JP2003064032A - Polymerizable compound, liquid crystalline composition and polymer of the same - Google Patents
Polymerizable compound, liquid crystalline composition and polymer of the sameInfo
- Publication number
- JP2003064032A JP2003064032A JP2001251291A JP2001251291A JP2003064032A JP 2003064032 A JP2003064032 A JP 2003064032A JP 2001251291 A JP2001251291 A JP 2001251291A JP 2001251291 A JP2001251291 A JP 2001251291A JP 2003064032 A JP2003064032 A JP 2003064032A
- Authority
- JP
- Japan
- Prior art keywords
- group
- compound
- polymerizable
- liquid crystal
- polymerizable compound
- 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.)
- Pending
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 125
- 229920000642 polymer Polymers 0.000 title claims abstract description 13
- 239000000203 mixture Substances 0.000 title claims description 45
- 239000007788 liquid Substances 0.000 title claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 30
- 125000005843 halogen group Chemical group 0.000 claims abstract description 19
- 125000003118 aryl group Chemical group 0.000 claims abstract description 16
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 15
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 9
- 125000004450 alkenylene group Chemical group 0.000 claims abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- 239000004973 liquid crystal related substance Substances 0.000 claims description 44
- 239000000126 substance Substances 0.000 claims description 32
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 125000006367 bivalent amino carbonyl group Chemical group [H]N([*:1])C([*:2])=O 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 abstract description 13
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 39
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- 239000010408 film Substances 0.000 description 20
- 125000004432 carbon atom Chemical group C* 0.000 description 18
- 125000001424 substituent group Chemical group 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 125000001309 chloro group Chemical group Cl* 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000005264 High molar mass liquid crystal Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000012788 optical film Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- 239000004988 Nematic liquid crystal Substances 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000004990 Smectic liquid crystal Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical group ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003098 cholesteric effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- SXYFKXOFMCIXQW-UHFFFAOYSA-N propanedioyl dichloride Chemical compound ClC(=O)CC(Cl)=O SXYFKXOFMCIXQW-UHFFFAOYSA-N 0.000 description 2
- ZDYVRSLAEXCVBX-UHFFFAOYSA-N pyridinium p-toluenesulfonate Chemical compound C1=CC=[NH+]C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 ZDYVRSLAEXCVBX-UHFFFAOYSA-N 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- 125000004806 1-methylethylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical group COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- ARBAMECCCQZCSR-UHFFFAOYSA-N 4-[2-(4-carboxyphenyl)ethynyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C#CC1=CC=C(C(O)=O)C=C1 ARBAMECCCQZCSR-UHFFFAOYSA-N 0.000 description 1
- JPVUWCPKMYXOKW-UHFFFAOYSA-N 4-phenylbenzoyl chloride Chemical compound C1=CC(C(=O)Cl)=CC=C1C1=CC=CC=C1 JPVUWCPKMYXOKW-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical compound C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 description 1
- 238000006000 Knoevenagel condensation reaction Methods 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000005548 dental material Substances 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- -1 malonic acid ester Chemical class 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000001393 microlithography Methods 0.000 description 1
- NZZGQZMNFCTNAM-UHFFFAOYSA-N naphthalene-2,6-dicarbonyl chloride Chemical compound C1=C(C(Cl)=O)C=CC2=CC(C(=O)Cl)=CC=C21 NZZGQZMNFCTNAM-UHFFFAOYSA-N 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Materials For Photolithography (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は光重合架橋性を有す
る化合物、それを含有する液晶性組成物、及びその重合
体に関するものであり、特に、架橋状態において光学構
成成分、パターニングされた構造体、又は電子材料構成
成分として使用できる液晶性組成物に関する。TECHNICAL FIELD The present invention relates to a compound having photopolymerization crosslinkability, a liquid crystal composition containing the compound, and a polymer thereof, and particularly to an optical component in a crosslinked state and a patterned structure. Or a liquid crystal composition that can be used as a constituent component of an electronic material.
【0002】[0002]
【従来の技術】液晶化合物は液晶表示装置に使用される
以外にも、その光学的、機械強度的、電気的異方性を利
用した、位相差膜や導波路、回析格子、光学フィルタ
ー、高強度繊維、導電性異方材料などの構成材料として
も盛んに研究がなされている。後者の用途の場合、液晶
の流動性がその用途にとって不具合となるため、これを
固体化する試みがなされている。例えば特開平5−61
039には、高分子液晶を用いて、ガラス転移温度以上
に加熱して、液晶相を示す温度領域で配向熟成を行った
後、急冷してガラス状態にして液晶分子の配向を固定化
する方法が記載されている。また、「液晶」、3
(1)、34(1999)に記載されているような、液
晶性モノマー又はジアクリレートモノマーを光重合させ
ることによって、配向を固定化する方法も知られてい
る。2. Description of the Related Art Liquid crystal compounds are used not only in liquid crystal display devices but also in retardation films, waveguides, diffractive gratings, optical filters, which utilize their optical, mechanical strength and electrical anisotropy. It is also being actively researched as a constituent material such as high-strength fiber and conductive anisotropic material. In the case of the latter application, the fluidity of the liquid crystal becomes a problem for that application, and therefore, attempts have been made to solidify the liquid crystal. For example, JP-A-5-61
For 039, a method in which a polymer liquid crystal is used to heat above the glass transition temperature to perform orientation aging in a temperature range showing a liquid crystal phase, and then to be rapidly cooled into a glass state to fix the orientation of liquid crystal molecules Is listed. Also, "liquid crystal", 3
There is also known a method of fixing the alignment by photopolymerizing a liquid crystalline monomer or a diacrylate monomer as described in (1), 34 (1999).
【0003】しかし、これらの方法を用いて固定化され
た膜や構造体は、比較的低いガラス転移温度を示すため
に、高温での使用時に配向が乱れて、光学異方性などの
性質が大きく変化する。また、膜強度が低いばかりでな
く、損傷も受け易く、更に、溶媒等の薬品に対する耐性
も低いという欠点があった。また、特開平8−1048
70号公報には、3官能性の重合性基を有する重合性液
晶化合物が示されている。しかし、この重合性液晶化合
物は2官能性液晶化合物との混和性が低いという問題点
がある。また、特開平7−278060号公報には、2
官能性の重合性液晶化合物を連結した形の4官能性の重
合性液晶化合物が示されている。しかし、この重合性液
晶化合物も屈折率の異方性が小さくなるという欠点を有
していた。また、Liquid Crystals 1
988,<3>,1047−1053には、前記一般式
(I)で示される化合物でP1〜P4の全てが重合性基で
はない化合物が開示されているが、この化合物もやはり
上記同様の欠点があった。However, since the film or structure immobilized by these methods has a relatively low glass transition temperature, the orientation is disturbed when used at a high temperature, and the properties such as optical anisotropy are generated. It changes a lot. Further, there are drawbacks that not only the film strength is low, but also the film is easily damaged and the resistance to chemicals such as a solvent is low. In addition, JP-A-8-1048
JP-A-70 discloses a polymerizable liquid crystal compound having a trifunctional polymerizable group. However, there is a problem that this polymerizable liquid crystal compound has low miscibility with the bifunctional liquid crystal compound. Further, in Japanese Patent Laid-Open No. 7-278060, 2
A tetrafunctional polymerizable liquid crystal compound is shown in the form of linked functional polymerizable liquid crystal compounds. However, this polymerizable liquid crystal compound also has a drawback that the anisotropy of the refractive index becomes small. Also, Liquid Crystals 1
988, <3>, 1047-1053 discloses a compound represented by the above general formula (I) in which all of P 1 to P 4 are not polymerizable groups. There was a drawback.
【0004】[0004]
【発明が解決しようとする課題】本発明は上記の問題点
に鑑みてなされたものであり、その第1の目的は、重合
体の高温使用時における光学的性質等の特性が変化せ
ず、また膜強度や耐スクラッチ性などの機械的特性に優
れる膜を形成しうる重合性の化合物を提供することにあ
る。SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and a first object of the present invention is not to change the characteristics such as optical properties of a polymer when it is used at high temperature. Another object is to provide a polymerizable compound capable of forming a film having excellent mechanical properties such as film strength and scratch resistance.
