阅读说明：本技术 用于硬质表面的复合聚合物膜耐磨层 (Composite polymer film wear layer for hard surfaces ) 是由 桑达·莫汉·拉奥 于 2018-07-24 设计创作，主要内容包括：本发明提供了一种用于用作表面保护层以赋予硬质表面基底低光泽度、较高耐刮擦性、耐磨性和在脚下的舒适性的应用的复合聚合物膜耐磨层。本发明还提供了用该复合材料制成的硬质表面基底以及用于该应用的方法。(The present invention provides a composite polymeric film abrasion resistant layer for use as a surface protection layer to impart low gloss, higher scratch resistance, abrasion resistance and comfort under the foot to a hard surface substrate. The invention also provides hard surface substrates made with the composite material and methods for use in such applications.)

1. A composite transparent floor layer comprising:

a. a base layer comprising a first polymeric continuous phase and a first discontinuous phase comprising a matting agent having a durometer Shore A hardness in the range of 50 to 100;

b. a top polymer layer comprising a second polymeric continuous phase and a second discontinuous phase, the second discontinuous phase comprising abrasion resistant particles,

wherein the top polymer layer has a durometer shore a hardness in the range of 50 to 100, and wherein the top layer comprises less than 5% matting agent; and

c. an intermediate buffer layer between the bottom polymer layer and the top layer.

2. The composite flooring layer of claim 1, wherein the first polymeric continuous phase comprises polyethylene, low density polyethylene, linear low density polyethylene, high density polyethylene, medium density polyethylene, biaxially oriented polypropylene, uniaxially oriented polyethylene, polyester, biaxially oriented polyester, nylon, polyvinyl chloride, polylactic acid, acrylic polymers, polycarbonate, bio-based polymers, biodegradable polymers, ethylene methacrylic acid copolymers, polymethyl methacrylate polymers, acetal polymers, ionomer polymers, and/or ethylene methacrylic acid copolymers.

3. The composite flooring layer of claim 2, wherein the first discontinuous phase comprises a material selected from silica, TiO₂Calcium carbonate, talc, ester waxes, polymethyl methacrylate, and combinations thereof.

4. The composite flooring layer of claim 1, wherein the second polymeric continuous phase comprises polyethylene, low density polyethylene, linear low density polyethylene, high density polyethylene, medium density polyethylene, biaxially oriented polypropylene, uniaxially oriented polyethylene, polyester, biaxially oriented polyester, nylon, polyvinyl chloride, polylactic acid, acrylic polymers, polycarbonate, bio-based polymers, biodegradable polymers, ethylene methacrylic acid copolymers, polymethyl methacrylate polymers, acetal polymers, ionomer polymers, and/or ethylene methacrylic acid copolymers.

5. The composite flooring layer of claim 4, wherein the second discontinuous phase comprises wear resistant particles selected from the group consisting of alumina, silicon carbide, synthetic diamond, calcium carbonate, homogeneous quartzite, pumice, rouge, sand, quartz, garnet, sandstone, diatomites, powdered feldspar, staurostone, boron nitride, ceramic iron oxides, glass particles, glass beads, glass spheres (hollow or filled), plastic gravel, hard plastic particles, zircon corundum, boron carbide, slag, and other particles having a Mohs hardness of 7 or greater, or combinations thereof.

6. The composite flooring layer of claim 1, wherein the intermediate cushioning layer between the bottom polymer layer and the top layer comprises polyvinyl chloride, polyethylene, low density polyethylene, linear low density polyethylene, high density polyethylene, medium density polyethylene, biaxially oriented polypropylene, uniaxially oriented polyethylene, polyester, biaxially oriented polyester, nylon, polylactic acid, acrylic polymers, polycarbonate, bio-based polymers, biodegradable polymers, ethylene methacrylic acid copolymer, polymethyl methacrylate polymer, acetal polymer, ionomer polymer, ethylene methacrylic acid copolymer, foamed PVC, foamed polypropylene, polyurethane, elastomeric polyurethane, thermoplastic elastomeric polymer, silicone rubber, butyl rubber, styrene butadiene rubber, polybutadiene, natural polyisoprene, and/or synthetic polyisoprene.

7. The composite floor layer according to any of the claims 1-6, wherein said intermediate cushioning layer has a Shore 00 hardness rating in the range of 20 to 100, preferably in the range of 40 to 100, and most preferably in the range of 70 to 90.

8. The composite flooring layer of any one of claims 1 to 6, wherein a coating is applied on the top surface of the top layer.

