KR20120007780A - Photoalignment layer comprising quantum dot and liquid crystal cell comprising the same - Google Patents

Abstract

PURPOSE: An oriented membrane is provided to have excellent orientation by including cinnamate-based photo reactive group, and to improve photo reaction speed by efficiently transferring the energy of polarized UV light to photo reaction. CONSTITUTION: A composition for an oriented membrane comprises: a norbonene-based polymer including a photoreactive group; a quantum dot, a methacrylate-based compound, and a photoinitiator. A manufacturing method of the oriented membrane comprises: a step of forming a membrane by dissolving the composition into solvent, and spreading on the surface of a substrate; a step of drying the spread solution; and a step of orientation treating by irradiating polarized ultraviolet ray on the surface of the membrane.

Description

An alignment layer including a quantum dot and a liquid crystal cell including the same {PHOTOALIGNMENT LAYER COMPRISING QUANTUM DOT AND LIQUID CRYSTAL CELL comprising THE SAME}

The present invention relates to a photoalignment film having excellent orientation and improved photoreactivity.

Due to the good properties of polymer materials, various types of polymers developed or discovered as needed are used for various purposes in various fields. In order to meet the needs of various fields and overcome the limitations of polymers, efforts have been made to improve the properties of polymers by adding various organic or inorganic materials. As the industry develops and new technologies are developed, inorganic-organic hybrids are in the spotlight as a way to overcome them because the physical properties of hybrids made of existing organic compounds are no longer satisfactory. In particular, nanoparticles that show characteristics not seen in existing inorganic materials are attracting attention.

Many of the new properties expected to be quantum-size effects of various kinds of metals, metal oxides, and semiconductor materials can be studied and applied to useful products, so that these nanoparticles have sufficient stability in solution for a long time. They should not be entangled with each other over time to form large insoluble masses, and should be able to form into thin films or suitable forms while retaining the properties of existing nanoparticles. In order to make this possible, not only the development of new synthetic methods for soluble nanoparticles, but also efficient surface treatment methods have been developed to ensure that the mixing with the matrix material to be mixed occurs at the molecular level without causing macroscopic separation between the materials. The physical properties of the nanoparticles must be maintained. Among them, the quantum dots can absorb almost all wavelengths, have good physical properties to control the emission wavelength according to the type and size of the quantum dots, and are excellent in stability by light than conventional organic materials.

Photo-alignment refers to a mechanism for forming a photopolymerizable liquid crystal alignment layer in which a photosensitive group bonded to a polymer by linearly polarized UV causes a photoreaction, and the main chain of the polymer is aligned in a predetermined direction, thereby aligning the liquid crystal.

Representative examples of such optical alignment are M. Schadt et al. (US Pat. No. 5,602,661, Jpn. J. Appl. Phys., Vol31. \, 1992, 2155), Dae S. Kang et al. (US Pat. No. 5,464,669), Yuriy Photoalignment by photopolymerization published by Reznikov (Jpn. J. Appl. Phys. Vol. 34, 1995, L1000).

As the photo-alignment polymer used in the above-mentioned existing patents and papers, polysinamate-based polymers such as poly (vinyl cinnamate) and PVMC (poly (vinyl methoxycinnamate) were mainly used. The double bond of cinnamate reacts with the [2 + 2] cycloaddition reaction by UV light, thereby forming a cyclobutane, resulting in anisotropy, thereby forming liquid crystal molecules in one direction. The alignment is induced to align the liquid crystal.

Appl. Phys. Lett., 2004, 85, 224. and J. of Photochem. Photobio. In A., 1998, 113 and 155, benzophenone series and pyrylium series photoactive agents were used to improve photoreactivity of photo-alignment materials such as cinnamate. However, in order to see a marked improvement in photoreactivity, the photoactive agent used in the same weight% as the alignment material had to be used in excess.

In general, to increase the speed of dimerization of vinyl group in the cinnamate (PVCi), which is known as a photo-alignment material, it is required to use less than conventional organic materials and to reduce the exposure time of ultraviolet rays.

In order to solve the above problems, it is an object of the present invention to provide a composition for a liquid crystal alignment film not only excellent in alignment, but also improved photoreactivity, and an optical alignment film prepared using the same and a liquid crystal cell including the same.

The present invention provides a composition for a liquid crystal alignment film comprising 1) a norbornene-based polymer having a photoreactive group, 2) a quantum dot, 3) a (meth) acrylate compound, and 4) a photoinitiator.

In addition, the present invention comprises the steps of a) dissolving the liquid crystal aligning composition according to the present invention in a solvent and then coating the surface of the substrate to form a coating film, b) drying the solvent contained in the coating film, c) the dried It provides a method for producing a liquid crystal alignment film comprising the step of performing an alignment treatment by irradiating polarized ultraviolet to the coating film surface.

In addition, the present invention provides a liquid crystal alignment layer comprising the composition for liquid crystal alignment.

Moreover, this invention provides the liquid crystal cell containing the said liquid crystal aligning film.

The photo-alignment film according to the present invention not only has excellent orientation, including cinnamate-based photoreactive groups, and also contains quantum dots, so that the energy of polarized UV can be efficiently transferred to the photoreaction, thereby improving the photoreaction rate. .

