KR101740655B1 - Cyclic olefin compound, photoreactive polymer and alignment layer comprising the same - Google Patents

Abstract

The present invention relates to a cyclic olefin compound, a photoreactive polymer and an alignment film comprising the same. The cyclic olefin compound according to the present invention makes it possible to provide a photoreactive polymer which exhibits excellent liquid crystal alignability and orientation rate and has a property of easily changing the alignment direction according to the polarization direction.

Description

TECHNICAL FIELD [0001] The present invention relates to a cyclic olefin compound, a photoreactive polymer, and an alignment film comprising the same. BACKGROUND ART [0002]

The present invention relates to a cyclic olefin compound, a photoreactive polymer and an alignment film comprising the same.

Recently, in accordance with the expansion and enlargement of the usage of the liquid crystal display, high definition, high quality and wide viewing angle of the liquid crystal display are required. Particularly, a thin film transistor liquid crystal display (TFT-LCD) driven by a thin film transistor independently drives individual pixels, so that the response speed of liquid crystal is very excellent and a high-quality moving image can be realized.

In order to use the liquid crystal as an optical switch in such a TFT-LCD, the liquid crystal must be initially oriented in a certain direction on a layer on which the innermost thin film transistor of the display cell is formed, and a liquid crystal alignment layer is used for this purpose.

For this liquid crystal alignment, a rubbing process in which a heat-resistant polymer such as polyimide is applied on a transparent glass to laminate a polymer alignment film and a rubbing cloth made of nylon, rayon or the like is wound around the rotating roller at high speed while the rubbing process Have been applied.

However, the rubbing process may cause mechanical scratches on the surface of the liquid crystal aligning agent at the time of rubbing, or generate high static electricity, so that the thin film transistor may be broken. In addition, defects are caused by fine fibers or the like generated in the rubbing cloth, which hinders the improvement of the production yield.

The newly proposed liquid crystal alignment system to overcome the problems of the rubbing process and innovate in the productive aspect is a liquid crystal alignment (hereinafter referred to as "photo alignment") by light such as UV.

The photo-alignment refers to a mechanism for forming a photopolymerizable liquid crystal alignment film in which a photosensitive group bonded to a certain photoreactive polymer by a linearly polarized UV causes a photoreaction and a main chain of the polymer is aligned in a certain direction, Quot;

Representative examples of such optical alignment are disclosed in M. Schadt et al. (Jpn. J. Appl. Phys., Vol. 31, 1992, 2155), Dae S. Kang et al. (US Patent No. 5,464,669), Yuriy Reznikov Phys., Vol. 34, 1995, L1000). The photo-alignment polymers used in these patents and articles are mainly polycinnamate-based polymers such as PVCN (poly (vinyl cinnamate)) or PVMC (poly (vinyl methoxycinnamate)). When the polycinnamate-based polymer is photo-aligned, the double bond of the cinnamate is cycled to the [2 + 2] cycloaddition reaction by the irradiation UV to form cyclobutane, As a result, anisotropy is formed and the liquid crystal molecules are aligned in one direction to induce orientation of the liquid crystal.

In addition, Japanese Patent Application Laid-Open No. 1999-181127 discloses a polymer having a side chain including a photosensitive group such as a cinnamic acid group in a main chain such as acrylate and methacrylate, and an orientation film containing the polymer. Korean Patent Laid-Open No. 2002-0006819 discloses the use of an alignment film made of a polymethacrylic polymer.

However, the above-mentioned photoreactive polymers for alignment films have a disadvantage in that the thermal stability of the polymer main chain is deteriorated and the stability of the orientation film is lowered, or the photoreactivity, liquid crystal orientation, or orientation rate becomes insufficient.

In addition, there are application fields that require a change in anisotropy direction in accordance with the polarization direction uniquely, for example, patterned retarders and patterned cell alignment layers, which are applied for realizing three-dimensional stereoscopic images, Polymers need polarization in the other direction once the direction of orientation is determined by polarization, the direction does not move, or, even if it moves, a stronger amount of light.

The present invention provides a cyclic olefin compound which makes it possible to provide a photoreactive polymer which exhibits excellent liquid crystal alignability and orientation speed and is easy to change in alignment direction along the polarization direction.

In addition, the present invention provides a photoreactive polymer having properties that exhibit excellent liquid crystal alignability and orientation rate and can easily change the alignment direction according to the polarization direction, and a method for producing the same.

The present invention also provides an alignment film and a display element comprising the photoreactive polymer.

According to the present invention, there is provided a cyclic olefin compound having a photoreactive group represented by the following general formula

[Chemical Formula 1]

In Formula 1,

p is an integer of 0 to 4,

At least one of R ¹ , R ² , R ³ , and R ⁴ is a group represented by the following formula (2)

R ¹ to R ^{4, which} are other than the group of Formula 2, are the same or different from each other and each independently hydrogen; halogen; A substituted or unsubstituted C1 to C20 linear or branched alkyl; Substituted or unsubstituted C2-C20 linear or branched alkenyl; A substituted or unsubstituted linear or branched alkynyl having 2 to 20 carbon atoms; A substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Substituted or unsubstituted C6-C40 aryl; And polar functional groups comprising at least one selected from oxygen, nitrogen, phosphorus, sulfur, silicon, and boron,

When R ¹ to R ⁴ are not hydrogen, halogen, or a polar functional group, at least one combination of R ¹ and R ² , R ³ and R ⁴ is connected to each other to form an alkylidene group having 1 to 10 carbon atoms Or R ¹ or R ² may be bonded to any one of R ³ and R ⁴ to form a saturated or unsaturated aliphatic ring having 4 to 12 carbon atoms or an aromatic ring having 6 to 24 carbon atoms,

(2)

In Formula 2,

A is independently a simple bond, carbonyl, -COO-, -OCO-, oxygen, sulfur or -NH-,

B represents a single bond, a substituted or unsubstituted alkylene having 1 to 20 carbon atoms, carbonyl, -COO-, -OCO-, a substituted or unsubstituted arylene having 6 to 40 carbon atoms, and a substituted or unsubstituted carbon number 6 ≪ / RTI > to about 40 heteroarylen,

R ⁵ is a single bond, a substituted or unsubstituted alkylene having 1 to 20 carbon atoms, a substituted or unsubstituted alkenylene having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene having 3 to 12 carbon atoms, A substituted or unsubstituted arylene group having 6 to 40 carbon atoms, a substituted or unsubstituted aralkylene group having 7 to 15 carbon atoms, and a substituted or unsubstituted alkynylene group having 2 to 20 carbon atoms,

At least one of R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ is an alkyl having from 1 to 20 carbon atoms having an electron withdrawing group or an aryl having from 6 to 40 carbon atoms having an electron-

R ⁶ to R ¹⁰ , which are the same or different from each other, are each independently selected from the group consisting of hydrogen, halogen, substituted or unsubstituted C 1 -C 20 alkyl; A substituted or unsubstituted C1-C20 alkoxy; A substituted or unsubstituted aryloxy having 6 to 30 carbon atoms; A substituted or unsubstituted aryl having 6 to 40 carbon atoms, and a heteroaryl having 6 to 40 carbon atoms containing a heteroatom of group 14, group 15 or group 16.

