JP3513888B2 - Liquid crystal display device and method of manufacturing the same - Google Patents
Liquid crystal display device and method of manufacturing the sameInfo
- Publication number
- JP3513888B2 JP3513888B2 JP29976193A JP29976193A JP3513888B2 JP 3513888 B2 JP3513888 B2 JP 3513888B2 JP 29976193 A JP29976193 A JP 29976193A JP 29976193 A JP29976193 A JP 29976193A JP 3513888 B2 JP3513888 B2 JP 3513888B2
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- crystal display
- display device
- diacrylate
- nematic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims description 100
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000000126 substance Substances 0.000 claims description 43
- -1 diacrylate compound Chemical class 0.000 claims description 32
- 239000004988 Nematic liquid crystal Substances 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 17
- 239000002131 composite material Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 210000000988 bone and bone Anatomy 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 37
- 125000004386 diacrylate group Chemical group 0.000 description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000010408 film Substances 0.000 description 8
- 230000007704 transition Effects 0.000 description 8
- 239000012043 crude product Substances 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 239000004642 Polyimide Substances 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
- 230000010287 polarization Effects 0.000 description 6
- 229920001721 polyimide Polymers 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000005158 Cholesterol Pelargonate Substances 0.000 description 3
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- WCLNGBQPTVENHV-MKQVXYPISA-N cholesteryl nonanoate Chemical compound C([C@@H]12)C[C@]3(C)[C@@H]([C@H](C)CCCC(C)C)CC[C@H]3[C@@H]1CC=C1[C@]2(C)CC[C@H](OC(=O)CCCCCCCC)C1 WCLNGBQPTVENHV-MKQVXYPISA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001934 cyclohexanes Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 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
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical class C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- SLOMXBIDVLSOOZ-UHFFFAOYSA-N 1,6-ditert-butylcyclohexa-2,4-dien-1-ol Chemical compound CC(C)(C)C1C=CC=CC1(O)C(C)(C)C SLOMXBIDVLSOOZ-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 1
- 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 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
- 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
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- QDBOAKPEXMMQFO-UHFFFAOYSA-N 4-(4-carbonochloridoylphenyl)benzoyl chloride Chemical compound C1=CC(C(=O)Cl)=CC=C1C1=CC=C(C(Cl)=O)C=C1 QDBOAKPEXMMQFO-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- JNTPTNNCGDAGEJ-UHFFFAOYSA-N 6-chlorohexan-1-ol Chemical compound OCCCCCCCl JNTPTNNCGDAGEJ-UHFFFAOYSA-N 0.000 description 1
- RWQUWTMOHXGTNN-UHFFFAOYSA-N 9-n,10-n-bis(4-butylphenyl)-9-n,10-n-bis(4-methylphenyl)phenanthrene-9,10-diamine Chemical compound C1=CC(CCCC)=CC=C1N(C=1C2=CC=CC=C2C2=CC=CC=C2C=1N(C=1C=CC(C)=CC=1)C=1C=CC(CCCC)=CC=1)C1=CC=C(C)C=C1 RWQUWTMOHXGTNN-UHFFFAOYSA-N 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol group Chemical group [C@@H]1(CC[C@H]2[C@@H]3CC=C4C[C@@H](O)CC[C@]4(C)[C@H]3CC[C@]12C)[C@H](C)CCCC(C)C HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 1
- XHRPOTDGOASDJS-UHFFFAOYSA-N cholesterol n-octadecanoate Natural products C12CCC3(C)C(C(C)CCCC(C)C)CCC3C2CC=C2C1(C)CCC(OC(=O)CCCCCCCCCCCCCCCCC)C2 XHRPOTDGOASDJS-UHFFFAOYSA-N 0.000 description 1
- XHRPOTDGOASDJS-XNTGVSEISA-N cholesteryl stearate Chemical compound C([C@@H]12)C[C@]3(C)[C@@H]([C@H](C)CCCC(C)C)CC[C@H]3[C@@H]1CC=C1[C@]2(C)CC[C@H](OC(=O)CCCCCCCCCCCCCCCCC)C1 XHRPOTDGOASDJS-XNTGVSEISA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- GCFAUZGWPDYAJN-UHFFFAOYSA-N cyclohexyl 3-phenylprop-2-enoate Chemical class C=1C=CC=CC=1C=CC(=O)OC1CCCCC1 GCFAUZGWPDYAJN-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Landscapes
- Liquid Crystal (AREA)
- Liquid Crystal Substances (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、液晶表示素子とその製
造方法に関し、さらに詳しくは、配向制御方法を改良し
た液晶表示素子とその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal display device and a manufacturing method thereof, and more particularly to a liquid crystal display device having an improved alignment control method and a manufacturing method thereof.
【０００２】[0002]
【従来の技術】現在、工業的に製造されているツイステ
ッドネマチック（ＴＮ）型液晶表示装置、スーパーツイ
ステッドネマチック（ＳＴＮ）型液晶表示装置、アクテ
ィブマトリックス（ＡＭ）型液晶表示装置の配向膜とし
ては、基板上に被覆したポリイミドの薄膜を一方向にラ
ビングしたものが広く用いられている。2. Description of the Related Art At present, as an alignment film of a twisted nematic (TN) type liquid crystal display device, a super twisted nematic (STN) type liquid crystal display device and an active matrix (AM) type liquid crystal display device which are industrially manufactured, A unidirectionally rubbed polyimide thin film coated on a substrate is widely used.
【０００３】しかし、この方法で作製したポリイミド配
向膜のプレチルト角は、配向膜の作製条件、膜厚、ラビ
ング布、ラビングの強さ、さらには液晶材料の種類によ
って大きく影響を受けるという欠点があった。この傾向
は４度以上の高いプレチルト角を得ようとしたとき顕著
になり、特に高いプレチルト角が必要なＳＴＮ型液晶表
示装置を製造する際、大きな問題となっていた。However, there is a drawback that the pretilt angle of the polyimide alignment film produced by this method is greatly affected by the alignment film production conditions, film thickness, rubbing cloth, rubbing strength, and the type of liquid crystal material. It was This tendency becomes remarkable when an attempt is made to obtain a high pretilt angle of 4 degrees or more, which has been a serious problem in manufacturing an STN type liquid crystal display device which requires a particularly high pretilt angle.
【０００４】これを解決する手段としては、フィリップ
・ジェー・ボス（Phillip J. Bos）等により、１９９３
年度エス・アイ・ディー・ダイジェスト（SID Digest '
93）８７７頁において、光重合性材料と液晶材料からな
る組成物を、配向処理を施した２枚の電極間に封入し、
前記組成物に電圧を印加しながら紫外線を照射して光重
合性材料を重合硬化させることにより、高いプレチルト
角を持った液晶表示素子と同様の特性を有する液晶表示
素子の製造方法が報告されている。As a means for solving this, Phillip J. Bos et al., 1993.
FY SID Digest '
93) on page 877, a composition comprising a photopolymerizable material and a liquid crystal material is enclosed between two electrodes that have been subjected to an alignment treatment,
A method for producing a liquid crystal display device having the same characteristics as a liquid crystal display device having a high pretilt angle has been reported by polymerizing and curing the photopolymerizable material by irradiating ultraviolet rays while applying a voltage to the composition. There is.
【０００５】しかし、上記製造方法に用いられた光重合
性材料は、液晶材料との相溶性が悪く、紫外線を照射し
た際に誘起される液晶材料と光重合性材料との相分離過
程において形成されるポリマーのネットワークが液晶材
料の配向を乱してしまい、均一な配向状態が得られない
という欠点があった。However, the photopolymerizable material used in the above manufacturing method has poor compatibility with the liquid crystal material, and is formed during the phase separation process between the liquid crystal material and the photopolymerizable material, which is induced upon irradiation with ultraviolet rays. The polymer network thus formed disturbs the alignment of the liquid crystal material, and there is a drawback that a uniform alignment state cannot be obtained.
【０００６】[0006]
【発明が解決しようとする課題】本発明が解決しようと
する課題は、液晶材料の配向状態を均一で、且つ高いプ
レチルト角を有する液晶表示素子と同様の特性を備えた
液晶表示素子及びその製造方法を提供することにある。The problem to be solved by the present invention is to provide a liquid crystal display device having a liquid crystal material in which the alignment state is uniform and having the same characteristics as a liquid crystal display device having a high pretilt angle, and to manufacture the same. To provide a method.