【0005】[0005]
【課題を解決するための手段】前記課題は、本発明の以
下の重合性化合物及びこれを用いる組成物並びにその重
合体を提供することによって解決される。即ち、本発明
は、
<1> 下記一般式(I)で表される重合性化合物。The above-mentioned problems can be solved by providing the following polymerizable compound of the present invention, a composition using the same, and a polymer thereof. That is, the present invention provides <1> a polymerizable compound represented by the following general formula (I).
【化4】
〔式(I)中、P1〜P4は夫々独立に重合性基、水素原
子、ハロゲン原子、水酸基、−NHR3(R3は水素原
子、アルキル基を表す)を表し、P1〜P4の内少なくと
も1つは重合性基を表す。L1〜L4は夫々独立にアルキ
レン基、アルケニレン基、アラルキレン基、単結合を表
す。R1とR2は夫々独立に水素原子、アルキル基、アリ
ール基を表す。X1とX2は夫々独立にハロゲン原子、ア
ルキル基、アルコキシ基を表す。Z1とZ2は夫々独立に
単結合、−COO−、−O−CO−、−CONH−、−
NHCO−、−CH=CH−、−C≡C−を表す。aと
bは0、1、2の整数を表す。[Chemical 4] [In formula (I), P 1 to P 4 each independently represent a polymerizable group, a hydrogen atom, a halogen atom, a hydroxyl group, —NHR 3 (R 3 represents a hydrogen atom or an alkyl group), and P 1 to P 4 At least one of 4 represents a polymerizable group. L 1 to L 4 each independently represent an alkylene group, an alkenylene group, an aralkylene group, or a single bond. R 1 and R 2 each independently represent a hydrogen atom, an alkyl group or an aryl group. X 1 and X 2 each independently represent a halogen atom, an alkyl group or an alkoxy group. Z 1 and Z 2 are each independently a single bond, —COO—, —O—CO—, —CONH—, —
Represents NHCO-, -CH = CH-, -C≡C-. a and b represent the integer of 0, 1, 2.
【化5】
<2> 前記一般式(I)において、P1〜P4が全て重
合性基である上記<1>に記載の重合性化合物。
<3> 前記重合性基が、下記の基で表されることを特
徴とする上記<1>又は<2>に記載の重合性化合物。[Chemical 5] <2> The polymerizable compound according to <1>, wherein in the general formula (I), P 1 to P 4 are all polymerizable groups. <3> The polymerizable compound according to <1> or <2>, wherein the polymerizable group is represented by the following group.
【化6】
<4> 少なくとも上記<1>乃至<3>に記載の重合性化
合物を含有する液晶性組成物。
<5> 少なくとも上記<1>乃至<3>に記載の重合性化
合物と光学活性化合物とを含有する液晶性組成物。
<6> 少なくとも上記<2>又は<3>に記載の重合性化
合物と分子内に重合性基を1つ又は2つ有する液晶性化
合物とを含有する液晶性組成物。
<7> 上記<4>乃至<6>に記載の液晶性組成物を重合
硬化してなる重合体。[Chemical 6] <4> A liquid crystal composition containing at least the polymerizable compound described in <1> to <3>. <5> A liquid crystal composition containing at least the polymerizable compound according to the above <1> to <3> and an optically active compound. <6> A liquid crystal composition containing at least the polymerizable compound according to the above <2> or <3> and a liquid crystal compound having one or two polymerizable groups in the molecule. <7> A polymer obtained by polymerizing and curing the liquid crystalline composition according to the above items <4> to <6>.
【0006】[0006]
【発明の実施の形態】(一般式(I)の化合物)最初
に、下記一般式(I)で表される重合性化合物について
詳細に説明する。BEST MODE FOR CARRYING OUT THE INVENTION (Compound of General Formula (I)) First, the polymerizable compound represented by the following general formula (I) will be described in detail.
【化7】 [Chemical 7]
【0007】上記一般式(I)において、P1〜P4は夫
々独立に重合性基、水素原子、ハロゲン原子、水酸基、
−NHR3(R3は水素原子、アルキル基を表す)を表
し、P 1〜P4の内少なくとも1つは重合性基を表す。In the above general formula (I), P1~ PFourIs a husband
Independently polymerizable group, hydrogen atom, halogen atom, hydroxyl group,
-NHR3(R3Represents a hydrogen atom or an alkyl group)
Then P 1~ PFourAt least one of them represents a polymerizable group.
【0008】P1〜P4で表される前記重合性基として
は、下記に示す重合性基が挙げられる。Examples of the polymerizable group represented by P 1 to P 4 include the following polymerizable groups.
【化8】
上式中のR4で表されるアルキル基は、置換基を有して
いてもよく、炭素数が1〜20のアルキル基が好まし
く、特に炭素数が1〜12のアルキル基が好ましい。[Chemical 8] The alkyl group represented by R 4 in the above formula may have a substituent, is preferably an alkyl group having 1 to 20 carbon atoms, and particularly preferably an alkyl group having 1 to 12 carbon atoms.
【0009】これらの重合性基の中でも、付加重合し得
る重合性基が好ましく、特に下記重合性基が好ましい。Among these polymerizable groups, a polymerizable group capable of addition polymerization is preferable, and the following polymerizable group is particularly preferable.
【化9】
また、P1〜P4で表される重合性基は、同一の重合性基
が好ましい。[Chemical 9] Further, the polymerizable groups represented by P 1 to P 4 are preferably the same polymerizable group.
【0010】P1〜P4で表されるハロゲン原子として
は、フッ素原子、塩素原子、臭素原子が好ましく、特に
塩素原子、臭素原子が好ましい。P1〜P4で表される−
NHR3としては、アミノ基或いは、アルキル基(置換
基を有していてもよく、炭素数が1〜20が好ましく、
炭素数が1〜12が更に好ましい。)で置換されたアミ
ノ基が挙げられる。これらの中でも、アミノ基が好まし
い。The halogen atom represented by P 1 to P 4 is preferably a fluorine atom, a chlorine atom or a bromine atom, and particularly preferably a chlorine atom or a bromine atom. Represented by P 1 to P 4 −
As NHR 3 , an amino group or an alkyl group (which may have a substituent, preferably has 1 to 20 carbon atoms,
More preferably, the carbon number is 1 to 12. ) And an amino group substituted with. Of these, an amino group is preferred.
【0011】以上のP1〜P4で表される基の内、重合性
基が好ましく、特にアクリル酸残基及びメタクリル酸残
基が好ましい。また、重合性基は2個以上があるのが好
ましく、3個以上が更に好ましく、4個とも重合性基で
あるのが最も好ましい。Of the groups represented by P 1 to P 4 above, a polymerizable group is preferable, and an acrylic acid residue and a methacrylic acid residue are particularly preferable. The number of polymerizable groups is preferably 2 or more, more preferably 3 or more, and most preferably 4 are polymerizable groups.
【0012】前記一般式(I)において、L1〜L4は夫
々独立にアルキレン基、アルケニレン基、アラルキレン
基、単結合を表す。L1〜L4で表される前記アルキレン
基としては、置換基を有していてもよく、炭素数が1〜
20のアルキレン基が好ましく、特に炭素数が2〜12
のアルキレン基が好ましい。置換基としては、ハロゲン
原子、アルコキシ基、アリール基、アルケニル基等が挙
げられる。また、アルキレン鎖中の1つの炭素原子又は
隣接しない2以上の炭素原子は、酸素原子又は硫黄原子
に置き換えられてもよい。このようなアルキレン基の例
としては、エチレン基、ブチレン基、1−メチル−エチ
レン基、−(CH2)2O(CH2)2−等が挙げられる。In the above general formula (I), L 1 to L 4 each independently represent an alkylene group, an alkenylene group, an aralkylene group or a single bond. The alkylene group represented by L 1 to L 4 may have a substituent and has 1 to 1 carbon atoms.
20 alkylene groups are preferable, and particularly 2 to 12 carbon atoms.
Is preferred. Examples of the substituent include a halogen atom, an alkoxy group, an aryl group, an alkenyl group and the like. Further, one carbon atom or two or more non-adjacent carbon atoms in the alkylene chain may be replaced with an oxygen atom or a sulfur atom. Examples of such alkylene groups include ethylene group, butylene group, 1-methyl - ethylene group, - (CH 2) 2 O (CH 2) 2 - and the like.
【0013】L1〜L4で表される上記アルケニレン基と
しては、置換基を有していてもよく、炭素数が2〜20
のアルケニレン基が好ましく、特に炭素数が2〜12の
アルケニレン基が好ましい。置換基としては、ハロゲン
原子、アルコキシ基、アリール基等が挙げられる。この
ようなアルケニレン基の例としては、−CH2CH=C
HCH2−、−CH2CH2CH=CHCH2−等が挙げら
れる。The alkenylene group represented by L 1 to L 4 may have a substituent and has 2 to 20 carbon atoms.
