JP2004029062A - Liquid crystal composition and liquid crystal phase difference film using the same - Google Patents
Liquid crystal composition and liquid crystal phase difference film using the same Download PDFInfo
- Publication number
- JP2004029062A JP2004029062A JP2002180700A JP2002180700A JP2004029062A JP 2004029062 A JP2004029062 A JP 2004029062A JP 2002180700 A JP2002180700 A JP 2002180700A JP 2002180700 A JP2002180700 A JP 2002180700A JP 2004029062 A JP2004029062 A JP 2004029062A
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- JP
- Japan
- Prior art keywords
- liquid crystal
- retardation film
- film
- composition
- 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.)
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 121
- 239000000203 mixture Substances 0.000 title claims abstract description 75
- 150000001875 compounds Chemical class 0.000 claims abstract description 68
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 18
- 239000012298 atmosphere Substances 0.000 claims description 8
- 238000010030 laminating Methods 0.000 claims description 7
- 230000003287 optical effect Effects 0.000 abstract description 6
- 230000007774 longterm Effects 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 41
- -1 acrylate compound Chemical class 0.000 description 21
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 13
- 239000003999 initiator Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 229920006254 polymer film Polymers 0.000 description 10
- 239000007795 chemical reaction product Substances 0.000 description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 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 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 210000002858 crystal cell Anatomy 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
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- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 3
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 2
- MLKIVXXYTZKNMI-UHFFFAOYSA-N 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one Chemical compound CCCCCCCCCCCCC1=CC=C(C(=O)C(C)(C)O)C=C1 MLKIVXXYTZKNMI-UHFFFAOYSA-N 0.000 description 2
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 2
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-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
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 229920005994 diacetyl cellulose Polymers 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- NGAZZOYFWWSOGK-UHFFFAOYSA-N heptan-3-one Chemical compound CCCCC(=O)CC NGAZZOYFWWSOGK-UHFFFAOYSA-N 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000000787 lecithin Substances 0.000 description 2
- 229940067606 lecithin Drugs 0.000 description 2
- 235000010445 lecithin Nutrition 0.000 description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 2
- 150000002848 norbornenes Chemical class 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
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- 239000004417 polycarbonate Substances 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- ULPMRIXXHGUZFA-UHFFFAOYSA-N (R)-4-Methyl-3-hexanone Natural products CCC(C)C(=O)CC ULPMRIXXHGUZFA-UHFFFAOYSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
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- AKSHNAJMGFSDRD-UHFFFAOYSA-N 2,2-dimethoxy-1,2-diphenylethanone 2-hydroxy-1,2-diphenylethanone Chemical class C1(=CC=CC=C1)C(=O)C(O)C1=CC=CC=C1.COC(C(=O)C1=CC=CC=C1)(C1=CC=CC=C1)OC AKSHNAJMGFSDRD-UHFFFAOYSA-N 0.000 description 1
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- UXCIJKOCUAQMKD-UHFFFAOYSA-N 2,4-dichlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC(Cl)=C3SC2=C1 UXCIJKOCUAQMKD-UHFFFAOYSA-N 0.000 description 1
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- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
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- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
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- QPXVRLXJHPTCPW-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-(4-propan-2-ylphenyl)propan-1-one Chemical compound CC(C)C1=CC=C(C(=O)C(C)(C)O)C=C1 QPXVRLXJHPTCPW-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
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- AGNTUZCMJBTHOG-UHFFFAOYSA-N 3-[3-(2,3-dihydroxypropoxy)-2-hydroxypropoxy]propane-1,2-diol Chemical compound OCC(O)COCC(O)COCC(O)CO AGNTUZCMJBTHOG-UHFFFAOYSA-N 0.000 description 1
- PFCHFHIRKBAQGU-UHFFFAOYSA-N 3-hexanone Chemical compound CCCC(=O)CC PFCHFHIRKBAQGU-UHFFFAOYSA-N 0.000 description 1
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- YDIYEOMDOWUDTJ-UHFFFAOYSA-N 4-(dimethylamino)benzoic acid Chemical compound CN(C)C1=CC=C(C(O)=O)C=C1 YDIYEOMDOWUDTJ-UHFFFAOYSA-N 0.000 description 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、液晶化合物を用いた位相差フィルムに関する。
