JP2019531398A - Photo-alignment copolymer material - Google Patents

Abstract

The present invention is for photo-alignment of liquid crystals, in particular for planar alignment of liquid crystals, comprising at least one monomer represented by formula (I) and one monomer represented by formula (II). Siloxane copolymers and their use for optical and electro-optical devices such as liquid crystal devices (LCDs).

Description

  The present invention relates to a copolymer for photoalignment of liquid crystals, crosslinkable liquid crystals or non-crosslinkable liquid crystals, for example for planar alignment of liquid crystals or for vertical alignment of liquid crystals. The invention further relates to a composition comprising said copolymer and its use for optical and electro-optical devices, for example liquid crystal devices (LCD).

  Several photo-alignment materials are known in the art, but there is still a need to develop new photo-alignment materials that have better optical quality, for example, for use in electro-optic applications. Homopolymers have limited flexibility in fine-tuning chemical and / or electro-optical properties. Accordingly, blends or formulations are often constructed that provide access to the desired chemical and / or electro-optical properties. However, there are disadvantages due to solubility problems, phase separation, inhomogeneities on the alignment layer surface and changes in electro-optical properties, which are undesirable. In order to avoid these drawbacks, there is a need for new photo-alignment materials that solve these problems and, in addition, exhibit the desired chemical and / or electro-optical properties. An example of such a photo-alignment copolymer material is described in WO2013 / 017467.

  In the present invention, a novel photo-alignment copolymer comprising at least a first monomer having a side chain represented by formula (I) and a second monomer having a side chain represented by formula (II) or (III) Is described. These photo-alignment copolymers have excellent optical properties and provide low energy consumption LCDs without reducing access to economical manufacturing processes and required optical properties.

で示される側鎖を有する第１のモノマーと、
式（ＩＩ）

又は式（ＩＩＩ）

で示される側鎖を有する第２のモノマーとを少なくとも含み、
ここで、ポリマー骨格は、ポリシロキサンである、
コポリマーを提供することである。 SUMMARY OF THE INVENTION A first object of the present invention is the formula (I)

A first monomer having a side chain represented by:
Formula (II)

Or formula (III)

At least a second monomer having a side chain represented by
Here, the polymer skeleton is polysiloxane.
It is to provide a copolymer.

  A second object of the present invention is to provide a composition comprising at least one said copolymer, a second polymer or copolymer different from the first, and optionally an additive.

  The third object of the present invention is to provide an alignment layer comprising one said copolymer.

  The fourth object of the present invention is to provide a method for producing an alignment layer containing the copolymer and an alignment layer obtained by such a method.

  The fifth object of the present invention is to align the liquid crystal, particularly for the liquid crystal display, for example, for in-plane switching (IPS), for the vertical alignment (VA) of the liquid crystal, for the twisted nematic alignment (TN). It is intended to provide the use of the alignment layer for the alignment of a liquid crystal containing a polymerizable liquid crystal or for the alignment of a liquid crystal sandwiched between a pair of alignment layers.

  A sixth object of the present invention is to provide a method for manufacturing a liquid crystal display including the photo-alignment material or the alignment layer.

  The seventh object of the present invention is to provide an optical or electro-optical unstructured or structured element comprising the copolymer or the alignment layer.

DETAILED DESCRIPTION OF THE INVENTION To this end, the present invention provides, in a first aspect, a side of formula (I) for photo-alignment of liquid crystals, for example for planar alignment of liquid crystals or for vertical alignment of liquid crystals. The present invention relates to a copolymer comprising a first monomer having a chain and a second monomer having a side chain represented by formula (II) or formula (III), wherein the polymer backbone is polysiloxane.

［式中、
ｎ_０は、０〜４、好ましくは０〜２、更により好ましくは０〜１の整数であり、
ｎ_１は、０〜１５、好ましくは１〜１０、より好ましくは１〜８、より好ましくは１〜５、最も好ましくは１〜３の整数であり、最も好ましくは、ｎ_１は、１であり、
ｎ_２は、０〜１５、好ましくは１〜１０、より好ましくは１〜８、より好ましくは１〜５、最も好ましくは１〜３の整数であり、最も好ましくは、ｎ_２は、１であり、
ｎ_３は、１〜１５、好ましくは１〜１０、より好ましくは１〜８、より好ましくは１〜５、最も好ましくは１〜３の整数であり、最も好ましくは、ｎ_３は、１であり、
Ｘ、Ｙは、それぞれ独立して、Ｈ、Ｆ、Ｃｌ、ＣＮを表わし、
Ｓ_２は、環状、芳香族、直鎖又は分岐鎖で置換又は非置換のＣ_１〜Ｃ_２４アルキレン、特に、Ｃ_１〜Ｃ_１２アルキレン、とりわけ、Ｃ_１〜Ｃ_８アルキレン、とりわけ、Ｃ_１〜Ｃ_６アルキレン、とりわけ、Ｃ_１〜Ｃ_４アルキレン、とりわけ、Ｃ_１〜Ｃ_２アルキレンを表わし、同アルキレンにおいて、１つ以上の−Ｃ−、−ＣＨ−、−ＣＨ_２−基は、連結基により置き換えられていることができ、ここで、２つ以上の−Ｃ−、−ＣＨ−、−ＣＨ_２−基が置き換えられている場合、連結基は、同じか又は異なることができ、
Ｅは、Ｏ、Ｓ、ＮＨ、Ｃ（Ｃ_１〜Ｃ_６アルキル）、ＮＲ^１２、ＯＣ、ＯＯＣ、ＯＣＯＮＨ、ＯＣＯＮＲ^４、ＳＣＳ、ＳＣを表わし、ここで、Ｒ^１２は、環状、直鎖又は分岐鎖で置換又は非置換Ｃ_１〜Ｃ_２４アルキルであり、ここで、１つ以上の−Ｃ−、−ＣＨ−、−ＣＨ_２−基は、それぞれ独立して、連結基により置き換えられていることができ、あるいは、好ましくは、Ｅは、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＯＯＣ−、Ｓ又はＮＨからなる群より選択され、
Ａは、ハロゲン又は置換もしくは非置換のＣ_１〜Ｃ_２４アルキル、置換もしくは非置換のＣ_１〜Ｃ_２４アルケニル、置換もしくは非置換のＣ_１〜Ｃ_２４アルキニル又はカルボン酸を表わし、ここで、１つ以上の−Ｃ−、−ＣＨ−、−ＣＨ_２−基は、それぞれ独立して、ヘテロ原子により置き換えられていることができ、好ましくは、Ａは、ハロゲン、Ｈ又はＣ_１〜Ｃ_２４アルコキシ又はカルボン酸であり、最も好ましくは、Ａは、Ｈ、Ｆ、Ｃ_１〜Ｃ_６アルキル、Ｃ_１〜Ｃ_６アルコキシ又はカルボン酸であり、
Ｚ_２は、その電子密度の非局在化を有し、及び／又は、その隣接する電子の電子密度の非局在化を誘引する化学基を表わし、
Ｔは、単結合、非置換又は置換の直鎖のＣ_１〜Ｃ_１６アルキルを表わし、
ここで、^＊は、ポリマー骨格への結合部位を指す］
と、式（ＩＩ）

［式中、
Ｅ_１は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＲ^８−、−ＮＲ^８ＣＯ−、−ＣＯＮＲ^８−、−ＮＲ^８ＣＯＯ−、−ＯＣＯＮＲ^８−、−ＮＲ^８ＣＯＮＲ^８−、−Ｃ＝Ｃ−、−Ｃ≡Ｃ−、−Ｏ−ＣＯＯ−からなる群より選択される架橋基であり、ここで、Ｒ^８は、水素原子又は低級アルキルであり、
好ましくは、架橋基は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−Ｃ＝Ｃ−、−Ｃ≡Ｃ−、−Ｏ−ＣＯＯ−から選択される。より好ましくは、架橋基は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＯＯＣ−から選択され、
Ｓ_３は、単結合、非置換又はシアノもしくはハロゲンにより置換されている直鎖又は分岐鎖のＣ_１〜Ｃ_２４アルキレン、好ましくは、１〜１６個、より好ましくは１〜１２個の炭素原子からなる群より選択されるスペーサ基であり、ここで、１つ以上のＣＨ_２基は、それぞれ独立して、ヘテロ原子又は−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＲ^８−、−ＮＲ^８ＣＯ−、−ＣＯＮＲ^８−、−ＮＲ^８ＣＯＯ−、−ＯＣＯＮＲ^８−、−ＮＲ^８ＣＯＮＲ^８−、−Ｃ＝Ｃ−、−Ｃ≡Ｃ−、−Ｏ−ＣＯＯ−からなる群より選択される基により置き換えられていることができ、ここで、Ｒ^８は、水素原子又は低級アルキルである。より好ましくは、１つ以上のＣＨ_２基は、ヘテロ原子又は−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−Ｃ＝Ｃ−、−Ｃ≡Ｃ−、−Ｏ−ＣＯＯ−からなる群より選択される基により置き換えられており、最も好ましくは、１つのＣＨ_２基は、ヘテロ原子により置換されており、更により好ましくは、１つのＣＨ_２基は、酸素により置換されており、
Ｙ_１及びＸ_１は、それぞれ独立して、シアノ又はハロゲンのいずれかであり、
Ａｒ_１及びＡｒ_２は、それぞれ独立して、５〜４０個の原子の環系を表わし、ここで、各環系は、電子共役（π−π結合）を介して式（ＩＩ）の二重結合に直接結合している少なくとも１つの不飽和を含み
環系は、非置換又はハロゲン原子、ヒドロキシル基及び／もしくは極性基、例えば、ニトロ、ニトリルもしくはカルボキシ基並びに／又は１〜３０個の炭素原子を有する環状、直鎖もしくは分岐鎖のアルキル残基により一置換もしくは多置換されていることができ、同アルキル残基は、置換されていないか、メチル、フッ素及び／又は塩素により一置換され又は多置換されており、ここで、１つ以上、好ましくは、隣接していない−ＣＨ_２−基は、−Ｏ−、−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−ＮＲ^９−、−ＮＲ^９−ＣＯ−、−ＣＯ−ＮＲ^９−、−ＮＲ^９−ＣＯ−Ｏ−、−Ｏ−ＣＯ−ＮＲ^９−、−ＮＲ^９−ＣＯ−、ＮＲ−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−Ｏ−ＣＯ−Ｏ−及び−Ｓｉ（ＣＨ_３）_２−Ｏ−Ｓｉ（ＣＨ_３）_２−、芳香族又は脂環式基から選択される基により独立して置き換えられていることができ、ここで、Ｒ^９は、水素原子又は低級アルキル及び／もしくは１〜２０個の炭素原子、好ましくは、１〜１０個の炭素原子を有するアクリロイルオキシ、アルコキシ、アルキルカルボニルオキシ、アルキルオキソカルボニルオキシ、メタクリロイルオキシ、ビニル、アリル、ビニルオキシ及び／もしくはアリルオキシ基であり、
Ｒ_１、Ｒ_２、Ｒ_３及びＲ_４は、それぞれ独立して、水素、Ｃ_１〜Ｃ_１２アルコキシ、ハロゲン、直鎖又は分岐鎖のハロゲンにより置換されている又は非置換のＣ_１〜Ｃ_２４アルキル、ニトリルであり、あるいは
Ｒ_１及びＲ_４は、水素であり、Ｒ_２及びＲ_３は共に、Ａｒ_２環に縮合している電子供与環の残り部分を形成しており、
Ｒ_５、Ｒ_６及びＲ_７は、それぞれ独立して、水素、Ｃ_１〜Ｃ_１２アルコキシ、ハロゲン、直鎖もしくは分岐鎖のハロゲンにより置換されている又は非置換のＣ_１〜Ｃ_２４アルキル、ニトリル又は電子供与性の単一置換基であり、あるいは
Ｒ_５及びＲ_６は共に、Ａｒ_１環に縮合している電子供与環の残り部分を形成しており、
ｎ_５及びｎ_６は、それぞれ独立して、０〜２の整数を表わし、
^＊は、ポリマー骨格への結合部位を指す］
で示される側鎖を有する第２のモノマー：そして
ポリマー骨格は、ポリシロキサンである。

[Where:
n ₀ is an integer from 0 to 4, preferably 0 to 2, even more preferably 0 to 1,
n ₁ is an integer from ₀ to 15, preferably 1 to 10, more preferably 1 to 8, more preferably 1 to 5, most preferably 1 to 3, most preferably n ₁ is 1. ,
n ₂ is an integer from 0 to 15, preferably 1 to 10, more preferably 1 to 8, more preferably 1 to 5, most preferably 1 to 3, most preferably n ₂ is 1. ,
n ₃ is an integer of 1 to 15, preferably 1 to 10, more preferably 1 to 8, more preferably 1 to 5, most preferably 1 to 3, most preferably n ₃ is 1. ,
X and Y each independently represent H, F, Cl, or CN;
S ₂ is cyclic, aromatic, linear or branched, substituted or unsubstituted C ₁ -C ₂₄ alkylene, especially C ₁ -C ₁₂ alkylene, especially C ₁ -C ₈ alkylene, especially C _1- C ₆ alkylene, especially C ₁ -C ₄ alkylene, especially C ₁ -C ₂ alkylene, in which one or more —C—, —CH—, —CH ₂ — groups are represented by a linking group Where two or more —C—, —CH—, —CH ₂ — groups are replaced, the linking groups can be the same or different;
E represents O, S, NH, C (C ₁ -C ₆ alkyl), NR ¹² , OC, OOC, OCONH, OCONR ⁴ , SCS, SC, wherein R ¹² is cyclic, linear or branched A chain substituted or unsubstituted C ₁ -C ₂₄ alkyl, wherein one or more —C—, —CH—, —CH ₂ — groups are each independently replaced by a linking group. Or, preferably, E is selected from the group consisting of -O-, -CO-, -COO-, -OCO-, -OOC-, S or NH;
A represents a halogen or a substituted or unsubstituted _C 1 _{-C 24} alkyl, substituted or unsubstituted _C 1 _{-C 24} alkenyl, a _C 1 _{-C 24} alkynyl, or carboxylic acid substituted or unsubstituted, where 1 Two or more —C—, —CH—, —CH ₂ — groups may each independently be replaced by a heteroatom, preferably A is halogen, H or C ₁ -C ₂₄ alkoxy. or a carboxylic acid, most preferably, _{a, H, F, C 1 ~C} 6 _alkyl, C 1 -C ₆ alkoxy or carboxylic acids,
Z ₂ represents a chemical group having delocalization of its electron density and / or inducing delocalization of its adjacent electron density,
T represents a single bond, unsubstituted or substituted linear C ₁ -C ₁₆ alkyl,
Here, ^* indicates a bonding site to the polymer backbone]
And formula (II)

[Where:
E ₁ represents —O—, —CO—, —COO—, —OCO—, —NR ⁸ —, —NR ⁸ CO—, —CONR ⁸ —, —NR ⁸ COO—, —OCONR ⁸ —, —NR ^8. CONR ⁸ —, —C═C—, —C≡C—, —O—COO—, which is a bridging group, wherein R ⁸ is a hydrogen atom or lower alkyl;
Preferably, the bridging group is selected from —O—, —CO—, —COO—, —OCO—, —C═C—, —C≡C—, —O—COO—. More preferably, the bridging group is selected from -O-, -CO-, -COO-, -OCO-, -OOC-,
S ₃ is a single bond, unsubstituted or straight or branched C ₁ -C ₂₄ alkylene substituted by cyano or halogen, preferably from 1 to 16, more preferably from 1 to 12 carbon atoms. A spacer group selected from the group consisting of one or more CH ₂ groups each independently a heteroatom or —O—, —CO—, —COO—, —OCO—, —NR ^8. —, —NR ⁸ CO—, —CONR ⁸ —, —NR ⁸ COO—, —OCONR ⁸ —, —NR ⁸ CONR ⁸ —, —C═C—, —C≡C—, —O—COO— It can be replaced by a group selected from the group, wherein R ⁸ is a hydrogen atom or lower alkyl. More preferably, one or more CH ₂ groups are from a heteroatom or —O—, —CO—, —COO—, —OCO—, —C═C—, —C≡C—, —O—COO—. Most preferably one CH ₂ group is substituted by a heteroatom, and even more preferably one CH ₂ group is substituted by oxygen. ,
Y ₁ and X ₁ are each independently either cyano or halogen;
Ar ₁ and Ar ₂ each independently represent a ring system of 5 to 40 atoms, wherein each ring system is a double of formula (II) via electron conjugation (π-π bond). The ring system containing at least one unsaturation directly attached to the bond may be unsubstituted or halogen atoms, hydroxyl groups and / or polar groups such as nitro, nitrile or carboxy groups and / or 1 to 30 carbon atoms Can be mono- or poly-substituted by cyclic, straight-chain or branched alkyl residues having the same, the alkyl residues are unsubstituted, mono-substituted by methyl, fluorine and / or chlorine or Polysubstituted, wherein one or more, preferably non-adjacent —CH ₂ — groups are —O—, —CO—, —CO—O—, —O—CO—, —NR ^{9. -,} - NR 9 ^{-CO-, -CO-NR 9 -, - NR} 9 -CO-O -, - O-CO-NR 9 -, - NR 9 -CO-, NR -, - CH = CH -, - C≡C -, - O- CO—O— and —Si (CH ₃ ) ₂ —O—Si (CH ₃ ) ₂ — can be independently replaced by a group selected from aromatic or alicyclic groups, where R ⁹ represents a hydrogen atom or lower alkyl and / or acryloyloxy, alkoxy, alkylcarbonyloxy, alkyloxocarbonyloxy, methacryloyloxy, vinyl having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Allyl, vinyloxy and / or allyloxy groups,
R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogenated, C ₁ -C ₁₂ alkoxy, halogen, linear or branched halogen substituted or unsubstituted C ₁ -C _24. Alkyl, nitrile, or R ₁ and R ₄ are hydrogen and R ₂ and R ₃ together form the remainder of the electron donor ring fused to the Ar ₂ ring;
R ₅ , R ₆ and R ₇ are each independently hydrogen, C ₁ -C ₁₂ alkoxy, halogen, substituted or unsubstituted C ₁ -C ₂₄ alkyl, nitrile, halogen, straight or branched halogen Or an electron-donating single substituent, or R ₅ and R ₆ together form the remainder of the electron-donating ring fused to the Ar ₁ ring;
n ₅ and n ₆ each independently represents an integer of 0 to 2,
^{* Indicates} the binding site to the polymer backbone]
A second monomer having a side chain represented by: and the polymer backbone is a polysiloxane.

  In the context of the present invention, the term “copolymer” refers to a polymer having a polymer backbone, where the polymer backbone can be the same or different, where the side chains of the copolymer are different. The copolymer of the present invention comprises at least one first monomer having a side chain represented by formula (I) and a second monomer having a side chain represented by formula (II) or formula (III). The copolymers of the present invention can be linear, branched or crosslinked. The term copolymer also has the meaning of a co-oligomer.

  The copolymers of the various non-limiting embodiments herein are alternating copolymers in polymer or oligomer form, periodic copolymers, random copolymers, statistical copolymers, block copolymers, graft copolymers, linear copolymers, gradient copolymers, branched copolymers, high copolymers. It can have branched copolymers, dendritic copolymers, star copolymers, brush copolymers and comb copolymers. The copolymers of the present invention can have the same or different polymer backbones. In a preferred embodiment, the copolymers of the present invention have the same polymer backbone and the monomers differ in their side chains. In a preferred embodiment, the copolymer of the present invention comprises at least one first monomer having a side chain of formula (I) and at least one first chain having a side chain of formula (II) or (III). 2 monomers. The order and configuration of the side chains are not limited to any preferred embodiment. Thus, the copolymer can have polymer chains having only monomers having side chains of formula (I), these chains being monomers having side chains of formula (II) or formula (III) Are linked to other chains with only These connections or forms can be as defined above. Alternatively, the copolymer of the present invention can have at least one monomer having a side chain represented by formula (I) and at least one monomer having a side chain represented by formula (II) or (III). Here, the monomers are randomly arranged. In certain non-limiting embodiments, the copolymer can include polymer chains, where different sections can have different forms, such as random polymer sections and block polymer sections. Formation of a copolymer having one or more mentioned forms can be achieved using polymerization methods known in the art. Polymerization methods include addition polymerization, step growth polymerization, condensation polymerization, controlled living polymerization, anionic polymerization, cationic polymerization, photopolymerization, radical polymerization, reversible addition-fragmentation chain transfer polymerization (RAFT) and metathesis polymerization. It is not limited to.

As used in the context of the present invention, the term “linking group” is preferably an unsubstituted or substituted alicyclic group, preferably cyclohexylene or an unsubstituted or substituted aromatic group, a single bond, heterocycle. Atoms, cationic hydrocarbon groups, such as -depending- (C +)-, -O-, -CO, -arylene-, -CO-O-, -O-CO-, -N =, -CN, -NR ^10- , -NR ¹⁰ -CO-, -CO-NR ^10- , -NR ¹⁰ -CO-O-, -O-CO-NR ^10- , -NR ¹⁰ -CO-NR ^10- , -CH = CH- , —C≡C—, —O—CO—O— and —Si (CH ₃ ) ₂ —O—Si (CH ₃ ) ₂ —, wherein
R ¹⁰ represents a hydrogen atom or C ₁ -C ₆ alkyl,
However, it is a condition that the oxygen atoms of the linking group are not directly connected to each other.

The substituted alicyclic or aromatic substituent on the linking group can be one or more, preferably halogen, such as fluoro, chloro, bromo, iodo, and preferably fluoro and / or chloro, preferably by arrangement, fluoro or C ₁ -C ₆ alkoxy, for example, preferably, methoxy or trifluoromethyl.

The term “each ring system contains at least one unsaturation bonded directly to a double bond via electron conjugation (π-π bond)” means that each ring system Ar ₁ and Ar ₂ has at least one It is understood to indicate that it contains an unsaturated bond, ie, a double bond that extends electronic conjugation by linking directly to the double bond in formula (II).

