# US 9,435,916 B2 · Antireflective articles and methods of making the same

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- Number: US 9,435,916 B2
- Document ID: US9435916B2
- Status: Granted
- Kind: B2
- Application number: 12/641,478
- Filed: 2009-12-18
- Published: 2010-07-01
- Granted: 2016-09-06
- Earliest claimed: 2008-12-30
- Assignees: 3M Innovative Properties Company
- Applicants: Moses M. David; Andrew K. Hartzell; Timothy J. Hebrink; Ta-Hua Yu; Jun-Ying Zhang; Kalc C. Vang; Ming Cheng
- Inventors: Moses M. David; Andrew K. Hartzell; Timothy J. Hebrink; Ta-Hua Yu; Jun-Ying Zhang; Kalc C. Vang; Ming Cheng
- Web page: https://patentgrep.com/patent/US9435916B2

## CPC

- G02B 1/118: having sub-optical wavelength surface structures designed to provide an enhanced transmittance, e.g. moth-eye structures
- B05D 3/107: {Post-treatment of applied coatings}
- B05D 5/06: to obtain multicolour or other optical effects (B05D5/02 takes precedence)
- B32B 7/12: using interposed adhesives or interposed materials with bonding properties
- B32B 17/06: comprising glass as the main or only constituent of a layer, next to another layer of a specific {material}
- B32B 37/02: characterised by a sequence of laminating steps, e.g. by adding new layers at consecutive laminating stations
- B32B 38/0008: {Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation (heat treatment B32B38/0036)}
- C08J 7/0423: {with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder}
- C08J 7/043: Improving the adhesiveness of the coatings per se, e.g. forming primers (adhesives in the form of films or foils characterised by the primer layers between the polymer carriers and the adhesives C09J7/50)
- C08J 7/044: Forming conductive coatings; Forming coatings having anti-static properties
- C08J 7/046: Forming abrasion-resistant coatings; Forming surface-hardening coatings
- C08J 7/054: Forming anti-misting or drip-proofing coatings
- C08J 7/056: Forming hydrophilic coatings
- C08J 7/123: {Treatment by wave energy or particle radiation (C08J7/18 takes precedence)}
- G02B 1/111: using layers comprising organic materials
- G02B 1/12: by surface treatment, e.g. by irradiation
- G02B 1/14: Protective coatings, e.g. hard coatings
- G02B 1/18: Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films (G02B1/16 takes precedence)
- G02B 27/0006: {with means to keep optical surfaces clean, e.g. by preventing or removing dirt, stains, contamination, condensation (G02B1/18 takes precedence; cleaning in general B08B)}
- B32B 2255/26: Polymeric coating
- B32B 2307/412: Transparent
- B32B 2307/42: Polarizing, birefringent, filtering
- B32B 2457/20: Displays, e.g. liquid crystal displays, plasma displays
- B32B 2457/202: LCD, i.e. liquid crystal displays
- B32B 2551/00: Optical elements
- C08J 2323/06: Polyethene
- C08J 2367/02: Polyesters derived from dicarboxylic acids and dihydroxy compounds; (C08J2367/06 takes precedence)
- C08J 2433/06: of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J 2433/08: Homopolymers or copolymers of acrylic acid esters
- C08J 2483/02: Polysilicates
- F24S 70/10: characterised by the absorbing material (absorbing coatings or surface treatment for increasing absorption F24S70/20)
- F24S 70/60: characterised by the structure or construction (absorbing coatings or surface treatment for increasing absorption F24S70/20; auxiliary coatings F24S70/30)
- Y10T 428/254: Polymeric or resinous material
- Y10T 428/257: Iron oxide or aluminum oxide
- Y10T 428/258: Alkali metal or alkaline earth metal or compound thereof
- Y10T 428/259: Silicic material
- Y10T 428/2848: Three or more layers
- G02B: OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- B05D: PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (conveying articles or workpieces through baths of liquid B65G, e.g. B65G49/02)
- B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- F24S: SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS (for producing mechanical power from solar energy F03G6/00)
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

A composite having (a) a substrate that has opposing first and second surfaces, the substrate being at least 90% transmissive in visible light and has less than 5% haze, (b) a nanostructured article including a matrix and a nanoscale dispersed phase and having a random nanostructured anisotropic surface; and (c) an optically clear adhesive disposed on the second surface of the substrate.

