Cardo-based binder resin, photosensitive resin composition comprising same, black matrix, color filter, and display device

Abstract

The present specification provides a cardo-based binder resin represented by Chemical Formula 1, and a photosensitive resin composition, a black matrix, a color filter and a display apparatus including the same.

Claims

1. A cardo-based binder resin represented by Chemical Formula 1: ##STR00020## wherein, in the Chemical Formula 1, R1 and R2 are hydrogen or represented by Chemical Formula 2; at least one of R1 and R2 is represented by the Chemical Formula 2; and n is an integer of 1 to 50, ##STR00021## wherein, in Chemical Formula 2, ##STR00022## represents a site linked to Chemical Formula 1, X1 to X6 are a substituted or unsubstituted alkylene group; or a substituted or unsubstituted alkylene oxide group; Y1 and Y2 are selected from the group consisting of a substituted or unsubstituted alkylene group; a substituted or unsubstituted cycloalkylene group; a substituted or unsubstituted cycloalkenylene group; and a substituted or unsubstituted arylene group; R3 to R5 are the same as or different from each other, and each independently hydrogen; or a substituted or unsubstituted alkyl group; A1 to A4 are the same as or different from each other, and each independently selected from the group consisting of hydrogen; deuterium; a halogen group; a nitrile group; a nitro group; a hydroxyl group; an ester group; an imide group; an amide group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted cycloalkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted phosphine oxide group; a substituted or unsubstituted phosphine group; a substituted or unsubstituted sulfonyl group; a substituted or unsubstituted amine group; a substituted or unsubstituted aryl group; and a substituted or unsubstituted heteroaryl group; and a1 to a4 are an integer of 0 to 4, and when a1 to a4 are 2 or greater, A1 to A4 are the same as or different from each other.

2. The cardo-based binder resin of claim 1, which has an acid value of 0 mg KOH/g to 50 mg KOH/g.

3. The cardo-based binder resin of claim 1, wherein X1 to X6 are a substituted or unsubstituted alkylene group having 1 to 3 carbon atoms; or a substituted or unsubstituted alkylene oxide group having 2 to 10 carbon atoms; and Y1 and Y2 are selected from the group consisting of a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; a substituted or unsubstituted cycloalkylene group having 3 to 10 carbon atoms; a substituted or unsubstituted cycloalkenylene group having 3 to 10 carbon atoms; and a substituted or unsubstituted arylene group having 6 to 20 carbon atoms.

4. The cardo-based binder resin of claim 1, wherein R1 and R2 are represented by the Chemical Formula 2.

5. The cardo-based binder resin of claim 1, which has a weight average molecular weight of 1,000 g/mol to 10,000 g/mol.

6. A photosensitive resin composition comprising the cardo-based binder resin of claim 1.

7. The photosensitive resin composition of claim 6, further comprising: a colorant; a multifunctional monomer; a photoinitiator; and a solvent.

8. The photosensitive resin composition of claim 7, further comprising at least one selected from the group of an acryl-based binder resin; an adhesion promoter; and a leveling agent.

9. The photosensitive resin composition of claim 8, comprising the cardo-based binder resin in 0.5 parts by weight to 10 parts by weight; the colorant in 1 part by weight to 50 parts by weight; the acryl-based binder resin in 0 part by weight to 10 parts by weight; the multifunctional monomer in 1 part by weight to 20 parts by weight; the photoinitiator in 0.1 parts by weight to 10 parts by weight; the adhesion promoter in 0.01 parts by weight to 5 parts by weight; the leveling agent in 0.01 parts by weight to 5 parts by weight; and the solvent in 20 parts by weight to 95 parts by weight, based on 100 parts by weight of the photosensitive resin composition.

10. A black matrix formed using from the photosensitive resin composition of claim 6.

11. A color filter comprising the black matrix of claim 10.

12. A display apparatus comprising the black matrix of claim 10.

Description

PREPARATION EXAMPLE

Synthesis Example 1

(1) In a 500 mL three-neck flask, 9,9-bisphenol fluorene diglycidyl ether (BPFG) (89 g, 0.19 mol), 4-cyclohexene-1,2-dicarboxylic acid (CDA) (51 g, 0.30 mol) and tetrabutylammonium bromide (TBAB) (1.4 g) were stirred together with propylene glycol methyl ether acetate (PGMEA) (260 g).

(2) Under the nitrogen atmosphere, the reaction mixture was heated to 120° C., and stirred for 24 hours. After cooling the reaction mixture to 80° C., inside the reactor was substituted with air, and after adding a polymerization inhibitor (BHT) (0.08 g) thereto, the result was stirred for 1 hour.

