WO2011112479A1

WO2011112479A1 - Golf ball having ionomer/hydrophobic thermoplastic polyurethane layers

Info

Publication number: WO2011112479A1
Application number: PCT/US2011/027334
Authority: WO
Inventors: Bradley C. Tutmark
Original assignee: Nike International Ltd.
Priority date: 2010-03-10
Filing date: 2011-03-07
Publication date: 2011-09-15
Also published as: US20110224023A1; JP5566480B2; CN103002956A; CN103002956B; JP2013521873A; EP2544776A1; EP2544776B1

Abstract

A golf ball has moisture resistant layer comprising a blend of at least one ionomer and hydrophobic thermoplastic polyurethane. The moisture resistant layer may be part of the cover layer, for example an inner layer of a two-layer cover layer. The moisture resistant layer may be an intermediate layer between the core and the cover.

Description

GOLF BALL HAVING IONOMER / HYDROPHOBIC THERMOPLASTIC

POLYURETHANE LAYERS

[0001] This application claims benefit from U.S. Provisional application No.

61/312,286, filed March 10, 2010, the whole contents of which are incorporated herein by reference in its entirety.

FIELD OF THE INVENTION

[0002] The present invention relates to golf balls. Particular example aspects of this invention relate to golf balls having materials that improve the moisture resistance of the ball as well as scruff resistance, softness, and flexibility of the golf ball layers.

BACKGROUND

[0003] Golf is enjoyed by a wide variety of players - players of different genders and dramatically different ages and/or skill levels. Golf is unique in the sporting world in that such diverse collections of players can play together in golf events, even in direct competition with one another (e.g., using handicapped scoring, different tee boxes, in team formats, etc.), and still enjoy the golf outing or competition. These factors, together with the increased availability of golf programming on television (e.g., golf tournaments, golf news, golf history, and/or other golf programming) and the rise of well known golf superstars, at least in part, have increased golfs popularity in recent years, both in the United States and across the world.

[0004] Golfers at all skill levels seek to improve their performance, lower their golf scores, and reach that next performance "level." Manufacturers of all types of golf equipment have responded to these demands, and in recent years, the industry has witnessed dramatic changes and improvements in golf equipment. For example, a wide range of different golf ball models now are available, with balls designed to complement specific swing speeds and/or other player characteristics or preferences, e.g., with some balls designed to fly farther and/or straighter; some designed to provide higher or flatter trajectories; some designed to provide more spin, control, and/or feel (particularly around the greens); some designed for faster or slower swing speeds; etc. A host of swing and/or teaching aids also are available on the market that promise to help lower one's golf scores.

[0005] Being the sole instrument that sets a golf ball in motion during play, golf clubs also have been the subject of much technological research and advancement in recent years. For example, the market has seen dramatic changes and improvements in putter designs, golf club head designs, shafts, and grips in recent years. Additionally, other technological advancements have been made in an effort to better match the various elements and/or characteristics of the golf club and characteristics of a golf ball to a particular user's swing features or characteristics (e.g., club fitting technology, ball launch angle measurement technology, ball spin rate measurement technology, ball fitting technology, etc.).

[0006] Modern golf balls generally comprise either a one-piece construction or several layers including an outer cover surrounding a core. Some golf ball layers include thermoplastic urethane (TPU) type materials. A problem experienced with thermoplastic urethane type layer materials is high Water Vapor Transmission Rate (WVTR.) The problem arises when moisture penetrates the ball over time and will harden the ball's rubber core, or any other rubber layer. This will change the ball's performance and durability.

[0007] While the industry has witnessed dramatic changes and improvements to golf equipment in recent years, some players continue to look for increased distance on their golf shots, particularly on their drives or long iron shots, and/or improved spin or control of their shots, particularly around the greens. Accordingly, there is room in the art for further advances in golf technology.

SUMMARY

[0008] The following presents a general summary of aspects of the disclosure in order to provide a basic understanding of the disclosure and various aspects of it. This summary is not intended to limit the scope of the disclosure in any way, but it simply provides a general overview and context for the more detailed description that follows. [0009] Aspects of this invention are directed to a golf ball having at least one layer comprising a blend of at least one ionomer and hydrophobic thermoplastic polyurethane. The at least one layer may be a core layer, a cover layer, or any intermediate layer.

[0010] Other aspects of this invention are directed to methods for making a golf ball having at least one layer applying a coating comprising at least one ionomer and hydrophobic thermoplastic polyurethane.

BRIEF DESCRIPTION OF THE DRAWINGS

[0011] A more complete understanding of the present invention and certain advantages thereof may be acquired by referring to the following detailed description in consideration with the accompanying drawings, in which:

[0012] FIG. 1 schematically illustrates a golf ball having dimples.

[0013] FIG. 2 schematically illustrates a cross-sectional view of a golf ball in accordance with FIG. 1.

[0014] FIG. 3 schematically illustrates another cross-sectional view of a golf ball in accordance with FIG. 1.

[0015] FIG. 4 provides Moisture Vapor Transmission Rates for various Hydrophobic

TPU blends.

[0016] The reader is advised that the various parts shown in these drawings are not necessarily drawn to scale.

DETAILED DESCRIPTION

[0017] In the following description of various example structures, reference is made to the accompanying drawings, which form a part hereof, and in which are shown by way of illustration various example golf ball structures. When the same reference number appears in more than one drawing, that reference number is used consistently in this specification and the drawings to refer to the same or similar parts throughout. Additionally, it is to be understood that other specific arrangements of parts and structures may be utilized and structural and functional modifications may be made without departing from the scope of the present invention. Also, while terms such as "top," "bottom," "front," "back," "rear," "side," "underside," "overhead," and the like may be used in this specification to describe various example features and elements of the invention, these terms are used herein as a matter of convenience, e.g., based on the example orientations shown in the figures and/or the orientations in typical use. Nothing in this specification should be construed as requiring a specific three dimensional or spatial orientation of structures.

A. General Description of Golf Balls and Manufacturing Systems and Methods

[0018] Golf balls may be of varied construction, e.g., one-piece balls, two-piece balls, three-piece balls (including wound balls), four-piece balls, five-piece balls, etc. The difference in play characteristics resulting from these different types of constructions can be quite significant. Generally, golf balls may be classified as solid or wound balls. Solid balls that have a two-piece construction, typically a cross-linked rubber core, e.g., polybutadiene cross-linked with zinc diacrylate and/or similar cross-linking agents, encased by a blended cover, e.g., ionomer resins, are popular with many average recreational golfers. The combination of the core and cover materials provide a relatively "hard" ball that is virtually indestructible by golfers and one that imparts a high initial velocity to the ball, resulting in improved distance. Because the materials from which the ball is formed are very rigid, two-piece balls tend to have a hard "feel" when struck with a club. Likewise, due to their hardness, these balls have a relatively low spin rate, which also helps provide greater distance.

