Abstract:
The present invention relates to a process and composition for stiffening materials for use in the manufacturing of footwear using a combination of stiffeners and adhesives.

Description:
[0001]     This application is a continuation-in-part application of U.S. patent application Ser. No. 11/159,688, which claims priority on U.S. Provisional Patent Appl. No. 60/584,519, filed Jul. 1, 2004 and U.S. Provisional Patent Appl. No. 60/640,947, filed Dec. 30, 2004. 
     
    
     BACKGROUND OF THE INVENTION  
       [0002]     1. Field of the Invention  
         [0003]     The invention relates to stiffeners, such as the stiffeners used in the manufacture of shoes to retain the shape of heel and toe portions of the footwear.  
         [0004]     2. Description of the Related Art  
         [0005]     There are a number of different types of stiffeners used in the shoe industry. U.S. Pat. Nos. 3,523,103; 3,590,411; 3,647,616; 3,891,785; 3,973,285; 4,814,037; 6,391,380 and 6,475,619 disclose methods and materials for improving the stiffness and adhesive qualities of materials for use in the footwear industry (all of which are incorporated by referenced). The stiffening plastic resins are selected from styrene butadiene, polystyrene, polyvinylacetate, acrylic as well as other polymer lattices that may be saturated into a needle punch non woven fabric. Some of these types of stiffeners have hot melt adhesives coated onto their surfaces and are heat activated to bond to the shoe upper and lining. Some are activated with solvents and do not have heat activated hot melt adhesives. A second group of stiffeners are premolded materials made from polyvinylchloride, ionomers or thermoplastic rubbers (TPR). These premolded stiffeners require an adhesive to be painted on the surface for bonding to the shoe components. There are stiffeners that are made via extrusion of a resin such as an ionomer or other thermoplastic polymers and then require an extrusion coating of an adhesive onto the polymer sheet. The last category comprises stiffeners that are made from powders that are admixtures of a filler or hard material with an adhesive or softer material. These polymer powder blends are then heat sintered to produce a stiffener.  
         [0006]     The ideal characteristic of the stiffener is to have high resiliency and good stiffness for a given weight of material. The saturated stiffeners can be made stiff but usually the stiffer grades do not have high resiliency. The saturated stiffeners, the premolded stiffeners and the extruded stiffeners all require an extra processing step to have an adhesive applied to the surface. The powder coated stiffeners usually involve a need for cryogrinding to be able to create a fine powder from a low melting point adhesive which results in added costs as well as a need for a critical particle size distribution. The powder coated materials, since they are sintered, are also less tough or strong and need extra weight for a given level of stiffness since the sintering action does not form a true melt of the material to maximize the physical properties. These materials also need high levels of the adhesive component in order to get good bonding to the various substrates that they will be attached to. This adds additional cost and additional weight. When hot melting the saturated materials or the extruded materials they need a significant amount of hot melt adhesive to be coated onto their surfaces in a separate step.  
         [0007]     There are processes and products that are used in the packaging industry where a tie layer of adhesive is added to another resin to produce a very thin layer to bond these various layers together. Usually this is done with adhesive tie layers in which the adhesive component is similar in melt viscosity and melting point to the other layers. The process to produce these materials is an extrusion process that uses multiple extruders and either a multicomponent die block or a manifold die.  
         [0008]     Additionally, there are processes and products that are used in the shoe industry and other industries where a stiffener is used and requires a fabric on one or two sides. The fabric can be used to add stability to the stiffener during the molding cycle and to also act as a protector in some cases where there may be stitching in the back seam area to prevent the stitching from penetrating and weakening the stiffener. A fabric backing can also be used if the end user needs to apply a latex cement or if the end user wants the fabric to be used as a lining. The fabric can be a woven material, a polyester, cotton, blends or a non-woven material of polyester. In many cases when a woven fabric is used one would like the core material to have an adhesive characteristic so when the laminate is heated and molded the adhesive will penetrate the fabric and bond the laminate to the leather outer material of the shoe and the lining of the shoe. Furthermore, there is an advantage in having the adhesive activate at a low temperature so that the leather is not burnt by too high a molding temperature.  
       SUMMARY OF THE INVENTION  
       [0009]     The present invention overcomes a number of the deficiencies listed above. The present invention uses a combination of a stiffening plastic resin such as polymers of polyethylene terephthalate glycol (PETG) copolyester and low melting point plastic adhesive resins such as polycaprolactone, to form a polymer sheet stiffener that has both stiffening properties and adhesive properties in one step. PETG is a saturated, thermoplastic, polyester resin made by condensing ethylene glycol and terephthalic acid. A preferred PETG is available from Eastman Chemical and is sold under the product name EASTAR PETG. The polymers of PETG copolyester and polycaprolactone may be combined in various manners to obtain the desired stiffening and adhesive properties.  
         [0010]     Additional stiffening plastic resins are known in the art, examples are styrene resins, styrene-butadiene resins, vinyl acetate resins, vinyl chloride resins, acrylic resins, extruded thermoplastic or powder coated thermoplastic materials which may be selected from the group consisting of polyvinyl chloride, ionomers, high, medium or low density polyethylene, polypropylene, polyesters, polystyrene and copolymers and compatible blends of such polymers. Examples of commercially available stiffeners are PETG, PET and copolyesters, such as, but not limited to, GP001 polyester, all of which are available from Eastman Chemicals.  
