JPWO2017195396A1 - Photoreactive liquid crystal composition, display element, optical element, method for producing display element, method for producing optical element - Google Patents
Photoreactive liquid crystal composition, display element, optical element, method for producing display element, method for producing optical element Download PDFInfo
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- JPWO2017195396A1 JPWO2017195396A1 JP2018516338A JP2018516338A JPWO2017195396A1 JP WO2017195396 A1 JPWO2017195396 A1 JP WO2017195396A1 JP 2018516338 A JP2018516338 A JP 2018516338A JP 2018516338 A JP2018516338 A JP 2018516338A JP WO2017195396 A1 JPWO2017195396 A1 JP WO2017195396A1
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
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- C—CHEMISTRY; METALLURGY
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
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- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
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- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
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- C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
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- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
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- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
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- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
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- C09K19/00—Liquid crystal materials
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- C09K19/38—Polymers
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- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
Abstract
本発明は、液晶配向膜を用いずに、液晶の配向性を液晶バルク内で制御して得られる素子、具体的には表示素子及び光学素子の提供、及び該素子を作製するための光反応性液晶組成物を提供する。特に、光反応性液晶組成物に用いる（Ｂ）低分子液晶との均一混合性が高い化合物を用いる、光反応性液晶組成物を提供する。該組成物により、液晶配向膜を用いずに、液晶の配向性を液晶バルク内で制御して得られる素子を提供する。本発明は、（Ａ）シロキサン骨格を備え且つ光反応性基を有する光反応性化合物；及び（Ｂ）低分子液晶；を有する光反応性液晶組成物を提供する。【選択図】なしThe present invention provides an element obtained by controlling the orientation of liquid crystal in a liquid crystal bulk without using a liquid crystal alignment film, specifically, a display element and an optical element, and a photoreaction for producing the element. A liquid crystal composition is provided. In particular, the present invention provides a photoreactive liquid crystal composition using a compound (B) that is used in the photoreactive liquid crystal composition and has a high uniform mixing property with a low molecular liquid crystal. The composition provides an element obtained by controlling the orientation of liquid crystal within a liquid crystal bulk without using a liquid crystal alignment film. The present invention provides a photoreactive liquid crystal composition having (A) a photoreactive compound having a siloxane skeleton and having a photoreactive group; and (B) a low molecular liquid crystal. [Selection figure] None
Description
本発明は、光反応性液晶組成物、該光反応性液晶組成物を有して形成される表示素子及び光学素子、並びに表示素子及び光学素子の製造方法に関する。 The present invention relates to a photoreactive liquid crystal composition, a display element and an optical element formed using the photoreactive liquid crystal composition, and a method for manufacturing the display element and the optical element.
現在の液晶表示素子は、高分子分散型液晶（Polymer Dispersed Liquid Crystal、ＰＤＬＣ）などの一部の素子を除いて、液晶を均一配向させるために配向処理を施した液晶配向膜を用いている（非特許文献１）。液晶配向膜の配向処理は液晶配向膜を塗布した後に、一般的にはラビング処理と呼ばれる、布を巻きつけたローラーで膜表面を擦る手法がとられているが、該手法は膜表面を物理的に擦る手法であるため、ラビングによる傷や削れカスが液晶表示素子の表示性能を低下させる問題点がある。さらに、この配向処理には、液晶配向膜形成工程、液晶配向処理工程、液晶配向膜の洗浄工程と数多くの工程を経る必要があり、製造工程を煩雑化していた。
そのため、該液晶配向膜を用いずに、液晶の配向性が制御できる液晶セルが作製できるとプロセス面及びコスト面で大きなメリットとなる。The current liquid crystal display element uses a liquid crystal alignment film that has been subjected to an alignment treatment to uniformly align the liquid crystal, except for some elements such as polymer dispersed liquid crystal (PDLC) ( Non-patent document 1). The alignment treatment of the liquid crystal alignment film is a method called rubbing treatment, which is generally called rubbing treatment after the liquid crystal alignment film is applied. Therefore, there is a problem that the display performance of the liquid crystal display element is deteriorated due to scratches and scraps caused by rubbing. Furthermore, this alignment process requires a number of processes including a liquid crystal alignment film forming process, a liquid crystal alignment process process, and a liquid crystal alignment film cleaning process, which complicates the manufacturing process.
For this reason, if a liquid crystal cell capable of controlling the orientation of the liquid crystal without using the liquid crystal alignment film can be produced, there are significant advantages in terms of process and cost.
実際に、液晶配向膜を用いずに、光学素子及び表示素子を提供できる光反応性液晶組成物を、特許文献１は開示する。特許文献１開示の光反応性液晶組成物は、（Ａ）（Ａ−１）光架橋及び（Ａ−２）光異性化からなる群から選ばれる少なくとも１種の反応を生じる光反応性側鎖を有する光反応性高分子液晶；及び（Ｂ）低分子液晶；を有する。該組成物をセルに注入し、偏光紫外線を照射することにより、（Ａ）光反応性高分子液晶及び（Ｂ）低分子液晶が配向性を示し、光学素子及び／又は表示素子を提供することができる。 Actually, Patent Document 1 discloses a photoreactive liquid crystal composition that can provide an optical element and a display element without using a liquid crystal alignment film. The photoreactive liquid crystal composition disclosed in Patent Document 1 is a photoreactive side chain that generates at least one reaction selected from the group consisting of (A) (A-1) photocrosslinking and (A-2) photoisomerization. And (B) a low molecular liquid crystal. By injecting the composition into a cell and irradiating with polarized ultraviolet rays, (A) a photoreactive polymer liquid crystal and (B) a low molecular liquid crystal exhibit orientation, and provide an optical element and / or a display element. Can do.
しかしながら、特許文献１開示の光反応性液晶組成物は、（Ａ）光反応性高分子液晶と（Ｂ）低分子液晶との均一混合性が良好ではない場合が生じる。特に、（Ａ）光反応性高分子液晶の量を多くすると、（Ｂ）低分子液晶との均一混合性が低下し、光反応性液晶組成物自体が製造できないという問題、ひいては光学素子及び／又は表示素子が提供できないという問題が生じる。 However, the photoreactive liquid crystal composition disclosed in Patent Document 1 may have a poor uniform mixing property between (A) the photoreactive polymer liquid crystal and (B) the low molecular liquid crystal. In particular, if the amount of (A) the photoreactive polymer liquid crystal is increased, (B) the problem that the uniform mixing property with the low molecular liquid crystal is reduced and the photoreactive liquid crystal composition itself cannot be produced, and the optical element and / Or the problem that a display element cannot be provided arises.
そこで、本発明の目的は、液晶配向膜を用いずに、液晶の配向性を液晶バルク内で制御して得られる素子、具体的には表示素子及び光学素子を提供すること、及び／又は該素子を作製するための光反応性液晶組成物を提供することにある。
特に、本発明の目的は、光反応性液晶組成物に用いる（Ｂ）低分子液晶との均一混合性が高い化合物を用いる、光反応性液晶組成物を提供することにあり、加えて、該組成物により、液晶配向膜を用いずに、液晶の配向性を液晶バルク内で制御して得られる素子、具体的には表示素子及び光学素子を提供することにある。
特に、上記目的に加えて、又は上記目的以外に、本発明の目的は、光反応性液晶組成物に用いる（Ｂ）低分子液晶との均一混合性が高い化合物を用いる、光反応性液晶組成物により、液晶配向膜を用いずに、液晶の配向性を液晶バルク内で制御して得られる素子、具体的には表示素子及び光学素子を製造する方法を提供することにある。Accordingly, an object of the present invention is to provide an element, specifically a display element and an optical element, obtained by controlling the alignment of liquid crystal in a liquid crystal bulk without using a liquid crystal alignment film, and / or It is providing the photoreactive liquid crystal composition for producing an element.
In particular, an object of the present invention is to provide a photoreactive liquid crystal composition using (B) a compound having a high uniform mixing property with a low molecular liquid crystal used in the photoreactive liquid crystal composition. An object of the present invention is to provide an element, specifically a display element and an optical element, obtained by controlling the orientation of liquid crystal in a liquid crystal bulk without using a liquid crystal alignment film.
In particular, in addition to the above object or in addition to the above object, the object of the present invention is to provide a photoreactive liquid crystal composition using (B) a compound having high uniform mixing with a low molecular liquid crystal used in the photoreactive liquid crystal composition. An object of the present invention is to provide a method for producing an element, specifically a display element and an optical element, obtained by controlling the orientation of liquid crystal in a liquid crystal bulk without using a liquid crystal alignment film.
本発明者らは、以下の発明を見出した。
＜１＞ （Ａ）シロキサン骨格を備え且つ光反応性基を有する光反応性化合物；及び
（Ｂ）低分子液晶；
を有する光反応性液晶組成物。The inventors have found the following invention.
<1> (A) a photoreactive compound having a siloxane skeleton and having a photoreactive group; and (B) a low molecular liquid crystal;
A photoreactive liquid crystal composition comprising:
本発明により、液晶配向膜を用いずに、液晶の配向性を液晶バルク内で制御して得られる素子、具体的には表示素子及び光学素子を提供すること、及び／又は該素子を作製するための光反応性液晶組成物を提供することができる。
特に、本発明により、光反応性液晶組成物に用いる（Ｂ）低分子液晶との均一混合性が高い化合物を用いる、光反応性液晶組成物を提供することができる。また、該組成物により、液晶配向膜を用いずに、液晶の配向性を液晶バルク内で制御して得られる素子、具体的には表示素子及び光学素子を提供することができる。
特に、本発明により、上記効果に加えて、又は上記効果以外に、光反応性液晶組成物に用いる（Ｂ）低分子液晶との均一混合性が高い化合物を用いる、光反応性液晶組成物により、液晶配向膜を用いずに、液晶の配向性を液晶バルク内で制御して得られる素子、具体的には表示素子及び光学素子を製造する方法を提供することができる。According to the present invention, an element obtained by controlling the alignment of liquid crystal within a liquid crystal bulk without using a liquid crystal alignment film, specifically, a display element and an optical element is provided and / or the element is manufactured. A photoreactive liquid crystal composition can be provided.
In particular, according to the present invention, it is possible to provide a photoreactive liquid crystal composition using (B) a compound having a high uniform mixing property with a low molecular liquid crystal used in the photoreactive liquid crystal composition. In addition, the composition can provide an element, specifically a display element and an optical element, obtained by controlling the orientation of liquid crystal in the liquid crystal bulk without using a liquid crystal alignment film.
In particular, according to the present invention, in addition to the above effect, or in addition to the above effect, (B) a photoreactive liquid crystal composition using a compound having a high uniform mixing property with a low molecular liquid crystal used in the photoreactive liquid crystal composition Further, it is possible to provide a method for producing an element, specifically a display element and an optical element, obtained by controlling the alignment of liquid crystal within the liquid crystal bulk without using a liquid crystal alignment film.
本願は、液晶配向膜を用いずに、液晶の配向性を液晶バルク内で制御して得られる素子、具体的には表示素子及び光学素子、及び／又は該素子を作製するための光反応性液晶組成物を提供する。特に、本願は、光反応性液晶組成物に用いる（Ｂ）低分子液晶との均一混合性が高い化合物を用いる、光反応性液晶組成物を提供する。
また、本願は、液晶配向膜を用いずに、液晶の配向性を液晶バルク内で制御して得られる素子を製造する方法を提供する。特に、本願は、光反応性液晶組成物に用いる（Ｂ）低分子液晶との均一混合性が高い化合物を用いる光反応性液晶組成物により、上記素子を製造する方法を提供する。
以下、光反応性液晶組成物、該組成物によって得られる素子、素子の製造方法を説明する。The present application relates to an element obtained by controlling the alignment of liquid crystal in a liquid crystal bulk without using a liquid crystal alignment film, specifically a display element and an optical element, and / or photoreactivity for producing the element. A liquid crystal composition is provided. In particular, the present application provides a photoreactive liquid crystal composition that uses a compound (B) that is used in the photoreactive liquid crystal composition and has a high uniform mixing property with a low molecular liquid crystal.
Moreover, this application provides the method of manufacturing the element obtained by controlling the orientation of a liquid crystal within a liquid crystal bulk, without using a liquid crystal aligning film. In particular, the present application provides a method for producing the above-described element by using a photoreactive liquid crystal composition using (B) a compound having a high uniform mixing property with a low molecular liquid crystal used in the photoreactive liquid crystal composition.
Hereinafter, a photoreactive liquid crystal composition, a device obtained by the composition, and a method for manufacturing the device will be described.
＜光反応性液晶組成物＞
本発明の光反応性液晶組成物は、（Ａ）シロキサン骨格を備え且つ光反応性基を有する光反応性化合物；及び（Ｂ）低分子液晶；を有する。
本発明の光反応性液晶組成物は、（Ａ）光反応性化合物；及び（Ｂ）低分子液晶；のみからなっても、該（Ａ）及び（Ｂ）の性質が変化しない程度のその他の成分を有する（Ａ）及び（Ｂ）のみから本質的になってもよい。また、本発明の光反応性液晶組成物は、（Ａ）又は（Ｂ）以外に、その他の成分を有してもよい。 <Photoreactive liquid crystal composition>
The photoreactive liquid crystal composition of the present invention has (A) a photoreactive compound having a siloxane skeleton and having a photoreactive group; and (B) a low molecular liquid crystal.
The photoreactive liquid crystal composition of the present invention comprises (A) a photoreactive compound; and (B) a low-molecular liquid crystal; and other components that do not change the properties of (A) and (B). It may consist essentially only of (A) and (B) having components. The photoreactive liquid crystal composition of the present invention may have other components in addition to (A) or (B).
