Multilayer Laminated Articles Including Poly(ureaurethane) Layers and Methods of Making the Same

Abstract

The present invention provides laminates including: (a) at least one layer of at least one polyurethane including a reaction product of components including: (i) at least one polyisocyanate; (ii) at least one branched polyol having 4 to 18 carbon atoms and at least 3 hydroxyl groups; and (iii) at least one diol having 2 to 18 carbon atoms wherein the reaction components are maintained at a temperature of at least about 100° C. for at least about 10 minutes; and (b) at least one layer of a substrate selected from the group consisting of paper, glass, ceramic, wood, masonry, textile, metal or organic polymeric material and combinations thereof; and methods of making the same.

1 - 10 . (canceled) 
     
     
         11 . A laminate comprising:
 (a) at least one layer of at least one poly(ureaurethane) comprising a reaction product of components comprising:
 (i) at least one isocyanate functional prepolymer comprising a reaction product of:
 1. at least one polyisocyanate; and 
 2. water; and 
 
 (ii) at least one branched polyol having 4 to 18 carbon atoms and at least 3 hydroxyl groups, 
   wherein the reaction product components are essentially free of amine curing agent; and   (b) at least one layer of a substrate selected from the group consisting of paper, glass, ceramic, wood, masonry, textile, metal or organic polymeric material and combinations thereof.   
     
     
         12 . A laminate comprising:
 (A) at least one layer of at least one poly(ureaurethane) comprising a reaction product of components comprising:
 (a) at least one isocyanate functional ureaurethane prepolymer comprising a reaction product of components comprising
 (1) at least one isocyanate functional urethane prepolymer comprising a reaction product of:
 a. a first amount of at least one polyisocyanate; and 
 b. a first amount of at least one branched polyol; and 
 
 (2) water,
 to form an isocyanate functional ureaurethane prepolymer; and 
 
 
 (b) a second amount of at least one polyisocyanate and a second amount of at least one branched polyol; and 
   (B) at least one layer of a substrate selected from the group consisting of paper, glass, ceramic, wood, masonry, textile, metal or organic polymeric material and combinations thereof.   
     
     
         13 . The laminate according to  claim 11 , wherein the equivalent ratio of NCO:water ranges from about 10:1 to about 2:1. 
     
     
         14 . The laminate according to  claim 11 , wherein the branched polyol is selected from the group consisting of glycerol, tetramethylolmethane, trimethylolethane, trimethylolpropane, erythritol, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitan, and mixtures thereof. 
     
     
         15 . The laminate according to  claim 11 , wherein the substrate is thermoplastic polycarbonate; polyester; poly(methyl methacrylate); polymerizate of a polyol(allyl carbonate) monomer; polymerizate of a copolymer of a polyol (allyl carbonate) with vinyl acetate, polyurethane having terminal diacrylate functionality, or aliphatic urethane having terminal allyl or acrylyl functional groups; poly(vinyl acetate); polyvinylbutyral; polyurethane; polymers of diethylene glycol dimethacrylate monomers, diisopropenyl benzene monomers, and ethoxylated trimethylol propane triacrylate monomers; cellulose acetate; cellulose propionate; cellulose butyrate; cellulose acetate butyrate; polystyrene; and copolymers of styrene with methyl methacrylate, vinyl acetate or acrylonitrile; and combinations thereof. 
     
     
         16 . The laminate according to  claim 11 , wherein the poly(ureaurethane) consists of a reaction product of components consisting of:
 (a) at least one isocyanate functional urea prepolymer comprising a reaction product of:
 (1) at least one polyisocyanate selected from the group consisting of polyisocyanate trimers and branched polyisocyanates, the polyisocyanate having at least three isocyanate functional groups; and 
 (2) water; and 
   (b) at least one branched polyol having 4 to 18 carbon atoms and at least 3 hydroxyl groups, wherein the branched polyol is selected from the group consisting of glycerol, tetramethylolmethane, trimethylolethane, trimethylolpropane, erythritol, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitan, and mixtures thereof.   
     