【０００７】[0007]
【課題を解決するための手段】本発明者らは上記課題を
解決するために、鋭意研究を行った結果、本発明に至っ
た。Means for Solving the Problems The inventors of the present invention have conducted extensive studies in order to solve the above-mentioned problems, and as a result, have reached the present invention.
【０００８】すなわち、本発明は上記課題を解決するた
めに、配向処理を施した透明電極を有する少なくとも一
方が透明な２枚の基板であって、２枚の基板上の配向方
向が１８０〜２７０゜の範囲にある基板間に、液晶／高
分子複合体を有し、該液晶／高分子複合体が、ネマチッ
ク液晶およびカイラル物質と液晶性骨格を有するジアク
リレート化合物との重合体を含有し、該液晶／高分子複
合体中に、該重合体と液晶との界面に沿って配向する液
晶分子を含有し、かつ、基板面に対し２〜５０゜の範囲
で傾斜している液晶分子を含有することを特徴とする液
晶表示素子を提供する。In other words, in order to solve the above-mentioned problems, the present invention has two transparent substrates having at least one transparent electrode having an alignment treatment, and the orientation directions on the two substrates are 180 to 270. A liquid crystal / polymer composite between the substrates in the range of 0 °, and the liquid crystal / polymer composite contains a nematic liquid crystal and a polymer of a chiral substance and a diacrylate compound having a liquid crystalline skeleton, The liquid crystal / polymer composite contains liquid crystal molecules aligned along the interface between the polymer and liquid crystal, and liquid crystal molecules tilted in the range of 2 to 50 ° with respect to the substrate surface. A liquid crystal display element is provided.
【０００９】本発明の液晶表示素子は、例えば、次の製
造方法に従って製造することができる。すなわち、配向
処理を施した透明電極を有する少なくとも一方が透明な
２枚の基板であって、２枚の基板上の配向方向が１８０
〜２７０゜の範囲にある基板間に、ネマチック液晶およ
びカイラル物質と液晶性骨格を有するジアクリレート化
合物とを含有する液晶／高分子複合体形成材料を挟持
し、該ネマチック液晶およびカイラル物質を配向させた
後、該液晶／高分子複合体形成材料に電圧を印加させな
がら、活性光線を照射し、液晶性骨格を有するジアクリ
レート化合物を重合させる方法。The liquid crystal display element of the present invention can be manufactured, for example, according to the following manufacturing method. That is, at least one of the two substrates having the transparent electrode subjected to the alignment treatment is transparent, and the alignment direction on the two substrates is 180.
A liquid crystal / polymer composite forming material containing a nematic liquid crystal and a chiral substance and a diacrylate compound having a liquid crystalline skeleton is sandwiched between substrates in the range of ˜270 ° to orient the nematic liquid crystal and the chiral substance. After that, while applying a voltage to the liquid crystal / polymer composite forming material, the liquid crystal / polymer composite is irradiated with an actinic ray to polymerize a diacrylate compound having a liquid crystalline skeleton.
【００１０】本発明で使用するネマチック液晶はネマチ
ック液晶以外の物質も含んでいてもよく、通常この技術
分野で液晶材料と認識されるものであればよく、そのう
ち正の誘電率異方性を有するものが好ましい。The nematic liquid crystal used in the present invention may contain a substance other than the nematic liquid crystal as long as it is generally recognized as a liquid crystal material in this technical field, and it has a positive dielectric anisotropy. Those are preferable.
【００１１】本発明で使用するネマチック液晶は、以下
に示した液晶化合物群から選ばれた１種以上の化合物か
らなる配合組成物が好ましく、液晶材料の特性、すなわ
ち、等方性液体と液晶の相転移温度、融点、粘度、Δε
（誘電率異方性）、Δｎ（屈折率異方性）を改善するこ
とを目的として適宜選択、配合して用いることができ
る。The nematic liquid crystal used in the present invention is preferably a compounded composition composed of one or more compounds selected from the liquid crystal compound group shown below, and has characteristics of the liquid crystal material, that is, an isotropic liquid and a liquid crystal. Phase transition temperature, melting point, viscosity, Δε
For the purpose of improving (dielectric anisotropy) and Δn (refractive index anisotropy), they can be appropriately selected and blended for use.
【００１２】上記液晶化合物としては、例えば、４−置
換安息香酸フェニルエステル、４−置換シクロヘキサン
カルボン酸４’−置換フェニルエステル、４−置換シク
ロヘキサンカルボン酸４’−置換ビフェニルエステル、
４−（４−置換シクロヘキサンカルボニルオキシ）安息
香酸４−置換フェニルエステル、４−（４−置換シクロ
ヘキシル）安息香酸フェニルエステル、４−（４−置換
シクロヘキシル）安息香酸４’−置換シクロヘキシルエ
ステル、４−置換４’−置換ビフェニル、４−置換４’
−置換シクロヘキサン、４−置換４”−置換ターフェニ
ル、４−置換ビフェニル４’−置換シクロヘキサン、２
−（４−置換フェニル）−５−置換ピリジン等を挙げる
ことができる。特に好ましいのは、これらの化合物の中
でも、少なくとも分子の一方の末端にシアノ基を有する
化合物である。Examples of the liquid crystal compound include 4-substituted benzoic acid phenyl ester, 4-substituted cyclohexanecarboxylic acid 4'-substituted phenyl ester, 4-substituted cyclohexanecarboxylic acid 4'-substituted biphenyl ester,
4- (4-Substituted cyclohexanecarbonyloxy) benzoic acid 4-substituted phenyl ester, 4- (4-substituted cyclohexyl) benzoic acid phenyl ester, 4- (4-substituted cyclohexyl) benzoic acid 4′-substituted cyclohexyl ester, 4- Substituted 4′-substituted biphenyl, 4-substituted 4 ′
-Substituted cyclohexane, 4-substituted 4 "-substituted terphenyl, 4-substituted biphenyl 4'-substituted cyclohexane, 2
Examples thereof include-(4-substituted phenyl) -5-substituted pyridine. Particularly preferred among these compounds are compounds having a cyano group at least at one end of the molecule.
【００１３】本発明で使用するカイラル物質としては、
例えば、光学活性基としてコレステリル基を有するペラ
ルゴン酸コレステロール、ステアリン酸コレステロー
ル、光学活性基として２−メチルブチル基を有する「Ｃ
Ｂ−１５」、「Ｃ−１５」（以上、ビー・ディー・エイ
チ（ＢＤＨ）社製）、「Ｓ１０８２」（メルク社製）、
「ＣＭ−１９」、「ＣＭ−２０」、「ＣＭ」（チッソ社
製）、光学活性基として１−メチルヘプチル基を有する
「Ｓ８１１」（メルク社製）、「ＣＭ−２１」、「ＣＭ
−２２」（以上、チッソ社製）を挙げることができる。The chiral substance used in the present invention includes:
For example, cholesterol pelargonate having a cholesteryl group as an optically active group, cholesterol stearate, and “C having a 2-methylbutyl group as an optically active group”
B-15 "," C-15 "(above, manufactured by BHD (BDH))," S1082 "(manufactured by Merck),
"CM-19", "CM-20", "CM" (manufactured by Chisso), "S811" (manufactured by Merck) having 1-methylheptyl group as an optically active group, "CM-21", "CM"
-22 "(above, manufactured by Chisso Co.).
【００１４】本発明で用いる液晶性骨格を有するジアク
リレート化合物は、必ずしも単体として液晶性を発現し
なくてもよく、The diacrylate compound having a liquid crystalline skeleton used in the present invention does not necessarily exhibit liquid crystallinity as a simple substance,
【００１５】[0015]
【化１０】 [Chemical 10]
【００１６】（式中、(Where
【００１７】[0017]
【化１１】 [Chemical 11]
【００１８】は各々独立的に、Each independently,
【００１９】[0019]
【化１２】 [Chemical 12]
【００２０】を表し、ＸまたはＹは各々独立的に、単結
合、−ＣＨ2ＣＨ2−、−ＯＣＯ−、−ＣＯＯ−、−ＣＨ
2Ｏ−、−ＯＣＨ2−または−Ｃ≡Ｃ−を表し、Ｄまたは
Ｅは各々独立的に単結合、エステル結合、エーテル結合
を表し、Ｚは水素原子またはメチル基を表し、ｍまたは
ｎは各々独立的に０〜６の整数を表し、ｐは０または１
の整数を表し、ｑは０、１または２の整数を表し、シク
ロヘキサン環はトランス−シクロヘキサン環を表す。）
で表される化合物を用いることができる。And each of X and Y independently represents a single bond, --CH 2 CH 2- , --OCO--, --COO--, --CH.