[0019] Wound balls are generally constructed from a liquid or solid center surrounded by tensioned elastomeric material and covered with a durable cover material, e.g., ionomer resin, or a softer cover material, e.g., balata or polyurethane. Wound balls are generally thought of as performance golf balls and have good resiliency, desirable spin characteristics, and good "feel" when struck by a golf club. However, wound balls are generally difficult to manufacture as compared to solid golf balls. [0020] More recently, three- and four-piece balls have gained popularity, both as balls for average recreational golfers as well as performance balls for professional and other elite level players. Such balls typically include a core (optionally a multipart core, such as an inner core and an outer core), one or more mantle or intermediate layers (also called "inner cover" layers), and an outer cover layer.

[0021] A variety of golf balls have been designed to provide particular playing characteristics. These characteristics generally include the initial velocity and spin of the golf ball, which can be optimized for various types of players. For instance, certain players prefer a ball that has a high spin rate in order to control and stop the golf ball around the greens. Other players prefer a ball that has a low spin rate and high resiliency to maximize distance. Generally, a golf ball having a hard core and a soft cover will have a high spin rate. Conversely, a golf ball having a hard cover and a soft core will have a low spin rate. Golf balls having a hard core and a hard cover generally have very high resiliency for distance, but they may "feel" hard and be difficult to control around the greens.

[0022] The carry distance of some conventional two-piece balls has been improved by altering the typical single layer core and single cover layer construction to provide a multi-layer ball, e.g., a dual cover layer, dual core layer, and/or a ball having an intermediate layer disposed between the cover and the core. Three- and four-piece balls are now commonly found and commercially available. Aspects of this invention may be applied to all types of ball constructions, including the wound, solid, and/or multi-layer ball constructions described above.

[0023] FIG. 1 is a perspective view of a solid golf ball 100 according to an aspect of the invention. Golf ball 100 may be generally spherical in shape with a plurality of dimples 102 arranged on the outer surface 108 of golf ball 100 in a pattern 112.

[0024] Internally, golf ball 100 may be generally constructed as a multilayer solid golf ball, having any desired number of pieces. In other words, multiple layers of material may be fused, blended, or compressed together to form the ball. The physical characteristics of a golf ball may be determined by the combined properties of the core layer(s), any optional mantle layers, and the cover. The physical characteristics of each of these components may be determined by their respective chemical compositions. The majority of components in golf balls comprise oligomers or polymers. The physical properties of oligomers and polymers may be highly dependent on their composition, including the monomer units included, molecular weight, degree of cross-linking, etc. Examples of such properties may include solubility, viscosity, specific gravity (SG), elasticity, hardness (e.g., as measured as Shore D hardness), rebound resilience, scuff resistance, etc. The physical properties of the oligomers and polymers used may also affect the industrial processes used to make the components of the golf ball. For example, where injection molding is the processing method used, extremely viscous materials may slow down the process and thus viscosity may become a limiting step of production.

[0025] As shown in FIG. 2, one aspect of such a golf ball (referred to generally as 200) includes a core 204, a cover 208, and an intermediate layer 206 between core 204 and cover 208. Cover 208 surrounds, encloses, encompasses, etc., the core and any other internal layers of the ball. Cover 208 has an outer surface that may include a dimple pattern comprising a plurality of dimples.

[0026] As shown in FIG. 3, another aspect of such a golf ball (referred to generally as

300) includes a core 304, a cover 308, and intermediate layers 306 and 310 between core 304 and cover 308. Cover 308 surrounds, encloses, encompasses, etc., the core and any other internal layers of the ball. Cover 308 has an outer surface that may include a dimple pattern comprising a plurality of dimples.

The Center

[0027] A golf ball may be formed, for example, with a center having a low compression, but still exhibit a finished ball COR and initial velocity approaching that of conventional two-piece distance balls. The center may have, for example, a compression of about 60 or less. The finished balls made with such centers have a COR, measured at an inbound speed of 125 ft./s., of about 0.795 to about 0.815. "COR" refers to Coefficient of Restitution, which is obtained by dividing a ball's rebound velocity by its initial (i.e., incoming) velocity. This test is performed by firing the samples out of an air cannon at a vertical steel plate over a range of test velocities (e.g., from 75 to 150 ft/s). A golf ball having a high COR dissipates a smaller fraction of its total energy when colliding with the plate and rebounding therefrom than does a ball with a lower COR.

[0028] The terms "points" and "compression points" refer to the compression scale or the compression scale based on the ΑΤΠ Engineering Compression Tester. This scale, which is well known to persons skilled in the art, is used in determining the relative compression of a center or ball.

[00291 The center may have, for example, a Shore C hardness of about 40 to about 80.

The center may have a diameter of about 0.75 inches to about 1.68 inches. The base composition for forming the center may include, for example, polybutadiene and about 20 to 50 parts of a metal salt diacrylate, dimethacrylate, or monomethacrylate. If desired, the polybutadiene can also be mixed with other elastomers known in the art, such as natural rubber, styrene butadiene, and/or isoprene, in order to further modify the properties of the center. When a mixture of elastomers is used, the amounts of other constituents in the center composition are usually based on 100 parts by weight of the total elastomer mixture. In other examples, the center (or core) may be made from resin materials, such as HPF resins (optionally with barium sulfate included therein), which are commercially available from E.I. DuPont de Nemours and Company of Wilmington, Delaware.

[0030] Metal salt diacrylates, dimethacrylates, and monomethacrylates include without limitation those wherein the metal is magnesium, calcium, zinc, aluminum, sodium, lithium or nickel. Zinc diacrylate, for example, provides golf balls with a high initial velocity in the United States Golf Association ("USGA") test.

