Hard coating composition, Anti-reflective film comprising hard coating composition

Abstract

Provided are a hard coating composition, an anti-reflective film including a hard coating layer, and an electronic device including the anti-reflective film. The anti-reflective film includes a substrate; a hard coating layer on the substrate; and a refractive layer on the hard coating layer, in which the hard coating layer may be formed from a polymer derived from a mixture containing silsesquioxane, an isocyanurate compound, and inorganic particles surface-treated with a silane having a fluorene skeleton.

Description

[0001] Cross-references to related applications

[0002] This application claims priority and benefit to Korean Patent Application No. 10-2024-0129751, filed with the Korean Intellectual Property Office on September 25, 2024, the entire contents of which are incorporated herein by reference. Technical Field

[0003] This disclosure relates to hard coating compositions, antireflective films comprising hard coatings, and electronic devices, and more particularly, to hard coating compositions, antireflective films comprising hard coatings formed using hard coating compositions, and electronic devices comprising said antireflective films. Background Technology

[0004] With the development of the information society, the demand for display devices is constantly increasing. For example, display devices are being used in various electronic devices, such as smartphones, digital cameras, laptops, navigation devices, and smart TVs.

[0005] In recent years, in order to increase the portability of display devices and provide wider displays, flexible display devices that allow the display area to be bent and foldable devices that allow the display area to be folded have been released one after another.

[0006] When display devices are used in environments with abundant ambient light from various lighting sources and natural light, the images created on the display may not be clearly visible to the user due to reflected light, or may cause eye strain. For these reasons, the demand for anti-reflective materials is increasing.

[0007] Methods for suppressing light reflection can include: dispersing a filler such as inorganic fine particles in a resin, coating the resin onto a base film, and providing roughness (anti-glare: AG coating); forming multiple layers with different refractive indices on the base film and utilizing optical interference (anti-reflection: AR coating); and combinations of both. Among these, AG coatings can achieve low reflection even when the absolute amount of reflected light is equivalent to that of a typical hard coating, by utilizing light scattering caused by roughness to reduce the amount of light reaching the eye. However, a drawback of the AG coating method is low image sharpness due to surface roughness. Therefore, extensive research has recently been conducted on AR coatings.

[0008] Antireflective films prepared using the AR coating method typically have a multilayer structure, in which a hard coating layer (high-refractive layer), a low-reflection coating layer, etc., are stacked on a substrate. Antireflective films can comprise multiple inorganic films with five or more layers, where high-refractive layers and low-refractive layers are alternately arranged as low-reflection coatings using distributed Bragg reflectors (DBRs). Unfortunately, a drawback of this multilayer inorganic film approach is that the formation of each layer is performed separately, and therefore, if compressive stress increases, the interlayer adhesion (interfacial adhesion) may weaken, leading to cracks in the multiple layers. Summary of the Invention

[0009] One aspect of this disclosure provides a hard coating and a hard coating composition for forming the hard coating, which can effectively prevent reflection of light from the outside and prevent cracks in the anti-reflective film even when the display device is folded and even when the display device has a small amount of refractive layer on the hard coating.

[0010] It should be noted that this disclosure is not limited to the effects and implementations explicitly described herein. Other effects of this disclosure will be apparent to those skilled in the art from the following description.

[0011] According to embodiments of this disclosure, the hard coating composition comprises: a polymer represented by the following chemical formula 1: [Chemical Formula 1]

[0012] At least two of R1 to R6 can be represented by chemical formula 2 or chemical formula 3, at least one can be represented by chemical formula 4, and the remainder can each independently be H, a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C6-C6 alkyl group, or a substituted or unsubstituted C6-C6 alkyl group. 60 The aryl group, substituted or unsubstituted C2-C6 alkenyl group, substituted or unsubstituted C1-C6 alkoxy group, substituted or unsubstituted silyl group or hydroxyl group, X1 and X2 can each independently be H, halogen, substituted or unsubstituted silyl group, and n1, n2 and n3 can each independently be an integer from 1 to 100. [Chemical Formula 2]

[0013] [Chemical Formula 3]

[0014] Among them, R7 to R 12 Each can be independently H, a substituted or unsubstituted C1-C6 alkyl group, or a substituted or unsubstituted C1-C6 alkoxy group, R7 to R 12One or more of them can be coupled to inorganic particles, and each of m1 and m2 can be an integer from 1 to 10 independently. [Chemical Formula 4]

[0015] Where R 13 It can be a substituted or unsubstituted C1-C6 alkylene group, R 14 and R 15 At least one of them can be or The other could be , Substituted or unsubstituted C1-C6 alkyl groups, substituted or unsubstituted C6-C 60 aryl group, substituted or unsubstituted C2-C6 alkenyl group, substituted or unsubstituted C1-C6 alkoxy group, or substituted or unsubstituted C4-C 10 acrylate group, R 16 To R 18 Each of these can be independently H, a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C2-C6 alkenyl group, or a substituted or unsubstituted C4-C group. 10 Acrylate group. Indicates the connection location.

[0016] The hard coating composition may further include at least one photoinitiator.

[0017] The inorganic particles may include at least one of ZrO2, SiO2, TiO2, Al2O3, ZnO, AlN, and Si3N4.

[0018] According to embodiments of this disclosure, the antireflective film includes a substrate; a hard coating layer on the substrate; and a refractive layer on the hard coating layer, wherein the hard coating layer may be formed from a hard coating composition comprising a polymer derived from a mixture containing silsesquioxane, isocyanurate compound, and inorganic particles surface-treated with a silane having a fluorene framework.

[0019] Each 100 parts by weight of the polymer contains 10 to 20 parts by weight of the sesquioxane; 10 to 20 parts by weight of the isocyanurate compound; 1 to 10 parts by weight of the silane having a fluorene skeleton; and 40 to 70 parts by weight of the inorganic particles.

[0020] The hard coating composition may further comprise at least one photoinitiator, wherein the amount of the photoinitiator in the hard coating composition is 1 to 5 parts by weight relative to 100 parts by weight of the polymer.

[0021] The silsesquioxane may have a random structure, a ladder structure, or a cage structure.

[0022] The isocyanurate compound may have at least one acrylate functional group.

[0023] The isocyanurate compound may have at least one C1-C6 alcohol group.

[0024] The inorganic particles may include at least one of ZrO2, SiO2, TiO2, Al2O3, ZnO, AlN, and Si3N4.

[0025] The size of the inorganic particles is 10 nm to 50 nm.

[0026] The silane may have the fluorene skeleton represented by the following chemical formula 5 or chemical formula 6: [Chemical Formula 5]

[0027] [Chemical Formula 6]

[0028] Among them, R7 to R 12 Each of them can be independently H, a substituted or unsubstituted C1-C6 alkyl group, or a substituted or unsubstituted C1-C6 alkoxy group, and each of m1 and m2 can be independently an integer from 1 to 10.

[0029] R7 to R 12 Each of them can be independently an H, a methoxy group, or an ethoxy group.

[0030] The refractive layer includes a first layer, a second layer, and a third layer.

[0031] The antireflective film may have a reflectivity of less than 1%.

[0032] The refractive index of the hard coating is 1.55 to 1.8.

[0033] According to embodiments of this disclosure, an electronic device includes a display panel; a window member on the display panel; and an antireflective film on the window member, wherein the antireflective film includes: a substrate; a hard coating on the substrate; and a refractive layer on the hard coating, wherein the hard coating is formed from a hard coating composition comprising a polymer derived from a mixture containing silsesquioxane, an isocyanurate compound, and inorganic particles surface-treated with a silane having a fluorene framework.

[0034] The refractive layer may include a first layer, a second layer, and a third layer.

[0035] The antireflective film may have a reflectivity of less than 1%.

[0036] The hard coating may have a refractive index of 1.55 to 1.8.

[0037] According to embodiments of this disclosure, by applying a hard coating with a high refractive index formed using a hard coating composition, a smaller number of refractive layers can be used on the hard coating to reduce reflectivity. This allows for reduced compressive stress in the anti-reflective film and suppression of cracks in the anti-reflective film when the display device is folded. Furthermore, the manufacturing process of the anti-reflective film can be simplified and manufacturing costs reduced.