In a preferred embodiment, the ring systems Ar ₁ and Ar ₂ are monocyclic with 4-6 atoms or at least two adjacent monocycles with 5 or 6 atoms, 8, 9 or 10 fused bicyclic systems. Or a carbocyclic or heterocyclic group selected from a fused tricyclic system of 13 or 14 atoms.

More preferably, the ring systems Ar ₁ and Ar ₂ are selected from pyrimidine, pyridine, thiophenylene, furanylene, phenanthrylene, naphthylene or phenylene.

More preferably, the ring system Ar ₁ is pyrimidine, pyridine, pyridine cation, thiophenylene, furanylene, phenanthrylene, 9,10-dihydrophenanthrylene, pyrene, naphthylene, 9H-fluorene, 9H-fluoren-9-one, 9 , 9-dimethyl-9H-fluorene or phenylene, wherein A1 is cyclohexane, cyclohexene, cyclohexadiene, pyrimidine, pyridine, thiophenylene, furanylene, phenanthrylene, naphthylene or phenylene or a steroid skeleton or rod-shaped adjacent aromatic and And / or selected from aromatic / alicyclic groups.

で示される環系であり、
Ａｒ_２は、式（Ｖ）：

で示される環系であり、
式中、
Ｃ^１、Ｃ^２は、それぞれ独立して、置換もしくは非置換の３〜４０個の原子の非芳香族又は芳香族、場合により置換されている５〜１４個の原子の炭素環基もしくは複素環基（好ましくは、架橋基Ｚ^１及びＺ^２を介して対向位置で互いに連結している）であり、ここで、置換Ｃ^１、Ｃ^２の置換基は、環Ａｒ_１についてのＲ^５、Ｒ^６又はＲ^７及び環Ａｒ_２についてのＲ^１、Ｒ^２、Ｒ^３又はＲ^４であり、
Ｚ^３、Ｚ^４は、それぞれ独立して、単結合又は−ＣＨ（ＯＨ）−、−Ｏ−、−ＣＨ_２（ＣＯ）−、−ＳＯ−、−ＣＨ_２（ＳＯ）−、−ＳＯ_２−、−ＣＨ_２（ＳＯ_２）−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＦ_２−、−ＣＦ_２ＣＯ−、−Ｓ−ＣＯ−、−ＣＯ−Ｓ−、−ＳＯＯ−、−ＯＳＯ−、−ＣＨ_２−ＣＨ_２−、−Ｏ−ＣＨ_２−、−ＣＨ_２Ｏ−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｓ−、−ＳＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＨ＝Ｎ−、−Ｃ（ＣＨ_３）＝Ｎ−、−Ｏ−ＣＯ−Ｏ−、−Ｎ＝Ｎ−もしくは１〜６個の炭素原子、好ましくは、１〜３個の炭素原子の短いアルキルスペーサから選択される基であり、
ａは、０、１、２又は３であり、好ましくは、ａは、０又は１、より好ましくは、０であり、
ただし、二重結合に直接連結しているＣ^２は、不飽和かつそれにコンジュゲートしているという条件である。 In a still further embodiment,
Ar ₁ is represented by formula (IV):

A ring system represented by
Ar ₂ represents formula (V):

A ring system represented by
Where
C ¹ and C ² are each independently a substituted or unsubstituted 3 to 40 atom non-aromatic or aromatic, optionally substituted carbocyclic group or heterocyclic ring of 5 to 14 atoms. A group (preferably linked to each other at opposite positions via bridging groups Z ¹ and Z ² ), wherein the substituents of the substituted C ¹ , C ² are R ⁵ , R for the ring Ar ₁ R ¹ , R ² , R ³ or R ⁴ for ⁶ or R ⁷ and the ring Ar ₂ ,
Z ³ and Z ⁴ are each independently a single bond or —CH (OH) —, —O—, —CH ₂ (CO) —, —SO—, —CH ₂ (SO) —, —SO ₂ —. , —CH ₂ (SO ₂ ) —, —COO—, —OCO—, —COF ₂ —, —CF ₂ CO—, —S—CO—, —CO—S—, —SOO—, —OSO—, — CH ₂ —CH ₂ —, —O—CH ₂ —, —CH ₂ O—, —CH═CH—, —C≡S—, —SH═CH—COO—, —OCO—CH═CH—, —CH _{= N -, - C (CH} 3) = N -, - O-CO-O -, - N = N- or 6 carbon atoms, preferably, short alkyl spacer of 1 to 3 carbon atoms A group selected from
a is 0, 1, 2 or 3, preferably a is 0 or 1, more preferably 0;
Provided that C ² directly linked to the double bond is unsaturated and conjugated to it.

The term “linked to each other in opposite positions via bridging groups Z ³ and Z ⁴ ” means that the 5- and 6-membered rings are preferably bonded in the 1,3- or 1,4-position. , Which means that the adjacent 1,2-positions are not bonded. Similar binding patterns in others, eg, higher number of rings, will be apparent to those skilled in the art.

を有する。 Ring system Ar ₂ has a structure similar to ring system Ar _{1 of} formula (IV), except that group Ar ₂ has a terminal group. Thus, at a = 0, the group C ² represents a terminal group, and at a> 0, the group C ¹ is linked via a bridging group Z ⁴ , where the final group C ¹ is Is a terminal group. Thus, at a = 1, the ring system A ² is

Have

を有する。 Similarly, in a = 2 or 3, the ring system ^{A 2} is represented by the following formula

Have

［式中、
Ｌは、ハロゲン、ヒドロキシル及び／又は極性基、例えば、ニトリル、シアノもしくはカルボキシ及び／又はアクリロイルオキシ、アルコキシ、例えば、メトキシ、エトキシ、プロポキシ、アルキルカルボニルオキシ、アルキルオキソカルボニルオキシ、メタクリロイルオキシ、ビニル、ビニルオキシ、アリル、アリルオキシ並びに（又は環状、直鎖もしくは分岐鎖のアルキル残基であり、同アルキル残基は、非置換、フッ素及び／もしくは塩素並びに／又はシラン基及び／もしくはシロキサン基により一置換又は多置換されており、ここで、アルキル残基は、１〜２０個のＣ原子を有し、ここで、１つ以上、好ましくは、隣接していないＣＨ２基は、−Ｏ−、−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−Ｏ−ＣＯ−Ｏ−、−Ｓｉ（ＣＨ_３）_２−Ｏ−Ｓｉ（ＣＨ_３）_２−から選択される基により独立して置き換えられ、好ましくは、Ｌは、メトキシ、ハロゲン、ＣＦ_３又は水素であり、
ｕ１は、０、１、２、３又は４であり、
ｕ２は、０、１、２又は３であり、
ｕ３は、０、１又は２であり、
ただし、二重結合に直接連結しているＣ^２は、不飽和かつそれにコンジュゲートしているという条件である］
のうちの１つを有する。 Preferably, C ¹ and C ² in formulas (IV) and (V) each independently have the following meanings:

[Where:
L is a halogen, hydroxyl and / or polar group such as nitrile, cyano or carboxy and / or acryloyloxy, alkoxy such as methoxy, ethoxy, propoxy, alkylcarbonyloxy, alkyloxocarbonyloxy, methacryloyloxy, vinyl, vinyloxy Allyl, allyloxy and (or cyclic, linear or branched alkyl residues which are monosubstituted or polysubstituted by unsubstituted, fluorine and / or chlorine and / or silane and / or siloxane groups. Substituted, wherein the alkyl residue has 1 to 20 C atoms, wherein one or more, preferably non-adjacent CH 2 groups are —O—, —CO—, —CO—O—, —O—CO—, —CH═CH—, —C≡C—, —O—. _{O-O -, - Si (} CH 3) 2 -O-Si (CH 3) 2 - replaced independently by a group selected from, preferably, L is methoxy, halogen, CF ₃ or hydrogen ,
u1 is 0, 1, 2, 3 or 4;
u2 is 0, 1, 2 or 3,
u3 is 0, 1 or 2;
Provided that the C ² directly linked to the double bond is unsaturated and conjugated to it]
One of them.

More preferably, C ¹ and C ² are phenanthryl, phenanthrylene, biphenyl, biphenylene, naphthyl, naphthylene, cyclohexyl, cyclohexylene, phenyl or phenylene, pyridine, pyridinylene; preferably naphthyl or naphthylene, phenyl or phenylene, pyridine or Pyridinylene.

Preferably, Z ³ and Z ⁴ in formulas (IV) and (V) are each independently a single bond, most preferably —CH (OH) —, —O—, —CH ₂ (CO) —, — _{COO -, - OCO -, -} COF 2 -, - CF 2 CO -, - CH 2 -CH 2 -, - O-CH 2 -, - CH 2 O -, - CH = CH -, - OCO-CH = CH—, —CH═N—, —C (CH ₃ ) ═N—, —O—CO—O—, —N═N— or 1 to 6 carbon atoms, preferably 1 to 3 carbons. It is a bridging group selected from alkyl short spacers.

More ^preferably, Z 3, ^{Z 4} are each independently a single _{bond, -O -, - CH 2 (} CO) -, - COO -, - OCO -, - CH 2 -CH 2 -, - OCO- CH = CH-, -N = N-, or a short alkyl spacer of 1 to 3 carbon atoms.

In the context of the present invention, the electron donor ring fused to the ring Ar ₂ is preferably unsubstituted or substituted —X ² -C ₁ -C ₂₄ alkylene- (X ³ ) _{0 or 1-} , or in particular, Unsaturated or saturated —X ² —C ₂ -C ₂₄ alkylene- (X ³ ) _{0 or 1} —, wherein X ² and X ³ are each independently a single bond, —O—, — S—, Se, —N—, —NH— and —NR ₁₁ , wherein R ₁₁ is a hydrogen atom or a straight chain having 1 to 12, more preferably 1 to 6 carbon atoms. A chain or branched alkyl or alkylene group, wherein one or more, preferably non-adjacent —CH ₂ — groups, are independently unsubstituted or preferably —O -, -CO-, -CO-O-, -O-C Can be replaced by a linking group selected from O—, —CH═CH—, —C≡C—, more preferably R ₁₁ is a hydrogen atom or methyl, or preferably R _11. Is optionally substituted C ₁ -C ₆ alkyl, more preferably R ₁₁ is hydrogen, and within the above given selection, where it is substituted -X ² -C ₁ -C ₂₄ alkylene - ^(X 3) _{0 or 1} - is _preferably, C 1 -C ₆ alkyl, e.g., methyl or ethyl, which _replaces the C 1 _{-C 24} alkylene position. Preferred X ² and X ³ are the same, more preferably X ² and X ³ are —O—. Further preferred ^-X 2 _-C 1 _{-C 24} alkylene - ^(X 3) _{0 or 1} - ^is, -X ₂ -C 1 _{-C 12} alkylene - ^(X 3) _{0 or 1} -, more preferably, -X ² -C ₁ -C ₆ alkylene - ^(X 3) _{0 or 1} -, and most ^preferably, -X 2 _-C 1 -C ₃ alkylene - ^(X 3) _{0 or 1} -, in particular, 1,3-propylene, 1,2-ethylene, _{methylene, -CH (CH 3) CH (} CH 3) -, - CH 2 CH (CH 3) CH 2 - is. More preferable X ² and X ³ are the same, and —O-propylene-O—, —O-ethylene-O—, —ethylene-O—, —O-methylene-O—, —OCH (CH ₃ ) CH ( CH ₃ ) —O—, —O—CH ₂ CH (CH ₃ ) CH ₂ —O—.

In the context of the present invention, the term “electron-donating single substituent” is preferably the group C ₁ -C ₂₄ alkyl, preferably methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert- butyl, pentyl, isopentyl, hexyl, isohexyl; or ^-X 4 _-C 1 _{~C 24} alkyl, ^preferably, -X _{4 -C} 1 ~C ₁₂ alkyl, more ^preferably, -X 4 _-C 1 _{~C 6} alkyl , Most preferably -X ⁴ -C ₁ -C ₃ alkyl, wherein X ⁴ is a single bond, -O-, -S-, Se, -N-, -NH- and -NR ₁₁ , preferably , —O—, wherein R ₁₁ is as described above and is within the given selection above; preferably —O-methyl, —O-ethyl, —O-propyl, — O-isopropyl,- O- butyl, -O-sec-butyl, -O-tert-butyl, -O- pentyl, -O- isopentyl, -O- hexyl or -O- isohexyl; or ^-X 4 _-C 1 _{~C 24} alkylene - Selected from aryl, preferably —O-benzylene, —O-methylene-phenyl, —O-ethylene-phenyl; or —O—CF ₃ , provided that in the residue C ₁ -C ₂₄ alkyl one or more The condition is that the C atom, CH— and CH ₂ group can be replaced by a linking group. Preferred _C 1 _{-C 24} alkyl _residue, C 1 _{-C 12} alkyl, more _preferably a C 1 -C ₆ alkyl, methyl, ethyl, propyl, isopropyl, butyl, tert- butyl, sec- butyl, isopentyl , Pentyl, hexyl or isohexyl are more preferred, and methyl and ethyl are most preferred. The most preferred electron donating single substituents are methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, —O—CF ₃ , —O-benzylene, —O-methylene-phenyl, —O. -Methyl, -O-ethyl, -O-propyl, -S-methyl, -S-ethyl, -S-propyl, -NR < ₁₁ > -methyl, -NR < ₁₁ > -ethyl, -NR < ₁₁ > -propyl (wherein R ₁₁ is hydrogen or methyl).

  In the context of the present invention, the term “polysiloxane” means any polymer, copolymer or oligomer comprising functional groups with Si—O—Si bonds. The polysiloxanes of the present invention can be linear, branched or cross-linked. Polysiloxanes are synthesized by methods well known in the art.

［式中、
Ｒ_ａは、ＯＨ、Ｃｌ、１〜２０個の炭素を有する、置換又は非置換のアルコキシ基、１〜２０個の炭素を有するアルキル基又は１〜２０個の炭素を有するアリール基を表わし、
Ｓ_１は、単結合又は直鎖もしくは分岐鎖で置換もしくは非置換のＣ_１〜Ｃ_２４アルキレン、特に、Ｃ_１〜Ｃ_１２アルキレン、とりわけ、Ｃ_１〜Ｃ_８アルキレン、とりわけ、Ｃ_１〜Ｃ_６アルキレン、とりわけ、Ｃ_１〜Ｃ_４アルキレン、とりわけ、Ｃ_１〜Ｃ_２アルキレンを表わし、同アルキレンにおいて、１つ以上の−Ｃ−、−ＣＨ−、ＣＨ_２−基は、連結基により置き換えられていることができ、
ｚは、０〜１５、好ましくは１〜１０、より好ましくは１〜８、より好ましくは１〜５、更により好ましくは、１〜３の整数であり、最も好ましくは、ｎは、１であり、
Ｚ_１は、単結合又は置換もしくは非置換のＣ_３〜Ｃ_１２、より好ましくは、Ｃ_３〜Ｃ_１０、更により好ましくは、Ｃ_５〜Ｃ_８、最も好ましくは、Ｃ_５〜Ｃ_６の脂肪族もしくは脂環式基を表わし、
Ｒ_０は、ＯＨ、Ｃｌ、１〜２０個の炭素を有する、直鎖又は分岐鎖で置換又は非置換のアルコキシ基を表わし、同アルコキシ基において、−Ｃ−、−ＣＨ−、−ＣＨ_２−は、非置換又は置換のＣ_６〜Ｃ_２０アリール基により置き換えられていることができ、
ここで、^＊は、側鎖への付着部位を指す］
で示されるモノマーを含むポリシロキサン骨格である。 More preferably, the formula

[Where:
R _a represents OH, Cl, a substituted or unsubstituted alkoxy group having 1 to 20 carbons, an alkyl group having 1 to 20 carbons or an aryl group having 1 to 20 carbons;
S ₁ is a single bond or a linear or branched substituted or unsubstituted C ₁ -C ₂₄ alkylene, especially C ₁ -C ₁₂ alkylene, especially C ₁ -C ₈ alkylene, especially C ₁ -C _6. alkylene, _especially, C 1 -C ₄ alkylene, _especially, represents a C 1 -C ₂ alkylene, in the alkylene, one or more _{-C -, - CH-, CH 2} - group is replaced by a linking group Can be
z is an integer from 0 to 15, preferably from 1 to 10, more preferably from 1 to 8, more preferably from 1 to 5, even more preferably from 1 to 3, and most preferably n is 1. ,
Z ₁ is a single bond or substituted or unsubstituted C ₃ -C ₁₂ , more preferably C ₃ -C ₁₀ , still more preferably C ₅ -C ₈ , most preferably C ₅ -C ₆ fat. Represents an alicyclic or alicyclic group,
R ₀ represents OH, Cl, a linear or branched, substituted or unsubstituted alkoxy group having 1 to 20 carbons, in which —C—, —CH—, —CH ₂ — may be replaced by C ₆ -C ₂₀ aryl group unsubstituted or substituted,
Where ^* indicates the site of attachment to the side chain]
A polysiloxane skeleton containing a monomer represented by

Formula (VI) (wherein Z ₁ represents a substituted or unsubstituted C _{5 to} C ₆ alicyclic group, and S ₁ represents a substituted or unsubstituted C _{1 to} C ₂₄ linear alkyl) Polysiloxanes having a skeleton containing the monomers shown are preferred. A polymer comprising a monomer represented by the formula (VI) (wherein Z ₁ represents a substituted or unsubstituted cyclohexanol group or a substituted or unsubstituted cyclohexane ether group, and S ₁ represents an ethyl group) Polysiloxane having a skeleton is more preferable.

  The polysiloxane skeleton containing the monomer of formula (VI) is a polymer chain that can be linear, branched or crosslinked. This polymer chain is substituted at least once by the side chain represented by formula (I) and at least once by the side chain represented by formula (II) or (III). At least one monomer of the polysiloxane skeleton containing the monomer represented by the formula (VI) is substituted with a side chain represented by the formula (I), and at least another polysiloxane skeleton containing the monomer represented by the formula (VI) is substituted. As long as the monomer of (II) is substituted by the side chain represented by formula (II) or (III), all the siloxane monomers of the polysiloxane skeleton including the monomer represented by formula (VI) are substituted by the side chain. There is no need.

  In the copolymers of the present invention, the polymer backbone can comprise the same or different polymer backbone comprising the monomer of formula (VI).

In the context of the present invention, the term “alkyl” includes straight-chain and branched-chain alkyl and saturated and unsaturated groups. The term “alkyl” means unsubstituted or substituted alkyl. Here, substituted alkyl also means alkylene. When used in the context of the present invention, alkyl, alkyloxy, alkoxy, alkylcarbonyloxy, acryloyloxyalkoxy, acryloyloxyalkyl, acryloyloxyalkene, alkyloxycarbonyloxy, alkylacryloyloxy, methacryloyloxyalkoxy, methacryloyloxyalkyl, methacryloyl Oxyalkene, alkylmethacryloyloxy, alkylmethacryloyloxy, alkylvinyl, alkylvinyloxy and alkylallyloxy, and alkylene are substituted or unsubstituted alkyl residues, cyclic alkylene, linear or branched, respectively. Alkyl, each referring to alkylene. In the same alkylene, one or more, preferably non-adjacent —C—, —CH— or —CH ₂ — groups can be unsubstituted or replaced by a linking group, preferably It can be replaced by -O-, NH, -COO, OCO.

Further, in the context of the present invention, “alkyl” is branched or straight chain, unsubstituted or substituted alkyl, preferably C ₁ -C ₄₀ alkyl, in particular C ₁ -C ₃₀ alkyl, preferably C _{1 to} C ₂₀ alkyl, more preferably C _{1 to} C ₁₆ alkyl, most preferably C _{1 to} C ₁₀ alkyl, and most preferably C _{1 to} C ₆ alkyl. Thus, alkylene, _e.g., C 1 _{-C 40} alkylene, in _particular, C 1 _{-C 30} alkylene, _preferably, C 1 _{-C 20} alkylene, more _preferably, C 1 _{-C 16} alkylene, and most preferably, _{C 1} -C ₁₀ alkylene, and particularly most _preferably C 1 -C ₆ alkylene. In the context of the present invention, the definitions for alkyl given below are equally applicable to alkylene.

C ₁ -C ₆ alkyl is, for example, methyl, ethyl, propyl, isopropyl, butyl, sec- butyl, tert- butyl, pentyl or hexyl.

C ₁ -C ₁₀ alkyl is, for example, methyl, ethyl, propyl, isopropyl, butyl, sec- butyl, tert- butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl.

C ₁ -C ₁₆ alkyl is, for example, methyl, ethyl, propyl, isopropyl, butyl, sec- butyl, heptyl tert- butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl Or hexadecyl.

C ₁ -C ₂₀ alkyl is, for example, methyl, ethyl, propyl, isopropyl, butyl, sec- butyl, heptyl tert- butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl Hexadecyl, heptadecyl, octadecyl, nanodecyl, and eicosyl.

C ₁ -C ₂₄ alkyl is, for example, methyl, ethyl, propyl, isopropyl, butyl, sec- butyl, heptyl tert- butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl Hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl.

C ₁ -C ₃₀ alkyl is, for example, methyl, ethyl, propyl, isopropyl, butyl, sec- butyl, heptyl tert- butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl , Hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, henecosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl or triacontyl.

C ₁ -C ₄₀ alkyl is, for example, methyl, ethyl, propyl, isopropyl, butyl, sec- butyl, heptyl tert- butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl , Hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl or tetracontyl.

C ₁ -C ₆ alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec- butoxy, tert- butoxy, pentoxy or hexoxy.

