KR20220122893A - A photosensitive resin composition for forming partition wall, a partition wall structure prepared using the composition, and a display device comprising the partition wall structure - Google Patents

Abstract

The present invention relates to a photosensitive resin composition for forming a partition wall, which contains: (A) a colorant comprising a white pigment; (B) a UV absorbing agent; (C) an alkali-soluble resin; (D) a photopolymerizable compound; (E) a photopolymerization initiator; and (F) a solvent, wherein the UV absorbing agent includes at least one of a benzotriazole-based UV absorbing agent or a triazine-based UV absorbing agent. The present invention also relates to a partition wall structure prepared by using the composition, and a display device comprising the partition wall structure. The photosensitive resin composition of the present invention has excellent reliability such as solvent resistance and excellent swelling characteristics, and thus can prevent surface staining problems.

Description

A photosensitive resin composition for forming a barrier rib, a barrier rib structure manufactured using the same, and a display device including the barrier rib structure STRUCTURE}

The present invention relates to a photosensitive resin composition for forming barrier ribs, a barrier rib structure manufactured using the same, and a display device including the barrier rib structure.

In the case of a conventional flat panel or liquid crystal display, research on a display using a color conversion panel has been recently conducted due to a display structure that loses a lot of light. In a simple example, in a structure consisting of a color conversion panel together with a backlight that emits blue, the blue color of the backlight can be used completely because the blue color of the backlight is used. In addition, since blue is converted to red or green and displayed in a pixel displaying red or green, more light is generated from the pixel compared to the conventional method of expressing a desired color using absorption and transmission.

A display manufactured using a low temperature process will have great characteristics compared to a display manufactured using a previous high temperature process. In general, it is common to increase the reliability of the pattern through a high-temperature process in order to increase the reliability of the material, but in the case of the recently developed OLED, it is difficult to proceed with the high-temperature process because the OLED is vulnerable to heat. Therefore, if each is manufactured and later bonded together to manufacture a display, it is difficult to manufacture a flexible or rollable display. Therefore, it is necessary to form a color conversion pixel through a photolithography process on the upper portion of the OLED panel, and the demand for a low-temperature process to form the color conversion pixel is increasing. In addition, as the display device is enlarged, the size of the exposure machine of the mass production line is increasing in order to shorten the exposure time in the process for process efficiency, and accordingly, high-intensity exposure is required.

In addition, in a display device including a color conversion panel, a barrier rib is formed between each color conversion pixel to prevent color mixing of each color conversion pixel. Due to the conversion efficiency of the color conversion pixel, the barrier rib between each color conversion pixel is 3 to 15 formed to a thickness of μm.

The conventional photosensitive resin composition for a black matrix has no problem in forming a pattern when the thickness of the prepared film is 1 to 1.5 μm, but the barrier rib of the color conversion pixel has a thickness of 3 to 15 μm. It is not preferable to be formed as In addition, when the barrier rib is formed with a thick film using the conventional black matrix, there is a problem that light is not irradiated to the lower end of the pattern due to a decrease in the transmittance of ultraviolet rays during the exposure process, and the lower part of the film is not photocured. After the development process, the undercut phenomenon was severely induced, and there was a disadvantage in that the process margin was weak.

In addition, the photosensitive resin composition for forming barrier ribs may include scattering particles such as white pigments or metal oxides to improve optical properties of pixels in a display structure including quantum dots. It may cause hardening of the unexposed part by scattering when it receives the light of In particular, this phenomenon occurred more severely in the exposure machine with high illuminance, and problems such as reverse taper angle, residual film, and non-development occurred. In addition, when the reliability of the barrier ribs such as solvent resistance is low, residues are generated inside the barrier ribs in a thermal process of manufacturing and passing through the barrier ribs, thereby reducing the efficiency and lifespan of the color conversion pixels.

Korean Patent Application Laid-Open No. 10-2007-0094460 aims to provide a photosensitive resin composition for forming a barrier rib having excellent shape stability against heat, but the above-described problem cannot be overcome.

Republic of Korea Patent Publication No. 10-2007-0094460 (published on Sep. 20, 2007)

An object of the present invention is to provide a photosensitive resin composition for forming a barrier rib, which is to improve the above-mentioned prior art problems, and has excellent reliability such as solvent resistance and excellent swelling properties to prevent surface stain problems. do.

Further, an object of the present invention is to provide a photosensitive resin composition for forming a barrier rib which does not generate a residual film or a residue even when exposed to high illuminance, and has excellent tapered process characteristics.

Another object of the present invention is to provide a barrier rib structure and a display device manufactured by using the photosensitive resin composition for forming barrier ribs.

The present invention relates to a photosensitizer for forming a partition wall comprising (A) a colorant containing a white pigment, (B) a UV absorber, (C) an alkali-soluble resin, (D) a photopolymerizable compound, (E) a photoinitiator, and (F) a solvent As a resin composition, the UV absorber provides a photosensitive resin composition for forming barrier ribs, characterized in that it includes any one or more of a benzotriazole-based or triazine-based UV absorber.

In addition, the present invention provides a barrier rib structure made of the photosensitive resin composition for forming barrier ribs and a display device including the same.

The photosensitive resin composition for forming a barrier rib and the barrier rib structure according to the present invention have excellent reliability such as solvent resistance and excellent swelling properties, thereby providing an effect of preventing a surface stain problem.

In addition, the photosensitive resin composition for forming a barrier rib and the barrier rib structure according to the present invention do not generate a residual film or residue even during high-intensity exposure, and may provide an effect of excellent tapered process characteristics.

1 is a diagram illustrating the evaluation criteria for residual film/residue characteristics of a barrier rib pattern cured film prepared from a photosensitive resin composition for forming barrier ribs according to Examples and Comparative Examples of the present invention.
FIG. 2 is a diagram of evaluation criteria for tapered properties of a barrier rib pattern cured film prepared from a photosensitive resin composition for forming barrier ribs according to Examples and Comparative Examples of the present invention.

