JP2008088291A - Polymerizable composition - Google Patents
Polymerizable composition Download PDFInfo
- Publication number
- JP2008088291A JP2008088291A JP2006270577A JP2006270577A JP2008088291A JP 2008088291 A JP2008088291 A JP 2008088291A JP 2006270577 A JP2006270577 A JP 2006270577A JP 2006270577 A JP2006270577 A JP 2006270577A JP 2008088291 A JP2008088291 A JP 2008088291A
- Authority
- JP
- Japan
- Prior art keywords
- polymerizable composition
- meth
- ring
- general formula
- rings
- 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
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- 239000000203 mixture Substances 0.000 title claims abstract description 90
- -1 acrylate compound Chemical class 0.000 claims abstract description 79
- 239000010408 film Substances 0.000 claims abstract description 63
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 36
- 229920006254 polymer film Polymers 0.000 claims abstract description 34
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 15
- 230000001747 exhibiting effect Effects 0.000 claims abstract 2
- 150000001875 compounds Chemical class 0.000 claims description 44
- 125000001624 naphthyl group Chemical group 0.000 claims description 17
- 239000007870 radical polymerization initiator Substances 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 4
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000012788 optical film Substances 0.000 claims description 3
- 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
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 abstract description 24
- 239000010409 thin film Substances 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 32
- 239000002904 solvent Substances 0.000 description 26
- 238000000034 method Methods 0.000 description 24
- 239000000758 substrate Substances 0.000 description 20
- 238000004519 manufacturing process Methods 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- 239000000126 substance Substances 0.000 description 12
- 239000013078 crystal Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000010419 fine particle Substances 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 6
- 229910052753 mercury Inorganic materials 0.000 description 6
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical class C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000004642 Polyimide Substances 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- 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
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 0 CC[C@@]1(C2CC2)[C@]2(*C)C1CCCC2 Chemical compound CC[C@@]1(C2CC2)[C@]2(*C)C1CCCC2 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004983 Polymer Dispersed Liquid Crystal Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 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
- 238000009835 boiling Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- OZLBDYMWFAHSOQ-UHFFFAOYSA-N diphenyliodanium Chemical compound C=1C=CC=CC=1[I+]C1=CC=CC=C1 OZLBDYMWFAHSOQ-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910000271 hectorite Inorganic materials 0.000 description 2
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 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
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 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 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 2
- 125000005409 triarylsulfonium group Chemical group 0.000 description 2
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical compound C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 2
- 239000012953 triphenylsulfonium Substances 0.000 description 2
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 2
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 description 2
- CVBASHMCALKFME-UHFFFAOYSA-N (4-methoxyphenyl)-diphenylsulfanium Chemical compound C1=CC(OC)=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 CVBASHMCALKFME-UHFFFAOYSA-N 0.000 description 1
- HHUWEOXSSNBWJK-UHFFFAOYSA-N (4-methoxyphenyl)-diphenylsulfanium;triphenylsulfanium Chemical compound C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC(OC)=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 HHUWEOXSSNBWJK-UHFFFAOYSA-N 0.000 description 1
- JZDQKBZKFIWSNW-UHFFFAOYSA-N (4-methoxyphenyl)-phenyliodanium Chemical compound C1=CC(OC)=CC=C1[I+]C1=CC=CC=C1 JZDQKBZKFIWSNW-UHFFFAOYSA-N 0.000 description 1
- MJYFYGVCLHNRKB-UHFFFAOYSA-N 1,1,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)CF MJYFYGVCLHNRKB-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- SVHAMPNLOLKSFU-UHFFFAOYSA-N 1,2,2-trichloroethenylbenzene Chemical compound ClC(Cl)=C(Cl)C1=CC=CC=C1 SVHAMPNLOLKSFU-UHFFFAOYSA-N 0.000 description 1
- OURODNXVJUWPMZ-UHFFFAOYSA-N 1,2-diphenylanthracene Chemical compound C1=CC=CC=C1C1=CC=C(C=C2C(C=CC=C2)=C2)C2=C1C1=CC=CC=C1 OURODNXVJUWPMZ-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- YNSNJGRCQCDRDM-UHFFFAOYSA-N 1-chlorothioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl YNSNJGRCQCDRDM-UHFFFAOYSA-N 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 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
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- VUBUXALTYMBEQO-UHFFFAOYSA-N 2,2,3,3,3-pentafluoro-1-phenylpropan-1-one Chemical compound FC(F)(F)C(F)(F)C(=O)C1=CC=CC=C1 VUBUXALTYMBEQO-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- HCCGPHJJZWLGNB-UHFFFAOYSA-N 2-[2-(4-butoxyphenyl)ethenyl]-1,3,5-triazine Chemical compound C1=CC(OCCCC)=CC=C1C=CC1=NC=NC=N1 HCCGPHJJZWLGNB-UHFFFAOYSA-N 0.000 description 1
- IJXPXNZUSXLSTF-UHFFFAOYSA-N 2-[2-(4-butoxyphenyl)ethenyl]-5-(trichloromethyl)-1,3,4-oxadiazole Chemical compound C1=CC(OCCCC)=CC=C1C=CC1=NN=C(C(Cl)(Cl)Cl)O1 IJXPXNZUSXLSTF-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 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
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-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
- NZTUTWYBJCOZCO-UHFFFAOYSA-N 4-methoxy-2-phenyl-4,6-bis(trichloromethyl)-1h-1,3,5-triazine Chemical compound N1C(C(Cl)(Cl)Cl)=NC(OC)(C(Cl)(Cl)Cl)N=C1C1=CC=CC=C1 NZTUTWYBJCOZCO-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明は、直鎖上に並んだ複数の環構造を有する単官能の（メタ）アクリル基を有する化合物及び二官能の（メタ）アクリル基を有する化合物を含有する重合性組成物に関する。かかる重合性組成物を重合してなる重合膜は、光学異方体として有用なものである。 The present invention relates to a polymerizable composition containing a compound having a monofunctional (meth) acryl group having a plurality of ring structures arranged in a straight chain and a compound having a bifunctional (meth) acryl group. A polymer film obtained by polymerizing such a polymerizable composition is useful as an optical anisotropic body.
液晶物質はＴＮ型やＳＴＮ型に代表されるディスプレイ表示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、弾性率、熱膨張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、輝度向上フィルム、ローパス・フィルター、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 addition to application to a display medium that uses reversible motion of liquid crystal molecules such as display displays represented by TN type and STN type, the liquid crystal substance has its orientation and refractive index, dielectric constant, magnetic susceptibility, elastic modulus, Utilizing anisotropy of physical properties such as coefficient of thermal expansion, application to optical anisotropic bodies such as retardation plates, polarizing plates, light polarizing prisms, brightness enhancement films, low-pass filters, and various optical filters is examined. Has been.
上記光学異方体の製造は、例えば、重合性官能基を有する液晶性化合物又はこの液晶性化合物を含有する重合性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り光重合させて、均一な配向状態を半永久的に固定化して重合膜を得る方法が採られている。 The optical anisotropic body can be produced, for example, by uniformly aligning a liquid crystalline compound having a polymerizable functional group or a polymerizable composition containing the liquid crystalline compound in a liquid crystal state, and then maintaining the liquid crystal state with ultraviolet rays. A method of obtaining a polymerized film by photopolymerization by irradiating an energy beam such as semi-permanently fixing a uniform alignment state is employed.
この重合膜に用いられる重合性組成物において、液晶相発現温度が高い場合、エネルギー線による光重合だけでなく意図しない熱重合も誘起されて液晶分子の均一な配向状態が失われるため、所望する配向の固定が困難である。従って、硬化時の温度管理を容易にするために、室温付近で液晶相を示す重合性組成物が求められる。 In the polymerizable composition used for this polymerized film, when the liquid crystal phase expression temperature is high, not only photopolymerization by energy rays but also unintentional thermal polymerization is induced, and the uniform alignment state of liquid crystal molecules is lost. It is difficult to fix the orientation. Therefore, a polymerizable composition that exhibits a liquid crystal phase near room temperature is required in order to facilitate temperature control during curing.
また、重合膜は重合性組成物を基板に塗布して重合することによって得られるが、非重合性化合物が含まれると得られる重合膜の強度が不足したり、膜内に応力歪みが残存したりする欠点がある。また非重合性化合物を溶媒などで取り除くと、膜の均質性が保てずムラが生じたりする問題がある。従って、膜厚が均一な重合膜を得るためには重合性組成物を溶剤に溶かしたものを塗工する方法が好ましく用いられ、液晶性化合物又はそれを含む重合性組成物の溶媒溶解性が良好であることが必要とされる。 A polymerized film can be obtained by applying a polymerizable composition to a substrate and polymerizing it. However, when a non-polymerizable compound is contained, the strength of the polymerized film obtained is insufficient or stress strain remains in the film. There are disadvantages. Further, when the non-polymerizable compound is removed with a solvent or the like, there is a problem that the uniformity of the film cannot be maintained and unevenness occurs. Therefore, in order to obtain a polymer film having a uniform film thickness, a method in which a polymerizable composition is dissolved in a solvent is preferably used, and the solvent solubility of the liquid crystalline compound or the polymerizable composition containing the liquid crystal compound is preferably used. It needs to be good.
