JP2005263789A - Polymerizable compound and polymerizable liquid crystal composition containing the compound - Google Patents
Polymerizable compound and polymerizable liquid crystal composition containing the compound Download PDFInfo
- Publication number
- JP2005263789A JP2005263789A JP2005039109A JP2005039109A JP2005263789A JP 2005263789 A JP2005263789 A JP 2005263789A JP 2005039109 A JP2005039109 A JP 2005039109A JP 2005039109 A JP2005039109 A JP 2005039109A JP 2005263789 A JP2005263789 A JP 2005263789A
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- JP
- Japan
- Prior art keywords
- general formula
- liquid crystal
- same
- formula
- polymerizable
- 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.)
- Granted
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 67
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 58
- 239000000203 mixture Substances 0.000 title claims abstract description 30
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 33
- 229920000642 polymer Polymers 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 11
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 229920001519 homopolymer Polymers 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 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 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 2
- 125000004959 2,6-naphthylene group Chemical group [H]C1=C([H])C2=C([H])C([*:1])=C([H])C([H])=C2C([H])=C1[*:2] 0.000 claims description 2
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 claims description 2
- 101150065749 Churc1 gene Proteins 0.000 claims description 2
- 102100038239 Protein Churchill Human genes 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 230000001747 exhibiting effect Effects 0.000 abstract description 2
- -1 acryl group Chemical group 0.000 description 34
- 238000000034 method Methods 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 10
- 230000003287 optical effect Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 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
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 238000012719 thermal polymerization Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920000106 Liquid crystal polymer Polymers 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011521 glass Substances 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
- 239000000463 material Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 230000010512 thermal transition Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QKXADDXIAYTIMP-UHFFFAOYSA-N (4-hydroxyphenyl) 4-(6-prop-2-enoyloxyhexoxy)benzoate Chemical compound C1=CC(O)=CC=C1OC(=O)C1=CC=C(OCCCCCCOC(=O)C=C)C=C1 QKXADDXIAYTIMP-UHFFFAOYSA-N 0.000 description 1
- WJOODRLJINTWLH-UHFFFAOYSA-N (4-hydroxyphenyl) 4-[3-(2-methylprop-2-enoyloxy)propoxy]benzoate Chemical compound OC1=CC=C(C=C1)OC(C1=CC=C(C=C1)OCCCOC(C(=C)C)=O)=O WJOODRLJINTWLH-UHFFFAOYSA-N 0.000 description 1
- 125000006018 1-methyl-ethenyl group Chemical group 0.000 description 1
- 125000004343 1-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C([H])([H])[H] 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 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
- 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
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ZJZSIKJZOWYOJX-UHFFFAOYSA-N 3-(4-prop-2-enoyloxyphenyl)propanoic acid Chemical compound OC(=O)CCC1=CC=C(OC(=O)C=C)C=C1 ZJZSIKJZOWYOJX-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
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-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 group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 125000003493 decenyl group Chemical group [H]C([*])=C([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])[H] 0.000 description 1
- 125000002704 decyl 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])C([H])([H])C([H])([H])* 0.000 description 1
- 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 1
- 125000006003 dichloroethyl group Chemical group 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 125000001400 nonyl 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])C([H])([H])[H] 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
- 230000020477 pH reduction Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003232 pyrogallols Chemical class 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000007767 slide coating Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000004079 stearyl 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])C([H])([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])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
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Abstract
Description
本発明は、直鎖上に並んだ環構造を有し、その両端に異なるスペーサーを介して（メタ）アクリル基を有する重合性化合物に関し、詳細には、（メタ）アクリル基を重合して硬化膜とした際に、優れた耐溶剤性と光学特性を示す光学異方体となる重合性化合物に関する。 The present invention relates to a polymerizable compound having a ring structure arranged in a straight chain and having (meth) acrylic groups via different spacers at both ends thereof. Specifically, the (meth) acrylic group is polymerized and cured. The present invention relates to a polymerizable compound which becomes an optical anisotropic body exhibiting excellent solvent resistance and optical properties when formed into a film.
近年、液晶物質は、ＴＮ型やＳＴＮ型に代表されるディスプレイ素子等の液晶分子の可逆的運動を利用した表示媒体への応用以外にも、その配向性と屈折率、誘電率、磁化率等の物理的性質の異方性を利用して、位相差板、偏光板、光偏光プリズム、各種光フィルター等の光学異方体への応用が検討されている。 In recent years, in addition to application to display media using reversible motion of liquid crystal molecules such as display elements typified by TN type and STN type, the liquid crystal substance has its orientation, refractive index, dielectric constant, magnetic susceptibility, etc. Utilizing the anisotropy of these physical properties, application to optical anisotropic bodies such as retardation plates, polarizing plates, light polarizing prisms, and various optical filters has been studied.
