JP2001220583A - Polymerizable liquid crystal composition, polymer liquid crystal prepared by polymerizing the composition and its use - Google Patents
Polymerizable liquid crystal composition, polymer liquid crystal prepared by polymerizing the composition and its useInfo
- Publication number
- JP2001220583A JP2001220583A JP2000364979A JP2000364979A JP2001220583A JP 2001220583 A JP2001220583 A JP 2001220583A JP 2000364979 A JP2000364979 A JP 2000364979A JP 2000364979 A JP2000364979 A JP 2000364979A JP 2001220583 A JP2001220583 A JP 2001220583A
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- Prior art keywords
- liquid crystal
- polymerizable liquid
- crosslinkable monomer
- crystal composition
- composition
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- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 69
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 57
- 239000005264 High molar mass liquid crystal Substances 0.000 title claims abstract description 52
- 230000000379 polymerizing effect Effects 0.000 title claims description 6
- 239000000178 monomer Substances 0.000 claims abstract description 47
- 125000005407 trans-1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])[C@]([H])([*:2])C([H])([H])C([H])([H])[C@@]1([H])[*:1] 0.000 claims abstract description 3
- 230000003287 optical effect Effects 0.000 claims description 19
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000005651 substituted 1,4-phenylene group Chemical group 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 27
- 238000006116 polymerization reaction Methods 0.000 description 17
- 229940125904 compound 1 Drugs 0.000 description 14
- 239000003999 initiator Substances 0.000 description 11
- 230000010287 polarization Effects 0.000 description 10
- 239000007788 liquid Substances 0.000 description 8
- 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 7
- 229940125782 compound 2 Drugs 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 125000006850 spacer group Chemical group 0.000 description 6
- 239000004988 Nematic liquid crystal Substances 0.000 description 5
- 229940126214 compound 3 Drugs 0.000 description 5
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 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
- 239000004677 Nylon Substances 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- -1 acryloyloxy group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 2
- UNILWMWFPHPYOR-KXEYIPSPSA-M 1-[6-[2-[3-[3-[3-[2-[2-[3-[[2-[2-[[(2r)-1-[[2-[[(2r)-1-[3-[2-[2-[3-[[2-(2-amino-2-oxoethoxy)acetyl]amino]propoxy]ethoxy]ethoxy]propylamino]-3-hydroxy-1-oxopropan-2-yl]amino]-2-oxoethyl]amino]-3-[(2r)-2,3-di(hexadecanoyloxy)propyl]sulfanyl-1-oxopropan-2-yl Chemical compound O=C1C(SCCC(=O)NCCCOCCOCCOCCCNC(=O)COCC(=O)N[C@@H](CSC[C@@H](COC(=O)CCCCCCCCCCCCCCC)OC(=O)CCCCCCCCCCCCCCC)C(=O)NCC(=O)N[C@H](CO)C(=O)NCCCOCCOCCOCCCNC(=O)COCC(N)=O)CC(=O)N1CCNC(=O)CCCCCN\1C2=CC=C(S([O-])(=O)=O)C=C2CC/1=C/C=C/C=C/C1=[N+](CC)C2=CC=C(S([O-])(=O)=O)C=C2C1 UNILWMWFPHPYOR-KXEYIPSPSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052799 carbon Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229940126543 compound 14 Drugs 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- AOSZTAHDEDLTLQ-AZKQZHLXSA-N (1S,2S,4R,8S,9S,11S,12R,13S,19S)-6-[(3-chlorophenyl)methyl]-12,19-difluoro-11-hydroxy-8-(2-hydroxyacetyl)-9,13-dimethyl-6-azapentacyclo[10.8.0.02,9.04,8.013,18]icosa-14,17-dien-16-one Chemical compound C([C@@H]1C[C@H]2[C@H]3[C@]([C@]4(C=CC(=O)C=C4[C@@H](F)C3)C)(F)[C@@H](O)C[C@@]2([C@@]1(C1)C(=O)CO)C)N1CC1=CC=CC(Cl)=C1 AOSZTAHDEDLTLQ-AZKQZHLXSA-N 0.000 description 1
- GLGNXYJARSMNGJ-VKTIVEEGSA-N (1s,2s,3r,4r)-3-[[5-chloro-2-[(1-ethyl-6-methoxy-2-oxo-4,5-dihydro-3h-1-benzazepin-7-yl)amino]pyrimidin-4-yl]amino]bicyclo[2.2.1]hept-5-ene-2-carboxamide Chemical compound CCN1C(=O)CCCC2=C(OC)C(NC=3N=C(C(=CN=3)Cl)N[C@H]3[C@H]([C@@]4([H])C[C@@]3(C=C4)[H])C(N)=O)=CC=C21 GLGNXYJARSMNGJ-VKTIVEEGSA-N 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- ONBQEOIKXPHGMB-VBSBHUPXSA-N 1-[2-[(2s,3r,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl]oxy-4,6-dihydroxyphenyl]-3-(4-hydroxyphenyl)propan-1-one Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=CC(O)=C1C(=O)CCC1=CC=C(O)C=C1 ONBQEOIKXPHGMB-VBSBHUPXSA-N 0.000 description 1
- 229940126657 Compound 17 Drugs 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000003098 cholesteric effect Effects 0.000 description 1
- 229940125773 compound 10 Drugs 0.000 description 1
- 229940125758 compound 15 Drugs 0.000 description 1
- 229940126142 compound 16 Drugs 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Landscapes
- Polarising Elements (AREA)
- Diffracting Gratings Or Hologram Optical Elements (AREA)
- Liquid Crystal Substances (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、重合性液晶組成
物、これを重合した高分子液晶およびその用途に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymerizable liquid crystal composition, a polymer liquid crystal obtained by polymerizing the composition, and a use thereof.
【０００２】[0002]
【従来の技術】液晶モノマに重合性官能基を付与した重
合性液晶モノマは、モノマとしての性質と液晶としての
性質を併有する。したがって、重合性液晶モノマを配向
させた状態で重合させると、配向が固定化された高分子
液晶が得られる。こうして得られる高分子液晶は、液晶
性骨格の屈折率異方性に基づく光学異方性を有し、液晶
配向状態の制御により特殊な特性も付与できるため、位
相差フィルムや偏光ホログラム等の光学素子に使用され
ている。2. Description of the Related Art A polymerizable liquid crystal monomer obtained by adding a polymerizable functional group to a liquid crystal monomer has both properties as a monomer and a property as a liquid crystal. Therefore, when the polymerizable liquid crystal monomer is polymerized in an oriented state, a polymer liquid crystal in which the orientation is fixed can be obtained. The polymer liquid crystal thus obtained has an optical anisotropy based on the refractive index anisotropy of the liquid crystalline skeleton, and can provide special characteristics by controlling the liquid crystal alignment state. Used in devices.
【０００３】このような重合性液晶モノマのなかでも、
特に光重合性官能基を有する光重合性液晶モノマは、通
常の液晶ディスプレイ等で使用される非重合性液晶と同
様な手法を用いて液晶モノマを配向制御した後に、光を
照射して重合させることで簡単に高分子液晶を作製でき
る優れた材料である。[0003] Among such polymerizable liquid crystal monomers,
In particular, a photopolymerizable liquid crystal monomer having a photopolymerizable functional group is polymerized by irradiating light after controlling the alignment of the liquid crystal monomer using the same method as a non-polymerizable liquid crystal used in a normal liquid crystal display or the like. This is an excellent material that can easily produce a polymer liquid crystal.
【０００４】この高分子液晶を用いた偏光ホログラム
は、偏光依存性を利用することにより高い光利用効率を
発現する。理想的な矩形格子形状においては、格子高さ
ｄ、高分子液晶の屈折率異方性Δｎ、波長λとすると、
Δｎ・ｄ＝λ／２を満たすとき、±１次の回折効率が最
大となる。[0004] A polarization hologram using this polymer liquid crystal exhibits high light use efficiency by utilizing the polarization dependence. In an ideal rectangular lattice shape, assuming that the lattice height is d, the refractive index anisotropy of the polymer liquid crystal is Δn, and the wavelength is λ,
When Δnd · λ / 2 is satisfied, the ± 1st-order diffraction efficiency is maximized.
