Photosensitive resin composition, photosensitive resin layer using same, display device, and method for producing photosensitive resin layer

Abstract

Provided are an antioxidant-free photosensitive resin composition, a photosensitive resin layer manufactured using the same, a display device including the photosensitive resin layer, and a method of manufacturing the photosensitive resin layer. The antioxidant-free photosensitive resin composition includes: (A) a binder resin; (B) a colorant; (C) a polymerizable monomer; (D) a polymerization initiator; and (E) a solvent in which a colorant and a polymerization initiator are included in an amount of about 80 wt% to about 95 wt% and about 0.65 wt% to about 1.3 wt%, the colorant including a green pigment and a yellow pigment, and the green pigment being included in an amount of greater than or equal to about 50 wt% based on the total amount of the colorant.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefits of Korean Patent Application No. 10-2023-0088563 filed in the Korean Intellectual Property Office on July 7, 2023, and Korean Patent Application No. 10-2024-0056932 filed in the Korean Intellectual Property Office on April 29, 2024, the entire contents of which are incorporated herein by reference. Technical Field

[0003] The present disclosure relates to a photosensitive resin composition, a photosensitive resin layer using the same, a display device, and a method for manufacturing the photosensitive resin layer. Background Art

[0004] Recently, as display panels are applied to virtual reality (VR), augmented reality (AR) and mixed reality (MR) devices, attention is increasing on self-luminous micro organic light emitting diode (OLED) display panels that emit light by themselves.

[0005] Since the micro OLED display panel has pixels that are about ten times smaller than those of a general OLED display panel, it is difficult to accurately form the red (R) / green (G) / blue (B) light emitting layers by the conventional fine metal mask (FMM) technology. In other words, when conventional liquid crystal displays are applied to devices such as VR devices, AR devices, and the like, the color filter has an excessively large pattern size and cannot improve the resolution.

[0006] Therefore, in order to achieve a high resolution of about 4000 pixels per inch (ppi) or more, OLED on Silicon (OLEDoS) technology has recently been introduced. This corresponding technology uses an OLED deposited on a silicon wafer as a backlight to pattern the color filter thereon. Although the color filters used in conventional liquid crystal displays use a pattern of about 100 μm on glass and are cured by exposure and post-baking at a high temperature of about 230°C or higher, the color filters on OLEDoS cannot be processed at high temperatures due to OLED, so they must be cured at low temperatures and must also be micro-patterned to improve resolution. In order to be applied to small-sized VR devices, AR devices, and MR devices, micropatterning is crucial to achieving the desired resolution.

[0007] However, since curing must be performed at a low temperature (about 100° C. or lower), it is difficult for a color filter formed of a conventional material to form a high-resolution pattern and ensure a color gamut and a viewing angle. Summary of the invention

[0008] Some embodiments provide a photosensitive resin composition that can be sufficiently cured even at low temperatures, has excellent high-resolution pattern forming properties, and can further ensure a high color gamut and viewing angle.

[0009] Some embodiments provide a photosensitive resin layer manufactured using the photosensitive resin composition.

[0010] Some embodiments provide a display device including a photosensitive resin layer.

[0011] Some embodiments provide a method for manufacturing a photosensitive resin layer.

[0012] Some embodiments provide an antioxidant-free photosensitive resin composition, the antioxidant-free photosensitive resin composition comprising: (A) a binder resin; (B) a colorant; (C) a polymerizable monomer; (D) a polymerization initiator; and (E) a solvent, wherein the colorant and the polymerization initiator are contained in an amount of about 80 wt % to about 95 wt % and about 0.65 wt % to about 1.3 wt %, respectively, the colorant comprises a green pigment and a yellow pigment, and the green pigment is contained in an amount greater than or equal to about 50 wt % based on the total amount of the colorant.

[0013] The green pigment and the yellow pigment may each be independently included in the form of a pigment dispersion.

[0014] The binder resin may be an acrylic binder resin.

[0015] The acrylic binder resin may have an acid value of greater than or equal to about 50 KOHm / g and a weight average molecular weight of less than or equal to about 7000 g / mol.

[0016] The acrylic binder resin may have a double bond equivalent weight of greater than or equal to about 360 g / mol.

[0017] The polymerizable monomer may include one or more compounds including three or more functional groups.

[0018] The polymerizable monomer may be a mixture of two types of compounds, and the two types of compounds may each independently be a compound including three or more functional groups.

[0019] The two types of compounds may be mixed with each other in a weight ratio of about 1:1.

[0020] The polymerizable monomer may be included in an amount greater than that of the binder resin.

[0021] The photosensitive resin composition may have a full width at half maximum (FWHM) of less than 105 nm.

[0022] The photosensitive resin composition may have a transmittance of less than about 8% at 630 nm.

[0023] The photosensitive resin composition may include: about 1 wt % to about 5 wt % of the (A) binder resin, about 80 wt % to about 95 wt % of the (B) colorant, about 1 wt % to about 10 wt % of the (C) polymerizable monomer, about 0.65 wt % to about 1.3 wt % of the (D) polymerization initiator, and the balance of the (E) solvent, based on the total amount of the photosensitive resin composition.

[0024] The photosensitive resin composition may further include the following additives: for example, malonic acid, 3-amino-1,2-propanediol, a silane coupling agent, a leveling agent, a surfactant, or a combination thereof.

[0025] The photosensitive resin composition may be a composition for a micro OLED display device.

[0026] Some embodiments provide a photosensitive resin layer, wherein the photosensitive resin layer is manufactured using the photosensitive resin composition.

[0027] Some embodiments provide a display device including a photosensitive resin layer.

[0028] The display device may be a micro OLED display device, which includes an OLED substrate and a color filter layer, wherein the OLED substrate is located on a silicon wafer, and the color filter layer is stacked on the OLED substrate and converts white light generated from the OLED substrate into light of multiple colors, wherein the color filter layer includes a red filter, a green filter, and a blue filter.

[0029] Some embodiments provide a method for manufacturing a photosensitive resin layer, the method comprising: coating the photosensitive resin composition; pre-baking at a temperature less than or equal to about 100° C. after the coating; and exposing to i-line and developing the photosensitive resin composition after the pre-baking.

[0030] Other embodiments are included in the detailed description that follows.

[0031] The photosensitive resin composition according to some embodiments can be cured at a low temperature of about 100° C. or less, can ensure high resolution by implementing fine patterns, and has excellent spectral characteristics, so that a wide color gamut can be ensured. In particular, the photosensitive resin composition is suitable for application to a micro OLED display device because it has excellent color characteristics and can produce fine patterns only by temperature and light curing (i-line exposure) when pre-baking is performed at about 100° C. or less. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 is a graph showing the spectrum of the photosensitive resin composition according to Example 1 and Comparative Example 3. DETAILED DESCRIPTION

[0033] Embodiments are described in detail below. However, these embodiments are exemplary, the present disclosure is not limited thereto, and the present invention is defined by the scope of the claims.