9. The composite flooring layer of claim 8, wherein the coating is a UV curable polyurethane.

10. The composite polymeric wear layer of claim 1, wherein the polymer is selected from pre-industrial recycled content, pre-consumer recycled content, post-industrial recycled content, post-consumer recycled content, renewable polymeric content, or combinations thereof.

11. The composite polymeric wear layer of claim 1, wherein the bottom, top, and middle polymeric layers comprise the same polymer.

12. The composite polymeric wear layer of claim 1, wherein at least two of the bottom, top, and middle polymeric layers comprise different polymers.

13. The composite polymeric wear layer of claim 1, wherein the bottom polymeric layer provides a gloss value in the range of 2 to 50.

14. The composite polymeric wear layer of claim 1, wherein the top polymeric layer provides scratch resistance, has a rating equal to or better than MSR-B3 of use procedure B or has a rating equal to or better than MSR-A3 of use procedure a, as measured by the EN 16094 test method.

15. The composite polymeric wear layer of claim 1 comprising a total thickness of 40 to 3000 microns.

16. The composite polymeric wear layer of claim 1, wherein the thickness of the bottom polymeric layer is 5 to 250 microns, preferably in the range of 10 to 150 microns, and most preferably in the range of 25 to 100 microns.

17. The composite polymeric wear layer of claim 1, wherein the thickness of the top polymeric layer is 5 to 250 microns, preferably in the range of 10 to 150 microns, and most preferably in the range of 25 to 100 microns.

18. The composite polymeric wear layer of claim 1, wherein the thickness of the intermediate polymeric layer is 25 to 2000 microns, preferably in the range of 100 to 1500 microns, and most preferably in the range of 250 to 1000 microns.

19. A composite polymeric wear layer comprising:

a. a bottom polymer layer comprising a polymer and a matting agent; and

b. a top polymer layer comprising a polymer and a plurality of wear resistant particles.

20. A hard surface floor comprising:

a. a bottom balancing layer;

b. a core layer on the bottom balancing layer;

c. a decorative layer or a printed layer on the core layer; and

d. the polymeric wear layer of claim 1, located on the decorative layer or print layer.

21. The hard surface floor of claim 20, wherein the bottom balancing layer, the core layer, and the decorative or printed layer comprise polyvinyl chloride.

22. The hard surface floor of claim 20, wherein the bottom balancing layer, the core layer, and the decorative or print layer comprise a non-vinyl polymer.

23. The hard surface flooring of claim 20, wherein the bottom balancing layer comprises wood, the core layer comprises a core deck, and the decorative or print layer comprises a wood veneer.

24. A hard surface floor comprising:

a. a bottom balancing layer;

b. a core layer on the bottom balancing layer;

c. a decorative print layer on the core layer, an

d. The polymeric wear layer of claim 1, the polymeric wear layer being on the core layer.

25. The hard surface floor of claim 24, wherein the bottom balancing layer, the core layer, and the decorative or printed layer comprise polyvinyl chloride.

26. The hard surface floor of claim 24, wherein the bottom balancing layer, the core layer, and the decorative or print layer comprise a non-vinyl polymer.

27. The hard surface flooring of claim 24, wherein the bottom balancing layer comprises wood, the core layer comprises a core deck, and the decorative or print layer comprises a wood veneer.

28. A hard surface substrate comprising:

a. a core substrate; and

b. the polymeric wear layer of any one of claims 1-19.

29. The hard surface substrate of claim 28, wherein the core substrate is selected from the group consisting of packaging films, countertops, flooring, wall coverings, and furniture.

30. A method for protecting the surface of a hard surface substrate from scratching, the method comprising applying the composite polymeric wear layer of any one of claims 1-19 to the surface of the hard surface substrate.

31. A method for imparting a lower gloss to a surface of a hard surface substrate, the method comprising applying the composite polymeric wear layer of any one of claims 1-19 to the surface of the hard surface substrate.

32. A composite transparent floor layer comprising:

a. a base layer comprising a first polymeric continuous phase and a first discontinuous phase comprising a matting agent having a durometer shore a hardness in the range of 50 to 100 and having reverse printing for use as a decorative layer;

b. a top polymer layer comprising a second polymeric continuous phase and a second discontinuous phase, the second discontinuous phase comprising abrasion resistant particles,

wherein the top polymer layer has a durometer Shore A hardness in the range of 50 to 100, and

wherein the elastomeric top layer comprises less than 5% matting agent; and

c. a transparent intermediate cushion layer between the bottom polymer layer and the top layer having a durometer Shore OO hardness in a range of 20 to 100.