【０００２】
【従来の技術】
位相差フィルムは、例えば、直線偏光を円偏光や楕円偏光に変換する機能を有するフィルムであり、偏光フィルムと粘着剤などを用いて積層した形態で、主に液晶ディスプレイ（ＬＣＤ）のコントラスト改善や、視野角特性の改善のために使用されている。この位相差フィルムは、従来、高分子フィルムを一軸または二軸延伸して作製されていたが、近年、重合性液晶化合物を特定の方向に配向させた後、重合等によって該配向状態を固定化させて作製する手法が開発されている。そのような例としては例えば、特表２０００−５１４２０２号や特開平１０−３１９４０８等が挙げられる。このような液晶化合物を用いてその配向を制御することにより、従来の延伸によって作製していた位相差フィルムでは実現することが困難な屈折率異方性を有する位相差フィルムを作製することができる。
【０００３】
【発明が解決しようとする課題】
位相差フィルムは、偏光フィルム等の他のフィルムとともにＬＣＤ等の画像表示装置に用いられるが、この画像表示装置が長期間、一定の表示機能を維持するためには使用される各フィルムにおいても長期間一定の特性を維持するための耐久性が要求される。この要求される耐久性とは、通常、高温乾熱雰囲気下または高湿熱雰囲気下に一定時間放置した後の光学特性（例えば、位相差フィルムであれば位相差値）が初期の光学特性をどの程度維持しているかどうかを調べる、いわゆる加速試験によって評価される。この温度、湿度、時間は、要求される耐久性によって異なるが、この耐久性を満足できなければ、例え、優れた初期光学特性をもつ位相差フィルムであっても、実際には使用することができない。特表２０００−５１４２０２号公報では反応性メソゲン化合物に２個または３個以上の重合性官能基を有する非メソゲン化合物を２０％までの量で含有することにより、ガラス転移温度や、熱および機械的安定性を変えることができると述べている。しかしながら、このような特性を変えることができるとしても、位相差フィルムとして実際に使用する上で重要な位相差値に対しては十分な耐久性を有してはいなかった。
【０００４】
【課題を解決するための手段】
本発明者らは、上記の課題を解決すべく鋭意検討を行った結果、１種以上の重合性液晶化合物と１種以上の一分子内に６個以上の重合性基を有する非液晶性の重合性化合物を含む非液晶性の重合性化合物の混合物および重合開始剤からなる液晶性組成物を用い、この層を基板上に形成し、特定の方向に配向させた後、該配向状態を固定化させた位相差フィルムを用いることにより、位相差値の変化を十分に抑え、耐久性を大幅に向上させることができることを新規に見出した。すなわち、本発明は、
（１）１種以上の重合性液晶化合物と１種以上の一分子内に６個以上の重合性基を有する非液晶性の重合性化合物を含む非液晶性の重合性化合物の混合物および重合開始剤を含有し、重合性液晶性化合物と非液晶性の重合性化合物の混合物との混合比が前者が８５重量％以上９９重量％以下で後者が１重量％以上１５重量％以下である液晶位相差フィルム用組成物、
（２）非液晶性の重合性化合物の混合物が１種以上の一分子内に６個以上の重合性基を有する非液晶性の重合性化合物と１種以上の一分子内に６個未満の重合性基を有する非液晶性の重合性化合物からなり、前者が５０重量％以上、後者が５０重量％未満であることを特徴とする（１）に記載の液晶位相差フィルム用組成物、
（３）（１）または（２）のいずれか１項に記載の液晶位相差フィルム用組成物からなる層を、該組成物層が特定の方向に配向させることができるように処理された基板上に形成し、特定の方向に配向させた後、重合により該配向状態を固定化させて得られる液晶位相差フィルム、
（４）液晶位相差フィルムの初期のある波長における位相差値をＲｒｅｆ、温度８５℃の乾熱雰囲気下で２４時間放置後の該組成物層の該放置前と同じ波長における位相差値をＲｄｕｒとしたとき、位相差値の変化率Ｒｃが下記式［１］を満たすことを特徴とする（３）に記載の液晶位相差フィルム、
｜（Ｒｒｅｆ−Ｒｄｕｒ）／Ｒｒｅｆ｜＝Ｒｃ≦０．１０ ［１］
（５）（３）または（４）のいずれか１項に記載の液晶位相差フィルムと他の位相差フィルムとを積層してなる積層位相差フィルム、
（６）（３）または（５）のいずれか１項に記載の液晶位相差フィルムまたは積層位相差フィルムと偏光フィルムを積層してなる積層偏光フィルム、
（７）（３）ないし（６）のいずれか１項に記載の液晶位相差フィルムまたは積層位相差フィルムまたは積層偏光フィルムを有する画像表示装置、
に関する。
【０００５】
【発明の実施の形態】
本発明で用いられる液晶位相差フィルム用組成物を構成する重合性液晶化合物とは、（メタ）アクリロイル基やエポキシ基といった重合可能な置換基を有し、ある温度範囲で液晶性を示し、重合開始剤の存在下で重合することが可能な化合物である。そのような化合物としては、例えば、特表２０００−５１４２０２号や、特開２００２−６９４５０号、ＷＯ９７／４４７０３号公報に記載の液晶アクリレート化合物またはエポキシ基を有する棒状の液晶化合物およびその混合物や特開平９−５２９６２号公報に記載のディスコティック液晶性を示す液晶アクリレート化合物等が挙げられるが、光重合開始剤の存在下で紫外線で重合が可能である液晶アクリレート化合物が好ましく、棒状の液晶化合物およびその混合物であることがより好ましい。このような液晶アクリレートは、１種でも使用可能であるが、液晶性を示す温度領域を拡大するためや、複屈折性を制御するために、通常２種以上の混合物で用いることが好ましい。
【０００６】
本発明で用いられる液晶位相差フィルム用組成物を構成する一分子内に６個以上の重合性基を有する非液晶性の重合性化合物としては、例えば、（メタ）アクリロイル基やエポキシ基といった重合可能な置換基を一分子内に６個以上有する化合物であり、通常の環境下では液晶性を示さない。そのような化合物としては、例えば、ジペンタエリスリトールヘキサ（メタ）アクリレート（一分子内のアクリロイル基数：６個）や、ジペンタエリスリトールペンタ（メタ）アクリレートと１，６−ヘキサメチレンジイソシアネートとの反応生成物（一分子内のアクリロイル基数：１０個）、イソシアヌル環を有するトリイソシアネートとペンタエリスリトールトリ（メタ）アクリレートとの反応性生物（一分子内のアクリロイル基数：９個）、ペンタエリスリトールトリ（メタ）アクリレートとイソホロンジイソシアネートとの反応生成物（一分子内のアクリロイル基数：６個）等が挙げられる。これらは単独でも複数の混合物としても使用することができる。
【０００７】
本発明で用いられる液晶位相差フィルム用組成物には、少なくとも１種の上記一分子内に６個以上の重合性基を有する非液晶性の重合性化合物を含んでいれば、一分子内に６個未満の重合性基を有する非液晶性の重合性化合物を含んでいても良い。一分子内に６個未満の重合性基を有する非液晶性の重合性化合物としては、例えば、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスルトールテトラ（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、ペンタエリスルトールトリ（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、ジトリメチロールプロパンテトラ（メタ）アクリレート、トリス（アクリロキシエチル）イソシアヌレート、トリス（メタアクリロキシエチル）イソシアヌレート、グリセロールトリグリシジルエーテルと（メタ）アクリル酸との反応生成物、カプロラクトン変性トリス（アクリロキシエチル）イソシアヌレート、トリメチロールプロパントリグリシジルエーテルと（メタ）アクリル酸との反応生成物、トリグリセロールジ（メタ）アクリレート、プロピレングリコールジグリシジルエーテルと（メタ）アクリル酸との反応生成物、ポリプロピレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（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、テトラエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、１，６−ヘキサンジオールジグリシジルエーテルと（メタ）アクリル酸との反応生成物、１，６−ヘキサンジオールジ（メタ）アクリレート、グリセロールジ（メタ）アクリレート、エチレングリコールジグリシジルエーテルと（メタ）アクリル酸との反応生成物、ジエチレングリコールジグリシジルエーテルと（メタ）アクリル酸との反応生成物、ビス（アクリロキシエチル）ヒドロキシエチルイソシアヌレート、ビス（メタアクリロキシエチル）ヒドロキシエチルイソシアヌレート、ビスフェノールＡジグリシジルエーテルと（メタ）アクリル酸との反応性生物、テトラヒドロフルフリル（メタ）アクリレート、カプロラクトン変性テトラヒドロフルフリル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、ポリプロピレングリコール（メタ）アクリレート、ポリエチレングリコール（メタ）アクリレート、フェノキシヒドロキシプロピル（メタ）アクリレート、アクリロイルモルホリン、メトキシポリエチレングリコール（メタ）アクリレート、メトキシテトラエチレングリコール（メタ）アクリレート、メトキシトリエチレングリコール（メタ）アクリレート、メトキシエチレングリコール（メタ）アクリレート、メトキシエチル（メタ）アクリレート、グリシジル（メタ）アクリレート、グリセロール（メタ）アクリレート、エチルカルビトール（メタ）アクリレート、２−エトキシエチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、２−シアノエチル（メタ）アクリレート、ブチルグリシジルエーテルと（メタ）アクリル酸との反応生成物、ブトキシトリエチレングリコール（メタ）アクリレート、ブタンジオールモノ（メタ）アクリレート等が挙げられる。これらは、上記一分子内に６個以上の重合性基を有する非液晶性の重合性化合物と共に、単独でも複数の混合物としても使用することができる。
【０００８】
本発明の液晶位相差フィルム用組成物は、前記重合性液晶性化合物と、１種以上の一分子内に６個以上の重合性基を有する非液晶性の重合性化合物および必要に応じて１種以上の一分子内に６個未満の重合性基を有する非液晶性の重合性化合物と重合開始剤を混合して得られる。重合性液晶性化合物と非液晶性の重合性化合物との混合比は、各々の化合物の相溶性や、該組成物からなる層を基板上に形成し、特定の方向に配向させたときに、該層の配向性と透明性を維持するために、前者が８５重量％以上９９重量％以下で後者が１重量％以上１５重量％以下、好ましくは、前者が９０重量％以上９５重量％以下で後者が５重量％以上１０重量％以下となるように混合するのが良い。
