Method of making polymeric articles

TECHNICAL FIELD [0001] The present invention relates to methods of making polymeric articles and articles made by the method, in particular to processes for the production of polymeric gel products and articles made by this method.

BACKGROUND [0002] Many frequently used objects include materials that are hard to touch for human and / or cause friction while being placed on the human body, especially with repetitive movements. It is generally considered desirable that the areas of such objects in contact with the body be made as soft as possible so that their use is more convenient for the user, e.g. by reducing pressure and / or friction. "In contact with the body" as used herein means contact with the skin and / or clothing of the user. There have been many attempts to make such items or areas of such objects in contact with the body more convenient for the user. For example, the relatively rigid grips of the shaving razor and the toothbrush are fitted with areas of softer materials, including softer areas in the ribs, which are easier to bend in thin dimensions. The hair brushes are provided with a relatively soft plastic polymer coating arranged around the rigid holder. Handles in suitcases, backpacks, briefcases and bags are equipped with relatively thick padded handles.

US6129799 discloses a method and apparatus for producing blisters filled with a high viscosity liquid or gel. The flexible film is placed over the cavity formed in the first mold half and drawn in vacuum to the shape of the cavity. A certain amount of liquid is deposited on the first film in the cavity, the first film and liquid being covered with a second film.

The second mold half is placed in alignment with the first mold half to connect opposing sealing surfaces along the outer circumference of the cavity. A vacuum is released to remove air from the cavity between the first and second foil through channels corresponding to the transverse grooves formed in the sealing surface of the first mold halve. The first and second foil are then welded at the sealing surfaces to form a sealed bubble filled with fluid and the fluid-filled bubble is removed from the mold halves.

US5932046 discloses a method of manufacturing a fabric covered cushion comprising the steps of coating one side of a stretchable fabric with a gel / foam to immunize said fabric for air flow therethrough, arranging the coated fabric on a mold adapted to vacuum-mold the chilled fabric and placing at least one strip member in the form with a fragment of the member in the form of a strip protruding beyond the boundary of the form. Thereafter, a vacuum is applied between the mold and the fabric to stretch the fabric and cause a close contact between the fabric and the mold. When applying a vacuum, an extra volume of foam is deposited on the fabric shell to allow the bond between the extra gel / foam volume, coated fabric, and the like.

EP 1 962 636 B1 a strip member. The additional gel / foam is allowed to be fixed and bonded to the fabric and the belt member, and the fabric-covered cushion is removed from the mold with the selected contour.

[0003] There is a need in the art for improved methods for making polymer products.

SUMMARY [0004] The present disclosure relates to a method for forming an article. The method includes selecting a first mold part including an upper surface, the top surface comprising a recessed area, and the recessed area containing a plurality of molding units disposed therein; placing a barrier layer on the upper surface of the mold, the barrier layer comprising a thermoplastic elastomer (TPE) material; dispensing a first portion of polymeric gel precursor onto the barrier layer; placing the stabilizing layer on the polymer gel precursor and forming a boundary plane between the gel precursor and the stabilizing layer; sliding the boundary plane, exerting pressure on the stabilizing layer adjacent to the boundary plane, until the gel precursor is covered by the stabilizing layer; closing the form; formation of a polymer gel from the gel precursor; and removing a sheet comprising a plurality of molded articles interconnected by means of a polymerized gel layer. The method may include release of molded articles from the sheet. The method may also include placing the fabric layer on the barrier layer prior to dispensing the first portion of polymeric gel precursor. The method may also include placing the fabric layer on the first portion of the gel precursor before placing the stabilizing layer; placing the fabric layer on the first portion of the gel precursor and placing a second portion of the gel precursor on the fabric layer. A gluing material can also be provided on the stabilizing layer and / or the layer of the fabric. Each layer, polymerized and stabilizing, may show adhesiveness, wherein the adhesion of the stabilizing layer is less than the adhesion of the polymerized layer. The barrier layer may comprise a support layer and the barrier layer may be placed on the mold with a support layer adjacent to the upper surface of the mold. The barrier layer and / or the stabilizing layer may comprise opposing surfaces and a release means may be provided on one or both of the opposing surfaces. The release agent may be located on the surface of the barrier and / or stabilizing layer adjacent to the gel precursor. The barrier layer and / or the stabilizing layer may comprise opposing surfaces and a release means may be provided on one or both of the opposing surfaces. The release agent may be located on the surface of the barrier and / or stabilizing layer adjacent to the gel precursor. The barrier layer and / or the stabilizing layer may comprise opposing surfaces and a release means may be provided on one or both of the opposing surfaces. The release agent may be located on the surface of the barrier and / or stabilizing layer adjacent to the gel precursor.

[0005] The method for using such an article may include manually removing the stabilizing film from the article and adhering the polymer gel to the surface.

[0006] The article, in particular the insole for shoes, can be made by the above method. The shoe insert may comprise a barrier layer of thermoplastic elastomer (TPE); a polymerized gel layer having a hardness ranging from about 30 Shore to 000 to about 75 Shore 00; and a stabilizing layer disposed adjacent to the polymerized gel layer and opposite the barrier layer. The TPE can be selected from the group consisting of thermoplastic polyurethane (TPU), silicone and combinations comprising at least one of the above. The barrier layer may comprise a support layer, and a TPE adjacent to the polymerized gel may be placed on the support layer. The release agent may be placed between the polymerized gel and the stabilizing layer.

