Process of adhering thermoplastic polyurethane film to a non-flat geometry

Abstract

A method of adhering a film to a non-flat geometry by providing thermoplastic polyurethane substrate having a non-flat geometry, providing a thermoplastic polyurethane film, applying an adhesive composition to the film in a discontinuous pattern, and applying the first surface of the film to the substrate.

Description

4846-01- 1 -TITLEProcess of Adhering Thermoplastic Polyurethane Film to a Non-Flat Geometry SUMMARY OF THE INVENTION

[0001] The present invention provides a method for adhering a substrate with thermoplastic polyurethane film to a non-flat geometry. The method includes the steps providing a substrate having a non-flat geometry, wherein the substrate is made from a first thermoplastic polyurethane composition, providing a film having a first surface and a second surface, wherein the film is formed from a second thermoplastic polyurethane composition, applying an adhesive composition to the first surface of the film, wherein the adhesive composition comprises an acrylic terpolymer having a Brookfield viscosity of 5 cps to 70 cps and 47% to 50% solids content and wherein the adhesive composition is applied to less than 75% of the first surface in a discontinuous pattern, applying the first surface of the film to the substrate.

[0002] The following embodiments of the present subject matter are contemplated:

[0003] 1. A method of adhering a film to a non-flat geometry, comprising the steps of providing a substrate having a non-flat geometry, wherein the substrate is made from a first thermoplastic polyurethane composition; providing a film having a first surface and a second surface, wherein the film is formed from a second thermoplastic polyurethane composition; applying an adhesive composition to the first surface of the film, wherein the adhesive composition comprises an acrylic terpolymer and wherein the adhesive composition is applied to less than 75% of the first surface in a discontinuous pattern; applying the first surface of the film to the substrate.

[0004] 2. The method of embodiment 1, wherein the adhesive composition is applied to 40% to 60% of the first surface of the film in a discontinuous pattern.

[0005] 3. The method of embodiment 1 or 2, wherein the first thermoplastic polyurethane composition comprises the reaction product of a polyol component, a diisocyanate, and a chain extender component and wherein a combined weight of the diisocyanate component and the chain extender component make up a hard segment of the first thermoplastic polyurethane composition, and wherein the first4846-01- 2 - thermoplastic polyurethane composition has a hard segment content of 30 wt% or less or 28 wt% or less or 20 wt% to 30 wt% or 24 wt% to 28 wt%.

[0006] 4. The method of any of embodiments 1 to 3, wherein the second thermoplastic polyurethane composition comprises the reaction product of a second polyol component, a second diisocyanate, and a second chain extender component.

[0007] 5. The method of embodiment 4, wherein the second polyol component comprises or consists of a butanediol adipate, the second diisocyanate comprises or consists of methylene diphenyl diisocyanate, and the second chain extender component comprises a mixture of 1,4-butanediol and neopentylglycol.

[0008] 6. The method of embodiment 5, wherein the second polyol component comprises a butanedi ol / hexanediol adipate, the second diisocyanate comprises or consists of methylene diphenyl diisocyanate, and the second chain extender component comprises or consists of 1,4-butanediol.

[0009] 7. The method of any of embodiments 1 to 6, wherein the adhesive composition comprises or consists of 2-ethylhexyl acrylate terpolymer.

[0010] 8. The method of any of embodiments 1 to 7, wherein the adhesive composition has a Brookfield viscosity (ASTM 2983) of 5 cps to 70 cps.

[0011] 9. The method of any of embodiments 1 to 8, wherein the adhesive composition has a solids content of 47 wt% to 50wt%.

[0012] 10. The method of any of embodiments 1 to 9, wherein the second surface of the film is adhered to a woven or nonwoven felt or fabric.

[0013] 11. A method of adhering a film to a non-flat geometry, comprising the steps of providing a substrate, wherein the substrate is a sphere or hemisphere defining an internal volume, wherein the substrate is entirely formed from a first thermoplastic polyurethane composition, wherein the substrate demonstrates a hysteresis at 18 lbs load of less than 30% measured according to ASTM D3574; providing a film having a first surface and a second surface, wherein the film is formed from a second thermoplastic polyurethane composition; applying an adhesive composition to the first surface of the film, wherein the adhesive composition comprises an acrylic terpolymer and wherein the adhesive composition is applied to less than 75% of the first surface in a discontinuous pattern; applying the first surface of the film to the substrate.4846-01- 3 -

[0014] 12. The method of embodiment 11, wherein the first thermoplastic polyurethane has a tan delta measured at 1 Hz and at 25°C or higher of less than 0.05 measured according to ASTM D5206.