【０００９】
さらに、一分子内に６個以上の重合性基を有する非液晶性の重合性化合物と一分子内に６個未満の重合性基を有する非液晶性の重合性化合物との割合は、本発明の目的である位相差値の変化に対する耐久性を向上させるために、前者が５０重量％以上、後者が５０重量％未満、より好ましくは前者が６０重量％以上、後者が４０重量％未満になるようにするのがよい。
【００１０】
本発明の液晶位相差フィルム用組成物に用いられる重合開始剤としては、該組成物を紫外線により重合させる場合、光重合開始剤が用いられる。光重合開始剤としては例えば、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルホリノプロパン−１（チバスペシャリティーケミカルズ製イルガキュアー９０７）、１−ヒドロキシシクロヘキシルフェニルケトン（チバスペシャリティーケミカルズ製イルガキュアー１８４）、４−（２−ヒドロキシエトキシ）−フェニル（２−ヒドロキシ−２−プロピル）ケトン（チバスペシャリティーケミカルズ製イルガキュアー２９５９）、１−（４−ドデシルフェニル）−２−ヒドロキシ−２−メチルプロパン−１−オン（メルク製ダロキュアー９５３）、１−（４−イソプロピルフェニル）−２−ヒドロキシ−２−メチルプロパン−１−オン（メルク製ダロキュアー１１１６）、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン（チバスペシャリティーケミカルズ製イルガキュアー１１７３）、ジエトキシアセトフェノン等のアセトフェノン系化合物、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル、２，２−ジメトキシ−２−フェニルアセトフェノン（チバスペシャリティーケミカルズ製イルガキュアー６５１）等のベンゾイン系化合物、ベンゾイル安息香酸、ベンゾイル安息香酸メチル、４−フェニルベンゾフェノン、ヒドロキシベンゾフェノン、４−ベンゾイル−４’−メチルジフェニルサルファイド、３，３’−ジメチル−４−メトキシベンゾフェノン（日本化薬製カヤキュアーＭＢＰ）等のベンゾフェノン系化合物、チオキサンソン、２−クロルチオキサンソン（日本化薬製カヤキュアーＣＴＸ）、２−メチルチオキサンソン、２，４−ジメチルチオキサンソン（カヤキュアーＲＴＸ）、イソプロピルチオキサンソン、２，４−ジクロオチオキサンソン（日本化薬製カヤキュアーＣＴＸ）、２，４−ジエチルチオキサンソン（日本化薬製カヤキュアーＤＥＴＸ）、２，４−ジイソプロピルチオキサンソン（日本化薬製カヤキュアーＤＩＴＸ）等のチオキサンソン系化合物等が挙げられる。これらの光重合開始剤は１種類でも複数でも任意の割合で混合して使用することができる。
【００１１】
ベンゾフェノン系化合物やチオキサンソン系化合物を用いる場合には、光重合反応を促進させるために、助剤を併用することも可能である。そのような助剤としては例えば、トリエタノールアミン、メチルジエタノールアミン、トリイソプロパノールアミン、ｎ−ブチルアミン、Ｎ−メチルジエタノールアミン、ジエチルアミノエチルメタアクリレート、ミヒラーケトン、４，４’―ジエチルアミノフェノン、４−ジメチルアミノ安息香酸エチル、４−ジメチルアミノ安息香酸（ｎブトキシ）エチル、４−ジメチルアミノ安息香酸イソアミル等のアミン系化合物が挙げられる。
【００１２】
前記光重合開始剤および助剤は直接重合しないため液晶層に存在する。従って、光重合開始剤の添加量は、後の液晶性化合物の配向および耐久性に影響を与えない範囲で使用することが好ましく、その量は、該組成物中の全（メタ）アクリレート化合物１００重量部に対して、好ましくは０．５重量部以上２０重量部以下、より好ましくは２重量部以上１５重量部以下がよい。また、助剤は光重合開始剤に対して、０．５倍から２倍量程度がよい。
【００１３】
このようにして得られた本発明の液晶位相差フィルム用組成物を用い、該組成物を直接または適当な溶剤を用いて希釈し、該組成物層が特定の方向に配向させることができるように処理された基板上に塗布する。その後加熱等により溶剤を除去し、次いで該組成物層を特定の方向に配向させた後、紫外線を照射する等して重合し、該配向状態を固定化することにより、本発明の液晶位相差フィルムを得ることができる。塗布する際に用いられる該組成物の溶液の溶剤としては、該組成物の溶解性、塗布時の基板上へのぬれ性に優れ、基板に対して塗布後の該組成物層の配向に影響を与えるほどの著しい表面性の低下を起こさないものであれば特に制限はない。そのような溶剤としては、例えば、トルエン、キシレン等の芳香族炭化水素類、アニソール、ジオキサン、テトラヒドロフラン等のエーテル類、メチルイソブチルケトン、メチルエチルケトン、シクロヘキサノン、シクロペンタノン、２−ペンタノン、３−ペンタノン、２−ヘキサノン、３−ヘキサノン、２−ヘプタノン、３−ヘプタノン、４−ヘプタノン、２，６−ジメチル−４−ヘプタノン等のケトン類、ｎ−ブタノール、２−ブタノール、シクロヘキサノール、イソプロピルアルコール等のアルコール類、メチルセロソルブ、酢酸メチルセロソルブ等のセロソルブ類、酢酸エチル、酢酸ブチル、乳酸メチル等のエステル類が挙げられるがこれらに限定されない。また、溶剤は単一でも混合物でもよい。該組成物を溶解する際の該組成物の濃度は溶剤溶解性、基板上へのぬれ性、塗布後の厚みなどによって異なるが、好ましくは５〜９５重量％、より好ましくは１０〜８０重量％程度がよい。
【００１４】
また、基板上へ塗布する際、該基板上へのぬれ性が乏しい場合や、形成された液晶組成物層の表面性が悪い場合は、それらを改善するために該組成物中に種々のレベリング剤を添加することも可能である。レベリング剤の種類としては、シリコン系、フッ素系、ポリエーテル系、アクリル酸共重合物系、チタネート系等の種々の化合物を用いることができる。これらのレベリング剤の添加量は、該組成物１００重量部中に０．０００１重量部以上０．００５重量部以下、より好ましくは該組成物１００重量部中に０．０００５重量部以上０．００３重量部以下程度がよい。
【００１５】
本発明の液晶位相差フィルム用組成物またはその溶液を基板に塗布する方法は特に限定されないが、得られる本発明の位相差フィルムの厚さが位相差値に影響するため、該組成物層の表面は極力平滑であることが好ましい。そのような該組成物層を得るための塗布方法としては、例えば、スピンコート方式、ワイヤーバーコート方式、グラビアコート方式、マイクログラビアコート方式、カレンダーコート方式、スプレーコート方式、メニスカスコート方式等などによる方法が挙げられる。該組成物層の厚さは、所望とする位相差値によって異なるために適宜定められるが、溶剤除去後の厚さが、好ましくは０．０１〜２０μｍ、より好ましくは０．０５〜１０μｍ程度がよく、そのような膜厚は溶液の濃度や塗布方法、塗布条件を調節することにより達成される。
【００１６】
本発明に用いられる液晶位相差フィルム用組成物を特定の方向に配向させる際の特定の方向とは、フィルム内のある方向と他の方向で屈折率の異方性が現れるような方向であり、本発明の液晶位相差フィルムにおいては、フィルム面内または厚さ方向で屈折率が最大となる方向を示す。該組成物を特定の方向に配向させることができるように処理された基板としては、例えば、ラビング処理された高分子フィルムや高分子フィルムに配向膜を形成し、必要に応じて該配向膜をさらにラビング処理した高分子フィルム等が挙げられる。高分子フィルムとしては、本発明の液晶組成物およびその溶液のぬれ性に優れ、得られる位相差フィルムの光学特性を低下させない程度の平滑性を有するものが好ましい。そのような高分子フィルムとしては例えば、ジアセチルセルロース、トリアセチルセルロース等のセルロース誘導体を主成分とするフィルムや、ノルボルネン誘導体などのシクロオレフィンポリマーを主成分とするフィルム、ポリエチレンテレフタレート、ポリエチレンナフタレート等のポリエステルを主成分とするフィルム、ポリカーボネートおよびその誘導体を主成分とするフィルム、ポリプロピレン、ポリエチレン等のポリアルキレンおよびその誘導体を主成分とするフィルム等が挙げられる。これらのフィルムは、一軸、若しくは二軸に延伸されていても良い。また、配向膜としては、本発明の液晶組成物およびその溶液のぬれ性に優れ、該組成物を特定の方向に配向させることができるものが好ましい。そのような配向膜としては、例えば、ポリアミド、ポリイミド、レシチン、シリカ、ポリビニルアルコール、エステル変性ポリビニルアルコール、ポリ酢酸ビニルの鹸化度を調節したポリマー、シランカップリング剤等を塗布等して形成した配向膜や、高分子フィルム上にアルミニウムや酸化アルミニウムを塗布または蒸着させた配向膜等が挙げられる。これら配向膜は、配向させたい方向にラビング処理を施すことで、該組成物を特定の方向、例えばラビング方向に配向させることができる。また、レシチン、シリカ、シランカップリング剤、アルミニウムや酸化アルミニウムを用いた配向膜を用いた場合は、ラビング処理などをすることなく、該組成物を基板面に対して垂直方向に配向させることができる。
【００１７】
上記該組成物層は、前記特定の方向に配向させることができるように処理された基板状に形成された際、加熱乾燥による溶剤除去と同時に、または溶剤除去後、液晶性を示す温度領域で一定時間放置させることにより、特定の方向に配向することができる。次いで、紫外線により重合させる場合であれば、該配向状態を維持できる条件下で紫外線を照射することにより該配向状態を維持したまま重合し、その結果該配向状態が固定化される。紫外線の照射量は、本発明の該組成物中の（メタ）アクリレート化合物の種類、光重合開始剤の種類と添加量、膜厚によって異なるが、１００〜１０００ｍＪ／ｃｍ２程度がよい。また、紫外線照射時の雰囲気は空気中、窒素などの不活性ガス中などが挙げられるが、膜厚が薄くなると、酸素障害により十分に硬化しないため、そのような場合は不活性ガス中で紫外線を照射して硬化させるのが好ましい。
【００１８】
このようにして得られた本発明の液晶位相差フィルムは、ある一定の位相差値を有するが、高温の乾熱雰囲気下や、高湿熱雰囲気下に一定時間放置しても該放置前の位相差値を維持することができる。具体的には、前記の方法で作製した本発明の液晶位相差フィルムの初期のある波長における位相差値をＲｒｅｆとし、温度８５℃の乾熱雰囲気下で２４時間放置後の該位相差フィルムの初期と同じ波長における位相差値をＲｄｕｒとしたとき、下記式（１）で求められる位相差値の変化率Ｒｃを一定値以下にする液晶位相差フィルムが好ましい。
｜（Ｒｒｅｆ−Ｒｄｕｒ）／Ｒｒｅｆ｜＝Ｒｃ≦０．１０ （１）