【０００５】近年、光ヘッドの小型化に伴い、偏光ホロ
グラムは格子ピッチｗの狭小化が求められている。フォ
トリソグラフィでの格子加工に際し、格子のアスペクト
比ｄ／ｗが大きいと理想的な矩形格子形状からのずれが
大きくなり、光利用効率が低下する問題がある。これを
解決するには、屈折率異方性の大きな高分子液晶を用い
ることが有効である。In recent years, with the miniaturization of the optical head, the polarization hologram is required to have a smaller grating pitch w. At the time of grating processing by photolithography, if the aspect ratio d / w of the grating is large, the deviation from the ideal rectangular lattice shape increases, and there is a problem that the light use efficiency decreases. In order to solve this, it is effective to use a polymer liquid crystal having a large refractive index anisotropy.
【０００６】屈折率異方性の大きな液晶モノマとして
は、下記式３で表される化合物（以下化合物３ともい
い、他の場合も同様にいう。）がある（特開平９−２０
８９５７号公報参照）。なお、本明細書において、Ｐｈ
は１，４−フェニレン基を示す。As a liquid crystal monomer having a large refractive index anisotropy, there is a compound represented by the following formula 3 (hereinafter also referred to as compound 3; the same applies to other cases) (JP-A-9-20).
No. 8957). In this specification, Ph
Represents a 1,4-phenylene group.
【０００７】CH2=CH-COO-(CH2)6-O-Ph-Ph-CN・・・式３ 化合物３は、重合性官能基であるアクリロイルオキシ基
と液晶性を発現する分子構造部分（以下、メソゲン骨格
という。）である４’−シアノ−４−ビフェニリル基と
の間にスペーサとしてヘキサメチレン基が導入されてい
るため、重合時の立体障害が低減され、屈折率異方性の
大きな高分子液晶が得られる。CH 2 = CH-COO- (CH 2 ) 6 -O-Ph-Ph-CN Formula 3 Compound 3 is a polymerizable functional group, an acryloyloxy group, and a molecular structure portion exhibiting liquid crystallinity. Since a hexamethylene group is introduced as a spacer between the compound and a 4′-cyano-4-biphenylyl group (hereinafter, referred to as a mesogen skeleton), steric hindrance during polymerization is reduced, and the refractive index anisotropy is reduced. Large polymer liquid crystals can be obtained.
【０００８】しかし、スペーサを含む化合物は、屈折率
異方性は大きいが、その温度依存性も大きい問題があ
る。このような化合物を重合した高分子液晶を用いた光
学素子を光ヘッドの部品とした場合には、該光ヘッドは
環境温度の変化に伴って回折効率が変動するため信号検
出に支障が出る。[0008] However, the compound containing a spacer has a problem in that although its refractive index anisotropy is large, its temperature dependence is also large. When an optical element using a polymer liquid crystal obtained by polymerizing such a compound is used as a component of an optical head, the diffraction efficiency of the optical head fluctuates with a change in environmental temperature, which hinders signal detection.
【０００９】環境温度の変化による回折効率の変動を少
なくするため、高分子液晶の屈折率異方性の温度依存性
を小さくする方法（特開平１０−２６５５３１号公報参
照）がある。これは、非架橋性モノマと架橋性モノマを
特定の質量比で含む液晶性組成物を用いることにより、
温度依存性を小さくする方法である。しかし、この方法
では温度依存性は小さくできるが、必ずしも屈折率異方
性が大きな高分子液晶は得られなかった。以上のよう
に、これまでは屈折率異方性が大きく、かつ、その温度
依存性が小さい高分子液晶は得られていなかった。In order to reduce the change in diffraction efficiency due to a change in environmental temperature, there is a method for reducing the temperature dependence of the refractive index anisotropy of a polymer liquid crystal (see Japanese Patent Application Laid-Open No. 10-265531). This is by using a liquid crystalline composition containing a non-crosslinkable monomer and a crosslinkable monomer in a specific mass ratio,
This is a method of reducing the temperature dependency. However, although this method can reduce the temperature dependency, a polymer liquid crystal having a large refractive index anisotropy was not always obtained. As described above, a polymer liquid crystal having a large refractive index anisotropy and a small temperature dependence has not been obtained.
【００１０】[0010]
【発明が解決しようとする課題】本発明の目的は、屈折
率異方性が大きく、かつ、その温度依存性が小さい高分
子液晶、その用途、およびそのための重合性液晶組成物
の提供にある。用途としては、偏光ホログラム、光ヘッ
ド、位相差フィルムなどがある。SUMMARY OF THE INVENTION An object of the present invention is to provide a polymer liquid crystal having a large refractive index anisotropy and a small temperature dependence, its use, and a polymerizable liquid crystal composition therefor. . Applications include polarization holograms, optical heads, retardation films, and the like.
【００１１】[0011]
【課題を解決するための手段】本発明は、下記式１で表
される非架橋性モノマと下記式２で表される架橋性モノ
マとを含む重合性液晶組成物であって、重合性液晶組成
物中の前記架橋性モノマの量が１０モル％より多いこと
を特徴とする、重合性液晶組成物を提供する。The present invention provides a polymerizable liquid crystal composition comprising a non-crosslinkable monomer represented by the following formula (1) and a crosslinkable monomer represented by the following formula (2): Provided is a polymerizable liquid crystal composition, wherein the amount of the crosslinkable monomer in the composition is more than 10 mol%.
【００１２】[0012]
【化２】 Embedded image
【００１３】式中の記号は以下の意味を示す。 Ｒ1、Ｒ3：それぞれ独立して、水素原子、ハロゲン原子
またはメチル基。 Ｒ2：水素原子、ハロゲン原子、シアノ基または置換さ
れていてもよいアルキル基。 Ｘ1、Ｘ2：それぞれ独立して、単結合、−ＣＯＯ−、−
ＯＣＯ−または−Ｏ−。 Ｙ1、Ｙ2：それぞれ独立して、−ＣＨ2―、−ＯＣＨ2Ｃ
Ｈ2−または−ＣＨ2ＣＨ2Ｏ−。 ｍ：１〜１２の整数。 ｎ、ｒ：それぞれ独立して、１〜１０の整数。 Ｚ1、Ｚ2、Ｚ3、Ｚ4、Ｚ5、Ｚ6、Ｚ7、Ｚ8、Ｚ9、
Ｚ10：それぞれ独立して、 単結合、−Ｏ−、−ＯＣＯ−、−ＣＯＯ−、−ＣＯ−、
−ＣＯＮＨ−、−ＮＨＣＯ−、−ＮＨ−、−Ｃ≡Ｃ−、
−ＣＨ＝ＣＨ−、−ＣＨ2ＣＨ2−、−Ｎ＝ＣＨ−、−Ｃ
Ｈ＝Ｎ−または−Ｎ＝Ｎ−。 Ｅ1、Ｅ2、Ｅ3、Ｅ4、Ｅ5、Ｅ6、Ｅ7、Ｅ8：それぞれ独
立して、置換されてていてもよい１，４−フェニレン基
または置換されていてもよいトランス−１，４−シクロ
ヘキシレン基。 ｐ、ｑ、ｓ、ｔ：それぞれ独立して、０または１。The symbols in the formula have the following meanings. R 1 and R 3 each independently represent a hydrogen atom, a halogen atom or a methyl group. R 2 : a hydrogen atom, a halogen atom, a cyano group or an optionally substituted alkyl group. X 1 , X 2 : each independently represents a single bond, -COO-,-
OCO- or -O-. Y 1 , Y 2 : each independently represents —CH 2 —, —OCH 2 C
H 2 — or —CH 2 CH 2 O—. m: an integer from 1 to 12. n and r: each independently an integer of 1 to 10. Z 1 , Z 2 , Z 3 , Z 4 , Z 5 , Z 6 , Z 7 , Z 8 , Z 9 ,
Z 10: each independently a single bond, -O -, - OCO -, - COO -, - CO-,
-CONH-, -NHCO-, -NH-, -C≡C-,
-CH = CH -, - CH 2 CH 2 -, - N = CH -, - C
H = N- or -N = N-. E 1 , E 2 , E 3 , E 4 , E 5 , E 6 , E 7 , E 8 : independently of each other, an optionally substituted 1,4-phenylene group or an optionally substituted trans -1,4-cyclohexylene group. p, q, s, t: 0 or 1 each independently.
