U.S. patent application number 14/299945 was filed with the patent office on 2014-12-11 for polymer interlayers having improved optical properties.
This patent application is currently assigned to SOLUTIA INC.. The applicant listed for this patent is Solutia Inc.. Invention is credited to WENJIE CHEN, JUN LU.
Application Number | 20140363651 14/299945 |
Document ID | / |
Family ID | 51059654 |
Filed Date | 2014-12-11 |
United States Patent
Application |
20140363651 |
Kind Code |
A1 |
LU; JUN ; et al. |
December 11, 2014 |
POLYMER INTERLAYERS HAVING IMPROVED OPTICAL PROPERTIES
Abstract
An interlayer comprised of a thermoplastic resin, at least one
high refractive index plasticizer and, optionally, a conventional
plasticizer. The use of a thermoplastic resin, a high refractive
index plasticizer, and, optionally, a conventional plasticizer
reduces or minimizes the optical defects caused by different
refractive indices without sacrificing other characteristics of the
interlayer.
Inventors: |
LU; JUN; (EAST LONGMEADOW,
MA) ; CHEN; WENJIE; (AMHERST, MA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Solutia Inc. |
St. Louis |
MO |
US |
|
|
Assignee: |
SOLUTIA INC.
ST. LOUIS
MO
|
Family ID: |
51059654 |
Appl. No.: |
14/299945 |
Filed: |
June 9, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61833205 |
Jun 10, 2013 |
|
|
|
Current U.S.
Class: |
428/217 |
Current CPC
Class: |
B32B 27/42 20130101;
C08K 5/13 20130101; B32B 7/02 20130101; B32B 27/08 20130101; B32B
2250/03 20130101; C08L 2205/02 20130101; B32B 2329/06 20130101;
B32B 17/10605 20130101; B32B 27/30 20130101; B32B 2250/246
20130101; C08L 2205/025 20130101; Y10T 428/24983 20150115; B32B
2307/56 20130101; B32B 2605/08 20130101; C08L 29/04 20130101; B32B
2307/412 20130101; B32B 2307/546 20130101; B32B 2307/418 20130101;
C08J 5/18 20130101; C08K 5/12 20130101; B32B 2457/12 20130101; B32B
2605/18 20130101; B32B 27/22 20130101; C08J 2329/14 20130101; C08K
5/101 20130101; C08K 5/11 20130101; B32B 27/306 20130101; C08K
5/0016 20130101; B32B 17/10036 20130101; B32B 17/1055 20130101;
B32B 2307/558 20130101; C08L 29/14 20130101; B32B 2250/02 20130101;
B32B 2419/00 20130101; B32B 17/10761 20130101 |
Class at
Publication: |
428/217 |
International
Class: |
B32B 7/02 20060101
B32B007/02; B32B 27/08 20060101 B32B027/08; B32B 27/30 20060101
B32B027/30 |
Claims
1. A multiple layer polymer interlayer comprising: poly(vinyl
butyral) resin; and at least one high refractive index plasticizer
having a refractive index of at least about 1.460; wherein the
multiple layer polymer interlayer has at least one soft layer and
at least one stiff layer, and wherein the difference between the
refractive index of the soft layer and the stiff layer (Delta RI)
is less than about 0.010.
2. The multiple layer polymer interlayer of claim 1, wherein the
high refractive index plasticizer has a refractive index of from
about 1.460 to about 1.560.
3. The multiple layer polymer interlayer of claim 1, wherein the
soft layer comprises a poly(vinyl butyral) resin having a residual
hydroxyl content from 8 to 21 wt. %, and wherein the stiff layer
comprises a poly(vinyl butyral) resin having a residual hydroxyl
content from 16 to 35 wt. %, and wherein the residual hydroxyl
content between the adjacent soft and stiff layers differs by at
least 2 wt. %.
4. The multiple layer polymer interlayer of claim 1, wherein the
soft layer has a plasticizer content of from 10 phr to 120 phr, and
wherein the stiff layer has a plasticizer content of from 5 phr to
60 phr.
5. The multiple layer polymer interlayer of claim 1, wherein the
polymer interlayer comprises at least two different high refractive
plasticizers, wherein each high refractive index plasticizer has a
refractive index of at least 1.460.
6. The multiple layer polymer interlayer of claim 1, wherein the
polymer interlayer comprises at least two different plasticizers,
wherein at least one plasticizer has a refractive index of at least
1.460 and wherein at least one plasticizer has a refractive index
of less than about 1.450.
7. The multiple layer polymer interlayer of claim 1, wherein the
high refractive index plasticizer is selected from dipropylene
glycol dibenzoate, tripropylene glycol dibenzoate, polypropylene
glycol dibenzoate, isodecyl benzoate, 2-ethylhexyl benzoate,
diethylene glycol benzoate, propylene glycol dibenzoate,
2,2,4-trimethyl-1,3-pentanediol dibenzoate,
2,2,4-trimethyl-1,3-pentanediol benzoate isobutyrate,
1,3-butanediol dibenzoate, 2,2,4-trimethyl-1,3-pentanediol
dibenzoate, diethylene glycol di-o-toluate, triethylene glycol
di-o-toluate, dipropylene glycol di-o-toluate, 1,2-octyl
dibenzoate, tri-2-ethylhexyl trimellitate, di-2-ethylhexyl
terephthalate, bis-phenol A bis(2-ethylhexaonate), ethoxylated
nonylphenol, and mixtures thereof.
8. The multiple layer polymer interlayer of claim 7, wherein the
high refractive index plasticizer is selected from dipropylene
glycol dibenzoate, tripropylene glycol dibenzoate, and
2,2,4-trimethyl-1,3-pentanediol dibenzoate.
9. The multiple layer polymer interlayer of claim 8, further
comprising an additional plasticizer, wherein the additional
plasticizer is triethylene glycol di-(2-ethylhexanoate).
10. The multiple layer polymer interlayer of claim 1, wherein the
multiple layer polymer interlayer further comprises a second stiff
layer, and wherein the soft layer is disposed between the stiff
layers, or a second soft layer and wherein the stiff layer is
disposed between the soft layers.
11. A multiple layer polymer interlayer comprising: poly(vinyl
butyral) resin; and a plasticizer mixture comprising: at least one
plasticizer selected from the group consisting of: triethylene
glycol di-(2-ethylhexanoate), triethylene glycol
di-(2-ethylbutyrate), triethylene glycol diheptanoate,
tetraethylene glycol diheptanoate, tetraethylene glycol
di-(2-ethylhexanoate), dihexyl adipate, dioctyl adipate, hexyl
cyclohexyladipate, diisononyl adipate, heptylnonyl adipate,
di(butoxyethyl) adipate, bis(2-(2-butoxyethoxy)ethyl) adipate,
dibutyl sebacate, and dioctyl sebacate; and at least one high
refractive index plasticizer having a refractive index of at least
1.460; wherein the refractive index of the plasticizer mixture is
at least 1.460; wherein the multiple layer polymer interlayer has
at least one soft layer and at least one stiff layer, and wherein
the difference between the refractive index (Delta RI) of the soft
layer and the stiff layer is less than about 0.010.
12. The multiple layer polymer interlayer of claim 11, wherein the
plasticizer mixture has a refractive index of from about 1.460 to
about 1.560.
13. The multiple layer polymer interlayer of claim 11, wherein the
soft layer comprises a poly(vinyl butyral) resin having a residual
hydroxyl content from 8 to 21 wt. %, and wherein the stiff layer
comprises a poly(vinyl butyral) resin having a residual hydroxyl
content from 16 to 35 wt. %, and wherein the residual hydroxyl
content between the adjacent soft and stiff layers differs by at
least 2 wt. %.
14. The multiple layer polymer interlayer of claim 11, wherein the
soft layer has a plasticizer content of from 10 phr to 120 phr, and
wherein the stiff layer has a plasticizer content of from 5 phr to
60 phr.
15. The multiple layer polymer interlayer of claim 11, wherein the
high refractive index plasticizer is selected from dipropylene
glycol dibenzoate, tripropylene glycol dibenzoate, polypropylene
glycol dibenzoate, isodecyl benzoate, 2-ethylhexyl benzoate,
diethylene glycol benzoate, propylene glycol dibenzoate,
2,2,4-trimethyl-1,3-pentanediol dibenzoate,
2,2,4-trimethyl-1,3-pentanediol benzoate isobutyrate,
1,3-butanediol dibenzoate, 2,2,4-trimethyl-1,3-pentanediol
dibenzoate, diethylene glycol di-o-toluate, triethylene glycol
di-o-toluate, dipropylene glycol di-o-toluate, 1,2-octyl
dibenzoate, tri-2-ethylhexyl trimellitate, di-2-ethylhexyl
terephthalate, bis-phenol A bis(2-ethylhexaonate), ethoxylated
nonylphenol, and mixtures thereof.
16. The multiple layer polymer interlayer of claim 11, wherein the
multiple layer polymer interlayer further comprises a second stiff
layer, and wherein the soft layer is disposed between the stiff
layers or a second soft layer and wherein the stiff layer is
disposed between the soft layers.
17. A multiple layer polymer interlayer comprising: poly(vinyl
butyral) resin; and at least one high refractive index plasticizer
having a refractive index of at least about 1.460; wherein the
multiple layer polymer interlayer has at least one soft layer and
at least two stiff layers wherein the soft layer is disposed
between the stiff layers, and wherein the difference between the
refractive index of the soft layer and the stiff layers is less
than about 0.010.
18. The multiple layer polymer interlayer of claim 17, wherein the
soft layer comprises a poly(vinyl butyral) resin having a residual
hydroxyl content from 8 to 21 wt. %, and wherein the stiff layer
comprises a poly(vinyl butyral) resin having a residual hydroxyl
content from 16 to 35 wt. %, and wherein the residual hydroxyl
content between the adjacent soft and stiff layers differs by at
least 2 wt. %.
19. The multiple layer polymer interlayer of claim 17, wherein the
soft layer has a plasticizer content of from 10 phr to 120 phr, and
wherein the stiff layer has a plasticizer content of from 5 phr to
60 phr.
20. The multiple layer polymer interlayer of claim 17, wherein the
polymer interlayer comprises at least two high different refractive
index plasticizers, wherein each high refractive index plasticizer
has a refractive index of at least 1.460.
Description
CROSS REFERENCE TO RELATED APPLICATION(S)
[0001] This application claims the benefit of U.S. Provisional
Patent Application Ser. No. 61/833,205, filed Jun. 10, 2013, the
entire disclosure of which is incorporated by reference herein.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] This disclosure is related to the field of polymer
interlayers for multiple layer panels and multiple layer panels
having at least one polymer interlayer sheet. Specifically, this
disclosure is related to the field of polymer interlayers having
improved optical properties, and more specifically, to polymer
interlayers comprising a high refractive index plasticizer.
[0004] 2. Description of Related Art
[0005] Multiple layer panels are generally panels comprised of two
sheets of a substrate (such as, but not limited to, glass,
polyester, polyacrylate, or polycarbonate) with one or more polymer
interlayers sandwiched therebetween. The laminated multiple layer
glass panels are commonly utilized in architectural window
applications, in the windows of motor vehicles and airplanes, and
in photovoltaic solar panels. The first two applications are
commonly referred to as laminated safety glass. The main function
of the interlayer in the laminated safety glass is to absorb energy
resulting from impact or force applied to the glass, to keep the
layers of glass bonded even when the force is applied and the glass
is broken, and to prevent the glass from breaking up into sharp
pieces. Additionally, the interlayer may also give the glass a much
higher sound insulation rating, reduce UV and/or IR light
transmission, and enhance the aesthetic appeal of the associated
window. In regard to the photovoltaic applications, the main
function of the interlayer is to encapsulate the photovoltaic solar
panels which are used to generate and supply electricity in
commercial and residential applications.
[0006] The interlayer may be a single layer, a combination of more
than one single layer, a multilayer that has been coextruded, a
combination of at least one single layer and at least one
multilayer, or a combination of multilayer sheets.
