CN101404907A - Methods of making polymeric articles and the polymeric articles formed thereby - Google Patents

Abstract

Low durometer polymeric gel articles and methods of making are provided herein.

Description

Process for making polymeric articles and polymeric articles formed therefrom

technical field

The present invention relates to methods of making polymeric articles and articles made therefrom, and in particular to methods of making polymeric gel articles and articles made therefrom.

related application

This application hereby claims priority to U.S. Provisional Patent Application No. 60/753,871, filed December 23, 2005, and U.S. Provisional Patent Application No. 60/777,292, filed February 28, 2006, both of which are hereby incorporated by reference in their entirety way is included in this article.

Background technique

Many frequently used objects contain materials that are hard to the touch and/or cause friction when placed adjacent to the human body, especially during repetitive motion. It is generally considered necessary to make the body contacting areas of such objects as soft as possible to make their use more comfortable for the user, eg by reducing pressure and/or friction. "Body contact" as used herein means contact with the user's skin and/or clothing. Many attempts have been made to make such objects, or body contact areas of such objects, more comfortable for users. For example, relatively stiff razor and toothbrush handles have provided areas of softer material, including placement of softer areas with "fins" that bend more easily when the thickness dimension is thin. Hairbrushes already have sheaths of relatively soft polymeric material disposed around their stiff handles. The handles of luggage, backpacks, briefcases and purses already have relatively thick padded handles.

There exists a need in the art for improved methods of making polymeric articles.

Summary of the invention

In one embodiment the invention relates to a method of molding an article. The method comprises: selecting a first mold part comprising an upper surface comprising a recessed area comprising a plurality of mold units disposed therein; disposing a barrier layer on the upper surface of the mold, the The barrier layer comprises a thermoplastic elastomer (TPE) material; dispensing a first portion of a polymeric gel precursor onto the barrier layer; placing a stabilizing layer on the polymeric gel precursor and forming between the gel precursor and the stabilizing layer interface; when pressure is applied to a stabilizing layer adjacent to the interface, advancing the interface until the gel precursor is covered by the stabilizing layer; closing the mold; forming a polymeric gel from the gel precursor; and removing the sheet, the sheet Consists of a plurality of moldings interconnected by polymeric gels. The method may include releasing the molded article from the sheet. The method may also include disposing a fabric layer on the barrier layer prior to dispensing the first portion of the polymerized gel precursor. The method may also include, prior to placing the barrier layer, disposing a fabric layer on the first partial gel precursor; disposing a fabric layer on the first partial gel precursor, and disposing a second partial gel precursor on the fabric layer. Adhesive material may also be arranged on the stabilizing layer and/or the fabric layer. The polymeric layer and the stabilizing layer may have respective cohesive strengths, and the cohesive strength of the stabilizing layer is less than the cohesive strength of the polymeric layer. The barrier layer may comprise a support layer, and the barrier layer may be disposed on the mold in such a manner that the support layer is adjacent to the upper surface of the mold. The barrier layer and/or the stabilization layer may comprise opposing surfaces, the release agent being able to be disposed on one or both of the opposing surfaces. The release agent can be disposed on the surface of the barrier and/or stabilization layer adjacent to the gel precursor.

Another embodiment relates to an article formed by the aforementioned method.

Another embodiment relates to methods of using such articles, and may include manually removing the stabilizing membrane from the article and adhering the polymeric gel to the surface.

Another embodiment relates to shoe inserts. The insole may comprise: a thermoplastic elastomer (TPE) barrier layer; a polymeric gel layer having a hardness of about 30 Shore 000 to about 75 Shore 00; adjacent to the polymeric gel layer and opposite the barrier layer Arrangement of stable layers. The TPE may be selected from thermoplastic polyurethane (TPU), silicone, and combinations comprising at least one of the foregoing. The barrier layer can comprise a support layer, and the TPE can be disposed on the support layer, adjacent to the polymeric gel. A release agent may be disposed between the polymeric gel and the stabilization layer. The release agent may be placed on the surface of the stabilization layer adjacent to the polymeric gel layer. The polymeric gel layer may comprise thermoplastic polyurethane. Active agents may be placed in the barrier layer, said active agents may be selected from the group consisting of: silver, tolnafate, undecylenic acid, allylamines, chlorine, copper, sodium bicarbonate, sodium omadine omadine), zinc omadine, azoles, and combinations comprising at least one of the foregoing. The polymeric gel may have sufficient adhesive strength to adhere to the inner surface of the shoe.

In another embodiment, the insole comprises: a thermoplastic elastomeric barrier layer comprising an active agent; a polymeric gel layer; a stabilization layer disposed adjacent to the polymeric gel layer and opposite the barrier layer. The active agent can be selected from silver, tolnaftate, undecylenic acid, allylamines, chlorine, copper, sodium bicarbonate, sodium omadine, zinc omadine, pyrroles, and at least one of the aforementioned combination of substances. The TPE may be selected from thermoplastic polyurethane (TPU), silicone, and combinations comprising at least one of the foregoing. The barrier layer can comprise a support layer, and the TPE can be disposed on the support layer, adjacent to the polymeric gel. The polymeric gel layer has a hardness of about 30 Shore 000 to about 75 Shore 00. A release agent can be placed between the polymeric gel and the stabilizing layer. A release agent may be placed on the surface of the stabilization layer adjacent to the polymeric gel layer. The polymeric gel layer may comprise thermoplastic polyurethane. The polymeric gel may have sufficient adhesive strength to adhere to the inner surface of the shoe.