Further, according to the present invention, there is provided a photoreactive polymer comprising repeating units of the following structural formula (3a) or (3b):

[Formula 3]

In the above formulas (3a) and (3b), n is independently from 50 to 5,000, and p, R ¹ , R ² , R ³ and R ⁴ are as defined in the above formula (1).

Further, according to the present invention, the cyclic olefin compound represented by the above formula (1) is subjected to addition polymerization in the presence of a catalyst composition comprising a procatalyst including a transition metal of Group 10 transition metal and a cocatalyst, And forming a photoreactive polymer on the surface of the photoreactive polymer.

According to the present invention, the cyclic olefin compound represented by the formula (1) is subjected to ring-opening polymerization in the presence of a catalyst composition comprising a precatalyst including a transition metal of Group 4, Group 6 or Group 8 and a cocatalyst To form a repeating unit of the above formula (3b).

Further, according to the present invention, there is provided an alignment film comprising the above-mentioned photoreactive polymer.

According to the present invention, there is also provided a liquid crystal phase difference film comprising the alignment film and a liquid crystal layer on the alignment film.

Further, according to the present invention, there is provided a display device comprising the alignment film.

The photoreactive polymer obtained from the cyclic olefin compound of the present invention has at least one electron withdrawing group bonded to the photoreactive unit. Such an electron attracting group induces a slope of the composition in the orientation film, thereby enabling to provide an orientation film having a more improved orientation. That is, at least one electron attracting group is bonded to the photoreactor, which affects the electron density of the double bond, resulting in a difference in the photoreaction rate. For example, when a strong electron attracting group such as -F, -NO ₂ is introduced into a photoreactor, the electron density of the double bond of the photoreactor is reduced, which weakens the binding force of the pp orbitals of the π-bond and breaks quickly It becomes easier to make [2 + 2] coupling with the surrounding double bonds. Through such an operation, an alignment film having a more improved alignment property can be provided.

In addition, since the photoreactive polymer can move relatively freely in the photoreactive polymer, a change in the orientation direction is remarkably free according to the polarization direction. Therefore, the photoreactive polymer and the alignment layer including the photoreactive polymer can be suitably applied to a patterned retarder and a patterned cell alignment layer, which are applied for realizing a three-dimensional stereoscopic image or the like.

Accordingly, such a photoreactive polymer can be suitably applied as a photo-alignment polymer in various coating compositions and alignment films formed therefrom, which are applied to various liquid crystal display devices and the like, and the alignment film including the photo-reactive polymer can exhibit excellent properties.

Fig. 1 schematically shows the structure of a typical alignment film.
2 is a scheme for synthesis of a cyclic olefin compound according to embodiments of the present invention.

Hereinafter, a cyclic olefin compound, a photoreactive polymer, a method for producing the same, an alignment film, and the like according to embodiments of the present invention will be described in detail.

Prior to that, the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. And, the singular forms used herein include plural forms unless the phrases expressly have the opposite meaning. Also, as used herein, the term " comprises " embodies specific features, regions, integers, steps, operations, elements or components, and does not exclude the presence of other specified features, regions, integers, steps, operations, elements, It does not.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

Cyclic olefin compound

According to one embodiment of the present invention, there is provided a cyclic olefin compound having a photoreactive group represented by the following general formula

[Chemical Formula 1]

In Formula 1,

p is an integer of 0 to 4,

At least one of R ¹ , R ² , R ³ , and R ⁴ is a group represented by the following formula (2)

R ¹ to R ^{4, which} are other than the group of Formula 2, are the same or different from each other and each independently hydrogen; halogen; A substituted or unsubstituted C1 to C20 linear or branched alkyl; Substituted or unsubstituted C2-C20 linear or branched alkenyl; A substituted or unsubstituted linear or branched alkynyl having 2 to 20 carbon atoms; A substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Substituted or unsubstituted C6-C40 aryl; And polar functional groups comprising at least one selected from oxygen, nitrogen, phosphorus, sulfur, silicon, and boron,

When R ¹ to R ⁴ are not hydrogen, halogen, or a polar functional group, at least one combination of R ¹ and R ² , R ³ and R ⁴ is connected to each other to form an alkylidene group having 1 to 10 carbon atoms Or R ¹ or R ² may be bonded to any one of R ³ and R ⁴ to form a saturated or unsaturated aliphatic ring having 4 to 12 carbon atoms or an aromatic ring having 6 to 24 carbon atoms,

(2)

In Formula 2,

A is independently a simple bond, carbonyl, -COO-, -OCO-, oxygen, sulfur or -NH-,

B represents a single bond, a substituted or unsubstituted alkylene having 1 to 20 carbon atoms, carbonyl, -COO-, -OCO-, a substituted or unsubstituted arylene having 6 to 40 carbon atoms, and a substituted or unsubstituted carbon number 6 ≪ / RTI > to about 40 heteroarylen,

R ⁵ is a single bond, a substituted or unsubstituted alkylene having 1 to 20 carbon atoms, a substituted or unsubstituted alkenylene having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene having 3 to 12 carbon atoms, A substituted or unsubstituted arylene group having 6 to 40 carbon atoms, a substituted or unsubstituted aralkylene group having 7 to 15 carbon atoms, and a substituted or unsubstituted alkynylene group having 2 to 20 carbon atoms,

At least one of R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ is an alkyl having from 1 to 20 carbon atoms having an electron withdrawing group or an aryl having from 6 to 40 carbon atoms having an electron-

R ⁶ to R ¹⁰ , which are the same or different from each other, are each independently selected from the group consisting of hydrogen, halogen, substituted or unsubstituted C 1 -C 20 alkyl; A substituted or unsubstituted C1-C20 alkoxy; A substituted or unsubstituted aryloxy having 6 to 30 carbon atoms; A substituted or unsubstituted aryl having 6 to 40 carbon atoms, and a heteroaryl having 6 to 40 carbon atoms containing a heteroatom of group 14, group 15 or group 16.