[0007] In order to achieve the certain property and performance
characteristics for the glass panel, it has become common practice
to utilize multiple layer or multilayered interlayers. As used
herein, the terms "multilayer" and "multiple layers" mean an
interlayer having more than one layer, and multilayer and multiple
layer may be used interchangeably. Multiple layer interlayers
typically contain at least one soft layer and at least one stiff
layer. Interlayers with one soft "core" layer sandwiched between
two more rigid or stiff "skin" layers have been designed with sound
insulation property for the glass panel. Interlayers having the
reverse configuration, that is, with one stiff layer sandwiched
between two more soft layers have been found to improve the impact
performance of the glass panel. Examples of multiple layer
interlayers also include the interlayers with at least one "clear"
or non-colored layer and at least one colored layer. Other examples
of multiple layer interlayers include interlayers with at least two
layers with different colors. The colored layer typically contains
pigments or dyes or some combination of pigments and dyes. The
layers of the interlayer are generally produced by mixing a polymer
resin such as poly(vinyl butyral) with one or more plasticizers and
melt processing the mix into a sheet by any applicable process or
method known to one of skill in the art, including, but not limited
to, extrusion, with the layers being combined by processes such as
co-extrusion and lamination. Other additional ingredients may
optionally be added for various other purposes. After the
interlayer sheet is formed, it is typically collected and rolled
for transportation and storage and for later use in the multiple
layer glass panel, as discussed below.
[0008] Contemplated polymer interlayers include, but are not
limited to, polyvinyl acetals (PVA) (such as polyvinyl butyral
(PVB)), polyurethane (PU), poly(ethylene-co-vinyl acetate) (EVA),
polyvinylchloride (PVC), polyethylenes, polyolefins, ethylene
acrylate ester copolymers, poly(ethylene-co-butyl acrylate),
silicone elastomers, epoxy resins, and acid copolymers such as
ethylene/carboxylic acid copolymers and its ionomers, derived from
any of the foregoing possible thermoplastic resins. Multilayer
laminates can include multiple layer glass panels and multilayer
polymer films. In certain embodiments, the multiple polymer films
in the multilayer laminates may be laminated together to provide a
multilayer film or interlayer. In certain embodiments, these
polymer films may have coatings, such as metal, silicone or other
applicable coatings known to those of ordinary skill in the art.
The individual polymer films which comprise the multilayer polymer
films may be laminated together using an adhesive as known to those
of ordinary skill in the art. The following offers a simplified
description of the manner in which multiple layer glass panels are
generally produced in combination with the interlayers. First, at
least one polymer interlayer sheet (single or multilayer) is placed
between two substrates and any excess interlayer is trimmed from
the edges, creating an assembly. It is not uncommon for multiple
polymer interlayer sheets or a polymer interlayer sheet with
multiple layers (or a combination of both) to be placed within the
two substrates creating a multiple layer glass panel with multiple
polymer interlayers. Then, air is removed from the assembly by an
applicable process or method known to one of skill in the art;
e.g., through nip rollers, vacuum bag or another deairing
mechanism. Additionally, the interlayer is partially press-bonded
to the substrates by any method known to one of ordinary skill in
the art. In a last step, in order to form a final unitary
structure, this preliminary bonding is rendered more permanent by a
high temperature and pressure lamination process, or any other
method known to one of ordinary skill in the art such as, but not
limited to, autoclaving.
[0009] One of the problems in the manufacture of multilayer
laminate glass panels having multiple layer interlayers is the
presence of mottle in the final unitary structure. The term
"mottle" refers to an objectionable visual defect in the final
unitary structure, namely the appearance of uneven spots, a form of
optical distortion. Stated differently, mottle is a measure of the
graininess or texture formed from the optical effect of reflecting
non-uniform distorted interfaces of the inner polymer interlayer or
polymer interlayers.
[0010] In multiple layer interlayers having at least one soft layer
and at least one stiff layer, the mottle is caused by small scale
surface variations at the interfaces between the layers wherein the
individual layers (or the soft and stiff layers) have different
refractive indices. When the polymer interlayer is produced,
surface roughness is formed at the utmost surface of the polymer
interlayer through melt fracture or embossing or both. The surface
roughness enables and improves removal of air during laminating of
polymer interlayers to produce multiple layer glass panels, and
helps to prevent the blocking of the polymer interlayers during
storage. Meanwhile, such surface roughness will also cause the
development of small scale surface variation at the interfaces
between layers of the multilayer interlayer.
[0011] The refractive index of a substance, such as an interlayer,
is the measure of the speed of light through the substance with
respect to the speed of light in vacuum. If there is a difference
between the refractive index of the layers, the result will be that
the surface variations are visible or even more visible due to
diffraction of the light at the layer interfaces. Mottle is
theoretically possible with any multiple layer interlayer,
especially where there is a sufficiently large difference in the
refractive indices between the layers and there is some degree of
interfacial variation between the layers.
[0012] The presence of mottle in the final unitary structure of a
multilayer laminate glass panel can be problematic because a
certain degree of optical quality is necessary in many (if not
most) of the end-use commercial applications of multilayer laminate
glass panels (e.g., vehicular, aeronautical and architectural
applications). Thus, the creation of multilayer laminate glass
panels with commercially acceptable levels of mottle (that is,
where the level of mottle is low) is paramount in the art of
multiple layer glass panel manufacturing.
[0013] To ascertain the level of mottle in a laminate, the severity
of the mottle is assessed and categorized by a side-to-side
qualitative comparison of the shadowgraph projections for a test
laminate with a set of standard laminate shadowgraphs representing
a series or scale of mottle values ranging from 1 to 4, with 1
representing a standard of low mottle (i.e., a low number of
disruptions) and 4 representing a standard of high mottle (i.e., a
high number of disruptions), which is optically objectionable.
Based upon a visual interpretation of which standard laminate
shadowgraph picture the test shadowgraph projection best
corresponds with, the test laminate is then placed into the mottle
category of the corresponding standard laminate. Shadowgraph
pictures can also be analyzed by digital image analysis tools to
give digitalized results or mottle ratings.
[0014] Clarity of the multiple layer panel is another important
optical quality. Clarity is determined by measuring the level of
haze in the multiple layer panel, as further described below. The
level of haze must be very low so that the multiple layer panel is
clear. In addition to haze, there are other optical quality
defects, such as visible optical defects in the interlayer, that
cause light scattering and make the defect visible to the eye that
may cause optical distortion in the glass panel as well. Both haze
and other visible optical defects are caused by light scattering
due to the blending or mixing of materials, such as different
polymers or plasticizers, together, or the contamination from such
different polymers or plasticizers where there is a sufficiently
large difference in the refractive index between the different
polymers or plasticizers, the matrix and the contaminants, or
both.
[0015] Summarized, optical quality defects such as mottle, haze and
other visible optical defects are common problems in the field of
multiple layer glass panels, particularly those used in
applications which require higher levels of optical or visual
quality. It is now common to use a multilayer interlayer in order
to provide high performance laminates. The use of multilayer
interlayers, however, has very often resulted in having optical
defect problems, such as mottle. Accordingly, there is a need in
the art for the development of an interlayer, and particularly a
multilayer interlayer, that resists or prevents the formation of
mottle without a reduction in other optical, mechanical, and
acoustic characteristics of a multilayer interlayer, and a need for
the development of any polymer interlayers including monolithic and
multilayer interlayers that are free from haze and other visible
optical defects.
SUMMARY OF THE INVENTION
[0016] Because of these and other problems in the art, described
herein, among other things is a polymer interlayer comprising: a
poly(vinyl butyral) resin; and at least one high refractive index
plasticizer. The polymer interlayer may be a multilayer polymer
interlayer.
[0017] In an embodiment, a polymer interlayer comprises: poly(vinyl
butyral) resin; and at least one high refractive index plasticizer
having a refractive index of at least about 1.460; wherein the
interlayer comprises about 5 to about 120 parts of the high
refractive index plasticizer mixture per 100 parts poly(vinyl
butyral) resin. In an embodiment, the high refractive index
plasticizer has a refractive index of at least about 1.470. In an
embodiment, the high refractive index plasticizer has a refractive
index of at least about 1.480. In an embodiment, the high
refractive index plasticizer has a refractive index of at least
about 1.490. In an embodiment, the high refractive index
plasticizer has a refractive index of from about 1.460 to about
1.560. In an embodiment, the difference between the refractive
index of the resin and the refractive index of the high refractive
index plasticizer is less than about 0.100, or less than about
0.075. In an embodiment, the difference between the refractive
index of the resin and the refractive index of the high refractive
index plasticizer is less than about 0.050. In an embodiment, the
polymer interlayer comprises at least two different high refractive
index plasticizers, wherein each high refractive index plasticizer
has a refractive index of at least 1.460. In an embodiment, the
polymer interlayer comprises at least two different plasticizers,
wherein at least one plasticizer has a refractive index of at least
1.460 and wherein at least one plasticizer has a refractive index
of less than about 1.450. In an embodiment, the high refractive
index plasticizer is selected from dipropylene glycol dibenzoate,
tripropylene glycol dibenzoate, polypropylene glycol dibenzoate,
isodecyl benzoate, 2-ethylhexyl benzoate, diethylene glycol
benzoate, propylene glycol dibenzoate,
2,2,4-trimethyl-1,3-pentanediol dibenzoate,
2,2,4-trimethyl-1,3-pentanediol benzoate isobutyrate,
1,3-butanediol dibenzoate, 2,2,4-trimethyl-1,3-pentanediol
dibenzoate, diethylene glycol di-o-toluate, triethylene glycol
di-o-toluate, dipropylene glycol di-o-toluate, 1,2-octyl
dibenzoate, tri-2-ethylhexyl trimellitate, di-2-ethylhexyl
terephthalate, bis-phenol A bis(2-ethylhexaonate), ethoxylated
nonylphenol, and mixtures thereof. In an embodiment, the high
refractive index plasticizer is selected from dipropylene glycol
dibenzoate, 2,2,4-trimethyl-1,3-pentanediol dibenzoate, and
tripropylene glycol dibenzoate. In an embodiment, the polymer
interlayer further comprises a second plasticizer, wherein the
second plasticizer is triethylene glycol di-(2-ethylhexanoate). In
an embodiment, the refractive index of the polymer interlayer is at
least 1.480.
[0018] In an embodiment, a polymer interlayer comprises: poly(vinyl
butyral) resin; and a plasticizer mixture comprising: at least one
plasticizer having a refractive index of less than about 1.450; and
at least one high refractive index plasticizer having a refractive
index of at least 1.460; wherein the refractive index of the
plasticizer mixture is at least 1.460; and wherein the interlayer
comprises about 5 to about 120 parts plasticizer mixture per 100
parts poly(vinyl butyral) resin. In an embodiment, the refractive
index of the plasticizer mixture is at least 1.480. In an
embodiment, the refractive index of the polymer interlayer is at
least 1.480.
[0019] In an embodiment, a polymer interlayer comprises: poly(vinyl
butyral) resin; and at least one high refractive index plasticizer
having a refractive index of at least about 1.460; wherein the
interlayer comprises about 5 to about 120 parts of the high
refractive index plasticizer mixture per 100 parts poly(vinyl
butyral) resin, and wherein the refractive index of the polymer
interlayer is at least 1.480. In an embodiment, the difference
between the refractive index of the resin and the refractive index
of the high refractive index plasticizer is less than about 0.100,
or less than about 0.075. In an embodiment, the difference between
the refractive index of the resin and the refractive index of the
high refractive index plasticizer is less than about 0.050. In an
embodiment, the polymer interlayer comprises at least two different
high refractive index plasticizers, wherein each high refractive
index plasticizer has a refractive index of at least 1.460. In an
embodiment, the polymer interlayer comprises at least two
plasticizers, wherein at least one plasticizer has a refractive
index of at least 1.460 and wherein at least one plasticizer has a
refractive index of less than about 1.450.
