KR100468400B1 - Triazine ring with one more photoactive groups based poly(amide-ester) copolymers composition for photoinduced liquid crystal alignment, the film for photoinduced liquid crystal thereby, preparation method thereof and the liguid crystal cell comprising the film - Google Patents

Abstract

Disclosed is a poly (amide-ester) copolymerized photosensitive polymer liquid crystal aligning agent composition using a triazine ring having at least one photoactive group, a photosensitive polymer liquid crystal aligning film using the same, a method of manufacturing the same, and a liquid crystal device including the liquid crystal aligning film. . Low alignment force due to weak physical bonding strength between the low thermal stability liquid crystal and the alignment layer (1), which is a problem of the optical alignment agent having a main chain of a conventional optical alignment agent, especially hydrocarbon-based polymers such as polyvinyl cinnamate, polymaleimide, polyolefin, etc. It can overcome the problems affected by the light stability in the cell manufacturing process, maintain the excellent mechanical and thermal properties of the polyamide and at the same time have the advantages of polyester through the copolymerization with polyester, improves the workability, in particular copolymerization It is possible to manufacture the optimized structure according to the process and use through the diversification of physical properties and structure, and it has high mechanical properties, heat resistance, etc., and also has optical transparency, chemical resistance, and processability. And high quality display image quality.

Description

Poly (amide-ester) copolymerized photosensitive polymer liquid crystal aligning composition using a triazine ring having at least one photoactive group, photosensitive polymer liquid crystal aligning film using the same, a manufacturing method and a liquid crystal device comprising the liquid crystal aligning film TECHNICAL FIELD PHOTOACTIVE GROUPS BASED POLY (AMIDE-ESTER) COPOLYMERS COMPOSITION FOR PHOTOINDUCED LIQUID CRYSTAL ALIGNMENT, THE FILM FOR PHOTOINDUCED LIQUID CRYSTAL THEREBY, PREPARATION METHOD THEREOF AND THE LIGUID CRYSTAL CELL COMPRISING THE FILM}

The present invention relates to a poly (amide-ester) copolymerized photosensitive polymer liquid crystal aligning agent composition using a triazine ring having at least one photoactive group, a photosensitive polymer liquid crystal aligning film using the same, a method of manufacturing the same, and a liquid crystal device including the liquid crystal aligning film. .

In the present specification, the photosensitive polymer liquid crystal aligning agent is used as a liquid crystal aligning agent of a device using the optical properties of the liquid crystal. Generally, the liquid crystal is formed by applying an alignment agent on the substrate 2 and irradiating ultraviolet light to the surface to form anisotropy on the surface. It means a combination of a material orienting materials and constituent materials thereof. The liquid crystal device using the photosensitive polymer liquid crystal aligning agent has various application fields such as a liquid crystal display (LCD), a compensator, and an optical part. It is not limited to this.

Liquid crystal display (LCD) is leading the flat panel display market because it has the advantages of easy portability and low power consumption, and it has been expanded to include wall-mounted TVs and high-definition TVs. Tue and wide viewing angles are required.

Such liquid crystal display devices are generally filled with liquid crystals oriented between two glass substrates 2 on which the alignment layer 1 is coated, and rearrangement (switching) of liquid crystal molecules is caused by an electric field applied from the outside. Use what happens to form the desired image. At this time, in order to obtain uniform brightness and high contrast ratio, it is essential to orient the liquid crystal uniformly in a specific direction.

As a method of orienting liquid crystals, techniques such as a silicon oxide gradient deposition method and a photo-alignment method are known as a rubbing process and a non-rubbing process.

1 is a schematic view showing an alignment step of a liquid crystal alignment film by a conventional rubbing method. The rubbing method of inducing orientation by using a rubbing technique to heat-resistant polymers such as polyimide, which are most widely used as an alignment layer, is to print a polymer compound such as polyimide on the substrate 2 as shown in FIG. The method is applied by a method or the like, and the surface is rubbed by high-speed rotation with a rubbing drum 3 wound with a cloth in which nylon or polyester rayon fibers are planted, thereby forming a very fine groove on the surface of the polymer. While the rubbing process, the liquid crystal molecules are aligned with a constant pretilt angle θ on the surface of the alignment material. This rubbing method is widely used industrially due to its simple process, large area, and high speed treatment.

However, since the shape of the microgrooves formed in the alignment layer 1 varies according to the friction strength between the alignment cloth and the alignment layer, the arrangement of liquid crystal molecules becomes nonuniform, resulting in phase distortion and light scattering. In addition, there is a problem in that the production yield is reduced due to damage to the substrate 2 due to electrostatic discharge (ESD) generated by rubbing the polymer surface and fine dust generated in the rubbing drum 3. In addition, as one of the methods for achieving a wide viewing angle, when a single pixel is divided into small pixels so that the liquid crystal alignment state of each divided pixel is changed, a multi-domain display for widening the viewing angle is used. Complex lithographic processes such as rubbing, coating of photoresist, exposure and development, rubbing, removal of photoresist and the like are required and are undesirable in terms of productivity.

As the non-rubbing method, the silicon oxide oblique deposition method is a method of depositing silicon oxide obliquely with respect to the substrate 2, and it is difficult to maintain uniformity of deposition angle and film thickness with respect to the substrate 2, There is a problem that the process is large.

As a non-rubbing method, the photo-alignment method inclines or vertically irradiates linearly polarized ultraviolet rays 4 or the like onto a substrate 2 coated with a photosensitive polymer, thereby allowing photo-dimerization or photoisomerization. isomerization) and a non-contact treatment of an oriented surface that results in anisotropy on the surface. The possibility of this photoalignment method has been found using azobenzene compounds (K. lchimura et al., Langmuir, 4, 1214, 1988), followed by polymaleimide (HJChoi et al., US Patent 6218501), polyolefins (RH). Herr et al. US Patent 6201087) have been developed as a photo-alignment material.

Polymers mainly used up to now include, for example, a photosensitive ethene group, and chalcone, cinnamoyl, coumarin and the like are typical photosensitive portions. The orientation direction has a constant direction with respect to the polarization direction of the linearly polarized ultraviolet light 4, which is determined by the structure of the photosensitive polymer used. In addition, the pretilt direction varies with the incident direction of the irradiated ultraviolet light 4, and the pretilt angle varies with the irradiation energy and the incident angle.