The present invention relates to a photosensitizer for forming a partition wall comprising (A) a colorant containing a white pigment, (B) a UV absorber, (C) an alkali-soluble resin, (D) a photopolymerizable compound, (E) a photoinitiator, and (F) a solvent As a resin composition, the UV absorber comprises any one or more of a benzotriazole-based or triazine-based UV absorber, a photosensitive resin composition for forming a barrier rib, a barrier rib structure made of the photosensitive resin composition for forming a barrier, and the same It relates to a display device that

Hereinafter, the present invention will be described in detail.

<Photosensitive resin composition for partition formation>

The photosensitive resin composition for forming a barrier rib according to the present invention comprises (A) a colorant including a white pigment, (B) a UV absorber, (C) an alkali-soluble resin, (D) a photopolymerizable compound, (E) a photopolymerization initiator, and (F) ) may contain a solvent.

(A) Colorant

The colorant according to the present invention is characterized in that it comprises (a1) a white pigment.

(a1) white pigment

The white pigment is for the reflective characteristics of the barrier rib structure, and specifically, it improves the reflectivity of the barrier rib structure with respect to light of a red and/or green wavelength, so that light generated from the color conversion element is directed toward the barrier rib. By reflecting light in a wavelength range, luminance can be improved. However, when only white pigment is used, as a scatterer, when light from the exposure machine is received, it may scatter and cause hardening of the unexposed area. Problems such as phenomena may occur.

It is preferable that the average particle size of the white pigment is 150 nm to 400 nm, and when the average particle size is less than 150 nm, it exhibits UV light blocking properties, so that UV light does not sufficiently penetrate downward during the exposure process, so pattern formation is not easy. , and the particle size is too small to improve the transmittance in the visible ray region, which may cause a problem in that the shielding properties are deteriorated. If the average particle size exceeds 400 nm, dispersibility and storage stability may be poor, the surface smoothness of the exposed part may be reduced, the interface between the exposed part and the non-exposed part may not be smooth, and the reflection characteristics may not be effective.

The white pigment (Pigment White) is titanium oxide (TiO ₂ ), silicon dioxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), tin oxide (SnO ₂ ), iron oxide (Fe2O ₃ ), zinc oxide (ZnO), Magnesium oxide (MgO), zirconium oxide (ZrO ₂ ), cerium oxide (CeO ₂ ), lithium oxide (Li ₂ O), silver oxide (AgO), antimony oxide (Sb ₂ O3, Sb ₂ O ₅ ) and calcium oxide (CaO) ) may be at least one selected from the group consisting of, preferably titanium oxide (TiO ₂ ) or zirconium oxide (ZrO ₂ ), and more preferably titanium oxide (TiO ₂ ). .

As the white pigment, if the above conditions are satisfied, a white pigment known in the art (C.I. Pigment White) may be used, and as the white pigment, for example, C.I. Pigment White 4, 5, 6, 6:1, 7, 18, 18:1, 19, 20, 22, 25, 26, 27, 28 and 32, etc., in terms of reflection efficiency and whiteness, C.I. It is preferred to include Pigment White 6 or 22, and C.I. It is more preferable to include Pigment White 6. These can be used individually or in mixture of 2 or more types.

Titanium oxide (TiO ₂ ) included in CI Pigment White 6 is inexpensive and has a high refractive index, so it can be used as an effective white pigment because it has excellent reflectance, and in terms of colorability and whiteness, it is preferable to have a rutile structure.

The titanium oxide (TiO ₂ ) is, if necessary, a resin treatment, a surface treatment using a pigment derivative into which an acidic group or a basic group is introduced, a graft treatment to the pigment surface with a polymer compound, etc., atomization treatment by a sulfuric acid atomization method, or the like It may be one that has been subjected to washing treatment with an organic solvent or water to remove impurities, or ionic impurity removal treatment by an ion exchange method or the like.

The titanium oxide (TiO ₂ ) is a surface-treated one or more selected from the group consisting of silicon oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), zirconium oxide (ZrO ₂ ) and organic materials. may, preferably, silicon oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ) and zirconium oxide (ZrO ₂ ) sequentially surface-treated may be used, and more preferably, the surface-treated oxide Titanium (TiO ₂ ) A surface treatment of the outermost surface of the organic material may be used. As the organic material, by coating titanium oxide (TiO ₂ ) with a single molecular layer of low polarity and surface treatment, the energy required for dispersion of titanium oxide (TiO ₂ ) is lowered, and titanium oxide (TiO ₂ ) is compressed and aggregated. It is not particularly limited as long as it is to prevent it, and in one or a plurality of embodiments, stearic acid, trimethylpropane (TMP), pentaerythritol, and the like may be used.

By surface-treating the titanium oxide (TiO ₂ ) as described above, it is possible to improve the reflective luminance characteristics while lowering the photocatalytic activity of the titanium oxide (TiO ₂ ). In particular, according to a preferred embodiment of the surface treatment, heat resistance and chemical resistance There is an advantage in terms of improved reliability, such as. The surface treatment may be a treatment by encapsulation.

The content of the titanium oxide (TiO ₂ ) core included in the surface-treated titanium oxide (TiO ₂ ) is preferably 85 to 95 wt%, based on the total weight of the surface-treated titanium oxide (TiO ₂ ). When the surface of the titanium oxide (TiO ₂ ) core is treated within the above range, the whiteness is excellent and the reflective brightness is excellent.

Commercial products of the titanium oxide (TiO ₂ ) include R-101, R-102, R-103, R-104, R-105, R-350, R-706, R-794, R of DuPont. -796, TS-6200, R-900, R-902, R-902+, R-931, R-960, etc. can be exemplified, and furthermore, Huntman's R-FC5, TR81, TR88 and I CR-57 by ISK, etc. can be illustrated.

The white pigment may be included in an amount of 1 to 30% by weight based on the total weight of the colorant (A) of the photosensitive resin composition for forming a barrier rib of the present invention. When the content of the white pigment is included in less than 1% by weight, the reflectance in the wavelength region of the red and green pixels is not sufficient, so improvement in light efficiency cannot be expected. A residual film may be formed on the surface, or the taper shape may deteriorate.