33. A composite flooring layer comprising:

a. a bottom buffer layer having a durometer shore OO hardness in the range of 20 to 100;

b. an intermediate layer comprising a first polymeric continuous phase and a first discontinuous phase comprising a matting agent having a durometer shore a hardness in the range of 50 to 100 and having reverse printing for use as a decorative layer; and

c. a top polymeric layer comprising a second polymeric continuous phase and a second discontinuous phase, the second discontinuous phase comprising abrasion resistant particles;

wherein the top polymer layer has a durometer Shore A hardness in the range of 50 to 100.

34. A composite flooring layer comprising:

a. a bottom buffer layer having a durometer shore OO hardness in the range of 20 to 100;

b. an intermediate layer comprising a first polymeric continuous phase and a first discontinuous phase comprising a matting agent having a durometer shore a hardness in the range of 50 to 100; and

c. a top polymer layer comprising a second polymeric continuous phase and a second discontinuous phase, the second discontinuous phase comprising abrasion resistant particles,

wherein the top polymer layer has a durometer Shore A hardness in the range of 50 to 100.

35. A composite flooring layer comprising:

a. a top transparent buffer layer comprising a polymer phase having a durometer shore OO hardness in the range of 20 to 100 and comprising abrasion resistant particles;

b. a transparent intermediate polymer layer comprising a second polymeric continuous phase and a second discontinuous phase comprising abrasion resistant particles, wherein the polymer layer has a durometer Shore A hardness in the range of 50 to 100 and it has a reverse printed surface at the bottom; and

c. an optional transparent elastomeric top coat layer comprising less than 5% matting agent.

36. A composite flooring layer comprising:

a. a transparent bottom cushion layer comprising a polymer phase having a durometer shore OO hardness in a range of 20 to 100 and comprising abrasion resistant particles;

b. a transparent intermediate polymer layer comprising a second polymeric continuous phase and a second discontinuous phase comprising abrasion resistant particles, wherein the polymer layer has a durometer shore a hardness in the range of 50 to 100; and

c. an optional elastomeric clear top coat layer on the intermediate layer and comprising less than 5% matting agent.

37. The composite flooring layer of claims 35-36, wherein the optional elastomeric top coat is a UV curable polyurethane.

Technical Field

The invention relates to a composite polymer film wear layer. The abrasion resistant layer of the present invention can be applied as a surface protection layer to impart lower gloss and higher scratch, abrasion and comfort to a hard surface substrate.

Background

A hard surface substrate such as a luxury vinyl flooring has a balance layer at the bottom, a core layer of polyvinyl chloride (PVC) and limestone, a printed layer of PVC, an abrasion resistant layer of clear PVC, and a top coating of UV curable polyurethane. To meet the low gloss requirement, the top coat layer typically contains silica particles having a particle size diameter of from about 1 micron to about 40 microns, which act as a matting agent. The coating also has an abrasion resistant agent, such as alumina, to resist scratching.

Various coatings and methods for application to hard surface substrates have been described.

U.S. patent No. 8,658,274 discloses a thermoplastic laminated tile with optional lamination. The laminate or wear layer is a laminated paper material that is clear in appearance when secured to the print layer of the tile. The preferred high abrasive laminate listed with alumina embedded in the surface of the paper impregnated with the aminoplast resin for the thermoplastic flat tile comprises a laminate obtained from a paper having product number TMO 361, 461(70 g/m)²Good quality laminates, available from Mead) and 561 of Mead specialty Paper.

Us patent No. 9,156,233 discloses waterproof engineered flooring and siding with a wear layer bonded to a core by a waterproof adhesive. The wear layer is disclosed as being waterproof and is selected from a wide variety of possible materials including tile or stone veneers, rubber, decorative plastics, decorative vinyl, linoleum and any material encapsulated in vinyl or resin such as cork, bamboo or wood veneers to make the layer waterproof and wear resistant. An optional overlay applied over the melamine resin veneer with alumina and polyurethane is also disclosed.

Us patent No. 8,800,245 discloses a sheet for flooring comprising a PVC wear layer, a pattern layer, a base layer and a backing layer.

Published U.S. patent application No. 2015/0375471 discloses tiles for ceilings, walls and floors having a wear layer comprising any suitable known wear resistant material, such as a wear resistant macromolecular material coated on an underlying layer, or a known ceramic bead coating. Alternatively, the abrasion resistant layer may comprise an organic polymer layer and/or an inorganic material layer such as a uv coating, or another combination of an organic polymer layer and a uv coating. Examples disclosed herein are ultraviolet coatings that can improve the scratch resistance, gloss, antimicrobial properties, and other properties of the product. Additional agents disclosed for inclusion as needed include organic polymers, polyvinyl chloride and vinyl resins, plasticizers, and other processing additives.