Since the photo-alignment method is a non-contact method, problems caused by the introduction of impurities and generation of static electricity can be basically excluded, so that the cleanliness is maintained and the alignment process is easy to improve the yield and is suitable for mass production. In addition, since a multi-domain can be formed by a relatively simple process of irradiating ultraviolet rays 4 while varying polarization directions according to regions by using a photomask, it is an advantageous method for improving a viewing angle.

However, the conventional photo-alignment method does not uniformly align the liquid crystal due to the low photosensitivity of the photo-alignment material and its weak anisotropy, so that a long irradiation time is required to solve this problem, thereby degrading fairness. In addition, the physical bonding force between the photosensitive polymer liquid crystal aligning agent and the liquid crystal in which the anisotropy is formed is weak, unstable to light, and weak in orientation due to heat.

For example, the conventional optical alignment material using a conventional polyvinyl alcohol hydrocarbon-based polymer as a main chain is not only low thermal stability, but also the alignment force, which is a physical bonding force between the alignment layer 1 and the liquid crystal, is higher than that of the polyimide alignment material obtained by the conventional rubbing process. Has the disadvantage of falling. In addition, the polymaleimide or polyimide photo-alignment material proposed in the existing Korean Patent Registration No. 1998-0028532 still has a limitation that the hydrocarbon-based main chain.

Therefore, for the practical use of the photo-alignment method has been required to solve the problem that the improvement of photochemical and thermal stability, the improvement of electro-optic properties and the amount of ultraviolet light is required.

Therefore, the present invention has been made to solve the above problems,

It is an object of the present invention to provide polyolefins with triazine rings having one or more photoactive groups which have good photochemical and thermal stability, good electro-optic properties and good orientation for liquid crystals, are also easy to form multidomains, and in particular have good processability. It provides an (amide-ester) copolymerizable photosensitive polymer liquid crystal aligning agent composition.

Another object of the present invention is to provide a photosensitive polymer liquid crystal aligning film 1 using the photosensitive polymer liquid crystal aligning agent composition.

Another object of the present invention is to provide a method for producing a liquid crystal alignment film 1 using the photosensitive polymer liquid crystal aligning agent composition.

Still another object of the present invention is to provide a liquid crystal element comprising the liquid crystal alignment film 1.

In order to achieve the above object,

The present invention is composed of a structure of formula 1 having at least one photoactive group in the side chain and a triazine ring as a main chain,

[Formula 1]

One of the photoactive groups may undergo photolysis, the other may undergo free filament shifting, and the remaining sites may undergo photodimerization or cross-crosslinking to enhance, modify and preserve the resulting orientation. The present invention provides a poly (amide-ester) copolymerized photosensitive polymer liquid crystal aligning agent composition using a triazine ring having at least one photoactive group prepared by copolymerization of polyamide and polyester.

In order to achieve the other object as described above,

The present invention provides a liquid crystal aligning film (1) comprising a poly (amide-ester) copolymerized photosensitive polymer liquid crystal aligning agent composition using a triazine ring having one or more photoactive groups.

In order to achieve another object as described above,

The present invention provides a method of dissolving a poly (amide-ester) copolymer photosensitive polymer liquid crystal aligning agent composition using a triazine ring having at least one photoactive group in an organic solvent, wherein the solution is spin coated or printed by a substrate (2). Forming an alignment layer 1 by applying it onto the surface of the alignment layer 1, or applying an inclined or vertical line to the surface of the alignment layer 1 by using a polarizer or a polarized ultraviolet ray 4 or an unpolarized ultraviolet ray 4 without using a polarizer. It provides a method for producing a photosensitive polymer liquid crystal alignment film 1 constituted by irradiation.

In order to achieve another object as described above,

The present invention provides a liquid crystal device comprising a liquid crystal aligning film (1) comprising a poly (amide-ester) copolymerized photosensitive polymer liquid crystal aligning agent composition using a triazine ring having at least one photoactive group.

1 is a schematic view showing an alignment process of a liquid crystal alignment film by a conventional rubbing method,

2 is a schematic view showing an irradiation step in the alignment process of the liquid crystal alignment film using the photosensitive polymer liquid crystal aligning agent composition according to the present invention.

* A brief description of the major reference marks *

1: Orientation Film 2: Substrate

3: rubbing drum 4: UV

Hereinafter, a poly (amide-ester) copolymerized photosensitive polymer liquid crystal aligning agent composition using a triazine ring having one or more photoactive groups according to the present invention, a photosensitive polymer liquid crystal aligning film using the same, a method of manufacturing the same, and a liquid crystal device comprising the liquid crystal aligning film It demonstrates in detail.

The poly (amide-ester) copolymerized photosensitive polymer liquid crystal aligning agent composition using a triazine ring having one or more photoactive groups according to the present invention has a triazine ring having one or more photoactive groups in a side chain thereof, Structured,

[Formula 1]

One of the photoactive groups may undergo photolysis, the other may undergo free filament shifting, and the remaining sites may undergo photodimerization or cross-crosslinking to enhance, modify and preserve the resulting orientation. have.

Preferably, the photoactive group is a cinnamate-based, coumarin-based, chalcone-based, maleimide-based compound.

More preferably, R ₁ of [Formula 1] is any _one of the following formulas (1a), (2a), (3a), (4a),

(The benzene ring may be ortho-, meta-, or a mixed structure of at least two ortho-, meta-, or para-structures.)

In Formula (1a), X is any one of the following formulas,

Wherein m and n are each 0 to 10, and the benzene ring may be an ortho- or meta-structure in addition to the para-structure, or a mixed structure of at least two of ortho-, meta-, and para-structures. It may have been done.)

And in the formula (1a) Y is any one of the following formula,

(The benzene ring may be ortho-, meta-, or a mixed structure of at least two ortho-, meta-, or para-structures.)

In the above formula, 1,2,3,4,5,6,7,8,9 are each selected from the following formula.