＜＜（Ｂ）低分子液晶＞＞
本発明の光反応性液晶組成物に含まれる（Ｂ）低分子液晶は、従来、液晶表示素子などに用いられているネマチック液晶や強誘電性液晶などをそのまま用いることができる。
具体的には、（Ｂ）低分子液晶として、４−シアノ−４’−ｎ−ペンチルビフェニル、４−シアノ−４’−ｎ−へプチルオキシビフェニル等のシアノビフェニル類；コレステリルアセテート、コレステリルベンゾエート等のコレステリルエステル類；４−カ ルボキシフェニルエチルカーボネート、４−カルボキシフェニル−ｎ−ブチルカーボネート等の炭酸エステル類；安息香酸フェニルエステル、フタル酸ビフェニ ルエステル等のフェニルエステル類；ベンジリデン−２−ナフチルアミン、４’−ｎ−ブトキシベンジリデン−４−アセチルアニリン等のシッフ塩基類；Ｎ，Ｎ’−ビスベンジリデンベンジジン、ｐ−ジアニスアルベンジジン等のベンジジン類；４，４’−アゾキシジアニソール、４，４’−ジ−ｎ−ブトキシ アゾキシベンゼン等のアゾキシベンゼン類；以下に具体的に示すフェニルシクロヘキシル系、ターフェニル系、フェニルビシクロヘキシル系などの液晶；などを挙げることができるがこれらに限定されない。<< (B) Low molecular liquid crystal >>
As the low molecular liquid crystal (B) contained in the photoreactive liquid crystal composition of the present invention, nematic liquid crystal, ferroelectric liquid crystal and the like conventionally used for liquid crystal display elements can be used as they are.
Specifically, as (B) low molecular liquid crystal, cyanobiphenyls such as 4-cyano-4′-n-pentylbiphenyl and 4-cyano-4′-n-heptyloxybiphenyl; cholesteryl acetate, cholesteryl benzoate, and the like Cholesteryl esters of: carbonates such as 4-carboxyphenylethyl carbonate and 4-carboxyphenyl-n-butyl carbonate; phenyl esters such as benzoic acid phenyl ester and phthalic acid biphenyl ester; benzylidene-2-naphthylamine; Schiff bases such as 4′-n-butoxybenzylidene-4-acetylaniline; benzidines such as N, N′-bisbenzylidenebenzidine and p-dianisalbenzidine; 4,4′-azoxydianisole, 4, 4'-di-n-butoxy such as azoxybenzene Zokishibenzen like; specifically shown phenylcyclohexyl system below, terphenyl liquid crystal, such as phenyl bicyclohexyl system; and the like can be mentioned but not limited thereto.
＜＜（Ａ）光反応性化合物＞＞
本発明に用いる（Ａ）光反応性化合物（以下、（Ａ）光反応性化合物を単に「（Ａ）成分」と略記する場合がある）は、シロキサン骨格を備え且つ光反応性基を有する。
本明細書において光反応性とは、（Ａ−１）光架橋、（Ａ−２）光異性化、（Ａ−３）光分解、及び（Ａ−４）光転移、のうちのいずれかの反応；及びこれらの任意に組合せの反応；を生じる性質をいう。
光反応性基は、（Ａ−１）光架橋、（Ａ−２）光異性化、（Ａ−３）光分解、及び（Ａ−４）光転移からなる群から選ばれる少なくとも１種の反応を生じるのがよく、好ましくは（Ａ−１）光架橋、及び（Ａ−２）光異性化からなる群から選ばれる少なくとも１種の反応を生じるのがよく、より好ましくは（Ａ−１）光架橋反応を生じるのがよい。
光反応性基として、下記構造及びその誘導体を挙げることができるがこれらに限定されない。<< (A) Photoreactive Compound >>
The (A) photoreactive compound used in the present invention (hereinafter, the (A) photoreactive compound may be simply abbreviated as “(A) component”) has a siloxane skeleton and has a photoreactive group.
In the present specification, photoreactivity is any of (A-1) photocrosslinking, (A-2) photoisomerization, (A-3) photolysis, and (A-4) phototransition. Reaction; and any combination of these;
The photoreactive group is at least one reaction selected from the group consisting of (A-1) photocrosslinking, (A-2) photoisomerization, (A-3) photolysis, and (A-4) phototransition. It is preferable that at least one reaction selected from the group consisting of (A-1) photocrosslinking and (A-2) photoisomerization is generated, and more preferably (A-1). A photocrosslinking reaction should occur.
Examples of the photoreactive group include the following structures and derivatives thereof, but are not limited thereto.
（Ａ）成分は、ｉ）所定の温度範囲で液晶性を発現する化合物であって、光反応性基を有する化合物であるのが好ましい。
（Ａ）成分は、ｉｉ）２５０ｎｍ〜４００ｎｍの波長範囲の光で反応し、かつ５０〜３００℃の温度範囲で液晶性を示すのがよい。
（Ａ）成分は、ｉｉｉ）２５０ｎｍ〜４００ｎｍの波長範囲の光、特に偏光紫外線に反応する光反応性基を有することが好ましい。
（Ａ）成分の光反応性基は、ｉｖ）５０〜３００℃の温度範囲で液晶性を示すためメソゲン基を有することが好ましい。The component (A) is preferably i) a compound that exhibits liquid crystallinity in a predetermined temperature range, and a compound having a photoreactive group.
The component (A) is preferably ii) reacts with light in the wavelength range of 250 nm to 400 nm and exhibits liquid crystallinity in the temperature range of 50 to 300 ° C.
The component (A) preferably has a photoreactive group that reacts to light in the wavelength range of 250 nm to 400 nm, particularly polarized ultraviolet rays.
The photoreactive group of the component (A) preferably has a mesogenic group because it exhibits liquid crystallinity in a temperature range of iv) 50 to 300 ° C.
（Ａ）成分は、下記式（Ａ）−１〜（Ａ）−４からなる群から選ばれる少なくとも１種であるのがよい。
なお、式（Ａ）−１〜（Ａ）−４中、Ｒ１０１〜Ｒ１０８は各々独立に、１価の有機基を表す。ただし、下記式（Ａ）−１のＲ１０３〜Ｒ１０５は、ｍ４の値に依存して定義される。詳細は後述する。
ここで、１価の有機基は、水素原子であるか又は直鎖または分岐鎖の炭素数１〜６のアルキル基、直鎖または分岐鎖の炭素数１〜６のアルコキシ基、置換または非置換のフェニル基、ビニル基、メルカプト基、（メタ）アクリル基、およびその組み合わせからなる基（炭素原子に結合している水素原子がハロゲン原子、水酸基で置換されていてもよい。また、隣り合わない炭素原子が−Ｏ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−ＮＨ−ＣＯ−Ｏ−、−Ｏ−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−ＮＨ−で置換されていてもよい）から選ばれる基であるのがよい。
Ｑ１〜Ｑ４、及びＱ８は各々独立に、光反応性基を表す。
Ｑ５〜Ｑ７は各々独立に、光反応性基であっても、Ｒ１０１〜Ｒ１０８と同様に１価の有機基であってもよい。Ｑ５〜Ｑ７が各々独立に１価の有機基である場合、該基はＲ１０１〜Ｒ１０８と同様の定義を有する。
Ｐ１は炭素数１〜１０の直鎖または分岐鎖のアルキレン基（炭素原子に結合している水素原子は１価の有機基で置換されていてもよい。また、アルキレン基中、隣り合わない炭素原子が−Ｏ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−ＮＨ−ＣＯ−Ｏ−、−Ｏ−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−ＮＨ−で置換されていてもよい。好ましくは、Ｐ１は炭素数１〜１０の直鎖のアルキレン基であるのがよい。
ｎ１１、ｎ１２、及びｎ１４は各々独立に、１〜２０、好ましくは１〜１０、より好ましくは１〜４の整数を表し、ｎ１３は３〜２０、好ましくは３〜１０、より好ましくは３〜５の整数を表す。
ｍ４は１〜４の整数を表す。上述したとおり、下記式（Ａ）−１のＲ１０３〜Ｒ１０５は、ｍ４の値に依存する。ｍ４＝１の場合、Ｒ１０３〜Ｒ１０５は、上述の１価の有機基を表す。ｍ４＝２の場合、Ｒ１０３〜Ｒ１０５のうち、いずれか２つが上述の１価の有機基であり、残りの１つがｍ４の括弧内で示された基であるのがよい。また、ｍ４＝３の場合、Ｒ１０３〜Ｒ１０５のうち、いずれか１つが上述の１価の有機基であり、残りの２つがｍ４の括弧内で示された基であるのがよい。さらに、ｍ４＝４の場合、Ｒ１０３〜Ｒ１０５の全てが、ｍ４の括弧内で示された基であるのがよい。The component (A) may be at least one selected from the group consisting of the following formulas (A) -1 to (A) -4.
In formulas (A) -1 to (A) -4, R 101 to R 108 each independently represents a monovalent organic group. However, R < 103 > -R < 105 > of following formula (A) -1 is defined depending on the value of m4. Details will be described later.
Here, the monovalent organic group is a hydrogen atom, or a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, substituted or unsubstituted A group consisting of a phenyl group, a vinyl group, a mercapto group, a (meth) acryl group, and a combination thereof (a hydrogen atom bonded to a carbon atom may be substituted with a halogen atom or a hydroxyl group. The carbon atom may be substituted with -O-, -CO-O-, -O-CO-, -NH-CO-O-, -O-CO-NH-, -NH-CO-NH-) It is good that it is a group selected from
Q 1 to Q 4 and Q 8 each independently represent a photoreactive group.
Q 5 to Q 7 may each independently be a photoreactive group or a monovalent organic group as in R 101 to R 108 . When Q 5 to Q 7 are each independently a monovalent organic group, the group has the same definition as R 101 to R 108 .
P 1 is a linear or branched alkylene group having 1 to 10 carbon atoms (the hydrogen atom bonded to the carbon atom may be substituted with a monovalent organic group. Also, in the alkylene group, they are not adjacent to each other. The carbon atom may be substituted with —O—, —CO—O—, —O—CO—, —NH—CO—O—, —O—CO—NH—, or —NH—CO—NH—. Preferably, P 1 is a linear alkylene group having 1 to 10 carbon atoms.
n11, n12, and n14 each independently represents an integer of 1 to 20, preferably 1 to 10, more preferably 1 to 4, and n13 is 3 to 20, preferably 3 to 10, more preferably 3 to 5. Represents an integer.
m4 represents an integer of 1 to 4. As described above, R 103 to R 105 in the following formula (A) -1 depend on the value of m4. When m4 = 1, R 103 to R 105 represent the above-described monovalent organic group. When m4 = 2, any two of R 103 to R 105 may be the above-described monovalent organic group, and the other one may be a group shown in parentheses of m4. When m4 = 3, any one of R 103 to R 105 may be the above-described monovalent organic group, and the remaining two may be groups shown in parentheses of m4. Furthermore, when m4 = 4, all of R 103 to R 105 are preferably groups shown in parentheses for m4.
本発明の光反応性液晶組成物において、（Ａ）光反応性化合物と（Ｂ）低分子液晶との重量比（（Ａ）光反応性化合物：（Ｂ）低分子液晶）は、０．２：９９．８〜２０：８０、好ましくは１：９９〜１５：８５、より好ましくは２：９８〜１０：９０であるのがよい。 In the photoreactive liquid crystal composition of the present invention, the weight ratio of (A) photoreactive compound to (B) low molecular liquid crystal ((A) photoreactive compound: (B) low molecular liquid crystal) is 0.2. : 99.8 to 20:80, preferably 1:99 to 15:85, more preferably 2:98 to 10:90.
（Ａ）成分は、上述のように、光反応性を有する光反応性基を有する。該基の構造は、特に限定されないが、上記（Ａ−１）〜（Ａ−４）のうちいずれか１種又は２種以上の反応を生じるのがよく、好ましくは上記（Ａ−１）及び／又は（Ａ−２）に示す反応を生じるのがよく、より好ましくは（Ａ−１）光架橋反応を生じるのがよい。（Ａ−１）光架橋反応を生じる構造は、その反応後の構造が、熱などの外部ストレスに曝されたとしても、（Ａ）成分の配向性を長期間安定に保持できる点で好ましい。
（Ａ）成分の光反応性基の構造は、剛直なメソゲン成分を有する方が、液晶の配向が安定するため、好ましい。（Ａ）成分が剛直なメソゲン成分を有し且つ液晶性を示すと、（Ｂ）成分の低分子液晶との相溶性が向上するため好ましい。The component (A) has a photoreactive group having photoreactivity as described above. The structure of the group is not particularly limited, but any one or two or more reactions among the above (A-1) to (A-4) may occur, and preferably the above (A-1) and The reaction shown in (A-2) should be caused, and (A-1) the photocrosslinking reaction should be caused more preferably. (A-1) A structure that causes a photocrosslinking reaction is preferable in that the orientation of the component (A) can be stably maintained for a long period of time even when the structure after the reaction is exposed to external stress such as heat.
As the structure of the photoreactive group of the component (A), it is preferable to have a rigid mesogenic component because the alignment of the liquid crystal is stable. It is preferable that the component (A) has a rigid mesogen component and exhibits liquid crystallinity because compatibility with the low molecular liquid crystal of the component (B) is improved.
メソゲン成分として、ビフェニル基、ターフェニル基、フェニルシクロヘキシル基、フェニルベンゾエート基、アゾベンゼン基などを挙げることができるがこれらに限定されない。
メソゲン基としては下記の構造が好ましい。Examples of the mesogenic component include, but are not limited to, a biphenyl group, a terphenyl group, a phenylcyclohexyl group, a phenylbenzoate group, and an azobenzene group.
As the mesogenic group, the following structure is preferable.
（Ａ）成分の光反応性基として、下記式（１）〜（６）の少なくとも１種からなる基であるのが好ましい。 The photoreactive group of the component (A) is preferably a group consisting of at least one of the following formulas (1) to (6).
