Polymer resin, window module containing the same, and display device including the window module

Abstract

The present disclosure relates to a polymer resin, a window module including the same, and a display device including the window module. According to one embodiment, the window module includes a window, a first printing layer, an ink layer, and a protective layer covering the ink layer. The protective layer includes a polymer resin polymerized from monomers, wherein the monomers include: a first monomer of an acrylic monomer substituted with a hydroxyl group; a second monomer containing an epoxy group; and at least one of a third monomer substituted with or containing an unsubstituted phenyl group and a fourth monomer of an acrylic monomer substituted with or containing an unsubstituted bicyclic alkyl group, thereby having excellent durability, chemical resistance, and wear resistance.

Description

Technical Field

[0001] The present disclosure relates to a polymer resin, a window module including the same, and a display device including the window module. More specifically, the present disclosure relates to a polymer resin with improved chemical resistance and wear resistance, a window module including the same, and a display device including the window module. Background Art

[0002] When a defect occurs in the manufacturing process of the display device, a rework process is required to save costs. In the rework process, in order to bond the window module and the display panel, a process of removing the adhesive layer configured on the window module may be included. For this purpose, the surface of the window module may be physically or chemically treated. At this time, problems such as damage or contamination of the ink printed on the window module may occur. Summary of the invention

[0003] An object of the present disclosure is to provide a polymer resin with improved durability, chemical resistance, and wear resistance.

[0004] An object of the present disclosure is to provide a window module comprising a polymer resin having improved durability, chemical resistance, and wear resistance.

[0005] An object of the present disclosure is to provide a display device including a window module with improved durability, chemical resistance, and wear resistance.

[0006] According to an embodiment of the present disclosure, a window module may include a window, a first printing layer, an ink layer, and a protective layer. The first printing layer may be arranged on the window and define an opening. The ink layer may fill the opening. The ink layer may include a base resin and at least one of a pigment and a dye dispersed in the base resin. The protective layer may cover the ink layer. The protective layer may include a polymer resin. The polymer resin may be polymerized from a monomer including a first monomer, a second monomer, and at least one of a third monomer and a fourth monomer. The first monomer may be an acrylic monomer substituted with a hydroxyl group. The second monomer may include an epoxy group. The third monomer may be substituted or include an unsubstituted phenyl group. The fourth monomer may be substituted or include an unsubstituted bicyclic alkyl group.

[0007] The first to fourth monomers are represented by the following Chemical Formulas 1 to 4, respectively.

[0008] [Chemical formula 1]

[0009]

[0010] [Chemical formula 2]

[0011]

[0012] [Chemical formula 3]

[0013]

[0014] [Chemical formula 4]

[0015]

[0016] In the chemical formula 1 to the chemical formula 4, R 1 , R 3 , R 4 , R 5 , R 7 and R 8 R may be independently a hydrogen atom or a methyl group. 2 It can be hydroxyl or hydroxymethyl. 6 It may be a hydrogen atom, or a substituted or unsubstituted alkyl group having a carbon number of 1 to 5. a and b may each independently be an integer of 0 to 5. The second monomer may be represented by the following Chemical Formula 2-1.

[0017] [Chemical formula 2-1]

[0018]

[0019] In the chemical formula 2-1, R 9 It can be a hydrogen atom or a methyl group. 10 It may be a methylene group or an oxymethylene group.

[0020] The polymer resin may contain all of the third monomer and the fourth monomer.

[0021] The first monomer may include at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate and hydroxypropyl acrylate. The second monomer may include at least one of bisphenol A type epoxy monomer, glycidyl methacrylate, glycidyl acrylate and allyl glycidyl ether. The third monomer may include at least one of isopropenylbenzene and tert-butylstyrene. The fourth monomer may include at least one of isobornyl acrylate and isobornyl methacrylate. The polymer resin may also be polymerized by a crosslinking agent.

[0022] The weight ratio of the cross-linking agent may be greater than or equal to 20 wt % and less than or equal to 25 wt % based on the total weight of the first to fourth monomers.

[0023] The cross-linking agent may include at least one of an isocyanate cross-linking agent and an amine cross-linking agent.

[0024] The protective layer may contain 10 mol% to 30 mol% of the first monomer based on the first to fourth monomers as a whole, 10 mol% to 30 mol% of the second monomer, 50 mol% to 80 mol% of at least one of the third monomer and the fourth monomer.

[0025] The polymer resin may further include inorganic particles. The inorganic particles may be barium sulfate.

[0026] The visible light transmittance of the protective layer with a central wavelength of 540 nm may be greater than 99%. The ink layer may include a first portion and a second portion. The first portion may fill the opening. The second portion may extend from the first portion and be disposed on the first printing layer.

[0027] In one embodiment, the window module may further include a second printing layer. The second printing layer may be disposed on the first printing layer. At least a portion of the second portion of the ink layer may be disposed between the first printing layer and the second printing layer.

[0028] A display device according to an embodiment of the present disclosure may include a window module, an infrared sensor, and a display panel. A frame area and a transmission area may be defined in the window module. The frame area may define a semi-transmission area that transmits infrared rays and a non-transmission area surrounding the semi-transmission area. The transmission area may be adjacent to the frame area. The infrared sensor may overlap the semi-transmission area. The display panel may overlap a portion of the frame area and the transmission area. The window module may include a window, a first printing layer, an ink layer, and a protective layer. The first printing layer may be configured in the non-transmission area. The ink layer may be configured in the semi-transmission area. The ink layer may include a base resin and at least one of a pigment and a dye dispersed in the base resin. The protective layer may cover the ink layer. The protective layer may include a polymer resin. The polymer resin may be polymerized by a monomer including a first monomer, a second monomer, and at least one of a third monomer and a fourth monomer. The first monomer may be an acrylic monomer substituted with a hydroxyl group. The second monomer may include an epoxy group. The third monomer may be substituted or include an unsubstituted phenyl group. The fourth monomer may be substituted or include an unsubstituted bicyclic alkyl group.

[0029] The first to fourth monomers may be represented by the above-mentioned Chemical Formulas 1 to 4, respectively.

