Primer layer, manufacturing method thereof, laminate comprising primer layer, display window, and display device

Abstract

The present invention relates to a primer layer, a manufacturing method therefor, a laminate comprising the primer layer, a display window, and a display device, wherein the primer layer is manufactured using a composition for forming a primer layer, the composition comprising a photocurable (meth)acrylate-based oligomer and an acrylic acid-based monomer, and the acrylic acid-based monomer is included in an amount of 50 to 90 parts relative to the total of 100 parts by weight. The primer layer does not comprise a silane coupling agent.

Description

Primer layer and method for manufacturing the same, laminate including the primer layer, display window and display device

[0001] The present invention relates to a primer layer and a method for manufacturing the same, a laminate including the primer layer, a display window, and a display device.

[0002]

[0003] Recently, thin display devices using display devices such as liquid crystal displays (LCDs) or organic light emitting diode displays (OLEDs) have attracted significant attention. In particular, these thin display devices are implemented in the form of touch screen panels and are widely used in various smart devices characterized by portability, such as smartphones, tablet PCs, and various wearable devices. Recently, thin glass with an average thickness of 300㎛ or less has been applied to further increase the portability and usability of portable devices. In particular, flexible ultra-thin glass with a thickness of 0.1㎜ (100㎛) or less can freely change its shape not only in portable devices but also in fixed devices, thereby improving space utilization.

[0004] Korean Patent Publication No. 10-2336592 relates to a coating composition applicable to one or both sides of a partially slimming glass, and provides a resin composition for coating a flexible cover window, characterized in that it comprises a urethane (meth) acrylate oligomer, a first photocurable acrylic monomer, a second photocurable acrylic monomer, an alkoxy silane coupling agent, a siloxane additive, and a photopolymerization initiator in respective content ranges, and a flexible cover window using the same. However, when applied to UTG (ultra-thin glass with a thickness of 100 ㎛ or less), a silane coupling agent containing a thiol group is used as a raw material to ensure adhesion, so a post-heat treatment process is essential, and in this step, the heat generated during the process may cause damage to the laminated film, and in addition to the complexity of the process due to the requirement of a heat treatment process, the silane coupling agent itself is very expensive compared to organic materials, which increases the overall process cost and worsens economic feasibility. In addition, the need for an additional heat treatment process complicates the process, which is a disadvantage.

[0005]

[0006] The present invention aims to provide a primer layer capable of achieving high initial adhesion between a glass substrate and a primer layer and high adhesion even under high temperature and high humidity conditions by using only pure organic substances without including a silane group in order to solve the above-described problem, a method for producing the same, and a laminate, a display window, and a display device including the primer layer.

[0007] However, the problems to be solved by the present invention are not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the description below.

[0008]

[0009] The present invention relates to a primer layer manufactured from a composition for forming a primer layer, which comprises a photocurable (meth)acrylate oligomer; and an acrylic acid monomer; and is characterized in that the composition is manufactured by including the acrylic acid monomer in an amount of 50 to 90 parts by weight based on 100 parts by weight of the total composition for forming a primer layer, and does not contain a silane coupling agent.

[0010] In the present invention, the acrylic acid-based monomer may include at least one selected from acrylic acid, methacrylic acid, 2-carboxyethylacrylic acid, 3-carboxypropylacrylic acid, 2-(meth)acryloyloxyacetic acid, 3-(meth)acryloyloxypropyl acid, and 4-(meth)acryloyloxybutyric acid.

[0011] According to the present invention, the composition for forming the primer layer may further include at least one selected from the group consisting of a leveling agent, an initiator, an anti-foaming agent, an anti-shrinkage agent, a stabilizer, and a solvent.

[0012] In the present invention, the leveling agent may be at least one selected from the group consisting of a silicone-based leveling agent, a fluorine-based leveling agent, and an acrylic-based leveling agent.

[0013] In the present invention, the thickness of the primer layer may be greater than 0.1 µm and less than 50 µm.

[0014] In addition, the present invention relates to a method for manufacturing the primer layer, and may be characterized in that it does not include a step for solvent drying and includes a UV curing step.

[0015] The present invention also relates to a laminate comprising a glass substrate and the primer layer on one surface of the glass substrate.

[0016] In the present invention, the thickness of the glass substrate may be 10 to 300 ㎛.

[0017] In the present invention, the thickness of the glass substrate may be 10 to 100 ㎛.

[0018] The present invention also relates to a display window including the laminate.

[0019] Additionally, according to one embodiment of the present invention, the display window may be flexible.

[0020] The present invention also relates to a display device including the laminate.

[0021]

[0022] The laminate, display window and display device including the primer layer according to the present invention have the advantages of excellent durability and / or optical properties, as they have high initial adhesion and excellent adhesion even under high temperature and high humidity conditions, excellent transmittance and no haze, without including a silane group in manufacturing the composition for forming the primer layer using only pure organic materials.

