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US5115007A Expired / Lapsed US ⏱️ 0.0 years remaining

Abrasion resistant polyurethane blend compositions

Assignee: Henniges Automotive Sealing Systems North America Inc
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Filing: 1991-02-21
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Granted: 1992-05-19
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Expires: 2011-02-21
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Abstract

Abstract The present invention relates to a primerless, one-part, storage stable, fast heat curable, abrasion-resistant coating composition useful as a low friction coating for an EPDM glass run channel in vehicles or similar applications. The coating composition comprises a blocked polyurethane prepolymer, a coreactive crosslinking agent, and a compatible silicone oil. The blocked polyurethane is desirably made from a hydroxyl terminated hydrogenated diene polymer or polyolefin, which is reacted with excess equivalents of a polyisocyanate reactant and the isocyanate groups blocked with a blocking agent. The cured polyurethane has very good abrasion resistance.

Inventors

  • 👤 Kohji Y. Chihara
  • 👤 Gerd M. Lenke

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-10-31 13:47
CPC Classifications
C; C08; C08L; C08L75/00; C08L75/04; B; B60; B60J; B60J10/00; B60J10/15; B60J10/17; C08G; C08G18/00; C08G18/06; C08G18/08; C08G18/10; C08G18/28; C08G18/40; C08G18/62; C08G18/6204; C08G18/6208; C09; C09D; C09D175/00; C09D175/04; Y; Y10; Y10T; Y10T428/00; Y10T428/31504; Y10T428/31551; Y10T428/31573; Y10T428/31598; Y10T428/31601

