WO2014038868A1 - Photoalignment polymer, and alignment layer and liquid crystal retardation film comprising same - Google Patents

Abstract

The present invention relates to a photoalignment polymer in which an alignment direction according to a polarization direction can be easily changed, and which photoalignment polymer can be desirably applied to an alignment layer or the like of a stereoscopic display device. The present invention also relates to an alignment layer and a liquid crystal retardation film comprising the photoalignment polymer. The photoalignment polymer comprises a cyclic olefin-based repeating unit substituted with one or more photoreactive functional groups. The photoalignment polymer has an absorption rate (AR) of 0.02 or higher defined by a specific formula when primary photoalignment is performed by radiating first polarized UV light having a wavelength of 280 to 315nm and a first polarization direction in the total quantity of light of 60 mJ/cm2 or less, and secondary photoalignment is performed by radiating second polarized UV light having a wavelength of 280 to 315nm and a second polarization direction which is changed by 90° from the first polarization direction in the total quantity of light of 60 mJ/cm2 or less.

Description

 【Specification】

 [Name of invention]

 Photo-alignment polymer, alignment film and liquid crystal retardation film comprising the same

 [Technical Field]

 The present invention relates to a photo-alignment polymer, an alignment film comprising the same, and a liquid crystal retardation film. More specifically, the present invention relates to an optical alignment polymer which can be easily changed in the alignment direction according to the polarization direction and can be preferably applied to an alignment film of a stereoscopic display device, an alignment film including the same, and a liquid crystal retardation film.

 Background technology

 As the size of liquid crystal displays increases, the use of mobile phones, laptops, and the like gradually expands to home use, such as wall-mounted TVs, and thus, high definition, high quality and wide viewing angles are required for liquid crystal displays. In particular, thin film transistor liquid crystal displays (TFT-LCDs) independently drive individual pixels, and thus, the response range of liquid crystals is very high, and high-quality moving images can be realized.

 In order to use a liquid crystal as an optical switch in such a TFT-LCD, the liquid crystal must be initially oriented in a predetermined 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 such liquid crystal alignment, a rubbing process in which a heat-resistant polymer such as polyimide is applied on a transparent glass to form a polymer alignment layer, and a rubbing process of rubbing the alignment layer while rotating a rotating roller wrapped with a rubbing cloth such as nylon or rayon at high speed is performed. It has been applied. However, the rubbing process may cause mechanical scratches on the surface of the liquid crystal aligning agent during rubbing, or may cause high static electricity, thereby destroying the thin film transistor. In addition, defects are generated due to the fine fibers generated in the rubbing cloth, which is an obstacle in improving production yield. In order to overcome the problems of this rubbing process and to innovate in terms of productivity, a newly designed liquid crystal alignment method is liquid crystal alignment (hereinafter, referred to as "optical alignment") by light such as UV.

 Photo-alignment refers to a mechanism that forms photopolymerizable liquid crystal alignment layers in which liquid crystals are oriented by the photosensitive groups bonded to a constant photo-alignment polymer by linearly polarized UV, causing photoreactions. Refers to.

 Representative examples of such photoalignment include M. Schadt et al. (Jpn. 丄 Appl. Phys., Vol 31., 1992, 2155), Dae S. Kang et al. (US Pat. Phys. Vol. 34, 1995, UOOO). The photo-oriented polymers used in these patents and papers are mainly polycinnamate-based polymers such as poly (vinyl cinnamate) (PVCN) or poly (inyl methoxycinnamate (PVMC). In the case of photo-alignment, the double bond of cinnamate reacts with [2 + 2] cycloaddition to form cyclobutane by irradiated UV, resulting in anisotropy. The alignment of the liquid crystal molecules is induced by arranging the liquid crystal molecules in one direction. In addition, Japanese Patent Laid-Open No. Hei 11-181127 discloses a polymer having a side chain including photosensitive groups such as cinnamate groups in a main chain such as acrylate and methacrylate, and an alignment film containing the same. In addition, Korean Patent Laid-Open Publication No. 2002- 0006819 discloses the use of an alignment film made of a polymethacrylic polymer.

Recently, photo-alignment polymers and photo-alignments using the same have been applied to the implementation of stereoscopic images. However, in order to implement a stereoscopic image using such photoalignment, it is necessary to include photoalignment polymers having different alignment directions together in a single alignment layer. Previously, after applying a composition containing a photo-alignment polymer on the substrate for this purpose, by irradiating the polarization in different directions for each region through two or more mask process, to adjust the orientation direction of the polymers included in each region differently It was. According to this prior art, because the mask process needs to be performed two or more times, the formation process of the alignment layer is very complicated, the yield of the process is also low, the unit cost is also very high.

 [Contents of the Invention]

 [Problem to solve]

 The present invention is to provide a photo-alignment polymer that can be easily changed in the alignment direction according to the polarization direction and can be preferably applied to the alignment film of the stereoscopic display device.

 The present invention also provides an alignment film and a liquid crystal retardation film containing the photoalignable polymer.

 Moreover, this invention provides the display element containing the said orientation film or liquid crystal retardation film. ,

 [Measures of problem]

The present invention relates to a photoalignable polymer comprising a cyclic olefin repeat unit in which at least one photoreactive functional group is substituted, the first UV polarization having a wavelength of 280 to 315 nm and a first polarization direction of 60 mJ / cm ² or less. After the first optical alignment by irradiating with the total amount of light, the second UV polarized light having a wavelength of 280 to 315 nm and a second polarization direction changed by 90 ^° from the first polarization direction to a total amount of light of 60 mJ / cm ² or less When irradiated with secondary photoalignment, a photoalignable polymer having an absorbance (AR) of at least 0.02, which is defined by Equation 1 below, is provided:

Equation ¹

 Absorbance (AR) = (| A1-A2 |) / (A1 + A2)

 Wherein A1 represents the absorbance of the photoalignable polymer measured at the maximum absorption wavelength among the wavelengths of 280 to 330 nm after the first photoalignment, and A2 is the maximum absorption wavelength among the wavelengths of 280 to 330 nm after the secondary photoalignment. The absorbance of the photoalignable polymer measured is shown.

In the photoalignable polymer, the cyclic olefin repeat unit may include a repeat unit of Formula 3a or 3b: [Formula 3a] [Formula 3b]

 In the formulas 3a and 3b, each independently, m is 50 to 5000, and at least one of R1, R2, R3, and R4 is a radical selected from the group consisting of Formulas 1a and 1b, and is a radical of Formula 1a or 1b. The remaining R1 to R4 except for the same or different from each other, each of which is hydrogen hydrogen; halogen; Substituted or unsubstituted linear or branched alkyl having 1 to 20 carbon atoms; Substituted or unsubstituted linear or branched alkenyl having 2 to 20 carbon atoms; Substituted or unsubstituted linear or branched alkynyl having 2 to 20 carbon atoms; Substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Substituted or unsubstituted aryl having 6 to 40 carbon atoms; And a polar functional group including at least one selected from oxygen, nitrogen, phosphorus, sulfur, silicon, and boron, wherein R1 to R4 are hydrogen; halogen; Or when it is not a polar functional group, one or more combinations selected from the group consisting of R1 and R2, R3 and 只 4 are connected to each other to form an alkylidene group having 1 to 10 carbon atoms, or R1 or R2 is any one of R3 and R4 To form a saturated or unsaturated aliphatic ring of 4 to 12 carbon atoms or an aromatic ring of 6 to 24 carbon atoms,

상기 화학식 1 a 및 1 t»에서， A는 단순결합, 산소, 황 또는 -NH-이고， B는 단순결합, 치환 또는 비치환된 탄소수 1 내지 20의 알킬렌, 카보닐， 카르복시 , 에스테르, 치환 또는 비치환된 탄소수 6 내지 40의 아릴렌, 및 치환 또는 비치환된 탄소수 6 내지 40의 헤테로아릴렌으로 이루어진 군에서 선택되고， X는 산소 또는 황이고; R9는 단순결합， 치환 또는 비 치환된 탄소수 1 내지 20의 알킬렌, 치환 또는 비치환된 탄소수 2 내지 20의 알케닐렌, 치환 또는 비치환된 탄소수 3 내지 12의 시클로알킬렌, 치환 또는 비 치환된 탄소수 6 내지 40의 아릴렌, 치환 또는 비 치환된 탄소수 7 내지 15의 아르알킬렌， 및 치환 또는 비치환된 탄소수 2 내지 20의 알키 닐렌으로 이루어진 군에서 선택되며， R10 내지 R14 중 적어도 하나는 -L-R15-R16- (치환 또는 비 치환된 탄소수 6 내지 40의 아릴)로 표시되는 라디칼이고， 이를 제외 한 나머지 R10 내지 R14는 서로 동일하거나 상이하고， 각각 독립적으로 수소， 할로겐, 치환 또는 비 치환된 탄소수 1 내지 20의 알킬; 치환 또는 비 치환된 탄소수 1 내지 20의 알콕시 ; 치환 또는 비치환된 탄소수 6 내지 30의 아릴옥시 ; 치환 또는 비 치환된 탄소수 6 내지 40의 아릴 및 14족, 15족 또는 16족의 헤테로 원소를 포함하는 탄소수 6 내지 40의 헤테로 아릴로 이루어진 군에서 선택되 고 L은 산소, 황, -NH-, 치환 또는 비치환된 탄소수 1 내지 20의 알킬렌, 카보닐, 카르복시 , -CONH- 및 치환 또는 비치환된 탄소수 6 내지 40의 아릴렌으로 이루어 진 군에서 선택되고， R15는 치환 또는 비 치환된 탄소수 1 내지 10의 알킬이고, R16은 단순결합， -0-, -C(=O)O-, -OC(=O)-, -NH-, -S- 및 -C(=O)-로 이루어진 군에서 선택된다.

In Formula 1 a and 1 t », A is a simple bond, oxygen, sulfur or -NH-, B is a simple bond, substituted or unsubstituted C 1-20 alkylene, carbonyl, carboxy, ester, substituted Or unsubstituted arylene having 6 to 40 carbon atoms, and substituted or unsubstituted heteroarylene having 6 to 40 carbon atoms, X is oxygen or sulfur; R9 is a simple bond, substituted or unsubstituted alkylene having 1 to 20 carbon atoms, substituted or unsubstituted alkenylene having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkylene having 3 to 12 carbon atoms, substituted or unsubstituted Arylene having 6 to 40 carbon atoms, substituted or unsubstituted aralkylene having 7 to 15 carbon atoms, and substituted or unsubstituted alkynylene having 2 to 20 carbon atoms, and at least one of R10 to R14 is- Radicals represented by L-R15-R16- (substituted or unsubstituted aryl having 6 to 40 carbon atoms), except for the remaining R10 to R14, which are the same as or different from each other, and are each independently hydrogen, halogen, substituted or unsubstituted Alkyl having 1 to 20 carbon atoms; Substituted or unsubstituted alkoxy having 1 to 20 carbon atoms; Substituted or unsubstituted aryloxy having 6 to 30 carbon atoms; Selected from the group consisting of substituted or unsubstituted aryl having 6 to 40 carbon atoms and hetero aryl having 6 to 40 carbon atoms including hetero group of 14, 15 or 16 group, L is oxygen, sulfur, -NH-, Selected from the group consisting of substituted or unsubstituted C1-20 alkylene, carbonyl, carboxy, -CONH- and substituted or unsubstituted C6-40 arylene, R15 is substituted or unsubstituted carbon number Alkyl of 1 to 10, R 16 is a simple bond, -0-, -C (= 0) O-, -OC (= 0)-, -NH-, -S- and -C (= 0)- Selected from the group.

 The present invention also provides an alignment film and a liquid crystal retardation film containing the photoalignable polymer.

 Moreover, this invention provides the display element containing the said oriented film or liquid crystal retardation film.

[Effects of the Invention】 In the photoalignable polymer of the present invention, a change in the orientation direction according to the polarization direction can be quite freely shown. For this reason, the photo-alignment polymer may be very preferably applied to a patterned retardation film or a patterned cell alignment film applied for realizing a three-dimensional stereoscopic image. In particular, since the photo-alignment polymer can change the orientation direction relatively freely, the patterned retardation film or the cell alignment film can be produced very efficiently by only one mask process.

 Therefore, the photo-alignment polymer and the alignment film including the same may be very preferably applied to various liquid crystal display devices applied for realizing a stereoscopic image.

 【Brief Description of Drawings】

 1 schematically shows an example of a conventional alignment layer structure.

[Specific Contents for Due Diligence]

 Hereinafter, a photoalignable polymer and an alignment layer in accordance with an embodiment of the present invention will be described in detail.

According to one embodiment of the invention, a photo-alignment polymer comprising a cyclic olefin repeat unit substituted with one or more photo-banung functional groups, the first UV polarization having a wavelength of 280 to 315nm, the first polarization direction) After irradiating with the total amount of light of mJ / cm ² or less and performing the first optical alignment, the second UV polarization having a wavelength of 280 to 315 nm and a second polarization direction changed by 90 ^° from the first polarization direction is about 60 mJ / When undergoing secondary photoalignment by irradiation with a total amount of light of cm ² or less, a photoalignable polymer having an absorbance (AR) of about 0.02 or more, which is defined by Equation 1 below, is provided:

 [Equation 1]

 Absorbance (AR) = (| A1-A2 |) / (A1 + A2)

In the above formula, A1 represents the absorbance of the photoalignable polymer measured at the maximum absorption wavelength of about 280 to 330 nm, for example, about 300 nm after the first photoalignment, and A2 after the second photoalignment, In a wavelength of about 280-330 nm Absorbance for the photoalignable polymer measured at the maximum absorption wavelength, for example about 300 nm.

 In general, when the photoalignment is performed by irradiating UV polarization in a predetermined polarization direction with respect to the photoalignment polymer, the double bond included in the photoreactive functional group causes dimerization, and thus the photoalignment polymers are in one direction. Arranged in the form of anisotropy and the optical orientation can proceed. However, after the dimerization and photo-alignment by the UV polarization irradiation, the absorbance is reduced because the structure capable of further photoreaction is reduced. Therefore, the difference between the absorbance after the first photoalignment and the absorbance after the second photoalignment becomes more than a certain level. When the second photoalignment is performed after the first photoalignment, the photoalignable polymers have a dimerization and a second photofold above a certain level. It may reflect that the fragrance is smooth.

