WO2014120563A1

WO2014120563A1 - Cushioning device

Info

Publication number: WO2014120563A1
Application number: PCT/US2014/012865
Authority: WO
Inventors: Philip C. Yang
Original assignee: Msd Consumer Care, Inc.
Priority date: 2013-01-29
Filing date: 2014-01-24
Publication date: 2014-08-07
Also published as: AR094581A1; US20140209229A1

Abstract

A cushioning device including a layer of styrenic based gel material having top and bottom surfaces, a first layer including: i. layer of maleic anhydride and ii. layer of thermoplastic polyurethane, wherein the first layer has a surface bonded to the top surface of the layer of styrenic based gel material, the second layer has a surface bonded to the bottom of the layer of styrenic based gel material and wherein a pressure sensitive adhesive coating is disposed on at least one of the first and second layers opposite to the layer of styrenic based gel material.

Description

CUSHIONING DEVICE

FIELD OF THE INVENTION

The present invention relates to a cushioning device including a layer of styrenic based gel material having top and bottom surfaces, a first layer including: i. layer of maleic anhydride (MAH), and ii. layer of thermoplastic polyurethane (TPU), wherein the first layer has a surface bonded to the top surface of the layer of styrenic based gel material, and the second layer has a surface bonded to the bottom surface of the layer of styrenic based gel material and a pressure sensitive adhesive coating is disposed on at least one of the first and second layers opposite to the layer of styrenic based gel material. BACKGROUND OF THE INVENTION

Cushioning devices made of soft gels are desirable for their comfort, flexibility, durability and look. Generally, such cushioning devices include a gel material having at least one layer of polyurethane film thereon that contacts the foot, sock or hosiery of the user and a pressure sensitive adhesive on the opposing side of the cushioning device that is in contact with the footwear of the user.

To effectively improve the comfort of users, soft gel cushioning devices require a certain level of tack to stay in place. For example, to prevent footwear from rubbing sensitive areas of skin (e.g., the heel area) soft gel cushioning devices must stay in place firmly during movement associated with normal use of footwear. However, tack of cushioning devices is reduced over time thereby rendering the cushioning device less effective.

Thus, there is a need for improved cushioning devices having a desirable level of tack that is retained for a greater period of time. SUMMARY OF THE INVENTION

The present invention provides cushioning devices including a layer of styrenic based gel material having top and bottom surfaces, a first layer including: i. layer of MAH, and ii. layer of TPU, and a second layer including: i. layer of MAH, and ii. layer of TPU, wherein the first layer has a surface bonded to the top surface of the layer of styrenic based gel material and wherein a pressure sensitive adhesive coating is disposed on at least one of the first and second layers opposite to the layer of styrenic based gel material

Advantageously, such cushioning devices provide a desirable level of tack which is retained for an extended period of time (e.g., following at least 3 -months accelerated aging at 50°C).

Additionally, desirable film surface friction is provided by cushioning devices wherein at least one of the first and second layers includes: iii. layer of MAH. Notably, the friction coefficient of the iii. layer of MAH in such cushioning devices is less than that of ii. layer of TPU in a film material.

Further, enhanced bonding strength is exhibited by a layer of a terpolymer having ethylene, butyl acrylate and MAH bonded to a layer of TPU as compared to a layer of MAH grafted linear low density polyethylene (MAH-LLDPE) bonded to a layer of TPU.

The present invention also provides methods for providing enhanced adhesion performance of a cushioning device in a shoe including providing the aforementioned cushioning devices wherein the pressure sensitive adhesive is positioned so as to attach the cushioning device inside of the shoe. BRIEF DESCRIPTION OF THE FIGURES

Figure 1 depicts a cross section of one embodiment of the cushioning device of the present invention.

Figure 2 depicts a cross section of another embodiment of the cushioning device of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

Referring to Figures 1 and 2, cushioning devices 10 of the present invention are shown. Cushioning device 10 is used in a manner well known in the art to provide a barrier so as to increase user comfort, for example, to prevent footwear from rubbing sensitive areas of skin (e.g., the heel area). Cushioning device 10 has a styrenic based gel material 12, having a top surface 22 and a bottom surface 24.