液晶性化合物が基板に対して水平方向、もしくはある角度で傾斜して配向しているときは、得られたフィルム面に対して垂直方向の位相差値が上記式（１）を満たすことができるが、液晶組成物の配向方向が基板に対して略垂直方向である場合、基板に対して垂直な方向における位相差値はほとんど０となる。そのような本発明の液晶位相差フィルムの場合には、例えば得られたフィルム面に対して垂直な方向から５０°傾斜させた時の位相差値を測定し、その値が上記式（１）を満たすことができる。このとき変化率の絶対値Ｒｃは好ましくは０．１０以下、より好ましくは０．０７以下、さらに好ましくは０．０５以下になるのが良い。また、位相差値は波長によって異なる場合があるため、位相差値を測定する波長は初期と加速試験後で同じでなければならない。好ましい波長としては、４００〜７５０ｎｍ、より好ましくは５００〜６００ｎｍ付近の波長が用いられる。本発明の液晶位相差フィルムは、前記高温雰囲気下に放置する加速試験においてもその位相差値の変化が極めて少いことから、優れた耐久性を有しており、長期間一定の光学特性を維持できる。
【００１９】
本発明の液晶位相差フィルムは、基板から粘着剤等で剥離して他の位相差フィルムと積層して使用することができる。また、基板そのものが位相差フィルムであれば、基板から剥離すること無しに使用することができる。このような本発明の液晶位相差フィルムと、他の位相差フィルムとを直接、または粘着剤や接着剤などを用いて積層することによって本発明の積層位相差フィルムが得られる。他の位相差フィルムとは、例えばポリカーボネート、ポリアリレート、ジアセチルセルロース、トリアセチルセルロース、ノルボルネン誘導体、シクロオレフィンポリマー等からなる高分子フィルムに複屈折性を付与したフィルムである。複屈折性は、該高分子フィルムの製膜時に自発的に発生する場合もあるし、該高分子フィルムを一軸または二軸に延伸することによって付与できる。
【００２０】
本発明の液晶位相差フィルムまたは積層位相差フィルムを粘着剤や接着剤などを用いて偏光フィルムと積層することによって、本発明の積層偏光フィルムが得られる。偏光フィルムは、ポリビニルアルコールのフィルムに多ヨウ素イオンや二色性染料等を含浸させ、ホウ酸温浴中にて一軸延伸して得られる偏光素子を表層がアルカリ処理されたトリアセチルセルロースフィルムでポリビニルアルコール系接着剤などを用いて挟持して得られる。本発明の液晶位相差フィルムは優れた耐久性を有しているため、同様に優れた耐久性を有する二色性染料を用いた偏光素子からなる偏光フィルムと組み合わせて用いることが特に好ましい。
【００２１】
このようにして得られた本発明の液晶位相差フィルムまたは積層位相差フィルムまたは積層偏光フィルムをＬＣＤや有機エレクトロルミネッセンスディスプレイ（有機ＥＬ）等に用いることにより本発明の画像表示装置が得られる。ＬＣＤで使用する場合は、通常偏光フィルムと組み合わせて使用されるが、ＬＣＤに用いられる液晶セルとしては、例えばツイステッドネマチック（ＴＮ）型、スーパーツイステッドネマチック（ＳＴＮ）型や、水平配向（ＥＣＢ）型、垂直配向ネマチック（ＶＡ）型、インプレーンスイッチング（ＩＰＳ）型、ベンドネマチック（ＯＣＢ）型、強誘電性液晶（ＳＳＦＬＣ）型、反強誘電液晶（ＡＦＬＣ）型液晶セルなど種々の液晶セルが挙げられる。さらにこれらの液晶セルを用いた液晶表示装置は、透過型、反射型、反射半透過型いずれの形でも使用することができる。このような種々のＬＣＤに、本発明の液晶位相差フィルムを用いることにより、コントラストや、色相、視野角特性を改善することができ、しかもその機能を長期間維持することができる。また有機ＥＬに使用する場合は、例えば、偏光フィルムと一軸延伸した位相差フィルムとを組み合わせた円偏光フィルムに本発明の垂直配向した液晶位相差フィルムを一軸延伸した位相差フィルム側に積層した形態で、画像表示面側に配置することにより、広い視野角で金属電極の反射を抑えることにより視認性を向上させることができ、しかもその機能を長期間維持することができる。
【００２２】
【実施例】
以下実施例と比較例を挙げて本発明をさらに具体的に説明する。
実施例１
【００２３】
【化１】
で示される化合物３６．６重量部、
【００２５】
【化２】
で示される化合物４２．１重量部及び
【００２７】
【化３】
で示される化合物９．３重量部を含有する紫外線硬化型液晶性化合物の混合物と光重合開始剤イルガキュアー９０７（チバスペシャリティーケミカルズ社製）１２重量部にジペンタエリスリトールヘキサアクリレート（一分子内のアクリロイル基数：６個、日本化薬製カヤラッドＤＰＳ−１００）８．８重量部をトルエン２４４．８重量部、シクロヘキサノン８１．６重量部の混合溶剤で溶解し、固形分濃度が２５％の本発明の液晶組成物の溶液を調製した。この溶液を、アルミニウムを蒸着させ、さらにアクリル系樹脂で蒸着層をコートしたポリエステルフィルムのアクリル系樹脂面にワイヤーバーを用いて均一に塗布し、加熱により溶媒を除去後、高圧水銀灯（１２０Ｗ／ｃｍ）を照射して重合させて本発明の液晶位相差フィルムを作製した。この位相差フィルムの厚さは０．８μｍであった。次に粘着剤を塗布したガラス板を用いて本発明の液晶位相差フィルムをポリエステルフィルムから剥離したところ、該位相差フィルムは透明であった。次にこのガラス板に転写した該位相差フィルムを、該位相差フィルム正面から傾斜させた時の位相差値の変化を自動複屈折測定器（王子計測機器社製：ＫＯＢＲＡ−２１ＡＤＨ）を用いて測定した。結果を図１に示した。図１より、本発明の液晶位相差フィルムは、該位相差フィルム面に対して垂直配向していることが分かった。また、該位相差フィルム面の垂直方向から５０°傾斜したときの５９０ｎｍにおける位相差値は３９．０ｎｍであった。次にこのガラス板に転写した本発明の液晶位相差フィルムを８５℃の乾熱雰囲気下に２４時間放置した。その後室温になるまで放冷した後、同様にフィルム面の垂直方向から５０°傾斜したときの５９０ｎｍにおける位相差値を測定したところ３７．３ｎｍであった。この結果から上記式（１）により変化率を求めた。結果を表１に示した。
【００２９】
実施例２
実施例１で用いたカヤラッドＤＰＳ−１００の代わりに、ジペンタエリルリトールヘキサアクリレート（一分子内のアクリロイル基数：６個）と、ジペンタエリスリトールペンタアクリレートと１，６−ヘキサメチレンジイソシアネートとの反応生成物（一分子内のアクリロイル基数：１０個）との混合物（日本化薬製カヤラッドＤＰＨＡ−４０Ｈ）を８．８重量部用いる以外は実施例１と同様の操作により、本発明の液晶位相差フィルムを得た。得られた該位相差フィルムは透明であった。また、この液晶位相差フィルムは実施例１と同様に該フィルム面に対して垂直配向していた。次にこの液晶位相差フィルムを実施例１と同様に評価した。結果を表１に示した。
【００３０】
実施例３
実施例１で用いたカヤラッドＤＰＳ−１００の代わりに、ジペンタエリスリトールヘキサアクリレート（一分子内のアクリロイル基数：６個）とジペンタエリスリトールペンタアクリレート（一分子内のアクリロイル基数：５個）との混合物（前者が６０部、後者が４０部）を８．８重量部用いる以外は実施例１と同様の操作により、本発明の液晶位相差フィルムを得た。得られた該位相差フィルムは透明であった。また、この液晶位相差フィルムは実施例１と同様に該フィルム面に対して垂直配向していた。次にこの液晶位相差フィルムを実施例１と同様に評価した。結果を表１に示した。
【００３１】
【比較例】
比較例１
実施例１で用いたカヤラッドＤＰＳ−１００の代わりに、特表２０００−５１４２０２号公報に準じて、ペンタエリスリトールテトラアクリレート（一分子内のアクリロイル基数：４個、日本化薬製カヤラッドＰＥＴ−４０）を８．８重量部用いる以外は実施例１と同様の操作により、液晶位相差フィルムを得た。得られた該位相差フィルムは透明であった。また、この液晶位相差フィルムも実施例１と同様に該フィルム面に対して垂直配向していた。次にこのフィルムを実施例１と同様に評価した。結果を表１に示した。
【００３２】
比較例２
実施例１で用いたカヤラッドＤＰＳ−１００の代わりに、特表２０００−５１４２０２号公報に準じて、ビスフェノールＡジグリシジルエーテルとアクリル酸との反応性生物（一分子内のアクリロイル基数：２個、日本化薬製カヤラッドＲ−１１５）を８．８重量部用いる以外は実施例１と同様の操作により、液晶位相差フィルムを得た。得られた該位相差フィルムは透明であった。また、この液晶位相差フィルムも実施例１と同様に該フィルム面に対して垂直配向していた。次にこのフィルムを実施例１と同様に評価した。結果を表１に示した。
【００３３】
比較例３
実施例１で用いたカヤラッドＤＰＳ−１００を用いないこと以外は実施例１と同様の操作により、液晶位相差フィルムを得た。得られた該位相差フィルムは透明であった。また、この液晶位相差フィルムも実施例１と同様に該フィルム面に対して垂直配向していた。次にこのフィルムを実施例１と同様に評価した。結果を表１に示した。
【００３４】
比較例４
実施例２で用いたカヤラッドＤＰＨＡ−４０Ｈを１７．６重量部、光重合開始剤イルガキュアー９０７（チバスペシャリティーケミカルズ社製）６重量部用いる以外は、実施例１と同様の操作を行ったが、該組成物層は配向しておらず、白濁してしまったため本発明の液晶位相差フィルムが作製できなかった。
【００３５】
【表１】
実施例１と比較例４の結果から、本発明の液晶位相差フィルム用組成物は非液晶性化合物を本発明の範囲内で加えることにより、特定の方向に配向した、透明な液晶位相差フィルムが得られることが分かる。また、比較例１、２と比較例３の結果から、特表２０００−５１４２０２号公報に記載の方法を用いても、高温の乾熱試験における位相差値の変化をある程度抑えることができるものの、十分ではない。これに対し、実施例１〜３と比較例１、２の結果から明らかなように、本発明の液晶位相差フィルムは、比較例に比べて高温の乾熱試験を行っても位相差値の変化が極めて少なく、安定した光学性能を維持していることが分かる。
【００３７】
【発明の効果】
本発明は、１種以上の重合性液晶化合物と１種以上の一分子内に６個以上の重合性基を有する非液晶性の重合性化合物を含む非液晶性の重合性化合物の混合物および重合開始剤からなり、重合性液晶性化合物と非液晶性の重合性化合物の混合物との混合比が前者が８５重量％以上９９重量％以下で後者が１重量％以上１５重量％以下である液晶位相差フィルム用組成物および、これを特定の方向に配向させて該配向状態を固定化させて得られる液晶位相差フィルムであって、このフィルムを用いることにより、長期間一定の光学特性を維持できる。
【図面の簡単な説明】
【図１】実施例１における本発明の液晶位相差フィルムの傾斜角による位相差値の変化を示したグラフである。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a retardation film using a liquid crystal compound.
