KR101555010B1 - Photoreactive polymer and preparation method thereof - Google Patents

Abstract

The present invention relates to a photoreactive polymer exhibiting a faster photoreaction rate and an excellent orientation property, a process for producing the same, and an alignment film comprising the same. The photoreactive polymer contains specific repeating units containing an azo-based functional group in an amount of 50 mol% or more in the entire polymer.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a photoreactive polymer,

The present invention relates to a photoreactive polymer exhibiting a faster photoreaction rate and an excellent orientation property, a process for producing the same, and an alignment film comprising the same.

Recently, liquid crystal displays are emerging as the most competitive display alternative to CRTs because they are lightweight and have low power consumption. In particular, since a thin film transistor liquid crystal display (TFT-LCD) driven by a thin film transistor independently drives individual pixels, the response speed of the liquid crystal is very excellent and high-quality moving images can be realized. It is expanding its scope.

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

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

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

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

The photopolymerization of the photopolymerizable layer by the linearly polarized ultraviolet (UV) light causes the photoreaction of the photoreactive group to form a polymer-oriented liquid crystal alignment layer in which the main chain of the polymer is aligned in a certain direction, Quot;

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

 However, the above-mentioned photo alignment polymers have disadvantages in that the thermal stability of the polymer main chain is deteriorated and the alignment stability or thermal stability of the alignment layer is lowered, or the liquid crystal alignment property is insufficient. For example, a polymer having an acrylic backbone has a disadvantage in that the stability of the alignment layer is greatly deteriorated due to low thermal stability. When the photosensitive group is bound to the main chain, the polymer does not rapidly react with the polarized light irradiated to the alignment layer, . As described above, when the liquid crystal alignment property or the alignment speed is lowered, the process efficiency may be lowered or the liquid crystal alignment of the liquid crystal display device may not be sufficient, so that the dichroic ratio may be small and the contrast may be deteriorated.

Bull. Korean Chem. Soc. 2002, Vol. 23, No. 957, a photoreactive polymer containing repeating units having an azo group bonded as a part of repeating units has been proposed. However, such a photoreactive polymer is not only insufficient in orientation, but also has a problem in that the photoreaction rate is slow and the process efficiency is deteriorated or the contrast of the liquid crystal display element is deteriorated.

The present invention provides a photoreactive polymer exhibiting a faster photoreaction rate and an excellent orientation property and a method for producing the same.

It is another object of the present invention to provide an alignment film including the above-mentioned photoreactive polymer, which can be preferably contained in a liquid crystal display element or the like.

The present invention provides a photoreactive polymer comprising repeating units of the following formula (3) or (4) in an amount of 50 mol% or more in the entire polymer:

[Chemical Formula 3]

Wherein at least one of R ₁ , R ₂ , R ₃ and R ₄ is represented by the following general formulas (1a), (1b) and (1c) And the others are each independently selected from the group consisting of hydrogen; halogen; A substituted or unsubstituted alkyl of 1 to 20 carbon atoms; A substituted or unsubstituted C2 to C20 alkenyl; Substituted or unsubstituted C2-C20 alkynyl; A substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Substituted or unsubstituted C6-C40 aryl; And polar functional groups comprising at least one selected from oxygen, nitrogen, phosphorus, sulfur, silicon, and boron, wherein R ₁ to R ₄ are independently selected from the group consisting of hydrogen; halogen; Alternatively, if a non-polar functional group, R ₁ and R _2, or R ₃ and R ₄ are connected to each other form an alkylidene group having 1 to 10 carbon atoms, or R ₁ or R ₂ is R ₃ and R ₄ in any one of To form a saturated or unsaturated ring having 4 to 12 carbon atoms or an aromatic ring having 6 to 24 carbon atoms,

 [Formula 1a]

[Chemical Formula 1b]

또는

or

[Chemical Formula 1c]

Each of n1, p1, r1 and m1 is an integer of 0 to 4, n2, p2, r2 and m2 are integers of 0 to 5, A is a substituted or unsubstituted B is oxygen, sulfur, -NH-, or a simple bond, and R ₉ is a straight-chain, branched or cyclic alkylene group having 1 to 20 carbon atoms, Substituted or unsubstituted alkylene having 1 to 20 carbon atoms, substituted or unsubstituted alkenylene having 2 to 20 carbon atoms, substituted or unsubstituted alkynylene having 2 to 20 carbon atoms, substituted or unsubstituted C3-C12 Substituted or unsubstituted arylene having 6 to 40 carbon atoms, or substituted or unsubstituted aralkylene having 7 to 15 carbon atoms, R ₁₀ and R ₁₁ are each independently selected from the group consisting of hydrogen, halogen, substituted or unsubstituted carbon number 1 to 20 alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted Is aryl unsubstituted aryloxy, or substituted or unsubstituted C 6 -C 30 unsubstituted 6 to 40 carbon atoms.

The present invention also relates to a process for producing a photoreactive composition comprising a step of subjecting a monomer of formula (1) to an addition polymerization to form a repeating unit of formula (3) in the presence of a catalyst composition comprising a procatalyst comprising a Group 10 transition metal and a cocatalyst, A process for preparing a polymer is provided:

[Chemical Formula 1]

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

The present invention also relates to a process for the production of a polymer comprising the steps of ring-opening polymerization of monomers of formula (1) in the presence of a catalyst composition comprising a cocatalyst and a precatalyst comprising a transition metal of group 4, 6 or 8, Reactive polymer comprising the steps of:

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

The present invention also provides a liquid crystal phase difference film comprising the alignment film and a liquid crystal layer on the alignment film.

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

The photoreactive polymer according to the present invention may exhibit excellent thermal stability by including norbornene repeating units having a high glass transition temperature as a main repeating unit. In addition, since the photoreactive polymer contains a norbornene repeating unit containing a specific azo type photoreactive unit in a relatively large content, it can exhibit a remarkably improved photoreaction rate as well as exhibit excellent orientation and light utilization efficiency .

Accordingly, it is possible to provide an alignment film and a liquid crystal retardation film having excellent properties using the above-mentioned photoreactive polymer, and the process efficiency can be greatly improved.

1 is the < 1 > H NMR data of the polymer obtained in Example 1. Fig.
2 is the 1 H NMR data of the polymer obtained in Comparative Example 1.
3 is a graph showing the results of measurement of anisotropy and UV reactivity measured in Test Example 3. Fig.

Hereinafter, a photoreactive polymer according to embodiments of the present invention, a method for producing the same, and an alignment layer including the photoreactive polymer will be described in detail.

