阅读说明：本技术 减反射涂层 (Antireflection coating ) 是由 王德岩 刘盛 于 2020-02-14 设计创作，主要内容包括：提供了一种用于形成减反射膜的可固化组合物。所述组合物包含：(a)中空二氧化硅纳米颗粒；(b)具有反应性基团的硅氧烷粘合剂；(c)至少一种具有反应性基团的附加材料；(d)引发剂；以及(e)溶剂。所述硅氧烷粘合剂以(硅氧烷粘合剂+具有反应性基团的附加材料)的总重量的至少50重量％的量存在。中空二氧化硅纳米颗粒与(硅氧烷粘合剂+具有反应性基团的附加材料)的总和的重量比是不大于1.75至1。(A curable composition for forming an antireflection film is provided. The composition comprises: (a) hollow silica nanoparticles; (b) a silicone adhesive having reactive groups; (c) at least one additional material having reactive groups; (d) an initiator; and (e) a solvent. The silicone adhesive is present in an amount of at least 50 wt% of the total weight of (silicone adhesive + additional material having reactive groups). The weight ratio of hollow silica nanoparticles to the sum of (silicone binder + additional material having reactive groups) is no greater than 1.75 to 1.)

1. A curable composition for forming an antireflection film, the composition comprising:

(a) hollow silica nanoparticles;

(b) a silicone adhesive having reactive groups;

(c) at least one additional material having reactive groups;

(d) an initiator; and

(e) a solvent;

wherein:

(i) the silicone adhesive is present in an amount of at least 50 wt% of the total weight of (silicone adhesive + additional material having reactive groups); and is

(ii) The weight ratio of hollow silica nanoparticles to the sum of (silicone binder + additional material having reactive groups) is no greater than 1.75 to 1.

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

3. The curable composition of claim 1, wherein the additional material (c) is selected from the group consisting of: monomers, oligomers, surfactants, and combinations thereof.

4. The curable composition of claim 1 wherein the additional material (c) comprises a fluorinated surfactant.

5. The curable composition of claim 1 wherein the additional material (c) comprises a fluorinated surfactant and an oligomer.

6. The curable composition of claim 3, wherein the reactive group is a (meth) acrylate group.

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

8. The curable composition of claim 1, wherein the silicone adhesive is present in an amount of at least 60 wt% of the total weight of (silicone adhesive + additional material having reactive groups).

9. The curable composition of claim 1, wherein the weight ratio of hollow silica nanoparticles to the sum of (silicone binder + additional material having reactive groups) is no greater than 1.50 to 1.

10. An antireflection film, which is produced by the following method:

(1) applying the above curable composition to a substrate to form an uncured film;

(2) drying the uncured film to form a dried uncured film;

(3) exposing the dried uncured film to one or both of UV radiation and heat to form the anti-reflective film.

11. The antireflection film of claim 10 wherein the dried uncured film is exposed to UV radiation and heat sequentially.

12. An electronic device having the antireflection film according to claim 10 thereon.

13. A curable composition for forming an antireflection film, the composition comprising:

(a) hollow silica nanoparticles;

(b) a silicone adhesive having reactive groups;

(c) at least one additional material having reactive groups;

(d) an initiator; and

(e) a solvent;

wherein no silicon-free binder is present in the composition.

Technical Field

The present invention relates to curable compositions for antireflective coatings, particularly for display devices.

Background

Anti-reflective (AR) coatings on the topmost surface of display devices have become increasingly important in the display industry. This is particularly true in order to achieve an enhanced visual experience, especially in strong ambient light environments. In addition to being used as an anti-reflective coating, this film layer is also expected to function as a scratch-resistant coating having anti-fingerprint properties. In essence, this is an ultra-thin hard coating on the surface of the mobile device. The Film Thickness (FT) is selected to ensure that the reflected light rays from the top and bottom surfaces of the AR film are opposite in phase, i.e., 180 ° out of phase, so that the light rays reflected from the top and bottom surfaces destructively interfere to cancel 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.

