SURFACE COVERING WITH WEAR LAYER HAVING DISPERSED THEREIN WEAR-RESISTANT ADDITIVES AND METHOD OF MAKING THE SAME
20200032083 ยท 2020-01-30
Inventors
- Daniel P BAKER (Downingtown, PA, US)
- Gary A. SIGEL (Columbia, PA, US)
- Dong Tian (Lancaster, PA)
- Kristy L. Gething (York, PA, US)
- Mark J. BOLDIZAR (Lancaster, PA, US)
Cpc classification
B32B27/304
PERFORMING OPERATIONS; TRANSPORTING
B32B2255/10
PERFORMING OPERATIONS; TRANSPORTING
B32B2272/00
PERFORMING OPERATIONS; TRANSPORTING
B32B27/28
PERFORMING OPERATIONS; TRANSPORTING
B32B2270/00
PERFORMING OPERATIONS; TRANSPORTING
B32B2264/104
PERFORMING OPERATIONS; TRANSPORTING
B32B2255/24
PERFORMING OPERATIONS; TRANSPORTING
B32B9/02
PERFORMING OPERATIONS; TRANSPORTING
B32B2264/108
PERFORMING OPERATIONS; TRANSPORTING
E04F15/107
FIXED CONSTRUCTIONS
B32B27/308
PERFORMING OPERATIONS; TRANSPORTING
B32B2307/546
PERFORMING OPERATIONS; TRANSPORTING
B32B2264/12
PERFORMING OPERATIONS; TRANSPORTING
C01P2004/64
CHEMISTRY; METALLURGY
Y10T428/24802
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
C01P2004/61
CHEMISTRY; METALLURGY
B32B27/302
PERFORMING OPERATIONS; TRANSPORTING
C09D5/00
CHEMISTRY; METALLURGY
C08K2201/005
CHEMISTRY; METALLURGY
B32B2307/4023
PERFORMING OPERATIONS; TRANSPORTING
B32B27/306
PERFORMING OPERATIONS; TRANSPORTING
B32B9/005
PERFORMING OPERATIONS; TRANSPORTING
B32B9/002
PERFORMING OPERATIONS; TRANSPORTING
B32B9/04
PERFORMING OPERATIONS; TRANSPORTING
B32B27/30
PERFORMING OPERATIONS; TRANSPORTING
C01P2004/62
CHEMISTRY; METALLURGY
C09D175/16
CHEMISTRY; METALLURGY
C09D167/00
CHEMISTRY; METALLURGY
E04F15/105
FIXED CONSTRUCTIONS
B32B27/20
PERFORMING OPERATIONS; TRANSPORTING
International classification
E04F15/10
FIXED CONSTRUCTIONS
B32B27/20
PERFORMING OPERATIONS; TRANSPORTING
Abstract
A wear-resistant composition which includes a polymeric hot-melt binder system which includes at least one wear-resistant additive which includes diamond particles dispersed therein. A surface covering includes a base layer, a wear-resistant layer, and optionally a topcoat layer. The wear-resistant layer is laminated to the base layer. The wear-resistant layer may be formed by dispersing a plurality of wear-resistant additive particles, which include diamonds, into a liquid to form a stable liquid dispersion, blending the stable liquid dispersion into a polymeric resin to form a mixture, and extruding the mixture to form the wear layer.
Claims
1. A wear-resistant hot-melt coating composition comprising: a binder composition comprising a hot-melt polymer and a wear-resistant additive comprising diamond, particles.
2. The wear-resistant hot-melt coating composition of claims 1, wherein the diamond particles have an average particle size of about 0.1 nm to about 1000 nm.
3. The wear-resistant hot-melt coating composition of claim 1, wherein the diamond particles have an average particle size of about 0.1 m to about 75 m.
4. The wear-resistant hot-melt coating composition of claim 1, wherein the diamond particles are present in the amount of about 1% to about 50% 1/i: to about 50% by weight of the total wear-resistant composition.
5. The wear-resistant hot-melt coating composition of claim 1, wherein the hot-melt polymer is a urethane hot-melt containing moisture curing groups.