このように液晶物質を構成材料とする光学異方体は、安定で均一な光学特性を得るために、液晶状態における液晶分子の均一な配向状態を半永久的に固定化して、機械的にも熱的にも安定なガラス転移温度（以下「Ｔｇ」という）の高い、配向性に優れた重合物とすることが必須である。 Thus, in order to obtain stable and uniform optical characteristics, an optical anisotropic body composed of a liquid crystal substance has a uniform alignment state of liquid crystal molecules in a liquid crystal state semi-permanently and is mechanically heated. In particular, it is essential that the polymer has a high glass transition temperature (hereinafter referred to as “Tg”) and excellent orientation.
液晶状態における液晶分子の均一な配向状態を半永久的に固定化する手段としては、例えば、重合性官能基を有する液晶性化合物又はこのような化合物を含有する重合性液晶組成物を液晶状態で均一に配向させた後、液晶状態を保持したまま紫外線等のエネルギー線を照射することによって光重合させて、均一な配向状態を半永久的に固定化する方法が既に知られている。 As a means for semi-permanently fixing the uniform alignment state of the liquid crystal molecules in the liquid crystal state, for example, a liquid crystal compound having a polymerizable functional group or a polymerizable liquid crystal composition containing such a compound is uniform in the liquid crystal state. There is already known a method of semi-permanently fixing a uniform alignment state by photopolymerization by irradiating energy rays such as ultraviolet rays after maintaining the liquid crystal state.
重合性官能基を有する液晶性化合物としては、（メタ）アクリル基を有する重合性化合物が知られている（例えば、特許文献１、特許文献２、特許文献３及び特許文献４を参照）。これらの文献に記載された重合性化合物は、液晶相を示す温度が高く、高温での重合、硬化が必要であった。 As liquid crystalline compounds having a polymerizable functional group, polymerizable compounds having a (meth) acryl group are known (see, for example, Patent Document 1, Patent Document 2, Patent Document 3 and Patent Document 4). The polymerizable compounds described in these documents have a high temperature showing a liquid crystal phase, and polymerization and curing at a high temperature are necessary.
高温での重合は、光重合と熱重合とが並行して起きるため、硬化物の物性が不均一になりやすく、配向状態の固定が困難である。また、硬化時の温度管理を容易にするために、液晶組成物がより低温で液晶相を示す液晶性化合物が求められていた。 Since polymerization at high temperature occurs in parallel with photopolymerization and thermal polymerization, the physical properties of the cured product are likely to be non-uniform, and it is difficult to fix the alignment state. Further, in order to facilitate temperature control during curing, a liquid crystalline compound in which the liquid crystal composition exhibits a liquid crystal phase at a lower temperature has been demanded.
本発明の目的は、配向性に優れ、低温で液晶相を示す新規な重合性化合物、及び該化合物を含有する重合性液晶組成物を提供することにある。 An object of the present invention is to provide a novel polymerizable compound that is excellent in orientation and exhibits a liquid crystal phase at a low temperature, and a polymerizable liquid crystal composition containing the compound.
本発明は、下記一般式（１）で表される重合性化合物、及び該化合物を含有する重合性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 achieves the above object by providing a polymerizable compound represented by the following general formula (1) and a polymerizable liquid crystal composition containing the compound.
また、本発明は、上記重合性化合物を重合してなる単独重合物を提供するものである。 The present invention also provides a homopolymer obtained by polymerizing the polymerizable compound.
また、本発明は、上記重合性化合物と他のエチレン性不飽和結合を有する化合物とを共重合してなる共重合物を提供するものである。 Moreover, this invention provides the copolymer formed by copolymerizing the said polymeric compound and the compound which has another ethylenically unsaturated bond.
本発明の重合性化合物は、室温付近で重合可能な、低温で液晶相を示す重合性液晶組成物を提供できるものである。本発明の単独重合物及び共重合物は、高耐熱性、高耐溶剤性を有する、液晶物質として有用なものである。 The polymerizable compound of the present invention can provide a polymerizable liquid crystal composition that can be polymerized at around room temperature and exhibits a liquid crystal phase at a low temperature. The homopolymer and copolymer of the present invention are useful as liquid crystal substances having high heat resistance and high solvent resistance.
以下、本発明の重合性化合物及び該化合物を含有する重合性液晶組成物について、その好ましい実施形態に基づき詳細に説明する。 Hereinafter, the polymerizable compound of the present invention and the polymerizable liquid crystal composition containing the compound will be described in detail based on preferred embodiments thereof.
本発明の重合性化合物を表す上記一般式（１）において、Ｍで示されるメソゲン基は、芳香環、脂環、複素環又は縮合環が連結鎖を介して又は直接結合した基を表し、下記一般式（２）で表すことができる。 In the above general formula (1) representing the polymerizable compound of the present invention, the mesogenic group represented by M represents a group in which an aromatic ring, an alicyclic ring, a heterocyclic ring or a condensed ring is bonded via a connecting chain or directly, It can represent with General formula (2).
上記一般式（２）で表されるＭとしては、例えば下記一般式（３）で表される基を挙げることができる。 Examples of M represented by the general formula (2) include a group represented by the following general formula (3).
