KR20180111257A - Coating type thin layer polarizing film and manufacturing method thereof and compounds using the same - Google Patents

Abstract

The present invention relates to a coating type thin film polarizing film which comprises a chromonic liquid crystal compound including a new compound which can form stable LLC mesophase, and reliable transparent optical film, and a basic functional group. A chromonic liquid crystal material according to the present invention requires less manufacturing steps to be efficiently manufactured and produce a high yield.

Description

[0001] The present invention relates to a coating type thin film polarizing film and a method of manufacturing the same,

The present invention relates generally to the field of organic chemistry and optically anisotropic coatings. More specifically, the present invention relates to lyotropic liquid crystal systems based on heterocyclic amino derivative compounds and methods of making optically anisotropic coatings based thereon.

Particularly, one of the important components in a modern image display system is an optically anisotropic film that combines optical characteristics and other characteristics that can be optimized to meet the requirements of a specific device.

As the popularity of liquid crystal displays (LCDs) has increased, various liquid crystal (LC) compounds have been actively studied. Early research has focused on thermotropic liquid crystals that can be oriented into anisotropic films by mechanical forces. However, the forced orientation of molecules in a thermotropic LC film tended to disappear when the force was interrupted. On the other hand, a liquid crystalline polymer (LLC) film can maintain its own dichroic orientation even after removing the mechanical force. Suitable materials for this include materials capable of forming an LC mesophase that can be oriented to form anisotropic films.

Various polymeric materials have been used in the production of optically anisotropic films. Films based on these materials can obtain optical anisotropy through uniaxial stretching and transformation with organic dyes or iodine. In many cases, polyvinyl alcohol (PVA) is used as the base polymer [Liquid Crystals: Applications and Uses, B. Bahadur (ed.), World Scientific, Singapore, N.Y. (1990), Vol. 1, p. 101]. However, PVA-based films may have limited applications due to their low thermal stability. Therefore, the development of new materials and methods for the synthesis of optically anisotropic films with improved properties can develop this field. Specifically, the new material should be capable of reproducibly forming a film that is more conveniently synthesized and has high heat resistance and improved optical properties.

Recently, there has been an increasing demand for films with high optical anisotropy, which also feature improved selectivity over a wide range of wavelengths. A film in which maximum absorption takes place at a different one of a wide range of spectral ranges from infrared (IR) to ultraviolet (UV) regions is highly desirable. Organic dichroic molecules are generally known to be clustered into supramolecular complexes, such as pillars. These columns form the basic structural unit of the intermediate phase, and the intermediate phase can be oriented to form an anisotropic film with strong dichroism. For example, an anisotropic material based on a water-soluble organic dye was synthesized in U.S. Patent No. 5,739,296, U.S. Patent No. 6,174,394 and European Patent EP 0961138. These materials exhibit high absorbance in the visible light spectral range. While these compounds may be advantageous for many applications, their absorbance profile limits their use in forming transparent double refraction films.

In addition, currently used film application techniques require careful selection and precise maintenance of process variables such as, for example, dye concentration, film formation temperature, etc. during film formation. However, even if all the film forming conditions are precisely controlled, misorientation regions and / or micro-defects may be formed, and irregular local changes may still occur in the coating regions. These irregular localized changes may be caused by non-uniform micro- and macro-crystallization processes in the solvent removal process after application of the LLC system (i.e., LLC solution) to the substrate surface. Also, with currently used dyes, there is a high probability that a coating with a non-uniform thickness will be formed, and this non-uniform thickness again reduces the reproducibility of the desired film parameters.

Thus, there is a general need for a film that is optically anisotropic and sufficiently transparent and colorless in the driving region, especially in the visible light range. The disclosure of the present invention describes a novel series of compounds capable of forming a stable LLC intermediate phase and a reliable transparent optical film.

U.S. Patent No. 5,739,296 U.S. Patent No. 6,174,394 European Patent No. 0961138

Liquid Crystals: Applications and Uses, B. Bahadur (ed.), World Scientific, Singapore, N.Y. (1990), Vol. 1, p. 101

Thus, there is a general need for a film that is optically anisotropic and sufficiently transparent and colorless in the driving region, especially in the visible light range.

One aspect of the present invention relates to a coating type thin film polarizing film comprising a chromonic liquid crystal compound comprising at least one basic functional group selected from the group consisting of compounds represented by the following general formulas (1) and (2).

