JP5077029B2 - Antioxidant liquid crystal composition - Google Patents
Antioxidant liquid crystal composition Download PDFInfo
- Publication number
- JP5077029B2 JP5077029B2 JP2008101337A JP2008101337A JP5077029B2 JP 5077029 B2 JP5077029 B2 JP 5077029B2 JP 2008101337 A JP2008101337 A JP 2008101337A JP 2008101337 A JP2008101337 A JP 2008101337A JP 5077029 B2 JP5077029 B2 JP 5077029B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- liquid crystal
- carbon atoms
- general formula
- crystal composition
- 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.)
- Expired - Lifetime
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- 239000004973 liquid crystal related substance Substances 0.000 title claims description 85
- 239000000203 mixture Substances 0.000 title claims description 59
- 239000003963 antioxidant agent Substances 0.000 title claims description 34
- 230000003078 antioxidant effect Effects 0.000 title claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 54
- -1 naphthalene-2,6-diyl group Chemical group 0.000 claims description 49
- 150000001875 compounds Chemical class 0.000 claims description 38
- 125000000217 alkyl group Chemical group 0.000 claims description 29
- 229910052731 fluorine Inorganic materials 0.000 claims description 20
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 17
- 125000003342 alkenyl group Chemical group 0.000 claims description 16
- 125000001153 fluoro group Chemical group F* 0.000 claims description 14
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical group 0.000 claims description 8
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 8
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 7
- 125000004786 difluoromethoxy group Chemical group [H]C(F)(F)O* 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 125000005407 trans-1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])[C@]([H])([*:2])C([H])([H])C([H])([H])[C@@]1([H])[*:1] 0.000 claims description 6
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 5
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 claims description 4
- 101150065749 Churc1 gene Proteins 0.000 claims description 4
- 102100038239 Protein Churchill Human genes 0.000 claims description 4
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 4
- 239000004990 Smectic liquid crystal Substances 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 4
- 0 *c1cc*(*)cc1 Chemical compound *c1cc*(*)cc1 0.000 description 3
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 3
- 239000004988 Nematic liquid crystal Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- 239000002530 phenolic antioxidant Substances 0.000 description 3
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 description 2
- GONPAIMDIMMKMK-UHFFFAOYSA-N 4-[3-carboxy-4-(3,5-ditert-butyl-4-hydroxyphenyl)butyl]sulfanyl-2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]butanoic acid Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC(CCSCCC(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(O)=O)C(O)=O)=C1 GONPAIMDIMMKMK-UHFFFAOYSA-N 0.000 description 2
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 description 2
- 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 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000001651 cyanato group Chemical group [*]OC#N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 150000003852 triazoles Chemical class 0.000 description 2
- RGASRBUYZODJTG-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C RGASRBUYZODJTG-UHFFFAOYSA-N 0.000 description 1
- MYMKXVFDVQUQLG-UHFFFAOYSA-N 1,3,7,9-tetratert-butyl-11-fluoro-5-methyl-5h-benzo[d][1,3,2]benzodioxaphosphocine Chemical compound CC1C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2OP(F)OC2=C1C=C(C(C)(C)C)C=C2C(C)(C)C MYMKXVFDVQUQLG-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- DXCHWXWXYPEZKM-UHFFFAOYSA-N 2,4-ditert-butyl-6-[1-(3,5-ditert-butyl-2-hydroxyphenyl)ethyl]phenol Chemical compound C=1C(C(C)(C)C)=CC(C(C)(C)C)=C(O)C=1C(C)C1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1O DXCHWXWXYPEZKM-UHFFFAOYSA-N 0.000 description 1
- PITPRNOGWXAZAW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-methoxyphenol Chemical compound COC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 PITPRNOGWXAZAW-UHFFFAOYSA-N 0.000 description 1
- ROHFBIREHKPELA-UHFFFAOYSA-N 2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]prop-2-enoic acid;methane Chemical compound C.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O ROHFBIREHKPELA-UHFFFAOYSA-N 0.000 description 1
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 1
- STEYNUVPFMIUOY-UHFFFAOYSA-N 4-Hydroxy-1-(2-hydroxyethyl)-2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CC(O)CC(C)(C)N1CCO STEYNUVPFMIUOY-UHFFFAOYSA-N 0.000 description 1
- ZGUBOEMAXMRLON-UHFFFAOYSA-N 4-butan-2-yl-2-[1-(5-butan-2-yl-3-tert-butyl-2-hydroxyphenyl)ethyl]-6-tert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)CC)=CC(C(C)C=2C(=C(C=C(C=2)C(C)CC)C(C)(C)C)O)=C1O ZGUBOEMAXMRLON-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZVVFVKJZNVSANF-UHFFFAOYSA-N 6-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]hexyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCCCCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 ZVVFVKJZNVSANF-UHFFFAOYSA-N 0.000 description 1
- HJCNGGKJQATACT-UHFFFAOYSA-N 6-tert-butyl-2-(3-tert-butyl-2-hydroxy-6-methylphenyl)sulfanyl-3-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1SC1=C(C)C=CC(C(C)(C)C)=C1O HJCNGGKJQATACT-UHFFFAOYSA-N 0.000 description 1
- ADRNSOYXKABLGT-UHFFFAOYSA-N 8-methylnonyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCC(C)C)OC1=CC=CC=C1 ADRNSOYXKABLGT-UHFFFAOYSA-N 0.000 description 1
- GICJPJUZKGEFIW-UHFFFAOYSA-N CN(c1ccccc11)N1Nc(cccc1)c1O Chemical compound CN(c1ccccc11)N1Nc(cccc1)c1O GICJPJUZKGEFIW-UHFFFAOYSA-N 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 1
- PTHQJSPLRQKBCQ-UHFFFAOYSA-N OP(O)OP(O)O.C(CCCCCCCCCCCCCCCCC)C(O)(C(CO)(CO)CO)CCCCCCCCCCCCCCCCCC.OP(O)OP(O)O.C(C)(C)(C)C1=C(C(=CC=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=CC=C1C(C)(C)C)C(C)(C)C Chemical compound OP(O)OP(O)O.C(CCCCCCCCCCCCCCCCC)C(O)(C(CO)(CO)CO)CCCCCCCCCCCCCCCCCC.OP(O)OP(O)O.C(C)(C)(C)C1=C(C(=CC=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=CC=C1C(C)(C)C)C(C)(C)C PTHQJSPLRQKBCQ-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 241001483078 Phyto Species 0.000 description 1
- STLLXWLDRUVCHL-UHFFFAOYSA-N [2-[1-[2-hydroxy-3,5-bis(2-methylbutan-2-yl)phenyl]ethyl]-4,6-bis(2-methylbutan-2-yl)phenyl] prop-2-enoate Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(C(C)C=2C(=C(C=C(C=2)C(C)(C)CC)C(C)(C)CC)OC(=O)C=C)=C1O STLLXWLDRUVCHL-UHFFFAOYSA-N 0.000 description 1
- IORUEKDKNHHQAL-UHFFFAOYSA-N [2-tert-butyl-6-[(3-tert-butyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenyl] prop-2-enoate Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)OC(=O)C=C)=C1O IORUEKDKNHHQAL-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 description 1
- GPKQLHLOONCFDY-UHFFFAOYSA-N bis(6-methylheptyl) phenyl phosphite Chemical compound CC(C)CCCCCOP(OCCCCCC(C)C)OC1=CC=CC=C1 GPKQLHLOONCFDY-UHFFFAOYSA-N 0.000 description 1
- SXXILWLQSQDLDL-UHFFFAOYSA-N bis(8-methylnonyl) phenyl phosphite Chemical compound CC(C)CCCCCCCOP(OCCCCCCCC(C)C)OC1=CC=CC=C1 SXXILWLQSQDLDL-UHFFFAOYSA-N 0.000 description 1
- JWXSMZJIYUUXSV-UHFFFAOYSA-N bis[2-tert-butyl-6-[(3-tert-butyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenyl] benzene-1,4-dicarboxylate Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)OC(=O)C=2C=CC(=CC=2)C(=O)OC=2C(=CC(C)=CC=2CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)C(C)(C)C)=C1O JWXSMZJIYUUXSV-UHFFFAOYSA-N 0.000 description 1
- GGAUUQHSCNMCAU-UHFFFAOYSA-N butane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)CC(C(O)=O)C(C(O)=O)CC(O)=O GGAUUQHSCNMCAU-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- OGVJEUDMQQIAPV-UHFFFAOYSA-N diphenyl tridecyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCCCCCCC)OC1=CC=CC=C1 OGVJEUDMQQIAPV-UHFFFAOYSA-N 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 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
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- MFPCPCHVMQLDJN-UHFFFAOYSA-N phenyl ditridecyl phosphite Chemical compound CCCCCCCCCCCCCOP(OCCCCCCCCCCCCC)OC1=CC=CC=C1 MFPCPCHVMQLDJN-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
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- Liquid Crystal Substances (AREA)
Description
本発明は電気光学的液晶表示材料として有用なネマチック液晶組成物及び、これを用いた液晶表示素子に関する。 The present invention relates to a nematic liquid crystal composition useful as an electro-optical liquid crystal display material and a liquid crystal display element using the same.