式中、Ａ、Ｂ、Ｄはそれぞれ独立に、単結合、−Ｏ−、−ＣＨ２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨ−ＣＯ−、−ＣＨ＝ＣＨ−ＣＯ−Ｏ−、又は−Ｏ−ＣＯ−ＣＨ＝ＣＨ−を表す；
Ｓは、炭素数１〜１２のアルキレン基であり、それらに結合する水素原子はハロゲン基に置き換えられていてもよい；
Ｔは、単結合または炭素数１〜１２のアルキレン基であり、それらに結合する水素原子はハロゲン基に置き換えられていてもよい；
Ｙ１は、１価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環および炭素数５〜８の脂環式炭化水素から選ばれる環を表すか、それらの置換基から選ばれる同一又は相異なった２〜６の環が結合基Ｂを介して結合してなる基であり、それらに結合する水素原子はそれぞれ独立に−ＣＯＯＲ０（式中、Ｒ０は水素原子又は炭素数１〜５のアルキル基を表す）、−ＮＯ２、−ＣＮ、−ＣＨ＝Ｃ（ＣＮ）２、−ＣＨ＝ＣＨ−ＣＮ、ハロゲン基、炭素数１〜５のアルキル基、又は炭素数１〜５のアルキルオキシ基で置換されても良い；
Ｙ２は、２価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環、炭素数５〜８の脂環式炭化水素、および、それらの組み合わせからなる群から選ばれる基であり、それらに結合する水素原子はそれぞれ独立に−ＮＯ２、−ＣＮ、−ＣＨ＝Ｃ（ＣＮ）２、−ＣＨ＝ＣＨ−ＣＮ、ハロゲン基、炭素数１〜５のアルキル基、又は炭素数１〜５のアルキルオキシ基で置換されても良い；
Ｒは、ヒドロキシ基、炭素数１〜６のアルコキシ基を表すか、又はＹ１と同じ定義を表す；
Ｘは、単結合、−ＣＯＯ−、−ＯＣＯ−、−Ｎ＝Ｎ−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＨ＝ＣＨ−ＣＯ−Ｏ−、又は−Ｏ−ＣＯ−ＣＨ＝ＣＨ−を表し、Ｘの数が２となるときは、Ｘ同士は同一でも異なっていてもよい；
Ｃｏｕは、クマリン−６−イル基またはクマリン−７−イル基を表し、それらに結合する水素原子はそれぞれ独立に−ＮＯ２、−ＣＮ、−ＣＨ＝Ｃ（ＣＮ）２、−ＣＨ＝ＣＨ−ＣＮ、ハロゲン基、炭素数１〜５のアルキル基、又は炭素数１〜５のアルキルオキシ基で置換されても良い；
ｑ１とｑ２は、一方が１で他方が０である；
ｑ３は０または１である；
Ｐ及びＱは、各々独立に、２価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環、炭素数５〜８の脂環式炭化水素、および、それらの組み合わせからなる群から選ばれる基である；ただし、Ｘが−ＣＨ＝ＣＨ−ＣＯ−Ｏ−、−Ｏ−ＣＯ−ＣＨ＝ＣＨ−である場合、−ＣＨ＝ＣＨ−が結合する側のＰ又はＱは芳香環であり、Ｐの数が２以上となるときは、Ｐ同士は同一でも異なっていてもよく、Ｑの数が２以上となるときは、Ｑ同士は同一でも異なっていてもよい；
ｌ１は０または１である；
ｌ２は０〜２の整数である；
ｌ１とｌ２がともに０であるときは、Ｔが単結合であるときはＡも単結合を表す；
ｌ１が１であるときは、Ｔが単結合であるときはＢも単結合を表す；
Ｈ及びＩは、各々独立に、２価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環、およびそれらの組み合わせから選ばれる基である。In the formula, A, B, and D are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—. Represents O— or —O—CO—CH═CH—;
S is an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced by a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced with a halogen group;
Y 1 represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are groups bonded through a bonding group B, and the hydrogen atoms bonded to them are each independently —COOR 0 (wherein R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group), —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. May be substituted with an alkyloxy group;
Y 2 is a group selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, The hydrogen atoms bonded to each independently represent —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of
R represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y 1 ;
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. When CH is 2 and the number of X is 2, X may be the same or different;
Cou represents coumarin-6-yl group or a coumarin-7-yl group, -NO 2 are each a hydrogen atom bonded to them independently, -CN, -CH = C (CN ) 2, -CH = CH- May be substituted with CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
one of q1 and q2 is 1 and the other is 0;
q3 is 0 or 1;
P and Q are each independently selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. Provided that when X is —CH═CH—CO—O— or —O—CO—CH═CH—, P or Q on the side to which —CH═CH— is bonded is an aromatic ring; When the number of P is 2 or more, the Ps may be the same or different, and when the number of Q is 2 or more, the Qs may be the same or different;
l1 is 0 or 1;
l2 is an integer from 0 to 2;
when l1 and l2 are both 0, A represents a single bond when T is a single bond;
when l1 is 1, B represents a single bond when T is a single bond;
H and I are each independently a group selected from a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and combinations thereof.
光反応性基は、下記式（７）〜（１０）からなる群から選ばれるいずれか１種であるのがよい。
式中、Ａ、Ｂ、Ｄ、Ｙ１、Ｘ、Ｙ２、及びＲは、上記と同じ定義を有する；
ｌは１〜１２の整数を表す；
ｍは、０〜２の整数を表し、ｍ１、ｍ２は１〜３の整数を表す；
ｎは０〜１２の整数（ただしｎ＝０のときＢは単結合である）を表す。The photoreactive group may be any one selected from the group consisting of the following formulas (7) to (10).
In which A, B, D, Y 1 , X, Y 2 and R have the same definition as above;
l represents an integer of 1 to 12;
m represents an integer of 0 to 2, and m1 and m2 represent an integer of 1 to 3;
n represents an integer of 0 to 12 (however, when n = 0, B is a single bond).
光反応性基は、下記式（１１）〜（１３）からなる群から選ばれるいずれか１種であるのがよい。
式中、Ａ、Ｘ、ｌ、ｍ、ｍ１及びＲは、上記と同じ定義を有する。The photoreactive group may be any one selected from the group consisting of the following formulas (11) to (13).
In the formula, A, X, l, m, m1 and R have the same definition as above.
光反応性基は、下記式（１４）又は（１５）で表される基であるのがよい。
式中、Ａ、Ｙ１、ｌ、ｍ１及びｍ２は上記と同じ定義を有する。The photoreactive group may be a group represented by the following formula (14) or (15).
In the formula, A, Y 1 , l, m1 and m2 have the same definition as above.
光反応性基は、下記式（１６）又は（１７）で表される基であるのがよい。
式中、Ａ、Ｘ、ｌ及びｍは、上記と同じ定義を有する。The photoreactive group may be a group represented by the following formula (16) or (17).
In the formula, A, X, l and m have the same definition as above.
光反応性基は、下記式（２０）で表される基であるのがよい。
式中、Ａ、Ｙ１、Ｘ、ｌ及びｍは上記と同じ定義を有する。The photoreactive group is preferably a group represented by the following formula (20).
In the formula, A, Y 1 , X, l and m have the same definition as above.
＜＜（Ａ）成分の例＞＞
（Ａ）成分として、具体的には、次のような化合物を挙げることができるがこれらに限定されない。<< Example of component (A) >>
Specific examples of the component (A) include, but are not limited to, the following compounds.
本発明の光反応性液晶組成物は、上述したように、（Ａ）成分又は（Ｂ）成分以外に、その他の成分を有してもよい。
その他の成分として、用いる（Ａ）成分及び（Ｂ）成分の用途などに依存するが、例えば、ヒンダートアミン類やヒンダートフェノール類などの酸化防止剤や１つ以上の末端に光重合または光架橋する基を有する重合性化合物などを挙げることができる。
重合性化合物の具体的な例として、以下に示す化合物（式中、Ｖは、単結合又は−Ｒ８Ｏ−、好ましくは−Ｒ８Ｏ−で表され、Ｒ８は炭素数１〜１０、好ましくは炭素数２〜６の直鎖又は分岐鎖のアルキレン基を示す。Ｗは、単結合又は−ＯＲ９−、好ましくは−ＯＲ９−で表され、Ｒ９は炭素数１〜１０、好ましくは炭素数２〜６の直鎖又は分岐鎖のアルキレン基を示す。Ｖ及びＷは同一の構造でも異なっていてもよいが、同一であると合成が容易である。Ｒ７はＨまたは炭素数１〜４のアルキル基を示す）を挙げることができるがこれらに限定されない。As described above, the photoreactive liquid crystal composition of the present invention may have other components in addition to the component (A) or the component (B).
Depending on the use of the component (A) and component (B) used as other components, for example, antioxidants such as hindered amines and hindered phenols, photopolymerization or photopolymerization at one or more terminals Examples thereof include a polymerizable compound having a crosslinkable group.
Specific examples of the polymerizable compound include the following compounds (in the formula, V is a single bond or —R 8 O—, preferably —R 8 O—, and R 8 has 1 to 10 carbon atoms, Preferably, it represents a linear or branched alkylene group having 2 to 6 carbon atoms, W is represented by a single bond or —OR 9 —, preferably —OR 9 —, and R 9 has 1 to 10 carbon atoms, preferably Represents a linear or branched alkylene group having 2 to 6 carbon atoms, and V and W may be the same or different, but can be easily synthesized if they are the same R 7 is H or a carbon number 1 to 4 alkyl groups), but is not limited thereto.
＜光反応性液晶組成物によって得られる素子及びその製造方法＞
本願は、上記の光反応性液晶組成物によって得られる素子、及び該素子の製造方法も提供する。
本発明の素子は、上記の光反応性液晶組成物を有する液晶セルを有して形成される。
素子として、表示素子；及び回折格子、レンズ、ミラーなどの光学素子；などを挙げることができる。<Element obtained by photoreactive liquid crystal composition and method for producing the same>
The present application also provides an element obtained by the above-described photoreactive liquid crystal composition and a method for producing the element.
The element of the present invention is formed having a liquid crystal cell having the above-described photoreactive liquid crystal composition.
Examples of the element include display elements; and optical elements such as diffraction gratings, lenses, and mirrors.
本発明の素子、具体的には表示素子又は光学素子は、セルに上記の光反応性液晶組成物を充填して形成することができる。
具体的には、本発明の素子は、次の工程により製造することができる。
［Ｉ］ （Ａ）シロキサン基を備え且つ光反応性基を有する光反応性化合物；及び（Ｂ）低分子液晶；を有する光反応性液晶組成物を、平行離間配置された２枚の透明基体間に形成される空間に充填して液晶セルを形成する工程；及び
［ＩＩ］ ［Ｉ］で得られた液晶セルに、前記２枚の透明基体のいずれか一方から、偏光した紫外線を照射する工程；
を有することにより、
本発明の素子を形成することができ、具体的には、液晶セル内で（Ｂ）低分子液晶が所定の配向性を有する素子が形成される。The element of the present invention, specifically, a display element or an optical element can be formed by filling a cell with the above-mentioned photoreactive liquid crystal composition.
Specifically, the device of the present invention can be manufactured by the following steps.
[I] Two transparent substrates in which a photoreactive liquid crystal composition having (A) a photoreactive compound having a siloxane group and having a photoreactive group; and (B) a low-molecular liquid crystal; A step of filling a space formed therebetween to form a liquid crystal cell; and [II] irradiating the liquid crystal cell obtained in [I] with polarized ultraviolet rays from one of the two transparent substrates. Process;
By having
The element of the present invention can be formed. Specifically, an element in which (B) a low molecular liquid crystal has a predetermined orientation is formed in a liquid crystal cell.
［Ｉ］工程は、上述の光反応性液晶組成物を、平行離間配置された少なくとも紫外線を照射する側の基体が透明な基体間に形成される空間に充填して液晶セルを形成する工程である。
液晶セルは、２枚の透明基体をある程度離間させて平行配置することにより空間を形成し、該空間に上述の光反応性組成物を充填して形成される。
基体は、例えば、ガラス；アクリルやポリカーボネート等のプラスチック等；を用いることができる。基体は、形成する素子に依存して、可撓性を有してもよい。The step [I] is a step of forming a liquid crystal cell by filling the above-mentioned photoreactive liquid crystal composition in a space formed between transparent substrates at least on the side irradiated with ultraviolet rays arranged in parallel and spaced apart. is there.
The liquid crystal cell is formed by forming a space by arranging two transparent substrates apart from each other in parallel and filling the space with the photoreactive composition described above.
As the substrate, for example, glass; plastic such as acrylic or polycarbonate, etc. can be used. The substrate may have flexibility depending on the element to be formed.
基体は、形成する素子に依存して、空間側に、種々の膜、例えば、ポリビニルアルコール、ポリエーテル、ポリエチレン、ＰＥＴ、ポリアミド、ポリイミド、アクリル、ポリカーボネート、ポリウレアなどから形成される膜を形成してもよい。なお、ここで用いる膜は、例えば、次のような作用を奏するのがよい。即ち、後述の［ＩＩ］工程において、（Ａ）光反応性化合物の光反応を誘起するためには、（Ａ）光反応性化合物の分子長軸が偏光を吸収するように、基板面内に水平に位置するのがよい。一方、（Ａ）光反応性化合物は（Ｂ）低分子液晶との組成物として液晶セル中に封入されるため、（Ａ）光反応性化合物の分子長軸が基板面内に水平に位置するためには（Ｂ）低分子液晶も同様に基板面内に水平に位置するのがよい。したがって、上述の膜は、光反応性組成物の分子長軸が基板面内に水平に位置できるものであるのがよく、そのような膜であれば材料に限定されない。 Depending on the element to be formed, the substrate is formed with various films on the space side, such as films formed from polyvinyl alcohol, polyether, polyethylene, PET, polyamide, polyimide, acrylic, polycarbonate, polyurea, etc. Also good. In addition, the film | membrane used here is good to show | play the following effects, for example. That is, in the step [II] to be described later, in order to induce the photoreaction of (A) the photoreactive compound, (A) the molecular long axis of the photoreactive compound absorbs polarized light so that It should be positioned horizontally. On the other hand, since (A) the photoreactive compound is enclosed in a liquid crystal cell as a composition with (B) a low-molecular liquid crystal, (A) the molecular long axis of the photoreactive compound is positioned horizontally in the substrate plane. For this purpose, (B) the low-molecular liquid crystal is preferably positioned horizontally within the substrate surface as well. Therefore, the above-described film should be one in which the molecular long axis of the photoreactive composition can be positioned horizontally within the substrate surface, and any material can be used as long as it is such a film.
［ＩＩ］工程は、［Ｉ］で得られた液晶セルに偏光した紫外線を照射する工程である。偏光した紫外線は、２枚の透明基体のいずれか一方の外側から照射するため、透明基体は、上述したように、偏光した紫外線を透過する基体である。
偏光した紫外線は、形成する素子に依存するが、波長１００ｎｍ〜４００ｎｍの範囲の紫外線を使用することができる。好ましくは、使用する塗膜の種類によりフィルター等を介して最適な波長を選択する。そして、例えば、選択的に光架橋反応を誘起できるように、波長２９０ｎｍ〜４００ｎｍの範囲の紫外線を選択して使用することができる。紫外線としては、例えば、高圧水銀灯から放射される光を用いることができる。
偏光した紫外線を照射する工程では、照射される偏光紫外線の偏光度の低下や、偏光紫外線の散乱を抑制するため、偏光された紫外線は（Ｂ）低分子液晶の等方相転移温度より１５℃低い温度以上で照射するのが良く、より好ましくは等方相転移温度以上で照射するのが良い。この温度範囲であれば、（Ａ）光反応性化合物の偏光光反応による二色性が維持され、（Ｂ）低分子液晶の配向が均一となる点で好ましい。The step [II] is a step of irradiating the liquid crystal cell obtained in [I] with polarized ultraviolet rays. Since the polarized ultraviolet rays are irradiated from the outside of one of the two transparent substrates, the transparent substrate is a substrate that transmits the polarized ultraviolet rays as described above.
