KR101735688B1 - 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 the like which enable to provide a photoreactive polymer having excellent solubility, while exhibiting excellent liquid crystal alignability and orientation rate and having a characteristic in which the direction of orientation along the polarization direction is easy to change And the like.

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. More specifically, the present invention relates to a cyclic olefin compound capable of providing a photoreactive polymer exhibiting excellent solubility while exhibiting excellent liquid crystal alignability and orientation rate and easily changing the orientation direction along the polarization direction, And an alignment film containing the same.

As liquid crystal displays have become larger in recent years, they are increasingly used for personal use such as mobile phones and notebooks, and for households such as wall-hanging TVs. Therefore, liquid crystal displays are required to have high image quality, high quality and wide viewing angle. 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.

In order to align such a liquid crystal, a rubbing process in which a polymer such as polyimide is applied on a transparent glass to form a polymer alignment layer, and a rotating roller wound with a rubbing cloth such as nylon, rayon, Has been applied.

However, in recent years, due to various problems of the rubbing process, a so-called "photo alignment" in which a predetermined polymer is oriented by irradiating light such as UV and aligning the liquid crystal is further studied and applied. In such a photo alignment, a photosensitive group bonded to a certain photoreactive polymer by linearly polarized UV causes a photoreaction, and in this process, the main chain of the polymer is aligned in a certain direction, and finally the liquid crystal is aligned, .

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 photo-alignment is performed, the double bond of cinnamate is reacted with [2 + 2] cycloaddition by the irradiated UV to form a cyclobutane, thereby forming an anisotropy And the liquid crystal molecules are aligned in one direction to induce alignment of the liquid crystal.

In addition, Japanese Patent Application Laid-Open No. 11-181127 discloses a polymer having a side chain including a photosensitive group such as a cinnamic acid group in the main chain of acrylate, methacrylate and the like, and an alignment 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. Further, the conventional photoreactive polymers are not so high solubility in an organic solvent, and there is a problem that a composition containing the same is applied and dried to make the process of forming an alignment layer poor.

In addition, there are application fields that require a change in anisotropic direction uniquely depending on the polarization direction, for example, patterned retarders and patterned cell alignment layers, which are applied for the realization of three-dimensional stereoscopic images, When the orientation direction is determined once by the polarized light, the reactive polymer is required to be polarized in the other direction having a stronger amount of light even if the direction does not move or moves.

The present invention is to provide a cyclic olefin compound which exhibits excellent liquid crystal alignability and orientation rate and is easy to change the alignment direction according to the polarization direction, and which can provide a photoreactive polymer having excellent solubility.

The present invention also provides a photoreactive polymer which exhibits excellent liquid crystal alignability and orientation rate and is easy to change the orientation direction according to the polarization direction, while exhibiting excellent solubility.

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

The present invention provides a cyclic olefin compound having a photoreactive group represented by the following general formula

 [Chemical Formula 1]

In Formula 1,

q is an integer of 0 to 4,

At least one of R 1, R 2, R 3, and R 4 is a radical selected from the group consisting of:

R1 to R4 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,

Wherein R1 to R4 are independently selected from the group consisting of hydrogen; halogen; Or a combination of at least one member selected from the group consisting 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 is any one of R 3 and R 4 A saturated or unsaturated aliphatic ring having 4 to 12 carbon atoms or an aromatic ring having 6 to 24 carbon atoms,

[Chemical Formula 1a] [Chemical Formula 1b]

In the above general formulas (1a) and (1b)

A is a simple bond, oxygen, sulfur or -NH-,

B is a single bond, a substituted or unsubstituted alkylene having 1 to 20 carbon atoms, a carbonyl, a carboxy, an ester, a substituted or unsubstituted arylene having 6 to 40 carbon atoms, and a substituted or unsubstituted hetero ring having 6 to 40 carbon atoms Arylene, < / RTI >

X is oxygen or sulfur;

R9 represents a simple 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 having 6 to 40 carbon atoms, substituted or unsubstituted aralkylene having 7 to 15 carbon atoms, and substituted or unsubstituted alkynylene having 2 to 20 carbon atoms,

At least one of R10 to R14 is a radical represented by -L-R15-R16- (substituted or unsubstituted cycloalkyl or heterocycloalkyl having 3 to 20 carbon atoms), and other R10 to R14 are the same or different from each other , Each independently selected from the group consisting of hydrogen, halogen, substituted or unsubstituted C1-C20 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,

L is selected from the group consisting of oxygen, sulfur, -NH-, substituted or unsubstituted alkylene having 1 to 20 carbon atoms, carbonyl, carboxy, -CONH- and substituted or unsubstituted arylene having 6 to 40 carbon atoms ,

R15 is a simple bonded, substituted or unsubstituted alkylene having 1 to 10 carbon atoms,

R16 is selected from the group consisting of a simple bond, -O-, -C (= O) O-, -OC (= O) -, -NH-, -S- and -C (= O) -.

The present invention also provides a photoreactive polymer comprising repeating units of formula (3a) or (3b): < EMI ID =

[Formula 3]

Each independently of the above-mentioned formulas (3a) and (3b)

q is an integer of 0 to 4,

m is from 50 to 5000,

At least one of R 1, R 2, R 3, and R 4 is a radical selected from the group consisting of:

R1 to R4 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,

Wherein R1 to R4 are independently selected from the group consisting of hydrogen; halogen; Or a combination of at least one member selected from the group consisting 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 is any one of R 3 and R 4 A saturated or unsaturated aliphatic ring having 4 to 12 carbon atoms or an aromatic ring having 6 to 24 carbon atoms,

[Chemical Formula 1a] [Chemical Formula 1b]

In the above general formulas (1a) and (1b)

A is a simple bond, oxygen, sulfur or -NH-,

B is a single bond, a substituted or unsubstituted alkylene having 1 to 20 carbon atoms, a carbonyl, a carboxy, an ester, a substituted or unsubstituted arylene having 6 to 40 carbon atoms, and a substituted or unsubstituted hetero ring having 6 to 40 carbon atoms Arylene, < / RTI >

X is oxygen or sulfur;

R9 represents a simple 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 having 6 to 40 carbon atoms, substituted or unsubstituted aralkylene having 7 to 15 carbon atoms, and substituted or unsubstituted alkynylene having 2 to 20 carbon atoms,

At least one of R10 to R14 is a radical represented by -L-R15-R16- (substituted or unsubstituted cycloalkyl or heterocycloalkyl having 3 to 20 carbon atoms), and other R10 to R14 are the same or different from each other , Each independently selected from the group consisting of hydrogen, halogen, substituted or unsubstituted C1-C20 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,

L is selected from the group consisting of oxygen, sulfur, -NH-, substituted or unsubstituted alkylene having 1 to 20 carbon atoms, carbonyl, carboxy, -CONH- and substituted or unsubstituted arylene having 6 to 40 carbon atoms ,

R15 is a simple bonded, substituted or unsubstituted alkylene having 1 to 10 carbon atoms,

R16 is selected from the group consisting of a simple bond, -O-, -C (= O) O-, -OC (= O) -, -NH-, -S- and -C (= O) -.

The present invention also provides an alignment film comprising the photoreactive polymer.

Further, the present invention provides a liquid crystal phase difference film comprising the above alignment film and a liquid crystal layer on an alignment film.

The present invention also provides a display device comprising the alignment film.

The photoreactive polymer obtained from the cyclic olefin compound of the present invention is bound to a bulky substituent containing a cycloalkyl or heterocycloalkyl at the end of the photoreactive group. Due to the influence of such bulky substituents, the above-mentioned photoreactive polymer has far superior liquid crystal alignment properties and orientation rates to conventional photoreactive polymers.

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.

In addition, the photoreactive polymer can exhibit good solubility in organic solvents due to the presence of the cycloalkyl or heterocycloalkyl-containing substituents. By using the composition containing the photoreactive polymer, a process of forming a good alignment film can be made easier.

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

Fig. 1 schematically shows an example of a typical alignment film structure.
2 is a graph showing the relationship between the orientation film (45 DEG) in which the primary orientation has been advanced and the orientation film (135 DEG) in which the secondary orientation has proceeded after 90 DEG rotation using the photoreactive polymer of Example 19 in Experimental Example 1 Image.

