U.S. patent application number 16/353801 was filed with the patent office on 2019-09-05 for light-weight, high stiffness glass laminate structure.
The applicant listed for this patent is CORNING INCORPORATED. Invention is credited to Christianus Johannes Jacobus Maas, Anurag Jain, Michael Laurin, Michael Aaron McDonald, Michael John Moore, Charlie Wood.
Application Number | 20190270283 16/353801 |
Document ID | / |
Family ID | 51535564 |
Filed Date | 2019-09-05 |
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United States Patent
Application |
20190270283 |
Kind Code |
A1 |
Jacobus Maas; Christianus Johannes
; et al. |
September 5, 2019 |
LIGHT-WEIGHT, HIGH STIFFNESS GLASS LAMINATE STRUCTURE
Abstract
A laminate structure having a first chemically strengthened
glass layer, a second chemically strengthened glass layer, and a
polymer interlayer structure intermediate the first and second
glass layers. The polymer interlayer structure can include a first
polymeric layer adjacent to the first glass layer, a second
polymeric layer adjacent to the second glass layer, and a polymeric
rigid core intermediate the first and second polymeric layers.
Inventors: |
Jacobus Maas; Christianus
Johannes; (Rilland, NL) ; Jain; Anurag;
(Painted Post, NY) ; Laurin; Michael; (San Pedro,
CA) ; McDonald; Michael Aaron; (Painted Post, NY)
; Moore; Michael John; (Corning, NY) ; Wood;
Charlie; (Peru, MA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
CORNING INCORPORATED |
Corning |
NY |
US |
|
|
Family ID: |
51535564 |
Appl. No.: |
16/353801 |
Filed: |
March 14, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14471830 |
Aug 28, 2014 |
10279567 |
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16353801 |
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61871928 |
Aug 30, 2013 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B32B 17/10779 20130101;
Y10T 428/31507 20150401; Y10T 428/31663 20150401; B32B 2367/00
20130101; Y10T 156/10 20150115; B32B 2369/00 20130101; B32B
17/10798 20130101; B32B 37/18 20130101; B32B 17/10761 20130101;
Y10T 428/24868 20150115; B32B 17/10036 20130101; E06B 3/66
20130101; B32B 2383/00 20130101; B32B 17/1077 20130101; B32B
17/10119 20130101; B32B 17/10678 20130101; B32B 17/10 20130101;
B32B 17/10788 20130101; B32B 2383/00 20130101; Y10T 428/24926
20150115; B32B 17/10 20130101; B32B 17/10752 20130101; B32B 2369/00
20130101; B32B 17/10137 20130101; Y10T 428/24967 20150115; Y10T
428/2495 20150115; B32B 17/10091 20130101; B32B 17/10018
20130101 |
International
Class: |
B32B 17/10 20060101
B32B017/10; E06B 3/66 20060101 E06B003/66; B32B 37/18 20060101
B32B037/18 |
Claims
1-14. (canceled)
15. A multilayer article comprising: a first glass layer, wherein
the first glass layer is comprised of a thin, chemically
strengthened glass having a surface compressive stress of between
about 250 MPa and about 350 MPa and a depth of layer of compressive
stress greater than 60 .mu.m; a first interlayer; and a polymer
layer; wherein the polymer layer comprises a polysiloxane, a
polyester, a polycarbonate, a copolymer comprising one or more of
the foregoing, or a blend comprising one or more of the foregoing;
wherein the first glass layer is 0.1 to 1.5 mm, the first
interlayer is 0.2 to 1.4 mm, and the polymer layer is 2 to 15
mm.
16. The multilayer article of claim 15, further comprising a second
glass layer and a second interlayer; wherein the second glass layer
is comprised of a thin, chemically strengthened glass having a
surface compressive stress of between about 250 MPa and 350 MPa and
a depth of layer (DOL) of compressive stress greater than about 60
.mu.m; wherein the second glass layer is 0.1 to 1.5 mm and the
second interlayer is 0.2 to 1.4 mm.
17. The multilayer article of claim 15, wherein the first
interlayer comprises a thermoplastic polyurethane.
18. The multilayer article of claim 15, wherein the first
interlayer comprises a poly(ethylene-co-vinyl acetate), wherein the
poly(ethylene-co-vinyl acetate) comprises 0 to 0.01 wt % hindered
amine stabilizer.
19. The multilayer article of claim 15, wherein the
poly(ethylene-co-vinyl acetate) comprises a vinyl acetate content
of 20 to 80 wt % based on the total weight of the
poly(ethylene-co-vinyl acetate).
20. The multilayer article of claim 15, wherein the polymer layer
comprises a polysiloxane copolymer comprising: a.) a polysiloxane
unit of the formula: ##STR00028## or of the formula: ##STR00029##
wherein E is 4 to 50; each R is the same or different and is a
C.sub.1-13 monovalent organic group, and each R.sup.2 is
independently a divalent C.sub.1-30 alkylene or C.sub.7-30
arylene-alkylene; and Ar is a C.sub.6-30 arylene group; and b.) an
arylate-containing unit consisting of 50 to 100 mole percent of
arylate ester units, less than 50 mole percent aromatic carbonate
units, less than 30 mole percent resorcinol carbonate units, and
less than 35 mole percent bisphenol carbonate units, wherein the
siloxane units of the polysiloxane unit are present in the
polysiloxane copolymer composition in an amount of 0.2 to 10 wt %
based on the weight of the polysiloxane copolymer composition.
21. The multilayer article of claim 15, wherein the polymer layer
comprises a polysiloxane-polycarbonate copolymer derived from at
least one dihydroxy aromatic containing polycarbonate unit, and at
least one polysiloxane bisphenol of formula (1), formula (2), or a
combination thereof ##STR00030## wherein R is each independently a
C.sub.1-30 hydrocarbon group, R.sup.2 is each independently a
C.sub.7-30 hydrocarbon group, Ar is a C.sub.6-30 aromatic group
and, E has an average value of 5 to 200; a second polycarbonate
comprising brominated carbonate units derived from
2,2',6,6'-tetrabromo-4,4'-isopropylidenediphenol and carbonate
units derived from at least one dihydroxy aromatic compound that is
not 2,2',6,6'-tetrabromo-4,4'-isopropylidenediphenol; and
optionally, a third polycarbonate different from the
polysiloxane-polycarbonate copolymer and second polycarbonate;
wherein the wt % of the polysiloxane-polycarbonate copolymer, the
second polycarbonate, and the optional third polycarbonate sum to
100 wt %; wherein the first polycarbonate is present in an amount
effective to provide the siloxane units in an amount of at least
0.3 wt %, based on the sum of the wt % of the
polysiloxane-polycarbonate copolymer, the second polycarbonate, and
the optional third polycarbonate, and the second polycarbonate is
present in an amount effective to provide the bromine of the second
polycarbonate in an amount of at least 7.8 wt %, based on the sum
of the wt % of the polysiloxane-polycarbonate copolymer, the second
polycarbonate, and the optional third polycarbonate.
22. The multilayer article of claim 15, wherein the polymer layer
comprises a first polymer comprising a polyetherimide-polysiloxane
copolymer comprising (a) a repeating polyetherimide unit, and (b) a
polysiloxane block unit, the polysiloxane block unit having the
formula: ##STR00031## wherein R is each independently a C.sub.1-30
hydrocarbon group, and E has an average value of 5 to 200; a second
polymer different from the first polymer and comprising bromine;
and an optional one or more third polymers comprising a
polycarbonate different from the first polymer and second polymer;
wherein the wt % of the first polymer, second polymer, and optional
one or more third polymers sum to 100 wt %; and where the siloxane
units are present in the composition in an amount of at least 0.3
wt %, based on the sum of the wt % of the first, second, and
optional one or more third polymers, and the bromine is present in
the composition in an amount of at least 7.8 wt %, based on the sum
of the wt % of the first, second, and optional one or more third
polymers.
23. The multilayer article of claim 15, wherein the polymer layer
comprises one or both of an antidrip agent and a flame
retardant.
24. The multilayer article of claim 15, wherein the polymer layer
comprises an organophosphorus compound in an amount effective to
provide 0.1 to 1.0 wt % of phosphorus, based on the total weight of
the composition one or more flame retardants
25. The multi layer article of claim 24, wherein the
organophosphorus compound is an aromatic organophosphorus compounds
having at least one organic aromatic group and at least one
phosphorus-containing group, or an organic compounds having at
least one phosphorus-nitrogen bond.
26. The multilayer article of claim 25, wherein the aromatic
organophosphorus compound comprises a C3-30 aromatic group and a
phosphate group, phosphite group, phosphonate group, phosphinate
group, phosphine oxide group, phosphine group, phosphazene, or a
combination comprising at least one of the foregoing
phosphorus-containing groups.
27. The multilayer article of claim 26, wherein the aromatic
organophosphorus compound is of the formula: ##STR00032## wherein
R16, R17, R18 and R19 are each independently C1-8 alkyl, C5-6
cycloalkyl, C6-20 aryl, or C7-12 arylalkylene, each optionally
substituted by C1-12 alkyl, and X is a mono- or poly-nuclear
aromatic C6-30 moiety or a linear or branched C2-30 aliphatic
radical, which can be OH-substituted and can contain up to 8 ether
bonds, provided that at least one of R16, R17, R18, R19, and X is
aromatic, n is each independently 0 or 1, and q is from 0.5 to
30.
28. The multilayer article of claim 27, wherein each of R.sup.16,
R.sup.17, R.sup.18, and R.sup.19 is phenyl, X is of the formula
##STR00033## each n is 1, and p is 1-5.
29. The multilayer article of claim 25, wherein the aromatic
organophosphorus compound is bisphenol A bis(diphenyl phosphate),
triphenyl phosphate, resorcinol bis(diphenyl phosphate), tricresyl
phosphate, or a combination comprising at least one of the
foregoing.
30. The multilayer article of claim 24, wherein organophosphorus
compound containing a nitrogen-phosphorus bond is a phosphazene,
phosphorus ester amide, phosphoric acid amide, phosphonic acid
amide, phosphinic acid amide, tris(aziridinyl) phosphine oxide, a
combination comprising at least one of the foregoing.
31. The multilayer article of claim 24, wherein the
organophosphorus compound is effective to provide phosphorus in an
amount of 0.3% to 0.8% of phosphorus, based on the weight of the
composition.
32. The multilayer article of claim 15, wherein the article has one
or more decorative layers applied to the polymer or glass layers by
methods including but not limited to screen printing, laser
marking, rotor gravure printing, pad printing, digital ink jet
printing, hydrographics, laser etching, laser printing, and
transfer printing.
33. The multilayer article of claim 15, wherein the article has one
or more of an OSU integrated 2 minute heat release test value of
less than 65 kW-min/m2; a peak heat release rate of less than 65
kW/m2 as measured using the method of FAR F25.4, in accordance with
Federal Aviation Regulation FAR 25.853 (d); an E662 smoke test Dmax
value of less than 200 when measured at a thickness of 1.6 mm.
34. The multilayer article of claim 15, wherein the article has one
or more of an OSU integrated 2 minute heat release test value of
less than 55 kW-min/m2; a peak heat release rate of less than 55
kW/m2 as measured using the method of FAR F25.4, in accordance with
Federal Aviation Regulation FAR 25.853 (d); an E662 smoke test Dmax
value of less than 200 when measured at a thickness of 1.6 mm.
35. The multilayer article of claim 15, wherein the article has a
heat release according to EN45545 and ISO 5660 of less than 90 kW;
a fire propagation in accordance with the method shown in EN45545
and ISO 5658-2 of greater than 20 kW; an EN 45545 and ISO 5659 for
a smoke density at 240 seconds, a smoke density of less than 300,
and a VOF4 smoke density of less than 600, and toxicity CITG, of
less than 0.9 for an HL2 rating and 1.2 for an HL1 rating.
36. The multilayer article of claim 15, wherein the article can
pass one or more of a SMP 800C and Boeing BSS 7239 test for
toxicity; the ASTM E162 test for flame spread; the ASTM E662 test
for smoke density; the FAR25.853 (d) Appendix F Part V for smoke
generation; the CFR 49, Chapter II, Federal Railroad
Administration, DOT, Part 223, Subpart B, Appendix A, Type I,
Ballistic Threat using caliber 0.22 LR (long rifle), 40.0-grain,
lead ammunition with a minimum impact velocity of 960 fps fired at
the center of the test sample; and a CFR 49, Chapter II, Federal
Railroad Administration, DOT, Part 223, Subpart B, Appendix A, Type
I, Block Threat using concrete blocks with a minimum weight of 25
lbs suspended and then dropped 30 feet, 1 inch onto the center of
the test sample.
37. The multilayer article of claim 15, wherein the article passes
a British test standards BS476 Part 7 test for flame spread; a
British test standards BS476 Part 6 for fire propagation; a British
test standards BS 6853:1999 Annex D8.4.for smoke generation; and a
British test standards BS 6853:1999 Annex B.2 for toxicity.
38. The multilayer article of claim 15, wherein polymer layer
comprises a flame retardant.
39. A double pane window comprising: a first pane comprising a
first glass layer, wherein the first glass layer is comprised of a
thin, chemically strengthened glass having a surface compressive
stress of between about 250 MPa and about 350 MPa and a depth of
layer (DOL) of compressive stress greater than 60 .mu.m; and a
first interlayer located in between the first glass layer and a
first polymer layer; wherein the first polymer layer comprises a
polysiloxane, a polyester, a polycarbonate, a copolymer comprising
one or more of the foregoing, or a blend comprising one or more of
the foregoing; a second pane comprising a third glass layer,
wherein the third glass layer is comprised of a thin, chemically
strengthened glass having a surface compressive stress of between
about 250 MPa and about 350 MPa and a depth of layer (DOL) of
compressive stress greater than 60 .mu.m; and a third interlayer
located in between the third glass layer and a second polymer
layer; wherein the second polymer layer comprises a polysiloxane, a
polyester, a polycarbonate, a copolymer comprising one or more of
the foregoing, or a blend comprising one or more of the foregoing;
a gap located in between the first pane and the second pane; and a
frame surrounding an edge of the first pane and the second
pane.
40. The window of claim 39, wherein the first pane further
comprises a second interlayer located in between a second glass
layer and the first polymer layer and/or the second pane further
comprises a fourth interlayer located in between a fourth glass
layer and the second polymer layer.
41. A method of making a multilayer article comprising: adding an
interlayer with a 0.2 to 1.4 mm interlayer thickness to a polymer
layer with a 2 to 15 mm polymer thickness; adding a glass layer
with a 0.1 to 1.5 mm glass layer thickness to the interlayer for
form a multilayer structure; and laminating the multilayer
structure to form the multilayer article; wherein the glass layer
is comprised of a thin, chemically strengthened glass having a
surface compressive stress of between about 250 MPa and about 350
MPa and a depth of layer (DOL) of compressive stress greater than
60 .mu.m; and wherein the polymer layer comprises a polysiloxane, a
polyester, a polycarbonate, a copolymer comprising one or more of
the foregoing, or a blend comprising one or more of the foregoing.
Description
[0001] This application claims the benefit of priority to U.S.
Application No. 61/871,928 filed Aug. 30, 2013, the content of
which is incorporated herein by reference in its entirety.
BACKGROUND
[0002] Glass laminates can be used as windows and glazing in
architectural and vehicle or transportation applications, including
automobiles, rolling stock, locomotive and airplanes. Glass
laminates can also be used as glass panels in balustrades and
stairs, and as decorative panels or coverings for walls, columns,
elevator cabs, kitchen appliances and other applications. As used
herein, a glazing or a laminated glass structure can be a
transparent, semi-transparent, translucent or opaque part of a
window, panel, wall, enclosure, sign or other structure. Common
types of glazing that are used in architectural and/or vehicular
applications include clear and tinted laminated glass
structures.
[0003] Conventional automotive glazing constructions for side
panels typically include a 5 mm thick monolithic soda lime glass
layer or two plies of 2.1 mm or 2.0 mm soda lime glass with an
intermediate tri-layer acoustic interlayer. These constructions
have certain advantages, including low cost and a sufficient impact
resistance for automotive and other applications. However, because
of their limited impact resistance and higher weight, these
laminates exhibit poor performance characteristics, including a
higher probability of breakage when struck by roadside debris,
vandals and other objects of impact as well as well as lower fuel
efficiencies for a respective vehicle.
[0004] As noted above such glass window panes are heavy and prone
to breakage from rock strike or other forms of vandalism. Efforts
have been made to replace the glass window panes with polymer
window panes as they are inherently lighter in weight than the
glass window panes and can be less prone to breakage. Polymer
window panes are also prone to breakage and often cannot meet the
Federal Railway Regulations for ballistic and block testing.
Furthermore, polymer window panes are prone to scratches and must
be replaced at regular intervals. Furthermore, polymer window panes
are generally not capable of passing strict flammability tests, for
example, one or more of the Federal Aviation Regulations, the
European Regulations, and British Regulations.
[0005] In applications where strength is important, the strength of
conventional glass can be enhanced by several methods, including
coatings, thermal tempering, and chemical strengthening (ion
exchange). Thermal tempering is conventionally employed in such
applications with thick, monolithic glass sheets, and has the
advantage of creating a thick compressive layer through the glass
surface, typically 20 to 25% of the overall glass thickness. The
magnitude of the compressive stress is relatively low, however,
typically less than 100 MPa. Furthermore, thermal tempering becomes
increasingly ineffective for relatively thin glass, e.g., less than
about 2 mm. In contrast, ion exchange (IX) techniques can produce
high levels of compressive stress in the treated glass, as high as
about 1000 MPa at the surface, and is suitable for very thin
glass.
[0006] Tempered glass (both thermally tempered and chemically
tempered) has the advantage of being more resistant to breakage
which can be desirable to enhance the reliability of laminated
automobile glazing. In particular, thin, chemically-tempered glass
can be desirable for use in making strong, lighter-weight auto
glazing. Thus, there is a need to provide an improved automotive
laminate structure. Furthermore, there is a need to provide an
improved window system comprising a polymer, for example, that is
capable of passing one or more of the Federal Aviation Regulations,
the European Regulations, the British Regulations, and the Federal
Railway Regulations.
SUMMARY
[0007] The embodiments disclosed herein generally relate to
glazings or laminates having laminated glass. Significant weight
savings can be achieved by replacing conventional monolithic glass
with an exemplary laminate structure having multiple sheets of
chemically strengthened glass (e.g., Gorilla.RTM. Glass) along with
a polymer interlayer (e.g., standard or acoustic polyvinyl
butryal). Simply replacing the conventional glass sheets in a
laminate structure with thinner chemically strengthened glass can
result in weight savings; however, the lowering of glass thickness
along with a soft polymer interlayer can result in the decrease of
overall structural rigidity of the laminated glass structure under
mechanical loading as the elastic modulus of typical interlayer
materials used in automotive side glass applications is
approximately 10.sup.4 to 10.sup.5 times lower than that of
glass.
[0008] Embodiments of the present disclosure can employ an
exemplary polycarbonate thermoplastic polymer as an interlayer
material for automotive side glass applications. The elastic
modulus of polycarbonate can be approximately 30 times lower than
that of Gorilla.RTM. Glass, and the density of polycarbonate can be
comparable to standard polymer interlayers employed in the
industry. Depending upon the thickness of the glass sheets in an
exemplary embodiment, polycarbonate thickness can be selected to
achieve maximum weight savings without compromising the mechanical
rigidity of the exemplary laminated glass structure.
[0009] Thus some embodiments provide improved window panes
comprising a polymer composition that can pass flammability tests
according to one or more of the Federal Aviation Regulations, the
European Regulations, and British Regulations and/or that can meet
one or both of the ballistic and block tests of the Federal Railway
Regulations. These regulations are difficult for polymer
compositions to pass and, to date, it is believed that all window
panes comprising a polymer have failed the British regulations.
Accordingly, an improved multilayer system was developed comprising
a hardened glass, an interlayer, and a polymer layer. In various
configurations, the multilayer system is able to pass one or more
of desired regulatory tests. The multilayer system is light weight
as compared to their glass window pane counter parts and provides
good scratch resistance. It is noted that while considered for
window panes, the disclosed multilayer structure can likewise be
used for doors (such as rail doors, platform doors, and elevator
doors), and in other applications with similar requirements such as
aircraft interior glazing, heavy truck glazing, agricultural
vehicle glazing, bus glazing, and automotive glazing. It is also
envisioned that the same or similar polymer formulations and
laminate stack ups will meet the needs for building and
construction glazing.
[0010] In accordance with one or more embodiments herein, thin
light-weight glass constructions are provided for a plurality of
transportation, architectural or other applications. In some
embodiment, thin light-weight glass constructions are provided for
automotive side windows, sunroofs, and the like, and can include
thin chemically strengthened glass (e.g., Gorilla.RTM. Glass) with
a polycarbonate as an interlayer material and additional polymer
interlayers (e.g., ethylene-vinyl acetate (EVA) or the like) as
intermediate layers between the polycarbonate and glass sheet(s).
In some embodiments, polycarbonate can impart a desired mechanical
rigidity to exemplary thin side window embodiments. In other
embodiments, the thickness of the polycarbonate can be selected
based upon outer glass sheet thicknesses so as not to alter side
window load-deflection characteristics. Exemplary polymer layers on
either side of the polycarbonate can promote adhesion between the
glass sheet(s) and polycarbonate and can also provide additional
acoustic performance for an exemplary laminate structure.
[0011] In some embodiments, a laminate structure is provided having
a first glass layer, a second glass layer, and a polymer interlayer
structure intermediate the first and second glass layers. The
polymer interlayer structure can include a first polymeric layer
adjacent to the first glass layer, a second polymeric layer
adjacent to the second glass layer, and a polymeric rigid core
intermediate the first and second polymeric layers, whereby the
first glass layer is comprised of a strengthened glass.
[0012] In other embodiments, a laminate structure is provided
having a first chemically strengthened glass layer, a second
chemically strengthened glass layer, and a polymer interlayer
structure intermediate the first and second glass layers. The
polymer interlayer structure can include a first polymeric layer
adjacent to the first glass layer, a second polymeric layer
adjacent to the second glass layer, and a polymeric rigid core
intermediate the first and second polymeric layers.
