Anti-adhesion hard coating film

Abstract

An anti-sticking hard coat film includes a transparent substrate and an anti-sticking hard coat layer on the transparent substrate, wherein the anti-sticking hard coat layer includes an acrylic binder resin, a plurality of silica nanoparticles, and an acrylate-ether group-containing surfactant, wherein the silica nanoparticles include a plurality of hydrophilic silica nanoparticles and a plurality of hydrophobic silica nanoparticles and form a plurality of micron-sized silica nanoparticle flocs, and a ratio of an average secondary particle diameter of the silica nanoparticle flocs to a thickness of the anti-sticking hard coat layer is between 0.80 and 1.80 and a water contact angle of a surface of the anti-sticking hard coat layer is not greater than 80 degrees. The anti-sticking hard coat film of the present invention has a concave-convex surface, can provide anti-sticking properties, and can provide effective anti-rainbow effects.

Description

TECHNICAL FIELD

[0001] The present application relates to an anti-sticking hard coat film, in particular, a hard coat film with anti-sticking property and low water contact angle. BACKGROUND

[0002] With the increasing dependence of consumers on touch panels and the increasing production yield of touch panels, liquid crystal displays with touch modules are moving towards medium and large sizes. Air bonding of the touch module to the liquid crystal display module in the mouth-shaped type is one of the mainstream trends, but the air layer and the refractive index of the glass between the touch module and the liquid crystal display module in the mouth-shaped type air bonding cause the optical effect to be affected when light passes through the liquid crystal display module, crosses the air layer, and reaches the touch module. The greater the size, the more the force exerted by the finger when pressing the touch module, which causes the touch module to bend and approach the surface of the liquid crystal display module, resulting in sticking or Newton's ring phenomenon, also known as water ripple phenomenon, which affects image quality.

[0003] To solve the water ripple phenomenon caused by the operation of the touch panel and resulting in poor image quality, an optical film with a rough surface is used on the surface of the liquid crystal display module and the touch module in the mouth-shaped type air bonding to reduce the sticking phenomenon between the touch module and the liquid crystal display module. However, increasing the surface roughness to avoid sticking between the films of the modules may cause the mouth-shaped type air bonding to be difficult to adhere, and may have problems such as poor haze and image clarity or difficulty in suppressing rainbow stripes, which affect the display quality. SUMMARY

[0004] The present application provides an anti-sticking hard coat film for air bonding of a touch module and a liquid crystal display module in the mouth-shaped type, which has excellent anti-sticking property and rainbow stripe suppression effect, good image clarity, and good adhesion in the mouth-shaped type air bonding of the liquid crystal display module and the touch module.

[0005] The anti-sticking hard coat film provided by the present application comprises a transparent substrate and an anti-sticking hard coat layer on the transparent substrate, wherein the anti-sticking hard coat layer comprises an acrylic binder resin, a plurality of silica nanoparticles, and an acrylic ester-ether group-containing surfactant, wherein the silica nanoparticles comprise a plurality of hydrophilic silica nanoparticles and a plurality of hydrophobic silica nanoparticles and form a plurality of micron-sized silica nanoparticle flocs, and the ratio of the average secondary particle size of the silica nanoparticle flocs to the thickness of the anti-sticking hard coat layer is between 0.80 and 1.80, and the water contact angle of the surface of the anti-sticking hard coat layer is not greater than 80 degrees.

[0006] The present invention provides an anti-adhesion hard coating film, wherein the total amount of these silica nanoparticles is between 0.5 parts by weight and 8 parts by weight per 100 parts by weight of acrylic adhesive resin, wherein the amount of hydrophilic silica nanoparticles is between 0.1 parts by weight and 6 parts by weight per 100 parts by weight of acrylic adhesive resin, and the amount of hydrophobic silica nanoparticles is between 0.4 parts by weight and 2 parts by weight per 100 parts by weight of acrylic adhesive resin.

[0007] The anti-adhesion hard coating of the present invention has a thickness between 1 micrometer (μm) and 5 micrometers (μm) on a transparent substrate.

[0008] The present invention provides an anti-adhesion hard coating film in which the average secondary particle size of these silica nanoparticle flocs is between 2400 nanometers (nm) and 3400 nanometers (nm).

[0009] The present invention provides an anti-adhesion hard coating film, wherein the average primary particle size of these hydrophilic silica nanoparticles is between 5 nanometers (nm) and 100 nanometers (nm).

[0010] The anti-adhesion hard coating of the present invention comprises hydrophilic silica nanoparticles comprising unmodified silica nanoparticles; and / or, the hydrophilic silica nanoparticles comprising silica nanoparticles surface-modified with silanes having methacryloyloxy, acryloyloxy, or epoxy groups.

[0011] The present invention provides an anti-adhesion hard coating film, wherein the average primary particle size of these hydrophobic silica nanoparticles is between 5 nanometers (nm) and 60 nanometers (nm).

[0012] The present invention provides an anti-adhesion hard coating film, wherein the hydrophobic silica nanoparticles are silica nanoparticles that have undergone surface modification with alkyl, phenyl, or vinyl silanes or cyclic siloxanes.

