JP2011195795A - Liquid crystal composition containing polymerizable compound and liquid crystal displaying element using the same liquid crystal composition - Google Patents
Liquid crystal composition containing polymerizable compound and liquid crystal displaying element using the same liquid crystal composition Download PDFInfo
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- JP2011195795A JP2011195795A JP2010067352A JP2010067352A JP2011195795A JP 2011195795 A JP2011195795 A JP 2011195795A JP 2010067352 A JP2010067352 A JP 2010067352A JP 2010067352 A JP2010067352 A JP 2010067352A JP 2011195795 A JP2011195795 A JP 2011195795A
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- Prior art keywords
- liquid crystal
- group
- crystal composition
- general formula
- carbon atoms
- Prior art date
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 130
- 150000001875 compounds Chemical class 0.000 title claims abstract description 109
- 239000000203 mixture Substances 0.000 title claims abstract description 89
- -1 naphthalene-2,6-diyl group Chemical group 0.000 claims abstract description 47
- 239000004988 Nematic liquid crystal Substances 0.000 claims abstract description 19
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims abstract description 11
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 61
- 125000000217 alkyl group Chemical group 0.000 claims description 40
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 31
- 125000003342 alkenyl group Chemical group 0.000 claims description 25
- 125000003545 alkoxy group Chemical group 0.000 claims description 23
- 125000005843 halogen group Chemical group 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 13
- 125000001153 fluoro group Chemical group F* 0.000 claims description 12
- 125000002560 nitrile group Chemical group 0.000 claims description 10
- 125000004434 sulfur atom Chemical group 0.000 claims description 10
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 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 claims description 6
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 10
- 230000009257 reactivity Effects 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 8
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 8
- 229910052753 mercury Inorganic materials 0.000 description 8
- 239000012071 phase Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 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 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- FFSAXUULYPJSKH-UHFFFAOYSA-N butyrophenone Chemical compound CCCC(=O)C1=CC=CC=C1 FFSAXUULYPJSKH-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 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 2
- 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 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- GJZFGDYLJLCGHT-UHFFFAOYSA-N 1,2-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(CC)C(CC)=CC=C3SC2=C1 GJZFGDYLJLCGHT-UHFFFAOYSA-N 0.000 description 1
- OURODNXVJUWPMZ-UHFFFAOYSA-N 1,2-diphenylanthracene Chemical compound C1=CC=CC=C1C1=CC=C(C=C2C(C=CC=C2)=C2)C2=C1C1=CC=CC=C1 OURODNXVJUWPMZ-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- IYDQUNGWLDBKOF-UHFFFAOYSA-N 1-(4-butylphenyl)-2,2,2-trichloroethanone Chemical compound CCCCC1=CC=C(C(=O)C(Cl)(Cl)Cl)C=C1 IYDQUNGWLDBKOF-UHFFFAOYSA-N 0.000 description 1
- VKQJCUYEEABXNK-UHFFFAOYSA-N 1-chloro-4-propoxythioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C(OCCC)=CC=C2Cl VKQJCUYEEABXNK-UHFFFAOYSA-N 0.000 description 1
- YNSNJGRCQCDRDM-UHFFFAOYSA-N 1-chlorothioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl YNSNJGRCQCDRDM-UHFFFAOYSA-N 0.000 description 1
- HSKPJQYAHCKJQC-UHFFFAOYSA-N 1-ethylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2CC HSKPJQYAHCKJQC-UHFFFAOYSA-N 0.000 description 1
- 125000006030 1-methyl-3-butenyl group Chemical group 0.000 description 1
- 125000006018 1-methyl-ethenyl group Chemical group 0.000 description 1
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- JHGGYGMFCRSWIZ-UHFFFAOYSA-N 2,2-dichloro-1-(4-phenoxyphenyl)ethanone Chemical compound C1=CC(C(=O)C(Cl)Cl)=CC=C1OC1=CC=CC=C1 JHGGYGMFCRSWIZ-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- IJXPXNZUSXLSTF-UHFFFAOYSA-N 2-[2-(4-butoxyphenyl)ethenyl]-5-(trichloromethyl)-1,3,4-oxadiazole Chemical compound C1=CC(OCCCC)=CC=C1C=CC1=NN=C(C(Cl)(Cl)Cl)O1 IJXPXNZUSXLSTF-UHFFFAOYSA-N 0.000 description 1
- HEQOJEGTZCTHCF-UHFFFAOYSA-N 2-amino-1-phenylethanone Chemical class NCC(=O)C1=CC=CC=C1 HEQOJEGTZCTHCF-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 description 1
- ZWVHTXAYIKBMEE-UHFFFAOYSA-N 2-hydroxyacetophenone Chemical class OCC(=O)C1=CC=CC=C1 ZWVHTXAYIKBMEE-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- HDDGHHVNVQKFIB-UHFFFAOYSA-N 2-naphthalen-2-yl-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC(C(Cl)(Cl)Cl)=NC(C=2C=C3C=CC=CC3=CC=2)=N1 HDDGHHVNVQKFIB-UHFFFAOYSA-N 0.000 description 1
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical class C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 1
- 150000005004 2-naphthylamines Chemical class 0.000 description 1
- HAZQZUFYRLFOLC-UHFFFAOYSA-N 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC(C(Cl)(Cl)Cl)=NC(C=2C=CC=CC=2)=N1 HAZQZUFYRLFOLC-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- YHHKOCQFUSUCCG-UHFFFAOYSA-N 3-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound OCC(C)C(=O)C1=CC=CC=C1 YHHKOCQFUSUCCG-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical class CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- 125000006042 4-hexenyl group Chemical group 0.000 description 1
- NZTUTWYBJCOZCO-UHFFFAOYSA-N 4-methoxy-2-phenyl-4,6-bis(trichloromethyl)-1h-1,3,5-triazine Chemical compound N1C(C(Cl)(Cl)Cl)=NC(OC)(C(Cl)(Cl)Cl)N=C1C1=CC=CC=C1 NZTUTWYBJCOZCO-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- FMWQYKDNAFZCNB-UHFFFAOYSA-N 9,10-dimethylbenzo[a]phenazine Chemical compound C1=CC=CC2=C(N=C3C(C=C(C(=C3)C)C)=N3)C3=CC=C21 FMWQYKDNAFZCNB-UHFFFAOYSA-N 0.000 description 1
- MTRFEWTWIPAXLG-UHFFFAOYSA-N 9-phenylacridine Chemical compound C1=CC=CC=C1C1=C(C=CC=C2)C2=NC2=CC=CC=C12 MTRFEWTWIPAXLG-UHFFFAOYSA-N 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
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- NKFVLNFSHDIILU-UHFFFAOYSA-N C(CCC)OC1=CC=C(C=CN2NC=CC=N2)C=C1 Chemical class C(CCC)OC1=CC=C(C=CN2NC=CC=N2)C=C1 NKFVLNFSHDIILU-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
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- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical class OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- DBHQYYNDKZDVTN-UHFFFAOYSA-N [4-(4-methylphenyl)sulfanylphenyl]-phenylmethanone Chemical compound C1=CC(C)=CC=C1SC1=CC=C(C(=O)C=2C=CC=CC=2)C=C1 DBHQYYNDKZDVTN-UHFFFAOYSA-N 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
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- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 125000005133 alkynyloxy group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 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
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- UOCJDOLVGGIYIQ-PBFPGSCMSA-N cefatrizine Chemical group S([C@@H]1[C@@H](C(N1C=1C(O)=O)=O)NC(=O)[C@H](N)C=2C=CC(O)=CC=2)CC=1CSC=1C=NNN=1 UOCJDOLVGGIYIQ-PBFPGSCMSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 230000003098 cholesteric effect Effects 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- NLCKLZIHJQEMCU-UHFFFAOYSA-N cyano prop-2-enoate Chemical class C=CC(=O)OC#N NLCKLZIHJQEMCU-UHFFFAOYSA-N 0.000 description 1
- 125000006003 dichloroethyl group Chemical group 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VSQYNPJPULBZKU-UHFFFAOYSA-N mercury xenon Chemical compound [Xe].[Hg] VSQYNPJPULBZKU-UHFFFAOYSA-N 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 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
- 125000005447 octyloxy 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])C([H])([H])O* 0.000 description 1
- IMACFCSSMIZSPP-UHFFFAOYSA-N phenacyl chloride Chemical class ClCC(=O)C1=CC=CC=C1 IMACFCSSMIZSPP-UHFFFAOYSA-N 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003232 pyrogallols Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection 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
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- IBBLKSWSCDAPIF-UHFFFAOYSA-N thiopyran Chemical compound S1C=CC=C=C1 IBBLKSWSCDAPIF-UHFFFAOYSA-N 0.000 description 1
- OKYDCMQQLGECPI-UHFFFAOYSA-N thiopyrylium Chemical compound C1=CC=[S+]C=C1 OKYDCMQQLGECPI-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Liquid Crystal Substances (AREA)
Abstract
Description
本発明は、重合性基として(メタ)アクリロイル基を有する重合性化合物を、特定の液晶組成物に添加してなる液晶組成物、及び該液晶組成物を基板で挟持して作製された電気光学表示素子に関する。 The present invention relates to a liquid crystal composition obtained by adding a polymerizable compound having a (meth) acryloyl group as a polymerizable group to a specific liquid crystal composition, and an electro-optic produced by sandwiching the liquid crystal composition between substrates. The present invention relates to a display element.