The chromonic liquid crystal material of the present invention can be produced efficiently and at a high yield because its preparation step is very short.

In addition, the chromonic liquid crystal material of the present invention is excellent in thermal characteristics, optical characteristics, heat resistance and durability, and is suitable for use as an OLED, an LCD polarizing film, a color filter, and a material for illumination.

1 is the 1 H NMR (400 MHz, CDCl 3) data of Synthesis Example 5.
2 is the 1 H NMR (400 MHz, CDCl 3) data of Synthesis Example 11.
3 shows the excellent characteristics of Production Example 16 (Black) as the PE (%) data of Production Example 15 (Green), Production Example 16 (Black) and Production Example 17 (Red).
4 shows the horizontal and vertical transmittances of Production Example 4 and Production Example 5. As the ratio of the formula (2-1) increases, the PE characteristic decreases.
Fig. 5 shows the horizontal and vertical transmittances of Production Example 16, which confirms that excellent physical properties are realized in Production Example 16.
6 is a graph simultaneously showing TT (%) and PE (%) of Production Examples 1 to 17, and shows Production Examples 8, 9, 10, 11 and 12 having TT (%) of 40 or more and PE , 13 and 16 show excellent performance for commercialization.

Hereinafter, various aspects and various embodiments of the present invention will be described in more detail.

According to an aspect of the present invention, there is provided a coating type thin film polarizing film comprising a chromonic liquid crystal compound containing at least one basic functional group selected from the following general formulas (1) and (2).

[Chemical Formula 1]

Wherein R 1 and R 4 are hydrogen, CN, halogen, alkylphenoxy, pyrrolyl, phenyl, alkylphenyl, biphenyl, alkylbiphenyl, alkoxyl group having 1 to 15 carbon atoms, (CH 2) nN (ALKYL) 2 group or a pyridine group, a primary to tertiary amine group, and y is an integer of 2 to 4, wherein n is 2 to 15, the ALKYL group is a C 1 to C 15 group,

(2)

Wherein R7 and R10 are independently selected from the group consisting of hydrogen, CN, halogen, alkylphenoxy, pyrrolyl, phenyl, alkylphenyl, biphenyl, alkylbiphenyl, alkoxyl of 1 to 15 carbon atoms, (CH2) nN (ALKYL) 2 wherein the alkyl group is an alkyl group having 1 to 15 carbon atoms, a pyridine group, a primary or tertiary amine group, and y is an integer of 3 to 4;

According to a preferred embodiment of the present invention, the coating type thin film of the present invention is characterized by comprising a chromonic liquid crystal compound represented by the following general formulas 1-1 to 1-9 or 2-1 to 2-4 .

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

[Chemical Formula 1-7]

[Chemical Formula 1-8]

[Chemical Formula 1-9]

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Chemical Formula 2-4]

In addition, the polarizing film of the present invention may further comprise a dichroic auxiliary dye in addition to the polarizing dichroic dye, wherein the dichroic auxiliary dye has a visible ray region in which the polarizing dichroic dye can not absorb or is weakly absorbed And preferably at least two kinds selected from the compounds represented by the following formulas (1-1) to (1-9) and the compounds represented by the following formulas (2-1) to And preferably three or more.

The dichroic auxiliary dye may be used in an amount of 0.1 to 5 parts by weight, preferably 0.5 to 4 parts by weight, more preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the polymer resin. At this time, if the amount of the dichroic auxiliary dye is less than 0.1 part by weight, an additional visible light absorbing effect due to use thereof may not be expected. If the amount is more than 5 parts by weight, the transmittance of the polarizing film decreases, Therefore, it is recommended to use within the above range.

Further, the polarizing film of the present invention may further use a crosslinking agent such as boric acid and the like in addition to the polymer resin, the polarizing dichroic dye, and the dichroic auxiliary dye.

The polarizing film of the present invention preferably has an average thickness of 10 to 150 μm, preferably 10 to 100 μm, more preferably 10 to 50 μm. If the average thickness is less than 10 μm, the polarizing film is too thin If it exceeds 150 μm, it is not suitable for peeling off the recent parts. Therefore, it is suitable in terms of transparency and mechanical strength to have a thickness within the above range.