C ₁ -C ₂₀ acryloyloxy alkylene, _preferably, C 1 _{-C 10} acryloyloxy _alkylene, C 1 -C ₆ acryloyloxy alkylene is, for example, acryloyloxy methylene, acryloyloxy ethylene, acryloyloxy propylene, acryloyloxy isopropylene, Acryloyloxybutylene, acryloyloxy-sec-butylene, acryloyloxypentylene, acryloyloxyhexylene, acryloyloxyheptylene, acryloyloxyoctylene, acryloyloxynonylene, acryloyloxydecylene, acryloyloxyundecylene, acryloyloxidedecane, acryloyloxidedecane Oxytridecylene, acryloyloxytetradecylene, acryloyloxypentyl Kang, acryloyloxy hexa de cyclohexylene, acryloyloxy hepta de cyclohexylene, acryloyloxy octadecylene, acryloyloxy Roh stroked Shiren, a acryloyloxy Eiko cyclohexylene.

C ₁ -C ₂₀ methacryloyloxy alkylene, preferably, C ₁ -C ₁₀ methacryloyloxy alkylene, C ₁ -C ₆ methacryloyloxy alkylene is, for example, methacryloyloxy methylene, methacryloyloxyethylene, methacryloyloxy propylene, methacryloyloxy isopropylene, Methacryloyloxybutylene, methacryloyloxy-sec-butylene, methacryloyloxypentylene, methacryloyloxyhexylene, methacryloyloxyheptylene, methacryloyloxyoctylene, methacryloyloxynonylene, methacryloyloxydecylene, methacryloyloxyundecylene, methacryloyloxidedecane Oxytridecylene, methacryloyloxytate Decylene, methacryloyloxy pentyl decane, methacryloyloxy hexadecene cyclohexylene, methacryloyloxy hept decylene, methacryloyloxy octadecylene, methacryloyloxy Bruno stroked cyclohexylene, a methacryloyloxy Eiko cyclohexylene.

C ₁ -C ₂₀ acryloyloxy alkoxy, preferably, C ₁ -C ₁₀ acryloyloxy alkoxy, C ₁ -C ₆ acryloyloxy alkoxy is, for example, acryloyloxy methoxy, acryloyloxy ethoxy, acryloyloxy propoxy, acryloyloxy-isopropoxy, Acryloyloxybutoxy, acryloyloxy-sec-butoxy, acryloyloxypentoxy, acryloyloxyhexoxy, acryloyloxyheptoxy, acryloyloxyoctoxy, acryloyloxynonoxy, acryloyloxydecoxy, acryloyloxyundecoxy, acryloyloxide deca Noxy, acryloyloxytridecyloxy.

C ₁ -C ₂₀ methacryloyloxy alkoxy, preferably, C ₁ -C ₁₀ methacryloyloxy alkoxy, C ₁ -C ₆ methacryloyloxy alkoxy is, for example, methacryloyloxy methoxy, methacryloyloxy ethoxy, methacryloyloxy propoxy, methacryloyloxy-isopropoxy, Methacryloyloxybutoxy, methacryloyloxy-sec-butoxy, methacryloyloxypentoxy, methacryloyloxyhexoxy, methacryloyloxyheptoxy, methacryloyloxyoctoxy, methacryloyloxynonoxy, methacryloyloxydecoxy, methacryloyloxyundecoxy, methacryloyloxide deca Noxy, methacryloyloxytridecyloxy.

  Aliphatic groups are, for example, saturated or unsaturated, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-valent alkyl, alkylene, alkyloxy. , Alkylcarbonyloxy, acryloyloxy, alkyl acryl, alkyl methacryl, alkyl (alkylene) acryl (acrylene), alkyl (alkylene) methacryl (methacrylene), alkyloxycarbonyloxy, alkyloxycarbonyloxy, methacryloyloxy, alkyl vinyl, alkyl vinyl Oxy or alkylallyloxy, which may contain one or more heteroatoms and / or bridging groups.

The alicyclic group is preferably a non-aromatic group or unit and can be substituted or unsubstituted. Preferably, the alicyclic group is a non-aromatic carbocyclic or heterocyclic group, for example a ring system having 3 to 30 carbon atoms, such as cyclopropane, cyclobutane, cyclopentane, cyclopentene, cyclohexane, cyclohexene. , Cyclohexadiene, decalin, tetrahydrofuran, dioxane, pyrrolidine, piperidine or a steroid skeleton such as cholesterol. A preferred alicyclic group is cyclohexane. Substituents of alicyclic groups are substituted or unsubstituted C ₁ -C ₆ alkoxy (ether groups, preferably methoxy or trifluoromethyl or one or more halogens, preferably fluoro or / and chloro or halogen Resulting in the formation of hydroxyl groups. Preference is given to cyclohexanol or cyclohexane groups substituted by C ₁ -C ₆ alkoxy, which in the context of the present invention are referred to as, for example, cycloxanether groups.

As used in the context of the present invention, the term “aromatic” preferably includes unsubstituted, substituted, 5, 6, 10 or 14 ring atoms and is uninterrupted or at least one Carbocycles and heterocyclic groups interrupted by heteroatoms and / or at least one bridging group such as furan, benzene or phenylene, pyridine, pyrimidine, naphthalene (these form ring assemblies such as biphenylene or triphenylene Or a fused polycyclic system such as phenanthrene, tetralin. Preferably, the aromatic group is benzene, phenylene, biphenylene or triphenylene. More preferred aromatic groups are benzene, phenylene and biphenylene. Particularly preferred substituents of the aromatic group or a carbocyclic or heterocyclic group, halogen, preferably fluoro and / or chloro, C ₁ -C ₆ alkoxy, preferably, methoxy or trifluoromethyl.

  A carbocyclic or heterocyclic aromatic group or alicyclic group is preferably 3, 4, 5, 6, 10 or 14 ring atoms such as aziridines, epoxies, cyclopropyls, furans, pyrrolidines, oxazolines, imidazoles , Benzene, pyridine, triazine, pyrimidine, naphthalene, phenanthrene, biphenylene or tetralin units, preferably naphthalene, phenanthrene, biphenylene or phenylene, more preferably naphthalene, biphenylene or phenylene, and most preferably phenylene.

Particularly preferred substituents of carbocyclic and heterocyclic aromatic group or an alicyclic group consisting of halogen, preferably fluoro and / or chloro, C ₁ -C ₆ alkoxy, preferably, methoxy or trifluoromethyl.

An unsubstituted or substituted carbocyclic or heterocyclic aromatic or alicyclic group is, for example, unsubstituted or mono- or polysubstituted. Preferred substituents for carbocyclic or heterocyclic aromatic groups are trifluoromethyl, halogen such as fluoro, chloro, bromo, iodo, especially fluoro or / and chloro, and especially fluoro; hydroxyl, polar groups, acryloyloxy , Alkylacryloyloxy, alkoxy, especially methoxy, ethoxy, propoxy; alkylcarbonyloxy, alkyloxycarbonyloxy, alkyloxocarbonyloxy, methacryloyloxy, vinyl, vinyloxy and / or allyloxy groups, wherein And the alkyl residue preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. Preferred polar groups are nitro, nitrile or carboxy groups and / or cyclic, linear or branched C ₁ -C ₃₀ alkyl, which alkyl is unsubstituted, monosubstituted or polysubstituted. Preferred substituents for C ₁ -C ₃₀ alkyl are methyl, fluorine and / or chlorine, wherein one or more, preferably non-adjacent —C—, —CH—, —CH ₂ — groups. Each independently can be replaced by a linking group. Preferably, the linking group is selected from -O-, -CO-, -COO- and / or -OCO-.

  A monocyclic ring of 5 or 6 atoms is, for example, furan, benzene, preferably phenylene, pyridine, pyrimidine, pyridine cation, pyrimidine cation.

  A bicyclic system of 8, 9 or 10 atoms is, for example, naphthalene, biphenylene or tetralin.

  A tricyclic system of 13 or 14 atoms is, for example, phenanthrene.

As used in the context of the present invention, the term “phenylene” preferably refers to an optionally substituted 1,2-, 1,3- or 1,4-phenylene group. Particularly preferred substituents of the phenylene are halogen, preferably fluoro and / or chloro, C ₁ -C ₆ alkoxy, preferably, methoxy or trifluoromethyl. The phenylene group is preferably either a 1,3- or 1,4-phenylene group. A 1,4-phenylene group is particularly preferred.

  The term “halogen” refers to a chloro, fluoro, bromo or iodo substituent, preferably a chloro or fluoro substituent, and more preferably fluoro.

  As used in the context of the present invention, the term “heteroatom” is a neutral, anionic or cationic heteroatom, mainly oxygen, sulfur and nitrogen, halogens such as fluoro, chloro, bromo, Iodo, and more preferably fluoro and / or chloro, and most preferably fluoro; preferably refers to halogen, oxygen and nitrogen. In the latter case, it is in the form of a primary amine, secondary amine, tertiary amine or quaternary ammonium cation, preferably —NH—.

As used in the context of the present invention, the term “optionally substituted” is primarily a lower alkyl, eg, C ₁ -C ₆ alkyl, lower alkoxy, eg, C ₁ -C ₆ alkoxy, hydroxy, It means substituted by halogen, for example fluorine or chlorine, or by a polar group, for example a cyano group.

Linear or branched alkyl, alkylene, alkoxy, alkylcarbonyloxy, acryloyloxyalkoxy, acryloyloxyalkyl, acryloyloxyalkene, alkyloxycarbonyloxy, alkylacryloyloxy, methacryloyloxyalkoxy, methacryloyloxyalkene, methacryloyloxyalkene, alkyl With respect to methacryloyloxy, alkylmethacryloyloxy, alkylvinyl, alkylvinyloxy, alkylallyloxy and alkylene groups, some or some of the —C—, —CH—, —CH ₂ — groups are, for example, by heteroatoms, provided It can also be replaced by other groups, preferably bridging groups. In such cases it is generally preferred that such substituents are not directly linked to one another. It is alternatively preferred that the heteroatoms, and in particular the oxygen atoms, are not directly linked to one another.

［式中、
ｎ_０、ｎ_１、ｎ_２、ｎ_３、Ｓ_２、Ａ、Ｔは、上記されたとおりであり、
Ｅは、Ｏ又はＳ又はＮＨを表わし、
Ｘ、Ｙは、Ｈであり、
Ｚ_２は、ＣＮであり、
^＊は、ポリマー骨格への結合部位を指す］
で示される側鎖を有する少なくとも１つのモノマーと、
式（ＩＩ）

［式中、
Ｅ_１、ｎ_５、ｎ_６、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４及びＲ_５は、上記されたのと同じ意味を有し、
Ｘ_１又はＹ_１のいずれかは、シアノであり、他方は、水素であり、
Ｓ_３は、直鎖又は分岐鎖のＣ_１〜Ｃ_２４アルキレン、より好ましくは、Ｃ_１〜Ｃ_１２アルキレン、更により好ましくは、Ｃ_４〜Ｃ_１２アルキレンであり、ここで、１つ以上の−ＣＨ_２−基は、それぞれ独立して、ヘテロ原子又は−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＲ^８−、−ＮＲ^８ＣＯ−、−ＣＯＮＲ^８−、−ＮＲ^８ＣＯＯ−、−ＯＣＯＮＲ^８−、−ＮＲ^８ＣＯＮＲ^８−、−Ｃ＝Ｃ−、−Ｃ≡Ｃ−、−Ｏ−ＣＯＯ−からなる群より選択される基により置き換えられていることができ、
ここで、Ｒ^８は、水素原子又は低級アルキルであり、
^＊は、ポリマー骨格への結合部位を指す］
で示される側鎖を有する第２のモノマーとを含み、
ここで、ポリマーは、ポリシロキサンである。 In a preferred embodiment, the first aspect of the present invention relates to a copolymer for photoalignment of liquid crystals, in particular for planar alignment of liquid crystals, said copolymer having the formula (I):

[Where:
n _0, n ₁ , n ₂ , n ₃ , S ₂ , A, T are as described above,
E represents O or S or NH;
X and Y are H,
Z ₂ is CN,
^{* Indicates} the binding site to the polymer backbone]
At least one monomer having a side chain represented by
Formula (II)

[Where:
E ₁ , n ₅ , n ₆ , R ₁ , R ₂ , R ₃ , R ₄ and R ₅ have the same meaning as described above;
Either X ₁ or Y ₁ is cyano, the other is hydrogen,
S ₃ is a linear or branched C ₁ -C ₂₄ alkylene, more preferably C ₁ -C ₁₂ alkylene, even more preferably C ₄ -C ₁₂ alkylene, wherein one or more- The CH ₂ — groups are each independently a hetero atom or —O—, —CO—, —COO—, —OCO—, —NR ⁸ —, —NR ⁸ CO—, —CONR ⁸ —, —NR ⁸ COO. ^{-, - OCONR 8 -, -} NR 8 CONR 8 -, - C = C -, - C≡C -, - O-COO- can be replaced by a group selected from the group consisting of,
Here, R ⁸ is a hydrogen atom or lower alkyl,
^{* Indicates} the binding site to the polymer backbone]
A second monomer having a side chain represented by
Here, the polymer is polysiloxane.

［式中、
ｎ_０、ｎ_１、ｎ_２、ｎ_３、Ｓ_２、Ｔは、上記されたとおりであり、
Ａは、Ｈ、１つ以上のハロゲン、１つ以上のメトキシ基又は１つ以上のカルボキシル基を表わし、
Ｅは、Ｏ又はＳ又はＮＨを表わし、
Ｘ、Ｙは、Ｈであり、
Ｚ_２は、ＣＮであり、
^＊は、ポリマー骨格への結合部位を指す］
で示される側鎖を有する少なくとも１つのモノマーと、
式（ＩＩＩ）

［式中、
Ｅ_１、ｎ_５、ｎ_６、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４及びＲ_５は、上記されたのと同じ意味を有し、
Ｘ_１又はＹ_１のいずれかは、シアノであり、他方は、水素であり、
Ｓ_３は、直鎖又は分岐鎖のＣ_１〜Ｃ_２４アルキレン、より好ましくは、Ｃ_１〜Ｃ_１２アルキレン、更により好ましくは、Ｃ_４〜Ｃ_１２アルキレンであり、ここで、１つ以上の−ＣＨ_２−基は、それぞれ独立して、ヘテロ原子又は−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＲ^８−、−ＮＲ^８ＣＯ−、−ＣＯＮＲ^８−、−ＮＲ^８ＣＯＯ−、−ＯＣＯＮＲ^８−、−ＮＲ^８ＣＯＮＲ^８−、−Ｃ＝Ｃ−、−Ｃ≡Ｃ−、−Ｏ−ＣＯＯ−からなる群より選択される基により置き換えられていることができ、
ここで、Ｒ^８は、水素原子又は低級アルキルであり、
^＊は、ポリマー骨格への結合部位を指す］
で示される側鎖を有する第２のモノマーとを含み、
ここで、ポリマーは、ポリシロキサンである。 In another preferred embodiment, the first aspect of the present invention relates to a copolymer for the photo-alignment of liquid crystals, in particular for the planar alignment of liquid crystals, said copolymer having the formula (I):

[Where:
n _0, n ₁ , n ₂ , n ₃ , S ₂ , T are as described above,
A represents H, one or more halogens, one or more methoxy groups or one or more carboxyl groups,
E represents O or S or NH;
X and Y are H,
Z ₂ is CN,
^{* Indicates} the binding site to the polymer backbone]
At least one monomer having a side chain represented by
Formula (III)

[Where:
E ₁ , n ₅ , n ₆ , R ₁ , R ₂ , R ₃ , R ₄ and R ₅ have the same meaning as described above;
Either X ₁ or Y ₁ is cyano, the other is hydrogen,
S ₃ is a linear or branched C ₁ -C ₂₄ alkylene, more preferably C ₁ -C ₁₂ alkylene, even more preferably C ₄ -C ₁₂ alkylene, wherein one or more- The CH ₂ — groups are each independently a hetero atom or —O—, —CO—, —COO—, —OCO—, —NR ⁸ —, —NR ⁸ CO—, —CONR ⁸ —, —NR ⁸ COO. ^{-, - OCONR 8 -, -} NR 8 CONR 8 -, - C = C -, - C≡C -, - O-COO- can be replaced by a group selected from the group consisting of,
Here, R ⁸ is a hydrogen atom or lower alkyl,
^{* Indicates} the binding site to the polymer backbone]
A second monomer having a side chain represented by
Here, the polymer is polysiloxane.

［式中、
ｎ_０、ｎ_１、ｎ_２、ｎ_３、Ｓ_２、Ｔは、上記されたとおりであり、
Ａは、Ｈ、ハロゲン、メトキシ基又はカルボキシル基を表わし、
Ｅは、Ｏを表わし、
Ｘ、Ｙは、Ｈであり、
Ｚ_２は、ＣＮであり、
^＊は、ポリマー骨格への結合部位を指す］
で示される側鎖を有する少なくとも１つのモノマーと、
式（ＩＩＩ）

［式中、
Ｅ_１、ｎ_５、ｎ_６、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４及びＲ_５は、上記されたのと同じ意味を有し、
Ｘ_１又はＹ_１のいずれかは、シアノであり、他方は、水素であり、
Ｓ_３は、直鎖又は分岐鎖のＣ_１〜Ｃ_２４アルキレン、より好ましくは、Ｃ_１〜Ｃ_１２アルキレン、更により好ましくは、Ｃ_４〜Ｃ_１２アルキレンであり、ここで、１つ以上の−ＣＨ_２−基は、それぞれ独立して、ヘテロ原子又は−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＲ^８−、−ＮＲ^８ＣＯ−、−ＣＯＮＲ^８−、−ＮＲ^８ＣＯＯ−、−ＯＣＯＮＲ^８−、−ＮＲ^８ＣＯＮＲ^８−、−Ｃ＝Ｃ−、−Ｃ≡Ｃ−、−Ｏ−ＣＯＯ−からなる群より選択される基により置き換えられていることができ、
ここで、Ｒ^８は、水素原子又は低級アルキルであり、
^＊は、ポリマー骨格への結合部位を指す］
で示される側鎖を有する第２のモノマーとを含み、
ここで、ポリマーは、ポリシロキサンである。 In another preferred embodiment, the first aspect of the present invention relates to a copolymer for the photo-alignment of liquid crystals, in particular for the planar alignment of liquid crystals, said copolymer having the formula (I):

[Where:
n _0, n ₁ , n ₂ , n ₃ , S ₂ , T are as described above,
A represents H, halogen, methoxy group or carboxyl group,
E represents O,
X and Y are H,
Z ₂ is CN,
^{* Indicates} the binding site to the polymer backbone]
At least one monomer having a side chain represented by
Formula (III)

[Where:
E ₁ , n ₅ , n ₆ , R ₁ , R ₂ , R ₃ , R ₄ and R ₅ have the same meaning as described above;
Either X ₁ or Y ₁ is cyano, the other is hydrogen,
S ₃ is a linear or branched C ₁ -C ₂₄ alkylene, more preferably C ₁ -C ₁₂ alkylene, even more preferably C ₄ -C ₁₂ alkylene, wherein one or more- The CH ₂ — groups are each independently a hetero atom or —O—, —CO—, —COO—, —OCO—, —NR ⁸ —, —NR ⁸ CO—, —CONR ⁸ —, —NR ⁸ COO. ^{-, - OCONR 8 -, -} NR 8 CONR 8 -, - C = C -, - C≡C -, - O-COO- can be replaced by a group selected from the group consisting of,
Here, R ⁸ is a hydrogen atom or lower alkyl,
^{* Indicates} the binding site to the polymer backbone]
A second monomer having a side chain represented by
Here, the polymer is polysiloxane.

［式中、
ｎ_０及びＴは、上記されたとおりであり、
Ａは、Ｈ、ハロゲン、メトキシ基又はカルボキシル基を表わし、
Ｅは、Ｏを表わし、
Ｘ、Ｙは、Ｈであり、
Ｚ_２は、ＣＮであり、
^＊は、ポリマー骨格への結合部位を指す］
で示される側鎖を有する少なくとも１つのモノマーと、
式（ＩＩ）

［式中、
Ｅ_１、ｎ_５、ｎ_６、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４及びＲ_５は、上記されたのと同じ意味を有し、
Ｘ_１又はＹ_１のいずれかは、シアノであり、他方は、水素であり、
Ｓ_３は、直鎖又は分岐鎖のＣ_１〜Ｃ_２４アルキレン、より好ましくは、Ｃ_１〜Ｃ_１２アルキレン、更により好ましくは、Ｃ_４〜Ｃ_１２アルキレンであり、ここで、１つ以上の−ＣＨ_２−基は、それぞれ独立して、ヘテロ原子又は−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＲ^８−、−ＮＲ^８ＣＯ−、−ＣＯＮＲ^８−、−ＮＲ^８ＣＯＯ−、−ＯＣＯＮＲ^８−、−ＮＲ^８ＣＯＮＲ^８−、−Ｃ＝Ｃ−、−Ｃ≡Ｃ−、−Ｏ−ＣＯＯ−からなる群より選択される基により置き換えられていることができ、
ここで、Ｒ^８は、水素原子又は低級アルキルであり、
^＊は、ポリマー骨格への結合部位を指す］
で示される側鎖を有する第２のモノマーとを含み、
ここで、ポリマーは、ポリシロキサンである。 In a further preferred embodiment, the first aspect of the present invention relates to a copolymer for photoalignment of liquid crystals, in particular for planar alignment of liquid crystals, said copolymer having the formula (Ia):

[Where:
n ₀ and T are as described above,
A represents H, halogen, methoxy group or carboxyl group,
E represents O,
X and Y are H,
Z ₂ is CN,
^{* Indicates} the binding site to the polymer backbone]
At least one monomer having a side chain represented by
Formula (II)

[Where:
E ₁ , n ₅ , n ₆ , R ₁ , R ₂ , R ₃ , R ₄ and R ₅ have the same meaning as described above;
Either X ₁ or Y ₁ is cyano, the other is hydrogen,
S ₃ is a linear or branched C ₁ -C ₂₄ alkylene, more preferably C ₁ -C ₁₂ alkylene, even more preferably C ₄ -C ₁₂ alkylene, wherein one or more- The CH ₂ — groups are each independently a hetero atom or —O—, —CO—, —COO—, —OCO—, —NR ⁸ —, —NR ⁸ CO—, —CONR ⁸ —, —NR ⁸ COO. ^{-, - OCONR 8 -, -} NR 8 CONR 8 -, - C = C -, - C≡C -, - O-COO- can be replaced by a group selected from the group consisting of,
Here, R ⁸ is a hydrogen atom or lower alkyl,
^{* Indicates} the binding site to the polymer backbone]
A second monomer having a side chain represented by
Here, the polymer is polysiloxane.

