Protective film, display device including the same, and method of manufacturing the protective film

Abstract

The present application relates to a protective film having low reflectivity and crack resistance, a display device including the protective film, and a method of manufacturing the protective film. The protective film includes a base layer, a hard coating layer disposed on the base layer, and a low refractive index layer disposed on the hard coating layer and containing dodecafluoroheptyl acrylate (DFHA).

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application is based on and claims the benefit of priority from Korean Patent Application No. 10-2023-0144169 filed in the Korean Intellectual Property Office on October 25, 2023, the disclosure of which is incorporated herein by reference in its entirety. Technical Field

[0003] The present disclosure relates to a protective film, a display device including the protective film, and a method for manufacturing the protective film. More specifically, the present disclosure relates to a protective film having low reflectivity and being resistant to cracking, a display device including the protective film, and a method for manufacturing the protective film. Background Art

[0004] The display device displays an image by receiving information about the image. The display device is used as a display part of a compact product such as a mobile phone, or as a display part of a large product such as a television.

[0005] The display device includes a plurality of pixels that emit light by receiving an electrical signal to display an image to the outside. Each pixel includes a light-emitting element, and for an organic light-emitting display device, an organic light-emitting diode is included as a light-emitting element. In a general organic light-emitting display device, a thin film transistor and an organic light-emitting diode are formed on a substrate, and the organic light-emitting diode emits light.

[0006] Such a display device is susceptible to external impact, and therefore, the display device may include a protective film for protecting a display surface from external impact. However, when the protective film is attached to the flexible display device, cracks may occur in the protective film in the folding area. Summary of the invention

[0007] One or more embodiments include a protective film having low reflectivity and being resistant to cracking, a display device including the protective film, and a method of manufacturing the protective film. However, such objects are examples, and the scope of the present disclosure is not limited thereto.

[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, a protective film includes a base layer, a hard coating layer disposed on the base layer, and a low refractive index layer disposed on the hard coating layer and including dodecafluoroheptyl acrylate (DFHA).

[0010] In an embodiment, the low refractive index layer includes a polymer compound composed of DFHA, and a degree of polymerization of the polymer compound may be any one of 6 to 12.

[0011] In an embodiment, the low refractive index layer includes a polymer compound composed of DFHA, and the degree of polymerization of the polymer compound may be 8.

[0012] In an embodiment, the low refractive index layer may include only DFHA.

[0013] In an embodiment, the low refractive index layer may have a thickness of about 70 nm to about 130 nm.

[0014] In an embodiment, the fluorine content of the low refractive index layer may be about 45 wt % to about 80 wt %.

[0015] In an embodiment, the infrared spectrum of the low refractive index layer may include two -CF 2 Peak and three-CF 3 peak.

[0016] In an embodiment, -CF 2 A peak may be included at about 1150 cm -1 About 1160cm -1 The first peak frequency in the range of about 1210 cm -1 To about 1220cm -1 The second peak frequency in the range.

[0017] In an embodiment, -CF 3 The peak may have a peak at about 975 cm -1 About 1280cm -1 Three peak frequencies within the range.

[0018] According to one or more embodiments, a display device includes a display module foldable relative to at least one folding axis and a protective film disposed on the display module, wherein the protective film includes a base layer, a hard coating layer disposed on the base layer, and a low refractive index layer disposed on the hard coating layer and including DFHA.

[0019] In an embodiment, the low refractive index layer includes a polymer compound composed of DFHA, and a degree of polymerization of the polymer compound may be any one of 6 to 12.

[0020] In an embodiment, the low refractive index layer includes a polymer compound composed of DFHA, and the degree of polymerization of the polymer compound may be 8.

[0021] In an embodiment, the low refractive index layer may include only DFHA.

[0022] In an embodiment, the low refractive index layer may have a thickness of about 70 nm to about 130 nm.

[0023] In an embodiment, the fluorine content of the low refractive index layer may be about 45 wt % to about 80 wt %.

[0024] In an embodiment, the infrared spectrum of the low refractive index layer may include two -CF 2 Peak and three-CF 3 peak.

[0025] In an embodiment, -CF 2 A peak may be included at about 1150 cm -1 About 1160cm -1 The first peak frequency in the range of about 1210 cm -1 To about 1220cm -1 The second peak frequency in the range.

[0026] In an embodiment, -CF 3 The peak may have a peak at about 975 cm -1 About 1280cm -1 Three peak frequencies within the range.

[0027] According to one or more embodiments, a method of manufacturing a protective film includes forming a base layer on a substrate, forming a hard coating layer on the base layer, and performing a vacuum deposition polymerization process to form a low refractive index layer including DFHA on the hard coating layer.

[0028] In an embodiment, the method may further include performing an ultraviolet (UV) ozone treatment process on an upper surface of the hard coating layer before performing the vacuum deposition polymerization process. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] The above and other aspects, features and advantages of certain embodiments of the present disclosure will become more apparent from the following description taken in conjunction with the accompanying drawings, in which:

[0030] Figure 1 is a schematic plan view of a display panel of a display device according to an embodiment;

[0031] Figure 2 for Figure 1 A schematic perspective view of a display device in a folded state;

[0032] Figure 3 is a schematic perspective view of a display panel of a display device according to another embodiment;

[0033] Figure 4 For along Figure 1 A schematic cross-sectional view of a pixel taken along line II';

[0034] Figure 5 for Figure 1 A schematic exploded perspective view of a display module, a cover member, and a protective film of a display device of FIG.

[0035] Figure 6For illustrative purposes Figure 5 A conceptual diagram of the stacked structure of the protective film;

[0036] Figure 7 To show Figure 6 A graph showing the result data of RAS-IR analysis of the low refractive index layer;

[0037] Figure 8 A flowchart schematically showing a method for manufacturing a protective film according to an embodiment; and

[0038] Fig. 9 For Figure 8 A conceptual diagram of the process used in the manufacturing method. DETAILED DESCRIPTION

[0039] Reference will now be made in detail to embodiments, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to like elements throughout. In this regard, the embodiments may have different forms and should not be construed as being limited to the description set forth herein. Accordingly, embodiments are described below simply by reference to the figures to explain aspects of the description. As used herein, the term "and / or" includes any and all combinations of one or more associated enumerated items. Throughout this disclosure, the expression "at least one of a, b, and c" indicates only a, only b, only c, both a and b, both a and c, both b and c, all a, b, and c, or variations thereof.

[0040] Various modifications may be applied to this embodiment, and specific embodiments will be illustrated in the drawings and described in the detailed description section. The effects and features of this embodiment and methods for achieving the effects and features will become clearer with reference to the detailed description below in conjunction with the drawings. However, this embodiment can be implemented in various forms and is not limited to the embodiments presented below.

[0041] Hereinafter, the embodiments will be described in detail with reference to the accompanying drawings, and in the description with reference to the drawings, the same or corresponding components will be denoted by the same reference numerals, and repeated descriptions thereof will be omitted.

[0042] In the following embodiments, it will be understood that although the terms "first", "second", etc. may be used herein to describe various elements, these elements should not be limited to the specific order of these terms. These elements are only used to distinguish one element from another element. In addition, in the following embodiments, as used herein, the singular forms "a", "an", and "the" are intended to also include plural forms, unless the context clearly indicates otherwise.