## Claims

### Claim 1

A composite comprising:
(a) a substrate having at least 90% transmission in visible light and less than 5% haze, the substrate having opposing first and second surfaces;
(b) a nanostructured article disposed on the first surface of the substrate, the nanostructured article comprising a matrix and a nanoscale dispersed phase, and having a major surface that is only an exposed etched random nanostructured anisotropic surface defined by nano-pillars or nano-columns comprising the matrix and nanoscale dispersed phase, wherein the nano-pillars and nano-columns are structural asperities having an aspect ratio of 5:1 or greater, and wherein the nanostructured article has a length along an x-direction, a width along a y-direction, and a thickness along a z-direction, wherein the nanoscale features comprise nano-pillars generally in the z-direction, wherein a majority of the nano-pillars are capped with physically exposed nanoscale dispersed phase from the nanoscale phase in the matrix;
(c) an optically clear adhesive disposed on the second surface of the substrate, the optically clear adhesive having at least 90% transmission in visible light and less than 5% haze.

### Claim 2 (depends on 1)

A display for electronic application comprising the composite of claim 1 laminated to a glass substrate such that the optically clear adhesive contacts the glass substrate, or a polarizer and assembling the laminates with a liquid display module.

### Claim 3 (depends on 1)

The composite of claim 1, wherein the matrix comprises a hardcoat comprising nanoparticles of SiO2, ZrO2 and combinations thereof dispersed in a crosslinkable matrix comprising multi(meth)acrylate, polyester, epoxy, fluoropolymer, urethane, siloxane, or blends or copolymers thereof.

### Claim 4 (depends on 1)

The composite of claim 1, wherein the nanoscale dispersed phase comprises nanoparticles of SiO2, ZrO2, TiO2, ZnO, Al2O3, calcium carbonate, magnesium silicate, indium tin oxide, antimony tin oxide, poly(tetrafluoroethylene), carbon, and combinations thereof.

### Claim 5 (depends on 4)

The composite of claim 4, wherein the nanoparticles having average particle size of less than about 100 nm.

### Claim 6 (depends on 5)

The composite of claim 5, wherein the nanoparticles are surface modified.

### Claim 7 (depends on 1)

The composite of claim 1, wherein the matrix comprises a polymer selected from the group consisting of polycarbonate, poly(meth)acrylate, polyester, nylon, siloxane, fluoropolymer, urethane, epoxy, cyclic olefin copolymer, triacetate cellulose, diacrylate cellulose or blends or copolymers thereof.

### Claim 8 (depends on 1)

The composite of claim 1, wherein the matrix comprises an inorganic material selected from the group of silicon oxide and tungsten carbide.

### Claim 9 (depends on 1)

The composite of claim 1, wherein the substrate comprises a cross-linkable material selected from multi(meth)acrylate, polyester, epoxy, fluoropolymer, urethane, siloxane, or blends or copolymers thereof.

### Claim 10 (depends on 1)

The composite of claim 1, wherein the substrate comprises a polymer selected from the group consisting of polycarbonate, poly(meth)acrylate, polyester, nylon, siloxane, fluoropolymer, urethane, epoxy, cyclic olefin copolymer, triacetate cellulose, diacrylate cellulose or blends or copolymers thereof.

### Claim 11 (depends on 1)

The composite of claim 1, wherein the substrate comprises a glass or a polarizer.

### Claim 12 (depends on 1)

The article of claim 1, wherein the matrix comprises an alloy or a solid solution.

### Claim 13 (depends on 1)

The composite of claim 1, wherein the concentration of the dispersed phase within the matrix is between about 5 and 90 weight percent.