(a2) additional pigments or dyes;

(A) color material according to the present invention may further include organic pigments, inorganic pigments, dyes, etc. commonly used in the art within the scope not impairing the object of the present invention, preferably black pigment, red pigment, One or more pigments selected from the group consisting of yellow pigments and blue pigments may be mixed and used.

As said black pigment, it can select suitably from a black organic pigment or a black inorganic pigment.

The black organic pigment may be at least one selected from the group consisting of lactam black, perylene black, cyanine black and aniline black, and the black inorganic pigment may be selected from the group consisting of carbon black, chromium oxide, iron oxide and titanium black. At least one selected type may be used, and depending on the purpose, a black organic pigment and a black inorganic pigment may be used alone or in combination of two or more types.

The red pigment (Pigment Red) may be at least one selected from diketopyrrole-based, anthraquinone-based, perylene-based and azo-based, preferably, the red pigment is C.I. red pigment 9, 81, 97, 105, 122, 123, 144, 149, 150, 155, 166, 168, 171, 175, 176, 177, 179, 180, 185, 192, 202, 208, 209, 214, 215, 216, 220, 222, 224, 242, 254, 255, 264, 269, 270 and 272 may be at least one selected from the group consisting of, more preferably, the red pigment is C.I. It may be at least one selected from the group consisting of red pigments 177, 179, 254, 264 and 269.

The yellow pigment (Pigment Yellow) may be at least one selected from anthraquinone-based, isoindolinone-based, and azo-based, preferably, the yellow pigment is C.I. Yellow pigment 11, 13, 20, 24, 31, 53, 83, 86, 93, 94, 95, 99, 108, 109, 110, 117, 125, 128, 129, 138, 139, 147, 148, 150, 151, 154, 155, 166, 167, 173, 180, 185 and 199 may be at least one selected from the group consisting of, more preferably, the yellow pigment is C.I. It may be at least one selected from the group consisting of yellow pigments 138, 139, 150 and 185.

The blue pigment (Pigment Blue) is C.I. Pigment Blue 15, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. It may be at least one selected from Pigment Blue 15:6.

The dye may be used without limitation as long as it has solubility in organic solvents or is dispersible. Preferably, it is preferable to use a dye having solubility in an organic solvent and ensuring reliability such as solubility in an alkali developer, heat resistance, and solvent resistance.

As the dye, an acid dye having an acid group such as sulfonic acid or carboxylic acid, a salt of an acid dye and a nitrogen-containing compound, a sulfonamide compound of an acid dye, and derivatives thereof may be used. In addition, azo-based, xanthene-based, phthalocyanine Acid dyes and derivatives thereof can also be selected.

Preferably, the dye is a compound classified as a dye in the color index (published by The Society of Dyers and Colorists), or a known dye described in a dyeing note (color dye).

Specific examples of the dye include,

C.I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35

C.I. Solvent Yellow 4, 14, 15, 16, 21, 23, 24, 38, 56, 62, 63, 68, 79, 82, 93, 94, 98, 99, 151, 162, 163

C.I. Solvent Blue 18, 35, 36, 45, 58, 59, 59:1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139

C.I. red dyes such as solvent red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, 179;

C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, Red dyes, such as 382, 383, 394, 401, 412, 417, 418, 422, 426, are mentioned.

The pigments and dyes may be used alone or in combination of two or more.

(a3) pigment dispersant

The pigment dispersant is added to deagglomerate and maintain stability of the pigment, and may be used without limitation in the art, and specific examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, Surfactants, such as polyester type and polyamine type, etc. are mentioned, These can be used individually or in combination of 2 or more types, respectively.

In addition, the pigment dispersant preferably includes an acrylate-based dispersant (hereinafter, acrylate-based dispersant) including butyl methacrylate (BMA) or N,N-dimethylaminoethyl methacrylate (DMAEMA). It is preferable to use the acrylate-based dispersant prepared by the living control method, and commercially available products include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070 or DISPER BYK-2150. The rate-based dispersant may be used alone or in combination of two or more.

As the pigment dispersant, a pigment dispersant of a resin type other than the acrylate-based dispersant may be used. The pigment dispersants of the other resin types include known resin type pigment dispersants, in particular polyurethane, polycarboxylic acid esters typified by polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acids (partially) amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphate salts, esters of hydroxyl-containing polycarboxylic acids and modified products thereof, or free ) oily dispersants such as amides or salts thereof formed by the reaction of a polyester having a carboxyl group with poly (lower alkyleneimine); water-soluble resins or water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinyl pyrrolidone; Polyester; modified polyacrylates; adducts of ethylene oxide/propylene oxide; and phosphate esters.

Commercial products of the above other resin-type pigment dispersants include, for example, BYK (Big) Chemi's trade names: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; BASF trade names: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; Trade names from Lubrizol: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; Kawaken Fine Chemicals' trade names: HINOACT T-6000, HINOACT T-7000, HINOACT T-8000; Trade names of Ajinomoto Corporation: AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB-823; Trade names of Kyoeisha Chemical Corporation: FLORENE DOPA-17HF, fluorene DOPA-15BHF, fluorene DOPA-33, fluorene DOPA-44, etc. are mentioned.

In addition to the acrylate-based dispersant, other resin-type pigment dispersants may be used alone or in combination of two or more, or may be used in combination with an acrylate-based dispersant.

The pigment dispersant may be included in an amount of 1 to 50 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of the solid content of the colorant. When the content of the pigment dispersant is within the above range, it is preferable because it is possible to obtain a dispersed pigment having a uniform particle size. If the content of the dispersant is more than 50 parts by weight, the viscosity may increase, and if it is less than 1 part by weight, it may be difficult to atomize the pigment, or it may cause problems such as gelation after dispersion.

(B) UV absorber

The UV absorber according to the present invention can reduce a CD bias due to diffraction as it partially absorbs UV, and thus can serve to implement a desired pattern. The CD means the embossed part of the pattern, and the CD bias means the degree to which the size of the pattern formed is larger than that of the mask pattern to be implemented.