The above described and other features are exemplified by the following figures and detailed description.

Description of drawings

Referring now to the drawings, which are exemplary embodiments in which like elements have the same numbering:

Figure 1 is a perspective view of an exemplary mold that can be used in the method according to the invention;

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

Fig. 3 is a schematic cross-sectional view of the mold shown in Fig. 1 passing through 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 the gel precursor to the barrier layer shown in Figure 4;

Figure 6 shows the application of a stabilization layer to the gel precursor shown in Figure 5;

Figure 7 shows a method for advancing the stable layer on the gel precursor shown in Figures 5 and 6;

Figure 8 shows covering the gel precursor with a stabilizing layer;

Figure 9 shows the mold being closed;

Figure 10 shows the closed mold and polymerization of the gel precursor;

Figure 11 shows the sheet of material comprising the molded unit after removal from the mould;

Figure 12 is a top view of an exemplary heel pad;

Figure 13 is a cross-sectional view of the heel pad of Figure 12 through line 13-13;

14 is a cross-sectional view of the heel pad of FIG. 12 through line 13-13 showing peeling of the stabilization layer from the adhesive layer;

Figure 15 is a top view of an exemplary rigid toothbrush handle having a polymeric gel handle pad according to the present invention, which will be shown in section;

Figure 16 is a cross-sectional view of the handle pad of Figure 15;

Figure 17 is a cross-sectional view of the handle pad of Figure 15 showing the peeling of the stabilization layer from the polymeric gel;

Figure 18 is a cross-sectional view of the hard toothbrush handle through line 18-18 showing the polymeric gel liner adhered to the hard handle recess;

Figure 19 is a cross-sectional view of an alternative toothbrush handle pad including flanges;

Figure 20 is a cross-sectional view of the handle of the hard toothbrush shown in Figure 15 showing the flange of the polymeric gel liner positioned in the recess of the hard handle.

Detailed description of the invention

The present invention relates to methods of making polymeric articles and articles made therefrom, and more particularly to methods of making relatively low durometer polymeric articles. Relatively low durometer polymeric materials can be very viscous, making them difficult or impossible to use in commercial processing techniques such as injection molding because the material will stick to the mold. Additionally, such materials have relatively low durability compared to other materials including other polymeric materials. Therefore, despite the favorable flexibility and softness properties of relatively low hardness polymeric gel materials, their applications are limited.

Figures 1-11, when taken together, represent an exemplary method of forming a polymeric gel article. The method includes selecting an appropriate mold 10 for a desired product, which may include opposing upper and lower surfaces 12,14 as shown in Figures 1-3. As shown, mold 10 may include a recessed region 16 defined in upper surface 12 of the mold that is recessed from upper surface 12 to a depth "D ₁ ". It should be understood that the terms "bottom" and "top" and/or "upper" and "lower" used herein, unless otherwise specified, are for convenience of description only and are not limited to any one position or spatial orientation. Moreover, it should be understood that the terms "first", "second", etc. herein do not denote any order, quantity, or importance, but are used to distinguish one element from another, and the terms herein "One" does not indicate a limitation on the number, but rather indicates that there is at least one of the mentioned items. Also, unless defined otherwise, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

Said mold 10 comprises 36 individual mold units 18 defined in recessed areas 16, each mold unit corresponding to the shape and size of the desired final molded article 19, in this case a heel pad. Although illustrated here in terms of a heel pad for convenience, it should be understood that a variety of products may be molded using this method. Each of the 36 individual mold units 18 is recessed from the upper surface 12 to a depth “D ₂ ”, which corresponds to the desired thickness of the final molded article 19 .

The mold 10 may also include a gasket groove 21 disposed between the recessed area 16 and the perimeter "P" of the mold 10, into which the gasket 20 can be placed. Alternatively, the gasket 20 may be placed directly on the upper surface 12 of the mold 10 . Gasket 20 may provide a seal sufficient to limit polymer flow from mold 10 . The gasket 20 or the mold 10 may contain periodic openings 22 to allow air trapped in the molding process to escape from the mold 10 . For example, gasket 20 can include opening 22 as shown. Optionally, mold 10 can include one or more registration guides 24 .

As shown in FIG. 4 , after selecting a suitable mold 10 , the method may include placing a barrier layer 26 on the mold 10 . The barrier layer 24 can be placed on the mold 10 as a sheet-like mass, or applied directly to the mold as a coating. When applied as a sheet 24 , then the barrier layer 24 can be applied over the mold and in physical contact with the gasket 20 . When applied as a sheet, then barrier layer 26 may also contain alignment guides (not shown) corresponding to alignment guides 24 in mold 10 to aid in its alignment with mold 10 and subsequent layers. If the barrier layer 26 is not arranged as a sheet, it can be placed directly on the upper surface 12 of the mold 10 . A release coating may be used to assist in the release of the barrier layer 12 from the upper surface 12 of the mold 10, if desired.

As shown in FIG. 5 , after barrier layer 26 is placed on upper surface 12 of mold 10 , gel precursor 28 may be dispensed onto barrier layer 26 . Gel precursor 28 may be placed on barrier layer 26 using a variety of techniques such as, but not limited to, casting, injection, and/or the like.