Claims Analysis

Total Claims: 33
Claim 1
Independent Claim 166 words
A heat curable, solvent-based, primerless, one-part, storage-stable composition, comprising: a blocked polyurethane prepolymer, the precursor polyurethane prepolymer being the reaction product of a hydroxyl functional hydrogenated polydiene or polyolefin intermediate with at least 1.8 equivalents of a polyisocyanate for each equivalent of said hydroxyl functional hydrocarbon intermediate, said hydrogenated polydiene or polyolefin having greater than 1.5 hydroxyl groups per average intermediate molecule and a number average molecular weight of from about 500 to about 15,000, and said precursor polyurethane prepolymer being blocked with a blocking agent; a crosslinking agent, said crosslinking agent having --NH 2 , --NHR 6 where said R 6 is an alkyl having from 1 to 4 carbon atoms, --OH, or --SH curing groups, the amount of said crosslinking agent being such that the ratio of blocked isocyanate groups to said curative groups is from about 0.8 to about 50, and from about 1 to about 100 parts by weight of silicone oil per 100 parts by weight of said blocked polyurethane prepolymer.
Claim 2
Dependent Claim 166 words
A heat curable, solvent-based, primerless, one-part, storage-stable composition, comprising: a blocked polyurethane prepolymer, the precursor polyurethane prepolymer being the reaction product of a hydroxyl functional hydrogenated polydiene or polyolefin intermediate with at least 1.8 equivalents of a polyisocyanate for each equivalent of said hydroxyl functional hydrocarbon intermediate, said hydrogenated polydiene or polyolefin having greater than 1.5 hydroxyl groups per average intermediate molecule and a number average molecular weight of from about 500 to about 15,000, and said precursor polyurethane prepolymer being blocked with a blocking agent; a crosslinking agent, said crosslinking agent having --NH 2 , --NHR 6 where said R 6 is an alkyl having from 1 to 4 carbon atoms, --OH, or --SH curing groups, the amount of said crosslinking agent being such that the ratio of blocked isocyanate groups to said curative groups is from about 0.8 to about 50, and from about 1 to about 100 parts by weight of silicone oil per 100 parts by weight of said blocked polyurethane prepolymer.
Claim 3
Dependent Claim 95 words
A composition according to claim 1, wherein said polyisocyanate has a formula ##STR8## wherein n is 2, 3, or 4 and R is aromatic, aliphatic, or combinations thereof, having form 4 to 100 carbon atoms, and wherein said hydroxyl functional hydrogenated polydiene or polyolefin is made by polymerizing an olefin monomer having from 2 to 6 carbon atoms, or a diene monomer having from 4 to 10 carbon atoms, and optionally, up to 50 mole percent of an ethylenically unsaturated comonomer, and optionally wherein said hydrogenated diene polymer is at least 50 mole percent hydrogenated.
Claim 4
Dependent Claim 79 words
A composition according to claim 2, wherein said crosslinking agent having --NH 2 or --NHR 6 groups is an aliphatic primary or secondary di, tri, or tetra-functional amine having a boiling point of at least 100° C., wherein said hydroxyl functional hydrogenated diene polymer is at least 95 mole percent hydrogenated, wherein R of said polyisocyanate has from 4 to 30 carbon atoms and wherein the viscosity of said silicone oil is from about 0.5 to about 2,500,000 centistokes.
Claim 5
Dependent Claim 127 words
A composition according to claim 3, wherein the equivalent ratio of said blocked isocyanate groups to said curative groups of said crosslinking agent is from about 2.0 to about 10.0, and wherein the equivalent ratio of said polyisocyanate to said hydroxyl functional hydrogenated diene polymer or polyolefin is from about 2.0 to about 8.0, the equivalent ratio of said polyisocyanate to said blocking agent being from about 0.5 to about 2.0, wherein the molecular weight of said hydroxyl functional hydrogenated diene polymer or polyolefin is from about 1,000 to about 8,000, wherein said hydroxyl functional hydrocarbon intermediate has from about 1.8 to about 6.0 hydroxyl groups per average intermediate molecule, wherein said polyisocyanate is 4,4-methylene diphenyl isocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, or 1,4-phenylene diisocyanate, or mixtures thereof.
Claim 6
Dependent Claim 250 words
A composition according to claim 4, wherein the equivalent ratio of said NCO groups to said blocking agent is from about 0.9 to about 1.1, wherein the molecular weight of said hydroxyl functional hydrocarbon intermediate is from about 1,000 to about 8,000, wherein said hydroxyl functional hydrogenated polydiene or polyolefin has the approximate formula ##STR9## wherein the x and y units are randomly distributed, wherein the x/y ratio is from 0.10 to about 10.0 and wherein the average number of OH groups per molecule is from about 1.5 to about 4.0, wherein said silicone oil has a backbone structure repeat unit of (--SiR*.sub.2 O--) wherein R* is methyl, wherein said silicone oil has a viscosity of from about 500 to about 1,000,000 centistokes, and wherein the amount of said silicone oil is from about 5 parts to about 80 number of OH groups per molecule is from about 1.5 to about 4.0, wherein said silicone oil has a backbone structure repeat unit of (--SiR*.sub.2 O--) wherein R* is methyl, wherein said silicone oil has a viscosity of from about 500 to about 1,000,000 centistokes, and wherein the amount of said silicone oil is from about 5 parts to about 80 parts by weight per 100 parts by weight of said blocked polyurethane intermediate, wherein said polyisocyanate is 4,4-methylene diphenyl isocyanate, wherein said blocking agent is caprolactam or a ketoxime having from 3 to 20 carbon atoms, and wherein said crosslinking agent contains said --NH 2 or said --NHR 6 groups.
