Flexible polyvinyl halide used for injection over-molding

Abstract

A polyvinyl halide compound, alone or alloyed with thermoplastic polyurethane, is used as a flexible layer for over-molding a rigid polymer substrate. Selection of types and amounts of calcium carbonate for the overmolding layer improves peel strength to achieve cohesive failure of the flexible overmolding layer rather than adhesive failure of the interface between the flexible overmolding layer and the rigid polymer substrate.

Claims

1. A polymer compound, comprising: polyvinyl halide having an inherent viscosity of less than about 0.9, as measured by using 0.2 grams of resin in 100 ml of cyclohexanone at 30° C. according to test method ASTM D 1243; an effective amount of plasticizer to provide a desired amount of flexibility to the polyvinyl halide and form a plasticized polyvinyl halide compound; and stearic acid-treated calcium carbonate fillers, or silane-treated calcium carbonate fillers, or both stearic acid-treated calcium carbonate fillers and silane-treated calcium carbonate fillers dispersed in the plasticized polyvinyl halide compound; wherein, when the plasticized polyvinyl halide compound is overmolded as a layer on to a Rigid PVC Test Substrate and undergoes a Modified ASTM D903 Adhesion Peel Strength Test, the layer of plasticized polyvinyl halide compound experiences cohesive failure; and wherein the plasticizer is present in an amount of at least about 20 weight parts per hundred weight parts of polyvinyl halide.

2. The polymer compound of claim 1, wherein the polyvinyl halide is polyvinyl chloride.

3. The polymer compound of claim 1, wherein the polyvinyl halide has a weight average molecular weight of from about 39,000 to about 150,000 where the molecular weight is measured by size exclusion chromatography.

4. The polymer compound of claim 1, wherein the polyvinyl halide has an inherent viscosity of from about 0.65 to about 0.85, as measured by using 0.2 grams of resin in 100 ml of cyclohexanone at 30° C. according to test method ASTM D 1243.

5. The polymer compound of claim 1, wherein the plasticizer is selected from the group consisting of phthalates, citrates, soyates, trimellitates, and combinations thereof.

6. The polymer compound of claim 3, wherein the plasticizer is selected from the group consisting of phthalates, citrates, soyates, trimellitates, and combinations thereof.

7. The polymer compound of claim 5, wherein the effective amount of plasticizer ranges from about 20 to about 150 weight parts per one hundred weight parts of polyvinyl halide.

8. The polymer compound of claim 6, wherein the effective amount of plasticizer ranges from about 20 to about 150 weight parts per one hundred weight parts of polyvinyl halide.

9. The polymer compound of claim 7, wherein the effective amount of plasticizer ranges from about 40 to about 100 weight parts per one hundred weight parts of polyvinyl halide.

10. The polymer compound of claim 8, wherein the effective amount of plasticizer ranges from about 40 to about 100 weight parts per one hundred weight parts of polyvinyl halide.

11. The polymer compound of claim 9, wherein: the calcium carbonate is Caribbean micritic limestone having a particle size of less than about 10 micrometers and having a purity of above 98%; and the limestone is treated with coupling agents comprising stearic acid or silane or both.

12. The polymer compound of claim 10, wherein: the calcium carbonate is Caribbean micritic limestone having a particle size of less than about 10 micrometers and having a purity of above 98%; and the limestone is treated with coupling agents comprising stearic acid or silane or both.

13. The polymer compound of claim 11, wherein the amount of calcium carbonate ranges from about 64 to about 150 weight parts per one hundred weight parts of polyvinyl halide.

14. The polymer compound of claim 12, wherein the amount of calcium carbonate ranges from about 64 to about 150 weight parts per one hundred weight parts of polyvinyl halide.

15. An overmolded polymer article comprising a layer comprising the polymer compound of claim 1 and a layer of rigid polyvinyl halide.

16. The polymer compound of claim 2, wherein the polyvinyl chloride is alloyed with thermoplastic polyurethane.

17. The polymer compound of claim 16, wherein the plasticizer is selected from the group consisting of phthalates, citrates, soyates, trimellitates, and combinations thereof.