Dispensing the gel precursor 28 can include pouring a sufficient amount of the gel precursor to fill each of the 36 individual mold units 18 rather than filling individual mold units 18 as in other methods such as injection molding. For example, other methods such as injection molding may include dispensing gel precursor 28 into each mold unit 18 individually. Therefore, using this mold requires 36 separate dispensing steps. In contrast, the present method may include dispensing gel precursor 28 onto barrier layer 26 only once, and the separate dispensing of gel precursor 28 can provide sufficient amount of gel precursor 28 to form in a single molding cycle. All die units 18. The present method can substantially reduce manufacturing time compared to other methods by dispensing the gel precursor 28 in bulk rather than individually.

As shown in FIG. 6, after dispensing the gel precursor 28 onto the barrier layer 26, the stabilizing layer 30 may be placed on the gel precursor 28, eg, as a sheet. If the mold 10 includes alignment guides 24, the stabilizing layer 30 may also include corresponding alignment guides (not shown) to aid in its alignment with the mold 10 and any subsequent layers. Disposing the stabilizing layer 30 onto the gel precursor may comprise disposing a portion of the stabilizing layer 30 onto a portion of the gel precursor 28 such that an interface 32 exists between the gel precursor 28 and the stabilizing layer 30 . The placement of the stabilization layer 30 on the gel precursor 28 can be done manually by using a tool such as a roller, as shown in Figure 7, or the process can be automated. By applying pressure to the stabilizing layer 30 behind the interface 32, the remaining portion of the stabilizing layer 30 can be advanced over the remaining portion of the gel precursor 28, and the interface 32 is advanced until the stabilizing layer 30 covers all of the gel precursor 28 , as shown in Figure 8. The application of pressure substantially minimizes the formation of air bubbles between the gel precursor 28 and the stabilizing layer 30 while advancing the stabilizing layer 30 .

As shown in FIG. 9 , for example, the mold can be closed by arranging a mold cover 10 a on the stabilization layer 30 . When the mold 10 is closed, the gel precursor 28 can flow into all areas of the mold 10 defined by the gasket 22 and any trapped air can flow out of the mold through the gasket opening 21 .

As shown in FIG. 10, gel precursor 28 may be allowed to form polymeric gel 29 in closed mold 10 for a predetermined period of time (eg, 30 seconds to 5 minutes). If necessary, pressure and/or vacuum can be applied to the mold for various reasons, such as to speed up processing; to improve the quality of the final material; to modify the surface properties of the polymerized gel, etc. As a result, the present method can substantially reduce the total processing time for producing a plurality of molded articles 19 compared to other methods such as injection molding. Additionally, since the time for dispensing the gel precursor 28 is reduced compared to other methods, it is possible to increase the curing speed by varying factors such as pressure, temperature, catalyst concentration (when used), etc. The use of pressure and/or vacuum during the forming process is desirable when the article to be formed requires more definition, such as undercuts and the like. When vacuum forming or thermoforming is used, it is desirable to utilize a mold formed at least in part from the porous composite material, which allows complex patterns and surface patterns to be formed in the molded article and eliminates the need for vent holes in the mold. An example of such a porous composite material is gas permeable aluminum, which is commercially available under the trade name METAPOR ^™ .

After curing, the mold 10 can be opened and the sheet 32 comprising the molding 19 can be removed from the mold 10, as shown in FIG. 11 . The presence of the barrier layer 26 and the stabilizing layer 30 can facilitate the handling of the sheet 32 because the polymeric gel 29 is sealed by the layers 26, 30, which can facilitate sealing when the polymeric gel 29 has adhesive properties, but this This will allow it to adhere to surfaces such as mold surfaces, the user's hand, and the like. Sheet 32 comprises a plurality of relatively thin regions 29a of polymeric gel 29 located between barrier layer 26 and stabilization layer 30 and interconnected with molding 19 . Region 29 of polymerized gel may comprise a thickness "T ₁ " corresponding to depth "D ₁ " of recessed region 16 of mold 10 . In order to reduce waste, the depth D ₁ of the recessed area 16 can be chosen to be as small as possible while still allowing unrestricted flow of the gel precursor 28 into the area defined by the gasket 22 . Thus, depth D ₁ and thickness "T ₁ " can vary.

Molded articles 19 may be separated from sheet 32 and from each other by cutting (eg, die cutting, etc.) through barrier layer 26 , polymeric gel region 29 a and stabilization layer 30 . Molded article 19 may be die cut between and/or via polymeric gel regions 29 and 29a. When the polymeric gel 29 has adhesive properties, it is desirable to die cut through a portion of the polymeric gel region 29 adjacent to the polymeric gel region 29a so that the side surface of the molded element 19 contains the polymeric gel exposed areas. The presence of stabilizing layer 30 prevents or minimizes shrinkage of polymeric gel 29 and barrier layer 26 during die cutting, thereby substantially maintaining the dimensions of molded article 19 compared to the dimensions of mold unit 18 . Since shrinkage of the molded article 19 can be minimized, shrinkage factors do not have to be factored into the mold design, as would otherwise be the case.

Optionally, layer 34 can be placed between any two of the aforementioned layers, for example between stabilization layer 30 and polymeric gel 29 and/or between polymeric gel 29 and barrier layer 26 . Also optionally, layer 34 may also be disposed in polymeric gel 29, for example by placing a first portion of gel precursor 28 over barrier layer 26; layer 34 is disposed on the first portion of gel precursor 28; A second portion of gel precursor 28 is disposed on layer 34 . Layer 34 may comprise a variety of materials including, but not limited to, paper, fabric, plastic film, etc., as well as composite materials and/or combinations comprising at least one of the foregoing. Layer 34 may also contain colours, graphics and/or indicia, including patterns. When layer 34 comprises a fabric layer, the fabric may be knitted, woven, nonwoven, synthetic, non-synthetic, and combinations comprising at least one of the foregoing. Arranging a fabric layer as layer 34 is advantageous because it traps and disperses air bubbles that would otherwise form in or between layers, resulting in a better appearance of the final molded article 19 . Also, when the other layers are formed from colorless and/or transparent materials, the colors, designs and/or indicia placed on layer 34 can propagate through them, which is desirable for aesthetic purposes, in Figure 15 does the best display.

