US4041208A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Transparent, impact-resistant polyesterurethane laminates
Assignee: PPG Industries Inc
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Filing: 1974-05-21
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Granted: 1977-08-09
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Expires: 1994-05-21
Abstract
Abstract Laminated glass articles useful as automobile windshields or in other safety glass applications comprising a polyesterurethane and at least one sheet of glass are described. The polyesterurethane is a thermoplastic, transparent material that is formed preferably from an aliphatic polyester, e.g., poly(1,4-butylene adipate), a cycloaliphatic diisocyanate, e.g., 4,4'-methylene-bis (cyclohexyl isocyanate), and a monomeric aliphatic diol, e.g., 1,4-butane diol.
Inventors
- 👤 Nelson V. Seeger
- 👤 Andrew J. Kaman
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-24 10:43
CPC Classifications
C; C09; C09J; C09J175/00; C09J175/04; C09J175/06; B; B32; B32B; B32B17/00; B32B17/06; B32B17/10; B32B17/10005; B32B17/10009; B32B17/10018; B32B17/1055; B32B17/10688; B32B17/10697; B32B17/1077; B32B17/10807; B32B17/10816; B32B17/10825; B32B17/10834; B32B17/10844; B32B17/10853; B32B17/10981; B32B27/00; B60; B60J; B60J1/00; B60J1/02; C08; C08G; C08G18/00; C08G18/06; C08G18/08; C08G18/10; C08G18/28; C08G18/40; C08G18/42; C08G18/65; C08G18/66; C08G18/6633; C08G18/70; C08G18/72; C08G18/74; C08G18/75; C09J157/00; C09J157/06; Y; Y10; Y10T; Y10T428/00; Y10T428/31504; Y10T428/31551; Y10T428/31598; Y10T428/31601
Claims Analysis
Total Claims: 28
Claim 1
Independent Claim
220 words
An optically-clear, energy-absorbing laminate, comprising at least one glass sheet bonded to a sheet of a substantially unreacted isocyanate free, thermoplastic, transparent polyesterurethane that is the reaction product of (a) essentially linear hydroxy-terminated polyester having a liquidus temperature of at least 44° C., said polyester being selected from the group consisting of poly(1,4-butylene adipate) and poly(1,4-butylene azelate) having a molecular weight of about 2000, (b) 4,4'-methylene-bis-(cyclohexyl isocyanate), and (c) aliphatic diol containing from 4 to 8 carbon atoms, the mole ratio of (c) to (a) being from about 1.5:1 to about 5:1, the isocyanate groups provided by (b) being substantially numerically equivalent to the sum of hydroxyl groups provided by (c) and (a) whereby to provide a polyesterurethane that is substantially free of unreacted isocyanate groups, said mole ratio of (c) to (a) being so proportioned within said range that a rigidly held laminate prepared from about 0.030 inch thick sheeting of said polyesterurethane sandwiched between two 12" × 12" × 1/8" glass sheets is non-brittle at 0° F. and exhibits a mean penetration velocity of at least 20 miles per hour at laminate temperatures of 0° F. and 70° F., and a mean penetration velocity of at least 17 miles per hour at a laminate temperature of 120° F. when impacted with a five pound free falling steel ball.
Claim 2
Dependent Claim
220 words
An optically-clear, energy-absorbing laminate, comprising at least one glass sheet bonded to a sheet of a substantially unreacted isocyanate free, thermoplastic, transparent polyesterurethane that is the reaction product of (a) essentially linear hydroxy-terminated polyester having a liquidus temperature of at least 44° C., said polyester being selected from the group consisting of poly(1,4-butylene adipate) and poly(1,4-butylene azelate) having a molecular weight of about 2000, (b) 4,4'-methylene-bis-(cyclohexyl isocyanate), and (c) aliphatic diol containing from 4 to 8 carbon atoms, the mole ratio of (c) to (a) being from about 1.5:1 to about 5:1, the isocyanate groups provided by (b) being substantially numerically equivalent to the sum of hydroxyl groups provided by (c) and (a) whereby to provide a polyesterurethane that is substantially free of unreacted isocyanate groups, said mole ratio of (c) to (a) being so proportioned within said range that a rigidly held laminate prepared from about 0.030 inch thick sheeting of said polyesterurethane sandwiched between two 12" × 12" × 1/8" glass sheets is non-brittle at 0° F. and exhibits a mean penetration velocity of at least 20 miles per hour at laminate temperatures of 0° F. and 70° F., and a mean penetration velocity of at least 17 miles per hour at a laminate temperature of 120° F. when impacted with a five pound free falling steel ball.