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.

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,

q is an integer of 0 to 4,

At least one of R 1, R 2, R 3, and R 4 is a radical selected from the group consisting of:

R1 to R4 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,

Wherein R1 to R4 are independently selected from the group consisting of hydrogen; halogen; Or a combination of at least one member selected from the group consisting 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 is any one of R 3 and R 4 A saturated or unsaturated aliphatic ring having 4 to 12 carbon atoms or an aromatic ring having 6 to 24 carbon atoms,

[Chemical Formula 1a] [Chemical Formula 1b]

In the above general formulas (1a) and (1b)

A is a simple bond, oxygen, sulfur or -NH-,

B is a single bond, a substituted or unsubstituted alkylene having 1 to 20 carbon atoms, a carbonyl, a carboxy, an ester, a substituted or unsubstituted arylene having 6 to 40 carbon atoms, and a substituted or unsubstituted hetero ring having 6 to 40 carbon atoms Arylene, < / RTI >

X is oxygen or sulfur;

R9 represents a simple 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 having 6 to 40 carbon atoms, substituted or unsubstituted aralkylene having 7 to 15 carbon atoms, and substituted or unsubstituted alkynylene having 2 to 20 carbon atoms,

At least one of R10 to R14 is a radical represented by -L-R15-R16- (substituted or unsubstituted cycloalkyl or heterocycloalkyl having 3 to 20 carbon atoms), and other R10 to R14 are the same or different from each other , Each independently selected from the group consisting of hydrogen, halogen, substituted or unsubstituted C1-C20 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,

L is selected from the group consisting of oxygen, sulfur, -NH-, substituted or unsubstituted alkylene having 1 to 20 carbon atoms, carbonyl, carboxy, -CONH- and substituted or unsubstituted arylene having 6 to 40 carbon atoms ,

R15 is a simple bonded, substituted or unsubstituted alkylene having 1 to 10 carbon atoms,

R16 is selected from the group consisting of a simple bond, -O-, -C (= O) O-, -OC (= O) -, -NH-, -S- and -C (= O) -.

In this cyclic olefin compound, the radical of -L-R15-R16- (substituted or unsubstituted cycloalkyl or heterocycloalkyl having 3 to 20 carbon atoms) is the linker L is oxygen, and the cycloalkyl or heterocyclo Alkyl and may be a radical represented by the following general formula (2), or a radical having various linkers L and the like:

(2)

Wherein R15 and R16 are as defined in Formula (1)

The ring C is a cycloalkyl having 5 to 20 carbon atoms or a heteroaryl cycloalkyl having 3 to 20 carbon atoms in which at least one hetero atom of oxygen, nitrogen or sulfur is contained in the ring,

R17 to R21 are the same as or different from each other, and each independently hydrogen; halogen; A substituted or unsubstituted alkyl of 1 to 20 carbon atoms; A substituted or unsubstituted C1-C20 alkoxy; A substituted or unsubstituted aryloxy having 6 to 30 carbon atoms; Substituted or unsubstituted C6-C40 aryl; A heteroaryl having 6 to 40 carbon atoms containing a heteroatom of Group 14, Group 15 or Group 16, and a substituted or unsubstituted alkoxyaryl having 6 to 40 carbon atoms.

More specifically, in this radical of formula (2), ring C may be cyclohexyl, cyclopentyl, adamantanyl or tetrahydropyranyl and the like, as well as various cycloalkyl or heterocycloalkyl .

Such a cyclic olefin compound is bound to a substituent represented by -L-R15-R16- (substituted or unsubstituted cycloalkyl or heterocycloalkyl having 3 to 20 carbon atoms) at the end of a photoreactive unit such as a cinnamate structure. Such a substituent includes a structure in which an alkylene and an aliphatic ring (cycloalkyl or heterocycloalkyl) are connected in series via a linker L. As such a bulky chemical structure is linked to the end of the photoreactor via linker L, a large free volume can be ensured between the photoreactors. This seems to be due to the steric hindrance of the bulk structures.

Therefore, in the photoreactive polymer and the orientation film produced from the cyclic olefin compound, the photoreactive groups such as the cinnamate structure can relatively move (flow) or react in the free space in which the large amount is secured, Or substituents are 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, a photoreactive group, such as a cinnamate structure, is optically oriented in such a way that dimerization and isomerization are simultaneously caused by polarization, 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.

In addition, as a result of experiments conducted by the present inventors, it has been found that as the structure containing the cycloalkyl or heterocycloalkyl is bonded to the end of the photoreactive group, the cyclic olefin compound and the photoreactive polymer formed therefrom have a higher solubility Of the total population. Accordingly, in the process of forming the alignment layer using the photoreactive polymer, the alignment layer can be more easily manufactured by forming the photoreactive polymer composition well and applying and drying the photoreactive polymer even if the amount of the organic solvent is reduced. In addition, in this process, coating and drying can be more easily performed, and the processability for forming an alignment film can be greatly improved.

As a result, the cyclic olefin compound enables the provision of 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 and exhibits excellent solubility and processability.

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

The polar functional group comprising at least one or more selected from the group consisting of oxygen, nitrogen, phosphorus, sulfur, silicon, and boron, which may be substituted in the above-mentioned cyclic olefin compound, may include the following functional groups And may be various polar functional groups including at least one selected from oxygen, nitrogen, phosphorus, sulfur, silicon or boron.

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_{-OR 6, -OC (O) OR} 6, -R 5 OC (O) OR 6, -C (O) OR 6, -R 5 C (O) OR 6, -C (O) R 6, -R _{5 C (O) R 6,} -OC (O) R 6, -R 5 OC (O) R 6, - (R 5 O) p -OR 6, - (OR 5) p -OR 6, -C ( _{O) -OC (O) R 6} , -R 5 C (O) -OC (O) R 6, -SR 6, -R 5 SR 6, -SSR 6, -R 5 SSR 6, -S (= O _{) R 6, -R 5 S (} = O) R 6, -R 5 C (= S) R 6 -, -R 5 C (= S) SR 6, -R 5 SO 3 R 6, -SO 3 R _{6, -R 5 N = C =} S, -N = C = S, -NCO, -R 5 -NCO, -CN, -R 5 CN, -NNC (= S) R 6, -R 5 NNC (= S) R ₆ , -NO ₂ , -R ₅ NO ₂ ,

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, And

In this polar functional group, p is independently an integer of 1 to 10, and R5 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; Linear or branched alkynylene having 2 to 20 carbon atoms which is unsubstituted; 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 substituted or unsubstituted alkoxysilene having 1 to 20 carbon atoms; R6, R7 and R8 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.

In the cyclic olefin compound, the substituted or unsubstituted aryl of 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:

In these functional groups, R'10 to R'18 may be the same or different from each other, and the remainder each independently represents a substituted or unsubstituted C1 to C20 linear or branched alkyl, substituted or unsubstituted C1 to C20 Substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, and substituted or unsubstituted aryl having 6 to 40 carbon atoms.

In the cyclic olefin compound, at least one of R 1 to R 4 in the formula (1) is a photoreactive group of formula (Ia) or (Ib), for example, at least one of R 1 and R 2 may be the photoreactive group. It becomes possible to provide a photoreactive polymer exhibiting excellent orientation properties and the like by using such a cyclic olefin compound.

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 20 ring hydrocarbons, including those further substituted by certain substituents described below, can do. Cyclobutyl, cyclopentyl, cyclohexyl, cyclohexyl, cycloheptyl, cyclooctyl, decahydronaphthalenyl, adamantanyl, norbonyl (i.e., bicyclo [ 1] hept-5-enyl).

"Heterocycloalkyl" refers to a monocyclic ring in which the hydrocarbon ring of the "cycloalkyl" contains one or more heteroatoms, such as nitrogen, oxygen, or sulfur, , Bicyclic or tricyclic region. Such heterocycloalkyl can be further substituted by a substituent described below.

"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 formula (1a) or (1b). For example, the cyclic olefin compound can be prepared by reacting a norbornene (alkyl) ole such as norbornene or norbornene methanol with a carboxylic acid compound or an acyl chloride compound having a photoreactive group of formula (I) or (Ib) 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 (1a) or (1b).