[0034] As used herein, when a specific definition is not otherwise provided, “alkyl” refers to a C1 to C20 alkyl group, “alkenyl” refers to a C2 to C20 alkenyl group, “cycloalkenyl” refers to a C3 to C20 cycloalkenyl group, “heterocycloalkenyl” refers to a C3 to C20 heterocycloalkenyl group, “aryl” refers to a C6 to C20 aryl group, “arylalkyl” refers to a C6 to C20 arylalkyl group, “alkylene” refers to a C1 to C20 alkylene group, “arylene” refers to a C6 to C20 arylene group, “alkylarylene” refers to a C6 to C20 alkylarylene group, “heteroarylene” refers to a C3 to C20 heteroarylene group, and “alkyleneoxy” refers to a C1 to C20 alkyleneoxy group.

[0035] As used herein, when a specific definition is not otherwise provided, “substituted” means that at least one hydrogen is replaced by a substituent selected from the group consisting of a halogen atom (F, Cl, Br or I), a hydroxyl group, a C1 to C20 alkoxy group, a nitro group, a cyano group, an amine group, an imino group, an azido group, an amidino group, a hydrazine group, a hydrazone group, a carbonyl group, a carbamoyl group, a thiol group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphate group or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C20 aryl group, a C3 to C20 cycloalkyl group, a C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, a C3 to C20 heteroaryl group or a combination thereof.

[0036] As used herein, when a specific definition is not otherwise provided, "hetero" means including at least one heteroatom of N, O, S and P in a chemical formula.

[0037] As used herein, when specific definition is not otherwise provided, “(meth)acrylate” refers to “acrylate” and “methacrylate”, and “(meth)acrylic acid” refers to “acrylic acid” and “methacrylic acid”.

[0038] As used herein, when no definition is otherwise provided, the term "combination" refers to mixing or copolymerization. In addition, "copolymerization" refers to block copolymerization to random copolymerization, and "copolymer" refers to block copolymer to random copolymer.

[0039] In the chemical formulae in the present specification, unless a specific definition is otherwise provided, when a chemical bond is not drawn where it should be given, a hydrogen bond is made at the position.

[0040] As used herein, when no definition is otherwise provided, "*" represents a point of connection to the same atom or different atoms or chemical formulas.

[0041] According to some embodiments, the photosensitive resin composition does not include an antioxidant, and as a composition without an antioxidant, may include: (A) a binder resin; (B) a colorant; (C) a polymerizable monomer; (D) a polymerization initiator; and (E) a solvent, wherein the colorant and the polymerization initiator are included in an amount of about 80 wt % to about 95 wt % and about 0.65 wt % to about 1.3 wt %, respectively, the colorant includes a green pigment and a yellow pigment, and the green pigment is included in an amount greater than or equal to about 50 wt % based on the total amount of the colorant.

[0042] Conventional color photoresists are negative photosensitive liquid materials that are implemented into red patterns, green patterns, and blue patterns, and have been technically developed in the direction of gradually modifying the composition of the liquid material. For example, attempts have been made to improve color purity by modifying the type or content of a pigment dispersion as a coloring material for implementing a color pattern, to improve patterning capability by modifying the composition of a binder resin or a photopolymerization initiator, or to improve coating properties and color uniformity by using other additives such as a leveling agent and the like.

[0043] However, unlike conventional color photoresists, some embodiments relate to a photosensitive resin composition applied to a color filter process used in a micro OLED display device, and particularly to a green photosensitive resin composition applied to a green color filter process.

[0044] Micro OLED refers to a white OLED (White OLED, WOLED) deposited on a silicon wafer. Among inventors, it is also called an organic light emitting diode on silicon (OLEDoS). And, a micro OLED display device refers to a display device applied on a micro OLED.

[0045] With the advancement of the era of the fourth industrial revolution and the rapid growth of the metaverse market, there is an increasing need to develop display devices that improve the authenticity and visibility of AR devices, VR devices, and MR devices but minimize dizziness. For this purpose, several candidate technologies have been developed, such as Liquid Crystal on Silicon (LCoS), Light Emitting Diode on Silicon (LEDoS), Organic Light Emitting Diode on Silicon (OLEDoS), and similar technologies. Among these technologies, OLEDoS technology, which has the advantages of high contrast, fast response speed, and self-emission to reduce the size and weight of the device to a relatively simple optical system, is developing rapidly in many fields.

[0046] Compared with conventional displays, OLEDoS requires forming very small pixels in the unit of several micrometers to realize a micro display with high resolution, and needs to form color filters through a low-temperature process to avoid damage to the lower OLED, which causes many difficulties in development.

[0047] In this context, the present inventors have developed a photosensitive resin composition to achieve low-temperature curing and micro-patterning by controlling the respective contents of a colorant and a polymerization initiator and further controlling the content of a green pigment in the colorant (but excluding an antioxidant), thereby completing micro-patterning and ensuring excellent color uniformity and a photosensitive resin composition curable at a low temperature of about 100° C. or less, and therefore, due to these characteristics, the photosensitive resin composition according to some embodiments can be applied to display devices for VR (virtual reality), AR (augmented reality) and MR (mixed reality) as next-generation displays (e.g., micro OLED display devices).

[0048] In the following, each component is described in detail.

[0049] (A) Binder resin

[0050] The binder resin may include an acrylic binder resin. For example, the binder resin may be an acrylic binder resin.

[0051] The acrylic binder resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and is a resin including at least one acrylic acid repeating unit.

[0052] The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer including at least one carboxyl group. Examples of the monomer include (meth)acrylic acid, maleic acid, itaconic acid, fumaric acid, or a combination thereof.

[0053] The first ethylenically unsaturated monomer may be included in an amount of about 5 wt % to about 50 wt %, for example, about 10 wt % to about 40 wt %, based on the total amount of the acrylic binder resin.