また、上記一般式（２）で表されるＭとしては、下記一般式（４）で表される基を挙げることもできる。 Moreover, as M represented by the said General formula (2), group represented by following General formula (4) can also be mentioned.
上記一般式（１）で表される本発明の重合性化合物としては、例えば下記一般式（５）で表される重合性化合物を挙げることができる。 Examples of the polymerizable compound of the present invention represented by the general formula (1) include a polymerizable compound represented by the following general formula (5).
また、上記一般式（１）で表される本発明の重合性化合物としては、下記一般式（６）で表される重合性化合物を挙げることもできる。 Moreover, as a polymeric compound of this invention represented by the said General formula (1), the polymeric compound represented by following General formula (6) can also be mentioned.
また、上記一般式（１）で表される本発明の重合性化合物としては、下記一般式（７）で表される重合性化合物を挙げることもできる。 Moreover, as a polymeric compound of this invention represented by the said General formula (1), the polymeric compound represented by following General formula (7) can also be mentioned.
また、上記一般式（１）で表される本発明の重合性化合物としては、下記一般式（８）で表される重合性化合物を挙げることもできる。 Moreover, as a polymeric compound of this invention represented by the said General formula (1), the polymeric compound represented by following General formula (8) can also be mentioned.
上記一般式（２）中、Ｒで表される炭素数１〜１８のアルキル基としては、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、２−エチルヘキシル、ノニル、イソノニル、デシル、ステアリル等が挙げられ、炭素数１〜１８のアルコキシ基としては、メチルオキシ、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、２−エチルヘキシルオキシ等が挙げられ、炭素数２〜１８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、プロペニル、ブテニル、イソブテニル、ペンテニル、ヘキセニル、ヘプテニル、オクテニル、デセニル、ぺンタデセニル、エイコセニル、トリコセニル等が挙げられ、炭素数２〜１８のアルケニルオキシ基としては、ビニルオキシ、１−メチルエテニルオキシ、２−メチルエテニルオキシ、プロペニルオキシ、ブテニルオキシ、イソブテニルオキシ、ペンテニルオキシ、ヘキセニルオキシ、ヘプテニルオキシ、オクテニルオキシ、デセニルオキシ、ぺンタデセニルオキシ、エイコセニルオキシ、トリコセニルオキシ等が挙げられ、置換基としてのハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。 In the general formula (2), the alkyl group having 1 to 18 carbon atoms represented by R is methyl, chloromethyl, trifluoromethyl, cyanomethyl, ethyl, dichloroethyl, propyl, isopropyl, butyl, sec-butyl, Tert-butyl, isobutyl, amyl, isoamyl, tert-amyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tertiary heptyl, n-octyl , Isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl, stearyl, etc., and examples of the alkoxy group having 1 to 18 carbon atoms include methyloxy, chloromethyloxy, trifluoromethyloxy, cyanomethyloxy, Ethyloxy, dichloroethyloxy, pro Ruoxy, isopropyloxy, butyloxy, sec-butyloxy, tert-butyloxy, isobutyloxy, amyloxy, isoamyloxy, tert-amyloxy, hexyloxy, cyclohexyloxy, heptyloxy, isoheptyloxy, tert-heptyloxy, n-octyloxy, Isooctyloxy, tertiary octyloxy, 2-ethylhexyloxy and the like. Examples of the alkenyl group having 2 to 18 carbon atoms include vinyl, 1-methylethenyl, 2-methylethenyl, propenyl, butenyl, isobutenyl, pentenyl, hexenyl, heptenyl , Octenyl, decenyl, pentadecenyl, eicocenyl, tricocenyl, etc., and examples of the alkenyloxy group having 2 to 18 carbon atoms include vinyloxy, 1-methylethenyloxy, 2- Tylethenyloxy, propenyloxy, butenyloxy, isobutenyloxy, pentenyloxy, hexenyloxy, heptenyloxy, octenyloxy, decenyloxy, pentadecenyloxy, eicosenyloxy, tricocenyloxy, etc. Examples of the halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
上記一般式（１）で表される本発明の重合性化合物の具体例としては、下記化合物Ｎｏ．１〜１２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 of the present invention represented by the general formula (1) include the following compound No. 1-12 are mentioned. However, the present invention is not limited by the following compounds.
上記一般式（１）で表される本発明の重合性化合物は、例えば、次の反応式に従って製造することができる。 The polymerizable compound of the present invention represented by the general formula (1) can be produced, for example, according to the following reaction formula.
