KR20150095222A - Photoalignment polymer, optical film comprising the polymer and method for fabricating the optical film - Google Patents

Abstract

Provided are a photoalignment polymer, an optical film comprising the same, and a manufacturing method thereof. A photoalignment polymer, as a polymer compound comprising a functional group having photopolymerization properties and a functional group having photoisomerization properties, can be effectively applied in various optical films and optical devices.

Description

TECHNICAL FIELD [0001] The present invention relates to a photo-orientable polymer, an optical film containing the same, and a method of manufacturing the same,

[0001] The present invention relates to a polymer having light-sensitive properties and a polymer polymerized using the compound as a monomer. More particularly, the present invention relates to a polymer which is sensitive to light of various wavelengths to cause a structural change, Compounds and optical alignment polymers polymerized using the above compounds as monomers, an optical film containing the same, and a process for producing the same.

In recent years, display devices have rapidly developed, and among them, liquid crystal display devices can be said to represent the present display devices.

Such a liquid crystal display (LCD) is a display device that displays pixels by using a principle of selectively passing light by a change in polarization action depending on the arrangement of liquid crystals positioned between polarizers. However, when the display device is formed of only the liquid crystal and the polarizing plate, when the screen is viewed at a viewing angle deviated by more than a certain angle from the front face perpendicular to the screen, the brightness or contrast is remarkably lowered or the light leakage phenomenon occurs.

In order to solve such problems, the polarizing plate is used in an optical film such as a retardation film or a viewing angle compensating film in addition to a polarizing element, or the retardation film or the viewing angle compensating film is separately attached to a display panel. Thus, when an optical film such as a retardation film or a viewing angle compensating film is inserted between a polarizing plate and a liquid crystal display, the color change of the liquid crystal display can be reduced, the viewing angle can be increased, and the brightness can be improved.

Optical films for use in the above-mentioned applications are roughly divided into a stretched film in which a polymer film is stretched to impart optical anisotropy, a liquid crystal film in which a polymerizable liquid crystal compound is coated on a plastic film substrate, and the film is dried and cured by irradiating ultraviolet light have. The stretched film and the liquid crystal film used as the optical film have optical anisotropy, and in particular, the liquid crystal film can have various types of optical properties that are difficult to realize in a stretched film.

That is, the liquid crystal can be divided into a disc-type type and a rod-type type according to the shape of the liquid crystal molecules. Among them, the liquid crystal of the rod-type type is planar, Since there are various orientations such as tilted, splay, and cholesteric, the resulting optical properties are varied and unique. Therefore, it is possible to directly apply the polymerizable liquid crystal compound directly to an acetyl cellulose substrate used as an optical film and use it as an optical film, so that various orientation characteristics of the liquid crystal can be applied as it is. It is possible to obtain a hard effect and at the same time to serve as an optical compensation film.

In general, the liquid crystal film (optically anisotropic film) as described above is prepared by first applying an alignment film composition for forming a liquid crystal alignment film on a plastic substrate, drying and curing it to form an alignment film, rubbing it again to give the alignment property, The polymerizable liquid crystal compound is generally coated, dried and cured to fix the polymerizable liquid crystal compound. However, in the case of the method of forming the alignment film by the rubbing method as described above, it is difficult in the manufacturing process due to weakness in the process. That is, the conventional rubbing method is a kind of contact method, which requires the presence of impurities and surface defects and a cleaning process to remove the impurities and surface defects, which complicates the process and increases the cost.

In order to solve this problem, there has been developed a technique for giving an orientation property to an orientation film by using light as a non-contact type. That is, in order to compensate for the disadvantages of the rubbing process, it is a reality to develop a photo alignment layer that gives orientation characteristics to the alignment layer in a non-contact manner using light, thereby simplifying the process and reducing costs. To this end, a light control functional material capable of controlling changes in optical, chemical, and physical properties by making structural changes corresponding to various specific wavelengths of light energy is required.

Accordingly, in order to overcome the disadvantages of the conventional rubbing alignment and to obtain a cost reduction and a process advantage, a compound having a photo-alignment property and a polymer using the compound, which can be applied for imparting an orientation property to an orientation film using light, is provided I want to.

In particular, the present invention provides a compound having both a functional group having a photopolymerization property and a functional group having a photoisomerization property at the same time, and a compound capable of performing a selective photoreaction with respect to arbitrary selected wavelengths and a polymer using the compound I want to.

Another object of the present invention is to provide an optical film and a display device using the polymer.

In order to solve the above problems, one aspect of the present invention provides a polymer compound comprising a functional group having a photopolymerization property and a functional group having a photoisomerization property.

The polymer compound is a photo-orientable polymer represented by the following formula (1).

≪ Formula 1 >

In Formula 1,

M is a vinyl polymerizable monomer unit constituting the polymer main chain,

L ¹ , P ¹ , L ² , P ² , L ³ and R ¹ are units constituting the polymer side chain,

L ¹ , L ² and L ³ are, independently of each other, a single bond; A straight or branched hydrocarbon group of 1 to 24 carbon atoms which is unsubstituted or substituted by a cyano group or a halogen group, wherein at least one of the CH ₂ groups of the hydrocarbon group may be independently replaced by a group A; A halogen group or a straight or branched alkyl residue having 1 to 24 carbon atoms wherein the alkyl residue may be unsubstituted or substituted with a cyano group or a halogen group and at least one of the CH ₂ groups of the alkyl residue One of which may be independently substituted by group A), wherein the aromatic or alicyclic hydrocarbon group may be a heterocycle comprising O, N or S,

And A is -O-, -S-, -CO-, -CO- O-, -O-CO-, -Si (CH 3) 2 -O-Si (CH 3) 2 -, -NR 2 -, ^{-NR 2 -CO-, -CO-NR 2} -, -NR 2 -CO-O-, -O-CO-NR 2 -, -NR 2 -CO-NR 3 -, -CH = CH-, -C -O-CO-O- wherein R ² and R ³ are, independently of each other, hydrogen or a lower alkyl group,

One of P ¹ and P ² is a photodimerizable group and the other is a photoisomerizable group,

R ¹ is a terminal crosslinking group, and n is 0 or 1.

In one embodiment of the present invention, the photo-dimer may include a group represented by the following formula (2) or (3).

(2)

(3)

In the above Formulas 2 and 3,

The broken line represents the bonding point in the side chain,

B is an unsubstituted or substituted group selected from the group consisting of a cyano group, a halogen group, or a straight, branched or cyclic alkyl residue of 1 to 24 carbon atoms wherein the alkyl residue may be unsubstituted or substituted by a cyano group or a halogen group, at least one of the CH ₂ groups is a group a independently can be substituted by (wherein, a is as defined above)] phenylene, pyrimidine-2,5-diyl is substituted by, pyridine-2,5- Diyl, 2,5-thiophenylene, 2,5-furanylene, 1,4-naphthylene or 2,6-naphthylene,

E is -O-, -OR ⁴ -, -NR ⁵ R ⁶ -, or an oxygen atom bonded to ring B at the ortho position to form a coumarin unit, wherein R ⁴ , R ⁵ and R ⁶ independently of one another are hydrogen (Wherein R ⁴ and R ⁶ are not hydrogen), or a straight, branched or cyclic hydrocarbon group of 1 to 18 carbon atoms, wherein the hydrocarbon group may be unsubstituted or substituted by a halogen group, and CH At least one of the _two groups may be independently replaced by -O-, -CO-, -CO-O-, -O-CO- or -CH = CH-, and R ⁵ and R ⁶ together form a bond To form an alicyclic ring of 5 to 8 atoms,

X and Y are each independently a hydrogen, a cyano group, a halogen group, or a hydrocarbon group of 1 to 12 carbon atoms substituted by unsubstituted or fluorine, wherein at least one of the CH ₂ groups of the hydrocarbon group is independently -O-, -CO-O-, -O-CO- or -CH = CH-), when E is an oxygen atom which bonds to ring B at the ortho position to form a coumarin unit, X and Y Either of which is a single bond or -O- bonded to L < ² > or L < ^{3 &} gt ;.

As a preferred example, the photo-dimer may include at least one selected from a cinnamate group and a coumarin group.

In one embodiment of the present invention, the photo-isomer includes at least one selected from the group consisting of an unsubstituted or cyano group, a halogen group, a nitro group, a hydroxyl group or an aryl azo group substituted with an alkyl residue having 1 to 12 carbon atoms and a heteroaryl azo group can do.

As a preferred example, the photo-isomer may include a group represented by the following formula (4).

≪ Formula 4 >

In the formula (4), the broken line indicates a bonding point in the side chain.

Meanwhile, as a more preferred example of the present invention, the photo-dimer includes a group represented by the formula (2) or (3), and the photo-isomer may include a group represented by the formula (4).

In one embodiment of the present invention, R ¹ may be selected from the group represented by the following formulas (5) to (14).

≪ Formula 5 >

(6)

≪ Formula 7 >

(8)

≪ Formula 9 >

≪ Formula 10 >

≪ Formula 11 >

≪ Formula 12 >

≪ Formula 13 >

≪ Formula 14 >

In the general formulas (5) to (14), the broken line represents a bonding point to L ³ ,

In Formula 5, x, y, and z are each an integer of 0 to 3 (provided that x + y + z = 3)

In Formula 7, o is an integer of 1 to 7.

That is, according to the photo-orientable polymer of the present invention, a crosslinking group represented by R ¹ is introduced at the side chain terminal and further crosslinking reaction is carried out in addition to photo dimerization by a method such as photo polymerization, thermal polymerization or polymerization with a radical initiator So that a more stabilized orientation can be imparted.

In one embodiment of the present invention, the vinyl polymerizable monomer is selected from the group consisting of acrylate, methacrylate, 2-chloroacrylate, 2-phenyl acrylate, N-lower alkyl substituted acrylamide, methacrylamide, Amide, 2-phenyl acrylamide, vinyl ether, vinyl ester, styrene and derivatives thereof.

Specifically, M in the formula (1) representing the vinyl polymerizable monomer unit may be selected from the group represented by the following formulas (15) to (26).

≪ Formula 15 >

≪ Formula 16 >

≪ Formula 17 >

≪ Formula 18 >

(19)

(20)

≪ Formula 21 >

(22)

≪ Formula 23 >

≪ EMI ID =

≪ Formula 25 >

(26)

In the general formulas (15) to (26), the broken line represents the point of attachment to the side chain,

In the above formulas (19) to (22), R ⁷ is hydrogen or a lower alkyl group.

On the other hand, the terms used in this specification can be defined as follows.

The term "photodimerizable group " refers to a photosensitive functional group that forms a dimer by interaction with another photodimer (e. G., A cyclization addition reaction) by light irradiation.

The term "photoisomerizable group" refers to a photosensitive functional group that undergoes isomerization (e.g., cis-trans transformation) via an excited state by light irradiation.

The term "aromatic" means an optionally substituted carbocyclic or heterocyclic group incorporating 5, 6 or 10 ring atoms, for example furan, phenyl, pyridine, pyrimidine, naphthalene or It should be understood to include a tetralin unit.

The term "alicyclic" refers to a nonaromatic carbocyclic or heterocyclic ring system having from 3 to 10 carbon atoms, such as cyclopropane, cyclobutane, cyclopentane, cyclopentene, cyclohexane, cyclohexene and cyclohexadiene, Should be understood to include.