In addition, the polarizing film of the present invention may further include a transparent protective film on one or both sides thereof. As the transparent protective film, materials generally excellent in transparency used in the related art can be used, and preferable examples thereof include polycarbonate, polyethylene At least one selected from terephthalate, cycloolefin copolymer, cycloolefin polymer, triacetylcellulose, polyether sulfone and polyether imide can be used.

In addition, an adhesive layer may be formed between the polarizing film and the transparent protective layer. As the adhesive used for the adhesive layer, one kind selected from among triacetyl cellulose, cycloolefin copolymer and cycloolefin polymer It is preferable to use an adhesive containing the above.

A method for producing the polarizing film of the present invention using the above-described composition will be described below.

Hereinafter, the present invention will be described in more detail with reference to Examples and the like, but the scope and content of the present invention can not be construed to be limited or limited by the following Examples. It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the present invention as set forth in the following claims. It is natural that it belongs to the claims.

In addition, the experimental results presented below only show representative experimental results of the embodiments and the comparative examples, and the respective effects of various embodiments of the present invention which are not explicitly described below will be specifically described in the corresponding part.

Example

[Synthesis Example]

Preparation Example 1: Preparation of chromonic liquid crystal compound

(1) Production of bis- (N, N'-diethylaminoethyl) perylene-3,4,9,10-tetracarboxylic diimide diformic acid

Add 80 mL of distilled water and 8.00 g of perylene-3,4,9,10-tetracarboxylic dianhydride (20.4 mmol) to a round flask and add 8 mL of N, N'-diethylethylenediamine (Aldrich, 57 mmol, 2.8 equiv) And refluxed at 100 < 0 > C for 24 hours. After the completion of the reaction, the reaction solution was cooled at room temperature. After washing with excess 1% KOH (aq) and distilled water, it was dried under vacuum. The reaction product, Bis- (N, N'-diethylaminoethyl) perylene-3,4,9,10-tetracarboxylic diimide, was obtained in an 88% yield of 10.6 g (18.0 mmol).

^{1 H NMR (400 MHz, CF} 3 COOD): 8.78 (4H, Ar-H), 8.75 (4H, Ar-H), 4.72 (4H, (CHO) 2 CH 2 CH 2 N +), 3.64 (4H, ( CHO) ₂ CH ₂ CH ₂ N +), 3.45 (8H, -NCH ₂ CH ₃ ), 1.40 (12H, -CH ₃ ) ppm.

¹³ CNMR (100 mHz, CF ₃ COOD): 166.12, 136.47, 133.23, 129.40, 126.46, 124.45, 121.53, 52.43, 49.17, 36.37, 7.44 ppm.

UV-vis (HCOOH, 4.5 * 10 ^-6 M)? _Abs (nm): 532 (77 800), 495 (49100), 465 (18400).

UV-vis (0.02 M HCl, 1.7 * 10 ^-5 M, 25 캜)? _Abs (nm): 501- (42 200), 540 (21 100) nm.

UV-vis (H2O, 5.5 * 10 ^-5 M)? _Abs (nm): 501 (33 200), 540 (16 000).

IR (KBr): 2969, 1695 , 1654, 1593, 1579, 1439, 1404, 1359, 1342, 1247, 1163, 1103, 850, 809, 797, 746cm -1.

HRMS-FABm / z calcd for [C36H37N4O4] + (MH +), 589.2815; found, 589.2788. mp 270 [deg.] C (dec).

[Formula 1-1]

(2) Preparation of bis- (N, N'diethylaminoethyl) -1,7-dibromo-perylene-3,4,9,10-tetracarboxylic diimide diformic acid

After adding 80 mL of distilled water and 8.00 g of 1,7-dibromo-perylene-3,4,9,10-tetracarboxylic dianhydride (20 mmol) into a round flask, add 8 mL of N, N'-diethylethylenediamine (Aldrich, 50 mmol , 3.0 equiv) was added and refluxed at 100 < 0 > C for 24 hours. After the completion of the reaction, the reaction solution was cooled at room temperature. After washing with excess 1% KOH (aq) and distilled water, it was dried under vacuum. Reaction product Bis- (N, N'diethylaminoethyl) -1,7-dibromo-perylene-3,4,9,10-tetracarbonic diimide was obtained in a yield of 90% of 11.0 g.