Particularly, in the photoalignable polymer of one embodiment, when the secondary photoalignment is performed by changing the polarization direction after the primary photoalignment, the absorbance of Equation 1 reaches about 0.02 or more. Such photo-orientable polymers can cause a significant degree of dimerization and secondary photo-alignment by changing the direction of polarization of the photoreactive functional groups, even when the photo-polarization group undergoes secondary photo-alignment. Therefore, in order to provide a patterned retardation film or an alignment film using such a photo-alignment polymer, the mask process does not need to be performed two or more times, and a patterning that shows excellent orientation in each region with a single mask process alone is required. A retardation film, an orientation film, etc. can be manufactured. That is, after applying the composition containing the photo-alignment polymer on the substrate, the first photo-alignment proceeds by irradiating UV polarization in a predetermined direction to the front surface first, only in a certain region through a single mask process When irradiating UV polarization having a changed polarization direction, it is possible to easily and efficiently obtain a patterned retardation film or an alignment film in which the orientation directions of the polymers are adjusted differently for each region. Therefore, the photo-alignment polymer of the above embodiment may be very preferably applied to a patterned retardation film or an alignment film applied for realizing a stereoscopic image. In contrast, none of the previously known photo-alignment polymers have satisfied the above-mentioned properties. In particular, existing photo-alignment polymers are not moved once the alignment direction is determined by polarization. Or, even if it is moving, it was necessary to proceed the secondary photo-alignment with the polarization of the other direction having a very strong light amount. Therefore, in the case of using the existing polymers, in order to obtain a patterned retardation film or the like, it was necessary to irradiate polarizations in one direction different from each other in each region, and at least two mask processes need to be performed for this purpose. there was.

 Hereinafter, the optical orientation polymer of one embodiment will be described in more detail.

The photo-orientation polymer has an optical absorption rate (AR of at least about 0.02), even though the primary and secondary photo-alignments proceed at a low total light amount of about 60 mJ / cm ² or less, for example, about 3 to 60 mJ / cm ² . More specifically, it may be about 0.02 to 0.08. As described above, even if the secondary optical alignment is performed by changing the polarization direction under a weak amount of light, the orientation direction is free to change, and as a result, the secondary optical alignment can be efficiently performed. Only a single mask process can provide a patterned retardation film or an alignment film very easily.

More specifically, the photo-alignment polymer, the light absorption rate when the total light amount in the primary photo-alignment is about 20 to 60 mJ / cm ² , the total light amount in the secondary photo-alignment is about 3 to 60 mJ / cm ² (AR) may be about 0.02 to 0.05. In addition, the photo-alignment polymer has a light absorption rate when the total light amount of the primary photo-alignment yarn is about 3 to 20 mJ / cm ² , the total light amount of the secondary photo-alignment is about 3 to 60 mJ / cm ² ) Is about 0.02 to 0.08, black is about 0.03 to 0.08, and when the total amount of light in the secondary photoalignment is about 15 to 60 mJ / cm ² , the absorbance (AR) is about 0.04 to 0.08 Can be.

As such, the optical alignment polymer exhibits a change in the orientation direction and the secondary photoalignment of a predetermined level or more according to the change in polarization direction even when the total light ½ in the primary photoalignment is relatively strong so that no additional light reflection structure remains. Can be represented. Furthermore, the photoalignable polymer has a higher degree of secondary photoalignment and orientation change due to a change in polarization direction when the total amount of light in the primary photoalignment is relatively weak and the total amount of light in the secondary photoalignment is relatively strong. Can be represented. As such, by adjusting the light irradiation time and the total amount of light in the first and second optical alignment, the degree of change in the orientation direction in the first and second optical alignment or the second optical alignment can be controlled. It can be used very efficiently to provide a patterned retardation film or an alignment film exhibiting the desired orientation for each region. In addition, the above-described photo-alignment polymer basically exhibits a certain level of absorbance after the first photo-alignment due to the excellent light reflection property and the photo-alignment, and also changes the orientation direction change and the secondary photo-alignment more than a certain level according to the polarization direction change. As shown, the above-described absorbance can be exhibited even after the secondary photoalignment. Therefore, the photoalignable polymer of one embodiment can be easily provided with a patterned retardation film or an alignment film without two mask processes. On the other hand, the above-described properties of the absorbance (AR), etc. of Formula 1 have not achieved any previously known photo-alignment polymers, it can be achieved by using a photo-alignment polymer obtained from a predetermined cyclic olefin compound . Hereinafter, such a cyclic olefin compound, a photoalignable polymer, and a method for producing the same will be described in detail.

 Properties according to the above-described embodiment can be achieved from the photo-alignment polymer obtained by using as a monomer a cyclic olefin compound having a photobanung functional group represented by the formula (1):

[Formula 1]

상기 화학식 1에서, q 는 0 내지 4의 정수이고, R1, R2, R3, 및 R4 중 적어도 하나는 하기 화학식 1a 및 1b로 이루어진 군으로부터 선택된 라디칼이며ᅳ 화학식 1a 또는 1b의 라디칼인 것을 제외한 나머지 R1 내지 R4는 서로 동일하거나 상이하고， 각각 독립적으로 수소; 할로겐; 치환 또는 바치환된 탄소수 1 내지 20의 선형 또는 분지형 알킬; 치환 또는 비치환된 탄소수 2 내지 20의 선형 또는 분지형 알케닐; 치환 또는 비치환된 탄소수 2 내지 20의 선형 또는 분지형 알키닐; 치환 또는 비치환된 탄소수 3 내지 12의 시클로알킬; 치환 또는 비치환된 탄소수 6 내지 40의 아릴; 및 산소， 질소, 인， 황， 실뫼콘, 및 보론 중에서 선택된 적어도 하나 이상을 포함하는 극성 작용기로 이루어진 군에서 선택되고， 상기 R1 내지 R4 가 수소; 할로겐; 또는 극성 작용기가 아닌 경우, R1 과 R2, R3 와 R4로 이루어진 군에서 선택된 하나 이상의 조합이 서로 연결되어 탄소수 1 내지 10의 알킬리덴 그룹을 형성하거나， 또는 R1 또는 R2 가 R3 및 R4 중의 어느 하나와 연결되어 탄소수 4 내지 12의 포화 또는 불포화 지방족 고리， 또는 탄소수 6 내지 24의 방향족 고리를 형성할 수 있으며,

In Chemical Formula 1, q is an integer of 0 to 4, at least one of R1, R2, R3, and R4 is a radical selected from the group consisting of Chemical Formulas 1a and 1b and 나머지 R1 except that it is a radical of Chemical Formula 1a or 1b. To R4 are the same as or different from each other, and each independently hydrogen; halogen; Substituted or substituted substituted linear or branched alkyl of 1 to 20 carbon atoms; Substituted or unsubstituted linear or branched alkenyl having 2 to 20 carbon atoms; Substituted or unsubstituted linear or branched alkynyl having 2 to 20 carbon atoms; Substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Substituted or unsubstituted aryl having 6 to 40 carbon atoms; And a polar functional group including at least one selected from oxygen, nitrogen, phosphorus, sulfur, silmecon, and boron, wherein R1 to R4 are hydrogen; halogen; Or when it is not a polar functional group, one or more combinations selected from the group consisting of R1 and R2, R3 and R4 are connected to each other to form an alkylidene group having 1 to 10 carbon atoms, or R1 or R2 is any one of R3 and R4 Linked to form a saturated or unsaturated aliphatic ring of 4 to 12 carbon atoms, or an aromatic ring of 6 to 24 carbon atoms,

 [Formula 1a] [Formula 1b]

상기 화학식 1 a 및 1 b에서 , A는 단순결합, 산소, 황 또는 -NH-이고， B는 단순결합， 치환 또는 비치환된 탄소수 1 내지 20의 알킬렌， 카보닐, 카르복시， 에스테르， 치환 또는 비치환된 탄소수 6 내지 40의 아릴렌， 및 치환 또는 비치환된 탄소수 6 내지 40의 해테로아릴렌으로 아루어진 군에서 선택되고， X는 산소 또는 황이고; R9는 단순결합, 치환 또는 비치환된 탄소수 1 내지 20와 알킬렌, 치환 또는 비치환된 탄소수 2 내지 20의 알케닐렌， 치환 또는 비치환된 탄소수 3 내지 12의 시클로알킬렌, 치환 또는 비 치환된 탄소수 6 내지 40의 아릴렌， 치환 또는 비치환된 탄소수 7 내지 15의 아르알킬렌， 및 치환 또는 비치환된 탄소수 2 내지 20의 알키 닐렌으로 이루어진 군에서 선택되며 , R10 내지 R14 중 적어도 하나는 -L-R15-R16- (치환 또는 비 치환된 탄소수 6 내지 40의 아릴)로 표시되는 라디칼이고, 이를 제외 한 나머지 R10 내지 R14는 서로 동일하거나 상이하고， 각각 독립적으로 수소, 할로겐, 치환 또는 비치환된 탄소수 1 내지 20의 알킬; 치환 또는 비치환된 탄소수 1 내지 20의 알콕시 ; 치환 또는 비치환된 탄소수 6 내지 30의 아릴옥시 ; 치환 또는 비치환된 탄소수 6 내지 40의 아릴 및 14족， 15족 또는 16족의 헤테로 원소를 포함하는 탄소수 6 내지 40의 헤테로 아릴로 이루어진 군에서 선택되고, L은 산소, 황, -NH-, 치환 또는 비치환된 탄소수 1 내지 20의 알킬렌, 카보닐, 카르복시， -CONH- 및 치환 또는 비치환된 탄소수 6 내지 40의 아릴렌으로 이루어진 군에서 선택되고， R15는 치환 또는 비 치환된 탄소수 ^'1 내지 10의 알킬이고, R16은 단순결합, -0-, -C(=0)0-, -OC(=O)-, -NH-, -S- 및 -C(=0)-로 이루어진 군에서 선택된다.

In Formula 1 a and 1 b, A is a simple bond, oxygen, sulfur or -NH-, B is a simple bond, substituted or unsubstituted C 1-20 alkylene, carbonyl, carboxy, ester, substituted or Unsubstituted arylene having 6 to 40 carbon atoms, and substituted or unsubstituted heteroarylene having 6 to 40 carbon atoms, X is oxygen or sulfur; R9 is a simple bond, substituted or unsubstituted C1-20 and alkylene, substituted or unsubstituted C2-20 alkenylene, substituted or unsubstituted C3-C12 cycloalkylene, 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, and at least one of R10 to R14 is- Radicals represented by L-R15-R16- (substituted or unsubstituted aryl having 6 to 40 carbon atoms), except for the remaining R10 to R14, which are the same as or different from each other, and are each independently hydrogen, halogen, substituted or unsubstituted Alkyl having 1 to 20 carbon atoms; Substituted or unsubstituted alkoxy having 1 to 20 carbon atoms; Substituted or unsubstituted aryloxy having 6 to 30 carbon atoms; Substituted or unsubstituted aryl having 6 to 40 carbon atoms and heteroaryl having 6 to 40 carbon atoms containing a hetero group of 14, 15 or 16, L is selected from 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 substituted or unsubstituted carbon number ^' Alkyl of 1 to 10, R16 consists of a simple bond, -0-, -C (= 0) 0-, -OC (= 0)-, -NH-, -S- and -C (= 0)- Selected from the group.

In the Russia a cyclic olefin compound, a radical of the -L-R15-R16- (substituted or unsubstituted aryl group having 6 to 40) wherein the linker L is an oxygen, the formula aryl is to be a ^"phenyl It may be a radical represented by 2, in addition to a radical having a variety of aryl and linker L:

[Formula 2]

 In Formula 2, R15 and R16 are as defined in Formula 1, R17 to R21 are the same as or different from each other, and each independently hydrogen; halogen; Substituted or unsubstituted alkyl having 1 to 20 carbon atoms; Substituted or unsubstituted alkoxy having 1 to 20 carbon atoms; Substituted or unsubstituted aryloxy having 6 to 30 carbon atoms; Substituted or unsubstituted aryl having 6 to 40 carbon atoms; It is selected from the group consisting of hetero aryl having 6 to 40 carbon atoms containing a hetero element of Group 14, 15 or 16, and substituted or unsubstituted alkoxy aryl having 6 to 40 carbon atoms. In a more specific example, the radical represented by Formula 2 may be unsubstituted or benzyloxy substituted with halogen or alkoxy having 1 to 3 carbon atoms.

 Such a cyclic leulevine compound has a substituent represented by -L-R15-R16- (substituted or unsubstituted aryl having 6 to 40 carbon atoms) at the terminal of a photoreactive functional group, such as cinnamate structure. Such substituents include those aralkyl structures in which alkyl and aryl are sequentially linked via a linker L. As a bulky chemical structure such as the aralkyl structure is connected to the end of the photoreactive functional group via a linker L, a large free volume can be secured between the photoreactive functional groups. This may be due to steric hindrance of the bulky aralkyl structures.

For this reason, in the photo-alignment polymer and the alignment film prepared from the cyclic ^' olefin compound, photoreactive functional groups such as cinnamate structure can be relatively freely moved (flowed) or reacted in a free space largely secured. Inhibition of other reaction groups or substituents is minimized. As a result, the photoreactive functional groups are relatively free with the change of polarization direction.

0800/CT0ZaM/X3d

0800 / CT0ZaM / X3d

₇₂₂ C OF ₁ o CHNs _i CHH ———— II——II

 刀

2 ₂₅ oC CHN Rs _i CHH—— II——I _I I—

5

 Unsubstituted cycloalkylene having 3 to 12 carbon atoms; Substituted or unsubstituted carbon number 6

Arylene from 10 to 40; Substituted or unsubstituted carbonyloxyylene having 1 to 20 carbon atoms;

Further, in the cyclic olefin compound, the substituted or unsubstituted carbon number

6 to 40 aryl; Or a hetero aryl having 6 to 40 carbon atoms, including a group 14, 15 or 16 hetero element, may be selected from the group consisting of the functional groups listed below, and in addition, may be various aryls or hetero aryls:

이러한 작용기에서, 상기 R ' 10 내지 R ' 18는 서로 동일하거나 상이하고, 나머지는 각각 독립적으로 치환 또는 비치환된 탄소수 1 내지 20의 선형 또는 분지형 알킬， 치환 또는 비치환된 탄소수 1 내지 20의 알콕시， 치환 또는 비치환된 탄소수 6 내지 30의 아릴옥시, 및 치환 또는 비치환된 탄소수 6 내지 40의 아릴로 이루어진 군에서 선택된다.

In such a functional group, the R '10 to R' 18 are the same or different from each other, and the rest are each independently substituted or unsubstituted linear or branched alkyl having 1 to 20 carbon atoms, substituted or unsubstituted C 1 to 20 carbon atoms Alkoxy, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, and substituted or unsubstituted aryl having 6 to 40 carbon atoms.

 In addition, in the cyclic leulevine compound, at least one of R1 to R4 of Formula 1 may be a photoreactive functional group of Formula 1a or 1b, for example, at least one of R1 or R2 may be the photoreactive functional group. have. It is possible to provide a photo-alignment polymer exhibiting the properties of one embodiment by using such a cyclic olepin compound.