[0038] It should be noted that the effects of the present invention are not limited to those described above, and other effects of the present invention will be apparent to those skilled in the art from the following description. Attached Figure Description

[0039] The above and other aspects and features of this disclosure will become more apparent from the detailed description of embodiments thereof with reference to the accompanying drawings, in which: Figure 1 This is a perspective view showing a display device in an unfolded state according to an embodiment of the present disclosure.

[0040] Figure 2 It is shown Figure 1 A perspective view of the display device in its folded state.

[0041] Figure 3 This is a perspective view showing a display device in an unfolded state according to another embodiment of the present disclosure.

[0042] Figure 4 It is shown Figure 3 A perspective view of the display device in its folded state.

[0043] Figure 5 This is a cross-sectional view showing a display device according to an embodiment of the present disclosure.

[0044] Figure 6 yes Figure 5 A schematic cross-sectional view of the display panel.

[0045] Figure 7 This is a cross-sectional view showing an anti-reflective film in a display device according to a first embodiment of the present disclosure.

[0046] Figure 8 This is a cross-sectional view showing an anti-reflective film in a display device according to a second embodiment of the present disclosure.

[0047] Figure 9 This is a graph showing the relationship between the refractive index of the hard coating of the antireflective film in a display device according to an embodiment of the present disclosure and the zirconium oxide (ZrO2) content of the hard coating composition used to form the hard coating.

[0048] Figure 10 This is a graph showing the relationship between the reflectivity of an antireflective film according to an embodiment of the present disclosure and the wavelength range. Detailed Implementation

[0049] The features of this disclosure and methods for implementing them will become clear from the embodiments described in detail below with reference to the accompanying drawings. However, this disclosure is not limited to the embodiments disclosed below, but can be implemented in various different forms, and these embodiments are provided only to make the content of this disclosure complete and fully inform those skilled in the art of its scope, and the inventive concept is defined by the scope of the claims.

[0050] When a first element or first layer is referred to as being "on" a second element or second layer, the first element or first layer may be directly disposed above the second element or second layer, or indirectly disposed above the second element or second layer via an intermediate element or layer. The same reference numerals denote the same components throughout the specification. The shapes, dimensions, ratios, angles, quantities, etc., disclosed in the drawings for explaining the embodiments are illustrative, and this disclosure is not limited to the specific details illustrated.

[0051] Although the terms "first" and "second" are used to describe various components, these components are not limited to a specific order or priority of these terms. These terms are used to primarily distinguish one component from another. Therefore, there is no doubt that the first component mentioned below can also be the second component within the technical concept of this disclosure.

[0052] The embodiments of this disclosure will be described in detail below with reference to the accompanying drawings.

[0053] As used herein, the term alkyl can include straight-chain or branched, saturated C1-C6 alkyl groups, and can include, but is not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, or all possible isomers thereof. As used herein, the term alkylene refers to a divalent group having substantially the same structure as an alkyl group.

[0054] As used herein, the term halogen can refer to an element in Group 17 of the periodic table and can include, but is not limited to, F, Cl, Br, or I.

[0055] As used herein, the term alkenyl means a monovalent hydrocarbon group having one or more carbon-carbon double bonds at the backbone (e.g., middle) and / or ends (e.g., tip) of an alkyl group having two or more carbon atoms, and may include C2-C6 alkenyl groups. Examples of alkenyl groups may include vinyl groups, propenyl groups, butenyl groups, pentenyl groups, hexenyl groups, or all possible isomers thereof, but embodiments of this disclosure are not limited thereto.

[0056] As used herein, the term alkoxy group refers to a group having the formula -OA. 101 The monovalent group, of which A 101 It is an alkyl group and may include C1-C6 alkoxy groups. Examples of alkoxy groups may include methoxy groups, ethoxy groups, propoxy groups, butoxy groups, pentoxy groups, hexoxy groups or all possible isomers thereof, but embodiments of the present disclosure are not limited thereto.

[0057] As used herein, the term aryl refers to a monovalent group having a carbocyclic aromatic system and may have 6 to 60 carbon atoms (e.g., 6 to 30, 6 to 20, 6 to 15, or 6 to 10 carbon atoms) derived from an aromatic hydrocarbon ring by any suitable functional group or substituent. Examples of aryl groups may include phenyl groups, naphthyl groups, fluorenyl groups, anthraceneyl groups, phenanthrene groups, biphenyl groups, triphenyl groups, tetraphenyl groups, pentaphenyl groups, hexaphenyl groups, benzo[a]phenanthrene groups, pyrene groups, benzo[a]fluorene anthracene groups, alkyl groups, etc., but embodiments of this disclosure are not limited thereto.

[0058] As used herein, the term silyl group includes alkylsilyl groups and arylsilyl groups. Examples of silyl groups may include trimethylsilyl groups, triethylsilyl groups, tert-butyldimethylsilyl groups, dimethylsilyl groups, propyldimethylsilyl groups, triphenylsilyl groups, diphenylsilyl groups, phenylsilyl groups, etc., but embodiments of this disclosure are not limited thereto.

[0059] As used herein, the term boron group may mean a boron atom bonded to an alkyl group and / or an aryl group as defined above. Boron groups include alkylboron groups and / or arylboron groups. Examples of boron groups may include dimethylboron groups, tert-butyldimethylboron groups, diphenylboron groups, phenylboron groups, etc., but embodiments of this disclosure are not limited thereto.

[0060] As used herein, the term heterocyclic group may contain at least one of B, O, N, P, Si, and S as a heteroatom, and the number of heteroatoms contained in the heterocyclic group may be 1 to 10, for example 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. If the heterocyclic group contains two or more heteroatoms, the two or more heteroatoms may be the same as or different from each other. The heterocyclic group may be a monocyclic heterocyclic group or a polycyclic heterocyclic group, and includes heteroaryl groups. The number of cyclic carbon atoms in the heterocyclic group may be 2 to 60, 2 to 50, 2 to 40, 2 to 30, 2 to 20, or 2 to 10.

[0061] Examples of aliphatic heterocyclic groups may include oxetecyclopropane groups, thiohexecyclopropane groups, pyrrolidinyl groups, piperidine groups, tetrahydrofuran groups, tetrahydrothiophene groups, thiohexane groups, tetrahydropyran groups, 1,4-dioxetecyclohexane groups, etc., but the embodiments of this disclosure are not limited thereto.

[0062] Examples of heteroaryl groups may include thiophene groups, furan groups, pyrrole groups, imidazole groups, pyridine groups, bipyridine groups, pyrimidine groups, triazine groups, triazole groups, acridine groups, pyridazine groups, pyrazine groups, quinoline groups, quinazoline groups, quinoxaline groups, phenoxazine groups, phthalazine groups, pyridopyrimidine groups, pyridopyrazine groups, pyrazinopyrazine groups, isoquinoline groups, indole groups, carbazole groups, and N-arylcarbazole groups. N-heteroarylcarbazole group, N-alkylcarbazole group, benzoxazole group, benzimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, thiophene-thiophene group, benzofuran group, phenanthroline group, thiazole group, isoxazole group, oxazole group, oxadiazole group, thiadiazole group, phenothiazine group, dibenzothiophene group, dibenzofuran group, etc., but the embodiments disclosed herein are not limited to these.

[0063] Features of each of the various embodiments of this disclosure can be combined, either partially or entirely, or combined with each other, and various technical connections and operations are possible. Each embodiment can be implemented independently of the other embodiments, or features from different embodiments can be implemented together.

[0064] The embodiments of this disclosure will be described in detail below with reference to the accompanying drawings. Figure 1 This is a perspective view showing a display device in an unfolded state according to an embodiment of the present disclosure. Figure 2 It is shown Figure 1 A perspective view of the display device in its folded state.

[0065] refer to Figure 1 and Figure 2 , Figure 1The diagram shows a first state in which the display device 10 is not folded along fold lines FL1 and FL2, and Figure 2 The second state in which the display device 10 is folded along fold lines FL1 and FL2 is shown.

[0066] The display device 10 according to embodiments of this disclosure is used to display moving or still images. The display device 10 can be used as a display screen for portable electronic devices such as mobile phones, smartphones, tablet PCs, smartwatches, watch phones, mobile communication terminals, e-notebooks, e-book readers, portable multimedia players (PMPs), navigation devices, and ultra-mobile PCs (UMPCs), as well as for various products such as televisions, laptops, monitors, billboards, and Internet of Things (IoT) devices.