The term "lower alkyl (group)" should be understood to include straight and branched hydrocarbon radicals having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. Particularly preferred are methyl, ethyl, propyl and isopropyl groups.

The term "straight-chain, branched or cyclic alkyl residue of 1 to 24 carbon atoms unsubstituted or substituted by halogen groups, wherein at least one of the CH ₂ groups of the alkyl moiety is independently -O-, -CO-, -CO -O-, -O-CO-, -CH = CH- or -C≡C- "is to be understood as meaning for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl, Butyl, tert-butyl, pentyl, isopentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, 3-methylpentyl, allyl, Yl, pent-4-en-1-yl, hex-5-en-1-yl, propynyl, butynyl, pentynyl, methoxy, ethoxy, propoxy, isopropoxy, Butoxy, isopentyloxy, cyclopentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy , Dodecyloxy, 3-methylpentyloxy, allyloxy, Propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isopropoxycarbonyl, isopropoxycarbonyl, isopropoxycarbonyl, isopropoxycarbonyl, isopropoxycarbonyl, isopropoxycarbonyl, isopropoxycarbonyl, Isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, cyclopentyloxycarbonyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, octyl 3-ethyloxycarbonyl, but-3-enyloxycarbonyl, pent-3-enyloxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl, undecyloxycarbonyl, dodecyloxycarbonyl, 3- methylpentyloxycarbonyl, Cyclohexylmethoxycarbonyl, cyclopentylmethoxycarbonyl, acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, isobutylcarbonyloxy , Sec-butylcarbonyloxy, tert-butylcarbonyloxy, pentylcarbonyloxy, isopentylcarbonyl Cyclohexylcarbonyloxy, octylcarbonyloxy, nonylcarbonyloxy, decylcarbonyloxy, undecylcarbonyloxy, dodecylcarbonyloxy, 3-methylpentyl, cyclohexylcarbonyloxy, cyclohexylcarbonyloxy, Propylcarbonyl, isopropylcarbonyl, butylcarbonyl, isobutylcarbonyl, sec-butylcarbonyl, pentylcarbonyl, sec-butylcarbonyl, sec-butylcarbonyl, sec-butylcarbamoyl, But are not limited to, carbonyl, isopentylcarbonyl, cyclohexylcarbonyl, octylcarbonyl, nonylcarbonyl, decylcarbonyl, undecylcarbonyl, dodecylcarbonyl, methoxyacetoxy, Butoxy, 3-butyl-1-oxy, 4-pentyne-1-oxy, 3-methoxy-1-propoxy, 2-methoxyethoxy, 2-isopropoxyethoxy, , 5-chloro-1-pentyne, 4-pentenecarbonyloxy, 6-propyloxyhexyl, 6-propyloxyhexyloxy, 2-fluoroethyl, trifluoromethyl, 2,2,2-trifluoro Ethyl, 1H, 1H-1H-pentadecafluor (Perfluorobutyl) ethyl, 2- (perfluorohexyl) -ethyl, 2- (perfluorohexyl) ethyl, Fluoropentyloxy, 2-fluoropropoxy, 1-fluoropentyloxy, 1-fluoropentyloxy, 1-fluoropentyloxy, 1-fluoropentyloxy, Fluoroethoxy, 2,2-difluoropropoxy, 3-fluoropropoxy, 3,3-difluoropropoxy, 3,3,3-trifluoropropoxy, trifluoromethoxy and the like.

The linking groups L &^lt; ^{1 >} , L &^lt; ^{2 >} and L < ³ >, except where L < ³ > is an end group, -CH ₂ -, or - (CH ₂ ) _r -; _{- (CH 2) r -O-,} - (CH 2) r -CO-, - (CH 2) r -CO-O-, - (CH 2) r -O-CO-, - (CH 2) r ^{-CO-NR 2 -, - (} CH 2) r -NR 2 -CO-, - (CH 2) r -NR 2 -, - (CH 2) r -O- (CH 2) s -, - (CH _{2) r -CO-O- (CH} 2) s -, - (CH 2) r -O-CO- (CH 2) s -, - (CH 2) r -NR 2 -CO- (CH 2) s _{-, - (CH 2) r} -NR 2 -CO-O- (CH 2) s -, - (CH 2) r -O- (CH 2) s -O-, - (CH 2) r -CO- _{O- (CH 2) s -O-,} - (CH 2) r -O-CO- (CH 2) s -O-, - (CH 2) r -NR 2 -CO- (CH 2) s -O _{-, - (CH 2) r} -NR 2 -CO-O- (CH 2) s -O-, -O- (CH 2) r -, -CO-O- (CH 2) r -, -O- _{CO- (CH 2) r -,} -NR 2 -CO- (CH 2) r -, CO-NR 2 - (CH 2) r -, -NR 2 - (CH 2) r -, -O- (CH _{2) r -CO-O-, -O-} (CH 2) r -O-CO-, -O- (CH 2) r -CO-NR 2 -, -O- (CH 2) r -NR 2 - _{, -O- (CH 2) r -O-} , -O- (CH 2) r -NR 2 -CO-, -NR 2 - (CH 2) r -CO-O-, -NR 2 - (CH 2 ^{_{) r -O-, -NR 2 - (}} CH 2) r -NR 3 -, -NR 2 - (CH 2) r -O-CO-, -CO-NR 2 - (CH 2) r -O-, _{^{-CO-NR 2 - (CH 2}} ) r -NR 3 -, -CO-NR 2 - (CH 2) r -O-CO-, -O-CO- (CH 2) r -CO-, -O- _{CO- (CH 2) r -O-,} -O-CO- (CH 2) r -NR 2 -, -O-CO- (CH 2) r -CO-O-, -O-CO- (CH 2 ) _r ^{-CO-NR 2 -, -O-} CO- (CH 2) r -NR 2 -CO-, -O- (CH 2) r -O- (CH 2) s -, -O- (CH 2) r _{-CO-O- (CH 2) s} -, -O- (CH 2) r -NR 2 -CO- (CH 2) s -, -O- (CH 2) r -NR 2 -CO-O- ( CH ₂ ) _s -, -O- (CH ₂ ) _r -CO-O- (CH ₂ ) _s -O-, -O- (CH ₂ ) _r -O- (CH ₂ ) _s -O-, -O - (CH ₂ ) _r -NR ² -CO- (CH ₂ ) _s -O-, -O- (CH ₂ ) _r -NR ² -CO-O- (CH ₂ ) _s -O-, -CO-O - (CH ₂ ) _r -O- (CH ₂ ) _s - or -CO-O- (CH ₂ ) _r -O- (CH ₂ ) _s -O- wherein r and s are each a number of 1 to 20 , R + s < = 20, and R < ² > and R < ³ > are each independently hydrogen or lower alkyl); Or C 1 straight-chain or branched alkyl residue of 1 to 24; wherein the alkyl moieties unsubstituted or substituted with cyano may be substituted by a group or a halogen, at least one of the moieties CH ₂ group is independently selected from A (wherein, A Quot; are as defined hereinbefore), as well as a spacer unit such as an aromatic or alicyclic hydrocarbon group.

In a further aspect, the present invention provides a use as an alignment layer for a liquid crystal, either as a polymer of the formula (I) alone or as a copolymer comprising the formula (I) or as a mixture thereof. Such an oriented layer can be unstructured or structured (patterned, multi-domained) and advantageously used for unstructured and structured optical elements and multilayer systems such as non-absorptive color filters, linear and annular polarizers, Layer and the like as well as the design of the LCD. These examples are disclosed in European Patent Publication No. 0611981, EP 0689084, EP 0753785 (both F. Hoffman-La Roche) and WO 98/52077 It is illustrated in Fig.

The polymer having the structure of the formula (1) as a repeating unit can be prepared by a method known to a person skilled in the art and a commercially available material.

The copolymers of the present invention together with acrylate, methacrylate, acrylamide, methacrylamide and styrene derivatives as repeating monomer units can in principle be prepared by two different processes. In addition to the direct polymerization of the preprocessed monomer, there is a possibility of polymer-homolog reaction of the reactive photoactive derivative with the functional polymer.

In the case of direct polymerization, monomers and comonomers are first prepared separately from the respective components. The formation of the copolymer can then be carried out in a known manner by the action of UV radiation, heat treatment, radical or ionic catalyst.

Examples of peroxide (peroxide) compounds that generate radicals include, but are not limited to, potassium peroxodisulfate, dibenzoyl peroxide (BPO), acetyl peroxide, di-tert-butyl peroxide, cumyl hydroperoxide, And azo compounds such as azobisisobutyronitrile (AIBN) are representative. The ionic catalyst is an alkali-organic compound such as phenyl lithium or naphthyl sodium or a Lewis acid such as BF ₃ , AlCl ₃ , SnCl ₃ or TiCl ₄ . The monomers may be polymerized in the form of solutions, suspensions or emulsions.

In the second step, the polymer may also be prepared from a polymer-homologous reaction from a pre-processed functional polymer and a suitable functionalized side chain derivative. A number of known processes, such as esterification, trans-esterification, amidation or etherification reactions, are suitable for polymer-homolog reaction.

The polymers according to the present invention may have a molecular weight (Mw) of 1,000 to 5,000,000.

Polymer is a homopolymer formed by a single monomer (or a single polymer; homopolymer) of the present invention may be in the form, or a compound represented by the formula (1) is M, L ¹ to L ^3, P ^1, P ^2, R ¹ and n, and may be in the form of a copolymer obtained by polymerizing these various compounds as monomers.

As a polymer having a compound represented by the formula (1) as a repeating unit, a polymer represented by the following formula (27) can be given as an example of a copolymer formed by polymerizing a monomer in which two or more different compounds are mixed.

≪ Formula 27 >

In Formula 27,

^{M ', L 1', P} 1 ', L 2', P 2 ', L 3', R 1 ' and n' are of ^{M, L 1, P 1,} L 2, P 2, L 3 formula (I), respectively , R ¹ and n, and may be selected from at least one of M, L ¹ , P ¹ , L ² , P ² , L ³ , R ¹ and n.

Another example of the above-mentioned copolymer is a polymer having a structure represented by the following formula (28).

(28)

In Formula 28,

M "is selected from the same group as M in the above formula (1)

L " is hydrogen; A straight or branched hydrocarbon group of 1 to 24 carbon atoms which is unsubstituted or substituted by a cyano group or a halogen group, wherein at least one of the CH ₂ groups of the hydrocarbon group may be independently replaced by a group A; A halogen group or a straight or branched alkyl residue having 1 to 24 carbon atoms wherein the alkyl residue may be unsubstituted or substituted by a cyano group or a halogen group and at least one of the CH ₂ groups of the alkyl residue One of which may be independently replaced by a group A, wherein A is as defined above, wherein the aromatic or alicyclic hydrocarbon group comprises O, N, or S Lt; / RTI > may be a heterocycle).

Monomers comprising M " and L &^lt; ¹ >' and methods for making polymers using them are known in the art.