 On the other hand, in the structure of the above-described cyclic olefin compound, the definition of each substituent in detail as follows:

 First, "alkyl" means a linear or branched saturated monovalent hydrocarbon moiety of 1 to 20, preferably 1 to 10, more preferably 1 to 6 carbon atoms. The alkyl group may encompass not only unsubstituted but also further substituted by a certain substituent described below. Examples of alkyl groups include methyl, ethyl, propyl, 2-propyl, n-butyl, iso-butyl, tert-butyl, pentyl, nucleus, dodecyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, Dichloromethyl, trichloromethyl, iodomethyl, bromomethyl and the like.

 "Alkenyl" means a linear or branched monovalent hydrocarbon moiety of 2 to 20, preferably 2 to 10, more preferably 2 to 6 carbon atoms comprising at least one carbon-carbon double bond. . Alkenyl groups may be bonded through a carbon atom comprising a carbon-carbon double bond or through a saturated carbon atom. Alkenyl groups may be broadly referred to as unsubstituted as well as those further substituted by the following substituents. Examples of the alkenyl group include ethenyl, 1-propenyl, 2-propenyl, 2-butenyl, 3-butenyl, pentenyl, 5-nucenenyl, dodecenyl, and the like.

"Cycloalkyl" is a saturated or unsaturated of 3 to 12 ring carbons It means a non-aromatic monovalent monocyclic, bicyclic or tricyclic hydrocarbon moiety, and may be referred to collectively further substituted by a certain substituent described below. For example, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclonuxyl, cyclonuxenyl, cycloheptyl, cyclooctyl, decahydronaphthalenyl, adamantyl, norbornyl (i.e., bicyclo [2,2, 1] hept-5-enyl).

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

 "Alkoxyaryl" means that at least one hydrogen atom of the aryl group as defined above is substituted with an alkoxy group. Examples of the alkoxy aryl group are mepsicyphenyl, ethoxyphenyl, propoxyphenyl, appendoxyphenyl, pentoxyphenyl, hexoxyphenyl, hepoxy, octoxy, nanoxy, methoxybiphenyl, methoxynaphthalenyl, Methoxy fluorenyl, methoxy anthracenyl, and the like.

 "Aralkyl" means that at least two hydrogen atoms of the alkyl group as defined above are substituted with an aryl group, and may also be referred to as those further substituted by a specific substituent described below. For example, benzyl, benzhydryl, trityl, etc. are mentioned.

"Alkynyl ¹ " is a linear or branched monovalent hydrocarbon moiety containing from 2 to 20 carbon atoms, preferably from 2 to 10, more preferably from 2 to 6 carbon atoms containing at least one carbon-carbon triple bond. An alkynyl group may be bonded through a carbon atom including a carbon-carbon triple bond or through a saturated carbon atom, and alkynyl group may be broadly referred to as further substituted by the following substituents. For example, ethynyl, propynyl, etc. are mentioned.

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

"Alkenylene ' ¹ is 2 to 1 containing at least one carbon-carbon double bond

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

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

¹¹ arylene "means a divalent monocyclic, bicyclic or tricyclic aromatic hydrocarbon moiety having from 6 to 20, preferably from 6 to 12 ring atoms, further substituted by the following substituents The aromatic moiety includes only carbon atoms, and examples of the arylene group include phenylene and the like.

 "Aralkylene '' means a divalent moiety in which at least one hydrogen atom of the alkyl group defined above is substituted with an aryl group, and may also be referred to as being further substituted by a specific substituent described below. , Benzylene and the like.

 "Alkynylene '' is from 2 to containing at least one carbon-carbon triple bond

20 carbon atoms, preferably 2 to 10, more preferably 2 to 6 linear or branched divalent hydrocarbon sites. Alkynylene groups are grouped via a carbon atom containing a carbon-carbon triple bond or through a saturated carbon atom. Can be combined through. Alkynylene groups can also be referred to collectively further substituted by certain substituents described below. For example, ethynylene, propynylene, etc. are mentioned.

The term "substituted or unsubstituted" described above encompasses not only each of these substituents themselves, but also those further substituted by certain substituents. Examples of substituents that may be substituted are halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy , Halocarbonyloxy, aryloxy, haloaryloxy, silyl, siloxy, or the aforementioned polar functional group ¹¹ containing oxygen, nitrogen, phosphorus, sulfur, silicon or boron.

 The above-mentioned cyclic olephine compound may be prepared according to a conventional method for introducing a cyclic olephine, for example, a predetermined substituent, more specifically, a photoreactive functional group of formula (1a) or (1b), to a norbornene-based compound. For example, condensation reaction of a norbornene (alkyl) ol such as norbornene methanol with a carboxylic acid compound having a photoreactive functional group of Formula 1a or 1b may be used to prepare the cyclic urelepine compound. According to the structure and type of the photoreactive functional group of 1b, the above-described cyclic olefin compound may be prepared by introducing the photoreactive functional group in various ways.

On the other hand, using the above-described cyclic olefin compound can be obtained a photo-oriented polymer to satisfy the characteristics of one embodiment. Such photo-orientable polymers are cyclic olefinic repeating units, which are the main repeating units, and may include repeating units of the following Chemical Formula 3a or 3b: [Formula 3a] [Formula 3b]

 In the formulas 3a and 3b, each independently, m is 50 to 5000, and q, R 1, R 2, R 3, and R 4 are as defined for Formula 1.

Such photo-orientable polymers contain repeating units derived from the above-mentioned cyclic olefin compounds, and because of the bulky aralkyl structure bonded via the linker Lol mediated at the end of the photoreactive functional group, there is a great freedom between the photoreactive functional groups. Space can be secured. For this reason, in the photo-alignment polymer, the photoreactive functional groups can move (flow) or react relatively freely in a free space largely secured. Accordingly, the photo-alignment polymer may exhibit a relatively free change in the orientation direction according to the change in the polarization direction and exhibit excellent secondary photo-alignment, and may satisfy the characteristics of the above-described embodiment. In addition, the photoalignable polymer includes a norbornene-based repeating unit of Formula 3a or 3b as a main repeating unit. Such norbornene-based repeating units are structurally hard, and photo-alignment polymers containing the same have a relatively high glass transition temperature (Tg) of about 30 C C or higher, preferably about 300 to 350 ^° C. It can exhibit excellent thermal stability compared to the.

 Since the definition of each substituent bonded to the photo-alignment polymer has already been described in detail with respect to the cyclic olefin compound of Formula 1, further description thereof will be omitted.

And, the photo-alignment polymer is a repeating unit of the formula 3a or 3b Although it may include only one or more repeating units selected from the group consisting of, it may be a copolymer further comprising other types of repeating units together. Examples of such repeating units include, but are not limited to, cinnamate-based chalcone-based or azo-based photoreactive functional groups (e.g., general photoreactive functional groups in which bulky aralkyl structures are not terminally introduced) It may be a fin repeating unit, an acrylate repeating unit or a cyclic ^' olefin repeating unit. Examples of such repeating units are disclosed in Patent Publication No. 2010-0021751 and the like.

 However, the photo-alignment polymer may be about 50 mol% or more, specifically about 50 to 100 mol%, preferably about 70 mol% so that various properties such as excellent orientation and orientation speed according to Chemical Formula 3a or 3b are not impaired. The above content may include Formula 3a or 3b and a repeating unit.

 In addition, the repeating unit of Formula 3a or 3b constituting the photoalignable polymer may have a polymerization degree of about 50 to 5,000, preferably a polymerization degree of about 100 to 4000, and more preferably about 1000 to 3000. In addition, the photo-alignment polymer may have a weight average molecular weight of about 10000 to 1000000, preferably about 20000 to 500000. Accordingly, the photo-alignment polymer may be appropriately included in the coating composition for forming the alignment layer to exhibit excellent coating properties, but the alignment layer formed therefrom may exhibit excellent liquid crystal alignment.

 The above-described photoalignable polymer may exhibit photoalignment under exposure of polarized light having a wavelength of about 150 to 450 nm, for example, UV Young having a wavelength of about 200 to 400 nm, more specifically, a wavelength of about 280 to 315 nm. Excellent photo-alignment property, orientation speed, etc. can be shown under exposure of the reverse polarization. More specifically, the photo-alignment polymer may absorb UV polarization in the wavelength region of about 270 to 340 nm, more specifically, about 300 nm, and may exhibit the above-described characteristic values with respect to absorbance (AR).

On the other hand, the above-described photo-alignment polymer is a repeating unit of formula 3a or 3b In the case of inclusion, it may be prepared according to the method described below. First, one embodiment of the production method is a step of addition polymerization of the monomer of Formula 1 to form a repeating unit of Formula 3a in the presence of a catalyst composition comprising a procatalyst and a cocatalyst comprising a transition metal of Group 10 Can include:

[Formula 1]

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

At this time, the polymerization reaction may be carried out at a temperature of 10 ^° C to 200 ^° C. If the reaction temperature is less than 10 ^° C. may be lowered the polymerization activity, if the reaction temperature is greater than 200 ^° C catalyst is decomposed it is not preferable.

 In addition, the cocatalyst may include a first cocatalyst which provides a Lewis base capable of weakly coordinating with the metal of the procatalyst; And a second co-catalyst for providing a compound comprising a group 15 electron donor ligand may comprise one or more selected from the group consisting of. Preferably, the cocatalyst may be a catalyst mixture comprising a first cocatalyst that provides the Lewis base, and a second cocatalyst, optionally comprising a neutral Group 15 electron donor ligand.

 In this case, the catalyst mixture may include 1 to 1000 moles of the first cocatalyst and 1 to 1000 moles of the second cocatalyst with respect to 1 mole of the procatalyst. When the content of the first or second cocatalyst is too small, the catalyst activation may not be performed properly, on the contrary, when the content of the first or second cocatalyst is too large, the catalytic activity may be lowered.

As the procatalyst including the Group 10 transition metal, Lewis base is used. Compounds with Lewis base functional groups that easily separate from the Lewis acid-base reactions and break away from the thickened metals are easily separated by the first promoter to provide so that the central transition metals can be converted into catalytically active species. Can be used. Such as [(Allyl) Pd (CI)] ₂ (Allylpalladium c Noride dimer), (CH ₃ C0 ₂ ) ₂ Pd [Palladium (n) acetate], [CH ₃ COCH = C (O−) CH ₃ ] ₂ Pd

[Palladium (?) Acetylacetonate], NiBr (NP (CH ₃ ) ₃ ) ₄ , [PdCI (NB) 0 (CH ₃ )] _2, and the like. In addition, the first co-catalyst that provides a Lewis base that can be weakly coordinated with the metal of the procatalyst is easily reacted with the Lewis base to form a vacancy in the transition metal, and also to stabilize the transition metal thus produced. In order to compound the weakly coordinated bond with the transition metal compound or a compound providing the same can be used. For example, borate such as B (C ₆ F ₅ ) ₃ or borate such as dimethylanilinium tetrakis (pentafluorophenyl) borate, methylaluminoxane (MAO) or AI (C ₂ H) ₅ ) alkyl aluminum such as ₃ , or transition metal halide such as AgSbF ₆ .

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

 In addition, although the first and second cocatalysts may be used separately, these two cocatalysts may be used as a compound to activate the catalyst by making one salt into one salt. For example, a compound or the like made by ion-bonding alkyl phosphine and borane or borate compound may be used.

Through the aforementioned method, a repeating unit of Chemical Formula 3a and a photoalignable polymer including the same may be prepared. In addition, when the photo-alignment polymer further contains an olefin repeat unit, a cyclic olefin repeat unit, an acrylate repeat unit, or the like, these repeat units are formed by a conventional production method of each repeat unit, and the method described above. The photoalignable polymer may be obtained by copolymerization with a repeating unit of Formula 3a. On the other hand, when the photo-alignment polymer includes a repeating unit of Formula 3b, it can be prepared according to another embodiment of the manufacturing method. In another embodiment of the present invention, in the presence of a catalyst composition comprising a procatalyst and a cocatalyst including a transition metal of Group 4, 6, or 8, the monomer of Formula 1 may be ring-opened to form a repeating unit of Formula 3b. Forming a step. As another selectable method, the photo-alignment polymer including the repeating unit represented by Chemical Formula 3b, in the presence of a catalyst composition comprising a procatalyst and a cocatalyst comprising a transition metal of Group 4, Group 6, or Group 8, Norbornene (alkyl) ols, such as norbornene methanol, may be prepared by ring-opening polymerization as a monomer to form a ring-opening polymer having a pentagonal ring, and then introducing a photoreactive functional group into the ring-opening polymer. In this case, the introduction of the photoreactive functional group may proceed as a reaction to condense the ring-opening polymer with a carboxylic acid compound or an acyl chloride compound having a photoreactive functional group corresponding to Formula 1a or 1b. In the ring-opening polymerization step, when hydrogen is added to the divalent bond in the norbornene ring included in the monomer of Chemical Formula 1, ring-opening may proceed, and the polymerization proceeds, so that the repeating unit of Chemical Formula 3b and the photo-oriented polymer including the same Can be prepared. Alternatively, the polymerization and ring opening may be sequentially performed to produce the photoalignable polymer.

The ring-opening polymerization is a procatalyst comprising a transition metal of Group 4 (e.g., Τί, Zr, Hf), Group 6 (e.g. Mo, W), or Group 8 (e.g. Ru, Os), the metal of the procatalyst In the presence of a catalyst mixture comprising a cocatalyst that provides a Lewis base capable of weakly coordinating with and a neutral group 15 and 16 activator that can optionally enhance the activity of the procatalyst metal, You can proceed. In addition, in the presence of such a catalyst mixture, linear alkene, such as 1-alkene and 2-alkene, which can adjust the molecular weight size, is added in an amount of 1 to 100 mol% based on the monomer, ^at a temperature of 10 ^° C. to 200 ^° C. and to proceed with the polymerization, Group 4 (for example, Ti, Zr) or Group 8 to Group 10 and a catalyst containing a transition metal addition of the monomer prepared from 1 to 30 parts by weight _^0/0 (for example, Ru, Ni, Pd) 10 ^° C to 250 ^° C The reaction of hydrogenating the double bond in the norbornene ring can proceed at a temperature.

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

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

 If the content of the promoter is less than 1 mole there is a problem that the catalyst activation is not made, if larger than 100,000 moles there is a problem that the catalyst activity is lowered is not preferred. The activator may not be necessary depending on the type of procatalyst. If the content of the activator is less than 1 mole there is a problem that the catalyst activation is not made, and if it is larger than 100 moles there is a problem that the molecular weight is lowered is not preferred.

 Group 4 (eg Ti, Zr) or Group 8 to be used for the hydrogenation reaction

Group 10 (for example, Ru, Ni, Pd) in the case where the content of the catalyst is smaller than the monomer prepared 1 weight ⁰ /. Containing a transition metal and is a problem in that the hydrogenation does not easily made large when poly than 30 weight _^0/0 It is not preferable because there is a problem of discoloration of the mer.