Referring to Figure 1, the cushioning device has two layers of a film material 14, each of the film material including i. layer of MAH 16 and ii. layer of TPU 18, wherein the first layer has a surface 26 bonded to the top surface 22 and the second layer has a surface 26 bonded to the bottom surface 24 of the layer of styrenic based gel material 12 and wherein a pressure sensitive adhesive coating 20 is disposed on a surface 28 of the second layer of the film material 14 that is opposite to the surface 26 of the film material bonded to the layer of styrenic based gel material 12. Optionally, a release liner 30 is present on the exposed surface of the pressure sensitive adhesive coating.

Referring to Figure 2, the cushioning device 10 has a first layer of film material 32 and a second layer of film material 14. The first layer 32 includes i. layer of MAH 16, ii. layer of TPU 18, and iii. layer of MAH 36. The second layer 14 includes i. layer of MAH 16 and ii. layer of TPU 18. The first layer 32 has a surface 34 bonded to the top surface 22 of the layer of styrenic based gel material 12. The second layer 14 has a surface 26 bonded to the bottom surface 24 of the layer of styrenic based gel material 12 and the second layer 14 has a pressure sensitive adhesive coating 20 disposed on a surface 28 of the second layer of the film material 14 that is opposite to the surface 26 of the film material bonded to the layer of styrenic based gel material 12. Optionally, a release liner 30 is present on the exposed surface of the pressure sensitive adhesive coating.

Styrenic based gel materials suitable for use in the present invention include, but are not limited to, the Kraton family of styrene-olefin-rubber block copolymers. In certain embodiments, elastomers are a Kraton block copolymer of styrene- isoprene-styrene (SIS), styrene-isobutylene-styrene (SIBS), styrene/ethylene-co- butylene/styrene (SEBS) or styrene/butadiene/styrene (SBS), and combinations of two or more thereof. In one embodiment, the gel material is a Kraton block copolymer of styrene/ethylene-co-butylene/styrene (SEBS). In certain embodiments, the styrenic based gel material includes mineral oil incorporated into the matrix as a plasticizer. In one preferred embodiment, the gel material is a Kraton block copolymer of styrene/ethylene-co-butylene/styrene (SEBS) with mineral oil incorporated into the matrix as a plasticizer.

As used herein, TPU will be understood to encompass polymers that contain a plurality of urethane linkages and comprise either aliphatic or aromatic isocyanate prepolymers, and combinations thereof, both with either di- or tri-functional polyol polymers or prepolymers. The TPU may optionally also contain other kinds of chemical linkages formed from the reactions of polyisocyanates, including but not limited to urea linkages, isocyanurate linkages, oxazolidone linkages, biuret linkages, allophanate linkages, combinations of these, and the like.

The gel materials useful in the invention may typically have a Shore 00 hardness of between about 10 and about 80. In certain embodiments, the gel materials used may have a Shore 00 hardness of between about 30 and about 60. In certain embodiments, the gel materials used may have a Shore 00 hardness of about 50. The gel materials may typically have a thickness of between about 1 and about 7 mm. In certain embodiments, the gel materials used may typically have a thickness of 2.5 mm.

The film material includes i. layer of MAH and ii. layer of TPU. In certain embodiments, each i. layer of MAH independently includes (i) MAH-LLDPE, (ii) a terpolymer having ethylene, butyl acrylate, butyl acetate or ethyl acetate, and maleic anhydride, or (iii) a combination of (i) and (ii). In one embodiment, the i. layer includes MAH-LLDPE.

In certain embodiments, the film material has a thickness ratio of the i. layer to the ii. layer of between 1 :3 and 3 : 1. In certain embodiments, the i. and ii. layers of the film material have a thickness ratio of i. layer to ii. layer of between 1 : 1 and 1 :2. For example, one or both of the first and second layers of the film material may have a thickness of i. layer of MAH that is about 0.04 mm and a thickness of ii. layer of TPU that is about 0.08 mm. Alternatively, one or both layers of the first and second layers of the film material may have a thickness of i. layer of MAH that is about 0.02 mm and a thickness of ii. layer of TPU that is about 0.04 mm.

