WO2016099178A1

WO2016099178A1 - Vertical alignment film comprising copolymer of cyclic olefin compounds

Info

Publication number: WO2016099178A1
Application number: PCT/KR2015/013878
Authority: WO
Inventors: 박정하; 박은석; 최대승; 황승연; 이민형
Original assignee: 주식회사 엘지화학
Priority date: 2014-12-18
Filing date: 2015-12-17
Publication date: 2016-06-23

Abstract

The present invention relates to a vertical alignment film comprising a copolymer of two or more different cyclic olefin compounds. More specifically, the present invention relates to a vertical alignment film comprising a copolymer of two or more different cyclic olefin compounds respectively having different particular substituents, thereby being capable of having orientation even in a low temperature process, and being capable of exhibiting excellent liquid crystal vertical orientation.

Description

[Name of invention]

Vertical alignment film containing cyclic olefin compound co-polymer [recited with related application (s)]

This application claims the benefit of priority based on Korean Patent Application No. 10-2014-0183432 dated December 18, 2014 and Korean Patent Application No. 10-2015-0180481 dated December 16, 2015. All content disclosed in the literature is included as part of this specification. Technical Field

The present invention relates to a vertical alignment film comprising a copolymer of a cyclic olefin compound. More specifically, the present invention relates to a vertical barrier layer including a copolymer of two or more cyclic olefin compounds each having a different specific substituent, which may have orientation even in a low temperature process, and may exhibit excellent liquid crystal vertical alignment. Background Art

In recent years, with the increase in the size of display devices, as applications are expanded to not only mobile devices such as smart phones and laptops but also large wall-mounted TVs, high quality, high quality, and wide viewing angles are required.

In particular, the TFT-LCD, which is driven by a thin film transistor, can independently drive individual pixels, so that the response speed of the liquid crystal is very fast, and thus high quality moving images can be realized. The range is expanding.

In such a TFT-LCD, an alignment layer is used under the liquid crystal layer so that the liquid crystal may be used as an optical switch. A photo-reflective copolymer is used in the alignment layer to apply a photo alignment using UV.

Here, the photo-alignment refers to a mechanism in which the functional groups (photo-amplitude groups) of the constant photo-reflective copolymer by the linearly polarized UV causes the photo-reaction, and the main chain of the polymer is aligned in a predetermined direction in the process, the liquid crystal is oriented. That is, in order to use a liquid crystal as an optical switch in a TFT-LCD, the liquid crystal should be initially oriented in a predetermined direction on the layer on which the thin film transistor inside the display cell is formed. For this purpose, an alignment film including a photoreactive copolymer is used.

Therefore, in order to cause such photo-alignment more effectively, the photo-reflective copolymer included in the alignment layer should be able to interact with molecules in the liquid crystal filling well, and in addition, it should be able to exhibit excellent photoreactivity.

In general, for such liquid crystal alignment, a method of applying a polyamic acid heat resistant polymer on a transparent glass and laminating a polyimide polymer alignment layer through heat treatment at a high temperature is used.

However, in the case of a display device applied to a flexible display or a smart window or the like, since a polymer film substrate is used, the above method of applying a polyamic acid polymer on the substrate and performing heat treatment at a high temperature is not suitable.

Accordingly, research on a vertical alignment film that can have an alignment property even at a low temperature process and can exhibit excellent liquid crystal alignment property is required.

[Content of invention]

[Problem to solve]

The present invention includes a copolymer of two or more cyclic olefin compounds having a specific substituent, to provide a vertical alignment layer that can have an orientation even in a low temperature process, and can exhibit excellent liquid crystal vertical alignment.

Moreover, this invention provides the liquid crystal cell containing the said vertical alignment film and the liquid crystal layer on an alignment film.

In addition, the present invention provides a display device including the vertical alignment layer.

[Measures of problem]

The present invention is a cyclic olefin compound represented by the formula (1) and ^' It provides an alignment film comprising a copolymer of the cyclic olefin compound represented by the formula (1-1).

[

In Chemical Formula 1,

q is an integer from 0 to 4,

At least one of R 1 to R 4 is a radical represented by the following Chemical Formula 1 a, except that R 1 to R 4 are the same as or different from each other except _a radical of the general formula i _a , and each independently hydrogen; halogen; Substituted or unsubstituted linear or branched alkyl having 1 to 20 carbon atoms; Substituted or unsubstituted linear or branched alkenyl having 2 to 20 carbon atoms; Substituted or unsubstituted linear or branched alkynyl having 2 to 20 carbon atoms; Substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Substituted or unsubstituted aryl having 6 to 40 carbon atoms; Substituted or unsubstituted arylalkyl having 5 to 12 carbon atoms; And a polar functional group including at least one selected from oxygen, nitrogen, phosphorus, sulfur, silicon, and boron,

R1 to R4 are hydrogen; halogen; Or when it is not a polar functional group, one or more combinations of R1 and R2 or R3 and R4 are connected to each other to form an alkylidene group having 1 to 10 carbon atoms, or R1 or R2 is connected to any one of R3 and R4 to 4 carbon atoms To form a saturated or unsaturated aliphatic ring of 12 to 12, or an aromatic ring of 6 to 24 carbon atoms,

[Formula 1 a] In Chemical Formula 1a

a1 and c1 are each independently a simple bond, substituted or unsubstituted alkylene having 1 to 5 carbon atoms,

This is an ester

n1 and n2 are each independently an integer of 0 to 5, n1 + n2 is an integer of 1 to 5,

Χι and X ₂ are substituents substituted in the benzene ring, each independently, a fluorine (F) atom, an alkyl fluoride having 1 to 5 carbon atoms, an alkoxy fluoride having 1 to 5 carbon atoms, an aryl fluoride having 6 to 20 carbon atoms, or 6 carbon atoms To 20 alkoxy aryl fluoride,

In Chemical Formula 2,

q 'is an integer from 0 to 4,

At least one of RV to R4 'is a radical represented by the formula 1-1 a,

Formula ii with the exception that the radical of _a R1 'to R4' are the same or different from each other, and each independently hydrogen; halogen; Substituted or unsubstituted linear or branched alkyl having 1 to 20 carbon atoms; Substituted or unsubstituted linear or branched alkenyl having 2 to 20 carbon atoms; Substituted or unsubstituted linear or branched alkynyl having 2 to 20 carbon atoms; Substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Substituted or unsubstituted aryl having 6 to 40 carbon atoms; Substituted or unsubstituted arylalkyl having 5 to 12 carbon atoms; And a polar functional group including at least one selected from oxygen, nitrogen, phosphorus, sulfur, silicon, and boron, R1 'to R4' is hydrogen; halogen; Or when not a polar functional group, one or more combinations of R1 "and R2 'or R3' and R4 'are connected to each other to form an alkylidene group having 1 to 10 carbon atoms, or R1' or R2 'is selected from R3' and R4 ' May be linked to any one of a saturated or ball-saturated aliphatic ring of 4 to 12 carbon atoms, or an aromatic ring of 6 to 24 carbon atoms,

[

In Chemical Formula 1-1a

a2 is a simple bond or a substituted or unsubstituted alkylene having 1 to 5 carbon atoms,

b2 is ester,

c2 is substituted or unsubstituted alkenylene having 2 to 5 carbon atoms,

n3 and n4 are each independently an integer of 0 to 5, n3 + n4 is 1 to 5

^' Integer,

X ₃ and X ₄ are substituents substituted in the benzene ring, each independently, a fluorine (F) atom, an alkyl fluoride having 1 to 5 carbon atoms, an alkoxy fluoride having 1 to 5 carbon atoms, an aryl fluoride having 6 to 20 carbon atoms, or a carbon atom 6-20 alkoxyaryl fluoride.