[0013] The present invention provides an anti-adhesion hard coating film, wherein these silica nanoparticle flocs form an uneven surface on the surface of the anti-adhesion hard coating film, wherein the centerline average roughness Ra of the uneven surface is between 0.015 micrometers (μm) and 0.090 micrometers (μm), the total roughness height Ry is between 0.150 micrometers (μm) and 0.650 micrometers (μm), the ten-point average height Rz is between 0.110 micrometers (μm) and 0.450 micrometers (μm), and the average peak spacing RSm is between 50 micrometers (μm) and 150 micrometers (μm).

[0014] The anti-adhesion hard coating of the present invention contains an acrylate-ether-based surfactant with an average molecular weight of 200 to 6,000 and an average ethylene oxide (EO) unit of 1 to 40 as determined by matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF MS).

[0015] The anti-adhesion hard coating of the present invention, wherein the anti-adhesion hard coating contains, relative to 100 parts by weight of acrylic adhesive resin, an acrylate-ether-based surfactant between 0.01 parts by weight and 2 parts by weight.

[0016] The haze of the anti-adhesion hard coating of the present invention is less than 1.5%, and preferably less than 1.3%.

[0017] The anti-adhesion hard coating of the present invention comprises a transparent substrate and an anti-adhesion hard coating layer on the transparent substrate, wherein the anti-adhesion hard coating layer comprises an acrylic adhesive resin, a plurality of silica nanoparticles and an acrylate-ether-based surfactant, wherein the silica nanoparticles form a plurality of micron-sized silica nanoparticle flocs, and the silica nanoparticle flocs form an uneven surface on the surface of the anti-adhesion hard coating layer, wherein the centerline average roughness Ra of the uneven surface is between 0.015 μm and 0.090 μm, the total roughness height Ry is between 0.150 μm and 0.650 μm, the ten-point average height Rz is between 0.110 μm and 0.450 μm, and the average peak-to-peak RSm is between 50 μm and 150 μm.

[0018] In the anti-adhesion hard coating of the present invention, the matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF MS) average molecular weight of the acrylate-ether surfactant in the anti-adhesion hard coating is between 200 and 6,000, and the average ethylene oxide (EO) unit is between 1 and 40. In the anti-adhesion hard coating of the present invention, the acrylate-ether surfactant content in the anti-adhesion hard coating may be between 0.01 parts by weight and 2 parts by weight per 100 parts by weight of acrylic adhesive resin.

[0019] In the anti-adhesion hard coating of the present invention, the acrylic adhesive resin of the anti-adhesion hard coating comprises a methacrylate composition or an acrylate composition and an initiator, wherein the methacrylate composition or acrylate composition in the acrylic adhesive resin comprises 35 to 50 parts by weight of a polyurethane methacrylate or polyurethane acrylate oligomer with a functionality of 6 to 15, 12 to 20 parts by weight of a methacrylate or acrylate monomer with a functionality of 3 to 6, and 1.5 to 12 parts by weight of a methacrylate or acrylate monomer with a functionality of less than 3.

[0020] The foregoing summary is intended to provide a simplified overview of the patent's contents, enabling the reader to gain a basic understanding. This summary is not a complete overview of the patent's contents, nor is it intended to identify key elements of the embodiments or define the scope of the invention. Upon reviewing the following embodiments, those skilled in the art will readily understand the basic spirit of the invention and the technical means and implementation methods employed. Detailed Implementation

[0021] To make the description of this invention more detailed and complete, illustrative descriptions of embodiments and specific examples of this invention are provided below; however, these are not the only forms of implementing or using the specific examples of this invention. The various embodiments disclosed below can be combined or substituted with each other where advantageous, and other embodiments can be added to one embodiment without further description or explanation.

[0022] The advantages, features, and technical methods of the present invention will be more readily understood by referring to exemplary embodiments, and the invention may be implemented in different forms. Therefore, it should not be understood as limited to the embodiments set forth herein. Rather, the embodiments provided will enable those skilled in the art to more thoroughly and completely convey the scope of the invention, and the invention will be defined only by the appended claims.

[0023] Unless otherwise defined, all terms (including technical and scientific terms) and proper nouns used below shall, in substance, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains, and those terms as defined in commonly used dictionaries shall be understood to have the same meaning as the content of the relevant field, and shall not be interpreted in an overly idealized or overly formal sense unless explicitly defined below.

[0024] Furthermore, in this article, "(meth)acrylate" refers to methacrylate or acrylate.

[0025] This invention provides an anti-adhesion hard coating for bonding within a U-shape of a touch module and a liquid crystal display module, which has excellent anti-adhesion and anti-rainbow effect.

[0026] This invention provides an anti-adhesion hard coating film comprising a transparent substrate and an anti-adhesion hard coating layer on the transparent substrate. The anti-adhesion hard coating layer comprises an acrylic adhesive resin, a plurality of silica nanoparticles, and an acrylate-ether-based surfactant. The silica nanoparticles include hydrophilic silica nanoparticles and hydrophobic silica nanoparticles, forming a plurality of micron-sized silica nanoparticle flocs. The ratio of the average secondary particle size of the silica nanoparticle flocs to the thickness of the anti-adhesion hard coating layer is between 0.80 and 1.80, and the water contact angle of the surface of the anti-adhesion hard coating layer is not greater than 80 degrees.

[0027] In the anti-adhesion hard coating of the present invention, the average secondary particle size of the silica nanoparticle flocs in the anti-adhesion hard coating is preferably between 1.0 and 1.70 mm compared with the thickness of the anti-adhesion hard coating. In the anti-adhesion hard coating, the silica nanoparticle flocs form an uneven surface to avoid adhesion or water ripple phenomenon between the touch module and the liquid crystal display module caused by pressing during use of the touch panel.