[0013] In some embodiments, a multilayer article is provided
comprising a first glass layer, wherein the first glass layer is
comprised of a thin, chemically strengthened glass having a surface
compressive stress of between about 250 MPa and about 350 MPa and a
depth of layer of compressive stress greater than 60 .mu.m. Such an
article includes a first interlayer and a polymer layer, where the
polymer layer comprises a polysiloxane, a polyester, a
polycarbonate, a copolymer comprising one or more of the foregoing,
or a blend comprising one or more of the foregoing. A first glass
layer can be from 0.5 to 1.5 mm, a first interlayer from 0.2 to 1.4
mm, and a polymer layer from 2 to 15 mm.
[0014] In some embodiments, a double pane window is provided
comprising a first pane comprising a first glass layer, wherein the
first glass layer is comprised of a thin, chemically strengthened
glass having a surface compressive stress of between about 250 MPa
and about 350 MPa and a depth of layer (DOL) of compressive stress
greater than 60 .mu.m, and a first interlayer located in between
the first glass layer and a first polymer layer, where the first
polymer layer comprises a polysiloxane, a polyester, a
polycarbonate, a copolymer comprising one or more of the foregoing,
or a blend comprising one or more of the foregoing. The window
further comprises a second pane comprising a third glass layer,
wherein the third glass layer is comprised of a thin, chemically
strengthened glass having a surface compressive stress of between
about 250 MPa and about 350 MPa and a depth of layer (DOL) of
compressive stress greater than 60 .mu.m, and a third interlayer
located in between the third glass layer and a second polymer
layer, where the second polymer layer comprises a polysiloxane, a
polyester, a polycarbonate, a copolymer comprising one or more of
the foregoing, or a blend comprising one or more of the foregoing.
The window may also include a gap located in between the first pane
and the second pane, and a frame surrounding an edge of the first
pane and the second pane.
[0015] It is to be understood that both the foregoing general
description and the following detailed description present
embodiments of the present disclosure, and are intended to provide
an overview or framework for understanding the nature and character
of the claimed subject matter. The accompanying drawings are
included to provide a further understanding of the present
disclosure, and are incorporated into and constitute a part of this
specification. The drawings illustrate various embodiments and
together with the description serve to explain the principles and
operations of the claimed subject matter.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] For the purposes of illustration, there are forms shown in
the drawings that are presently preferred, it being understood,
however, that the embodiments disclosed and discussed herein are
not limited to the precise arrangements and instrumentalities
shown.
[0017] FIG. 1 is a flow diagram illustrating some embodiments of
the present disclosure.
[0018] FIG. 2 is a cross-sectional illustration of a single sided
multilayer article.
[0019] FIG. 3 is a cross-sectional illustration of a dual sided
multilayer article.
[0020] FIG. 4 is a plot of polycarbonate thickness versus glass
thickness.
[0021] FIG. 5 is a plot of polycarbonate laminate mass for
different outer glass thicknesses.
[0022] FIG. 6 is another plot of polycarbonate thickness versus
glass thickness.
[0023] FIG. 7 is another plot of polycarbonate laminate mass for
different outer glass thicknesses.
[0024] FIG. 8 is a plot comparing the acoustic performance of
embodiments of the present disclosure with a monolithic soda lime
glass structure.
[0025] FIG. 9 is a plot comparing the acoustic performance of
embodiments of the present disclosure with a soda lime glass
laminate structure.
[0026] FIG. 10 is a cross-sectional illustration of an exemplary
multi-pane multilayer article.
[0027] FIG. 11 is a cross-sectional illustration of another
exemplary multi-pane multilayer article.
DETAILED DESCRIPTION
[0028] In the following description, like reference characters
designate like or corresponding parts throughout the several views
shown in the figures. It is also understood that, unless otherwise
specified, terms such as "top," "bottom," "outward," "inward," and
the like are words of convenience and are not to be construed as
limiting terms. In addition, whenever a group is described as
comprising at least one of a group of elements and combinations
thereof, it is understood that the group may comprise, consist
essentially of, or consist of any number of those elements recited,
either individually or in combination with each other.
[0029] Similarly, whenever a group is described as consisting of at
least one of a group of elements or combinations thereof, it is
understood that the group may consist of any number of those
elements recited, either individually or in combination with each
other. Unless otherwise specified, a range of values, when recited,
includes both the upper and lower limits of the range. As used
herein, the indefinite articles "a," and "an," and the
corresponding definite article "the" mean "at least one" or "one or
more," unless otherwise specified
[0030] The following description of the present disclosure is
provided as an enabling teaching thereof and its best,
currently-known embodiment. Those skilled in the art will recognize
that many changes can be made to the embodiment described herein
while still obtaining the beneficial results of the present
disclosure. It will also be apparent that some of the desired
benefits of the present disclosure can be obtained by selecting
some of the features of the present disclosure without utilizing
other features. Accordingly, those of ordinary skill in the art
will recognize that many modifications and adaptations of the
present disclosure are possible and can even be desirable in
certain circumstances and are part of the present disclosure. Thus,
the following description is provided as illustrative of the
principles of the present disclosure and not in limitation
thereof.
[0031] FIG. 1 is a flow diagram illustrating some embodiments of
the present disclosure. With reference to FIG. 1, some embodiments
include the application of one or more processes for producing a
relatively thin glass sheet (on the order of about 2 mm or less)
having certain characteristics, such as relatively moderate
compressive stress (CS), relatively high depth of compressive layer
(DOL), and/or moderate central tension (CT). The process includes
preparing a glass sheet capable of ion exchange (step 100). The
glass sheet can then be subjected to an ion exchange process (step
101), and thereafter the glass sheet can be subjected to an anneal
process (step 103) if necessary. Of course, if the CS and DOL of
the glass sheet is desired at the levels resulting from the ion
exchange step (step 101), then no annealing step (step 103) is
required. In other embodiments, an acid etching process (step 105)
can be used to increase the CS on appropriate glass surfaces.
[0032] The ion exchange process 101 can involve subjecting the
glass sheet to a molten salt bath including KNO.sub.3, preferably
relatively pure KNO.sub.3 for one or more first temperatures within
the range of about 400-500.degree. C. and/or for a first time
period within the range of about 1-24 hours, such as, but not
limited to, about 8 hours. It is noted that other salt bath
compositions are possible and would be within the skill level of an
artisan to consider such alternatives. Thus, the disclosure of
KNO.sub.3 should not limit the scope of the claims appended
herewith. Such an exemplary ion exchange process can produce an
initial compressive stress (iCS) at the surface of the glass sheet,
an initial depth of compressive layer (iDOL) into the glass sheet,
and an initial central tension (iCT) within the glass sheet.
[0033] In general, after an exemplary ion exchange process, the
initial compressive stress (iCS) can exceed a predetermined (or
desired) value, such as being at or greater than about 500 MPa, and
can typically reach 600 MPa or higher, or even reach 1000 MPa or
higher in some glasses and under some processing profiles.
Alternatively, after an exemplary ion exchange process, initial
depth of compressive layer (iDOL) can be below a predetermined (or
desired) value, such as being at or less than about 75 .mu.m or
even lower in some glasses and under some processing profiles.
Alternatively, after an exemplary ion exchange process, initial
central tension (iCT) can exceed a predetermined (or desired)
value, such as above a predetermined frangibility limit of the
glass sheet, which can be at or above about 40 MPa, or more
particularly at or above about 48 MPa in some glasses.
[0034] If the initial compressive stress (iCS) exceeds a desired
value, initial depth of compressive layer (iDOL) is below a desired
value, and/or initial central tension (iCT) exceeds a desired
value, this can lead to undesirable characteristics in a final
product made using the respective glass sheet. For example, if the
initial compressive stress (iCS) exceeds a desired value (reaching
for example, 1000 MPa), then facture of the glass under certain
circumstances might not occur. Although this may be
counter-intuitive, in some circumstances the glass sheet should be
able to break, such as in an automotive glass application where the
glass must break at a certain impact load to prevent injury.
[0035] Further, if the initial depth of compressive layer (iDOL) is
below a desired value, then under certain circumstances the glass
sheet can break unexpectedly and under undesirable circumstances.
Typical ion exchange processes can result in an initial depth of
compressive layer (iDOL) being no more than about 40-60 .mu.m,
which can be less than the depth of scratches, pits, etc.,
developed in the glass sheet during use. For example, it has been
discovered that installed automotive glazing (using ion exchanged
glass) can develop external scratches reaching as deep as about 75
.mu.m or more due to exposure to abrasive materials such as silica
sand, flying debris, etc., within the environment in which the
glass sheet is used. This depth can exceed the typical depth of
compressive layer, which can lead to the glass unexpectedly
fracturing during use.
[0036] Finally, if the initial central tension (iCT) exceeds a
desired value, such as reaching or exceeding a chosen frangibility
limit of the glass, then the glass sheet can break unexpectedly and
under undesirable circumstances. For example, it has been
discovered that a 4 inch.times.4 inch.times.0.7 mm sheet of Corning
Gorilla.RTM. Glass exhibits performance characteristics in which
undesirable fragmentation (energetic failure into a large number of
small pieces when broken) occurs when a long single step ion
exchange process (8 hours at 475.degree. C.) was performed in pure
KNO.sub.3. Although a DOL of about 101 .mu.m was achieved, a
relatively high CT of 65 MPa resulted, which was higher than the
chosen frangibility limit (48 MPa) of the subject glass sheet.
[0037] In accordance with one or more embodiments, however, after
the glass sheet has been subject to ion exchange, the glass sheet
can be subjected to an annealing process 104 by elevating the glass
sheet to one or more second temperatures for a second period of
time. For example, the annealing process 104 can be carried out in
an air environment, can be performed at second temperatures within
the range of about 400-500.degree. C., and can be performed in a
second time period within the range of about 4-24 hours, such as,
but not limited to, about 8 hours. The annealing process 104 can
thus cause at least one of the initial compressive stress (iCS),
the initial depth of compressive layer (iDOL), and the initial
central tension (iCT) to be modified.
[0038] For example, after the annealing process 104, the initial
compressive stress (iCS) can be reduced to a final compressive
stress (fCS) which is at or below a predetermined value. By way of
example, the initial compressive stress (iCS) can be at or greater
than about 500 MPa, but the final compressive stress (fCS) can be
at or less than about 400 MPa, 350 MPa, or 300 MPa. It is noted
that the target for the final compressive stress (fCS) can be a
function of glass thickness as in thicker glass a lower fCS can be
desirable, and in thinner glass a higher fCS can be tolerable.
[0039] Additionally, after the annealing process 104, the initial
depth of compressive layer (iDOL) can be increased to a final depth
of compressive layer (IDOL) at or above the predetermined value. By
way of example, the initial depth of compressive layer (iDOL) can
be at or less than about 75 .mu.m, and the final depth of
compressive layer (fDOL) can be at or above about 80 .mu.m or 90
.mu.m, such as 100 .mu.m or more.
[0040] Alternatively, after the annealing process 104, the initial
central tension (iCT) can be reduced to a final central tension
(fCT) at or below the predetermined value. By way of example, the
initial central tension (iCT) can be at or above a chosen
frangibility limit of the glass sheet (such as between about 40-48
MPa), and the final central tension (fCT) can be below the chosen
frangibility limit of the glass sheet. Additional examples for
generating exemplary ion exchangeable glass structures are
described in co-pending U.S. application Ser. No. 13/626,958, filed
Sep. 26, 2012 and U.S. application Ser. No. 13/926,461, filed Jun.
25, 2013 the entirety of each being incorporated herein by
reference.
[0041] As noted above the conditions of the ion exchange step and
the annealing step can be adjusted to achieve a desired compressive
stress at the glass surface (CS), depth of compressive layer (DOL),
and central tension (CT). The ion exchange step can be carried out
by immersion of the glass sheet into a molten salt bath for a
predetermined period of time, where ions within the glass sheet at
or near the surface thereof are exchanged for larger metal ions,
for example, from the salt bath. By way of example, the molten salt
bath can include KNO.sub.3, the temperature of the molten salt bath
can be within the range of about 400-500.degree. C., and the
predetermined time period can be within the range of about 1-24
hours, and preferably between about 2-8 hours. The incorporation of
the larger ions into the glass strengthens the sheet by creating a
compressive stress in a near surface region. A corresponding
tensile stress can be induced within a central region of the glass
sheet to balance the compressive stress.
[0042] By way of further example, sodium ions within the glass
sheet can be replaced by potassium ions from the molten salt bath,
though other alkali metal ions having a larger atomic radius, such
as rubidium or cesium, can also replace smaller alkali metal ions
in the glass. According to some embodiments, smaller alkali metal
ions in the glass sheet can be replaced by Ag+ ions. Similarly,
other alkali metal salts such as, but not limited to, sulfates,
halides, and the like can be used in the ion exchange process.
[0043] The replacement of smaller ions by larger ions at a
temperature below that at which the glass network can relax
produces a distribution of ions across the surface of the glass
sheet resulting in a stress profile. The larger volume of the
incoming ion produces a compressive stress (CS) on the surface and
tension (central tension, or CT) in the center region of the glass.
The compressive stress is related to the central tension by the
following approximate relationship:
CS = CT ( t - 2 DOL DOL ) ##EQU00001##
where t represents the total thickness of the glass sheet and DOL
represents the depth of exchange, also referred to as depth of
compressive layer.
[0044] In some embodiments, acid etching (step 105) of a glass
surface can reduce the number, size and severity of flaws in the
respective surface of the glass sheet. Surface flaws act as
fracture sites in glass sheets. Reducing the number, the size and
severity of the flaws in these surfaces can remove and minimize the
size of potential fracture initiation sites in these surfaces to
thereby strengthen the surface of the respective glass sheets. The
use of an acid etch surface treatment can comprise contacting one
surface of a glass sheet with an acidic glass etching medium and
can be versatile, readily tailored to most glasses, and readily
applied to both planar and complex cover glass sheet geometries.
Further, exemplary acid etching has been found to be effective to
reduce strength variability, even in glass having a low incidence
of surface flaws, including up-drawn or down-drawn (e.g.,
fusion-drawn) glass sheet that are conventionally thought to be
largely free of surface flaws introduced during manufacture or
during post-manufacturing processing. An exemplary acid treatment
step can provide a chemical polishing of a glass surface that can
alter the size, alter the geometry of surface flaws, and/or reduce
the size and number of surface flaws but have a minimal effect on
the general topography of the treated surface. In general, acid
etching treatments can be employed to remove not more than about 4
.mu.m of surface glass, or in some embodiments not more than 2
.mu.m of surface glass, or not more than 1 .mu.m of surface glass.
The acid etch treatment can be advantageously performed prior to
lamination to protect the respective surface from the creation of
any new flaws.
[0045] Acid removal of more than a predetermined thickness of
surface glass from chemically tempered glass sheet should be
avoided to ensure that the thickness of the surface compression
layer and the level of surface compressive stress provided by that
layer are not unacceptably reduced as this could be detrimental to
the impact and flexural damage resistance of a respective glass
sheet. Additionally, excessive etching of the glass surface can
increase the level of surface haze in the glass to objectionable
levels. For window, automotive glazing, and consumer electronics
display applications, typically no or very limited visually
detectable surface haze in the glass cover sheet for the display is
permitted.
[0046] A variety of etchant chemicals, concentrations, and
treatment times can be used to achieve a desirable level of surface
treatment and strengthening in embodiments of the present
disclosure. Exemplary chemicals useful for carrying out the acid
treatment step include fluoride-containing aqueous treating media
containing at least one active glass etching compound including,
but not limited to, HF, combinations of HF with one or more of HCL,
HNO.sub.3 and H.sub.2SO.sub.4, ammonium bifluoride, sodium
bifluoride and other suitable compounds. For example, an aqueous
acidic solution having 5 vol. % HF (48%) and 5 vol. %
H.sub.2SO.sub.4 (98%) in water can improve the ball drop
performance of ion-exchange-strengthened alkali aluminosilicate
glass sheet having a thickness in the range of about 0.5 mm to
about 1.5 mm using treatment times as short as one minute in
duration. It should be noted that exemplary glass layers not
subjected to ion-exchange strengthening or thermal tempering,
whether before or after acid etching, can require different
combinations of etching media to achieve large improvements in ball
drop test results.
[0047] Maintaining adequate control over the thickness of the glass
layer removed by etching in HF-containing solutions can be
facilitated if the concentrations of HF and dissolved glass
constituents in the solutions are closely controlled. While
periodic replacement of the entire etching bath to restore
acceptable etching rates is effective for this purpose, bath
replacement can be expensive and the cost of effectively treating
and disposing of depleted etching solutions can be high. Exemplary
methods for etching glass layers is described in co-pending
International Application No. PCT/US13/43561, filed May 31, 2013,
the entirety of which is incorporated herein by reference.
[0048] Satisfactorily strengthened glass sheets or layers can
retain a compressive surface layer having a DOL of at least 30
.mu.m or even 40 .mu.m, after surface etching, with the surface
layer providing a peak compressive stress level of at least 500
MPa, or even 650 MPa. To provide thin alkali aluminosilicate glass
sheets offering this combination of properties, sheet surface
etching treatments of limited duration can be required. In
particular, the step of contacting a surface of the glass sheet
with an etching medium can be carried out for a period of time not
exceeding that required for effective removal of 2 .mu.m of surface
glass, or in some embodiments not exceeding that required for
effective removal of 1 .mu.m of surface glass. Of course, the
actual etching time required to limit glass removal in any
particular case can depend upon the composition and temperature of
the etching medium as well as the composition of the solution and
the glass being treated; however, treatments effective to remove
not more than about 1 .mu.m or about 2 .mu.m of glass from the
surface of a selected glass sheet can be determined by routine
experiment.
[0049] An alternative method for ensuring that glass sheet
strengths and surface compression layer depths are adequate can
involve tracking reductions in surface compressive stress level as
etching proceeds. Etching time can then be controlled to limit
reductions in surface compressive stress necessarily caused by the
etching treatment. Thus, in some embodiments the step of contacting
a surface of a strengthened alkali aluminosilicate glass sheet with
an etching medium can be carried out for a time not exceeding a
time effective to reduce the compressive stress level in the glass
sheet surface by 3% or another acceptable amount. Again, the period
of time suitable for achieving a predetermined amount of glass
removal can depend upon the composition and temperature of the
etching medium as well as the composition of the glass sheet, but
can also readily be determined by routine experiment. Additional
details regarding glass surface acid or etching treatments can be
found in co-pending U.S. patent application Ser. No. 12/986,424
filed Jan. 7, 2011, the entirety of which is hereby incorporated by
reference.
[0050] Additional etching treatments can be localized in nature.
For example, surface decorations or masks can be placed on a
portion(s) of the glass sheet or article. The glass sheet can then
be etched to increase surface compressive stress in the area
exposed to the etching but the original surface compressive stress
(e.g., the surface compressive stress of the original ion exchanged
glass) can be maintained in the portion(s) underlying the surface
decoration or mask. Of course, the conditions of each process step
can be adjusted based on the desired compressive stress at the
glass surface(s), desired depth of compressive layer, and desired
central tension.
[0051] Any number of specific glass compositions can be employed in
producing the glass sheet. For example, ion-exchangeable glasses
suitable for use in the embodiments herein include alkali
aluminosilicate glasses or alkali aluminoborosilicate glasses,
though other glass compositions are contemplated. As used herein,
"ion exchangeable" means that a glass is capable of exchanging
cations located at or near the surface of the glass with cations of
the same valence that are either larger or smaller in size.
[0052] For example, a suitable glass composition comprises
SiO.sub.2, B.sub.2O.sub.3 and Na.sub.2O, where
(SiO.sub.2+B.sub.2O.sub.3).gtoreq.66 mol. %, and Na.sub.2O.gtoreq.9
mol. %. In an embodiment, the glass sheets include at least 6 wt. %
aluminum oxide. In a further embodiment, a glass sheet includes one
or more alkaline earth oxides, such that a content of alkaline
earth oxides is at least 5 wt. %. Suitable glass compositions, in
some embodiments, further comprise at least one of K.sub.2O, MgO,
and CaO. In a particular embodiment, the glass can comprise 61-75
mol. % SiO.sub.2; 7-15 mol. % Al.sub.2O.sub.3; 0-12 mol. %
B.sub.2O.sub.3; 9-21 mol. % Na.sub.2O; 0-4 mol. % K.sub.2O; 0-7
mol. % MgO; and 0-3 mol. % CaO.
[0053] A further example glass composition suitable for forming
hybrid glass laminates comprises: 60-70 mol. % SiO.sub.2; 6-14 mol.
% Al.sub.2O.sub.3; 0-15 mol. % B.sub.2O.sub.3; 0-15 mol. %
Li.sub.2O; 0-20 mol. % Na.sub.2O; 0-10 mol. % K.sub.2O; 0-8 mol. %
MgO; 0-10 mol. % CaO; 0-5 mol. % ZrO.sub.2; 0-1 mol. % SnO.sub.2;
0-1 mol. % CeO.sub.2; less than 50 ppm As.sub.2O.sub.3; and less
than 50 ppm Sb.sub.2O.sub.3; where 12 mol. %
(Li.sub.2O+Na.sub.2O+K.sub.2O).ltoreq.20 mol. % and 0 mol.
%.ltoreq.(MgO+CaO).ltoreq.10 mol. %.
[0054] A still further example glass composition comprises:
63.5-66.5 mol. % SiO.sub.2; 8-12 mol. % Al.sub.2O.sub.3; 0-3 mol. %
B.sub.2O.sub.3; 0-5 mol. % Li.sub.2O; 8-18 mol. % Na.sub.2O; 0-5
mol. % K.sub.2O; 1-7 mol. % MgO; 0-2.5 mol. % CaO; 0-3 mol. %
ZrO.sub.2; 0.05-0.25 mol. % SnO.sub.2; 0.05-0.5 mol. % CeO.sub.2;
less than 50 ppm As.sub.2O.sub.3; and less than 50 ppm
Sb.sub.2O.sub.3; where 14 mol.
%.ltoreq.(Li.sub.2O+Na.sub.2O+K.sub.2O).ltoreq.18 mol. % and 2 mol.
%.ltoreq.(MgO+CaO).ltoreq.7 mol. %.
[0055] In another embodiment, an alkali aluminosilicate glass
comprises, consists essentially of, or consists of: 61-75 mol. %
SiO.sub.2; 7-15 mol. % Al.sub.2O.sub.3; 0-12 mol. % B.sub.2O.sub.3;
9-21 mol. % Na.sub.2O; 0-4 mol. % K.sub.2O; 0-7 mol. % MgO; and 0-3
mol. % CaO.