In addition, the present invention provides a liquid crystal cell including the vertical alignment layer and the liquid crystal layer formed on the vertical alignment layer.

【Effects of the Invention】

The vertical alignment layer of the present invention includes a copolymer of a cyclic olefin compound having a structure in which a specific cyclic substituent is substituted, and may exhibit improved interaction with liquid crystal molecules even at a low temperature process, and thus may have excellent photo alignment. .

[Brief Description of Drawings]

1 schematically illustrates a structure of a liquid crystal cell according to an embodiment of the present invention. It is shown.

[Specific contents to carry out invention]

Also, the terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting of the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. As used herein, the terms "comprise", "comprise" or "have" are intended to indicate that the features, numbers, steps, components, or combinations thereof are present, one or more other features. It is to be understood that the present invention does not exclude the possibility of the presence or the addition of numbers, steps, components, or combinations thereof.

Also, in the present invention, when each layer or element is referred to as being formed "on" or "on" of each layer or element, it means that each layer or element is directly formed on each layer or element, or It means that a layer or element can be additionally formed between each filling, on the object, the substrate. As the invention allows for various changes and numerous modifications, particular embodiments will be illustrated and described in detail below. It is to be understood, however, that the intention is not to limit the invention to the particular form disclosed, but to include all modifications, equivalents, and substitutes falling within the spirit and scope of the invention.

Prior to describing the present invention, the definition of each substituent used herein is described in detail as follows:

First, "alkyl" means a linear or branched saturated monovalent hydrocarbon moiety of 1 to 20, preferably 1 to 10, more preferably 1 to 6 carbon atoms. The alkyl group may encompass not only unsubstituted but also further substituted by a certain substituent described below. Examples of the alkyl group include methyl, ethyl, propyl, 2-propyl, n-butyl, iso-butyl, tert-butyl, pentyl, nucleus, dodecyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, Dichloromethyl, trichloromethyl, iodomethyl, bromomethyl and the like. "Alkenyl" means a linear or branched monovalent hydrocarbon moiety of 2 to 20, preferably 2 to 10, more preferably 2 to 6 carbon atoms comprising at least one carbon-carbon double bond. . Alkenyl groups may be bonded through a carbon atom comprising a carbon-carbon double bond or through a saturated carbon atom. Alkenyl groups may be broadly referred to as unsubstituted as well as those further substituted by the following substituents. Examples of the alkenyl group include ethenyl, 1-propenyl, 2-propenyl, 2-butenyl, 3-butenyl, pentenyl, 5-nucenenyl, dodecenyl, and the like.

"Cycloalkyl" refers to a saturated or unsaturated non-aromatic monovalent monocyclic, bicyclic or tricyclic hydrocarbon moiety of 3 to 12 ring carbons, which is further encompassed further by certain substituents described below. can do. For example, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclonuxyl, cyclonuxenyl, cycloheptyl, cyclooctyl, decahydronaphthalenyl, adamantyl, norbornyl (ie, bicyclo [2,2, 1] hept-5-enyl).

"Aryl" means a monovalent monocyclic, bicyclic or tricyclic aromatic hydrocarbon moiety having from 6 to 40, preferably from 6 to 12 ring atoms, encompassing those further substituted by certain substituents described below May be referred to. Examples of the aryl group include phenyl phenyl naphthalenyl, fluorenyl and the like.

"Alkoxyaryl" means that at least one hydrogen atom of the aryl group as defined above is substituted with an alkoxy group. Examples of the alkoxyaryl group are methoxyphenyl, epoxyphenyl, propoxyphenyl, butoxyphenyl, phenoxyphenyl, nucleooxyphenyl, hepoxy, oxoxy, nanoxy, methoxybiphenyl methoxynaphthalenyl, methoxy Cyfluorenyl black includes mesocyananthracenyl and the like.

"Arylalkyl" means that at least one hydrogen atom of the alkyl group defined above is substituted with an aryl group, and may be referred to collectively further substituted by a specific substituent described below. For example, benzyl, benzhydryl, trityl, etc. are mentioned.

"Alkynyl" means a linear or branched monovalent hydrocarbon moiety of from 2 to 20 carbon atoms, preferably from 2 to 10, more preferably from 2 to 6, containing at least one carbon-carbon triple bond. do. Alkynyl groups may be bonded through a carbon atom containing a carbon-carbon triple bond or through a saturated carbon atom. Can be. Alkynyl groups may also be referred to collectively further substituted by certain substituents described below. For example, ethynyl, propynyl, etc. are mentioned.

"Alkylene" means a linear or branched saturated divalent hydrocarbon moiety of 1 to 20, preferably 1 to 10, more preferably 1 to 6 carbon atoms. The alkylene group can also be referred to collectively further substituted by certain substituents described below. As an example of an alkylene group, methylene, ethylene, propylene-butylene, nuxylene, etc. are mentioned.

"Alkenylene" means a linear or branched divalent hydrocarbon moiety of 2 to 20, preferably 2 to 10, more preferably 2 to 6 carbon atoms comprising at least one carbon-carbon double bond. do. Alkenylene groups may be bonded through a carbon atom comprising a carbon-carbon double bond and / or through a saturated carbon atom. Alkenylene group can also refer to what is further substituted by the specific substituent mentioned later.

"Cycloalkylene" means a saturated or unsaturated non-aromatic dicyclic monocyclic bicyclic or tricyclic hydrocarbon moiety of 3 to 12 ring carbons, and also encompasses those further substituted by certain substituents described below. can do. For example, cyclopropylene, cyclobutylene, etc. are mentioned.

"Arylene" means a divalent monocyclic, bicyclic or tricyclic aromatic hydrocarbon moiety having from 6 to 20, preferably from 6 to 12 ring atoms, further substituted by the following substituents It may be referred to inclusively. The aromatic moiety contains only carbon atoms. Phenylene etc. are mentioned as an example of an arylene group.

"Alkynylene" means a linear or branched divalent hydrocarbon site of 2 to 20 carbon atoms, preferably 2 to 10, more preferably 2 to 6, carbon atoms containing at least one carbon-carbon triple bond. do. Alkynylene groups may be bonded through a carbon atom comprising a carbon-carbon triple bond or through a saturated carbon atom. Alkynylene groups can also be referred to collectively further substituted by certain substituents described below. For example, ethynylene, propynylene, etc. are mentioned.

The substituents described above are " substituted or unsubstituted " It is meant to encompass not only the substituents themselves, but also those further substituted by certain substituents. In the present specification, unless specifically defined otherwise, examples of the substituent which may be further substituted with each substituent include halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, Arylalkyl, haloarylalkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, haloaryloxy, silyl, siloxy or the following "oxygen, nitrogen, phosphorus, sulfur, silicon or boron Polar functional groups ”and the like.

In addition, the copolymer encompasses all copolymers (copolymers, terpolymers) composed of polymerization of at least two different monomers.

In addition, in this specification, "vertical alignment film" is a kind of alignment film that determines the alignment state of the liquid crystal molecules before the voltage is applied to the liquid crystal molecules having dielectric anisotropy in the liquid crystal display device, the initial orientation of the liquid crystal molecules is the normal direction of the substrate Is formed to be completely parallel to the substrate or slightly inclined from the normal direction of the substrate toward one direction in the substrate surface, so that the liquid crystal molecules are parallel to the substrate by voltage application, falling through a desired constant direction, or falling without a constant direction, thereby causing an orientation change. It means an alignment film which arises.

The vertically oriented optical film including the vertical alignment layer may be used alone or in combination with other films, such as TN (Twist Nematic) mode, STN (Super Twist Nematic) mode, IPS (ln Plane Switching) mode, VA (Vertical Alignment) mode, In a liquid crystal display (LCD) device such as an OCB (Optically Compensated Birefringence) mode, the liquid crystal display may be used as an alignment layer for alignment of liquid crystals, and may be manufactured by coating a liquid crystal after forming a thin alignment layer by coating an alignment agent. Hereinafter, a vertical alignment layer according to an embodiment of the present invention will be described in detail.