[0067] like Figure 1 and Figure 2 As shown, the first direction DR1 can refer to a direction parallel to the width of the display device 10, for example, the horizontal direction of the display device 10 when viewed from the top. The second direction DR2 can refer to a direction parallel to the length of the display device 10, for example, the vertical direction of the display device 10 when viewed from the top. The third direction DR3 can refer to the thickness direction of the display device 10.

[0068] The display device 10 may have a quadrilateral shape, such as a rectangular shape when viewed from above. Each of the corners of the display device 10 may form a right angle or may be a rounded corner. The front surface of the display device 10 may include two shorter sides extending in a first direction DR1 and two longer sides extending in a second direction DR2.

[0069] The display device 10 may include a display area DA and a non-display area NDA. When viewed from above, the shape of the display area DA may resemble the shape of the display device 10. For example, if the display device 10 has a rectangular shape when viewed from above, the display area DA may also have a rectangular shape when viewed from above.

[0070] The display area DA may include multiple pixels to display an image. The non-display area NDA may not contain pixels and therefore may not display an image. The non-display area NDA may be positioned around the display area DA. The non-display area NDA may surround the display area DA, but embodiments of this disclosure are not limited thereto. The display area DA may be at least partially surrounded by the non-display area NDA.

[0071] The display device 10 can remain unfolded in a first state or folded or bent in a second state. For example... Figure 2As shown, the display device 10 can be folded inward (referred to herein as "inward fold") such that the two front surfaces of the display device DA in the unfolded state face each other. In this inward fold, a portion of the front surface of the display device 10 can face or even contact another portion of the front surface. Alternatively, the display device 10 can be folded outward (referred to herein as "outward fold") such that a portion of the rear surface in the folded state faces or even contacts another portion of the rear surface.

[0072] Display device 10 may include a folding region FDA, a first non-folding region NFA1, and a second non-folding region NFA2. Display device 10 may be bent or folded at the folding region FDA, but not at the first non-folding region NFA1 and the second non-folding region NFA2. According to embodiments of this disclosure, the first non-folding region NFA1 and the second non-folding region NFA2 may be flat areas of display device 10.

[0073] The first non-folding region NFA1 may be on one side, for example, to the left of the folding region FDA. The second non-folding region NFA2 may be on the opposite side, for example, to the right of the folding region FDA. The folding region FDA may be defined by a first fold line FL1 and a second fold line FL2, and the display device 10 may be bent at a predetermined curvature between the first fold line FL1 and the second fold line FL2. The first fold line FL1 may be the boundary between the folding region FDA and the first non-folding region NFA1, and the second fold line FL2 may be the boundary between the folding region FDA and the second non-folding region NFA2.

[0074] The first fold line FL1 and the second fold line FL2 can be as follows: Figure 1 and Figure 2 The display device 10 extends along the second direction DR2 shown in the diagram, and the display device 10 can be folded relative to the folding axis extending along the second direction DR2. Therefore, the width of the display device 10 in the first direction DR1 can be reduced to about half, making the display device 10 easy to carry.

[0075] When the first fold line FL1 and the second fold line FL2 are as follows Figure 1 and Figure 2 When the folded region FDA extends along the second direction DR2 as shown, its length along the second direction DR2 can be greater than its width along the first direction DR1. Furthermore, the length of the first non-folded region NFA1 along the second direction DR2 can be greater than its width along the first direction DR1. The length of the second non-folded region NFA2 along the second direction DR2 can be greater than its width along the first direction DR1.

[0076] Each of the display area DA and the non-display area NDA can overlap at least one of the folded area FDA, the first non-folded area NFA1, and the second non-folded area NFA2. Figure 1 and Figure 2 In the example shown, each of the overlapping folded regions FDA, first non-folded region NFA1, and second non-folded region NFA2 in the display region DA and non-display region NDA.

[0077] Figure 3 This is a perspective view showing a display device in an unfolded state according to another embodiment of the present disclosure. Figure 4 It is shown Figure 3 A perspective view of the display device in its folded state.

[0078] Figure 3 and Figure 4 The implementation plan is basically the same as Figure 1 and Figure 2 The implementation scheme is the same, except that the first fold line FL1 and the second fold line FL2 extend in the first direction DR1 and the display device 10 can be folded relative to the folding axis extending in the first direction DR1. When folded, the length of the display device 10 in the second direction DR2 can be reduced to about half. (The following will not be described in detail...) Figure 1 and Figure 2 The same components Figure 3 and Figure 4 To avoid redundancy of components.

[0079] refer to Figure 3 and Figure 4 , Figure 3 The diagram shows a first state in which the display device 10 is not folded along fold lines FL1 and FL2, and Figure 4 The second state in which the display device 10 is folded along fold lines FL1 and FL2 is shown.

[0080] In the first state in which the display device 10 is unfolded, the length of the display device 10 extending in the second direction DR2 may be longer than the width of the display device 10 extending in the first direction DR1.

[0081] The first fold line FL1 and the second fold line FL2 can be as follows: Figure 3 and Figure 4 The device extends along a first direction DR1 as shown in the diagram, and the display device 10 can be folded relative to a folding axis extending along the first direction DR1.

[0082] The first non-folding region NFA1 can be on one side, for example, the first side of the folded region FDA. The second non-folding region NFA2 can be on the opposite side, for example, the second side of the folded region FDA.

[0083] In the first fold line FL1 and the second fold line FL2, as shown Figure 3 and Figure 4 When extending along the first direction DR1 as shown, the width of the folded region FDA in the first direction DR1 can be greater than its length in the second direction DR2. For the first non-folded region NFA1, the length of the first non-folded region NFA1 in the second direction DR2 can be greater than its width in the first direction DR1. For the second non-folded region NFA2, the length of the second non-folded region NFA2 in the second direction DR2 can be greater than its width in the first direction DR1.

[0084] In the following description, for the sake of illustration, Figure 3 and Figure 4 The implementation schemes will be described as examples, but this disclosure is not limited thereto. For example, the following description can be applied equally to... Figure 1 and Figure 2 The implementation plan.

[0085] Figure 5 This is a cross-sectional view showing a display device according to an embodiment of the present disclosure.

[0086] refer to Figure 5 The display device 10 according to the embodiments of the present disclosure may include an anti-reflective film 100, a window member 200, a first adhesive member 300, an upper protective member 400, and a display panel 500.

[0087] First, the display panel 500 can be a panel for displaying images. The display panel 500 can be an organic light-emitting display panel including an organic light-emitting layer, a quantum dot light-emitting display panel including a quantum dot light-emitting layer, an inorganic light-emitting display panel using inorganic semiconductor elements as light-emitting elements, or a micro light-emitting display panel using micro light-emitting diodes as light-emitting elements. In the following description, an organic light-emitting display panel is used as the display panel 500. However, it should be understood that this disclosure is not limited thereto.

[0088] Display panel 500 may include a light-transmitting region LTA overlapping an optical device OPD on a third-direction DR3. The optical device OPD is an optical sensor that detects light and may be, for example, a camera sensor, a proximity sensor, and an illuminance sensor. The light-transmitting region LTA may be part of the display region DA.

[0089] The light-transmitting region (LTA) may include a transmissive area that allows light to pass through. Optionally, the light-transmitting region LTA may be a through-hole extending through the display panel. The transmittance of the light-transmitting region LTA may be higher than the transmittance of the display area DA excluding the light-transmitting region LTA. Furthermore, due to the transmissive area of ​​the light-transmitting region LTA, the pixel density or integration level in the light-transmitting region LTA may be lower than the pixel density or integration level in the display area DA excluding the light-transmitting region LTA. For example, the number of pixels per unit area in the light-transmitting region LTA may be lower than the number of pixels per unit area in the display area DA outside the light-transmitting region LTA. Optionally, the number of pixels per inch (PPI) in the light-transmitting region LTA may be less than the number of PPIs in the display area DA outside the light-transmitting region LTA.

[0090] The upper protective member 400 may be located on the front surface of the display panel 500. The upper protective member 400 may dampen vibrations to protect the display panel 500 from external impacts. For example, the upper protective member 400 may comprise a material with high flexibility and high rigidity.

[0091] Window member 200 can be attached to the front surface of upper protective member 400 via first adhesive member 300. Window member 200 is made of a transparent material and can be, for example, glass or plastic. For example, window member 200 can be ultra-thin glass (UTG) with a thickness of 0.1 mm or less, or a transparent polyimide film.