The polymer according to the present invention may be made up of other various monomer units but it is also possible to include one or more reactive functional groups capable of directly or indirectly linking the monomer units to the epoxy components, It may be desirable to provide for the formation of an interpolymer network. These reactive functional groups may be any known reactive group, such as hydroxy (-OH) or acidic (e.g., carboxyl, -COOH) reactive groups. Such groups may be included in polyacrylates, for example, by including monomers suitable for preparing polyacrylates, such as acrylic acid monomers. Alternatively, this interaction between the polyacrylate and the epoxy can be achieved by using a bi- or multifunctional monomer such as an epoxy acrylate with a graphing agent that can be reacted with the polyacrylate.

As described above, it is possible to prepare various copolymers by using various kinds of monomers. Those skilled in the art can prepare various kinds of copolymers by using various compounds having different M, L ¹ , P ¹ , L ² , P ² , L ³ , R ¹ , can do.

The copolymers according to the present invention may also be used alone or as a mixture with one or more other polymers or other copolymers. Accordingly, a further aspect of the present invention includes a photoreactive mixture containing the inventive interpolymer. Mixing partners are known components for photo-alignment properties, such as those disclosed in EP-A-0611786, WO 96/10049, EP-A-0763552, EP-A-0860455, May be a component as exemplified in International Patent Publication No. WO 99/15576, WO 00/59966 and PCT / EP 00/06788.

Another aspect of the present invention provides a method for producing an optical film comprising a photo-orientable polymer.

The method of manufacturing an optical film includes: preparing a substrate; Coating the photo-orientable polymer represented by Formula 1, Formula 27 or Formula 28 on the substrate; And irradiating the coated photo-orientable polymer with light to photo-isomerize and photo-dimerize the polymer.

The substrate may be a glass, a cyclic olefin polymer film (COC or COP), a triacetylcellulose (TAC) film, a polyethylene terephthalate (PET) film, a polycarbonate (PC) film, a polyisocyanate And polyimide (PI) films.

In one embodiment, the step of coating the photo-orientable polymer may be performed by applying a solution in which the photo-orientable polymer is dissolved to a substrate to form a coating film, and then drying the solvent contained in the coating film. The concentration of the polymer solution, the kind of the solvent, and the method of application can be determined depending on the kind of polymer used and the intended use.

The solid concentration of the polymer may be selected in consideration of the molecular weight, viscosity, volatility, etc. of the polymer used. In order to achieve the desired liquid crystal alignment effect and have the desired coating properties and appropriate viscosity, It is preferable to set the polymer to be contained in the range of 0.1 to 10 wt%.

The coating layer comprising the photo-orientable polymer can be prepared by applying a polymer solution to the substrate to produce a uniform layer having a thickness of 0.05 to 50 mu m. The substrate may be provided with an electrode layer, such as any additional component, for example, an indium-tin oxide (ITO) layer. Application of the polymer solution can be performed using various coating techniques such as spin coating, fine coating, wire coating, slot coating, offset printing, flexographic printing, gravure printing and the like.

The solvent of the polymer solution may be any organic solvent which is soluble in the monomer and the polymer produced. As non-limiting examples, phenyl-based compounds such as ethyl acetate, chloroform, tetrahydrofuran, benzene, or toluene and xylene (including ortho- and meta-para-form) can be used.

After application of the polymer solution, the solvent may be dried by heating the coating film or using a vacuum evaporation method or the like. In this case, the drying of the solvent is preferably carried out at 50 to 250 DEG C for 10 to 90 minutes in consideration of the thickness of the coating film and the kind of the polymer.

The dried coating film can be subjected to alignment treatment by irradiating polarized ultraviolet rays having a wavelength range of 150 to 450 nm. That is, the photo-isomerization polymer coated on the substrate can be irradiated with light having a wavelength in the UV region to promote optical isomerization and photo-dimerization reaction, thereby imparting orientation. At this time, the intensity of the exposure differs depending on the type of the polymer, the thickness of the coating film, the desired degree of orientation, the use of the wavelength selective filter, and the like, and energy of 10 mJ / cm 2 to 10 J / cm 2 can be irradiated.

On the other hand, in the process of irradiating ultraviolet rays, as described above, it is possible to irradiate the applied polymer material with uniform light without using or using a wavelength selective filter which transmits only ultraviolet rays suitable for photoisomerization and / or photo-dimerization reaction .

When the wavelength corresponding to the optical isomerization and the wavelength corresponding to the optical dimerization are simultaneously irradiated through the wavelength selection filter, the orientation and the crosslinking (meaning crosslinking due to the dimerization of light) proceed simultaneously, and the wavelength corresponding to the optical isomerization When irradiating a wavelength corresponding to photodimerization sequentially and sequentially, the crosslinking of the photo-alignment polymer proceeds after the alignment. That is, when the wavelength selection filter is used, the wavelengths of two or more specific regions can be simultaneously or sequentially inspected to properly control the alignment and crosslinking.

The light irradiation can also simultaneously irradiate a wide range of wavelengths without using a wavelength selection filter, so that optical isomerization and optical diminution can proceed at the same time.

The choice of a specific wavelength range for photo-alignment and photo-crosslinking is basically determined by the type of photoreactive functional group and the degree of delocalization in the polymer structure, and the theoretical values for azobenzene (360 nm), chalcone (342 nm), cinnamate nm, an absorption wavelength range of coumarin (325 nm), and a maximum absorption wavelength region obtained in the UV spectrum of an experimentally synthesized polymer. The light irradiation time depends on the material, the use of the wavelength selection filter, and the amount of light source used.

The photo-orientable polymer according to the present invention may have a directionality because it has a photosensitivity whose arrangement is changed by light irradiation. Therefore, the polymer can be usefully applied to an alignment film of an optical film.

Meanwhile, the method for producing an optical film may further include cross-linking a terminal crosslinking group contained in a side chain of the photo-orientable polymer coated on the substrate. That is, when the photo-orientable polymer has a crosslinking group represented by R ¹ or R ¹ 'as shown in the above formulas (1), (27) and (28), an additional crosslinking reaction can be caused at the side chain terminal of the photo-orientable polymer.

The terminal crosslinking group may be crosslinked by light irradiation, heat treatment, acid treatment or catalytic treatment. In particular, when the terminal crosslinking group is a group capable of crosslinking by light irradiation, the crosslinking reaction of the terminal crosslinking group can proceed simultaneously in the photo-isomerization and photo-dimerization reaction steps, thereby simplifying the process. At this time, energy corresponding to each wavelength may be varied depending on the light source, and the light source may be, for example, a high pressure mercury vapor lamp, a xenon lamp, or a pulsed UV laser.

When an additional crosslinking reaction is carried out using a terminal crosslinking group, the solubility is decreased and the interfacial stability of the photo alignment layer is improved.

In addition, the compounds which have been applied to conventional alignment layers generally have photosensitivity to one or two wavelengths, but the photo-orientable polymer according to the present invention is sensitive to at least two or more wavelengths and easily controls each photoreactive group It can be applied to various fields.

In order to solve the above problems, another aspect of the present invention provides an optical film comprising a photo-orientable polymer.

The above optical film can be produced by the optical film production method described above. That is, the optical film includes a substrate; And a coating layer disposed on the substrate and comprising a photo-orientable polymer represented by Formula (1), Formula (27), or Formula (28).

At this time, the coating layer may be an alignment layer formed to have a uniform orientation by light irradiation.

The optical film may be used as a retardation film, a viewing angle compensation film, and a protective film as materials showing optical characteristics. However, the kind and use thereof are not limited thereto.

According to another aspect of the present invention, there is provided a display device including the optical film. The device may be a liquid crystal display device, but the type and use thereof are not particularly limited.

Since the polymer according to the present invention and the monomer compound used therein exhibit a nematic thermotropic liquid crystal characteristic having liquid crystal properties corresponding to heat, the interaction with the liquid crystal is higher than that of the compound or polymer used in the conventional alignment film. great. In addition, since a compound other than a polymer alone can have a liquid crystal property, it can be applied in various fields. Therefore, the optical film according to the present invention can be particularly usefully applied to a retardation film, a liquid crystal display device, and the like.

The photo-orientable polymer according to the present invention has at least two or more photosensitive groups and is capable of easily expressing the desired characteristics by light irradiation, and thus can be used in various fields of application. In addition, since the film containing the photo-orientable polymer can be imparted with the orientation property in a non-contact manner, impurities and surface defects can be reduced as compared with the conventional rubbing orientation method, and the process can be simplified and the cost can be reduced.

In addition, since the monomers and polymers used in the present invention exhibit the characteristics of a nematic thermotropic liquid crystal having liquid crystal properties corresponding to heat, the interaction with the liquid crystal in comparison with the compound or polymer used in the conventional alignment film great.

Further, since the polymer according to the present invention has a photopolymerizable functional group, it has excellent chemical resistance, heat resistance and frictional resistance in a film state.

Further, the polymer according to the present invention can obtain a more stabilized orientation property in the film state through the terminal cross-linking reaction unit of the side chain.

In particular, when a film is formed using the photo-orientable polymer according to the present invention, the photo-isomerization reaction and the photo-dimerization reaction can be selectively controlled by irradiating light in a specific wavelength range.

1 is a synthesis reaction formula of a monomer compound constituting the polymer represented by the formula (29).
2A, 2B, and 2C are ¹ H-NMR, FT-IR, and UV spectra of the polymer represented by Formula 30, respectively.
3A, 3B, and 3C are ¹ H-NMR, FT-IR, and UV spectra of the polymer represented by Formula 31, respectively.
4, 5, 6, 7, 8, 9, and 10 are comparative examples 1, 5, 5-1, 5-2, 5-3, 5-4, and Example 5-5, respectively, showing the on / off state of the cell.
Figs. 11, 12, 13, 14, 15 and 16 are diagrams for explaining examples 6, 6-1, 6-2, 6-3, 6-4, 5 shows the on / off state of the cell fabricated with an optical microscope.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments.

≪ Example 1 > Preparation of polymer represented by formula (29)

(E) -3-methoxy-3-oxoprop-1-enyl) phenyl 4- (2- (methacryloyloxy) ethoxy) phenyl) diazenyl) benzoate

First, BPO (benzoyl peroxide), a polymerization initiator, was purchased from ACROS and recrystallized from chloroform / methanol (1: 1, v / v). The solvent anhydrous benzene was purchased from Aldrich and used immediately without any purification. (5 mol%) of 4 - ((E) -3-methoxy-3-oxoprop-1-enyl) phenyl 4 - benzene was added and dissolved. The ampoule containing the mixture was repeated four times with freeze-degas-thaw method using liquid nitrogen and vacuum pump, and the ampoule was sealed with a gas torch under vacuum after the gas was completely removed. The mixture was allowed to stand at room temperature and polymerized at 80 DEG C for 24 hours. After 24 hours, the reaction was cooled to 0 < 0 > C and precipitated in excess methanol to terminate the polymerization reaction. The resulting precipitate was filtered, washed several times with methanol, and then dried in a vacuum oven at room temperature for 24 hours to obtain a pale orange polymer represented by Chemical Formula (29).

The monomer of the polymer represented by Formula 29 may be synthesized through the process shown in FIG.

