Colored photosensitive resin composition and multilayer cured film prepared therefrom

Abstract

To provide a colored photosensitive resin composition, and a multilayer curable film prepared from the same.SOLUTION: A colored photosensitive resin composition has an excellent reflectance RSCI measured by an SCI (including regularly reflected light) method, reflectance RSCE measured by an SCE (not including regularly reflected light), and ratio (RSCE / RSCI) therebetween while maintaining excellent resolution, visibility and / or the like, and has a uniform film in an appropriate range. The composition can be formed on a multilayer curable film satisfying physical characteristics such as high reflectance and high light-shielding property at the same time. In addition, when the curable film is formed from the composition, a pattern can be formed on a multilayer film through a single development process. Therefore, the composition can be advantageously used for a quantum dot display device.SELECTED DRAWING: Figure 5

Description

[Technical Field]

[0001] The present invention relates to a colored photosensitive resin composition having excellent light-shielding properties and reflectivity applicable as a quantum dot barrier rib, and to a multilayer cured film for quantum dot barrier ribs prepared from this composition. [Background technology]

[0002] In recent years, there has been growing interest in various electronic devices that utilize quantum dots (QDs).

[0003] Quantum dots are materials that exhibit quantum confinement effects as nanocrystals of semiconductor material with a diameter of approximately 10 nm or less. These quantum dots are composed of hundreds of thousands of electrons, but most are tightly bound to the atomic nucleus, resulting in a limited number of unbound free electrons, approximately 1 to 100. In such cases, the electron energy levels are discontinuously restricted, exhibiting different electrical and optical properties compared to semiconductors in a bulk state that form a continuous band. These quantum dots can produce various colors by generating light wavelengths of different lengths for each particle size, even without changing the material type. Because of their advantages in high color purity and photosafety compared to conventional light-emitting materials, quantum dots are currently used in various fields such as displays, solar cells, biosensors, and lighting, and are attracting attention as next-generation light-emitting devices.

[0004] Figure 1 is a schematic diagram illustrating a typical quantum dot device. Referring to Figure 1, the substrate structure (100) of this quantum dot device includes a transparent substrate (110) and barrier ribs (120) formed on the substrate (110) to divide areas. Within each divided area are different quantum dot solutions (i.e., a first quantum dot solution (130), a second quantum dot solution (140), and a third quantum dot solution (150)). The first quantum dot solution (130), the second quantum dot solution (140), and the third quantum dot solution (150) consist of quantum dots with different energy levels. That is, these quantum dot solutions are configured to have different emission wavelength bands when the size or material of the quantum dots is manipulated.

[0005] Generally, the barrier ribs (120) described above can be formed as a cured film from a photosensitive resin composition. The barrier ribs (120) should function as a partitioning separator (or blocking) so as to prevent the mixing of the respective color compositions that have flowed into the partitioned areas. In addition, the barrier ribs (120) should be able to prevent deterioration of contrast and color purity caused by light leakage from light sources such as colored OLEDs. Therefore, in recent years, there has been a demand for cured films that have high reflectivity and light-shielding properties.

[0006] In addition, for application to quantum dot devices, it is necessary to achieve a uniform film and appropriate film thickness to maintain excellent resolution. For example, if the film is not uniform or the film thickness is excessively small, the film is not suitable for the barrier ribs, and therefore the quantum dot solution may overflow the barrier ribs, resulting in color mixing or a deterioration of resolution due to insufficient color purity. If the film thickness is adjusted by thickly coating and curing the photosensitive resin composition to solve this problem, it is difficult to achieve a uniform coating, and therefore there is a problem that dirt or contamination may occur. [Prior art documents]

Patent Document

[0007]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0008] An object of the present invention is to provide a colored photosensitive resin composition having high light shielding properties and high reflectivity while maintaining excellent resolution and pattern characteristics, and a multilayer cured film prepared therefrom.

Means for Solving the Problems

[0009] The present invention provides a colored photosensitive resin composition comprising (A) a copolymer, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a colorant. When the copolymer (A) contains the first copolymer (A1), the colorant (D) contains a white colorant (D1). When the copolymer (A) contains the second copolymer (A2), the colorant (D) contains a colorant other than white (D2). The first copolymer (A1) includes structural units derived from (a1) an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a combination thereof; (a2) structural units derived from an ethylenically unsaturated compound containing an aromatic ring; (a3) structural units derived from an ethylenically unsaturated compound containing an epoxy group; and (a4) structural units derived from an ethylenically unsaturated compound different from (a1) to (a3). The second copolymer (A2) includes structural units derived from (b1) an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a combination thereof; (b2) structural units derived from an ethylenically unsaturated compound containing an epoxy group; and (b3) structural units derived from an ethylenically unsaturated compound containing fluorine; and at least one of (b4) structural units derived from an ethylenically unsaturated compound different from (b1) to (b3).

[0010] To achieve another objective, the present invention provides a multilayer cured film comprising a first cured film formed from a first colored photosensitive resin composition and a second cured film formed from a second colored photosensitive resin composition, wherein the first colored photosensitive resin composition comprises (A1) a first copolymer; (B) a photopolymerizable compound; (C) a photopolymerization initiator; and (D1) a white colorant, the second colored photosensitive resin composition comprises (A2) a second copolymer; (B) a photopolymerizable compound; (C) a photopolymerization initiator; and (D2) a colorant other than white, and the multilayer cured film has a total thickness of 6 μm or more.

[0011] To achieve yet another objective, the present invention provides a process for preparing a multilayer cured film, comprising: (1) coating a substrate with a first colored photosensitive resin composition and curing it to form a first cured film; (2) coating a second colored photosensitive resin composition on the first cured film and curing it to form a second cured film; and (3) exposing and developing the second cured film to form a pattern and then post-baking it, wherein the first colored photosensitive resin composition comprises (A1) a first copolymer; (B) a photopolymerizable compound; (C) a photopolymerization initiator; and (D1) a white colorant, the second colored photosensitive resin composition comprises (A2) a second copolymer; (B) a photopolymerizable compound; (C) a photopolymerization initiator; and (D2) a colorant other than white, and the multilayer cured film having a total thickness of 6 μm or more.

[0012] Advantageous effects of the invention The colored photosensitive resin composition of the present invention maintains excellent resolution, visibility, and similar properties, while its reflectance R, as measured by the SCI (including specular reflection) method, is excellent. SCI The reflectance R was measured by the SCE (Specular Reflection-Free) method. SCE and the ratio between them (R SCE / R SCIThis composition exhibits excellent properties and has a uniform film thickness within an appropriate range. Therefore, it can be formed into a multilayer cured film that simultaneously satisfies physical properties such as high reflectivity and high light shielding. In addition, when a cured film is formed from this composition, it is possible to form a pattern on the multilayer film in a single development process. Therefore, this composition can be advantageously used for quantum dot display devices. [Brief explanation of the drawing]

[0013] [Figure 1] This is a schematic diagram illustrating a typical quantum dot device. [Figure 2] This is a schematic diagram of a multilayer cured film including a two-layer cured film according to an embodiment of the present invention. [Figure 3] This is a schematic diagram of a multilayer cured film including a three-layer cured film according to another embodiment of the present invention. [Figure 4] This is a schematic diagram of a multilayer cured film including an n+1 layer cured film according to yet another embodiment of the present invention. [Figure 5] The images show cross-sectional and side views of the multilayer cured films of Examples 3-14 as observed with an optical microscope. [Figure 6] These are photographs of the cross-section and side view of the multilayer cured films of Comparative Examples 1-9, observed with an optical microscope. [Modes for carrying out the invention]

[0014] The present invention is not limited to what is described below. Rather, it can be modified in various forms, as long as the spirit of the invention is not altered. The present invention may include the following embodiments 1 to 19. [Aspect 1] A colored photosensitive resin composition, (A) Copolymer; (B) Photopolymerizable compound; (C) Photopolymerization initiator; and (D) Coloring agent Includes, If the copolymer (A) includes a first copolymer (A1), the coloring agent (D) includes a white coloring agent (D1). If the copolymer (A) includes a second copolymer (A2), the coloring agent (D) includes a coloring agent other than white (D2). The first copolymer (A1) comprises (a1) structural units derived from ethylenically unsaturated carboxylic acids, ethylenically unsaturated carboxylic acid anhydrides, or combinations thereof; (a2) structural units derived from ethylenically unsaturated compounds containing aromatic rings; (a3) ​​structural units derived from ethylenically unsaturated compounds containing epoxy groups; and (a4) structural units derived from ethylenically unsaturated compounds different from (a1) to (a3), and The second copolymer (A2) is a colored photosensitive resin composition comprising (b1) structural units derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a combination thereof; (b2) structural units derived from an ethylenically unsaturated compound containing an epoxy group, and (b3) structural units derived from an ethylenically unsaturated compound containing fluorine; and (b4) at least one structural unit derived from an ethylenically unsaturated compound different from (b1) to (b3). [Aspect 2] The aforementioned white coloring agent (D1) is titanium dioxide (TiO 2 ), zirconium oxide (ZrO 2 ), zinc oxide (ZnO) and silicon dioxide (SiO 2 A colored photosensitive resin composition according to embodiment 1, which is at least one selected from the group consisting of ). [Aspect 3] The colored photosensitive resin composition according to Embodiment 1, wherein the white coloring agent (D1) is used in an amount of 20 to 65 parts by weight (based on solid content) per 100 parts by weight of the first copolymer (A1). [Aspect 4] The colored photosensitive resin composition according to Embodiment 1, wherein the white coloring agent (D1) has a particle size of 120 nm to 400 nm. [Aspect 5] The colored photosensitive resin composition according to Embodiment 1, wherein the coloring agent other than white (D2) is at least one selected from the group consisting of yellow coloring agents, purple coloring agents, red coloring agents, orange coloring agents, blue coloring agents, and black coloring agents. [Aspect 6] The colored photosensitive resin composition according to Embodiment 1, wherein the coloring agent other than white (D2) is used in an amount of 3 to 30 parts by weight (based on solid content) per 100 parts by weight of the second copolymer (A2). [Aspect 7] The coloring agent other than white (D2) has a particle size of 50 nm to 200 nm, as described in Embodiment 1 of the colored photosensitive resin composition. [Aspect 8] The colored photosensitive resin composition according to embodiment 1, further comprising at least one additive selected from the group consisting of epoxy compounds, photobase generators, thiol compounds, compounds derived from epoxy resins, and adhesion aids. [Aspect 9] A multilayer cured film comprising a first cured film formed from a first colored photosensitive resin composition and a second cured film formed from a second colored photosensitive resin composition, The first colored photosensitive resin composition comprises (A1) a first copolymer; (B) a photopolymerizable compound; (C) a photopolymerization initiator; and (D1) a white coloring agent. The second colored photosensitive resin composition comprises (A2) a second copolymer; (B) a photopolymerizable compound; (C) a photopolymerization initiator; and (D2) a colorant other than white, and The multilayer cured film is a multilayer cured film having a total thickness of 6 μm or more. [Aspect 10] The reflectance R of the aforementioned multilayer cured film was measured by the SCI (including specular reflection) method. SCI and reflectance R measured by the SCE (non-specular reflection) method. SCE The relationships are as follows: (Relationship 1) 50% ≤ R SCI (Relationship 2) 40% ≤ R SCE (Relationship 3) 50% ≤ R SCE / R SCI A multilayer cured film according to embodiment 9 that satisfies the requirements. [Aspect 11] The multilayer cured film according to embodiment 9, wherein the first cured film and the second cured film each have a thickness of 10 μm or less. [Aspect 12] The multilayer cured film according to embodiment 11, wherein the second cured film is composed of multiple layers. [Aspect 13] The multilayer cured film according to embodiment 12, wherein the second cured film is composed of 2 to 10 layers. [Aspect 14] A multilayer cured film according to embodiment 9, having a total thickness of 6 μm to 20 μm. [Aspect 15] A multilayer cured film according to embodiment 9, used as a structure for quantum dot barrier ribs. [Aspect 16] A process for preparing a multilayer cured film, (1) Coating a first colored photosensitive resin composition onto a substrate and curing it to form a first cured film; (2) Coating the first cured film with a second colored photosensitive resin composition and curing it to form a second cured film; and (3) Exposing and developing the second cured film to form a pattern, and then post-baking it. Includes, The first colored photosensitive resin composition comprises (A1) a first copolymer; (B) a photopolymerizable compound; (C) a photopolymerization initiator; and (D1) a white coloring agent. The second colored photosensitive resin composition comprises (A2) a second copolymer; (B) a photopolymerizable compound; (C) a photopolymerization initiator; and (D2) a colorant other than white, and The process for the multilayer cured film having a total thickness of 6 μm or more. [Aspect 17] A process for preparing a multilayer cured film according to embodiment 16, wherein the curing in steps (1) and (2) is performed at 70 to 140°C for 50 to 900 seconds. [Aspect 18] The curing process is a process for preparing a multilayer cured film according to embodiment 17, comprising a pre-bake at 70-100°C for 50-400 seconds and a mid-bake at 80-140°C for 100-500 seconds. [Aspect 19] The post-baking in step (3) is performed at 150 to 300°C for 10 to 60 minutes, a process for preparing a multilayer cured film according to embodiment 16. .