液晶化合物の特性である光学(屈折率)異方性(Δn)(以下、単に「Δn」ということがある)や誘電率異方性(Δε)(以下、単に「Δε」ということがある)を利用した液晶表示素子は、これまで多数作られており、時計を始め、電卓、各種測定機器、自動車用パネル、ワープロ、電子手帳、携帯電話、プリンター、コンピューター、テレビ等に広く利用され、需要も年々高くなってきている。液晶化合物には固体相と液体相との中間に位置する固有の液晶相があり、その相形態はネマチック相、スメクチック相及びコレステリック相に大別されるが、これらのうち、表示素子用にはネマチック相が現在最も広く利用されている。また、液晶表示素子に応用されている方式のうち、表示方式としては、その代表的なものにTN(捩れネマチック)型、STN(超捩れネマチック)型、DS(動的光散乱)型、GH(ゲスト・ホスト)型、IPS(インプレーンスイッチング)型、OCB(光学補償複屈折)型、ECB(電圧制御複屈折)型、VA(垂直配向)型、CSH(カラースーパーホメオトロピック)型、あるいはFLC(強誘電性液晶)等を挙げることができる。また、駆動方式としては、従来のスタティック駆動からマルチプレックス駆動が一般的になり、単純マトリックス方式、最近ではTFT(薄膜トランジスタ)やMIMにより駆動されるアクティブマトリックス(AM)方式が主流となっている。 Optical (refractive index) anisotropy (Δn) (hereinafter sometimes simply referred to as “Δn”) and dielectric anisotropy (Δε) (hereinafter sometimes simply referred to as “Δε”), which are characteristics of liquid crystal compounds Many liquid crystal display elements that use the above have been made, and are widely used in watches, calculators, various measuring instruments, automotive panels, word processors, electronic notebooks, mobile phones, printers, computers, televisions, etc. It is getting higher year by year. A liquid crystal compound has an intrinsic liquid crystal phase located between a solid phase and a liquid phase, and the phase form is roughly classified into a nematic phase, a smectic phase, and a cholesteric phase. The nematic phase is currently most widely used. Among the methods applied to liquid crystal display elements, typical display methods include TN (twisted nematic) type, STN (super twisted nematic) type, DS (dynamic light scattering) type, GH. (Guest / host) type, IPS (in-plane switching) type, OCB (optical compensation birefringence) type, ECB (voltage controlled birefringence) type, VA (vertical alignment) type, CSH (color super homeotropic) type, or Examples thereof include FLC (ferroelectric liquid crystal). Further, as a driving method, multiplex driving is generally used instead of conventional static driving, and a simple matrix method, and recently an active matrix (AM) method driven by a TFT (thin film transistor) or MIM has become mainstream.
従来、AM方式の液晶ディスプレイとしては、誘電率異方性(Δε)が正の液晶材料を、基板面に水平に、かつ対向する基板間で90度捻れるように配向させたTN型の液晶表示装置が主流であった。しかしながら、このTN型は視野角が狭いという問題点を有しており、広視野角化に向けたさまざまな検討が行われてきた。 Conventionally, as an AM liquid crystal display, a TN liquid crystal in which a liquid crystal material having a positive dielectric anisotropy (Δε) is aligned horizontally with respect to the substrate surface and twisted by 90 degrees between the opposing substrates. Display devices were mainstream. However, this TN type has a problem that the viewing angle is narrow, and various studies have been conducted for widening the viewing angle.
このTN型に変わる方式として、VA型、MVA型、PVA型が開発され、大幅に視野角特性を改善することに成功している。これらは、誘電率異方性が負の液晶材料を2つの基板間に垂直配向させ、かつ基板表面に設けた突起やスリットにより電圧印加時の液晶分子の傾斜方向を規制している方式である。また、最近では、特許文献1〜3に記載されているように、光又は熱により重合するモノマーやオリゴマー等を含有する液晶材料を基板間に封止し、液晶層に印加する電圧を調整しながら重合性成分を重合して液晶の配向方向を決定する液晶表示装置等も提案され、PS(高分子安定化)型やPSA(高分子安定化配向)型の液晶ディスプレイと呼ばれている。PS(A)の技術はMVA等の液晶表示装置における光透過率と応答速度の間にあるトレードオフを改善するためPSA−VA型(又はPS−VA型)として、開発がすすめられている(特許文献1〜4)。 VA type, MVA type, and PVA type have been developed as a method to replace this TN type, and the viewing angle characteristics have been greatly improved. These are systems in which a liquid crystal material having a negative dielectric anisotropy is vertically aligned between two substrates, and the tilt direction of the liquid crystal molecules during voltage application is regulated by protrusions and slits provided on the substrate surface. . In addition, recently, as described in Patent Documents 1 to 3, a liquid crystal material containing a monomer or oligomer that is polymerized by light or heat is sealed between substrates, and the voltage applied to the liquid crystal layer is adjusted. However, liquid crystal display devices that polymerize polymerizable components to determine the alignment direction of liquid crystals have been proposed, and are called PS (polymer stabilization) type or PSA (polymer stabilization alignment) type liquid crystal displays. The PS (A) technology is being developed as a PSA-VA type (or PS-VA type) in order to improve the trade-off between light transmittance and response speed in a liquid crystal display device such as MVA ( Patent Documents 1 to 4).
PSA−VA型液晶ディスプレイでは、電圧印加した状態で重合性化合物を重合する。その重合体がMVA型における突起の役割を果たし、電圧印加時の分子傾斜方向を規制する。したがって分子配向領域の分割化を行うことにより、MVA型等と同様に視野角を広げることが可能である。またMVA型では、その突起のため入射光に対する透明性が低下し、輝度・コントラストの改善が望まれていたが、PSA型では突起が不要となるため、それらの特性が向上し、加えて製造工程の簡略化が可能となる。PSA型では重合性化合物の傾きを保持することが重要であり、そのためには高い反応性が求められている。しかしながら、液晶性の重合性化合物では電圧印加時に液晶組成物と同様の傾きが容易に得られるが、反応性が低かったり、溶解度が低いため液晶組成物中に析出してしまう等の問題があった。また、非液晶性の重合性化合物においては、反応性が高くても分子傾斜方位の規制が得られない等の問題があった。また、いずれの重合性化合物においても、液晶材料中で重合性化合物を紫外線等のエネルギー線照射によって重合させるため、信頼性(電圧保持率)が大きく低下する等といった問題もあった。 In a PSA-VA type liquid crystal display, a polymerizable compound is polymerized with a voltage applied. The polymer serves as a protrusion in the MVA type, and regulates the molecular tilt direction when a voltage is applied. Therefore, by dividing the molecular orientation region, it is possible to widen the viewing angle as in the MVA type or the like. In addition, the MVA type has reduced the transparency to incident light due to the protrusions, and improvement in brightness and contrast has been desired. However, since the PSA type does not require protrusions, these characteristics are improved, and in addition The process can be simplified. In the PSA type, it is important to maintain the inclination of the polymerizable compound, and high reactivity is required for that purpose. However, the liquid crystalline polymerizable compound can easily obtain the same inclination as the liquid crystal composition when a voltage is applied, but has problems such as low reactivity and precipitation in the liquid crystal composition due to low solubility. It was. In addition, the non-liquid crystalline polymerizable compound has a problem that the regulation of the molecular tilt direction cannot be obtained even if the reactivity is high. Moreover, in any polymerizable compound, since the polymerizable compound is polymerized in the liquid crystal material by irradiation with energy rays such as ultraviolet rays, there is a problem that reliability (voltage holding ratio) is greatly reduced.
従って、本発明の目的は、重合性化合物の反応性が高く、紫外線等のエネルギー線照射後に、信頼性(電圧保持率)が低下することのない液晶表示素子を与える液晶組成物を提供することにある。 Accordingly, an object of the present invention is to provide a liquid crystal composition that gives a liquid crystal display element in which the reactivity of the polymerizable compound is high and the reliability (voltage holding ratio) does not decrease after irradiation with energy rays such as ultraviolet rays. It is in.
本発明は、誘電率異方性(Δε)が負であるネマチック液晶組成物100質量部に対し、下記一般式(I)で表される重合性化合物を0.01〜3質量部含有させてなる液晶組成物を提供することにより、上記目的を達成したものである。 The present invention contains 0.01 to 3 parts by mass of a polymerizable compound represented by the following general formula (I) with respect to 100 parts by mass of a nematic liquid crystal composition having a negative dielectric anisotropy (Δε). The above object is achieved by providing a liquid crystal composition.
X1及びX2は(メタ)アクリロイルオキシ基を表し、
Y1は、直接結合、−L1−、−L1O−、−L1S−、−L1O−CO−、−L1CO−O−又は−L1O−CO−O−であり、Y2は、直接結合、−L2−、−OL2−、−SL2−、−O−COL2−、−CO−OL2−又は−O−CO−OL2−であり、L1及びL2は、それぞれ独立に、分岐を有してもよい炭素原子数1〜8のアルキレン基、1,4−フェニレン基又はナフタレン−2,6−ジイル基を表し、該アルキレン基は−O−、−S−、−CH=CH−、−C≡C−、1,4−フェニレン基又はナフタレン−2,6−ジイル基で中断されてもよく、該中断は酸素原子同士、硫黄原子同士又は酸素原子と硫黄原子が隣り合わない。)
X 1 and X 2 represent a (meth) acryloyloxy group,
Y 1 is a direct bond, -L 1 -, - L 1 O -, - L 1 S -, - L 1 O-CO -, - L 1 CO-O- or -L 1 O-CO-O- in There, Y 2 is a direct bond, -L 2 -, - OL 2 -, - SL 2 -, - O-COL 2 -, - CO-OL 2 - , or -O-CO-OL 2 - a is, L 1 and L 2 each independently represents an optionally branched alkylene group having 1 to 8 carbon atoms, 1,4-phenylene group or naphthalene-2,6-diyl group, and the alkylene group is- O—, —S—, —CH═CH—, —C≡C—, 1,4-phenylene group or naphthalene-2,6-diyl group, may be interrupted by oxygen atoms, sulfur atoms Or oxygen atoms and sulfur atoms are not adjacent to each other. )
また、本発明は、上記液晶組成物を、少なくとも一方の基板上に、液晶分子に電圧を印加するための電極を備えた一対の基板で挟持した後、該液晶組成物にエネルギー線を照射して、該液晶組成物が含有する上記一般式(I)で表される重合性化合物を重合させてなる電気光学表示素子を提供するものである。 In the present invention, the liquid crystal composition is sandwiched between a pair of substrates each provided with an electrode for applying a voltage to liquid crystal molecules on at least one substrate, and then the liquid crystal composition is irradiated with energy rays. Thus, an electro-optic display element obtained by polymerizing the polymerizable compound represented by the general formula (I) contained in the liquid crystal composition is provided.
本発明の液晶組成物は、含まれる重合性化合物の析出が発生しにくく、紫外線等のエネルギー線を照射しても電圧保持率が低下せず、高速応答が可能な液晶表示素子を作成でき有用である。また、エネルギー線照射時に該重合性化合物の反応性は高く、且つ液晶組成物中で傾きが保持できるため有用である。 The liquid crystal composition of the present invention is useful for producing a liquid crystal display device capable of high-speed response without causing a decrease in voltage holding ratio even when irradiated with energy rays such as ultraviolet rays, which hardly causes precipitation of the contained polymerizable compound. It is. In addition, the reactivity of the polymerizable compound during energy ray irradiation is high and the tilt can be maintained in the liquid crystal composition, which is useful.
