Photocurable composition and method of manufacturing display device

Abstract

The invention relates to a photocurable composition and a method of manufacturing a display device. The photocurable composition includes: a photocurable oligomer; a photocurable monomer including a monofunctional (meth) acrylate monomer and a polyfunctional (meth) acrylate monomer; a functional raw material including an antioxidant and a surface additive; and a photoinitiator. The photocurable oligomer may include at least one of a (meth) acrylate, a polyester-based (meth) acrylate, an epoxy (meth) acrylate, and a urethane (meth) acrylate. The photocurable oligomer may be included in an amount of about 15 wt% to about 25 wt% based on the total weight of the photocurable composition, and the photocurable oligomer has a weight average molecular weight of about 500 g / mol to about 10000 g / mol.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2023-0143124 filed in the Korean Intellectual Property Office on October 24, 2023, the entire contents of which are incorporated herein by reference. Technical Field

[0003] Embodiments of the present disclosure described herein relate to a photocurable composition and a method of manufacturing a display device. Background Art

[0004] With the development of information technology, the importance of display devices as a connection medium between information and users has increased. Accordingly, display devices (such as organic light emitting display devices, liquid crystal display devices (LCDs), electrophoretic display devices, and / or quantum dot display devices) are increasingly used.

[0005] The display device may be manufactured by forming a plurality of panels on a mother substrate and then cutting the mother substrate. In order to improve the reliability of the manufacturing process, a strategy, design and / or planning for disposing a protective film over the plurality of panels may be applied or advanced. Summary of the invention

[0006] Aspects according to one or more embodiments of the present disclosure relate to a photocurable composition and a method of manufacturing a display device using the same, which may simplify a manufacturing process of a protective film for protecting a panel in a manufacturing process of the display device.

[0007] Aspects according to one or more embodiments of the present disclosure relate to a photocurable composition and a method of manufacturing a display device using the photocurable composition, which can minimize or reduce changes in characteristics of a protective film under a harsh environment (eg, a high temperature and humid environment).

[0008] Additional aspects will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the presented embodiments of the disclosure.

[0009] According to one or more embodiments of the present disclosure, the photocurable composition may include: a photocurable oligomer; a photocurable monomer including a monofunctional (meth)acrylate monomer and a multifunctional (meth)acrylate monomer; a functional raw material including an antioxidant and a surface additive; and a photoinitiator, wherein the photocurable oligomer includes at least one of (meth)acrylate, polyether (meth)acrylate, epoxy (meth)acrylate and urethane (meth)acrylate, and wherein the photocurable oligomer is included in an amount of about 15 wt % to about 25 wt % based on the total weight of the photocurable composition, and the photocurable oligomer has a weight average molecular weight of about 500 g / mol to about 10,000 g / mol.

[0010] According to one or more embodiments, the monofunctional (meth)acrylate monomer may include at least one of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl acrylate, methyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, isononyl acrylate, tridecyl (meth)acrylate, cyclohexyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, norbornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentyl (meth)acrylate and dicyclopentyloxyethyl (meth)acryloyl vinyl norbornanone. The multifunctional (meth)acrylate monomer may include at least one of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol monohydroxy penta(meth)acrylate, and dipropylene glycol diacrylate.

[0011] According to one or more embodiments, the monofunctional (meth)acrylate monomer may be included in an amount of about 65 wt % to about 75 wt % based on the total weight of the photocurable composition. The multifunctional (meth)acrylate monomer may be included in an amount of about 1 wt % to about 50 wt % based on the total weight of the photocurable composition.

[0012] According to one or more embodiments, the photocurable monomer has a viscosity in a range of about 1 cps to about 1000 cps at about 25°C.

[0013] According to one or more embodiments, the antioxidant may include 2,2'-thiodiethylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and / or at least one selected from the group consisting of IRGANOX 1135, IRGANOX 1035, IRGANOX 1520L, IRGANOX 1076, IRGANOX 1010, IRGAFOS168 and IRGAFOS126 manufactured by IGM Resins BV.

[0014] According to one or more embodiments, the antioxidant may be included in an amount of about 0.001 wt % to about 5 wt % based on the total weight of the photocurable composition.

[0015] According to one or more embodiments, the surface additive may include at least one of a polyacrylate-based surfactant, a silicon-containing surfactant, and an acrylic surfactant.

[0016] According to one or more embodiments, the surface additive may be included in an amount of about 0.1 wt % to about 5 wt % based on the total weight of the photocurable composition.

[0017] According to one or more embodiments, the photoinitiator may include benzophenone, a compound including a benzyl group, benzoin, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, p-, p-'-bisdiethylaminobenzophenone, benzoin methyl ether, benzoin isobutyl ether, benzoin n-butyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 2,2-diethoxyacetophenone, 4-N,N'-dimethylacetophenone, benzoquinone, anthraquinone, diphenyl disulfide, dibenzyl disulfide, tetraethylthiuram disulfide , tetramethylammonium monosulfide, azobisisobutyronitrile, 2,2'-azobispropane, hydrazine, thioxanthone, 2-methylthioxanthone benzoyl peroxide, di-tert-butyl peroxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-propane-1-one, 2-hydroxy-1-4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl-2-methyl-propane-1-one, methyl benzoylformate, 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone and 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone.

[0018] According to one or more embodiments, the photoinitiator may be included in an amount of about 0.1 wt % to about 10 wt % based on the total weight of the photocurable composition.

[0019] According to one or more embodiments of the present disclosure, a method for manufacturing a display device may include: forming (or providing) a panel on a mother substrate; and forming (or providing) a protective film on top of each panel, wherein forming (or providing) the protective film on top of each panel includes: applying a photocurable composition on top of each panel using an inkjet printing device; and photocuring the photocurable composition, wherein the photocurable composition includes: a photocurable oligomer; a photocurable monomer including a monofunctional (meth)acrylate monomer and a multifunctional (meth)acrylate monomer; a functional raw material including an antioxidant and a surface additive; and a photoinitiator, wherein the photocurable oligomer includes at least one of (meth)acrylate, polyether (meth)acrylate, epoxy (meth)acrylate and urethane (meth)acrylate, and wherein the photocurable oligomer is included in an amount of about 15 wt % to about 25 wt % based on the total weight of the photocurable composition, and the photocurable oligomer has a weight average molecular weight of about 500 g / mol to about 10,000 g / mol.

[0020] According to one or more embodiments, the monofunctional (meth)acrylate monomer may be included in an amount of about 65 wt % to about 75 wt % based on the total weight of the photocurable composition. The multifunctional (meth)acrylate monomer may be included in an amount of about 1 wt % to about 50 wt % based on the total weight of the photocurable composition.

[0021] According to one or more embodiments, the antioxidant may include at least one of a phenolic antioxidant, a phosphorus antioxidant, and a sulfur antioxidant, and the antioxidant is included in an amount of about 0.001 wt % to about 5 wt % based on the total weight of the photocurable composition. The surface additive may include at least one of a polyacrylate surfactant, a silicon-containing surfactant, and an acrylic surfactant, and the surface additive is included in an amount of about 0.1 wt % to about 5 wt % based on the total weight of the photocurable composition.

[0022] According to one or more embodiments, the photoinitiator may include at least one of a phosphine photoinitiator, a hydroxyketone photoinitiator, a carbonyl photoinitiator, a sulfide photoinitiator, a quinone photoinitiator, an azo photoinitiator, and a peroxide photoinitiator, and the photoinitiator is included in an amount of about 0.1 wt % to about 10 wt % based on the total weight of the photocurable composition.

[0023] According to one or more embodiments, the photocuring of the photocurable composition may include curing the photocurable composition using ultraviolet light. The ultraviolet light may have a wavelength of about 350 nanometers (nm) to about 400 nm and have a strength of about 3 joules per square centimeter (J / cm 2 ) to about 5J / cm 2 The accumulated light amount.

[0024] According to one or more embodiments, in the photocuring of the photocurable composition, the photocurable composition may be cured at an oxygen concentration of about 100 parts per minute (ppm) to about 5000 ppm.

[0025] According to one or more embodiments, the method may further include removing the protective film. The removal of the protective film may include removing the protective film using a tape, the tape including at least one of a thermal peeling tape, an ultraviolet peeling tape, and a weak adhesive tape. When removing the protective film, the peel strength of the protective film may become smaller as it approaches the central area of ​​the protective film.

[0026] According to one or more embodiments, the photocurable composition may have a viscosity of about 15 centipoise (cps) to 25 cps and a surface tension of about 20 dyne / cm to about 30 dyne / cm at 25° C. When applying the photocurable composition on top of each panel using an inkjet printing device, the photocurable composition may be applied by a head of the inkjet printing device. The head may have a temperature range of about 30° C. to about 50° C.

