Anti-reflective coating

Abstract

A curable composition for forming an antireflective film is provided. The composition comprises: (a) hollow silica nanoparticles; (b) a siloxane binder having reactive groups; (c) at least one additive material having reactive groups; (d) an initiator; and (e) a solvent. The siloxane binder is present in an amount of at least 50% by weight of the total weight of the siloxane binder and the additive material having reactive groups. The weight ratio of the hollow silica nanoparticles to the total weight of the siloxane binder and the additive material having reactive groups is no greater than 1.75 to 1.

Description

Technical Field

[0001] This invention relates to curable compositions for antireflective coatings, particularly for display devices. Background Technology

[0002] Anti-reflective (AR) coatings on the top surface of display devices have become increasingly important in the display industry. This is especially true for achieving enhanced visual experiences, particularly in strong ambient light conditions. In addition to serving as an anti-reflective coating, this layer is also expected to act as a scratch-resistant coating with fingerprint-resistant properties. Essentially, it is an ultra-thin, hard coating on the surface of the mobile device. The film thickness (FT) is chosen to ensure that the reflected light from the top and bottom surfaces of the AR film is out of phase—that is, the phase difference is 180°—so that the light reflected from the top and bottom surfaces cancels each other out. If the magnitudes of the reflected light from the top and bottom surfaces are the same, there is no reflected light of the target wavelength. To achieve this, the AR coating needs to have a low refractive index.

[0003] There is a continued need for AR coatings with improved properties. Summary of the Invention

[0004] A curable composition for forming an antireflective coating is provided, the composition comprising:

[0005] (a) Hollow silica particles;

[0006] (b) Siloxane adhesives with reactive groups;

[0007] (c) At least one additional material having a reactive group;

[0008] (d) Initiator; and

[0009] (e) Solvent;

[0010] in:

[0011] (i) The siloxane adhesive is present in an amount of at least 50% by weight of the total weight of (siloxane adhesive + additional material having reactive groups); and

[0012] (ii) The weight ratio of hollow silica particles to (siloxane binder + additional materials with reactive groups) is not greater than 1.75.

[0013] A further antireflective film is provided, which is manufactured by the following:

[0014] (1) The above curable composition is coated onto a substrate to form an uncured film;

[0015] (2) Dry the uncured film to form a dried uncured film;

[0016] (3) Expose the dried, uncured film to one or both of UV radiation and heat to form the AR film.

[0017] Furthermore, an electronic device having the aforementioned antireflective film is provided.

[0018] definition

[0019] As used herein, the term "adhesive" is intended to refer to a material that holds particles and other materials together and provides mechanical strength and uniform consistency.

[0020] The term "curable" when applied to a composition is intended to refer to a material that becomes harder when exposed to radiation and / or heat and has less solubility in solvents.

[0021] The term "hollow silica particles" is intended to refer to silica particles that have voids on the particle surface and / or inside the particle.

[0022] The term "(meth)acrylate" is intended to refer to a group that is an acrylate or a methacrylate.

[0023] The term "polyhedron" is intended to refer to a cage-like structure with polygonal faces.

[0024] The term "porosity" when referring to silica particles is intended to mean the percentage of void volume to the total volume of the particles.

[0025] The term "reactive group" is intended to refer to a group that is capable of polymerizing or crosslinking when exposed to radiation and / or heat.

[0026] The term "siloxane" is intended to refer to a material having a molecular structure based on alternating chains of silicon and oxygen atoms, in which organic groups are attached to silicon atoms.

[0027] The term "sesquioxane" is intended to refer to a substance with the chemical formula [RSiO] 1.5 ] n A siloxane compound, where n is an even integer and R can be H or an organic functional group. R can be the same or different each time it appears.

[0028] The term "solvent" is intended to refer to an organic compound that is a liquid at room temperature. The term is intended to cover a single organic compound or a mixture of two or more organic compounds.

[0029] All ranges are inclusive of end values ​​and can be combined. For example, the term “range of 50 to 3000 cPs, or 100 or more cPs” would include each of 50 to 100 cPs, 50 to 3000 cPs, and 100 to 3000 cPs.