18. The polymer compound of claim 16, wherein: the calcium carbonate is Caribbean micritic limestone having a particle size of less than about 10 micrometers and having a purity of above 98%; and the limestone is treated with coupling agents comprising stearic acid or silane or both.

19. The polymer compound of claim 1, wherein the polyvinyl halide is suspension polymerized vinyl chloride.

20. A composition comprising: polyvinyl halide; and a plasticizer; wherein, when the composition is overmolded as a layer on to a Rigid PVC Test Substrate and undergoes a Modified ASTM D903 Adhesion Peel Strength Test, the layer experiences cohesive failure; and wherein the plasticizer is present in an amount of at least about 20 weight parts per hundred weight parts of polyvinyl halide.

21. The composition of claim 20, wherein the polyvinyl halide has an inherent viscosity of less than about 0.9, as measured by using 0.2 grams of resin in 100 ml of cyclohexanone at 30° C. according to test method ASTM D 1243.

22. The composition of claim 21, wherein the polyvinyl halide has an inherent viscosity of from about 0.65 to about 0.85, as measured by using 0.2 grams of resin in 100 ml of cyclohexanone at 30° C. according to test method ASTM D 1243.

23. The composition of claim 20, wherein the polyvinyl halide has a weight average molecular weight of from about 39,000 to about 150,000 where the molecular weight is measured by size exclusion chromatography.

24. The composition of claim 20, wherein the polyvinyl halide is polyvinyl chloride.

25. The composition of claim 20, wherein the polyvinyl halide is suspension polymerized vinyl chloride.

26. A composition, comprising: polyvinyl halide having an inherent viscosity of less than 0.9, as measured by using 0.2 grams of resin in 100 ml of cyclohexanone at 30° C. according to test method ASTM D 1243; plasticizer; and calcium carbonate present in an amount of from 64 weight parts to 150 weight parts per 100 weight parts of the polyvinyl halide; wherein the plasticizer is present in an amount of at least about 20 weight parts per hundred weight parts of polyvinyl halide.

27. The composition of claim 26, wherein the polyvinyl halide has an inherent viscosity of from about 0.65 to about 0.85, as measured by using 0.2 grams of resin in 100 ml of cyclohexanone at 30° C. according to test method ASTM D 1243.

28. The composition of claim 26, wherein the polyvinyl halide has a weight average molecular weight of from about 39,000 to about 150,000 where the molecular weight is measured by size exclusion chromatography.

29. The composition of claim 26, wherein the polyvinyl halide is polyvinyl chloride.

30. The composition of claim 26, wherein the polyvinyl halide is suspension polymerized vinyl chloride.

31. An article, comprising: a layer comprising polyvinyl halide and plasticizer; and a rigid substrate comprising polyvinyl halide, the rigid substrate in contact with the layer comprising the polyvinyl halide and the plasticizer; wherein, when a peel force is applied to the layer, the layer experiences cohesive failure before being peeled away from the rigid substrate.

32. The article of claim 31, wherein the polyvinyl halide has an inherent viscosity of less than about 0.9, as measured by using 0.2 grams of resin in 100 ml of cyclohexanone at 30° C. according to test method ASTM D 1243.

33. The article of claim 31, wherein the polyvinyl halide has an inherent viscosity of from about 0.65 to about 0.85, as measured by using 0.2 grams of resin in 100 ml of cyclohexanone at 30° C. according to test method ASTM D 1243.

34. The article of claim 31, wherein the polyvinyl halide is polyvinyl chloride.

35. The article of claim 31, wherein the polyvinyl halide has a weight average molecular weight of from about 39,000 to about 150,000 where the molecular weight is measured by size exclusion chromatography.

36. The article of claim 31, wherein the polyvinyl halide is suspension polymerized vinyl chloride.

37. The composition of claim 20, wherein the plasticizer is present in an amount ranging from about 20 to about 150 weight parts per hundred weight parts of polyvinyl halide.

38. The composition of claim 26, wherein the plasticizer is present in an amount ranging from about 20 to about 150 weight parts per hundred weight parts of polyvinyl halide.