2 O—, —OCH 2 — or —C≡C—, D or E each independently represents a single bond, an ester bond, an ether bond, Z represents a hydrogen atom or a methyl group, and m or n represents Each independently represent an integer of 0 to 6, and p is 0 or 1
Represents an integer of 0, q represents an integer of 0, 1 or 2, and the cyclohexane ring represents a trans-cyclohexane ring. )
The compound represented by can be used.
【００２１】また、これらの液晶性骨格を有するジアク
リレート化合物は、上記一般式において、Ｚが互いに同
一であっても、異なっていてもよい。さらに、好ましい
ものとしては、下記に示す化合物が挙げられる。In the above general formula, the diacrylate compounds having a liquid crystal skeleton may have the same Z or different Z. Furthermore, the compounds shown below are preferred.
【００２２】[0022]
【化１３】 [Chemical 13]
【００２３】（上記式中、Ｚは水素原子またはメチル基
を表し、シクロヘキサン環はトランス−シクロヘキサン
環を表す。）(In the above formula, Z represents a hydrogen atom or a methyl group, and the cyclohexane ring represents a trans-cyclohexane ring.)
【００２４】[0024]
【化１４】 [Chemical 14]
【００２５】[0025]
【化１５】 [Chemical 15]
【００２６】[0026]
【化１６】 [Chemical 16]
【００２７】（上記式中、Ｚは水素原子またはメチル基
を表し、ｍまたはｎは各々独立的に２、４または６を表
し、シクロヘキサン環はトランス−シクロヘキサン環を
表す。）(In the above formula, Z represents a hydrogen atom or a methyl group, m or n each independently represents 2, 4 or 6, and the cyclohexane ring represents a trans-cyclohexane ring.)
【００２８】[0028]
【化１７】 [Chemical 17]
【００２９】[0029]
【化１８】 [Chemical 18]
【００３０】（上記式中、Ｚは水素原子またはメチル基
を表し、ｍまたはｎは各々独立的に１、３または５を表
し、シクロヘキサン環はトランス−シクロヘキサン環を
表す。）(In the above formula, Z represents a hydrogen atom or a methyl group, m or n each independently represents 1, 3 or 5, and the cyclohexane ring represents a trans-cyclohexane ring.)
【００３１】[0031]
【化１９】 [Chemical 19]
【００３２】（上記式中、Ｚは水素原子またはメチル基
を表し、ｍは２、４または６を表し、ｎは１、３または
５を表し、シクロヘキサン環はトランス−シクロヘキサ
ン環を表す。）(In the above formula, Z represents a hydrogen atom or a methyl group, m represents 2, 4 or 6, n represents 1, 3 or 5, and the cyclohexane ring represents a trans-cyclohexane ring.)
【００３３】[0033]
【化２０】 [Chemical 20]
【００３４】（上記式中、Ｚは水素原子またはメチル基
を表し、ｍは１、３または５を表し、ｎは２、４または
６を表し、シクロヘキサン環はトランス−シクロヘキサ
ン環を表す。）(In the above formula, Z represents a hydrogen atom or a methyl group, m represents 1, 3 or 5, n represents 2, 4 or 6, and the cyclohexane ring represents a trans-cyclohexane ring.)
【００３５】[0035]
【化２１】 [Chemical 21]
【００３６】（上記式中、Ｚは水素原子またはメチル基
を表し、ｍは２、４または６を表し、ｎは１、３または
５を表し、シクロヘキサン環はトランス−シクロヘキサ
ン環を表す。）(In the above formula, Z represents a hydrogen atom or a methyl group, m represents 2, 4 or 6, n represents 1, 3 or 5, and the cyclohexane ring represents a trans-cyclohexane ring.)
【００３７】[0037]
【化２２】 [Chemical formula 22]
【００３８】（上記式中、Ｚは水素原子またはメチル基
を表し、ｍは１、３または５を表し、ｎは２、４または
６を表し、シクロヘキサン環はトランス−シクロヘキサ
ン環を表す。）(In the above formula, Z represents a hydrogen atom or a methyl group, m represents 1, 3 or 5, n represents 2, 4 or 6, and the cyclohexane ring represents a trans-cyclohexane ring.)
【００３９】[0039]
【化２３】 [Chemical formula 23]
【００４０】（上記式中、Ｚは水素原子またはメチル基
を表し、シクロヘキサン環はトランス−シクロヘキサン
環を表す。）(In the above formula, Z represents a hydrogen atom or a methyl group, and the cyclohexane ring represents a trans-cyclohexane ring.)
【００４１】[0041]
【化２４】 [Chemical formula 24]
【００４２】（上記式中、Ｚは水素原子またはメチル基
を表し、ｍまたはｎは各々独立的に１、３または５を表
し、シクロヘキサン環はトランス−シクロヘキサン環を
表す。）(In the above formula, Z represents a hydrogen atom or a methyl group, m or n each independently represents 1, 3 or 5, and the cyclohexane ring represents a trans-cyclohexane ring.)
【００４３】[0043]
【化２５】 [Chemical 25]
【００４４】（上記式中、Ｚは水素原子またはメチル基
を表し、ｍまたはｎは各々独立的に２、４または６を表
し、シクロヘキサン環はトランス−シクロヘキサン環を
表す。）(In the above formula, Z represents a hydrogen atom or a methyl group, m or n each independently represents 2, 4 or 6, and the cyclohexane ring represents a trans-cyclohexane ring.)
【００４５】[0045]
【化２６】 [Chemical formula 26]
【００４６】（上記式中、Ｚは水素原子またはメチル基
を表し、ｍは１、３または５を表し、ｎは２、４または
６を表し、シクロヘキサン環はトランス−シクロヘキサ
ン環を表す。）(In the above formula, Z represents a hydrogen atom or a methyl group, m represents 1, 3 or 5, n represents 2, 4 or 6, and the cyclohexane ring represents a trans-cyclohexane ring.)
【００４７】[0047]
【化２７】 [Chemical 27]
【００４８】（上記式中、Ｚは水素原子またはメチル基
を表し、ｍは２、４または６を表し、ｎは１、３または
５を表し、シクロヘキサン環はトランス−シクロヘキサ
ン環を表す。）これらのジアクリレートの中でも、一般
式（ａ）〜（ｃ）(In the above formula, Z represents a hydrogen atom or a methyl group, m represents 2, 4 or 6, n represents 1, 3 or 5, and the cyclohexane ring represents a trans-cyclohexane ring.) Among the diacrylates of, general formulas (a) to (c)
【００４９】[0049]
【化２８】 [Chemical 28]
【００５０】（式中、Ｚ1及びＺ2はそれぞれ独立的に、
水素原子またはメチル基を表す。）で表される化合物は
新規化合物であり、本発明はこれらの化合物も提供す
る。(In the formula, Z 1 and Z 2 are each independently
Represents a hydrogen atom or a methyl group. ) Are novel compounds, and the present invention also provides these compounds.
【００５１】本発明で使用する液晶性骨格を有するジア
クリレートは、ネマチック液晶およびカイラル物質中
に、１〜２０重量％の割合で溶解するのが好ましく、さ
らに好ましくは１〜３重量％の割合で溶解するのが好ま
しい。The diacrylate having a liquid crystalline skeleton used in the present invention is preferably dissolved in the nematic liquid crystal and the chiral substance at a ratio of 1 to 20% by weight, and more preferably at a ratio of 1 to 3% by weight. It is preferably dissolved.