[0043] It will be understood that when a component such as a layer, film, region or panel is referred to as being “on” another component such as a layer, film, region or panel, the component can be directly on the other component such as a layer, film, region or panel or intervening components may be present thereon.

[0044] For convenience of explanation, the size of the components in the drawings may be exaggerated. For example, because the size (eg, thickness) of the elements in the drawings is arbitrarily explained for convenience of explanation, the following embodiments are not limited thereto.

[0045] In the following embodiments, it will be further understood that the terms “comprises” and / or “comprising” used herein indicate the presence of stated features or elements, but do not preclude the presence or addition of one or more other features or elements.

[0046] In the following embodiments, it will be understood that when an element (such as a layer, film, region or panel) is referred to as being "on" another element (such as a layer, film, region or panel), the element may be directly on the other element (such as a layer, film, region or panel) or intervening elements may be present thereon.

[0047] When a certain embodiment can be implemented differently, a specific process order can be performed differently from the described order. For example, two processes described in succession can be performed substantially simultaneously or in the reverse order of the described order.

[0048] In the specification, a statement such as "A and / or B" may include A, B, or A and B. A statement such as "at least one of A and B" may include A, B, or A and B.

[0049] In the following embodiments, it will be understood that when a layer, region, or component is referred to as being "connected to" another layer, region, or component, it may be directly connected to the other layer, region, or component or indirectly connected to the other layer, region, or component via an intervening layer, region, or component. For example, in the specification, when a layer, region, or component is referred to as being electrically connected to another layer, region, or component, it may be directly electrically connected to the other layer, region, or component or indirectly electrically connected to the other layer, region, or component via an intervening layer, region, or component.

[0050] In the following embodiments, the x-direction, the y-direction, and the z-direction are not limited to the directions corresponding to the three axes of the rectangular coordinate system, and can be interpreted in a broader sense. For example, the x-direction, the y-direction, and the z-direction may be perpendicular to each other, or may represent different directions that are not perpendicular to each other. The -x-direction, the -y-direction, and the -z-direction may represent the direction opposite to the x-direction, the direction opposite to the y-direction, and the direction opposite to the z-direction, respectively.

[0051] Hereinafter, a protective film, a display device including the protective film, and a method of manufacturing the protective film according to an embodiment based on the above contents will be described in detail as follows.

[0052] Figure 1 is a schematic plan view of a display panel 10 of a display device according to an embodiment, and Figure 2 for Figure 1 A schematic perspective view of a display device in a folded state.

[0053] like Figure 1 As explained in the foregoing, a display device according to an embodiment may include a display panel 10. Such a display device may be any device including the display panel 10. For example, the display device may include various devices such as a smart phone, a tablet computer, a laptop computer, a television, or a billboard, etc. A display device according to an embodiment may include a thin film transistor and a capacitor, etc., which may be implemented by a conductive layer and an insulating layer.

[0054] like Figure 1 As explained in FIG. 1 , the display panel 10 may include a display area DA and a peripheral area PA located outside the display area DA. Figure 1 In the embodiment, the display area DA is illustrated as having a rectangular shape. However, the present disclosure is not limited thereto. The display area DA may have various shapes, such as a circle, an ellipse, other polygons, and a specific figure.

[0055] The display area DA is a portion for displaying an image, and a plurality of pixels PX may be arranged therein. Each pixel PX may include a display element, such as an organic light emitting diode. Each pixel PX may emit, for example, red light, green light, or blue light. The pixel PX may be connected to a pixel circuit including a thin film transistor (TFT) and a storage capacitor, etc. The pixel circuit may be connected to a scan line SL for transmitting a scan signal, a data line DL that crosses the scan line SL and transmits a data signal, and a drive voltage line PL for supplying a drive voltage, etc. The scan line SL may extend in the y direction, and the data line DL and the drive voltage line PL may extend in the x direction.

[0056] The pixel PX may emit light having a brightness corresponding to an electrical signal from a pixel circuit electrically connected to the pixel PX. The display area DA may display a predetermined image by light emitted from the pixel PX. For reference, as described above, the pixel PX may be defined as an emission area that emits any one of red light, green light, and blue light.

[0057] The peripheral area PA, which is an area where the pixels PX are not arranged, may be an area where no image is displayed. A power line for driving the pixels PX may be located in the peripheral area PA. In addition, a plurality of pads may be arranged in the peripheral area PA, and a printed circuit board or an integrated circuit element (such as a driver IC) including a driving circuit portion may be arranged to be electrically connected to the pads.

[0058] For reference, since the display panel 10 includes a substrate 100 (see Figure 4 ), so it can be said that the substrate 100 includes a display area DA and a peripheral area PA. The substrate 100 (see FIG. Figure 4 ).

[0059] In addition, a plurality of transistors may be arranged in the display area DA. In the transistor, depending on the type of the transistor (N-type or P-type) and / or its operating conditions, the first terminal of the transistor may be a source electrode or a drain electrode, and the second terminal thereof may be an electrode different from the first terminal. For example, when the first terminal is a source electrode, the second terminal may be a drain electrode.

[0060] The transistors may include a driving transistor, a data writing transistor, a compensation transistor, an initialization transistor, an emission control transistor, etc. The driving transistor may be connected between the driving voltage line PL and the organic light emitting diode, and the data writing transistor may be connected between the data line DL and the driving transistor and may perform a switching operation to transmit a data signal transmitted through the data line DL.

[0061] The compensation transistor may be turned on in response to a scan signal received through the scan line SL to connect the driving transistor to the organic light emitting diode, thereby compensating for a threshold voltage of the driving transistor.

[0062] The initialization transistor may be turned on in response to a scan signal received through the scan line SL to transmit an initialization voltage to the gate electrode of the driving transistor, thereby initializing the gate electrode of the driving transistor. The scan line connected to the initialization transistor may be a different scan line from the scan line connected to the compensation transistor.

[0063] The emission control transistor may be turned on in response to an emission control signal received through the emission control line, and as a result, a driving current may flow to the organic light emitting diode.

[0064] The organic light emitting diode may include a pixel electrode (anode) and a counter electrode (cathode), and the counter electrode (cathode) may receive a second power supply voltage (ELVSS). The organic light emitting diode may display an image by receiving a driving current from a driving transistor and emitting light.

[0065] As in Figure 1 and Figure 2As explained in the , the display panel 10 according to the embodiment may include at least one folding area (FAi) and a plurality of non-folding areas (NFAj), where "i" and "j" are integers. For example, the display panel 10 may include a first folding area FA1 and a second folding area FA2, and the display panel 10 may also include a first non-folding area NFA1, a second non-folding area NFA2, and a third non-folding area NFA3.

[0066] For example, the first folding area FA1 as a part of the display panel 10 may be bent or folded relative to a first folding axis. The first folding axis may be a virtual axis extending in the x-direction. The first folding area FA1 may have a folded state and an unfolded state. The folded state may refer to a state in which the first folding area FA1 is folded relative to the first folding axis, and the unfolded state may refer to a state in which the first folding area FA1 is not folded and is flat.