Is preferred, and an alkenylene group having 2 to 12 carbon atoms is particularly preferred. Examples of the substituent include a halogen atom, an alkoxy group, an aryl group and the like. Examples of such alkenylene groups, -CH 2 CH = C
HCH 2 -, - CH 2 CH 2 CH = CHCH 2 - , and the like.
【0014】L1〜L4で表される上記アラルキレン基と
しては、置換基を有していてもよく、炭素数が8〜30
のアラルキレン基が好ましく、特に炭素数が8〜20の
アラルキレン基が好ましい。置換基としては、ハロゲン
原子、アルキル基、アリール基、アルコキシ基、アルケ
ニル基等が挙げられる。このようなアラルキレン基の例
としては、下記のアラルキレン基が挙げられる。The aralkylene group represented by L 1 to L 4 may have a substituent and has 8 to 30 carbon atoms.
Is preferred, and an aralkylene group having 8 to 20 carbon atoms is particularly preferred. Examples of the substituent include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an alkenyl group and the like. Examples of such an aralkylene group include the following aralkylene groups.
【化10】 [Chemical 10]
【0015】以上のL1〜L4で表される基の中でも、特
にアルキレン基が好ましく、またL 1〜L4で表される基
は、同一の基であるのが好ましい。The above L1~ LFourAmong the groups represented by
Is preferably an alkylene group, and L 1~ LFourGroup represented by
Are preferably the same group.
【0016】前記一般式(I)において、R1とR2は夫
々独立に水素原子、アルキル基、アリール基を表す。R
1とR2で表される上記アルキル基としては、置換基を有
していてもよく、炭素数が1〜20のアルキル基が好ま
しく、特に炭素数が1〜12のアルキル基が好ましい。
置換基としては、ハロゲン原子、アルコキシ基等が挙げ
られる。このようなアルキル基の例としては、メチル
基、イソブチル基、トリフルオロメチル基等が挙げられ
る。In the general formula (I), R 1 and R 2 each independently represent a hydrogen atom, an alkyl group or an aryl group. R
The alkyl group represented by 1 and R 2 may have a substituent and is preferably an alkyl group having 1 to 20 carbon atoms, and particularly preferably an alkyl group having 1 to 12 carbon atoms.
Examples of the substituent include a halogen atom and an alkoxy group. Examples of such an alkyl group include a methyl group, an isobutyl group, a trifluoromethyl group and the like.
【0017】R1とR2で表される上記アリール基として
は、置換基を有していてもよく、炭素数が6〜30のア
リール基が好ましく、特に炭素数が6〜20のアリール
基が好ましい。置換基としては、ハロゲン原子、アルコ
キシ基、アルキル基等が挙げられる。このようなアリー
ル基の例としては、フェニル基、4−クロロフェニル
基、2−メチルフェニル基等が挙げられる。The aryl group represented by R 1 and R 2 may have a substituent and is preferably an aryl group having 6 to 30 carbon atoms, and particularly an aryl group having 6 to 20 carbon atoms. Is preferred. Examples of the substituent include a halogen atom, an alkoxy group, an alkyl group and the like. Examples of such an aryl group include a phenyl group, a 4-chlorophenyl group, a 2-methylphenyl group and the like.
【0018】以上のR1とR2で表される基の中でも、水
素原子、アルキル基が好ましく、特に水素原子が好まし
い。またR1とR2で表される基は、同一の基が好まし
い。Among the groups represented by R 1 and R 2 above, a hydrogen atom and an alkyl group are preferable, and a hydrogen atom is particularly preferable. Further, the groups represented by R 1 and R 2 are preferably the same groups.
【0019】前記一般式(I)において、X1とX2は夫
々独立にハロゲン原子、アルキル基、アルコキシ基を表
す。X1とX2で表される上記ハロゲン原子としては、フ
ッ素原子、塩素原子、臭素原子が好ましく、特に塩素原
子、臭素原子が好ましい。In the above general formula (I), X 1 and X 2 each independently represent a halogen atom, an alkyl group or an alkoxy group. The halogen atom represented by X 1 and X 2 is preferably a fluorine atom, a chlorine atom or a bromine atom, and particularly preferably a chlorine atom or a bromine atom.
【0020】X1とX2で表される上記アルキル基として
は、置換基を有していてもよく、炭素数が1〜12のア
ルキル基が好ましく、特に炭素数が1〜6のアルキル基
が好ましい。X1とX2で表される上記アルコキシ基とし
ては、置換基を有していてもよく、炭素数が1〜12の
アルコキシ基が好ましく、特に炭素数が1〜6のアルコ
キシ基が好ましい。The alkyl group represented by X 1 and X 2 may have a substituent and is preferably an alkyl group having 1 to 12 carbon atoms, particularly an alkyl group having 1 to 6 carbon atoms. Is preferred. The alkoxy group represented by X 1 and X 2 may have a substituent and is preferably an alkoxy group having 1 to 12 carbon atoms, and particularly preferably an alkoxy group having 1 to 6 carbon atoms.
【0021】以上のようなR1とR2で表される基の中で
も、ハロゲン原子とアルキル基が好ましく、特にハロゲ
ン原子が好ましい。また、R1とR2で表される基は、同
一の基が好ましい。Among the groups represented by R 1 and R 2 as described above, a halogen atom and an alkyl group are preferable, and a halogen atom is particularly preferable. Further, the groups represented by R 1 and R 2 are preferably the same groups.
【0022】前記一般式(I)において、Z1とZ2は夫
々独立に単結合、−COO−、−O−CO−、−CON
H−、−NHCO−、−CH=CH−、−C≡C−を表
す。Z1とZ2としては、−COO−、−O−CO−、−
CONH−、−NHCO−が好ましく、特に−O−CO
−が好ましい。また、Z1とZ2は、同一の基が好まし
い。尚、上記の二価結合基において、一般式(I)の環
Aには右側の結合手で連結するものとする。In the above general formula (I), Z 1 and Z 2 are each independently a single bond, —COO—, —O—CO—, —CON.
Represents H-, -NHCO-, -CH = CH-, -C≡C-. Z 1 and Z 2 are -COO-, -O-CO-,-
CONH- and -NHCO- are preferable, and especially -O-CO.
− Is preferable. Further, Z 1 and Z 2 are preferably the same group. In the above divalent linking group, the ring A of the general formula (I) is to be linked by the right hand bond.
【0023】前記一般式(I)において、aとbは0、
1、2の整数を表す。aとbは0、1が好ましく、特に
0が好ましい。In the general formula (I), a and b are 0,
Represents an integer of 1 or 2. 0 and 1 are preferred for a and b, and 0 is particularly preferred.
【0024】前記一般式(I)において、環Aは下記に
示す二価の芳香族環乃至脂肪族環乃至複素環基を表す。In the general formula (I), ring A represents a divalent aromatic ring, aliphatic ring or heterocyclic group shown below.
【化11】
〔上式中、Y1〜Y14はハロゲン原子、アルキル基、ア
ルコキシ基を表し、Z3〜Z5は−COO−、−O−CO
−、−CONH−、−NHCO−を表す。c〜pは0、
1、2の整数を表す。〕[Chemical 11] [In the above formula, Y 1 to Y 14 represent a halogen atom, an alkyl group or an alkoxy group, and Z 3 to Z 5 are —COO— or —O—CO.
Represents-, -CONH-, and -NHCO-. cp is 0,
Represents an integer of 1 or 2. ]
【0025】Y1〜Y14で表される上記のハロゲン原
子、アルキル基、アルコキシ基は、一般式(I)のX1
とX2で表されるハロゲン原子、アルキル基、アルコキ
シ基と同義である。The above halogen atom, alkyl group and alkoxy group represented by Y 1 to Y 14 are each represented by X 1 of the general formula (I).
And X 2 have the same meaning as the halogen atom, alkyl group and alkoxy group.