[0027] According to one or more embodiments, the protection film may be formed (or provided) to have a thickness of about 30 micrometers (μm) to about 150 μm.

[0028] According to one or more embodiments, the protective film may have a cure index of about 85% to about 95% and a hardness of about 0.7 gigapascals (GPa) to about 2 GPa in Fourier transform infrared spectroscopy (FT-IR) measurement. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 A schematic plan view for explaining a display device according to some embodiments of the present disclosure.

[0030] Figure 2 Schematic cross-sectional views for explaining display devices according to some embodiments of the present disclosure.

[0031] Figure 3 A schematic flow chart for explaining a method for manufacturing a display device according to some embodiments of the present disclosure.

[0032] Figure 4 To explain Figure 3 A schematic plan view of step S100 is shown in FIG.

[0033] Figure 5 For along Figure 4 Schematic cross-sectional view taken along line AA′ shown in FIG.

[0034] Figure 6 To explain Figure 3 A schematic flow chart of step S200 is shown in FIG.

[0035] Figure 7 and Figure 8 To explain Figure 5 Schematic cross-sectional view of the process steps shown in FIG.

[0036] Fig. 9 To explain Figure 3 A schematic plan view of step S300 is shown in FIG.

[0037] Fig.10 To explain Figure 3 A schematic cross-sectional view of step S400 is shown in FIG.

[0038] Fig.11 An enlarged view schematically illustrating the panel and the protective film. DETAILED DESCRIPTION

[0039] The present disclosure can be modified in one or more suitable ways and has many forms, and therefore specific embodiments will be illustrated in the drawings and described in more detail in the detailed description of the present disclosure. However, it should be understood that it is not intended to limit the present disclosure to the specific forms disclosed, but is intended to cover all modifications, equivalents and alternatives that fall within the spirit and scope of the present disclosure.

[0040] It will be understood that although the terms "first", "second", etc. may be used herein to describe one or more appropriate elements, these elements should not be limited by these terms. These terms are only used to distinguish one element from another element. Therefore, without departing from the teachings of the present disclosure, the "first" element discussed herein may also be referred to as the "second" element. As used herein, the singular form is intended to also include the plural form, unless the context clearly indicates otherwise.

[0041] It will be further understood that when the terms "includes" and / or "including" are used in this specification, it indicates the presence of the described features, integers, steps, operations, elements, components and / or groups thereof, but does not exclude the presence and / or addition of one or more other features, integers, steps, operations, elements, components and / or groups thereof. In addition, the statement that an element (such as a layer, region, substrate or board) is placed "on" or "above" another element (such as a layer, region, substrate or board) not only indicates the situation in which the element is "directly placed "on" or "just on" another element, but also indicates the situation in which another element is inserted between the element and the other element. In contrast, the statement that an element (such as a layer, region, substrate or board) is placed "under" or "below" another element (such as a layer, region, substrate or board) not only indicates the situation in which the element is "directly placed "under" or "just on" another element, but also indicates the situation in which another element is inserted between the element and the other element.

[0042] In the present disclosure, “(meth)acrylate” refers to acrylate or methacrylate, “(meth)acrylic acid” refers to acrylic acid or methacrylic acid, and “(meth)acryloyl” refers to acryl or methacryloyl.

[0043] In the present disclosure, a monomer refers to a compound distinguished from an oligomer and having a weight average molecular weight of less than about 500 g / mol. An oligomer refers to a compound having a weight average molecular weight of about 500 g / mol or more.

[0044] In the present disclosure, a "polymerizable functional group" is a group that participates in a polymerization reaction, and may be, for example, a (meth)acrylate group.

[0045] The present disclosure generally relates to a photocurable composition and a method for manufacturing a display device. Hereinafter, a photocurable composition and a method for manufacturing a display device according to some embodiments of the present disclosure will be described with reference to the accompanying drawings.

[0046] First, refer to Figure 1 and Figure 2 A display device DD that can be manufactured according to the method of manufacturing a display device according to the present disclosure is described. Figure 1 A schematic plan view for explaining a display device according to some embodiments of the present disclosure. Figure 2 Schematic cross-sectional views for explaining display devices according to some embodiments of the present disclosure.

[0047] refer to Figure 1 The display device DD may be configured to emit light. The display device DD may include a light emitting element LD (see Figure 2). In some embodiments, the display device DD is a device that can display moving images or still images. The display device DD can be used not only as a display screen of a portable electronic device (such as a mobile phone, a smart phone, a tablet personal computer (PC), a smart watch, and / or a watch phone), but also as a display screen of one or more suitable products (such as a television, a notebook computer, a monitor, a billboard, an Internet of Things (IoT) device, and / or a microdisplay). However, the application field of the display device DD is not limited to the specific example.

[0048] The display device DD may be formed (or provided) in a rectangular plane having a short side in a first direction DR1 and a long side in a second direction DR2 intersecting or crossing the first direction DR1. The angle at which the short side in the first direction DR1 and the long side in the second direction DR2 intersect each other may be formed (or provided) as a circle having a set or predetermined curvature, or formed (or provided) as a right angle. The planar shape of the display device DD is not limited to a quadrilateral shape, and the display device DD may be formed (or provided) as other shapes, such as another polygonal shape, a circular shape, or an elliptical shape. The display device DD may be formed (or provided) as flat, but the present disclosure is not limited thereto. For example, the display device DD may include a curved portion formed (or provided) at the left end / right end and having a constant curvature or a variable curvature. In some embodiments, the display device DD may be formed (or provided) as having sufficient flexibility so as to be warpable, bendable, bendable, foldable, or curlable.

[0049] In the present disclosure, the first direction DR1 may be a "horizontal" direction that is a row direction of the pixels PXL. The second direction DR2 may be a column direction of the pixels PXL. The third direction DR3 may be a display direction of the display device DD or a normal (e.g., vertical) direction of a plane on which the base layer BSL is disposed.

[0050] The display device DD may include a display area DA and a non-display area NDA. The non-display area NDA may refer to an area other than the display area DA. The non-display area NDA may surround at least a portion of the display area DA.

[0051] The display area DA may refer to an area in which the pixels PXL are disposed. The non-display area NDA may refer to an area in which the pixels PXL are not disposed. Driving circuits, lines, and pads connected to the pixels PXL of the display area DA may be disposed in the non-display area NDA.

[0052] In some embodiments, each pixel PXL (or sub-pixel SPX) may include a first sub-pixel SPX1, a second sub-pixel SPX2, and a third sub-pixel SPX3. At least one first sub-pixel SPX1, at least one second sub-pixel SPX2, and at least one third sub-pixel SPX3 may constitute a pixel unit capable of emitting light of one or more appropriate colors. Figure 1 In the embodiment, each pixel PXL includes three sub-pixels SPX1, SPX2, and SPX3, that is, a first sub-pixel SPX1, a second sub-pixel SPX2, and a third sub-pixel SPX3. The embodiments of the present disclosure are not limited thereto.

[0053] In some embodiments, the structure can be arranged according to stripes and / or The pixels PXL (or sub-pixels SPX) are arranged by arranging structures, etc. However, the present disclosure is not limited thereto.

[0054] The first subpixel SPX1 may be configured to emit a first light, the second subpixel SPX2 may be configured to emit a second light, and the third subpixel SPX3 may be configured to emit a third light. The first light may be light in a red wavelength band, the second light may be light in a green wavelength band, and the third light may be light in a blue wavelength band. The red wavelength band may be a wavelength band of about 600nm to about 750nm, the green wavelength band may be a wavelength band of about 480nm to about 560nm, and the blue wavelength band may be a wavelength band of about 370nm to about 460nm. However, embodiments of the present disclosure are not limited thereto.

[0055] Each of the first subpixel SPX1, the second subpixel SPX2, and the third subpixel SPX3 is a light emitting element capable of emitting light, and may include an inorganic light emitting element including an inorganic semiconductor or an organic light emitting diode (OLED). However, the present disclosure is not limited to specific examples.

[0056] refer to Figure 2 The display device DD may include a panel PNL. The panel PNL may include a pixel circuit layer PCL and a light emitting element layer LML.

[0057] The pixel circuit layer PCL may be a layer including a pixel circuit for driving the light emitting element LD. The pixel circuit layer PCL may include a base layer BSL, a conductive layer for forming (or providing) the pixel circuit, and an insulating layer disposed between the conductive layers.

[0058] In some embodiments, the pixel circuit may include at least one transistor, and be electrically connected to the light emitting element LD to provide an electrical signal for causing the light emitting element LD to emit light.