また、光学異方体のコントラスト比に関わるリターデーションＲは、Ｒ＝Δｎ・ｄ（式中、Δｎは光学（屈折率）異方性、ｄは膜厚）によって表される。Ｒは用途に応じて特定の値に設定する必要があるので、Δｎを大きくすればｄを小さくすることができる。この光学異方体の薄膜化は、重合時の液晶の配向制御が容易となり、製造時の歩溜まりが改善されて製造効率が向上する等の効果を得ることが可能である。 The retardation R related to the contrast ratio of the optical anisotropic body is represented by R = Δn · d (where Δn is optical (refractive index) anisotropy and d is a film thickness). Since R needs to be set to a specific value according to the application, d can be reduced by increasing Δn. This thinning of the optically anisotropic body makes it easy to control the orientation of the liquid crystal during polymerization, and it is possible to obtain effects such as an improvement in production yield and an increase in production efficiency.
光学異方体に用いられる重合性液晶化合物としては、重合性官能基が(メタ)アクリル基である化合物は重合反応性が高く、高い透明性を有する重合物が得られるので、光学異方体としての利用が盛んに検討されている。 As a polymerizable liquid crystal compound used for an optical anisotropic body, a compound having a polymerizable functional group of (meth) acrylic group has high polymerization reactivity, and a polymer having high transparency can be obtained. The use as is being studied actively.
単官能(メタ)アクリル基を有する化合物としては、例えば、特許文献１〜特許文献４に開示されている。また、単官能（メタ）アクリレート化合物と二官能（メタ）アクリレート化合物を併用してなる重合性組成物としては、例えば、特許文献５〜特許文献７に開示されている。しかしながら、これらの文献に開示されている重合性組成物では、何れも膜厚を薄くした場合の製膜の制御が困難である問題があった。 As a compound which has a monofunctional (meth) acryl group, it is disclosed by patent document 1-patent document 4, for example. Moreover, as a polymeric composition formed by using together a monofunctional (meth) acrylate compound and a bifunctional (meth) acrylate compound, it is disclosed by patent document 5-patent document 7, for example. However, the polymerizable compositions disclosed in these documents have a problem that it is difficult to control film formation when the film thickness is reduced.
一般に、重合膜の膜厚が厚い場合、重合性組成物中の液晶分子の配向制御が困難で重合膜の透過率が低下したり、着色が現れたりする等の問題がある。一方、膜厚の薄い重合膜を作製しようとすると、薄膜化により膜の全範囲にわたって良好な配向制御が得られるものの膜厚制御が困難で表面が不均一になったり、結晶化しやすくなったりする問題があった。また、製膜の際配向制御した液晶状態の安定性が乏しく、紫外線照射等の硬化前に配向が乱れる場合があり、従来既知の重合性組成物では満足できる重合膜は得られなかった。 In general, when the thickness of the polymer film is large, there is a problem that it is difficult to control the alignment of the liquid crystal molecules in the polymerizable composition, and the transmittance of the polymer film is lowered or coloring occurs. On the other hand, if an attempt is made to produce a polymer film with a small film thickness, good film orientation control can be obtained over the entire range of the film, but the film thickness control is difficult, the surface becomes non-uniform, and crystallization tends to occur. There was a problem. In addition, the stability of the liquid crystal state in which the orientation is controlled during film formation is poor, and the orientation may be disturbed before curing such as ultraviolet irradiation. Thus, satisfactory polymerized films cannot be obtained with conventionally known polymerizable compositions.
尚、特許文献１及び特許文献２には、本発明を構成する単官能（メタ）アクリレート化合物を請求範囲に含む重合性組成物が開示されているが、特許文献１又は特許文献２に明示されている化合物は、液晶性骨格において、（メタ）アクリル基とは対極の位置にある液晶性骨格の末端がシアノ基又はアルキル基である化合物であり、末端が水素原子である本願発明化合物とは異なる。また、特許文献１の発明は、単官能（メタ）アクリレート化合物とオキセタニル基を有する化合物とを併用して重合することにより、コレステリック液晶として選択反射波長に優れた効果が得られることを示めしたものであり、特許文献２は、着色の低減する液晶組成物を提案した発明であって、特許文献１及び特許文献２のいずれにも、本願発明のように薄膜化した場合でも製膜の制御が優れるという効果については、何ら記載がなく示唆すらされていない。 Patent Documents 1 and 2 disclose a polymerizable composition containing the monofunctional (meth) acrylate compound constituting the present invention in the scope of claims. In the liquid crystalline skeleton, the compound of the present invention in which the terminal of the liquid crystalline skeleton at the position opposite to the (meth) acryl group is a cyano group or an alkyl group, and the terminal is a hydrogen atom Different. In addition, the invention of Patent Document 1 shows that an effect excellent in selective reflection wavelength can be obtained as a cholesteric liquid crystal by polymerizing a monofunctional (meth) acrylate compound and a compound having an oxetanyl group in combination. Patent Document 2 is an invention that proposes a liquid crystal composition that reduces coloring, and both Patent Document 1 and Patent Document 2 control film formation even when the film thickness is reduced as in the present invention. There is no description or suggestion about the effect of being excellent.
従って、本発明の目的は室温付近で液晶相を示し、溶媒溶解性に優れる重合性組成物であって、かかる重合性組成物を硬化して得られる重合膜に対して、重合膜を薄膜化しても、均一な膜状態を維持し、耐熱性や配向制御及び光学特性に優れる重合性組成物を提供することにある。 Accordingly, an object of the present invention is a polymerizable composition that exhibits a liquid crystal phase near room temperature and is excellent in solvent solubility. The polymer film is made thinner than a polymer film obtained by curing such a polymerizable composition. However, it is to provide a polymerizable composition that maintains a uniform film state and is excellent in heat resistance, orientation control, and optical characteristics.
本発明者等は、上記課題を解決するため、鋭意検討を行った結果、特定の化学構造を有する化合物を含有する重合性組成物により、上記目的を達成できることを見い出し、本発明を完成するに至った。
即ち、下記一般式（１）で表される単官能（メタ）アクリレート化合物及び下記一般式（３）で表される二官能（メタ）アクリレート化合物を含有する重合性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。
In order to solve the above-mentioned problems, the present inventors have intensively studied and found that the above object can be achieved by a polymerizable composition containing a compound having a specific chemical structure, thereby completing the present invention. It came.
That is, by providing a polymerizable composition containing a monofunctional (meth) acrylate compound represented by the following general formula (1) and a bifunctional (meth) acrylate compound represented by the following general formula (3): The above objective has been achieved.
また、本発明は、上記一般式（１）において、環Ａ1、Ａ2及びＡ3のうちの少なくとも一つがナフタレン環である重合性組成物を提供するものである。 The present invention also provides a polymerizable composition in which at least one of the rings A 1 , A 2 and A 3 in the general formula (1) is a naphthalene ring.
また、本発明は、上記一般（１）において、ｐが０、Ｌ1が−（ＣＨ2）l−Ｏ−、Ｌ2が−ＣＯＯ−、環Ａ1及び環Ａ3がナフタレン環である重合性組成物を提供するものである。 In the general formula (1), the present invention provides a polymerization wherein p is 0, L 1 is — (CH 2 ) 1 —O—, L 2 is —COO—, ring A 1 and ring A 3 are naphthalene rings. The composition is provided.
また、本発明の重合性組成物は、上記一般式（１）中において、ｐが０、Ｌ1が−（ＣＨ2）l−Ｏ−、Ｌ2が−ＣＯＯ−、環Ａ1がベンゼン環、環Ａ3がナフタレン環である重合性組成物を提供するものである。 The polymerizable composition of the present invention is the above general formula (1), wherein p is 0, L 1 is — (CH 2 ) 1 —O—, L 2 is —COO—, and ring A 1 is a benzene ring. A polymerizable composition in which ring A 3 is a naphthalene ring is provided.
また、本発明は、上記一般式（３）において、環Ａ4、Ａ5及びＡ6のうちの少なくとも一つがナフタレン環である重合性組成物を提供するものである。 The present invention also provides a polymerizable composition in which at least one of rings A 4 , A 5 and A 6 in the general formula (3) is a naphthalene ring.
また、本発明は、さらに光学活性化合物を含有し、コレステリック相を発現する重合性組成物を提供するものである。 Moreover, this invention provides the polymeric composition which contains an optically active compound and expresses a cholesteric phase.
また、本発明は、さらにラジカル重合開始剤及び界面活性剤を含有する重合性組成物を提供するものである。 The present invention further provides a polymerizable composition containing a radical polymerization initiator and a surfactant.
また、本発明は、３０℃以下で液晶相を示す重合性組成物を提供するものである。 Moreover, this invention provides the polymeric composition which shows a liquid crystal phase at 30 degrees C or less.
また、本発明は、上記重合性組成物が液晶相を示す状態で、光重合させることにより作製された重合膜を提供するものである。 The present invention also provides a polymer film prepared by photopolymerization in a state where the polymerizable composition exhibits a liquid crystal phase.
また、本発明は、上記重合膜を使用してなるディスプレイ用光学フィルムを提供するものである。 Moreover, this invention provides the optical film for a display formed using the said polymeric film.
