KR20110126393A - Azo dye derivatives containing acrylate group and the dye-basd color filters using the derivatives - Google Patents

Abstract

PURPOSE: An azo dye compound for a color resist is provided to secure light-proof properties, heat resistance and chemical resistance and to obtain a color filter for dye with high contrast and accurate color embodiment. CONSTITUTION: An azo dye compound for a color resist is represented by chemical formula (1). In chemical formula (1), R1 and R2 are independently selected from a substituted or unsubstituted acrylate group or a methacrylate group; R3 is selected from an acetamino group or a C1-C6 alkyl group; R4 is selected from hydrogen, a substituted or unsubstituted azo group or a substituted or unsubstituted diazo group. The color filter for dye for a liquid crystal display comprises the azo dye compound.

Description

Azo dye derivatives substituted with acrylic derivatives and dye type color filters for liquid crystal display using the same {Azo dye derivatives containing acrylate group and the dye-basd color filters using the derivatives}

The present invention relates to an azo dye substituted with an acrylic derivative and a method for producing a dye type color filter for a liquid crystal display using the same, and more particularly, an azo dye compound for use in a color filter for a liquid crystal display having both heat resistance and chemical resistance. It relates to a color filter using the same.

Color filters are an important factor in determining image quality for color LCDs and other imaging devices. The color filter generally includes a glass substrate, a black matrix, a color layer, a coating layer and an ITO layer. Color filters are made of dyes or pigments of red, green and blue. Such a dye material serves to change the white light of the backlight unit to each corresponding color. The color filter material is required to have high color reproducibility such as high color purity, transmittance, and contrast. The color filter material has an unnecessary wavelength other than the absorption wavelength where the spectrum of the dye material used in the color filter is required and has an absorption band having a narrow width. In addition, it must have high heat resistance, light resistance, and chemical resistance that does not fade or discolor under ultraviolet, acid, and basic conditions exposed during the etching of the color resist.

To date, there are four techniques for manufacturing color filters: dyeing, vapor deposition, printing, and pigment dispersion. Since the initial pigment dispersion technology was not excellent, the dyeing method using dyes with excellent color reproducibility was used, but the pigment dispersion method produced a color filter while improving pigment dispersion technology to secure excellent color reproducibility and durability against heat, light and humidity. It is applied as the most common technique.

Although the pigment dispersion method is being applied as the most common technique of manufacturing a color filter, this technique causes a problem of poor transmittance and contrast due to aggregation of pigment particles. Therefore, it takes a lot of time and money to make a pigment dispersion of more stable fine particles without agglomeration of molecules, which is one cause to increase the cost of LCD panel manufacturing. Dye-type color filters that do not require a dispersion process have high permeability and contrast characteristics because they have little aggregation between molecules and thus have little effect of particle scattering by molecular particles. However, due to weak heat resistance, light resistance, and chemical resistance, which are disadvantages of the dye type color filter, it has become a big problem in the actual LCD panel manufacturing. In particular, improving the heat resistance, which is a requirement for the commercialization of the dye type color filter, is the main issue.

The first technical problem to be solved by the present invention is to provide an azo dye compound for color resists with improved heat resistance and chemical resistance.

The second technical problem to be solved by the present invention is to provide a dye type color filter for a liquid crystal display comprising the azo dye compound.

In order to solve the first technical problem, the present invention provides an azo compound for a color resist represented by the following general formula (1):

(1)

(One)

Where

R ₁ and R ₂ are each independently selected from a substituted or unsubstituted acrylate group or methacrylate group,

R ₃ is selected from acetamino group or C ₁ -C ₆ alkyl group,

R ₄ is selected from hydrogen, a substituted or unsubstituted azo group, or a substituted or unsubstituted diazo group.

According to one embodiment of the present invention, the azo compound may be a compound characterized by the following formula (2).

(2)

(2)

Where

R ₁ and R ₂ are each independently selected from a substituted or unsubstituted acrylate group or methacrylate group,

R ₃ is selected from acetamino group or C ₁ -C ₆ alkyl group,

R ₅ is selected from substituted or unsubstituted phenyl, substituted or unsubstituted thiazole group, and substituted or unsubstituted thiophene group.

According to another embodiment of the present invention, in the formula (2) R ₅ is preferably selected from the group consisting of dibromonitrobenzene, dicyanonitrobenzene, dinitrothiophene, nitrothiazole, benzothiazole For example, it may be a compound of the following formula.

          AZ-1 AZ-2

         AZ-3 AZ-4

         AZ-5 AZ-6

         AZ-7 AZ-8

         AZ-9 AZ-10

AZ-11 AZ-12

AZ-11 AZ-12

         AZ-13 AZ-14

AZ-15 AZ-16

In order to solve the second technical problem, the present invention provides a dye type color filter for a liquid crystal display, comprising the azo dye compound of the formula (1).

The present invention uses a dye having a very high solubility in a solvent other than the pigment dispersion PGMEA under the same conditions as the color resist process prepared using a conventional pigment dispersion millbase, and also substituted acrylate or methacrylate groups The lithography process has great significance in that it participates in the UV curing process of the binder in the same manner and secures light, heat resistance, and chemical resistance of the color.

Unlike pigment-disperse color filters that reach the limits of color, contrast, and lifespan, dye-type color filters, which can achieve high contrast and precise color, are still in the research stage. It is expected.

1 is a diagram illustrating a synthesis process of diazo dyes AZ-7 to 8 according to an embodiment of the present invention.
2 is a view illustrating a synthesis process of diazo dyes AZ-9 to 12 according to an embodiment of the present invention.
3 is a diagram illustrating a synthesis process of diazo dyes AZ-13 to 16 according to one embodiment of the present invention.
4 is a view showing color filter color coordinates of a diazo dye according to an embodiment of the present invention.
5 is a graph showing the results of measuring the thermal stability (30 minutes at 120 ~ 230 ℃) of the dyes (AZ-9 and 10) according to an embodiment of the present invention.
Figure 6 is a graph showing the results of measuring the thermal stability (30 minutes at 120 ~ 230 ℃) of the dye (AZ-11, 12, 14 and 16) according to an embodiment of the present invention.
7 is a view showing the TGA curve on the synthetic dyes (AZ-9, AZ-10) and the existing pigments and their films according to an embodiment of the present invention.
8 is a view showing the TGA curve on the synthetic dyes (AZ-11, 12, 14 and 16) and the existing pigments and their films according to an embodiment of the present invention.
9 is a graph showing the dissolution curve of the dye in the developer 2.28% KOH (immersion).
10 is OM image of Pigment Blue, binder and synthesized dye film (magnification 100 ×, high resolution (≦ 30 μm)).
11 is an OM image of the synthesized dye (AZ-9, 10, 13 and 15) film (magnification 100 ×, high resolution (≦ 30 μm)).
12 is an OM image of the synthesized dye (AZ-11, 12, 14, 16) film (magnification 100 ×, high resolution (≦ 30 μm)).
13 is a cross sectional view of only negative photoresist, pigment and dye (AZ-9, 10).
14 is a cross sectional view of the dyes AZ-11, 12, 14 and 16;

Hereinafter, embodiments of the present invention will be described in detail.

The azo compound for color resists according to the present invention is characterized by the following general formula (1):

(1)

(One)

Where

R ₁ and R ₂ are each independently selected from a substituted or unsubstituted acrylate group or methacrylate group,

R ₃ is selected from acetamino group or C ₁ -C ₆ alkyl group,

R ₄ is selected from hydrogen, a substituted or unsubstituted azo group, or a substituted or unsubstituted diazo group.