[0028] The anti-adhesion hard coating of the present invention has a water contact angle of no more than 80 degrees, and preferably no more than 70 degrees. Because the surface of the anti-adhesion hard coating has high surface energy, it can bond well with the adhesive to provide sufficient adhesive strength during the subsequent in-cell bonding of the liquid crystal display module and the touch module.

[0029] The anti-adhesion hard coating of the present invention has a thickness of between 1 micrometer (μm) and 5 micrometers (μm) on a transparent substrate, preferably between 1 micrometer (μm) and 3 micrometers (μm).

[0030] The anti-adhesion hard coating of the present invention has an average secondary particle size of silica nanoparticles between 2400 nanometers (nm) and 3400 nanometers (nm), and preferably between 2500 nanometers (nm) and 3300 nanometers (nm).

[0031] The anti-adhesion hard coating of the present invention comprises, relative to 100 parts by weight of acrylic adhesive resin, silica nanoparticles ranging from 0.5 parts by weight to 8 parts by weight, wherein the hydrophilic silica nanoparticles are between 0.1 parts by weight and 6 parts by weight relative to 100 parts by weight of acrylic adhesive resin, and the hydrophobic silica nanoparticles are between 0.4 parts by weight and 2 parts by weight relative to 100 parts by weight of acrylic adhesive resin.

[0032] The anti-adhesion hard coating of the present invention, wherein the hydrophilic silica nanoparticles may be unmodified silica nanoparticles; and / or, the hydrophilic silica nanoparticles may be silica nanoparticles that have been surface-modified with silanes having (meth)acryloyloxy or epoxy groups. In one embodiment of the present invention, the hydrophilic silica nanoparticles may be, for example, unmodified silica nanoparticles or silica nanoparticles modified with 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, (3-epoxypropoxypropyl)triethoxysilane, (3-epoxypropoxypropyl)methyldiethoxysilane, (3-epoxypropoxypropyl)trimethoxysilane, 2-(3,4-epoxycyclohexylethyl)trimethoxysilane or similar materials, but are not limited thereto.

[0033] The anti-adhesion hard coating of the present invention, wherein the hydrophobic silica nanoparticles are silica nanoparticles surface-modified with alkyl, phenyl, or vinyl silanes or cyclic siloxanes, that is, the hydrophobic silica nanoparticles are silica nanoparticles surface-modified with alkyl, phenyl, or vinyl silanes, and / or silica nanoparticles surface-modified with alkyl, phenyl, or vinyl cyclic siloxanes. In one embodiment of the present invention, the hydrophobic silica nanoparticles may be, for example, silica nanoparticles modified with octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecylcyclohexasiloxane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, styryltrimethoxysilane, dimethyldichlorosilane, hexamethyldisilazane, or similar materials, but are not limited thereto.

[0034] The hydrophilic silica nanoparticles of the anti-adhesion hard coating suitable for the present invention can be selected from silica nanoparticles with an average primary particle size between 5 nanometers (nm) and 100 nanometers (nm), and preferably between 5 nanometers (nm) and 80 nanometers (nm); the suitable hydrophobic silica nanoparticles can be selected from silica nanoparticles with an average primary particle size between 5 nanometers (nm) and 60 nanometers (nm), and preferably between 10 nanometers (nm) and 50 nanometers (nm).

[0035] In the anti-adhesion hard coating of the present invention, these silica nanoparticles form multiple micron-sized silica nanoparticle flocs, and the average secondary particle size of these silica nanoparticle flocs can be between 2400 nanometers (nm) and 3400 nanometers (nm), and preferably between 2500 nanometers (nm) and 3300 nanometers (nm). These silica nanoparticle flocs form an uneven surface on the surface of the hard coating, wherein the average roughness Ra of the centerline of the uneven surface is between 0.015 micrometers (μm) and 0.090 micrometers (μm), the total roughness height Ry is between 0.150 micrometers (μm) and 0.650 micrometers (μm), the ten-point average height Rz is between 0.110 micrometers (μm) and 0.450 micrometers (μm), and the average peak spacing RSm is between 50 micrometers (μm) and 150 micrometers (μm). In a preferred embodiment of the anti-adhesion hard coating of the present invention, the surface roughness of the anti-adhesion hard coating is as follows: the centerline average roughness Ra is between 0.019 micrometers (μm) and 0.085 micrometers (μm), the total roughness height Ry is between 0.160 micrometers (μm) and 0.630 micrometers (μm), the ten-point average height Rz is between 0.115 micrometers (μm) and 0.430 micrometers (μm), and the average peak spacing RSm is between 60 micrometers (μm) and 140 micrometers (μm).

[0036] The haze of the anti-adhesion hard coating of the present invention is less than 1.5%, and preferably less than 1.3%, which is a low haze anti-adhesion hard coating.

[0037] The anti-adhesion hard coating of the present invention, measured by an image sharpness meter with fixed optical comb widths (i.e., 0.125 mm, 0.25 mm, 0.5 mm, 1.0 mm, 2.0 mm) from the largest to the smallest optical comb, and the calculated image sharpness (%) is greater than 70%, preferably greater than 75%. The anti-adhesion hard coating of the present invention has low image distortion and high visibility.