【0026】環Aで表される二価の芳香族環乃至脂肪族
環乃至複素環基としては、上記の内、、、、
で示される二価の芳香族環基が好ましく、特に、、
の二価芳香族環が好ましい。Z3〜Z5は−CONH
−、−NHCO−が好ましい。c〜pは0、1が好まし
く、特に0が好ましい。Examples of the divalent aromatic ring, aliphatic ring or heterocyclic group represented by ring A include the following:
The divalent aromatic ring group represented by is particularly preferable,
The divalent aromatic ring of is preferred. Z 3 to Z 5 are -CONH
-, -NHCO- are preferable. 0 to 1 are preferable, and 0 is particularly preferable for c to p.
【0027】環Aで表される二価の芳香族環乃至脂肪族
環乃至複素環基の具体例を、下記に示す。但し、本発明
はこれらに限定されるものではない。Specific examples of the divalent aromatic ring, aliphatic ring or heterocyclic group represented by ring A are shown below. However, the present invention is not limited to these.
【化12】
本発明の前記一般式(I)で表される重合性化合物の具
体例を、下記に示す。但し、本発明はこれらに限定され
るものではない。[Chemical 12] Specific examples of the polymerizable compound represented by the general formula (I) of the present invention are shown below. However, the present invention is not limited to these.
【0028】[0028]
【化13】 [Chemical 13]
【0029】[0029]
【化14】 [Chemical 14]
【0030】[0030]
【化15】 [Chemical 15]
【0031】[0031]
【化16】 [Chemical 16]
【0032】[0032]
【化17】 [Chemical 17]
【0033】[0033]
【化18】 [Chemical 18]
【0034】[0034]
【化19】 [Chemical 19]
【0035】(一般式(I)化合物の製造方法)本発明
の前記一般式(I)で表される重合性化合物は、例えば
下記に示す反応式(1)に従う方法により製造すること
ができる。(Production Method of Compound of General Formula (I)) The polymerizable compound represented by the above general formula (I) of the present invention can be produced, for example, by a method according to the following reaction formula (1).
【0036】[0036]
【化20】 [Chemical 20]
【0037】また、一般式(I)のZ1とZ2が−COO
−、−O−CO−、−CONH−、−NHCO−を表す
場合には、下記反応式(2)に従う方法により製造する
ことができる。Further, Z 1 and Z 2 in the general formula (I) are --COO.
When-, -O-CO-, -CONH- or -NHCO- is represented, it can be produced by a method according to the following reaction formula (2).
【0038】[0038]
【化21】 [Chemical 21]
【0039】上記反応式(2)において、RはR1又は
R2を表し、XはX1又はX2を表し、rはa又はbを表
す。B及びEは、結合して基Z1又はZ2を形成する基を
表す。本反応は通常のエステル化或いはアミド化反応に
より行うことができる。In the above reaction formula (2), R represents R 1 or R 2 , X represents X 1 or X 2 , and r represents a or b. B and E represent a group which is bonded to form the group Z 1 or Z 2 . This reaction can be carried out by a usual esterification or amidation reaction.
【0040】上記化合物(A)は、例えば下記反応式
(3)に従う方法により製造することができる。The above compound (A) can be produced, for example, by the method according to the following reaction formula (3).
【0041】[0041]
【化22】 [Chemical formula 22]
【0042】即ち、化合物(B)と化合物(C)の縮合
反応であり、好適にはKnoevenagel反応により行われ
る。化合物(B)は芳香族アルデヒド又は芳香族ケトン
であり、市販品又は公知の方法により合成したものを用
いることができる。化合物(C)は、マロン酸エステル
誘導体であり、マロン酸ジクロリドとHO−L−Pとの
反応により得ることができる。That is, it is a condensation reaction of the compound (B) and the compound (C), and is preferably carried out by the Knoevenagel reaction. The compound (B) is an aromatic aldehyde or aromatic ketone, and a commercially available product or one synthesized by a known method can be used. The compound (C) is a malonic acid ester derivative and can be obtained by the reaction of malonic acid dichloride and HO-LP.
【0043】また、化合物(A)は下記反応式(4)に
示すように、化合物(B)と化合物(D)とから一旦化
合物(E)を製造した後に、重合性基等を導入すること
により製造することができる。Further, as shown in the following reaction formula (4), the compound (A) is prepared by once preparing the compound (E) from the compound (B) and the compound (D) and then introducing a polymerizable group and the like. Can be manufactured by.
【0044】[0044]
【化23】 [Chemical formula 23]
【0045】上記反応式(4)で、G及びJは、−L−
GとP−Jが結合して基−L−Pを形成するような基を
表し、例えば、P−Jがアクリル酸を表す場合は、Gは
臭素原子、塩素原子、ヨウ素原子を表し、P−Jがアク
リル酸クロリドを表す場合は、Gは水酸基又はアミノ基
を表す。In the above reaction formula (4), G and J are -L-
Represents a group in which G and P-J combine to form a group -LP; for example, when P-J represents acrylic acid, G represents a bromine atom, a chlorine atom, an iodine atom, P When -J represents acrylic acid chloride, G represents a hydroxyl group or an amino group.
【0046】上記反応式(2)〜反応式(4)に従う製
造方法は、Z1とZ2が単結合、−CH=CH−、−C≡
C−を表す場合でも、環A中にZ3〜Z5を含んでいる場
合には同様に適用され得る。In the production method according to the above reaction formulas (2) to (4), Z 1 and Z 2 are single bonds, -CH = CH-, -C≡.
Even when C- is represented, it can be similarly applied when the ring A contains Z 3 to Z 5 .
【0047】(液晶性組成物)本発明の一般式(I)で
表される重合性化合物は、それ自身液晶性を示すことは
必ずしも必要ではなく、他の液晶性化合物との混合物に
おいて、液晶性を示すような組成比で混合することによ
り、液晶性組成物として好適に使用することができる。
更に、高分子液晶が用いられる用途にも適用可能であ
る。(Liquid Crystalline Composition) The polymerizable compound represented by the general formula (I) of the present invention does not necessarily need to exhibit liquid crystallinity itself. A liquid crystal composition can be suitably used by mixing them in a composition ratio that exhibits the property.
Further, it can be applied to applications in which polymer liquid crystals are used.
【0048】本発明の前記一般式(I)の重合性化合物
を含む液晶性組成物に、光学活性化合物を添加すること
により、コレステリック相或いはカイラルスメクチック
相を誘起することもできる。この場合の光学活性化合物
の含有量としては、液晶性組成物の全固形分(質量)の
0.1〜20質量%が好ましく、特に2〜15質量%が
好ましい。このような光学活性化合物としては、公知の
光学活性化合物を使用することができる。例えば、特開
2000−44451号公報、特表平10−50972
6号公報、WO98/00428、特表2000−50
6873号公報、特表平9−506088号公報、特願
2000−382516号公報等に記載されている光学
活性化合物を用いることができる。It is also possible to induce a cholesteric phase or a chiral smectic phase by adding an optically active compound to the liquid crystalline composition containing the polymerizable compound of the general formula (I) of the present invention. In this case, the content of the optically active compound is preferably 0.1 to 20% by mass, and particularly preferably 2 to 15% by mass of the total solid content (mass) of the liquid crystal composition. As such an optically active compound, a known optically active compound can be used. For example, Japanese Unexamined Patent Publication No. 2000-44451 and Japanese Patent Publication No. 10-50972.
No. 6, gazette, WO98 / 00428, special table 2000-50
The optically active compounds described in, for example, Japanese Patent No. 6873, Japanese Patent Publication No. 9-506088, Japanese Patent Application No. 2000-382516 can be used.
【0049】本発明の重合性化合物を他の液晶性化合物
と混合して用いる場合には、当該液晶性化合物として
は、その屈折率異方性Δnが、0.10〜0.40の液
晶化合物、高分子液晶化合物、重合性基を1又は2個有
する液晶性化合物の中から適宜選択することができる。
例えば、スメクティック液晶化合物、ネマチック液晶化
合物などを挙げることができ、中でも、ネマチック液晶
化合物が好ましい。前記液晶性化合物は、溶融時の液晶
状態にある間に、例えばラビング処理等の配向処理を施
した配向基板を用いる等により配向させることができ
る。また、液晶状態を固相にして固定化する場合には、
冷却、重合等の手段を用いることができる。When the polymerizable compound of the present invention is used as a mixture with another liquid crystal compound, the liquid crystal compound has a refractive index anisotropy Δn of 0.10 to 0.40. , A polymer liquid crystal compound, and a liquid crystal compound having one or two polymerizable groups can be appropriately selected.