以下、本発明について、その好ましい実施形態について詳細に説明する。 Hereinafter, preferred embodiments of the present invention will be described in detail.
本発明の液晶組成物は、誘電率異方性(Δε)が負であるネマチック液晶組成物100質量部に対して、上記一般式(I)で表される重合性化合物を0.01〜3質量部含有するものであり、該ネマチック液晶組成物100質量部に対して、該重合性化合物を0.01〜2質量部含有することが好ましい。該重合性化合物が0.01質量部未満になると応答速度が遅くなったり、上記一般式(I)で表される重合性化合物が液晶組成物中で傾きを保持できなくなり、3質量部を超えると溶解性が悪くなる。さらに、該ネマチック液晶組成物100質量部に対して、該重合性化合物が0.05〜1質量部であると、電圧保持率が特に良好であるためより好ましい。 In the liquid crystal composition of the present invention, the polymerizable compound represented by the general formula (I) is added in an amount of 0.01 to 3 with respect to 100 parts by mass of the nematic liquid crystal composition having a negative dielectric anisotropy (Δε). It is preferable to contain 0.01-2 mass parts of this polymeric compound with respect to 100 mass parts of this nematic liquid crystal composition. When the polymerizable compound is less than 0.01 parts by mass, the response speed becomes slow, or the polymerizable compound represented by the general formula (I) cannot maintain the inclination in the liquid crystal composition, and exceeds 3 parts by mass. And the solubility becomes worse. Furthermore, it is more preferable that the polymerizable compound is 0.05 to 1 part by mass with respect to 100 parts by mass of the nematic liquid crystal composition because the voltage holding ratio is particularly good.
上記一般式(I)中のL1及びL2で表される炭素原子数1〜8の分岐を有してもよいアルキレン基としては、メチレン、エチレン、プロピレン、メチルエチレン、ブチレン、1−メチルプロピレン、2−メチルプロピレン、1,2−ジメチルプロピレン、1,3−ジメチルプロピレン、1−メチルブチレン、2−メチルブチレン、3−メチルブチレン、4−メチルブチレン、2,4−ジメチルブチレン、1,3−ジメチルブチレン、ペンチレン、ヘキシレン、へプチレン、オクチレン等が挙げられる。L1及びL2で表される分岐を有してもよい炭素原子数1〜8のアルキレン基の水素原子は、ハロゲン原子、ニトリル基で置換されていてもよい。また、L1及びL2で表される1,4−フェニレン基及びナフタレン−2,6−ジイル基の水素原子は、ハロゲン原子、ニトリル基、炭素原子数1〜8の分岐を有してもよいアルキル基で置換されていてもよい。 Examples of the alkylene group optionally having 1 to 8 carbon atoms represented by L 1 and L 2 in the general formula (I) include methylene, ethylene, propylene, methylethylene, butylene, and 1-methyl. Propylene, 2-methylpropylene, 1,2-dimethylpropylene, 1,3-dimethylpropylene, 1-methylbutylene, 2-methylbutylene, 3-methylbutylene, 4-methylbutylene, 2,4-dimethylbutylene, 1, Examples include 3-dimethylbutylene, pentylene, hexylene, heptylene, octylene and the like. The hydrogen atom of the alkylene group having 1 to 8 carbon atoms which may have a branch represented by L 1 and L 2 may be substituted with a halogen atom or a nitrile group. The hydrogen atoms of the 1,4-phenylene group and naphthalene-2,6-diyl group represented by L 1 and L 2 may have a halogen atom, a nitrile group, or a branch having 1 to 8 carbon atoms. It may be substituted with a good alkyl group.
上記一般式(I)中のX1−Y1−及び−Y2−X2としては、例えば、下記式(II)〜(V)に示す重合性官能基が好ましい。 X 1 -Y 1 in the general Formulas (I) - as the and -Y 2 -X 2, for example, preferably a polymerizable functional group represented by the following formula (II) ~ (V).
上記一般式(I)中のAで表される置換基を有してもよい、2個以上の6員環からなる環集合としては、ベンゼン環及びシクロヘキサン環等の6員環の組み合わせによって得られるものであればよく、例えば、ビフェニル、テルフェニル、クアテルフェニル、4−フェニル−シクロヘキシル、4−シクロヘキシル−フェニル、ジシクロヘキシル等が挙げられる。また、上記環集合は、アルキレン基、二重結合、三重結合、カルボニル基又はエーテル結合を6員環同士の連結基として含むものであってもよい。Aで表される環集合を構成する6員環の数は、2又は3であることが好ましい。 The ring assembly composed of two or more 6-membered rings which may have a substituent represented by A in the general formula (I) is obtained by a combination of 6-membered rings such as a benzene ring and a cyclohexane ring. Examples thereof include biphenyl, terphenyl, quaterphenyl, 4-phenyl-cyclohexyl, 4-cyclohexyl-phenyl, and dicyclohexyl. The ring assembly may include an alkylene group, a double bond, a triple bond, a carbonyl group, or an ether bond as a linking group of 6-membered rings. The number of 6-membered rings constituting the ring assembly represented by A is preferably 2 or 3.
また、上記6員環は、炭素原子が窒素原子又は硫黄原子で置換されたものであってもよく、窒素原子で置換された6員環としては、例えば、ピリジン、ピラジン、ピリミジン、ピリダジン、トリアジン、ピペリジン又はピペラジン等が挙げられ、硫黄原子で置換された6員環としては、チオピラン又はチオピリリウム等が挙げられる。 The 6-membered ring may be a carbon atom substituted with a nitrogen atom or a sulfur atom. Examples of the 6-membered ring substituted with a nitrogen atom include pyridine, pyrazine, pyrimidine, pyridazine, and triazine. , Piperidine or piperazine, and the 6-membered ring substituted with a sulfur atom includes thiopyran or thiopyrylium.
上記環集合は、水素原子、ハロゲン原子、ニトリル基、炭素原子数1〜8の分岐を有してもよいアルキル基、炭素原子数1〜8の分岐を有してもよいアルコキシ基、炭素原子数2〜8の分岐を有していてもよいアルケニル基、又はこれらの組み合わせで置換されていてもよい。 The ring assembly includes a hydrogen atom, a halogen atom, a nitrile group, an alkyl group that may have 1 to 8 carbon atoms, an alkoxy group that may have 1 to 8 carbon atoms, and a carbon atom. It may be substituted with an alkenyl group optionally having 2 to 8 branches, or a combination thereof.
上記ハロゲン原子としては、フッ素、塩素、臭素、ヨウ素が挙げられる。上記炭素原子数1〜8の分岐を有してもよいアルキル基としては、例えば、メチル、クロロメチル、トリフルオロメチル、シアノメチル、エチル、ジクロロエチル、プロピル、イソプロピル、ブチル、第二ブチル、第三ブチル、イソブチル、アミル、イソアミル、第三アミル、ヘキシル、2−ヘキシル、3−ヘキシル、シクロヘキシル、1−メチルシクロヘキシル、ヘプチル、2−ヘプチル、3−ヘプチル、イソヘプチル、第三ヘプチル、n−オクチル、イソオクチル、第三オクチル又は2−エチルヘキシル等の直鎖又は分岐のアルキル基が挙げられる。 Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Examples of the alkyl group having 1 to 8 carbon atoms may include, for example, methyl, chloromethyl, trifluoromethyl, cyanomethyl, ethyl, dichloroethyl, propyl, isopropyl, butyl, sec-butyl, tertiary Butyl, isobutyl, amyl, isoamyl, tertiary amyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tertiary heptyl, n-octyl, isooctyl , A linear or branched alkyl group such as tertiary octyl or 2-ethylhexyl.
上記炭素原子数1〜8の分岐を有してもよいアルコキシ基としては、例えば、メチルオキシ、エチルオキシ、クロロメチルオキシ、トリフルオロメチルオキシ、シアノメチルオキシ、エチルオキシ、ジクロロエチルオキシ、プロピルオキシ、イソプロピルオキシ、ブチルオキシ、第二ブチルオキシ、第三ブチルオキシ、イソブチルオキシ、アミルオキシ、イソアミルオキシ、第三アミルオキシ、ヘキシルオキシ、シクロヘキシルオキシ、ヘプチルオキシ、イソヘプチルオキシ、第三ヘプチルオキシ、n−オクチルオキシ、イソオクチルオキシ、第三オクチルオキシ又は2−エチルヘキシルオキシ等の直鎖又は分岐のアルコキシ基が挙げられる。 Examples of the alkoxy group having 1 to 8 carbon atoms may include, for example, methyloxy, ethyloxy, chloromethyloxy, trifluoromethyloxy, cyanomethyloxy, ethyloxy, dichloroethyloxy, propyloxy, isopropyl Oxy, butyloxy, sec-butyloxy, tert-butyloxy, isobutyloxy, amyloxy, isoamyloxy, tert-amyloxy, hexyloxy, cyclohexyloxy, heptyloxy, isoheptyloxy, tert-heptyloxy, n-octyloxy, isooctyloxy And linear or branched alkoxy groups such as tertiary octyloxy or 2-ethylhexyloxy.
上記炭素原子数2〜8の分岐を有してもよいアルケニル基としては、例えば、ビニル、プロペニル、イソプロペニル、ブテニル、イソブテニル、オクテニル等の直鎖又は分岐のアルケニル基が挙げられる。 Examples of the alkenyl group having 2 to 8 carbon atoms may include linear or branched alkenyl groups such as vinyl, propenyl, isopropenyl, butenyl, isobutenyl and octenyl.
上記アルキル基、アルコキシ基又はアルケニル基中の−CH2−は、硫黄原子又は酸素原子で置換されていてもよく、該アルキル基、アルコキシ基又はアルケニル基中の水素原子は、ハロゲン原子又はニトリル基で置換されていてもよい。 —CH 2 — in the alkyl group, alkoxy group or alkenyl group may be substituted with a sulfur atom or an oxygen atom, and a hydrogen atom in the alkyl group, alkoxy group or alkenyl group is a halogen atom or a nitrile group. May be substituted.