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

[Formula 3]

Independently of one another, m is from 50 to 5000 and q, R1, R2, R3 and R4 are as defined for formula (I).

Such a photoreactive polymer includes repeating units derived from the above-mentioned cyclic olefin compound. Due to the structure of the bulky cycloalkyl or heterocycloalkyl bonded through the linker L to the end of the photoreactive group, A large free space can be secured. 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.

In addition, since the photoreactive polymer exhibits excellent solubility in an organic solvent, the photoreactive polymer can exhibit better processability such as coating and drying in the step of forming an orientation film, and the use amount of the organic solvent can be reduced.

The photoreactive polymer contains a norbornene repeating unit 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 photoreactive polymer has already been described in detail with respect to the cyclic olefin compound of the formula (1), and a further explanation thereof will be omitted.

The photoreactive polymer may include at least one repeating unit selected from the group consisting of the repeating units represented by the general formula (3a) or (3b), but may also be a copolymer including another repeating unit. Examples of such repeating units include, but are not limited to, cinnamate-based, chalconic or azo-based photoreactive groups (for example, general photoreactive groups in which a bulky aralkyl structure is not terminally introduced) Unit, an acrylate-based repeating unit, or a cyclic olefin-based repeating unit. Examples of such repeating units are disclosed in JP-A-2010-0021751 and the like.

However, the photoreactive polymer may be used in an amount of about 50 mol% or more, specifically about 50 to 100 mol%, preferably about 70 mol% or more, so as not to impair various properties such as good orientation and orientation rate according to Formula 3a or 3b. Or more of the repeating unit represented by the above formula (3a) or (3b).

Further, 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 1000 to 3,000. The photoreactive polymer may have a weight average molecular weight of about 10000 to 1000000, or about 20000 to 500000, or about 80000 to 300000. Accordingly, the above-mentioned photoreactive polymer can be suitably included in the coating composition for forming an alignment film to exhibit excellent coating properties, and the alignment film formed therefrom can exhibit excellent orientation 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.

On the other hand, the above-mentioned photoreactive polymer can be produced according to the method described below. One embodiment of the method of the present invention comprises a step of addition polymerization of a monomer of formula (1) to form a repeating unit of formula (3a) in the presence of a catalyst composition comprising a cocatalyst and a precatalyst comprising a Group 10 transition metal Includes:

[Chemical Formula 1]

In Formula 1, q, R1, R2, R3, and R4 are as defined in Formula 3a.

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 1000 moles of the first co-catalyst per 1 mole of the catalyst, and may contain 1 to 1000 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 repeating unit represented by the formula (3a) and the photoreactive polymer of one embodiment containing the same can be prepared. 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, when the photoreactive polymer comprises the repeating unit of the formula (3b), it can be produced according to another embodiment of the above production method. The production method of this other embodiment is a method of ring-opening polymerization of the monomer of the above formula (1) in the presence of a catalyst composition comprising a procatalyst containing a transition metal of Group 4, Group 6 or Group 8 and a cocatalyst, . 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) ole such as norbornene or 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 photoreactive unit 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 (Ia) or (Ib).

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 to the monomer and polymerization is carried out at a temperature of 10 to 200 ° C. And a catalyst comprising a transition metal of Group 4 (e.g., Ti, Zr) or Group 8 to Group 10 (e.g. Ru, Ni, Pd) is added to the monomer in an amount of 1 to 30 wt% Lt; RTI ID = 0.0 > C, < / RTI > the double bond in the norbornene ring can be hydrogenated.

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) so that the off center by easily be replaced with a transition metal catalyst active species, a Lewis acid _{- TiCl 4, WCl 6, MoCl} 5 , which join the base to easily react with the functional groups falling off from the metal center Or a transition metal compound such as RuCl ₃ or ZrCl ₄ .

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 repeating unit of the formula (3b) and the photoreactive polymer of one embodiment including the repeating unit of the formula (3b) can be prepared. 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).

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 an 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, and the photoinitiator, dissolving the mixture in an organic solvent to obtain a coating composition, coating the coating composition on the substrate, drying, and UV curing. At this time, since the photoreactive polymer exhibits excellent solubility with respect to an organic solvent, the process of forming the alignment layer can be more easily performed, and the amount of the organic solvent used can be further reduced.

As the binder, a (meth) acrylate-based compound can be used. More specifically, it is possible to use a binder such as pentaerythritol triacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, or tris 2-ethylhexyloxy) isocyanurate, and the like.

As the photoinitiator, a typical photoinitiator known to be usable for an alignment film can be used without any limitation. 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. Since the above-mentioned photoreactive polymer exhibits excellent solubility for various organic solvents, various organic solvents can be used without limitation.

In the coating composition, the solid concentration including the photoreactive polymer, the binder and the photoinitiator may be 1 to 15% by weight, and preferably 10 to 15% by weight for casting the alignment film into a film, But 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. The substrate may be a substrate comprising a cyclic polymer, a substrate comprising an acrylic polymer, or a substrate comprising a cellulose polymer. The coating composition may be applied by various methods such as bar coating, spin coating and blade coating It may be coated on a substrate and UV-cured to form an alignment film.

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: (1) 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, soda lime free glass, etc., (2) a polarizer on which fine aluminum or metal wires are deposited, The polarized UV selected from the polarized UV can be applied in such a way as to pass through or reflect the Brewster polarizer or the like due to the reflection of the 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.

According to another embodiment of the present invention, there is provided a display device including the alignment layer. 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.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. However, the following embodiments are intended to illustrate the invention, but the invention is not limited thereto.

Example 1: Preparation of 4- (cyclohexylmethoxy) -cinnamate-5-norbornene (Preparation of cyclic olefin compound)

4-hydroxy-benzaldehyde (10 g, 82 mmol), (boromomethyl) cyclohexane (1.1 eq) and K ₂ CO ₃ (1 eq) were dissolved in DMF (5 eq) and stirred for 12 hours. After removal of the solvent, 4- (cyclohexylmethoxy) -benzaldehyde was obtained.

4- (cyclohexylmethoxy) -benzaldehyde (10 g, 46 mmol), malonic acid (2 eq) and piperidine (0.1 eq) were dissolved in pyridine (5 eq) and stirred at 80 ° C for 5 hours. After the reaction, the temperature was lowered to room temperature and neutralized with 3M HCl. The resulting white solid was obtained by filtration. This solid was dried in a vacuum oven to give 4- (cyclohexylmethoxy) -cinnamic acid.

The cyclohexylmethoxy-cinnamic acid (5g, 19mmol), norbornene-5-ol (19mmol) and Zr (AcAc) (0.2mol%) were added to xylene and stirred at 190 ° C for 24 hours. After stirring, the reaction mixture was washed with 1 M HCl, 1 M NaHCO3 aqueous solution, and the solvent was removed to obtain solid 4- (cyclohexylmethoxy) -cinnamate-5-norbornene.

_{NMR (CDCl 3 (500MHz),} ppm): 1.27 ~ 1.52 (4, m) 1.43 ~ 1.53 (4, m) 1.47 ~ 1.49 (2, m) 1.50 ~ 1.75 (2, m) 1.63 ~ 1.88 (2, m ) 2.27 (1, m) 2.86 (1, m) 3.90 (2, d) 4.01 (1, q) 6.05 (2, d)

Example 2: Preparation of 4- (cyclohexylmethoxy) -cinnamate-5-methyl norbornene (Preparation of cyclic olefin compound)

4- (cyclohexylmethoxy) cinnamate-5-methyl norbornene was prepared by proceeding in the same manner and under the same conditions except that norbornene-5-methanol was used instead of norbornene-5-ol in Example 1.

_{NMR (CDCl 3 (500MHz),} ppm): 1.27 ~ 1.60 (13, m) 1.75 (1, m) 1.94 (1, m) 2.13 (1, m) 2.27 (1, m) 2.58 (1, m) 3.90 (2, d) 4.25 (1, dd) 4.50 (1, dd) 6.05 (2, dd) 6.31

Example 3: Preparation of 4- (cyclohexylmethoxy) -cinnamate-5-ethyl norbornene (Preparation of cyclic olefin compound)

4- (cyclohexylmethoxy) -cinnamate-5-ethyl norbornene was prepared by proceeding in the same manner and under the same conditions except that norbornene-5-ethanol was used instead of norbornene-5-ol in Example 1.