         [0011]     GP001 is a copolyester with a vicat softening temperature of 74° C. and a glass transition temperature of 75° C. The GP001 has an inherent viscosity of 0.7 At a thickness of 10 mils, a film of GP001 copolyester exhibited a density of 1.30 g/m 3 , an Elmendorf tear resistance of 7.5 N (M.D. and T.D.), a PPT tear resistance of 61 (M.D.) and 66 N (T.D.), a tensile strength at break of 53 Mpa (7600 psi at M.D. and T.D.), a tensile modulus of (M.D.) 1570 Mpa (2.3×10 5  psi) and (T.D.) 1560 (2.3×10 5  psi), a dart impact at 23° C. of 355 g, an elongation at break of 5% (M.D. and T.D.), a Tear Propagation Resistance, Split Tear Method (at 254 mm/min) (M.D. and T.D.) of 15.7N. The GP001 Mechanical properties for injection molding are as follows, tensile stress at break of 3200 psi, tensile stress at yield of 7400 psi, and elongation at break of 184%, a tensile modulus of 3.3×10 5  psi, a flexural yield strength of 10600 psi.  
         [0012]     Polycaprolactone has good water, oil, solvent and chlorine resistance. It has a low melting-point (58-60° C.) and low viscosity, and it is easy to process. Additional low melting point plastic adhesive resins, such as plastic resins with a melting point below 85° C. can also be employed in the present invention. An additional low melting point plastic adhesive resin is ethylene methyl acrylate copolymer, sold commercially as 2260 EMAC by Eastman Chemicals. 2260 EMAC has a melting point of 76° C.  
         [0013]     EMAC 2260 is ethylene methyl acrylate copolymer with a melt index of 2.1 g/10 min., a density of 944 kg/m 3 , a vicat softening temperature of 50° C., a brittleness temperature of &lt;−73° C., a durometer hardness (Shore D Scale) of 37, a methyl acrylate content of 24%, a tensile stress at break (500 mm/min) of 11 Mpa, and an elongation at break (500 mm/min) of 835%, and a melting point of 76-77° C.  
         [0014]     The stiffener may be evaluated to determine the adhesive bonding strength of the finished product by die cutting a piece of the stiffener to be tested and inserting the stiffener between two pieces of a non-woven lining material that is a 35% poly ester blend having a thickness of 0.029 inches. The three pieces are held together and placed into a back part heel counter molding machine with the female mold at 180° F. and the male mold at 290° F. The mold is closed and held in position for 17 seconds. The mold is opened and the laminate is placed, at room temperature, in a laminate cooling station having the desired shape of the final product. The shaped heel counter is now rigid and the stiffener is bonded to the two pieces of non-woven lining material. The adhesive test requires that the three part laminate remain bonded together when manual pressure is applied to pull the components apart. This determines if the stiffening material has good adhesive qualities. The resiliency test is based on making a thumb indent on the side of the heel counter and evaluating the degree with which the indent bounces back. An acceptable bounce is when the indent bounces back immediately with a “ping-pong” sound. This determines if the stiffening material is resilient.  
         [0015]     One process involves co-extruding with either a coextrusion block or a manifold die using polymers of PETG copolyester with adhesives such as polycaprolactone, to form a polymer sheet stiffener that has both stiffening properties and adhesive properties in one step. The uniqueness of the process and the material is that it allows for two materials of significantly different melting points and viscosity to form a sheet material in one step. These sheets can then be heat activated to form a bond with the shoe components when heated and molded and at the same time produce a stiff material depending on the ratio of the ingredients and their weight. The formulation produces a stiff material with high resiliency and toughness. The two unique characteristics of this product and process are the fact that they can coextrude and form an acceptable sheet from two highly different melt index and melting point materials. Additionally it is more cost effective to perform in one step what usually takes two steps and at the same time it is possible to use a smaller amount of the adhesive resin since it all sits on the two outer surfaces of the sheet. It is also possible to use regrind in place of virgin polymer.  
         [0016]     A second process involves mixing polymer blends of copolyester with adhesives, such as a polycaprolactone to form a dry mixture in a continuous mixer or an extruder. This results in a polymer sheet stiffener that has both stiffening properties and adhesive properties in a single step. The unique process and the material allows for two materials of significantly different melting points to form a homogeneous mix. These sheets can then be heat activated to form a bond with the shoe components when heated and molded and at the same time produce a stiff material depending on the ratio of the ingredients and their weight. The formulation produces a stiff material with high resiliency and toughness.  
         [0017]     The following is an additional process using a novel composition that will give the desired characteristics of stiffness and adhesive properties. The core material is made of a coextruded plastic matrix using Eastman Chemical Company&#39;s Copolyester GP001 and Dow Chemical Companies Tone 767 Polycaprolactone polymer with a melting point of 61° C. and a molecular weight greater than 42,000 daltons.  
         [0018]     This process for making a core material uses two extruders such that most of the adhesive properties of the core material will be on the surface. It is possible to use two extruders with a coextrusion block or to use a manifold die to the keep the outer layers of the core separated until they meet at the die. The fabric, which can be, but is not limited to PGI Difco 1.9 oz/yd 2  woven cotton Osnaburg, is then laminated at the nip of a set of calendar rolls where the die extrudate comes in contact with the nip areas of the rolls. Additionally, the fabric being fed into the area to be coated by the extruded melt is squeezed together by the calendar rolls. Various thicknesses can be achieved by adjusting the gap set between the rolls. The thickness will also influence the stiffness of the material. These characteristics are further described below in Examples 26-30 and Tables X-XV. 
     
    
     BRIEF DESCRIPTION OF THE DRAWINGS  
       [0019]      FIG. 1  is a cross sectional view of the stiffener material of the present invention in combination with two fabric materials according to Examples 26-30.  
     