[0015] Throughout this specification, where a part is referred to as "containing" a certain element, unless otherwise specified, it should be understood that other elements may be included, rather than being excluded. In addition, all figures and expressions relating to the quantities of ingredients, reaction conditions, and similar matters used herein should be understood to be modified by the term "approximately" unless otherwise specified.

[0016] The present invention relates to a colored photosensitive resin composition comprising (A) copolymer; (B) photopolymerizable compound; (C) photopolymerization initiator; and (D) colorant, wherein if copolymer (A) comprises a first copolymer (A1), colorant (D) comprises a white colorant (D1); and if copolymer (A) comprises a second copolymer (A2), colorant (D) comprises a colorant other than white (D2); and the first copolymer (A1) comprises (a1) structural units derived from ethylenically unsaturated carboxylic acids, ethylenically unsaturated carboxylic acid anhydrides, or combinations thereof; (a2) structural units derived from ethylenically unsaturated compounds containing aromatic rings; and (a3) ​​epoxy groups. The present invention provides a colored photosensitive resin composition comprising: a structural unit derived from an ethylenically unsaturated compound; and (a4) a structural unit derived from an ethylenically unsaturated compound different from (a1) to (a3); and the second copolymer (A2) comprising (b1) a structural unit derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a combination thereof; and (b2) a structural unit derived from an ethylenically unsaturated compound containing an epoxy group, and (b3) a structural unit derived from an ethylenically unsaturated compound containing fluorine; and (b4) at least one structural unit derived from an ethylenically unsaturated compound different from (b1) to (b3).

[0017] Specifically, this colored photosensitive resin composition may be a first colored photosensitive resin composition comprising a first copolymer (A1); a photopolymerizable compound (B); a photopolymerization initiator (C); and a white coloring agent (D1). In addition, this colored photosensitive resin composition may be a second colored photosensitive resin composition comprising a second copolymer (A1); a photopolymerizable compound (B); a photopolymerization initiator (C); and a coloring agent other than white (D2).

[0018] [First colored photosensitive resin composition] The first colored photosensitive resin composition may comprise (A1) a first copolymer; (B) a photopolymerizable compound; (C) a photopolymerization initiator; and (D1) a white colorant. The first colored photosensitive resin composition may optionally further comprise (E) a surfactant, (F) an additive, such as an epoxy compound, a thiol compound, a photobase generator, and an adhesion aid, and / or (G) a solvent.

[0019] A first cured film can be formed from a first colored photosensitive resin composition. The first cured film is formed by coating it onto a substrate. Since the first cured film contains the following components, the first cured film can satisfy high reflectivity characteristics.

[0020] The following sections will explain each component in detail.

[0021] In the following, the term "(meth)acrylic" refers to "acrylic" and / or "methacrylic," and the term "(meth)acrylate" refers to "acrylate" and / or "methacrylate."

[0022] The weight-average molecular weight (g / mol or Da) of each component described below was measured by gel permeation chromatography (GPC, eluate: tetrahydrofuran) using a polystyrene standard as the reference.

[0023] (A1) First copolymer The first copolymer (A1) includes (a1) structural units derived from ethylenically unsaturated carboxylic acids, ethylenically unsaturated carboxylic acid anhydrides, or combinations thereof; (a2) structural units derived from ethylenically unsaturated compounds containing aromatic rings; (a3) ​​structural units derived from ethylenically unsaturated compounds containing epoxy groups; and (a4) structural units derived from ethylenically unsaturated compounds different from (a1) to (a3).

[0024] The first copolymer is an alkali-soluble resin for developing properties and functions as a binder in this composition. Specifically, since the first copolymer contains both an aromatic ring and an epoxy group in its structure, the cured film, once formed, can serve as a base after the composition is coated and as a structure for executing the final pattern.

[0025] (a1) Structural units derived from ethylenically unsaturated carboxylic acids, ethylenically unsaturated carboxylic acid anhydrides, or combinations thereof The structural unit (a1) may be derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a combination thereof.

[0026] Ethylene-unsaturated carboxylic acids and ethylenically unsaturated carboxylic acid anhydrides can be polymerizable unsaturated monomers containing at least one carboxyl group in the molecule. Examples include: unsaturated monocarboxylic acids, e.g., (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; unsaturated dicarboxylic acids and their anhydrides, e.g., maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid; unsaturated polycarboxylic acids with a valency of 3 or more and their anhydrides; and mono[(meth)acryloyloxyalkyl] esters of polycarboxylic acids with a valency of 2 or more, e.g., mono[2-(meth)acryloyloxyethyl]succinate, mono[2-(meth)acryloyloxyethyl]phthalate, and the like.

[0027] Among the above, structural units derived from unsaturated monocarboxylic acids (for example, structural units derived from (meth)acrylic acid) are preferred from the viewpoint of developability and polymerizability. Structural units derived from the compounds exemplified above may be contained in this copolymer alone or in combination of two or more.

[0028] The content of structural unit (a1) may be 5-65 mol%, 10-65 mol%, 10-50 mol%, 10-40 mol%, 10-35 mol%, or 15-35 mol%, based on the total number of moles of structural units constituting the first copolymer. Within the above range, structural unit (a1) may have favorable developability.

[0029] (a2) Structural units derived from ethylenically unsaturated compounds containing aromatic rings The structural unit (a2) may originate from an ethylenically unsaturated compound containing an aromatic ring.

[0030] Specific examples of ethylenically unsaturated compounds containing aromatic rings include: phenyl (meth)acrylate, benzyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, p-nonylphenoxypolyethylene glycol (meth)acrylate, p-nonylphenoxypolypropylene glycol (meth)acrylate, tribromophenyl (meth)acrylate; styrene; styrene containing alkyl substituents, such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, and hexylstyrene. , heptylstyrene and octylstyrene; halogen-containing styrenes, such as fluorostyrene, chlorostyrene, bromostyrene and iodostyrene; alkoxy substituent-containing styrenes, such as methoxystyrene, ethoxystyrene and propoxystyrene; 4-hydroxystyrene, p-hydroxy-α-methylstyrene, acetylstyrene; and vinyltoluene, divinylbenzene, vinylphenol, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl ether, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether and the like.

[0031] The structural units derived from the compounds exemplified above may be included in the copolymer individually or in combination of two or more. Among these examples, structural units derived from styrene compounds are preferred for the polymerizability of the composition. These structural units can adjust the reactivity of the first copolymer and increase its solubility in alkaline aqueous solutions, thereby significantly improving the coating properties of the composition.

[0032] The content of structural unit (a2) may be 1 to 70 mol%, 1 to 60 mol%, 1 to 50 mol%, 1 to 45 mol%, or 3 to 45 mol%, based on the total number of moles of structural units constituting the first copolymer. Within the above range, structural unit (a2) is more advantageous in terms of chemical resistance.

[0033] (a3) Structural units derived from ethylenically unsaturated compounds containing epoxy groups The structural unit (a3) ​​may originate from an ethylenically unsaturated compound containing an epoxy group.

[0034] Specific examples of ethylenically unsaturated compounds containing epoxy groups include: glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 4,5-epoxypentyl (meth)acrylate, 5,6-epoxyhexyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, 2,3-epoxycyclopentyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, α-ethylglycidyl acrylate, α- n-propylglycidyl acrylate, α-n-butylglycidyl acrylate, N-(4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl)acrylamide, N-(4-(2,3-epoxypropoxy)-3,5-dimethylphenylpropyl)acrylamide, 4-hydroxybutyl (meth)acrylate glycidyl ether, 4-hydroxybutyl acrylate glycidyl ether, allyl glycidyl ether, 2-methylallyl glycidyl ether, and similar compounds. Structural units derived from the compounds exemplified above may be included in this copolymer alone or in combination of two or more.

[0035] Among the above, at least one selected from structural units derived from glycidyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether, and 4-hydroxybutyl (meth)acrylate glycidyl ether is more preferred from the viewpoint of improving polymerizability and the strength of the cured film. Specifically, this enables the formation of a structure by a crosslinking reaction (i.e., the formation of a cured film with sufficient film strength). Furthermore, this can impart chemical resistance to the cured film. In addition, this makes it possible to adjust the pattern fluidity of the composition during curing while maintaining sufficient film base strength, thereby enabling the formation of patterns on the cured film and improving the bonding strength with the underlying material.

[0036] The content of structural unit (a3) ​​may be 1 mol% to 40 mol%, 1 mol% to 30 mol%, 1 mol% to 20 mol%, 1 mol% to 10 mol%, 5 mol% to 30 mol%, 5 mol% to 20 mol%, 5 mol% to 15%, or 5 mol% to 12 mol%, based on the total number of moles of structural units constituting the first copolymer. Within the above range, structural unit (a3) ​​may be more advantageous in terms of process residue and pre-bake margin.

[0037] (a4) Structural units derived from ethylenically unsaturated compounds different from (a1) to (a3) Structural unit (a4) may include structural units derived from ethylenically unsaturated compounds different from (a1) to (a3).

[0038] Specific examples of structural units derived from ethylenically unsaturated compounds different from structural units (a1) to (a3) ​​include: unsaturated carboxylic acid esters, e.g., methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, cyclohexyl (meth)acrylate, ethylhexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, hydroxyethyl (meth)acrylate. , 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerol (meth)acrylate, methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, propyl α-hydroxymethyl acrylate, butyl α-hydroxymethyl acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxytriethyl Poly(ethylene glycol) methyl ether (meth)acrylate, trifluoroethyl (meth)acrylate, trifluoro(meth)acrylate, tetrafluoropropyl (meth)acrylate, hexafluoroisopropyl (meth)acrylate, octafluoropentyl (meth)acrylate, heptadecafluorodecyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclo Pentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate and dicyclopentenyloxyethyl (meth)acrylate; tertiary amines containing an N-vinyl group, such as N-vinylpyrrolidone, N-vinylcarbazole and N-vinylmorpholine; unsaturated ethers, such as vinyl methyl ether and vinyl ethyl ether; unsaturated imides, such as N-phenylmaleimide, N-(4-chlorophenyl)maleimide, N-(4-hydroxyphenyl)maleimide, N-cyclohexylmaleimide and the like.The structural units derived from the compounds exemplified above may be included in this copolymer individually or in combination of two or more.

[0039] Among the above, at least one structural unit derived from an unsaturated carboxylic acid ester and a saturated imide (for example, a structural unit derived from methyl (meth)acrylate and N-phenylmaleimide) is more preferred from the viewpoint of improving polymerizability and the strength of the cured film.

[0040] The content of structural unit (a4) may be 1 to 80 mol%, 10 to 80 mol%, 10 to 70 mol%, 10 to 60 mol%, 10 to 55 mol%, 20 to 50 mol%, or 20 to 55 mol%, based on the total number of moles of structural units constituting the first copolymer. Within the above range, the storage stability of the composition can be maintained, and the film retention rate can be more advantageously improved.

[0041] According to one embodiment, examples of a first copolymer having structural units (a1) to (a4) include: a copolymer of (meth)acrylic acid / styrene / glycidyl (meth)acrylate / methyl (meth)acrylate, a copolymer of (meth)acrylic acid / styrene / 4-hydroxybutyl acrylate glycidyl ether / methyl (meth)acrylate, a copolymer of (meth)acrylic acid / styrene / glycidyl (meth)acrylate / N-phenylmaleimide, a copolymer of (meth)acrylic acid / styrene / glycidyl (meth)acrylate / N-cyclohexylmaleimide, and a copolymer of (meth)acrylic acid / styrene / 4-hydroxybutyl acrylate glycidyl ether / N-phenylmaleimide.

[0042] The first copolymer (A1) may include (a1) structural units derived from methacrylic acid; (a2) structural units derived from styrene; (a3) ​​structural units derived from glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether or mixtures thereof; and (a4) structural units derived from methyl methacrylate, N-phenylmaleimide or mixtures thereof.