[0067] For example, the second folding area FA2 as a part of the display panel 10 may be bent or folded relative to the second folding axis. The second folding axis, as a virtual axis extending in the x-direction, may be parallel to the first folding axis and spaced apart from the first folding axis. The second folding area FA2 may have a folded state and an unfolded state. The folded state may refer to a state in which the second folding area FA2 is folded relative to the second folding axis, and the unfolded state may refer to a state in which the second folding area FA2 is not folded and is flat.

[0068] For example, the first folding area FA1 in the unfolded state may be arranged between the first non-folding area NFA1 and the second non-folding area NFA2. The second folding area FA2 in the unfolded state may be arranged between the second non-folding area NFA2 and the third non-folding area NFA3. The second non-folding area NFA2 in the unfolded state may be arranged between the first folding area FA1 and the second folding area FA2.

[0069] For example, the first folding area FA1 is folded in a different (e.g., opposite) direction from the second folding area FA2. For example, when the first folding area FA1 is in a folded state, the rear side of the first non-folding area NFA1 and the rear side of the second non-folding area NFA2 may face each other. When the second folding area FA2 is in a folded state, the front side of the second non-folding area NFA2 and the front side of the third non-folding area NFA3 may face each other.

[0070] However, as described above, the direction in which the first folding area FA1 is folded and the direction in which the second folding area FA2 is folded are merely examples. Figure 2 In addition to or in lieu of the examples depicted Figure 2 As shown in the example depicted in FIG. 1 , the display panel 10 can also be folded in various directions.

[0071] In the following description, an organic light-emitting display device is described as an example of a display device according to an embodiment, and the display device according to the embodiment is not limited thereto. In another embodiment, the display device according to the embodiment may include a display device such as an inorganic light-emitting display device (or an inorganic EL display device) or a quantum dot light-emitting display device. For example, the emission layer of the display element in the display device may include an organic material or an inorganic material. In addition, the display device may include an emission layer and quantum dots located on the path of light emitted from the emission layer.

[0072] Figure 3 is a schematic perspective view of a display panel 10 of a display device according to another embodiment.

[0073] For reference, it can be omitted Figure 3 With the above Figure 1 and Figure 2 Same or duplicate descriptions between.

[0074] like Figure 3 As explained in the above, the display panel 10 of the display device according to the present embodiment may include: Figure 1 and Figure 2 The display area DA and the peripheral area PA in the display panel 10.

[0075] The display panel 10 may include a folding region and a non-folding region extending from the opposite side of the folding region. For example, in the non-folding state, the folding region may be arranged between the non-folding regions. Although not explicitly shown in the figure, when the folding regions are in the "folded state", the front sides of the non-folding regions may face each other, or the rear sides of the non-folding regions may face each other.

[0076] Although not explicitly shown, Figure 3 The display area DA may include Figure 1 The pixel structure is the same as the pixel structure, and for convenience, the above presentation Figure 1 The pixel structure of the illustration and description is used for Figure 3 Explanation and description of the pixel structure.

[0077] Figure 4 For along Figure 1 Schematic cross-sectional view of a pixel taken along line II'.

[0078] For reference, it can be omitted Figure 4 With the above Figures 1 to 3 Same or duplicate descriptions between.

[0079] As described above, the substrate 100 may include an area corresponding to the display area DA and a peripheral area PA outside the display area DA. The substrate 100 may include various materials having flexible or bendable properties. For example, the substrate 100 may include glass, metal, or a polymer resin. In addition, the substrate 100 may include a polymer resin such as polyethersulfone, polyacrylate, polyetherimide, polyethylene naphthalate, polyethylene terephthalate, polyphenylene sulfide, polyarylate, polyimide, polycarbonate, or cellulose acetate propionate. The substrate 100 may be modified in various ways, such as being modified to have a multilayer structure including two layers (each layer including a polymer resin as described above) and an isolation layer including an inorganic material (silicon oxide, silicon nitride, silicon oxynitride, etc.) provided between the two layers.

[0080] The buffer layer 201 may be disposed on the substrate 100. The buffer layer 201 may prevent diffusion of impurity ions, prevent penetration of moisture or external air, and serve as an isolation layer and / or barrier layer for surface planarization. The buffer layer 201 may include silicon oxide, silicon nitride, or silicon oxynitride. In addition, the buffer layer 201 may adjust a heat supply speed during a crystallization process for forming the first semiconductor layer 210 so that the first semiconductor layer 210 is uniformly crystallized.

[0081] The first semiconductor layer 210 may be disposed on the buffer layer 201. The first semiconductor layer 210 may include polycrystalline silicon, and may include a channel region in which impurities are not doped, and a source region and a drain region arranged on opposite sides of the channel region and in which impurities are doped. The impurities are different from each other depending on the type of the thin film transistor, and may include N-type impurities or P-type impurities.

[0082] The first gate insulating film 202 may be disposed on the first semiconductor layer 210. The first gate insulating film 202 may be provided to ensure insulation between the first semiconductor layer 210 and the first gate layer 220 to be described below. The first gate insulating film 202 may include an inorganic material, such as silicon oxide, silicon nitride and / or silicon oxynitride, etc., and may be provided between the first semiconductor layer 210 and the first gate layer 220 to be described below. In addition, the first gate insulating film 202 may be formed to correspond to the entire surface of the substrate 100, and may have a structure in which a contact hole is formed in a preset portion. As such, an insulating film including an inorganic material may be formed by chemical vapor deposition (CVD) or atomic layer deposition (ALD). This is the same as the embodiment described below and its variations.

[0083] The first gate layer 220 may be disposed on the first gate insulating film 202. The first gate layer 220 may be located at a position vertically overlapping the first semiconductor layer 210, and may include at least one metal of molybdenum (Mo), aluminum (Al), platinum (Pt), palladium (Pd), silver (Ag), magnesium (Mg), gold (Au), nickel (Ni), neodymium (Nd), iridium (Ir), chromium (Cr), lithium (Li), calcium (Ca), titanium (Ti), tungsten (W), and copper (Cu).

[0084] The first interlayer insulating film 203 may be disposed on the first gate layer 220. The first interlayer insulating film 203 may cover the first gate layer 220. The first interlayer insulating film 203 may include an inorganic material. For example, the first interlayer insulating film 203 may include a metal oxide or a metal nitride, and specifically, the inorganic material may include silicon oxide SiO x 、Silicon Nitride SiN y , silicon oxynitride SiON, aluminum oxide Al 2 O 3 , titanium oxide TiO 2 , Tantalum oxide Ta 2 O 5 、HfO 2 or zinc oxide (ZnO x , which may be ZnO and / or ZnO 2 ) etc. In some embodiments, the first interlayer insulating film 203 may include SiO x / SiN y or SiN x / SiO y The dual structure.

[0085] The second gate layer 230 may be disposed on the first interlayer insulating film 203. In some cases, the second gate layer 230 may be omitted. The second gate layer 230 may be located at a position vertically overlapping with the first gate layer 220.