The polymerized gel is The polymerized gel layer may comprise a thermoplastic polyurethane. An active agent can be placed in the barrier layer, wherein the active agent can be selected from the group consisting of silver, tolnaftate, undecenoic acid, allylamines, chlorine, copper, bicarbonate, sodium omadine, omadine-zinc, azoles and combinations containing at least one of the above . The polymerized gel may have sufficient adhesion to adhere to the inner surface of the shoe.

[0007] The shoe insert may comprise a barrier layer of a thermoplastic elastomer, wherein the barrier layer comprises an active agent; a polymerized gel layer; and a stabilizing layer disposed adjacent to the polymerized gel layer and opposite the barrier layer. The active agent can be selected from the group consisting of silver, tolnaftate, undecenoic acid, allylamines, chlorine, copper, baking soda, sodium omadine, omadine zinc, azoles and combinations containing at least one of the above. The TPE can be selected from the group consisting of thermoplastic polyurethane (TPU), silicone and combinations comprising at least one of the above. The barrier layer may comprise a support layer, and a TPE adjacent to the polymerized gel may be placed on the support layer. The polymerized gel layer may have a hardness ranging from about 30 Shore to 000 to about 75 Shore 00. The release agent may be placed between the polymerized gel and the stabilizing layer. The release agent may be placed on the surface of the stabilizing layer adjacent to the polymerized gel layer. The polymerized gel layer may comprise a thermoplastic polyurethane. The polymerized gel may have sufficient adhesion to adhere to the inner surface of the shoe.

[0008] The above-described and other features are exemplified by means of the following figures and detailed description.

DRAWINGS [0009] Referring now to the figures which are exemplary embodiments, and on which similar elements are similarly numbered:

Figure 1 is a perspective view of an exemplary form that can be used in the method of the present disclosure;

Figure 2 is an enlarged perspective view of a portion of the mold of Figure 1;

Figure 3 is a schematic cross-sectional view of the mold shown in Figure 1, along line 3-3;

Figure 4 shows the application of the barrier layer to the mold shown in Figure 3;

Figure 5 shows the application of a gel precursor to the barrier layer shown in Figure 4;

Figure 6 shows the application of a stabilizing layer on the gel precursor shown in Figure 5;

Figure 7 shows a method for shifting the stabilizing layer on the precursor of the gel shown in Figures 5 and 6;

EP 1 962 636 B1

Figure 8 shows a stabilizing layer covering the gel precursor;

Figure 9 shows the mold during closure;

Figure 10 shows the post-closure mold and polymerization of the gel precursor;

Figure 11 shows a plastic sheet comprising molded units after demoulding;

Figure 12 is a top view of an exemplary insole under the heel of a shoe;

Figure 13 is a sectional view of the insert of Figure 12, along line 13-13;

Figure 14 is a cross-sectional view of the insert of Figure 12, along line 13-13 illustrating the release of the stabilizing layer from the adhesive layer;

Figure 15 is a plan view of an exemplary rigid toothbrush holder with a polymeric gel overlay on a holder according to the present disclosure and showing a phantom text;

Figure 16 is a cross-sectional view of the cap on the holder of Figure 15;

Figure 17 is a sectional view of the handle overlay of Figure 15, showing release of the stabilizing layer from the polymeric gel;

Figure 18 is a cross-sectional view of a rigid toothbrush holder, taken along line 1818, depicting an overlay of polymeric gel stuck in a recess in a rigid holder;

Figure 19 is a sectional view of an alternative cover for a toothbrush holder containing a collar;

Figure 20 is a sectional view of the rigid toothbrush holder shown in Figure 15 showing a polymer gel pad flange positioned in a cavity in a rigid holder.

DETAILED DESCRIPTION [0010] The present disclosure relates to methods of making polymeric products and articles made by this method, particularly methods for making polymer products with a relatively low durometer. Polymer products with a relatively low durometer can be extremely sticky, which makes it difficult or impossible to use them in commercial processing technologies, such as injection molding, because plastics will stick to molds. In addition, such materials may have relatively low durability compared to other materials, including other polymeric materials. Thus, applications for polymeric gel materials with a relatively low durometer are limited, despite their beneficial properties of plasticity and softness.

[0011] Figures 1 - 11, taken together, illustrate an exemplary method of forming articles from a polymer gel. The present method includes selecting a suitable form for the desired product, as shown in Figures 1-3, which may include opposite top and bottom surfaces 12,

EP 1 962 636 B1

14. As shown, the mold 10 may include a recessed area 16 defined in the mold upper surface 12 that is recessed from the upper surface 12 to a depth "D1". It is to be understood that the terms "underside" and "top" and / or "upper" and "lower" are used herein, unless otherwise indicated, merely for convenience of description and are not limited to any single position or spatial orientation. Furthermore, it should be understood that the terms "first", "second" and the like do not indicate any order, quantity or validity here, but rather are used to distinguish one element from another, and the nouns mentioned here in the singular do not indicate a limitation of quantity, rather they indicate the presence of at least one reference position. In addition, unless otherwise specified,

[0012] The present mold 10 comprises thirty-six (36) individual forming units 18 defined in the recessed area 16, each corresponding to the shape and size of the desired final molded product 19, which in this case is a heel insert for the shoe. Although, for convenience, a heel insole is illustrated here, it should be understood that various products can be formed using this method. Each of the thirty-six (36) individual forming units 18 is recessed from the upper surface 12 by a depth "D2" which corresponds to the desired thickness of the final molded product 19.