Claim 3
Dependent Claim
17 words
The laminate of claim 1 wherein the polyesterurethane sheet is an interlayer between two sheets of glass.
Claim 4
Dependent Claim
13 words
The laminate of claim 1 wherein the polyesterurethane is a random block polymer.
Claim 5
Dependent Claim
25 words
The laminate of claim 1 wherein the stereoisomer content of the 4,4'-methylene-bis-(cyclohexyl isocyanate) is about 55 percent total trans and about 45 percent total cis.
Claim 6
Dependent Claim
34 words
The laminate of claim 1 wherein the stereoisomer content of the 4,4'-methylene-bis-(cyclohexyl isocyanate) is about 19 to 21 percent trans, trans, 17 to 18 percent cis, cis, and 62 to 64 percent cis, trans.
Claim 7
Dependent Claim
11 words
The laminate of claim 1 wherein the aliphatic diol is 1,4-butanediol.
Claim 8
Dependent Claim
28 words
The laminate of claim 1 wherein the polyesterurethane is prepared by simultaneously reacting reactants (a), (b) and (c) at temperatures of between about 65° C. and 180° C.
Claim 9
Dependent Claim
18 words
The laminate of claim 1 wherein the polyesterurethane has a urethane content of from 10 to 20 percent.
Claim 10
Dependent Claim
18 words
The laminate of claim 1 wherein the hard segment of the polyesterurethane comprises from 15 to 45 percent.
Claim 11
Dependent Claim
30 words
The laminate of claim 1 wherein the polyesterurethane has an inherent viscosity of from 0.8 to 1.6 dl/g, as measured at a 0.5 percent concentration in N-methyl-2-pyrrolidone at 30° C.
Claim 12
Dependent Claim
52 words
The laminate of claim 1 wherein the polyester is poly(1,4-butylene adipate) having a molecular weight of about 2000, the stereoisomer content of the 4,4'-methylene-bis-(cyclohexyl isocyanate) is about 19 to 21 percent trans, trans, 17 to 18 percent cis, cis, and 62 to 64 percent cis, trans, and the aliphatic diol is 1,4-butanediol.
Claim 13
Dependent Claim
17 words
The laminate of claim 11 wherein the polyesterurethane sheet is an interlayer between two sheets of glass.
Claim 14
Dependent Claim
18 words
The laminate of claim 12 wherein the polyesterurethane sheet has a thickness of from 15 to 45 mils.
Claim 15
Dependent Claim
30 words
The laminate of claim 11 wherein the polyesterurethane has an inherent viscosity of from 0.8 to 1.6 dl/g, as measured at a 0.5 percent concentration in N-methyl-2-pyrollidone at 30° C.
Claim 16
Dependent Claim
18 words
The laminate of claim 14 wherein the polyesterurethane has a urethane content of from 12 to 17.5 percent.
Claim 17
Dependent Claim
18 words
The laminate of claim 15 wherein the hard segment of the polyesterurethane is from 20 to 36 percent.
Claim 18
Dependent Claim
17 words
The laminate of claim 13 wherein the thickness of the sheet is from 18 to 22 mils.
Claim 19
Dependent Claim
52 words
The laminate of claim 1 wherein the polyester is poly(1,4-butylene azelate) having a molecular weight of about 2000, the stereoisomer content of the 4,4'-methylene-bis-(cyclohexyl isocyanate) is about 19 to 21 percent trans, trans, 17 to 18 percent cis, cis, and 62 to 64 percent cis, trans, and the aliphatic diol is 1,4-butanediol.