For example, a smectic liquid crystal compound, a nematic liquid crystal compound, etc. can be mentioned, and among them, a nematic liquid crystal compound is preferable. The liquid crystalline compound can be aligned while it is in a liquid crystal state when melted, for example, by using an alignment substrate that has been subjected to an alignment treatment such as a rubbing treatment. Also, when immobilizing the liquid crystal in the solid phase,
Means such as cooling and polymerization can be used.
【0050】前記重合性基を1又は2個有する液晶性化
合物の具体例としては、WO95/22586、特願2
000−51089、特願2000−68479、特願
平11−91162に記載の化合物を挙げることができ
る。但し、本発明においては、これらに制限されるもの
ではない。このような液晶性化合物の一例を下記に示
す。Specific examples of the liquid crystal compound having one or two polymerizable groups are WO95 / 22586, Japanese Patent Application No. 2
000-51089, Japanese Patent Application No. 2000-68479 and Japanese Patent Application No. 11-91162 can be mentioned. However, the present invention is not limited to these. An example of such a liquid crystal compound is shown below.
【0051】[0051]
【化24】 [Chemical formula 24]
【0052】[0052]
【化25】 [Chemical 25]
【0053】前記液晶性化合物の含有量としては、液晶
性組成物の全固形分(質量)の10〜90質量%が好ま
しく、特に20〜80質量%が好ましい。The content of the liquid crystalline compound is preferably 10 to 90% by mass, and more preferably 20 to 80% by mass based on the total solid content (mass) of the liquid crystalline composition.
【0054】(その他用途)本発明の一般式(I)の重
合性化合物はクロロホルム、テトラヒドロフラン、N−
メチルピロリドン等の通常の溶媒に良く溶解し又その際
の粘度もあまり高くないので、スピンコート法等の方法
により容易に基板に被覆することができる。更に、本発
明の化合物は光重合性を有するので、紫外線を照射する
ことにより容易に重合させることができる。(Other Uses) The polymerizable compound of the general formula (I) of the present invention is chloroform, tetrahydrofuran, N-
Since it is well dissolved in an ordinary solvent such as methylpyrrolidone and the viscosity at that time is not so high, the substrate can be easily coated by a method such as spin coating. Furthermore, since the compound of the present invention has photopolymerizability, it can be easily polymerized by irradiation with ultraviolet rays.
【0055】また、本発明の重合性化合物を含む組成物
を液晶相を示す温度において重合させる(たとえば光重
合)と、得られる重合体は光学異方性等の異方性を示
し、そしてこの重合体は、従来の2官能性の重合性液晶
化合物からの重合体に比べ硬度や強度に優れているの
で、従来のものより耐摩耗性の良好な光学フィルムが得
られる。また、その耐摩耗性のため、光学フィルムに限
らず、耐摩耗性が要求される種々の被覆剤に適用するこ
とが可能である。When the composition containing the polymerizable compound of the present invention is polymerized at a temperature showing a liquid crystal phase (for example, photopolymerization), the obtained polymer exhibits anisotropy such as optical anisotropy, and Since the polymer is excellent in hardness and strength as compared with the polymer made from the conventional bifunctional polymerizable liquid crystal compound, an optical film having better abrasion resistance than the conventional polymer can be obtained. Further, because of its abrasion resistance, it can be applied not only to optical films, but also to various coating agents that require abrasion resistance.
【0056】本発明の前記一般式(I)で表される重合
性化合物は、重合性特に光重合性を有し、重合性モノマ
ー特に光重合性モノマーとして一般的に用いられる用途
に適用可能である。例えば、本発明の重合性化合物は、
その重合性(光重合性)を利用して印刷回路板製造用、
マイクロリソグラフィー用、光ファイバーコーティング
用、磁気記録媒体塗料用、インク用、接着剤用、歯科材
用、医科材用等に応用することができる。その際、適宜
他の重合性モノマーを組み合せて使用することができ
る。更に、本発明の重合性化合物は従来の重合性液晶化
合物との相溶性も良好であり、両者の混合物は、広い温
度範囲にわたり液晶の性質を示すので、該混合物を重合
させた場合、良好な光学異方性(複屈折)が得られる。
また、従来の重合性液晶化合物に本発明の重合性化合物
を添加して重合させた場合、得られる膜等の硬度、強
度、耐スクラッチ性等の機械的性質も改善される。The polymerizable compound represented by the above general formula (I) of the present invention has a polymerizability, especially a photopolymerizability, and is applicable to a general use as a polymerizable monomer, particularly a photopolymerizable monomer. is there. For example, the polymerizable compound of the present invention is
Utilizing its polymerizability (photopolymerizability) for manufacturing printed circuit boards,
It can be applied to microlithography, optical fiber coating, magnetic recording medium paints, inks, adhesives, dental materials, medical materials and the like. At that time, other polymerizable monomers can be appropriately used in combination. Furthermore, the polymerizable compound of the present invention has good compatibility with conventional polymerizable liquid crystal compounds, and the mixture of the two exhibits liquid crystal properties over a wide temperature range. Therefore, when the mixture is polymerized, good results are obtained. Optical anisotropy (birefringence) is obtained.
Further, when the polymerizable compound of the present invention is added to a conventional polymerizable liquid crystal compound and polymerized, mechanical properties such as hardness, strength and scratch resistance of a film obtained are improved.
【0057】本発明はまた、前記一般式(I)で表され
る重合性化合物を含む組成物及びその重合体にも関す
る。該組成物には、前記一般式(I)で表される重合性
化合物の他、他の重合性モノマー、従来の1又は2官能
性の重合性液晶化合物、高分子液晶、光学活性或いはコ
レステリック液晶化合物、重合開始剤、有機色素、分光
増感剤、界面活性剤等を含有させることができる。そし
て、該組成物はコレステリックカラーフィルター、位相
差膜、オーバーコート層等の他、前記の本発明の重合性
化合物の用途において述べた用途にも使用することがで
きる。The present invention also relates to a composition containing the polymerizable compound represented by the general formula (I) and a polymer thereof. In the composition, in addition to the polymerizable compound represented by the general formula (I), other polymerizable monomers, conventional mono- or bifunctional polymerizable liquid crystal compounds, polymer liquid crystals, optically active or cholesteric liquid crystals. A compound, a polymerization initiator, an organic dye, a spectral sensitizer, a surfactant, etc. can be contained. The composition can be used not only for the cholesteric color filter, the retardation film, the overcoat layer and the like, but also for the applications described above for the application of the polymerizable compound of the invention.
【0058】また、本発明の重合性化合物、又はこれを
含む組成物から、カラーフィルター、位相差膜、STN
素子用光学補償膜、拡散フィルム等の光学フィルムを作
製することができる。光学フィルムは、本発明の重合性
化合物、又はこれを含む組成物の粘度を適宜溶剤により
調節し、更に必要に応じ重合触媒を加えた後、基体上に
塗布し重合させるなどによって作製される。Further, from the polymerizable compound of the present invention or a composition containing the same, a color filter, a retardation film, an STN
An optical film such as an optical compensation film for a device or a diffusion film can be produced. The optical film is produced by appropriately adjusting the viscosity of the polymerizable compound of the present invention or the composition containing the same with a solvent, further adding a polymerization catalyst if necessary, and then coating the composition on a substrate for polymerization.
【0059】[0059]
【実施例】以下に実施例を示し本発明を更に具体的に説
明するが、本発明はこれらの実施例により限定されるも
のではない。尚、本実施例において「部」及び「%」は
全て、「質量部」及び「質量%」を表す。EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In this example, "parts" and "%" all represent "parts by mass" and "% by mass".
【0060】[実施例1]:例示化合物(1−2)の合
成
下記に示す合成手順に従って、例示化合物(1−2)を
合成した。Example 1 Synthesis of Exemplified Compound (1-2) Exemplified Compound (1-2) was synthesized according to the synthetic procedure shown below.
【0061】[0061]
【化26】 [Chemical formula 26]
【0062】<化合物(1)の合成>1,4−ブタンジオ
ール66.3ml、ピリジニウムp−トルエンスルホナ
ート12.5g及びTHF180mlを混合し、氷冷下
3,4−ジヒドロ−2H−ピラン42gのTHF50m
l溶液を30分掛けて滴下した。室温で1時間半攪拌し
た後に、炭酸水素ナトリウム水溶液にあけ、酢酸エチル
にて抽出した。酢酸エチル層を濃縮後、残渣をカラムク
ロマトグラフィーにて精製し、化合物(1)を50.8
g得た。収率は58%であった。<Synthesis of Compound (1)> 66.3 ml of 1,4-butanediol, 12.5 g of pyridinium p-toluenesulfonate and 180 ml of THF were mixed, and 42 g of 3,4-dihydro-2H-pyran was added under ice cooling. THF 50m
1 solution was added dropwise over 30 minutes. After stirring for one and a half hours at room temperature, the mixture was poured into an aqueous sodium hydrogen carbonate solution and extracted with ethyl acetate. After concentrating the ethyl acetate layer, the residue was purified by column chromatography to give compound (1) 50.8.
g was obtained. The yield was 58%.
