Flexible polyurethane material

Abstract

The present invention provides a flexible two component polyurethane and method for producing the polyurethane. The cured polyurethane is flexible, durable and weather resistant. The polyurethane is suitable for use as a protective layer on various substrates. The flexible polyurethane is the reaction product of solvent-free reaction components. The first component includes one or more polyols, optionally, one or more diols, and a catalyst. The second component includes a primary aliphatic isocyante crosslinker.

What is claimed is: 
     
       1. An article comprising:
 a) a substrate selected from polymeric material, wood, fabric, reinforced polymers, metal, reflective sheeting, and a combination thereof, wherein the polymeric material or the polymer of the reinforced polymer comprises a polyvinyl chloride, polyester, acrylic polymer, polycarbonate, polyurethane, polyethylene acrylic acid copolymer, or polyvinyl acetate; and 
 b) a clear polyurethane applied as a protective layer on a first surface of said substrate, said polyurethane is a reaction product of,
 i) a first component comprising one or more polyols having an equivalent weight in the range from about 28 to about 3000, optionally one or more diols having an equivalent weight in the range from about 30 to about 4000, and a catalyst; and 
 ii) a second component comprising at least 50 weight percent of a primary polyisocyanate having a functionality of at least three, and wherein the first and second components together are solvent free, and wherein any isocyanate source in the clear protective polyurethane layer consists of the primary polyisocyanate. 
 
 
     
     
       2. An article as recited in  claim 1 , wherein an adhesive is applied onto a second surface of said substrate opposite to the first surface of said substrate. 
     
     
       3. An article as recited in  claim 1 , further comprising indicia applied onto the first surface of said substrate and covered by said polyurethane. 
     
     
       4. An article as recited in  claim 3 , wherein said indicia is three dimensional. 
     
     
       5. An article as recited in  claim 3 , wherein said polyurethane layer covers all exposed surfaces of the indicia and the first surface of said substrate. 
     
     
       6. An article as recited in  claim 4 , wherein said three dimensional indicia comprises a cured polyurethane body having a mounting surface, a tie layer bonded to the mounting surface, and an adhesive body adhered to the tie layer. 
     
     
       7. An article as recited in  claim 1 , wherein said substrate is a base substrate and one or more secondary articles are applied over said base substrate, each of said secondary articles comprising an adhesive attachment system, a substrate, and indicia. 
     
     
       8. An article as recited in  claim 7 , wherein said base substrate includes indicia and said secondary articles are applied over the indicia of said base substrate. 
     
     
       9. An article as recited in  claim 7 , wherein said one or more secondary articles include three dimensional articles. 
     
     
       10. An article as recited in  claim 1 , wherein said catalyst is a tin-based catalyst and said polyurethane, upon exposure to moisture or carboxyl groups, does not exhibit a substantial amount of outgassing. 
     
     
       11. An article as recited in  claim 1 , wherein the second component further comprises one or more monomeric isocyanates. 
     
     
       12. An article as recited in  claim 1 , wherein the first and second components form a solvent-free admixture having an NCO:OH ratio of about 0.75 to about 1.25. 
     
     
       13. An article as recited in  claim 1 , wherein the polyurethane contains up to about 20 weight percent of polyether segments. 
     
     
       14. An article comprising:
 a) a substrate selected from polymeric material, wood, fabric, reinforced polymers, metal, reflective sheeting, and a combination thereof, wherein the polymeric material or the polymer of the reinforced polymer comprises a polyvinyl chloride, polyester, acrylic polymer, polycarbonate, polyurethane, polyethylene acrylic acid copolymer, or polyvinyl acetate; and 
 b) a clear protective polyurethane layer on directly contacting a first surface of the substrate, wherein the clear protective polyurethane layer contains primary aliphatic isocyanate crosslinking, and wherein about 25% or more of the total crosslink density is contributed by a polyisocyanate components component having a functionality of at least three, said clear protective polyurethane layer exhibiting at least one property selected from the group consisting of a flexural modulus of 1.0×108 1.0×10 8  pascals or less, a storage modulus of 1.0×108 1.0×10 8  pascals or less, a Shore A hardness of less than 94, a Hoffman scratch-hardness test result of 2 or less, and a color shift, in accordance with heat aging test ASTM D2244-79, within 1 delta E, wherein the clear protective polyurethane layer comprises a polyester polyurethane, polycarbonate polyurethane, polyacrylate polyurethane, polyalkylene polyurethane, polyether polyurethane, or a combination thereof and wherein any isocyanate source in the clear protective polyurethane layer consists of the polyisocyanate component. 
 