6. The wear-resistant hot-melt coating composition of claim 1, wherein the moisture curing groups are isocyanate groups.
7. A floor covering having enhanced wear-resistance comprising: a substrate; and a coating layer comprising a hot-melt polymer binder composition and a wear-resistant additive comprising diamond particles dispersed therein, wherein the diamond particles are present in amounts of about 1% to about 50% by total weight of the binder composition.
8. The floor covering composition of claim 7, wherein the diamond particles have an average particle size of about 0.1 nm to about 1000 nm.
9. The floor covering composition of claim 7, wherein the diamond panicles have an average particle size of about 0.1 m to about 75 m.
10. A surface covering comprising a laminate structure comprising: abase layer; and a wear layer atop the base layer, the wear layer comprising a polymeric hot-melt binder and wear resistance particles dispersed in the polymer binder: said wear-resistant particles comprising diamonds.
11. The surface covering of claim 10, further including a topcoat layer over the wear layer.
12. The surface covering of claim 10, wherein the ratio of the base layer thickness to the wear-layer thickness is from about 1:1 to about 1:40.
13. The surface covering of claim 10, wherein the ratio of the wear-resistant thickness to the topcoat layer is from about 1:1 to about 1:12.
14. The surface covering of claim 10, wherein the laminate structure further comprises a print layer positioned between the base layer and the wear layer.
15. The surface covering of claim 10, wherein the print layer is embossed.
16. The surface covering of claim 10, wherein the wear resistance particles have a size ranging from about 10 nm to about 500 nm.
17. The surface covering of claim 1, wherein the wear resistance particles are present in an amount of about 1% to about 50% by weight of the wear layer.
18. The surface covering of claim 10, wherein the laminate structure has a thickness ranging from about 35 mils to 170 mils.
19. The surface covering of claim 1, wherein the first thickness of the wear layer ranges from about 1 mil to about 40 mils.
20-37. (canceled)
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0025]
[0026]
[0027]
[0028]
DETAILED DESCRIPTION OF THE INVENTION
[0029] For purposes of the present invention, the following definitions will apply:
[0030] Average diameter is calculated by measuring the diameter of each piece of a material (e.g., diamond material), and then calculating the average. If the material (e.g., diamond material) has different diameters, e.g., if the material (e.g., diamond material) is not a sphere, then the average diameter is calculated by measuring the longest diameter of each piece of material (e.g., diamond material), and then calculating the average. It should be noted that any calculations involving material (e.g., distance between pieces of a material, distance of some material from a layer's surface, etc.) should use the relevant edge of the material, as opposed to the center of the material.
[0031] Coating or coating layer means a composition that has been applied to a surface, such as a substrate, and then cured. Coating may refer to a single coating layer or to the totality of coating layers. Coating layers may be the same as, or different from, each other in terms of composition, average thickness, etc.
[0032] Curing or cured or similar means the process whereby polymeric materials are formed by cross-linking, creating properties such as (but not limited to) increased viscosity and hardness. The curing process may be initiated via several methods, e.g., application of heat and/or radiation such as (but not limited to) light, e.g., visible light or UV light. A complete cure or similar means that all polymeric materials have cross-linked. Substantially complete cure or similar means that the vast majority of polymeric materials have cross-linked such that it is difficult or impossible to determine if a complete cure has taken place. A partial cure or partially complete cure or similar means that the curing process has been initiated but has not yet reached the point of meeting the definition of a complete cure or of a substantially complete cure.
[0033] Dispersing agent is any chemical or compound that acts to distribute, or to assist in distributing, at least the abrasion resistant material throughout a composition prior to curing.
[0034] Floor covering is any substrate which may be useful in creating a floor surface in building operations. The substrate forming the floor covering may be either coated with at least one coating layer, or it may be uncoated.
[0035] Substrate is any material upon which one or more coating layers are able to be applied. In some instances, a substrate coated with a coating layer may be considered to form another substrate. For example, a substrate may be, e.g., a vinyl tile. However, a vinyl tile with a coating layer on its surface may also be considered to be a substrate.