[0092] The first adhesive component 300 may be a transparent adhesive film or a transparent adhesive resin. For example, the first adhesive component 300 may include a transparent adhesive, such as a pressure-sensitive adhesive (PSA) and an optically clear adhesive (OCA). The first adhesive component 300 may contain an acrylic adhesive material.

[0093] An anti-reflective film 100 may be present on the front surface of the window member 200. The anti-reflective film 100 may include multiple refractive layers with different refractive indices. The anti-reflective film 100 can reduce reflected light passing through the multiple refractive layers. The anti-reflective film 100 is a key feature of this disclosure and will be described in detail later.

[0094] A light-blocking layer (not shown) for absorbing light incident from the outside, a buffer layer (not shown) for absorbing impacts from the outside, and a heat dissipation layer for effectively dissipating heat from the display panel 500 may be further included below the display panel 500.

[0095] A light-blocking layer blocks light transmission, thus preventing components positioned beneath the light-blocking layer from being seen from above the display panel 500. The light-blocking layer may include light-absorbing materials, such as black pigments and black dyes.

[0096] The buffer layer absorbs external vibrations to prevent damage to the display panel 500. The buffer layer can consist of a single layer or multiple layers. For example, the buffer layer can contain polymer resins such as polyurethane, polycarbonate, polypropylene, and polyethylene, or it can contain elastic materials such as rubber and sponges obtained by foaming urethane-based or acrylic-based materials.

[0097] The heat sink layer may include a first heat dissipation layer containing graphite or carbon nanotubes, and the second heat dissipation layer may include a thin metal film, such as copper, nickel, ferrite, and silver, which can block electromagnetic waves and has high thermal conductivity.

[0098] Figure 6 yes Figure 5 A schematic cross-sectional view of the display panel 500.

[0099] refer to Figure 6 The display panel 500 may include a substrate SUB, a display layer DISL on the substrate SUB, and a touch detection layer TDL disposed on the display layer DISL. The display layer DISL may include a thin film transistor layer TFTL, an emissive material layer EML, and an encapsulation layer TFEL.

[0100] The thin-film transistor layer (TFTL) can be on the substrate (SUB). The TFTL may include a barrier layer (BR), a thin-film transistor (TFT1), a first capacitor electrode (CAE1), a second capacitor electrode (CAE2), a first anode connection electrode (ANDE1), a second anode connection electrode (ANDE2), a gate insulator (530), a first intermediate dielectric film (541), a second intermediate dielectric film (542), a first planarization film (560), and a second planarization film (580).

[0101] The substrate SUB can be made of an insulating material, such as a polymer resin. For example, the substrate SUB can be made of polyimide. The substrate SUB can be a flexible substrate that can be bent, folded, or rolled up.

[0102] The barrier layer BR can be on the substrate SUB. The barrier layer BR is a film used to protect the thin-film transistor TFT1 of the thin-film transistor layer TFTL and the emitter layer 572 of the emitter material layer EML. The barrier layer BR can be composed of multiple inorganic films stacked on top of each other in an alternating manner. For example, the barrier layer BR can be composed of multiple layers in which one or more of the inorganic layers of silicon nitride layer, silicon oxide nitride layer, silicon oxide layer, titanium oxide layer and aluminum oxide layer are stacked on top of each other alternately.

[0103] The thin-film transistor TFT1 can be on the barrier layer BR. The active layer ACT1 of the thin-film transistor TFT1 can be on the barrier layer BR. The active layer ACT1 of the thin-film transistor TFT1 can include polycrystalline silicon, monocrystalline silicon, low-temperature polycrystalline silicon, amorphous silicon, or oxide semiconductor.

[0104] The active layer ACT1 may include a channel region CHA1, a source region TS1, and a drain region TD1. The channel region CHA1 may overlap with the gate electrode TG1 on a third-direction DR3, which is the thickness direction of the substrate SUB. The source region TS1 may be on one side of the channel region CHA1, and the drain region TD1 may be on the opposite side of the channel region CHA1. The source region TS1 and the drain region TD1 may not overlap with the gate electrode TG1 on the third-direction DR3. The source region TS1 and the drain region TD1 may be formed by doping silicon semiconductor or oxide semiconductor with ions or impurities to achieve conductivity.

[0105] The gate insulator 530 may be on the active layer ACT1 of the thin-film transistor TFT1. The gate insulator 530 may include an inorganic layer, such as a silicon nitride layer, a silicon oxide nitride layer, a silicon oxide layer, a titanium oxide layer, or an aluminum oxide layer.

[0106] The gate electrode TG1 and the first capacitor electrode CAE1 of the thin-film transistor TFT1 can be on the gate insulator 530. The gate electrode TG1 can overlap with the channel region CHA1 on the third-direction DR3. Although in Figure 6 In the example shown, the gate electrode TG1 and the first capacitor electrode CAE1 are spaced apart from each other, but the gate electrode TG1 and the first capacitor electrode CAE1 can be connected to each other as a single component. The gate electrode TG1 and the first capacitor electrode CAE1 can be composed of a single layer or multiple layers of one of molybdenum (Mo), aluminum (Al), chromium (Cr), gold (Au), titanium (Ti), nickel (Ni), neodymium (Nd) and copper (Cu) or their alloys.

[0107] The first intermediate dielectric film 541 can be on the gate electrode TG1 and the first capacitor electrode CAE1 of the thin-film transistor TFT1. The first intermediate dielectric film 541 may include an inorganic layer, such as a silicon nitride layer, a silicon oxide nitride layer, a silicon oxide layer, a titanium oxide layer, or an aluminum oxide layer. The first intermediate dielectric film 541 may be made of multiple inorganic films.

[0108] The second capacitor electrode CAE2 can be on the first intermediate dielectric film 541. The second capacitor electrode CAE2 can overlap with the first capacitor electrode CAE1 of the thin-film transistor TFT1 on the third-direction DR3. Furthermore, if the gate electrode TG1 and the first capacitor electrode CAE1 are formed as a single component, the second capacitor electrode CAE2 can overlap with the gate electrode TG1 on the third-direction DR3. Because the first intermediate dielectric film 541 has a predetermined dielectric constant, the capacitor can be formed by the first capacitor electrode CAE1, the second capacitor electrode CAE2, and the first intermediate dielectric film 541 disposed therebetween. The second capacitor electrode CAE2 can be composed of a single layer or multiple layers of one of molybdenum (Mo), aluminum (Al), chromium (Cr), gold (Au), titanium (Ti), nickel (Ni), neodymium (Nd), and copper (Cu) or their alloys.

[0109] The second intermediate dielectric film 542 can be disposed above the second capacitor electrode CAE2. The second intermediate dielectric film 542 may include an inorganic layer, such as a silicon nitride layer, a silicon oxide nitride layer, a silicon oxide layer, a titanium oxide layer, or an aluminum oxide layer. The second intermediate dielectric film 542 may be made of multiple inorganic films.

[0110] The first anode connection electrode ANDE1 can be located on the second intermediate dielectric film 542. The first anode connection electrode ANDE1 can be connected to the drain region TD1 of the thin-film transistor TFT1 via a first connection contact hole ANCT1 extending through the gate insulator 530, the first intermediate dielectric film 541, and the second intermediate dielectric film 542. The first anode connection electrode ANDE1 can be composed of a single layer or multiple layers of one or an alloy of molybdenum (Mo), aluminum (Al), chromium (Cr), gold (Au), titanium (Ti), nickel (Ni), neodymium (Nd), and copper (Cu).

[0111] A first planarization film 560 may be disposed above the first anode connection electrode ANDE1 to provide a flat surface for horizontal differences caused by the thin-film transistor TFT1. The first planarization film 560 may include an organic layer, such as an acrylic resin layer, an epoxy resin layer, a phenolic resin layer, a polyamide resin layer, and a polyimide resin layer.

[0112] The second anode connection electrode ANDE2 can be on the first planarization film 560. The second anode connection electrode ANDE2 can be connected to the first anode connection electrode ANDE1 through a second connection contact hole ANCT2 extending through the first planarization film 560. The second anode connection electrode ANDE2 can be composed of a single layer or multiple layers of one or an alloy of molybdenum (Mo), aluminum (Al), chromium (Cr), gold (Au), titanium (Ti), nickel (Ni), neodymium (Nd) and copper (Cu).

