Impact resistant soft coated laminates and process for making the same

Abstract

Improved impact or shock resistant soft coated laminates including a back polycarbonate lamina opposite the direction of impact or shock, such polycarbonate lamina having a soft overlying or exposed layer or coating opposite the direction of impact, are provided. The laminates exhibit excellent resistance to failure and spalling of the polycarbonate surface opposite the impact or shock receiving surface. The soft coal is a self-healing, chemically resistant polyurethane having an excess of free hydroxyl groups over isocyanate groups and confers on the laminates excellent scratch resistance, good resistance against swelling and stress cracking while at the same time the laminates exhibit good clarity and integrity in addition to good chemical and permeation resistance, as well as resistance to failure and spalling. The process employs the polyurethane in film form as a cap sheet.

I claim: 
     
       1. An impact and shock-resistant laminate comprising a plurality of laminae including a back polycarbonate layer and a soft, overlying, exposed layer, opposite the direction of impact, of a self-healing, chemically resistant polyurethane having an excess of free hydroxyl groups over isocyanate groups .Iadd.and including a mar-resistant coating on the exposed, impact receiving surface of the polycarbonate layer.Iaddend.. .[.2. A laminate according to claim 1 including a mar-resistant coating on the exposed, 
     
     
        impact receiving surface of the polycarbonate layer..]. 3. A laminate according to claim 2 wherein the mar-resistant coating is a self-healing chemically resistant polyurethane having an excess of free hydroxyl groups 
     
     
        over isocyanate groups. 4. An impact and shock-resistant laminate comprising a plurality of laminae including a back polycarbonate layer coated with a soft, overlying, exposed layer, opposite the direction of impact, of a self-healing, chemically resistant polyurethane having an excess of free hydroxyl groups over isocyanate groups, at least one layer of other material and at least one interlayer of a compatible adhesive. 
     
     
           A laminate according to claim 4 wherein the adhesive interlayer is 
     
     
        polysiloxane-polycarbonate block copolymer. 6. A laminate according to claim 4 wherein the adhesive interlayer is a polysiloxane-polycarbonate block copolymer having the average formula: ##STR6## wherein n is at least 1, a is equal to from 1 to about 200 inclusive, b has an average value from about 15 to about 90, the ratio of a to b can vary from about 0.05 to about 3 inclusive d is 1 or more, y is ##STR7## A is a member selected from the group consisting of hydrogen and ##STR8## R is a member selected from the group consisting of hydrogen, monovalent hydrocarbon radicals and halogenated monovalent hydrocarbon radicals, R' is a member selected from the group consisting of monovalent hydrocarbon radicals and cyanoalkyl radicals, R" is a member selected from the group consisting of monovalent hydrocarbon radicals and halogenated hydrocarbon radicals, and Z is a member selected from the group consisting of 
     
     
        hydrogen, halogen and lower alkyl radicals and mixtures thereof. 7. A laminate according to claim 6 wherein in formula I n is an integer equal from 1 to about 1000 inclusive and the ratio of a to b is from about 0.067 
     
     
        to about 0.45 inclusive. 8. A laminate according to claim 4 wherein the 
     
     
        other material is polycarbonate. 9. A laminate according to claim 4 
     
     
        wherein the other material is solid resinous material. 10. A laminate according to claim 9 wherein the solid resinous material is an acrylic 
     
     
        resin. 11. A laminate according to claim 4 wherein the other material is 
     
     
        glass. 12. A laminate according to claim 4 including a mar-resistant 
     
     
        coating on the exposed surface of the other material. 13. A laminate according to claim 12 wherein the mar-resistant coating is a self-healing, chemically resistant polyurethane having an excess of free hydroxyl groups 
     
     
        over isocyanate groups. 14. A laminate according to claim 4 which is 
     
     
        symmetrical. 15. A laminate according to claim 14 including a 
     
     
        mar-resistant coating on the exposed surface of the other material. 16. A laminate according to claim 15 wherein the mar-resistant coating is a self-healing, chemically resistant polyurethane having an excess of free 
     
     
        hydroxyl groups over isocyanate groups. 17. An impact and shock-resistant laminate comprising a plurality of laminae including a back polycarbonate layer coated with a soft, overlying exposed layer, opposite the direction of impact, of a self-healing, chemically resistant polyurethane having an excess of free hydroxyl groups over isocyanate groups, a polysiloxane-polycarbonate block copolymer adhesive interlayer and an 
     
     
        outboard layer of polycarbonate. 18. A laminate according to claim 17 including a mar-resistant coating on the exposed surface of the outboard 
     
     
        polycarbonate layer. 19. A laminate according to claim 18 wherein the mar-resistant coating is a self-healing, chemically resistant polyurethane 
     
     
        having an excess of free hydroxyl groups over isocyanate groups. 20. An impact and shock-resistant laminate comprising a plurality of laminae including a back polycarbonate layer coated with a soft, overlying exposed layer, opposite the direction of impact, of a self-healing, chemically resistant polyurethane having an excess of free hydroxyl groups over isocyanate groups, an outboard layer of polycarbonate, a layer of polycarbonate disposed between the back and outboard polycarbonate layers and polysiloxane-polycarbonate adhesive interlayers between said 
     