The mold 10 may also include a recess 21 for a seal disposed between the recessed area 16 and the circumference "P" of the mold 10 in which the gasket 20 can be arranged. Alternatively, the gasket 20 may be disposed directly on the upper surface 12 of the mold 10. The gasket 20 may provide a seal sufficient to restrict the polymer flow from the mold 10. The seal 20 or mold 10 may include periodic openings 22 to allow the entrapped air to escape out of the mold 10 during the molding process. For example, as shown, the gasket 2 may include openings 22. Optionally, the mold 10 may include one or more alignment guides 24.

[0014] As shown in Figure 4, after selecting the appropriate mold 10, the method may include placing the barrier layer 26 on the mold 10. The barrier layer 24 may be placed on the mold 10 as a plastic sheet or as a coating applied directly onto the mold. When applied as a sheet 24, the barrier layer 24 may be applied to the mold and physically in contact with the seal 20. When applied as a sheet 24, the barrier layer 26 may include leveling guides (not shown) corresponding to the equalizer guides 24 in the form. 10, to assist its alignment with the mold 10 and further layers. If the barrier layer 26 is not placed as a sheet, then it can be placed directly on the upper surface 12 of the mold 10.

[0015] As shown in Figure 5, after the barrier layer 26 is placed on the upper surface 12 of the mold 10, the gel precursor 28 can be dispensed onto the barrier layer 26. The gel precursor 28 can be placed on the barrier layer 26 by various techniques such as, e.g. in a non-limiting manner, casting, injection and / or the like.

[0016] Dosing the gel precursor 28 may involve casting a sufficient amount of gel precursor to fill each of the thirty six (36) individual forming units 18, instead of filling a single forming unit 18, as in other processes such as injection molding. . For example, other methods, such as injection molding, may include dispensing the gel precursor 28 separately to each forming unit 18. Therefore, using this mold, thirty-six (26) separate dispensing steps would be required. However, the present method may comprise dispensing the gel precursor 28 only once per barrier layer 26, wherein a single dosage of the gel precursor 28 may provide a sufficient amount of the gel precursor 28 to form all of the forming units 18 in a single molding cycle.

[0017] As shown in Figure 6, after dispensing the gel precursor 28 on the barrier layer 26, the stabilizing layer 30 may be placed on the precursor of the gel 28, e.g. as a sheet. If the mold 10 includes alignment guides 24, then the stabilizing layer 30 may also include appropriate compensatory guides (not shown) to assist in aligning it with the mold 10 and with all further layers. The placement of the stabilizing layer 30 on the gel precursor may include placing the stabilizing layer 30 on a portion of the gel precursor 28 such that a boundary plane 32 will exist between the gel precursor 28 and the stabilizing layer 30. The placing of the stabilizing layer 30 on the gel precursor 28 can be done by hand, using a tool such as a roller, as illustrated in Figure 7, or the process can be automated. The remaining portion of the stabilizing layer 30 can be shifted to the remainder of the gel precursor 28 by applying pressure to the stabilizing layer 30 behind the boundary plane 32, wherein the advancing of the boundary plane 32 up to the stabilizing layer 30 covers the entire gel precursor 28 as depicted in FIG. The pressure when shifting the stabilizing layer 30 essentially minimizes the formation of air bubbles between the gel precursor 28 and the stabilizing layer 30.

[0018] As shown in Figure 9, the mold 10 can be closed, e.g. by placing the mold cover 10a on the stabilizing layer 30. When the mold 10 is closed, the gel precursor 28 can flow into all mold areas 10 defined by the seal 22 and any trapped air can flow out of the mold through the gasket holes 21.

[0019] As shown in Figure 10, the gel precursor 28 may be allowed to form the polymerized gel 29 in a closed mold for a defined period of time (e.g., from 30 seconds to 5 minutes). If desired, pressure or vacuum in the mold can be applied for various reasons, e.g. to increase the processing speed to improve the quality of the final material to change the surface properties of the polymerized gel and / or the like. As a result, the total processing time for the production of numerous molded products 19 can be substantially shortened compared to other methods, such as injection molding. In addition, since the time used to dispense the gel precursor 28 is reduced compared to other methods, it is possible to increase the curing speed by changing a number of factors such as

For example, pressure, temperature, catalyst concentration (if used) and / or the like. The use of pressure and / or vacuum during the forming process may be desirable when the articles to be formed require a more accurate determination, such as undercuts and the like. In vacuum shaping or thermoforming, it may be desirable to use molds formed at least partially from a porous composite material, which allows the formation of complicated details and surface patterns in the molded article and eliminates the need for ventilation openings in the mold. One example of such a porous composite material is breathable aluminum, which is commercially available under the trade name METAPOR ™.

[0020] After curing, the mold 10 can be opened and the sheet 33 comprising the molded products 19 can be removed from the mold 10 as shown in figure 11. The presence of the barrier layer 26 and the stabilizing layer 30 can facilitate the handling of the sheet 33, because the polymerized gel 29 is closed by layers 26, 30, which may be advantageous when the polymerized gel 29 has adhesive properties which would otherwise cause it to adhere to surfaces such as the mold surface, user hand and the like. The sheet 33 comprises a plurality of relatively thin regions 29a of the polymerized gel 29 disposed between the barrier layer 26 and the stabilizing layer 30s and joining the molded products 19. The regions 29a of the polymerized gel may have a thickness "Ti" corresponding to the depth Di of the cavity 16 of the mold 10.