(3) After adding glycidyl methacrylate (GMA) (29.6 g, 0.21 mol) and propylene glycol methyl ether acetate (PGMEA) (29.6 g) to the reaction mixture, the result was stirred for 24 hours at 120° C.

(4) A cardo-based binder resin obtained in Synthesis Example 1 is represented by the following Chemical Formula 3.

(5) ##STR00013##

(6) wherein, in Chemical Formula 3, n is from 3 to 8. The cardo-based binder resin has a mixture form of the compound represented by Chemical Formula 3 in which n is in the above-mentioned range.

(7) In the prepared cardo-based binder resin, the solid content was 40.0%, the acid value was 0 mgKOH/g, and the weight average molecular weight was 3,040 g/mol.

Synthesis Example 2

(8) A cardo-based binder resin was synthesized in the same manner as in Synthesis Example 1 except that 22.2 g (0.16 mol) of the glycidyl methacrylate and 22.2 g of the propylene glycol methyl ether acetate were used.

(9) The cardo-based binder resin obtained in Synthesis Example 2 was a mixture of a compound represented by the following Chemical Formula 3, a compound represented by the following Chemical Formula 4 and a compound represented by the following Chemical Formula 5.

(10) ##STR00014##

(11) wherein, in Chemical Formula 3 to Chemical Formula 5, n is from 3 to 8. The cardo-based binder resin has a mixture form of the compound represented by Chemical Formula 3 in which n is in the above-mentioned range, the compound represented by Chemical Formula 4 in which n is in the above-mentioned range and the compound represented by Chemical Formula 5 in which n is in the above-mentioned range.

(12) In the prepared cardo-based binder resin, the solid content was 39.4%, the acid value was 28 mgKOH/g, and the weight average molecular weight was 2,940 g/mol.

Synthesis Example 3

(13) A cardo-based binder resin was synthesized in the same manner as in Synthesis Example 1 except that 14.8 g (0.10 mol) of the glycidyl methacrylate and 14.8 g of the propylene glycol methyl ether acetate were used.

(14) The cardo-based binder resin obtained in Synthesis Example 3 was a mixture of the compound represented by Chemical Formula 3, the compound represented by Chemical Formula 4 and the compound represented by Chemical Formula 5.

(15) In Chemical Formula 3 to Chemical Formula 5, n is from 3 to 8. The cardo-based binder resin has a mixture form of the compound represented by Chemical Formula 3 in which n is in the above-mentioned range, the compound represented by Chemical Formula 4 in which n is in the above-mentioned range and the compound represented by Chemical Formula 5 in which n is in the above-mentioned range.

(16) In the prepared cardo-based binder resin, the solid content was 38.2%, the acid value was 44 mgKOH/g, and the weight average molecular weight was 2,890 g/mol.

Comparative Synthesis Example 1

(17) In a 500 mL three-neck flask, 9,9-bisphenol fluorene diglycidyl ether (89 g, 0.19 mol), 4-cyclohexene-1,2-dicarboxylic acid (51 g, 0.30 mol) and tetrabutylammonium bromide (1.4 g) were stirred together with propylene glycol methyl ether acetate (260 g). Under the nitrogen atmosphere, the reaction mixture was heated to 120° C., and stirred for 24 hours. After cooling the reaction mixture to room temperature, the reaction was terminated. A binder resin prepared in Comparative Synthesis Example 1 is represented by the following Chemical Formula 5.

(18) ##STR00015##

(19) wherein, in Chemical Formula 5, n is from 3 to 8. The cardo-based binder resin has a mixture form of the compound represented by Chemical Formula 5 in which n is in the above-mentioned range.

(20) In the prepared binder resin, the solid content was 33.9%, the acid value was 86 mgKOH/g, and the weight average molecular weight was 2,700 g/mol.

Comparative Synthesis Example 2

(21) In a 500 mL three-neck flask, 9,9-bisphenol fluorene diglycidyl ether (BPFG) (89 g, 0.19 mol), 4-cyclohexene-1,2-dicarboxylic acid (CDA) (51 g, 0.30 mol) and tetrabutylammonium bromide (TBAB) (1.4 g) were stirred together with propylene glycol methyl ether acetate (PGMEA) (260 g). Under the nitrogen atmosphere, the reaction mixture was heated to 120° C., and stirred for 24 hours. After cooling the reaction mixture to 80° C., inside the reactor was substituted with air, and after adding a polymerization inhibitor (BHT) (0.08 g) thereto, the result was stirred for 1 hour. After adding methacryloyloxyethyl isocyanate (MOI) (32.2 g, 0.21 mol) and propylene glycol methyl ether acetate (PGMEA) (32.2 g) to the reaction mixture, the result was stirred for 24 hours at 80° C. A binder resin prepared in Comparative Synthesis Example 2 is represented by the following Chemical Formula 6.