[0113] The second planarization film 580 can be on the second anode connection electrode ANDE2. The second planarization film 580 can be formed as an organic layer, such as an acrylic resin layer, an epoxy resin layer, a phenolic resin layer, a polyamide resin layer, and a polyimide resin layer.

[0114] The light-emitting element (LEL) and the emitting material layer (EML) of block 590 can be on the second planarization film 580. Each of the light-emitting elements (LEL) includes a pixel electrode 571, an emitting layer 572, and a common electrode 573.

[0115] The pixel electrode 571 can be on the second planarization film 580. The pixel electrode 571 can be connected to the second anode connection electrode ANDE2 through a third connection contact hole ANCT3 extending through the second planarization film 580.

[0116] In the top emission structure where light is emitted from the emission layer 572 toward the common electrode 573, the pixel electrode 571 can be made of a metallic material with high reflectivity, such as a stacked structure of aluminum and titanium (Ti / Al / Ti), a stacked structure of aluminum (Al) and ITO (indium tin oxide) (ITO / Al / ITO), an APC alloy, and a stacked structure of APC alloy and ITO (ITO / APC / ITO). The APC alloy is an alloy of silver (Ag), palladium (Pd), and copper (Cu).

[0117] Block 590 may separate pixel electrodes 571 on the second planarization film 580 to define emission regions EA1 and EA2. Block 590 may be configured to cover the edges of pixel electrodes 571. Block 590 may include organic films, such as acrylic resin films, epoxy resin films, phenolic resin films, polyamide resin films, and polyimide resin films.

[0118] In each of the first emission region EA1 and the second emission region EA2, the pixel electrode 571, the emission layer 572 and the common electrode 573 are stacked on top of each other in sequence, such that holes from the pixel electrode 571 and electrons from the common electrode 573 recombine with each other in the emission layer 572 to emit light.

[0119] The emission layer 572 can be located on the pixel electrode 571 and the block 590. The emission layer 572 can contain organic materials to emit light of a specific color. For example, the emission layer 572 can include a hole transport layer, an organic material layer, and an electron transport layer.

[0120] The common electrode 573 may be on the emitter layer 572. The common electrode 573 may be configured to cover the emitter layer 572. The common electrode 573 may be a common layer that shares a common span across the first emitter region EA1 and the second emitter region EA2.

[0121] In a top-emitting organic light-emitting diode (OLED), the common electrode 573 may include a transparent conductive material (TCP) that can transmit light, such as ITO and IZO; or a semi-transmissive conductive material, such as magnesium (Mg), silver (Ag), or an alloy of magnesium (Mg) and silver (Ag). If the common electrode 173 includes a semi-transmissive metallic material, light extraction efficiency can be improved by using a microcavity.

[0122] Spacer 591 may be present on block 590. During the process of fabricating emitter layer 572, spacer 591 may support the mask. Spacer 591 may include organic layers, such as acrylic resin layers, epoxy resin layers, phenolic resin layers, polyamide resin layers, and polyimide resin layers.

[0123] According to some embodiments of this disclosure, the display panel 500 may further include a capping layer CPL on a common electrode 573. The capping layer CPL may be made of an inorganic material. For example, the capping layer CPL may contain at least one of the following: silicon nitride, aluminum nitride, zirconium nitride, titanium nitride, hafnium nitride, tantalum nitride, silicon oxide, aluminum oxide, titanium oxide, tin oxide, cerium oxide, and silicon nitride.

[0124] The encapsulation layer TFEL can be on the common electrode 573. The encapsulation layer TFEL may include at least one inorganic layer to prevent oxygen or moisture from penetrating into the emitter material layer EML. In addition, the encapsulation layer TFEL may include at least one organic film to protect the emitter material layer EML from particles such as dust. For example, the encapsulation layer TFEL may include a first inorganic encapsulation layer TFE1, an organic encapsulation layer TFE2, and a second inorganic encapsulation layer TFE3.

[0125] The first inorganic encapsulation film TFE1 can be on the common electrode 573, the organic encapsulation film TFE2 can be on the first inorganic encapsulation film TFE1, and the second inorganic encapsulation film TFE3 can be on the organic encapsulation film TFE2. The first inorganic encapsulation film TFE1 and the second inorganic encapsulation film TFE3 can be composed of multiple layers, wherein one or more inorganic layers, including silicon nitride layers, silicon oxide nitride layers, silicon oxide layers, titanium oxide layers, and aluminum oxide layers, are alternately stacked. The organic encapsulation film TFE2 can be an organic film, such as an acrylic resin film, epoxy resin film, phenolic resin film, polyamide resin film, polyimide resin film, etc.

[0126] The touch detection layer (TDL) can be on the encapsulation layer (TFEL). The touch detection layer (TDL) includes a first touch insulating film (TINS1), a connection electrode (BE), a second touch insulating film (TINS2), a driving electrode (TE), a sensing electrode (RE), and a third touch insulating film (TINS3).

[0127] The first touch insulating film TINS1 may be on the encapsulation layer TFEL. The first touch insulating film TINS1 may include an inorganic film, such as a silicon nitride layer, a silicon oxide nitride layer, a silicon oxide layer, a titanium oxide layer, or an aluminum oxide layer.

[0128] The connecting electrode BE can be on the first touch insulating film TINS1. The connecting electrode BE can be composed of a single layer or multiple layers of one or an alloy of molybdenum (Mo), aluminum (Al), chromium (Cr), gold (Au), titanium (Ti), nickel (Ni), neodymium (Nd) and copper (Cu).

[0129] The second touch insulating film TINS2 may be located above the connecting electrode BE. The second touch insulating film TINS2 may include an inorganic layer, such as a silicon nitride layer, a silicon oxide nitride layer, a silicon oxide layer, a titanium oxide layer, or an aluminum oxide layer. Optionally, the second touch insulating film TINS2 may include an organic layer, such as an acrylic resin layer, an epoxy resin layer, a phenolic resin layer, a polyamide resin layer, or a polyimide resin layer.

[0130] The driving electrode TE and the sensing electrode RE can be on the second touch insulating film TINS2. The driving electrode TE and the sensing electrode RE can be composed of a single layer or multiple layers of one of molybdenum (Mo), aluminum (Al), chromium (Cr), gold (Au), titanium (Ti), nickel (Ni), neodymium (Nd) and copper (Cu) or their alloys.

[0131] The driving electrode TE and the sensing electrode RE can overlap with the connecting electrode BE on the third-direction DR3. The driving electrode TE can be connected to the connecting electrode BE through a touch contact hole TCNT1 extending through the first touch insulating film TINS1.

[0132] The third touch insulating film TINS3 can be formed on the driving electrode TE and the sensing electrode RE. The third touch insulating layer TINS3 can provide a flat surface on the driving electrode TE, the sensing electrode RE, and the connection electrode BE, which have different heights. The third touch insulating layer TINS3 may include organic layers, such as acrylic resin layers, epoxy resin layers, phenolic resin layers, polyamide resin layers, and polyimide resin layers.

[0133] In the following description, various embodiments of the antireflective film 100 according to the present disclosure will be described with reference to the accompanying drawings.

[0134] Figure 7 This is a cross-sectional view showing an anti-reflective film in a display device according to a first embodiment of the present disclosure.

[0135] refer to Figure 7 The antireflective film 100 according to the first embodiment may include a substrate 110, a hard coating 120, and a refractive layer 130.

[0136] The substrate 110 can be the window member 200. That is, the hard coating 120 can be on the window member 200. The hard coating 120 can protect the window member 200 from external impacts. The hard coating 120 can have a higher strength than the window member 200. The hard coating 120 can prevent damage such as fine cracks, dents and deformation caused by external compression or impact.

[0137] The substrate 110 can be implemented as a separate substrate. The substrate can be a plastic, glass, or metal substrate.

[0138] The antireflective film 100 according to the embodiment will be described in detail later. Hereinafter, a hard coating composition for forming the hard coating 120 included in the antireflective film 100 according to the embodiment will be described.

[0139] The hard coating composition may comprise a polymer derived from a mixture containing silsesquioxane, isocyanurate compound, and inorganic particles surface-treated with a silane having a fluorene framework. The hard coating composition may also comprise polymer units derived from a mixture containing silsesquioxane, isocyanurate compound, and inorganic particles surface-treated with a silane having a fluorene framework.