According to one embodiment of the present invention, the azo compound may be a compound characterized by the following formula (2).

(2)

(2)

Where

R ₁ and R ₂ are each independently selected from a substituted or unsubstituted acrylate group or methacrylate group,

R ₃ is selected from acetamino group or C ₁ -C ₆ alkyl group,

R ₅ is selected from substituted or unsubstituted phenyl, substituted or unsubstituted thiazole group, and substituted or unsubstituted thiophene group.

According to another embodiment of the present invention, in the formula (2) R ₅ is preferably selected from the group consisting of dibromonitrobenzene, dicyanonitrobenzene, dinitrothiophene, nitrothiazole, benzothiazole For example, it may be a compound described in Synthesis Examples below.

In addition, the dye-type color filter for a liquid crystal display according to the invention is characterized in that it comprises an azo dye compound of the formula (1).

Synthetic example  1: 2,2 '-(3- Acetamidophenyl ) Vis (Ethane-2,1- Dill ) Diacrylate

AZ-1

AZ-1

Dissolve 3-N, N-dihydroxyethylaminoacetanilide (35.74 g, 0.15 mol) in 70 ml acetone, cool with an ice bath, and add triethylamine (33.36 g, 0.33 mol) to the reaction solution. . Acryloyl chloride (28.51 g, 0.315 mol) is mixed with 30 ml of acetone, cooled to a temperature of 10 ° C. or lower, and slowly dropped into the reaction solution. After completion of the dropwise addition, the mixture is stirred vigorously at room temperature for 3 hours. After completion of the reaction, the crystals are filtered off and washed with acetone. Thereafter, the filtered solution is removed and purified using a developing solution in which the ethyl acetate and hexane are in a 1: 1 ratio.

(yellowish oil, 86%); IR (KBr pellet): v (cm ⁻¹ ) 1725 (C═O), 1635, 1602 (C═C); H-NMR (300 MHz, CDCl ₃ ) δ: 2.09 (s, CH ₃ , 3 protons), 3.61 (t, methylene, J = 6.3 Hz, 4 protons), 4.28 (t, methylene, J = 6.0 Hz, 4 protons ), 5.80 (d, vinyl CH ₂ , J = 10.2 Hz, 2 protons), 6.04-6.13 (m, vinyl CH, 2 protons), 6.35 (d, vinyl CH ₂ , J = 10.4 Hz, 2 protons), 6.48 (d, Ar-H, J = 8.4 Hz, 1 proton), 6.76 (d, Ar-H, J = 8.1 Hz, 1 proton); 7.06-7.16 (m, Ar-H, 2 protons), 8.20 (s, Ar-NH, 1 proton); Elemental Anal. Calcd. For C ₁₈ H ₂₂ N ₂ O ₅ : C, 62.42; H, 6. 40; N, 8.09; O, 23.10. Found: C, 62.40; H, 6. 42; N, 8.06; O, 23.14

Synthetic example  2: 3,3 '-(2,2'-(3- Acetamidophenylazanediyl ) Vis (Ethane-2,1- Dill ) Vis ( Oxy ))- Bis (2-hydroxypropane-3,1-diyl) bis (2- Methyl acrylate )

AZ-2

AZ-2

Glycidyl methacrylate (59.70 g, 0.42 mol) is dissolved in 100 ml of dimethylformamide and stirred for 10 minutes under nitrogen filling. To 30 ml of dimethylformamide, 3-N, N-dihydroxyethylaminoacetanilide (47.65 g, 0.20 mol) was added dropwise slowly. The reaction solution is heated at 70-80 ° C. for 20 hours, and after cooling, cold water is added. The reaction solution is then extracted several times with dichloromethane, and water is removed using anhydrous sodium sulfate. Purify using a developing solution made only of ethyl acetate (dark brownish viscous oil, 62%); IR (KBr pellet): v (cm ⁻¹ ) 3382 (OH, broad), 1740 (C═O), 1681, 1596 (C═C); ¹ H-NMR (300 MHz, CDCl ₃ ) δ: 1.92 (s, CH ₃ , 6 protons), 2.14 (s, CH ₃ , 3 protons), 3.40-3.92 (m, methylene, 12 protons), 4.18-4.45 ( m, methylene and CH, 6 protons), 5.56 (s, vinyl CH ₂ , 2 protons), 6.08 (s, vinyl CH ₂ , 2 protons), 6.53 (d, Ar-H, J = 8.1 Hz, 1 proton) , 6.75 (d, Ar-H, J = 7.8 Hz, 1 proton); 7.10-7.18 (m, Ar-H, 2 protons), 7.34 (s, Ar-NH, 1 proton), OH (undetermined); Elemental Anal. Calcd. For C ₂₆ H ₃₈ N ₂ 0 ₉ : C, 59.76; H, 7. 33; N, 5.36; O, 27.55. Found: C, 59.74; H, 7. 35; N, 5.36; O, 27.57

Synthetic example  3: 2,2 '-(3- Acetamido -4-((2,6- Dibromo -4- Nitrophenyl ) Diazenyl ) Phenyl - Azanedil ) Vis (Ethane-2,1- Dill ) Diacrylate

AZ-3

AZ-3

NaNO 2 (7.34 g, 0.1064 mol) is dissolved in 50 ml of concentrated sulfuric acid, and 40 ml of mixed acid is administered below 20 ° C. in a ratio of propionic acid and acetic acid 1: 5. Then, the temperature is lowered to 0-5 ° C., and 2,6-dibromo-4-nitrobenzeneamine (28.1 g, 0.095 mol) is added dropwise to 50 ml of concentrated sulfuric acid at 5 ° C. or lower. When the mixture is stirred at 0 to 5 ° C. for 2 hours, the reaction is first terminated. Then, acrylate coupler 1 (32.9 g, 0.095 mol) is dissolved in 100 ml of 10% sulfuric acid, and the solution is slowly added dropwise for 1 hour while keeping the temperature below 5 ° C.

After stirring for 2 hours with ice (30 g) at 5 ° C or less, the crystals are filtered and washed several times with water. After drying and recrystallization with methanol, column purification is carried out using a developing solution made only of ethyl acetate.

(dark powder, 87%); mp = 108-112 ° C .; IR (KBr pellet): v (cm ⁻¹ ) 1732 (C═O), 1644, 1611 (C═C), 1498 (N = N); ¹ H-NMR (300 MHz, CDCl ₃ ) δ: 2.29 (s, CH ₃ , 3 protons), 3.85 (t, methylene, J = 6.0 Hz, 4 protons), 4.19 (t, methylene, J = 6.0 Hz, 4 protons), 5.86 (d, vinyl CH ₂ , J = 10.2 Hz, 2 protons), 6.08-6.17 (m, vinyl CH, 2 protons), 6.42 (d, vinyl CH ₂ , J = 10.4 Hz, 2 protons), 6.64 (d, Ar-H, J = 9.3 Hz, 1 proton), 7.83 (d, Ar-H, J = 9.3 Hz, 1 proton); 8.28 (s, Ar-H, 1 proton), 8.51 (s, Ar-H, 2 protons), 10.42 (s, Ar-NH, 1 proton); Elemental Anal. Calcd. For C ₂₄ H ₂₃ Br ₂ N ₅ O ₇ : C, 44.12; H, 3.55; N, 10.72; O, 17.14. Found: C, 44.15; H, 3.55; N, 10.74; 0, 17.18; GC / MS (EI): m / e = 654 (M ⁺ ), (calcd. 653.28).