Description

EXAMPLES

(1) Modified ASTM D903 Adhesion Peel Strength Test

(2) Adhesion Peel Strength Test Method ASTM D903 for 180° peel adhesion was modified as described here for testing adhesion between flexible PVC laminate and rigid PVC and defined for this purpose as “Modified ASTM D903 Adhesion Peel Strength Test”.

(3) The rigid PVC chosen for the test, and defined for this purpose to be “Rigid PVC Test Substrate”, was Geon™ Resilience™ HC8220 White 1612 rigid PVC from PolyOne Corporation. Key properties of this grade of PVC, in SI typical values, are: Specific Gravity: 1.33 (ASTM D792); Spiral Flow: 86.4 cm; Molding Shrinkage—Flow: 0.20-0.5% (ASTM D955); Tensile Modulus: 2690 MPa (ASTM D638, Type 1 51 mm/min); Tensile Strength Yield: 48.3 MPa (ASTM D638, Type 1 51 mm/min); Tensile Strength Elongation: 22% (ASTM D638, Type 1 51 mm/min); Flexural Modulus: 2760 MPa (ASTM D790); Flexural Strength: 75.8 MPa (ASTM D790); Notched Izod Impact at −18° C. and 3.18 mm, Injection Molded: 110 J/m (ASTM D256A); Notched Izod Impact at 0° C. and 3.18 mm, Injection Molded: 690 J/m (ASTM D256A); Notched Izod Impact at 23° C. and 3.18 mm, Injection Molded: 1100 J/m (ASTM D256A); Durometer Hardness in Shore D scale: 79 (ASTM D2290); Deflection Temperature under Load at 0.45 MPa, unannealed and 3.18 mm: 68.9° C. (ASTM D648); Deflection Temperature under Load at 0.45 MPa, annealed and 3.18 mm: 72.8° C. (ASTM D648); Deflection Temperature under Load at 1.8 MPa, unannealed and 3.18 mm: 68.9° C. (ASTM D648); Deflection Temperature under Load at 1.8 MPa, annealed and 3.18 mm: 72.8° C. (ASTM D648); RTI Elec: 50.0° C. (UL 746); RTI Imp: 50.0° C. (UL 746); RTI Str: 50.0° C. (UL 746); and Processing (Melt) Temp.: 199-210° C.

(4) Sample Preparation By Injection Molding:

(5) (1) injection mold Geon™ Resilience™ HC8220 White 1612 rigid PVC into a 3 inch×6.5 inch×0.125 inch (7.62 cm×16.51 cm×0.317 cm) plaque using an 85T Van Dorn molding machine.

(6) (2) then use transparent tape to cover about 3″×2″ (7.62 cm×5.08 cm) area of the molded Geon™ HC8220 White 1612 plaque used as the substrate in the Series I Experiments (Comparative Examples A-E and Example 1). (Based on Series 1 Experiment, the cover area of the molded Geon™ HC8220 White 1612 plaque by transparent tape was adjusted from 3″×2″ (7.62 cm×5.08 cm) to about 3″×4″ (7.62 cm×10.16 cm) area used as substrate to keep each specimen slightly longer than 2″ (5.08 cm) in the remaining experiments.)

(7) (3) Next, injection over-mold of the various flexible PVC materials of the examples onto the molded Geon™ HC8220 White 1612 plaque with about 0.045″ (0.1143 cm) thickness of flexible PVC layer using molding conditions identified in the Tables.

(8) (4) Finally cut a flexural bar of 1″ (2.54 cm) wide out of the final molded parts for the Modified ASTM D903 Adhesion Peel Strength Test.

(9) Test Procedure of Modified ASTM D903 Adhesion Peel Strength Test:

(10) ASTM D903 Adhesion Peel Strength Test Method (which can be seen at youtube.com/watch?v=wxCdtIisXxQ as of the filing date of this application) was modified to measure peeling strength of the various flexible PVC molding layers of about 0.045″ (0.1143 cm) thickness from the overmolded Geon™ HC8220 White 1612 substrate using an Instron™ 4204 testing machine.

(11) The differences between the official ASTM D903 method and the modified one are in that (1) the sample used in ASTM D903 is longer than the 2″ (5.08 cm) sample as used in the modified one and (2) testing is terminated on a half way of the sample length in ASTM D903 whereas in the modified method, testing was terminated when the sample was peeled off from the substrate due to either adhesive failure or cohesive failure.