There is a continuing need for AR coatings with improved properties.

Disclosure of Invention

There is provided a curable composition for forming an antireflective coating, the composition comprising:

(a) hollow silica particles;

(b) a silicone adhesive having reactive groups;

(c) at least one additional material having reactive groups;

(d) an initiator; and

(e) a solvent;

wherein:

(i) the silicone adhesive is present in an amount of at least 50 wt% of the total weight of (silicone adhesive + additional material having reactive groups); and

(ii) the weight ratio of hollow silicon dioxide particles to the sum of (silicone binder + additional material having reactive groups) is not more than 1.75.

Further provided is an antireflection film, which is manufactured by:

(1) applying the above curable composition to a substrate to form an uncured film;

(2) drying the uncured film to form a dried uncured film;

(3) exposing the dried uncured film to one or both of UV radiation and heat to form the AR film.

There is further provided an electronic device having the above antireflection film thereon.

Definition of

As used herein, the term "binder" is intended to mean a material that holds particles and other materials together and provides mechanical strength and a uniform consistency.

The term "curable" as it applies to a composition is intended to mean a material that becomes harder and less soluble in a solvent when exposed to radiation and/or heat.

The term "hollow silica particles" is intended to mean silica particles having voids on the surface of the particles and/or inside the particles.

The term "(meth) acrylate" is intended to mean a group that is an acrylate or a methacrylate.

The term "polyhedron" is intended to mean a cage-like structure with polygonal faces.

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

The term "reactive group" is intended to mean a group capable of polymerizing or crosslinking upon exposure to radiation and/or heat.

The term "siloxane" is intended to mean a material having a molecular structure based on chains of alternating silicon and oxygen atoms, with organic groups attached to the silicon atoms.

The term "silsesquioxane" is intended to mean a silsesquioxane having the formula [ RSiO_1.5]_nWherein n is an even integer and R can be H or an organofunctional group. R may be the same or different at each occurrence.

The term "solvent" is intended to mean an organic compound that is liquid at room temperature. The term is intended to encompass a single organic compound or a mixture of two or more organic compounds.

All ranges are inclusive and combinable. For example, the term "a range of 50 to 3000cPs, or 100 or more cPs" will include each of 50 to 100cPs, 50 to 3000cPs, and 100 to 3000 cPs.

In this specification, unless the context of usage clearly dictates otherwise or indicates to the contrary, where an embodiment of the inventive subject matter is stated or described as comprising, including, containing, having, consisting of or consisting of certain features or elements, one or more features or elements other than those explicitly stated or described may also be present in the embodiment. Alternative embodiments of the disclosed subject matter are described as consisting essentially of certain features or elements, wherein embodiment features or elements that would materially alter the principle of operation or the distinguishing characteristics of the embodiments are not present here. Another alternative embodiment of the subject matter described is described as consisting of certain features or elements, in which embodiment, or in insubstantial variations thereof, only the features or elements specifically stated or described are present.

Also, the use of "a/an" is used to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

Unless defined otherwise, 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 belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described below. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

To the extent not described herein, many details regarding specific materials, processing acts, and circuits are conventional and may be found in textbooks and other sources within the photoresist, organic light emitting diode display, photodetector, photovoltaic cell, and semiconductor component arts.

Detailed Description

The curable compositions described herein may be used to form an anti-reflective ("AR") film. The curable composition may be applied to a device or substrate and cured to form an AR film. Such films have been found to have improved scratch resistance. Such films have further been found to have improved anti-fingerprint properties.

The curable composition comprises:

(a) hollow silica particles;

(b) a silicone adhesive having reactive groups;

(c) at least one additional material having reactive groups;

(d) an initiator; and

(e) a solvent.

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.

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

In some embodiments, a majority of the voids in the hollow silica particles are within the particles; in some embodiments, substantially all of the voids are within the particle.