NMR (CDCl ₃ (500 MHz) _, ppm): 1.27-1.60 (16, m) 1.75 (1, m) 1.94 (1, m) 2.27 (2, t) 6.05 (2, dd) 6.31 (1, d) 6.94 (2,

Example 4: Preparation of 4-cyclohexyloxy-cinnamate-5-norbornene (Preparation of cyclic olefin compound)

4-cyclohexyloxy-cinnamate-5-norbornene was prepared by proceeding in the same manner and under the same conditions except that 4-cyclohexyloxy-benzaldehyde was used instead of 4- (cyclohexyloxymethoxy) -benzaldehyde in Example 1.

NMR (CDCl ₃ (500 MHz) _, ppm): 1.43-1.95 (14, m) 2.27 (1, m) 2.86 (1, m) 3.64 (1, d) 6.94 (2, d) 7.48 (1, d) 7.62 (2,

Example 5: Preparation of 4-cyclohexyloxy-cinnamate-5-methyl norbornene (Preparation of cyclic olefin compound)

4-cyclohexyloxy-cinnamate-5-methyl norbornene was prepared by proceeding in the same manner and under the same conditions except that norbornene-5-methanol was used instead of norbornene-5-ol in Example 4.

NMR (CDCl ₃ (500 MHz) _, ppm): 1.43-1.75 (12, m) 1.95 (2, m) 2.13 (1, m) 2.27 (1, m) 4.50 (1, m) 6.05 (2, dd) 6.31 (1, d) 6.94 (2,

Example 6: Preparation of 4-cyclohexyloxy-cinnamate-5-ethyl norbornene (Preparation of cyclic olefin compound)

4-cyclohexyloxy-cinnamate-5-ethyl norbornene was prepared by proceeding in the same manner and under the same conditions except that norbornene-5-ethanol was used instead of norbornene-5-ol in Example 4.

_{NMR (CDCl 3 (500MHz),} ppm): 1.43 ~ 1.75 (15, m) 1.95 (2, m) 2.27 (1, m) 2.58 (1, m) 3.64 (1, m) 4.15 (2, t) 6.05 (2, d) 6.31 (1, d) 6.94 (2, d) 7.48 (1,

Example 7: Preparation of 4- (cyclopentylmethoxy) -cinnamate-5-norbornene (Preparation of cyclic olefin compound)

4- (cyclopentylmethoxy) -cinnamate-5-norbornene was prepared by proceeding in the same manner and under the same conditions except that 4- (cyclopentylmethoxy) -benzaldehyde was used instead of 4- (cyclohexylmethoxy) -benzaldehyde in Example 1 .

_{NMR (CDCl 3 (500MHz),} ppm): 1.35 ~ 1.88 (12, m) 2.27 (1, m) 2.86 (1, m) 3.90 (2, d) 4.01 (1, q) 6.05 (2, dd) 6.31 (1, d) 6.94 (2, d) 7.48 (1, d) 7.62 (2,

Example 8: Preparation of 4- (cyclopentylmethoxy) -cinnamate-5-methyl norbornene (Preparation of cyclic olefin compound)

4- (cyclopentylmethoxy) -cinnamate-5-methyl norbornene was prepared by proceeding in the same manner and under the same conditions except that norbornene-5-methanol was used instead of norbornene-5-ol in Example 7.

_{NMR (CDCl 3 (500MHz),} ppm): 1.35 ~ 1.75 (12, m) 2.01 (1.m) 2.13 (1, m) 2.27 (1, m) 2.58 (1, m) 3.90 (2, d) 4.25 (1, dd) 4.50 (1, dd) 6.05 (2, dd) 6.31 (1, d) 6.94 (2,

Example 9: Preparation of 4- (cyclopentylmethoxy) -cinnamate-5-ethyl norbornene (Preparation of cyclic olefin compound)

4- (cyclopentylmethoxy) -cinnamate-5-ethyl norbornene was prepared by proceeding in the same manner and under the same conditions except that norbornene-5-ethanol was used instead of norbornene-5-ol in Example 7.

_{NMR (CDCl 3 (500MHz),} ppm): 1.35 ~ 1.60 (13, m) 1.75 (1, m) 2.01 (1, m) 2.27 (1, m) 2.58 (1, m) 3.90 (2, d) 4.15 (2, d) 6.05 (2, dd) 6.31 (1, d) 6.94 (2,

Example 10: Preparation of 4-cyclopentyloxy-cinnamate-5-norbornene (Preparation of cyclic olefin compound)

4-cyclopentyloxy-cinnamate-5-norbornene was prepared by proceeding in the same manner and under the same conditions except that 4-cyclopentyloxy-benzaldehyde was used instead of 4- (cyclohexylmethoxy) -benzaldehyde in Example 1.

NMR (CDCl ₃ (500 MHz) _, ppm): 1.50-2.01 (12, m) 2.27 (1, m) 2.86 (1, m) 3.71 (1, d) 6.94 (2, d) 7.48 (1, d) 7.62 (2,

Example 11: Preparation of 4-cyclopentyloxy-cinnamate-5-methyl norbornene (Preparation of cyclic olefin compound)

4-cyclopentyloxy-cinnamate-5-methyl norbornene was prepared by following the same procedure and under the same conditions as in Example 10 except that norbornene-5-methanol was used instead of norbornene-5-ol.

NMR (CDCl ₃ (500 MHz) _, ppm): 1.35-1.75 (8, m) 1.76-2.27 (6, m) 2.58 (1, ) 6.31 (1, d) 6.94 (2, d) 7.48 (1, d) 7.62 (2,

Example 12: Preparation of 4-cyclopentyloxy-cinnamate-5-ethyl norbornene (Preparation of cyclic olefin compound)

4-cyclopentyloxy-cinnamate-5-ethyl norbornene was prepared by proceeding in the same manner and under the same conditions except that norbornene-5-ethanol was used instead of norbornene-5-ol in Example 10.

_{NMR (CDCl 3 (500MHz),} ppm): 1.35 ~ 1.75 (11, m) 1.50 (1, m) 1.75 (1, m) 2.27 (1, m) 2.58 (1, m) 3.71 (1, m) 4.15 (2, m) 6.05 (2, dd) 6.31 (1, d) 6.94 (2,

Example 13: Preparation of 4- (1-adamantanyloxy) -cinnamate-5-norbornene (Preparation of cyclic olefin compound)

The reaction was carried out in the same manner as in Example 1 except that 4- (1-adamantanyloxy) -benzaldehyde was used instead of 4- (cyclohexylmethoxy) -benzaldehyde to obtain 4- (1-adamantanyloxy) -cinnamate-5- norbornene was prepared.

NMR (CDCl ₃ (500 MHz) _, ppm): 1.50-1.88 (10, m) 2.02 (6, m) 2.14 (6, d) 2.27 (2, d) 6.31 (1, d) 6.94 (2, d) 7.48 (1,

Example 14: Preparation of 4- (1-adamantanyloxy) -cinnamate-5-methyl norbornene (Preparation of cyclic olefin compound)

4- (1-adamantanyloxy) -cinnamate-5-methyl norbornene was prepared by proceeding in the same manner and under the same conditions except that norbornene-5-methanol was used instead of norbornene-5-ol in Example 13.

_{NMR (CDCl 3 (500MHz),} ppm): 1.35 ~ 1.75 (13, m) 2.02 ~ 2.14 (13, m) 2.27 (1, m) 2.58 (1, m) 4.25 (1, dd) 6.05 (2, dd ) 6.31 (1, d) 6.94 (2, d) 7.48 (1, d) 7.62 (2,

Example 15: Preparation of 4- (1-adamantanyloxy) -cinnamate-5-ethyl norbornene (Preparation of cyclic olefin compound)

4- (1-adamantanyloxy) -cinnamate-5-ethyl norbornene was prepared by proceeding in the same manner as in Example 13 except that norbornene-5-ethanol was used instead of norbornene-5-ol.