1A is a schematic diagram showing the structure of a simplified TFT-Cell according to the present invention.
1B is a schematic diagram showing a cell structure for implementing an IPS TFT-Cell according to the present invention.
Figure 1c is a schematic diagram showing a cell structure for implementing a TN TFT-Cell according to the present invention.
2 is a TEM image of a quantum dot of the present invention.
Figure 3 shows the light transmittance of the alignment film including a quantum dot according to the present invention.
Figure 4 shows the light absorption / light emission of the alignment layer including a quantum dot according to the present invention.
5A and 5B show measurement results of photoreaction and anisotropy of an alignment layer including a quantum dot according to the present invention.

Hereinafter, the present invention will be described in more detail.

The photoreactive norbornene-based polymer according to the present invention is used together with a quantum dot including a norbornene-based monomer containing a specific photoreactive functional group, thereby undergoing photoreaction by UV irradiation to have curing and orientation in accordance with the UV direction.

The quantum dots also include quantum dots including photoreactive functional groups prepared by surface treatment with cinnamate having photoreactive properties.

      Specifically, the photo-alignment material used in combination with the quantum dots is obtained by the light energy efficiently by the quantum dots is improved photoreactivity.

Specifically, the composition for liquid crystal alignment provided in the present invention is characterized by including 1) a norbornene-based polymer having a photoreactive group, 2) a quantum dot 3) a (meth) acrylate compound, and 4) a photoinitiator. .

In the composition for liquid crystal alignment of the present invention, it is preferable that the norbornene-based polymer having 1) photoreactive group contains a norbornene-based monomer represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

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 Formula 2,

The others may be the same or different from each other, and each independently hydrogen; halogen; Substituted or unsubstituted alkyl having 1 to 20 carbon atoms; Substituted or unsubstituted alkenyl having 2 to 20 carbon atoms; Substituted or unsubstituted cycloalkyl having 5 to 12 carbon atoms; Substituted or unsubstituted aryl having 6 to 40 carbon atoms; Substituted or unsubstituted arylalkyl having 7 to 15 carbon atoms; Substituted or unsubstituted alkynyl having 2 to 20 carbon atoms; And a non-hydrocarbonaceous polar group comprising at least one element selected from the group consisting of oxygen, nitrogen, phosphorus, sulfur, silicon, and boron,

R ₁ , R ₂ , R ₃ , and R ₄ are not hydrogen, halogen, or a polar functional group, and R ₁ and R ₂ , or R ₃ and R ₄ may be linked to each other to form an alkylidene group having 1 to 10 carbon atoms. Or R ₁ or R ₂ is R ₃ and R ₄ Connected to 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 2]

In Chemical Formula 2,

A is a simple bond, substituted or unsubstituted alkylene having 1 to 20 carbon atoms, carbonyl (-CO-), carbonyloxy (-(CO) O-), substituted or unsubstituted arylene having 6 to 40 carbon atoms , And substituted or unsubstituted heteroarylene having 6 to 40 carbon atoms,

B is selected from the group consisting of simple bonds, oxygen, sulfur, and -NH-,

R9 is a simple bond, substituted or unsubstituted alkylene having 1 to 20 carbon atoms, substituted or unsubstituted alkenylene having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkylene having 5 to 12 carbon atoms, substituted or unsubstituted Arylene having 6 to 40 carbon atoms, substituted or unsubstituted arylalkylene having 7 to 15 carbon atoms, and substituted or unsubstituted alkynylene having 2 to 20 carbon atoms,

R10, R11, R12, R13, and R14 may be the same as or different from each other, and each independently substituted or unsubstituted alkyl having 1 to 20 carbon atoms; Substituted or unsubstituted alkoxy having 1 to 20 carbon atoms; Substituted or unsubstituted aryloxy having 6 to 30 carbon atoms; Substituted or unsubstituted aryl having 6 to 40 carbon atoms; Hetero aryl having 6 to 40 carbon atoms containing group 14, 15 or 16 hetero elements; It may be selected from the group consisting of substituted or unsubstituted alkoxyaryl having 6 to 40 carbon atoms and a halogen element.

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Examples of the non-hydrocarbonaceous polar group in Formula 1 include, but are not limited to, the following functional groups. Specifically, -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) _k -OR ₆ ,-(OR ₅ ) _k -OR ₆ , -C (O) -OC (O) R ₆ , -R ₅ C (O) -OC (O) R ₆ , -SR ₆ , -R ₅ SR ₆ , -SSR ₆ , -R ₅ SSR ₆ , -S (= O) R ₆ , -R ₅ S (= O) R ₆ , -R ₅ C (= S) R _6- , -R ₅ C (= S) SR ₆ , -R ₅ SO ₃ R ₆ ,- SO ₃ R ₆ , -R ₅ N = C = S, -N = C = S, -NCO, -R ₅ -NCO, -CN, -R ₅ CN, -NNC (= S) R ₆ , -R ₅ NNC (= S) R ₆ , -NO ₂ , -R ₅ NO ₂ ,

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Is;

In the polar functional group,

R ₅ is the same as or different from each other, and each independently halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, Linear or branched alkylene having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from carbonyloxy, halocarbonyloxy, aryloxy, haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkenylene having 2 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkynylene having 3 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Cycloalkylene having 3 to 12 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Arylene having 6 to 40 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Alkoxylene having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Or halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy , Carbonyloxyylene having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy,

R ₆ , R ₇ and R ₈ are the same as or different from each other, and each independently hydrogen; Hydrogen, halogen, halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy Linear or branched alkyl having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from aryloxy, haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkenyl of 2 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkynyl having 3 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Cycloalkyl having 3 to 12 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Aryl having 6 to 40 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Alkoxy having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Or halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy , Carbonyloxy of 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy,

k is an integer of 1-10 each independently.