     
         17 . The laminate according to  claim 11 , wherein the poly(ureaurethane) consists of a reaction product of components consisting of:
 (a) at least one isocyanate functional urea prepolymer comprising a reaction product of:
 (1) at least one polyisocyanate selected from the group consisting of polyisocyanate trimers and branched polyisocyanates, the polyisocyanate having at least three isocyanate functional groups; and 
 (2) water; 
   (b) at least one branched polyol having 4 to 18 carbon atoms and at least 3 hydroxyl groups, wherein the branched polyol is selected from the group consisting of glycerol, tetramethylolmethane, trimethylolethane, trimethylolpropane, erythritol, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitan, and mixtures thereof; and   (c) at least one compound selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-ethanediol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, dodecane diol, sorbitol, mannitol, cyclopentanediol, 1,4-cyclohexanediol, cyclohexanedimethanol, 1,4-benzenedimethanol, xylene glycol, hydroxybenzyl alcohol, dihydroxytoluene, 1,4-bis(hydroxyethyl)piperazine, N,N′,bis(2-hydroxyethyl)oxamide and mixtures thereof.   
     
     
         18 . The laminate according to  claim 17 , wherein the compound (c) is selected from the group consisting of butanediol, pentanediol, cyclohexane dimethanol and mixtures thereof. 
     
     
         19 . The laminate according to  claim 17 , wherein the amount of compound (c) used to form the poly(ureaurethane) is about 0.3 to about 0.9 equivalents. 
     
     
         20 . The laminate according to  claim 11 , wherein the poly(ureaurethane) consists of a reaction product of components consisting of:
 (a) at least one isocyanate functional urea prepolymer comprising a reaction product of:
 (1) at least one polyisocyanate selected from the group consisting of polyisocyanate trimers and branched polyisocyanates, the polyisocyanate having at least three isocyanate functional groups; and 
 (2) water; 
   (b) at least one branched polyol having 4 to 18 carbon atoms and at least 3 hydroxyl groups, wherein the branched polyol is selected from the group consisting of glycerol, tetramethylolmethane, trimethylolethane, trimethylolpropane, erythritol, pentaerythritol, dipentaerythritol, trip entaerythritol, sorbitan, and mixtures thereof; and   (c) at least one of acrylamides, polyvinyl alcohols, allyl alcohols, dihydroxy oxamides, dihydroxyamides, dihydroxy piperidines, and mixtures thereof.   
     
     
         21 . The laminate according to  claim 11 , wherein the poly(ureaurethane) consists of a reaction product of components consisting of:
 (a) at least one isocyanate functional urea prepolymer consisting of a reaction product of:
 (1) at least one polyisocyanate selected from the group consisting of polyisocyanate trimers and branched polyisocyanates, the polyisocyanate having at least three isocyanate functional groups; and 
 (2) water; 
   (b) at least one branched polyol having 4 to 18 carbon atoms and at least 3 hydroxyl groups, wherein the branched polyol is selected from the group consisting of glycerol, tetramethylolmethane, trimethylolethane, trimethylolpropane, erythritol, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitan, alkoxylated derivatives thereof and mixtures thereof;   (c) at least one compound selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-ethanediol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, dodecane diol, sorbitol, mannitol, cyclopentanediol, 1,4-cyclohexanediol, cyclohexanedimethanol, 1,4-benzenedimethanol, xylene glycol, hydroxybenzyl alcohol, dihydroxytoluene, 1,4-bis(hydroxyethyl)piperazine, N,N′,bis(2-hydroxyethyl)oxamide and mixtures thereof; and   (d) at least one of acrylamides, polyvinyl alcohols, allyl alcohols, dihydroxy oxamides, dihydroxyamides, dihydroxy piperidines, and mixtures thereof.   
     
     
         22 . An article comprising the laminate of  claim 11 . 
     
     
         23 . The laminate according to  claim 11 , wherein the layer of polyurethane and layer of substrate are heated to form the laminate. 
     
     
         24 . The laminate according to  claim 11 , wherein the layer of polyurethane and layer of substrate are heated in an autoclave at a temperature of about 300° F. (149° C.) for about 2 hours to form the laminate. 
     
     
         25 . The laminate according to  claim 11 , wherein at least one of the polyurethane layers is thermally laminated to at least one of the substrate layers to form the laminated article. 
     
     
         26 . The laminate according to  claim 12 , wherein the polyisocyanate is 4,4′-methylene-bis-(cyclohexyl isocyanate). 
     
     
         27 . The laminate according to  claim 12 , wherein the branched polyol is selected from the group consisting of glycerol, glycerin, tetramethylolmethane, trimethylolethane, trimethylolpropane, erythritol, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitan, and mixtures thereof. 
     