[0031] Free radical initiators often are used to promote cross-linking of the metal salt diacrylate, dimethacrylate, or monomethacrylate and the polybutadiene. Suitable free radical initiators include, but are not limited to peroxide compounds, such as dicumyl peroxide; 1 , 1 -di(t-butylperoxy) 3,3,5-trimethyl cyclohexane; bis (t- butylperoxy) diisopropylbenzene; 2,5-dimethyl-2,5 di (t-butylperoxy) hexane; or di-t-butyl peroxide; and mixtures thereof. The initiator(s) at 100 percent activity may be added in an amount ranging from about 0.05 to about 2.5 pph based upon 100 parts of butadiene, or butadiene mixed with one or more other elastomers. Often the amount of initiator added ranges from about 0.15 to about 2 pph, and more often from about 0.25 to about 1.5 pph. The golf ball centers may incorporate 5 to 50 pph of zinc oxide (ZnO) in a zinc diacrylate-peroxide cure system that cross-links polybutadiene during the core molding process.

[0032] The center compositions may also include fillers, added to the elastomeric (or other) composition to adjust the density and/or specific gravity of the center. Non-limiting examples of fillers include zinc oxide, barium sulfate, and regrind, e.g., recycled core molding matrix ground to about 30 mesh particle size. The amount and type of filler utilized is governed by the amount and weight of other ingredients in the composition, bearing in mind a maximum golf ball weight of 1.620 oz has been established by the USGA. Fillers usually range in specific gravity from about 2.0 to about 5.6. The amount of filler in the center may be lower such that the specific gravity of the center is decreased.

[0033] The specific gravity of the center may range, for example, from about 0.8 to about 1.3, depending upon such factors as the size of the center, cover, intermediate layer and finished ball, as well as the specific gravity of the cover and intermediate layer. Other components such as accelerators, e.g., tetra methylthiuram, processing aids, processing oils, plasticizers, dyes and pigments, antioxidants, as well as other additives well known to the skilled artisan may also be used in amounts sufficient to achieve the purpose for which they are typically used.

Intermediate Laver(s)

[0034] The golf ball also may have one or more intermediate layers formed, for example, from dynamically vulcanized thermoplastic elastomers, functionalized styrene- butadiene elastomers, thermoplastic rubbers, polybutadiene rubbers, natural rubbers, thermoset elastomers, thermoplastic urethanes, metallocene polymers, thermoset urethanes, ionomer resins, or blends thereof. For example, an intermediate layer may include a thermoplastic or thermoset polyurethane. Non- limiting of commercially available dynamically vulcanized thermoplastic elastomers include SANTOPRENE^®, SARLINK^®, VYRAM^®, DYTRON^®, and VISTAFLEX^®. SANTOPRENE^® is a dynamically vulcanized PP/EPDM. Examples of functionalized styrene-butadiene elastomers, i.e., styrene-butadiene elastomers with functional groups such as maleic anhydride or sulfonic acid, include KRATON FG-1901x and FG-1921x, which are available from the Shell Corporation of Houston, Tex.

[0035] Examples of suitable thermoplastic polyurethanes include ESTANE^® 58133,

ESTANE^® 58134 and ESTANE^® 58144, which are commercially available from the Lubrizol of Cleveland, Ohio.

[0036] Examples of metallocene polymers, i.e., polymers formed with a rnetallocene catalyst, include those commercially available from Sentinel Products of Hyannis, Mass. Suitable thermoplastic polyesters include polybutylene terephthalate.

Thermoplastic ionomer resins may be obtained by providing a cross metallic bond to polymers of monoolefin with at least one member selected from the group consisting of unsaturated mono- or di-carboxylic acids having 3 to 12 carbon atoms and esters thereof (the polymer contains 1 to 50 percent by weight of the unsaturated mono- or di-carboxylic acid and/or ester thereof). More particularly, low modulus ionomers such as acid-containing ethylene copolymer ionomers, include E/X/Y copolymers where E is ethylene, X is a softening comonomer such as acrylate or methacrylate. Non-limiting examples of ionomer resins include SURLYN^® and IOTEK®, which are commercially available from DuPont and Exxon, respectively.

[0037] Alternatively, the intermediate layer(s) may be a blend of a first and a second component wherein the first component is a dynamically vulcanized thermoplastic elastomer, a functionalized styrene-butadiene elastomer, a thermoplastic or thermoset polyurethane or a metallocene polymer and the second component is a material such as a thermoplastic or thermoset polyurethane, a thermoplastic polyetherester or polyetheramide, a thermoplastic ionomer resin, a thermoplastic polyester, another dynamically vulcanized elastomer, another a functionalized styrene-butadiene elastomer, another a metallocene polymer or blends thereof. At least one of the first and second components may include a thermoplastic or thermoset polyurethane. [0038] One or more intermediate layers also may be formed from a blend containing an ethylene methacrylic/acrylic acid copolymer. Non-limiting examples of acid- containing ethylene copolymers include ethylene/acrylic acid; ethylene/methacrylic acid; ethylene/acrylic acid/n- or isobutyl acrylate; ethylene/methacrylic acid/n- or iso-butyl acrylate; ethylene/acrylic acid/methyl acrylate; ethylene/methacrylic acid/methyl acrylate; ethylene/acrylic acid/iso- bornyl acrylate or methacrylate and ethylene/methacrylic acid isobornyl acrylate or methacrylate. Examples of commercially available ethylene methacrylic/acrylic acid copolymers include NUCREL^® polymers, available from DuPont.

[0039] Alternatively, the intermediate layer(s) may be formed from a blend which includes an ethylene methacrylic/acrylic acid copolymer and a second component which includes a thermoplastic material. Suitable thermoplastic materials for use in the intermediate blend include, but are not limited to, polyesterester block copolymers, polyetherester block copolymers, polyetheramide block copolymers, ionomer resins, dynamically vulcanized thermoplastic elastomers, styrene- butadiene elastomers with functional groups such as maleic anhydride or sulfonic acid attached, thermoplastic polyurethanes, thermoplastic polyesters, metallocene polymers, and/or blends thereof.

[0040] An intermediate layer often has a specific gravity of about 0.8 or more. In some examples the intermediate layer has a specific gravity greater than 1.0, e.g., ranging from about 1.02 to about 1.3. Specific gravity of the intermediate layer may be adjusted, for example, by adding a filler such as barium sulfate, zinc oxide, titanium dioxide and combinations thereof.

[0041] The intermediate layer blend may have a flexural modulus of less than about

15,000 psi, often from about 5,000 to about 8,000 psi. The intermediate layers often have a Shore D hardness of about 35 to 70. The intermediate layer and core construction together may have a compression of less than about 65, often from about 50 to about 65. Usually, the intermediate layer has a thickness from about 0.020 inches to about 0.2 inches. The golf balls may include a single intermediate layer or a plurality of intermediate layers. In the case where a ball includes a plurality of intermediate layers, a first intermediate layer outside the core may include, for example, a thermoplastic material or a rubber material (synthetic or natural) having a hardness greater than that of the core.