^{1 H NMR (400 MHz, CDCl} 3):

8.21 (2H, Ar-H), 8.14 (2H, Ar-H), 7.85 (2H, Ar-H), 3.16 (4H), 2.57 (4H), 2.46 (8H), 0.94 (12H)

¹³ C NMR (100 MHz, CDCl ₃ ): 165.0, 159.3, 136.2, 131.8, 130.9, 128.1, 127.7, 126.2, 125.3, 123.8, 50.2, 49.6, 38.4, 13.3 ppm.

HRMS-FAB m / z calcd for [C ₃₆ H ₃₄ Br ₂ N ₄ O ₄ ] + (MH +), 746.50; found, 746.09

[Formula 1-2]

(3) Production of bis- (N, N'diethylaminoethyl) -1,7-dichloro-perylene-3,4,9,10-tetracarboxylic diimide diformic acid

After adding 80 mL of distilled water and 8.00 g of 1,7-dichloro-perylene-3,4,9,10-tetracarboxylic dianhydride (20.4 mmol) into a round flask, add 8 mL of N, N'-diethylethylenediamine (Aldrich, 60 mmol , 3.0 equiv) was added and refluxed at 100 < 0 > C for 24 hours. After the completion of the reaction, the reaction solution was cooled at room temperature. After washing with excess 1% KOH (aq) and distilled water, it was dried under vacuum. Reaction product Bis- (N, N'diethylaminoethyl) -1,7-dichloro-perylene-3,4,9,10-tetracarbonic diimide was obtained in a yield of 86% at 10.4 g.

^{1 H NMR (400 MHz, CDCl} 3):

8.23 (2H, Ar-H), 7.93 (2H, Ar-H), 7.82 (2H, Ar-H), 3.19 (4H), 2.64 (4H), 2.50 (8H), 0.98 (12H)

^{13 C} NMR (100 mHz, CDCl ₃ ): 160.1, 132.4, 130.6, 129.3, 125.3, 123.1, 50.4, 50.0, 39.0, 13.5 ppm.

HRMS-FABm / z: calcd for [C 36 H 34 Cl 2 N 4 O 4] + (MH +), 656.20; found,

[Formula 1-3]

(4) Preparation of bis- (N, N'diethylaminoethyl) -1,7-difluoro-perylene-3,4,9,10-tetracarboxylic diimide diformic acid

After adding 80 mL of distilled water and 10.00 g of 1,7-difluoro-perylene-3,4,9,10-tetracarboxylic dianhydride (20 mmol) into a round flask, add 8 mL of N, N'-diethylethylenediamine (Aldrich, 60 mmol , 3.0 equiv) was added and refluxed at 100 < 0 > C for 24 hours. After the completion of the reaction, the reaction solution was cooled at room temperature. After washing with excess 1% KOH (aq) and distilled water, it was dried under vacuum. 10.8 g (19.0 mmol) of the reaction product (Formula 1-1) was obtained in a yield of 88%.

^{1 H NMR (400 MHz, CDCl} 3):

8.23 (2H, Ar-H), 7.93 (2H, Ar-H), 7.82 (2H, Ar-H), 3.19 (4H), 2.64 (4H), 2.50 (8H), 0.98 (12H)

_{^{13 CNMR (100 mHz, CDCl 3}} ): 162.1, 133.1, 130.5, 128.3, 125.3, 123.4, 50.5, 50.1, 39.3, 13.9 ppm.

HRMS-FAB m / z calcd for [C ₃₆ H ₃₄ F ₂ N ₄ O ₄ ] + (MH +), 624.25; found,

[Formula 1-4]

(5) Formula 1-5: Preparation of bis- (N, N'diethylaminoethyl) -1,7-dicyano-perylene-3,4,9,10-tetracarboxylic diimide diformic acid

After adding 80 mL of distilled water and 10.00 g of 1,7-dicyano-perylene-3,4,9,10-tetracarboxylic dianhydride (20 mmol) into a round flask, add 8 mL of N, N'-diethylethylenediamine (Aldrich, 60 mmol , 3.0 equiv) was added and refluxed at 100 < 0 > C for 24 hours. After the completion of the reaction, the reaction solution was cooled at room temperature. After washing with excess 1% KOH (aq) and distilled water, it was dried under vacuum. 11 g of the reaction product (Formula 1-1) was obtained in a yield of 89%.