(22) ##STR00016##

(23) wherein, in Chemical Formula 6, n is from 3 to 8. The cardo-based binder resin has a mixture form of the compound represented by Chemical Formula 6 in which n is in the above-mentioned range.

(24) In the prepared binder resin, the solid content was 40.8%, the acid value was 69 mgKOH/g, and the weight average molecular weight was 2,890 g/mol.

Comparative Synthesis Example 3

(25) In a 500 mL three-neck flask, 9,9-bisphenol fluorene diglycidyl ether (BPFG) (89 g, 0.19 mol), 4-cyclohexene-1,2-dicarboxylic acid (CDA) (51 g, 0.30 mol) and tetrabutylammonium bromide (TBAB) (1.4 g) were stirred together with propylene glycol methyl ether acetate (PGMEA) (260 g). Under the nitrogen atmosphere, the reaction mixture was heated to 120° C., and stirred for 24 hours. After cooling the reaction mixture to 80° C., inside the reactor was substituted with air, and after adding a polymerization inhibitor (BHT) (0.08 g) thereto, the result was stirred for 1 hour. After adding acryloyloxyethyl isocyanate (AOI) (29.3 g, 0.21 mol) and propylene glycol methyl ether acetate (PGMEA) (29.3 g) to the reaction mixture, the result was stirred for 24 hours at 80° C. A binder resin prepared in Comparative Synthesis Example 3 is represented by the following Chemical Formula 7.

(26) ##STR00017##

(27) wherein, in Chemical Formula 7, n is from 3 to 8. The cardo-based binder resin has a mixture form of the compound represented by Chemical Formula 7 in which n is in the above-mentioned range.

(28) In the prepared binder resin, the solid content was 40.2%, the acid value was 72 mgKOH/g, and the weight average molecular weight was 2,810 g/mol.

Comparative Synthesis Example 4

(29) In a 500 mL three-neck flask, 9,9-bisphenol fluorene epoxy acrylate (BPFE) (100.6 g, 0.17 mol), isophorone diisocyanate (IPDI) (19.4 g, 0.09 mol) and tetrabutylammonium bromide (TBAB) (0.8 g) were stirred together with propylene glycol methyl ether acetate (PGMEA) (180 g). The reaction mixture was heated to 120° C., and reacted for 24 hours to produce urethane bonds. After cooling the reaction mixture to room temperature, the reaction was terminated. A binder resin prepared in Comparative Synthesis Example 4 is represented by the following Chemical Formula 8.

(30) ##STR00018##

(31) wherein, in Chemical Formula 8, n is from 3 to 8. The cardo-based binder resin has a mixture form of the compound represented by Chemical Formula 8 in which n is in the above-mentioned range.

(32) In the prepared binder resin, the solid content was 33.6%, the acid value was 0 mgKOH/g, and the weight average molecular weight was 2,660 g/mol.

Comparative Synthesis Example 5

(33) In a 500 mL three-neck flask, 9,9-bisphenol fluorene epoxy acrylate (BPFE) (100.6 g, 0.17 mol), isophorone diisocyanate (IPDI) (19.4 g, 0.09 mol) and tetrabutylammonium bromide (TBAB) (0.8 g) were stirred together with propylene glycol methyl ether acetate (PGMEA) (180 g). The reaction mixture was heated to 120° C., and reacted for 24 hours to produce urethane bonds. After cooling the reaction mixture to 90° C., tetrahydrophthalic anhydride (THPA) (13.9 g) and propylene glycol methyl ether acetate (PGMEA) (11.5 g) were added thereto, and the result was further reacted for 12 hours at 90° C. to synthesize a cardo-based resin including an acid group. A binder resin prepared in Comparative Synthesis Example 5 is represented by the following Chemical Formula 9.

(34) ##STR00019##

(35) wherein, in Chemical Formula 9, n is from 3 to 8. The cardo-based binder resin has a mixture form of the compound represented by Chemical Formula 9 in which n is in the above-mentioned range.

(36) In the prepared binder resin, the solid content was 29.5%, the acid value was 40 mgKOH/g, and the weight average molecular weight was 2,920 g/mol.

(37) The compositions included in the preparation examples are summarized and described in the following Table 1.