[0038] In the anti-adhesion hard coating of the present invention, the anti-adhesion hard coating contains an acrylate-ether-based surfactant, which is a polymeric compound formed by polymerization of one or more unsaturated monomers having a vinyl or (meth)acryloyl group with a monofunctional or polyfunctional group and one or more polyether monomers represented by formula (I):

[0039]

[0040] Where R1 is hydrogen or methyl, and R2 is hydrogen, C1 to C2. 10Hydrocarbon, phenyl, or (meth)acryloyl group, where a is an integer from 1 to 40 and b is an integer from 0 to 40, wherein the total amount of polyether monomer represented by formula (I) is between 0.1 molar percentage (or molar percentage, the same below) and 60 molar percentage of the acrylate-ether surfactant.

[0041] It should be noted that the aforementioned “one or more unsaturated monomers having vinyl or (meth)acryloyl groups with monofunctionality or polyfunctionality” refers to at least one unsaturated monomer, which is a monofunctional unsaturated monomer having vinyl or (meth)acryloyl groups, and / or a polyfunctional unsaturated monomer having vinyl or (meth)acryloyl groups.

[0042] The matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF MS) method used in this invention, which employs acrylate-ether surfactants, has an average molecular weight between 200 and 3,000 and an average ethylene oxide (EO) unit between 1 and 30.

[0043] In the polyether monomers of formula (I) above, the ethylene oxide (EO) unit and the propylene oxide (PO) unit are linked by random copolymerization, alternating copolymerization, or block copolymerization. In the polyether monomers of formula (I) above, when R2 is C1 to C2... 10 When a hydrocarbon group is used, the hydrocarbon group can be a substituted C1 to C2 group. 10 The hydrocarbon group can be a hydrocarbon group, an alkenyl group, a hydroxyl group, a phenyl group, an alkoxy group, or an epoxy group.

[0044] The unsaturated monomer with monofunctionality or polyfunctionality having vinyl or (meth)acryloyl groups used to form the acrylate-ether-based surfactant of the present invention is preferably at least one monofunctional unsaturated monomer having vinyl or (meth)acryloyl groups, and / or at least one polyfunctional unsaturated monomer having vinyl or (meth)acryloyl groups. That is, it is preferably at least one monofunctional unsaturated monomer having vinyl or (meth)acryloyl groups, and / or at least one polyfunctional unsaturated monomer having vinyl or (meth)acryloyl groups.

[0045] Preferred examples of monofunctional unsaturated monomers having vinyl or (meth)acryloyl groups suitable for forming the acrylate-ether-based surfactants of the present invention include, but are not limited to, styrene, α-methyl styrene, vinyl ether monomers such as ethyl vinyl ether, n-Butyl vinyl ether, and cyclohexyl vinyl ether, ethyl (meth)acrylate (E(M)A), n-butyl (meth)acrylate (nB(M)A), 2-ethylhexyl (meth)acrylate (2-EH(M)A), and 2-hydroxyethyl (meth)acrylate. (meth)acrylate, 2-HE(M)A), 2-ethoxyethyl(meth)acrylate, tetrahydrofuran(meth)acrylate (THF(M)A), isobornyl(meth)acrylate (IBO(M)A), 2-phenoxyethyl(meth)acrylate (PHE(M)A), perfluoroalkyl(meth)acrylate, (meth)acrylate functionalized polydimethylsiloxane, caprolactone and / or valerol modified (meth)acrylate hydroxyalkyl esters, etc. Furthermore, the aforementioned monofunctional unsaturated monomers can also selectively use chain transfer agents containing vinyl groups to control molecular weight, such as 2,4-dicyanopent-1-ene, 2,4-dicyanopent-4-methylpent-1-ene, 2,4-diphenyl-4-methylpent-1-ene, 2-cyano-4-methyl-4-phenyl-pent-1-ene, dimethyl 2,2-dimethyl-4-methylenepentane-1,5-dicarboxylate, and dibutyl 2,2-dimethyl-4-methylenepentane-1,5-dicarboxylate.

[0046] Preferred examples of polyfunctional unsaturated monomers having vinyl or (meth)acryloyl groups suitable for forming the acrylate-ether-based surfactants of the present invention include, but are not limited to, ethylene glycol di(meth)acrylate (EGD(M)A), diethylene glycol di(meth)acrylate (DEGD(M)A), 1,6-hexanediol di(meth)acrylate (HDD(M)A), polyethylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate.

[0047] The aforementioned acrylate-ether-based surfactants may be, for example, but not limited to, BYK-3440, BYK-3441, BYK-3560, BYK-3565, BYK-3566 or BYK-UV3535 (manufactured by BYK-Chemie GmbH, Germany).

[0048] In the anti-adhesion hard coating of the present invention, the amount of acrylate-ether surfactant contained in the anti-adhesion hard coating relative to every 100 parts by weight of acrylic adhesive resin may be between 0.01 parts by weight and 2 parts by weight, and preferably between 0.04 parts by weight and 1.1 parts by weight.

[0049] In the anti-adhesion hard coating of the present invention, the acrylic adhesive resin used in the anti-adhesion hard coating comprises a (meth)acrylate composition and an initiator, wherein the (meth)acrylate composition in the acrylic adhesive resin comprises 35 to 50 parts by weight of a polyurethane (meth)acrylate oligomer with a functionality of 6 to 15, 12 to 20 parts by weight of a (meth)acrylate monomer with a functionality of 3 to 6, and 1.5 to 12 parts by weight of a (meth)acrylate monomer with a functionality of less than 3.