液晶表示装置(LCD)は、電卓のディスプレイとして登場して以来、コンピューターの開発と歩みを同じくして、TN-LCD(捻れネマチック液晶表示装置)から、STN-LCDへと表示容量の拡大に対応してきた。STN-LCDは、シェファー(Scheffer)等［SID ’85 Digest, 120頁(1985年)］、あるいは衣川等［SID ’86 Digest, 122頁(1986年)］によって、開発され、ワードプロセッサ、パーソナルコンピュータなどの高情報処理用の表示に広く普及しはじめている。特に、各画素に薄膜トランジスタをつけたアクティブマトリクス液晶表示素子(AM-LCD)は、CRTにも代替できる高画質を備え、フラット化、省エネルギー化の後押しを受けて、もっとも将来性のあるディスプレイとして期待されている。 AM-LCDではコントラストを上げるために、各画素に薄膜トランジスタやダイオードのスイッチング素子をつけて、画素に電圧を供給する。 The liquid crystal display (LCD) has been used as a calculator display, and it has been the same as the development of computers to support the expansion of display capacity from TN-LCD (twisted nematic liquid crystal display) to STN-LCD. I have done it. STN-LCD was developed by Scheffer et al. [SID '85 Digest, p. 120 (1985)] or Kinukawa et al. [SID '86 Digest, p. 122 (1986)]. Word processors, personal computers, etc. It has begun to spread widely in the display for high information processing. In particular, the active matrix liquid crystal display element (AM-LCD) with thin film transistors attached to each pixel has high image quality that can be substituted for CRT, and is expected to be the most promising display with flattening and energy saving boosts. Has been. In the AM-LCD, in order to increase the contrast, a switching element such as a thin film transistor or a diode is attached to each pixel to supply a voltage to the pixel.
AM-LCDはTN、STNのパッシブ駆動方式とは異なり、スイッチング素子を通して、各画素に数十msec毎に電荷を供給することにより駆動する。このため、電荷が供給されてから数十msec後の次の書き込み時間までの間は、与えられた電荷を完全に保持できないと、表示の悪化をきたすことになる。電荷が逃げると電極間の電位が下がり、透過光強度が変化してコントラストが低下してしまう。このため、AM-LCDでは、高い電圧保持特性が求められる。高い電圧保持特性を得るため、AM-LCD用液晶組成物は、高比抵抗を維持しやすい材料を取捨選択して使用する必要がある。 Unlike the TN and STN passive drive systems, the AM-LCD is driven by supplying electric charge to each pixel every several tens of milliseconds through a switching element. For this reason, if the applied charge cannot be held completely until the next writing time after several tens of milliseconds after the charge is supplied, the display is deteriorated. When the electric charge escapes, the potential between the electrodes is lowered, the transmitted light intensity is changed, and the contrast is lowered. For this reason, AM-LCDs require high voltage holding characteristics. In order to obtain a high voltage holding characteristic, it is necessary to select and use a material that can easily maintain a high specific resistance for the liquid crystal composition for AM-LCD.
近年携帯を目的としたノート型コンピューターの需要が高まり、屋外での使用を可能とする広い使用温度範囲や長時間のバッテリー駆動を可能とする低消費電力の要請が強まっている。低消費電力には低電圧で駆動できるしきい値電圧の低い液晶組成物が求められている。しきい値電圧を低くするためには、誘電率異方性Δεを大きくする材料が必要であるが、誘電率異方性が大きい系では、粘性が増大し、レスポンスが悪化することに加え、周囲の汚染の影響を受けやすくなるため、高抵抗を維持することが難しくなるという問題があった。このため、TN、STN、AM-LCD等の液晶表示素子用液晶組成物には、
(1) 屋外でも使用できる広い液晶相温度範囲
(2) 高温条件でも使用できる安定性
(3) 低いしきい値電圧
(4) 高い電圧保持率
(5) 色づきを防ぎ、広い視角で最適なコントラストを得るために調節可能なΔn
が求められている。
In recent years, demand for notebook computers for portable purposes has increased, and there has been a growing demand for low power consumption that enables a wide operating temperature range that allows outdoor use and long-time battery operation. For low power consumption, a liquid crystal composition having a low threshold voltage that can be driven at a low voltage is required. In order to lower the threshold voltage, a material that increases the dielectric anisotropy Δε is necessary. However, in a system with a large dielectric anisotropy, the viscosity increases and the response deteriorates. There is a problem that it is difficult to maintain a high resistance because it is easily affected by surrounding contamination. For this reason, liquid crystal compositions for liquid crystal display elements such as TN, STN, AM-LCD, etc.
(1) Wide liquid crystal phase temperature range that can be used outdoors
(2) Stability that can be used even at high temperatures
(3) Low threshold voltage
(4) High voltage holding ratio
(5) Adjustable Δn to prevent coloring and obtain optimum contrast over a wide viewing angle
Is required.
従来の液晶組成物は、これらの要請に必ずしも応えることができず、高温での電圧保持率の低下によるコントラスト低下、低温での結晶析出やスメクチック相の発現が見られた。また、屋外の高温やUV光・太陽光暴露下に放置されると、保持率低下や表示不良がみられた。 Conventional liquid crystal compositions are not always able to meet these requirements, and a decrease in contrast due to a decrease in voltage holding ratio at a high temperature, a crystal precipitation at a low temperature, and an appearance of a smectic phase were observed. In addition, when it was left outdoors under high temperature or UV light / sunlight exposure, the retention rate decreased and display was poor.
すなわち、高いネマチック-アイソトロピック転移温度、低いクリスタル(若しくはスメクチック)転移温度、低電圧駆動可能な低いしきい値電圧、高速応答を可能とする低粘性、かつ高温での高い保持率を同時に満足する液晶組成物及び液晶表示素子はなかった。
たとえば、トリフルオロ化合物とジフルオロ化合物とを用いた液晶組成物の例が開示されているが（特許文献１参照）、液晶温度範囲が狭かったり、しきい値電圧が高い等多くの問題点を抱えているのが現状である。
That is, high nematic-isotropic transition temperature, low crystal (or smectic) transition temperature, low threshold voltage that can be driven at low voltage, low viscosity that enables high-speed response, and high retention at high temperature. There were no liquid crystal composition and liquid crystal display element.
For example, although an example of a liquid crystal composition using a trifluoro compound and a difluoro compound is disclosed (see Patent Document 1), it has many problems such as a narrow liquid crystal temperature range and a high threshold voltage. This is the current situation.
本発明の課題は、低温安定性に優れ、広いネマティック温度範囲を有しまたその加熱安定性に優れた液晶組成物を提供し、これを用いた、高温度での高い電圧保持率、低い閾値電圧、適切な誘電率異方性、屈折率異方性を有し、使用温度範囲が広く、高速応答性に優れ、これらの諸特性の経時変化の少ない液晶表示素子を提供する、若しくは従来より上記の欠点を改善した液晶組成物及び液晶表示素子(TN、STN、AM-LCD)を提供することにある。 An object of the present invention is to provide a liquid crystal composition having excellent low-temperature stability, a wide nematic temperature range and excellent heat stability, and using this, a high voltage holding ratio at a high temperature, a low threshold value Providing a liquid crystal display element with voltage, appropriate dielectric anisotropy, refractive index anisotropy, wide operating temperature range, excellent high-speed response, and little change with time in these characteristics, or conventionally An object of the present invention is to provide a liquid crystal composition and a liquid crystal display element (TN, STN, AM-LCD) in which the above-mentioned drawbacks are improved.