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS  
       [0020]     The copolyester of the coextruded stiffener preferably is the Eastman Chemical Eastar 6763, which has a softening point of 85° C. (185° F.) and is usually extruded into a film at extrusion temperatures of 246-274° C. (475-525° F.). The adhesive preferably is a polycaprolactone and most preferably Dow Chemical Tone 767 (Tone) which has a melting point of 60° C. (140° F.) and a melt flow of 1.9 or Tone 787 with a melt index of 0.5. The melt index is determined via ASTM D1238-73, which is run at 80° C. and at 44 psi and measured in g/10 min. The PETG has a flex modulus of 300,000 psi and the Tone has a flex modulus of 63,000 psi. Therefore, the PETG is the component that adds stiffness to the material and varying its level will vary the level of stiffness. The Tone normally extrudes at 93-120° C. (200-250° F.). The uniqueness of the process and the product is the fact that these two materials are brought together in the die and they maintain their integral integrity. The Tone remains on the outer surfaces as an adhesive and the PETG forms the internal core to add the stiffness quality.  
         [0021]     While the two materials listed above are illustrated one is not limited to these materials and one could coextrude PET polyester as the core or iononmer and use the above adhesive, ethylene vinyl acetate adhesives, ethylene methacrylate adhesives or copolyesters.  
         [0022]     The below examples resulted in several novel discoveries. The manifold die works well forming an “ABA” structure wherein the adhesive is on both sides of the polymer stiffener. The PETG regrind does not need to be dried under environmental conditions 75° F. and less than 50% humidity. The Tone can run at higher temperatures without too much reduction in viscosity and still results in a good coating. The casting rolls can be run at a temperature of about 55° F. The use of higher temperatures at the die, the Tone feed pipes and the extruder reduces and/or eliminates the potential of score die lines. These lines come from the adhesive coating and not from the stiffener polymer. The use of a flex lip die and the 100 mesh screen pack help in giving a better surface and minimize contamination. A cast roll works well, but these rolls do not allow for gauge control. The gauge control occurs from the extruder speed and the die opening. There is a limitation on how much turn down one can get with a single die lip, and die modifications can be made to increase the turn down. Good bonds occurred with the Tone coating and the Tone coating stayed on the polymer surfaces even at higher temperatures. Good bonds occurred with the 90/10 PETG/Tone ratio even at lower weights where the Tone layers were less than 50 g/m 2 . PET regrind that is dried will also work on in the present invention with the Tone even though it has to be extruded at much higher extrusion temperatures and higher die temperatures. The polyethylene terephthalate (PET) required at least 550° F. for the PET extruder, which then resulted in good Tone flow and good bonding.  
         [0023]      FIG. 1  shows a cross sectional representation of the stiffener material of the present invention as disclosed in Examples 26-30. More, specifically,  FIG. 1  shows the layers of one embodiment of the present invention. The layers represent a first fabric ( 11 ) a layer of stiffener/adhesive ( 13   a ), a core layer of stiffener/adhesive ( 14 ), a layer of stiffener/adhesive ( 13   b ) and a second fabric ( 12 ).  
         [0024]     The following examples illustrate the process and the materials produced.  
         [0025]     Examples 1-9 related to the process of mixing the polymer stiffener and the adhesive material to produce a polymer sheet stiffener in a single mixing and/or extruding step.  
       Example 1  
       [0026]     The copolyester is a PETG copolyester, specifically Eastman Chemical Eastar 6763 and the adhesive is a polycaprolactone, specifically Tone 767. The materials have significantly different properties that can be made homogeneous by processing them through a READCO continuous mixer (READCO Company, York, Pa.) at temperatures in the range of 380-400° F. This equipment does not require a powder form of the material and allows for the dissimilar materials to form a homogeneous melt that will produce a tough, stiff and adhesive activated sheet of material. 40 parts of Tone 767 and 60 parts of PETG copolyester were fed separately into a READCO 2 inch continuous mixer with the temperatures set at 375° F. and the slot die at 425° F. The feed rate was 60 lbs/hr at a screw speed of 150 rpm. The resulting sheet was passed through a set of cooling rolls to produce a sheet with a thickness of 40-43 mils.  
       Example 2  
       [0027]     This example had the same conditions as Example 1 except 50 parts of Tone and 50 parts of PETG were fed into the mixer to produce the same thickness sheet.  
       Example 3  
       [0028]     This example had the same conditions as Example 1 except that 60 parts of Tone and 40 Parts of PETG were used to produce a sheet in the range of 40-43 mils.  
       Example 4  
       [0029]     This example had the same conditions as Example 1 except 60 parts of Tone and 40 parts of PETG were used to produce a sheet of approximately 60 mils in thickness.  
       Example 5  
       [0030]     This example had the same conditions as Example 1 except that 50 parts of Tone and 50 parts of PETG were used to produce a sheet that was 60 mils thick.  
       Example 6  
       [0031]     This example had the same conditions as Example 1 except that 40 parts of Tone and 60 parts of PETG were used to produce a sheet that was 60 mils thick.  
       Example 7  
       [0032]     This example had the same conditions as Example 1 except that 40 parts of Tone and 60 Parts of PETG were used to produce a sheet that was 80 mils thick.  
       Example 8  
       [0033]     This example had the same conditions as Example 1 except that 50 parts of Tone and 50 parts of PETG were used to produce a sheet that was 80 mils thick.  
       Example 9  
       [0034]     This example had the same conditions as Example 1 except that 60 parts of Tone and 40 parts of PETG were used to produce a sheet that was 70-75 mils thick.  
         [0035]     The materials produced from Examples 1-9 were tested for stiffness and resiliency using the Satra test procedures # TM 83. This test is a standard that is used in the footwear industry. The results are shown in Table I below:  
                                                                                                             TABLE I                           STIFFNESS AND RESILIENCY                Example No:                1   2   3   4   5   6   7   8   9                        Wt. (g/m 2 )   1293   1344   1317   1627   1741   1867   2511   2496   2236       Thickness (mils)   40-42   41-46   42-43   52-57   54-57   60-62   80-83   80-84   73-75       1 st  Collapse (kg)   17   16.5   11.4   19.7   26.4   37.1   63.2   51.8   43       10 th  Collapse (kg)   12.4   9.6   7.7   14.2   16.6   24.5   40.4   38.6   28.9       % Resiliency   73   58   68   72   63   66   64   75   67                  
 
