Laminated safety glass

• US 4,663,228 A
• Filed: 12/17/1985
• Issued: 05/05/1987
• Est. Priority Date: 05/03/1983
• Status: Expired due to Term

• Current Assignee: Artistic Glass Products Co.
• Original Assignee: Advanced Glass Systems Corporation
• Inventors: Smith, W. Novis Jr., Bolton, Nelson P.
• Primary Examiner(s): Robinson, Ellis P.
• Application Number:
  US06/809,847
• Time in Patent Office: 504 Days
• Field of Search: 428/441, 428/442, 428/412, 428/426, 428/429, 428/334, 428/411.1, 156/99, 156/106, 156/306.6, 156/331.6, 156/334
• US Class Current: 428/334
• CPC Class Codes: B32B 15/04 comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material next to a bituminous or tarry layer B32B11/08; next to a water-setting substance layer B32B13/06; next to a glass layer B32B17/061; next to a cellulosic plastic layer B32B23/042
• CPC Class Codes: B32B 17/10005 laminated safety glass or glazing
• CPC Class Codes: B32B 17/10018 comprising only one glass sheet
• CPC Class Codes: B32B 17/10036 comprising two outer glass sheets
• CPC Class Codes: B32B 17/10045 with at least one intermediate layer consisting of a glass sheet
• CPC Class Codes: B32B 17/10137 Chemical strengthening
• CPC Class Codes: B32B 17/1033 Laminated safety glass or glazing containing temporary protective coatings or layers
• CPC Class Codes: B32B 17/10743 containing acrylate (co)polymers or salts thereof
• CPC Class Codes: B32B 2333/08 Polymers of acrylic acid esters, e.g. PMA, i.e. polymethylacrylate
• CPC Class Codes: B32B 2369/00 Polycarbonates
• CPC Class Codes: B32B 27/30 comprising vinyl (co)polymers; comprising acrylic (co)polymers
• CPC Class Codes: B32B 27/36 comprising polyesters
• CPC Class Codes: F41H 5/0407 Transparent bullet-proof laminatesinformative reference: layered products essentially comprising glass in general B32B17/06, e.g. B32B17/10009; manufacture or composition of glass, e.g. joining glass to glass C03; permanent multiple-glazing windows, e.g. with spacing therebetween, E06B3/66
• CPC Class Codes: Y10T 428/263 Coating layer not in excess of 5 mils thick or equivalent
• CPC Class Codes: Y10T 428/31504 Composite [nonstructural laminate]
• CPC Class Codes: Y10T 428/31507 Of polycarbonate
• CPC Class Codes: Y10T 428/31612 As silicone, silane or siloxane
• CPC Class Codes: Y10T 428/31645 Next to addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31649 Ester, halide or nitrile of addition polymer

Abstract

Laminated articles, particularly safety glass, comprising a lamina of ionomer resin film laminated to a sheet of glass. The ionomer resin film is preferably an ionically crosslinked ethylene-methacrylic acid copolymer. The laminated articles may also comprise a sheet of polycarbonate laminated to the ionomer resin film opposite the glass. The laminated articles may further comprise an ionomer resin film sandwiched between two sheets of glass. The laminated articles may still further comprise a sheet of polycarbonate or other plastics sandwiched between sheets of ionomer resin film, which are in turn sandwiched between sheets of glass.

Claims

1. A transparent laminated article comprising:

a first lamina consisting essentially of an ionomer resin film, said ionomer resin film being water insoluble and the metal salt of an ionomer resin prepared from ethylene and methacrylic acid monomers, said ionomer resin being partially neutralized by an organic diamine or triamine; and

one sheet of primed or unprimed glass laminated to said first ionomer.

2. A transparent laminated article as claimed in claim 1, further comprising a second sheet laminated to said first lamina on the surface thereof opposite said sheet of glass, whereby said first lamina is sandwiched between said sheet of glass and said second sheet, said second sheet being comprised of polycarbonate.