[0054] The second ethylenically unsaturated monomer may be an aromatic vinyl compound such as styrene, α-methylstyrene, vinyltoluene, vinylbenzyl methyl ether, and the like; an unsaturated carboxylic acid ester compound such as methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, benzyl(meth)acrylate, cyclohexyl(meth)acrylate, phenyl(meth)acrylate, and the like; an unsaturated aminoalkylcarboxylic acid ester compound such as 2-aminoethyl(meth)acrylate, 2-dimethylaminoethyl(meth)acrylate, and the like; a carboxylic acid vinyl ester compound such as vinyl acetate, vinyl benzoate, and the like; an unsaturated glycidylcarboxylic acid ester compound such as glycidyl(meth)acrylate, and the like; a vinyl cyanide compound such as (meth)acrylonitrile, and the like; an unsaturated amide compound such as (meth)acrylamide, and the like; and the like, and the compounds may be used alone or in the form of a mixture of two or more thereof.

[0055] Specific examples of the acrylic binder resin may be (meth)acrylic acid / benzyl methacrylate copolymer, (meth)acrylic acid / benzyl methacrylate / styrene copolymer, (meth)acrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer, (meth)acrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, and the like, but are not limited thereto, and these acrylic resins may be used alone or in the form of a mixture of two or more.

[0056] The acrylic binder resin may have a weight average molecular weight of less than or equal to about 7,000 g / mol, for example, about 3,000 g / mol to about 7,000 g / mol, and an acid value of greater than or equal to about 50 KOHm / g, for example, about 50 KOHm / g to about 90 KOHm / g, for example, about 60 KOHm / g to about 80 KOHm / g, and may have a double bond equivalent weight of greater than or equal to about 360 g / mol. When the weight average molecular weight, acid value, and double bond equivalent weight of the acrylic binder resin are within the above ranges, excellent pattern forming properties may be achieved, and the resulting film may have excellent mechanical and thermal properties.

[0057] The binder resin may further include an epoxy-based binder resin.

[0058] The binder resin may improve heat resistance by further including an epoxy-based binder resin. The epoxy-based binder resin may be, for example, phenol novolac epoxy resin, tetramethylbiphenyl epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, alicyclic epoxy resin or a combination thereof, but is not limited thereto.

[0059] Furthermore, the binder resin including the epoxy-based binder resin ensures dispersion stability of a colorant such as a pigment, which will be described later, and helps to form pixels having a desired resolution during a development process.

[0060] The epoxy-based binder resin may be included in an amount of about 1 wt % to about 10 wt %, for example, about 5 wt % to about 10 wt %, based on the total amount of the binder resin. If the epoxy-based binder resin is included within the above range, the film residual rate and chemical resistance may be greatly improved.

[0061] The epoxy equivalent weight of the epoxy resin may be about 150 g / eq to about 200 g / eq. If the binder resin includes an epoxy binder resin having an epoxy equivalent within the above range, it has an advantageous effect in improving the degree of curing of the formed pattern and fixing the colorant in the structure in which the pattern is formed.

[0062] The binder resin may be included in an amount of about 1 wt % to about 5 wt %, such as about 1 wt % to about 4 wt %, such as about 2 wt % to about 4 wt %, based on the total amount of the photosensitive resin composition. When the binder resin is included within the above range, excellent sensitivity, developability, resolution and linearity of the pattern may be obtained.

[0063] (B) Colorants

[0064] The photosensitive resin composition according to some embodiments may be a green photosensitive resin composition, and in this case, the colorant in the composition may include a green pigment and a yellow pigment.

[0065] The green pigment may be CI green pigment 7, CI green pigment 36, CI green pigment 58, CI green pigment 59 and the like in a color index, and the green pigment may be used alone or in a mixture of two or more thereof, but the present disclosure is not limited thereto.

[0066] The yellow pigment in the color index may be: isoindoline pigments, such as CI yellow pigment 185, CI yellow pigment 139 and similar pigments; quinophthalone pigments, such as CI yellow pigment 138; nickel complex pigments, such as CI yellow pigment 150. The yellow pigments may be used alone or in the form of a mixture of two or more thereof, but the present disclosure is not limited thereto.

[0067] At this time, green pigment can be included in a weight greater than yellow pigment. Specifically, in terms of the total amount of colorant, green pigment is included in an amount greater than or equal to about 50% by weight. In addition, in terms of the total amount of the photosensitive resin composition according to some embodiments, the colorant including green pigment and yellow pigment can be about 80% by weight to about 95% by weight, for example, about 80% by weight to about 90% by weight, for example, about 80% by weight to about 85% by weight. When the content of the colorant is controlled as described above, when the content of the green pigment in the colorant is further controlled as described above, the full width at half maximum (full width at half maximum, FWHM) is narrowed, the color gamut is increased, and the transmittance at 630nm is reduced, making it very easy to achieve the effect of improving the viewing angle.

[0068] For example, the photosensitive resin composition according to some embodiments may have a full width at half maximum (FWHM) of less than 105 nm, and thus may be advantageous in increasing a color gamut.

[0069] For example, the photosensitive resin composition according to some embodiments may have a transmittance of less than about 8% at 630 nm, and thus may have an excellent viewing angle improvement effect.

[0070] The colorant may include a purple pigment in addition to a green pigment and a yellow pigment.

[0071] The violet pigment in the color index may be CI violet pigment 23 (V.23), CI violet pigment 29, dioxazine violet, first violet B, methyl violet lake, indanethrene brilliant violet and similar pigments, and the violet pigments may be used alone or in the form of a mixture of two or more thereof, but the present disclosure is not limited thereto.

[0072] These pigments may be used alone or in admixture of two or more.

[0073] The pigment may be used after pretreatment with a water-soluble inorganic salt and a wetting agent. When the pigment is used after pretreatment, the average particle size of the pigment may become finer.

[0074] The pretreatment can be carried out by kneading the pigment with a water-soluble inorganic salt and a wetting agent, and then filtering and washing the kneaded pigment.

[0075] Kneading may be performed at a temperature ranging from about 40° C. to about 100° C., and filtering and washing may be performed by filtering the pigment after washing away the inorganic salt with water and the like.

[0076] Examples of water-soluble inorganic salts may be sodium chloride, potassium chloride and similar materials, but are not limited thereto. The wetting agent allows the pigment to be uniformly mixed with the water-soluble inorganic salt and crushed. Examples of wetting agents include: alkylene glycol monoalkyl ethers, such as ethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether and the like; and alcohols, such as ethanol, isopropanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerol polyethylene glycol and the like. The materials may be used alone or in combination of two or more.

[0077] The kneaded pigment may have an average particle size of about 5 nm to about 200 nm, for example, about 5 nm to about 150 nm. When the average particle size of the pigment is within the above range, the stability of the pigment mill base (pigment dispersion) is excellent, and there is no concern about degradation of pixel resolution.

[0078] The pigments (eg, green pigment and yellow pigment) can each be used independently together with a dispersant and a solvent in the form of a pigment dispersion (eg, mill base).