Synthetic example  4: 2,2 '-(3- Acetamido -4-((2,6- Dibromo -4- Methylphenyl ) Diazenyl ) Phenylazanediyl ) Vis -(Ethane-2,1- Dill ) Diacrylate

AZ-4

AZ-4

NaNO 2 (7.34 g, 0.1064 mol) is dissolved in 50 ml of concentrated sulfuric acid, and 40 ml of mixed acid is administered below 20 ° C. in a ratio of propionic acid and acetic acid 1: 5. Thereafter, the temperature is reduced to 0 to 5 ° C, and 2,6-dibromo-4-methylbenzeneamine (25.2 g, 0.095 mol) is added dropwise to 50 ml of concentrated sulfuric acid at 5 ° C or lower. When the mixture is stirred at 0 to 5 ° C. for 2 hours, the reaction is first terminated. Then, acrylate coupler 1 (32.9 g, 0.095 mol) is dissolved in 100 ml of 10% sulfuric acid, and the solution is slowly added dropwise for 1 hour while maintaining the temperature below 5 ° C. After stirring for 2 hours with ice (30 g) and below 5 ° C, the crystals are filtered and washed several times with water. After drying and recrystallization with methanol, column purification is carried out using a developing solution made only of ethyl acetate.

(dark powder, 72%); mp = 78-82 ° C .; IR (KBr pellet): v (cm ⁻¹ ) 1736 (C═O), 1639, 1611 (C═C), 1498 (N = N); ¹ H-NMR (300 MHz, CDCl ₃ ) δ: 2.28 (s, CH ₃ , 3 protons), 2.35 (s, CH ₃ , 3 protons), 3.81 (t, methylene, J = 6.0 Hz, 4 protons), 4.38 (t, methylene, J = 6.0 Hz, 4 protons), 5.85 (d, vinyl CH ₂ , J = 10.5 Hz, 2 protons), 6.03-6.16 (m, vinyl CH, 2 protons), 6.42 (d, vinyl CH ₂ , J = 10.5 Hz, 2 protons), 6.59 (d, Ar-H, J = 9.2 Hz, 1 proton), 7.59 (d, Ar-H, J = 9.0 Hz, 1 proton); 7.68 (s, Ar-H, 1 proton), 8.07 (s, Ar-H, 2 protons), 10.64 (s, Ar-NH, 1 proton); Elemental Anal. Calcd. For C ₂₅ H ₂₆ Br ₂ N ₄ O ₅ : C, 48.25; H, 4. 21; N, 9.00; 0, 12.85. Found: C, 48.26; H, 4. 23; N, 9.00; 0, 12.87; GC / MS (EI): m / e = 622 (M ⁺ ), (calcd. 622.31).

Synthetic example  5: 3,3 '-(2,2'-(3- Acetamido -4-((2,6- Dibromo -4- Nitrophenyl ) Diazenyl ) Phenylazanediyl) Vis -(Ethane-2,1- Dill ) Vis ( Oxy ) Vis (2-hydroxypropane-3,1- Dill ) (2- Methyl acrylate )

AZ-5

AZ-5

NaNO 2 (7.34 g, 0.1064 mol) is dissolved in 50 ml of concentrated sulfuric acid, and 40 ml of mixed acid is administered below 20 ° C. in a ratio of propionic acid and acetic acid 1: 5. Thereafter, the temperature was lowered to 0-5 ° C., and 2,6-dibromo-4-nitrobenzeneamine (28.1 g, 0.095 mol) was added dropwise to 50 ml of concentrated sulfuric acid at 5 ° C. or lower. When the mixture is stirred at 0 to 5 ° C. for 2 hours, the reaction is first terminated. Then, add Methylacrylate Coupler 2 (49.6g, 0.095mol) to 100ml of 10% sulfuric acid, dissolve, and slowly add dropwise solution of diazonium salt prepared for 1 hour while maintaining the temperature below 5 ℃. After stirring for 4 hours with ice (30 g) at 5 ° C or less, the crystals are filtered and then washed several times with water. After drying, the mixture was recrystallized with methanol, and column purification was performed using a developing solution of ethyl acetate and n-hexane 1: 1.

(dark powder, 79%); mp = 110-115 ° C .; IR (KBr pellet): v (cm ⁻¹ ) 3389 (OH, broad), 1742 (C═O), 1687, 1601 (C═C), 1560 (N = N); ¹ H-NMR (300 MHz, CDCl ₃ ) δ: 1.96 (s, CH ₃ , 6 protons), 2.22 (s, CH ₃ , 3 protons), 3.76-3.94 (m, methylene, 12 protons), 4.08-4.46 ( m, methylene and CH, 6 protons), 5.59 (s, vinyl CH ₂ , 2 protons), 6.10 (s, vinyl CH ₂ , 2 protons), 6.67 (d, Ar-H, J = 9.3 Hz 1 proton); 7.84 (d, Ar-H, J = 9.3 Hz, 1 proton); 8.28 (s, Ar-H, 1 proton), 8.51 (s, Ar-H, 2 protons), 10.42 (s, Ar-NH, 1 proton), OH (undetermined); Elemental Anal. Calcd. For C ₃₂ H ₃₉ Br ₂ N ₅ O ₁₁ : C, 46.33; H, 4. 74; N, 8. 44; O, 21.22. Found: C, 46.35; H, 4. 74; N, 8.47; 0, 21.24; GC / MS (EI): m / e = 829 (M ⁺ ), (calcd. 829.49).

Synthetic example  6: 3,3 '-(2,2'-(3- Acetamido -4-((2,6- Dibromo -4- Methylphenyl ) Diazenyl ) Phenylazanediyl ) Vis -(Ethane-2,1- Dill ) Vis ( Oxy ) Vis (2-hydroxypropane-3,1- Dill ) Vis (2- Methyl acrylate )

AZ-6

AZ-6

NaNO 2 (7.34 g, 0.1064 mol) is dissolved in 50 ml of concentrated sulfuric acid, and 40 ml of mixed acid is administered below 20 ° C. in a ratio of propionic acid and acetic acid 1: 5. Thereafter, the temperature is reduced to 0 to 5 ° C., and 2,6-dibromo-4-methylbenzeneamine (25.2 g, 0.095 mol) is added dropwise to 50 ml of concentrated sulfuric acid at 5 ° C. or lower. When the mixture is stirred at 0 to 5 ° C. for 2 hours, the reaction is first terminated. Then, add Methylacrylate Coupler 2 (49.6g, 0.095mol) to 100ml of 10% sulfuric acid, dissolve, and slowly add dropwise solution of diazonium salt prepared for 1 hour while maintaining the temperature below 5 ℃.

After stirring for 4 hours with ice (30 g) and below 5 ° C, the crystals are filtered and washed several times with water. After drying, the mixture was recrystallized with methanol, and column purification was performed using a developing solution containing 1: 1 of ethyl acetate and n-hexane.