The molded products 19 can be separated from the sheet 33 and from one another by cutting (e.g., punching and the like) through the barrier layer 26, regions of the polymerized gel 29a and the stabilizing layer 30. The molded products 19 can be die-cut between regions of the polymerized gels 29 and 29a and / or through the region 29 of the polymerized gel. When the polymerized gel 29 has adhesive properties, it may be desirable to cut a section of the regions of the polymerized gel adjacent to the region 29a of the polymerized gel so that the sides of the molded units 19 comprise the exposed area of ​​the polymerized gel. During die cutting, the presence of the stabilizing layer 30 prevents or minimizes the shrinkage of the polymerized gel 29 and the barrier layer 26,

[0022] Optionally, the layer 34 can be sandwiched between any of the above layers, e.g. between the stabilizing layer 30 and the polymerized gel 29 and / or between the polymerized gel 29 and the barrier layer 26. Also optionally the layer 34 can be placed in the polymer gel 29, e.g. by placing the first portion of the gel precursor 28 on the barrier layer 26, placing the layer 34 on the first portion of the gel precursor 28 and placing a second portion of the gel precursor 28 on the layer 34. The layer 34 can contain a plurality of materials, including in a manner

Non-limiting paper, fabric, plastic film and / or the like as well as composites and / or combinations comprising at least one of the above. Layer 34 can have color, graphics and / or markings, including text. When the layer 34 comprises a fabric layer, the fabric may be knitted, woven, nonwoven, synthetic, non-synthetic and combinations comprising at least one of the above. Placing the fabric layer as a layer 34 may be advantageous and give a better appearance to the final molded products 19 because it can entrap and disperse the air bubbles that otherwise form in or between the layers. In addition, the color, graphics and / or markings on layer 34 may pass through other layers when they are made of colorless and / or transparent materials,

[0023] Also optionally, the layer 34 may be used instead of the stabilizing layer 30. If the layer 34 replaces the stabilizing layer 34, it may be applied in the same manner as described above with respect to the stabilizing layer 34.

[0024] In some cases, it may be desirable to be able to glue the molded products 19 to different surfaces. Therefore, optionally an adhesive (not shown) may be provided on one or more of the end surfaces of the molded products 19. Also optionally, the adhesive may be arranged and / or on one or more surfaces of the layers 26, 28, 30 and 34. For example, in with reference to Figure 11, the adhesive may be placed on the surface 30b and the adhesive may be held by a release and / or carrier layer (not shown). Some possible adhesives may include pressure-sensitive adhesives, thermoplastic adhesives and the like, as well as combinations comprising at least one of the above. One example of such a material is available at 3M as product number 7026.

[0025] In some cases, the polymerized gel 29 may exhibit sufficient adhesion to adhere to the surface in the absence of a separate adhesive. In such cases, it may be desirable for the stabilizing layer 30 to be manually released from the polymerized gel 29. Therefore, optionally the stabilizing layer 30 may include a release coating (not shown), such as a silicone, placed on the surface 30a that may assist manual release a stabilizing layer 30 from the polymerized gel 29.

[0026] W powyższych sposobach można stosować różne tworzywa, aby wytworzyć powyższe formowane produkty 29. Barierowa warstwa 26 może zawierać dowolne tworzywo zdolne do zapewnienia dostatecznej elastyczności, aby zapobiec rozdzieraniu i/lub rozciąganiu, gdy wywierana jest na nie siła; dostatecznej integralności strukturalnej do utworzenia w uprzednio określonych kształtach; i które będzie zdolne do wytrzymania w środowisku, w którym ma być stosowane, bez znacznej degradacji. Barierowa warstwa 26 może być również tak dobrana, aby ułatwiała manipulację warstwą polimeryzowanego żelu, który może mieć właściwości klejące w pewnych przypadkach. Dlatego też po formowaniu barierowa warstwa 26 może być tak dobrana, aby miała stosunkowo nielepką powierzchnię i być stosunkowo gładka w dotyku dla człowieka. Pewne możliwe tworzywa na barierową warstwę 26 obejmują poliolefiny, polistyreny, PVC, gumę lateksową i termoplastyczne elastomery (TPE) i/lub tym podobne, i kombinacje obejmujące co najmniej jedno z powyższych tworzyw.

EP 1 962 636 B1

Some possible TPE materials include polyurethane, silicone and / or the like, and combinations comprising at least one of the above materials. The barrier layer 26 may have an elongation from about 100 percent (%) to about 1500%, more preferably from about 200% to about 1000%, and even more preferably from about 300% to about 700%. It should be understood that the modifier "about" used in connection with the quantity includes the given value and has the meaning dictated by the context (e.g., includes the error rate associated with the measurement of a given amount).

[0027] The barrier layer 26 may be of any thickness. For practical reasons, it has been found that thinner layers can provide a better grip feel, while thicker layers can provide increased durability. Therefore, it is desirable to use the thinnest possible barrier layer to prevent punctures in the barrier layer 26. When the polymerized gel 29 is tacky, the puncture of the barrier layer 26 can detect the base viscous material of the polymerized gel 29, making handling difficult. The barrier layer 26 may have a thickness ranging from about 0.005 mm (~ 0.2 mil-inch) (hereinafter "miles") to about 0.13 mm (~ 5 mil), more preferably from about 0.013 mm (~ 0, 5 mil) to about 0.08 mm (~ 3 mil), more preferably from about 0.015 mm (~ 0.6 mil) to about 0.05 mm (~ 2 mil).