[0086] The second gate layer 230 may include at least one metal of Mo, Al, Pt, Pd, Ag, Mg, Au, Ni, Nd, Ir, Cr, Li, Ca, Ti, W, and Cu.

[0087] In some cases, second gate layer 230 and first gate layer 220 may form a storage capacitor. First gate layer 220 may include a first electrode of the storage capacitor, and second gate layer 230 may include a second electrode of the storage capacitor.

[0088] The second interlayer insulating film 204 may be disposed on the second gate layer 230. The second interlayer insulating film 204 may cover the second gate layer 230. The second interlayer insulating film 204 may include an inorganic material. For example, the second interlayer insulating film 204 may include a metal oxide or a metal nitride, and specifically, the inorganic material may include silicon oxide SiO x 、Silicon Nitride SiN y , silicon oxynitride SiON, aluminum oxide Al 2 O 3 , titanium oxide TiO 2 , Tantalum oxide Ta 2 O 5 、HfO 2 or zinc oxide (ZnO x , which may be ZnO and / or ZnO 2 ) etc. In some embodiments, the second interlayer insulating film 204 may include SiO x / SiN y or SiN x / SiO y The dual structure.

[0089] The second semiconductor layer 240 may be disposed on the second interlayer insulating film 204. The second semiconductor layer 240 may include polysilicon or silicon oxide. The second semiconductor layer 240 may include a channel region in which impurities are not doped, and a source region and a drain region arranged on opposite sides of the channel region and in which impurities are doped. The impurities are different from each other depending on the type of the thin film transistor, and may include N-type impurities or P-type impurities.

[0090] The second gate insulating film 205 may be disposed on the second semiconductor layer 240. The second gate insulating film 205 may be provided to ensure insulation between the second semiconductor layer 240 and the third gate layer 250 to be described below. The second gate insulating film 205 may include an inorganic material, such as silicon oxide, silicon nitride and / or silicon oxynitride, etc., and may be provided between the second semiconductor layer 240 and the third gate layer 250 to be described below. In addition, the second gate insulating film 205 may be formed to correspond to the entire surface of the substrate 100, and may have a structure in which a contact hole is formed in a preset portion. As such, an insulating film including an inorganic material may be formed by CVD or ALD. This is the same as the embodiment described below and its variations.

[0091] The third gate layer 250 may be disposed on the second gate insulating film 205. The third gate layer 250 may be disposed at a position vertically overlapping the second semiconductor layer 240, and may include at least one metal of Mo, Al, Pt, Pd, Ag, Mg, Au, Ni, Nd, Ir, Cr, Li, Ca, Ti, W, and Cu.

[0092] The third interlayer insulating film 206 may be disposed on the third gate layer 250. The third interlayer insulating film 206 may cover the third gate layer 250. The third interlayer insulating film 206 may include an inorganic material. For example, the third interlayer insulating film 206 may include a metal oxide or a metal nitride, and specifically, the inorganic material may include silicon oxide SiO x 、Silicon Nitride SiN y , silicon oxynitride SiON, aluminum oxide Al 2 O 3 , titanium oxide TiO 2 , Tantalum oxide Ta 2 O 5 、HfO 2 or zinc oxide (ZnO x , which may be ZnO and / or ZnO 2 ) etc. In some embodiments, the third interlayer insulating film 206 may include SiO x / SiN y or SiN x / SiO y The dual structure.

[0093] The fourth gate layer 260 may be disposed on the third interlayer insulating film 206. In some cases, the fourth gate layer 260 may be omitted.

[0094] The fourth gate layer 260 may be located at a position vertically overlapping the third gate layer 250 and may include at least one metal of Mo, Al, Pt, Pd, Ag, Mg, Au, Ni, Nd, Ir, Cr, Li, Ca, Ti, W, and Cu.

[0095] In some cases, fourth gate layer 260 and third gate layer 250 may form a storage capacitor.Fourth gate layer 260 may include a first electrode of the storage capacitor, and third gate layer 250 may include a second electrode of the storage capacitor.

[0096] The fourth interlayer insulating film 207 may be disposed on the fourth gate layer 260. The fourth interlayer insulating film 207 may cover the fourth gate layer 260. The fourth interlayer insulating film 207 may include an inorganic material. For example, the fourth interlayer insulating film 207 may include a metal oxide or a metal nitride, and specifically, the inorganic material may include silicon oxide SiO x 、Silicon Nitride SiN y , silicon oxynitride SiON, aluminum oxide Al 2 O 3 , titanium oxide TiO 2 , Tantalum oxide Ta 2 O 5 、HfO 2 or zinc oxide (ZnO x, which may be ZnO and / or ZnO 2 ) etc. In some embodiments, the fourth interlayer insulating film 207 may include SiO x / SiN y or SiN x / SiO y The dual structure.

[0097] The first conductive layer 270 may be disposed on the fourth interlayer insulating film 207. The first conductive layer 270 may serve as an electrode connected to the source / drain regions of the first semiconductor layer 210 through a via penetrating the fourth interlayer insulating film 207 to the first gate insulating film 202.

[0098] The first conductive layer 270 may function as an electrode connected to the source / drain region of the second semiconductor layer 240 through a via hole penetrating the fourth interlayer insulating film 207 to the second gate insulating film 205 .

[0099] The first conductive layer 270 may include one or more metals selected from Al, Pt, Pd, Ag, Mg, Au, Ni, Nd, Ir, Cr, Li, Ca, Mo, Ti, W, and Cu. For example, the first conductive layer 270 may include a Ti layer, an Al layer, and / or a Cu layer.

[0100] The first conductive layer 270 may form at least a portion of a data line or wiring to be described below.

[0101] The first organic insulating layer 208a may be disposed on the first conductive layer 270. The first organic insulating layer 208a may cover the first conductive layer 270 and substantially have a flat upper surface, and may be an organic insulating layer used as a planarization film. The first organic insulating layer 208a may include an organic material such as acrylic acid, benzocyclobutene (BCB), or hexamethyldisiloxane (HMDSO), etc. The first organic insulating layer 208a may be variously modified, such as a single layer or a multilayer, etc.

[0102] The second conductive layer 280 may be disposed on the first organic insulating layer 208a. The second conductive layer 280 may be used as an electrode that passes through a through hole in the first organic insulating layer 208a to connect to a source region / drain region of the first semiconductor layer 210. The second conductive layer 280 may include one or more metals selected from Al, Pt, Pd, Ag, Mg, Au, Ni, Nd, Ir, Cr, Li, Ca, Mo, Ti, W, and Cu. For example, the second conductive layer 280 may include a Ti layer, an Al layer, and / or a Cu layer.

[0103] The first conductive layer 270 and the second conductive layer 280 may form at least a portion of a data line or wiring to be described below.

[0104] The second organic insulating layer 208b may be disposed on the second conductive layer 280. The second organic insulating layer 208b may cover the second conductive layer 280 and have a substantially flat upper surface, and may be an organic insulating layer used as a planarization film. The second organic insulating layer 208b may include an organic material such as acrylic acid, BCB, or HMDSO. The second organic insulating layer 208b may be variously modified, such as a single layer or a multilayer, etc.