本発明の重合性化合物を重合性液晶性単量体として重合する場合には、単独で又は２種以上を組み合わせて用いることができる。また、本発明の重合性化合物を、他の液晶性単量体、及び（メタ）アクリル酸エステル等のエチレン性不飽和結合を有する化合物と共重合することができる。これらの他の液晶性単量体及び化合物の使用量は、全単量体中、本発明の重合性化合物が１質量％以上、特に３質量％以上となるような範囲が好ましいが、該液晶性単量体及び化合物の構造に応じて適当な使用量とされる。 When the polymerizable compound of the present invention is polymerized as a polymerizable liquid crystalline monomer, it can be used alone or in combination of two or more. Moreover, the polymerizable compound of the present invention can be copolymerized with other liquid crystalline monomers and compounds having an ethylenically unsaturated bond such as (meth) acrylic acid ester. The amount of these other liquid crystal monomers and compounds used is preferably in the range where the polymerizable compound of the present invention is 1% by mass or more, particularly 3% by mass or more, based on the total monomers. The amount used is appropriate depending on the structure of the functional monomer and compound.
上記他の液晶性単量体の具体例としては、下記化合物Ｎｏ．１３〜３２が挙げられる。 Specific examples of the other liquid crystal monomers include the following compound No. 13-32 is mentioned.
上記の（メタ）アクリル酸エステル等のエチレン性不飽和結合を有する化合物としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、第二ブチル（メタ）アクリレート、第三ブチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、グリシジル（メタ）アクリレート、アリル（メタ）アクリレート、アリルオキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、１−フェニルエチル（メタ）アクリレート、２−フェニルエチル（メタ）アクリレート、フルフリル（メタ）アクリレート、ジフェニルメチル（メタ）アクリレート、ナフチル（メタ）アクリレート、ペンタクロルフェニル（メタ）アクリレート、２−クロルエチル（メタ）アクリレート、メチル−α−クロル（メタ）アクリレート、フェニル−α−ブロモ（メタ）アクリレート、トリフルオロエチル（メタ）アクリレート、テトラフルオロプロピル（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、１, ４−ブタンジオールジ（メタ）アクリレート、１, ６−ヘキサンジオールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等の（メタ）アクリル酸エステル、ジアセトンアクリルアミド、スチレン、ビニルトルエン、ジビニルベンゼン等が挙げられる。 Examples of the compound having an ethylenically unsaturated bond such as (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and second butyl (meth) ) Acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, allyl (meth) acrylate, allyloxyl (meth) Acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 1-phenylethyl (meth) acrylate, 2-phenylethyl (meth) acrylate, furfuryl (meth) acrylate, diphenylmethyl (meth) ) Acrylate, naphthyl (meth) acrylate, pentachlorophenyl (meth) acrylate, 2-chloroethyl (meth) acrylate, methyl-α-chloro (meth) acrylate, phenyl-α-bromo (meth) acrylate, trifluoroethyl (meth) ) Acrylate, tetrafluoropropyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate (Meth) acrylic acid esters such as silicate, diacetone acrylamide, styrene, vinyl toluene, divinyl benzene and the like.
本発明の重合性化合物は、上述したように、重合物とすることにより、液晶性重合体として有用なものである。 As described above, the polymerizable compound of the present invention is useful as a liquid crystalline polymer by forming a polymer.
本発明の重合性液晶組成物は、光学素子を構成する場合には、少なくとも室温付近で液晶相を示し、望ましくは１５℃以下で液晶相を示すことが好ましい。 When the polymerizable liquid crystal composition of the present invention constitutes an optical element, it preferably exhibits a liquid crystal phase at least near room temperature, and desirably exhibits a liquid crystal phase at 15 ° C. or lower.
本発明の重合性液晶組成物には、本発明の重合性化合物以外の液晶化合物を添加することもできる。しかし、液晶組成物を用いて作成する高分子の耐熱性を保持する意味で、該液晶化合物の添加量は重合性液晶組成物中３０質量％以下が好ましい。 A liquid crystal compound other than the polymerizable compound of the present invention can be added to the polymerizable liquid crystal composition of the present invention. However, the amount of the liquid crystal compound added is preferably 30% by mass or less in the polymerizable liquid crystal composition in order to maintain the heat resistance of the polymer prepared using the liquid crystal composition.
本発明の重合性液晶組成物には、その重合反応性を向上させることを目的として、熱重合開始剤、光重合開始剤等の重合開始剤を添加することもできる。熱重合開始剤としては、例えば、過酸化ベンゾイル、２，２−アゾビスイソブチロニトリル等が挙げられる。また、光重合開始剤としては、例えば、ベンゾインエーテル類、ベンゾフェノン類、アセトフェノン類、ベンジルケタール類等が挙げられる。重合開始剤を添加する場合は、該重合性液晶組成物に対して、１０質量％以下であることが好ましく、５質量％以下が特に好ましく、０．５〜１．５質量％の範囲が更に好ましい。 For the purpose of improving the polymerization reactivity, a polymerization initiator such as a thermal polymerization initiator and a photopolymerization initiator can be added to the polymerizable liquid crystal composition of the present invention. Examples of the thermal polymerization initiator include benzoyl peroxide and 2,2-azobisisobutyronitrile. Examples of the photopolymerization initiator include benzoin ethers, benzophenones, acetophenones, and benzyl ketals. When adding a polymerization initiator, it is preferably 10% by mass or less, particularly preferably 5% by mass or less, and more preferably in the range of 0.5 to 1.5% by mass with respect to the polymerizable liquid crystal composition. preferable.