[0079] The dispersant helps the pigment to be uniformly dispersed in the dispersion, and nonionic dispersants, anionic dispersants or cationic dispersants can be used respectively. Specifically, polyalkylene glycol or its ester, polyoxyalkylene, polyol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonate, carboxylate, carboxylate, alkylamide alkylene oxide adduct, alkylamine, etc. can be used, and the dispersant can be used alone or in combination of two or more.

[0080] Commercially available examples of dispersants may include: DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, DISPERBYK-166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001 and similar materials made by BYK Co., Ltd.; Co.); Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000 and similar materials made by Zeneka Co.; or PB711 or PB821 made by Ajinomoto Inc.

[0081] The dispersant may be included in an amount of about 0.1 wt % to about 15 wt % based on the total amount of the photosensitive resin composition. If the dispersant is included within the above range, the composition has excellent dispersibility, and thus when a photosensitive resin layer is manufactured, stability, developability, and patterning ability are excellent.

[0082] Such pigment dispersions may include a dispersing aid, a dispersing resin, in addition to the pigment, dispersant, and (dispersing) solvent. Based on the total amount of the pigment dispersion, the solid pigment may be included in an amount of about 5 wt % to about 20 wt %, for example, about 8 wt % to about 15 wt %.

[0083] The (dispersion) solvent used for the pigment dispersion may be ethylene glycol acetate, ethyl celulose, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether and the like, and propylene glycol methyl ether acetate is preferable.

[0084] The dispersion resin may be an acrylic resin including a carboxyl group, which may improve the stability of the pigment dispersion and may also improve pixel patterning capability.

[0085] The colorant may include a pigment, and may also include a dye, and in this case, the photosensitive resin composition of some embodiments may be a mixed composition. In addition, the dye is not particularly limited, but may include a metal complex dye.

[0086] The metal complex dye may be a compound having a maximum absorbance in the wavelength range of 200 nm to 650 nm, and metal complex dyes of all colors dissolved in an organic solvent may be used if the compound has an absorbance in the above range to match the color coordinates with the combination of dyes.

[0087] Specifically, the metal complex dye may be a green dye having a maximum absorbance in a wavelength range of 530 nm to 680 nm, a yellow dye having a maximum absorbance in a wavelength range of 200 nm to 400 nm, an orange dye having a maximum absorbance in a wavelength range of 300 nm to 500 nm, a red dye having a maximum absorbance in a wavelength range of 500 nm to 650 nm, or a combination thereof.

[0088] The metal complex dye can be a direct dye, an acid dye, a basic dye, an acid mordant dye, a sulfide dye, a vat dye, an ice dye, a disperse dye, a reactive dye, an oxidation dye, an oil-soluble dye, an azo dye, an anthraquinone dye, an indigo dye, a carbonium ion dye, a phthalocyanine dye, a nitro dye, a quinoline dye, a cyanine dye, a polymethine dye, or a combination thereof.

[0089] The metal complex dye may include at least one metal ion selected from Mg, Ni, Cu, Co, Zn, Cr, Pt, Pd and Fe.

[0090] The metal complex dye may be a complex of at least one selected from the group consisting of: CI solvent dyes such as CI Solvent Green 1, CI Solvent Green 3, CI Solvent Green 4, CI Solvent Green 5, CI Solvent Green 7, CI Solvent Green 28, CI Solvent Green 29, CI Solvent Green 32, CI Solvent Green 33, CI Solvent Green 34, CI Solvent Green 35 and similar dyes; CI acid dyes such as CI Acid Green 1, CI Acid Green 3, CI Acid Green 5, CI Acid Green 6, CI Acid Green 7, CI Acid Green 8, CI Acid Green 9, CI Acid Green 11, CI Acid Green 13, CI Acid Green 14, CI Acid Green 15, CI Acid Green 16, CI Acid Green 17, CI Acid Green 18, CI Acid Green 19, CI Acid Green 20, CI Acid Green 21, CI Acid Green 22, CI Acid Green 23, CI Acid Green 24, CI Acid Green 25 and similar dyes; CI Acid Green 15, CI Acid Green 16, CI Acid Green 22, CI Acid Green 25, CI Acid Green 27, CI Acid Green 28, CI Acid Green 41, CI Acid Green 50, CI Acid Green 50:1, CI Acid Green 58, CI Acid Green 63, CI Acid Green 65, CI Acid Green 80, CI Acid Green 104, CI Acid Green 105, CI Acid Green 106, CI Acid Green 109 and similar dyes; CI direct dyes, for example CI Direct Green 25, CI Direct Green 27, CI Direct Green 31, CI Direct Green 32, CI Direct Green 34, CI Direct Green 37, CI Direct Green 63 , CI Direct Green 65, CI Direct Green 66, CI Direct Green 67, CI Direct Green 68, CI Direct Green 69, CI Direct Green 72, CI Direct Green 77, CI Direct Green 79, CI Direct Green 82 and similar dyes; CI basic dyes, such as CI Basic Green 1 and similar dyes; CI mordant dyes, such as CI Mordant Green 1, CI Mordant Green 3, CI Mordant Green 4, CI Mordant Green 5, CI Mordant Green 10, CI Mordant Green 13, CI Mordant Green 15, CI Mordant Green 19, CI Mordant Green 21, CI Mordant Green 23, CI Mordant Green 26, CI Mordant Green 29, CI Mordant Green 31, CI Mordant Green 32, CI Mordant Green 33, CI Mordant Green 34, CI Mordant Green 35, CI Mordant Green 36, CI Mordant Green 37, CI Mordant Green 38, CI Mordant Green 39, CI Mordant Green 40, CI Mordant Green 41, CI Mordant Green 42, CI Mordant Green 43, CI Mordant Green 44, CI Mordant Green 45, CI Mordant Green 46, CI Mordant Green 47, CI Mordant Green 48, CI Mordant Green 49, CI Mordant Green 50, CI Mordant Green 51, CI Mordant Green 52 CI Mordant Green 33, CI Mordant Green 34, CI Mordant Green 35, CI Mordant Green 41, CI Mordant Green 43, CI Mordant Green 53 and similar dyes; CI green pigments, such as Pigment Green 7, Pigment Green 36, Pigment Green 58 and similar pigments; Solvent Yellow 19, Solvent Yellow 21, Solvent Yellow 25, Solvent Yellow 79, Solvent Yellow 82, Solvent Yellow 88, Solvent Orange 45, Solvent Orange 54, Solvent Orange 62, Solvent Orange 99, Solvent Red 8, Solvent Red 32, Solvent Red 109, Solvent Red 112, Solvent Red 119, Solvent Red 124, Solvent Red 160, Solvent Red 132 and Solvent Red 218, and metal ions.