［式中、
ｎ_０及びＴは、上記されたとおりであり、
Ａは、Ｈ、ハロゲン、メトキシ基又はカルボキシル基を表わし、
Ｅは、Ｏを表わし、
Ｘ、Ｙは、Ｈであり、
Ｚ_２は、ＣＮであり、
^＊は、ポリマー骨格への結合部位を指す］
で示される側鎖を有する少なくとも１つのモノマーと、
式（ＩＩＩ）

［式中、
Ｅ_１、ｎ_５、ｎ_６、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４及びＲ_５は、上記されたのと同じ意味を有し、
Ｘ_１又はＹ_１のいずれかは、シアノであり、他方は、水素であり、
Ｓ_３は、直鎖又は分岐鎖のＣ_１〜Ｃ_２４アルキレン、より好ましくは、Ｃ_１〜Ｃ_１２アルキレン、更により好ましくは、Ｃ_４〜Ｃ_１２アルキレンであり、ここで、１つ以上の−ＣＨ_２−基は、それぞれ独立して、ヘテロ原子又は−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＲ^８−、−ＮＲ^８ＣＯ−、−ＣＯＮＲ^８−、−ＮＲ^８ＣＯＯ−、−ＯＣＯＮＲ^８−、−ＮＲ^８ＣＯＮＲ^８−、−Ｃ＝Ｃ−、−Ｃ≡Ｃ−、−Ｏ−ＣＯＯ−からなる群より選択される基により置き換えられていることができ、
ここで、Ｒ^８は、水素原子又は低級アルキルであり、
^＊は、ポリマー骨格への結合部位を指す］
で示される側鎖を有する第２のモノマーとを含み、
ここで、ポリマーは、ポリシロキサンである。 In a further preferred embodiment, the first aspect of the present invention relates to a copolymer for the photo-alignment of liquid crystals, in particular for the planar alignment of liquid crystals, said copolymer having the formula (Ia):

[Where:
n ₀ and T are as described above,
A represents H, halogen, methoxy group or carboxyl group,
E represents O,
X and Y are H,
Z ₂ is CN,
^{* Indicates} the binding site to the polymer backbone]
At least one monomer having a side chain represented by
Formula (III)

[Where:
E ₁ , n ₅ , n ₆ , R ₁ , R ₂ , R ₃ , R ₄ and R ₅ have the same meaning as described above;
Either X ₁ or Y ₁ is cyano, the other is hydrogen,
S ₃ is a linear or branched C ₁ -C ₂₄ alkylene, more preferably C ₁ -C ₁₂ alkylene, even more preferably C ₄ -C ₁₂ alkylene, wherein one or more- The CH ₂ — groups are each independently a hetero atom or —O—, —CO—, —COO—, —OCO—, —NR ⁸ —, —NR ⁸ CO—, —CONR ⁸ —, —NR ⁸ COO. ^{-, - OCONR 8 -, -} NR 8 CONR 8 -, - C = C -, - C≡C -, - O-COO- can be replaced by a group selected from the group consisting of,
Here, R ⁸ is a hydrogen atom or lower alkyl,
^{* Indicates} the binding site to the polymer backbone]
A second monomer having a side chain represented by
Here, the polymer is polysiloxane.

［式中、
ｎ_０及びＴは、上記されたとおりであり、
Ａは、Ｈ、ハロゲン、メトキシ基又はカルボキシル基を表わし、
Ｅは、Ｏを表わし、
Ｘ、Ｙは、Ｈであり、
Ｚ_２は、ＣＮであり、
^＊は、ポリマー骨格への結合部位を指す］
で示される側鎖を有する１つのモノマーと、
式（ＩＩＩ）

［式中、
Ｅ_１、ｎ_５、ｎ_６、Ｓ_３、Ｒ_４及びＲ_５は、上記されたのと同じ意味を有し、
Ｘ_１又はＹ_１のいずれかは、シアノであり、他方は、水素であり、
Ｒ_１、Ｒ_２及びＲ_３は、それぞれ独立して、Ｈ又は−ＣＦ_３−又はメトキシであり、
^＊は、ポリマー骨格への結合部位を指す］
で示される側鎖を有する第２のモノマーとを含み、
ここで、ポリマーは、ポリシロキサンである。 In a further preferred embodiment, the first aspect of the present invention relates to a copolymer for photoalignment of liquid crystals, in particular for planar alignment of liquid crystals, said copolymer having the formula (Ia):

[Where:
n ₀ and T are as described above,
A represents H, halogen, methoxy group or carboxyl group,
E represents O,
X and Y are H,
Z ₂ is CN,
^{* Indicates} the binding site to the polymer backbone]
One monomer having a side chain represented by
Formula (III)

[Where:
E ₁ , n ₅ , n ₆ , S ₃ , R ₄ and R ₅ have the same meaning as described above;
Either X ₁ or Y ₁ is cyano, the other is hydrogen,
R ₁ , R ₂ and R ₃ are each independently H or —CF ₃ — or methoxy;
^{* Indicates} the binding site to the polymer backbone]
A second monomer having a side chain represented by
Here, the polymer is polysiloxane.

［式中、
ｎ_０及びＴは、上記されたとおりであり、
Ａは、Ｈ、ハロゲン、メトキシ基又はカルボキシル基を表わし、
Ｅは、Ｏを表わし、
Ｘ、Ｙは、Ｈであり、
Ｚ_２は、ＣＮであり、
^＊は、ポリマー骨格への結合部位を指す］
で示される側鎖を有する１つのモノマーと、
式（ＩＩＩ）

［式中、
Ｅ_１、ｎ_５、ｎ_６、Ｓ_３、Ｒ_４及びＲ_５は、上記されたのと同じ意味を有し、
Ｘ_１又はＹ_１のいずれかは、シアノであり、他方は、水素であり、
Ｒ_１、Ｒ_２及びＲ_３は、それぞれ独立して、Ｈ又は−ＣＦ_３−又はメトキシであり、
Ｓ_３は、Ｃ_４アルキレン又はＣ_５アルキレン又はＣ_６アルキレン又はＣ_７アルキレン又はＣ_８アルキレン又はＣ_９アルキレン又はＣ_１０アルキレン又はＣ_１１アルキレン又はＣ_１２アルキレンであり、
^＊は、ポリマー骨格への結合部位を指す］
で示される側鎖を有する第２のモノマーとを含み、
ここで、ポリマーは、ポリシロキサンである。 In a further preferred embodiment, the first aspect of the present invention relates to a copolymer for photoalignment of liquid crystals, in particular for planar alignment of liquid crystals, said copolymer having the formula (Ia):

[Where:
n ₀ and T are as described above,
A represents H, halogen, methoxy group or carboxyl group,
E represents O,
X and Y are H,
Z ₂ is CN,
^{* Indicates} the binding site to the polymer backbone]
One monomer having a side chain represented by
Formula (III)

[Where:
E ₁ , n ₅ , n ₆ , S ₃ , R ₄ and R ₅ have the same meaning as described above;
Either X ₁ or Y ₁ is cyano, the other is hydrogen,
R ₁ , R ₂ and R ₃ are each independently H or —CF ₃ — or methoxy;
S ₃ is C ₄ alkylene or C ₅ alkylene or C ₆ alkylene or C ₇ alkylene or C ₈ alkylene or C ₉ alkylene or C ₁₀ alkylene or C ₁₁ alkylene or C ₁₂ alkylene,
^{* Indicates} the binding site to the polymer backbone]
A second monomer having a side chain represented by
Here, the polymer is polysiloxane.

  The present invention includes a first monomer having a side chain represented by formula (I) or formula (Ia) and a second monomer having a side chain represented by formula (II) or (III), With respect to the total amount of monomers of formula (I) or formula (Ia) and formula (II) or (III), the molar ratio of the second monomer of formula (II) or formula (III) is 0.01 % To 50%, preferably 0.01% to 25%, more preferably 0.01% to 15%.

  In a second embodiment, the present invention relates to a composition comprising at least one of the above-mentioned copolymers and a second polymer or copolymer different from the first copolymer.

  In a preferred second embodiment, the present invention relates to a composition comprising at least one copolymer as described above, a second polymer or copolymer different from the first copolymer, and an additive.

  The second polymer or copolymer in the second embodiment of the present invention includes polyamic acid, polyamic acid ester, polyimide, polymerizable liquid crystal, polymerized liquid crystal (LCP), polysiloxane, polyacrylate, polymethacrylate, polyacrylamide, Polymethacrylamide, polyvinyl ether, polyvinyl ester, polyallyl ether, polyallyl ester, polystyrene, polyamideimide, polymaleic acid, polyfumaric acid, polyurethane and derivatives thereof, polystyrene, polyester, polyurethane, polyethylene, polypropylene, polyvinyl chloride, polytetra Group consisting of fluoroethylene, polycarbonate, polysilane, polymaleimide, polynorbornene, polyterephthalate, polycyanostilbene and dendrimer Ri is a polymer or copolymer is selected.

  The more preferred second polymer or copolymer in the second embodiment of the present invention is polyamic acid or polyimide. Polyamic acid is most preferred.

  It should be understood that the term “diamine” or “diamine compound” designates a chemical structure that has at least two amino groups, ie, may also have three or more amino groups.

  When the second polymer or copolymer is a diamine, the diamine represents an aliphatic, aromatic or cycloaliphatic diamino group having 1 to 40 carbon atoms and optionally substituted, preferably A group of the following structure: aniline, p-phenylenediamine, m-phenylenediamine, benzidine, diaminofluorene or a derivative thereof (provided that the compounds listed as having no two amino groups have at least one further amino group and Prepared from or selected from the same group, and more preferably prepared from the following commercially available amino compounds (examples of suppliers: Aldrich, ABCR, ACROS, Fluka) Selected from. These are also comonomer: 4-amino-2,3,5,6-tetrafluorobenzoic acid, 4-amino-3,5-diiodobenzoic acid, 3,4-diaminobenzoic acid, 4-amino-3- Methylbenzoic acid, 4-amino-2-chlorobenzoic acid, 4-aminosalicylic acid, 4-aminobenzoic acid, 4-aminophthalic acid, 1- (4-aminophenyl) ethanol, 4-aminobenzyl alcohol, 4-amino- 3-methoxybenzoic acid, 4-aminophenylethylcarbinol, 4-amino-3-nitrobenzoic acid, 4-amino-3,5-dinitrobenzoic acid, 4-amino-3,5-dichlorobenzoic acid, 4- Amino-3-hydroxybenzoic acid, 4-aminobenzyl alcohol hydrochloride, 4-aminobenzoic acid hydrochloride, pararose aniline base, 4-amino-5-chloro-2 Methoxybenzoic acid, 4- (hexafluoro-2-hydroxyisopropyl) aniline, piperazine-p-aminobenzoate, 4-amino-3,5-dibromobenzoic acid, isonicotinic acid hydrazide p-aminosalicylate, 4-amino -3,5-diiodosalicylic acid, 4-amino-2-methoxybenzoic acid, 2- [2- (4-aminophenyl) -2-hydroxy-1- (hydroxymethyl) ethyl] isoindoline-1,3- Dione, 4-amino-2-nitrobenzoic acid, 2,4-diaminobenzoic acid, p-aminobenzoic acid, [3,5-3h] -4-amino-2-methoxybenzoic acid, L-(+)- Threo-2-amino-1- (4-aminophenyl) -1,3-propanediol, L-(+)-threo-2- (N, N-dimethylamino) -1- (4 -Aminophenyl) -1,3-propanediol, ethyl 2- (4-aminophenyl) -3,3,3-trifluoro-2-hydroxypropanoate, ethyl 2- (4-amino-3-methylphenyl) ) -3,3,3-trifluoro-2-hydroxypropanoate, ethyl 2- (4-amino-3-methoxyphenyl) -3,3,3-trifluoro-2-hydroxypropanoate, 3, 4-diaminobenzyl alcohol dihydrochloride, 4-aminonaphthalene-1,8-dicarboxylic acid, 4-amino-3-chloro-5-methylbenzoic acid, 4-amino-2,6-dimethylbenzoic acid, 4-amino -3-fluorobenzoic acid, 4-amino-5-bromo-2-methoxybenzenecarboxylic acid, 2,7-diaminofluorene, 4,4'-diaminooctafluoro Phenyl, 3,3′-diaminobenzidine, 3,3 ′, 5,5′-tetramethylbenzidine, 3,3′-dimethoxybenzidine, o-tolidine, 3,3′-dinitrobenzidine, 2-nitrobenzidine, 3 , 3′-dihydroxybenzidine, o-tolidinesulfone, benzidine, 3,3′-dichlorobenzidine, 2,2 ′, 5,5′-tetrachlorobenzidine, benzidine-3,3′-dicarboxylic acid, 4,4 ′ -Diamino-1,1'-binaphthyl, 4,4'-diaminodiphenyl-3,3'-diglycolic acid, dihydroethidium, o-dianisidine, 2,2'-dichloro-5,5'-dimethoxybenzidine, 3 -Methoxybenzidine, 3,3'-dichlorobenzidine (diphenyl-d6), 2,7-diamino-9-fluorenone, 3,5 3 ′, 5′-tetrabromo-biphenyl-4,4′-diamine, 2,2′-bis (trifluoromethyl) benzidine, 2,2′-dichloro [1,1′-biphenyl] -4,4′- Diamine, 3,9-diamino-1,11-dimethyl-5,7-dihydro-dibenzo (a, c) cyclopenten-6-one, 3,3′-bis (trifluoromethyl) benzidine, dibenzo (1,2 ) Dithiin-3,8-diamine, 3,3′-tolidine-5-sulfonic acid, 3,3′-dichlorobenzidine-d6, tetramethylbenzidine, 3,3′-diaminobenzophenone, 3,3′-diaminodiphenylmethane 4,4-bis- (3-amino-4-hydroxyphenyl) -valeric acid, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane, tetrabromomethylenedianiline, 2,7-diamino-9-fluorenone, 2,2-bis (3-aminophenyl) hexafluoropropane, Bis- (3-amino-4-chloro-phenyl) -methanone, bis- (3-amino-4-dimethylamino-phenyl) -methanone, 3- [3-amino-5- (trifluoromethyl) benzyl]- It can also be used as 5- (trifluoromethyl) aniline, 1,5-diaminonaphthalene or a derivative thereof. However, it is again provided that the listed compounds not having two amino groups are used as derivatives with at least one further amino group.

  Further preferred examples of other diamines include ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, 1,5-pentylenediamine, 1,6-hexylenediamine, 1,7-heptylenediamine. 1,8-octylenediamine, 1,9-nonylenediamine, 1,10-decylenediamine, 1,11-undecylenediamine, 1,12-dodecylenediamine, α, α'-diamino-m- Xylene, α, α′-diamino-p-xylene, (5-amino-2,2,4-trimethylcyclopentyl) methylamine, 1,2-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 1,3- Bis (methylamino) cyclohexane, 4,9-dioxadodecane-1,12-diamine, 3,5-diaminobenzoic acid methyl ester 3,5-diaminobenzoic acid hexyl ester, 3,5-diaminobenzoic acid dodecyl ester, 3,5-diaminobenzoic acid isopropyl ester, 4,4′-methylenedianiline, 4,4′-ethylenedianiline, 4 , 4′-diamino-3,3′-dimethyldiphenylmethane, 3,3 ′, 5,5′-tetramethylbenzidine, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl ether, 1,5-diamino Naphthalene, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,4′-diaminodiphenyl ether, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 4,4′-diamino-2, 2′-dimethylbibenzyl, bis [4- (4-aminophenoxy) phenyl] sulfone, 1,4-bi (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 2,7-diaminofluorene, 9,9-bis (4- Aminophenyl) fluorene, 4,4′-methylenebis (2-chloroaniline), 4,4′-bis (4-aminophenoxy) biphenyl, 2,2 ′, 5,5′-tetrachloro-4,4′- Diaminobiphenyl, 2,2′-dichloro-4,4′-diamino-5,5′-dimethoxybiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 4,4 ′-(1,4- Phenyleneisopropylidene) bisaniline, 4,4 ′-(1,3-phenyleneisopropylidene) bisaniline, 2,2-bis [4- (4-aminophenoxy) phenyl] pro 2,2-bis [3- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [3-amino-4-methylphenyl] hexafluoropropane, 2,2-bis (4-amino) Phenyl) hexafluoropropane, 2,2′-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4′-diamino-2,2′-bis (trifluoromethyl) ) Biphenyl and 4,4′-bis [(4-amino-2-trifluoromethyl) phenoxy] -2,3,5,6,2 ′, 3 ′, 5 ′, 6′-octafluorobiphenyl; and US 6,340,506, WO 00/59966, and 01/53384. All of these documents are expressly incorporated herein by reference.

  The diamine compounds of the present invention can be prepared using methods known to those skilled in the art.

In addition, preferred diamines are the commercial products listed below.
Polymer poly (3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride-co-4,4′-oxydianiline / 1,3-phenylenediamine) amidic acid solution, poly (3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride-co-4,4′-oxydianiline / 1,3-phenylenediamine) amic acid solution, poly (pyromellitic dianhydride-co-4,4 ′ -Oxydianiline) amic acid solution.

