JP2001279245A - Polymer liquid crystal - Google Patents
Polymer liquid crystalInfo
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- JP2001279245A JP2001279245A JP2000091894A JP2000091894A JP2001279245A JP 2001279245 A JP2001279245 A JP 2001279245A JP 2000091894 A JP2000091894 A JP 2000091894A JP 2000091894 A JP2000091894 A JP 2000091894A JP 2001279245 A JP2001279245 A JP 2001279245A
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- liquid crystal
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は高分子液晶に関し、より
詳細には、光学、表示、記録材料等として利用される
（メタ）アクリル構造を有する液晶（類似）化合物と水
素結合可能なヒドロキシ基を有する（メタ）アクリル酸
エステルとの共重合体からなる高分子液晶に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer liquid crystal, and more particularly, to a hydroxy group capable of hydrogen bonding with a liquid crystal (similar) compound having a (meth) acrylic structure used as an optical, display, or recording material. The invention relates to a polymer liquid crystal comprising a copolymer with a (meth) acrylate ester having the following formula:
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】近年、
液晶物質はＴＮ型やＳＴＮ型に代表されるディスプレイ
素子等の液晶分子の可逆的運動を利用した表示媒体への
応用以外にも、その配向性と屈折率、誘電率、磁化率等
の物理的性質の異方性を利用して、位相差板、偏光板、
光偏光プリズム、各種光フィルター等の光学異方体への
応用が検討されている。2. Description of the Related Art In recent years,
Liquid crystal materials are not only applied to display media using reversible motion of liquid crystal molecules such as display elements such as TN type or STN type, but also have physical properties such as orientation, refractive index, dielectric constant, and magnetic susceptibility. Utilizing the anisotropy of properties, retardation plates, polarizing plates,
Applications to optically anisotropic bodies such as light polarizing prisms and various optical filters are being studied.
【０００３】このように、液晶物質を構成材料とする光
学異方体には、安定で均一な光学特性を得るために、液
晶状態における液晶分子の均一な配向状態を半永久的に
固定化して、機械的に安定な、配向性に優れた重合体と
することが必須である。As described above, in order to obtain stable and uniform optical characteristics, a uniform alignment state of liquid crystal molecules in a liquid crystal state is fixed semipermanently to an optically anisotropic material having a liquid crystal material as a constituent material. It is essential that the polymer be mechanically stable and have excellent orientation.
【０００４】液晶状態における液晶分子の均一な配向状
態構造を半永久的に固定化する手段としては、例えば、
重合性官能基を有する液晶性化合物又はこのような化合
物を含有する重合性液晶組成物を、光又は熱により重合
して高分子液晶とした後、溶液として基材に塗布し、乾
燥して溶媒を除去する方法や、重合性液晶性組成物の溶
液を基材に塗布し、液晶状態で均一に配向させた後、液
晶状態を保持したまま紫外線等のエネルギー線を照射す
ることによって光重合させて、均一な配向状態を半永久
的に固定化する方法が既に知られている。As means for semi-permanently fixing a uniform alignment state structure of liquid crystal molecules in a liquid crystal state, for example,
A liquid crystalline compound having a polymerizable functional group or a polymerizable liquid crystal composition containing such a compound is polymerized by light or heat to form a polymer liquid crystal, and then applied to a substrate as a solution, dried, and dried. After applying a solution of the polymerizable liquid crystal composition to a substrate and uniformly aligning the liquid crystal state, the photopolymerization is performed by irradiating energy rays such as ultraviolet rays while maintaining the liquid crystal state. Thus, a method for semi-permanently fixing a uniform alignment state has already been known.
【０００５】このように、高分子液晶は基材上に固定さ
れて利用され、基材としては用途に応じてガラスやプラ
スチック等の種々の材料が用いられる。As described above, the polymer liquid crystal is used by being fixed on a base material, and various materials such as glass and plastic are used as the base material depending on the application.
【０００６】そのため、基材上に形成される液晶高分子
は、高分子液晶自身の安定性のほかに、基材に対する密
着性が要求される。Therefore, the liquid crystal polymer formed on the base material is required to have not only the stability of the polymer liquid crystal itself but also adhesion to the base material.