[0030] In this specification, unless explicitly indicated or contrary to the context, one or more features or elements other than those explicitly stated or described may also be present in embodiments of the subject matter of the invention when they are stated or described as comprising, including, containing, having, consisting of, or constituted by certain features or elements. Alternative embodiments of the disclosed subject matter of the invention are described as consisting primarily of certain features or elements, wherein features or elements that would substantially alter the operating principle or embodiment are absent. Another alternative embodiment of the subject matter of the invention described is described as consisting of certain features or elements in which only the specifically stated or described features or elements are present, either in the embodiment or in its non-essential variations.

[0031] Furthermore, the term "a / an" is used to describe the elements and components described herein. This is done for convenience and to give a general meaning to the scope of the invention. This description should be interpreted as including one / an or at least one / an, and the singular form includes the plural form, unless it is obvious that it refers to something else.

[0032] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. While similar or equivalent methods and materials described herein may be used in the practice or testing of embodiments of the invention, suitable methods and materials are described below. Furthermore, the materials, methods, and examples are illustrative only and are not intended to be limiting.

[0033] As for the scope not described in this article, many details about specific materials, processing behaviors, and circuits are conventional and can be found in textbooks and other sources in the fields of photoresists, organic light-emitting diode displays, photodetectors, photovoltaic cells, and semiconductor components. Detailed Implementation

[0034] The curable compositions described herein can be used to form antireflective (“AR”) films. The curable compositions can be applied to a device or substrate and cured to form an AR film. Such films have been found to have improved scratch resistance. Furthermore, such films have been found to have improved anti-fingerprint properties.

[0035] The curable composition comprises:

[0036] (a) Hollow silica particles;

[0037] (b) Siloxane adhesives with reactive groups;

[0038] (c) At least one additional material having a reactive group;

[0039] (d) Initiator; and

[0040] (e) Solvent.

[0041] The curable composition comprises hollow silica particles. The hollow silica particles may have any shape or may be amorphous. In some embodiments, the hollow silica particles are spherical or tubular.

[0042] In some embodiments, the hollow silica particles have a porosity of about 10%-75%; in some embodiments, 40%-60%.

[0043] In some embodiments, most of the voids in the hollow silica particles are inside the particles; in other embodiments, substantially all voids are inside the particles.

[0044] In some embodiments, the hollow silica particles have a particle size of less than 1 μm; in some embodiments, less than 500 nm. In some embodiments, the number-average particle size is 10 nm to 500 μm; in some embodiments, 50 nm to 250 μm.

[0045] Hollow silica particles are readily available commercially.

[0046] In some embodiments, the hollow silica particles are present in an amount of 30-80% by weight based on the total weight of solids in the curable composition; in some embodiments, 35-70% by weight; and in some embodiments, 40-65% by weight. As used herein, the total weight of solids in the curable composition is considered to be the weight of the composition minus the weight of the solvent.

[0047] The curable composition comprises a siloxane binder having reactive groups. In some embodiments, the curable composition does not contain a silicone-free binder. "Silicone-free" means a material in which no Si atoms are present.

[0048] In some embodiments, the siloxane adhesive is selected from the group consisting of silsesquioxanes, oligomeric siloxanes, polymeric siloxanes, and combinations thereof.

[0049] In some embodiments, the siloxane adhesive is a polyhedral oligomeric silsesquioxane (“POSS”). The POSS may have 6, 8, 10, or 12 Si vertices, corresponding to the formula [RSiO]. 1.5 ] n The "n" in the figure. In some embodiments, n = 8. In some embodiments, POSS is a mixture of polyhedra with 6-12 vertices.

[0050] In some embodiments, the siloxane adhesive is a siloxane oligomer. In some embodiments, the siloxane oligomer has fluorine substituents. In some embodiments, the siloxane oligomer has a fluorine content of 1-25% by weight.

[0051] In some embodiments, the siloxane oligomer does not have fluorine substituents.

[0052] In some embodiments, the siloxane oligomer has a weight-average molecular weight (Mw) of 1,000-10,000.

[0053] The siloxane adhesive has at least one reactive group. In some embodiments, the siloxane adhesive has multiple reactive groups. In some embodiments, 50%-100% of the Si atoms are bonded to the reactive groups; in some embodiments, 75%-100%.