The procatalyst comprising a transition metal of Group 4 (e.g. Ti, Zr, Hf), Group 6 (e.g. Mo, W), or Group 8 (e.g. Ru, OS) may be added to the cocatalyst for providing Lewis acid. Such as TiCI ₄ , WCI ₆₎ M0CI5, or RuCI ₃ or ZrCI ₄ , which have a functional group that readily participates in the Lewis acid-base reaction and is separated from the central metal so that it can be easily separated and converted into a catalytically active species. Transition metal It may refer to a compound.

In addition, the co-catalyst which provides a Lewis base that can weakly coordinate with the metal of the procatalyst may be borane or borate such as B (C ₆ F ₅ ) ₃ , methylaluminoxane (MAO) or AI (C ₂ H _5). Alkyl aluminum, alkyl aluminum halide, and aluminum halide such as AI ₃ (CH ₃ ) CI ₂ can be used. Alternatively, instead of aluminum, substituents such as lithium, magnesium, germanium, lead, zinc, tin, and silicon may be used. The compound black, which is weakly coordinated with the transition metal compound to stabilize the transition metal thus formed by reacting easily with the Lewis base to make the transition metal empty, is a compound providing the same.

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

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

Through the aforementioned method, a repeating unit of Chemical Formula 3b and a photoalignable polymer including the same may be prepared. Moreover, even when the said photo-alignment polymer further contains an olefin type repeating unit, a cyclic olefin type repeating unit, or an acrylate type repeating unit, these repeating units are prepared by the conventional manufacturing method of each repeating unit. The photo-alignment polymer may be obtained by forming and copolymerizing with the repeating unit of Formula 3b prepared by the above-described method.

 On the other hand, according to another embodiment of the invention, there is provided an alignment film comprising the above-described photo-alignment polymer. Such an alignment film may also include an alignment film in the form of a film as well as a thin film. According to another embodiment of the invention, there is provided a liquid crystal retardation film comprising such an alignment film and a liquid crystal layer on the alignment film.

 Such an alignment film and a liquid crystal retardation film may be manufactured using constituents and production methods known in the art, except for including the above-described photoalignable polymer.

 For example, the alignment layer may be formed by mixing the photo-alignment polymer, the binder resin and the photoinitiator and dissolving it in an organic solvent to obtain a coating composition, then coating the coating composition on a substrate and performing UV curing. At this time, the binder resin may be an acrylate-based resin, more specifically, pentaerythritol triacrylate, dipentaerythroxy nuxaacrylate, trimethylolpropane triacrylate, tris (2-acryl Monooxyethyl) isocyanurate or the like can be used.

 In addition, as the photoinitiator, a conventional photoinitiator known to be usable for the alignment layer may be used without particular limitation, and for example, a photoinitiator known under the trade name 1¾3) " 690 thereof 819 may be used.

 As the organic solvent, toluene, anisole, chlorobenzene, dichloroethane, cyclonucleic acid, cyclopentane, propylene glycol methyl ether acetate, and the like can be used. Since the photo-orientation polymer described above exhibits excellent solubility in various organic solvents, various organic solvents may be used without particular limitation.

In the coating composition, the optical orientation of the polymer, the solid concentration, which comprises a binder resin and a photo-initiator may be about 1 to 15% by weight, about 10 to 15 parts by weight _^0/0 in order to cast the film, the alignment film to form Preferably, in order to form a thin film, about 1 to 5 weight ⁰ /. Is preferable.

 The alignment layer thus formed may be formed on the substrate, for example, as illustrated in FIG. 1, and may be formed under the liquid crystal to align the same. In this case, the substrate may include a substrate including a cyclic polymer, a substrate including an acrylic polymer, or a substrate including a cellulose polymer, and various methods such as bar coating, spin coating, and blade coating of the coating composition. After coating on the substrate to form an alignment film by UV curing.

Photo-alignment may occur due to the UV curing. In this step, alignment may be performed by irradiating polarized UV in a wavelength range of about 150 to 450 nm. In this case, the intensity of the exposure may be about 50 mJ / cin ² to 10 J / cuf of energy, preferably about 500 mJ / cu to 5J / crf. The UV is 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, ② a polarizer plate finely deposited aluminum or metal wire, or ③ quartz Polarized UV selected from polarized UV may be applied by passing or reflecting the Brewster polarizer round due to the reflection of the glass.

As for the substrate temperature at the time of irradiating the said UV, normal temperature is preferable. However, in some cases, it may be irradiated with UV in a heated state within a temperature range of 100 ^° C or less. The film thickness of the final coating film formed by the above series of processes is preferably 30 to 1000 rai.

An alignment film is formed by the method mentioned above, a liquid crystal layer is formed on it, and a liquid crystal phase difference film can be manufactured in accordance with a conventional method. Such a liquid crystal retardation film may be a patterned liquid crystal retardation film applied for realizing a stereoscopic image or the like. In the patterned retardation film, the alignment layer includes two types of alignment layers having different alignment directions of the photo-alignment polymers, and the liquid crystal layer is divided into two regions oriented by each alignment layer and patterned. Can be. As already mentioned above, using the photoalignable polymer of one embodiment,

The patterned liquid crystal retardation film can be produced very easily and efficiently through the front exposure of UV polarization and the secondary exposure of UV polarization applying a single mask process. In particular, such a patterned liquid crystal retardation film may exhibit excellent orientation and the like for each region, and may greatly contribute to the implementation of a good stereoscopic image.

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

 Accordingly, according to another embodiment of the present invention, a display device including the alignment layer or the liquid crystal retardation film is provided. The display device may be a liquid crystal display device in which the alignment film is included for alignment of liquid crystals, or a stereoscopic image display device included in an optical film or a filter such as a liquid crystal retardation film for realizing a stereoscopic image. However, the configuration of these display elements is in accordance with the configuration of the conventional elements, except that the above-described photo-alignment polymer, the alignment film and the like, and the like, detailed description thereof will be omitted. Hereinafter, preferred embodiments are presented to help understand the invention. However, the following examples are only to illustrate the invention, not limited to the invention only. Example 1 Preparation of 4-benzyloxy-dnnamate-5-norbornene (Preparation of Cyclic Olefin Compound)

4-Benzyloxy-benzaldehyde (1 Og, 47 mmol), malonic acid (2eq) and piperidine (O.leq) were dissolved in pyridine (5eq) and stirred at 80 ^° C for 5 hours. After reaction, the phase was lowered to silver and neutralized with 3M HCI. A white solid formed was obtained by filtration. This solid was dried in a vacuum oven to obtain 4-benzyloxy-cinnamic acid. The 4-benzyloxy-cinnamic acid (5g, 19.7mmol), norbornene-5-ol (19mmol), Zr (AcAc) (0.2m ⁰ /.) Was put in xylene, and stirred at 190 ^° C for 24 hours. After stirring, the mixture was washed with 1M HCI and 1M NaHCO 3 aqueous solution, and the solvent was removed to obtain 4-benzyloxy-cinnamate-5-norbornene as a pale yellow solid. NMR (CDCI ₃ (500MHz), ppm): 0.6 (1, m) 1.22 to 1.27 (2, m) 1.47 (1, d) 1.87 (1, m) 2.56 (1, m) 2.93 (1, s) 5.11 (2, s) 5.98 to 6.19 (2, m) 6.36 (1, d) 7.3 to 7.5 (9, m) 7.63 (2, d). Example 2: Preparation of 4-benzyloxy-cinnamate-5-methyl norbornene (Preparation of Cyclic Olefin Compound)

Example 1 Except for using norbornene-5-methanol instead of norbornene-5-ol in Example 1, the reaction was carried out in the same manner and conditions to prepare 4-benzyloxy-cinnamate-5-methyl norbornene. NMR (CDCI ₃ (500MHz) _, ppm): 0.6 (1, m) 1.22 to 1.27 (2, m) 1.47 (1, d) 1.87 (1, m) 2.47 (1, m) 2.93 (1, s) 3.8 To 4.25 (2, m) 5.11 (2, s) 5.98 to 6.19 (2, m) 6.36 (1, d) 7.3 to 7.5 (9, m) 7.63 (2, d). Example 3: Preparation of 4-benzyloxy-cinnamate-5-ethyl norbornene (Preparation of Cyclic Olefin Compound)

Except for using norbomene-5-ethanc> l instead of norbornene-5-ol in Example 1, the reaction was carried out in the same manner and conditions to prepare 4-benzyloxy-cinnamate-5-ethyl norbornene. NMR (CDCI ₃ (500MHz) _, ppm): 0.6 (1, m) 1.22 to 1.27 (2, m) 1.33 to 1.6 (3, m) 1.8 (1, m) 2.43 (1, m) 2.90 (1, s 3.3 to 3.9 (2, m) 5.11 (2, s) 5.95 to 6.17 (2, m) 6.36 (1, d) 7.3 to 7.5 (9, m) 7.63 (2, d). Example 4: Preparation of 4- (4-fluoro-benzyloxy) -cinnamate-5-norbornene ≤ (preparation of cyclic olefin compounds)

4- (4-fluoro-benzyloxy)-instead of 4-benzyloxy-benzaldehyde in Example-1 Except for using benzaldehyde, the reaction was carried out in the same manner and conditions to prepare 4- (4-fluoro-benzyloxy) -cinnamate-5-norbornene¾-. NMR (CDCI ₃ (500MHz), ppm): 0.6 (1, m) 1.22 to 1.27 (2, m) 1.47 (1, d) 1.88 (1, m) 2.67 (1, m) 2.93 (1, s) 5.05 (2, s) 5.97 to 6.11 (2, m) 6.30 (1, d) 6.97 (2, d) 7.1 (2, m) 7.4 (2, m) 7.49 (2, d) 7.65 (1, s). Example 5: Preparation of 4- (4-fluoro-benzyloxy) -cinnamate-5-methyl norbornene (Preparation of Cyclic Olefin Compound)

 Except for using norbornene-5-methan instead of norbornene-5-ol in Example 4, the reaction was carried out in the same manner and conditions to prepare 4- (4-fluora- benzyloxy) -cinnamate-5-methyl norbornene It was.

NMR (CDCI ₃ (500MHz), ppm): 0.6 (1, m) 1.22 to 1.27 (2, m) 1.47 (1, d) 1.88 (1, m) 2.47 (1, m) 2.93 (1, s) 3.75 To 4.3 (2, m) 5.05 (2, s) 5.97 to 6.11 (2, m) 6.30 (1, d) 6.97 (2, d) 7.1 (2, m) 7.4 (2, m) 7.49 (2, d ) 7.65 (1's).

'

 Example 6 Preparation of 4- (4-fluoro-benzyloxy) -cinnamate-5-ethyl norbornene (Preparation of Cyclic Olefin Compound)

Except for using norbornene-5-ethan instead of norbornene-5-ol in Example 4, the reaction was carried out in the same manner and conditions to prepare 4- (4-fluoro-bennzyloxy) -cinnamate-5-ethyl norbornene It was. NMR (CDCI ₃ (500MHz), ppm): 0.6 (1, m) 1.22 to 1.27 (2, m) 1.36 to 1.6 (3, m) 1.86 (1, m) 2.45 (1, m) 2.91 (1, s ) 3.32 to 3.96 (2, m) 5.05 (2, s) 5.97 to 6.11 (2, m) 6.30 (1, d) 6.97 (2, d) 7.1 (2, m) 7.4 (2, m) 7.49 (2 , d) 7.65 (1, s). Example 7: Preparation of 4- (4-methyl-benzyloxy) -cinnamate-5-norbornene ≦ l (Preparation of Cyclic Olefin Compound)

Except for using 4- (4-methyl-benzyloxy) -benzaldehyde instead of 4-Benzyloxy-benzaldehyde in Example 1, the reaction was carried out in the same manner and conditions, 4- (4-methyl-benzyloxy) -cinnamate- 5-norbornene¾ was prepared. NMR (CDCI ₃ (500 MHz), ppm): 0.6 (1, m) 1.21 to 1.27 (2, m) 1.47 (1, d) 1.88 (1, m) 2.37 (3, s) 2.67 (1, m) 2.93 (1, s) 5.05 (2, s) 5.97 to 6.11 (2, m) 6.30 (1, d) 6.97 (2, m) 7.1 (2, m) 7.4 (2, m) 7.45 (2, d) 7.65 (1, s). Example 8: Preparation of 4- (4-methyl-benzyloxy) -cinnamate-5-methyl norbomene (preparation of cyclic olefin compounds) _:

Except for using norbornene-5-methanol instead of norbomene-5-ol in Example 7, the reaction was carried out in the same manner and conditions to prepare 4- (4-methyl-benzyloxy) -cinnamate-5-methyl norbomene It was. NMR (CDCI ₃ (500MHz), ppm): 0.6 (1, m) 1.22 to 1.27 (2, m) 1.47 (1, d) 1.88 (1, m) 2.37 (3, s) 2.47 (1, m) 2.93 (1, s) 3.74 to 4.28 (2, m) 5.05 (2, s) 5.97 to 6.11 (2, m) 6.30 (1, d) 6.97 (2, d) 7.1 (2, m) 7.4 (2, m ) 7.47 (2, d) 7.65 (1, s). Example 9: Preparation of 4- (4-methyl-benzyloxy) -cinnamate-5-ethyl norbomene (Preparation of Cyclolephine Compound)

In Example 7, except that norbornene-5-ethanol was used instead of ^Λ 1 ", the reaction was carried out in the same manner and under the same procedure. 4- (4-methyl-bennzyloxy) -cinnamate-5-ethyl norbomene was prepared.