【０００７】しかしながら、高分子液晶は基材上に重合
体や単量体を直接塗布して用いるため、基板との間に接
着剤等は用いられず、基板との密着性において満足のい
くものではなかった。However, since the polymer liquid crystal is used by directly coating a polymer or monomer on the substrate, no adhesive or the like is used between the polymer liquid crystal and the substrate, and the polymer liquid crystal has satisfactory adhesiveness with the substrate. Was not.
【０００８】従って、本発明の目的は、基板への密着性
に優れた高分子液晶を提供することにある。Therefore, an object of the present invention is to provide a polymer liquid crystal having excellent adhesion to a substrate.
【０００９】[0009]
【課題を解決するための手段】本発明者らは、かかる現
状に鑑み、鋭意検討を重ねた結果、重合性液晶（類似）
化合物にアルコールやカルボン酸等の水素結合可能なヒ
ドロキシ基を持つ重合性化合物を共重合することで基板
との密着性に優れた高分子液晶を提供できることを見出
し、本発明に到達した。Means for Solving the Problems The present inventors have made intensive studies in view of the present situation, and as a result, have found that polymerizable liquid crystals (similar)
The inventors have found that a polymer liquid crystal having excellent adhesion to a substrate can be provided by copolymerizing a polymerizable compound having a hydroxyl group capable of hydrogen bonding, such as an alcohol or a carboxylic acid, with the compound, and arrived at the present invention.
【００１０】即ち、本発明は、（Ａ）（Ａ−１）重合性
液晶化合物及び/ 又は（Ａ−２）重合性液晶類似化合物
と（Ｂ）水素結合可能なヒドロキシ基を有する（メタ）
アクリル酸エステルとの共重合体からなる高分子液晶を
提供するものである。That is, the present invention relates to (A) a polymerizable liquid crystal compound (A-1) and / or (A-2) a polymerizable liquid crystal analog compound, and (B) a (meth) method having a hydrogen group capable of hydrogen bonding.
An object of the present invention is to provide a polymer liquid crystal comprising a copolymer with an acrylate ester.
【００１１】[0011]
【発明の実施の形態】以下に本発明を詳細に説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
【００１２】本発明における重合性液晶化合物及び重合
性液晶類似化合物とは、重合性不飽和基を有し、該重合
性不飽和基に、６員環構造を有する基２〜４個が直接結
合、エステル結合、エーテル結合及びアルキレン基で結
合した棒状構造を有する基が結合した構造を有する単量
体で、単独で液晶性を有する、又は、単独で重合した重
合体が液晶性を有する重合性液晶性化合物、単独では液
晶性を示さないものの、重合性液晶性化合物や他の重合
性液晶性類似化合物と共重合すると液晶性を示す化合物
を重合性液晶性類似化合物という。The polymerizable liquid crystal compound and the polymerizable liquid crystal analog compound in the present invention have a polymerizable unsaturated group, and two to four groups having a 6-membered ring structure are directly bonded to the polymerizable unsaturated group. , A monomer having a structure in which a group having a rod-like structure bonded by an ester bond, an ether bond and an alkylene group is bonded, and has a liquid crystallinity alone, or a polymer polymerized alone has a liquid crystallinity. A liquid crystal compound, which does not exhibit liquid crystallinity by itself, but exhibits a liquid crystallinity when copolymerized with a polymerizable liquid crystal compound or another polymerizable liquid crystal similar compound, is referred to as a polymerizable liquid crystal similar compound.
【００１３】上記重合性液晶性（類似）化合物として
は、より具体的には、以下の一般式（Ｉ）で表される化
合物が挙げられる。As the polymerizable liquid crystalline (similar) compound, more specifically, a compound represented by the following general formula (I) is exemplified.