Wherein m and n are each 0 to 10, A and B are H, F, Cl, CN, CF ₃ or CH ₃ , and the benzene ring may be ortho- or meta-structure in addition to para-structure. Or it may be a mixture of at least two ortho-, meta- and para-structures.)

In Formulas (2a) and (3a), n is 0 to 10, and 1,2,3,4,5 is any one of the following formulas.

Wherein m and n are each 0 to 10, A and B are H, F, Cl, CN, CF ₃ or CH ₃ , and the benzene ring may be ortho- or meta-structure in addition to para-structure. Or may be a mixture of at least two ortho-, meta- and para-structures)

In the formula (4a), Y is any one selected from the following formula,

Wherein m and n are each 0 to 10, and the benzene ring may be an ortho- or meta-structure in addition to the para-structure, or a mixed structure of at least two ortho-, meta-, and para-structures. May be

In the formula (4a), 1 and 2 are each selected from the following formula.

(A is H, F, CN, CF ₃ or CH ₃ )

The amide bond connecting R ₂ , R ₄ and R ₅ in [Formula 1] is obtained by the reaction of amine and carboxylic acid, and the general form of the reaction is shown in the following [Scheme 1].

[Scheme 1]

The ester bond connecting R ₃ , R ₄ , and R ₅ in [Formula 1] is formed by the reaction of diol and carboxylic acid, and the general form of the reaction is shown in the following [Scheme 2].

[Scheme 2]

Therefore, the amide bond and the ester bond, which are the linking moieties of [Formula 1], are obtained by the reaction of carboxylic acid, amine, and alcohol, and consist of a mixed reaction of [Scheme 1] and [Scheme 2].

R ₂ in [Formula 1] is due to the amine of [Scheme 1] is any one selected from the following formula.

Wherein m and n are each 0 to 10, and the benzene ring may be an ortho- or meta-structure in addition to the para-structure, or a mixed structure of at least two of ortho-, meta-, and para-structures. May be

And in the above [Formula 1] R ₃ is due to the alcohol of [Scheme 2] is any one selected from the following formula.

Wherein m and n are each 0 to 10, and A, 1,2,3,4,5,6,7,8 are each H, F, Cl, CN, CF ₃ or CH ₃ , and the benzene ring May be an ortho-structure, a meta-structure, or a mixed structure of at least two of ortho-, meta-, and para-structures in addition to the para-structure)

R ₄ and R ₅ in the above [Formula 1] is due to the carboxylic acid of [Scheme 1] and [Scheme 2] is any one selected from the following formula.

(Wherein m and n are 0 to 10, the benzene ring may be an ortho- or meta-structure other than a para-structure, or a mixed structure of at least two ortho-, meta-, and para-structures). May be)

The copolymerization ratio of [Formula 1] is controlled by the ratio of the diol and diamine in the equivalent ratio of the triazine monomer corresponding to the dicarboxylic acid, the copolymer is the sequence, time, amount, etc. of the diol and the diamine to participate in the polymerization reaction According to the change of random, random blocks, each of the blocks or they may be formed of a copolymer structure mixed with each other, and thus can be manufactured in an optimized structure according to the process or use through the diversification of physical properties and structures.

The photosensitive polymer liquid crystal aligning film according to the present invention is a photosensitive polymer liquid crystal aligning film 1 comprising a poly (amide-ester) copolymerized photosensitive polymer liquid crystal aligning agent composition using a triazine ring having one or more photoactive groups.

Preferably, the composition is applied to a substrate and included, and ultraviolet rays are irradiated to have liquid crystal alignment.

2 is a schematic view showing an irradiation step in the alignment process of the liquid crystal aligning film 1 using the photosensitive polymer liquid crystal aligning agent composition according to the present invention.

The method for producing a liquid crystal aligning film (1) using a poly (amide-ester) copolymerized photosensitive polymer liquid crystal aligning agent composition using a triazine ring having one or more photoactive groups according to the present invention firstly comprises a triazine having one or more photoactive groups. The poly (amide-ester) copolymerized photosensitive polymer liquid crystal aligning agent composition using a ring was selected from chlorobenzene, N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), and N, N-dimethylimidazolidinone ( DMI), N, N-dipropylimidazolidinone (DPI), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), cyclopentanone, cyclohexanone, dichloroethane, butyl 1 to 100 cps by dissolving in an organic solvent composed of any one or at least any two or more mixed solvents selected from the group consisting of cellulsolve, gamma butyrolactone and tetrahydrofuran (THF) Create a viscosity.

Next, the solution is applied onto the substrate 2, for example, an ITO glass substrate 2, by a thickness of 10 to 500 nm by spin coating or printing to form an alignment layer 1.

The surface of the alignment layer 1 is inclined or vertically irradiated with ultraviolet (4) linearly polarized using a polarizer or unpolarized ultraviolet (4) without polarizer for 2 seconds to 10 minutes, and then onto the substrate (2). The liquid crystal aligning film 1 is manufactured in this.

The irradiation time depends on the power of the lamp. The larger the power, the shorter the irradiation time. The smaller the power, the larger the irradiation time. For lamps of approximately 500W, tilt or level for 2 seconds to 10 minutes.

The poly (amide-ester) copolymerized photosensitive polymer liquid crystal aligning agent composition using a triazine ring having one or more photoactive groups according to the present invention may change the pretilt angle of the liquid crystal oriented according to the inclination angle of the ultraviolet ray 4 which is obliquely irradiated. The pretilt angle may be set to 0 ° by manipulating the change in chemical structure or the irradiation angle of ultraviolet ray 4.

The driving mode of a liquid crystal display device manufactured using a poly (amide-ester) copolymerized photosensitive polymer liquid crystal aligning agent composition using a triazine ring having one or more photoactive groups according to the present invention is STN (Super Twisted Nematic), TN (Twisted) It can be applied to various modes such as Nematic), In Plane Switching (IPS), and Vertically Alligned Twisted Nematic (VATN) mode.

The manufacturing method of the liquid crystal element containing the liquid crystal aligning film (1) using the poly (amide-ester) copolymerized photosensitive polymer liquid crystal aligning agent composition using the triazine ring which has one or more photoactive groups which concerns on this invention is as follows.