_{NMR (CDCl 3 (500MHz),} ppm): 1.35 ~ 1.75 (13, m) 2.02 (6, m) 2.14 (6, d) 2.17 (1, d) 2.58 (1, d) 4.15 (2, t) 6.05 (2, d) 6.31 (1, d) 6.94 (2, d) 7.48 (1,

Example 16: Preparation of 4- (tetrahydro-2H-pyran2-2yloxy) -5-cinnamate-5-norbornene (Preparation of cyclic olefin compound)

4-hydroxy-benzaldehyde (10 g, 82 mmol), 3,4-dihydro-2H-pyran (1.1 eq) and p-toluenesulfonic acid monohydrate (1 eq) were dissolved in MC (50 ml) and stirred for 12 hours. After removal of the solvent, the residue was purified by silica column chromatography to obtain 4- (tetrahydro-2H-pyran2-2yloxy) -benzaldehyde.

(10 eq, 45.4 mmol), malonic acid (2 eq) and piperidine (0.1 eq) were dissolved in pyridine (5 eq) and stirred at 80 ° C for 5 hours. After the reaction, the temperature was lowered to room temperature and neutralized with 3M HCl. The resulting white solid was obtained by filtration. This solid was dried in a vacuum oven to give 4- (tetrahydro-2H-pyran2-2yloxy) -cinnamic acid.

4-tetrahydro-2H-pyran-2-yloxy) cinnamic acid (5 g, 20.1 mmol), norbornene-5-ol (19 mmol) and Zr (AcAc) (0.2 mol% Lt; / RTI > After stirring, the reaction mixture was washed with 1M HCl, 1M NaHCO3 aqueous solution, and the solvent was removed to obtain a solid 4- (tetrahydro-2H-pyran2-2yloxy) -5-cinnamate-5-norbornene.

_{NMR (CDCl 3 (500MHz),} ppm): 1.50 ~ 2.11 (10, m) 2.27 (1, m) 2.86 (1, m) 3.55 ~ 3.66 (2, m) 4.01 (1, m) 5.80 (1, t ) 6.05 (2, dd) 6.31 (1, d) 6.94 (2, d) 7.48 (1,

Example 17: Preparation of 4- (tetrahydro-2H-pyran2-2yloxy) -cinnamate-5-methyl norbornene (Preparation of cyclic olefin compound)

The reaction was carried out in the same manner as in Example 16 except that norbornene-5-methanol was used in place of norbornene-5-ol to prepare 4- (tetrahydro-2H- pyran2-2yloxy) -cinnamate-5-methyl norbornene .

NMR (CDCl ₃ (500 MHz) _, ppm): 1.35-1.86 (9, m) 2.11-2.77 (3, m) 2.58 (1, m) 3.55-3.66 dd) 5.80 (1, t) 6.05 (2, dd) 6.31 (1, d) 6.94 (2,

Example 18: Preparation of 4- (tetrahydro-2H-pyran2-2yloxy) -cinnamate-5-ethyl norbornene (Preparation of cyclic olefin compound)

The reaction was carried out in the same manner as in Example 16 except that norbornene-5-ethanol was used instead of norbornene-5-ol to prepare 4- (tetrahydro-2H- pyran2-2yloxy) -cinnamate- .

NMR (CDCl ₃ (500 MHz) _, ppm): 1.35-1.86 (12, m) 2.11 (1, m) 2.27 (1, m) 3.55-3.65 ) 6.05 (2, dd) 6.31 (1, d) 6.94 (2, d) 7.48 (1,

Comparative Example 1: Preparation of 4- (benzyloxy) -cinnamate-5-norbornene (Preparation of cyclic olefin compound)

4-benzyloxy-benzaldehyde (10 g, 47 mmol), malonic acid (2 eq) and piperidine (0.1 eq) were dissolved in pyridine (5 eq) and stirred at 80 ° C for 5 hours. After the reaction, the temperature was lowered to room temperature and neutralized with 3M HCl. The resulting white solid was obtained by filtration. This solid was dried in a vacuum oven to give 4-benzyloxy-cinnamic acid.

The above 4-benzyloxy-cinnamic acid (5 g, 19.7 mmol), norbornene-5-ol (19 mmol) and Zr (AcAc) (0.2 mol%) were added to xylene and stirred at 190 ° C for 24 hours. After stirring, the reaction mixture was washed with 1M HCl, 1M NaHCO3 aqueous solution, and the solvent was removed to obtain solid 4-benzyloxy-cinnamate-5-norbornene.

NMR (CDCl ₃ (500 MHz) _, ppm): 0.6 (1, m) 1.22-1.27 (2, m) 1.47 (1, d) 1.87 (2, s) 5.98-6.19 (2, m) 6.36 (1, d) 7.3-7.5 (9,

Comparative Example 2: Preparation of 4- (benzyloxy) -cinnamate-5-methyl norbornene (Preparation of cyclic olefin compound)

(Benzyloxy) -cinnamate-5-methyl norbornene was prepared in the same manner as in Example 1 except that norbornene-5-methanol was used instead of norbornene-5-ol.

NMR (CDCl ₃ (500 MHz) _, ppm): 0.6 (1, m) 1.22-1.27 (2, m) 1.47 (1, d) 1.87 (2, s) 3.8 to 4.25 (2, m) 5.11 (2, s) 5.98 to 6.19 (2, m) 6.36 (1,

Example 19: Polymerization of 4- (cyclohexylmethoxy) -cinnamate-5-norbornene

4- (cyclohexylmethoxy) -cinnamate-5-norbornene (50 mmol) of Example 1 and toluene (400% by weight) purified by a solvent were added to a 250 ml Schlenk flask as a monomer. Then, 1-octene (10 mol%) was added. The temperature was raised to 90 ° C while stirring, and Pd (OAc) ₂ (16 μmol) and tricyclohexylphosphine (32 μmol) dissolved in 1 ml of dichloromethane as a catalyst and dimethylanilinium tetrakispentafluorophenyl borate dimethylanilinium tetrakis (pentafluorophenyl) borate (32 μmol) was added and reacted for 16 hours at 90 ° C. with stirring.

After the reaction, the reaction product was poured into an excess amount of ethanol to obtain a white polymer precipitate. The precipitate was filtered with a glass funnel and the recovered polymer was dried in a vacuum oven at 60 DEG C for 24 hours to obtain a polymer (Mw = 187k, PDI = 3.27, yield = 66%).

Example 20: Polymerization of 4- (cyclohexylmethoxy) -cinnamate-5-methyl norbornene

Except that 4- (cyclohexylmethoxy) -cinnamate-5-methyl norbornene (50 mmol) of Example 2 was used as a monomer instead of 4- (cyclohexylmethoxy) -cinnamate-5-norbornene of Example 1 (Mw = 174k, PDI = 3.36, yield = 79%).

Example 21: Polymerization of 4- (cyclohexylmethoxy) -cinnamate-5-ethyl norbornene

Except that 4- (cyclohexylmethoxy) -cinnamate-5-ethyl norbornene (50 mmol) of Example 3 was used instead of 4- (cyclohexylmethoxy) -cinnamate-5-norbornene of Example 1 as a monomer. (Mw = 171k, PDI = 3.26, yield = 84%).

Example 22: Polymerization of 4-cyclohexyloxy-cinnamate-5-norbornene

Except that 4-cyclohexyloxy-cinnamate-5-norbornene (50 mmol) of Example 4 was used instead of 4- (cyclohexylmethoxy) -cinnamate-5-norbornene of Example 1 as a monomer. The polymer of Example 22 was obtained (Mw = 168k, PDI = 3.32, yield = 87%).

Example 23: Polymerization of 4-cyclohexyloxy-cinnamate-5-methyl norbornene

Except that 4-cyclohexyloxy-cinnamate-5-methyl norbornene (50 mmol) of Example 5 was used as a monomer instead of 4- (cyclohexylmethoxy) -cinnamate-5-norbornene of Example 1, To obtain the polymer of Example 23 (Mw = 161k, PDI = 3.57, yield = 82%).

Example 24: Polymerization of 4-cyclohexyloxy-cinnamate-5-ethyl norbornene

Except that 4-cyclohexyloxy-cinnamate-5-ethyl norbornene (50 mmol) of Example 6 was used as a monomer instead of 4- (cyclohexylmethoxy) -cinnamate-5-norbornene of Example 1, (Mw = 167 k, PDI = 3.02, yield = 81%).