(38) TABLE-US-00001 TABLE 1 Preparation Step 1 Preparation Step 2 BPFG BPFE CDA IPDI TBAB PGMEA BHT GMA MOI AOI THPA PGEMA (g) (g) (g) (g) (g) (g) (g) (g) (g) (g) (g) (g) Synthesis 89 — 51 — 1.4 260 0.08 29.6 — — — 29.6 Example 1 Synthesis 89 — 51 — 1.4 260 0.08 22.2 — — — 22.2 Example 2 Synthesis 89 — 51 — 1.4 260 0.08 14.8 — — — 14.8 Example 3 Compar- 89 — 51 — 1.4 260 — — — — — — ative Synthesis Example 1 Compar- 89 — 51 — 1.4 260 0.08 — 32.2 — — 32.2 ative Synthesis Example 2 Compar- 89 — 51 1.4 260 0.08 — — 29.3 — 29.3 ative Synthesis Example 3 Compar- — 100.6 — 19.4 0.8 180 — — — — — — ative Synthesis Example 4 Compar- — 100.6 — 19.4 0.8 180 — — — — 13.9 11.5 ative Synthesis Example 5

(39) In Table 1, BPFG means 9,9-bis(4-glycidyloxyphenyl)fluorine, BPFE means 9.9-bis[4-(2-hydroxy-3-acryloyloxypropoxy)phenyl]fluorine, CDA means 4-cyclohexene-1,2-dicarboxylic acid, IPDI means isophorone diisocyanate, TBAB means tetrabutylammomium bromide, PGMEA means propylene glycol monomethyl ether acetate, BHT means 2,6-di-tert-butyl-4-methylphenol, MOI means 2-methacryloyloxyethyl isocyanate, AOI means 2-acryloyloxyethyl isocyanate, THPA means 1,2,3,6-tetrahydrophthalic anhydride, and GMA means glycidyl methacrylate.

Example 1

(40) Based on 100 parts by weight of a photosensitive resin composition, 35 parts by weight of a carbon black dispersion (Tokushiki Co., Ltd. BK 5075 content 15%), 5 parts by weight of the binder resin synthesized in Synthesis Example 1 (Mw=3040 g/mol, acid value=0 mgKOH/g), 5 parts by weight of a resin polymer including styrene/FA-513M and a reactive group as an acryl-based binder (Mw=8000 g/mol to 12000 g/mol, acid value=50 mgKOH/g to 100 mgKOH/g), 12 parts by weight of dipentaerythritol hexaacrylate as a multifunctional monomer, 1.0 parts by weight of Oxe 02 of BASF Corporation as a photoinitiator, 0.5 parts by weight of 3-methacryloxypropyltrimethoxysilane (KBM-503) as an adhesion promoter, 0.5 parts by weight of F-475 (DIC Corporation) as a leveling agent, and 33 parts by weight of propylene glycol monomethyl ether acetate and 8 parts by weight of 3-methoxybutyl acetate as a solvent were mixed.

(41) Then, the mixture was stirred for 5 hours to prepare a black photosensitive resin composition.

(42) After spin coating the photosensitive resin composition prepared as above on a glass substrate, the result was preheat treated for 100 seconds at approximately 100° C. to form a film having a thickness of approximately 2.0 μm to 3.0 μm.

(43) Then, the result was cooled at room temperature, and exposed using a photomask with energy of 30 mJ/cm.sup.2 to 100 mJ/cm.sup.2 under a high-pressure mercury lamp. The exposed substrate was developed in a 0.04% aqueous potassium hydroxide (KOH) solution at a temperature of 25° C. using a spray method, then washed with pure water, dried, and post-baked for 20 minutes in a convection oven at 230° C.

(44) The film obtained as above was obtained as a clean film having no surface defects caused from each process, a favorable pattern having a film thickness of 1.5 μm to 3.0 μm was able to be secured at mask transmittance of 100%, and a favorable pattern having a film thickness of 1.0 μm to 2.5 μm was able to be secured at mask transmittance of 10% or less.

Example 2

(45) Based on 100 parts by weight of a photosensitive resin composition, 35 parts by weight of a carbon black dispersion (Tokushiki Co., Ltd. BK_5075 content 15%), 5 parts by weight of the binder resin synthesized in Synthesis Example 2 (Mw=2940 g/mol, acid value=28 mgKOH/g), 5 parts by weight of a resin polymer including styrene/FA-513M and a reactive group as an acryl-based binder (Mw=8000 g/mol to 12000 g/mol, acid value=50 mgKOH/g to 100 mgKOH/g), 12 parts by weight of dipentaerythritol hexaacrylate as a multifunctional monomer, 1.0 parts by weight of Oxe 02 of BASF Corporation as a photoinitiator, 0.5 parts by weight of 3-methacryloxypropyltrimethoxysilane as an adhesion promoter, 0.5 parts by weight of F-475 (DIC Corporation) as a leveling agent, and 33 parts by weight of propylene glycol monomethyl ether acetate and 8 parts by weight of 3-methoxybutyl acetate as a solvent were mixed.

