Shoe components and methods of manufacture

• US 20050027025A1
• Filed: 06/25/2004
• Published: 02/03/2005
• Est. Priority Date: 06/26/2003
• Status: Active Grant

• Current Assignee: Taylor Made Golf Co., Inc.
• Original Assignee: Taylor Made Golf Co., Inc.
• Inventors: Kim, Hyun Jin, Grott, Marco, Erb, Robert
• Granted Patent: US 7,073,277 B2
• Time in Patent Office: Days
• US Class Current: 521/50
• CPC Class Codes: A43B 17/003 characterised by the material made of wood A43B17/12, made of sponge, rubber or plastic materials A43B17/14
• CPC Class Codes: A43B 7/28 Adapting the inner sole or the side of the upper of the shoe to the sole of the foot
• CPC Class Codes: C08J 2203/22 Expandable microspheres, e.g. Expancel®
• CPC Class Codes: C08J 2375/04 Polyurethanes
• CPC Class Codes: C08J 9/32 from compositions containing microballoons, e.g. syntactic foams

Abstract

The invention relates to the field of shoes in general, and more specifically to the application of microspheres in shoe material formulations to yield desired shoe properties. Even more specifically, the invention relates to a shoe component prepared from a closed cell foam incorporating microspheres to yield controlled cell size, cell size distribution and expansion characteristics. In another embodiment, the invention also relates to an inner sole for a shoe prepared from the reaction product of a polymer matrix component and a curing agent where the curing agent is incorporated in microspheres to yield a material conformable to the user'"'"'s foot shape.

Claims

1. A closed-cell foam comprising:

a. from about 0.25 pph to about 20 pph of polymeric microspheres, each polymeric microsphere having a diameter less than 100 microns; and

b. a polymeric matrix resin including a polymer selected from the group consisting of a thermoset polymer and a thermoplastic polymer.

2. The closed-cell foam according to claim 1, wherein:

a. the polymeric microspheres are present in amount of from about 0.50 pph to about 15 pph, each polymeric microsphere having a diameter less than 80 microns;

b. the polymeric microspheres include a polymeric outer shell and an encapsulated gas within the polymeric outer shell; and

c. the polymeric matrix resin is selected from the group consisting of synthetic and natural rubbers, polycarbonates, polyolefins, functionalized polyolefins, ionomers, polyamides, polyesters, polyvinyl alcohols, polystyrenes, polyurethanes, polyarylates, polyacrylates, polyphenyl ethers, modified-polyphenyl ethers, polystyrenes, polyphthalates polymer, styrenic block copolymers, acrylonitrile-styrene-butadiene (ABS), styrene-acrylonitrile (SAN), styrene-maleic anhydryde (S/MA) polymers, styrenic copolymers, styrenic terpolymers, functionalized styrenic copolymer, functionalized styrenic terpolymer, cellulose polymers, liquid crystal polymers (LCP), ethylene-propylene-diene terpolymer (EPDM), ethylene-propylene copolymer, ethylene vinyl acetate (EVA), polyurea, and any and all combinations thereof.

3. The closed-cell foam according to claim 1, wherein:

a. the polymeric microspheres are present in amount of from about 1 pph to about 15 pph, and each polymeric microsphere has a diameter less than 60 microns;

b. each of the polymeric microspheres includes a polymeric outer shell and an encapsulated gas within the polymeric outer shell;

c. the encapsulated gas is selected from the group consisting of carbon dioxide, nitrogen, argon, isobutene, nitrogen, and any and all combinations therof; and

d. the polymeric matrix resin is selected from the group consisting of ethylene vinyl acetate (EVA), thermoplastic polyurethane, thermoset polyurethane, styrenic block copolymer, styrenic block copolymer with a functional group, cis-polyisoprene, trans-polyisoprene, syndiotactic 1,2-polybutadiene, silicone, and any and all combinations thereof.

4. The closed-cell foam according to claim 3, further comprising at least one additional component selected from the group consisting of organic, inorganic, or metallic fillers, organic, inorganic, or metallic fibers in the form of continuous or non-continuous fibers, fatty acids, fatty acid salts, catalysts, activators, co-activators, crosslinking agents, co-crosslinking agents, accelerators, co-accelerators, retardants, vulcanizing agents, colorants, optical brightener, uv stabilizers, anti-oxidants, processing aids, mold release agents, and any and all combinations thereof.

9. A shoe having a component including the closed cell foam according to claim 1 or claim 5.

10. The shoe according to claim 9, wherein the component is a shoe sole.

11. The shoe according to claim 9, wherein the shoe is selected from the group consisting of a golf shoe, athletic shoe, running shoe, hiking shoe, cycling shoe, and ski boot.