【0063】<化合物(2)の合成>上記化合物(1)4
9.5g、ジメチルアニリン37.6ml及びTHF3
00mlを混合し、氷冷下、マロン酸ジクロリド20g
のTHF30ml溶液を滴下した。室温で1時間攪拌
後、酢酸エチルと炭酸水素ナトリウム水溶液を加えて分
液後、酢酸エチル層を留去した。残渣をカラムクロマト
グラフィーにて精製し、油状物である化合物(2)を3
2.4g得た。(収率55%)<Synthesis of Compound (2)> Above Compound (1) 4
9.5 g, dimethylaniline 37.6 ml and THF3
Mix 00 ml and under ice cooling, 20 g of malonic acid dichloride
30 ml of THF solution was added dropwise. After stirring at room temperature for 1 hour, ethyl acetate and aqueous sodium hydrogen carbonate solution were added to separate the layers, and the ethyl acetate layer was evaporated. The residue was purified by column chromatography, and the compound (2) which was an oily substance was purified by 3
2.4 g was obtained. (55% yield)
【0064】<化合物(3)の合成>上記化合物(2)3
2.4g、p−ヒドロキシベンズアルデヒド9.5gと
トルエン250mlの混合物に、ピペリジン1.54m
l、酢酸0.44mlを加え、ディーン・スタークトラ
ップを用いて1時間半還流した。反応混合物を濃縮し、
カラムクロマトグラフィーで精製することにより、黄色
油状物である化合物(3)を34.8g得た。(収率8
6%)<Synthesis of Compound (3)> Compound (2) 3
1.5 g of piperidine was added to a mixture of 2.4 g, 9.5 g of p-hydroxybenzaldehyde and 250 ml of toluene.
1, 0.44 ml of acetic acid were added, and the mixture was refluxed for 1 and a half hours using a Dean Stark trap. The reaction mixture is concentrated,
Purification by column chromatography yielded 34.8 g of compound (3) as a yellow oil. (Yield 8
6%)
【0065】<化合物(4)の合成>上記化合物(3)3
4.8gをDMF100mlに混合し、イミダゾール
5.5g、t−ブチル−ジメチルシリルクロリド12g
を添加した。室温で4時間半攪拌後、食塩水を加え、酢
酸エチルで抽出した。濃縮後、残渣をカラムクロマトグ
ラフィーで精製し、黄色油状物である化合物(4)を3
2.6g得た。(収率77%)<Synthesis of Compound (4)> Compound (3) 3
4.8 g was mixed with 100 ml of DMF, 5.5 g of imidazole and 12 g of t-butyl-dimethylsilyl chloride.
Was added. After stirring for 4 hours and a half at room temperature, brine was added, and the mixture was extracted with ethyl acetate. After concentration, the residue was purified by column chromatography to give compound (4) which was a yellow oily substance to 3
2.6 g were obtained. (Yield 77%)
【0066】<化合物(5)の合成>上記化合物(4)3
2.6gをエタノール100mlと混合し、ピリジニウ
ムp−トルエンスルホナート1.3gを加え、60℃で
4時間攪拌した。反応溶媒を濃縮し、食塩水を加え、酢
酸エチルで抽出した。硫酸マグネシウムで乾燥した後
に、酢酸エチルを留去して化合物(5)を得た。<Synthesis of Compound (5)> Compound (4) 3
2.6 g of ethanol was mixed with 100 ml of ethanol, 1.3 g of pyridinium p-toluenesulfonate was added, and the mixture was stirred at 60 ° C. for 4 hours. The reaction solvent was concentrated, brine was added, and the mixture was extracted with ethyl acetate. After drying over magnesium sulfate, ethyl acetate was distilled off to obtain compound (5).
【0067】<化合物(6)の合成>上記で得られた化合
物(5)全量とジメチルアニリン15.5mlをTHF
100mlに混合し、氷冷下、アクリル酸クロリド1
0.0mlのTHF10mlの溶液を滴下した。室温で
1時間攪拌後、希塩酸にあけ、酢酸エチルで抽出し、希
塩酸、炭酸水素ナトリウム水溶液、食塩水の順で洗浄
後、酢酸エチル層を濃縮し、化合物(6)を得た。<Synthesis of Compound (6)> The whole amount of the compound (5) obtained above and 15.5 ml of dimethylaniline were mixed with THF.
Mix with 100 ml, and under cooling with ice, acrylic acid chloride 1
A solution of 0.0 ml of THF in 10 ml was added dropwise. After stirring at room temperature for 1 hour, the mixture was poured into diluted hydrochloric acid, extracted with ethyl acetate, washed with diluted hydrochloric acid, an aqueous sodium hydrogen carbonate solution and brine in this order, and then the ethyl acetate layer was concentrated to obtain a compound (6).
【0068】<化合物(7)の合成>上記で得られた化合
物(6)全量をTHF100mlに混合し、氷冷下、テ
トラブチルアンモニウムクロリドのTHF溶液(1M)
46mlを滴下した。室温で5時間攪拌後、希塩酸にあ
け、酢酸エチルで抽出した。酢酸エチルを留去後、残渣
をカラムクロマトグラフィーにより精製し、黄色油状物
である化合物(7)を21g得た。化合物(4)からの
収率は89%であった。<Synthesis of Compound (7)> The whole amount of the compound (6) obtained above was mixed with 100 ml of THF and, under ice cooling, a solution of tetrabutylammonium chloride in THF (1M).
46 ml was dropped. After stirring at room temperature for 5 hours, the mixture was poured into diluted hydrochloric acid and extracted with ethyl acetate. After distilling off ethyl acetate, the residue was purified by column chromatography to obtain 21 g of a yellow oily compound (7). The yield based on the compound (4) was 89%.
【0069】<例示化合物(1−2)の合成>上記化合物
(7)5gと4−ジメチルアミノピリジン0.1gをT
HF30mlに混合し、4,4’−ビフェニルカルボン
酸クロリド1.21gを加えた後に、トリエチルアミン
2.26mlのTHF5mlの溶液を滴下した。室温で
1時間半攪拌した後に、希塩酸を加え、酢酸エチルで抽
出した。酢酸エチルを濃縮後、残渣をカラムクロマトグ
ラフィーにより精製し、得られた固体をメタノールに分
散し、濾取することで白色固体状である例示化合物(1
−2)を3.38g得た。(収率69%)<Synthesis of Exemplified Compound (1-2)> 5 g of the above compound (7) and 0.1 g of 4-dimethylaminopyridine are added to T
After mixing with 30 ml of HF and adding 1.21 g of 4,4'-biphenylcarboxylic acid chloride, a solution of 2.26 ml of triethylamine in 5 ml of THF was added dropwise. After stirring for one and a half hours at room temperature, diluted hydrochloric acid was added, and the mixture was extracted with ethyl acetate. After concentrating ethyl acetate, the residue was purified by column chromatography, the obtained solid was dispersed in methanol, and collected by filtration to give a white solid exemplary compound (1
2.38 g of -2) was obtained. (Yield 69%)
【0070】上記により得られた化合物(1−2)を同
定した結果を、下記に示す。
C93℃(N77.3℃)I。1
H−NMR(CDCl3):δ(TMS)8.30(4H,d)
7.82(4H,d) 7.75(2H,s) 7.55(4H,d) 7.30(4H,d) 6.
44-5.80(12H,m) 4.30-4.12(16H,m) 1.80-1.65(16H,m)The results of identifying the compound (1-2) obtained above are shown below. C93 ° C. (N77.3 ° C.) I. 1 H-NMR (CDCl 3 ): δ (TMS) 8.30 (4H, d)
7.82 (4H, d) 7.75 (2H, s) 7.55 (4H, d) 7.30 (4H, d) 6.