[0020] In an embodiment, a multiple layer polymer interlayer
comprises: poly(vinyl butyral) resin; and at least one high
refractive index plasticizer having a refractive index of at least
about 1.460; wherein the multiple layer polymer interlayer has at
least one soft layer and at least one stiff layer, and wherein the
difference between the refractive index of the soft layer and the
stiff layer (Delta RI) is less than about 0.010. In embodiments,
the high refractive index plasticizer has a refractive index of
from about 1.460 to about 1.560. In embodiments, the soft layer
comprises a poly(vinyl butyral) resin having a residual hydroxyl
content from 8 to 21 wt. %, and the stiff layer comprises a
poly(vinyl butyral) resin having a residual hydroxyl content from
16 to 35 wt. %, and the residual hydroxyl content between the
adjacent soft and stiff layers differs by at least 2 wt. %. In
embodiments, the soft layer has a plasticizer content of from 10
phr to 120 phr, and the stiff layer has a plasticizer content of
from 5 phr to 60 phr. In embodiments, the polymer interlayer
comprises at least two different high refractive plasticizers,
wherein each high refractive plasticizer has a refractive index of
at least 1.460. In embodiments, the polymer interlayer comprises at
least two different plasticizers, wherein at least one plasticizer
has a refractive index of at least 1.460 and wherein at least
plasticizer has a refractive index of less than about 1.450. In
embodiments, the high refractive index plasticizer is selected from
dipropylene glycol dibenzoate, tripropylene glycol dibenzoate,
polypropylene glycol dibenzoate, isodecyl benzoate, 2-ethylhexyl
benzoate, diethylene glycol benzoate, propylene glycol dibenzoate,
2,2,4-trimethyl-1,3-pentanediol dibenzoate,
2,2,4-trimethyl-1,3-pentanediol benzoate isobutyrate,
1,3-butanediol dibenzoate, 2,2,4-trimethyl-1,3-pentanediol
dibenzoate, diethylene glycol di-o-toluate, triethylene glycol
di-o-toluate, dipropylene glycol di-o-toluate, 1,2-octyl
dibenzoate, tri-2-ethylhexyl trimellitate, di-2-ethylhexyl
terephthalate, bis-phenol A bis(2-ethylhexaonate), ethoxylated
nonylphenol, and mixtures thereof. In embodiments, the high
refractive index plasticizer is selected from dipropylene glycol
dibenzoate, tripropylene glycol dibenzoate, and
2,2,4-trimethyl-1,3-pentanediol dibenzoate. In embodiments, the
multiple layer polymer interlayer further comprises a second
plasticizer, wherein the second plasticizer is triethylene glycol
di-(2-ethylhexanoate). In embodiments, the multiple layer polymer
interlayer further comprises a second stiff layer, and wherein the
soft layer is disposed between the stiff layers, or a second soft
layer and wherein the stiff layer is disposed between the soft
layers.
[0021] In an embodiment, a polymer interlayer is disclosed, the
polymer interlayer comprising: poly(vinyl butyral) resin; and at
least one high refractive index plasticizer having a refractive
index of at least about 1.460; wherein the interlayer comprises
about 5 to about 120 parts of the high refractive index plasticizer
per 100 parts poly(vinyl butyral) resin. In embodiments, the
multiple layer polymer interlayer has at least one soft layer and
at least one stiff layer, and wherein the difference between the
refractive index of the soft layer and the stiff layer (Delta RI)
is less than about 0.010.
[0022] In embodiments, the high refractive index plasticizer has a
refractive index of at least about 1.470, or at least about 1.480,
or at least about 1.490, or at least about 1.500, or at least about
1.510, or at least about 1.520.
[0023] In embodiments, the difference between the refractive index
of the resin and the refractive index of the plasticizer may be
less than about 0.100, or less than about 0.075, or less than about
0.070, or less than about 0.065, or less than about 0.060, or less
than about 0.055, or less than about 0.050, or less than about
0.040, or less than about 0.030, or less than about 0.020, or less
than about 0.010, or about 0.000.
[0024] In embodiments, the polymer interlayer may comprise at least
two different high refractive index plasticizers, wherein each high
refractive index plasticizer has a refractive index of at least
1.460, or the polymer interlayer may comprise at least two
different plasticizers, wherein at least one plasticizer has a
refractive index of at least 1.460 and wherein at least plasticizer
has a refractive index of less than about 1.450.
[0025] In embodiments, the polymer interlayer has a refractive
index of at least 1.480, or at least 1.485.
[0026] In embodiments, the high refractive index plasticizer is
selected from dipropylene glycol dibenzoate, tripropylene glycol
dibenzoate, polypropylene glycol dibenzoate, isodecyl benzoate,
2-ethylhexyl benzoate, diethylene glycol benzoate, propylene glycol
dibenzoate, 2,2,4-trimethyl-1,3-pentanediol dibenzoate,
2,2,4-trimethyl-1,3-pentanediol benzoate isobutyrate,
1,3-butanediol dibenzoate, diethylene glycol di-o-toluate,
triethylene glycol di-o-toluate, dipropylene glycol di-o-toluate,
1,2-octyl dibenzoate, tri-2-ethylhexyl trimellitate,
di-2-ethylhexyl terephthalate, bis-phenol A bis(2-ethylhexaonate),
ethoxylated nonylphenol, and mixtures thereof, or the plasticizer
may be selected from dipropylene glycol dibenzoate,
2,2,4-trimethyl-1,3-pentanediol dibenzoate, and tripropylene glycol
dibenzoate.
[0027] In embodiments, the polymer interlayer may further comprise
an additional plasticizer. In embodiments, the additional
plasticizer is triethylene glycol di-(2-ethylhexanoate).
[0028] In embodiments, the soft layer comprises a poly(vinyl
butyral) resin having a residual hydroxyl content from 8 to 21 wt.
%, and the stiff layer comprises a poly(vinyl butyral) resin having
a residual hydroxyl content from 16 to 35 wt. %, and the residual
hydroxyl content between the adjacent soft and stiff layers differs
by at least 2 wt. %.
[0029] In another embodiment, a multiple layer polymer interlayer
comprises: poly(vinyl butyral) resin; and a plasticizer mixture
comprising: at least one plasticizer selected from the group
consisting of: triethylene glycol di-(2-ethylhexanoate),
triethylene glycol di-(2-ethylbutyrate), triethylene glycol
diheptanoate, tetraethylene glycol diheptanoate, tetraethylene
glycol di-(2-ethylhexanoate), dihexyl adipate, dioctyl adipate,
hexyl cyclohexyladipate, diisononyl adipate, heptylnonyl adipate,
di(butoxyethyl) adipate, bis(2-(2-butoxyethoxy)ethyl) adipate,
dibutyl sebacate, and dioctyl sebacate; and at least one high
refractive index plasticizer having a refractive index of at least
1.460; wherein the refractive index of the plasticizer mixture is
at least 1.460; wherein the multiple layer polymer interlayer has
at least one soft layer and at least one stiff layer, and wherein
the difference between the refractive index (Delta RI) of the soft
layer and the stiff layer is less than about 0.010. In embodiments,
the plasticizer mixture has a refractive index of from about 1.460
to about 1.560. In embodiments, the soft layer comprises a
poly(vinyl butyral) resin having a residual hydroxyl content from 8
to 21 wt. %, and the stiff layer comprises a poly(vinyl butyral)
resin having a residual hydroxyl content from 16 to 35 wt. %, and
the residual hydroxyl content between the adjacent soft and stiff
layers differs by at least 2 wt. %. In embodiments, the soft layer
has a plasticizer content of from 10 phr to 120 phr, and the stiff
layer has a plasticizer content of from 5 phr to 60 phr. In
embodiments, the high refractive index plasticizer is selected from
dipropylene glycol dibenzoate, tripropylene glycol dibenzoate,
polypropylene glycol dibenzoate, isodecyl benzoate, 2-ethylhexyl
benzoate, diethylene glycol benzoate, propylene glycol dibenzoate,
2,2,4-trimethyl-1,3-pentanediol dibenzoate,
2,2,4-trimethyl-1,3-pentanediol benzoate isobutyrate,
1,3-butanediol dibenzoate, 2,2,4-trimethyl-1,3-pentanediol
dibenzoate, diethylene glycol di-o-toluate, triethylene glycol
di-o-toluate, dipropylene glycol di-o-toluate, 1,2-octyl
dibenzoate, tri-2-ethylhexyl trimellitate, di-2-ethylhexyl
terephthalate, bis-phenol A bis(2-ethylhexaonate), ethoxylated
nonylphenol, and mixtures thereof. In embodiments, the multiple
layer polymer interlayer further comprises a second stiff layer,
and wherein the soft layer is disposed between the stiff layers or
a second soft layer and wherein the stiff layer is disposed between
the soft layers.
[0030] In another embodiment, a multiple layer polymer interlayer
comprises: poly(vinyl butyral) resin; and at least one high
refractive index plasticizer having a refractive index of at least
about 1.460; wherein the multiple layer polymer interlayer has at
least one soft layer and at least two stiff layers wherein the soft
layer is disposed between the stiff layers, and wherein the
difference between the refractive index of the soft layer and the
stiff layers is less than about 0.010. In embodiments, the soft
layer comprises a poly(vinyl butyral) resin having a residual
hydroxyl content from 8 to 21 wt. %, and the stiff layer comprises
a poly(vinyl butyral) resin having a residual hydroxyl content from
16 to 35 wt. %, and the residual hydroxyl content between the
adjacent soft and stiff layers differs by at least 2 wt. %. In
embodiments, the soft layer has a plasticizer content of from 10
phr to 120 phr, and the stiff layer has a plasticizer content of
from 5 phr to 60 phr. In embodiments, the polymer interlayer
comprises at least two different high refractive index
plasticizers, wherein each high refractive index plasticizer has a
refractive index of at least 1.460.
[0031] In another embodiment, a multiple layer polymer interlayer
comprises: poly(vinyl butyral) resin; and at least one high
refractive index plasticizer having a refractive index of at least
about 1.460; wherein the multiple layer polymer interlayer has at
least one soft layer and at least one stiff layer, and wherein the
difference between the refractive index of the soft layer and the
stiff layer (Delta RI) is less than about 0.010.
[0032] In another embodiment, a polymer interlayer comprising:
poly(vinyl butyral) resin; and a plasticizer mixture comprising: at
least one plasticizer selected from the group consisting of:
triethylene glycol di-(2-ethylhexanoate), triethylene glycol
di-(2-ethylbutyrate), triethylene glycol diheptanoate,
tetraethylene glycol diheptanoate, tetraethylene glycol
di-(2-ethylhexanoate), dihexyl adipate, dioctyl adipate, hexyl
cyclohexyladipate, diisononyl adipate, heptylnonyl adipate, dibutyl
sebacate, dioctyl sebacate; and at least one high refractive index
plasticizer having a refractive index of at least 1.460; wherein
the refractive index of the plasticizer mixture is at least 1.460;
and wherein the interlayer comprises about 5 to about 120 parts
plasticizer mixture per 100 parts poly(vinyl butyral) resin is
disclosed. In embodiments, the high refractive index plasticizer
has a refractive index of at least about 1.470, or at least about
1.480, or at least about 1.490, or at least about 1.500, or at
least about 1.510, or at least about 1.520. In embodiments, the
refractive index of the plasticizer mixture is at least about
1.470, or at least about 1.480, or at least about 1.490. In
embodiments, the polymer interlayer has a refractive index of at
least 1.480, or at least 1.485. In embodiments, at least one
plasticizer is triethylene glycol di-(2-ethylhexanoate). In certain
embodiments, the high refractive index plasticizer is selected from
dipropylene glycol dibenzoate, tripropylene glycol dibenzoate,
polypropylene glycol dibenzoate, isodecyl benzoate, 2-ethylhexyl
benzoate, diethylene glycol benzoate, propylene glycol dibenzoate,
2,2,4-trimethyl-1,3-pentanediol dibenzoate,
2,2,4-trimethyl-1,3-pentanediol benzoate isobutyrate,
1,3-butanediol dibenzoate, diethylene glycol di-o-toluate,
triethylene glycol di-o-toluate, dipropylene glycol di-o-toluate,
1,2-octyl dibenzoate, tri-2-ethylhexyl trimellitate,
di-2-ethylhexyl terephthalate, bis-phenol A bis(2-ethylhexaonate),
ethoxylated nonylphenol, and mixtures thereof, or the high
refractive index plasticizer is selected from dipropylene glycol
dibenzoate, 2,2,4-trimethyl-1,3-pentanediol dibenzoate, and
tripropylene glycol dibenzoate, or one plasticizer is triethylene
glycol di-(2-ethylhexanoate) and the high refractive index
plasticizer is selected from dipropylene glycol dibenzoate,
2,2,4-trimethyl-1,3-pentanediol dibenzoate, and tripropylene glycol
dibenzoate.