NMR (CDCI ₃ (500MHz), ppm): 0.6 (1, m) 1.22 to 1.27 (2, m) 1.35 to 1.6 (3, m) 1.86 (1, m) 2.37 (3, s) 2.45 (1 ， m ) 2.91 (1, s) 3.33 to 3.96 (2, m) 5.05 (2, s) 5.97 to 6/11 (2, m) 6.30 (1, d) 6.97 (2, d) 7.1 (2, m) 7.4 (2, m) 7.49 (2, d) 7.65 (1, s). Example 10 Preparation of 4- (4-methoxy-benzyloxy) -cinnamate-5-norbornene≤] (Preparation of Cyclic Olefin Compound)

In Example 1, except that 4- (4-methoxy-benzyloxy) -benzaldehyde was used instead of 4-Benzyloxy-benzaldehyde, the reaction was carried out in the same manner and conditions. 4- (4-methoxy-benzyloxy) -cinnamate -5-norbornene was prepared. NMR (CDCI ₃ (500 MHz), ppm): 0.6 (1, m) 1.20 to 1.27 (2, m)

1.47 (1, d) 1.88 (1, m) 2.67 (1, m) 2.93 (1, s) 4.44 (3, s) 5.05 (2, s) 5.98 to 6.11 (2, m) 6.30 (1, d) 7.01 (2, d) 7.16 (2, m) 7.44 (2, m) 7.51 (2, d) 7.65 (1, s). Example 11: Preparation of 4- (4-methoxy-benzyloxy) -cinnamate-5-methyl norbornene (Preparation of Cycloolefin Compound)

The reaction proceeded in the same manner and under the same procedure, except that norbornene-5-methanol was used instead of norbornene-5-ol in Example 10, 4- (4-methoxy-benzyloxy) -cinnamate-5-methyl norbornene Manufactured. NMR (CDCI ₃ (500 MHz), ppm): 0.6 (1, m) 1.22 to 1.27 (2, m) 1.47 (1, d) 1.88 (1, m) 2.47 (1, m) 2.93 (1, s) 3.75 To 4.3 (2, m) 5.05 (2, s) 5.97 to 6.11 (2, m) 6.30 (1, d) 6.97 (2, d) 7.01 (2, d) 7.16 (2, m) 7.44 (2, m) ) 7.51 (2, d) 7.65 (1, s). Example 12 Preparation of 4- (4-m ethoxy-benzyloxy) -ci n na mate-5-ethyl norbornene (Preparation of Ring-type Elefin Compound)

Embodiment, except that instead of norbomene-5-ethan) yonghan the ^{l Λ} 'norbornene-5-} ol in ^10', the process proceeds to banung by the same method under the same condition, 4- (4-methoxy- benzyloxy) -cinnamate- 5-ethyl norbornene was prepared. NMR (CDCI ₃ (500MHz), ppm): 0.6 (1, m) 1.22 to 1.27 (2, m) 1.33 to 1.57 (3, m) 1.86 (1, m) 2.45 (1, m) 2.92 (1, s ) 3.32 to 3.96 (2, m) 5.05 (2, s) 5.97 to 6.11 (2, m) 6.30 (1, d) 7.01 (2, d) 7.16 (2, m) 7.44 (2, m) 7.51 (2 , d) 7.65 (1, s). Example 13: Preparation of 4- (2-naphthalene-methyloxy) -cinnamate-5-norbornene≤l (Preparation of Cycloolefin Compound)

Except for using 4- (2-naphthalene-methyloxy) -benzaldehyde instead of 4-Benzyloxy-benzaldehyde in Example 1, the reaction was carried out in the same manner and conditions, 4- (2 4- naphthalene-methyloxy) -cinnamate- 5-norbomene was prepared. NMR (CDCI ₃ (500 MHz), ppm): 0.6 (1, m) 1.22 to 1.27 (2, m) 1.47 (1, d) 1.88 (1, m) 2.64 (1, m) 2.93 (1, s) 5.28 (2, s) 5.97 to 6.11 (2, m) 6.31 (1, d) 6.63 (2, d) 7.5 (6, m) 7.9 (4, m). Example 14 Preparation of 4- (2-naphthalene-methyloxy) -cinnamate-5-methyl norbornene (Preparation of Cyclolephleine Compound)

Except for using norbornene-5-methanol-ir instead of norbornene-5-ol in Example 13, reaction was carried out in the same manner and under the same manner, to form 4- (2-naphthalene-methyloxy) -cinnamate-5-methyl norbornene. Prepared. NMR (CDCI ₃ (500 MHz), ppm): 0.6 (1, m) 1.22 to 1, 27 (2, m) 1.47 (1, d) 1.88 (1, m) 2.48 (1, m) 2.91 (1, s ) 3.75 to 4.3 (2, m) 5.28 (2, s) 5.97 to 6.11 (2, m) 6.31 (1, d) 6.63 (2, d) 7.5 (6, m) 7.9 (4, m). Example 15 Preparation of 4- (2-naphthalene-methyloxy) -cinnamate-5-ethyl norbornene (Preparation of Cycloolefin Compound)

Except for using norbornene-5-ethan instead of norbomene-5-ol in Example 13, the reaction was carried out in the same manner and conditions to prepare 4- (2-naphthalene-methyloxy) -cinnamate-5-ethyl norbornene It was. NMR (CDCI ₃ (500 MHz), ppm): 0.6 (1, m) 1.21 to 1.27 (2, m) 1.37 to 1.6 (3, m)

1.86 (1, m) 2.45 (1, m) 2.90 (1, s) 3.62 to 4.05 (2, m) 5.05 (2, s) 5.97 to 6. "(2, m) 6.31 (1, d) 6.63 ( 2, d) 7.5 (6, m) 7.9 (4, m) Example 16: Preparation of 4- (4-methylketone benzyloxy) -dnnamate-5-norbornene (preparation of cyclic olefin compounds)

Thread | Except for the use of 4- (4-methylketone bezyloxy) -benzaldehyde instead of 4-Benzyloxy-benzaldehyde, the reaction was carried out in the same manner and under the same conditions, and 4- (4-methylketone benzyloxy) -cinnamate-5- norbornene was prepared. NMR (CDCI3 (500 MHz), ppm): 0.6 (1, m) 1.22 to 1.27 (2, m) 1.47 (1, d) 1.88 (1, m) 2.67 (1, m) 2.93 (1, s) 3.66 ( 3, s) 5.05 (2, s) 5.97 to 6.11 (2, m) 6.27 (1, d) 7.0 (2, d) 7.1 (2, m) 7.4 (2, m) 7.50 (2, d) 7.65 ( 1, s). Example 17: 4- (4-methylketone benzyloxy) -cinnamate-5-methyl Preparation of norbornene (production of cyclic olefin compounds)

Except for using norbomene-5-methanol ^-instead of norbornene-5-ol in Example 16, the reaction was carried out in the same manner and conditions to prepare 4- (4-methylketone benzyloxy) -cinnamate-5-methyl norbornene It was. NMR (CDCI ₃ (500 MHz), ppm): 0.6 (1, m) 1.22 to 1.27 (2, m) 1.47 (1, d) 1.87 (1, m) 2.47 (1, m) 2.93 (1, s) 3.66 (3, s) 3.8 to 4.25 (2, m) 5.05 (2, s) 5.97 to 6.11 (2, m) 6.27 (1, d) 7.0 (2, d) 7.1 (2, m) 7.4 (2, m ) 7.50 (2, d) 7.65 (1, s). Example 18 Preparation of 4- (4-methylketone benzyloxy) -cinnamate-5-ethyl norbornene (Preparation of Ring-type Elefin Compound)

Except for using norbornene-5-ethanol instead of norbornene-5-ol in Example 16, the reaction was carried out in the same manner and under the same procedure. 4- (4-methylketone benzyloxy) -cinnamate-5-ethyl norbornene Was prepared. NMR (CDCI ₃ (500MHz), ppm): 0.6 (1, m) 1.24 to 1.29 (2, m) 1.33 to 1.6 (3, m) 1.8 (1, m) 2.43 (1, m) 2.90 (1, s ) 3.66 (3, s) 3.8 to 4.25 (2, m) 5.05 (2, s) 5.97 to 6.11 (2 ᅳ m) 6.27 (1, d) 7.0 (2, d) 7.1 (2, m) 7.4 (2 M) 7.50 (2, d) 7.65 (1, s). ^Embodiment, for example 19: 4- (1 -phenyl perfluoroheptyloxy) Preparation of -cinnamate-5-norbornene (Preparation of cyclic eulre pin compound)

Except that 4- (1 -phenyl perfluoroheptyloxy) -benzaldehyde was used instead of 4-Benzyloxy-benzaldehyde in Example 1, reaction was conducted in the same manner and conditions to prepare 4- (1 -phenyl perfluoroheptyloxy) -benzaldehyde. . NMR (CDCI ₃ (500 MHz), ppm): 0.6 (1, m) 1.22 to 1.27 (2, m) 1.47 (1, d) 1.87 (1, m) 2.56 (1, m) 2.93 (1, s) 5.10 (2, s) 5.96 to 6.16 (2, m) 6.55 (1, d) 7.4 to 7.55 (5, m) 7.65 (2, d) 7.68 (4, m). Example 20 Preparation of 4- (1-phenyl perfluoroheptyloxy) -cinnamate-5-methyl norbornene (prepared with a cyclic olefin compound) Except for using norbornene-5-methanol instead of norbornene-5-ol in Example 19, 4- (1-phenyl perfluoroheptyloxy) -cinnamate-5-methyl norbornene was prepared in the same manner and reaction. . NMR (CDCI ₃ (500 MHz), ppm): 0.6 (1, m) 1.22 to 1.27 (2, m) 1.47 (1, d) 1.87 (1, m) 2.56 (1, m) 2.93 (1, s) 3.75 To 4.3 (2, m) 5.10 (2, s) 5.96 to 6.16 (2, m) 6.55 (1, d) 7.4 to 7.55 (5, m) 7.65 (2, d) 7.68 (4, m). Example 21 Preparation of 4- (1-phenyl perfluoroheptyloxy) -cinnamate-5-ethyl norbornene (Preparation of Cycloolefin Compound)

In Example 19, except that norbornene-5-ethanol-i- was used instead of norbornene-5-ol, the reaction was carried out according to the same method and conditions as for 4- (1 -phenyl perfluoroheptyloxy) -cinnamate-5-ethyl norbornene. Prepared. NMR (CDCI ₃ (500MHz), ppm): 0.6 (1, m) 1.22 to 1.27 (2, m) 1.34 to 1.59 (3, m) 1.86 (1, m) 2.56 (1, m) 2.92 (1, s ) 3.31 to 3.96 (2, m) 5.10 (2, s) 5.96 to 6,16 (2, m) 6.55 (1, d) 7.4 to 7.55 (5, m) 7.65 (2, d) 7.68 (4, m ). Example 22 Preparation of 4- (4-benzyloxy) -benzyloxy-cinnamate-5-norbornene ≦ l (Preparation of Cycloolefin Compound)

Example ^{■ The} reaction was carried out in the same manner and conditions except that 4- (4-benzyloxy) -benzyloxy-benzaldehyde was used instead of 4-Benzyloxy-benzaldehyde in Example 1, and 4- (4-benzyloxy) -benzyloxy-cinnamate -5- norbornene was prepared. NMR (CDCI ₃ (500 MHz) .ppm): 0.6 (1, m) 1.22 to 1.27 (2, m) 1.47 (1, d) 1.88 (1, m) 2.67 (1, m) 2.93 (1, s) 5.16 (4, s) 5.97 to 6.11 (2, m) 6.30 (1, d) 6.99 to 7.15 (8, d) 7.4 to 7.51 (5, d) 7.61 (1, s). Example 23 Preparation of 4- (4-benzyloxy) -benzyloxy-cinnamate-5-methyl norbornene (Preparation of Cyclolephine Compound)

In Example 22, norbornene-5-methanol instead of norbornene-5-ol Except for those used, the reaction was carried out in the same manner and conditions to prepare 4- (4-benzyloxy) -benzyloxy-cinnamate-5-methyl norbornene. NMR (CDCI ₃ (500MHz), ppm): 0.6 (1, m) 1.22 to 1.27 (2, m) 1.47 (1, d) 1.88 (1, m) 2.47 (1, m) 2.93 (1, s) 3.75 To 4.3 (2, m) 5.16 (4, s) 5.97 to 6.11 (2, m) 6.30 (1, d) 6.99 to 7.15 (8, d) 7.4 to 7.51 (5, d) 7.61 (1, s). Example 24 Preparation of 4- (4-benzyloxy) -benzyloxy-cinnamate-5-ethyl norbornene (Preparation of Cyclic Olefin Compound)

In Example 22, except for using norbornene-5-ethanol ^ r instead of norbornene-5-ol, the reaction was carried out according to the same method and conditions to obtain 4- (4-benzyloxy) -benzyloxy-cinnamate-5-ethyl norbornene. Prepared. NMR (CDCI ₃ (500 MHz), ppm): 0.6 (1, m) 1.22 to 1.27 (2, m) 1.36 to 1.6 (3, m) 1.86 (1, m) 2.45 (1, m) 2.91 (1, s ) 3.32 to 3.96 (2, m) 5.16 (4, s) 5.97 to 6.11 (2, m) 6.30 (1, d) 6.99 to 7.15 (8, d) 7.4 to 7.51 (5, d) 7.61 (1, s ). Example 25: 4- (4-fluoro-phenyloxy) -benzyloxy-cinnamate-5-norbornene ^ | Preparation (Preparation of Cyclolephine Compound)

The reaction was conducted in the same manner and under the same conditions, except that 4- (4-fluoro-phenyloxy) -benzyloxy-benzaldehyde was used instead of 4-benzyloxy-benzaldehyde in 1 1 1 1 of the sealant, and 4- (4-fluoro- phenyloxy) -benzyloxy-cinnamate-5-norbornene was prepared. NMR (CDCI ₃ (500MHz) _, ppm): 0.6 (1, m) 1.22 to 1.27 (2, m) 1.47 (1, d) 1.88 (1, m) 2.55 (1, m) 2.91 (1, s) 5.08 (4, s) 5.91 to 6.11 (2, m) 6.30 (1, d) 6.97 (2, d) 7.20 (2, m) 7.31 to 7.63 (8, m) 7.68 (1, s) 7.84 (2, d ). Example 26 Preparation of 4- (4-fluoro-phenyloxy) -benzyloxy-cinnamate-5-methyl norbornene (Preparation of Cyclolephine Compound)

In Example 25 norbornene-5-methanol instead of norbornene-5-ol Except for the use, reaction was carried out in the same manner and conditions to prepare 4- (4-fluoro-phenyloxy) -benzyloxy-cinnamate-5-methyl norbornene. NMR (CDCI ₃ (500 MHz), ppm): 0.6 (1, m) 1.22 to 1.27 (2, m) 1.47 (1, d) 1.88 (1, m) 2.55 (1, m) 2.92 (1, s ) 3.75 to 4.3 (2, m) 5.08 (4, s) 5.91 to 6/11 (2, m) 6.30 (1, d) 6.97 (2, d) 7.20 (2, m) 7.31 to 7.63 (8, m 7.68 (1, s) 7.84 (2, d). Example 27 Preparation of 4- (4-fluoro-phenyloxy) -benzyloxy-cinnamate-5-ethyl norbornene (Preparation of Cycloolefin Compound)

Except for using norbomene-5-ethanol instead of norbomene-5-ol in Example 25, the reaction was carried out in the same manner and conditions, 4- (4-fluoro-phenyloxy) -benzyloxy-cinnamate-5-ethyl norbornene Was prepared. NMR (CDCI ₃ (500 MHz), ppm): 0.6 (1, m) 1.22 to 1.27 (2, m) 1.36 to 1.6 (3, m) 1.86 (1, m) 2.55 (1, m) 2.92 (1, s ) 3.32 to 3.96 (2, m) 5.08 (4, s) 5.91 to 6.11 (2, m) 6.30 (1, d) 6.97 (2, d) 7.20 (2, m) 7.31 to 7.63 (8, m) 7.68 (1, s) 7.84 (2, d). Example 28: Preparation of 4- (4-trifluoromethyl) -benzyloxy-cinnamate-5-norbornene (Preparation of Cycloolefin Compound)