[0030] In one embodiment, the display device may further include a second printing layer disposed on the first printing layer. The ink layer may include a first portion and a second portion. The first portion may be disposed in the semi-transmissive region. The second portion may extend from the first portion and be disposed in the non-transmissive region.

[0031] The polymer resin may also be polymerized from at least one of an isocyanate crosslinking agent and an amine crosslinking agent.

[0032] The polymer resin according to an embodiment of the present disclosure can be polymerized by a first monomer, a second monomer, a third monomer, a fourth monomer, and at least one selected from an isocyanate crosslinking agent and an amine crosslinking agent. The first monomer, the second monomer, the third monomer, and the fourth monomer can be represented by the above-mentioned chemical formulas 1 to 4.

[0033] The first monomer may include at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate and hydroxypropyl acrylate. The second monomer may be a bisphenol A type epoxy monomer. The third monomer may include at least one of isopropenylbenzene and tert-butylstyrene. The fourth monomer may include at least one of isobornyl acrylate and isobornyl methacrylate.

[0034] (Effect of Publicity)

[0035] The polymer resin according to an embodiment can improve durability, chemical resistance, and wear resistance.

[0036] The window module according to an embodiment includes a polymer resin with improved durability, chemical resistance, and wear resistance, thereby improving the efficiency of a rework process.

[0037] A display device according to an embodiment includes a window module having improved durability, chemical resistance, and wear resistance, and thus can improve efficiency of a rework process. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 is a perspective view of a display device according to an embodiment.

[0039] Figure 2 is an exploded perspective view of a display device according to an embodiment.

[0040] Figure 3 It is along Figure 1 A cross-sectional view of the display device taken along line II′.

[0041] Figure 4 is a cross-sectional view of a display panel according to an embodiment.

[0042] Figure 5 It is along Figure 1A cross-sectional view of the display device taken along line II-II′.

[0043] Figure 6 It is along Figure 2 A cross-sectional view of the window module taken along line III-III′.

[0044] Figure 7 is along with Figure 2 The cross-sectional view of the window module corresponding to the surface intercepted by line III-III′.

[0045] Description of Reference Numerals

[0046] DD: Display Device WDM: Window Module

[0047] WD: Window PTL: Printing Layer

[0048] IKL: ink layer PL: protective layer DETAILED DESCRIPTION

[0049] In this specification, when it is mentioned that a certain constituent element (or region, layer, part, etc.) is "located on" other constituent elements, "connected" or "combined with" other constituent elements, it means that it can be directly configured / connected / combined on other constituent elements or a third constituent element can be configured between them.

[0050] The same reference numerals refer to the same components. In addition, in the drawings, the thickness, proportion and size of the components are exaggerated for the purpose of effectively explaining the technical content.

[0051] “And / or” includes all combinations that can define more than one of the related components.

[0052] The terms first, second, etc. may be used to describe a variety of constituent elements, but the constituent elements should not be limited to the terms. The terms are used only to distinguish one constituent element from other constituent elements. For example, without departing from the scope of the present disclosure, the first constituent element may be named the second constituent element, and similarly the second constituent element may be named the first constituent element. Unless otherwise expressly stated in the context, a singular expression includes a plural expression.

[0053] In addition, the terms such as “lower”, “lower side”, “above”, “upper”, and “upper side” are used to explain the correlation relationship of the configurations shown in the drawings. The above terms are relative concepts and are explained based on the directions shown in the drawings.

[0054] Unless otherwise defined, all terms (including technical terms and scientific terms) used in this specification have the same meanings as those commonly understood by those skilled in the art to which the present disclosure belongs. In addition, terms that are the same as terms defined in commonly used dictionaries should be interpreted as having meanings consistent with the context of the relevant technology, and are clearly interpreted as the meanings defined in this specification unless they are interpreted as ideal or overly formal.

[0055] Terms such as "including" or "having" should be understood as being used to specify the existence of features, numbers, steps, actions, constituent elements, parts or combinations thereof recorded in the specification, and do not exclude in advance the existence or additional possibilities of one or more other features or numbers, steps, actions, constituent elements, parts or combinations thereof.

[0056] Hereinafter, embodiments of the present disclosure will be described with reference to the drawings.

[0057] Figure 1 is a perspective view of a display device DD according to an embodiment. Figure 2 is an exploded perspective view of a display device DD according to an embodiment.

[0058] Figure 1 In the figure, a portable terminal in which all the edges of the four sides are provided as curved surfaces is exemplarily shown as a display device DD. However, the embodiment is not limited to this, and can be applicable to various display devices DD such as a flat display device, a curved display device, a bent display device, a scroll display device, a folding display device, and a stretching display device. In addition, although not separately illustrated, the display device DD according to the present disclosure can be used in large electronic devices such as televisions or external billboards, as well as personal computers, notebook computers, personal digital terminals, car navigation systems, game consoles, portable electronic devices, watch-type electronic devices, and small and medium-sized electronic devices such as cameras. These are only shown as embodiments, and can of course be used in other electronic devices as long as they do not deviate from the concept of the present disclosure.

[0059] The display device DD includes a plurality of areas distinguished on a display surface. The display device DD may include a display area DA displaying an image IM and a non-display area NDA adjacent to the display area DA. Figure 1 , a clock widget is shown as an example of the image IM. The non-display area NDA may surround the display area DA. The non-display area NDA may include a semi-transmission area HTA and a non-transmission area NTA surrounding the semi-transmission area HTA, and the details will be described later.

[0060] In this embodiment, the front (or top surface) and the back (or bottom surface) of each component are defined based on the direction in which the image IM is displayed. The front and the back can be opposite to each other in the third direction DR3, and the normal directions of the front and the back are parallel to the third direction DR3. On the other hand, the directions pointed by the first direction DR1, the second direction DR2 and the third direction DR3 are relative concepts and can be converted into other directions. Hereinafter, the first direction to the third direction are the directions pointed by the first direction DR1, the second direction DR2 and the third direction DR3, respectively, and refer to the same figure marks. In this specification, "on a plane" can mean the situation when observed from the third direction DR3, that is, from the normal direction.

[0061] Reference Figure 2 The display device DD may include a window module WDM, a display panel DP, an infrared sensor EM-IR and a housing CU.