[0033] A multiple layer polymer interlayer comprising: poly(vinyl
butyral) resin; and at least one high refractive index plasticizer
having a refractive index of at least about 1.460; wherein the
multiple layer polymer interlayer has at least one soft layer and
at least one stiff layer, and wherein the difference between the
refractive index of the soft layer and the stiff layer is less than
about 0.010 is also disclosed. In embodiments, the difference
between the refractive index of the soft layer and the stiff layer
is less than about 0.009, less than about 0.008, less than about
0.007, less than about 0.006, less than about 0.005, less than
about 0.004, less than about 0.003, less than about 0.002, less
than about 0.001, or about 0.000. The plasticizer may have a
refractive index of at least about 1.470, or at least about 1.480,
or at least about 1.490, or at least about 1.500, or at least about
1.510, or at least about 1.520. In embodiments, the polymer
interlayer has a refractive index of at least 1.480. In
embodiments, the polymer interlayer comprises at least two
different high refractive index plasticizers, wherein each high
refractive index plasticizer has a refractive index of at least
1.460, or the polymer interlayer comprises at least two different
plasticizers, wherein at least one plasticizer has a refractive
index of at least 1.460 and wherein at least one plasticizer has a
refractive index of less than about 1.450. The high refractive
index plasticizer may be selected from dipropylene glycol
dibenzoate, tripropylene glycol dibenzoate, polypropylene glycol
dibenzoate, isodecyl benzoate, 2-ethylhexyl benzoate, diethylene
glycol benzoate, propylene glycol dibenzoate,
2,2,4-trimethyl-1,3-pentanediol dibenzoate,
2,2,4-trimethyl-1,3-pentanediol benzoate isobutyrate,
1,3-butanediol dibenzoate, diethylene glycol di-o-toluate,
triethylene glycol di-o-toluate, dipropylene glycol di-o-toluate,
1,2-octyl dibenzoate, tri-2-ethylhexyl trimellitate,
di-2-ethylhexyl terephthalate, bis-phenol A bis(2-ethylhexaonate),
ethoxylated nonylphenol, and mixtures thereof, or the high
refractive index plasticizer may be selected from dipropylene
glycol dibenzoate, 2,2,4-trimethyl-1,3-pentanediol dibenzoate, and
tripropylene glycol dibenzoate. In an embodiment, the polymer
interlayer may further comprise an additional plasticizer. In an
embodiment, the additional plasticizer is triethylene glycol
di-(2-ethylhexanoate). In an embodiment, the polymer interlayer may
further comprise a second stiff layer, and wherein the soft layer
is disposed between the two stiff layers. In an embodiment, the
polymer interlayer may further comprise a second soft layer,
wherein the stiff layer is disposed between the two soft layers. In
embodiments, the polymer interlayer may comprise additional soft
and/or stiff layers.
[0034] In another embodiment, a multiple layer polymer interlayer
is disclosed, the multiple layer polymer interlayer comprising:
poly(vinyl butyral) resin; and a plasticizer mixture comprising: at
least one plasticizer selected from the group consisting of:
triethylene glycol di-(2-ethylhexanoate), triethylene glycol
di-(2-ethylbutyrate), triethylene glycol diheptanoate,
tetraethylene glycol diheptanoate, tetraethylene glycol
di-(2-ethylhexanoate), dihexyl adipate, dioctyl adipate, hexyl
cyclohexyladipate, diisononyl adipate, heptylnonyl adipate, dibutyl
sebacate, dioctyl sebacate, di(butoxyethyl) adipate, and
bis(2-(2-butoxyethoxy)ethyl) adipate; and at least one high
refractive index plasticizer having a refractive index of at least
1.460; wherein the refractive index of the plasticizer mixture is
at least about 1.460; wherein the multiple layer polymer interlayer
has at least one soft layer and at least one stiff layer, and
wherein the difference between the refractive index of the soft
layer and the stiff layer is less than about 0.010. The difference
between the refractive index of the soft layer and the stiff layer
may be less than about 0.009, less than about 0.008, less than
about 0.007, less than about 0.006, less than about 0.005, less
than about 0.004, less than about 0.003, less than about 0.002,
less than about 0.001, or about 0.000. In an embodiment, the
polymer interlayer may further comprise a second stiff layer, and
wherein the soft layer is disposed between the two stiff layers. In
an embodiment, the polymer interlayer may further comprise a second
soft layer, wherein the stiff layer is disposed between the two
soft layers. In embodiments, the polymer interlayer may comprise
additional soft and/or stiff layers.
[0035] In another embodiment, a multiple layer polymer interlayer
comprises: poly(vinyl butyral) resin; and at least one high
refractive index plasticizer having a refractive index of at least
about 1.460; wherein the multiple layer polymer interlayer has at
least one soft layer and at least two stiff layers wherein the soft
layer is disposed between the stiff layers, and wherein the
difference between the refractive index of the soft layer and the
stiff layers is less than about 0.010. In embodiments, the soft
layer comprises a poly(vinyl butyral) resin having a residual
hydroxyl content from 8 to 21 wt. %, and the stiff layer comprises
a poly(vinyl butyral) resin having a residual hydroxyl content from
16 to 35 wt. %, and the residual hydroxyl content between the
adjacent soft and stiff layers differs by at least 2 wt. %. In
embodiments, the soft layer has a plasticizer content of from 10
phr to 120 phr, and the stiff layer has a plasticizer content of
from 5 phr to 60 phr. In embodiments, the polymer interlayer
comprises at least two different high refractive index
plasticizers, wherein each high refractive index plasticizer has a
refractive index of at least 1.460.
[0036] In an embodiment, a multiple layer polymer interlayer
comprises: a first layer comprising poly(vinyl butyral) resin and a
first plasticizer; a second layer comprising poly(vinyl butyral)
resin and a second plasticizer; and a third layer comprising
poly(vinyl butyral) resin and a third plasticizer disposed between
the first layer and the second layer; and wherein at least one of
the first, second and third plasticizers is a high refractive index
plasticizer having a refractive index of at least about 1.460;
wherein at least one layer is a soft layer and at least one layer
is a stiff layer, and wherein the difference between the refractive
index of the soft layer and the stiff layer (Delta RI) is less than
about 0.010. In an embodiment, the high refractive index
plasticizer has a refractive index of from about 1.460 to about
1.560. In an embodiment, the soft layer comprises a poly(vinyl
butyral) resin having a residual hydroxyl content from 8 to 21 wt.
%, and the stiff layer comprises a poly(vinyl butyral) resin having
a residual hydroxyl content from 16 to 35 wt. %, and the residual
hydroxyl content between the adjacent soft and stiff layers differs
by at least 2 wt. %. In an embodiment, the soft layer has a
plasticizer content of from 10 phr to 120 phr, and the stiff layer
has a plasticizer content of from 5 phr to 60 phr. In an
embodiment, the multiple layer interlayer comprises at least two
different high refractive plasticizers, wherein each high
refractive index plasticizer has a refractive index of at least
1.460. In an embodiment, the at least two high refractive
plasticizers are in the same layer. In another embodiment, the at
least two high refractive plasticizers are in different layers. In
an embodiment, the multilayer interlayer comprises at least two
different plasticizers, wherein at least one plasticizer has a
refractive index of at least 1.460 and wherein at least one
plasticizer has a refractive index of less than about 1.450. In an
embodiment, the first and second layers comprise at least one
plasticizer having a refractive index of at least 1.460, and
wherein the third layer comprises at least one plasticizer having a
refractive index of less than 1.450. In an embodiment, the third
layer comprises at least one plasticizer having a refractive index
of at least 1.460, and wherein the first and second layers comprise
at least one plasticizer having a refractive index of less than
1.450. In an embodiment, the first and second layers are stiff
layers, and wherein the third layer is a soft layer. In an
embodiment, the first and second layers are soft layers, and
wherein the third layer is a stiff layer.
[0037] In an embodiment, a multiple layer polymer interlayer
comprises: a first layer comprising poly(vinyl butyral) resin and a
first plasticizer; a second layer comprising poly(vinyl butyral)
resin and a second plasticizer; and a third layer comprising
poly(vinyl butyral) resin and a third plasticizer disposed between
the first layer and the second layer; wherein at least one of the
first, second and third plasticizers is a mixture comprising: at
least one plasticizer having a refractive index of less than about
1.450; and at least one high refractive index plasticizer having a
refractive index of at least 1.460; wherein the refractive index of
the plasticizer mixture is at least 1.460; wherein at least one of
the layers is a soft layer and at least one of the layers is a
stiff layer, and wherein the difference between the refractive
index (Delta RI) of the soft layer and the stiff layer is less than
about 0.010. In an embodiment, the plasticizer mixture has a
refractive index of from about 1.460 to about 1.560. In an
embodiments, the soft layer comprises a poly(vinyl butyral) resin
having a residual hydroxyl content from 8 to 21 wt. %, and the
stiff layer comprises a poly(vinyl butyral) resin having a residual
hydroxyl content from 16 to 35 wt. %, and the residual hydroxyl
content between the adjacent soft and stiff layers differs by at
least 2 wt. %. In an embodiment, the soft layer has a plasticizer
content of from 10 phr to 120 phr, and the stiff layer has a
plasticizer content of from 5 phr to 60 phr.
[0038] In an embodiment, a multiple layer polymer interlayer
comprises: a first stiff layer comprising poly(vinyl butyral) resin
and a first plasticizer, wherein the first plasticizer is present
in an amount of from 5 phr to 60 phr; a second stiff layer
comprising poly(vinyl butyral) resin and a second plasticizer,
wherein the second plasticizer is present in an amount of from 5
phr to 60 phr; and a first soft layer comprising poly(vinyl
butyral) resin and a third plasticizer, wherein the third
plasticizer is present in an amount of from 10 phr to 120 phr, and
wherein the first soft layer is disposed between the first stiff
layer and the second stiff layer; wherein at least one of the
first, second and third plasticizers is a high refractive index
plasticizer having a refractive index of at least about 1.460;
wherein the difference between the refractive index of the soft
layer and the stiff layers is less than about 0.010. In
embodiments, the soft layer comprises a poly(vinyl butyral) resin
having a residual hydroxyl content from 8 to 21 wt. %, and the
stiff layer comprises a poly(vinyl butyral) resin having a residual
hydroxyl content from 16 to 35 wt. %, and the residual hydroxyl
content between the adjacent soft and stiff layers differs by at
least 2 wt. %. In embodiments, the polymer interlayer comprises at
least two different high refractive index plasticizers, wherein
each high refractive index plasticizer has a refractive index of at
least 1.460. In embodiments, the multilayer interlayer comprises at
least two different plasticizers, wherein at least one plasticizer
has a refractive index of at least 1.460 and wherein at least one
plasticizer has a refractive index of less than about 1.450.
[0039] A multiple layer panel is also disclosed. The multiple layer
panel comprises at least one rigid substrate, and a polymer
interlayer or multiple layer polymer interlayer as disclosed
herein. The panel has improved optical properties.
[0040] A method of making a polymer interlayer is also disclosed,
wherein the multilayer interlayer comprises a poly(vinyl butyral)
resin and at least one high refractive index plasticizer, as
disclosed herein. The polymer interlayer may be a multiple layer
polymer interlayer.
[0041] In certain embodiments, the rigid substrate is glass. In
other embodiments, the panel may further comprise a photovoltaic
cell, with the interlayer encapsulating the photovoltaic cell.
DESCRIPTION OF THE PREFERRED EMBODIMENT(S)
[0042] Described herein, among other things, are interlayers
comprised of a thermoplastic resin, at least one high refractive
index plasticizer, and optionally a conventional plasticizer,
wherein the interlayers have improved optical quality. Also
described are multiple layer glass panels comprising the
interlayers, and methods of making the polymer interlayers. The use
of a thermoplastic resin, and at least one high refractive index
plasticizer having a refractive index of at least about 1.460, or
at least about 1.470, or greater than about 1.470, or at least
about 1.480, or greater than about 1.480, or at least about 1.490,
or greater than about 1.490, or at least about 1.500, or greater
than about 1.500, or at least about 1.510, or greater than 1.520,
creates an interlayer having decreased mottle and/or low haze
without sacrificing other characteristics. In this regard, the use
of at least one high refractive index plasticizer or combination of
plasticizers, when selected to have a certain refractive index
compared to interlayers comprising only conventional plasticizer,
and the resin and other additives, results in an interlayer having
excellent optical properties as measured by at least mottle and
haze. As a result, higher quality, optically clear multiple layer
glass panels are produced, less scrap or off grade material is
generated, and operational efficiency is improved. As noted here,
the refractive index (also known as index of refraction) of a
plasticizer or a resin used in the entirety of this disclosure is
either measured in accordance with ASTM D542 at a wavelength of 589
nm and 25.degree. C. or reported in literature in accordance with
the ASTM D542.