According to one embodiment of the invention, there is provided a vertical alignment layer comprising a copolymer of a cyclic olefin compound represented by the following Chemical Formula 1 and a cyclic olefin compound represented by the following Chemical Formula 1-1.

[Formula 1]

3 R2

In Chemical Formula 1,

q is an integer from 0 to 4,

At least one of R 1 to R 4 is a radical represented by the following Chemical Formula 1 a, except that R 1 to R 4 are the same as or different from each other except _a radical of the general formula i _a , and each independently hydrogen; halogen; Substituted or unsubstituted linear or branched alkyl having 1 to 20 carbon atoms; Unsubstituted or unsubstituted linear or branched alkenyl having 2 to 20 carbon atoms; Substituted or unsubstituted linear or branched alkynyl having 2 to 20 carbon atoms; Substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Substituted or unsubstituted aryl having 6 to 40 carbon atoms; Substituted or unsubstituted arylalkyl having 5 to 12 carbon atoms; And a polar functional group including at least one selected from oxygen, nitrogen, phosphorus, sulfur, silicon, and boron,

R1 to R4 are hydrogen; halogen; Or when it is not a polar functional group, one or more combinations of R1 and R2 or R3 and R4 are connected to each other to have 1 to

Or an alkylidene group of 10, or R1 or R2 may be linked to either of R3 and R4 to form a saturated or unsaturated aliphatic ring having 4 to 12 carbon atoms, or an aromatic ring having 6 to 24 carbon atoms,

[anger

In Formula i _a

a1 and c1 are each independently a simple bond or a substituted or unsubstituted alkylene having 1 to 5 carbon atoms, h is ester

Χι and X2 are substituents substituted in the benzene ring, each independently a fluorine (F) atom, alkyl of 1 to 5 carbon atoms, alkoxy fluoride of 1 to 5 carbon atoms, aryl fluoride of 6 to 20 carbon atoms, or 6 to 20 is alkoxy aryl fluoride,

In Chemical Formula 2,

q 'is an integer from 0 to 4,

At least one of R 1 'to R 4' is a radical represented by the following Chemical Formula 1-1 a,

Except for being a radical of formula (ii _a) , R 1 ′ to R 4 ′ are the same as or different from each other, and each independently hydrogen; halogen; Substituted or unsubstituted linear or branched alkyl having 1 to 20 carbon atoms; Substituted or unsubstituted linear or branched alkenyl having 2 to 20 carbon atoms; Substituted or unsubstituted linear or branched alkynyl having 2 to 20 carbon atoms; Substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Substituted or unsubstituted aryl having 6 to 40 carbon atoms; Substituted or unsubstituted arylalkyl having 5 to 12 carbon atoms; And a polar functional group comprising at least one subphase selected from oxygen, nitrogen, phosphorus, sulfur, silicon, and boron,

R1 'to R4' is hydrogen; halogen; Or when it is not a polar functional group, one or more combinations of R1 'and R2' or R3 'and R4' are connected to each other to form an alkylidene group having 1 to 10 carbon atoms, or R1 'or R2' is R3 'and R4' Of May be linked to any one of a saturated or unsaturated aliphatic ring having 4 to 12 carbon atoms or an aromatic ring having 6 to 24 carbon atoms,

[

In Chemical Formula 1-1a

b2 is ester,

c2 is substituted or unsubstituted alkenylene having 2 to 5 carbon atoms,

n3 and n4 are each independently an integer of 0 to 5, η3 + π4 is an integer of 1 to 5,

₃ and ₄ are substituents substituted in the benzene ring, and each independently represent a fluorine (F) atom, an alkyl fluoride having 1 to 5 carbon atoms, an alkoxy fluoride having 1 to 5 carbon atoms, an aryl fluoride having 6 to 20 carbon atoms, or a carbon atom 6 to 20 fluorinated ⁰ cocciaryl.

The compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 1-1 may each have a predetermined substituent in a cyclic olefin structure that may be used as a precursor or a monomer of a polymer of various compounds. Or may have Formula 1-1 a). For example, in the case of Formula 1a, it may have a chemical structure in which a functional group such as a substituted benzoic acid ester structure or a phenyl ester structure is introduced, and in the case of Formula 1-1a, a benzene ring substituted cinnamic acid ester structure It may have a chemical structure introducing a photoreactor such as.

This functional group, or because of a photoreactive chemical structure is introduced into the annular eulre pin compound or cyclic eulre pin compounds of the formula 1 of the formula (1) may be ^'used in aligning the compound in itself.

In addition, various compounds or copolymers may be prepared from the compound of Formula 1 or the compound of Formula 1-1 due to the characteristics of the cyclic olefinic structure which may be used as a precursor. It can exhibit excellent light response. Thus, the annular It is possible to prepare various photoreactive compounds or copolymers applicable to various optical applications using an elepin compound.

In addition, the cyclic olefin compound of Formula 1 may be a benzoic acid ester or a fluorine atom, an alkyl fluoride group, an alkoxy fluoride group, an aryl fluoride group substituted with a fluorine atom, an alkyl fluoride group, an alkoxy fluoride group, an aryl fluoride group, or an alkoxy fluoride group Or a phenyl ester substituted with a phenyl ester substituted with an alkoxy fluoride group, wherein the cyclic olefin compound represented by Formula 1-1 has a benzene ring having a fluorine atom, an alkyl fluoride group, an alkoxy fluoride group, an aryl fluoride group, or an alkoxy fluoride group The cinnamic acid ester substituted with a group may have a chemical structure bonded thereto.

Due to this chemical structure, the photocyclic acopolymer obtained from the cyclic olefin compound represented by Chemical Formula 1 and the cyclic olefin compound represented by Chemical Formula 1-1 may exhibit improved interaction with liquid crystal molecules, and may be a low temperature process. Also, since it can cause photo-alignment more effectively and does not require a separate high temperature imidation process, it can be preferably used for a liquid crystal alignment film or the like which requires a relatively low temperature process compared to an alignment film using polyimide.

In addition, the structural increase of Formula 1a, a1 and c1 may be adjusted with alkylene of various lengths, or X and X ₂ may be adjusted with substituents of various structures, and the structural increase of Formula 1-1 a, a2 To adjust alkylene of various lengths, to c2 to alkenylene of various lengths, or to X ₃ and X 4 with substituents of various structures, thereby easily adjusting the photoreaction properties at low temperatures for the copolymers obtained therefrom. It becomes possible.

Hereinafter, the cyclic olefin compound and the photoreactive copolymer obtained therefrom will be described in more detail.