本発明は、上記課題を解決するために、種々の液晶化合物と酸化防止剤の組み合わせを検討した結果、以下に記載する液晶組成物及びそれらを用いた液晶表示素子を見いだした。
一般式(I)
In order to solve the above-mentioned problems, the present invention has studied combinations of various liquid crystal compounds and antioxidants, and as a result, found the following liquid crystal compositions and liquid crystal display elements using them.
Formula (I)
（式中、Ｒ及びＺはハロゲンで置換されていても良い、炭素原子数１〜１６のアルキル基、アルコキシ基、炭素原子数２〜１６のアルケニル基、炭素原子数３〜１６のアルケニルオキシ基、炭素原子数１〜１０のアルコキシ基で置換された炭素原子数１〜１２のアルキル基を表し、あるいはＺは水素原子、フッ素原子、塩素原子、トリフルオロメトキシ基、ジフルオロメトキシ基、トリフルオロメチル基、３，３，３−トリフルオロエトキシ基、シアノ基、シアナト基、水酸基もしくはカルボキシル基を表し、ｍ及びｎはそれぞれ独立的に０〜２の整数を表すがｍ＋ｎ≦３であり、存在するＬ及びＭは同一でも異なっていてもよい−ＣＨ２ＣＨ２−、−ＣＨ（ＣＨ３）ＣＨ２−、−ＣＨ２ＣＨ（ＣＨ３）−、−ＣＨ２Ｏ−、−ＯＣＨ２−、−ＣＦ２Ｏ−、−ＯＣＦ２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−ＣＦ＝ＣＨ−、−ＣＨ＝ＣＦ−、フッ素以外のハロゲン化されていても良い−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−Ｏ（ＣＨ２）３−、−（ＣＨ２）３Ｏ−、−（ＣＨ２）４−もしくは単結合を表し、存在する環Ａ、環Ｂ及び環Ｓは同一でも異なっていてもよく、基中に存在する１個のＣＨ２基または隣接していない２個以上のＣＨ２基が−Ｏ−及びまたは−Ｓ−に置き換えられても良いトランス−１，４−シクロへキシレン基、基中に存在する１個のＣＨ基または隣接していない２個以上のＣＨ基が−Ｎ＝に置き換えられてもよい１，４−フェニレン基、１，４−シクロヘキセニレン基、１，４−ビシクロ（２．２．２）オクチレン基、ピペリジン−１，４−ジイル基、ナフタレン−２，６−ジイル基、トランス−デカヒドロナフタレン−トランス−２，６−ジイル基もしくは１，２，３，４−テトラヒドロナフタレン−２，６−ジイル基を表し、これらはシアノ基もしくはハロゲンで置換されていても良い。）の化合物群のうち、
一般式（Ｉ−３）
(In the formula, R and Z may be substituted with halogen, an alkyl group having 1 to 16 carbon atoms, an alkoxy group, an alkenyl group having 2 to 16 carbon atoms, and an alkenyloxy group having 3 to 16 carbon atoms. Represents an alkyl group having 1 to 12 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, or Z represents a hydrogen atom, a fluorine atom, a chlorine atom, a trifluoromethoxy group, a difluoromethoxy group, or trifluoromethyl. Represents a group, 3,3,3-trifluoroethoxy group, cyano group, cyanato group, hydroxyl group or carboxyl group, and m and n each independently represents an integer of 0 to 2, but m + n ≦ 3 and exist. L and M -CH 2 may be the same or different are CH 2 -, - CH (CH 3) CH 2 -, - CH 2 CH (CH 3) -, - CH 2 O -, - OC 2 -, - CF 2 O - , - OCF 2 -, - COO -, - OCO -, - CH = CH -, - CF = CF -, - CF = CH -, - CH = CF-, halogen other than fluorine Represents —CH═CH—, —C≡C—, —O (CH 2 ) 3 —, — (CH 2 ) 3 O—, — (CH 2 ) 4 — or a single bond, ring a to ring B and ring S may be the same or different, two or more CH 2 groups not one CH 2 group or adjacent present in groups -O- and or -S- A trans-1,4-cyclohexylene group which may be replaced with one CH group present in the group or two or more CH groups which are not adjacent to each other may be replaced with -N = 4-phenylene group, 1,4-cyclohexenylene group, 1,4-bicyclo (2.2.2) octyl Group, piperidine-1,4-diyl group, naphthalene-2,6-diyl group, trans-decahydronaphthalene-trans-2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2,6 - represents a diyl group, these are among the group of compounds may be substituted with a cyano group or a halogen).
Formula (I-3)
（式中、Ｒ３及びＺ３はハロゲンで置換されていても良い、炭素原子数１〜１６のアルキル基、アルコキシ基、炭素原子数２〜１６のアルケニル基、炭素原子数３〜１６のアルケニルオキシ基、炭素原子数１〜１０のアルコキシ基で置換された炭素原子数１〜１２のアルキル基を表し、あるいはＺ３は水素原子、フッ素原子、塩素原子、トリフルオロメトキシ基、ジフルオロメトキシ基、トリフルオロメチル基もしくは３，３，３−トリフルオロエトキシ基を表し、ｍ３及びｎ３はそれぞれ独立的に０〜２の整数を表すがｍ３＋ｎ３≦３であり、存在するＬ３及びＭ３は同一でも異なっていてもよい−ＣＨ(In the formula, R3 and Z3 may be substituted with halogen, an alkyl group having 1 to 16 carbon atoms, an alkoxy group, an alkenyl group having 2 to 16 carbon atoms, and an alkenyloxy group having 3 to 16 carbon atoms. Represents an alkyl group having 1 to 12 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, or Z3 represents a hydrogen atom, a fluorine atom, a chlorine atom, a trifluoromethoxy group, a difluoromethoxy group, or trifluoromethyl. Group, or 3,3,3-trifluoroethoxy group, m3 and n3 each independently represents an integer of 0 to 2, but m3 + n3 ≦ 3, and L3 and M3 present may be the same or different. -CH ２2 ＣＨCH ２2 −、−ＣＨ（ＣＨ-, -CH (CH ３3 ）ＣＨ) CH ２2 −、−ＣＨ-, -CH ２2 ＣＨ（ＣＨCH (CH ３3 ）−、−ＣＨ)-, -CH ２2 Ｏ−、−ＯＣＨO-, -OCH ２2 −、−ＣＦ-, -CF ２2 Ｏ−、−ＯＣＦO-, -OCF ２2 −、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−ＣＦ＝ＣＨ−、−ＣＨ＝ＣＦ−、フッ素以外のハロゲン化されていても良い−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−Ｏ（ＣＨ-, -CH = CH-, -CF = CF-, -CF = CH-, -CH = CF-, optionally halogenated other than fluorine -CH = CH-, -C≡C-, -O (CH ２2 ）) ３3 −、−（ＣＨ-,-(CH ２2 ）) ３3 Ｏ−、−（ＣＨO-,-(CH ２2 ）) ４4 −もしくは単結合を表し、存在する環Ａ３及び環Ｂ３は同一でも異なっていてもよく、基中に存在する１個のＣＨ-Represents a single bond, ring A3 and ring B3 present may be the same or different, and one CH present in the group ２2 基または隣接していない２個以上のＣＨ2 or more CHs not adjacent or adjacent ２2 基が−Ｏ−に置き換えられても良いトランス−１，４−シクロへキシレン基、１，４−フェニレン基、１，４−シクロヘキセニレン基、１，４−ビシクロ（２．２．２）オクチレン基、ナフタレン−２，６−ジイル基、トランス−デカヒドロナフタレン−トランス−２，６−ジイル基もしくは１，２，３，４−テトラヒドロナフタレン−２，６−ジイル基を表し、これらはハロゲンで置換されていても良い、Ｘ４、Ｘ５、Ｘ６、Ｘ７、Ｘ８及びＸ９はそれぞれ独立的にフッ素原子、塩素原子もしくは水素原子を表す。）の化合物から１種もしくは２種以上の化合物を少なくとも５質量％含有し、一般式（ＶＩ）又は（ＶＩＩ）Trans-1,4-cyclohexylene group, 1,4-phenylene group, 1,4-cyclohexenylene group, 1,4-bicyclo (2.2.2), in which the group may be replaced by —O— Represents an octylene group, a naphthalene-2,6-diyl group, a trans-decahydronaphthalene-trans-2,6-diyl group or a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, which are halogenated X4, X5, X6, X7, X8 and X9 which may be substituted with each independently represent a fluorine atom, a chlorine atom or a hydrogen atom. ) Containing at least 5% by mass of one or more compounds from the compound of general formula (VI) or (VII)
（式中ｔ−Ｂｕ−は（ＣＨ(Where t-Bu- is (CH ３3 ）) ３3 Ｃ−を表す。）の構造を部分構造として有する（二つの構造を同時に有する化合物を除く。）フェノール系酸化防止剤の少なくとも１種を０．０００１〜５質量％含有する液晶組成物。C- is represented. ) As a partial structure (excluding compounds having two structures at the same time). A liquid crystal composition containing 0.0001 to 5% by mass of at least one phenolic antioxidant.