[0043] Multilayer interlayers, such as an interlayer having two or
more layers (such as a trilayer interlayer having three layers),
often comprise at least one soft layer and at least one stiff
layer. The soft layer(s) is often the inner or core layer in
interlayers having at least three layers. The soft core layer(s)
may be specifically designed for acoustic attenuation, and the
polymer interlayer may have stiffer skin or outer layers. In the
interlayer comprising poly(vinyl butyral) ("PVB") resin and
plasticizer, it has been common that plasticizer is selected the
group of triethylene glycol di-(2-ethylhexanoate) ("3GEH"),
triethylene glycol di-(2-ethylbutyrate), triethylene glycol
diheptanoate, tetraethylene glycol diheptanoate, tetraethylene
glycol di-(2-ethylhexanoate), dihexyl adipate, dioctyl adipate,
hexyl cyclohexyladipate, diisononyl adipate, heptylnonyl adipate,
dibutyl sebacate, dioctyl sebacate, di(butoxyethyl) adipate, and
bis(2-(2-butoxyethoxy)ethyl) adipate, and mixtures thereof. These
plasticizers have refractive indices of 1.442 to 1.449. As used
herein, the plasticizer having a refractive index of about 1.450 or
less is referred as "conventional plasticizer". 3GEH (refractive
index=1.442) is the most common plasticizer present in interlayers
manufactured for various properties and applications. In the
multilayer interlayer having conventional plasticizer, the
plasticizer (such as triethylene glycol di-(2-ethylhexanoate)
(3GEH)) in the core and skin layers often partitions (as it reaches
equilibrium state) in favor of the softer layer over the stiffer or
harder layer, in a proportion predominated by the characteristics
of the particular resins used in the skin and core layers. Because
PVB resin has a refractive index of approximately 1.485 to 1.495,
and because more plasticizer ends up in the softer layer than in
the stiffer layer, the softer layer has a different, and lower,
refractive index than the stiffer layer, creating a refractive
index ("RI") difference ("Delta RI") between the layers. It has
been determined that this difference in refractive index
contributes to an undesirable optical defect known as mottle or the
mottle defect.
[0044] Some terminology used throughout this application will be
explained to provide a better understanding of the invention. The
terms "polymer interlayer sheet," "interlayer," and "polymer melt
sheet" as used herein, generally may designate a single-layer sheet
or a multilayered interlayer. A "single-layer sheet," as the name
implies, is a single polymer layer extruded as one layer. A
multilayered interlayer, on the other hand, may comprise multiple
layers, including separately extruded layers, co-extruded layers,
or any combination of separately and co-extruded layers. Thus the
multilayered interlayer could comprise, for example: two or more
single-layer sheets combined together ("plural-layer sheet"); two
or more layers co-extruded together ("co-extruded sheet"); two or
more co-extruded sheets combined together; a combination of at
least one single-layer sheet and at least one co-extruded sheet; a
combination of a single-layer sheet and a plural-layer sheet; and a
combination of at least one plural-layer sheet and at least one
co-extruded sheet. In various embodiments of the present
disclosure, a multilayered interlayer comprises at least two
polymer layers (e.g., a single layer or multiple layers co-extruded
and/or laminated together) disposed in direct contact with each
other, wherein each layer comprises a polymer resin, as detailed
more fully below. As used herein for multilayer interlayers having
at least three layers, "skin layer" generally refers to the outer
layers of the interlayer and "core layer" generally refers to the
inner layer(s). Thus, one exemplary embodiment would be: skin
layer//core layer//skin layer. As used herein, "stiff layer" or
"stiffer layer" generally refers to a layer that is stiffer or more
rigid than another layer and that has a glass transition
temperature that is generally at least two degrees C. (2.degree.
C.) higher than another layer. As used herein, the "soft layer" or
"softer layer" generally refers to a layer that is softer than
another layer and that has a glass transition temperature that is
generally at least two degrees C. (2.degree. C.) lower than another
layer. The soft layer and stiff layer can be differentiated when
both layers contain the same plasticizer and each has a plasticizer
loading of 30 phr. The soft layer and stiff layer can be further
differentiated when the soft and stiff layers are in contact with
each other and the plasticizer partitions to reach equilibrium
state between the layers. Of course, this differentiation can also
be made at other plasticizer loadings as long as the loadings are
within limits of compatibility of the plasticizer to resins. In the
multilayer interlayers having skin layer//core layer//skin layer
configuration, in some embodiments the skin layer maybe stiffer and
the core layer may be softer, while in other embodiments the skin
layer may be softer and the core layer may be stiffer. It should be
noted, however, further embodiments include interlayers having only
two layers or interlayers having more than three layers (e.g., 4,
5, 6, or up to 10 or more individual layers). Additionally, any
multilayer interlayer utilized can be varied by manipulating the
composition, thickness, or positioning of the layers and the like.
For example, in one trilayer polymer interlayer sheet, the two
stiff (or outer or skin) layers may comprise poly(vinyl butyral)
("PVB") resin with a plasticizer or mixture of plasticizers, while
the softer (inner or core) layers may comprise the same or
different PVB resin or a different thermoplastic material with a
the same or different plasticizer and/or mixture of plasticizers.
Thus, it is contemplated that the stiff or skin layers and the soft
or core layer(s) of the multilayered interlayer sheets may be
comprised of the same thermoplastic material or different
thermoplastic materials and the same or different plasticizer or
plasticizers. Either or both layers may include additional
additives as known in the art, as desired. In multilayer
interlayers, the plasticizers or mixture of plasticizers in the
stiff or skin and soft or core layers are selected such that the
difference in refractive indices of the stiff or skin layer(s) and
soft or core layer(s) is minimized, and the mottle is reduced. For
example, in some embodiments, the difference between the refractive
index of the soft or core layer(s) and the refractive index of the
stiff or skin layer(s) (Delta RI) may be less than 0.010, or less
than 0.009, or less than 0.008, or less than 0.007, or less than
0.006, or less than 0.005, or less than 0.004, or less than 0.003,
or less than 0.002, or less than 0.001, or even about 0.000. The
Delta RI may be positive or negative, or may be taken as the
absolute value of the difference between the layers. In some
embodiments, the difference between the refractive index of the
resin and the refractive index of the plasticizer (Delta RI) may be
less than 0.100, or less than 0.075, or less than 0.070, or less
than 0.065, or less than 0.060, or less than 0.055, or less than
0.050, or less than 0.040, or less than 0.030, or less than 0.020,
or less than 0.010, or about 0.000.
[0045] Although the embodiments described below refer to the
polymer resin as being PVB, it would be understood by one of
ordinary skill in the art that the polymer may be any polymer
suitable for use in a multiple layer panel. Typical polymers
include, but are not limited to, polyvinyl acetals (PVA) (such as
poly(vinyl butyral) (PVB)), polyurethane (PU),
poly(ethylene-co-vinyl acetate) (EVA), polyvinylchloride (PVC),
poly(vinylchloride-co-methacrylate), polyethylenes, polyolefins,
ethylene acrylate ester copolymers, poly(ethylene-co-butyl
acrylate), silicone elastomers, epoxy resins, and acid copolymers
such as ethylene/carboxylic acid copolymers and its ionomers,
derived from any of the foregoing possible thermoplastic resins,
combinations of the foregoing, and the like. PVB, polyvinyl
chloride, and polyurethane are useful polymers generally for
interlayers; PVB is particularly useful when used in conjunction
with the interlayers of this disclosure comprising high refractive
index plasticizers.
[0046] Prior to discussing the addition of the specific plasticizer
or plasticizers selected to produce the interlayer having improved
optical quality, some common components found in an interlayer,
both generally and in interlayers of the present disclosure, and
the formation thereof, will be discussed.
[0047] The PVB resin is produced by known aqueous or solvent
acetalization processes by reacting polyvinyl alcohol ("PVOH") with
butyraldehyde in the presence of an acid catalyst, separation,
stabilization, and drying of the resin. Such acetalization
processes are disclosed, for example, in U.S. Pat. Nos. 2,282,057
and 2,282,026 and Vinyl Acetal Polymers, in Encyclopedia of Polymer
Science & Technology, 3rd edition, Volume 8, pages 381-399, by
B. E. Wade (2003), the entire disclosures of which are incorporated
herein by reference. The resin is commercially available in various
forms, for example, as Butvar.RTM. Resin from Solutia Inc., a
wholly owned subsidiary of Eastman Chemical Company.
[0048] As used herein, residual hydroxyl content (calculated as %
PVOH by weight) in PVB refers to the amount of hydroxyl groups
remaining on the polymer chains after processing is complete. For
example, PVB can be manufactured by hydrolyzing poly(vinyl acetate)
to PVOH, and then reacting the PVOH with butyraldehyde. In the
process of hydrolyzing the poly(vinyl acetate), typically not all
of the acetate side groups are converted to hydroxyl groups.
Further, reaction with butyraldehyde typically will not result in
all hydroxyl groups being converted to acetal groups. Consequently,
in any finished PVB resin, there typically will be residual acetate
groups (as vinyl acetate groups) and residual hydroxyl groups (as
vinyl hydroxyl groups) as side groups on the polymer chain. As used
herein, residual hydroxyl content is measured on a weight percent
basis per ASTM 1396.
[0049] In various embodiments, the PVB resin comprises about 8 to
about 35 weight percent (wt. %) hydroxyl groups calculated as %
PVOH, about 13 to about 30 wt. %, about 8 to about 22 wt. %, or
about 15 to about 22 wt. %; and, for certain embodiments, about
17.75 to about 19.85 wt. % hydroxyl groups calculated as % PVOH.
The resin can also comprise less than 25 wt. % residual ester
groups, less than 20 wt. % residual ester groups, less than 15 wt.
% residual ester groups, less than 13 wt. %, less than 11 wt. %,
less than 9 wt. %, less than 7 wt. %, less than 5 wt. %, or less
than 1 wt. % residual ester groups calculated as polyvinyl ester,
e.g., acetate, with the balance being an acetal, such as
butyraldehyde acetal, but optionally being other acetal groups,
such as a 2-ethyl hexanal acetal group, or a mix of butyraldehyde
acetal and 2-ethyl hexanal acetal groups.
[0050] In various embodiments, where the interlayer is a multilayer
interlayer such as a trilayer, the residual hydroxyl contents of
the PVB resins used in the stiff (or skin) layer(s) and soft (or
core) layer(s) can be different to provide certain performance
characteristics. The resin for the soft layer(s), for example, can
comprise about 8 to about 21 wt. %, about 8 to about 18 wt. %, or
about 8 to about 16 wt. %, or about 8 to about 14 wt. % residual
hydroxyl groups calculated as % PVOH. The resin for the stiff
layer(s), for example, can comprise about 13 to about 35 wt. %,
about 16 to about 35 wt. %, or about 15 to about 22 wt. %; and, for
certain embodiments, about 17.25 to about 22.25 wt. % residual
hydroxyl groups calculated as % PVOH. In various embodiments, the
residual hydroxyl content of adjacent stiff and soft layers can
differ by at least 2 wt. %, or at least 4 wt. %, or at least 6 wt.
%, or at least 8 wt. %, or at least by 10 wt. %. The resin for the
soft layer(s) or for the stiff layer(s) or for both the soft
layer(s) and stiff layer(s) can also comprise less than 25 wt. %
residual ester groups, less than 20 wt. % residual ester groups,
less than 15 wt. %, less than 13 wt. %, less than 11 wt. %, less
than 9 wt. %, less than 7 wt. %, less than 5 wt. %, or less than 1
wt. % residual ester groups calculated as polyvinyl ester, e.g.,
acetate, with the balance being an acetal, such as butyraldehyde
acetal, but optionally being other acetal groups, such as a 2-ethyl
hexanal acetal group, or a mix of butyraldehyde acetal and 2-ethyl
hexanal acetal groups, as previously discussed.
[0051] In various embodiments, where the interlayer is a multilayer
interlayer such as a trilayer, the skin layer(s) could have higher
residual hydroxyl groups calculated as % PVOH than the core
layer(s), or the skin layer(s) could be stiffer than the core
layer(s); in other embodiments, the skin layer(s) could have lower
residual hydroxyl groups calculated as % PVOH than the core
layer(s), or the skin layer(s) could be softer. If there are more
than two or three layers, any combination of stiff/soft/stiff/soft,
such as soft/stiff/soft/stiff, soft/stiff/stiff/soft,
stiff/soft/soft/stiff, and any number of layers, may be used,
depending on the desired properties and application.
[0052] For a given type of plasticizer, the compatibility of the
plasticizer in the PVB polymer is largely determined by the
hydroxyl content of the polymer. PVB with greater residual hydroxyl
content is typically, but not always, correlated with reduced
plasticizer compatibility or capacity, i.e., less plasticizer could
be incorporated. Conversely, PVB with a lower residual hydroxyl
content typically, but not always, will result in increased
plasticizer compatibility or capacity, i.e., more plasticizer could
be incorporated. For some plasticizer types, such correlation might
be reversed. Generally, this correlation between the residual
hydroxyl content of a polymer and plasticizer
compatibility/capacity will allow for the addition of the proper
amount of plasticizer to the polymer resin and more importantly to
stably maintain differences in plasticizer content between multiple
layers.