【００１４】[0014]
【化５】 （式中、Ｒ1 は水素原子又はメチル基を、Ｒ2 は炭素原
子数１〜８のアルキル基、アルコキシ基、ハロゲン置換
アルキル基、ハロゲン置換アルコキシ基、アルキルオキ
シアルキル基、ハロゲン原子又はシアノ基を、Ｙ1 及び
Ｙ2 は各々独立に水素原子、ハロゲン原子を、Ａ、Ｂ、
Ｃ、Ｄの６員環は各々独立に、Embedded image (Wherein, R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group, a halogen-substituted alkyl group, a halogen-substituted alkoxy group, an alkyloxyalkyl group, a halogen atom or a cyano group. And Y 1 and Y 2 each independently represent a hydrogen atom or a halogen atom, A, B,
The 6-membered rings of C and D are each independently
【化６】 （Ｒ3 及びＲ4 は各々独立に水素原子、ハロゲン原子、
シアノ基又はメチル基を、Ｒ5 、Ｒ6 及びＲ7 は各々独
立に水素原子又はハロゲン原子を表す）を、Ｘ1、Ｘ2
及びＸ3 は各々独立に直接結合、又はEmbedded image (R 3 and R 4 are each independently a hydrogen atom, a halogen atom,
A cyano group or a methyl group, R 5 , R 6 and R 7 each independently represent a hydrogen atom or a halogen atom), X 1 , X 2
And X 3 are each independently a direct bond, or
【化７】 のいずれかの結合手を、ｎは２〜８の数を、ｍ１及びｍ
２は各々独立に０又は１の数を表す）Embedded image N is a number of 2 to 8, m1 and m
2 independently represents a number of 0 or 1)
【００１５】Ｒ2 で表される炭素原子数１〜８のアルキ
ル基としては、メチル、エチル、プロピル、イソプロピ
ル、ブチル、イソブチル、第二ブチル、第三ブチル、ペ
ンチル、ヘキシル、ヘプチル、オクチル等が挙げられ、
アルコキシ基としては、上記アルキル基に対応する基が
挙げられ、ハロゲン置換アルキル基としては、トリフル
オロメチル、２，２−ジフルオロエチル、２，２，２−
トリフルオロエチル等が挙げられ、ハロゲン置換アルコ
キシ基としては、２，２−ジフルオロエチル、２，２，
２−トリフルオロエチル等が挙げられ、アルキルオキシ
アルキル基としてはメトキシメチル、メトキシエチル、
エトキシメチル、エトキシエチル等が挙げられ、ハロゲ
ン原子としてはフッ素、塩素、臭素等が挙げられる。Examples of the alkyl group having 1 to 8 carbon atoms represented by R 2 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl and the like. And
Examples of the alkoxy group include groups corresponding to the above alkyl groups, and examples of the halogen-substituted alkyl group include trifluoromethyl, 2,2-difluoroethyl, 2,2,2-
Trifluoroethyl and the like, and examples of the halogen-substituted alkoxy group include 2,2-difluoroethyl,
2-trifluoroethyl and the like, and examples of the alkyloxyalkyl group include methoxymethyl, methoxyethyl,
Ethoxymethyl, ethoxyethyl and the like can be mentioned, and as the halogen atom, fluorine, chlorine, bromine and the like can be mentioned.
【００１６】Ｙ1 及びＹ2 で表されるハロゲン原子とし
ては、フッ素、塩素、臭素等が挙げられる。The halogen atom represented by Y 1 and Y 2 includes fluorine, chlorine, bromine and the like.
【００１７】Ｒ3 〜Ｒ7 で表されるハロゲン原子として
は、フッ素、塩素、臭素等が挙げられる。Examples of the halogen atom represented by R 3 to R 7 include fluorine, chlorine, bromine and the like.
【００１８】ｍ１及びｍ２は各々０〜２を示し、０≦ｍ
１＋ｍ２≦２であり、２より大きいと得られる重合体が
剛直になり配向性に乏しくなる。M1 and m2 each represent 0 to 2, and 0 ≦ m
1 + m2 ≦ 2, and if it is larger than 2, the obtained polymer becomes rigid and poor in orientation.
【００１９】本発明に用いられる化合物は、それ自身液
晶を示しても示さなくても良く、単独で又は他の重合性
化合物との共重合体において液晶性を示し、得られるポ
リマーのＴｇが高く、有機溶媒への耐溶解性に優れ、塗
布性、配向性にも優れる液晶性ポリマーを与えるもので
あれば良い。The compound used in the present invention may or may not show a liquid crystal by itself, shows liquid crystallinity alone or in a copolymer with another polymerizable compound, and has a high Tg of the obtained polymer. Any material can be used as long as it provides a liquid crystalline polymer having excellent resistance to dissolution in an organic solvent, and excellent in coatability and orientation.