According to an embodiment of the present invention, there is provided a photoreactive polymer comprising repeating units of the following formula (3) or (4) in an amount of 50 mol% or more in the whole polymer:

[Chemical Formula 3]

Wherein at least one of R ₁ , R ₂ , R ₃ and R ₄ is represented by the following general formulas (1a), (1b) and (1c) And the others are each independently selected from the group consisting of hydrogen; halogen; A substituted or unsubstituted alkyl of 1 to 20 carbon atoms; A substituted or unsubstituted C2 to C20 alkenyl; Substituted or unsubstituted C2-C20 alkynyl; A substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Substituted or unsubstituted C6-C40 aryl; And polar functional groups comprising at least one selected from oxygen, nitrogen, phosphorus, sulfur, silicon, and boron, wherein R ₁ to R ₄ are independently selected from the group consisting of hydrogen; halogen; Alternatively, if a non-polar functional group, R ₁ and R _2, or R ₃ and R ₄ are connected to each other form an alkylidene group having 1 to 10 carbon atoms, or R ₁ or R ₂ is R ₃ and R ₄ in any one of To form a saturated or unsaturated ring having 4 to 12 carbon atoms or an aromatic ring having 6 to 24 carbon atoms,

 [Formula 1a]

[Chemical Formula 1b]

또는

or

[Chemical Formula 1c]

Each of n1, p1, r1 and m1 is an integer of 0 to 4, n2, p2, r2 and m2 are integers of 0 to 5, A is a substituted or unsubstituted B is oxygen, sulfur, -NH-, or a simple bond, and R ₉ is a straight-chain, branched or cyclic alkylene group having 1 to 20 carbon atoms, Substituted or unsubstituted alkylene having 1 to 20 carbon atoms, substituted or unsubstituted alkenylene having 2 to 20 carbon atoms, substituted or unsubstituted alkynylene having 2 to 20 carbon atoms, substituted or unsubstituted C3-C12 Substituted or unsubstituted arylene having 6 to 40 carbon atoms, or substituted or unsubstituted aralkylene having 7 to 15 carbon atoms, R ₁₀ and R ₁₁ are each independently selected from the group consisting of hydrogen, halogen, substituted or unsubstituted carbon number 1 to 20 alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted Is aryl unsubstituted aryloxy, or substituted or unsubstituted C 6 -C 30 unsubstituted 6 to 40 carbon atoms.

Such a photoreactive polymer includes a norbornene repeating unit represented by the general formula (3) or (4) to which the specific azo type photoreactive group represented by the general formulas (1a) to (1c) is bonded as a main repeating unit. Since the norbornene repeating unit is structurally hard and the photoreactive polymer containing it is relatively high at a glass transition temperature (Tg) of about 300 DEG C or higher, preferably about 300 to 350 DEG C, It can exhibit excellent thermal stability. In addition, the photoreactive polymer can exhibit excellent orientation because the photoreactive group can move relatively freely in the polymer main chain due to the structural characteristic that the photoreactive group is bonded to the norbornene repeating unit.

As a result of experiments conducted by the inventors of the present invention, the photoreactive polymer exhibits a very rapid photoreaction rate and an orientation rate as previously known, as a specific azo-based photoreactor is combined. . The azo-based photoreactor is capable of absorbing the polarized light and causing a trans-cis isomerization in one direction, thereby inducing a liquid crystal alignment. These photoreaction and orientation mechanisms are predicted to cause faster optical reaction rate and orientation rate than other photoreactive reactors.

In particular, the photoreactive polymer of one embodiment may comprise at least about 50 mole%, specifically about 50 to 100 mole%, more specifically about 60 to 100 mole%, of repeating units of Formula 3 or 4 to which the azo- Or in a high content of about 70 to 100 mol%. Accordingly, the rapid optical reaction rate according to the azo-type photoreactor can be maximized and expressed. On the other hand, as is also supported by the following comparative examples and the like, the repeating unit bonded with the azo-based photoreactor has a low content of about 50 mol% or less, about 40 mol% or less, for example, about 20 mol% It has been found that in the case of the polymers contained, a fast photoreaction rate by the azo-based photoreactor can not be substantially realized. This is due to the low content range, although the photoreaction mechanism of the azo-based photoreactor described above, for example, trans-cis isomerization takes place partially, the low content of the azo-based photoreactive unit contained in the alignment layer Due to the fact that the liquid crystal alignment is not properly expressed or is affected by other randomly disturbing repeating units and is not oriented in the desired direction.

In contrast, the photoreactive polymer of one embodiment can exhibit excellent orientation and thermal stability along with a very high photoreaction rate and orientation rate, and therefore can be suitably applied to an alignment film of a liquid crystal display element and the like, The process efficiency can be greatly improved.

Hereinafter, the photoreactive polymer will be described in more detail.

Although the photoreactive polymer may be a polymer containing only 100 mol% of the repeating units selected from the group consisting of the repeating units of the above formulas (3) and (4), the effect of the photoreactive polymer on the repeating units of the formulas But may further include other repeating units within the range not inhibiting the repeating units. For example, the photoreactive polymer may be a copolymer further comprising a repeating unit represented by the following formula (2a) or (2b), and further includes a repeating unit of the above formula (2a) or (2b) belonging to the norbornene system, Can be represented:

[Chemical Formula 2b]

In Formula 2a and 2b, each independently, m is 50 to 5000, q 'is an integer from 0 to _{4, R 1', R 2} ', R 3' and R ₄ 'are each independently of formula (2c) Radical; Hydrogen; halogen; A substituted or unsubstituted alkyl of 1 to 20 carbon atoms; A substituted or unsubstituted C2 to C20 alkenyl; Substituted or unsubstituted C2-C20 alkynyl; A substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Substituted or unsubstituted C6-C40 aryl; And polar functional groups comprising at least one member selected from the group consisting of oxygen, nitrogen, phosphorus, sulfur, silicon, and boron, and wherein R ₁ 'to R ₄ ' are selected from the group consisting of hydrogen; halogen; Or polarity is not a functional group, R ₁ 'and R _2' or R ₃ 'and R _4' are connected to each other form an alkylidene group having 1 to 10 carbon atoms, or R ₁ 'or R _2' is R ₃ 'And R ₄ ' to form a saturated or unsaturated ring having 4 to 12 carbon atoms or an aromatic ring having 6 to 24 carbon atoms,

[Chemical Formula 2c]

In Formula 2c, 1 is 0 or 1, and D and D 'are each independently a simple bond, a nitrogen, oxygen, sulfur, substituted or unsubstituted linear or branched alkylene having 1 to 20 carbon atoms; A substituted or unsubstituted cycloalkylene having 3 to 12 carbon atoms; A substituted or unsubstituted linear or branched alkylene oxide having 1 to 20 carbon atoms; And a substituted or unsubstituted cycloalkylene oxide having 3 to 12 carbon atoms, X and Y are each independently selected from the group consisting of hydrogen; halogen; Cyano; And substituted or unsubstituted linear or branched alkyl having 1 to 20 carbon atoms, and R ₁₀ 'to R ₁₄ ' are each independently selected from the group consisting of hydrogen, halogen, cyano, substituted or unsubstituted C1- 20 alkyl; A substituted or unsubstituted C1-C20 alkoxy; A substituted or unsubstituted aryloxy having 6 to 30 carbon atoms; Substituted or unsubstituted C6-C40 aryl; A heteroaryl having 6 to 40 carbon atoms containing a heteroatom of Group 14, Group 15 or Group 16, and a substituted or unsubstituted alkoxyaryl having 6 to 40 carbon atoms.