In certain embodiments, the i. and ii. layers of the film material in the cushioning device will have a thickness of about 0.5 mm. In certain embodiment, the i. and ii. layers of the film material in the cushioning device may have a total thickness of about 0.4 mm. In certain embodiments, the i. and ii. layers of the film material in the cushioning device will have a thickness of 0.2 mm.

In certain embodiments, at least one of the first and second layers of the film material further includes iii. layer of MAH. For example, the iii. layer of MAH includes (i) maleic anhydride grafted linear low density polyethylene, (ii) a terpolymer having ethylene, butyl acrylate, butyl acetate or ethyl acetate, and maleic anhydride, or (iii) a combination of (i) and (ii).

In certain embodiments, the film material has a thickness ratio of the i. layer to the ii. layer of between 1 :3 and 3 : 1 and a thickness ratio of the ii. layer to the iii. layer of between 3 : 1 and 1 :3. In one embodiment, the i. layer, ii. layer and iii. layer of the film material in the cushioning device has a thickness ratio of 1 : 1 : 1.

In one embodiment, the film material has i. layer of MAH-LLDPE, ii. layer of TPU and iii. layer of MAH-LLDPE. In another embodiment, the film material has i. layer of MAH-LLDPE, ii. layer of TPU and iii. layer of a terpolymer of ethylene, butyl acrylate, butyl acetate or ethyl acetate, and MAH. In yet another embodiment, the film material has i. layer of a terpolymer of ethylene, butyl acrylate, butyl acetate or ethyl acetate, and MAH, ii. layer of TPU and iii. layer of MAH-LLDPE. In still yet another embodiment, the film material has i. layer of a terpolymer of ethylene, butyl acrylate, butyl acetate or ethyl acetate, and MAH, ii. layer of TPU and iii. layer of a terpolymer of ethylene, butyl acrylate, butyl acetate or ethyl acetate, and MAH. In yet still another embodiment, the film material has i. layer of MAH-LLDPE and/or a terpolymer of ethylene, butyl acrylate, butyl acetate or ethyl acetate, and MAH, ii. layer of TPU and iii. layer of MAH-LLDPE and/or a terpolymer of ethylene, butyl acrylate, butyl acetate or ethyl acetate, and MAH.

In one embodiment, the i. layer, ii. layer and iii. layer of the film material in the cushioning device each have a thickness of about 0.08 mm. For example, in one embodiment, the film material has i. layer of MAH-LLDPE with a thickness of 0.08 mm, ii. layer of TPU with a thickness of 0.08 TPU and iii. layer of MAH-LLDPE with a thickness of 0.08 mm.

Suitable materials for use in the present invention in each layer of MAH independently include (i) MAH-LLDPE; (ii) a terpolymer having ethylene, butyl acrylate, butyl acetate or ethyl acetate, and maleic anhydride, or (iii) a combination of (i) and (ii). In certain embodiments, the i. layer of MAH includes MAH-LLDPE. In certain embodiments, the iii. layer of MAH includes a terpolymer of ethylene, butyl acrylate, butyl acetate or ethyl acetate, and MAH. In certain embodiments, either or both the i. layer of MAH and iii. layer of MAH includes a combination of MAH- LLDPE and a terpolymer of ethylene, butyl acrylate, butyl acetate or ethyl acetate, and MAH. Such combinations can readily be achieved by blending components as is well known to a skilled artisan.

The MAH content of MAH-LLDPE is about 1% or less. The MAH content of suitable terpolymers of ethylene, butyl acrylate, butyl acetate or ethyl acetate, and MAH is 1 to 4% (e.g., greater than 1 wt % to 4 wt %). Exemplary suitable terpolymers of ethylene, butyl acrylate, butyl acetate or ethyl acetate, and MAH include, but are not limited to, Lotader® 3210 resin (a random terpolymer of ethylene, butyl acrylate and MAH having a 3% MAH content), Lotader® 3410 resin (a random terpolymer of ethylene, butyl acrylate and MAH having a 3% MAH content), Lotader® 4210 resin (a random terpolymer of ethylene, butyl acrylate and MAH having a 3.8% MAH content, Lotader® 2210 (a random terpolymer of ethylene, acrylic ester and MAH having a 2.8% MAH content), and Lotader® 2308 (a random terpolymer of ethylene, acrylic ester and MAH having a 1.5% MAH content), all of which are available from Arkema, Colombes, France.