[0054] In some embodiments, the reactive group is selected from the group consisting of acrylates, methacrylates, vinyl groups, epoxy groups, isocyanates, and combinations thereof.

[0055] In some embodiments, the reactive groups on the siloxane adhesive are acrylates or methacrylates.

[0056] A specific example of a siloxane adhesive with reactive groups is acrylo-POSS. Acrylo-POSS is a mixture of cage-like structures having 8, 10, and 12 Si atoms, with each Si atom bonded to an acrylopropyl group. Additional siloxane adhesives with reactive groups are shown in the examples.

[0057] In some embodiments, the siloxane adhesive having reactive groups is present in an amount of 15-70% by weight based on the weight of solids in the curable composition; in some embodiments, 30-60% by weight; and in some embodiments, 40-50% by weight.

[0058] The curable composition comprises at least one additional material having a reactive group. In some embodiments, the additional material having a reactive group is selected from the group consisting of monomers, oligomers, surfactants, and combinations thereof. The reactive group can be any of those described above.

[0059] In some embodiments, the additional material having reactive groups is a monomer. The monomer has a molecular weight Mw of less than 1000; in some embodiments, less than 750.

[0060] In some embodiments, the monomer has two or more acrylate or methacrylate groups.

[0061] In some embodiments, the monomer has two or more diisocyanate groups.

[0062] In some embodiments, the monomer has two or more epoxy groups.

[0063] Specific examples of monomers include, but are not limited to, dipentaerythritol penta(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene glycol di(meth)acrylate, xylene diisocyanate, hexamethylene diisocyanate, ethylene glycol diglycidyl ether, and combinations thereof.

[0064] In some embodiments, the monomer is present in an amount of 0-15% by weight based on the weight of solids in the curable composition; in some embodiments, 0-10% by weight; in some embodiments, 0-5% by weight.

[0065] In some embodiments, no monomers are present in the curable composition.

[0066] In some embodiments, the additional material having reactive groups is an oligomer. In some embodiments, the oligomer is selected from the group consisting of: (meth)acrylates, urethane-modified (meth)acrylates, polyester (meth)acrylates, epoxide (meth)acrylates, ether (meth)acrylates, and mixtures thereof.

[0067] In some embodiments, the additional material having reactive groups is a (meth)acrylate oligomer.

[0068] In some embodiments, the oligomer having reactive groups has a weight-average molecular weight Mw of 1,000-10,000.

[0069] In some embodiments, the oligomer having reactive groups is present in an amount of 1.5-7.0% by weight based on the weight of solids in the curable composition; in some embodiments, 3.0-6.0% by weight; in some embodiments, 4.0-5.0% by weight.

[0070] In some embodiments, the additive material having reactive groups is a surfactant. In some embodiments, the additive material having reactive groups is a fluorinated surfactant. In some embodiments, the fluorinated surfactant has a fluorine content of 1-25% by weight.

[0071] In some embodiments, the surfactant having reactive groups is present in an amount of 0.1-5.0% by weight based on the weight of solids in the curable composition; in some embodiments, 0.5-1.0% by weight.

[0072] Surfactants and fluorinated surfactants are well known and commercially available in the art.

[0073] The curable composition contains an initiator. The initiator is present to generate an active substance that initiates the polymerization and / or crosslinking of reactive groups in the curable composition.

[0074] In some embodiments, the initiator is a photoinitiator. Any known photoinitiator can be used. Some examples of photoinitiators include, but are not limited to, aromatic ketones, acetophenones, benzoin, benzoin ethers, and onium salts. In some embodiments, a combination of photoinitiators is used.

[0075] In some embodiments, the initiator is a thermal initiator. Any known thermal initiator can be used. Some examples of thermal initiators include, but are not limited to, azo compounds, peroxides, persulfates, and redox initiators. In some embodiments, a combination of thermal initiators is used.

[0076] In some embodiments, both a photoinitiator and a thermal initiator are present in the curable composition.

[0077] In some embodiments, the total amount of initiator present is 0.5-5% by weight based on the weight of solids in the curable composition; in some embodiments, it is 1-3% by weight.