     
     
       15. An article as recited in  claim 14 , wherein the polyurethane is a reaction product of:
 (i) a first component comprising one or more polyols having an equivalent weight in the range from about 28 to about 3000, optionally one or more diols having an equivalent weight in the range from about 30 to about 4000, and a catalyst; and 
 (ii) a second component comprising at least 50 weight percent of a primary polyisocyanate having a functionality of at least three, and wherein the first and second components together are solvent free. 
 
     
     
       16. An article as recited in  claim 14 , further comprising indicia on a portion of the first surface of the substrate, wherein the polyurethane covers all exposed surfaces of the indicia and the first surface of said substrate. 
     
     
       17. An article as recited in  claim 14 , further comprising an adhesive layer on a second surface of the substrate, wherein the second surface is opposite the first surface of said substrate. 
     
     
       18. An article comprising:
 a) a substrate having a first surface, said substrate selected from polymeric material, wood, fabric, reinforced polymers, metal, reflective sheeting, and a combination thereof, wherein the polymeric material or the polymer of the reinforced polymer comprises a polyvinyl chloride, polyester, acrylic polymer, polycarbonate, polyurethane, polyethylene acrylic acid copolymer, or polyvinyl acetate; 
 b) indicia on at least a portion of the first surface of the substrate; and 
 c) a clear polyurethane applied as a protective layer over the indicia and any exposed portions of the first surface of said substrate, wherein the polyurethane is a reaction product of:
 i) a first component comprising one or more polyols having an equivalent weight in the range from about 28 to about 3000, optionally one or more diols having an equivalent weight in the range from about 30 to about 4000, and a catalyst; and 
 ii) a second component comprising at least 50 weight percent of a primary polyisocyanate having a functionality of at least three, and wherein the first and second components together are solvent free; 
 
 wherein the first and second components form a solvent-free admixture having an NCO:OH ratio of about 0.75 to about 1.25, and wherein any isocyanate source in the clear protective polyurethane layer consists of the polyisocyanate component. 
 
     
     
       19. An article as recited in  claim 18 , further comprising an adhesive layer on a second surface of the substrate, wherein the second surface is opposite the first surface of said substrate. 
     
     
       20. An article comprising:
 a) a substrate selected from polymeric material, wood, fabric, reinforced polymers, metal, reflective sheeting, and a combination thereof, wherein the polymeric material or the polymer of the reinforced polymer comprises a polyvinyl chloride, polyester, acrylic polymer, polycarbonate, polyurethane, polyethylene acrylic acid copolymer, or polyvinyl acetate; and   b) a flexible clear polyurethane applied as a layer on a surface of said substrate, said flexible polyurethane comprising a reaction product of,
 i) a first component included one or more polyols having an equivalent weight in the range from about 28 to about 3000, optionally one or more diols having an equivalent weight in the range from about 30 to bout 4000, and a catalyst; and 
 ii) a second component comprising a primary aliphatic isocyanate crosslinker having at least 50 weight percent polyisocyanate, 
   wherein the first and second components together are solvent free.   
     
     
       21. An article as recited in  claim 1 , wherein the first component comprises greater than about 20 weight percent polyester. 
     
     
       22. An article as recited in  claim 1 , wherein the primary polyisocyanate comprises a primary aliphatic polyisocyanate. 
     
     
       23. An article as recited in  claim 18 , wherein the first component comprises greater than about 20 weight percent polyester. 
     
     
       24. An article as recited in  claim 18 , wherein the primary polyisocyanate comprises a primary aliphatic polyisocyanate. 
     