^{1 H NMR (400 MHz, CDCl} 3): 8.25 (2H, Ar-H), 7.96 (2H, Ar-H), 7.84 (2H, Ar-H), 3.20 (4H), 2.66 (4H), 2.51 ( 8H), 0.99 (12H) ppm.

_{^{13 CNMR (100 mHz, CDCl 3}} ): 162.6, 133.1, 130.5, 128.7, 125.3, 123.4, 50.5, 50.1, 39.5, 14.0ppm.

HRMS-FABm / z: calcd for [C 36 H 34 F 2 N 4 O 4] + (MH +), 638.26; found,

[Formula 1-5]

(6) Preparation of bis- (N, N'diethylaminoethyl) -1,7-di (4-hexyl) phnoxy-perylene-3,4,9,10-tetracarboxylic diimide diformic acid

After adding 80 mL of distilled water and 8.00 g of 1,7-di (4-hexyl) perylene-3,4,9,10-tetracarboxylic dianhydride (20 mmol) into a round flask, add 8 mL of N, N'-diethylethylenediamine Aldrich, 60 mmol, 3.0 equiv) was added and refluxed at 100 < 0 > C for 24 hours. After the completion of the reaction, the reaction solution was cooled at room temperature. After washing with excess 1% KOH (aq) and distilled water, it was dried under vacuum. Reaction product Bis- (N, N'diethylaminoethyl) -1,7-di (4-hexyl) phnoxy-perylene-3,4,9,10-tetracarbonic diimide was obtained in 90% yield of 12 g.

^{1 H NMR (400 MHz, CDCl} 3): 8.23 (2H, Ar-H), 7.93 (2H, Ar-H), 7.82 (2H, Ar-H), 7.32 to 7.28 (8H, Ar-H) 6.95 ( 4H, ArH), 4.06 (4H), 3.16 (4H), 2.57 (4H), 2.46 (8H), 1.80 (4H), 1.47 ) ppm.

^{13 C} NMR (100 mHz, CDCl ₃ ): 162.1, 159.3, 133.1, 130.8, 127.7, 117.2, 110.5, 50.5, 50.1, 39.3, 29.6, 25.6, 22.7, 14.1, 13.9 ppm.

HRMS-FAB m / z calcd for [C ₃₆ H ₃₄ F ₂ N ₄ O ₄ ] + (MH +), 973.22; found, 972.50

[Chemical Formula 1-6]

(7) Preparation of bis- (N, N'diethylaminoethyl) -1,7-di- (4-tert-butylphenoxy) perylene-3,4,9,10-tetracarbonic diimide diformic acid

80 mL of distilled water and 8.00 g of 1,7-di- (4-tert-butyl nhenoxy) perylene-3,4,9,10-tetracarboxylic dianhydride (20.0 mmol) were added to a round flask, and 8 mL of N, N '-diethylethylenediamine (Aldrich, 30 mmol, 3.0 equiv) was added and refluxed at 100 ° C for 24 hours. After the completion of the reaction, the reaction solution was cooled at room temperature. After washing with excess 1% KOH (aq) and distilled water, it was dried under vacuum. Reaction product Bis- (N, N'diethylaminoethyl) -1,7-di- (4-tert-butylphenoxy) perylene-3,4,9,10-tetracarbonic diimide was obtained in 95% yield of 12 g.

¹ H NMR (400 MHz, CDCl ₃ ): 8.25 (2H, Ar-H), 7.93 (2H, Ar-H), 7.82 ), 4.06 (4H), 3.18 (4H), 2.58 (4H), 2.46 (8H), 1.80 (4H), 1.47 (4H), 1.35 (18H), 0.90 (12H)

^{13 C} NMR (100 mHz, CDCl ₃ ): 159.4, 153.9, 153.9, 144.4, 133.1, 130.8, 127.4, 117.2, 110.5, 50.5, 50.1, 38.4, 34.2, 29.6, 25.6, 22.7, 14.1, 13.2 ppm.