(12) 6″/min (15.24 cm/min) was used as pulling speed.

(13) Five samples for each Comparative Example and Example were tested, and the results averaged. The numerical results are expressed in pound-force per inch (lbf/in) units, wherein each pound-force per inch equals 0.175127 Newtons per millimeter (N/mm).

(14) Observation of Results:

(15) Adhesive failure was not desired where the bond of the flexible overmolding layer to the substrate was not so strong that a failure occurred at the interface between the flexible PVC overmolding layer and the rigid PVC substrate causing the flexible material to be peeled off from the substrate during peeling test without loss of integrity or leaving of any amount of the black flexible overmolding layer on the white rigid substrate.

(16) On the other hand, cohesive failure was desired where the bond of the overmolding layer to the substrate exceeded the internal strength of the flexible PVC layer so that the flexible PVC layers were broken during the peeling test with portions of the overmolding layer remaining adhered to the substrate. The remaining flexible overmolding layer fragments were black as compared with the white rigid substrate. In other words, the integrity of the PVC overmolding layer itself failed before the adhesive bond between the flexible PVC overmolding layer and the rigid PVC overmolded substrate.

(17) In the case of cohesive failure, because the measured peeling strength reflected more internal mechanical strength other than actual bond strength, the peeling strength for all flexible PVC layers was reported as greater than the measured peeling strength in this patent application.

Comparative Examples A-E and Example 1

(18) Table 3 shows the preparation and results of Comparative Examples A-E and Example 1.

(19) Inherent Viscosity or IV is measured using ASTM D1243 test method and expressed in dl/g units.

(20) Comparative Examples A and B and Example 1 explored the performance of the overmolding layer based on the differences in inherent viscosity of the PVC resin. Comparative Examples A and B showed that an inherent viscosity of the PVC resin should not be more than about 0.79, because the Modified Peel Strength Test showed that the formulation of Example 1 had a higher peel strength but also with cohesive failure instead of adhesive failure.

(21) Comparative Examples C and D and Example 1 explored the performance of using calcium carbonate fillers with a PVC resin for all three which had an inherent viscosity of about 0.79. The Modified ASTM D903 Adhesion Peel Strength Test results showed that calcium carbonate is necessary for acceptable bonding strength at the interface between the rigid overmolded substrate and the flexible overmolding layer. The type of plasticizer was not a controlling factor.

(22) Comparative Examples A, B, E, and Example 1 all used the same amount of a mixture of calcium carbonate fillers, all more that about 64 PHR. Example 1 was the only one to peel acceptably because of the inherent viscosity of the PVC resin of about 0.79.

(23) Comparative Example E showed that the use of a blowing agent could not overcome the higher inherent viscosity of the PVC resin to provide an acceptable test result because Comparative Example E only showed adhesive failure, no cohesive failure.

Comparative Example F and Examples 2-10

(24) This series of experiments shown in Table 4 explored the use of a variety of calcium carbonate fillers in a PVC resin having an IV of about 0.79 dl/g with the same rigid PVC overmolded substrate described for Example 1. All of the calcium carbonate choices were commercially available. The result found is that untreated calcium carbonate filler cannot be the dominant amount of calcium carbonate used in the formulation. Only Comparative Example F, which had no treated calcium carbonate, was not acceptable in peel strength as tested.

(25) Without being limited to a particular theory, it is believed that the treatment of calcium carbonate provides better dispersion of fillers in PVC matrix and hence more homogenous surface so as to result in better adhesion of the flexible overmolding layer to the rigid overmolded substrate.

Examples 11-16 and Comparative Examples G-H

(26) This series of experiments shown in Table 5 explored the use of a variety of amounts of a single calcium carbonate filler in a PVC resin having an IV of about 0.79 dl/g with the same rigid PVC overmolded substrate described for Example 1. The series also explored alternative plasticizers of various types and use of second PVC, a Geon E-44 DE-glossing PVC resin. The result found is that treated calcium carbonate at 40 or less PHR (Comparative Examples G and H) was insufficient for peel strength due to adhesive failure, and that treated calcium carbonate at 80 and above PHR (Examples 15 and 16) had increasing peel strength with experiencing cohesive failure during peeling strength test. Therefore, the amount of calcium carbonate in the overmolding layer can range from about 45 to about 150 and preferably from about 60 to about 100 PHR.