The repeating unit of formula (2a) or (2b) may be a general norbornene repeating unit, but may be a photoreactive repeating unit to which the cinnamate-based photoreactive unit of formula (2c) is bonded. Preferably, at least one of R ₁ ', R ₂ ', R ₃ 'and R ₄ ' is a radical of formula (2c), and the repeating unit of formula (2a) or (2b) may be a photoreactive repeating unit.

As the photoreactive polymer further includes such a cinnamate-based photoreactive repeating unit, it can exhibit better photoreactivity and orientation. In particular, while the azo-based photoreactor exhibits photoreactivity to light in the longer wavelength region that is closer to visible light, the cinnamate-based photoreactor tends to exhibit good photoreactivity to light in the relatively short wavelength UV region. Therefore, when the photoreactive polymer further contains a cinnamate-based repeating unit of formula (2a) or (2b) together with the repeating unit of the formula (3) or (4), the light utilization efficiency can be further improved when a conventional light source is used Light reactivity and orientation.

The repeating unit of the above formula (2a) or (2b) may be contained in an amount excluding the above-mentioned formula (3) or (4), for example, from about 0 mol% to 50 mol% % Or less than or equal to about 0 mole% and less than or equal to 20 mole%. When at least a part of the repeating units of formula (2a) or (2b) comprises a photoreactive unit of formula (2c), about 10 to 50 mol%, more specifically about 20 to 50 mol% Mol%. ≪ / RTI >

On the other hand, in the repeating unit represented by the formula (3) or (4) or the repeating unit represented by the formula (2a) or (2b) constituting the above-mentioned photoreactive polymer, the polar functional group may be selected from the group consisting of the following functional groups, , Sulfur, silicon, or boron. ≪ RTI ID = 0.0 >

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

Each independently of the above-mentioned functional groups, r is an integer of 1 to 10, and R ₅ is substituted or unsubstituted alkylene of 1 to 20 carbon atoms; Substituted or unsubstituted C2-C20 alkenylene; Substituted or unsubstituted C2-C20 alkynylene; A substituted or unsubstituted cycloalkylene having 3 to 12 carbon atoms; Substituted or unsubstituted arylene having 6 to 40 carbon atoms; Substituted or unsubstituted carbonyloxysylene having 1 to 20 carbon atoms; Or a substituted or unsubstituted alkoxysilene having 1 to 20 carbon atoms,

R ₆ , R ₇ , and R ₈ are independently selected from the group consisting of hydrogen; halogen; A substituted or unsubstituted alkyl of 1 to 20 carbon atoms; A substituted or unsubstituted C2 to C20 alkenyl; Substituted or unsubstituted C2-C20 alkynyl; A substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Substituted or unsubstituted C6-C40 aryl; A substituted or unsubstituted C1-C20 alkoxy; And substituted or unsubstituted carbonyloxy of 1 to 20 carbon atoms.

The repeating unit represented by the formula (3) or (4) or the repeating unit represented by the formula (2a) or (2b) constituting the photoreactive polymer has a degree of polymerization of about 50 to 5,000, preferably about 100 to 4000, more preferably about 1000 to 3000 And may have a degree of polymerization. As these repeating units have a polymerization degree within this range, the photoreactive polymer may suitably contain an orienting agent composition for forming an orientation film, thereby exhibiting excellent coating properties.

On the other hand, in the structure of the above-mentioned photoreactive polymer, the definition of each substituent will be specifically described as follows:

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

"Alkenyl" means a linear or branched monovalent hydrocarbon moiety of 2 to 20, preferably 2 to 10, more preferably 2 to 6 carbon atoms, comprising at least one carbon-carbon double bond . The alkenyl group may be bonded through a carbon atom containing a carbon-carbon double bond or through a saturated carbon atom. The alkenyl group is not only unsubstituted, but may also be referred to as being further substituted by a certain substituent group described later. Examples of the alkenyl group include ethenyl, 1-propenyl, 2-propenyl, 2-butenyl, 3-butenyl, pentenyl, 5-hexenyl and dodecenyl.

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

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

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

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

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

"Alkylene" means a linear or branched, saturated divalent hydrocarbon moiety of 1 to 20, preferably 1 to 10, more preferably 1 to 6 carbon atoms. The alkylene group may be referred to as being further substituted by a certain substituent group described later. Examples of the alkylene group include methylene, ethylene, propylene, butylene, hexylene and the like.

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

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

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

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

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

The substitution of the substituents described above with "substituted or unsubstituted" means that not only each of the substituents themselves but also those further substituted by a certain substituent are included. As used herein, examples of the substituent which may be further substituted for each substituent include halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, Alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, haloaryloxy, silyl or siloxy.

The above-mentioned photoreactive polymer may exhibit photoreactivity under exposure to polarized light having a wavelength of about 150 to 450 nm, and may exhibit photoreactivity, for example, a wavelength of about 200 to 400 nm, more specifically a wavelength of about 300 to 390 nm It may exhibit photoreactivity under exposure. Unlike other types of photoreactive reactors, which generally exhibit photoreactivity only for the polarization of the UV region of short wavelength, the photoreactive groups contained in the repeating units of the above formula (3) or (4), i.e., the azo-type functional groups of the formulas And can exhibit excellent photoreactivity and fast photoreaction rate even for long wavelengths of polarized light. Accordingly, the above-mentioned photoreactive polymer and the alignment layer including the same using a light source such as general i-line can exhibit excellent light utilization efficiency. This is because, in the case of an ordinary light source such as the i-line, a light of a wavelength belonging to or near to visible light is also generated in a substantial amount. That is, when the photoreactive polymer is used, the light utilization and efficiency can be further improved because the photoreaction and orientation can proceed by using the light of the wavelength belonging to or near to the visible light generated from the light source. Furthermore, since the photoreactive polymer includes the repeating unit of formula (2a) or (2b) having a cinnamate-based photoreactive group, the photoreaction and orientation can proceed using a larger area of light generated in the light source, The utilization efficiency can be further improved.