Although polarized ultraviolet rays depend on the element to be formed, ultraviolet rays having a wavelength in the range of 100 nm to 400 nm can be used. Preferably, the optimum wavelength is selected through a filter or the like depending on the type of coating film to be used. For example, ultraviolet rays having a wavelength in the range of 290 nm to 400 nm can be selected and used so that the photocrosslinking reaction can be selectively induced. As the ultraviolet light, for example, light emitted from a high-pressure mercury lamp can be used.
In the step of irradiating the polarized ultraviolet light, the polarized ultraviolet light is 15 ° C. from the isotropic phase transition temperature of the low molecular liquid crystal in order to suppress the decrease in the degree of polarization of the irradiated polarized ultraviolet light and the scattering of the polarized ultraviolet light. Irradiation is preferably performed at a low temperature or higher, and more preferably, irradiation is performed at an isotropic phase transition temperature or higher. If it is this temperature range, the dichroism by the polarization photoreaction of (A) photoreactive compound is maintained, (B) It is preferable at the point from which the orientation of a low molecular liquid crystal becomes uniform.
光学素子の第１の位置、該第１の位置とは異なる第２の位置に対して、異なる偏光紫外線を照射することにより、該第１の位置と第２の位置において（Ｂ）低分子液晶が異なる配向性を有する素子、例えば光学素子を形成することができる。
具体的には、第１の位置に対して第１の偏光軸とする偏光紫外線を照射し、第２の位置に対して第１の偏光軸とは異なる第２の偏光軸とする偏光紫外線を照射することにより、光学素子の第１及び第２の位置において（Ｂ）低分子液晶が異なる配向性を有する素子を形成することができる。
また、例えば、形成する素子が、回折格子の場合、偏光紫外線を液晶セルに干渉露光させることにより、素子の位置において配向性が異なる配向性分布、具体的には周期的に配向性が異なる配向性分布を有する光学素子である回折格子を形成することができる。By irradiating different polarized ultraviolet rays to the first position of the optical element and the second position different from the first position, (B) the low molecular liquid crystal at the first position and the second position. Elements having different orientations, for example, optical elements can be formed.
Specifically, the first position is irradiated with polarized ultraviolet light having a first polarization axis, and the second position is irradiated with polarized ultraviolet light having a second polarization axis different from the first polarization axis. By irradiating, (B) an element having different orientations in the low molecular liquid crystal can be formed at the first and second positions of the optical element.
In addition, for example, when the element to be formed is a diffraction grating, an alignment distribution with different orientations at the position of the element, specifically, an orientation with periodically different orientations, is obtained by interference exposure of polarized ultraviolet rays to the liquid crystal cell. A diffraction grating which is an optical element having a property distribution can be formed.
偏光紫外線を照射すると、液晶セル内で、次のようなメカニズムが生じるものと考えられる。即ち、液晶セル内の（Ａ）光反応性化合物は、該偏光紫外線に応じた配向性を有することとなる。
また、（Ｂ）低分子液晶は、（Ａ）光反応性化合物の配向性にしたがって、配向する。
これにより、（Ａ）光反応性化合物及び（Ｂ）低分子液晶は、偏光紫外線に応じて、配向性を有することとなる。
例えば、上述のように、偏光紫外線を液晶セルに干渉露光することにより、素子の位置において、（Ａ）光反応性化合物が、異なる配向性を有し、これにしたがって、（Ｂ）低分子液晶も、素子の位置によって異なる配向性を有することとなる。よって、偏光紫外線を液晶セルに干渉露光することにより、素子の位置において配向性が異なる配向性分布、具体的には周期的に配向性が異なる配向性分布を有する光学素子である回折格子を形成することができる。It is considered that the following mechanism occurs in the liquid crystal cell when irradiated with polarized ultraviolet rays. That is, the (A) photoreactive compound in the liquid crystal cell has an orientation according to the polarized ultraviolet light.
Further, (B) the low molecular liquid crystal is aligned according to the alignment of (A) the photoreactive compound.
Thereby, (A) a photoreactive compound and (B) low molecular liquid crystal will have orientation according to polarized ultraviolet rays.
For example, as described above, by subjecting polarized ultraviolet rays to a liquid crystal cell by interference exposure, (A) a photoreactive compound has different orientations at the element position, and (B) a low molecular liquid crystal However, it has different orientation depending on the position of the element. Therefore, a diffraction grating, which is an optical element having an orientation distribution with different orientations at the position of the element, specifically, an orientation distribution with periodically different orientations, is formed by interference exposure of polarized ultraviolet rays to the liquid crystal cell. can do.
＜合成例１：光反応性化合物Ｓｉ−１の合成＞ <Synthesis Example 1: Synthesis of photoreactive compound Si-1>
＜＜化合物Ｃの合成＞＞
２Ｌ四つ口フラスコに、化合物［Ｂ］（９０．８ｇ、４１２ｍｍｏｌ）、トリフェニルホスフィン（以下、ＰＰｈ３と記載）（１３０．０ｇ、４９５ｍｍｏｌ）、テトラヒドロフラン（以下、ＴＨＦと記載）（７００ｇ）を加え、窒素置換して溶液を０℃に冷却した。その後、アゾジカルボン酸ジイソプロピル（以下、ＤＩＡＤと記載）（４９．５ｇ、４９６ｍｏｌ）のＴＨＦ（１００ｇ）溶液を徐々に加え、その後、化合物［Ａ］（４９．５ｇ、４９６ｍｏｌ）のＴＨＦ（１００ｇ）溶液をさらに加えた後、２３℃でさらに反応を行った。ＨＰＬＣにて反応追跡を行い、反応終了を確認後、反応溶液を酢酸エチル／ブラインで洗浄し、有機層を硫酸マグネシウムで乾燥した。その後、ろ過、エバポレーターにて溶媒留去することで、オイル状の粗物を得た。得られた粗物にヘキサン（１Ｌ）を加え、−２０℃で冷却撹拌し、結晶化した固体をろ過で除去し、ろ液をシリカゲルカラムクロマトグラフィーにて精製し黄色固体として、化合物［Ｃ］を１１０．３ｇ得た（収率９８％）。
1H-NMR(400MHz, CDCl3, δppm):7.54(1H, d), 7.44(2H, d), 6.87(2H, d), 5.86-5.78(1H, m), 5.87-5.78(1H, m), 5.10-4.97(2H, m), 3.99(2H, t), 2.22-2.09(2H, m), 1.84-1.76(2H,m), 1.61-1.52(2H, m), 1.43(9H, s).<< Synthesis of Compound C >>
In a 2 L four-necked flask, compound [B] (90.8 g, 412 mmol), triphenylphosphine (hereinafter referred to as PPh 3 ) (130.0 g, 495 mmol), tetrahydrofuran (hereinafter referred to as THF) (700 g) were added. In addition, the solution was cooled to 0 ° C. by replacing with nitrogen. Thereafter, a solution of diisopropyl azodicarboxylate (hereinafter referred to as DIAD) (49.5 g, 496 mol) in THF (100 g) was gradually added, and then a solution of compound [A] (49.5 g, 496 mol) in THF (100 g) was added. After further adding, the reaction was further carried out at 23 ° C. The reaction was traced by HPLC, and after confirming the completion of the reaction, the reaction solution was washed with ethyl acetate / brine, and the organic layer was dried over magnesium sulfate. Thereafter, filtration and evaporation of the solvent with an evaporator gave an oily crude product. Hexane (1 L) was added to the obtained crude product, and the mixture was cooled and stirred at −20 ° C., the crystallized solid was removed by filtration, and the filtrate was purified by silica gel column chromatography to obtain a compound [C] as a yellow solid. 110.3 g was obtained (yield 98%).
1 H-NMR (400 MHz, CDCl 3 , δ ppm): 7.54 (1H, d), 7.44 (2H, d), 6.87 (2H, d), 5.86-5.78 (1H, m), 5.87-5.78 (1H, m ), 5.10-4.97 (2H, m), 3.99 (2H, t), 2.22-2.09 (2H, m), 1.84-1.76 (2H, m), 1.61-1.52 (2H, m), 1.43 (9H, s ).
＜＜化合物Ｅの合成＞＞
３００ｍＬ四つ口フラスコに、化合物［Ｄ］（２９．４３ｇ、１９８ｍｍｏｌ）、化合物［Ｃ］（３０．００ｇ、９９．２ｍｍｏｌ）、Ｋａｒｓｔｅｄｔ触媒（１ｍｍｏｌ）、トルエン（１６０ｇ）を加え、窒素置換後、加熱還流を行った。ＨＰＬＣにて反応追跡を行い、反応終了後、反応溶液をエバポレーターで濃縮し、シリカゲルカラムクロマトグラフィーにて精製し、オイル状の化合物［Ｅ］を２９．４ｇ得た（収率６６％）。
1H-NMR(400MHz, CDCl3, δppm):7.50(1H, d), 7.41(2H, d), 6.84(2H, d), 6.19(1H,d), 3.94(2H, t), 1.83-1.71(2H, m), 1.42(9H, s), 1.40-1.17(4H, m), 0.54-0.42(2H, m), 0.07-0.03(15H, m).<< Synthesis of Compound E >>
Compound [D] (29.43 g, 198 mmol), compound [C] (30.00 g, 99.2 mmol), Karstedt catalyst (1 mmol), toluene (160 g) were added to a 300 mL four-necked flask, and after nitrogen substitution, Heating to reflux was performed. The reaction was monitored by HPLC, and after completion of the reaction, the reaction solution was concentrated by an evaporator and purified by silica gel column chromatography to obtain 29.4 g of an oily compound [E] (yield 66%).
1 H-NMR (400 MHz, CDCl 3 , δ ppm): 7.50 (1H, d), 7.41 (2H, d), 6.84 (2H, d), 6.19 (1H, d), 3.94 (2H, t), 1.83- 1.71 (2H, m), 1.42 (9H, s), 1.40-1.17 (4H, m), 0.54-0.42 (2H, m), 0.07-0.03 (15H, m).
＜＜光反応性化合物Ｓｉ−１の合成＞＞
３００ｍＬ四つ口フラスコに、化合物［Ｅ］（２９．４８ｇ、６５．４ｍｍｏｌ）とギ酸（１２０ｇ）を加え、４０℃で加熱撹拌を行った。ＨＰＬＣにて反応追跡を行い、反応終了後、蒸留水（８００ｇ）に反応液を注ぎ、ヘキサン/酢酸エチルで分液した。有機層を蒸留水で３回洗浄し有機層をエバポレーターで濃縮後、シリカゲルカラムクロマトグラフィーにて精製し、白色固体の光反応性化合物Ｓｉ−１を１０．５ｇ得た（収率４１％）
1H-NMR(400MHz, CDCl3, δppm):7.74(1H, d), 7.49(2H, d), 6.90(2H, d), 6.31(1H,d), 4.12(2H, t), 1.83-1.74(2H, m), 1.48-1.31(6H, m), 0.54-0.50(2H, m), 0.07-0.03(15H, m).<< Synthesis of Photoreactive Compound Si-1 >>
Compound [E] (29.48 g, 65.4 mmol) and formic acid (120 g) were added to a 300 mL four-necked flask, and the mixture was heated and stirred at 40 ° C. The reaction was traced by HPLC, and after completion of the reaction, the reaction solution was poured into distilled water (800 g) and separated with hexane / ethyl acetate. The organic layer was washed three times with distilled water, and the organic layer was concentrated with an evaporator and purified by silica gel column chromatography to obtain 10.5 g of a white solid photoreactive compound Si-1 (yield 41%).
1 H-NMR (400 MHz, CDCl 3 , δ ppm): 7.74 (1H, d), 7.49 (2H, d), 6.90 (2H, d), 6.31 (1H, d), 4.12 (2H, t), 1.83- 1.74 (2H, m), 1.48-1.31 (6H, m), 0.54-0.50 (2H, m), 0.07-0.03 (15H, m).
＜合成例２：光反応性化合物Ｓｉ−２の合成＞ <Synthesis Example 2: Synthesis of Photoreactive Compound Si-2>
化合物［Ｄ］を化合物［Ｆ］に変更した以外、合成例１と同様な手法を用いて光反応性化合物Ｓｉ−２を１７．２ｇ得た（収率５６％）
1H-NMR(400MHz, CDCl3, δppm):7.74(1H, d), 7.49(2H, d), 6.89(2H, d), 6.31(1H,d), 4.00-3.95(2H, m), 1.81-1.74(2H, m), 1.46-1.33(6H, m), 0.54-0.50(2H, m), 0.16-0.03(21H, m).17.2 g of photoreactive compound Si-2 was obtained using the same method as in Synthesis Example 1 except that the compound [D] was changed to the compound [F] (yield 56%).
1 H-NMR (400 MHz, CDCl 3 , δ ppm): 7.74 (1H, d), 7.49 (2H, d), 6.89 (2H, d), 6.31 (1H, d), 4.00-3.95 (2H, m), 1.81-1.74 (2H, m), 1.46-1.33 (6H, m), 0.54-0.50 (2H, m), 0.16-0.03 (21H, m).
＜合成例３：光反応性化合物Ｓｉ−３の合成＞ <Synthesis Example 3: Synthesis of Photoreactive Compound Si-3>
化合物［Ｄ］を化合物［Ｈ］に変更した以外、合成例１と同様な手法を用いて光反応性化合物Ｓｉ−３を１３．５ｇ得た（収率８９％）
1H-NMR(400MHz, CDCl3, δppm):7.73(1H, d), 7.48(2H, d), 6.82(2H, d), 6.31(1H,d), 3.97-3.91(2H, m), 1.79-1.74(2H, m), 1.43-1.33(6H, m), 0.54-0.50(2H, m), 0.16-0.03(21H, m).13.5 g of photoreactive compound Si-3 was obtained in the same manner as in Synthesis Example 1 except that the compound [D] was changed to the compound [H] (yield 89%).