[0105] In addition, despite Figure 4 Although not illustrated in the drawings, an additional conductive layer and an additional insulating layer may be provided between the second conductive layer 280 and the pixel electrode 290, and various embodiments thereof are available. In this state, the additional conductive layer may include the same material as that of the above-mentioned conductive layer and may have the same layer structure. The additional insulating layer may include the same material as that of the above-mentioned organic insulating layer and may have the same layer structure.

[0106] The pixel electrode 290 may be disposed on the second organic insulating layer 208b. The pixel electrode 290 may be connected to the second conductive layer 280 through a contact hole formed in the second organic insulating layer 208b. A display element may be disposed on the pixel electrode 290. An organic light emitting diode (OLED) may be used as a display element. In other words, the organic light emitting diode (OLED) may be provided on, for example, the pixel electrode 290. The pixel electrode 290 may include a light-transmitting conductive oxide (such as ITO, In 2 O 3 The pixel electrode 290 may include a light-transmitting conductive layer including ITO or IZO and a reflective layer including a metal such as Al or Ag. For example, the pixel electrode 290 may have a three-layer structure of ITO / Ag / ITO.

[0107] The pixel defining layer 209 may be disposed on the second organic insulating layer 208b to cover the edge of the pixel electrode 290. In other words, the pixel defining layer 209 may cover the edge of the pixel electrode 290. The pixel defining layer 209 may have a shape corresponding to the pixel PX (see Figure 1 ), and the opening portion may be formed so that at least a central portion of the pixel electrode 290 is exposed. The pixel defining layer 209 may include an organic material such as polyimide or HMDSO.

[0108] The intermediate layer 295 and the counter electrode 296 may be located in the opening portion of the pixel defining layer 209. The intermediate layer 295 may include a low molecular weight material or a polymer material, and when including a low molecular weight material, the intermediate layer 295 may include a hole injection layer, a hole transport layer, an emission layer, an electron transport layer and / or an electron injection layer, etc. When including a polymer material, the intermediate layer 295 may have a structure including a hole transport layer and an emission layer.

[0109] The counter electrode 296 may include a light-transmitting conductive oxide (such as ITO, In 2 O 3 The pixel electrode 290 serves as an anode, and the counter electrode 296 serves as a cathode. The electrodes may have opposite polarities.

[0110] The structure of the intermediate layer 295 is not limited to the structure of the examples explicitly shown in the present disclosure, and may have various structures. For example, at least any one of the layers constituting the intermediate layer 295 may be formed integrally with the counter electrode 296. In another embodiment, the intermediate layer 295 may include a layer patterned to correspond to the pixel electrode 290.

[0111] The counter electrode 296 may be arranged in the display area DA (see Figure 1 ) to cover the display area DA (see Figure 1 ) of the entire surface. In other words, the counter electrode 296 may be integrally formed to cover a plurality of pixels PX (see Figure 1 The counter electrode 296 may be electrically connected to the peripheral area PA (see Figure 1 ) in a common power line (not shown). In an implementation, the counter electrode 296 may extend to a partition wall (not shown).

[0112] The cover member 300 may cover the entire display area DA (see FIG. Figure 1 ), and towards the peripheral area PA (see Figure 1 ) extends to cover the peripheral area PA (see Figure 1 ). The cover member 300 may be a thin film encapsulation layer or a layer formed of a rigid member (eg, glass, etc.).

[0113] When the cover member 300 is a thin film encapsulation layer, the thin film encapsulation layer may include a first inorganic encapsulation layer (not shown), a second inorganic encapsulation layer (not shown) and an organic encapsulation layer (not shown) therebetween. The first inorganic encapsulation layer and the second inorganic encapsulation layer may each include one or more inorganic materials, such as aluminum oxide, titanium oxide, tantalum oxide, hafnium oxide, zinc oxide, silicon oxide, silicon nitride, silicon oxynitride, and the like.

[0114] The first inorganic encapsulation layer and the second inorganic encapsulation layer may each be a single layer or a multilayer including the above-mentioned material. The first inorganic encapsulation layer and the second inorganic encapsulation layer may each include the same material or different materials. The thicknesses of the first inorganic encapsulation layer and the second inorganic encapsulation layer may be different from each other. The thickness of the first inorganic encapsulation layer may be greater than the thickness of the second inorganic encapsulation layer. Optionally, the thickness of the second inorganic encapsulation layer may be greater than the thickness of the first inorganic encapsulation layer, or the thicknesses of the first inorganic encapsulation layer and the second inorganic encapsulation layer may be the same as each other.

[0115] The organic encapsulation layer may include a monomer material or a polymer material. The polymer material may include acrylic resin, epoxy resin, polyimide or polyethylene, etc. In an embodiment, the organic encapsulation layer may include acrylate.

[0116] like Figure 4 As explained in the figure, a first-1 thin film transistor TFT1-1 and a first-2 thin film transistor TFT1-2 for realizing a pixel circuit in the display area DA may be arranged. The first-1 thin film transistor TFT1-1 may refer to a transistor structure mainly configured by the first semiconductor layer 210, and the first-2 thin film transistor TFT1-2 may refer to a transistor structure mainly configured by the second semiconductor layer 240.

[0117] Figure 5 for Figure 1 1 is a schematic exploded perspective view of a display module 200 , a cover member 300 , and a protective film 400 of a display panel 10 . Figure 6 For illustrative purposes Figure 5 A conceptual diagram of a stacked structure of a protective film 400.

[0118] For reference, it can be omitted Figure 5 and Figure 6 With the above Figures 1 to 4 Same or duplicate descriptions between.

[0119] like Figure 5 As explained in FIG. 1 , the display module 200 may include a display area DA and a peripheral area PA. The cover member 300 may be disposed on the display module 200. The protective film 400 may be disposed on the cover member 300.

[0120] like Figure 6 As explained in FIG. 4 , the protective film 400 may include a base layer 410, a hard coating layer 420, and a low refractive index layer 430. The protective film 400 is transparent, and even when the protective film 400 is provided as described above, image information displayed in the display area DA may be observed through the protective film 400.

[0121] The base layer 410 may be disposed on Figure 5 For example, the base layer 410 may be disposed on the cover member 300. Figure 4 and Figure 5 The display module 200 of the substrate 410 is provided on the substrate 410. The substrate 410 may be formed of an optically transparent and flexible resin. The resin may include at least one type of polyimide resin and polyamide-imide resin. The polyimide resin and the polyamide-imide resin may each be manufactured by a typical method well known to those skilled in the art. The substrate 410 may support the protective film 400 to increase the mechanical strength of the protective film 400.

[0122] For example, the base layer 410 may be a single-layer film. However, in some cases, the base layer 410 may have a stacked structure in which two resin films of the same type or different types are stacked on top of each other and attached with an adhesive layer (e.g., a pressure-sensitive adhesive layer) interposed therebetween.

[0123] The hard coating layer 420 may be disposed on the base layer 410. The hard coating layer 420 may include a composition for the hard coating layer 420, the composition including at least one type of acrylic resin and a solvent. The composition for the hard coating layer 420 may further include at least one type of a cross-linking agent and an initiator. For example, the hard coating layer 420 may have a low refractive index compared to the base layer 410. For example, the lower surface of the hard coating layer 420 may be in direct contact with the upper surface of the base layer 410.