【００２０】より具体的には、以下の化合物Ｎｏ．１〜
２２が挙げられる。但し、本発明は以下の化合物により
制限を受けるものではない。More specifically, the following compound No. 1 to
22. However, the present invention is not limited by the following compounds.
【００２１】[0021]
【化８】 Embedded image
【００２２】[0022]
【化９】 Embedded image
【００２３】[0023]
【化１０】 Embedded image
【００２４】[0024]
【化１１】 Embedded image
【００２５】[0025]
【化１２】 Embedded image
【００２６】[0026]
【化１３】 Embedded image
【００２７】[0027]
【化１４】 Embedded image
【００２８】[0028]
【化１５】 Embedded image
【００２９】[0029]
【化１６】 Embedded image
【００３０】[0030]
【化１７】 Embedded image
【００３１】[0031]
【化１８】 Embedded image
【００３２】[0032]
【化１９】 Embedded image
【００３３】[0033]
【化２０】 Embedded image
【００３４】[0034]
【化２１】 Embedded image
【００３５】[0035]
【化２２】 Embedded image
【００３６】[0036]
【化２３】 Embedded image
【００３７】[0037]
【化２４】 Embedded image
【００３８】[0038]
【化２５】 Embedded image
【００３９】[0039]
【化２６】 Embedded image
【００４０】[0040]
【化２７】 Embedded image
【００４１】[0041]
【化２８】 Embedded image
【００４２】[0042]
【化２９】 Embedded image
【００４３】本発明に用いられる水素結合可能なヒドロ
キシ基を有する（メタ）アクリル酸エステルとしては、
カルボン酸、スルホン酸、リン酸等の酸やヒドロキシ基
を有する（メタ）アクリル酸エステル化合物が挙げら
れ、末端にこれらの反応基を有するアルコール又はフェ
ノール化合物と（メタ）アクリル酸のエステル化合物と
しては、以下の一般式（II）で表される化合物が挙げら
れる。The (meth) acrylate having a hydroxy group capable of hydrogen bonding used in the present invention includes:
(Meth) acrylic acid ester compounds having an acid such as carboxylic acid, sulfonic acid, and phosphoric acid and a hydroxy group, and an ester compound of (meth) acrylic acid and an alcohol or phenol compound having these reactive groups at the terminal are And compounds represented by the following general formula (II).
【００４４】[0044]
【化３０】 （式中、Ｒ8 は水素原子又はメチル基を、Ｘ4 は炭素原
子数１〜１２のアルキレン基、シクロアルキレン基又は
アリーレン基を、Ｒ9 はアルキレン基又はアリーレン基
を、Ｙ3 は−ＯＨ、−ＣＯＯＨ、−ＳＯ3 Ｈ、−ＰＯ3
Ｈ2 又は−ＰＯ 4 Ｈ2 を、ｎは０又は１を表す）Embedded image(Where R8Represents a hydrogen atom or a methyl group;FourIs a carbon source
An alkylene group having 1 to 12 children, a cycloalkylene group or
An arylene group is represented by R9Is an alkylene group or an arylene group
And YThreeIs -OH, -COOH, -SOThreeH, -POThree
HTwoOr -PO FourHTwoAnd n represents 0 or 1.)
【００４５】上記式中、Ｘ4 で表されるアルキレン基と
しては、メチレン、エチレン、プロピレン、トリメチレ
ン、テトラメチレン、ペンタメチレン、２，２−ジメチ
ルトリメチレン、ヘキサメチレン、ヘプタメチレン、オ
クタメチレン、デカメチレン等が、シクロアルキレンと
しては、１，３−シクロへキシレン、１，４−シクロへ
キシレン等が、アリーレン基としては、フェニレン、ビ
フェニレン、ナフチレン等が挙げられる。In the above formula, examples of the alkylene group represented by X 4 include methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, heptamethylene, octamethylene, and decamethylene. Examples of cycloalkylene include 1,3-cyclohexylene and 1,4-cyclohexylene, and examples of the arylene group include phenylene, biphenylene, and naphthylene.
【００４６】Ｒ9 で表されるアルキレン基としては、メ
チレン、エチレン、プロピレン、トリメチレン、テトラ
メチレン、ペンタメチレン、２，２−ジメチルトリメチ
レン、ヘキサメチレン、ヘプタメチレン、オクタメチレ
ン、デカメチレン等が、アリーレン基としては、フェニ
レン、ビフェニレン、ナフチレン等が挙げられる。Examples of the alkylene group represented by R 9 include methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, heptamethylene, octamethylene, decamethylene and the like. Examples of the group include phenylene, biphenylene, naphthylene and the like.