[0078] The curable composition comprises a solvent. Any solvent may be used in the curable composition, provided that the other components are sufficiently dissolved or dispersed to allow the composition to be coated to form a film. In some embodiments, the solvent is selected from the group consisting of ketones, alcohols, acetates, ethers, combinations thereof, and mixtures thereof.

[0079] Specific examples of solvents include, but are not limited to, methyl isobutyl ketone, isobutanol, propylene glycol methyl ether acetate, tetrahydrofuran, etc.

[0080] In some embodiments, the solvent is present in such an amount that the total solids content of the curable composition is from 1% to 50% by weight; in some embodiments, it is from 10% to 30% by weight.

[0081] In some embodiments of the curable compositions described herein, the weight of the siloxane binder is at least 50% of the total weight of the materials having reactive groups. This means that the siloxane is 50% of the total weight of (siloxane binder with reactive groups + oligomer with reactive groups + surfactant with reactive groups + monomer with reactive groups + any other materials with reactive groups). In some embodiments, the siloxane binder is at least 60% of the total weight of the materials having reactive groups; in some embodiments, at least 70%; in some embodiments, at least 80%; and in some embodiments, at least 90%.

[0082] In some embodiments of the curable composition, the weight ratio of the total weight of the hollow silica particles to the material having reactive groups is not greater than 1.75; in some embodiments, it is not greater than 1.6; in some embodiments, it is not greater than 1.5; and in some embodiments, it is not greater than 1.4.

[0083] The curable compositions described herein can be used to manufacture AR films. Methods for manufacturing AR films include:

[0084] (1) The above curable composition is coated onto a substrate to form an uncured film;

[0085] (2) Dry the uncured film to form a dried uncured film;

[0086] (3) Expose the dried, uncured film to one or both of UV radiation and heat to form the AR film.

[0087] The curable composition can be applied to the substrate using any known liquid deposition method. Such methods include, but are not limited to, slot die coating, spin coating, spray coating, bar coating, dip coating, and gravure coating.

[0088] The substrate can be any material on which the AR coating is desired. The substrate can be glass or a polymer material.

[0089] In some embodiments, the uncured film is dried by heating. In some embodiments, the drying temperature is 50°C-120°C; in some embodiments, it is 70°C-100°C. In some embodiments, the drying time is 30 seconds to 2 minutes.

[0090] In some embodiments, the dried, uncured film is cured by exposure to UV radiation. The exact exposure conditions will depend on the nature of the photoinitiator in the curable composition. Typically, broadband UV radiation can be used for exposure times of a few seconds.

[0091] In some embodiments, the dried, uncured film is cured by heating. In some embodiments, the heating temperature is 150°C-250°C; in some embodiments, it is 175°C-225°C. In some embodiments, the heating time is 30-120 minutes.

[0092] In some embodiments, the dried, uncured film is cured by exposure to UV radiation and by heating. In some embodiments, the dried, uncured film is first exposed to UV radiation and then heated. The exposure and heating conditions are as described above.

[0093] The thickness of the AR film is typically 1-2000 nm; in some embodiments, 10-1500 nm; in some embodiments, 50-1000 nm; in some embodiments, 50-500 nm; and in some embodiments, 100-200 nm. The film thickness should satisfy the following optical relationship with the target wavelength in the visible spectrum:

[0094] FT = k(λ / 4)

[0095] in:

[0096] λ=λ o / n

[0097] λ o It is the target wavelength in a vacuum.

[0098] n is the refractive index of the AR coating, and

[0099] k is an odd integer

[0100] The target wavelength in the visible spectrum was chosen to be 555 nm, which corresponds to the color that the human eye is most sensitive to (yellow-green).

[0101] The AR film described herein has a low refractive index. In some embodiments, the refractive index is less than 1.5; in some embodiments, it is less than 1.4; and in some embodiments, it is less than 1.3.

[0102] The AR film described herein has high visible light transmittance. In some embodiments, the transmittance is greater than 90%; in some embodiments, it is greater than 95%.

[0103] The AR film described herein has a high contact angle with water. In some embodiments, the contact angle is greater than 100°; in some embodiments, it is greater than 110°; and in some embodiments, it is greater than 115°. The high contact angle results in improved anti-fouling and anti-fingerprint properties.

[0104] The AR film described in this article has improved scratch resistance. This is further illustrated in the examples.