Except for using 4- (4-trifluoromethyl) -benzyloxy-benzaldehyde instead of 4-Benzyloxy-benzaldehyde in Example 1, the reaction was carried out in the same manner and conditions, 4- (4-trifluoromethyl) -benzyloxy-cinnamate- 5-norbomene was prepared. NMR (CDCI ₃ (500 MHz) _, ppm): 0.6 (1, m) 1.22 to 1.27 (2, m) 1.47 (1, d) 1.88 (1, m) 2.67 (1, m) 2.93 (1, s) 5.05 (2, s) 5.97 to 6.1 1 (2, m) 6.30 (1, d) 7.11 to 7.25 (4, m) 7.4 (2, m) 7.60 to 7.68 (3, m). Example 29 Preparation of 4- (4-trifluoromethyl) -benzyloxy-cinnamate-5-methyl norbornene (Preparation of Ring-type Elefin Compound)

In Example 28, the reaction was carried out by the same method and conditions except for the use of norbornene-5-methanol instead of norbornene-5-ol, to obtain 4- (4- Trifluoromethyl) -benzyloxy-cinnamate-5-methyl norbornene was prepared. NMR (CDCI ₃ (500 MHz), ppm): 0.6 (1, m) 1.22 to 1.27 (2, m) 1.47 (1, d) 1.88 (1, m) 2.47 (1, m) 2.93 (1, s) 3.74 To 4.28 (2, m) 5.05 (2, s) 5.97 to 6.11 (2, m) 6.30 (1, d) 7.11 to 7.25 (4, m) 7.4 (2, m) 7.60 to 7.68 (3, m). Example 30 Preparation of 4- (4-trifluoromethyl) -benzyloxy-cinnamate-5-ethyl norbornene (prepared with a cyclic olefin compound)

In Example 28, except that norbornene-5-ol was used instead of norbornene-5-ethan, the reaction was carried out by the same method and conditions to prepare 4- (4-trifluoromethyl) -benzyloxy-cinnamate-5-ethyl norbornene. All. NMR (CDCI ₃ (500MHz), ppm): 0.6 (1, m) 1.22 to 1.27 (2, m) 1.36 to 1.6 (3, m) 1.86 (1, m) 2.45 (1, m) 2.91 (1, s ) 3.32 to 3.96 (2, m) 5.05 (2, s) 5.97 to 6.11 (2, m) 6.30 (1, d) 7.11 to 7.25 (4, m) 7.4 (2, m) 7.60 to 7.68 (3, m ). Example 31 Preparation of 4- (4-bromo-benzyloxy) -cinnamate-5-norbornene ^ (Preparation of Cyclolephine Compound)

Except for using 4- (4-bromo-benzyloxy) -benzaldehyde instead of 4-Benzyloxy-benzaldehycle in Example 1, the reaction was carried out in the same manner and conditions, 4- (4-bromo-benzyloxy) -cinnamate- 5-norbornene was prepared. NMR (CDCI ₃ (500 MHz), ppm): 0.6 (1, m) 1.22 to 1.27 (2, m) 1.47 (1, d) 1.88 (1, m)

2.67 (1, m) 2.93 (1, s) 5.05 (2, s) 5.97 to 6.11 (2, m) 6.30 (1, d) 6.97 (2, d) 7.1 (2, m) 7.30 (2, m) 7.45 (2, d) 7.61 (1, s). Example 32 Preparation of 4- (4-bromo-benzyloxy) -cinnamate-5-methyl norbornene (Preparation of Cyclic Olefin Compound)

Except for using norbomene-5-methan instead of norbornene-5-ol in Example 31, the reaction was carried out in the same manner and conditions to prepare 4- (4-bromo-benzyloxy) -cinnamate-5-methyl norbornene It was. NMR (CDCI ₃ (500MHz), ppm): 0.6 (1, m) 1.22 to 1.27 (2, m) 1.47 (1, d) 1.88 (1, m) 2.47 (1, m) 2.93 (1, s) 3.75 To 4.3 (2, m) 5.05 (2, s) 5.97 to 6.11 (2, m) 6.30 (1, d) 6.97 (2, d) 7.1 (2, m) 7.30 (2, m) 7.45 (2, d ) 7.61 (1, s). Example 33 Preparation of 4- (4-bromo-benzyloxy) -cinnamate-5-ethyl norbomene (Preparation of Cyclolephine Compound)

Except for using norbornene-5-ethanol instead of norbornene-5-ol in Example 31, the reaction was carried out in the same manner and conditions to prepare 4- (4-bramo- benzyloxy) -cinnamate-5-ethyl norbornene. . NMR (CDCI ₃ (500MHz), ppm): 0.6 (1, m) 1.22 to 1.27 (2, m) 1.36 to 1.6 (3, m) 1.86 (1, m) 2.45 (1, m) 2.91 (1, s ) 3.32 to 3.96 (2, m) 5.05 (2, s) 5.97 to 6.11 (2, m) 6.30 (1, d) 6.97 (2, d) 7.1 (2, m) 7.30 (2, m) 7.45 (2 , d) 7.61 (1, s). Example 34 4-benzyloxy-cinhamate-5-norbornene ≦] integration

A Schlenk with 250 (schlenk) 4- benzyloxy-cinnamate- 5-norbornene (50mmol) and the solvent of Example 1, a flask was charged with the purified monomer to toluene (400 parts by weight ⁰ /.). And 1-octene (10 mol%) was added. The temperature was lowered to 90 ^° C with stirring, and dissolved in dichloromethane 11 as a catalyst.

_{Pd (OAc) 2 (16 |} jmol) and tricyclo haeksil phosphine (32μ ι), impregnated the borate (dimethylanilinium tetrakiss (pentafluorophenyl) borate) (32μηιοΙ) with dimethylanilinium tetrakispentafluorophenyl not Dimethyl as co-catalyst ^7, For 16 years

The reaction was stirred at 90 ^° C.

After reaction, the reaction product was added to an excess 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 ^° C. for 24 hours to obtain a polymer (Mw = 198 k,

PDI = 3.22, yield = 68%). Example 35 4-benzyloxy-cinnamate-5-methyl norbornene ≤ l polymerization seal I 4-in Example 2 instead of 4-benzyloxy-cinnamate-5-norbornene of Example 1 Except for using benzyloxy-cinnamate-5-methyl norbornene (50mmol) as a monomer, the polymer of Example 35 was obtained in the same manner and in the same manner as in Example 34 (Mw = 162k, PDI = 3.16, yield = 81%). Example 36 4-benzyloxy-cinnamate-5-ethyl norbornene ≦ l thickening

Except for using 4-benzyloxy-cinnamate-5-ethyl norbornene (50mmol) of Example 3 as a monomer instead of 4-benzyloxy-cinnamate-5-norbornene of Example 1 36 polymers were obtained (Mw = 159k, PDI = 4.10, yield = 80%). Example 37 4- (4-fluoro-benzyloxy) -cinnamate-5-norbornene ^ Polymerization 4-benzyloxy-cinnamate-5-norbornene of Example 1 _. Example 4 instead of 4- (4-fluoro-benzyloxy) -cinnamate-5-norbornene (50mmol) ^ r a monomer, except that ^"is carried out in the same manner and conditions as in Example 34, Example 37 to give the polymer of ( Mw = 121 k, PDI = 3.52, yield = 62%). Example 38: Polymerization of 4- (4-fluoro-benzyloxy) -cinnamate-5-methyl norbornene

 Except for 4-benzyloxy-cinnamate-5-norbornene of Example 1, except that 4- (4-fluoro-benzyloxy) -cinnamate-5-methyl norbomene (50minol) of Example 5 was used as the monomer, and was the same as that of Example 34. The polymer of Example 38 was obtained by the method and condition (Mw = 135 k, PDI = 2.94, yield = 82%). Example 39 Polymerization of 4- (4-fluoro-benzyloxy) -cinnamate-5-ethyl norbornene

Example 4 except that 4- (4-fluoro-benzyloxy) -cinnamate-5-ethyl norbornene (50mmol) of Example 6 was used instead of 4-benzyloxy-cinnamate-5-norbornene of Example I 1. Example 39 in the same manner and conditions as in 34 A polymer was obtained (Mw = 144k, PDI = 4.03, yield = 74%). Example 40 4- (4-metyl-benzyloxy) -cinnamate-5-norbornene ^ polymerization 4- (4-methyl-benzyloxy)-of Example 7 instead of 4-benzyloxy-cinnamate-5-norbornene of Example 1 Except for using cinnamate-5-norbornene (50 mmol) as a monomer, the polymer of Example 40 was obtained by the same method and conditions as in Example 34 (Mw = 111 k, PDI = 3.56, yield = 58%). Example 41 Polymerization of 4- (4-methyl-benzyloxy) -cinnamate-5-methyl norbomene

 Except for 4-benzyloxy-cinnamate-5-norbomene of Example 1, except that 4- (4-methyl-benzyloxy) -cinnamate-5-methyl norbomene (50 mmol) of Example 8 was used as the monomer, and was the same as that of Example 34. The methods and conditions gave the polymer of Example 41 (Mw = 134k, PDI = 3.71, yield = 75%). Example 42: Incorporation of 4- (4-methyl-benzyloxy) -cinnamate-5-ethyl norbomene

Example 1 except that 4- (4-methyl-benzyloxy) -cinnamate-5-ethyl norbomene (50mmol) of Example 9 was used instead of 4-benzyloxy-cinnamate-5-norbornene as a monomer. The polymer of Example 42 was obtained by the same method and conditions as 34 (Mw = 130k, PDI = 4.00, yield = 71%). Example 43: 4- (4-methoxy- benzyloxy) -cinnamate-5-norbornene polymerization in Example 1 of 4-benzyloxy-cinnamate-5- norbornene ' instead Example 10 4- (4-methoxy-benzyloxy ) of the - The polymer of Example 43 was obtained in the same manner and in the same manner as in Example 34, except that cinnamate-5-norbornene (50 mmol) was used as the monomer (Mw = 146k, PDI = 3.42, yield = 74%). Example 44: 4- (4-methoxy-benzyloxy) -cinnamate-5-methyl norbomene polymerization

 Same as Example 34, except that 4- (4-methoxy-benzyloxy) -cinnamate-5-methyl norbornene (50mmol) of Example 11 was used as the monomer instead of 4-benzyloxy-cinnamate-5-norbornene of Example 1 The methods and conditions gave the polymer of Example 44 (Mw = 144k, PDI = 3.04, yield = 79%). Example 45 Polymerization of 4- (4-methoxy-benzyloxy) -cinnamate-5-ethyl norbornene

Example 34 except that 4- (4-methoxy-benzyloxy) -cinnamate-5-ethyl norbornene ^■ (50 mmol) of Example 12 was used as the monomer instead of 4-benzyloxy-cinnamate-5-norbornene of Example 1 The polymer of Example 45 was obtained by the same method and conditions as (Mw = 123k, PDI = 3.69, yield = 71%). Example 46: 4- (2-naphthalene-methyloxy) -cinnamate-5-norbornene ^ polymerization

Example 1 of the 4-benzyloxy-cinnamate-5- norbornene instead of the embodiment 13 of the ^■ 4- (2-naphthalene-methyloxy) in the same manner as Example 34 except that the monomers used in -cinnamate-5-norbornene (50mmol) The methods and conditions gave the polymer of Example 46 (Mw = 91 k, PDI = 4.01, yield = 54%). Example 47: Integration of 4- (2-naphthalene-methyloxy) -cinnamate-5-methyl norbornene

Same as Example 34, except that 4- (2-naphthalene-methyloxy) -cinnamate-5-methyl norbornene (50 mmol) of Example 14 was used as the monomer instead of 4-benzyloxy-cinnamate-5-norbornene of Example 1 The polymer of Example 47 was obtained by the method and the conditions (Mw = 83k, PDI = 3.97, yield = 61%). Example 48: 4- (2-naphthalene-methyloxy) -cinnamate-5-ethyl norbornene β 9uaujoqjou-g-9iBUJBUU! 0- (Axo | Aicl9LjOJon | jj8d | Au9L | di: gg ^ γ ^-

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 4-benzyloxy-cinnamate-5-norbornene of Example 1. Instead, the polymer of Example 52 was obtained by the same method and conditions as in Example 34, except that 4- (1 -phenyl perfluoroheptyloxy) -cinnamate-5-norbornene (50 mmol) of Example 19 was used as the monomer (Mw = 1 16k, PDI = 3.09, yield = 57%). Example 53 Polymerization of 4- (1 -phenyl perfluoroheptyloxy) -cinnamate-5-methyl norbornene

Example 1 of the 4-benzyloxy-cinnamate-5- norbornene against ^", except that a new embodiment 20 of 4- (1 -phenyl perfluoroheptyloxy) -cinnamate- 5-methyl norbornene (50mmol) as the monomer in Example 34 and In the same manner and under the same conditions, the polymer of Example 53 was obtained (Mw = 105 k, P = 3.88, yield = 69%). Example 54 Polymerization of 4- (1 -phenyl perfluoroheptyloxy) -cinnamate-5-ethyl norbornene

 Except for 4-benzyloxy-cinnamate-5-norbornene of Example 1, except that 4- (1 -phenyl pert I uoroheptyloxy) -ci n na mate-5-ethyl norbornene (50 mmol) of Example 21 was used as a monomer. In the same manner and conditions as in Example 34, the polymer of Example 54 was obtained (Mw = 87 k, P = 4.62, yield = 51%). Example 55 Polymerization of 4- (4-benzyloxy) -benzyloxy-cinnamate-5-norbornene

The same method as in Example 34, except that 4- (4-benzyloxy) -benzyloxy-cinnamate-5-norbornene (50 mmol) of Example 22 was used as the monomer instead of 4-benzyloxy-cinnamate-5-norbomene of Example 1. And the polymer of Example 55 was obtained under conditions (Mw = 137k, P = 3.19, yield = 68%). Example 56: 4- (4-benzyloxy) -benzyloxy-cinnamate-5-methyl norbornene _// u O sssooS _O SMld 8988sAV

polymerization of norbornene

 Example 34 except that 4- (4-fluoro-phenyloxy) -benzyloxy-cinnamate-5-ethyl norbornene (50 mmol) of Example 27 was used as the monomer instead of 4-benzyloxy-cinnamate-5-norbornene of Example 1 The polymer of Example 60 was obtained by the same method and conditions as (Mw = 116k, PDI = 4.17, yield = 68%). Example 61: Polymerization of 4- (4-trifluoromethyl) -benzyloxy-cinnamate-5-norbornene

 The same method as in Example 34, except that 4- (4-trifluoromethyl) -benzyloxy-cinnamate-5-norbornene (50 mmol) of Example 28 was used as the monomer instead of 4-benzyloxy-cinnamate-5-norbornene of Example 1 And the polymer of Example 61 was obtained under conditions (Mw = 133k, PDI = 3.10, yield = 44%). Example 62: Polymerization of 4- (4-trifluoromethyl) -benzyloxy-cinnamate-5-methyl norbornene