【００１４】[0014]
【発明の実施の形態】本発明における非架橋性モノマ
は、重合性官能基とメソゲン骨格の間にスペーサを有す
る化合物１である。重合性液晶組成物は、２種以上の化
合物１を含んでもよい。BEST MODE FOR CARRYING OUT THE INVENTION The non-crosslinkable monomer in the present invention is Compound 1 having a spacer between a polymerizable functional group and a mesogen skeleton. The polymerizable liquid crystal composition may contain two or more compounds 1.
【００１５】化合物１のＥ1、Ｅ2、Ｅ3、Ｅ4において、
置換された１，４−フェニレン基としては、＝ＣＨ−が
＝Ｎ−に置換された基、または、１つ以上の水素原子が
メチル基またはハロゲン原子（フッ素原子、塩素原子
等）に置換された基等が挙げられる。たとえば、＝Ｎ−
に置換された場合は屈折率異方性が大きくなり、メチル
基またはハロゲン原子に置換された場合は一般に融点が
低下し、特に水素原子がフッ素原子に置換された場合は
粘度も低下する。そのため、目的に応じて置換基を選択
するのが好ましい。In Compound 1, E 1 , E 2 , E 3 , and E 4
Examples of the substituted 1,4-phenylene group include a group in which ＣＨCH— is substituted with ＮN—, or a compound in which one or more hydrogen atoms are substituted with a methyl group or a halogen atom (such as a fluorine atom or a chlorine atom). And the like. For example, = N-
When the compound is substituted with a compound, the refractive index anisotropy increases, and when the compound is substituted with a methyl group or a halogen atom, the melting point generally decreases. In particular, when a hydrogen atom is substituted with a fluorine atom, the viscosity also decreases. Therefore, it is preferable to select a substituent according to the purpose.
【００１６】化合物１におけるメソゲン骨格としては、
−Ｐｈ−Ｐｈ−Ｒ2、−Ｐｈ−ＣＨ＝ＣＨ−Ｐｈ−Ｒ2、
−Ｐｈ−Ｃ≡Ｃ−Ｐｈ−Ｒ2、−Ｐｈ−Ｎ＝ＣＨ−Ｐｈ
−Ｒ 2、−Ｐｈ−Ｎ＝Ｎ−Ｐｈ−Ｒ2等が、屈折率異方性
を大きくし、融点を比較的低くすることから好ましい。
特に、上記メソゲン骨格におけるＲ2がシアノ基である
場合には、屈折率異方性を大きくするため好ましい。The mesogen skeleton in compound 1 includes:
-Ph-Ph-RTwo, -Ph-CH = CH-Ph-RTwo,
-Ph-C≡C-Ph-RTwo, -Ph-N = CH-Ph
-R Two, -Ph-N = N-Ph-RTwoEtc., refractive index anisotropy
And the melting point is relatively low.
In particular, R in the mesogen skeletonTwoIs a cyano group
In this case, it is preferable to increase the refractive index anisotropy.
【００１７】また化合物１におけるスペーサは、重合後
に配向性が阻害されないための緩衝の役割を持つ。しか
し、スペーサが長すぎると、重合後の高分子液晶が柔ら
かくなり、屈折率異方性の温度依存性が大きくなる。そ
のため、化合物１においては、Ｙ1が−ＣＨ2−かつｍが
４〜１０の整数、または、Ｙ1が−ＣＨ2ＣＨ2Ｏ−かつ
ｍが２〜４の整数、であることが好ましい。The spacer in the compound 1 has a buffering role so that the orientation is not hindered after the polymerization. However, if the spacer is too long, the polymer liquid crystal after polymerization becomes soft, and the temperature dependence of the refractive index anisotropy increases. Therefore, in compound 1, it is preferable that Y 1 is —CH 2 — and m is an integer of 4 to 10, or Y 1 is —CH 2 CH 2 O— and m is an integer of 2 to 4.
【００１８】一方、架橋性モノマは、重合性官能基とメ
ソゲン骨格の間にスペーサを有し、重合性官能基を分子
中に２つ有する化合物２である。化合物２のＥ5、Ｅ6、
Ｅ7、Ｅ8において、置換された１，４−フェニレン基と
しては、前述のＥ1、Ｅ2、Ｅ3、Ｅ4と同様の基が挙げら
れる。On the other hand, the crosslinkable monomer is a compound 2 having a spacer between a polymerizable functional group and a mesogen skeleton and having two polymerizable functional groups in a molecule. E 5 , E 6 ,
In E 7 and E 8 , examples of the substituted 1,4-phenylene group include the same groups as those described above for E 1 , E 2 , E 3 and E 4 .
【００１９】化合物２におけるメソゲン骨格としては、
−Ｐｈ−Ｐｈ−、−Ｐｈ−ＣＨ＝ＣＨ−Ｐｈ−、−Ｐｈ
−Ｃ≡Ｃ−Ｐｈ−、−Ｐｈ−Ｎ＝ＣＨ−Ｐｈ−、−Ｐｈ
−Ｎ＝Ｎ−Ｐｈ−等が好ましい。また化合物２として
は、ｎ＝ｒである化合物が、合成が容易であるため好ま
しい。The mesogen skeleton in compound 2 includes:
-Ph-Ph-, -Ph-CH = CH-Ph-, -Ph
-C≡C-Ph-, -Ph-N = CH-Ph-, -Ph
-N = N-Ph- or the like is preferable. Further, as the compound 2, a compound in which n = r is preferable because of easy synthesis.
【００２０】化合物１または化合物２の液晶性について
は、化合物１および化合物２はそれぞれ液晶性を有する
ことが好ましいが、それを含んでなる重合性液晶組成物
が液晶性を発現すればよく、化合物１および化合物２が
必ずしも単独で液晶性を発現しなくてもよい。Regarding the liquid crystallinity of the compound 1 or the compound 2, it is preferable that the compound 1 and the compound 2 each have a liquid crystallinity, but it is sufficient that a polymerizable liquid crystal composition containing the compound exhibits the liquid crystallinity. It is not necessary that Compound 1 and Compound 2 independently exhibit liquid crystallinity.
【００２１】架橋性モノマ（化合物２）の分子長は、非
架橋性モノマ（化合物１）の分子長以上であることが好
ましい。このことにより、屈折率異方性の大きな高分子
液晶が得られる。以下、この分子長について説明する。
分子長とは、非架橋性モノマまたは架橋性モノマにおい
て、重合後に主鎖を構成する二重結合部位を除いた部分
の長さ、すなわち側鎖長を意味する。非架橋性モノマの
分子長をＬ1、架橋性モノマの分子長をＬ2と記す。The molecular length of the crosslinkable monomer (compound 2) is preferably longer than the molecular length of the non-crosslinkable monomer (compound 1). Thereby, a polymer liquid crystal having a large refractive index anisotropy can be obtained. Hereinafter, the molecular length will be described.
The molecular length means a length of a non-crosslinkable monomer or a crosslinkable monomer excluding a double bond site constituting a main chain after polymerization, that is, a side chain length. The molecular length of the non-crosslinkable monomer is denoted by L 1 , and the molecular length of the crosslinkable monomer is denoted by L 2 .