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

Hollow silica particles are readily commercially available.

In some embodiments, the hollow silica particles are present in an amount of 30 to 80 weight percent based on the total weight of solids in the curable composition; in some embodiments, 35-70 wt%; in some embodiments, 40-65 wt%. 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.

The curable composition includes a silicone adhesive having reactive groups. In some embodiments, the curable composition is free of a non-silicon containing adhesive. "silicon-free" refers to materials in which no Si atoms are present.

In some embodiments, the silicone adhesive is selected from the group consisting of: silsesquioxanes, oligomeric siloxanes, polymeric siloxanes, and combinations thereof.

In some casesIn an embodiment, the silicone 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"n" in (1). In some embodiments, n-8. In some embodiments, POSS are mixtures of polyhedrons having 6-12 vertices.

In some embodiments, the silicone adhesive is a silicone oligomer. In some embodiments, the siloxane oligomer has a fluorine substituent. In some embodiments, the siloxane oligomer has a fluorine content of 1 to 25 weight percent.

In some embodiments, the siloxane oligomer has no fluorine substituents.

In some embodiments, the siloxane oligomer has a weight average molecular weight Mw of 1000-.

The silicone adhesive has at least one reactive group. In some embodiments, the silicone adhesive has a plurality of reactive groups. In some embodiments, 50% to 100% of the Si atoms are bonded to the reactive groups; in some embodiments, 75% -100%.

In some embodiments, the reactive group is selected from the group consisting of: acrylates, methacrylates, vinyls, epoxies, isocyanates, and combinations thereof.

In some embodiments, the reactive group on the silicone adhesive is an acrylate or methacrylate.

One specific example of a silicone adhesive having a reactive group is acryl-POSS (acrylo-POSS). acryloyl-POSS is a mixture of cage structures with 8, 10, and 12 Si atoms, and each Si atom is bonded to an acryloylpropyl group. Additional silicone adhesives with reactive groups are shown in the examples.

In some embodiments, the silicone adhesive having reactive groups is present in an amount of 15 to 70 weight percent based on the weight of solids in the curable composition; in some embodiments, 30-60 wt%; in some embodiments, 40-50 wt%.

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 may be any of those described above.

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

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

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

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

Some 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.

In some embodiments, the monomer is present in an amount of 0 to 15 weight percent based on the weight of solids in the curable composition; in some embodiments, 0-10 wt%; in some embodiments, 0-5 wt%.

In some embodiments, no monomer is present in the curable composition.

In some embodiments, the additional material having a reactive group 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.

In some embodiments, the additional material having a reactive group is a (meth) acrylate oligomer.

In some embodiments, the oligomer having a reactive group has a weight average molecular weight Mw of 1000-10,000.

In some embodiments, the oligomer having a reactive group is present in an amount of 1.5 to 7.0 weight percent based on the weight of solids in the curable composition; in some embodiments, 3.0-6.0 wt%; in some embodiments, 4.0-5.0 wt%.

In some embodiments, the additional material having a reactive group is a surfactant. In some embodiments, the additional material having a reactive group is a fluorosurfactant. In some embodiments, the fluorosurfactant has a fluorine content of 1-25 wt%.

In some embodiments, the surfactant having a reactive group is present in an amount of 0.1 to 5.0 wt% based on the weight of solids in the curable composition; in some embodiments, 0.5-1.0 wt%.

Surfactants and fluorosurfactants are well known in the art and are commercially available.

The curable composition includes an initiator. An initiator is present to produce a reactive species that initiates polymerization and/or crosslinking of reactive groups in the curable composition.

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

In some embodiments, the initiator is a thermal initiator. Any known thermal initiator may 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.

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

In some embodiments, the total amount of initiator present is 0.5 to 5 weight percent based on the weight of solids in the curable composition; in some embodiments, 1-3 wt%.

The curable composition includes a solvent. Any solvent may be used in the curable composition so long as the other components are sufficiently dissolved or dispersed so that the composition can 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.