本発明の重合性組成物は、室温付近において液晶状態で重合可能であり、溶媒溶解性に優れた重合性組成物である。該重合性組成物を光重合させることにより作製される本発明の重合膜は、均一な膜状態を維持し、耐熱性、耐溶剤性及び光学特性に優れた液晶物質として有用である。 The polymerizable composition of the present invention is a polymerizable composition that can be polymerized in a liquid crystal state near room temperature and has excellent solvent solubility. The polymer film of the present invention produced by photopolymerizing the polymerizable composition is useful as a liquid crystal substance that maintains a uniform film state and is excellent in heat resistance, solvent resistance, and optical properties.
以下、本発明の重合性組成物及び該組成物を光重合させることにより作製される本発明の重合膜について、その好ましい実施形態に基づき詳細に説明する。 Hereinafter, the polymerizable composition of the present invention and the polymerized film of the present invention produced by photopolymerizing the composition will be described in detail based on preferred embodiments thereof.
上記一般式（１）中の環Ａ1、Ａ2、Ａ3、及び上記一般式（３）中の環Ａ4、Ａ5及びＡ6を置換する分岐を有してもよい炭素原子数１〜８のアルキル基としては、例えば、メチル、クロロメチル、トリフルオロメチル、シアノメチル、エチル、ジクロロエチル、プロピル、イソプロピル、ブチル、第二ブチル、第三ブチル、イソブチル、アミル、イソアミル、第三アミル、ヘキシル、２−ヘキシル、３−ヘキシル、シクロヘキシル、１−メチルシクロヘキシル、ヘプチル、２−ヘプチル、３−ヘプチル、イソヘプチル、第三ヘプチル、ｎ−オクチル、イソオクチル、第三オクチル又は２−エチルヘキシル等が挙げられ、
上記環Ａ1、Ａ2、Ａ3、Ａ4、Ａ5及びＡ6を置換する分岐を有してもよい炭素原子数１〜８のアルコキシ基としては、例えば、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又は２−エチルヘキシルオキシ等が挙げられる。
Number of carbon atoms that may have a branch for substituting the rings A 1 , A 2 , A 3 in the general formula (1) and the rings A 4 , A 5, and A 6 in the general formula (3) 1 As the alkyl group of ˜8, for example, methyl, chloromethyl, trifluoromethyl, cyanomethyl, ethyl, dichloroethyl, propyl, isopropyl, butyl, sec-butyl, sec-butyl, isobutyl, amyl, isoamyl, tertiary amyl, Hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tertiary heptyl, n-octyl, isooctyl, tertiary octyl or 2-ethylhexyl ,
Examples of the alkoxy group having 1 to 8 carbon atoms which may have a branch for substituting the rings A 1 , A 2 , A 3 , A 4 , A 5 and A 6 include, for example, methyloxy, chloromethyloxy, Trifluoromethyloxy, cyanomethyloxy, ethyloxy, dichloroethyloxy, propyloxy, isopropyloxy, butyloxy, sec-butyloxy, tert-butyloxy, isobutyloxy, amyloxy, isoamyloxy, tert-amyloxy, hexyloxy, cyclohexyloxy, heptyl Examples thereof include oxy, isoheptyloxy, tertiary heptyloxy, n-octyloxy, isooctyloxy, tertiary octyloxy and 2-ethylhexyloxy.
上記一般式（１）で表される単官能（メタ）アクリレート化合物の具体例としては、下記化合物Ｎｏ．１−１〜Ｎｏ．１−１５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 monofunctional (meth) acrylate compound represented by the general formula (1) include the following compound No. 1-1-No. 1-15. However, the present invention is not limited by the following compounds.
これら単官能（メタ）アクリレート化合物の中でも、上記一般式（１）における環Ａ1、Ａ2及びＡ3のうちの少なくとも一つがナフタレン環である化合物は、結晶性が低く、溶媒溶解性及び相溶性に優れるため好ましい。
さらに、上記一般式（１）におけるｐが０、Ｌ1が−(ＣＨ2)r−Ｏ−、Ｌ2が−ＣＯＯ−、環Ａ1及び環Ａ3がナフタレン環である化合物、及び、上記一般式（１）におけるｐが０、Ｌ1が−(ＣＨ2)r−Ｏ−、Ｌ2が−ＣＯＯ−、環Ａ1がベンゼン環、環Ａ3がナフタレン環である化合物がより好ましい。
Among these monofunctional (meth) acrylate compounds, a compound in which at least one of the rings A 1 , A 2 and A 3 in the general formula (1) is a naphthalene ring has low crystallinity, solvent solubility and phase. It is preferable because of its excellent solubility.
Furthermore, in the above general formula (1), p is 0, L 1 is — (CH 2 ) r —O—, L 2 is —COO—, ring A 1 and ring A 3 are naphthalene rings, and A compound in which p in the general formula (1) is 0, L 1 is — (CH 2 ) r —O—, L 2 is —COO—, ring A 1 is a benzene ring, and ring A 3 is a naphthalene ring is more preferable.
上記一般式（３）で表される二官能（メタ）アクリレート化合物の具体例としては、下記化合物Ｎｏ．２−１〜Ｎｏ．２−１８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 bifunctional (meth) acrylate compound represented by the general formula (3) include the following compound No. 2-1. 2-18. However, the present invention is not limited by the following compounds.
これら二官能（メタ）アクリレート化合物の中でも上記一般式（３）における環Ａ4、Ａ5及びＡ6のうちの少なくとも一つがナフタレン環である化合物は、結晶性が低く、溶媒溶解性及び相溶性に優れ、さらに光学（屈折率）異方性（Δｎ）が大きいため好ましい。 Among these bifunctional (meth) acrylate compounds, a compound in which at least one of the rings A 4 , A 5 and A 6 in the general formula (3) is a naphthalene ring has low crystallinity, solvent solubility and compatibility. And optical (refractive index) anisotropy (Δn) is large.
上記一般式（１）で表される単官能（メタ）アクリレート化合物に対する上記一般式（３）で表される二官能（メタ）アクリレート化合物の好ましい質量比は、５／９５〜５０／５０であり、特に好ましくは１０／９０〜４０／６０である。上記一般式（１）で表される単官能（メタ）アクリレート化合物の比率が５より小さいと、重合性組成物の配向制御が困難となる場合があり、上記一般式（３）で表される二官能（メタ）アクリレート化合物の比率が５０より小さいと、重合して得られる重合膜の耐熱性や耐溶剤性が不足する場合がある。また、上記単官能（メタ）アクリレート化合物及び上記二官能（メタ）アクリレート化合物の含有量の和は、本発明の重合性組成物（但し、溶剤を除く）１００質量部中、少なくとも５０質量部以上であることが好ましく、７０質量部以上が特に好ましい。 A preferable mass ratio of the bifunctional (meth) acrylate compound represented by the general formula (3) to the monofunctional (meth) acrylate compound represented by the general formula (1) is 5/95 to 50/50. Particularly preferred is 10/90 to 40/60. When the ratio of the monofunctional (meth) acrylate compound represented by the general formula (1) is smaller than 5, it may be difficult to control the orientation of the polymerizable composition, and is represented by the general formula (3). If the ratio of the bifunctional (meth) acrylate compound is less than 50, the heat resistance and solvent resistance of the polymerized film obtained by polymerization may be insufficient. The sum of the contents of the monofunctional (meth) acrylate compound and the bifunctional (meth) acrylate compound is at least 50 parts by mass in 100 parts by mass of the polymerizable composition of the present invention (excluding the solvent). It is preferable that it is 70 mass parts or more.
また、本発明の重合性組成物は、少なくとも室温付近、具体的には３０℃以下で液晶相を示すことが好ましく、特に２５℃以下で液晶相を示すことがより好ましい。 The polymerizable composition of the present invention preferably exhibits a liquid crystal phase at least near room temperature, specifically 30 ° C. or less, and more preferably exhibits a liquid crystal phase at 25 ° C. or less.
また、本発明の重合性組成物には、必要に応じて用いられる他の単量体（エチレン性不飽和結合を有する化合物）をラジカル重合開始剤と共に溶剤に溶解して溶液にすることができる。 In addition, in the polymerizable composition of the present invention, another monomer (a compound having an ethylenically unsaturated bond) used as necessary can be dissolved in a solvent together with a radical polymerization initiator to form a solution. .
上記他の単量体としては、例えば、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。
ただし、本発明の重合性組成物を用いて作製される重合膜の耐熱性及び光学特性を付与するために、他の単量体の含有量は、上記単官能（メタ）アクリレート化合物及び上記二官能（メタ）アクリレート化合物の合計１００質量部に対して、５０質量部以下が好ましく、特に３０質量部以下がより好ましい。
Examples of the other monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, secondary butyl (meth) acrylate, and tertiary 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, Ntachlorophenyl (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 , (Meth) acrylic acid esters such as pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, diacetone Riruamido, styrene, vinyltoluene, divinylbenzene and the like.
However, in order to impart heat resistance and optical properties of the polymer film produced using the polymerizable composition of the present invention, the content of the other monomer may be the above monofunctional (meth) acrylate compound and the above two monomers. 50 mass parts or less are preferable with respect to a total of 100 mass parts of a functional (meth) acrylate compound, and especially 30 mass parts or less are more preferable.