 Except for 4-benzyloxy-cinnamate-5-norbornene of Example 1, except that 4- (4-trifluoromethyl) -benzyloxy-cinnamate-5-methyl norbornene (50 mmol) of Example 29 was used as the monomer, and was the same as that of Example 34. The polymer of Example 62 was obtained by the method and condition (Mw = 121 k, PDI = 3.38, yield = 48%). Example 63: Incorporation of 4- (4-trifluoromethyl) -benzyloxy-cinnamate-5-ethyl norbornene

Except for 4-benzyloxy-cinnamate-5-norbornene of Example ¹ , except that 4- (4-trifluoromethyl) -benzyloxy-cinnamate-5-ethyl norbornene (50 mmol) of Example 30 was used as the monomer, and was the same as that of Example 34. The polymer of Example 63 was obtained by the method and condition (Mw = 127k, PDI = 3.32, yield = 41%). Example 64: Polymerization of 4- (4-bromo-benzyloxy) -cinnamate-5-norbornene The same method as in Example 34, except that 4- (4-bromo-benzyloxy) -cinnamate-5-norbornene (50 mmol) of Example 31 was used as the monomer instead of 4-benzyloxy-cinnamate-5-norbornene of Example 1. And the conditions of Example 64 were obtained (Mw = 168k, PDI = 3.06, yield = 74%). Example 65 Polymerization of 4- (4-bromo-benzyloxy) -cinnamate-5-methyl norbomene

 Example 34 and 34 except that 4- (4-bromo-benzyloxy) -cinnamate-5-methyl norbomene (50 mmol) of Example 32 was used as the monomer instead of 4-benzyloxy-cinnamate-5-norbornene of Example 1 1. In the same manner and under the same conditions, the polymer of Example 65 was obtained (Mw = 160k, PDI = 3.24, yield = 83%). Example 66: Polymerization of 4- (4-bromo-benzyloxy) -cinnamate-5-ethyl norbomene

 Example 33 Instead of 4-benzyloxy-cinnamate-5-norbomene of Example 1

The polymer of Example 66 was obtained by the same method and conditions as in Example 34, except that 4- (4-bromo-benzyloxy) -cinnamate-5-ethyl norbomene (50 mmol) was used as the monomer (Mw = 146k, PDI = 3.52, yield = 72%). Example 67 Preparation of Polymers by 4-benzyloxy-cinnamate-5-norbornene ≦ l ring opening methathesis polymerization and hydrogenation reaction

It was charged with 250 ml Schlenk (schlenk) 4-benzyloxy- cinnamate- 5-norbomene toluene (600 parts by weight _^0/0), the information deleted by the solvent into a (50 mmol) into a flask under Ar atmosphere. Triethyl aluminum (1 mmol) as a cocatalyst was first introduced while maintaining the polar flask at a polymerization temperature of 80 ^° C. Then 1 ml of 0.01 M (mol / L) toluene solution (WCI ₈ O.OI mmol, ethane 0.03 mmol) with tungsten hexachloride (WCI ₈ ) and ethanol at a ratio of 1: 3 was added to the flask. It was. Finally, 1-octene as a molecular weight regulator After addition to the (15 mol%) ol polarsk it was reacted with stirring at 80 ^° C. for 18 hours. After the reaction was completed, a small amount of ethyl vinyl ether, a polymerization terminator, was added to the polymerization solution and stirred for 5 minutes.

The polymerization solution was transferred to a 300 mL high pressure reactor, and then 0.06 triethyl aluminum (TEA) was added. Then 0.5 g of grace raney Nickel (slurry phase in water) was added and reacted with stirring at 15 CTC for 2 hours while maintaining the hydrogen pressure at 80 atm. After the reaction was completed, the polymerization solution was dropped into acetone to precipitate, and then filtered and dried in a vacuum oven at 70 ^° C for 15 hours. As a result, a ring-opened hydrogenated polymer of 4-benzyloxy-cinnamate-5-norbornene was obtained (Mw = 83k, PDI = 4.92, yield = 88%,). Example 68 Polymerization by Ring Opening and Hydrogenation of 4-benzyloxy-cinnamate-5-methyl norbornene

 Except for using 4-benzyloxy-cinnamate-5-methyl norbomene (50mmol) of Example 2 as a monomer instead of 4-benzyloxy-cinnamate-5-norbornene of Example 1 in the same manner and in the same manner as in Example 67 A polymer of 68 was obtained (Mw = 87 k, PDI = 4.22, yield = 87%). Example 69: Preparation of polymers by ring-opening polymerization of 4-benzyloxy-cinnamate-5-ethyl norbornene and hydrogenation reaction

Example 1 of the embodiment with 4-benzyloxy-cinnamate-5- norbornene instead the same manner and conditions as in Example 3 4- benzyloxy-cinnamate-5-ethyl norbornene in Example 67 except (50mniol) that a ^"used as a monomer The polymer of Example 69 was obtained (Mw = 71 k, PDI = 4.18, yield = 80%). Example 70 Polymerization by 4- (4-fluoro-benzyloxy) -cinnamate-5-norbornene and Polymer Preparation by Hydrogenation Same as Example 67 except for using the 4- (4-fluoro-benzyloxy) -cinnamate-5-norbornene (50mmol) ¾- monomer of Example 4 instead of the 4-benzyloxy-cinnamate-5-norbornene of Example 1 The polymer of Example 70 was obtained by the method and condition (Mw = 90 k, PDI = 3.40, yield = 71%). Example 71: Polymerization by Ring Opening Polymerization of 4- (4-fluoro-benzyloxy) -cinnamate-5-methyl norbornene and Hydrogenation

 Same as Example 67 except that 4- (4-fluoro-benzyloxy) -cinnamate-5-methyl norbornene (50 mmol) of Example 5 was used as the monomer instead of 4-benzyloxy-cinnamate-5-norbornene of Example 1 The methods and conditions gave the polymer of the example group (Mw = 87k, PDI = 3.98, yield = 76%). Example 72 Preparation of Polymer by Ring Opening Polymerization Hydrogenation of 4- (4-fluoro-benzyloxy) -cinnamate-5-ethyl norbornene

 4- of Example 6 instead of 4-benzyloxy-cinnamate-5-norbornene of Example 1

The polymer of Example 72 was obtained by the same method and conditions as in Example 67, except that (4-fluoro-benzyloxy) -cinnamate-5-ethyl norbornene (50 mmol) was used as the monomer (Mw = 68 k, PDI = 3.51, Yield = 74%). Example 73 Preparation of Polymers by 4- (4-methyl-benzyloxy) -cinnamate-5-norbornene ≦ l Ring Opening Polymerization and Hydrogenation

Example 67 and except that 4- (4-methyl-benzy! Oxy) -cinnamate-5-norbornene (50 mmol) of Example 7 was used as the monomer instead of 4-benzyloxy-cinnamate-5-norbornene of Example 1 In the same manner and under the same conditions, the polymer of Example 73 was obtained (Mw = 69k, PDI = 4.13, yield = 77%). Example 74: Polymerization by Ring Opening Polymerization and Hydrogenation of 4- (4-methyl-benzyloxy) -cinnamate-5-methyl norbornene Same as Example 67 except that 4- (4-methyl-benzyloxy) -cinnamate-5-methyl norbornene (50 mmol) of Example 8 was used as the monomer instead of 4-benzyloxy-cinnamate-5-norbornene of Example 1 The methods and conditions gave the polymer of Example 74 (Mw = 81 k, PDI = 3.49, yield = 84%). Example 75: Polymerization by Ring Opening Polymerization of 4- (4-methyl-benzyloxy) -cinnamate-5-ethyl norbornene and Hydrogenation

 Except for 4-benzyloxy-cinnamate-5-norbornene of Example 1, except that 4- (4-methyl-benzyloxy) -cinnamate-5-ethyl norbornene (50 mmol) of Example 9 was used as the monomer, and was the same as that of Example 67. The polymer of Example 75 was obtained by the method and the conditions (Mw = 55k, PDI = 5.37, yield = 68%). Example 76: Preparation of Polymers by 4- (4-methoxy-benzyloxy) -cinnamate-5-norbornene ^ 'Ring Opening Polymerization and Hydrogenation

 Example 10 instead of 4-benzyloxy-cinnamate-5-norbomene of Example 1

The polymer of Example 76 was obtained by the same method and conditions as in Example 67, except that 4- (4-methoxy-benzyloxy) -cinnamate-5-norbornene (50 mmol) was used as the monomer (Mw = 88 k, PDI = 3.56) , Yield = 84%) Example 77: Preparation of polymer by ring-opening polymerization of 4- (4-m ethoxy-benzyloxy) -ci n mate-5-methyl norbornene and hydrogenation reaction

Same as Example 67 except that 4- (4-methoxy-benzyloxy) -cinnamate-5-methyl norbornene (50mmol) of Example 11 was used as the monomer instead of 4-benzyloxy-cinnamate-5-norbornene of Example 1 The polymer of Example 77 was obtained by the method and condition (Mw = 81 k, PDI = 3.14, yield = 80%). Example 78: Polymerization by Ring Opening Polymerization and Hydrogenation of 4- (4-methoxy-benzyloxy) -cinnamate-5-ethyl norbornene Except for 4-benzyloxy-cinnamate-5-norbornene of Example 1, except that 4- (4-methoxy-benzyloxy) -cinnamate-5-ethyl norbornene (50 mmol) of Example 12 was used as the monomer, and was the same as that of Example 67. The methods and conditions gave the polymer of Example 78 (Mw = 84 k, PDI = 3.90, yield = 73%). Example 79: Polymer preparation by 4- (2-naphthalene-methyloxy) -cinnamate-5-norbornene ^ ring-opening polymerization and hydrogenation reaction

 The same method as in Example 67, except that 4- (2-naphthalene-methyloxy) -cinnamate-5-norbornene (50 mmol) of Example 13 was used as the monomer instead of 4-benzyloxy-cinnamate-5-norbornene of Example 1 And the polymer of Example 79 was obtained under conditions (Mw = 49 k, PDI = 4.53, yield = 55%). Example 80 Polymerization by Ring Opening Polymerization of 4- (2-naphthalene-methyloxy) -cinnamate-5-methyl norbornene and Hydrogenation

 Example 14 instead of 4-benzyloxy-cinnamate-5-norbornene of Example 1

The polymer of Example 80 was obtained by the same method and conditions as in Example 67, except that 4- (2-naphthalene-methyloxy) -cinnamate-5-methyl norbornene (50 mmol) was used as a monomer (Mw = 53 k, PDI = 3.91, yield = 51%). Example 81: Polymerization by Ring Opening Polymerization and Hydrogenation of 4- (2-naphthalene-methyloxy) -cinnamate-5-ethyl norbornene

Same as Example 67, except that 4- (2-naphthalene-methyloxy) -cinnamate-5-ethyl norbornene (50 mmol) of Example 15 was used as the monomer instead of 4-benzyloxy-cinnamate-5-norbornene of Example 1 The polymer of Example 81 was obtained by the method and the conditions (Mw = 59 k, PDI = 3.99, yield = 54%). Example 82 Preparation of Polymers by Ring Opening Polymerization and Hydrogenation of 4- (4-methylketone benzyloxy) -cinnamate-5-norbornene The same method as in Example 67, except that 4- (4-methylketone benzyloxy) -cinnamate-5-norbornene (50 mmol) of Example 16 was used as the monomer instead of 4-benzyloxy-cinnamate-5-norbornene of Example 1 and The polymer of Example 82 was obtained under conditions (Mw = 93 k, PDI = 3.49, yield = 88%). Example 83 Polymer Preparation by Ring Opening Polymerization and Hydrogenation of 4- (4-methylketone benzyloxy) -cinnamate-5-methyl norbornene

 The same method as in Example 67, except that 4- (4-methylketone benzyloxy) -cinnamate-5-methyl norbornene (50 mmol) of Example 17 was used as the monomer instead of 4-benzyloxy-cinnamate-5-norbornene of Example 1. And the polymer of Example 83 was obtained under conditions (Mw = 85k, PDI = 4.26, yield = 81%). Example 84 Polymer Preparation by 4- (4-methylketone benzyloxy) -cinnamate-5-ethyl norbornene ring-opening polymerization and hydrogenation reaction

Instead of 4-benzyloxy-cinnamate-5-norbomene of Example 1 ^{■ of} Example 18

The polymer of Example 84 was obtained by the same method and conditions as in Example 67, except that 4- (4-methylketone benzyloxy) -cinnamate-5-ethyl norbornene (50 mmol) was used as a monomer (Mw = 94 k, PDI = 4.56). , Yield = 71%). Example 85 Polymerization by Ring Opening and Hydrogenation of 4- (1 -phenyl perfluoroheptyloxy) -cinnamate-5-norbornene

The same method as in Example 67, except that 4- (1 -phenyl perfluoroheptyloxy) -cinnamate-5-norbornene (50 mmol) of Example 19 was used as the monomer instead of 4-benzyloxy-cinnamate-5-norbornene of Example 1 and The polymer of Example 85 was obtained under conditions (Mw = 42k, PDI = 4.37, yield = 54%). Example 86: Polymerization by Ring Opening Polymerization of 4- (1 -phenyl perfluoroheptyloxy) -cinnamate-5-methyl norbornene and Hydrogenation The same method as in Example 67, except that 4- (1 -phenyl perfluoroheptyloxy) -cinnamate-5-methyl norbornene (50mmol) of Example 20 was used as the monomer instead of 4-benzyloxy-cinnamate-5-norbornene of Example 1. And the polymer of Example 86 was obtained under conditions (Mw = 45 k, PDI = 3.92, yield = 52%). Example 87: Preparation of polymers by ring-opening polymerization of 4- (1-phenyl perfluoroheptyloxy) -cinnamate-5-ethyl norbornene and hydrogenation reaction

 The same method as in Example 67, except that 4- (1 -phenyl perfluoroheptyloxy) -cinnamate-5-ethyl norbornene (50 mmol) of Example 21 was used as the monomer instead of 4-benzyloxy-cinnamate-5-norbornene of Example 1. And the polymer of Example 87 was obtained under conditions (Mw = 44 k, PDI = 4.52, yield = 43%). Example 88: Preparation of polymer by ring-opening synthesis of 4- (4-benzyloxy) -benzyloxy-cinnamate-5-norbornene and hydrogenation reaction

 Of Example 1 by conducting instead of 4-benzyloxy-cinnamate-5-norbornene]

The polymer of Example 88 was obtained by the same method and conditions as in Example 67, except that 4- (4-benzyloxy) -benzyloxy-cinnamate-5-norbomene (50 mmol) was used as the monomer (Mw = 82 k, PDI = 3.44 , Yield = 70%). Example 89 Preparation of Polymer by Ring Opening and Hydrogenation of 4- (4-benzyloxy) -benzyloxy-cinnamate-5-methyl norbornene