[0015] 13. The method of embodiment 11 or 12, wherein the first thermoplastic polyurethane has a rebound as measured by ASTM D2632 of greater than 50 inches or greater than 60 inches.

[0016] 14. The method of any of embodiments 11 to 13, wherein the substrate demonstrates a forward deformation of 0.21 inches.

[0017] 15. The method of any of embodiments 11 to 14, wherein the first thermoplastic polyurethane has a Tc of greater than 60°C or 60°C to 120°C measured according to ASTM D3418.

[0018] 16. The method of any of embodiments 11 to 15, wherein the adhesive composition is applied to 40% to 60% of the first surface of the film in a discontinuous pattern.

[0019] 17. The method of embodiments 11 to 16, wherein the first thermoplastic polyurethane composition comprises the reaction product of a polyol component, a diisocyanate, and a chain extender component, wherein a combined weight of the diisocyanate component and the chain extender component make up a hard segment of the thermoplastic polyurethane, and wherein the thermoplastic polyurethane comprises 30 wt% or less or 28 wt% or less hard segment.

[0020] 18. The method of embodiment 17, wherein the thermoplastic polyurethane comprises 20 wt% to 30 wt% hard segment or 24 wt% to 28 wt% hard segment.

[0021] 19. The method embodiment 17 or 18, wherein the polyol component comprises or consists of a polyether polyol.

[0022] 20. The method of embodiment 19, wherein the poly ether polyol comprises or consists of polytetramethylene ether glycol.

[0023] 21. The method of embodiment 17 or 18, wherein the polyol component comprises a copolymer of poly tetramethylene ether glycol and polycaprolactone polyol.

[0024] 22. The method of embodiment 17 or 18, wherein the polyol component comprises or consists of a polyester polyol.4846-01- 4 -

[0025] 23. The method of embodiment 22, wherein the polyester polyol is prepared from the reaction of adipic acid with a mixture of 1,4 butanediol and 1,6 hexanediol.

[0026] 24. The method of any of embodiments 17 to 23, wherein the chain extender component comprises or consists of hydroquinone bis(2-hydroxyethyl) ether.

[0027] 25. The method of any of embodiments 17 to 23, wherein the diisocyanate component comprises or consists of methylene diphenyl diisocyanate.

[0028] 26. The method of any of embodiments 11 to 25, wherein the second thermoplastic polyurethane composition comprises reaction product of a second polyol component, a second diisocyanate, and a second chain extender component.

[0029] 27. The method of embodiment 26, wherein the second polyol component comprises or consists of a butanediol adipate, the second diisocyanate comprises or consists of methylene diphenyl diisocyanate, and the second chain extender component comprises a mixture of 1,4-butanediol and neopentylglycol.

[0030] 28. The method of embodiment 26, wherein the second polyol component comprises a butanedi ol / hexanediol adipate, the second diisocyanate comprises or consists of methylene diphenyl diisocyanate, and the second chain extender component comprises or consists of 1,4-butanediol.

[0031] 29. The method of any of embodiments 11 to 28, wherein the second surface of the film is adhered to a felt or fabric.

[0032] 30. The method of any of embodiments 11 to 29, wherein the adhesive composition has a Brookfield viscosity (ASTM 2983) of 5 cps to 70 cps.

[0033] 31. The method of any of embodiments 11 to 30, wherein the adhesive composition has a solids content of 47 wt% to 50wt%.

[0034] 32. An article formed from the method of any of embodiments 1 to 31.

[0035] 33. The article of embodiment 32, wherein the article is a ball.

[0036] 34. The article of embodiment 33, wherein the ball is a tennis ball.BRIEF DESCRIPTION OF THE DRAWINGS

[0037] FIG. l is a sectional view of a hollow thermoplastic article.

