrate and excellent in solvent resistance when used.
[0009]
[Means for Solving the Problems]
As a result of intensive studies, the present inventors have obtained a copolymer of a polymerizable liquid crystal monomer and a polymerizable monomer having a carboxylic acid group, and a compound having two or more oxazoline groups in the molecule It was found that a thermosetting composition comprising:
[0010]
The present invention has been made based on the above findings, moles of Ri Do from the following components (A) and (B), a carboxylic acid group having the said component (A), and oxazoline group of the component (B) A thermosetting composition having a ratio (the former / the latter) in the range of 0.8 to 1.2 is provided.
(A): a polymerizable liquid crystal monomer (a) having no carboxylic acid group, a polymerizable liquid crystal monomer (b) having a carboxylic acid group, and a carboxylic acid group A liquid crystalline polymer having a carboxylic acid group, obtained by copolymerizing at least two monomers selected from the group consisting of non-liquid crystalline polymerizable monomers (c), wherein the polymerizable liquid crystal A monomer represented by the general formula (I) of the following [Chemical Formula 1] (in the case of (a), R 2 is a group other than a carboxyl group, (b) for R 2 is Ri carboxyl group) der, and the total content of the structural unit portion consisting of polymerizable liquid crystalline monomer (a) and / or (b) is, in the component (a) A liquid crystalline polymer that is 50% by weight or more in a certain liquid crystalline polymer.
(B); a compound having two or more oxazoline groups in the molecule.
[Chemical 1]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the thermosetting composition of the present invention will be described in detail.
The liquid crystalline polymer having a carboxylic acid group, which is the component (A) used in the present invention, has a polymerizable liquid crystalline monomer (a) having no carboxylic acid group or a carboxylic acid group. The polymerizable liquid crystalline monomer (b) is a compound represented by the following general formula (I) of the following [Chemical formula 2] (same as the above [Chemical formula 1]) (in the case of (a), R 2 is groups other than carboxyl group, R 2 is a carboxyl group) in the case of (b).
[0012]
[Chemical 2]
Here, in the above general formula (I), examples of the group composed of a hydrocarbon 6-membered ring or a hetero 6-membered ring represented by rings A, B, C and D include 1,4-phenylene, 1,4 -Cyclohexylene, 1,4-cyclohexenylene, dioxanylene, pyridylene, pyrimidylene, etc. are mentioned, and naphthylene etc. are mentioned as a condensed ring.
[0014]
Examples of the alkyl group represented by R 2 include methyl, ethyl, propyl, butyl, isobutyl, pentyl, hexyl, heptyl, octyl, and examples of the alkoxy group include alkoxy groups corresponding to the above alkyl groups. Examples of the alkoxyalkyl group include methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl, etc., and examples of the fluoroalkyl group include fluoroalkyl groups corresponding to the above alkyl groups such as trifluoromethyl and pentafluoroethyl. Is mentioned.
[0015]
Examples of the halogen atom represented by R 2 , X 1 and X 2 include fluorine, chlorine and bromine, and fluorine is preferred because the resulting compound is excellent in stability.
[0016]
Moreover, l represents 0-14, and when l is larger than 14, the stability of the alignment state of the liquid crystalline polymer obtained by polymerizing the liquid crystalline monomer is lowered.
[0017]
N, p, q and r each independently represent 0 or 1, and 2 ≦ n + p + q + r ≦ 4. When the sum of these is 1, the obtained polymer may have poor liquid crystallinity and is larger than 4. In some cases, the resulting polymer is rigid and poor in orientation.
[0018]
Therefore, as the polymerizable liquid crystal monomer (a) having no carboxylic acid group and the polymerizable liquid crystal monomer (b) having the carboxylic acid group, more specifically, the former Of the following compounds [Chemical Formula 3] to [Chemical Formula 19]. 1 to 17 and the like. Examples of the latter include compound Nos. 18-20 are mentioned. However, the polymerizable liquid crystalline monomer (a) and the polymerizable liquid crystalline monomer (b) according to the present invention are not limited by the following compounds.