Some specific examples of solvents include, but are not limited to, methyl isobutyl ketone, isobutanol, propylene glycol methyl ether acetate, tetrahydrofuran, and the like.

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

In some embodiments of the curable composition described herein, the weight of the silicone adhesive is at least 50% of the total weight of the material 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 material with reactive groups). In some embodiments, the silicone adhesive is at least 60% of the total weight of the material having reactive groups; in some embodiments, at least 70%; in some embodiments, at least 80%; in some embodiments, at least 90%.

In some embodiments of the curable composition, the weight ratio of hollow silica particles to the total weight of the material having reactive groups is no greater than 1.75; in some embodiments, no greater than 1.6; in some embodiments, no greater than 1.5; in some embodiments, no greater than 1.4.

The curable compositions described herein may be used to make AR films. The method of manufacturing an AR film includes:

(1) applying the above curable composition to a substrate to form an uncured film;

(2) drying the uncured film to form a dried uncured film;

(3) exposing the dried uncured film to one or both of UV radiation and heat to form the AR film.

The curable composition may 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, rod coating, dip coating, and gravure coating.

The substrate may be any on which an AR coating is desired. The substrate may be glass or a polymeric material.

In some embodiments, the uncured film is dried by heating. In some embodiments, the drying temperature is from 50 ℃ to 120 ℃; in some embodiments, from 70 ℃ to 100 ℃. In some embodiments, the drying time is 30 seconds to 2 minutes.

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. Generally, broadband UV radiation can be used with an exposure time of a few seconds.

In some embodiments, the dried uncured film is cured by heating. In some embodiments, the heating temperature is from 150 ℃ to 250 ℃; in some embodiments, 175 ℃ -225 ℃. In some embodiments, the heating time is 30-120 minutes.

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.

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; in some embodiments, 100 and 200 nm. The film thickness should satisfy the following optical relationship with the target wavelength in the visible spectrum:

FT＝k(λ/4)

wherein:

λ＝λ_o/n

λ_ois the target wavelength in the vacuum and,

n is the refractive index of the AR coating, and

k is an odd integer

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

The AR films described herein have a low refractive index. In some embodiments, the refractive index is less than 1.5; in some embodiments, less than 1.4; in some embodiments, less than 1.3.

The AR films described herein have high visible light transmission. In some embodiments, the transmittance is greater than 90%; in some embodiments, greater than 95%.

The AR films described herein have a high contact angle with water. In some embodiments, the contact angle is greater than 100 °; in some embodiments, greater than 110 °; in some embodiments, greater than 115 °. High contact angles result in improved anti-smudge and anti-fingerprint properties.

The AR films described herein have improved scratch resistance. This is further illustrated in the examples.

The AR film may be used in any application where AR properties are desired. In some embodiments, the AR film is used on the topmost surface of the display device.

Examples of the invention

The concepts described herein are further illustrated in the following examples, which do not limit the scope of the invention described in the claims.

Materials:

DU-1008 ═ DU-1008SIV, hollow silica particles from catalyst and Chemicals (catalysis and Chemicals Ltd.) (japan); this material was provided as a 20% dispersion in methyl isobutyl ketone ("MIBK").

Acryloyl POSS ═ POSS with acrylate functionality, from mixed plastics corporation (hybrid plastics) (usa).

KY-1203 is a fluorosurfactant from ShinEtsu USA (japan); this material was provided as a 20% solution in MIBK.

DAC-HP (Optool DAC-HP), a fluorosurfactant from Daikin, japan; this material was provided as a 20% solution in 1,1,2,2,3,3, 4-heptafluorocyclopentane and PGME.

SR399 ═ dipentaerythritol pentaacrylate from Sartomer (U.S.A.)