As a result, the photoreactive polymer can exhibit excellent photoreactivity and a fast photoreaction rate when exposed to polarized light having a wavelength of about 150 to 450 nm. More specifically, when hayeoteul exposure to polarized light having a wavelength of about 150 to 450nm to the photo-reactive polymer to the strength of about 50 ~ 900mJ / cm ^2, preferably hayeoteul exposed with intensity of approximately 50 ~ 500 mJ / cm ² (T _1/2 ) until the intensity of the stretching mode of the C = C bond included in the above formulas (1a) to (1c) becomes half of the initial value is about 1.5 minutes or less, more specifically about 1 to 1.5 minutes As shown in FIG.

On the other hand, according to another embodiment of the present invention, a method for producing the above-mentioned photoreactive polymer is provided. One embodiment of this method of production comprises the step of addition polymerization of the monomer of formula (1) to form a repeating unit of formula (3) in the presence of a catalyst composition comprising a cocatalyst and a precatalyst comprising a Group 10 transition metal :

[Chemical Formula 1]

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

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

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

At this time, the catalyst mixture may contain 1 to 1000 moles of the first co-catalyst per 1 mole of the catalyst, and the first co-catalyst may include 1 to 1000 moles of the second co-catalyst. If the content of the first catalyst or the second catalyst is excessively small, the catalyst may not be activated properly. On the contrary, if the content of the first catalyst or the second catalyst is excessively large, the catalyst activity may be lowered.

As the precatalyst including the Group 10 transition metal, it is easily separated by the first co-catalyst providing Lewis base and easily participates in the Lewis acid-base reaction so that the central transition metal can be converted into the catalytically active species. A compound having a Lewis base functional group which is released from the metal can be used. For example [(Allyl) Pd (Cl) ] 2 (Allylpalladiumchloride dimer), (CH 3 CO 2) 2 Pd [Palladium (Ⅱ) acetate], [CH 3 COCH = C (O-) CH 3] 2 Pd [Palladium ( ⅱ) acetylacetonate], NiBr (NP (CH 3) 3) 4, [PdCl (NB) O (CH 3)] there are _two and more.

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

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

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

Through the above-described method, the repeating unit represented by formula (3) and the photoreactive polymer of one embodiment including the repeating unit represented by formula (3) can be prepared. Also, a repeating unit represented by the formula (2a) can also be produced through such a production method, thereby forming a photoreactive polymer in the form of a copolymer containing repeating units of the formulas (3) and / or (2a).

On the other hand, when the photoreactive polymer comprises a repeating unit of the formula (4) or alternatively contains a repeating unit of the formula (2b), it can be produced according to another embodiment of the production method. The process of this alternative embodiment is a process for ring-opening polymerization of the monomer of the above formula (1) in the presence of a catalyst composition comprising a precatalyst comprising a transition metal of group 4, 6 or 8 and a cocatalyst, .

In the ring-opening polymerization step, when hydrogen is added to the double bond in the norbornene ring contained in the monomer of the formula (1), the ring opening can proceed and, at the same time, the polymerization proceeds and the repeating unit of the formula (4) and the photoreactive polymer . This production method can also be applied to the production of the repeating unit of formula (2b) and the photoreactive polymer containing it.

The ring-opening polymerization can be carried out in the presence of a catalyst comprising a transition metal of Group 4 (e.g., Ti, Zr, Hf), Group 6 (e.g. Mo, W) or Group 8 (e.g. Ru, Os) In the presence of a catalyst mixture comprising a cocatalyst providing a Lewis base capable of weakly coordinating with the catalyst and optionally a neutral Group 15 and Group 16 activator capable of promoting the activity of the precatalyst metal, . Also, in the presence of such a catalyst mixture, 1 to 100 mol% of a linear alkene such as 1-alkene or 2-alkene capable of controlling the molecular weight size is added to the monomer and polymerization is carried out at a temperature of 10 to 200 ° C. And a catalyst containing a transition metal of Group 4 (e.g., Ti, Zr) or Group 8 to Group 10 (e.g., Ru, Ni, Pd) is added in an amount of 1 to 30 wt% Lt; RTI ID = 0.0 > C, < / RTI > the double bond in the norbornene ring can be hydrogenated.

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

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

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

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

The procatalyst comprising the transition metal of Group 4 (e.g. Ti, Zr, Hf), Group 6 (e.g. Mo, W) or Group 8 (e.g. Ru, Os) Such as TiCl ₄ , WCl ₆ , MoCl _5, or RuCl ₃ or ZrCl ₄ , which have functional groups that are readily involved in the Lewis acid-base reaction and fall off from the center metal, Metal compounds.

The cocatalyst providing the Lewis base capable of weakly coordinating with the metal of the precatalyst may be borane or borate such as B (C ₆ F ₅ ) ₃ , methylaluminoxane (MAO) or Al (C ₂ H ₅ ) _3, Al (CH ₃ ) Cl ₂ , alkylaluminum halides, and aluminum halides. Alternatively, substituents such as lithium, magnesium, germanium, lead, zinc, tin and silicon may be used instead of aluminum. As such, it is a compound which forms a transition metal easily by easily reacting with a Lewis base and weakly binds to a transition metal compound in order to stabilize the transition metal thus produced, or a compound providing the same.

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

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

Through the above-described method, the repeating unit represented by formula (4) and the photoreactive polymer of one embodiment including the repeating unit represented by formula (4) can be prepared. In addition, a repeating unit represented by the formula (2b) can also be produced through such a production method, thereby forming a photoreactive polymer in the form of a copolymer containing repeating units of the formulas (4) and / or (2b).

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

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

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

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

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

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

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

The thus formed alignment film can be formed on the substrate, and can be formed under the liquid crystal and can function to orient it. The substrate may be a substrate comprising a cyclic polymer, a substrate comprising an acrylic polymer, or a substrate comprising a cellulose polymer. The coating composition may be applied by various methods such as bar coating, spin coating and blade coating It may be coated on a substrate and UV-cured to form an alignment film.

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

Examples of the UV include: (1) a polarizing device using a substrate coated with a dielectric anisotropic material on the surface of a transparent substrate such as quartz glass, soda lime glass, soda lime free glass, etc., (2) a polarizer on which fine aluminum or metal wires are deposited, The polarized UV selected from the polarized UV can be applied in such a way as to pass through or reflect the Brewster polarizer or the like due to the reflection of the glass.

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

A liquid crystal phase difference film can be produced according to a conventional method by forming an orientation film by the above-mentioned method, forming a liquid crystal layer thereon.