[0059] The light emitting element layer LML may be disposed on the pixel circuit layer PCL. In some embodiments, the light emitting element layer LML may include at least one light emitting element LD, a pixel defining layer PDL, and an encapsulation layer TFE.

[0060] The light emitting element LD may be disposed on the pixel circuit layer PCL. In some embodiments, the light emitting element LD may include a first electrode ELT1, a light emitting portion EL, and a second electrode ELT2.

[0061] One surface of the light emitting portion EL may be electrically connected to the first electrode ELT1 , and the other surface of the light emitting portion EL may be electrically connected to the second electrode ELT2 .

[0062] The first electrode ELT1 may be an anode electrode of the light emitting portion EL, and the second electrode ELT2 may be a cathode electrode of the light emitting portion EL. In some embodiments, the first electrode ELT1 and the second electrode ELT2 may include a conductive material. For example, the first electrode ELT1 may include a conductive material having a reflective property, and the second electrode ELT2 may include a transparent conductive material. However, the present disclosure is not necessarily limited thereto. The first electrode ELT1 may be a cathode electrode of the light emitting portion EL, and the second electrode ELT2 may be an anode electrode of the light emitting portion EL.

[0063] The light emitting portion EL may be configured to emit light based on an electrical signal supplied from an anode electrode (eg, the first electrode ELT1 ) and a cathode electrode (eg, the second electrode ELT2 ).

[0064] A pixel defining layer PDL may be disposed on the first electrode ELT1. The pixel defining layer PDL may define a position where the light emitting part EL is disposed.

[0065] The pixel defining layer PDL may include an inorganic material. For example, the inorganic material may include at least one selected from the group consisting of silicon nitride (SiN x ), silicon oxide (SiO x ), silicon oxynitride (SiO x N y ) and aluminum oxide (AlO x ). However, the present disclosure is not limited thereto. The pixel defining layer PDL may include an organic material. For example, the pixel defining layer PDL may include at least one selected from the group consisting of acrylic resin, epoxy resin, phenolic resin, polyamide resin, and polyimide resin.

[0066] At least a portion of the second electrode ELT2 may be disposed on the light emitting portion EL. At least a portion of the second electrode ELT2 may be disposed directly on the light emitting portion EL. At least a portion of the second electrode ELT2 may cover the light emitting portion EL.

[0067] The encapsulation layer TFE may be disposed on the light emitting element LD (e.g., the second electrode ELT2). The encapsulation layer TFE may eliminate or reduce the step difference caused by the light emitting element LD and the pixel defining layer PDL. The encapsulation layer TFE may include a plurality of insulating layers covering the light emitting element LD. In some embodiments, the encapsulation layer TFE may have a structure in which inorganic layers and organic layers are alternately stacked. In some embodiments, the encapsulation layer TFE may be a thin film encapsulation layer.

[0068] In some embodiments, when manufacturing the panel PNL, the protective film PF (see Figure 8 ) can be arranged on the encapsulation layer TFE. Protective film PF (see Figure 8 ) can protect the panel PNL of the display device DD. The protective film PF (see Figure 8 ) can be used to cure the photocurable composition 1000 (see Figure 7 ) to manufacture (e.g., form).

[0069] Hereinafter, a photocurable composition 1000 according to the present disclosure will be described.

[0070] The photocurable composition 1000 is a composition for manufacturing a protection film PF. The photocurable composition 1000 may be cured to form (or provide) a protection film PF.

[0071] The photocurable composition 1000 may include a photocurable material. The photocurable composition 1000 may be cured by ultraviolet (UV) light.

[0072] The photocurable composition 1000 may be a resin for inkjet printing. The photocurable composition 1000 may be discharged on the encapsulation layer TFE by an inkjet printing device. However, the present disclosure is not limited thereto. For example, in addition to inkjet printing, the photocurable composition 1000 may be supplied on the encapsulation layer TFE by other process methods for supplying resin.

[0073] In some embodiments, the photocurable composition 1000 may include an oligomer, a monomer, a functional raw material, and a photoinitiator. Hereinafter, the configuration of the photocurable composition 1000 will be described in more detail.

[0074] (1) Oligomers

[0075] The oligomer may include a photocurable oligomer (e.g., a monomer of a photocurable type or kind). The oligomer is a main component of the photocurable composition 1000 that forms (or provides) a coating film after photopolymerization, and may form (or provide) a cross-linked structure, thereby controlling the modulus properties, flexibility properties, adhesive properties and / or film properties of the cured product (e.g., the protective film PF).

[0076] The oligomer may include at least one of (meth)acrylate, polyether (meth)acrylate, epoxy (meth)acrylate, and urethane (meth)acrylate.

[0077] The oligomer may have a weight average molecular weight of about 500 g / mol to about 10,000 g / mol.

[0078] In some embodiments, the oligomer may be a compound including a functional group represented by the following chemical formula 1. In some embodiments, the oligomer may be a central carbon compound or a compound in which the functional group represented by the following chemical formula 1 is disposed at (e.g., opposite) both ends of the central carbon compound. In some embodiments, the central carbon compound is a hydrocarbon-based material, and the amount of carbon may be controlled or selected so that the weight average molecular weight of the oligomer becomes about 500 g / mol to about 10,000 g / mol.

[0079] Chemical formula 1

[0080]

[0081] In some embodiments, X in Chemical Formula 1 may be hydrogen (H) or a methyl group.

[0082] In some embodiments, when the oligomer includes urethane (meth) acrylate, the urethane (meth) acrylate may be prepared by reacting a diol having hydroxyl groups at (e.g., opposite) ends of the molecule, a (meth) acrylate having a hydroxyl group in the molecule, and a compound having an isocyanate group in the presence of a catalyst.

[0083] For example, the diol having hydroxyl groups at (eg, opposite) both ends of the molecule may be at least one selected from the group consisting of polyethylene oxide, polyethylene glycol, polycyclobutane oxide, polypropylene oxide, polyisobutylene, polyethylene adipate, and polycaprolactone.

[0084] For example, the (meth)acrylate having a hydroxyl group in the molecule may be at least one selected from the group consisting of 2-hydroxyethyl (meth)acrylate, 2-hydroxyisopropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, caprolactone ring-opening hydroxy acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate.

[0085] For example, the compound having an isocyanate group may be at least one selected from the group consisting of 1,4-diisocyanate butane, 1,6-diisocyanate hexane, 1,8-diisocyanate octane, 1,12-diisocyanate dodecane, 1,5-diisocyanate-2-methylpentane, trimethyl-1,6-diisocyanate hexane, 1,3-bis(isocyanatomethyl)cyclohexane, trans-1,4-cyclohexene diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate) ), isophorone diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, xylene-1,4-diisocyanate, tetramethylxylene-1,3-diisocyanate, 1-chloromethyl-2,4-diisocyanate, 4,4'-methylenebis(2,6-dimethylphenylisocyanate), 4,4'-oxybis(phenylisocyanate), trifunctional isocyanates derived from hexamethylene diisocyanate, and trimethane propanol addition toluenediisocyanate.

[0086] The oligomer may be included in an amount of about 1 wt % to about 50 wt % based on the total weight of the photocurable composition 1000. In some embodiments, the oligomer may be included in an amount of about 15 wt % to about 25 wt % based on the total weight of the photocurable composition 1000. When the oligomer is included in an amount of less than about 1 wt % based on the total weight of the photocurable composition 1000, it may be difficult to ensure film properties when forming (or providing) the protective film PF. When the oligomer is included in an amount exceeding about 50 wt % based on the total weight of the photocurable composition 1000, the viscosity of the photocurable composition 1000 may increase. Therefore, the photocurable composition 1000 may be difficult to remove from the inkjet printing device 100 (see Figure 7 ), and the manufacturing time of the display device DD may be increased.

[0087] (2) Monomer

[0088] The monomer may be a photocurable monomer (e.g., a photocurable type or type monomer). The monomer, together with the oligomer, is a main component of the photocurable composition 1000 that forms (or provides) a coating film after photopolymerization, and may include at least one (meth) acrylate functional group in the molecule. The monomer may control the viscosity of the photocurable composition 1000 and control the hardness of the cured product. For example, the monomer may form (or provide) a suitable or appropriate viscosity, with which the photocurable composition 1000 is discharged from the inkjet printing device 100, and may make the cured product have a suitable or appropriate hardness for protecting the panel PNL.

[0089] The monomer has a viscosity in the range of about 1 cps to about 1000 cps at about 25° C. When the monomer has a viscosity within the above numerical range, the photocurable composition 1000 may be properly discharged from the inkjet printing apparatus 100 .