LED 02-thiol-modified polyester acrylate from Zhanxin (Allnex) (USA)

KTO ═ Esacure KTO 46, free radical photoinitiators from IGM company (USA)

Ebecryl 8602, an aliphatic urethane acrylate oligomer from Zhanxin

Photomer 4356, a triacrylate monomer from IGM (usa)

TfbMBA ═ thermal acid generator from Korea E & I company (E & I Korea)

Test method

Contact angle

The contact angle of the AR coating surface with water was determined using a KRUSS droplet shape analyzer (model 100). In this test, the water drop size is 1 to 2. mu.l.

Refractive index

This was determined using a laboratory refractometer.

Marker pen testing

This is a qualitative test for the oleophobicity of AR membranes. The marker used was a red, blue or black sharp (Sharpie) permanent marker. This test is based on surfaces that have not been treated for anti-fingerprint properties. The surface is rendered with a marker to show clear and distinct marker traces. AR coatings with good anti-fingerprint properties are not drawable with a marker pen, showing ink build-up by forming droplets along the drawn line.

Steel wool test

This test was carried out using a 5900 reciprocating mill from Taber Industries. Steel wool used in the test was fromNippon Steel Wool Co.Ltd. (Nippon Steel Wool Co. Ltd.). in this test, 2 × 2cm on an AR membrane²A 1kg force was used on the test area with a stroke length of 5cm and a stroke rate of 1 cycle/second.

Synthesis example 1

This example illustrates the preparation of a fluorinated silicone adhesive SB-1.

To a 100ml round bottom flask was added 4.5383g acryloxypropyltrimethoxysilane, 10.5331g nonafluorohexyltrimethoxysilane, 2.5350g DI water, 0.8262g acetic acid, 10.1202g cyclopentanol, and 0.0358g butylated hydroxytoluene ("BHT"). The flask was connected to a condenser and the contents of the flask were heated to 80 ℃ and held at 80 ℃ for 6 hours with stirring.

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

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

Synthesis example 2

This example illustrates the preparation of a silicone adhesive SB-2.

To a 100ml round bottom flask was added 18.5672g of acryloxypropyltrimethoxysilane, 16.4758g of tetraethylorthosilicate ("TEOS"), 8.9860g of DI water, 1.7723g of acetic acid, and 0.0308g of BHT. The flask was connected to a condenser and the contents of the flask were heated to 80 ℃ and held at 80 ℃ for 2 hours with stirring.

Then 35g PGMEA was added to the flask. The solution was rotary evaporated at 50 ℃ to remove methanol, ethanol, acetic acid and water.

Using the weight loss method, the solids content of the silicone adhesive SB-2 was found to be 53.85%.

Synthesis example 3

This example illustrates the preparation of a silicone adhesive SB-3.

To a 100ml round bottom flask was added 30.1587g acryloxypropyltrimethoxysilane, 7.3297g DI water, 1.8534g acetic acid and 0.0300g BHT. The flask was connected to a condenser and the contents of the flask were heated to 80 ℃ and held at 80 ℃ for 2 hours with stirring.

Then 40g of PGMEA was added to the flask. The solution was rotary evaporated at 50 ℃ to remove methanol, acetic acid and water.

Using the weight loss method, the solids content of the silicone adhesive SB-3 was found to be 48.7%.

Examples 1 and 2

This example illustrates the improvement in contact angle with water when the film is cured with both UV exposure and heat. Siloxane SB-1 from Synthesis example 1 was used.

(a) 4.0712g of DU-1008SIV were diluted into 16.0804g of PGMEA to form a 5% solution.

(b) 0.6499g of Ebecryl 8602 were diluted into 12.9879g of PGMEA to form a 5% solution. To this was added 0.0260g Esacure KTO 46.