上記一般式(I)において、Aで表される環集合としては、下記一般式(VI−1)〜(VI−8)から選択されるいずれかであることが好ましい。 In the general formula (I), the ring assembly represented by A is preferably any one selected from the following general formulas (VI-1) to (VI-8).
p、q及びrは、ベンゼン環又はシクロヘキサン環の取り得る置換基の最大数を表し、複数あるR2、R3及びR4は各々異なるものであってもよい。)
p, q, and r represent the maximum number of substituents that a benzene ring or a cyclohexane ring can take, and a plurality of R 2 , R 3, and R 4 may be different from each other. )
上記R2、R3及びR4で表されるハロゲン原子、炭素原子数1〜8の分岐を有してもよいアルキル基、炭素原子数1〜8の分岐を有してもよいアルコキシ基、及び炭素原子数2〜8の分岐を有してもよいアルケニル基としては、上記一般式(I)中のAの説明で例示したものが挙げられる。 The halogen atom represented by R 2 , R 3 and R 4 , an alkyl group optionally having 1 to 8 carbon atoms, an alkoxy group optionally having 1 to 8 carbon atoms, Examples of the alkenyl group which may have a branch having 2 to 8 carbon atoms include those exemplified in the description of A in the general formula (I).
これらの環構造の中でも、上記一般式(VI−5)で表される環構造、即ち下記環構造が特に好ましく、中でも下記環構造における全てのR2及びR3が水素原子であるものがとりわけ好ましい。 Among these ring structures, the ring structure represented by the above general formula (VI-5), that is, the following ring structure is particularly preferable, and in particular, all of R 2 and R 3 in the following ring structure are hydrogen atoms. preferable.
上記一般式(I)で表される重合性化合物の具体例としては、以下に示す構造の化合物が挙げられる。ただし、本発明は以下の化合物により制限を受けるものではない。 Specific examples of the polymerizable compound represented by the general formula (I) include compounds having the following structures. However, the present invention is not limited by the following compounds.
以上に挙げた上記一般式(I)で表される重合性化合物の具体例において、X1−Y1−及びX2−Y2−は、下記に示す構造であることが好ましい。下記に示すものの中でも、式(II)で表される構造、式(IV−1)で表される構造であることがとりわけ好ましい。
尚、下記式(II)は前記式(II)と同じであり、下記式(III−1)は前記式(III)に含まれるものであり、下記式(IV−1)及び(IV−2)は前記式(IV)に含まれるものであり、下記式(V−1)及び(V−2)は前記式(V)に含まれるものである。
In the specific examples of the polymerizable compound represented by the above general formula (I), X 1 —Y 1 — and X 2 —Y 2 — are preferably the structures shown below. Among those shown below, a structure represented by the formula (II) and a structure represented by the formula (IV-1) are particularly preferable.
The following formula (II) is the same as the above formula (II), the following formula (III-1) is included in the above formula (III), and the following formulas (IV-1) and (IV-2) ) Is included in the formula (IV), and the following formulas (V-1) and (V-2) are included in the formula (V).
上記一般式(I)で表される重合性化合物のより具体的な化合物としては、特に、下記化合物No.1〜No.4の化合物が好ましいものとして挙げられる。 As more specific compounds of the polymerizable compound represented by the general formula (I), in particular, the following compound No. 1-No. The compound of 4 is mentioned as a preferable thing.
上記一般式(I)で表される重合性化合物は、その製造方法には特に制限はなく、周知の反応を適宜応用して製造することができる。例えば、特開2008−163052号公報に記載の方法で製造可能である。 The production method of the polymerizable compound represented by the general formula (I) is not particularly limited, and can be produced by appropriately applying a known reaction. For example, it can be manufactured by the method described in JP2008-163052.
本発明の液晶組成物には、重合性官能基を有する化合物として上記一般式(I)で表される重合性化合物に加えてその他の重合性化合物を用いることが出来る。該その他の重合性化合物としては、通常一般に使用されるものを用いることができ、その具体例としては、特に制限するものではないが、特開2005−15473号公報の段落〔0172〕〜〔0314〕に挙げられる化合物、又は、以下に示す化合物等が挙げられる。
尚、該その他の重合性化合物は上記一般式(I)で表される重合性化合物に対して0〜95質量%含有させることができ、好ましくは0〜70質量%であり、さらに好ましくは0〜50質量%であり、ただし、95%以上含有させると重合性化合物の反応性が低下したり、電圧保持率が低下するため好ましくない。
In the liquid crystal composition of the present invention, other polymerizable compounds can be used as the compound having a polymerizable functional group in addition to the polymerizable compound represented by the general formula (I). As the other polymerizable compounds, those generally used can be used, and specific examples thereof are not particularly limited, but are described in paragraphs [0172] to [0314] of JP-A-2005-15473. Or the compounds shown below.
The other polymerizable compound can be contained in an amount of 0 to 95% by weight, preferably 0 to 70% by weight, more preferably 0, based on the polymerizable compound represented by the general formula (I). However, it is not preferable to contain 95% or more because the reactivity of the polymerizable compound is lowered or the voltage holding ratio is lowered.
また、本発明に用いられる誘電率異方性(Δε)が負である上記ネマチック液晶組成物としては、公知の液晶化合物等を適宜用いて誘電率異方性(Δε)が負となるように調製したものを用いることができるが、下記一般式(VII)で表される液晶化合物を30〜100質量%含有するものが、液晶表示特性が特に優れるため望ましい。下記一般式(VII)で表される液晶化合物は、一種のみで用いてもよく二種以上を組み合わせて用いてもよい。 In addition, as the nematic liquid crystal composition having a negative dielectric anisotropy (Δε) used in the present invention, a known liquid crystal compound or the like is appropriately used so that the dielectric anisotropy (Δε) becomes negative. Those prepared can be used, but those containing 30 to 100% by mass of the liquid crystal compound represented by the following general formula (VII) are preferable because the liquid crystal display characteristics are particularly excellent. The liquid crystal compounds represented by the following general formula (VII) may be used alone or in combination of two or more.
Y1、Y2及びY3は、それぞれ独立に、直接結合、−CH2−CH2−、−CF2−CF2−、−CH=CH−、−CF=CF−、−CH2−O−、−O−CH2−、−CF2−O−、−O−CF2−、−CH2−S−、−S−CH2−、−CF2−S−、−S−CF2−、−O−CF2−C2H4−、−C2H4−CF2−O−、−CO−O−、−O−CO−、−CH2−CH2−CO−O−、−O−CO−CH2−CH2−又は−C≡C−を表し、
R3及びR4は、それぞれ独立に、炭素原子数1〜6のアルキル基又は炭素原子数2〜6のアルケニル基を表し、
j、k及びmは、それぞれ独立に0又は1であり、かつj+k+m≧1であり、nは0又は1である。)
Y 1, Y 2 and Y 3 each independently represent a direct bond, -CH 2 -CH 2 -, - CF 2 -CF 2 -, - CH = CH -, - CF = CF -, - CH 2 -O -, - O-CH 2 - , - CF 2 -O -, - O-CF 2 -, - CH 2 -S -, - S-CH 2 -, - CF 2 -S -, - S-CF 2 - , -O-CF 2 -C 2 H 4 -, - C 2 H 4 -CF 2 -O -, - CO-O -, - O-CO -, - CH 2 -CH 2 -CO-O -, - O—CO—CH 2 —CH 2 — or —C≡C—
R 3 and R 4 each independently represents an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms,
j, k, and m are each independently 0 or 1, and j + k + m ≧ 1, and n is 0 or 1. )
上記一般式(VII)中のB1、B2、B3及びB4で表される環の水素原子を置換してもよい炭素原子数1〜3のアルキル基としては、メチル、エチル、プロピル、イソプロピルが挙げられ、炭素原子数1〜3のアルコキシ基としては、メトキシ、エトキシ、プロポキシ、イソプロポキシが挙げられる。 Examples of the alkyl group having 1 to 3 carbon atoms that may replace the ring hydrogen atom represented by B 1 , B 2 , B 3 and B 4 in the general formula (VII) include methyl, ethyl, propyl And isopropyl, and examples of the alkoxy group having 1 to 3 carbon atoms include methoxy, ethoxy, propoxy, and isopropoxy.
上記一般式(VII)中のR3及びR4で表される炭素原子数1〜6のアルキル基としては、メチル、エチル、プロピル、イソプロピル、ブチル、s−ブチル、t−ブチル、イソブチル、アミル、イソアミル、t−アミル、ヘキシル、2−ヘキシル、3−ヘキシル等が挙げられ、上記一般式(VII)中のR3及びR4で表される炭素原子数2〜6のアルケニル基としては、ビニル、1−メチルエテニル、2−メチルエテニル、2−プロペニル、1−メチル−3−プロペニル、3−ブテニル、1−メチル−3−ブテニル、イソブテニル、3−ペンテニル、4−ヘキセニル等が挙げられる。 Examples of the alkyl group having 1 to 6 carbon atoms represented by R 3 and R 4 in the general formula (VII) include methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, isobutyl, amyl , Isoamyl, t-amyl, hexyl, 2-hexyl, 3-hexyl and the like, and examples of the alkenyl group having 2 to 6 carbon atoms represented by R 3 and R 4 in the general formula (VII) include Examples include vinyl, 1-methylethenyl, 2-methylethenyl, 2-propenyl, 1-methyl-3-propenyl, 3-butenyl, 1-methyl-3-butenyl, isobutenyl, 3-pentenyl, 4-hexenyl and the like.
本発明において、上記一般式(VII)で表される液晶化合物の中でも、下記一般式(VIII)で表される液晶化合物を含有する上記ネマチック液晶組成物を用いると、液晶表示特性が特に優れるため好ましい。 In the present invention, among the liquid crystal compounds represented by the general formula (VII), when the nematic liquid crystal composition containing the liquid crystal compound represented by the following general formula (VIII) is used, the liquid crystal display characteristics are particularly excellent. preferable.