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

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

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

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

의 중합Example 1:

Polymerization of

1.26 g(3 m㏖)과 용매로 정제된 톨루엔 3 ㎖를 투입하였다. 이 플라스크에 촉매로 디클로로메탄 1 ㎖에 녹인 Pd(OAc)₂ 6.73㎎과 트리사이클로헥실포스핀 7.76 mg, 조촉매로 디메틸아닐리늄 테트라키스펜타플루오로페닐 보레이트(dimethylanilinium tetrakiss(pentafluorophenyl)borate) 6.53 mg을 넣고, 18시간 동안 90 ℃ 에서 교반하면서 반응시켰다. To a 250 mL Schlenk flask was added monomer

1.26 g (3 mmol) of triethylamine and 3 ml of toluene purified with a solvent were added. To this flask was added 6.73 mg of Pd (OAc) ₂ , 7.76 mg of tricyclohexylphosphine and 6.53 mg of dimethylanilinium tetrakis (pentafluorophenyl) borate as a co-catalyst, dissolved in 1 ml of dichloromethane as a catalyst. And the reaction was carried out with stirring at 90 ° C for 18 hours.

After 18 hours of the reaction, the reaction product was poured into an excess amount of ethanol to obtain a white polymer precipitate. The precipitate was filtered with a glass funnel and the recovered polymer was dried in a vacuum oven at 60 DEG C for 24 hours to obtain 1.19 g of a polymer (Mw = 31,000, PDI = 1.7, yield = 94%). The < 1 > H NMR data of the polymer of Example 1 is shown in Fig.

의 중합Example 2:

Polymerization of

3.0 g(6.69 m㏖)과 용매로 정제된 톨루엔 4 ㎖를 투입하였다. 이 플라스크에 촉매로 디클로로메탄 1 ㎖에 녹인 Pd(OAc)₂ 0.75㎎과 트리사이클로헥실포스핀 0.86 mg, 조촉매로 디메틸아닐리늄 테트라키스펜타플루오로페닐 보레이트(dimethylanilinium tetrakiss(pentafluorophenyl)borate) 0.72 mg을 넣고, 18시간 동안 90 ℃ 에서 교반하면서 반응시켰다. To a 250 mL Schlenk flask was added monomer

3.0 g (6.69 mmol) of toluene and 4 ml of solvent-refined toluene were charged. 0.75 mg of Pd (OAc) ₂ dissolved in 1 ml of dichloromethane as a catalyst, 0.86 mg of tricyclohexylphosphine, 0.72 mg of dimethylanilinium tetrakis (pentafluorophenyl) borate as a co-catalyst And the reaction was carried out with stirring at 90 ° C for 18 hours.

After 18 hours of the reaction, the reaction product was poured into an excess amount of ethanol to obtain a white polymer precipitate. The precipitate was filtered with a glass funnel and the recovered polymer was dried in a vacuum oven at 60 DEG C for 24 hours to obtain 2.55 g of a polymer (Mw = 56,000, PDI = 1.9, yield = 85%).

와

의 공중합Example 3:

Wow

Copolymerization of

0.628 g(1.5 m㏖)와

0.249 g(1.5 m㏖)과 용매로 정제된 톨루엔 3 ㎖를 투입하였다. 이 플라스크에 촉매로 디클로로메탄 1 ㎖에 녹인 Pd(OAc)₂ 6.73㎎과 트리사이클로헥실포스핀 7.76 mg, 조촉매로 디메틸아닐리늄 테트라키스펜타플루오로페닐 보레이트(dimethylanilinium tetrakiss(pentafluorophenyl)borate) 6.53 mg을 넣고, 18시간 동안 90 ℃ 에서 교반하면서 반응시켰다. To a 250 mL Schlenk flask was added monomer

0.628 g (1.5 mmol) and

0.249 g (1.5 mmol) of triethylamine and 3 ml of toluene purified with a solvent were added. To this flask was added 6.73 mg of Pd (OAc) ₂ , 7.76 mg of tricyclohexylphosphine and 6.53 mg of dimethylanilinium tetrakis (pentafluorophenyl) borate as a co-catalyst, dissolved in 1 ml of dichloromethane as a catalyst. And the reaction was carried out with stirring at 90 ° C for 18 hours.

After 18 hours of the reaction, the reaction product was poured into an excess amount of ethanol to obtain a white polymer precipitate. The precipitate was filtered with a glass funnel and the recovered polymer was dried in a vacuum oven at 60 DEG C for 24 hours to obtain 0.75 g of a copolymer (Mw = 29,000, PDI = 2.1, yield = 86%).

의 중합Example 4:

Polymerization of

1.46 g(3 m㏖)과 용매로 정제된 톨루엔 3 ㎖를 투입하였다. 이 플라스크에 촉매로 디클로로메탄 1 ㎖에 녹인 Pd(OAc)₂ 6.73㎎과 트리사이클로헥실포스핀 7.76 mg, 조촉매로 디메틸아닐리늄 테트라키스펜타플루오로페닐 보레이트(dimethylanilinium tetrakiss(pentafluorophenyl)borate) 6.53 mg을 넣고, 18시간 동안 90 ℃ 에서 교반하면서 반응시켰다. To a 250 mL Schlenk flask was added monomer

1.46 g (3 mmol) of toluene and 3 ml of solvent-refined toluene were added. To this flask was added 6.73 mg of Pd (OAc) ₂ , 7.76 mg of tricyclohexylphosphine and 6.53 mg of dimethylanilinium tetrakis (pentafluorophenyl) borate as a co-catalyst, dissolved in 1 ml of dichloromethane as a catalyst. And the reaction was carried out with stirring at 90 ° C for 18 hours.

After 18 hours of reaction, the reaction product was poured into excess ethanol to obtain a yellow polymer precipitate. The precipitate was filtered with a glass funnel and the recovered polymer was dried in a vacuum oven at 60 DEG C for 24 hours to obtain 0.88 g of a copolymer (Mw = 61,000, PDI = 2.6, yield = 64%).

의 중합Example 5:

Polymerization of

1.2 g(3 m㏖)과 용매로 정제된 톨루엔 3 ㎖를 투입하였다. 이 플라스크에 촉매로 디클로로메탄 1 ㎖에 녹인 Pd(OAc)₂ 6.73㎎과 트리사이클로헥실포스핀 7.76 mg, 조촉매로 디메틸아닐리늄 테트라키스펜타플루오로페닐 보레이트(dimethylanilinium tetrakiss(pentafluorophenyl)borate) 6.53 mg을 넣고, 18시간 동안 90 ℃ 에서 교반하면서 반응시켰다. To a 250 mL Schlenk flask was added monomer

1.2 g (3 mmol) of triethylamine and 3 ml of toluene purified with a solvent were added. To this flask was added 6.73 mg of Pd (OAc) ₂ , 7.76 mg of tricyclohexylphosphine and 6.53 mg of dimethylanilinium tetrakis (pentafluorophenyl) borate as a co-catalyst, dissolved in 1 ml of dichloromethane as a catalyst. And the reaction was carried out with stirring at 90 ° C for 18 hours.

After 18 hours of reaction, the reaction product was poured into excess ethanol to obtain a yellow polymer precipitate. The precipitate was filtered with a glass funnel, and the recovered polymer was dried in a vacuum oven at 60 DEG C for 24 hours to obtain 1.06 g of a copolymer (Mw = 47,000, PDI = 3.5, yield = 51%).