[0042] A second intermediate layer may be disposed around the first intermediate layer and may have a greater hardness than that of the first intermediate layer. The second intermediate layer may be formed of materials such as polyether or polyester thermoplastic urethanes, thermoset urethanes, and ionomers such as acid-containing ethylene copolymer ionomers.

[0043] In addition, if desired, a third intermediate layer (or even more layers) may be disposed in between the first and second intermediate layers. The third intermediate layer may be formed of the variety of materials as discussed above. For example, the third intermediate layer may have a hardness greater than that of the first intermediate layer.

The Cover Layer

[0044] A golf ball also typically has a cover layer that includes one or more layers of a thermoplastic or thermosetting material. A variety of materials may be used such as ionomer resins, thermoplastic polyurethanes, balata and blends thereof.

[0045] The cover may be formed of a composition including very low modulus ionomers

(VLMIs). As used herein, the term "very low modulus ionomers," or the acronym "VLMIs," are those ionomer resins further including a softening comonomer X, commonly a (meth)acrylate ester, present from about 10 weight percent to about 50 weight percent in the polymer. VLMIs are copolymers of an a-olefin, such as ethylene, a softening agent, such as n-butyl-acrylate or iso- butyl-acrylate, and an a, β-unsaturated carboxylic acid, such as acrylic or methacrylic acid, where at least part of the acid groups are neutralized by a magnesium cation. Other examples of softening comonomers include n-butyl methacrylate, methyl acrylate, and methyl methacrylate. Generally, a VLMI has a flexural modulus from about 2,000 psi to about 10,000 psi. VLMIs are sometimes referred to as "soft" ionomers.

Ionomers, such as acid-containing ethylene copolymer ionomers, include E/X/Y copolymers where E is ethylene, X is a softening comonomer such as acrylate or methacrylate present in 0 to 50 weight percent of the polymer, and Y is acrylic or methacrylic acid present in 5 to 35 (often 10 to 20) weight percent of the polymer, wherein the acid moiety is neutralized 1 to 90 percent (usually at least 40 percent) to form an ionomer by a cation such as lithium, sodium, potassium, magnesium, calcium, barium, lead, tin, zinc or aluminum, or a combination of such cations, lithium, sodium and zinc being the most preferred. Specific acid- containing ethylene copolymers include ethylene/acrylic acid, ethylene/methacrylic acid, ethylene/acrylic acid/n-butyl acrylate, ethylene/methacrylic acid/n-butyl acrylate, ethylene/methacrylic acid/iso-butyl acrylate, ethylene/acrylic acid/iso-butyl acrylate, ethylene/methacrylic acid/n- butyl methacrylate, ethylene/acrylic acid/methyl methacrylate, ethylene/acrylic acid/methyl acrylate, ethylene/methacrylic acid/methyl acrylate, ethylene/methacrylic acid/methyl methacrylate, and ethylene/acrylic acid/n-butyl methacrylate.

[0047] To aid in the processing of the cover stock, ionomer resins may be blended in order to obtain a cover having desired characteristics. For this reason, the cover may be formed from a blend of two or more ionomer resins. The blend may include, for example, a very soft material and a harder material. Ionomer resins with different melt flow indexes are often employed to obtain the desired characteristics of the cover stock. SURLYN^® 81 18, 7930 and 7940 have melt flow indices of about 1.4, 1.8, and 2.6 g/10 min., respectively. SURLYN^® 8269 and SURLYN^® 8265 each have a melt flow index of about 0.9 g/10 min. A blend of ionomer resins may be used to form a cover having a melt flow index, for example, of from about 1 to about 3 g/10 min. The cover layer may have a Shore D hardness, for example, ranging from about 45 to about 80.

[0048] The cover also may include thermoplastic and/or thermoset materials. For example, the cover may include a thermoplastic material such as urethane or polyurethane. Polyurethane is a product of a reaction between a polyurethane prepolymer and a curing agent. The polyurethane prepolymer is a product formed by a reaction between a polyol and a diisocyanate. Often, a catalyst is employed to promote the reaction between the curing agent and the polyurethane prepolymer. In the case of cast polyurethanes, the curing agent is typically either a diamine or glycol.

[0049] As another example, a thermoset cast polyurethane may be used. Thermoset cast polyurethanes are generally prepared using a diisocyanate, such as 2,4-toluene diisocyanate (TDI), methylenebis-(4-cyclohexyl isocyanate) (HMDI), or para- phenylene diisocyanate ("PPDI") and a polyol which is cured with a polyamine, such as methylenedianiline (MDA), or a trifunctional glycol, such as trimethylol propane, or tetrafunctional glycol, such as N,N,N',N'-tetrakis(2- hydroxpropyl)ethylenediamine. Other suitable thermoset materials include, but are not limited to, thermoset urethane ionomers and thermoset urethane epoxies. Other examples of thermoset materials include polybutadiene, natural rubber, polyisoprene, styrene-butadiene, and styrene-propylene-diene rubber.

[0050] When the cover includes more than one layer, e.g., an inner cover layer and an outer cover layer, various constructions and materials are suitable. For example, an inner cover layer may surround the intermediate layer with an outer cover layer disposed thereon or an inner cover layer may surround a plurality of intermediate layers. When using an inner and outer cover layer construction, the outer cover layer material may be a thermoset material that includes at least one of a castable reactive liquid material and reaction products thereof, as described above, and may have a hardness from about 30 Shore D to about 60 Shore D.