In this cyclic olefin compound, the electron attracting group is preferably a group selected from the group consisting of -F, -Cl, -Br, -I, -C _n F _{2n +1} , -OC _n F _{2n +1} ), -CN, and -NO < ₂ >.

According to one embodiment, at least one of R ¹ , R ² , R ³ , and R ⁴ in Formula 1 may be a group represented by Formula 2; For example, at least one of R ¹ and R ² may be a group represented by the general formula (2).

These cyclic olefin compounds have at least one electron withdrawing group attached to the photoreactor. Such an electron attracting group induces a slope of the composition in the orientation film, thereby enabling to provide an orientation film having a more improved orientation. That is, when at least one electron attracting group is bonded to the photoreactor as shown in Formula 2, the electron density of the double bond is influenced thereby causing a difference in the photoreaction rate. For example, when a strong electron attracting group such as -F, -NO ₂ is introduced into a photoreactor, the electron density of the double bond of the photoreactor is reduced, which weakens the binding force of the pp orbitals of the π-bond and breaks quickly It becomes easier to make [2 + 2] coupling with the surrounding double bonds. Through such an operation, an alignment film having a more improved alignment property can be provided.

Further, since a bulky group such as an aralkyl structure is connected to the end of the photoreactive group in the cyclic olefin compound, a large free volume can be ensured between the photoreactive groups. This seems to be due to the steric hindrance of the bulk alkyl aralkyl structures.

Accordingly, in the photoreactive polymer and the alignment layer prepared from the cyclic olefin compound, the photoreactive groups having a structure similar to the cinnamate structure or the chalcone structure can relatively move (flow) or react And inhibition of other reactors or substituents therefrom is minimized. As a result, the photoreactive polymers and the photoreactors in the orientation film can exhibit better photoreactivity, orientation rate, photo-orientation, and the like. In particular, the photoreactor is optically oriented in such a way as to cause dimerization and isomerization at the same time by polarized light, which can occur more smoothly and smoothly without significant inhibition in the large free space. As a result, the photoreactive polymer and the alignment film produced from the cyclic olefin compound can exhibit better photoreactivity, orientation and orientation speed.

Further, in the above-mentioned photoreactive polymer and alignment film, since a large free space is ensured between the photoreactors, the photoreactors can change the alignment direction relatively freely according to the change of the polarization direction. As a result, it is possible to more smoothly change the alignment direction according to the polarization direction, and can be preferably applied to the patterned retarder and the patterned cell alignment film, which are applied for the realization of stereoscopic images and the like.

In recent years, attempts have been made to implement a wide viewing angle by replacing a TFT-cell alignment layer with a photo alignment layer and patterning the liquid crystal layer in accordance with the demand for a wide viewing angle. However, since the alignment direction of the existing alignment film is determined by the polarization direction, a process using two masks is required if a pattern in that direction is required. However, since the above-mentioned photoreactive polymer and the alignment layer containing the same can change the alignment direction once again by polarization in the other direction after the polarization is irradiated, a desired alignment layer can be realized by one mask process.

As a result, the cyclic olefin compound can provide a photoreactive polymer that exhibits excellent liquid crystal alignability and orientation rate, and is easy to change the alignment direction according to the polarization direction, so that it can be applied to various alignment films.

On the other hand, in the cyclic olefin compound, the polar functional group including at least one or more selected from the group consisting of polar functional groups that can be substituted for R ¹ to R ⁴ , that is, oxygen, nitrogen, phosphorus, sulfur, ≪ / RTI > and the like. However, it may be various polar functional groups including at least one selected from oxygen, nitrogen, phosphorus, sulfur, silicon or boron.

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In the polar functional group,

m is independently an integer of 1 to 10,

L ¹ is a substituted or unsubstituted, linear or branched alkylene having 1 to 20 carbon atoms; A substituted or unsubstituted linear or branched alkenylene having 2 to 20 carbon atoms; Substituted or unsubstituted C2-C20 linear or branched alkynylene; A substituted or unsubstituted cycloalkylene having 3 to 12 carbon atoms; Substituted or unsubstituted arylene having 6 to 40 carbon atoms; Substituted or unsubstituted carbonyloxysylene having 1 to 20 carbon atoms; Or a substituted or unsubstituted alkoxysilene having 1 to 20 carbon atoms,

L ² , L ³ and L ⁴ are each independently hydrogen; halogen; A substituted or unsubstituted C1 to C20 linear or branched alkyl; Substituted or unsubstituted C2-C20 linear or branched alkenyl; A substituted or unsubstituted linear or branched alkynyl having 2 to 20 carbon atoms; A substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Substituted or unsubstituted C6-C40 aryl; A substituted or unsubstituted C1-C20 alkoxy; And substituted or unsubstituted carbonyloxy of 1 to 20 carbon atoms.

Further, in the cyclic olefin compound, the substituted or unsubstituted aryl group having 6 to 40 carbon atoms; Or a heteroaryl group having 6 to 40 carbon atoms including a heteroatom of Group 14, Group 15 or Group 16 may be selected from the group consisting of the following functional groups and may be variously substituted with aryl or heteroaryl:

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In this functional group, E ¹ to E ⁹ are the same or different from each other and each independently represents hydrogen, substituted or unsubstituted linear or branched alkyl having 1 to 20 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, Or unsubstituted aryloxy having 6 to 30 carbon atoms, and substituted or unsubstituted aryl having 6 to 40 carbon atoms.

On the other hand, in the structure of the above-mentioned cyclic olefin compound, the definition of each substituent will be specifically described 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 is not only unsubstituted but can also be referred to as being further substituted by a certain substituent group described later. Examples of alkyl groups include methyl, ethyl, propyl, 2-propyl, n-butyl, iso-butyl, tert- butyl, pentyl, hexyl, 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 . The alkenyl group may be bonded through a carbon atom containing a carbon-carbon double bond or through a saturated carbon atom. The alkenyl group is not only unsubstituted, but may also be referred to as being further substituted by a certain substituent group described later. Examples of the alkenyl group include ethenyl, 1-propenyl, 2-propenyl, 2-butenyl, 3-butenyl, pentenyl, 5-hexenyl and dodecenyl.

"Cycloalkyl" means a saturated or unsaturated nonaromatic monovalent monocyclic, bicyclic or tricyclic hydrocarbon moiety of 3 to 12 ring carbons, inclusive of those further substituted by certain substituents described below, can do. Cyclopentyl, cyclopentyl, cyclohexyl, cyclohexenyl, cycloheptyl, cyclooctyl, decahydronaphthalenyl, adamantyl, norbonyl (i.e., bicyclo [ 1] hept-5-enyl).