The norbornene-based polymer according to the present invention may be represented by the following formula 3, including the norbornene monomer of the formula (1).

(3)

In Chemical Formula 3,

n is 50 to 5,000,

p, R ₁ , R ₂ , R ₃ , and R ₄ are as defined above.

Method for producing a norbornene-based polymer represented by the formula (2) is a cocatalyst capable of weakly coordinating the norbornene monomer represented by the formula (1), a precatalyst containing a transition metal of Group 10 and the metal of the precatalyst In the presence of a catalyst mixture comprising, characterized in that the polymerization at a temperature of 10 ℃ to 200 ℃.

If the reaction temperature is less than 10 ℃ may cause a problem that the polymerization activity is very low, if it exceeds 200 ℃ may not decompose the catalyst is not preferred.

The catalyst mixture preferably contains 1 to 1,000 moles of cocatalyst which provides a Lewis base capable of weakly coordinating with the metal of the precatalyst with respect to 1 mole of the procatalyst comprising a transition metal of Group 10. If the content of the promoter is less than 1 mole may cause a problem that the catalyst activation does not occur, and if the content of the promoter exceeds 1,000 moles, rather than the catalyst activity of the procatalyst may be lowered is not preferred not.

The norbornene-based polymer according to the present invention may be represented by the following formula (4), including the norbornene monomer of the formula (1).

[Formula 4]

In Chemical Formula 4,

n is 50 to 5,000,

p, R ₁ , R ₂ , R ₃ , and R ₄ are as defined above.

The method for producing a norbornene-based polymer represented by Formula 4 may include the norbornene monomer represented by Formula 1 as Group 4 (eg, Ti, Zr, Hf), Group 6 (eg, Mo, W), Group 8 (eg, , Ru, Os), a procatalyst comprising a transition metal, a cocatalyst that provides a Lewis base capable of weakly coordinating with the metal of the procatalyst, and optionally a neutral 15 that can enhance the activity of the procatalyst metal. In the presence of a catalyst mixture consisting of activators of Groups and Groups 16, 1 to 100 mol% of linear alkene, such as 1-alkene and 2-alkene, whose molecular weight can be adjusted, is added to 10 1 to 30% by weight of a catalyst comprising a transition metal of Group 4 (eg Ti, Zr) or Group 8 to 10 (eg Ru, Ni, Pd) after polymerization at a temperature of Hydrogen to the double bonds remaining in the main chain at a temperature of 10 ° C. to 250 ° C. Characterized in that for performing Add.

If the reaction temperature is less than 10 ℃ causes a problem that the polymerization activity is very low, and if the reaction temperature is larger than 200 ℃ may cause a problem of decomposition of the catalyst is not preferred. When the hydrogenation reaction temperature is less than 10 ℃ causes a problem that the activity of the hydrogenation reaction is very low, and when larger than 250 ℃ causes the problem of decomposition of the catalyst is not preferred.

The catalyst mixture is precatalyst with respect to one mole of procatalyst comprising transition metals of Group 4 (e.g. Ti, Zr, Hf), Group 6 (e.g. Mo, W), Group 8 (e.g. Ru, Os). An activator comprising 1 to 100,000 moles of a cocatalyst that provides a Lewis base capable of weakly coordinating with the metal of the metal, and optionally a group of neutral group 15 and 16 elements that can enhance the activity of the procatalyst metal ( activator) from 1 to 100 moles per mole of procatalyst.

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

Hydrogenation when the content of the catalyst containing transition metals of Group 4 (eg Ti, Zr) or Groups 8 to 10 (eg Ru, Ni, Pd) used in the hydrogenation reaction is less than 1% by weight relative to the monomers. It is not preferable because there is a problem that is not well made and there is a problem that the polymer is discolored when larger than 30% by weight.

The procatalyst comprising transition metals of Group 4 (eg Ti, Zr, Hf), Group 6 (eg Mo, W) and Group 8 (eg Ru, Os) is provided by a promoter which provides a Lewis acid. It means a transition metal such as TiCl4, WCl6, MoCl5 or RuCl3 or ZrCl4, which has a functional group that easily participates in the Lewis acid-base reaction and is separated from the central metal so that the core transition metal can be easily converted into a catalytically active species.

In addition, the co-catalyst that provides a Lewis base that can weakly coordinate with the metal of the procatalyst is borane or borate such as B (C6F5) 3, methylaluminoxane (MAO) or Al (C2H5) 3, Al (CH3). Alkyl aluminum, such as Cl2, alkyl aluminum halide, and aluminum halide can be used. Alternatively, instead of aluminum, substituents such as lithium, magnesium, germanium, lead, zinc, tin, and silicon may be used. In this way, the compound easily reacts with the Lewis base to form a vacancy of the transition metal, and also weakly coordinates with the transition metal compound to provide a stabilized transition metal, or a compound providing the same.