[0062] The window module WDM can protect the display panel DP from external impact and provide an input surface for the user. The window module WDM can include glass or plastic. The window module WDM can have a transparent property so that the light generated in the display panel DP can pass through. The window module WDM can be a rigid substrate or a flexible substrate.

[0063] The window module WDM may include a frame area BZA and a transmissive area TA adjacent to the frame area. The frame area BZA may surround the transmissive area TA. Figure 1 The transmissive area TA may be an area corresponding to the non-display area NDA. Figure 1 However, the embodiment is not limited thereto, and the frame area BZA and the non-display area NDA may not necessarily be consistent, and the transmission area TA and the display area DA may not necessarily be consistent.

[0064] The display panel DP may generate an image IM. In one embodiment, the display panel DP may be a light-emitting display panel, but the embodiment is not particularly limited. For example, the display panel DP may be an organic light-emitting display panel, a quantum dot light-emitting display panel, a plasma display panel, an electrophoretic display panel, or an electrowetting display panel. The light-emitting layer of the organic light-emitting display panel may include an organic light-emitting substance. The light-emitting layer of the quantum dot light-emitting display panel may include quantum dots and quantum rods, etc. In the following, the display panel DP is described as an organic light-emitting display panel.

[0065] The infrared sensor EM-IR may not overlap with the display panel DP in a plane. That is, the infrared sensor EM-IR may be stored as a separate electronic device. However, the embodiment is not limited thereto, and the infrared sensor EM-IR may be integrally included in the display panel DP.

[0066] Although not shown in the figure, the infrared sensor EM-IR may include, for example, an emitting unit (not shown) that emits infrared rays and a light receiving unit (not shown). The light receiving unit may be a unit that receives infrared rays reflected by an external object when the infrared rays emitted from the emitting unit are reflected by the external object to generate an electrical signal. For example, the infrared sensor EM-IR may be a biometric sensor such as an iris recognition sensor.

[0067] The display device DD may further include electronic modules such as a camera module (not shown) and a short-range illumination sensor (not shown) in addition to the infrared sensor EM-IR.

[0068] The housing CU can accommodate the display panel DP and the infrared sensor EM-IR, and is combined with the window WD. The housing CU can include a main body assembled or injection molded from multiple parts. The housing CU can include glass, plastic or metal.

[0069] Figure 3 It is along Figure 1 sectional view of the display device DD taken along line II′. Figure 3 The diagram is simply shown for the purpose of explaining the stacking relationship of the functional components constituting the display device DD.

[0070] like Figure 3 As shown, the display device DD may include a display panel DP, an input sensing layer ISL, a reflection prevention plate RPP, and a window WD. The input sensing layer ISL may be directly disposed on the display panel DP. In this specification, "the B structure is directly disposed on the A structure" means that no additional adhesive layer / adhesive component is disposed between the A structure and the B structure. The B structure may be formed on the substrate surface where the A structure is provided by a continuous process after the A structure is formed.

[0071] The display panel DP and the input sensing layer ISL directly configured on the display panel DP may be included in the display module DM. An optically transparent adhesive component may be configured between the display module DM and the anti-reflection plate RPP and between the anti-reflection plate RPP and the window WD. The adhesive component may be an optically transparent adhesive component OCA.

[0072] The display panel DP generates an image, and the input sensing layer ISL obtains coordinate information of external input (e.g., a touch event). Although not shown separately, the display module DM according to an embodiment of the present disclosure may also include a protective component configured on the bottom surface of the display panel DP. The protective component and the display panel DP may be combined by an adhesive component.

[0073] The anti-reflection plate RPP reduces the reflectivity of external light incident from the upper side of the window WD. The anti-reflection plate RPP according to an embodiment of the present disclosure may include a phase retarder and a polarizer. The phase retarder may be a film type or a liquid crystal coating type, and may include a λ / 2 phase retarder and / or a λ / 4 phase retarder. The polarizer is also a film type, and may include an extended synthetic resin film. The phase retarder and the polarizer may also include a protective film. The phase retarder and the polarizer themselves or the protective film may be defined as the base layer of the anti-reflection plate RPP.

[0074] The anti-reflection plate RPP according to an embodiment of the present disclosure may include a color filter. The color filter has a predetermined arrangement. The arrangement of the color filter may be determined in consideration of the luminous color of the pixels included in the display panel DP. The anti-reflection plate RPP may further include a black matrix adjacent to the color filter.

[0075] Figure 4 is a cross-sectional view of a display panel DP according to an embodiment. Figure 4 , the display panel DP is an organic light emitting display panel. Figure 4 The display panel DP includes a base substrate BL, a circuit element layer DP-CL, a display element layer DP-OLED, and an encapsulation layer TFE. Although not shown in the figure, the display panel DP may further include functional layers such as a reflection prevention layer and a refractive index adjustment layer.

[0076] The base substrate BL may be a stacked structure including a glass substrate, a silicon substrate, a plastic substrate, an insulating film, or a plurality of insulating layers.

[0077] The circuit element layer DP-CL can be configured on the base substrate BL. The circuit element layer DP-CL includes at least one insulating layer and a circuit element. Hereinafter, the insulating layer included in the circuit element layer DP-CL is referred to as an intermediate insulating layer. The intermediate insulating layer includes at least one intermediate inorganic film and at least one intermediate organic film. The circuit element includes a signal line, a pixel driving circuit, etc. The circuit element layer DP-CL can be formed by an insulating layer, a semiconductor layer, and a conductive layer forming process based on coating, evaporation, etc. and an insulating layer, a semiconductor layer, and a conductive layer patterning process based on a photolithography process.

[0078] The display element layer DP-OLED may be arranged on the circuit element layer DP-CL. The display element layer DP-OLED includes a light emitting element. The display element layer DP-OLED may include an organic light emitting diode. The display element layer DP-OLED may also include an organic film such as a pixel defining film.

[0079] The encapsulation layer TFE is configured on the display element layer DP-OLED to seal the display element layer DP-OLED. The encapsulation layer TFE includes at least one insulating layer. The encapsulation layer TFE according to an embodiment of the present disclosure may include at least one inorganic film (hereinafter, encapsulation inorganic film). The encapsulation layer TFE according to an embodiment of the present disclosure may include at least one organic film (hereinafter, encapsulation organic film) and at least one encapsulation inorganic film.