上記ラジカル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、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、ジアリールヨードニウム塩、トリアリールスルホニウム塩、ジフェニルヨードニウムテトラフルオロボレート、ジフェニルヨードニウムヘキサフルオロホスホネート、ジフェニルヨードニウムヘキサフルオロアルセネート、ジフェニルヨードニウムテトラ（ペンタフルオロフェニル）ボレート、４−メトキシフェニルフェニルヨードニウムテトラフルオロボレート、４−メトキシフェニルフェニルヨードニウムヘキサフルオロホスホネート、４−メトキシフェニルフェニルヨードニウムヘキサフルオロアルセネート、ビス（４−ｔｅｒｔ−ブチルフェニル）ヨードニウムジフェニルヨードニウムテトラフルオロボレート、ビス（４−ｔｅｒｔ−ブチルフェニル）ヨードニウムジフェニルヨードニウムヘキサフルオロアルセネート、ビス（４−ｔｅｒｔ−ブチルフェニル）ヨードニウムジフェニルヨードニウムトリフルオロメタンスルホネート、トリフェニルスルホニウムヘキサフルオロホスホネート、トリフェニルスルホニウムヘキサフルオロアルセネート、トリフェニルスルホニウムテトラ（ペンタフルオロフェニル）ボレート、４−メトキシフェニルジフェニルスルホニウムテトラフルオロボレート、４−メトキシフェニルジフェニルスルホニウムヘキサフルオロホスホネート、４−メトキシフェニルジフェニルスルホニウムヘキサフルオロアルセネート、４−メトキシフェニルジフェニルスルホニウムトリフルオロメタンスルホナート、４−メトキシフェニルジフェニルスルホニウムトリフェニルスルホニウムテトラ（ペンタフルオロフェニル）ボレート、４−フェニルチオフェニルジフェニルスルホニウムテトラフルオロボレート、４−フェニルチオフェニルジフェニルスルホニウムヘキサフルオロホスホネート、４−フェニルチオフェニルジフェニルスルホニウムヘキサフルオロアルセネート、ｐ−メトキシフェニル−２，４−ビス（トリクロロメチル）−ｓ−トリアジン、２−（ｐ−ブトキシスチリル）−ｓ−トリアジン、２−（ｐ−ブトキシスチリル）−５−トリクロロメチル−１，３，４−オキサジアゾール、９−フェニルアクリジン、９，１０−ジメチルベンズフェナジン、ベンゾフェノン／ミヒラーズケトン、ヘキサアリールビイミダゾール／メルカプトベンズイミダゾール、ベンジルジメチルケタール、チオキサントン／アミン、トリアリールスルホニウムヘキサフルオロホスフェート、ビス（２，４，６−トリメチルベンゾイル）−フェニルホスフィンオキシド等が挙げられる。 Examples of the radical polymerization initiator include benzoyl peroxide, 2,2′-azobisisobutyronitrile, benzoin ethers, benzophenones, acetophenones, benzyl ketals, diaryl iodonium salts, triaryl sulfonium salts, diphenyl Iodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium tetra (pentafluorophenyl) borate, 4-methoxyphenylphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4- Methoxyphenylphenyliodonium hexafluoroarsenate, bis (4-tert-butylphenol) Nyl) iodonium diphenyliodonium tetrafluoroborate, bis (4-tert-butylphenyl) iodonium diphenyliodonium hexafluoroarsenate, bis (4-tert-butylphenyl) iodonium diphenyliodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphonate, tri Phenylsulfonium hexafluoroarsenate, triphenylsulfonium tetra (pentafluorophenyl) borate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4 -Methoxyphenyl diphe Rusulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium triphenylsulfonium tetra (pentafluorophenyl) borate, 4-phenylthiophenyldiphenylsulfonium tetrafluoroborate, 4-phenylthiophenyldiphenylsulfonium hexafluorophosphonate, 4-phenylthio Phenyldiphenylsulfonium hexafluoroarsenate, p-methoxyphenyl-2,4-bis (trichloromethyl) -s-triazine, 2- (p-butoxystyryl) -s-triazine, 2- (p-butoxystyryl) -5 -Trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-dimethylbenzphenazine, benzophenone / Michler's ketone Hexaarylbiimidazole / mercaptobenzimidazole, benzyl dimethyl ketal, thioxanthone / amine, triarylsulfonium hexafluorophosphate, bis (2,4,6-trimethylbenzoyl) - phenylphosphine oxide, and the like.
また、上記ラジカル重合開始剤と増感剤の組合せも好ましく使用することができる。かかる増感剤としては、例えば、チオキサントン、フェノチアジン、クロロチオキサントン、キサントン、アントラセン、ジフェニルアントラセン、ルプレン等が挙げられる。上記ラジカル重合開始剤及び／又は上記増感剤を添加する場合は、本発明の重合性組成物１００質量部に対して、１０質量部以下であることが好ましく、５質量部以下がさらに好ましく、０．５〜３質量部の範囲内がより好ましい。 Moreover, the combination of the said radical polymerization initiator and a sensitizer can also be used preferably. Examples of such sensitizers include thioxanthone, phenothiazine, chlorothioxanthone, xanthone, anthracene, diphenylanthracene, and lupine. When adding the radical polymerization initiator and / or the sensitizer, it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, with respect to 100 parts by mass of the polymerizable composition of the present invention. A range of 0.5 to 3 parts by mass is more preferable.
上記溶剤としては、例えば、ベンゼン、トルエン、キシレン、メシチレン、ｎ−ブチルベンゼン、ジエチルベンゼン、テトラリン、メトキシベンゼン、１，２−ジメトキシベンゼン、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロペンタノン、シクロヘキサノン、酢酸エチル、乳酸メチル、乳酸エチル、エチレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、γ−ブチロラクトン、２−ピロリドン、Ｎ−メチル−２−ピロリドン、ジメチルホルムアミド、クロロホルム、ジクロロメタン、四塩化炭素、ジクロロエタン、トリクロロエチレン、テトラクロロエチレン、クロロベンゼン、ｔ−ブチルアルコール、ジアセトンアルコール、グリセリン、モノアセチレン、エチレングリコール、トリエチレングリコール、ヘキシレングリコール、エチレングリコールモノメチルエーテル、エチルセルソルブ、ブチルセルソルブなどである。溶剤は単一化合物であってもよいし、または混合物であってもよい。これらの溶剤の中でも、沸点が６０〜２５０℃のものが好ましく、６０〜１８０℃のものが特に好ましい。６０℃より低いと塗布工程で溶媒が揮発して膜の厚さにムラが生じやすく、２５０℃より高いと脱溶媒工程で減圧しても溶媒が残留したり、高温での処理による熱重合を誘起したりして配向性が低下する場合がある。 Examples of the solvent include benzene, toluene, xylene, mesitylene, n-butylbenzene, diethylbenzene, tetralin, methoxybenzene, 1,2-dimethoxybenzene, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexane. Pentanone, cyclohexanone, ethyl acetate, methyl lactate, ethyl lactate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, γ-butyrolactone, 2-pyrrolidone, N-methyl-2-pyrrolidone, dimethyl Formamide, chloroform, dichloromethane, carbon tetrachloride, dichloroethane, trichloro Styrene, tetrachlorethylene, chlorobenzene, and the like t- butyl alcohol, diacetone alcohol, glycerin, mono-acetylene, ethylene glycol, triethylene glycol, hexylene glycol, ethylene glycol monomethyl ether, ethyl cellosolve, butyl cellosolve. The solvent may be a single compound or a mixture. Among these solvents, those having a boiling point of 60 to 250 ° C are preferable, and those having a boiling point of 60 to 180 ° C are particularly preferable. If the temperature is lower than 60 ° C., the solvent is volatilized in the coating process and the film thickness is likely to be uneven. If the temperature is higher than 250 ° C., the solvent remains even when the pressure is reduced in the desolvation step. In some cases, the orientation may be reduced.
また、本発明の重合性組成物に、さらに光学活性化合物を含有させることによって、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ができ、コレステリック液晶相を固定化することができる。かかる光学活性化合物を含有させる場合、本発明の重合性組成物（但し、溶剤を除く）１００質量部に対して、０．１〜１００質量部の範囲内が好ましく、１〜５０質量部がより好ましい。かかる光学活性化合物としては、例えば下記〔化３７〕〜〔化５４〕の化合物を挙げることができる。 Further, by adding an optically active compound to the polymerizable composition of the present invention, a polymer having a helical structure of a liquid crystal skeleton can be obtained, and a cholesteric liquid crystal phase can be fixed. When such an optically active compound is contained, it is preferably in the range of 0.1 to 100 parts by weight, more preferably 1 to 50 parts by weight with respect to 100 parts by weight of the polymerizable composition of the present invention (excluding the solvent). preferable. Examples of such an optically active compound include the following [Chemical Formula 37] to [Chemical Formula 54].