[0053] The PVB resin (or resins) of the present disclosure
typically has a molecular weight of greater than 50,000 Daltons, or
less than 500,000 Daltons, or about 50,000 to about 500,000
Daltons, or about 70,000 to about 500,000 Daltons, or more
preferably about 100,000 to about 425,000 Daltons, as measured by
size exclusion chromatography using low angle laser light
scattering. As used herein, the term "molecular weight" means the
weight average molecular weight.
[0054] Various adhesion control agents ("ACAs") can be used in the
interlayers of the present disclosure to control the adhesion of
the interlayer sheet to glass. In various embodiments of
interlayers of the present disclosure, the interlayer can comprise
about 0.003 to about 0.15 parts ACAs per 100 parts resin; about
0.01 to about 0.10 parts ACAs per 100 parts resin; and about 0.01
to about 0.04 parts ACAs per 100 parts resin. Such ACAs, include,
but are not limited to, the ACAs disclosed in U.S. Pat. No.
5,728,472 (the entire disclosure of which is incorporated herein by
reference), residual sodium acetate, potassium acetate, magnesium
bis(2-ethyl butyrate), and/or magnesium bis(2-ethylhexanoate).
[0055] Other additives may be incorporated into the interlayer to
enhance its performance in a final product and impart certain
additional properties to the interlayer. Such additives include,
but are not limited to, dyes, pigments, stabilizers (e.g.,
ultraviolet stabilizers), antioxidants, anti-blocking agents, flame
retardants, IR absorbers or blockers (e.g., indium tin oxide,
antimony tin oxide, lanthanum hexaboride (LaB.sub.6) and cesium
tungsten oxide), processing aides, flow enhancing additives,
lubricants, impact modifiers, nucleating agents, thermal
stabilizers, UV absorbers, dispersants, surfactants, chelating
agents, coupling agents, adhesives, primers, reinforcement
additives, and fillers, among other additives known to those of
ordinary skill in the art.
[0056] In various embodiments of interlayers of the present
disclosure, the interlayer can comprise 0 to about 100 or more, 0
to about 80, about 0 to 45, about 10 to about 75, about 15 to about
60, about 15 to about 50, about 25 to about 50, about 10 to about
40, about 15 to about 40, about 25 to about 38, about 29 to about
32, and about 30 phr (parts per hundred parts resin) conventional
plasticizer. Of course, other quantities can be used as is
appropriate for the particular application and the desired
properties.
[0057] In various embodiments of interlayers of the present
disclosure, the interlayer comprises greater than 5 phr, about 5 to
about 120 phr, about 5 to 100, about 10 to about 80 phr, about 20
to about 70 phr, about 30 to about 60 phr, or less than 120 phr, or
less than 110 phr, or less than 100 phr, or less than 90 phr, or
less than 80 phr, or less than 70 phr, or less than 60 phr total
plasticizer. While the total plasticizer content is indicated
above, the plasticizer content in the skin layer(s) or core
layer(s) can be different from the total plasticizer content. In
addition, the skin layer(s) and core layer(s) can have different
plasticizer types and plasticizer contents, in the ranges
previously discussed, as each respective layer's plasticizer
content at the equilibrium state is determined by the layer's
respective residual hydroxyl contents, as disclosed in U.S. Pat.
No. 7,510,771 (the entire disclosure of which is incorporated
herein by reference). For example, at equilibrium the interlayer
could comprise two skin layers, each with 38 phr plasticizer, and a
core layer with 75 phr plasticizer, for a total plasticizer amount
for the interlayer of about 54.3 phr when the combined skin layer
thickness equals that of the core layer. As used herein, the amount
of plasticizer, or any other component in the interlayer, can be
measured as parts per hundred parts resin (phr), on a weight per
weight basis. For example, if 30 grams of plasticizer is added to
100 grams of polymer resin, then the plasticizer content of the
resulting plasticized polymer would be 30 phr. As used herein, when
the plasticizer content of the interlayer is given, the plasticizer
content is determined with reference to the phr of the plasticizer
in the mix or melt that was used to produce the interlayer. In
embodiments of a multilayer interlayer having a stiff layer and a
soft layer, the stiff layer may have from 5 to 60 phr plasticizer
and the soft layer may have from 10 to 120 phr plasticizer.
[0058] In some embodiments, the conventional plasticizer includes,
for example, triethylene glycol di-(2-ethylhexanoate) ("3GEH"),
triethylene glycol di-(2-ethylbutyrate), triethylene glycol
diheptanoate, tetraethylene glycol diheptanoate, tetraethylene
glycol di-(2-ethylhexanoate), dihexyl adipate, dioctyl adipate,
hexyl cyclohexyladipate, diisononyl adipate, heptylnonyl adipate,
dibutyl sebacate, dioctyl sebacate, di(butoxyethyl) adipate,
bis(2-(2-butoxyethoxy)ethyl) adipate, and mixtures thereof. In some
embodiments, the conventional plasticizer is 3GEH.
[0059] Increasing the refractive index of one or more of the
layers, such as a soft or core layer, to be closer to the
refractive index of the other layer(s) can minimize the difference
in refractive index between the layers (such as the stiff (or skin)
and soft (or core) layers), thereby minimizing the amount of mottle
in the multilayer interlayer. One way to increase the refractive
index of one of the layers is to use a high refractive index
plasticizer. As used herein, a "high refractive index plasticizer"
is a plasticizer having a refractive index of at least about 1.460.
The refractive index of one conventional and commonly used
plasticizer, such as 3GEH, is about 1.442. The refractive indices
of the conventional plasticizers listed above are from about 1.442
to about 1.449. Examples of plasticizers having a high refractive
index that may be used include, but are not limited to,
polyadipates (RI of about 1.460 to about 1.485); epoxides such as
epoxidized soybean oils (RI of about 1.460 to about 1.480);
phthalates and terephthalates (RI of about 1.480 to about 1.540);
benzoates (RI of about 1.480 to about 1.550); and other specialty
plasticizers (RI of about 1.490 to about 1.520). The refractive
index of poly(vinyl butyral) resin is approximately 1.485 to
1.495.
[0060] Examples of the high refractive index plasticizer include,
but are not limited to, esters of a polybasic acid or a polyhydric
alcohol, polyadipates, epoxides, phthalates, terephthalates,
benzoates, toluates, mellitates and other specialty plasticizers,
among others. Examples of suitable plasticizers include, but are
not limited to, dipropylene glycol dibenzoate, tripropylene glycol
dibenzoate, polypropylene glycol dibenzoate, isodecyl benzoate,
2-ethylhexyl benzoate, diethylene glycol benzoate, propylene glycol
dibenzoate, 2,2,4-trimethyl-1,3-pentanediol dibenzoate,
2,2,4-trimethyl-1,3-pentanediol benzoate isobutyrate,
1,3-butanediol dibenzoate, diethylene glycol di-o-toluate,
triethylene glycol di-o-toluate, dipropylene glycol di-o-toluate,
1,2-octyl dibenzoate, tri-2-ethylhexyl trimellitate,
di-2-ethylhexyl terephthalate, bis-phenol A bis(2-ethylhexaonate),
ethoxylated nonylphenol, and mixtures thereof. In some embodiments,
examples of high refractive index plasticizers are dipropylene
glycol dibenzoate, 2,2,4-trimethyl-1,3-pentanediol dibenzoate, and
tripropylene glycol dibenzoate.
[0061] In multilayer interlayers, comprising, for example, stiff
and soft layers, the stiff and soft layers could each comprise a
conventional plasticizer in combination with a one or more high
refractive index plasticizer, or comprise a single high refractive
index plasticizer alone or a combination of high refractive index
plasticizers, so long as the difference in the refractive indices
(Delta RI) between layers is minimized. Concentrations of the
plasticizers incorporated into the melts of the different layers,
such as the soft or stiff layers, are as described above.
[0062] In any of these embodiments, the plasticizer(s) can be any
of those described above. In embodiments, the plasticizer(s) is
selected such that the Delta RI between the layers of the
interlayer is minimized (that is, as close to 0.000 as possible),
or less than 0.010, or less than 0.009, or less than 0.008, or less
than 0.007, or less than 0.006, or less than 0.005, or less than
0.004, or less than 0.003, or less than 0.002, or less than 0.001,
or about 0.000. In other embodiments, the plasticizer is selected
such that the Delta RI between the resin and plasticizer is less
than 0.075, or less than 0.070, or less than about 0.065, or less
than 0.060, or less than 0.055, or less than 0.050, or less than
0.040, or less than 0.030, or less than 0.020, or less than 0.010,
or about 0.000. In various embodiments, the high refractive index
plasticizer(s) is selected such that the refractive index of the
plasticizer is at least about 1.460, or greater than about 1.470,
or greater than about 1.480, or greater than about 1.490, or
greater than about 1.500, or greater than 1.510, or greater than
about 1.520. In some embodiments, the high refractive index
plasticizer(s) is used in conjunction with a conventional
plasticizer, and in some embodiments, if included, the conventional
plasticizer is triethylene glycol di-(2-ethylhexanoate) ("3GEH").
In some embodiments, the refractive index of the plasticizer
mixture is at least greater than 1.460.
[0063] Plasticizers work by embedding themselves between chains of
polymers, spacing them apart (increasing the "free volume") and
thus significantly lowering the glass transition temperature
(T.sub.g) of the polymer resin (typically by 0.5 to 4.degree.
C./phr), making the material softer. In this regard, the amount of
plasticizer in the interlayer can be adjusted to affect the glass
transition temperature (T.sub.g). The glass transition temperature
(T.sub.g) is the temperature that marks the transition from the
glassy state of the polymer to the rubbery state. In general,
higher amounts of plasticizer loading will result in lower T.sub.g.
Conventional interlayers generally have a T.sub.g in the range of
about 0.degree. C. for acoustic (noise reducing) interlayer to
about 45.degree. C. for hurricane and aircraft interlayer
applications. A particularly preferred T.sub.g for certain
embodiments is in the range of about 28.degree. C. to about
35.degree. C. for the stiffer layer(s) and about -2.degree. C. to
about 5.degree. C. for the softer layer(s).
[0064] An interlayer's glass transition temperature (T.sub.g) is
also correlated with the stiffness of the interlayer, and in
general, the higher the glass transition temperature, the stiffer
the interlayer. Generally, an interlayer with a glass transition
temperature of 30.degree. C. or higher increases windshield
strength and torsional rigidity. A soft interlayer (generally
characterized by an interlayer with a glass transition temperature
of lower than 30.degree. C.), on the other hand, contributes to the
sound dampening effect (i.e., the acoustic characteristics). The
interlayers of the present disclosure may have glass transition
temperatures of about 30.degree. C. or greater, or about 35.degree.
C. or greater for the stiffer layer(s), and about 10.degree. C. or
less, or about 4.degree. C. or less, or about -5.degree. C. or
less, or about -10.degree. C. or less for the soft layer(s). In
some embodiments, the multilayered interlayers of the present
disclosure combine these two advantageous properties (i.e.,
strength and acoustic) by utilizing harder or stiffer skin layers
laminated with a softer core layer (e.g., stiff//soft//stiff) and
softer skin layers laminated with a stiffer core layer (e.g.,
soft//stiff//soft), while also matching the refractive indices of
the layers to reduce and/or minimize or eliminate mottle. In
various embodiments, the multilayered interlayers generally
comprise stiffer layer(s) with a glass transition temperature of
about 25.degree. C. to about 40.degree. C., about 20.degree. C. to
about 35.degree. C., about 25.degree. C. to 35.degree. C., about
25.degree. C. or greater, about 30.degree. C. or greater, and about
35.degree. C. or greater, and softer layer(s) of about 10.degree.
C. or less, or about 4.degree. C. or less, or about -5.degree. C.
or less, or about -10.degree. C. or less. For example, the
following are some typical multilayered configurations:
[0065] (T.sub.g>25.degree. C.)//(T.sub.g<10.degree.
C.)//(T.sub.g>25.degree. C.) or (stiff//soft//stiff);
[0066] (25.degree. C.<T.sub.g<40.degree.
C.)//(T.sub.g<10.degree. C.)//(25.degree.
C.<T.sub.g<40.degree. C.) or (stiff//soft//stiff);
[0067] (T.sub.g<35.degree. C.)//(T.sub.g>35.degree.
C.)//(T.sub.g<35.degree. C.) or (soft//stiff//soft); and
[0068] (20.degree. C.<T.sub.g<35.degree.
C.)//(T.sub.g>35.degree. C.)//(20.degree.
C.<T.sub.g<35.degree. C.) or (soft//stiff//soft).
