Moisture curable polyurethane composition

Claim 2

A polyurethane adhesive composition, comprising: a blend of at least polyurethane Prepolymers A, B, and C, an effective amount of carbon black to improve mechanical properties and sag resistance, and an effective amount of a resin having a polyamide backbone to improve sag resistance, said adhesive composition being a one-part moisture curable system; each said prepolymer being a reaction product of a polyol and an isocyanate, wherein the polyol used in the formation of at least one of said prepolymers is generally incompatible with the polyols used in the formaiton of said other prepolymers, wherein said polyol of each of said prepolymers is a linear or branched polyol having a backbone of polyacrylate, polybutadiene, polycarbonate, polycaprolactone, polyether, polyester, polythioether, or polyurethane, said polyols each having at least two terminal primary and/or secondary hydroxyl groups; wherein said isocyanate of said polyurethane Prepolymer A is an aromatic (poly)isocyanate, wherein said isocyanate of said polyurethane Prepolymer C is an aliphatic or cycloaliphatic (poly)isocyanate and wherein said isocyanate of said polyurethane Prepolymer B is an aromatic (poly)isocyanate or an aliphatic or a cycloaliphatic (poly)isocyanate.

Claim 3

The composition of claim 1, wherein said polyol of each of said Prepolymers A and C is a polyether backbone polyol of polyoxyethylene, polyoxypropylene, copolymers of polyoxyethylene and polyoxypropylene, polyoxybutylene, or polyoxytetramethylene, and wherein said polyol of said Prepolymer B is a polyether or a polyester backbone polyol of polyoxyethylene, polyoxypropylene, copolymers of polyoxyethylene and polyoxypropylene, polyoxybutylene, or polyoxytetramethylene, wherein said aromatic (poly)isocyanate of said polyurethane Prepolymer A is 4,4'-diphenylmethanediisocyanate (MDI), toluene diisocyanate, naphthylene-1,5-diisocyanate, 1,3- or 1,4-phenylene-diisocyanate, triphenylmethane-4,4',4"-triisocyanate, poly phenyl-polymethylene polyisocyante, or derivaties thereof, wherein said aliphatic or cycloaliphatic (poly)isocyanate of said polyurethane Prepolymer C is hexamethylene diisocyanate, 1,12-dodecanediisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- or 1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanate-methylcyclohexane, 2,4- or 2,6-hexahydrotolyenediisocyanate, hexahydro-1,3- or -1,4-phenyidiisocyanate, or perhydro-2,4'- or -4,4'-dicyclohexylmethanediisocyanate (H 12 MDI), and wherein said aromatic (poly)isocyanate of said polyurethane Prepolymer B is 4,4'-diphenylmethanediisocyanate (MDI), toluene diisocyanate, naphthylene-1,5-diisocyanate, 1,3- or 1,4-phenylene-diisocyanate, triphenylmethane-4,4',4"-triisocyanate, poly phenyl-polymethylene polyisocyanate, or derivatives thereof, and wherein said aliphatic or said cycloaliphatic (poly)isocyanate of said polyurethane Prepolymer B is hexamethylene diisocyanate, 1,12-dodecanediisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- or -1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanate-methylcyclohexane, 2,4- or 2,6-hexahydrotolyenediisocyanate, hexahydro-1,3- or -1,4-phenyidiisocyanate, or perhydro-2,4'or 4,4'-dicylohexylmethanediisocyanate.

Claim 4

The composition of claim 2, wherein said polyol of each of said prepolymers A and C is polyoxypropylene triol (PPG), and said polyol of said Prepolymer B is polyoxytetramethylene (PTMG) or polycaprolactone (PCL); and wherein said isocyanate of each of said Prepolymers A and B is MDI and said isocyanate of said Prepolymer C is H 12 MDI.