[0056] In a particular embodiment, an alkali aluminosilicate glass
comprises alumina, at least one alkali metal and, in some
embodiments, greater than 50 mol. % SiO.sub.2, in other embodiments
at least 58 mol. % SiO.sub.2, and in still other embodiments at
least 60 mol. % SiO.sub.2, wherein the ratio where
Al 2 O 3 + B 2 O 3 modifiers > 1 , ##EQU00002##
in the ratio the components are expressed in mol. % and the
modifiers are alkali metal oxides. This glass, in particular
embodiments, comprises, consists essentially of, or consists of:
58-72 mol. % SiO.sub.2; 9-17 mol. % Al.sub.2O.sub.3; 2-12 mol. %
B.sub.2O.sub.3; 8-16 mol. % Na.sub.2O; and 0-4 mol. % K.sub.2O,
wherein the ratio
Al 2 O 3 + B 2 O 3 modifiers > 1. ##EQU00003##
[0057] In yet another embodiment, an alkali aluminosilicate glass
substrate comprises, consists essentially of, or consists of: 60-70
mol. % SiO.sub.2; 6-14 mol. % Al.sub.2O.sub.3; 0-15 mol. %
B.sub.2O.sub.3; 0-15 mol. % Li.sub.2O; 0-20 mol. % Na.sub.2O; 0-10
mol. % K.sub.2O; 0-8 mol. % MgO; 0-10 mol. % CaO; 0-5 mol. %
ZrO.sub.2; 0-1 mol. % SnO.sub.2; 0-1 mol. % CeO.sub.2; less than 50
ppm As.sub.2O.sub.3; and less than 50 ppm Sb.sub.2O.sub.3; wherein
12 mol. %.ltoreq.Li.sub.2O+Na.sub.2O+K.sub.2O.ltoreq.20 mol. % and
0 mol. %.ltoreq.MgO+CaO.ltoreq.10 mol. %.
[0058] In still another embodiment, an alkali aluminosilicate glass
comprises, consists essentially of, or consists of: 64-68 mol. %
SiO.sub.2; 12-16 mol. % Na.sub.2O; 8-12 mol. % Al.sub.2O.sub.3; 0-3
mol. % B.sub.2O.sub.3; 2-5 mol. % K.sub.2O; 4-6 mol. % MgO; and 0-5
mol. % CaO, wherein: 66 mol.
%.ltoreq.SiO.sub.2+B.sub.2O.sub.3+CaO.ltoreq.69 mol. %;
Na.sub.2O+K.sub.2O+B.sub.2O.sub.3+MgO+CaO+SrO>10 mol. %; 5 mol.
%.ltoreq.MgO+CaO+SrO.ltoreq.8 mol. %;
(Na.sub.2O+B.sub.2O.sub.3).ltoreq.Al.sub.2O.sub.3 2 mol. %; 2 mol.
%.ltoreq.Na.sub.2O Al.sub.2O.sub.3.ltoreq.6 mol. %; and 4 mol.
%.ltoreq.(Na.sub.2O+K.sub.2O).ltoreq.Al.sub.2O.sub.3.ltoreq.10 mol.
%. Additional compositions of exemplary glass structures are
described in co-pending U.S. application Ser. No. 13/626,958, filed
Sep. 26, 2012 and U.S. application Ser. No. 13/926,461, filed Jun.
25, 2013 the entirety of each being incorporated herein by
reference.
[0059] FIG. 2 is a cross-sectional illustration of a single sided
multilayer article. With reference to FIG. 2, an exemplary
multilayer article can be a single sided article 2 with a polymer
layer 30 having a polymer side 32 and polymer side 34, an
interlayer 20 that has an interlayer side 22 and interlayer side
24, and a glass layer 10 that has a glass side 12 and glass side
14. FIG. 2 illustrates that the glass side 14 is in direct contact
with the interlayer side 22, and the interlayer side 24 is in
direct contact with the polymer side 32. The total thickness of a
single sided multilayer article can be from about 2 to 20 mm,
specifically, from about 4 to 16 mm, more specifically, from about
5 to 14 mm and all sub-ranges in between. In an embodiment a
decorative layer is disposed onto the polymer side 32. In another
embodiment a decorative layer is disposed onto the glass side 14.
In an embodiment, a decorative layer is disposed onto the polymer
side 32 and the glass side 14. It is also contemplated that a
decorative layer could be disposed onto glass side 12 and/or
polymer side 34 separately or in addition to having decorative
layers on the aforementioned layers of the multilayer article.
[0060] The multilayer article can be a dual sided article that
comprises a polymer layer with a polymer side A and a polymer side
B; a first glass layer located on the polymer side A with a first
interlayer located in between the first glass layer and the polymer
layer; and a second glass layer located on the polymer side B with
a second interlayer located in between the first glass layer and
the polymer layer. FIG. 3 is a cross-sectional illustration of a
dual sided multilayer article 4 with a polymer layer 30 that has a
polymer side 32 and polymer side 34, an interlayer 20 that has an
interlayer side 22 and interlayer side 24, an interlayer 40 that
has an interlayer side 42 and interlayer side 44, a glass layer 50
that has a glass side 52 and glass side 54, and a glass layer 10
that has a glass side 12 and glass side 14. FIG. 3 illustrates that
the glass side 14 is in direct contact with the interlayer side 22,
the interlayer side 24 is in direct contact with the polymer side
32, the polymer side 34 is in direct contact with the interlayer
side 42, and the interlayer side 44 is in direct contact with the
glass side 52. It is noted that one or both of the glass layers 10
and 50 can comprise hardened glass. The total thickness of a dual
sided multilayer article can be from about 2 to 25 mm,
specifically, from about 4 to 18 mm, more specifically, from about
5 to 14 mm and all sub-ranges in between. In an embodiment a
decorative layer is disposed onto the polymer side 32 and/or 34. In
another embodiment a decorative layer is disposed onto the glass
side 14 and/or 52. In an embodiment, a decorative layer is disposed
onto the polymer side 32 and/or polymer side 34 and/or the glass
side 14 and/or the glass side 52. It is also contemplated that a
decorative layer could be disposed onto glass side 12 and/or 54
separately or in addition to having decorative layers on the
aforementioned layers of the multilayer article.
[0061] With continued reference to FIGS. 2 and 3, some embodiments
of the present disclosure can include one layer of chemically
strengthened glass (FIG. 2) or two layers of chemically
strengthened glass (FIG. 3), e.g., Gorilla.RTM. Glass, that have
been heat treated, ion exchanged, annealed, and/or chemically
etched as described above. In additional embodiments, one or both
layers of chemically strengthened glass, as applicable, have only
been heat treated and ion exchanged. In some embodiments, a
laminate or article 4 can be comprised of an outer layer 10 of
glass having a thickness of less than or equal to about 1.0 mm and
having a residual surface CS level of between about 250 MPa to
about 350 MPa with a DOL of greater than 60 microns if annealed
after an ion exchange process. In other embodiments, the CS level
of the outer layer 10 can be greater than 350 MPa and can be
between 400 MPa and 900 MPa depending upon the processes performed
on the embodiment as described above. The laminate or article 4
also includes a polymeric interlayer comprising a rigid polymeric
core 30 and two outer polymeric layers 20, 40. The article 4
further includes an inner layer of glass 50 also having a thickness
of less than or equal to about 1.0 mm and having a residual surface
CS level of between about 250 MPa to about 350 MPa with a DOL of
greater than 60 microns if annealed after an ion exchange process.
In other embodiments, the CS level of the inner layer 50 can be
greater than 350 MPa and can be between 400 MPa and 900 MPa
depending upon the processes performed on the embodiment as
described above. In some embodiments, the rigid core 30 is formed
from a polycarbonate material or other suitable material. This
rigid core 30 can impart the desired mechanical rigidity to the
exemplary article 4 and any resulting window construction
therefrom. The thickness of polycarbonate can be selected based
upon outside glass ply thicknesses so as not to alter the
automotive window load-deflection characteristic. Exemplary
thicknesses of the polymeric interlayers can range in thicknesses
from 0.1 mm to 0.3 mm to 0.5 mm to 0.8 mm or more. Exemplary
thicknesses of the rigid core 30 can range in thicknesses from 2.0
mm to 3.8 mm to 5.0 mm or more. Exemplary materials for the two
outer polymeric layers 20, 40 and also the rigid polymeric core 30
will be discussed in further detail below but include and are not
limited to poly vinyl butyral (PVB), polycarbonate, acoustic PVB,
ethylene vinyl acetate (EVA), thermoplastic polyurethane (TPU),
ionomer, a thermoplastic material, and combinations thereof.
Exemplary thicknesses of the polymeric interlayers can range in
thicknesses from 0.1 mm to 0.3 mm to 0.5 mm to 0.8 mm or more.
Exemplary outer polymeric layers 20, 40 on either side of the rigid
polymeric core 30 can promote adhesion between the glass layers 10,
50 and the rigid polymeric core 30 as well as add to the respective
window acoustic performance.
[0062] In another embodiment of the present disclosure, at least
one layer of thin but high strength glass can be used to construct
an exemplary laminate structure. In such an embodiment, chemically
strengthened glass, e.g., Gorilla.RTM. Glass, can be used for the
outer layer 10 and/or inner layer 50 of glass for an exemplary
article 4. In another embodiment, the inner layer 50 of glass can
be conventional soda lime glass, annealed glass, or the like.
Exemplary thicknesses of the outer and/or inner layers 10, 50 can
range in thicknesses from 0.55 mm to 1.5 mm to 2.0 mm or more.
Additional thicknesses can range from about 0.1 mm to 2.0 mm, 0.1
to 0.3 mm, 0.1 to 0.5 mm, 0.1 to 1.5 mm or more and all sub-ranges
in between. Additionally, the thicknesses of the outer and inner
layers 10, 50 can be different in a laminate structure or article
4. Exemplary glass layers can be made by fusion drawing, as
described in U.S. Pat. Nos. 7,666,511, 4,483,700 and 5,674,790, the
entirety of each being incorporated herein by reference, and then
chemically strengthening such drawn glass. Exemplary glass layers
10, 50 can thus possess a deep DOL of CS and can present a high
flexural strength, scratch resistance and impact resistance.
Exemplary embodiments can also include acid etched or flared
surfaces to increase the impact resistance and increasing the
strength of such surfaces by reducing the size and severity of
flaws on these surfaces. If etched immediately prior to lamination,
the strengthening benefit of etching or flaring can be maintained
on surfaces bonded to the inter-layer.
[0063] In some experiments, flat rectangular glass panels were
evaluated using non-linear finite element analysis calculations.
The dimension of the glass panels were approximately 1000 mm by 800
mm which is similar to that of a Ford Taurus side window. The glass
panels were assumed to be supported on all four edges with a
uniform pressure load of approximately 2000 Pa (0.3 psi) applied on
one of the faces of the glass panel to approximate typical windload
pressures. In one experiment, an approximately 5 mm thick
conventional monolithic glass was used as a benchmark to compare
the deflection of the monolithic glass sheet with embodiments of
the present disclosure. In another experiment, a two ply laminate
construction having two 2.1 mm glass sheets was also used as a
benchmark to compare the deflection of this conventional laminate
structure with embodiments of the present disclosure. Table A
provided below summarizes the deflection of conventional 5 mm
monolithic glass and conventional two ply laminate constructions
having two 2.1 mm glass sheets.
TABLE-US-00001 TABLE A Deflection (mm) Mass (Kg/lbs) 5 mm monolith
5.4 10/22 Two ply (2.1/2.1 mm) 7.4 8.8/19.3 laminate structure
[0064] The values provided in Table A above were used as a
benchmark to evaluate laminate constructions according to
embodiments of the present disclosure. Table B provided below shows
mechanical properties of various materials used in the
experiments.
TABLE-US-00002 TABLE B Elastic modulus Density (MPa) Poisson's
ratio (Kg/m.sup.3) Chemically 71,700 0.21 2440 strengthened glass
Polycarbonate 2200 0.37 1210 EVA 10 (at 1 Hz at 20.degree. C.) 0.49
1000 Standard PVB 15 (at 1 Hz at 20.degree. C.) 0.49 1069 Acoustic
PVB 3 (at 1 Hz at 20.degree. C.) 0.49 1069
[0065] FIG. 4 is a plot of polycarbonate thickness versus glass
thickness. With reference to FIG. 4, a plot of glass thickness
versus polycarbonate thickness in a laminated glass panel is
illustrated that will have a same deflection as a 5.0 mm monolith
glass equal to 5.4 mm for the pressure and support/loading
conditions described above. The curve generally illustrates the
thickness of an exemplary rigid or polycarbonate core necessary to
achieve a deflection of 5.4 mm when modifying the thickness of
outer chemically strengthened glass layers. Thus, as the thickness
of outer glass layers in an embodiment of the present disclosure is
lowered, the thickness of the rigid core, e.g., polycarbonate,
should be increased to achieve the same deflection as a 5 mm
monolithic structure.
[0066] FIG. 5 is a plot of polycarbonate laminate mass for
different outer glass thicknesses. With reference to FIG. 5, a plot
of outer glass ply thickness versus total laminate weight is
illustrated. The plot generally indicates that, compared to a 5 mm
monolithic glass structure, maximum weight savings of approximately
20% can be achieved when using 0.8 mm thick chemically strengthened
glass (e.g., Gorilla.RTM. Glass). In such an embodiment, the
laminate structure could require the use of an approximately 4.5 mm
thick polycarbonate core (see FIG. 4) to achieve a desired
deflection. It also follows that if 0.7 mm thick chemically
strengthened glass were utilized (e.g., Gorilla.RTM. Glass), the
weight savings would be approximately 19% and the use of an
approximately 5 mm thick polycarbonate core should be employed.
[0067] FIG. 6 is another plot of polycarbonate thickness versus
glass thickness. FIG. 7 is another plot of polycarbonate laminate
mass for different outer glass thicknesses. With reference to FIG.
6, a plot of glass thickness versus polycarbonate thickness in a
laminated glass panel is illustrated that will have a same
deflection as a conventional two ply laminated structure (two
sheets of 2.1 mm soda lime glass) for the pressure and
support/loading conditions described above. With reference to FIG.
7, a plot of outer glass ply thickness versus total laminate weight
is illustrated for this same conventional two ply laminated
structure. These two plots indicate that when using an
approximately 0.7 mm thick chemically strengthened glass (e.g.,
Gorilla.RTM. Glass) as an outer glass layer, a 21.5% weight savings
can be achieved with an approximately 4 mm thick polycarbonate
core. Such an exemplary construction would have the same deflection
as a conventional two ply laminate structure under pressure and
support conditions discussed above. Thus, for embodiments of the
present disclosure, a weight reduction of as much as 20% or more
can be achieved over conventional structures. Such exemplary
constructions can also meet customer deflection and acoustic
requirements as well as pass standard certification tests.
[0068] FIG. 8 is a plot comparing the acoustic performance of
embodiments of the present disclosure with a monolithic soda lime
glass structure. FIG. 9 is a plot comparing the acoustic
performance of embodiments of the present disclosure with a soda
lime glass laminate structure. With reference to FIG. 8, it can be
observed that embodiments of the present disclosure having 0.7 mm
thick chemically strengthened glass (e.g., Gorilla.RTM. Glass) with
0.3 mm EVA layers and a 5 mm rigid core of polycarbonate
substantially correspond to the flexural properties of an
approximately 5 mm thick monolithic soda lime glass structure while
providing a 20% weight savings. Further, FIG. 8 illustrates
comparable transmission losses between embodiments of the present
disclosure and the monolithic soda lime glass structure; however,
as expected the transmission loss is slightly less for embodiments
of the present disclosure as these embodiments are 20% lighter than
the 5 mm thick monolithic glass. It should be noted, however, that
very little transmission loss difference was observed at the
coincidence frequency and, in some cases, additional dampening with
embodiments of the present disclosure was observed. With reference
to FIG. 9, it can be observed that embodiments of the present
disclosure having 0.7 mm thick chemically strengthened glass (e.g.,
Gorilla.RTM. Glass) with 0.3 mm EVA layers and a 3.8 mm rigid core
of polycarbonate substantially correspond to the flexural
properties of a conventional two ply soda lime glass laminate
structure having two sheets of 2.1 mm soda lime glass with an
intermediate acoustic PVB interlayer while providing a 30% weight
savings. It can also be observed that transmission loss of
embodiments of the present disclosure are about 2 dB less than that
of the conventional two ply soda lime glass laminate due to the 30%
weight savings of such embodiments. At the coincidence frequency of
2500 Hz, some embodiments can provided less transmission loss than
the conventional 2.1 mm soda lime glass laminate structure due to
the acoustic PVB in the soda lime glass laminate structure acting
to reduce the depth of the coincidence dip and to shift it to
higher frequencies. At frequencies above about 5000 Hz,
transmission losses for embodiments of the present disclosure were
about 3 dB greater than that of the soda lime glass laminate
structure.
[0069] In some embodiments, an exemplary multilayer article can be
a double pane article comprising a first and a second pane with a
gap located there between as illustrated in FIG. 10. The double
pane article can comprise at least one single sided multilayer or
at least one dual sided multilayer pane. The second pane can be,
for example, a single sided multilayer, a dual sided multilayer
pane, a glass pane, or a polymer pane. The gap can be from about 4
to 25 mm, specifically, from about 6 to 20 mm, more specifically,
from about 10 to 14 mm and all sub-ranges in between. The gap may
be made to contain a liquid or gas such as Argon to improve
insulation properties of the construction. It is also contemplated
to decorate any and/or all layers and sides within this
construction.
[0070] The double pane article depicted in FIG. 10 can comprise two
single sided multilayers, where the polymer layers of each of the
single sided multilayers can be in contact with a gap located in
between the two panes. For example, FIG. 10 illustrates a double
pane article comprising two single sided multilayers 2 and 102 with
an intermediate gap 90. FIG. 10 illustrates a first glass layer 10
and first polymer layer 30 having an intermediate first interlayer
20 as well as a fourth glass layer 110 and second polymer layer 130
with an intermediate fourth interlayer 120. A gap 90 is illustrated
intermediate the polymer layers 30 and 130. It is noted that one or
more of glass layers 10 and 110 can comprise hardened glass. It is
also contemplated to decorate any and/or all layers and sides
within this construction.
[0071] In other embodiments, the double pane article can comprise
two dual sided multilayers with a gap located there between. For
example, FIG. 11 illustrates a double pane article comprising two
dual sided multilayers 4 and 104 comprising first polymer layer 30
and first polymer layer 130, respectively. The article includes a
second glass layer 50 and third glass layer 150 are located next to
a gap 90 with the first glass layer 10 and fourth glass layer 110
being the external surfaces of the double pane article. A first
interlayer 20 and second interlayer 40 are intermediate the first
polymer layer 30 and first glass layer 10 and intermediate the
first polymer layer 30 and second glass layer 50, respectively. The
fourth interlayer 120 and third interlayer 140 are intermediate the
second polymer layer 130 and fourth glass layer 110 and
intermediate the second polymer layer 130 and third glass layer
150, respectively. Of course, one or more of glass layers 10, 50,
150, and 110 can comprise hardened glass.
[0072] One or more decorative layers for a single pane or double
pane article may also be applied to the polymer and/or glass layers
by methods including but not limited to screen printing, laser
marking, rotor gravure printing, pad printing, digital ink jet
printing, hydrographics, laser etching, laser printing, and
transfer printing. In some embodiments, the multilayer articles can
be used in a confined or sealed area, such as, for example, the
interior of an aircraft. For such applications, various flame
retardant properties are of high importance. In the airline
transportation industry, useful flame retardant properties, in
particular, the heat release rate, of thermoplastic materials is
typically measured and regulated according to Federal Aviation
Regulations (FARs), in particular FAR 25.853 (d). The heat release
rate standard described in FAR F25.4 (FAR Section 25, Appendix F,
Part IV) is one such specified property, and thermoplastic
materials conforming to this standard are required to have a 2
minute (min) integrated heat release rate of less than or equal to
65 kilowatt-minutes per square meter (kW-min/m.sup.2) and a peak
heat release rate of less than 65 kilowatts per square meter
(kW/m.sup.2) determined using the Ohio State University
calorimeter, abbreviated as OSU 65/65 (2 min/peak). In some more
stringent applications where a greater heat release rate
performance is called for, a 2 minute integrated heat release rate
of less than or equal to 55 kW-min/m.sup.2 and a peak heat release
rate of less than 55 kW/m.sup.2 (abbreviated as OSU 55/55) can be
required. In addition, for many applications, the thermoplastic
materials need to have a smoke density (D.sub.s) as described in
FAR F25.5 (FAR Section 25, Appendix F, Part V) of less than 200,
measured after 4 minutes in either flame or non-flame scenario,
according to ASTM F814-83. In some embodiments, the multilayer
articles can meet Bombardier SMP 800C and Boeing BSS 7239 for
toxicity testing.
[0073] In some embodiments, the multilayer articles can meet the
requirements of the Federal Railroad Administration (FRA) for
ballistic threat and block threat. In some embodiments, the
multilayer articles can pass the CFR 49, Chapter II, Federal
Railroad Administration, DOT, Part 223, Subpart B, Appendix A, Type
I, Ballistic Threat using caliber 0.22 LR (long rifle), 40.0-grain,
lead ammunition with a minimum impact velocity of 960 feet per
second (fps) fired at the center of the test sample. In some
embodiments, the multilayer article can pass CFR 49, Chapter II,
Federal Railroad Administration, DOT, Part 223, Subpart B, Appendix
A, Type I, Block Threat using concrete blocks with a minimum weight
of 25 pounds (lbs) suspended and then dropped 30 feet (9.14 meters
(m)), 1 inch (2.54 centimeters (cm)) onto the center of the test
sample.
[0074] In the transportation industry, useful flame retardant
properties, in particular the heat release rate, of thermoplastic
materials can be measured and regulated according to the European
test standards EN45545 and ISO 5660. Accordingly, in some
embodiments, the multilayer article can have a heat release
according to EN45545 and ISO 5660 of less than 90 kilowatts (kW).
In some embodiments, the multilayer article can have a fire
propagation in accordance with the method shown in EN45545 and ISO
5658-2 of greater than 20 kW. In some embodiments, the multilayer
article can have a smoke density in accordance with the method
shown in EN 45545-2 and ISO 5659 for a smoke density at 240
seconds, where the multilayer article can have a smoke density of
less than 300, and/or VOF.sub.4, the article can have a the smoke
density of less than 600. In some embodiments, the multilayer
article can have a toxicity level in accordance with the method
shown in ISO 5659-2 using FTIR for gas analysis as required by
EN45545-2 Annex C (50 kW) where the multilayer article can have a
toxicity level with a CITG of less than 0.9 for an HL2 rating or
less than 1.2 for an HL1 rating.