本発明の液晶材料及び酸化防止剤の組み合わせによって、低温安定性に優れ、広いネマティック温度範囲を有し、またその加熱安定性に優れ、高温度での高い電圧保持率等を有する液晶組成物、若しくは従来より上記の欠点を改善した液晶組成物を得ることができた。これを用いた低い閾値電圧、適切な誘電率異方性、屈折率異方性を有し、使用温度範囲が広く、高速応答性を有し、これらの諸特性の経時変化の少ない液晶表示素子、若しくは従来より上記の欠点を改善した液晶表示素子(TN、STN、AM-LCD)を作成することができた。この液晶表示素子は信頼性が高く、表示品位の優れたものであり、STN、AM-LCDを始めとする液晶ディスプレイとして非常に実用的である。 By combining the liquid crystal material and the antioxidant of the present invention, a liquid crystal composition having excellent low temperature stability, having a wide nematic temperature range, excellent heat stability, high voltage holding ratio at high temperature, etc., Or the liquid crystal composition which improved the said fault conventionally was able to be obtained. A liquid crystal display device having a low threshold voltage, suitable dielectric anisotropy and refractive index anisotropy, a wide operating temperature range, high-speed response, and little change with time in these characteristics. Alternatively, liquid crystal display elements (TN, STN, AM-LCD) that have improved the above-described drawbacks can be produced. This liquid crystal display element has high reliability and excellent display quality, and is very practical as a liquid crystal display including STN and AM-LCD.
以下に本発明の一例について説明する。
一般式(I)の化合物として一般式(I-1)、一般式(I-2)及び一般式(I-3)
An example of the present invention will be described below.
General formula (I-1), general formula (I-2) and general formula (I-3) as compounds of general formula (I)
(式中、R1、R2、R3、Z1、Z2及びZ3はハロゲンで置換されていても良い、炭素原子数1〜16のアルキル基、アルコキシ基、炭素原子数2〜16のアルケニル基、炭素原子数3〜16のアルケニルオキシ基、炭素原子数1〜10のアルコキシ基で置換された炭素原子数1〜12のアルキル基を表し、あるいはZ1、Z2及びZ3は水素原子、フッ素原子、塩素原子、トリフルオロメトキシ基、ジフルオロメトキシ基、トリフルオロメチル基、3,3,3-トリフルオロエトキシ基、シアノ基、シアナト基、水酸基もしくはカルボキシル基を表し、m1、m2、m3、n1、n2及びn3はそれぞれ独立的に0〜2の整数を表すがm1+n1≦3、m2+n2≦3、m3+n3≦3であり、存在するL1、L2、L3、M1、M2及びM3は同一でも異なっていてもよい-CH2CH2-、-CH(CH3)CH2-、-CH2CH(CH3)-、-CH2O-、-OCH2-、-CF2O-、-OCF2-、-COO-、-OCO-、-CH=CH-、-CF=CF-、-CF=CH-、-CH=CF-、フッ素以外のハロゲン化されていても良い-CH=CH-、-C≡C-、-O(CH2)3-、-(CH2)3O-、-(CH2)4-もしくは単結合を表し、存在する環A1、環B1、環A2、環B2、環A3及び環B3は同一でも異なっていてもよく、基中に存在する1個のCH2基または隣接していない2個以上のCH2基が-O-及びまたは-S-に置き換えられても良いトランス-1,4-シクロへキシレン基、基中に存在する1個のCH基または隣接していない2個以上のCH基が-N=に置き換えられてもよい1,4-フェニレン基、1,4-シクロヘキセニレン基、1,4-ビシクロ(2.2.2)オクチレン基、ピペリジン-1,4-ジイル基、ナフタレン-2,6-ジイル基、トランス-デカヒドロナフタレン-トランス-2,6-ジイル基もしくは1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基を表し、これらはシアノ基もしくはハロゲンで置換されていても良い、X1、X2、X3、X4、X5、X6、X7、X8及びX9はそれぞれ独立的にフッ素原子、塩素原子もしくは水素原子を表す。)の化合物群から選択される化合物が好ましい。
更に、一般式(IV)及び一般式(V)
(Wherein, R1, R2, R3, Z1, Z2 and Z3 may be substituted with a halogen, an alkyl group having 1 to 16 carbon atoms, an alkoxy group, an alkenyl group having 2 to 16 carbon atoms, a carbon atom An alkenyloxy group having 3 to 16 carbon atoms, an alkyl group having 1 to 12 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, or Z1, Z2 and Z3 are a hydrogen atom, a fluorine atom, a chlorine atom, Represents a trifluoromethoxy group, a difluoromethoxy group, a trifluoromethyl group, a 3,3,3-trifluoroethoxy group, a cyano group, a cyanato group, a hydroxyl group or a carboxyl group, and m1, m2, m3, n1, n2 and n3 are Each independently represents an integer of 0 to 2, but m1 + n1 ≦ 3, m2 + n2 ≦ 3, m3 + n3 ≦ 3, and existing L1, L2, L3, M1, M2 and M3 are the same or different. -CH 2 CH 2- , -CH (CH 3 ) CH 2- , -CH 2 CH (CH 3 )-, -CH 2 O-, -OCH 2- , -CF 2 O-, -OCF 2 -, -COO-, -OCO-, -C H = CH-, -CF = CF-, -CF = CH-, -CH = CF-, optionally halogenated other than fluorine -CH = CH-, -C≡C-, -O (CH 2 ) 3 -,-(CH 2 ) 3 O-,-(CH 2 ) 4 -or a single bond, and existing ring A1, ring B1, ring A2, ring B2, ring A3 and ring B3 are the same or different. A trans-1,4-cyclohexylene group in which one CH2 group present in the group or two or more non-adjacent CH2 groups may be replaced by -O- and / or -S- , One CH group present in the group or two or more non-adjacent CH groups may be replaced by -N =, 1,4-phenylene group, 1,4-cyclohexenylene group, 1, 4-bicyclo (2.2.2) octylene group, piperidine-1,4-diyl group, naphthalene-2,6-diyl group, trans-decahydronaphthalene-trans-2,6-diyl group or 1,2,3, Represents 4-tetrahydronaphthalene-2,6-diyl group, which is substituted with cyano group or halogen May have, X1, X2, X3, X4, X5, X6, X7, respectively X8 and X9 independently fluorine atom, a chlorine atom or a hydrogen atom. A compound selected from the group of compounds) are preferred.