また、本発明の重合性組成物は、空気界面側に分布する排除体積効果を有する界面活性剤をさらに含有させることが好ましい。界面活性剤は重合性組成物を支持基板などに塗布することを容易にしたり、液晶相の配向を制御したりする等の効果を得られるものが好ましい。かかる界面活性剤としては、例えば、４級アンモニウム塩、アルキルアミンオキサイド、ポリアミン誘導体、ポリオキシエチレン−ポリオキシプロピレン縮合物、ポリエチレングリコール及びそのエステル、ラウリル硫酸ナトリウム、ラウリル硫酸アンモニウム、ラウリル硫酸アミン類、アルキル置換芳香族スルホン酸塩、アルキルリン酸塩、ペルフルオロアルキルスルホン酸塩、ペルフルオロアルキルカルボン酸塩、ペルフルオロアルキルエチレンオキシド付加物、ペルフルオロアルキルトリメチルアンモニウム塩等が挙げられる。界面活性剤の好ましい使用割合は、界面活性剤の種類、組成物の成分比などに依存するが、本発明の重合性組成物１００質量部に対して０．０１〜５質量部の範囲内であることが好ましく、０．０５〜１質量部の範囲内がより好ましい。 Moreover, it is preferable that the polymerizable composition of the present invention further contains a surfactant having an excluded volume effect distributed on the air interface side. The surfactant is preferably a surfactant that can easily apply the polymerizable composition to a support substrate or the like or can control the orientation of the liquid crystal phase. Examples of such surfactants include quaternary ammonium salts, alkylamine oxides, polyamine derivatives, polyoxyethylene-polyoxypropylene condensates, polyethylene glycol and esters thereof, sodium lauryl sulfate, ammonium lauryl sulfate, amines of lauryl sulfate, alkyls. Examples thereof include substituted aromatic sulfonates, alkyl phosphates, perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl ethylene oxide adducts, and perfluoroalkyl trimethyl ammonium salts. A preferable use ratio of the surfactant depends on the kind of the surfactant, the component ratio of the composition, and the like, but within a range of 0.01 to 5 parts by mass with respect to 100 parts by mass of the polymerizable composition of the present invention. It is preferable that it is within the range of 0.05 to 1 part by mass.
また、本発明の重合性組成物には、必要に応じて添加物をさらに含有してもよい。重合性組成物の特性を調製するための添加物としては、例えば、保存安定剤、酸化防止剤、紫外線吸収剤、赤外線吸収剤、無機物、有機物等の微粒子化物、ポリマー等の機能性化合物を含有させてもよい。 Moreover, you may further contain an additive in the polymeric composition of this invention as needed. Additives for adjusting the characteristics of the polymerizable composition include, for example, storage stabilizers, antioxidants, ultraviolet absorbers, infrared absorbers, fine particles such as inorganic and organic substances, and functional compounds such as polymers. You may let them.
上記保存安定剤は、重合性組成物の保存安定性を向上させる効果を付与することができる。使用できる安定剤としては、例えば、ヒドロキノン、ヒドロキノンモノアルキルエーテル類、第三ブチルカテコール類、ピロガロール類、チオフェノール類、ニトロ化合物類、２−ナフチルアミン類、２−ヒドロキシナフタレン類等が挙げられる。これらを添加する場合は、本発明の重合性組成物１００質量部に対して、１質量部以下であることが好ましく、０．５質量部以下が特に好ましい。 The said storage stabilizer can provide the effect which improves the storage stability of polymeric composition. 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 these, it is preferable that it is 1 mass part or less with respect to 100 mass parts of polymeric compositions of this invention, and 0.5 mass part or less is especially preferable.
上記酸化防止剤としては、特に制限がなく公知の化合物を使用することができ、例えば、ヒドロキノン、２，６−ジ−ｔ−ブチル−ｐ−クレゾール、２，６−ジ−ｔ−ブチルフェノール、トリフェニルホスファイト、トリアルキルホスファイト等が挙げられる。 The antioxidant is not particularly limited and a known compound can be used. Examples thereof include hydroquinone, 2,6-di-t-butyl-p-cresol, 2,6-di-t-butylphenol, Examples thereof include phenyl phosphite and trialkyl phosphite.
上記紫外線吸収剤としては、特に制限がなく公知の化合物を使用することができ、例えば、サリチル酸エステル系化合物、ベンゾフェノール系化合物、ベンゾトリアゾール系化合物、シアノアクリレート系化合物又はニッケル錯塩系化合物等によって紫外線吸収能をもたせたものであってもよい。 The ultraviolet absorber is not particularly limited, and a known compound can be used. For example, a salicylic acid ester compound, a benzophenol compound, a benzotriazole compound, a cyanoacrylate compound, a nickel complex compound, or the like It may have absorptive capacity.
上記微粒子化物は光学（屈折率）異方性（Δｎ）を調整したり、重合膜の強度を上げたりするために用いることができる。微粒子化物の材質としては無機物、有機物、金属などが挙げられ、凝集防止のため、微粒子化物は０．００１〜０．１μｍの粒子径が好ましく利用することができ、さらに好ましくは０．００１〜０．０５μｍの粒子径である。粒子径の分布はシャープであるものが好ましい。本発明の重合性組成物１００質量部に対して、微粒子化物は、０．１〜３０質量部の範囲内で好ましく使用することができる。 The fine particles can be used for adjusting the optical (refractive index) anisotropy (Δn) and increasing the strength of the polymer film. Examples of the material of the fine particles include inorganic substances, organic substances, metals, and the like. To prevent aggregation, the fine particles can preferably have a particle diameter of 0.001 to 0.1 μm, and more preferably 0.001 to 0. .05 μm particle size. A sharp particle size distribution is preferred. The finely divided product can be preferably used within a range of 0.1 to 30 parts by mass with respect to 100 parts by mass of the polymerizable composition of the present invention.
上記無機物としては、例えば、セラミックス、フッ素金雲母、フッ素四ケイ素雲母、テニオライト、フッ素バーミキュライト、フッ素ヘクトライト、ヘクトライト、サポナイト、スチブンサイト、モンモリロナイト、バイデライト、カオリナイト、フライポンタイト、ＺｎＯ、ＴｉＯ2、ＣｅＯ2、Ａｌ2Ｏ3、Ｆｅ2Ｏ3、ＺｒＯ2、ＭｇＦ2、ＳｉＯ2、ＳｒＣＯ3、Ｂａ（ＯＨ）2、Ｃａ（ＯＨ）2、Ｇａ（ＯＨ）3、Ａｌ（ＯＨ）3、Ｍｇ（ＯＨ）2、Ｚｒ（ＯＨ）4等が挙げられる。尚、炭酸カルシウムの針状結晶などの微粒子は光学異方性を有し、このような微粒子によって重合体の光学異方性を調節できる。上記有機物としては、例えばカーボンナノチューブ、フラーレン、デンドリマー、ポリビニルアルコール、ポリメタクリレート、ポリイミド等が挙げられる。 Examples of the inorganic material include ceramics, fluorine phlogopite, fluorine tetrasilicon mica, teniolite, fluorine vermiculite, fluorine hectorite, hectorite, saponite, stevensite, montmorillonite, beidellite, kaolinite, frypontite, ZnO, TiO 2 , CeO 2, Al 2 O 3, Fe 2 O 3, ZrO 2, MgF 2, SiO 2, SrCO 3, Ba (OH) 2, Ca (OH) 2, Ga (OH) 3, Al (OH) 3, Mg (OH) 2 , Zr (OH) 4 and the like. Fine particles such as calcium carbonate needle-like crystals have optical anisotropy, and the optical anisotropy of the polymer can be adjusted by such fine particles. Examples of the organic substance include carbon nanotubes, fullerenes, dendrimers, polyvinyl alcohol, polymethacrylates, and polyimides.
上記ポリマーは、重合膜の電気特性や配向性を制御することができ、上記溶剤に可溶性の高分子化合物が好ましく使用することができる。かかる高分子化合物としては、例えば、ポリアミド、ポリウレタン、ポリウレア、ポリエポキサイド、ポリエステル、ポリエステルポリオール等が挙げられる。 The polymer can control the electrical properties and orientation of the polymer film, and a polymer compound soluble in the solvent can be preferably used. Examples of such a polymer compound include polyamide, polyurethane, polyurea, polyepoxide, polyester, polyester polyol, and the like.
本発明の重合膜は、上記重合性組成物を溶媒に溶解した後、支持基板に塗布して、重合性組成物中の液晶分子を配向させた状態で脱溶媒し、次いでエネルギー線を照射して重合することにより得ることができる。 The polymer film of the present invention is prepared by dissolving the polymerizable composition in a solvent, applying the solution to a support substrate, removing the solvent in a state where liquid crystal molecules in the polymerizable composition are aligned, and then irradiating energy rays. Can be obtained by polymerization.
上記支持基板としては、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。このような支持基板上にポリイミド配向膜又はポリビニルアルコール配向膜を施したものが特に好ましく使用することができる。 The support substrate is not particularly limited, but preferred examples include glass plates, polyethylene terephthalate plates, polycarbonate plates, polyimide plates, polyamide plates, polymethyl methacrylate plates, polystyrene plates, polyvinyl chloride plates, polytetrafluoroethylene plates. , Cellulose plate, silicon plate, reflector plate, calcite plate and the like. What provided the polyimide alignment film or the polyvinyl alcohol alignment film on such a support substrate can be used especially preferably.
上記支持基板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及び流延成膜法等を用いることができる。尚、上記重合膜の膜厚は用途等に応じて適宜選択されるが、好ましくは０．０５〜１０μｍの範囲から選択される。 As a method of applying to the support substrate, 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, slide coating method. The method, the printing coating method, the casting film forming method, and the like can be used. In addition, although the film thickness of the said polymer film is suitably selected according to a use etc., Preferably it is selected from the range of 0.05-10 micrometers.