     
         28 . The laminate according to  claim 12 , wherein the components comprise less than about 5 weight percent of polyester polyol, less than about 5 weight percent of polycarbonate polyol, and less than about 5 weight percent of polyether polyol. 
     
     
         29 . The laminate according to  claim 12 , wherein the reaction product components further comprise at least one of sorbitol, mannitol, ethylene glycol, diethylene glycol, 1,2-ethanediol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, dodecane diol, cyclopentanediol, 1,4-cyclohexanediol, cyclohexanedimethanol, 1,4-benzenedimethanol, xylene glycol, hydroxybenzyl alcohol, dihydroxytoluene, 1,4-bis(hydroxyethyl)piperazine, N,N′,bis(2-hydroxyethyl)oxamide and mixtures thereof. 
     
     
         30 . The laminate according to  claim 12 , wherein the components further comprise one or more polyurethane polyols, acrylamides, polyvinyl alcohols, hydroxy functional acrylates, hydroxy functional methacrylates, allyl alcohols, dihydroxy oxamides, dihydroxyamides, dihydroxy piperidines, dihydroxyethyl hydroquinones and mixtures thereof. 
     
     
         31 . The laminate according to  claim 12 , wherein the reaction product components are essentially free of amine curing agent. 
     
     
         32 . An article comprising the laminate of  claim 11 . 
     
     
         33 . The laminate according to  claim 12 , wherein the layer of polyurethane and layer of substrate are heated to form the laminate. 
     
     
         34 . The laminate according to  claim 12 , wherein the layer of polyurethane and layer of substrate are heated in an autoclave at a temperature of about 300° F. (149° C.) for about 2 hours to form the laminate. 
     
     
         35 . The laminate according to  claim 12 , wherein at least one of the polyurethane layers is thermally laminated to at least one of the substrate layers to form the laminated article. 
     
     
         36 . A laminate comprising:
 (a) at least one layer of at least one poly(ureaurethane) comprising a reaction product of components consisting of:
 (1) at least one isocyanate functional urea prepolymer consisting of a reaction product of:
 (i) at least one polyisocyanate selected from the group consisting of polyisocyanate trimers and branched polyisocyanates, the polyisocyanate having at least three isocyanate functional groups; and 
 (ii) water; and 
 
 (2) at least one aliphatic polyol having 4 to 18 carbon atoms and at least 2 hydroxyl groups, and 
   (b) at least one layer of a substrate selected from the group consisting of paper, glass, ceramic, wood, masonry, textile, metal or organic polymeric material and combinations thereof.   
     
     
         37 . A laminate comprising:
 (a) at least one layer of at least one poly(ureaurethane) consisting of a reaction product of components consisting of:
 (1) at least one isocyanate functional urea prepolymer consisting of a reaction product of:
 (i) at least one polyisocyanate selected from the group consisting of polyisocyanate trimers and branched polyisocyanates, the polyisocyanate having at least three isocyanate functional groups; and 
 (ii) water; 
 
 (2) at least one aliphatic polyol having 4 to 18 carbon atoms and at least 2 hydroxyl groups; and 
 (3) one or more polyurethane polyols, acrylamides, polyvinyl alcohols, hydroxy functional acrylates, hydroxy functional methacrylates, allyl alcohols, dihydroxy oxamides, dihydroxyamides, dihydroxy piperidines, dihydroxy phthalates, dihydroxyethyl hydroquinoncs and mixtures thereof, and 
   (b) at least one layer of a substrate selected from the group consisting of paper, glass, ceramic, wood, masonry, textile, metal or organic polymeric material and combinations thereof.   
     
     
         38 . A laminate comprising:
 (a) at least one layer of at least one poly(ureaurethane) consisting essentially of a reaction product of components, wherein the components used to prepare the reaction product are essentially free of polyester polyol, polycarbonate polyol, polyether polyol and amine curing agent, the components consisting essentially of:   (1) at least one isocyanate functional ureaurethane prepolymer consisting essentially of the reaction product of:
 (i) at least one isocyanate functional urethane prepolymer consisting essentially of the reaction product of:
 (A) one equivalent of at least one polyisocyanate selected from the group consisting of polyisocyanate trimers and branched polyisocyanates, the polyisocyanate having at least three isocyanate functional groups; and 
 (B) about 0.1 to about 1 equivalents of at least one aliphatic polyol, wherein the aliphatic polyol is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, 1,2-ethanediol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, dodecane diol, sorbitol, mannitol, cyclopcntanediol, 1,4-cyclohexanediol, cyclohexanedimethanol, 1,4-benzenedimethanol, xylene glycol, hydroxybenzyl alcohol, dihydroxytoluene, 1,4-bis(hydroxyethyl)piperazine, N,N′,bis(2-hydroxyethyl)oxamide, glycerol, glycerin, tetramethylolmethane, trimethylolethane, trimethylolpropane, erythritol, pentaerythritol, dipentaerythritol, tripentaerythritol, and mixtures thereof; and 
 