HRMS-FAB m / z calcd for [C ₅₆ H ₆₀ N ₄ O ₆ ] + (MH +), 885.12; found, 885.45

[Chemical Formula 1-7]

(8) Preparation of bis- (N, N'diethylaminoethyl) -1,7-di-hexyloxy perylene-3,4,9,10-tetracarboxylic diimide diformic acid

Insert the 1, 7-di-hexyloxyperylene- 3,4,9,10-tetracarboxylic dianhydride (20 mmol) in 100 mL of distilled water and 10.00 g round bottom flask, 8 mL of N, N'-diethylethylenediamine (Aldrich, 60 mmol , 3.0 equiv) was added and refluxed at 100 < 0 > C for 24 hours. After the completion of the reaction, the reaction solution was cooled at room temperature. After washing with excess 1% KOH (aq) and distilled water, it was dried under vacuum. The reaction product, Bis- (N, N'diethylaminoethyl) -1,7-di-hexyloxy perylene-3,4,9,10-tetracarbonic diimide, was obtained in a yield of 87% of 9.1 g.

¹ H NMR (400 MHz, CDCl ₃ ): 8.25 (2H, Ar-H), 7.77 (2H, Ar-H), 7.02 2.59 (4H), 2.46 (8H), 1.80 (4H), 1.47 (4H), 1.35 (18H), 0.90 (12H) ppm.

¹³ CNMR (100 mHz, CDCl ₃ ): 159.4, 153.9, 153.9, 144.4, 133.1, 130.8, 127.4, 117.2, 110.5, 105.4, 50.5, 50.1, 38.4, 34.2, 29.6, 25.6, 22.7, 14.5, 14.1, 13.2 ppm .

HRMS-FAB m / z calcd for [C ₄₈ H ₆₀ N ₄ O ₆ ] + (MH +), 788.45; found, 789.03.

[Chemical Formula 1-8]

(9) Preparation of bis- (N, N'diethylaminoethyl) - (1,7-dipyrrolidinyl) -perylene-3,4,9,10-tetracarbonic diimide diformic acid

After adding 100 mL of distilled water and 10.00 g of 1,7-dipyrrolidinylperylene-3,4,9,10-tetracarboxylic dianhydride (20 mmol) into a round flask, add 8 mL of N, N'-diethylethylenediamine (Aldrich, 60 mmol, equiv) was added and refluxed at 100 < 0 > C for 24 hours. After the completion of the reaction, the reaction solution was cooled at room temperature. After washing with excess 1% KOH (aq) and distilled water, it was dried under vacuum. Reaction product Bis- (N, N'diethylaminoethyl) - (1,7-dipyrrolidinyl) -perylene-3,4,9,10-tetracarbonic diimide was obtained in a yield of 90% of 10.1 g.

^{1 H NMR (400 MHz, CDCl} 3): 8.21 (2H, Ar-H), 7.75 (2H, Ar-H), 7.02 (2H, Ar-H), 3.46 (8H), 3.31 (8H), 3.12 ( 4H), 1.54 (4H), 1.40 (4H), 0.93 (6H) ppm.

^{13 C} NMR (100 mHz, CDCl ₃ ): 158.3, 153.8, 134.3, 130.9, 129.2, 127.7, 118.0, 54.7, 41.1, 29.5, 25.6, 19.8, 13.8 ppm.

HRMS-FAB m / z calcd for [C ₃₉ H ₄₉ N ₄ O ₄ ] + (MH +), 640.78; found, 640.30.

[Chemical Formula 1-9]

(10) Preparation of bis- (N, N'diethylaminoethyl) terylene-3,4,11,12-tetracarboxylic diimide diformic acid

To a round flask, toluene / EtOH (25: 1) and 0.4 M and 10.0 g 20 mmol (ethylaminoethyl) -3 -bromo naphthalene insert the _{imide, Pd (PPh 3) 4} 10 ml%, K 2 CO 3 (3.0eq) Boric acid (1.02 eq) was added and refluxed at 80 < 0 > C for 24 hours. After the completion of the reaction, the reaction solution was cooled at room temperature. After the filter was dried in a vacuum state. Then, it was heated with K ₂ CO ₃ (2.0 eq) and ethanol amine at 80 ° C for 16 hours. (N, N'diethylaminoethyl) terylene-3,4,11,12-tetracarboxylic diimide (TFA, DMSO / H2O) was obtained by heating the reaction product at 50 ° C for 18 hours. Was obtained in a yield of 92%.