Furthermore, general formula (IV) and general formula (V)
(式中、R4、R5及びR6はそれぞれ独立的にフッ素置換されていても良い炭素原子数1〜16のアルキル基またはアルコキシル基、炭素原子数2〜16のアルケニル基、炭素原子数3〜16のアルケニルオキシ基、または炭素原子数1〜10のアルコキシル基で置換された炭素原子数1〜12のアルキル基を表し、環A4、環A5、環B4、環C1及び環C2はそれぞれ独立的にフッ素原子により置換されていてもよい1,4-フェニレン基、2-メチル-1,4-フェニレン基、3-メチル-1,4-フェニレン基、ナフタレン-2,6-ジイル基、フェナントレン-2,7-ジイル基、フルオレン-2,7-ジイル基、トランス-1,4-シクロヘキシレン基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基、デカヒドロナフタレン-2,6-ジイル基、トランス-1,3ジオキサン-2,5-ジイル基、ピリジン-2,5-ジイル基、ピリミジン-2,5-ジイル基、ピラジン-2,5-ジイル基またはピリダジン-2,5-ジイル基を表し、n4、m4はそれぞれ独立的に0、1もしくは2を表し、L4、L5、M4及びM5ははそれぞれ独立的に-CH2CH2-、-CH2CH(CH3)-、-CH(CH3)CH2-、-CH2O-、-OCH2-、-CF2O-、-OCF2-、-CH2CH2CH2CH2-、-CH=CHCH2CH2-、-CH2CH=CHCH2-、-CH2CH2CH=CH-、-OCH2CH2CH2-、-CH2OCH2CH2-、-CH2CH2OCH2-、-CH2CH2CH2O-、-CF2OCH2CH2-、-CH2CH2OCF2-、-CF=CF-、-CH=CH-、-C≡C-または単結合を表し、Y2はシアノ基、フッ素原子、塩素原子、トリフルオロメトキシ基、トリフルオロメチル基、ジフルオロメトキシ基、水素原子、3,3,3-トリフルオロエトキシ基、R’または-OR’を表し、R’は炭素原子数1〜12の直鎖状アルキル基または、2〜12の直鎖状アルケニル基を表し、Y1、Y3は水素原子、フッ素原子または塩素原子を表す。)の化合物群から選ばれる1種もしくは2種以上の化合物を含有することが好ましく、具体的には一般式(I-1)の化合物として以下で表される一般式(I-1a)〜(I-1d)化合物が、一般式(I-2)の化合物として以下で表される一般式(I-2a)〜(I-2e)が、一般式(I-3)の化合物として以下で表される一般式(I-3a)〜(I-3g)がより好ましい。 (In the formula, R4, R5 and R6 each independently may be fluorine-substituted alkyl group or alkoxyl group having 1 to 16 carbon atoms, alkenyl group having 2 to 16 carbon atoms, or 3 to 16 carbon atoms. Or an alkyl group having 1 to 12 carbon atoms substituted with an alkoxyl group having 1 to 10 carbon atoms, and ring A4, ring A5, ring B4, ring C1 and ring C2 are each independently 1,4-phenylene group, 2-methyl-1,4-phenylene group, 3-methyl-1,4-phenylene group, naphthalene-2,6-diyl group, phenanthrene-2 which may be substituted by fluorine atom , 7-diyl group, fluorene-2,7-diyl group, trans-1,4-cyclohexylene group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6 -Diyl group, trans-1,3 dioxane-2,5-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyra N-2,5-diyl group or pyridazine-2,5-diyl group, n4 and m4 each independently represent 0, 1 or 2, and L4, L5, M4 and M5 each independently represent- CH 2 CH 2- , -CH 2 CH (CH 3 )-, -CH (CH 3 ) CH 2- , -CH 2 O-, -OCH 2- , -CF 2 O-, -OCF 2- , -CH 2 CH 2 CH 2 CH 2- , -CH = CHCH 2 CH 2- , -CH 2 CH = CHCH 2- , -CH 2 CH 2 CH = CH-, -OCH 2 CH 2 CH 2- , -CH 2 OCH 2 CH 2- , -CH 2 CH 2 OCH 2- , -CH 2 CH 2 CH 2 O-, -CF 2 OCH 2 CH 2- , -CH 2 CH 2 OCF 2- , -CF = CF-, -CH = CH-, -C≡C- or a single bond, Y2 is a cyano group, a fluorine atom, a chlorine atom, a trifluoromethoxy group, a trifluoromethyl group, a difluoromethoxy group, a hydrogen atom, 3,3,3-tri Fluoroethoxy group, R ′ or —OR ′, where R ′ represents a linear alkyl group having 1 to 12 carbon atoms or a linear alkenyl group having 2 to 12 carbon atoms, Y1, Y3 are hydrogen atoms, fluorine Represents an atom or a chlorine atom.) It is preferable to contain one or two or more selected compounds, specifically, compounds represented by the following general formulas (I-1a) to (I-1d) as compounds of the general formula (I-1) Are represented by the following general formulas (I-2a) to (I-2e) represented by the general formula (I-2): I-3a) to (I-3g) are more preferable.
(式中、R1、R2、X1、X2、X3、Z1及びZ2は一般式(I-1)、一般式(I-2)におけると同じ意味を表し、l及びkはそれぞれ独立的に1〜4を表す。) (In the formula, R1, R2, X1, X2, X3, Z1 and Z2 represent the same meaning as in general formula (I-1) and general formula (I-2), and l and k are each independently 1 to Represents 4.)
(式中、R3、Z3、X4、X5、X6、X7、X8及びX9は一般式(I-3)におけると同じ意味を表し、l及びkはそれぞれ独立的に1〜4を表す。)
本発明において、R1〜R6はそれぞれ独立して、炭素原子数1〜10のアルキル基もしくは炭素原子数2〜10のアルケニル基が好ましく、非置換の直鎖状炭素原子数1〜8のアルキル基もしくは炭素原子数2〜8のアルケニル基がより好ましく、非置換の直鎖状炭素原子数1〜5のアルキル基もしくは炭素原子数2〜5のアルケニル基が特に好ましい。またR4a、R4b、R5a、R5bはそれぞれ独立して非置換の直鎖状炭素原子数1〜5のアルキル基もしくは炭素原子数2〜5のアルケニル基が好ましい。
(Wherein R3, Z3, X4, X5, X6, X7, X8 and X9 represent the same meaning as in general formula (I-3), and l and k each independently represent 1 to 4).
In the present invention, R1 to R6 are each independently preferably an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and an unsubstituted linear alkyl group having 1 to 8 carbon atoms. Alternatively, an alkenyl group having 2 to 8 carbon atoms is more preferable, and an unsubstituted linear alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms is particularly preferable. R4a, R4b, R5a and R5b are each independently preferably an unsubstituted linear alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms.
またZ1〜Z3はそれぞれ独立に水素原子、フッ素原子、塩素原子、トリフルオロメトキシ基、ジフルオロメトキシ基、トリフルオロメチル基、3,3,3-トリフルオロエトキシ基、シアノ基であることが好ましく、水素原子、フッ素原子、トリフルオロメトキシ基、トリフルオロメチル基であることが特に好ましい。 Z1 to Z3 are each independently preferably a hydrogen atom, a fluorine atom, a chlorine atom, a trifluoromethoxy group, a difluoromethoxy group, a trifluoromethyl group, a 3,3,3-trifluoroethoxy group, or a cyano group, Particularly preferred are a hydrogen atom, a fluorine atom, a trifluoromethoxy group, and a trifluoromethyl group.
本発明では液晶組成物中に1種以上の酸化防止剤を含有させるが、この酸化防止剤としてはフェノール系酸化防止剤、ホスファイト系酸化防止剤、ホスフォオイト系酸化防止剤、イオウ系酸化防止剤、ヒンダードアミン系酸化防止剤、トリアゾール系酸化防止剤等が挙げられる。
本発明においてフェノール系酸化防止剤としては、特に限定されないが、下記一般式(VI)と(VII)の構造を部分構造として有する化合物が例示される。
In the present invention, the liquid crystal composition contains one or more antioxidants. Examples of the antioxidants include phenol-based antioxidants, phosphite-based antioxidants, phosphorite-based antioxidants, and sulfur-based antioxidants. Hindered amine antioxidants, triazole antioxidants, and the like.