[0023] Furthermore, the method for manufacturing a primer layer according to the present invention does not include a silane group, so no separate heat treatment for solvent drying is required, and adhesion to glass can be secured solely through a UV curing process, thereby preventing damage to the substrate due to heat. Accordingly, the method for manufacturing a primer layer according to the present invention also has advantages in terms of process convenience and / or economic feasibility.

[0024]

[0025] FIG. 1 is a cross-sectional view simply illustrating a laminate according to one embodiment of the present invention.

[0026] In the above drawing, each symbol represents the following:

[0027] 10: Laminate

[0028] 100: Primer layer

[0029] 200: Glassware

[0030]

[0031] The present invention relates to a primer layer manufactured from a composition for forming a primer layer, wherein the composition for forming a primer layer comprises a photocurable (meth)acrylate-based oligomer; and an acrylic acid-based monomer; and wherein the acrylic acid-based monomer is contained in an amount of 50 to 90 parts by weight based on a total of 100 parts by weight of the composition for forming a primer layer, and does not contain a silane coupling agent. The present invention relates to a primer layer and a method for manufacturing the same, a laminate including the primer layer, a display window, and a display device, wherein the display window and the display device may be applied to a flexible display.

[0032] FIG. 1 is a simplified diagram of a laminate according to an embodiment of the present invention. Referring to FIG. 1, a laminate (10) according to an embodiment of the present invention may include a glass substrate (200); and a primer layer (100) on one surface of the glass substrate, more preferably, on the upper surface of the glass substrate. Specifically, the present invention relates to a laminate and / or a display window including a glass substrate and a primer layer, wherein the primer layer may be manufactured from a composition for forming a primer layer. The composition for forming a primer layer includes a photocurable (meth)acrylate-based oligomer; and an acrylic acid-based monomer; and is manufactured by including the acrylic acid-based monomer in an amount of 50 to 90 parts by weight based on 100 parts by weight of the total composition for forming a primer layer, and may further include one or more selected from the group consisting of a leveling agent, an initiator, an anti-foaming agent, an anti-shrinkage agent, a stabilizer, and / or a solvent.

[0033] In general, conventional glass substrates (e.g., thin glass (TG)) have poor adhesion to organic materials, so they contain a material having a silane group capable of a silane coupling reaction to ensure adhesion through a post-heat treatment process. That is, compared to the conventional technology in which a heat treatment process is essential to ensure adhesion, the primer layer according to an embodiment of the present invention can secure adhesion to the glass substrate with only a pure organic material, without including a compound having a silane group, such as a silane coupling agent, in the composition for forming the primer layer. In addition, by not including the silane group, it is possible to provide a highly reliable laminate, a display window, and a display device including the same, which have excellent optical properties, such as transmittance, and excellent adhesion and durability, without requiring additional heat treatment, such as a pre-bake and / or a post-bake for drying the solvent during the process.

[0034] Hereinafter, embodiments of the present invention will be described in more detail with reference to the drawings. However, the following drawings attached to this specification illustrate preferred embodiments of the present invention and, together with the contents of the invention described above, serve to further understand the technical concept of the present invention. Therefore, the present invention should not be interpreted as being limited to the matters described in such drawings.

[0035] As used herein, the terms "comprises" and / or "comprising" are used to mean that they do not exclude the presence or addition of one or more other components, steps, operations, and / or elements other than the mentioned components, steps, operations, and / or elements. Like reference numerals refer to like elements throughout the specification.

[0036] Spatially relative terms such as "below," "bottom," "lower," "above," "top," and "upper" can be used to easily describe the relationship between one component and other components, as illustrated in the drawings. Spatially relative terms should be understood to include different orientations of the components during use or operation in addition to the orientations depicted in the drawings. For example, if a component depicted in the drawings were flipped over, something described as "below" or "lower" of another component could actually be placed "above" the other component. Thus, the exemplary term "below" can include both below and above directions. Components can also be oriented in other directions, and thus spatially relative terms can be interpreted based on their orientation.

[0037] <Primer layer (100)>

[0038] The primer layer (100) of the present invention can be manufactured using a composition for forming a primer layer, and specifically, can be formed by curing the composition for forming a primer layer. The composition for forming a primer layer comprises a photocurable (meth)acrylate-based oligomer; and an acrylic acid-based monomer; and can be manufactured by including the acrylic acid-based monomer in an amount of 50 to 90 parts by weight based on 100 parts by weight of the total of the composition for forming a primer layer, and is characterized in that it does not contain a silane coupling agent. In addition, the composition may further include known components such as one or more selected from the group consisting of a leveling agent, an initiator, an anti-foaming agent, an anti-shrinkage agent, a stabilizer, and / or a solvent known in the art for a primer layer and / or a hard coating layer, within a range that does not impair the purpose of the present invention. Preferably, the primer layer is characterized in that it does not contain a silane coupling agent, and thus may not contain a solvent, and thus, can be cured without a heat treatment process for drying a solvent before photocuring, and is characterized in that curing is possible only through a UV curing step.