"Aryl" means a monovalent monocyclic, bicyclic or tricyclic aromatic hydrocarbon moiety having 6 to 40, preferably 6 to 12, ring atoms, which is further substituted by a certain substituent group . Examples of the aryl group include phenyl, naphthalenyl and fluorenyl.

"Alkoxyaryl" means that at least one hydrogen atom of the above-defined aryl group is substituted with an alkoxy group. Examples of alkoxyaryl groups include methoxyphenyl, ethoxyphenyl, propoxyphenyl, butoxyphenyl, pentoxyphenyl, hexoxyphenyl, heptoxy, octoxy, noxy, methoxybiphenyl, methoxynaphthalenyl, Methoxyfluorenyl, methoxyanthracenyl and the like.

The term "aralkyl" means that at least one hydrogen atom of the above-defined alkyl group is substituted with an aryl group, and those further substituted by a certain substituent group described later may be collectively referred to. Examples thereof include benzyl, benzhydryl and trityl.

"Alkynyl" refers to a linear or branched monovalent hydrocarbon moiety of 2 to 20 carbon atoms, preferably 2 to 10, more preferably 2 to 6 carbon atoms, including one or more carbon-carbon triple bonds. do. Alkynyl groups may be bonded through a carbon atom comprising a carbon-carbon triple bond or through a saturated carbon atom. The alkynyl group may be further encompassed by a substituent which is further substituted by a certain substituent group described later. For example, ethynyl, propynyl and the like.

"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 may be referred to as being further substituted by a certain substituent group described later. Examples of the alkylene group include methylene, ethylene, propylene, butylene, hexylene and the like.

"Alkenylene" refers to a linear or branched divalent hydrocarbon moiety of from 2 to 20, preferably from 2 to 10, more preferably from 2 to 6 carbon atoms comprising at least one carbon-carbon double bond do. The alkenylene group may be bonded through a carbon atom containing a carbon-carbon double bond and / or through a saturated carbon atom. The alkenylene group may be referred to as being further substituted by a certain substituent group described later.

Means a saturated or unsaturated nonaromatic bivalent monocyclic, bicyclic, or tricyclic hydrocarbon moiety of 3 to 12 ring carbons, inclusive of which is further substituted by a given substituent group . Examples thereof include cyclopropylene and cyclobutylene.

"Arylene" means a divalent monocyclic, bicyclic or tricyclic aromatic hydrocarbon moiety having 6 to 20, preferably 6 to 12, ring atoms, which is further substituted by a constant substituent group It can be referred to collectively. The aromatic moiety contains only carbon atoms. Examples of the arylene group include phenylene and the like.

The term "aralkylene" means a divalent moiety in which at least one hydrogen atom of the alkyl group defined above is substituted with an aryl group, which may be further encompassed by a substituent which is further substituted by a certain substituent group described later. For example, benzylene and the like.

"Alkynylene" refers to a linear or branched divalent hydrocarbon moiety of from 2 to 20 carbon atoms, preferably from 2 to 10, more preferably from 2 to 6 carbon atoms comprising at least one carbon-carbon triple bond do. The alkynylene group may be bonded through a carbon atom containing a carbon-carbon triple bond or through a saturated carbon atom. The alkynylene group may be referred to collectively as being further substituted by a certain substituent group described later. For example, ethynylene or propynylene.

The substitution of the substituents described above with "substituted or unsubstituted" means that not only each of the substituents themselves but also those further substituted by a certain substituent are included. In the present specification, examples of substituents which can be further substituted for each substituent, unless otherwise defined, include halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, Is selected from the group consisting of oxygen, nitrogen, phosphorus, silicon, or boron, such as, for example, alkyl, alkenyl, "And the like.

The above-mentioned cyclic olefin compound can be produced according to a conventional method of introducing a predetermined substituent group into a cyclic olefin, for example, a norbornene-based compound, more specifically, a photoreactive group of the general formula (2). For example, the cyclic olefin compound can be produced by condensation reaction of a norbornene (alkyl) ole such as norbornene methanol with a carboxylic acid compound having a photoreactive group of the formula (2). In addition, the above-mentioned cyclic olefin compound can be prepared by introducing the photoreactive group by various methods depending on the structure and kind of the photoreactive unit of formula (2).

Photoreactive  polymer

On the other hand, according to another embodiment of the present invention, there is provided a photoreactive polymer comprising repeating units of the following structural formula (3a) or (3b)

[Formula 3]

In the above formulas (3a) and (3b), n is independently from 50 to 5,000, and p, R ¹ , R ² , R ³ and R ⁴ are as defined in the above formula (1).

The photoreactive polymer includes repeating units derived from the above-mentioned cyclic olefin compound. Particularly, the photoreactive polymer includes a photoreactive group in which at least one electron withdrawing group is bonded to a repeating unit of the photoreactive polymer, so that a slope of the composition can be induced in the alignment film, thereby providing an alignment film with improved orientation. It is possible.

In addition, the end of the photoreactive unit included in the photoreactive polymer has a bulky aralkyl structure, so that a large free space can be secured between the photoreactive groups. For this reason, in the photoreactive polymer, the photoreactors can move (flow) or react relatively freely in a largely ensured free space. Thus, the photoreactive polymer can exhibit better photoreactivity, orientation rate and photo-orientation. In addition, the photoreactive polymer can change the alignment direction of the light reactors relatively freely according to the change of the polarization direction. Therefore, the change of the alignment direction along the polarization direction can occur more smoothly, and can be preferably applied to the patterned retarder, the patterned cell alignment film, and the like.

The photoreactive polymer contains norbornene repeating units represented by the general formula (3a) or (3b) as a main repeating unit. Since the norbornene repeating unit is structurally hard and the photoreactive polymer containing it is relatively high at a glass transition temperature (Tg) of about 300 DEG C or higher, preferably about 300 to 350 DEG C, It can exhibit excellent thermal stability.

The definition of each substituent bonded to the above-mentioned photoreactive polymer is changed to the description of the cyclic olefin compound of formula (1).

The photoreactive polymer may include at least one repeating unit selected from the group consisting of the repeating units of the above-mentioned general formulas (3a) and (3b), but may also be a copolymer containing another kind of repeating units. Examples of such repeating units include, but are not limited to, a cinnamate-based, chalconic or azo-based photoreactive group (for example, a general photoreactive group in which a bulky aralkyl structure is not introduced at the terminal) Repeat unit; Acrylate repeating units; Or a cyclic olefin-based repeating unit. Examples of such repeating units are disclosed in Korean Patent Laid-Open Publication No. 2010-0021751.