[0105] AR film can be used in any application where AR properties are desired. In some embodiments, AR film is used on the topmost surface of a display device.

[0106] Examples

[0107] The concepts described herein will be further illustrated in the following examples, which do not limit the scope of the invention as described in the claims.

[0108] Material:

[0109] DU-1008 = DU-1008SIV, hollow silica particles, from Catalystsand Chemicals Ltd. (Japan); this material is supplied as a 20% dispersion in methyl isobutyl ketone (“MIBK”).

[0110] Acryloyl POSS = POSS with acrylate functional groups, from Hybrid Plastics (USA).

[0111] KY-1203 = a fluorinated surfactant from Shin-Etsu Corporation (Japan); this material is supplied as a 20% solution in MIBK.

[0112] DAC-HP = Optool DAC-HP, a fluorinated surfactant from Daikin Corporation (Japan); this material is supplied as a 20% solution in 1,1,2,2,3,3,4-heptafluorocyclopentane and PGME.

[0113] SR399 = Dipentaerythritol pentaacrylate from Sartomer (USA)

[0114] LED02 = mercapto-modified polyester acrylate, from Allnex (USA).

[0115] KTO = Esacure KTO 46, a free radical photoinitiator from IGM Corporation (USA).

[0116] Ebecryl = Ebecryl 8602, an aliphatic urethane acrylate oligomer from Zhanxin Company.

[0117] Photomer = Photomer 4356, a triacrylate monomer from IGM Corporation (USA).

[0118] TfBDMBA = Hot acid generator, from E&I Korea.

[0119] Test methods

[0120] Contact angle

[0121] The contact angle between the AR-coated surface and water was determined using a KRUSS droplet shape analyzer (model 100). In this test, the water droplet size ranged from 1 to 2 μl.

[0122] Refractive index

[0123] This was determined using a laboratory refractometer.

[0124] Marker pen test

[0125] This is a qualitative test of the oleophobicity of the AR film. The markers used were red, blue, or black Sharpie permanent markers. This test was performed on a surface not treated for anti-fingerprint properties. This surface could be drawn on with the marker, showing clear and distinct marker marks. AR coatings with good anti-fingerprint properties could not be drawn on with the marker, showing ink accumulation by forming droplets along the drawn lines.

[0126] Steel wool test

[0127] This test was conducted using a 5900 reciprocating grinding mill from TABER Industries. The steel wool used in the test was from Nippon Steel Wool Co., Ltd. In this test, a 2×2cm layer was applied to the AR film. 2 A force of 1 kg was applied to the test area, with a stroke length of 5 cm and a stroke rate of 1 cycle / second.

[0128] Synthesis Example 1

[0129] This example illustrates the preparation of fluorinated siloxane adhesive SB-1.

[0130] Add 4.5383 g acryloyloxypropyltrimethoxysilane, 10.5331 g nonafluorohexyltrimethoxysilane, 2.5350 g DI water, 0.8262 g acetic acid, 10.1202 g cyclopentanol, and 0.0358 g butyric acid to a 100 ml round-bottom flask. Connect the flask to a condenser and heat the contents to 80 °C, maintaining the temperature at 80 °C with stirring for 6 hours.

[0131] Then, 10 g of cyclopentanol was added to the flask. The slightly turbid solution was then rotary evaporated at 50 °C to remove methanol, acetic acid, and water. Then, 10 ml of propylene glycol methyl ether acetate (“PGMEA”) was added to the solution to obtain a clear, homogeneous solution of the fluorinated siloxane material SB-1.

[0132] Using the loss-in-weight method, the solid content of SB-1 was found to be 53.0%.

[0133] Synthesis Example 2

[0134] This example illustrates the preparation of the siloxane adhesive SB-2.

[0135] Add 18.5672 g of acryloyloxypropyltrimethoxysilane, 16.4758 g of tetraethyl orthosilicate (“TEOS”), 8.9860 g of DI water, 1.7723 g of acetic acid, and 0.0308 g of BHT to a 100 ml round-bottom flask. Connect the flask to a condenser and heat the contents to 80 °C, maintaining the temperature at 80 °C with stirring for 2 hours.