[0039]

[0040] The above photocurable (meth)acrylate oligomer includes epoxy (meth)acrylate, urethane (meth)acrylate, etc., and urethane (meth)acrylate is more preferred. The above urethane (meth)acrylate can be produced in the presence of a catalyst by combining a polyfunctional (meth)acrylate having a hydroxyl group in the molecule and a compound having an isocyanate group. Specific examples of the (meth)acrylate having a hydroxy group in the molecule include at least one selected from the group consisting of 2-hydroxyethyl (meth)acrylate, 2-hydroxyisopropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, caprolactone ring-opening hydroxyacrylate, pentaerythritol tri / tetra(meth)acrylate mixture, and dipentaerythritol penta / hexa(meth)acrylate mixture. In addition, specific examples of compounds having the above isocyanate group include 1,4-diisocyanatobutane, 1,6-diisocyanatohexane, 1,8-diisocyanatooctane, 1,12-diisocyanatododecane, 1,5-diisocyanato-2-methylpentane, trimethyl-1,6-diisocyanatohexane, 1,3-bis(isocyanatomethyl)cyclohexane, trans-1,4-cyclohexenediisocyanate, 4,4'-methylenebis(cyclohexylisocyanate), isophoronediisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, xylene-1,4-diisocyanate, tetramethylxylene-1,3-diisocyanate, At least one may be selected from the group consisting of 1-chloromethyl-2,4-diisocyanate, 4,4'-methylenebis(2,6-dimethylphenylisocyanate), 4,4'-oxybis(phenylisocyanate), a trifunctional isocyanate derived from hexamethylene diisocyanate, and trimethanepropanol adduct toluene diisocyanate.

[0041] The photocurable (meth)acrylate oligomers exemplified above can be used alone or in combination of two or more.

[0042] The above photocurable (meth)acrylate oligomer is not particularly limited, but is preferably included in an amount of 1 to 80 parts by weight based on 100 parts by weight of the total composition for forming the primer layer. If it is less than 1 part by weight, it is difficult to achieve sufficient hardness improvement, and if it exceeds 80 parts by weight, there is a problem that curling of the laminate becomes severe.

[0043]

[0044] In addition, the composition for forming a primer layer of the present invention may further include a photocurable (meth)acrylate monomer in addition to the photocurable (meth)acrylate oligomer described above. The photocurable (meth)acrylate monomer is not particularly limited, but may, for example, have an unsaturated group such as a (meth)acryloyl group, a vinyl group, a styryl group, or an allyl group in the molecule as a photocurable functional group, and among these, a monomer having a (meth)acryloyl group is more preferable. The monomer having the above (meth)acryloyl group includes, as specific examples, neopentyl glycol acrylate, 1,6-hexanediol (meth)acrylate, propylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, 1,2,4-cyclohexane tetra(meth)acrylate, pentaglycerol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, From the group consisting of dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol tri(meth)acrylate, tripentaerythritol hexatri(meth)acrylate, bis(2-hydroxyethyl)isocyanurate di(meth)acrylate, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, hydroxybutyl(meth)acrylate, isooctyl(meth)acrylate, iso-dexyl(meth)acrylate, stearyl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, phenoxyethyl(meth)acrylate, and isoborneol(meth)acrylate More than one type can be selected.As the above photocurable urethane (meth)acrylate oligomer commercially available products, those having an aliphatic main chain structure, such as PU210, PU212, PU256, PU2100, PU320, PU340, PU3000, PU3450, PU5000 of Miwon Specialty Chemical Co., Ltd., UN333, UN2700, UN3230HS of Negami Industrial Co., Ltd., UN6200, UN6300, UN7700 of Negami Industrial Co., Ltd., having an ester group in the aliphatic main chain, and UN9000PEP of Negami Industrial Co., Ltd., having a carbonate group in the aliphatic main chain, etc. can be used.

[0045]

[0046] The above acrylic acid monomer is included in the composition to achieve adhesion through chemical bonding with a glass substrate, and is characterized by having an acid group within the molecule. Specifically, adhesion is achieved by hydrogen bonding between the hydroxyl group on the surface of the hydrophilic-treated glass substrate and the carboxylic acid group of acrylic acid.