However, the photoreactive polymer may be used in an amount of about 50 mol% or more, specifically about 50 to 100 mol%, and preferably about 70 mol%, for example, in order to prevent the various properties such as orientation and orientation rate according to Formula 3a or 3b from being impaired. % Or more of the repeating unit represented by the above formula (3a) or (3b).

The repeating unit of the formula (3a) or (3b) constituting the photoreactive polymer may have a degree of polymerization of about 50 to 5,000, preferably a degree of polymerization of about 100 to 4,000, more preferably a degree of polymerization of about 1,000 to 3,000. The photoreactive polymer may have a weight average molecular weight of 10,000 to 1,000,000, preferably 20,000 to 500,000. Accordingly, the above-mentioned photoreactive polymer can be appropriately included in a coating composition for forming an alignment film to exhibit excellent coating properties, and an alignment film formed therefrom can exhibit excellent liquid crystal alignability and the like.

The above-mentioned photoreactive polymer can exhibit photoreactivity under exposure to polarized light having a wavelength of about 150 to 450 nm, and can be used in a UV region having a wavelength of, for example, about 200 to 400 nm, more specifically, a wavelength of about 250 to 350 nm Can exhibit excellent light reactivity and orientation under exposure to polarized light.

Photoreactive  Method of producing polymer

According to another embodiment of the present invention, there is provided a process for producing the photoreactive polymer.

One embodiment of such a production method is a process for producing a cyclic olefin compound represented by the general formula (1) by addition polymerization of a cyclic olefin compound represented by the following formula (1) in the presence of a catalyst composition comprising a procatalyst containing a transition metal of Group 10 and a cocatalyst, The method comprising:

[Chemical Formula 1]

In Formula 1, p, R ¹ , R ² , R ³ , and R ⁴ are as defined in Formula 1.

At this time, the polymerization reaction may be carried out at a temperature of 10 ° C to 200 ° C. When the reaction temperature is lower than 10 ° C, the polymerization activity may be lowered, and when it is higher than 200 ° C, the catalyst may be decomposed.

The cocatalyst may further include a first cocatalyst to provide a Lewis base capable of weakly coordinating with the metal of the precatalyst; And a second co-catalyst to provide a compound comprising a Group 15 electron donor ligand. Preferably, the cocatalyst can be a catalyst mixture comprising a first co-catalyst providing the Lewis base and, optionally, a second co-catalyst comprising a neutral 15 group electron donor ligand.

At this time, the catalyst mixture may contain 1 to 1,000 moles of the first co-catalyst per 1 mole of the catalyst, and 1 to 1,000 moles of the second co-catalyst. If the content of the first catalyst or the second catalyst is excessively small, the catalyst may not be activated properly. On the contrary, if the content of the first catalyst or the second catalyst is excessively large, the catalyst activity may be lowered.

As the precatalyst including the Group 10 transition metal, it is easily separated by the first co-catalyst providing Lewis base and easily participates in the Lewis acid-base reaction so that the central transition metal can be converted into the catalytically active species. A compound having a Lewis base functional group which is released from the metal can be used. For example [(Allyl) Pd (Cl) ] 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, [PdCl (NB) O (CH 3)] there are _two and more.

In addition, as the first co-catalyst which provides a Lewis base capable of weakly coordinating with the metal of the precatalyst, it readily reacts with the Lewis base to form vacancies of the transition metal, and in order to stabilize the transition metal thus produced, A compound capable of weakly coordinating with the metal compound or a compound providing the same can be used. Borates such as borane or dimethylanilinium tetrakis (pentafluorophenyl) borate such as B (C ₆ F ₅ ) ₃ , methylaluminoxane (MAO) or Al (C ₂ H ₅₎ ) ₃ , or a transition metal halide such as AgSbF ₆ .

As the second cocatalyst for providing the compound containing the neutral 15 group electron donating ligand, alkylphosphine, cycloalkylphosphine or phenylphosphine may be used.

The first co-catalyst and the second co-catalyst may be used separately, but these two co-catalysts may be used as a compound for activating the catalyst by making one salt. For example, a compound prepared by ion-binding an alkylphosphine and a borane or a borate compound or the like may be used.

Through the above-described method, the photoreactive polymer of the repeating unit represented by the formula (3a) and an embodiment including the repeating unit represented by the formula (3a) can be produced. In addition, when the above-mentioned photoreactive polymer further contains an olefin-based repeating unit, a cyclic olefin-based repeating unit, or an acrylate-based repeating unit, these repeating units may be formed by the usual production method of each repeating unit, The photoreactive polymer may be copolymerized with the repeating unit of formula (3a).

On the other hand, the photoreactive polymer containing the repeating unit of the above formula (3b) may be prepared according to the preparation method and other embodiments. The production method of this other embodiment is characterized in that the cyclic olefin compound represented by the above formula (1) is subjected to a ring-opening polymerization reaction in the presence of a catalyst composition comprising a procatalyst containing a transition metal of Group 4, Group 6 or Group 8, To form a repeating unit of formula (3b).

As another selectable method, the photoreactive polymer comprising the repeating unit of the above formula (3b) can be produced by reacting, in the presence of a catalyst composition comprising a precatalyst comprising a transition metal of Group 4, Group 6 or Group 8 and a cocatalyst, (Alkyl) ol such as norbornene methanol as a monomer to form a ring-opening polymer having a pentane ring, and then introducing a photoreactive group into the ring-opening polymer. At this time, the introduction of the photoreactor can be carried out by a condensation reaction of the ring opening polymer with a carboxylic acid compound or an acyl chloride compound having a photoreactive group corresponding to formula (2).

In the ring-opening polymerization step, when hydrogen is added to the double bond in the norbornene ring contained in the monomer represented by the formula (1) or the like, the ring opening can proceed and, at the same time, the polymerization proceeds to form a repeating unit represented by the formula (3b) Polymers can be prepared. Or the polymerization and the ring opening may be progressed sequentially to produce the photoreactive polymer.