     
       25. An article as recited in  claim 20 , wherein the first component comprises greater than about 20 weight percent polyester. 
     
     
       26. An article as recited in claim  14  35, wherein the first component comprises greater than about 20 weight percent polyester. 
     
     
       27. An article as recited in  claim 1 , wherein said clear polyurethane protective layer has a curved outer surface. 
     
     
       28. An article as recited in  claim 14 , wherein said clear protective polyurethane layer has a curved outer surface. 
     
     
       29. An article as recited in  claim 18 , wherein said clear polyurethane protective layer has a curved outer surface. 
     
     
       30. An article as recited in  claim 20 , wherein said clear polyurethane layer has a curved outer surface. 
     
     
       31. The article of  claim 1 , wherein at least a portion of the substrate is visible through the polyurethane protective layer. 
     
     
       32. The article of  claim 14 , wherein at least a portion of the substrate is visible through the polyurethane protective layer. 
     
     
       33. The article of  claim 18 , wherein at least a portion of the substrate is visible through the polyurethane protective layer. 
     
     
       34. The article of  claim 20 , wherein at least a portion of the substrate is visible through the polyurethane protective layer. 
     
     
       35. An article as recited in claim 14, wherein the clear protective polyurethane layer is a reaction product of:
 (i) a first component comprising one or more diols selected from the group consisting of: polyester diols, polycarbonate diols, polyacrylate diols, polyalkylene diols, and polyether diols, or a combination thereof; and   (ii) a second component comprising the polyisocyanate component.   
     
     
       36. An article as recited in claim 35, wherein the diols comprise up to about 65 weight percent of the first component. 
     
     
       37. An article as recited in claim 35, wherein the one or more diols include a short chain diol having an equivalent weight in the range from about 30 to about 400 and a long chain diol having an equivalent weight in the range of from about 400 to about 4000. 
     
     
       38. An article as recited in claim 14, wherein the clear protective polyurethane layer is a reaction product of:
 (i) a first component comprising one or more polyols having an equivalent weight in the range from about 28 to about 3000, optionally one or more diols having an equivalent weight in the range from about 30 to about 4000, and a catalyst; and   (ii) a second component comprising at least 50 weight percent of the polyisocyanate component.   
     
     
       39. An article as recited in claim 38, wherein the catalyst is a tin-based catalyst and the clear protective polyurethane layer, upon exposure to moisture or carboxyl groups, does not exhibit a substantial amount of outgassing. 
     
     
       40. An article as recited in claim 14, wherein the clear protective polyurethane layer contains up to about 20 weight percent of polyether segments. 
     
     
       41. An article as recited in claim 40, wherein the clear protective polyurethane layer contains up to about 15 weight percent of polyether segments. 
     
     
       42. An article as recited in claim 14, wherein the substrate is a base substrate and one or more secondary articles are applied over the base substrate, each of the secondary articles comprising an adhesive attachment system, a substrate, and indicia. 
     
     
       43. An article as recited in claim 42, wherein the base substrate includes indicia and the secondary articles are applied over the indicia of the base substrate. 
     
     
       44. An article as recited in claim 14, further comprising:
 c) an adhesive layer directly contacting a second surface of the substrate, wherein the second surface is opposite the first surface of said substrate.   
     
     
       45. An article as recited in claim 14, wherein the clear protective polyurethane layer is a reaction product of a diol. 
     
     
       46. An article as recited in claim 14, wherein the substrate comprises a polymeric material. 
     
     
       47. An article as recited in claim 46, wherein the polymeric material comprises polyurethane. 
     
     
       48. An article as recited in claim 47, wherein the clear protective polyurethane layer comprises a polyester polyurethane. 
     
     
       49. An article as recited in claim 48, wherein the clear protective polyurethane layer further comprises a polyacrylate polyurethane. 
     
     
       50. An article as recited in claim 14, wherein the clear protective layer is a reaction product of one or more diol or polyol compounds comprising polyesters, polycarbonates, polyacrylates, polyalkylenes, and polyethers, and combinations thereof.