[0090] The monomer may include at least one of a monofunctional (meth)acrylate monomer and a multifunctional (meth)acrylate monomer including at least two meth(acrylate) functional groups.

[0091] The monofunctional (meth)acrylate monomer may include at least one selected from the group consisting of: a monofunctional (meth)acrylate monomer having a polar hydroxyl group in the molecule, a monofunctional (meth)acrylate monomer having no polar group in the molecule, and a monofunctional meth (acrylate) monomer having an ethylenically unsaturated double bond and a cyclic aliphatic group in the molecule.

[0092] For example, the monofunctional (meth)acrylate monomer having a polar hydroxyl group in a molecule may include at least one selected from the group consisting of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl acrylate.

[0093] The monofunctional (meth)acrylate monomer having no polar group in the molecule may have a linear structure. For example, the monofunctional (meth)acrylate monomer having no polar group in the molecule may include at least one selected from the group consisting of methyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, isononyl acrylate, and tridecyl (meth)acrylate.

[0094] A monofunctional meth(acrylate) monomer having an ethylenically unsaturated double bond and a cyclic aliphatic group in the molecule is a photopolymerizable monomer and may include, for example, at least one of materials having a vinyl group, such as cyclohexyl(meth)acrylate, norbornyl(meth)acrylate, isobornyl(meth)acrylate, norbornyl(meth)acrylate, dicyclopentenyl(meth)acrylate, dicyclopentenyloxyethyl(meth)acrylate, dicyclopentyl(meth)acrylate, dicyclopentyloxyethyl(meth)acrylate vinylnorbornyl ketone and vinylnorvornylnane.

[0095] For example, the multifunctional (meth)acrylate monomer may include at least one selected from the group consisting of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol monohydroxy penta(meth)acrylate, and dipropylene glycol diacrylate.

[0096] The monofunctional (meth)acrylate monomer may be included in an amount of about 10 wt % to about 97.699 wt % based on the total weight of the photocurable composition 1000. In some embodiments, the monofunctional (meth)acrylate monomer may be included in an amount of about 10 wt % to about 100 wt % based on the weight of the photocurable composition 1000 excluding the photoinitiator.

[0097] In some embodiments, the monofunctional (meth)acrylate monomer may be included in an amount of about 65 wt % to about 75 wt % based on the total weight of the photocurable composition 1000. The monofunctional (meth)acrylate monomer may control the viscosity of the photocurable composition 1000. Therefore, when the monofunctional (meth)acrylate monomer is included in an amount of less than about 10 wt % based on the total weight of the photocurable composition 1000, it may be difficult to ensure the viscosity of the photocurable composition 1000 discharged from the inkjet printing apparatus 100, and the photoinitiator may be difficult to dissolve in the photocurable composition 1000.

[0098] Based on the total weight of the photocurable composition 1000, the multifunctional (meth) acrylate monomer may be included in an amount of about 1wt% to about 50wt%. In some embodiments, based on the total weight of the photocurable composition 1000, the multifunctional (meth) acrylate monomer may be included in an amount of about 5wt% to about 10wt%. The multifunctional (meth) acrylate monomer may control the hardness of the cured product formed (or provided) by the photocurable composition 1000. Therefore, when the multifunctional (meth) acrylate monomer is included in an amount of less than about 1wt% based on the total weight of the photocurable composition 1000, it may be difficult to ensure the hardness of the cured product (for example, the cured product may not be cured). When the multifunctional (meth) acrylate monomer is included in an amount exceeding about 50wt% based on the total weight of the photocurable composition 1000, the cured product may break due to the high hardening of the cured product.

[0099] (3) Functional raw materials

[0100] Functional raw materials may include antioxidants and surface additives.

[0101] The antioxidant may include at least one of a free radical chain inhibitor and a peroxide decomposer.

[0102] The free radical chain inhibitor can remove free radicals that are otherwise generated after curing, thereby preventing or reducing the progress of the free radical chain reaction. The free radical chain inhibitor is a primary antioxidant and may include a phenolic antioxidant.

[0103] The phenolic antioxidant is a primary antioxidant and may include, for example, 2,2'-diethylthiobis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and / or at least one selected from the group consisting of IRGANOX 1135, IRGANOX 1035, IRGANOX 1520L, IRGANOX 1076 and IRGANOX 1010 manufactured by IGM Resins.

[0104] The peroxide decomposer may include at least one of a phosphorus-based antioxidant as a second antioxidant and a sulfur-based antioxidant as a third antioxidant. The peroxide decomposer may decompose the generated hydroperoxide into a form (eg, ion) in which free radicals are not generated.

[0105] The phosphorus-based antioxidant may include at least one selected from the group consisting of IRGAFOS 168 and IRGAPOS 126 manufactured by IGM Resins, Inc. The sulfur-based antioxidant may include, for example, thiol esters.

[0106] In some embodiments, the antioxidant may be a phenolic antioxidant. However, the present disclosure is not limited thereto. In some embodiments, the antioxidant may have a phenolic antioxidant functional group and a phosphorus antioxidant functional group in one molecule at the same time (e.g., synchronously), or have a phenolic antioxidant functional group and a sulfur antioxidant functional group in one molecule at the same time (e.g., synchronously).

[0107] In some embodiments, the antioxidant may be 2,2'-thiodiethylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0108] The antioxidant may be included in an amount of about 0.001 wt % to about 5 wt % based on the total weight of the photocurable composition 1000. In some embodiments, the antioxidant may be included in an amount of about 0.05 wt % to about 0.5 wt % based on the total weight of the photocurable composition 1000.

[0109] The antioxidant may prevent or reduce the photocurable composition 1000 from being thermally cured. Therefore, when the antioxidant is included in an amount of less than about 0.001 wt % based on the total weight of the photocurable composition 1000, the photocurable composition 1000 may be cured at a high temperature (e.g., about 85° C. or higher), and therefore, cracks may occur in the cured product. When the antioxidant is included in an amount exceeding about 5 wt % based on the total weight of the photocurable composition 1000, crosslinking of oligomers or monomers may be interrupted or reduced.

[0110] The surface additive may include, for example, at least one selected from the group consisting of a polyacrylate-based surfactant, a silicon-containing surfactant, and an acrylic surfactant.

[0111] For example, the surface additive can be selected from at least one of the following groups: low molecular weight acidic polyesters, unsaturated polyaminoamide salts, high molecular weight alkanolaminoamides, high molecular weight block copolymers, alkylammonium salts of high molecular weight copolymers, acrylate copolymers, hydroxyl functional carboxylates, polyether modified polydimethylsiloxanes, acrylic acid modified polymethylalkylsiloxanes, polyether modified polydimethylsiloxanes, and any combination thereof.

[0112] In some embodiments, the surface additive may be selected from at least one of the group consisting of BYK-306, BYK-310, BYK-320, BYK-331, BYK-333, BYK-342, BYK-350, BYK-354, BYK-355, BYK-356, BYK-358N, BYK-359, BYK-361N, BYK-381, BYK-370, BYK-371, BYK-378, BYK-388, BYK-392, BYK-394, BYK-399, BYK-3440, BYK-3441, BYK-UV3500, BYK-UV3530, and BYK-UV3570 manufactured by TEGO, and BYK-UV3500, BYK-UV3530, and BYK-UV3570 manufactured by TEGO. 2100, Rad 2011, Glide 100, Glide 410 and Glide 450 manufactured by Sumitomo 3M, Fluorad FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C and FC-430 manufactured by Sumitomo 3M, or Zonyl FS-300, FSN, FSN-100 and FSO manufactured by Dupont, and any combination thereof.

[0113] In some embodiments, the surface additive may include at least one selected from the group consisting of BYK-UV3500, BYK-UV3530, and BYK-UV3570 manufactured by BYK. When the photocurable composition 1000 includes at least one selected from the group consisting of BYK-UV3500, BYK-UV3530, and BYK-UV3570 manufactured by BYK, migration after curing may be reduced. Migration may refer to a phenomenon in which unreacted components (unreacted materials) in the photocurable composition 1000 remain on the surface of the cured product when the components move on the surface of the cured product.

[0114] In some embodiments, the surface additive may be a material satisfying Chemical Formula 2 below.

[0115] Chemical formula 2

[0116]

[0117] In some embodiments, in Chemical Formula 2, n may be selected in a range where the weight average molecular weight of Chemical Formula 2 has a range of about 1000 g / mol to about 100000 g / mol. For example, in some embodiments, n may be a natural number of 1 or more and 3000 or less. When the photocurable composition 1000 is applied on the encapsulation layer TFE, the surface additive may improve the leveling characteristics and application characteristics of the applied photocurable composition 1000, and improve the characteristics of the photocurable composition 1000 being peeled off from the encapsulation layer TFE after curing.