After spraying a spacer having a predetermined size on the two photoreacted substrates (2) having a liquid crystal alignment film (1) prepared as described above, by attaching the adhesive between the two substrates (2) to have a constant thickness between the two The cell is subjected to a curing process at 130 ° C. for 1 hour and then the adhesive is cured so that the two substrates are completely bonded to each other to prepare a cell. Thereafter, a liquid crystal is injected into the cell, heat is applied at 100 to 130 ° C. for about 1 hour, and then a heat treatment process is performed once to lower the temperature to room temperature.

Hereinafter, the present invention will be described in more detail by explaining preferred embodiments of the present invention. However, the present invention is not limited to the following examples, and various forms of embodiments can be implemented within the scope of the appended claims, and the following examples are only common to those skilled in the art to complete the present disclosure. It is intended to facilitate the implementation of the invention to those with knowledge.

Example 1

Example 1 relates to a poly (amide-ester) copolymerized photosensitive polymer liquid crystal aligning agent composition using a triazine ring having a cinnamate photosensitive functional group, a method for preparing a liquid crystal aligning film using the same, and a method for manufacturing a liquid crystal device including the liquid crystal aligning film. .

(1) Modification of triazine ring

27.1 g of 4- (2-tetrahydropyranylmethoxy) bromobenzene was dissolved in tetrahydrofuran dehydrated with 250 ml of water in a three-necked flask filled with nitrogen, and then reacted with 3 g of magnesium for 24 hours. The solution was reacted for 12 hours while slowly dropping at -20 ° C into a solution in which 18.4 g of cyanuric chloride was dissolved in 200 ml of dehydrogenated tetrahydrofuran in a three-necked flask filled with nitrogen. After the reaction was terminated, the reaction solution was decompressed at room temperature to remove tetrahydrofuran and dissolved in ethyl acetate. The solution was mixed with a basic aqueous solution, and impurities were extracted with vigorous stirring. The aqueous phase was separated and removed under reduced pressure at room temperature to remove ethyl acetate. The solvent was removed and the remaining solid material was recrystallized from n-nucleic acid to give 2- (4- (2-tetrahydropyranylmethoxy) phenyl) -4,5-dichloro-1,3,5-triazine.

(2) Introduction of hydroxy functional group to triazine ring

34.0 g of 2- (4- (2-tetrahydropyranylmethoxy) phenyl) -4,5-dichloro-1,3,5-triazine was added to a round bottom flask and dissolved in 300 ml of tetrahydrofuran. After adding 0.3 g of pyridinium paratoluene sulfonate, 50 ml of ethanol was added thereto, and the reaction was performed for 24 hours. After completion of the reaction, the solvent was removed by distillation under reduced pressure, and the remaining solids were dissolved in methylene chloride again, and then mixed with distilled water in a separatory funnel to extract impurities twice. Calcium chloride was added to the methylene chloride solution to remove moisture, and the solvent was removed by distillation under reduced pressure. This solid phase was recrystallized in a mixed solvent of methylene chloride and normal nucleic acid to obtain 2- (4-hydroxymethyl) phenyl-4,6-dichloro-1,3,5-triazine.

(3) Synthesis of triazine ring having cinnamate side chain

25.6 g of the obtained 2- (4-hydroxymethyl) phenyl-4,6-dichloro-1,3,5-triazine was added to a round-bottomed flask filled with nitrogen, followed by dissolving 200 ml of tetrahydrofuran from which water was removed. . After 15.2 g of triethylamine was added to the solution, the temperature was lowered to -5 ° C. Then, 25 g of cinnamoyl chloride was added to 100 ml of tetrahydrofuran from which water was removed, and the diluted cinnamoyl chloride solution was slowly added dropwise while stirring for 12 hours. I was. After completion of the reaction, the reaction solution was distilled under reduced pressure to remove tetrahydrofuran, dissolved in methylene chloride, passed through a filter filled with silica gel, and then distilled under reduced pressure to remove the solvent. Finally, the mixture was recrystallized from a mixed solvent of methylene chloride and normal nucleic acid, and then filtered under reduced pressure. The obtained solid substance was vacuum dried to obtain triazine having cinnamate side chains.

(4) Synthesis of Triazine Monomer Having Two Amine Functions

38.6 g of the triazine obtained in the above (3) was placed in a round bottom flask and dissolved in 400 ml of chloroform. 32.8 g of 4-aminophenol and 12 g of sodium hydroxide were dissolved in 300 ml of distilled water dissolved in 3 g of cetyltrimethylammonium bromide, mixed with the previous triazine solution, and reacted vigorously for 24 hours. After completion of the reaction, the organic solution phase was separated, transferred to a separatory funnel, washed three times with distilled water to extract impurities, and then water was removed with calcium chloride. The water-removed solution was distilled under reduced pressure to remove chloroform, an organic solvent, and then recrystallized from a mixed solvent of methylene chloride and normal nucleic acid. The precipitated crystals were filtered under reduced pressure and dried in vacuo to obtain a triazine monomer.

(5) Synthesis of Triazine Monomer Having Two Alcohol Functional Groups

25.6 g of the triazine obtained in the above (3) was placed in a round bottom flask filled with nitrogen, and 200 ml of tetrahydrofuran from which water was removed was dissolved. This solution was substituted by 4- (2-tetrahydropyranylmethoxy) benzene after remaining two chlorine of the triazine of said (3) by the method of said (1), and was removed by the method of said (1). The obtained substance was reacted by the method of said (2), and the triazine monomer which has two hydroxyl functional groups was obtained.

(6) Polymerization of poly (amide-ester) copolymerizable photosensitive polymer liquid crystal aligning agent having cinnamate photosensitive functional group

26.5 g of a triazine monomer having an amine function obtained by the method of (4) above and 26.5 g of a triazine monomer having an alcohol function obtained by the method of (5) above were placed in a round bottom flask filled with nitrogen to remove water. Dissolve in 400 ml of hydrofuran. 20.238 g of triethylamine is added to this solution. After dissolving 20.3 g of terephthaloyl chloride in 100 ml of tetrahydrofuran from which water was removed, the mixture was stirred vigorously while slowly dropping into the solution containing the two triazine monomers and triethyl amine, followed by reaction for 12 hours. After completion of the reaction, the reaction solution was slowly poured into methanol, precipitated, and filtered. The precipitate was dried in vacuo. The obtained precipitate was again dissolved in tetrahydrofuran, and then precipitated in methanol twice. After vacuum drying, a poly (amide-ester) copolymerized photosensitive polymer liquid crystal aligning agent having a cinamate photosensitive functional group was finally used using a triazine ring. Was prepared.