さらに、本発明において、上記一般式(VIII)におけるE1、E2、E3及びE4が水素原子又はフッ素原子である液晶化合物(即ち、E1とE2、E3とE4の組み合わせのうち、一方の組み合わせはフッ素原子のみからなり、他方の組み合わせは水素原子のみからなるか、又は両方の組み合わせがフッ素原子のみからなる液晶化合物)を含有する上記ネマチック液晶組成物を用いると、応答速度等の表示特性及び信頼性がとりわけ優れるため好ましい。また、本発明において、上記一般式(VIII)におけるE3及びE4がフッ素原子であり、Y2が直接結合であり、kが1であり、mが0である液晶化合物を含有する上記ネマチック液晶組成物を用いると、応答速度等の表示特性及び信頼性がさらに一層優れるため、より好ましい。 Further, in the present invention, a liquid crystal compound in which E 1 , E 2 , E 3 and E 4 in the general formula (VIII) are hydrogen atoms or fluorine atoms (that is, a combination of E 1 and E 2 , E 3 and E 4 ) When one of the combinations is composed of only fluorine atoms and the other combination is composed of only hydrogen atoms, or the above nematic liquid crystal composition containing a liquid crystal compound in which both combinations are composed only of fluorine atoms, the response It is preferable because display characteristics such as speed and reliability are particularly excellent. In the present invention, the nematic liquid crystal compound containing a liquid crystal compound in which E 3 and E 4 in the general formula (VIII) are fluorine atoms, Y 2 is a direct bond, k is 1, and m is 0. Use of a liquid crystal composition is more preferable because display characteristics such as response speed and reliability are further improved.
上記一般式(VII)で表される化合物の具体例としては、以下に示す構造の化合物が挙げられる。ただし、本発明は以下の化合物により制限を受けるものではない。尚、以下に示す化学式中、R13は、炭素原子数2〜5のアルキル基を表し、R14は、炭素原子数1〜5のアルキル基を表す。 Specific examples of the compound represented by the general formula (VII) include compounds having the following structures. However, the present invention is not limited by the following compounds. In the chemical formulas shown below, R 13 represents an alkyl group having 2 to 5 carbon atoms, and R 14 represents an alkyl group having 1 to 5 carbon atoms.
これらの中でも、以下の化合物が好ましく用いられる。尚、以下に示す化合物は、一般式(VIII)で表される液晶化合物に包含されるものである。 Among these, the following compounds are preferably used. The compounds shown below are included in the liquid crystal compound represented by the general formula (VIII).
本発明に用いられる誘電率異方性(Δε)が負である上記ネマチック液晶組成物として、さらに下記一般式(IX)で表される液晶化合物を含有するものを用いると、液晶表示特性がさらに一層優れるため好ましい。上記ネマチック液晶組成物におけるその含有量は好ましくは5〜50質量%であり、さらに好ましくは10〜50質量%である。5質量%未満であると使用効果が乏しく、50質量%を超えて使用すると電圧保持率が低下しやすい。 When the nematic liquid crystal composition having a negative dielectric anisotropy (Δε) used in the present invention further contains a liquid crystal compound represented by the following general formula (IX), the liquid crystal display characteristics are further improved. It is preferable because it is more excellent. The content of the nematic liquid crystal composition is preferably 5 to 50% by mass, and more preferably 10 to 50% by mass. If it is less than 5% by mass, the effect of use is poor, and if it exceeds 50% by mass, the voltage holding ratio tends to decrease.
X1及びX2は、それぞれ独立に、直接結合、−CH2−CH2−、−CF2−CF2−、−CH=CH−、−CF=CF−、−CH2−O−、−O−CH2−、−CF2−O−、−O−CF2−又は−C≡C−を表し、
R1及びR2は、それぞれ独立に、炭素原子数1〜6のアルキル基又は炭素原子数2〜6のアルケニル基を表し、
g及びhは、それぞれ独立に、0又は1である。)
X 1 and X 2 are each independently a direct bond, -CH 2 -CH 2 -, - CF 2 -CF 2 -, - CH = CH -, - CF = CF -, - CH 2 -O -, - Represents O—CH 2 —, —CF 2 —O—, —O—CF 2 — or —C≡C—,
R 1 and R 2 each independently represent an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms,
g and h are each independently 0 or 1. )
上記一般式(IX)中のA1、A2及びA3で表される環の水素原子を置換してもよい炭素原子数1〜3のアルキル基及び炭素原子数1〜3のアルコキシ基としては、上記一般式(VII)中のB1、B2、B3及びB4で表される環の水素原子を置換してもよい炭素原子数1〜3のアルキル基及び炭素原子数1〜3のアルコキシ基で例示したものが挙げられる。 As an alkyl group having 1 to 3 carbon atoms and an alkoxy group having 1 to 3 carbon atoms that may substitute for the hydrogen atom of the ring represented by A 1 , A 2, or A 3 in the general formula (IX) Is an alkyl group having 1 to 3 carbon atoms and 1 to 1 carbon atoms which may be substituted for the hydrogen atom of the ring represented by B 1 , B 2 , B 3 and B 4 in the general formula (VII). What was illustrated by the alkoxy group of 3 is mentioned.
上記一般式(IX)中のR1及びR2で表される炭素原子数1〜6のアルキル基、炭素原子数2〜6のアルケニル基としては、上記一般式(VII)中のR3及びR4で表される炭素原子数1〜6のアルキル基、炭素原子数2〜6のアルケニル基として例示したものが挙げられる。 Examples of the alkyl group having 1 to 6 carbon atoms and the alkenyl group having 2 to 6 carbon atoms represented by R 1 and R 2 in the general formula (IX) include R 3 in the general formula (VII) and Examples thereof include those exemplified as the alkyl group having 1 to 6 carbon atoms and the alkenyl group having 2 to 6 carbon atoms represented by R 4 .
上記一般式(IX)で表される化合物の具体例としては、以下に示す構造の化合物が挙げられる。ただし、本発明は以下の化合物により制限を受けるものではない。尚、以下に示す化学式中、R11及びR12は、炭素原子数1〜6のアルキル基又は炭素原子数2〜6のアルケニル基を表す。 Specific examples of the compound represented by the general formula (IX) include compounds having the following structures. However, the present invention is not limited by the following compounds. In the chemical formulas shown below, R 11 and R 12 represent an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms.
これらの中でも、以下の化合物が好ましく用いられる。尚、以下に示す化学式中、R21及びR22は、炭素原子数2〜5のアルキル基又は炭素原子数2〜6のアルケニル基を表す。 Among these, the following compounds are preferably used. In the chemical formulas shown below, R 21 and R 22 represent an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 6 carbon atoms.
本発明の液晶組成物に用いる上記ネマチック液晶組成物には、誘電率異方性(Δε)が負となる範囲で、その他にも、通常一般に使用される液晶化合物を使用することができ、該液晶化合物の具体例としては、特に制限するものではないが、例えば、下記の各化合物が挙げられる。尚、以下の化学式中、W1は、水素原子、又は分岐を有してもよい炭素原子数1〜8のアルキル基、アルコキシ基、アルケニル基、アルケニルオキシ基、アルキニル基、アルキニルオキシ基、アルコキシアルキル基、アルカノイルオキシ基若しくはアルコキシカルボニル基を表し、これらはハロゲン原子、シアノ基等で置換されていてもよく、W2は、シアノ基、ハロゲン原子、又はW1で表される基を示し、W3、W4及びW5は、水素原子、ハロゲン原子又はシアノ基を示す。ただし、前記一般式(VII)及び(IX)に該当する化合物を除く。 In the nematic liquid crystal composition used in the liquid crystal composition of the present invention, generally used liquid crystal compounds can be used in addition to the range where the dielectric anisotropy (Δε) is negative. Specific examples of the liquid crystal compound are not particularly limited, and examples thereof include the following compounds. In the following chemical formula, W 1 represents a hydrogen atom or an optionally branched alkyl group having 1 to 8 carbon atoms, alkoxy group, alkenyl group, alkenyloxy group, alkynyl group, alkynyloxy group, alkoxy group. Represents an alkyl group, an alkanoyloxy group or an alkoxycarbonyl group, which may be substituted with a halogen atom, a cyano group or the like, and W 2 represents a cyano group, a halogen atom or a group represented by W 1 ; W 3 , W 4 and W 5 represent a hydrogen atom, a halogen atom or a cyano group. However, compounds corresponding to the general formulas (VII) and (IX) are excluded.
また、本発明の液晶組成物には、さらに光重合開始剤を添加して使用することもできる。この光重合開始剤としては、従来既知の化合物を用いることが可能であり、例えば、ベンゾインブチルエーテル等のベンゾインエーテル類;ベンジルジメチルケタール等のベンジルケタール類;1−ヒドロキシ−1−ベンゾイルシクロヘキサン、2−ヒドロキシ−2−ベンゾイルプロパン、2−ヒドロキシ−2−(4’−イソプロピル)ベンゾイルプロパン等のα−ヒドロキシアセトフェノン類;4−ブチルベンゾイルトリクロロメタン、4−フェノキシベンゾイルジクロロメタン等のクロロアセトフェノン類;1−ベンジル−1−ジメチルアミノ−1−(4’−モルホリノベンゾイル)プロパン、2−モルホリル−2−(4’−メチルメルカプト)ベンゾイルプロパン、9−n−ブチル−3,6−ビス(2’−モルホリノイソブチロイル)カルバゾール、2−メチル−1−[4−(メチルチオ)フェニル]−2−モルホリノプロパン−1−オン等のα−アミノアセトフェノン類;ビス(2,4,6−トリメチルベンゾイル)−フェニルホスフィンオキシド等のアシルホスフィンオキシド類;ベンジル、ベンゾイル蟻酸メチル等のα−ジカルボニル類;p−メトキシフェニル−2,4−ビス(トリクロロメチル)−s−トリアジン、2−メチル−4,6−ビス(トリクロロメチル)−s−トリアジン、2−フェニル−4,6−ビス(トリクロロメチル)−s−トリアジン、2−ナフチル−4,6−ビス(トリクロロメチル)−s−トリアジン、2−(p−ブトキシスチリル)−s−トリアジン等のトリアジン類;特開2000−80068号公報、特開2001−233842号公報、特開2005−97141号公報、特表2006−516246号公報、特許第3860170号公報、特許第3798008号公報、WO2006/018973号公報に記載の化合物等のα−アシルオキシムエステル類;過酸化ベンゾイル、2,2’−アゾビスイソブチロニトリル、エチルアントラキノン、1,7−ビス(9'−アクリジニル)ヘプタン、チオキサントン、1
−クロル−4−プロポキシチオキサントン、イソプロピルチオキサントン、ジエチルチオキサントン、ベンゾフェノン、フェニルビフェニルケトン、4−ベンゾイル−4'−メチ
ルジフェニルスルフィド、2−(p−ブトキシスチリル)−5−トリクロロメチル−1,3,4−オキサジアゾール、9−フェニルアクリジン、9,10−ジメチルベンズフェナジン、ベンゾフェノン/ミヒラーズケトン、ヘキサアリールビイミダゾール/メルカプトベンズイミダゾール、チオキサントン/アミン等が挙げられる。これらの中でも、ベンゾインエーテル類、ベンジルケタール類、α−ヒドロキシアセトフェノン類及びα−アミノアセトフェノン類が好ましい。
Further, the liquid crystal composition of the present invention can be used by further adding a photopolymerization initiator. As this photopolymerization initiator, conventionally known compounds can be used. For example, benzoin ethers such as benzoin butyl ether; benzyl ketals such as benzyldimethyl ketal; 1-hydroxy-1-benzoylcyclohexane, 2- Α-hydroxyacetophenones such as hydroxy-2-benzoylpropane and 2-hydroxy-2- (4′-isopropyl) benzoylpropane; chloroacetophenones such as 4-butylbenzoyltrichloromethane and 4-phenoxybenzoyldichloromethane; 1-benzyl -1-dimethylamino-1- (4′-morpholinobenzoyl) propane, 2-morpholyl-2- (4′-methylmercapto) benzoylpropane, 9-n-butyl-3,6-bis (2′-morpholinoiso) Butyroyl) carba , Α-aminoacetophenones such as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one; bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, etc. Acyl phosphine oxides; α-dicarbonyls such as benzyl and methyl benzoylformate; p-methoxyphenyl-2,4-bis (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) ) -S-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-butoxystyryl) Triazines such as -s-triazine; JP 2000-80068 A, JP 2001-233842 A, JP Α-acyloxime esters such as compounds described in JP-A-005-97141, JP-T-2006-516246, JP-A-3860170, JP-A-3798008, and WO2006 / 018933; benzoyl peroxide, 2, 2′-azobisisobutyronitrile, ethyl anthraquinone, 1,7-bis (9′-acridinyl) heptane, thioxanthone, 1
-Chloro-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, benzophenone, phenylbiphenyl ketone, 4-benzoyl-4'-methyldiphenyl sulfide, 2- (p-butoxystyryl) -5-trichloromethyl-1,3,4 -Oxadiazole, 9-phenylacridine, 9,10-dimethylbenzphenazine, benzophenone / Michler's ketone, hexaarylbiimidazole / mercaptobenzimidazole, thioxanthone / amine and the like. Among these, benzoin ethers, benzyl ketals, α-hydroxyacetophenones and α-aminoacetophenones are preferable.