[0036] Other relevant information and/or definitions may be found in several other applications that were filed concurrently or approximately with the present application, bearing Attorney Reference Nos. 2589-21 P (U.S. Provisional Application Ser. No. 62/404,479, filed Oct. 5, 2016, titled Floor Coatings Comprising a Resin, a Cure System and Diamond Particles and Methods of Making the Same), 2589-22 P (U.S. Provisional Application Ser. No. 62/404,389, filed Oct. 5, 2016, titled Testing of Wear Resistance), 2589-23 P (U.S. Provisional Application Ser. No. 62/404,445, filed Oct. 5, 2016, titled Coating Compositions Including Diamond and Either Cationic Curable Resin Systems or Thiol-Ene Curable Systems), and 2589-24 P (U.S. Provisional Application Ser. No. 62/404,503, filed Oct. 5, 2016, titled LED Curable Coatings for Flooring Comprising Diamond Particles and Methods of Making the Same); each of which is incorporated by reference herein in its entirety.
[0037]
The Base Layer of the Surface Covering
[0038] The present invention includes laminate structures which have a base layer and a wear-resistant layer. The base-layer 2 may have a thickness of about 35-170 mils and includes a polymeric resin which serves as a base-layer binder for additional components, such as fillers, plasticizers, stabilizing aids, processing aids and pigments. The base-layer binder may be, for example, a polymeric resin, such as a vinyl resin, mixed with a plasticizer, stabilizer, and processing aids. The polymeric resin may include, for example, a homopolymer, copolymer, terpolymer or combinations thereof. The homopolymer may include, for example, polyvinyl chloride, polyvinyl acetate, polyvinyl propionate, polyvinyl butyrate, polymerized vinylidene chloride, polymerized acrylic acid, polymerized ethyl acrylate, polymerized methyl acrylate, polymerized propyl acrylate, polymerized butyl acrylate, polyethylene, polypropylene, or mixtures thereof. The copolymer may include, for example, polyvinyl chloride/polyvinyl acetate, vinylidene chloride/vinyl chloride, methyl methacrylate/vinyl chloride, methyl acrylate/eth acrylate, ethyl acrylate/butyl acrylate copolymer, ethylene propylene copolymers, ethylene styrene copolymers, or mixtures thereof. The terpolymers may include, for example, polyvinyl chloride/polyvinyl acetate/carbon monoxide, or polyvinyl chloride/polyvinyl; Acetate/acrylic polymer. Alternatively, the base-layer binder may be, for example, a thermoplastic polyester resin including at least one recyclable or renewable component. Additional base-layer binders may include polyethyleneterephthalate (PET), glycolated polyethyleneterephthalate (PETG), polybutylene terephthalate (PBT), polypropylene terephthalate (PPT), or a thermoplastic ionomer resin, such as SURLYN from E. I. du Pont de Nemours and Company. The polymeric resin may also consist, for example, of recycled material, such as recycled polyethyleneterephthalate (PET) or polybutylene terephthalate (PBT) modified by renewable polyesters.
[0039] Each of the layers of a laminate structure may include various additives such as plasticizers, stabilizers, catalysts, modifiers, pigments, dyes, tints fillers and the like.
[0040] The plasticizer may include, for example, ester type plasticizers, such as orthophthalates, non-orthopthalates, phosphates, benzoates, modified benzoates, tartrates, sebacates, adipates, citrates, hexanoates, soyates, trimellitates, sulfonates, rubbery plasticizers, such as butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, or ethylene vinyl acetate, or other materials which function as plasticizers, such as epoxidized drying oils, aromatic hydrocarbon condensates and, chlorinated paraffins. The amount of plasticizer useful may vary from about 0% to about 20% by weight of the layer in which it is used.
[0041] Where certain flexible soft vinyl resins are used, such as polymers containing large proportions of ethyl acrylate, no plasticizer may be needed. The stabilizer may include, for example, a mixed metal stabilizer, such as a calcium-zinc composition. The processing aids may include, for example, hydrocarbon resins, polystyrene resins, impact modifiers, flow modifiers, or fusion promoters, such as acrylic copolymers or polyethylene oxide.