In the cyclic olefin compound, a polar functional group that may be substituted with R 1 to R 4 and R 1 ′ to R 4 ′, ie, a polar functional group including at least one selected from oxygen, nitrogen, phosphorus, sulfur, silicon, and boron It may be selected from the group consisting of the functional groups listed in the above, in addition to various polar functional groups containing one or more selected from oxygen, nitrogen, phosphorus, sulfur, silicon or boronosis:

-OR ₆ , -OC (0) OR ₆ , -R ₅ OC (O) OR ₆ , -C (O) OR ₆ , -R ₅ C (O) OR ₆ , -C (O) R ₆ ,-

-p ^{p ((() (() ()) (55655} 6,, CoccORcOROORORcO9O ROR0c-- ^, ---

CI

-R ₅ — H ₂ ⁺ -R ₅ — — R ₅ — Si ᅳ R

R,

R _P OR ₍

CI

-R ₅ — NH ₂ ⁺ -R ₅ — N— R ₅ ^" Si" OR ₇

R

In these polar functional groups, p is each independently an integer of 1 to 10, and R ₅ is a substituted or unsubstituted linear or branched alkylene having 1 to 20 carbon atoms; Substituted or unsubstituted linear or branched alkenylene having 2 to 20 carbon atoms; Unsubstituted linear or branched alkynylene having 2 to 20 carbon atoms; Substituted or unsubstituted cycloalkylene having 3 to 12 carbon atoms; Substituted or unsubstituted arylene having 6 to 40 carbon atoms; Substituted or unsubstituted carbonyloxyylene having 1 to 20 carbon atoms; Or substituted or unsubstituted alkoxylene having 1 to 20 carbon atoms, and R ₆ , R ₇ and R ₈ are each independently hydrogen; halogen; Substituted or unsubstituted linear or branched alkyl having 1 to 20 carbon atoms; Substituted or unsubstituted linear or branched alkenyl having 2 to 20 carbon atoms; Substituted or unsubstituted linear or branched alkynyl having 2 to 20 carbon atoms; Substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Substituted or unsubstituted aryl having 6 to 40 carbon atoms; Substituted or unsubstituted alkoxy having 1 to 20 carbon atoms; And substituted or unsubstituted carbonyloxy having 1 to 20 carbon atoms.

In addition, in the structure of Formula 1a, the benzene ring linked to the cyclic olefin through a simple bond or alkylene group of a1 and c1, and a fluorine atom, an alkyl fluoride group, an alkoxy fluoride group, an aryl fluoride group corresponding to X ₂ Or 1-5 substituted by an alkoxy fluoride group. Specifically, for example, X and X ₂ are each independently a fluorine atom (F); A linear or branched alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with the fluorine atom; Straight or branched chain of 1 to 5 carbon atoms, wherein at least one hydrogen is substituted with said fluorine atom An alkoxy group; An aryl group having 5 to 20 carbon atoms in which at least one hydrogen is substituted with the fluorine atom; At least one hydrogen contained in the alkoxy group may be an alkoxyaryl fluoride group having 5 to 20 carbon atoms substituted with the fluorine atom.

And, in the structure of Formula 1-1 a, the benzene ring linked to the cyclic olefin through a2, b2, and c2, fluorine atom, alkyl fluoride group, alkoxy fluoride group, aryl fluoride corresponding to X ₃ and X ₄ It may be 1 to 5 substituted by a group or an alkoxy fluoride group. Specifically, for example, X ₃ and X ₄ are each independently a fluorine atom (F); A linear or branched alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with the fluorine atom; C1-C5 linear or branched alkoxy group in which at least one hydrogen is substituted with the said fluorine atom; An aryl group having 5 to 20 carbon atoms in which at least one hydrogen is substituted with the fluorine atom; At least one hydrogen contained in the alkoxy group may be an alkoxy fluorinated aryl group having 5 to 20 carbon atoms substituted with the fluorine atom.

Since the specific substituents described above are introduced into the cyclic olefin, the cyclic olefin compound of Formula 1 or the cyclic olefin compound of Formula 1-1 has a strong hydrophobic surface energy, and the initial orientation of the liquid crystal molecules is perpendicular to the film. It can have a feature that can be arranged as.

The above-mentioned cyclic olefin compound is prepared according to a conventional method of introducing a cyclic olefin, for example, a predetermined substituent to the norbornene-based compound, more specifically, the functional group of Formula 1a or the photoreactor of Formula 1-1a. Can be. For example, the cyclic olefin compound may be prepared by condensing norbornene methane with a norbornene alkylol such as a carboxylic acid compound or an acyl chloride compound having a functional group corresponding to Formulas 1a and 1-1a, respectively; and, by introducing the photoreactive in different ways, depending on the functional group and the structure and type of the photoreactive of formula 1-1 a of the other _a formula i can be prepared by cyclic olefin compound mentioned above.

According to one embodiment of the invention, the copolymer may be a light semi-coagulant copolymer comprising a repeating unit of the formula 2a or 2b.

[Formula 2a]

Independently represented by Formula 2a and 2b,

m and m 'are 50 to 5000,

q and q 'are integers from 0 to 4,

R1 to R4 are the same as defined in Chemical Formula 1 of Claim 1, and R1 'to R4' are the same as defined in Chemical Formula 1-1 of Claim 1. Such photoreactive copolymers include each repeating unit derived from the above-described cyclic olefin compounds, and may exhibit excellent photoreactivity. In particular, as the different repeating units each have the structure of Formula 1a or Formula 1-1a as described above, it may exhibit improved interaction with the liquid crystal molecules and may exhibit excellent photoreactivity. In addition, a1 and c1 of the substituents of the general formula (1a) are selected and adjusted with alkylene of various lengths, and the substituent-substituted benzene ring is selected from a fluorine atom, an alkyl fluoride group, an alkoxy fluoride group, an aryl fluoride group, and an alkoxy fluoride aryl group. And adjusting, a2 in the substituent of Formula 1-1a to alkylene of various lengths. Selective control, by selecting and controlling c2 with alkenylene of various lengths, and also selecting and controlling substituents of the benzene ring among fluorine atoms, fluorinated alkyl groups, alkoxy fluoride groups, aryl fluoride groups, and alkoxy aryl fluoride groups, It can exhibit excellent light response to.

In addition, the photoreactive copolymer includes a norbornene-based repeating unit of Formula 2a or 2b as a main repeating unit. Such norbornene-based repeating units are structurally rigid, and the photoreaction copolymer comprising them has a relatively high light transition temperature (Tg) of about 300 ° C. or higher, preferably about 300 to 350 ^° C. It can exhibit excellent thermal stability compared to the reactive copolymer. In addition, the photobanung copolymer may exhibit excellent orientation since the photoreactor may move relatively freely in the polymer backbone due to its structural characteristics in which the photoreactor is bonded to the norbornene-based repeating unit.

Therefore, the photo-reflective copolymer may be preferably used in the liquid crystal alignment layer for photoalignment, and may be preferably applied to various other optical processing fields.

In addition, the photoreactive copolymer may include only one or more repeating units selected from the group consisting of repeating units of Formula 2a or 2b, but may also be a copolymer further including other types of repeating units. Examples of such repeating units may include any olefinic repeating unit, acrylate repeating unit, or cyclic olefinic repeating unit, in which cinnamate-based, chalcone-based or azo-based photoreactors are bonded or unbonded. Examples of such repeating units are disclosed in patent publication no. 2010-0021751 and the like.

However, the photoreactive copolymer is about 50 mol% or more, specifically about 50 to about 100 mol%, preferably about 70 mol% or more so that the excellent photoreaction property according to Chemical Formula 2a or 2b is not inhibited. It may include a repeating unit of Formula 2a or 2b.

In addition, the repeating unit of Formula 2a or 2b constituting the photoreactive copolymer may have a polymerization degree of about 50 to about 5,000, preferably a polymerization degree of about 100 to about 4,000, and more preferably about 1,000 to about 3,000. Can have And, the light semi-coagulant copolymer is about 10,000 to about 1,000,000 g / mol, It may preferably have a weight average molecular weight of about 100,000 to about 300,000 g / mol. Accordingly, the photoreactive copolymer may be suitably included in the coating composition for forming the alignment layer to exhibit excellent coating properties, and the alignment layer formed therefrom may exhibit excellent liquid crystal alignment.