[0136] Then 35 g of PGMEA was added to the flask. The solution was then rotary evaporated at 50 °C to remove methanol, ethanol, acetic acid, and water.

[0137] Using the loss-in-weight method, it was found that the solid content of the siloxane adhesive SB-2 was 53.85%.

[0138] Synthesis Example 3

[0139] This example illustrates the preparation of the siloxane adhesive SB-3.

[0140] Add 30.1587 g acryloyloxypropyltrimethoxysilane, 7.3297 g DI water, 1.8534 g acetic acid, and 0.0300 g BHT to a 100 ml round-bottom flask. Connect the flask to a condenser and heat the contents to 80 °C, maintaining the temperature at 80 °C for 2 hours with stirring.

[0141] Then 40 g of PGMEA was added to the flask. The solution was then rotary evaporated at 50 °C to remove methanol, acetic acid, and water.

[0142] Using the loss-in-weight method, it was found that the solid content of the siloxane adhesive SB-3 was 48.7%.

[0143] Examples 1 and 2

[0144] This example illustrates the improved contact angle with water when the film is cured under both UV exposure and heat. Siloxane SB-1 from Synthesis Example 1 was used.

[0145] (a) Dilute 4.0712 g DU-1008SIV to 16.0804 g PGMEA to form a 5% solution.

[0146] (b) Dilute 0.6499 g Ebecryl 8602 to 12.9879 g PGMEA to form a 5% solution. Add 0.0260 g Esacure KTO 46 to this solution.

[0147] (c) Mix 8.3523 g of solution (a) and 2.1142 g of solution (b) to prepare the following two formulations:

[0148] Example 1 Example 2

[0149] 5.0095g 5.3404g Solution (c)

[0150] 0.0521g 0.0888g SB-1 solution

[0151] The resulting solvent is a mixture of MIBK and PGMEA. The final amounts of each component in the curable composition are given in Table 1 below.

[0152] Table 1. Solid composition (grams)

[0153] sample <![CDATA[h-SiO2]]> SB-1 Ebecryl KTO46 Example 1 0.202 0.028 0.0506 0.00202 Example 2 0.215 0.047 0.0540 0.00215

[0154] h-SiO2 is the weight of the hollow silica solid; SB-1 is the weight of the siloxane binder.

[0155] The solutions from Examples 1 and 2 were filtered three times using a 1.0 μm PTFE syringe filter and then spin-coated onto an 8-inch silicon wafer at 1500 rpm. The coated wafers were baked at 90°C for 60 seconds to dry the film. The wafers were then cut in half, with one half cured only under broadband UV radiation and the other half UV-cured plus thermally cured (at 200°C for 1 hour). The contact angle (CA) and refractive index (RI) of the film were measured, and the results are given in Table 2.

[0156] Table 2. Results

[0157] sample Curing CA RI Example 1 UV only 99.2° 1.288 Example 1 UV + heat 125.1° 1.288 Example 2 UV only 100.9° 1.288 Example 2 UV + heat 127.6° 1.287

[0158] CA = Angle of contact with water; RI = Refractive index

[0159] This example demonstrates an improvement (increase) in the contact angle when using both UV and thermosetting methods.

[0160] Example 3

[0161] This example illustrates the preparation of AR films using the siloxane binder SB-2 from Synthesis Example 2.

[0162] (a) Dilute 30.0536 g of the binder solution from Synthesis Example 2 to 64.8297 g of PGMEA to form a 25% solution. Add 0.8280 g of Esacure KTO 46, 1.6916 g of LED 02, 0.4091 g of TfBDMBA thermal acid generator and 1.6059 g of KY 1203 fluorinated surfactant to this solution.

[0163] (b) Mix 3.0319g of DU-1008SIV with 1.6015g of (a) (above).

[0164] The solid composition of (b) is summarized below, where the amounts are in grams.

[0165]

[0166] In the above composition:

[0167] The percentage of siloxane binder by weight of the total material with reactive groups = 89% (hollow silica / total reactive material = 1.44%)

[0168] Preparation (b) was filtered three times using a 1.0 μm PTFE syringe filter and then spin-coated onto an 8-inch silicon wafer at 1000 rpm. The coated wafer was baked at 90°C for 60 seconds to dry the film. The coated wafer was cut in half, with one half cured by broadband UV only and the other half cured by UV plus thermal curing (200°C / 1 hour). The contact angles with water for the films cured by UV only and UV plus thermal curing were measured to be 103° and 120°, respectively.