[0043] The first copolymer may have a weight-average molecular weight (Mw) of 4,000-20,000 Da, 4,000-15,000 Da, 5,000-20,000 Da, 5,000-15,000 Da, or 10,000-15,000 Da. Within the above range, a favorable pattern profile during development may be obtained, and properties such as film retention and chemical resistance may be improved.

[0044] The first copolymer (A) can be prepared by filling a reactor with monomers from which the above structural units (a1) to (a4) may be derived, a radical polymerization initiator, and a solvent, followed by filling with nitrogen, and polymerizing the mixture by gently stirring.

[0045] Radical polymerization initiators may be, but are not limited to, azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile); or benzoyl peroxides, lauryl peroxides, t-butyl peroxypivalate, 1,1-bis(t-butylperoxy)cyclohexane, or similar. Radical polymerization initiators may be used alone or in combination of two or more.

[0046] The solvent can be any conventional solvent commonly used in the preparation of copolymers, such as propylene glycol monomethyl ether acetate (PGMEA).

[0047] (B) Photopolymerizable compound The first colored photosensitive resin composition may contain a photopolymerizable compound as described below. This photopolymerizable compound may be a monofunctional ester compound or a polyfunctional ester compound having at least one ethylenically unsaturated double bond. In particular, from the viewpoint of chemical resistance, this photopolymerizable compound may be a polyfunctional compound having at least two functional groups.

[0048] Photopolymerizable compounds include dipentaerythritol hexaacrylate, di(trimethylolpropane)tetraacrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, monoester of pentaerythritol tri(meth)acrylate and succinic acid, and penta The following may be selected, but are not limited, from the group consisting of erythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, monoester of dipentaerythritol penta(meth)acrylate and succinic acid, pentaerythritol triacrylate-hexamethylene diisocyanate (reaction product of pentaerythritol triacrylate and hexamethylene diisocyanate), tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, bisphenol A epoxy acrylate, ethylene glycol monomethyl ether acrylate, and mixtures thereof.

[0049] Examples of commercially available photopolymerizable compounds include: (i) monofunctional (meth)acrylates, such as Aronix M-101, M-111 and M-114 from Toagosei Co., Ltd., KAYARAD T4-110S, T-1420 and T4-120S from Nippon Kayaku Co., Ltd., and V-158 and V-2311 from Osaka Organic Chemical Industry Co., Ltd.; (ii) difunctional (meth)acrylates, such as Aronix M-210, M-240 and M-6200 from Toagosei Co., Ltd., KAYARAD HDDA, HX-220 and R-604 from Nippon Kayaku Co., Ltd., and V-260, V-312 and V-335 HP from Osaka Organic Chemical Industry Co., Ltd.; and (iii) trifunctional or more (meth)acrylates, such as Aronix from Toagosei Co., Ltd. M-309, M-400, M-403, M-405, M-450, M-7100, M-8030, M-8060 and TO-1382, KAYARAD TMPTA, DPHA and DPHA-40H manufactured by Nippon Kayaku Co., Ltd., and V-295, V-300, V-360, V-GPT, V-3PA, V-400 and V-802 manufactured by Osaka Organic Chemical Industry Co., Ltd.

[0050] The content of the photopolymerizable compound may be 10 to 200 parts by weight, 10 to 150 parts by weight, 50 to 150 parts by weight, 70 to 150 parts by weight, 70 to 130 parts by weight, 80 to 150 parts by weight, 80 to 120 parts by weight, 90 to 120 parts by weight, or 90 to 100 parts by weight per 100 parts by weight of the first copolymer (A1), based on the solid content excluding the solvent.

[0051] When the amount of photopolymerizable compound is within the above range, excellent pattern developability and coating properties may be achieved while maintaining a constant film retention rate. If the amount of photopolymerizable compound is below the above range, the development time will be longer, which may affect the process and residue. If the amount of photopolymerizable compound exceeds the above range, a problem of excessively high pattern resolution may occur.

[0052] (C) Photopolymerization initiator The first colored photosensitive resin composition may contain a photopolymerization initiator as described below. This photopolymerization initiator may be any known photopolymerization initiator.

[0053] The photopolymerization initiator may be selected from the group consisting of acetophenone compounds, biimidazole compounds, triazine compounds, onium salt compounds, benzoin compounds, benzophenone compounds, polynuclear quinone compounds, thioxanthone compounds, diazo compounds, imidosulfonate compounds, oxime compounds, carbazole compounds, sulfonium borate compounds, ketone compounds, and mixtures thereof.

[0054] Specifically, the photopolymerization initiator may be an oxime compound, a triazine compound, or a combination thereof. More specifically, a combination of an oxime compound and a triazine compound may be used.

[0055] Specific examples of photopolymerization initiators include 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), benzoyl peroxide, lauryl peroxide, t-butyl peroxypivalate, 1,1-bis(t-butylperoxy)cyclohexane, p-dimethylaminoacetophenone, and 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1- Tanone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, benzophenone, benzoinpropyl ether, diethylthioxanthone, 2,4-bis(trichloromethyl)-6-p-methoxyphenyl-s-triazine, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 9-phenylacridin, 3-methyl-5-amino-((s-triazine-2-yl)amino)-3-phen Lucoumarin, 2-(o-chlorophenyl)-4,5-diphenylimidazoyl dimer, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-[4-(phenylthio)phenyl]-octane-1,2-dione-2-(o-benzoyloxime), o-benzoyl-4'-(benzmercapto)benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenylcarbonyl-diphenylphosphonyl oxide, Examples include, but are not limited to, hexafluorophosphorotrialkylphenylsulfonium salts, 2-mercaptobenzimidazole, 2,2'-benzothiazolyl disulfide, 2-[4-(2-phenylethenyl)phenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholine-4-ylphenyl)-butan-1-one and mixtures thereof.

[0056] For reference, examples of commercially available oxime-based photopolymerization initiators include at least one selected from OXE-01 (BASF), OXE-02 (BASF), OXE-03 (BASF), N-1919 (ADEKA), NCI-930 (ADEKA), NCI-831 (ADEKA), SPI05 (Samyang), SPI02 (Samyang), and SPI03 (Samyang). Examples of triazine-based photopolymerization initiators include (E)-2-(4-styrylphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[4-(2-phenylethenyl)phenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine (Triazine Y,Tronly), and similar products.

[0057] The content of the photopolymerization initiator may be 1 to 20 parts by weight, 1 to 15 parts by weight, 1 to 13 parts by weight, 3 to 20 parts by weight, 3 to 15 parts by weight, or 3 to 13 parts by weight per 100 parts by weight of the first copolymer, based on the solid content excluding the solvent.

[0058] Specifically, per 100 parts by weight of the first copolymer (A1), an oxime compound in an amount of 1 to 20 parts by weight, 1 to 15 parts by weight, 3 to 20 parts by weight, or 3 to 15 parts by weight may be used as a photopolymerization initiator.

[0059] In addition, a triazine compound may be used as a photopolymerization initiator in an amount of 0.05 to 4 parts by weight, 0.5 to 4 parts by weight, 1 to 4 parts by weight, 1 to 3 parts by weight, 1 to 2.5 parts by weight, 1 to 2 parts by weight, or 1 to 1.5 parts by weight per 100 parts by weight of the first copolymer (A1).

[0060] When oxime compounds are used in amounts within the above range, high sensitivity, development characteristics, and coating characteristics can be improved. In addition, when triazine compounds are used in amounts within the above range, a cured film can be obtained that exhibits high sensitivity, as well as excellent chemical resistance and taper angle during pattern formation.

[0061] (D1) White coloring agent The first colored photosensitive resin composition may contain a white coloring agent (D1) to impart high reflectivity.

[0062] The white colorant may be a white metallic colorant. For example, the white colorant may be at least one selected from the group consisting of titanium oxide (TiO2), zirconium oxide (ZrO2), zinc oxide (ZnO), and silicon dioxide (SiO2).

[0063] Because the white colorant has light-reflecting properties, it functions to improve reflectivity when the cured film is formed from the first colored photosensitive resin composition. Specifically, since the white colorant is composed of particles with a high refractive index, almost 100% of the incident light is reflected and scattered, which helps to improve reflectivity. If the colorant particles are colorless and transparent, the light is not absorbed and scattered.

[0064] The content of the white colorant (D1) may be 10 to 80 parts by weight, 10 to 70 parts by weight, 20 to 80 parts by weight, 20 to 70 parts by weight, 20 to 65 parts by weight, 30 to 70 parts by weight, or 30 to 65 parts by weight per 100 parts by weight of the first copolymer (A1), based on the solid content excluding the solvent. Within the above range, the white colorant (D1) can achieve high reflectivity.

[0065] Specifically, the white coloring agent may include, for example, titanium dioxide (TiO2).

[0066] For example, the white coloring agent may contain titanium dioxide (TiO2), which may be used in amounts of 10-80 parts by weight, 10-70 parts by weight, 20-80 parts by weight, 20-70 parts by weight, 20-65 parts by weight, 30-70 parts by weight, or 30-65 parts by weight per 100 parts by weight of the first copolymer (A1), based on the solid content. Within the above ranges, the white coloring agent can achieve high reflectivity.

[0067] The particle size of the white colorant may be 120nm-400nm, 150nm-400nm, 200nm-400nm, 230nm-350nm, 230nm-330nm, 250nm-400nm, 250nm-380nm, or 280nm-350nm. When the particle size of the white colorant is within the above range, the white colorant can achieve high reflectivity. For example, the white colorant may contain rutile-type TiO2 with a diameter of 120nm-400nm or 250nm-400nm. In such cases, the white colorant may be more advantageous for achieving high reflectivity.

[0068] (E) Surfactants The first colored photosensitive resin composition may further contain a surfactant to improve coating properties and prevent the occurrence of defects.

[0069] The type of surfactant is not particularly limited, but for example, fluorine-based surfactants or silicone-based surfactants may be used.

[0070] Examples of commercially available silicone-based surfactants include: DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 from Dow Corning Toray Silicone Co., Ltd.; TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, and TSF-4452 from GE Toshiba Silicone Co., Ltd.; and BYK-333, BYK-307, BYK-3560, BYK UV-3535, BYK-361N, BYK-354, and BYK-399 from BYK, and similar products. These can be used individually or in combination of two or more of them.

[0071] Examples of commercially available fluorine-based surfactants include Megaface F-470, F-471, F-475, F-482, F-489, and F-563, manufactured by Dainippon Ink and Chemicals, Inc. (DIC).

[0072] Among these surfactants, preferred from the viewpoint of coating properties of the composition are BYK-333 and BYK-307 manufactured by BYK, and F-563 manufactured by DIC.

[0073] The surfactant content may be 0.01 to 5 parts by weight, 0.01 to 3 parts by weight, 0.1 to 3 parts by weight, 0.1 to 1 part by weight, or 0.1 to 0.5 parts by weight per 100 parts by weight of the first copolymer (A1), based on the solid content excluding the solvent. Within the above range, the photosensitive resin composition can be smoothly coated.

[0074] (F) Additives In addition, the first colored photosensitive resin composition may further contain at least one additive selected from the group consisting of epoxy compounds, photobase generators, thiol compounds, compounds derived from epoxy resins, and adhesion aids, to the extent that the physical properties of the multilayer cured film are not adversely affected.

[0075] Epoxy compounds may be unsaturated monomers containing at least one epoxy group, or homooligomers or heterooligomers thereof. Examples of unsaturated monomers containing at least one epoxy group include: glycidyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether, 3,4-epoxybutyl (meth)acrylate, 4,5-epoxypentyl (meth)acrylate, 5,6-epoxyhexyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, 2,3-epoxycyclopentyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, α-ethylglycylated glycidyl acrylate. Glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, N-(4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl)acrylamide, N-(4-(2,3-epoxypropoxy)-3,5-dimethylphenylpropyl)acrylamide, allyl glycidyl ether, 2-methylallyl glycidyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, or mixtures thereof. Specifically, glycidyl (meth)acrylate may be used.

[0076] An example of a commercially available homooligomer of an unsaturated monomer containing at least one epoxy group is MIPHOTO GHP-03HHP (glycidyl methacrylate, Miwon Commercial Co., Ltd.).