【００２２】たとえば、非架橋性モノマである前記化合
物３の分子長とは、末端のシアノ基のＮと二重結合の炭
素Ｃ2［式３’に化合物３の二重結合の炭素に番号を付
記］の間の距離のことである。同様に、たとえば架橋性
モノマの分子長とは、下記式４で表される化合物におい
てＣ4とＣ5の間の距離のことである。For example, the molecular length of the compound 3, which is a non-crosslinkable monomer, is defined as N of the terminal cyano group and carbon C 2 of the double bond [Formula 3 ′ indicates the number of the carbon of the double bond of the compound 3 Note). Similarly, for example, the molecular length of the crosslinkable monomer is the distance between C 4 and C 5 in the compound represented by the following formula 4.
【００２３】[0023]
【化３】 Embedded image
【００２４】分子長Ｌ１およびＬ２は、Ｃｈｅｍ ３Ｄ
（Ｃａｍｂｒｉｄｇｅ Ｓｃｉｅｎｔｉｆｉｃ Ｃｏｍ
ｐｕｔｉｎｇ Ｉｎｃ．製、商品名）を用いて、分子構
造から計算によって求められる。具体的には、化合物３
のＬ１は２．０７ｎｍ、化合物４のＬ２は３．００ｎｍ
である。The molecular lengths L1 and L2 are as defined in Chem 3D
(Cambridge Scientific Com
putting Inc. (Product name, product name). Specifically, Compound 3
L1 of the compound 4 was 2.07 nm, and L2 of the compound 4 was 3.00 nm.
It is.
【００２５】ところで高分子液晶において、その秩序性
が保たれると屈折率異方性は大きくなる。高分子液晶の
秩序性は、ネットワーク構造（架橋構造）を形成する架
橋性モノマの秩序性に依るところが大きく、これはＬ2
とＬ1の関係に依る。In the polymer liquid crystal, the refractive index anisotropy increases when the order is maintained. Orderliness of the polymer liquid crystal, a large place due to ordering of the crosslinkable monomer for forming a network structure (crosslinked structure), which is L 2
And L 1 .
【００２６】Ｌ2＜Ｌ1の場合は、重合性液晶組成物にお
いては保たれていた秩序性が、重合後には低下する。こ
のため、Ｌ2＜Ｌ1である架橋性モノマを重合性液晶組成
物中に含むと、高分子液晶の屈折率異方性が小さくな
る。Ｌ2≧Ｌ1の場合は、重合後も秩序性の低下が少ない
かまたは秩序性が良好に保たれるため、屈折率異方性の
大きな高分子液晶を得ることができる。When L 2 <L 1 , the order maintained in the polymerizable liquid crystal composition decreases after polymerization. Therefore, when the polymerizable liquid crystal composition contains a crosslinkable monomer satisfying L 2 <L 1 , the refractive index anisotropy of the polymer liquid crystal decreases. When L 2 ≧ L 1 , a decrease in order is small or the order is kept good even after polymerization, so that a polymer liquid crystal having a large refractive index anisotropy can be obtained.
【００２７】重合性液晶組成物中の架橋性モノマの量
は、１０モル％より多いことが必要であり、２０〜９０
モル％が好ましい。この量が少なすぎると、重合後の高
分子液晶の屈折率異方性が大きくなる効果が十分でなか
ったり、温度依存性が低い高分子液晶が得られない等の
問題がある。また、多すぎると、一般に融点が高くなっ
て作業性が損なわれたり、重合時の収縮が大きくなって
クラックが生じる等の問題がある。The amount of the crosslinkable monomer in the polymerizable liquid crystal composition needs to be more than 10 mol%, and 20 to 90%
Molar% is preferred. If the amount is too small, there are problems that the effect of increasing the refractive index anisotropy of the polymer liquid crystal after polymerization is not sufficient, and that a polymer liquid crystal having low temperature dependence cannot be obtained. On the other hand, if the amount is too large, there is a problem that the melting point generally becomes high and the workability is impaired, and the shrinkage during polymerization becomes large and cracks occur.
【００２８】さらに式１において、ｐ＋ｑ＝１（すなわ
ち、ｐおよびｑのいずれか一方が０であり、ｐおよびｑ
のいずれか他方が１である。）である化合物１（この化
合物１を以下、化合物１Ａという。）は高温域で液晶相
を発現する。したがって化合物１Ａを含む重合性液晶組
成物は、広い温度範囲で液晶相となるため好ましい。特
にＲ2がシアノ基である場合には、屈折率異方性が大き
い点からより好ましい。Ｒ2がシアノ基である化合物１
Ａは、重合性液晶組成物中に１０〜８０モル％含まれる
ことが好ましい。１０モル％より少ないと前記効果が少
なく、８０モル％より多いと重合温度が高く使用しにく
くなるため、好ましくない。Further, in the expression 1, p + q = 1 (that is, one of p and q is 0, p and q
One of the two is 1. Compound 1 (hereinafter, this compound 1 is referred to as compound 1A) exhibits a liquid crystal phase in a high temperature range. Therefore, a polymerizable liquid crystal composition containing compound 1A is preferable because it becomes a liquid crystal phase in a wide temperature range. In particular, when R 2 is a cyano group, it is more preferable since the refractive index anisotropy is large. Compound 1 wherein R 2 is a cyano group
A is preferably contained in the polymerizable liquid crystal composition at 10 to 80 mol%. If the amount is less than 10 mol%, the above effect is small, and if it is more than 80 mol%, the polymerization temperature is high and it is difficult to use, which is not preferable.
【００２９】重合性液晶組成物中には、他の重合性モノ
マを含んでいてもよい。他の重合性モノマは、用途、要
求性能等により異なるが、低温で液晶性を示す重合性液
晶モノマ、低粘性の重合性モノマ、屈折率異方性を向上
させる重合性モノマ、コレステリック性を付与させる重
合性モノマ、その他各種重合性モノマが挙げられる。The polymerizable liquid crystal composition may contain another polymerizable monomer. Other polymerizable monomers vary depending on applications, required performance, etc., but polymerizable liquid crystal monomers exhibiting liquid crystallinity at low temperatures, polymerizable monomers having low viscosity, polymerizable monomers improving refractive index anisotropy, and cholesteric properties are provided. And various other polymerizable monomers.
【００３０】本発明の重合性液晶組成物を重合させるこ
とにより、高分子液晶を得ることができる。屈折率異方
性の大きな高分子液晶を得るためには、重合性液晶組成
物の屈折率異方性が０．１５以上であることが好まし
い。A polymer liquid crystal can be obtained by polymerizing the polymerizable liquid crystal composition of the present invention. In order to obtain a polymer liquid crystal having a large refractive index anisotropy, the polymerizable liquid crystal composition preferably has a refractive index anisotropy of 0.15 or more.
【００３１】該重合としては、光重合が好ましい。光重
合に用いる光としては、紫外線、可視光線等が挙げられ
る。光重合を行う場合には、光重合開始剤を用いると効
率よく反応させうる。光重合開始剤としては特に限定さ
れず、アセトフェノン類、ベンゾフェノン類、ベンゾイ
ン類、ベンジル類、ミヒラーケトン類、ベンゾインアル
キルエーテル類、ベンジルジメチルケタール類、チオキ
サントン類等が好ましく使用できる。また必要に応じ、
２種以上の光重合開始剤を混合して使用してもよい。光
重合開始剤の使用量は、重合性液晶組成物に対して０．
１〜１０質量％が好ましく、特に０．５〜２質量％が好
ましい。As the polymerization, photopolymerization is preferred. Examples of light used for photopolymerization include ultraviolet light and visible light. In the case of performing photopolymerization, the reaction can be efficiently performed by using a photopolymerization initiator. The photopolymerization initiator is not particularly limited, and acetophenones, benzophenones, benzoins, benzyls, Michler's ketones, benzoin alkyl ethers, benzyldimethyl ketals, thioxanthones, and the like can be preferably used. If necessary,
Two or more photopolymerization initiators may be used as a mixture. The amount of the photopolymerization initiator used is 0.1 to the polymerizable liquid crystal composition.