[0038] FIG. 2 is a view of a thermoplastic polyurethane film having an adhesive composition applied in a discontinuous pattern.4846-01- 5 -

[0039] FIG. 3 illustrates how two hemispheres having non-flat geometry may be used to form a spherical non-flat geometry.

[0040] FIG. 4 illustrates one embodiment of a pattern of adhesive material applied to a film.

[0041] FIG. 5 illustrates another embodiment of a pattern of adhesive material applied to a film.DETAILED DESCRIPTION OF THE INVENTION

[0042] The present invention provides a method of adhering a thermoplastic polyurethane film to a non-flat geometry. The non-flat geometry used herein may include an article, such as a ball or sphere, wherein the sphere or hemisphere is formed from a first thermoplastic polyurethane, wherein the thermoplastic polyurethane has a tan delta of less than 0.05, a crystallization temperature of greater than 60°C, and a rebound of greater than 50 inches or greater than 60 inches, and wherein the injection molded sphere or hemisphere demonstrates a hysteresis at 18 lbs load of less than 30% and a forward deformation of 0.21 inches or less.

[0043] The method provided herein further includes the steps of providing a film having a first surface and a second surface, wherein the film is formed from a second thermoplastic polyurethane. An adhesive composition is applied to a surface of the film in a discontinuous pattern that covers less than 75% of a surface of the film. The surface of the film to which the adhesive is applied is then applied to the non-flat geometry.Thermoplastic Polyurethane

[0044] The non-flat geometry component as well as the film component of the present invention are constructed from thermoplastic polyurethane (TPU) compositions. A thermoplastic polyurethane is generally prepared by reacting a diisocyanate with a polyol intermediate, and, optionally, a chain extender component, all of which are well known to those skilled in the art.

[0045] Thermoplastic polyurethanes used in the present invention are made using a polyisocyanate component. In some embodiments, the polyisocyanate component includes one or more diisocyanates. Useful diisocyanates may be selected from aromatic diisocyanates or aliphatic diisoyisocyanates or combinations thereof. Examples of useful diisocyanates include, but are not limited to aromatic diisocyanates4846-01- 6 - such as 4,4'-methylenebis(phenyl isocyanate) (MDI), m-xylene diisocyanate (XDI), phenylene-l,4-diisocyanate, 3,3’-dimethyl-4,4’-biphenylene diisocyanate (TODI), 1,5 -naphthalene diisocyanate (ND I), and toluene diisocyanate (TDI), as well as aliphatic diisocyanates such as isophorone diisocyanate (IPDI), 1,6-hexamethylene diisocyanate (HDI), 1,4-cyclohexyl diisocyanate (CHDI), decane- 1,10-diisocyanate, lysine diisocyanate (LDI), 1,4-butane diisocyanate (BDI), and dicyclohexylmethane- 4,4'-diisocyanate (H12MDI). In some embodiments, mixtures of two or more polyisocyanates may be used.

[0046] In some embodiments, the polyisocyanate component comprises or consists of one or more aromatic diisocyanates. In some embodiments, the polyisocyanate component is essentially free of, or even completely free of, aliphatic diisocyanates.

[0047] Thermoplastic polyurethane compositions used in the present invention are also made using a polyol intermediate. Polyol intermediates may include, but are not limited to polyether polyols and polyester polyols or combinations thereof.

[0048] Polyether polyols that may be useful as the polyol component of the TPU of the present invention include polyether polyols derived from a diol or polyol having a total of from 2 to 15 carbon atoms. In some embodiments, the hydroxyl terminated polyether is an alkyl diol or glycol which is reacted with an ether comprising an alkylene oxide having from 2 to 6 carbon atoms, typically ethylene oxide or propylene oxide or mixtures thereof. For example, hydroxyl functional polyether can be produced by first reacting propylene glycol with propylene oxide followed by subsequent reaction with ethylene oxide. Primary hydroxyl groups resulting from ethylene oxide are more reactive than secondary hydroxyl groups and thus are preferred. Useful commercial polyether polyols include poly(ethylene glycol) comprising ethylene oxide reacted with ethylene glycol, polypropylene glycol) comprising propylene oxide reacted with propylene glycol, poly(tetramethylene glycol) comprising water reacted with tetrahydrofuran which can be described as polymerized tetrahydrofuran, and which is commonly referred to as PTMEG. IN some embodiments, the polyether polyols may have a number average molecular weight (Mn) of 500 to 5000, for example, 1000 to 3000 or mixtures thereof.4846-01- 7 -