Synthesis of Ethyl 4 - ((4-hydroxyphenyl) diazenyl) benzoate (Intermediate 1)

Ethyl 4-aminobenzoate (10 g, 60.6 mmol) is dissolved in 1 mol of hydrochloric acid (100 mL) and kept at 0 ° C in ice water. This solution is added slowly to an aqueous solution of NaNO ₂ (4.2 g, 60.8 mmol) dissolved in water (30 mL) and stirred for 30 min. NaOH (7.2 g, 0.18 mol) and phenol (5.8 g, 61.7 mmol) were dissolved in water (80 mL) and stirred at 0 ° C. for 30 minutes. Thereafter, the mixed aqueous solution is stirred for 1 hour while maintaining the temperature at 0 ° C. After the mixed mixture is poured into water and diluted, the aqueous solution is neutralized with 5% hydrochloric acid and precipitated. The precipitate was obtained by filtration under reduced pressure, and then recrystallized twice from ethanol to obtain intermediate 1, a red crystal. (11.8 g, yield: 72%, mp: 153-154 [deg.] C).

Fig. 2 (a) is an FT-IR spectrum of the intermediate (1), and Fig. 2 (b) is a ¹ H-NMR spectrum of the intermediate (1).

Synthesis of Ethyl 4 - ((4- (2-hydroxyethoxy) phenyl) diazenyl) benzoate (Intermediate 2)

Ethyl 4 - ((4-hydroxyphenyl) diazenyl) benzoate (18.7 g, 69.3 mmol) was dissolved in EtOH (100 mL). The solution is slowly added to a solution of KOH (4.3 g, 76.2 mmol) in EtOH (100 mL). 1-Cholo-2-ethanol (14.5 g, 103.9 mmol) and KI (3 g, 18.1 mmol) were added to the solution, and the mixture was refluxed for 30 hours. After the reaction, the product is extracted three times with water (100 mL) and CHCl ₃ (100 mL, divided by 20 mL), and the organic layer is separated. The separated organic layer was dried with Na ₂ SO ₄ , and the solvent was removed by vacuum distillation. The obtained product was dried in a vacuum oven at 40 ° C and recrystallized twice from EtOH to obtain Intermediate 2. (19.5 g, yield: 76%, mp: 90-91 [deg.] C)

Synthesis of 4 - ((4- (2-hydroxyethoxy) phenyl) diazenyl) benzoic acid (Intermediate 3)

A mixture of slurry and KOH (0.6 g, 10 mmol) in EtOH (300 mL) + distilled water (100 mL) was added to the slurry overnight at room temperature And then refluxed with heating. The mixture is precipitated in acidified distilled water at a pH of 3 in a 10-fold amount. Suller NaCl is added to produce a yellow or orange suspension on the surface of the aqueous solution, followed by filtration under reduced pressure to obtain a solid. The resulting solid is washed with a large amount of water until the pH is about 7. The obtained product was dried in a vacuum oven at 40 DEG C for two days, recrystallized twice with MeOH, and then completely dried in a vacuum oven at 40 DEG C to obtain a light orange crystal, Intermediate 3. (0.7 g, yield: 53%)

Synthesis of 4 - ((4- (2- (methacryloyloxy) ethoxy) phenyl) diazenyl) benzoic acid (Intermediate 4)

4- (6-Hydroxyhexyloxy) phenylazobenzoic acid (1g, 2.9mmol) was dissolved in THF (10ml) at 0 ° C, (100 mL). When a dark red colored solution is formed, it is reacted at 40 ° C for 48 hours. The solution is dissolved in acetic acid at 120 ° C and n-hexane is added until crystals are first seen. When crystals begin to be formed, the mixture is cooled to 5 ° C and kept overnight, after which the solid is separated by vacuum filtration. The obtained solid was dissolved in acetic acid at 120 ° C, cooled to room temperature (about 4 hours), stored at 5 ° C overnight, and filtered under reduced pressure to obtain a solid crystal. The obtained crystals were washed and then dried in a vacuum oven at 40 DEG C to obtain an intermediate 4 as an orange powder. (0.9 g, yield: 76%)

Synthesis of Methyl 3- (4-hydroxyphenyl) -acrylate (Intermediate 5)

51.2 g (312 mmol) of p-coumaric acid were dissolved in 330 ml of methanol and treated with 10 ml of concentrated sulfuric acid. The solution was heated under reflux for 2 hours. Subsequently, most of the methanol (about 200 ml) was distilled off and the remaining residue was poured into ice water. The separated ester was filtered off with suction and washed successively with cold water, a small amount of cold NaHCO ₃ solution and again with cold water. Drying in a water-jet vacuum at 50 < 0 > C gave Intermediate 5 (51.1 g) in the form of a pale brown powder.

Preparation of 4 - ((E) -3-methoxy-3-oxoprop-1-enyl) phenyl 4 - ((4- (2- (methacryloyloxy) ethoxy) phenyl) diazenyl) benzoate

Dissolve 4 - ((4- (2- (methacryloyloxy) ethoxy) phenyl) diazenyl) benzoic acid (4.5 mmol) in distilled THF (50 mL) under argon atmosphere. Add (COCl) ₂ (0.81 mL, 9.5 mmol) to the solution slowly with a syringe, drop three drops of DMF into the syringe, allow to react for 2 hours, and then remove the solvent with a rotary evaporator. Dilute Methyl 3- (4-hydroxyphenyl) acrylate (5.4 mmol) in purified THF (17 mL) and slowly inject TEA (1.25 mL, 5.4 mmol) in an Argon atmosphere with a syringe. The reaction was slowly added to purified THF (33 mL) and stirred at room temperature for 15 hours. The reaction product is added to a mixture of distilled water and dichloromethane and extracted three times to separate the organic layer. The solvent is then removed by drying under reduced pressure. The obtained product was separated and purified by a column chromatography method to obtain an orange solid compound. (Yield: 95%)

The following compounds can be synthesized by methods similar to those described above.

≪ When n = 0 in the structure of formula (1) >

M L ¹ P ¹ L ² P ² L ³

Equivalent to structure of formula 29

Except that 1-Cholo-4-buhanol was used instead of 1-Cholo-2-ethanol in the synthesis of the intermediate (1) in the synthesis step of the formula (29) shown in Example 1,

Except that 1-Cholo-2-ethanol was used instead of 1-Cholo-2-ethanol in the synthesis of the intermediate (1) in the synthesis step of the formula (29) shown in Example 1,

Except that (2-chloroethoxy) methanol was used instead of 1-Cholo-2-ethanol in the synthesis of the intermediate (1) in the synthesis of the compound of the formula (29) shown in Example 1,

The reaction of the intermediate (1) with 4-chloro-1,1,2,2,3,3-hexafluorobutan-1-ol was carried out in the same manner as in Example 1, except that 1-Cholo- The remainder except the used was prepared in the same manner

Except that 2-chloroethylcarbamic acid was used instead of 1-Cholo-2-ethanol in the synthesis of the intermediate (1) in the synthesis of the compound of the formula (29) shown in Example 1,

Except that (chloromethyl) dimethylsilyl hydroxydimethylsilyl ether was used instead of 1-Cholo-2-ethanol in the synthesis of the intermediate (1) in the synthesis step of the formula (29) shown in Example 1,

(1E, 3E) -4-chlorobuta-1,3-dien-1-ol was used instead of 1-Cholo-2-ethanol in the synthesis of the compound of the formula The remainder were manufactured in the same manner

Except that 4-chlorophenol was used instead of 1-Cholo-2-ethanol in the synthesis of the intermediate (1) in the synthesis step of the formula (29) shown in Example 1,

Except that 5-chloro-2-hydroxybenzonitrile was used instead of 1-Cholo-2-ethanol in the synthesis of the intermediate (1) in the synthesis step of the formula (29) shown in Example 1,

Except that 4-chloro-2-methoxyphenol was used instead of 1-Cholo-2-ethanol in the synthesis of the intermediate (1) in the synthesis step of the formula (29) shown in Example 1,

Except that acrylic acid anhydride was used instead of methacrylic acid anhydride in the synthesis step of the chemical formula 29 shown in Example 1 and the intermediate 1 was reacted with the intermediate 3 without reacting the intermediate 1 with the intermediate 2, Were prepared in the same manner

Except that acrylic acid anhydride was used instead of methacrylic acid anhydride in the synthesis of the compound of Formula 29 shown in Example 1 and 6-chloronaphthalen-2-ol was used in place of 1-Cholo-2- The remainder was prepared in the same manner

Acrylic acid anhydride was used instead of methacrylic acid anhydride in the synthesis of the compound of Formula 29 shown in Example 1 and 1-chloro-2-ethanol was used instead of 1-Cholo-2-ethanol to react with the intermediate (1) Except that the 7-hydroxy-4-methyl-2H-1-benzopyran-2-one was used in place of the intermediate (5)

Acrylic acid anhydride was used instead of methacrylic acid anhydride in the synthesis of the compound of Formula 29 shown in Example 1 and 1-chloro-4-butanol was used instead of 1-Cholo-2-ethanol as a reactant for the intermediate (1) Except that the 7-hydroxy-4-methyl-2H-1-benzopyran-2-one was used in place of the intermediate (5)

Except that acrylic acid anhydride was used instead of methacrylic acid anhydride in the synthesis step of Chemical Formula 29 shown in Example 1 and 1-chloro-6-hexanol was used instead of 1-Cholo-2-ethanol as a substance reacting with Intermediate (1) The remainder was prepared in the same manner

Instead of methacrylic acid anhydride, acrylic anhydride was used in the synthesis of the compound of the formula (29) shown in Example 1, and 1-chloro-3-hydroxypropane-1,2 was used instead of 1-Cholo- The remainder except for using 3-tricarbonitrile was prepared by the same method

Acrylic acid anhydride was used instead of methacrylic acid anhydride in the synthesis of the compound of the formula 29 shown in Example 1, and a substance reacting with the intermediate (1) was used instead of 1-Cholo-2-ethanol, 1,1,2,2,3,3 , And 4-heptachlorobutan-1-ol were used in the same manner.