The photoreactive copolymers described above can exhibit photoreaction under exposure to polarized light having a wavelength of about 150 to about 450 nm, for example, a wavelength of about 200 to about 400 nm, more specifically a wavelength of about 250 to about 350 nm. Photoreactivity can be exhibited under exposure of polarized light having In particular, among the functional groups a1, c1 and a2 are selected and controlled by various lengths of alkylene, c2 is selected and controlled by various lengths of alkenylene, and the substituents of each benzene ring are substituted with fluorine atoms, alkyl fluoride groups and alkoxy fluoride groups. , according to the fire screen eu aryl groups also, and select and adjust the fluorinated alkoxy aryl group ^", and can exhibit excellent photo-reactive with respect to the polarization of light and, in various directions over a wide wavelength band light above.

The above-described light semi-coagulant copolymer can be prepared by the following method.

One embodiment of the production method is a repeat of the formula (2a) by addition polymerization of the monomer of Formula 1 and the monomer of Formula 1-1 in the presence of a catalyst composition comprising a procatalyst and a promoter comprising a transition metal of Group 10 Forming a unit.

At this time, the polymerization reaction may be carried out at a temperature of 10 ^° C to 20 C C. When the reaction temperature is less than io ° C, the polymerization activity may be lowered, and when the reaction temperature is greater than 2 (xrc, the catalyst may be decomposed, which is not preferable.

In addition, the cocatalyst may include a first cocatalyst which provides a Lewis base capable of weakly coordinating with the metal of the procatalyst; And a second cocatalyst which provides a compound comprising a Group 15 electron donor ligand. Preferably, the cocatalyst may be a catalyst mixture comprising a first cocatalyst which provides the Lewis base, and optionally a second cocatalyst of a compound comprising a neutral Group 15 electron donor ligand.

In this case, the catalyst mixture may include about 1 to about 1000 moles of the crab co-catalyst with respect to 1 mol of the procatalyst, and about 1 to about 1000 moles of the crab co-catalyst. Too much content of the first catalyst or the second tank catalyst If small, the catalyst activation may not be performed properly, on the contrary, if too large, the catalytic activity may be lowered.

In addition, the procatalyst including the Group 10 transition metal may be easily separated by the first cocatalyst to provide a Lewis base so that the central transition metal may be converted into a catalytically active species. It is possible to use compounds having Lewis base functional groups which break away from the metal. For example, [(Allyl) Pd (CI)] 2 (Allylpalladiumchloride dimer), (CH ₃ CO ₂ ) ₂ Pd [Palladium (II) acetate], [CH ₃ COCH = C (O−) CH ₃ ] ₂ Pd [Palladium ( II) acetylacetonate], NiBr (NP (CH ₃ ) ₃ ) ₄ '

[PdCI (NB) 0 (CH ₃ )] ₂ and the like.

In addition, the first procatalyst, which provides a Lewis base capable of weakly coordinating with the metal of the procatalyst, easily reacts with the Lewis base to form a vacancy in the transition metal, and also to stabilize the transition metal thus formed. Compounds that weakly coordinate with metal compounds can be used as compounds that provide them. For example, boranes such as B (C ₆ F ₅ ) ₃ or borates such as dimethylanilinium tetrakis (pentafluorophenyl) borate, methylaluminoxane (MAO) or AI (C ₂ H ₅ ) there is a transition metal halide such as such as ₃ _and> alkylaluminum eu or AgSbF ₆ like.

In addition, an alkyl phosphine, a cycloalkyl phosphine, or a phenyl phosphine may be used as the second cocatalyst for providing a compound including the neutral group 15 electron donor ligand.

The first and second cocatalysts may also be used separately, but these two cocatalysts may be used as a compound to make a salt to activate a catalyst. For example, a compound made by ion bonding an alkyl phosphine and a borane or a borate compound may be used.

Through the above-described method, a photoreactive copolymer of one embodiment including the repeating unit of Formula 2a and the same may be prepared. In addition, in the case where the light semicoherent co-polymer further includes an leupin-based repeating unit, a cyclic olefin-based repeating unit, an acrylate-based repeating unit, or the like, these repeating units are formed by a conventional production method of each repeating unit, and the aforementioned Formula prepared by the method The photoreactive copolymer may be obtained by copolymerization with a repeating unit of 2a.

On the other hand, when the light semi-coagulant copolymer comprises a repeating unit of Formula 2b, it can be prepared according to another embodiment of the preparation method.

In another embodiment of the present invention, a ring-opening polymerization of a norbornenol-based monomer or a norbornenealkyl-based monomer in the presence of a catalyst composition comprising a procatalyst and a co-catalyst comprising a transition metal of Group 4, 6, or 8 To form a ring-opening polymer; And introducing a functional group represented by Chemical Formula 1a and a photoreaction group represented by Chemical Formula 1-1 a to the ring-opening polymer to form a repeating unit of Chemical Formula 2b.

In this case, the introduction of the photoreactor may proceed with reaction to condense the ring-opening polymer with a mixture of a carboxylic acid compound or an acyl chloride compound having a functional group corresponding to Formula 1 a and Formula 1-1 a, respectively.

Alternatively, the monomer of Formula 1 and the monomer of Formula 2 may be ring-opened copolymerized in the presence of a catalyst composition comprising a procatalyst and a promoter including a transition metal of Group 4, 6, or 8 It may be produced through the step of forming a repeating unit of 2b.

In the ring-opening polymerization step, when hydrogen is added to a double bond in the norbornene ring included in the monomer of Formula 1 and the monomer of Formula 1-1, ring-opening may proceed, and co-polymerization proceeds to repeat the process of Formula 2b. Units and photoreactive copolymers comprising the same can be prepared.

The ring-opening polymerization or ring-opening copolymerization is a procatalyst comprising a transition metal of Group 4 (e.g. Ti, Zr, Hf), Group 6 (e.g. Mo, W), or Group 8 (e.g. Ru, Os). Catalyst mixture comprising a cocatalyst that provides a Lewis base capable of weakly coordinating with the metal of the catalyst and a neutral group 15 and 16 activator that can optionally enhance the activity of the procatalyst metal Exist ί, can proceed. In addition, in the presence of such a catalyst mixture, about 1 to about 100 mol% of linear alkene, such as 1-alkene and 2-alkene, which can adjust the molecular weight size, is added to the monomer, and it is about 10 ^° C to about 200 ^° C. The polymerization may be carried out at a temperature of C, and a catalyst containing a transition metal of Group 4 (eg, Ti, Zr) black, or Group 8 to 10 (eg, Ru, Ni, Pd) may be present in a range of about 1 to about 30 About 10 ^° C by adding weight% The reaction may be carried out by hydrogenation of the ^' double bond in the norbornene ring at a temperature of from about 250 ^° C.

If the reaction temperature is too low, there is a problem that the polymerization activity is lowered, and if the reaction temperature is too high, the catalyst is decomposed, which is not preferable. In addition, when the hydrogenation reaction temperature is too low, there is a problem that the activity of the hydrogenation reaction is lowered, and when too high, the catalyst is decomposed, which is not preferable.

The catalyst mixture may be added to one mole of the procatalyst comprising a transition metal of Group 4 (e.g., Π, Zr, Hf), Group 6 (e.g. Mo, W), or Group 8 (e.g. Ru, Os). From about 1 to about 100,000 moles of cocatalyst that provides a Lewis base capable of weakly coordinating with the metal of the procatalyst, and optionally a group of neutral Group 15 and 16 elements that can enhance the activity of the procatalyst metal Activator comprises about 1 to about 100 moles per mole of procatalyst.

When the content of the promoter is less than about 1 mole, there is a problem that the catalyst activation is not made, and when the content of the promoter is greater than about 100,000 moles, the catalyst activity is lowered, which is not preferable. The activator may not be necessary depending on the type of procatalyst. When the content of the activator is less than about 1 mole, there is a problem that the catalyst activation is not made, and when the content of the activator is greater than about 100 moles, the molecular weight is lowered, which is not preferable.