(7) Preparation of Liquid Crystal Alignment Film

The obtained photo-alignment agent was dissolved in a mixed solvent of NMP and butyl cellussolve at a concentration of 8 wt%, and then passed through a solution having a micropore size of 0.1 μm to remove undissolved impurity particles. The solution was printed on a glass substrate 2 coated with a transparent electrode to a thickness of 300 nm to apply a photoalignment agent, and the glass substrate 2 was dried at 200 ° C. for about 1 hour to remove the solvent. This glass substrate 2 is used to induce a complex photoreaction such as photopolymerization of cinnamate group and photodegradation of polymer chain through one light irradiation for 2 seconds to 10 minutes at an angle of 20 ° with respect to ultraviolet rays 4 of 500W mercury lamp. To prepare a polymer liquid crystal alignment film.

(8) Fabrication of liquid crystal elements

After spraying a spacer having a size of 4 ~ 5 ㎛ on the photoreaction two glass substrate (2), using a epoxy adhesive so that the cell gap between the two glass substrate (2) to 4 ~ 5㎛ Attached. The cell was cured for one hour at 130 ° C. to cure the epoxy adhesive so that the two glass substrates 2 were completely adhered to complete the manufacture of the cell. After injecting the liquid crystal into the finished cell was heated for 1 hour at 100 ~ 130 ℃ and then the heat treatment step of dropping the temperature back to room temperature was performed once.

The electro-optical properties, thermal stability, photostability, residual DC, and VHR characteristics of the liquid crystal cell prepared above were measured and the results are shown in Table 1, Table 2, Table 3, and Table 4.

Example 2

Embodiment 2 relates to a poly (amide-ester) copolymerized photosensitive polymer liquid crystal aligning agent composition using a triazine ring having a chalcone photosensitive functional group, a liquid crystal aligning film production method using the same, and a liquid crystal device manufacturing method including the liquid crystal aligning film.

(1) Synthesis of chalcone photosensitive functional groups

10 g of 4-methoxychalcone and 2.05 g of sodium cyanide were dissolved in 100 ml of dimethyl sulfoxide and allowed to react for 24 hours. After completion of the reaction, the reaction solution was mixed with chloroform and stirred with distilled water to extract impurities. After removing the aqueous phase, chloroform was removed under reduced pressure at room temperature. The remaining solid phase was recrystallized in methanol and then dried in vacuo at 40 ° C. to obtain side chain 4-hydroxychalcone for photoreaction.

(2) Introduction of chalcone photosensitive functional group in triazine ring

23.8 g of the obtained 4-hydroxychalcone is placed in a round bottom flask filled with nitrogen and dissolved in 240 ml of tetrahydrofuran from which moisture is removed. 2.4 g of sodium hydride was added thereto and allowed to react for 6 hours at room temperature. Into this solution, 18.4 g of triazine was added to a round-bottomed flask as in Example 1 (1), and the mixture was reacted for 24 hours with vigorous stirring while slowly dropping at -5 ° C to a solution of 200 ml of dehydrogenated tetrahydrofuran. . After completion of the reaction, distillation under reduced pressure was carried out to remove tetrahydrofuran, and the obtained solid was dissolved in chloroform again. The solution was washed three times with distilled water in a separatory funnel to extract impurities, and then water was removed with calcium chloride. The solution was distilled under reduced pressure again to remove chloroform and recrystallized with a mixed solvent of methylene chloride and normal nucleic acid. The obtained material was filtered under reduced pressure and then vacuum dried to obtain triazine having a chalcone photosensitive functional group.

(3) Synthesis of Triazine Monomer Having Two Amine Functions

38.6 g of the triazine having the above-described chalcone photosensitive functional group was dissolved in 300 ml of distilled water in which 32.8 g of 4-aminophenol and 12 g of sodium hydroxide were dissolved in 3 g of cetyltrimethylammonium bromide, followed by a vigorous reaction for 24 hours. After completion of the reaction, the organic solution phase was separated, transferred to a separatory funnel, washed three times with distilled water to extract impurities, and then water was removed with calcium chloride. The water-removed solution was distilled under reduced pressure to remove chloroform, an organic solvent, and then recrystallized from a mixed solvent of methylene chloride and normal nucleic acid. The precipitated crystals were filtered under reduced pressure and dried in vacuo to obtain a triazine monomer.

(4) Synthesis of Triazine Monomer Having Diol Functional Group

51.4 g of 4- (2-tetrahydropyranyloxy) bromobenzene was dissolved in 300 ml of water-removed tetrahydrofuran and reacted with 7.2 g of magnesium for 6 hours under nitrogen. In this solution, 38.6 g of triazine having a chalcone photosensitive functional group synthesized in (2) was dissolved in 300 ml of dehydrated tetrahydrofuran, and then dropwise added to the Grignard reagent solution prepared in Example (1) at room temperature. The reaction was carried out for 12 hours. After the reaction was terminated, 3 g of pyridinium paratoluene sulfonate was added to the reaction solution, and the reaction was further performed for 6 hours. Finally, the reaction solution was terminated and the reaction solution was distilled under reduced pressure to remove tetrahydrofuran, dissolved in methylene chloride, passed through a filter filled with silica gel, and then distilled under reduced pressure to remove the solvent. Finally, the mixture was recrystallized from a 1: 1 mixed solvent of methylene chloride and normal nucleic acid, and then filtered under reduced pressure. The obtained solid substance was vacuum dried to obtain a triazine monomer having a diol functional group.