[0002]
[Prior art]
The retardation film is, for example, a film having a function of converting linearly polarized light into circularly polarized light or elliptically polarized light, and is mainly formed by laminating a polarizing film and an adhesive to improve contrast of a liquid crystal display (LCD). , For improving viewing angle characteristics. Conventionally, this retardation film has been produced by uniaxially or biaxially stretching a polymer film.In recent years, after aligning a polymerizable liquid crystal compound in a specific direction, the alignment state is fixed by polymerization or the like. A method of manufacturing the semiconductor device has been developed. Such examples include, for example, JP-T-2000-514202 and JP-A-10-319408. By controlling the orientation using such a liquid crystal compound, a retardation film having a refractive index anisotropy that is difficult to be realized by a retardation film produced by conventional stretching can be produced. .
[0003]
[Problems to be solved by the invention]
A retardation film is used in an image display device such as an LCD together with another film such as a polarizing film, and in order to maintain a constant display function for a long period of time, this image display device has a long length in each film used. Durability is required to maintain constant characteristics for a period. The required durability generally means that the optical characteristics (for example, the retardation value in the case of a retardation film) after leaving for a certain period of time in a high-temperature dry heat atmosphere or a high-humidity heat atmosphere It is evaluated by a so-called accelerated test that checks whether the degree is maintained. The temperature, humidity, and time vary depending on the required durability. If the durability is not satisfied, even if the retardation film has excellent initial optical characteristics, it can be actually used. Can not. JP-T-2000-514202 discloses that a reactive mesogen compound contains a non-mesogen compound having two or more than three polymerizable functional groups in an amount of up to 20%, thereby increasing the glass transition temperature, heat and mechanical properties. States that the stability can be changed. However, even if such characteristics can be changed, the film does not have sufficient durability with respect to a retardation value which is important for actually using the film as a retardation film.
[0004]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that one or more polymerizable liquid crystal compounds and one or more polymerizable non-liquid crystal compounds having six or more polymerizable groups in one molecule. Using a liquid crystal composition comprising a mixture of a non-liquid crystal polymerizable compound containing a polymerizable compound and a polymerization initiator, this layer is formed on a substrate, and after being oriented in a specific direction, the alignment state is fixed. It has been newly discovered that the use of the retardation film formed as above makes it possible to sufficiently suppress the change in the retardation value and greatly improve the durability. That is, the present invention
(1) A mixture of one or more polymerizable liquid crystal compounds and one or more non-liquid crystal polymerizable compounds including a non-liquid crystal polymerizable compound having six or more polymerizable groups in one molecule and initiation of polymerization And a mixture ratio of a polymerizable liquid crystal compound and a non-liquid crystal polymerizable compound is 85% to 99% by weight and the latter is 1% to 15% by weight. Composition for phase difference film,
(2) A mixture of a non-liquid crystal polymerizable compound and a non-liquid crystal polymerizable compound having 6 or more polymerizable groups in one or more molecules and less than 6 in one or more molecules. The composition for a liquid crystal retardation film according to (1), comprising a non-liquid crystal polymerizable compound having a polymerizable group, wherein the former is 50% by weight or more and the latter is less than 50% by weight,
(3) A substrate obtained by treating a layer comprising the composition for a liquid crystal retardation film according to any one of (1) and (2) so that the composition layer can be oriented in a specific direction. Formed on top, after being oriented in a specific direction, a liquid crystal retardation film obtained by fixing the orientation state by polymerization,
(4) The initial retardation value of the liquid crystal retardation film at a certain wavelength is Rref, and the retardation value of the composition layer after standing for 24 hours in a dry heat atmosphere at a temperature of 85 ° C. is Rdur at the same wavelength as before the standing. Wherein the rate of change Rc of the retardation value satisfies the following formula [1], wherein the liquid crystal retardation film according to (3),
| (Rref−Rdur) /Rref|=Rc≦0.10 [1]
(5) a laminated retardation film obtained by laminating the liquid crystal retardation film according to any one of (3) or (4) and another retardation film;
(6) a laminated polarizing film obtained by laminating a polarizing film with a liquid crystal retardation film or a laminated retardation film according to any one of (3) and (5);
(7) An image display device having the liquid crystal retardation film, the laminated retardation film, or the laminated polarizing film according to any one of (3) to (6),
About.
[0005]
BEST MODE FOR CARRYING OUT THE INVENTION
The polymerizable liquid crystal compound constituting the composition for a liquid crystal retardation film used in the present invention has a polymerizable substituent such as a (meth) acryloyl group or an epoxy group, exhibits liquid crystallinity in a certain temperature range, It is a compound that can be polymerized in the presence of an initiator. Examples of such compounds include liquid crystal acrylate compounds described in JP-T-2000-514202, JP-A-2002-69450 and WO97 / 44703, rod-like liquid crystal compounds having an epoxy group, and mixtures thereof, and JP-A-Hei. Examples of the liquid crystal acrylate compound exhibiting discotic liquid crystallinity described in JP-A-9-52962 include a liquid crystal acrylate compound that can be polymerized by ultraviolet light in the presence of a photopolymerization initiator, and a rod-shaped liquid crystal compound and More preferably, it is a mixture. Such a liquid crystal acrylate can be used alone, but it is usually preferable to use a mixture of two or more kinds in order to expand a temperature range exhibiting liquid crystallinity and to control birefringence.
[0006]
Examples of the non-liquid crystalline polymerizable compound having 6 or more polymerizable groups in one molecule constituting the composition for a liquid crystal retardation film used in the present invention include, for example, a polymerizable compound such as a (meth) acryloyl group or an epoxy group. It is a compound having six or more possible substituents in one molecule and does not exhibit liquid crystallinity under a normal environment. Examples of such a compound include dipentaerythritol hexa (meth) acrylate (the number of acryloyl groups in one molecule: 6), and the reaction product of dipentaerythritol penta (meth) acrylate with 1,6-hexamethylene diisocyanate. Product (number of acryloyl groups in one molecule: 10), reactive product of triisocyanate having an isocyanuric ring with pentaerythritol tri (meth) acrylate (number of acryloyl groups in one molecule: 9), pentaerythritol tri (meth) Reaction products of acrylate and isophorone diisocyanate (the number of acryloyl groups in one molecule: 6) and the like can be mentioned. These can be used alone or as a mixture of a plurality.