[0140] Silsesquioxanes can include random, ladder-like, or cage-like structures. Each 100 parts by weight of polymer contained in the hard coating composition may contain 10 to 20 parts by weight of silsesquioxane. If the silsesquioxane content is less than 10 parts by weight relative to each 100 parts by weight of polymer contained in the hard coating composition, the flexibility of the hard coating formed using the hard coating composition may not be improved. If the silsesquioxane content is greater than 20 parts by weight relative to each 100 parts by weight of polymer contained in the hard coating composition, the surface hardness of the hard coating containing the hard coating composition may be reduced.

[0141] Isocyanurate compounds may have at least one acrylate functional group.

[0142] Isocyanurate compounds may have at least one C1-C6 alcohol group. For example, isocyanurate compounds may have at least one of the following: methanol group, ethanol group, propanol group, butanol group, pentanol group, and hexanol group. For example, isocyanurate compounds may have a hydroxyl group as a terminal group. The hydroxyl group may form a crosslink with silsesquioxane.

[0143] Isocyanurate compounds may include at least one of the following: (2-[3-(2-hydroxyethyl)-2,4,6-trioxo-5-(2-prop-2-enoyloxyethyl)-1,3,5-triazin-1-yl]ethylprop-2-enoate); bis(acryloyloxyethyl)hydroxyethyl isocyanurate; and bis(methacryloyloxyethyl)hydroxyethyl isocyanurate.

[0144] The polymer contained in the hard coating composition may contain 10 to 20 parts by weight of isocyanurate compound per 100 parts by weight of polymer. If the content of isocyanurate compound is less than 10 parts by weight relative to 100 parts by weight of polymer contained in the hard coating composition, the surface hardness and strength of the hard coating 120 may be reduced. If the content of isocyanurate compound is greater than 20 parts by weight relative to 100 parts by weight of polymer contained in the hard coating composition, the brittleness of the hard coating 120 may increase, and therefore, in the event of bending of the hard coating, flexibility may decrease and cracking may increase.

[0145] The mixture forming the polymer contained in the hard coating composition may contain surface-treated inorganic particles. The inorganic particles may be surface-treated with a silane having a fluorene framework.

[0146] Inorganic particles can be spherical and can have a substantially monodisperse particle size distribution or a polydisperse distribution obtained by mixing multiple particles with monodisperse distributions. For example, the average size of inorganic particles can be from 10 nm to 50 nm. The average size of inorganic particles can represent the average diameter of the inorganic particles. For example, the average diameter of inorganic particles can be from 10 nm to 50 nm.

[0147] If the average size of the inorganic particles exceeds 50 nm in diameter, the optical transparency of the hard coating comprising the hard coating composition according to embodiments of this disclosure may be reduced. If the average size of the inorganic particles is less than 10 nm, the surface hardness may not be sufficiently improved and the refractive index may be reduced.

[0148] The inorganic particles may be at least one of ZrO2, SiO2, TiO2, Al2O3, ZnO, AlN, and Si3N4.

[0149] Inorganic particles surface-treated with silanes having a fluorene framework can increase the content of inorganic particles in a hard coating composition due to increased compatibility with silsesquioxanes through surface modification. Therefore, the hard coating composition according to embodiments of this disclosure can form a hard coating with improved surface hardness, strength, and refractive index by including inorganic particles surface-treated with silanes having a fluorene framework, thereby increasing the proportion of inorganic particles.

[0150] Figure 9 This is a graph showing the relationship between the refractive index of the hard coating of the antireflective film in a display device according to an embodiment of the present disclosure and the zirconium oxide (ZrO2) content of the hard coating composition used to form the hard coating.

[0151] refer to Figure 9 As can be seen, the refractive index increases with the increase of the zirconium oxide content used as inorganic particles.

[0152] The polymer contained in the hard coating composition may contain 40 to 70 parts by weight of inorganic particles per 100 parts by weight of polymer. If the content of inorganic particles is less than 40 parts by weight relative to 100 parts by weight of polymer contained in the hard coating composition, the refractive index of the hard coating may decrease, reducing surface hardness and strength. If the content of inorganic particles is more than 70 parts by weight relative to 100 parts by weight of polymer contained in the hard coating composition, cracking may increase when the hard coating is bent.

[0153] In hard coating compositions, inorganic particles surface-treated with silane having a fluorene framework can be bonded to silsesquioxane and provided as integrally formed polymers.

[0154] Silanes with a fluorene framework can be represented by the following chemical formula 5 or chemical formula 6: [Chemical Formula 5]

[0155] [Chemical Formula 6]

[0156] Among them, R7 to R 12 It can be H, a substituted or unsubstituted C1-C6 alkyl group, or a substituted or unsubstituted C1-C6 alkoxy group, and m1 and m2 can be integers from 1 to 10, such as 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

[0157] R7 to R 12 Each of these can be an H, a methoxy group, or an ethoxy group.

[0158] In silanes with a fluorene framework, R7 to R 12 One or more of them can be linked to inorganic particles.

[0159] Each 100 parts by weight of polymer contained in the hard coating composition may contain 1 to 10 parts by weight of a silane with a fluorene backbone. If the content of the silane with a fluorene backbone is less than 1 part by weight, the bonding strength between the inorganic particles and the silsesquioxane may be reduced.

[0160] The sum of m1 and m2 can be between 2 and 20. As the sum of m1 and m2 increases, the flexibility of the hard coating can be increased.

[0161] The hard coating composition may comprise a polymer formed by reacting a mixture containing silsesquioxane, isocyanurate compound, and inorganic particles surface-treated with a silane having a fluorene backbone.

[0162] The hard coating composition according to the embodiments may comprise a polymer represented by the following chemical formula 1: [Chemical Formula 1]

[0163] Wherein at least two of R1 to R6 are represented by chemical formula 2 or chemical formula 3, at least one by chemical formula 4, and the remainder are H, substituted or unsubstituted C1-C6 alkyl groups, substituted or unsubstituted C6-C6 alkyl groups. 60 The aryl group, substituted or unsubstituted C2-C6 alkenyl group, substituted or unsubstituted C1-C6 alkoxy group, substituted or unsubstituted silyl group or hydroxy group, X1 and X2 are H, halogen, substituted or unsubstituted silyl group, and n1, n2 and n3 are integers from 1 to 100, such as 1, 2, 10, 20, 30, 40, 60, 80, 90 or 100.

[0164] [Chemical Formula 2]

[0165] [Chemical Formula 3]

[0166] Among them, R7 to R 12 It can be H, a substituted or unsubstituted C1-C6 alkyl group, or a substituted or unsubstituted C1-C6 alkoxy group, R7 to R 12 One or more of them can be coupled to inorganic particles, and m1 and m2 can be integers from 1 to 10, such as 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

[0167] [Chemical Formula 4]

[0168] Where R 13 It can be a substituted or unsubstituted C1-C6 alkylene group, R 14 and R 15 At least one of them can be or The other could be , Substituted or unsubstituted C1-C6 alkyl groups, substituted or unsubstituted C6-C 60 aryl group, substituted or unsubstituted C2-C6 alkenyl group, substituted or unsubstituted C1-C6 alkoxy group, or substituted or unsubstituted C4-C 10 acrylate group, R 16 To R 18 It can be H, a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C2-C6 alkenyl group, or a substituted or unsubstituted C4-C group. 10 Acrylate group.

[0169] Isocyanurate compounds combined with sesquioxanes can be represented by the above chemical formula 4.

[0170] Silanes with a fluorene skeleton bonded to silsesquioxanes can be represented by the above chemical formulas 2 and / or 3.

[0171] As used herein, the expression "substituted or unsubstituted" may mean substituted with or unsubstituted by at least one substituent selected from deuterium, halogen, cyano, nitrile, nitro, amino, silyl, boron, phosphine oxide, alkyl, alkenyl, fluorenyl, aryl, and heterocyclic groups.

[0172] As used in this article, the symbol - Indicates the connection location. Connection can refer to a chemical bond.

[0173] Chemical Formula 1 can represent a polymer derived from a mixture containing sesquioxane, isocyanurate compound, and inorganic particles surface-treated with a silane having a fluorene skeleton.

[0174] According to embodiments of this disclosure, the hard coating composition may further comprise at least one photoinitiator.

[0175] Photoinitiators may include at least one of the following: acetophenone-based photoinitiators, benzophenone-based photoinitiators, thioxanone-based photoinitiators, benzoin-based photoinitiators, and triazine-based photoinitiators.

