Patent US4652494A successfully refreshed from Google Patents.
US4652494A
Expired / Lapsed
US
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Bilayer laminate and preformed sheet for use therein
Assignee: Saint Gobain Vitrage SA
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Filing: 1984-07-10
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Granted: 1987-03-24
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Expires: 2004-07-10
Abstract
Abstract Preformed, energy-absorbing, scratch resistant, optical, flexible, and self-healing polyurethane sheets, which are adhesive under the influence of heat and pressure; bilayer glazing laminates and bilayer safety windshields including said sheets; wherein said polyurethane sheet is prepared preferably by reactive-casting on a horizontal support and formed preferably from a polyisocyanate monomer including about 2 to about 10 wt. % of urea groups.
Inventors
- 👤 Jean L. Bravet
- 👤 Daniel Colmon
- 👤 Gerard Daude
- 👤 Michel J. Moncheaux
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-02 22:06
CPC Classifications
C; C08; C08J; C08J5/00; C08J5/18; B; B32; B32B; B32B17/00; B32B17/06; B32B17/10; B32B17/10005; B32B17/10009; B32B17/10018; B32B17/1055; B32B17/1077; B32B17/10807; B32B17/10899; B32B17/10908; B32B27/00; B32B27/04; C08G; C08G18/00; C08G18/06; C08G18/28; C08G18/65; C08G18/66; C08G18/6603; C08G18/6607; C08G18/6611; C08G18/6625; C08G18/70; C08G18/72; C08G18/73; C08G18/74; C08G18/75; C08G18/751; C08G18/752; C08G18/753; C08G18/755; C08G18/77; C08G18/78; C08G18/7806; C08G18/7818; C08G18/7825; C08J2375/00; C08J2375/04; C08J2375/08; Y; Y10; Y10T; Y10T428/00; Y10T428/31504; Y10T428/31507; Y10T428/31551; Y10T428/31554; Y10T428/31573; Y10T428/31576; Y10T428/31598; Y10T428/31601
Claims Analysis
Total Claims: 29
Claim 1
Independent Claim
203 words
A preformed flexible transparent sheet effective for use in a glazing laminate having optical, moisture resistant, and energy-absorbing properties and comprising polyurethane which is substantially non-tacky at room temperature, but which is capable of itself being adhesive under the influence of heat and pressure, said sheet characterized in that, as an exposed ply in a glazing laminate, it is capable of maintaining, in the absence of an adhesion promoter, effective adhesion as measured by the temperature and moisutre conditions of ANSI-Z26, Test Nos. 3 and 4, said polyurethane being prepared from a solvent-free mixture of monomers comprising: (A) a cycloaliphatic polyisocyanate component including about 2 to about 10 wt. % of urea groups and about 30 to about 33 wt. % of NCO groups; (B) a polyol component including: (1) about 30 to about 45 OH equivalent percent of a polymeric diol having a MW of about 500 to about 4000; (2) about 20 to about 70 OH equivalent percent of a chain extender diol; and (3) about 0 to about 35 OH equivalent percent of a polyol having an OH functionality greater than two; and (C) a polyurethane-forming catalyst; wherein the NCO/OH ratio of said mixture is about 0.8:1 to about 1:1.
Claim 2
Dependent Claim
203 words
A preformed flexible transparent sheet effective for use in a glazing laminate having optical, moisture resistant, and energy-absorbing properties and comprising polyurethane which is substantially non-tacky at room temperature, but which is capable of itself being adhesive under the influence of heat and pressure, said sheet characterized in that, as an exposed ply in a glazing laminate, it is capable of maintaining, in the absence of an adhesion promoter, effective adhesion as measured by the temperature and moisutre conditions of ANSI-Z26, Test Nos. 3 and 4, said polyurethane being prepared from a solvent-free mixture of monomers comprising: (A) a cycloaliphatic polyisocyanate component including about 2 to about 10 wt. % of urea groups and about 30 to about 33 wt. % of NCO groups; (B) a polyol component including: (1) about 30 to about 45 OH equivalent percent of a polymeric diol having a MW of about 500 to about 4000; (2) about 20 to about 70 OH equivalent percent of a chain extender diol; and (3) about 0 to about 35 OH equivalent percent of a polyol having an OH functionality greater than two; and (C) a polyurethane-forming catalyst; wherein the NCO/OH ratio of said mixture is about 0.8:1 to about 1:1.