本発明の重合性組成物中の液晶分子を配向させる方法としては、例えば支持基板上に事前に配向処理を施す方法が挙げられる。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又はポリビニルアルコール系配向膜からなる液晶配向層を支持基板上に設け、ラビング等の処理を行う方法が挙げられる。また、支持基板上の組成物に磁場や電場等を印加する方法等も挙げられる。 Examples of the method for aligning the liquid crystal molecules in the polymerizable composition of the present invention include a method in which an alignment treatment is performed in advance on a support substrate. As a preferred method for performing the alignment treatment, there is a method in which a liquid crystal alignment layer composed of various polyimide alignment films or polyvinyl alcohol alignment films is provided on a support substrate and a treatment such as rubbing is performed. Moreover, the method of applying a magnetic field, an electric field, etc. to the composition on a support substrate is also mentioned.
本発明の重合性組成物を重合させる方法は熱又は電磁波を用いる公知の方法を適用できる。電磁波による重合反応としては、ラジカル重合、アニオン重合、カチオン重合、配位重合、リビング重合等があげられる。重合性組成物が液晶相を示す条件下で、重合を行なわせることが容易だからである。また磁場や電場を印加しながら架橋させることも好ましい。支持基板上に形成した液晶（共）重合体は、そのまま使用しても良いが、必要に応じて、支持基板から剥離したり、他の支持基板に転写したりして使用してもよい。 As a method for polymerizing the polymerizable composition of the present invention, a known method using heat or electromagnetic waves can be applied. Examples of the polymerization reaction using electromagnetic waves include radical polymerization, anionic polymerization, cationic polymerization, coordination polymerization, and living polymerization. This is because it is easy to perform polymerization under the condition that the polymerizable composition exhibits a liquid crystal phase. It is also preferable to crosslink while applying a magnetic field or electric field. The liquid crystal (co) polymer formed on the support substrate may be used as it is, but may be used after peeling from the support substrate or transferring to another support substrate, if necessary.
上記光の好ましい種類は、紫外線、可視光線、赤外線等である。電子線、Ｘ線などの電磁波を用いてもよい。通常は、紫外線または可視光線が好ましい。好ましい波長の範囲は１５０〜５００ｎｍである。さらに好ましい範囲は２５０〜４５０ｎｍであり、最も好ましい範囲は３００〜４００ｎｍである。光源は、低圧水銀ランプ（殺菌ランプ、蛍光ケミカルランプ、ブラックライト）、高圧放電ランプ（高圧水銀ランプ、メタルハライドランプ）、またはショートアーク放電ランプ（超高圧水銀ランプ、キセノンランプ、水銀キセノンランプ）などが挙げられるが、超高圧水銀ランプが好ましく使用することができる。光源からの光はそのまま重合性組成物に照射してもよく、フィルターによって選択した特定の波長（または特定の波長領域）を重合性組成物に照射してもよい。好ましい照射エネルギー密度は、２〜５０００ｍＪ／ｃｍ2であり、さらに好ましい範囲は１０〜３０００ｍＪ／ｃｍ2であり、特に好ましい範囲は１００〜２０００ｍＪ／ｃｍ2である。好ましい照度は０．１〜５０００ｍＷ/ｃｍ2であり、さらに好ましい照度は１〜２０００ｍＷ/ｃｍ2である。重合性組成物が液晶相を有するように、光を照射するときの温度を設定できるが、好ましい照射温度は１００℃以下である。１００℃以上の温度では熱による重合が起こりうるので良好な配向が得られないときがある。 Preferred types of the light are ultraviolet rays, visible rays, infrared rays and the like. Electromagnetic waves such as electron beams and X-rays may be used. Usually, ultraviolet rays or visible rays are preferable. A preferable wavelength range is 150 to 500 nm. A more preferable range is 250 to 450 nm, and a most preferable range is 300 to 400 nm. The light source is a low-pressure mercury lamp (sterilization lamp, fluorescent chemical lamp, black light), high-pressure discharge lamp (high-pressure mercury lamp, metal halide lamp), or short arc discharge lamp (ultra-high pressure mercury lamp, xenon lamp, mercury xenon lamp). Among them, an ultrahigh pressure mercury lamp can be preferably used. Light from the light source may be irradiated to the polymerizable composition as it is, or a specific wavelength (or a specific wavelength region) selected by a filter may be irradiated to the polymerizable composition. Preferred irradiation energy density is 2~5000mJ / cm 2, more preferably ranges are 10~3000mJ / cm 2, particularly preferred range is 100 to 2000 mJ / cm 2. A preferable illuminance is 0.1 to 5000 mW / cm 2 , and a more preferable illuminance is 1 to 2000 mW / cm 2 . The temperature at which light is irradiated can be set so that the polymerizable composition has a liquid crystal phase, but the preferable irradiation temperature is 100 ° C. or lower. Polymerization due to heat can occur at a temperature of 100 ° C. or higher, so that good alignment may not be obtained.
本発明の重合膜は、光学異方性を有する成形体として利用することができる。この成形体の用途としては、例えば、位相差板（１／２波長板、１／４波長板など）、偏光素子、二色性偏光板、液晶配向膜、反射防止膜、選択反射膜、視野角補償膜等の光学補償に用いることができる。その他にも、液晶レンズ、マイクロレンズ等の光学レンズ、高分子分散型液晶（ＰＤＬＣ）電子ペーパー、デジタルペーパー等の情報記録材料にも利用することができる。 The polymer film of the present invention can be used as a molded article having optical anisotropy. Examples of uses of the molded body include a retardation plate (1/2 wavelength plate, 1/4 wavelength plate, etc.), polarizing element, dichroic polarizing plate, liquid crystal alignment film, antireflection film, selective reflection film, field of view. It can be used for optical compensation of an angle compensation film or the like. In addition, it can also be used for information recording materials such as optical lenses such as liquid crystal lenses and microlenses, polymer dispersed liquid crystal (PDLC) electronic paper, and digital paper.
以下、合成例及び実施例をもって本発明を更に説明する。しかしながら、本発明は以下の合成例及び実施例によって制限を受けるものではない。尚、下記合成例１〜２は、本発明に係る化合物の製造例を示すものであり、下記製造例１は、本発明の重合性組成物の調製例及び、該重合性組成物を用いた本発明の重合膜の製造例を示すものであり、下記実施例１〜３は、本発明の重合膜の製造例及び評価例を示すものである。 Hereinafter, the present invention will be further described with synthesis examples and examples. However, the present invention is not limited by the following synthesis examples and examples. In addition, the following synthesis examples 1-2 show the manufacture example of the compound which concerns on this invention, and the following manufacture example 1 used the preparation example of this polymerizable composition of this invention, and this polymerizable composition. The manufacture example of the polymeric film of this invention is shown, and the following Examples 1-3 show the manufacture example and evaluation example of the polymeric film of this invention.
〔合成例１〕（化合物Ｎｏ．１−１の製造）
化合物Ｎｏ．１−１を〔化５５〕に示す反応式に従い、下記の手順で合成した。
[Synthesis Example 1] (Production of Compound No. 1-1)
Compound No. 1-1 was synthesized according to the following procedure according to the reaction formula shown in [Chemical Formula 55].
４−［６−（アクリロイルオキシ）−ヘキシルキシ］−２−ナフトエ酸 ５．０ｇ（１４．６ｍｍｏｌ）、β−ナフトール２．２１ｇ（１５．３ｍｍｏｌ）、４−ジメチルアミノピリジン（ＤＭＡＰ）０．０９ｇ（０．７ｍｍｏｌ）をジクロロメタン５０ｇに溶解した。水冷下において、Ｎ，Ｎ’−ジシクロヘキシルカルボジイミド（ＤＣＣ）３．１６ｇ（１５．３ｍｍｏｌ）をジクロロメタン４．７ｇに溶解させたものを滴下して１時間攪拌した。攪拌後、析出物をろ別して溶媒を留去した。残渣をシリカゲルカラムクロマトグラフィー（展開溶媒：トルエン）により精製した後、エタノール／トルエンの混合溶媒で再結晶し、白色結晶（５．４ｇ、収率７８．９％）を得た。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．１−１であると確認された。これらの分析結果について下記に示す。 4- [6- (acryloyloxy) -hexyloxy] -2-naphthoic acid 5.0 g (14.6 mmol), β-naphthol 2.21 g (15.3 mmol), 4-dimethylaminopyridine (DMAP) 0.09 g ( 0.7 mmol) was dissolved in 50 g of dichloromethane. Under water cooling, a solution prepared by dissolving 3.16 g (15.3 mmol) of N, N′-dicyclohexylcarbodiimide (DCC) in 4.7 g of dichloromethane was added dropwise and stirred for 1 hour. After stirring, the precipitate was filtered off and the solvent was distilled off. The residue was purified by silica gel column chromatography (developing solvent: toluene) and then recrystallized with a mixed solvent of ethanol / toluene to obtain white crystals (5.4 g, yield 78.9%). When the obtained white crystals were analyzed, the white crystals were the target compound No. 1. 1-1. The results of these analyzes are shown below.