The ring-opening polymerization can be carried out in the presence of a catalyst 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) In the presence of a catalyst mixture comprising a cocatalyst providing a Lewis base capable of weakly coordinating with the catalyst and optionally a neutral Group 15 and Group 16 activator capable of promoting the activity of the precatalyst metal, . Also, in the presence of such a catalyst mixture, 1 to 100 mol% of a linear alkene such as 1-alkene or 2-alkene, which can control the molecular weight, is added in an amount of 1 to 100 mol% . A catalyst containing a transition metal of Group 4 (for example, Ti, Zr) or Group 8 to Group 10 (for example, Ru, Ni, Pd) is added to the monomer in an amount of 1 to 30 wt% The reaction of hydrogenating the double bond in the norbornene ring at the temperature can be carried out.

When the reaction temperature is too low, the polymerization activity is lowered. When the reaction temperature is too high, the catalyst is decomposed. In addition, when the hydrogenation reaction temperature is too low, the activity of the hydrogenation reaction is lowered, and when the hydrogenation reaction temperature is too high, the catalyst is decomposed.

The catalyst mixture may comprise one or more elements selected from the group consisting of Group 1 (e.g., Ti, Zr, Hf), Group 6 (e.g., Mo, W), or Group 8 1 to 100,000 moles of a cocatalyst providing a Lewis base capable of weakly coordinating with the metal of the catalyst and optionally an activator comprising neutral elements of group 15 and group 16 capable of promoting the activity of the catalytic metal and 1 to 100 moles of activator per mole of the catalyst.

When the content of the cocatalyst is less than 1 mol, there is a problem that the catalyst is not activated, and when it is more than 100,000 mol, the catalyst activity is lowered. The activating agent may not be required depending on the kind of the catalyst. When the content of the activating agent is less than 1 mol, there is a problem that the catalyst is not activated, while when it is more than 100 mol, the molecular weight is lowered.

When the content of the catalyst containing a transition metal of Group 4 (e.g., Ti, Zr) or Group 8 to Group 10 (e.g. Ru, Ni, Pd) used in the hydrogenation reaction is less than 1 wt% And when it is more than 30% by weight, there is a problem that the polymer is discolored, which is not preferable.

The procatalyst comprising the transition metal of Group 4 (e.g. Ti, Zr, Hf), Group 6 (e.g. Mo, W) or Group 8 (e.g. Ru, Os) Such as TiCl ₄ , WCl ₆ , MoCl ₅ , RuCl ₃ , and ZrCl ₄ , which are readily involved in the Lewis acid-base reaction and have functional groups that break away from the center metal, Metal compounds.

The cocatalyst providing the Lewis base capable of weakly coordinating with the metal of the precatalyst may be borane or borate such as B (C ₆ F ₅ ) ₃ , methylaluminoxane (MAO) or Al (C ₂ H ₅ ) ₃ , Al (CH ₃ ) Cl ₂ , alkylaluminum halides, and aluminum halides. Alternatively, substituents such as lithium, magnesium, germanium, lead, zinc, tin and silicon may be used instead of aluminum. As such, it is a compound which forms a transition metal easily by easily reacting with a Lewis base and weakly binds to a transition metal compound in order to stabilize the transition metal thus produced, or a compound providing the same.

An activator for polymerization may be added, but it may not be necessary depending on the kind of the catalyst. Activators comprising neutral elements of group 15 and group 16 that can enhance the activity of the precatalyst metal include water, methanol, ethanol, isopropyl alcohol, benzyl alcohol, ethyl mercaptan ), 2-chloroethanol, trimethylamine, triethylamine, pyridine, ethylene oxide, benzoyl peroxide, t-butyl peroxide and the like.

Catalysts comprising Group 4 (e.g., Ti, Zr) or transition metals of Group 8 to Group 10 (such as Ru, Ni, Pd) used in the hydrogenation reaction may be in a homogeneous form Or the metal catalyst complex is supported on a particulate support. The particulate support is preferably silica, titania, silica / chromia, silica / chromia / titania, silica / alumina, aluminum phosphate gel, silanized silica, silica hydrogel, montmorillonite clay or zeolite.

By the above-described method, the photoreactive polymer of the recurring unit of the formula (3b) and an embodiment including the repeating unit of the formula (3b) can be produced. When the above-mentioned photoreactive polymer further contains an olefin-based repeating unit, a cyclic olefin-based repeating unit, or an acrylate-based repeating unit, these repeating units may be formed by a usual production method of each repeating unit, To obtain a photoreactive polymer by copolymerization with the repeating unit of formula (3b).

Alignment film, liquid crystal Phase difference  Film and display elements

According to another embodiment of the present invention, there is provided an alignment film comprising the above-mentioned photoreactive polymer. Such an orientation film may include not only a thin film but also an orientation film in the form of a film.

According to another embodiment of the invention, there is provided a liquid crystal phase difference film comprising such an orientation film and a liquid crystal layer on the orientation film.

Such an orientation film and a liquid crystal retardation film can be produced using components and manufacturing methods known in the art, except that the above-mentioned photoreactive polymer is included as a photo alignment polymer.

For example, the alignment layer may be formed by mixing the photoreactive polymer, the binder resin, and the photoinitiator and dissolving the same in an organic solvent to obtain a coating composition, coating the coating composition on the substrate, and conducting UV curing.

As the binder resin, an acrylate resin may be used. Specific examples of the binder resin include pentaerythritol triacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, tris (2-acryloyloxy Ethyl) isocyanurate and the like can be used.

As the photoinitiator, a conventional photoinitiator known to be usable for an orientation film can be used without any limitations. For example, a photoinitiator known under the trade names Irgacure 907, 819 can be used.

Examples of the organic solvent include toluene, anisole, chlorobenzene, dichloroethane, cyclohexane, cyclopentane, propylene glycol methyl ether acetate, and the like. The above-mentioned photoreactive polymer exhibits excellent solubility for various organic solvents, so that various organic solvents can be used without limitation.

In the coating composition, the solid concentration of the photoreactive polymer, the binder resin, and the photoinitiator may be 1 to 15 wt%, and preferably 10 to 15 wt% in order to cast the alignment film into a film form. It is preferably 1 to 5% by weight.

The thus formed alignment film can be formed on the substrate, for example, as shown in Fig. 1, and can be formed below the liquid crystal to function to orient it. At this time, as the substrate, a substrate including an annular polymer, a substrate including an acrylic polymer, or a substrate including a cellulose polymer can be used. The coating composition may be coated on a substrate by various methods such as bar coating, spin coating, and blade coating, followed by UV curing to form an alignment layer.

The UV curing may cause a photo-conversion. In this step, the alignment treatment can be performed by irradiating the polarized UV in the wavelength range of about 150 to 450 nm. At this time, the intensity of the exposure may be an energy of about 50 mJ / cm 2 to 10 J / cm 2, preferably about 500 mJ / cm 2 to 5 J / cm 2.