[0049] Polyester polyols may also be useful as the polyol intermediate in the present invention. In general, polyester intermediates are produced by (1) an esterification reaction of one or more glycols with one or more dicarboxylic acids or anhydrides or (2) by transesterification reaction, i.e., the reaction of one or more glycols with esters of dicarboxylic acids. Mole ratios generally in excess of more than one mole of glycol to acid are preferred so as to obtain linear chains having a preponderance of terminal hydroxyl groups. The dicarboxylic acids polyester may include aliphatic, cycloaliphatic, aromatic, or combinations thereof. Dicarboxylic acids may be used alone or in mixtures and generally have a total of from 4 to 15 carbon atoms and include: succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, isophthalic, terephthalic, cyclohexane dicarboxylic, and the like. Anhydrides of the above dicarboxylic acids such as phthalic anhydride, tetrahydrophthalic anhydride, or the like, can also be used. The glycols which are reacted to form a desirable polyester intermediate can be aliphatic, aromatic, or combinations thereof, and have a total of from 2 to 20 or from 2 to 12 carbon atoms. Suitable examples include ethylene glycol, 1,2-propanediol, 1,3 -propanediol, 1,3-butanediol, 1,4- butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-l,3-propanediol, 1,4- cyclohexanedimethanol, decamethylene glycol, dodecamethylene glycol, and mixtures thereof.

[0050] In one embodiment, the polyol component comprises a polycaprolactone polyester polyol. The polycaprolactone polyester polyols useful for making the TPU compositions described herein include polyester diols derived from caprolactone monomers. The polycaprolactone polyester polyols are terminated by primary hydroxyl groups. Suitable polycaprolactone polyester polyols may be made from s-caprolactone and a bifunctional initiator such as di ethylene glycol, 1,4-butanediol, or any of the other glycols and / or diols known in the art for this purpose. In some embodiments, the polycaprolactone polyester polyols are linear polyester diols derived from caprolactone monomers.

[0001] Useful examples include CAPA™ 2202A, a 2000 number average molecular weight (Mn) linear polyester diol, and CAPA™ 2302 A, a 3000 Mn linear polyester diol, both of which are commercially available. These materials may also be described as polymers of 2-oxepanone and 1,4-butanediol.4846-01- 8 -

[0051] The polycaprolactone polyester polyols may be prepared from 2-oxepanone and a diol, where the diol may be 1,4-butanediol, di ethylene glycol, monoethylene glycol, hexane diol, 2, 2-dimethyl- 1,3 -propanediol, or any combination thereof. In some embodiments, the diol used to prepare the polycaprolactone polyester polyol is linear.

[0052] The TPU used in the present invention optionally includes a chain extender component. Suitable chain extenders include relatively small polyhydroxy compounds, for example lower aliphatic or short chain glycols having from 2 to 20, or 2 to 12, or 2 to 10 carbon atoms. Suitable examples include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol (BDO), 1,6-hexanediol (HDO), 1,3-butanediol, 1,5-pentanediol, neopentylglycol, 1,4-cyclohexanedimethanol (CHDM), 2,2-bis[4- (2-hydroxyethoxy) phenyl]propane (HEPP), heptanediol, nonanediol, dodecanediol, 3-methyl-l,5-pentanediol, and hydroxyethyl resorcinol (HER), pentaspiro glycol (PSG), hydroquinone bis(2 -hydroxyethyl) ether (HQEE), dipropylene glycol (DPG), 2-methyl-l,3-propane diol, 2-butyl-2-ethyl-l,3-propane diol (BEPD), and the like, as well as mixtures thereof. .

