Transparent, impact-resistant polyesterurethane laminates

• US 4,041,208 A
• Filed: 05/21/1974
• Issued: 08/09/1977
• Est. Priority Date: 06/21/1971
• Status: Expired due to Term

• Current Assignee: PPG Industries Incorporated (Nouryon BV)
• Original Assignee: PPG Industries Incorporated (Nouryon BV)
• Inventors: Seeger, Nelson V., Kaman, Andrew J.
• Primary Examiner(s): Lesmes, George F.
• Assistant Examiner(s): Roche, R. J.
• Application Number:
  US05/472,019
• Time in Patent Office: 1,176 Days
• Field of Search: 161/190, 260/75 P, 260/75 R, 260/77.5 AP, 260/77.5 AT, 260/77.5 AN, 260/75 NT, 260/77.5 AM, 428/423-425, 296/84 A
• US Class Current: 428/425.6
• CPC Class Codes: B32B 17/10018 comprising only one glass sheet
• CPC Class Codes: B32B 17/10688 Adjustment of the adherence to the glass layers
• CPC Class Codes: B32B 17/10697 being cross-linked
• CPC Class Codes: B32B 17/1077 containing polyurethane
• CPC Class Codes: B32B 17/10853 the membrane being bag-shaped
• CPC Class Codes: B32B 17/10981 Pre-treatment of the layers
• CPC Class Codes: B32B 27/00 Layered products comprising a layer of synthetic resin fibrous or filamentary layer made of a synthetic resin B32B5/02; particulate layer made of a synthetic resin B32B5/16; foamed layer made of a synthetic resin B32B5/18
• CPC Class Codes: B60J 1/02 arranged at the vehicle front , e.g. structure of the glazing, mounting of the glazing on windscreen mounted antenna wire H01Q1/1271
• CPC Class Codes: C08G 18/10 Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• CPC Class Codes: C08G 18/3203 Polyhydroxy compounds
• CPC Class Codes: C08G 18/42 Polycondensates having carboxylic or carbonic ester groups in the main chain
• CPC Class Codes: C08G 18/6633 Compounds of group C08G18/42
• CPC Class Codes: C08G 18/75 cycloaliphatic
• CPC Class Codes: C09J 157/06 Homopolymers or copolymers containing elements other than carbon and hydrogen
• CPC Class Codes: C09J 175/06 from polyesters
• CPC Class Codes: Y10T 428/31601 Quartz or glass

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.

Claims

1. 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.

2. The laminate of claim 1 wherein the polyesterurethane sheet is an interlayer between two sheets of glass.

3. The laminate of claim 1 wherein the polyesterurethane is a random block polymer.

4. 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.

5. 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.

6. The laminate of claim 1 wherein the aliphatic diol is 1,4-butanediol.

7. 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.

8. The laminate of claim 1 wherein the polyesterurethane has a urethane content of from 10 to 20 percent.

9. The laminate of claim 1 wherein the hard segment of the polyesterurethane comprises from 15 to 45 percent.

10. 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.

11. 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.

12. The laminate of claim 11 wherein the polyesterurethane sheet is an interlayer between two sheets of glass.

13. The laminate of claim 12 wherein the polyesterurethane sheet has a thickness of from 15 to 45 mils.

14. 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.

15. The laminate of claim 14 wherein the polyesterurethane has a urethane content of from 12 to 17.5 percent.

16. The laminate of claim 15 wherein the hard segment of the polyesterurethane is from 20 to 36 percent.

17. The laminate of claim 13 wherein the thickness of the sheet is from 18 to 22 mils.

18. 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.

19. 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.

20. The laminate of claim 19 wherein the aliphatic diol is 1,4-butanediol.

21. 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.

22. 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.

23. The laminate of claim 22 wherein the polyesterurethane sheet has a thickness of from 15 to 45 mils.

24. The laminate of claim 22 wherein the polyesterurethane has a urethane content of from 12 to 17.5 percent.

25. The laminate of claim 24 wherein the hard segment of the polyesterurethane is from 20 to 36 percent.

26. 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.