[0169] For films cured only by UV, the marking pen test rating is good.

[0170] For films that use both UV and heat curing, the marking pen test rating is excellent.

[0171] Example 4

[0172] This example illustrates the preparation of AR films using the siloxane binder SB-3 from Synthesis Example 3.

[0173] (a) 8.3421 g of the siloxane oligomer SB-3 from Synthesis Example 3 was diluted in 16.2630 g of PGMEA to form a 25% solids solution. To this solution, 0.2097 g of Esacure KTO 46 photoinitiator, 0.4086 g of LED 02 acrylate oligomer, 0.4069 g of KY 1203 fluorinated surfactant, and 1.0093 g of SR399 monomer were added.

[0174] (b) Mix 3.0158g of DU-1008SIV with 1.6025g of (above).

[0175] The solid composition of (b) is summarized below, where the quantities are expressed in g of solids.

[0176]

[0177] In the above composition:

[0178] The percentage of siloxane binder by weight of the total material with reactive groups = 73% (Hollow silica / Total reactive material = 1.24%)

[0179] Preparation (b) was filtered three times using a 1.0 μm PTFE syringe filter and then spin-coated onto an 8-inch silicon wafer at 1000 rpm. The coated wafer was baked at 90°C for 60 seconds to dry the film. The coated film was then UV-cured at 150°C for 30 minutes. The film contact angle was measured to be 110°, and under a 1 kg load, it measured 2 × 2 cm. 2 After 250 cycles or 500 times of steel wool testing in the contact area, the water contact angle became 102°.

[0180] For films cured only by UV, the marking pen test rating is good.

[0181] For films that use both UV and heat curing, the marking pen test rating is excellent.

[0182] The second sample was treated as described above, except that it was heat-cured at 200°C for 1 hour. This film exhibited a water contact angle of 115°.

[0183] Example 5 and Comparative Example A

[0184] This example illustrates the preparation of AR films.

[0185] The compositions were prepared in a similar manner to those described above and are summarized in Table 3 below. In both cases, the weight ratio of hollow silica to the total amount of all materials with reactive groups was 1.3.

[0186] Table 3 Solid composition (grams)

[0187]

[0188] h-SiO2 = Hollow silica solid; Monomer = SR399; A-POSS = Acryloyl-POSS; Fluorinated surfactant = Solid from KY-1203; A-POSS% is the percentage by weight of acryloyl-POSS relative to the total weight of all materials with reactive groups (monomer + A-POSS + LEDO2 + fluorinated surfactant).

[0189] Each of the two formulations described above, with a total solids content of 21.55%, was filtered three times using a 1.0 μm PTFE syringe filter and then spin-coated onto an 8-inch silicon wafer at 1000 rpm. The coated wafer was baked at 90°C for 60 seconds to dry the film. The coated film was then UV-cured under a nitrogen atmosphere and subsequently heat-cured at 150°C for 30 minutes (in air). Initial and steel wool tests (1 kg load at 2 × 2 cm) were conducted. 2 The water contact angle was measured at different stages of the contact area, as summarized in Table 4 below.

[0190] Table 4. Test Results

[0191]

[0192] ---Indicates that the contact angle could not be measured due to severe scratching damage to the membrane.

[0193] As can be seen, the scratch resistance is greatly improved in the film of Example 5, where the weight of the siloxane binder is greater than 50% of the total weight of the material with reactive groups.

[0194] Examples 6 and 7 and comparison example BD

[0195] These examples illustrate the preparation of AR films with different ratios of hollow silica and materials containing all reactive groups.

[0196] The compositions were prepared in a similar manner to those described above and are summarized in Table 5 below.