(46) Then, the mixture was stirred for 5 hours to prepare a black photosensitive resin composition.

(47) After spin coating the photosensitive resin composition prepared as above on a glass substrate, the result was preheat treated for 100 seconds at approximately 100° C. to form a film having a thickness of approximately 2.0 μm to 3.0 μm. Then, the result was cooled at room temperature, and exposed using a photomask with energy of 30 mJ/cm.sup.2 to 100 mJ/cm.sup.2 under a high-pressure mercury lamp. The exposed substrate was developed in a 0.04% aqueous potassium hydroxide (KOH) solution at a temperature of 25° C. using a spray method, then washed with pure water, dried, and post-baked for 20 minutes in a convection oven at 230° C.

(48) The film obtained as above was obtained as a clean film having no surface defects caused from each process, a favorable pattern having a film thickness of 1.5 μm to 3.0 μm was able to be secured at mask transmittance of 100%, and a favorable pattern having a film thickness of 1.0 μm to 2.5 μm was able to be secured at mask transmittance of 10% or less.

Example 3

(49) Parts by weight of a carbon black dispersion (Tokushiki Co., Ltd. BK_5075 content 15%), 5 parts by weight of the binder resin synthesized in Synthesis Example 3 (Mw=2890 g/mol, acid value=44 mgKOH/g), 5 parts by weight of a resin polymer including styrene/FA-513M and a reactive group as an acryl-based binder (Mw=8000 g/mol to 12000 g/mol, acid value=50 mgKOH/g to 100 mgKOH/g), 12 parts by weight of dipentaerythritol hexaacrylate as a multifunctional monomer, 1.0 parts by weight of Oxe 02 of BASF Corporation as a photoinitiator, 0.5 parts by weight of 3-methacryloxypropyltrimethoxysilane as an adhesion promoter, 0.5 parts by weight of F-475 (DIC Corporation) as a leveling agent, and 33 parts by weight of propylene glycol monomethyl ether acetate and 8 parts by weight of 3-methoxybutyl acetate as a solvent were mixed.

(50) Then, the mixture was stirred for 5 hours to prepare a black photosensitive resin composition.

(51) After spin coating the photosensitive resin composition prepared as above on a glass substrate, the result was preheat treated for 100 seconds at approximately 100° C. to form a film having a thickness of approximately 2.0 μm to 3.0 μm. Then, the result was cooled at room temperature, and exposed using a photomask with energy of 30 mJ/cm.sup.2 to 100 mJ/cm.sup.2 under a high-pressure mercury lamp. The exposed substrate was developed in a 0.04% aqueous potassium hydroxide (KOH) solution at a temperature of 25° C. using a spray method, then washed with pure water, dried, and post-baked for 20 minutes in a convection oven at 230° C.

(52) The film obtained as above was obtained as a clean film having no surface defects caused from each process, a favorable pattern having a film thickness of 1.5 μm to 3.0 μm was able to be secured at mask transmittance of 100%, and a favorable pattern having a film thickness of 1.0 μm to 2.5 μm was able to be secured at mask transmittance of 10% or less.

Comparative Example 1

(53) Parts by weight of a carbon black dispersion (Tokushiki Co., Ltd. BK_5075 content 15%), 5 parts by weight of the binder resin synthesized in Comparative Synthesis Example 1 (Mw=2700 g/mol, acid value=86 mgKOH/g), 5 parts by weight of a resin polymer including styrene/FA-513M and a reactive group as an acryl-based binder (Mw=8000 g/mol to 12000 g/mol, acid value=50 mgKOH/g to 100 mgKOH/g), 12 parts by weight of dipentaerythritol hexaacrylate as a multifunctional monomer, 1.0 parts by weight of Oxe 02 of BASF Corporation as a photoinitiator, 0.5 parts by weight of 3-methacryloxypropyltrimethoxysilane as an adhesion promoter, 0.5 parts by weight of F-475 (DIC Corporation) as a leveling agent, and 33 parts by weight of propylene glycol monomethyl ether acetate and 8 parts by weight of 3-methoxybutyl acetate as a solvent were mixed.

(54) Then, the mixture was stirred for 5 hours to prepare a black photosensitive resin composition.