[0007]
In the composition for a liquid crystal retardation film used in the present invention, if at least one kind of the non-liquid crystalline polymerizable compound having 6 or more polymerizable groups in one molecule is contained, it is possible to have one molecule in one molecule. A non-liquid crystalline polymerizable compound having less than 6 polymerizable groups may be included. Examples of the non-liquid crystal polymerizable compound having less than 6 polymerizable groups in one molecule include dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and pentaerythritol tetra (meth) acrylate. ) Acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, tris (acryloxyethyl) isocyanurate, tris (methacryloxyethyl) isocyanurate, Reaction product of glycerol triglycidyl ether and (meth) acrylic acid, caprolactone-modified tris (acryloxyethyl) isocyanurate, trimethylolpropane triglycidyl ether and (meth) acrylic acid Reaction product, triglycerol di (meth) acrylate, reaction product of propylene glycol diglycidyl ether and (meth) acrylic acid, polypropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polyethylene glycol di ( Reaction products of (meth) acrylate, tetraethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, 1,6-hexanediol diglycidyl ether and (meth) acrylic acid , 1,6-hexanediol di (meth) acrylate, glycerol di (meth) acrylate, reaction product of ethylene glycol diglycidyl ether and (meth) acrylic acid, diethylene glycol Reaction product of diglycidyl ether and (meth) acrylic acid, bis (acryloxyethyl) hydroxyethyl isocyanurate, bis (methacryloxyethyl) hydroxyethyl isocyanurate, bisphenol A diglycidyl ether and (meth) acrylic acid Reactive products, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polypropylene glycol (meth) acrylate, polyethylene glycol (Meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, acryloylmorpholine, methoxypolyethylene glycol (meth) acrylate, methoxy Citetraethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxyethyl (meth) acrylate, glycidyl (meth) acrylate, glycerol (meth) acrylate, ethyl carbitol (meth) A) acrylate, 2-ethoxyethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, 2-cyanoethyl (meth) acrylate, the reaction product of butyl glycidyl ether with (meth) acrylic acid, butoxytriethylene Glycol (meth) acrylate, butanediol mono (meth) acrylate and the like can be mentioned. These can be used alone or as a mixture of a plurality of them together with the non-liquid crystalline polymerizable compound having six or more polymerizable groups in one molecule.
[0008]
The composition for a liquid crystal retardation film of the present invention comprises the polymerizable liquid crystalline compound, one or more non-liquid crystalline polymerizable compounds having 6 or more polymerizable groups in one molecule, and 1 It is obtained by mixing a non-liquid crystal polymerizable compound having less than 6 polymerizable groups in one molecule of one or more species with a polymerization initiator. The mixing ratio of the polymerizable liquid crystal compound and the non-liquid crystal polymerizable compound is compatible with each compound, when a layer made of the composition is formed on a substrate and oriented in a specific direction, In order to maintain the orientation and transparency of the layer, the former is 85 to 99% by weight, the latter is 1 to 15% by weight, preferably the former is 90 to 95% by weight. It is preferable to mix the latter so that the latter is 5% by weight or more and 10% by weight or less.
[0009]
Further, the ratio of the non-liquid crystalline polymerizable compound having 6 or more polymerizable groups in one molecule to the non-liquid crystalline polymerizable compound having less than 6 polymerizable groups in one molecule is determined according to the present invention. In order to improve the durability against a change in the retardation value, the former is 50% by weight or more, the latter is less than 50% by weight, more preferably the former is 60% by weight or more, and the latter is less than 40% by weight. It is better to do so.
[0010]
As the polymerization initiator used in the composition for a liquid crystal retardation film of the present invention, when the composition is polymerized by ultraviolet rays, a photopolymerization initiator is used. Examples of the photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 (Irgacure 907 manufactured by Ciba Specialty Chemicals) and 1-hydroxycyclohexyl phenyl ketone (Ciba Specialty). Chemicals Irgacure 184), 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone (Irgacure 2959 from Ciba Specialty Chemicals), 1- (4-dodecylphenyl) -2-hydroxy 2-methylpropan-1-one (Darocur 953 manufactured by Merck), 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one (Darocur 1116 manufactured by Merck), 2-hydroxy-2- Methyl-1-phenylpropane- -One (Irgacure 1173 manufactured by Ciba Specialty Chemicals), acetophenone-based compounds such as diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-2-phenylacetophenone Benzoin compounds such as (Irgacure 651 manufactured by Ciba Specialty Chemicals), benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyldiphenylsulfide, 3,3′-dimethyl Benzophenone compounds such as -4-methoxybenzophenone (Kayacure MBP manufactured by Nippon Kayaku), thioxanthone, 2-chlorothioxanthone (Kayacure CTX manufactured by Nippon Kayaku), 2-methylthioxanthone, 2,4-dimethylthioxanthone (Kayacure RTX), isopropylthioxanthone, 2,4-dichlorothioxanthone (Kayacure CTX manufactured by Nippon Kayaku), Thioxanthone-based compounds such as 2,4-diethylthioxanthone (Kayacure DETX manufactured by Nippon Kayaku) and 2,4-diisopropylthioxanthone (Kayacure DITX manufactured by Nippon Kayaku) are exemplified. One or more of these photopolymerization initiators can be used by mixing at an arbitrary ratio.
[0011]
When a benzophenone-based compound or a thioxanthone-based compound is used, an auxiliary agent can be used in combination to promote the photopolymerization reaction. Such auxiliaries include, for example, triethanolamine, methyldiethanolamine, triisopropanolamine, n-butylamine, N-methyldiethanolamine, diethylaminoethyl methacrylate, Michler's ketone, 4,4'-diethylaminophenone, 4-dimethylaminobenzoic acid Examples thereof include amine compounds such as ethyl, ethyl 4- (dimethylaminobenzoate) (n-butoxy), and isoamyl 4-dimethylaminobenzoate.
[0012]
Since the photopolymerization initiator and the auxiliary do not directly polymerize, they are present in the liquid crystal layer. Therefore, the addition amount of the photopolymerization initiator is preferably used within a range that does not affect the orientation and durability of the liquid crystal compound later, and the amount is preferably the total (meth) acrylate compound 100 in the composition. It is preferably from 0.5 to 20 parts by weight, more preferably from 2 to 15 parts by weight, based on parts by weight. The amount of the auxiliary agent is preferably about 0.5 to 2 times the amount of the photopolymerization initiator.
[0013]
Using the composition for a liquid crystal retardation film of the present invention thus obtained, the composition is diluted directly or with an appropriate solvent so that the composition layer can be oriented in a specific direction. On the substrate that has been treated. Thereafter, the solvent is removed by heating or the like, and then the composition layer is oriented in a specific direction, then polymerized by irradiating ultraviolet rays or the like, and the orientation state is fixed, whereby the liquid crystal retardation of the present invention is obtained. A film can be obtained. As a solvent for the solution of the composition used in the application, the solubility of the composition, excellent wettability on the substrate at the time of application, affects the orientation of the composition layer after application to the substrate. There is no particular limitation as long as it does not cause a significant decrease in surface properties enough to give Examples of such a solvent include aromatic hydrocarbons such as toluene and xylene, ethers such as anisole, dioxane and tetrahydrofuran, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-pentanone, and 3-pentanone. Ketones such as 2-hexanone, 3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2,6-dimethyl-4-heptanone, and alcohols such as n-butanol, 2-butanol, cyclohexanol, and isopropyl alcohol , Cellosolves such as methyl cellosolve and methyl cellosolve acetate, and esters such as ethyl acetate, butyl acetate and methyl lactate, but are not limited thereto. The solvent may be a single solvent or a mixture. The concentration of the composition at the time of dissolving the composition varies depending on solvent solubility, wettability on a substrate, thickness after coating, etc., but is preferably 5 to 95% by weight, more preferably 10 to 80% by weight. Good degree.
[0014]
In addition, when the composition is applied on a substrate, when the wettability on the substrate is poor, or when the surface property of the formed liquid crystal composition layer is poor, various leveling in the composition is required to improve them. It is also possible to add an agent. As the type of the leveling agent, various compounds such as a silicon type, a fluorine type, a polyether type, an acrylic acid copolymer type and a titanate type can be used. The amount of these leveling agents to be added is preferably 0.0001 to 0.005 parts by weight, more preferably 0.0005 to 0.003 parts by weight, per 100 parts by weight of the composition. It is preferable that the amount is not more than weight part.
[0015]
The method for applying the composition for a liquid crystal retardation film of the present invention or a solution thereof to a substrate is not particularly limited, but the thickness of the obtained retardation film of the present invention affects the retardation value. The surface is preferably as smooth as possible. Examples of a coating method for obtaining such a composition layer include, for example, a spin coating method, a wire bar coating method, a gravure coating method, a microgravure coating method, a calendar coating method, a spray coating method, a meniscus coating method, and the like. Method. The thickness of the composition layer is appropriately determined because it varies depending on the desired retardation value, but the thickness after removing the solvent is preferably 0.01 to 20 μm, more preferably about 0.05 to 10 μm. Often, such a film thickness is achieved by adjusting the concentration of the solution, the coating method, and the coating conditions.