Aromatic diamine 2,7-diaminofluorene, 1,5-diaminoanthraquinone, 2,6-diaminoanthraquinone, pararose aniline hydrochloride, 3,6-acridinediamine, 4,4′-diaminooctafluorobiphenyl, 2,2 '-Dithiodianiline, 3,3', 5,5'-tetramethylbenzidine, 3,3'-diaminodiphenylsulfone, 4,4'-diamino-2,2'-dimethylbibenzyl, 4,4'- Diaminodiphenyl ether, 4,4′-dithiodianiline, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylmethane, 4,4′-ethylenedianiline, 3,3′-dimethoxybenzidine, 2,2 ′ -Dithiobis (1-naphthylamine), 3,7-diamino-2-methoxyfluorene, 3,6-diamino-10-methyla Lidinium chloride, propidium iodide, o-dianisidine dihydrochloride, 2,7-diaminofluorene dihydrochloride, pararose aniline acetate, 3,6-diamino-10-methylacridinium chloride hydrochloride, proflavine di Hydrochloride, o-tolidine dihydrochloride, 3,3 ′, 5,5′-tetramethylbenzidine dihydrochloride, 3,3′-diaminobenzidine tetrahydrochloride, 4,4′-diaminostilbene dihydrochloride, 4 , 4′-diaminodiphenylamine sulfate, proflavine hemisulphate, 2,2′-ethylene dianiline diphosphate, 1,5-diamino-4,8-dihydroxyanthraquinone, o-tolidine, 3,3′-diaminobenzophenone 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 2,2-bis [4- (4-Aminophenoxy) phenyl] hexafluoropropane, 4,4′-diamino-1,1′-dianthramide, 3,3′-dinitrobenzidine, 4,4′-diamino-5,5′-dimethyl-2, 2'-biphenyldisulfonic acid, 4,4'-diaminostilbene-2,2'-disulfonic acid, 3-amino-4-hydroxyphenylsulfone, 4,4-bis- (3-amino-4-hydroxyphenyl)- Valeric acid, 2,2′-diamino-4,4′-difluorobibenzyl, 2-amino-4-chlorophenyl disulfide, 3,3 ′-(decamethylenedioxy) dianiline, 3,3 ′-(pentamethylenedi) Oxy) dianiline, 4- (p-aminoanilino) -3-sulfoaniline, 4- [3- (4-aminophenoxy) propoxy] aniline, 2-nitrobenzidine Benzidine-3-sulfonic acid, 4,4′-diaminodiphenyl sulfide, 4,4′-diaminobenzanilide, n, n′-bis (3-aminophenylsulfonyl) ethylenediamine, 2,2′-biphenyldiamine, 3, 4'-diaminodiphenyl ether, proflavine hemisulphate, phenosafranine, 4,4'-diaminobenzophenone, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-amino-4- Hydroxyphenyl) hexafluoropropane, 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane, 3,3′-dihydroxybenzidine, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4 , 4′-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4 Aminophenoxy) phenyl] propane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, 9,9 -Bis (4-aminophenyl) fluorene, o-tolidine sulfone, benzidine, 3,3'-dichlorobenzidine dihydrochloride, benzidine dihydrochloride, 3,6-thioxanthenediamine-10,10-dioxide, 4,4 '-Diamino-2,2'-biphenyldisulfonic acid, 4,4'-azodianiline, 2,5-bis- (4-aminophenyl)-(1,3,4) oxadiazole, 3,3'-dimethyl Naphthidine, benzidine sulfate, 1,3-bis (3-aminophenoxy) benzene, 3,3′-dichlorobenzidine, 2,2 ′, 5,5 ′ -Tetrachlorobenzidine, 4,4'-diamino-1,1'-binaphthyl, diamine bordeaux, benzoflavine, chrysanillin, 2,2'-thiobis (5-aminobenzenesulfonic acid), 4,4'-methylene-bis (2-chloroaniline), tetrabromomethylene dianiline, 4,4′-diamino-3,3′-dinitrodiphenyl ether, benzidine pyrophosphate, 3,6-diaminothioxanthene-10-dioxide dihcl, 4,4 '' -Diamino-p-terphenyl, 1,8-diamino-4,5-dihydroxyanthraquinone, bis (p-aminophenoxy) dimethylsilane, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4 '-Methylenedi-2,6-xylidine, 2-aminobenzaldehyde-ethylene-diimine, 3- Tilbenzidine dihydrochloride, 3,3′-diethylbenzidine dihydrochloride, 3,6-diaminoacridine hydrochloride, 4,4′-diamino-5,5′-dimethyl-2,2′-biphenyldisulfonic acid disodium salt Salt, 4,4'-methylenebis (3-chloro-2,6-diethylaniline), 4,4'-methylene-bis- (2,6-diethylaniline), 4,4'-methylenebis- (2,6 -Diisopropylaniline), toluylenediamine, 3,8-diamino-6-phenylphenanthridine, thionine perchlorate, dihydroethidium, thionine, 4,4-diaminobenzenesulfonylanilide, o-dianisidine hcl, 2,2 '-Dichloro-5,5'-dimethoxybenzidine, 3-methoxybenzidine, 2,2'-(hexamethylenedioxy) dianiline, 2, '-(Pentamethylenedioxy) dianiline, 2,2'-(ethylenedioxy) dianiline, 4- [4- (4-aminophenoxy) butoxy] aniline, 2,2'-diamino-4'-methoxy-4 -Methylbenzanilide, 5,5'-dimethyl-2,2'-dinitrobenzidine, n, n'-bis (2-aminophenyl) -1,3-propanediamine, 3,4'-diaminochalcone, 2, 3 ′, 4,5 ′, 6-pentaphenyl-3,4′-biphenyldiamine, 2-([1- (4- (1-[(2-aminophenyl) thio] -2-nitroethyl) phenyl)- 2-nitroethyl] thio) aniline, 2-((2-[(2-aminophenyl) thio] ethyl) thio) aniline, 2-((4-[(2-aminophenyl) thio] but-2-enyl) Thio) aniline, 4,4 '-Diamino-3,3'-dimethyldiphenylmethane, 2,2'-diaminobibenzyl, trimethylenebis (4-aminobenzoate), fluoresceinamine, benzidine mixture, 3-nitro-4,4'-methylenedianiline 4,4-diamino-2,2′-dichlorodiphenyl disulfide, 1,6-diaminopyrene, 1,8-diaminopyrene, 3,6-diaminocarbazole, 4,4 ′ (5 ′)-diamino- [2 , 4] -Dibenzo-18-crown-6, dihydrochloride, 4,4′-diaminostilbene-2,2′-disulfonic acid, disodium salt, (r)-(+)-2,2′-diamino -1,1'-binaphthyl, proflavine hemisulfate dihydrate, 3,6-diaminoacridine hemisulfate hemihydrate, dimidium bromide monohydrate, o-tolidine Hydrochloride hydrate, 3,3 ′, 5,5′-tetramethylbenzidine dihydrochloride hydrate, 3,3′-diaminobenzidine tetrahydrochloride dihydrate, 3,6- [bis (4-amino- 3- (sodiumsulfonato) phenylamino)]-2,5-dichloro 4-benzoquinone, 2,2'-dimethylbenzidine hydrochloride, 2,2 '-(phenylmethylenebis) bis (4-methylaniline), 3 , 4′-diaminobiphenyl, 2,7-diamino-9-fluorenone, n, n′-bis (2-aminophenyl) oxamide, 2- [2- (2-aminophenyl) diaza-1-enyl] aniline, 3,5,3 ′, 5′-tetrabromo-biphenyl-4,4′-diamine, n, n′-bis (4-aminophenyl) -1,3-bis (aminomethyl) benzene dihydrochloride, 4 ′ , 4 ″ (5 ″)-Diaminodi Nzo-15-crown-5,2,2'-bis (trifluoromethyl) benzidine, bis (4-amino-2,3-dichlorophenyl) methane, alpha, alpha'-bis (4-aminophenyl) -1 , 4-diisopropylbenzene, 2,2-bis (3-aminophenyl) hexafluoropropane, 3,10-diamino-6,13-dichlorobenzo [5,6] [1,4] oxazino [2,3-b ] Phenoxazine-4,11-disulfo, n1- (2-amino-4-methylphenyl) -2-aminobenzamide, n1- (2-amino-4-chlorophenyl) -2-aminobenzamide, 2,2′- Dichloro [1,1′-biphenyl] -4,4′-diamine, 4,4 ′ (5 ′)-diaminodibenzo-15-crown-5 dihydrochloride, rcl s19,413-1 Bis- (4-amino-3-nitro-phenyl) -methanone, bis- (3-amino-4-chloro-phenyl) -methanone, bis- (3-amino-4-dimethylamino-phenyl) -methanone, n, n′-bis- (4-amino-2-chloro-phenyl) -isophthalamide, n, n′-bis- (4-amino-2-chloro-phenyl) -terephthalamide, 3,9-diamino- 1,11-dimethyl-5,7-dihydro-dibenzo (a, c) cyclopenten-6-one, 2-aminobenzaldehyde n-[(z)-(2-aminophenyl) methylidene] hydrazone, 3,3′- Bis (trifluoromethyl) benzidine, dicarboxyzine 2hcl, 4,4 ′-(1,3-phenylenediisopropylidene) bisaniline, 1,4-phenylenebis [[4- 4-aminophenoxy) phenyl] methanone], 2-((5-[(2-aminophenyl) thio] -3,4-dinitro-2-thienyl) thio) aniline, n′1- (2-aminobenzoyl) 2-aminobenzene-1-carbohydrazide, 2- [4- (5-amino-1h-benzimidazol-2-yl) phenyl] -1h-benzimidazol-5-amine, 4- [4- (4- Aminophenoxy) -2,3,5,6-tetrafluorophenoxy] aniline, 3,3′-dinitro-4,4′-diaminodiphenylsulfone, 3,3 ′, 4,4′-tetraaminodiphenylsulfone, 4 -[1- (4-aminophenyl) -1-methylethyl] aniline, 3,3-diaminodiphenylurea, bis (4-aminophenyl) acetylene, dibenzo (1,2) di In-3,8-diamine, ethidium homodimer-2, 4,4'-bis- (2-aminobenzenesulfonyl) bis-phenol ester, neopentyl glycol bis (4-aminophenyl) ether, 2,2 '-Oxydianiline, 4,4'-diaminodiphenylamine-2,2-disulfonic acid, 4,4-diaminodiphenylurea, 3,3'-tolidine-5-sulfonic acid, n1- (3-[(2- Aminobenzoyl) amino] propyl) -2-aminobenzamide, 2-((6-[(2-aminophenyl) sulfanyl] -5-nitro-2-pyridyl) sulfanyl) aniline, 2-((6-amino-1) , 3-Benzothiazol-2-yl) dithio) -1,3-benzothiazol-6-ylamine, tetramethylbenzidine, 2-([6-[(2 Aminophenyl) sulfanyl] -3,5-di (trifluoromethyl) -2-pyridyl] sulfanyl) anil, 3,6-diaminothioxanthene-10-dioxide dihydrochloride, m-tolidine dihydrochloride hydrate, 2 -Amino-n- [2-amino-4- (trifluoromethyl) phenyl] -5-methylbenzamide, 2-([2-[(2-aminophenyl) thio] -6-nitro-4- (trifluoro Methyl) phenyl] thio) aniline, 2-[(3-([(2-aminophenyl) thio] methyl) -2,4,6-trimethylbenzyl) thio] aniline, 3- [3-amino-5- ( Trifluoromethyl) benzyl] -5- (trifluoromethyl) aniline, 2-((5-[(2-aminophenyl) thio] -4-chloro-2-nitrophenyl) thio) Niline, 4- (1- (4-aminophenyl) -2- [4- (dimethylamino) phenyl] vinyl) aniline, 1,5-bis (4-aminophenoxy) pentane, 2,3′-dichlorobenzidine Hydrochloride, 3,3′-diamino-4,4′-dichlorodiphenylsulfone, 3- (bis- (4-amino-phenyl) -methyl) -2,3-dihydro-isoindol-1-one, 4, 4-diaminodiphenyl-2-sulfonic acid, 4,4′-diamino-diphenylene-cyclohexane, 4,5′-diamino- (1,1 ′) bianthracenyl-9,10,9 ′, 10′-tetron.

Alicyclic diamine 4,4'-methylenebis (cyclohexylamine), 4,4'-methylenebis (2-methylcyclohexylamine).

Aliphatic diamine 1,8-diamino-p-menthane, 4,4′-methylenebis (cyclohexylamine), d-cystine, 1-cystine dimethyl ester dihydrochloride, neamine, bis (2-aminopropyl) amine, (h -Cys-beta-na) 2 2hcl, l-cystine dibenzyl ester ditosylate, 1.4-diaminocyclohexane, (h-cys-pna) 2, dl-2-aminopropanoic anhydride, l-cystine ( Di-b-naphthylamide) hydrochloride, l-cystine-bis-p-nitroanilide dihydrobromide, l-cystine diethyl ester dihydrochloride, trans-1,4-cyclohexanediamine, 4,4′-methylenebis (2-methylcyclohexylamine), l-leucine thiol oxide dihydrochloride, 1,3-diaminoadamantane dihydrochloride , L-leucine thiol disulfide 2HCl, l-cystine disodium salt monohydrate, l-homo cystine methyl ester hydrochloride, 1,3-adamantane diamine, tetracyclo [8.2.1.1 (8,11). 0 (2,7)] tetradeca-2,4,6-triene-10,11-diamine, tricyclo [3.3.1.0 (3,7)] nonane-3,7-diamine.

From the classification of commercially available diamines, those listed below are preferred.
Alicyclic diamine 4,4'-methylenebis (cyclohexylamine), 4,4'-methylenebis (2-methylcyclohexylamine)
Aliphatic diamine 4,4′-methylenebis (cyclohexylamine), 1,4-diaminocyclohexane, trans-1,4-cyclohexanediamine, 4,4′-methylenebis (2-methylcyclohexylamine), 1,3-adamantanediamine Aromatic diamine 2,7-diaminofluorene, 2,6-diaminoanthraquinone, 4,4'-diaminooctafluorobiphenyl, 4,4'-diaminodiphenyl ether, 4,4'-dithiodianiline, 4,4'-diamino Diphenylmethane, 4,4′-ethylenedianiline, 3,3′-dimethoxybenzidine, o-tolidine, 3,3′-diaminobenzophenone, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 2,2 -Bis [4- (4-aminophenoxy) phenyl] hexaful Oropropane, 4- [3- (4-aminophenoxy) propoxy] aniline, 4,4′-diaminodiphenyl sulfide, 4,4′-diaminobenzophenone, 2,2-bis (4-aminophenyl) hexafluoropropane, 4 , 4′-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis ( 4-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, 9,9-bis (4-aminophenyl) fluorene, benzidine, 4,4′-azodianiline, 1,3-bis (3 -Aminophenoxy) benzene, 4,4'-diamino-1,1'-binaphthyl, 4,4 "-diamino-p-terphenyl, bis p-aminophenoxy) dimethylsilane, 4- [4- (4-aminophenoxy) butoxy] aniline, 3,4'-diaminochalcone, trimethylenebis (4-aminobenzoate), 3,4'-diaminobiphenyl, 2,7-diamino-9-fluorenone, 4 ′, 4 ″ (5 ″)-diaminodibenzo-15-crown-5,2,2′-bis (trifluoromethyl) benzidine, alpha, alpha′-bis (4-aminophenyl) -1,4-diisopropylbenzene, 3,3′-bis (trifluoromethyl) benzidine, 4,4 ′-(1,3-phenylenediisopropylidene) bisaniline, 1,4-phenylenebis [[4- (4-Aminophenoxy) phenyl] methanone], 4- [4- (4-Aminophenoxy) -2,3,5,6-tetrafluorofe Xyl] aniline, 4- [1- (4-aminophenyl) -1-methylethyl] aniline, neopentyl glycol bis (4-aminophenyl) ether, 4,4-diaminodiphenyl or 1,5-bis (4- Aminophenoxy) pentane.

From the classification of commercially available diamines (L), those listed below are more preferred.
Aromatic diamine 2,7-diaminofluorene, 4,4′-diaminooctafluorobiphenyl, 4,4′-diaminodiphenyl ether,
4,4′-diaminodiphenylmethane, 4,4′-ethylenedianiline, 3,3′-diaminobenzophenone, 4- [3- (4-aminophenoxy) propoxy] aniline, 4,4′-diaminodiphenyl sulfide, 4 , 4′-diaminobenzophenone, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4′-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) Phenyl] propane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, benzidine, bis (p-amino) Phenoxy) dimethylsilane, 4- [4- (4-aminophenoxy) butoxy] aniline, 3,4'-diaminochalcone, Trimethylene bis (4-aminobenzoate), 3,4′-diaminobiphenyl, 2,7-diamino-9-fluorenone, 4 ′, 4 ″ (5 ″)-diaminodibenzo-15-crown-5, 4- [4- (4-aminophenoxy) -2,3,5,6-tetrafluorophenoxy] aniline, 4- [1- (4-aminophenyl) -1-methylethyl] aniline, 1,5-bis (4-Aminophenoxy) pentane aliphatic diamine 4,4′-methylenebis (cyclohexylamine), 1,4-diaminocyclohexanealicyclic diamine 4,4′-methylenebis (cyclohexylamine).

  Preferably, the further polymer, homo- or copolymer or oligomer comprises at least a diamine as one basic building block and a tetracarboxylic anhydride, preferably a tetracarboxylic anhydride of the formula (VII). Including.

［式中、
Ｔは、四価の有機基を表わす］
のものである。 Preferably, the substituted or unsubstituted, preferably substituted or unsubstituted tetracarboxylic anhydride in the polar group is of formula (VII):

[Where:
T represents a tetravalent organic group]
belongs to.

  The tetravalent organic group T is preferably obtained from an aliphatic, alicyclic or aromatic tetracarboxylic dianhydride.

  The tetravalent organic group T is preferably obtained from an aliphatic, alicyclic or aromatic tetracarboxylic dianhydride.

  Preferred examples of the aliphatic or alicyclic tetracarboxylic dianhydride include 1,1,4,4-butanetetracarboxylic dianhydride, ethylene maleic dianhydride, 1,2,3,4-cyclobutane. Tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride; 2,3,5-tricarboxycyclopentylacetic acid dianhydride ("2,3,5-tricarboxycyclopentylacetic acid dianhydride For the term "anhydride" all isomers of this compound are included, in particular exo and / or endo isomers) (2,3,5-tricarboxycyclopentylacetic acid-1,2: 3,4-dianhydride For example, JP 59-190945, 60-13740 and 58-109479, DE 1078120 and JP 58-1094, respectively. 9 or GB 872,355 and JP 4-458299, which is incorporated herein by reference); Tetrahydro-4,8-methanofuro [3,4 -D] oxepin-1,3,5,7-tetron, 3- (carboxymethyl) -1,2,4-cyclopentanetricarboxylic acid 1,4: 2,3-dianhydride, hexahydrofuro [3 ' , 4 ′: 4,5] cyclopenta [1,2-c] pyran-1,3,4,6-tetron, 3,5,6-tricarboxy-norbornyl acetic acid dianhydride, 2,3,4,5 -Tetrahydrofuran tetracarboxylic dianhydride, rel- [1S, 5R, 6R] -3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2 ', 5'-dione), 4- (2,5-dioxotetrahydrofuran-3-yl) tetrahydronaphthalene-1,2-dicarboxylic dianhydride, 5- (2,5-dioxotetrahydro-furan-3 -Yl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride Bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic dianhydride, 1,8-dimethylbicyclo [2.2.2] oct-7-ene-2,3,5 , 6-tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, 3,3 ′ , 4,4'-Diphenylsulfonetetracar Acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-difluoro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3-trimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2, 3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1-methyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,4,5,8 -Naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3', 4,4'-tetrafe Rusilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4 ′ -Bis (3,4-dicarboxyphenoxy) -diphenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-biphenyl Tetracarboxylic dianhydride, ethylene glycol bis (trimellitic acid) dianhydride, 4,4 '-(1,4-phenylene) bis (phthalic acid) dianhydride, 4,4'-(1,3- Phenylene) bis (phthalic acid) dianhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic dianhydride, 4-tert-butyl-6- (2,5-dioxotetrahydro-3-furanyl) 2-benzofuran-1,3-dione, 5- (2,5-dioxotetrahydro-3-furanyl) -3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3- Dione, 5- (2,5-dioxotetrahydro-3-furanyl) -5-methyl-3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione, 5- ( 2,5-dioxotetrahydro-3-furanyl) -6-methylhexahydro-2-benzofuran-1,3-dione, 5- (2,5-dioxotetrahydro-3-furanyl) -7-methyl-3a , 4,5,7a-tetrahydro-2-benzofuran-1,3-dione, 6- (2,5-dioxotetrahydro-3-furanyl) -4-methylhexahydro-2-benzofuran-1,3-dione 9-Isop Lopyloctahydro-4,8-ethenofuro [3 ′, 4 ′: 3,4] cyclobuta [1,2-f] [2] benzofuran-1,3,5,7-tetron, 1,2,5 6-cyclooctanetetracarboxylic dianhydride, octahydro-4,8-ethenofuro [3 ′, 4 ′: 3,4] cyclobuta [1,2-f] [2] benzofuran-1,3,5,7- Tetron, octahydrofuro [3 ′, 4 ′: 3,4] cyclobuta [1,2-f] [2] benzofuran-1,3,5,7-tetron, tetrahydro-3,3′-bifuran-2, 2 ', 5,5'-tetron, 4,4'-oxydi (1,4-phenylene) bis (phthalic acid) dianhydride and 4,4'-methylenedi (1,4-phenylene) bis (phthalic acid) Dianhydride.

  Preferred examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, 3 , 3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetra Carboxylic acid dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, ethylene glycol bis (trimellitic acid) Anhydride, 4,4 ′-(1,4-phenylene) bis (phthalic acid) dianhydride, 4,4 ′-(1,3-phenylene) bis (phthalic acid) dianhydride, 4,4′- (Hexafluoroisopropylidene) diphthalic acid diacid water, 4,4′-oxydi (1,4-phenylene) bis (phthalic acid) dianhydride, 4,4′-methylenedi (1,4-phenylene) bis ( Phthalic acid) dianhydride, 4-tert-butyl-6- (2,5-dioxotetrahydro-3-furanyl) -2-benzofuran-1,3-dione, and the like.

  More preferably, the tetracarboxylic dianhydride used to form the tetravalent organic group T is 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4- Cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, tetrahydro-4,8-methanofuro [3,4-d] oxepin-1,3,5,7-tetron, 3 -(Carboxymethyl) -1,2,4-cyclopentanetricarboxylic acid 1,4: 2,3-dianhydride, hexahydrofuro [3 ′, 4 ′: 4,5] cyclopenta [1,2-c] Pyran-1,3,4,6-tetron, 5- (2,5-dioxotetrahydrofuran-3-yl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, pyromellitic acid 2 Anhydride, 4- 2,5-dioxotetrahydrofuran-3-yl) tetrahydronaphthalene-1,2-dicarboxylic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -5-methyl-3a, 4,5 , 9b-tetrahydronaphtho [1,2-c] furan-1,3-dione, 5- (2,5-dioxotetrahydro-3-furanyl) -3a, 4,5,9b-tetrahydronaphtho [1,2 -C] furan-1,3-dione, 5- (2,5-dioxotetrahydro-3-furanyl) -7-methyl-3a, 4,5,7a-tetrahydro-2-benzofuran-1,3-dione 4-tert-butyl-6- (2,5-dioxotetrahydro-3-furanyl) -2-benzofuran-1,3-dione, 4,4 ′-(hexafluoroneopropylidene) diphthalic acid Is selected from the object and bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride.

  In the context of the present invention, the term “polyimide” means a partially or fully imidized polyamic acid or polyamic acid ester. Similarly, the term “imidization” means partial or complete imidization in the context of the present invention.

  The second embodiment of the present invention, among others, is that the second polymer or copolymer is 100% imidized, or 1 to 99% by weight, preferably 5 to 50% by weight, more preferably 10 to 10%. It relates to a composition having a degree of imidization in the range of 40% by weight.

  In the context of the second embodiment of the present invention, the composition comprises a siloxane copolymer as described above, a second polymer or copolymer different from the first, and the first and second polymers of the composition. Or at least one further polymer or copolymer different from the copolymer.

  In a second preferred embodiment, the present invention comprises at least one siloxane copolymer as described above, a second polymer or copolymer different from the first, and an additive, which additive is It relates to a composition which is a known additive.

  Additives include nucleating agents, fining agents, antistatic agents, antioxidants, slip agents, silica, talc, stabilizers, UV stabilizers, lubricants, coupling agents, antibacterial agents, cross-linking agents, and crosslinking of polymer backbones. Agents to improve, eg acid generators, base generators or tetra-alkoxy-siloxanes, eg tetraethoxysilane or siloxane monomers, eg trialkoxysilanes; surfactants, photoactivators, photosensitizers, light Selected from the group consisting of generators.

  Additives such as silane-containing compounds and epoxy-containing crosslinking agents can be added.

  Suitable silane-containing additives are described in Plast. Eng. 36 (1996), (Polyimides, fundamentals and applications), Marcel Dekker, Inc.

  Suitable epoxy-containing crosslinkable additives are 4,4′-methylene-bis- (N, N-diglycidylaniline), trimethylolpropane triglycidyl ether, benzene-1,2,4,5-tetracarboxylic acid 1 2,4,5-N, N′-diglycidyl diimide, polyethylene glycol diglycidyl ether, N, N-diglycidyl cyclohexylamine and the like.

  Suitable photoactivators are 2,2-dimethoxyphenylethanone, a mixture of diphenylmethanone and N, N-dimethylbenzenamine or ethyl 4- (dimethylamino) -benzoate, xanthone, thioxanthone, 1-hydroxy- Cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, Irgacure® 500 (1-hydroxy-cyclohexyl-phenyl-ketone and benzophenone 1: 1 (by weight) mixture) and 2,2-dimethoxy-1,2-diphenylethane-1-one, Michler's ketone, tertiary sulfonium salt and the like.

  The composition, preferably the blend, of the second embodiment of the present invention comprises a copolymer of the definition and selection of the present invention and a second polymer or copolymer different from the first, optionally with an organic solvent. In addition. In the context of the present invention, organic solvent means any solvent generally known in the art. In particular, the organic solvent is selected from the group consisting of hydrocarbons, ketones, esters, ethers and alcohols.