【００５２】また、ネマチック液晶およびカイラル物質
と、液晶性骨格を有するジアクリレート化合物との重合
体に、紫外線照射による該液晶性骨格を有するジアクリ
レート化合物の重合硬化を促進する目的で、光重合開始
剤を溶解させてもよく、その濃度は、液晶性骨格を有す
るジアクリレート化合物に対して、１〜２０重量％が好
ましく、さらに好ましくは２〜１０重量％である。Further, in order to accelerate polymerization and curing of a diacrylate compound having a liquid crystalline skeleton by irradiation of ultraviolet rays, a polymer of a nematic liquid crystal or chiral substance and a diacrylate compound having a liquid crystalline skeleton is used to initiate photopolymerization. The agent may be dissolved, and the concentration thereof is preferably 1 to 20% by weight, more preferably 2 to 10% by weight, based on the diacrylate compound having a liquid crystal skeleton.
【００５３】上記重合開始剤としては、例えば、２−ヒ
ドロキシ−２−メチル−１−フェニルプロパン−１−オ
ン（メルク社製「ダロキュア１１７３」）、１−ヒドロ
キシシクロヘキシルフェニルケトン（チバ・ガイギー社
製「イルガキュア１８４」）、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（メルク社製「ダロキュア１１１６」）、ベンジ
ルジメチルケタール（チバ・ガイギー社製「イルガキュ
ア６５１」）、２−メチル−１−［４−（メチルチオ）
フェニル］−２−モルホリノプロパノン−１（チバ・ガ
イギー社製「イルガキュア９０７」）、２，４−ジエチ
ルチオキサントン（日本化薬社製「カヤキュアＤＥＴ
Ｘ」）とｐ−ジメチルアミノ安息香酸エチル（日本化薬
社製「カヤキュアＥＰＡ」）との混合物、イソプロピル
チオキサントン（ワードプレキンソップ社製「カンタキ
ュアＩＴＸ」）とｐ−ジメチルアミノ安息香酸エチルと
の混合物等が挙げられる。Examples of the above-mentioned polymerization initiator include 2-hydroxy-2-methyl-1-phenylpropan-1-one (“Darocur 1173” manufactured by Merck), 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Geigy). "Irgacure 184"), 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1
-One (“Darocur 1116” manufactured by Merck), benzyl dimethyl ketal (“Irgacure 651” manufactured by Ciba Geigy), 2-methyl-1- [4- (methylthio)
Phenyl] -2-morpholinopropanone-1 (“Irgacure 907” manufactured by Ciba Geigy), 2,4-diethylthioxanthone (“Kayacure DET manufactured by Nippon Kayaku Co., Ltd.”)
X ") and ethyl p-dimethylaminobenzoate (" Kayacure EPA "manufactured by Nippon Kayaku Co., Ltd.), isopropylthioxanthone (" Cantacure ITX "manufactured by Ward Prekinsop) and ethyl p-dimethylaminobenzoate. A mixture etc. are mentioned.
【００５４】本発明で使用する基板は、堅固な材料、例
えば、ガラス、金属等であってもよく、柔軟性を有する
材料、例えば、プラスチックフィルムの如きものであっ
てもよい。そして、その少なくとも一方は透明性を有
し、それらの２枚の間に挟持される液晶／高分子複合体
を外界から視覚させるものでなければならない。ただ
し、完全な透明性を必須とするものではない。The substrate used in the present invention may be a rigid material such as glass or metal, or a flexible material such as a plastic film. At least one of them must be transparent so that the liquid crystal / polymer composite sandwiched between the two can be seen from the outside world. However, complete transparency is not essential.
【００５５】２枚の電極間の間隔は、２〜２０μｍが好
ましく、４〜８μｍが特に好ましい。電極間に電圧を印
加する手段としては、通常の液晶表示素子に使用される
駆動手段が使用でき、印加電圧は０．５〜５０Ｖの交流
電圧が好ましく、０．５〜１０Ｖがさらに好ましい。The distance between the two electrodes is preferably 2 to 20 μm, particularly preferably 4 to 8 μm. As a means for applying a voltage between the electrodes, a driving means used in a normal liquid crystal display element can be used, and the applied voltage is preferably an AC voltage of 0.5 to 50V, more preferably 0.5 to 10V.
【００５６】本発明で用いる基板に施す配向処理として
は、例えば、透明電極に被覆したポリイミド等の有機薄
膜のラビング処理、またはＳｉＯの斜方蒸着等、この技
術分野における通常の知識を有するものにとって既知で
ある配向処理法が挙げられる。The alignment treatment applied to the substrate used in the present invention is, for example, a rubbing treatment of an organic thin film of polyimide or the like coated on a transparent electrode, or oblique vapor deposition of SiO, for those having ordinary knowledge in this technical field. Known alignment treatment methods can be mentioned.
【００５７】[0057]
【実施例】以下、本発明の実施例を示し、本発明をさら
に具体的に説明する。しかしながら、本発明はこれらの
実施例に限定されるものではない。なお、以下の合成
例、実施例、調製例、比較例において「％」は「重量
％」を表す。EXAMPLES The present invention will now be described more specifically by showing examples of the present invention. However, the invention is not limited to these examples. In the following synthesis examples, examples, preparation examples and comparative examples, "%" represents "% by weight".
【００５８】（実施例１） ジアクリレート（１）の合
成Example 1 Synthesis of diacrylate (1)
【００５９】[0059]
【化２９】 [Chemical 29]
【００６０】（第１段階） 中間体（１）の合成(Step 1) Synthesis of Intermediate (1)
【００６１】[0061]
【化３０】 [Chemical 30]
【００６２】２−（ヒドロキシフェニル）エチルアルコ
ール１０．０ｇ、アクリル酸２０．７５ｇ、およびｐ−
トルエンスルホン酸３ｇを、ベンゼン１５０ml中に溶解
し、ディーンスターク水分離器を用いて生成する水分を
分離しながら１０時間加熱還流した。室温まで冷却後、
反応液を水洗し、ベンゼンを減圧留去して１２．６ｇの
粗生成物を得た。これをシリカゲルカラムクロマトグラ
フィー（酢酸エチル：ｎ−ヘキサン＝１：１、Ｒｆ＝
０．５３）を用いて精製し、１０．３ｇの中間体（１）
を得た。10.0 g of 2- (hydroxyphenyl) ethyl alcohol, 20.75 g of acrylic acid, and p-
Toluenesulfonic acid (3 g) was dissolved in benzene (150 ml), and the mixture was heated under reflux for 10 hours while separating generated water using a Dean-Stark water separator. After cooling to room temperature,
The reaction solution was washed with water and benzene was distilled off under reduced pressure to obtain 12.6 g of a crude product. This was subjected to silica gel column chromatography (ethyl acetate: n-hexane = 1: 1, Rf =
0.53) and 10.3 g of intermediate (1)
Got
【００６３】（第２段階） 中間体（２）の合成(Second Step) Synthesis of Intermediate (2)
【００６４】[0064]
【化３１】 [Chemical 31]
【００６５】４−ヒドロキシメチル安息香酸５．０ｇ、
アクリル酸７．４ｇ、ｐ−トルエンスルホン酸３．８
ｇ、ヒドロキノン１．１ｇを、ベンゼン１００mlに溶解
し、ディーンスターク水分離器を用いて生成する水分を
分離しながら５時間加熱還流した。室温まで冷却後、反
応液を水洗し、ベンゼンを減圧留去して１０．４ｇの粗
生成物を得た。これをシリカゲルカラムクロマトグラフ
ィー（酢酸エチル：ｎ−ヘキサン＝１：１、Ｒｆ＝０．
４５）およびｎ−ヘキサン５０mlと酢酸エチル１８mlの
混合溶媒からの再結晶により精製して２．７ｇの中間体
（２）を得た。5.0 g of 4-hydroxymethylbenzoic acid,
Acrylic acid 7.4 g, p-toluenesulfonic acid 3.8
g and hydroquinone (1.1 g) were dissolved in 100 ml of benzene, and the mixture was heated under reflux for 5 hours while separating water produced using a Dean-Stark water separator. After cooling to room temperature, the reaction solution was washed with water and benzene was distilled off under reduced pressure to obtain 10.4 g of a crude product. This was subjected to silica gel column chromatography (ethyl acetate: n-hexane = 1: 1, Rf = 0.
45) and purified by recrystallization from a mixed solvent of 50 ml of n-hexane and 18 ml of ethyl acetate to obtain 2.7 g of intermediate (2).