[0019]
[Chemical 3]
[Formula 4]
[Chemical formula 5]
[Chemical 6]
[Chemical 7]
[Chemical 8]
[Chemical 9]
[Chemical Formula 10]
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The polymerizable liquid crystalline monomers (a) and (b) can be used alone or in combination of two or more, and are composed of the polymerizable liquid crystalline monomers (a) and / or (b). the total content of the constituent unit parts, are use in an amount of obtained liquid crystalline polymer [component (a)] 5 0 wt% or more. If the total content is less than 30% by weight, the resulting polymer may not exhibit liquid crystallinity, or the temperature range showing a liquid crystal phase may be narrow even if it is shown.
[0040]
Moreover, as the non-liquid crystalline polymerizable monomer (c) having a carboxylic acid group, for example, a compound represented by the following general formula (II) of [Chemical Formula 23] is used.
[0041]
Embedded image
Specific examples of the compound represented by the general formula (II) include, for example, acrylic acid, methacrylic acid, acryloyloxybenzoic acid, methacryloyloxybenzoic acid, 4-acryloyloxybenzoic acid, 4-methacryloyloxybenzoic acid, 4 Examples include-(2-acryloyloxyethyloxy) benzoic acid, 4- (6-methacryloyloxyhexyloxy) benzoic acid, 4-carboxystyrene, 4- (2-carboxyphenoxymethyl) styrene, and the like.
[0043]
Further, when obtaining the component (A), in order to adjust mechanical properties such as Tg of the obtained liquid crystalline polymer, in addition to the monomers (a), (b) and (c), as necessary. Other monomers can be used. The other monomer is preferably used in such a range that the monomer (a) and / or (b) does not deviate from the content range. Examples of the other monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate tetrahydrofurfuryl (meth) acrylate, tert-butyl (meth) acrylate, Examples include (meth) acrylic acid esters such as glycidyl (meth) acrylate, trifluoroethyl (meth) acrylate, and tetrafluoropropyl (meth) acrylate, diacetone acrylamide, styrene, and vinyltoluene.
[0044]
Moreover, when obtaining the said (A) component, the usage-amount of the monomer [(a) and (b)] which has a carboxylic acid group makes the carboxylic acid equivalent of the obtained liquid crystalline polymer 500-50000. In particular, an amount in the range of 1000 to 10,000 is preferred. When the carboxylic acid equivalent is less than 500, a cured film formed after the composition of the present invention is cured may not retain liquid crystallinity, and when it is more than 50000, sufficient thermosetting property may not be obtained.
[0045]
Further, at least two kinds of single monomers selected from the group consisting of the polymerizable liquid crystalline monomer (a), the polymerizable liquid crystalline monomer (b), and the non-liquid crystalline polymerizable monomer (c) are used. The method for copolymerizing the monomer is not particularly limited, and examples thereof include a method obtained by thermal polymerization using a radical initiator or photopolymerization using a photoinitiator.
[0046]
The number average molecular weight of the liquid crystalline polymer as the component (A) is preferably 3000 to 500000, and particularly preferably 5000 to 300000. If the number average molecular weight is less than 3000, the cured film obtained is insufficient in mechanical strength and is not practical. If it is more than 500,000, the solubility in an organic solvent is lowered and it is difficult to apply the solution as a solution to a substrate. become.