         [0036]     Examples 10-25 relate to the process of co-extruding the polymer stiffener and the adhesive material to produce a polymer sheet stiffener in a single extruding step.  
       Example 10  
       [0037]     Two WELEX extruders are used in this example along with a WELEX coextrusion block. A sheet die with a maximum gap of 40 mils was used. A 2¼ inch WELEX extruder is used to extrude the PETG core material with a temperature profile of 325° F., 350° F., 375° F. and 400° F. The die temperature was maintained between 390-410° F. A temperature profile of 325° F., 375° F., 410° F. and 420° F. was also evaluated. PETG in the form of regrind chips was used as the feed to the extruder. The second extruder was a 1-inch WELEX extruder that employed Tone pellets. This second extruder was maintained at a temperature profile of 165° F., 230° F. and 255° F. The PETG was fed into the center of the coextrusion die block and the Tone into the two outer areas. The profile produced was a sheet of 33 mils in thickness that was extruded onto a set of 3 cooling rolls and wound up. The extrusion rate of the PETG was kept constant at 72 #/hr and the extrusion rate of the Tone was varied to give products that had ratios of PETG/Tone of 70/30, 80/20 and 90/10. The 70/30 ratio resulted from an extrusion speed of 72 #/hr of PETG and 30 #hr of the Tone, whereas the 90/10 ratio had an extrusion speed of 72 #/hr of PETG and 7.8 #/hr of Tone. The Tone formed on both sides of the PETG. Samples of the sheets were placed on a melting point bar apparatus that had varying temperatures and the surface tack of the pieces was measured by feeling them at various temperatures. All samples tested at 60-100° C. (140-212° F.) yielded good tack, which meant that the Tone was on the surface, If The Tone was not there then at these temperatures there would be no tack. Samples of the sheets were taken and placed between a piece of leather and lining material, which was then placed in a mold where the bondline temperature was 70° C. (150° F.), and the materials were compressed. The PETG/Tone material formed an excellent bond to the leather and the lining.  
         [0038]     Surprisingly the lower melting point resin did not dissolve in the higher melting point resin and the adhesive still maintained its integrity to form a separate coating on the PETG.  
         [0039]     A sample sheet of 31-33 mils was cut into a circle and molded to form a dome looking piece to be tested via the Satra dome testing measurement to determine stiffness and resiliency. Table II reproduces the obtained data:  
                             TABLE II                       STIFFNESS AND RESILIENCY EXAMPLE 10                                    Wt. (g/m 2 )   1035           Thickness (mils)   31-33           1 st  Collapse (kg)   15.3           10 th  Collapse (kg)   14.5           % Resiliency   95                      
 
