Solid polymeric substrate having adherent resin component derived from curable silylated polyurethane composition
View Patent ↗A solid polymeric substrate having a resin derived from curable silylated polyurethane composition exhibiting superior properties adhered thereto. The silylated polyurethane is prepared by reacting a polyol component with a diisocyanate component to form a hydroxyl-terminated prepolymer and endcapping the prepolymer with an isocyanate silane.
1. A solid polymeric substrate having adhered to at least a portion of a surface thereof a cured composition obtained from curing of a curable resin composition while in contact with said substrate, wherein said curable resin composition comprising:
a) a curable silyl-terminated polyurethane polymer; and
b) at least one additional component selected from the group consisting of filler, UV stabilizer, antioxidant, catalyst, adhesion promoter, cure accelerator, thixotropic agent, plasticizer, moisture scavenger, pigment, dye, surfactant, defoamer, solvent and biocide, and
wherein the curable silyl-terminated polyurethane polymer is prepared by
(i) the reaction of a stoichiometric excess of a polyether polyol with polyisocyanate to form a hydroxyl group-terminated polyurethane prepolymer; and
(ii) endcapping the hydroxyl group-terminated polyurethane of step (i) with an isocyanatosilane.
2. The solid polymeric substrate having adhered to at least a portion of a surface thereof the cured composition of claim 1 wherein the polyether polyol is a polyether diol derived from ethylene oxide and/or propylene oxide and the polyisocyanate is a diisocyanate.
3. The solid polymeric substrate having adhered to at least a portion of a surface thereof the cured composition of claim 1 wherein polyether diol possesses a number average molecular weight of from about 2,000 to about 16,000 grams per mole.
4. The solid polymeric substrate having adhered to at least a portion of a surface thereof the cured composition of claim 1 wherein the polyether diol possesses a number average molecular weight of from about 8,000 to about 16,000 grams per mole.
5. The solid polymeric substrate having adhered to at least a portion of a surface thereof the cured composition of claim 1 wherein the diisocyanate is at least one member selected from the group consisting of aliphatic diisocyanate, cycloaliphatic diisocyanate, araliphatic diisocyanate and aromatic diisocyanate.
6. The solid polymeric substrate having adhered to at least a portion of a surface thereof the cured composition of claim 5 wherein the diisocyanate is at least one member selected from the group consisting of hexamethylene diisocyanate, para-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenyl-methanediisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-bis-(isocyanatomethyl)cyclohexane, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, naphathalene-1,5-diisocyanate, tetramethylxylyene diisocyanate and mixtures thereof.
7. The solid polymeric substrate having adhered to at least a portion of a surface thereof the cured composition of claim 1 wherein the stoichiometric excess of a polyether polyol with polyisocyanate is from about 1.05 to about 3.3 hydroxyl to isocyanate equivalent ratio and the hydroxyl group-terminated polyurethane prepolymer contains at least one hydroxyl functional group.
8. The solid polymeric substrate having adhered to at least a portion of a surface thereof the cured composition of claim 7 wherein the hydroxyl to isocyanate equivalent ratio is from about 1.2 to about 2.0 and the hydroxyl group-terminated polyurethane prepolymer contains at least one hydroxyl functional group.
9. The solid polymeric substrate having adhered to at least a portion of a surface thereof the cured composition of claim 1 wherein the isocyanatosilane possesses the general formula:
OCN—R 1 —Si(R 2 ) m (OR 3 ) 3-m
wherein R 1 is a divalent hydrocarbon group, to endcap the hydroxyl groups on said prepolymer with said isocyanatosilane, R 2 is alkyl group containing 1 to 4 carbon atoms, R 3 is alkyl group containing 1 to 4 carbon atoms and m is 0, 1 or 2.
10. The solid polymeric substrate having adhered to at least a portion of a surface thereof the cured composition of claim 9 wherein R 1 is an arylene, straight, cyclic or branched alkylene containing from 1 to about 12 carbon atoms.
11. The solid polymeric substrate having adhered to at least a portion of a surface thereof the cured composition of claim 9 wherein R 1 is a lower alkylene having 1 to 3 carbon atoms.
12. The solid polymeric substrate having adhered to at least a portion of a surface thereof the cured composition of claim 9 wherein R 1 has about 3 carbon atoms.
13. The solid polymeric substrate having adhered to at least a portion of a surface thereof the cured composition of claim 9 wherein said isocyanatosilane is at least one selected from the group consisting of gamma-isocyanatopropyltrimethoxysilane, gamma-isocyanatopropyl-triethoxysilaneisocyanatomethyldimethoxysilane, isocyanatomethyltrimethoxysilane, isocyanatopropyldimethylmethoxysilane, isocyanatopropyltrimethoxysilane, isocyanatoisopropyltrimethoxysilane, isocyanato-n-butyltrimethoxysilane, isocyanato-t-butyltrimethoxysilane, isocyanatopropyltriethoxysilane, isocyanatoisopropyltriethoxysilane, isocyanato-n-butyltriethoxysilane, and isocyanato-t-butyltriethoxysilane.
14. The solid polymeric substrate having adhered to at least a portion of a surface thereof the cured composition of claim 1 wherein the solid polymeric substrate is at least one selected from the group consisting of paper, cotton, fiberboard, paperboard, wood, woven or nonwoven fabrics, elastomers, polycarbonates phenol resins, epoxy resins, polyesters, polyethylencarbonate, synthetic and natural rubber, silicon, and silicone polymers.
15. The solid polymeric substrate having adhered to at least a portion of a surface thereof the cured composition of claim 14 wherein the solid polymeric substrate is at least one selected from the group consisting of polymethyl(meth)acrylate, polypropylenecarbonate, polybutenecarbonate, polystyrene, acrylonitrile-butadiene-styrene resin, acrylic resin, polyvinyl chloride, polyvinyl alcohol, polycarbonates, polyethylene terephthalate, polyurethanes and polyimides.