  Examples of the hydrocarbon include toluene and xylene, examples of the ketone include methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone and cyclohexanone, examples of the ester include ethyl acetate, n-butyl acetate, acetic acid Examples of the alcohols include i-amyl, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate and ethyl lactate, examples of the ethers include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran and dioxane. 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethyl Including glycol mono -n- butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol mono -n- propyl ether. Among these, a water-insoluble organic solvent is preferable.

  Further examples of organic solvents are chlorobenzene, pyrrolidone solvents, preferably N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone; imidazolidinone, dimethyl sulfoxide, dimethylformamide, Toluene, chloroform, organic esters, such as acetic acid acetyl ester or acetic acid butyl ester, acetic acid pentyl ester, acetic acid hexyl ester; And propylene glycol dimethyl ether and diisobutyl ketone monoethylene glycol dimethyl ether. These solvents can be used alone or in a mixture thereof.

  The amount of the organic solvent is preferably 0.5 to 150,000 parts by weight, preferably 100 to 100000 parts by weight, more preferably 150 to 25000 parts by weight, based on 100 parts by weight of all copolymer compounds. .

  An organic solvent can be used individually or in combination of 2 or more.

  A third object of the present invention is to provide an alignment layer comprising one said copolymer.

  In the context of the present invention, the term “polymer or oligomer layer” means “polymer layer, copolymer layer or oligomer layer”.

  In the context of the present invention, the term “alignment layer” has the same meaning as “alignment film”.

  The copolymers of the present invention can be used alone or in the form of an alignment layer, depending on the application to which the polymer or oligomer layer is added, or other polymers, copolymers, oligomers, monomers, photoactive polymers, photoactive oligomers and / or photoactive monomers. Can be used in combination. Thus, it is understood that by changing the composition of the copolymer layer, specific and desired properties such as good surface wetting, high voltage holding ratio, specific holding energy, etc. can be controlled.

  The fourth object of the present invention is to provide a method for producing an alignment layer containing the copolymer by exposing the copolymer to alignment light, and an alignment layer obtained by such a method.

  The copolymer contains at least one photoreactive group in its side chain.

  Preferably, the photoreactive group of this side chain reacts upon exposure to alignment light.

  In the context of the present invention, the term “photoreactive group” means a group capable of reacting by interaction with light, preferably orientation light.

  The treatment with orientation light can be performed in one step or in a plurality of separate steps. In a preferred embodiment of the invention, the treatment with orientation light is performed in one step.

  In the context of the present invention, photoreactive groups preferably mean dimerizable, isomerizable, polymerizable and / or crosslinkable groups.

  In the context of the present invention, alignment light, preferably polarized light, is light of a wavelength such that photo alignment can be initiated. Preferably, this wavelength is in the UV-A, UVB and / or UV / C range or the visible range. This wavelength is determined by the photoalignment compound whose wavelength is appropriate. Preferably, the photoreactive group is sensitive to visible light and / or UV light. A further embodiment of the present invention relates to generating alignment light by laser light.

  The instantaneous direction of the orientation light can be perpendicular to the substrate or can be any oblique angle.

  More preferably, the orientation light is at least partially linearly polarized, elliptically polarized, such as circularly polarized or unpolarized, most preferably at least circularly polarized or partially linearly polarized, or unpolarized exposed from an oblique direction. . In particular, most preferred alignment light refers to substantially polarized light, particularly linearly polarized light, or alignment light refers to non-polarized light applied by oblique illumination.

  A more preferred embodiment of the invention relates to a method for producing alignment layers by exposing the copolymer to polarized light, in particular linearly polarized light, or by oblique irradiation with non-polarized light.

The copolymer is a copolymer gel or copolymer network, and / or where the copolymer has an intrinsic viscosity in the range of 0.01 to 10 dL / g, preferably in the range of 0.02 to 5 dL / g. And / or-where the copolymer is 1-6'000'000, 1'000-6'000'000, 2'000-1'000'000, 2'000-500'000, more preferably Having a molecular weight of 5'000 to 250'000,
Where the copolymer contains 2 to 20000 repeat units, in particular 4 to 2000 repeat units, in particular 6 to 1000 repeat units, and / or where the copolymer or oligomer is a random copolymer of In form,
Even more preferred are the copolymers of the present invention.

  A further preferred embodiment of the present invention relates to a copolymer which preferably has an intrinsic viscosity in the range of 0.01 to 10 dL / g, more preferably in the range of 0.01 to 1 dL / g. In this specification, the intrinsic viscosity (ηinh = lnηrel / C) is a 0.5 g / 100 ml solution of copolymer for evaluation of its viscosity at 30 ° C. using N-methyl-2-pyrrolidone as a solvent. Is determined by measuring a solution containing

  In addition, a preferred embodiment of the present invention relates to a copolymer containing 2 to 20000 repeat units, in particular 4 to 2000 repeat units, in particular 6 to 1000 repeat units.

  The copolymer layer can be easily prepared from the copolymer of the present invention, and a further embodiment of the present invention preferably relates to a copolymer layer comprising the copolymer of the present invention prepared by treatment with oriented light.

  Preferably, the present invention relates to a copolymer layer comprising a copolymer of the present invention or produced according to the present invention.

  The copolymer layer is preferably prepared by applying one or more copolymers or compositions of the present invention to a support and irradiating the copolymer or copolymer mixture with oriented light after or without imidization. . Oriented light has the meaning and choice given above.

  As used in the context of the present invention, the term “support” is preferably transparent or opaque, preferably by a glass or plastic substrate, a polymer film, eg optionally indium tin oxide (ITO). Examples include, but are not limited to, polyethylene terephthalate (PET), tri-acetylcellulose (TAC), and polypropylene.

  In general, compositions comprising the copolymers of the present invention are applied by common coating and printing methods known in the art. For example, spin coating, meniscus coating, wire coating, slot coating, offset printing, flexographic printing, gravure printing, in-jet printing can be used. Coating methods include, for example, spin coating, air doctor coating, blade coating, knife coating, reverse roll coating, transfer roll coating, gravure roll coating, kiss roll coating, cast coating, spray coating, slot orifice coating, calendar coating, electrodeposition Coating, dip coating or die coating.

  Generally inflexible, optionally coated with indium tin oxide (ITO) or Pedot: PSS (poly (3,4-ethylenedioxythiophene) poly (styrene sulfonate) or graphene-based materials A transparent support that is a substrate or a flexible substrate is used, for example glass or plastic, which is used for flexible LCDs.

  The printing method is, for example, letterpress printing, for example flexographic printing, ink jet printing, intaglio printing, for example direct gravure printing or offset gravure printing, lithographic printing, for example offset printing or stencil printing, for example screen printing. A further preferred embodiment of the invention relates to an alignment layer that is unstructured or structured.

  In addition, the present invention relates to a method for producing a structured copolymer layer comprising varying the orientation direction and / or tilt angle within the copolymer layer. This change in the orientation direction and / or tilt angle can be performed, for example, by controlling the direction of orientation light irradiation. It is understood that by selectively irradiating a specific region of the polymer, copolymer or oligomer layer, a very specific region of this layer can be oriented. In this way, a layer having a defined tilt angle can be provided.

  The irradiation time is determined by the output of each lamp and can vary from a few seconds to several hours. However, for example, a photoreaction can be performed by irradiation of a homogeneous layer using a filter that can pass only irradiation suitable for the reaction.

  More preferred is a method for preparing a copolymer layer, for preparing a planar multi-domain orientation of the copolymer layer, and / or for preparing a copolymer layer having a tilt angle within the predetermined meaning and choice of the present invention. .

  A further preferred embodiment of the present invention relates to an alignment layer comprising one or more copolymers of the present invention.

  In the context of the present invention, the alignment layer has the same meaning and selection as the alignment layer, copolymer layer, and is preferably a photo-alignment layer.

  In the context of the present invention, the alignment layer is used for planar alignment of liquid crystals (in-plane switching) or vertical alignment of liquid crystals.

  In a more preferred embodiment, the present invention relates to the alignment layer of the present invention and its use for the planar alignment of liquid crystals.

  In the context of the present invention, the term “liquid crystal alignment” means that the liquid crystal has a tilt angle.

  As used in the context of the present invention, the term tilt angle is the angle between the liquid crystal director and the alignment layer surface. The liquid crystal director shall mean the average direction of the major axis of the liquid crystal molecules. In the context of the present invention, planar orientation shall mean that the tilt angle is less than 30 °, preferably 0-30 °.

  In a preferred embodiment, the tilt angle of the liquid crystal attracted by the photo-alignment layer is less than 10 °, preferably 0-10 °. In a more preferred embodiment, the tilt angle is less than 5 °, preferably 0-5 °, and in the most preferred embodiment, the tilt angle is less than 1 °, preferably 0-1 °, even more preferably. 0 ° to 0.5 °. The tilt angle is preferably 0.2 ° or less than 0.1 °.

  In the context of the present invention, the vertical alignment is a tilt angle of 70 °, greater than 75 °, preferably 80 °, greater than 85 °, more preferably 85 ° -90 °, and even more preferably 86 ° -87 °. Or it is meant to be 87 ° to 88 ° or 88 ° to 89 ° or 89 ° to 90 °.

The fifth embodiment of the present invention is:
a) a liquid crystal composition comprising one or more polymerizable liquid crystal monomers or comprising one or more liquid crystal polymers or oligomers which are polymerized forms of said polymerizable liquid crystal monomers, and / or b) one or more polymerizable liquid crystals. A liquid crystal composition comprising one or more liquid crystal polymers or oligomers containing a monomer or a polymerized form of the polymerizable liquid crystal monomer, wherein the liquid crystal composition is sandwiched between a pair of alignment layers Of things
Use of the alignment layer for orientation, in particular for planar orientation.

  Examples of liquid crystal polymers (LCP) are described in US 2012/114907. This document is incorporated by reference.

As used in the context of the present application, LCP material shall mean a liquid crystal material comprising liquid crystal monomers and / or liquid crystal dimers and / or liquid crystal polymers and / or cross-linked liquid crystals. When the liquid crystal material includes a liquid crystal monomer, such a monomer can typically be polymerized after anisotropy has occurred in the LCP material by contact with the photoalignment material. The polymerization can be initiated by heat treatment or, preferably, exposure to active light including UV light.
The LCP material can consist of one type of liquid crystal compound, but can also be a composition of various polymerizable and / or non-polymerizable compounds. Here, not all of the compounds need to be liquid crystal compounds. In addition, the LCP material can contain additives such as photoinitiators or isotropic or anisotropic fluorescent agents and / or non-fluorescent dyes.

  Furthermore, the present invention preferably relates to the use of the alignment layer of the present invention to induce planar alignment of adjacent liquid crystal layers, and in particular to operate a cell. Here, the planar orientation is, for example, IPS, for example, IPS mode, for example, S-IPS (Super IPS), AS-IPS (Advanced Super IPS), E-IPS (Enhanced IPS), H-IPS (Horizontal IPS). , UH-IPS, S-IPS II, e-IPS, p-IPS (performance IPS), PLS technology (plane-to-line switching), PS-IPS (polymer stabilized IPS), electric field induced photoreactive alignment IPS FFS ( Provided for fringe field switching), TN (twisted nematic), STN (super twisted nematic).

  The liquid crystal composition of the present invention contains a polymerizable monomer or a polymer or oligomer that is a polymerization form of the polymerizable monomer. The polymerizable monomer or polymer or oligomer is difunctional and / or has a hard core (eg, benzene). Even more preferred are polymerizable monomers or polymers or oligomers having one or more rings or fused ring structures and functional groups directly attached to the rings or fused ring structures.

−ＮＲ^１２−により置き換えられていることができ、ここで、置換基は、好ましくは、少なくとも１つＣ_１〜Ｃ_６アルキル、好ましくは、メチルであり、ここで、Ｒ^１２は、低級アルキルであり、
Ａｂ_１及びＡｂ_２は、環状構造であり、本発明において与えられた意味及び選択で、非置換又は置換の炭素環もしくは複素環芳香族又は脂環式基から独立して選択され、１，４−フェニレン、ナフタレン−２，６−ジイル、ターフェニル、クオーターフェニル、フェナントレン基が特に好ましく、
Ｚｂ_１は、−Ｏ−、−ＣＯ−、−ＣＨ（ＯＨ）−、−ＣＨ_２（ＣＯ）−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−Ｏ−ＣＨ_２−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−（ＣＯ）−（ＣＯ）−、−ＯＣＦ_２−、−ＣＦ_２Ｏ−、−ＣＦ_２−、−ＣＯＮ（Ｃ_１〜Ｃ_１６アルキル）−、−（Ｃ_１〜Ｃ_１６アルキル）ＮＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＨＮＯＣＯ−、−ＯＣＯＮＨ−、−ＮＨＣＯＮＨ−、−ＯＣＯＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−、−ＣＳＳ、−ＳＯＯ−、−ＯＳＯ−、−ＳＯＳ−、−ＳＯ−、−ＣＨ_２（ＳＯ）−、−ＳＯ_２−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＨ＝Ｎ−、−Ｃ（ＣＨ_３）＝Ｎ−、−Ｎ＝Ｎ−もしくは単結合；又は環状、直鎖もしくは分岐鎖で、置換もしくは非置換のＣ_１〜Ｃ_２４アルキレンから選択され、同アルキレンにおいて、１つ以上のＣ−原子、ＣＨ−又はＣＨ_２−基は、それぞれ独立して、連結基により置き換えられていることができ、
好ましくは、Ｚｂ_１は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯ−、−ＯＣＦ_２−、−ＣＦ_２Ｏ−、−ＣＯＮ（ＣＨ_３）−、−（ＣＨ_３）ＮＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−、−ＣＳＳ、−ＳＯＯ−、−ＯＳＯ−、−ＣＳＳ−、−ＳＯＯ−、−ＯＳＯ−、−ＣＨ_２（ＳＯ_２）−、−ＣＨ_２−ＣＨ_２−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−又は単結合であり、
より好ましくは、Ｚｂ_１は、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯ−、−ＯＣＦ_２−、−ＣＦ_２Ｏ−、−ＣＯＮ（ＣＨ_３）−、−（ＣＨ_３）ＮＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−、−ＣＳ−Ｓ−、−ＳＯＯ−、−ＯＳＯ、特に、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＦ_２−、−ＣＦ_２Ｏ−、−ＣＯＮ（ＣＨ_３）−、−（ＣＨ_３）ＮＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−又は単結合であり、
最も好ましいＺｂ_１は、単結合、−ＣＯＯ−又は−ＯＣＯ−であり、
ｇは、１、２又は３の整数である］
で示されるモノマーを有する。 More preferred liquid crystal has the formula (VIII)
P ₁ -S _a -Ab _1- (Zb ₁ -Ab ₂ ) _g -S _b -P ₂ (VIII)
[Where:
P ₁ and P ₂ are functional groups and are independent of acrylate, methacrylate, halogen acrylate, eg fluoroacrylate, chloroacrylate; oxetanyl, maleimidyl, allyl, allyloxy, vinyl, vinyloxy and epoxy groups. Selected,
S _a and S _b are each independently a single bond or a spacer unit, and the spacer unit is preferably a linear or branched, substituted or unsubstituted C _{1 to} C ₂₄ alkylene, and In alkylene, one or more, preferably non-adjacent C-atoms, CH— or CH ₂ — groups can be replaced by linking groups within the meaning and choice given above, preferably Is a single bond, —O—, —O (CO), —S—, — (CO) O— or

-NR ^12- can be substituted, wherein the substituent is preferably at least one C ₁ -C ₆ alkyl, preferably methyl, wherein R ¹² is lower alkyl Yes,
Ab ₁ and Ab ₂ are cyclic structures, and are independently selected from unsubstituted or substituted carbocyclic or heterocyclic aromatic or alicyclic groups with the meaning and choice given in the present invention; -Phenylene, naphthalene-2,6-diyl, terphenyl, quarterphenyl, phenanthrene groups are particularly preferred,
Zb ₁ is —O—, —CO—, —CH (OH) —, —CH ₂ (CO) —, —OCH ₂ —, —CH ₂ O—, —O—CH ₂ —O—, —COO—. _{, -OCO -, - (CO)} - (CO) -, - OCF 2 -, - CF 2 O -, - CF 2 -, - CON (C 1 ~C 16 _{alkyl) -, - (C 1 ~C} 16 Alkyl) NCO-, -CONH-, -NHCO-, -HNOCO-, -OCONH-, -NHCONH-, -OCOO-, -CO-S-, -S-CO-, -CSS, -SOO-, -OSO _{-, - SOS -, - SO} -, - CH 2 (SO) -, - SO 2 -, - CH = CH -, - C≡C -, - CH = CH-COO -, - OCO-CH = CH- _{, -CH = N -, - C} (CH 3) = N -, - N = N- or a single bond; or a cyclic, straight-chain or branched-chain Is selected from _C 1 _{-C 24} alkylene substituted or unsubstituted, in the alkylene, one or more C- atoms, CH- or CH ₂ - groups are each independently be replaced by a linking group Can
Preferably, Zb ₁ is —O—, —CO—, —COO—, —OCO—, —OCOO—, —OCF ₂ —, —CF ₂ O—, —CON (CH ₃ ) —, — (CH ₃ ) NCO-, -CONH-, -NHCO-, -CO-S-, -S-CO-, -CSS, -SOO-, -OSO-, -CSS-, -SOO-, -OSO-, -CH ₂ (SO ₂ ) —, —CH ₂ —CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CH═CH—, —C≡C—, —CH═CH—COO—, —OCO—CH═ CH— or a single bond,
More preferably, Zb ₁ is —COO—, —OCO—, —OCOO—, —OCF ₂ —, —CF ₂ O—, —CON (CH ₃ ) —, — (CH ₃ ) NCO—, —CONH—. , —NHCO—, —CO—S—, —S—CO—, —CS—S—, —SOO—, —OSO, in particular —COO—, —OCO—, —OCF ₂ —, —CF ₂ O— _{, -CON (CH 3) -,} - (CH 3) NCO -, - CONH -, - NHCO- or a single bond,
Most preferred Zb ₁ is a single bond, —COO— or —OCO—,
g is an integer of 1, 2 or 3]
It has the monomer shown by these.

In formula (VI), P ₁ and P ₂ are preferably acrylate or methacrylate groups, S ₁ and S ₂ are single bonds, Zb ₁ is preferably a single bond, and g is , Preferably 0 or 1.

［式中、
Ｐ_１及びＰ_２は、それぞれ独立して、アクリラート、メタクリラート、オキセタン、マレインイミド、アリル、アリルオキシ、ビニル、ビニルアミド、ビニルオキシ及びエポキシ基、エポキシ誘導体、ブトキシ及びブトキシ誘導体であり、
Ｂは、単結合、−ＣＯ−Ｃ（Ｃ_１〜Ｃ_６アルコキシ）_２−、−ＣＯＯ−、−ＯＣＯ−であり、
液晶のＹ_１、Ｙ_２、Ｙ_３、Ｙ_４、Ｙ_５、Ｙ_６は、それぞれ独立して、水素、直鎖又は分岐鎖のＣ_１〜Ｃ_１６アルキル基（同アルキル基は、非置換又は、フッ素、ジ−（Ｃ_１〜Ｃ_１６アルキル）アミノ、Ｃ_１〜Ｃ_１５アルキルオキシ、ニトロ、ニトリル及び／又は塩素により置換されており、ここで、１つ以上Ｃ−原子、ＣＨ−又はＣＨ_２−基は、それぞれ独立して、連結基により置き換えられていることができ）；ハロゲン又はニトリルであり、好ましい置換基は、Ｃ_１〜Ｃ_６アルキル基、特に、メチル又はエチル、Ｃ_１〜Ｃ_６アルコキシ基、特に、メトキシ又はエトキシ、塩素、フッ素又はニトリル、より好ましくは、メトキシ、塩素、フッ素又はＣＮ、及び最も好ましくは、メトキシ、塩素又はフッ素であり、更に、芳香族基が置換されている場合には、好ましくは、１回又は２回置換されており、
液晶のＳ_１、Ｓ_２は、それぞれ独立して、単結合又はスペーサ単位であり、同スペーサ単位は、好ましくは、直鎖又は分岐鎖で置換又は非置換のＣ_１〜Ｃ_２４アルキレンであり、同アルキレンにおいて、１つ以上の、好ましくは、隣接していないＣ−原子、ＣＨ−又はＣＨ_２−基は、上記所定の意味及び選択内の連結基により置き換えられていることができ、
かつ、好ましくは、単結合、−Ｏ−、−Ｏ（ＣＯ）、−Ｓ−、−（ＣＯ）Ｏ−又は

−ＮＲ^１２−により置き換えられていることができ、ここで、置換基は、好ましくは、少なくとも１つＣ_１〜Ｃ_６アルキル、好ましくは、メチルであり、ここで、Ｒ^１２は、低級である］
のいずれか１つにより示される化合物が最も好ましい。 The liquid crystal has the formula (IX), (X), (Xa), (XI) or (XIb)

[Where:
P ₁ and P ₂ are each independently acrylate, methacrylate, oxetane, maleimide, allyl, allyloxy, vinyl, vinylamide, vinyloxy and epoxy groups, epoxy derivatives, butoxy and butoxy derivatives;
B is a single bond, —CO—C (C ₁ -C ₆ alkoxy) ₂ —, —COO—, —OCO—,
Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ and Y ₆ of the liquid crystal are each independently hydrogen, a linear or branched C _{1 to} C ₁₆ alkyl group (the alkyl group is unsubstituted or , Fluorine, di- (C ₁ -C ₁₆ alkyl) amino, C ₁ -C ₁₅ alkyloxy, nitro, nitrile and / or chlorine, wherein one or more C-atoms, CH— or CH _{The 2} -groups can each independently be replaced by a linking group); halogen or nitrile, preferred substituents are C ₁ -C ₆ alkyl groups, in particular methyl or ethyl, C _1- C ₆ alkoxy group, especially methoxy or ethoxy, chlorine, fluorine or nitrile, and more preferably, methoxy, chlorine, fluorine or CN, and most preferably, methoxy, chlorine or fluorine, furthermore, When the aromatic group is substituted, it is preferably substituted once or twice,
S ₁ and S ₂ of the liquid crystal are each independently a single bond or a spacer unit, and the spacer unit is preferably a linear or branched substituted or unsubstituted C _{1 to} C ₂₄ alkylene, In the same alkylene, one or more, preferably non-adjacent C-atoms, CH— or CH ₂ — groups can be replaced by a linking group within the given meaning and selection above,
And preferably, a single bond, —O—, —O (CO), —S—, — (CO) O— or

-NR ^12- can be substituted, wherein the substituent is preferably at least one C ₁ -C ₆ alkyl, preferably methyl, where R ¹² is lower ]
The compound represented by any one of is most preferable.