U.S. patent No. 4,176,210 discloses a decorative sheet covering having a PVC and polyurethane abrasion resistant layer prepared by forming a sheet of gelled, foamable PVC plastisol or organosol on a substrate and then applying and gelling a layer of non-foamable PVC plastisol or organosol onto the gelled foamable layer without curing. A polyurethane layer is then applied to the gelled non-foamable layer and the entire sheet is heated to a temperature sufficient to decompose the foaming agent in the foamable layer and cure both the PVC layer and the polyurethane layer.

European patent No. 242491 l discloses Ultraviolet (UV) V-spectrum light emitting diode curable coatings for flooring and other applications to enhance their durability and finish.

PCT/US2008/071446 discloses a floor tile comprising a first sheet having at least one substrate layer, a printed design located above the substrate layer, and at least one wear layer located above the printed design and a second sheet adhered to a lower surface of the first sheet, wherein two adjacent sides of the second sheet have projections to interlock projections on adjacent floor tiles having complementary shapes to each other in interlocking engagement with corresponding projections or recesses on adjacent floor tiles. The preferred abrasion resistant layer disclosed herein is a transparent PVC layer of about 5 mils to about 50 mils. Other examples of the disclosed abrasion resistant layers include acrylic polymers, polyolefins, and the like. Further, it is disclosed that the wear layer topcoat may be a thermoset layer or a thermoplastic layer. Additional examples of wear resistant layers are disclosed in U.S. patent nos. 4,333,987; 4,180,615, respectively; 4,393,187, respectively; 4,507,188, respectively; and 8,591,696 and published U.S. patent application No. 2016/0201324.

However, these types of coatings result in several negative effects. For example, when the surface is scratched for 45 cycles using a Martindale scratch tester with a No. 100 grit sandpaper, it produces white powder of silica and polymer dust and abrasives from the coating, which is undesirable and involves the consumer. Furthermore, these coatings are expensive, since for example industry standard manufacturing processes have to include a production line for coating the substrate, which is done with UV lamps and optionally thermal annealing. In addition, due to poor adhesion, the coating may crack or fail, thereby creating unnecessary waste.

Similar problems exist in wood flooring with up to nine coatings, wherein the top coating consists of UV curable polyurethane.

Furthermore, hard surfaces are known to be uncomfortable under the foot compared to soft surfaces such as carpets and carpets. Standing on a hard floor for extended periods of time can cause more fatigue and can cause joint pain. Homeowners attempt to address this problem by using soft gel pads on hard surfaces in the kitchen and elsewhere where long standing is required. The backing of the mat layer underneath the core substrate does not help in this respect.

Accordingly, a protective layer for a hard substrate surface minimizes or eliminates white powder due to scratching, and eliminates expensive coating chemicals and additional process steps for applying the coating, and thus is a long felt need. Further, there is a need for a hard surface that has a softer and more comfortable feel under the foot while maintaining existing advantages such as design and appearance, and ease of installation of the click-lock joint.

Disclosure of Invention

One aspect of the present invention relates to a composite polymeric film wear layer for hard surfaces.

In one non-limiting embodiment, the composite polymeric wear layer includes a bottom polymeric layer comprising a polymer and a matting agent dispersed therein, and a top polymeric layer comprising a polymer and a plurality of wear resistant particles. In some embodiments, the top layer further comprises a matting agent to reduce gloss. In some embodiments, an intermediate polymer layer is between the bottom polymer layer and the top polymer layer.

In another non-limiting embodiment, a composite polymeric abrasion resistant layer includes a bottom polymeric layer comprising a polymer and a matting agent dispersed therein, and a light transmissive transparent polymeric layer and a top polymeric layer comprising a polymer and a plurality of abrasion resistant particles.

In another non-limiting embodiment, a composite polymeric wear layer includes a bottom polymeric layer comprising a polymer and a matting agent dispersed therein, and a top polymeric layer comprising a polymer and a plurality of wear resistant particles. The two layers may have a shore a hardness scale of 50 to 100. In this non-limiting embodiment, between the bottom polymer layer and the top polymer layer is a light transmissive and transparent intermediate polymer layer that is softer and has a shore OO hardness rating of 20 to 100. This provides comfort under the foot when the layer is mounted on a hard surface core. The composite layer may be mounted on top of a printed layer, which in turn is mounted on a core substrate or on a digitally printed core substrate to create a floor.

In another non-limiting embodiment, a composite polymeric wear layer includes a bottom polymeric layer comprising a polymer and a matting agent dispersed therein, and a top polymeric layer comprising a polymer and a plurality of wear resistant particles. In this non-limiting embodiment, the bottom polymer layer may be reverse printed to provide the design. The two layers may have a shore a hardness scale of 50 to 100. Underlying the base layer is a polymer layer which is softer and has a shore OO hardness rating of 20 to 100. This may or may not be transparent. The composite layer can be mounted on top of a hard base core to create a floor.