In one embodiment, when an SEBS gel material is used in the cushioning device, the ii. layer of TPU includes SEBS. The ii. layer of TPU may typically have a Shore A hardness of between about 40 to about 95. The ii. layer of TPU may typically have a thickness of between 0.025 mm and 0.25 mm.

In certain other embodiments, individual layers of the film material in the cushioning device will have different thicknesses. In practice, varying the thickness of the film material will affect the softness and flexibility of the film material and will likewise affect the softness and flexibility of the final cushioning product.

As used herein, pressure sensitive adhesives (also known as contact adhesives) are those that form viscoelastic bonds that are aggressively and permanently tacky, adhere without the need of more than slight pressure, and require no activation by water, solvent or heat. Pressure sensitive adhesives are typically available in solvent and latex or water based forms and are often based on non-crosslinked rubber adhesives, acrylics or polyurethanes.

In certain embodiments of the invention, the pressure sensitive adhesives may comprise acrylic and methacrylate adhesives, rubber-based pressure sensitive adhesives, styrene copolymers such as styrene-isoprene-styrene (SIS) and styrene- butadiene-styrene (SBS) copolymers with at least one tackifier, and silicones. Acrylic adhesives often use an acrylate system such as ethylene ethyl acrylate (EEA) or ethylene methyl acrylate (EMA) copolymers, which are used to form hot melt PSA adhesives. Natural rubber, synthetic rubber or elastomer adhesives may typically comprise a variety of materials such as silicone, polyurethane, chloroprene, butyl, polybutadiene, isoprene or neoprene. Rubber and elastomers are characterized by their high degree of flexibility and elasticity. In certain embodiments, the pressure sensitive adhesive material may include aery late-based adhesive materials. The thickness of the layer of the pressure sensitive adhesive material may be varied by those of ordinary skill in the art according to the adhesive material used and the desired tack. In certain embodiments, the pressure sensitive adhesive may have a thickness of between about 0.012 mm and about 0.075 mm. In certain embodiments, the pressure sensitive adhesive will have a thickness of 0.012 mm.

In one embodiment, probe tack is at least about 300 g. In certain embodiments, probe tack is at least about 300 g following incubation at 50°C for at least 3 months.

Although desirable for use in cushioning devices, it is known that gel materials such as SEBS do not readily bond to a TPU film. To overcome this limitation, a film material, including a layer of TPU and layer of MAH, was utilized. The film material was manufactured by a co-extrusion process. The layer of MAH serves as an anchoring layer for the SEBS gel so that the SEBS gel can be bonded to the film material having a TPU layer on the opposing surface to that bound to the SEBS gel. The film material is used as a covering for the SEBS gel. Desirably, the delamination strength between a gel material comprising SEBS and a film material including a layer of MAH and a layer of TPU was found to be about 1.5 lb/in which is sufficient for applications associated therewith.

An injection molding process may be used in a manner well known in the art to bond the layer of MAH of the film material to the SEBS gel. Specifically, in preparation for injection molding, a film material is placed next to the SEBS gel with the layer of MAH of the film material facing the SEBS gel. Additionally, prior to injection molding, a pressure sensitive adhesive is applied to one TPU layer side of the film material. The mold can be treated to resist bonding of the pressure sensitive adhesive or a release liner material can be applied in the mold before application of the pressure sensitive adhesive. Typically, the mold temperature is between 160 °C and 210 °C and the cycle time is approximately 1 min.