[0016]
The specific direction when the liquid crystal retardation film composition used in the present invention is oriented in a specific direction is a direction in which anisotropy of the refractive index appears in one direction and another direction in the film. In the liquid crystal retardation film of the present invention, the direction in which the refractive index becomes maximum in the plane of the film or in the thickness direction is shown. As the substrate treated so that the composition can be oriented in a specific direction, for example, an alignment film is formed on a rubbed polymer film or a polymer film, and if necessary, the alignment film is formed. Further, a rubbed polymer film or the like may be used. As the polymer film, those having excellent wettability of the liquid crystal composition of the present invention and a solution thereof and having such a smoothness that the optical properties of the obtained retardation film are not deteriorated are preferable. Examples of such a polymer film include, for example, a film mainly containing a cellulose derivative such as diacetyl cellulose and triacetyl cellulose, a film mainly containing a cycloolefin polymer such as a norbornene derivative, polyethylene terephthalate, and polyethylene naphthalate. Examples of the film include a film mainly containing polyester, a film mainly containing polycarbonate and a derivative thereof, and a film mainly containing polyalkylene such as polypropylene and polyethylene and a derivative thereof. These films may be uniaxially or biaxially stretched. Further, as the alignment film, those which are excellent in the wettability of the liquid crystal composition of the present invention and the solution thereof and which can align the composition in a specific direction are preferable. Examples of such an alignment film include, for example, polyamide, polyimide, lecithin, silica, polyvinyl alcohol, ester-modified polyvinyl alcohol, a polymer having an adjusted saponification degree of polyvinyl acetate, and an alignment formed by applying a silane coupling agent or the like. Examples include a film and an alignment film in which aluminum or aluminum oxide is applied or deposited on a polymer film. By subjecting these alignment films to a rubbing treatment in a direction in which the alignment is desired, the composition can be oriented in a specific direction, for example, a rubbing direction. When an alignment film using lecithin, silica, a silane coupling agent, aluminum or aluminum oxide is used, the composition can be oriented in a direction perpendicular to the substrate surface without performing rubbing treatment or the like. it can.
[0017]
When the composition layer is formed into a substrate that has been treated so that it can be oriented in the specific direction, at the same time as the removal of the solvent by heating and drying, or after the removal of the solvent, in a temperature region showing liquid crystallinity. By leaving it for a certain period of time, it can be oriented in a specific direction. Next, in the case of polymerizing with ultraviolet light, the polymer is polymerized while maintaining the alignment state by irradiating ultraviolet light under conditions capable of maintaining the alignment state, and as a result, the alignment state is fixed. The irradiation amount of the ultraviolet ray varies depending on the type of the (meth) acrylate compound, the type and the addition amount of the photopolymerization initiator, and the film thickness in the composition of the present invention, but is 100 to 1000 mJ / cm. 2 Good degree. The atmosphere at the time of ultraviolet irradiation may be in the air, in an inert gas such as nitrogen, and the like. However, if the film thickness is small, the film is not sufficiently cured due to oxygen damage. It is preferable to cure by irradiation.
[0018]
The liquid crystal retardation film of the present invention thus obtained has a certain retardation value. The phase difference value can be maintained. Specifically, the initial retardation value of the liquid crystal retardation film of the present invention produced by the above method at a certain wavelength is defined as Rref, and the retardation film of the liquid crystal retardation film after standing for 24 hours in a dry heat atmosphere at a temperature of 85 ° C. Assuming that the phase difference value at the same wavelength as the initial time is Rdur, a liquid crystal phase difference film that makes the rate of change Rc of the phase difference value obtained by the following equation (1) equal to or less than a certain value is preferable.
| (Rref−Rdur) /Rref|=Rc≦0.10 (1)
When the liquid crystalline compound is oriented in a horizontal direction or at a certain angle with respect to the substrate, the retardation value in the vertical direction with respect to the obtained film surface can satisfy the above formula (1). However, when the orientation direction of the liquid crystal composition is substantially perpendicular to the substrate, the phase difference value in the direction perpendicular to the substrate is almost zero. In the case of such a liquid crystal retardation film of the present invention, for example, a retardation value when tilted by 50 ° from a direction perpendicular to the obtained film surface is measured, and the value is calculated by the above equation (1). Can be satisfied. At this time, the absolute value Rc of the change rate is preferably 0.10 or less, more preferably 0.07 or less, and further preferably 0.05 or less. Further, since the phase difference value may be different depending on the wavelength, the wavelength at which the phase difference value is measured must be the same at the initial stage and after the acceleration test. As a preferable wavelength, a wavelength around 400 to 750 nm, more preferably around 500 to 600 nm is used. The liquid crystal retardation film of the present invention has excellent durability because the change in the retardation value is extremely small even in the accelerated test in which the film is left under the high-temperature atmosphere. Can be maintained.
[0019]
The liquid crystal retardation film of the present invention can be peeled off from the substrate with an adhesive or the like and used by being laminated with another retardation film. If the substrate itself is a retardation film, it can be used without peeling off from the substrate. The laminated retardation film of the present invention can be obtained by laminating such a liquid crystal retardation film of the present invention and another retardation film directly or using an adhesive or an adhesive. The other retardation film is, for example, a film obtained by imparting birefringence to a polymer film made of polycarbonate, polyarylate, diacetyl cellulose, triacetyl cellulose, a norbornene derivative, a cycloolefin polymer, or the like. The birefringence may be spontaneously generated during the formation of the polymer film, or may be imparted by uniaxially or biaxially stretching the polymer film.
[0020]
The laminated polarizing film of the present invention can be obtained by laminating the liquid crystal retardation film or the laminated retardation film of the present invention with a polarizing film using an adhesive or an adhesive. A polarizing film is obtained by impregnating a polyalcohol film with a polyiodide ion or a dichroic dye, and then uniaxially stretching the film in a boric acid warm bath. It is obtained by sandwiching using a system adhesive or the like. Since the liquid crystal retardation film of the present invention has excellent durability, it is particularly preferable to use the liquid crystal retardation film in combination with a polarizing film including a polarizing element using a dichroic dye having also excellent durability.
[0021]
The image display device of the present invention can be obtained by using the thus obtained liquid crystal retardation film, laminated retardation film, or laminated polarizing film of the present invention for an LCD, an organic electroluminescence display (organic EL), or the like. When used in an LCD, it is usually used in combination with a polarizing film. Examples of a liquid crystal cell used in the LCD include a twisted nematic (TN) type, a super twisted nematic (STN) type, and a horizontal alignment (ECB) type. And various liquid crystal cells such as a vertical alignment nematic (VA) type, an in-plane switching (IPS) type, a bend nematic (OCB) type, a ferroelectric liquid crystal (SSFLC) type, and an antiferroelectric liquid crystal (AFLC) type liquid crystal cell. Can be Further, a liquid crystal display device using these liquid crystal cells can be used in any of a transmission type, a reflection type and a reflection semi-transmission type. By using the liquid crystal retardation film of the present invention for such various LCDs, the contrast, hue, and viewing angle characteristics can be improved, and the functions thereof can be maintained for a long period of time. When used for an organic EL, for example, a vertically polarized liquid crystal retardation film of the present invention is laminated on a uniaxially stretched retardation film side on a circularly polarizing film obtained by combining a polarizing film and a uniaxially stretched retardation film. By arranging it on the image display surface side, visibility can be improved by suppressing reflection of the metal electrode with a wide viewing angle, and its function can be maintained for a long time.
[0022]
【Example】
Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.
Example 1
[0023]
Embedded image
36.6 parts by weight of a compound represented by the following formula:
[0025]
Embedded image
42.1 parts by weight of a compound represented by the formula:
[0027]
Embedded image
A mixture of a UV-curable liquid crystalline compound containing 9.3 parts by weight of a compound represented by the following formula and 12 parts by weight of a photopolymerization initiator Irgacure 907 (manufactured by Ciba Specialty Chemicals) was added to dipentaerythritol hexaacrylate (in one molecule). 8.8 parts by weight of acryloyl group: 6, Nippon Kayaku Kayarad DPS-100) is dissolved in a mixed solvent of 244.8 parts by weight of toluene and 81.6 parts by weight of cyclohexanone, and the present invention has a solid concentration of 25%. Was prepared. This solution is uniformly coated on a surface of an acrylic resin of a polyester film having a vapor-deposited layer coated with an aluminum resin, using a wire bar. The solvent is removed by heating, and then a high-pressure mercury lamp (120 W / cm ) To polymerize the liquid crystal retardation film of the present invention. The thickness of this retardation film was 0.8 μm. Next, when the liquid crystal retardation film of the present invention was peeled from the polyester film using a glass plate coated with an adhesive, the retardation film was transparent. Next, the change in the retardation value when the retardation film transferred to the glass plate was inclined from the front of the retardation film was measured using an automatic birefringence measuring instrument (KOBRA-21ADH manufactured by Oji Scientific Instruments). It was measured. The results are shown in FIG. From FIG. 1, it was found that the liquid crystal retardation film of the present invention was oriented vertically to the surface of the retardation film. The retardation value at 590 nm when tilted at 50 ° from the perpendicular direction of the retardation film surface was 39.0 nm. Next, the liquid crystal retardation film of the present invention transferred to the glass plate was left in a dry heat atmosphere at 85 ° C. for 24 hours. Thereafter, the film was allowed to cool to room temperature, and similarly, the retardation value at 590 nm when the film was inclined at 50 ° from the vertical direction of the film surface was 37.3 nm. From this result, the rate of change was determined by the above equation (1). The results are shown in Table 1.