2-chloro-2-propenoic acid was used instead of methacrylic acid anhydride in the synthesis of the compound of the formula 29 shown in Example 1 and 1-chloro-2-propanol was used instead of 1-Cholo- except that hexanol was used in the same manner

2-chloro-2-propenoic acid was used instead of methacrylic acid anhydride in the synthesis of the compound of Formula 29 shown in Example 1, and a substance reacting with the intermediate (1) was replaced with 5-chlorothiophen-2 except that 7-hydroxy-4-methoxy-2H-1-benzopyran-2-one was used instead of intermediate (5)

Acrylic acid anhydride was used in place of methacrylic acid anhydride in the synthesis of the compound represented by the formula (29) shown in Example 1 and 3-ethoxy-5-chlorothiophen-2-ol was used instead of 1-Cholo- Except for using 7-hydroxy-4-methoxy-2H-1-benzopyran-2-one in place of Intermediate (5)

Acrylic acid anhydride was used in place of methacrylic acid anhydride in the synthesis of the compound of Formula 29 shown in Example 1 and 5-chlorothiophen-2-ol was used instead of 1-Cholo-2-ethanol to react with the intermediate (1) Except that ethyl 3- (4-hydroxyphenyl) -acrylate was used in place of Intermediate (5), the same procedure

2-chloro-2-propenoic acid was used instead of methacrylic acid anhydride in the synthesis of the compound of the formula (29) shown in Example 1, and the compound reacting with the intermediate (1) Except that 7-hydroxy-4-methoxy-2H-1-benzopyran-2-one was used in place of Intermediate (5)

2-chloro-2-propenoic acid was used instead of methacrylic acid anhydride in the synthesis of the compound of Formula 29 shown in Example 1 and 2-chloroacetylcarbamic acid was used instead of 1-Cholo-2-ethanol to react with the intermediate (1) Except that 7-hydroxy-4-methoxy-2H-1-benzopyran-2-one was used instead of intermediate (5)

Acrylic acid anhydride was used instead of methacrylic acid anhydride in the synthesis of the compound of Formula 29 shown in Example 1 and 4-chlorocyclohexanol was used instead of 1-Cholo-2-ethanol to react with the intermediate (1) Except that ethyl 3- (4-hydroxy-2-methoxyphenyl) acrylate was used instead of ethyl 3-

Instead of 1-Cholo-2-ethanol (chloroamino) methanol was used instead of 1-Cholo-2-ethanol, and the reaction with intermediate (1) was carried out using 2-methoxyprop-1-ene instead of methacrylic acid anhydride in the synthesis of Except for using ethyl 3- (4-hydroxy-2-methoxyphenyl) acrylate in place of Intermediate (5)

M L ¹ P ¹ L ² P ² L ³

2-phenyl-2-propenoic acid was used in place of methacrylic acid anhydride in the synthesis of the compound of the formula 29 shown in Example 1 and 1-chloro-2-ethanol was used instead of 1-Cholo- except for using ethyl 3- (4-hydroxy-2-methoxyphenyl) acrylate instead of Intermediate (5)

2-phenyl-2-propenoic acid was used instead of methacrylic acid anhydride in the synthesis of the compound of the formula 29 shown in Example 1, and the compound reacting with the intermediate (1) was replaced by chloroamino methanol instead of 1-Cholo- 4-aminophenoxy) carbonylamino) acetate instead of Ethyl 4-aminobenzoate used in the preparation of Intermediate (1) and 7-hydroxy-4-methoxy-2H-1-benzopyran -2-one was used in the same manner.

2-phenyl-2-propenoic acid was used in place of methacrylic acid anhydride in the synthesis of the compound of the formula 29 shown in Example 1 and the compound reacted with the intermediate (1) was replaced with 5-chlorothiophen-2- 4-aminophenyl ethyl fumarate was used instead of Ethyl 4-aminobenzoate used in the preparation of intermediate (1), and 7-hydroxy-4-methoxy-2H-1-benzopyran-2-one Except for using the same method

2-methoxyprop-1-ene was used instead of methacrylic acid anhydride in the synthesis step of the chemical formula 29 shown in Example 1, and the material reacting with the intermediate (1) was replaced with 4-chloro-2-methoxyphenol 4-aminophenyl ethyl terephthalate was used instead of Ethyl 4-aminobenzoate used in the preparation of intermediate 1 and 7-hydroxy-4-methoxy-2H-1-benzopyran-2-one was used instead of intermediate (5) The remainder except the used was prepared in the same manner

2-methoxyprop-1-ene was used instead of methacrylic acid anhydride in the synthesis of the compound of the formula (29) shown in Example 1, and 4-chlorophenol was used instead of 1-Cholo- Except that 4-aminophenyl 4- (ethoxymethyl) benzoate was used instead of Ethyl 4-aminobenzoate used in the preparation of Intermediate (1) and pentyl 3- (4-chloro-2-methoxyphenyl) acrylate was used instead of Intermediate (5) Were prepared in the same manner

(2-methoxyprop-1-ene) was used instead of methacrylic acid anhydride in the synthesis of the compound of the formula (29) shown in Example 1 and the compound reacting with the intermediate (1) methanol was used instead of ethyl 4-aminobenzoate and 4-aminophenyl 2,3-dicyano-3-hydroxypropanoate was used in place of ethyl 4-aminobenzoate used in the preparation of intermediate (1) methoxyphenyl) acrylate were used in the same manner.

M L ¹ P ¹ L ² P ² L ³

Except that 1-chloro-4-methoxycyclohexane was used instead of methanol in the synthesis of intermediate (5) in the synthesis of the compound represented by formula (29) shown in Example 1, the same procedure

2-Propenoic acid was used instead of methacrylic acid anhydride in the synthesis of the compound of Formula 29 shown in Example 1 and the compound reacted with the intermediate (1) was replaced with chloro (methyl) amino ) methanol, except that 1 - ((2-chloroethoxy) methoxy) propane was used in place of methanol in the preparation of intermediate (5)

2-phenyl-2-propenoic acid was used instead of methacrylic acid anhydride in the synthesis of the compound of the formula 29 shown in Example 1, and the compound reacted with the intermediate (1) was replaced with 4-chloro-2- hydroxybutane-1,2,3-tricarbonitrile and 4- (2,2,3,3,4,4-hexafluoropentyloxy) -7-hydroxy-2H-chromen-2-one instead of Intermediate The remainder were manufactured in the same manner

Acrylic acid anhydride was used instead of methacrylic acid anhydride in the synthesis of the compound of Formula 29 shown in Example 1 and 1-chloro-3-hydroxypropane-1,2-diol was used instead of 1-Cholo- Except that 3-tricarbonitrile was used and 7-hydroxy-4- (4- (octyloxy) phenoxy) -2H-chromen-2-one was used in place of Intermediate (5)

2-chloro-2-propenoic acid was used instead of methacrylic acid anhydride in the synthesis of the compound of Formula 29 shown in Example 1, and the substance reacting with the intermediate (1) was replaced with 5-chlorothiophen-2- except that furan-2-yl 2,3-dicyano-3- (4-hydroxyphenyl) acrylate was used in place of the intermediate (5)

Acrylic acid anhydride was used instead of methacrylic acid anhydride and 4-chloro-2-methoxyphenol was used instead of 1-Cholo-2-ethanol to react with intermediate (1) in the synthesis step of chemical formula 29 shown in Example 1, Except that the 1- (3- (4-hydroxy-2-methoxyphenyl) acryloyloxy) urea was used in place of the intermediate (5)

2-chloro-2-propenoic acid was used instead of methacrylic acid anhydride in the synthesis of the compound of Formula 29 shown in Example 1, and the compound reacting with the intermediate (1) was replaced with 3- (chloromethyl) Except that heptan-4-yl 3- (4-hydroxy-2-methoxyphenyl) acrylate was used instead of Intermediate (5) and 1,1,3,3-tetramethyl-

When n = 1 and L ³ is a single covalent bond in the structure of formula (1)

M L ¹ P ¹ L ² P ² R ¹

2-chloroacetylcarbamic acid was used instead of 1-Cholo-2-ethanol and oxiran-2-yl 2,3-dichloroacetylcarbamic acid was used instead of intermediate 5 in the synthesis of the compound of Formula 29 shown in Example 1, except for using dicyano-3- (4-hydroxyphenyl) acrylate.

2-phenyl-2-propenoic acid was used instead of methacrylic acid anhydride in the synthesis of the compound of the formula 29 shown in Example 1, and 4-Cholocyclohexanol was used instead of 1-Cholo-2-ethanol as a substance reacting with the intermediate (1) , Except that 6-oxabicyclo [3.1.0] hexan-2-ol was used instead of methanol in the production step of intermediate (5)

2-phenyl-2-propenoic acid was used in place of methacrylic acid anhydride in the synthesis of the compound of the formula 29 shown in Example 1 and the compound reacted with the intermediate (1) was replaced with 5-chlorothiophen-2- except that vinyl 3- (4-hydroxy-2-methoxyphenyl) acrylate was used instead of intermediate (5)

Acrylic acid anhydride was used in place of methacrylic acid anhydride in the synthesis of the compound of Formula 29 shown in Example 1 and the compound reacting with the intermediate (1) was replaced with 3- (chloromethyl) -1,1,3 Except that 3-tetramethyl-1-disiloxanol was used and acrylic 3- (4-chlorophenyl) propanoic anhydride was used in place of Intermediate (5).

2-chloro-2-propenoic acid was used instead of methacrylic acid anhydride in the synthesis of the compound of the formula (29) shown in Example 1, and the compound reacting with the intermediate (1) was used instead of 1-Cholo- Except that 3- (4-chlorophenyl) propanoic methacrylic anhydride was used in place of Intermediate (5) using 2,3,3,4-heptafluorobutan-1-ol,

Acrylic acid anhydride was used instead of methacrylic acid anhydride in the synthesis of the compound of the formula 29 shown in Example 1 and the compound reacted with the intermediate (1) was replaced with 1-chloro-3-methylbutan-2- except that N- (7-hydroxy-2-oxo-2H-chromen-4-yloxy) acrylamide was used instead of Intermediate (5)

2-chloro-2-propenoic acid was used instead of methacrylic acid anhydride in the synthesis of the compound of the formula 29 shown in Example 1, and the compound reacting with the intermediate (1) was replaced with chloro (isopropyl) amino ) methanol, except that N- (7-hydroxy-2-oxo-2H-chromen-4-yloxy) methacrylamide was used in place of Intermediate (5)

2-phenyl-2-propenoic acid was used instead of methacrylic acid anhydride in the synthesis of the compound of the formula (29) shown in Example 1 and 2-chloroethoxy-methanol was used instead of 1-Cholo- Except that 2,5-dioxo-2,5-dihydro-1H-pyrrol-1-yl 3- (4-chlorophenyl) propanoate was used in place of Intermediate (5)

Acrylic acid anhydride was used instead of methacrylic acid anhydride in the synthesis of the compound of the formula 29 shown in Example 1 and 2-chloroethylcarbamic acid was used instead of 1-Cholo-2-ethanol to react with the intermediate (1) Except that 2.5-dioxo-2,5-dihydro-1H-pyrrol-1-yl 3- (4-hydroxy-2-methoxyphenyl) acrylate was used instead of 2,5-

M L ¹ P ¹ L ² P ² L ³ R ¹

2-chloro-2-propenoic acid was used instead of methacrylic acid anhydride in the synthesis of the compound of the formula (29) shown in Example 1, and the compound reacting with the intermediate (1) Except for using 3- (4-hydroxy-2-methoxyphenyl) acrylic 4- (diethoxy (methyl) silyl) -4-oxobut-2-enoic anhydride in place of Intermediate 5

2-chloroacetylcarbamic acid was used in place of 1-Cholo-2-ethanol and 2,3-dicyano-3- ( 4-hydroxyphenyl) acrylic 4 - (oxirane-2-carbonyl) benzoic anhydride,

2-phenyl-2-propenoic acid was used instead of methacrylic acid anhydride in the synthesis of the compound of the formula 29 shown in Example 1, and 4-Cholocyclohexanol was used instead of 1-Cholo-2-ethanol as a substance reacting with the intermediate (1) , Except for using 3- (6-oxabicyclo [3.1.0] hexan-2-yl) -2,3-dicyanopropanoic acid in place of methanol in the preparation of intermediate (5)

2-phenyl-2-propenoic acid was used in place of methacrylic acid anhydride in the synthesis of the compound of the formula 29 shown in Example 1 and the compound reacted with the intermediate (1) was replaced with 5-chlorothiophen-2- except for using 3- (4-hydroxy-2-methoxyphenyl) acrylic 2-oxo-2- (vinyloxy) ethylcarbamic anhydride instead of Intermediate (5)

Chloro-2-ol instead of 1-Cholo-2-ethanol in the synthesis of the compound of the formula (29) shown in Example 1 and 3- (4-chloro -2-methoxyphenyl) acrylic 2-oxo-2- (vinyloxy) ethylcarbamic anhydride.