[0051] The inner cover layer may be formed from a wide variety of hard (e.g., about 50

Shore D or greater), high flexural modulus resilient materials, which are compatible with the other materials used in the adjacent layers of the golf ball. The inner cover layer material may have a flexural modulus of about 65,000 psi or greater. Suitable inner cover layer materials include the hard, high flexural modulus ionomer resins and blends thereof, which may be obtained by providing a cross metallic bond to polymers of monoolefin with at least one member selected from the group consisting of unsaturated mono- or di-carboxylic acids having 3 to 12 carbon atoms and esters thereof (the polymer contains 1 to 50 percent by weight of the unsaturated mono- or di-carboxylic acid and/or ester thereof). More particularly, such acid-containing ethylene copolymer ionomer component includes E/X/Y copolymers where E is ethylene, X is a softening comonomer such as acrylate or methacrylate present in 0-50 weight percent of the polymer, and Y is acrylic or methacrylic acid present in 5-35 weight percent of the polymer, wherein the acid moiety is neutralized about 1-90 percent to form an ionomer by a cation such as lithium, sodium, potassium, magnesium, calcium, barium, lead, tin, zinc, or aluminum, or a combination of such cations. Specific examples of acid-containing ethylene copolymers include ethylene/acrylic acid, ethylene/methacrylic acid, ethylene/acrylic acid/n-butyl acrylate, ethylene/methacrylic acid/n-butyl acrylate, ethylene/methacrylic acid/iso-butyl acrylate, ethylene/acrylic acid/iso-butyl acrylate, ethylene/methacrylic acid n- butyl methacrylate, ethylene/acrylic acid/methyl methacrylate, ethylene/acrylic acid/methyl acrylate, ethylene/methacrylic acid/methyl acrylate, ethylene/methacrylic acid/methyl methacrylate, and ethylene/acrylic acid/n-butyl methacrylate.

[0052] Examples of other suitable inner cover materials include thermoplastic or thermoset polyurethanes, polyetheresters, polyetheramides, or polyesters, dynamically vulcanized elastomers, functionalized styrene-butadiene elastomers, metallocene polymers, polyamides such as nylons, acrylonitrile butadiene-styrene copolymers (ABS), or blends thereof.

Manufacturing Process

[0053] While golf balls in accordance with examples of this invention may be made in any desired manner without departing from this invention, including in conventional manners as are known and used in the art, one common technique for manufacturing golf balls is a laminate process. In order to form multiple layers around the center, a laminate is first formed. The laminate includes at least two layers and sometimes includes three layers. The laminate may be formed by mixing uncured core material to be used for each layer and calendar rolling the material into thin sheets. Alternatively, the laminate may be formed by mixing uncured intermediate layer material and rolling the material into sheets. The laminate sheets may be stacked together to form a laminate having three layers, using calender rolling mills. Alternatively, the sheets may be formed by extrusion. [0054] A laminate also may be formed using an adhesive between each layer of material.

For example, an epoxy resin may be used as adhesive. The adhesive should have good shear and tensile strength, for example, a tensile strength over about 1500 psi. The adhesive often has a Shore D hardness of less than about 60 when cured. The adhesive layer applied to the sheets should be very thin, e.g., less than about 0.004 inches thick.

[0055] Preferably, each laminate sheet is formed to a thickness that is slightly larger than the thickness of the layers in the finished golf ball. Each of these thicknesses can be varied, but all have a thickness of preferably less than about 0.1 inches. The sheets should have very uniform thicknesses.

[0056] The next step in the method is to form multiple layers around the center. This may be accomplished by placing two laminates between a top mold and a bottom mold. The laminates may be formed to the cavities in the mold halves. The laminates then may be cut into patterns that, when joined, form a laminated layer around the center. For example, the laminates may be cut into figure 8-shaped or barbell-like patterns, similar to a baseball or a tennis ball cover. Other patterns may be used, such as curved triangles, hemispherical cups, ovals, or other patterns that may be joined together to form a laminated layer around the center. The patterns may then be placed between molds and formed to the cavities in the mold halves. A vacuum source often is used to form the laminates to the mold cavities so that uniformity in layer thickness is maintained.

[0057] After the laminates have been formed to the cavities, the centers are then inserted between the laminates. The laminates are then compression molded about the center under conditions of temperature and pressure that are well known in the art. The mold halves usually have vents to allow flowing of excess layer material from the laminates during the compression molding process. As an alternative to compression molding, the core and/or intermediate layer(s) may be formed by injection molding or other suitable technique.

The next step involves forming a cover around the golf ball core. The core, including the center and any intermediate layers, may be supported within a pair of cover mold-halves by a plurality of retractable pins. The retractable pins may be actuated by conventional means known to those of ordinary skill in the art.

[0059] After the mold halves are closed together with the pins supporting the core, the cover material is injected into the mold in a liquid state through a plurality of injection ports or gates, such as edge gates or sub-gates. With edge gates, the resultant golf balls are all interconnected and may be removed from the mold halves together in a large matrix. Sub-gating automatically separates the mold runner from the golf balls during the ejection of the golf balls from mold halves.

[0060] The retractable pins may be retracted after a predetermined amount of cover material has been injected into the mold halves to substantially surround the core. The liquid cover material is allowed to flow and substantially fill the cavity between the core and the mold halves, while maintaining concentricity between the core and the mold halves. The cover material is then allowed to solidify around the core, and the golf balls are ejected from the mold halves and subjected to finishing processes, including coating, painting, and/or other finishing processes, including processes in accordance with examples of this invention, as will be described in more detail below.

B. General Description of the Ionomer/Hydrophobic TPU Layer

[0061] The Ionomer/hydrophobic TPU layer comprises a blend of at least one ionomer and hydrophobic thermoplastic polyurethane (hydrophobic TPU). The blend is applied to a golf ball in any suitable manner such as with a molding process step.

[0062] The ionomer/ hydrophobic TPU layer may be part of the cover layer, for example, an inner layer of the cover layer, or may be one of the intermediate or inner layers between the core and the cover layer.

C. Aspects of Invention

[0063] An aspect of this invention relate to golf balls having an ionomer/ hydrophobic

TPU inner layer positioned between the core layer and the cover layer. The ionomer/ hydrophobic TPU layer comprises a blend of at least one ionomer and hydrophobic thermoplastic polyurethane. In one aspect the ionomer/ hydrophobic TPU layer is an inner layer adjacent the cover layer. In another aspect the ionomer/ hydrophobic TPU layer is an inner layer adjacent the core.

[0064] Another aspect of this invention relate to golf balls having a cover comprising at least one layer comprising a blend of at least one ionomer and hydrophobic thermoplastic polyurethane.

[0065] Given the general description of various example aspects of the invention provided above, more detailed descriptions of various specific examples of golf ball structures according to the invention are provided below.

D. Detailed Description of Example Golf Balls, and Methods According to Aspects of the Invention

[0066] The following discussion and accompanying figures describe various example golf balls in accordance with aspects of the present invention.

[0067] Aspects of the invention utilize an ionomer/ hydrophobic TPU layer comprising a blend of ionomer and hydrophobic thermoplastic polyurethane (hydrophobic TPU). The ionomer/ hydrophobic TPU layer has a Shore D hardness suitable for golf balls but also provides effective moisture protection to the golf ball.