[0042] The filler may include, for example, an inorganic or organic material, such as calcium carbonate, magnesium carbonate, silica, diatomaceous earth, dolomite, clay, or mixtures thereof. The filler may be a recyclable or renewable material. The optional pigment may include, for example, titanium dioxide, iron oxides, phthalocyanine blue, phthalocyanine green, azo red, benzidene yellow, carbon black, or mixtures thereof.
[0043] The formulation of the base layer 2 may contain, for example, about 5 to about 80% weight of the binder, preferably about 10 to about 60% weight of the binder, and more preferably about 15 to about 35% weight of the binder. Additionally, the base layer 2 contains, for example, about 20 to about 95% weight of the filler, preferably about 40 to about 90% weight of the filler, and more preferably about 65 to about 85% weight of the filler.
Wear-Resistant Composition And Layer
[0044] The wear-resistant layer 3 may be a coating composition comprising a polymer hot-melt binder system having dispersed therein at least one with the wear-resistant additive which includes diamond particles 4. The wear-resistant layer 3 may have a thickness of about 1-40 mils, preferably about 2 mils to about 12 mils, and more preferably about 2 to about 4 mils. The polymer hot-melt binder system may include, for example, a polymeric hot-melt resin mixed with an additive package and a plasticizer. In one particularly useful aspect of the invention the polymeric hot-melt resin may be a resin having a backbone prepared from a polyurethane, polyether, polyester, polyetherester, polyesterether, polyolefin, polycaprolactone, polybutadiene, polycarbonate, polyacetal, polyester amide, styrene-butadiene-styrene (SBS), epoxy, polythioether or combinations thereof. Desirably the hot-melt resin is a reactive hot-melt, meaning that it has reactive groups which serve to polymerize even after the hot-melt is cooled and physically set. For example, the hot-melt may have moisture-curing groups present which may react with ambient moisture to crosslink once the hot-melt has be shaped to the desired form. Such reactive groups present on the hot-melt binder system may be selected from isocyanate groups, alkoxy groups, silanol groups and combinations thereof.
[0045] Examples of hot-melts useful in the present invention include, without limitation, those described in U.S. Pat. No. 4,946933; U.S. Pat. No. 5,166,302; U.S. Pat. No. 6,015,865; U.S. Pat. No. 8,163,824; U.S. Pat. No. 9,023946; Publication US20030010442 A1; all of which are incorporated in their entirety by reference herein.
[0046] Desirably the hot-melt binder is a polyurethane-containing polymer having reactive isocyanate groups present, which moisture cure.
[0047] The hot-melt binder may also be a clear layer that contains the wear-resistant additive and which may be then laminated to the another layer or substrate. A combination of clear and non-clear layers may be useful as well
[0048] Wear-resistant additives can be added to the hot-melt binder by mixing the additives into the hot-melt, or the additives may be sprinkled onto the surface of the hot-melt resin and embedded into the hot-melt using heat and pressure, e.g. calendaring or laminating, such as using a flat-bed press.
[0049] The diamond additive dispersed in the polymeric hot-melt includes, but is not limited to, diamond particles, diamond dust, diamond shards, diamond fragments and whole diamonds, or combinations of the foregoing. In related aspects the average diameter of the diamond material may be in the nanometer range or in the micrometer range. For example, when in the nanoparticle range, the average diameter may be in ranges of from about 0.1 nm to about 1,000 nm; preferably from about 0.2 nm to about 900 nm; more preferably from about 0.5 nm to about 800 nm; even more preferably from about 1 nm to about 600 nm; yet even more preferably from about 2 nm to about 500 nm; and most preferably from about 10 nm to about 500 nm, from about 20 nm to about 500 nm, from about 25 nm to about 250 nm, from about 35 nm to about 175 nm, from about 50 nm to about 150 nm, from about 75 nm to about 125 nm or from about 20 nm to about 40 nm.
[0050] When in the micrometer range, the average diameter of the diamond additive may be in ranges of from about 0.01 m to about 100 m; preferably from about 0.1 m to about 75 m; more preferably from about 0.5 m to about 50 m; even more preferably from about 0.75 m to about 25 m; yet even more preferably from about 1 m to about 10 m; and most preferably from about 1 m to about 5 m, from about 5 m to about 10 m, from about 2.5 m to about 7.5 m, or from about 6 m to about 10 m.