本発明の重合性液晶組成物には、その保存安定性を向上させるために、安定剤を添加することもできる。使用できる安定剤としては、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。安定剤を添加する場合は、該重合性液晶組成物に対して、１質量％以下であることが好ましく、０．５質量％以下が特に好ましい。 In order to improve the storage stability of the polymerizable liquid crystal composition of the present invention, a stabilizer may be added. Examples of the 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 a stabilizer, it is preferable that it is 1 mass% or less with respect to this polymeric liquid crystal composition, and 0.5 mass% or less is especially preferable.
本発明の重合性液晶組成物には、液晶骨格のらせん構造を内部に有する高分子を得ることを目的として、光学活性化合物を添加することもできる。該化合物としては、例えば以下の化合物を挙げることができる。 An optically active compound can also be added to the polymerizable liquid crystal composition of the present invention for the purpose of obtaining a polymer having a helical structure of a liquid crystal skeleton inside. Examples of the compound include the following compounds.
本発明の重合性液晶組成物を偏光フィルムや配向膜の原料、又は印刷インキ及び塗料、保護膜等の用途に利用する場合には、その目的に応じて、金属、金属錯体、染料、顔料、色素、蛍光材料、燐光材料、界面活性剤、レベリング剤、チキソ剤、ゲル化剤、多糖、紫外線吸収剤、赤外線吸収剤、抗酸化剤、イオン交換樹脂、酸化チタン等の金属酸化物、重合禁止剤、光増感剤、架橋剤、液晶配向助剤等を添加することもできる。 When the polymerizable liquid crystal composition of the present invention is used for a polarizing film, a raw material for an alignment film, or printing inks and paints, protective films, etc., depending on the purpose, a metal, a metal complex, a dye, a pigment, Dyes, fluorescent materials, phosphorescent materials, surfactants, leveling agents, thixotropic agents, gelling agents, polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants, ion exchange resins, metal oxides such as titanium oxide, polymerization prohibition An agent, a photosensitizer, a crosslinking agent, a liquid crystal alignment aid and the like can also be added.
本発明の重合性液晶組成物の（共）重合体からなる硬化膜は、例えば、本発明の重合性液晶組成物を必要に応じて溶媒に溶解し、支持体上に塗布し、紫外線等を照射して重合させることにより製造される。上記支持体としては、特に限定されないが、好ましい例としてはガラス板、ポリエチレンテレフタレート板、ポリカーボネート板、ポリイミド板、ポリアミド板、ポリメタクリル酸メチル板、ポリスチレン板、ポリ塩化ビニル板、ポリテトラフルオロエチレン板、セルロース板、シリコン板、反射板、方解石板等が挙げられる。液晶組成物を支持体に塗布する方法としては、公知の方法を用いることができ、例えばカーテンコーティング法、押し出しコーティング法、ロールコーティング法、スピンコーティング法、ディップコーティング法、バーコーティング法、スプレーコーティング法、スライドコーティング法、印刷コーティング法等を用いることができる。 The cured film made of the (co) polymer of the polymerizable liquid crystal composition of the present invention may be prepared by, for example, dissolving the polymerizable liquid crystal composition of the present invention in a solvent as necessary, coating the support, and applying ultraviolet rays or the like. Manufactured by irradiation and polymerization. Although it does not specifically limit as said support body, As a preferable example, a glass plate, a polyethylene terephthalate board, a polycarbonate board, a polyimide board, a polyamide board, a polymethyl methacrylate board, a polystyrene board, a polyvinyl chloride board, a polytetrafluoroethylene board , Cellulose plate, silicon plate, reflector plate, calcite plate and the like. As a method of applying the liquid crystal composition to the support, known methods can be used, for example, curtain coating method, extrusion coating method, roll coating method, spin coating method, dip coating method, bar coating method, spray coating method. A slide coating method, a printing coating method, or the like can be used.
本発明の重合性液晶組成物の（共）重合体を製造する際に用いられる溶媒としては、例えばテトラヒドロフラン、シクロヘキサノン、メチルエチルケトン等が挙げられる。 Examples of the solvent used when producing the (co) polymer of the polymerizable liquid crystal composition of the present invention include tetrahydrofuran, cyclohexanone, methyl ethyl ketone, and the like.