Examples of the UV include: i) a polarizing device using a substrate coated with a dielectric anisotropic material on the surface of a transparent substrate such as quartz glass, soda lime glass, or soda lime free glass; ii) a polarizer plate on which aluminum or metal wires are finely deposited; iii) Polarized UV selected from the polarized UV can be applied by passing or reflecting through a Brewster polarizer or the like by reflection of quartz glass.

The substrate temperature at the time of irradiating the UV is preferably room temperature. However, in some cases, it is also possible to irradiate UV in a heated state within a temperature range of 100 DEG C or less. The film thickness of the final coating formed through the above-described series of steps is preferably 30 to 1000 nm.

A liquid crystal phase difference film can be produced according to a conventional method by forming an orientation film by the above-mentioned method, forming a liquid crystal layer thereon. Such an orientation film can exhibit excellent interaction with the liquid crystal molecules as the inclusion of the above-mentioned photoreactive polymer, thereby enabling effective optical alignment to proceed.

The above-mentioned alignment film or liquid crystal retardation film may be applied to an optical film or an optical filter for realizing a stereoscopic image.

For example, according to another embodiment of the invention, there is provided a display device comprising the alignment film. Such a display device may be a liquid crystal display device in which the alignment film is included for alignment of liquid crystal, or a stereoscopic image display device in which the alignment film is incorporated in an optical film or filter such as a liquid crystal retardation film for realizing a stereoscopic image. However, the constitution of these display elements is the same as that of a conventional device, except that it includes the above-mentioned photoreactive polymer and an alignment film, and thus a further detailed description thereof will be omitted.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are intended to illustrate the present invention without limiting it thereto.

[ Example  1 to 4: Synthesis of cyclic olefin compound]

According to the scheme shown in FIG. 2, cyclic olefin compounds were synthesized in the following manner.

Example  One

Compound 1-1 ((E) -4- (3- (4-fluorophenoxy) -3-oxoprop-1-en-1-yl) benzoic acid was dissolved in dichloromethane, and thionyl chloride was added dropwise . After the reaction solution was stirred at 80 ° C for 24 hours, the thionyl chloride of the reaction mixture was removed under reduced pressure to obtain the compound 2-1 ((E) -4-fluorophenyl 3- (4- (chlorocarbonyl) phenyl) acrylate .

Norbornene methanol and triethylamine were dissolved in dichloromethane, and the mixture was stirred for 30 minutes. Then, a solution prepared by dissolving compound 2-1 in dichloromethane was slowly added thereto, and the mixture was stirred at room temperature for 24 hours. Then, the residue was purified by column chromatography using a 4: 1 ethyl acetate / hexane mixture to obtain about 3.8 g of compound 3-1 ((1R, 2S, 4R) -bicyclo [2.2.1] hept-5-en- 4 - ((E) -3- (4-fluorophenoxy) -3-oxoprop-1-en-1-yl) benzoate.

Example  2

Except that Compound 1-2 ((E) -4-cyanophenyl 3- (4- (chlorocarbonyl) phenyl) acrylate was used in place of Compound 1-1, Compound 3-2 ((1R, 2S, 4R) -bicyclo [2.2.1] hept-5-ene-2-ylmethyl 4 - ((E) -3- (4-cyanophenoxy) -3-oxoprop- .

Example  3

Except that Compound 1-3 ((E) -4- (trifluoromethoxy) phenyl 3- (4- (chlorocarbonyl) phenyl) acrylate was used in place of Compound 1-1. (1R, 2S, 4R) -bicyclo [2.2.1] hept-5-en-2-ylmethyl 4 - ((E) -3-oxo-3- (4- (trifluoromethoxy) phenoxy) prop- 1-yl) benzoate.

Example  4

Except that the compound 1-4 ((E) -4- (trifluoromethyl) phenyl 3- (4- (chlorocarbonyl) phenyl) acrylate was used in place of the compound 1-1. (1R, 2S, 4R) -bicyclo [2.2.1] hept-5-en-2-ylmethyl 4 - ((E) -3-oxo-3- (4- (trifluoromethyl) phenoxy) prop- 1-yl) benzoate.

[ Example  5 to 8: Photoreactive  Preparation of polymer]

Using the compounds synthesized in Examples 1 to 4, a photoreactive polymer was prepared in the following manner.

Example  5

Compound 3-1 (5 g, 0.0127 mol) was dissolved in toluene (20 ml) and stirred for 30 minutes under a nitrogen atmosphere. The temperature was raised to 90 占 폚 and methylene (1 mol) solution of Pd (acetate) ₂ (0.00019 mg, 0.00033 mol) and tris (cyclohexyl) hydrogenphosphonotetrakis (pentafluorobenz) Chloride (1 ml) was added. This was stirred at 90 < 0 > C for 15 hours. After the reaction, the temperature was lowered to room temperature, precipitated using ethanol, filtered and then dried in a vacuum oven to obtain a polymer (yield = 57%, Mw = 72000, PDI = 3.09).

Example  6

A polymer was obtained in the same manner as in Example 5 (Yield = 50%, Mw = 65000, PDI = 2.8), except that Compound 3-2 (5 g, 0.0125 mol)

Example  7

A polymer was obtained in the same manner as in Example 5 (Yield = 41%, Mw = 58000, PDI = 2.2) except that Compound 3-3 (5 g, 0.0109 mol)

Example  8

A polymer was obtained in the same manner as in Example 5 (Yield = 49%, Mw = 63000, PDI = 2.6) except that Compound 3-4 (5 g, 0.0120 mol)

[ Manufacturing example : Preparation of orientation film]

Manufacturing example  One

A solution obtained by dissolving the photoreactive polymer according to Example 5 at a concentration of 2% by weight in cyclopentanone was dried on a base material (polyethylene terephthalate, manufacturer: SKC, product name: SH71) Å. This was dried in an oven at about 80 캜 for 3 minutes to obtain a coating film from which the solvent had been removed. Then, polarized UV was irradiated to the coating film for 5 seconds to obtain an alignment film. At this time, a wire-grid polarizer manufactured by Moxtek Co., Ltd., which uses a high-pressure mercury lamp of 200 mW / cm 2 intensity, was used for exposure, and polarized UV was emitted perpendicular to the film traveling direction.

Separately, a polymerizable reactive liquid crystal solution was prepared by adding toluene to a composition containing 95% by weight of a UV-polymerizable cyanobiphenyl acrylate and 5% by weight of Irgacure 907 (Ciba-Geigy) as a photoinitiator About 25 parts by weight liquid crystal content per weight part).