44-5.80 (12H, m) 4.30-4.12 (16H, m) 1.80-1.65 (16H, m)
【0071】[実施例2]:例示化合物(1−7)の合
成
実施例1における前記化合物(7)2.68gと、2,
6−ナフタレンジカルボン酸クロリド0.7gをTHF
20mlに混合し、トリエチルアミン1.5mlを滴下
した。室温で1時間攪拌した後、前記<例示化合物(1
−2)の合成>と同様な操作をして、白色固体状である
例示化合物(1−7)を1.44g得た。(収率47
%)Example 2 Synthesis of Exemplified Compound (1-7) 2.68 g of the compound (7) in Example 1
0.7 g of 6-naphthalenedicarboxylic acid chloride in THF
After mixing with 20 ml, 1.5 ml of triethylamine was added dropwise. After stirring for 1 hour at room temperature, the above <exemplified compound (1
Synthesis of -2 >> was performed to obtain 1.44 g of Exemplified compound (1-7) as a white solid. (Yield 47
%)
【0072】上記により得られた化合物(1−7)を同
定した結果を、下記に示す。
C 55℃ I。1
H−NMR(CDCl3):δ(TMS)8.86(2H,s)
8.30(2H,d) 8.14(2H,d) 7.80(2H,s) 7.56(4H,d) 7.
32(4H,d)6.45-5.80(12H,m) 4.34-4.15(16H,m) 1.80-
1.70(16H,m)The results of identifying the compound (1-7) obtained above are shown below. C 55 ° C I. 1 H-NMR (CDCl 3 ): δ (TMS) 8.86 (2H, s)
8.30 (2H, d) 8.14 (2H, d) 7.80 (2H, s) 7.56 (4H, d) 7.
32 (4H, d) 6.45-5.80 (12H, m) 4.34-4.15 (16H, m) 1.80-
1.70 (16H, m)
【0073】[実施例3]:例示化合物(1−18)の
合成
実施例2において、2,6−ナフタレンジカルボン酸ク
ロリド0.7gをトラン−4,4’−ジカルボン酸クロ
リド0.8gに変更した以外は、実施例2と同様な操作
を行い、白色固体状である例示化合物(1−18)を
1.15g得た。(収率33%)Example 3 Synthesis of Exemplified Compound (1-18) In Example 2, 0.7 g of 2,6-naphthalenedicarboxylic acid chloride was changed to 0.8 g of tolan-4,4′-dicarboxylic acid chloride. The same operation as in Example 2 was carried out except that the above procedure was performed to obtain 1.15 g of the exemplary compound (1-18) in the form of a white solid. (Yield 33%)
【0074】上記により得られた化合物(1−18)を
同定した結果を、下記に示す。
C 73℃ N98.6℃ I。1
H−NMR(CDCl3):δ(TMS)8.20(4H,d)
7.75(2H,s) 7.70(4H,d) 7.55(4H,d) 7.28(4H,d) 6.
45-5.76(12H,m) 4.35-4.12(16H,m) 1.80-1.66(16H,m)The results of identifying the compound (1-18) obtained above are shown below. C 73 ° C N 98.6 ° C I. 1 H-NMR (CDCl 3 ): δ (TMS) 8.20 (4H, d)
7.75 (2H, s) 7.70 (4H, d) 7.55 (4H, d) 7.28 (4H, d) 6.
45-5.76 (12H, m) 4.35-4.12 (16H, m) 1.80-1.66 (16H, m)
【0075】[実施例4]:液晶組成物 下記の液晶組成物を調製した。[Example 4]: Liquid crystal composition The following liquid crystal composition was prepared.
【化27】 [Chemical 27]
【0076】この溶液を、ガラス基板上に日立化成デュ
ポン社製のポリイミド配向膜LX−1400膜を形成し
てラビングを行ったものに滴下し、1000rpmでス
ピンコートをおこなった。次に、これを105℃で5分
間保持した後、高圧水銀ランプを用いて紫外線を照射
し、重合を行った。この膜はラビング方向に光学軸を有
する、光学異方性を示した。この膜のレターデーション
は550nmの波長において220nmであった。This solution was added dropwise to a glass substrate on which a polyimide alignment film LX-1400 film made by Hitachi Chemical DuPont was formed and rubbed, and the solution was spin-coated at 1000 rpm. Next, this was held at 105 ° C. for 5 minutes and then irradiated with ultraviolet rays using a high pressure mercury lamp to carry out polymerization. This film exhibited optical anisotropy having an optical axis in the rubbing direction. The retardation of this film was 220 nm at a wavelength of 550 nm.
【0077】[実施例5]:コレステリック液晶組成物
上記の配向膜付ガラス基板の該配向膜上に、下記処方に
て調製した感光性樹脂層用塗布液をスピンコーターによ
り塗布し、これを100℃のオーブンで2分間乾燥して
感光性樹脂層を形成した。[Example 5]: Cholesteric liquid crystal composition A coating solution for a photosensitive resin layer prepared according to the following formulation was applied on the orientation film of the above-mentioned glass substrate with an orientation film by a spin coater, and then 100 A photosensitive resin layer was formed by drying in an oven at ℃ for 2 minutes.
【0078】[0078]
【化28】 [Chemical 28]
【0079】次いで、ガラス基板の表面で接触するよう
に100℃のホットプレート上に5分間保持し、感光性
樹脂層を発色させたところ、コレステリック液晶相由来
の青色の選択反射が得られた。Next, when the photosensitive resin layer was developed by holding it on a hot plate at 100 ° C. for 5 minutes so that the surface of the glass substrate was in contact with it, blue selective reflection derived from the cholesteric liquid crystal phase was obtained.
【0080】次に、窒素ガスを吹き付けながら超高圧水
銀灯により照射エネルギー500mJ/cm2で全面を
露光し、重合硬化した。この膜の引掻き硬度をJIS−
K5401の方法で測定したところ、3Hであった。一
方、例示化合物(1−18)を用いないで化合物(Z)
だけの場合の引掻き硬度は1Hであり、本発明の重合性
化合物が共存することにより引掻き硬度が向上したこと
が分かった。また、この重合膜の固さを(株)アカシ社
製の「微小表面材料特性評価システム MZT−3」を
用いて測定したところ、固さ値が65であった。一方、
例示化合物(1−18)を用いないで化合物(Z)だけ
の場合の固さ値は50であり、本発明の重合性化合物の
共存により重合体の固さ(硬度)が向上したことが分か
った。Next, the entire surface was exposed with an irradiation energy of 500 mJ / cm 2 by an ultra-high pressure mercury lamp while blowing nitrogen gas, and was polymerized and cured. The scratch hardness of this film is JIS-
It was 3H when measured by the method of K5401. On the other hand, the compound (Z) without using the exemplified compound (1-18)
The scratch hardness in this case was 1H, and it was found that the scratch hardness was improved by the coexistence of the polymerizable compound of the present invention. Further, the hardness of the polymer film was measured using "Micro Surface Material Property Evaluation System MZT-3" manufactured by Akashi Co., Ltd., and the hardness value was 65. on the other hand,
The hardness value of the compound (Z) alone without using the exemplified compound (1-18) was 50, and it was found that the hardness (hardness) of the polymer was improved by the coexistence of the polymerizable compound of the present invention. It was
【0081】[0081]
【発明の効果】本発明の重合性化合物は、通常の溶媒に
良く溶解し又その際の粘度も高くないので、スピンコー
ト法等の方法により容易に基板に被覆することができ
る。本発明の重合性化合物から得られる重合体フィルム
は光学異方性等の異方性を示し、また該フィルムは機械
的強度や硬度に優れている。更に、本発明の重合性化合
物は従来の重合性液晶化合物との相溶性も良好であり、
両者の混合物は、広い温度範囲にわたり液晶の性質を示
すので、該混合物を重合させた場合、良好な光学異方性
(複屈折)が得られる。また、従来の重合性液晶化合物
に本発明の重合性化合物を添加して重合させた場合、得
られる膜の強度や耐スクラッチ性等の機械的性質も改善
される。EFFECT OF THE INVENTION Since the polymerizable compound of the present invention is well dissolved in an ordinary solvent and the viscosity at that time is not high, the substrate can be easily coated by a method such as spin coating. The polymer film obtained from the polymerizable compound of the present invention exhibits anisotropy such as optical anisotropy, and the film is excellent in mechanical strength and hardness. Furthermore, the polymerizable compound of the present invention has good compatibility with conventional polymerizable liquid crystal compounds,
Since the mixture of both exhibits liquid crystal properties over a wide temperature range, good optical anisotropy (birefringence) can be obtained when the mixture is polymerized. In addition, when the polymerizable compound of the present invention is added to a conventional polymerizable liquid crystal compound and polymerized, mechanical properties such as strength and scratch resistance of the obtained film are improved.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 FI テーマコート゛(参考) G02F 1/13 500 G02F 1/13 500 G03F 7/027 502 G03F 7/027 502 (72)発明者 林 圭一郎 静岡県富士宮市大中里200番地 富士写真 フイルム株式会社内 Fターム(参考) 2H025 AB14 BC13 BC44 BC83 4H006 AA01 AA03 AB64 BJ50 BM30 BM73 BT22 BV74 KC30 4H027 BA02 BA11 BD02 BD07 BD14 4J100 AL71 AL74 AL75 AM54 BA02 BC43 BC53 BC54 JA32 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 identification code FI theme code (reference) G02F 1/13 500 G02F 1/13 500 G03F 7/027 502 G03F 7/027 502 (72) Inventor Keiichiro Hayashi Fujinomiya City, Fujinomiya-shi, 200, F-Term, Fuji Photo Film Co., Ltd. (Reference) 2H025 AB14 BC13 BC44 BC83 4H006 AA01 AA03 AB64 BJ50 BM30 BM73 BT22 BV74 KC30 4H027 BA02 BA11 BD02 BD07 BD14 4J100 AL71 AL74 AL75 AM54 BA02 BC43 BC43