(27) The results of Examples 11, 12, 13 and 14 showed that plasticizer type and use of the Geon E-44 to replace part of PVC, was not significant to the determination of peel strength. All these four Examples exhibited cohesive failure.

Examples 17-20 and Comparative Examples I-J

(28) Comparative Examples I and J and Examples 17-20 explored the performance of a PVC/TPU alloy as the overmolding layer based on the differences in use of treated calcium carbonate. Comparative Examples I and J showed that the absence of calcium carbonate in the PVC/TPU alloy compound caused no cohesive strength, as compared with Examples 17-20. It is also noted that Example 17 had some attributes of both cohesive failure and adhesive failure, indicating that 40 parts per hundred of PVC resin is the practical lower limit of calcium carbonate loading to provide an acceptable polymer compound. In comparison of the peel strengths of Examples 17-19, it is noted that the progression of 40 parts (Ex. 17) to 64 parts (Ex. 18) achieved higher peel strength with adhesion failure mode transition from the combined adhesive and cohesive failure mode to the cohesive failure mode whereas from 64 parts (Ex. 18) to 80 parts (Ex. 19) did not achieve even higher measured peel strength but still with cohesive failure mode.

(29) A comparison between Ex. 18 and Ex. 20 demonstrates how similar performance results can be achieved when using similar amounts of different types of plasticizer, although the TOTM plasticizer used in Ex. 18 in five more parts in the formulation yielded a higher peel strength.

(30) Table 6 shows the results of these Examples and Comparative Examples.

(31) TABLE-US-00003 TABLE 3 Ingredients Comp. A Comp. B Example 1 Comp. C Comp. D Comp. E SUSP RESIN OV240 PVC 100.00 resin from Oxyvinyls (K Value: 70, IV: 1.02) SUSP RESIN OV220F PVC 100.00 100.00 resin from Oxyvinyls (K Value: 67, IV: 0.92) SUSP RESIN OV195F PVC 100.00 100.00 100.00 resin from Oxyvinyls (K Value: 60, IV: 0.79) MARK 4716, Barium zinc 2.00 2.00 2.00 2.00 2.00 2.00 phosphite liquid stabilizer from Galata Chemicals DINP Generic plasticizer, Di- 86.00 86.00 86.00 82.00 86.00 Isononyl Phthalate Synplast TOTM plasticizer 89 Epoxidized Soybean Oil 5.00 5.00 5.00 5.00 5.00 5.00 (ESO) Ground and uncoated 19.00 19.00 19.00 0.00 0.00 19.00 CALCIUM CARBONATE 3.5U, particle size from 2.5 to 3.5 um CAL-CARB 2.0TR (OPTIFIL 45.00 45.00 45.00 0.00 0.00 45.00 T) from, which is treated calcium carbonate with particle size of from 1.2 to 1.8 um from Huber Engineered Materials Fully Refined Paraffin Wax 1, 0.50 0.50 0.50 0.50 0.50 0.50 Paraffin Wax 165 from Honeywell as lubricant Expancel 930 DU120 used as 2.00 blowing agent METEOR BLACK 9880 1.00 1.00 1.00 1.00 1.00 1.00 carbon black used to check how much the material to be left after peeling testing Total, phr 258.50 258.50 258.50 190.50 197.50 260.50 Mixing and Milling/Pelletizing Equipment Henschel 10 liter mixer Mixing speed, rpm 900 Order to addition of PVC resin, stabilizer, plasticizer, lubricants, calcium carbonate and carbon black/blowing agent Ingredients Drop Temperarure, ° F. 205 Form of product free flow powder Equipment Banbury Mixing speed, rpm 90 Chamber Temperature,° F. 300 Drop Temperature, ° F. 280~290 Two Roll Mill with 0.14 in. gap Rear Roll Temperature, ° F. 285~290 Front Roll Temperature, ° F. 270~275 Rear Roll Mixing speed, rpm 25 Front Roll Mixing speed, rpm 17 Time on mill until thoroughly mixed Form of product Kept the milled slabs in freezer for overnight and then cut into cubes Injection Molding of Flexible Overmolding Layer Over Rigid PVC Plaque Equipment 85T Van Dorn Molding machine Rear Barrel Temperature, ° F. 335 335 335 335 335 335 Center Barrel Temperature, ° F. 340 340 340 340 340 340 Front Barrel Temperature, ° F. 350 350 350 350 350 350 Nozzle Barrel Temperature, ° F. 340 340 340 340 340 340 Screw Speed, rpm 100 100 100 100 100 100 Injection speed, in/sec 0.8 0.8 0.8 0.8 0.8 0.8 Injection pressure, psig 776 714 584 555 548 688 Hold pressure, psig 400 400 400 400 400 400 Short size, inch 2 2 2 2 2 2 Cushion, inch 0.216 0.205 0.196 0.196 0.19 0.3 Hold time, second 4 4 4 4 4 4 Cooling time, second 40 40 40 40 40 40 Modified ASTM D903 Adhesion Peel Strength Test Failure Mode: Cohesive = C and Adhesive = A Peel strength, (lb.sub.f/in) 7.02 9.20 >13.77 4.60 4.17 10.92 Failure Mode A A C A A A