Also optionally, layer 34 may be used in place of stabilization layer 30 . If layer 34 is used instead of stabilizing layer 30 , it can be applied in the same way as described above with respect to stabilizing layer 34 .

In some cases, it may be desirable to be able to adhere the molded article 19 to various surfaces. Thus, optionally, an adhesive (not shown) may be placed on one or more surfaces of the final molded article 19 . Also optionally, an adhesive may be placed and/or disposed on one or more surfaces of layers 26 , 28 , 30 and 34 . For example, referring to FIG. 11, an adhesive may be placed on face 30b, and the adhesive may be supported by a release layer and/or a support layer (not shown). Some possible adhesives may include pressure sensitive adhesives, thermoplastic adhesives, etc., as well as combinations comprising at least one of the foregoing. An example of such a material is product number 7026 available from 3M.

In some cases, polymeric gel 29 may have sufficient adhesive strength to be adhered to a surface in the absence of a separate adhesive. In this case, it is desirable that the stabilizing layer 30 can be manually peeled off from the polymeric gel 29 . Thus, optionally, the stabilizing layer 30 can comprise a release coating (not shown) such as silicone, which is placed on the surface 30a, which can assist manual peeling of the stabilizing layer 30 from the polymeric gel 29.

Various materials can be used in the aforementioned method to manufacture the aforementioned molded article 29 . Barrier layer 26 may comprise any material that provides: sufficient elasticity to resist tearing and/or stretching when a force is applied thereto; sufficient structural integrity to form a predetermined shape; and the ability to Withstand the environment in which it will be used without substantial degradation. The barrier layer 26 can also be selected for ease of handling of the polymeric gel layer, which in some cases can have adhesive properties. Thus, after molding, the barrier layer 26 can be selected to include a relatively non-stick surface and a relatively soft feel to the human body. Some possible materials for barrier layer 26 include polyolefins, polystyrene, PVC, latex rubber, and thermoplastic elastomers (TPEs), among others, as well as combinations comprising at least one of the foregoing. Some possible TPE materials include polyurethanes, silicones, etc., as well as combinations comprising at least one of the foregoing. Barrier layer 26 may comprise an elongation of about 100% to about 1500%, more specifically about 200% to about 1000%, still more specifically about 300% to about 700%. It should be understood that use of the modifier "about" with respect to a quantity is inclusive of the stated value and has the meaning dictated by the context (eg, includes the degree of error in measurement of the particular quantity).

Barrier layer 26 may be of any thickness. It has been found that, for practical purposes, thinner layers provide improved hand, while thicker layers provide enhanced durability. Therefore, to prevent punctures in the barrier layer 26, it is desirable to use the thinnest layer possible. When the polymeric layer 29 is tacky, piercing the barrier layer 26 can expose the tacky material of the underlying polymeric gel 29, making it difficult to handle. Barrier layer 26 may have a thickness of about 0.2 mils (hereinafter "mil") to about 5 mils, more specifically about 0.5 mils to about 3 mils, and still more specifically about 0.6 mils ~ about 2 mils.

As noted above, the barrier layer 26 may be applied as a single piece of material during the molding process. In sheet form, especially when the barrier layer is relatively thin, the insulation material can be very flexible and can wrinkle and/or fold very easily during handling, which is undesirable. Accordingly, the barrier layer 26 may also contain a support layer (not shown), which facilitates handling 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 barrier material coating and away from the upper surface 12, which can be removed prior to die cutting if desired or necessary. .

As also mentioned above, if the barrier layer 26 is not applied as a sheet, it may be applied as a coating of material during or after the forming process. If applied after the molding process, the barrier layer may be placed on the polymeric gel 28 after the mold unit 18 is formed, by painting, spraying, hand brushing, etc., for example. During the molding process, when the barrier layer 26 is not arranged as a sheet or as a coating, then the gel precursor 28 can be placed directly on the upper surface 12 of the mold 10 where it may be necessary to use Stripping agent.

The polymeric gel 29, 29a may comprise any polymeric material having sufficient structural integrity to form a predetermined shape, including foamed polymeric materials; sufficient softness and/or flexibility to provide comfort to the human body; and It can withstand the environment in which it will be used without substantial degradation. The polymeric material may comprise thermosetting polymeric materials, elastomeric polymeric materials, thermoplastic materials including thermoplastic elastomeric materials, and compositions comprising at least one of the foregoing materials. Some possible materials for the polymeric gel 29, 29a include polyurethane, silicone, etc., as well as combinations comprising at least one of the foregoing.

Formation of gel precursor 28 can be performed by a variety of methods known to those of ordinary skill in the art. For example, the formation of polyurethane gels may involve the reaction of suitable prepolymerized precursor materials, such as polyols and isocyanates, in the presence of a catalyst. In some embodiments, the polymeric gel 29, 29a can have sufficient adhesive strength to adhere to a selected surface (eg, the interior surface of a shoe). The adhesive strength of the polymeric gel 29, 29a can be varied by eg varying the hardness of the material used to form the layer. Additionally, the hardness of the polymeric gel 29, 29a may be selected to provide an article and/or region of the article with a predetermined hardness, making it suitable for particular shock absorbing and/or anti-wear applications.