Example 6: Ring opening methathesis polymerization and hydrogenation of 5-norbornene-2-methanol [

In a 250 ml Schlenk flask under argon atmosphere, 6.20 g (50 mmol) of 5-norbornene-2-methanol was added, and then 34 g of toluene purified by a solvent was added thereto. The flask was charged with 11.4 mg (1.0 mmol) of triethyl aluminum as a cocatalyst while maintaining the polymerization temperature at 80 ° C. Then, 1 ml of a 0.01 M (mol / L) toluene solution (0.01 mmol of WCl ₈ , 0.03 mmol of ethanol) in which tungsten hexachloride (WCl ₈ ) and ethanol were mixed at a ratio of 1: 3 was added to the flask. Finally, 0.84 g (7.5 mmol) of 1-octene as a molecular weight regulator was added to the flask and reacted for 18 hours at 80 ° C with stirring. After the reaction was completed, a small amount of ethylvinyl ether as a polymerization terminator was added to the polymerization solution, and the mixture was stirred for 5 minutes.

The polymerization solution was transferred to a 300 mL high pressure reactor and 0.06 mL triethylaluminum (TEA) was added. Then, 0.50 g of grace raney nickel (slurry phase in water) was added and reacted with stirring at 150 캜 for 2 hours while maintaining the hydrogen pressure at 80 atm. After the reaction was completed, the polymerization solution was dropped on acetone to be precipitated, then filtered and dried in a vacuum oven at 70 캜 for 15 hours. As a result, 5.62 g of a ring-opened hydrogenated polymer of 5-norbornene-2-methanol was obtained (yield = 90.6%, Mw = 69,900, PDI = 4.92).

의 개환 수소첨가 중합체(ring-opened hydrogenated polymer)의 합성Example 7:

Synthesis of Ring-opened Hydrogenated Polymers

(32.5 g, 0.133 mol)를 60 ml THF에 녹인 후, 첨가 플라스크(additional flask)를 사용하여 천천히 넣어주었다. 10분후 반응물을 상온으로 올린 후 18시간 더 교반시켜 주었다. 에틸 아세테이트로 용액을 희석시키고 분액 깔대기로 옮긴 다음 물과 NaHC0₃로 여러 번 씻어준 후 반응액을 아세톤에 떨어뜨려 침전시킨 다음 이를 여과하여 70 ℃ 진공오븐에서 15시간 동안 건조시켰다(수율: 93 %).
(15 g, 0.121 mol) and triethylamine (Aldrich, 61.2 g, 0.605 mol) of the 5-norbornene-2-methanol obtained in Example 6 were added to a 250 mL 2-neck flask, , 50 ml of THF, and the mixture was stirred in an ice-water bath at 0 ° C.

(32.5 g, 0.133 mol) was dissolved in 60 ml of THF and slowly added using an additional flask. After 10 minutes, the reaction was allowed to warm to room temperature and stirred for another 18 hours. The solution was diluted with ethyl acetate, transferred to a separatory funnel, washed several times with water and NaHCO ₃ , and the reaction solution was dropped on acetone to precipitate. The precipitate was filtered and dried in a 70 ° C. vacuum oven for 15 hours (yield: 93% ).

와

의 공중합Example 8:

Wow

Copolymerization of

0.674 g(1.5 m㏖)와

0.43 g(1.5 m㏖)과 용매로 정제된 톨루엔 3 ㎖를 투입하였다. 이 플라스크에 촉매로 디클로로메탄 1 ㎖에 녹인 Pd(OAc)₂ 6.73㎎과 트리사이클로헥실포스핀 7.76 mg, 조촉매로 디메틸아닐리늄 테트라키스펜타플루오로페닐 보레이트(dimethylanilinium tetrakiss(pentafluorophenyl)borate) 6.53 mg을 넣고, 18시간 동안 90 ℃ 에서 교반하면서 반응시켰다. To a 250 mL Schlenk flask was added monomer

0.674 g (1.5 mmol) and

0.43 g (1.5 mmol) of triethylamine and 3 ml of toluene purified with a solvent were added. To this flask was added 6.73 mg of Pd (OAc) ₂ , 7.76 mg of tricyclohexylphosphine and 6.53 mg of dimethylanilinium tetrakis (pentafluorophenyl) borate as a co-catalyst, dissolved in 1 ml of dichloromethane as a catalyst. And the reaction was carried out with stirring at 90 ° C for 18 hours.

After 18 hours of reaction, the reaction product was poured into excess ethanol to obtain a pale yellow polymer precipitate. The precipitate was filtered with a glass funnel and the recovered polymer was dried in a vacuum oven at 60 DEG C for 24 hours to obtain 0.91 g of a copolymer (Mw = 92,000, PDI = 2.96, yield = 82%).

와

의 공중합≪ Comparative Example 1 >

Wow

Copolymerization of

0.251 g(0.6 m㏖)와

0.398 g(2.4 m㏖)과 용매로 정제된 톨루엔 3 ㎖를 투입하였다. 이 플라스크에 촉매로 디클로로메탄 1 ㎖에 녹인 Pd(OAc)₂ 6.73㎎과 트리사이클로헥실포스핀 7.76 mg, 조촉매로 디메틸아닐리늄 테트라키스펜타플루오로페닐 보레이트(dimethylanilinium tetrakiss(pentafluorophenyl)borate) 6.53 mg을 넣고, 18시간 동안 90 ℃ 에서 교반하면서 반응시켰다. To a 250 mL Schlenk flask was added monomer

0.251 g (0.6 mmol) of

0.398 g (2.4 mmol) of triethylamine and 3 ml of solvent-refined toluene were added. To this flask was added 6.73 mg of Pd (OAc) ₂ , 7.76 mg of tricyclohexylphosphine and 6.53 mg of dimethylanilinium tetrakis (pentafluorophenyl) borate as a co-catalyst, dissolved in 1 ml of dichloromethane as a catalyst. And the reaction was carried out with stirring at 90 ° C for 18 hours.

After 18 hours of the reaction, the reaction product was poured into an excess amount of ethanol to obtain a white polymer precipitate. The precipitate was filtered with a glass funnel, and the recovered polymer was dried in a vacuum oven at 60 DEG C for 24 hours to obtain 0.53 g of a copolymer (Mw = 26,000, PDI = 1.88, yield = 82%). The < 1 > H NMR data of the polymer of Comparative Example 1 is shown in Fig.