[0077] Epoxy compounds may further contain the following structural units:

[0078] Specific examples include structural units derived from the following: styrene; styrene containing alkyl substituents, e.g., methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene, and octylstyrene; styrene containing halogens, e.g., fluorostyrene, chlorostyrene, bromostyrene, and iodostyrene; styrene containing alkoxy substituents, e.g., methoxystyrene, ethoxystyrene, and propoxystyrene; p-hydroxy-α-methylstyrene, acetylstyrene; ethylenically unsaturated compounds containing aromatic rings, e.g., divinylbenzene, vinylphenol, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl ether;Unsaturated carboxylic acid esters, e.g., methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, cyclohexyl (meth)acrylate, ethylhexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, 4-hydroxypropyl Roxybutyl (meth)acrylate, glycerol (meth)acrylate, methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, propyl α-hydroxymethyl acrylate, butyl α-hydroxymethyl acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxytripropylene glycol (meth)acrylate, poly(ethylene glycoside) Methyl ether (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, p-nonylphenoxypolyethylene glycol (meth)acrylate, p-nonylphenoxypolypropylene glycol (meth)acrylate, tetrafluoropropyl (meth)acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth)acrylate, octafluoropentyl (meth)acrylate , heptadecafluorodecyl (meth)acrylate, tribromophenyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate and dicyclopentenyloxyethyl (meth)acrylate; tertiary amines containing an N-vinyl group, such as N-vinylpyrrolidone, N-vinylcarbazole and N-vinylmorpholine; unsaturated ethers, such as vinyl methyl ether and vinyl ethyl ether;Unsaturated imides, such as N-phenylmaleimide, N-(4-chlorophenyl)maleimide, N-(4-hydroxyphenyl)maleimide, N-cyclohexylmaleimide, and similar. Structural units derived from the compounds exemplified above may be included in epoxy compounds individually or in combinations of two or more of these.

[0079] Epoxy compounds may have weight-average molecular weights of 100-30,000 Da, 1,000-30,000 Da, 1,000-20,000 Da, 3,000-20,000 Da, 3,000-18,000 Da, 5,000-20,000 Da, or 5,000-15,000 Da. Within the above ranges, process differences due to lower patterns may be advantageously improved, and the pattern profile during development may be favorable.

[0080] The epoxy compound content may be 1 to 30 parts by weight, 1 to 10 parts by weight, or 1 to 5 parts by weight per 100 parts by weight of the first copolymer (A1), based on the solid content excluding the solvent. Within this range, a favorable pattern profile during development may be obtained, and chemical resistance and elastic recovery strength may be improved.

[0081] Photobase generators may include compounds that have the property of generating bases when irradiated with light (or activation energy rays). For example, photobase generators may include highly sensitive compounds that have a photosensitive range even at wavelengths of 300 nm or greater.

[0082] The photobase generator may include a crosslinkable compound containing a polyamine photobase generator component. Because the present invention includes such a photobase generator, it is possible to cure the cured film at low temperatures and / or in a short period of time, and to form fine patterns. In addition, since the photobase generator generates bases when irradiated with light (e.g., UV), it is not inhibited by oxygen in the air, and as a result is useful in preventing corrosion or deterioration of the cured film.

[0083] When the photobase generator is exposed to light, the pendant photobase groups of the polyamine photobase generator component are fragmented or photodegraded, generating amine groups. These amine groups can react with the amine-reactive groups of the polyfunctional amine-reactive component to crosslink the (meth)acrylate copolymer component.

[0084] Examples of photobase generators include: WPBG-018 (Wako, CAS No. 122831-05-7, 9-anthrylmethyl-N,N-diethylcarbamate), WPBG-027 (CAS No. 1203424-93-4, (E)-1-piperidino-3-(2-hydroxyphenyl)-2-propen-1-one), WPBG-266 (CAS No. 1632211-89-2, 1,2-diisopropyl-3-bis(dimethylamino)methylene)guanidium-2-(3-benzoylphenyl)propionate), WPBG-300 (CAS No. 1801263-71-7, 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidinium n-butyltriphenylborate) and similar products. Photobase generators can be used alone or in combination of two or more types.

[0085] The content of the photobase inhibitor may be 0 to 10 parts by weight, 0 to 6 parts by weight, or 0.01 to 5 parts by weight based on the solid content excluding the solvent, per 100 parts by weight of the first copolymer (A1). Within the above range, a favorable pattern profile during development and excellent chemical resistance may be obtained.

[0086] Thiol compounds can be used as additives for free radical or catalytic functions. Thiol compounds can increase the photocuring conversion rate by UV irradiation or thermal reaction, and can also increase the epoxy conversion rate by lowering the reaction energy of thermal reactions. Thiol compounds prevent the elimination of radicals by oxygen. Thiol compounds also increase the degree of crosslinking by photopolymerizable compound (B), thereby improving the degree of curing even at low temperatures and resulting in a denser structure.

[0087] Examples of thiol compounds include compounds having two or more mercapto groups in their molecule. For example, this compound may be an aliphatic thiol compound or an aromatic thiol compound.

[0088] Examples of aliphatic thiol compounds include: methanedithiol, 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,2-cyclohexanedithiol, 3,4-dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol, 1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropyl methyl ether, Bis(2-mercaptoethyl) ether, tetrakis(mercaptomethyl)methane, bis(mercaptomethyl) sulfide, bis(mercaptomethyl) disulfide, bis(mercaptoethyl) sulfide, bis(mercaptoethyl) disulfide, bis(mercaptomethylthio)methane, bis(2-mercaptoethylthio)methane, 1,2-bis(2-mercaptomethylthio)ethane, 1,2-bis(2-mercaptoethylthio)ethane, 1,3-bis(mercaptomethylthio)propane, 1,3- Bis(2-mercaptoethylthio)propane, 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3-mercaptopropylthio)propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4, 8-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, 1,1,3,3-Tetrakis(mercaptomethylthio)propane, 4,6-Bis(mercaptomethylthio)-1,3-Dithiane, 2-(2,2-Bis(mercaptomethylthio)ethyl)-1,3-Dithiethane, Tetrakis(mercaptomethylthiomethyl)methane, Tetrakis(2-mercaptoethylthiomethyl)methane, Bis(2,3-Dimercaptopropyl)sulfide, 2,5-Bismercaptomethyl-1,4-Dithiane, ethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), diethylene glycol bis(2-mercaptoacetate), diethylene glycol bis(3-mercaptopropionate), 2,3-dimercapto-1-propanol(3-mercaptopropionate), 3-mercapto-1,2-propanediol bis(2-mercaptoacetate), 3-mercapto-1,2-propanediol di(3-mercaptopropionate), trimethylolpropane tris(2-mercapto Trimethylolpropanetetrakis (2-mercaptoacetate), trimethylolpropanetris (3-mercaptopropionate), ditrimethylolpropanetetrakis (3-mercaptopropionate), trimethylolethanetris (2-mercaptoacetate), trimethylolethanetris (3-mercaptopropionate), pentaerythritoltetrakis (2-mercaptoacetate), dipentaerythritolhexa (2-mercaptoacetate), pentaerythritol di(3-mercaptopropionate) Pentaerythritol tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate) (PETMP), dipentaerythritol hexa(3-mercaptopropionate), glycerin di(2-mercaptoacetate), glycerin tris(2-mercaptoacetate), glycerin di(3-mercaptopropionate), glycerin tris(3-mercaptopropionate), 1,4-cyclohexanediol bis(2-mercaptoacetate), 1,4-cyclohexanediol bis(3-mercaptopropionate lopionate), hydroxymethyl sulfide bis(2-mercaptoacetate), hydroxymethyl sulfide bis(3-mercaptopropionate), hydroxyethyl sulfide (2-mercaptoacetate), hydroxyethyl sulfide (3-mercaptopropionate), hydroxymethyl disulfide (2-mercaptoacetate), hydroxymethyl disulfide (3-mercaptopropionate), bis(2-mercaptoethyl ester) thioglycolate, bis(2-mercaptoethyl ester) thiodipropionate and N,N',N''-Tris(β-mercaptopropylcarbonyloxyethyl) isocyanurate.

[0089] Examples of aromatic thiol compounds include: 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis(mercaptomethyl)benzene, 1,4-bis(mercaptomethyl)benzene, 1,2-bis(mercaptoethyl)benzene, 1,4-bis(mercaptoethyl)benzene, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris(mercaptomethyl)benzene, 1,2,4-tris(mercaptomethyl)benzene, 1,3,5-tris(mercaptomethyl)benzene, 1,2,3-tris(mercaptoethyl)benzene, 1,3,5-tris(mercaptoethyl)benzene, 1,2,4-tris(mercaptoethyl)benzene , 2,5-toluenedithiol, 3,4-toluenediol, 1,4-naphthalenediol, 1,5-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, 1,2,3,4-tetramercaptobenzene, 1,2,3,5-tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene, 1,2,3,4-tetrakis(mercaptomethyl)benzene, 1,2,3,5-tetrakis(mercaptomethyl)benzene, 1,2,4,5-tetrakis(mercaptomethyl)benzene, 1,2,3,4-tetrakis(mercaptoethyl)benzene, 1,2,3,5-tetrakis(mercaptoethyl)benzene, 1,2,4,5-tetrakis(mercaptoethyl)benzene, 2,2'-dimercaptobiphenyl and 4,4'-dimercaptobiphenyl.

[0090] Thiol compounds can be aliphatic thiol compounds. Specifically, these include pentaerythritol tetra(3-mercaptopropionate) (PETMP), SIRIUS-501 (SUBARU-501, Osaka Organic Chemical Industry Co., Ltd.), and glycolyl derivatives (TS-G, Shikoku Chemicals Co., Ltd.).

[0091] The content of the thiol compound may be 1 to 30 parts by weight, 1 to 20 parts by weight, 1 to 15 parts by weight, or 1 to 10 parts by weight per 100 parts by weight of the first copolymer (A1), based on the solid content excluding the solvent. When the amount of the thiol compound is within the above range, the pattern profile during development may be advantageous and the chemical resistance may be excellent.

[0092] Compounds derived from epoxy resins may have at least one double bond and a cardo main chain structure, may be novolac resins, or may be acrylic acid resins containing double bonds in their side chains.

[0093] The weight-average molecular weight (Mw) of compounds derived from epoxy resin, when determined by gel permeation chromatography relative to polystyrene, may be in the range of 3,000 to 18,000 Da or 5,000 to 10,000 Da. When the amount of compounds derived from epoxy resin falls within this range, a favorable pattern profile during development may be obtained, and properties such as chemical resistance and elastic resilience may be improved.

[0094] Specifically, compounds derived from epoxy resins are given by the following formula 1: [ka] (In Equation 1, Each X is independent of the others. [ka] And; L1 is independent of C 1~10 Alkylene group, C 3~20 Cycloalkylene group or C 1~10 It is an alkylene oxy group; R1 to R7 are each independently H and C 1~10 Alkyl alkyl group, C 1~10 Alkoxy group, C 2~10 Alkenyl group or C 6~14It is an aryl group; R8 is H, methyl, ethyl, CH3CHCl-, CH3CHOH-, CH2=CHCH2-, or phenyl; n is an integer between 0 and 10. It may be a compound having a cardo main chain structure represented by [the given formula].

[0095] C 1~10 Specific examples of alkylene groups include: methylene, ethylene, propylene, isopropylene, butylene, isobutylene, sec-butylene, t-butylene, pentylene, isopentylene, t-pentylene, hexylene, heptylene, octylene, isooctylene, t-octylene, 2-ethylhexylene, nonylene, isononylene, decylene, isodecylene, and the like. 3~20 Specific examples of cycloalkylene groups include: cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, decalinylene, adamantylene, and similar groups. 1~10 Specific examples of alkylene oxy groups include: methylene oxy, ethylene oxy, propylene oxy, butylene oxy, sec-butylene oxy, t-butylene oxy, pentylene oxy, hexylene oxy, heptylene oxy, octylene oxy, 2-ethyl-hexylene oxy and the like. 1~10 Specific examples of alkyl groups include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, pentyl, isopentyl, t-pentyl, hexyl, heptyl, octyl, isooctyl, t-octyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, and similar. 1~10 Specific examples of alkoxy groups include: methoxy, ethoxy, propoxy, butyloxy, sec-butoxy, t-butoxy, pentoxy, hexyloxy, heptoxy, octyloxy, 2-ethylhexyloxy, and similar groups. 2~10 Specific examples of alkenyl groups include vinyl, allyl, butenyl, propenyl, and similar groups. 6~14Specific examples of aryl groups include phenyl, tolyl, xylyl, naphthyl, and similar groups.