[0047] The above acrylic acid monomer may include, for example, at least one selected from acrylic acid, methacrylic acid, 2-carboxyethylacrylic acid, 3-carboxypropylacrylic acid, 2-(meth)acryloyloxyacetic acid, 3-(meth)acryloyloxypropyl acid, and 4-(meth)acryloyloxybutyric acid, and preferably includes acrylic acid in that the equivalent ratio of carboxylic acid groups per unit volume is high, thereby providing excellent glass adhesion even at a small content. The above-mentioned acrylic acid monomers may be used alone and / or in combination of two or more.

[0048] The acrylic acid monomer is not particularly limited, but is preferably included in an amount of 50 to 90 parts by weight based on 100 parts by weight of the total composition for forming the primer layer. If it is less than 50 parts by weight, the chemical bonding portion with the glass substrate is small, resulting in insufficient adhesion. If it exceeds 90 parts by weight, the problem of severe curling of the laminate may occur.

[0049]

[0050] The composition for forming the primer layer may further include a leveling agent, and the leveling agent is added to improve the smoothness and coatability of the coating film when applying the composition, and may include at least one selected from the group consisting of a silicone-based leveling agent, a fluorine-based leveling agent, and an acrylic-based leveling agent. When the leveling agent is included in the composition for forming the primer layer, there is an advantage in that smoothness and coatability can be provided when forming the coating film. Specifically, the leveling agent is BYK-323, BYK-331, BYK-333, BYK-337, BYK-373, BYK-375, BYK-377, BYK-378, BYK-3530, BYK-3560, BYK-358N, BYK-361N of BYK Chemical Co., Ltd., and TEGO Glide 410, TEGO Glide 411, TEGO Glide 415, TEGO Glide 420, TEGO Glide 432, TEGO Glide 435, TEGO Glide 440, TEGO Glide 450, TEGO Glide 455, TEGO Rad 2100, TEGO Rad 2200N, TEGO Rad 2250, TEGO of Daegu Chemical Co., Ltd. Rad 2300, TEGO Rad 2500, 3M's FC-4430, FC-4432, etc. can be used, but are not limited thereto, and leveling agents commonly used in the industry can be applied.

[0051] The leveling agent may be included in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the primer layer forming composition, but is not limited thereto. However, when the leveling agent is included in the primer layer forming composition within the above range, there is an advantage in that the smoothness and coatability of the coating film can be maximized while maintaining the hardness and flexibility excellently.

[0052]

[0053] The above initiator may be used without limitation as long as it is used in the relevant technical field. For example, one or more selected from the group consisting of hydroxyketones, aminoketones, hydrogen-abstracting initiators, and combinations thereof may be used. Specifically, the initiator may be at least one selected from the group consisting of 2-methyl-1-[4-(methylthio)phenyl]2-morpholinepropanone-1, diphenyl ketone, benzyldimethyl ketal, 2-hydroxy-2-methyl-1-phenyl-1-one, 4-hydroxycyclophenyl ketone, 2,2-dimethoxy-2-phenyl-acetophenone, anthraquinone, fluorene, triphenylamine, carbazole, 3-methylacetophenone, 4-xenoloacetophenone, 4,4-dimethoxyacetophenone, 4,4-diaminobenzophenone, 1-hydroxycyclohexylphenyl ketone, benzophenone, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, and combinations thereof.

[0054] These initiators are used in an amount of 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the total composition for forming a primer layer. If the content is less than the above range, the curing speed of the composition is slow and under-curing occurs, resulting in poor mechanical properties. Conversely, if the content exceeds the above range, cracks may occur in the coating film due to over-curing.

[0055]

[0056] The above solvent can be used without limitation as long as it is known as a solvent for a composition for forming a coating layer in the technical field of the present invention that can dissolve or disperse the composition mentioned above. Available solvents include alcohols (methanol, ethanol, isopropanol, butanol, methyl cellusob, ethylsolusob, etc.), ketones (methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, cyclohexanone, etc.), acetates (ethyl acetate, propyl acetate, normal butyl acetate, tert-butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate, etc.), hexane-based solvents (hexane, heptane, octane, etc.), benzene-based solvents (benzene, toluene, xylene, etc.), ether-based solvents (diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, etc.) can be preferably used. The solvents exemplified above can be used alone or in combination of two or more.

[0057] The composition for forming a primer layer may or may not contain a solvent, and when it contains a solvent, the solvent may be included as a residual amount compared to other components. Specifically, the "residual amount" in the present invention means the residual amount so that the total weight of the composition including the essential components of the present invention and other additional components becomes 100% by weight, and the meaning of the "residual amount" is not limited to the composition of the present invention not containing additional components. For example, the solvent may be used in an amount of 20 to 98 parts by weight based on 100 parts by weight of the total composition for forming a primer layer. If the content of the solvent is less than the content, the viscosity is high, which reduces workability and makes it impossible to reduce the thickness of the coating layer, which may result in a decrease in flexibility. On the other hand, if it exceeds the above range, the desired film thickness cannot be formed, and the coating solution may flow down during the drying process, contaminating the opposite surface of the glass or film and causing stains. Therefore, it is necessary to appropriately control the amount within the above range.