また、上記光重合開始剤と増感剤との組合せも好ましく使用することができる。該増感剤としては、例えば、チオキサントン、フェノチアジン、クロロチオキサントン、キサントン、アントラセン、ジフェニルアントラセン、ルプレン等が挙げられる。
上記光重合開始剤及び/又は上記増感剤を添加する場合、それらの添加量は、合計で、上記一般式(I)で表される重合性化合物及びその他の重合性化合物の合計100質量部に対して、10質量部以下であることが好ましく、5質量部以下がさらに好ましく、0.1〜3質量部の範囲内がより好ましい。
Moreover, the combination of the said photoinitiator and a sensitizer can also be used preferably. Examples of the sensitizer include thioxanthone, phenothiazine, chlorothioxanthone, xanthone, anthracene, diphenylanthracene, and lupine.
When the photopolymerization initiator and / or the sensitizer are added, the total amount of these is 100 parts by mass of the polymerizable compound represented by the general formula (I) and other polymerizable compounds. The amount is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and more preferably in the range of 0.1 to 3 parts by mass.
また、本発明の液晶組成物には、必要に応じて添加物をさらに含有させてもよい。液晶組成物の特性を調整するための添加物としては、例えば、保存安定剤、酸化防止剤、紫外線吸収剤、赤外線吸収剤、無機物及び有機物等の微粒子化物、並びにポリマー等の機能性化合物が挙げられる。 Further, the liquid crystal composition of the present invention may further contain additives as necessary. Examples of additives for adjusting the characteristics of the liquid crystal composition include storage stabilizers, antioxidants, ultraviolet absorbers, infrared absorbers, fine particles such as inorganic and organic substances, and functional compounds such as polymers. It is done.
上記保存安定剤は、液晶組成物の保存安定性を向上させる効果を付与することができる。使用できる保存安定剤としては、例えば、ヒドロキノン、ヒドロキノンモノアルキルエーテル類、第三ブチルカテコール類、ピロガロール類、チオフェノール類、ニトロ化合物類、2−ナフチルアミン類、2−ヒドロキシナフタレン類等が挙げられる。これらを添加する場合は、上記一般式(I)で表される重合性化合物及びその他の重合性化合物の合計100質量部に対して、1質量部以下であることが好ましく、0.5質量部以下が特に好ましい。 The said storage stabilizer can provide the effect which improves the storage stability of a liquid crystal composition. Examples of the storage stabilizer that can be used include hydroquinone, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, 2-naphthylamines, 2-hydroxynaphthalenes, and the like. When adding these, it is preferable that it is 1 mass part or less with respect to a total of 100 mass parts of the polymeric compound represented by the said general formula (I), and another polymeric compound, 0.5 mass part The following are particularly preferred:
上記酸化防止剤としては、特に制限がなく公知の化合物を使用することができ、例えば、ヒドロキノン、2,6−ジ−t−ブチル−p−クレゾール、2,6−ジ−t−ブチルフェノール、トリフェニルホスファイト、トリアルキルホスファイト等が挙げられる。 The antioxidant is not particularly limited and a known compound can be used. Examples thereof include hydroquinone, 2,6-di-t-butyl-p-cresol, 2,6-di-t-butylphenol, Examples thereof include phenyl phosphite and trialkyl phosphite.
上記紫外線吸収剤としては、特に制限がなく公知の化合物を使用することができ、例えば、サリチル酸エステル系化合物、ベンゾフェノール系化合物、ベンゾトリアゾール系化合物、トリアジン系化合物、シアノアクリレート系化合物又はニッケル錯塩系化合物等によって紫外線吸収能をもたせたものを用いることができる。 As the ultraviolet absorber, known compounds can be used without any particular limitation. For example, salicylic acid ester compounds, benzophenol compounds, benzotriazole compounds, triazine compounds, cyanoacrylate compounds, or nickel complex salts. What gave the ultraviolet absorptivity with a compound etc. can be used.
本発明の液晶組成物に必要に応じて含有させる上記添加物は、特に制限無く、作製される重合体の特性を損なわない範囲で適宜使用することができるが、好ましくは、誘電率異方性(Δε)が負である上記ネマチック液晶組成物、上記一般式(I)で表される重合性化合物及びその他の重合性化合物の合計量100質量部に対して、全任意成分の合計で好ましくは30質量部以下、より好ましくは10質量部以下となるようにする。 The additive to be contained in the liquid crystal composition of the present invention as needed is not particularly limited and can be appropriately used within a range not impairing the properties of the produced polymer. Preferably, the dielectric anisotropy is used. Preferably, the total of all the optional components is preferably 100 parts by mass of the total amount of the nematic liquid crystal composition having a negative (Δε), the polymerizable compound represented by the general formula (I) and the other polymerizable compound. 30 parts by mass or less, more preferably 10 parts by mass or less.
本発明の液晶組成物は、光、電磁波又は熱を用いる公知の方法を適用して上記重合性化合物を重合させて用いられる。上記光の好ましい種類は、紫外線、可視光線、赤外線等である。電子線、X線等の電磁波を用いてもよい。通常は、紫外線又は可視光線が好ましい。好ましい波長の範囲は150〜500nmである。さらに好ましい範囲は250〜450nmであり、最も好ましい範囲は300〜400nmである。光源としては、低圧水銀ランプ(殺菌ランプ、蛍光ケミカルランプ、ブラックライト)、高圧放電ランプ(高圧水銀ランプ、メタルハライドランプ)、ショートアーク放電ランプ(超高圧水銀ランプ、キセノンランプ、水銀キセノンランプ)等が挙げられるが、高圧水銀ランプ、超高圧水銀ランプが好ましく使用することができる。光源からの光はそのまま液晶組成物に照射してもよく、フィルターによって選択した特定の波長(又は特定の波長領域)を液晶組成物に照射してもよい。好ましい照射エネルギー密度は、10〜50000mJ/cm2であり、さらに好ましい範囲は10〜20000mJ/cm2である。好ましい照度は0.1〜5000mW/cm2であり、さらに好ましい照度は1〜2000mW/cm2である。露光量が少ないと重合が不十分となりやすく、露光量が多いと電圧保持率(VHR)が低下する恐れがある。 The liquid crystal composition of the present invention is used by polymerizing the polymerizable compound by applying a known method using light, electromagnetic waves or heat. Preferred types of the light are ultraviolet rays, visible rays, infrared rays and the like. You may use electromagnetic waves, such as an electron beam and an X-ray. Usually, ultraviolet rays or visible rays are preferable. A preferable wavelength range is 150 to 500 nm. A more preferable range is 250 to 450 nm, and a most preferable range is 300 to 400 nm. Low light mercury lamps (sterilization lamps, fluorescent chemical lamps, black lights), high pressure discharge lamps (high pressure mercury lamps, metal halide lamps), short arc discharge lamps (super high pressure mercury lamps, xenon lamps, mercury xenon lamps), etc. Among them, a high-pressure mercury lamp and an ultra-high pressure mercury lamp can be preferably used. The light from the light source may be irradiated to the liquid crystal composition as it is, or the liquid crystal composition may be irradiated with a specific wavelength (or a specific wavelength region) selected by a filter. A preferable irradiation energy density is 10 to 50000 mJ / cm 2 , and a more preferable range is 10 to 20000 mJ / cm 2 . A preferable illuminance is 0.1 to 5000 mW / cm 2 , and a more preferable illuminance is 1 to 2000 mW / cm 2 . If the exposure amount is small, the polymerization tends to be insufficient, and if the exposure amount is large, the voltage holding ratio (VHR) may decrease.
次に、本発明の電気光学表示素子について説明する。本発明の電気光学表示素子は、本発明の液晶組成物を、少なくとも一方の基板上に、液晶分子に電圧を印加するための電極を備えた一対の基板で挟持した後、紫外線等のエネルギー線照射により、上記一般式(I)で表される重合性化合物を重合して作製されたものである。 Next, the electro-optic display element of the present invention will be described. The electro-optic display element of the present invention includes an energy ray such as ultraviolet rays after the liquid crystal composition of the present invention is sandwiched between a pair of substrates provided with electrodes for applying a voltage to liquid crystal molecules on at least one substrate. It is produced by polymerizing the polymerizable compound represented by the general formula (I) by irradiation.