The polymeric gel 29, 29a may have a hardness of about 0.01 Shore 00 to less than or equal to about 70 Shore A, more specifically less than 70 Shore 00, still more specifically less than 60 Shore 00. In some cases, the polymeric gel 29, 29a may need to have adhesive properties in order to preclude the use of a separate adhesive to adhere the molded element 29 to the desired surface. In this case, the polymeric gel may comprise a hardness of about 30 Shore 000 to about 85 Shore 000. Such relatively low hardness range polymeric gel materials can have a jelly-like consistency. One possible material with such adhesive properties is a polyurethane gel having a hardness of about 70 Shore 00 to about 85 Shore 00, which provides sufficient adhesive strength to adhere to a desired surface, such as a shoe. Inner surface or hard plastic surface like polypropylene. Polymeric gel 29 and/or barrier layer 26 may include one or more additives such as, but not limited to, modifiers, colorants, stabilizers, phase transfer materials, UV inhibitors, and/or active agents and at least one combination of the aforementioned substances. The concentration of additives can vary depending on the desired effect of the agent.

One possible phase transfer material may comprise phase transfer microspheres (available under the product name Outlast), which contain substances capable of changing phase states when approaching body temperature. Thus, thermal energy can be stored in the barrier, resulting in a product that can feel cold or hot.

Suitable active agents can comprise tolnaftate, undecylenic acid, allylamines, chlorine, copper, sodium bicarbonate, sodium omadine, zinc omadine, pyrroles, silver, etc., and at least one of the foregoing combination of substances. Silver, for example, can provide an antifungal/antibacterial effect. For reasons of economy and efficiency, when an active agent is used, it has been found to be advantageous to include the active agent in the barrier layer 26 . Since the barrier layer 26 is relatively thin compared to the polymeric gel 29, disposing such reagents in the barrier layer 26 allows a similar effective concentration to be achieved using a reduced total amount of reagents compared to a thicker layer, thereby reducing the need for The cost of additives. In addition, the placement of such agents in the barrier layer 26 ensures that the agents are placed in the outermost layer of the article, ie the body contact area, rather than in areas remote from the user, which can increase the effectiveness of the agent.

In some cases, it may be desirable to use a colorless material for each of the barrier layer, polymeric gel layer, and stabilization layer, for aesthetic reasons. For example, it may be desirable to use a colorless insole, especially in women's shoes, which are sometimes open-toed or open-heeled.

)下商业获得。稳定层30可以包含约0.2密耳～约10密耳的厚度，更具体的约0.5密耳～约5密耳，还更具体的约1密耳～约2密耳。Stabilizing layer 30 may comprise a material having properties capable of substantially minimizing shrinkage of barrier layer 26, gel precursor 28, and/or polymeric gel 29 during or after processing; 29 provides support; and can facilitate the handling of the polymeric gel 29 and barrier layer 26 . Stabilizing layer 30 may comprise any material that is substantially inelastic compared to polymeric gel 29 so as to provide dimensional stability to sheet 32 and/or molded article 19 during or after processing. Some possible materials for the stabilization layer 30 include, but are not limited to, fabric, paper, plastic (e.g., polyester, polyethylene, polyvinyl chloride (PVC), etc.), metal, metallized plastic, etc., and materials comprising at least one Combinations of the foregoing. One possible material is oriented polyester film, which is available from a variety of sources and under a variety of different product names (e.g.,

) under commercial acquisition. Stabilizing layer 30 may comprise a thickness of about 0.2 mil to about 10 mil, more specifically about 0.5 mil to about 5 mil, still more specifically about 1 mil to about 2 mil.

The aforementioned methods and materials can facilitate the manufacture of polymeric articles and/or parts of articles that are desirable for aesthetics and/or to minimize wear and/or friction. The method can be used to form polymeric articles and/or portions of articles comprising any size, thickness or geometry. The size, thickness, geometry, flexibility, and bond strength of the article and/or article sections may be selected to optimize its design conditions. Examples in which the aforementioned polymeric materials can be used for articles include, but are not limited to, personal care items such as handles for hairbrushes, toothbrushes, and razors; medical devices such as face masks, crutches, and plaster casts; household items such as handles for brooms; handles for luggage, Straps for backpacks, briefcases and purses; clothing such as cycling shorts, underwear and shoes; useful items such as mouse pads, keyboard pads; handles and/or straps for consumer goods such as bottles and/or cases, laundry detergent handles ;Sporting equipment and accessories such as racket handles, bat handles, fishing rod handles, guns, and bicycle handlebars. In addition, the article may comprise indicia such as labels with colours, patterns and/or designs, and the like.

12-14 illustrate an exemplary article, heel pad 40 (hereinafter "heel pad"), which may be formed using the methods and materials previously described. The heel pad 40 may include opposing upper and lower surfaces 40a, 40b. In this exemplary embodiment, heel pad 40 may comprise a thickness of about 1/8 inch. Barrier layer 30 may be disposed adjacent to polymeric gel layer 29 , and stabilization layer 30 may be disposed on the side of gel layer 29 opposite barrier layer 26 . Heel pad 40 may contain an antifungal agent disposed within barrier layer 26, if desired. In an exemplary embodiment, barrier layer 26 may contain an active agent, such as silver, to prevent and/or treat athlete's foot conditions. One possible barrier layer 26 comprising such an active agent is Vacuflex 18411, available from Omniflex, Inc.