（１）ＩＲ［ＫＢｒ錠剤法］（ｃｍ-1）
３０５９，２９３９，２８５８，１７２８，１６２８，１５０８，１４６６，１４０８，１３８９，１２８１，１２４６，１１９６，１１５７，１１２６，１０６９，９８８，９６１，８９９，８５６，８０６，７４１，４７５，４５１
（２）ＮＭＲ［ＣＤＣｌ3］（ｐｐｍ）
１．２−２．２（ｍ；８Ｈ），４．２（ｑ；４Ｈ），５．７−６．５（ｍ；３Ｈ），７．２−７．６（ｍ；５Ｈ），７．７−８．０（ｍ；６Ｈ），８．１（ｑ；１Ｈ），８．７（ｄ；１Ｈ）
（３）相転移温度（℃）
示差走査熱量測定機（サーモプラスＴＧ８１２０；（株）リガク製）にて、窒素雰囲気下（１０ｍｌ／ｍｉｎ）、５℃／ｍｉｎの速度で室温（２５℃）から１２０℃まで加熱し、化合物の相転移温度を求めた。尚、液晶相（ネマチック相）の同定は、上記示差走査熱量測定機による分析で転移熱を求め、さらに、化合物を二枚のガラス板間にはさみ、ホットステージ付き偏光顕微鏡による光学組織観察を行うことにより同定した。
(1) IR [KBr tablet method] (cm −1 )
3059, 2939, 2858, 1728, 1628, 1508, 1466, 1408, 1389, 1281, 1246, 1196, 1157, 1126, 1069, 988, 961, 899, 856, 806, 741, 475, 451
(2) NMR [CDCl 3 ] (ppm)
1.2-2.2 (m; 8H), 4.2 (q; 4H), 5.7-6.5 (m; 3H), 7.2-7.6 (m; 5H), 7. 7-8.0 (m; 6H), 8.1 (q; 1H), 8.7 (d; 1H)
(3) Phase transition temperature (° C)
In a differential scanning calorimeter (Thermo Plus TG8120; manufactured by Rigaku Corporation), the mixture was heated from room temperature (25 ° C.) to 120 ° C. at a rate of 5 ° C./min under a nitrogen atmosphere (10 ml / min). The transition temperature was determined. The liquid crystal phase (nematic phase) is identified by obtaining the heat of transition by analysis with the above differential scanning calorimeter, and further sandwiching the compound between two glass plates and observing the optical structure with a polarizing microscope with a hot stage. Was identified.
〔合成例２〕（化合物Ｎｏ．１−３の製造）
化合物Ｎｏ．１−３を〔化５７〕に示す反応式に従い、下記の手順で合成した。
[Synthesis Example 2] (Production of Compound No. 1-3)
Compound No. 1-3 was synthesized according to the following procedure according to the reaction formula shown in [Chemical Formula 57].
４−［６−（メタクリロイルオキシ）−エチルオキシ］安息香酸 ８．８ｇ（３５ｍｍｏｌ）、β−ナフトール５．１ｇ（３５ｍｍｏｌ）、４−ジメチルアミノピリジン（ＤＭＡＰ）０．４ｇ（３．６ｍｍｏｌ）をクロロホルム４０ｍｌに溶解した。水冷下において、Ｎ，Ｎ’−ジシクロヘキシルカルボジイミド（ＤＣＣ）７．６ｇ（３７ｍｍｏｌ）をクロロホルム１５ｍｌに溶解させたものを滴下して１時間攪拌した。攪拌後、析出物はろ別して溶媒を留去した。残渣をシリカゲルカラムクロマトグラフィー（展開溶媒：クロロホルム）により精製した後、メタノール／酢酸エチルの混合溶媒で再結晶し、白色結晶（１０．５ｇ、収率８１％）を得た。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．１−３であると同定された。これらの分析結果について下記に示す。 4- [6- (methacryloyloxy) -ethyloxy] benzoic acid 8.8 g (35 mmol), β-naphthol 5.1 g (35 mmol), 4-dimethylaminopyridine (DMAP) 0.4 g (3.6 mmol) in chloroform 40 ml Dissolved in. Under water cooling, 7.6 g (37 mmol) of N, N′-dicyclohexylcarbodiimide (DCC) dissolved in 15 ml of chloroform was added dropwise and stirred for 1 hour. After stirring, the precipitate was filtered off and the solvent was distilled off. The residue was purified by silica gel column chromatography (developing solvent: chloroform) and then recrystallized with a mixed solvent of methanol / ethyl acetate to obtain white crystals (10.5 g, yield 81%). When the obtained white crystals were analyzed, the white crystals were the target compound No. 1. Identified as 1-3. The results of these analyzes are shown below.
（分析結果）
（１）ＩＲ［ＫＢｒ錠剤法］（ｃｍ-1）
３０５９，２９５９，２９２８，１７３２，１７１３，１６３６，１６０５，１５７８，１５１２，１４５０，１４１２，１３５４，１２８１，１２５８，１２１１，１１６９，１０６５，９６１，９４１，８５３，８１４，７４８，６９１，６６０，６２９，４７８
（２）1Ｈ−ＮＭＲ［ＣＤＣｌ3］（ｐｐｍ）
２．０（ｓ；３Ｈ），４．３（ｔ；２Ｈ），４．５（ｔ；２Ｈ），５．６−６．２（ｍ；２Ｈ），７．０−８．３（ｍ；１１Ｈ）
（３）融点（℃）
示差走査熱量測定機（サーモプラスＴＧ８１２０；（株）リガク製）にて、窒素雰囲気下（１０ｍｌ／ｍｉｎ）、５℃／ｍｉｎの速度で室温（２５℃）から１００℃まで加熱して化合物の融点を求めたところ、８７．９℃であった。
(result of analysis)
(1) IR [KBr tablet method] (cm −1 )
3059, 2959, 2928, 1732, 1713, 1636, 1605, 1578, 1512, 1450, 1412, 1354, 1281, 1258, 1211, 1169, 1065, 961, 941, 853, 814, 748, 691, 660, 629, 478
(2) 1 H-NMR [CDCl 3 ] (ppm)
2.0 (s; 3H), 4.3 (t; 2H), 4.5 (t; 2H), 5.6-6.2 (m; 2H), 7.0-8.3 (m; 11H)
(3) Melting point (° C)
With a differential scanning calorimeter (ThermoPlus TG8120; manufactured by Rigaku Corporation), the melting point of the compound was heated from room temperature (25 ° C) to 100 ° C at a rate of 5 ° C / min in a nitrogen atmosphere (10 ml / min). Was 87.9 ° C.
〔製造例１〕（重合膜の作製）
下記の手順（［１］試料の調製、［２］支持基板の製作、［３］支持基板への塗布）に従い本発明の重合性組成物から重合膜を作製した。
[Production Example 1] (Preparation of polymerized film)
A polymerized film was produced from the polymerizable composition of the present invention according to the following procedures ([1] Preparation of sample, [2] Production of support substrate, [3] Application to support substrate).
［１］重合性組成物溶液の調製
表１に記載の重合性組成物１．０ｇを溶媒（シクロヘキサノン／２−ブタノン＝１／１（質量比））４．０ｇに添加して溶解した後、ラジカル重合開始剤（Ｎ−１９１９；株式会社ＡＤＥＫＡ製）０．０３ｇを加えて完全に溶解した後に、０．４５μｍフィルターでろ過処理を実施して重合性組成物溶液を調製した。
[1] Preparation of Polymerizable Composition Solution After adding 1.0 g of the polymerizable composition described in Table 1 to 4.0 g of solvent (cyclohexanone / 2-butanone = 1/1 (mass ratio)) and dissolving, After 0.03 g of radical polymerization initiator (N-1919; manufactured by ADEKA Corporation) was added and completely dissolved, filtration treatment was performed with a 0.45 μm filter to prepare a polymerizable composition solution.
［２］支持基板の製作
中性洗剤で洗浄後、純水で洗い流し乾燥したガラス板にポリビニルアルコール５％水溶液をスピンコーターで均一に塗工し、１００℃で３分間乾燥させた。乾燥後、ガラス基板に支持されたポリビニルアルコールの表面をレーヨン布で一定方向に擦り、支持基板を製作した。
[2] Production of Support Substrate After washing with a neutral detergent, a 5% aqueous solution of polyvinyl alcohol was uniformly applied on a glass plate washed with pure water and dried with a spin coater, and dried at 100 ° C. for 3 minutes. After drying, the surface of the polyvinyl alcohol supported on the glass substrate was rubbed with a rayon cloth in a certain direction to produce a supporting substrate.
［３］支持基板への塗布
上記［１］で調製した重合性組成物溶液を、上記［２］で製作した支持基板上にスピンコーターで塗工を行った。塗工は膜厚が約１．０μｍになるようにスピンコーターの回転数及び時間を調整して実施した。塗工後、ホットプレートを用いて１００℃で３分間乾燥して室温下で３分間冷却した後に、高圧水銀灯（１２０Ｗ／ｃｍ）で２０秒間照射し、膜を硬化させて重合膜を得た。
[3] Application to Support Substrate The polymerizable composition solution prepared in [1] above was applied on the support substrate manufactured in [2] using a spin coater. The coating was carried out by adjusting the rotation speed and time of the spin coater so that the film thickness was about 1.0 μm. After coating, it was dried at 100 ° C. for 3 minutes using a hot plate and cooled at room temperature for 3 minutes, and then irradiated with a high-pressure mercury lamp (120 W / cm) for 20 seconds to cure the film to obtain a polymer film.