【００６６】（第３段階） ジアクリレート（１）の合
成
中間体（２）１．０ｇ、２，６−ジ−tert−ブチルフェ
ノール ０．０１ｇに塩化チオニル４ml、さらにジメチ
ルホルムアミド０．０１ｇを加えて、室温で１０分間撹
拌した後、未反応の塩化チオニルを減圧留去してテトラ
ヒドロフランを１５ml加えた。この溶液に、中間体
（１）０．９３ｇとトリエチルアミン１．０６ｇをテト
ラヒドラフラン２０mlに溶解させた溶液を５分間かけて
滴下して後、さらに４時間撹拌した。この反応液を塩化
メチレンを用いて抽出し、有機層を水洗後、有機溶媒を
減圧留去して１．７ｇの粗生成物を得た。これをシリカ
ゲルカラムクロマトグラフィー（酢酸エチル：ｎ−ヘキ
サン＝１：５、Ｒｆ＝０．２１）およびエタノール１０
mlからの再結晶により精製して０．７ｇのジアクリレー
ト（１）を得た。融点を測定したところ、７９℃であっ
た。(Third stage) 1.0 g of a synthetic intermediate (2) of diacrylate (1), 0.01 g of 2,6-di-tert-butylphenol, 4 ml of thionyl chloride and 0.01 g of dimethylformamide were added. After stirring at room temperature for 10 minutes, unreacted thionyl chloride was distilled off under reduced pressure and 15 ml of tetrahydrofuran was added. A solution prepared by dissolving 0.93 g of intermediate (1) and 1.06 g of triethylamine in 20 ml of tetrahydrafuran was added dropwise to this solution over 5 minutes, and the mixture was further stirred for 4 hours. The reaction solution was extracted with methylene chloride, the organic layer was washed with water, and the organic solvent was distilled off under reduced pressure to obtain 1.7 g of a crude product. This was subjected to silica gel column chromatography (ethyl acetate: n-hexane = 1: 5, Rf = 0.21) and ethanol 10
Purification by recrystallization from ml gave 0.7 g of diacrylate (1). The melting point was measured and found to be 79 ° C.
【００６７】（合成例） ジアクリレート（２）の合成(Synthesis Example) Synthesis of diacrylate (2)
【００６８】[0068]
【化３２】 [Chemical 32]
【００６９】アクリル酸２−ヒドロキシエチル２．８
ｇ、トリエチルアミン４．９ｇをテトラヒドロフラン１
５mlに溶解後、この溶液に４，４’−ビフェニルジカル
ボニルクロリド３．０ｇを溶解させた１０mlのＴＨＦ溶
液を５分間かけて滴下した。さらに、３時間撹拌後、塩
化メチレンを用いて抽出し、有機層を水洗後、有機溶媒
を減圧留去して、４．１ｇの粗生成物を得た。これをエ
タノール２０mlからの再結晶により精製して２．２ｇの
ジアクリレート（２）を得た。融点を測定したところ、
７２℃であった。2-hydroxyethyl acrylate 2.8
g, triethylamine 4.9 g tetrahydrofuran 1
After dissolving in 5 ml, 10 ml of a THF solution in which 3.0 g of 4,4'-biphenyldicarbonyl chloride was dissolved was added dropwise to this solution over 5 minutes. After stirring for 3 hours, the mixture was extracted with methylene chloride, the organic layer was washed with water, and the organic solvent was distilled off under reduced pressure to obtain 4.1 g of a crude product. This was purified by recrystallization from 20 ml of ethanol to obtain 2.2 g of diacrylate (2). When the melting point was measured,
It was 72 ° C.
【００７０】（実施例２） ジアクリレート（３）の合
成Example 2 Synthesis of diacrylate (3)
【００７１】[0071]
【化３３】 [Chemical 33]
【００７２】トランス−１，４−シクロヘキサンジカル
ボン酸０．５ｇに、塩化チオニル４ml、さらにジメチル
ホルムアミド０．０１ｇを加えて、室温で３０分間撹拌
した後、未反応の塩化チオニルを減圧留去してテトラヒ
ドロフランを１０ml加えた。この溶液に、中間体（１）
１．１１ｇとトリエチルアミン１．４０ｇをテトラヒド
ロフラン２０mlに溶解させた溶液を５分間かけて滴下し
て後、さらに４時間撹拌した。この反応液を塩化メチレ
ンを用いて抽出し、有機層を水洗後、有機溶媒を減圧留
去して１．６ｇの粗生成物を得た。これをエタノール１
８mlからの再結晶により精製して１．０ｇのジアクリレ
ート（３）を得た。この化合物はモノトロピックなネマ
チック液晶相を有し、等方性液体相からネマチック相に
１２６℃で転移し、結晶相から等方性液体相に１３２℃
で転移した。To 0.5 g of trans-1,4-cyclohexanedicarboxylic acid, 4 ml of thionyl chloride and 0.01 g of dimethylformamide were added, and the mixture was stirred at room temperature for 30 minutes, and then unreacted thionyl chloride was distilled off under reduced pressure. 10 ml of tetrahydrofuran was added. In this solution, the intermediate (1)
A solution prepared by dissolving 1.11 g and 1.40 g of triethylamine in 20 ml of tetrahydrofuran was added dropwise over 5 minutes, and the mixture was further stirred for 4 hours. The reaction solution was extracted with methylene chloride, the organic layer was washed with water, and then the organic solvent was distilled off under reduced pressure to obtain 1.6 g of a crude product. This is ethanol 1
Purification by recrystallization from 8 ml gave 1.0 g of diacrylate (3). This compound has a monotropic nematic liquid crystal phase, transitions from an isotropic liquid phase to a nematic phase at 126 ° C., and a crystalline phase to an isotropic liquid phase at 132 ° C.
It was transferred at.
【００７３】（実施例３） ジアクリレート（４）の合
成Example 3 Synthesis of diacrylate (4)
【００７４】[0074]
【化３４】 [Chemical 34]
【００７５】（第１段階） 中間体（３）の合成(First Step) Synthesis of Intermediate (3)
【００７６】[0076]
【化３５】 [Chemical 35]
【００７７】４−ヒドロキシ安息香酸２０．０ｇにエタ
ノール６０ｍｌ、及び５５ｍｌの水に溶解した水酸化ナ
トリウムを加えて攪拌した。これにヨウ化カリウム１．
８ｇと６−クロロ−１−ヘキサノール１４．４ｇを加え
て２０時間加熱還流した。加熱還流後、反応溶液に２０
０ｍｌの水を加えてから、反応溶液を希塩酸水溶液を用
いて中和した。反応溶液中に生成した沈澱物を濾取し、
これを５５ｍｌのエタノールから再結晶して１９．９ｇ
の中間体（３）を得た。To 20.0 g of 4-hydroxybenzoic acid, 60 ml of ethanol and 55 ml of sodium hydroxide dissolved in water were added and stirred. Potassium iodide 1.
8 g and 14.4 g of 6-chloro-1-hexanol were added, and the mixture was heated under reflux for 20 hours. After heating under reflux, add 20 to the reaction solution.
After adding 0 ml of water, the reaction solution was neutralized with a dilute aqueous hydrochloric acid solution. The precipitate formed in the reaction solution was collected by filtration,
This was recrystallized from 55 ml of ethanol to give 19.9 g.
The intermediate (3) of was obtained.
【００７８】（第２段階） 中間体（４）の合成(Second Step) Synthesis of Intermediate (4)
【００７９】[0079]
【化３６】 [Chemical 36]
【００８０】中間体（３）１６．０ｇ、アクリル酸１
５．０ｇ、ｐ−トルエンスルホン酸８．０ｇ、ヒドロキ
ノン０．５ｇを、ベンゼン２１０ｍｌに溶解し、ディー
ンスターク水分離器を用いて生成する水分を分離しなが
ら１２時間加熱還流した。室温まで冷却後、反応液を水
洗し、ベンゼンを減圧留去して３４．６ｇの粗生成物を
得た。これをヘキサン１５０ｍｌとジクロロメタン５０
ｍｌの混合溶媒からの再結晶により精製して１３．６ｇ
の中間体（４）を得た。Intermediate (3) 16.0 g, acrylic acid 1
5.0 g, p-toluenesulfonic acid 8.0 g, and hydroquinone 0.5 g were dissolved in benzene 210 ml, and the mixture was heated under reflux for 12 hours while separating generated water using a Dean-Stark water separator. After cooling to room temperature, the reaction solution was washed with water and benzene was distilled off under reduced pressure to obtain 34.6 g of a crude product. Add 150 ml of hexane and 50 ml of dichloromethane.