[0197] Table 5. Solid composition (grams)

[0198]

[0199] h-SiO2 = Hollow silica solid; A-POSS = Acryloyl POSS; Fluorinated surfactant = Solid from KY-1203

[0200] Each formulation was filtered three times using a 1.0 μm PTFE syringe filter and then spin-coated onto an 8-inch silicon wafer at 1000 rpm. The coated wafer was baked at 90°C for 60 seconds to dry the film. The coated film was then subjected to broadband UV curing under a nitrogen atmosphere and subsequently heat-cured at 150°C for 30 minutes (in air). Initial and steel wool tests (1 kg load at 2 × 2 cm) were performed. 2 The water contact angle was measured after 500 cycles in the contact area. The results are summarized in Table 6 below.

[0201] Table 6. Results

[0202]

[0203] A-POSS% is the percentage of the weight of acryloyl-POSS relative to the total weight of all materials with reactive groups (A-POSS + LED02 + fluorinated surfactant); h-SiO2 / total acrylate = the weight ratio of hollow silica to the total weight of all materials with reactive groups (A-POSS + LED02 + fluorinated surfactant); %CA loss = the percentage change in contact angle relative to the initial contact angle.

[0204] As can be seen from Table 6, when the total weight ratio of hollow silica to materials with reactive groups is greater than 1.75, both the initial contact angle and scratch resistance are greatly reduced.

[0205] It should be noted that not all of the activities described above in the general description or examples are necessary; some specific activities may not be necessary, and one or more other activities may be performed in addition to those described. Furthermore, the order of the listed activities does not necessarily represent the order in which they are performed.

[0206] In the foregoing specification, the concepts have been described with reference to specific embodiments. However, those skilled in the art will understand that various modifications and changes can be made without departing from the scope of the invention as defined in the following claims. Therefore, the specification and drawings should be considered exemplary rather than limiting, and all such modifications are intended to be included within the scope of the invention.

[0207] The benefits, other advantages, and solutions to problems have been described above with reference to specific embodiments. However, the benefits, advantages, solutions to problems, and any one or more features that may cause any benefit, advantage, or solution to appear or make it more apparent shall not be construed as key, essential, or fundamental features of any or all claims.

[0208] It should be understood that, for clarity, certain features described herein in the context of individual embodiments may also be provided in combination in a single embodiment. Conversely, for brevity, the various features described in the context of a single embodiment may also be provided individually or in any sub-combination. The use of numerical values ​​within the various ranges specified herein is expressed as approximations, as if both the minimum and maximum values ​​within the range were preceded by the word "approximately". In this way, slightly higher and lower than the ranges can achieve substantially the same results as values ​​within these ranges. Moreover, the disclosure of these ranges is intended as a continuous range including each value between the minimum and maximum average values, including fractional values ​​that may be produced when some components of a value are mixed with components of different values. Furthermore, when wider and narrower ranges are disclosed, it is in the intention of the invention to match the minimum value from one range with the maximum value from another range, and vice versa.

Claims

1. A curable composition for forming an antireflective film, the composition comprising: (a) Hollow silica nanoparticles; (b) Siloxane adhesives with reactive groups; (c) At least one additional material having a reactive group, said additional material comprising monomers, oligomers and surfactants; (d) Initiator; and (e) Solvent; in: (i) The siloxane adhesive is present in an amount of at least 80% by weight of the total weight of (siloxane adhesive + additional material having reactive groups); and (ii) The weight ratio of hollow silica nanoparticles to (siloxane binder + additives with reactive groups) is (600 / 729):1 to 1.44:

1.

2. The curable composition of claim 1, wherein, The siloxane adhesive (b) is selected from the group consisting of siloxane polymers, silsesquioxanes, and combinations thereof.

3. The curable composition of claim 1, wherein, The surfactant is a fluorinated surfactant.

4. The curable composition of claim 1, wherein, The reactive group is a (meth)acrylate group.

5. The curable composition of claim 1, wherein, The initiator (d) is selected from the group consisting of: photoinitiators, thermal initiators, and combinations thereof.

6. An antireflective coating manufactured by the following method: (1) Applying the curable composition of any one of claims 1-5 onto a substrate to form an uncured film; (2) Dry the uncured film to form a dried uncured film; (3) Expose the dried, uncured film to one or both of UV radiation and heat to form the antireflective film.

7. The antireflective coating as described in claim 6, wherein, The dried, uncured film is subsequently exposed to UV radiation and heat.

8. An electronic device having an antireflective coating as claimed in claim 6 thereon.

Images