       Example 11  
       [0040]     Three extruders were used in this experiment. Two were Crompton Davis Standard 1¼ inch extruders and one was a  2½ inch extruder. The larger extruder fed the PETG at a constant rate and the two smaller extruders fed the Tone. The materials were fed into a sheet manifold die where the center received the PETG melt and the two outer layers received the Tone.    
         [0041]     The equipment used was as follows:  
         [0042]     Extruders: One 2½-inch Davis Standard extruder with a 30/I L/D single stage barrier screw. Five zone heat and cooling. Two 1¼-inch Davis Standard extruders with a 24/1 L/D barrier single stage screw. All extruders did not have gear pumps or static mixers on them. A gravimetric feeder was above the 2½-inch extruder. The two 1¼-inch extruders fed to the side of the die and the  2½-inch fed to the center of the die. All extruders had throat cooling and throat cooled to  50° F.;  
         [0043]     Die: Three layer manifold flexible lip die with separate heating on outer manifolds and center as well as lip. The die was an Extrusion Dies Industries 12 inch wide unit with a coextrusion block for ABA coextrusion. Screen changers on all machines with 20/100/20 mesh packs;  
         [0000]     Rolls: Two casting rolls parallel to each other in horizontal plain of 30-inch face with cooling on both rolls;  
         [0000]     Thickness monitor: Beta type gauge;  
         [0000]     Wind-up station;  
         [0000]     Cutting table with paper cutter to cut sheet;  
         [0000]     Chiller: for rolls and extruders.  
         [0044]     (Note: thickness controlled by die lips and not rolls. Wind up used during start up and each thickness change until reach equilibrium and then bypassed wind up to go to cutting table to cut sheets about 3 feet long.)  
         [0045]     The PETG was not dried and was fed into the 2½-inch extruder. The Tone was not dried and was fed into the feed hopper feed to each of the 1¼-inch extruders at PETG Regrind—2½-extruder—start-up at 10 rpm. The extruder was maintained at a temperature of 325° F., 375° F., 400° F., 410° F. and 420° F. The screen changer, clamps and other piping were maintained at 410° F. The output was 46 #/hr. The feed throat was maintained at 50° F. The die was maintained at 400° F. The die lip heater was maintained at 100% and also used an air knife. There were no noticeable lines in the extrudate or the sheet of PETG.  
         [0046]     The Tone extruders were set at 150° F., 230° F. and 250° F. and the die at 250° F. The co-extruders were set at 18/11/11 rpms (PETG/Tone A/Tone C) to produce 154#/hr. The rolls temperature was set at 45° F. The die gap was set at 50 mils. The Roll temperature was then raised to 55° F. This produced sheet with a thickness of 10½ inches wherein the Tone coated section was about 7½ inches wide. The pressure in PETG extruder was 2065 psi, the pressure in the Tone A extruder was 574 psi and the pressure in the Tone C extruder was 387 psi. Roll speed was set at 7.5 fpm. The Melt temperature was set at 397 F. The air knife was placed at the exit of die and helped to cool the sheet before they were transferred to the rolls. This process produced sheet with a thickness of 53-55 mils and a weight of about 1700 g/m 2 , sheets with a thickness of 51-56 mils and a weight of 1611 g/m 2 , and sheets with a thickness of 45-48 mils and a weight of about 1500 g/m 2 . All three materials were tested on a melting point bar and produced good tack at 70-90° C. (158-194° F.).  
         [0047]     There was a pressure difference between the two Tone extruders because of the longer run of pipe to the die.  
         [0048]     The following examples illustrate the various formulations evaluated and the test results obtained on the finished sheets produced.  
       Example 12  
       [0049]     This example was prepared in accordance with Example 11, however, the extrusion rates were reduced to 16/10/10 rpm to produce sheets with a thickness of 40 mils and a weight of about 1300 g/m 2 . Extrusion pressure was 1896 psi for the PETG and 539 psi and 341 psi for the Tone A and Tone C extruders respectively. The temperature in all the melt pipes was set at 400° F., the die temperature was set at 400° F. and roll speeds were set at 7.5 fpm. This resulted in sheets with a width of 11 inches. Circles of sheet had thickness of 42-45 mils and a weight of 1306 g/m 2  and a thickness of 40 mils and a weight of 1273 g/m 2 .  
       Example 13  
       [0050]     This example was prepared in accordance with Example 12, however, the extrusion rates were reduced to 14/9/9 rpm to produce a thickness of 35 mils and a weight of 1000 g/m 2 . A thickness of 36-38 mils produced a weight of 1131 g/m 2 . This produced a very good bond on the melting point bar and was also tried between two pieces of lining. Extrusion pressure on the PETG extruder was 1678 psi, the Tone A was 499 psi and the Tone C was 313 psi.  
       Example 14  
       [0051]     This example was prepared in accordance with Example 13, however, the extrusion rates were reduced to 12/8/8 rpm to produce sheets of 30 mils thickness. The extruder pressure was 1643 psi for the PETG, and 472 psi and 279 psi for the A and C Tone extruders respectively. The melt temperature was set at 396° F. The roll speed remained at 7.5 fpm. The die gap was set at 30 mils. This produced sheets with a thickness of 32 mils and a weight of 964 g/m 2 . Sheets were also produced with a thickness of 25-28 mils and a weight of 762 g/m 2 .  
       Example 15  
       [0052]     This example was prepared in accordance with Example 14, however, the extrusion rates were reduced to 10/7/7 rpm to obtain a sheet with a thickness of 23-25 mils. This produced very good bonds when tested on the melting point bar. The extrusion pressure for the PETG extruder was 1314 psi and the Tone A and Tone C extruders were at 432 psi and 243 psi respectively. The melt temperature was set at 396° F. and the roll speed remained at 7.5 fpm.  
       Example 16  
       [0053]     This example was prepared in accordance with Example 15, however, the extrusion rates were reduced to 8/6/6 rpm to obtain sheets with a 20 mils thickness. Also, the extrusion rates were set at 9/6/6 rpm to obtain sheets with a thickness of around 17-20 mils, this produced very good bonds when tested on the melting point bar. At a thickness of 16-22 mils sheets were produced with a weight of 508 g/m 2 . Table III and IV below shows the dome test results for Example 11-16 above.  
                                                                             TABLE III                           Dome Test Results for a Examples 11-16                Material PETG/Tone                90/10   90/10   90/10   90/10   90/10                        Thickness (mils)   32   40   17   41-42   49-50       Thickness (mm)   0.81   1.01   0.43   1.04-1.07   1.24-1.27       Weight (g/m 2 )   964   1273   523   1297   1592       1 st  Collapse (kg)   10.1   20.4   3.2   20.0   43.1       10 th  Collapse (kg)   10.0   16.2   2.3   16.3   25.8       % Resiliency   99   79   72   82   60       Mold Time (min)   7   7   6   6   9                  
 
         [0054]    
       
         
               
             
               
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                 TABLE IV 
               
             
             
               
                   
               
               
                   
               
               
                 Dome Test Results for a Examples 11-16 
               
             
          
           
               
                   
                 Material PETG/Tone 
               
             
          
           
               
                   
                 90/10 
                 90/10 
                 90/10 
                 90/10 
                 90/10 
               
               
                   
                   
               
             
          
           
               
                 Thickness 
                 34-37 
                 46-50 
                 47-51 
                 36-38 
                 36-39 
               
               
                 (mils) 
               
               
                 Thickness 
                 0.86-0.94 
                 1.17-1.27 
                 1.19-1.29 
                 0.91-0.96 
                 0.91-0.99 
               