[0096] As an example, compounds derived from epoxy resins having a cardo main chain structure can be prepared by the following synthetic route represented by reaction scheme 1. [ka] In reaction scheme 1, Hal is a halogen; X, R1, R2, and L1 are the same as those defined in equation 1 above.

[0097] Compounds derived from epoxy resins having a cardo backbone structure can be obtained by reacting an epoxy resin having a cardo backbone structure with an unsaturated basic acid to produce an epoxy adduct, and then reacting the epoxy adduct thus obtained with a polybasic acid anhydride, or by further reacting the product thus obtained with a monofunctional epoxy compound or a polyfunctional epoxy compound. Any unsaturated basic acid known in the art (e.g., acrylic acid, (meth)acrylic acid, crotonic acid, cinnamic acid, sorbic acid, and the like) can be used. Any polybasic acid anhydride known in the art (e.g., succinic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, hexahydrophthalic anhydride, and the like) can be used. Any monofunctional or polyfunctional epoxy compound known in the art (e.g., glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, bisphenol Z glycidyl ether, and the like) may be used.

[0098] As an example, a compound derived from an epoxy resin having a cardo main chain structure can be prepared by the following synthetic route represented by reaction scheme 2. [ka] In reaction scheme 2, R9 is independently H, C 1~10 Alkyl alkyl group, C 1~10 Alkoxy group, C 2~10 Alkenyl group or C 6~14 It is an aryl group; R 10 and R 11 Each of these is independently a saturated or unsaturated aliphatic or aromatic ring having six carbon atoms; n is an integer from 1 to 10; and X, R1, R2, and L1 are the same as those defined in Equation 1 above.

[0099] When compounds derived from epoxy resins having a cardo backbone structure are used, the cardo backbone structure can improve the adhesion of the cured material to the substrate, alkali resistance, processability, strength, and similar properties. Furthermore, images at fine resolution can be formed as patterns when the uncured portions are removed during development.

[0100] The content of the epoxy resin-derived compound may be 0 to 50 parts by weight, 0 to 40 parts by weight, 0.01 to 50 parts by weight, 0.01 to 40 parts by weight, or 0.01 to 30 parts by weight per 100 parts by weight of the first copolymer (A1), based on the solid content excluding the solvent. When the epoxy resin-derived compound is used within the above amount range, the developability and pattern profile during development may be advantageous.

[0101] The first colored photosensitive resin composition may further contain an adhesion aid to improve adhesion to the substrate.

[0102] The adhesion aid may have at least one reactive group selected from the group consisting of carboxyl groups, (meth)acryloyl groups, isocyanate groups, amino groups, mercapto groups, vinyl groups, and epoxy groups. Preferably, this adhesion aid may have an isocyanate group.

[0103] Examples of adhesive auxiliaries include: trimethoxysilyl benzoic acid, γ-methacrylateoxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-isocyanatetopropyltriethoxysilane, 3-isocyanatetopropyltriethoxysilane, and mixtures thereof.

[0104] Preferably, the adhesion aid may be γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, 3-isocyanatetopropyltrimethoxysilane, 3-isocyanatetopropyltriethoxysilane, or N-phenylaminopropyltrimethoxysilane. More preferably, the adhesion aid may be N-phenylaminopropyltrimethoxysilane, 3-isocyanatetopropyltrimethoxysilane, 3-isocyanatetopropyltriethoxysilane, or a mixture thereof, which are adhesion aids containing an isocyanate group.

[0105] The content of the adhesive aid may be 0.001 to 5 parts by weight, 0.01 to 5 parts by weight, 0.01 to 4 parts by weight, 0.01 to 3 parts by weight, 0.1 to 4 parts by weight, 0.1 to 3 parts by weight, or 0.1 to 0.2 parts by weight per 100 parts by weight of the first copolymer (A1), based on the solid content. Within the above range, adhesion to the substrate can be further improved.

[0106] (G) Solvent The first colored photosensitive resin composition may be prepared as a liquid composition in which the above components and a solvent are mixed. Any solvent known in the art that is compatible with but does not react with the components in the first colored photosensitive resin composition may be used as a solvent in the preparation of the photosensitive resin composition.

[0107] Examples of solvents include: glycol ethers, e.g., ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates, e.g., ethyl cellosolve acetate; esters, e.g., ethyl 2-hydroxypropionate; diethylene glycols, e.g., diethylene glycol monomethyl ether; propylene glycol alkyl ether acetates, e.g., propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate; and alkoxyalkyl acetates, e.g., 3-methoxybutyl acetate. The solvents may be used alone or in combination of two or more.

[0108] The solvent content is not specifically limited, but from the viewpoint of coating properties and stability of the first colored photosensitive resin composition, it may be 50 to 200 parts by weight or 80 to 150 parts by weight per 100 parts by weight of the first copolymer (A1), based on the solid content excluding the solvent. Within the above range, the resin composition coats smoothly and has a small delay margin that may occur in the work process.

[0109] In addition, the first colored photosensitive resin composition may further contain other additives (e.g., antioxidants and stabilizers) to the extent that the physical properties of the cured film are not adversely affected.

[0110] A first colored photosensitive resin composition containing the components described above can be prepared as a liquid composition by conventional mixing methods. For example, a colorant may be pre-mixed with a dispersion resin, dispersant and solvent, and dispersed using a bead mill until the average particle size of the colorant reaches a desired value, thereby preparing a colorant dispersion. In such cases, a surfactant and / or copolymer may be partially or completely blended in. The copolymer and the remainder of the surfactant, a photopolymerizable compound and a photopolymerization initiator are added to this colorant dispersion. If necessary, additives such as epoxy compounds or additional solvents may be further blended in to a specific concentration, and then the mixture may be thoroughly stirred to prepare the first colored photosensitive resin composition in liquid phase.

[0111] The present invention can provide a first cured film by coating such a first colored photosensitive resin composition onto a substrate and curing it. Specifically, the first colored photosensitive resin composition is coated onto a pre-treated substrate to a desired thickness (e.g., 4 μm to 8 μm) by a spin coating method, slit coating method, roll coating method, screen printing method, applicator method or similar, and the first colored photosensitive resin composition is cured by removing the solvent therefrom to form a first cured film. The final thickness of the first cured film may be 10 μm or less, 8 μm or less, 6 μm or less, 4 μm to 9 μm, or 5 μm to 9 μm.

[0112] [Second colored photosensitive resin composition] The second colored photosensitive resin composition may comprise (A2) the second copolymer; (B) a photopolymerizable compound; (C) a photopolymerization initiator; and (D2) a colorant other than white. The second colored photosensitive resin composition may optionally further comprise (E) a surfactant, (F) an additive, such as epoxy compounds, thiol compounds, photobase generators and adhesion aids, and / or (G) a solvent, as described above.

[0113] A second colored photosensitive resin composition can be coated onto the first cured film to form a second cured film. The second cured film can satisfy high light-shielding properties because it contains the following components.

[0114] The following sections will explain each component in detail.

[0115] (A2) Second copolymer The second copolymer (A2) includes (b1) structural units derived from ethylenically unsaturated carboxylic acids, ethylenically unsaturated carboxylic acid anhydrides, or combinations thereof; and (b2) structural units derived from ethylenically unsaturated compounds containing epoxy groups, and (b3) structural units derived from ethylenically unsaturated compounds containing fluorine; and (b4) at least one structural unit derived from ethylenically unsaturated compounds different from (b1) to (b3).

[0116] According to one embodiment, the second copolymer may comprise structural units (b1), (b2), and (b3).

[0117] According to another embodiment, the second copolymer may comprise structural units (b1), (b2), and (b4).

[0118] In yet another embodiment, the second copolymer may include structural units (b1) to (b4).

[0119] The second copolymer is an alkali-soluble resin for developing properties, and can serve as a base when a cured film is formed, as well as as a structure for forming the final pattern.

[0120] (b1) Structural units derived from ethylenically unsaturated carboxylic acids, ethylenically unsaturated carboxylic acid anhydrides, or combinations thereof The structural unit (b1) may be derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a combination thereof.

[0121] Ethylene-unsaturated carboxylic acids and ethylenically unsaturated carboxylic acid anhydrides can be polymerizable unsaturated monomers containing at least one carboxyl group in their molecule. These may be the same compounds exemplified above from which structural unit (a1) may be derived.

[0122] The content of structural unit (b1) may be 5-65 mol%, 10-65 mol%, 10-50 mol%, 10-40 mol%, 10-35 mol%, 15-35 mol%, 20-35 mol%, or 20-30 mol%, based on the total number of moles of structural units constituting the second copolymer. Within the above range, structural unit (b1) may have favorable developability.

[0123] (b2) Structural units derived from ethylenically unsaturated compounds containing epoxy groups The structural unit (b2) may originate from an ethylenically unsaturated compound containing an epoxy group.

[0124] For example, an ethylenically unsaturated compound containing this epoxy group may be the same as the compound exemplified above, from which structural unit (a3) ​​may be derived.

[0125] The content of structural unit (b2) may be 1 mol% to 40 mol, 1 mol% to 30 mol%, 1 mol% to 20 mol%, 1 mol% to 10 mol%, 5 mol% to 30 mol%, 5 mol% to 20 mol%, 5 mol% to 15 mol%, or 5 mol% to 12 mol%, based on the total number of moles of structural units constituting the second copolymer. Within the above range, structural unit (b2) may be more advantageous in terms of process residue and pre-bake margins.

[0126] (b3) Structural units derived from fluorine-containing ethylenically unsaturated compounds The structural unit (b3) may originate from an ethylenically unsaturated compound containing fluorine.

[0127] Examples of fluorine-containing ethylenically unsaturated compounds include nonafluorophenyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, hexafluoroisopropyl (meth)acrylate, and octafluorophenyl (meth)acrylate. Structural units (b2) derived from fluorine-containing ethylenically unsaturated compounds function to enable clear resolution and pattern formation even when ink is injected into the compartments between barrier ribs when a multilayer cured film containing a second cured film is used as a quantum dot barrier rib. Specifically, when a fluorine-containing cured film is applied to a quantum dot barrier rib, it is possible to prevent the release of the quantum dot solution due to overflow into adjacent areas when the quantum dot solution is filled by an inkjet method.

[0128] The content of structural unit (b3) may be 10-80 mol%, 10-70 mol%, 20-70 mol%, 20-60 mol%, 30-70 mol%, 30-60 mol%, 40-60 mol%, or 50-60 mol%, based on the total number of moles of structural units constituting the second copolymer. Within the above range, the light-shielding properties of the cured film can be further improved.

[0129] (b4) Structural units derived from ethylenically unsaturated compounds different from (b1) to (b3) Structural unit (b4) may originate from an ethylenically unsaturated compound different from (b1) to (b3).

[0130] For example, ethylenically unsaturated compounds different from (b1) to (b3) may be the same as the compounds exemplified above, from which structural units (a2) and / or (a4) may be derived.

[0131] The content of structural unit (b4) may be 10-80 mol%, 10-70 mol%, 20-70 mol%, 20-60 mol%, 20-50 mol%, 20-40 mol%, or 20-30 mol%, based on the total number of moles of structural units constituting the second copolymer. Within the above range, the storage stability of the composition can be maintained, and the film retention rate can be more advantageously improved.

[0132] According to one embodiment, examples of structural units constituting the second copolymer include: a copolymer of (meth)acrylic acid / glycidyl (meth)acrylate / styrene / methyl (meth)acrylate; a copolymer of (meth)acrylic acid / glycidyl (meth)acrylate / nonafluorophenyl (meth)acrylate / 2,2,2-trifluoroethyl (meth)acrylate; a copolymer of (meth)acrylic acid / glycidyl (meth)acrylate / styrene / nonafluorophenyl (meth)acrylate; and a copolymer of (meth)acrylic acid / glycidyl (meth)acrylate / styrene / methyl (meth)acrylate / nonafluorophenyl (meth)acrylate.

[0133] The second copolymer comprises (b1) a structural unit derived from methacrylic acid; and (b2) a structural unit derived from glycidyl methacrylate, and may also comprise (b3) a structural unit derived from nonafluorophenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, or a mixture thereof; and (b4) a structural unit derived from styrene, methyl methacrylate, or a mixture thereof.

[0134] The second copolymer may have a weight-average molecular weight (Mw) of 4,000-20,000 Da, 4,000-16,000 Da, 5,000-20,000 Da, 5,000-16,000 Da, or 10,000-16,000 Da. Within the above range, process differences due to lower patterns may be advantageously improved, the pattern profile during development may be favorable, and film retention and chemical resistance may be improved.