[0050] In a preferred embodiment of the present invention, the polyurethane (meth)acrylate oligomer with a functionality of 6 to 15 is preferably an aliphatic polyurethane (meth)acrylate oligomer with a molecular weight between 1,500 and 4,500.

[0051] In a preferred embodiment of the present invention, the (meth)acrylate monomer with a functionality of 3 to 6 is a (meth)acrylate monomer with a molecular weight of less than 800. Suitable (meth)acrylate monomers with a functionality of 3 to 6 for use in the present invention are one or a combination of pentaerythritol triacrylate (PETA), dipentaerythritol hexaacrylate (DPHA), and dipentaerythritol pentaacrylate (DPPA), but are not limited thereto.

[0052] In a preferred embodiment of the present invention, the (meth)acrylate monomer with a functionality of less than 3 may be a (meth)acrylate monomer having a functionality of 1 or 2 and a molecular weight of less than 500. This (meth)acrylate monomer with a functionality of less than 3 may preferably be one or a combination of 1,6-hexanediol diacrylate (HDDA), cyclotrihydromethylpropane methyl acetal acrylate (CTFA), 2-phenoxyethyl acrylate (PHEA), or isobornyl acrylate (IBOA), but is not limited thereto.

[0053] In the acrylate-based binder resin of the present invention, suitable initiators can be those widely known and applicable in this art, without particular limitation. For example, acetophenone initiators, diphenyl ketone initiators, phenylacetone initiators, benzoyl initiators, bifunctional α-hydroxy ketone initiators, or acylphosphine oxide initiators can be used. The aforementioned initiators can be used alone or in combination.

[0054] In one embodiment of the present invention, a suitable transparent substrate may be a film material with good mechanical strength and light transmittance, which may be, but is not limited to, resin film materials such as polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), triacetyl cellulose (TAC), polyimide (PI), polyethylene (PE), polypropylene (PP), polyvinyl alcohol (PVA), polyvinyl chloride (PVC), or cyclic olefin copolymer (COC).

[0055] In a preferred embodiment of the present invention, the selected transparent substrate preferably has a light transmittance of 80% or more, and more preferably 90% or more. In a preferred embodiment of the present invention, the applicable thickness of the transparent substrate is approximately between 10 micrometers (μm) and 500 micrometers (μm), preferably between 15 micrometers (μm) and 250 micrometers (μm), and particularly preferably between 20 micrometers (μm) and 100 micrometers (μm).

[0056] Another object of the present invention is to provide a method for preparing an anti-adhesion hard coating film. The method for preparing the anti-adhesion hard coating film of the present invention includes mixing a polyurethane (meth)acrylate oligomer with a functionality of 6 to 15 in a (meth)acrylate composition, at least one (meth)acrylate monomer with a functionality of 3 to 6, at least one (meth)acrylate monomer with a functionality of less than 3, and an initiator with a suitable solvent to form an acrylic adhesive resin; adding hydrophilic silica nanoparticles and hydrophobic silica nanoparticles, an acrylate-ether-based surfactant, and an organic solvent to the acrylic adhesive resin, and mixing them to form an anti-adhesion hard coating solution; coating the anti-adhesion hard coating solution onto a transparent substrate, drying the transparent substrate coated with the anti-adhesion hard coating solution, and then curing it by radiation or electron beam to form an anti-adhesion hard coating on the transparent substrate to obtain an anti-adhesion hard coating film.

[0057] The solvent used in the aforementioned method for preparing the anti-adhesion hard coating of the present invention can be any organic solvent commonly used in this technical field, such as ketones, aliphatic or cycloaliphatic hydrocarbons, aromatic hydrocarbons, ethers, esters, or alcohols. One or more organic solvents can be used in both the acrylate composition and the anti-adhesion hard coating solution. Suitable solvents include, for example, acetone, butanone, cyclohexanone, methyl isobutyl ketone, hexane, cyclohexane, dichloromethane, dichloroethane, toluene, xylene, propylene glycol methyl ether, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isopropanol, n-butanol, isobutanol, cyclohexanol, diacetone alcohol, propylene glycol methyl ether acetate, or tetrahydrofuran, or similar substances, but are not limited thereto.

[0058] The aforementioned method for applying an anti-adhesion hard coating solution can employ, for example, roller coating, doctor blade coating, dip coating, roller coating, spin coating, spray coating, slot coating, and other coating methods commonly used in this technical field.

[0059] The following embodiments are used to further illustrate the present invention, but the content of the present invention is not limited thereto.

[0060] Example

[0061] Preparation Example 1: Preparation of Acrylic Adhesive Resin

[0062] 42 parts by weight of polyurethane acrylate oligomer (functionality 6, molecular weight approximately 2,600, viscosity approximately 70,000 cps (25°C), purchased from Miwon Specialty Chemical Co., Ltd., South Korea), 4.5 parts by weight of pentaerythritol triacrylate (PETA), 12 parts by weight of dipentaerythritol hexaacrylate (DPHA), 3 parts by weight of isobornyl acrylate (IBOA), 4 parts by weight of photoinitiator (Chemcure-481, purchased from Heng Chiao Industry, Taiwan, China), 24.5 parts by weight of ethyl acetate (EAC), and 10 parts by weight of n-butyl acetate (nBAC) were mixed and stirred for 1 hour to form an acrylate-based adhesive resin.