(c) 8.3523g of solution (a) and 2.1142g of solution (b) were mixed and the following two formulations were made:

example 1 Example 2

5.0095g 5.3404g solution (c)

0.0521g of 0.0888g of SB-1 solution

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

TABLE 1 solid ingredients (g)

Sample (I)	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

h-SiO2 is the weight of the hollow silica solid; SB-1 is the weight of the silicone adhesive

The solutions of examples 1 and 2 were filtered 3 times with 1.0 μm PTFE syringe filters, respectively, and then spin-coated onto 8 inch silicon wafers at 1500 rpm. The coated wafer was baked at 90 ℃ for 60 seconds to dry the film. The wafer was then cut in half, with one half cured only under broadband UV radiation and the other half UV plus thermal cure (200 ℃ for 1 hour). Film Contact Angles (CA) and Refractive Indices (RI) were measured and the results are given in table 2.

TABLE 2 results

Sample (I)	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

CA ═ contact angle with water; RI ═ refractive index

This example shows the improvement (increase) in contact angle when using both UV and thermal curing.

Example 3

This example illustrates the preparation of an AR film using the silicone adhesive SB-2 from synthesis example 2.

(a) 30.0536g of the binder solution from synthesis example 2 was diluted into 64.8297g of PGMEA to form a 25% solution. To this solution was added 0.8280g Esacure KTO 46, 1.6916g LED02, 0.4091g TfBDMBA thermal acid generator, and 1.6059g KY 1203 fluorosurfactant.

(b) 3.0319g DU-1008SIV was mixed with 1.6015g (a) (above).

(b) The solid components of (a) are summarized below, wherein the amounts are in g.

In the above composition:

siloxane binder as a percentage of total weight of material with reactive groups 89 hollow silica/total reactive material 1.44

Formulation (b) was filtered 3 times with a 1.0 μm PTFE syringe filter and then spin-coated on an 8 inch silicon wafer at 1000 rpm. The coated wafer was baked at 90 ℃ for 60 seconds to dry the film. The coated wafer was cut in half, one half of which was cured with broadband UV only and the other half was cured with UV plus heat (200 ℃/1 hour). For films cured by UV only and UV plus heat, the contact angles of the film with water were measured as 103 ° and 120 °, respectively.

For films cured using only UV, the rating of the marker test was good.

The rating of the marker test was excellent for films using both UV plus thermal curing.

Example 4

This example illustrates the preparation of an AR film using the silicone adhesive SB-3 from synthesis example 3.

(a) 8.3421g of the siloxane oligomer SB-3 from Synthesis example 3 were diluted into 16.2630g of PGMEA to form a 25% solids solution. To this solution was added 0.2097g Esacure KTO 46 photoinitiator, 0.4086g LED02 acrylate oligomer, 0.4069g KY 1203 fluorosurfactant and 1.0093g SR399 monomer.

(b) 3.0158g of DU-1008SIV were mixed with 1.6025g a (above).

(b) The solid components of (a) are summarized below, wherein the amounts are in g of solid.

In the above composition:

siloxane binder as a percentage of total weight of material having reactive groups 73 hollow silica/total reactive material 1.24

Formulation (b) was filtered 3 times with a 1.0 μm PTFE syringe filter and then spun on an 8 inch silicon wafer at 1000rpm the coated wafer was baked at 90 ℃ for 60 seconds to dry the film, the coated film was cured with UV plus heat at 150 ℃ for 30 minutes the film contact angle was measured as 110 °, and under a 1kg load at 2 × 2cm²The water contact angle becomes 102 deg. after 250 cycles or 500 cycles of steel wool testing of the contact area.

For films cured using only UV, the rating of the marker test was good.

The rating of the marker test was excellent for films using both UV plus thermal curing.

The second sample was treated as described above except that the heat curing was performed at 200 ℃ for 1 hour. This film showed a water contact angle of 115 °.

Example 5 and comparative example A

This example illustrates the preparation of an AR film.

Compositions were prepared in a similar manner to that described above and are summarized in table 3 below. In both cases, the weight ratio of hollow silica to the sum of all materials having reactive groups was 1.3.