(55) After spin coating the photosensitive resin composition prepared as above on a glass substrate, the result was preheat treated for 100 seconds at approximately 100° C. to form a film having a thickness of approximately 2.0 μm to 3.0 μm. Then, the result was cooled at room temperature, and exposed using a photomask with energy of 30 mJ/cm.sup.2 to 100 mJ/cm.sup.2 under a high-pressure mercury lamp. The exposed substrate was developed in a 0.04% aqueous potassium hydroxide (KOH) solution at a temperature of 25° C. using a spray method, then washed with pure water, dried, and post-baked for 20 minutes in a convection oven at 230° C.

(56) The film obtained as above was obtained as a clean film having no surface defects caused from each process, a favorable pattern having a film thickness of 1.5 μm to 3.0 μm was able to be secured at mask transmittance of 100%, and a favorable pattern having a film thickness of 1.0 μm to 2.5 μm was able to be secured at mask transmittance of 10% or less.

Comparative Example 2

(57) Parts by weight of a carbon black dispersion (Tokushiki Co., Ltd. BK_5075 content 15%), 5 parts by weight of the binder resin synthesized in Comparative Synthesis Example 2 (Mw=2890 g/mol, acid value=69 mgKOH/g), 5 parts by weight of a resin polymer including styrene/FA-513M and a reactive group as an acryl-based binder (Mw=8000 g/mol to 12000 g/mol, acid value=50 mgKOH/g to 100 mgKOH/g), 12 parts by weight of dipentaerythritol hexaacrylate as a multifunctional monomer, 1.0 parts by weight of Oxe 02 of BASF Corporation as a photoinitiator, 0.5 parts by weight of 3-methacryloxypropyltrimethoxysilane as an adhesion promoter, 0.5 parts by weight of F-475 (DIC Corporation) as a leveling agent, and 33 parts by weight of propylene glycol monomethyl ether acetate and 8 parts by weight of 3-methoxybutyl acetate as a solvent were mixed.

(58) Then, the mixture was stirred for 5 hours to prepare a black photosensitive resin composition.

(59) After spin coating the photosensitive resin composition prepared as above on a glass substrate, the result was preheat treated for 100 seconds at approximately 100° C. to form a film having a thickness of approximately 2.0 μm to 3.0 μm. Then, the result was cooled at room temperature, and exposed using a photomask with energy of 30 mJ/cm.sup.2 to 100 mJ/cm.sup.2 under a high-pressure mercury lamp. The exposed substrate was developed in a 0.04% aqueous potassium hydroxide (KOH) solution at a temperature of 25° C. using a spray method, then washed with pure water, dried, and post-baked for 20 minutes in a convection oven at 230° C.

(60) The film obtained as above was obtained as a clean film having no surface defects caused from each process, a favorable pattern having a film thickness of 1.5 μm to 3.0 μm was able to be secured at mask transmittance of 100%, and a favorable pattern having a film thickness of 1.0 μm to 2.5 μm was able to be secured at mask transmittance of 10% or less.

Comparative Example 3

(61) Parts by weight of a carbon black dispersion (Tokushiki Co., Ltd. BK_5075 content 15%), 5 parts by weight of the binder resin synthesized in Comparative Synthesis Example 3 (Mw=2810 g/mol, acid value=72 mgKOH/g), 5 parts by weight of a resin polymer including styrene/FA-513M and a reactive group as an acryl-based binder (Mw=8000 g/mol to 12000 g/mol, acid value=50 mgKOH/g to 100 mgKOH/g), 12 parts by weight of dipentaerythritol hexaacrylate as a multifunctional monomer, 1.0 parts by weight of Oxe 02 of BASF Corporation as a photoinitiator, 0.5 parts by weight of 3-methacryloxypropyltrimethoxysilane as an adhesion promoter, 0.5 parts by weight of F-475 (DIC Corporation) as a leveling agent, and 33 parts by weight of propylene glycol monomethyl ether acetate and 8 parts by weight of 3-methoxybutyl acetate as a solvent were mixed.

(62) Then, the mixture was stirred for 5 hours to prepare a black photosensitive resin composition.

(63) After spin coating the photosensitive resin composition prepared as above on a glass substrate, the result was preheat treated for 100 seconds at approximately 100° C. to form a film having a thickness of approximately 2.0 μm to 3.0 μm. Then, the result was cooled at room temperature, and exposed using a photomask with energy of 30 mJ/cm.sup.2 to 100 mJ/cm.sup.2 under a high-pressure mercury lamp. The exposed substrate was developed in a 0.04% aqueous potassium hydroxide (KOH) solution at a temperature of 25° C. using a spray method, then washed with pure water, dried, and post-baked for 20 minutes in a convection oven at 230° C.