Another aspect of the invention relates to a hard surface floor. In one non-limiting embodiment, a hard surface flooring comprises a bottom balancing layer, a core layer located on top of the bottom balancing layer; a decorative or printed layer on top of the core layer; and a composite polymeric wear layer of the present invention. In one non-limiting embodiment, the bottom balancing layer, the core layer, and the decorative or print layer of the hard surface flooring comprise polyvinyl chloride. In another non-limiting embodiment, the bottom balancing layer, the core layer, and the decorative or print layer of the hard surface flooring comprise a non-vinyl polymer. In another non-limiting embodiment of the hard surface flooring, the bottom balancing layer comprises wood, the core layer comprises a core deck, and the decorative layer or print layer comprises a wood veneer.

Another aspect of the present invention relates to a hard surface substrate comprising a core substrate and a composite polymeric wear layer of the present invention. Non-limiting examples of core substrates that may be protected by the present invention include packaging films, countertops, and furniture.

Another aspect of the present invention relates to a method of protecting a surface of a hard surface substrate from scratching by applying the composite polymeric wear layer of the present invention to the hard surface substrate.

Another aspect of the present invention relates to a method of imparting a lower gloss to the surface of a hard surface substrate by applying the composite polymeric wear layer of the present invention to the hard surface substrate.

Detailed Description

Before the present disclosure is described in greater detail, it is to be understood that this disclosure is not limited to particular embodiments described, as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting, since the scope of the present disclosure will be limited only by the appended claims.

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 disclosure belongs. Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present disclosure, the preferred methods and materials are now described.

All publications and patents cited in this specification are herein incorporated by reference as if each individual publication or patent were specifically and individually indicated to be incorporated by reference and were set forth in its entirety herein to disclose and describe the methods and/or materials in connection with which the publications were cited. The citation of any publication is for its disclosure prior to the filing date and should not be construed as an admission that the present disclosure is not entitled to antedate such publication by virtue of prior disclosure. Further, the publication date provided may be different from the actual publication date that may need to be independently confirmed.

As will be apparent to those of skill in the art upon reading this disclosure, each of the various embodiments described and illustrated herein has discrete components and features that can be readily separated from or combined with the features of any of the other several embodiments without departing from the scope or spirit of the present disclosure. Any recited method may be performed in the order of events recited or in any other order that is logically possible.

Unless otherwise indicated, embodiments of the present disclosure will employ chemical, textile, plastic, and like techniques within the skill of the art. Such techniques are explained fully in the literature.

Before the embodiments of the present disclosure are described in detail, it is to be understood that unless otherwise specified, the present disclosure is not limited to particular materials, reagents, reaction materials, manufacturing methods, or the like, as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting. In the present disclosure, steps may also be performed in a different order, where logically possible.

It is noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a support" includes a plurality of supports. In this specification and the claims which follow, reference will be made to a number of terms which shall be defined to have the following meanings unless a contrary intention is apparent.

The present invention provides a composite polymeric film abrasion resistant layer that can be applied to serve as a surface protection layer to impart low gloss and high scratch, abrasion and comfort to a hard surface substrate.

In one non-limiting embodiment, the composite polymeric wear layer includes a bottom polymeric layer comprising a polymer and a matting agent dispersed therein. In one non-limiting embodiment, the underlayer comprises a first polymeric continuous phase and a first discontinuous phase comprising a matting agent.

Non-limiting examples of polymers that may be used in the bottom layer include, but are not limited to, PVC or various film producing polymers. Examples of such polymers include: polyethylene, low density polyethylene, linear low density polyethylene, high density polyethylene, medium density polyethylene, biaxially oriented polypropylene, uniaxially oriented polyethylene, polyester, biaxially oriented polyester, nylon, polyvinyl chloride, polylactic acid, acrylic polymers, polycarbonate, bio-based polymers, biodegradable polymers, ethylene methacrylic acid copolymers, polymethyl methacrylate polymers, acetal polymers, ionomer polymers, ethylene methacrylic acid copolymers, and other suitable film forming polymers. These polymers may also have recycled content, including pre-and post-industrial recycled content, renewable polymer content, and combinations thereof.