Example 25: Polymerization of 4- (cyclopentylmethoxy) -cinnamate-5-norbornene

Except that 4- (cyclopentylmethoxy) -cinnamate-5-norbornene (50 mmol) of Example 7 was used as a monomer instead of 4- (cyclohexylmethoxy) cinnamate-5-norbornene of Example 1, , The polymer of Example 25 was obtained (Mw = 162k, PDI = 3.16, yield = 76%).

Example 26: Polymerization of 4- (cyclopentylmethoxy) -cinnamate-5-methyl norbornene

Except that 4- (cyclopentylmethoxy) -cinnamate-5-methyl norbornene (50 mmol) of Example 8 was used as a monomer instead of 4- (cyclohexylmethoxy) cinnamate-5-norbornene of Example 1 (Mw = 171k, PDI = 3.49, yield = 80%).

Example 27: Polymerization of 4- (cyclopentylmethoxy) -cinnamate-5-ethyl norbornene

Except that 4- (cyclopentylmethoxy) -cinnamate-5-ethyl norbornene (50 mmol) of Example 9 was used as a monomer instead of 4- (cyclohexylmethoxy) -cinnamate-5-norbornene of Example 1 (Mw = 159k, PDI = 3.60, yield = 77%).

Example 28: Polymerization of 4-cyclopentyloxy-cinnamate-5-norbornene

Except that 4-cyclopentyloxy-cinnamate-5-norbornene (50 mmol) of Example 10 was used instead of 4- (cyclohexylmethoxy) -cinnamate-5-norbornene of Example 1 as a monomer. To obtain the polymer of Example 28 (Mw = 185k, PDI = 4.01, yield = 85%).

Example 29: Polymerization of 4-cyclopentyloxy-cinnamate-5-methyl norbornene

Except that 4-cyclopentyloxy-cinnamate-5-methyl norbornene (50 mmol) of Example 11 was used as a monomer instead of 4- (cyclohexylmethoxy) -cinnamate-5-norbornene of Example 1, , The polymer of Example 29 was obtained (Mw = 176k, PDI = 3.72, yield = 83%).

Example 30: Polymerization of 4-cyclopentyloxy-cinnamate-5-ethyl norbornene

Except that 4-cyclopentyloxy-cinnamate-5-ethyl norbornene (50 mmol) of Example 12 was used as a monomer instead of 4- (cyclohexylmethoxy) -cinnamate-5-norbornene of Example 1, To obtain the polymer of Example 30 (Mw = 161k, PDI = 3.26, yield = 74%).

Example 31: Polymerization of 4- (1-adamantanyloxy) -cinnamate-5-norbornene

The same procedure as in Example 19 was repeated, except that 4- (1-adamantanyloxy) -cinnamate-5-norbornene (50 mmol) of Example 13 was used as a monomer instead of 4- (cyclohexylmethoxy) (Mw = 143k, PDI = 3.44, yield = 70%).

Example 32: Polymerization of 4- (1-adamantanyloxy) -cinnamate-5-methyl norbornene

Example 19 was repeated except that 4- (1-adamantanyloxy) -cinnamate-5-methyl norbornene (50 mmol) of Example 14 was used as a monomer instead of 4- (cyclohexylmethoxy) The polymer of Example 32 was obtained with the same method and conditions (Mw = 176 k, PDI = 3.75, yield = 75%).

Example 33: Polymerization of 4- (1-adamantanyloxy) -cinnamate-5-ethyl norbornene

Example 19 was repeated except that 4- (1-adamantanyloxy) -cinnamate-5-ethyl norbornene (50 mmol) of Example 15 was used as a monomer instead of 4- (cyclohexylmethoxy) The polymer of Example 33 was obtained with the same method and conditions (Mw = 166 k, PDI = 3.18, yield = 71%).

Example 34: Polymerization of 4- (tetrahydro-2H-pyran2-2yloxy) -5-cinnamate-5-norbornene

Except that 4- (tetrahydro-2H-pyran2-2yloxy) -5-cinnamate-5-norbornene (50 mmol) of Example 16 was used as a monomer instead of 4- (cyclohexylmethoxy) (Mw = 176 k, PDI = 3.36, yield = 84%) was obtained in the same manner as in Example 19.

Example 35: Polymerization of 4- (tetrahydro-2H-pyran2-2yloxy) -cinnamate-5-methyl norbornene

Except that 4- (tetrahydro-2H-pyran2-2yloxy) -cinnamate-5-methyl norbornene (50 mmol) of Example 17 was used as a monomer instead of 4- (cyclohexylmethoxy) The polymer of Example 35 was obtained (Mw = 167 k, PDI = 3.28, yield = 81%) in the same manner and under the same conditions as in Example 19.

Example 36: Polymerization of 4- (tetrahydro-2H-pyran2-2yloxy) -cinnamate-5-ethyl norbornene

Except that 4- (tetrahydro-2H-pyran2-2yloxy) -cinnamate-5-ethylnorbornene (50 mmol) of Example 18 was used as a monomer instead of 4- (cyclohexylmethoxy) The polymer of Example 36 was obtained (Mw = 172k, PDI = 3.01, yield = 79%) under the same conditions and conditions as in Example 19.

Example 37: Polymer preparation by ring opening methathesis polymerization and hydrogenation of 4- (cyclohexylmethoxy) -cinnamate-5-norbornene

4- (cyclohexylmethoxy) -cinnamate-5-norbornene (50 mmol) was added to a 250 ml Schlenk flask under an Ar atmosphere, and then toluene (600 wt%) purified by a solvent was added thereto. The flask was maintained at a polymerization temperature of 80 ° C, and triethyl aluminum (1 mmol), which is a cocatalyst, was initially charged. Subsequently, 1 ml of a 0.01 M (mol / L) toluene solution in which tungsten hexachloride (WCl ₈ ) and ethanol were mixed at a ratio of 1: 3 (WCl ₈ 0.01 mmol, 0.03 mmol of ethanol) was added to the flask. Finally, 1-octene (15 mol%), a molecular weight regulator, was added to the flask and reacted for 18 hours at 80 ° C with stirring. After the reaction was completed, a small amount of ethylvinyl ether as a polymerization terminator was added to the polymerization solution, and the mixture was stirred for 5 minutes.

The polymerization solution was transferred to a 300-mL high-pressure reactor and 0.06 mL triethylaluminum (TEA) was added. Subsequently, 0.5 g of grace raney nickel (slurry phase in water) was added, and the mixture was reacted at 150 DEG C for 2 hours while maintaining the hydrogen pressure at 80 atm. After the reaction was completed, the polymerization solution was dropped on acetone to be precipitated, then filtered and dried in a vacuum oven at 70 캜 for 15 hours. As a result, a ring-opened hydrogenated polymer of 4- (cyclohexylmethoxy) -cinnamate-5-norbornene was obtained (Mw = 89k, PDI = 4.12, yield = 87%).

Example 38: Polymerization by ring-opening polymerization and hydrogenation of 4- (cyclohexylmethoxy) -cinnamate-5-methyl norbornene

Except that 4- (cyclohexylmethoxy) -cinnamate-5-methyl norbornene (50 mmol) of Example 2 was used as a monomer instead of 4- (cyclohexylmethoxy) -cinnamate-5-norbornene of Example 1 (Mw = 89k, PDI = 4.12, yield = 87%).

Example 39: Polymerization by ring-opening polymerization and hydrogenation of 4- (cyclohexylmethoxy) -cinnamate-5-ethyl norbornene

Except that 4- (cyclohexylmethoxy) -cinnamate-5-ethyl norbornene (50 mmol) of Example 3 was used instead of 4- (cyclohexylmethoxy) -cinnamate-5-norbornene of Example 1 as a monomer. And the conditions of Example 39 were obtained (Mw = 95k, PDI = 4.32, yield = 91%).

Example 40: Polymerization by ring-opening polymerization and hydrogenation of 4-cyclohexyloxy-cinnamate-5-norbornene

Except that 4-cyclohexyloxy-cinnamate-5-norbornene (50 mmol) of Example 4 was used instead of 4- (cyclohexylmethoxy) cinnamate-5-norbornene of Example 1 as a monomer. To obtain the polymer of Example 40 (Mw = 91k, PDI = 3.92, yield = 94%).