[0091] In the solvent used in the photosensitive resin composition according to some embodiments (i.e., a solvent to be described later), the metal complex dye may have a solubility of greater than or equal to about 5, specifically, about 5 to about 10. The solubility can be obtained by the amount (g) of the dye dissolved in 100 g of the solvent. If the solubility of the metal complex dye is within the above range, compatibility with other components constituting the photosensitive resin composition according to some embodiments and tinting power can be ensured, and precipitation of the dye can be prevented.

[0092] The solvent may be, for example, propylene glycol monomethyl etheracetate (PGMEA), ethyl lactate (EL), ethylene glycol ethyl acetate (EGA), cyclohexanone, 3-methoxy-1-butanol, or a combination thereof.

[0093] The metal complex dye may be included in an amount of about 0.01 wt % to about 1 wt %, for example, about 0.01 wt % to about 0.5 wt %, based on the total amount of the photosensitive resin composition. If a metal complex dye within the above range is used, high brightness and contrast may be expressed in desired color coordinates.

[0094] If the dye and the pigment are mixed and used, the dye and the pigment may be mixed in a weight ratio of about 0.1:99.9 to about 99.9:0.1, specifically, about 1:9 to about 9: 1. If mixed within the above weight ratio range, chemical resistance and maximum absorption wavelength may be controlled within appropriate ranges, and high brightness and contrast may be expressed in desired color coordinates.

[0095] As described above, the colorant may be included in an amount of about 80 wt % to about 95 wt %, for example, about 80 wt % to about 90 wt %, for example, about 80 wt % to about 85 wt %, based on the total amount of the photosensitive resin composition. If the colorant is included in a very high content as described above, in the micro OLED display device, the coloring effect and developability are excellent, making it easy to ensure high color gamut and viewing angle characteristics.

[0096] (C) polymerizable monomer

[0097] The polymerizable monomer in the photosensitive resin composition according to some embodiments may include one or more compounds including three or more functional groups. Herein, the functional group may be a (meth)acrylate group, an epoxy group, etc., but is not necessarily limited thereto.

[0098] According to some embodiments, the photosensitive resin composition has been developed for micro-OLED display devices, and the low temperature curing process is crucial. However, in the case of low temperature curing pattern process, the contribution of thermal curing is reduced, and the influence of photocuring is bound to increase. Therefore, maximizing the photocuring efficiency is conducive to ensuring excellent patterning ability under low temperature curing. According to some embodiments, by using a compound having at least three functional groups in a monomer as a polymerizable monomer, the photocuring efficiency can be maximized. Specifically, the photocuring efficiency is greatly affected by the weight average molecular weight of the polymerizable monomer and the number of functional groups. In general, the smaller the weight average molecular weight of the polymerizable monomer and the more the number of functional groups in the polymerizable monomer, the higher the photocuring efficiency. For example, a compound having at least three functional groups in a monomer has a small weight average molecular weight and a large number of functional groups, and is therefore conducive to maximizing the photocuring efficiency.

[0099] For example, the polymerizable monomer may be a mixture of two types of compounds, and the two types of compounds may each independently be a compound containing three or more functional groups. For example, the polymerizable monomer may be a mixture of a polymerizable compound including three functional groups and a polymerizable compound including 4 to 6 functional groups. When the polymerizable monomer has the above mixed composition, the photocuring efficiency can be maximized while maintaining the above color characteristics, making it easy to form a low-temperature curing pattern.

[0100] For example, the two types of compounds may be mixed with each other at a weight ratio of about 1: 1. If the above two types of compounds are mixed at the same weight ratio, the low temperature curing patterning capability may be improved to the greatest extent.

[0101] For example, the polymerizable compound including the three functional groups may be represented by Chemical Formula 1, but is not necessarily limited thereto.

[0102] [Chemical formula 1]

[0103]

[0104] In Chemical Formula 1,

[0105] L 1 To L 4 are each independently a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C1 to C20 oxyalkylene group, or a combination thereof,

[0106] R 1 to R 4 Each is independently hydrogen, hydroxyl, epoxy or substituted or unsubstituted (meth)acrylate, with the proviso that R 1 to R 4The three of them must be epoxy groups or substituted or unsubstituted (meth)acrylate groups.

[0107] For example, the compound including 4 to 6 functional groups may include pentaerythritol tetra(meth)acrylate, pentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, but is not necessarily limited thereto.

[0108] For example, the polymerizable monomer may be included in an amount greater than the binder resin. Conventional photosensitive resin compositions for color filters generally include a larger amount of binder resin than polymerizable monomers, but since the photosensitive resin compositions according to some embodiments applied to micro OLED display devices including WOLEDs deposited on silicon wafers rather than glass substrates or polyimide substrates as light sources must require low temperature curing, the case where a larger amount of polymerizable monomers than the binder resin is included may be more advantageous in terms of improving patterning capabilities. Specifically, if the polymerizable monomer is included in an amount greater than the binder resin, the polymerizable monomer may be fully polymerized with the photopolymerization initiator during exposure in a low-temperature pattern forming process (to be described later), thereby forming a pattern having excellent heat resistance, light resistance, and chemical resistance in a low-temperature process of about 100°C or less. Since conventional color filters for liquid crystal displays (LCDs) use resists to form patterns of about 100 μm, which is too large a size for use in micro OLED display devices, the present inventors control the contents of polymerizable monomers and binder resins, as well as the content of a photopolymerization initiator described later, to implement micropatterning and achieve low-temperature curing.

[0109] The polymerizable monomers may be treated with anhydrides to provide excellent developability.

[0110] The polymerizable monomer may be included in an amount of about 1 wt % to about 10 wt %, for example, about 1 wt % to about 5 wt %, based on the total amount of the photosensitive resin composition. If the polymerizable monomer is included within the range, sufficient curing may occur in a low-temperature pattern forming process, achieving excellent reliability, heat resistance, light resistance and chemical resistance of the pattern, resolution and adhesion.

[0111] (D) Polymerization initiator

[0112] The photosensitive resin composition according to some embodiments includes a polymerization initiator. In this article, the polymerization initiator is controlled to be about 0.65 wt % to about 1.3 wt %, for example, about 0.65 wt % to about 1.0 wt %, based on the total amount of the photosensitive resin composition. If the content of the polymerization initiator is controlled as above, an optimal pattern can be formed in a low temperature curing process together with the composition of the aforementioned polymerizable monomer, binder resin and colorant. When a polymerization initiator outside the above content range is used together with the composition of the aforementioned polymerizable monomer, binder resin and colorant, this may be undesirable because the patterning ability is greatly reduced during the low temperature curing process.