Claim 5

The composition of claim 3, wherein said carbon black additive is a carbon black conforming to ASTM N330; wherein the molecular weight of each of said Prepolymers A and C is from about 1,000 to about 20,000; wherein the functionality of each of said Prepolymers A, B, and C is from about 1.6 to about 3.0; and wherein the amount of Prepolymers A, B, and C utilized per 100 parts by weight of the blend of prepolymers is from about 98 to about 50 parts of Prepolymer A, from about 1 to about 10 parts of Prepolymer B, and from about 1 to about 40 parts of Prepolymer C.

Claim 6

The composition of claim 4, wherein the molecular weight of each of said Prepolymers A and C is from about 2,000 to about 7,000; wherein the amount of said Prepolymers A, B, and C utilized per 100 parts by weight of the blend of prepolymers is from about 79 to about 67 parts of Prepolymer A, from about 1 to about 3 parts of Prepolymer B, and from about 20 to about 30 parts of Prepolymer C; wherein said carbon black is utilized in an amount of from about 6 to about 24 weight percent based on the weight of said adhesive composition; and wherein said resin having a polyamide backbone is utilized in an amount of from about 0.2 to about 10 weight percent based on the weight of said adhesive composition.

Claim 7

The composition of claim 5, wherein the molecular weight of said Prepolymers A and C each is from about 4,000 to about 7,000; wherein the molecular weight of said Prepolymer B is from about 500 to about 3,000; wherein the functionality-of said Prepolymers A, B, and C each is from about 1.7 to about 2.4; wherein the amount of said Prepolymers A, B, and C utilized per 100 parts by weight of the blend of prepolymers is about 68 parts for Prepolymer A, about 2 parts for Prepolymer B, and about 30 parts for Prepolymer C; wherein said carbon black is utilized in an amount of from about 16 to about 20 weight percent based on the weight of said adhesive composition; and wherein said resin having a polyamide backbone is utilized in an amount of from about 1 to about 4 weight percent based on the weight of said adhesive composition.

Claim 8

The composition of claim 6, wherein said adhesive composition includes first and second cocatalysts designated as Cocatalysts I and II, respectively; wherein said Cocatalyst I is an organometallic catalyst and said Cocatalyst II is a tertiary amine or a nitrogen containing material other than said tertiary amine; wherein said Cocatalysts I and II each is used in an amount of from about 0 to about 2 weight percent based on the weight of said adhesive composition.

Claim 9

The composition of claim 7, wherein said organometallic catalyst of Cocatalyst I is i) napthenate or octoate salts of tin, lead, bismuth, cobalt, or manganese, or ii) organometallic compounds of dibutyl tin malate, dibutyl tin dilaurate, or dibutyl tin diacetate; wherein said tertiary amine or nitrogen-containing materials of Cocatalyst II is N-alkyl morphiline, N-alkyl aliphatic polyamine, N-alkyl piperazine, triethylene diamine, bis-2-N,N-dimethylaminoethyl ether, or dimorpholinodiethyl ether (DMDEE); wherein said Cocatalysts I and II each is utilized in an amount of from about 0 to about 0.5 weight percent based on the weight of said adhesive composition.

Claim 10

The composition of claim 8, wherein said Cocatalyst I is dibutyl tin diacetate and is utilized in an amount from about 0 to about 0.3 weight percent based on the weight of said adhesive composition; and wherein said Cocatalyst 11 is DMDEE and is utilized in an amount from about 0 to about 0.19 weight percent based on the weight of said adhesive composition.

Claim 11

A polyurethane adhesive composition, comprising: a blend including at least two polyurethane prepolymers selected from Prepolymers A, C, or B, other than the blend of Prepolymers A and C, and an effective amount of carbon black to improve mechanical properties and sag resistance; wherein said adhesive composition is a one-part moisture curable system; each said prepolymer being a reaction product of a polyol and an isocyanate, wherein the polyol used in the formation of at least one of said prepolymers is generally incompatible with the polyols used in the formation of said other prepolymers, wherein said polyol of each of said prepolymers is a linear or branched polyol having a backbone of polyacrylate, polybutadiene, polycarbonate, polycaprolactone, polyether, polyester, polythioether, or polyurethane, said polyols each having at least two terminal primary and/or secondary hydroxyl groups; wherein said isocyanate of said polyurethane Prepolymer A is an aromatic (poly)isocyanate, wherein said isocyanate of said polyurethane Prepolymer C is an aliphatic of cycloaliphatic (poly)isocyanate, and wherein said isocyanate of said polyurethane Prepolymer B is an aromatic (poly)isocyanate or an aliphatic or a cycloaliphatic (poly)isocyanate.