(dark powder, 68%); mp = 64-68 ° C .; IR (KBr pellet): v (cm ⁻¹ ) 3376 (OH, broad), 1740 (C═O), 1684, 1605 (C═C), 1552 (N = N); ¹ H-NMR (300 MHz, CDCl ₃ ) δ: 1.96 (s, CH ₃ , 6 protons), 2.22 (s, CH ₃ , 3 protons), 2.34 (s, CH ₃ , 3 protons), 3.61-3.84 (m , methylene, 12 protons), 4.18-4.48 (m, methylene and CH, 6 protons), 5.61 (s, vinyl CH ₂ , 2 protons), 6.15 (s, vinyl CH ₂ , 2 protons), 6.63 (d, Ar -H, J = 9.3 Hz 1 proton), 7.46 (s, Ar-H, 1 proton), 7.82 (d, Ar-H, J = 9.0 Hz, 1 proton), 8.27 (s, Ar-H, 2 protons ), 10.64 (s, Ar-NH, 1 proton), OH (undetermined); Elemental Anal. Calcd. For C ₃₃ H ₄₂ Br ₂ N ₄ O ₉ : C, 49.64; H, 5. 30; N, 7.02; O, 18.03. Found: C, 49.62; H, 5. 32; N, 7.04; 0, 18.05; GC / MS (EI): m / e = 799 (M ⁺ ), (calcd. 798.52).

Synthetic example  7: 2,2 '-(3- Acetamido -4-((5- Nitrothiazole -2 days) Diazenyl ) Phenylazanediyl ) Vis -(Ethane-2,1- Dill ) Diacrylate

AZ-7

AZ-7

NaNO 2 (7.34 g, 0.1064 mol) is dissolved in 50 ml of concentrated sulfuric acid, and 100 ml of mixed acid is administered at 20 ° C. or lower in a ratio of propionic acid and acetic acid 2: 3. Thereafter, the temperature is lowered to 0 to 5 ° C., and 2,6-dibromo-4-methylbenzeneamine (25.2 g, 0.095 mol) is added dropwise to 50 ml of concentrated sulfuric acid at 5 ° C. or lower. When the mixture is stirred at 0 to 5 ° C. for 2 hours, the reaction is first terminated. Then, acrylate coupler 1 (38.1 g, 0.11 mol) is dissolved in 100 ml of 10% sulfuric acid, and the solution is slowly added dropwise to the diazonium salt solution for 1 hour while maintaining the temperature below 5 ° C. After stirring for 3 hours with ice (30 g) and below 5 ° C, the crystals are filtered and washed several times with water. After drying, the mixture was recrystallized from hexane and methanol, and column purification was performed using a developing solution of 1: 1 ethyl acetate and n-hexane.

(dark blue powder, 89%); mp: 143-146 ° C .; IR (KBr pellet): v (cm ⁻¹ ) 1730 (C═O), 1638, 1610 (C═C), 1600-1640 (C = N), 1559 (N = N); ¹ H-NMR (300 MHz, CDCl ₃ ) δ: 2.31 (s, CH ₃ , 3 protons), 3.89 (t, methylene, J = 5.7 Hz, 4 protons), 4.45 (t, methylene, J = 5.7 Hz, 4 protons), 5.87 (d, vinyl CH ₂ , J = 10.8 Hz, 2 protons), 6.06-6.15 (m, vinyl CH, 2 protons), 6.41 (d, vinyl CH ₂ , J = 10.8 Hz, 2 protons), 6.70 (broad s, Ar-H, 1 proton), 7.59-8.02 (broad m, Ar-H, 1 proton), 8.39 (s, Ar-H, 1 proton), 8.57 (s, Ar-H, 1 proton ), 8.97 (s, Ar-NH, 1 proton); Elemental Anal. Calcd. For C ₂₁ H ₂₂ N ₆ O ₇ S: C, 50.19; H, 4.41; N, 16.72; 0, 22.29; S, 6.38. Found: C, 50.18; H, 4.41; N, 16.72; 0, 22.27; S, 6.36; GC / MS (EI): m / e = 503 (M ⁺ ), (calcd. 502.5).

Synthetic example  8: 3,3 '-(2,2'-(3- Acetamido -4-((5- Nitrothiazole -2 days) Diazenyl ) Phenylazanediyl ) Vis -(Ethane-2,1- Dill ) Vis ( Oxy ) Vis (2-hydroxypropane-3,1- Dill ) Vis (2-methylacrylate)

AZ-8

AZ-8

NaNO 2 (7.34 g, 0.1064 mol) is dissolved in 50 ml of concentrated sulfuric acid, and 100 ml of mixed acid is administered at 20 ° C. or lower in a ratio of propionic acid and acetic acid 2: 3. Thereafter, the temperature is lowered to 0-5 占 폚, 5-nitrothiazol-2-amine (14.51 g, 0.10 mol) is added dropwise to 50 ml of concentrated sulfuric acid at 5 占 폚 or lower. When the mixture is stirred at 0 to 5 ° C. for 2 hours, the reaction is first terminated. Then, methacrylate coupler 2 (57.48 g, 0.11 mol) is dissolved in 100 ml of 10% sulfuric acid, and the mixture is slowly added dropwise for 1 hour while maintaining the temperature below 5 ° C. After stirring for 3 hours with ice (30 g) and below 5 ° C, the crystals are filtered and then washed several times with water. After drying, the mixture was recrystallized from hexane and methanol, and column purification was performed using a developing solution of ethyl acetate and n-hexane 1: 1.

(dark blue powder, 86%); mp: 170-173 ° C .; IR (KBr pellet): v (cm ^-1 ) 3376 (OH, broad), 1740 (C = O), 1687, 1606 (C = C), 1602-1642 (C = N), 1570 (N = N) ; ¹ H-NMR (300 MHz, CDCl ₃ ) δ: 1.92 (s, CH ₃ , 6 protons), 2.31 (s, CH ₃ , 3 protons), 3.85-4.01 (m, methylene, 12 protons), 4.28-4.54 ( m, methylene and CH, 6 protons), 5.60 (s, vinyl CH ₂ , 2 protons), 6.09 (s, vinyl CH ₂ , 2 protons), 6.73 (broad s, Ar-H, 1 proton), 7.60-8.05 (broad m, Ar-H, 1 proton), 8.41 (s, Ar-H, 1 proton), 8.58 (s, Ar-H, 1 proton), 8.97 (s, Ar-NH, 1 proton), OH ( undetermined); Elemental Anal. Calcd. For C ₂₉ H ₃₈ N ₆ 0 ₁₁ S: C, 51.32; H, 5. 64; N, 12.38; 0, 25.93; S, 4.72. Found: C, 51.30; H, 5. 66; N, 12.38; 0, 25.95; S, 4.75; GC / MS (EI): m / e = 679 (M ⁺ ), (calcd. 678.71).

Synthetic example  9: 2,2 '-(3- Acetamido -4-((3,5- Dinitrothiophene -2 days) Diazenyl ) Phenylazanediyl ) Vis -(Ethane-2,1- Dill ) Diacrylate

AZ-9

AZ-9

NaNO 2 (7.34 g, 0.1064 mol) is dissolved in 50 ml of concentrated sulfuric acid, and 100 ml of mixed acid is administered at 20 ° C. or lower in a ratio of propionic acid and acetic acid 2: 3. Thereafter, the temperature is reduced to 0 to 5 ° C., and 3,5-dinitrothiophen-2-amine (18.9 g, 0.10 mol) is added dropwise to 50 ml of concentrated sulfuric acid at 5 ° C. or lower. When the mixture is stirred at 0 to 5 ° C. for 2 hours, the reaction is first terminated. After acrylate coupler 1 (38.1 g, 0.11 mol) is dissolved in 100 ml of 10% sulfuric acid, the solution is slowly added dropwise for 1 hour while keeping the temperature below 5 ° C. After stirring for 3 hours while administering ice (30 g) below 5 ° C, the crystals are filtered and then washed several times with water. After drying, the mixture was recrystallized from hexane and methanol, and column purification was performed using a developing solution of ethyl acetate and n-hexane 1: 1.