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

Catalysts containing transition metals of Group 4 (e.g. Ti, Zr) or Groups 8-10 (e.g. Ru, Ni, Pd) used in the hydrogenation reaction are homogeneous forms that can be immediately mixed with the solvent. Or the metal catalyst complex supported on the 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.

According to an embodiment of the present invention, a cocatalyst and optionally a procatalyst metal which provide a procatalyst including a transition metal of Group 4, 6, and 8, and a Lewis base capable of weakly coordinating with the metal of the precatalyst. A catalyst mixture comprising neutral group 15 and 16 activators and the like capable of enhancing activity is prepared. In addition, linear alkene can be added to control the molecular weight. Thereafter, a solution containing the norbornene monomer represented by Formula 1 in the presence of an organic solvent and the catalyst mixture is subjected to hydrogenation after ring-opening polymerization. However, the order of administering the catalyst, the monomer and the solvent is not limited.

The norbornene-based polymer according to the present invention is a homopolymer of the norbornene monomer represented by Formula 1, a copolymer comprising two or more different norbornene monomers represented by Formula 1, norbornene monomer represented by Formula 1 And it may be in various forms such as a copolymer of the norbornene monomer represented by the formula (2).

In Formula 1, a hetero aryl group having 6 to 40 carbon atoms or an aryl group having 6 to 40 carbon atoms containing a hetero element of Group 14, 15 or 16 is one selected from the group consisting of compounds represented by the following formula: It may include, but is not limited to:

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In the above formula,

R _'10 , R _'11 , R' ₁₂ , R _'13 , R' ₁₄ , R _'15 , R' ₁₆ , R _'17 , And R _'18 At least one of substituted or unsubstituted alkoxy having 1 to 20 carbon atoms or substituted or unsubstituted aryloxy having 6 to 30 carbon atoms,

The remainder may be the same or different and each independently substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, or substituted Or unsubstituted aryl having 6 to 40 carbon atoms.

Looking at the definition of the above-described substituents in detail as follows.

"Alkyl" means a straight or branched chain saturated monovalent hydrocarbon moiety of 1 to 20, preferably 1 to 10, more preferably 1 to 6 carbon atoms. Alkyl groups may be optionally substituted by one or more halogen substituents. 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 straight or branched chain monovalent hydrocarbon moiety of 2 to 20, preferably 2 to 10, more preferably 2 to 6 carbon atoms comprising at least one carbon-carbon double bond. . Alkenyl groups may be bonded through a carbon atom comprising a carbon-carbon double bond or through a saturated carbon atom. Alkenyl groups may be optionally substituted by one or more halogen substituents. Examples of the alkenyl group include ethenyl, 1-propenyl, 2-propenyl, 2-butenyl, 3-butenyl, pentenyl, 5-hexenyl, dodecenyl, and the like.

"Cycloalkyl" means a saturated or unsaturated non-aromatic monovalent monocyclic, bicyclic or tricyclic hydrocarbon moiety of 3 to 12 ring carbons and may be optionally substituted by one or more halogen substituents. For example, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, cyclooctyl, decahydronaphthalenyl, adamantyl, norbornyl (ie bicyclo [2.2.1] Hept-5-enyl), and the like.

"Aryl" means a monovalent monocyclic, bicyclic or tricyclic aromatic hydrocarbon moiety having 6 to 20, preferably 6 to 12 ring atoms, which may be optionally substituted by one or more halogen substituents or the like. . Examples of the aryl group include phenyl, naphthalenyl, fluorenyl and the like.

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

"Arylalkyl" means that at least one hydrogen atom of the alkyl group as defined above is substituted with an aryl group, and may be optionally substituted with one or more halogen substituents. For example, benzyl, benzhydryl, trityl, etc. are mentioned.

"Alkynyl" means a monovalent hydrocarbon moiety of 2 to 20 carbon atoms, preferably 2 to 10, more preferably 2 to 6, straight or branched chains containing at least one carbon-carbon triple bond. do. Alkynyl groups may be bonded through a carbon atom comprising a carbon-carbon triple bond or through a saturated carbon atom. Alkynyl groups may be optionally substituted by one or more halogen substituents. For example, ethynyl, propynyl, etc. are mentioned.

"Alkylene" means a straight or branched chain saturated divalent hydrocarbon moiety of 1 to 20, preferably 1 to 10, more preferably 1 to 6 carbon atoms. Alkylene groups may be optionally substituted by one or more halogen substituents. Examples of the alkyl group include methylene, ethylene, propylene, butylene, hexylene and the like.

"Alkenylene" means a straight or branched chain divalent hydrocarbon site of 2 to 20, preferably 2 to 10, more preferably 2 to 6 carbon atoms containing at least one carbon-carbon double bond. do. Alkenylene groups may be bonded through a carbon atom comprising a carbon-carbon double bond and / or through a saturated carbon atom. Alkenylene groups may be optionally substituted by one or more halogen substituents.

"Cycloalkylene" means a saturated or unsaturated non-aromatic divalent monocyclic, bicyclic or tricyclic hydrocarbon moiety of 3 to 12 ring carbons and may be optionally substituted by one or more halogen substituents. For example, cyclopropylene, cyclobutylene, etc. are mentioned.

"Arylene" means a divalent monocyclic, bicyclic or tricyclic aromatic hydrocarbon moiety having 6 to 20, preferably 6 to 12 ring atoms, which may be optionally substituted by one or more halogen substituents. have. The aromatic portion of the aryl group contains only carbon atoms. Phenylene etc. are mentioned as an example of an arylene group.