5. A closed-cell foam comprising:

a. from about 0.25 pph to about 20 pph of polymeric microspheres, each of the polymeric microspheres including a polymeric outer shell and an encapsulated chemical agent within the polymeric outer shell; and

b. a polymeric matrix resin including a polymer selected from the group consisting of a thermoset polymer and a thermoplastic polymer;

c. wherein the encapsulated chemical agent is present in an amount to cause expansion of the polymeric microspheres in volume by at least 10% after the polymeric microspheres are subjected to foaming conditions.

6. The closed-cell foam according to claim 5, wherein:

a. the polymeric microspheres are present in amount of from about 0.50 pph to about 15 pph;

b. the encapsulated chemical agent is present in an amount to cause expansion of the polymeric microspheres in volume by at least 50% after the polymeric microspheres are subjected to the foaming conditions, and the encapsulated chemical agent is selected from the group consisting of aliphatic hydrocarbons having 1-9 carbon atoms, aliphatic alcohols having 1-3 carbon atoms, fully and partially halogenated aliphatic hydrocarbons having 1-4 carbon atoms, and any and all combinations thereof; and

c. the polymeric matrix resin is selected from the group consisting of synthetic and natural rubbers, polycarbonates, polyolefins, functionalized polyolefins, ionomers, polyamides, polyesters, polyvinyl alcohols, polystyrenes, polyurethanes, polyarylates, polyacrylates, polyphenyl ethers, modified-polyphenyl ethers, polystyrenes, polyphthalates polymer, styrenic block copolymers, acrylonitrile-styrene-butadiene (ABS), styrene-acrylonitrile (SAN), styrene-maleic anhydryde (S/MA) polymers, styrenic copolymers, styrenic terpolymers, functionalized styrenic copolymer, functionalized styrenic terpolymer, cellulose polymers, liquid crystal polymers (LCP), ethylene-propylene-diene terpolymer (EPDM), ethylene-propylene copolymer, ethylene vinyl acetate (EVA), polyurea, and any and all combinations thereof.

7. The closed-cell foam according to claim 5, wherein:

a. the polymeric microspheres are present in amount of from about 1 to about 10 pph;

b. the encapsulated chemical agent is present in an amount to cause expansion of the polymeric microspheres in volume by at least 100% after the polymeric microspheres are subjected to the foaming conditions; and

c. the polymeric matrix resin is selected from the group consisting of ethylene vinyl acetate (EVA), thermoplastic polyurethane, thermoset polyurethane, styrenic block copolymer, styrenic block copolymer with a functional group, cis-polyisoprene, trans-polyisoprene, syndiotactic 1,2-polybutadiene, silicone, and any and all combinations thereof.

8. The closed-cell foam according to claim 7, further comprising at least one additional component selected from the group consisting of organic, inorganic, or metallic fillers, organic, inorganic, or metallic fibers in the form of continuous or non-continuous fibers, fatty acids, fatty acid salts, catalysts, activators, co-activators, crosslinking agents, co-crosslinking agents, accelerators, co-accelerators, retardants, vulcanizing agents, colorants, optical brightener, uv stabilizers, anti-oxidants, processing aids, mold release agents, and any and all combinations thereof.

12. A shoe comprising an inner sole, the inner sole including the reaction product of:

a. polymeric microspheres, each polymeric microsphere having a diameter less than 1000 microns, the polymeric microspheres including a polymeric outer shell and an encapsulated curing agent within the polymeric outer shell; and

b. a polymeric matrix including a polymer having substituents on the polymer chain selected from the group consisting of alcohols including diols and polyols, isocyanates, amines, and any and all mixtures thereof.

13. The shoe according to claim 12, wherein the polyol in the polymeric matrix is selected from the group consisting of polyester polyols, polyether polyols, polycarbonate polyols, polybutadiene polyols, and any and all mixtures thereof.

14. The shoe according to claim 12, wherein the isocyanate in the polymeric matrix is selected from the group consisting of trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, ethylene diisocyanate, diethylidene diisocyanate, propylene diisocyanate, butylene diisocyanate, bitolyelene diisocyanate, tolidine isocyanate, isophorone diisocyanate, dimeryl diisocyanate, dodecane-1,12-diisocyanate, 1,10-decamethylene diisocyanate, cyclohexylene-1,2-diisocyanate, 1,10-decamethylene diisocyanate, 1-chlorobenzene-2,4-diisocyanate, furfurylidene diisocyanate,2,4,4-trimethyl hexamethylene diisocyanate,2,2,4-trimethyl hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,3-cyclobutane diisocyanate, 1,4-cyclohexane diisocyanate,4,4′