Purified by recrystallization from 1 ml of mixed solvent (13.6 g)
The intermediate (4) of was obtained.
【００８１】（第３段階） ジアクリレート（４）の合
成
中間体（４）０．７５ｇ、１，２−ジ−tert−ブチルフ
ェノール０．０１ｇに塩化チオニル２．２ｍｌ、更にジ
メチルホルムアミド０．０１ｇを加えて、室温で１０分
間攪拌した後、未反応の塩化チオニルを減圧留去してト
ルエン１０ｍｌを加えた。この溶液を、中間体（１）
０．４９ｇとピリジン０．８ｇを溶解させた２０ｍｌの
トルエン溶液に５分間かけて滴下した。更に２時間攪拌
後、有機層を水洗、更に有機層を減圧留去して１．１０
ｇの粗生成物を得た。これをシリカゲルカラムクロマト
グラフィー（酢酸エチル：ｎ−ヘキサン＝１：２、Ｒｆ
＝０．４７）及びエタノール５ｍｌからの再結晶により
精製して、０．２２ｇのジアクリレート（４）を得た。
融点を測定したところ４２℃であった。(Third step) 0.75 g of synthetic intermediate (4) of diacrylate (4), 0.01 g of 1,2-di-tert-butylphenol, 2.2 ml of thionyl chloride, and 0.01 g of dimethylformamide. In addition, after stirring at room temperature for 10 minutes, unreacted thionyl chloride was distilled off under reduced pressure, and 10 ml of toluene was added. This solution is used as an intermediate (1)
It was added dropwise to a 20 ml toluene solution in which 0.49 g and 0.8 g of pyridine were dissolved over 5 minutes. After stirring for another 2 hours, the organic layer was washed with water, and the organic layer was evaporated under reduced pressure to give 1.10.
g of crude product was obtained. This was subjected to silica gel column chromatography (ethyl acetate: n-hexane = 1: 2, Rf
= 0.47) and recrystallized from 5 ml of ethanol to obtain 0.22 g of diacrylate (4).
The melting point was measured and found to be 42 ° C.
【００８２】（調製例） ネマチック液晶組成物（Ａ）
の調製Preparation Example Nematic liquid crystal composition (A)
Preparation of
【００８３】[0083]
【化３７】 [Chemical 37]
【００８４】からなるネマチック液晶組成物（Ａ）を調
製した。この液晶組成物の物性は、以下に示すとおりで
あった。
転移温度 ６８．７℃（Ｎ−Ｉ）
ｎe ＝１．７０２
ｎo ＝１．５１３
Δｎ＝０．１８９
Δε＝７．１７
以下、参考例１〜４において、本発明で使用する液晶性
骨格を有するジアクリレート化合物を用いた場合の液晶
表示素子の傾斜配向角を測定した。また、参考例５にお
いて、液晶性骨格を有していないジアクリレート化合物
を用いた場合の液晶表示素子の傾斜配向角を測定した。
測定した結果は、表１に示した。A nematic liquid crystal composition (A) consisting of was prepared. The physical properties of this liquid crystal composition were as follows. Transition temperature 68.7 ℃ (N-I) n e = 1.702 n o = 1.513 Δn = 0.189 Δε = 7.17 or less, in Reference Examples 1-4, crystalline framework for use in the present invention The tilted orientation angle of the liquid crystal display device was measured when the diacrylate compound having the formula was used. In addition, in Reference Example 5, the tilt orientation angle of the liquid crystal display device when a diacrylate compound having no liquid crystalline skeleton was used was measured.
The measured results are shown in Table 1.
【００８５】（参考例１）液晶組成物（Ａ）９７％と合
成例１で合成したジアクリレート（１）３％のネマチッ
ク液晶組成物を作製し、ネマチック−等方性液体転移温
度を測定したところ６２．４℃であった。このネマチッ
ク液晶組成物に、ジアクリレート（１）の量に対して８
％に当たる量の重合開始剤「イルガキュア６５１」（チ
バ・ガイギー社製ベンジルジメチルケタール）を加えて
混合物を作製し、ポリイミド配向膜を形成したセルギャ
ップ１０μｍのアンチパラレルセルに注入した。そし
て、この混合物が、前記セル中でラビング方向に配向し
ているのを偏光顕微鏡観察により確認した。Reference Example 1 A nematic liquid crystal composition containing 97% of the liquid crystal composition (A) and 3% of the diacrylate (1) synthesized in Synthesis Example 1 was prepared, and the nematic-isotropic liquid transition temperature was measured. The temperature was 62.4 ° C. This nematic liquid crystal composition contains 8 parts by weight of diacrylate (1).
% Of a polymerization initiator “Irgacure 651” (benzyl dimethyl ketal manufactured by Ciba-Geigy) was added to prepare a mixture, which was then injected into an anti-parallel cell having a cell gap of 10 μm on which a polyimide alignment film was formed. Then, it was confirmed by polarization microscope observation that this mixture was oriented in the rubbing direction in the cell.
【００８６】前記セルに周波数１KHz、電圧１Ｖの正弦
波を印加しながら、２８℃の温度で紫外線を照射してジ
アクリレート化合物を重合させて液晶表示素子を作製し
た。重合はメタルハライドランプ（１２０Ｗ／cm2）の
下を４ｍ／分の速度で２回通過させ、１５００mＪ／cm2
に相当するエネルギーを照射することによって行った。While applying a sine wave having a frequency of 1 KHz and a voltage of 1 V to the above cell, ultraviolet rays were irradiated at a temperature of 28 ° C. to polymerize the diacrylate compound to prepare a liquid crystal display device. Polymerization was passed under a metal halide lamp (120 W / cm 2 ) twice at a speed of 4 m / min, 1500 mJ / cm 2
Was performed by irradiating with energy corresponding to.
【００８７】得られた液晶表示素子を偏光顕微鏡で観察
した結果、液晶分子の配向は均一で紫外線照射後も乱れ
ていないことを確認した。また、この液晶表示素子の傾
斜配向角を、プレチルト角を測定するのに用いられてい
るクリスタルローテーション法を適用して測定した。３
mmずつ間隔をおいて３ケ所の測定をした結果、その値は
それぞれ、２．８°、２．９°、２．９°であった。こ
の結果から、液晶表示素子内での液晶の配向が乱れてい
ないことは明らかである。As a result of observing the obtained liquid crystal display device with a polarization microscope, it was confirmed that the alignment of liquid crystal molecules was uniform and was not disturbed even after irradiation with ultraviolet rays. The tilt orientation angle of this liquid crystal display device was measured by applying the crystal rotation method used for measuring the pretilt angle. Three
As a result of measuring at three points at intervals of mm, the values were 2.8 °, 2.9 °, and 2.9 °, respectively. From this result, it is clear that the alignment of the liquid crystal in the liquid crystal display element is not disturbed.
【００８８】（参考例２）参考例１においてジアクリレ
ート（２）を使用した以外は参考例１と同様にして、液
晶表示素子を得た。液晶組成物（Ａ）９７％とジアクリ
レート（２）３％のネマチック液晶組成物のネマチック
−等方性液体転移温度は、６２．４℃であった。Reference Example 2 A liquid crystal display device was obtained in the same manner as in Reference Example 1 except that the diacrylate (2) was used in Reference Example 1. The nematic-isotropic liquid transition temperature of the nematic liquid crystal composition of 97% liquid crystal composition (A) and 3% diacrylate (2) was 62.4 ° C.
【００８９】また、この液晶表示素子を偏光顕微鏡で観
察した結果、液晶分子の配向は均一で紫外線照射後も乱
れていないことを確認した。３mmずつ間隔をおいて３ケ
所の測定をした傾斜配向角の値は、それぞれ３．１°、
３．２°、３．２°であった。As a result of observing this liquid crystal display element with a polarization microscope, it was confirmed that the alignment of liquid crystal molecules was uniform and was not disturbed even after irradiation with ultraviolet rays. The value of the tilt orientation angle measured at 3 points at intervals of 3 mm is 3.1 °,
The angles were 3.2 ° and 3.2 °.