2-chloro-2-propenoic acid was used instead of methacrylic acid anhydride in the synthesis of the compound of the formula (29) shown in Example 1, and the compound reacting with the intermediate (1) was used instead of 1-Cholo- Except that 2,3,3,4-heptafluorobutan-1-ol was used and 2-fluoro-4- (2- (3- (4-hydroxyphenyl) propanoyloxy) ethyl) phenethyl methacrylate was used in place of Intermediate (5) Were prepared in the same manner

Acrylic acid anhydride was used instead of methacrylic acid anhydride in the synthesis of the compound of the formula 29 shown in Example 1 and the compound reacted with the intermediate (1) was replaced with 1-chloro-3-methylbutan-2- except that N- (6- (7-hydroxy-2-oxo-2H-chromen-4-yloxy) naphthalen-2-yl) acrylamide was used in place of Intermediate (5) Produce

2-chloro-2-propenoic acid was used instead of methacrylic acid anhydride in the synthesis of the compound of the formula 29 shown in Example 1, and the compound reacting with the intermediate (1) was replaced with chloro (methyl) amino ) methanol was used and the remainder except for using N- (2- (4-hydroxycyclohexyl) ethyl) methacrylamide instead of methanol in the preparation of intermediate (5)

2-phenyl-2-propenoic acid was used instead of methacrylic acid anhydride in the synthesis of the compound of the formula (29) shown in Example 1 and 2-chloroethoxy-methanol was used instead of 1-Cholo- 2,5-dihydro-1H-pyrrol-1-yl) -N- (2- (7-hydroxy-2-oxo- 2H-chromen -4-yloxy) ethyl) acetamide.

Acrylic acid anhydride was used instead of methacrylic acid anhydride in the synthesis of the compound of the formula 29 shown in Example 1 and 2-chloroethylcarbamic acid was used instead of 1-Cholo-2-ethanol to react with the intermediate (1) (E) -3,4,5-tricyano-6- (2,5-dioxo-2,5-dihydro-1H-pyrrol-1-yl) hexyl 3- (4-hydroxy-2-methoxyphenyl) acrylate Except for using the same method

≪ Example 2 > Preparation of polymer represented by formula (30)

(E) - (4 - ((4 - ((E) -3-methoxy-3-oxoprop- 1-enyl) phenoxy) phenoxy) ethyl) 1-methyl 2-ethyl-2,4,4-trimethylpentanedioate-co-methyl methacrylate

Polymerization was carried out in the same manner as in Example 1, except that methyl methacrylate was added to the method of Example 1.

Figures 2a, 2b and 2c show the < 1 > H-NMR, FT-IR and UV spectra of the photo-alignment polymer having the structure of formula (30), respectively.

The formula (30) corresponds to an example of the copolymer represented by the formula (28), and the repeating unit composed of M "and L ¹ " in the formula (28) can be synthesized to have the following structure using a method similar to the above-described method.

M " L ¹ "

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Acrylic acid anhydride was used instead of methacrylic acid anhydride in the synthesis method of Intermediate 4 shown in Fig. 1 and Example 1, and instead of Intermediate 3

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2-phenyl-2-propenoic acid was used instead of methacrylic acid anhydride in the synthesis of Intermediate 4 shown in FIG. 1 and Example 1, and instead of Intermediate 3

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2-chloro-2-propenoic acid was used instead of methacrylic acid anhydride in the synthesis of Intermediate 4 shown in Fig. 1 and Example 1,

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1 < / RTI > and in the method of synthesis of intermediate 4 shown in Example 1

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,

,

,

,,

or

2-methoxyprop-1-ene was used instead of methacrylic acid anhydride in the synthesis method of Intermediate 4 shown in Fig. 1 and Example 1, and instead of Intermediate 3

,

,

,

,

or

Manufacturing

,

,

,

,

or

In the synthesis of Intermediate 4 shown in Fig. 1 and Example 1, 4-vinylphenol was used instead of methacrylic acid anhydride, and instead of Intermediate 3

,

,

,

,

or

Manufacturing

,

,

,

,

,

or

(4-vinylphenyl) methanol was used instead of methacrylic acid anhydride in the synthesis method of Intermediate 4 shown in Fig. 1 and Example 1, and instead of Intermediate 3

,

,

,

,

or

Manufacturing

Accordingly, in addition to the structure represented by the formula (30) including the monomers having the structure of M " and L &^lt; ¹ &^gt;, the structure corresponding to the formula (28) can be variously synthesized. Other synthetic examples of the polymer corresponding to the formula (28) are shown below.

(Example 2-1) In the polymerization step of the chemical formula 29 shown in Example 1, methyl methacrylate was further added and 4 - ((E) -3-methoxy-3-oxoprop- (E) -3-hexyloxy-3-oxoprop-1-enyl) phenyl 4 - ((4- (2- (methacryloyloxy) hexyloxy) phenyl ) diazenyl) benzoate was used as a polymerization initiator.

<Example 2-2> In the polymerization step of the chemical formula (29) shown in Example 1, methyl methacrylate was further added, and 4 - ((E) -3-methoxy-3-oxoprop- 3- (2,5-dioxocyclopent-3-enyl) propanoyloxy) phenyl) -3-oxopropionic acid was used instead of 4- (2- (methacryloyloxy) 1-enyl) phenyl 4 - ((E) - (4- (6- (methacryloyloxy) hexyloxy) phenyl) diazenyl) benzoate was used.

Example 2-3 In the polymerization step of Chemical Formula 29 shown in Example 1, 2-chloro-N-methylacrylamide was further added, and 4 - ((E) -3-methoxy-3-oxoprop- 4 - ((4- (2- (dimethyl (dimethyl) -2-oxo-2- (prop-1-ene) 2-yloxy) ethyl) silyloxy) silyloxy) propan-2-yloxy) phenyl) diazenyl) phenyl 4 - ((E) -3-ethoxy-3-oxoprop-1-enyl) phenyl terephthalate The polymerization was carried out in the same manner as in Example 1.

Example 2-4> In the polymerization step of the chemical formula 29 shown in Example 1, N-methylmethacrylamide was further added and 4 - ((E) -3-methoxy-3-oxoprop- (E) - (4- (2- (3-acryloylureido) -2-oxoethoxy) phenyl) diazenyl) phenyl 4 - ((E) - The polymerization was carried out in the same manner as in Example 1 except that 3- (hexyloxy) -3-oxoprop-1-enyl) -3-methoxyphenyl succinate was used.

(Example 2-5) 4- (1-chlorovinyl) -2-ethoxy-1-methoxybenzene was further added in the polymerization step of Chemical Formula 29 shown in Example 1 to obtain 4 - ((E) -3- methoxy- 3-methoxy-3-oxoprop-1-enyl) phenyl 4- ((4- (2- (methacryloyloxy) ethoxy) phenyl) diazenyl) ((E) - (4- (6- (2-phenylacryloyloxy) hexyloxy) phenyl) diazenyl) benzoate was used.

Example 2-6 In the polymerization step of the chemical formula 29 shown in Example 1, 1- (butoxymethyl) -4-vinylbenzene was further added and 4 - ((E) -3-methoxy-3-oxoprop- (E) - ((E) -3-ethoxy-3-oxoprop-1-enyl) phenyl 4 - ((4- Polymerization was carried out in the same manner as in Example 1, except that 4- (methacryloyloxy) cyclopenta-1,3-dienyloxy) phenyl) diazenyl) phenyl fumarate was used.

Example 2-7 In the polymerization step of the chemical formula 29 shown in Example 1, 2-chloro-N-methylacrylamide was further added, and 4 - ((E) -3-methoxy-3-oxoprop- (E) -3- (5- (6-oxabicyclo [3.1.0] hexan-2-yl) -3,2,3,4-tetrahydroisoquinoline in place of 4- (2- (methacryloyloxy) 4-dicyano-2-oxopentyloxy) -3-oxoprop-1-enyl) phenyl 4 - ((E) -4- (2,4,4- 2-yloxy) hexan-2-yloxy) phenyl) diazenyl) phenyl terephthalate was used as the initiator.

(Example 2-8) In the polymerization step of the chemical formula 29 shown in Example 1, 1- (2-phenylacryloyloxy) urea was further added and 4 - ((E) -3-methoxy-3-oxoprop- 2,5-dioxo-2,5-dihydro-1H-benzoate was used instead of 4- ((4- (2- (methacryloyloxy) phenyl) diazenyl) benzoate was prepared by the same procedure as in (1), except that (4-methylpyrrolidin-1-yl) The polymerization was carried out in the same manner as in Example 1, except that the catalyst was used.

&Lt; Example 3 > Preparation of polymer represented by formula (31)

2-oxo-2H-chromen-7-yloxy) carbonyl) phenyl) diazenyl) phenoxy (2-oxo- ) ethyl) 2,2,4,5-tetramethylhexanedioate-co-methyl methacrylate]

Polymerization was carried out in the same manner as in Example 1, except that methyl methacrylate was added to the method of Example 1.

Figs. 3A, 3B and 3C show the &lt; 1 &gt; H-NMR, FT-IR and UV spectra of the photo-alignment polymer having the structure of Formula 31, respectively.

(31) corresponds to an example of the copolymer represented by the formula (28). In addition to the structure represented by the formula (31) including the monomer having the structure of M "and L ¹ ", the structure corresponding to the formula (28) can be variously synthesized . Another synthesis example of the polymer corresponding to the formula (28) is shown below.

<Example 3-1> N-pentyl-2-phenylacrylamide was further added to the polymerization step of the chemical formula 29 shown in Example 1, and 4 - ((E) -3-methoxy-3-oxoprop- 4-methyl-2-oxo-2H-chromen-7-yl 4 - [(4- {2- [4- (4- (2- (methacryloyloxy) ethoxy) phenyl) - (prop-1-en-2-yl) benzyloxy) ethoxy) phenyl) diazenyl) benzo

<Example 3-2> In a polymerization step of the chemical formula 29 shown in Example 1, prop-1-en-2-yl 2,2,3,3-tetrafluoro-3-methoxypropanoate was further added and 4 - ((E ) -3-methoxy-3-oxoprop-1-enyl) phenyl 4- (3- (6-oxabicyclo [3.1.0] hexane 2-yl) -2,3-dicyanopropanoyloxy) -2-oxo-2H-chromen-7-yl 4 - ((E) The polymerization was carried out in the same manner as in Example 1 except for the following.

Example 3-3 In the polymerization step of the chemical formula 29 shown in Example 1, N- (2- (methoxymethoxy) ethyl) acrylamide was further added and 4 - ((E) -3-methoxy- (E) -4- (3- (chlorodiethoxysilyl) propylcarbamoyloxy) -2-oxo-2H-chromen-7-yl The polymerization was carried out in the same manner as in Example 1 except that 4 - ((4- (2- (2- (4- (1-phenylvinyl) phenoxy) ethoxy) ethoxy) phenyl) diazenyl) benzoate.

<Example 3-4> 3-oxopentyl methacrylate was further added to the polymerization step of the chemical formula 29 shown in Example 1 and 4 - ((E) -3-methoxy-3-oxoprop- (Acryloyloxy) -2-oxo-2H-chromen-7-yl 4 - ((E) - (4- (3-oxo- (Vinylamino) propoxy) methylcarbamoyloxy) phenyl) diazenyl) phenyl fumarate was used as a polymerization initiator.