(64) The film obtained as above was obtained as a clean film having no surface defects caused from each process, a favorable pattern having a film thickness of 1.5 μm to 3.0 μm was able to be secured at mask transmittance of 100%, and a favorable pattern having a film thickness of 1.0 μm to 2.5 μm was able to be secured at mask transmittance of 10% or less.

Comparative Example 4

(65) 35 Parts by weight of a carbon black dispersion (Tokushiki Co., Ltd. BK_5075 content 15%), 5 parts by weight of the binder resin synthesized in Comparative Synthesis Example 4 (Mw=2660 g/mol, acid value=0 mgKOH/g), 5 parts by weight of a resin polymer including styrene/FA-513M and a reactive group as an acryl-based binder (Mw=8000 g/mol to 12000 g/mol, acid value=50 mgKOH/g to 100 mgKOH/g), 12 parts by weight of dipentaerythritol hexaacrylate as a multifunctional monomer, 1.0 parts by weight of Oxe 02 of BASF Corporation as a photoinitiator, 0.5 parts by weight of 3-methacryloxypropyltrimethoxysilane as an adhesion promoter, 0.5 parts by weight of F-475 (DIC Corporation) as a leveling agent, and 33 parts by weight of propylene glycol monomethyl ether acetate and 8 parts by weight of 3-methoxybutyl acetate as a solvent were mixed.

(66) Then, the mixture was stirred for 5 hours to prepare a black photosensitive resin composition.

(67) After spin coating the photosensitive resin composition prepared as above on a glass substrate, the result was preheat treated for 100 seconds at approximately 100° C. to form a film having a thickness of approximately 2.0 μm to 3.0 μm. Then, the result was cooled at room temperature, and exposed using a photomask with energy of 30 mJ/cm.sup.2 to 100 mJ/cm.sup.2 under a high-pressure mercury lamp. The exposed substrate was developed in a 0.04% aqueous potassium hydroxide (KOH) solution at a temperature of 25° C. using a spray method, then washed with pure water, dried, and post-baked for 20 minutes in a convection oven at 230° C.

(68) The film obtained as above was obtained as a clean film having no surface defects caused from each process, a favorable pattern having a film thickness of 1.5 μm to 3.0 μm was able to be secured at mask transmittance of 100%, and a favorable pattern having a film thickness of 1.0 μm to 2.5 μm was able to be secured at mask transmittance of 10% or less.

Comparative Example 5

(69) Parts by weight of a carbon black dispersion (Tokushiki Co., Ltd. BK_5075 content 15%), 5 parts by weight of the binder resin synthesized in Comparative Synthesis Example 5 (Mw=2920 g/mol, acid value=40 mgKOH/g), 5 parts by weight of a resin polymer including styrene/FA-513M and a reactive group as an acryl-based binder (Mw=8000 g/mol to 12000 g/mol, acid value=50 mgKOH/g to 100 mgKOH/g), 12 parts by weight of dipentaerythritol hexaacrylate as a multifunctional monomer, 1.0 parts by weight of Oxe 02 of BASF Corporation as a photoinitiator, 0.5 parts by weight of 3-methacryloxypropyltrimethoxysilane as an adhesion promoter, 0.5 parts by weight of F-475 (DIC Corporation) as a leveling agent, and 33 parts by weight of propylene glycol monomethyl ether acetate and 8 parts by weight of 3-methoxybutyl acetate as a solvent were mixed.

(70) Then, the mixture was stirred for 5 hours to prepare a black photosensitive resin composition.

(71) After spin coating the photosensitive resin composition prepared as above on a glass substrate, the result was preheat treated for 100 seconds at approximately 100° C. to form a film having a thickness of approximately 2.0 μm to 3.0 μm. Then, the result was cooled at room temperature, and exposed using a photomask with energy of 30 mJ/cm.sup.2 to 100 mJ/cm.sup.2 under a high-pressure mercury lamp. The exposed substrate was developed in a 0.04% aqueous potassium hydroxide (KOH) solution at a temperature of 25° C. using a spray method, then washed with pure water, dried, and post-baked for 20 minutes in a convection oven at 230° C.

(72) The film obtained as above was obtained as a clean film having no surface defects caused from each process, a favorable pattern having a film thickness of 1.5 μm to 3.0 μm was able to be secured at mask transmittance of 100%, and a favorable pattern having a film thickness of 1.0 μm to 2.5 μm was able to be secured at mask transmittance of 10% or less.

(73) Parts by weight of the compositions used in the examples and the comparative examples are summarized and described in the following Table 2.