-methylenebis(cyclohexyl isocyanate),4,4′

-methylenebis(phenyl isocyanate), 1-methyl-2,4-cyclohexane diisocyanate, 1-methyl-2,6-cyclohexane diisocyanate, 1,3-bis(isocyanato-methyl)cyclohexane, 1,6-diisocyanato-2,2,4,4-tetramethylhexane, 1,6-diisocyanato-2,4,4-tetra-trimethylhexane, trans-cyclohexane-1,4-diisocyanate, 3-isocyanato-methyl-3,5,5-trimethylcyclo-hexyl isocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, cyclo-hexyl isocyanate, dicyclohexylmethane-4,4′

-diisocyanate, 1,4-bis(isocyanatomethyl) cyclohexane, m-phenylene diisocyanate, m-xylylene diisocyanate, m-tetramethylxylylene diisocyanate, p-phenylene diisocyanate, p,p′

-biphenyl diisocyanate, 3,3′

-dimethyl-4,4′

-biphenylene diisocyanate, 3,3′

-dimethoxy-4,4′

-biphenylene diisocyanate, 3,3′

-diphenyl-4,4′

-biphenylene diisocyanate, 4,4′

-biphenylene diisocyanate, 3,3′

-dichloro-4,4′

-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, metaxylene diisocyanate, 2,4-toulene diisocyanate, 2,4′

-diphenylmethane diisocyanate, 2,4-chlorophenylene diisocyanate, 4,4′

-diphenylmethane diisocyanate, p,p′

-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolyene diisocyanate, 2,2-diphenylpropane-4,4′

-diisocyanate, 4,4′

-toluidine diisocyanate, dianidine diisocyanate, 4,4′

-diphenyl ether diisocyanate, 1,3-xylylene diisocyanate, 1,4-naphthylene diisocyanate, azobenzene-4,4′

-diisocyanate, diphenyl sulfone-4,4′

-diisocyanate, triphenylmethane 4,4′

,4″

-triisocyanate, isocyanatoethyl methacrylate, 3-isopropenyl-α

,α

-dimethylbenzyl-isocyanate, dichlorohexamethylene diisocyanate, ω

,ω

′

-diisocyanato-1,4-diethylbenzene, polymethylene polyphenylene polyisocyanate, isocyanurate modified compounds, carbodiimide modified compounds, biuret modified compounds of the above polyisocyanates, and any and all mixtures thereof.

15. The shoe according to claim 12, wherein:

a. each of the polymeric microspheres has a diameter less than 100 microns; and

b. the isocyanate in the polymeric matrix is selected from the group consisting of tetramethylene diisocyanate, hexamethylene diisocyanate, propylene diisocyanate, isophorone diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate,4,4′

-methylenebis(cyclohexyl isocyanate),4,4′

-methylenebis(phenyl isocyanate), dicyclohexylmethane-4,4′

-diisocyanate, m-phenylene diisocyanate, m-xylylene diisocyanate, m-tetramethylxylylene diisocyanate, p-phenylene diisocyanate, p,p′

-biphenyl diisocyanate, 3,3′

-dimethyl-4,4′

-biphenylene diisocyanate, 2,4-toulene diisocyanate, 2,4′

-diphenylmethane diisocyanate, 4,4′

-diphenylmethane diisocyanate, p,p′

-diphenylmethane diisocyanate1,4-naphthylene diisocyanate, and any and all mixtures thereof.

16. The shoe according to claim 12, wherein:

a. each of the polymeric microspheres has a diameter less than 100 microns; and

b. the polyol in the polymeric matrix is selected from the group consisting of polyester polyols, polyether polyols, polycarbonate polyols, polybutadiene polyols and any and all mixtures thereof.

17. The shoe according to claim 12, wherein:

a. each of the polymeric microspheres has a diameter less than 500 microns; and

b. the curing agent is selected from the group consisting of a chain extender, a crosslinking agent, and any and all mixtures thereof.

18. The shoe according to claim 17, wherein:

a. each of the polymeric microspheres has a diameter less than 100 microns; and

b. the cross linking agent is selected from the group consisting of organic peroxides, sulfur compounds, and a precious metal-containing materials.

19. The shoe according to claim 17, wherein:

a. each of the polymeric microspheres has a diameter less than 100 microns; and

b. the chain extender is selected form the group consisting of diols, polyols, diisocyanates, polyisocyanates, diamines, polyamines, dendrimers, urethane prepolymers, and any and all mixtures thereof.

20. A shoe comprising an inner sole, the inner sole including the reaction product of:

a. polymeric microspheres, each of the polymeric microspheres having a diameter less than 1000 microns, the polymeric microspheres including a polymeric outer shell and an encapsulated catalyst within the polymeric outer shell; and

b. a polymeric matrix including a silicone material.