Except for 4-benzyloxy-cinnamate-5-norbornene of Example 1, except that 4- (4-benzyloxy) -benzyloxy-cinnamate-5-methyl norbornene (50 mmol) of Example 23 was used as the monomer, and was the same as that of Example 67. The polymer of Example 89 was obtained by the method and the conditions (Mw = 76k, PDI = 3.67, yield = 73%). Example 90: Ring-opening polymerization of 4- (4-benzyloxy) -benzyloxy-cinnamate-5-ethyl norbornene and polymer preparation by hydrogenation reaction Except for 4-benzyloxy-cinnamate-5-norbornene of Example 1, except that 4- (4-benzyloxy) -benzyloxy-cinnamate-5-ethyl norbornene (50 mmol) of Example 24 was used as the monomer, and was the same as that of Example 67. The polymer of Example 90 was obtained by the method and condition (Mw = 68k, PDI = 4.81, yield = 65%). Example 91 Preparation of Polymer by Ring Opening Polymerization and Hydrogenation of 4- (4-fluoro-phenyloxy) -benzyloxy-cinnamate-5-norbornene

 Example 67 except that 4- (4-fluoro-phenyloxy) -benzyloxy-cinnamate-5-norbornene (50 mmol) of I 25 was used as the monomer instead of 4-benzyloxy-cinnamate-5-norbornene of Example 1 The polymer of Example 91 was obtained by the same methods and conditions as in (Mw = 51k, PDI = 4.72, yield = 41%). Example 92 Preparation of Polymers by Ring Opening Polymerization and Hydrogenation of 4- (4-fluoro-phenyloxy) -benzyloxy-cinnamate-5-methyl norbornene

 Example 1 except that 4- (4-fluoro-phenyloxy) -benzyloxy-cinnamate-5-methyl norbornene (50 mmol) of Example 26 was used instead of 4-benzyloxy-cinnamate-5-norbomene of Example 1 1. The polymer of Example 92 was obtained by the same method and condition as 67 (Mw = 55k, PDI = 4.13, yield = 47%). Example 93: Polymerization by Ring Opening Polymerization of 4- (4-fluoro-phenyloxy) -benzyloxy-cinnamate-5-ethyl norbornene and Hydrogenation

Example 67 except that 4- (4-fluoro-phenyloxy) -benzyloxy-cinnamate-5-ethyl norbornene (50 mmol) of Example 27 was used as the monomer instead of 4-benzyloxy-cinnamate-5-norbornene of Example 1 The polymer of Example 93 was obtained by the same methods and conditions as in (Mw = 49k, PDI = 4.11, yield = 42%). Example 94: Polymerization by Ring Opening Polymerization of 4- (4-trifluoromethyl) -benzyloxy-cinnamate-5-norbornene and Hydrogenation The same method as in Example 67, except that 4- (4-trifluoromethyl) -benzyloxy-cinnamate-5-norbornene (50 mmol) of Example 28 was used as the monomer instead of 4-benzyloxy-cinnamate-5-norbornene of Example 1 And the polymer of Example 94 was obtained under conditions (Mw = 53 k, PDI = 3.01, yield = 56%). Example 95: Polymerization by Ring Opening Polymerization of 4- (4-trifluoromethyl) -benzyloxy-cinnamate-5-methyl norbornene and Hydrogenation

 Except for 4-benzyloxy-cinnamate-5-norbornene of Example 1, except that 4- (4-trifluoromethyl) -benzyloxy-cinnamate-5-methyl norbornene (50 mmol) of Example 29 was used as the monomer, and was the same as that of Example 67. The polymer of Example 95 was obtained by the method and the conditions (Mw = 72k, PDI = 3.95, yield = 55%). Example 96: Polymerization by Ring Opening Polymerization and Hydrogenation of 4- (4-trifluoromethyl) -benzyloxy-cinnamate-5-ethyl norbornene

 Example 30 instead of 4-benzyloxy-cinnamate-5-norbornene of Example 1

The polymer of Example 96 was obtained by the same method and conditions as in Example 67, except that 4- (4-trifluoromethyl) -benzyloxy-cinnamate-5-ethyl norbornene (50 mmol) was used as a monomer (Mw = 59 k, PDI = 3.72, yield = 50%). Example 97: Polymerization by Ring Opening Polymerization of 4- (4-bromo-benzyloxy) -cinnamate-5-norbomene and Hydrogenation

The same method as in Example 67, except that 4- (4-bromo-benzyloxy) -cinnamate-5-norbornene (50 mmol) of Example 31 was used as the monomer instead of 4-benzyloxy-cinnamate-5-norbornene of Example 1. And the polymer of Example 97 was obtained under conditions (Mw = 97 k, PDI = 3.14, yield = 80%). Example 98: Preparation of polymers by ring-opening polymerization of 4- (4-bromo-benzyloxy) -cinnamate-5-methyl norbornene and hydrogenation reaction Same as Example 67 except that 4- (4-bromo-benzyloxy) -cinnamate-5-methyl norbornene (50 mmol) of Example 32 was used as the monomer instead of 4-benzyloxy-cinnamate-5-norbornene of Example 1 The polymer of Example 98 was obtained by the method and condition (Mw = 93 k, PDI = 3.28, yield = 83%). Example .99 Preparation of Polymer by Ring Opening Polymerization and Hydrogenation of 4- (4-bromo-benzyloxy) -cinnamate-5-ethyl norbornene

 Except for 4-benzyloxy-cinnamate-5-norbornene of Example 1, except that 4- (4-bromo-benzyloxy) -cinnamate-5-ethyl norbornene (50 mmol) of Example 33 was used as the monomer, and was the same as that of Example 67. The methods and conditions gave the polymer of Example 99 (Mw = 88 k, PDI = 3.93, yield = 81%).

Experimental Example Preparation and Characterization of the Alignment Film

The toluene solution in which the photo-oriented polymers (2 to 3 wt% of the solution) of Examples 35 and 44 were dissolved on the glass substrate was dropped, and spin coating was performed. After drying for 2 minutes at 10C C, the wavelength of 280 to 315nm and UV polarization having a predetermined polarization direction was irradiated to proceed with the first photoalignment, and the alignment layer was rotated by 90 ^° to turn the polarization direction. UV polarization was performed under the same conditions as the primary photoalignment to proceed the secondary photoalignment. The total light amount during the primary and secondary photo-alignment was adjusted through the irradiation time, the total light amount was as summarized in Table 1 below.

 On the other hand, absorbance was measured through UV absorbance after the first and second photo alignment. At this time, the reference wavelength was used 300nm, and the absorbance was measured using a UV-vis spectrometer. From these absorbance measurement results, the absorbances A1 and A2 after primary and secondary photoalignment were derived, and absorbance (AR) was obtained from Equation 1 below and is shown in Table 1 below.

 [Equation 1]

Absorbance (AR) = (| A1-A2 |) / (A1 + A2) In the above formula, A1 represents the absorbance of the photoalignable polymer measured after the first photoalignment at the maximum absorption wavelength (about 300 nm in this test example) of about 280 to 330 nm, and A2 after the second photoalignment, The flaw of the photo-oriented polymer measured at the maximum absorption wavelength (about 300 nm in this test example) of the wavelength of about 280 to 330 nm.

 In addition, after the first and second optical alignment is performed, the area ratio of the unoriented part (visual discrimination) to the area of the entire alignment layer is calculated, and accordingly, the orientation is evaluated on a five-point basis, and the results are shown in Table 1 below. .

TABLE 1

상기 표 1을 참고하면， 약 0.02 이상의 흡광율 (AR)을 층족하는 ENTRY 1 내지 33는 실시 예의 광배향성 중합체를 사용한 실험 결과로서， 1차 및 2차 배향 후에 우수한 배향성을 나타냄이 확인되 었고， 특히， 2차 배향 후에도 편광 방향에 따른 배향방향의 변화가 자유로워 우수한 배향성을 나타냄이 확인되 었다.

Referring to Table 1, ENTRY 1 to 33 that satisfies the absorbance (AR) of about 0.02 or more, as an experimental result using the photoalignable polymer of the embodiment, it was confirmed that exhibits excellent orientation after the primary and secondary orientation, In particular, it was confirmed that even after the secondary alignment, the change in the orientation direction according to the polarization direction was free, thereby showing excellent orientation.

Claims

Claims [1] A photoalignable polymer comprising a cyclic olefin repeat unit in which at least one photoreactive functional group is substituted, the first UV polarization having a wavelength of 280 to 315 nm and a first polarization direction. After irradiating with a total amount of light of mJ / cm 2 or less and performing the first optical alignment, a second UV polarization having a wavelength of 280 to 315 nm and a second polarization direction changed by 90 ° in the first polarization direction is 60 mJ / cm 2 or less A photoalignable polymer having an absorbance (AR) of 0.02 or more, which is defined by Equation 1 when irradiated with the total amount of light and proceeds with secondary photoalignment: [Equation 1]  Absorbance (AR) = (| A1-A2 |) / (A1 + A2)  Wherein A1 represents the absorbance of the photoalignable polymer measured at the maximum absorption wavelength in wavelengths of 280 to 330 nm after the primary photoalignment, and A2 is measured at the maximum absorption wavelength in wavelengths of 280 to 330 nm after the secondary photoalignment. Absorbance of the photoalignable polymer. [Claim 2]  The photoalignable polymer of claim 1, wherein the absorbance (AR) is 0.02 to 0.08. [Claim 3] The absorbance AR according to claim 1, wherein when the total light amount in the first photoalignment is 20 to 60 mJ / cm ² and the total light amount in the second photoalignment is 3 to 60 mJ / cm ² , Photo-oriented polymer that is 0.05. [Claim 4] The method of claim 1, wherein the total amount of light in the first photo-alignment is 3 to 20 mJ / cm ² , When the total amount of light at the time of ^secondary photo-alignment is 3 to 60 mJ / cm ² , the light absorption polymer (AR) is 0.02 to 0.08. [Claim 5] The photoalignment polymer of claim 4, wherein when the total amount of light upon secondary photoalignment is 15 to 60 mJ / cm ² , the absorbance (AR) is 0.04 to 0.08. [Claim 6]  The photoalignable polymer of claim 1, wherein the cyclic olefin repeat unit comprises a repeat unit of Formula 3a or 3b:  [Formula 3a] [Formula 3b]

 Each independently in Chemical Formulas 3a and 3b,  m is 50 to 5000,  At least one of R1, R2, R3, and R4 is a radical selected from the group consisting of Formulas 1a and 1b, The remaining R 1 to R 4, which is one of the radicals of Formula 1a or 1b, are the same as or different from each other, and each independently hydrogen; halogen; Substituted or unsubstituted linear or branched alkyl having 1 to 20 carbon atoms; Substituted or unsubstituted linear or branched alkenyl having 2 to 20 carbon atoms; Substituted or unsubstituted linear or branched alkynyl having 2 to 20 carbon atoms; Substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Substituted or unsubstituted aryl having 6 to 40 carbon atoms; And oxygen Selected from the group consisting of polar functional groups containing at least one selected from nitrogen, phosphorus, sulfur, silicon, and boron,  R1 to R4 are hydrogen; halogen; Or when it is not a polar functional group, at least one combination selected from the group consisting of R1 and R2, R3 and R4 is connected to each other to form an alkylidene group having 1 to 10 carbon atoms, or R1 or R2 is any one of R3 and R4 May be linked with to form a saturated or unsaturated aliphatic ring having 4 to 12 carbon atoms, or an aromatic ring having 6 to 24 carbon atoms,  [Formula 1a] [Formula 1 b]

In Chemical Formulas 1a and 1 b,  A is a simple bond, oxygen, sulfur or -NH-,  B is a simple bond, substituted or unsubstituted C1-C20 alkylene, carbonyl, carboxy, ester, substituted or unsubstituted C6-C40 arylene, and substituted or unsubstituted C6-C40 hetero Selected from the group consisting of arylene,  X is oxygen or sulfur;  R9 is a simple bond, substituted or unsubstituted alkylene having 1 to 20 carbon atoms, substituted or unsubstituted alkenylene having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkylene having 3 to 12 carbon atoms, substituted or unsubstituted Arylene having 6 to 40 carbon atoms, substituted or unsubstituted 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 aryl having 6 to 40 carbon atoms), except for the remaining R10. O 2014/038868 To R14 are the same as or different from each other, and each independently hydrogen, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms; Substituted or unsubstituted alkoxy having 1 to 20 carbon atoms; Substituted or unsubstituted aryloxy having 6 to 30 carbon atoms; It is selected from the group consisting of substituted or unsubstituted aryl having 6 to 40 carbon atoms and hetero aryl having 6 to 40 carbon atoms containing a hetero element of Group 14, 15 or 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 substituted or unsubstituted alkyl having 1 to 10 carbon atoms,  R16 is selected from the group consisting of a simple bond, -0-, -C (= 0) 0-, -OC (= 0)-, -NH-, -S- and -C (= 0)-. [Claim 7]  The photoalignable polymer of claim 6, wherein the radical of -L-R15-R16- (substituted or unsubstituted aryl having 6 to 40 carbon atoms) is a radical represented by Formula 2 below:  [Formula 2]

R15 and R16 in Chemical Formula 2 are as defined in Chemical Formula 1, and R17 to R21 are the same as or different from each other, and each independently hydrogen; halogen; Substituted or unsubstituted alkyl having 1 to 20 carbon atoms; Substituted or unsubstituted alkoxy having 1 to 20 carbon atoms; Substituted or unsubstituted aryloxy having 6 to 30 carbon atoms; Substituted or unsubstituted aryl having 6 to 40 carbon atoms; 14, 15, or It is selected from the group consisting of hetero aryl having 6 to 40 carbon atoms containing a hetero group of group 16, and substituted or unsubstituted alkoxyaryl having 6 to 40 carbon atoms. [Claim 8]  The photoalignable polymer of claim 7, wherein the radical represented by Chemical Formula 2 is unsubstituted or substituted with halogen or alkoxy having 1 to 3 carbon atoms. [Claim 9]  7. The photoalignable polymer of claim 6 having a weight average molecular weight of 10000 to 1000000. [Claim 10]  The alignment film containing the photo-alignment polymer of any one of Claims 1-9. [Claim 11]  A liquid crystal retardation film comprising the alignment film of claim 10 and a liquid crystal layer on the alignment film. [Claim 12]  The liquid crystal retardation film of claim 11, wherein the alignment layer comprises two types of alignment layers having different alignment directions of photoalignable polymers, and the liquid crystal layer is divided into two regions oriented by the alignment layers and patterned. [Claim 13]  A display element comprising the alignment film of claim 10. [Claim 14] The display element containing the liquid crystal retardation film of Claim 11 or 12. Claim 15  A display element according to claim 14, which is a stereoscopic display device.