[0113] The polymerization initiator may be an acetophenone compound, a benzophenone compound, a thioxanthone compound, a benzoin compound, a triazine compound, an oxime compound or a combination thereof.

[0114] Examples of the acetophenone-based compounds may be 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, and the like.

[0115] Examples of the benzophenone-based compound may be benzophenone, benzoyl benzoate, benzoyl methyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, and the like.

[0116] Examples of the thioxanthone-based compound may be thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, and the like.

[0117] Examples of the benzoin-based compound may include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, and the like.

[0118] Examples of triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, triazine, 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-phenylvinyl-s-triazine, 2-(naphthol-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthol-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-bis(trichloromethyl)-6-piperonyl-s-triazine, 2-4-bis(trichloromethyl)-6-(4-methoxyphenylvinyl)-s-triazine and the like.

[0119] Examples of oxime compounds may be O-acyl oxime compounds, 2-(O-benzoyl oxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(O-acetyl oxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one and the like. Specific examples of O-acyl oxime compounds may be 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 1-(4-phenylsulfanylphenyl)-butane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1-one oxime-O-acetate, and 1-(4-phenylsulfanylphenyl)-butan-1-one oxime-O-acetate and the like, but are not necessarily limited thereto.

[0120] In addition to the above compounds, the polymerization initiator may include, for example, a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, and a biimidazole compound.

[0121] (E) Solvent

[0122] The solvent may be a material that is compatible with but does not react with the pigment dispersion including the colorant, the binder resin, the polymerizable monomer, and the polymerization initiator.

[0123] Examples of the solvent may be alcohols such as methanol, ethanol, and the like; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methyl phenyl ether, tetrahydrofuran, and the like; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, and the like; celulose acetates such as methyl celulose acetate, ethyl celulose acetate, diethyl celulose acetate, and the like; carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, and the like; propylene glycol alkyl ether acetate , such as propylene glycol methyl ether acetate, propylene glycol propyl ether acetate and the like; aromatic hydrocarbons such as toluene, xylene and the like; ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone, 2-heptanone and the like; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, isobutyl acetate and the like; lactic acid esters such as methyl lactate, ethyl lactate and the like; oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate and the like; alkoxyacetic acid alkyl esters such as methoxy Methyl acetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate and the like; alkyl 3-oxopropionates such as methyl 3-oxopropionate, ethyl 3-oxopropionate and the like; alkyl 3-alkoxypropionates such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate and the like; alkyl 2-oxopropionates such as methyl 2-oxopropionate, ethyl 2-oxopropionate, propyl 2-oxopropionate and the like; alkyl 2-alkoxypropionates such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate , ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate and the like; 2-oxy-2-methylpropionic acid esters, such as methyl 2-oxy-2-methylpropionic acid, ethyl 2-oxy-2-methylpropionic acid and the like; monooxymonocarboxylic acid alkyl esters of 2-alkoxy-2-methylpropionic acid alkyl esters, such as methyl 2-methoxy-2-methylpropionic acid, ethyl 2-ethoxy-2-methylpropionic acid and the like; esters, such as 2-hydroxyethyl propionic acid ester, 2-hydroxy-2-methylethyl propionic acid ester, hydroxyethyl acetate, 2-hydroxy-3-methylethyl butyrate and the like; ketoesters, such as ethyl pyruvate and the like. In addition, high boiling point solvents such as N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl celulose acetate and the like can also be used.

[0124] In view of compatibility and reactivity, it is preferable to use: glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol ethyl methyl ether and the like; ethylene glycol alkyl ether acetates such as ethyl celulose acetate and the like; esters such as 2-hydroxyethyl propionate and the like; carbitols such as diethylene glycol monomethyl ether and the like; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate and the like.

[0125] The solvent may be included in an amount of a balance, such as about 0.1 wt % to about 10 wt %, such as about 0.1 wt % to about 5 wt %, such as about 0.1 wt % to about 3 wt %, based on the total amount of the photosensitive resin composition. When the solvent is included within the above range, the photosensitive resin composition has an appropriate viscosity and thus improves the processability of manufacturing the photosensitive resin layer.

[0126] (F) Other additives

[0127] Meanwhile, the photosensitive resin composition may further include the following additives: malonic acid, 3-amino-1,2-propanediol, a silane coupling agent, a leveling agent, a surfactant or a combination thereof, but does not include an antioxidant.

[0128] The photosensitive resin composition according to some embodiments includes the binder resin, colorant, polymerizable compound, polymerization initiator and solvent of the aforementioned composition, and therefore, if an antioxidant is further included, the photocuring reaction does not proceed completely, the pattern formation is incomplete during the low temperature curing process, and thus high-resolution pattern formation may not be achieved. Therefore, the photosensitive resin composition according to some embodiments does not include an antioxidant, that is, has a composition without an antioxidant.

[0129] The silane-based coupling agent may have a reactive substituent of a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, an epoxy group, and the like to improve the close contact property with the substrate.

[0130] Examples of the silane-based coupling agent may include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and the like, and the silane-based coupling agent may be used alone or in the form of a mixture of two or more thereof.

[0131] The silane-based coupling agent may be included in an amount of about 0.01 parts by weight to about 10 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the silane-based coupling agent is included within the above range, adhesion, storage properties, and the like are improved.

[0132] In addition, if necessary, the photosensitive resin composition may further include a surfactant, such as a fluorine-based surfactant and / or a silicone-based surfactant, to improve coating properties and prevent defects.

[0133] Examples of fluorine-based surfactants include commercial fluorine-based surfactants such as BM Chemie Inc. and the like; MEGAFACE F of Dainippon Ink Kagaku Kogyo Co., Ltd. Megafa F Megafa F Megafa F Megafa F Megafa F and the like; FULORAD of SUMITOMO 3M Co., Ltd. Florard Florard Florard and the like; SURFLON of Asahi Glass Co., Ltd. Saffron Saffron Saffron Saffron and the like; Toray Silicone Co., Ltd. and the like.

[0134] The silicone-based surfactant may be a commercial silicone-based surfactant, such as BYK-307, BYK-333, BYK-361N, BYK-051, BYK-052, BYK-053, BYK-067A, BYK-077, BYK-301, BYK-322, BYK-325 and the like from BYK Chem.

[0135] The surfactant may be used in an amount of about 0.001 to about 5 parts by weight based on 100 parts by weight of the total amount of the photosensitive resin composition. When the surfactant is included within the range, coating uniformity may be ensured, stains may not be generated, and wettability on an indium zinc oxide (IZO) substrate or a glass substrate may be improved.