In an exemplary embodiment, polymeric gel layer 29 may comprise sufficient adhesive strength to allow it to adhere to a surface, such as the interior surface of a shoe. Accordingly, stabilization layer 30 can optionally include a release coating (not shown), such as silicone, disposed on surface 30a, which can facilitate manual peeling of stabilization layer 30 from polymeric gel 29, thereby exposing The gel 29 is polymerized so that it adheres to the surface.

In another exemplary embodiment, an adhesive (not shown) may be placed on surface 40b of stabilization layer 30 such that heel pad 40 is adhered to a surface, such as the interior surface of a shoe. Such an option may be useful, for example, if stabilization layer 30 does not comprise a release coating on surface 30a.

Figures 15-18 illustrate another exemplary article, which is a generally stiff toothbrush handle 41 comprising a liner 42 (hereinafter "handle liner") that can be formed using the methods and materials previously described. The handle pad 42 includes an upper surface 42a opposite a lower surface 42b. The handle pad 42 may comprise a thickness of about 1/8 inch to 3/8 inch. In this exemplary embodiment, the handle pad 42 may comprise a barrier layer 26 disposed adjacent to the polymeric gel layer 29, a fabric layer 34 disposed on the side of the polymeric gel layer 29 opposite the barrier layer 26, and A stabilizing layer 30 is disposed adjacent to the fabric layer and opposite the gel layer 29 . In this exemplary embodiment, an adhesive may be disposed between fabric layer 34 and stabilization layer 30 . If desired, the handle pad 42 may contain an antifungal agent disposed in the barrier layer 26, as in the previous embodiments. As shown in Figure 18, the handle pad can be placed in the generally stiffer toothbrush handle 41 .

Figures 19-20 illustrate another exemplary article, which is a toothbrush handle 41' that includes a slot for receiving a raised portion of the handle pad. The handle pad 42' comprises the same material as the previous embodiment and additionally comprises a flange 42a disposed around the pad. As in the previous embodiments, the handle 41 may include a recess (not shown) configured to receive the handle pad 42, including a groove (not shown) for receiving the flange 42a. Placing the handle pad 42 into the toothbrush handle 41 may include placing the flange 42a into the groove and the body portion into the recess. If further protection of the handle pad 41 is desired, the stabilizing layer 30 can be peeled off from the fabric layer 34 and the handle pad 42 can be placed in the recess and adhered in the recess using an adhesive, as shown in FIG. 20 .

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

Example

Example 1

Formation of colorless, transparent self-adhesive heel pads for shoes

Choose to use a metal mold limited to 36 heel pads. The mold contained a recessed area of about 0.020", and the perimeter of the mold edge and the recessed area were spaced apart with gaskets. Each of the 36 mold units measured about 4 inches by about 1/2 inch, and the The depth of the above mold unit is the same.

The mold was preheated to about 150°F, and the barrier layer was placed as a sheet on the upper surface of the mold. The barrier layer is Vacuflex 18411 (available from Omniflex, Inc.), which is a colorless, clear polyurethane film about 0.75 mil thick with an elongation of about 400% to about 500% supported at a thickness of about 1.5 mil. mil polyethylene support layer. The barrier layer was placed on the upper surface of the mold so that the polyethylene layer faced the mold and the polyurethane film avoided the mold.

Approximately 243 grams (gm) of the gel precursor was prepared and manually poured over the barrier layer. The gel precursor was a thermoset polyurethane gel system, WE369-1 from Isotec International, and was prepared using approximately 0.02 weight percent (wt %) based on the weight of the gel precursor. No pigment was added to the gel precursor.

A stabilizing film is disposed on a portion of the gel precursor. The stabilizing film was a piece of Hostaphan 2000 2SLK (available from Mitsubishi), which is a polyester film with a silicone release agent on one surface. The thickness of the film was about 2 mils. A stabilizing film is disposed on the gel precursor such that the surface of the film coated with the silicone release agent is in contact with the gel precursor. Applying manual pressure to the stabilizing membrane located behind the interface between the gel precursor and the stabilizing membrane advances the stabilizing membrane over the gel precursor until the entire surface of the gel precursor is covered by the stabilizing membrane.

The mold is closed and pressurized to about 25 pounds per square inch (psi). After about 4 minutes, the mold was opened and the colorless, clear sheet containing 36 molded heel pads was manually removed from the mold. The sheet can be manually removed from the mold without sticking to the mold surface or the operator's hands.

The polyethylene support/carrier layer for the barrier layer was removed and the sheet was die cut along the perimeter of each of the 36 heel pads. The sheet was able to be die cut without sticking to the die cutting machine as a result of the stability provided by the polyester layer and barrier layer. The molded heel pad is then removed from the sheet.

Each molded, die-cut heel pad measures approximately 4 inches by 1.3 inches. The molded insole is pliable, flexible, colorless and transparent, and it shows little shrinkage compared to the individual heel pad mold dimensions.

To apply the heel pad to the interior of the shoe, the polyester layer was manually removed from the heel pad, thus exposing the underlying polyurethane gel. The polyurethane gel lays out against the inside of the shoe. The polyurethane gel is very tacky, enabling it to adhere to the inner surface of the heel of a shoe in the absence of a separate or added adhesive. The heel pad does not adhere to the user's foot due to the presence of the barrier layer, which provides a smooth surface against the user's heel. Polyurethane gels are very soft and flexible, and the polyurethane barrier bends with the movement of the gel. Since the heel pad is colorless and transparent, it is invisible to the casual observer.