[0058] More preferably, in one embodiment of the present invention, the composition for forming a primer layer may not include a solvent. By including an acrylic acid-based monomer or the like in place of the solvent, glass adhesion can be achieved, and since the monomer itself has a very low viscosity, the dilution ability is excellent, making it easy to control the viscosity of the primer composition. In addition, if a solvent is not included, heat treatment processes such as pre-bake and / or post-bake for drying the solvent during the process can be omitted.

[0059]

[0060] <Method for manufacturing the primer layer>

[0061] The above primer layer (100) can be formed by applying and curing a composition for forming a primer layer on a glass substrate (200). The application is not particularly limited, and known methods such as slit coating, knife coating, spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, screen printing, gravure printing, flexographic printing, offset printing, inkjet coating, dispenser printing, nozzle coating, and capillary coating can be used.

[0062] According to one embodiment of the present invention, the primer layer (100) is characterized in that it can sufficiently secure adhesion to the glass substrate through a UV curing process without performing a thermal curing process such as a pre-bake and / or a post-bake after applying a primer layer forming composition according to the present invention to one surface of a glass substrate (200) to be described later. Specifically, adhesion can be secured and / or optical performance can be improved by forming a hydrogen bond between the carboxylic acid group of acrylic acid and the hydroxyl group on the surface of the glass substrate. In the case of photocuring (UV curing), 300 to 2000 mJ / cm 2 It is desirable to form a primer layer by examining the UV accumulated light amount.

[0063] The above primer layer (100) preferably has a thickness of more than 0.1 μm and less than 50 μm. More preferably, the thickness is more than 5.0 μm and less than 40 μm, which is advantageous in terms of adhesion to the glass substrate and optical properties. If the thickness is too thin, which is less than the above range, adhesion to the upper portion of the primer layer may be reduced, and conversely, if the thickness of the primer layer (100) is too thick, problems such as curling of the laminate including the glass substrate and severe haze of the primer layer may occur.

[0064]

[0065] <Laminates, display windows and display devices>

[0066] A laminate (10) according to one embodiment of the present invention may include a glass substrate (200); and a primer layer (100) on one surface of the glass substrate.

[0067] The primer layer (100) described above may be applied to the contents of the above-described <primer layer (100)>, so description thereof will be omitted. The primer layer (100) may be positioned on one or both sides of the glass substrate (200). The primer layer is not limited thereto, and may include various functional layers known to be usable in the art depending on the intended use. By including the primer layer (100) on the glass substrate (200), excellent glass adhesion can be achieved through bonding with hydroxyl groups on the glass surface. Therefore, high adhesion can be maintained even after initial exposure to high temperature and high humidity conditions. In addition, the laminate or display window according to the present invention has a high transmittance of 85% or more, preferably 90% or more, for the entire visible light range, specifically, for all light, and haze generation is suppressed, so that a display window with excellent optical properties can be provided.

[0068]

[0069] Glassware (200)

[0070] The glass substrate (200) of the present invention is intended to support other substrates and / or panels, and any transparent glass can be used without limitation, and preferably silicate glass can be used. The silicate glass is a glass mainly composed of anhydrous silica (silica) that exists naturally in the form of silica sand. The structure of the silicate glass has a very high density and very strong bonds with oxygen and water, so it exhibits high transmittance, making it suitable for use as a display substrate. In addition, it is stable without shrinkage or warping even when going through a photocuring process.

[0071] In addition, the glass substrate used in the above-described material may be a thin glass (TG) having a thickness of 10 to 300 ㎛. More specifically, unlike existing glass, it may be an ultra-thin glass (Ultra Thin Glass, UTG) having a thickness of 100 ㎛ or less in order to have excellent bending resistance that does not break even when bent or folded for use in a flexible display substrate. In this case, it is more preferable to have a thickness of 60 ㎛ or less, and glass having a thickness thinner than 10 ㎛ has a problem in that it is easy to break during the process.

[0072]

[0073] In addition, the glass substrate (200) may have the same thickness as a whole, and according to another embodiment of the present invention, may have a flat portion and a curved portion with different thicknesses in one or more locations as needed. The flat portion may apply the contents of the glass substrate (200) described above, and the curved portion refers to a portion that is formed by slimming to be thinner than the flat portion, and the curved portion may be an area corresponding to a region where a flexible display is folded in half or a folding portion that is bent in the case of ultra-thin glass (UTG). In this case, the folding portion may include both in-folding and out-folding.