In addition, when the photosensitive resin composition containing scattering particles such as the white pigment or metal oxide is exposed to high illuminance (15,000 mW or more), problems of residual film and residue may occur, and the UV absorber of the present invention is exposed to high illuminance. In the process, it helps to maintain the sensitivity of the deep part while lowering the sensitivity on the surface, thereby suppressing the residual film in the form of drag caused by the difference in sensitivity between the upper and lower parts, thereby preventing the remaining film and residues from being generated.

The UV absorber according to the present invention includes a UV absorber that absorbs an i-line wavelength, and includes at least one of a benzotriazole-based and a triazine-based UV absorber as an essential component.

The benzotriazole-based and triazine-based UV absorbers have superior absorption at a maximum absorption wavelength of 365 nm compared to other types of UV absorbers, and thus may be advantageous for high-intensity exposure.

As the benzotriazole-based UV absorber, for example, octyl 3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate , 2-ethylhexyl 3-(3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl)propionate, [3-[3-(2H) -Benzotriazol-2-yl)-5-(1,1-methylethyl)-4-hydroxyphenyl]-1-oxopropyl]-w-[3-[3-(2H-benzotriazole-2) -yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]poly(oxy-1,2-ethanediyl), (3-(3-(2H- Benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl)-1-oxopropyl)-hydroxypoly(oxo-1,2-ethanediyl), 2- (3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chloro-2H-benzotriazole, 2-(2H-benzotriazol-2-yl)-4,6-ditertpentylphenol; 3-(2H-benzotriazolyl)-5-(1,1-dimethylethyl)-4-hydroxy-benzinpropionic acid octyl ester, 2-(2H-benzotriazol-2-yl)-4,6-bis (1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3- tetramethylbutyl)phenol; and the like.

Examples of the triazine-based UV absorber include 2-(4,6-dimethyl-1,3,5-triazin-2-yl)-5-((hexyl)oxy)-phenol, 2-(4 -(2-hydroxy-3-tridecyloxypropyl)oxy)-2-hydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-( 4-(2-hydroxy-3-didecyloxypropyl)oxy)-2-hydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2- (2-hydroxy-4-(3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy)phenyl)-4,6-bis(2,4-dimethylphenyl)-1,3, 5-triazine, 2,2'-[6-(2,4-dibutoxyphenyl)-1,3,5-triazine-2,4-diyl]bis(5-butoxyphenol), 6 -methylheptyl 2-{4-[4,6-di(4-biphenylyl)-1,3,5-triazin-2-yl]-3-hydroxyphenoxy}propanoate; have.

The content of the UV absorber is preferably 0.05 to 10% by weight based on the total weight of the solid content of the photosensitive resin composition for forming a barrier rib of the present invention. When the content of the UV absorber is less than the above range, it is difficult to exhibit the expected effect by using the UV absorber. .

(C) alkali-soluble resin

The alkali-soluble resin of the present invention is a component that imparts solubility to the alkali developer used in the developing step, and acts as a dispersion medium for the pigment.

The alkali-soluble resin may be used without limitation as long as it is soluble in an alkali developer, and may preferably include a cardo-based resin, an acrylic resin, or a mixture thereof.

The cardo-based resin has reactivity and alkali solubility under the action of light or heat, and the cardo-based resin contained in the photosensitive resin composition for forming a barrier rib of the present invention functions as a binder resin for a colorant including a white pigment, It is not limited as long as it is a resin soluble in an alkaline developing solution.

The cardo-based resin of the present invention may include one or more of the compounds represented by Chemical Formulas 1-1 and 1-2.

[Formula 1-1]

[Formula 1-2]

이며,In Formula 1-1 or Formula 1-2, R1, R2, R3 and R4 are each independently an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, or

is,

X is a hydrogen atom; an alkyl group having 1 to 5 carbon atoms; or a hydroxyl group,

R5 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

In the present invention, the compound represented by Formula 1-1 may be synthesized as a compound represented by Formula 2-1 below, and the compound represented by Formula 1-2 may be synthesized using a compound represented by Formula 2-2. .

[Formula 2-1]

[Formula 2-2]

As said acrylic alkali-soluble resin, it is preferable to manufacture by copolymerizing the ethylenically unsaturated monomer which has a carboxyl group.

Specific examples of the ethylenically unsaturated monomer having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid; and an anhydride of said dicarboxylic acid; Polymer mono(meth)acrylates having a carboxyl group and a hydroxyl group at both terminals, such as ω-carboxypolycaprolactone mono(meth)acrylate, etc. are mentioned, and acrylic acid and methacrylic acid are preferable.

In addition, the alkali-soluble resin can be prepared by polymerizing the ethylenically unsaturated monomer having the carboxyl group and the copolymerizable unsaturated monomer.

Specific examples of the copolymerizable unsaturated polymerization monomer include glycidyl methacrylate, which is an unsaturated monomer having a glycidyl group; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, N -ethylenically unsaturated monomers having a hydroxyl group such as hydroxyethyl (meth)acrylates such as hydroxyethyl acrylamide; Styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinyl aromatic vinyl compounds such as benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N-m -N-substituted maleimide compounds, such as methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, and N-p-methoxyphenylmaleimide; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth)acrylates such as sec-butyl (meth)acrylate and t-butyl (meth)acrylate; Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6 ] decan-8-yl (meth) acrylate, 2- alicyclic (meth)acrylates such as dicyclopentanyloxyethyl (meth)acrylate and isobornyl (meth)acrylate; aryl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate; 3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane; 3-(methacryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, etc. of unsaturated oxetane compounds; and the like, but is not limited thereto.

Each of the above copolymerizable unsaturated monomers may be used alone or in combination of two or more.

It is preferable that the acid value of the alkali-soluble resin is 30 to 200 mgKOH/g. When the acid value of the alkali-soluble resin is less than 30 mgKOH/g, it is difficult for the photosensitive resin composition for forming barrier ribs to secure a sufficient development speed. A problem occurs in compatibility with the colorant, and the colorant in the photosensitive resin composition is precipitated, or the storage stability of the photosensitive resin composition is lowered and the viscosity tends to increase.

The 'acid value' is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can be usually obtained by titration using an aqueous potassium hydroxide solution.