[0063] Example 1: Preparation of an anti-adhesion hard coating

[0064] 220 parts by weight of the acrylic adhesive resin of Preparation Example 1, 7.5 parts by weight of hydrophilic silica nanoparticle dispersion sol (MEK-ST-UP, solid content 20%, solvent: methyl ethyl ketone, purchased from Nissan Chemical, Japan), 3 parts by weight of hydrophobic silica nanoparticle dispersion sol (NanoBYK-3650, solid content 31%, solvent: propylene glycol methyl ether acetate / propylene glycol methyl ether, purchased from BYK, Germany), 3.75 parts by weight of acrylate-ether-based surfactant (BYK-UV3535, solid content 10%, solvent: ethyl acetate, purchased from BYK, Germany), 120 parts by weight of ethyl acetate (EAC) and 120 parts by weight of n-butyl acetate (nBAC) were mixed and stirred for 1 hour to achieve uniform dispersion, thus forming an anti-adhesion hard coating solution.

[0065] The anti-adhesion hard coating solution was applied to a polyethylene terephthalate (PET) substrate with a thickness of 75 micrometers (μm). After drying, it was photocured under a nitrogen atmosphere with a UV lamp at a radiation dose of 80 mJ / cm² to form an anti-adhesion hard coating with a thickness of 2.4 micrometers (μm) on the PET substrate. The aforementioned thickness was evaluated using an electronic comparability meter Extramess 2001 (Mahr Inc., Germany) according to the description in JIS K5600-1-7:2014.

[0066] The obtained anti-adhesion hard coating was subjected to the following optical and physical property analyses, and the results are listed in Table 1.

[0067] Transmittance measurement: The transmittance was evaluated using the NDH-2000 (Nippon Denshoku Corp.) according to the description in JIS K7361.

[0068] Haze measurement: Haze was evaluated using an NDH-2000 (Nippon Denshoku Corp.) according to the description in JIS K7136. A haze range of 1.5% or less was considered passing.

[0069] Gloss measurement: The anti-adhesion hard coating was bonded to a black acrylic plate with transparent optical adhesive. The gloss was measured using a BYK micro-gloss meter according to the description of JIS Z 8741, and gloss values ​​at 20, 60 and 85 degrees were selected.

[0070] Clarity measurement: The hard coating was cut into 5x8 cm2 pieces and measured using a SUGA ICM-IT image clarity meter according to the description of JIS K7374. The values ​​of the 0.125mm, 0.25mm, 0.50mm, 1.00mm and 2.00mm slit measurements were summed.

[0071] Pencil Hardness Measurement: Based on the description in JIS K 5400, the pencil hardness of the hard coating surface is measured. An automatic pencil hardness tester (instrument model 553-M, manufactured by Yasuda Seiki Seisakusho) is used to apply a 500g load. A Mitsubishi hardness pencil marked "Nikkatsu Inspection Solution" is used, moving the pencil at a speed of 1mm / s. Five pencil hardness measurements are performed against the adhesive hard coating. If two or more scratches are found, the hardness is deemed unsatisfactory. The maximum hardness that passes the test is recorded.

[0072] Water contact angle measurement: The anti-adhesion hard coating was attached to the stage, and the contact angle was measured using a Surface Electro Optics (SEO) Phoenix-150 contact angle meter by adding one drop of water (approximately 0.01 ml) at a time.

[0073] Measurement of tape adhesion: Cut an appropriate size of anti-adhesion hard coating film, attach a protective film with antistatic agent to the anti-adhesion hard coating surface, let the hard coating film with protective film stand at room temperature for 24 hours, then remove the protective film, attach the hard coating film to the glass substrate with transparent optical adhesive, attach 3M VHB tape to the hard coating surface of the hard coating film and let stand for 1 hour, measure the 180-degree peel strength with a tensile tester, collect 5 data points and average them to obtain the adhesion value.

[0074] Evaluation of anti-adhesion effect: Cut an appropriate size anti-adhesion hard coating and a polarizer with a hard coating of approximately 98 degrees water contact angle. Attach the anti-adhesion hard coating and the polarizer to a glass substrate using transparent optical adhesive. Then, overlap the hard coating surfaces of the anti-adhesion hard coating and the polarizer. Apply a load of 1000 g / cm² and leave for 2 minutes. Remove the load and evaluate the anti-adhesion effect. No adhesion is rated as "Excellent" (〇). Adhesion that disappears within 3 seconds is rated as "Medium" (Δ). Partial or complete adhesion after 3 seconds is rated as "Poor" (×).

[0075] Evaluation of the degree of rainbow effect: The anti-adhesion hard coating is bonded to a black acrylic plate with transparent optical adhesive. Under a test table with 6 36W fluorescent tubes and a diffuser plate covering them, the degree of rainbow effect of the anti-adhesion hard coating is evaluated at a 60-degree angle. If there is no obvious rainbow effect, it is rated as "extremely excellent" (◎). If there is a slight rainbow effect but no problem in use, it is rated as "excellent" (〇). If there is an obvious rainbow effect, it is rated as "poor" (×).