【００４７】上記一般式（ＩＩ）で表される化合物とし
ては、より具体的には、以下の化合物Ｎｏ．２３〜２７
が挙げられる。As the compound represented by the above general formula (II), more specifically, the following compound No. 23-27
Is mentioned.
【００４８】[0048]
【化３１】 Embedded image
【００４９】[0049]
【化３２】 Embedded image
【００５０】[0050]
【化３３】 Embedded image
【００５１】[0051]
【化３４】 Embedded image
【００５２】[0052]
【化３５】 Embedded image
【００５３】本発明の高分子液晶は、成分（Ａ）と成分
（Ｂ）のみ、又は他の共重合成分と組成物として熱又は
光により重合されて液晶性高分子として種々の用途に用
いられる。The polymer liquid crystal of the present invention is polymerized by heat or light as a composition with only the component (A) and the component (B) or with other copolymerization components, and is used for various applications as a liquid crystalline polymer. .
【００５４】共重合に用いられる他の重合性成分として
は、特に限定されるものではなく、例えば、４−アクリ
ロイルオキシ−４’−デシルビフェニル、４−アクリロ
イルオキシ−４’−シアノビフェニル、４−アクリロイ
ルオキシ−４’−プロピルシクロヘキシルフェニル、４
−メタクリロイル−４’−ブチルビシクロヘキシル、４
−アクリロイル−４’−アミルトラン、４−アクリロイ
ル−４’−（３，４−ジフルオロフェニル）ビシクロヘ
キシル等のモノアクリレート化合物、１，４−ビス（４
−（６−アクリロイルオキシヘキシルオキシ）ベンゾイ
ルオキシ）ベンゼン、１，４−ビス（４−（２−アクリ
ロイルオキシエチルオキシ）ベンゾイルオキシ）ベンゼ
ン、ビス（４−（２−アクリロイルオキシエチルオキ
シ）フェニル）テレフタレート、４−（４−アクリロイ
ルオキシフェニル）カルボニルオキシ−（６−アクリロ
イルオキシヘキシルオキシフェニル）カルボニルオキシ
ベンゼン、４−（４−アクリロイルオキシフェニル）カ
ルボニルオキシ−（３−アクリロイルオキシプロピルオ
キシフェニル）カルボニルオキシベンゼン、４−アクリ
ロイルオキシ安息香酸−４−（２−アクリロイルオキシ
エチル）フェニルエステル、４−アクリロイルオキシ安
息香酸−４−（３−アクリロイルオキシプロピル）フェ
ニルエステル等のジアクリレート化合物、４−（２−ア
クリロイルオキシエチルオキシ）安息香酸−４−
（３’，４’−ビス（アクリロイルオキシ）ベンゾイル
オキシフェニル）エステル、４−（６−アクリロイルオ
キシヘキシルオキシ）安息香酸−４−（３’，４’−ビ
ス（アクリロイルオキシ）ベンゾイルオキシフェニル）
エステル、４−アクリロイルオキシフェニル−３，４−
ビス（アクリロイルオキシ）安息香酸エステル等のトリ
アクリレート化合物が挙げられる。The other polymerizable components used in the copolymerization are not particularly restricted but include, for example, 4-acryloyloxy-4′-decylbiphenyl, 4-acryloyloxy-4′-cyanobiphenyl, Acryloyloxy-4′-propylcyclohexylphenyl, 4
-Methacryloyl-4'-butylbicyclohexyl, 4
Monoacrylate compounds such as -acryloyl-4'-amyltran, 4-acryloyl-4 '-(3,4-difluorophenyl) bicyclohexyl, and 1,4-bis (4
-(6-acryloyloxyhexyloxy) benzoyloxy) benzene, 1,4-bis (4- (2-acryloyloxyethyloxy) benzoyloxy) benzene, bis (4- (2-acryloyloxyethyloxy) phenyl) terephthalate 4- (4-acryloyloxyphenyl) carbonyloxy- (6-acryloyloxyhexyloxyphenyl) carbonyloxybenzene, 4- (4-acryloyloxyphenyl) carbonyloxy- (3-acryloyloxypropyloxyphenyl) carbonyloxybenzene And 4-acryloyloxybenzoic acid-4- (2-acryloyloxyethyl) phenyl ester and 4-acryloyloxybenzoic acid-4- (3-acryloyloxypropyl) phenyl ester. Acrylate compounds, 4- (2-acryloyloxyethyloxy) benzoic acid 4-
(3 ′, 4′-bis (acryloyloxy) benzoyloxyphenyl) ester, 4- (6-acryloyloxyhexyloxy) benzoic acid-4- (3 ′, 4′-bis (acryloyloxy) benzoyloxyphenyl)
Ester, 4-acryloyloxyphenyl-3,4-
And triacrylate compounds such as bis (acryloyloxy) benzoate.