These configurations are merely exemplary and are in no way meant
to be limiting to the types of multilayered configurations
contemplated by this disclosure.
[0069] Additionally, it is contemplated that polymer interlayer
sheets as described herein may be produced by any suitable process
known to one of ordinary skill in the art of producing polymer
interlayer sheets that are capable of being used in a multiple
layer panel (such as a glass laminate or a photovoltaic module or
solar panel). For example, it is contemplated that the polymer
interlayer sheets may be formed through solution casting,
compression molding, injection molding, melt extrusion, melt
blowing or any other procedures for the production and
manufacturing of a polymer interlayer sheet known to those of
ordinary skill in the art. Further, in embodiments where multiple
polymer interlayers are utilized, it is contemplated that these
multiple polymer interlayers may be formed through co-extrusion,
blown film, dip coating, solution coating, blade, paddle,
air-knife, printing, powder coating, spray coating or other
processes known to those of ordinary skill in the art. While all
methods for the production of polymer interlayer sheets known to
one of ordinary skill in the art are contemplated as possible
methods for producing the polymer interlayer sheets described
herein, this application will focus on polymer interlayer sheets
produced through the extrusion and co-extrusion processes. The
final multiple layer glass panel laminate and photovoltaic module
of the present invention are formed using processes known in the
art.
[0070] In its most basic sense, extrusion is a process used to
create objects of a fixed cross-sectional profile. This is
accomplished by pushing or drawing a material through a die of the
desired cross-section for the end product.
[0071] Generally, in the extrusion process, thermoplastic resin and
plasticizers, including any of those resins and plasticizers
described above, are pre-mixed and fed into an extruder device.
Additives such as ACAs, colorants and UV inhibitors (in liquid,
powder, or pellet form) are often used and can be mixed into the
thermoplastic resin or plasticizer(s) prior to arriving in the
extruder device. These additives are incorporated into the
thermoplastic polymer resin, and by extension the resultant polymer
interlayer sheet, to enhance certain properties of the polymer
interlayer sheet and its performance in the final multiple layer
glass panel product (or photovoltaic module).
[0072] In the extruder device, the particles of the thermoplastic
raw material and plasticizers, and any other additives described
above, are further mixed and melted, resulting in a melt that is
generally uniform in temperature and composition. Once the melt
reaches the end of the extruder device, the melt is propelled into
the extruder die. The extruder die is the component of the
thermoplastic extrusion process which gives the final polymer
interlayer sheet product its profile. Generally, the die is
designed such that the melt evenly flows from a cylindrical profile
coming out of the die and into the product's end profile shape. A
plurality of shapes can be imparted to the end polymer interlayer
sheet by the die so long as a continuous profile is present.
[0073] Notably, for the purposes of this application, the polymer
interlayer at the state after the extrusion die forms the melt into
a continuous profile will be referred to as a "polymer melt sheet."
At this stage in the process, the extrusion die has imparted a
particular profile shape to the thermoplastic resin, thus creating
the polymer melt sheet. The polymer melt sheet is highly viscous
throughout and in a generally molten state. In the polymer melt
sheet, the melt has not yet been cooled to a temperature at which
the sheet generally completely "sets." Thus, after the polymer melt
sheet leaves the extrusion die, generally the next step in
presently employed thermoplastic extrusion processes is to cool the
polymer melt sheet with a cooling device. Cooling devices utilized
in the previously employed processes include, but are not limited
to, spray jets, fans, cooling baths, and cooling rollers. The
cooling step functions to set the polymer melt sheet into a polymer
interlayer sheet of a generally uniform non-molten cooled
temperature. In contrast to the polymer melt sheet, this polymer
interlayer sheet is not in a molten state and is not highly
viscous. Rather, it is the set final-form cooled polymer interlayer
sheet product. For the purposes of this application, this set and
cooled polymer interlayer will be referred to as the "polymer
interlayer sheet."
[0074] In some embodiments of the extrusion process, a co-extrusion
process may be utilized. Co-extrusion is a process by which
multiple layers of polymer material are extruded simultaneously.
Generally, this type of extrusion utilizes two or more extruders to
melt and deliver a steady volume throughput of multiple different
thermoplastic melts of different viscosities or other properties
through a co-extrusion die into the desired final form. The
thickness of the multiple polymer layers leaving the extrusion die
in the co-extrusion process can generally be controlled by
adjustment of the relative speeds of the melt through the extrusion
die and by the sizes of the individual extruders processing each
molten thermoplastic resin material.
[0075] Generally, the thickness, or gauge, of the polymer
interlayer sheet will be in a range from about 15 mils to 100 mils
(about 0.38 mm to about 2.54 mm), about 15 mils to 60 mils (about
0.38 mm to about 1.52 mm), about 20 mils to about 50 mils (about
0.51 to 1.27 mm), and about 15 mils to about 35 mils (about 0.38 to
about 0.89 mm). In various embodiments, each of the layers, such as
the skin and core layers, of the multilayer interlayer may have a
thickness of about 1 mil to 99 mils (about 0.025 to 2.51 mm), about
1 mil to 59 mils (about 0.025 to 1.50 mm), 1 mil to about 29 mils
(about 0.025 to 0.74 mm), or about 2 mils to about 28 mils (about
0.05 to 0.71 mm).
[0076] As noted above, the interlayers of the present disclosure
may be used as a single-layer sheet or a multilayered sheet. In
various embodiments, the interlayers of the present disclosure
(either as a single-layer sheet or as a multilayered sheet) can be
incorporated into a multiple layer panel.
[0077] As used herein, a multiple layer panel can comprise a single
substrate, such as glass, acrylic, or polycarbonate with a polymer
interlayer sheet disposed thereon, and most commonly, with a
polymer film further disposed over the polymer interlayer. The
combination of polymer interlayer sheet and polymer film is
commonly referred to in the art as a bilayer. A typical multiple
layer panel with a bilayer construct is: (glass)//(polymer
interlayer sheet)//(polymer film), where the polymer interlayer
sheet can comprise multiple interlayers, as noted above. The
polymer film supplies a smooth, thin, rigid substrate that affords
better optical character than that usually obtained with a polymer
interlayer sheet alone and functions as a performance enhancing
layer. Polymer films differ from polymer interlayer sheets, as used
herein, in that polymer films do not themselves provide the
necessary penetration resistance and glass retention properties,
but rather provide performance improvements, such as infrared
absorption characteristics. Poly(ethylene terephthalate) ("PET") is
the most commonly used polymer film. Generally, as used herein, a
polymer film is thinner than a polymer sheet, such as from about
0.001 to 0.2 mm thick.
[0078] Further, the multiple layer panel can be what is commonly
known in the art as a solar panel, with the panel further
comprising a photovoltaic cell, as that term is understood by one
of ordinary skill in the art, encapsulated by the polymer
interlayer(s). In such instances, the interlayer is often laminated
over the photovoltaic cell, with a construct such as:
(glass)//(polymer interlayer)//(photovoltaic cell)//(polymer
interlayer)//(glass or polymer film).
[0079] The interlayers of the present disclosure will most commonly
be utilized in multiple layer panels comprising two substrates,
preferably a pair of glass sheets (or other rigid materials, such
as polycarbonate or acrylic, known in the art), with the
interlayers disposed between the two substrates. An example of such
a construct would be: (glass)//(polymer interlayer sheet)//(glass),
where the polymer interlayer sheet can comprise multilayered
interlayers, as noted above, and wherein the layers of the
multilayer interlayer comprise refractive index matching
plasticizers or one or more high refractive index plasticizer or
combination of plasticizers wherein the refractive index of the
mixture or combination is within the desired range. Stated
differently, the Delta RI between the layers is minimized (less
than 0.010), or the Delta RI between the resin and plasticizer is
minimized (less than 0.100 or less than 0.075), or the plasticizer
is a high refractive index plasticizer (at least about 1.460), such
that mottle in the multiple layer panel is reduced, and the clarity
of the multiple layer panel is excellent (that is, having minimal
haze). These examples of multiple layer panels are in no way meant
to be limiting, as one of ordinary skill in the art would readily
recognize that numerous constructs other than those described above
could be made with the interlayers of the present disclosure.
[0080] The typical glass lamination process comprises the following
steps: (1) assembly of the two substrates (e.g., glass) and
interlayer; (2) heating the assembly via an IR radiant or
convective means for a short period; (3) passing the assembly into
a pressure nip roll for the first deairing; (4) heating the
assembly a second time to about 60.degree. C. to about 120.degree.
C. to give the assembly enough temporary adhesion to seal the edge
of the interlayer; (5) passing the assembly into a second pressure
nip roll to further seal the edge of the interlayer and allow
further handling; and (6) autoclaving the assembly at temperatures
between 135.degree. C. and 150.degree. C. and pressures between 150
psig and 200 psig for about 30 to 90 minutes. The actual steps, as
well as the times and temperatures, may vary as necessary, as known
by one skilled in the art.
[0081] Other means for use in de-airing of the interlayer-glass
interfaces (steps 2-5) known in the art and that are commercially
practiced include vacuum bag and vacuum ring processes in which a
vacuum is utilized to remove the air.
[0082] Mottle is one measure of optical quality of a laminate. It
is seen as texture or graininess and is considered a visual defect
if the level of mottle is too high or too severe (and thus
objectionable). As previously discussed, mottle is assessed and
categorized by a side-to-side qualitative comparison of the
shadowgraph projections for a test laminate with a set of standard
laminate shadowgraphs representing a series or scale of mottle
values ranging from 1 to 4, with 1 representing a standard of low
mottle (i.e., a low number of disruptions) and 4 representing a
standard of high mottle (i.e., a high number of disruptions). High
mottle is generally considered optically objectionable,
particularly in glass panels such as windshields. Optionally, a
laminate having a single layer interlayer with zero mottle (or no
mottle) is used to facilitate the evaluation of mottle in the test
laminate with a mottle rating lower than the scale of the standard
set, such as lower than a rating of 1. The test laminate that shows
a shadowgraph projection similar to that of a "zero" mottle
laminate is assessed to have a mottle rating of zero (0).
[0083] Another parameter used to describe the polymer interlayers
disclosed herein is the clarity, which is determined by measuring
the haze value or percent. Light that is scattered upon passing
through a film or sheet of a material can produce a hazy or smoky
field when objects are viewed through the material. Thus, the haze
value is a quantification of the scattered light by a sample in
contrast to the incident light. The test for percent haze is
performed with a hazemeter, such as Model D25 available from Hunter
Associates (Reston, Va.), and in accordance with ASTM D1003-61
(Re-approved 1977)-Procedure A using Illuminant C, at an observer
angle of 2 degrees. The interlayers of the present disclosure have
a percent haze of less than about 5%, less than about 4%, less than
about 3%, less than about 2%, less than about 1%, or less than
about 0.5%.
[0084] The glass transition temperature also is used to describe
the polymer interlayers of the present disclosure. The glass
transition temperature (T.sub.g) was determined by dynamical
mechanical thermal analysis (DMTA). The DMTA measures the storage
(elastic) modulus (G') in Pascals, loss (viscous) modulus (G'') in
Pascals, loss (damping) factor (LF or tan(delta)) of the specimen
as a function of temperature at a given frequency, and temperature
sweep rate. A frequency of 1 Hz and temperature sweep rate of
3.degree. C./min were used herein. The T.sub.g is then determined
by the position of the loss factor peak on the temperature scale in
.degree. C.
[0085] Pummel adhesion is another parameter used to describe the
polymer interlayers disclosed herein. The Pummel Adhesion Test is
widely used throughout the world and has been a standard Solutia
Inc., a subsidiary of Eastman Chemical Company, procedure for over
30 years. It measures the adhesion level of glass to the interlayer
in a laminate construction. The interlayer to glass adhesion has a
large effect on the impact resistance and long term stability of
glass-interlayer structures. In this test, the laminates are cooled
to 0.degree. F. (about -18.degree. C.) and manually pummeled with a
1 lb. (about 0.45 kg.) hammer on a steel plate at a 45 degree
angle. The samples are then allowed to come to room temperature and
all broken glass unadhered to the interlayer is then removed. The
amount of glass left adhered to the interlayer is visually compared
with a set of standards. The standards correspond to a scale in
which varying degrees of glass remained adhered to the interlayer.
For example, at a pummel standard of zero, essentially no glass is
left adhered to the interlayer. On the other hand, at a pummel
standard of ten, essentially 100% of the glass remains adhered to
the interlayer. Pummel values are grouped and averaged for like
specimens. Reported values state the average pummel value for the
group and the maximum range of the pummel adhesion rating for
individual surfaces. The interlayers of the present disclosure have
a pummel adhesion rating of at least 2, greater than 2, greater
than 4, greater than 6, and greater than 8.