[0118] The surface additive may be included in an amount of about 0.1 wt % to about 5 wt % based on the total weight of the photocurable composition 1000. In some embodiments, the surface additive may be included in an amount of about 0.1 wt % to about 1 wt % based on the total weight of the photocurable composition 1000.

[0119] When the surface additive is included in an amount of less than about 0.1 wt % based on the total weight of the photocurable composition 1000, it may be difficult to ensure leveling characteristics and application characteristics when the photocurable composition 1000 is applied on the encapsulation layer TFE. When the surface additive is included in an amount exceeding about 5 wt % based on the total weight of the photocurable composition 1000, unreacted materials of the cured photocurable composition 1000 may cause stains.

[0120] In some embodiments, within the range where the effects of the present disclosure are not impaired, the functional raw materials may further include at least one of an antistatic agent, a catalyst, an inorganic filler, an organic filler, a metal powder, a pigment, a softener, a plasticizer, an anti-aging agent, a conductive agent, a UV absorber, a light stabilizer, a surface lubricant, a corrosion inhibitor, a heat stabilizer, a polymerization inhibitor, a lubricant, a degradation inhibitor (e.g., a light stabilizer), a silane coupling agent, an adhesion promoter, a thermal polymerization inhibitor, and a saturated fatty acid having eight or more carbons.

[0121] For example, the silane coupling agent may include at least one selected from the group consisting of vinyl trimethoxysilane, vinyl triethoxysilane, trimethoxysilane (meth) acrylate, and vinyl triethoxysilane (meth) acrylate. For example, the thermal polymerization inhibitor may include at least one selected from the group consisting of hydroquinone, methyl ether hydroquinone, and 2,6-di-tert-butyl-4-methylphenol. The functional raw material may include one or more appropriate materials in the art.

[0122] (4) Photoinitiator

[0123] The photoinitiator can be excited by ultraviolet light or the like to initiate photopolymerization. The photoinitiator may include, for example, at least one of a phosphine photoinitiator, a hydroxyketone photoinitiator, a carbonyl photoinitiator, a sulfide photoinitiator, a quinone photoinitiator, an azo photoinitiator, and a peroxide photoinitiator.

[0124] In some embodiments, the photoinitiator may include a phosphine photoinitiator and a hydroxyketone photoinitiator. The phosphine photoinitiator may be a long wavelength (e.g., about 395 nm) photoinitiator. The hydroxyketone photoinitiator may be a short wavelength (e.g., about 305 nm) photoinitiator.

[0125] In some embodiments, the photoinitiator may include at least one selected from the group consisting of benzophenone, a compound including a benzyl group, benzoin, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, p-, p-bis(diethylamino)benzophenone, benzoin methyl ether, benzoin isobutyl ether, benzoin n-butyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 2,2-diethoxyacetophenone, 4-N,N'-dimethylacetophenone, benzoquinone, anthraquinone, diphenyl disulfide, dibenzyl disulfide, Tetraethylthiuram disulfide, tetramethylammonium monosulfide, azobisisobutyronitrile, 2,2'-azobispropane, hydrazine, thioxanthone, 2-methylthioxanthone benzoyl peroxide, di-tert-butyl peroxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-propane-1-one, 2-hydroxy-1-4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl-2-methyl-propane-1-one, methyl benzoylformate, 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone or 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone. However, the present disclosure is not limited thereto, and a common photoinitiator in the prior art can be used without limitation.

[0126] In some embodiments, the phosphine-based photoinitiator may be phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide. In some embodiments, the hydroxyketone-based photoinitiator may be 1-hydroxycyclohexylphenylketone.

[0127] In some embodiments, the photocurable composition 1000 may further include a photosensitizer to improve the photoinitiating efficiency of the photoinitiator. In some embodiments, the photosensitizer may be at least one of thioxanthone and a benzophenone derivative.

[0128] The photoinitiator may be included in an amount of about 0.1 wt % to about 10 wt % based on the total weight of the photocurable composition 1000. In some embodiments, the photoinitiator may be included in an amount of about 0.1 wt % to about 5 wt % based on the total weight of the photocurable composition 1000. In some embodiments, the photoinitiator may be included in an amount of about 0.1 wt % to about 3 wt % based on the total weight of the photocurable composition 1000. In some embodiments, the phosphine photoinitiator may be included in an amount of about 0.1 wt % to about 3 wt % based on the total weight of the photocurable composition 1000. In some embodiments, the hydroxyketone photoinitiator may be included in an amount of about 0.1 wt % to about 3 wt % based on the total weight of the photocurable composition 1000.

[0129] When the photoinitiator is included in an amount of less than about 0.1 wt % based on the total weight of the photocurable composition 1000, photoinitiation does not occur, and therefore, it may be difficult to ensure the hardening modulus of the cured product. When the photoinitiator is included in an amount exceeding about 10 wt % based on the total weight of the photocurable composition 1000, the yellowness index may increase to about 1 or more, and migration after curing may occur due to unreacted photoinitiator.

[0130] The photocurable composition 1000 of the present disclosure includes each of the oligomer, the monomer, the functional raw material and the photoinitiator in a weight corresponding to the above numerical range, so as to form (or provide) the protective film PF by rapid curing by ultraviolet light when manufacturing the display device DD. In addition, the photocurable composition 1000 enables the protective film PF to have suitable or appropriate adhesion so that the protective film PF can be easily removed after the protective film PF is formed (or provided).

[0131] In the following, reference will be made to Figures 3 to 10 A method of manufacturing a display device is described, the method including a method of forming (or providing) a protective film PF using the photocurable composition 1000 according to the present disclosure.

[0132] Figure 3 A schematic flow chart for explaining a method for manufacturing a display device according to some embodiments of the present disclosure. Figure 4 To explain Figure 3 Schematic plan view of the steps (eg, actions or tasks) S100 shown in FIG. Figure 5 For along Figure 4 Schematic cross-sectional view taken along line AA′ shown in FIG. Figure 6 To explain Figure 3 A schematic flow chart of step S200 is shown in FIG. Figure 7 and Figure 8 To explain Figure 5 Schematic cross-sectional view of the process steps shown in FIG. Fig. 9 To explain Figure 3A schematic plan view of step S300 is shown in FIG. Fig.10 To explain Figure 3 A schematic cross-sectional view of step S400 is shown in FIG.

[0133] refer to Figure 3 The method of manufacturing a display device DD may include a step S100 of forming (or providing) a panel on a mother substrate, a step S200 of forming (or providing) a protective film on top of each panel, a step S300 of cutting the mother substrate, a step S400 of removing the protective film, and a step S500 of separating the mother substrate.

[0134] refer to Figure 2 , Figure 4 and Figure 5 In step S100 of forming (or providing) a panel on a mother substrate, a plurality of panels PNL may be formed (or provided) on a mother substrate BG. The mother substrate BG may be a substrate that supports the plurality of panels PNL before the plurality of panels PNL are separated into individual panels PNL. In some embodiments, the mother substrate BG may be a glass substrate, but the present disclosure is not limited thereto.

[0135] In the step (e.g., action or task) of forming (or providing) the panel PNL, a base layer BSL may be disposed on the mother substrate BG, and a pixel circuit layer PCL including a pixel circuit for driving the light-emitting element LD may include the base layer BSL, a conductive layer for forming the pixel circuit, and an insulating layer disposed between the conductive layers.

[0136] In some embodiments, the components disposed on the base layer BSL may be formed (or provided) through a general patterning process (eg, a photolithography process, etc.) using a mask.

[0137] After forming (or providing) the pixel circuit layer PCL, the first electrode ELT1 may be formed (or provided). The first electrode ELT1 may be deposited on the pixel circuit layer PCL and then etched. In some embodiments, when the first electrode ELT1 is deposited, the first electrode ELT1 may be electrically connected to the driving transistor through a hole penetrating the protective layer in the pixel circuit layer PCL. The first electrode ELT1 may be etched so that at least a portion of the pixel circuit layer PCL is exposed.

[0138] In the present disclosure, at least one of a chemical vapor deposition (CVD) process and an atomic layer deposition (ALD) process may be used as a process for depositing components of the display device DD. In the present disclosure, at least one of wet etching and dry etching may be used as an etching process. However, the present disclosure is not limited to specific examples.