[0053] In one embodiment, the non-flat geometry used in the present invention is formed from a thermoplastic polyurethane wherein the thermoplastic polyurethane comprises the reaction product of a polyol component wherein the polyol component comprises or consists of a polyether polyol, such as poly tetramethylene ether glycol, a diisocyanate comprising or consisting of methylene diphenyl diisocyanate, and a chain extender comprising or consisting of hydroquinone bi s(2 -hydroxy ethyl) ether. In another embodiment, the non-flat geometry of the present invention is formed from a thermoplastic polyurethane wherein the thermoplastic polyurethane comprises or consists of the reaction product of a polyol component wherein the polyol component comprises or consists of a copolymer of polytetramethylene ether glycol and a polycaprolactone polyol, a diisocyanate comprising or consisting of methylene diphenyl diisocyanate, and a chain extender comprising or consisting of hydroquinone bi s(2 -hydroxy ethyl) ether. In another embodiment, non-flat geometry of the present invention is formed from a thermoplastic polyurethane wherein the thermoplastic polyurethane comprises the reaction product of a polyol component, wherein the polyol component comprises or consists of a polyester polyol, such as a4846-01- 9 - polyester polyol prepared from the reaction of adipic acid with a mixture of 1,4 butanediol and 1,6 hexanediol, a diisocyanate comprising or consisting of methylene diphenyl diisocyanate, and a chain extender comprising or consisting of hydroquinone bi s(2 -hydroxy ethyl) ether. The combined weight of the diisocyanate and the chain extender used in the preparation of the thermoplastic polyurethane make up the “hard segment” of the thermoplastic polyurethane. For applications contemplated in the present application, the thermoplastic polyurethane has a hard segment content of 30 wt% or less or 28 wt% or less or further for example 20 wt% to 30 wt% or even 24 wt% to 30 wt%.

[0054] For certain applications of the non-flat geometry, the properties of the TPU material are important to ensure that the article meets certain performance requirements. For example, the TPU used in the present invention has a tan delta measured according to ASTM D5026 (Tension Mode, sample size 20 mm x 6.35 x 0.08 mm at 1 Hz and at 25°C or higher, or 25°C to 50°C) of less than 0.05. For certain applications of the non-flat geometry, the TPU has a crystallization temperature of greater than 60°C or 60°C to 120°C measured by ASTM D3418. In addition, the TPU used in the present invention may also have a rebound measured according to ASTM D2632 of greater than 50 inches or greater than 60 inches, wherein the rebound is measured using a compression molded plaque.

[0055] The non-flat articles of the present invention may be spheres or hemispheres. The spheres or hemispheres may be prepared using methods now known to those skilled in the art of forming thermoplastic materials or hereafter developed and known in the art. Examples of methods include but are not limited to injection molding, roto-molding, spin molding, blowing molding, or 3D printing. FIG. 1 illustrates a hemisphere 1 prepared using the TPU material described herein. FIG. 2 is a second view of a hemisphere 2 having a hollow interior 3. However, it is contemplated that solid hemispheres or spheres may be included in the scope of the invention. FIG. 3 illustrates two hemispheres 4 and 5 being assembled to form a sphere 6. In one embodiment of the present invention, the article is a ball. In another embodiment of the present invention, the article makes up the core of a tennis ball.

[0056] Regardless of the method of preparation of the non-flat geometry, it is an aspect of the present invention that the non-flat geometry demonstrate a hysteresis at4846-01- 10 -181bs load of less than 30% as measured according to ASTM D3574 (5 cycles, 1 inch displacement length, 20 cm / min). In another aspect, the non-flat geometry exhibits a forward deformation of 0.21 inches or less (measured using the method specified in the ITF Technical Booklet at pages 14-15 with the modification that the contact load of 15.57 + 0.5 N (3.5 + 0.1 Ibf is not applied - this accounts for the fact that the measurements in this case are made on a sphere without the need to compress a felt layer)). In one embodiment, the non-flat geometry also demonstrates a load at 1 inch displacement of less than 100 Ibs-force measured according to ASTM D3574.

[0057] The invention also provides a method of adhering a film to a non-flat geometry, wherein the method includes the steps of providing a substrate having a non-flat geometry, wherein the substrate is made from a first thermoplastic polyurethane composition, providing a film having a first surface and a second surface, wherein the film is formed from a second thermoplastic polyurethane composition, applying an adhesive composition to the first surface of the film, wherein the adhesive composition comprises an acrylic terpolymer having a Brookfield viscosity of 5 cps to 70 cps and 47% to 50% solids content and wherein the adhesive composition is applied to less than 75% of the first surface in a discontinuous pattern, applying the first surface of the film to the substrate.