[0176] Photoinitiators may include at least one of the following: α-hydroxy ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-one, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propanoyl)-benzyl]-phenyl}-2-methylprop-1-one, phenyl glyoxylate, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoprop-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) )-But-1-one, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-but-1-one, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine ester, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, [1-(4-phenylthioalkylbenzoyl)heptylamino]benzoate, [1-[9-ethyl-6-(2-methylbenzoyl)carbazole-3-yl]ethyleneamino]acetate, and bis(2,4-cyclopentadienyl)bis[2,6-difluoro-3-(1-pyrrole)phenyl]titanium (IV).

[0177] The hard coating composition may contain 1 to 5 parts by weight of photoinitiator relative to every 100 parts by weight of polymer contained in the hard coating composition.

[0178] The photoinitiator can be an initiator activated by ultraviolet light and can increase the hardness on the surface of a hard coating comprising a hard coating composition according to an embodiment of the present disclosure.

[0179] The hard coating composition may further contain additives and / or solvents.

[0180] The solvent contained in the hard coating composition may include at least one of the following: 1-methoxy-2-methyl-2-propanol (PGM), 2-butanone, propylene glycol methyl ether acetate (PGMEA), propylene glycol ethyl ether acetate (PGEEA), propylene glycol methyl ether (PGME), propylene glycol propyl ether (PGPE), ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol methyl acetate, dipropylene glycol methyl ether, methyl ethoxypropionate, ethyl ethoxypropionate, ethyl acetate, butyl acetate, cyclohexanone, acetone, methyl isobutyl ketone, dimethylformamide, N,N'-dimethylacetamide, N-methylpyrrolidone, and toluene.

[0181] It may further contain additives well known in the art, unless they degrade the effect of the hard coating composition. For example, the hard coating composition according to the embodiments may further contain at least one of surfactants, antioxidants, antistatic agents, leveling agents, and ultraviolet absorbers.

[0182] A hard coating 120 can be formed on the substrate 110 using a hard coating composition. Specifically, the hard coating 120 can be formed by applying a hard coating composition to the substrate 110 and then photocuring it.

[0183] The coating method may include at least one of roller coating, spin coating, deep coating, flow coating and spray coating.

[0184] UV or LED lamps can be used as light sources for photocuring. During photocuring, UV or LED lamps can irradiate light with a concentration of 1,000 mJ / cm². 2 Up to 5,000 mJ / cm 2 Light of high intensity.

[0185] The refractive index of the hard coating 120 formed using the hard coating composition according to the embodiment can be from 1.55 to 1.8. This is higher than the refractive index of 1.5 for hard coatings formed using polymers commonly used in hard coatings, such as urethane resins, epoxy resins, acrylic resins, and acrylate resins.

[0186] The hard coating 120 can have a thickness range that does not increase the repulsive force against the shape deformed when the display device 10 is folded.

[0187] The refractive layer 130 may be on the hard coating layer 120. The refractive layer may include a first refractive layer 131 and a second refractive layer 132 having different refractive indices.

[0188] The first refractive layer 131 may be on the hard coating layer 120. The first refractive layer 131 may be deposited on the hard coating layer 120 by vacuum deposition. The first refractive layer 131 may have a higher refractive index than the second refractive layer 132. The refractive index of the first refractive layer 131 may be, but is not limited to, 1.70 to 2.80. The first refractive layer 131 may have the same thickness as the second refractive layer 132. The first refractive layer 131 may have a higher refractive index than the hard coating layer 120.

[0189] The first refractive layer 131 may comprise a high-refractive-index oxide. For example, the high-refractive-index inorganic oxide may include at least one of the following: titanium niobate (Ti4Nb3O4). 35 ), titanium dioxide (TiO2), zirconium dioxide (ZrO2), lithium niobate (LiNbO3), lithium tantalate (LiTaO3), and lanthanum titanate (LaTiO2).

[0190] The second refractive layer 132 may be on the first refractive layer 131. The second refractive layer 132 may be deposited on the first refractive layer 131 by vacuum deposition. The second refractive layer 132 may have a lower refractive index than the first refractive layer 131. The second refractive layer 132 may have a lower refractive index than the hard coating 120. The refractive index of the second refractive layer 132 may be, but is not limited to, 1.20 to 1.50. The second refractive layer 132 may have the same thickness as the first refractive layer 131.

[0191] The second refractive layer 132 may comprise a low-refractive oxide. For example, the low-refractive oxide may comprise at least one of silicone resin, silica, and silicon dioxide (SiO2).

[0192] In summary, typical antireflective films have a multilayer structure of five or more layers by utilizing a distributed Bragg reflector (DBR) to alternate between high-refractive-index and low-refractive-index layers made of inorganic films. To address this drawback, according to embodiments of this disclosure, the hard coating 120 has a higher refractive index than a hard coating formed using polymers such as urethane resins, epoxy resins, acrylic resins, and acrylate resins. The hard coating 120 can be used as a component of the distributed Bragg reflector, such as... Figure 7 As shown in the figure. Therefore, even if the number of refractive layers on the hard coating 120 used to form the distributed Bragg reflector is reduced to three layers or less, the reflective properties of the antireflective film 100 can be maintained.

[0193] Furthermore, by reducing the number of refractive layers on the hard coating 120, cracks can be prevented from forming in the refractive layers of the antireflective film 100 due to compressive stress from the folded display device 10. Additionally, the number of manufacturing processes can be reduced, thus lowering manufacturing costs.

[0194] Figure 8 This is a cross-sectional view showing an anti-reflective film in a display device according to a second embodiment of the present disclosure.

[0195] Figure 8 The implementation plan is basically the same as Figure 7 The implementation scheme is the same, but the antireflective film 100 further includes a third refractive layer 133; therefore, any redundant description will be omitted.

[0196] refer to Figure 8The third refractive layer 133 may be disposed on the second refractive layer 132. The third refractive layer 133 may be deposited on the second refractive layer 132 by vacuum deposition. The third refractive layer 133 may have a higher refractive index than the second refractive layer 132. The refractive index of the third refractive layer 133 may be, but is not limited to, 1.70 to 2.80. The third refractive layer 133 may have the same thickness as the second refractive layer 132. The third refractive layer 133 may be substantially the same as the first refractive layer 131. The third refractive layer 133 may have a higher refractive index than the hard coating 120.

[0197] Although a high-refractive-index first refractive layer 131, a low-refractive-index second refractive layer 132, and a high-refractive-index third refractive layer 133 have been described according to embodiments of this disclosure, a low-refractive-index first refractive layer 131, a high-refractive-index second refractive layer 132, and a low-refractive-index third refractive layer 133 may be used according to another embodiment. In the latter case, the first refractive layer 131 may have a lower refractive index than the hard coating 120, the second refractive layer 132 may have a higher refractive index than the hard coating 120, and the third refractive layer 133 may have a lower refractive index than the hard coating 120.

[0198] The embodiments of this disclosure will be described in more detail below. It should be understood that the embodiments of this disclosure are exemplary only and are not intended to limit the scope of this disclosure.

[0199] 1. Preparation of inorganic particles surface-treated with silane having a fluorene framework

[0200] First, in reaction formula 1 below, 1.0 equivalents of 9,9-bis(4-allyloxyphenyl)fluorene and 2.0 equivalents of (3-mercaptopropyl)trimethoxysilane are mixed in a reaction vessel. Then, 1-hydroxycyclohexylphenyl ketone as a photoinitiator and tetrahydrofuran (THF) as a solvent are added to the reaction vessel, and the mixture is irradiated with ultraviolet light for two minutes to produce a silane with a fluorene backbone.

[0201] Subsequently, 3 equivalents of silane with a fluorene framework and 65 equivalents of zirconium oxide were subjected to a bead milling process to produce inorganic particles with a silane surface treatment having a fluorene framework.

[0202] [Reaction Formula 1]

[0203] 2. Preparation of hard coating composition

[0204] 15 equivalents of a random-structured silsesquioxane, 15 equivalents of 2-[3-(2-hydroxyethyl)-2,4,6-trioxo-5-(2-prop-2-enoyloxyethyl)-1,3,5-triazinyl-1-yl]ethylprop-2-enoate (ethanol-modified isocyanurate diacrylate), and the obtained inorganic particles surface-treated with a silane having a fluorene backbone were placed in a reaction vessel and mixed. Subsequently, 1.5 equivalents of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide as a photoinitiator and 2-butanone as a solvent were added to the reaction vessel and stirred for 1 hour to produce a hard coating composition.