     
        polycarbonate layers. 21. A laminate according to claim 20 including a mar-resistant coating on the exposed surface of the outboard polycarbonate 
     
     
        layer. 22. A laminate according to claim 21 wherein the mar-resistant coating is a self-healing, chemically resistant polyurethane having an 
     
     
        excess of free hydroxyl groups over isocyanate groups. 23. A process for making an impact and shock-resistant laminate comprising applying a .Iadd.self healing chemically resistant .Iaddend.polyurethane film having an excess of free hydroxyl groups over isocyanate groups to a 
     
     
        polycarbonate sheet layer with the application of heat. 24. A process according to claim 23 including subjecting the laid up layer to pressure. 
     
     
         5. A process for making an impact and shock-resistant laminate comprising applying a primer to a polyurethane film having an excess of free hydroxyl groups over isocyanate groups, applying the primed film as a cap sheet to a polycarbonate sheet, subjecting the laid up sheets to heat and pressure and forming a laminate having a soft coated polyurethane inboard layer of 
     
     
        polycarbonate. 26. A process for making an impact and shock-resistant laminate comprising applying a primer in a thickness in a range of about 500 Å to about 2000 Å to a polyurethane film, having an excess of free hydroxyl over isocyanate groups, applying the primed polyurethane film as a cap sheet to a polycarbonate sheet and subjecting the laid up sheets to a temperature in a range of from about 250° F. to about 300° F. and a uniform pressure for a time sufficient to laminate said laid up sheets and forming a soft coated polyurethane inboard layer 
     
     
        of polycarbonate. 27. A process according to claim 26 wherein the primer comprises 6.8% trimethylolpropane, 21.4% diethylene glycol, 38% azelaic 
     
     
        acid and 33.8% urethane. .Iadd.28.  An impact and shock-resistant laminate as defined in claim 4 wherein the soft, overlying, exposed layer opposite the direction of impact, of a self-healing, chemically resistant polyurethane having an excess of free hydroxyl groups over isocyanate groups is obtained by curing (1) a polyglycol ether resulting from the condensation of propylene oxide with trimethylolpropane and having about 10.5 percent to about 12.5 percent free hydroxyl groups and (2) a biuret of 1,6-hexamethylene diisocyanate having about 21 percent to about 22 percent isocyanate groups, the weight ratio of the biuret to the polyglycol ether being about 0.9 to 1.1. .Iaddend. .Iadd.29. An impact and shock-resistant laminate as defined in claim 28 wherein the adhesive interlayer is a polysiloxane-polycarbonate block copolymer. .Iaddend. .Iadd.30. An impact and shock resistant laminate as defined in claim 29 wherein the adhesive interlayer is a polysiloxane-polycarbonate block copolymer having the average formula ##STR9## wherein n is at least 1, a is equal to from about 200 inclusive, b has an average value from about 15 to about 90, the ratio of a to b can vary from about 0.5 to about 3 inclusive d is 1 or more, y is ##STR10## A is a member selected from the group consisting of hydrogen and ##STR11## R is a member selected from the group consisting of hydrogen, monovalent hydrocarbon radicals and halogenated monovalent hydrocarbon radicals, R' is a member selected from the group consisting of monovalent hydrocarbon radicals and cyanoalkyl radicals, R" is a member selected from the group consisting of monovalent hydrocarbon radicals and halogenated hydrocarbon radicals, and Z is a member selected from the group consisting of hydrogen halogen and lower alkyl radicals and mixtures thereof. .Iaddend. 
     
     
        .Iadd.     A laminate according to claim 6 wherein formula I, n is an integer equal from 1 to about 1000 inclusive. .Iaddend. .Iadd.32. A laminate according to claim 4 wherein the other material is polycarbonate. 
     
     
        .Iaddend. .Iadd.33.  A laminate according to claim 4 wherein the other material is solid resinous material. .Iaddend. .Iadd.34. A laminate to claim 9 wherein the solid resinous material is an acrylic resin. .Iaddend. .Iadd.35. A laminate according to claim 4 wherein the other material is glass. .Iaddend. .Iadd.36. A laminate according to claim 4 including a mar-resistant coating on the exposed surface of the other material. .Iaddend. .Iadd.37. A laminate according to claim 12 wherein the mar-resistant coating is a self-healing, chemically resistant polyurethane having an excess of free hydroxyl groups over isocyanate groups. .Iaddend. .Iadd.38. A laminate according to claim 4 which is symmetrical. .Iaddend. .Iadd.39. A laminate according to claim 14 including a mar-resistant coating on the exposed surface of the other material. .Iaddend. .Iadd.40. A laminate according to claim 15 including a mar-resistant coating in a self-healing, chemically resistant polyurethane having an excess of free hydroxyl groups over isocyanate groups. .Iaddend.