[0028] As noted above, the barrier layer 26 could be applied as a plastic sheet during the forming process. In the form of a sheet, and especially when the barrier layer is relatively thin, the barrier material can be very flexible and can very easily wrinkle and / or bend during handling, which is not desirable. Therefore, the barrier layer 26 may also include a support layer (not illustrated) that supports manipulation of the material. If the barrier layer 26 comprises such a support layer, then the support layer can be placed adjacent to the upper surface 12 of the mold 10 with the plastic barrier layer facing away from the upper surface 12, which can be removed prior to matrix cutting, if desired or necessary.

[0029] Also as noted above, if the barrier layer 26 is not applied as a sheet, it can be applied as a coating of the material during or after the molding process. If applied after the molding process, the barrier layer can be placed on the polymer gel 28 after forming the molded units 18, for example by painting, spraying, manual brushing and / or the like. When the barrier layer 26 is not placed as a sheet or is not placed as a coating during the molding process, the gel precursor 28 can be placed directly on the upper surface 12 of the mold 10, which may require the use of a release agent on the upper surface 12.

[0030] The polymerized gel 29, 29a may comprise any polymeric material exhibiting sufficient structural integrity to form in predetermined shapes; including foam polymeric materials; sufficient softness and / or deformability to provide comfort to the body; and which will be able to withstand the environment in which it is to be used, without significant degradation. The polymeric material may comprise a thermoset polymeric material, an elastomeric polymeric material, a thermoplastic, including a thermoplastic elastomeric material and combinations comprising at least one of the foregoing. Some possible materials on

The polymerized gel 29, 29a includes polyurethane, silicone and / or the like, and combinations comprising at least one of the above materials.

[0031] The formation of the gel precursor 28 can take place by various methods known to those skilled in the art. For example, the formation of a polyurethane gel may involve reacting with suitable pre-polymer precursor materials, e.g. reacting a polyol and an isocyanate in the presence of a catalyst. In certain embodiments, the polymerized gel 29, 29a may exhibit sufficient adhesion to adhere to a selected surface (such as the inner surface of the shoe). It is possible to change the adhesiveness of the polymerized gel 29, 29a by changing, for example, the durometer of the material used to form the layer. In addition, the durometer of the polymerized gel 29, 29a may be selected so as to give the products and / or product areas a predetermined hardness,

The polymerized gel 29, 29a may have a durometer in the range of about 0.01 on a Shore scale of 00 to less than or equal to about 70 Shore A, more preferably less than 70 on the Shore scale 00, even more preferably below 60 in the Shore 00 scale. In some cases, it may be desirable for the polymerized gel 29, 29a to have adhesive properties to eliminate the use of a separate adhesive to adhere the molded units to the desired surface. In such cases, the polymerized gel may exhibit a durometer of from about 30 Shore on the Shore scale to about 85 on the Shore scale 00. Polymeric gel materials in such relatively low durometer ranges may show a gelatinous consistency. One possible material having such adhesive properties is a polyurethane gel exhibiting a durometer in the range of about 70 Shore 00 to about 85 Shore 00, which can impart sufficient adhesion to adhere to a desired surface, such as the surface of the inner shoe or rigid plastic, such as polypropylene. The polymeric gel 29 and / or barrier layer 26 may contain one or more additives, such as, but not limited to, modifiers, dyes, stabilizers, phase change materials, ultraviolet inhibitors and / or active agents, as well as combinations comprising at least one of the above. The concentration of the additive may vary depending on the desired effectiveness of the agent. which may impart sufficient adhesion to adhere to a desired surface, such as the surface of the inner shoe, or rigid plastic, such as polypropylene. The polymeric gel 29 and / or barrier layer 26 may contain one or more additives, such as, but not limited to, modifiers, dyes, stabilizers, phase change materials, ultraviolet inhibitors and / or active agents, as well as combinations comprising at least one of the above. The concentration of the additive may vary depending on the desired effectiveness of the agent. which may impart sufficient adhesion to adhere to a desired surface, such as the surface of the inner shoe, or rigid plastic, such as polypropylene. The polymeric gel 29 and / or barrier layer 26 may contain one or more additives, such as, but not limited to, modifiers, dyes, stabilizers, phase change materials, ultraviolet inhibitors and / or active agents, as well as combinations comprising at least one of the above. The concentration of the additive may vary depending on the desired effectiveness of the agent. such as, but not limited to, modifiers, dyes, stabilizers, phase change materials, ultraviolet inhibitors and / or active agents, as well as combinations comprising at least one of the foregoing. The concentration of the additive may vary depending on the desired effectiveness of the agent. such as, but not limited to, modifiers, dyes, stabilizers, phase change materials, ultraviolet inhibitors and / or active agents, as well as combinations comprising at least one of the foregoing. The concentration of the additive may vary depending on the desired effectiveness of the agent.

[0033] One of the possible phase change materials may comprise phase change microspheres (available under the product name Outlast) that contain materials that can change phases near body temperature. As a result, thermal energy can be stored in the barrier layer, providing a product that will give a feeling of coolness or warmth.

Suitable active agents may include tolnaftate, undecenoic acid, allylamines, chlorine, copper, baking soda, sodium omadine, zinc omadine, azole, silver and / or the like, and combinations containing at least one of the foregoing. For example, silver can provide antifungal / antibacterial effects. For reasons of economy and efficacy, it has been found advantageous to include active agents when used in the barrier layer 26. Because the barrier layer 26 is relatively thin compared to the polymer gel 29, placing such agents in the barrier layer 26 allows the use of reduced total amounts.