[0075] In the transportation industry, useful flame retardant
properties, in particular the flame spread and fire propagation, of
thermoplastic materials can be measured and regulated according to
the British test standards BS476 Part 7 and Part 6, respectively.
Accordingly, in some embodiments, the multilayer article can have a
flame spread of_less than or equal to 165 mm according to BS476
Part 7. In some embodiments, the multilayer article can have a fire
propagation of_less than or equal to 12 according to BS476 Part
6.
[0076] In the transportation industry, useful flame retardant
properties, in particular the smoke development and toxicity of the
gases from a fire, of thermoplastic materials can be measured and
regulated according to the British test standards BS 6853:1999
Annex D8.4 Panel Smoke test and Annex B.2 Toxicity test,
respectively. Accordingly, in some embodiments, the multilayer
article can have an Ao (On) of less than 2.6 and an Ao (off) of
less than 3.9 according to BS 6853:1999 Annex D8.4. In some
embodiments, the multilayer article can have a toxicity of less
than 1 according to BS 6853:1999 Annex B.2.
[0077] Exemplary multilayer articles can be opaque. Exemplary
multilayer articles can also have excellent transparency. For
example, the multilayer article can have a haze of less than 10%
and a transmission greater than 70%, each measured using the color
space CIE1931 (Illuminant C and a 2.degree. observer), or according
to ASTM D 1003 (2007) using illuminant C at a 0.125 inch (3.2 mm)
thickness.
[0078] In some embodiments, a 1,467 mm by 1,215 mm test sample can
have a maximum deflection of less than or equal to 5 mm when
subjected to an applied load of 2,500 Newtons per meter squared
(N/m.sup.2). In other embodiments, a 1,512 mm by 842 mm test sample
can have a maximum deflection of less than or equal to 5 mm when
subjected to an applied load of 6,000 N/m.sup.2.
[0079] In further embodiments, at least one of the glass layers
comprises a hardened glass sheet. As noted above and discussed with
reference to FIG. 1, the hardened glass sheet can be prepared by
placing a glass sheet in a solution comprising a replacement ion
and exchanging sodium ions present in the glass sheet with the
replacement ion. The glass sheet can comprise sodium oxide plus an
oxide of silicon, calcium, aluminum, magnesium, boron, barium,
lanthanum, cerium, lead, germanium, or a combination comprising one
or more of the foregoing. The glass sheet can comprise sodium oxide
plus an oxide of silicon, calcium, aluminum, boron, or a
combination comprising one or more of the foregoing. The glass
sheet can be, for example, a sodium aluminosilicate or a sodium
aluminoborosilicate glass. In an exemplary ion exchanging process,
the replacement ion can be an ion with a larger atomic radius than
sodium, for example, a potassium ion, a rubidium ion, a cesium ion,
or a combination comprising one or more of the foregoing. The
replacement ion can be present in the solution as sulfates,
halides, and the like. The solution can comprise KNO.sub.3,
specifically, the solution can consist of molten KNO.sub.3. The
replacing can occur at a temperature of 400 to 500 degrees Celsius
(.degree. C.). The glass sheet can be in the solution for 4 to 24
hours, specifically, 6 to 10 hours. In some embodiments, an
exemplary ion exchange process can produce: (i) an iCS at the
surface of the hardened glass sheet, (ii) an iDOL into the hardened
glass sheet, and (iii) an iCT within the hardened glass sheet. Of
course, after replacement of the ions, the hardened sheet can be
subjected to one or both of an acid etching step and an annealing
step as described above. The acid etching step can comprise
introducing the hardened glass to an acid solution. The acid can
comprise hydrofluoric acid, hydrochloric acid, nitric acid,
sulfuric acid, ammonium bifluoride, sodium bifluoride, or a
combination comprising one or more of the foregoing. The acid
etching step can remove less than or equal to 4 micrometers,
specifically, less than or equal to 2 micrometers, more
specifically, less than or equal to 1 micrometer of the surface
glass. In the annealing step, the hardened glass sheet can be
subjected to an elevated temperature, for example, of 400 to
500.degree. C. The annealing step can occur in air or in an inert
environment. The annealing step can occur for 4 to 24 hours,
specifically, 6 to 10 hours to reduce the iCS to an fCS. The fCS
can be less than or equal to 400 MPa, specifically, less than or
equal to 350 MPa, more specifically, less than or equal to 300 MPa.
The fCS can also be 200 to 400 MPa, specifically, 250 to 350 MPa.
The annealing step can increase the iDOL to a fDOL greater than or
equal to 60 micrometers, specifically, greater than or equal to 80
micrometers, more specifically, greater than or equal to 90
micrometers, even more specifically, greater than or equal to 100
micrometers. Again, the annealing step can reduce the iCT to an fCT
below the chosen frangibility limit of the glass sheet.
[0080] An exemplary hardened glass layer can have a surface
compressive stress of 400 to 900 MPa and a depth of layer of
compressive stress of greater than or equal to 30 micrometers.
Specifically, the hardened glass can have a surface compressive
stress of 250 to 350 MPa with a depth of layer of compressive
stress of greater than or equal to 60 micrometers.
[0081] The glass layer can be 0.5 to 1.5 millimeters (mm),
specifically, 0.55 to 0.7 mm or 0.8 to 1 mm. If more than one glass
layer is present, each glass layer individually can be 0.5 to 1.5
mm, specifically, 0.55 to 0.7 mm or 0.8 to 1 mm. Additionally, the
glass layer can provide improved resistance to scratching. For
example, using a Vicker's indentor on a hardened glass, a load of
3,000 to 7,000 grams is needed to cause damage to the glass. As
compared to a standard safety glass, a load of only 1,000 grams is
enough to cause damage to the safety glass.
[0082] In some embodiments, the interlayer can be a layer that
allows the polymer layer and the glass layer to adhere to each
other. The interlayer can comprise a thermoplastic urethane (TPU),
a poly(ethylene-co-vinyl acetate) (EVA), or a combination
comprising one or both of the foregoing. The interlayer can
comprise EVA.
[0083] The TPU can comprise long polyol chains that are tied
together by shorter hard segments formed by the diisocyanate and
chain extenders if present. Polyol chains are typically referred to
as soft segments, which impart low-temperature flexibility and
room-temperature elastomeric properties. Generally, the higher the
soft segment concentration, the lower will be the modulus, tensile
strength, hardness, while elongation will increase. Polyols for use
as tie-layers in the multilayer article of the present invention
can be generally broken into three categories: 1) polyether
polyols, 2) polyester polyols, and 3) polyols based on
polybutadiene. In one embodiment of the invention, tie-layers
comprising polyols having polyether backbones are found to have
excellent hydrolytic stability especially desired for automotive
applications.
[0084] The EVA can have a vinyl acetate content of 20 to 80 wt %,
specifically, 20 to 50 wt %, more specifically, 25 to 35 wt % based
on the total weight of the EVA. The EVA can comprise maleic
anhydride functionalized EVA copolymers. The EVA can be free of
hindered amine light stabilizers (HALS) so that it will not attack
the polycarbonate. As used herein, EVA that is free of hindered
amine light stabilizers means that the EVA has less than or equal
to 0.1 wt %, specifically, 0 to 0.01 wt % of hindered amine light
stabilizers based on the total weight of the interlayer.
[0085] Examples of hindered amine light stabilizers that the
interlayer can be free of include 4-piperidinol derivative having
the general formula (2):
##STR00001##
wherein X is oxygen, and Y is hydrogen, hydroxyalkyl, aminoalkyl,
or C.sub.1-20 alkyl substituted by both hydroxyl and amino groups.
R.sup.6 and R.sup.7 are each independently selected from the group
consisting of a hydrogen atom, an alkyl group, an alkenyl group, or
an arylalkyl group. For example, R.sup.6 and R.sup.7 can each be
hydrogen. R.sup.8, R.sup.9, R.sup.10, and R.sup.11 can each
independently be selected from the group consisting of a C.sub.1-6
alkyl group, phenyl, an arylalkyl group, a C.sub.5-6 aromatic
heterocyclic group, and containing an oxygen, sulfur or nitrogen
atom, or R.sup.8, R.sup.9, R.sup.10 and R.sup.11 respectively,
together or with the carbon atom to which they are attached can
represent a C.sub.5-12 cycloalkyl group. R.sup.8, R.sup.9,
R.sup.10, and R.sup.11 can be methyl. Z is an oxy radical, an alkyl
group, an alkenyl group, an alkoxyalkyl group, an arylalkyl group
that is unsubstituted or which has one or more substituents in its
aryl moiety, including, for example, 2,3-epoxypropyl. Z can be
represented by the formula --CH.sub.2COOR.sup.12, wherein R.sup.12
is an alkyl group, an alkenyl group, a phenyl group, an aryfalkyl
group, or a cyclohexyl group. Z can have the formula
--CH.sub.2CH(R.sup.14)OR.sup.13, wherein R.sup.14 is a hydrogen
atom, a methyl group or a phenyl group and R.sup.13 is a hydrogen
atom, an alkyl group, an ester, a carbonyl, an acyl group, an
aliphatic acyl group, or a group represented by the formula
--COOR.sup.15, or --OCR.sup.15, wherein R.sup.15 is an alkyl group,
a benzyl group, a phenyl group, and the like.
[0086] Commercially available examples of HALS are TINUVIN.TM. 622
(Ciba Specialty Chemicals, Inc., Basel Switzerland), TINUVIN.TM.770
(Ciba Specialty Chemicals, Inc., Basel Switzerland), CYASORB.TM.
UV-3529 (Cytec), CYASORB.TM. UV-3631 (Cytec) CYASORB.TM. UV-3346
(Cytec), CYASORB.TM. UV-4593 (Cytec), UVINUL.TM. 5050 H (BASF), and
SANDUVOR.TM. 3058 (Clariant).
[0087] The interlayer can be 0.2 to 1.4 mm, specifically, 0.2 to
0.7 mm, specifically, 0.3 to 0.6 mm, more specifically, 0.35 to 0.5
mm. The polymer layer can comprise a polymer composition that can
comprise a polysiloxane, a polyester, a polycarbonate, a copolymer
comprising one or more of the foregoing, or a blend comprising one
or more of the foregoing. The polymer layer can comprise a
polycarbonate. The polycarbonate can be polymerized by, for
example, in an interfacial process. Although the reaction
conditions for interfacial polymerization can vary, an exemplary
process generally involves dissolving or dispersing a dihydric
phenol reactant in an aqueous base, adding the resulting mixture to
a water-immiscible solvent medium, and contacting the reactants
with a carbonate precursor in the presence of a catalyst such as,
for example, triethylamine or a phase transfer catalyst, under
controlled pH conditions, e.g., 8 to 11. The water immiscible
solvent can include one or more of methylene chloride,
1,2-dichloroethane, chlorobenzene, toluene, and the like.
Generally, a chelant, such as an iron scavenger, can be used as
well to remove impurities and contaminants.
[0088] Exemplary carbonate precursors include, for example, a
carbonyl halide such as carbonyl bromide or carbonyl chloride, or a
haloformate such as a bishaloformates of a dihydric phenol (e.g.,
the bischloroformates of bisphenol-A, hydroquinone, or the like) or
a glycol (e.g., the bishaloformate of ethylene glycol, neopentyl
glycol, polyethylene glycol, or the like). Combinations comprising
at least one of the foregoing types of carbonate precursors can
also be used. An interfacial polymerization reaction to form
carbonate linkages uses phosgene as a carbonate precursor, and can
be referred to as a phosgenation reaction.
[0089] Although the reaction conditions for interfacial
polymerization can vary, an exemplary process generally involves
dissolving or dispersing a dihydric phenol reactant in aqueous
caustic soda or potash, adding the resulting mixture to a
water-immiscible solvent medium, and contacting the reactants with
a carbonate precursor in the presence of a catalyst such as, for
example, triethylamine or a phase transfer catalyst, under
controlled pH conditions, e.g., 8 to 11. The most commonly used
water immiscible solvents include methylene chloride,
1,2-dichloroethane, chlorobenzene, toluene, and the like.
[0090] Among the phase transfer catalysts that can be used are
catalysts of the formula (R.sub.3).sub.4Q+X, wherein each R.sub.3
is the same or different, and is a C.sub.1-10 alkyl group; Q is a
nitrogen or phosphorus atom; and X is a halogen atom or a C.sub.1-8
alkoxy group or C.sub.6-18 aryloxy group. Exemplary phase transfer
catalysts include, for example, [CH.sub.3(CH.sub.2).sub.3].sub.4NX,
[CH.sub.3(CH.sub.2).sub.3].sub.4PX,
[CH.sub.3(CH.sub.2).sub.5].sub.4NX, [CH.sub.3(CH.sub.2)6].sub.4NX,
[CH.sub.3(CH.sub.2).sub.4].sub.4NX,
CH.sub.3[CH.sub.3(CH.sub.2).sub.3].sub.3NX, and
CH.sub.3[CH.sub.3(CH.sub.2).sub.2].sub.3NX, wherein X is Cl
Br.sup.-, a C.sub.1-8 alkoxy group or a C.sub.6-18 aryloxy group.
An effective amount of a phase transfer catalyst can be 0.1 to 10
wt % based on the weight of bisphenol in the phosgenation mixture.
An effective amount of phase transfer catalyst can be 0.5 to 2 wt %
based on the weight of bisphenol in the phosgenation mixture. The
dihydric phenol reactant can be of very high purity and very low
color, e.g., it can be at least 99.80% pure.
[0091] A common polymerization process uses bisphenol-A (BPA) for
the dihydric phenol reactant, aqueous sodium hydroxide (NaOH), and
phosgene as the carbonate precursor. BPA can be produced in two
grades, polycarbonate grade and epoxy grade. Polycarbonate grade
BPA is higher purity and has a lower color, as measured by APHA at
325 nm. Generally, high purity BPA has a measured APHA of less than
10 while lower purity, epoxy grade BPA has an APHA of greater than
40. The BPA used to form the polycarbonate resins of the present
disclosure can have a purity of greater than or equal to 99.65%,
specifically, greater than or equal to 99.80%. The organic purity
can be defined as 100 wt % minus the sum of known and unknown
impurities detected using ultraviolet (UV) (see HPLC method in
Nowakowska et al., Polish J. Appl. Chem., XI(3), 247-254 (1996)).
Such high quality bisphenol-A is commercially available. The BPA
for polycarbonates can be the para,para isomer of BPA. The BPA can
have a sulfur level of less than or equal to 4 parts per million by
weight (ppm), specifically, less than or equal to 2 ppm, even more
specifically, less than or equal to 1.5 ppm as measured by a
commercially available Total Sulfur Analysis based on combustion
and coulometric detection.
[0092] Methylene chloride can be used as a solvent to form the
polycarbonate. The methylene chloride can be purified by steam
precipitation to leave contaminants behind. For example, the
methylene chloride can contain less than 10 ppm of calcium, less
than 1 ppm of iron, less than 0.5% salt, and/or less than 0.1%
degraded polymer. The aqueous base can be aqueous sodium hydroxide
(NaOH). NaOH can be used to maintain the reaction pH within a
typical range of 9.5 to 10.0, and to neutralize the HCl formed from
the reaction of BPA with phosgene (turning the water into brine).
NaOH can be made by the electrolysis of sodium chloride. One
impurity formed in the electrolysis and present in the NaOH is
sodium chlorate (NaClO.sub.3). The amount of NaClO.sub.3 can be
reduced by reacting the NaOH stream with hydrogen using a ruthenium
catalyst supported on carbon. However, it is not possible to
guarantee that all the NaClO.sub.3 present is reacted, so some will
always remain in the treated NaOH solution. NaClO.sub.3 is an
oxidant and has been demonstrated to react with BPA. While the
reaction products of NaClO.sub.3 with BPA have not been completely
characterized, it is believed that the oxidation of the phenol
group of BPA causes the formation of quinone structures, which are
typically highly colored. It has been demonstrated that producing
polycarbonate resin using NaOH with high levels of NaClO.sub.3
results in a resin that when molded is high in color and has poor
color stability. The NaOH used in the present disclosure can
contain less than 10 ppm of NaClO.sub.3. Additionally, solid
particulates can be removed from the NaOH solution by filtration
using 10 micron absolute media.
[0093] High quality phosgene can be used in the polymerization of
the polycarbonate. Phosgene can be produced by the reaction of
carbon monoxide and chlorine. This reaction is typically run with
an excess of carbon monoxide, which is inert in the interfacial
polymerization. However, small amounts of un-reacted chlorine can
be present in the phosgene. Chlorine can react with NaOH in the
interfacial polymerization reaction to produce sodium hypochlorite
(NaClO) which can react with BPA in a manner similar to
NaClO.sub.3. The chlorine can also react directly with BPA.
Chlorine reaction with BPA can result in chlorination of the
polymer backbone. Polycarbonate produced when free chlorine levels
in the phosgene are greater than 500 ppm can result in
polycarbonate resin that can have greater than 200 ppm bound
chlorine atoms. This resin can have increased yellowness and
decreased color stability. The level of incorporated chlorine atoms
in the polycarbonate resin can be less than 20 ppm when phosgene
containing less than 100 ppm free chlorine is used. Thus, it is
important to control the amount of chlorine introduced via
phosgene.
[0094] The reaction of phosgene with BPA to produce the
polycarbonate powder can be run with phosgene to ensure complete
molecular weight build and minimize the amount of residual,
un-reacted BPA monomer. Generally, 8 to 10 mole % excess phosgene
is adequate. When less than 8 mole % excess phosgene is used, there
is a greater risk of incomplete batch events that result in the
polymer having a weight average molecular weight (Mw) that is lower
than desired, having higher that desired OH end group levels, and a
risk of elevated residual monomer. Generally, there can be less
than 50 ppm of hydroxyl end groups in the polycarbonate and less
than 50 ppm residual BPA monomer in the polycarbonate.
[0095] The weight average molecular weight (Mw) of the
polycarbonate powder can be controlled by adding a chain stopping
or endcapping agent. Exemplary endcapping agents include phenol,
para-t-butylphenol, and p-cumyl phenol (PCP). The amount of
endcapping agent can be 2.25 to 5.5 mole % and can result in a Mw
of 36,000 to 17,000 grams per mole (g/mol) as determined by gel
permeation chromatography (GPC) using polycarbonate standards. More
commonly, the amount of endcapping agent can be 2.9 to 4.3 mole
percent (mol %) and can result in a Mw of 30,000 to 21,000 g/mol.
An endcapping agent can be employed in the reaction such that the
resultant composition comprising polycarbonate comprises a free
hydroxyl level less than or equal to 150 ppm, more specifically, of
25 to 150 ppm, even more specifically, 30 to 100 ppm.
[0096] The post reaction processing of the polycarbonate can be
important in producing a low color and color stable polycarbonate
resin. The reaction mixture, containing polycarbonate, brine, water
immiscible solvent, and impurities, can be considered to be a
batch. The batch can be discharged and purified through a series of
purifying stages. Each stage can be made up, for example, of one or
more liquid-liquid centrifuges.
[0097] In a first purifying stage, the brine phase can be separated
from the methylene chloride phase that contains dissolved
polycarbonate. In a second purifying stage, the catalyst can be
extracted from the methylene chloride phase. This can be done using
dilute aqueous hydrochloric acid. In a third purifying stage,
residual ionic species can be removed by washing the methylene
chloride phase using high quality water. High quality water has
generally been condensed from steam or has been purified using
de-ionization, such that few contaminants are present in the water.
For example, the conductivity of the high quality water can be less
than 10 micro-siemens per centimeter (micro-siemens/cm). As a
result, the polycarbonate can have low residual chloride ions. It
has been shown that when water containing mineral and metal
impurities such as calcium, silicate, iron, sulfate or the like is
used, molded parts made from the subsequent polycarbonate resin can
have increased haze and yellowness.
[0098] After purification, the non-aqueous phase containing the
dissolved polycarbonate can be optionally filtered using 1 to 10
micrometer absolute filters. The polycarbonate can then be
concentrated and isolated by means of steam precipitation, which
instantly flashes the dichloromethane solvent during direct contact
with steam. The steam used for precipitation can be very low in
mineral and ion content, preferably with a conductivity value of
less than one micro-siemens/cm. The steam used for isolation, can
optionally be filtered using 1 to 50 micron absolute filters.
Precipitation of resin using steam with high mineral or ion content
(greater than 10 micro-siemens/cm) can result in high yellowness
and poor melt stability for the polycarbonate resin.
[0099] The dichloromethane and steam vapors can be separated from
the wet polycarbonate. The dichloromethane and steam vapors can
themselves be condensed and separated. The recovered
dichloromethane can be high purity by virtue of being flashed, and
can be reused in future polymerization of BPA. The recovered water
can also be high purity, and can be used in the purifying stages
for washing or the extraction of catalyst. The recovered
catalyst/water mixture can be reused in future polymerization of
BPA.
[0100] Residual dichloromethane can be removed from the wet
polycarbonate in a plug flow column using counter current steam
flow. Residual water can be removed from the wet polycarbonate in a
fluid bed dryer using heated air. The resulting polycarbonate
powder can then be collected.
[0101] To summarize, a number of steps can be taken to produce high
quality polycarbonate. High purity BPA that is low color and
especially color stable can be used. The NaOH base can be low in
sodium chlorate content and can be filtered. The phosgene can be
low in non-reacted chlorine content. Conservative reaction
conditions that ensure complete polymerization can be used. High
purity water should be used during the purifying stages of
obtaining the polycarbonate.
[0102] Next, the compounding processes that form the polycarbonate
resin can be optimized as well. Initially, the high quality
polycarbonate, which has been made can be isolated and segregated
to designated silos in the compounding operation. Each silo can be
cleaned of any residual powder to ensure there is no
cross-contamination. The transfer lines used to move polycarbonate
powder from the silos to the extrusion line can also be cleaned out
prior to transferring. Filtered air can be used for transferring.
Any additives (colorants, stabilizers, etc.) can be metered
directly into the extruder using dedicated feeders.
[0103] The compounding of the polycarbonate powder can be performed
in an extruder. An extruder can be used for compounding, molding,
pelletization or forming films, sheets or profiles. Such extruders
typically have a heated extrusion barrel and one or two screws
revolving within the barrel to compress, melt, and extrude the
polycarbonate through an orifice in an extrusion nozzle. The barrel
can be divided into several different zones, such as feed,
transition, mixing, dispersion, and metering zones.
