Poly(vinyl alcohol) and silica nanoparticle multilayer coatings and methods

• US 10,040,953 B2
• Filed: 04/25/2014
• Issued: 08/07/2018
• Est. Priority Date: 05/30/2013
• Status: Active Grant

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Riddle, Justin A., Armstrong, Paul B., Jindal, Karan, Carpenter, Samuel J., Lachmansingh, Garry W., Dudley, William R., Petrin, Jason T., Jing, Naiyong
• Primary Examiner(s): Vo, Hai
• Application Number:
  US14/893,232
• Publication Number:
  US 20160177107A1
• Time in Patent Office: 1,565 Days
• CPC Class Codes: B05D 2201/02 Polymeric substrate
• CPC Class Codes: B05D 2507/00 Polyolefins
• CPC Class Codes: B05D 2518/10 Silicon-containing polymers
• CPC Class Codes: B05D 5/00 Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
• CPC Class Codes: B05D 7/54 No clear coat specified
• CPC Class Codes: B05D 7/544 the first layer is let to dry at least partially before applying the second layer
• CPC Class Codes: B05D 7/546 each layer being cured, at least partially, separately
• CPC Class Codes: B05D 7/584 at least some layers being let to dry, at least partially, before applying the next layer B05D7/587 takes precedence
• CPC Class Codes: B05D 7/586 each layer being cured, at least partially, separately
• CPC Class Codes: C03C 17/007 containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
• CPC Class Codes: C03C 17/42 at least one coating of an organic material and at least one non-metal coating
• CPC Class Codes: C03C 2217/425 consisting of a porous layer
• CPC Class Codes: C08J 7/0423 with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
• CPC Class Codes: 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
• CPC Class Codes: C08J 7/046 Forming abrasion-resistant coatings; Forming surface-hardening coatings
• CPC Class Codes: C08J 7/054 Forming anti-misting or drip-proofing coatings
• CPC Class Codes: C08J 7/056 Forming hydrophilic coatings
• CPC Class Codes: C09D 129/04 Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
• CPC Class Codes: C09D 5/002 Priming paints C09D5/08 takes precedence
• CPC Class Codes: C09D 5/1618 inorganic
• CPC Class Codes: C09D 5/1668 : Vinyl-type polymers
• CPC Class Codes: C09D 5/1693 : as part of a multilayer system

Abstract

Articles having poly(vinyl alcohol) (PVA) and silica nanoparticle multilayer coatings are provided. More specifically, the articles include a substrate and a multilayer coating attached to the substrate. The multilayer coating includes a silica layer that is the outermost layer, the silica layer containing acid-sintered interconnected silica nanoparticles arranged to form a continuous three-dimensional porous network. The multilayer coating also includes a PVA layer disposed between a surface of the substrate and the outermost silica layer. The PVA and silica nanoparticle coatings can be used on a large variety of substrates and tend to be resistant to impacts, scratches, wet abrasions, soil and fog.

Claims

1. An article comprising:

a. a substrate;

b. a multilayer coating attached to the substrate, the multilayer coating comprising

i. a first silica layer that is an outermost layer of the multilayer coating, the first silica layer comprising a plurality of acid-sintered interconnected silica nanoparticles arranged to form a continuous three-dimensional porous network;

ii. a first poly(vinyl alcohol) (PVA) layer disposed between a surface of the substrate and the outermost silica layer; and

iii. a second silica layer disposed between the substrate and the first PVA layer, wherein the second silica layer comprises a plurality of acid-sintered interconnected silica nanoparticles arranged to form a continuous three-dimensional porous network.

2. The article of claim 1, further comprising one or more second PVA layers disposed between the first PVA layer and the first silica layer, between the first PVA layer and the substrate, or both.

3. The article of claim 2, wherein at least one of the first PVA layer and the second PVA layer comprises crosslinked PVA.

4. The article of claim 2, wherein the first PVA layer, the second PVA layer, or both comprises a silane-modified PVA.

5. The article of claim 1, wherein the first silica layer further comprises PVA.

6. The article of claim 1, wherein the first PVA layer further comprises a plurality of silica nanoparticles.

7. The article of claim 1, wherein the plurality of acid-sintered interconnected silica nanoparticles are formed from a dispersion comprising the silica nanoparticles acidified with an acid having a pKa less than 3.5 to a pH in a range of 2 to 5.

8. The article of claim 1, wherein the second silica layer is attached directly to the substrate.

9. The article of claim 1, wherein the second silica layer further comprises PVA.

10. A method of making an article, the method comprising:

a. providing a substrate;

b. attaching a multilayer coating to a surface of the substrate, the attaching comprising

i. forming a first PVA layer adjacent to the substrate;

ii. forming a first silica layer, wherein the first silica layer is an outermost layer of the multilayer coating, the first silica layer comprising a plurality of acid-sintered interconnected silica nanoparticles arranged to form a continuous three-dimensional porous network; and

iii. forming a second silica layer disposed between the first PVA layer and the substrate, wherein the second silica layer comprises a plurality of acid-sintered interconnected silica nanoparticles arranged to form a continuous three-dimensional porous network.

11. The method of claim 10, wherein the second silica layer is attached directly to the substrate.

12. The method of claim 10, wherein the first PVA layer further comprises a plurality of silica nanoparticles.

13. The method of claim 10, wherein forming the first silica layer comprises preparing a dispersion containing the silica nanoparticles acidified with an acid having a pKa less than 3.5 to a pH in a range of 2 to 5, coating the dispersion on the substrate, and drying the coating to form the plurality of acid-sintered silica nanoparticles.

14. The method of claim 13, wherein the dispersion containing the silica nanoparticles comprises silica nanoparticles having a bi-modal size distribution.

15. The method of claim 13, wherein the dispersion containing the silica nanoparticles comprises silica nanoparticles having average particle diameters up to 20 nanometers.

16. The method of claim 10, wherein the first silica layer further comprises PVA.

17. The method of claim 10, wherein the first PVA layer comprises a silane-modified PVA.