[0080] The encapsulated inorganic film protects the display element layer DP-OLED from moisture / oxygen, and the encapsulated organic film protects the display element layer DP-OLED from foreign matter such as dust particles. The encapsulated inorganic film may include a silicon nitride layer, a silicon oxynitride layer, a silicon oxide layer, a titanium oxide layer, or an aluminum oxide layer, etc., without particular limitation thereto. The encapsulated organic film may include an acrylic organic film, without particular limitation thereto. Figure 3 The input sensing layer ISL ( Figure 3 ) can be directly configured on the packaging layer TFE.

[0081] Figure 5 It is along Figure 1 A cross-sectional view of the display device DD taken along the line II-II′. Figure 5 The window module WDM may include a window WD, a printing layer PTL, an ink layer IKL and a protective layer PL.

[0082] The printing layer PTL may be disposed on the window WD. An opening OP-PTL may be defined in the printing layer PTL. The printing layer PTL may define a frame area BZA. That is, in the frame area BZA, the portion where the printing layer PTL is disposed may be defined as a non-transmissive area NTA, and the portion where the opening OP-PTL is defined may be defined as a semi-transmissive area HTA.

[0083] The printed layer PTL may include a shielding ink layer for shielding light. For example, the shielding ink layer may include a base material and a shielding ink. The shielding ink may be carbon black particles. However, the embodiment is not limited thereto, and the shielding ink may include one or more known pigments, dyes, or mixtures thereof in addition to carbon black particles. The printed layer PTL may prevent the internal structure of the display device DD from being recognized from the outside.

[0084] The ink layer IKL may be disposed on the window WD to fill the opening OP-PTL. The ink layer may include a matrix resin and at least one of a pigment and a dye dispersed in the matrix resin. The ink layer IKL may define the semi-transmissive area HTA.

[0085] Since the ink layer IKL contains a pigment or a dye and may have a color, the infrared sensor EM-IR accommodated in the display device DD may not be recognized from the outside.

[0086] The ink layer IKL can selectively transmit infrared rays among visible rays and infrared rays. That is, the ink layer IKL can absorb visible rays and transmit infrared rays. For example, the ink layer IKL can absorb more than 90% of visible rays and can transmit more than 80% or more than 90% of infrared rays. Therefore, infrared rays emitted from the infrared sensor EM-IR are emitted to the outside through the ink layer IKL, and infrared rays reflected by external substances can reach the infrared sensor EM-IR through the ink layer IKL. In contrast, visible rays are mostly absorbed by the ink layer IKL, so the sensitivity of the infrared sensor EM-IR can be improved.

[0087] It may be that at least one of the matrix resin, the dye, and the pigment contained in the ink layer IKL absorbs visible light and transmits infrared light.

[0088] The protection layer PL may be disposed between the window WD and the ink layer IKL. The protection layer PL may cover the ink layer IKL. The protection layer PL may be directly disposed on the ink layer IKL to cover the ink layer IKL.

[0089] The infrared sensor EM-IR may overlap with the semi-transmissive area HTA. Although not shown, a portion of the infrared sensor EM-IR may overlap with the non-transmissive area NTA.

[0090] The protective layer may have a visible light transmittance of 99% or more. The weight average molecular weight of the polymer resin may be 20,000 or more and 40,000 or less. Specifically, the weight average molecular weight of the polymer resin may be 20,000 or more and 30,000 or less.

[0091] The protective layer PL may include a polymer resin obtained by polymerizing monomers including a first monomer, a second monomer, and a third monomer or a fourth monomer. That is, the polymer resin may include the first monomer and the second monomer, and may include at least one of the third monomer and the fourth monomer. Preferably, the polymer resin may include all of the first monomer to the fourth monomer.

[0092] The first monomer may be an acrylic monomer containing a substituted hydroxyl group. The second monomer may be a monomer containing an epoxy group. For example, the second monomer may be an acrylic monomer containing an epoxy group. The third monomer may be a monomer containing a substituted or unsubstituted phenyl group. The fourth monomer may be an acrylic monomer containing a bicyclic alkyl group. Each of the first to fourth monomers may contain an alkenyl group.

[0093] The polymer resin polymerized from the monomers containing the third monomer and the fourth monomer may have a glass transition temperature of 80° C. to 140° C. Specifically, the polymer resin polymerized from at least one of the third monomer and the fourth monomer containing 50 mol % to 80 mol % may have a glass transition temperature of 80° C. to 140° C. For example, a polymer resin having a glass transition temperature of 90° C. to 130° C. may be obtained by polymerizing the monomers containing the third monomer and the fourth monomer.

[0094] The first to fourth monomers may be represented by the following Chemical Formulas 1 to 4, respectively.

[0095] [Chemical formula 1]

[0096]

[0097] [Chemical formula 2]

[0098]

[0099] [Chemical formula 3]

[0100]

[0101] [Chemical formula 4]

[0102]

[0103] In the chemical formula 1 to the chemical formula 4, R 1 , R 3 , R 4 , R 5 , R 7 and R 8 R may be independently a hydrogen atom or a methyl group. 2 It can be hydroxyl or hydroxymethyl. 6 It may be a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms. 6 When R is a substituted or unsubstituted alkyl group, 6It may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl. a and b may each independently be an integer of 0 to 5. For example, a and b may each independently be 0 or 1.

[0104] The second monomer can also be represented by the following Chemical Formula 2-1.

[0105] [Chemical formula 2-1]

[0106]

[0107] In the chemical formula 2-1, R 9 It can be a hydrogen atom or a methyl group. 10 It may be a methylene group or an oxymethylene group.

[0108] The first monomer may include at least one of hydroxyethyl acrylate (HEA), hydroxyethyl methacrylate (HEMA), and hydroxypropyl acrylate (HPA).

[0109] The second monomer may include at least one of a bisphenol A type epoxy monomer, glycidyl methacrylate, glycidyl acrylate, and allyl glycidyl ether.

[0110] The bisphenol A type epoxy monomer may be formed by reacting a bisphenol A epoxy derivative (derivative) with acrylic acid. The bisphenol A type epoxy monomer may be formed by reacting one epoxy group of a bisphenol A epoxy derivative having two epoxy groups with acrylic acid. For example, the bisphenol A type epoxy monomer may be formed by the following reaction.