TABLE 3 solid ingredients (g)

h-SiO₂A hollow silica solid; SR 399; a-POSS ═ acryloyl POSS; fluorosurfactants-solids from KY-1203; A-POSS% is the weight percentage of acryloyl-POSS based on the total weight of all materials having reactive groups (monomer + A-POSS + LED02+ fluorosurfactant)

Each of the two formulations above, having a total solids content of 21.55%, was filtered 3 times with a 1.0 μm PTFE syringe filter, respectively, and then spin-coated at 1000rpm onto an 8 inch silicon wafer. The coated wafer was baked at 90 ℃ for 60 seconds to dry the film. The coated film was UV cured under nitrogen atmosphere and then thermally cured at 150 ℃ for 30 minutes (in air). Most preferablyPrimary and secondary steel wool test (1kg load at 2 × 2cm 2)²Contact area) were measured at different stages of the process as summarized in table 4 below.

TABLE 4 test results

- -indicates that the contact angle cannot be measured due to severe scratch damage to the film

As can be seen, in the film of example 5, the scratch resistance was greatly improved, with the weight of the siloxane binder being greater than 50% of the total weight of the material having reactive groups.

Examples 6 and 7 and comparative examples B-D

These examples illustrate the preparation of AR membranes with different ratios of hollow silica to materials with all reactive groups.

Compositions were prepared in a similar manner to that described above and are summarized in table 5 below.

TABLE 5 solid content (g)

h-SiO₂A hollow silica solid; a-POSS ═ acryloyl POSS; fluorosurfactants-KY-1203 solids

Each formulation was filtered 3 times with a 1.0 μm PTFE syringe filter and then spun onto an 8 inch silicon wafer at 1000rpm the coated wafer was baked at 90 ℃ for 60 seconds to dry the film the coated film was broadband UV cured under nitrogen atmosphere and then thermally cured at 150 ℃ for 30 minutes (in air)²Contact area) was measured after 500 cycles. The results are summarized in table 6 below.

TABLE 6 results

A-POSS% is the weight percentage of acryloyl-POSS based on the total weight of all materials having reactive groups (A-POSS + LED02+ fluorosurfactant); h-SiO₂Total acrylate-weight ratio of hollow silica to total weight of all materials with reactive groups (a-POSS + LED02+ fluorosurfactant); % CA loss-percent change in contact angle relative to initial contact angle

As can be seen from table 6, when the ratio of the hollow silica to the total weight of the material having the reactive group is greater than 1.75, both the initial contact angle and the scratch resistance are greatly reduced.

It should be noted that not all of the activities described above in the general description or the examples are required, that a portion of a specific activity may not be required, and that one or more other activities may be performed in addition to those described. Further, the order of activities listed are not necessarily the order in which they are performed.

In the foregoing specification, the concepts have been described with reference to specific embodiments. However, one of ordinary skill in the art appreciates that various modifications and changes can be made without departing from the scope of the present invention as set forth in the claims below. Accordingly, the specification and figures are to be regarded in an illustrative rather than a restrictive sense, and all such modifications are intended to be included within the scope of present invention.

Benefits, other advantages, and solutions to problems have been described above with regard to specific embodiments. The benefits, advantages, solutions to problems, and any feature or features that may cause any benefit, advantage, or solution to occur or become more pronounced, however, are not to be construed as critical, required, or essential features of any or all the claims.

It is appreciated that certain features are, for clarity, described herein in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any subcombination. The use of numerical values in the various ranges specified herein is stated to be approximate as if both the minimum and maximum values in the ranges were preceded by the word "about". In this manner, slight variations above and below the stated ranges can be used to achieve substantially the same results as values within the ranges. Moreover, the disclosure of these ranges is intended as a continuous range including every value between the minimum and maximum average values, including fractional values that may result when some components of one value are mixed with components of a different value. Further, when broader and narrower ranges are disclosed, it is within the contemplation of the invention to match the minimum values from one range with the maximum values from the other range, and vice versa.