In formula (IX), P ₁ and P ₂ are preferably acrylate or methacrylate groups, S ₁ and S ₂ are single bonds, Z ₁ is preferably a single bond, and n is , Preferably 0 or 1.

  In formulas (IX) and (XI), the substituents for the benzene ring are in the o-position, m-position or p-position. In the formula (X), the substituents for the naphthalene ring are o-position, m-position, p-position, ana-position, E (epi) -position, kata-position, pen-position, pros-position, amphi. Present in the -position or the 2,7-position. The substituent for the benzene ring is preferably present in the p-position among the above positions. The substituent for the naphthalene ring is preferably present in the amphi-position among the above positions.

が好ましい。

Is preferred.

  In general, the liquid crystal composition or the liquid crystal layer is not particularly limited, provided that they contain the mono- or / and multi-polymerizable monomers described above. For this reason, the liquid crystal composition or the liquid crystal layer can be manufactured from any of various liquid crystal materials known to the public. The liquid crystal composition or the liquid crystal layer can be manufactured from the same liquid crystal material as the display application or a liquid crystal material different from the same application.

  In a sixth embodiment, the present invention relates to a method for manufacturing a liquid crystal display.

  In the context of the present invention, the term “display” has the same meaning as the term “panel”.

  The method for manufacturing the liquid crystal display panel may be by using a polymerization initiator, for example, methyl ethyl ketone peroxide and a benzoyl ether compound.

  Preferably, the invention provides at least one LCP on the siloxane polymer, copolymer or oligomer layer of the first or second embodiment of the invention or, preferably, the alignment layer of the fourth embodiment of the invention. The present invention relates to a method for manufacturing a liquid crystal display, comprising coating on and polymerizing the LCP.

  In general, the polymerization of LCP is carried out by irradiation or high temperature.

  LCP can be applied in any amount on the alignment layer. Such amount is not particularly limited. This amount can be appropriately set according to each thickness of the LCP polymer film formed by polymerization of the monomer LCP, for example.

  Furthermore, the present invention provides a liquid crystal composition comprising the above-described polymerizable liquid crystal monomer or a polymer or oligomer that is a polymerization form of the polymerizable liquid crystal monomer, preferably facing each other with at least one alignment layer of the present invention. The present invention relates to a method for manufacturing a liquid crystal display, comprising contacting two alignment layers that are present and polymerizing the polymerizable liquid crystal monomer.

  In general, the polymerization process is not limited as long as it does not have an adverse effect on the manufactured device. Preferably the polymerization is carried out by irradiation, in particular UV irradiation or heat.

  More specifically, a method for producing a liquid crystal display, preferably an LCD comprising a planarly oriented liquid crystal, in particular an LCD comprising an IPS mode, comprising an alignment layer and an electrode according to the present invention is a Exposure, preferably a first exposure, which induces an orientation direction of the liquid crystal perpendicular to the polarization or / and exposure, preferably a first exposure, aligns the liquid crystal. The direction is attracted and the polarization direction makes an angle greater than 70 °, or / and where the exposure with polarized light, preferably the first exposure, is an angle> 70 ° between the electrode and the direction of polarization Including exposure.

  The seventh object of the present invention relates to an optical or electro-optical unstructured or structured element comprising the copolymer of the present invention or the alignment layer of the present invention.

  In a preferred embodiment, the device is a liquid crystal display cell.

  In the context of the present invention, elements, devices, cells, structures all refer to an object comprising a polymerized or polymerizable liquid crystal that is aligned by the copolymer of the present invention.

Preferably, the invention further relates to an unstructured or structured-element optical or electro-optical device, in particular an LCD comprising a pair of substrates facing each other. Here, the base material includes a pair of alignment layers of the present invention,
-A) optionally an LCP polymer film, wherein the polymer film comprises an LCP polymer thin film formed on the alignment layer, or -b), preferably comprising at least a polymer formed from a polymerizable liquid crystal monomer A liquid crystal composition, wherein the liquid crystal composition is provided together with a liquid crystal composition sandwiched between a pair of alignment layers.

  The invention also preferably relates to the alignment of liquid crystals in the manufacture of unstructured or structured optical or electro-optical elements, preferably in the manufacture of hybrid layer elements, preferably for planar alignment. It relates to the use of such an alignment layer. Preferably, these optical or electro-optical devices have at least one alignment layer and unstructured and structured optical elements and multilayer systems. A layer or each layer can contain one or more regions of different spatial orientation.

  The polarization direction means a line of intersection between the alignment layer surface and the polarization plane of polarized light during exposure. When the polarization is elliptical polarization, the plane of polarization shall mean the plane defined by the incident direction of light and by the principal axis of the polarization ellipsoid.

  The term polarization direction, in the context of the present invention, not only describes the direction of the duration of the exposure process, but also refers to the direction of polarization on the same alignment layer applied during exposure after exposure. Also used.

  The electrodes are preferably in the form of parallel strip, zigzag or comb electrodes.

  Preferably, the present invention provides optical and electro-optical unstructured or structured structural elements, preferably liquid crystal display cells, multilayers and hybrid layers, comprising at least one polymer layer, copolymer or oligomer layer of the present invention. It relates to an element.

  In the present invention, the term optical or electro-optical element is preferably a display waveguide, security or brand protection element, bar code, optical grating, filter, retarder, compensation film, refractive polarizing film, absorbing polarizing film, Anisotropic scattering film Compensation and retardation film, twist retarder film, cholesteric liquid crystal film, guest-host liquid crystal film, monomer corrugated film, smectic liquid crystal film, polarizer, piezoelectric cell, thin film exhibiting nonlinear optical properties, decoration Optical element, brightness enhancement film, wavelength band compensation component, multi-domain compensation component, multi-view liquid crystal display component, achromatic retarder, polarization correction / adjustment film, optical or electrical Optical sensor components, brightness enhancement film components, optical telecommunication device components, G / H polarizers with anisotropic absorbers, refractive circular polarizers, refractive linear polarizers, MC (monomer corrugated film) ), Twisted nematic (TN) liquid crystal display, hybrid alignment nematic (HAN) liquid crystal display, electrically controlled birefringence (ECB) liquid crystal display, super twisted nematic (STN) liquid crystal display, optically compensated birefringence (OCB) liquid crystal display, pi- Cellular liquid crystal display, PLS technology (plane to line switching), PS-IPS (polymer stabilized IPS), in-plane switching (IPS) liquid crystal display, eg IPS mode, eg S-IP (Super IPS), AS-IPS (Advanced Super IPS), E-IPS (Enhanced IPS), H-IPS (Horizontal IPS), UH-IPS, S-IPS II, e-IPS, p-IPS (Performance IPS) , Field-induced photo-reactive alignment IPS, fringe field-switching (FFS) liquid crystal display, (FPA) field-induced photo-reactive alignment, hybrid FPA, VA-IPS mode liquid crystal display or for producing a display using blue phase liquid crystal , Meaning multilayer system or device. All the above display types are applied in either transmissive or reflective or transflective mode.

  More preferred optical or electro-optic elements are PLS technology (plane-to-line switching), PS-IPS (polymer stabilized IPS), in-plane switching (IPS) liquid crystal display, eg IPS mode, eg S-IPS ( Super IPS), AS-IPS (Advanced Super IPS), E-IPS (Enhanced IPS), H-IPS (Horizontal IPS), UH-IPS, S-IPS II, e-IPS, p-IPS (Performance IPS), Field-induced photoreactive alignment IPS, fringe field switching (FFS) liquid crystal display, (FPA) field-induced photoreactive alignment, hybrid FPA, VA-IPS mode liquid crystal display or display using blue phase liquid crystal. All the above display types are applied in either transmissive or reflective or transflective mode.

  The advantages of the present invention are not anticipated by those skilled in the art. Surprisingly, it has been found that the copolymers of the invention become polymerized or polymerizable liquid crystals upon irradiation with polarized light. Furthermore, the photo-alignment material exhibits good and homogeneous planar alignment quality and good electro-optical quality, eg good transmission retention ratio or, in particular, good seizure characteristics at high annealing temperatures. By way of further illustration, it will be demonstrated that the copolymers of the invention have good or very good image sticking properties, contrast ratios and voltage holding ratios.

  Further illustrations are non-limiting choices of illustrations that will further illustrate the invention.

Examples Definitions used in the examples
¹ H NMR: ¹ H nuclear magnetic resonance spectroscopy DMSO-d ₆ : deuterated dimethyl sulfoxide 300 MHz: 300 megahertz M: multiplet D: doublet Dd: doublet doublet t: triplet s: singlet q: quadruplet qi: quintet br: broad peak HCl: hydrochloric acid HCl solution (25%): volume%
NaOH: Sodium hydroxide NaOH (30%): wt%
MeOH: methanol EtOAc: ethyl acetate NMP: N-methyl-2-pyrrolidone THF: tetrahydrofuran TBME: tert. Butyl methyl ether DMF: N, N-dimethylformamide DBU 1,8-diazabicyclo [5.4.0] undec-7-ene NaHCO ₃ : sodium bicarbonate H ₂ SO ₄ : sulfuric acid RT: room temperature, usually 18 ° C. -28 ° C. range [η]: Viscosity v. t. %:volume%
GPC: Gel filtration chromatography, GPC is measured with UV detector and polystyrene as standard.
Mw: Molecular weight PI: Polydispersity index MLC7067: A mixture of liquid crystals available from Merck KGA, having a dielectric anisotropy of 10.3, an optical anisotropy of 0.1025 and a rotational viscosity of 81 m.Pa.s.

Example 1
Preparation of 4- (3-cyanopropoxy) benzoic acid 1 46.8 g (307 mmol) Methyl-4-hydroxybenzoate, 50 g (338 mmol) 4-Bromobutanenitrile is dissolved in 535 mL NMP. 5.1 g (31 mmol) potassium iodide and 128 g (93 mmol) potassium carbonate are added and the suspension is heated to 80 ° C. After 48 hours, a mixture of 15 g sodium hydroxide and 49 mL water is added. The reaction mixture is heated to 100 ° C. for 5 hours. The solution is then cooled and 480 mL of water is added. The aqueous layer is removed and the organic phase is poured into 1.5 L of ice water. Add 81 mL of 25% HCl solution. The precipitate is filtered, washed with 250 mL water, and the resulting product is included in 600 mL MeOH. The suspension is then stirred for 1 hour and filtered to give 50.1 g (80%) of compound 1 as a white powder, which is used without further purification.

Example 2
Preparation of (2E) -3- (4-{[4- (3-nitrilepropoxy) benzoyl] oxy} phenyl) prop-2-enoic acid 2 16.8 g (82 mmol) 1 was suspended in 56 mL of toluene and DMF Add a few drops. The suspension is heated to 75 ° C. and 10.7 g (90 mmol) thionyl chloride is added. After 2 hours, excess thionyl chloride is removed under pressure. Cool the solution to room temperature. 10.2 g (83 mmol) 4-hydroxybenzaldehyde, 0.5 g (4 mmol) 4-diaminopyridine and 28 g (355 mmol) pyridine are added. After 3 hours, 14.5 g (140 mmol) malonic acid and 3 g (42 mmol) pyrrolidine are added. The reaction mixture is reacted at 80 ° C. for 30 minutes. Then 16.8 mL of MeOH is included and the suspension is cooled and maintained at 0 ° C. for 1 hour. The product is filtered and suspended in a solution of 57 mL MeOH solution, 11 mL water and 7.5 g 25% HCL solution for 2 hours. The solid is filtered and washed with MeOH and heptane. The product is crystallized in acetonitrile to give 23 g (80%) compound 2 as a white powder.
¹ H NMR (300MHz) in DMSO-d ₆ : 12.44 (s, 1H), 8.10 (d, 2H), 7.80 (d, 2H), 7.63 (d, 1H), 7.33 (d, 2H), 7.15 (d , 2H), 6.55 (d, 1H), 4.17 (t, 2H), 2.69 (t, 2H), 2.08 (qi, 2H).

Example 3
Preparation of methyl 6- [4- (cyanomethyl) phenoxy] hexanoate compound 3 5.65 g (42 mmol) (4-hydroxyphenyl) acetonitrile and 9.1 g (44 mmol) Methyl 6-bromohexanoate was converted to N, N- Dissolve in 75 mL of dimethylformamide. 6.45 g (46 mmol) potassium carbonate and 0.7 g (4 mmol) potassium iodide are added and the suspension is heated to 80 ° C. After 5 hours, the mixture is cooled to 0 ° C. in an ice bath. 375 ml of H ₂ O and 12.4 g 37% HCl were slowly added. The precipitate is filtered and washed with 500 ml H ₂ O. The white solid is dried at 40 ° C. under vacuum overnight to give 11.2 g 6- [4- (cyanomethyl) phenoxy] hexanoic acid.

Examples 3a, 3b, 3c and 3d
Compounds 4, 5, 6, and 7 were converted to methyl 6-bromohexanoate, methyl 4-bromobutanoate, methyl 5-bromopentanoate, methyl 8-bromooctanoate, methyl 11-bromoundecano, respectively. Prepared according to the methods described for compound 3 provided that it is replaced by art.

Example 4
Preparation of methyl 6- (4-formylphenoxy) hexanoate compound 8 Compound 8 is prepared according to the method described for compound 3 with the exception that (4-hydroxyphenyl) acetonitrile is replaced by methyl 4-hydroxybenzaldehyde.

Examples 4a, 4b, 4c and 4d
Compounds 9, 10, 11, and 12 were converted to methyl 6-bromohexanoate, methyl 4-bromobutanoate, methyl 5-bromopentanoate, methyl 8-bromooctanoate, methyl 11-bromoundecano, respectively. Prepared according to the methods described for compound 8, provided that it is replaced by art.

Example 5
Preparation of 6- [4- (1-cyano-2-phenyl-vinyl) phenoxy] hexanoic acid compound 13 8.85 g (35 mmol) Compound 3, 3.8 g (35 mmol) Dissolve benzaldehyde in 30 mL propan-2-ol. . The solution is heated to 60 ° C. and 1.77 mL (1.9 mmol) of a 2M solution of tetrabutylammonium hydroxide in methanol are added dropwise. After 2 hours at 60 ° C., the reaction mixture is cooled to 0 ° C. The precipitate is filtered and washed with cold propan-2-ol. The 7.4 g solid was dissolved in 55 ml dimethylacetamide and then a solution of 1.35 g NaOH and 1.2 g H ₂ O in 55 ml MeOH was added. When the reaction is complete, the reaction mixture is slowly poured into a solution of 13.2 g 25% HCl and 316 g H ₂ O. The precipitate is filtered and dried under vacuum to give 6.5 g white powder.
¹ H NMR (300MHz) in DMSO-d ₆ : 12.00 (s, 1H), 7.90 (m, 3H), 7.70 (d, 2H), 7.53 (m, 3H), 7.07 (d, 2H), 4.03 (t , 2H), 2.25 (t, 2H), 1.75 (qi, 2H), 1.59 (qi, 2H), 1.44 (m, 2H).

Examples 5a, 5b, 5k, 5l
Compounds 14, 15, 23, 24 are prepared according to the method described for compound 13, with the exception that compound 3 is replaced by compound 5, compound 7, respectively compound 6, each compound 6, each compound 4.
¹ H NMR (300MHz) in THF-d8 of compound 14: 10.68 (s, 1H), 7.95 (dd, 2H), 7.70 (m, 3H), 7.47 (m, 3H), 7.04 (d, 2H), 4.08 (t, 2H), 2.35 (t, 2H), 1.83 (m, 4H).
¹ H NMR (300MHz) in DMSO-d ₆ of compound 15: 11.95 (s, 1H), 7.90 (m, 3H), 7.70 (d, 2H), 7.52 (m, 3H), 7.07 (d, 2H), 4.03 (t, 2H), 2.19 (t, 2H), 1.73 (qi, 2H), 1.2 (m, 14H).
¹ H NMR (300MHz) in DMSO-d ₆ of compound 23: 11.98 (s, 1H), 7.90 (m, 3H), 7.71 (d, 2H), 7.59 (br., 3H), 7.06 (dd, 2H) , 4.03 (t, 2H), 2.24 (t, 2H), 1.75 (m, 2H), 1.6-1.2 (m, 8H).
¹ H NMR (300MHz) in DMSO-d ₆ of compound 24: 12.01 (s, 1H), 7.91 (m, 3H), 7.71 (d, 2H), 7.52 (m, 3H), 7.08 (d, 2H), 4.03 (t, 2H), 2.41 (t, 2H), 1.97 (qi, 2H).

Examples 5c and 5d
Compounds 17 and 18 are prepared according to the method described for compound 13 with the exception that benzaldehyde is replaced by 4-fluorobenzaldehyde and 4-trifluoromethylbenzaldehyde, respectively.
¹ H NMR (300MHz) in DMSO-d ₆ of compound 17: 12.04 (s, 1H), 7.98 (dd, 2H), 7.92 (s, 1H), 7.68 (d, 2H), 7.38 (dd, 2H), 7.07 (d, 2H), 4.03 (t, 2H), 2.24 (t, 2H), 1.74 (qi, 2H), 1.58 (qi, 2H), 1.45 (m, 2H).
¹ H NMR (300MHz) in DMSO-d ₆ of compound 18: 12.05 (s, 1H), 8.06 (m, 3H), 7.89 (d, 2H), 7.73 (d, 2H), 7.09 (d, 2H), 4.05 (t, 2H), 2.30 (t, 2H), 1.80 (m, 4H).

Example 5e
Compound 19 is prepared according to the method described for compound 13 with the exception that compound 3 is replaced by compound 8 and benzaldehyde is replaced by benzonitrile.
¹ H NMR (300MHz) in DMSO-d ₆ of compound 19: 12.00 (s, 1H), 7.95 (m, 3H), 7.74 (d, 2H), 7.42 (m, 3H), 7.10 (d, 2H), 4.06 (t, 2H), 2.25 (t, 2H), 1.75 (qi, 2H), 1.58 (qi, 2H), 1.45 (m, 2H).

Example 5f, 5j
Compounds 20 and 25 are prepared according to the method described for compound 19 with the exception that compound 8 is replaced by compound 12 and compound 10, respectively.
¹ H NMR (300MHz) in DMSO-d ₆ of compound 20: 12.00 (s, 1H), 7.95 (m, 3H), 7.74 (d, 2H), 7.42 (m, 3H), 7.10 (d, 2H), 4.06 (t, 2H), 2.19 (t, 2H), 1.74 (qi, 2H), 1.40 (m, 14H).
¹ H NMR (300MHz) in DMSO-d ₆ of compound 25: 12.05 (s, 1H), 7.94 (m, 3H), 7.73 (d, 2H), 7.51 (m, 3H), 7.11 (d, 2H), 4.07 (t, 2H), 2.30 (t, 2H), 1.80-1.60 (m, 4H).

Example 5g
Compound 21 is prepared according to the method described for compound 19 with the exception that compound 8 is replaced by compound 10 and benzaldehyde is replaced by 4-trifluoromethylbenzaldehyde.
¹ H NMR (300MHz) in DMSO-d ₆ of compound 21: 12.05 (s, 1H), 8.13 (s, 1H), 7.97 (m, 4H), 7.86 (d, 2H), 7.13 (d, 2H), 4.09 (t, 2H), 2.31 (t, 2H), 1.76 (m, 4H).

Example 5h
Compound 22 is prepared according to the method described for compound 21 with the replacement of 4-trifluoromethylbenzaldehyde with 2- (3,5-dimethylmethoxyphenyl) acetonitrile.
¹ H NMR (300MHz) in DMSO-d ₆ of compound 21: 12.05 (s, 1H), 7.96 (m, 3H), 7.11 (d, 2H), 6.86 (d, 2H), 6.57 (s, 1H), 4.07 (t, 2H), 3.82 (s, 6H), 2.15 (t, 2H), 1.70 (m, 4H).

Example 5i
Compound 26 is prepared according to the method described for compound 21 with the exception that 4-trifluoromethylbenzaldehyde is replaced by 4-fluorobenzaldehyde.
¹ H NMR (300MHz) in DMSO-d ₆ of compound 26: 12.05 (s, 1H), 7.92 (m, 3H), 7.77 (m, 2H), 7.35 (t, 2H), 7.10 (d, 2H), 4.07 (t, 2H), 2.30 (m, 2H), 1.80-1.60 (m, 4H).