21. The shoe according to claim 20, wherein:

a. each of the polymeric microspheres has a diameter less than 500 microns;

b. the encapsulated catalyst includes a precious metal selected from the group consisting of rhodium, ruthenium, palladium, osmium, iridium, platinum, and any and all mixtures thereof; and

c. the silicone material in the polymeric matrix is selected from the group consisting of trimethylsiloxy-endblocked dimethylsiloxane-methylhexenylsiloxane copolymers, dimethylhexenlylsiloxy-endblocked dimethylsiloxane-methylhexenylsiloxane copolymers, trimethylsiloxy-endblocked dimethylsiloxane-methylvinylsiloxane copolymers, trimethylsiloxy-endblocked methylphenylsiloxane-dimethylsiloxane-methylvinylsiloxane copolymers, dimethylvinylsiloxy-endblocked dimethylpolysiloxanes, dimethylvinylsioxy-endblocked dimethylsiloxane-methylvinylsiloxane copolymners, dimethylvinylsiloxy-endblocked methylphenylpolysiloxanes, dimethylvinylsiloxy-endblocked methylphenylsiloxane-dimethylsiloxane-methylvinylsiloxane copolymers, and any and all mixtures thereof.

22. The shoe according to claim 21, further comprising at least one additional component selected from the group consisting of organic, inorganic, or metallic fillers, organic, inorganic, or metallic fibers in the form of continuous or non-continuous fibers, fatty acids, fatty acid salts, catalysts, activators, co-activators, crosslinking agents, co-crosslinking agents, accelerators, co-accelerators, retardants, vulcanizing agents, colorants, optical brightener, uv stabilizers, anti-oxidants, processing aids, mold release agents, and any and all combinations thereof.

23. A shoe comprising an inner sole, the inner sole including the reaction product of:

a. polymeric microspheres, each of the polymeric microspheres having a diameter less than 1000 microns, the polymeric microspheres including a polymeric outer shell and an encapsulated crosslinking agent within the polymeric outer shell; and

b. a polymeric matrix including a silicone material;

24. The shoe according to claim 23, wherein:

a. each of the polymeric microspheres has a diameter less than 500 microns;

b. the encapsulated crosslinking agent is selected from the group consisting of organic peroxides, sulfur compounds, and any and all mixtures thereof; and

c. the silicone material in the polymeric matrix is selected from the group consisting of trimethylsiloxy-endblocked dimethylsiloxane-methylhexenylsiloxane copolymers, dimethylhexenlylsiloxy-endblocked dimethylsiloxane-methylhexenylsiloxane copolymers, trimethylsiloxy-endblocked dimethylsiloxane-methylvinylsiloxane copolymers, trimethylsiloxy-endblocked methylphenylsiloxane-dimethylsiloxane-methylvinylsiloxane copolymers, dimethylvinylsiloxy-endblocked dimethylpolysiloxanes, dimethylvinylsioxy-endblocked dimethylsiloxane-methylvinylsiloxane copolymners, dimethylvinylsiloxy-endblocked methylphenylpolysiloxanes, dimethylvinylsiloxy-endblocked methylphenylsiloxane-dimethylsiloxane-methylvinylsiloxane copolymers, and any and all mixtures thereof.

25. The shoe according to claim 24, further comprising at least one additional component selected from the group consisting of organic, inorganic, or metallic fillers, organic, inorganic, or metallic fibers in the form of continuous or non-continuous fibers, fatty acids, fatty acid salts, catalysts, activators, co-activators, crosslinking agents, co-crosslinking agents, accelerators, co-accelerators, retardants, vulcanizing agents, colorants, optical brightener, uv stabilizers, anti-oxidants, processing aids, mold release agents, and any and all combinations thereof.

26. A shoe comprising an inner sole, the inner sole including a responsive polymer network that reversibly changes mechanical properties when subject to a change in a parameter selected from the group consisting of temperature, moisture, ionic strength, pH, and solvent composition.

27. The shoe according to claim 26, wherein the responsive polymer network includes a polymer selected from the group consisting of:

a. a polyoxyalkylene, wherein at least one polyoxyalkylene repeating unit has hydrophobic characteristics and at least one polyoxyalkylene repeating unit has hydrophilic characteristics;

b. polyacrylic acid;

c. poly(alkyl-co-oxyalkylene); and

d. polyacrylamide.

28. A shoe comprising an inner sole, the inner sole including a responsive polymer network that reversibly changes mechanical properties when subjected to irradiation.

29. The shoe according to claim 28, wherein the responsive polymer network includes a polymer selected from the group consisting of:

a. a polyoxyalkylene, wherein at least one polyoxyalkylene repeating unit has hydrophobic characteristics and at least one polyoxyalkylene repeating unit has hydrophilic characteristics;

b. polyacrylic acid;

c. poly(alkyl-co-oxyalkylene); and

d. polyacrylamide.