               
                 (mm) 
               
               
                 Weight 
                 1089 
                 1561 
                 1541 
                 1152 
                 1164 
               
               
                 (g/m 2 ) 
               
               
                 1 st  Collapse 
                 12.0 
                 31.6 
                 35.5 
                 16.1 
                 17.0 
               
               
                 (kg) 
               
               
                 10 th  Collapse 
                 11.6 
                 24.2 
                 25.6 
                 15.1 
                 15.1 
               
               
                 (kg) 
               
               
                 % Resiliency 
                 997 
                 77 
                 72 
                 94 
                 89 
               
               
                 Mold Time 
                 7 
                 7 
                 9 
                 7 
                 7 
               
               
                 (min) 
               
               
                   
               
             
          
         
       
     
       Example 17  
       [0055]     This example was prepared in accordance with Example 16. The extruders remained at 9/7/7 rpm, but the die temperature was raised to 450° F. and the PETG extruder temperature profile was set at 325° F., 425° F., 450° F., 450° F. and 450° F. The extrusion pressure was 1394 psi for the PETG extruder and 440 psi and 250 psi for the Tone A and Tone C extruders respectively. The Tone extruders remained at the prior temperature profiles. This reduced the die lines from the Tone. Also, this did not result in the Tone mixing into the PETG. Additionally, this yielded a good viscosity for the Tone, there was no roll sticking and the material had good bonding characteristics.  
       Example 18  
       [0056]     This example was prepared in accordance with Example 17, however at higher temperatures the edges of the sheet from the PETG got very runny and the extrusion rates were set to 14/9/9 rpm to obtain 35-mil sheets. This produced no die score lines.  
       Example 19  
       [0057]     This example was prepared in accordance with Example 18, however polyethylene terephthalate (PET) (predried) was used in place of PETG. The temperature profile on the extruder (which had previously been used for the PETG) was increased to 325° F., 425° F., 450° F., 450° F. and 450° F. and the die temperature was set at 450° F. The extruders were set at 14/9/9 rpms. The temperature profile for the Tone extruders was set at 175° F., 350° F. and 350° F. and the temperature for the melt pipe was set at 400° F. This produced sheets with thicknesses of 16-20 mils and 22-25 mils. This produced non-uniform coating and no die score lines from the Tone.  
       Example 20  
       [0058]     This example was prepared in accordance with Example 19, however the PET extruder temperature was increased to 500° F. and the die temperature was increased to 500° F. The extrusion rate was set at 24/12/12 rpms, the extrusion pressures of the PET was 193 psi, and 591 psi and 354 psi for the Tone A and Tone C extruders respectively. The melt temperature was set at 300° F. The flow was not good, but there were no score lines in the Tone coating.  
       Example 21  
       [0059]     This example was prepared in accordance with Example 20, however the temperature was increased to 550° F. for the die and for the co-extrusion block. The PET extruder temperature profile was set at 450° F., 500° F., 500° F., 500° F. and 500° F. The PET melt pipe temperature was set at 550° F. The temperature profile for the Tone extruders were set at 175° F., 350° F. and 350° F., and the pipe temperature was set at 300° F. The extruders were set at 14/9/9 rpms. The Tone exiting the lip was somewhere between 300° F. and 550° F. and showed no score die lines.  
       Example 22  
       [0060]     This example was prepared in accordance with Example 21, however the extruders flow rate was increased to 24/15/15 rpms resulting in 97 #/hr total output. This rate was then reduced to 24/12/12 rpms and the sheets were placed on casting rolls. The extruder pressure was 144 psi for the PET and 596 psi and 340 psi for the Tone A and Tone C extruders respectively. The roll speed remained at 7.5 fpm. This resulted in a good surface look and very good Tone coating with very good bonding. The gauge was around 29/31 mils and 1000 g/m 2 . The very high temperature did not hurt the flow of the Tone and eliminated the Tone die score lines. The sheet looked very good and resulted in a width of 10⅝ inches, where the Tone coated section was 9⅛inches. Material with a thickness of 35/36 mils had a weight of around 1200 g/m 2 . With the rolls temperature set at 55° F. there was no sticking. The coated sections were tough and flexible. The total output was around 112 #/hr with a Tone percent of around 20%. The Gauge was 34-36 mils and the weight was 1118 g/m 2 . Table V below shows the dome test results for Example 22.  
                             TABLE V                       Dome Test Results For a Sample       Molded at 180° C. for 2 minutes                                    PETG/TONE   80/20           Thickness (mils)   33-34           Thickness (mm)   0.84-0.86           Weight (g/m 2 )   1081           1 st  Collapse (kg)   13.1           10 th  Collapse (kg)   12.9           % Resiliency   98                      
 