[0058] The non-flat geometry and the TPU used to create such non-flat geometry is described above.

[0059] The TPU useful for the second TPU used in the TPU film described above, comprises the reaction product of a polyester polyol, a diisocyanate and a chain extender as described above. In one embodiment, the polyester polyol used to prepare the TPU film comprises polyester polyol that is the reaction product of 1,4- butanediol, 1,6-hexanediol, or mixtures thereof with adipic acid. In one embodiment, the polyester polyol comprises or consists of butanediol adipate. In another embodiment, the polyester polyol comprises or consists of a hexandiol / butanediol adipate. Useful chain extenders for the second TPU include 1,4-butanediol and neopentylglycol. Diisocyanates listed above for preparation of the non-flat geometry are also useful for the preparation of the TPU film and include diphenylmethane diisocyanate.4846-01- 11 -

[0060] The adhesive composition useful for adhering the film to the non-flat geometry may comprise an acrylic terpolymer based adhesive, also referred to as a tackifier. The acrylic terpolymer adhesive may have a Brookfield viscosity (ASTM D2196) of 5 cps to 70 cps and a solids content of 47% to 50% by weight. In one embodiment, the adhesive comprises or consists of a 2-ethylhexyl acrylate based terpolymer adhesive.

[0061] FIG. 4 and FIG. 5 illustrate TPU films useful in the present invention (7, 8). As shown in FIG. 4 and FIG. 5, the films have a first surface and a second surface. The adhesive is applied in a discontinuous pattern (10, 1 l)_on the first surface of the film. The pattern may be formed by applying adhesive “dots” to the film, where the “dots” may have any shape including circular, elliptical, square, rectangular, or the like. In one embodiment, the dots have a diameter of approximately 5mm and are spaced 9mm-10mm apart, for example, 9.1mm, 9.2mm, 9.3mm, 9.4mm, 9.5mm, 9.6mm, 9.7mm, 9.8mm, 9.9mm or 10mm. The discontinuous pattern is applied to the first surface in a discontinuous pattern that covers less than 75% of the first surface of the film, for example, 40% to 60% of the surface, or 50% of the surface.

[0062] The second surface of the TPU film is adhered to a felt or fabric. The felt or fabric can be a woven or non-woven material. The fabric layer may be any material or a combination of materials and in one embodiment provides the article with a high friction, soft surface.

[0063] The TPU film form panels which can be adhered to the surface of a non- flat geometry to substantially cover the entire surface of the non-flat geometry. For example, a plurality of films as shown in FIG. 4 and FIG. 5 may be used to cover the entirety of the surface of a sphere as shown in FIG. 3 (6).

[0064] Without intending to limit the scope of the invention, the following examples illustrate preparation and evaluation of examples of non-flat geometries and application of films to the non-flat geometry.EXAMPLES

[0065] A series of thermoplastic polyurethane materials was prepared as set forth in Table 1.4846-01- 12 -Table 11Combined weight of chain extender and isocyanate.2ASTM D34183ASTM D5026, Tension Mode, Sample size 20 mm x 6.35 x 0.08 mm at 1 Hz and at 25°C or higher 4 ASTM D263251,4-butanediol6Ethylene glycol7Hydroquinone bis(2-hydroxylethyl) ether8Dipropylene glycol 9 Trimethylol propane10Undetected

[0066] The TPU compositions from Table 1 were injected molded into hemispheres which were assembled into spheres (as shown in FIG. 3) and evaluated for suitability for use in certain articles. The results are summarized in Table 2.Table 24846-011ASTM D3574 (changes from standard are test speed of 20 in / min, 5 cycles with 1 inch displacement length, during this test hysteresis is reported at 18 lbs. load).2ASTM D3574 (changes from standard are test speed of 20 in / min, 5 cycles with 1 inch displacement length, during this test load required to displace one inch is reported)3Measured using the method specified in the 2024 ITF Technical Booklet (ITF Approved Tennis Balls, Classified Surfaces & Recognised Courts A Guide to Products & Test Methods available a with the modification that the contact load of 15.57 + 0.5 N (3.5 + 0.1 Ibf is not applied at pages 14-15.