"Arylalkylene" means a divalent moiety wherein at least one hydrogen atom of the alkyl group as defined above is substituted with an aryl group, and may be optionally substituted by one or more halogen substituents. For example, benzylene etc. can be mentioned.

"Alkynylene" means a divalent hydrocarbon moiety of 2 to 20 carbon atoms, preferably 2 to 10, more preferably 2 to 6, straight or branched chains containing at least one carbon-carbon triple bond. do. Alkynylene groups may be bonded through a carbon atom comprising a carbon-carbon triple bond or through a saturated carbon atom. Alkynylene groups may be optionally substituted by one or more halogen substituents. For example, ethynylene, propynylene, etc. are mentioned.

In the liquid crystal aligning composition according to the present invention, the 1) norbornene-based polymer is a procatalyst including a transition metal of Group 10, and a first cocatalyst which provides a Lewis base capable of weakly coordinating with the metal of the precatalyst. , And optionally in the presence of a catalyst mixture consisting of a second cocatalyst which provides a compound containing a neutral Group 15 electron donor ligand and a norbornene-based monomer having a photoreactive group, at a temperature of 10 ° C. to 200 ° C. . If the reaction temperature is less than 10 ℃ causes a problem that the polymerization activity is very low, and if the reaction temperature is larger than 200 ℃ may cause the problem of decomposition of the catalyst is not preferred.

The catalyst mixture comprises 1 to 1,000 moles of a first cocatalyst which provides a Lewis base capable of weakly coordinating with the metal of the precatalyst with respect to 1 mole of procatalyst comprising a Group 10 transition metal, and optionally neutral It is preferable to include 1 to 1,000 moles of the second cocatalyst which provides a compound containing a group 15 electron donor ligand. When the content of the first and second cocatalysts is less than 1 mole, there is a problem that the catalyst activation is not made, and when the content of the first and second cocatalysts is greater than 1,000 moles, the catalyst activity is lowered.

The procatalyst comprising the Group 10 transition metal is easily separated by the first cocatalyst which provides the Lewis acid to easily participate in the Lewis acid-base reaction so that the central transition metal can be converted into a catalytically active species. Compounds with Lewis base groups leaving off can be used. For example, [(Allyl) Pd (Cl)] ₂ (Allylpalladium chloride 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 )] _2, and the like.

In addition, the first cocatalyst, which provides a Lewis base capable of weakly coordinating with the metal of the procatalyst, easily reacts with the Lewis base to form a vacancy in the transition metal, and also in order to stabilize the transition metal thus formed. Compounds that weakly coordinate with metal compounds or compounds that provide them can be used. For example, boranes such as B (C ₆ F ₅ ) ₃ or borates such as dimethylanilinium tetrakis (pentafluorophenyl) borate, methylaluminoxane (MAO) or Al (C ₂ H ₅ ) there is a transition metal halide such as an alkyl aluminum, or AgSbF _6, such as _3.

In addition, a compound which activates the catalyst by making the first promoter and the second promoter into one salt may be used. For example, a compound made by ion bonding an alkyl phosphine and a borane compound may be used.

In the liquid crystal alignment composition according to the present invention, 2) quantum dots may include CdSe / ZnS, CdSe / ZnSe, ZnO, but are not limited thereto.

In the composition for liquid crystal alignment according to the present invention, the 3) (meth) acrylate-based compound is pentaerythritol triacrylate, tri (2-acrylolyloxyethyl) isocinurate (tris (2) -acrylolyloxyethyl) isocynurate), trimethylolpropane triacrylate and dipentaerythritol hexaacrylate may include one or more selected from the group consisting of, but is not limited thereto.

In the composition for liquid crystal alignment according to the present invention, Irgacure 907 and 819 may be used as the photoinitiator, but the present invention is not limited thereto.

The composition for liquid crystal alignment according to the present invention may further include an organic solvent. Preferred organic solvents include toluene, anisole, chlorobenzene, dichloroethane, cyclohexane, cyclopentane, propylene glycol methyl ether acetate acetate) and the like, but is not limited thereto.

The composition for liquid crystal alignment according to the present invention is based on the total weight of the composition 1) 50 to 70% by weight of the photoreactive polymer, 2) 1 to 20% by weight of quantum dots, 3) 20 to 40% by weight of the (meth) acrylate compound, And 4) 1 to 15% by weight of photoinitiator, but is not limited thereto.

In addition, the solid component in the composition for liquid crystal alignment according to the present invention is 1 to 15% relative to the solution in order to achieve the desired liquid crystal alignment effect, to have the desired coating properties, to have an appropriate viscosity, and to cast into a film 10 to 15% is preferable and 1-5% is preferable in order to make into a thin film.

In addition, the present invention comprises the steps of a) dissolving the liquid crystal aligning composition according to the present invention in a solvent and then coating the surface of the substrate to form a coating film, b) drying the solvent contained in the coating film, c) the dried It provides a method for producing a liquid crystal alignment film comprising the step of performing an alignment treatment by irradiating polarized ultraviolet to the coating film surface.

In step a), the concentration of the solution, the type of solvent and the coating method may be determined according to the type and use of the norbornene-based polymer, the (meth) acrylate-based compound, the acrylate-based reactive mesogen and the photoinitiator.