       Example 23  
       [0061]     An ABA structure was made with Eastman GP001 polyester with a softening point of 74° C. (165° F.) and EMAC® 2260 ethylene methyl acrylate polymer. The adhesive two outer layers were the EMAC and the core was the GP001. A three-extruder coextrusion block system was used. The GP001 was extruded through a 2 inch Davis Standard extruder at 430° F. and the EMAC® through two 1¼ inch Davis Standard extruders at 450° F. The die temperature was 420° F. and a 22-inch die was used. The GP001 was predried before extrusion. The extrudate was cast onto a three roll casting system with the extrudate going onto the middle roll. Adjusting the die and the middle extruder&#39;s speed formed various sheet thicknesses. Sheets were produced that were 20, 25, 29, 35, 45 and 50 mils thick. The table below lists the dome test results on the sheets produced. The total of the A layers represented 18% of the total thickness of the finished sheet. The Dome test results of 5 molded at 95° C. for 8 minutes in accordance with Example 23 are shown in Table III below. The dome test results of 1 sample molded at 100° C. for seven minutes in accordance with Example 23 is shown in Tables VI and VII below.  
                                                                             TABLE VI                           Dome Test Results for a Sample Molded at 95° C. for 8 Minutes                Sample                A   B   C   D   E                        Thickness (mils)   19   24-25   27-29   44-48   48-50       Weight (g/m 2 )   587   761   874   1436   1529       1 st  Collapse (kg)   2.2   4.4   6.7   30.0   37.3       10 th  Collapse (kg)   2.1   4.1   6.4   21.0   21.8       % Resiliency   95   93   96   70   58                  
 
         [0062]    
       
         
               
             
               
               
             
               
               
               
             
           
               
                 TABLE VII 
               
             
             
               
                   
               
               
                   
               
               
                 Dome Test Results For a Sample 
               
               
                 Molded at 100° C. for 7 minutes 
               
             
          
           
               
                   
                 Sample 
               
               
                   
                 35 
               
               
                   
                   
               
             
          
           
               
                   
                 Thickness (mils) 
                 35-38 
               
               
                   
                 Weight (g/m 2 ) 
                 1140 
               
               
                   
                 1 st  Collapse (kg) 
                 15.1 
               
               
                   
                 10 th  Collapse (kg) 
                 14.3 
               
               
                   
                 % Resiliency 
                 95 
               
               
                   
                   
               
             
          
         
       
     
       Example 24  
       [0063]     This example was prepared in accordance with Example 23, except that the ABA structure used as the “A” layers a blend of 55% Tone and 45% GP001. The dome test data is recorded in Table VIII below. All samples displayed good adhesive properties.  
                                                                 TABLE VIII                           Dome Test Results For Samples Molded at 100° C. for 7 Minutes                Sample                A   B   C                            Thickness (mils)   25-26   34-36   45-47           Thickness (mm)   0.63-0.66   0.86-0.91   1.14-1.19           Weight (g/m 2 )   820   1116   1427           1 st  Collapse (kg)   8.9   18   34           10 th  Collapse (kg)   8.4   15.8   23.6           % Resiliency   94   88   69                      
 
       Example 25  
       [0064]     This example uses the same conditions and equipment as in example 23, but the “A” layers are a blend of 55% Tone and 45% EMAC 2260. The dome data is shown in Table IX below. All samples showed good adhesive properties.  
                                                                 TABLE IX                           Dome Test Results For Samples Molded at 100° C. for 7 Minutes                Sample                D   E   F                            Thickness (mils)   45-47   35-36   25-26           Thickness (mm)   1.14-1.19   0.89-0.91   0.63-0.66           Weight (g/m 2 )   1399   1108   770           1 st  Collapse (kg)   27.3   14.2   5.1           10 th  Collapse (kg)   20.2   12.6   6.1           % Resiliency   74   89   119                      
 
       Example 26  
       [0065]     A preblend of 90 parts of Tone 767 pellets and 10 parts of Copolyester GP001 pellets are fed into a 2½ inch extruder with a temperature profile of 380° F. A preblend of 52 parts of Tone 767 and 48 parts of GP001 are fed into a 4 inch extruder with a temperature profile of 430° F. The melt from both extruders are then fed into a manifold die with the two outer layers of the die having the melt from the 2½inch extruder, and the center section of the die yielding the melt from the 4 inch extruder. This produces a material with a core comprising one composition of the Tone/GP001 material and a second external composition (with a different or similar composition and said core composition) that surrounds said core composition. The total output is 600 #/hour with the 2½ inch unit delivering 135 #/hour and the 4 inch delivering 450 #/hr. The die has an opening of 40 mils and the sheet from the extruder is fed into the nip of a set of cold calendar rolls having an opening of 33 mils. Simultaneously, the Difco woven fabric is fed between the bottom roll of the calendar roll stack from an unwind unit and a second piece of fabric is fed around the middle roll of the roll stack from a second unwind unit such that extruded sheet is in between the two fabrics to form a laminate of the plastic sheet and the two outer fabrics. The total thickness of the laminate is 35 mils. The material is tested for its stiffness and resiliency via the Strata Dome test procedure. The results of this dome testing are illustrated in the TABLE X below for the various thicknesses the laminates produced. A sample of this material was then placed between a piece of leather and lining material then heat molded with 80 psig pressure to reach a bondline temperature of 75° C. between the leather and the laminate. The molded piece was then chilled on a mold at 5° C. for 20 seconds and removed. The leather/laminate/lining was then tested for bonding. The laminate could not be pulled away from either the lining or leather by hand, which illustrated a very good bond. Additionally, it showed that the outer adhesive layer of the laminate was able to penetrate the woven fabric and bond to the leather and the lining.  
                                                                         TABLE X                           Dome Test Results for a Sample Molded at 95° C. for 8 Minutes                Sample                    A   B   C   D                        Thickness (mils)   31   35   40   44       Thickness (mm)   0.79   0.89   1.02   1.12       Weight (g/m 2 )   868   943/967   1108   1226/1216       1 st  Collapse (kg)   4.8   5.2/6.2   8.4/8.4     9/9.4       10 th  Collapse (kg)   3.1   3.3/4.2   4.6/5.3   5.3/6.8       % Resiliency   65   63/68   55/63   59/72                  
 