3. A transparent laminated article as claimed in claim 1, further comprising:

a second sheet laminated to said first lamina on the surface thereof opposite said glass sheet;

a second lamina laminated to said second sheet, said second sheet being comprised of polycarbonate and sandwiched between said first and second lamina;

a second sheet of glass laminated to said second lamina on the surface thereof opposite said second sheet, whereby said second lamina is sandwiched between said second sheet and said second sheet of glass; and

said second lamina consisting essentially of an extruded ionomer resin film, said ionomer resin film being water insoluble and selected from the group of ionomer resins which are ionically cross-linked copolymers prepared from ethylene and methacrylic acid monomers.

4. A transparent laminated article as claimed in claims 1, 2, or 3, wherein the surfaces laminated to said ionomer resin films are primed with a silane coupling agent.

5. A transparent lamina as claimed in claim 1, wherein said ionomer resin is a sodium salt of ethylene-methacrylic acid copolymer.

6. A transparent laminated article as claimed in claim 1, wherein said ionomer resin is a zinc salt of ethylene-methacrylic acid copolymer.

7. A transparent laminated article as claimed in claim 1, wherein said ionomer resin is a mixture of metal salts of ethylene-methacrylic acid copolymer.

8. A transparent laminated article as claimed in claim 1, wherein said first lamina has a thickness of 20 to 200 mils.

26. The laminated article of claim 1 wherein said organic diamine is selected from the group consisting of 1,3-diaminomethyl xylene, isophorone diamine and a monocyclic alicyclic compound of the formula:

##STR2## R" and R'"'"'" represent hydrogen or lower alkyl;

Z is 0-5;

W is 0-4; and

X is 0-4, with the proviso that together X and Y equal 4.

27. The laminated article of claim 26 wherein said organic diamine is bis(1,3-aminomethyl)cyclohexane.

28. The laminated article of claim 26 wherein said metal is selected from the group consisting of alkali metals, aluminum and zinc.

9. A method of forming a transparent laminated glass article comprising the steps of:

providing a primed or unprimed glass sheet; and

laminating a first lamina consisting essentially of an ionomer resin film to said glass sheet, said ionomer resin film being water insoluble and the metal salt of an ionomer resin prepared from ethylene and methacrylic acid monomers, said ionomer resin being partially neutralized by an organic diamine or triamine.

10. A method as claimed in claim 9, further comprising priming said glass surface adjacent said first lamina with a silane coupling agent before laminating said first lamina thereto.

11. A method as claimed in claim 10, wherein said laminating step comprises:

heating said glass sheet and first lamina to a temperature in the range of approximately 180°

F. to approximately 310°

F.;

maintaining the temperature for approximately 15 minutes to approximately one hour; and

cooling as rapidly as possible without damaging the laminate.

12. A method as claimed in claim 11, wherein said heating occurs in an autoclave under a pressure of approximately 10 atmospheres.

13. A method as claimed in claim 9, further comprising the steps of covering the otherwise exposed surface of said first lamina with a hard coat material.

14. A method as claimed in claim 9, further comprising the step of laminating a second sheet to the otherwise exposed surface of said first lamina, said second sheet being selected from the group of materials consisting of polycarbonate, acrylic and metal.

15. A method as claimed in claim 14, wherein said second sheet is polycarbonate and further comprising the step of priming the surface of said polycarbonate to be bonded to said first lamina with a silane coupling agent.

16. A method as claimed in claim 15, further comprising the step of covering the otherwise exposed surface of said sheet of polycarbonate with a hard coat material.

17. A method as claimed in claim 9, further comprising the steps of:

laminating a second sheet to the otherwise exposed surface of said first lamina, said second sheet being comprised of polycarbonate;

laminating a second lamina to the otherwise exposed surface of said second sheet, said second lamina consisting essentially of an extruded ionomer resin film, said ionomer resin film being water insoluble and selected from the group of ionomer resins which are ionically cross-linked copolymers prepared from ethylene and methacrylic acid monomers; and

laminating a second sheet of glass to the otherwise exposed surface of said second lamina.

18. A method as claimed in claim 17, further comprising the step of priming all surfaces to be bonded to said first and second laminas with a silane coupling agent.