[0111]

[0112] The bisphenol A type epoxy monomer may be, for example, 2-hydroxy-3-(4-(2-(4-(oxiran-2-yloxy)phenyl)propan-2-yl)phenoxy)propyl acrylate.

[0113] The third monomer may include at least one of isopropenyl benzene and t-butyl styrene. The fourth monomer may include at least one of isobornyl acrylate (IBOA) and isobornyl methacrylate (IBOMA).

[0114] Preferably, the first monomer may be hydroxyethyl methacrylate which forms a polymer having a high glass transition temperature when polymerized among the above-mentioned first monomers.

[0115] The first monomer contains a hydroxyl group, so when a cross-linking agent is added, a cross-linking bond can be formed. Therefore, since the polymer resin of one embodiment contains the first monomer, durability can be improved.

[0116] The second monomer includes an epoxy group that improves the firmness of the cross-linked structure. Therefore, the polymer resin of one embodiment includes the second monomer, thereby having excellent durability.

[0117] The third monomer and the fourth monomer respectively contain a bicyclic group and a phenyl group, and thus have good durability against chemical substances and a high glass transition temperature. Therefore, since the polymer resin of one embodiment contains the third monomer and the fourth monomer, it can have excellent chemical resistance and wear resistance.

[0118] The polymer resin may be polymerized from a compound containing a crosslinking agent in addition to the first to fourth monomers mentioned above. The crosslinking agent may be a difunctional crosslinking agent. The crosslinking agent may be at least one of an isocyanate crosslinking agent and an amine crosslinking agent.

[0119] The isocyanate crosslinking agent can be a diisocyanate crosslinking agent. The diisocyanate crosslinking agent can be combined with the hydroxyl groups of the two first monomers connected to each other on the main chain (main chain) to form a crosslinking bond. For example, the isocyanate group of the diisocyanate crosslinking agent and the hydroxyl group of the first monomer can react to form a urethane group by crosslinking. The diisocyanate crosslinking agent can be isophorone diisocyanate (IPDI), toluene diisocyanate (TDI) or hexamethylene diisocyanate (HDI), but the embodiment is not limited thereto. For example, in addition, as an isocyanate crosslinking agent, a trifunctional isocyanate crosslinking agent can also be used to replace the diisocyanate crosslinking agent. For example, as an isocyanate crosslinking agent, a triisocyanate crosslinking agent can be used. At this time, the content of the triisocyanate crosslinking agent can be added less than the content of the diisocyanate crosslinking agent.

[0120] The amine crosslinking agent may have multiple functional groups. For example, the amine crosslinking agent may have more than two amine groups. Specifically, the amine crosslinking agent may be diethylenetriamine (DETA) having three amine groups or triethylenetetramine (TETA) having four amine groups. However, the embodiment is not limited thereto.

[0121] In the step of mixing the amine crosslinking agent with the first monomer to the fourth monomer, the hydroxyl group of the first monomer or the epoxy group of the second monomer may react with the amine crosslinking agent to form a crosslinking bond. Specifically, the hydroxyl group of the first monomer may react with the amino group of the amine crosslinking agent to form a urea group through crosslinking.

[0122] In one embodiment, in order to adjust the cross-linking speed during polymerization to form an appropriate cross-linking bond, the functional group of the cross-linking agent can be treated as a protection group through a protection reaction. For example, an isocyanate cross-linking agent can be treated with a protection group. The polymerization reaction can actively occur at a high temperature above room temperature, and the protection group of the cross-linking agent can be removed by a deprotection reaction if a specific temperature at which the polymerization reaction actively occurs is reached. Therefore, it is possible to prevent the phenomenon that the cross-linking agent with a faster reaction speed than the first to fourth monomers reacts first before the reaction temperature is reached.

[0123] The cross-linking agent of one embodiment forms cross-linking bonds as described above, so that the polymer resin can have a high cross-linking density, thereby improving the paint film strength, durability, and barrier properties of the polymer resin.

[0124] The polymer resin may contain 10 mol% to 30 mol% of the first monomer, 10 mol% to 30 mol% of the second monomer, 50 mol% to 80 mol% of the third monomer and at least one of the fourth monomer, based on the first to fourth monomers as a whole. Preferably, the polymer resin may contain 15 mol% to 25 mol% of the first monomer, 15 mol% to 25 mol% of the second monomer, 60 mol% to 70 mol% of the third monomer and at least one of the fourth monomer, based on the first to fourth monomers as a whole.

[0125] When the ratio of the first monomer is less than 10 mol%, the number of hydroxyl groups that can be cross-linked decreases, so the cross-linking density of the polymer resin may decrease. Therefore, the wear resistance and barrier properties of the protective layer PL may decrease. The glass transition temperature of the first monomer is lower than that of the third monomer and the fourth monomer, so when the ratio of the first monomer exceeds 30 mol%, the overall glass transition temperature of the polymer resin decreases, and the wear resistance of the protective layer PL may decrease.

[0126] When the ratio of the second monomer is less than 10 mol%, the hardness of the polymer resin may become too large. Therefore, the protective layer PL may be easily damaged even by a small impact. When the ratio of the second monomer exceeds 40 mol%, the polymer resin may yellow. Therefore, the yellow protective layer may be recognized from the outside.

[0127] The third monomer and the fourth monomer have a phenyl group or a bicycloalkyl group, so the glass transition temperature is high and the chemical resistance is strong. When the ratio of at least one of the third monomer and the fourth monomer is less than 50 mol%, the scratch resistance and chemical resistance of the polymer resin may be reduced. When the ratio of at least one of the third monomer and the fourth monomer exceeds 80 mol%, the hardness of the polymer resin may become too large. Therefore, the protective layer PL may be easily damaged even under a small impact.

[0128] Preferably, the polymer resin may contain both the third monomer and the fourth monomer. In this case, based on the first to fourth monomers as a whole, the ratio of the third monomer to the fourth monomer may be 25 mol% or more and 40 mol% or less, respectively. Preferably, based on the first to fourth monomers as a whole, the ratio of the third monomer to the fourth monomer may be 30 mol% or more and 35 mol% or less, respectively.