(dark blue powder, 78%); mp: 101-104 ° C .; IR (KBr pellet): v (cm ⁻¹ ) 1738 (C═O), 1637, 1617 (C═C), 1548 (N = N); ¹ H-NMR (300 MHz, CDCl ₃ ) δ: 2.43 (s, CH ₃ , 3 protons), 3.93 (t, methylene, J = 5.7 Hz, 4 protons), 4.67 (t, methylene, J = 5.7 Hz, 4 protons), 5.89 (d, vinyl CH ₂ , J = 10.5 Hz, 2 protons), 6.06-6.16 (m, vinyl CH, 2 protons), 6.42 (d, vinyl CH ₂ , J = 10.5 Hz, 2 protons), 6.80 (d, Ar-H, J = 9.6 Hz, 1 proton), 7.63 (d, Ar-H, J = 9.3 Hz, 1 proton), 8.38 (s, Ar-H, 1 proton), 8.56 (s, Ar-H, 1 proton), 8.98 (s, Ar-NH, 1 proton); Elemental Anal. Calcd. For C ₂₂ H ₂₂ N ₆ O ₉ S: C, 48.35; H, 4.06; N, 15.38; 0, 26.35; S, 5.87. Found: C, 48.37; H, 4.06; N, 15.38; 0, 26.36; S, 5.88; GC / MS (EI): m / e = 547 (M ⁺ ), (calcd. 546.51).

Synthetic example  10: 3,3 '-(2,2'-(3- Acetamido -4-((3,5- Dinitrothiophene -2 days) Phenylazanediyl ) Vis -(Ethane-2,1- Dill ) Vis ( Oxy ) Vis (2-hydroxypropane-3,1- Dill ) Vis (2- Methyl acrylate )

AZ-10

AZ-10

NaNO 2 (7.34 g, 0.1064 mol) is dissolved in 50 ml of concentrated sulfuric acid, and 100 ml of mixed acid is administered at 20 ° C. or lower in a ratio of propionic acid and acetic acid 2: 3. Thereafter, the temperature is lowered to 0-5 ° C., and 3,5-dinitrothiophen-2-amine (18.9 g, 0.10 mol) is added dropwise to 50 ml of concentrated sulfuric acid at 5 ° C. or lower. When the mixture is stirred at 0 to 5 ° C. for 2 hours, the reaction is first terminated. Then, methacrylate coupler 2 (57.48 g, 0.11 mol) is dissolved in 100 ml of 10% sulfuric acid, and the solution is slowly added dropwise for 1 hour while keeping the temperature below 5 ° C. After stirring for 3 hours with ice (30 g) and below 5 ° C, the crystals are filtered and washed several times with water. After drying, the mixture was recrystallized from hexane and methanol, and column purification was performed using a developing solution of ethyl acetate and n-hexane 1: 1.

(dark blue powder, 72%); mp: 120-123 ° C .; IR (KBr pellet): v (cm ⁻¹ ) 3388 (OH, broad), 1740 (C═O), 1680, 1601 (C═C), 1556 (N = N); ¹ H-NMR (300 MHz, CDCl ₃ ) δ: 1.93 (s, CH ₃ , 6 protons), 2.44 (s, CH ₃ , 3 protons), 3.82-4.01 (m, methylene, 12 protons), 4.38-4.58 ( m, methylene and CH, 6 protons), 5.62 (s, vinyl CH ₂ , 2 protons), 6.10 (s, vinyl CH ₂ , 2 protons), 6.82 (d, Ar-H, J = 9.6 Hz, 1 proton) , 7.14 (d, Ar-H, J = 9.6 Hz, 1 proton), 8.40 (s, Ar-H, 1 proton), 8.58 (s, Ar-H, 1 proton), 8.98 (s, Ar-NH, 1 proton), OH (undetermined); Elemental Anal. Calcd. For C ₃₀ H ₃₈ N ₆ 0 ₁₃ S: C, 49.86; H, 5. 30; N, 11.63; 0, 28.78; S, 4.44. Found: C, 49.88; H, 5. 32; N, 11.64; 0, 28.78; S, 4.45; GC / MS (EI): m / e = 723 (M ⁺ ), (calcd. 722.72).

Synthetic example  11: 3,3 '-(3- Acetamido -4-((5,6- Dichlorobenzo [d] thiazole -2 days) Diazenyl ) Phenylazanediyl) Vis -(Ethane-2,1- Dill ) Diacrylate

AZ-11

AZ-11

NaNO 2 (7.34 g, 0.1064 mol) is dissolved in 50 ml of concentrated sulfuric acid, and 100 ml of mixed acid is administered at 20 ° C. or lower in a ratio of propionic acid and acetic acid 1: 5. Thereafter, the temperature was lowered to 0 to 5 ° C., and 5,6-dichlorobenzo [d] thiazol-2-amine (21.91 g, 0.10 mol) was added dropwise to 50 ml of concentrated sulfuric acid at 5 ° C. or lower. When the mixture is stirred at 0 to 5 ° C. for 2 hours, the reaction is first terminated. Then, acrylate coupler 1 (38.1 g, 0.11 mol) is dissolved in 100 ml of 10% sulfuric acid, and the mixture is slowly added dropwise for 1 hour while maintaining the temperature below 5 ° C. After stirring for 2 hours with ice (30 g) at 5 ° C or less, the crystals are filtered and washed several times with water. After drying, the mixture was recrystallized from hexane and methanol, and then purified by column using a developing solution made only of ethyl acetate.

(redish powder, 76%); mp: 132-136 ° C .; IR (KBr pellet): v (cm ⁻¹ ) 1736 (C═O), 1648, 1627 (C═C), 1554 (N = N); ¹ H-NMR (300 MHz, CDCl ₃ ) δ: 2.34 (s, CH ₃ , 3 protons), 3.79 (t, methylene, J = 5.7 Hz, 4 protons), 4.45 (t, methylene, J = 5.7 Hz, 4 protons), 5.87 (d, vinyl CH ₂ , J = 10.8 Hz, 2 protons), 6.08-6.17 (m, vinyl CH, 2 protons), 6.42 (d, vinyl CH ₂ , J = 10.8 Hz, 2 protons), 6.61-6.67 (broad m, Ar-H, 1 proton), 7.40 (s, Ar-H, 1 proton), 7.64 (d, Ar-H, J = 9.3 Hz, 1 proton), 7.90 (s, Ar- H, 1 proton), 8.11 (s, Ar-H, 1 proton), 8.27 (s, Ar-NH, 1 proton); Elemental Anal. Calcd. For C ₂₅ H ₂₃ C _{l 2} N ₅ O ₅ S: C, 52.09; H, 4.02; N, 12.15; 0, 13.88; S, 5.56. Found: C, 52.08; H, 4.04; N, 12.15; 0, 13.90; S, 5.56; GC / MS (EI): m / e = 576 (M ⁺ ), (calcd. 576.45).