[0067] TPU Films were prepared by extruding or coextruding TPU A made from the reaction product of a polyester polyol (butanediol adipate), 1,4 butanediol chain extender, and MDI having a Shore A hardness of 75 A (+3) and / or the TPU of Example 2 from Table 1. Films were applied to spherical TPU articles using the following process: Felt was applied to an outer surface of a TPU film. To the other surface of the TPU film, an Tackifier layer of an acrylic terpolymer adhesive (Hystretch™ V60) having a Brookfield viscosity (ASTM D2196) of 5 cps to 70 cps and a solids content of 47% to 50% by weight was applied as set forth in Table 3. The surface of the film to which the adhesive was applied was adhered to a substrate core having a non-flat geometry and comprising the TPU of Example 12 above. The peel strength was measured using ASTM DI 876 after conditioning as set forth in the test method.Table 34846-01- 14 -

[0068] It is known that some of the materials described above may interact in the final formulation, so that the components of the final formulation may be different from those that are initially added. The products formed thereby, including the products formed upon employing lubricating grease compositions of the present invention in its intended use, may not be susceptible of easy description. Nevertheless, all such modifications and reaction products are included within the scope of the present invention; the present invention encompasses lubricating grease compositions prepared by admixing the components described above.

[0069] Each of the documents referred to above is incorporated herein by reference. Except in the Examples, or where otherwise explicitly indicated, all numerical quantities in this description specifying amounts of materials, reaction conditions, molecular weights, number of carbon atoms, and the like, are to be understood as modified by the word "about." Unless otherwise indicated, each chemical or composition referred to herein should be interpreted as being a commercial grade material which may contain the isomers, by-products, derivatives, and other such materials which are normally understood to be present in the commercial grade. However, the amount of each chemical component is presented exclusive of any solvent or diluent oil, which may be customarily present in the commercial material, unless otherwise indicated. It is to be understood that the upper and lower amount, range, and ratio limits set forth herein may be independently combined. Similarly, the ranges and amounts for each element of the invention may be used together with ranges or amounts for any of the other elements.

[0070] While the invention has been explained in relation to its preferred embodiments, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading the specification. Therefore, it is to be understood that the invention disclosed herein is intended to cover such modifications as fall within the scope of the appended claims.

Claims

4846-01- 15 -What is claimed is:

1. A method of adhering a film to a non-flat geometry, comprising the steps of: providing a substrate having a non-flat geometry, wherein the substrate is made from a first thermoplastic polyurethane composition; providing a film having a first surface and a second surface, wherein the film is formed from a second thermoplastic polyurethane composition; applying an adhesive composition to the first surface of the film, wherein the adhesive composition comprises an acrylic terpolymer and wherein the adhesive composition is applied to less than 75% of the first surface in a discontinuous pattern; applying the first surface of the film to the substrate.

2. The method of claim 1, wherein the adhesive composition is applied to 40% to 60% of the first surface of the film in a discontinuous pattern.

3. The method of claim 1 or 2, wherein the first thermoplastic polyurethane composition comprises the reaction product of a polyol component, a diisocyanate, and a chain extender component and wherein a combined weight of the diisocyanate component and the chain extender component make up a hard segment of the first thermoplastic polyurethane composition, and wherein the first thermoplastic polyurethane composition has a hard segment content of 30 wt% or less.

4. The method of any of claims 1 to 3, wherein the second thermoplastic polyurethane composition comprises the reaction product of a second polyol component, a second diisocyanate, and a second chain extender component.

5. The method of claim 4, wherein the second polyol component comprises a butanediol adipate, the second diisocyanate comprises methylene diphenyl diisocyanate, and the second chain extender component comprises a mixture of 1,4-butanediol and neopentylglycol.

6. The method of claim 5, wherein the second polyol component comprises a butanediol / hexanediol adipate, the second diisocyanate comprises methylene4846-01- 16 - diphenyl diisocyanate, and the second chain extender component comprises 1,4- butanediol.

7. The method of any of claims 1 to 6, wherein the adhesive composition comprises 2-ethylhexyl acrylate terpolymer.

8. The method of any of claims 1 to 7, wherein the adhesive composition has a Brookfield viscosity (ASTM 2983) of 5 cps to 70 cps.