Group 4 (eg Ti, Zr) or Group 8 to be used in the hydrogenated reaction reaction

Group 10 (for example, Ru, Ni, Pd) in the case where the content of the catalyst monomer preparation is less than about 1 weight ^_0/0 containing a transition metal and is a problem in that the hydrogenation does not easily achieved greater than about 30 weight ^_0/0 It is not preferable because there is a problem that the polymer is discolored.

Procatalysts comprising transition metals of Group 4 (e.g. Ti, Zr), Group 6 (e.g. Mo, W), or Group 8 (e.g. Ru, Os) are readily available by cocatalysts providing Lewis acids. Transition metal compounds, such as TiCI ₄ , WCI ₆ , M0CI _5, or RuCI ₃ or ZrCI ₄ , which have functional groups that readily participate in Lewis acid-base reactions and dissociate from the central metal so that they can be converted into catalytically active species. May be referred to.

In addition, Lewis capable of weakly coordinating with the metal of the procatalyst Cocatalysts that provide a base include borane or borate, such as B (C ₆ F ₅ ) ₃ , methylaluminoxane (MAO) or AI (C ₂ H ₅ ) ₃ , alkylaluminum, such as AI (CH ₃ ) CI ₂ , Alkyl aluminum halide and aluminum halide can be used. Alternatively, instead of aluminum, substituents such as lithium, magnesium, germanium, lead, zinc, tin, and silicon may be used. In this way, the compound easily reacts with the Lewis base to form a vacancy of the transition metal, and also weakly coordinates with the transition metal compound to provide a stabilized transition metal, or a compound providing the same.

Although an activator of polymerization can be added, it may not be necessary depending on the kind of procatalyst. An activator containing neutral Group 15 and 16 elements capable of enhancing the activity of the procatalyst metal is water, methane, ethanol, isopropyl alcohol, benzyl alcohol, phenol, ethyl mercaptan (ethyl). mercaptan), 2-chloroethanol, trimethylamine, triethylamine, pyridine, ethylene oxide, benzoyl peroxide, t-butyl peroxide, and the like.

Catalysts containing transition metals of Group 4 (e.g. Ti, Zr) or Groups 8-10 (e.g. Ru, Ni, Pd) used in the hydrogenation reaction are homogeneous forms that can be immediately mixed with the solvent. Or a metal catalyst complex supported on the particulate support. Preferably, the particulate support is silica, titania, silica / chromia, silica / chromia / titania, silica / alumina, aluminum phosphate gel, silanized silica, silica hydrogel, montmorillonite clay or zeolite. .

Through the above-described method, a photoreactive copolymer of one embodiment including the repeating unit of Formula 2b and the same may be prepared. Moreover, even when the said photo-banung copolymer further contains an olefin type repeating unit, a cyclic olefin type repeating unit, or an acrylate type repeating unit, these repeating units are formed by the conventional manufacturing method of each repeating unit, The photo-reflective copolymer may be obtained by copolymerization with a repeating unit represented by Chemical Formula 2b.

The vertical alignment layer including the photoreactive copolymer described above may include not only a thin film but also an oriented film in the form of a film. According to still another embodiment of the present invention, a liquid crystal cell including the vertical alignment layer and a liquid crystal layer on the vertical alignment layer is provided.

1 schematically illustrates a structure of a liquid crystal cell including a vertical alignment layer according to an embodiment of the present invention. Referring to FIG. 1, it can be seen that the liquid crystal cell includes a substrate 100, a vertical alignment layer 200 formed on the substrate, and a liquid crystal layer 300 on the vertical alignment layer.

For another example, two substrates 100 on which the alignment layer 200 is formed may overlap, and a liquid crystal may be injected therebetween to form the liquid crystal layer 300.

Such a vertical alignment layer and a liquid crystal cell may be manufactured using constituents and manufacturing methods known in the art, except for including the above-described light semicoagulant copolymer as a photoalignment copolymer.

For example, the vertical alignment layer may be formed by mixing the photoreactive copolymer, the binder resin and the photoinitiator and dissolving it in an organic solvent to obtain a coating composition, then coating the coating composition on a substrate and performing UV curing. .

At this time, the binder resin may be an acrylate resin, and more specifically, pentaerythritol triacrylate, dipentaerythroxy nuxaacrylate, trimethylolpropane triacrylate, tris (2-acryl Monooxyethyl) isocyanurate or the like can be used.

In addition, as the photoinitiator, a conventional photoinitiator known to be usable for the vertical alignment layer may be used without particular limitation, and for example, a trade name 1 3 (“6 907, 819 known as photoinitiator may be used).

In addition, as the organic solvent, toluene, anisole, chlorobenzene, dichloroethane, cyclonucleic acid, cyclopentane, propylene glycol methyl ether acetate and the like can be used. Since the photoreactive norbornene-based copolymer described above exhibits excellent solubility in various organic solvents, various organic solvents may be used without particular limitation.

In the coating composition, the solid content concentration including the light semi-coagulant copolymer, the binder resin and the photoinitiator may be 1 to 15% by weight ⁰ /., In order to cast the vertical alignment layer in the form of a film, 10 to 15 by weight ⁰ /. are preferred, from 1 to 5 parts by weight ^_0/0 is preferred in order to form a thin-film form. The vertical alignment layer thus formed may be formed on the substrate, for example, as shown in FIG. 1, and may be formed under the liquid crystal to align the same. In this case, the substrate may include a substrate including a cyclic polymer, a substrate including an acrylic polymer, or a substrate including a cellulose polymer. The coating composition may be variously coated, such as bar coating, spin coating, blade coating, or the like. The coating may be performed on a substrate and then UV cured to form a vertical alignment layer. Photo-alignment may occur by the UV curing. In this step, alignment may be performed by irradiating polarized UV in a wavelength range of about 150 nm to about 450 nm. In this case, the intensity of the exposure may be about 50 mJ / cuf to about 10 J / cuf of energy, preferably about 500 mJ / cuf to about 5 J / citf. The UV is a polarizing device using a substrate coated with a dielectric anisotropic substance on the surface of a transparent substrate, such as quartz glass, soda lime glass, soda lime free glass, ② polarizing plate finely deposited aluminum or metal wire, or ③ quartz Polarized UV selected from the polarized UV may be applied by passing or reflecting through the Brewster polarizer by reflection of the glass or the like.

As for the substrate temperature at the time of irradiating the said UV, normal temperature is preferable. However, in some cases, UV may be irradiated in a heated state within a silver range of 100 ^° C. or less. The film thickness of the final coating film formed by the above series of processes is about

It is preferred that it is from 30 to about 1000 nm.

A vertical alignment film is formed by the method mentioned above, a liquid crystal layer is formed on it, and a liquid crystal cell can be manufactured by a conventional method. As the vertical alignment layer includes the photoreactive copolymer, the vertical alignment layer may exhibit excellent interaction with the liquid crystal molecules, thereby enabling efficient photo alignment.

The above-described vertical alignment layer or liquid crystal cell may be applied to an optical film or an optical filter for implementing a stereoscopic image.

Accordingly, according to another embodiment of the present invention, a display device including the vertical alignment layer is provided. The display device may be a liquid crystal display device in which the vertical alignment layer is included for alignment of liquid crystals, or a stereoscopic image display device in which the vertical alignment layer is included in an optical film or a filter for realizing a stereoscopic image. However, the configuration of these display elements is the photoreactive copolymer and the vertical Except for including the alignment layer, since the configuration of the conventional device, the detailed description thereof will be omitted. Hereinafter, preferred embodiments are presented to help understand the invention. However, the following examples are only to illustrate the invention, not limited to the invention only.