In order to achieve similar effective concentrations compared to thicker layers, this reduces the costs associated with the additives. Furthermore, placing such means in the barrier layer 26 will ensure that the means will be located in the outermost layer of the article, i.e. areas in contact with the body, instead of in areas remote from the user, which can increase the effectiveness of the means.

[0035] In some cases, it may be desirable for each of the layers: a barrier polymerised gel and stabilize the use of colorless materials, which may be desirable for aesthetic reasons. For example, it may be desirable to use colorless insoles for shoes, particularly for women's shoes that sometimes have open toes or open heels.

[0036] The stabilizing layer 30 may comprise a material that is capable of substantially minimizing the shrinkage of the barrier layer 26, the gel precursor 28 and / or the polymerized gel 29 during and after processing; providing a substrate for the polymerized gel 29; and which is capable of facilitating the manipulation of the polymerized gel 29 and the barrier layer 26. The stabilizing layer 30 may comprise any material that is substantially inflexible compared to the polymerized gel 29 to be able to provide dimensional stability to the sheet and / or molded products 19 during and after processing. Certain possible materials for the stabilizing layer 30 include, but are not limited to, fabric, paper, plastic (e.g., polyester, polyethylene, polyvinyl chloride (PVC) and the like), metal, metallised plastic and / or the like, and combinations comprising at least one of the above materials. One of the possible materials is an oriented polyester film that is available commercially from various sources and under different product names (e.g., Mylar (R)). The stabilizing layer 30 may have a thickness ranging from about 0.2 miles to about 10 miles, more preferably from about 0.5 miles to about 5 miles, and even more preferably from about 1 miles to about 2 miles.

[0037] The above methods and materials may facilitate the production of polymeric articles and / or areas of articles that may be desirable for aesthetic reasons and / or to minimize abrasion and / or friction. Methods for making polymeric articles and / or areas of articles having any size, thickness and geometry may be used. The size, thickness, geometry, softness and adhesiveness of articles and / or pieces of articles can be chosen so as to optimize the conditions for which they are intended. Examples of articles in which the above polymeric materials may be useful include, but are not limited to, handles of body care items, such as hair brushes, toothbrushes and razors; holders of household items, such as brooms; belts for luggage, backpacks, briefcases and purses; clothes such as cycling shorts, underwear and shoes; useful items, such as mouse pads, keyboard supports; handles and / or belts for consumer goods, such as bottles and / or boxes, holders for the laundry detergent compartment; sports equipment and accessories, such as rocket handles, kii grips for games, fishing rod holders, guns and handles for the steering wheel of a bicycle; and the like. In addition, the articles may include markings such as labels with color, text and / or graphics, and the like. pistols and handles for the steering wheel of the bicycle; and the like. In addition, the articles may include markings such as labels with color, text and / or graphics, and the like. pistols and handles for the steering wheel of the bicycle; and the like. In addition, the articles may include markings such as labels with color, text and / or graphics, and the like.

[0038] Figures 12-14 show an illustrative article (an insole 40 for the heel of a shoe (hereinafter referred to as the "heel insert")) which can be formed by the above methods and

EP 1 962 636 B1. The heel insert 40 may include opposed upper and lower faces 40a, 40b. In this illustrative embodiment, the heel insert 40 may have a thickness of about 3.17 mm (~ 1/8 inch). The barrier layer 30 may be placed adjacent to the polymerized gel layer 29, and the stabilizing layer 30 may be positioned on the gel layer side opposite the barrier layer 26. If desired, the heel insert 40 may include an antifungal agent placed in the barrier layer 26. In an illustrative example barrier layer 26 may include an active agent, such as silver, to prevent and / or treat athlete's foot. One of the possible barrier layers 26 containing such active agent is Vacuflex 18411, available from Omniflex, Inc.

[0039] In an illustrative embodiment, the polymerised gel layer 29 may exhibit sufficient adhesion to allow it to adhere to a surface, such as the inner surface of a shoe. Thus, the stabilizing layer 30 may optionally comprise a release coating (not shown), such as a silicone, placed on the surface 30a, which may assist in manually releasing the stabilizing layer 30 from the polymerized gel 29, thereby exposing the polymerized gel 29 to allow it to adhere to the gel. surface.

[0040] In a further illustrative embodiment, the adhesive (not shown) may be provided on the surface 40b of the stabilizing layer 30 to allow the underfoot pad 40 to adhere to a surface, such as the inner surface of the shoe. Such an option may be useful, for example if the stabilizing layer 30 does not contain a release coating on the surface 30a.

[0041] Figures 15-18 show another illustrative product which is a substantially rigid toothbrush holder 41 comprising a pad 42 (hereinafter "handle pad") that can be formed by the above methods and materials. The holder pad 42 includes a top surface 42a facing the bottom surface 42b. The grip pad 42 may have a thickness that varies from about 3.17 mm (~ 1/8 inches) to 9.52 mm (~ 3/8 inches). In this illustrative embodiment, the handle pad 42 may include a barrier layer 26 disposed adjacent to the polymerized gel layer 29, a fabric layer 34 located on the polymerizable gel layer 29 opposite the barrier layer 26 and a stabilizing layer 30 adhered to the fabric layer opposite the gel layer 29. In this illustrative embodiment, the adhesive may be sandwiched between the fabric layer 34 and the stabilizing layer 30. If desired, the handle pad 42 may include an antifungal agent placed in the barrier layer 26, as in the previous embodiment. As shown in Figure 18, it can also be placed in a substantially rigid toothbrush holder 41.