[0068] In particular, the ionomer and hydrophobic TPU blend provides a moisture barrier layer having a Water Vapor Transmission Rate (WVTR) of less than 1300 in grams/m² after 168 hrs at 25°C and 50% relative humidity for instance less than 1000, preferably less than 750.

[0069] The Shore D hardness of an ionomer/TPU cover layer or inner layer is between

20 and 85. "Shore D hardness" refers to a measure of the hardness of a material by a durometer, and especially the material's resistance to indentation. Shore D hardness may be measured with a durometer directly on the curved surface of the core, layer, cover, etc., according to ASTM method D2240. In other embodiments, the hardness may be measured using standard plaques. An alternative scale to Shore D is Shore A hardness. Shore A hardness is generally between 60 and 99 or more.

[0070] The specific gravity of the ionomer/TPU layer is generally greater than 0.80 and less than 1.0. The specific gravity of the composite of layers of a golf ball should be sufficiently high enough to approach but not exceed the USGA limit of 1.620 oz. in order to have a USGA conforming ball. "Specific gravity (SG)" refers to the conventional meaning of the ratio of the density of a given solid (or liquid) to the density of water at a specific temperature and pressure.

[0071] Hydrophobic TPU is described in US Publication 20090192262 and is a semicrystalline, thermoplastic polyurethane which is comprised of the reaction product of (1) a hydrophobic polyol, (2) a polyisocyanate, and (3) a linear chain extender containing 5 carbon atoms or 7 to 12 carbon atoms; wherein the hydrophobic polyol has a number average molecular weight which is within the range of about 1,000 to about 4,000; wherein the semicrystalline, thermoplastic polyurethane has a weight average molecular weight which is within the range of 50,000 to 1 ,000,000; and wherein the semicrystalline, thermoplastic polyurethane has a melting point which is within the range of 80 °C to 150 °C. US Publication 20090192262 is hereby incorporated by reference in its entirety.

[0072] The hydrophobic polyol can be a diol of a conjugated diolefm monomer, a polyisobutylene diol, a polyester polyol prepared from fatty diols and/or fatty diacids, or mixtures thereof. For instance, the hydrophobic polyol can be prepared from dimer fatty alcohols and/or dimer fatty acids. The diols of conjugated olefin monomers that can be used include hydrogenated polybutadienediols, and hydrogenated polyisoprene diol. Hydrogenated polybutadiene polyols are sold by Mitsubishi Chemical Corporation under the trade name POL YT AIL and Kraton polyols sold by Kraton Polymers of Houston, Tex.

[0073] Dimeric acid polyester polyols may contain from about 18 to about 44 carbon atoms Dimer acids (and esters thereof) are a well known commercially available class of dicarboxylic acids (or esters). The dimer acid material will usually contain 26 to 44 carbon atoms. Particularly, examples include dimer acids (or esters) derived from Q₈ and C₂₂ unsaturated monocarboxylic acids (or esters) which will yield, respectively, C₃₆ and C₄₄ dimer acids (or esters). Dimer acids derived from C₁₈ unsaturated acids, which include acids such as linoleic and linolenic are particularly well known (yielding C₃₆ dimer acids). The dimer acid products will normally also contain a proportion of trimer acids (C₅₄ acids when using C₁ starting acids), possibly even higher oligomers and also small amounts of the monomer acids. Several different grades of dimer acids are available from commercial sources and these differ from each other primarily in the amount of monobasic and trimer acid fractions and the degree of unsaturation. Priplast™ polyester polyols are branched C₃₆ dimerized fatty acids which are particularly useful as the hydrophobic polyol. Priplast™ polyester polyols are commercially available from Uniqema of Gouda, Netherlands. The hydrophobic polyol used in synthesizing the hydrophobic TPU will typically have a number average molecular weight which is within the range of about 1,500 to about 4,000 and a number average molecular weight which is within the range of about 2,000 to about 3,000.

[0074] The linear chain extender used in making the hydrophobic TPU will typically be of the structural formula:

[0075] wherein n represents the integer 5 or an integer from 7 to 12. Accordingly, the linear chain extender may be selected from the group consisting of 1,5-pentane diol, 1,7-heptane diol, 1,8-octane diol, 1,9-nonane diol, 1,10-decane diol, 1,11- undecane diol, 1,12-dodecane diol, and mixtures thereof.

[0076] The polyisocyanate may be a diisocyanate such as aliphatic diisocyanates and aromatic diisocyanates. Multifunctional isocyanate compounds, i.e., triisocyanates, etc., which cause crosslinking, are generally avoided and thus the amount used, if any, is generally less than 4 mole percent and preferably less than 2 mole percent based upon the total moles of all of the various isocyanates used. Suitable diisocyanates include aromatic diisocyanates such as: 4,4'-methylene bis-(phenyl isocyanate) (MDI); m-xylene diisocyanate (XDI), phenylene-1-4- diisocyanate, naphthalene- 1 ,5-diisocyanate, diphenylmethane-3,3'-dimethoxy- 4,4'-diisocyanate, and toluene diisocyanate (TDI); as well as aliphatic diisocyanates such as isophorone diisocyanate (IPDI), 1 ,4-cyclohexyl diisocyanate (CHDI), decane-l,10-diisocyanate, and dicyclohexylmethane-4,4'- diisocyanate. Dimers and trimers of the above diisocyanates may also be used as well as a blend of two or more diisocyanates may be used. [0077] The polyisocyanate may be in the form of a low molecular weight polymer or oligomer which is end capped with an isocyanate. For example, the hydroxyl terminated polyether intermediate described above may be reacted with an isocyanate-containing compound to create a low molecular weight polymer end capped with isocyanate. In the TPU art, such materials are normally referred to as pre-polymers. Such pre-polymers normally have a number average molecular weight (Mn) which is within the range of about 500 to about 10,000.

[0078] The mole ratio of the one or more diisocyanates is generally from about 0.95 to about 1.05, or from about 0.98 to about 1.03 moles per mole of the total moles of the one or more hydrophobic polyols and the one or more chain extenders. The molar ratio of the chain extender to the polyol will typically be within the range of about 0.3: 1 to 10: 1 and will more typically be within the range of about 0.4:1 to 5: 1. The molar ratio of the chain extender to the polyol may be within the range of about 0:5:1 to 3: 1 or the range of about 0.5:1 to 2:1.