[0139] After forming (or providing) the first electrode ELT1, a pixel defining layer PDL may be formed (or provided). The pixel defining layer PDL may be etched after being deposited on the pixel circuit layer PCL. The pixel defining layer PDL may be etched to expose at least a portion of the first electrode ELT1. The pixel defining layer PDL may be etched to overlap with the remaining portion of the first electrode ELT1 in a plan view.

[0140] After forming (or providing) the pixel defining layer PDL, the light emitting part EL may be formed (or provided). The light emitting part EL may be formed (or provided) in a region defined by the pixel defining layer PDL. The light emitting part EL may be formed (or provided) in an opening formed (or provided) by the pixel defining layer PDL.

[0141] After the light emitting portion EL is formed (or provided), the second electrode ELT2 may be formed (or provided). The second electrode ELT2 may be deposited on the pixel defining layer PDL and the light emitting portion EL, and then etched.

[0142] After forming (or providing) the second electrode ELT2, an encapsulation layer TFE may be formed (or provided). The encapsulation layer TFE may be formed (or provided) on the second electrode ELT2. The encapsulation layer TFE may completely cover the second electrode ELT2. In some embodiments, the encapsulation layer TFE may be formed (or provided) to have a structure in which inorganic layers and organic layers are alternately stacked.

[0143] After forming (or providing) a plurality of panels PNL, each panel PNL may be cut to form (or provide) a display device DD. Before each panel PNL is cut, a protective film PF may be formed (or provided) on the top of each panel PNL. Figure 6 , the step S200 of forming (or providing) a protective film on the top of each panel may include a step S210 of applying a photocurable composition on the top of each panel using an inkjet printing device and a step S230 of photocuring the photocurable composition.

[0144] refer to Figure 7 In the step S210 of applying the photocurable composition on the top of each panel using the inkjet printing device, the photocurable composition 1000 may be applied on the panel PNL by the inkjet printing device 100 .

[0145] According to the method of manufacturing a display device DD according to some embodiments of the present disclosure, when a protective film PF is formed (or provided) on a panel PNL, a photocurable composition 1000 for forming (or providing) the protective film PF may be applied by an inkjet printing process and cured by light (e.g., ultraviolet light).

[0146] Conventionally, in order to protect the panel PNL, a protective layer including polyethylene terephthalate is formed (or provided) to completely cover the mother substrate BG. After the protective layer is attached to the panel PNL through a lamination process, at least a portion of the protective layer is cut using a laser so as to form (or provide) the protective layer in a desired or appropriate area (e.g., an area corresponding to the panel PNL). Since the process simultaneously (e.g., synchronously) includes a process of laminating the protective layer on the panel PNL and a process of cutting the protective layer, the number of process steps for forming (or providing) the protective layer increases. Therefore, the manufacturing yield associated with the manufacturing process of the display device is reduced. In addition, in order to form (or provide) the protective layer in the desired or appropriate area, the laser precision of the laser cutting process is also required or desired.

[0147] On the other hand, according to the method for manufacturing a display device DD disclosed in the present invention, a method in which a photocurable composition 1000 is applied by an inkjet printing process and then cured by light can be used to manufacture the protective film PF. Since the photocurable composition 1000 is applied by an inkjet printing process, it is easy to form (or provide) the protective film PF in a desired or appropriate area, and no process for laminating the protective film PF is performed separately. Therefore, the manufacturing process can be simplified. Accordingly, the manufacturing yield of the display device DD can be increased.

[0148] The photocurable composition 1000 may be discharged through the inkjet printing apparatus 100. The photocurable composition 1000 may be injected into the inkjet printing apparatus 100 to be discharged through a nozzle included in the inkjet printing apparatus 100. The photocurable composition 1000 may have a viscosity of about 15 cps to about 25 cps at about 25° C. and a surface tension of about 20 dyne / cm to about 30 dyne / cm.

[0149] When the photocurable composition 1000 has a viscosity of less than about 15 cps and a surface tension of less than about 20 dynes / cm at about 25° C., the photocurable composition 1000 may not be discharged at some nozzles of the inkjet printing device 100 when the photocurable composition 1000 is discharged from the inkjet printing device 100. This may cause stains to be left in the protective layer (for example, a mark is left in a partial area on the panel PNL because the photocurable composition 1000 is not applied). When the photocurable composition 1000 has a viscosity of more than about 25 cps and a surface tension of more than about 30 dynes / cm at about 25° C., the photocurable composition 1000 may be excessively discharged at the nozzle of the inkjet printing device 100, and therefore, mura may appear at the surface of the protective film PF. During the inspection process, the occurrence of stains and mura may be identified as a defect.

[0150] Since the photocurable composition 1000 according to some embodiments of the present disclosure has a viscosity of about 15 cps to about 25 cps at about 25° C. and a surface tension of about 20 dyne / cm to about 30 dyne / cm, the occurrence of stains and moire may be reduced.

[0151] When the photocurable composition 1000 is discharged, the temperature of the nozzle (or head) of the inkjet printing device 100 may be included in the range of about 30° C. to about 50° C. In some embodiments, the temperature of the nozzle (or head) of the inkjet printing device 100 may be included in the range of about 35° C. to about 40° C. When the temperature of the nozzle (or head) of the inkjet printing device 100 is less than about 30° C., the photocurable composition 1000 may not be discharged at some nozzles of the inkjet printing device 100. When the temperature of the nozzle (or head) of the inkjet printing device 100 exceeds about 50° C., the durability of the nozzle (or head) of the inkjet printing device 100 may be reduced, and the roughness of the protective film PF may increase due to excessive discharge of the photocurable composition 1000 at the nozzle of the inkjet printing device 100.

[0152] In the method of manufacturing a display device DD according to some embodiments of the present disclosure, since the photocurable composition 1000 is discharged from the nozzle (or head) of the inkjet printing device 100, when the protective film PF is formed (or provided), the nozzle (or head) is in the range of about 30°C to about 50°C, so a suitable or appropriate amount of the photocurable composition 1000 can be discharged, the risk of reduced durability of the nozzle (or head) of the inkjet printing device 100 can be reduced, and the roughness of the protective film PF can be basically uniform.

[0153] The photocurable composition 1000 may be discharged from the inkjet printing device 100 to be applied on one surface of the panel PNL. The photocurable composition 1000 may completely cover one surface of the panel PNL. For example, the photocurable composition 1000 may completely cover the first surface S1 of the panel PNL. The first surface S1 of the panel PNL may be a surface spaced apart from the mother substrate BG. The first surface S1 of the panel PNL may be an upper surface of the panel PNL. In the present disclosure, the upper direction is defined as the base layer BSL (see Figure 2 ) in a thickness direction (eg, a third direction DR3). The photocurable composition 1000 may be applied so that an end portion of the photocurable composition 1000 and an end portion of the panel PNL may coincide with each other.

[0154] After the photocurable composition 1000 is applied on the panel PNL, in the step S230 of photocuring the photocurable composition, the photocurable composition 1000 may be cured by light. Figure 8, the photocurable composition 1000 may be cured by ultraviolet light UV to form (or provide) a protective film PF. The protective film PF may be formed (or provided) to have a thickness of about 30 μm to about 150 μm, but the present disclosure is not limited thereto. The end of the protective film PF and the end of the panel PNL may correspond to each other. The end of the protective film PF and the end of the panel PNL may be consistent with each other.

[0155] The ultraviolet light UV may have a wavelength of about 350 nm to about 400 nm. The cumulative light amount (eg, total light amount) of the ultraviolet light UV may be about 3 J / cm 2 To about 5J / cm 2 In some embodiments, the cumulative light amount (eg, total light amount) of the ultraviolet light UV may be about 4 J / cm 2 When the accumulated light intensity (e.g., total light intensity) of the ultraviolet light UV is less than about 3 J / cm 2 When the accumulated light amount (for example, the total light amount) of the ultraviolet light UV exceeds about 5 J / cm 2 When the curing degree of the protective film PF is saturated.

[0156] In the step S230 of photocuring the photocurable composition, the space SA (eg, the region in contact with the protective film PF) where curing of the photocurable composition 1000 occurs may have an oxygen (O) content of about 100 ppm to about 5000 ppm. 2 The protective film PF may be provided with oxygen (O) concentration of about 100 ppm to about 5000 ppm. 2 When the space SA in which the curing of the photocurable composition 1000 occurs has an oxygen (O) content of less than about 100 ppm, 2 ) concentration, when the protective film PF is peeled off from the panel PNL, the protective film PF may not be peeled off. For example, since the protective film PF is over-cured, the protective film PF may not be peeled off from the panel PNL. When the space SA where the curing of the photocurable composition 1000 occurs has an oxygen (O) concentration of more than about 5000 ppm, the protective film PF may not be peeled off from the panel PNL. 2 ) concentration, tackiness (or stickiness) may occur at the surface of the protection film PF. For example, since the protection film PF is not cured, the stickiness of the surface of the protection film PF may be increased.