[0129] The weight ratio of the crosslinking agent can be based on the total weight of the first to fourth monomers, and can be added at a weight ratio of 20 wt% or more and 25 wt% or less. For example, when 100 g of the first to fourth monomers are added, 20 to 25 g of the crosslinking agent can be added. In this specification, wt% can mean mass%.

[0130] When the crosslinking agent is added at a ratio of 20 wt % or less, the crosslinking density of the polymer resin may be reduced. Therefore, the wear resistance and barrier properties of the protective layer PL may be reduced. When the crosslinking agent is added at a ratio of 25 wt % or more, the transmittance of the polymer resin may be reduced.

[0131] The polymer resin according to one embodiment of the present disclosure may further include a defoamer. Specifically, the defoamer can destroy bubbles generated in the composition to prevent poor appearance when forming a paint film. The defoamer can be a silicon-based defoamer.

[0132] The polymer resin may further contain inorganic particles. The inorganic particles can destroy the bubbles generated in the composition and prevent poor appearance when the paint film is formed. For example, barium sulfate can remove the holes generated by the aggregation of the polymer resin. Preferably, barium sulfate can be included as the inorganic particles. Barium sulfate has excellent chemical resistance and heat resistance. In one embodiment, based on the total weight of the first monomer to the fourth monomer and the cross-linking agent, the inorganic particles can be included at a ratio of more than 1wt% and less than 3wt%. When the ratio of the inorganic particles meets the above range, it can have excellent paint film properties without affecting the transmittance of the polymer resin.

[0133] Figure 6 It is along Figure 2 A cross-sectional view of the window module WDM taken along line III-III′. Figure 7 is along with Figure 2 The cross-sectional view of the window module WDM-1 corresponding to the surface intercepted by line III-III′.

[0134] Reference Figure 6 In the window module WDM, the printed layer PTL may be one layer. However, the embodiment is not limited thereto, and the printed layer PTL may be a structure in which multiple layers are stacked.

[0135] The ink layer IKL may include a first portion IKL1 and a second portion IKL2. The first portion IKL1 may fill the opening OP-PTL. The second portion IKL2 may extend from the first portion IKL1 and be disposed on the printing layer PTL. The first portion IKL1 and the second portion IKL2 may be in an integral shape. The protective layer PL may be configured to cover the ink layer IKL. The protective layer PL may be directly disposed on the ink layer IKL to cover the ink layer IKL. A portion of the protective layer PL may be disposed on the printing layer PTL.

[0136] exist Figure 7 In the example, the window module WDM-1 is configured with two layers of printing layers PTL. The printing layer PTL may include a first printing layer PTL1 and a second printing layer PTL2. At least a portion of the second portion IKL2 of the ink layer IKL may be disposed between the first printing layer PTL1 and the second printing layer PTL2.

[0137] A part of the protection layer PL may be directly arranged on the ink layer IKL, and a part of the protection layer PL may be arranged on the second printed layer PTL2.

[0138] Reference Figure 6 as well as Figure 7In the manufacturing process of the window module WDM, the printing layer PTL, the ink layer IKL and the protective layer PL may be stacked in sequence. When the printing layer PTL includes a first printing layer PTL1 and a second printing layer PTL2, in the manufacturing process of the window module WDM-1, the first printing layer PTL1, the ink layer IKL, the second printing layer PTL2 and the protective layer PL may be stacked in sequence.

[0139] When a defect occurs in the manufacturing process of the display device DD, rework is required to save process costs. At this time, in order to remove the adhesive layer configured on the window module WDM, physical rubbing with a dust-free cloth and chemical rubbing with alcohol cleaning are performed at the same time. At this time, the ink layer IKL is damaged, and defects such as staining of the pigment or dye contained in the ink layer IKL may occur.

[0140] According to an embodiment, the window module WDM includes a protective layer PL containing a polymer resin, so that the ink layer IKL can be prevented from being damaged during the rubbing process. In particular, the protective layer PL according to an embodiment includes a polymer resin formed by polymerization of monomers, which has excellent chemical resistance and wear resistance, so that it is less damaged during the rubbing process and can effectively protect the ink layer IKL, wherein the monomers include: a first monomer of an acrylic monomer substituted with a hydroxyl group; a second monomer containing an epoxy group; and at least one of a third monomer substituted with or containing an unsubstituted phenyl group and a fourth monomer of an acrylic monomer substituted with or containing an unsubstituted bicycloalkyl group.

[0141] The present disclosure is described in more detail below through specific examples and comparative examples. The following examples are merely examples to help understanding of the present disclosure, and the scope of the present disclosure is not limited thereto.

[0142] 1. Polymerization of polymer resin

[0143] (Polymerization Example of Polymer Resin)

[0144] Ethyl carbitol acetate (ECA) was added as a solvent in a round flask (2L) and maintained at 80°C. After the first to fourth monomers (750g in total) were mixed in the ratios described in the following table, AIBN (azobisisobutyronitrile) as a free radical initiator was stirred and dissolved with the monomer mixture. The amount of initiator was based on the molar number of the entire monomer, and about 0.2 mol% was added. After that, the mixture of the monomer and the initiator was dripped into the solvent drop by drop for 2 hours. After the mixture was fully added, the reaction was maintained for another 4 hours, and then the polymer resin contained in the protective layer of one embodiment was prepared through cooling and filtering.

[0145] [Table 1]

[0146]

[0147] Table 1 shows the molecular weight and glass transition temperature of the polymer resin based on the molar ratio of the first to fourth monomers. The weight average molecular weight of the acrylic resins represented by Polymerization Examples 1 to 5 satisfies the range of 20,000 to 30,000, and the glass transition temperature satisfies the range of 80°C to 92°C.

[0148] In the polymerization example, HPA (hydroxypropyl acrylate), EA (epoxy acrylate), styrene, and IBOA (isobornyl acryalte) were used as the first to fourth monomers, respectively.

[0149] The structure of epoxy acrylate used in the polymerization example is as follows, and the same applies to the following.