Example 2

Formation of a colorless, transparent self-adhesive heel strap insert for women's slingback shoes

It was chosen to use a metal mold containing 140 mold units, each unit used to define the heel strap pad. The mold contained a recessed area of about 0.020", and the perimeter of the mold edge and the recessed area were spaced apart by gaskets. Each of the 140 mold units measured about 3.0 inches by about 0.3125 inches. In this example The materials and methods used in are the same as those used in Example 1.

Each molded, die-cut heel strap insert measures about 3.01 inches by about 0.3225 inches. Thus, the molded heel strap pad exhibits little shrinkage compared to the individual heel strap pad mold dimensions. The molded heel strap insert is bendable, flexible, colorless and transparent. The polyester layer is manually removed from the heel strap insert, exposing the underlying polyurethane gel, which is very tacky, allowing it to adhere to the slingback shoe in the absence of a separate or added adhesive inner surface of the belt. The heel pad does not adhere to the user's foot due to the presence of the barrier layer, which provides a smooth surface against the user's heel. The polyurethane gel is very soft and flexible, and the barrier bends with the movement of the gel. Since the heel pad is transparent, it is invisible to casual observers.

Example 3

Formation of colored, self-adhesive liners for rigid toothbrush handles

Choose to use a metal mold limited to 50 toothbrush handle pads. The mold contained a recessed area of approximately 0.020", and the perimeter of the mold edge and the recessed area were spaced apart by spacers. The dimensions of each of the 50 mold units were as follows: approximately 4 inches long by approximately 1 /8 inch to about 3/8 inch. The depth of the mold unit is about 1/8 inch to about 3/8 inch. In addition to adding about 0.4wt% chemical dye (available from Pat Products' Blue TR Repliplast to the gel precursor) 67798), the materials and methods used in this example are the same as those used in Example 1.

Each molded, die-cut toothbrush handle measures about 4.25 inches by about 0.625 inches.

The resulting single molded toothbrush handle pad was a blue, transparent, pliable and flexible mass that showed little shrinkage compared to the dimensions of the individual toothbrush handle mold units.

The Hostaphan polyester film was manually removed from the toothbrush handle pad, thereby exposing the underlying blue polyurethane gel. Polyurethane gel is so sticky that it can adhere to recessed areas of hard toothbrush handles in the absence of a separate or added adhesive. The blue handle pad meets the user's aesthetic requirements.

The pad portion of the handle is thicker than the depth of the recessed area on the hard portion of the toothbrush handle. Therefore, the handle pad portion is elevated relative to the hard handle surface. Polyurethane gels are very soft and flexible, and the barrier bends as the gel moves. The surface of the polyurethane release film provides a smooth surface for the user's hand. Antifungal/antimicrobial agents in polyurethane barrier films provide protection against bacterial/fungal growth in high humidity bathroom environments.

Example 4

Formation of colored, patterned self-adhesive liners for rigid toothbrush handles

The mold and material used in this example are the same as those used in Example 3. After placing the gel precursor on the barrier layer, the fabric layer is placed as a sheet on a portion of the gel precursor. The fabrics come in a variety of colors and patterns. Manual pressure is applied to the fabric layer behind the interface of the gel precursor and fabric layer, at which point the fabric layer advances over the remaining exposed gel precursor until the fabric layer covers the entire gel precursor surface.

A pressure sensitive adhesive is placed on the fabric layer. The pressure sensitive adhesive is product number 950 from 3M.

Place a piece of Hostaphan 2000 2SLK Stabilizing Film over the pressure sensitive adhesive, allowing the silicone release agent to contact the pressure sensitive adhesive.

The mold is closed and pressurized to about 25 pounds per square inch (psi). After about 4 minutes, the mold was opened and the patterned piece containing the molded toothbrush handle pad was manually removed from the mold and die cut as in the previous examples.

The toothbrush handle pad is a pliable and flexible substance that exhibits little shrinkage compared to the dimensions of the individual toothbrush handle mold units.

The Hostaphan polyester film was manually removed from the toothbrush handle pad, exposing the underlying pressure sensitive adhesive placed on the fabric layer, and thus the handle pad was adhered to the recessed area of the hard toothbrush handle. The pattern of the fabric can be seen through the Isotec Gel and Vacuflex membrane, thus meeting the user's aesthetic requirements.

The method of the present disclosure can comprise one or more of the following advantages: 1) The use of a relatively thin barrier and release layer on the side opposite the polymeric gel layer allows relatively low durometer polymeric materials to be produced in the forming device The device operator handles without sticking to the device and/or the operator; 2) the use of a relatively thin barrier layer reduces the total amount of additive used, which reduces cost; 3) the relatively thin barrier layer Use enables relatively low durometer polymeric materials to be molded into a variety of shapes, sizes, opacities and to form articles with cross-sections of varying sizes, shapes and opacities; 4) reduced use of stabilizing layers and/or Or eliminate the shrinkage of gel precursors, polymeric gels and/or barrier layers during or after processing; 5) When using polyurethane gels, this method can provide colorless, transparent articles rather than as usual Polyurethane turns yellow after exposure to UV energy.