In the present invention, the phenolic antioxidant is not particularly limited, and examples thereof include compounds having the following general formulas (VI) and (VII) as partial structures.
(式中t-Bu-は(CH3)3C-を表す。)
好ましい具体例としては、2,6-ジ-t-ブチル-4-メチルフェノール、ペンタエリスリチル-テトラキス〔3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート、オクタデシル-3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート、1,3,5-トリメチル-2,4,6-トリス(3,5-ジ-t-ブチル-4-ヒドロキシベンジル)ベンゼン、2,2’-メチレンビス(6-t-ブチル-4-メチルフェノール)、2-t-ブチル-6-(3-t-ブチル-2-ヒドロキシ-5-メチルベンジル)-4-メチルフェニルアクリレート、2-［1-(2-ヒドロキシ-3,5-ジ-t-ペンチルフェニル)エチル］-4,6-ジ-t-ペンチルフェニルアクリレート、4,4’-ブチリデンビス(6-t-ブチル-3-メチルフェノール)、3,9’-ビス［2-｛3-(3-t-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオニルオキシ｝-1,1-ジメチルエチル］-2,4,8,10-テトラオキサスピロ［5・5］ウンデカン-2-(3,5-ジ-t-ブチル-4-ヒドロキシアニリノ)-4,6-ビス(n-オクチルチオ)-1,3,5-トリアジン、2,2’-エチリデンビス(4,6-ジ-t-ブチルフェノール)、2,2’-エチリデンビス(4-sec-ブチル-6-t-ブチルフェノール)、2,2’-チオビス(6-t-ブチル-3-メチルフェノール)、1,1,3-トリス(5-t-ブチル-4-ヒドロキシ-2-メチルフェニル)ブタン、ビス［2-t-ブチル-4-メチル-6-(3-t-ブチル-2-ヒドロキシ-5-メチルベンジル)フェニル］テレフタレート、テトラキス［メチレン-3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート］メタン、2,2’-チオジエチレンビス［3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート］、トリエチレングリコールビス［3-(3-t-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオネート］、1,6-ヘキサンジオールビス［3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート］、1,3,5-トリス(3,5-ジ-t-ブチル-4-ヒドロキシベンジル)イソシアヌレート、1,3,5-トリス［2-｛3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオニルオキシ｝エチル］イソシアヌレート、1,3,5-トリス(4-t-ブチル-3-ヒドロキシ-2,6-ジメチルベンジル)イソシアヌレート、1,3,5-トリス(3,5-ジ-t-ブチル-4-ヒドロキシベンジル)-2,4,6-トリメチルベンゼン等が挙げられる。
また、本発明においてイオウ系酸化防止剤としては、特に限定されないが、下記一般式(VIII)、一般式(IX)の部分構造を持った化合物が例示される。
(Wherein t-Bu- represents (CH 3 ) 3 C-)
Preferred examples include 2,6-di-t-butyl-4-methylphenol, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, octadecyl-3 -(3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) Benzene, 2,2'-methylenebis (6-t-butyl-4-methylphenol), 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl Acrylate, 2- [1- (2-Hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, 4,4'-butylidenebis (6-t-butyl -3-methylphenol), 3,9'-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4 , 8,10-Tetraoxaspiro [5 ・ 5] undecane-2- (3,5 -Di-t-butyl-4-hydroxyanilino) -4,6-bis (n-octylthio) -1,3,5-triazine, 2,2'-ethylidenebis (4,6-di-t-butylphenol ), 2,2'-ethylidenebis (4-sec-butyl-6-t-butylphenol), 2,2'-thiobis (6-t-butyl-3-methylphenol), 1,1,3-tris ( 5-t-butyl-4-hydroxy-2-methylphenyl) butane, bis [2-t-butyl-4-methyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) phenyl] terephthalate Tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, 2,2'-thiodiethylenebis [3- (3,5-di-t-butyl-4 -Hydroxyphenyl) propionate], triethylene glycol bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate], 1,6-hexanediol bis [3- (3,5-di- t-Butyl-4-hydroxyphenyl) propionate 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris [2- {3- (3,5-di-t-butyl -4-hydroxyphenyl) propionyloxy} ethyl] isocyanurate, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris ( 3,5-di-t-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene and the like.
In the present invention, the sulfur-based antioxidant is not particularly limited, and examples thereof include compounds having partial structures of the following general formula (VIII) and general formula (IX).
(式中、R8 はアルキル基を、好ましくは、炭素原子数12のアルキル基を表す。)
好ましい具体例としては、ジラウリル 3,3’-チオジプロピオネート、ジミリスチル 3,3’-チオジプロピオネート、ジステアリル 3,3’-チオジプロピオネート、テトラキス(3-ラウリルチオプロピオニルオキシメチル)メタン等が挙げられる。
さらに、本発明においてホスファイト系酸化防止剤及びホスフォオイト系酸化防止剤としては、特に限定されないが、下記の式一般式(X)から一般式(XIV)の化合物が例示される。
(Wherein R8 represents an alkyl group, preferably an alkyl group having 12 carbon atoms.)
Preferred examples include dilauryl 3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3,3′-thiodipropionate, tetrakis (3-laurylthiopropionyloxymethyl) Examples include methane.
Furthermore, in the present invention, the phosphite antioxidant and the phosphoite antioxidant are not particularly limited, but compounds of the following formulas (X) to (XIV) are exemplified.
(式中R11、R12及びR13は、各々独立に、水素原子又は炭素原子数1〜8のアルキル基を表し、R14はフッ素原子又はアルキル基を表し、X10は単結合、酸素原子又は窒素原子を表す。) (Wherein R11, R12 and R13 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R14 represents a fluorine atom or an alkyl group, X10 represents a single bond, an oxygen atom or a nitrogen atom. Represents.)
(式中、R17は水素原子又はアルキル基を表す。)
好ましい具体例としては、トリス(ノニルフェニル) ホスファイト、トリス(2,4-ジ-t-ブチルフェニル) ホスファイト、テトラキス(2,4-ジ-t-ブチルフェニル) 4,4’-ビフェニレンジホスフォナイト、ビス(2,4-ジ-t-ブチルフェニル) ペンタエリスリトール ジホスファイト、ビス(2,6-ジ-t-ブチルフェニル) ペンタエリスリトール ジホスファイト
ジステアリル ペンタエリスリトール ジホスファイト、フェニル ジイソオクチル ホスファイト、フェニル ジイソデシル ホスファイト、フェニル ジ(トリデシル) ホスファイト、ジフェニル イソオクチルホスファイト、ジフェニル イソデシル ホスファイト、ジフェニル トリデシル ホスファイト、4,4’-イソプロピリデンビス(フェニルジアルキル ホスファイト)、2,2’-メチレンビス(4,6-ジ-t-ブチルフェニル)オクチル ホスファイト、2,2’-エチリデンビス(4,6-ジ-t-ブチルフェニル)フルオロホスフォナイト等が挙げられる。
本発明においてヒンダードアミン系酸化剤としては、特に限定されないが、下記一般式(XV)の構造を部分構造として有する化合物が例示される。
(In the formula, R17 represents a hydrogen atom or an alkyl group.)
Preferred examples include tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) 4,4′-biphenylenedi Phosphonite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butylphenyl) pentaerythritol diphosphite distearyl pentaerythritol diphosphite, phenyl diisooctyl phosphite, Phenyl diisodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl tridecyl phosphite, 4,4'-isopropylidene bis (phenyldialkyl phosphite), 2,2'-methylene bis (4,6-di-t-butylphenyl) octyl phos Phyto, 2,2′-ethylidenebis (4,6-di-t-butylphenyl) fluorophosphonite and the like.
In the present invention, the hindered amine-based oxidizing agent is not particularly limited, and examples thereof include compounds having the structure of the following general formula (XV) as a partial structure.