≪ Preparation Example 1 >: Example 1 Production of alignment film using polymer

모노머를 이용한 광반응성 중합체를 c-펜타논 (c-pentanone) 용매에 2 중량%의 농도로 용해하고, 두께 80 마이크론의 폴리에틸렌 테레프탈레이트 (상품명: SH71, 한국의 SKC사 제조) 기판상에, 건조 후 두께가 1000Å 되도록 롤 코팅 방법으로 코팅하였다. 그 후, 80 ℃ 오븐에서 3 분간 가열하여 코팅막 내부의 용매를 제거하여 코팅막을 형성하였다. The compound prepared in Example 1

A photoreactive polymer using a monomer was dissolved in a c-pentanone solvent at a concentration of 2% by weight, and then dried on a substrate of 80-micron thick polyethylene terephthalate (trade name: SH71, SKC, Korea) Followed by coating with a roll coating method such that the thickness was 1000 Å. Thereafter, the coating film was heated in an oven at 80 캜 for 3 minutes to remove the solvent in the coating film to form a coating film.

The exposure was performed using a high-pressure mercury lamp of 200 mW / cm 2 intensity as a light source and using a wire-grid polarizer manufactured by Moxtek Inc. to emit polarized UV perpendicularly to the direction of the film, To form an alignment film.

Thereafter, a solid content in which 95.0% by weight of a UV-polymerizable cyanobiphenyl acrylate and 5.0% by weight of a photo initiator, IGACURE 907 (manufactured by Ciba-Geigy Co., Switzerland) were mixed was added so that the liquid crystal content per 100 parts by weight of the liquid crystal solution was 25 parts by weight And dissolved in toluene to prepare a polymerizable reactive liquid crystal solution.

The prepared liquid crystal solution was coated on the formed photo alignment layer by a roll coating method to a dry thickness of 1 占 퐉 and then dried at 80 占 폚 for 2 minutes to align the liquid crystal molecules. The orientated liquid crystal film was irradiated with unpolarized UV using a high pressure mercury lamp of 200 mW / cm 2 intensity as a light source to fix the alignment state of the liquid crystal to prepare a retardation film.

The orientation properties of the prepared retardation film were measured by measuring transmittance of light leakage between polarizing plates, and the quantitative retardation value was measured using Axoscan (manufactured by Axomatrix).

<Comparative Production Example 1>

모노머의 중합체를 이용한 광반응성 중합체 대신 모노머로

와

=2:8 (투여한 모노머 mol 비율)의 공중합체를 이용한 점을 제외하고는 제조예 1과 동일한 방법으로 배향막을 제조하였다.
The pure 100%

As a monomer instead of a photoreactive polymer using a polymer of a monomer

Wow

= 2: 8 (molar ratio of the monomer to be administered) was used.

&Lt; Test Example 1 >

Photoreactivity evaluation - FT-IR spectrum

The photoreactivity of the alignment layer was measured by observing the FT-IR spectrum of the liquid crystal alignment layer prepared in Production Example 1 to Comparative Production Example 1 and exposing (using a mercury lamp having an intensity of 20 mW / cm 2) (T _1/2 ) and energy (E _1/2 = 20 mW / cm 2 x t _1/2 ) until the intensity of the stretching mode of C = C bond in 1c becomes half of the initial value . The results are shown in Table 1 below.

Comparing t _1/2 , it can be seen that Production Example 1 is shorter than Comparative Production Example 1 by about 1/2 or more. Thus, it is confirmed that the alignment rate of the liquid crystal alignment layer is excellent when the polymer of the embodiment is used.

T _{1/2 (minutes)} E _{1/2 (J / cm} ² ₎ Production Example 1 0.9 1.1 Comparative Preparation Example 1 2.2 2.6

&Lt; Test Example 2 &

Orientation  evaluation( Degree of light leakage  evaluation)

The orientation of the alignment film was observed with a polarizing microscope between the two polarizers vertically arranged in the liquid crystal retardation film produced in Production Example 1 and Comparative Production Example 1. That is, the liquid crystal phase difference film prepared in Production Example 1 and Comparative Production Example 1 was inserted between vertically arranged polarizers on the basis of polyethylene terephthalate (product name: SH71, manufactured by SKC Co., Ltd., Korea) having a thickness of 80 microns The degree of light leakage was measured by observing with a polarizing microscope how much the transmitted light passed through the polarizing plate and the retardation film. The orientation direction of the liquid crystal was uniform in the retardation film of Production Example 1 regardless of the wavelength of the incident light, but when the alignment film of Comparative Production Example 1 was applied, it was confirmed that the orientation force was lowered and the orientation direction of the liquid crystal was shaken as a result .

&Lt; Test Example 3 >

Anisotropy and UV reactivity were tested using the photoreactive polymer synthesized in Example 1. The 2 wt% cyclopentane solution in which the polymer was dissolved was spin-coated on a silicon wafer at a speed of 1000 rpm and then dried in an 80 ° oven for 1 minute. The change was measured while irradiating the polarized UV from a UV lamp (level 82%) having a capacity of 15 mW / cm 2 for about 60 seconds (irradiating with 0.9 J / cm 2 energy based on 365 nm). The results are shown in Fig. Referring to FIG. 3, anisotropy formation was confirmed immediately after polarized UV irradiation. When the sample is placed in the orthogonal direction than when the sample is placed in the direction parallel to the polarized UV, it can be seen that the absorbance value is large and anisotropy is formed in the orthogonal direction of the polarized UV. Also, from these test results, it was confirmed that the photoreactive polymer of the examples exhibited excellent photoreactivity against polarized light having a long wavelength of about 365 nm, in which the conventional photoreactive polymer does not exhibit photoreactivity well.

Claims (14)

A photoreactive polymer comprising repeating units of the following formula (3) in an amount of 50 mol% or more in the entire polymer:
(3)

In Formula 3,
n is from 50 to 5000, p is an integer from 0 to 4,
At least one of R ₁ , R ₂ , R ₃ , and R ₄ is a radical selected from the group consisting of the following formulas 1a, 1b, and 1c,
Each independently, hydrogen; halogen; A substituted or unsubstituted alkyl of 1 to 20 carbon atoms; A substituted or unsubstituted C2 to C20 alkenyl; Substituted or unsubstituted C2-C20 alkynyl; A substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Substituted or unsubstituted C6-C40 aryl; And polar functional groups comprising at least one selected from oxygen, nitrogen, phosphorus, sulfur, silicon, and boron,
Wherein R ₁ to R ₄ are hydrogen; halogen; Alternatively, if a non-polar functional group, R ₁ and R _2, or R ₃ and R ₄ are connected to each other form an alkylidene group having 1 to 10 carbon atoms, or R ₁ or R ₂ is R ₃ and R ₄ in any one of To form a saturated or unsaturated ring having 4 to 12 carbon atoms or an aromatic ring having 6 to 24 carbon atoms,
[Formula 1a]

[Chemical Formula 1b]

or

[Chemical Formula 1c]