[0029]
Example 2
Reaction of dipentaerythritol hexaacrylate (number of acryloyl groups in one molecule: 6), dipentaerythritol pentaacrylate and 1,6-hexamethylene diisocyanate instead of kayarad DPS-100 used in Example 1 The same procedure as in Example 1 was carried out, except that 8.8 parts by weight of a mixture (manufactured by Nippon Kayaku Kayarad DPHA-40H) with the product (number of acryloyl groups in one molecule: 10) was used. A film was obtained. The obtained retardation film was transparent. Further, this liquid crystal retardation film was vertically oriented with respect to the film surface as in Example 1. Next, this liquid crystal retardation film was evaluated in the same manner as in Example 1. The results are shown in Table 1.
[0030]
Example 3
A mixture of dipentaerythritol hexaacrylate (the number of acryloyl groups in one molecule: 6) and dipentaerythritol pentaacrylate (the number of acryloyl groups in one molecule: 5) instead of Kayarad DPS-100 used in Example 1 A liquid crystal retardation film of the present invention was obtained in the same manner as in Example 1, except that 8.8 parts by weight (60 parts for the former and 40 parts for the latter) were used. The obtained retardation film was transparent. Further, this liquid crystal retardation film was vertically oriented with respect to the film surface as in Example 1. Next, this liquid crystal retardation film was evaluated in the same manner as in Example 1. The results are shown in Table 1.
[0031]
[Comparative example]
Comparative Example 1
In place of kayarad DPS-100 used in Example 1, pentaerythritol tetraacrylate (the number of acryloyl groups in one molecule: 4, kayarad PET-40 manufactured by Nippon Kayaku) was used in accordance with JP-T-2000-514202. A liquid crystal retardation film was obtained in the same manner as in Example 1 except that 8.8 parts by weight was used. The obtained retardation film was transparent. This liquid crystal retardation film was also vertically oriented with respect to the film surface as in Example 1. Next, this film was evaluated in the same manner as in Example 1. The results are shown in Table 1.
[0032]
Comparative Example 2
A reactive product of bisphenol A diglycidyl ether and acrylic acid (the number of acryloyl groups in one molecule: two, Japan A liquid crystal retardation film was obtained in the same manner as in Example 1, except that 8.8 parts by weight of Kayrad R-115) (manufactured by Kayaku) was used. The obtained retardation film was transparent. This liquid crystal retardation film was also vertically oriented with respect to the film surface as in Example 1. Next, this film was evaluated in the same manner as in Example 1. The results are shown in Table 1.
[0033]
Comparative Example 3
A liquid crystal retardation film was obtained in the same manner as in Example 1, except that kayrad DPS-100 used in Example 1 was not used. The obtained retardation film was transparent. This liquid crystal retardation film was also vertically oriented with respect to the film surface as in Example 1. Next, this film was evaluated in the same manner as in Example 1. The results are shown in Table 1.
[0034]
Comparative Example 4
The same operation as in Example 1 was performed except that 17.6 parts by weight of kayarad DPHA-40H used in Example 2 and 6 parts by weight of a photopolymerization initiator Irgacure 907 (manufactured by Ciba Specialty Chemicals) were used. Since the composition layer was not oriented and became cloudy, the liquid crystal retardation film of the present invention could not be produced.
[0035]
[Table 1]
From the results of Example 1 and Comparative Example 4, the composition for a liquid crystal retardation film of the present invention was oriented in a specific direction by adding a non-liquid crystalline compound within the scope of the present invention, and thus a transparent liquid crystal retardation film was obtained. Is obtained. Also, from the results of Comparative Examples 1 and 2 and Comparative Example 3, although the method described in JP-T-2000-514202 can be used, the change in the phase difference value in a high-temperature dry heat test can be suppressed to some extent. Not enough. On the other hand, as is clear from the results of Examples 1 to 3 and Comparative Examples 1 and 2, the liquid crystal retardation film of the present invention exhibited a higher retardation value even when subjected to a dry heat test at a higher temperature than the Comparative Example. It can be seen that the change is extremely small and stable optical performance is maintained.
[0037]
【The invention's effect】
The present invention relates to a mixture and polymerization of a non-liquid crystal polymerizable compound including at least one polymerizable liquid crystal compound and at least one non-liquid crystal polymerizable compound having at least six polymerizable groups in one molecule. A liquid crystal composition comprising an initiator, wherein the mixture ratio of the polymerizable liquid crystal compound and the non-liquid crystal polymerizable compound is 85% to 99% by weight of the former and 1% to 15% by weight of the latter. A composition for a retardation film and a liquid crystal retardation film obtained by orienting the composition in a specific direction and fixing the orientation state, and by using this film, constant optical characteristics can be maintained for a long time. .
[Brief description of the drawings]
FIG. 1 is a graph showing a change in retardation value according to an inclination angle of a liquid crystal retardation film of the present invention in Example 1.
Claims (7)
｜（Ｒｒｅｆ−Ｒｄｕｒ）／Ｒｒｅｆ｜＝Ｒｃ≦０．１０ （１）When the initial retardation value of the liquid crystal retardation film at a certain wavelength is Rref, and the retardation value of the composition layer after standing for 24 hours in a dry heat atmosphere at a temperature of 85 ° C. at the same wavelength as before the leaving is Rdur. The liquid crystal retardation film according to claim 3, wherein the rate of change Rc of the retardation value satisfies the following equation (1).
| (Rref−Rdur) /Rref|=Rc≦0.10 (1)
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007522533A (en) * | 2005-02-16 | 2007-08-09 | エルジー・ケム・リミテッド | Retardation film including vertically aligned liquid crystal film and method for producing the same |
| JP2008523443A (en) * | 2004-12-11 | 2008-07-03 | エルジー・ケム・リミテッド | Homeotropic alignment liquid crystal film which does not require alignment film and method for producing the same |
| WO2008096556A1 (en) * | 2007-02-09 | 2008-08-14 | Adeka Corporation | Polymerizable composition |
| JP2009271216A (en) * | 2008-05-01 | 2009-11-19 | Sumitomo Chemical Co Ltd | Method for producing retardation layer, and color filter |
| JP2010152069A (en) * | 2008-12-25 | 2010-07-08 | Dic Corp | Polymerizable liquid crystal composition and optical anisotropic body |
| JP2011095514A (en) * | 2009-10-30 | 2011-05-12 | Nippon Kayaku Co Ltd | Retardation element |
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2002
- 2002-06-21 JP JP2002180700A patent/JP2004029062A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008523443A (en) * | 2004-12-11 | 2008-07-03 | エルジー・ケム・リミテッド | Homeotropic alignment liquid crystal film which does not require alignment film and method for producing the same |
| JP2007522533A (en) * | 2005-02-16 | 2007-08-09 | エルジー・ケム・リミテッド | Retardation film including vertically aligned liquid crystal film and method for producing the same |
| US7807235B2 (en) | 2005-02-16 | 2010-10-05 | Lg Chem, Ltd. | Retardation film having a homeotropic alignment liquid crystal film |
| WO2008096556A1 (en) * | 2007-02-09 | 2008-08-14 | Adeka Corporation | Polymerizable composition |
| CN101583638A (en) * | 2007-02-09 | 2009-11-18 | 株式会社艾迪科 | Polymerizable composition |
| US7931825B2 (en) | 2007-02-09 | 2011-04-26 | Adeka Corporation | Polymerizable composition |
| KR101441092B1 (en) | 2007-02-09 | 2014-09-19 | 가부시키가이샤 아데카 | Polymerizable composition |
| JP2009271216A (en) * | 2008-05-01 | 2009-11-19 | Sumitomo Chemical Co Ltd | Method for producing retardation layer, and color filter |
| JP2010152069A (en) * | 2008-12-25 | 2010-07-08 | Dic Corp | Polymerizable liquid crystal composition and optical anisotropic body |
| JP2011095514A (en) * | 2009-10-30 | 2011-05-12 | Nippon Kayaku Co Ltd | Retardation element |
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