It is preferably from 1 to 10% by mass, particularly preferably from 0.5 to 2% by mass.
【００３２】本発明の重合性液晶組成物を重合させる際
には、複数枚の支持体の間にガラスビーズ等を配置し、
該支持体を所望の間隔に制御して対向させ、支持体の間
に本発明の重合性液晶組成物を注入し、充填させて重合
させるのが好ましい。該支持体としては、ガラス板、プ
ラスチック板等を使用できる。When polymerizing the polymerizable liquid crystal composition of the present invention, glass beads or the like are arranged between a plurality of supports,
It is preferable that the supports are controlled to face each other at a desired distance, and the polymerizable liquid crystal composition of the present invention is injected between the supports, filled and polymerized. As the support, a glass plate, a plastic plate or the like can be used.
【００３３】また、支持体表面には配向処理が施されて
いるのが好ましい。配向処理は、支持体面を、斜方蒸着
するか、綿、羊毛等の天然繊維、ナイロン、ポリエステ
ル等の合成繊維等で直接ラビングするか、またはポリイ
ミド、ポリアミド等を塗布しその面を上記繊維等でラビ
ングする、のがよい。It is preferable that the surface of the support is subjected to an orientation treatment. In the orientation treatment, the surface of the support is obliquely vapor-deposited, directly rubbed with natural fibers such as cotton and wool, and synthetic fibers such as nylon and polyester, or coated with polyimide, polyamide or the like, and the surface is coated with the above-mentioned fibers or the like. Rubbing is good.
【００３４】重合性液晶組成物を液晶状態に保つために
は、雰囲気温度を融点Ｔm［℃］以上、等方相相転移温
度Ｔc［℃］以下の範囲にするのが好ましいが、Ｔcに近
い温度では屈折率異方性がきわめて小さいので、雰囲気
温度の上限は（Ｔc−１０）℃以下とするのがより好ま
しい。本発明の重合性液晶組成物は、重合時に比較的安
定に液晶状態を保持していれば、過冷却状態のような短
期的に安定な液晶状態で重合してもよい。In order to keep the polymerizable liquid crystal composition in a liquid crystal state, it is preferable that the ambient temperature is in a range from a melting point T m [° C.] to an isotropic phase transition temperature T c [° C.]. Since the refractive index anisotropy is extremely small at a temperature close to c , the upper limit of the ambient temperature is more preferably (T c -10) ° C. or less. The polymerizable liquid crystal composition of the present invention may be polymerized in a short-term stable liquid crystal state such as a supercooled state as long as the liquid crystal state is maintained relatively stably during polymerization.
【００３５】本発明の高分子液晶は、支持体に挟んだま
ま用いてもよく、支持体から剥離して用いてもよい。本
発明の高分子液晶の屈折率異方性の温度依存性は小さい
が、これは架橋性モノマを添加しているためである。本
発明の高分子液晶は、光学素子に好適である。光学素子
としては、位相差フィルムや偏光ホログラム素子等が挙
げられる。該高分子液晶を用いた偏光ホログラム素子は
光利用効率が高く、回折効率の温度依存性も小さい。該
偏光ホログラム素子を光ヘッドの部品として用いれば、
光利用効率の高い光ヘッドを作製できる。The polymer liquid crystal of the present invention may be used while being sandwiched between supports, or may be used after being separated from the support. Although the temperature dependence of the refractive index anisotropy of the polymer liquid crystal of the present invention is small, this is because a crosslinkable monomer is added. The polymer liquid crystal of the present invention is suitable for an optical element. Examples of the optical element include a retardation film and a polarization hologram element. The polarization hologram element using the polymer liquid crystal has a high light use efficiency and a small temperature dependence of the diffraction efficiency. If the polarization hologram element is used as a component of an optical head,
An optical head having high light use efficiency can be manufactured.
【００３６】[0036]
【実施例】以下の各例で用いた化合物６〜１７はそれぞ
れ式６〜１７で表される化合物である。EXAMPLES Compounds 6 to 17 used in the following examples are compounds represented by formulas 6 to 17, respectively.
【００３７】[0037]
【化４】 Embedded image
【００３８】［例１（実施例）］以下の化合物を（ ）
内のモル比にて含む組成物Ａを調製した。化合物６［Ｌ
1＝１．３１ｎｍ］（０．２５）、化合物７［Ｌ1＝１．
７５ｎｍ］（０．１０）、化合物８［Ｌ1＝２．０７ｎ
ｍ］（０．３６）、化合物９［Ｌ1＝１．８１ｎｍ］
（０．１０）、化合物１０［Ｌ1＝１．９１ｎｍ］
（０．１９）。組成物Ａに、架橋性モノマとして化合物
１１［Ｌ2＝３．００ｎｍ］を組成物Ｂ全量中に２０モ
ル％となるように加え、組成物Ｂを調製した。[Example 1 (Example)]
The composition A containing the above molar ratio was prepared. Compound 6 [L
1 = 1.31 nm] (0.25), compound 7 [L 1 = 1.
75 nm] (0.10), compound 8 [L 1 = 2.07 n
m] (0.36), compound 9 [L 1 = 1.81 nm]
(0.10), compound 10 [L 1 = 1.91 nm]
(0.19). Compound B was prepared by adding Compound 11 [L 2 = 3.00 nm] as a crosslinkable monomer to Composition A such that the total amount of Compound 11 was 20 mol% in the total amount of Composition B.
【００３９】［例２（実施例）］配向剤であるポリイミ
ドをスピンコータで塗布し、熱処理した後、ナイロンク
ロスで一定方向にラビング処理したガラス板を支持体と
し、配向処理した面が向かいあうように２枚の支持体を
接着剤を用いて貼り合わせ、その１辺にガラスブロック
を挿入して、くさび形状となるセルＭを作製した。セル
Ｍにおける、くさび頂角は約１．６度、寸法は縦１７ｍ
ｍ、横３０ｍｍであり、ラビング方向はくさび先端の頂
辺方向に対して１８０度である。Example 2 (Example) Polyimide as an aligning agent was applied by a spin coater, and after heat treatment, a glass plate rubbed in a certain direction with a nylon cloth was used as a support. Two substrates were bonded together using an adhesive, and a glass block was inserted into one side of the two substrates, thereby producing a cell M having a wedge shape. In cell M, the wedge apex angle is about 1.6 degrees and the size is 17 m in length.
m, 30 mm in width, and the rubbing direction is 180 degrees with respect to the top side direction of the wedge tip.
【００４０】組成物Ｂに光重合開始剤「イルガキュアー
９０７（チバガイギー社製）」を０．５質量％添加した
ものを、上記のように作製したセルＭに８０℃で先端部
に注入した。次に４０℃で波長３６５ｎｍにおいて５ｍ
Ｗ／ｃｍ2の強度の紫外線を３００秒照射し、光重合を
行った。重合後、フィルム状の高分子液晶Ｂが得られ
た。この高分子液晶は可視域で透明であり、散乱も見ら
れなかった。A composition B to which 0.5% by mass of a photopolymerization initiator “Irgacure 907 (manufactured by Ciba Geigy)” was added was injected into the cell M prepared as described above at 80 ° C. at the tip. Next, 5 m at a wavelength of 365 nm at 40 ° C.
Photopolymerization was performed by irradiating with ultraviolet light having an intensity of W / cm 2 for 300 seconds. After the polymerization, a film-like polymer liquid crystal B was obtained. This polymer liquid crystal was transparent in the visible region, and no scattering was observed.