[0079] US Publication 20090192262 further describes various processes of making the hydrophobic TPU. Any suitable method is acceptable for the present application.

[0080] Catalysts such as stannous and other metal carboxylates as well as tertiary amines may be used to prepare the hydrophobic TPU. Examples of metal carboxylates catalysts include stannous octoate, dibutyl tin dilaurate, phenyl mercuric propionate, lead octoate, iron acetylacetonate, magnesium acetylacetonate, and the like. Examples of tertiary amine catalysts include triethylene diamine, and the like. The amount of the one or more catalysts is generally from about 50 to about 100 parts by weight per million parts by weight of the end TPU polymer formed.

[0081] The weight average molecular weight (Mw) of the hydrophobic TPU polymer range from about 50,000 to about 500,000 Daltons, from about 100,000 to about 500,000 Daltons, and from about 120,000 to about 300,000 Daltons. The Mw of the TPU polymer is measured according to gel permeation chromatography (GPC) against polystyrene standard.

[0082] When a higher molecular weight hydrophobic TPU polymer is desired, it can be achieved by using a small amount of a cross linking agent having an average functionality greater than 2.0 to induce cross linking. The amount of cross linking agent used is less than 2 mole percent of the total moles of chain extender, or less than 1 mole percent. Less than 1 mole percent of the chain extender may be replaced with trimethylol propane (TMP). The cross linking is accomplished by adding a cross linking agent having an average functionality greater than 2.0 together with the hydrophobic polyol, the isocyanate compound, and chain extender in the reaction mixture to manufacture the TPU polymer. The amount of cross linking agent used in the reaction mixture to make the TPU polymer will depend on the desired molecular weight and the effectiveness of the particular cross linking agent used. Usually, less than 2.0 mole percent, or less than 1.0 mole percent, based on the total moles of chain extender used in making the TPU polymer are used. The level of cross linking agent used is generally from about 0.05 mole percent to about 2.0 mole percent based on the total moles of chain extender.

[0083] The cross linking agents can be any monomeric or oligomeric materials which have an average functionality of greater than 2.0 and have the ability to cross link the TPU polymer. Such materials are well known in the art of thermoset polyurethanes such as trimethylol propane (TMP) and pentaerythritol.

[0084] The hydrophobic TPU has a melting point which is within the range of about 80

°C to about 150 °C. It will typically have a melting point which is within the range of about 90 °C to about 145 °C, and will more typically have a melting point which is within the range of about 110 °C to about 140 °C.

[0085] Hydrophobic TPU is much more effective as a moisture barrier than ordinary

TPU. However, hydrophobic TPU is a very soft material, 60-70A, which is very soft for a golf ball. TPUs are segmented polymers having soft segments and hard segments. This feature accounts for their excellent elastic properties. The soft segments are derived from the hydroxyl terminated polyether or polyester and the hard segments are derived from the isocyanate and the chain extender. The chain extender is typically one of a variety of glycols, such as 1,4-butane glycol.

Ionomers, such as acid-containing ethylene copolymer ionomers, include E/X/Y copolymers where E is ethylene, X is a softening comonomer such as acrylate or methacrylate present in 0 to 50 weight percent of the polymer, and Y is acrylic or methacrylic acid present in 5 to 35 (often 10 to 20) weight percent of the polymer, wherein the acid moiety is neutralized 1 to 90 percent (usually at least 40 percent) to form an ionomer by a cation such as lithium, sodium, potassium, magnesium, calcium, barium, lead, tin, zinc or aluminum, or a combination of such cations, lithium, sodium and zinc being the most preferred. Specific acid- containing ethylene copolymers include ethylene/acrylic acid, ethylene/methaciylic acid, ethylene/acrylic acid/n-butyl acrylate, ethylene/methacrylic acid/n-butyl acrylate, ethylene/methacrylic acid/iso-butyl acrylate, ethylene/acrylic acid/iso-butyl acrylate, ethylene/methacrylic acid/n- butyl methacrylate, ethylene/acrylic acid/methyl methacrylate, ethylene/acrylic acid/methyl acrylate, ethylene/methacrylic acid/methyl acrylate, ethylene/methacrylic acid/methyl methacrylate, and ethylene/acrylic acid/n-butyl methacrylate.

[0087] The ionomer may include a blend of two or more ionomer resins. The blend may include, for example, a very soft material and a harder material. Ionomer resins with different melt flow indexes are often employed to obtain the desired characteristics of the cover stock. SURLYN^® 81 18, 7930 and 7940 have melt flow indices of about 1.4, 1.8, and 2.6 g/10 min., respectively. SURLYN^® 8269 and SURLYN^® 8265 each have a melt flow index of about 0.9 g/10 min. A blend of ionomer resins may be used to form a cover having a melt flow index, for example, of from about 1 to about 3 g/10 min. The cover layer may have a Shore D hardness, for example, ranging from about 45 to about 80.

[0088] In accordance with aspects of the invention, the hydrophobic TPU is blended with one or more ionomers to make a "hardness-suitable" but still moisture resistant layer cover layer. For example, the blend may provide a softer cover to add wedge-spin performance of a typical ionomer covered ball and improve scruff resistance.

[0089] In accordance with other aspects of the invention, the hydrophobic TPU is blended with one or more ionomers to add softness or flexibility as well as moisture-resistant properties to inner layers such as mantle or core layers. [0090] The amount of the ionomer is from about 5 percent to about 95 percent by weight based upon the total weight of the ionomer and hydrophobic TPU blend, 15 percent to about 85 percent, and also between 20 percent and about 80 percent, or between 30 percent and 70 percent. The amount of the hydrophobic TPU is from about 95 percent by weight to about 5 percent by weight based upon the total weight of the Ionomer and hydrophobic TPU blend, 15 percent to about 85 percent, and also between 20 percent and about 80 percent, or between 30 percent and 70 percent.

[0091] The hydrophobic TPU and ionomer are mixed or blended in a suitable manner.

The mixing can utilize conventional melt processing techniques and can either be batch or continuous such as through the use of a single or a twin screw extruder. The mixing temperature is generally above the melting point of the ionomer, and the hydrophobic TPU. Such temperatures are generally from about 180 °C to about 240 °C. The mixing time will naturally vary depending upon the amount of components being blended together, the mixing equipment used, and the mixing temperature.

[0092] Additional additives optionally may be incorporated into the ionomer/TPU blend, such as flow additives, mar/slip additives, adhesion promoters, thickeners, gloss reducers, flexibilizers, cross-linking additives, isocyanates or other agents for toughening or creating scratch resistance, optical brighteners, UV absorbers, and the like. The amount of such additives usually ranges from 0 to about 20 wt%, often from 0 to about 6 wt%.