[0150]

[0151] 2. Evaluation of polymer resin properties

[0152] [Table 2]

[0153]

[0154] Table 2 is a table showing the results of evaluating the properties of polymer resins prepared by mixing monomers, inorganic particles and crosslinking agents at the ratios described above. In the examples, HPA (hydroxypropyl acrylate), EA (epoxy acrylate), styrene and IBOA (isobornyl acryalte) were used as the first to fourth monomers, respectively. In Comparative Example 6, BA (butyl acrylate) was used. As a crosslinking agent, hexamethylene diisocyanate was used to protect the isocyanate group as a protecting group.

[0155] The alcohol rubbing evaluation is to screen print the polymer resin on the glass, harden it at 150°C for 30 minutes, leave it for 24 hours, and then use an alcohol rubbing machine under a load of 1000g to measure the number of rubbing times required for the polymer resin to be completely removed. The situation where the number of rubbing times exceeds 150 times is evaluated as good.

[0156] The cross-cut evaluation is to print the polymer resin on the glass screen, harden it at 150°C for 30 minutes, leave it for 24 hours, and then use a knife to make scratches in a grid shape with a certain width. After that, stick a tape on the applied polymer resin and peel it off at a certain speed. The case where the result of 4B or more is derived is evaluated as good, and the case where the result of 3B or less is derived is evaluated as poor.

[0157] The light transmittance was evaluated by screen-printing the polymer resin on glass, curing it at 150° C. for 30 minutes, leaving it for 24 hours, and then measuring the transmittance of visible light having a central wavelength of 540 nm.

[0158] Example 1, Example 2, Comparative Example 1 and Comparative Example 2 are examples and comparative examples for determining the ratio of the crosslinking agent. When the addition ratio of the crosslinking agent is less than 20wt% based on the total weight of the monomer, the number of alcohol rubbings decreases, the crosslinking density of the polymer resin decreases, and the chemical resistance decreases. When it exceeds 25wt%, the light transmittance decreases.

[0159] Example 3 and Comparative Examples 3 to 6 are examples and comparative examples for determining the ratio of monomers. Example 3 showed excellent results in transmittance evaluation, alcohol rubbing evaluation, and cross-cutting evaluation. Referring to Comparative Examples 3 and 4, when the second monomer and the third monomer were mixed at a ratio of 80 mol%, the cross-cutting characteristics were reduced, and the hardness was too high, resulting in low durability. Referring to Comparative Example 6, when butyl acrylate was added to replace the second monomer, the number of alcohol rubbings was reduced, showing a characteristic of reduced chemical resistance. That is, when referring to Comparative Example 6, it can be seen that it is not simply reducing T g In order for the polymer resin to show good properties, it is necessary to contain a certain amount of the second monomer.

[0160] Referring to Comparative Example 5, excellent results were shown in all of the transmittance evaluation, alcohol rubbing evaluation, and cross cut evaluation. However, as described later with reference to Table 3, poor characteristics were shown in the yellowing evaluation.

[0161] [Table 3]

[0162]

[0163] Table 3 shows the results of evaluating the properties of polymer resins prepared by mixing monomers, inorganic particles, and a crosslinking agent at the ratios described above.

[0164] Yellowing evaluation was performed by printing the polymer resin on glass, irradiating it with ultraviolet rays (UV A and UV B) for 72 hours, and then measuring the change in color coordinates (Delta E, ΔE). When the change in color coordinates was less than 0.2, it was evaluated as good.

[0165] For pencil hardness evaluation, pencils with different hardness were placed at a 45-degree angle on the polymer resin printed on the glass, and the polymer resin was scraped with a load of 1 kg and a speed of 100 mm / min. After that, the damage on the polymer resin surface was visually confirmed and tested. The polymer resin scraped with a 2H hardness pencil was recorded as 2H, and the polymer resin scraped with a 3H hardness pencil was recorded as 3H.

[0166] The cross-cut evaluation was performed in the same manner as described in Table 2.

[0167] Referring to Comparative Examples 5 to 7, when the mol% of epoxy acrylate exceeds 40, the amount of change in color coordinates exceeds 0.2, and it is judged that excellent effects can be achieved when the ratio of epoxy acrylate is about 30 mol% or less.

[0168] When the embodiments and comparative examples in Tables 2 and 3 are combined, it is judged that when the polymer resin of one embodiment is based on the first monomer to the fourth monomer as a whole, it contains 10 mol% or more and 30 mol% or less of the first monomer, 10 mol% or more and 30 mol% or less of the second monomer, and 50 mol% or more and 80 mol% or less of at least one of the third monomer and the fourth monomer, an excellent effect can be achieved. In addition, it is judged that when the cross-linking agent is added at a ratio of 20 wt% or more and 25 wt% or less of the weight of the first monomer to the fourth monomer and the cross-linking agent as a whole, an excellent effect can be achieved.

[0169] The polymer resin according to an embodiment is polymerized from monomers, wherein the monomers include: a first monomer of an acrylic monomer having a substituted hydroxyl group; a second monomer including an epoxy group; and at least one of a third monomer of an acrylic monomer having a substituted or unsubstituted phenyl group or a fourth monomer of an acrylic monomer having a substituted or unsubstituted bicycloalkyl group. Therefore, the polymer resin can have excellent durability, wear resistance, and chemical resistance.

[0170] According to an embodiment of the present invention, the window module and the display device include a protective layer containing the polymer resin described above, thereby improving the efficiency of the rework process.

[0171] The present invention has been described with reference to the embodiments, but a person skilled in the art will understand that various modifications and variations can be made to the present invention without departing from the concept and scope of the present invention as recorded in the claims. In addition, the embodiments disclosed in the present invention are not intended to limit the technical concept of the present invention, and should be interpreted as including all technical concepts in the claims and their equivalents in the scope of the present invention.

Claims

1. A window module, in, include: window; A first printing layer is disposed on the window and defines an opening; an ink layer filling the opening and comprising a matrix resin and at least one of a pigment and a dye dispersed in the matrix resin; and a protective layer covering the ink layer, The protective layer comprises a polymer resin formed by polymerization of monomers, wherein the monomers comprise: a first monomer of an acrylic monomer substituted with a hydroxyl group; a second monomer comprising an epoxy group; and at least one of a third monomer of an acrylic monomer substituted with or comprising an unsubstituted phenyl group and a fourth monomer of an acrylic monomer substituted with or comprising an unsubstituted bicycloalkyl group. The protective layer is based on the entirety of the first monomer to the fourth monomer. containing 10 mol % or more and 30 mol % or less of the first monomer, containing 10 mol % or more and 30 mol % or less of the second monomer, At least one of the third monomer and the fourth monomer is contained in an amount of 50 mol % or more and 80 mol % or less.