In addition, all operations dealing with air or water sensitive compounds in the following examples were carried out using the standard Schlenk technique or dry box technique. Nuclear magnetic resonance (NMR) spectra were obtained using a Bruker 300 spectrometer, where ¹ H NMR was measured at 300 MHz and ¹³ C NMR at 75 MHz, respectively. The molecular weight and molecular weight distribution of the ring-opening hydrogenated polymer were measured using gel permeation chromatography (GPC), and polystyrene (p ystyrene) samples were used as the standard. Toluene was purified by distillation in potassium / benzophenone. Dichloromethane was distilled off in CaH ₂ .

Preparation of Photopolymerizable Olefin Compound

[Production Example 1]

Synthesis of bicyclo [2.2.1] hept-5-en-2-ylmethyl 4 '-(trifluoromethoxy) biphenyl-4-carboxylate

For 4 '-(trifluoromethoxy) biphenyl-4-carboxylic acid 1eq.er ^' , 1.1eq.Norbornene-5-methanol and zirconium (IV) acetylacetonate (CATM (0.001eq.) Together with xylene, dine The reactor was placed in a multi reactor equipped with stock and stirred for 48 hours at a reaction temperature of 200 ^° C.

Dehydration reaction confirmed that water was missing in the Deanstock portion, and a sample was taken and analyzed by GC to confirm that all acid components were consumed.

The reaction mixture was filtered with silica to remove CATM and residues. Column purification with Hex: EA = 10: 1 gave a compound of the above formula.

1 H NMR (CDCI3, TMS): 8.02 (d, 2H), 7.75 (d, 2H), 7.61 (d, 2H), 7.03 (d,

_{_{_{) Ί ^ (H)寸0}}} } (H2寸9寸(H3 1} 0ε382)寸82999Η ι 9 I / - EbEEω- ,, - eu - eu - - - - -

S

t $ a ^ι ΐ ^ * is ¾ ^ ¾§ο

y ^I N ⁽ H ⁾ P ⁾寸^{\ (} Η ⁾ 6s 寸 0 卜 6Z 5 寸 99 寸 ∞g2bΕ---. - ^. --.

) ⁽ Η ⁾ 2 ⁽工⁽ u ⁸ 3 ^ι寸 82 H ⁾⁾ 0S ^l 3 ⁹ 9 ^: / ε ^t Ε _--. ᅳ--·---

[ _// : _/ O 8 _/ -820 _S SSMl _> d 8 _/ . _Ϊ 6609 _Ϊ 0Ζ AV

It was put in a multi-reactor installed and stirred for 48 hours at a reaction temperature of 20C.

The reaction mixture was filtered with silica to remove CATM and residues. The remaining xylene was removed under reduced pressure, recrystallized with xylene again, and dried in a filter to obtain a compound of the above formula.

H NMR (CDCI ₃ , TMS): 7.68 (d, 2H), 7.48 (d, 1H), 6.88 (d, 2H), 6.31 (d, 1H), 5.98 (q, 2H), 4.55 (m, 2H), 2.84 (M, 1H), 2.58 (m, 1H), 2.13 (m, 1H), 1.75 (m, 2H), 1.56 (m, 2H)

[Comparative Production Example 1]

Synthesis of Cholestrerol-norbomene

Cholesterol (0.62 mol), N- (3-dimethylaminopropyl) -N'-ethylcarbodiimide hydrochloride (EDCI, 142.83 g, 0.92 mol, Fw = 155.25), N, N-dimethylamidopyridine (DMAP, 112.40 g, 0.92 mol, Fw = 122.17) was added to the flask and 1000 ml of CH ₂ CI ₂ was added.

5-norbornene-2-methane (76.99 g, 0.28 mol, Fw = 124.18) was added and stirred at room temperature for 20 hours.

After the reaction was completed, water was added and extracted with an organic layer, and then the organic layer was washed with brine.

The organic worms were dried over magnesium sulfate, filtered and filtered through column chromatography (EA: Hex = 1: 7) to obtain a compound of the above formula.

H-NMR (CDCI3 500MHz, ppm)

0.84 (3, s), 0.88 (3, d), 0.91 (6, d), 10.1 (3, s), 1.04-2.37 (32, m), 2.84 (1, m),

Preparation of 3.69 (1, m), 4.60 (1, quin), 5.27 (1, t), 6.05 (2, dd) photobanung copolymers

[Production Example 1 a]

Copolymerization of Preparation Example 1 and Preparation Example 1-1 Into the flask, the compounds of Preparation Example 1 and Preparation Example 1-1 were added together with toluene and heated to 90 ^° C. Pd cat (1/750) and cat H were added under a nitrogen atmosphere, and polymerization was performed for 18 hours.

Excess ethanol was poured into the obtained polymer solution, and the precipitate was again precipitated and washed twice with ethanol: acetone = 1: 1 solution, filtered, and dried in a vacuum oven to obtain a polymer.

Production Example 2a

-Copolymerization of Preparation Example 2 and Preparation Example 1-1

The same procedure was followed as in Preparation Example 1 a, except that the monomers used were different.

Production Example 3a

Copolymerization of Preparation Example 3 and Preparation Example 1-1

To the flask was added the compound of Preparation Example 3 and Preparation Example 1-1 together with toluene and 1 mol% of 1- octene, and heated to 90 ^° C. Pd cat (1/4000) and cat H were added under a nitrogen atmosphere, and polymerization was performed for 18 hours.

Excess ethanol was poured into the obtained polymer solution, precipitated, and washed and filtered twice in an ethanol: acetone = 1: 1 solution, followed by drying in a vacuum oven to obtain a polymer.

Production Example 4a

Copolymerization of Preparation Example 4 and Preparation Example 1 1

The monomers used were different, and the same procedure as in Preparation Example 1 a was carried out except that the catalyst amounts were different.

Production Example 5a

Copolymerization of Preparation Example 5 and Preparation Example 1-1

The same procedure as in Preparation Example 3a was conducted except that the monomers used were different. [Comparative Production Example 1a]

Copolymerization of Comparative Preparation Example 1 and Preparation Example 1-1

The same procedure as in Preparation Example 3a was conducted except that the monomers used were different. The polymerization conditions are summarized in Table 1 below.

Table 11

Comparative Example 1a Comparative Production Example 1

One

20 80 1/4 000 148 178 1.18 93

50 50 1/4 000 128 151 1.18 68

Preparation of alignment film and film

The copolymer according to Preparation Example 3 by weight ⁰ /, acrylate 1.0 Increased ⁰ / binder (PETA), a photoinitiator. (Irgacure 907, manufacturer: Ciba) is dissolved in toluene solvent such that 0.5 ⁰ /. The solution was then spin-coated on a COP film.

After drying at 100 ^° C. for 2 minutes, a sealant (epoxy resin) was applied to the edge of the COP film coated with the alignment film, and another COP film coated with the alignment film was folded and pressed, and UV (100mW / cm ² ) was applied thereto. Was investigated. At this time, a high pressure mercury lamp of 100mW / cm ² intensity was used as a light source in a nitrogen atmosphere, the amount of UV light was adjusted by time.

Liquid crystal was injected into two compressed films, a liquid crystal injector, the liquid crystal injection site was blocked with a sealant, and heat treated at 90 ^° C for 20 minutes to complete the liquid crystal cell.

Experimental Example

Orientation Evaluation

Between the two polarizers arranged vertically, each cell prepared above was placed, and the degree of light leakage was measured by observing with a polarizing microscope how much incident light transmitted through the polarizer and the cell.

According to the degree of light leakage, the evaluation was based on 10 out of 10, summarized in Table 2 below.

(10: No disclination occurs, 1: Disdination occurrence and no orientation) [Table 2]

Remarks Alignment after liquid crystal injection 95 ^° C (T _N , temperature above)

Preparation Example 2a 9 9

Preparation Example 3a 10 10

Preparation 5a 9 9

Comparative Example 1 a 10 1 Referring to Table 2, in the case of the comparative example, the orientation after the liquid crystal injection is excellent, it can be confirmed that the orientation is hardly maintained at a temperature of T _NI or more.