1 H-NMR (400 MHz, CDCl 3 , δ ppm): 7.73 (1H, d), 7.48 (2H, d), 6.82 (2H, d), 6.31 (1H, d), 3.97-3.91 (2H, m), 1.79-1.74 (2H, m), 1.43-1.33 (6H, m), 0.54-0.50 (2H, m), 0.16-0.03 (21H, m).
＜合成例４：光反応性化合物Ｓｉ−４の合成＞ <Synthesis Example 4: Synthesis of Photoreactive Compound Si-4>
＜＜化合物Ｋの合成＞＞
２Ｌ四つ口フラスコに、化合物［Ｊ］（８４．０ｇ、４５１ｍｍｏｌ）、トリフェニルホスフィン（以下、ＰＰｈ３と記載）（１３０．０ｇ、４９５ｍｍｏｌ）、ＴＨＦ（７００ｇ）を加え、窒素置換して溶液を０℃に冷却した。その後、ＤＩＡＤ（４９．５ｇ、４９６ｍｏｌ）のＴＨＦ（１００ｇ）溶液を徐々に加え、その後、化合物[Ａ] （４９．５ｇ、４９６ｍｏｌ）のＴＨＦ（１００ｇ）溶液をさらに加えた後、２３℃でさらに反応を行った。ＨＰＬＣにて反応追跡を行い、反応終了を確認後、反応溶液を酢酸エチル／ブラインで洗浄し、有機層を硫酸マグネシウムで乾燥した。その後、ろ過、エバポレーターにて溶媒留去することで、化合物［Ｋ］の粗物を得た。得られた粗物をシリカゲルカラムクロマトグラフィーにて精製し化合物［Ｋ］を５６．７ｇ得た（収率４７％）。
1H-NMR(400MHz, CDCl3, δppm):9.70(1H, s), 7.64-7.62(2H, m), 7.44-7.41(2H, m), 7.01-6.98(2H, m), 6.85-6.82(2H, m), 5.88-5.79(1H, m), 5.10-4.97(2H, m), 3.99(2H, t), 2.22-2.09(2H, m), 1.84-1.76(2H,m), 1.61-1.52(2H, m).<< Synthesis of Compound K >>
Compound [J] (84.0 g, 451 mmol), triphenylphosphine (hereinafter referred to as PPh 3 ) (130.0 g, 495 mmol), THF (700 g) was added to a 2 L four-necked flask, and the solution was purged with nitrogen. Was cooled to 0 ° C. Thereafter, a THF (100 g) solution of DIAD (49.5 g, 496 mol) was gradually added, and then a THF (100 g) solution of compound [A] (49.5 g, 496 mol) was further added, and further at 23 ° C. Reaction was performed. The reaction was traced by HPLC, and after confirming the completion of the reaction, the reaction solution was washed with ethyl acetate / brine, and the organic layer was dried over magnesium sulfate. Thereafter, filtration and evaporation of the solvent with an evaporator gave a crude product of compound [K]. The obtained crude product was purified by silica gel column chromatography to obtain 56.7 g of compound [K] (yield 47%).
1 H-NMR (400 MHz, CDCl 3 , δ ppm): 9.70 (1H, s), 7.64-7.62 (2H, m), 7.44-7.41 (2H, m), 7.01-6.98 (2H, m), 6.85-6.82 (2H, m), 5.88-5.79 (1H, m), 5.10-4.97 (2H, m), 3.99 (2H, t), 2.22-2.09 (2H, m), 1.84-1.76 (2H, m), 1.61 -1.52 (2H, m).
＜＜化合物Ｍの合成＞＞ << Synthesis of Compound M >>
３００ｍＬ四つ口フラスコに、化合物［Ｋ］（１０．００ｇ、３７．３ｍｍｏｌ）、化合物［Ｌ］（６．６５ｇ、３７．３ｍｍｏｌ）、１−（３−ジメチルアミノプロピル）−３−エチルカルボジイミド塩酸塩（以下、ＥＤＣと記載）（６．９５ｇ、４４．８ｍｍｏｌ）、Ｎ，Ｎ’−ジメチルアミノピリジン（以下、ＤＭＡＰと記載）（０．４６、３．７３ｍｍｏｌ）、ＴＨＦ（１５０ｇ）を加え２３℃で反応を行った。ＨＰＬＣにて反応追跡を行い、反応終了を確認後、反応溶液を酢酸エチル／蒸留水で洗浄、分液操作にて水層を除去した。有機層をさらに蒸留水で２回洗浄した後、有機層を硫酸マグネシウムで乾燥した。その後、ろ過、エバポレーターにて溶媒留去することで、化合物［Ｍ］の粗物を得た。得られた粗物をシリカゲルカラムクロマトグラフィーにて精製し化合物［Ｍ］を１５．２ｇ得た（収率９５％）。
1H-NMR(400MHz, CDCl3, δppm):7.83(1H, d), 7.68-7.67(2H, m), 7.58-7.56(2H, m), 7.55-7.48(2H, m), 7.23-7.19(2H, m), 7.06-7.05(2H, m), 6.89-6.93(2H, m), 6.30(1H, d), 5.87-5.80(1H, m), 5.11-4.99(2H, m), 3.98(2H, t), 3,85 (3H, s), 2.23-2.10(2H, m), 1.83-1.77(2H,m), 1.62-1.52(2H, m).In a 300 mL four-necked flask, compound [K] (10.00 g, 37.3 mmol), compound [L] (6.65 g, 37.3 mmol), 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride Salt (hereinafter referred to as EDC) (6.95 g, 44.8 mmol), N, N′-dimethylaminopyridine (hereinafter referred to as DMAP) (0.46, 3.73 mmol), THF (150 g) were added, and 23 The reaction was performed at 0 ° C. The reaction was traced by HPLC, and after confirming the completion of the reaction, the reaction solution was washed with ethyl acetate / distilled water, and the aqueous layer was removed by a liquid separation operation. The organic layer was further washed twice with distilled water, and then the organic layer was dried over magnesium sulfate. Thereafter, filtration and evaporation of the solvent with an evaporator gave a crude product of the compound [M]. The obtained crude product was purified by silica gel column chromatography to obtain 15.2 g of compound [M] (yield 95%).
1 H-NMR (400 MHz, CDCl 3 , δ ppm): 7.83 (1H, d), 7.68-7.67 (2H, m), 7.58-7.56 (2H, m), 7.55-7.48 (2H, m), 7.23-7.19 (2H, m), 7.06-7.05 (2H, m), 6.89-6.93 (2H, m), 6.30 (1H, d), 5.87-5.80 (1H, m), 5.11-4.99 (2H, m), 3.98 (2H, t), 3,85 (3H, s), 2.23-2.10 (2H, m), 1.83-1.77 (2H, m), 1.62-1.52 (2H, m).
＜＜光反応性化合物Ｓｉ−４の合成＞＞ << Synthesis of Photoreactive Compound Si-4 >>
３００ｍＬ四つ口フラスコに、化合物［Ｄ］（０．８ｇ、５．２ｍｍｏｌ）、化合物［Ｍ］（１．５ｇ、３．５ｍｍｏｌ）、Ｋａｒｓｔｅｄｔ触媒（０．１ｍｍｏｌ）、トルエン（８０ｇ）を加え、窒素置換後、室温で２２時間撹拌した。ＨＰＬＣにて反応追跡を行い、反応終了後、反応溶液をエバポレーターで濃縮し、シリカゲルカラムクロマトグラフィーにて精製し、光反応性化合物［Ｓｉ−４］を０．６ｇ得た（収率３８％）。
1H-NMR(400MHz, CDCl3, δppm):7.85(1H, d), 7.68-7.67 (2H, m), 7.47-7.55(4H, m), 7.2(2H, d), 6.92-6.96(4H, m), 6.48-6.52(1H, d), 4.00(2H, t), 3,85 (3H, s), 1.35-1.80(8H, m), 0.51-0.53(2H, t), 0.02-0.05(15H, m).To a 300 mL four-necked flask, compound [D] (0.8 g, 5.2 mmol), compound [M] (1.5 g, 3.5 mmol), Karstedt catalyst (0.1 mmol), toluene (80 g) were added, After purging with nitrogen, the mixture was stirred at room temperature for 22 hours. The reaction was monitored by HPLC, and after completion of the reaction, the reaction solution was concentrated by an evaporator and purified by silica gel column chromatography to obtain 0.6 g of photoreactive compound [Si-4] (yield 38%). .
1 H-NMR (400 MHz, CDCl 3 , δ ppm): 7.85 (1H, d), 7.68-7.67 (2H, m), 7.47-7.55 (4H, m), 7.2 (2H, d), 6.92-6.96 (4H , m), 6.48-6.52 (1H, d), 4.00 (2H, t), 3,85 (3H, s), 1.35-1.80 (8H, m), 0.51-0.53 (2H, t), 0.02-0.05 (15H, m).
＜合成例５：光反応性化合物Ｓｉ−５の合成＞ <Synthesis Example 5: Synthesis of Photoreactive Compound Si-5>
化合物［Ｆ］を化合物［Ｎ］に変更し、化合物［Ｎ］に対して、化合物［Ｍ］の仕込比を２倍にした以外、合成例４と同様な手法を用いて光反応性化合物Ｓｉ−５を０．２ｇ得た（収率１１％）
1H-NMR(400MHz, CDCl3, δppm):7.85(2H, d), 7.68-7.67(4H, m), 7.58-7.56(4H, m), 7.55-7.48(4H, m), 7.23-7.19(4H, m), 7.06-7.05(4H, m), 6.89-6.93(4H, m), 6.50(2H, d), 4.02-3.97(4H, m), 3.85 (3H, s), 1.81-1.74(4H, m), 1.46-1.33(12H, m), 0.51-0.53(4H, m), 0.02-0.05(12H, m).The compound [F] is changed to the compound [N], and the photoreactive compound Si is used in the same manner as in Synthesis Example 4 except that the charge ratio of the compound [M] is doubled with respect to the compound [N]. 0.2g of -5 was obtained (yield 11%)
1 H-NMR (400 MHz, CDCl 3 , δ ppm): 7.85 (2H, d), 7.68-7.67 (4H, m), 7.58-7.56 (4H, m), 7.55-7.48 (4H, m), 7.23-7.19 (4H, m), 7.06-7.05 (4H, m), 6.89-6.93 (4H, m), 6.50 (2H, d), 4.02-3.97 (4H, m), 3.85 (3H, s), 1.81-1.74 (4H, m), 1.46-1.33 (12H, m), 0.51-0.53 (4H, m), 0.02-0.05 (12H, m).
＜合成例６：光反応性化合物Ｓｉ−６の合成＞ <Synthesis Example 6: Synthesis of Photoreactive Compound Si-6>
化合物［Ｆ］を化合物［Ｈ］に変更した以外、合成例４と同様な手法を用いて光反応性化合物Ｓｉ−５を１１．４ｇ得た（収率８２％）
1H-NMR(400MHz, CDCl3, δppm):7.82(1H, d), 7.67-7.68(2H, m), 7.60-7.58(2H, m), 7.54-7.49(2H, m), 7.24-7.18(2H, m), 7.05-7.05(2H, m), 6.89-6.93(2H, m), 6.30(1H, d), 4.02-3.97(2H, m), 3,85 (3H, s), 1.82-1.73(2H, m), 1.44-1.31(6H, m), 0.54-0.50(2H, m), 0.17-0.04(21H, m).11.4 g of photoreactive compound Si-5 was obtained using the same method as in Synthesis Example 4 except that the compound [F] was changed to the compound [H] (yield 82%).
1 H-NMR (400 MHz, CDCl 3 , δ ppm): 7.82 (1H, d), 7.67-7.68 (2H, m), 7.60-7.58 (2H, m), 7.54-7.49 (2H, m), 7.24-7.18 (2H, m), 7.05-7.05 (2H, m), 6.89-6.93 (2H, m), 6.30 (1H, d), 4.02-3.97 (2H, m), 3,85 (3H, s), 1.82 -1.73 (2H, m), 1.44-1.31 (6H, m), 0.54-0.50 (2H, m), 0.17-0.04 (21H, m).
（実施例１）
合成例４で合成されたＳｉ−４で表される光反応性化合物５重量部を、低分子液晶ＺＬＩ−４７９２（メルク社製）９５重量部に添加した後、室温で３０分間撹拌し、光反応性液晶組成物Ａ１を得た。撹拌後、該光反応性液晶組成物はＺＬＩ−４７９２に対するＳｉ−４の析出も見られず、均一に混合されていることを確認した（表２）。なお、Ｓｉ−４で表される光反応性高分子液晶は、１１８℃以上で液晶性を発現した。結果を表１に示す。なお、表１において、「Ｃ」は結晶相（液晶になる前の結晶状態）であること、「Ｎ」はネマティック相（液晶相の１種）であること、「Ｉ」は等方相であることを示す。また、「Ｃ」と「Ｎ」との間の数値は、結晶相からネマティック相に転移する温度を示し、「Ｎ」と「Ｉ」との数値は、ネマティック相から等方相へと転移する温度を示す。より具体的には、表１の「Ｓｉ−４」の熱特性は、１１８℃で結晶相からネマティック相に転移し、１９８℃でネマティック相から等方相へと転移することを示している。
別途、基板の両面にＩＴＯを備える２枚のガラス基板をＩＴＯが向かい合うように張り合わせ、１０μｍギャップの並行平板の空セルを得た。この空セルに該光反応性液晶組成物をキャピラリー法により注入した後、該光反応性液晶組成物の等方相温度以上である１１０℃に加熱した状態で、高圧水銀ランプを用いて直線偏光紫外線を照射することにより配向処理が施された液晶セルＡ２を得た。配向処理に用いた直線偏光紫外線の波長は３１５ｎｍ（５０ｍＷ／ｃｍ２）で、露光量は５００ｍＪ／ｃｍ２であった。Example 1
After 5 parts by weight of the photoreactive compound represented by Si-4 synthesized in Synthesis Example 4 was added to 95 parts by weight of low-molecular liquid crystal ZLI-4792 (manufactured by Merck), the mixture was stirred at room temperature for 30 minutes, Reactive liquid crystal composition A1 was obtained. After stirring, the photoreactive liquid crystal composition was confirmed to be uniformly mixed with no precipitation of Si-4 on ZLI-4792 (Table 2). The photoreactive polymer liquid crystal represented by Si-4 exhibited liquid crystallinity at 118 ° C. or higher. The results are shown in Table 1. In Table 1, “C” is a crystal phase (crystal state before becoming a liquid crystal), “N” is a nematic phase (one type of liquid crystal phase), and “I” is an isotropic phase. Indicates that there is. The numerical value between “C” and “N” indicates the temperature at which the crystal phase changes to the nematic phase, and the numerical value between “N” and “I” changes from the nematic phase to the isotropic phase. Indicates temperature. More specifically, the thermal characteristics of “Si-4” in Table 1 indicate that a transition from a crystalline phase to a nematic phase at 118 ° C. and a transition from a nematic phase to an isotropic phase at 198 ° C.