(32) TABLE-US-00004 TABLE 4 Ingredients Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Comp. F Ex. 8 Ex. 9 Ex. 10 SUSP RESIN 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 OV195F PVC resin from Oxyvinyls (K Value: 60, IV: 0.79) MARK 4716, 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Barium zinc phosphite liquid stabilizer from Galata Chemicals Di- Isononyl 86.00 86.00 86.00 86.00 86.00 86.00 86.00 86.00 86.00 86.00 Phthalate Plasticizer Epoxidized 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 Soybean Oil Ground and 19.00 19.00 uncoated CALCIUM CARBONATE 3.5 μm, particle size from 2.5 to 3.5 μm CAL-CARB 45.00 45.00 64.00 2.0TR (OPTIFIL T) treated calcium carbonate 1.2 pm to 1.8 μm particle size (Huber) KOTAMITE, 64.00 3.0 μm Treated GCC calcium carbonate Omyacarb 64.00 UFT, 1 μm GCC treated calcium carbonate Omyacarb FT, 64.00 1.4 μm wet GCC calcium carbonate Magnum Gloss 64.00 32.00 SAT, 0.4 μm PCC treated calcium carbonate Magnum Gloss 64.00 32.00 M, 0.4 μm PCC non-treated calcium carbonate ULTRAPFLEX 64.00 treated calcium carbonate with 0.07 μm particle Fully Refined 0.50 Paraffin Wax 165 from Honeywell Stearic acid FDA 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 NF listed, lubricant Carbon black, 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 UV grade METEOR 1.00 BLACK 9880 carbon black Total, PHR 258.50 258.20 258.20 258.20 258.20 258.20 258.20 258.20 258.20 258.20 Mixing and Milling/Pelletizing Equipment Henschel 10 liter mixer Mixing speed, 950 rpm Order to addition PVC resin, stabilizer, plasticizer, lubricants, calcium carbonate and carbon black of Ingredients Drop 205 Temperature, ° F. Form of product free flow powder Equipment Banbury Mixing speed, 90 rpm Chamber 300 Temperature ° F. Drop 290~305 Temperature, ° F. Two Roll Mill with 0.14 in. gap Rear Roll 270 Temperature, ° F. Front Roll 285 Temperature, ° F. Rear Roll 25 Mixing speed, rpm Front Roll 17 Mixing speed, rpm Time on mill until thoroughly mixed Form of product Kept the milled slaps in freezer for overnight and then cut into cubes Injection Molding of Flexible Overmolding Layer Over Rigid PVC Plaque Equipment 85T Van Dorn Molding Machine Rear Barrel 335 335 335 335 335 335 335 335 335 335 Temperature, ° F. Center Barrel 340 340 340 340 340 340 340 340 340 340 Temperature, ° F. Front Barrel 350 350 350 350 350 350 350 350 350 350 Temperature, ° F. Nozzle Barrel 340 340 340 340 340 340 340 340 340 340 Temperature, ° F. Screw Speed, 70 70 70 70 70 70 70 70 70 70 rpm Injection speed, 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 in/sec Injection 602 614 573 574 591 591 636 587 562 602 pressure, psig Hold pressure, 400 400 400 400 400 400 400 400 400 400 Psig Short size, inch 2 2 2 2 2 2 2 2 2 2 Cushion, inch 0.212 0.201 0.196 0.194 0.187 0.187 0.176 0.176 0.174 0.165 Hold time, 4 4 4 4 4 4 4 4 4 4 second Cooling time, 40 40 40 40 40 40 40 40 40 40 seconds Modified ASTM D903 Adhesion Peel Strength Test Failure Mode: Cohesive = C and Adhesive = A Peel strength, (lb.sub.f/in) >9.52 >8.34 >7.49 >7.31 >7.95 >7.98 4.78 >9.32 >7.86 >8.53 Failure Mode C C C C C C A C C C