[0042] Figures 19-20 show another illustrative product which is a toothbrush holder 41 'comprising a channel for receiving a flanged portion of the handle cap. The handle pad 42 'comprises the same materials as in the previous embodiment and additionally comprises a collar 42a disposed around the overlay. As in the previous embodiment, the handle 41 may include a recess (not shown) configured to receive the handle pad 42, including a channel (not shown) for receiving the collar 42a. Placement of the cap 42 on the holder in the toothbrush holder 41 may include placing the collar 42a in the channel i

The fragment of the body in the recess. If it is desired to provide additional protection to the handle pad 41, the stabilizing layer 30 can be released from the fabric layer 34, and the holder pad 42 can be placed in the recess and glued in the cavity using adhesive, as shown in Figure 20.

[0043] The following non-limiting examples further illustrate various embodiments described herein.

WORKING EXAMPLES

EXAMPLE 1 [0044] Creation of a colorless transparent self-adhesive insole under the heel of a shoe.

[0045] A metal mold designating thirty-six (36) heel inserts was selected for use. The mold contained a recessed area of ​​about 0.508 mm (~ 0.020 ") and a gasket away from both the circumference of the mold edge and the recessed area. The dimensions of each of the 36 forming units were 101.6 mm (~ 4 inches) by about 12.7 mm (~ Y inch), and the depth of forming units was equal.

[0046] The mold was preheated to about 150 ° F, and the barrier layer was placed as a sheet on the top surface of the mold. The barrier layer was Vacuflex 18411 (available from Omnifiex, Inc.), which is a colorless, transparent, polyurethane film about 0.75 miles thick, elongation from about 400% to about 500%, and held on a polyethylene support layer of about 0.038 mm (~ 1.5 miles). The barrier layer was placed on the upper surface of the mold, so that the polyethylene layer was facing the mold, and the polyurethane film was turned away from the mold.

[0047] About 243 grams (g) of the gel precursor were prepared and manually cast on the barrier layer. The gel precursor was a thermoset polyurethane gel system available as WE 369-1 from Isotec International and was prepared with about 0.02 mass percent (wt.%) Based on the weight of the gel precursor. No staining was added to the gel precursor.

[0048] A stabilizing film sheet was placed on a portion of the gel precursor. The stabilizing foil was Hostaphan 2000 2SLK (available from Mitsubishi), which is a polyester foil with a silicone release agent on one surface. The foil had a thickness of about 0.05 mm (~ 2 miles). The stabilizing film was placed on the gel precursor so that the surface of the film that was coated with the silicone release agent was in contact with the gel precursor. A manual pressure was exerted on the stabilizing foil behind the boundary plane between the gel precursor and the stabilizing foil and the stabilizing foil was shifted after the gel precursor until it covered with the foil stabilizing the entire surface of the gel precursor.

[0049] The mold was closed and introduced under a pressure of about 172.37 kPa, i.e. 25 pounds per square inch (psi). After about four (4) minutes the mold was opened and a colorless, transparent sheet containing thirty-six (36) molded under-heel inserts was manually removed from the mold.

EP 1 962 636 B1

The sheet could be manually removed from the mold, so that it did not stick to the surface of the mold or the operator's hand.

[0050] The polyethylene support / transfer layer for the barrier layer was removed and then the sheet was die-molded around the perimeter of each of the thirty-six (36) heel inserts. The sheet was able to be cut without sticking to the cutting die as a result of the stability provided by the polyester layer and the barrier layer. The molded heel inserts were then removed from the sheet.

[0051] The dimensions of each molded, die-cut heel inserts were approximately 101.6 mm (~ four (4) inches) to 33.02 mm (~ 1.3 inches). Molded heel inserts were flexible, flexible, colorless and transparent, and showed minimal shrinkage compared to the dimensions of the individual forms of heel inserts.

[0052] To insert the heel insert into the inside of the shoe, the polyester layer was manually removed from the heel insert, thus revealing the base polyurethane gel. The polyurethane gel was placed on the inside of the shoe. The polyurethane gel was extremely viscous, so that it adhered to the inner surface of the heel shoe part in the absence of a separate or added glue. The heel insert did not stick to the user's foot due to the presence of a barrier layer that provided a smooth surface on the wearer's heel. The polyurethane gel was very soft and susceptible, and the polyurethane barrier layer bent with the gel movement. Because the heel insert was colorless and transparent, it was not visible to the casual observer.

EXAMPLE 2 [0053] Creation of a colorless, transparent self-adhesive insole under the heel in the form of a strap for women's shoes with an exposed heel and thong.

[0054] A metal mold comprising one hundred and forty (140) forming units is selected for use, each of which defines a heel insert in the form of a strip. The mold contained a recessed area of ​​about 0.508 mm (~ 0.020 ") and a gasket away from both the edge of the mold edge and the recessed area. The dimensions of each one hundred and forty (140) forming units were about 76.2 mm (~ 3.0 inches) ) at about 7.9 mm (~ 0.3125 in.) The same materials and process used in Example 1 were used in this example.