       Example 27  
       [0066]     The procedure according to Example 26 was repeated, except that fabric was only used on one side of the laminate and the other side was just plastic. The Satra Dome test results are shown in TABLE XI below. The sample was molded as in Example 26 and produced excellent bonds with very good adhesion.  
                                                                                     TABLE XI                           Dome Test Results for a Sample Molded at 95° C. for 8 Minutes                Sample                A   B   C   D   E   F                        Thickness (mils)   16   20   34   39   40   45       Thickness (mm)   0.41   0.51   0.86   0.99   1.02   1.14       Weight (g/m 2 )   4.25   547   884   1073   1018   1176       1 st  Collapse (kg)   0.7   1.4   4.6   6.7   5.9   7.4       10 th  Collapse (kg)   0.6   1.1   3.2   4.3   4.1   5.2       % Resiliency   86   79   70   64   69   70                  
 
       Example 28  
       [0067]     A preblend of 80 parts of Tone 767 and 20 parts of Copolyester GP001 were fed into a 2½ inch extruder using the conditions described in Example 26. A preblend of 55 parts of Tone 767 and 45 parts of GP001 were fed into a 4 inch extruder under the conditions described in Example 26. These materials were then processed according to Example 26 to produce finished sheets of 40 mils in thickness having two sides of woven fabric. The materials were then Dome tested according to the Satra procedure and the data is presented in TABLE XII below. The material was then molded as described in Example 26, between leather and a lining at 90° C. and the material bonded well to the leather and the lining.  
                                                                 TABLE XII                           Dome Test Results for a Sample Molded at 95° C. for 8 Minutes                Sample                        A   B                            Thickness (mils)   41   43           Thickness (mm)   1.04   1.09           Weight (g/m 2 )   1132   1226           1 st  Collapse (kg)   8.8   9.7           10 th  Collapse (kg)   5.7   7.4           % Resiliency   65   76                      
 
       Example 29  
       [0068]     The formulation according to Example 28 was used in accordance with the process described in Example 27 to produce a sheet with fabric on one side and thicknesses of 38 and 39 mils. The material was then Dome tested and the data is shown in Table XIII below. This material was placed between a lining and leather and molded at a 90° C. The material showed very good bonds.  
                                                                 TABLE XIII                           Dome Test Results for a Sample Molded at 95° C. for 8 Minutes                Sample                        A   B                            Thickness (mils)   38   39           Thickness (mm)   0.97   0.99           Weight (g/m 2 )   1144   1073           1 st  Collapse (kg)   7.1   9.2           10 th  Collapse (kg)   4.8   4.6           % Resiliency   68   50                      
 
       Example 30  
       [0069]     A preblend of 60 parts of the Tone 767 and 40 parts of the Copolyester GP001 were fed to both a 2½ inch and 4 inch extruder at a an extrusion temperature of 430° F. and processed as illustrated in Example 26. Laminates were made with two sides of fabric as illustrated in Example 27. Various total thicknesses were made and Dome tested. The results are illustrated in Table XIV and XV below. Samples were placed between leather and lining and molded to produce a bonded product that was made with a bondline temperature of 100° C.  
                                       TABLE XIV                           Dome Test Results for a Sample Molded at 95° C. for 8 Minutes                Sample           A                            Thickness (mils)   46           Thickness (mm)   1.17           Weight (g/m 2 )   1293           1 st  Collapse (kg)   8.1           10 th  Collapse (kg)   5.0           % Resiliency   62                      
 
         [0070]    
       
         
               
             
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE XV 
               
             
             
               
                   
               
               
                   
               
               
                 Dome Test Results for a Sample Molded at 95° C. for 8 Minutes 
               
             
          
           
               
                   
                 Sample 
               
             
          
           
               
                   
                 B 
                 C 
                 D 
                 E 
                 F 
                 G 
               
               
                   
                   
               
             
          
           
               
                 Thickness 
                 16 
                 20 
                 25 
                 30 
                 35 
                 39 
               
               
                 (mils) 
               
               
                 Thickness 
                 0.41 
                 0.51 
                 0.63 
                 0.76 
                 0.89 
                 0.99 
               
               
                 (mm) 
               
               
                 Weight 
                 440 
                 558 
                 719 
                 833 
                 982 
                 1148 
               
               
                 (g/m 2 ) 
               
               
                 1 st  Collapse 
                 0.7 
                 1.6 
                 3.1 
                 3.6 
                 5.6 
                 10 
               
               
                 (kg) 
               
               
                 10 th  Collapse 
                 0.7 
                 1.4 
                 2.4 
                 2.8 
                 3.6 
                 6.1 
               
               
                 (kg) 
               
               
                 % Resiliency 
                 100 
                 88 
                 77 
                 78 
                 64 
                 61 
               
               
                   
               
             
          
         
       
     
         [0071]     Examples 26-30 illustrate the composition and process to manufacture a counter material that has either one side or two sides of fabric with a plastic core using a coextrusion process and calendar rolls. The composition is such that there are two outer layers of the plastic core that have adhesive properties and can be heat activated in such a manner that the adhesive can penetrate the woven fabric and under low heat and pressure bond to the lining and leather to produce a stiffener material that can be used in shoes. The material has high resiliency and good stiffness and can be made in various thicknesses and weights, both of which will influence the stiffness of the final product.  
         [0072]     While certain preferred and alternative embodiments of the invention have been set forth for purposes of disclosing the invention, modifications to the disclosed embodiments may occur to those who are skilled in the art. Accordingly, the appended claims are intended to cover all embodiments of the invention and modifications thereof which do not depart from the spirit and scope of the invention.