(式中、R18は水素原子もしくはアルキル基を表す。)
好ましい具体例としては、ビス(2,2,6,6-テトラメチル-4-ピペリジル) セバケート、ビス(N-メチル-2,2,6,6-テトラメチル-4-ピペリジル) セバケート、N,N’ビス(2,2,6,6-テトラメチル-4-ピペリジル)-1,6-ヘキサメチレンジアミン、2-メチル-2-(2,2,6,6-テトラメチル-4-ピペリジル)アミノ-N-(2,2,6,6-テトラメチル-4-ピペリジル)プロピオンアミド、テトラキス(2,2,6,6-テトラメチル-4-ピペリジル) (1,2,3,4-ブタンテトラカルボキシレート、ポリ〔｛6-(1,1,3,3-テトラメチルブチル)イミノ-1,3,5-トリアジン-2,4-ジイル｝｛(2,2,6,6-テトラメチル-4-ピペリジル)イミノ｝ヘキサメチル｛(2,2,6,6-テトラメチル-4-ピペリジル)イミノ｝〕、ポリ〔(6-モルホリノ-1,3,5-トリアジン-2,4-ジイル)｛(2,2,6,6-テトラメチル-4-ピペリジル)イミノ｝ヘキサメチン｛(2,2,6,6-テトラメチル-4-ピペリジル)イミノ｝〕、コハク酸ジメチルと 1-(2-ヒドロキシエチル)-4-ヒドロキシ-2,2,6,6-テトラメチルピペリジンとの重縮合物、N,N’4,7-テトラキス〔4,6-ビス｛N-ブチル-N-(1,2,2,6,6-ペンタメチル-4-ピペリジル)アミノ｝-1,3,5-トリアジン-2-イル〕-4,7-ジアザデカン-1,10-ジアミン等が挙げられる。
本発明において、トリアゾール系酸化防止剤としては、特に限定されないが、下記一般式(XVI)の構造を部分構造として有する化合物が例示される。
(In the formula, R18 represents a hydrogen atom or an alkyl group.)
Preferred examples include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N, N'bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4-piperidyl) Amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3,4-butane Tetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl -4-piperidyl) imino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazine-2,4-diyl) {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}] Polycondensate of dimethyl succinate with 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine, N, N'4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10- Examples include diamines.
In the present invention, the triazole antioxidant is not particularly limited, and examples thereof include compounds having the structure of the following general formula (XVI) as a partial structure.
具体例としては、2-(2-ヒドロキシ-5-メトキシフェニル)ベンゾトリアゾール、2-(2-ヒドロキシ-3,5-t-ブチルフェニル)ベンゾトリアゾール等が挙げられる。 Specific examples include 2- (2-hydroxy-5-methoxyphenyl) benzotriazole, 2- (2-hydroxy-3,5-t-butylphenyl) benzotriazole and the like.
上述した酸化防止剤の中でも特に一般式(VI)、一般式(VII)で表されるヒンダードフェノール系酸化防止剤が好ましく、さらに酸化防止剤の分子量が400以上であれば液晶素子の製造プロセスにおける加熱、脱気過程において酸化防止剤の揮発がなく安定した組成を維持できるため最も好ましい。ただし、酸化防止剤の分子量があまりに大きくなりすぎると液晶組成物への相溶性が低下するので、分子量2000以下が好ましい。また、酸化防止剤分子中の一般式(VI)、一般式(VII)で表されるヒンダードフェノール部位の割合が多いほど酸化防止効果が高まるので、その他の特性を損なわない範囲内でこの割合を増やすことが好ましい。酸化防止剤の分子量600当たりヒンダードフェノール部位が一つ以上存在することが好ましい。具体例としては、ペンタエリスリチル-テトラキス〔3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート、オクタデシル-3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート、1,3,5-トリメチル-2,4,6-トリス(3,5-ジ-t-ブチル-4-ヒドロキシベンジル)ベンゼン、3,9’-ビス［2-｛3-(3-t-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオニルオキシ｝-1,1-ジメチルエチル］-2,4,8,10-テトラオキサスピロ［5・5］ウンデカン-2-(3,5-ジ-t-ブチル-4-ヒドロキシアニリノ)-4,6-ビス(n-オクチルチオ)-1,3,5-トリアジン、1,1,3-トリス(5-t-ブチル-4-ヒドロキシ-2-メチルフェニル)ブタン、ビス［2-t-ブチル-4-メチル-6-(3-t-ブチル-2-ヒドロキシ-5-メチルベンジル)フェニル］テレフタレート、テトラキス［メチレン-3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート］メタン、2,2’-チオジエチレンビス［3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート］、トリエチレングリコールビス［3-(3-t-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオネート］、1,6-ヘキサンジオールビス［3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート］、1,3,5-トリス(3,5-ジ-t-ブチル-4-ヒドロキシベンジル)イソシアヌレート、1,3,5-トリス［2-｛3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオニルオキシ｝エチル］イソシアヌレート、1,3,5-トリス(4-t-ブチル-3-ヒドロキシ-2,6-ジメチルベンジル)イソシアヌレート、1,3,5-トリス(3,5-ジ-t-ブチル-4-ヒドロキシベンジル)-2,4,6-トリメチルベンゼン等が挙げられる。また、これら酸化防止剤の添加量は、0.0001〜5%であるが、添加量が少なすぎると加熱時の特性が悪化し、添加量が多すぎると液晶表示素子としての諸特性に影響が出ることから、0.0005%〜1%が好ましく、0.001%〜0.5%がより好ましく、0.01%〜0.1%が特に好ましい。 Among the above-mentioned antioxidants, hindered phenolic antioxidants represented by general formula (VI) and general formula (VII) are particularly preferred, and if the molecular weight of the antioxidant is 400 or more, the process for producing a liquid crystal device In the heating and degassing process, the antioxidant is not volatilized, and it is most preferable because a stable composition can be maintained. However, if the molecular weight of the antioxidant becomes too large, the compatibility with the liquid crystal composition is lowered, so that the molecular weight is preferably 2000 or less. In addition, since the antioxidant effect increases as the proportion of the hindered phenol moiety represented by the general formula (VI) or general formula (VII) in the antioxidant molecule increases, this proportion is within the range that does not impair other properties. Is preferably increased. It is preferred that there be at least one hindered phenol moiety per 600 molecular weight of the antioxidant. Specific examples include pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl). ) Propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 3,9'-bis [2- {3- (3 -t-Butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5 ・ 5] undecan-2- (3,5 -Di-t-butyl-4-hydroxyanilino) -4,6-bis (n-octylthio) -1,3,5-triazine, 1,1,3-tris (5-t-butyl-4-hydroxy -2-methylphenyl) butane, bis [2-t-butyl-4-methyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) phenyl] terephthalate, tetrakis [methylene-3- (3 , 5-Di-t-butyl-4-hydroxyphenyl) propionate] methane, 2,2 '-Thiodiethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethyleneglycolbis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) Propionate], 1,6-hexanediol bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-t-butyl- 4-hydroxybenzyl) isocyanurate, 1,3,5-tris [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} ethyl] isocyanurate, 1,3,5 -Tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -2,4 , 6-trimethylbenzene and the like. Moreover, the addition amount of these antioxidants is 0.0001 to 5%, but if the addition amount is too small, the characteristics at the time of heating deteriorate, and if the addition amount is too large, the characteristics as a liquid crystal display element are affected. Therefore, 0.0005% to 1% is preferable, 0.001% to 0.5% is more preferable, and 0.01% to 0.1% is particularly preferable.
組成物中の各化合物の含有量は一般式(I-1)、一般式(I-2)及び一般式(I-3)の化合物群の含有率が5〜90質量%の範囲であることが好ましく、一般式(I-1)、一般式(I-2)及び一般式(I-3)の化合物群から選ばれる化合物を少なくとも2種含有することが好ましい、
一般式(IV)及び一般式(V)の化合物群の含有率が5〜90質量%の範囲であることが好ましいが、一般式(IV)の化合物として一般式(IVa)
The content of each compound in the composition is such that the content of the compound group of general formula (I-1), general formula (I-2) and general formula (I-3) is in the range of 5 to 90% by mass. It is preferable that it contains at least two compounds selected from the compound group represented by general formula (I-1), general formula (I-2) and general formula (I-3).