9. The method of any of claims 1 to 8, wherein the adhesive composition has a solids content of 47 wt% to 50 wt%.

10. The method of any of claims 1 to 9, wherein the second surface of the film is adhered to a woven or nonwoven felt or fabric.

11. A method of adhering a film to a non-flat geometry, comprising the steps of providing a substrate, wherein the substrate is a sphere or hemisphere defining an internal volume, wherein the substrate is entirely formed from a first thermoplastic polyurethane composition, wherein the substrate demonstrates a hysteresis at 18 lbs load of less than 30% measured according to ASTM D3574; providing a film having a first surface and a second surface, wherein the film is formed from a second thermoplastic polyurethane composition; applying an adhesive composition to the first surface of the film, wherein the adhesive composition comprises an acrylic terpolymer and wherein the adhesive composition is applied to less than 75% of the first surface in a discontinuous pattern; applying the first surface of the film to the substrate.

12. The method of claim 11, wherein the first thermoplastic polyurethane has a tan delta measured at 1 Hz and at 25°C or higher of less than 0.05 measured according to ASTM D5206.4846-01- 17 -13. The method of claim 11 or 12, wherein the first thermoplastic polyurethane has a rebound as measured by ASTM D2632 of greater than 50 inches.

14. The method of any of claims 11 to 13, wherein the substrate demonstrates a forward deformation of 0.21 inches.

15. The method of any of claims 11 to 14, wherein the first thermoplastic polyurethane has a Tc of greater than 60°C measured according to ASTM D3418.

16. The method of any of claims 11 to 15, wherein the adhesive composition is applied to 40% to 60% of the first surface of the film in a discontinuous pattern.

17. The method of claims 11 to 16, wherein the first thermoplastic polyurethane composition comprises the reaction product of a polyol component, a diisocyanate, and a chain extender component, wherein a combined weight of the diisocyanate component and the chain extender component make up a hard segment of the thermoplastic polyurethane, and wherein the thermoplastic polyurethane comprises 30 wt% or less hard segment.

18. The method of claim 17, wherein the thermoplastic polyurethane comprises 20 wt% to 30 wt% hard segment.

19. The method claim 17 or 18, wherein the polyol component comprises a polyether polyol.

20. The method of claim 19, wherein the polyether polyol comprises polytetramethylene ether glycol.

21. The method of claim 17 or 18, wherein the polyol component comprises a copolymer of polytetram ethylene ether glycol and poly caprolactone polyol.4846-01- 18 -22. The method of claim 17 or 18, wherein the polyol component comprises a polyester polyol.

23. The method of claim 22, wherein the polyester polyol is prepared from the reaction of adipic acid with a mixture of 1,4 butanediol and 1,6 hexanediol.

24. The method of any of claims 17 to 23, wherein the chain extender component comprises hydroquinone bis(2-hydroxyethyl) ether.

25. The method of any of claims 17 to 23, wherein the diisocyanate component comprises methylene diphenyl diisocyanate.

26. The method of any of claims 11 to 25, wherein the second thermoplastic polyurethane composition comprises reaction product of a second polyol component, a second diisocyanate, and a second chain extender component.

27. The method of claim 26, wherein the second polyol component comprises a butanediol adipate, the second diisocyanate comprises methylene diphenyl diisocyanate, and the second chain extender component comprises a mixture of 1,4-butanediol and neopentylglycol.

28. The method of claim 26, wherein the second polyol component comprises a butanedi ol / hexanediol adipate, the second diisocyanate comprises methylene diphenyl diisocyanate, and the second chain extender component comprises 1,4- butanediol.

29. The method of any of claims 11 to 28, wherein the second surface of the film is adhered to a felt or fabric.

30. The method of any of claims 11 to 29, wherein the adhesive composition has a Brookfield viscosity (ASTM 2983) of 5 cps to 70 cps.4846-01- 19 -31. The method of any of claims 11 to 30, wherein the adhesive composition has a solids content of 47 wt% to 50 wt%.

32. An article formed from the method of any of claims 1 to 31.

33. The article of claim 32, wherein the article is a ball.

34. The article of claim 33, wherein the ball is a tennis ball.

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