(5) Polymerization of the photosensitive polymer liquid crystal aligning agent having a chalcone photosensitive functional group

26.575 g of the triazine monomer obtained by the method of (3) and 20.05 g of the triazine monomer obtained by the method of (4) are placed in a round bottom flask filled with nitrogen and dissolved in 400 ml of tetrahydrofuran from which water is removed. 20.24 g of triethylamine is added to this solution. After dissolving 20.3 g of terephthaloyl chloride in 100 ml of tetrahydrofuran from which water was removed, the mixture was stirred vigorously while slowly dropping into the solution of the previous triazine monomer and triethyl amine, followed by reaction for 12 hours. After completion of the reaction, the reaction solution was slowly poured into methanol, precipitated, and filtered. The precipitate was dried in vacuo. The obtained precipitate was again dissolved in tetrahydrofuran and then precipitated in methanol twice. After vacuum drying, a poly (amide-ester) copolymer photosensitive polymer liquid crystal aligning agent having a chalcon photosensitive functional group was finally used using a triazine ring. Prepared.

(6) Preparation of liquid crystal aligning film

The obtained photo-alignment agent was dissolved in a mixed solvent of NMP and butyl cellussolve at a concentration of 8 wt%, and then passed through a solution having a micropore size of 0.1 μm to remove undissolved impurity particles. The solution was printed on a glass substrate 2 coated with a transparent electrode to a thickness of 300 nm to apply a photoalignment agent, and the glass substrate 2 was dried at 200 ° C. for about 1 hour to remove the solvent. The glass substrate 2 is subjected to complex photoreaction such as photopolymerization of chalcone group and photodegradation of polymer chain through one light irradiation for 2 seconds to 10 minutes at an angle of 20 ° to ultraviolet light 4 of 500W mercury lamp. A polymer liquid crystal aligning film was prepared.

(7) Fabrication of liquid crystal elements

After spraying a spacer having a size of 4 ~ 5 ㎛ on the photoreaction two glass substrate (2), using a epoxy adhesive so that the cell gap between the two glass substrate (2) to 4 ~ 5㎛ Attached. The cell was cured for one hour at 130 ° C. to cure the epoxy adhesive so that the two glass substrates 2 were completely adhered to complete the manufacture of the cell. After injecting the liquid crystal into the finished cell was heated for 1 hour at 100 ~ 130 ℃ and then the heat treatment step of dropping the temperature back to room temperature was performed once.

The electro-optical properties, thermal stability, photostability, residual DC, and VHR characteristics of the liquid crystal cell prepared above were measured and the results are shown in Table 1, Table 2, Table 3, and Table 4.

Example 3

Example 3 relates to a poly (amide-ester) copolymerized photosensitive polymer liquid crystal aligning agent composition using a triazine ring having a coumarin photosensitive functional group, a method for preparing a liquid crystal aligning film using the same, and a method for manufacturing a liquid crystal device including the liquid crystal aligning film.

(1) Introduction of coumarin photosensitive functional group

16.2 g of 7-hydroxycoumarin and 2.4 g of sodium hydride are placed in a round-bottomed flask filled with nitrogen, dissolved in 160 ml of tetrahydrofuran from which water is removed, followed by vigorous stirring for 6 hours. Into this solution, 18.4 g of triazine was added to a round-bottomed flask as in Example 1 (1), and the mixture was reacted for 24 hours with vigorous stirring while slowly dropping at -5 ° C to a solution of 200 ml of dehydrogenated tetrahydrofuran. . After completion of the reaction, distillation under reduced pressure was carried out to remove tetrahydrofuran, and the obtained solid was dissolved in chloroform again. The solution was washed three times with distilled water in a separatory funnel to extract impurities, and then water was removed with calcium chloride. The solution was distilled under reduced pressure again to remove chloroform and recrystallized with a mixed solvent of methylene chloride and normal nucleic acid. The obtained material was filtered under reduced pressure and then vacuum dried to obtain triazine having a coumarin photosensitive functional group.

(2) Synthesis of Triazine Monomer Having Two Amine Functions

31.1 g of the triazine having the coumarin photosensitive functional group synthesized above was dissolved in 300 ml of distilled water in which 32.8 g of 4-aminophenol and 12 g of sodium hydroxide were dissolved in 3 g of cetyltrimethylammonium bromide, followed by a vigorous reaction for 24 hours. After completion of the reaction, the organic solution phase was separated, transferred to a separatory funnel, washed three times with distilled water to extract impurities, and then water was removed with calcium chloride. The water-removed solution was distilled under reduced pressure to remove chloroform, an organic solvent, and then recrystallized from a mixed solvent of methylene chloride and normal nucleic acid. The precipitated crystals were filtered under reduced pressure and dried in vacuo to obtain a triazine monomer.

(3) Synthesis of Triazine Monomer Having Diol Functional Group

51.4 g of 4- (2-tetrahydropyranyloxy) bromobenzene was dissolved in 300 ml of water-removed tetrahydrofuran and reacted with 7.2 g of magnesium for 6 hours under nitrogen. 31.1 g of a triazine having a coumarin photosensitive functional group synthesized in (1) was dissolved in 300 ml of tetrahydrofuran from which water was removed, and then added dropwise to the Grignard reagent solution prepared in (1) of Example 1 at room temperature. The reaction was time. After the reaction was terminated, 3 g of pyridinium paratoluene sulfonate was added to the reaction solution, and the reaction was further performed for 6 hours. Finally, the reaction solution was terminated and the reaction solution was distilled under reduced pressure to remove tetrahydrofuran, dissolved in methylene chloride, passed through a filter filled with silica gel, and then distilled under reduced pressure to remove the solvent. Finally, the mixture was recrystallized from a 1: 1 mixed solvent of methylene chloride and normal nucleic acid, and then filtered under reduced pressure. The obtained solid substance was vacuum dried to obtain a triazine monomer having a diol functional group.

(4) polymerization of a photosensitive polymer liquid crystal aligning agent having a coumarin photosensitive functional group

22.77 g of the triazine monomer obtained by the method of (2) and 22.75 g of the triazine monomer obtained by the method of (3) are placed in a round bottom flask filled with nitrogen and dissolved in 400 ml of tetrahydrofuran from which water is removed. 20.24 g of triethylamine is added to this solution. After dissolving 20.3 g of terephthaloyl chloride in 100 ml of tetrahydrofuran from which water was removed, the mixture was stirred vigorously while slowly dropping into the solution of the previous triazine monomer and triethyl amine, followed by reaction for 12 hours. After completion of the reaction, the reaction solution was slowly poured into methanol, precipitated, and filtered. The precipitate was dried in vacuo. The obtained precipitate was again dissolved in tetrahydrofuran and then precipitated in methanol twice. After vacuum drying, a poly (amide-ester) copolymer photosensitive polymer liquid crystal aligning agent having a coumarin photosensitive functional group was finally used by using a triazine ring. Prepared.