【００５５】本発明の成分（Ａ）、成分（Ｂ）と他の重
合性成分との共重合体における重量比は特に限定される
ものではないが、全重合性成分中で成分（Ａ）は３０重
量％〜９９重量％が好ましく、成分（Ｂ）は１重量％〜
３０重量％が好ましく、その他の成分は５０重量％未満
が好ましい。（Ａ）成分が上記の範囲を外れると得られ
る液晶高分子の光学特性が低下し、（Ｂ）成分が上記の
範囲を外れると基材に対する十分な密着性が得られな
い。その他の成分は過剰に用いると密着性が不足した
り、光学特性が低下したりする。The weight ratio of the copolymers of the components (A) and (B) of the present invention and other polymerizable components is not particularly limited, but the component (A) in the total polymerizable components is not limited. 30% by weight to 99% by weight is preferable, and the component (B) is 1% by weight to
The content is preferably 30% by weight, and other components are preferably less than 50% by weight. If the component (A) is out of the above range, the optical properties of the obtained liquid crystal polymer will deteriorate, and if the component (B) is out of the above range, sufficient adhesion to the substrate will not be obtained. If the other components are used in excess, the adhesion may be insufficient or the optical properties may be reduced.
【００５６】[0056]
【実施例】以下、実施例等に基づき本発明を具体的に説
明する。The present invention will be specifically described below based on examples and the like.
【００５７】〔実施例１−１〜１−３及び比較例１−１
〜１−３〕 （共重合体の合成）表１記載（モル％）の組成物４ｇに
重合開始剤として過酸化ベンゾイル０．０５２ｇ（２モ
ル％）を加え、テトラヒドロフラン３０ｍｌ中に溶解し
て還流下、８時間反応後に３０℃まで冷却し、５℃メタ
ノール４５０ｍｌを滴下して、析出した沈殿をろ過によ
り取り出し、５℃のメタノールで洗浄した。[Examples 1-1 to 1-3 and Comparative Example 1-1]
(1-3) (Synthesis of copolymer) To 4 g of the composition shown in Table 1 (mol%), 0.052 g (2 mol%) of benzoyl peroxide was added as a polymerization initiator, dissolved in 30 ml of tetrahydrofuran and refluxed. After reaction for 8 hours, the mixture was cooled to 30 ° C., 450 ml of 5 ° C. methanol was added dropwise, and the deposited precipitate was taken out by filtration and washed with 5 ° C. methanol.
【００５８】（基材への塗布）得られた高分子液晶１ｇ
をシクロヘキサノン／メチルエチルケトン＝４／１（重
量比）混合溶媒４ｇに溶解した。調製した溶液を、表面
を中性洗剤で洗浄後、さらに、イソプロパノールで洗浄
したポリエチレンテレフタレートフィルムに２μｍ厚で
バーコーターにより塗布した。室温で１時間予備乾燥
後、３０℃減圧下で溶媒を除去した。得られた高分子液
晶膜の基材への密着性を、ＪＩＳ Ｋ５４００ ８．
５．２（碁盤目テープ法）に準じて評価した。結果は、
碁盤目状に切れ目の入った高分子液晶の区分が全て剥離
しなかった場合を１００として剥がれた区分数の１００
分率により示した。すなわち、評価結果においては、数
値が高いほど基材との密着性に優れる。結果を表１に示
す。(Coating on a substrate) 1 g of the obtained polymer liquid crystal
Was dissolved in 4 g of a mixed solvent of cyclohexanone / methyl ethyl ketone = 4/1 (weight ratio). After the prepared solution was washed with a neutral detergent on its surface, it was further applied to a polyethylene terephthalate film washed with isopropanol at a thickness of 2 μm using a bar coater. After preliminary drying at room temperature for 1 hour, the solvent was removed under reduced pressure at 30 ° C. 7. The adhesion of the obtained polymer liquid crystal film to the substrate was measured according to JIS K5400.