Separately, two glass substrates provided with ITO on both sides of the substrate were laminated so that the ITO faces each other, and a parallel plate empty cell with a 10 μm gap was obtained. The photoreactive liquid crystal composition is injected into the empty cell by a capillary method, and then linearly polarized using a high-pressure mercury lamp in a state heated to 110 ° C. which is higher than the isotropic phase temperature of the photoreactive liquid crystal composition. A liquid crystal cell A2 subjected to alignment treatment was obtained by irradiating with ultraviolet rays. The wavelength of the linearly polarized ultraviolet light used for the alignment treatment was 315 nm (50 mW / cm 2 ), and the exposure amount was 500 mJ / cm 2 .
＜光反応性液晶組成物の配向状態＞
Ａ２作製後、偏光顕微鏡観察によって、室温における低分子液晶の配向状態を確認した。結果を図１、及び表３に示す。図１の結果から次のことが分かる。即ち、液晶セルの光学軸が偏光子と検光子に対して４５度傾いた場合に明状態となり、偏光子と検光子のいずれかに対して、０度か９０度に配置された場合に暗状態となることから、液晶セル内の低分子液晶が一軸に配向していることが分かる。<Alignment state of photoreactive liquid crystal composition>
After the preparation of A2, the alignment state of the low-molecular liquid crystal at room temperature was confirmed by polarizing microscope observation. The results are shown in FIG. The following can be understood from the results of FIG. That is, when the optical axis of the liquid crystal cell is tilted by 45 degrees with respect to the polarizer and the analyzer, it becomes bright, and when it is placed at 0 degree or 90 degrees with respect to either the polarizer or the analyzer, it is dark. Since it will be in a state, it turns out that the low molecular liquid crystal in a liquid crystal cell has aligned uniaxially.
（実施例２）
光反応性液晶組成物に添加するＳｉ−４の量を２重量部及び低分子液晶の量を９８重量部に変更した以外、実施例１と同様な手法で光反応性液晶組成物Ｂ１を得た。
該光反応性液晶組成物Ｂ１はＺＬＩ−４７９２に対するＳｉ−４の析出も見られず、均一に混合されていることを確認した。結果を表２に示す。
次に、実施例１と同様に該光反応性液晶組成物が封入された液晶セルＢ２を作成した後、偏光顕微鏡観察により、室温における低分子液晶の配向状態を確認した。結果を表３に示す。なお、表３中、「良好」とは、「配向が均一」であったことを示し、「配向可能」とは、「液晶の配向は誘起できるが、欠陥などの配向不良が一部に見られ、配向が均一でない」ことを示している。(Example 2)
A photoreactive liquid crystal composition B1 was obtained in the same manner as in Example 1 except that the amount of Si-4 added to the photoreactive liquid crystal composition was changed to 2 parts by weight and the amount of the low molecular liquid crystal was changed to 98 parts by weight. It was.
The photoreactive liquid crystal composition B1 was confirmed to be uniformly mixed with no precipitation of Si-4 with respect to ZLI-4792. The results are shown in Table 2.
Next, after producing the liquid crystal cell B2 in which the photoreactive liquid crystal composition was encapsulated in the same manner as in Example 1, the alignment state of the low-molecular liquid crystals at room temperature was confirmed by observation with a polarizing microscope. The results are shown in Table 3. In Table 3, “good” means “alignment was uniform”, and “alignment possible” means “alignment of liquid crystal can be induced, but alignment defects such as defects are partially observed. The orientation is not uniform ”.
（実施例３）
光反応性液晶組成物に添加するＳｉ−４をＳｉ−５に変更した以外、実施例１と同様な手法で光反応性液晶組成物Ｃ１を得た。
該光反応性液晶組成物Ｃ１はＺＬＩ−４７９２に対するＳｉ−５の析出も見られず、均一に混合されていることを確認した。結果を表２に示す。
次に、照射する直線偏光紫外線の露光量を１０００ｍＪ／ｃｍ２とした以外、実施例１と同様に該光反応性液晶組成物が封入された液晶セルＣ２を作成した後、偏光顕微鏡観察により、室温における低分子液晶の配向状態を確認した。その結果、図示しないが、実施例１と同様に、液晶セル内の低分子液晶が一軸に配向し、配向均一性が良好であることを確認した（表３を参照のこと）。(Example 3)
A photoreactive liquid crystal composition C1 was obtained in the same manner as in Example 1 except that Si-4 added to the photoreactive liquid crystal composition was changed to Si-5.
The photoreactive liquid crystal composition C1 was confirmed to be uniformly mixed with no precipitation of Si-5 with respect to ZLI-4792. The results are shown in Table 2.
Next, after producing the liquid crystal cell C2 in which the photoreactive liquid crystal composition was encapsulated in the same manner as in Example 1 except that the exposure amount of the linearly polarized ultraviolet light to be irradiated was 1000 mJ / cm 2 , The alignment state of the low-molecular liquid crystal at room temperature was confirmed. As a result, although not shown, it was confirmed that the low-molecular liquid crystal in the liquid crystal cell was uniaxially aligned and the alignment uniformity was good as in Example 1 (see Table 3).
（実施例４）
光反応性液晶組成物に添加するＳｉ−４をＳｉ−６に変更した以外、実施例１と同様な手法で光反応性液晶組成物Ｄ１を得た。該光反応性液晶組成物Ｄ１はＺＬＩ−４７９２に対するＳｉ−５の析出も見られず、均一に混合されていることを確認した。結果を表２に示す。
次に、実施例３と同様に該光反応性液晶組成物が封入された液晶セルＤ２を作成した後、偏光顕微鏡観察により、室温における低分子液晶の配向状態を確認した。その結果、図示しないが、実施例１と同様に、液晶セル内の低分子液晶が一軸に配向し、配向均一性が良好であることを確認した（表３を参照のこと）。Example 4
A photoreactive liquid crystal composition D1 was obtained in the same manner as in Example 1 except that Si-4 added to the photoreactive liquid crystal composition was changed to Si-6. The photoreactive liquid crystal composition D1 was confirmed to be uniformly mixed with no precipitation of Si-5 with respect to ZLI-4792. The results are shown in Table 2.
Next, after producing the liquid crystal cell D2 in which the photoreactive liquid crystal composition was encapsulated in the same manner as in Example 3, the alignment state of the low molecular liquid crystals at room temperature was confirmed by observation with a polarizing microscope. As a result, although not shown, it was confirmed that the low-molecular liquid crystal in the liquid crystal cell was uniaxially aligned and the alignment uniformity was good as in Example 1 (see Table 3).
（実施例５）
実施例１で用いた低分子液晶：ＺＬＩ−４７９２（メルク社製）をＥ７（メルク社製）に変更した以外、実施例１と同様な手法で光反応性液晶組成物Ｅ１を得た。(Example 5)
A photoreactive liquid crystal composition E1 was obtained in the same manner as in Example 1 except that the low molecular liquid crystal used in Example 1: ZLI-4792 (Merck) was changed to E7 (Merck).
該光反応性液晶組成物Ｅ１はＥ７に対するＳｉ−４の析出も見られず、均一に混合されていることを確認した。結果を表２に示す。
次に、実施例１と同様に該光反応性液晶組成物が封入された液晶セルＥ２を作成した後、偏光顕微鏡観察により、室温における低分子液晶の配向状態を確認した。その結果、図示しないが、実施例１と同様に、液晶セル内の低分子液晶が一軸に配向し、配向均一性が良好であることを確認した（表３を参照のこと）。The photoreactive liquid crystal composition E1 was confirmed to be uniformly mixed with no precipitation of Si-4 with respect to E7. The results are shown in Table 2.
Next, after producing the liquid crystal cell E2 in which the photoreactive liquid crystal composition was encapsulated in the same manner as in Example 1, the alignment state of the low-molecular liquid crystal at room temperature was confirmed by observation with a polarizing microscope. As a result, although not shown, it was confirmed that the low-molecular liquid crystal in the liquid crystal cell was uniaxially aligned and the alignment uniformity was good as in Example 1 (see Table 3).
光反応性液晶組成物に添加するＳｉ−４をＳｉ−１に変更した以外、実施例１と同様な手法で光反応性液晶組成物Ｆ１を得た。
該光反応性液晶組成物Ｆ１はＺＬＩ−４７９２に対するＳｉ−１の析出も見られず、均一に混合されていることを確認した。結果を表２に示す。
次に、実施例１と同様に該光反応性液晶組成物が封入された液晶セルＦ２を作成した後、偏光顕微鏡観察により、室温における低分子液晶の配向状態を確認した。その結果、図示しないが、実施例１と同様に、液晶セル内の低分子液晶が一軸に配向し、配向均一性が良好であることを確認した（表３を参照のこと）。A photoreactive liquid crystal composition F1 was obtained in the same manner as in Example 1 except that Si-4 added to the photoreactive liquid crystal composition was changed to Si-1.
The photoreactive liquid crystal composition F1 was confirmed to be uniformly mixed with no precipitation of Si-1 with respect to ZLI-4792. The results are shown in Table 2.
Next, after producing the liquid crystal cell F2 in which the photoreactive liquid crystal composition was encapsulated in the same manner as in Example 1, the alignment state of the low molecular liquid crystals at room temperature was confirmed by observation with a polarizing microscope. As a result, although not shown, it was confirmed that the low-molecular liquid crystal in the liquid crystal cell was uniaxially aligned and the alignment uniformity was good as in Example 1 (see Table 3).
（実施例７）
光反応性液晶組成物に添加するＳｉ−１の量を１０重量部に変更した以外は、実施例６と同様な手法で光反応性液晶組成物Ｇ１を得た。
該光反応性液晶組成物Ｇ１はＺＬＩ−４７９２に対するＳｉ−４の析出も見られず、均一に混合されていることを確認した。結果を表２に示す。
次に、実施例１と同様に該光反応性液晶組成物が封入された液晶セルＧ２を作成した後、偏光顕微鏡観察により、室温における低分子液晶の配向状態を確認した。その結果、図示しないが、実施例１と同様に、液晶セル内の低分子液晶が一軸に配向し、配向均一性が良好であることを確認した（表３を参照のこと）。(Example 7)
A photoreactive liquid crystal composition G1 was obtained in the same manner as in Example 6 except that the amount of Si-1 added to the photoreactive liquid crystal composition was changed to 10 parts by weight.
The photoreactive liquid crystal composition G1 was confirmed to be uniformly mixed with no precipitation of Si-4 with respect to ZLI-4792. The results are shown in Table 2.
Next, after producing the liquid crystal cell G2 in which the photoreactive liquid crystal composition was sealed in the same manner as in Example 1, the alignment state of the low molecular liquid crystals at room temperature was confirmed by observation with a polarizing microscope. As a result, although not shown, it was confirmed that the low-molecular liquid crystal in the liquid crystal cell was uniaxially aligned and the alignment uniformity was good as in Example 1 (see Table 3).
（実施例８）
光反応性液晶組成物に添加するＳｉ−４をＳｉ−１とし、添加量を１重量部に変更した以外、実施例１と同様な手法で光反応性液晶組成物Ｈ１を得た。
該光反応性液晶組成物Ｈ１はＺＬＩ−４７９２に対するＳｉ−１の析出も見られず、均一に混合されていることを確認した。結果を表２に示す。
次に、実施例１と同様に該光反応性液晶組成物が封入された液晶セルＨ２を作成した後、偏光顕微鏡観察により、室温における低分子液晶の配向状態を確認した。その結果、図示しないが、実施例１と同様に、液晶セル内の低分子液晶が一軸に配向し、配向均一性が良好であることを確認した（表３を参照のこと）。(Example 8)
A photoreactive liquid crystal composition H1 was obtained in the same manner as in Example 1 except that Si-4 added to the photoreactive liquid crystal composition was changed to Si-1 and the addition amount was changed to 1 part by weight.
The photoreactive liquid crystal composition H1 was confirmed to be uniformly mixed with no precipitation of Si-1 with respect to ZLI-4792. The results are shown in Table 2.
Next, after producing the liquid crystal cell H2 in which the photoreactive liquid crystal composition was encapsulated in the same manner as in Example 1, the alignment state of the low-molecular liquid crystal at room temperature was confirmed by observation with a polarizing microscope. As a result, although not shown, it was confirmed that the low-molecular liquid crystal in the liquid crystal cell was uniaxially aligned and the alignment uniformity was good as in Example 1 (see Table 3).
（実施例９）
光反応性液晶組成物に添加するＳｉ−４をＳｉ−２に変更した以外、実施例７と同様な手法で光反応性液晶組成物Ｉ１を得た。
該光反応性液晶組成物Ｉ１はＺＬＩ−４７９２に対するＳｉ−２の析出も見られず、均一に混合されていることを確認した。結果を表２に示す。
次に、実施例１と同様に該光反応性液晶組成物が封入された液晶セルＩ２を作成した後、偏光顕微鏡観察により、室温における低分子液晶の配向状態を確認した。その結果、図示しないが、実施例１と同様に、液晶セル内の低分子液晶が一軸に配向し、配向均一性が良好であることを確認した（表３を参照のこと）。Example 9
Photoreactive liquid crystal composition I1 was obtained in the same manner as in Example 7, except that Si-4 added to the photoreactive liquid crystal composition was changed to Si-2.
The photoreactive liquid crystal composition I1 was confirmed to be uniformly mixed with no precipitation of Si-2 with respect to ZLI-4792. The results are shown in Table 2.
Next, after producing the liquid crystal cell I2 in which the photoreactive liquid crystal composition was encapsulated in the same manner as in Example 1, the alignment state of the low molecular liquid crystals at room temperature was confirmed by observation with a polarizing microscope. As a result, although not shown, it was confirmed that the low-molecular liquid crystal in the liquid crystal cell was uniaxially aligned and the alignment uniformity was good as in Example 1 (see Table 3).