(5) Preparation of Liquid Crystal Alignment Film

The obtained photo-alignment agent was dissolved in a mixed solvent of NMP and butyl cellussolve at a concentration of 8 wt%, and then passed through a solution having a micropore size of 0.1 μm to remove undissolved impurity particles. The solution was printed on a glass substrate 2 coated with a transparent electrode to a thickness of 300 nm to apply a photoalignment agent, and the glass substrate 2 was dried at 200 ° C. for about 1 hour to remove the solvent. The glass substrate 2 was subjected to a complex photoreaction such as photopolymerization of coumarin groups and photolysis of polymer chains through one irradiation of light for 2 seconds to 10 minutes at an angle of 20 ° to the ultraviolet rays 4 of the 500W mercury lamp. A polymer liquid crystal aligning film was prepared.

(6) Fabrication of liquid crystal elements

After spraying a spacer having a size of 4 ~ 5 ㎛ on the photoreaction two glass substrate (2), using a epoxy adhesive so that the cell gap between the two glass substrate (2) to 4 ~ 5㎛ Attached. The cell was cured for one hour at 130 ° C. to cure the epoxy adhesive so that the two glass substrates 2 were completely adhered to complete the manufacture of the cell. After injecting the liquid crystal into the finished cell was heated for 1 hour at 100 ~ 130 ℃ and then the heat treatment step of dropping the temperature back to room temperature was performed once.

The electro-optical properties, thermal stability, photostability, residual DC, and VHR characteristics of the liquid crystal cell prepared above were measured and the results are shown in Table 1, Table 2, Table 3, and Table 4.

Table 1 shows the change of the pretilt angle according to the heat treatment.

division Example 1 Example 2 Example 3 fair Light irradiation Light irradiation Light irradiation density 8wt% 8wt% 8wt% Pretilt Room temperature 0 to 7 ° 0 to 5 ° 0 to 6 ° After heat treatment 0 to 7 ° 0 to 5 ° 0 to 6 ° Contrast 196 194 195

* The pretilt angle was measured by the crystal angle rotation method.

* The heat treatment is carried out for 3 minutes at 150 ° C, the baking temperature.

As shown in the table, it can be seen that there is no change of the pretilt angle even after the heat treatment. When the photoalignment liquid crystal display device is manufactured using the alignment agent, a multi-domain liquid crystal alignment can be obtained by a simple process, and the pretilt angle of the liquid crystal is maintained even after the high temperature process of silbaking, and thus the alignment characteristic of the liquid crystal is remarkably oriented. Therefore, it can be applied to a liquid crystal display device that requires high quality and wide viewing angle.

The thermal stability of the liquid crystal display device according to Examples 1, 2, and 3 is evaluated by measuring the change of the pretilt angle with time at room temperature while measuring the initial pretilt angle of the liquid crystal display device and thermally aging at 200 ° C. It was. Table 2 shows the results of the thermal stability evaluation.

division Example 1 Example 2 Example 3 Pretilt To 3 ° To 5 ° To 6 ° Thermal aging temperature 200 ℃ 200 ℃ 200 ℃ Heat aging time 48 hours 48 hours 48 hours Pretilt variation none none none

In the case of unstable thermal stability, the pretilt angle changed over time. As shown in Table 2, the photo-alignment agent according to the present embodiment has excellent thermal stability in which the alignment and pretilt angles of the liquid crystals are stably maintained even in a long time thermal aging state, and thus the basic characteristics for application to a liquid crystal display device. Satisfies

The liquid crystal display element for measuring photostability was manufactured by the method for manufacturing the liquid crystal display element according to Examples 1, 2, and 3. In the light stability measurement, the alignment surface of one liquid crystal display device was irradiated with ultraviolet light 4 and light in the visible light region for 1 to 10 minutes, and then the change of alignment characteristics of the irradiation surface and non-irradiation surface of the liquid crystal display device was visually confirmed. Table 3 shows the results of light stability evaluation.

division Example 1 Example 2 Example 3 Light irradiation 0.5J / cm ² No change No change No change 1 J / cm ² No change No change No change 2J / cm ² No change No change No change Wide angle 90 ° No change No change No change 80 ° No change No change No change 70 ° No change No change No change

In the present embodiment, as shown in Table 3, there is no change in the orientation characteristic, so it can be seen that the light stability is excellent. Accordingly, there is no problem in that the alignment characteristics of the liquid crystal are changed to show a sharp difference with the non-irradiated surface, or the alignment of the liquid crystal is broken so that the alignment direction of the liquid crystal is mixed in an unspecified direction and thus cannot be used in the display device.

Residual DC was applied to both ends of the liquid crystal display while varying the DC voltage between -10V and 10V. At this time, the capacitance was measured and the residual DC was calculated from the magnitude of the hysteresis value. The liquid crystal display element used in the experiment was prepared by the above-described manufacturing method with samples of the TN structure having a thickness of 4 ~ 6㎛. The two electrodes of the prepared liquid crystal display device were connected to an LCD meter (FLUKE 6306), and the change of capacitance was recorded at 1 kHz while the DC power was changed from 0 V to 10 V, 0 V, and -10 V. The hysteresis of the capacitance change with respect to voltage was obtained and the residual DC was measured therefrom. Voltage holding ratio (VHR) was measured by applying a pulse having a width of 64 로 at a period of ± 1 V and 60 Hz to measure the rate at which the initially applied voltage was maintained in one cycle. It is a result.

division Example 1 Example 2 Example 3 R-DC 20 ℃ 9 mV 12 mV 12 mV 60 ℃ 26 mV 28 mV 30 mV VHR 20 ℃ 99% 99% 99% 60 ℃ 99% 98% 97%

As shown in Table 4, in Examples 1, 2, and 3, low residual DCs of 9 to 12 mV were measured at 20 ° C., and VHR was 98 to 99%. This indicates that the optical alignment agents according to the first, second and third embodiments of the present invention satisfy the basic characteristics for use as display elements.