Claim 7
Dependent Claim 11 words
A cured thermoset composition comprising, the cured composition of claim 1.
Claim 8
Dependent Claim 11 words
A cured thermoset composition comprising, the cured composition of claim 3.
Claim 9
Dependent Claim 11 words
A cured thermoset composition, comprising the cured composition of claim 5.
Claim 10
Dependent Claim 21 words
A cured thermoset composition according to claim 6, wherein said composition has a crockmeter abrasion resistance of at least 5,000 cycles.
Claim 11
Dependent Claim 21 words
A cured thermoset composition according to claim 7, wherein said composition has a crockmeter abrasion resistance of at least 10,000 cycles.
Claim 12
Dependent Claim 21 words
A cured thermoset composition according to claim 8, wherein said composition has a crockmeter abrasion resistance of at least 20,000 cycles.
Claim 13
Dependent Claim 10 words
An elastomer substrate coated with the composition of claim 1.
Claim 14
Dependent Claim 10 words
An elastomer substrate coated with the composition of claim 4.
Claim 15
Dependent Claim 10 words
An elastomer substrate coated with the composition of claim 6.
Claim 16
Dependent Claim 10 words
An elastomer substrate coated with the composition of claim 8.
Claim 17
Dependent Claim 10 words
An elastomer substrate coated with the composition of claim 9.
Claim 18
Dependent Claim 10 words
An elastomer substrate coated with the composition of claim 11.
Claim 19
Dependent Claim 165 words
A process for making a heat-curable, solvent-based, primerless, one-part composition, comprising the steps of: reacting a hydroxyl functional hydrogenated polydiene or polyolefin with at least 1.8 equivalents of a polyisocyanate for each equivalent of said hydrogenated polydiene or polyolefin to form a prepolymer, said hydrogenated polydiene or polyolefin having at least 1.5 hydroxyl groups per average molecule and a number average molecular weight of from about 500 to about 15,000, blocking said prepolymer to form a blocked prepolymer composition, adding a crosslinking agent to said blocked prepolymer composition, said crosslinking agent containing --NH 2 , --NHR 6 where said R 6 is an alkyl having from 1 to 4 carbon atoms, --OH, or --SH curing groups, the amount of said crosslinking agent being such that the ratio of blocked isocyanate groups to said curative groups is from about 8.0 to about 50, and adding from about to about I00 parts by weight of silicone oil per 100 parts by weight of said blocked polyurethane prepolymer.
Claim 20
Dependent Claim 165 words
A process for making a heat-curable, solvent-based, primerless, one-part composition, comprising the steps of: reacting a hydroxyl functional hydrogenated polydiene or polyolefin with at least 1.8 equivalents of a polyisocyanate for each equivalent of said hydrogenated polydiene or polyolefin to form a prepolymer, said hydrogenated polydiene or polyolefin having at least 1.5 hydroxyl groups per average molecule and a number average molecular weight of from about 500 to about 15,000, blocking said prepolymer to form a blocked prepolymer composition, adding a crosslinking agent to said blocked prepolymer composition, said crosslinking agent containing --NH 2 , --NHR 6 where said R 6 is an alkyl having from 1 to 4 carbon atoms, --OH, or --SH curing groups, the amount of said crosslinking agent being such that the ratio of blocked isocyanate groups to said curative groups is from about 8.0 to about 50, and adding from about to about I00 parts by weight of silicone oil per 100 parts by weight of said blocked polyurethane prepolymer.
Claim 21
Dependent Claim 163 words
The process according to claim 18, wherein said intermediate is a hydrogenated polydiene having the approximate formula ##STR10## wherein the x and y units are randomly distributed, wherein the x/y ratio is from 0.10 to about 10.0 and wherein the average number of OH groups per molecule is from about 1.5 to about 4.0, wherein said silicone oil has a backbone structure repeat unit of (--SiR*.sub.2 O--) wherein R* is methyl, wherein said silicone oil has a viscosity of from about 500 to about 1,000,000 centistokes, wherein the amount of said silicone oil is from about 5 parts to about 80 parts by weight per 100 parts by weight of said blocked polyurethane intermediate, wherein said polyisocyanate is 4,4-methylene diphenyl isocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, or i,4-phenylene diisocyanate, or mixtures thereof, wherein said curing agent has --NH 2 or --NHR 6 groups and is an aliphatic primary or secondary di, tri, or tetra-functional amine having a boiling point of at least 100° C.