[0135] The second copolymer can be prepared by filling a reactor with monomers from which the above structural units (b1), (b2), (b3) and / or (b4) may be derived, a radical polymerization initiator and a solvent, followed by filling with nitrogen, and polymerizing the mixture by gently stirring.

[0136] Radical polymerization initiators may be, but are not limited to, azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile); or benzoyl peroxides, lauryl peroxides, t-butyl peroxypivalate, 1,1-bis(t-butylperoxy)cyclohexane, or similar. Radical polymerization initiators may be used alone or in combination of two or more.

[0137] The solvent can be any conventional solvent commonly used in the preparation of copolymers, such as propylene glycol monomethyl ether acetate (PGMEA).

[0138] (B) Photopolymerizable compound The second colored photosensitive resin composition may contain the photopolymerizable compound described above.

[0139] The content of the photopolymerizable compound may be 10 to 200 parts by weight, 10 to 150 parts by weight, 50 to 150 parts by weight, 70 to 150 parts by weight, 70 to 130 parts by weight, 80 to 150 parts by weight, 80 to 120 parts by weight, 90 to 110 parts by weight, or 95 to 100 parts by weight per 100 parts by weight of the second copolymer (A2), based on the solid content excluding the solvent.

[0140] When the amount of photopolymerizable compound is within the above range, excellent pattern developability and coating properties may be achieved while maintaining a constant film retention rate. If the amount of photopolymerizable compound is below the above range, the development time will be longer, which may affect the process and residue. If the amount of photopolymerizable compound exceeds the above range, a problem of excessively high pattern resolution may occur.

[0141] (C) Photopolymerization initiator The second colored photosensitive resin composition may contain the photopolymerization initiator described above.

[0142] The amount of photopolymerization initiator may be 1 to 20 parts by weight, 1 to 15 parts by weight, 1 to 10 parts by weight, or 1 to 5 parts by weight per 100 parts by weight of the second copolymer (A2), based on the solid content excluding the solvent.

[0143] Specifically, per 100 parts by weight of the second copolymer (A2), an oxime compound may be used in an amount of 0.05 to 4 parts by weight, 0.5 to 4 parts by weight, 1 to 4 parts by weight, 1 to 3 parts by weight, 1 to 2.5 parts by weight, or 1 to 2 parts by weight as a photopolymerization initiator.

[0144] In addition, a triazine compound may be used as a photopolymerization initiator in an amount of 0.05 to 4 parts by weight, 0.5 to 4 parts by weight, 1 to 4 parts by weight, 1 to 3 parts by weight, or 1 to 2.5 parts by weight per 100 parts by weight of the second copolymer (A2).

[0145] When oxime compounds are used in amounts within the above range, high sensitivity, development characteristics, and coating characteristics can be improved. In addition, when triazine compounds are used in amounts within the above range, a cured film can be obtained that exhibits high sensitivity, as well as excellent chemical resistance and taper angle during pattern formation.

[0146] (D2) Colorants other than white The second colored photosensitive resin composition may contain a colorant that has high color development and excellent heat resistance in order to provide light-shielding properties. This colorant may be a colorant other than white (D2).

[0147] Other colorants may be at least one selected from the group consisting of yellow colorants, purple colorants, red colorants, orange colorants, blue colorants, and black colorants.

[0148] The colorants other than white are the colored colorants described above, and when a cured film is formed from the second colored photosensitive resin composition, they function to improve light shielding properties.

[0149] Colorants other than white may include any compound classified as a colorant in the Color Index (published by the British Society of Dye and Coloring), and may also include any dye known in the art.

[0150] Specific examples of yellow, purple, red, orange, and blue colorants include: CIPigment Yellow 139, 138, 154, 180, and 181; CIPigment Violet 13, 14, 19, 23, 25, 27, 29, 32, 33, 36, 37, and 38; CIPigment Red 254 and 177; CIPigment Orange 64 and 71; CIPigment Blue 15 (15:3, 15:4, 15:6, etc.), 16, 21, 28, 60, 64, and 76. From the viewpoint of high light-shielding and high reflectivity, CIPigment Yellow 139, CIPigment Violet 29, CIPigment Red 254, CIPigment Orange 64, and CIPigment Blue 15:6 and 60 are preferred.

[0151] The black coloring agent may be a black organic coloring agent, a black inorganic coloring agent, or a mixture thereof.

[0152] The black organic colorant may be at least one selected from the group consisting of aniline black, lactam black, and perylene black. Specifically, the black organic colorant may be BK-7539 (Tokushiki Co., Ltd.) which contains organic black. In such a case, high reflectivity, high light shielding, optical density, and the like may be improved.

[0153] The black inorganic colorant may be carbon black, titanium black, metal oxides (e.g., Cu-Fe-Mn oxides), synthetic iron black, or similar. Specifically, the black inorganic colorant may be BK-7544 (Tokushiki Co., Ltd.), which contains carbon black.

[0154] The amount of yellow coloring agent may be 3 to 50 parts by weight, 3 to 30 parts by weight, 3 to 20 parts by weight, 3 to 10 parts by weight, or 5 to 10 parts by weight per 100 parts by weight of the second copolymer (A2).

[0155] The amount of purple coloring agent may be 3 to 50 parts by weight, 3 to 30 parts by weight, 3 to 20 parts by weight, 3 to 10 parts by weight, or 5 to 10 parts by weight per 100 parts by weight of the second copolymer (A2).

[0156] The amount of red coloring agent may be 3 to 50 parts by weight, 3 to 30 parts by weight, 3 to 20 parts by weight, 3 to 10 parts by weight, or 5 to 10 parts by weight per 100 parts by weight of the second copolymer (A2).

[0157] The content of the orange coloring agent may be 3 to 50 parts by weight, 3 to 30 parts by weight, 3 to 20 parts by weight, 3 to 10 parts by weight, or 5 to 10 parts by weight per 100 parts by weight of the second copolymer (A2).

[0158] The amount of blue coloring agent may be 3 to 50 parts by weight, 3 to 30 parts by weight, 3 to 20 parts by weight, 3 to 10 parts by weight, or 5 to 10 parts by weight per 100 parts by weight of the second copolymer (A2).

[0159] The content of black organic colorants, black inorganic colorants, or mixtures thereof may be 3 to 50 parts by weight, 3 to 30 parts by weight, 3 to 20 parts by weight, 3 to 10 parts by weight, or 5 to 10 parts by weight per 100 parts by weight of the second copolymer (A2).

[0160] If two or more colorants other than white are used, the total content of these colorants may be 3 to 30 parts by weight, 3 to 20 parts by weight, 3 to 15 parts by weight, or 3 to 10 parts by weight based on 100 parts by weight of the second copolymer (A2), with respect to the solid content excluding the solvent.

[0161] Within the above range, the transmittance is low, and therefore, the desired high light-shielding properties can be satisfied, while at the same time, high reflectivity properties can be obtained.

[0162] The particle size of colorants other than white may be 40nm-200nm, 45nm-200nm, 50nm-200nm, 50nm-180nm, 50nm-150nm, 55nm-130nm, 55nm-127nm, or 55nm-120nm. When the particle size of colorants other than white is within the above range, color development and heat resistance may be further improved, which may be advantageous for achieving high reflectivity characteristics.

[0163] (E) Surfactants The second colored photosensitive resin composition may further contain the surfactant described above in order to improve coverage and prevent the occurrence of defects.

[0164] The surfactant content may be 0.01 to 5 parts by weight, 0.01 to 3 parts by weight, 0.1 to 3 parts by weight, 0.1 to 1 part by weight, or 0.1 to 0.5 parts by weight per 100 parts by weight of the second copolymer (A2), based on the solid content excluding the solvent. Within the above range, the photosensitive resin composition can be smoothly coated.

[0165] (F) Additives In addition, the second colored photosensitive resin composition may further contain at least one additive selected from the group consisting of epoxy compounds, photobase generators, thiol compounds, compounds derived from epoxy resins, and adhesion aids described above, to the extent that the physical properties of the multilayer cured film are not adversely affected.

[0166] Here, the epoxy compound content may be 1 to 30 parts by weight, 1 to 10 parts by weight, or 1 to 5 parts by weight per 100 parts by weight of the second copolymer (A2), based on the solid content excluding the solvent.

[0167] In addition, the content of the photobase inhibitor may be 0 to 10 parts by weight per 100 parts by weight of the second copolymer (A2), based on the solid content excluding the solvent, more specifically 0 to 6 parts by weight, and more specifically 0.01 to 5 parts by weight. Within the above range, the pattern profile during development may be advantageous and the chemical resistance may be excellent.

[0168] In addition, the content of the thiol compound may be 1 to 30 parts by weight, 1 to 20 parts by weight, 1 to 15 parts by weight, or 1 to 10 parts by weight per 100 parts by weight of the second copolymer (A2), based on the solid content excluding the solvent. When the amount of the thiol compound is within the above range, the pattern profile during development may be advantageous and the chemical resistance may be excellent.

[0169] In addition, the content of the compound derived from the epoxy resin may be 0 to 50 parts by weight per 100 parts by weight of the second copolymer (A2), based on the solid content excluding the solvent, more specifically 0 to 40 parts by weight, and more specifically 0.01 to 50 parts by weight, 0.01 to 40 parts by weight, or 0.01 to 30 parts by weight. When the compound derived from the epoxy resin is used within the above range, the developability and pattern profile during development may be advantageous.

[0170] (G) Solvent A second colored photosensitive resin composition may be prepared as a liquid composition in which the above components and a solvent are mixed. A solvent that is compatible with but does not react with the components in the second colored photosensitive resin composition described above may be the same as the solvent described for the first colored photosensitive resin composition.

[0171] The solvent content is not specifically limited, but from the viewpoint of coating properties and stability of the second colored photosensitive resin composition, it may be 50 to 200 parts by weight or 80 to 150 parts by weight per 100 parts by weight of the second copolymer (A2), based on the solid content excluding the solvent. Within the above range, this resin composition coats smoothly and has a small delay margin that may occur in the work process.

[0172] In addition, the second colored photosensitive resin composition may further contain other additives (e.g., antioxidants and stabilizers) to the extent that the physical properties of the cured film are not adversely affected.

[0173] A second colored photosensitive resin composition containing the components described above can be prepared as a liquid composition by conventional mixing methods. For example, a colorant may be pre-mixed with a dispersion resin, dispersant and solvent, and dispersed using a bead mill until the average particle size of the colorant reaches a desired value, thereby preparing a colored dispersion. In such cases, a surfactant and / or copolymer may be partially or completely blended in. The copolymer and the remainder of the surfactant, a photopolymerizable compound and a photopolymerization initiator may be added to this colorant dispersion. If necessary, additives such as epoxy compounds or additional solvents may be further blended to a specific concentration, and then thoroughly stirred to prepare a second colored photosensitive resin composition in liquid phase.

[0174] The present invention can provide a second cured film by coating such a second colored photosensitive resin composition onto a first cured film and curing it. Specifically, the second photosensitive resin composition is coated onto the first cured film to a desired thickness (e.g., 4 μm to 8 μm), and the second photosensitive resin composition is cured by removing the solvent therefrom to form a second cured film.

[0175] The final thickness of the second cured film may be 10 μm or less, 8 μm or less, 6 μm or less, 4 μm to 9 μm, or 5 μm to 9 μm.

[0176] [Curing film] The present invention may provide a multilayer cured film formed from a first colored photosensitive resin composition and a second colored photosensitive resin composition.

[0177] Specifically, the multilayer cured film of the present invention comprises a first cured film formed from a first colored photosensitive resin composition and a second cured film formed from a second colored photosensitive resin composition, wherein the first colored photosensitive resin composition comprises (A1) a first copolymer; (B) a photopolymerizable compound; (C) a photopolymerization initiator; and (D1) a white coloring agent, and the second colored photosensitive resin composition comprises (A2) a second copolymer; (B) a photopolymerizable compound; (C) a photopolymerization initiator; and (D2) a coloring agent other than white, and the multilayer cured film has a total thickness of 6 μm or more.

[0178] This multilayer cured film can be used as a structure for quantum dot barrier ribs.

[0179] In a multilayer cured film according to one embodiment, patterns can be formed at regular intervals, as shown in Figures 2 to 4. This multilayer cured film may consist of one first cured film and multiple second cured films. In such a case, the second cured film may have 2 to 10 layers, and these layers can be sequentially laminated on the first cured film.

[0180] The first cured film and the second cured film may have thicknesses of 10 μm or less, 8 μm or less, 6 μm or less, 4 μm to 9 μm, or 5 μm to 9 μm, respectively. In addition, the multilayer cured film including the first cured film and the second cured film may have a total thickness of 6 μm or less, 6 μm to 20 μm, 6 μm to 18 μm, or 10 μm to 18 μm.