[0076] Measurement of the secondary particle size of nanoparticles: The anti-adhesion hard coating was cut into an appropriate size and placed in a Mitutoyo SV-320 high-magnification optical microscope. The light transmission image of the anti-glare film was captured by a CCD camera at a magnification of 10x eyepiece and 20x objective lens. The secondary particle size of the nanoparticles was calculated by image measurement software. At least 15 data points were sampled and their average value was taken.

[0077] Surface roughness measurement: The centerline average roughness (Ra), total roughness height (Ry), ten-point average height (Rz), and average peak spacing (RSm) were measured using a Mitutoyo CN-H5000CNC surface roughness / profilometry instrument according to the descriptions in JIS B0601 (1994) and JIS B0031 (1994). Each item was tested at least 3 times and the average value was taken.

[0078] Example 2: Preparation of an anti-adhesion hard coating

[0079] Example 2 uses the same method as Example 1 to prepare an anti-adhesion hard coating film, except that 7.5 parts by weight of hydrophilic silica nanoparticle dispersion sol (MEK-ST-UP) is replaced with 15 parts by weight of hydrophilic silica nanoparticle dispersion sol (MEK-ST-UP), and an anti-adhesion hard coating solution is formed.

[0080] The anti-adhesion hard coating solution was applied to a polyethylene terephthalate (PET) substrate with a thickness of 75 micrometers (μm). After drying, it was photocured in a nitrogen atmosphere with a UV lamp with a radiation dose of 80 mJ / cm2 to form an anti-adhesion hard coating with a thickness of 2.2 micrometers (μm) on the PET substrate.

[0081] The anti-adhesion hard coating obtained in Example 2 was evaluated for optical and physical properties in accordance with Example 1, and the results are listed in Table 1.

[0082] Example 3: Preparation of an anti-adhesion hard coating

[0083] Example 3 uses the same method as Example 1 to prepare an anti-adhesion hard coating film, except that 7.5 parts by weight of hydrophilic silica nanoparticle dispersion sol (MEK-ST-UP) is replaced with 30 parts by weight of hydrophilic silica nanoparticle dispersion sol (MEK-ST-UP), and an anti-adhesion hard coating solution is formed.

[0084] The anti-adhesion hard coating solution was applied to a polyethylene terephthalate (PET) substrate with a thickness of 75 micrometers (μm). After drying, it was photocured in a nitrogen atmosphere with a UV lamp with a radiation dose of 80 mJ / cm2 to form an anti-adhesion hard coating with a thickness of 2.4 micrometers (μm) on the PET substrate.

[0085] The anti-adhesion hard coating obtained in Example 3 was evaluated for optical and physical properties in accordance with Example 1, and the results are listed in Table 1.

[0086] Example 4: Preparation of an anti-adhesion hard coating

[0087] Example 4 uses the same method as Example 1 to prepare an anti-adhesion hard coating film, except that 7.5 parts by weight of hydrophilic silica nanoparticle dispersion sol (MEK-ST-UP) is replaced with 1 part by weight of hydrophilic silica nanoparticle dispersion sol (MEK-AC-4130Y, solid content 30%, solvent is methyl ethyl ketone, purchased from Nissan Chemical, Japan), and the acrylate-ether surfactant is replaced with 0.75 parts by weight of acrylate-ether surfactant (BYK-3440, solid content 10%, solvent is dipropylene glycol monomethyl ether, purchased from BYK, Germany), and an anti-adhesion hard coating solution is formed.

[0088] The anti-adhesion hard coating solution was applied to a polyethylene terephthalate (PET) substrate with a thickness of 75 micrometers (μm). After drying, it was photocured in a nitrogen atmosphere with a UV lamp with a radiation dose of 80 mJ / cm2 to form an anti-adhesion hard coating with a thickness of 2.2 micrometers (μm) on the PET substrate.

[0089] The anti-adhesion hard coating obtained in Example 4 was evaluated for optical and physical properties in accordance with Example 1, and the results are listed in Table 1.

[0090] Example 5: Preparation of an anti-adhesion hard coating

[0091] Example 5 uses the same method as Example 1 to prepare an anti-adhesion hard coating film, except that 7.5 parts by weight of hydrophilic silica nanoparticle dispersion sol (MEK-ST-UP) is replaced with 15 parts by weight of hydrophilic silica nanoparticle dispersion sol (MEK-ST-UP), and 15 parts by weight of acrylate-ether surfactant (BYK-3535) is replaced with acrylate-ether surfactant to form an anti-adhesion hard coating solution.

[0092] The anti-adhesion hard coating solution was applied to a polyethylene terephthalate (PET) substrate with a thickness of 75 micrometers (μm). After drying, it was photocured in a nitrogen atmosphere with a UV lamp with a radiation dose of 80 mJ / cm2 to form an anti-adhesion hard coating with a thickness of 2.9 micrometers (μm) on the PET substrate.

[0093] The anti-adhesion hard coating obtained in Example 5 was evaluated for optical and physical properties in accordance with Example 1, and the results are listed in Table 1.

[0094] Table 1: Optical and physical property evaluation of the anti-adhesion hard coatings of Examples 1 to 5

[0095]

[0096]

[0097] The anti-adhesion hard coatings obtained in Examples 1 to 5 have a haze of less than 1.3% and a water contact angle of less than 70 degrees to provide higher surface energy, which is beneficial for bonding with adhesives during subsequent bonding. When tested with 3M VHB tape, the tensile strength is above 664gf / 10mm, and the tensile strength of the anti-adhesion hard coating obtained in Example 2 can be as high as 988gf / 10mm.