Claim 22
Dependent Claim 10 words
The process according to claim 18, including curing said prepolymer.
Claim 23
Dependent Claim 23 words
The process according to claim 19, including said curing said prepolymer at a temperature of from about 120° C. to about 250° C.
Claim 24
Dependent Claim 20 words
The process according to claim 18, including applying said composition to an elastomer substrate and curing said prepolymer composition thereon.
Claim 25
Dependent Claim 32 words
The process according to claim 19, including applying said composition to an elastomer substrate and curing said prepolymer composition thereon at a temperature of from about 125° C. to about 250° C.
Claim 26
Dependent Claim 138 words
A heat curable, primerless, composition useful as a low friction coating composition, comprising: a blocked polyurethane prepolymer, the precursor polyurethane prepolymer being the reaction product of a hydroxyl functional hydrogenated polydiene or polyolefin intermediate with a polyisocyanate, said hydrogenated polydiene or polyolefin having greater than 1.5 hydroxyl groups per average intermediate molecule and a number average molecular weight of from about 500 to about 15,000, and said precursor polyurethane prepolymer being blocked with a blocking agent, an effective amount of a crosslinking agent to cure the composition, said crosslinking agent having --NH 2 , --NHR 6 where said R 6 is an alkyl having from 1 to 4 carbon atoms, --OH, or --SH curing groups, and from about 1 to about 100 parts by weight of silicone oil per 100 parts by weight of said blocked polyurethane prepolymer.
Claim 27
Dependent Claim 138 words
A heat curable, primerless, composition useful as a low friction coating composition, comprising: a blocked polyurethane prepolymer, the precursor polyurethane prepolymer being the reaction product of a hydroxyl functional hydrogenated polydiene or polyolefin intermediate with a polyisocyanate, said hydrogenated polydiene or polyolefin having greater than 1.5 hydroxyl groups per average intermediate molecule and a number average molecular weight of from about 500 to about 15,000, and said precursor polyurethane prepolymer being blocked with a blocking agent, an effective amount of a crosslinking agent to cure the composition, said crosslinking agent having --NH 2 , --NHR 6 where said R 6 is an alkyl having from 1 to 4 carbon atoms, --OH, or --SH curing groups, and from about 1 to about 100 parts by weight of silicone oil per 100 parts by weight of said blocked polyurethane prepolymer.
Claim 28
Dependent Claim 156 words
A composition according to claim 24, wherein said precursor polyurethane prepolymer is a reaction of a hydroxyl functional hydrogenated polydiene and a polyisocyanate wherein said polydiene has the approximate formula ##STR11## wherein the x and y units are randomly distributed, wherein the x/y ratio is from 0.10 to about 10.0 and wherein the average number of OH groups per molecule is from about 1.5 to about 4.0, wherein said polyisocyanate is 4,4l-methylene diphenyl isocyanate, wherein said blocking agent is caprolactam or ketoxime having from 3 to 20 carbon atoms, wherein said crosslinking agent contains said --NH 2 or said --NH 6 groups, wherein the equivalent ratio of said curative groups to said blocked isocyanate groups is from about 0.8 to about 50, and wherein said silicone oil has a backbone structure repeat unit of (--SiR*.sub.2 O--) wherein R* is methyl, and wherein said silicone oil has a viscosity of from about 500 to about 1,000,000 centistokes.
Claim 29
Dependent Claim 19 words
An elastomer substrate coated with the cured coating composition of claim 1, wherein said substrate is a glass-run channel.
Claim 30
Dependent Claim 22 words
An elastomer substrate coated with the cured coating composition of claim 3, wherein said substrate is a glass-run channel for an automobile.
Claim 31
Dependent Claim 23 words
An elastomer substrate coated with the cured coating composition of claim 6, wherein said substrate is an EPDM glass-run channel for an automobile.
Claim 32
Dependent Claim 23 words
An elastomer substrate coated with the cured coating composition of claim 8, wherein said substrate is an EPDM glass-run channel for an automobile.
Claim 33
Dependent Claim 21 words
An elastomer substrate coated with the cured coating composition of claim 11, wherein said substrate is a sponge bulb weather strip.

References Cited (Backward Citations)

JPS59201838A Cited
JPS60173011A Cited
JPS6241215A Cited
JPS63130616A Cited
JPS646017A Cited
US4898919A Cited

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1995-05-19 1995-11-18 1996-05-19 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1999-05-19 1999-11-18 2000-05-19 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 2003-05-19 2003-11-18 2004-05-19 $7700.00 Window Closed / Lapsed

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