[0104] The polycarbonate, along with additives, can be melt
extruded at a controlled temperature. 58 mm or 70 mm extruders can
be typically used for high-grade polycarbonate resins. The
polycarbonate can be melt filtered through a 30 micrometer filter
stack to reduce particulate contamination. It is possible to use a
smaller mesh filter (10 micrometer) to further improve the quality
of the product. Stainless steel water baths with 0.5
micrometer-filtered water can be used to minimize contamination.
Polycarbonate resin exiting the extruder can be pelletized and
collected in packaging such as bulk boxes or super sacks. Care can
be taken during the extrusion and packaging processes to exclude
particulates that can be present in air and water transfer
systems.
[0105] In this respect, two aspects of the compounding process can
be relevant to obtaining the high quality polycarbonate resins of
the present disclosure. First, as the melt filter sizes get
smaller, shear forces and heat can increase as the polycarbonate
passes through the filter channels. This can result in an increase
in yellowness in the resulting polycarbonate. Second, an amount of
blue colorant can be added to the polycarbonate to offset any
yellowness. Once the extruder has reached stable operating state
and pellets are being produced, a small sample of pellets can be
molded into a color plaque at a specified thickness. Color
measurements can be recorded and compared to the desired
specifications of the product. The amount of colorant or their
strength can then be adjusted to bring the polycarbonate product
within specifications. Again, by controlling the yellowness of the
polycarbonate, the amount of colorant needed to meet the colorant
specification (b*) can be reduced, which increases the brightness
(L*).
[0106] To obtain the high quality polycarbonate having increased
light transmission and cleanliness, the feed rate to the extruder,
the torque of the extruder, the set point for the colorant, and the
temperature of the extruder can be optimized. This can be done
using a feedback loop to obtain the desired product. The colorant
is typically measured as a percentage of the line rate. The torque
can be 70% to 90%.
[0107] In certain cases in compounding polyester carbonates, along
with its additives, it can be beneficial to use extruders designed
to minimize shear heating and black speck generation. For example,
a co-rotating intermeshing twin screw extruder with mild screw
designs and with mild extrusion conditions is preferred.
Co-rotating intermeshing extruders have the advantage of
self-wiping screw elements thus minimizing black speck generation.
Mild screws designs are known in the art and typically minimize the
number of high shear mixing elements such as wide to medium wide
kneading blocks, and/or left handed kneading blocks (utilizing two
or three lobe elements) to achieve melting and use low shear mixing
elements such as ZMEs (Zahn Mixing Elements), TMEs (Turbine Mixing
Elements), and/or SMEs (Screw Mixing Elements) for good
distributive mixing of any additives/colorants. Single screw
extruders can provide low shear melting and mixing but have the
disadvantage of higher black speck generation because it lacks
self-wiping capabilities.
[0108] In addition to the use of low shear extruders, for the
lowest color, highest transmission resin, it can also be beneficial
to use mild extrusion conditions. These conditions are known in the
art and typically minimized the specific energy and/or maximize the
torque. The feed rate to the extruder, the screw speed, the
colorant concentration, and the temperature of the extruder can be
optimized to minimize the specific energy, maximize the torque and
optimize the color and transmission.
[0109] To obtain high optical quality polyester carbonate resin and
articles, it is often advantageous to exclude the contamination of
non-miscible resins. Non-miscible haze cause resins could include
for example, BPA polycarbonate. A "polycarbonate" means
compositions having repeating structural carbonate units of formula
(1):
##STR00002##
in which at least 60% of the total number of R.sup.1 groups contain
aromatic moieties and the balance thereof are aliphatic, alicyclic,
or aromatic.
[0110] The polycarbonate can be derived from bisphenol-A. Each
R.sup.1 group can be a divalent aromatic group, for example,
derived from an aromatic dihydroxy compound of the formula (3):
HO-A.sup.1-Y.sup.1-A.sup.2-OH (3)
wherein each of A.sup.1 and A.sup.2 is a monocyclic divalent
arylene group, and Y.sup.1 is a single bond or a bridging group
having one or two atoms that separate A.sup.1 from A.sup.2. When
each of A.sup.1 and A.sup.2 is phenylene, Y.sup.1 can be para to
each of the hydroxyl groups on the phenylenes. Illustrative
non-limiting examples of groups of this type are --O--, --S--,
--S(O).sub.2--, --C(O)--, methylene, cyclohexyl-methylene,
2-[2.2.1]-bicycloheptylidene, ethylidene, isopropylidene,
neopentylidene, cyclohexylidene, cyclopentadecylidene,
cyclododecylidene, and adamantylidene. The bridging group Y.sup.1
can be a hydrocarbon group or a saturated hydrocarbon group such as
methylene, cyclohexylidene, or isopropylidene. In an embodiment,
one atom separates A.sup.1 from A.sup.2.
[0111] Included within the scope of formula (3) are bisphenol
compounds of general formula (4):
##STR00003##
wherein R.sup.a and R.sup.b each represent a halogen atom or a
monovalent hydrocarbon group and can be the same or different; p
and q are each independently integers of 0 to 4; and X.sup.a
represents a single bond or one of the groups of formulas (5) or
(6):
##STR00004##
wherein R.sup.e and R.sup.d are each independently hydrogen,
C.sub.1-12 alkyl, C.sub.1-12 cycloalkyl, C.sub.7-12 arylalkyl,
C.sub.1-12 heteroalkyl, or cyclic C.sub.7-12 heteroarylalkyl, and
R.sup.e is a divalent C.sub.1-12 hydrocarbon group. R.sup.e and
R.sup.d can each be the same hydrogen or C.sub.1-4 alkyl group,
specifically, the same C.sub.1-3 alkyl group, even more
specifically, methyl.
[0112] R.sup.c and R.sup.d can be taken together to represent a
C.sub.3-20 cyclic alkylene group or a heteroatom-containing
C.sub.3-20 cyclic alkylene group comprising carbon atoms and
heteroatoms with a valency of two or greater. These groups can be
in the form of a single saturated or unsaturated ring, or a fused
polycyclic ring system wherein the fused rings are saturated,
unsaturated, or aromatic. A specific heteroatom-containing cyclic
alkylene group comprises at least one heteroatom with a valency of
2 or greater, and at least two carbon atoms. Exemplary heteroatoms
in the heteroatom-containing cyclic alkylene group include --O--,
--S--, and --N(Z)--, where Z is a substituent group selected from
hydrogen, hydroxy, C.sub.1-12 alkyl, C.sub.1-12 alkoxy, or
C.sub.1-12 acyl.
[0113] X.sup.a can be a substituted C.sub.3-18 cycloalkylidene of
the formula (7):
##STR00005##
wherein each R.sup.r, R.sup.p, R.sup.q, and R.sup.t is
independently hydrogen, halogen, oxygen, or C.sub.1-12 organic
group; I is a direct bond, a carbon, or a divalent oxygen, sulfur,
or --N(Z)-- wherein Z is hydrogen, halogen, hydroxy, C.sub.1-12
alkyl, C.sub.1-12 alkoxy, or C.sub.1-12 acyl; h is 0 to 2, j is 1
or 2, i is an integer of 0 or 1, and k is an integer of 0 to 3,
with the proviso that at least two of R.sup.r, R.sup.p, R.sup.q,
and R.sup.t taken together are a fused cycloaliphatic, aromatic, or
heteroaromatic ring. It will be understood that where the fused
ring is aromatic, the ring as shown in formula (7) will have an
unsaturated carbon-carbon linkage where the ring is fused. When k
is 1 and i is 0, the ring as shown in formula (7) contains 4 carbon
atoms, when k is 2, the ring as shown contains 5 carbon atoms, and
when k is 3, the ring contains 6 carbon atoms. Two adjacent groups
(e.g., R.sup.q and R.sup.t taken together) can be taken together to
form an aromatic group. Further, multiple groups can be taken
together to form greater than one aromatic groups (e.g. R.sup.q and
R.sup.t taken together form one aromatic group and R.sup.r and
R.sup.p taken together form a second aromatic group).
[0114] When k is 3 and i is 0, bisphenols containing substituted or
unsubstituted cyclohexane units are used, for example, bisphenols
of formula (8):
##STR00006##
wherein each R.sup.f is independently hydrogen, C.sub.1-12 alkyl,
or halogen; and each R.sup.g is independently hydrogen or
C.sub.1-12 alkyl. The substituents can be aliphatic or aromatic,
straight chain, cyclic, bicyclic, branched, saturated, or
unsaturated. Such cyclohexane-containing bisphenols, for example,
the reaction product of two moles of a phenol with one mole of a
hydrogenated isophorone, are useful for making polycarbonate
polymers with high glass transition temperatures and high heat
distortion temperatures. Cyclohexyl bisphenol containing
polycarbonates, or a combination comprising at least one of the
foregoing with other bisphenol polycarbonates, are supplied by
Bayer Co. under the APEC* trade name.
[0115] Other possible dihydroxy compounds having the formula
HO--R.sup.1--OH include aromatic dihydroxy compounds of formula
(9):
##STR00007##
wherein each R.sup.h is independently a halogen atom, a C.sub.1-10
hydrocarbyl such as a C.sub.1-10 alkyl group, a halogen substituted
C.sub.1-10 hydrocarbyl such as a halogen-substituted C.sub.1-10
alkyl group, and n is 0 to 4. The halogen can be bromine.
[0116] Some illustrative examples of dihydroxy compounds include
the following: 4,4'-dihydroxybiphenyl, 1,6-dihydroxynaphthalene,
2,6-dihydroxynaphthalene, bis(4-hydroxyphenyl)methane,
bis(4-hydroxyphenyl)diphenylmethane,
bis(4-hydroxyphenyl)-1-naphthylmethane,
1,2-bis(4-hydroxyphenyl)ethane,
1,1-bis(4-hydroxyphenyl)-1-phenylethane,
2-(4-hydroxyphenyl)-2-(3-hydroxyphenyl)propane,
bis(4-hydroxyphenyl)phenylmethane,
2,2-bis(4-hydroxy-3-bromophenyl)propane,
1,1-bis(hydroxyphenyl)cyclopentane,
1,1-bis(4-hydroxyphenyl)cyclohexane,
1,1-bis(4-hydroxyphenyl)isobutene,
1,1-bis(4-hydroxyphenyl)cyclododecane,
trans-2,3-bis(4-hydroxyphenyl)-2-butene,
2,2-bis(4-hydroxyphenyl)adamantine, alpha,
alpha'-bis(4-hydroxyphenyl)toluene,
bis(4-hydroxyphenyl)acetonitrile,
2,2-bis(3-methyl-4-hydroxyphenyl)propane,
2,2-bis(3-ethyl-4-hydroxyphenyl)propane,
2,2-bis(3-n-propyl-4-hydroxyphenyl)propane,
2,2-bis(3-isopropyl-4-hydroxyphenyl)propane,
2,2-bis(3-sec-butyl-4-hydroxyphenyl)propane,
2,2-bis(3-t-butyl-4-hydroxyphenyl)propane,
2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane,
2,2-bis(3-allyl-4-hydroxyphenyl)propane,
2,2-bis(3-methoxy-4-hydroxyphenyl)propane,
2,2-bis(4-hydroxyphenyl)hexafluoropropane,
1,1-dichloro-2,2-bis(4-hydroxyphenyl)ethylene,
1,1-dibromo-2,2-bis(4-hydroxyphenyl)ethylene,
1,1-dichloro-2,2-bis(5-phenoxy-4-hydroxyphenyl)ethylene,
4,4'-dihydroxybenzophenone, 3,3-bis(4-hydroxyphenyl)-2-butanone,
1,6-bis(4-hydroxyphenyl)-1,6-hexanedione, ethylene glycol
bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)ether,
bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide,
bis(4-hydroxyphenyl)sulfone, 9,9 to bis(4-hydroxyphenyl)fluorine,
2,7-dihydroxypyrene,
6,6'-dihydroxy-3,3,3',3'-tetramethylspiro(bis)indane
("spirobiindane bisphenol"), 3,3-bis(4-hydroxyphenyl)phthalide,
2,6-dihydroxydibenzo-p-dioxin, 2,6-dihydroxythianthrene,
2,7-dihydroxyphenoxathin, 2,7-dihydroxy-9,10-dimethylphenazine,
3,6-dihydroxydibenzofuran, 3,6-dihydroxydibenzothiophene, and
2,7-dihydroxycarbazole, resorcinol, substituted resorcinol
compounds such as 5-methyl resorcinol, 5-ethyl resorcinol, 5-propyl
resorcinol, 5-butyl resorcinol, 5-t-butyl resorcinol, 5-phenyl
resorcinol, 5-cumyl resorcinol, 2,4,5,6-tetrafluoro resorcinol,
2,4,5,6-tetrabromo resorcinol, or the like; catechol; hydroquinone;
substituted hydroquinones such as 2-methyl hydroquinone, 2-ethyl
hydroquinone, 2-propyl hydroquinone, 2-butyl hydroquinone,
2-t-butyl hydroquinone, 2-phenyl hydroquinone, 2-cumyl
hydroquinone, 2,3,5,6-tetramethyl hydroquinone,
2,3,5,6-tetra-t-butyl hydroquinone, 2,3,5,6-tetrafluoro
hydroquinone, 2,3,5,6-tetrabromo hydroquinone, and the like, as
well as combinations comprising at least one of the foregoing
dihydroxy compounds.
[0117] Specific examples of bisphenol compounds that can be
represented by formula (3) include 1,1-bis(4-hydroxyphenyl)
methane, 1,1-bis(4-hydroxyphenyl) ethane, 2,2-bis(4-hydroxyphenyl)
propane (hereinafter "bisphenol-A" or "BPA"),
2,2-bis(4-hydroxyphenyl) butane, 2,2-bis(4-hydroxyphenyl) octane,
1,1-bis(4-hydroxyphenyl) propane, 1,1-bis(4-hydroxyphenyl)
n-butane, 2,2-bis(4-hydroxy-1-methylphenyl) propane,
1,1-bis(4-hydroxy-t-butylphenyl) propane, 3,3-bis(4-hydroxyphenyl)
phthalimidine, 2-phenyl-3,3-bis(4-hydroxyphenyl) phthalimidine
(PPPBP), and 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane (DMBPC).
Combinations comprising at least one of the foregoing dihydroxy
compounds can also be used.
[0118] "Polycarbonate" as used herein includes homopolycarbonates,
copolymers comprising different R.sup.1 moieties in the carbonate
(referred to herein as "copolycarbonates"), and copolymers
comprising carbonate units and other types of polymer units, such
as ester units. The polycarbonate can be a linear homopolymer or
copolymer comprising units derived from bisphenol-A, in which each
of A.sup.1 and A.sup.2 is p-phenylene and Y.sup.1 is isopropylidene
in formula (3). More specifically, at least 60%, more specifically,
at least 80% of the R.sup.1 groups in the polycarbonate can be
derived from bisphenol-A.
[0119] Branched polycarbonate blocks can be prepared by adding a
branching agent during polymerization. These branching agents
include polyfunctional organic compounds containing at least three
functional groups selected from hydroxyl, carboxyl, carboxylic
anhydride, haloformyl, and mixtures of the foregoing functional
groups. Specific examples include trimellitic acid, trimellitic
anhydride, trimellitic trichloride (TMTC), tris-p-hydroxy phenyl
ethane (THPE), 3,3-bis-(4-hydroxyphenyl)-oxindole (also known as
isatin-bis-phenol), tris-phenol TC
(1,3,5-tris((p-hydroxyphenyl)isopropyl)benzene), tris-phenol PA
(4(4(1,1-bis(p-hydroxyphenyl)-ethyl) alpha, alpha-dimethyl
benzyl)phenol), 4-chloroformyl phthalic anhydride, trimesic acid,
and benzophenone tetracarboxylic acid. The branching agents can be
added at a level of 0.05 to 2.0 wt %. Mixtures comprising linear
polycarbonates and branched polycarbonates can be used.
[0120] A particular type of branching agent can be used to create
branched polycarbonate materials. These branched polycarbonate
materials have statistically more than two end groups. The
branching agent is added in an amount (relative to the bisphenol
monomer) that is sufficient to achieve the desired branching
content, that is, more than two end groups. The molecular weight of
the polymer can become very high upon addition of the branching
agent and can lead to viscosity problems during phosgenation.
Therefore, an increase in the amount of the chain termination agent
can be used in the polymerization. The amount of chain termination
agent used when the particular branching agent is used is generally
higher than if only a chain termination agent alone is used. The
amount of chain termination agent used is generally above 5 mol %
and less than 20 mol % compared to the bisphenol monomer.
[0121] The branching agent can be a structure derived from a
triacid trichloride of the formula (21):
##STR00008##
wherein Z is hydrogen, a halogen, C.sub.1-3 alkyl group, C.sub.1-3
alkoxy group, C.sub.7-12 arylalkyl, alkylaryl, or nitro group, and
z is 0 to 3; or a branching agent derived from a reaction with a
tri-substituted phenol of the formula (22):
##STR00009##
wherein T is a C.sub.1-20 alkyl group, C.sub.1-20 alkyleneoxy
group, C.sub.7-12 arylalkyl, or alkylaryl group, S is hydrogen, a
halogen, C.sub.1-3 alkyl group, C.sub.1-3 alkoxy group, C.sub.7-12
arylalkyl, alkylaryl, or nitro group, s is 0 to 4.
[0122] In another embodiment, the branching agent is a structure
having formula (23):
##STR00010##
[0123] Examples of specific branching agents that are particularly
effective in embodiments include trimellitic trichloride (TMTC),
tris-p-hydroxy phenyl ethane (THPE) and isatin-bis-phenol. In
formula (21), Z can be hydrogen and z can be 3. In formula (22), S
can be hydrogen, T can be methyl, and s can be 4.
[0124] The relative amount of branching agents used in the
manufacture of a polymer according to embodiments will depend on a
number of considerations, for example, the type of R.sup.1 groups,
the amount of cyanophenol, and the desired molecular weight of the
polycarbonate. In general, the amount of branching agent is
effective to provide 0.1 to 10 branching units per 100 R.sup.1
units, specifically, 0.5 to 8 branching units per 100 R.sup.1
units, and more specifically, 0.75 to 5 branching units per 100
R.sup.1 units. For branching agents having formula (21), the amount
of branching agent tri-ester groups are present in an amount of 0.1
to 10 branching units per 100 R.sup.1 units, specifically, 0.5 to 8
branching units per 100 R.sup.1 units, and more specifically, 0.75
to 5 tri-ester units per 100 R.sup.1 units. For branching agents
having formula (22), the amount of branching agent tricarbonate
groups are present in an amount of 0.1 to 10 branching units per
100 R.sup.1 units, specifically, 0.5 to 8 branching units per 100
R.sup.1 units, and more specifically, 0.75 to 5 tri-phenylcarbonate
units per 100 R.sup.1 units. In some embodiments, a combination of
two or more branching agents can be used. In one embodiment, the
polycarbonate of a composition has a branching level of greater
than or equal to 1%, or greater than or equal to 2%, or greater
than or equal to 3%, or 1% to 3%.
[0125] Various types of end-capping agents can be utilized for
embodiments encompassed by this disclosure. The end-capping agent
can be selected based upon the molecular weight of said
polycarbonate and said branching level imparted by said branching
agent. The end-capping agents can be selected from at least one of
the following: phenol or a phenol containing one or more
substitutions with at least one of the following: aliphatic groups,
olefinic groups, aromatic groups, halogens, ester groups, and ether
groups. The end-capping agents can be selected from at least one of
the following: phenol, para-t-butylphenol or para-cumylphenol.
[0126] The polycarbonate encompassed by this disclosure can exclude
the utilization of a melt polymerization process to make at least
one of said polycarbonates. Protocols can be adjusted so as to
obtain a desired product within the scope of the disclosure and
this can be done without undue experimentation. In some
embodiments, the polymer composition can comprise a polyester. The
polyester contains repeating units of formula (10):
##STR00011##
wherein D is a divalent group derived from a dihydroxy compound,
and can be, for example, a C.sub.2-10 alkylene group, a C.sub.6-20
alicyclic group, a C.sub.6-20 aromatic group or a polyoxyalkylene
group in which the alkylene groups contain 2 to 6 carbon atoms,
specifically, 2, 3, or 4 carbon atoms; and T is a divalent group
derived from a dicarboxylic acid, and can be, for example, a
C.sub.2-10 alkylene group, a C.sub.6-20 alicyclic group, a
C.sub.6-20 alkyl aromatic group, or a C.sub.6-20 aromatic group. D
can be a C.sub.2-30 alkylene group having a straight chain,
branched chain, or cyclic (including polycyclic) structure. D can
be derived from an aromatic dihydroxy compound of formula (4) above
and/or D can be derived from an aromatic dihydroxy compound of
formula (9) above.
[0127] Examples of aromatic dicarboxylic acids that can be used to
prepare the polyester units include isophthalic or terephthalic
acid, 1,2-di(p-carboxyphenyl)ethane, 4,4'-dicarboxydiphenyl ether,
4,4'-bisbenzoic acid, and combinations comprising at least one of
the foregoing acids. Acids containing fused rings can also be
present, such as in 1,4-, 1,5-, or 2,6-naphthalenedicarboxylic
acids. Specific dicarboxylic acids are terephthalic acid,
isophthalic acid, naphthalene dicarboxylic acid, cyclohexane
dicarboxylic acid, or combinations thereof. A specific dicarboxylic
acid comprises a combination of isophthalic acid and terephthalic
acid wherein the weight ratio of isophthalic acid to terephthalic
acid is 91:9 to 2:98. D can be a C.sub.2-6 alkylene group and T can
be p-phenylene, m-phenylene, naphthalene, a divalent cycloaliphatic
group, or a combination thereof. This class of polyester includes
the poly(alkylene terephthalates).