Claim 3
Dependent Claim
14 words
A preformed sheet according to claim 1 which comprises a single ply of polyurethane.
Claim 4
Dependent Claim
76 words
A preformed sheet according to claim 1 having an initial tear strength at 20° C. greater than or equal to about 90 daN/cm; an elongation to rupture at 20° C. of about 250 to about 500%; a tensile strength at break at 40° C. of greater than or equal to about 200 daN/cm 2 ; and a tensile strength at 10% elongation at -20° C. of less than or equal to about 300 daN/cm 2 .
Claim 5
Dependent Claim
104 words
A preformed sheet according to claim 3 comprising a polyurethane prepared by: (1) forming on a horizontal support a liquid film comprising a solvent-free mixture of monomers capable of forming a polyurethane and a polyurethane-forming catalyst; (2) maintaining said liquid film at a temperature and for a time sufficient to permit the formation of a uniformly thick and level film; and (3) raising the temperature of said uniformly level liquid film and maintaining the film at an elevated temperature sufficient to fully polymerize the film into a solid polyurethene sheet within less than about one hour while it is positioned on said horizontal support.
Claim 6
Dependent Claim
24 words
A preformed sheet according to claim 4 wherein said mixture of monomers includes a polyisocyanate monomer component comprising urea-containing polyisocyanate monomers and diisocyanate monomers.
Claim 7
Dependent Claim
32 words
A preformed sheet according to claim 5 wherein said polyol monomer component comprises a mixture of polymeric diol and chain extender diol in a molar ratio of about 0.3:1 to about 1:1.
Claim 8
Dependent Claim
23 words
A preformed sheet according to claim 6 wherein said molar ratio of polymeric diol to chain extender is about 0.5:1 to about 0.8:1.
Claim 9
Dependent Claim
32 words
A preformed sheet according to claim 7 wherein said polyol mixture includes a triol monomer and the mole ratio of said polymeric diol to said triol is about 1.5:1 to about 4:1.
Claim 10
Dependent Claim
60 words
A preformed sheet according to claim 8 having scratch and abrasion resistant properties, which, when used to form a bilayer laminate, exhibits scratch resistant properties of greater than about 20 g, as measured by the Erichsen 413 apparatus, and abrasion resistant properties of less than about 4% haze, as measured by the Taber Abraser, pursuant to ANSI-Z26, Test No. 17.
Claim 11
Dependent Claim
13 words
A preformed sheet according to claim 11 wherein said sheet has self-healing properties.
Claim 12
Dependent Claim
39 words
A preformed sheet according to claim 1 wherein said polyisocyanate component includes isophorone diisocyanate and the urea adduct of about 2 moles of isophorone diisocyanate and about one mole of water, and said polymeric diol is a polyether diol.
Claim 13
Dependent Claim
14 words
A preformed sheet according to claim 11 wherein said urea adduct comprises N,N'-bis(isophorone isocyanate)urea.
Claim 14
Dependent Claim
39 words
A preformed sheet according to claim 12 wherein: said polymeric diol is polytetramethylene glycol having a MW of about 1000; said chain extender diol is 1,4-butanediol; and said polyol having an OH functionality greater than two is polycaprolactone triol.
Claim 15
Dependent Claim
81 words
A preformed transparent sheet having optical properties, comprising an energy absorbing polyurethane ply, characterized in that said polyurethane ply is prepared by reactive casting, on a level horizontal support, a reaction mixture including: an isocyanate component, having a viscosity of less than 5000 mPaS at 40° C., and comprising an aliphatic diisocyanate, a cycloaliphatic diisocyanate or an isocyanate prepolymer; and, a polyol component comprising a polymeric diol having a MW of about 500 to about 4000, and a short chain diol.
Claim 16
Dependent Claim
81 words
A preformed transparent sheet having optical properties, comprising an energy absorbing polyurethane ply, characterized in that said polyurethane ply is prepared by reactive casting, on a level horizontal support, a reaction mixture including: an isocyanate component, having a viscosity of less than 5000 mPaS at 40° C., and comprising an aliphatic diisocyanate, a cycloaliphatic diisocyanate or an isocyanate prepolymer; and, a polyol component comprising a polymeric diol having a MW of about 500 to about 4000, and a short chain diol.