Synthetic example  12: 3,3 '-(, 2'-(3- Acetamido -4-((5,6- Dichlorobenzo [d] thiazole -2 days) Diazenyl ) Phenylazanediyl ) Vis (Ethane-2,1- Dill ) Vis ( Oxy ) Vis (2-hydroxypropane-3,1-diyl) Vis (2- Methyl acrylate )

AZ-12

AZ-12

NaNO 2 (7.34 g, 0.1064 mol) is dissolved in 50 ml of concentrated sulfuric acid, and 100 ml of mixed acid is administered at 20 ° C. or less in a ratio of propionic acid and acetic acid 1: 5. Thereafter, the temperature was lowered to 0 to 5 ° C, and 5,6-dichlorobenzo [d] thiazol-2-amine (21.91 g, 0.10 mol) was added dropwise to 50 ml of concentrated sulfuric acid at 5 ° C or lower. When the mixture is stirred at 0 to 5 ° C. for 2 hours, the reaction is first terminated. Then, methacrylate coupler 2 (57.48g, 0.11mol) is dissolved in 100 ml of 10% sulfuric acid, and the solution is slowly added dropwise for 1 hour while maintaining the temperature below 5 ° C.

After stirring for 2 hours with ice (30 g) and below 5 ° C, the crystals are filtered and washed several times with water. After drying, the mixture was recrystallized from hexane and methanol, and column purification was performed using a developing solution of 1: 1 ethyl acetate and n-hexane.

(redish powder, 68%); mp: 130-135 ° C .; IR (KBr pellet): v (cm ⁻¹ ) 3388 (OH, broad), 1740 (C═O), 1688, 1614 (C═C), 1543 (N = N); ¹ H-NMR (300 MHz, CDCl ₃ ) δ: 1.93 (s, CH ₃ , 6 protons), 2.33 (s, CH ₃ , 3 protons), 3.78-4.02 (m, methylene, 12 protons), 4.32-4.58 ( m, methylene and CH, 6 protons), 5.60 (s, vinyl CH ₂ , 2 protons), 6.10 (s, vinyl CH ₂ , 2 protons), 6.62-6.68 (broad m, Ar-H, 1 proton), 7.39 (s, Ar-H, 1 proton), 7.63 (d, Ar-H, J = 9.3 Hz, 1 proton), 7.89 (s, Ar-H, 1 proton), 8.10 (s, Ar-H, 1 proton ), 8.28 (s, Ar-NH, 1 proton), OH (undetermined); Elemental Anal. Calcd. For C ₃₃ H ₃₉ C _{l 2} N ₅ O ₉ S: C, 52.66; H, 5. 22; N, 9.30; 0, 19.13; S, 4.26. Found: C, 52.67; H, 5. 22; N, 9. 32; 0, 19.15; S, 4.26; GC / MS (EI): m / e = 753 (M ⁺ ), (calcd. 752.66).

Synthetic example  13: 2,2 '-(3- Acetamido -4-((2,6- Dicyano -4- Nitrophenyl ) Diazenyl ) Phenylazanediyl ) Vis (Ethane-2,1- Dill ) Diacrylate

AZ-13

AZ-13

Dibromonated compound 3 (41 g, 51.34 mmol) was dissolved in 50 ml of dimethylformamide, and zinc cyanide (6.21 g, 52.8 mmol) and copper cyanide (0.23 g, 2.57 mmol) were added thereto, and the mixture was stirred at 100 ° C. for 1 hour. do. After that, the crystals are added with 100 ml of cold water, stirred, filtered, and washed with distilled water, hexane and methanol and dried. Thereafter, the column was purified using a developing solution of 1: 1 ethyl acetate and n-hexane.

(dark blue powder, 78%); mp = 136-139 ° C .; IR (KBr pellet): v (cm ⁻¹ ) 2205 (CN), 1732 (C═O), 1643, 1614 (C═C), 1508 (N = N); ¹ H-NMR (300 MHz, CDCl ₃ ) δ: 2.32 (s, CH ₃ , 3 protons), 3.88 (t, methylene, J = 6.0 Hz, 4 protons), 4.45 (t, methylene, J = 6.0 Hz, 4 protons), 5.87 (d, vinyl CH ₂ , J = 10.5 Hz, 2 protons), 6.08-6.17 (m, vinyl CH, 2 protons), 6.42 (d, vinyl CH ₂ , J = 10.7 Hz, 2 protons), 6.70 (d, Ar-H, J = 9.5 Hz, 1 proton), 8.01 (d, Ar-H, J = 9.8 Hz, 1 proton), 8.34 (s, Ar-H, 1 proton), 8.72 (s, Ar-H, 2 protons), 9.26 (s, Ar-NH, 1 proton); Elemental Anal. Calcd. For C ₂₆ H ₂₃ N ₇ O ₇ : C, 57.25; H, 4. 25; N, 17.97; O, 20.53. Found: C, 57.26; H, 4. 25; N, 17.96; 0, 20.54; GC / MS (EI): m / e = 546 (M ⁺ ), (calcd. 545.5).

Synthetic example  14: 2,2 '-(3- Acetamido -4-((2,6- Dicyano -4- Methylphenyl ) Diazenyl ) Phenylazanediyl ) Vis (Ethane-2,1- Dill ) Diacrylate

AZ-14

AZ-14

Dibromine compound 4 (31.9 g, 51.34 mmol) was dissolved in 50 ml of dimethylformamide, and zinc cyanide (6.21 g, 52.8 mmol) and copper cyanide (0.23 g, 2.57 mmol) were added thereto, and the mixture was stirred at 100 ° C. for 1 hour. Do it. The crystals are then poured into 100 ml of cold water, stirred and filtered to obtain, washed with distilled water, hexane and methanol and dried. Thereafter, the column was purified using a developing solution of 1: 1 ethyl acetate and n-hexane.

(redish powder, 65%); mp = 105-108 ° C .; IR (KBr pellet): v (cm ⁻¹ ) 2206 (CN), 1736 (C═O), 1640, 1612 (C═C), 1505 (N = N); ¹ H-NMR (300 MHz, CDCl ₃ ) δ: 2.30 (s, CH ₃ , 3 protons), 2.36 (s, CH ₃ , 3 protons), 3.83 (t, methylene, J = 6.0 Hz, 4 protons), 4.42 (t, methylene, J = 6.0 Hz, 4 protons), 5.86 (d, vinyl CH ₂ , J = 10.5 Hz, 2 protons), 6.04-6.17 (m, vinyl CH, 2 protons), 6.42 (d, vinyl CH ₂ , J = 10.5 Hz, 2 protons), 6.63 (d, Ar-H, J = 9.3 Hz, 1 proton), 7.48 (d, Ar-H, J = 9.3 Hz, 1 proton); 7.79 (s, Ar-H, 1 proton), 8.30 (s, Ar-H, 2 protons), 9.81 (s, Ar-NH, 1 proton); Elemental Anal. Calcd. For C ₂₇ H ₂₆ N ₆ O ₅ : C, 63.03; H, 5.09; N, 16.33; O, 15.55. Found: C, 63.05; H, 5.11; N, 16.33; 0, 15.57; GC / MS (EI): m / e = 515 (M ⁺ ), (calcd. 514.53).

Synthetic example  15: 3,3 '-(2,2'-(3- Acetamido -4-((2,6- Dicyano -4- Nitrophenyl ) Diazenyl ) Phenylazanediyl) Vis (Ethane-2,1- Dill ) Vis ( Oxy ) Vis (2-hydroxypropane-3,1- Dill ) Vis (2- Methyl acrylate )

AZ-15

AZ-15

Dibrominated compound 5 (40 g, 48.2 mmol) was dissolved in 50 ml of dimethylformamide, and zinc cyanide (6.21 g, 52.8 mmol) and copper cyanide (0.23 g, 2.57 mmol) were added thereto. do. The crystals are then poured into 100 ml of cold water, stirred and filtered to obtain, washed with distilled water, hexane and methanol and dried. Thereafter, the column was purified using a developing solution of 1: 1 ethyl acetate and n-hexane.