上記基板としては、特に制限はなく、従来から電気光学表示素子に用いられているものを用いることができ、目的の駆動方式及び表示方式に適したものを用いればよい。上記エネルギー線としては、紫外線のほかに、上述の光、電磁波又は熱によるものが挙げられる。 There is no restriction | limiting in particular as said board | substrate, The thing conventionally used for the electro-optic display element can be used, What is necessary is just to use the thing suitable for the target drive system and display system. Examples of the energy rays include those caused by the above-mentioned light, electromagnetic waves or heat in addition to ultraviolet rays.
本発明の電気光学表示素子は、AM方式、パッシブマトリクス(PM)方式のいずれで駆動をしてもよい。AM方式又はPM方式で駆動する液晶表示素子は、反射型、透過型、半透過型、いずれの液晶ディスプレイ等にも適用ができる。 The electro-optic display element of the present invention may be driven by either an AM method or a passive matrix (PM) method. The liquid crystal display element driven by the AM method or the PM method can be applied to any liquid crystal display such as a reflective type, a transmissive type, and a transflective type.
また、本発明の電気光学表示素子は、導電剤を添加した液晶組成物を用いたDS(dynamic scattering)モード素子や、液晶組成物をマイクロカプセル化して作製したNCAP(nematic curvilinear aligned phase)素子や、液晶組成物中に三次元の網目状高分子を形成させたPD(polymer dispersed)素子、例えばPN(polymer network)素子としても使用できる。 The electro-optic display device of the present invention includes a DS (dynamic scattering) mode device using a liquid crystal composition to which a conductive agent is added, a NCAP (nematic curvilinear aligned phase) device manufactured by microencapsulating a liquid crystal composition, Also, it can be used as a PD (polymer dispersed) element in which a three-dimensional network polymer is formed in a liquid crystal composition, for example, a PN (polymer network) element.
本発明の液晶組成物は上述のような特性を有するので、中でも負の誘電率異方性を利用した表示モード、例えば、VAモード、IPSモード等で表示するAM方式の液晶表示素子に好適に使用でき、特に、VAモードで表示するAM方式の液晶表示素子に好適に使用できる。 Since the liquid crystal composition of the present invention has the characteristics as described above, it is particularly suitable for an AM liquid crystal display element that displays in a display mode utilizing negative dielectric anisotropy, for example, a VA mode, an IPS mode, or the like. In particular, it can be suitably used for an AM liquid crystal display element that displays in the VA mode.
VAモード等で表示する液晶表示素子においては、電場の方向は、液晶層に対して垂直である。一方、IPSモード等で表示する液晶表示素子においては、電場の方向は、液晶層に対して平行である。VAモードで表示する液晶表示素子の構造は、例えば、K. Ohmuro, S. Kataoka, T. Sasaki and Y. Koike, SID ’97 Digest of Technical Papers, 28, 845 (1997)に報告されており、IPSモードで表示する液晶表示素子の構造は、例えば、国際公開第91/10936号パンフレット(ファミリー:US5576867)に報告されている。 In a liquid crystal display element that displays in VA mode or the like, the direction of the electric field is perpendicular to the liquid crystal layer. On the other hand, in the liquid crystal display element that displays in the IPS mode or the like, the direction of the electric field is parallel to the liquid crystal layer. The structure of the liquid crystal display element displaying in the VA mode is, for example, K.I. Ohmuro, S.M. Kataoka, T .; Sasaki and Y.S. Koike, SID '97 Digest of Technical Papers, 28, 845 (1997). The structure of a liquid crystal display element that displays in the IPS mode is described in, for example, International Publication No. 91/10936 (pamphlet: US5576867). It has been reported.
本発明の液晶組成物を用いてなる電気光学表示素子は、時計、電卓、測定器、自動車用計器、複写機、カメラ、OA機器、PDA、ノートパソコン、モニター、テレビ、携帯電話、調光窓、光シャッタ、偏光交換素子等の用途に使用することができるが、特にその特性から、大型なPDA、ノートパソコン、モニター、テレビ用途に好適に使用される。 The electro-optic display device using the liquid crystal composition of the present invention includes a clock, a calculator, a measuring instrument, an automotive instrument, a copying machine, a camera, an OA device, a PDA, a notebook computer, a monitor, a television, a mobile phone, and a light control window. It can be used for applications such as an optical shutter and a polarization exchange element, but is particularly suitable for large PDA, notebook personal computer, monitor and television applications because of its characteristics.
以下、実施例等を示して本発明を更に詳細に説明するが、本発明はこれらの実施例等により限定されるものではない。 EXAMPLES Hereinafter, although an Example etc. are shown and this invention is demonstrated further in detail, this invention is not limited by these Examples.
下記参考例においては、Δεが負である本発明に係るネマチック液晶組成物を作製した。下記実施例1、2及び比較例1、2では、本発明に係る重合性化合物又は比較用重合性化合物を、参考例で作製した本発明に係るネマチック液晶組成物に配合して、重合性化合物を含有する液晶組成物を作製した。実施例1及び比較例1では、得られた液晶組成物のPSA機能の発現性を評価し、実施例2及び比較例2では、得られた液晶組成物の溶解性、配向性、重合性化合物の反応率、電圧保持率を評価した。 In the following reference examples, nematic liquid crystal compositions according to the present invention having negative Δε were prepared. In the following Examples 1 and 2 and Comparative Examples 1 and 2, the polymerizable compound according to the present invention or the polymerizable compound for comparison is blended with the nematic liquid crystal composition according to the present invention prepared in the reference example, and the polymerizable compound A liquid crystal composition containing was prepared. In Example 1 and Comparative Example 1, the expression of the PSA function of the obtained liquid crystal composition was evaluated. In Example 2 and Comparative Example 2, the solubility, orientation, and polymerizable compound of the obtained liquid crystal composition were evaluated. The reaction rate and voltage holding rate were evaluated.
[参考例]Δεが負であるネマチック液晶組成物の作製
液晶化合物No.1〜No.10を下記の配合(合計100質量部)に従って混合して、液晶組成物No.1を作成した。なお、液晶化合物No.1〜No.4は上記一般式(IX)に該当する化合物であり、液晶化合物No.5〜No.10は上記一般式(VII)に該当する化合物である。
[Reference Example] Preparation of nematic liquid crystal composition having negative Δε 1-No. 10 was mixed according to the following composition (100 parts by mass in total). 1 was created. In addition, liquid crystal compound No. 1-No. 4 is a compound corresponding to the general formula (IX). 5-No. 10 is a compound corresponding to the general formula (VII).
上記参考例で得られた液晶組成物No.1、上記一般式(I)で表される重合性化合物である化合物No.1〜No.2及び比較化合物No.1〜No.3を用いて、以下の実施例及び比較例を行なった。尚、比較化合物No.1〜No.3は以下の通りである。 Liquid crystal composition Nos. Obtained in the above reference examples. 1. Compound No. 1 which is a polymerizable compound represented by the above general formula (I). 1-No. 2 and comparative compound no. 1-No. The following examples and comparative examples were carried out using No. 3. In addition, comparative compound No. 1-No. 3 is as follows.
[実施例1及び比較例1−1〜1−2]PSA機能発現性(重合性化合物傾き保持確認)
液晶組成物No.1の100質量部に対し、〔表1〕に示す化合物をそれぞれ1質量部加えて、重合性化合物を含有する液晶組成物とした。重合性化合物を含有する該液晶組成物を、液晶評価用テストセル(セル厚5μm、電極面積8mm×8mm、配向膜JALS−2096、アンチパラレルラビング)に注入し、注入口を封止剤で封止した。封止したテストセルに、印加電圧0V及び4V状態で高圧水銀ランプ(照度40mW/cm2、光量20J/cm2)にてエネルギー線照射した後、電圧印加を解除し、該テストセルをクロスニコル下にて偏光顕微鏡観察した。この観察時の顕微鏡写真を〔図1〕に示す。
[Example 1 and Comparative Examples 1-1 to 1-2] PSA function expression (confirmation of tilt retention of polymerizable compound)
Liquid crystal composition no. 1 part by mass of each of the compounds shown in [Table 1] was added to 100 parts by mass of 1, thereby obtaining a liquid crystal composition containing a polymerizable compound. The liquid crystal composition containing a polymerizable compound is injected into a test cell for liquid crystal evaluation (cell thickness 5 μm, electrode area 8 mm × 8 mm, alignment film JALS-2096, anti-parallel rubbing), and the injection port is sealed with a sealant. Stopped. The sealed test cell was irradiated with energy rays with a high-pressure mercury lamp (illuminance: 40 mW / cm 2 , light amount: 20 J / cm 2 ) at an applied voltage of 0 V and 4 V, the voltage application was canceled, and the test cell was crossed Nicol Observation under a polarizing microscope. A micrograph at the time of this observation is shown in FIG.
図1より、本発明の液晶組成物は電圧印加時に重合することで固定され、PSA機能を発現することが明らかである。 From FIG. 1, it is clear that the liquid crystal composition of the present invention is fixed by polymerization when a voltage is applied and exhibits a PSA function.
[実施例2−1〜2−2及び比較例2−1〜2−4]
<重合性化合物を含有する液晶組成物の調製>
液晶組成物No.1の100質量部に対し、〔表2〕に示す重合性化合物をそれぞれ0.5質量部加え、重合性化合物を含有する液晶組成物を得た。得られた重合性化合物を含有する液晶組成物の溶解性、配向性、重合性化合物の反応率及び電圧保持率(VHR)について、それぞれ以下の方法で評価・測定した。
[Examples 2-1 to 2-2 and Comparative examples 2-1 to 2-4]
<Preparation of liquid crystal composition containing polymerizable compound>
Liquid crystal composition no. 0.5 parts by mass of the polymerizable compound shown in [Table 2] was added to 100 parts by mass of 1 to obtain a liquid crystal composition containing the polymerizable compound. The solubility, the orientation, the reaction rate of the polymerizable compound and the voltage holding ratio (VHR) of the liquid crystal composition containing the obtained polymerizable compound were evaluated and measured by the following methods, respectively.