Claim 12

A polyurethane adhesive composition, comprising: a blend including at least two polyurethane prepolymers selected from Prepolymers A, C, or B, other than the blend of Prepolymers A and C, and an effective amount of carbon black to improve mechanical properties and sag resistance; wherein said adhesive composition is a one-part moisture curable system; each said prepolymer being a reaction product of a polyol and an isocyanate, wherein the polyol used in the formation of at least one of said prepolymers is generally incompatible with the polyols used in the formation of said other prepolymers, wherein said polyol of each of said prepolymers is a linear or branched polyol having a backbone of polyacrylate, polybutadiene, polycarbonate, polycaprolactone, polyether, polyester, polythioether, or polyurethane, said polyols each having at least two terminal primary and/or secondary hydroxyl groups; wherein said isocyanate of said polyurethane Prepolymer A is an aromatic (poly)isocyanate, wherein said isocyanate of said polyurethane Prepolymer C is an aliphatic of cycloaliphatic (poly)isocyanate, and wherein said isocyanate of said polyurethane Prepolymer B is an aromatic (poly)isocyanate or an aliphatic or a cycloaliphatic (poly)isocyanate.

Claim 13

The composition of claim 10 wherein said polyol of each of said Prepolymers A and C is a polyether backbone polyol polyoxyethylene, polyoxypropylene, copolymers of polyoxyethylene and polyoxypropylene, polyoxybutylene, or polyoxytetramethylene, and wherein said polyol of said Prepolymer B is a polyether or a polyester backbone polyol polyoxyethylene, polyoxypropylene, copolymers of polyoxyethylene and polyoxypropylene, polyoxybutylene, or polyoxytetramethylene, wherein said aromatic (poly)isocyanate of said polyurethane Prepolymer A is 4,4'-diphenylmethanediisocyanate (MDI), toluene diisocyanate, naphthylene-1,5-diisocyanate, 1,3- or 1,4-phenylene-diisocyanate, triphenylmethane-4,4',4"-triisocyanate, poly phenyl-polymethylene polyisocyanate, or derivatives thereof, wherein said aliphatic or cycloaliphatic (poly)isocyanate of said polyurethane Prepolymer C is hexamethylene diisocyanate, 1,12-dodecanediisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- or 1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanate-methylcyclohexane, 2,4- or 2,6-hexahydrotolyenediisocyanate, hexahydro-1,3- or -1,4-phenyldiisocyanate, or perhydro-2,4'- or -4,4'-dicyclohexylmethanediisocyanate (H 12 MDI), and wherein said aromatic (poly)isocyanate of said polyurethane Prepolymer B is 4,4'-diphenylmethanediisocyante (MDI), toluene diisocyanate, naphthylene-1,5-diisocyanate, 1,3- or 1,4-phenylene-diisocyanate, triphenylmethane-4,4',4"-triisocyanate, poly phenyl-polymethylene polyisocyanate, or derivatives thereof, and wherein said aliphatic or said cycloaliphatic (poly)isocyanate of said polyurethane Prepolymer B is hexamethylene diisocyanate, 1,12-dodecanediisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- or -1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanate-methylcyclohexane, 2,4- or 2,6-hexahydrotolyenediisocyanate, hexahydro-1,3- or 1,4-phenyldiisocyanate, or perhydro-2,4' or 4,4'-dicyclohexylmethane-diisocyanate.