[0047]
The compound having two or more oxazoline groups in the molecule as the component (B) used in the present invention (hereinafter, also referred to as “oxazoline compound”) is not particularly limited. 2'-bis (2-oxazoline), 2,2'-bis (4-methyl-2-oxazoline), 2,2'-bis (5-methyl-2-oxazoline), 2,2'-bis (5 , 5'-dimethyloxazoline), 2,2'-bis (4,4,4 ', 4'-tetramethyl-2-oxazoline), 1,2-bis (2-oxazolin-2-yl) ethane, 1 , 4-Bis (2-oxazolin-2-yl) butane, 1,6-bis (2-oxazolin-2-yl) hexane, 1,8-bis (2-oxazolin-2-yl), 1,4- Bis (2-oxazolin-2-yl) cyclohexane, 1,2-bis (2-oxazolin-2-yl) benzene, 1,3-bis (2-oxazolin-2-yl) benzene, 1,4-bis ( 2-Oxazolin-2-yl) benzene, 1,2-bis (5-methyl) -2-Oxazolin-2-yl) benzene, 1,3-bis (5-methyl-2-oxazolin-2-yl) benzene, 1,4-bis (5-methyl-2-oxazolin-2-yl) Benzene, 1,4-bis (4,4′-dimethyl-2-oxazolin-2-yl) Bisoxazoline compound such as benzene, and two chemical equivalents of the oxazoline group of the bisoxazoline compound and a polybasic carboxylic acid (for example, 1 chemical equivalent of carboxyl group of maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, chlorendic acid, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, etc. And compounds having a terminal oxazoline group obtained by reacting with.
[0048]
In the present invention, the ratio (molar ratio) of the oxazoline compound [component (B)] to the liquid crystalline polymer [component (A)] is included in the liquid crystalline polymer [component (A)]. Since the carboxylic acid group reacts with the oxazoline group of the oxazoline compound [component (B)] and cures, the liquid crystalline polymer is modified to provide solvent resistance. Acid group / oxazoline group is 0 . It is used so as to be 8 to 1.2 . When the amount of the oxazoline compound is excessively large (below the lower limit of the above range), the resulting cured film contains a large amount of unreacted oxazoline compound, so that the solvent resistance may be lowered. Is extremely insufficient (exceeding the upper limit of the above range), the curing is not sufficiently performed, the solvent resistance of the resulting cured film is lowered, or a large amount of unreacted carboxylic acid groups remain, resulting in the electrical properties of the cured film. May adversely affect characteristics.
[0049]
As a curing method for obtaining a cured film using the thermosetting composition of the present invention, there are usually known methods. For example, the component (A) and the component (B) are dissolved in a solvent. Examples of the method include obtaining a coating solution, applying the obtained coating solution on a substrate such as a glass substrate with a spin coater or the like, and then heating and curing at a desired temperature and time.
[0050]
Cured films obtained from the thermosetting composition of the present invention are used as various liquid crystal substances such as display media such as display elements, optical anisotropic bodies such as retardation plates, polarizing plates, light polarizing prisms, and various optical filters. Used for applications.
[0051]
【Example】
Hereinafter, the thermosetting composition of the present invention will be described in more detail with reference to synthesis examples and examples. However, the present invention is not limited by these synthesis examples and examples.
[0052]
First, specific synthesis examples of the compounds used in Examples and Comparative Examples are shown.
[Synthesis of copolymers No. 1 to No. 7 and comparative copolymers]
Dissolve the polymerizable liquid crystalline monomer (see [Table 1] below) and 4- (6-methacryloyloxyhexyloxy) benzoic acid (hereinafter also referred to as “MAHBA”) in 200 ml of tetrahydrofuran to a total of 20 g. Then, benzoyl peroxide was added in an amount of 3 mol% based on the total amount of the monomers, and the reaction was carried out at 65 ° C. for 8 hours after argon substitution. After the reaction, the resulting reaction solution was added to 2000 ml of methanol, and the resulting white precipitate was collected by filtration. The yield and yield of the obtained copolymer, and the number average molecular weight (Mn) and weight average molecular weight / number average molecular weight (Mw / Mn) in terms of monodisperse polystyrene (GPC: tetrahydrofuran) were measured. It shows in the following [Table 1]. Moreover, the phase transition temperature of the obtained copolymer was measured, and the result is shown in the following [Table 2].