【００４１】［例３（実施例）］ピッチ６μｍ、深さ３
μｍの矩形格子が形成された直径７５ｍｍの円板状のガ
ラス基板上に、配向剤であるポリイミドをスピンコータ
で塗布し、熱処理した後、ナイロンクロスで格子方向に
対して平行方向にラビング処理を行ったものと、配向処
理を同様に行ったガラス平板基板とを、配向処理面が向
かいあい、セルギャップが３μｍになるように接着剤を
用いて貼り合わせて、セルＮを作製した。その際、配向
方向が平行になるようにした。Example 3 (Example) Pitch: 6 μm, Depth: 3
Polyimide as an aligning agent is applied on a disk-shaped glass substrate having a diameter of 75 mm on which a rectangular grid of μm is formed by a spin coater, and after heat treatment, rubbing is performed with a nylon cloth in a direction parallel to the grid direction. And a glass plate substrate that was similarly subjected to the alignment treatment, and was bonded using an adhesive so that the alignment treatment surfaces faced each other and the cell gap was 3 μm, thereby producing a cell N. At that time, the orientation directions were made parallel.
【００４２】組成物Ｂに光重合開始剤「イルガキュアー
９０７（チバガイギー社製）」を０．５質量％添加した
ものを、上記のように作製したセルＮに８０℃で注入
し、格子状凹部を組成物Ｂにより充填した。次に、４０
℃で波長３６５ｎｍにおいて５ｍＷ／ｃｍ2の強度の紫
外線を３００秒照射し、光重合を行った。このセルＮの
片面に１／４波長板を積層し、偏光ホログラムビームス
プリッタ（光学素子）を作製した。この偏光ホログラム
ビームスプリッタを光ヘッドの部品に用いたところ、該
光ヘッドは波長６５０ｎｍのレーザ光源にて、±１次の
回折効率の合計で５０％の光利用効率を得た。A composition B to which 0.5% by mass of a photopolymerization initiator “Irgacure 907 (manufactured by Ciba Geigy)” was added was injected into the cell N prepared at 80 ° C. at 80 ° C. Was filled with composition B. Next, 40
Ultraviolet rays having an intensity of 5 mW / cm 2 at a wavelength of 365 nm and a wavelength of 365 nm were irradiated for 300 seconds to perform photopolymerization. A quarter-wave plate was laminated on one side of the cell N to produce a polarization hologram beam splitter (optical element). When this polarization hologram beam splitter was used as a component of an optical head, the optical head obtained a total of ± 1st-order diffraction efficiencies of 50% using a laser light source having a wavelength of 650 nm.
【００４３】［例４（比較例）］例２において、組成物
Ｂの代わりに組成物Ａを用い、紫外線照射を４０℃の代
わりに３０℃で行う以外は例２と同様にして、高分子液
晶Ａが得られた。この高分子液晶は可視域で透明であ
り、散乱も見られなかった。Example 4 (Comparative Example) A polymer was prepared in the same manner as in Example 2 except that the composition A was used in place of the composition B and the ultraviolet irradiation was performed at 30 ° C. instead of 40 ° C. Liquid crystal A was obtained. This polymer liquid crystal was transparent in the visible region, and no scattering was observed.
【００４４】「例５（比較例）」組成物Ａに、化合物１
１を組成物Ｃ全量中に１０モル％となるように加え、組
成物Ｃを調製した。例４において、組成物Ａの代わりに
組成物Ｃを用いる以外は例４と同様にして、高分子液晶
Ｃを得た。この高分子液晶は可視域で透明であり、散乱
も見られなかった。Example 5 (Comparative Example) Compound 1 was added to composition A.
Composition C was prepared by adding 1 to 10 mol% of the total amount of Composition C. Polymer liquid crystal C was obtained in the same manner as in Example 4, except that composition C was used instead of composition A. This polymer liquid crystal was transparent in the visible region, and no scattering was observed.
【００４５】［例６（比較例）］組成物Ａに、化合物１
２［Ｌ2＝１．４１ｎｍ］を組成物Ｄ全量中に１０モル
％となるように加え、組成物Ｄを調製した。例４におい
て、組成物Ａの代わりに組成物Ｄを用いる以外は例４と
同様にして、高分子液晶Ｄが得られた。この高分子液晶
は可視域で透明であり、散乱も見られなかった。Example 6 (Comparative Example) Compound 1 was added to composition A.
2 [L 2 = 1.41 nm] was added so as to be 10 mol% in the total amount of the composition D to prepare a composition D. Polymer liquid crystal D was obtained in the same manner as in Example 4, except that composition D was used instead of composition A. This polymer liquid crystal was transparent in the visible region, and no scattering was observed.
【００４６】［例７（実施例）］化合物６［Ｌ1＝１．
３１ｎｍ］（０．２０）、化合物８［Ｌ1＝２．０７ｎ
ｍ］（０．３５）、化合物１３［Ｌ1＝２．６９ｎｍ］
（０．１５）、化合物１１［Ｌ2＝３．００ｎｍ］
（０．３０）からなる組成物Ｅを調製した。組成物Ｅは
５５〜７４℃の範囲でネマチック液晶であった。これに
光重合開始剤「イルガキュアー９０７（チバガイギー社
製）」を０．５質量％添加したものを、例２記載のセル
Ｍに８０℃で注入した。次に６０℃で波長３６５ｎｍに
おいて５ｍＷ／ｃｍ2の強度の紫外線を３００秒照射
し、光重合を行った。重合後、フィルム状の高分子液晶
Ｅが得られた。この高分子液晶は可視域で透明であり、
散乱も見られなかった。Example 7 (Example) Compound 6 [L 1 = 1.
31 nm] (0.20), compound 8 [L 1 = 2.07 n
m] (0.35), compound 13 [L 1 = 2.69 nm]
(0.15), compound 11 [L 2 = 3.00 nm]
Composition E consisting of (0.30) was prepared. Composition E was a nematic liquid crystal in the range of 55 to 74 ° C. To this, a photopolymerization initiator “Irgacure 907 (manufactured by Ciba Geigy)” added in an amount of 0.5% by mass was injected at 80 ° C. into the cell M described in Example 2. Next, ultraviolet light having an intensity of 5 mW / cm 2 at a wavelength of 365 nm at a temperature of 60 ° C. was irradiated for 300 seconds to perform photopolymerization. After the polymerization, a polymer liquid crystal E in the form of a film was obtained. This polymer liquid crystal is transparent in the visible range,
No scattering was seen.
【００４７】［例８（実施例）］例７において、化合物
１１の代わりに化合物１４［Ｌ2＝２．８２ｎｍ］
（０．３０）を用いる以外は例７と同様にして、組成物
Ｆを調製した。組成物Ｆは４４〜７９℃の範囲でネマチ
ック液晶であった。これに光重合開始剤「イルガキュア
ー９０７（チバガイギー社製）」を０．５質量％添加し
たものを、例２記載のセルＭに８０℃で注入した。次に
５０℃で波長３６５ｎｍにおいて５ｍＷ／ｃｍ 2の強度
の紫外線を３００秒照射し、光重合を行った。重合後、
フィルム状の高分子液晶Ｆが得られた。この高分子液晶
は可視域で透明であり、散乱も見られなかった。Example 8 (Example) In Example 7, the compound
Compound 14 [L instead of 11Two= 2.82 nm]
A composition was prepared in the same manner as in Example 7 except that (0.30) was used.
F was prepared. Composition F is nematic at 44-79 ° C.
Liquid crystal. Add the photopolymerization initiator “Irgacure
-907 (manufactured by Ciba-Geigy) ".
This was injected at 80 ° C. into the cell M described in Example 2. next
5 mW / cm at a wavelength of 365 nm at 50 ° C. TwoStrength of
For 300 seconds to perform photopolymerization. After polymerization,
A film-like polymer liquid crystal F was obtained. This polymer liquid crystal
Was transparent in the visible region and no scattering was observed.
【００４８】［例９（実施例）］例７において、化合物
１１の代わりに化合物１５［Ｌ2＝３．３２ｎｍ］
（０．３０）を用いる以外は例７と同様にして、組成物
Ｇを調製した。組成物Ｇは５７〜７９℃の範囲でネマチ
ック液晶であった。これに光重合開始剤「イルガキュア
ー９０７（チバガイギー社製）」を０．５質量％添加し
たものを、例２記載のセルＭに８５℃で注入した。次に
６０℃で波長３６５ｎｍにおいて５ｍＷ／ｃｍ 2の強度
の紫外線を３００秒照射し、光重合を行った。重合後、
フィルム状の高分子液晶Ｇが得られた。この高分子液晶
は可視域で透明であり、散乱も見られなかった。Example 9 (Example)
Compound 15 [L instead of 11Two= 3.32 nm]
A composition was prepared in the same manner as in Example 7 except that (0.30) was used.