[0093] The hydrophobic TPU and Ionomer blend is applied to a golf ball with one molding process step, for example. The method of applying the resin is not limited.

[0094] The thickness of the applied blend (after drying, curing, cooling, hardening, or setting) typically ranges from of about 0.5 to about 5.0 mm, and in some examples, from about 0.75 to about 3.0 mm.

[0095] The golf ball body of the present invention has no limitation on its structure and includes a one-piece golf ball, a two-piece golf ball, a multi-piece golf ball comprising at least three layers, and a wound-core golf ball. The present invention can be applied for all types of the golf ball.

[0096] Example

[0097] The tables below display 6 different blends and their corresponding Moisture

Vapor Transmission Rates (WVTR). Fig. 4 displays the trend in vapor transmission as the % hydrophobic TPU (H-TPU) is increased from 0% to 5% to 10%. It is desirable to keep shore A hardness below 90A to maintain good wedge abrasion. Blend 6 has the lowest transmission but is too hard.

Blends:

Performance:

Conclusion

The present invention is described above and in the accompanying drawings with reference to a variety of example structures, features, elements, and combinations of structures, features, and elements. The purpose served by the disclosure, however, is to provide examples of the various features and concepts related to the invention, not to limit the scope of the invention. One skilled in the relevant art will recognize that numerous variations and modifications may be made to the embodiments described above without departing from the scope of the present invention, as defined by the appended claims. For example, the various features and concepts described above in conjunction with the figures may be used individually and/or in any combination or subcombination without departing from this invention.

Claims

We Claim:

1. A golf ball, comprising at least one layer comprising a blend of ionomer and hydrophobic thermoplastic polyurethane.

2. A golf ball, comprising:

a core; and

a cover comprising a moisture barrier layer and an outer layer wherein the moisture barrier layer comprises a blend

hydrophobic thermoplastic polyurethane.

3. The golf ball according to claim 1 or claim 2 wherein the hydrophobic thermoplastic polyurethane comprises the reaction product of (1) a hydrophobic polyol, (2) a polyisocyanate, and (3) a linear chain extender containing 5 carbon atoms or 7 to 12 carbon atoms; wherein the hydrophobic polyol has a number average molecular weight which is within the range of about 1,000 to about 4,000; wherein the semicrystalline, thermoplastic polyurethane has a weight average molecular weight which is within the range of 50,000 to 1,000,000; and wherein the semicrystalline, thermoplastic polyurethane has a melting point which is within the range of 80 °C to 150 °C.

4. The golf ball according to any of claims 1 to 3 wherein the at least one layer or the moisture barrier layer has a Water Vapor Transmission Rate (WVTR) of less than

1300g/m² after 168 hrs at 25C and 50% relative humidity, or less than 1000g/m² after 168 hrs

2

at 25C and 50% relative humidity, or less than 750g/m after 168 hrs at 25C and 50% relative humidity.

5. The golf ball according to any of claims 1 to 4 wherein the at least one layer or the moisture barrier layer has a Shore D hardness is between 20 and 85.

6. The golf ball according to any of claims 1 to 5 wherein the at least one layer or the moisture barrier layer has a specific gravity of greater than 0.80 and less than 1.00.

7. The golf ball according to any of claims 1 to 6 wherein the ionomer is an acid- containing ethylene copolymer ionomer.

8. The golf ball according to claim 7 wherein the acid-containing ethylene copolymer ionomer is selected from the group consisting of ethylene/acrylic acid, ethylene/methacrylic acid, ethylene/acrylic acid/n-butyl acrylate, ethylene/methacrylic acid/n- butyl acrylate, ethylene/methacrylic acid/iso-butyl acrylate, ethylene/acrylic acid/iso-butyl acrylate, ethylene/methacrylic acid/n-butyl methacrylate, ethylene/acrylic acid/methyl methacrylate, ethylene/acrylic acid/methyl acrylate, ethylene/methacrylic acid/methyl acrylate, ethylene/methacrylic acid/methyl methacrylate, and ethylene/acrylic acid/n-butyl methacrylate.

9. The golf ball according to any of claims 1 to 8 wherein the ionomer is a blend of ionomers.

10. The golf ball according to any of claims 1 to 9 wherein the at least one layer or the moisture barrier layer comprises from about 5 percent to about 95 percent by weight ionomer based upon the total weight of the ionomer and hydrophobic thermoplastic polyurethane blend and from about 95 percent by weight to about 5 percent by weight hydrophobic thermoplastic polyurethane based upon the total weight of the ionomer and hydrophobic thermoplastic polyurethane blend.

11. The golf ball according to any of claims 1 to 10 wherein the at least one layer or the moisture barrier layer comprises from about 15 percent to about 85 percent by weight ionomer based upon the total weight of the ionomer and hydrophobic thermoplastic polyurethane blend and from about 15 percent by weight to about 85 percent by weight hydrophobic thermoplastic polyurethane based upon the total weight of the ionomer and hydrophobic thermoplastic polyurethane blend.

12. A method of improving moisture resistance of a golf ball comprising applying a moisture barrier layer to a golf ball, the moisture barrier layer comprising a blend of ionomer and hydrophobic thermoplastic polyurethane.

13. The method according to claim 12 wherein the moisture barrier layer is molded onto a core or intermediate layer of the golf ball.

14. The method according to claim 12 or claim 13 wherein the hydrophobic thermoplastic polyurethane comprises the reaction product of (1) a hydrophobic polyol, (2) a polyisocyanate, and (3) a linear chain extender containing 5 carbon atoms or 7 to 12 carbon atoms; wherein the hydrophobic polyol has a number average molecular weight which is within the range of about 1,000 to about 4,000; wherein the semicrystalline, thermoplastic polyurethane has a weight average molecular weight which is within the range of 50,000 to 1,000,000; and wherein the semicrystalline, thermoplastic polyurethane has a melting point which is within the range of 80 °C to 150 °C.

15. The method according to any of claims 12 to 14 wherein the moisture barrier layer has a Water Vapor Transmission Rate (WVTR) of less than 1300g/m² after 168 hrs at 25C and 50% relative humidity, or less than 1000g/m² after 168 hrs at 25C and 50% relative humidity, or less than 750g/m² after 168 hrs at 25C and 50% relative humidity.