[0098] The surface roughness analysis of the anti-adhesion hard coatings obtained in Examples 1 to 5 is shown in Table 1. The anti-adhesion hard coatings obtained in Examples 1 to 5 have an uneven surface, which can provide anti-adhesion properties and provide an effective anti-rainbow effect.

[0099] Of course, the present invention may have other various embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and modifications according to the present invention, but these corresponding changes and modifications should all fall within the protection scope of the appended claims.

Claims

1. An anti-sticking hard coat film, characterized by Comprising: a transparent substrate; and an anti-adhesion hard coat layer on the transparent substrate, a water contact angle of a surface of the anti-adhesion hard coat layer being not more than 70 degrees, the anti-adhesion hard coat layer comprising: an acrylic binder resin; a plurality of silica nanoparticles, wherein the plurality of silica nanoparticles comprises a plurality of hydrophilic silica nanoparticles and a plurality of hydrophobic silica nanoparticles and forms a plurality of silica nanoparticle flocculates of a micrometer scale, and a ratio of an average secondary particle diameter of the plurality of silica nanoparticle flocculates to a thickness of the anti-adhesion hard coat layer is between 0.80 and 1.80; and an acrylate-ether group-containing surfactant.

2. The anti-sticking hard coat film according to claim 1, characterized by, a total amount of the plurality of silica nanoparticles is between 0.5 parts by weight and 8 parts by weight per 100 parts by weight of the acrylic binder resin, wherein an amount of the plurality of hydrophilic silica nanoparticles is between 0.1 parts by weight and 6 parts by weight per 100 parts by weight of the acrylic binder resin, and an amount of the plurality of hydrophobic silica nanoparticles is between 0.4 parts by weight and 2 parts by weight per 100 parts by weight of the acrylic binder resin.

3. The anti-sticking hard coat film according to claim 1, characterized by, a thickness of the anti-adhesion hard coat layer on the transparent substrate is between 1 micrometer and 5 micrometers.

4. The anti-sticking hard coat film according to claim 1, characterized by, an average secondary particle diameter of the plurality of silica nanoparticle flocculates is between 2400 nanometers and 3400 nanometers.

5. The anti-sticking hard coat film according to claim 1, wherein an average primary particle diameter of the plurality of hydrophilic silica nanoparticles is between 5 nanometers and 100 nanometers.

6. The anti-sticking hard coat film according to claim 1, wherein the plurality of hydrophilic silica nanoparticles comprises unmodified silica nanoparticles; and / or, the plurality of hydrophilic silica nanoparticles comprises silica nanoparticles surface-modified with a silane having a methacryloyloxy group, an acryloyloxy group, or an epoxy group.

7. The anti-sticking hard coat film according to claim 1, wherein an average primary particle diameter of the plurality of hydrophobic silica nanoparticles is between 5 nanometers and 60 nanometers.

8. The anti-sticking hard coat film according to claim 1, wherein the plurality of hydrophobic silica nanoparticles comprises silica nanoparticles surface-modified with a silane having an alkyl group, a phenyl group, or a vinyl group; and / or, the plurality of hydrophobic silica nanoparticles comprises silica nanoparticles surface-modified with a cyclic siloxane having an alkyl group, a phenyl group, or a vinyl group.

9. The anti-sticking hard coat film according to claim 1, wherein the plurality of silica nanoparticle flocculates forms a concavo-convex surface on a surface of the anti-adhesion hard coat layer, the concavo-convex surface having a center line average roughness of between 0.015 micrometers and 0.090 micrometers, a total roughness height of between 0.150 micrometers and 0.650 micrometers, a ten-point average height of between 0.110 micrometers and 0.450 micrometers, and an average peak-to-peak distance of between 50 micrometers and 150 micrometers.

10. The anti-sticking hard coat film according to claim 1, wherein the acrylate-ether group-containing surfactant has a matrix-assisted laser desorption ionization-time of flight mass spectrometry average molecular weight of between 200 and 6,000 and an average oxyethylene group number of between 1 and 40.

11. The anti-sticking hard coat film according to claim 1, characterized by, in the anti-adhesion hard coat layer, the acrylate-ether group-containing surfactant is between 0.01 parts by weight and 2 parts by weight per 100 parts by weight of the acrylic binder resin.

12. The anti-sticking hard coat film according to claim 1, characterized by, the acrylic binder resin of the anti-adhesion hard coat layer comprises a starter; the acrylic binder resin of the anti-adhesion hard coat layer further comprises a methacrylate composition; wherein the methacrylate composition in the acrylic binder resin comprises, 35 to 50 parts by weight of a polyurethane methacrylate oligomer having a functionality of 6 to 15, 12 to 20 parts by weight of a methacrylate monomer having a functionality of 3 to 6, and 1.5 to 12 parts by weight of a methacrylate monomer having a functionality of less than 3; and / or the acrylic binder resin of the anti-sticking hard coat layer further comprises an acrylate composition; wherein the acrylate composition in the acrylic binder resin comprises, 35 to 50 parts by weight of a polyurethane acrylate oligomer having a functionality of 6 to 15, 12 to 20 parts by weight of an acrylate monomer having a functionality of 3 to 6, and 1.5 to 12 parts by weight of an acrylate monomer having a functionality of less than 3.

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