[0053]
Synthesis of Copolymer No. 8 Copolymer No. 8 was obtained in the same manner as Copolymer No. 3, except that MAHBA was changed to methacrylic acid. The yield, yield, Mn and Mn / Mw of the obtained copolymer were measured, and the results are shown in the following [Table 1]. Moreover, the phase transition temperature of the obtained copolymer was measured, and the result is shown in the following [Table 2].
[0054]
[Table 1]
[Table 2]
Examples 1-1 to 1-8 and Comparative Example 1-1
3 g of the copolymer obtained by the above synthesis example, and 1,3-phenylenebisoxazoline in an amount that reacts with the carboxylic acid group of the copolymer without excess or deficiency, were cyclohexanone / methyl ethyl ketone = 8/2 (wt / wt). wt) (hereinafter also referred to as “CH / MEK”) 17 g to obtain a coating solution. The obtained coating solution was applied to a glass substrate with a spin coater and thermally cured at 150 ° C. for 1 hour. All of the obtained cured films maintained birefringence, which is an optical characteristic. One drop of chloroform or CH / MEK was dropped on the obtained cured film, and the presence or absence of changes such as swelling of the film was visually observed to evaluate the solvent resistance. Evaluation was made with ◯ indicating no change, Δ indicating a slight swelling, and × indicating an obvious change such as swelling. The results are shown in [Table 3] below.
[0057]
Comparative Example 1-2
A film was obtained in the same manner as in Example 1-1 except that the oxazoline compound was not included, and the same evaluation was performed. The results are shown in [Table 3] below.
[0058]
[Table 3]
From the above results, the thermosetting composition of the present invention (Example 1-1) comprising a specific liquid crystalline polymer having a carboxylic acid group [the component (A)] and a specific oxazoline compound (component (B)). It is apparent that ˜1-8) is excellent in solubility in a solvent and can provide an excellent cured film after curing.
[0060]
【The invention's effect】
The thermosetting composition of this invention is excellent in the solubility to a solvent, and the cured film after hardening is excellent in solvent resistance. For this reason, according to the thermosetting composition of this invention, the polymer liquid crystal film excellent in solvent resistance can be provided.
Claims (1)
（Ａ）；カルボン酸基を有していない重合性液晶性単量体（ａ）、カルボン酸基を有している重合性液晶性単量体（ｂ）およびカルボン酸基を有している非液晶性の重合性単量体（ｃ）からなる群より選ばれる少なくとも２種の単量体を共重合して得られる、カルボン酸基を有する液晶性重合体であって、上記重合性液晶性単量体（ａ）および（ｂ）が、下記〔化１〕の一般式（Ｉ）で表される化合物（但し、（ａ）の場合はＲ2がカルボキシル基以外の基、（ｂ）の場合はＲ2がカルボキシル基）であり、かつ、該重合性液晶性単量体（ａ）および／または（ｂ）からなる構成単位部分の含有量の合計が、該（Ａ）成分である液晶性重合体中５０重量％以上である液晶性重合体。
（Ｂ）；分子中に２個以上のオキサゾリン基を有する化合物。
(A): a polymerizable liquid crystal monomer (a) having no carboxylic acid group, a polymerizable liquid crystal monomer (b) having a carboxylic acid group, and a carboxylic acid group A liquid crystalline polymer having a carboxylic acid group, obtained by copolymerizing at least two monomers selected from the group consisting of non-liquid crystalline polymerizable monomers (c), wherein the polymerizable liquid crystal A monomer represented by the general formula (I) of the following [Chemical Formula 1] (in the case of (a), R 2 is a group other than a carboxyl group, (b) for R 2 is Ri carboxyl group) der, and the total content of the structural unit portion consisting of polymerizable liquid crystalline monomer (a) and / or (b) is, in the component (a) A liquid crystalline polymer that is 50% by weight or more in a certain liquid crystalline polymer.
(B); a compound having two or more oxazoline groups in the molecule.
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