(dark blue powder, 79%); mp 135-140 ° C .; IR (KBr pellet): v (cm ⁻¹ ) 3391 (OH, broad), 2235 (CN), 1745 (C═O), 1690, 1605 (C═C), 1525 (N = N); ¹ H-NMR (300 MHz, CDCl ₃ ) δ: 1.86 (s, CH ₃ , 6 protons), 2.25 (s, CH ₃ , 3 protons), 3.76-4.01 (m, methylene, 12 protons), 4.10-4.48 ( m, methylene and CH, 6 protons), 5.54 (s, vinyl CH ₂ , 2 protons), 6.03 (s, vinyl CH ₂ , 2 protons), 6.64 (d, Ar-H, J = 9.6 Hz 1 proton); 8.04 (d, Ar-H, J = 9.6 Hz, 1 proton); 8.28 (s, Ar-H, 1 proton), 8.62 (s, Ar-H, 2 protons), 9.26 (s, Ar-NH, 1 proton), OH (undetermined); Elemental Anal. Calcd. For C ₃₄ H ₃₉ N ₇ 0 ₁₁ : C, 56.58; H, 5. 45; N, 13.59; O, 24.39. Found: C, 56.58; H, 5. 45; N, 13.59; 0, 24.40; GC / MS (EI): m / e = 722 (M ⁺ ), (calcd. 721.71).

Synthetic example  16: 3,3 '-(2,2'-(3- Acetamido -4-((2,6- Dicyano -4- Methylphenyl ) Diazenyl ) Phenylazanediyl ) Vis (Ethane-2,1- Dill ) Vis ( Oxy ) Vis (2-hydroxypropane-3,1-diyl) Vis (2- Methyl acrylate )

AZ-16

AZ-16

Dibrominated compound 6 (38.48g, 48.2mmol) was added to 50 ml of dimethylformamide and dissolved. Zinc cyanide (6.21 g, 52.8 mmol) and copper cyanide (0.23 g, 2.57 mmol) were added thereto and stirred at 100 ° C for 2 hours. Do it. The crystals are then poured into 100 ml of cold water, stirred and filtered to obtain, washed with distilled water, hexane and methanol and dried. Thereafter, the column was purified using a developing solution of 1: 1 ethyl acetate and n-hexane.

(redish powder, 71%); mp 88-92 ° C .; IR (KBr pellet): v (cm ⁻¹ ) 3376 (OH, broad), 2235 (CN), 1742 (C═O), 1684, 1606 (C═C), 1554 (N = N); ¹ H-NMR (300 MHz, CDCl ₃ ) δ: 1.96 (s, CH ₃ , 6 protons), 2.22 (s, CH ₃ , 3 protons), 2.34 (s, CH ₃ , 3 protons), 3.60-3.85 (m , methylene, 12 protons), 4.15-4.49 (m, methylene and CH, 6 protons), 5.61 (s, vinyl CH ₂ , 2 protons), 6.14 (s, vinyl CH ₂ , 2 protons), 6.63 (d, Ar -H, J = 9.5 Hz 1 proton), 7.74 (s, Ar-H, 1 proton), 8.17 (d, Ar-H, J = 9.3 Hz, 1 proton), 8.28 (s, Ar-H, 2 protons ), 9.82 (s, Ar-NH, 1 proton), OH (undetermined); Elemental Anal. Calcd. For C ₃₅ H ₄₂ N ₆ 0 ₉ : C, 60.86; H, 6. 13; N, 12.17; O, 20.85. Found: C, 60.86; H, 6. 13; N, 12.17; 0, 20.85; GC / MS (EI): m / e = 691 (M ⁺ ), (calcd. 690.74).

Table 1 below shows the maximum absorption wavelength and molar extinction coefficient of the synthetic dye according to the embodiment of the present invention on chloroform.

compound λ max (nm) / Abs. Molar extinction coefficient (l / mole * cm) Blue 15: 3 674 / 1.1012 49,942 AZ-7 566 / 1.3102 55,283 AZ-8 568 / 1.3890 57,983 AZ-9 615 / 1.2287 52,732 AZ-10 620 / 1.3014 55,681 AZ-11 520 / 1.1525 51,563 AZ-12 524 / 1.2445 58,651 AZ-13 487 / 1.1041 44,520 AZ-14 582 / 1.0978 41,862 AZ-15 516 / 1.2466 50,266 AZ-16 605 / 1.2474 49,378

Example  1: dye type Color resist  Ink manufacturing

The color resist ink is 15% reference blue pigment or synthesized azo dye with the same transmittance as reference blue 15: 6, 24.5% for blue photoresist, 28.5% for red photoresist with additional initiator, solvent Made using PGMEA. The mixed solution was stirred in a dark room at room temperature for at least 2 hours. Teflon-based membrane filters (diameter 1.0 μm) were used to minimize the exposure of the solution to light after the filter.

The total solids content between the photoresist and color millbase was maintained at 1: 1. In order to maintain high color film adhesion, spin coating was performed at 3500 rpm for 35 seconds using hexamethyldisilazane (HMDS), followed by baking at 150 ° C. on a hot plate for 1 hour.

Table 2 below shows the dye and photoresist composition ratios of the dye-type color resist ink according to the present invention.

Violet Blue Magenta Red 7 8 13 15 Pigment 9 10 11 12 14 16 Millbase (g) 4.76 4.63 3.57 4.76 3.33 5.00 4.63 5.00 4.76 3.85 4.00 PR (g) ^a 2.04 2.04 2.04 2.04 2.04 2.04 2.04 1.75 1.75 1.75 1.75

a: Total solids content (%) of 24.5% acrylic photoresist (Violet and Blue) and 28.5% acrylic photoresist (Red and Magenta)

Example  2: Color resist  Coating film production using spin coating method of ink

TSTI Co's SMART-CUBE-M spin coater was used to coat the transparent glass substrate surface-treated with HMDS with pigment and dye type color register ink. The film was prepared by using a negative photolithography method on an organic substrate of 5 cm by 5 cm size. Coating rates were injected for 5 seconds at 400 rpm for pigments and 100 rpm for dyes. Thereafter, the coating speed was pigment 920 rpm, and in the case of dye, forming a film for 10 seconds in the range of 200 to 500 rpm, an average 1.6 μm thick film was prepared.

Wet coated color filter removes solvent at 100 ℃ for 150 seconds and exposed to high mercury lamp (300 W of strength at 365 nm) within 10 seconds using photomask coated with microchrome coating on quartz. Was done. Thereafter, hard baking was performed at 230 ° C. for 30 minutes. However, to prevent sublimation and degradation of the dye at high temperatures, the coated film was soft baked at 100 ° C. for 150 seconds.

The coated film was exposed to a high mercury lamp (300 W of strength at 365 nm) within 30 seconds using a photomask coated with a microchrome layer on quartz. Thereafter, the temperature was increased by 30 ° C. per 30 minutes from 120 to 230 ° C., and all the films were confirmed to have a thickness of 1.6 μm.

Table 3 below shows the color (CIE 1931 chromaticity diagram color coordinates) and contrast of the color filter using spin coating of Pigment Blue 15: 3 and the novel synthetic dyes.