The composition for liquid crystal alignment in step a) may be applied onto the surface of the substrate formed by patterning a transparent conductive film or a metal electrode using a method such as a roll coater method, a spinner method, a printing method, an inkjet spraying method, or a slit nozzle method. have.

In the application of the solution, the functional silane-containing compound, the functional fluoro-containing compound, and the functional titanium-containing compound are previously applied to the substrate in order to further improve the adhesion of the substrate surface, the transparent conductive film, the metal electrode and the coating film. In some cases.

In step b), the solvent may be dried by heating the coating or vacuum evaporation.

Drying of the solvent of step b) is preferably carried out at 50 to 250 ℃ for 20 to 90 minutes.

In step c), the dried coating surface obtained in step b) may be subjected to an alignment treatment by irradiating polarized ultraviolet rays in a wavelength range of 150 to 450 nm. At this time, the intensity of exposure varies depending on the type of polymer, and energy of 50 mJ / cm 2 to 10 J / cm 2, preferably 500 mJ / cm 2 to 5 J / cm 2, can be irradiated.

As the ultraviolet rays, ① a polarizing device using a substrate coated with a dielectric anisotropic substance on the surface of a transparent substrate such as quartz glass, soda lime glass, soda lime free glass, ② a polarizing plate finely deposited aluminum or metal wire, or ③ An alignment treatment is performed by irradiating polarized ultraviolet rays selected from polarized ultraviolet rays by a method of passing or reflecting through a Brewster polarizer or the like by reflection of quartz glass. In this case, the polarized ultraviolet rays may be irradiated perpendicularly to the substrate surface, or may be irradiated at an inclined angle at a specific angle. In this way, the alignment ability of the liquid crystal molecules is imparted to the coating film.

The substrate temperature when irradiating the ultraviolet rays of step c) is preferably room temperature. However, in some cases, ultraviolet rays may be irradiated in a heated state within a temperature range of 100 ° C or lower.

It is preferable that the film thickness of the final coating film formed by a series of processes as mentioned above is 30-1000 nm.

Moreover, this invention provides the liquid crystal aligning film containing the said liquid crystal aligning composition.

In addition, the present invention provides a liquid crystal cell comprising a substrate and a liquid crystal alignment film coated with the composition for liquid crystal alignment on the substrate.

The liquid crystal display device may be manufactured according to conventional methods known in the art. For one embodiment thereof, one of the two glass substrates with the photoreaction with the liquid crystal alignment layer according to the present invention is applied to the end of the glass substrate by applying a photoreactive adhesive containing a ball spacer to the end of the glass substrate The glass substrates are bonded together, and only the portion to which the adhesive is applied is irradiated with ultraviolet rays to bond the cells. After the liquid crystal is injected into the completed cell and heat treatment, the liquid crystal cell is completed. (Fig. 1)

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are merely provided to more easily understand the present invention, and the contents of the present invention are not limited thereto.

Preparation Example 1 Synthesis of Quantum Dots

14.75 g (manufactured by Aldrich) zinc acetate were dissolved in 120 ml of methanol (manufactured by JT Baker) at 65 ° C. After the temperature was lowered to room temperature, 30 ml of a methanol solution in which 7.4 g of potassium hydroxide (manufacturer: Samjeon) was prepared was added, and stirred rapidly under reflux. After 3 days, the filtrate was removed by centrifugation at 4,000 rpm for 20 minutes, and the precipitate was dispersed by adding methanol. The redispersed solution was centrifuged again, the filtrate was removed, and the above procedure of dispersing methanol in the precipitate was repeated three times. Finally, the precipitate obtained was dried in an oven at 70 ° C. for 1 hour to obtain 4.8 g of ZnO nanorods.

<Examples 1-8> Preparation of a liquid crystal aligning film

Photoreactive polyvinyl cinnamate and the quantum dot ZnO prepared in Preparation Example 1, pentaerythritol triacrylate as a (meth) acrylate-based compound, and Shiva Irgacure 907 as a photoinitiator. Was dissolved in a solvent, spin-coated (2000 rpm, 20 sec) on a quartz glass plate, and dried at 80 ° C. for 2 minutes. And 15mw / cm <_2> of light was irradiated for 2 minutes using UV irradiator, respectively, and the liquid crystal aligning film was produced. At this time, the polarizing plate was placed in front of the UV lamp to proceed.

Comparative Example 1

A liquid crystal aligning film was prepared in the same manner as described in Example 1, except that the content shown in Table 1 was used.

Experimental Example

Quantum dots  Confirm

Take a drop of a solution in which the solid state ZnO nanorod prepared in Preparation Example 1 was dispersed in methanol, drop onto a carbon-coated Cu grid, and dry at room temperature for one day. Manufacturer: Hitachi, H-7600) is shown in Figure 2 the size and shape.

Photoreactivity  And Anisotropy  Measure

The absorbances of the liquid crystal alignment films prepared in Examples 1, 2, 4, and 6 in the vertical direction (A ′) and the horizontal direction (A∥) were measured, and then anisotropic ((A′-A∥) / (A⊥ + A)) is calculated and shown in FIG.

As can be seen in FIG. 5, the anisotropy is lower than without ZnO, but increases as the amount of ZnO increases.