[0136] In addition, the photosensitive resin composition may include a predetermined amount of other additives (eg, stabilizer) unless the additives deteriorate the properties of the photosensitive resin composition.

[0137] The photosensitive resin composition according to some embodiments may be positive or negative, but should be negative to completely remove residues in a pattern-exposed region after exposing and developing the composition having a light-blocking property.

[0138] Some embodiments provide a photosensitive resin layer manufactured by low-temperature curing, exposure and development of the above-mentioned photosensitive resin composition. Compared with the traditional LCD process, the difference is that no post-curing (post-baking) process is required.

[0139] The method for producing the photosensitive resin layer is as follows.

[0140] (1) Coating and film formation (low temperature curing)

[0141] The photosensitive resin composition is coated on a substrate (e.g., a glass substrate or an ITO substrate and the like) that has been pre-treated to have a desired thickness using a spin coating method or a slit coating method, a roll coating method, a screen printing method, an applicator method, and the like, and heated at 100° C. or less, e.g., 85° C. for 1 to 10 minutes to remove the solvent and form a photosensitive resin layer. Through this step, image quality and unevenness can be improved.

[0142] (2) Exposure

[0143] After a mask is set to form a necessary pattern on the obtained photosensitive resin layer, exposure is performed by irradiating actinic rays of i-line. As a light source for irradiation, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an argon laser, etc. can be used, and in some cases, X-rays, electron beams, and similar light sources can be used.

[0144] The exposure dose varies depending on the type of each component in the composition, the mixing amount and the dry film thickness, but when a high-pressure mercury lamp is used, it can be less than or equal to about 500 mJ / cm 2 (measured on a 365 nm sensor). However, in some cases, the exposure dose may exceed about 500 mJ / cm 2 (via a 365nm sensor). This step allows the pixel size to be fine-tuned, allowing for high resolution.

[0145] (3) Development

[0146] In the development method, after the exposure step, an alkaline aqueous solution is used as a developer to dissolve and remove unnecessary parts, leaving only the exposed parts to form a pattern. Through this step, contours can be formed to achieve high resolution, and color uniformity can be ensured to improve clarity.

[0147] Some embodiments provide a display device including a photosensitive resin layer.

[0148] The display device may be a micro organic light emitting diode (OLED) display device.

[0149] The micro organic light emitting diode (OLED) display device may include an OLED substrate and a color filter layer, wherein the OLED substrate is located on a silicon wafer, and the color filter layer is stacked on the OLED substrate and converts white light generated from the OLED substrate into light of multiple colors, wherein the color filter layer includes a red filter, a green filter, and a blue filter.

[0150] For example, a micro organic light emitting diode (OLED) display device includes: an OLED substrate deposited on a silicon wafer; an inorganic layer deposited on the OLED substrate; an adhesive protective layer deposited on the inorganic layer; and a color filter layer deposited on the inorganic layer and converting white light generated from the OLED substrate into light of multiple colors, wherein the color filter may include a red filter, a green filter, and a blue filter.

[0151] For example, the photosensitive resin composition according to some embodiments is a green photosensitive resin composition, and the green color filter in the micro OLED display device may be a low-temperature cured layer of the green photosensitive resin composition.

[0152] Conventionally, an OLED substrate in which the OLED is deposited on a glass substrate or a polyimide substrate has been used, but a micro OLED display device according to some embodiments has an OLED deposited on a silicon wafer, which may be more advantageous in implementing a micro display. These micro displays have attracted much attention as next-generation displays, and it is expected that micro displays will be applied to devices such as MR. In fact, Apple, Meta, LG Display, etc. have entered or announced their entry into the next-generation MR device market.

[0153] For example, the micro OLED display device may further include a micro lens array, which may be disposed on the adhesive protection layer and surround the color filter layer.

[0154] The micro OLED display device having the above structure can be driven on a pixel basis because the WOLED is deposited on a highly integrated silicon wafer, and the transmission wavelength can be easily controlled by a color filter layer patterned with a resolution of about 3μm or less, which can advantageously ensure high color reproduction and high resolution.

[0155] For example, the adhesive protection layer may have a thickness of less than or equal to about 1 μm. Herein, the effect may be further maximized.

[0156] For example, the color filter layer may have a thickness of about 1.1 μm to about 1.6 μm.

[0157] If the color filter layer is controlled to have a thickness within the range, it may be more advantageous to implement a micro OLED display device.

[0158] For example, the inorganic layer may have a thickness of less than or equal to about 2 μm. Even in WOLED, since light does not always diffuse in the vertical direction relative to the OLED substrate, color mixing of red, green, and blue inevitably occurs, and in order to prevent such color mixing, an inorganic layer is conventionally deposited on the OLED substrate. However, since color mixing cannot be completely prevented by depositing an inorganic layer, some embodiments attempt to thin the inorganic layer, for example, controlling the thickness of the inorganic layer to about 2 μm or less, to prevent fine light leakage.

[0159] Finally, as described above, since the photosensitive resin composition according to some embodiments can be formed into a film only by low temperature curing (about 100° C.) and i-line photocuring during pre-baking, there will inevitably be a huge difference in the resolution to be achieved compared to conventional display devices.

[0160] Hereinafter, examples of the present invention are described. However, the following examples are only preferred examples of the present invention, and the present invention is not limited to the following examples.

[0161] (Example)

[0162] (Preparation of photosensitive resin composition)

[0163] Examples 1 to 23 and Comparative Examples 1 to 14

[0164] Using each composition shown in Table 1 to Table 5, a polymerization initiator was dissolved in a solvent and then stirred at room temperature for 2 hours. Herein, a binder resin and a polymerizable monomer were added thereto and then stirred at room temperature for 1 hour. After adding other additives and a colorant thereto and then stirring at room temperature for 1 hour, the obtained solution was stirred for 2 hours. The solution was filtered three times to remove impurities, thereby preparing a photosensitive resin composition.

[0165] [Table 1]

[0166] (Unit: weight %)

[0167]

[0168] [Table 2]

[0169] (Unit: weight %)

[0170]

[0171] [Table 3]

[0172] (Unit: weight %)

[0173]

[0174] [Table 4]

[0175] (Unit: weight %)

[0176]

[0177] [Table 5]

[0178] (Unit: weight %)

[0179]

[0180] (A) Binder resin

[0181] (A-1) Acrylic binder resin (SP-RY38; Showa Denko) (69 KOH mg / g, 6000 g / mol, 370 g / mol)

[0182] (A-2) Acrylic binder resin (SP-RY92; Showa Denko) (35 KOH mg / g, 6000 g / mol, 350 g / mol)

[0183] (A-3) Acrylic binder resin (SP-RY92-M10; Showa Denko) (34 KOH mg / g, 9000 g / mol, 340 g / mol)

[0184] (B) Colorants

[0185] (B-1) Green pigment dispersion (Sanyo, G58)

[0186] (B-2) Yellow pigment dispersion (Sanyo, Y139)

[0187] (C) polymerizable monomer

[0188] (C-1) Pentaerythritol triacrylate (PE-3A, Gongyoungsa Co., Ltd.)