Claim 14

The composition of claim 11, wherein said polyol of each of said prepolymers A and C is polyoxypropylene triol (PPG), and said polyol of said Prepolymer B is polyoxytetramethylene (PTMG) or polycaprolactone (PCL); and wherein said isocyanate of each of said Prepolymers A and B is MDI and said isocyanate of said Prepolymer C is H 12 MDI.

Claim 15

The composition of claim 12, wherein said blend of polyurethane prepolymers includes Prepolymers A, B, and C; wherein said carbon black additive is a carbon black conforming to ASTM N330; wherein the molecular weight of each of said Prepolymers A and C is from about 1,000 to about 20,000; wherein the functionality of each of said Prepolymers A, B, and C is from about 1.6 to about 3.0; and wherein the amount of Prepolymers A, B, and C utilized per 100 parts by weight of the blend of prepolymers is from about 98 to about 50 parts of Prepolymer A, from about 1 to about 10 parts of Prepolymer B, and from about 1 to about 40 parts of Prepolymer C.

Claim 16

The composition of claim 13, wherein the molecular weight of each of said Prepolymers A and C is from about 2,000 to about 7,000; wherein the amount of said Prepolymers A, B, and C utilized per 100 parts by weight of the blend of prepolymers is from about 79 to about 67 parts of Prepolymer A, from about I to about 3 parts of Prepolymer B, and from about 20 to about 30 parts of Prepolymer C; wherein said carbon black is utilized in an amount of from about 6 to about 24 weight percent based on the weight of said adhesive composition.

Claim 17

The composition of claim 14, wherein the molecular weight of said Prepolymers A and C each is from about 4,000 to about 7,000; wherein the molecular weight of said Prepolymer B is from about 500 to about 3,000; wherein the functionality of said Prepolymers A, B, and C each is from about 1.7 to about 2.4; wherein the amount of said Prepolymers A, B, and C utilized per 100 parts by weight of the blend of prepolymers is about 68 parts for Prepolymer A, about 2 parts for Prepolymer B, and about 30 parts for Prepolymer C; wherein said carbon black is utilized in an amount of from about 16 to about 20 weight percent based on the weight of said adhesive composition.

Claim 18

The composition of claim 15, wherein said adhesive composition includes first and second cocatalysts designated as Cocatalysts I and II, respectively; wherein said Cocatalyst I is an organometallic catalyst and said Cocatalyst 11 is a tertiary amine or other nitrogen containing material; wherein said Cocatalysts I and 11 each is used in an amount of from about 0 to about 2 weight percent based on the weight of said adhesive composition.

Claim 19

The composition of claim 16, wherein said organometallic catalyst of Cocatalyst I is (i) napthenate or octoate salts of tin, lead, bismuth, cobalt, or manganese, or (ii) organometallic compounds of dibutyl tin malate, dibutyl tin dilaurate, or dibutyl tin diacetate; wherein said tertiary amine or nitrogen-containing materials of Cocatalyst II is N-alkyl morphiline, N-alkyl aliphatic polyamine, N-alkyl piperazine, triethylene diamine, bis-2-N,N-dimethylaminoethyl ether, or dimorpholinodiethyl ether (DMDEE); wherein said Cocatalysts I and II each is utilized in an amount of from about 0 to about 0.5 weight percent based on the weight of said adhesive composition.

Claim 20

The composition of claim 17, wherein said Cocatalyst I is dibutyl tin diacetate and is utilized in an amount from about 0 to about 0.3 weight percent based on the weight of said adhesive composition; and wherein said Cocatalyst II is DMDEE and is utilized in an amount from about 0 to about 0.19 weight percent based on the weight of said adhesive composition.