The products of the invention can be formed into any shape suitable for use as a cushioning device, for example for insertion into footwear to prevent rubbing between sensitive skin and hard or exposed surfaces of the footwear. The cushioning elements can also be applied to other garments (e.g., hats, helmets, protective sporting gear such as elbow and knee pads and other garments requiring extra padding for comfort, sizing and/or safety). Cushioning elements according to the invention may also be applied to surfaces which come in contact with body parts to provide protection from injury (e.g., chairs, desks, cabinets, tables, doors and door frames, among others). Depending on the size and shape of the object to which the cushioning element is applied, certain shapes will better protect different areas of the body from contact with the object. In certain example embodiments, the products are molded in the shape of circles, parabolas, stars, squares, rectangles, rounded rectangles, half-moon, among others. The appropriate shape of the cushioning element can be determined based on the size and surface of the object to which the cushioning element will be applied. In alternative example embodiments, the cushioning element can be provided as a sheet of material that the user can cut to a desired shape. The sheet of material can also be provided with preformed shapes that can be removed as desired for the appropriate protection from contact with the object.

It will be appreciated by those skilled in the art that changes could be made to the embodiments described above without departing from the broad inventive concept thereof. It is understood, therefore, that this invention is not limited to the particular embodiments disclosed, but is intended to cover modifications that are within the spirit and scope of the invention, as defined by the appended claims. EXAMPLES

Example 1

The cushioning device of the present invention in accordance with the embodiment depicted in Figure 1 wherein the layer of MAH is a layer of MAH- LLDPE was compared to a cushioning device having a linear low density polyethylene single layer film bound to a SEBS gel with a pressure sensitive adhesive bound to an exposed surface of the linear low density polyethylene single-layer film. In particular, a probe tack test was conducted on both cushioning devices in accordance with ASTM D 2979-01 to measure the force required to separate an adhesive and adherend shortly after they have been contacted under a defined load of known duration and at a specified temperature. The results of the probe tack test are reflected in Table 1. Table 1

Film in cushioning device Probe Tack (g) Probe Tack (g)

after 3-month accelerated aging

Multi-layer film 317 ± 15 321 ± 17

Single-layer film (comparative 187 ± 24 32 ± 1

example)

Unexpectedly, the probe tack of the cushioning device employing a multi-layer film was much higher than that of the single-layer linear low density polyethylene single- layer film. Further, following a 3 -month accelerated aging period during which the cushioning devices were incubated in a 50°C oven, the probe tack of the pressure sensitive adhesive of the cushioning device was much better retained in the multilayer film as compared to the single-layer film. In fact, whereas the probe tack in the cushioning device of the multi-layer film was maintained at a desirable level, that of the single-layer film was insufficient for applications such as for use in a heel cushioning device.

Example 2

The film surface friction was assayed in cushioning devices of the present invention in accordance with the embodiments depicted in Figures 1 and 2 wherein each of the layers of MAH is a layer of MAH-LLDPE. In particular, the film surface friction of the skin/sock-contact layer, that is the ii. layer of TPU 18 of the film material in accordance with Figure 1 and the iii. layer of MAH 36 of the film material in accordance with Figure 2 was assessed. The assay was conducted in accordance with (ASTM D 1894) to quantify the friction coefficient of the film surfaces. The results of this film surface friction assay are reflected in Table 2.

The lower the film surface friction, the better the rubbing relief. Accordingly, cushioning devices having a layer of MAH-LLDPE as the skin/sock-contact layer provide much better rubbing relief than those having a layer of TPU as the skin/sock- contact layer. Further, the low level of friction coefficient of the film surface achieved by a layer of MAH-LLDPE could not be achieved by a single layer of TPU film.

Example 3

The bonding strength was assayed in a film material having a layer containing

Lotader® 3210 (available from Arkema, Colombes, France) and a TPU layer. In particular, the film material had a layer of Lotader® 3210 with a thickness of 0.04 mm and a layer of TPU with a thickness of 0.14 mm. The bonding strength was assayed in accordance with (ASTM D 3807). The bonding strength between the layers of the film material was so strong that the layers could not be delaminated from each other. Such bonding strength may provide a more durable film material in applications associated therewith. In comparison, the typical bonding strength between a layer of MAH-LLDPE and a TPU layer is about 1.5 lb/in which is sufficient for applications associated with cushioning devices. Comparable delamination strength would be expected between a layer of other terpolymers having ethylene, butyl acrylate, butyl acetate or ethyl acetate, and MAH and a TPU layer.