[0128] The polyester can also comprise arylate ester units of the
arylate-containing units and are derived from the reaction product
of one equivalent of an isophthalic acid derivative and/or
terephthalic acid derivative. An arylate unit is illustrated in
formula (9):
##STR00012##
wherein R.sup.1 and u are previously defined for formula (7), and m
is greater than or equal to 4. In an embodiment, m is 4 to 50,
specifically, 5 to 30, more specifically, 5 to 25, and still more
specifically, 10 to 20. Also in an embodiment, m is less than or
equal to 100, specifically, less than or equal to 90, more
specifically, less than or equal to 70, and still more
specifically, less than or equal to 50. It will be understood that
the low and high endpoint values for m are independently
combinable. In another embodiment, the molar ratio of isophthalate
to terephthalate can be about 0.25:1 to about 4.0:1. In a specific
embodiment, the arylate ester units consist of
isophthalate-terephthalate ester units. In another embodiment, the
arylate ester units are derived from the reaction product of one
equivalent of an isophthalic acid derivative and/or a terephthalic
acid derivative with a resorcinol of formula (7). Such arylate
ester units correspond to the R.sup.1 being derived from
resorcinol.
[0129] Exemplary arylate ester units are aromatic polyester units
such as isophthalate-terephthalate-resorcinol ester units,
isophthalate-terephthalate-bisphenol ester units, or a combination
comprising each of these. Specific arylate ester units include
poly(isophthalate-terephthalate-resorcinol) esters,
poly(isophthalate-terephthalate-bisphenol-A) esters,
poly[(isophthalate-terephthalate-resorcinol)
ester-co-(isophthalate-terephthalate-bisphenol-A)] ester, or a
combination comprising at least one of these. In an embodiment, a
arylate ester unit is a poly(isophthalate-terephthalate-resorcinol)
ester. In an embodiment, the arylate ester unit comprises
isophthalate-terephthalate-resorcinol ester units in an amount
greater than or equal to 95 mol %, specifically, greater than or
equal to 99 mol %, and still more specifically, greater than or
equal to 99.5 mol % based on the total number of moles of ester
units in the polyarylate unit. In another embodiment, the arylate
ester units are not substituted with non-aromatic
hydrocarbon-containing substituents such as, for example, alkyl,
alkoxy, or alkylene substituents.
[0130] The polyester can comprise a copolymer comprising alkylene
terephthalate repeating ester units with another ester group.
Specifically, ester units can include different alkylene
terephthalate units, which can be present in the polymer chain as
individual units, or as units of poly(alkylene terephthalates). For
example, a polyester copolymer can comprise
poly(1,4-cyclohexanedimethylene terephthalate)-co-poly(ethylene
terephthalate), abbreviated as PETG where the polymer comprises
greater than or equal to 50 mole % of poly(ethylene terephthalate),
and abbreviated as PCTG where the polymer comprises greater than 50
mole % of poly(1,4-cyclohexanedimethylene terephthalate).
[0131] The polyester can comprise a poly(alkylene
cyclohexanedicarboxylate). Of these, a specific example is
poly(1,4-cyclohexane-dimethanol-1,4-cyclohexanedicarboxylate)
(PCCD), having recurring units of formula (34):
##STR00013##
wherein, as described using formula (8), D is a dimethylene
cyclohexane group derived from cyclohexane dimethanol, and T is a
cyclohexane ring derived from cyclohexanedicarboxylate or a
chemical equivalent thereof and is selected from the cis-isomer,
trans-isomer, or a combination of cis- and trans-isomers.
[0132] The polymer composition can comprise a polysiloxane. The
polysiloxane (also referred to herein as "polydiorganosiloxane")
has repeat units of formula (11)
##STR00014##
wherein each occurrence of R is same or different, and is a
C.sub.1-13 monovalent organic group. For example, each R can
independently be a C.sub.1-13 alkyl group, C.sub.1-13 alkoxy group,
C.sub.2-13 alkenyl group, C.sub.2-13 alkenyloxy group, C.sub.3-6
cycloalkyl group, C.sub.3-6 cycloalkoxy group, C.sub.6-14 aryl
group, C.sub.6-10 aryloxy group, C.sub.7-13 arylalkyl group,
C.sub.7-13 arylalkoxy group, C.sub.7-13 alkylaryl group, or
C.sub.7-13 alkylaryloxy group. The foregoing groups can be fully or
partially halogenated with fluorine, chlorine, bromine, or iodine,
or a combination thereof. Combinations of the foregoing R groups
can be used in the same copolymer. In an embodiment, the
polysiloxane comprises R groups can have a minimum hydrocarbon
content. An R group with a minimum hydrocarbon content can be a
methyl group.
[0133] The value of E in formula (11) can vary widely depending on
the type and relative amount of each component in the polymer
composition, the desired properties of the composition, and like
considerations. Herein, E can have an average value of 2 to 1,000,
specifically, 10 to 100, more specifically, 25 to 75, more
specifically, 40 to 50. E can have an average value of 4 to 60,
specifically, 16 to 50, specifically, 20 to 45, and more
specifically, 25 to 45. E can have an average value of 4 to 15,
specifically, 5 to 15, more specifically, 6 to 15, and still more
specifically, 7 to 12.
[0134] Polydiorganosiloxane units can be derived from dihydroxy
aromatic compound of formula (12):
##STR00015##
wherein E is as defined above; each R can independently be the same
or different, and is as defined above; and each Ar can
independently be the same or different, and is a substituted or
unsubstituted C.sub.6-30 arylene group, wherein the bonds are
directly connected to an aromatic moiety. Exemplary Ar groups in
formula (12) can be derived from a C.sub.6-30 dihydroxy aromatic
compound, for example, a dihydroxy aromatic compound of formula
(3), (4), (8), or (9) above. Combinations comprising at least one
of the foregoing dihydroxy aromatic compounds can also be used.
Exemplary dihydroxy aromatic compounds are resorcinol (i.e.,
1,3-dihydroxybenzene), 4-methyl-1,3-dihydroxybenzene,
5-methyl-1,3-dihydroxybenzene, 4,6-dimethyl-1,3-dihydroxybenzene,
1,4-dihydroxybenzene, 1,1-bis(4-hydroxyphenyl) methane,
1,1-bis(4-hydroxyphenyl) ethane, 2,2-bis(4-hydroxyphenyl) propane,
2,2-bis(4-hydroxyphenyl) butane, 2,2-bis(4-hydroxyphenyl) octane,
1,1-bis(4-hydroxyphenyl) propane, 1,1-bis(4-hydroxyphenyl)
n-butane, 2,2-bis(4-hydroxy-1-methylphenyl) propane,
1,1-bis(4-hydroxyphenyl) cyclohexane, bis(4-hydroxyphenyl sulfide),
and 1,1-bis(4-hydroxy-t-butylphenyl) propane. Combinations
comprising at least one of the foregoing dihydroxy compounds can
also be used. The dihydroxy aromatic compound can be unsubstituted,
or not substituted with non-aromatic hydrocarbon-containing
substituents such as, for example, alkyl, alkoxy, or alkylene
substituents.
[0135] When Ar is derived from resorcinol, the polydiorganosiloxane
repeating units can be derived from dihydroxy aromatic compounds of
formula (13):
##STR00016##
or, when Ar is derived from bisphenol-A, the polydiorganosiloxane
repeating units can be derived from dihydroxy aromatic compounds of
formula (14):
##STR00017##
wherein E is as defined above.
[0136] Polydiorganosiloxane units can be derived from dihydroxy
aromatic compound of formula (15):
##STR00018##
wherein R and E are as described above, and each occurrence of
R.sup.2 is independently a divalent C.sub.1-30 alkylene or
C.sub.7-30 arylene-alkylene, and wherein the polymerized
polysiloxane unit is the reaction residue of its corresponding
dihydroxy aromatic compound. When R.sup.2 is C.sub.7-30
arylene-alkylene, the polydiorganosiloxane units can be derived
from dihydroxy aromatic compound of formula (16):
##STR00019##
wherein R (such as aryl (such as phenyl, chlorophenyl or tolyl) or
C.sub.1-8 alkyl (such as methyl, haloalkyl (such as
trifluoropropyl), or cyanoalkyl) and E are as defined above. Each
R.sup.3 is independently a divalent C.sub.2-8 aliphatic group (such
as dimethylene, trimethylene or tetramethylene). Each M can be the
same or different, and can be a halogen (such as bromo or chloro),
cyano, nitro, C.sub.1-8 alkylthio, C.sub.1-8 alkyl (such as methyl,
ethyl, or propyl), C.sub.1-8 alkoxy (such as methoxy, ethoxy, or
propoxy), C.sub.2-8 alkenyl, C.sub.2-8 alkenyloxy group, C.sub.3-8
cycloalkyl, C.sub.3-8 cycloalkoxy, C.sub.6-10 aryl (such as phenyl,
chlorophenyl, or tolyl), C.sub.6-10 aryloxy, C.sub.7-12 arylalkyl,
C.sub.7-12 arylalkoxy, C.sub.7-12 alkylaryl, or C.sub.7-12
alkylaryloxy, wherein each n is independently 0, 1, 2, 3, or 4. For
example, M can be methoxy, n can be one, R.sup.2 can be a divalent
C.sub.1-C.sub.3 aliphatic group, and R can be methyl.
[0137] M can be bromo or chloro, an alkyl group such as methyl,
ethyl, or propyl, an alkoxy group such as methoxy, ethoxy, or
propoxy, or an aryl group such as phenyl, chlorophenyl, or tolyl;
R.sup.3 can be a dimethylene, trimethylene or tetramethylene group;
and R can be a C.sub.1-8 alkyl, haloalkyl such as trifluoropropyl,
cyanoalkyl, or aryl such as phenyl, chlorophenyl or tolyl. R can be
methyl, or a combination of methyl and trifluoropropyl, or a
combination of methyl and phenyl. M can be methoxy, n can be 0 or
1, R.sup.3 can be a divalent aliphatic group, and R can be
methyl.
[0138] The polydiorganosiloxane units can be derived from a
dihydroxy aromatic compound of formula (17):
##STR00020##
wherein E is as described above.
[0139] The polydiorganosiloxane units can be derived from dihydroxy
aromatic compound of formula (18):
##STR00021##
wherein E is as defined above.
[0140] Dihydroxy polysiloxanes typically can be made by
functionalizing a substituted siloxane oligomer of formula
(19):
##STR00022##
wherein R and E are as previously defined, and Z is H, halogen
(e.g., Cl, Br, I), or carboxylate. Exemplary carboxylates include
acetate, formate, benzoate, and the like. In an exemplary
embodiment, where Z is H, compounds of formula (19) can be prepared
by platinum catalyzed addition with an aliphatically unsaturated
monohydric phenol. Exemplary aliphatically unsaturated monohydric
phenols include, for example, eugenol, 2-allylphenol,
4-allylphenol, 4-allyl-2-methylphenol, 4-allyl-2-phenylphenol,
4-allyl-2-bromophenol, 4-allyl-2-t-butoxyphenol,
4-phenyl-2-allylphenol, 2-methyl-4-propenylphenol,
2-allyl-4,6-dimethylphenol, 2-allyl-4-bromo-6-methylphenol,
2-allyl-6-methoxy-4-methylphenol, and 2-allyl-4,6-dimethylphenol.
Combinations comprising at least one of the foregoing can also be
used. Where Z is halogen or carboxylate, functionalization can be
accomplished by reaction with a dihydroxy aromatic compound of
formulas (3), (4), (8), (9), or a combination comprising at least
one of the foregoing dihydroxy aromatic compounds. Compounds of
formula (12) can be formed from an alpha,
omega-bisacetoxypolydiorangonosiloxane and a dihydroxy aromatic
compound under phase transfer conditions.
[0141] The polymer composition can comprise one or more copolymers.
Examples of copolymers include polycarbonate-polyesters,
polycarbonate-polysiloxanes, polyester-polysiloxanes, and
polycarbonate-polyester-polysiloxanes.
[0142] A polyester-polycarbonate copolymer can have a molar ratio
of ester units to carbonate units of 1:99 to 99:1, specifically,
10:90 to 90:10, more specifically, 25:75 to 75:25. The
polyester-polycarbonate can have the structure shown in formula
(114):
##STR00023##
wherein R.sup.f, u, m, n, and R.sup.1 are defined above. The molar
ratio of the isophthalate-terephthalate ester units to the
carbonate units in the polyester-polycarbonate can be 1:99 to 99:1,
specifically, 5:95 to 90:10, more specifically, 10:90 to 80:20.
R.sup.1 can comprise a resorcinol repeat unit. R.sup.1 can comprise
a diaryl carbonate repeat unit. If R.sup.1 comprises both a
resorcinol repeat unit and a diaryl carbonate repeat unit, they can
be present in a molar ratio of resorcinol carbonate units to
bisphenol carbonate units of 1:99 to 100:0. The MW of the arylate
block can be controlled by adjusting the molar excess resorcinol to
diacid chlorides, molar ratio of caustic to diacid chlorides during
the diacid chloride addition and salt concentration during the
oligomerization step as known in the art (for example US Pat. Appl.
2006 0160961 A1). The arylate-containing unit(s) in the
polyester-polycarbonate unit can have an M.sub.w of 2,000 to
100,000 g/mol, specifically, 3,000 to 75,000 g/mol, more
specifically, 4,000 to 50,000 g/mol, more specifically, 5,000 to
18,000 g/mol, and still more specifically, 9,000 to 14,000 g/mol.
Molecular weight determinations are performed using GPC using a
crosslinked styrene-divinyl benzene column, at a sample
concentration of 1 milligram per milliliter, and as calibrated with
polycarbonate standards. Samples are eluted at a flow rate of about
1.0 ml/min with methylene chloride as the eluent.
[0143] The polycarbonate-polysiloxane copolymer can be a
polycarbonate that is end group functionalized with polysiloxane
repeat units. The polysiloxane end groups can have less than or
equal to 15 siloxane units. The polycarbonate-polysiloxane
copolymer can comprise 1 to 60 mol %, specifically, 3 to 50 mol %
of polydiorganosiloxane blocks relative to the moles of
polycarbonate blocks. The polysiloxane copolymer can comprise ester
repeat units (such as isophthalate-terephthalate-resorcinol ester
repeat units), carbonate units (such as bisphenol A repeat units),
or a combination comprising one or both of the foregoing. The
polysiloxane copolymer can comprise an arylate containing unit, for
example, in a polyester and/or in a polycarbonate repeat unit. The
arylate-containing polysiloxane copolymer can comprise of 50 to 99
mol % of arylate ester units, specifically, 58 to 90 mol % arylate
ester units; 0 to 50 mol % aromatic carbonate units (e.g.,
resorcinol carbonate units, bisphenol carbonate units, and other
carbonate units such as aliphatic carbonate units) based on the
total moles of repeat units in the polysiloxane copolymer.
Specifically, the arylate-containing polysiloxane copolymer can
comprise 0 to 30 mol % resorcinol carbonate units, specifically, 5
to 20 mol % resorcinol carbonate units; and 0 to 35 mol % bisphenol
carbonate units, specifically, 5 to 35 mol % bisphenol carbonate
units based on the total moles of repeat units in the polysiloxane
copolymer.
[0144] The polycarbonate-polyester-polysiloxane includes those with
polycarbonate units of formula (1) wherein R.sup.1 is a C.sub.6-30
arylene group, polysiloxane units derived from siloxane diols of
formula (14), (17) or (18), and polyester units wherein T is a
C.sub.6-30 arylene group. T can be derived from isophthalic and/or
terephthalic acid, or reactive chemical equivalents thereof.
R.sup.1 can be derived from the carbonate reaction product of a
resorcinol of formula (9), or a combination of a resorcinol of
formula (9) and a bisphenol of formula (4).
[0145] The polycarbonate-polyester-polysiloxane copolymer can
comprise siloxane units in an amount of 0.1 to 25 weight percent
(wt %), specifically, 0.2 to 10 wt %, more specifically, 0.2 to 6
wt %, even more specifically, 0.2 to 5 wt %, and still more
specifically, 0.25 to 2 wt %, based on the total weight of the
polycarbonate-polyester-polysiloxane copolymer, with the proviso
that the siloxane units are provided by polysiloxane units
covalently bonded in the polymer backbone of the
polycarbonate-polyester-polysiloxane terpolymer. The
polycarbonate-polyester-polysiloxane copolymer can comprise 0.1 to
49.85 wt % carbonate units, 50 to 99.7 wt % ester units, and 0.2 to
6 wt % polysiloxane units, based on the total weight of the
polysiloxane units, ester units, and carbonate units.
Alternatively, the polycarbonate-polyester-polysiloxane copolymer
can comprise 0.25 to 2 wt % polysiloxane units, 60 to 96.75 wt %
ester units, and 3.25 to 39.75 wt % carbonate units, based on the
total weight of the polysiloxane units, ester units, and carbonate
units.
[0146] The polycarbonate-polyester-polysiloxane copolymer can
comprise repeat units that are randomly distributed throughout the
copolymer. Alternatively, it may be desirable to distribute the
polysiloxane units in the polycarbonate units, and thereby exclude
the formation of polysiloxane-ester linkages. Alternatively, it may
be desirable to distribute the polysiloxane units predominately in
the polyester units. In an embodiment, oligomerization to form the
polyester unit is completed in the presence of the end-group
functionalized polysiloxane at which time significant amount of the
siloxane is incorporated into the polyarylate block. After the
addition of the second dihydroxy aromatic compound, the remaining
unreacted end-group functionalized polysiloxane is incorporated
into the carbonante block by addition of a carbonyl source. In a
second embodiment, oligomerization to form the polyester unit is
completed in the absence of the end-group functionalized
polysiloxane, and the end group functionalized polysiloxane is
charged to the reaction concomitantly with a dihydroxy aromatic
compound, followed by addition of a carbonyl source. In an
embodiment, the end-group functionalized polysiloxane is a hydroxy
end-capped polysiloxane. In another embodiment, the hydroxy
end-capped polysiloxane is added prior to the dihydroxy aromatic
compound, and is reacted with a portion of the charge of the
carbonyl source. Some of the hydroxy end-capped polysiloxanes
(e.g., those derived from eugenol) as discussed herein, can have
lower reactivity than dihydroxy aromatic compounds such as
resorcinol and/or bisphenols, and hence may provide a distribution
of polysiloxane which is more enriched in the polymer segments
formed late in the reaction. In another embodiment, the dihydroxy
aromatic compound and carbonyl source are added in portions to the
polymerization after addition of the hydroxy end-capped
polysiloxane. In an embodiment, where the end group functionalized
polysiloxane has less than or equal to 15 siloxane units, a
polysiloxane copolymer composition prepared according to this
method has low haze.
[0147] In another embodiment, wherein it is desirable to distribute
the polysiloxane units randomly with carbonate units in the
polycarbonate unit, the dihydroxy aromatic compound and/or hydroxy
end-capped polysiloxane is converted to its corresponding
bis-chloroformate prior to condensation to form the carbonate
linking groups of the polycarbonate. In this process, the
polyarylate oligomer is initially prepared in a biphasic medium
using a phase transfer catalyst, without an amine or condensation
catalyst present. In an embodiment, the polyarylate oligomer is
prepared using a resorcinol, where the resorcinol comprises the
oligomer end groups. The polyarylate oligomer and excess resorcinol
can be phosgenated at a pH of 2 to 11. In an embodiment, the
polyarylate oligomer is phosgenated at pH of 4 to 10, specifically,
5 to 8 to provide chloroformate end groups, and are subsequently
reacted with the hydroxy end-capped polysiloxane at a pH of about
8.5 to about 11, for a sufficient time, e.g., less than or equal to
20 min. A further charge of dihydroxy aromatic compound, such as a
resorcinol and/or bisphenol, and additional charge of carbonyl
source (e.g., phosgene) can be made. Molecular weight of the
polymer can be increased in the reaction by addition of a
condensation catalyst such as, for example, a tertiary amine.
Optionally, additional phosgene can be added to ensure that
substantially all of the phenolic end groups are incorporated. In
another embodiment, oligomerization to prepare the hydroxy
end-capped polyarylate is performed using a phase transfer
catalyst, and the hydroxy end-capped polysiloxane is added. In an
exemplary embodiment, a phase transfer catalyst has the formula
(R).sub.4Q.sup.-X, wherein R, Q, and X are as defined above. The
combination is phosgenated to convert the phenolic hydroxy end
groups to chloroformate groups, at a pH or 2 to 11, specifically,
at a pH of 4 to 10, and more specifically, at a pH of 4 to 7. A
second dihydroxy aromatic compound, such as a resorcinol and/or
bisphenol, is added to the combination of chloroformates and
condensed at a pH of 7.7 to 11.5, specifically, at a pH of 8 to 9,
and the chloroformates and dihydroxy aromatic compound are reacted
with additional phosgene and tertiary amine. Additional phosgene
can be added if required to complete the polymerization.
[0148] Optionally, a second dihydroxy aromatic compound can be
added to the polyarylate oligomer containing the hyrdoxy end-capped
siloxane, excess resorcinol and tertiary amine catalyst followed by
phosgenation at a pH of 2 to 11. In an embodiment, the mixture is
phosgenated at pH of 6 to 8 for the first half of the required
phosgene, followed by a pH of 8.5 to 10.5 for the second half of
the phosgenation.
[0149] The siloxane-polyester-polycarbonate copolymer can have an
M.sub.w of 15,000 to 100,000 g/mol, specifically, 16,000 to 75,000
g/mol, more specifically, 17,000 to 50,000 g/mol, more
specifically, 17,000 to 45,000 g/mol, and still more specifically,
18,000 to 30,000 g/mol. Molecular weight determinations are
performed using GPC using a crosslinked styrene-divinyl benzene
column, at a sample concentration of 1 milligram per milliliter,
and as calibrated with polycarbonate standards. Samples are eluted
at a flow rate of about 1.0 ml/min with methylene chloride as the
eluent.
[0150] The polymer composition can comprise two or more of a
polysiloxane, a polyester, a polycarbonate, and a copolymer
comprising one or more of the foregoing. The polymer composition
can comprise a polysiloxane-polycarbonate copolymer and a
polycarbonate and the polysiloxane-polycarbonate copolymer can be
present in an amount of 5 to 50 parts by weight, more specifically,
10 to 40 parts by weight, based on 100 parts by weight of the
polycarbonate and any impact modifier.
[0151] For example, the polymer composition can comprise a
polysiloxane copolymer composition and polyester in a weight ratio
of 1:99 to 99:1, specifically, 10:90 to 90:10, and more
specifically, 30:70 to 70:30, based on the total weight of
polysiloxane copolymer composition and polyester.