（実施例１０）
照射する直線偏光紫外線の露光量を１０００ｍＪ／ｃｍ２へと変更した以外、実施例１と同様に該光反応性液晶組成物Ａ１が封入された液晶セルＡ３を作成した後、偏光顕微鏡観察により、室温における低分子液晶の配向状態を確認した。その結果、図示しないが、実施例１と同様に、液晶セル内の低分子液晶が一軸に配向し、配向均一性が良好であることを確認した（表３を参照のこと）。(Example 10)
A liquid crystal cell A3 encapsulating the photoreactive liquid crystal composition A1 was prepared in the same manner as in Example 1 except that the exposure amount of the linearly polarized ultraviolet light to be irradiated was changed to 1000 mJ / cm 2 . The alignment state of the low-molecular liquid crystal at room temperature was confirmed. As a result, although not shown, it was confirmed that the low-molecular liquid crystal in the liquid crystal cell was uniaxially aligned and the alignment uniformity was good as in Example 1 (see Table 3).
（実施例１１）
実施例４において、照射する直線偏光紫外線の露光量を１５００ｍＪ／ｃｍ２へと変更した以外、実施例４と同様に該光反応性液晶組成物Ｄ１が封入された液晶セルＤ３を作成した後、偏光顕微鏡観察により、室温における低分子液晶の配向状態を確認した。その結果、図示しないが、実施例１と同様に、液晶セル内の低分子液晶が一軸に配向し、配向均一性が良好であることを確認した（表３を参照のこと）。(Example 11)
In Example 4, after producing the liquid crystal cell D3 encapsulating the photoreactive liquid crystal composition D1 in the same manner as in Example 4 except that the exposure amount of the linearly polarized ultraviolet light to be irradiated was changed to 1500 mJ / cm 2 , The alignment state of the low-molecular liquid crystal at room temperature was confirmed by observation with a polarizing microscope. As a result, although not shown, it was confirmed that the low-molecular liquid crystal in the liquid crystal cell was uniaxially aligned and the alignment uniformity was good as in Example 1 (see Table 3).
（実施例１２）
実施例４において、光反応性液晶組成物に添加するＳｉ−６の量を１０重量部及び低分子液晶の量を９０重量部に変更した以外、実施例４と同様な手法で光反応性液晶組成物Ｊ１を得た。該光反応性液晶組成物はＺＬＩ−４７９２に対するＳｉ−６の析出も見られず、均一に混合されていることを確認した。結果を表２に示す。
次に、実施例４と同様に該光反応性液晶組成物が封入された液晶セルＪ２を作成した後、偏光顕微鏡観察により、室温における低分子液晶の配向状態を確認した。その結果、図示しないが、実施例４と同様に、液晶セル内の低分子液晶が一軸に配向し、配向均一性が良好であることを確認した（表３を参照のこと）。(Example 12)
In Example 4, the photoreactive liquid crystal was prepared in the same manner as in Example 4 except that the amount of Si-6 added to the photoreactive liquid crystal composition was changed to 10 parts by weight and the amount of the low molecular liquid crystal was changed to 90 parts by weight. Composition J1 was obtained. The photoreactive liquid crystal composition was confirmed to be uniformly mixed with no precipitation of Si-6 with respect to ZLI-4792. The results are shown in Table 2.
Next, after producing liquid crystal cell J2 in which the photoreactive liquid crystal composition was encapsulated in the same manner as in Example 4, the alignment state of the low molecular liquid crystals at room temperature was confirmed by observation with a polarizing microscope. As a result, although not shown, it was confirmed that the low-molecular liquid crystal in the liquid crystal cell was uniaxially aligned and the alignment uniformity was good as in Example 4 (see Table 3).
（比較例１）
下記式Ｍ６ＣＢで表される光反応性液晶モノマー１０重量部を、低分子液晶ＺＬＩ−４７９２（メルク社製）９５重量部に添加した後、室温で３０分間撹拌し、光反応性液晶組成物Ｋ１を得た。しかしながら、該光反応性液晶組成物Ｋ１は、上記式Ｍ６ＣＢで表される化合物のＺＬＩ−４７９２に対する溶解性が悪く、均一な混合ができなかった。結果を表２に示す。
組成物が均一混合できなかったため、液晶セルが作成できなかった。(Comparative Example 1)
After adding 10 parts by weight of a photoreactive liquid crystal monomer represented by the following formula M6CB to 95 parts by weight of low molecular liquid crystal ZLI-4792 (manufactured by Merck & Co., Inc.), the mixture is stirred at room temperature for 30 minutes, and photoreactive liquid crystal composition K1 Got. However, the photoreactive liquid crystal composition K1 had poor solubility in the ZLI-4792 of the compound represented by the formula M6CB, and could not be uniformly mixed. The results are shown in Table 2.
Since the composition could not be uniformly mixed, a liquid crystal cell could not be prepared.
（比較例２）
下記式Ｐ６ＣＢで表される光反応性高分子液晶５重量部を、低分子液晶ＺＬＩ−４７９２（メルク社製）９５重量部に添加した後、室温で３０分間撹拌し、光反応性液晶組成物Ｌ１を得た。しかしながら、該光反応性液晶組成物Ｌ１は、上記式Ｐ６ＣＢで表される高分子液晶のＺＬＩ−４７９２に対する溶解性が悪く、均一な混合ができなかった。結果を表２に示す。
組成物が均一混合できなかったため、液晶セルが作成できなかった。(Comparative Example 2)
After adding 5 parts by weight of photoreactive polymer liquid crystal represented by the following formula P6CB to 95 parts by weight of low molecular liquid crystal ZLI-4792 (manufactured by Merck & Co., Inc.), the mixture is stirred at room temperature for 30 minutes, and photoreactive liquid crystal composition L1 was obtained. However, the photoreactive liquid crystal composition L1 was poorly soluble in the polymer liquid crystal represented by the formula P6CB in ZLI-4792, and could not be uniformly mixed. The results are shown in Table 2.
Since the composition could not be uniformly mixed, a liquid crystal cell could not be prepared.
（比較例３）
偏光紫外線を照射する温度を４５度とした以外、実施例１と同様な手法で光反応性液晶組成物Ａ１が封入された液晶セルＡ４を得た。その後、偏光顕微鏡観察によって、室温における低分子液晶の配向状態を確認した。結果を図２、及び表３に示す。
図２の結果から次のことが分かる。即ち、液晶セルの光学軸が偏光子と検光子に対して４５度傾いた場合と、偏光子と検光子のいずれかに対して０度か９０度に配置された場合のいずれにおいても、明暗が確認されなかったことから、液晶セル内の低分子液晶は配向していないことが分かる。(Comparative Example 3)
A liquid crystal cell A4 in which the photoreactive liquid crystal composition A1 was encapsulated was obtained in the same manner as in Example 1 except that the temperature at which the polarized ultraviolet light was irradiated was 45 degrees. Then, the alignment state of the low molecular liquid crystal at room temperature was confirmed by polarizing microscope observation. The results are shown in FIG.
The following can be understood from the results of FIG. That is, whether the optical axis of the liquid crystal cell is tilted 45 degrees with respect to the polarizer and the analyzer, or whether the optical axis of the liquid crystal cell is disposed at 0 degree or 90 degrees with respect to either the polarizer or the analyzer, From this, it can be seen that the low-molecular liquid crystal in the liquid crystal cell is not oriented.
実施例１〜１２及び比較例１〜３から、本出願で開示された光反応性化合物は低分子液晶への溶解性が高く、光反応性液晶組成物の作成が容易であることが分かる。
また、該光反応性化合物を封入した液晶セルに直線偏光紫外線を照射することで、液晶配向膜を用いずとも均一に液晶が配向した液晶セルが作成できることが分かった。From Examples 1 to 12 and Comparative Examples 1 to 3, it can be seen that the photoreactive compounds disclosed in the present application have high solubility in low-molecular liquid crystals, and it is easy to prepare photoreactive liquid crystal compositions.
It was also found that a liquid crystal cell in which liquid crystals were uniformly aligned could be created without using a liquid crystal alignment film by irradiating the liquid crystal cell encapsulating the photoreactive compound with linearly polarized ultraviolet rays.
Claims (16)
（Ｂ）低分子液晶；
を有する光反応性液晶組成物。(A) a photoreactive compound having a siloxane skeleton and having a photoreactive group; and (B) a low-molecular liquid crystal;
A photoreactive liquid crystal composition comprising:
（式中、Ｒ１０１〜Ｒ１０８は各々独立に、１価の有機基を表し；
Ｑ１〜Ｑ４、及びＱ８は各々独立に、光反応性基を表し；
Ｑ５〜Ｑ７は各々独立に、光反応性基であるか又は１価の有機基を表し；
Ｐ１は、炭素数１〜１０の直鎖または分岐鎖のアルキレン基（炭素原子に結合している水素原子は１価の有機基で置換されていてもよい。また、アルキレン基中、隣り合わない炭素原子が−Ｏ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−ＮＨ−ＣＯ−Ｏ−、−Ｏ−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−ＮＨ−で置換されていてもよい）を表し；
ｎ１１、ｎ１２、及びｎ１４は各々独立に、１〜２０の整数を表し；
ｎ１３は３〜２０の整数を表し；
ｍ４は１〜４の整数を表す。）
からなる群から選ばれる少なくとも１種である請求項１〜３のいずれか１項に記載の組成物。
(Wherein R 101 to R 108 each independently represents a monovalent organic group;
Q 1 to Q 4 and Q 8 each independently represent a photoreactive group;
Q 5 to Q 7 each independently represent a photoreactive group or a monovalent organic group;
P 1 is a linear or branched alkylene group having 1 to 10 carbon atoms (the hydrogen atom bonded to the carbon atom may be substituted with a monovalent organic group. No carbon atoms may be substituted with —O—, —CO—O—, —O—CO—, —NH—CO—O—, —O—CO—NH—, —NH—CO—NH—. );
n11, n12, and n14 each independently represents an integer of 1 to 20;
n13 represents an integer of 3 to 20;
m4 represents an integer of 1 to 4. )
The composition according to any one of claims 1 to 3, which is at least one selected from the group consisting of:
（式中、Ａ、Ｂ、Ｄはそれぞれ独立に、単結合、−Ｏ−、−ＣＨ２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨ−ＣＯ−、−ＣＨ＝ＣＨ−ＣＯ−Ｏ−、又は−Ｏ−ＣＯ−ＣＨ＝ＣＨ−を表す；
Ｓは、炭素数１〜１２のアルキレン基であり、それらに結合する水素原子はハロゲン基に置き換えられていてもよい；
Ｔは、単結合または炭素数１〜１２のアルキレン基であり、それらに結合する水素原子はハロゲン基に置き換えられていてもよい；
Ｙ１は、１価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環および炭素数５〜８の脂環式炭化水素から選ばれる環を表すか、それらの置換基から選ばれる同一又は相異なった２〜６の環が結合基Ｂを介して結合してなる基であり、それらに結合する水素原子はそれぞれ独立に−ＣＯＯＲ０（式中、Ｒ０は水素原子又は炭素数１〜５のアルキル基を表す）、−ＮＯ２、−ＣＮ、−ＣＨ＝Ｃ（ＣＮ）２、−ＣＨ＝ＣＨ−ＣＮ、ハロゲン基、炭素数１〜５のアルキル基、又は炭素数１〜５のアルキルオキシ基で置換されても良い；
Ｙ２は、２価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環、炭素数５〜８の脂環式炭化水素、および、それらの組み合わせからなる群から選ばれる基であり、それらに結合する水素原子はそれぞれ独立に−ＮＯ２、−ＣＮ、−ＣＨ＝Ｃ（ＣＮ）２、−ＣＨ＝ＣＨ−ＣＮ、ハロゲン基、炭素数１〜５のアルキル基、又は炭素数１〜５のアルキルオキシ基で置換されても良い；
Ｒは、ヒドロキシ基、炭素数１〜６のアルコキシ基を表すか、又はＹ１と同じ定義を表す；
Ｘは、単結合、−ＣＯＯ−、−ＯＣＯ−、−Ｎ＝Ｎ−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＨ＝ＣＨ−ＣＯ−Ｏ−、又は−Ｏ−ＣＯ−ＣＨ＝ＣＨ−を表し、Ｘの数が２となるときは、Ｘ同士は同一でも異なっていてもよい；
Ｃｏｕは、クマリン−６−イル基またはクマリン−７−イル基を表し、それらに結合する水素原子はそれぞれ独立に−ＮＯ２、−ＣＮ、−ＣＨ＝Ｃ（ＣＮ）２、−ＣＨ＝ＣＨ−ＣＮ、ハロゲン基、炭素数１〜５のアルキル基、又は炭素数１〜５のアルキルオキシ基で置換されても良い；
ｑ１とｑ２は、一方が１で他方が０である；
ｑ３は０または１である；
Ｐ及びＱは、各々独立に、２価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環、炭素数５〜８の脂環式炭化水素、および、それらの組み合わせからなる群から選ばれる基である；ただし、Ｘが−ＣＨ＝ＣＨ−ＣＯ−Ｏ−、−Ｏ−ＣＯ−ＣＨ＝ＣＨ−である場合、−ＣＨ＝ＣＨ−が結合する側のＰ又はＱは芳香環であり、Ｐの数が２以上となるときは、Ｐ同士は同一でも異なっていてもよく、Ｑの数が２以上となるときは、Ｑ同士は同一でも異なっていてもよい；
ｌ１は０または１である；
ｌ２は０〜２の整数である；
ｌ１とｌ２がともに０であるときは、Ｔが単結合であるときはＡも単結合を表す；
ｌ１が１であるときは、Ｔが単結合であるときはＢも単結合を表す；
Ｈ及びＩは、各々独立に、２価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環、およびそれらの組み合わせから選ばれる基である。）
からなる群から選ばれるいずれか１種を有する請求項１〜４のいずれか１項に記載の組成物。
(In the formula, A, B and D are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO; Represents —O— or —O—CO—CH═CH—;
S is an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced by a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced with a halogen group;
Y 1 represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are groups bonded through a bonding group B, and the hydrogen atoms bonded to them are each independently —COOR 0 (wherein R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group), —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. May be substituted with an alkyloxy group;
Y 2 is a group selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, The hydrogen atoms bonded to each independently represent —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of
R represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y 1 ;
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. When CH is 2 and the number of X is 2, X may be the same or different;
Cou represents coumarin-6-yl group or a coumarin-7-yl group, -NO 2 are each a hydrogen atom bonded to them independently, -CN, -CH = C (CN ) 2, -CH = CH- May be substituted with CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
one of q1 and q2 is 1 and the other is 0;
q3 is 0 or 1;
P and Q are each independently selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. Provided that when X is —CH═CH—CO—O— or —O—CO—CH═CH—, P or Q on the side to which —CH═CH— is bonded is an aromatic ring; When the number of P is 2 or more, the Ps may be the same or different, and when the number of Q is 2 or more, the Qs may be the same or different;
l1 is 0 or 1;
l2 is an integer from 0 to 2;
when l1 and l2 are both 0, A represents a single bond when T is a single bond;
when l1 is 1, B represents a single bond when T is a single bond;
H and I are each independently a group selected from a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and combinations thereof. )
The composition according to any one of claims 1 to 4, comprising any one selected from the group consisting of:
（式中、Ａ、Ｂ、Ｄはそれぞれ独立に、単結合、−Ｏ−、−ＣＨ２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨ−ＣＯ−、−ＣＨ＝ＣＨ−ＣＯ−Ｏ−、又は−Ｏ−ＣＯ−ＣＨ＝ＣＨ−を表す；
Ｙ１は、１価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環および炭素数５〜８の脂環式炭化水素から選ばれる環を表すか、それらの置換基から選ばれる同一又は相異なった２〜６の環が結合基Ｂを介して結合してなる基であり、それらに結合する水素原子はそれぞれ独立に−ＣＯＯＲ０（式中、Ｒ０は水素原子又は炭素数１〜５のアルキル基を表す）、−ＮＯ２、−ＣＮ、−ＣＨ＝Ｃ（ＣＮ）２、−ＣＨ＝ＣＨ−ＣＮ、ハロゲン基、炭素数１〜５のアルキル基、又は炭素数１〜５のアルキルオキシ基で置換されても良い；
Ｘは、単結合、−ＣＯＯ−、−ＯＣＯ−、−Ｎ＝Ｎ−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＨ＝ＣＨ−ＣＯ−Ｏ−、又は−Ｏ−ＣＯ−ＣＨ＝ＣＨ−を表し、Ｘの数が２となるときは、Ｘ同士は同一でも異なっていてもよい；
ｌは１〜１２の整数を表す；
ｍは、０〜２の整数を表し、ｍ１、ｍ２は１〜３の整数を表す；
ｎは０〜１２の整数（ただしｎ＝０のときＢは単結合である）を表す；
Ｙ２は、２価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環、炭素数５〜８の脂環式炭化水素、および、それらの組み合わせからなる群から選ばれる基であり、それらに結合する水素原子はそれぞれ独立に−ＮＯ２、−ＣＮ、−ＣＨ＝Ｃ（ＣＮ）２、−ＣＨ＝ＣＨ−ＣＮ、ハロゲン基、炭素数１〜５のアルキル基、又は炭素数１〜５のアルキルオキシ基で置換されても良い；
Ｒは、ヒドロキシ基、炭素数１〜６のアルコキシ基を表すか、又はＹ１と同じ定義を表す）
からなる群から選ばれるいずれか１種を有する請求項１〜５のいずれか１項に記載の組成物。
(In the formula, A, B and D are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO; Represents —O— or —O—CO—CH═CH—;
Y 1 represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are groups bonded through a bonding group B, and the hydrogen atoms bonded to them are each independently —COOR 0 (wherein R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group), —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. May be substituted with an alkyloxy group;
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. When CH is 2 and the number of X is 2, X may be the same or different;
l represents an integer of 1 to 12;
m represents an integer of 0 to 2, and m1 and m2 represent an integer of 1 to 3;
n represents an integer of 0 to 12 (provided that when n = 0, B is a single bond);
Y 2 is a group selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, The hydrogen atoms bonded to each independently represent —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of
R represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y 1 ).