[0124] The low refractive index layer 430 may be disposed on the hard coating layer 420. For example, a lower surface of the low refractive index layer 430 may be in direct contact with an upper surface of the hard coating layer 420. For example, the low refractive index layer 430 may include a monomer.

[0125] The low refractive index layer 430 may include dodecafluoroheptyl acrylate (C 10 H 6 F 12 O 2 , hereinafter "DFHA"). For example, the low refractive index layer 430 may include only DFHA. The low refractive index layer 430 including only DFHA may have the effect of allowing desired physical properties according to film forming conditions.

[0126] [Formula 1]

[0127]

[0128] For example, n of DFHA may be any one of 6, 8, 10, and 12. For example, n of DFHA may be about 6 to about 12. When n of DFHA is less than 6, it may have an adverse effect on the strength of the protective film 400 or the low refractive index layer 430, and when n of DFHA is greater than 12, it may have an adverse effect on the deposition efficiency in the vacuum deposition polymerization process. In particular, the low refractive index layer 430 may include a monomer in which n of DFHA is 8.

[0129] In this specification, n of DFHA is defined as the degree of polymerization. The term "degree of polymerization" refers to the number of repeating units or monomer units constituting a polymer. The degree of polymerization may be described as n. For example, the low refractive index layer 430 may include a polymer compound composed of DFHA, and the degree of polymerization of the polymer compound may be any one of 6, 8, 10, and 12. For example, the low refractive index layer 430 may include a polymer compound composed of DFHA, and the degree of polymerization of the polymer compound may be 8.

[0130] For example, the low refractive index layer 430 may have a thickness of about 70 nm to about 130 nm, for example, about 90 nm to about 100 nm.

[0131] When the thickness of the low refractive index layer 430 is less than 70 nm, the wear resistance and hardness of the protective film 400 may be adversely affected, and when the thickness of the low refractive index layer 430 is greater than 130 nm, the transparency of the protective film 400 may be adversely affected. In addition, when the thickness of the low refractive index layer 430 is about 90 nm to about 100 nm, the protective film 400 may have sufficient transparency while having sufficient wear resistance and hardness.

[0132] For example, the base layer 410 may have a thickness of about 50 μm to about 150 μm. The base layer 410 may have a thickness greater than that of the low refractive index layer 430 and that of the hard coating layer 420 .

[0133] For example, the hard coating layer 420 may have a thickness of about 1 μm to about 25 μm. The hard coating layer 420 may have a thickness greater than that of the low refractive index layer 430 and less than that of the base layer 410 .

[0134] The thickness of the base layer 410 may be the largest among the layers constituting the protective film 400, and the thickness of the hard coating layer 420 may be greater than that of the low refractive index layer 430. Since the thickness of the hard coating layer 420 is greater than that of the low refractive index layer 430, the overall hardness of the protective film 400 may be improved.

[0135] For example, the fluorine content of the low refractive index layer 430 may be about 45 wt % to about 80 wt %. When the fluorine content of the low refractive index layer 430 is less than 45 wt % or greater than 80 wt %, reflectivity and contact angle (especially initial contact angle) may be adversely affected.

[0136] In the present specification, the term “contact angle (°)” may be defined as an angle formed between a liquid-gas interface and a liquid-solid interface when a liquid droplet is located on a solid surface.

[0137] Figure 7 To show Figure 6 FIG. 4 is a graph showing result data of RAS-IR analysis of the low refractive index layer 430. FIG.

[0138] For reference, it can be omitted Figure 7 With the above Figures 1 to 6 Same or duplicate descriptions between.

[0139] like Figure 7 As explained in Figure 6 The result data of the RAS-IR analysis of the low refractive index layer 430 may be an infrared spectrum of the low refractive index layer 430 .

[0140] exist Figure 7 In the graph, the horizontal axis represents the wave number (cm -1 ), and the vertical axis represents a normalized size in which the maximum value may be 1. Since the graph shows the normalized size, for convenience of explanation, Figure 7 The vertical axis can be omitted.

[0141] For example, the infrared spectrum of the low refractive index layer 430 may include two -CF 2 Peak and three-CF 3 Peak. -CF 2 The peak may have a peak at about 1150 cm -1 About 1160cm -1 A peak frequency in the range of 1210 cm -1 To about 1220cm -1 A peak frequency within the range. -CF 3 The peak may have a peak at about 975 cm -1 To about 1280cm -1 The three peak frequencies within the range, and specifically, -CF 3 The peak is about 981 cm -1 、About 1159cm -1 and about 1278cm -1 The peak frequency.

[0142] Table 1 below shows double-sided reflectivity (%) and crack strain (%) for each thickness of the low refractive index layer 430 including a monomer in which n of DFHA is 8.

[0143] [Table 1]

[0144]

[0145] “-” means “data not measured”.

[0146] However, it is assumed that the remaining characteristics except the thickness of the low refractive index layer 430 remain unchanged.

[0147] The double-sided reflectivity (%) may refer to a reflectivity measured in a transmission mode of a reflectivity measuring device, and the double-sided reflectivity (%) may be converted into a reflectivity measured in a reflection mode of the reflectivity measuring device.

[0148] According to Table 1, the double-sided reflectivity measured when the thickness of the low refractive index layer 430 is 250nm is greater than the double-sided reflectivity measured when the thickness of the low refractive index layer 430 is 200nm. In addition, the double-sided reflectivity measured when the thickness of the low refractive index layer 430 is 200nm is greater than the double-sided reflectivity measured when the thickness of the low refractive index layer 430 is 90nm.

[0149] The double-sided reflectivity measured when the thickness of the low refractive index layer 430 is 90nm is 5.35%, and when converted into the reflectivity measured in the reflection mode, the amount is about 1.35%. Accordingly, when the thickness of the low refractive index layer 430 is 90nm, a protective film 400 with low reflectivity (e.g., a reflectivity target value of 2% or less) can be provided.

[0150] According to Table 1, when the thickness of the low refractive index layer 430 is 90 nm, it can be confirmed that the difference in crack strain (%) before and after the low refractive index layer 430 is attached is small.

[0151] Table 2 below shows the contact angle of the low refractive index layer 430 including a monomer in which n of DFHA is 8.

[0152] [Table 2]

[0153]

[0154] The term " eraser " in the table 2 may refer to the " eraser test " carried out under predetermined conditions, and the term " K " in the table 2 may mean 1,000 reciprocating cycles. The eraser test is a kind of wear resistance test carried out on the surface of target. It can be carried out by industrial eraser being pressed on the surface, and then moving the eraser left and right. The predetermined conditions in the eraser test may comprise the amount of the surperficial force applied to target, the quantity moving left and right and the specification of the industrial eraser.

[0155] However, it is assumed that the remaining features of the protective film 400 remain unchanged except for the inclusion of the low refractive index layer 430. The low refractive index layer 430 of Table 2 has a thickness of 90 nm, and the refractive index of the low refractive index layer 430 may be 1.342.