[0157] At about 100 ppm to about 5000 ppm of oxygen (O 2 ) concentration by having a wavelength of about 350nm to about 400nm and about 3J / cm 2 To about 5J / cm 2The protective film PF cured by ultraviolet light UV with a cumulative light amount of 100 nm may have a hardness of about 0.7 GPa to about 2 GPa. The protective film PF may have an elongation of about 10% to about 50%. The transmittance of the protective film PF may be about 90% or more. In FT-IR measurement, the curing index of the protective film PF may be about 85% to about 95%.

[0158] refer to Fig. 9 After forming (or providing) the protective film PF, in the step S300 of cutting the mother substrate (see Figure 3 ), the mother substrate BG may be cut along the cutting line CL. In a plan view, the cutting line CL may be formed (or provided) to be spaced apart from the corner of the protective film PF along the edge of the protective film PF. Since the mother substrate BG is cut, the plurality of panels PNL may be separated into individual panels PNL.

[0159] refer to Fig.10 In step S400 (see Figure 3 ), the protective film PF on the panel PNL may be removed using a peeling tape 300. In some embodiments, the peeling tape 300 may be wound around a roller or the like. In some embodiments, the peeling tape 300 may be one of a thermal peeling tape whose adhesiveness is weakened by heating, an ultraviolet peeling tape whose adhesiveness is weakened by irradiation of ultraviolet light, and a weak adhesive tape whose adhesiveness is weak in a normal state. The peeling tape 300 may have an adhesive strength of about 100 gf / inch or more.

[0160] The characteristic change of the protective film PF according to the present disclosure can be minimized or reduced at high temperature and high humidity. For example, although the protective film PF is exposed at about 120° C. for about one week, no cracks will appear in the protective film PF. For example, although the protective film PF is exposed at about 85° C. for about 500 hours, no cracks will appear in the protective film PF.

[0161] Therefore, although the panel PNL is exposed to a high temperature and high humidity environment during the process of transporting the panel PNL, the protection film PF according to some embodiments of the present disclosure can stably protect the panel PNL. The risk of the protection film PF being damaged (eg, cracked) is reduced, and the protection film PF can be properly peeled off.

[0162] When cracks occur in the protective film PF, the protective film PF may break when the protective film PF is peeled off, and since the protective film PF is not peeled off, the encapsulation layer TFE may be peeled off. The protective film PF according to some embodiments of the present disclosure can reduce the risk of cracks occurring under high temperature and high humidity. In some embodiments, the protective film PF according to some embodiments of the present disclosure can be appropriately peeled off.

[0163] When the protective film PF is peeled off, the encapsulation layer TFE may be exposed. The first surface S1 of the encapsulation layer TFE from which the protective film PF is removed may have a hydrophobic surface. Since the encapsulation layer TFE has a hydrophobic surface, when a water drop is dropped on the first surface S1 after the protective film PF is peeled off, the contact angle of water is measured, and the contact angle of water may be increased compared to before the protective film PF is formed (or provided).

[0164] In the step S500 of separating the mother substrate, the mother substrate BG may be separated from the panel PNL. The process of separating the mother substrate BG from the panel PNL may be a laser lift-off (LLO) process. However, the present disclosure is not limited thereto. After the mother substrate BG is separated from the panel PNL, the display device DD may be completed.

[0165] In the following, further reference will be made to Fig.11 Describe the characteristics of the protective film PF. Fig.11 An enlarged view schematically illustrating the panel and the protective film.

[0166] refer to Fig.11 , the protective film PF may include a first portion 1, a second portion 2, and a third portion 3. The first portion 1 may be an edge region (e.g., an edge portion) of the protective film PF. The third portion 3 may be a central region of the protective film PF. The second portion 2 may be a region located between the first portion 1 and the third portion 3.

[0167] The protective film PF may have a thickness that becomes thicker as it approaches the third part 3 from the first part 1. The protective film PF may have a thickness that becomes thicker as it approaches the center area from the edge area. In the protective film PF, the third part 3 may have a thickness thicker than the thickness of the first part 1. Since the protective film PF is formed (or provided) to have a thickness difference, the amount of the photocurable composition 1000 exposed to ultraviolet light when the photocurable composition 1000 is cured may vary. For example, experimentally, compared to the third part 3 (compared to the third part 3), the first part 1 having a thickness thinner than the thickness of the third part 3 may be more exposed (for example, the first part 1 may be more exposed to ultraviolet light than the third part 3). Because the amount of the protective film PF exposed to ultraviolet light varies, the first part 1 and the third part 3 may have different degrees of curing. For example, since the first part 1 is exposed relatively large (for example, exposed more) compared to the third part 3, the degree of curing of the first part 1 may be greater than that of the third part 3.

[0168] Because the curing degree of the third part 3 and the curing degree of the first part 1 are different from each other, a stress difference may occur in the protective film PF when the protective film PF is formed (or provided). When the stress difference occurs in the protective film PF, the peeling strength for peeling off the protective film PF may vary. For example, the peeling strength may become smaller as it approaches the central area (e.g., the third part 3) of the protective film PF. For example, when the protective film PF is exposed to oxygen (O 2 ) atmosphere, the first portion 1 may have a peel strength of about 10 gf / inch to about 30 gf / inch. For example, the third portion 3 may have a peel strength of about 1 gf / inch to about 5 gf / inch.

[0169] The peel strength is a characteristic value indicating the magnitude of the force required when the protection film PF is peeled off from the panel PNL. The peel strength may vary according to the degree of curing of the material. For example, the peel strength may increase as the degree of curing of the material increases.

[0170] When the protection film PF is peeled with different peel strengths in some regions, a residual pattern may be formed (or provided) on the encapsulation layer TFE (eg, an uneven pattern is formed (or provided) at a portion of the surface of the encapsulation layer TFE).

[0171] According to the present disclosure, a photocurable composition and a method of manufacturing a display device using the photocurable composition can be provided, which can simplify a manufacturing process of a protective film for protecting a panel in a manufacturing process of the display device.

[0172] According to the present disclosure, a photocurable composition and a method of manufacturing a display device using the photocurable composition can be provided, which can minimize or reduce changes in characteristics of a protective film under a harsh environment (eg, a high temperature and humid environment).

[0173] In the present disclosure, unless the context clearly indicates otherwise, a singular expression may include a plural expression. It will be further understood that the terms "comprise(s)", "include(s)" or "have / has" when used in the present disclosure indicate the presence of the recited features, integers, steps, operations, elements, components and / or groups thereof, but do not exclude the presence or addition of one or more other features, integers, steps, operations, elements, components and / or groups thereof. As used herein, " / " may be interpreted as "and" or may be interpreted as "or", as the case may be.

[0174] Throughout the present disclosure, when it is mentioned that a component (such as a layer, film, region, or plate) is placed "on" another component (such as a layer, film, region, or plate), it will be understood that it can be directly on the other component (such as a layer, film, region, or plate), or other components (such as layers, films, regions, or plates) can be interposed therebetween. In some embodiments, "directly on..." can mean that there are no additional layers, films, regions, plates, etc. between the layer, film, region, plate, etc. and other components. For example, "directly on..." can mean that two layers or two components are arranged without using additional components (such as bonding components) therebetween.

[0175] In the present disclosure, although the terms "first", "second", etc. may be used herein to describe one or more elements, components, regions and / or layers, these elements, components, regions and / or layers should not be limited by these terms. These terms are only used to distinguish one component from another component.

[0176] As used herein, the singular forms "a", "an", "one", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. In addition, when describing embodiments of the present disclosure, the use of "may" refers to "one or more embodiments of the present disclosure."

[0177] In the present disclosure, when a particle (e.g., a nanoparticle) is spherical, "size" indicates a particle diameter or an average particle diameter, and when a particle is non-spherical, "size" indicates a major axis length or an average major axis length. The diameter (or size) of a particle can be measured using a scanning electron microscope or a particle size analyzer. As a particle size analyzer, for example, a HORIBA, LA-950 laser particle size analyzer can be used. When the size of a particle is measured using a particle size analyzer, the average particle diameter (or size) is referred to as D 50 . D 50 Refers to the average diameter (or size) of particles whose cumulative volume corresponds to 50% by volume in a particle size distribution (e.g., cumulative distribution), and refers to the value of the particle size corresponding to 50% from the smallest particle size when the total number of particles is 100% in a distribution curve accumulated in the order from the smallest particle size to the largest particle size.