[0152] The polymer composition can comprise a
polysiloxane-polycarbonate copolymer and a brominated
polycarbonate. For example, the polymer composition can comprise
greater than or equal to 5 wt %, specifically, 5 to 80 wt % of a
poly(siloxane-co-carbonate); greater than or equal to 20 wt %,
specifically, 20 to 95 wt % of a brominated polycarbonate (for
example, a brominated polycarbonate derived from
2,2',6,6'-tetrabromo-4,4'-isopropylidenediphenol
(2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane (TBBPA) and carbonate
units derived from at least one dihydroxy aromatic compound that is
not TBBPA ("TBBPA copolymer")); and optionally a polycarbonate that
is different from the poly(siloxane-co-carbonate) and the TBBPA
copolymer. The third polycarbonate can be present in an amount of 8
to 12 wt % based on the total weight of the
poly(siloxane-co-carbonate), TBBPA copolymer, and optional third
polycarbonate.
[0153] The polymer composition can comprise a
polysiloxane-polycarbonate copolymer and a brominated oligomer. The
polymer composition can comprise greater than or equal to 5 wt %,
specifically, 5 to 80 wt % of a poly(siloxane-co-carbonate);
greater than or equal to 20 wt %, specifically, 20 to 95 wt % of a
brominated oligomer; and optionally a polycarbonate that is
different from the poly(siloxane-co-carbonate) and the brominated
oligomer. The polymer composition can comprise greater than or
equal to 0.3 wt % of siloxane and greater than or equal to 7.8 wt %
of bromine based on the total weight of the
poly(siloxane-co-carbonate), the brominated oligomer, and optional
third polycarbonate. The third polycarbonate can be present in an
amount of 8 to 12 wt % based on the total weight of the
poly(siloxane-co-carbonate), the brominated oligomer, and optional
third polycarbonate. The brominated oligomer can have a weight
average molecular weight of 1000 to 10,000.
[0154] The polymer composition comprising a
polysiloxane-polycarbonate copolymer and a brominated oligomer or a
brominated polycarbonate can comprise greater than or equal to 0.3
wt % of siloxane and greater than or equal to 7.8 wt % of bromine
based on the total weight polymer composition.
[0155] In some embodiments, the polymer layer can be 2 to 15 mm,
specifically, 6 to 13 mm, more specifically, 8 to 13 mm. The
polymer layer can be 2 to 15 mm, specifically, 2 to 12 mm, more
specifically, 5 to 8 mm.
[0156] The polymer layer can comprise FRPC3 and can have a
thickness of 2 to 15 mm, specifically, 6 to 15 mm, more
specifically, 8 to 13 mm or less than or equal to 12 mm,
specifically, 2 to 12 mm, more specifically, 5 to 8 mm. The polymer
layer can comprise NonFRPC and can have a thickness of 2 to 15 mm,
specifically, 6 to 13 mm, more specifically, 8 to 13 mm. The
polymer layer can comprise FRPC1 and can have a thickness of 2 to
15 mm, specifically, 3 to 13 mm. The polymer layer can comprise
FRPC2 and can have a thickness of 2 to 15 mm, specifically, 3 to 13
mm. The polymer layer can comprise FRPC4 and can have a thickness
of 2 to 15 mm, specifically, 3 to 13 mm. The polymer layer can
comprise FST1 and can have a thickness of 2 to 15 mm, specifically,
3 to 13 mm and can be laminated to a glass layer thickness of
greater than 0.7 mm, specifically, greater than or equal to 0.8 mm.
The polymer layer can comprise FST2 and can have a thickness of 2
to 15 mm, specifically, 3 to 13 mm. The polymer layer can comprise
FST3 and can have a thickness of 2 to 15 mm, specifically, 3 to 13
mm. The polymer layer can comprise a flame retardant. Flame
retardants include organic compounds that include phosphorus,
bromine, and/or chlorine. Non-brominated and non-chlorinated
phosphorus-containing flame retardants can be preferred in certain
applications for regulatory reasons, for example, organic
phosphates and organic compounds containing phosphorus-nitrogen
bonds.
[0157] One type of organic phosphate is an aromatic phosphate of
the formula (GO).sub.3P.dbd.O, wherein each G is independently an
alkyl, cycloalkyl, aryl, alkylaryl, or aralkyl group, provided that
at least one G is an aromatic group. Two of the G groups can be
joined together to provide a cyclic group, for example, diphenyl
pentaerythritol diphosphate. Aromatic phosphates include, phenyl
bis(dodecyl) phosphate, phenyl bis(neopentyl) phosphate, phenyl
bis(3,5,5'-trimethylhexyl) phosphate, ethyl diphenyl phosphate,
2-ethylhexyl di(p-tolyl) phosphate, bis(2-ethylhexyl) p-tolyl
phosphate, tritolyl phosphate, bis(2-ethylhexyl) phenyl phosphate,
tri(nonylphenyl) phosphate, bis(dodecyl) p-tolyl phosphate, dibutyl
phenyl phosphate, 2-chloroethyl diphenyl phosphate, p-tolyl
bis(2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyl diphenyl
phosphate, or the like. A specific aromatic phosphate is one in
which each G is aromatic, for example, triphenyl phosphate,
tricresyl phosphate, isopropylated triphenyl phosphate, and the
like.
[0158] Di- or polyfunctional aromatic phosphorus-containing
compounds are illustrated in the formulas below:
##STR00024##
wherein each G.sup.1 is independently a hydrocarbon having 1 to 30
carbon atoms; each G is independently a hydrocarbon or
hydrocarbonoxy having 1 to 30 carbon atoms; each X is independently
a bromine or chlorine; m is 0 to 4, and n is 1 to 30. Di- or
polyfunctional aromatic phosphorus-containing compounds of this
type include resorcinol tetraphenyl diphosphate (RDP), the
bis(diphenyl) phosphate of hydroquinone and the bis(diphenyl)
phosphate of bisphenol A, respectively, their oligomeric and
polymeric counterparts, and the like.
[0159] Flame retardant compounds containing phosphorus-nitrogen
bonds include phosphonitrilic chloride, phosphorus ester amides,
phosphoric acid amides, phosphonic acid amides, phosphinic acid
amides, and tris(aziridinyl) phosphine oxide. Specific examples
include phosphoramides of the formula:
##STR00025##
wherein each A moiety is a 2,6-dimethylphenyl moiety or a
2,4,6-trimethylphenyl moiety. These phosphoramides are
piperazine-type phosphoramides.
[0160] Other flame retardant compounds containing
phosphorus-nitrogen bonds include phosphazenes. Specific examples
include phosphazenes of the formula:
##STR00026##
where X is --O-Phenyl, alkyl-phenyl, dialkylphenyl or trialkyl
phenyl. An illustrative example of the phosphazenes would include
SPB-100 from Otsuka Chemical Co.,Ltd (X=phenyl).
[0161] When used, phosphorus-containing flame retardants can be
present in amounts of 0.1 to 30 parts by weight, specifically, 1 to
20 parts by weight, based on 100 parts by weight of the total
composition, excluding any filler.
[0162] Halogenated materials can also be used as flame retardants,
for example, halogenated compounds and polymers of formula
(20):
##STR00027##
wherein R is an alkylene, alkylidene, or cycloaliphatic linkage
(e.g., methylene, ethylene, propylene, isopropylene,
isopropylidene, butylene, isobutylene, amylene, cyclohexylene,
cyclopentylidene, and the like), a linkage selected from oxygen
ether, carbonyl, amine, a sulfur containing linkage (e.g., sulfide,
sulfoxide, or sulfone), a phosphorus containing linkage, and the
like, or R can also consist of two or more alkylene or alkylidene
linkages connected by such groups as aromatic, amino, ether,
carbonyl, sulfide, sulfoxide, sulfone, a phosphorus containing
linkage, and the like; Ar and Ar' can be the same or different and
are mono- or polycarbocyclic aromatic groups such as phenylene,
biphenylene, terphenylene, naphthylene, and the like; Y is an
organic, inorganic or organometallic radical such as halogen (e.g.,
chlorine, bromine, iodine, or fluorine), ether group of the general
formula OE wherein E is a monovalent hydrocarbon radical similar to
X, monovalent hydrocarbon groups of the type represented by R, or
other substituents (e.g., nitro, cyano, or the like), the
substituents being essentially inert provided there be at least one
and preferably two halogen atoms per aryl nucleus; each X is the
same or different, and is a monovalent hydrocarbon group such as
alkyl (e.g., methyl, ethyl, propyl, isopropyl, butyl, decyl, and
the like), aryl (e.g., phenyl, naphthyl, biphenyl, xylyl, tolyl,
and the like), arylalkylene (e.g., as benzyl, ethylenephenyl, and
the like), cycloaliphatic (e.g., cyclopentyl, cyclohexyl, and the
like), as well as monovalent hydrocarbon groups containing inert
substituents therein; the letter d represents a whole number from 1
to a maximum equivalent to the number of replaceable hydrogens
substituted on the aromatic rings comprising Ar or Ar'; the letter
e represents a whole number from 0 to a maximum equivalent to the
number of replaceable hydrogens on R; the letters a, b, and c
represent whole numbers including 0, provided that when b is not 0,
neither a nor c can be 0, or that either a or c, but not both, can
be 0, or that where b is 0, the aromatic groups are joined by a
direct carbon-carbon bond; the hydroxyl and Y substituents on the
aromatic groups, Ar and Ar' can be varied in the ortho, meta or
para positions on the aromatic rings and the groups can be in any
possible geometric relationship with respect to one another.
[0163] Included within the scope of the above formula are:
2,2-bis-(3,5-dichlorophenyl)-propane; bis-(2-chlorophenyl)-methane;
bis(2,6-dibromophenyl)-methane; 1,1-bis-(4-iodophenyl)-ethane;
1,2-bis-(2,6-dichlorophenyl)-ethane;
1,1-bis-(2-chloro-4-iodophenyl)ethane;
1,1-bis-(2-chloro-4-methylphenyl)-ethane;
1,1-bis-(3,5-dichlorophenyl)-ethane;
2,2-bis-(3-phenyl-4-bromophenyl)-ethane;
2,6-bis-(4,6-dichloronaphthyl)-propane;
2,2-bis-(2,6-dichlorophenyl)-pentane;
2,2-bis-(3,5-dibromophenyl)-hexane;
bis-(4-chlorophenyl)-phenyl-methane;
bis-(3,5-dichlorophenyl)-cyclohexylmethane;
bis-(3-nitro-4-bromophenyl)-methane;
bis-(4-hydroxy-2,6-dichloro-3-methoxyphenyl)-methane; and
2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane 2,2
bis-(3-bromo-4-hydroxyphenyl)-propane. Also included within the
above structural formula are: 1,3-dichlorobenzene,
1,4-dibromobenzene, 1,3-dichloro-4-hydroxybenzene, and biphenyls
such as 2,2'-dichlorobiphenyl, polybrominated 1,4-diphenoxybenzene,
2,4'-dibromobiphenyl, and 2,4'-dichlorobiphenyl as well as
decabromo diphenyl oxide, and the like.
[0164] Also useful are oligomeric and polymeric halogenated
aromatic compounds, such as a copolycarbonate of bisphenol A and
tetrabromobisphenol A and a carbonate precursor, e.g., phosgene.
Metal synergists, e.g., antimony oxide, can also be used with the
flame retardant. When present, the halogen containing flame
retardant can be present in an amount of 1 to 25 parts by weight,
specifically, 2 to 20 parts by weight, based on 100 parts by weight
of the total composition, excluding any filler.
[0165] The polymer composition can be essentially free of chlorine
and bromine. Essentially free of chlorine and bromine refers to
materials produced without the intentional addition of chlorine or
bromine or chlorine or bromine containing materials. It is
understood however that in facilities that process multiple
products a certain amount of cross contamination can occur
resulting in bromine and/or chlorine levels typically on the parts
per million by weight scale. With this understanding, it can be
readily appreciated that essentially free of bromine and chlorine
can be defined as having a bromine and/or chlorine content of less
than or equal to 100 parts per million by weight (ppm), less than
or equal to 75 ppm, or less than or equal to 50 ppm. When this
definition is applied to the fire retardant, it is based on the
total weight of the fire retardant. When this definition is applied
to the polymer composition it is based on the total weight of the
composition, excluding any filler.
[0166] Inorganic flame retardants can also be used, for example,
salts of C.sub.2-16 alkyl sulfonates such as potassium
perfluorobutane sulfonate (Rimar salt), potassium perfluoroctane
sulfonate, and tetraethylammonium perfluorohexane sulfonate, salts
of aromatic sulfonates such as sodium benzene sulfonate, sodium
toluene sulfonate (NATS), and the like, salts of aromatic sulfone
sulfonates such as potassium diphenylsulfone sulfonate (KSS), and
the like; salts formed by reacting for example, an alkali metal or
alkaline earth metal (e.g., lithium, sodium, potassium, magnesium,
calcium and barium salts) and an inorganic acid complex salt, for
example, an oxo-anion (e.g., alkali metal and alkaline-earth metal
salts of carbonic acid, such as Na.sub.2CO.sub.3, K.sub.2CO.sub.3,
MgCO.sub.3, CaCO.sub.3, and BaCO.sub.3, or a fluoro-anion complex
such as Li.sub.3AlF.sub.6, BaSiF.sub.6, KBF.sub.4,
K.sub.3AlF.sub.6, KAlF.sub.4, K.sub.2SiF.sub.6, and/or
Na.sub.3AlF.sub.6 or the like. Rimar salt and KSS and NATS, alone
or in combination with other flame retardants, are particularly
useful. When present, inorganic flame retardant salts are generally
present in amounts of 0.01 to 10 parts by weight, more
specifically, 0.02 to 1 parts by weight, based on 100 parts by
weight of polycarbonate and impact modifier. Rimar salt and KSS and
NATS, alone or in combination with other flame retardants, are
particularly useful. The perfluoroalkyl sulfonate salt can be
present in an amount of 0.30 to 1.00 wt %, specifically, 0.40 to
0.80 wt %, more specifically, 0.45 to 0.70 wt %, based on the total
weight of the composition. The aromatic sulfonate salt can be
present in the final polymer composition in an amount of 0.01 to
0.1 wt %, specifically, 0.02 to 0.06 wt %, and more specifically,
0.03 to 0.05 wt %. Exemplary amounts of aromatic sulfone sulfonate
salt can be 0.01 to 0.6 wt %, specifically, 0.1 to 0.4 wt %, and
more specifically, 0.25 to 0.35 wt %, based on the total weight of
the polymer composition.
[0167] Combinations comprising at least one of the foregoing salts
can be used, for example, a perfluoroalkyl sulfonate salt and an
aromatic phosphate ester, or a combination of an aromatic phosphate
ester and a polycarbonate-polysiloxane copolymer. Metal synergists,
e.g., antimony oxide, can also be used with the flame
retardant.
[0168] Anti-drip agents can also be used in the composition, for
example, a fibril forming or non-fibril forming fluoropolymer such
as polytetrafluoroethylene (PTFE). The anti-drip agent can be
encapsulated by a rigid copolymer as described above, for example,
styrene-acrylonitrile copolymer (SAN). PTFE encapsulated in SAN is
known as TSAN. Encapsulated fluoropolymers can be made by
polymerizing the encapsulating polymer in the presence of the
fluoropolymer, for example, an aqueous dispersion. TSAN can provide
significant advantages over PTFE, in that TSAN can be more readily
dispersed in the composition. A TSAN can comprise 50 wt % PTFE and
50 wt % SAN, based on the total weight of the encapsulated
fluoropolymer. The SAN can comprise, for example, 75 wt % styrene
and 25 wt % acrylonitrile based on the total weight of the
copolymer. Alternatively, the fluoropolymer can be pre-blended in
some manner with a second polymer, such as, an aromatic
polycarbonate or SAN to form an agglomerated material for use as an
anti-drip agent. Either method can be used to produce an
encapsulated fluoropolymer. An antidrip agent can be present in an
amount of 0.1 to 10 percent by weight, based on 100 percent by
weight of polycarbonate and impact modifier.
[0169] Exemplary multilayer articles can be prepared by adding an
interlayer to a polymer layer; adding a glass layer to the
interlayer to form a multilayer structure; and laminating the
multilayer structure to form the multilayer article. For example, a
multilayer article can be prepared by creating a laminate stack by
placing a first interlayer on top of a first glass layer, then
placing a polymer layer onto the first interlayer, then placing a
second interlayer onto the polymer layer, and finally placing a
second glass layer onto the second interlayer. A laminate stack of
the multilayer article can be prepared similarly by placing a first
interlayer on top of a first glass layer, then placing a polymer
layer onto the first interlayer. The laminate stack used to create
the multilayer article must then go through a lamination process
where heat, pressure, and vacuum are applied to the material stack.
During this process the interlayer material must soften to a point
where it forms a bond between the glass and polymer layers of the
material stack. The lamination process can be performed by a
variety of processes known in the art and may include autoclave
lamination, vacuum bag lamination, vacuum lamination, and/or
parallel platen lamination.
[0170] In an embodiment, a multilayer article was prepared by
placing the laminate stack in a vacuum bag and then placing the
vacuum bagged laminate stack into an autoclave. From room
temperature of 60.degree. to 75.degree. F., and specifically
66.degree. F., the temperature in the autoclave was increased until
the temperature in the laminate stack reached 115.degree. to
135.degree. F., specifically 125.degree. F. at a rate of 1 to 5
degrees Farenheit per minute (.degree. F./min), specifically
3.1.degree. F./min. The laminate stack temperature was allowed to
stabilize at this temperature for 3 to 10 minutes, specifically 5
minutes. After this stabilization step, the pressure and the
temperature in the autoclave were increased. Pressure in the
autoclave was gradually increased and then held at 100 to 125,
specifically 115 pounds per square inch (psi) over 20 to 50,
specifically 35 minutes. The temperature of the laminate stack was
gradually increased to 260 to 290.degree. F., and specifically to
275.degree. F., over 30 minutes to 1 hour and 30 minutes, and
specifically 52 minutes. The temperature was held at 260 to
290.degree. F., and specifically to 275.degree. F., for 10 to 60
minutes, specifically 15 minutes. The laminate stack was allowed to
cool gradually at -1 to -5.degree. F./min, specifically
-2.24.degree. F./min, to 100.degree. to 130.degree. F.,
specifically 120.degree. F. where the pressure in the autoclave was
released. The autoclave was opened and the laminate stack was
allowed to return to room temperature.
[0171] In another embodiment, a multilayer article was prepared by
placing the laminate stack in a vacuum laminator. From room
temperature of 30.degree. C. a vacuum was pulled in the vacuum
laminator so that the pressure read 0 mBar. This condition was held
for 15 minutes. The temperature was increased from 30 to 90.degree.
C. at 1.degree. C./min while a pressure of 1 Bar was added to the
vacuum pressure. The laminate stack was held at 90.degree. C., 0
bar vacuum and 1 bar pressure for 4 hours. The temperature was
increased from 90.degree. C. to 115.degree. C. at VC/min while
maintaining the vacuum and pressure. The laminate stack was held at
115.degree. C., 0 bar vacuum, and 1 bar pressure for 5 hours and 30
minutes. The vacuum and the pressure were then released and the
sample was allowed to return to room temperature before removing it
from the vacuum laminator. In this example, the polymer layer was
dried in an oven for 12 hours at the glass transition temperature
of the polymer, specifically 250.degree. F. for polycarbonate.
[0172] The following examples are provided to illustrate the flame
retardant properties of the multilayer article. The examples are
merely illustrative and are not intended to limit devices made in
accordance with the disclosure to the materials, conditions, or
process parameters set forth therein.
EXAMPLES
[0173] The materials listed in Table 1 were used in the below
examples.
TABLE-US-00003 TABLE 1 Material Details Supplier Glass Hardened
Gorilla Glass Corning TPU Thermoplastic Huntsman polyurethane HALS
free EVA Poly(ethylene-co-vinyl STR acetate) without hindered amine
light stabilizers NonFRPC Non flame retardant, UV SABIC's
Innovative stabilized bisphenol-A Plastics business polycarbonate
FRPC1 5-7 wt % Brominated Flame SABIC's Innovative retardant
bisphenol-A Plastics business polycarbonate FRPC2 2-4 wt %
Brominated Flame SABIC's Innovative retardant bisphenol-A Plastics
business polycarbonate FRPC3 Non-brominated flame SABIC's
Innovative retardant bisphenol-A Plastics business polycarbonate
FRPC4 Mineral filled flame SABIC's Innovative retardant impact
modified Plastics business bisphenol-A polycarbonate FST1 A 50/50
blend of a SABIC's Innovative polysiloxane-ITR Plastics business
(Isophthalic acid- terephthalic acid- resorcinol) - bisphenol-A
copolyesterearbonate copolymer; with an ester content 83 mol %,
siloxane content 1 wt % (average siloxane chain length about 10),
interfacial polymerization, Mw = 22,500 to 26,500 g/mol, para-cumyl
phenol end- capped, an ITR (Isophthalic acid-terephthalic acid-
resorcinol) - bisphenol-A copolyesterearbonate copolymer; with an
ester content 83 mol %, Mw = 22,500 to 26,500 g/mol, para-cumyl
phenol end- capped and a phosphite heat stabilizer FST2 A blend of
a polysiloxane- SABIC's Innovative ITR (Isophthalic acid- Plastics
business terephthalic acid- resorcinol) - bisphenol-A
copolyestercarbonate copolymer; with an ester content 83 mol %,
siloxane content 1 wt % (average siloxane chain length about 10),
Mw ~21,000 g/mol, para-cumyl phenol end- capped, ~8 wt % BPADP and
a phosphite heat stabilizer FST3 A 50/40/10 blend of a SABIC's
Innovative polydimethylsiloxane - Plastics business bisphenol A
polycarbonate copolymer, produced via interfacial polymerization, 6
wt % siloxane, average PDMS block length of ~45 units (D45), Mw
~23,000 g/mol, para-cumylphenol (PCP) end-capped/A
tetrabromo-bisphenol A (TBBPA) and bisphenol A (BPA)
copolycarbonate (~30 mol % TBBPA) with an average Mw of ~22,500
g/mol, p-cumyl phenol (PCP) endcap/BPA polycarbonate, Mw of ~22,500
g/mol, p-cumyl phenol and a phosphite heat stabilizer
Examples 1-6: FAR Testing of Dual Sided Multilayer Articles
[0174] Dual sided multilayer articles with hardened glass layer,
TPU or HALS free EVA interlayers, and polycarbonate polymer layers
were prepared and tested for compliance with Federal Aviation
Regulations as shown in Table 2.