While the disclosure has been described with reference to exemplary embodiments, it will be understood that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the disclosure by those skilled in the art. In addition, various modifications may be made in light of the teachings of the invention and a particular situation or material without departing from the essential scope thereof. Therefore, it is intended that this summary not be limited to carrying out the particular embodiment disclosed herein as the best mode contemplated, but that this summary will include all embodiments falling within the scope of the appended claims.

Claims (29)

1. the method for a molded products, it comprises:

Selection comprises first mold of upper surface, and described upper surface comprises recessed region, and described recessed region comprises a plurality of die units that are placed in one;

The barrier layer is placed on the upper surface of mould, described barrier layer comprises thermoplastic elastomer (TPE) (TPE) material;

The first of polymeric gel precursor is assigned on the described barrier layer;

Stabilized zone is placed on the described polymeric gel precursor, and between described gel precursors and described stabilized zone, form the interface;

When the stabilized zone adjacent with described interface exerted pressure, making the reach of described interface, covered by described stabilized zone until described gel precursors;

Closed mould;

Form polymeric gel by described gel precursors; And

Taking-up comprises the sheet by the interconnective a plurality of mechanograph of polymeric gel layer.

2. the method for claim 1, it comprises: peel off described mechanograph from described.

3. the method for claim 1, it comprises: before the first that distributes described polymeric gel precursor, tissue layer is placed on the barrier layer.

4. the method for claim 1, it comprises:

Before arranging stabilized zone, tissue layer is placed in the first of described gel precursors;

Tissue layer is placed in the first of described gel precursors; And

The second portion of gel precursors is placed on the described tissue layer.

5. method as claimed in claim 4, it comprises: adhesive material is placed on stabilized zone and/or the tissue layer.

6. the method for claim 1, wherein said polymer layer and described stabilized zone have bonding strength separately, and the bonding strength of described stabilized zone is less than the bonding strength of described polymer layer.

7. the method for claim 1, wherein said barrier layer comprises supporting layer, and described method comprises: the mode adjacent with the mould upper surface with supporting layer places described barrier layer on the described mould.

8. the method for claim 1, wherein said barrier layer and/or described stabilized zone comprise the apparent surface, and remover are placed on one or two surface of described apparent surface.

9. the method for claim 1, it comprises: described remover is placed on the surface of barrier layer adjacent with described gel precursors and/or stabilized zone.

10. goods that form by the method for claim 1.

11. a method of using the goods of claim 10 comprises: stabilising membrane is manually removed from goods, and polymeric gel is adhered to the surface.

12. a shoe-pad, it comprises:

Thermoplastic elastomer (TPE) (TPE) barrier layer;

Hardness is the polymeric gel layer of about 30 Shores 000～about 75 Shores 00; And

Be arranged as adjacent with described polymeric gel layer and relative stabilized zone with described barrier layer.

13. shoe-pad as claimed in claim 12, wherein said TPE is selected from: thermoplastic polyurethane (TPU), organosilicon and the combination that comprises at least a aforementioned substances.

14. shoe-pad as claimed in claim 12, wherein said barrier layer comprises supporting layer, and described TPE is placed on the described supporting layer and is adjacent with polymeric gel.

15. shoe-pad as claimed in claim 12, it comprises the remover that places between polymeric gel layer and the stabilized zone.

16. shoe-pad as claimed in claim 15, wherein said remover are placed on the surface of the stabilized zone adjacent with the polymeric gel layer.

17. shoe-pad as claimed in claim 12, wherein said polymeric gel layer comprises thermoplastic polyurethane.

18. shoe-pad as claimed in claim 12 also comprises the activating agent that places the barrier layer.

19. shoe-pad as claimed in claim 18, wherein said activating agent is selected from: silver, Tolnaftate, undecenoic acid, propylamine, chlorine, copper, sodium acid carbonate, sodium omadine, Ao Maiding zinc, pyroles and comprise the combination of at least a aforementioned substances.

20. shoe-pad as claimed in claim 12, wherein said polymeric gel has the bonding strength that is enough to adhere to the shoes inner surface.

21. a shoe-pad, it comprises:

Thermoplastic elastomer barrier layer, described barrier layer comprises activating agent;

The polymeric gel layer; And

Be arranged as adjacent with described polymeric gel layer and relative stabilized zone with described barrier layer.

22. shoe-pad as claimed in claim 21, wherein said activating agent is selected from: silver, Tolnaftate, undecenoic acid, propylamine, chlorine, copper, sodium acid carbonate, sodium omadine, Ao Maiding zinc, pyroles and comprise the combination of at least a aforementioned substances.

23. shoe-pad as claimed in claim 21, wherein said TPE is selected from: thermoplastic polyurethane (TPU), organosilicon and the combination that comprises at least a aforementioned substances.

24. shoe-pad as claimed in claim 21, wherein said barrier layer comprises supporting layer, and described TPE is placed on the described supporting layer, and is adjacent with polymeric gel.

25. shoe-pad as claimed in claim 21, wherein said polymeric gel layer have the hardness of about 30 Shores 000～about 75 Shores 00.

26. shoe-pad as claimed in claim 21, wherein said remover is placed between polymeric gel and the stabilized zone.

27. shoe-pad as claimed in claim 21, wherein said remover are placed on the surface of the stabilized zone adjacent with the polymeric gel layer.

28. shoe-pad as claimed in claim 21, wherein said polymeric gel layer comprises thermoplastic polyurethane.

29. shoe-pad as claimed in claim 21, wherein said polymeric gel has the bonding strength that is enough to adhere to the shoes inner surface.

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