〔実施例１−１〜１−３、比較例１−１〜１−３〕
上記の方法で得られた重合膜について、下記の試験を実施し、これらの結果について下記表１に併せて示す。
（１）リターデーション（Ｒ）
上記製造例１で得た重合膜に対して、偏光顕微鏡を用いてセナルモン法に基づく複屈折測定法に従い、室温２５℃で波長５４６ｎｍにおけるリターデーション（Ｒ）を測定した。
[Examples 1-1 to 1-3, Comparative Examples 1-1 to 1-3]
The polymer film obtained by the above method was subjected to the following test, and the results are also shown in Table 1 below.
(1) Retardation (R)
For the polymer film obtained in Production Example 1, retardation (R) at a wavelength of 546 nm was measured at room temperature of 25 ° C. according to a birefringence measurement method based on the Senarmon method using a polarizing microscope.
（２）膜厚（ｄ）
得られた重合膜に対して、触針式表面形状測定器（Ｄｅｋｔａｋ６Ｍ；（株）アルバック製）を用いて室温２５℃で膜厚（ｄ）を測定した。
(2) Film thickness (d)
With respect to the obtained polymer film, the film thickness (d) was measured at a room temperature of 25 ° C. using a stylus type surface shape measuring instrument (Dektak 6M; manufactured by ULVAC, Inc.).
（３）光学（屈折率）異方性（△ｎ）
重合膜の光学（屈折率）異方性は、下記式（４）のリターデーション関係式において上記のリターデーション（Ｒ）及び膜厚（ｄ）を代入して算出した。
光学（屈折率）異方性（Δｎ）＝リターデーション（Ｒ）／膜厚（ｄ）・・（４）
(3) Optical (refractive index) anisotropy (Δn)
The optical (refractive index) anisotropy of the polymer film was calculated by substituting the above retardation (R) and film thickness (d) in the retardation relational expression of the following formula (4).
Optical (refractive index) anisotropy (Δn) = retardation (R) / film thickness (d) (4)
（４）均質性
重合膜の均質性について偏光顕微鏡を用いて評価した。試料を、クロスニコル下で重合膜を設置したステージを回転させることによって、重合膜の配向状態を観察し、膜の均質性について評価した。重合膜の配向が均一に得られていれば○、配向が得られても不均一であれば△、重合膜に結晶等が発生して配向が全く得られていなければ×とした。
(4) Homogeneity The homogeneity of the polymer film was evaluated using a polarizing microscope. The orientation of the polymer film was observed by rotating the stage on which the polymer film was placed under crossed Nicols, and the homogeneity of the film was evaluated. If the orientation of the polymer film was obtained uniformly, it was evaluated as ◯, if the orientation was obtained, it was Δ if it was not uniform, and if the orientation was not obtained at all due to the formation of crystals or the like in the polymer film.
（５）製膜の安定性
上記重合性組成物溶液をスピンコーターで塗工し、ホットプレートを用いて１００℃で３分間乾燥後直ちに２５℃の室温下に放置し、液晶状態の安定性を評価した。安定性の評価は、室温下に放置後３０分間以上液晶状態を保った場合は○、１５分を超えて３０分までに結晶が析出した場合は△、１５分以内に結晶が析出した場合は×とした。
(5) Stability of film formation The above polymerizable composition solution was applied with a spin coater, dried at 100 ° C. for 3 minutes using a hot plate, and immediately left at room temperature of 25 ° C. to stabilize the liquid crystal state. evaluated. The stability is evaluated as ○ when the liquid crystal state is maintained for 30 minutes or more after being left at room temperature, Δ when the crystal is precipitated by more than 15 minutes and 30 minutes, and when the crystal is precipitated within 15 minutes. X.
〔実施例２−１〜２−３，比較例２−１、２−２〕
下記表２に記載の重合性組成物を製造例１と同様にして重合膜を作製し、均質性及び製膜の安定性を評価した。これらの結果について下記表２に併せて示す。
[Examples 2-1 to 2-3, comparative examples 2-1 and 2-2]
Polymeric films of the polymerizable compositions described in Table 2 below were prepared in the same manner as in Production Example 1, and the homogeneity and film formation stability were evaluated. These results are also shown in Table 2 below.
〔実施例３−１及び３−２、比較例３−１〕
下記表３に記載の重合性組成物１．０ｇを溶媒（メチルエチルケトン）４ｇに添加して溶解した後、ラジカル重合開始剤（Ｎ−１９１９；株式会社ＡＤＥＫＡ製）０．０２２５ｇを加え、完全に溶解させた後に０．１μｍフィルターでろ過処理を実施して溶液を調製し、上記製造例１で製作した支持基板上にスピンコーターで調整した溶液を均一に塗工し、ホットプレートを用いて１００℃で３分間乾燥後、室温下で１分間冷却し、高圧水銀灯（１２０Ｗ／ｃｍ）で２０秒間照射して硬化させることによって重合膜を得た。得られた重合膜について選択反射と膜の均質性の評価を実施した。これらの結果について下記表３に併せて示す。
[Examples 3-1 and 3-2, Comparative Example 3-1]
After adding 1.0 g of the polymerizable composition shown in Table 3 below to 4 g of a solvent (methyl ethyl ketone) and dissolving, 0.0225 g of a radical polymerization initiator (N-1919; manufactured by ADEKA Corporation) is added and completely dissolved. After that, a solution is prepared by performing a filtration treatment with a 0.1 μm filter, and the solution prepared with a spin coater is uniformly applied onto the support substrate produced in Production Example 1 above, and is heated to 100 ° C. using a hot plate. After drying for 3 minutes, it was cooled at room temperature for 1 minute and cured by irradiation with a high-pressure mercury lamp (120 W / cm) for 20 seconds to obtain a polymerized film. The obtained polymerized film was evaluated for selective reflection and film homogeneity. These results are also shown in Table 3 below.
上記表１より、重合性組成物として、本発明以外の単官能（メタ）アクリレート化合物（比較化合物１又は２）及び本発明の二官能（メタ）アクリレート化合物を含有するもの（比較例１−１及び１−２）、並びに本発明の単官能（メタ）アクリレート化合物及び本発明以外の二官能（メタ）アクリレート化合物（比較化合物３）を含有するもの（比較例１−３）から作製された重合膜は、均質な膜が得られなかったり、結晶が析出したりして満足できるものが得られないのに対し、本発明の重合性組成物から作製された重合膜は、実施例１−１〜１−３より、配向制御及び製膜の安定性において優れた効果が得られた。 From Table 1 above, the polymerizable composition containing a monofunctional (meth) acrylate compound other than the present invention (Comparative Compound 1 or 2) and the bifunctional (meth) acrylate compound of the present invention (Comparative Example 1-1) And 1-2), and a polymerization prepared from a monofunctional (meth) acrylate compound of the present invention and a bifunctional (meth) acrylate compound other than the present invention (Comparative Compound 3) (Comparative Example 1-3) As for the film, a homogeneous film cannot be obtained, or a satisfactory film cannot be obtained due to precipitation of crystals. On the other hand, the polymer film prepared from the polymerizable composition of the present invention has a thickness of Example 1-1. From 1-3, the outstanding effect in orientation control and stability of film formation was acquired.
上記表２より、上記一般式（１）で表される単官能（メタ）アクリレート化合物及び上記一般式（３）で表される二官能（メタ）アクリレート化合物を含有する重合性組成物において、単官能（メタ）アクリレート化合物の比率が５より少ないと製膜の安定性が悪化し（比較例２−１）、上記一般式（３）で表される二官能（メタ）アクリレート化合物の比率が５０より少ないと（比較例２−２）配向状態が悪く、膜の硬化も不安定であったのに対し、本発明の重合性組成物は均一な膜状態を維持し、光学的特性に優れた重合膜を得られることを確認した。 From the above Table 2, in the polymerizable composition containing the monofunctional (meth) acrylate compound represented by the general formula (1) and the bifunctional (meth) acrylate compound represented by the general formula (3), When the ratio of the functional (meth) acrylate compound is less than 5, the stability of the film formation deteriorates (Comparative Example 2-1), and the ratio of the bifunctional (meth) acrylate compound represented by the general formula (3) is 50. When less (Comparative Example 2-2), the orientation state was poor and the film was unstable in curing, whereas the polymerizable composition of the present invention maintained a uniform film state and was excellent in optical characteristics. It was confirmed that a polymerized film could be obtained.
上記表３より、本発明の重合膜（実施例３−１及び３−２）は、赤色の選択反射が重合膜の全面にわたって、良好な配向が得られていることを確認できたのに対し、本発明の単官能（メタ）アクリレート化合物を含まない重合膜（比較例３−１）は、選択反射が確認されるものの、ムラがあり配向が不均一であることが確認された。以上より、本発明の重合性組成物にさらに光学活性化合物を含有させることによって、コレステリック液晶の重合膜作製用材料として好適に用いることができることが明らかである。また、本発明の重合膜は均一な光学特性を必要とするディスプレイ用光学フィルムに好適に用いることができる。 From Table 3 above, the polymer films (Examples 3-1 and 3-2) of the present invention confirmed that the red selective reflection had a good orientation over the entire surface of the polymer film. The polymer film containing no monofunctional (meth) acrylate compound of the present invention (Comparative Example 3-1) was confirmed to have unevenness and non-uniform orientation although selective reflection was confirmed. From the above, it is clear that the polymerizable composition of the present invention can be suitably used as a material for preparing a polymer film of a cholesteric liquid crystal by further containing an optically active compound. In addition, the polymer film of the present invention can be suitably used for an optical film for display that requires uniform optical characteristics.
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