G was prepared. Composition G is nematic at 57-79 ° C.
Liquid crystal. Add the photopolymerization initiator “Irgacure
-907 (manufactured by Ciba-Geigy) ".
Was injected into the cell M described in Example 2 at 85 ° C. next
5 mW / cm at a wavelength of 365 nm at 60 ° C. TwoStrength of
For 300 seconds to perform photopolymerization. After polymerization,
A film-like polymer liquid crystal G was obtained. This polymer liquid crystal
Was transparent in the visible region and no scattering was observed.
【００４９】［例１０（実施例）］例７において、化合
物１１の代わりに化合物１６［Ｌ2＝３．８２ｎｍ］
（０．３０）を用いる以外は例７と同様にして、組成物
Ｈを調製した。組成物Ｈは６６〜８１℃の範囲でネマチ
ック液晶であった。これに光重合開始剤「イルガキュア
ー９０７（チバガイギー社製）」を０．５質量％添加し
たものを、例２記載のセルＭに８５℃で注入した。次に
７０℃で波長３６５ｎｍにおいて５ｍＷ／ｃｍ 2の強度
の紫外線を３００秒照射し、光重合を行った。重合後、
フィルム状の高分子液晶Ｈが得られた。この高分子液晶
は可視域で透明であり、散乱も見られなかった。Example 10 (Example)
Compound 16 [L instead of compound 11Two= 3.82 nm]
A composition was prepared in the same manner as in Example 7 except that (0.30) was used.
H was prepared. Composition H is nematic at 66-81 ° C.
Liquid crystal. Add the photopolymerization initiator “Irgacure
-907 (manufactured by Ciba-Geigy) ".
Was injected into the cell M described in Example 2 at 85 ° C. next
5 mW / cm at 365 ° C. at 70 ° C. TwoStrength of
For 300 seconds to perform photopolymerization. After polymerization,
A film-like polymer liquid crystal H was obtained. This polymer liquid crystal
Was transparent in the visible region and no scattering was observed.
【００５０】［例１１（実施例）］化合物１３（０．２
０）、化合物１７［Ｌ1＝２．０８ｎｍ］（０．５
０）、化合物１４（０．３０）からなる組成物Ｉを調製
した。組成物Ｉは５２〜８３℃の範囲でネマチック液晶
であった。これに光重合開始剤「イルガキュアー９０７
（チバガイギー社製）」を０．５質量％添加したもの
を、例２記載のセルＭに８５℃で注入した。次に６０℃
で波長３６５ｎｍにおいて５０ｍＷ／ｃｍ2の強度の紫
外線を６０秒照射し、光重合を行った。重合後、フィル
ム状の高分子液晶Ｉが得られた。この高分子液晶は可視
域で透明であり、散乱も見られなかった。Example 11 (Example) Compound 13 (0.2
0), compound 17 [L 1 = 2.08 nm] (0.5
0) and composition I consisting of compound 14 (0.30) were prepared. Composition I was a nematic liquid crystal in the range of 52 to 83 ° C. The photopolymerization initiator “Irgacure 907
(Manufactured by Ciba-Geigy) "was added to the cell M described in Example 2 at 85 ° C. Then 60 ° C
In the ultraviolet intensity of 50 mW / cm 2 was irradiated for 60 seconds at a wavelength 365 nm, was photopolymerization. After the polymerization, a film-like polymer liquid crystal I was obtained. This polymer liquid crystal was transparent in the visible region, and no scattering was observed.
【００５１】各重合性液晶組成物について、重合性液晶
組成物全量中の架橋性モノマの割合Ｖ［モル％］、Ｔc
［℃］、ネマチック液晶温度範囲［℃］および（ ）内
の温度［℃］での波長５８９ｎｍの光におけるΔｎを表
１に示す。表１の組成物Ａ〜Ｄのネマチック液晶温度範
囲においては、過冷却状態のネマチック液晶温度範囲を
含む。各高分子液晶の３０℃、８０℃での波長５８９ｎ
ｍの光におけるΔｎおよびその温度によるΔｎの変化率
Ｕ：１００×（Δｎ（８０℃）−Δｎ（３０℃））／Δ
ｎ（３０℃）（温度依存性）を表２に示す。For each polymerizable liquid crystal composition, the ratio V [mol%] of the crosslinkable monomer in the total amount of the polymerizable liquid crystal composition, T c
Table 1 shows Δn for light having a wavelength of 589 nm in [° C.], a nematic liquid crystal temperature range [° C.], and a temperature [° C.] in parentheses. The nematic liquid crystal temperature range of the compositions A to D in Table 1 includes the supercooled nematic liquid crystal temperature range. Wavelength 589n at 30 ° C and 80 ° C of each polymer liquid crystal
change rate of Δn due to Δn in m light and its temperature U: 100 × (Δn (80 ° C.) − Δn (30 ° C.)) / Δ
Table 2 shows n (30 ° C.) (temperature dependence).
【００５２】[0052]
【表１】 [Table 1]
【００５３】[0053]
【表２】 [Table 2]
【００５４】[0054]
【発明の効果】本発明の重合性液晶組成物を用いれば、
屈折率異方性が大きく、かつ、その温度依存性が小さい
高分子液晶を得ることができる。この高分子液晶は散乱
もないため、光学素子（位相差フィルムや偏光ホログラ
ム素子等）の材料として好適であり、該光学素子は光ヘ
ッド等の部品として好適である。本発明は、本発明の効
果を損しない範囲内で、種々応用できる。According to the polymerizable liquid crystal composition of the present invention,
A polymer liquid crystal having a large refractive index anisotropy and a small temperature dependency can be obtained. Since this polymer liquid crystal does not scatter, it is suitable as a material for an optical element (a retardation film, a polarization hologram element, or the like), and the optical element is suitable as a component such as an optical head. The present invention can be applied variously within a range that does not impair the effects of the present invention.