2. The window module according to claim 1, in, The first monomer to the fourth monomer are respectively represented by the following chemical formulas 1 to 4: [Chemical formula 1] [Chemical formula 2] [Chemical formula 3] [Chemical formula 4] In the chemical formula 1 to the chemical formula 4, R 1 , R 3 , R 4 , R 5 , R 7 and R 8 are each independently a hydrogen atom or a methyl group, R 2 is a hydroxyl group or a hydroxymethyl group, R 6 is a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a and b are each independently an integer of 0 to 5.

3. The window module according to claim 1, in, The second monomer is represented by the following chemical formula 2-1: [Chemical formula 2-1] In the chemical formula 2-1, R 9 is a hydrogen atom or a methyl group, R 10 It is methylene or oxymethylene.

4. The window module according to claim 1, in, The polymer resin contains all of the third monomer and the fourth monomer.

5. The window module according to claim 1, in, The first monomer includes at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate and hydroxypropyl acrylate, The second monomer includes at least one of bisphenol A type epoxy monomer, glycidyl methacrylate, glycidyl acrylate and allyl glycidyl ether, The third monomer includes at least one of isopropenylbenzene and tert-butylstyrene, The fourth monomer includes at least one of isobornyl acrylate and isobornyl methacrylate.

6. The window module according to claim 1, in, The polymer resin is also polymerized with a cross-linking agent.

7. The window module according to claim 6, in, Based on the total weight of the first to fourth monomers, the weight ratio of the cross-linking agent is greater than or equal to 20 wt % and less than or equal to 25 wt %.

8. The window module according to claim 6, in, The cross-linking agent includes at least one of an isocyanate cross-linking agent and an amine cross-linking agent.

9. The window module according to claim 1, in, The polymer resin further includes inorganic particles.

10. The window module according to claim 9, in, The inorganic particles are barium sulfate.

11. The window module according to claim 1, in, The protective layer has a visible light transmittance of 99% or more with a central wavelength of 540 nm.

12. The window module according to claim 1, in, The ink layer includes: a first portion filling the opening; and a second portion extending from the first portion and disposed on the first printing layer.

13. The window module according to claim 12, in, The window module further includes: a second printing layer, arranged on the first printing layer, At least a portion of the second portion of the ink layer is disposed between the first printed layer and the second printed layer.

14. A display device, in, include: A window module, defined by a frame area and a transmission area adjacent to the frame area, wherein the frame area includes a semi-transmission area for transmitting infrared rays and a non-transmission area surrounding the semi-transmission area; an infrared sensor overlapping the semi-transmissive area; as well as A display panel overlaps a portion of the frame area and the transmission area, The window module comprises: window; A first printing layer is arranged in the non-transmitting area; an ink layer disposed in the semi-transmissive region and comprising a matrix resin and at least one of a pigment and a dye dispersed in the matrix resin; and a protective layer covering the ink layer, The protective layer comprises a polymer resin formed by polymerization of monomers, wherein the monomers comprise: a first monomer of an acrylic monomer substituted with a hydroxyl group; a second monomer comprising an epoxy group; and at least one of a third monomer of an acrylic monomer substituted with or comprising an unsubstituted phenyl group and a fourth monomer of an acrylic monomer substituted with or comprising an unsubstituted bicycloalkyl group. The protective layer is based on the entirety of the first monomer to the fourth monomer. containing 10 mol % or more and 30 mol % or less of the first monomer, containing 10 mol % or more and 30 mol % or less of the second monomer, At least one of the third monomer and the fourth monomer is contained in an amount of 50 mol % or more and 80 mol % or less.

15. The display device according to claim 14, in, The first monomer to the fourth monomer are respectively represented by the following chemical formulas 1 to 4: [Chemical formula 1] [Chemical formula 2] [Chemical formula 3] [Chemical formula 4] In the chemical formula 1 to the chemical formula 4, R 1 , R 3 , R 4 , R 5 , R 7 and R 8 are each independently a hydrogen atom or a methyl group, R 2 is a hydroxyl group or a hydroxymethyl group, R 6 is a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a and b are each independently an integer of 0 to 5.

16. The display device according to claim 14, in, The display device further includes a second printing layer, which is disposed on the first printing layer. The ink layer includes: a first portion disposed in the semi-transmission area; and a second portion extending from the first portion and disposed in the non-transmission area.

17. The display device according to claim 14, in, The polymer resin is also polymerized from at least one of an isocyanate crosslinking agent and an amine crosslinking agent.

18. A polymer resin, in, The polymer resin is polymerized by a first monomer represented by the following chemical formula 1, a second monomer represented by the following chemical formula 2, a third monomer represented by the following chemical formula 3, a fourth monomer represented by the following chemical formula 4, and at least one selected from an isocyanate crosslinking agent and an amine crosslinking agent. The polymer resin is based on the entirety of the first monomer to the fourth monomer. containing 10 mol % or more and 30 mol % or less of the first monomer, containing 10 mol % or more and 30 mol % or less of the second monomer, Containing 50 mol % or more and 80 mol % or less of at least one of the third monomer and the fourth monomer, [Chemical formula 1] [Chemical formula 2] [Chemical formula 3] [Chemical formula 4] In the chemical formula 1 to the chemical formula 4, R 1 , R 3 , R 4 , R 5 , R 7 and R 8 are each independently a hydrogen atom or a methyl group, R 2 is a hydroxyl group or a hydroxymethyl group, R 6 is a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a and b are each independently an integer of 0 to 5.

19. The polymer resin according to claim 18, in, The first monomer includes at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate and hydroxypropyl acrylate, The second monomer includes a bisphenol A type epoxy monomer, The third monomer includes at least one of isopropenylbenzene and tert-butylstyrene, The fourth monomer includes at least one of isobornyl acrylate and isobornyl methacrylate.

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