[0074] As described above, when applying a composition for forming a primer layer to the same glass substrate as the curved portion, the primer layer applied on the glass substrate can be applied in different portions so that the laminate has an overall flat surface. In another embodiment, a primer layer of uniform thickness can be formed along the flat portion and / or the curved portion of the glass substrate so that the laminate has an overall different thickness.

[0075]

[0076] In addition, the laminate (10) may be surface-treated as needed. Such surface treatments include dry treatments such as plasma treatment, corona treatment, and primer treatment, and chemical treatments such as alkaline treatment including saponification treatment.

[0077]

[0078] The present invention encompasses a display window comprising the laminate. The display window may be a flexible display window when using ultra-thin glass having a thickness of 100 μm or less. Furthermore, the present invention provides a display device comprising the display window, which has excellent adhesion between a glass substrate and a polyimide film, excellent transmittance, and reduced defective pixels such as haze. Specifically, the display device may be used as a display window for displays such as LCDs, OLEDs, LEDs, and FEDs, or for various mobile communication terminals utilizing the same, or for touch panels of smartphones or tablet PCs.

[0079]

[0080] The above display device may be a variety of display devices such as a conventional liquid crystal display, an electroluminescent display, a plasma display, and a field emission display, and may be a display device including a touch sensor.

[0081]

[0082] Hereinafter, specific embodiments of the present invention will be described. However, the present invention is not limited to the embodiments disclosed below, but can be implemented in various different forms. These embodiments are provided only to ensure that the disclosure of the present invention is complete and to fully inform those skilled in the art of the scope of the invention, and the present invention is defined only by the scope of the claims. In the examples, "%" and "parts" represent mass% and mass parts, respectively, unless otherwise specified.

[0083]

[0084] Manufacturing Example 1: Manufacturing of Composition 1 for Forming a Primer Layer

[0085] 48.9 parts by weight of bifunctional urethane acrylate (Negami Kogyo Co., Ltd., UN-9000PEP), 50 parts by weight of acrylic acid, 1 part by weight of photoradical initiator (1-hydroxycyclohexylphenyl ketone), and 0.1 part by weight of silicone-based leveling agent (BYK, BYK-333) were mixed using a stirrer and filtered using a PP material filter to prepare a composition 1 for forming a primer layer.

[0086]

[0087] Manufacturing Example 2: Manufacturing of Composition 2 for Forming a Primer Layer

[0088] 29.7 parts by weight of bifunctional urethane acrylate (Negami Kogyo Co., Ltd., UN-9000PEP), 69.2 parts by weight of acrylic acid, 1 part by weight of photoradical initiator (1-hydroxycyclohexylphenyl ketone), and 0.1 part by weight of silicone-based leveling agent (BYK, BYK-333) were mixed using a stirrer and filtered using a PP material filter to prepare a composition 2 for forming a primer layer.

[0089]

[0090] Manufacturing Example 3: Manufacturing of Composition 3 for Forming a Primer Layer

[0091] 9.9 parts by weight of bifunctional urethane acrylate (Negami Kogyo Co., Ltd., UN-9000PEP), 89 parts by weight of acrylic acid, 1 part by weight of photoradical initiator (1-hydroxycyclohexylphenyl ketone), and 0.1 part by weight of silicone-based leveling agent (BYK, BYK-333) were mixed using a stirrer and filtered using a PP material filter to prepare a composition 3 for forming a primer layer.

[0092]

[0093] Manufacturing Example 4: Manufacturing of Composition 4 for Forming a Primer Layer

[0094] 29.7 parts by weight of trifunctional urethane acrylate (Miwon Specialty Chemical, PU3000), 69.2 parts by weight of acrylic acid, 1 part by weight of photoradical initiator (1-hydroxycyclohexylphenyl ketone), and 0.1 part by weight of silicone-based leveling agent (BYK, BYK-333) were mixed using a stirrer and filtered using a PP material filter to prepare a composition 4 for forming a primer layer.

[0095]

[0096] Manufacturing Example 5: Manufacturing of Composition 5 for Forming a Primer Layer

[0097] 69.2 parts by weight of trifunctional urethane acrylate (Miwon Specialty Chemical, PU3000), 29.7 parts by weight of acrylic acid, 1 part by weight of photoradical initiator (1-hydroxycyclohexylphenyl ketone), and 0.1 part by weight of silicone-based leveling agent (BYK, BYK-333) were mixed using a stirrer and filtered using a PP material filter to prepare a composition 5 for forming a primer layer.