Claim 21

A polyurethane adhesive, comprising: a blend including at least two polyurethane prepolymers selected from Prepolymers A, B, or C, other than the blend of Prepolymers A and B, and an effective amount of carbon black to improve mechanical properties and sag resistance; wherein said adhesive composition is a one-part moisture curable system; each said prepolymer being a reaction product of a polyol and an isocyanate, wherein the polyol used in the formation of said Prepolymer B is generally incompatible with the polyols used in the formation of said other prepolymers, wherein said polyol of each of said prepolymers is a linear or branched polyol having a backbone of polyacrylate, polybutadiene, polycarbonate, polycaprolactone, polyether, polyester, polythioether, or polyurethane, said polyols each having at least two terminal primary and/or secondary hydroxyl groups; wherein said isocyanate of said polyurethane Prepolymer A is an aromatic (poly)isocyanate, wherein said isocyanate of said polyurethane Prepolymer C is an aliphatic or cycloaliphatic (poly)isocyanate, and wherein said isocyanate of said polyurethane Prepolymer B is an aromatic (poly)isocyanate or an aliphatic or a cycloaliphatic (poly)isocyanate.

Claim 22

A polyurethane adhesive, comprising: a blend including at least two polyurethane prepolymers selected from Prepolymers A, B, or C, other than the blend of Prepolymers A and B, and an effective amount of carbon black to improve mechanical properties and sag resistance; wherein said adhesive composition is a one-part moisture curable system; each said prepolymer being a reaction product of a polyol and an isocyanate, wherein the polyol used in the formation of said Prepolymer B is generally incompatible with the polyols used in the formation of said other prepolymers, wherein said polyol of each of said prepolymers is a linear or branched polyol having a backbone of polyacrylate, polybutadiene, polycarbonate, polycaprolactone, polyether, polyester, polythioether, or polyurethane, said polyols each having at least two terminal primary and/or secondary hydroxyl groups; wherein said isocyanate of said polyurethane Prepolymer A is an aromatic (poly)isocyanate, wherein said isocyanate of said polyurethane Prepolymer C is an aliphatic or cycloaliphatic (poly)isocyanate, and wherein said isocyanate of said polyurethane Prepolymer B is an aromatic (poly)isocyanate or an aliphatic or a cycloaliphatic (poly)isocyanate.

Claim 23

The composition of claim 19, wherein said polyol of each of said Prepolymers A and C is a polyether backbone polyol of polyoxyethylene, polyoxypropylene, copolymers of polyoxyethylene and polyoxypropylene, polyoxybutylene, or polyoxytetramethylene, and wherein said polyol of said Prepolymer B is a polyether or a polyester backbone polyol of polyoxyethylene, polyoxypropylene, copolymers of polyoxyethylene and polyoxypropylene, polyoxybutylene, or polyoxytetramethylene, wherein said aromatic (poly)isocyanate of said polyurethane Prepolymer A is 4,4'-diphenylmethanediisocyanate (MDI), toluene diisocyanate, naphthylene-1,5-diisocyanate, 1,3- or 1,4-phenylene-diisocyanate, triphenylmethane-4,4',4"-triisocyanate, poly phenyl-polymethylene polyisocyanate, or derivatives thereof, wherein said aliphatic or cycloaliphatic (poly)isocyanate of said polyurethane Prepolymer C is hexamethylene diisocyanate, 1,12-dodecanediisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- or 1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanate-methylcyclohexane, 2,4- or 2,6'-hexahydrotolyenediisocyanate, hexahydro-1,3- or 1,4-phenyldiisocyanate, or perhydro-2,4'- or 4,4'-dicyclohexylmethanediisocyanate (H 12 MDI), and wherein said aromatic (poly)isocyanate of said polyurethane Prepolymer B is 4,4'-diphenylmethanediisocyanate (MDI), toluene diisocyanate, naphthylene-1,5-diisocyanate, 1,3- or 1,4-phenylene-diisocyanate, triphenylmethane-4,4',4"-triisocyanate, poly pehnyl-polymethylene polyisocyanate, or derivatives thereof, and wherein said aliphatic or said cycloaliphatic (poly)isocyanate of said polyurethane Prepolymer B is hexamethylene diisocyanate, 1,12-dodecanediisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- or 1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanate-methylcyclohexane, 2,4- or 2,6-hexahydrotolyenediisocyanate, hexahydro-1,3- or -1,4-phenyldiisocyanate, or perhydro-2,4' or 4,4'-dicyclohexylmethane-diisocyanate.