<溶解性>
液晶組成物への重合性化合物の溶解性を確認し、室温で溶解したものを○、溶解しなかったものを×として評価した。
<Solubility>
The solubility of the polymerizable compound in the liquid crystal composition was confirmed. Evaluation was made as ○ for those dissolved at room temperature, and × for those not dissolved.
<配向性>
得られた液晶組成物を液晶評価用テストセル(セル厚5μm、電極面積8mm×8mm、配向膜JALS2096)に注入後、注入口を封止剤にて封止した。その後、高圧水銀ランプ(照度40mW/cm2、光量10J/cm2)で光を照射し、サンプルを得た。得られたサンプルについて、偏光顕微観察(クロスニコル下にて電圧OFF時の配向状態)を目視で行い、配向性を確認し、配向が良好だったものを○、配向が乱れていたものを×として評価した。
<Orientation>
The obtained liquid crystal composition was injected into a test cell for liquid crystal evaluation (cell thickness 5 μm, electrode area 8 mm × 8 mm, alignment film JALS2096), and the injection port was sealed with a sealant. Then, light was irradiated with the high pressure mercury lamp (illuminance 40mW / cm < 2 >, light quantity 10J / cm < 2 >), and the sample was obtained. About the obtained sample, polarization microscopic observation (orientation state when the voltage is OFF under crossed Nicols) is visually performed to confirm the orientation, ○ that the orientation is good is ○, and that the orientation is disordered × As evaluated.
<重合性化合物の反応率>
(光照射前のサンプル)
重合性化合物を含有する液晶組成物をアセトニトリルに溶解し、サンプルとした。
(光照射後のサンプル)
配向性評価に用いた、高圧水銀ランプ(照度40mW/cm2、光量10J/cm2)で光を照射した液晶評価用テストセルを解体し、液晶組成物をアセトニトリルに抽出し、サンプルとした。
得られた光照射前後サンプルを液体クロマトグラフィーにて分析し、光照射前に比較した場合の光照射後における液晶組成物中の重合性化合物の残存率から、反応率を算出した。
<Reaction rate of polymerizable compound>
(Sample before light irradiation)
A liquid crystal composition containing a polymerizable compound was dissolved in acetonitrile to prepare a sample.
(Sample after light irradiation)
The test cell for liquid crystal evaluation irradiated with light with a high-pressure mercury lamp (illuminance 40 mW / cm 2 , light amount 10 J / cm 2 ) used for the evaluation of orientation was disassembled, and the liquid crystal composition was extracted into acetonitrile to prepare a sample.
The obtained sample before and after light irradiation was analyzed by liquid chromatography, and the reaction rate was calculated from the residual ratio of the polymerizable compound in the liquid crystal composition after light irradiation when compared before light irradiation.
<VHR(光照射後)>
上記配向性の評価において得られたサンプルに対して、以下の装置及び条件によりVHRの測定を行った。
・装置:東陽テクニカ社製VHR−A1
・条件:パルス電圧幅60μs、フレーム周期16.7ms、波高±5V、測定温度25℃及び60℃
<VHR (after light irradiation)>
With respect to the sample obtained in the evaluation of the orientation, VHR was measured using the following apparatus and conditions.
・ Device: VHR-A1 manufactured by Toyo Technica
-Conditions: pulse voltage width 60 μs, frame period 16.7 ms, wave height ± 5 V, measurement temperature 25 ° C. and 60 ° C.
以上の各種評価・測定結果を〔表2〕に示す。 The above various evaluation and measurement results are shown in [Table 2].
〔表2〕の結果の通り、比較化合物No.1は溶解性及び配向性は良好であるが、重合性化合物の反応性が低く、VHRに劣る。比較化合物No.2は、溶解性は良好であるが、配向が乱れていた。また、比較化合物3は溶解性が劣っていた。一方、本発明の液晶組成物に用いる上記一般式(I)で表される重合性化合物は、溶解性、配向性に優れ、紫外線等のエネルギー線の照射に対して高い反応性を有し、重合性化合物の添加によるVHRの低下が無い。 As shown in Table 2, the comparative compound No. No. 1 has good solubility and orientation, but the reactivity of the polymerizable compound is low and it is inferior to VHR. Comparative Compound No. No. 2 had good solubility but disordered orientation. Moreover, the comparative compound 3 was inferior in solubility. On the other hand, the polymerizable compound represented by the general formula (I) used in the liquid crystal composition of the present invention is excellent in solubility and orientation, and has high reactivity to irradiation of energy rays such as ultraviolet rays. There is no decrease in VHR due to the addition of a polymerizable compound.
以上の実施例、比較例より、本発明の液晶組成物は、紫外線等のエネルギー線照射後に、信頼性(電圧保持率)の低下が抑制されること、及び、重合性基の反応性が高く重合後に液晶組成物中で移動しにくいためコントラストの低下が抑制された液晶表示素子を与え得ることが明らかである。 From the above examples and comparative examples, the liquid crystal composition of the present invention has a reduced reliability (voltage holding ratio) after irradiation with energy rays such as ultraviolet rays and a high reactivity of the polymerizable group. It is apparent that a liquid crystal display element in which a decrease in contrast is suppressed can be provided because it is difficult to move in the liquid crystal composition after polymerization.
Claims (11)
X1及びX2は、各々独立して(メタ)アクリロイルオキシ基を表し、
Y1は、直接結合、−L1−、−L1O−、−L1S−、−L1O−CO−、−L1CO−O−又は−L1O−CO−O−であり、Y2は、直接結合、−L2−、−OL2−、−SL2−、−O−COL2−、−CO−OL2−又は−O−CO−OL2−であり、L1及びL2は、それぞれ独立に、分岐を有してもよい炭素原子数1〜8のアルキレン基、1,4−フェニレン基又はナフタレン−2,6−ジイル基を表し、該アルキレン基は−O−、−S−、−CH=CH−、−C≡C−、1,4−フェニレン基又はナフタレン−2,6−ジイル基で中断されてもよく、該中断は酸素原子同士、硫黄原子同士又は酸素原子と硫黄原子が隣り合わない。) A liquid crystal composition comprising 0.01 to 3 parts by mass of a polymerizable compound represented by the following general formula (I) with respect to 100 parts by mass of a nematic liquid crystal composition having a negative dielectric anisotropy (Δε). .
X 1 and X 2 each independently represent a (meth) acryloyloxy group,
Y 1 is a direct bond, -L 1 -, - L 1 O -, - L 1 S -, - L 1 O-CO -, - L 1 CO-O- or -L 1 O-CO-O- in There, Y 2 is a direct bond, -L 2 -, - OL 2 -, - SL 2 -, - O-COL 2 -, - CO-OL 2 - , or -O-CO-OL 2 - a is, L 1 and L 2 each independently represents an optionally branched alkylene group having 1 to 8 carbon atoms, 1,4-phenylene group or naphthalene-2,6-diyl group, and the alkylene group is- O—, —S—, —CH═CH—, —C≡C—, 1,4-phenylene group or naphthalene-2,6-diyl group, may be interrupted by oxygen atoms, sulfur atoms Or oxygen atoms and sulfur atoms are not adjacent to each other. )
p、q及びrは、ベンゼン環又はシクロヘキサン環の取り得る置換基の最大数を表し、複数あるR2、R3及びR4は各々異なるものであってもよい。) 3. The liquid crystal composition according to claim 1, wherein A in the general formula (I) is a ring assembly selected from the following general formulas (VI-1) to (VI-8): .
p, q, and r represent the maximum number of substituents that a benzene ring or a cyclohexane ring can take, and a plurality of R 2 , R 3, and R 4 may be different from each other. )
Y1、Y2及びY3は、それぞれ独立に、直接結合、−CH2−CH2−、−CF2−CF2−、−CH=CH−、−CF=CF−、−CH2−O−、−O−CH2−、−CF2−O−、−O−CF2−、−CH2−S−、−S−CH2−、−CF2−S−、−S−CF2−、−O−CF2−C2H4−、−C2H4−CF2−O−、−CO−O−、−O−CO−、−CH2−CH2−CO−O−、−O−CO−CH2−CH2−又は−C≡C−を表し、
R3及びR4は、それぞれ独立に、炭素原子数1〜6のアルキル基又は炭素原子数2〜6のアルケニル基を表し、
j、k及びmは、それぞれ独立に、0又は1であり、かつj+k+m≧1であり、nは0又は1である。) 6. The matic liquid crystal composition having a negative dielectric anisotropy (Δε) contains 30 to 100% by mass of a liquid crystal compound represented by the following general formula (VII): The liquid crystal composition described in 1.
Y 1, Y 2 and Y 3 each independently represent a direct bond, -CH 2 -CH 2 -, - CF 2 -CF 2 -, - CH = CH -, - CF = CF -, - CH 2 -O -, - O-CH 2 - , - CF 2 -O -, - O-CF 2 -, - CH 2 -S -, - S-CH 2 -, - CF 2 -S -, - S-CF 2 - , -O-CF 2 -C 2 H 4 -, - C 2 H 4 -CF 2 -O -, - CO-O -, - O-CO -, - CH 2 -CH 2 -CO-O -, - O—CO—CH 2 —CH 2 — or —C≡C—
R 3 and R 4 each independently represents an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms,
j, k, and m are each independently 0 or 1, and j + k + m ≧ 1, and n is 0 or 1. )
X1及びX2は、それぞれ独立に、直接結合、−CH2−CH2−、−CF2−CF2−、−CH=CH−、−CF=CF−、−CH2−O−、−O−CH2−、−CF2−O−、−O−CF2−又は−C≡C−を表し、
R1及びR2は、それぞれ独立に、炭素原子数1〜6のアルキル基又は炭素原子数2〜6のアルケニル基を表し、
g及びhは、それぞれ独立に、0又は1である。) The nematic liquid crystal composition having a negative dielectric anisotropy (Δε) further contains 5 to 50% by mass of a liquid crystal compound represented by the following general formula (IX). A liquid crystal composition according to claim 1.
X 1 and X 2 are each independently a direct bond, -CH 2 -CH 2 -, - CF 2 -CF 2 -, - CH = CH -, - CF = CF -, - CH 2 -O -, - Represents O—CH 2 —, —CF 2 —O—, —O—CF 2 — or —C≡C—,
R 1 and R 2 each independently represent an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms,
g and h are each independently 0 or 1. )
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