Non-limiting examples of matting agents dispersed in the underlayer include silica, TiO₂Calcium carbonate, talc, ester wax, polymethyl methacrylate, and combinations thereof. The matting agent in the form of a masterbatch can be incorporated into a polymer for cast or blown film during extrusion. Another manufacturing method requires spreading the matting agent particles in a uniform manner on a preformed film and then pressing the film under heat to embed the particles in the film. Other suitable manufacturing methods may also be implemented. The thickness of the film may be in the range of about 5 microns to about 250 microns, preferably in the range of about 10 microns to about 150 microns, and most preferably in the range of about 25 microns to about 100 microns. By usingThe concentration of the matting agent in the underlayer can range from about 1% to about 50%, preferably 5% to 25%, and most preferably 5% to 15%.

In one non-limiting embodiment, the bottom polymer layer is formulated to provide a gloss in the range of 2 to 50, where gloss is measured by a gloss meter such as a micro-trigloss meter model 4563 (available from BYK-Gardner GmbH.).

In this non-limiting embodiment, the composite polymeric wear layer further comprises a top polymeric layer comprising a polymer and a plurality of wear resistant particles. In one non-limiting embodiment, the top polymeric layer includes a second polymeric continuous phase and a second discontinuous phase containing abrasion resistant particles. In some embodiments, the top polymer layer further comprises a matting agent as described herein to reduce gloss. In one non-limiting embodiment, the elastomeric top layer contains less than 5% matting agent. In one non-limiting embodiment, the top polymer layer has a durometer shore a hardness in the range of 50 to 100.

Non-limiting examples of polymers that may be used for the top layer include PVC, or various film producing polymers. Examples of such polymers include: polyethylene, low density polyethylene, linear low density polyethylene, high density polyethylene, medium density polyethylene, biaxially oriented polypropylene, uniaxially oriented polyethylene, polyester, biaxially oriented polyester, nylon, polyvinyl chloride, polylactic acid, acrylic polymers, polycarbonate, bio-based polymers, biodegradable polymers, ethylene methacrylic acid copolymers, polymethyl methacrylate polymers, acetal polymers, ionomer polymers, ethylene methacrylic acid copolymers, ethylene vinyl acetate, and other suitable film forming polymers, copolymers and blends thereof. These polymers may also have recycled content, including pre-and post-industrial recycled content, renewable polymer content, and combinations thereof.

Using procedure a, the top polymer layer is formulated to pass industry standard tests, such as EN-16094 test method, with a minimum rating of MSR-a3 or better, and if procedure B is used, with a minimum rating of MSR-B3 or better.

Non-limiting examples of wear resistant particles included in the top layer include aluminum oxide, silicon carbide, synthetic diamond, calcium carbonate, homogeneous quartzite, pumice, rouge, sand, quartz, garnet, sandstone, diatomites, powdered feldspar, staygorskite, boron nitride, ceramic iron oxide, glass particles, glass beads, glass spheres (hollow or filled), plastic gravel, hard plastic particles, zircon corundum, boron carbide, slag, and other particles having a mohs hardness of 7 or greater, or combinations thereof. The abrasion resistant particles in the form of a masterbatch may be incorporated into a polymer for cast or blown film during extrusion. Another effective manufacturing method is to spread the wear resistant particles in a uniform manner over a preformed film and then press the film under heat to embed the particles into the film. Other suitable manufacturing methods may be implemented. The thickness of the film may range from about 5 microns to about 250 microns, preferably in the range of 10 microns to 150 microns, and most preferably in the range of 25 microns to 100 microns. The concentration may range from 0.5% to 75%, preferably from 5% to 60%, and most preferably from 10% to 50%.

In one non-limiting embodiment, an intermediate polymer layer is between the bottom polymer layer and the top polymer layer of the composite polymeric wear layer. In one non-limiting embodiment, the intermediate layer is a buffer layer. In one non-limiting embodiment, the intermediate buffer layer has a shore 00 hardness scale in the range of 20 to 100, preferably in the range of 40 to 100, and more preferably in the range of 70 to 90.

Non-limiting examples of polymers that may be used in the intermediate layer include, but are not limited to, PVC or various film-producing polymers, polyethylene, low density polyethylene, linear low density polyethylene, high density polyethylene, medium density polyethylene, biaxially oriented polypropylene, uniaxially oriented polyethylene, polyester, biaxially oriented polyester, nylon, polyvinyl chloride (PVC), polylactic acid, acrylic polymers, polycarbonate, biobased polymers, biodegradable polymers, ethylene methacrylic acid copolymers, polymethyl methacrylate polymers, acetal polymers, ionomer polymers, ethylene methacrylic acid copolymers, and other suitable film-forming polymers, foamed PVC, foamed polypropylene, polyurethane, elastomeric polyurethane, thermoplastic elastomeric polymers, silicone rubber, butyl rubber, styrene-butadiene rubber, polybutadiene, natural polyisoprene, polyethylene, polypropylene, polyethylene, polypropylene, Ethylene-vinyl acetate, synthetic polyisoprene copolymers and blends thereof. These polymers may also have recycled content, including pre-and post-industrial recycled content, renewable polymer content, and combinations thereof. The thickness of the film may range from about 25 microns to about 2000 microns, preferably in the range of 100 microns to 1500 microns, and most preferably in the range of 250 microns to 1000 microns. The polymer layer may be transparent or opaque and colored.