Example 6
Are suspended prepared 5.05 g (14 mmol) of compound 2 and 0.27 g (0.7 mmol) of compound 14 polymer P3 in 4-methyl-2-pentanone 35ml and 0.54 g H ₂ O. 0.16 g (0.75 mmol) tetraethylammonium bromide is added to give a white suspension. 4.25 g (14.2 mmol) 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane is added dropwise. The mixture is stirred at reflux for 48 hours. The suspension is cooled. The upper liquid phase is removed and the polymer is rinsed with 25 ml of 4-methyl-2-pentanone. 20 ml of tetrahydrofuran and 50 ml of ethyl acetate are added and the mixture is extracted with 15 ml of water. The resulting solution is slowly poured into 240 mL of cold tert-butyl methyl ether. The solid is filtered and washed with 10 mL of tert-butyl methyl ether. The resulting white solid is dried under vacuum to give 5.45 g polymer.
Mw (DA): 17120, Mn (DA): 75600, PI: 2.26

Example 7
Preparation of polymer P2 Polymer P2 is prepared according to the method described for polymer P1 using 5.05 g (14 mmol) compound 2 and 0.162 g (0.56 mmol) compound 14.
Mw (DA): 56450, Mn (DA): 34780, PI: 1.62

Example 8
Preparation of polymer P1 Polymer P3 is prepared according to the method described for polymer P1 using 5.05 g (14 mmol) compound 2 and 0.216 g (0.42 mmol) compound 14.
Mw (DA): 40960, Mn (DA): 25866, PI: 1.58

Example 9
Preparation of polymer P4 Polymer P4 is prepared according to the method described for polymer P1 using 5.05 g (14 mmol) of compound 2 and 0.378 g (0.98 mmol) of compound 14.
Mw (DA): 95700, Mn (DA): 59550, PI: 1.6

Example 10
Preparation of polymer P5 Polymer P5 is prepared according to the method described for polymer P1 using 5.05 g (14 mmol) compound 2 and 0.486 g (1.26 mmol) compound 14.
Mw (DA): 74130, Mn (DA): 41580, PI: 1.78

Example 11
Preparation of polymer P6 Polymer P6 is prepared according to the method described for P1, with the exception that compound 14 is replaced by compound 15.
Mw (DA): 98100, Mn (DA): 41400, PI: 2.37

Example 12
Preparation of polymer P7 Polymer P7 is prepared according to the method described for P2, with the exception that compound 14 is replaced by compound 13.
Mw (DA): 63100, Mn (DA): 36600, PI: 1.72

Example 13
Preparation of polymer P8 Polymer P8 is prepared according to the method described for P3, with the exception that compound 14 is replaced by compound 19.
Mw (DA): 86080, Mn (DA): 41030, PI: 2.1

Example 14
Preparation of polymer P9 Polymer P9 is prepared according to the method described for P1, with the exception that compound 14 is replaced by compound 20.
Mw (DA): 117320, Mn (DA): 65240, PI: 1.8

Example 15
Preparation of polymer P10 Polymer P10 is prepared according to the method described for P3, with the exception that compound 14 is replaced by compound 17.
Mw (DA): 128800, Mn (DA): 54640, PI: 2.36

Example 16
Preparation of polymer P11 Polymer P11 is prepared according to the method described for P2, with the exception that compound 14 is replaced by compound 17.
Mw (DA): 40390, Mn (DA): 26650, PI: 1.52

Example 17
Preparation of polymer P12 Polymer P12 is prepared according to the method described for P3, with the exception that compound 14 is replaced by compound 21.
Mw (DA): 81530, Mn (DA): 44500, PI: 1.83

Example 18
Preparation of polymer P13 Polymer P13 is prepared according to the method described for P3, with the exception that compound 14 is replaced by compound 18.
Mw (DA): 77920, Mn (DA): 40320, PI: 1.93

Example 19
Preparation of polymer P14 Polymer P14 is prepared according to the method described for P3, with the exception that compound 14 is replaced by compound 22.
Mw (DA): 72780, Mn (DA): 40218, PI: 1.8

Preparation of polymer P15 Polymer P15 is prepared according to the method described for polymer P1, provided that compound 14 is replaced by compound 23.
Mw (DA): 124830, Mn (DA): 43000, PI: 2.9

Preparation of polymer P16 Polymer P16 is prepared according to the method described for polymer P3, with the exception that compound 14 is replaced by compound 23.
Mw (DA): 131250, Mn (DA): 45950, PI: 2.85

Preparation of polymer P17 Polymer P17 is prepared according to the method described for polymer P1, provided that compound 14 is replaced by compound 24.
Mw (DA): 104670, Mn (DA): 37800, PI: 2.8

Preparation of polymer P18 Polymer P18 is prepared according to the method described for polymer P3, with the exception that compound 14 is replaced by compound 24.
Mw (DA): 123240, Mn (DA): 46560, PI: 2.7

Preparation of polymer P19 Polymer P18 is prepared according to the method described for polymer P3, with the exception that compound 14 is replaced by compound 25.
Mw (DA): 125500, Mn (DA): 49740, PI: 2.5

Preparation of polymer P20 Polymer P20 is prepared according to the method described for polymer P3, with the exception that compound 14 is replaced by compound 20.
Mw (DA): 88125, Mn (DA): 32830, PI: 2.7

Preparation of polymer P21 Polymer P21 is prepared according to the method described for polymer P4, with the exception that compound 14 is replaced by compound 17.
Mw (DA): 90110, Mn (DA): 43400, PI: 2

Preparation of polymer P22 Polymer P22 is prepared according to the method described for polymer P1, provided that compound 14 is replaced by compound 26.
Mw (DA): 87260, Mn (DA): 45360, PI: 1.9

Preparation of polymer P23 Polymer P23 is prepared according to the method described for polymer P3, with the exception that compound 14 is replaced by compound 26.
Mw (DA): 114970, Mn (DA): 48850, PI: 2.4

Example 20
Comparative Example CP1
49.2 g Compound 2 is suspended in 375 ml 4-methyl-2-pentanone and 5 g water. 1.5 g Tetraethylammonium bromide is added to give a white suspension. 38.4 g 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane is added dropwise. The mixture is stirred at reflux for 48 hours. The suspension is cooled. The upper liquid phase is removed and the polymer is rinsed with 150 ml of 4-methyl-2-pentanone. 140 mL of tetrahydrofuran is added and the mixture is heated with stirring to a (yellow) solution at 50-60 ° C. The resulting yellowish solution is slowly poured into chilled 1.5 L within 10 minutes. The solid is filtered over a 15 cm Buchner equipped with filter paper (duration: 2 minutes) and washed with 500 mL of tert-butyl methyl ether. The resulting white solid (70.0 g) is dried under vacuum to give 70 g polymer.
Mw (DA): 34500, Mn (DA): 22700, PI: 1.52

Example 21
Preparation of PAA-1 0.666 g (3.4 mmol) 1,2,3,4-cyclobutanetetracarboxylic acid 8.6 g 0.69 g (3.47 mmol) of 4- (4-aminophenoxy) aniline in NMP Add to solution. The mixture is then stirred at 0 ° C. for 2 hours. The polymer mixture is diluted with 50 mL of NMP, precipitated into 300 mL of water, and after drying under vacuum at 40 ° C., 2.1 g of polymeric acid PAA-1 is produced in the form of a white powder.
[Η] = 0.40 dL / g

Preparation of PAA-2 0.69 g (3.1 mmol) 2,3,5-tricarboxycyclopentylacetic acid-1,2: 3,4-dianhydride 5.1 g in NMP 1.5 g (3.1 mmol) Add to solution of 4- (4-aminophenoxy) aniline. The mixture is then stirred at 0 ° C. for 2 hours. The polymer mixture is diluted with 30 g NMP, precipitated into 300 mL water, and after drying under vacuum at 40 ° C., 1.9 g polymer acid PAA-2 is produced in the form of a white powder.
[Η] = 0.40 dL / g

Preparation of PAA-3 3.2 g (14.1 mmol) 2,3,5-tricarboxycyclopentylacetic acid-1,2: 3,4-dianhydride 35 g 3 g (14.1 mmol) 4,4 ′ in NMP -Add to solution of ethylenedianiline. The mixture is then stirred at 0 ° C. for 2 hours. The polymer mixture is then diluted with 47 g acetone and precipitated into 500 mL water to produce 6.5 g polymer acid PAA-3 in the form of a white powder after drying at 40 ° C. under vacuum.
[Η] = 0.52 dL / g

Preparation of PAA-4 5.6 g (25.2 mmol) 2,3,5-tricarboxycyclopentylacetic acid-1,2: 3,4-dianhydride 60 g 5 g (25.2 mmol) in NMP 4,4 ′ Add to a solution of methylenedianiline. The mixture is then stirred at 0 ° C. for 2 hours. The mixture is subsequently allowed to react for 1 hour at room temperature. The polymer mixture is then diluted with 100 g NMP and 78 g acetone, precipitated into 3500 mL water and, after drying under vacuum at 40 ° C., 14 g polymer acid PAA-4 is produced in the form of a white powder.
[Η] = 0.52 dL / g

Application Example Example 22
A liquid crystal cell is prepared in which the liquid crystal is aligned by photoreactive P1, and an electric field is applied between the two planar electrodes in the cell gap on each side.

A 6.3 wt% solution was prepared by mixing P1 and polymer acid PAA-1 in a ratio of 10:90 (wt%) in NMP to form a blend composition and thoroughly until the solid dissolved Stir. The second solvent, butyl cellosolve (BC), is then added and the entire composition is stirred thoroughly to obtain the final solution. The solvent ratio between NMP and butyl cellosolve is 1: 1. The polymer solution was spin coated on two ITO coated glass substrates for 30 seconds at a spin speed of 3600 rpm. After spin coating, the substrate is subjected to a baking procedure consisting of pre-baking at 130 ° C. for 1.5 minutes and post-baking at 200 ° C. for 40 minutes. The resulting layer thickness is about 90-110 nm. A substrate having a polymer layer coated on top is exposed to linearly polarized UV light (LPUV) at an incident angle of 0 ° relative to the normal of the substrate surface. The plane of polarization was an in-plane extending in the light propagation direction perpendicular to the substrate. The added exposure is 100 mJ / cm ² . After LPUV exposure, the cell with the two substrates is assembled such that the exposed polymer layer faces the inside of the cell. The substrates are adjusted to each other so that the induced orientation directions are parallel to each other. The cell is a capillary filled with liquid crystal MLC7067 (Merck KGA). The liquid crystal had positive dielectric anisotropy. The cell is then optionally annealed at 130 ° C. for 30 minutes and slowly cooled to room temperature. The alignment quality of the liquid crystal in the cell is confirmed by placing the cell between two intersecting polarizers and adjusted to obtain a dark state. When the dark state shows no defects and the liquid crystal is sufficiently oriented, the orientation quality is defined as good. If the dark state has light leakage due to the slightly inhomogeneous alignment of the liquid crystal in some areas of the cell, the alignment quality is defined as medium. When the liquid crystal is not aligned in a state lacking a dark state, the alignment quality is defined as poor.

  The liquid crystal in the cell showed a well-defined and homogeneous planar alignment of the cell. Tilt angles below 0.2 ° are measured using rotational analysis from Shintech.

Example 22a
A liquid crystal cell is made according to the method described in Example 22 except that an incident angle of 40 ° with respect to the normal of the substrate surface is used for linearly polarized UV. The liquid crystal in the cell showed a well-defined and homogeneous planar alignment before and after thermal annealing of the cell. Tilt angles below about 0.2 ° are measured using rotational analysis from Shintech.

Example 23
Implement cells with P2, P3, P4, P5, P6, P7, P8, P9, P10, P11, P12, P13, P14, P15, P16, P17, P18, P19, P20, P21, P22, P23 and CP1 Prepared according to the method described in Example 22. The liquid crystal in the cell showed a well-defined and homogeneous planar alignment after the thermal annealing of the cell. Tilt angles below 0.2 ° are measured using rotational analysis from Shintech.

Example 24
The image sticking of the cells produced in Examples 22 and 23 was measured. IPS cell seizure is measured by using an Optipro-250 from Shintech. A wavelength of 589 nm is used. An unbiased sample consisting of two independent pixels is placed between crossed polarizers with the sample orientation direction parallel to the first polarizer. 1% transmittance and the voltage amplitude _{V 100} for the highest transmittance _{T 100} to find the voltage amplitude _{V 1} of the when it reaches the _(T 1 [0]), the voltage-transmittance curves of both pixels 60Hz Measure by applying a square wave voltage. A 60 Hz square wave voltage with amplitude V ₁₀₀ is applied to the first pixel (referred to as the measurement pixel, M) for a period of 24 hours while keeping the second (reference, R) pixel biased. Samples are stored protected from light and room temperature during this period. After 24 hours, the transmittance T ₁ [24h] is measured again by using the same voltage V ₁ for both pixels. The burn-in of the sample is burn-in (24h) = [TM1 (24h) / TM1 (0h)] × [TR1 (0h) / TR1 (24h)] × 100. Where M refers to the measurement pixel and R refers to the reference pixel. Cell burn-in is considered very good (●) for values below 109%, good (□) for values between 109% and 113%, and poor (x) for values above 113%.

  As demonstrated by Example 24, the image sticking with the copolymer of the present invention is very good or good compared to the image sticking of Comparative Example CP1, which is poor.

Example 25
The alignment quality of the cells from Examples 22 and 23 is quantified by contrast ratio (CR). Transmission microscope composed of a backlight, a polarizer and an analyzer, an optical system between the polarizers (condenser lens, microscope objective lens), and a photomultiplier tube for measuring the transmitted light output. Is used to determine the light leakage. An LED backlight from ELDIM is used as the light source. The backlight is similar to a backlight from a commercial display. The measurement area on the focal plane (sample) of the microscope objective lens is about 1 mm ² . A sample-free polarizer is brought to an orthogonal position from the microscope (detection signal displays a minimum). An unbiased sample is placed under the microscope objective and rotated in-plane until the detector displays a minimum value V ₀ (the cell orientation is parallel to the polarizer). By maintaining the in-plane position of the sample, the analyzer is rotated up to 90 ° (until the detector displays the maximum value V _max ). The contrast of the sample is CR = V _max / V ₀ .

  If CR is below 1000, the contrast is said to be “bad”. When CR is 1000 to 2000, CR is medium (●). When CR is 2000 to 3000, the contrast is said to be good (□). If the CR is greater than 3000, the CR is said to be very good (x to □).

Example 26
The voltage holding ratio (VHR) of the cells from Examples 22 and 23 was measured at room temperature using an LCM-1 instrument from Toyo, Japan. VHR was measured using the short term frame (T). The voltage decay V (T = 20 ms) of a voltage surge of 64 μs (V ₀ (V at t = 0) = 5 V) is then measured over a period of T = 20 ms. The voltage holding ratio given by the integration of the measurement curve between V ₀ and V, weighted by the region for 100% VHR, is then determined at room temperature. The results show VHR ≧ 99% for all cells tested.

Claims (15)

i. Formula (I)

[Where:
n ₀ is an integer from ₀ to 4,
n ₁ is an integer from 0 to 15,
n ₂ is an integer of 0 to 15,
n ₃ is an integer of 1 to 15,
X and Y each independently represent H, F, Cl, or CN;
S ₂ represents a cyclic, aromatic, linear or branched substituted or unsubstituted C ₁ -C ₂₄ alkylene, in which one or more —C—, —CH—, —CH ₂ The group can be replaced by a linking group;
E represents O, S, NH, C (C ₁ -C ₆ alkyl), NR ⁴ , OC, OOC, OCONH, OCONR ¹² , SCS, SC, wherein R ¹² is cyclic, linear or branched a _C 1 _{-C 24} alkyl substituted or unsubstituted with a chain, wherein one or more of -C -, - CH -, - CH 2 - groups are each independently replaced by a linking group It is possible,
A represents a halogen or a substituted or unsubstituted _C 1 _{-C 24} alkyl, substituted or unsubstituted _C 1 _{-C 24} alkenyl, a _C 1 _{-C 24} alkynyl, or carboxylic acid substituted or unsubstituted, where 1 One or more of -C -, - CH -, - CH 2 - groups are each independently, can be replaced by a heteroatom,
Z ₂ represents a chemical group having delocalization of its electron density and / or inducing delocalization of its adjacent electron density,
T represents a single bond, unsubstituted or substituted linear C ₁ -C ₁₆ alkyl,
Where ^* indicates a bond to the polymer backbone]
A first monomer having a side chain represented by:
ii. Formula (II)

[Where:
n ₅ and n ₆ are each independently 0, 1 or 2,
E ₁ represents —O—, —CO—, —COO—, —OCO—, —NR ⁶ —, —NR ⁶ CO—, —CONR ⁶ —, —NR ⁶ COO—, —OCONR ⁶ —, —NR ^6. CONR ⁶ —, —C═C—, —C≡C—, —O—COO—, a bridging group selected from the group consisting of:
S ₃ is a spacer group selected from the group consisting of a single bond, unsubstituted or linear or branched C ₁ -C ₂₄ alkylene substituted by cyano or halogen, wherein one or more CH ₂ groups, each independently, a heteroatom or ^{-O -, - CO -, -} COO -, - OCO -, - NR 6 -, - NR 6 CO -, - CONR 6 -, - NR 6 COO-, -OCONR ^6- , -NR ⁶ CONR ^6- , -C = C-, -C≡C-, -O-COO- can be substituted by a group selected from the group consisting of:
Y ₁ and X ₁ are each independently either cyano or halogen;
Ar ₁ and Ar ₂ each independently represent a ring system of 5 to 40 atoms, wherein each ring system is a double of formula (II) via electron conjugation (π-π bond). Including at least one unsaturation bonded directly to the bond;
R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen, C ₁ -C ₁₂ alkoxy, halogen, linear or branched, substituted or unsubstituted C ₁ -C ₂₄ alkyl, nitrile. Or R ₁ and R ₄ are hydrogen and R ₂ and R ₃ together form the remainder of the electron donor ring fused to the Ar ₂ ring;
R ₅ , R ₆ and R ₇ are each independently hydrogen, C ₁ -C ₁₂ alkoxy, halogen, linear or branched substituted or unsubstituted C ₁ -C ₂₄ alkyl, nitrile or electron donating A single substituent, or R ₅ and R ₆ together form the remainder of the electron donating ring fused to the Ar ₁ ring;
^{* Indicates} bond to polymer backbone]
A second monomer having a side chain represented by
Here, the polymer skeleton is polysiloxane.
Copolymer. The monomer of the polymer backbone in the first monomer and the second monomer has the formula (VI)

[Where:
R _a represents OH, Cl, a substituted or unsubstituted alkoxy group having 1 to 20 carbons, an alkyl group having 1 to 20 carbons, or an aryl group having 1 to 20 carbons;
R ₀ represents OH, Cl, 1 to 20 carbon atoms, a linear or branched, substituted or unsubstituted alkoxy group, and in the alkoxy group, —C—, —CH—, —CH ₂ — may be replaced by C ₆ -C ₂₀ aryl group unsubstituted or substituted,
S ₁ is a single bond or linear or branched substituted or unsubstituted C ₁ -C ₂₄ alkylene, especially C ₁ -C ₁₂ alkylene, especially C ₁ -C ₈ alkylene, especially C ₁ -C ₆ alkylene, _especially, C 1 -C ₄ alkylene, _especially, C 1 -C ₂ alkylene, in the alkylene, one or more _{-C -, - CH-, CH 2} - group, is replaced by a linking group Can
z is an integer of 0 to 15,
Z ₁ represents a single bond or a substituted or unsubstituted C _{3 to} C ₁₂ aliphatic or alicyclic group;
^* Refers to the bond to the monomer of formula (I)]
The copolymer of claim 1 represented by: R _a and R ₀ are as described above,
Z ₁ represents a substituted or unsubstituted C ₅ -C ₆ alicyclic group,
The copolymer according to claim 2, wherein S ₁ represents a substituted or unsubstituted C ₁ -C ₂₄ linear alkyl. R _a and R ₀ are as described above,
Z ₁ represents a substituted or unsubstituted cyclohexanol group or a substituted or unsubstituted cyclohexane ether group;
Copolymer according to claim 2 or 3, wherein S ₁ represents an ethyl group. In the first monomer having a side chain represented by formula (I):
n ₀ , n ₁ , n ₂ , n ₃ , S ₂ , T are as described above,
A represents H, one or more halogens, one or more methoxy groups or one or more carboxylic acid groups;
E represents O or S or NH;
X and Y are H,
The copolymer of claim 1, wherein Z ₂ is CN. In the first monomer having a side chain represented by formula (I):
n ₀ , n ₁ , n ₂ , n ₃ , S ₂ , T, A, X, Y and Z ₂ are as described above,
6. Copolymer according to claim 5, wherein E represents O. In the first monomer having a side chain represented by formula (II):
S ₃ , Ar ₁ , Ar ₂ , X ₁ , Y ₁ , R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , n ₅ and n ₆ are as defined above. ,
E ₁ is, -O -, - CO -, - COO -, - OCO -, - OOC- is selected from the group consisting of, claims 1 copolymer according. In the second monomer having a side chain represented by formula (II):
Is S _3, a linear or branched unsubstituted _C 1 _{-C 24} alkylene in the chain, one or more CH ₂ groups are each independently, can be is replaced by -O-, claim 7. Copolymer according to 7. R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen, C ₁ -C ₁₂ alkoxy, halogen, linear or branched, substituted or unsubstituted C ₁ -C ₂₄ alkyl, nitrile. A copolymer according to claim 7 or 8. R ₁ and R ₄ are hydrogen,
R ₂ and R ₃ together form the remainder of the electron donating ring fused to the Ar ₂ ring,
Alternatively, where R ₁ , R _2, R ₃ and R ₄ are each independently substituted or unsubstituted by hydrogen, C ₁ -C ₁₂ alkoxy, halogen, linear or branched halogen a C ₁ -C ₂₄ alkyl, nitrile, claim 7 or 8 copolymer according. R _{5, R 6} and _{R 7} are hydrogen, any one copolymer according to claim 7-10. Comprising at least one of the first copolymer according to any one of claims 1 to 11 and a second polymer or copolymer not identical to the first copolymer, and optionally an additive,
Composition. Comprising at least one copolymer according to any one of claims 1 to 11 or a composition according to claim 12.
Alignment layer.   Use of an alignment layer according to claim 13 for the alignment of liquid crystals. Comprising at least one linear, branched or cross-linked copolymer according to any one of claims 1 to 11 or a composition according to claim 12 or an alignment layer according to claim 13.
Optical or electronic unstructured or structured elements, preferably liquid crystal display cells, multilayer and hybrid layer elements.