[0205] 3. Preparation of antireflective film

[0206] 1) Example 1

[0207] The obtained hard coating composition was spin-coated onto a polymethyl methacrylate (PMMA) plastic substrate that had been cleaned using a cleaning process. The coating was then applied using a high-pressure mercury UV lamp at 1600 mJ / cm². 2 The polymethyl methacrylate spin-coated with the hard coating composition was irradiated with high power for 3 minutes to form a hard coating.

[0208] Subsequently, titanium niobate (Ti4Nb3O) 35 Vacuum deposition is performed on the hard coating to form the first refractive layer.

[0209] Subsequently, silicon dioxide (SiO2) is vacuum deposited on the first refractive layer to form the second refractive layer, thereby producing an antireflective film (two refractive layers in Example 1).

[0210] 2) Example 2

[0211] The hard coating was obtained in a manner similar to that of Example 1. A first refractive layer was formed by vacuum depositing silicon dioxide (SiO2) onto the hard coating.

[0212] Subsequently, titanium niobate (Ti4Nb3O) 35 Vacuum deposition is performed on the first refractive layer to form the second refractive layer.

[0213] Subsequently, silicon dioxide (SiO2) is vacuum deposited on the second refractive layer to form the third refractive layer, thereby producing an antireflective film (three refractive layers in Example 2).

[0214] [evaluate]

[0215] 1. Reflectivity of antireflective coatings

[0216] The reflectivity of the antireflective films manufactured in Examples 1 and 2 was measured relative to the wavelength range, and the results were... Figure 10 As shown in the image.

[0217] according to Figure 10 The results shown indicate that the antireflective film of Example 1 has a reflectivity of 0.05% at a wavelength of 550 nm, and the antireflective film of Example 2 has a reflectivity of 0.14% at a wavelength of 550 nm.

[0218] Previously, low reflectivity could be achieved by using distributed Bragg reflectors to alternately arrange high-refractive-index and low-refractive-index layers in five or more layers. However, with the formation of a large number of layers, the number of processes and costs increase, and cracks may occur during folding. In contrast, according to embodiments of this disclosure, by applying a hard coating to the antireflective film using a hard coating composition, a reflectivity of less than 1% can be achieved even using three or fewer refractive layers.

[0219] 2. Radius of curvature of the antireflective coating

[0220] The radius of curvature was evaluated using a mandrel test. Bending characteristics were measured by wrapping an antireflective film having a hard coating formed therein around a test rod and varying the rod's diameter to find the minimum diameter that did not produce cracks in the hard coating. The radius of curvature of the antireflective films manufactured in Examples 1 and 2 was 1.5 mm.

[0221] 3. Evaluation of the folding behavior of the antireflective coating

[0222] The folding behavior was evaluated by repeatedly folding an antireflective film, including a hard coating, 200,000 times at room temperature to observe cracks and changes in appearance.

[0223] Based on the evaluation of the folding behavior, it can be seen that after folding the antireflective films of Examples 1 and 2 according to this disclosure 200,000 times at room temperature, there was no cracking or change in appearance. Based on those data, it can be concluded that the antireflective film including the hard coating has good folding properties.

[0224] Although embodiments of this disclosure have been described with reference to the accompanying drawings, those skilled in the art will understand that this disclosure can be implemented in other specific forms without altering the technical concept or essential characteristics of the disclosure. Therefore, it should be understood that the above embodiments are examples and not limitations.

Claims

1. A hard coating composition comprising: a polymer represented by the following chemical formula 1: [Chemical Formula 1] In this embodiment, at least two of R1 to R6 are represented by chemical formula 2 or chemical formula 3, at least one is represented by chemical formula 4, and the remainder are each independently H, a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C6-C6 alkyl group, or a substituted or unsubstituted C6-C6 alkyl group. 60 The aryl group, substituted or unsubstituted C2-C6 alkenyl group, substituted or unsubstituted C1-C6 alkoxy group, substituted or unsubstituted silyl group or hydroxyl group, X1 and X2 are each independently H, halogen, substituted or unsubstituted silyl group, and n1, n2 and n3 are each independently an integer from 1 to 100. [Chemical Formula 2] [Chemical Formula 3] Among them, R7 to R 12 Each of the following is independently H, a substituted or unsubstituted C1-C6 alkyl group, or a substituted or unsubstituted C1-C6 alkoxy group, wherein R7 to R 12 One of them may be connected to an inorganic particle, and m1 and m2 are each an independent integer from 1 to 10. [Chemical Formula 4] Where R 13 It is a substituted or unsubstituted C1-C6 alkylene group, R 14 and R 15 At least one of them is or The other is , Substituted or unsubstituted C1-C6 alkyl groups, substituted or unsubstituted C6-C 60 aryl group, substituted or unsubstituted C2-C6 alkenyl group, substituted or unsubstituted C1-C6 alkoxy group, or substituted or unsubstituted C4-C 10 acrylate group, R 16 To R 18 Each is independently H, a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C2-C6 alkenyl group, or a substituted or unsubstituted C4-C group. 10 acrylate groups, - Indicates the connection location.

2. The composition of claim 1, further comprising: at least one photoinitiator.

3. The composition of claim 1, wherein the inorganic particles are at least one selected from ZrO2, SiO2, TiO2, Al2O3, ZnO, AlN, and Si3N4.

4. Anti-reflective coating, including: Base; A hard coating on the substrate; as well as The refractive layer on the hard coating, The hard coating is formed from a hard coating composition comprising a polymer derived from a mixture containing silsesquioxane, isocyanurate compound, and inorganic particles surface-treated with a silane having a fluorene framework.

5. The antireflective film of claim 4, wherein each 100 parts by weight of the polymer contains 10 to 20 parts by weight of the sesquioxane; 10 to 20 parts by weight of the isocyanurate compound; 1 to 10 parts by weight of the silane having a fluorene framework; and 40 to 70 parts by weight of the inorganic particles.

6. The antireflective film of claim 4, wherein the hard coating composition further comprises at least one photoinitiator, wherein the amount of the photoinitiator in the hard coating composition is 1 to 5 parts by weight relative to 100 parts by weight of the polymer.

7. The antireflective film according to claim 4, wherein the silsesquioxane has a random structure, a ladder structure, or a cage structure.

8. The antireflective film of claim 4, wherein the isocyanurate compound has at least one acrylate functional group.

9. The antireflective film of claim 8, wherein the isocyanurate compound has at least one C1-C6 alcohol group.

10. The antireflective film of claim 4, wherein the inorganic particles are at least one of ZrO2, SiO2, TiO2, Al2O3, ZnO, AlN, and Si3N4.

11. The antireflective film of claim 4, wherein the size of the inorganic particles is from 10 nm to 50 nm.

12. The antireflective film of claim 4, wherein the silane having the fluorene framework is represented by chemical formula 5 or chemical formula 6: [Chemical Formula 5] [Chemical Formula 6] Among them, R7 to R 12 Each of them is independently H, a substituted or unsubstituted C1-C6 alkyl group, or a substituted or unsubstituted C1-C6 alkoxy group, and each of m1 and m2 is independently an integer from 1 to 10.

13. The antireflective film of claim 12, wherein R7 to R 12 Each of them is independently an H, a methoxy group, or an ethoxy group.

14. The antireflective film of claim 4, wherein the refractive layer comprises a first layer, a second layer, and a third layer.

15. The antireflective film of claim 14, wherein the antireflective film has a reflectivity of less than 1%.

16. The antireflective coating of claim 4, wherein the refractive index of the hard coating is 1.55 to 1.

8.

17. Electronic devices, including: Display panel; Window components on the display panel; as well as The anti-reflective film on the window component, The antireflective film comprises: Base; A hard coating on the substrate; and The refractive layer on the hard coating, The hard coating is formed from a hard coating composition comprising a polymer derived from a mixture containing silsesquioxane, isocyanurate compound, and inorganic particles surface-treated with a silane having a fluorene framework.

18. The electronic device of claim 17, wherein the refractive layer comprises a first layer, a second layer, and a third layer.

19. The electronic device of claim 17, wherein the antireflective film has a reflectivity of less than 1%.

20. The electronic device of claim 17, wherein the hard coating has a refractive index of 1.55 to 1.8.

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