[0175] Heat release testing was performed on 15.2.times.15.2
centimeter (cm) plaques 1.5 mm thick using the Ohio State
University (OSU) 65/65 rate-of-heat release apparatus, in
accordance with the method shown in FAR 25.853 (d), and in Appendix
F, section IV (FAR F25.4). Total heat release was measured up to
the two-minute mark in kW-min/m.sup.2. Peak heat release was
measured as kW/m.sup.2. The heat release test method is also
described in the "Aircraft Materials Fire Test Handbook"
DOT/FAA/AR-00/12, Chapter 5 "Heat Release Test for Cabin
Materials." In order to obtain a "pass," the two-minute total heat
release had to be less than or equal to 65 kW-min/m.sup.2 and the
peak heat release rate had to be less than or equal to 65
kW/m.sup.2.
[0176] Flame Spread per the method shown in ASTM E-162 was
performed on 15.24 cm.times.45.72 cm samples with thicknesses
ranging from 5 mm to 17 mm. In order to obtain a "pass", the Flame
Spread Index had to be less than or equal to 100. Smoke density and
toxicity testing per the methods shown in ASTM E-162, ASTM
E-662-83, Bombardier SNIP 800-C, ASTM F-814-83, Airbus ABD0031, and
Boeing BSS 7239 was performed on 7.5.times.7.5 cm plaques with
thicknesses ranging from 5 mm to 17 mm. Smoke density was measured
under flaming mode at 4.0 min. In order to obtain a "pass," the
smoke density had to be less than or equal to 200 at 4 minutes. In
order to obtain a "pass" for the toxicity tests, the toxic gas
generated from material combustion could not exceed the specified
maxima as indicated here with for the associated toxic gasses: 3500
for Carbon Monoxide, 90000 for Carbon Dioxide, 100 for Nitrogen
Oxides, 100 for Sulfur Dioxide, 500 for Hydrogen Chloride, 100 for
Hydrogen Fluoride, 100 for Hydrogen Bromide, 100 for Hydrogen
Cyanide. Smoke Generation according to the method shown in FAR
25.853 (d), Amendment No. 25-83, and in Appendix F, section V
(DOT/FAA/AR-00/12)(FAR F25.5) was performed on 7.62 cm.times.30.48
cm samples with thicknesses ranging from 5 mm to 17 mm. In order to
obtain a "pass," the smoke generation had to be less than or equal
to 200.
TABLE-US-00004 TABLE 2 1 2 3 4 5 6 Interlayer TPU TPU EVA EVA EVA
EVA material Lexan NonFRPC NonFRPC NonFRPC NonFRPC FRPC3 FRPC3
grade First glass 0.7 0.7 0.7 0.7 0.7 0.7 layer (mm) First TPU 0.38
1.27 0.46 0.46 0.46 0.46 layer (mm) Polymer 3.18 12.7 6.35 12.7
6.35 12.7 layer (mm) Second TPU 0.38 1.27 0.46 0.46 0.46 0.46 layer
(mm) Second glass 0.7 0.7 0.7 0.7 0.7 0.7 layer (mm) Flame spread:
Pass Pass Pass Pass Pass Pass ASTM E162 Smoke density: Pass Pass
Pass Pass Pass Pass ASTM E662 Smoke Pass Pass Pass Pass Pass Pass
generation: FAR 25.853 (d) Appendix F Part V Toxicity: Pass Pass
Pass Pass Pass Pass SMP 800C and Boeing BSS 7239
[0177] Table 2 shows that the multilayer articles with glass layer
thicknesses, TPU interlayers or HALS free EVA interlayers, and a
NonFRPC or FRPC3 polymer layer were able to pass the Federal
Aviation Regulations for flame spread, smoke density, smoke
generation, and toxicity.
Examples 7-14: Ballistic Testing of Single and Dual Sided
Multilayer Articles
[0178] Single sided multilayer articles (Examples 7-8) and dual
sided multilayer articles (Example 9-11) were prepared and tested
for compliance with Ballistic and Block tests according to the
Federal Railway Regulations and are shown in Table 3.
TABLE-US-00005 TABLE 3 7 8 9 10 11 12 13 14 Interlayer material TPU
EVA TPU EVA TPU -- -- TPU First glass 0.7 0.55 0.7 0.55 0.7 -- --
0.7 layer (mm) First interlayer 0.38 0.46 0.38 0.46 0.38 -- -- 0.38
(mm) NonFRPC polymer 6.35 6.35 9.53 9.53 12.7 9.53 12.7 6.35 layer
(mm) Second interlayer -- -- 0.38 0.46 0.38 -- -- 0.38 (mm) Second
glass layer -- -- 0.7 0.55 0.7 -- -- 0.7 (mm) Ballistic Threat FRA
Pass Fail Pass Fail Pass Fail Pass Fail CFR 49 Type I Block Threat
FRA Pass Pass Pass Pass Pass Pass Pass Pass CFR 49 Type I
[0179] Table 3 shows that for a single sided multilayer article,
the glass layer should be greater than or equal to 0.7 mm and the
polymer layer should be greater than or equal to 6 mm in order to
pass the Ballistic and Block tests. Table 3 shows that for a dual
sided multilayer article, the glass layer should be greater than or
equal to 0.7 mm and the polymer layer should be greater than or
equal to 9 mm in order to pass the Ballistic and Block tests. Table
3 shows that the polymer layer without any glass laminate should be
greater than or equal to 12 mm in order to pass the Ballistic and
Block tests.
Examples 15-25: Testing of Dual Sided Multilayer Articles for
Compliance with the European Flammability Test
[0180] Dual sided multilayer articles with hardened glass layer,
TPU or HALS free EVA interlayers, and polycarbonate polymer and
copolymer layers were prepared and tested for compliance with
European flammability regulations as shown in Table 4.
[0181] Heat release testing was performed on 10.times.10 centimeter
(cm) plaques ranging in thickness from 4.5 to 17 mm, in accordance
with the method shown in EN45545 and ISO 5660. Maximum average heat
release (MARHE) was measured in kiloWatts per square meter
(kW/m.sup.2)] In order to obtain an HL2 level "pass," the heat
release had to be less than 90 kW/m.sup.2.
[0182] Fire propagation testing was performed on 80.times.15.5
centimeter (cm) plaques ranging in thickness from 4.5 to 17 mm
thick, in accordance with the method shown in EN45545 and ISO
5658-2. In order to obtain a "pass," the critical flux at
extinguishment (CFE) had to be greater than 20 kW/m.sup.2.
[0183] Smoke density and toxicity testing was performed on
7.5.times.7.5 cm plaques ranging in thickness from 4.5 to 17 mm
according to the method shown in EN 45545 and ISO 5659-2 for a
smoke density at 240 seconds, where in order to obtain a "pass,"
the smoke density had to be less than 300, and VOF.sub.4, where in
order to obtain a "pass," the smoke density had to be less than
600, and CIT.sub.G, where in order to obtain a "pass," the toxicity
had to be less than 0.9 for an HL2 rating and 1.2 for an HL1
rating.
TABLE-US-00006 TABLE 4 15 16 17 18 19 20 21 22 23 24 25 26
polymer/Lexan grade NonFRPC NonFRPC NonFRPC NonFRPC FRPC1 FRPC3
FRPC3 FST2 FST1 FST3 FRPC2 FRPC2 Interlayer material TPU EVA TPU
EVA EVA EVA EVA EVA EVA EVA EVA EVA First glass layer (mm) 0.7 0.7
0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 First interlayer (mm) 0.38
0.46 0.38 0.46 0.46 0.46 0.46 0.46 0.46 0.46 0.46 0.46 polymer
layer (mm) 6.35 6.35 12.7 12.7 3.18 12.7 5 3 3 3 3 8 Second
interlayer (mm) 0.38 0.46 0.38 0.46 0.46 0.46 0.46 0.46 0.46 0.46
0.46 0.46 Second glass layer (mm) 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7
0.7 0.7 0.7 0.7 Heat release EN45545 Fail Fail Fail Pass Pass Fail
Fail Pass Pass Pass Pass Pass (ISO 5660) Fire Propagation Pass Fail
Pass Pass Pass Pass Pass Pass Pass Pass Pass Pass EN45545 (ISO
5658-2) Smoke Density EN45545 Pass Pass Pass Pass Pass Pass Pass
Pass Pass Pass Pass Pass (ISO 5659-2) DS 240 s Smoke Density
EN45545 Pass Pass Pass Pass Pass Pass Pass Pass Pass Pass Pass Pass
(ISO 5659-2) VOF.sub.4 Toxicity EN45545 Not Not Not Pass Pass Not
Not Pass Pass Pass Pass Pass (ISO 5659-2) CIT.sub.G tested tested
tested HL2 HL1 tested tested HL2 HL2 HL3 HL2 HL2
[0184] Table 4 above shows that Examples 18,19, 22-26 were
surprisingly able to pass all the European flammability tests.
Table 4 also shows that neither of Examples 15 and 17 with a TPU
interlayer were able to pass the heat release test, even at thinner
interlayer thicknesses. Table 4 also shows that materials with not
enough flame retardant do not pass as shown in examples 16, 20, and
21. Table 4 also shows that materials with high levels of bromine
for flame retardant result in a lower class rating for toxicity as
seen in example 19.
Examples 27-37: Testing of Dual Sided Multilayer Articles for
Compliance with the British Flammability Test
[0185] Dual sided multilayer articles 27-37 with hardened glass
layer, HALS free EVA interlayers, and polycarbonate polymer and
copolymer layers were prepared and tested for compliance with
British flammability regulations as shown in Table 5.
[0186] Flame spread testing was performed in accordance with the
method shown in BS476, Part 7. In order to obtain a "pass," the
flame spread had to be less than or equal to 165 mm. Fire
propagation testing was performed in accordance with the method
shown in BS476, Part 6. In order to obtain a "pass," the fire
propagation had to be less than or equal to 12. Smoke generation
testing was performed in accordance with the method shown in BS
6853:1999 Annex D8.4 Panel Smoke test. In order to obtain a "pass,"
the tested article must have an Ao (On) of less than 2.6 and an Ao
(off) of less than 3.9. Toxicity testing was performed in
accordance with the method shown in BS 6853:1999 Annex B.2. In
order to obtain a "pass," the toxicity had to be less than or equal
to 1.
TABLE-US-00007 TABLE 5 27 28 29 30 31 32 33 34 35 36 37 Lexan grade
FRPC3 FRPC3 FRPC3 FRPC4 FRPC3 FRPC1 FRPC1 FST1 FST1 FST2 FST3 First
glass layer (mm) 0.7 1 0.7 0.7 1 0.7 1 0.7 1 0.7 1 First interlayer
(mm) 0.46 0.46 0.46 0.46 0.46 0.46 0.46 0.46 0.46 0.46 0.46 Polymer
layer (mm) 6.35 6.35 12.7 2 12.7 3.18 3.18 3.18 3.18 3.18 3.18
Second interlayer (mm) 0.46 0.46 0.46 0.46 0.46 0.46 0.46 0.46 0.46
0.46 0.46 Second glass layer (mm) 0.7 1 0.7 0.7 1 0.7 1 0.7 1 0.7 1
Flame spread BS476 no no no Fail Fail no no Pass Pass Pass Pass
Part 7 test test test test test Fire Propagation BS476 Fail Fail
Fail Pass Fail Fail Fail Fail Pass Pass Pass Part 6 Smoke BS6853
Annex no no no no no no no no Pass Pass Pass D8.4 test test test
test test test test test Toxicity BS6853 Annex no no no no no no no
no Pass Pass Pass B.2 test test test test test test test test
[0187] Table 5 shows that Examples 35, 36 and 37 are surprisingly
able to pass the flame spread, the fire propagation, the smoke, and
the toxicity tests. Comparing Examples 34 and 35, Example 35 has an
increased glass layer of 1 mm and was able to pass the tests, where
Example 34 had a glass layer of only 0.7 mm and was not able to
pass the fire propagation test. Example 36, with a polymer layer of
FST2 and a glass layer thickness of 0.7 mm was able to pass all
tests.
Examples 38-43: Deflection Testing of Dual Sided Multilayer
Articles for Compliance with the Rail Standards
[0188] Simulations were performed using finite element analysis. In
the simulations, double paned, single and dual sided multilayer
articles with hardened glass layers, interlayers that perfectly
bond the glass layers to the polymer layers, and polycarbonate
polymer layers were simulated and tested for deflection as shown in
Tables 6 and 7. Examples 38-40 and 44-45 are dual sided double pane
examples similar to FIG. 11, where pane 4 comprising the first
polymer layer is the outside pane and pane 104 comprising the
second polymer layer is the inside pane. Examples 41-43 and 46-47
are single sided double pane examples similar to FIG. 10, where
pane 2 comprising the first polymer layer is the outside pane and
pane 102 comprising the second polymer layer is the inside
pane.
[0189] Table 6 shows a deflection test for intercity trains where a
1,467 mm by 1,215 mm test sample with an applied load of 2,500
Newtons per meter squared (N/m.sup.2) to the inside pane was
considered to pass as it had a maximum deflection of less than or
equal to 5 mm.
TABLE-US-00008 TABLE 6 38 39 40 41 42 43 First glass layer (mm) 0.7
0.7 0.7 0.7 0.7 0.7 First polymer layer (mm) 12 9.5 6 12 12.7 3.18
Second glass layer (mm) 0.7 0.7 0.7 -- -- -- Air gap (mm) 12 12 12
12 12 12 Third glass layer (mm) 0.7 0.7 0.7 -- -- -- Second polymer
layer (mm) 6 6 6 6 6 6 Fourth glass layer (mm) 0.7 0.7 0.7 0.7 0.7
0.7 Outside pane max Pass Pass Fail Fail Fail Fail deformation (mm)
Outside pane max stress Pass Pass Fail Fail Fail Fail (MPa) Inside
pane max Fail Fail Fail Fail Fail Fail deformation (mm) Inside pane
max stress Fail Fail Fail Fail Fail Fail (MPa)
[0190] Table 6 shows that the outside pane of Example 38 and 39
were able to pass the maximum deflection test. It is noted, that
while the remaining panes did not pass the maximum deflection test,
modifying the pane, for example, by decreasing the area of the pane
and/or by increasing the layer thickness of one or both of the
polymer layer and/or a glass layer would likely result in a
pass.
[0191] Table 7 shows a deflection test for high speed trains where
a 1,512 mm by 842 mm test sample with an applied load of 6,000
N/m.sup.2 to the inside pane was considered to pass as it had a
maximum deflection of less than or equal to 5 mm.
TABLE-US-00009 TABLE 7 44 45 46 47 First glass layer (mm) 0.7 0.7
0.7 0.7 First polymer layer (mm) 12.7 10 12.7 10 Second glass layer
(mm) 0.7 0.7 -- -- Air gap (mm) 12 12 12 12 Third glass layer (mm)
0.7 0.7 -- -- Second polymer layer (mm) 6 6 6 6 Fourth glass layer
(mm) 0.7 0.7 0.7 0.7 Outside pane max deformation (mm) Pass Pass
Pass Fail Outside pane max stress (MPa) Pass Pass Pass Fail Inside
pane max deformation (mm) Pass Pass Fail Fail Inside pane max
stress (MPa) Pass Pass Fail Fail
[0192] Table 7 shows that the outside and inside panes of Example
44 and 45 and the outside pane of Example 46 were able to pass the
maximum deflection test. It is noted, that while the remaining
panes did not pass the maximum deflection test, modifying the pane,
for example, by decreasing the area of the panes and/or increasing
the layer thickness of one or both of the polymer layer and/or a
glass layer would likely result in a pass.
Examples 48-56: Testing of Dual Sided Multilayer Articles for
Compliance with Federal Aviation Regulations (FARs), in Particular
the Heat Release Rate Standard Described in FAR 25.853(d) Appendix
F, Part IV and Determined Using the Ohio State University
Calorimeter
[0193] Dual sided multilayer articles 48-56 with hardened glass
layer, HALS free EVA interlayers, and polycarbonate polymer and
copolymer layers were prepared and tested for compliance with FAR
25.853(d) Appendix F, Part IV and determined using the Ohio State
University calorimeter. In order to have a "pass," the article must
have a 2 minute (min) integrated heat release rate of less than or
equal to 65 kilowatt-minutes per square meter (kW-min/m.sup.2) and
a peak heat release rate of less than 65 kilowatts per square meter
(kW/m.sup.2) determined using the Ohio State University
calorimeter, abbreviated as OSU 65/65 (2 min/peak). In order to
have a "pass," to the more stringent test, the article must have a
2 minute integrated heat release rate of less than or equal to 55
kW-min/m.sup.2 and a peak heat release rate of less than 55
kW/m.sup.2 (abbreviated as OSU 55/55).
TABLE-US-00010 TABLE 8 48 49 50 51 52 53 54 55 56 polymer/Lexan
grade NonFRPC NonFRPC FRPC3 FRPC3 FRPC2 FRPC2 FST1 FST2 FST3
Interlayer material EVA EVA EVA EVA EVA EVA EVA EVA EVA First glass
layer (mm) 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 First interlayer
(mm) 0.46 0.46 0.46 0.46 0.46 0.46 0.46 0.46 0.46 polymer layer
(mm) 3 12 3 12 3 8 3 3 3 Second interlayer (mm) 0.46 0.46 0.46 0.46
0.46 0.46 0.46 0.46 0.46 Second glass layer (mm) 0.7 0.7 0.7 0.7
0.7 0.7 0.7 0.7 0.7 OSU 65/65 Fail Fail Pass Fail Pass Pass Pass
Pass Pass OSU 55/55 Fail Fail Fail Fail Fail Fail Pass Pass
Pass
[0194] Table 8 shows that examples of multilayer articles made with
a polymer or copolymer that did not have a flame retardant in its
composition as in examples 48 and 49 did not pass the OSU 65/65 or
55/55 tests. Adding some flame retardant to the polymer
composition, as shown in example 50 or a brominated flame retardant
as shown in examples 52 and 53 resulted in a pass to the 65/65
standard. The use of a copolymer as shown in examples 54, 55, and
56 resulted in a pass of both the 65/65 and the 55/55 tests.
[0195] Embodiments may alternately comprise, consist of, or consist
essentially of, any appropriate components herein disclosed.
Furthermore, embodiments, may additionally, or alternatively, be
formulated so as to be devoid, or substantially free, of any
components, materials, ingredients, adjuvants or species used in
the prior art compositions or that are otherwise not necessary to
the achievement of the function and/or objectives of the present
disclosure.
[0196] All ranges disclosed herein are inclusive of the endpoints,
and the endpoints are independently combinable with each other
(e.g., ranges of "up to 25 wt %, or, more specifically, 5 to 20 wt
%", is inclusive of the endpoints and all intermediate values of
the ranges of "5 to 25 wt %," etc.). "Combination" is inclusive of
blends, mixtures, alloys, reaction products, and the like.
Furthermore, the terms "first," "second," and the like, herein do
not denote any order, quantity, or importance, but rather are used
to denote one element from another. The terms "a" and "an" and
"the" herein do not denote a limitation of quantity, and are to be
construed to cover both the singular and the plural, unless
otherwise indicated herein or clearly contradicted by context. The
suffix "(s)" as used herein is intended to include both the
singular and the plural of the term that it modifies, thereby
including one or more of that term (e.g., the film(s) includes one
or more films). Reference throughout the specification to "one
embodiment," "another embodiment," "an embodiment," and so forth,
means that a particular element (e.g., feature, structure, and/or
characteristic) described in connection with the embodiment is
included in at least one embodiment described herein, and may or
may not be present in other embodiments. In addition, it is to be
understood that the described elements may be combined in any
suitable manner in the various embodiments.
[0197] While particular embodiments have been described,
alternatives, modifications, variations, improvements, and
substantial equivalents that are or may be presently unforeseen may
arise to Applicants or others skilled in the art. Accordingly, the
appended claims as filed and as they may be amended are intended to
embrace all such alternatives, modifications variations,
improvements, and substantial equivalents.
[0198] Compounds are described using standard nomenclature. For
example, any position not substituted by any indicated group is
understood to have its valency filled by a bond as indicated, or a
hydrogen atom. A dash ("-") that is not between two letters or
symbols is used to indicate a point of attachment for a
substituent. For example, --CHO is attached through carbon of the
carbonyl group. In addition, it is to be understood that the
described elements may be combined in any suitable manner in the
various embodiments.
[0199] With respect to the figures, it is noted that these figures
are merely schematic representations based on convenience and the
ease of demonstrating the present disclosure, and are, therefore,
not intended to indicate relative size and dimensions of the
devices or components thereof and/or to define or limit the scope
of the exemplary embodiments. Although specific terms are used in
the description for the sake of clarity, these terms are intended
to refer only to the particular structure of the embodiments
selected for illustration in the drawings, and are not intended to
define or limit the scope of the disclosure. In the drawings and
the description herein, it is to be understood that like numeric
designations refer to components of like function.
[0200] Disclosure of a narrower range in addition to a broader
range is not a disclaimer of the broader range.
[0201] All cited patents, patent applications, and other references
are incorporated herein by reference in their entirety. However, if
a term in the present application contradicts or conflicts with a
term in the incorporated reference, the term from the present
application takes precedence over the conflicting term from the
incorporated reference.
[0202] While this description can include many specifics, these
should not be construed as limitations on the scope thereof, but
rather as descriptions of features that can be specific to
particular embodiments. Certain features that have been heretofore
described in the context of separate embodiments can also be
implemented in combination in a single embodiment. Conversely,
various features that are described in the context of a single
embodiment can also be implemented in multiple embodiments
separately or in any suitable subcombination. Moreover, although
features can be described above as acting in certain combinations
and can even be initially claimed as such, one or more features
from a claimed combination can in some cases be excised from the
combination, and the claimed combination can be directed to a
subcombination or variation of a subcombination.
[0203] Similarly, while operations are depicted in the drawings or
figures in a particular order, this should not be understood as
requiring that such operations be performed in the particular order
shown or in sequential order, or that all illustrated operations be
performed, to achieve desirable results. In certain circumstances,
multitasking and parallel processing can be advantageous.
[0204] As shown by the various configurations and embodiments
illustrated in FIGS. 1-11, various embodiments for methods for
light-weight, high stiffness glass laminate structures have been
described.
[0205] While preferred embodiments of the present disclosure have
been described, it is to be understood that the embodiments
described are illustrative only and that the scope of the invention
is to be defined solely by the appended claims when accorded a full
range of equivalence, many variations and modifications naturally
occurring to those of skill in the art from a perusal hereof
* * * * *