【００９０】（参考例３）参考例１においてジアクリレ
ート（３）を使用した以外は参考例１と同様にして液晶
表示素子を得た。液晶組成物（Ａ）９７％とジアクリレ
ート（３）３％のネマチック液晶組成物のネマチック−
等方性液体転移温度は、６６．７℃であった。Reference Example 3 A liquid crystal display device was obtained in the same manner as in Reference Example 1 except that the diacrylate (3) was used in Reference Example 1. Nematic liquid crystal composition (A) 97% and diacrylate (3) 3% nematic liquid crystal composition-
The isotropic liquid transition temperature was 66.7 ° C.
【００９１】また、この液晶表示素子を偏光顕微鏡で観
察した結果、液晶分子の配向は均一で紫外線照射後も乱
れていないことを確認した。３mmずつ間隔をおいて３ケ
所の測定をした傾斜配向角の値は、それぞれ３．１°、
３．１°、３．１°であった。As a result of observing this liquid crystal display element with a polarization microscope, it was confirmed that the alignment of liquid crystal molecules was uniform and was not disturbed even after irradiation with ultraviolet rays. The value of the tilt orientation angle measured at 3 points at intervals of 3 mm is 3.1 °,
It was 3.1 ° and 3.1 °.
【００９２】（参考例４）参考例１において、特開昭６
３−６４０２９号公報に記載の液晶性ジアクリレート
（５）Reference Example 4 In Reference Example 1, JP-A-6
Liquid crystalline diacrylate (5) described in JP-A-3-64029.
【００９３】[0093]
【化３８】 [Chemical 38]
【００９４】を使用した以外は参考例１と同様にして、
液晶表示素子を得た。液晶組成物（Ａ）９７％とジアク
リレート（４）３％のネマチック液晶組成物のネマチッ
ク−等方性液体転移温度は、６９．０℃であった。ま
た、この液晶表示素子を偏光顕微鏡で観察した結果、液
晶分子の配向は均一で、紫外線照射後も乱れていないこ
とを確認した。３mmずつ間隔をおいて３ケ所の測定をし
た傾斜配向角の値は、それぞれ５．０°、５．０°、
５．０°であった。In the same manner as in Reference Example 1, except that
A liquid crystal display device was obtained. The nematic-isotropic liquid transition temperature of the nematic liquid crystal composition of 97% liquid crystal composition (A) and 3% diacrylate (4) was 69.0 ° C. Moreover, as a result of observing this liquid crystal display element with a polarization microscope, it was confirmed that the alignment of the liquid crystal molecules was uniform and was not disturbed even after irradiation with ultraviolet rays. The values of the tilted orientation angle measured at 3 points at intervals of 3 mm are 5.0 °, 5.0 °,
It was 5.0 °.
【００９５】（参考例５）参考例１においてジアクリレ
ートとして液晶性骨格を有していないジアクリレート
（６）Reference Example 5 Diacrylate (6) having no liquid crystal skeleton as diacrylate in Reference Example 1
【００９６】[0096]
【化３９】 [Chemical Formula 39]
【００９７】を使用した以外は参考例１と同様にして液
晶表示素子を得た。液晶組成物（Ａ）９７％とジアクリ
レート（５）３％のネマチック液晶組成物のネマチック
−等方性液体転移温度は、５９．３℃であった。この液
晶表示素子を偏光顕微鏡で観察した結果、液晶分子の配
向が乱れている場所があることを確認した。また、３mm
ずつ間隔をおいて３ケ所の測定をした傾斜配向角の値
は、それぞれ１．２°、５．０°、４．４°であった。A liquid crystal display device was obtained in the same manner as in Reference Example 1 except that was used. The nematic-isotropic liquid transition temperature of the nematic liquid crystal composition of 97% liquid crystal composition (A) and 3% diacrylate (5) was 59.3 ° C. As a result of observing this liquid crystal display element with a polarization microscope, it was confirmed that there were places where the alignment of liquid crystal molecules was disturbed. Also, 3 mm
The values of the tilt orientation angles measured at three positions at intervals of 1.2 °, 5.0 ° and 4.4 °, respectively.
【００９８】[0098]
【表１】 [Table 1]
【００９９】表１に示した液晶表示素子の傾斜配向角か
ら明らかなように、液晶性骨格を有するジアクリレート
化合物（ジアクリレート（１）〜（５））は、液晶性骨
格を有していないジアクリレート化合物（ジアクリレー
ト（６））に比較して、液晶分子の配向の均一性が優れ
ている。As is clear from the tilted orientation angles of the liquid crystal display device shown in Table 1, the diacrylate compounds having a liquid crystal skeleton (diacrylates (1) to (5)) do not have a liquid crystal skeleton. Compared to the diacrylate compound (diacrylate (6)), the alignment uniformity of liquid crystal molecules is excellent.
【０１００】（実施例４）液晶組成物（Ａ）にペラルゴ
ン酸コレステロールを２．４％加えてカイラル混合物を
作製し、ピッチを測定したところ８．５３μｍであっ
た。このカイラル混合物９８％と合成例１で合成したジ
アクリレート（１）２％のネマチック液晶組成物を作製
した。このネマチック液晶組成物に、ジアクリレート
（１）の量に対して８％にあたる量の重合開始剤「イル
ガキュア６５１」（チバ・ガイギー社製ベンジルジメチ
ルケタール）を加えて混合物を作製し、２枚の基板上の
配向方向が２７０゜であるポリイミド配向膜を形成した
セルギャップ４．９μｍのＴＮセルに注入した。このセ
ルに周波数１KHz、電圧８Ｖの正弦波を印加しながら、
２８℃の温度で紫外線を照射してジアクリレート化合物
を重合させて液晶表示素子を作製した。重合はメタルハ
ライドランプ（１２０Ｗ／cm2）の下を４ｍ／分の速度
で２回通過させ、１５００mＪ／cm2に相当するエネルギ
ーを照射することによって行なった。直交する２枚の偏
光板の間に得られた液晶表示素子を置き、これに電圧を
印加したところ、動作するのが確認できた。また、偏光
顕微鏡観察下、得られた液晶表示素子に電圧を印加して
も、ストライプドメインの発生は確認されなかった。Example 4 2.4% of cholesterol pelargonate was added to the liquid crystal composition (A) to prepare a chiral mixture, and the pitch was measured and found to be 8.53 μm. A nematic liquid crystal composition containing 98% of this chiral mixture and 2% of diacrylate (1) synthesized in Synthesis Example 1 was prepared. To this nematic liquid crystal composition, a polymerization initiator “Irgacure 651” (benzyl dimethyl ketal manufactured by Ciba-Geigy) in an amount corresponding to 8% of the amount of diacrylate (1) was added to prepare a mixture, and two sheets of the mixture were prepared. The film was injected into a TN cell having a cell gap of 4.9 μm on which a polyimide alignment film having an alignment direction of 270 ° was formed on a substrate. While applying a sine wave with a frequency of 1 KHz and a voltage of 8 V to this cell,
Ultraviolet rays were irradiated at a temperature of 28 ° C. to polymerize the diacrylate compound to prepare a liquid crystal display device. The polymerization was carried out by passing it under a metal halide lamp (120 W / cm 2 ) twice at a speed of 4 m / min and irradiating it with energy corresponding to 1500 mJ / cm 2 . When the obtained liquid crystal display element was placed between two polarizing plates which were orthogonal to each other and a voltage was applied to it, it was confirmed to operate. Further, generation of stripe domains was not confirmed even when a voltage was applied to the obtained liquid crystal display element under observation with a polarizing microscope.
【０１０１】（比較例１）液晶組成物（Ａ）にペラルゴ
ン酸コレステロールを２．４％加えてカイラル混合物を
作製し、ピッチを測定したところ８．５３μｍであっ
た。この混合物をポリイミド配向膜を形成したセルギャ
ップ４．９μｍのＴＮセルに注入して液晶表示素子を得
た。直交する２枚の偏光板の間に得られた液晶表示素子
を置き、これに電圧を印加したところ、動作するのが確
認できた。しかし、偏光顕微鏡観察下、得られた液晶表
示素子に電圧を印加すると、ストライプドメインが発生
した。Comparative Example 1 2.4% of cholesterol pelargonate was added to the liquid crystal composition (A) to prepare a chiral mixture, and the pitch was measured and found to be 8.53 μm. This mixture was injected into a TN cell having a polyimide alignment film and a cell gap of 4.9 μm to obtain a liquid crystal display device. When the obtained liquid crystal display element was placed between two polarizing plates which were orthogonal to each other and a voltage was applied to it, it was confirmed to operate. However, when a voltage was applied to the obtained liquid crystal display device under observation with a polarizing microscope, stripe domains were generated.