Claims (7)
物。 【化1】 〔式(I)中、P1〜P4は夫々独立に重合性基、水素原
子、ハロゲン原子、水酸基、−NHR3(R3は水素原
子、アルキル基を表す)を表し、P1〜P4の内少なくと
も1つは重合性基を表す。L1〜L4は夫々独立にアルキ
レン基、アルケニレン基、アラルキレン基、単結合を表
す。R1とR2は夫々独立に水素原子、アルキル基、アリ
ール基を表す。X1とX2は夫々独立にハロゲン原子、ア
ルキル基、アルコキシ基を表す。Z1とZ2は夫々独立に
単結合、−COO−、−O−CO−、−CONH−、−
NHCO−、−CH=CH−、−C≡C−を表す。aと
bは0、1、2の整数を表す。 【化2】 1. A polymerizable compound represented by the following general formula (I). [Chemical 1] [In formula (I), P 1 to P 4 each independently represent a polymerizable group, a hydrogen atom, a halogen atom, a hydroxyl group, —NHR 3 (R 3 represents a hydrogen atom or an alkyl group), and P 1 to P 4 At least one of 4 represents a polymerizable group. L 1 to L 4 each independently represent an alkylene group, an alkenylene group, an aralkylene group, or a single bond. R 1 and R 2 each independently represent a hydrogen atom, an alkyl group or an aryl group. X 1 and X 2 each independently represent a halogen atom, an alkyl group or an alkoxy group. Z 1 and Z 2 are each independently a single bond, —COO—, —O—CO—, —CONH—, —
Represents NHCO-, -CH = CH-, -C≡C-. a and b represent the integer of 0, 1, 2. [Chemical 2]
全て重合性基である請求項1に記載の重合性化合物。2. The polymerizable compound according to claim 1, wherein in the general formula (I), P 1 to P 4 are all polymerizable groups.
とを特徴とする請求項1又は2に記載の重合性化合物。 【化3】 3. The polymerizable compound according to claim 1 or 2, wherein the polymerizable group is represented by the following group. [Chemical 3]
性化合物を含有する液晶性組成物。4. A liquid crystal composition containing at least the polymerizable compound according to claim 1.
性化合物と光学活性化合物とを含有する液晶性組成物。5. A liquid crystal composition containing at least the polymerizable compound according to claim 1 and an optically active compound.
性化合物と分子内に重合性基を1つ又は2つ有する液晶
性化合物とを含有する液晶性組成物。6. A liquid crystal composition containing at least the polymerizable compound according to claim 2 or 3 and a liquid crystal compound having one or two polymerizable groups in the molecule.
重合硬化してなる重合体。7. A polymer obtained by polymerizing and curing the liquid crystalline composition according to claim 4.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2001251291A JP2003064032A (en) | 2001-08-22 | 2001-08-22 | Polymerizable compound, liquid crystalline composition and polymer of the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2001251291A JP2003064032A (en) | 2001-08-22 | 2001-08-22 | Polymerizable compound, liquid crystalline composition and polymer of the same |
Publications (1)
Publication Number | Publication Date |
---|---|
JP2003064032A true JP2003064032A (en) | 2003-03-05 |
Family
ID=19079960
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2001251291A Pending JP2003064032A (en) | 2001-08-22 | 2001-08-22 | Polymerizable compound, liquid crystalline composition and polymer of the same |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2003064032A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005105866A1 (en) * | 2004-04-28 | 2005-11-10 | Toyo Ink Mfg. Co., Ltd. | Photocurable composition and antireflective film using same |
US7125500B2 (en) * | 1999-09-03 | 2006-10-24 | Merck Patent Gmbh | Multireactive polymerizable mesogenic compounds |
CN104718498A (en) * | 2012-10-17 | 2015-06-17 | 富士胶片株式会社 | Process for producing permanent film for optical material, cured film produced thereby, and organic EL display device and liquid-crystal display device each obtained using said cured film |
-
2001
- 2001-08-22 JP JP2001251291A patent/JP2003064032A/en active Pending
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7125500B2 (en) * | 1999-09-03 | 2006-10-24 | Merck Patent Gmbh | Multireactive polymerizable mesogenic compounds |
WO2005105866A1 (en) * | 2004-04-28 | 2005-11-10 | Toyo Ink Mfg. Co., Ltd. | Photocurable composition and antireflective film using same |
CN100455607C (en) * | 2004-04-28 | 2009-01-28 | 东洋油墨制造株式会社 | Photocurable composition and antireflective film using same |
CN104718498A (en) * | 2012-10-17 | 2015-06-17 | 富士胶片株式会社 | Process for producing permanent film for optical material, cured film produced thereby, and organic EL display device and liquid-crystal display device each obtained using said cured film |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP3866307B2 (en) | Photocrosslinkable liquid crystal | |
JP4205195B2 (en) | Photocrosslinkable silane derivative | |
JP4058481B2 (en) | Polymerizable liquid crystal compound and optical film | |
JP5220969B2 (en) | Liquid crystal compound | |
JP4006608B2 (en) | Liquid crystalline (meth) acrylate compound, composition containing the compound, and optical anisotropic body using the same | |
JP2001505879A (en) | Polymerizable oligomesogen | |
JP4058480B2 (en) | Liquid crystalline (meth) acrylate compound, liquid crystal composition containing the compound, and optical film using them | |
KR20090107018A (en) | Polymerizable optically-active compound, and polymerizable composition comprising the polymerizable optically-active compound | |
JP2005502730A (en) | Transversely polymerizable liquid crystal compound | |
KR20090098956A (en) | Polymerizable compounds and polymerizable compositions | |
JP2003321430A (en) | Polymerizable compound, liquid crystalline composition containing the same and its polymer | |
JP2021102766A (en) | Photoreactive liquid crystal composition, display device, optical device, method for manufacturing display device, and method for manufacturing optical device | |
EP3990568A1 (en) | New polymerizable liquid crystal having a quinoxaline-hydrazone core | |
Andersson et al. | Synthesis and Polymerization of Liquid Crystalline Donor− Acceptor Monomers | |
JP2003064032A (en) | Polymerizable compound, liquid crystalline composition and polymer of the same | |
JP7269317B2 (en) | compound, liquid crystal composition, cured product, optically anisotropic object, reflective film | |
JP2004277488A (en) | Polymerizable liquid crystal composition and optical anisotropic material | |
JP2003073669A (en) | Liquid crystal composition, display and optical film | |
JP2003012762A (en) | Polymerizable liquid crystal compound, composition, and optically anisotropic product | |
JP2001233837A (en) | Compound and composition and optical film using the same | |
JP4872219B2 (en) | Polymerizable compound | |
JP4756296B2 (en) | Maleimide derivative and method for producing photoalignment film using the same | |
WO2020049957A1 (en) | Compound, composition, cured product, optically anisotropic body, and reflective film | |
JP3972430B2 (en) | Liquid crystalline (meth) acrylate compound, composition containing the compound, and optical anisotropic body using the same | |
JP2012025959A (en) | Polymerizable compound |