Evaluation was performed according to 5.2 (cross-cut tape method). Result is,
The number of peeled sections is 100, where 100 is the case where all the sections of the polymer liquid crystal having cuts in a grid pattern are not peeled off.
Indicated by fraction. That is, in the evaluation results, the higher the numerical value, the better the adhesion to the substrate. Table 1 shows the results.
【００５９】[0059]
【表１】 [Table 1]
【００６０】[0060]
【００６１】本発明の高分子液晶は、水素結合可能なヒ
ドロキシ構造を有する重合性の化合物を組み込むことに
より、基材への密着性に優れる。The polymer liquid crystal of the present invention is excellent in adhesion to a substrate by incorporating a polymerizable compound having a hydroxy structure capable of hydrogen bonding.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 2H049 BA02 BA06 BA42 BC22 4H027 BA13 BD24 4J100 AL08P AL08Q AL09Q AL92P AR05P AT08P BA02P BA02Q BA05P BA15P BA16Q BA40P BA56Q BA64Q BB00P BB07P BC04P BC43P BC44P BC49P BC69P BC73P ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H049 BA02 BA06 BA42 BC22 4H027 BA13 BD24 4J100 AL08P AL08Q AL09Q AL92P AR05P AT08P BA02P BA02Q BA05P BA15P BA16Q BA40P BA56Q BA64Q BB00P BB07P BC04P BC43P BC44P BC49P
Claims (4)
/ 又は（Ａ−２）重合性液晶類似化合物と（Ｂ）水素結
合可能なヒドロキシ基を有する（メタ）アクリル酸エス
テルとの共重合体からなる高分子液晶。(A) (A-1) a polymerizable liquid crystal compound and
And / or a polymer liquid crystal comprising a copolymer of (A-2) a polymerizable liquid crystal analog and (B) a (meth) acrylate having a hydroxy group capable of hydrogen bonding.
が、アルコール又はカルボン酸に由来するヒドロキシ基
である請求項１記載の高分子液晶。2. The polymer liquid crystal according to claim 1, wherein the (B) hydroxy group capable of hydrogen bonding is a hydroxy group derived from an alcohol or a carboxylic acid.
及び/ 又は（Ａ−２）重合性液晶類似化合物が、下記一
般式（Ｉ）で表される請求項１記載の高分子液晶。 【化１】 （式中、Ｒ1 は水素原子又はメチル基を、Ｒ2 は炭素原
子数１〜８のアルキル基、アルコキシ基、ハロゲン置換
アルキル基、ハロゲン置換アルコキシ基、アルキルオキ
シアルキル基、ハロゲン原子又はシアノ基を、Ｙ1 及び
Ｙ2 は各々独立に水素原子、ハロゲン原子を、Ａ、Ｂ、
Ｃ、Ｄの６員環は各々独立に、 【化２】 （Ｒ3 及びＲ4 は各々独立に水素原子、ハロゲン原子、
シアノ基又はメチル基を、Ｒ5 、Ｒ6 及びＲ7 は各々独
立に水素原子又はハロゲン原子を表す）を、Ｘ1、Ｘ2
及びＸ3 は各々独立に直接結合、又は 【化３】 のいずれかの結合手を、ｎは２〜８の数を、ｍ１及びｍ
２は各々独立に０又は１の数を表す）3. The polymer according to claim 1, wherein said (A) (A-1) polymerizable liquid crystal compound and / or (A-2) polymerizable liquid crystal analog compound is represented by the following general formula (I). liquid crystal. Embedded image (Wherein, R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group, a halogen-substituted alkyl group, a halogen-substituted alkoxy group, an alkyloxyalkyl group, a halogen atom or a cyano group. And Y 1 and Y 2 each independently represent a hydrogen atom or a halogen atom, A, B,
The 6-membered rings of C and D are each independently: (R 3 and R 4 are each independently a hydrogen atom, a halogen atom,
A cyano group or a methyl group, R 5 , R 6 and R 7 each independently represent a hydrogen atom or a halogen atom), X 1 , X 2
And X 3 are each independently a direct bond, or N is a number of 2 to 8, m1 and m
2 independently represents a number of 0 or 1)
を有する（メタ）アクリル酸エステルが、下記一般式
（II）で表される請求項１記載の高分子液晶。 【化４】 （式中、Ｒ8 は水素原子又はメチル基を、Ｘ4 は炭素原
子数１〜１２のアルキレン基、シクロアルキレン基又は
アリーレン基を、Ｒ9 はアルキレン基又はアリーレン基
を、Ｙ3 は−ＯＨ、−ＣＯＯＨ、−ＳＯ3 Ｈ、−ＰＯ3
Ｈ2 又は−ＰＯ 4 Ｈ2 を、ｎは０又は１を表す）4. The (B) hydroxy group capable of hydrogen bonding