 (ii) about 0.05 to about 0.5 equivalents of water, to form an isocyanate functional ureaurethane prepolymer; and 
   (2) a second amount of at least one polyisocyanate and a second amount of at least one aliphatic polyol, wherein the aliphatic polyol is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, 1,2-ethanediol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, dodecane diol, sorbitol, mannitol, cyclopentanediol, 1,4-cyclohexanediol, cyclohexanedimethanol, 1,4-benzenedimethanol, xylene glycol, hydroxybenzyl alcohol, dihydroxytoluene, 1,4-bis(hydroxyethyl)piperazine, N,N′,bis(2-hydroxyethyl)oxamide, glycerol, glycerin, tetramethylolmethane, trimethylolethane, trimethylolpropane, erythritol, pentaerythritol, dipentaerythritol, tripentaerythritol, and mixtures thereof, and wherein the ratio of number of isocyanate groups to the number of hydroxyl groups is in the range of about 1.05:1 to about 1:1; and,   (3) optionally, one or more of acrylamide, methacrylamide, dimethylacrylamide, polyvinyl alcohols, hydroxy functional acrylates, hydroxy functional methacrylates, allyl alcohols, dihydroxy oxamides, dihydroxyamides, dihydroxy piperidines, dihydroxyethyl hydroquinones and mixtures thereof, and   (b) at least one layer of a substrate selected from the group consisting of paper, glass, ceramic, wood, masonry, textile, metal or organic polymeric material and combinations thereof.   
     
     
         39 . A laminate comprising:
 (a) at least one layer of at least one poly(ureaurethane) consisting of a reaction product of components, wherein the components used to prepare the reaction product are free of polyester polyol, polycarbonate polyol, polyether polyol and amine curing agent, the components consisting of:   (1) at least one isocyanate functional ureaurethane prepolymer consisting of the reaction product of:
 (i) at least one isocyanate functional urethane prepolymer consisting of the reaction product of:
 (A) one equivalent of at least one polyisocyanate selected from the group consisting of polyisocyanate trimers and branched polyisocyanates, the polyisocyanate having at least three isocyanate functional groups; and 
 (B) about 0.1 to about 1 equivalents of at least one aliphatic polyol, wherein the aliphatic polyol is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, 1,2-ethanediol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, dodecane diol, sorbitol, mannitol, cyclopentanediol, 1,4-cyclohexanediol, cyclohexanedimethanol, 1,4-benzenedimethanol, xylene glycol, hydroxybenzyl alcohol, dihydroxytoluene, 1,4-bis(hydroxyethyl)piperazine, N,N′,bis(2-hydroxyethyl)oxamide, glycerol, glycerin, tetramethylolmethane, trimethylolethane, trimethylolpropane, erythritol, pentaerythritol, dip entaerythritol, tripentaerythritol, and mixtures thereof; and 
 
 (ii) about 0.05 to about 0.5 equivalents of water, to form an isocyanate functional ureaurethane prepolymer; and 
   (2) a second amount of at least one polyisocyanate and a second amount of at least one aliphatic polyol, wherein the aliphatic polyol is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, 1,2-ethanediol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, dodecane diol, sorbitol, mannitol, cyclopentanediol, 1,4-cyclohexanediol, cyclohexanedimethanol, 1,4-benzenedimethanol, xylene glycol, hydroxybenzyl alcohol, dihydroxytoluene, 1,4-bis(hydroxyethyl)piperazine, N,N′,bis(2-hydroxyethyl)oxamide, glycerol, glycerin, tetramethylolmethane, trimethylolethane, trimethylolpropane, erythritol, pentaerythritol, dipentaerythritol, trip entaerythritol, and mixtures thereof, and wherein the ratio of number of isocyanate groups to the number of hydroxyl groups is in the range of about 1.05:1 to about 1:1; and,   (3) optionally, one or more of acrylamide, methacrylamide, dimethylacrylamide, polyvinyl alcohols, hydroxy functional acrylates, hydroxy functional methacrylates, allyl alcohols, dihydroxy oxamides, dihydroxyamides, dihydroxy piperidines, dihydroxyethyl hydroquinones and mixtures thereof, and   (b) at least one layer of a substrate selected from the group consisting of paper, glass, ceramic, wood, masonry, textile, metal or organic polymeric material and combinations thereof.   
     