16. The solid polymeric substrate having adhered to at least a portion of a surface thereof the cured composition of claim 15 wherein the solid polymeric substrate is at least one selected from the group consisting of wood, polystyrene, nylon, and acrylonitrile-butadiene-styrene.
17. The solid polymeric substrate having adhered to at least a portion of a surface thereof the cured composition of claim 1 wherein the filler is at least one selected from the group consisting of fumed silica, precipitated silica, calcium carbonates, calcium, and carbon black, the antioxidant is at least one selected from the group consisting of tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane, octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 2,6-di-tert-butyl-4-(N,N′-dimethylaminomethyl)phenol, 2,6-di-tert-butyl-4-methylphenol; 2,2,6,6-tetramethyl-1-piperidinyloxy, 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy (4-hydroxy-TEMPO), 2-(3,5-di-tert-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole; dimethyl succinate polymer with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol; poly(oxy-1,2-ethanediyl), and (alpha-(3-(3-(2H-benzotriazol-2-yl-5-(1,1-dimethylethyl)-4-hydroxyphenyl)-1-oxopropyl)-omega-hydroxy, the catalyst is at least one selected from the group consisting of dibutyltin dilaurate, dibutyltin acetate, tertiary amines, stannous octoate, and stannous acetate, the adhesion promoter is at least one selected from the group consisting of N-2-aminoethyl-3-aminopropyltrimethoxysilane, N-2-aminoethyl-3-aminopropyltriethoxysilane, 1,3,5-tris(trimethoxysilylpropyl)isocyanurate, gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, bis-gamma-trimethoxysilypropyl)amine, N-Phenyl-gamma-aminopropyltrimethoxysilane, triaminofunctionaltrimethoxysilane, gamma-aminopropylmethyldiethoxysilane, gamma-aminopropylmethyldiethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-methylaminopropyltrimethoxysilane, gamma-glycidoxypropylethyldimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxyethyltrimethoxysilane, beta-(3,4-epoxycyclohexyl)propyltrimethoxysilane, beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, beta-(3,4-epoxycyclohexyl)ethyltriethoxysilane, beta-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, gamma-isocyanatopropyltriethoxysilane, gamma-isocyanatopropylmethyldimethoxysilane, beta-cyanoethyltrimethoxysilane, gamma-acryloxypropyltrimethoxysilane, gamma-methacryloxypropylmethyldimethoxysilane, 4-amino-3,3,-dimethylbutyltrimethoxysilane, and N-ethyl-3-trimethoxysilyl-2-methylpropanamine, the thixotropic agent is at least one selected from the group consisting of castor waxes, fumed silica, treated clays and polyamides, the plasticizer is at least one selected from the group consisting of phthalates, diproplyene and diethylene glycol dibenzoates, the moisture scavenger is at least one selected from the group consisting of vinyltrimethoxysilane, methyltrimethoxysilane, and ethyltrimethoxysilane.
18. The solid polymeric substrate having adhered to at least a portion of a surface thereof the cured composition of claim 1 wherein the filler is present in an amount of from about 80 to about 200 parts per 100 parts of the curable resin composition, the UV stabilizer is present in an amount from about 0 to about 5 parts per 100 parts of the curable resin composition, the antioxidant is present in an amount from about 0 to about 5 parts per 100 parts of the curable resin composition, the adhesion promoter is present in an amount of from about 0.5 to about 5 parts per 100 parts of the curable resin composition, the cure accelerator is present in an amount from about 0 to about 3 parts per 100 parts of the curable resin composition, the thixotropic agent is present in an amount from about 0 to about 10 parts per 100 parts of the curable resin composition, the plasticizer is present in an amount of from about 40 to about 200 parts per 100 parts of the curable resin composition, the moisture scavenger is present in an amount from about 0 to about 5 parts per 100 parts of the curable resin composition, and the catalyst is present in an amount from about 0 to about 3 parts per 100 parts of the curable resin composition.
19. The solid polymeric substrate having adhered to at least a portion of a surface thereof the cured composition of claim 1 wherein the polyether polyol is polypropylene ether, the diisocyanate is isophorone diisocyanate and the isocyanatosilane is gamma-isocyanatopropyltrimethoxysilane.
20. The solid polymeric substrate having adhered to at least a portion of a surface thereof the cured composition of claim 19 wherein the solid polymeric substrate is at least one selected from the group consisting of polystyrene, nylon, and acrylonitrile-butadiene-styrene.
21. The solid polymeric substrate having adhered to at least a portion of a surface thereof the cured composition of claim 1 wherein the curable resin composition is provided as a sealant.
22. The solid polymeric substrate having adhered to at least a portion of a surface thereof the cured composition of claim 1 wherein the curable resin composition is provided as a coating.
23. The solid polymeric substrate having adhered to at least a portion of a surface thereof cured composition of claim 22 wherein the solid polymeric substrate is at least one selected from the group consisting of wood, polystyrene, nylon, acrylonitrile-butadiene-styrene and polyurethane foam.
24. The solid polymeric substrate having adhered to at least a portion of a surface thereof the cured composition of claim 1 wherein the curable resin composition is provided as an adhesive.
25. The solid polymeric substrate having adhered to at least a portion of a surface thereof the cured composition of claim 22 wherein the filler is present in an amount of from about 5 to about 100 parts per 100 parts of the curable resin composition.
26. The solid polymeric substrate having adhered to at least a portion of a surface thereof a the cured composition of claim 25 wherein the filler is fumed silica present at about 5 to about 20 parts per 100 parts of the curable resin composition.