[0156] The initial contact angle of the protective film 400 including the low refractive index layer 430 according to the embodiment is 111.2°, and the protective film including the low refractive index layer 430 has more improved water resistance than the protective film 400 not including the low refractive index layer 430 .

[0157] refer to Figures 5 to 7 , the above-mentioned protective film 400 included in the display device according to the embodiment may have the following characteristics and effects.

[0158] (1) a reflectivity (at 550 nm) of about 0.5% to about 2.0% (especially about 1.0% to about 1.5%),

[0159] (2) a crack strain of about 6% to about 15% (especially about 8% to about 12%),

[0160] (3) Initial contact angle of 100° or greater (water)

[0161] In detail, when the reflectivity (at 550 nm) of the low refractive index layer 430 is less than 0.5% or greater than 2.0%, external light has an adverse effect on display quality.

[0162] In detail, when the crack strain of the low refractive index layer 430 is less than 6%, the protective film 400 or the low refractive index layer 430 may be damaged by the folding operation when the flexible display device is implemented. When the crack strain of the low refractive index layer 430 is greater than 15%, the stability or reliability of the protective film 400 or the low refractive index layer 430 is adversely affected when the flexible display device is implemented.

[0163] In detail, when the initial contact angle (water) of the low refractive index layer 430 is less than 100°, it may be difficult to protect the display module 200 or the display panel 10 from moisture.

[0164] Figure 8 FIG. 1 is a flow chart schematically showing a method for manufacturing a protective film according to an embodiment.

[0165] For reference, it can be omitted Figure 8 With the above Figures 1 to 7 Same or duplicate descriptions between.

[0166] like Figure 4 and Figure 8 As explained in , the method of manufacturing the protective film 400 may include: forming a base layer 410 on a substrate (S1100); forming a hard coating layer 420 on the base layer 410 (S1200); and performing a vacuum deposition polymerization process to form a low refractive index layer 430 including DFHA on the hard coating layer 420 (S1300).

[0167] The vacuum deposition polymerization process may be performed under the first condition and the second condition, and the first condition may mean that the substrate temperature is -20°C and the second condition may mean that the ion acceleration voltage is 100 V. Like the first and second conditions, the substrate temperature and the ion acceleration voltage may be included in the film forming conditions.

[0168] Table 3 shows the component contents of the low refractive index layer 430 measured using XPS analysis.

[0169] [Table 3]

[0170]

[0171] (All substrate temperatures are -20°C.)

[0172] The monomer layer in which n of DFHA is 8 and no ion acceleration voltage is used is a comparative example, and its component contents are as above.

[0173] In embodiment A, the low refractive index layer 430 is formed by a vacuum deposition polymerization process, wherein an ion acceleration voltage of 100 V is applied to the monomer (where n of DFHA is 8). In embodiment B, the low refractive index layer 430 is formed by a vacuum deposition polymerization process, wherein an ion acceleration voltage of 500 V is applied to the monomer (where n of DFHA is 8).

[0174] It is observed that the fluorine content of Embodiment A and Embodiment B is less than that of Comparative Example. In detail, the fluorine content of Embodiment A is less than that of Comparative Example, and the fluorine content of Embodiment B is less than that of Embodiment A.

[0175] The above trend of fluorine content may be due to the fact that fluorine bonds are broken with increasing ion acceleration voltage. Accordingly, under film forming conditions, the fluorine content decreases with increasing ion acceleration voltage.

[0176] As for the oxygen content, it was observed that the oxygen content of Embodiment A and Embodiment B was less than that of Comparative Example. In detail, the oxygen content of Embodiment A was less than that of Comparative Example, and the oxygen content of Embodiment B was less than that of Embodiment A.

[0177] As for the carbon content, it is observed that the carbon content of Embodiment A and Embodiment B is higher than that of Comparative Example. In detail, the carbon content of Embodiment A is greater than that of Comparative Example, and the carbon content of Embodiment B is greater than that of Embodiment A.

[0178] According to Table 3, the fluorine content of the low refractive index layer 430 is higher under the film forming condition of 100 V than under the film forming condition of 500 V. The higher the fluorine content, the lower the surface energy of the low refractive index layer 430, and as a result, as indicated in Table 4 described below, the initial contact angle increases.

[0179] Accordingly, in summarizing Table 3, the low refractive index layer 430 according to the embodiment may have the following characteristics.

[0180] (1) The fluorine content of the low refractive index layer 430 is about 45 wt % to about 80 wt %.

[0181] (2) The fluorine content / carbon content of the low refractive index layer 430 is about 1 to about 1.5.

[0182] (3) The oxygen content / carbon content of the low refractive index layer 430 is about 0.1 to about 0.5.

[0183] (4) The fluorine content / oxygen content of the low refractive index layer 430 is about 6 to about 8.6.

[0184] Table 4 below shows the reflectivity (here, "reflectivity" means "double-sided reflectivity") and contact angle evaluation results according to the film-forming conditions.

[0185] [Table 4]

[0186]

[0187] (All substrate temperatures are -20°C.)

[0188] The term "wear and tear" in the above-mentioned table 4 may refer to a "wear and tear test" carried out under predetermined conditions, the term "eraser" in the table 4 may refer to an "eraser test" carried out under predetermined conditions, and the term "K" in the table 4 may mean 1,000 reciprocating cycles. The wear and tear test may be carried out by pressing a hard object onto the surface of the target, and then moving the hard object left and right. The term "hard object" may refer to articles made of metal, such as a rod or a sphere. The predetermined conditions in the wear and tear test and the eraser test may include the amount of force applied to the surface of the target, the quantity moving left and right, the material of the hard object, and the specifications of the industrial eraser.

[0189] In Embodiments 1 to 8, the low refractive index layer 430 has the same thickness and is formed by performing a vacuum deposition polymerization process on DFHA having n of 8. The various conditions applied to Embodiments 1 to 8 may further include conditions other than those shown in Table 4.

[0190] Table 4 shows a summary of reflectivity and contact angle data for various embodiments according to the magnitude of the ion acceleration voltage, whether pre-treatment is performed, whether post-treatment is performed, and the like.

[0191] The pretreatment process may be a UV ozone treatment process performed at room temperature. Oxygen molecules in the atmosphere are decomposed by the UV ozone treatment process. As a result, ozone is generated, and therefore, the organic material on the upper surface of the hard coating 420 can be removed by the generated ozone. In the UV ozone treatment process used herein, the UV irradiation distance and the UV irradiation time may be about 10 mm to about 100 mm and about 0 minutes to about 15 minutes, respectively. The "UV irradiation distance" and "UV irradiation time" of embodiments 3 to 8 in Table 4 may be 15 minutes and 10 mm, respectively. For example, when the UV irradiation distance is 10 mm and the UV irradiation time is 15 minutes, the contact angle of the low refractive index layer 430 may be minimum.

[0192] The post-treatment process may be a baking process of heating the low refractive index layer 430 formed by the vacuum deposition polymerization process at 150° C. for 30 minutes. In other words, the post-treatment process may be a baking process of heating the low refractive index layer 430 at 150° C. for 30 minutes in a chamber after the vacuum deposition polymerization process.