Independently of one another in the formulas (1a), (1b) and (1c)
n1, p1, r1 and m1 are integers of 0 to 4, n2, p2, r2 and m2 are integers of 0 to 5,
A is a substituted or unsubstituted alkylene, carbonyl, carboxy, substituted or unsubstituted arylene having 6 to 40 carbon atoms, or a simple bond,
B is oxygen, sulfur, -NH-, or a simple bond,
R ₉ is a simple bond, substituted or unsubstituted C2 has 1 to 20 alkylene, alkynylene, substituted or unsubstituted substituted or unsubstituted C2 to C20 alkenylene, a substituted or unsubstituted 2 to 20 carbon atoms in the unsubstituted ring A substituted or unsubstituted arylene group having 6 to 40 carbon atoms, or a substituted or unsubstituted arylene group having 7 to 15 carbon atoms,
R ₁₀ and R ₁₁ are independently selected from the group consisting of hydrogen, halogen, substituted or unsubstituted C 1 -C 20 alkyl, substituted or unsubstituted C 1 -C 20 alkoxy, substituted or unsubstituted C 6 -C 30 aryloxy, And unsubstituted aryl having 6 to 40 carbon atoms.
The photoreactive polymer according to claim 1, further comprising a repeating unit represented by the following formula (2a):
(2a)

In the above formula (2a)
m is from 50 to 5000, q 'is an integer from 0 to 4,
R ₁ ', R ₂ ', R ₃ ', and R ₄ ' are each independently a radical of formula (2c); Hydrogen; halogen; A substituted or unsubstituted alkyl of 1 to 20 carbon atoms; A substituted or unsubstituted C2 to C20 alkenyl; Substituted or unsubstituted C2-C20 alkynyl; A substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Substituted or unsubstituted C6-C40 aryl; And polar functional groups comprising at least one selected from oxygen, nitrogen, phosphorus, sulfur, silicon, and boron,
Wherein R ₁ 'to R ₄ ' are hydrogen; halogen; Or polarity is not a functional group, R ₁ 'and R _2' or R ₃ 'and R _4' are connected to each other form an alkylidene group having 1 to 10 carbon atoms, or R ₁ 'or R _2' is R ₃ 'And R ₄ ' to form a saturated or unsaturated ring having 4 to 12 carbon atoms or an aromatic ring having 6 to 24 carbon atoms,
[Chemical Formula 2c]

In Formula 2c, 1 is 0 or 1,
D and D 'are each independently a simple bond, nitrogen, oxygen, sulfur, substituted or unsubstituted linear or branched alkylene having 1 to 20 carbon atoms; A substituted or unsubstituted cycloalkylene having 3 to 12 carbon atoms; A substituted or unsubstituted linear or branched alkylene oxide having 1 to 20 carbon atoms; And a substituted or unsubstituted cycloalkylene oxide having 3 to 12 carbon atoms,
X and Y are each independently hydrogen; halogen; Cyano; And substituted or unsubstituted linear or branched alkyl having 1 to 20 carbon atoms,
R ₁₀ 'to R ₁₄ ' are each independently hydrogen, halogen, cyano, substituted or unsubstituted alkyl of 1 to 20 carbon atoms; A substituted or unsubstituted C1-C20 alkoxy; A substituted or unsubstituted aryloxy having 6 to 30 carbon atoms; Substituted or unsubstituted C6-C40 aryl; A heteroaryl having 6 to 40 carbon atoms containing a heteroatom of Group 14, Group 15 or Group 16, and a substituted or unsubstituted alkoxyaryl having 6 to 40 carbon atoms.
The photoreactive polymer of claim 2, wherein at least one of R ₁ ', R ₂ ', R ₃ ', and R ₄ ' is a radical of formula (2c).
The photoreactive polymer of claim 1 or 2, wherein the polar functional group is selected from the group consisting of the following functional groups:
_{-R 5 OR 6, -OR 6,} -OC (O) OR 6, -R 5 OC (O) OR 6, -C (O) OR 6, -R 5 C (O) OR 6, -C (O _{) r 6, -R 5 C (} O) r 6, -OC (O) r 6, -R 5 OC (O) r 6, - (r 5 O) r -OR 6, - (OR 5) r - _{OR 6, -C (O) -OC} (O) R 6, -R 5 C (O) -OC (O) R 6, -SR 6, -R 5 SR 6, -SSR 6, -R 5 SSR 6 _{, -S (= O) R 6} , -R 5 S (= O) R 6, -R 5 C (= S) R 6 -, -R 5 C (= S) SR 6, -R 5 SO 3 R _{6, -SO 3 R 6, -R} 5 N = C = S, -N = C = S, -NCO, -R 5 -NCO, -CN, -R 5 CN, -NNC (= S) R 6, -R ₅ NNC (= S) R ₆ , -NO ₂ , -R ₅ NO ₂ ,

Each independently of the above-mentioned functional groups, r is an integer of 1 to 10, and R ₅ is substituted or unsubstituted alkylene of 1 to 20 carbon atoms; Substituted or unsubstituted C2-C20 alkenylene; Substituted or unsubstituted C2-C20 alkynylene; A substituted or unsubstituted cycloalkylene having 3 to 12 carbon atoms; Substituted or unsubstituted arylene having 6 to 40 carbon atoms; Substituted or unsubstituted carbonyloxysylene having 1 to 20 carbon atoms; Or a substituted or unsubstituted alkoxysilene having 1 to 20 carbon atoms,
R ₆ , R ₇ , and R ₈ are independently selected from the group consisting of hydrogen; halogen; A substituted or unsubstituted alkyl of 1 to 20 carbon atoms; A substituted or unsubstituted C2 to C20 alkenyl; Substituted or unsubstituted C2-C20 alkynyl; A substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Substituted or unsubstituted C6-C40 aryl; A substituted or unsubstituted C1-C20 alkoxy; And substituted or unsubstituted carbonyloxy of 1 to 20 carbon atoms.
The photoreactive polymer according to claim 1, which comprises 100 mol% of the repeating units of formula (3).
The photoreactive polymer according to Claim 2 or 3, wherein the photoreactive polymer is a copolymer comprising from 50 mol% to less than 100 mol% of the repeating unit represented by Formula (3) and from 0 mol% to 50 mol%
The photoreactive polymer according to claim 1, which exhibits photoreactive under exposure to polarized light having a wavelength of 150 to 450 nm.
delete A process for preparing a photoreactive polymer of claim 1 comprising the step of subjecting a monomer of formula (1) to a recurring unit of formula (3) in the presence of a catalytic composition comprising a transition metal comprising a transition metal of group 10, Way:
[Chemical Formula 1]

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


delete delete An alignment film comprising the photoreactive polymer of claim 1.
13. A liquid crystal phase difference film comprising the alignment film of claim 12 and a liquid crystal layer on an alignment film.
A display device comprising the alignment film of claim 12.

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