本発明の重合性化合物を配向させる方法としては、例えば上述の支持体に事前に配向処理を施す方法が挙げられる。支持体に配向処理を施す好ましい方法としては、各種ポリイミド系配向膜、ポリビニルアルコール系配向膜等からなる液晶配向層を支持体の上に設け、ラビング等の処理を行う方法が挙げられる。また、重合性液晶組成物中の重合性化合物を配向させる方法としては、支持体上の液晶組成物に磁場や電場等を印加する方法等が挙げられる。 As a method for aligning the polymerizable compound of the present invention, for example, a method in which the above-mentioned support is subjected to an alignment treatment in advance can be mentioned. As a preferred method for performing an alignment treatment on the support, a method of providing a liquid crystal alignment layer composed of various polyimide alignment films, polyvinyl alcohol alignment films, etc. on the support and performing a treatment such as rubbing can be mentioned. Examples of a method for aligning the polymerizable compound in the polymerizable liquid crystal composition include a method of applying a magnetic field or an electric field to the liquid crystal composition on the support.
本発明の重合性液晶組成物は、熱又は電磁波を用いる公知の方法により重合させることができる。電磁波による重合反応としては、光重合開始剤を用いて紫外光を照射するラジカル重合が好ましい。また、磁場や電場を印加しながら架橋するのも好ましい。支持体上に形成した液晶重合体はそのまま使用しても良いが、必要に応じて支持体から剥離したり、他の支持体に転写しても良い。 The polymerizable liquid crystal composition of the present invention can be polymerized by a known method using heat or electromagnetic waves. As the polymerization reaction by electromagnetic waves, radical polymerization in which ultraviolet light is irradiated using a photopolymerization initiator is preferable. It is also preferable to perform crosslinking while applying a magnetic field or an electric field. The liquid crystal polymer formed on the support may be used as it is, but may be peeled off from the support or transferred to another support as necessary.
本発明の重合性液晶組成物は、液晶ディスプレイの位相差フイルム、液晶ディスプレイの光学補償板（位相差板）、偏光板、反射フィルム、カラーフィルター、ホログラフィー素子、偏光プリズム、光ヘッド等の光学素子、ローパスフィルター、偏光ビームスプリッター等として使用できる。 The polymerizable liquid crystal composition of the present invention is an optical element such as a retardation film of a liquid crystal display, an optical compensation plate (retardation plate) of a liquid crystal display, a polarizing plate, a reflective film, a color filter, a holographic element, a polarizing prism, and an optical head. It can be used as a low-pass filter, a polarizing beam splitter, etc.
以下、合成例、実施例等をもって本発明を更に詳細に説明する。しかしながら、本発明は以下の合成例、実施例等によって制限を受けるものではない。 Hereinafter, the present invention will be described in more detail with reference to synthesis examples and examples. However, the present invention is not limited by the following synthesis examples and examples.
[合成例１] 化合物Ｎｏ．１の合成
＜ステップ１＞アクリル酸エステルの合成
下記アクリル酸エステルを、以下のようにして合成した。
[Synthesis Example 1] Compound No. 1 Synthesis of 1 <Step 1> Synthesis of acrylic ester The following acrylic ester was synthesized as follows.
３−（４−ヒドロキシフェニル）プロピオン酸１８．３６ｇ（０．１１モル）、水酸化ナトリウム１１．０５ｇ（０．２８モル）及び水１００ｇを仕込み、２０℃で攪拌しながら塩化アクリロイル１０ｇ（０．１１モル）を滴下し、２時間反応させた。反応後、４ｍｏｌ／ｌ塩酸を滴下して酸性とした後、析出物を濾取し風乾した。この析出物をメタノール／水＝３／４混合溶媒から再結晶し、白色固体（収量１１．６８ｇ、収率４８％）を得た。 First, 18.36 g (0.11 mol) of 3- (4-hydroxyphenyl) propionic acid, 11.05 g (0.28 mol) of sodium hydroxide and 100 g of water were charged, and 10 g of acryloyl chloride (0. 11 mol) was added dropwise and reacted for 2 hours. After the reaction, 4 mol / l hydrochloric acid was added dropwise for acidification, and the precipitate was collected by filtration and air-dried. This precipitate was recrystallized from a methanol / water = 3/4 mixed solvent to obtain a white solid (yield 11.68 g, yield 48%).
得られた白色固体の赤外吸収スペクトル（ＩＲ）測定結果は次の通りであり、該白色固体は、目的物であるアクリル酸エステルであることを確認した。
[ＩＲ] （ｃｍ-1）
２９２０、１７４０、１６９７、１５０８、１４４７、１４０８、１３６６、１２９６、１２５４、１２００、１１７３、１１５０、１０１８
The infrared absorption spectrum (IR) measurement result of the obtained white solid was as follows, and it was confirmed that the white solid was an acrylic ester that was the target product.
[IR] (cm -1 )
2920, 1740, 1697, 1508, 1447, 1408, 1366, 1296, 1254, 1200, 1173, 1150, 1018
＜ステップ２＞化合物Ｎｏ．１の合成
化合物Ｎｏ．１を、以下のようにして合成した。
<Step 2> Compound No. Synthesis of Compound No. 1 1 was synthesized as follows.