     
         40 . A laminate comprising:
 (a) at least one layer of at least one poly(ureaurethane) comprising a reaction product of components comprising:
 (1) about 1 equivalent of at least one polyisocyanate selected from the group consisting of polyisocyanate trimers and branched polyisocyanates, the polyisocyanate having at least three isocyanate functional groups; 
 (2) about 0.1 to about 0.9 equivalents of at least one polyol having 4 to 18 carbon atoms and at least 2 hydroxyl groups, the polyol being selected from the group consisting of sorbitol, mannitol, glycerol, glycerin, tetramethylolmethane, trimethylolethane, trimethylolpropane, erythritol, pentaerythritol, dipentaerythritol, tripentaerythritol, and mixtures thereof; and 
 (3) at least one amine curing agent selected from the group consisting of: 4,4′-methylenebis (3-chloro-2,6-diethyl aniline), 2,4-di amino-3,5-diethyl-toluene, 2,6-diamino-3,5-diethyl-toluene, dimethylthiotoluenediamine (DMTDA) 4,4′-methylene-bis-(2-chloroaniline), ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), piperazine, morpholine, substituted morpholine, piperidine, substituted piperidine, diethylenediamine (DEDA), and 2-amino-1-ethylpiperazine, C 1 -C 3  dialkyl toluenediamine, methylene dianiline or trimethyleneglycol di(para-aminobenzoate), compounds of formulae (XVI)-(XXX): 
   
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
       wherein R 3  and R 4  are each independently C 1 -C 3  alkyl, and R 5  is selected from hydrogen and halogen; 
       
         
           
           
               
               
           
         
       
       wherein R 20 , R 21 , R 22 , and R 23  are each independently selected from H, C 1 -C 3  alkyl, CH 3 —S— and halogen, and mixtures thereof;
 wherein the reaction product components comprise less than about 5 weight percent of polyester polyol, less than about 5 weight percent of polycarbonate polyol and less than about 5 weight percent of polyether polyol, and 
 (b) at least one layer of a substrate selected from the group consisting of paper, glass, ceramic, wood, masonry, textile, metal or organic polymeric material and combinations thereof. 
 
     
     
         41 . A laminate comprising:
 (a) at least one layer of at least one poly(ureaurethane) comprising a reaction product of components comprising:
 (1) about 1 equivalent of at least one polyisocyanate selected from the group consisting of polyisocyanate trimers and branched polyisocyanates, the polyisocyanate having at least three isocyanate functional groups; 
 (2) about 0.1 to about 0.9 equivalents of at least one polyol selected from the group consisting of ethylene glycol, diethylene glycol, 1,2-ethanediol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, dodecane diol, sorbitol, mannitol, cyclopentanediol, 1,4-cyclohexanediol, cyclohexanedimethanol, 1,4-benzenedimethanol, xylene glycol, hydroxybenzyl alcohol, dihydroxytoluene bis(2-hydroxyethyl) terephthalate, 1,4-bis(hydroxyethyl)piperazine, N,N′,bis(2-hydroxyethyl)oxamide, glycerol, glycerin, tetramethylolmethane, trimethylolethane, trimethylolpropane, erythritol, pentaerythritol, dipentaerythritol, tripentaerythritol, and mixtures thereof; and 
 (3) at least one amine curing agent selected from the group consisting of: ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), piperazine, morpholine, substituted morpholine, piperidine, substituted piperidine, diethylenediamine (DEDA), and 2-amino-1-ethylpiperazine; 
   wherein the reaction product components comprise less than about 5 weight percent of polyester polyol, less than about 5 weight percent of polycarbonate polyol and less than about 5 weight percent of polyether polyol, and   (b) at least one layer of a substrate selected from the group consisting of paper, glass, ceramic, wood, masonry, textile, metal or organic polymeric material and combinations thereof.