───────────────────────────────────────────────────── 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） Ｇ０２Ｂ 5/30 Ｇ０２Ｂ 5/30 5/32 5/32 Ｇ０２Ｆ 1/13 ５００ Ｇ０２Ｆ 1/13 ５００ ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification code FI Theme coat ゛ (Reference) G02B 5/30 G02B 5/30 5/32 5/32 G02F 1/13 500 G02F 1/13 500
Claims (9)
式２で表される架橋性モノマとを含む重合性液晶組成物
であって、重合性液晶組成物中の前記架橋性モノマの量
が１０モル％より多いことを特徴とする、重合性液晶組
成物。 【化１】 式中の記号は以下の意味を示す。 Ｒ1、Ｒ3：それぞれ独立して、水素原子、ハロゲン原子
またはメチル基。 Ｒ2：水素原子、ハロゲン原子、シアノ基または置換さ
れていてもよいアルキル基。 Ｘ1、Ｘ2：それぞれ独立して、単結合、−ＣＯＯ−、−
ＯＣＯ−または−Ｏ−。 Ｙ1、Ｙ2：それぞれ独立して、−ＣＨ2―、−ＯＣＨ2Ｃ
Ｈ2−または−ＣＨ2ＣＨ2Ｏ−。 ｍ：１〜１２の整数。 ｎ、ｒ：それぞれ独立して、１〜１０の整数。 Ｚ1、Ｚ2、Ｚ3、Ｚ4、Ｚ5、Ｚ6、Ｚ7、Ｚ8、Ｚ9、
Ｚ10：それぞれ独立して、単結合、−Ｏ−、−ＯＣＯ
−、−ＣＯＯ−、−ＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ
−、−ＮＨ−、−Ｃ≡Ｃ−、−ＣＨ＝ＣＨ−、−ＣＨ2
ＣＨ2−、−Ｎ＝ＣＨ−、−ＣＨ＝Ｎ−または−Ｎ＝Ｎ
−。 Ｅ1、Ｅ2、Ｅ3、Ｅ4、Ｅ5、Ｅ6、Ｅ7、Ｅ8：それぞれ独
立して、置換されていてもよい１，４−フェニレン基ま
たは置換されていてもよいトランス−１，４−シクロヘ
キシレン基。 ｐ、ｑ、ｓ、ｔ：それぞれ独立して、０または１。1. A polymerizable liquid crystal composition comprising a non-crosslinkable monomer represented by the following formula 1 and a crosslinkable monomer represented by the following formula 2, wherein the crosslinkable monomer in the polymerizable liquid crystal composition is Is more than 10 mol%, a polymerizable liquid crystal composition. Embedded image The symbols in the formula have the following meanings. R 1 and R 3 each independently represent a hydrogen atom, a halogen atom or a methyl group. R 2 : a hydrogen atom, a halogen atom, a cyano group or an optionally substituted alkyl group. X 1 , X 2 : each independently represents a single bond, -COO-,-
OCO- or -O-. Y 1 , Y 2 : each independently represents —CH 2 —, —OCH 2 C
H 2 — or —CH 2 CH 2 O—. m: an integer from 1 to 12. n and r: each independently an integer of 1 to 10. Z 1 , Z 2 , Z 3 , Z 4 , Z 5 , Z 6 , Z 7 , Z 8 , Z 9 ,
Z 10: each independently a single bond, -O -, - OCO
-, -COO-, -CO-, -CONH-, -NHCO
-, - NH -, - C≡C -, - CH = CH -, - CH 2
CH 2 -, - N = CH -, - CH = N- or -N = N
-. E 1 , E 2 , E 3 , E 4 , E 5 , E 6 , E 7 , E 8 : each independently represents an optionally substituted 1,4-phenylene group or an optionally substituted trans- 1,4-cyclohexylene group. p, q, s, t: 0 or 1 each independently.
性モノマの分子長以上である、請求項１に記載の重合性
液晶組成物。2. The polymerizable liquid crystal composition according to claim 1, wherein a molecular length of the crosslinkable monomer is equal to or longer than a molecular length of the non-crosslinkable monomer.
量が２０〜９０モル％である、請求項１または２に記載
の重合性液晶組成物。3. The polymerizable liquid crystal composition according to claim 1, wherein the amount of the crosslinkable monomer in the polymerizable liquid crystal composition is 20 to 90 mol%.
ｑ＝１であり、かつＲ2がシアノ基である非架橋性モノ
マであり、重合性液晶組成物中の該非架橋性モノマの量
が１０〜８０モル％である請求項１、２または３に記載
の重合性液晶組成物。4. The method according to claim 1, wherein the non-crosslinkable monomer is p +
The non-crosslinkable monomer wherein q = 1 and R 2 is a cyano group, and the amount of the non-crosslinkable monomer in the polymerizable liquid crystal composition is 10 to 80 mol%. The polymerizable liquid crystal composition according to the above.
項１、２、３または４に記載の重合性液晶組成物。5. The polymerizable liquid crystal composition according to claim 1, having a refractive index anisotropy of 0.15 or more.
合性液晶組成物を重合させてなる高分子液晶。6. A polymer liquid crystal obtained by polymerizing the polymerizable liquid crystal composition according to claim 1, 2, 3, 4, or 5.
り重合させてなる請求項６に記載の高分子液晶。7. The polymer liquid crystal according to claim 6, which is polymerized by irradiating ultraviolet light or visible light.
いてなる光学素子。8. An optical element using the polymer liquid crystal according to claim 6.
ヘッド。9. An optical head using the optical element according to claim 8.
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| JP2002256031A (en) * | 2001-02-28 | 2002-09-11 | Jsr Corp | Liquid crystal material, its production method, liquid crystal film, its production method and method of use |
| WO2006112338A1 (en) * | 2005-04-13 | 2006-10-26 | Asahi Glass Company, Limited | Polymerizable liquid crystal composition, optical anisotropic material, optical element, and optical head device |
| JP2007169363A (en) * | 2005-12-20 | 2007-07-05 | Asahi Glass Co Ltd | Polymerizable liquid crystal composition, liquid crystalline polymer, optical element and terphenyl derivative |
| JP2007293255A (en) * | 2006-03-29 | 2007-11-08 | Fujifilm Corp | Holographic recording composition, and optical recording medium and method |
| WO2008102838A1 (en) * | 2007-02-23 | 2008-08-28 | Zeon Corporation | Liquid crystalline compound, liquid crystalline composition, optical film, and optical laminate |
| WO2009145321A1 (en) | 2008-05-30 | 2009-12-03 | 旭硝子株式会社 | Compound, polymerizable liquid crystalline composition, optical element, and optical information recording/reproduction device |
| US10048420B2 (en) | 2012-12-21 | 2018-08-14 | Merck Patent Gmbh | Reactive mesogens |
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| JP2000239402A (en) * | 1999-02-19 | 2000-09-05 | Nippon Mitsubishi Oil Corp | Liquid crystal film and optical element |
| JP2000515201A (en) * | 1997-04-29 | 2000-11-14 | コーニンクレッカ フィリップス エレクトロニクス エヌ ヴィ | Method for producing macroscopically oriented crosslinked polymer |
| JP2001201635A (en) * | 2000-01-21 | 2001-07-27 | Fuji Photo Film Co Ltd | Porlarized light element |
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| JP2000515201A (en) * | 1997-04-29 | 2000-11-14 | コーニンクレッカ フィリップス エレクトロニクス エヌ ヴィ | Method for producing macroscopically oriented crosslinked polymer |
| JP2000239402A (en) * | 1999-02-19 | 2000-09-05 | Nippon Mitsubishi Oil Corp | Liquid crystal film and optical element |
| JP2001201635A (en) * | 2000-01-21 | 2001-07-27 | Fuji Photo Film Co Ltd | Porlarized light element |
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| JP2002256031A (en) * | 2001-02-28 | 2002-09-11 | Jsr Corp | Liquid crystal material, its production method, liquid crystal film, its production method and method of use |
| US7534370B2 (en) | 2005-04-13 | 2009-05-19 | Asahi Glass Company, Limited | Polymerizable liquid crystal composition, optical anisotropic material, optical element and optical head device |
| WO2006112338A1 (en) * | 2005-04-13 | 2006-10-26 | Asahi Glass Company, Limited | Polymerizable liquid crystal composition, optical anisotropic material, optical element, and optical head device |
| JP5151479B2 (en) * | 2005-04-13 | 2013-02-27 | 旭硝子株式会社 | Polymerizable liquid crystal composition, optically anisotropic material, optical element and optical head device |
| JP2007169363A (en) * | 2005-12-20 | 2007-07-05 | Asahi Glass Co Ltd | Polymerizable liquid crystal composition, liquid crystalline polymer, optical element and terphenyl derivative |
| JP2007293255A (en) * | 2006-03-29 | 2007-11-08 | Fujifilm Corp | Holographic recording composition, and optical recording medium and method |
| CN102924326A (en) * | 2007-02-23 | 2013-02-13 | 日本瑞翁株式会社 | Liquid crystalline compound, liquid crystalline composition, optical film, and optical laminate |
| WO2008102838A1 (en) * | 2007-02-23 | 2008-08-28 | Zeon Corporation | Liquid crystalline compound, liquid crystalline composition, optical film, and optical laminate |
| US8425990B2 (en) | 2007-02-23 | 2013-04-23 | Zeon Corporation | Liquid crystalline compound, liquid crystalline composition, optical film, and optical laminate |
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| US10048420B2 (en) | 2012-12-21 | 2018-08-14 | Merck Patent Gmbh | Reactive mesogens |
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