The composition according to any one of claims 1 to 5, comprising any one selected from the group consisting of:
（式中、Ａは、それぞれ独立に、単結合、−Ｏ−、−ＣＨ２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨ−ＣＯ−、−ＣＨ＝ＣＨ−ＣＯ−Ｏ−、又は−Ｏ−ＣＯ−ＣＨ＝ＣＨ−を表す；
Ｘは、単結合、−ＣＯＯ−、−ＯＣＯ−、−Ｎ＝Ｎ−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＨ＝ＣＨ−ＣＯ−Ｏ−、又は−Ｏ−ＣＯ−ＣＨ＝ＣＨ−を表し、Ｘの数が２となるときは、Ｘ同士は同一でも異なっていてもよい；
ｌは、１〜１２の整数を表し、ｍは０〜２の整数を表し、ｍ１は１〜３の整数を表す；
Ｒは、１価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環および炭素数５〜８の脂環式炭化水素から選ばれる環を表すか、それらの置換基から選ばれる同一又は相異なった２〜６の環が結合基Ｂを介して結合してなる基であり、それらに結合する水素原子はそれぞれ独立に−ＣＯＯＲ０（式中、Ｒ０は水素原子又は炭素数１〜５のアルキル基を表す）、−ＮＯ２、−ＣＮ、−ＣＨ＝Ｃ（ＣＮ）２、−ＣＨ＝ＣＨ−ＣＮ、ハロゲン基、炭素数１〜５のアルキル基、又は炭素数１〜５のアルキルオキシ基で置換されても良いか、又はヒドロキシ基もしくは炭素数１〜６のアルコキシ基を表す）
からなる群から選ばれるいずれか１種を有する請求項１〜５のいずれか１項に記載の組成物。
(In the formula, each A is independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—O—, Or -O-CO-CH = CH-;
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. When CH is 2 and the number of X is 2, X may be the same or different;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, and m1 represents an integer of 1 to 3;
R represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or a phase selected from those substituents. A group in which different 2 to 6 rings are bonded through a bonding group B, and the hydrogen atoms bonded to them are each independently -COOR 0 (wherein R 0 is a hydrogen atom or a carbon number of 1 to 5). represents an alkyl group), - NO 2, -CN, -CH = C (CN) 2, -CH = CH-CN, a halogen group, an alkyl group of 1 to 5 carbon atoms, or alkyl of 1 to 5 carbon atoms (It may be substituted with an oxy group or represents a hydroxy group or an alkoxy group having 1 to 6 carbon atoms)
The composition according to any one of claims 1 to 5, comprising any one selected from the group consisting of:
（式中、Ａはそれぞれ独立に、単結合、−Ｏ−、−ＣＨ２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨ−ＣＯ−、−ＣＨ＝ＣＨ−ＣＯ−Ｏ−、又は−Ｏ−ＣＯ−ＣＨ＝ＣＨ−を表す；
Ｙ１は、１価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環および炭素数５〜８の脂環式炭化水素から選ばれる環を表すか、それらの置換基から選ばれる同一又は相異なった２〜６の環が結合基Ｂを介して結合してなる基であり、それらに結合する水素原子はそれぞれ独立に−ＣＯＯＲ０（式中、Ｒ０は水素原子又は炭素数１〜５のアルキル基を表す）、−ＮＯ２、−ＣＮ、−ＣＨ＝Ｃ（ＣＮ）２、−ＣＨ＝ＣＨ−ＣＮ、ハロゲン基、炭素数１〜５のアルキル基、又は炭素数１〜５のアルキルオキシ基で置換されても良い；
ｌは１〜１２の整数を表し、ｍ１、ｍ２は１〜３の整数を表す）
で表される光反応性側鎖を有する請求項１〜５のいずれか１項に記載の組成物。
(In the formula, each A is independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—O—, Or -O-CO-CH = CH-;
Y 1 represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are groups bonded through a bonding group B, and the hydrogen atoms bonded to them are each independently —COOR 0 (wherein R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group), —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. May be substituted with an alkyloxy group;
l represents an integer of 1 to 12, and m1 and m2 represent an integer of 1 to 3)
The composition of any one of Claims 1-5 which has a photoreactive side chain represented by these.
Ｘは、単結合、−ＣＯＯ−、−ＯＣＯ−、−Ｎ＝Ｎ−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＨ＝ＣＨ−ＣＯ−Ｏ−、又は−Ｏ−ＣＯ−ＣＨ＝ＣＨ−を表し、Ｘの数が２となるときは、Ｘ同士は同一でも異なっていてもよい；
ｌは、１〜１２の整数を表し、ｍは０〜２の整数を表す）
で表される基を有する請求項１〜５のいずれか１項に記載の組成物。
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. When CH is 2 and the number of X is 2, X may be the same or different;
l represents an integer of 1 to 12, and m represents an integer of 0 to 2)
The composition of any one of Claims 1-5 which has group represented by these.
Ｙ１は、１価のベンゼン環、ナフタレン環、ビフェニル環、フラン環、ピロール環および炭素数５〜８の脂環式炭化水素から選ばれる環を表すか、それらの置換基から選ばれる同一又は相異なった２〜６の環が結合基Ｂを介して結合してなる基であり、それらに結合する水素原子はそれぞれ独立に−ＣＯＯＲ０（式中、Ｒ０は水素原子又は炭素数１〜５のアルキル基を表す）、−ＮＯ２、−ＣＮ、−ＣＨ＝Ｃ（ＣＮ）２、−ＣＨ＝ＣＨ−ＣＮ、ハロゲン基、炭素数１〜５のアルキル基、又は炭素数１〜５のアルキルオキシ基で置換されても良い；
Ｘは、単結合、−ＣＯＯ−、−ＯＣＯ−、−Ｎ＝Ｎ−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＨ＝ＣＨ−ＣＯ−Ｏ−、又は−Ｏ−ＣＯ−ＣＨ＝ＣＨ−を表し、Ｘの数が２となるときは、Ｘ同士は同一でも異なっていてもよい；
ｌは１〜１２の整数を表し、ｍは０〜２の整数を表す）で表される基を有する請求項１〜５のいずれか１項に記載の組成物。
Y 1 represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are groups bonded through a bonding group B, and the hydrogen atoms bonded to them are each independently —COOR 0 (wherein R 0 is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group), —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. May be substituted with an alkyloxy group;
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. When CH is 2 and the number of X is 2, X may be the same or different;
1 represents the integer of 1-12, m represents the integer of 0-2), The composition of any one of Claims 1-5 which have group represented.
［ＩＩ］ ［Ｉ］で得られた液晶セルに、前記２枚の透明基体のいずれか一方から、偏光した紫外線を照射する工程；
を有することにより、液晶セル内で（Ｂ）低分子液晶が所定の配向性を有する光学素子が形成される、光学素子の製造方法。[I] Two transparent substrates in which a photoreactive liquid crystal composition having (A) a siloxane skeleton and having a photoreactive group; and (B) a low-molecular liquid crystal; A step of filling a space formed therebetween to form a liquid crystal cell; and [II] irradiating the liquid crystal cell obtained in [I] with polarized ultraviolet rays from one of the two transparent substrates. Process;
A method of manufacturing an optical element, in which an optical element in which (B) a low molecular liquid crystal has a predetermined orientation is formed in a liquid crystal cell.
［ＩＩ］ ［Ｉ］で得られた液晶セルに、前記２枚の透明基体のいずれか一方から、偏光した紫外線を照射する工程；
を有することにより、液晶セル内で（Ｂ）低分子液晶が所定の配向性を有する表示素子が形成される、表示素子の製造方法。[I] Two transparent substrates in which a photoreactive liquid crystal composition having (A) a siloxane skeleton and having a photoreactive group; and (B) a low-molecular liquid crystal; A step of filling a space formed therebetween to form a liquid crystal cell; and [II] irradiating the liquid crystal cell obtained in [I] with polarized ultraviolet rays from one of the two transparent substrates. Process;
A display element manufacturing method in which (B) a low molecular liquid crystal has a predetermined orientation is formed in a liquid crystal cell.
（式中、Ｒ１０１〜Ｒ１０８は各々独立に、１価の有機基を表し；
Ｑ１〜Ｑ４、及びＱ８は各々独立に、光反応性基を表し；
Ｑ５〜Ｑ７は各々独立に、光反応性基であるか又は１価の有機基を表し；
Ｐ１は、炭素数１〜１０の直鎖または分岐鎖のアルキレン基（炭素原子に結合している水素原子は１価の有機基で置換されていてもよい。また、アルキレン基中、隣り合わない炭素原子が−Ｏ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−ＮＨ−ＣＯ−Ｏ−、−Ｏ−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−ＮＨ−で置換されていてもよい）を表し；
ｎ１１、ｎ１２、及びｎ１４は各々独立に、１〜２０の整数を表し；
ｎ１３は３〜２０の整数を表し；
ｍ４は１〜４の整数を表す。）
からなる群から選ばれる少なくとも１種で表される化合物。
(Wherein R 101 to R 108 each independently represents a monovalent organic group;
Q 1 to Q 4 and Q 8 each independently represent a photoreactive group;
Q 5 to Q 7 each independently represent a photoreactive group or a monovalent organic group;
P 1 is a linear or branched alkylene group having 1 to 10 carbon atoms (the hydrogen atom bonded to the carbon atom may be substituted with a monovalent organic group. No carbon atoms may be substituted with —O—, —CO—O—, —O—CO—, —NH—CO—O—, —O—CO—NH—, —NH—CO—NH—. );
n11, n12, and n14 each independently represents an integer of 1 to 20;
n13 represents an integer of 3 to 20;
m4 represents an integer of 1 to 4. )
A compound represented by at least one selected from the group consisting of:
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| JPH0862561A (en) * | 1994-08-19 | 1996-03-08 | Ricoh Co Ltd | Liquid crystal prepolymer composition and liquid crystal display element using same |
| JP2002520472A (en) * | 1998-07-14 | 2002-07-09 | ロリク アーゲー | Composition |
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| WO2015114864A1 (en) * | 2014-01-30 | 2015-08-06 | 公立大学法人兵庫県立大学 | Photoreactive liquid crystal composition, display element, optical element, method for manufacturing display element, and method for manufacturing optical element |
| US20150353668A1 (en) * | 2013-01-11 | 2015-12-10 | Cheil Industries Inc. | Photocurable composition, barrier layer comprising same, and encapsulated device comprising same |
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| JPH03181490A (en) * | 1989-12-05 | 1991-08-07 | Consortium Elektrochem Ind Gmbh | Cyclic organosiloxane, its preparation and composition containing same and having nonlinear optical characteristics |
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