However, in the embodiment of the present application after the liquid crystal injection, or T _NI or more

It can be seen that the orientation is maintained very well even at the temperature.

[Explanation of code]

100: substrate

200: vertical alignment layer

300: liquid crystal layer

Claims

[Patent Claims]

[Claim 1]

A vertical alignment layer comprising a copolymer of the cyclic olefin compound represented by the following Chemical Formula 1 and the cyclic olefin compound represented by the following Chemical Formula 1-1:

In Chemical Formula 1,

q is an integer of 0 to 4,

At least one of R 1 to R 4 is a radical represented by the following Chemical Formula 1 a, except that R 1 to R 4 are the same as or different from each other, and are each independently hydrogen; halogen; Substituted or unsubstituted linear or branched alkyl having 1 to 20 carbon atoms; Substituted or unsubstituted linear or branched alkenyl having 2 to 20 carbon atoms; Substituted or unsubstituted linear or branched alkynyl having 2 to 20 carbon atoms; Substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Substituted or unsubstituted aryl having 6 to 40 carbon atoms; Substituted or unsubstituted arylalkyl having 5 to 12 carbon atoms; And a polar functional group including at least one selected from oxygen, nitrogen, phosphorus, sulfur, silicon, and boron,

R1 to R4 are hydrogen; halogen; Or when it is not a polar functional group, one or more combinations of f¾1 and R2 or R3 and R4 are connected to each other to form an alkylidene group having 1 to 10 carbon atoms, or R1 or R2 is connected to any one of R3 and R4 to 4 carbon atoms It may form a saturated or unsaturated aliphatic ring of 12 to 12, or an aromatic ring of 6 to 24 carbon atoms,

[Formula 1 a] ^ 놰 Χΐ) η1

In Formula i _a

a1 and c1 are each independently a simple bond or a substituted or unsubstituted alkylene having 1 to 5 carbon atoms,

This is ester,

Χι and X ₂ are substituents substituted in the benzene ring, and are each independently a fluorine (F) atom, an alkyl fluoride having 1 to 5 carbon atoms, an alkoxy fluoride having 1 to 5 carbon atoms, an aryl fluoride having 6 to 20 carbon atoms, or carbon atoms. 6-20 alkoxyaryl fluoride

[Formula 1-1]

In Chemical Formula 2,

q 'is an integer from 0 to 4,

At least one of R1 'to R4' is a radical represented by the following Chemical Formula 1-1a,

Except for being a radical of Formula 1-1 _a , the remaining R1 'to R4' are the same as or different from each other, and each independently hydrogen; halogen; Substituted or unsubstituted linear or branched alkyl having 1 to 20 carbon atoms; Substituted or unsubstituted linear or branched alkenyl having 2 to 20 carbon atoms; Substituted or unsubstituted linear or branched alkynyl having 2 to 20 carbon atoms; Substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Substituted or unsubstituted aryl having 6 to 40 carbon atoms; Substitution or Unsubstituted arylalkyl having 5 to 12 carbon atoms; And a polar functional group including at least one selected from oxygen, nitrogen, phosphorus, sulfur, silicon, and boron,

R1 'to R4' is hydrogen; halogen; Or when it is not a polar functional group, one or more combinations of RV and R2 'or R3' and R4 'are connected to each other to form an alkylidene group having 1 to 10 carbon atoms, or R1' or R2 'is selected from R3' and R4 ' May be linked with any one to form a saturated or unsaturated aliphatic ring having 4 to 12 carbon atoms or an aromatic ring having 6 to 24 carbon atoms,

[

*

In Chemical Formula 1 -1 _a

b2 is ester,

c2 is substituted or unsubstituted alkenylene having 2 to 5 carbon atoms,

n3 and n4 are each independently an integer of 0 to 5, n3 + n4 is an integer of 1 to 5,

X ₃ and X 4 are substituents substituted in the benzene ring, each independently, a fluorine (F) atom, an alkyl fluoride having 1 to 5 carbon atoms, an alkoxy fluoride having 1 to 5 carbon atoms, an aryl fluoride having 6 to 20 carbon atoms, or 6 carbon atoms To 20 alkoxy aryl fluoride.

[Claim 2]

The method of claim 1,

Wherein the polar functional group comprising at least one selected from oxygen, nitrogen, phosphorus, sulfur, silicon, and boron is selected from the group consisting of the functional groups listed below:

-OR ₆ , -OC (O) OR ₆ , -R ₅ OC (O) OR _6> -C (O) OR ₆ , -R ₅ C (0) OR ₆ , -C (O) R ₆ ,-R ₅ C (O) R ₆ , -OC (0) R ₆ , -R ₅ OC (O) R ₆ ,-(R ₅ O) _p -OR ₆ ,-(OR ₅ ) _p -OR ₆ , -C ( 0) -OC (O) R ₆ ,-

^{^{() (55366, - 36,}} 5 -, p 5 SSRCSSRR0RSRRNCNCSNcCS0 R ===== - - - - - = - (()) ((¾¾¾¾6, 5,,, 5 6, 5 ScoS_s p S P RSS (S ⁰ RS ⁰ co ^O FR R ==--------

ci-

-N- 一 R?

\

6 OR ₆

CI

NH ₂ ⁺一 R ₅ — N—— R ₅ — Si—— OR ₇

OR ₈ -R ₅一

In the polar functional group, p are each independently an integer of 1 to 10,

R ₅ is substituted or unsubstituted linear or branched alkylene having 1 to 20 carbon atoms; Substituted or unsubstituted linear or branched alkenylene having 2 to 20 carbon atoms; Substituted or unsubstituted linear or branched alkynylene having 2 to 20 carbon atoms; Substituted or unsubstituted cycloalkylene having 3 to 12 carbon atoms; Substituted or unsubstituted arylene having 6 to 40 carbon atoms; Substituted or unsubstituted carbonyloxyylene having 1 to 20 carbon atoms; Or substituted or unsubstituted alkoxylene having 1 to 20 carbon atoms,

Re, R / and R ₈ are each independently hydrogen; halogen; Substituted or unsubstituted linear or branched alkyl having 1 to 20 carbon atoms; Substituted or unsubstituted linear or branched alkenyl having 2 to 20 carbon atoms; Substituted or unsubstituted linear or branched alkynyl having 2 to 20 carbon atoms; Substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Substituted or unsubstituted aryl having 6 to 40 carbon atoms; Substituted or unsubstituted alkoxy having 1 to 20 carbon atoms; And substituted or unsubstituted carbonyloxy having 1 to 20 carbon atoms.

[Claim 3]

According to claim 12,

Each of the functional groups of R ₅ to R ₈ is unsubstituted, halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, arylalkyl, haloarylalkyl, alkoxy Haloalcohol, carbonyloxy, halocarbonyloxy, aryloxy, A vertical alignment film substituted with a functional group selected from the group consisting of haloaryloxy, silyl and siloxy.

[Claim 4]

The method of claim 1,

The copolymer is a photoreactive copolymer comprising a repeating unit of Formula 2a or 2b, a vertical alignment layer:

[

Each independently in Chemical Formulas 2a and 2b,

m and m 'are 50 to 5000,

q and q 'are integers from 0 to 4,

R1 to R4 are the same as defined in Formula 1 of claim 1,

R1 'to R4' is as defined in the general formula 1-1 of claim 1.

[Claim 5]

A liquid crystal cell comprising the liquid crystal layer of the vertical alignment layer and the vertical alignment layer according to any one of claims 1 to 4.

[Claim 6]

A display element comprising the vertical alignment layer of claim 1.