ステップ１で得られたアクリル酸エステル３．３０ｇ（０．０１５ｍｏｌ）、４−（６−アクリロイルオキシヘキシロキシ）安息香酸（４−ヒドロキシフェニル）エステル４．８０ｇ（０．０１３モル）、Ｎ, Ｎ−ジメチルアミノピリジン０．４５８ｇ（３．７５ミリモル）及びクロロホルム３０ｇを仕込み、２０℃で攪拌しながらジシクロヘキシルカルボジイミド３．０９ｇ（０．０１５モル）をクロロホルム３０ｇに溶解させたものを滴下し、３時間反応させた。反応後、析出物を濾別し、濾液を脱溶媒し、カラムクロマトグラフィー（シリカゲル、酢酸エチル／ｎ−ヘキサン＝１／３）で精製して白色結晶を得た（収量３．１７ｇ、収率４３％）。得られた白色結晶について分析を行ったところ、該白色結晶は、目的物である化合物Ｎｏ．１であると確認された。分析結果を以下に示す。 3.30 g (0.015 mol) of the acrylate ester obtained in Step 1, 4.80 g (0.013 mol) of 4- (6-acryloyloxyhexyloxy) benzoic acid (4-hydroxyphenyl) ester, N, N -A solution prepared by dissolving 0.458 g (3.75 mmol) of dimethylaminopyridine and 30 g of chloroform and dissolving 3.09 g (0.015 mol) of dicyclohexylcarbodiimide in 30 g of chloroform while stirring at 20 ° C was added dropwise for 3 hours. Reacted. After the reaction, the precipitate was filtered off, the filtrate was desolvated, and purified by column chromatography (silica gel, ethyl acetate / n-hexane = 1/3) to obtain white crystals (yield 3.17 g, yield). 43%). When the obtained white crystal was analyzed, the white crystal was found to be the target compound No. 1. 1 was confirmed. The analysis results are shown below.
（分析結果）
（１） [ＩＲ] （ｃｍ-1）
２９３９、２８６２、１７２８、１６０４、１５０８、１４０８、１２５８、１１６９、１１４２、１０７２、１０１５
（２）（ＮＭＲ）（ｐｐｍ）
９．２（ｄ；２Ｈ），７．３−６．９（ｍ；８Ｈ）、６．６−５．７（ｍ；４Ｈ）、４．３−３．９（ｍ；４Ｈ）、３．０（ｍ；４Ｈ）、１．９−１．４（ｍ；１２Ｈ）
（３）熱転移挙動
(result of analysis)
(1) [IR] (cm -1 )
2939, 2862, 1728, 1604, 1508, 1408, 1258, 1169, 1422, 1072, 1015
(2) (NMR) (ppm)
9.2 (d; 2H), 7.3-6.9 (m; 8H), 6.6-5.7 (m; 4H), 4.3-3.9 (m; 4H), 3. 0 (m; 4H), 1.9-1.4 (m; 12H)
(3) Thermal transition behavior
[合成例２] 化合物Ｎｏ．２の合成
化合物Ｎｏ．２を、以下のようにして合成した。
[Synthesis Example 2] Compound No. Synthesis of Compound No. 2 2 was synthesized as follows.
４−アクリロイルオキシベンゼンプロパン酸０．７０ｇ（３ミリモル）、４−（３−メタクリロイルオキシプロピロキシ）安息香酸（４−ヒドロキシフェニル）エステル１．０７ｇ（３ミリモル）及び４−ジメチルアミノピリジン０．０３ｇ（０．３ミリモル）を塩化メチレン８ｍｌに溶解させて攪拌した。ジシクロヘキシルカルボジイミド０．６８ｇ（３．３ミリモル）を塩化メチレン２ｍｌに溶解させたものを室温で滴下し、１時間反応させた後、析出物を濾別した。濾液を脱溶媒し、カラムクロマトグラフィー（シリカゲル、塩化メチレン）により精製し、アセトン／メタノール混合溶媒から再結晶して白色結晶を得た（収量１．１ｇ、収率６５％）。得られた白色結晶について分析を行ったところ、該白色結晶は、目的物である化合物Ｎｏ．２であると確認された。分析結果を以下に示す。 4-acryloyloxybenzenepropanoic acid 0.70 g (3 mmol), 4- (3-methacryloyloxypropoxy) benzoic acid (4-hydroxyphenyl) ester 1.07 g (3 mmol) and 4-dimethylaminopyridine 0.03 g (0.3 mmol) was dissolved in 8 ml of methylene chloride and stirred. A solution prepared by dissolving 0.68 g (3.3 mmol) of dicyclohexylcarbodiimide in 2 ml of methylene chloride was added dropwise at room temperature and reacted for 1 hour, and then the precipitate was separated by filtration. The filtrate was desolvated, purified by column chromatography (silica gel, methylene chloride), and recrystallized from an acetone / methanol mixed solvent to obtain white crystals (yield 1.1 g, yield 65%). When the obtained white crystal was analyzed, the white crystal was found to be the target compound No. 1. 2 was confirmed. The analysis results are shown below.