Claims

WHAT IS CLAIMED IS:

1. A cushioning device comprising a layer of styrenic based gel material comprising top and bottom surfaces, a first layer comprising: i. layer of maleic anhydride, and ii. layer of thermoplastic polyurethane, and a second layer comprising: i. layer of maleic anhydride, and ii. layer of thermoplastic polyurethane, wherein the first layer has a surface bonded to the top surface of the layer of styrenic based gel material, and the second layer has a surface bonded to the bottom surface of the layer of styrenic based gel material and wherein a pressure sensitive adhesive coating is disposed on at least one of the first and second layers opposite to the layer of styrenic based gel material.

2. The cushioning device of Claim 1, further comprising a release liner on an exposed surface of the pressure sensitive adhesive coating.

3. The cushioning device of Claim 1, wherein the styrenic based gel material has a Shore 00 hardness of between about 10 and about 80.

4. The cushioning device of Claim 1, wherein the styrenic based gel material has a Shore 00 hardness of between about 30 and about 60.

5. The cushioning device of Claim 1, wherein the styrenic based gel material has a Shore 00 hardness of Shore 00 hardness of about 50.

6. The cushioning device of Claim 1, wherein the styrenic based gel material has a thickness of between 0.3 mm and 3 mm.

7. The cushioning device of Claim 1, wherein the styrenic based gel material comprises styrene copolymers selected from styrene-isoprene-styrene (SIS), styrene-isobutylene-styrene (SIBS), styrene-ethylene-butylene-styrene (SEBS), styrene-butadiene-styrene (SBS) copolymers, and combinations of two or more thereof.

8. The cushioning device of Claim 1, wherein the styrenic based gel material comprises styrene-ethylene-butylene-styrene (SEBS).

9. The cushioning device of Claim I, wherein the i. layer to the ii. layer has a thickness ratio of between 1 :3 and 3 : 1.

10. The cushioning device of Claim I, wherein the ii. layer has a Shore A hardness of between about 40 to about 95.

11. The cushioning device of Claim I, wherein the ii. layer has a thickness of between 0.025 mm and 0.25 mm.

12. The cushioning device of Claim I, wherein the ii. layer has a thickness of at least 0.025 mm.

13. The cushioning device of Claim I, wherein the ii. layer comprises SEBS material.

14. The cushioning device of Claim I, wherein the pressure sensitive adhesive coating comprises acrylic adhesives, methacrylate adhesives, or rubber- based adhesives.

15. The cushioning device of Claim 1, wherein the pressure sensitive adhesive coating is an adhesive based on styrene copolymers, silicones or combinations thereof.

16. The method of Claim 1, wherein the pressure sensitive adhesive coating has a thickness of between about 0.0125 mm and about 0.25 mm.

17. The cushioning device of Claim 1, wherein probe tack of the pressure sensitive adhesive coating to an adherend conducted in accordance with ASTM D 2979-01 is at least about 300 g.

18. The cushioning device of Claim 1, wherein probe tack of the pressure sensitive adhesive coating to an adherend conducted in accordance with ASTM D 2979-01 is at least about 300 g following incubation at 50°C for at least 3 months.

19. The cushioning device of Claim 1 which is a heel cushioning device.

20. The cushioning device of Claim 1, wherein each i. layer of maleic anhydride independently comprises (i) maleic anhydride grafted linear low density polyethylene, (ii) a terpolymer having ethylene, butyl acrylate, butyl acetate or ethyl acetate, and maleic anhydride, or (iii) a combination of (i) and (ii).

21. The cushioning device of Claim 1 , wherein at least one of the first and second layers further comprises: iii. layer comprising maleic anhydride.

22. The cushioning device of Claim 21, wherein the iii. layer comprises (i) maleic anhydride grafted linear low density polyethylene, (ii) a terpolymer comprising ethylene, butyl acrylate, butyl acetate or ethyl acetate, and maleic anhydride, or (iii) a combination of (i) and (ii).

23. A method for providing enhanced adhesion performance of a cushioning device in a shoe, comprising providing the cushioning device of Claim 1 wherein the pressure sensitive adhesive is positioned so as to attach the cushioning device inside of the shoe.