^{1 H NMR (400 MHz, CDCl} 3): 8.94 (8H, m, Ar-H), 8.60 (4H, m, Ar-H), 3.12 (4H), 2.56 (4H), 2.46 (8H), 0.90 ( 12H) ppm.

^{13 C} NMR (100 mHz, CDCl ₃ ): 158.3, 153.8, 134.3, 130.9, 129.2, 127.7, 118.0, 54.7, 41.1, 29.5, 25.6, 19.8, 13.8 ppm.

HRMS-FABm / z calcd for [C36H37N4O4] + (MH +), 712.30; found, 712.85.

[Formula 2-1]

(11) Preparation of bis- (N, N'dimethylaminoethyl) terylene-3,4,9,10-tetracarboxylic diimide diformic acid

10 ml of toluene / EtOH (25: 1) and 20 mmol (methylaminoethyl) -3-bromo naphthalene imide of 10.0 g were added to a round flask and 10 ml of Pd (PPh ₃ ) ₄ and 3.0 eq of K ₂ CO ₃ Boric acid (1.02 eq) was added and refluxed at 80 < 0 > C for 24 hours. After the completion of the reaction, the reaction solution was cooled at room temperature. After the filter was dried in a vacuum state. Then, it was heated with K ₂ CO ₃ (2.0 eq) and ethanol amine at 80 ° C for 16 hours. After the reaction, the reaction product was heated at 50 ° C under TFA and DMSO / H2O conditions for 18 hours to finally obtain the reaction product Bis- (N, N'dimethylaminoethyl) terylene-3,4,11,12-tetracarbonic acid diimide was obtained in a yield of 92%.

^{1 H NMR (400 MHz, CDCl} 3): 8.94 (8H, m, Ar-H), 8.60 (4H, m, Ar-H), 3.12 (4H), 2.56 (4H), 2.46 (8H), 0.90 ( 12H) ppm.

^{13 C} NMR (100 mHz, CDCl ₃ ): 158, ₃ , 153.8, 134.3, 130.9, 129.2, 127.7, 118.0, 54.7, 41.1, 29.5, 25.6, 19.8, 13.8 ppm.

HRMS-FABm / z calcd for [C36H37N4O4] + (MH +), 656.74; found,

[Formula 2-2]

(12) Preparation of bis- (N, N'dimethylaminoethyl) terarylene-3,4,9,10-tetracarboxylic diimide diformic acid

To a round flask, toluene / EtOH (25: 1) and 0.4 M and 10.0 g 20 mmol (methylaminoethyl) -9 -bromo perylene insert the _{imide, Pd (PPh 3) 4} 10 ml%, K 2 CO 3 (3.0eq) Boric acid (1.02 eq) was added and refluxed at 80 < 0 > C for 24 hours. After the completion of the reaction, the reaction solution was cooled at room temperature. After the filter was dried in a vacuum state. Then, it was heated with K ₂ CO ₃ (2.0 eq) and ethanol amine at 80 ° C for 16 hours. After purification, the reaction product was heated at 50 ° C under TFA and DMSO / H2O conditions for 18 hours to finally obtain the reaction product Bis- (N, N'dimethylaminoethyl) tetrarylene-3,4,11,12-tetracarbonic acid diimide was obtained in a yield of 92%.

^{1 H NMR (400 MHz, CDCl} 3): 8.78 (4H, Ar-H), 8.75 (4H, Ar-H), 4.72 (4H, (CHO) 2 CH 2 CH 2 N +), 3.64 (4H, (CHO ) ₂ CH ₂ CH ₂ N +), 3.45 (8H, -NCH ₂ CH ₃ ), 1.40 (12H, -CH ₃ ) ppm.

^{13 C} NMR (100 mHz, CDCl ₃ ):? 166.12, 136.47, 133.23, 129.40, 126.46, 124.45, 121.53, 52.43, 49.17, 36.37, 7.44 ppm.