In some embodiments, the intermediate polymer layer further comprises a matting agent as described herein. In one non-limiting embodiment, the intermediate layer comprises less than 5% matting agent.

In one non-limiting embodiment of the composite polymeric abrasion resistant layer of the present invention, a bottom polymeric layer comprising a polymer and a matting agent dispersed therein and a transparent intermediate polymeric layer that is light transmissive are combined into a single layer. A top polymer layer comprising a polymer and a plurality of wear resistant particles is then applied to the combined layer.

In another non-limiting embodiment, the composite polymeric wear layer of the present invention can include a bottom polymeric layer comprising a polymer and a matting agent dispersed therein, and a top polymeric layer comprising a polymer and a plurality of wear resistant particles. The two layers may have a shore a hardness scale of 50 to 100. In this non-limiting embodiment, between the bottom polymer layer and the top polymer layer is a light transmissive and transparent intermediate polymer layer that is softer and has a shore OO hardness rating of 20 to 100. This provides comfort under the foot when the layer is mounted on a hard surface core. The composite layer may be mounted on top of a printed layer, which in turn is mounted on a core substrate or on a digitally printed core substrate to create a floor.

In another non-limiting embodiment, the composite polymeric wear layer of the present invention can include a bottom polymeric layer comprising a polymer and a matting agent dispersed therein, and a top polymeric layer comprising a polymer and a plurality of wear resistant particles. In this non-limiting embodiment, the bottom polymer layer may be reverse printed to provide the design. The two layers may have a shore a hardness scale of 50 to 100. Underlying the base layer is a polymer layer which is softer and has a shore OO hardness rating of 20 to 100. This may or may not be transparent. The composite layer can be mounted on top of a hard base core to create a floor.

As will be understood by the skilled artisan upon reading this disclosure, the above-described layers and their functions may be rearranged in these composites and may not be necessary, but optional, and the invention is not necessarily constrained by the number of layers and their order described above.

Thus, additional non-limiting embodiments of the composite material of the present invention include:

a composite transparent flooring layer comprising a base layer comprising a first polymeric continuous phase and a first discontinuous phase comprising a matting agent having a durometer shore a hardness in the range of 50 to 100 and having reverse printing for use as a decorative layer. This non-limiting embodiment may also include a top polymer layer including a second polymeric continuous phase and a second discontinuous phase, the second discontinuous phase including abrasion resistant particles. The top polymer layer also has a durometer shore a hardness in the range of 50 to 100. In addition, the top polymer layer may also contain a matting agent, preferably less than 5% matting agent. Further, the transparent composite includes a transparent intermediate cushion layer between the bottom polymer layer and the top layer having a durometer shore OO hardness in a range of 20 to 100;

a composite flooring layer comprising: a bottom buffer layer having a durometer Shore OO hardness in the range of 20 to 100. This non-limiting embodiment further includes an intermediate layer comprising a first polymeric continuous phase and a first discontinuous phase comprising a matting agent having a durometer shore a hardness in the range of 50 to 100. In this non-limiting embodiment, the intermediate layer may have reverse printing to serve as a decorative layer. This non-limiting embodiment further includes a top polymer layer comprising a second polymeric continuous phase and a second discontinuous phase comprising abrasion resistant particles, wherein the top polymer layer further has a durometer shore a hardness in the range of 50 to 100;

a composite flooring layer comprising: a bottom buffer layer having a durometer shore OO hardness in the range of 20 to 100; an intermediate layer comprising a first polymeric continuous phase and a first discontinuous phase comprising a matting agent having a durometer shore a hardness in the range of 50 to 100; and a top polymer layer comprising a second polymeric continuous phase and a second discontinuous phase comprising abrasion resistant particles, wherein the top polymer layer has a durometer shore a hardness in the range of 50 to 100;

a composite flooring layer comprising: a top transparent buffer layer comprising a polymer phase having a durometer shore OO hardness in the range of 20 to 100 and comprising abrasion resistant particles; and a transparent intermediate polymer layer comprising a second polymeric continuous phase and a second discontinuous phase comprising abrasion resistant particles, wherein the polymer layer has a durometer shore a hardness in the range of 50 to 100. In this non-limiting embodiment, the middle layer may have a reverse printing surface at the bottom. In this embodiment, a transparent elastomeric top coat layer containing less than 5% matting agent may optionally be included; and

a composite flooring layer comprising: a transparent bottom cushion layer comprising a polymer phase having a durometer Shore OO hardness in a range of 20 to 100 and containing abrasion resistant particles. This non-limiting embodiment further includes a transparent intermediate polymer layer including a second polymeric continuous phase and a second discontinuous phase, the second discontinuous phase including abrasion resistant particles. The intermediate polymer layer has a durometer shore a hardness in the range of 50 to 100. In this embodiment, an elastomeric transparent top coat layer comprising less than 5% matting agent may optionally be applied on top of the intermediate layer.