(33) TABLE-US-00005 TABLE 5 Ingredients Ex. 11 Ex. 12 Ex. 13 Ex. 14 Comp. G Comp. H Ex. 15 Ex. 16 SUSP RESIN 100.00 100.00 100.00 80.00 100.00 100.00 100.00 100.00 OV195F PVC (K Value: 60, IV: 0.79) Geon E-44 PVC 20.00 resin (PolyOne) MARK 4716, 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Barium zinc phosphite liquid stabilizer from Galata Chemicals Di- Isononyl 86.00 86.00 86.00 86.00 86.00 86.00 Phthalate Synplast TOTM 86.00 plasticizer Palamoll 654 84.00 polymeric plasticizer Epoxidized 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 Soybean Oil Omyacarb 64.00 64.00 64.00 64.00 20.00 40.00 80.00 100.00 UFT, 1 μm GCC treated calcium carbonate Stearic acid FDA 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 NF listed, lubricant Carbon black 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 UV grade Total, phr 258.20 258.20 256.20 258.20 214.20 234.20 274.20 294.20 Mixing and Milling/Pelletizing Equipment Henschel 10 liter mixer Mixing speed, 1000 rpm Order to addition PVC resin, stabilizer, plasticizer, lubricants, calcium carbonate and carbon black of Ingredients Drop 205 Temperature, ° F. Form of product free flow powder Equipment Banbury Mixing speed, 100 rpm Chamber 300 Temperature, ° F. Drop 290 Temperature, ° F. Two Roll Mill with 0.12 in. gap Rear Roll 270 Temperature, ° F. Front Roll 290 Temperature, ° F. Rear Roll 24 Mixing speed, rpm Front Roll 28 Mixing speed, rpm Time on mill until thoroughly mixed Form of product Kept the milled slaps in freezer for overnight and then cut into cubes Injection Molding of Flexible Overmolding Layer Over Rigid PVC Plaque Equipment 85T Van Dorn Molding machine Rear Barrel 330 330 330 330 330 330 330 330 Temperature, ° F. Center Barrel 340 340 340 340 340 340 340 340 Temperature, ° F. Front Barrel 350 350 350 350 350 350 350 350 Temperature, ° F. Nozzle Barrel 350 350 350 350 350 350 350 350 Temperature, ° F. Screw Speed, 90 90 90 90 90 90 90 90 rpm Injection speed, 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 in/sec Injection 575 649 745 614 542 575 603 614 pressure, psig Hold pressure, 400 400 400 400 400 400 400 400 psig Short size, inch 2 2 2 2 2 2 2 2 Cushion, inch 0.205 0.203 0.19 0.196 0.194 0.194 0.183 0.176 Hold time, 4 4 4 4 4 4 4 4 second Cool time, (sec.) 40 40 40 40 40 40 40 40 Modified ASTM D903 Adhesion Peel Strength Test Failure Mode: Cohesive = C and Adhesive = A Peel strength, (lb.sub.f/in) >7.2 >6.6 >8.8 >6.1 4.2 5.4 >11.8 >9.9 Failure Mode C C C C A A C C