The prepared liquid crystal solution was coated on the alignment film by drying to a thickness of about 1 mu m after drying and then dried in an oven at about 80 DEG C for 2 minutes to align the liquid crystal molecules. A non-polarized UV using a high-pressure mercury lamp of 200 mW / cm 2 intensity as the light source was irradiated to the oriented liquid crystal film to fix the alignment state of the liquid crystal to obtain a retardation film.

Manufacturing example  2

A retardation film was obtained in the same manner as in Production Example 1, except that the photoreactive polymer according to Example 6 was used in place of the photoreactive polymer of Example 5.

Control Example

A retardation film was obtained in the same manner as in Production Example 1 except that a photo-alignment polymer (Mw 59,000 g / mol, PDI = 2.1) having no electron-attracting group bonded thereto was used in place of the photoreactive polymer of Example 5 .

[ Test Example ]

Each retardation film according to the production example and the control example was observed with a polarizing microscope between two vertically disposed polarizers to evaluate the orientation.

That is, the retardation film was inserted between two polarizers vertically arranged on the basis of a polyethylene terephthalate film (manufacturer: SKC, product name: SH71) having a thickness of 80 μm and the incident light passed through the polarizer and the retardation film to some extent And the degree of light leakage was measured by observing with a polarizing microscope. At this time, 5 out of 5 points were evaluated based on the degree of light leakage.

Then, the quantitative retardation value of the retardation film was measured using Axoscan (manufactured by Axomatrix). At this time, the retardation value in the film plane direction was measured using light of a wavelength of 550 nm.

Orientation Phase difference value Production Example 1 4 points 128 nm Production Example 2 4 points 123 nm Control Example 2 points 100 nm

Referring to Table 1, the retardation films according to Production Examples 1 and 2 exhibited excellent alignment properties because the alignment direction of the liquid crystal was uniform regardless of the wavelength of the incident light. In addition, it was confirmed that the retardation films of Production Examples 1 and 2 had 128 nm and 123 nm in-plane retardation values respectively, and the anisotropy due to liquid crystal was well realized.

On the other hand, it was confirmed that the retardation film of the control example was relatively low in orientation, shook the orientation direction of the liquid crystal, and had low phase retardation value despite the same liquid crystal thickness, so that the anisotropy was not well realized.

Claims (13)

CLAIMS What is claimed is: 1. A cyclic olefin compound having a photoreactive group represented by the following formula
[Chemical Formula 1]

In Formula 1,
p is an integer of 0 to 4,
One of R ¹ , R ² , R ³ , and R ⁴ is a group represented by the following formula (2)
R ¹ to R ⁴ are the same or different from each other and each independently represent hydrogen, halogen, linear or branched alkyl having 1 to 20 carbon atoms, linear or branched alkenyl having 2 to 20 carbon atoms , Linear or branched alkynyl having 2 to 20 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, or aryl having 6 to 40 carbon atoms,
(2)

In Formula 2,
A is independently a simple bond, carbonyl, -COO-, -OCO-, oxygen, sulfur or -NH-,
B is a simple bond, alkylene having 1 to 20 carbon atoms, carbonyl, -COO-, or -OCO-,
R ⁵ is a simple bond, an alkylene having 1 to 20 carbon atoms, or an alkenylene having 2 to 20 carbon atoms,
R ⁶ , R ⁷ , R ⁸ , and R ⁹ are each hydrogen,
R ¹⁰ is selected from -F, -Cl, -Br, -I, -C _n F _{2n + 1} , -OC _n F _{2n + 1} (wherein n is a natural number of 1 to 6), -CN, and -NO ₂ Alkyl having 1 to 20 carbon atoms with one or more electron withdrawing groups selected from the group consisting of aryl or aryl having 6 to 40 carbon atoms having said electron-attracting group.
delete delete delete delete A photoreactive polymer comprising recurring units of the following formula (3a) or (3b):
[Formula 3]

In the above formulas (3a) and (3b)
n is independently from 50 to 5,000,
p is independently an integer of 0 to 4,
One of R ¹ , R ² , R ³ , and R ⁴ is a group represented by the following formula (2)
R ¹ to R ⁴ are the same or different from each other and each independently represent hydrogen, halogen, linear or branched alkyl having 1 to 20 carbon atoms, linear or branched alkenyl having 2 to 20 carbon atoms , Linear or branched alkynyl having 2 to 20 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, or aryl having 6 to 40 carbon atoms,
(2)

In Formula 2,
A is independently a simple bond, carbonyl, -COO-, -OCO-, oxygen, sulfur or -NH-,
B is a simple bond, alkylene having 1 to 20 carbon atoms, carbonyl, -COO-, or -OCO-,
R ⁵ is a simple bond, an alkylene having 1 to 20 carbon atoms, or an alkenylene having 2 to 20 carbon atoms,
R ⁶ , R ⁷ , R ⁸ , and R ⁹ are each hydrogen,
R ¹⁰ is selected from -F, -Cl, -Br, -I, -C _n F _{2n + 1} , -OC _n F _{2n + 1} (wherein n is a natural number of 1 to 6), -CN, and -NO ₂ Alkyl having 1 to 20 carbon atoms with one or more electron withdrawing groups selected from the group consisting of aryl or aryl having 6 to 40 carbon atoms having said electron-attracting group.
delete The method according to claim 6,
A photoreactive polymer having a weight average molecular weight of 10,000 to 1,000,000.
A step of forming a repeating unit of the formula (3a) by addition polymerization of a cyclic olefin compound represented by the following formula (1) in the presence of a catalyst composition containing a transition metal containing a transition metal of Group 10 of the formula
A method for producing a photoreactive polymer according to claim 6, comprising:
[Chemical Formula 1]

In Formula 1, p, R ¹ , R ² , R ³ , and R ⁴ are as defined in Formula 3a.
A cyclic olefin compound represented by the following formula (1) is subjected to ring-opening polymerization in the presence of a catalyst composition comprising a promoter containing a transition metal of Group 4, Group 6, or Group 8 and a cocatalyst to form a repeating unit represented by Formula Step
A method for producing a photoreactive polymer according to claim 6, comprising:
[Chemical Formula 1]

In Formula 1, p, R ¹ , R ² , R ³ , and R ⁴ are as defined in Formula 3b.
An alignment film comprising the photoreactive polymer according to claim 6.
12. A liquid crystal phase difference film comprising the alignment film of claim 11 and a liquid crystal layer on the alignment film.
A display device comprising the alignment film of claim 11.

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