(Meth) acrylic acid ester having the following general formula
The polymer liquid crystal according to claim 1, which is represented by (II). Embedded image(Where R8Represents a hydrogen atom or a methyl group;FourIs a carbon source
An alkylene group having 1 to 12 children, a cycloalkylene group or
An arylene group is represented by R9Is an alkylene group or an arylene group
And YThreeIs -OH, -COOH, -SOThreeH, -POThree
HTwoOr -PO FourHTwoAnd n represents 0 or 1.)
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Cited By (8)
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|---|---|---|---|---|
| WO2005005573A1 (en) * | 2003-07-12 | 2005-01-20 | Merck Patent Gmbh | Polymerised liquid crystal film with improved adhesion |
| WO2005083695A1 (en) * | 2004-02-17 | 2005-09-09 | Koninklijke Philips Electronics N.V. | Optical recording medium comprising molecules with hydrogen bonds |
| WO2006115033A1 (en) * | 2005-04-20 | 2006-11-02 | Nissan Chemical Industries, Ltd. | Polymerizable compound, polymerizable liquid crystal composition, and polymer and film of those |
| JP2008248157A (en) * | 2007-03-30 | 2008-10-16 | Dic Corp | Polymerizable liquid crystal composition |
| JP2008250108A (en) * | 2007-03-30 | 2008-10-16 | Dic Corp | Polymerizable liquid crystal composition |
| JP2008291213A (en) * | 2007-04-23 | 2008-12-04 | Univ Of Yamanashi | Proton transporting material, electrolyte using the same, ion exchanger, membrane electrode assembly, fuel cell, and hydrophobic monomer |
| JP2014028916A (en) * | 2012-06-27 | 2014-02-13 | Jnc Corp | Polymerizable liquid crystal composition |
| CN106471023A (en) * | 2014-06-23 | 2017-03-01 | Dic株式会社 | Polymerizable composition, polymerizable composition and use its film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101124834B1 (en) * | 2003-07-12 | 2012-03-26 | 메르크 파텐트 게엠베하 | Polymerised liquid crystal film with improved adhesion |
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| WO2005083695A1 (en) * | 2004-02-17 | 2005-09-09 | Koninklijke Philips Electronics N.V. | Optical recording medium comprising molecules with hydrogen bonds |
| WO2006115033A1 (en) * | 2005-04-20 | 2006-11-02 | Nissan Chemical Industries, Ltd. | Polymerizable compound, polymerizable liquid crystal composition, and polymer and film of those |
| JP2008250108A (en) * | 2007-03-30 | 2008-10-16 | Dic Corp | Polymerizable liquid crystal composition |
| JP2008248157A (en) * | 2007-03-30 | 2008-10-16 | Dic Corp | Polymerizable liquid crystal composition |
| JP2008291213A (en) * | 2007-04-23 | 2008-12-04 | Univ Of Yamanashi | Proton transporting material, electrolyte using the same, ion exchanger, membrane electrode assembly, fuel cell, and hydrophobic monomer |
| JP2014028916A (en) * | 2012-06-27 | 2014-02-13 | Jnc Corp | Polymerizable liquid crystal composition |
| CN106471023A (en) * | 2014-06-23 | 2017-03-01 | Dic株式会社 | Polymerizable composition, polymerizable composition and use its film |
| US20170190819A1 (en) * | 2014-06-23 | 2017-07-06 | Dic Corporation | Polymerizable composition and film using the same |
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