[0051] The wear-resistant particle sizes have a narrow distribution which may have a standard deviation of less than 35% of the average particle size. In some aspects of the invention a ratio of the average wear-resistant coating layer thickness to average wear-resistant additive particle size ranges from 0.6:1 to 2:1.
[0052] The wear-resistant additive particles which include diamond particles, may be present in an amount ranging from about 1% to about 50% , desirably about 1% to about 20% and even more desirably about 2 wt. % to about 6 wt.% based on the total weight of the wear-resistant coating composition.
[0053] In order to determine wt. %, a sample size of a cured coating layer may be tested. The sample may be of any size, e.g., 1 cm.sup.2, 10 cm.sup.2, 100 cm.sup.2, or any other size useful for testing. The thickness of the coating layer sample being tested should, statistically, have the same average thickness as the rest of the coating layer.
[0054] Additional wear-resistant additives may also be included, including more than one form or size of diamond additive. The second wear-resistant additive may be any material that has a Mohs hardness value of at least 6 including, but not limited to, aluminum oxide and feldspar, or a combination of both. The average diameter of one of the wear-resistant materials may be in the nanometer range, while the other abrasion resistant material may have an average diameter in the micrometer range. Alternatively, both abrasion resistant materials may have average diameters in the nanometer range, or both abrasion resistant materials may have average diameters in the micrometer range
[0055] The hot-melt binder may further include a cure system which includes one or more plasticizers, catalysts, stabilizers, modifiers, processing aids, internal and/or external lubricant packages, ultraviolet absorbers, tints, pigments, other specialty additives, or any combination thereof, such as those described herein with respect to the base-layer.
[0056] For a polymer hot-melt binder system comprising a polyurethane resin, the additive package may include, for example, a stabilizer, a modifier, an acrylic processing aid, an internal and external lubricant package, an ultraviolet absorber, tint, other specialty additives, or any combination thereof.
[0057] When present, the stabilizer may be incorporated at a level of about 0.7 to about 3 parts per hundred parts by weight of the polymeric hot-melt resin (phr) and [may comprise for example, a thermal stabilizer, such as organo tin, calcium zinc, or other metallic salt.
[0058] A hot-melt resin modifier may be present in the film, for example, at a level of about 4 to about 15 parts per hundred parts by weight of the polymeric hot-melt resin (phr) and may include, for example, an impact strength modifier, such as methylmethacrylate butadiene styrene (MBS), acrylonitrile butadiene styrene (ABS), or all-acrylic. An acrylic processing aid may be present in the film, for example, at a level of about 1-3 parts per hundred parts by weight of the polymeric resin (phr). An internal and external lubricant package may be present in the film, for example, at a level of about 0.2 to about 1.5 parts per hundred parts by weight of the polymeric hot-melt resin (phr) and may include, for example, glycerol monooleate, glycerides, or ester wax. The ultraviolet absorber may be present in the film, for example, at a level of about 0.0 to about 0.8 parts per hundred parts by weight of the polymeric hot-melt resin (phr). The tint may include, for example, transparent or filled titanium dioxide opaque color tints or transparent clear tints.
[0059] In one aspect of the invention, the film may be a rigid film, and more preferably a rigid vinyl film. A rigid film is generally known in the art as a film that is free of or substantially free of plasticizers, e.g., comprising less than 5 parts of the plasticizer per hundred parts by weight of the polymeric resin (phr). It will be appreciated by those skilled in the art, however, that the film may alternatively be a semi-rigid film or a flexible film. A semi-rigid film is defined herein as a film which includes about 5 to about 10 parts of the plasticizer per hundred parts by weight of the polymeric hot-melt resin (phr). A flexible film is defined herein as a film comprising greater than about 10 parts of the plasticizer per hundred parts by weight of the polymeric hot-melt resin (phr).
[0060] The wear-resistant additive particles 4 dispersed in the polymer hot-melt binder system of the film include diamond particles and optionally additional wear-resistant additives such as aluminum oxide (Al.sub.2O.sub.3) particles, crystalline classes of silicon carbide, hard plastics, reinforced polymers, nylon, organics, or any combination thereof.