[0181] According to one embodiment, as shown in Figure 2, the multilayer cured film (200) may consist of two layers, including a first cured film (211) and a second cured film (212) formed on a substrate (210). Specifically, the multilayer cured film (200) may be a two-layer multilayer cured film (200) prepared by exposing and developing a two-layer cured film to form a pattern, and then post-baking it, and this two-layer cured film includes a first cured film (211) formed by coating a first colored photosensitive resin composition onto a substrate (210) and curing it, and a second cured film (212) formed by coating a second colored photosensitive resin composition onto the first cured film (211) and curing it.

[0182] According to another embodiment, as shown in Figure 3, the multilayer cured film (300) may consist of three layers, including one first cured film (311) and two second cured films (312, 313). Specifically, the multilayer cured film (300) may be a three-layer multilayer cured film (300) prepared by exposing and developing a three-layer cured film to form a pattern, and then post-baking it, the three-layer cured film including a first cured film (311) formed by coating a first colored photosensitive resin composition onto a substrate (310) and curing it, a second cured film (312) formed by coating a second colored photosensitive resin composition onto the first cured film (311) and curing it, and a third cured film (313) formed by coating a second colored photosensitive resin composition onto the second cured film (312) and curing it.

[0183] In yet another embodiment, as shown in Figure 4, the multilayer cured film (400) may be an n+1 layer multilayer cured film (400) comprising one first cured film (411) and n layers of second cured films (412, 413...n). Specifically, the multilayer cured film (400) may be an n+1 layer multilayer cured film (400), which is prepared by exposing and setting an n+1 layer cured film to form a pattern, and then post-baking it, and this n+1 layer cured film includes a first cured film (411) formed by coating a first colored photosensitive resin composition onto a substrate (410) and curing it, and n layers of second cured films (412, 413...n) formed by repeatedly coating a second colored photosensitive resin composition onto the first cured film (411) and curing it. Here, n can be 2 or greater, specifically 2 to 10, 2 to 8, 2 to 6, or 2 to 5.

[0184] In this multilayer cured film, the thickness of each cured film may be the same or different.

[0185] The thickness of this multilayer cured film is measured using the SCAN PLUS alpha-step profilometer, based on the height difference caused by the vertical movement of the instrument's probe tip. The thickness of this cured film is obtained from this result. The final film thickness refers to the value measured for the final multilayer cured film prepared by forming a pattern through exposure and development, and then post-baking. This value covers the entire multilayer cured film. The final film thickness can be 6 μm or more, 6 μm to 20 μm, 6 μm to 18 μm, or 10 μm to 18 μm.

[0186] In addition, the reflectance R of this multilayer cured film was measured by the SCI (including specular reflection) method at wavelengths of 360 nm to 740 nm or 550 nm. SCI and reflectance R measured by the SCE (non-specular reflection) method. SCE The relationships are as follows: (Relationship 1) 50% ≤ R SCI (Relationship 2) 40% ≤ R SCE (Relationship 3) 50% ≤ R SCE / R SCI It may satisfy the requirement.

[0187] Specifically, R SCI This could be 50% or more, 51% or more, 52% or more, 50-90%, 50-80%, or 53-70%; R SCE This could be 40% or more, 42% or more, 44% or more, 45% or more, 40-90%, 40-80%, 43-80%, 44-70%, or 44-60%; the ratio between these (R SCE / R SCI The reflective properties can be 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, 80-99%, 80-95%, 90-99%, or 90-95%. Therefore, the properties of high reflectivity and high light shielding can be satisfied, and leakage of yellow, red, purple, or similar colored light can be prevented. The multilayer cured film prepared in this way has excellent properties and can therefore be advantageously used for quantum dot display devices.

[0188] [Preparation of multilayer cured films] The present invention allows for the preparation of a multilayer cured film by the following method. In a single development process, it is possible to form a multilayer pattern having a uniform film thickness suitable for quantum dot barrier ribs.

[0189] Specifically, the process for preparing a multilayer cured film includes (1) coating a substrate with a first colored photosensitive resin composition and curing it to form a first cured film; (2) coating the first cured film with a second colored photosensitive resin composition and curing it to form a second cured film; and (3) exposing and developing the second cured film to form a pattern and then post-baking it. In such a case, the first colored photosensitive resin composition comprises (A1) a first copolymer; (B) a photopolymerizable compound; (C) a photopolymerization initiator; and (D1) a white colorant, and the second colored photosensitive resin composition comprises (A2) a second copolymer; (B) a photopolymerizable compound; (C) a photopolymerization initiator; and (D2) a colorant other than white.

[0190] The first colored photosensitive resin composition and the second colored photosensitive resin composition are as described above.

[0191] More specifically, a process for preparing a multilayer cured film according to a certain embodiment may include (Step 1) coating a substrate with a first colored photosensitive resin composition and curing it to form a first cured film.

[0192] In the step of forming the first cured film, the photosensitive resin composition according to the present invention is coated onto a pre-treated substrate to a desired thickness (for example, 4 μm to 8 μm) by a spin coating method, slit coating method, roll coating method, screen printing method, applicator method or similar, and the photosensitive resin composition is cured by removing the solvent therefrom to form the first cured film.

[0193] Various inorganic substrates can be used as base materials (e.g., glass substrates, ITO vapor-deposited substrates, SiN x Vapor deposition substrate and SiON x A vapor deposition substrate may be used. Any material can be used as a substrate, as long as it can be used to form the structure of the quantum dot barrier rib.

[0194] The curing process to form the first cured film can be carried out at 70°C to 140°C for 50 to 900 seconds. The curing process can be carried out once or more times.

[0195] When curing is performed in a single step, the curing can be carried out over a period of 50 to 800 seconds, 100 to 800 seconds, 150 to 600 seconds, or 150 to 500 seconds at a temperature of 70°C to 140°C, 80°C to 130°C, or 90°C to 130°C.

[0196] If curing is performed more than once, for example, the curing can be performed as a pre-bake for 50 to 400 seconds, 50 to 300 seconds, or 100 to 300 seconds at 70°C to 100°C or 70°C to 90°C, and then as a mid-bake for 100 to 500 seconds or 100 to 300 seconds at 80°C to 140°C or 90°C to 130°C.

[0197] A process for preparing a multilayer cured film according to a certain embodiment may include (step 2) coating a second colored photosensitive resin composition onto a first cured film and curing it to form a second cured film.

[0198] In the step of forming the second cured film, the second colored photosensitive resin composition is coated onto the first cured film obtained in step 1 to a desired thickness (for example, 4 μm to 8 μm), and the second colored photosensitive resin composition is cured by removing the solvent therefrom to form the second cured film.

[0199] Curing to form a second cured film can be carried out at 70°C to 140°C for 50 to 900 seconds. Curing can be carried out once or more times.

[0200] When curing is performed in a single step, the curing can be carried out over a period of 50 to 800 seconds, 100 to 800 seconds, 150 to 600 seconds, or 150 to 500 seconds at a temperature of 70°C to 140°C, 80°C to 130°C, or 90°C to 130°C.

[0201] If curing is performed more than once, for example, the curing can be performed as a pre-bake for 50 to 400 seconds, 50 to 300 seconds, or 100 to 300 seconds at 70°C to 100°C or 70°C to 90°C, and then as a mid-bake for 100 to 500 seconds or 100 to 300 seconds at 80°C to 140°C or 90°C to 130°C.

[0202] The curing conditions for the first cured film and the curing conditions for the second cured film may be the same or different.

[0203] Immediately after step 2 and before step 3, an additional n layers of the second cured film may be formed on the second cured film, followed by exposure and development. In such a case, the photosensitive resin composition used to prepare one or more cured films formed on the second cured film may be the same as or different from the photosensitive resin composition used to prepare the second cured film. However, the final cured film (the nth cured film) should be formed from the second colored photosensitive resin composition. In such a case, it is more advantageous from the viewpoint of light shielding to use a copolymer containing structural units (b3) derived from fluorine-containing ethylenically unsaturated compounds in the second colored photosensitive resin composition.

[0204] A process for preparing a multilayer cured film according to one embodiment includes exposing and developing the multilayer cured film to form a pattern, and then post-baking it (step 3).

[0205] In Step 3, in order to form a pattern on the first cured film and the second cured film, a mask having a predetermined shape is placed thereon, and then an actinic ray of 200 nm to 500 nm is irradiated. As the light source used for irradiation, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an argon gas laser or the like can be used. If necessary, X-rays, electron beams or the like can also be used. The irradiation amount of light for exposure can vary depending on the type and composition ratio of the components of the composition and the thickness of the dry coating. When a high-pressure mercury lamp is used, the irradiation amount is (at a wavelength of 365 nm) 500 mJ / cm 2 may be as follows.

[0206] After the exposure step, an aqueous alkaline solution (sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide or the like) is used as a developer to dissolve and remove the unnecessary portions, whereby only the exposed portions remain and a pattern is formed. The image pattern obtained by development is cooled to room temperature and post-baked in a hot air circulation type drying oven, thereby obtaining the final pattern.

[0207] Exposure can be carried out by placing a mask such that the interval between each pattern is 10 μm to 30 μm and irradiating this mask with an actinic ray.

[0208] Development can be carried out over 50 seconds to 300 seconds, specifically over 100 seconds to 300 seconds.

[0209] Curing (i.e., post-baking) during pattern formation can be carried out for 10 minutes to 60 minutes, 20 minutes to 50 minutes or 20 minutes to 40 minutes at 150°C to 300°C, 180°C to 280°C or 200°C to 260°C.

[0210] According to the process for preparing a multilayer cured film according to an embodiment, it is possible to form a pattern (i.e., a multilayer pattern) on each layer, and further, this pattern has a uniform film thickness suitable for a quantum dot barrier rib in a single development process.

[0211] Embodiments for Carrying Out the Present Invention Hereinafter, the present invention will be described in more detail with reference to the following examples. However, these examples are provided to illustrate the present invention, and the scope of the present invention is not limited only to these examples.

[0212] In the following synthesis examples, the weight-average molecular weight is determined by gel permeation chromatography (GPC, eluent: tetrahydrofuran) based on polystyrene standards.

Example

[0213] Preparation Example 1: Preparation of the First Copolymer (A1-1) Into a 500 ml round-bottom flask equipped with a reflux condenser and a stirrer, 100 g of a monomer mixture composed of 23 mol% methacrylic acid, 43 mol% styrene, 9 mol% glycidyl methacrylate, and 25 mol% methyl methacrylate was charged together with 2 g of 2,2'-azobis(2,4-dimethylvaleronitrile) as a radical polymerization initiator, and these mixtures were dissolved in 300 g of propylene glycol monomethyl ether acetate (PGMEA). Then, this liquid mixture was heated to 70°C and stirred for 5 hours for polymerization to obtain a copolymer A1-1 having a solid content of 31% by weight. The copolymer A'1-1 thus prepared had a weight-average molecular weight of 12,000 Da, an acid value of 100 mg KOH / g, and a polydispersity (Mw / Mn) of 2.80.

[0214] Preparation Example 2: Preparation of the First Copolymer (A-2) The same procedure as in Preparation Example 1 was carried out except that the types and contents of the monomers were changed as shown in Table 1 below to prepare a copolymer A1-2 having a solid content of 31% by weight. The copolymer A1-2 thus prepared had a weight-average molecular weight of 14,000 Da, an acid value of 100 mg KOH / g, and a polydispersity (Mw / Mn) of 2.48.

[0215] Preparation Example 3: Preparation of the second copolymer (A2-1) Copolymer A2-1 with a solid content of 31% by weight was prepared by following the same procedure as in Preparation Example 1, except that the type and content of monomers were changed as shown in Table 2 below. The copolymer A2-1 thus prepared had a weight-average molecular weight of 14,100 Da, an acid value of 100 mg KOH / g, and a polydispersity (Mw / Mn) of 3.23.

[0216] Preparation Example 4: Preparation of the second copolymer (A2-2) A 250 ml round-bottom flask equipped with a reflux condenser and stirrer was filled with 30 g of a monomer mixture consisting of 30 mol% methacrylic acid, 10 mol% glycidyl methacrylate, 50 mol% nonafluorophenyl methacrylate, and 10 mol% trifluorohexyl methacrylate, along with 2.74 g of V-59 as a radical polymerization initiator. This mixture was then dissolved in 30 g of propylene glycol monomethyl ether acetate (PGMEA). Subsequently, this liquid mixture was added dropwise over 4 hours to a flask containing a solvent heated to 80°C under a nitrogen atmosphere, and polymerization was carried out over 20 hours to obtain copolymer A2-2 with a solid content of 30-33 wt%. The copolymer A2-2 thus prepared had a weight-average molecular weight of 15,000 Da, an acid value of 90-100 mg KOH / g, and a polydispersity (Mw / Mn) of 2.04.