In addition, the polystyrene reduced weight average molecular weight (hereinafter simply referred to as 'weight average molecular weight') measured by gel permeation chromatography (GPC; tetrahydrofuran is used as the elution solvent) is 2,000 to 20,000, preferably 3,000 to 10,000. A cardo-type resin or an acrylic-type alkali-soluble resin is preferable. Within the molecular weight range, film loss in the developing process may be suppressed and pattern stability may be improved.

The alkali-soluble resin may be included in an amount of 5 to 85% by weight, preferably 5 to 60% by weight, based on the total weight of the solid content of the photosensitive resin composition for forming a barrier rib according to the present invention. When the alkali-soluble resin is included within the above range, the solubility in the developer is sufficient to facilitate the formation of a cured film, and the film reduction of the pixel portion of the exposed portion is prevented during development, so that the omission property of the unexposed portion is improved. .

(D) photopolymerizable compound

The photopolymerizable compound is a compound that can be polymerized by the action of the photopolymerization initiator (D) below, and may be a monofunctional monomer, a bifunctional monomer or a polyfunctional monomer, and preferably a polyfunctional monomer having a bifunctional or higher function may be used. .

Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, or N-vinyl acrylate. Rollidone, and the like, but is not limited thereto.

Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate. , bis (acryloyloxyethyl) ether of bisphenol A, or 3-methylpentanediol di (meth) acrylate, but is not limited thereto.

Specific examples of the polyfunctional monomer include trimethylol propane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol hexa(meth) acrylate or dipentaerythritol hexa(meth)acrylate, but is not limited thereto.

In addition, the photopolymerizable compound may be included in an amount of 5 to 50% by weight, preferably 7 to 45% by weight, based on the total weight of the solid content of the photosensitive resin composition for forming a barrier rib. When the photopolymerizable compound is included within the above range, it is preferable in terms of strength and smoothness.

(E) photoinitiator

The photopolymerization initiator according to the present invention is a compound that generates a radical capable of initiating polymerization of the photopolymerizable compound by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, or X-ray.

As the photopolymerization initiator, for example, an acetophenone-based compound, a benzophenone-based compound, a biimidazole-based compound, a triazine-based compound, an oxime ester-based compound, and a thioxanthone-based compound may be used.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1-[4-(2-hydroxyl) oxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one; 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane-1 -one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, etc. are mentioned.

Specific examples of the benzophenone-based compound include benzophenone, methyl O-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'-tetra (tert) -Butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned.

Specific examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichloro Phenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole , 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (trialkoxyphenyl) biimidazole, 2,2-bis (2,6-dichlorophenyl) -4, 4'5,5'-tetraphenyl-1,2'-biimidazole or the imidazole compound in which the phenyl group at the 4,4',5,5'-position is substituted by the carboalkoxy group, etc. are mentioned. Among them, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4' ,5,5'-tetraphenylbiimidazole and 2,2-bis(2,6-dichlorophenyl)-4,4'5,5'-tetraphenyl-1,2'-biimidazole are preferably used do.

Specific examples of the triazine-based compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6 -(4-Methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2- yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl )-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine etc. are mentioned.

Specific examples of the oxime ester compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, 1,2-octadione,-1-(4-phenylthio)phenyl, -2 -(o-benzoyloxime), ethanone,-1-(9-ethyl)-6-(2-methylbenzoyl-3-yl)-,1-(o-acetyloxime), etc. are mentioned, Commercially available products CGI-124, CGI-224 from Ciba-Geigi, Irgacure® OXE-01, Irgacure® OXE-02, Irgacure® OXE-03 from BASF, N-1919 from Adeka, PBG-327 from NCI-831 Tronley, PBG-345 etc. are mentioned.

Specific examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like. have.

The photopolymerization initiator may be used alone or in combination of two or more.

The photopolymerization initiator may be included in an amount of 0.01 to 10% by weight, preferably 0.01 to 5% by weight, based on the total weight of the solid content of the photosensitive resin composition for forming barrier ribs. When the photopolymerization initiator is included within the above range, it is preferable because the photopolymerization reaction rate is appropriate to prevent an increase in the overall process time and to prevent deterioration of the physical properties of the final cured film due to overreaction.

The photosensitive resin composition for forming a barrier rib according to the present invention may further include a photopolymerization initiator auxiliary in addition to the photopolymerization initiator. When a photopolymerization initiation auxiliary is used together with the photopolymerization initiator, the photosensitive resin composition becomes more sensitive and productivity is improved.

The photopolymerization initiation adjuvant is a compound used to promote polymerization of a polymerizable compound whose polymerization is initiated by the photopolymerization initiator, and at least one compound selected from the group consisting of amines and carboxylic acid compounds may be preferably used.

When the photopolymerization initiation aid is included, its content may be typically greater than 0 mol to 10 mol or less, preferably 0.01 mol to 5 mol, based on 1 mol of the photopolymerization initiator. When the photopolymerization initiation adjuvant is included within the above range, it is preferable because the productivity improvement effect can be expected by improving the photopolymerization efficiency.

(F) solvent

As the solvent, an organic solvent known in the art may be used without particular limitation.

Specific examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether , Diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ethers such as ether and dipropylene glycol dibutyl ether; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; 3-Ethoxy ethyl propionate, 3-methoxymethyl propionate, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-methyl Toxybutyl acetate, 3-methyl-3-methoxy-1-butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol Esters such as monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate and γ-butyrolactone can be heard The solvent may be used one or a mixture of two or more selected from the group consisting of the exemplified solvents.

Preferably, an organic solvent having a boiling point of 100 to 200° C. in terms of applicability and dryness among the solvents may be used, and more preferably, alkylene glycol alkyl ether acetates, ketones, 3-ethoxypropionate ethyl, or 3-methyl Esters such as methyl oxypropionate may be used, and more preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxypropionate ethyl, 3-methoxypropionate methyl, etc. may be used. can These solvents can be used individually or in mixture of 2 or more types, respectively.