19. A method as claimed in claim 9, wherein said first lamina has a thickness of 20 to 200 mils.

29. The method of claim 9 wherein said organic diamine is selected from the group consisting of 1,3-diaminomethyl xylene, isophorone diamine and a monocyclic compound of the formula:

##STR3## wherein;

R" and R'"'"'" represent hydrogen or lower alkyl;

Z is 0-5;

W is 0-4; and

X is 0-4, with the proviso that together X and Y equal 4.

30. The method of claim 29 wherein said organic diamine is bis(1,3-aminomethyl)cyclohexane.

31. The method of claim 9 wherein said metal is selected from the group consisting of alkali metals, aluminum and zinc.

20. A transparent laminated article comprising:

a first lamina having a thickness of at least 20 mils consisting essentially of an extruded ionomer resin film, said ionomer resin film being water insoluble and the metal salt of an ionomer resin prepared from ethylene and methacrylic acid monomers, said ionomer resins being partially neutralized by an organic diamine or triamine; and

a sheet of primed or unprimed glass laminated to said first ionomer resin on one side and a sheet of plastic material on the other side.

32. The laminated article of claim 20 wherein said organic diamine is selected from the group consisting of 1,3-diaminomethyl xylene, isophorone diamine and a monocyclic compound of the formula:

##STR4## wherein;

R" and R'"'"'" represent hydrogen or lower alkyl;

Z is 0-5;

W is 0-4; and

X is 0-4, with the proviso that together X and Y equal 4.

33. The laminated article of claim 32 wherein said diamine is bis(1,3-aminomethyl)cyclohexane.

34. The laminated article of claim 20 wherein said metal is selected from the group consisting of alkali metals, aluminum and zinc.

21. A method of forming a transparent laminated glass article comprising the steps of:

providing a primed or unprimed glass sheet; and

laminating a first lamina consisting of an extruded ionomer resin film having a thickness of at least 20 mils to said glass sheet, said ionomer resin film being water insoluble and the metal salt of an ionomer resin resins which are ionically cross-linked copolymers prepared from ethylene and methacrylic acid monomers, said ionomer being partially neutralized by an organic diamine or triamine.

22. In a laminated product having at least one glass surface bonded with an opposing surface by an ionomer resin film, the improvement which comprises said ionomer resin film being a mixture of a zinc ionomer resin and a sodium ionomer resin, said ionomer being a copolymer prepared from ethylene or an alpa-olefin and carboxylic acid, and an organic polyamine partially neutralizing said resins for causing optical clarity of said ionomer resin.

23. The laminated product of claim 22, wherein said sodium and zinc ionomer resins are in a ratio of 95:

5 to 5;

95.

24. The laminate product of claim 22, wherein said organic polyamine is present in an amount of from about 0.5 to about 20% by weight of resin.

25. The laminate product of claim 22, wherein said opposing surface comprises a polycarbonate.

35. The laminated product of claim 22 wherein said organic diamine is selected from the group consisting of 1,3-diaminomethyl xylene, isophorone diamine and a monocyclic compound of the formula:

##STR5## wherein;

R" and R'"'"'" represent hydrogen or lower alkyl;

Z is 0-5;

W is 0-4; and

X is 0-4, with the proviso that together X and Y equal 4.

36. The laminated product of claim 35 wherein said diamine is bis(1,3-aminomethyl)cyclohexane.

37. A transparent laminated article comprising:

a first lamina consisting essentially of a Mylar film

a second lamina consisting essentially of an extruded ionomer resin film, said ionomer resin film being water insoluble and the metal salt of an ionomer resin prepared from ethylene and methacrylic acid monomers, said resin being partially neutralized by an organic polyamine, and

a sheet of transparent plastic material selected from the group consisting of polycarbonate, polyurethane and acrylic plastic.

38. The laminated product of claim 37 wherein said organic polyamine is selected from the group consisting of 1,3-diaminomethyl xylene, isophorone diamine and a monocyclic compound of the formula:

##STR6## wherein;

R" and R'"'"'" represent hydrogen or lower alkyl;

Z is 0-5;

W is 0-4; and

X is 0-4, with the proviso that together X and Y equal 4.

39. The laminated article of claim 38 wherein said polyamine is bis(1,3-aminomethyl)cyclohexane.

40. The laminated article of claim 38, wherein said metal is selected from the group consisting of sodium, zinc and mixtures thereof.