[0217] Preparation Example 5: Preparation of the second copolymer (A2-3) A 500 ml round-bottom flask equipped with a reflux condenser and stirrer was filled with 100 g of a monomer mixture consisting of 23 mol% methyl methacrylate, 50 mol% cyclohexyl methacrylate, and 27 mol% methacrylic acid, along with 300 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent and 2 g of 2,2'-azobis(2,4-dimethylvaleronitrile) as a radical polymerization initiator. The mixture was then heated to 70°C and stirred for 5 hours to obtain copolymer A2-3 with a solid content of 31 wt%. Copolymer A2-3 thus prepared had an acid value of 107 mg KOH / g and a weight-average molecular weight (Mw) based on polystyrene, as measured by gel permeation chromatography, of 34,432 Da.

[0218] Preparation Example 6: Preparation of the second copolymer (A2-4) A 500 ml round-bottom flask equipped with a reflux condenser and stirrer was filled with 100 g of a monomer mixture consisting of 26 mol% methyl methacrylate, 40 mol% styrene, and 34 mol% methacrylic acid, along with 300 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent and 2 g of 2,2'-azobis(2,4-dimethylvaleronitrile) as a radical polymerization initiator. The mixture was then heated to 70°C and stirred for 5 hours to obtain copolymer A2-4 with a solid content of 31 wt%. Copolymer A2-4 thus prepared had an acid value of 161 mg KOH / g and a weight-average molecular weight (Mw) based on polystyrene, as measured by gel permeation chromatography, of 16,313 Da.

[0219] [Table 1]

[0220] [Table 2]

[0221] Example: Preparation of a photosensitive resin composition The components used in the following examples are as follows:

[0222] [Table 3]

[0223] Example 1: Preparation of the first colored photosensitive resin composition 80 parts by weight of the first copolymer (A1-1) from Preparation Example 1, 20 parts by weight of the first copolymer (A1-2) from Preparation Example 2, 92 parts by weight of DPHA as a photopolymerizable compound (B), 8.5 parts by weight of SPI05(C-1), 1.4 parts by weight of SPI02(C-2), and 1.4 parts by weight of Triazine-Y(C-3) as photopolymerization initiators (C), 65 parts by weight of TIS-010 as a white coloring agent (D1), 0.2 parts by weight of F-563 as a surfactant (E), and 3 parts by weight of epoxy compounds (F-1) and 0.3 parts by weight of XS1075(F-2) as additives were uniformly blended. Here, the respective contents are based on the solid content excluding the solvent. This mixture was dissolved in PGMEA as a solvent so that the solid content of the mixture was 27% by weight. The resulting mixture was mixed using a stirrer for 2 hours to prepare a first colored photosensitive resin composition in liquid phase.

[0224] Example 2: Preparation of a second colored photosensitive resin composition 100 parts by weight of the second copolymer (A2-1) from Preparation Example 3, 100 parts by weight of DPHA as a photopolymerizable compound (B), 1.1 parts by weight of SPI02 (C-2) and 2.2 parts by weight of Trizine-Y (C-3) as photopolymerization initiators (C), 6 parts by weight of PY139-3 (D-1) as a colorant other than white (D2), and 0.2 parts by weight of F-563 as a surfactant (E) were uniformly blended. Here, the respective contents are based on the solid content excluding the solvent. This mixture was dissolved in PGMEA as a solvent so that the solid content of the mixture was 19% by weight. The resulting mixture was mixed using a stirrer for 2 hours to prepare the second colored photosensitive resin composition in liquid phase.

[0225] Example 3: Preparation of Multilayer Cured Film Using the first colored photosensitive resin composition and / or the second colored photosensitive resin composition prepared in Examples 1 and 2, a cured film was prepared by the following method.

[0226] The first colored photosensitive resin composition was pretreated using a 1-μm syringe filter, coated onto a glass substrate using a spin coater, and prebaked at 90°C for 150 seconds to form a coating film having a thickness of 6.0 μm or more. This coating film was further subjected to mid-bake at 130°C for 300 seconds to remove the solvent, thereby forming the first cured film (i.e., the lower film).

[0227] Next, the second colored photosensitive resin composition pretreated using a 1-μm syringe filter was coated onto the first cured film, prebaked at 90°C for 150 seconds to form a second cured film (i.e., the upper film) having a thickness of 6.0 μm or more, thereby obtaining a two-layer multilayer cured film.

[0228] A mask was placed on this multilayer cured film such that an area of 5 cm × 5 cm was 100% exposed and the gap with the substrate was minimized to contact. Then, using an aligner device (model name: MA6) that emits light with a wavelength of 200 nm to 450 nm, for a specific period, based on a wavelength of 365 nm, an exposure amount of 150 mJ / cm 2 was performed. Next, it was developed with an aqueous developer of 0.04% by weight of potassium hydroxide at 23°C until the unexposed portions were completely washed away. The pattern thus formed was post-baked in an oven at 230°C for 30 minutes to obtain a multilayer cured film having a total thickness of 6.0 to 18 (±0.5) μm.

[0229] Examples 4 to 14 Multilayer cured films of Examples 4 to 14 were prepared in the same manner as in Example 3, except that a first colored photosensitive resin composition and a second colored photosensitive resin composition having the components and contents shown in Tables 4 and 5 were used.

[0230] [Table 4]

[0231] [Table 5]

[0232] Comparative Examples 1-9 The multilayer cured films of Comparative Examples 1 to 9 were prepared in the same manner as in Example 3, except that the first and second colored photosensitive resin compositions had the components and contents shown in Tables 6 and 7.

[0233] [Table 6]

[0234] [Table 7]

[0235] Evaluation Example 1: Development Time In the process of preparing the cured film, the time it took for the unexposed areas to be completely washed away with a 0.04 wt% potassium hydroxide aqueous solution (the time until the O-ring of the development device under the substrate was completely visible) was measured. ○: If the development time was 200 seconds or less ×: If the development time exceeds 200 seconds

[0236] Evaluation Example 2: Resolution To measure the pattern resolution and limiting dimension (CD; unit: μm) of the linear patterns in the cured films obtained in the examples, the line CD was observed using a micro-optical microscope (STM6-LM, manufacturer: OLYMPUS) and an X-ray scanning electron microscope (SEM; S4300). The results are shown in Tables 8 and 9 and Figure 5 below. ○: When the line CD is greater than 0 μm and 40 μm ×: If the line CD is greater than 40 μm or 0 μm

[0237] Evaluation Example 3: Film Thickness The cured films obtained in each example were measured using the SCAN PLUS alpha-step profilometer, specifically in relation to the height difference caused by the vertical movement of the instrument's probe tip. The thickness of the cured film was obtained from these results.

[0238] Regarding the initial film thickness, the thickness of the film formed immediately after pre-baking of the upper film was measured. Regarding the final film thickness, the thickness of the film after post-baking was measured. ○: When the initial thickness and final thickness are both 6 μm or more. ×: When the initial thickness and final thickness are both less than 6 μm.

[0239] Evaluation Example 4: Reflectance The cured films obtained in the examples were each measured using a spectrophotometer device (CM-3700A) to obtain the reflectance R using the SCI (including specular reflection) method. SCI and reflectance R by the SCE (non-specular reflection) method. SCE The ratio between these was measured (R SCE / R SCI ) was calculated.

[0240] Total reflectance (R SCI If the percentage was 50% or higher, it was evaluated as ○; if it was less than 50%, it was evaluated as ×.

[0241] Scattered reflectance (R SCEIf the percentage was 40% or higher, it was evaluated as ○; if it was less than 40%, it was evaluated as ×.

[0242] Ratio R SCE / R SCI If the percentage was 50% or higher, it was evaluated as ○; if it was less than 50%, it was evaluated as ×.

[0243] Evaluation Example 5: Contact Angle The cured films obtained in the examples were measured for contact angle using deionized water (DI water) and a contact angle measuring device (DM300, Kyowa), respectively.

[0244] [Table 8]

[0245] [Table 9]

[0246] Referring to the results in Tables 8 and 9, the multilayer cured films of Examples 3 to 14 each maintained excellent resolution and pattern characteristics while possessing high light-shielding properties and high reflectivity.

[0247] Specifically, the multilayer cured films of Examples 3 to 14 each had a total thickness of 6 μm to 20 μm, thereby forming a thickness sufficient for use as a quantum dot barrier rib. When a multilayer cured film with a thickness within the above range is used as a quantum dot barrier rib, the quantum dot solution will not overflow the barrier rib when dropped onto it. Therefore, colored compositions will not be mixed, and it is possible to prevent a deterioration of resolution.

[0248] In addition, the multilayer cured films of Examples 3-14 exhibit excellent R SCE Value and R SCI Not only did it show the values, but also the ratios between them (R SCE / R SCI The maximum reflectivity was 92.7%, which satisfied the requirement for high reflectivity.

[0249] On the other hand, it was confirmed that the reflectance varies depending on the TiO2 content in the white coloring agent and the particle size of the white coloring agent and the non-white coloring agents.

[0250] Specifically, the multilayer cured films of Examples 3 and 4 exhibited significantly superior reflectivity compared to the multilayer cured films of Comparative Examples 1 to 9, and were further improved compared to the multilayer cured films of Examples 5 to 14.

[0251] In addition, Figure 5 shows photographs of the cross-section and side view of the multilayer cured films of Examples 3 to 14 as observed with an optical microscope. As can be seen from Figure 5, the multilayer cured films of Examples 3 to 14 all had clear and distinct line widths and colors, and the film thickness was uniform and thick.

[0252] In contrast, as can be seen from Figure 6, the multilayer cured films of Comparative Examples 1-9 had less distinct line width and color, poor thickness uniformity, or excessively low film thickness compared to the cured films of Examples 3-14, and were therefore unsuitable as barrier ribs. [Explanation of Symbols]

[0253] 100 Base material structure 110 Transparent base material 120 Barrier Ribs 130 First quantum dot solution 140 Second quantum dot solution 150 Third quantum dot solution 200, 300, 400 multilayer cured film 210, 310, 410 base material 211, 311, 411 First curing film 212, 312, 313, 412, 413, n Second curing film

Claims

1. A colored photosensitive resin composition, (A) Copolymer; (B) photopolymerizable compound; (C) Photopolymerization initiator; (D) Colorants; and (E) Glycidyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether, 3,4-epoxybutyl (meth)acrylate, 4,5-epoxypentyl (meth)acrylate, 5,6-epoxyhexyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, 2,3-epoxycyclopentyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, α-ethylglycidyl acrylate, α-n-propylglycidyl acrylate α-n-butylglycidyl acrylate, N-(4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl)acrylamide, N-(4-(2,3-epoxypropoxy)-3,5-dimethylphenylpropyl)acrylamide, allyl glycidyl ether, 2-methylallyl glycidyl ether, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether, and epoxy compounds selected from the group consisting of these. Includes, The copolymer (A) comprises the first copolymer (A1), The aforementioned coloring agent (D) includes a white coloring agent (D1), The first copolymer (A1) is (a1) Structural units derived from ethylenically unsaturated carboxylic acids, ethylenically unsaturated carboxylic acid anhydrides, or combinations thereof; (a2) Structural units derived from ethylenically unsaturated compounds containing aromatic rings; (a3) Structural units derived from ethylenically unsaturated compounds containing epoxy groups; and (a4) Structural units derived from ethylenically unsaturated compounds different from (a1) to (a3) A colored photosensitive resin composition containing [the specified element].

2. The aforementioned white coloring agent (D1) is titanium dioxide (TiO ２ ), zirconium oxide (ZrO ２ ), zinc oxide (ZnO) and silicon dioxide (SiO ２ The colored photosensitive resin composition according to claim 1, which is at least one selected from the group consisting of ).

3. The colored photosensitive resin composition according to claim 1, wherein the white coloring agent (D1) is used in an amount of 20 to 65 parts by weight (based on solid content) per 100 parts by weight of the first copolymer (A1).

4. The colored photosensitive resin composition according to claim 1, wherein the white coloring agent (D1) has a particle size of 120 nm to 400 nm.

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