[0055] The dimensions of each molded die-cut strip inserts in the form of a strip were about 76.5 mm (~ 3.01 inches) by about 8.2 mm (~ 0.3225 inches). Thus, molded heel inserts in the form of a belt showed minimal shrinkage compared to the dimensions of the individual forms of the heel inserts in the form of a belt. Molded inserts under the heel in the form of a belt were flexible, flexible, colorless and transparent. The polyester layer was manually removed from the heel in the form of a belt, revealing the underlying polyurethane gel, which was extremely viscous, allowing it to adhere to the inner surface of a women's heel with an exposed heel, in the absence of a separate or added glue. The heel insert did not stick to the user's foot due to the presence of a barrier layer, which provided a smooth surface on the wearer's heel. The polyurethane gel was very soft and susceptible, and the barrier layer bent together

EP 1 962 636 B1 with gel movement. Because the heel insert was transparent, it was not visible to an accidental observer.

EXAMPLE 3 [0056] Creation of a colored, self-adhesive overlay for a rigid toothbrush holder.

[0057] A metal mold defining fifty (50) overlays for a toothbrush holder was selected for use. The mold contained a recessed area of ​​about 0.508 mm (~ 0.020 ") and a gasket away from both the edge of the mold edge and the recessed area. The dimensions of each of the forming units were approximately 101.6 mm (~ 4 inches) long and the width which it ranged from about 3.17 mm (~ 1/8 inch) to about 9.52 mm (~ 3/8 in.) The depth of forming units ranged from 3.17 mm (~ 1/8 inch) to around 9, 52 mm (~ 3/8 in.) The same materials and process as used in Example 1 were used in this example, with the addition of about 0.4% by weight chemical dye to the gel precursor (Blue TR Repliplast 67798 available from Pat Products) ).

[0058] The dimensions of each molded die-cut toothbrush holder were about 107.9 mm (~ 4.25 inches) by about 15.9 mm (~ 0.625 inches).

[0059] The individual toothbrush pads obtained were blue, transparent, flexible and compliant and exhibited minimal shrinkage compared to the dimensions of the individual molding units of the toothbrush holder.

[0060] The Hostaphan polyester film was manually removed from the toothbrush holder, thus revealing the base blue polyurethane gel. The polyurethane gel was extremely viscous, allowing adhesion to the recessed area of ​​the rigid toothbrush holder in the absence of a separate or added adhesive. The blue color of the handle pad provided an aesthetic appearance. [0061] Fragments of the handle pad were thicker than the depth of the recessed area in the rigid portion of the toothbrush holder. Therefore, the fragments of the handle pad were raised relative to the surface of the rigid holder. The polyurethane gel was very soft and susceptible, and the barrier layer bent with the gel movement. The surface of the polyurethane barrier film provided a smooth surface on the user's hand.

EXAMPLE 4 [0062] Creating a colored, patterned self-adhesive overlay for a rigid toothbrush holder.

[0063] The same mold and materials used in Example 3 were used in this example. After placing the gel precursor on the barrier layer, the fabric layer was placed as a sheet on a portion of the gel precursor. The fabric had different colors and patterns. Hand pressure was exerted on the fabric layer behind the boundary plane of the gel precursor and fabric layer,

While moving the fabric layer over the remaining exposed gel precursor, the fabric layer covered the entire surface of the gel precursor.

[0064] A pressure sensitive adhesive was placed on the fabric layer. Pressure sensitive adhesive was the product number 950 from the company 3M.

[0065] The Hostaphan 2000 2SLK stabilizing sheet was placed on a pressure-sensitive adhesive so that the silicone release agent was in contact with the pressure-sensitive adhesive.

[0066] The mold was closed and introduced under a pressure of about 25 pounds per square inch (psi). After about four (4) minutes, the mold was opened, and the patterned sheet containing the molded overlays for the toothbrush holder was manually removed from the mold and cut out as in the previous examples.

[0067] Toothbrush pads were flexible and compliant and exhibited minimal shrinkage compared to the dimensions of the individual molding units of the toothbrush holder.

[0068] The Hostaphan polyester film was manually removed from the toothbrush holder overlay, thus revealing the underlying pressure sensitive adhesive that was applied to the fabric layer, and the handle pad was thus glued to the recessed area of ​​the rigid brush holder. for teeth. The fabric pattern was visible through the Isotec gel and Vacuflex film, providing an aesthetic appearance.

[0069] The method (s) of the present disclosure may comprise one or more of the following advantages: 1) the use of a relatively thin barrier layer and release layer on opposite sides of the polymerized gel layer allows manipulation of polymer materials with a relatively low durometer in molding equipment and using equipment operators, without sticking to equipment and / or operators; 2) the use of relatively thin barrier layers allows the use of reduced total amounts of additives, which reduces costs; 3) the use of a relatively thin barrier layer allows the formation of polymer materials with a relatively low durometer to various shapes, sizes, densities and manufacture of articles in which the cross-sectional area changes in size, shape and density; 4) use of the stabilizing layer reduces and / or eliminates shrinkage of the gel precursor, polymer gel and / or barrier layer during and after processing; 5) thanks to the use of a polyurethane gel, the process allows to provide colorless and transparent products that do not turn yellow, which is typical for polyurethanes after exposure to ultraviolet energy.

[0070] Although the disclosure has been described with reference to an exemplary embodiment, those skilled in the art will understand that various changes may be made and its elements may be replaced by equivalents without departing from the scope of the disclosure. In addition, many modifications can be made to adapt a particular situation or material to the recommendations of the disclosure without departing from its essential scope. Therefore, the disclosure is not intended to be limited to a particular embodiment disclosed as the best considered way of doing so

EP 1 962 636 B1 discloses, but the disclosure will include all embodiments falling within the scope of the appended claims.

[0071] The reference marks used in the claims should not be regarded as limiting the scope of the matter protected by the claims; reference designations are used only in the illustrative sense to help the recipient understand the objections.