Example 3-5 In the polymerization step of the chemical formula 29 shown in Example 1, 2-acetoxyethyl acrylate was further added and 4 - ((E) -3-methoxy-3-oxoprop- (E) -4- (4 - ((4- (2- (4- (1-chlorovinyl) benzyloxy) ethylcarbamoyloxy) phenyl) diazenyl) phenyl ester instead of 4- (2- (methacryloyloxy) Yl) methoxy) -2-oxo-2H-chromen-7-yl) -2-fluoro-3-methyl- The polymerization was carried out in the same manner as in Example 1.

&Lt; Example 4 > Preparation of polymer represented by formula (32)

(32)

(E) -6-methyl 1- (2- (4 - ((4 - ((4-methyl-2-oxo-2H- chromen-7-yloxy) carbonyl) phenyl) diazenyl) phenoxy ) ethyl) 2,2,4,5-tetramethylhexanedioate was added to the reaction mixture.

(32) corresponds to an example of the copolymer represented by the formula (27). In addition to the structure represented by the formula (32), the structure corresponding to the formula (27) can be variously synthesized. Other synthetic examples of the polymer corresponding to the formula (27) are shown below.

Example 4-1 Preparation of 4 - ((E) -3-methoxy-3-oxoprop-1-enyl) phenyl 4 - [(4- (2- (methacryloyloxy) 2,5-dihydro-1H-pyrrol-1-yl) ethoxy) phenyl) diazenyl) benzoate was used instead of 4- ( (E) - (4- (3-oxo-3- (1-phenylvinyloxy) propoxy) phenyl) diazenyl) benzoate and (1E, 3E ) -4- (4-methyl-2-oxo-2H-chromen-7-yloxy) buta-1,3dienyl 4 - ((E) benzoate was used as the polymerization initiator.

Example 4-2 The procedure of Example 4-2 was repeated except that 4 - ((E) -3-methoxy-3-oxoprop-1-enyl) phenyl 4- (2- (methacryloyloxy) (E) -2,3-dicyano-3- (4 - ((E) -3- (4- (methyl (trichlorosilyl) methyl) carbamoyloxy) phenyl) -3-oxoprop- 1-enyl) phenoxy) allyl 4 - ((E) - (4 - ((vinyloxymethylamino) methoxy) phenyl) diazenyl) benzoate and 4 - ((E) -3- (4- (methacryloyloxy) cyclohexyloxy) ) -3-oxoprop-1-enyl) phenyl 4 - ((E) - (4- (2-chloro-N-isopropylacrylamido) ethoxy) phenyl) diazenyl) benzoate. Polymerization proceeded in the same manner.

Example 4-3 Preparation of 4 - ((E) -3-methoxy-3-oxoprop-1-enyl) phenyl 4 - [(4- (2- (methacryloyloxy) 2-oxo-2H-chromen-7-yl 4 - [(4- (2-ethyl- 3-isopropoxypentyloxy) phenyl) diazenyl) benzoate and (E) -4 - ((2- (acryloyloxy) ethoxy) carbonyloxy) -2-oxo- - (4- (1-phenylethyl) phenoxy) butan-2-yloxy) propoxy) phenyl) diazenyl) benzoate was used as the initiator.

Example 4-4 Synthesis of 4 - ((E) -3-methoxy-3-oxoprop-1-enyl) phenyl 4 - ((4- (2- (methacryloyloxy) (4 - ((E) -3- (4- (2- (3-methyl-2,5-dioxo-2,5-dihydro-1H- pyrrol- 1-yl phenyloxy) -3, 5-dioxopentyl 4 - ((E) - (4- ) -4- (1-fluoro-2- (methacryloyloxy) ethoxy) -2-oxo-2H-chromen-7-yl 4 - {(4- {N- ethyl- 2- (2-phenylacryloyloxy) acetamido) methoxy ) phenyl) diazenyl) benzoate was used as a polymerization initiator.

&Lt; Example 5 > Production of substrate and cell including polymer photo alignment layer

(E) -3-methoxy-3-oxoprop-1-enyl) phenyl 4 - ((4- (2- (methacryloyloxy) ethoxy) phenyl) diazenyl represented by the chemical formula 29 prepared in Example 1 ) benzoate was dissolved in a chloroform solvent at a concentration of 1 wt% to prepare a solution. The solution was spin-coated on the ITO glass surface and dried in an oven at 70 ° C. for 1 hour. The dried substrate was exposed to 4.0 mW / cm ² of linearly polarized UV light for 4 seconds, and was oriented at an energy of 16 mJ / cm ² . The cell was assembled by cementation.

&Lt; Example 5-1 > Production of substrate and cell including polymer photo alignment layer

A cell was fabricated in the same manner as in Example 5 except that the polymer prepared in Example 2-2 was used.

&Lt; Example 5-2 > Production of substrate and cell including polymer photo alignment layer

A cell was prepared in the same manner as in Example 5, except that the polymer prepared in Example 2 was used.

Example 5-3 Fabrication of Substrate and Cell Containing Polymer Photo-alignment Layer

A cell was fabricated in the same manner as in Example 5, except that the polymer prepared in Example 2-8 was used.

Example 5-4 Fabrication of Substrate and Cell Containing Polymer Photo-alignment Layer

A cell was fabricated in the same manner as in Example 5 except that the polymer prepared in Example 3 was used.

Example 5-5 Fabrication of Substrate and Cell Containing Polymer Photo Orientated Film

A cell was prepared in the same manner as in Example 5, except that the polymer prepared in Example 3-5 was used.

Example 6 Fabrication of Substrate and Cell Containing Polymer Photo Orientated Film

UV light irradiation was performed using the same method as in Example 5-2 except that the wavelength of 357 nm corresponding to the photo-isomerization was sequentially irradiated after first irradiating 284 nm corresponding to the light quantization using a wavelength selective filter To prepare a cell.

&Lt; Example 6-1 > Production of substrate and cell including polymer photo alignment layer

UV light irradiation was performed using the same method as in Example 5-2 except that the wavelength of 284 nm corresponding to the optical dimming was sequentially irradiated after 357 nm corresponding to optical isomerization was first irradiated using a wavelength selective filter To prepare a cell.

&Lt; Example 6-2 > Production of substrate and cell including polymer photo alignment layer

UV light irradiation was performed using the same method as in Example 5-2 except that the wavelength region of 357 nm corresponding to photoisomerization and the wavelength region of 284 nm corresponding to light quantization were simultaneously examined using a wavelength selection filter Respectively.

&Lt; Example 6-3 > Production of substrate and cell including polymer photo alignment layer

UV light irradiation was performed using the same method as in Example 5-4 except that the wavelength of 357 nm corresponding to the photo-isomerization was sequentially irradiated after first irradiating 325 nm corresponding to light quantization using a wavelength selective filter To prepare a cell.

Example 6-4 Fabrication of Substrate and Cell Containing Polymer Photo-alignment Layer

UV light irradiation was performed using the same method as in Example 5-4 except that 357 nm corresponding to optical isomerization was first irradiated using a wavelength selective filter and then a wavelength region of 325 nm corresponding to the optical dimming was sequentially irradiated To prepare a cell.

&Lt; Example 6-5 > Preparation of substrate and cell including polymer photo alignment layer

UV light irradiation was performed using the same method as in Example 5-4, except that the wavelength range of 357 nm corresponding to optical isomerization and 325 nm corresponding to light quantization were simultaneously examined using a wavelength selective filter Respectively.

&Lt; Comparative Example 1 > Production of substrate and cell including a polymer photo alignment layer

A cell was prepared using the same method as in Example 5 except that ROP108, a photo-oriented polymer of Rolic Co., was used.

EXPERIMENTAL EXAMPLE 1 Measurement of Uniformity of Orientation of Polymer Photo-alignment Layer

The on / off characteristics of the cells prepared according to Comparative Examples 1 and 5 to 5 to 5 were compared using an optical microscope. The on / off characteristics of the cells were compared with those of the polarizer. It was observed whether the light was transmitted or not, and the cell was rotated 45 degrees to observe whether the dark side was uniformly blocked by the light off state.

Figures 4, 5, 6, 7, 8, 9 and 10 show comparative examples 1, 5, 5-1, 5-2, 5-3, 5-4, The photograph of the on / off state of the cell fabricated in 5-5 is taken by optical microscope.

<Experimental Example 2> Measurement of optical stability of a polymer photo-alignment layer

The cells were irradiated with light by changing the direction of linearly polarized light after drying of the substrate during the cell preparation process according to Comparative Example 1 and Examples 5 to 5-5, And the alignment uniformity of the liquid crystal was confirmed.

The evaluation standard is usually a case where the alignment uniformity is lowered due to the additional alignment of the alignment film and the light leakage phenomenon is observed throughout the alignment film. In general, there is a difference in the alignment uniformity, but when the light leakage phenomenon partially occurs, the light leakage phenomenon can be confirmed through the microscope Were classified as excellent.

EXPERIMENTAL EXAMPLE 3 Measurement of chemical resistance of a polymer photo alignment layer

Cells were produced under the same conditions except for spin-coating the photo-alignment layer in the cell preparation process according to Comparative Example 1 and Example 5 to 5-5, and drying the substrate after it was dried in a chloroform solution for 30 seconds and then dried. The photo alignment layer was washed to confirm whether there was a portion where the liquid crystal could not be aligned.

The evaluation criteria were classified as excellent when the part of the photo alignment film melted out so as to be visible to the naked eye.

<Experimental Example 4> Measurement of thermal stability of a polymer photo alignment layer

The Tg values of the photo-alignment polymers used in Comparative Examples 1 and 5 to 5 were measured using a DSC instrument in a powder state. The Tg was measured at a temperature ranging from room temperature to 200 ° C., .

<Experimental Example 5> Measurement of photocrosslinking degree of polymer optical alignment layer

The substrates coated with the photo-alignment layers obtained in Comparative Examples 1 and 5 to 5 to 5 were subjected to an alignment treatment by using an ultraviolet spectroscopic analyzer to measure the absorption wavelength band of the ultraviolet region (Chalcone : 340 nm, Cinnamate: 284 nm, coumarine: 325 nm).

The evaluation criterion was classified as below 5% of light bridging, excellent as less than 10%, and excellent as 10% or more.

Table 10 below summarizes the results of the tests for Comparative Examples 1 and 5 to 5-5.

division Cell On / Off Comparison Orientation
Uniformity ore
stability Chemical resistance Thermal
stability
(° C) ore
Bridging degree
(%) On Off Comparative Example
One 4 usually usually usually 125.25 2 (a) (b) Example
5 5 Great Great Great 130.65 5 (a) (b) Example
5-1 6 Extremely
Great Extremely
Great Extremely
Great 136.75 8 (a) (b) Example
5-2 7 Great Great Great 129.15 8 (a) (b) Example
5-3 8 Extremely
Great Extremely
Great Extremely
Great 140.25 12 (a) (b) Example
5-4 9 Great Great Great 136.45 6 (a) (b) Example
5-5 10 Extremely
Great Extremely
Great Extremely
Great 146.25 10 (a) (b)

Referring to Table 10, it can be seen that the use of the photo-orientable polymer according to the present invention shows excellent results in both of the alignment uniformity, the light stability, the chemical resistance, the thermal stability and the photo-crosslinking. In particular, Examples 5-1, 5-3 and 5-5, which have terminal crosslinking groups in the side chain of the photo-orientable polymer and can perform additional photo-crosslinking reaction, show the best characteristics.