[0178] As used herein, the terms "substantially," "about," or similar terms are used as terms of approximation and not as terms of degree, and are intended to account for the inherent deviations in measurements or calculations that one of ordinary skill in the art will recognize. As used herein, the term "about" includes the stated value and means within an acceptable range of deviations of the particular value determined by one of ordinary skill in the art taking into account the measurement in question and the errors associated with the measurement of the particular quantity (i.e., the limitations of the measurement system). For example, "about" may mean within one or more standard deviations, or within ±30%, ±20%, ±10%, or ±5% of the stated value.

[0179] In the present disclosure, "not including one or any 'component'", "excluding one or any 'component'" and / or "no 'component'" etc. refer to "components" that are not added, selected or used as components in the compound / composition / structure, but due to other impurities and / or external factors in the composition, less than the appropriate amount of "component" may still be included.

[0180] Any numerical range set forth in this article is intended to include all sub-ranges of the same numerical precision falling within the range set forth. For example, the range of "1.0 to 10.0" is intended to include between the minimum value 1.0 set forth and the maximum value 10.0 set forth (and including 1.0 and 10.0), that is, all sub-ranges with a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0, such as, for example, 2.4 to 7.6. Any maximum numerical limit set forth in this article is intended to include all lower numerical limits falling therein, and any minimum numerical limit set forth in this specification is intended to include all higher numerical limits falling therein. Accordingly, the applicant reserves the right to modify this specification (including claims) to explicitly set forth any sub-range falling within the range explicitly set forth herein.

[0181] As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items. Throughout this disclosure, the expressions "at least one of a, b, and c," "at least one of ac," "at least one of a to c," "a, b and / or c," "at least one of a to c," etc., indicate only a, only b, only c, (e.g., simultaneously) both a and b, (e.g., simultaneously) both a and c, (e.g., simultaneously) both b and c, all a, b, and c, or variations thereof.

[0182] In this specification, “including A or B”, “A and / or B”, etc. means A or B, or A and B.

[0183] The light-emitting device, display device, electronic device, electronic equipment or any other related device or component according to the embodiments of the present disclosure described herein can be implemented using any appropriate hardware, firmware (e.g., a dedicated integrated circuit), software, or a combination of software, firmware and hardware. For example, the various components of the device can be formed on an integrated circuit (IC) chip or on a separate IC chip. In addition, the various components of the device can be implemented on a flexible printed circuit film, a tape carrier package (TCP) or a printed circuit board (PCB), or formed on a substrate. In addition, the various components of the device can be processes or threads running on one or more processors in one or more computing devices, executing computer program instructions and interacting with other system components to perform the various functions described herein. The computer program instructions are stored in a memory, which can be implemented in a computing device using a standard memory device, such as, for example, a random access memory (RAM). The computer program instructions can also be stored in other non-temporary computer-readable media, such as, for example, a CD-ROM or a flash drive, etc. Moreover, it should be recognized by those skilled in the art that, without departing from the scope of the embodiments of the present disclosure, the functions of various computing devices can be combined or integrated into a single computing device, or the functions of a dedicated computing device can be distributed on one or more other computing devices.

[0184] Example embodiments are disclosed herein, and although specific terms are employed, they are used and interpreted in a general and descriptive sense only and not for purposes of limitation. In some cases, as would be apparent to one of ordinary skill in the art at the time of filing this application, unless specifically indicated otherwise, features, characteristics, and / or elements described in conjunction with a particular embodiment may be used alone or in combination with features, characteristics, and / or elements described in conjunction with other embodiments. Accordingly, it will be understood by those skilled in the art that one or more appropriate changes may be made in form and detail without departing from the spirit and scope of the present disclosure as set forth in the claims and their equivalents.

Claims

1. A photocurable composition comprising: Photocurable oligomers; Photocurable monomers including monofunctional (meth)acrylate monomers and multifunctional (meth)acrylate monomers; Functional raw materials including antioxidants and surface additives; as well as Photoinitiator, wherein the photocurable oligomer comprises at least one of (meth)acrylate, polyether (meth)acrylate, epoxy (meth)acrylate and urethane (meth)acrylate, and The amount of the photocurable oligomer is 15 wt % to 25 wt % based on the total weight of the photocurable composition, and the photocurable oligomer has a weight average molecular weight of 500 g / mol to 10000 g / mol.

2. The photocurable composition according to claim 1, wherein the monofunctional (meth)acrylate monomer comprises at least one of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl acrylate, methyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, isononyl acrylate, tridecyl (meth)acrylate, cyclohexyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, norbornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentyl (meth)acrylate and dicyclopentyloxyethyl (meth)acryloyl vinyl norbornanone, wherein the multifunctional (meth)acrylate monomer comprises at least one of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol monohydroxy penta(meth)acrylate and dipropylene glycol diacrylate, wherein the amount of the monofunctional (meth)acrylate monomer is 65 wt % to 75 wt % based on the total weight of the photocurable composition, and Wherein, based on the total weight of the photocurable composition, the amount of the multifunctional (meth)acrylate monomer is 1 wt % to 50 wt %.

3. The photocurable composition according to claim 2, wherein the antioxidant comprises 2,2'-diethylthiobis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and / or at least one selected from the group consisting of IRGANOX 1135, IRGANOX 1035, IRGANOX 1520L, IRGANOX 1076, IRGANOX 1010, IRGAFOS 168 and IRGAFOS 126 manufactured by IGM Resins, Inc., and Wherein, based on the total weight of the photocurable composition, the amount of the antioxidant is 0.001 wt % to 5 wt %.

4. The photocurable composition according to claim 2, wherein the surface additive comprises at least one of a polyacrylate surfactant, a silicon-containing surfactant and an acrylic surfactant, and wherein the amount of the surface additive is 0.1 wt % to 5 wt % based on the total weight of the photocurable composition.

5. The photocurable composition according to claim 2, wherein the photoinitiator comprises benzophenone, a compound comprising a benzyl group, benzoin, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, p-, p-bis(diethylamino)benzophenone, benzoin methyl ether, benzoin isobutyl ether, benzoin n-butyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 2,2-diethoxyacetophenone, 4-N,N'-dimethylacetophenone, benzoquinone, anthraquinone, diphenyl disulfide, dibenzyl disulfide, tetraethyl disulfide at least one of thiuram, tetramethylammonium monosulfide, azobisisobutyronitrile, 2,2'-azobispropane, hydrazine, thioxanthone, 2-methylthioxanthone benzoyl peroxide, di-tert-butyl peroxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-propane-1-one, 2-hydroxy-1-4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl-2-methyl-propane-1-one, methyl benzoylformate, 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone and 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone, and Wherein, based on the total weight of the photocurable composition, the amount of the photoinitiator is 0.1 wt % to 10 wt %.

6. A method for manufacturing a display device, the method comprising: forming a panel on a mother substrate; as well as forming a protective film on top of each of the panels, Wherein forming the protective film on the top of each of the panels comprises: applying a photocurable composition according to any one of claims 1 to 5 on the top of each of the panels using an inkjet printing device; as well as The photocurable composition is photocured.

7. The method according to claim 6, wherein the antioxidant comprises at least one of a phenol antioxidant, a phosphorus antioxidant and a sulfur antioxidant, And wherein the photoinitiator includes at least one of a phosphine photoinitiator, a hydroxyketone photoinitiator, a carbonyl photoinitiator, a sulfide photoinitiator, a quinone photoinitiator, an azo photoinitiator and a peroxide photoinitiator.

8. The method according to claim 6, wherein the photocuring of the photocurable composition comprises curing the photocurable composition using ultraviolet light, The ultraviolet light has a wavelength of 350nm to 400nm and has a power of 3J / cm 2 Up to 5J / cm 2 The accumulated light amount, and wherein in the photocuring of the photocurable composition, the photocurable composition is cured at an oxygen concentration of 100 ppm to 5000 ppm.

9. The method according to claim 6, further comprising removing the protective film, wherein the removing of the protective film comprises removing the protective film using a tape, the tape comprising at least one of a heat-peeling tape, an ultraviolet-peeling tape, and a weak-adhesive tape, and When the protective film is removed, the peel strength of the protective film becomes smaller as approaching the central area of ​​the protective film.

10. The method according to claim 6, wherein the photocurable composition has a viscosity of 15 cps to 25 cps and a surface tension of 20 dyne / cm to 30 dyne / cm at 25°C, wherein when applying the photocurable composition on the top of each of the panels using the inkjet printing device, the photocurable composition is applied by a head of the inkjet printing device, and Wherein the head has a temperature range of 30°C to 50°C.

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