[0098]

[0099] Manufacturing Example 6: Manufacturing of Composition 6 for Forming a Primer Layer

[0100] 48.9 parts by weight of trifunctional urethane acrylate (Miwon Specialty Chemical, PU3000), 50 parts by weight of methyl ethyl ketone, 1 part by weight of photoradical initiator (1-hydroxycyclohexyl phenyl ketone), and 0.1 part by weight of acrylic leveling agent (BYK, BYK-361N) were mixed using a stirrer and filtered using a PP material filter to prepare a composition 6 for forming a primer layer.

[0101]

[0102] Manufacturing Example 7: Manufacturing of Composition 7 for Forming a Primer Layer

[0103] 93.9 parts by weight of trifunctional urethane acrylate (Miwon Specialty Chemical, PU3000), 5 parts by weight of epoxy silane coupling agent (Shin-Etsu, KBM-503), 1 part by weight of photoradical initiator (1-hydroxycyclohexyl phenyl ketone), and 0.1 part by weight of silicone leveling agent (BYK, BYK-307) were mixed using a stirrer (using paste mixing equipment) and filtered using a PP material filter to prepare a composition 7 for forming a primer layer.

[0104]

[0105] Manufacturing Example 8: Manufacturing of Composition 8 for Forming a Primer Layer

[0106] 40.9 parts by weight of epoxy-acrylate (Kongyoungsa, SMP-220AP-E5), 2.33 parts by weight of epoxysilane (Asia Industrial 330L hardener), 2.5 parts by weight of photoradical initiator (1-hydroxycyclohexylphenyl ketone), 2.5 parts by weight of cationic initiator ((4-methylphenyl) [4-(2-methylpropyl) phenyl] iodonium hexafluorophosphate), 0.2 parts by weight of silicone-based leveling agent (BYK, BYK-307), and 51.57 parts by weight of methyl ethyl ketone (MEK) were mixed using a stirrer and filtered using a PP material filter to prepare a composition 8 for forming a primer layer.

[0107]

[0108] Examples and Comparative Examples: Manufacturing of Laminates

[0109] <Example 1>

[0110] The composition 1 for forming a primer layer manufactured in the above manufacturing example 1 was coated on a glass substrate (thickness 50 ㎛) to a thickness of 20 ㎛, and then UV accumulated light intensity was 1,000 mJ / cm in a nitrogen atmosphere. 2 The laminate of Example 1 was manufactured by investigating.

[0111]

[0112] <Example 2>

[0113] A laminate of Example 2 was manufactured in the same manner as Example 1, except that the composition 2 for forming a primer layer manufactured in Manufacturing Example 2 was used instead of the composition 1 for forming a primer layer.

[0114]

[0115] <Example 3>

[0116] A laminate of Example 3 was manufactured in the same manner as Example 1, except that the composition 3 for forming a primer layer manufactured in Manufacturing Example 3 was used instead of the composition 1 for forming a primer layer.

[0117]

[0118] <Example 4>

[0119] A laminate of Example 4 was manufactured in the same manner as Example 1, except that the composition 4 for forming a primer layer manufactured in Manufacturing Example 4 was used instead of the composition 1 for forming a primer layer.

[0120]

[0121] <Example 5>

[0122] A laminate of Example 5 was manufactured using the same method as Example 1, except that a glass substrate (flat surface thickness 100 ㎛, curved surface thickness 50 ㎛) manufactured to have curved portions in some portions was used, using the technology disclosed in Korean Patent Publication No. 10-2272926.

[0123]

[0124] <Comparative Example 1>

[0125] A laminate of Comparative Example 1 was manufactured in the same manner as Example 1, except that the primer layer forming composition 5 manufactured in Manufacturing Example 5 was used instead of the primer layer forming composition 1.

[0126]

[0127] Comparative Example 2

[0128] A laminate of Comparative Example 2 was manufactured in the same manner as Example 1, except that the primer layer forming composition 6 manufactured in Manufacturing Example 6 was used instead of the primer layer forming composition 1.

[0129]

[0130] <Comparative Example 3>

[0131] A laminate of Comparative Example 3 was manufactured in the same manner as Example 1, except that the primer layer forming composition 7 manufactured in Manufacturing Example 7 was used instead of the primer layer forming composition 1.

[0132]

[0133] <Comparative Example 4>

[0134] Instead of the composition 1 for forming a primer layer, the composition 8 for forming a primer layer prepared in the above manufacturing example 8 was dried in a solvent at 120°C for 2 minutes and 15 seconds, and then heated under nitrogen conditions at 1,000 mJ / cm 2 The laminate of Comparative Example 3 was manufactured by irradiating UV with a light amount of .

[0135]

[0136] Experimental example

[0137] The physical properties of the laminates of each of the above-mentioned examples and comparative examples were measured as follows, and the results are shown in Table 1 below.

[0138]

[0139] (1) Transmittance, haze

[0140] The transmittance and haze of the laminates manufactured in the above examples and comparative examples were measured using a haze meter (HM-150, Murakami).