Example 41: Polymerization by ring-opening polymerization and hydrogenation of 4-cyclohexyloxy-cinnamate-5-methyl norbornene

Except that 4-cyclohexyloxy-cinnamate-5-methyl norbornene (50 mmol) of Example 5 was used as a monomer instead of 4- (cyclohexylmethoxy) -cinnamate-5-norbornene of Example 1, , The polymer of Example 41 was obtained (Mw = 86k, PDI = 3.56, yield = 90%).

Example 42: Polymerization by ring-opening polymerization and hydrogenation of 4-cyclohexyloxy-cinnamate-5-ethyl norbornene

Except that 4-cyclohexyloxy-cinnamate-5-ethyl norbornene (50 mmol) of Example 6 was used as a monomer instead of 4- (cyclohexylmethoxy) -cinnamate-5-norbornene of Example 1, , The polymer of Example 42 was obtained (Mw = 89k, PDI = 4.32, yield = 86%).

Example 43: Polymerization by ring-opening polymerization and hydrogenation of 4- (cyclopentylmethoxy) -cinnamate-5-norbornene

Except that 4- (cyclopentylmethoxy) -cinnamate-5-norbornene (50 mmol) of Example 7 was used instead of 4- (cyclohexylmethoxy) -cinnamate-5-norbornene of Example 1 as a monomer. (Mw = 94k, PDI = 3.87, yield = 89%).

Example 44: Polymerization by ring-opening polymerization and hydrogenation of 4- (cyclopentylmethoxy) -cinnamate-5-methyl norbornene

Except that 4- (cyclopentylmethoxy) -cinnamate-5-methyl norbornene (50 mmol) of Example 8 was used instead of 4- (cyclohexylmethoxy) -cinnamate-5-norbornene of Example 1 as a monomer. (Mw = 87k, PDI = 4.12, yield = 95%).

Example 45: Polymerization by ring-opening polymerization and hydrogenation of 4- (cyclopentylmethoxy) cinnamate-5-ethyl norbornene

Except that 4- (cyclopentylmethoxy) -cinnamate-5-ethyl norbornene (50 mmol) of Example 9 was used instead of 4- (cyclohexylmethoxy) -cinnamate-5-norbornene of Example 1 as a monomer. (Mw = 82k, PDI = 3.79, yield = 89%).

Example 46: Polymerization by ring-opening polymerization and hydrogenation of 4-cyclopentyloxy-cinnamate-5-norbornene

Except that 4-cyclopentyloxy-cinnamate-5-norbornene (50 mmol) of Example 10 was used instead of 4- (cyclohexylmethoxy) cinnamate-5-norbornene of Example 1 as a monomer. The polymer of Example 46 was obtained (Mw = 101k, PDI = 3.63, yield = 88%).

Example 47: Polymerization by ring-opening polymerization and hydrogenation of 4-cyclopentyloxy-cinnamate-5-methyl norbornene

Except that 4-cyclopentyloxy-cinnamate-5-methyl norbornene (50 mmol) of Example 11 was used as a monomer instead of 4- (cyclohexylmethoxy) cinnamate-5-norbornene of Example 1, , The polymer of Example 47 was obtained (Mw = 98k, PDI = 4.22, yield = 92%).

Example 48: Polymerization by ring-opening polymerization and hydrogenation of 4-cyclopentyloxy-cinnamate-5-ethyl norbornene

Except that 4-cyclopentyloxy-cinnamate-5-ethyl norbornene (50 mmol) of Example 12 was used as a monomer instead of 4- (cyclohexylmethoxy) -cinnamate-5-norbornene of Example 1, , The polymer of Example 48 was obtained (Mw = 102k, PDI = 3.98, yield = 91%).

Example 49: Polymerization by ring-opening polymerization and hydrogenation of 4- (1-adamantanyloxy) -cinnamate-5-norbornene

The procedure of Example 37 was repeated except that 4- (1-adamantanyloxy) -cinnamate-5-norbornene (50 mmol) of Example 13 was used as a monomer instead of 4- (cyclohexylmethoxy) (Mw = 92k, PDI = 3.85, yield = 89%).

Example 50: Polymerization by ring-opening polymerization and hydrogenation of 4- (1-adamantanyloxy) -cinnamate-5-methyl norbornene

Example 37 was repeated except that 4- (1-adamantanyloxy) -cinnamate-5-methyl norbornene (50 mmol) of Example 14 was used as a monomer instead of 4- (cyclohexylmethoxy) The polymer of Example 50 was obtained with the same method and conditions (Mw = 99k, PDI = 4.12, yield = 92%).

Example 51: Polymerization by ring-opening polymerization and hydrogenation of 4- (1-adamantanyloxy) -cinnamate-5-ethyl norbornene

Example 37 was repeated except that 4- (1-adamantanyloxy) -cinnamate-5-ethyl norbornene (50 mmol) of Example 15 was used as a monomer instead of 4- (cyclohexylmethoxy) The polymer of Example 51 was obtained (Mw = 86k, PDI = 3.23, yield = 92%) in the same manner and under the same conditions.

Example 52: Polymerization by ring-opening polymerization and hydrogenation of 4- (tetrahydro-2H-pyran2-2yloxy) -5-cinnamate-5-norbornene

Except that 4- (tetrahydro-2H-pyran2-2yloxy) -5-cinnamate-5-norbornene (50 mmol) of Example 16 was used as a monomer instead of 4- (cyclohexylmethoxy) (Mw = 85k, PDI = 4.12, yield = 89%) was obtained in the same manner and under the same conditions as in Example 37.

Example 53: Polymerization by ring-opening polymerization and hydrogenation of 4- (tetrahydro-2H-pyran2-2yloxy) -cinnamate-5-methyl norbornene

Except that 4- (tetrahydro-2H-pyran2-2yloxy) -cinnamate-5-methyl norbornene (50 mmol) of Example 17 was used as a monomer instead of 4- (cyclohexylmethoxy) The polymer of Example 53 was obtained (Mw = 96k, PDI = 3.81, yield = 92%) in the same manner and under the same conditions as in Example 37.

Example 54: Polymerization by ring-opening polymerization and hydrogenation of 4- (tetrahydro-2H-pyran2-2yloxy) -cinnamate-5-ethyl norbornene

Except that 4- (tetrahydro-2H-pyran2-2yloxy) -cinnamate-5-ethylnorbornene (50 mmol) of Example 18 was used as a monomer instead of 4- (cyclohexylmethoxy) The polymer of Example 54 was obtained (Mw = 92 k, PDI = 3.19, yield = 89%) under the same conditions and conditions as in Example 37.

Comparative Example 3: Polymerization of 4- (benzyloxy) -cinnamate-5-norbornene

Except that 4- (benzyloxy) -cinnamate-5-norbornene (50 mmol) of Comparative Example 1 was used as a monomer in place of 4- (cyclohexylmethoxy) cinnamate-5-norbornene of Example 1, , The polymer of Comparative Example 3 was obtained (Mw = 163 k, PDI = 2.13, yield = 88%).

Comparative Example 4: Polymerization of 4- (benzyloxy) -cinnamate-5-methyl norbornene

Except that 4- (benzyloxy) -cinnamate-5-methyl norbornene (50 mmol) of Comparative Example 2 was used as a monomer instead of 4- (cyclohexylmethoxy) cinnamate-5-norbornene of Example 1 (Mw = 154k, PDI = 2.74, yield = 84%).

≪ Experimental Example 1 > Production of liquid crystal film

2 to 3% by weight of the photoreactive polymer of Examples 19 to 54 and Comparative Examples 3 to 4, 0.5 to 1.0% by weight of the binder (acrylic binder of PETA, DPHA or triacryl isocyanurate), 0.05 of the photoinitiator (Ciba irgacure 907) To 1% by weight of the solution was dissolved in toluene solvent, and the solution was coated on a glass substrate or a polymer film (COC or COP cycloolefin stretched film or TAC film) by bar coating. After drying at 80 ° C for 2 minutes, polarized UV was irradiated. In order to confirm the rotation of the liquid crystal direction, half of the cured alignment film was covered, rotated 90 degrees, and polarized UV was irradiated again. The amount of polarized UV light was adjusted with time. A-plate liquid crystal (25 wt% in toluene) was dropped on the alignment layer, bar coated, dried at 60 ° C for 2 minutes, and then cured by irradiating 20 mJ of UV.