The alignment uniformity and the photo-crosslinking degree according to the light irradiation method were measured and are shown in Table 11 below.

Figs. 11, 12, 13, 14, 15, and 16 respectively show the results of the measurements This is a photograph of the on / off state of the cell taken with an optical microscope.

division UV
Investigation method Research
energy
(mJ / cm ² ) Cell On / Off Comparison Orientation
Uniformity ore
Bridging degree
(%) On Off Example
5-2 Wave field 16 7 Great 5 (a) (b) Example
6 Crosslinking (284 nm)
-> orientation (357 nm) Bridging: 8
Orientation: 8 11 Great 14 (a) (b) Example
6-1 Orientation (357 nm)
-> bridging (284 nm) Orientation: 8
Bridging: 8 12 Extremely
Great 7 (a) (b) Example
6-2 Crosslinking (284 nm)
+ Orientation (357 nm) 16 13 Great 5 (a) (b) Example
5-4 Wave field 16 9 Great 5 (a) (b) Example
6-3 Crosslinking (325 nm)
-> orientation (357 nm) Bridging: 8
Orientation: 8 14 Great 12 (a) (b) Example
6-4 Orientation (357 nm)
-> bridging (325 nm) Orientation: 8
Bridging: 8 15 Extremely
Great 6 (a) (b) Example
6-5 Crosslinking (325 nm)
+ Orientation (357 nm) 16 16 Great 6 (a) (b)

Referring to Table 11, it can be understood that the case of irradiating light having a selective wavelength corresponding to the orientation and crosslinking (i.e., photoisomerization and photo-dimerization), respectively, is more uniform than the case of irradiating light corresponding to the UV propagation region, And it shows excellent results in terms of the degree of crosslinking. In addition, the successive irradiation of the light having the selective wavelength corresponding to the orientation and the crosslinking showed better results than the simultaneous irradiation, and it can be confirmed that the order of irradiation also influences the orientation and crosslinking characteristics.

Claims (19)

1. A photo-orientable polymer represented by the following formula (1): < EMI ID =
&Lt; Formula 1 &gt;

In Formula 1,
M is a vinyl polymerizable monomer unit constituting the polymer main chain,
L ¹ , P ¹ , L ² , P ² , L ³ and R ¹ are units constituting the polymer side chain,
L ¹ , L ² and L ³ are, independently of each other, a single bond; A straight or branched hydrocarbon group of 1 to 24 carbon atoms which is unsubstituted or substituted by a cyano group or a halogen group, wherein at least one of the CH ₂ groups of the hydrocarbon group may be independently replaced by a group A; A halogen group or a straight or branched alkyl residue having 1 to 24 carbon atoms wherein the alkyl residue may be unsubstituted or substituted with a cyano group or a halogen group and at least one of the CH ₂ groups of the alkyl residue One of which may be independently substituted by group A), wherein the aromatic or alicyclic hydrocarbon group may be a heterocycle comprising O, N or S,
And A is -O-, -S-, -CO-, -CO- O-, -O-CO-, -Si (CH 3) 2 -O-Si (CH 3) 2 -, -NR 2 -, ^{-NR 2 -CO-, -CO-NR 2} -, -NR 2 -CO-O-, -O-CO-NR 2 -, -NR 2 -CO-NR 3 -, -CH = CH-, -C -O-CO-O- wherein R ² and R ³ are, independently of each other, hydrogen or a lower alkyl group,
Wherein one of P ¹ and P ² is a photo-isomerizing group containing a group represented by the following formula (2) or (3) and the other is a photo-isomerizing group containing a group represented by the following formula (4)
R ¹ is a terminal crosslinking group, and n is 1.

(2)

(3)

In the above Formulas 2 and 3,
The broken line represents the bonding point in the side chain,
B is an unsubstituted or substituted group selected from the group consisting of a cyano group, a halogen group, or a straight, branched or cyclic alkyl residue of 1 to 24 carbon atoms wherein the alkyl residue may be unsubstituted or substituted by a cyano group or a halogen group, CH ₂ groups may be independently replaced by a group A wherein A is as defined in claim 1, pyrimidine-2, 5-diyl, pyridin-2 , 5-diyl, 2,5-thiophenylene, 2,5-furanylene, 1,4-naphthylene or 2,6-
E is -O-, -OR ⁴ -, -NR ⁵ R ⁶ -, or an oxygen atom bonded to ring B at the ortho position to form a coumarin unit, wherein R ⁴ , R ⁵ and R ⁶ independently of one another are hydrogen (Wherein R ⁴ and R ⁶ are not hydrogen), or a straight, branched or cyclic hydrocarbon group of 1 to 18 carbon atoms, wherein the hydrocarbon group may be unsubstituted or substituted by a halogen group, and CH At least one of the _two groups may be independently replaced by -O-, -CO-, -CO-O-, -O-CO- or -CH = CH-, and R ⁵ and R ⁶ together form a bond To form an alicyclic ring of 5 to 8 atoms,
X and Y are each independently a hydrogen, a cyano group, a halogen group, or a hydrocarbon group of 1 to 12 carbon atoms substituted by unsubstituted or fluorine, wherein at least one of the CH ₂ groups of the hydrocarbon group is independently -O-, -CO-O-, -O-CO- or -CH = CH-), when E is an oxygen atom which bonds to ring B at the ortho position to form a coumarin unit, X and Y Either one is a single bond connected to L &lt; ² &gt; or L &lt; ³ &gt; or -O-.
&Lt; Formula 4 &gt;

In the formula (4), the broken line indicates a bonding point in the side chain. The method according to claim 1,
Wherein the photo-dimer comprises at least one selected from a cinnamate group and a coumarin group. The method according to claim 1,
Wherein R < ¹ > is selected from the group of the following formulas (5) to (14):
&Lt; Formula 5 >

(6)

&Lt; Formula 7 >

(8)

&Lt; Formula 9 >

&Lt; Formula 10 >

&Lt; Formula 11 >

&Lt; Formula 12 >

&Lt; Formula 13 >

&Lt; Formula 14 >

In the general formulas (5) to (14), the broken line represents a bonding point to L ³ ,
In Formula 5, x, y, and z are each an integer of 0 to 3 (provided that x + y + z = 3)
In Formula 7, o is an integer of 1 to 7. The method according to claim 1,
The vinyl polymerizable monomers may be selected from the group consisting of acrylate, methacrylate, 2-chloroacrylate, 2-phenyl acrylate, N-lower alkyl substituted acrylamide, methacrylamide, 2-chloroacrylamide, Vinyl ethers, vinyl esters, styrenes, and derivatives thereof. The method according to claim 1,
Wherein M is a photo-orientable polymer selected from the group consisting of the following formulas (15) to (26):
&Lt; Formula 15 >

&Lt; Formula 16 >

&Lt; Formula 17 >

&Lt; Formula 18 >

(19)

(20)

&Lt; Formula 21 >

(22)

&Lt; Formula 23 >

&Lt; EMI ID =

&Lt; Formula 25 &gt;

(26)

In the general formulas (15) to (26), the broken line represents the point of attachment to the side chain,
In the above formulas (19) to (22), R ⁷ is hydrogen or a lower alkyl group. A photo-orientable polymer comprising an interpolymer composed of two or more different compounds represented by the following formula (27)
&Lt; Formula 27 >

In Formula 27,
M, L ¹ , P ¹ , L ² , P ² , L ³ , R ¹ and n are the same as defined in the formula (1)
^{M ', L 1', P} 1 ', L 2', P 2 ', L 3', R 1 ' and n' are each ^{M, L 1, P 1,} L 2, P 2, L 3, R 1 And n, and is selected from at least one of M, L ¹ , P ¹ , L ² , P ² , L ³ and R ¹ . A photo-orientable polymer comprising an interpolymer composed of two or more different compounds represented by the following formula (28):
(28)

In Formula 28,
M, L ¹ , P ¹ , L ² , P ² , L ³ , R ¹ and n are the same as defined in the formula (1)
M "is selected from the same group as M,
L ¹ "is hydrogen or a linear or branched hydrocarbon group having 1 to 24 carbon atoms which is unsubstituted, substituted by a cyano group or a halogen group, wherein at least one of the CH ₂ groups of the hydrocarbon group is independently substituted by a group A Or a linear or branched alkyl residue of 1 to 24 carbon atoms in which the alkyl residue may be unsubstituted or substituted by a cyano group or a halogen group, Wherein at least one of the CH ₂ groups of the aromatic or alicyclic hydrocarbon group may be independently replaced by a group A, wherein the aromatic or alicyclic hydrocarbon group is a heterocyclic group containing O, N or S ),
And A is -O-, -S-, -CO-, -CO- O-, -O-CO-, -Si (CH 3) 2 -O-Si (CH 3) 2 -, -NR 2 -, ^{-NR 2 -CO-, -CO-NR 2} -, -NR 2 -CO-O-, -O-CO-NR 2 -, -NR 2 -CO-NR 3 -, -CH = CH-, -C -O-CO-O- wherein R ² and R ³ are, independently of each other, hydrogen or a lower alkyl group. Preparing a substrate;
Coating the photo-orientable polymer of any one of claims 1 to 7 on the substrate; And
Irradiating the coated photo-orientable polymer with light to photo-isomerize and photo-dimerize the polymer;
&Lt; / RTI &gt; 9. The method of claim 8,
And cross-linking a terminal crosslinking group contained in side chains of the coated photo-orientable polymer. 10. The method of claim 9,
The step of cross-linking the terminal cross-linking group is carried out by at least one method selected from light irradiation, heat treatment, acid treatment and catalytic treatment. 9. The method of claim 8,
Wherein the step of photo-isomerizing and photo-dimerizing the polymer is performed by irradiating light corresponding to the wavelength of the UV region. 9. The method of claim 8,
Wherein the step of photo-isomerizing and photo-dimerizing the polymer is performed by simultaneously irradiating light having a maximum absorption wavelength region of the photo-isomerizer and a maximum absorption wavelength region of the photo-dimer. 9. The method of claim 8,
Wherein the step of photo-isomerizing and photo-dimerizing the polymer is conducted by sequentially irradiating light having a maximum absorption wavelength region of the photo-isomerizer and a maximum absorption wavelength region of the photo-dimer. 11. The method of claim 10,
Wherein the step of cross-linking the terminal cross-linking group is performed by light irradiation, wherein the optical isomerization and photo-dimerization are performed simultaneously. Board; And
A coating layer which is disposed on the substrate and comprises the photo-orientable polymer according to any one of claims 1 to 7;
&Lt; / RTI &gt; 16. The method of claim 15,
Wherein the substrate is selected from the group consisting of glass, a cyclic olefin polymer film, a triacetylcellulose film, a polyethylene terephthalate film, a polycarbonate film, a polyisocyanate film, and a polyimide film. 16. The method of claim 15,
Wherein the coating layer forms an alignment film. 16. The method of claim 15,
Wherein the optical film is used as one of a retardation film, a viewing angle compensation film, and a protective film. A display device comprising the optical film of claim 15.

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