The total thickness of the composite of the present invention is in the range of 40 to 3000 microns.

The polymeric material used for the layers may be the same material or different for each layer. For example, the top layer can be differentiated to include functions such as antimicrobial efficacy, stain resistance, high chemical resistance, and self-healing properties. The top polymer layer can be made of a more expensive polymer because the layer is thinner and it is the most effective location to position these enhanced and differentiated properties in favor of the consumer.

Further, in some non-limiting embodiments, the composite polymeric wear layer may also include a substrate with an adhesive to provide good adhesion to the substrate.

With the composite material according to the invention, only the top layer will normally be affected during any scraping process. However, unlike prior art coatings, the top layer of the composite of the present invention does not have matting agents such as silica particles to produce a large amount of white powder. Thus, any powder produced is minimized by the present invention. Furthermore, the presence of wear resistant particles in the top layer of the composite material of the present invention also minimizes the effect of scratches. The intermediate layer in the composite of the present invention is light transmissive and completely transparent, provides further resistance to abrasion, and provides a high grade in abrasion-based end-use performance testing. The bottom layer of the composite is designed to provide the gloss level required for a particular product by the matting agent while preventing any scratching that would release white powder through the top and middle layers.

Further, the composite polymer layer may be applied by various means including, but not limited to, a co-extrusion process, or depending on the thickness, a blown film process may also be employed.

Alternatively, the composite layer may be prepared separately and laminated via a laminator to prepare the composite. The laminate can then be applied as an abrasion resistant layer to a hard surface substrate such as a luxury vinyl substrate or flat tile in a continuous or batch process. This eliminates the need for a coating line having multiple coating application units, multiple tanks for storing coatings, and multiple UV curing stations, as well as the health and safety issues associated with such coatings.

Another alternative for use is to bring together the individual layers of the composite and stack them together with, for example, a print layer, a core layer and a balancing layer, and then press all the layers together in a single process to form a luxurious vinyl substrate (LVT) or luxurious vinyl tile (LVP).

The present invention also provides hard surface flooring and other hard surface substrates protected by the polymeric wear layer described herein.

Non-limiting examples of hard surface flooring that may be protected by the wear layer of the present disclosure may include a bottom balancing layer, a core layer on top of the bottom balancing layer, and a decorative or printed layer on top of the core layer. In the present invention, a polymeric wear layer as described herein is applied on top of the decorative layer or printed layer according to any of the methods described herein. The components used in the bottom balancing layer, core layer and decorative printed layer are well known to those skilled in the art and may include, but are not limited to, bottom balancing layers, core layers and decorative layers or printed layers comprising polyvinyl chloride, bottom balancing layers, core layers and decorative layers or printed layers comprising non-vinyl polymers, and bottom balancing layers comprising wood, core layers comprising core platforms, such as high density fiberboard, or wood plastic composites, or multi-ply plywood, or mineral board, and decorative layers or printed layers comprising wood veneers.

Non-limiting examples of additional core substrates to which the polymeric abrasion resistant layers of the present invention can be applied include packaging films, countertops, and furniture.

In addition, the present invention is directed to methods for applying the composite polymeric wear layer of the present invention to a hard surface substrate to protect the hard surface substrate from scratching and/or impart a lower gloss to the surface of the hard surface substrate.

The following examples and test methods are set forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how to perform the methods and use the compositions and compounds disclosed and claimed herein. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.) but some errors and deviations should be accounted for. Unless otherwise indicated, parts are parts by weight, temperature is in units of ° c, and pressure is in units of atmospheric pressure. The standard temperature and pressure are defined as 25 ℃ and 1 atmosphere.

Test method

THE TEST was carried out using a Martindale scratch tester according to ASTM D5178 and EN 16094 ("LAMINATE FLOORCOVERINGS-TEST METHOD FOR THE DETERMINATION OF MICRO-SCRATCH RESISTANCE").

The shore a hardness of a given substrate was measured according to ASTM D2240 using an ASKER Super EX durometer.