HRMS-FABm / z calcd for [C36H37N4O4] + (MH +), 589.2815; found, 589.2788. mp

[Formula 2-3]

(13) Preparation of bis- (N, N'diethylaminoethyl) terarylene-3,4,9,10-tetracarboxylic diimide diformic acid

To a round flask, toluene / EtOH (25: 1) and 0.4 M and 10.0 g 20 mmol (methylaminoethyl) -9 -bromo perylene insert the _{imide, Pd (PPh 3) 4} 10 ml%, K 2 CO 3 (3.0eq) Boric acid (1.02 eq) was added and refluxed at 80 < 0 > C for 24 hours. After the completion of the reaction, the reaction solution was cooled at room temperature. After the filter was dried in a vacuum state. Then, it was heated with K ₂ CO ₃ (2.0 eq) and ethanol amine at 80 ° C for 16 hours. (N, N'diethylaminoethyl) tetrarylene-3,4,11,12-tetracarboxylic diimide (TFA, DMSO / H2O) Was obtained in a yield of 92%.

^{1 H NMR (400 MHz, CDCl} 3):

HRMS-FABm / z calcd for [C36H37N4O4] + (MH +), 589.2815; found, 589.2788. mp 270 [deg.] C (dec).

HRMS-FAB m / z calcd for [C36H37N4O4] + (MH +), 780.27d, 780.88

[Chemical Formula 2-4]

[ Example ]

Examples 1 to 17: Preparation of polarizing film.

A compound was prepared in the same manner as in Synthesis Example 1, and an aqueous solution containing 10 to 30% by weight of a compound as shown in the following Table 1 and formic acid (2 eq) was prepared. Or slot coater, and dried at room temperature.

Production Example 1: Evaluation of physical properties

The transmittance (%) and the degree of polarization (transparency) of the polarizing film after being coated on the 25 μm PET (Toray Advanced Material) base material or glass, cycloolefin, triacetylcellulose or the like prepared in Examples 1 to 17 by using a Bar coater Respectively.

(1) Method of measuring transmittance

The transmittance of the polarizing film was measured using a spectrophotometer (Minolta, CM 3500d).

(2) Method of measuring polarization degree

The polarization degree of the polarizing film was measured using a phase difference film optical material inspection apparatus.

The photographs in the above table are actual photographs of the film drawings produced according to the production example and show vertical and horizontal transmittance.

Claims (7)

A coating type thin film polarizing film characterized by comprising a chromonic liquid crystal compound comprising at least one basic functional group selected from the group consisting of compounds represented by the following general formulas (1) and (2).

Wherein R 1 and R 4 are hydrogen, CN, halogen, alkylphenoxy, pyrrolyl, phenyl, alkylphenyl, biphenyl, alkylbiphenyl, alkoxyl group having 1 to 15 carbon atoms, (CH 2) nN (ALKYL) 2 group or a pyridine group, a primary to tertiary amine group, and y is an integer of 2 to 4, wherein n is 2 to 15, the ALKYL group is a C 1 to C 15 group,
(2)

Wherein R7 and R10 are independently selected from the group consisting of hydrogen, CN, halogen, alkylphenoxy, pyrrolyl, phenyl, alkylphenyl, biphenyl, alkylbiphenyl, alkoxyl of 1 to 15 carbon atoms, (CH2) nN (ALKYL) 2 wherein the alkyl group is an alkyl group having 1 to 15 carbon atoms, a pyridine group, a primary or tertiary amine group, and y is an integer of 3 to 4; The liquid crystal composition according to claim 1, wherein the basic chromonic liquid crystal compound in the weight ratio of the chromonic liquid crystal composition; (1) or (2) in a weight ratio of 1.0: 0.1 to 0.9. 3. The process for producing a chromonic liquid crystal coating film according to claim 2, wherein the basic chromonic liquid crystal compound is contained in an amount of 3 to 30% by weight based on 100% by weight of the mordant chromonic liquid crystal composition. 4. The composition of claim 3, further comprising a basic chromonic liquid crystal compound having a basic functionality; An orientation step of orienting a coating film composed of the chromonic liquid crystal composition; Method of orienting shear. The coated thin film polarizing film according to claim 4, wherein an average transmittance (TT) is 30 to 60% and a polarization degree is 70 to 99.9% in measuring the degree of polarization. The thin film polarizing film according to claim 4, wherein the coating thickness of the chromonic liquid crystal coating film oriented using a sheer is 25 to 0.5 μm. The method as claimed in claim 6, wherein the base substrate is made of a material selected from the group consisting of polycarbonate (PC), polyethylene terephthalate (PET), cycloolefin copolymer (COC), cycloolefin polymer (COP), triacetylcellulose (TAC) ) And a polyetherimide (PEI).

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