(74) TABLE-US-00002 TABLE 2 Compar- Compar- Compar- Compar- Compar- ative ative ative ative ative Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- ple ple ple ple ple ple ple ple 1 2 3 1 2 3 4 5 Organic 35 35 35 35 35 35 35 35 Black Dispersion (BK_5075) Binder Synthesis 5 — — — — — — — Resin Example 1 Synthesis — 5 — — — — — — Example 2 Synthesis — — 5 — — — — — Example 3 Compar- — — — 5 — — — — ative Synthesis Example 1 Compar- — — — — 5 — — — ative Synthesis Example 2 Compar- — — — — — 5 — — ative Synthesis Example 3 Compar- — — — — — — 5 — ative Synthesis Example 4 Compar- — — — — — — — 5 ative Synthesis Example 5 Acryl- 5 5 5 5 5 5 5 5 based Multifunctional 12 12 12 12 12 12 12 12 Monomer (DPHA) Photoinitiator 1 1 1 1 1 1 1 1 (OXE-02) KBM-503 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 F475 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Solvent 33 33 33 33 33 33 33 33 (PGMEA) Solvent 8 8 8 8 8 8 8 8 (3-MBA)

(75) In Table 2, DPHA, the multifunctional monomer, means dipentaerythritol hexaacrylate, and as the solvent, PGMEA means propylene glycol methyl ether acetate and 3-MBA means 3-methoxybutyl acetate. In order to evaluate developability and pattern adhesive strength of the films prepared in Examples 1 to 3 and Comparative Examples 1 to 5, a 5% transmittance smallest pattern (μm) and a level difference (A) were measured and described in the following Table 3. The 5% transmittance smallest pattern (μm) means a size of the smallest pattern attached on the substrate after development when performing exposure using a mask having transmittance of 5%. For example, when the exposure amount of the following Table 3 is 50 mJ/cm.sup.2 and the mask transmittance is 5%, energy actually used in the exposure is 2.5 mJ/cm.sup.2.

(76) The level difference means a difference between the thickness of the pattern formed when the mask transmittance is 100% (A) and the thickness of the pattern formed when the mask transmittance is 5% (B), and is calculated by the value subtracting (B) from (A).

(77) After calculating the thickness of the pattern formed when the mask transmittance was 100% (A) and the thickness of the pattern formed when the mask transmittance was 5% (B) in Examples 1 to 3 and Comparative Examples 1 to 5, the value subtracting (B) from (A) (level difference) was calculated and described in the following Table 3.

(78) TABLE-US-00003 TABLE 3 5% Transmittance Exposure Smallest Pattern Level Amount (μm) Difference (mJ/cm.sup.2) 0 Days 3 Weeks (Å) Example 1 45 14 14 ⊙ 50 12 12 ⊙ 55 12 12 ⊙ Example 2 45 17 17 ⊙ 50 15 16 ⊙ 55 14 16 ⊙ Example 3 45 X X X 50 17 19 ⊙ 55 16 17 ⊙ Comparative 45 X X X Example 1 55 X X X Comparative 45 X X X Example 2 50 X X X 55 19 25 ◯ Comparative 45 X X X Example 3 50 X X X 55 17 24 ∇ Comparative 45 X X X Example 4 50 15 16 Δ 55 13 15 Δ Comparative 45 X X X Example 5 50 17 19 Δ 55 16 18 Δ ⊙—8000 Å to 9500 Å ◯—7000 Å to 8000 Å Δ—6000 Å to 7000 Å ∇—6000 Å or less X—Pattern fall out

(79) As shown in Table 3, it was seen that Examples 1 to 3 had either the same or a smaller 5% transmittance smallest pattern (μm) compared to Comparative Examples 1 to 5. In addition, it was seen that Examples 1 to 3 had a larger level difference compared to Comparative Examples 1 to 5.

(80) When sensitivity is excellent, a size of a smallest pattern attached at 5% transmittance decreases due to increases in adhesive strength and developability resistance, however, a level difference tends to decrease due to sufficient curing even at a low exposure amount. Pattern adhesion and level difference are in a trade-off relationship, and when pattern adhesive strength increases, a level difference decreases, or when pattern adhesive strength decreases, a level difference increases.

(81) However, by introducing a photocurable group, the cardo-based binder resin of the present disclosure has excellent sensitivity and increased developability resistance due to a decrease in the acid group, and, despite the decrease in the size of the 5% transmittance smallest pattern, a level difference increases by a small thickness of the 5% transmittance pattern (B). Accordingly, the present disclosure is capable of increasing both pattern adhesive strength and a level difference.

(82) Hereinbefore, preferred embodiments of the present disclosure have been described, however, the present disclosure is not limited thereto, and various modifications may be made within the scope of the claims and the detailed descriptions of the disclosure, and these also fall within the category of the disclosure.