[0141]

[0142] (2) Initial adhesion

[0143] After bonding the laminate to the glass with the primer layer facing upward, 100 squares were scratched in the upper surface of the primer layer with a cutter knife at 1 mm intervals in the horizontal and vertical directions, and then an adhesion test was performed three times using niche tape.

[0144] <Evaluation Criteria>

[0145] 5B: Unpeeled

[0146] 4B: Less than 5% delamination

[0147] 3B: 5% or more but less than 15% peeling

[0148] 2B: 15% or more but less than 35% peeling

[0149] 1B: 35% or more but less than 65% peeling

[0150] 0B: 65% or more peeling

[0151]

[0152] (3) Adhesive durability

[0153] The laminate was left in a 60℃ / 90%RH environment for 10 days and the adhesion test was conducted using the same method as the initial adhesion evaluation.

[0154] <Evaluation Criteria>

[0155] 5B: Unpeeled

[0156] 4B: Less than 5% delamination

[0157] 3B: 5% or more but less than 15% peeling

[0158] 2B: 15% or more but less than 35% peeling

[0159] 1B: 35% or more but less than 65% peeling

[0160] 0B: 65% or more peeling

[0161] Example Comparative Example 1 2 3 4 5 1 2 3 4 Tt (%) 9 1.9 9 2.0 9 1.9 9 1.9 9 1.8 9 2.0 9 2.1 9 2.0 9 0.4 Hz (%) 0.1 0.2 0.1 0.2 0.2 0.2 0.2 0.1 0.2 1.9 Initial Adhesion 5 B 5 B 5 B 5 B 5 B 5 B 0 B 0 B 1 B 5 B Adhesion Durability 5 B 5 B 5 B 5 B 5 B 0 B 0 B 1 B 5 B

[0162] According to the experimental data in Table 1 above, the laminate according to the present invention showed excellent evaluation results in all of the evaluations of transmittance, haze, initial adhesion, and adhesion durability. On the other hand, in the case of Comparative Example 1 where the content of the acrylic acid-based monomer was insufficient during the manufacture of the primer layer, Comparative Example 2 which did not include the acrylic acid-based monomer, and Comparative Example 3 which did not include the acrylic acid-based monomer but included a silane coupling agent, it was confirmed that the initial adhesion and adhesion durability were poor, and in the case of Comparative Example 4, which included a photocurable (meth)acrylate-based oligomer and epoxy silane, adhesion to glass could be secured because silane was included, but the optical characteristics were poor due to phase separation between the oligomer and the silane.

[0163]

[0164]

[0165] The laminate, display window and display device including the primer layer according to the present invention have the advantages of excellent durability and / or optical properties, as they have high initial adhesion and excellent adhesion even under high temperature and high humidity conditions, excellent transmittance and no haze, without including a silane group in manufacturing the composition for forming the primer layer using only pure organic materials.

Claims

1. Photocurable (meth)acrylate oligomer; and A primer layer manufactured from a composition for forming a primer layer including an acrylic acid monomer; The above acrylic acid monomer is included in an amount of 50 to 90 parts by weight based on 100 parts by weight of the total composition for forming a primer layer. A primer layer characterized in that it does not contain a silane coupling agent.

2. In claim 1, A primer layer, wherein the acrylic acid monomer comprises at least one selected from acrylic acid, methacrylic acid, 2-carboxyethylacrylic acid, 3-carboxypropylacrylic acid, 2-(meth)acryloyloxyacetic acid, 3-(meth)acryloyloxypropyl acid, and 4-(meth)acryloyloxybutyric acid.

3. In claim 1, The composition for forming the primer layer further comprises at least one selected from the group consisting of a leveling agent, an initiator, an anti-foaming agent, an anti-shrinkage agent, a stabilizer, and a solvent.

4. In claim 3, The primer layer, wherein the leveling agent is at least one selected from the group consisting of a silicone-based leveling agent, a fluorine-based leveling agent, and an acrylic-based leveling agent.

5. In claim 1, A primer layer having a thickness of more than 0.1㎛ and less than 50㎛.

6. A method for manufacturing the primer layer of claim 1, A method for manufacturing a primer layer, characterized in that it does not include a step for solvent drying and includes a UV curing step.

7. Glass materials; and A laminate comprising a primer layer according to claim 1 on one side of the glass substrate.

8. In claim 7, A laminate having a thickness of the above glass substrate of 10 to 300 ㎛.

9. In claim 7, A laminate having a thickness of the above glass substrate of 10 to 100 ㎛.

10. A display window comprising a laminate according to any one of claims 7 to 9.

11. In claim 10, The above display window is a flexible display window.

12. A display device comprising a laminate according to any one of claims 7 to 9.

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