Claim 17
Dependent Claim
102 words
A method for the preparation of a preformed, flexible, transparent polyurethane sheet according to claim 1, comprising: (1) forming on a horizontal support a liquid film comprising a mixture of monomers and a polyurethane-forming catalyst; (2) maintaining said liquid film at a temperature and for a time sufficient to permit the formation of a uniformly thick and level liquid film; (3) raising the temperature of said uniformly level liquid film and maintaining the film at an elevated temperature sufficient to fully polymerize the film into a solid polyurethane sheet within less than about one hour while it is positioned on said support.
Claim 18
Dependent Claim
53 words
A method according to claim 15 wherein said liquid film is maintained at a temperature of about 35° to about 45° C. for about 0.5 to about 5 minutes and is raised to a temperature of about 80° to about 140° C. within a period of time of less than about 3 minutes.
Claim 19
Dependent Claim
30 words
A method according to claim 16 wherein said liquid film is fully polymerized by maintaining a temperature of about 80° to about 140° C. for less than about 30 minutes.
Claim 20
Dependent Claim
41 words
A method according to claim 17 wherein said liquid film comprises a mixture of monomers including a polyisocyanate component containing urea groups, a polyol component comprising a polyether diol, and a chain extender diol, wherein the NCO/OH ratio is about 1:1.
Claim 21
Dependent Claim
23 words
A method according to claim 18 wherein about 0.05 to about 35 OH equivalent percent of the polyol component comprises a polymeric triol.
Claim 22
Dependent Claim
34 words
A method according to claim 18 wherein said liquid film includes greater than about 0.01 to about 0.05 wt. % of a tin catalyst based on the total weight of the liquid film composition.
Claim 23
Dependent Claim
34 words
A method according to claim 19 wherein said polyisocyanate monomer component comprises a mixture of isophorone diisocyanate and the urea adduct of about two moles of isophorone diisocyanate and about one mole of water.
Claim 24
Dependent Claim
165 words
A composition which is liquid at a temperature greater than about 25° C. and which exhibits a viscosity at about 35° to about 45° C. sufficient to permit the formation on a horizontal support of a uniformly thick and level film thereof, and comprising a solvent-free mixture which is capable of forming a solid polyurethane upon heating, and which cqmprises: (A) a cycloaliphatic polyisocyanate component including about 2 to about 10 wt. % of urea groups and about 30 to about 33 wt. % of NCO groups; (B) a polyol component including: (1) about 30 to about 45 OH equivalent percent of a polymeric diol having a MW of about 500 to about 3000; (2) about 20 to about 70 OH equivalent percent of a chain extender diol; and (3) about 0 to about 35 OH equivalent percent of a polyol having greater than two OH functionality; and (C) a polyurethane-forming catalyst; wherein the NCO/OH ratio of said mixture is about 0.8:1 to about 1:1.
Claim 25
Dependent Claim
165 words
A composition which is liquid at a temperature greater than about 25° C. and which exhibits a viscosity at about 35° to about 45° C. sufficient to permit the formation on a horizontal support of a uniformly thick and level film thereof, and comprising a solvent-free mixture which is capable of forming a solid polyurethane upon heating, and which cqmprises: (A) a cycloaliphatic polyisocyanate component including about 2 to about 10 wt. % of urea groups and about 30 to about 33 wt. % of NCO groups; (B) a polyol component including: (1) about 30 to about 45 OH equivalent percent of a polymeric diol having a MW of about 500 to about 3000; (2) about 20 to about 70 OH equivalent percent of a chain extender diol; and (3) about 0 to about 35 OH equivalent percent of a polyol having greater than two OH functionality; and (C) a polyurethane-forming catalyst; wherein the NCO/OH ratio of said mixture is about 0.8:1 to about 1:1.
Claim 26
Dependent Claim
30 words
A composition according to claim 22 wherein said polyisocyanate component includes isophorone diisocyanate and the urea adduct of about 2 moles of isophorone diisocyanate and about one mole of water.
Claim 27
Dependent Claim
14 words
A composition according to claim 23 wherein said polymeric diol is a polyether diol.
Claim 28
Dependent Claim
37 words
A composition according to claim 24 wherein said polyether diol is polytetramethylene glycol having a MW of about 1000; said chain extender diol is 1,4-butanediol; and said polyol having greater than two OH functionality is polycaprolactone triol.
Claim 29
Dependent Claim
10 words
A composition according to claim 22 including a sheeting agent.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1990-03-23 | 1990-09-22 | 1991-03-24 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1994-03-23 | 1994-09-22 | 1995-03-24 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1998-03-23 | 1998-09-22 | 1999-03-24 | $7700.00 | Window Closed / Lapsed |