The content of the solvent may be included in a residual amount such that the total weight of the photosensitive resin composition for forming a barrier rib is 100% by weight. Specifically, in the present invention, "residual amount" means a remaining amount such that the total weight of the composition further including the essential components and other additional components of the present invention is 100% by weight, and due to the meaning of the "residual amount", the The photosensitive resin composition for forming barrier ribs is not limited to those that do not contain additional components.

For example, the solvent may be included in an amount of 60 to 90% by weight, preferably 70 to 85% by weight, based on the total weight of the photosensitive resin composition for forming barrier ribs, but is not limited thereto. but. When the solvent is contained within the above content range, the effect of improving the applicability when applied with an application device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as a die coater), inkjet, etc. It is preferable to provide

(G) Epoxy compound

The photosensitive resin composition for forming a barrier rib of the present invention may further include an epoxy compound, and by including the epoxy compound, reliability such as heat resistance and solvent resistance of a coating film can be improved, and low-temperature curability characteristics can be improved.

As the epoxy compound, an alicyclic epoxy compound, a bisphenol A-type epoxy compound, a bisphenol F-type epoxy compound, a novolak-type epoxy compound, a polyfunctional amine epoxy compound, etc. may be used, and these may be used alone or in combination of two or more. have. Preferably, an alicyclic epoxy compound, more preferably a bifunctional alicyclic epoxy compound is used, which is excellent in low-temperature curing properties and solvent resistance.

Examples of the alicyclic epoxy compound include 1,2-epoxy-4-vinylcyclohexane vinylcyclohexene monoxide, 1,2:8,9 diepoxylimonene, 3,4-epoxycyclohexenylmethyl- 3'4'-epoxycyclohexenecarboxylate, limonene dioxide, di(3,4-epoxycyclohexyl)adipate, (3,4-epoxycyclohexyl)methyl-3,4-epoxycyclohexanecarboxylate, (3 ,4-Epoxy-6-methylcyclohexyl)methyl-3,4-epoxy-6-methylcyclohexanecarboxylate, ethylene-1,2-di(3,4-epoxycyclohexanecarboxylic acid) ester, bis(3 ,4-epoxycyclohexylmethyl) adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, diethylene glycol bis(3,4-epoxycyclohexylmethyl ether), ethylene glycol bis(3) ,4-epoxycyclohexylmethyl ether), 4-(3,4-epoxycyclohexyl)-2,6-dioxa-8,9-epoxyspiro[5.5]undecane, 4-vinylcyclohexenedioxide, bis- 2,3-epoxycyclopentyl ether, dicyclopentadiene dioxide, etc. are mentioned. Among these, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl alcohol, and 3,4-epoxycyclohexylethyltrimethoxysilane are preferable.

In addition, the alicyclic epoxy compound may be synthesized or a commercially available product may be used. Commercially available alicyclic epoxy compounds include "Celoxide 2000 (CEL2000: vinylcyclohexene monoxide 1,2-epoxy-4-vinylcyclohexane)" manufactured by Daicel Chemical Industry Co., Ltd., "Celoxide 3000 (CEL3000)" : 1,2:8,9 diepoxylimonene)", "Celoxide 2021P (CEL2021P: 3,4-epoxycyclohexenylmethyl-3', 4'-epoxy cyclohexene carboxylate)", etc., It is not limited thereto, and these may be used alone or in combination of two or more.

The epoxy compound may be included in an amount of 5 to 50 wt%, preferably 7 to 45 wt%, based on the total weight of the solid content of the photosensitive resin for forming the barrier rib. When the epoxy compound is included within the above range, it is preferable in terms of improving low-temperature curing and solvent resistance.

additive

The photosensitive resin composition for forming a barrier rib according to the present invention may further include additives such as fillers, other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, and anti-aggregation agents, if necessary. The above additives may be used alone or in combination of two or more.

As the filler, specifically, glass, silica, alumina, etc. may be used, but the present invention is not limited thereto.

Specific examples of the other high molecular compounds include curable resins such as epoxy resins and maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane. However, the present invention is not limited thereto.

Examples of the surfactant include silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, and amphoteric surfactants, and these may be used alone or in combination of two or more. .

The antioxidant may include, for example, at least one selected from the group consisting of phosphorus-based antioxidants, sulfur-based antioxidants, and phenol-based antioxidants, and in this case, color change that may occur at high temperatures during the process or a light source after display manufacturing It can inhibit the occurrence of yellowing that can be caused by The antioxidant may include at least one selected from the group consisting of a phenolic compound, a phosphorus compound, and a sulfur compound, which are a phenolic-phosphorus compound, a phenolic-sulfur compound, a phosphorus-sulfur compound, or a phenolic-phosphorus compound. -Can be used in combination with sulfur compounds.

The adhesion promoter is specifically, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N -(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltri One or a mixture thereof selected from the group consisting of methoxysilane, 3-isocyanatepropyltrimethoxysilane and 3-isocyanatepropyltriethoxysilane may be used.

The aggregation inhibitor may be specifically sodium polyacrylate, but is not limited thereto.

The additive may be appropriately added and used by those skilled in the art in a range that does not impair the effects of the present invention. For example, the additive may be used in an amount of 0.05 to 10% by weight, preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight, based on the total weight of the photosensitive resin composition for forming barrier ribs, but is not limited thereto.

<Bulkhead structure and display device>

The present invention provides a barrier rib structure made of the photosensitive resin composition for forming barrier ribs and a display device including the same.

In a display device including a color conversion panel, since each pixel is driven to form a color, a barrier rib structure capable of distinguishing each pixel from each other is required. A display device including a barrier rib structure formed by using the photosensitive resin composition for forming barrier ribs of the present invention prevents color mixing between pixels, is advantageous for forming a fine pattern, and has a barrier rib with little line width change according to a change in development time in the developing process can be manufactured. When the change in the line width of the barrier rib is small, the color conversion pixel can secure sufficient space and has the advantage of realizing a high-quality image.

In addition, the barrier rib structure is preferably formed to have a height or thickness of 3 to 20 μm, preferably 3 to 15 μm, and more preferably 3 to 12 μm.