[0189] (C-2) Dipentaerythritol hexa(meth)acrylate (DPHA, Nippon Kayaku Co. Ltd.)

[0190] (C-3) Compound represented by Chemical Formula A (M200, Miwon Chemical Co., Ltd.)

[0191] [Chemical formula A]

[0192]

[0193] (D) Polymerization initiator

[0194] Oxime initiator (SPI-03, Samyang Corp.)

[0195] (E) Solvent

[0196] Propylene glycol monomethyl ether acetate (PGMEA, Daicel Co., Ltd.)

[0197] (F) Other additives

[0198] (F-1) Leveling agent (F-556, DIC Co., Ltd.)

[0199] (F-2) Silane coupling agent (KBM503, ShinEtsu)

[0200] (F-3) Antioxidant (2-methylhydroquinone, JH Chemical (JHChem))

[0201] Rating 1

[0202] By using K-spin 8 (front-end coating and development (Track)) equipment, the photosensitive compositions of Examples 1 to 23 and Comparative Examples 1 to 14 were coated on 8-inch silicon wafers, respectively, at revolutions per minute (rpm) capable of reaching a predetermined thickness (1.5 μm). Subsequently, the coated wafers were baked at 100° C. for 3 minutes or at 85° C. for 6 minutes on a heating plate of the Track equipment, and then exposed to patterning by controlling the exposure dose using an i-line stepper manufactured by Nikon Corp. Then, development was continued to obtain a pattern. The 1.6 μm pattern CD obtained was measured by a critical dimension-scanning electron microscope (CD-SEM) manufactured by Hitachi, Ltd.

[0203] To evaluate color characteristics, a pattern (substrate) was obtained in the same manner as above except that a glass wafer was used, wherein two substrates were manufactured per sample because the target thickness (1.5 μm) was accurately obtained. The color of the pattern was measured using a fine pattern colorimeter (LCF).

[0204] The experimental results are provided in Tables 6 and 7.

[0205] [Table 6]

[0206]

[0207] [Table 7]

[0208]

[0209] Referring to Table 6 and Table 7, the photosensitive resin composition according to some embodiments can realize a fine pattern and ensure a wide color gamut due to excellent color characteristics despite being cured at a low temperature.

[0210] Although the present disclosure has been described in conjunction with what are currently considered to be practical exemplary embodiments, it should be understood that the present invention is not limited to the disclosed embodiments, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. Therefore, it should be understood that the foregoing embodiments are exemplary and do not limit the present invention in any way.

Claims

1. A photosensitive resin composition free of antioxidant, comprising: Binder resin; Colorants; polymerizable monomers; Polymerization initiator; as well as Solvents, wherein the colorant and the polymerization initiator are contained in an amount of 80 wt % to 95 wt % and 0.65 wt % to 1.3 wt %, respectively, The colorant includes a green pigment and a yellow pigment, and The green pigment is included in an amount of greater than or equal to 50 wt % based on the total amount of the colorant.

2. The antioxidant-free photosensitive resin composition according to claim 1, wherein The green pigment and the yellow pigment are each independently contained in the form of a pigment dispersion.

3. The antioxidant-free photosensitive resin composition according to claim 1, wherein The binder resin is an acrylic binder resin.

4. The antioxidant-free photosensitive resin composition according to claim 3, wherein The acrylic binder resin has an acid value greater than or equal to 50 KOHm / g and a weight average molecular weight less than or equal to 7000 g / mol.

5. The antioxidant-free photosensitive resin composition according to claim 4, wherein The acrylic binder resin has a double bond equivalent weight greater than or equal to 360 g / mol.

6. The antioxidant-free photosensitive resin composition according to claim 1, wherein The polymerizable monomer includes one or more compounds including three or more functional groups.

7. The antioxidant-free photosensitive resin composition according to claim 6, wherein The polymerizable monomer is a mixture of two types of compounds, and The two types of compounds are each independently a compound including three or more functional groups.

8. The antioxidant-free photosensitive resin composition according to claim 7, wherein The two types of compounds were mixed with each other in a weight ratio of 1:

1.

9. The antioxidant-free photosensitive resin composition according to claim 1, wherein The polymerizable monomer is included in an amount greater than that of the binder resin.

10. The antioxidant-free photosensitive resin composition according to claim 1, wherein The photosensitive resin composition not containing an antioxidant has a full width at half maximum of less than 105 nm.

11. The antioxidant-free photosensitive resin composition according to claim 1, wherein The photosensitive resin composition without an antioxidant has a transmittance of less than 8% at 630 nm.

12. The antioxidant-free photosensitive resin composition according to claim 1, wherein the antioxidant-free photosensitive resin composition comprises: Based on the total amount of the photosensitive resin composition not containing an antioxidant, 1 wt % to 5 wt % of said binder resin; 80 to 95 wt % of said colorant; 1 wt % to 10 wt % of said polymerizable monomer; 0.65 wt % to 1.3 wt % of the polymerization initiator; and The balance is the solvent.

13. The antioxidant-free photosensitive resin composition according to claim 1, wherein The photosensitive resin composition without antioxidant further comprises the following additives: malonic acid, 3-amino-1,2-propylene glycol, a silane coupling agent, a leveling agent, a surfactant or a combination thereof. 14 . A photosensitive resin layer produced using the antioxidant-free photosensitive resin composition according to claim 1 .

15. A display device comprising the photosensitive resin layer according to claim 14.

16. The display device according to claim 15, wherein The display device is a micro organic light emitting diode display device, which includes an organic light emitting diode substrate and a color filter layer, wherein the organic light emitting diode substrate is located on a silicon wafer, and the color filter layer is stacked on the organic light emitting diode substrate and converts white light generated by the organic light emitting diode substrate into light of multiple colors, and The color filter layer includes a red color filter, a green color filter, and a blue color filter.

17. A method for manufacturing a photosensitive resin layer, comprising: Applying the photosensitive resin composition containing no antioxidant as claimed in any one of claims 1 to 13; Pre-baking at a temperature of 100° C. or lower after the coating; exposing to i-line after performing the pre-bake; as well as The photosensitive resin composition is developed.

Images