[0193] The ion acceleration voltage applied to the manufacturing methods of Embodiment 1 and Embodiment 2 is 100V, and the manufacturing methods of Embodiment 1 and Embodiment 2 do not include a pre-treatment process. In this state, Embodiment 1 relates to a low refractive index layer 430 to which a post-treatment process is not applied, and Embodiment 2 relates to a low refractive index layer 430 to which a post-treatment process is applied. It can be confirmed that the difference in reflectivity and contact angle between Embodiment 1 and Embodiment 2 is not significant.

[0194] The ion acceleration voltage applied to the manufacturing method of Embodiment 3 is 100 V, and the manufacturing method of Embodiment 3 includes the above-mentioned pretreatment process. It can be confirmed that the reflectivity of Embodiment 3 is higher than that of Embodiment 1, and the contact angle of Embodiment 3 is smaller than that of Embodiment 1.

[0195] The ion acceleration voltage applied to the manufacturing method of Embodiment 4 is 100 V, and the manufacturing method of Embodiment 4 includes the above-mentioned pretreatment process. However, unlike the manufacturing method of Embodiment 3, the manufacturing method of Embodiment 4 may further include a condition of heating the monomer layer at about 10° C. to about 90° C. when performing the vacuum deposition polymerization process. The heating temperature of the monomer layer may be particularly about 40° C. to about 50° C.

[0196] The result is to confirm that the reflectivity of embodiment 4 is less than the reflectivity of embodiment 3, and the initial contact angle of embodiment 4 is less than the initial contact angle of embodiment 3, but compared with the wear characteristics and eraser characteristics of embodiment 4, the wear characteristics and eraser characteristics of embodiment 3 are improved. The wear characteristics refer to the contact angle after the wear test, and the eraser characteristics can refer to the contact angle after the eraser test. In this case, the improvement of the wear characteristics and eraser characteristics can indicate that the size of the contact angle has been reduced.

[0197] The ion acceleration voltage applied to the manufacturing methods of Embodiment 5 and Embodiment 6 is 100V, and the manufacturing methods of Embodiment 5 and Embodiment 6 include a pretreatment process. In this state, Embodiment 5 relates to a low refractive index layer 430 to which a post-treatment process is applied, and Embodiment 6 relates to a low refractive index layer 430 to which a post-treatment process is not applied. It can be confirmed that the difference in reflectivity and contact angle between Embodiment 5 and Embodiment 6 is not significant.

[0198] However, the reflectivity of Embodiment 5 is greater than that of Embodiment 3, and the contact angle of Embodiment 5 is also greater than that of Embodiment 3. The difference between Embodiment 5 and Embodiment 3 is whether a post-treatment process is performed.

[0199] The ion acceleration voltage applied to the manufacturing methods of Embodiment 7 and Embodiment 8 is 300V, and the manufacturing methods of Embodiment 7 and Embodiment 8 include a pre-treatment process. In this state, Embodiment 7 relates to a low-refractive index layer 430 to which a post-treatment process is applied, and Embodiment 8 relates to a low-refractive index layer 430 to which a post-treatment process is not applied. It can be confirmed that the reflectivity of Embodiment 7 increases compared to the reflectivity of Embodiment 8. It can be confirmed that the difference between the contact angle of Embodiment 7 and the contact angle of Embodiment 8 is not significant.

[0200] As a result, according to Table 3 and Table 4, in the method of manufacturing the protection film 400 according to the embodiment, the vacuum deposition polymerization process may be characterized as follows.

[0201] (1) The ion acceleration voltage is about 80 V to about 120 V, especially 100 V.

[0202] (2) A pretreatment process is performed before the vacuum deposition polymerization process.

[0203] (3) A post-treatment process is performed after the vacuum deposition polymerization process.

[0204] Since the method of manufacturing the protective film 400 according to the embodiment includes the above three features, it can have the significant effects of low reflectivity and high initial contact angle of the embodiments of Table 3 and Table 4.

[0205] Fig. 9 For Figure 8 A conceptual diagram of the process used in the manufacturing method.

[0206] For reference, it can be omitted Fig. 9 With the above Figures 1 to 8 Same or duplicate descriptions between.

[0207] like Fig. 9 As explained in Figure 8 The vacuum deposition polymerization process of the manufacturing method may be a dry deposition method performed in the chamber CB. The DFHA may be ejected from the monomer storage container BT through the monomer nozzle GN, and the argon molecules Ar 2 It may be ejected from the ion source SC. The ion source SC may receive necessary power from the voltage generator PW, and the above-mentioned DFHA may be deposited on a target TG (such as a substrate) or the like.

[0208] According to the above-described embodiments, a protective film having low reflectivity and being resistant to cracking, a display device including the protective film, and a method of manufacturing the protective film can be realized. The scope of the present disclosure is not limited by the above-described effects.

[0209] It should be understood that the embodiments described herein should be considered in a descriptive sense only and not for limiting purposes. The description of features or aspects within each embodiment should generally be considered to be applicable to other similar features or aspects in other embodiments. Although one or more embodiments have been described with reference to the figures, it will be understood by those of ordinary skill in the art that various changes in form and detail may be made therein without departing from the spirit and scope defined by the claims.

Claims

1. A protective film comprising: basal layer; a hard coating layer disposed on the base layer; and A low refractive index layer is disposed on the hard coating layer and includes dodecafluoroheptyl acrylate. 2 . The protective film according to claim 1 , wherein the low refractive index layer includes a polymer compound composed of the dodecafluoroheptyl acrylate, and a degree of polymerization of the polymer compound is any one of 6 to 12. 3 . 3 . The protective film according to claim 1 , wherein the low refractive index layer comprises a polymer compound composed of the dodecafluoroheptyl acrylate, and a degree of polymerization of the polymer compound is 8. 4 . The protective film according to claim 1 , wherein the low refractive index layer comprises only the dodecafluoroheptyl acrylate. The protective film according to claim 1 , wherein the low refractive index layer has a thickness of 70 nm to 130 nm. 6 . The protective film according to claim 1 , wherein the fluorine content of the low refractive index layer is 45 wt % to 80 wt %. 7 . The protective film according to claim 1 , wherein the infrared spectrum of the low refractive index layer includes two -CF2 peaks and three -CF3 peaks.

8. The protective film according to claim 7, wherein the -CF2 peak is included at 1150 cm -1 Up to 1160cm -1 The first peak frequency in the range and at 1210 cm -1 Up to 1220cm -1 The second peak frequency in the range.

9. The protective film according to claim 8, wherein the -CF3 peak has a peak at 975 cm -1 Up to 1280cm -1 Three peak frequencies within the range.

10. A display device, comprising: a display module foldable about at least one folding axis; and The protective film according to any one of claims 1 to 9 is disposed on the display module.

11. A method for manufacturing a protective film, the method comprising: forming a base layer on a substrate; forming a hard coating layer on the base layer; and A vacuum deposition polymerization process is performed to form a low refractive index layer including dodecafluoroheptyl acrylate on the hard coating layer. 12 . The method according to claim 11 , further comprising performing an ultraviolet ozone treatment process on an upper surface of the hard coating layer before performing the vacuum deposition polymerization process.

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