Claim 24

The composition of claim 20, wherein said polyol of each of said Prepolymers A and C is polyoxypropylene triol (PPG), and said polyol of said Prepolymer B is polyoxytetramethylene (PTMG) or polycaprolactone (PCL); and wherein said isocyanate of each of said Prepolymers A and B is MDI and said isocyanate of said Prepolymer C is H 12 MDI.

Claim 25

The composition of claim 21, wherein said blend of polyurethane prepolymers includes Prepolymers A, B, and C; wherein said carbon black additive is a carbon black conforming to ASTM N330; wherein the molecular weight of each of said Prepolymers A and C is from about 1,000 to about 20,000; wherein the functionality of each of said Prepolymers A, B, and C is from about 1.6 to about 3.0; and wherein the amount of Prepolymers A, B, and C utilized per 100 parts by weight of the blend of prepolymers is from about 98 to about 50 parts of Prepolymer A, from about 1 to about 10 parts of Prepolymer B, and from about 1 to about 40 parts of Prepolymer C.

Claim 26

The composition of claim 22, wherein the molecular weight of each of said Prepolymers A and C is from about 2,000 to about 7,000; wherein the amount of said Prepolymers A, B, and C utilized per 100 parts by weight of the blend of prepolymers is from about 79 to about 67 parts of Prepolymer A, from about 1 to about 3 parts of Prepolymer B, and from about 20 to about 30 parts of Prepolymer C; wherein said carbon black is utilized in an amount of from about 6 to about 24 weight percent based on the weight of said adhesive composition.

Claim 27

The composition of claim 23, wherein the molecular weight of said Prepolymers A and C each is from about 4,000 to about 7,000; wherein the molecular weight of said Prepolymer B is from about 500 to about 3,000; wherein the functionality of said Prepolymers A, B, and C each is from about 1.7 to about 2.4; wherein the amount of said Prepolymers A, B, and C utilized per 100 parts by weight of the blend of prepolymers is about 68 parts for Prepolymer A, about 22 parts for Prepolymer B, and about 30 parts for Prepolymer C; wherein said carbon black is utilized in an amount of from about 16 to about 20 weight percent based on the weight of said adhesive composition.

Claim 28

The composition of claim 24, wherein said adhesive composition includes first and second cocatalysts designated as Cocatalysts I and II, respectively; wherein said Cocatalyst I is an organometallic catalyst and said Cocatalyst II is a tertiary amine or other nitrogen containing material; wherein said Cocatalysts I and II each is used in an amount of from about 0 to about 2 weight percent based on the weight of said adhesive composition.

Claim 29

The composition of claim 25, wherein said organometallic catalyst of Cocatalyst I is (i) napthenate or octoate salts of tin, lead, bismuth, cobalt, or manganese, or (ii) organometallic compounds of dibutyl tin malate, dibutyl tin dilaurate, or dibutyl tin diacetate; wherein said tertiary amine or nitrogen-containing materials of Cocatalyst II is N-alkyl morphiline, N-alkyl aliphatic polyamine, N-alkyl piperazine, triethylene diamine, bis-2-N,N-dimethylaminoethyl ether, or dimorpholinodiethyl ether (DMDEE); wherein said Cocatalysts I and II each is utilized in an amount of from about 0 to about 0.5 weight percent based on the weight of said adhesive composition.

Claim 30

The composition of claim 26, wherein said Cocatalyst I is dibutyl tin diacetate and is utilized in an amount from about 0 to about 0.3 weight percent based on the weight of said adhesive composition; and wherein said Cocatalyst II is DMDEE and is utilized in an amount from about 0 to about 0.19 weight percent based on the weight of said adhesive composition.

Claim 31

A composition of claim 10, including an aliphatic or cycloaliphatic (polyisocyanate).

Claim 32

A composition of claim 13, including a cycloaliphatic (polyisocyanate).

Claim 33

A composition of claim 16, including H 12 MDI.