The content of the compound group of the general formula (IV) and the general formula (V) is preferably in the range of 5 to 90% by mass, but as the compound of the general formula (IV), the general formula (IVa)
本発明の液晶組成物は150℃で1時間加熱後、80℃におけるフレームタイム200msの電圧保持率(VHR)が88%以上であることが好ましい。 The liquid crystal composition of the present invention preferably has a voltage holding ratio (VHR) of 88% or more at a frame time of 200 ms after heating at 150 ° C. for 1 hour.
本発明の液晶組成物を用いた液晶表示素子としては種々のものに使用することができるが、ねじれ角が220°〜270°の超捩れネマチック(STN)液晶表示素子、アクティブマトリックス(AM)液晶表示素子、反射型液晶表示素子が好ましい。 The liquid crystal display device using the liquid crystal composition of the present invention can be used for various types, but a super twisted nematic (STN) liquid crystal display device having a twist angle of 220 ° to 270 °, an active matrix (AM) liquid crystal A display element and a reflective liquid crystal display element are preferable.
以下、実施例を挙げて本発明を更に詳述するが、本発明はこれらの実施例に限定されるものではない。また、以下の実施例及び比較例の組成物における「%」は『質量%』を意味し、液晶相温度範囲(ネマチック液晶相温度範囲)とは特に指定がない限り、固体相又はスメクチック相-ネマチック相転移温度からネマチック相-等方性液体相転移温度までを意味する。 EXAMPLES Hereinafter, although an Example is given and this invention is further explained in full detail, this invention is not limited to these Examples. Further, in the compositions of the following examples and comparative examples, ``% '' means `` mass% '', and unless otherwise specified, the liquid crystal phase temperature range (nematic liquid crystal phase temperature range) is a solid phase or a smectic phase- It means from the nematic phase transition temperature to the nematic phase-isotropic liquid phase transition temperature.
実施例中、測定した特性は以下の通りである。
TN-I ：ネマチック相-等方性液体相転移温度(℃)
T→N ：固体相又はスメクチック相-ネマチック相転移温度(℃)
Vth ：セル厚6μm、25℃におけるのTN-LCDを構成した時のしきい値電圧
(V)
Δε ：25℃における誘電異方性
Δn ：25℃における屈折率異方性
τr=τd：25℃における応答速度 (msec)
VHR ：空気中150℃で1時間加熱し、これを用いてセル厚6μmのTN-LCDを構
成し、80℃の測定環境下5Vの電圧パルスを与えた時、フレームタイ
ム200msecの電位保持率(%)
(実施例1)
下記組成を持つ液晶組成物(A)を調製した。
In the examples, the measured characteristics are as follows.
TN-I: Nematic phase-isotropic liquid phase transition temperature (℃)
T → N: Solid phase or smectic phase-nematic phase transition temperature (℃)
Vth: threshold voltage when a TN-LCD with a cell thickness of 6μm and 25 ° C is constructed
(V)
Δε: Dielectric anisotropy at 25 ° C Δn: Refractive index anisotropy at 25 ° C τr = τd: Response speed at 25 ° C (msec)
VHR: Heated in air at 150 ° C for 1 hour, and used to construct a TN-LCD with a cell thickness of 6μm.
When a voltage pulse of 5V is applied in a measurement environment at 80 ° C,
200msec potential holding rate (%)
(Example 1)
A liquid crystal composition (A) having the following composition was prepared.
上記液晶組成物(A)に酸化防止剤として式(VI-1)に示すオクタデシル-3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate represented by the formula (VI-1) as an antioxidant in the liquid crystal composition (A)
(実施例2)
実施例1と同様にして液晶組成物(A)を調製し、これに酸化防止剤として式(VI-1)の化合物を0.2％添加し液晶組成物を調整した。
(実施例3)
実施例1と同様にして液晶組成物(A)を調製し、これに酸化防止剤として式(VI-1)の化合物を0.02％添加し液晶組成物を調整した。
(Example 2)
A liquid crystal composition (A) was prepared in the same manner as in Example 1, and 0.2% of the compound of formula (VI-1) was added as an antioxidant to prepare a liquid crystal composition.
(Example 3)
A liquid crystal composition (A) was prepared in the same manner as in Example 1, and 0.02% of the compound of formula (VI-1) was added thereto as an antioxidant to prepare a liquid crystal composition.
(実施例4)
実施例1と同様にして液晶組成物(A)を調製し、これに酸化防止剤として式(VI-2)に示すペンタエリスリチル-テトラキス［3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート］
(Example 4)
A liquid crystal composition (A) was prepared in the same manner as in Example 1, and pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-) represented by the formula (VI-2) was used as an antioxidant. 4-hydroxyphenyl) propionate]
(実施例5)
実施例1と同様にして液晶組成物(A)を調製し、これに酸化防止剤として式(VI-2)の化合物を0.02％添加し液晶組成物を調整した。
(実施例6)
下記組成を持つ液晶組成物(B)を調製した。
(Example 5)
A liquid crystal composition (A) was prepared in the same manner as in Example 1, and 0.02% of the compound of formula (VI-2) was added thereto as an antioxidant to prepare a liquid crystal composition.
(Example 6)
A liquid crystal composition (B) having the following composition was prepared.
この液晶組成物(B)に、酸化防止剤として式(VI-2)の化合物を0.02％添加し液晶組成物を調整した。
(実施例7)
実施例1と同様にして母液晶組成物Aを調製し、これに酸化防止剤としてトリエチレングリコール-ビス[3-(3-t-ブチル-5-メチル-4-ヒドロキシフェニル)プロピオネート]
To this liquid crystal composition (B), 0.02% of a compound of formula (VI-2) was added as an antioxidant to prepare a liquid crystal composition.
(Example 7)
A mother liquid crystal composition A was prepared in the same manner as in Example 1, and triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] was used as an antioxidant.
(参考例１)
実施例6と同様にして液晶組成物(B)を調製し、これに酸化防止剤として式(XV-1)に示すビス(2,2,6,6-テトラメチル-4-ピペリジル) セバケート
(Reference Example 1)
A liquid crystal composition (B) was prepared in the same manner as in Example 6, and bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate represented by the formula (XV-1) was used as an antioxidant.
(比較例1)
実施例1と同様にして液晶組成物(A)を調製し、酸化防止剤は添加しなかった。
(Comparative Example 1)
A liquid crystal composition (A) was prepared in the same manner as in Example 1, and no antioxidant was added.
(比較例2)
実施例6と同様にして液晶組成物(B)を調製し、酸化防止剤は添加しなかった。
以上の実施例及び比較例で調整した液晶組成物について物性値を評価した結果及びこれらの液晶組成物を用いて液晶表示素子を作成し特性を評価した結果を表1に示す。
(Comparative Example 2)
A liquid crystal composition (B) was prepared in the same manner as in Example 6, and no antioxidant was added.
Table 1 shows the results of evaluating the physical properties of the liquid crystal compositions prepared in the above examples and comparative examples, and the results of evaluating liquid crystal display elements using these liquid crystal compositions and evaluating the characteristics.
実施例では加熱によるTN-Iの低下(ΔT)が比較例より大幅に少なく、加熱時の電圧保持率が極めて高い液晶表示素子を作成することができた。また、液晶表示素子の諸特性も優れ、この表示素子の表示品位は経時変化の少ない優れたものであった。 In the example, a decrease in T NI (ΔT) due to heating was significantly less than that of the comparative example, and a liquid crystal display element having an extremely high voltage holding ratio during heating could be produced. Further, the liquid crystal display element has various characteristics, and the display quality of the display element is excellent with little change with time.
ガスクロマトグラフ(GC)により、加熱前後の比較を行ったところ、比較例に示した液晶組成物では、酸化劣化物の発生が見られたが、本発明の液晶材料と酸化防止剤の組み合わせによる系(実施例1〜7)では、酸化劣化物の発生は見られなかった。 When a comparison between before and after heating was performed by gas chromatograph (GC), in the liquid crystal composition shown in the comparative example, the generation of oxidation degradation products was observed, but the system based on the combination of the liquid crystal material of the present invention and the antioxidant was used. In (Examples 1 to 7), no oxidative degradation was observed.
Claims (14)
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