(34) TABLE-US-00006 TABLE 6 Ingredients Comp. I Comp. J Ex. 17 Ex. 18 Ex. 19 Ex. 20 SUSP RESIN OV195F PVC resin from 100.00 100.00 100.00 100.00 100.00 Oxyvinyls (K Value: 60, IV: 0.79) SUSP RESIN OV 240 PAS@ Bulk Rail 100.00 from Oxyvinyls (K value: 70, IV: 1.02) NAFTOSAFE PLP-3000 (calcium zinc 2.10 2.10 2.10 2.10 2.10 2.10 stabilizer) from Chemson Inc. IROGRAN PS 455-200 Thermoplastic 40.00 40.00 40.00 40.00 40.00 40.00 Polyurethane Elastomer from Huntsman WESTON EHDP (2 Ethyl Hexyl Diphenyl 1.00 1.00 1.00 1.00 1.00 1.00 Phosphite) from Addivant Corporation Synplast TOTM plasticizer 90.00 90.00 90.00 90.00 90.00 Palamoll 654 polymeric plasticizer 85.00 Epoxidized Soybean Oil (ESO) 5.00 5.00 5.00 5.00 5.00 5.00 Omyacarb UFT, 1u GCC treated calcium 40.00 64.00 80.00 64.00 carbonate from Omya Paraloid K120ND, acrylic based processing 1.75 1.75 1.75 1.75 1.75 1.75 aid from Dow Chemical PARALOID K-175, acrylic based 1.50 1.50 1.50 1.50 1.50 1.50 processing aid from Dow OPE -AC-629A Oxidized Polyethylene 0.20 0.20 0.20 0.20 0.20 0.20 Homopolymer from Honeywell Carbon black UV grade used to check how 1.00 1.00 1.00 1.00 1.00 1.00 much the material to be left after peeling testing Total, phr 242.55 242.55 282.55 306.55 322.55 301.55 Mixing and Milling/Pelletizing Equipment Henschel 10 liter mixer Mixing speed, rpm 680 Order to addition of Ingredients PVC resin, stabilizer, plasticizer, lubricants, calcium carbonate and carbon black Drop Temperature, ° F. 210 Form of product free flow powder Equipment Banbury Order of addition of Ingredients Melt the above made PVC free flow powder compound up to 300 F., then added IROGRAN PS 455-200 TPU into the melt Mixing speed, rpm 90 Chamber Temperature, ° F. 330 Drop Temperature, ° F. 330 Two Roll Mill with 0.12 in. gap Rear Roll Temperature, ° F. 340 Front Roll Temperature, ° F. 325 Rear Roll Mixing speed, rpm 24 Front Roll Mixing speed, rpm 17 Time on mill until thoroughly mixed Form of product Kept the milled slaps in freezer for overnight and then cut into cubes Injection Molding of Flexible Overmolding Layer Over Rigid PVC Plaque Equipment 85T Van Dorn Molding machine Rear Barrel Temperature, ° F. 335 335 335 335 335 335 Center Barrel Temperature, ° F. 340 340 340 340 340 340 Front Barrel Temperature, ° F. 350 350 350 350 350 350 Nozzle Barrel Temperature, ° F. 350 350 350 350 350 350 Screw Speed, rpm 100 100 100 100 100 100 Injection speed, in/sec 0.8 0.8 0.8 0.8 0.8 0.8 Injection pressure, psig 790 631 691 702 742 790 Hold pressure, psig 400 400 400 400 400 400 Short size, inch 2 2 2 2 2 2 Cushion, inch 0.205 0.201 0.205 0.196 0.203 0.205 Hold time, second 4 4 4 4 4 4 Cool time, (sec.) 40 40 40 40 40 40 Modified ASTM D903 Adhesion Peel Strength Test Failure Mode: Cohesive = C and Adhesive = A Peel strength, (lb.sub.f/in) 1.32 3.59 >9.82 >12.19 >12.13 >9.95 Failure Mode A A C & A C C C

(35) Without undue experimentation, those having ordinary skill in the art can utilize the written description, including the Examples, to make and use the present invention.

(36) All documents cited in the Embodiments of the Invention are incorporated herein by reference in their entirety unless otherwise specified. The citation of any document is not to be construed as an admission that it is prior art with respect to the present invention.

(37) While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of the present invention.