Fig. 2 shows an image between the polarizing plate between the alignment film (45 deg.) Where the primary alignment advances and the alignment film (135 deg. Fig. 2 is a photograph of the orientation film using the polymer of Example 19 prepared from the monomer of Example 1 as a photo-alignment material, after the secondary alignment was carried out.

Referring to FIG. 2, it was confirmed that, in the alignment film using the polymer of Example 19, when the polarization direction was changed in the secondary alignment, the alignment direction was well changed and a good image could be obtained.

<Experimental Example 2> Evaluation of solubility

5%, 7% and 10% by weight of the photoreactive polymers of Examples 19 to 54 and Comparative Examples 3 and 4 were respectively dissolved in toluene and xylene, and the turbidity was measured to evaluate the solubility. The evaluation results of Example 19, Example 20 and Comparative Examples 3 and 4 are summarized in Table 1 below.

toluene Xylene 5 wt% 7 wt% 10 wt% 5 wt% 7 wt% 10 wt% Example 19 3.4 4.1 5.7 3.1 3.8 4.8 Example 20 3.7 4.9 6.2 3.3 4.3 5.5 Comparative Example 3 9.8 12.1 15.7 10.7 13.1 16.9 Comparative Example 4 8.7 11.8 13.9 9.4 12.5 15.4

Referring to the above Table 1, it was confirmed that the polymers of Comparative Examples 3 and 4 exhibited low solubility and high turbidity, while the polymers of Examples 19 and 20 showed excellent solubility in organic solvents and low turbidity.

Claims (10)

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,
q is an integer of 0 to 4,
At least one of R 1, R 2, R 3, and R 4 is a radical selected from the group consisting of:
R1 to R4 are the same or different from each other and each independently 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; Aryl having 6 to 40 carbon atoms; And polar functional groups comprising at least one selected from oxygen, nitrogen, phosphorus, sulfur, silicon, and boron,
Wherein R1 to R4 are independently selected from the group consisting of hydrogen; halogen; Or a combination of at least one member selected from the group consisting 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 is any one of R 3 and R 4 A saturated or unsaturated aliphatic ring having 4 to 12 carbon atoms or an aromatic ring having 6 to 24 carbon atoms,
[Chemical Formula 1a] [Chemical Formula 1b]

In the above general formulas (1a) and (1b)
A is a simple bond, oxygen, sulfur or -NH-,
B is selected from the group consisting of a simple bond, alkylene having 1 to 20 carbon atoms, carbonyl, carboxy, ester, arylene having 6 to 40 carbon atoms, and heteroarylene having 6 to 40 carbon atoms,
X is oxygen or sulfur;
R9 represents a simple bond, an alkylene having 1 to 20 carbon atoms, an alkenylene having 2 to 20 carbon atoms, a cycloalkylene having 3 to 12 carbon atoms, an arylene having 6 to 40 carbon atoms, an aralkylene having 7 to 15 carbon atoms, Lt; / RTI &gt; to 20 carbon atoms,
At least one of R10 to R14 is a radical represented by the following general formula (2), and the remaining R10 to R14 are the same or different and each independently represents hydrogen, halogen, alkyl of 1 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryloxy having 6 to 30 carbon atoms; Aryl having 6 to 40 carbon atoms and heteroaryl having 6 to 40 carbon atoms containing hetero elements of Group 14, Group 15 or Group 16,
(2)

L is selected from the group consisting of oxygen, sulfur, -NH-, alkylene having 1 to 20 carbon atoms, carbonyl, carboxy, -CONH- and arylene having 6 to 40 carbon atoms,
R15 is a simple bond, alkylene having 1 to 10 carbon atoms,
R16 is selected from the group consisting of a simple bond, -O-, -C (= O) O-, -OC (= O) -, -NH-, -S- and -C
The ring C is a cycloalkyl having 5 to 20 carbon atoms or a heteroaryl cycloalkyl having 3 to 20 carbon atoms in which at least one hetero atom of oxygen, nitrogen or sulfur is contained in the ring,
R17 to R21 are the same as or different from each other, and each independently hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryloxy having 6 to 30 carbon atoms; Aryl having 6 to 40 carbon atoms; A heteroaryl having 6 to 40 carbon atoms, including a heteroatom of Group 14, Group 15 or Group 16, and an alkoxyaryl having 6 to 40 carbon atoms.
delete The cyclic olefin compound according to claim 2, wherein the ring C is cyclohexyl, cyclopentyl, adamantanyl or tetrahydropyranyl.
The cyclic olefin compound according to claim 1, wherein at least one of R 1 and R 2 in Formula 1 is represented by Formula 1a or Formula 1b.
A photoreactive polymer comprising repeating units of the following formula (3a) or (3b):
[Formula 3]

Each independently of the above-mentioned formulas (3a) and (3b)
m is from 50 to 5000,
q is an integer of 0 to 4,
At least one of R 1, R 2, R 3, and R 4 is a radical selected from the group consisting of:
R1 to R4 are the same or different from each other and each independently 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; Aryl having 6 to 40 carbon atoms; And polar functional groups comprising at least one selected from oxygen, nitrogen, phosphorus, sulfur, silicon, and boron,
Wherein R1 to R4 are independently selected from the group consisting of hydrogen; halogen; Or a combination of at least one member selected from the group consisting 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 is any one of R 3 and R 4 A saturated or unsaturated aliphatic ring having 4 to 12 carbon atoms or an aromatic ring having 6 to 24 carbon atoms,
[Chemical Formula 1a] [Chemical Formula 1b]

In the above general formulas (1a) and (1b)
A is a simple bond, oxygen, sulfur or -NH-,
B is selected from the group consisting of a simple bond, alkylene having 1 to 20 carbon atoms, carbonyl, carboxy, ester, arylene having 6 to 40 carbon atoms, and heteroarylene having 6 to 40 carbon atoms,
X is oxygen or sulfur;
R9 represents a simple bond, an alkylene having 1 to 20 carbon atoms, an alkenylene having 2 to 20 carbon atoms, a cycloalkylene having 3 to 12 carbon atoms, an arylene having 6 to 40 carbon atoms, an aralkylene having 7 to 15 carbon atoms, Lt; / RTI &gt; to 20 carbon atoms,
At least one of R10 to R14 is a radical represented by the following general formula (2), and the remaining R10 to R14 are the same or different and each independently represents hydrogen, halogen, alkyl of 1 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryloxy having 6 to 30 carbon atoms; Aryl having 6 to 40 carbon atoms and heteroaryl having 6 to 40 carbon atoms containing hetero elements of Group 14, Group 15 or Group 16,
(2)

L is selected from the group consisting of oxygen, sulfur, -NH-, alkylene having 1 to 20 carbon atoms, carbonyl, carboxy, -CONH- and arylene having 6 to 40 carbon atoms,
R15 is a simple bond, alkylene having 1 to 10 carbon atoms,
R16 is selected from the group consisting of a simple bond, -O-, -C (= O) O-, -OC (= O) -, -NH-, -S- and -C
The ring C is a cycloalkyl having 5 to 20 carbon atoms or a heteroaryl cycloalkyl having 3 to 20 carbon atoms in which at least one hetero atom of oxygen, nitrogen or sulfur is contained in the ring,
R17 to R21 are the same as or different from each other, and each independently hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryloxy having 6 to 30 carbon atoms; Aryl having 6 to 40 carbon atoms; A heteroaryl having 6 to 40 carbon atoms, including a heteroatom of Group 14, Group 15 or Group 16, and an alkoxyaryl having 6 to 40 carbon atoms.
delete The photoreactive polymer of claim 5, having a weight average molecular weight of from 10,000 to 1,000,000.
An alignment film comprising the photoreactive polymer of claim 5.
10. A liquid crystal phase difference film comprising the alignment film of claim 8 and a liquid crystal layer on an alignment film.
 A display device comprising the alignment film of claim 9.

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