（分析結果）
（１） [ＩＲ] （ｃｍ-1）
３０７１、２９２８、１７３６、１６３９、１６０５、１５１２、１２５８、１１８８、１１６５、１１３４、１０７６、１０５７、１０１１
（２）（ＮＭＲ）（ｐｐｍ）
８．２−６．９（ｍ；１２Ｈ）、６．４−５．５（ｍ；４Ｈ）、４．３（ｔ；２Ｈ）、４．１（ｔ；２Ｈ）、３．２−２．７（ｍ；４Ｈ）、２．４−１．９（ｍ；８Ｈ）
（３）熱転移挙動
(result of analysis)
(1) [IR] (cm -1 )
3071, 2928, 1736, 1639, 1605, 1512, 1258, 1188, 1165, 1134, 1076, 1057, 1011
(2) (NMR) (ppm)
8.2-6.9 (m; 12H), 6.4-5.5 (m; 4H), 4.3 (t; 2H), 4.1 (t; 2H), 3.2-2. 7 (m; 4H), 2.4-1.9 (m; 8H)
(3) Thermal transition behavior
〔実施例１〜４及び比較例１〜５〕共重合体の合成
上記合成例１及び２によって合成した本発明の重合性化合物及び同様にして合成した比較化合物それぞれを表１に示す配合（単位：ｇ）で混合し、配合物１ｇをジクロロメタン５ｇに溶解して攪拌後、脱溶媒して液晶組成物を得た。光重合開始剤（イルガキュア６５１：チバスペシャルティー・ケミカルズ社製）０．０５ｇを加え、シクロヘキサノン２ｇに溶解した。調製した溶液を、ラビング処理を施したポリイミド配向膜を有するガラス板にスピンコーターで塗布し、室温、減圧下で溶媒を除去した。得られたキャスト膜に水銀ランプで３３０ｍＪ／ｃｍ2 に相当する紫外線を照射して硬化膜（共重合体）を得た。得られた硬化膜は、触針法により測定したところ、膜厚０．９〜１．２μｍであった。
[Examples 1 to 4 and Comparative Examples 1 to 5] Synthesis of Copolymers The polymerizable compounds of the present invention synthesized according to Synthesis Examples 1 and 2 and the comparative compounds synthesized in the same manner are shown in Table 1. G), 1 g of the formulation was dissolved in 5 g of dichloromethane, stirred and then desolvated to obtain a liquid crystal composition. 0.05 g of a photopolymerization initiator (Irgacure 651: manufactured by Ciba Specialty Chemicals) was added and dissolved in 2 g of cyclohexanone. The prepared solution was applied to a glass plate having a rubbed polyimide alignment film with a spin coater, and the solvent was removed at room temperature under reduced pressure. The cast film thus obtained was irradiated with ultraviolet rays corresponding to 330 mJ / cm 2 with a mercury lamp to obtain a cured film (copolymer). When the obtained cured film was measured by a stylus method, the film thickness was 0.9 to 1.2 μm.
上記の各共重合体について、共重合前の相転移温度（Ｎ→Ｃ点）を測定した。また、各共重合体を１５０℃で２４時間保持した後の偏光顕微鏡による観察において、屈折率異方性を保持したものを○、若干失ったものを△、失ったものを×とし、耐熱性評価とした。さらに、シクロヘキサノン及びクロロホルムを硬化膜上にそれぞれ１滴滴下し、膨潤などの変化の認められないものを○、若干の膨潤が認められたものを△、明らかな膨潤や膜の剥がれが認められたものを×として、耐溶剤性評価とした。その結果を表２に示す。 About each said copolymer, the phase transition temperature (N-> C point) before copolymerization was measured. In addition, in the observation with a polarizing microscope after holding each copolymer at 150 ° C. for 24 hours, the one holding the refractive index anisotropy was evaluated as “◯”, the one slightly lost as “△”, and the lost one as “X”. It was evaluated. Furthermore, one drop each of cyclohexanone and chloroform was dropped on the cured film, ○ where no change such as swelling was observed, △ when slight swelling was observed, and obvious swelling and peeling of the film were observed. The thing was set as x and it was set as solvent-proof evaluation. The results are shown in Table 2.
表２に示す結果から明らかなように、本発明の重合性化合物を含む重合物である実施例１〜４の共重合体は、液晶温度範囲が低温で、且つ得られる硬化膜の耐熱性及び耐溶剤性が高いのに対し、比較例１〜５の共重合体は、液晶温度範囲が高かったり、硬化膜の耐熱性及び耐溶剤性が低いものであった。
As is apparent from the results shown in Table 2, the copolymers of Examples 1 to 4 which are polymers containing the polymerizable compound of the present invention have a low liquid crystal temperature range and the heat resistance of the resulting cured film and Whereas the solvent resistance is high, the copolymers of Comparative Examples 1 to 5 have a high liquid crystal temperature range or low heat resistance and solvent resistance of the cured film.
Claims (12)
A polymerizable liquid crystal composition containing the polymerizable compound according to claim 1.
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