【０１０２】（実施例５）実施例４においてジアクリレ
ートとして実施例３で合成したジアクリレート（４）を
使用した以外は実施例４と同様にして液晶表示素子を得
た。直交する２枚の偏光板の間に得られた液晶表示素子
を置き、これに電圧を印加したところ動作するのが確認
出来た。また偏光顕微鏡観察下、得られた液晶表示素子
に電圧を印加しても、ストライプドメインの発生は確認
されなかった。Example 5 A liquid crystal display device was obtained in the same manner as in Example 4, except that the diacrylate (4) synthesized in Example 3 was used as the diacrylate in Example 4. It was confirmed that the obtained liquid crystal display element was placed between two polarizing plates which were orthogonal to each other, and a voltage was applied thereto to operate. Further, when a voltage was applied to the obtained liquid crystal display element under observation with a polarizing microscope, generation of stripe domains was not confirmed.
【０１０３】以上の結果から、本発明の液晶表示素子
は、高いプレチルト角を有する液晶表示素子と同様にス
トライプドメインが発生せず、また配向の均一性も優れ
ていることは明らかである。From the above results, it is apparent that the liquid crystal display element of the present invention does not generate stripe domains and has excellent alignment uniformity as in the liquid crystal display element having a high pretilt angle.
【０１０４】[0104]
【発明の効果】本発明の液晶表示素子は、液晶の配向状
態が均一で、かつ高いプレチルト角を有する液晶表示素
子と同様の特性を有する液晶表示素子であり、ＴＮ型、
ＳＴＮ型表示素子への応用が可能である。The liquid crystal display device of the present invention is a liquid crystal display device having a uniform liquid crystal alignment state and the same characteristics as a liquid crystal display device having a high pretilt angle.
It can be applied to STN type display elements.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平３−140921（ＪＰ，Ａ) 特開 平３−21904（ＪＰ，Ａ) 特開 昭63−64029（ＪＰ，Ａ) 特開 平６−289374（ＪＰ，Ａ) 欧州特許出願公開331233（ＥＰ，Ａ １) (58)調査した分野(Int.Cl.7，ＤＢ名) G02F 1/1337 G02F 1/133 500 G02F 1/13 500 G02F 1/137 C09K 19/38 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-3-140921 (JP, A) JP-A-3-21904 (JP, A) JP-A-63-64029 (JP, A) JP-A-6- 289374 (JP, A) European patent application publication 331233 (EP, A 1) (58) Fields investigated (Int.Cl. 7 , DB name) G02F 1/1337 G02F 1/133 500 G02F 1/13 500 G02F 1 / 137 C09K 19/38
Claims (5)
くとも一方が透明な２枚の基板であって、２枚の基板上
の配向方向が１８０〜２７０゜の範囲にある基板間に、
液晶／高分子複合体を有し、該液晶／高分子複合体が、
ネマチック液晶およびカイラル物質と液晶性骨格を有す
るジアクリレート化合物との重合体を含有し、該液晶／
高分子複合体中に、該重合体と液晶との界面に沿って配
向する液晶分子を含有し、かつ、基板面に対し２〜５０
゜の範囲で傾斜している液晶分子を含有し、該液晶性骨
格を有するジアクリレート化合物が、一般式（ａ） 【化１】 （式中、Ｚ １ 及びＺ ２ はそれぞれ独立的に、水素原子ま
たはメチル基を表す。）、一般式（ｂ） 【化２】 （式中、Ｚ １ 及びＺ ２ はそれぞれ独立的に、水素原子ま
たはメチル基を表す。）又は一般式（ｃ） 【化３】 （式中、Ｚ １ 及びＺ ２ はそれぞれ独立的に、水素原子ま
たはメチル基を表す。）で表される化合物であることを
特徴とする液晶表示素子。1. A transparent substrate having at least one of which has a transparent electrode subjected to an alignment treatment, wherein the two substrates are transparent, and the alignment direction on the two substrates is in the range of 180 to 270 °.
A liquid crystal / polymer composite, wherein the liquid crystal / polymer composite is
A nematic liquid crystal and a polymer of a chiral substance and a diacrylate compound having a liquid crystalline skeleton are contained.
The polymer composite contains liquid crystal molecules aligned along the interface between the polymer and the liquid crystal, and is 2 to 50 relative to the substrate surface.
Containing liquid crystal molecules are inclined in DEG, the liquid crystal bone
The diacrylate compound having a case is represented by the general formula (a) : (In the formula, Z 1 and Z 2 are each independently a hydrogen atom or
Or represents a methyl group. ), The general formula (b) : (In the formula, Z 1 and Z 2 are each independently a hydrogen atom or
Or represents a methyl group. ) Or the general formula (c) : (In the formula, Z 1 and Z 2 are each independently a hydrogen atom or
Or represents a methyl group. ) A liquid crystal display device comprising a compound represented by
物が、ネマチック液晶およびカイラル物質に、１〜２０
重量％の範囲で存在することを特徴とする請求項１記載
の液晶表示素子。2. A diacrylate compound having a liquid crystal skeleton is added to a nematic liquid crystal and a chiral substance in an amount of 1 to 20.
The liquid crystal display device according to claim 1, wherein the liquid crystal display device is present in the range of weight%.
くとも一方が透明な２枚の基板であって、２枚の基板上
の配向方向が１８０〜２７０゜の範囲にある基板間に、
ネマチック液晶およびカイラル物質と液晶性骨格を有す
るジアクリレート化合物とを含有する液晶／高分子複合
体形成材料を挟持し、該ネマチック液晶およびカイラル
物質を配向させた後、該液晶／高分子複合体形成材料に
電圧を印加させながら、活性光線を照射し、液晶性骨格
を有するジアクリレート化合物を重合させることを特徴
とする請求項１記載の液晶表示素子の製造方法。3. At least one transparent substrate having an alignment-treated transparent electrode, wherein the two substrates have an orientation direction in the range of 180 to 270 ° between the two substrates.
A liquid crystal / polymer composite forming material containing a nematic liquid crystal and a chiral substance and a diacrylate compound having a liquid crystalline skeleton is sandwiched, and the nematic liquid crystal and the chiral substance are aligned, and then the liquid crystal / polymer composite is formed. The method for producing a liquid crystal display device according to claim 1, wherein the material is irradiated with an actinic ray while applying a voltage to polymerize the diacrylate compound having a liquid crystalline skeleton.
にあることを特徴とする請求項３記載の液晶表示素子の
製造方法。4. The method of manufacturing a liquid crystal display device according to claim 3, wherein the applied voltage used is in the range of 0.5 to 50V.
物が、ネマチック液晶およびカイラル物質に、１〜２０
重量％の範囲で存在することを特徴とする請求項４記載
の液晶表示素子の製造方法。5. A diacrylate compound having a liquid crystal skeleton is added to a nematic liquid crystal and a chiral substance in an amount of 1 to 20.
It exists in the range of weight%, The manufacturing method of the liquid crystal display element of Claim 4 characterized by the above-mentioned.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29976193A JP3513888B2 (en) | 1993-08-16 | 1993-11-30 | Liquid crystal display device and method of manufacturing the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5-202369 | 1993-08-16 | ||
| JP20236993 | 1993-08-16 | ||
| JP29976193A JP3513888B2 (en) | 1993-08-16 | 1993-11-30 | Liquid crystal display device and method of manufacturing the same |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003364641A Division JP3790929B2 (en) | 1993-08-16 | 2003-10-24 | Polymerizable liquid crystal compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07110469A JPH07110469A (en) | 1995-04-25 |
| JP3513888B2 true JP3513888B2 (en) | 2004-03-31 |
Family
ID=26513330
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29976193A Expired - Lifetime JP3513888B2 (en) | 1993-08-16 | 1993-11-30 | Liquid crystal display device and method of manufacturing the same |
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| Country | Link |
|---|---|
| JP (1) | JP3513888B2 (en) |
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- 1993-11-30 JP JP29976193A patent/JP3513888B2/en not_active Expired - Lifetime
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|---|---|
| JPH07110469A (en) | 1995-04-25 |
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