The display device may include a liquid crystal display device, an organic light emitting diode, a flexible display, and the like, but is not limited thereto, and all display devices known in this field that can be applied may be exemplified.

In order to prepare a color conversion barrier rib, a method commonly used in the art can be applied without particular limitation by using the composition for forming a barrier rib according to the present invention,

For example, the barrier rib may be formed by applying the above-described composition on one surface of a substrate and forming a cured film through photocuring and developing processes. The color conversion pixel and the color conversion panel barrier rib structure for distinguishing the pixel may be formed using a photolithography process.

Specifically, each photosensitive resin composition is applied on one surface of a substrate to form a barrier rib, and then volatile components such as a solvent are removed by heating and drying to obtain a smooth cured film.

The coating method of the composition is not particularly limited, and examples thereof include spin coating, cast coating method, roll coating method, slit and spin coating or slit coating method.

After applying the composition, heat drying (pre-baking, pre-baking) is performed, or drying under reduced pressure is followed by heating to volatilize volatile components such as solvents. The heating temperature may be typically 70 to 150 °C, preferably 80 to 130 °C, but is not limited thereto.

In order to form a target pattern on the thus formed coating film, ultraviolet rays are irradiated through a mask so that the portion irradiated with ultraviolet rays is cured. At this time, it is preferable to use a device such as a mask aligner or a stepper to uniformly irradiate parallel rays to the entire exposed portion and to adjust the positions of the mask and the cured film substrate to be precisely aligned. As the ultraviolet rays, g-rays (wavelength: 436 nm), h-rays, i-rays (wavelength: 365 nm), etc. may be used, and the amount of ultraviolet radiation may be appropriately selected as needed.

A cured film of a target pattern can be formed by contacting the cured coating film with a developer to dissolving the unexposed portion and developing.

The cured film formed in this way can be cured harder than the cured product through an additional heat curing process (post-baking, post-calcination), in this case, the heating temperature may be 90 to 180 ℃, and the heating time is 5 to 180 minutes , preferably 15 to 90 minutes, but is not limited thereto.

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

However, the following examples are provided to explain the present invention in more detail, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

In addition, "%" and "part" indicating the content below are based on weight unless otherwise specified.

Synthesis Example: Synthesis of alkali-soluble resin and dispersion resin

277 g of methoxybutyl acetate was put into a detachable flask with an internal volume of 1 liter, and the temperature was raised to 80 301 g of a mixture of 4-epoxytricyclo[5.2.1.0(2,6)]decan-8-ylacrylate in a molar ratio of 50:50, 49 g of methacrylic acid, and 23 g of azobisdimethylvaleronitrile The mixed solution dissolved in 350 g of methoxybutyl acetate was dripped over 5 hours, and the alkali-soluble resin and dispersion resin [solid content (NV) 35.0 weight%] were obtained by aging for 3 hours.

<Production of photosensitive resin composition>

With reference to the compositions and parts by weight described in Tables 1 and 2 below, colorants and photosensitive resin compositions according to Examples and Comparative Examples were prepared.

(A) Colorant component (wt%) white pigment dispersion resin dispersant solvent total content 15 3.00 2.50 79.5 100.0

(weight%) Example comparative example One 2 3 4 5 6 7 8 One 2 3 4 (A) Colorant 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 UV
absorbent B-1 0.5 - - - - - - 3.0 - - - - B-2 - 0.5 - - - - - - - - - - B-3 - - 0.5 - - - - - - - - - B-4 - - - 0.5 1.2 1.2 0.2 - - - - - B-5 - - - - - - - - - - 0.5 - B-6 - - - - - - - - - - - 0.5 Alkali-soluble resin 8.5 8.5 8.5 8.5 8.2 9.4 8.6 7.5 8.7 8.8 8.5 8.5 photopolymerizable compound 8.5 8.5 8.5 8.5 8.2 9.4 8.6 7.5 8.7 8.8 8.5 8.5 photopolymerization initiator 0.5 0.5 0.5 0.5 0.5 0.6 0.5 0.5 0.5 0.2 0.5 0.5 epoxy compound 3.4 3.4 3.4 3.4 3.3 - 3.5 2.9 3.5 3.6 3.4 3.4 additive 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 solvent 75 75 75 75 75 75 75 75 75 75 75 75 total amount 100 100 100 100 100 100 100 100 100 100 100 100

- White pigment: TiO2 (Ti-Pure R-101, Dupont)

- Dispersion resin: resin of synthetic example

- Dispersant: DISPERBYK-2000

- B-1: Tinuvin 326 (benzotriazole-based UV absorber, Basf Corporation)

- B-2: Tinuvin 328 (benzotriazole-based UV absorber, Basf Corporation)

- B-3: Tinuvin 479 (triazine-based UV absorber, Basf)

- B-4: Tinuvin 928 (benzotriazole-based UV absorber, Basf Corporation)

- B-5: Chimassorb 90 (benzophenone-based UV absorber, Basf)

- B-6: Tinuvin 5100 (HALS-based UV absorber, Basf)

- Alkali-soluble resin: Synthetic resin

- Photopolymerizable monomer: Dipentaerythritol pentaacrylate/Dipentaerythritol hexaacrylate (A9570NS, Shin-Nakamura)

- Photoinitiator: OXE-03 (basf)

- Epoxy compound: Celloxide 2021P (Dacel)

- Solvent: propylene glycol monomethyl ether acetate (PGMEA)

- Additive: F554 (DIC)

<Experimental example>

(1) Preparation of a barrier rib pattern cured film

A 5 cm × 5 cm glass substrate (Corning) was washed with a neutral detergent and water, and then dried. Each of the photosensitive resin compositions according to Examples and Comparative Examples was spin-coated on the glass substrate to a final film thickness of 10 μm, pre-baked at 80° C., and dried for 2 minutes to remove the solvent. Thereafter, a mask including a line/space pattern of 1 to 100 μm and a rectangular pattern with a width of 1 to 200 μm having a barrier rib of 1 to 100 μm between the patterns is exposed at an illuminance of 25,000 mW with an exposure dose of 100 mJ/cm ² , An aqueous alkali solution was used to remove the unexposed portion. The prepared cured film was then baked at 180° C. for 30 minutes to prepare a barrier rib pattern cured film having a thickness of 10 μm.