According to the present invention, due to the weak physical bonding strength between the low thermal stability liquid crystal and the alignment layer 1, which is a problem of the conventional optical alignment agent, in particular, the optical alignment agent having a hydrocarbon-based polymer such as polyvinyl cinnamate, polymaleimide, polyolefin, etc. It can overcome the problem of low orientation force and light stability in the cell manufacturing process, maintain the excellent mechanical and thermal properties of polyamide, and at the same time have the advantages of polyester through copolymerization with polyester, and processability is improved. In particular, it is possible to manufacture the optimized structure according to the process and use through the diversification of physical properties and structure during copolymerization, and has high mechanical properties, heat resistance, and the like, optical transparency, chemical resistance, processability, etc. When applied to, high quality and high quality display quality can be realized.

Although the present invention has been described in connection with the above-mentioned preferred embodiments, it is possible to make various modifications or variations without departing from the spirit and scope of the invention. Accordingly, the appended claims will cover such modifications and variations as fall within the spirit of the invention.

Claims (11)

A poly (amide-ester) copolymerized photosensitive polymer liquid crystal aligning using a triazine ring having at least one photoactive group having a structure of [Formula 1] having at least one photoactive group in a side chain and having a triazine ring as a main chain Agent composition. [Formula 1] R ₁ of [Formula 1] is any _one of the following formulas (1a), (2a), (3a), (4a), In Formula (1a), X is any one of the following formulas, (Where m and n are each 0 to 10) In the formula (1a) Y is any one of the following formula, In the above formula, 1,2,3,4,5,6,7,8,9 are each selected from the following formula, (Where m and n are each 0 to 10 and A and B are H, F, Cl, CN, CF ₃ or CH ₃ ) In Formulas (2a) and (3a), n is 0 to 10, and 1,2,3,4,5 is any one of the following formulas. (Where m and n are each 0 to 10 and A and B are H, F, Cl, CN, CF ₃ or CH ₃ ) In the formula (4a), Y is any one selected from the following formula, (M and n are each 0 to 10) In the formula (4a), 1 and 2 are each selected from the following formula. (A is H, F, CN, CF ₃ or CH ₃ ) The amide bond connecting R ₂ to R ₄ and R ₅ in [Formula 1] is obtained by the reaction of amine and carboxylic acid. The general form of the reaction is as shown in [Scheme 1]. [Scheme 1] The ester bond connecting R ₃ to R ₄ and R ₅ in [Formula 1] is formed by the reaction of diol and carboxylic acid. The general form of the reaction is as shown in [Scheme 2]. [Scheme 2] R ₂ in [Formula 1] is due to the amine of [Scheme 1] is any one selected from the following formula. (Where m and n are each 0 to 10) And in the above [Formula 1] R ₃ is due to the alcohol of [Scheme 2] is any one selected from the following formula. (Where m and n are each 0 to 10) R ₄ and R ₅ in the above [Formula 1] is due to the carboxylic acid of [Scheme 1] and [Scheme 2] is any one selected from the following formula. (Where m and n are 0 to 10) The method of claim 1, The benzene ring has a triazine ring having one or more photoactive groups, further comprising an ortho- or meta-structure or a para-structure or a mixed structure of at least two of ortho-, meta- and para-structures. Poly (amide-ester) copolymerized photosensitive polymer liquid crystal aligning agent composition using. The method of claim 1, The polymer of [Formula 1] is a poly using a triazine ring having at least one photoactive group, characterized in that having a copolymerization ratio adjusted according to the fraction of diol and diamine in the equivalent ratio of the triazine monomer corresponding to the dicarboxylic acid (Amide-ester) copolymerized photosensitive polymer liquid crystal aligning agent composition. The method of claim 1, The polymer of [Formula 1] is a triazine ring having at least one photoactive group, characterized in that it has at least one copolymer structure selected from the group consisting of a random copolymer structure, a random block copolymer structure and a block copolymer structure Poly (amide-ester) copolymerized photosensitive polymer liquid crystal aligning agent composition using. Dissolving a poly (amide-ester) copolymerized photosensitive polymer liquid crystal aligning agent composition using a triazine ring having at least one photoactive group according to any one of claims 1 to 4 in an organic solvent (S1); Applying the solution onto the substrate (2) by spin coating or printing to form an alignment layer (S2); And It characterized in that it comprises a step (S3) of oblique irradiation or vertical irradiation of the ultraviolet (4) linearly polarized using a polarizer on the surface of the alignment layer (1) or non-polarized ultraviolet (4) not using a polarizer The manufacturing method of the photosensitive polymer liquid crystal aligning film. The method of claim 5, wherein The concentration of the organic solvent of the step S1 is 1 to 20wt% concentration and the viscosity is 1 to 100cps method for producing a photosensitive polymer liquid crystal aligning film. The method of claim 5, wherein The thickness of the alignment film (1) to be applied on the substrate (2) of the step S2 is 10 to 500nm, the manufacturing method of the photosensitive polymer liquid crystal alignment film. The method of claim 5, wherein The organic solvent is chlorobenzene, N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), N, N-dimethylimidazolidinone (DMI), N, N-dipropylimidazolidinone (DPI), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), cyclopentanone, cyclohexanone, dichloroethane, butylcellulose, gamma butyrolactone and tetrahydrofuran (THF Method for producing a photosensitive polymer liquid crystal aligning film, characterized in that any one or at least any two or more mixed solvents selected from the group consisting of A photosensitive polymer liquid crystal aligning film comprising a poly (amide-ester) copolymerized photosensitive polymer liquid crystal aligning agent composition using a triazine ring having at least one photoactive group according to any one of claims 1 to 4. A liquid crystal element comprising the liquid crystal aligning film (1) according to claim 9. The method of claim 10, The liquid crystal device is characterized in that it has one of the driving mode of the Super Twisted Nematic (STN), Twisted Nematic (TN), In Plane Switching (IPS), Vertically Alligned Twisted Nematic (VATN) mode.