[0061] The wear-resistant layer 3 may be prepared by dispersing the wear-resistant particles 4 in a compatible liquid to form a stable liquid dispersion. The liquid may be, for example, a liquid component of the polymer hot-melt binder system, such as the plasticizer or a liquid component of the additive package. The stable liquid dispersion may then be blended in the polymeric hot-melt resin, as well as any remaining components of the polymer hot-melt binder system, using a high speed mixer to a temperature of about 60-90 degrees Celsius to form a mixture. The mixture containing the polymer hot-melt binder system and the wear-resistant particles 4 is thermally compressed, fused, and compounded and preferably extruded or continuously mixed to a temperature of about 160-200 degrees Celsius. The mixture is then preferably calendared to form the wear layer 3. For the wear layer 3, comprising the vinyl resin, the calendaring temperatures may range, for example, from about 190-225 degrees Celsius. Because the processes of blending, compounding, extruding, and calendaring a mixture to form a film is well known in the art, further description thereof has been omitted.
[0062] As shown in
[0063] In certain aspects of the invention, the invention provides a floor covering which includes a substrate prepared according to any of the above-described methods. The substrate may be, but is not necessarily limited to, tile (e.g., vinyl tile, ceramic tile, porcelain tile and wood tile), linoleum, laminate, engineered wood, wood (e.g., ash, birch, cherry, exotic, hickory, maple, oak, pecan and walnut), cork, stone, bamboo, vinyl sheet, and combinations of any of the foregoing.
[0064] In another aspect of the invention, the abrasion resistant material may protrude from the top surface of a coating layer at a distance of from about 1-50% of the average coating thickness. The ratio of the average coating thickness to the average diameter of the abrasion resistant material may sometimes be in the range of from about 0.6:1 to about 2:1. In some instances, the average distance between two pieces of abrasion resistant material is from about 20-75 m.
[0065]
[0066]
[0067] The polymer binder system may comprise, for example, a polymeric resin mixed with an additive package and a plasticizer. The polymeric resin may be, for example, a vinyl resin, such as polyvinyl chloride. Alternatively, the polymeric resin may be, for example, polyethyleneterephthalate (PET), glycolated polyethyleneterephthalate (PETG), polybutylene terephthalate (PBT), polypropylene terephthalate (PPT), or a thermoplastic ionomer resin, such as SURLYN from E. I. du Pont de Nemours and Company. The polymeric resin may also consist, for example, of recycled material, such as recycled polyethyleneterephthalate (PET) or polybutylene terephthalate (PBT) modified by renewable polyesters. The plasticizer may include, for example, unsaturated glycerides or phthalate esters. The additive package may include, for example, a stabilizer, a modifier, an acrylic processing aid, an internal and external lubricant package, an ultraviolet absorber, tint, other specialty additives, or any combination thereof.
[0068] In
[0069] The print layer 7 is laminated to the base layer 2 between the base layer 2 and the wear layer 3. The print layer 7 is laminated to the base layer 2 between the base layer 2 and the wear layer 3, for example, using a conventional standard stack press or a conventional rolling nip-type laminator.
[0070] In the surface covering 1 according some embodiments of the invention described herein, the wear layer 3, may form the outmost surface of the surface covering 1, and may include dispersed therein the wear-resistant additive 4 comprising diamond particles, which provides the wear layer 3 with added abrasion and chemical resistance properties. The surface covering 1 according to the invention thereby can be easily constructed to have an outermost surface with added abrasion and chemical resistance properties while eliminating unnecessary processing steps and reducing costs.
[0071] The foregoing illustrates some of the possibilities for practicing the invention. Many other embodiments are possible within the scope and spirit of the invention. For example, although the wear layer 3, is shown and described herein as being used in conjunction with the surface coverings 1, which are related to flooring surfaces, it will be appreciated by those skilled in the art that the wear layer could be used in conjunction with other types of surface coverings, such as wall paper, countertops, automobile structures, furniture surfaces, protective case surfaces, and the like, and still exhibit the same added abrasion and chemical resistance properties. It is, therefore, intended that the foregoing description be regarded as illustrative rather than limiting, and that the scope of the invention is given by the appended claims together with their full range of equivalents.