Claim 20
Dependent Claim
210 words
An optically-clear, energy-absorbing laminate, comprising at least one glass sheet bonded to a sheet of a substantially unreacted isocyanate free, thermoplastic, transparent polyesterurethane that is the reaction product of (a) essentially linear poly(epsilon caprolactone) diol having a molecular weight of between about 1000 and about 2000 and a liquidus temperature of at least 44° C., (b) 4,4'-methylene-bis(cyclohexyl isocyanate), and (c) aliphatic diol containing from 4 to 8 carbon atoms, the mole ratio of (c) to (a) being from about 0.4:1 to about 5:1, the isocyanate groups provided by (b) being substantially numerically equivalent to the hydroxyl groups provided by (a) and (c) whereby to provide a polyesterurethane that is substantially free of unreacted isocyanate groups, said mole ratio of (c) to (a) being so proportioned within said range that a rigidly held laminate prepared from about 0.030 inch sheeting of said polyesterurethane sandwiched between two 12" × 12" × 1/8 inch sheets of glass is non-brittle at 0° F. and exhibits a mean penetration velocity of at least 20 miles per hour at laminate temperatures of 0° F. and 70° F., and a mean penetration velocity of at least 17 miles per hour at a laminate temperature of 120° F. when impacted with a five pound free falling steel ball.
Claim 21
Dependent Claim
210 words
An optically-clear, energy-absorbing laminate, comprising at least one glass sheet bonded to a sheet of a substantially unreacted isocyanate free, thermoplastic, transparent polyesterurethane that is the reaction product of (a) essentially linear poly(epsilon caprolactone) diol having a molecular weight of between about 1000 and about 2000 and a liquidus temperature of at least 44° C., (b) 4,4'-methylene-bis(cyclohexyl isocyanate), and (c) aliphatic diol containing from 4 to 8 carbon atoms, the mole ratio of (c) to (a) being from about 0.4:1 to about 5:1, the isocyanate groups provided by (b) being substantially numerically equivalent to the hydroxyl groups provided by (a) and (c) whereby to provide a polyesterurethane that is substantially free of unreacted isocyanate groups, said mole ratio of (c) to (a) being so proportioned within said range that a rigidly held laminate prepared from about 0.030 inch sheeting of said polyesterurethane sandwiched between two 12" × 12" × 1/8 inch sheets of glass is non-brittle at 0° F. and exhibits a mean penetration velocity of at least 20 miles per hour at laminate temperatures of 0° F. and 70° F., and a mean penetration velocity of at least 17 miles per hour at a laminate temperature of 120° F. when impacted with a five pound free falling steel ball.
Claim 22
Dependent Claim
11 words
The laminate of claim 19 wherein the aliphatic diol is 1,4-butanediol.
Claim 23
Dependent Claim
25 words
The laminate of claim 20 wherein the 4,4'-methylene-bis(cyclohexyl isocyanate) has a stereoisomer content of about 55 percent total trans and about 45 percent total cis.
Claim 24
Dependent Claim
34 words
The laminate of claim 20 wherein the 4,4'-methylene-bis(cyclohexyl isocyanate) has a stereoisomer content of about 19 to 21 percent trans, trans, 17 to 18 percent cis, cis and 62 to 64 percent cis, trans.
Claim 25
Dependent Claim
18 words
The laminate of claim 22 wherein the polyesterurethane sheet has a thickness of from 15 to 45 mils.
Claim 26
Dependent Claim
18 words
The laminate of claim 22 wherein the polyesterurethane has a urethane content of from 12 to 17.5 percent.
Claim 27
Dependent Claim
18 words
The laminate of claim 24 wherein the hard segment of the polyesterurethane is from 20 to 36 percent.
Claim 28
Dependent Claim
42 words
The laminate of claim 25 wherein the polyesterurethane sheet is an interlayer between two sheets of glass and the sheet has an inherent viscosity of from 0.8 to 1.6 dl/g, as measured at a 0.5 percent concentration in N-methyl-2-pyrrolidone at 30° C.
References Cited (Backward Citations)
US3620905A
Cited
US3823060A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1980-08-08 | 1981-02-07 | 1981-08-09 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1984-08-08 | 1985-02-07 | 1985-08-09 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1988-08-08 | 1989-02-07 | 1989-08-09 | $7700.00 | Window Closed / Lapsed |