The properties of the prepared barrier rib pattern cured film were evaluated according to the following evaluation criteria, and the results are shown in Table 3 below.

(2) Residual film/residue characteristic evaluation

The surface of the cured film of the barrier rib pattern prepared from the photosensitive resin composition according to Examples and Comparative Examples was observed using an optical microscope, and the residual film/residue characteristic evaluation criteria shown in FIG. 1 were evaluated, and the results are shown in Table 3 below. indicated.

<Residual film/residue evaluation criteria>

○: No residual film/residue

△: residue generation

X: residual film

In addition, 30 mW (KarlSuss Mask Aligner), 600 mW (Canon, MPA 600 super), 25,000 mW (Canon, MPA-7500) for the cured film of the barrier rib pattern prepared with the photosensitive resin composition according to Example 1 and Comparative Example 1 CF) and 45,000 mW (Canon, MPA-8500 CF) conditions were exposed to high illuminance to check whether residual films/residues were generated, and are shown in Table 4 below.

(3) Taper characteristics evaluation

A line pattern of 100 μm was cut out of the cured film of the barrier rib pattern prepared by using the photosensitive resin composition prepared according to the above Examples and Comparative Examples, and cross-section using a scanning electron microscope (SEM, SU-8100, manufactured by Hitachi) was observed. As shown in FIG. 2 , the difference between the maximum line width (a) and the minimum line width (b) length in the cross section was calculated and evaluated according to the following evaluation criteria.

<Taper characteristics evaluation criteria>

◎: 10 μm or less

○: more than 10, 20 μm or less

△: more than 20, 30 μm or less

X: more than 30 μm

(4) Evaluation of swelling characteristics

After the cured film made of the photosensitive resin composition according to the above Examples and Comparative Examples was post-fired at 180 ° C., 30 minutes, 85 ° C., and 60 minutes, respectively, white-ink was added dropwise inside the cured film and left for 30 minutes, followed by a pattern It was checked whether swelling stains occurred on the surface.

<Swelling evaluation criteria>

○: No swelling

△: Swelling drug generation

X: Swelling strength

remnant/residue taper characteristics
(line width difference) swelling
(180℃, 30min) swelling
(85℃, 60min) Example 1 ○ ◎ ○ ○ Example 2 ○ ◎ ○ ○ Example 3 ○ ○ ○ ○ Example 4 ○ ○ ○ ○ Example 5 ○ ◎ ○ ○ Example 6 ○ ◎ ○ △ Example 7 △ ○ ○ ○ Example 8 ○ △ △ △ Comparative Example 1 X △ ○ ○ Comparative Example 2 △ X △ X Comparative Example 3 X X ○ ○ Comparative Example 4 X X ○ ○

leftover/remnant 30mW 600mW 25000mW 45000mW Example 1 ○ ○ ○ ○ Comparative Example 1 ○ X X X

Referring to Tables 3 and 4, the cured film of the barrier rib pattern prepared by using the photosensitive resin composition according to the embodiment can prevent the generation of residual films and residues during high-intensity exposure, and the difference in the line width of the taper is small, so the taper The shape is excellent, problems such as undercut may occur, and the effect of excellent swelling characteristics may also be confirmed.

On the other hand, when the UV absorber according to the present invention is not included (Comparative Examples 1 and 2), or contains a UV absorber other than the benzotriazole-based or triazine-based UV absorber (Comparative Examples 3 and 4), high-intensity exposure Residual films and residues occurred during the process, and the difference in the line width of the taper was also large, so there was a problem of defective taper shape and undercut generation, and it was confirmed that the swelling characteristics were also inferior to those of the embodiment.

Claims (13)

(A) a colorant containing a white pigment, (B) a UV absorber, (C) an alkali-soluble resin, (D) a photopolymerizable compound, (E) a photopolymerization initiator, and (F) a solvent. ,
The UV absorber comprises any one or more of a benzotriazole-based or triazine-based UV absorber, the photosensitive resin composition for forming a barrier rib.
The method according to claim 1,
The photosensitive resin composition for forming barrier ribs, characterized in that the white pigment has an average particle size of 150 to 400 nm.
The method according to claim 1,
The white pigment comprises titanium oxide (TiO ₂ ), the photosensitive resin composition for forming a barrier rib.
4. The method of claim 3,
The titanium oxide (TiO ₂ ) is characterized in that its surface is surface-treated with at least one selected from the group consisting of silicon oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), zirconium oxide (ZrO ₂ ) and organic materials. The photosensitive resin composition for barrier rib formation.
The method according to claim 1,
The (A) colorant further comprises at least one pigment selected from the group consisting of a black pigment, a red pigment, a yellow pigment and a blue pigment, the photosensitive resin composition for forming a barrier rib.
The method according to claim 1,
The photosensitive resin composition for forming barrier ribs, characterized in that the white pigment is included in an amount of 1 to 30% by weight based on the total weight of the colorant (A) of the photosensitive resin composition.
The method according to claim 1,
The photosensitive resin composition for forming a barrier rib, characterized in that the UV absorber is included in an amount of 0.05 to 10% by weight based on the total weight of the solid content of the photosensitive resin composition for forming the barrier rib.
The method according to claim 1,
The (C) alkali-soluble resin is characterized in that it contains any one or more of a cardo-based resin or an acrylic resin, the photosensitive resin composition for forming a barrier rib.
The method according to claim 1,
The photosensitive resin composition for partition formation, characterized in that it further comprises an epoxy compound.
10. The method of claim 9,
The epoxy compound is an alicyclic epoxy compound, characterized in that the photosensitive resin composition for forming a barrier rib.
The method according to claim 1,
A photosensitive resin composition for forming barrier ribs further comprising at least one selected from the group consisting of fillers, polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, and anti-aggregation agents.
A barrier rib structure made of the photosensitive resin composition for forming a barrier rib according to any one of claims 1 to 11.
A display device including the barrier rib structure of claim 12 .

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