CIE CIEx CIEy Y Blue 15: 3 1.6 μm 0.1365 0.1139 14.059 4789 Violet 23 1.6 μm 0.1797 0.0456 2.225 1023 AZ-7 (Violet) 1.6 μm 0.2288 0.1720 9.718 6483 AZ-8 (Violet) 1.6 μm 0.2421 0.2039 13.552 8660 AZ-9 (Blue) 1.6 μm 0.1434 0.1271 5.416 8852 AZ-10 (Blue) 1.6 μm 0.1429 0.1622 8.137 8996 AZ-11 (Magenta) 1.6 μm 0.4654 0.2281 13.709 6125 AZ-12 (Magenta) 1.6 μm 0.392 0.2119 18.309 7253 AZ-13 (Violet) 1.6 μm 0.2093 0.0938 7.437 6948 AZ-14 (Red) 1.6 μm 0.6716 0.3283 11.923 7825 AZ-15 (Violet) 1.6 μm 0.2349 0.0956 12.812 7120 AZ-16 (Red) 1.6 μm 0.6918 0.3078 13.096 8178

In addition, Fig. 4 shows the color coordinates (CIE 1931 chromaticity diagram) of the color filter of the dye synthesized according to the synthesis example of the present invention, it can be seen that the color purity of the dye according to the present invention is good.

Solubility Measurement

For synthetic dyes, quantitative solubility was measured using 2 g dye and 8 g of solvent using PGMEA which is widely used in industry as a solvent. After stirring for 24 hours at room temperature, it was determined how much the dye is dissolved in the solvent. The less dissolved dye filtered the solution with a 1.0 μm filter. The amount of melt was then calculated in weight percent.

Table 4 shows the solubility in PGMEA at 25 ° C.

color Blue Violet Magenta Red Dys 9 10 7 8 13 15 11 12 14 16 solubility 14.3% 16.9% 13.5% 15.6% 14.8% 17.6% 10.2% 12.8% 13.0% 14.8%

Heat resistance probe

Pigment, dye, and film were used to determine the thermal analysis and UV transmittance by TGA. First, the thermally analyzed pigments, dyes, and films were left at 110 ° C. for 10 minutes to remove any remaining solvent or water. After that, while maintaining the temperature at 230 ℃ 30 minutes, a heat resistance experiment was assumed assuming the color filter manufacturing temperature. Then, the pyrolysis temperature of the sample was measured, heating up to 500 degreeC. All experiments were raised at 10 ° C./min under nitrogen gas. In addition, the permeability change was observed in order to see the thermal stability while heating the pigment, dye, coated film from 120 to 230 ℃.

5 and 6 show the results of measuring the thermal stability of AZ-9, 10, 11, 12, 14, and 16 synthesized in the synthesis example of the present invention, it can be seen that the results are quite excellent.

7 and 8 also show the synthetic dyes (AZ-9 and AZ-10) according to the present invention and conventional pigments and TGA curves on their films, and FIG. 8 shows synthetic dyes (AZ-11, 12, 14 and 16) and their TGA curves on film.

Chemical resistance

In the LCD manufacturing process, color filters are exposed to many organic solvents, so chemical resistance is an important problem. Film in solvents of strong organic solvents N-methyl-2-pyrrolidone (NMP), γ-butylarolactone, propylene glycol methyl ether acetate (PGMEA), ethyl lactate (EL), and isopropyl alcohol (IPA) After soaking for 30 minutes, stability analysis was performed while observing whether there was any swelling or peeling phenomenon before or after treatment. Then, the chemical resistance was measured by the color spectrometer the degree of change.

Table 5 shows the chemical resistance of the color filter of the existing pigments and dyes according to the present invention, it can be seen that the chemical resistance of the color filter according to the present invention is very improved.

In general, when the ΔEab value (color coordinate change) is 3 or less, the color change cannot be identified by the naked eye. It can be seen that in the PGMEA used in the production of all 3 or less. As such, Table 5 is meaningful in that the chemical resistance to PGMEA can be confirmed.

Chemical Chromatic Chagne (△ Eab) after dipping for 30min Blue 15: 3 9 10 11 12 14 16 NMP 0.73 2.81 2.78 2.79 2.21 2.45 1.98 γ-butyrolactone 0.27 4.03 3.91 5.63 4.25 4.86 4.32 PGMEA 0.22 2.62 2.33 2.20 1.77 2.88 2.75 EL 0.47 2.77 2.65 2.43 2.12 2.23 1.88 IPA 0.56 2.80 2.21 2.65 2.38 2.53 2.31

Developability  And lithographic characterization

After spin coating the color register ink on the organic substrate, it was baked for 1 hour at 110 ℃. The film thickness was approximately 1.6 μm. The coated film was exposed to light using a photomask coated with a 30 μm microchrome layer on quartz manufactured by NEPCO. Thereafter, development was carried out with a developer to remove unexposed portions. Post-bake was performed at 150 ° C. for 10 minutes.

10 is OM image of Pigment Blue, binder and synthesized dye film (magnification 100 ×, high resolution (≦ 30 μm)).

11 is an OM image of the synthesized dye (AZ-9, 10, 13 and 15) film (magnification 100 ×, high resolution (≦ 30 μm)).

12 is an OM image of the synthesized dye (AZ-11, 12, 14, 16) film (magnification 100 ×, high resolution (≦ 30 μm)).

10-12 shows color dispersion and pattern consistency (no cracks or dusts) when a pattern of a color resist using a binder or a binder and a conventional blue pigment and a pattern of a color resist using an inventive dye are shown. The figure showing.

FIG. 13 is a cross sectional view of only negative photoresist, pigment and dyes AZ-9, 10, and FIG. 14 is a cross sectional view of dyes AZ-11, 12, 14, and 16. FIG.

13-14 Also, when the pattern is prepared using a binder, the edges of the pattern are clear, but the pattern of the color resist using the blue pigment and the pattern of the color resist using the inventive dye are relatively etched at the bottom and the upper part of the pattern. Although there is, there is no big difference with the blue pigment commonly used under the same process conditions.

Claims (5)

Azo compounds for color resists represented by the following general formula (1):

(One)
Where
R ₁ and R ₂ are each independently selected from a substituted or unsubstituted acrylate group or methacrylate group,
R ₃ is selected from acetamino group or C ₁ -C ₆ alkyl group,
R ₄ is selected from hydrogen, a substituted or unsubstituted azo group, or a substituted or unsubstituted diazo group. The method of claim 1,
An azo compound represented by the following general formula (2):

(2)
Where
R ₁ and R ₂ are each independently selected from a substituted or unsubstituted acrylate group or methacrylate group,
R ₃ is selected from acetamino group or C ₁ -C ₆ alkyl group,
R ₅ is selected from substituted or unsubstituted phenyl, substituted or unsubstituted thiazole group, and substituted or unsubstituted thiophene group. The method of claim 2,
R ₅ is azo compound, characterized in that selected from the group consisting of dibromonitrobenzene, dicyanonitrobenzene, dinitrothiophene, nitrothiazole, benzothiazole. The method of claim 1,
An azo compound characterized in that the compound represented by the following formula:

AZ-1 AZ-2

AZ-3 AZ-4

AZ-5 AZ-6

AZ-7 AZ-8

AZ-9 AZ-10

AZ-11 AZ-12

AZ-13 AZ-14

AZ-15 AZ-16 Dye type color filter for liquid crystal display containing the azo dye compound of Claim 1.

Images