Cinnamate reactivity was compared through the amount of olefins remaining in cinnamate. In Figure 5, it can be seen that the reactivity is similar regardless of the amount of ZnO. As the amount of ZnO increases, the reaction is thought to decrease because the density of cinnamate decreases, but similar reactivity was obtained.

Black luminance measurement

The liquid crystal alignment layer substrates prepared in Examples 1 to 7 and Comparative Example 1 were laminated with a sealant containing a spacer having a thickness of 2 μm, and the spacer was cured with UV. Then, the IPS liquid crystal was injected through a capillary action. The cell into which the liquid crystal was injected was stabilized at 90 ° C. for about 10 minutes, and the polarizers were attached to the cell upper and lower plates in a cross. In addition, the black luminance was measured by a photometer and the values are shown in Table 1.

As can be seen in Table 1, it can be seen that black brightness is obtained similarly to the reference. Reference is much superior to the material of the present invention in terms of fairness because it requires a considerably long UV irradiation time and pre-treatment such as imidization in order to be applied as an alignment layer.

Photoreactive Polyvinyl Cinnamate (wt%) ZnO
(wt%) Acrylate
Binder (wt%) Irgacure 907 (wt%) Black Luminance ¹ Example 1 2 0 One 0.25 2.0 Example
2 2 One 2 0.25 2.0 Example
3 2 3 One 0.25 2.1 Example
4 2 5 2 0.25 2.1 Example
5 2 7 One 0.25 2.5 Example
6 2 10 2 0.25 2.3 Example
7 2 15 One 0.125 2.1 Example
8 2 20 One 0.25 2.2 Comparative example
One Reference ² - - - 1.9

1: cd / cm2 (backlight: 5980cd / cm2)

2: polyimide photo-alignment material

Light transmittance  Measure

10 ml of 10% by weight of PVCi dissolved in THF was added to the 1, 3 and 5 wt% of quantum dot solution, respectively, and stirred for 30 minutes, and 2 ml of THF was further stirred for 30 minutes, followed by spin coating (spin coater, Laurell, WS-400-6NPP / LITE) was run at 4,000 rpm for 30 seconds. In order to see the transparency of the prepared thin film, samples were prepared on slide glass (Marienfeld, width 76 × length 26 × thickness 1 mm) and the transmittance was measured using a UV-Visible spectrometer. (Figure 3)

Light absorption Luminescence measurement

3 ml of ZnO nanorod solution dispersed in methanol was taken and placed in a cuvette. Absorption spectra were obtained using a UV-Visible spectrometer (manufactured by Senko, S-3100), and a Carly eclipse fluorescence spectrophotometer (manufacturer: Varian Assoc.) The emission spectrum (excitation wavelength = 300 nm) was obtained using (Fig. 4).

Claims (19)

1) A norbornene-based polymer having a photoreactive group, 2) A quantum dot 3) A (meth) acrylate compound, and 4) A composition for liquid crystal alignment comprising a photoinitiator. The composition of claim 1, wherein the norbornene-based polymer comprises a norbornene monomer represented by Formula 1 below:
[Formula 1]

In Chemical Formula 1,
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 Formula 2,
The others may be the same or different from each other, and each independently hydrogen; halogen; Substituted or unsubstituted alkyl having 1 to 20 carbon atoms; Substituted or unsubstituted alkenyl having 2 to 20 carbon atoms; Substituted or unsubstituted cycloalkyl having 5 to 12 carbon atoms; Substituted or unsubstituted aryl having 6 to 40 carbon atoms; Substituted or unsubstituted arylalkyl having 7 to 15 carbon atoms; Substituted or unsubstituted alkynyl having 2 to 20 carbon atoms; And a non-hydrocarbonaceous polar group comprising at least one element selected from the group consisting of oxygen, nitrogen, phosphorus, sulfur, silicon, and boron,
R ₁ , R ₂ , R ₃ , and R ₄ are not hydrogen, halogen, or a polar functional group, and R ₁ and R ₂ , or R ₃ and R ₄ may be linked to each other to form an alkylidene group having 1 to 10 carbon atoms. Or R ₁ or R ₂ is R ₃ and R ₄ Connected to 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,
(2)

In Chemical Formula 2,
A is a simple bond, substituted or unsubstituted alkylene having 1 to 20 carbon atoms, carbonyl (-CO-), carbonyloxy (-(CO) O-), substituted or unsubstituted arylene having 6 to 40 carbon atoms , And substituted or unsubstituted heteroarylene having 6 to 40 carbon atoms,
B is selected from the group consisting of simple bonds, oxygen, sulfur, and -NH-,
R9 is a simple bond, substituted or unsubstituted alkylene having 1 to 20 carbon atoms, substituted or unsubstituted alkenylene having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkylene having 5 to 12 carbon atoms, substituted or unsubstituted Arylene having 6 to 40 carbon atoms, substituted or unsubstituted arylalkylene having 7 to 15 carbon atoms, and substituted or unsubstituted alkynylene having 2 to 20 carbon atoms,
R10, R11, R12, R13, and R14 may be the same as or different from each other, and each independently substituted or unsubstituted alkyl having 1 to 20 carbon atoms; Substituted or unsubstituted alkoxy having 1 to 20 carbon atoms; Substituted or unsubstituted aryloxy having 6 to 30 carbon atoms; Substituted or unsubstituted aryl having 6 to 40 carbon atoms; Hetero aryl having 6 to 40 carbon atoms containing group 14, 15 or 16 hetero elements; It may be selected from the group consisting of substituted or unsubstituted alkoxyaryl having 6 to 40 carbon atoms and a halogen element. The composition for liquid crystal alignment according to claim 2, wherein the non-hydrocarbon polar group is selected from the following functional groups.
-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) _k -OR ₆ ,-(OR ₅ ) _k -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 , -R ₅ NNC (= S) R ₆ , -NO ₂ , -R ₅ NO ₂ ,

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And
In the polar functional group,
R ₅ is the same as or different from each other, and each independently halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, Linear or branched alkylene having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from carbonyloxy, halocarbonyloxy, aryloxy, haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkenylene having 2 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkynylene having 3 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Cycloalkylene having 3 to 12 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Arylene having 6 to 40 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Alkoxylene having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Or halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy , Carbonyloxyylene having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy,
R ₆ , R ₇ and R ₈ are the same as or different from each other, and each independently hydrogen; Hydrogen, halogen, halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy Linear or branched alkyl having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from aryloxy, haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkenyl of 2 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkynyl having 3 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Cycloalkyl having 3 to 12 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Aryl having 6 to 40 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Alkoxy having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Or halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy , Carbonyloxy of 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy,
k is an integer of 1-10 each independently. The heteroaryl group having 6 to 40 carbon atoms or the aryl group having 6 to 40 carbon atoms containing the hetero group of Group 14, 15 or 16 is selected from the group consisting of a compound represented by the following formula A composition for liquid crystal alignment films;

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In the above formulas,
R _'10 , R _'11 , R' ₁₂ , R _'13 , R' ₁₄ , R _'15 , R' ₁₆ , R _'17 , And R _'18 At least one of substituted or unsubstituted alkoxy having 1 to 20 carbon atoms or substituted or unsubstituted aryloxy having 6 to 30 carbon atoms,
The remainder may be the same or different and each independently substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, or substituted Or unsubstituted aryl having 6 to 40 carbon atoms. The polymer according to claim 1, wherein the norbornene-based polymer comprises a repeating unit represented by Formula 3 below:
(3)

In Chemical Formula 3,
n is 50 to 5,000,
p, R ₁ , R ₂ , R ₃ , and R ₄ are as defined in formula 1 of claim 1. The polymer according to claim 1, wherein the norbornene-based polymer comprises a repeating unit represented by Formula 4 below:
[Chemical Formula 4]

In Chemical Formula 4,
n is 50 to 5,000,
p, R ₁ , R ₂ , R ₃ , and R ₄ are as defined in formula 1 of claim 1. The norbornene-based polymer according to claim 1, wherein the norbornene-based polymer is a homopolymer of the norbornene monomer represented by Formula 1 or a copolymer including two or more different kinds of norbornene monomers represented by Formula 1. The composition for a liquid crystal alignment film of claim 1, wherein the 2) quantum dot comprises at least one selected from the group consisting of CdSe / ZnS, CdSe / ZnSe, and ZnO. The method according to claim 1, wherein the (meth) acrylate compound is pentaerythritol triacrylate (pentaerythritol triacrylate), tri (2-acryloyl oxyethyl) isosinurate (tris (2-acrylolyloxyethyl) isocynurate), trimethylol propane A composition for a liquid crystal alignment film, characterized in that at least one member selected from the group consisting of trimethylolpropane triacrylate and dipentaerythritol hexaacrylate. The composition of claim 1, wherein the photoinitiator is Irgacure 907 or Irgacure 819 from Ciba. The method of claim 1, wherein the composition for the liquid crystal alignment layer is toluene, anisole, chlorobenzene, dichloroethane, cyclohexane, cyclopentane, cyclopentane and propylene glycol methyl ether Acetate (propylene glycol methyl ether acetate) The composition for a liquid crystal alignment film comprising at least one organic solvent selected from the group consisting of. The composition according to claim 1, wherein the composition for liquid crystal alignment is based on the total weight of the liquid crystal alignment composition 1) 50 to 70% by weight of norbornene-based polymer having a photoreactive group, 2) 1 to 20% by weight of quantum dots, 3) (meth) acrylic 20 to 40% by weight of the rate compound, and 4) 1 to 15% by weight of the photoinitiator, the composition for liquid crystal alignment. a) dissolving the liquid crystal aligning composition according to any one of claims 1 to 12 in a solvent and then coating the substrate to form a coating film, b) drying the solvent included in the coating film, c) the Method of manufacturing a liquid crystal alignment film comprising the step of performing an alignment treatment by irradiating the polarized ultraviolet rays to the dried coating film surface. The method of claim 13, wherein the exposure and heat treatment are performed at 50 mJ / cm 2 to 10 J / cm 2 and 100 to 250 ° C., respectively. The liquid crystal aligning film containing the composition for liquid crystal aligning as described in any one of Claims 1-12. The liquid crystal aligning film of Claim 15 whose thickness of the said liquid crystal aligning film is 30-1000 nm. Liquid crystal cell containing the liquid crystal aligning film of Claim 15. The liquid crystal cell of claim 17, wherein the liquid crystal cell is a liquid crystal cell for IPS (In-Plane Switching) liquid crystal. The liquid crystal cell according to claim 17, wherein the liquid crystal cell is a liquid crystal cell for twisted-neutral (TN) liquid crystal.

Images