[0086] The refractive index (RI) of the interlayers was measured in
accordance with ASTM D542. The reported RI values are obtained at a
wavelength of 589 nm and at 25.degree. C.
[0087] The invention also includes the following Embodiments 1 to
36, set forth below.
[0088] Embodiment 1 is a polymer interlayer comprising: poly(vinyl
butyral) resin; and at least one high refractive index plasticizer
having a refractive index of at least about 1.460; wherein the
interlayer comprises about 5 to about 120 parts of the high
refractive index plasticizer mixture per 100 parts poly(vinyl
butyral) resin.
[0089] Embodiment 2 is a polymer interlayer comprising: poly(vinyl
butyral) resin; and at least one high refractive index plasticizer
having a refractive index of at least about 1.460; wherein the
interlayer comprises about 5 to about 120 parts of the high
refractive index plasticizer mixture per 100 parts poly(vinyl
butyral) resin, and wherein the refractive index of the polymer
interlayer is at least 1.480.
[0090] Embodiment 3 is a multiple layer polymer interlayer
comprising: poly(vinyl butyral) resin; and at least one high
refractive index plasticizer having a refractive index of at least
about 1.460; wherein the multiple layer polymer interlayer has at
least one soft layer and at least one stiff layer, and wherein the
difference between the refractive index of the soft layer and the
stiff layer (Delta RI) is less than about 0.010.
[0091] Embodiment 4 is a multiple layer polymer interlayer
comprising: poly(vinyl butyral) resin; and at least one high
refractive index plasticizer having a refractive index of at least
about 1.460; wherein the multiple layer polymer interlayer has at
least one soft layer and at least two stiff layers wherein the soft
layer is disposed between the stiff layers, and wherein the
difference between the refractive index of the soft layer and the
stiff layers is less than about 0.010.
[0092] Embodiment 5 is a multiple layer polymer interlayer
comprising: a first layer comprising poly(vinyl butyral) resin and
a first plasticizer; a second layer comprising poly(vinyl butyral)
resin and a second plasticizer; and a third layer comprising
poly(vinyl butyral) resin and a third plasticizer disposed between
the first layer and the second layer; and wherein at least one of
the first, second and third plasticizers is a high refractive index
plasticizer having a refractive index of at least about 1.460;
wherein at least one layer is a soft layer and at least one layer
is a stiff layer, and wherein the difference between the refractive
index of the soft layer and the stiff layer (Delta RI) is less than
about 0.010.
[0093] Embodiment 6 is a multiple layer polymer interlayer
comprising: a first stiff layer comprising poly(vinyl butyral)
resin and a first plasticizer, wherein the first plasticizer is
present in an amount of from 5 phr to 60 phr; a second stiff layer
comprising poly(vinyl butyral) resin and a second plasticizer,
wherein the second plasticizer is present in an amount of from 5
phr to 60 phr; and a first soft layer comprising poly(vinyl
butyral) resin and a third plasticizer, wherein the third
plasticizer is present in an amount of from 10 phr to 120 phr, and
wherein the first soft layer is disposed between the first stiff
layer and the second stiff layer; wherein at least one of the
first, second and third plasticizers is a high refractive index
plasticizer having a refractive index of at least about 1.460;
wherein the difference between the refractive index of the soft
layer and the stiff layers is less than about 0.010.
[0094] Embodiment 7 is a polymer interlayer that includes the
features of any of Embodiments 1 to 6, wherein the high refractive
index plasticizer has a refractive index of at least about
1.470.
[0095] Embodiment 8 is a polymer interlayer that includes the
features of any of Embodiments 1 to 7, wherein the high refractive
index plasticizer has a refractive index of at least about
1.480.
[0096] Embodiment 9 is a polymer interlayer that includes the
features of any of Embodiments 1 to 8, wherein the high refractive
index plasticizer has a refractive index of at least about
1.490.
[0097] Embodiment 10 is a polymer interlayer that includes the
features of any of Embodiments 1 to 9, wherein the difference
between the refractive index of the resin and the refractive index
of the high refractive index plasticizer is less than about
0.075.
[0098] Embodiment 11 is a polymer interlayer that includes the
features of any of Embodiments 1 to 10, wherein the difference
between the refractive index of the resin and the refractive index
of the high refractive index plasticizer is less than about
0.050.
[0099] Embodiment 12 is a polymer interlayer that includes any of
the features of Embodiments 1 to 11, wherein the high refractive
index plasticizer has a refractive index of from about 1.460 to
about 1.560.
[0100] Embodiment 13 is a multiple layer polymer interlayer that
includes the features of any of Embodiments 3 to 12, wherein the
soft layer comprises a poly(vinyl butyral) resin having a residual
hydroxyl content from 8 to 21 wt. %, and wherein the stiff layer
comprises a poly(vinyl butyral) resin having a residual hydroxyl
content from 16 to 35 wt. %, and wherein the residual hydroxyl
content between the adjacent soft and stiff layers differs by at
least 2 wt. %.
[0101] Embodiment 14 is a multiple layer polymer interlayer that
includes the features of any of Embodiments 3 to 13, wherein the
soft layer has a plasticizer content of from 10 phr to 120 phr, and
wherein the stiff layer has a plasticizer content of from 5 phr to
60 phr.
[0102] Embodiment 15 is a polymer interlayer that includes the
features of any of Embodiments 1 to 14, wherein the polymer
interlayer comprises at least two different high refractive
plasticizers, wherein each high refractive index plasticizer has a
refractive index of at least 1.460.
[0103] Embodiment 16 is a polymer interlayer that includes the
features of any of Embodiments 1 to 14, wherein the polymer
interlayer comprises at least two plasticizers, wherein at least
one plasticizer has a refractive index of at least 1.460 and at
least one plasticizer has a refractive index of less than about
1.450.
[0104] Embodiment 17 is a polymer interlayer that includes the
features of any of Embodiments 1 to 16, wherein the high refractive
plasticizer is selected from dipropylene glycol dibenzoate,
tripropylene glycol dibenzoate, polypropylene glycol dibenzoate,
isodecyl benzoate, 2-ethylhexyl benzoate, diethylene glycol
benzoate, propylene glycol dibenzoate,
2,2,4-trimethyl-1,3-pentanediol dibenzoate,
2,2,4-trimethyl-1,3-pentanediol benzoate isobutyrate,
1,3-butanediol dibenzoate, 2,2,4-trimethyl-1,3-pentanediol
dibenzoate, diethylene glycol di-o-toluate, triethylene glycol
di-o-toluate, dipropylene glycol di-o-toluate, 1,2-octyl
dibenzoate, tri-2-ethylhexyl trimellitate, di-2-ethylhexyl
terephthalate, bis-phenol A bis(2-ethylhexaonate), ethoxylated
nonylphenol, and mixtures thereof.
[0105] Embodiment 18 is a polymer interlayer that includes the
features of Embodiments 1 to 17, wherein the high refractive
plasticizer is selected from dipropylene glycol dibenzoate,
tripropylene glycol dibenzoate, and 2,2,4-trimethyl-1,3-pentanediol
dibenzoate.
[0106] Embodiment 19 is a polymer interlayer that includes the
features of any of Embodiments 1 to 18, further comprising an
additional plasticizer, wherein the additional plasticizer is
triethylene glycol di-(2-ethylhexanoate).
[0107] Embodiment 20 is a multiple layer polymer interlayer that
includes the features of any of Embodiments 3 to 19, wherein the
multiple layer polymer interlayer further comprises a second stiff
layer, and wherein the soft layer is disposed between the stiff
layers, or a second soft layer and wherein the stiff layer is
disposed between the soft layers.
[0108] Embodiment 21 is a multiple layer polymer interlayer that
includes the features of Embodiment 15, wherein the at least two
different high refractive plasticizers are in the same layer.
[0109] Embodiment 22 is a multiple layer polymer interlayer that
includes the features of Embodiment 15, wherein the at least two
different high refractive plasticizers are in different layers.
[0110] Embodiment 23 is a multiple layer polymer interlayer that
includes the features of any of Embodiments 5 to 22, wherein the
first and second layers comprise the plasticizer having a
refractive index of at least 1.460, and wherein the third layer
comprises the plasticizer having a refractive index of less than
1.450.
[0111] Embodiment 24 is a multiple layer polymer interlayer that
includes the features of any of Embodiments 5 to 22, wherein the
third layer comprises the plasticizer having a refractive index of
at least 1.460, and wherein the first and second layers comprise
the plasticizer having a refractive index of less than 1.450.
[0112] Embodiment 25 is a multiple layer polymer interlayer that
includes the features of any of Embodiments 5 to 24, wherein the
first and second layers are stiff layers, and wherein the third
layer is a soft layer.
[0113] Embodiment 26 is a multiple layer polymer interlayer that
includes the features of any of Embodiments 5 to 24, wherein the
first and second layers are soft layers, and wherein the third
layer is a stiff layer.
[0114] Embodiment 27 is a polymer interlayer comprising: poly(vinyl
butyral) resin; and a plasticizer mixture comprising: at least one
plasticizer having a refractive index of less than about 1.450; and
at least one high refractive index plasticizer having a refractive
index of at least 1.460; wherein the refractive index of the
plasticizer mixture is at least 1.460; and wherein the interlayer
comprises about 5 to about 120 parts plasticizer mixture per 100
parts poly(vinyl butyral) resin.
[0115] Embodiment 28 is a multiple layer polymer interlayer
comprising: poly(vinyl butyral) resin; and a plasticizer mixture
comprising: at least one plasticizer selected from the group
consisting of: triethylene glycol di-(2-ethylhexanoate),
triethylene glycol di-(2-ethylbutyrate), triethylene glycol
diheptanoate, tetraethylene glycol diheptanoate, tetraethylene
glycol di-(2-ethylhexanoate), dihexyl adipate, dioctyl adipate,
hexyl cyclohexyladipate, diisononyl adipate, heptylnonyl adipate,
di(butoxyethyl) adipate, bis(2-(2-butoxyethoxy)ethyl) adipate,
dibutyl sebacate, and dioctyl sebacate; and at least one high
refractive index plasticizer having a refractive index of at least
1.460; wherein the refractive index of the plasticizer mixture is
at least 1.460; wherein the multiple layer polymer interlayer has
at least one soft layer and at least one stiff layer, and wherein
the difference between the refractive index (Delta RI) of the soft
layer and the stiff layer is less than about 0.010.
[0116] Embodiment 29 is a multiple layer polymer interlayer
comprising: a first layer comprising poly(vinyl butyral) resin and
a first plasticizer; a second layer comprising poly(vinyl butyral)
resin and a second plasticizer; and a third layer comprising
poly(vinyl butyral) resin and a third plasticizer disposed between
the first layer and the second layer; wherein at least one of the
first, second and third plasticizers is a mixture comprising: at
least one plasticizer having a refractive index of less than about
1.450; and at least one high refractive index plasticizer having a
refractive index of at least 1.460; wherein the refractive index of
the plasticizer mixture is at least 1.460; wherein at least one of
the layers is a soft layer and at least one of the layers is a
stiff layer, and wherein the difference between the refractive
index (Delta RI) of the soft layer and the stiff layer is less than
about 0.010.
[0117] Embodiment 30 is a polymer interlayer that includes the
features of any of Embodiments 27 to 29, wherein the plasticizer
mixture has a refractive index of from about 1.460 to about
1.560.
[0118] Embodiment 31 is a multiple layer polymer interlayer that
includes the features of any of Embodiments 28 to 30, wherein the
soft layer comprises a poly(vinyl butyral) resin having a residual
hydroxyl content from 8 to 21 wt. %, and wherein the stiff layer
comprises a poly(vinyl butyral) resin having a residual hydroxyl
content from 16 to 35 wt. %, and wherein the residual hydroxyl
content between the adjacent soft and stiff layers differs by at
least 2 wt. %.
[0119] Embodiment 32 is a multiple layer polymer interlayer that
includes the features of any of Embodiments 28 to 31, wherein the
soft layer has a plasticizer content of from 10 phr to 120 phr, and
wherein the stiff layer has a plasticizer content of from 5 phr to
60 phr.
[0120] Embodiment 33 is a polymer interlayer that includes the
features of any of Embodiments 27 to 32, wherein the high
refractive index plasticizer is selected from dipropylene glycol
dibenzoate, tripropylene glycol dibenzoate, polypropylene glycol
dibenzoate, isodecyl benzoate, 2-ethylhexyl benzoate, diethylene
glycol benzoate, propylene glycol dibenzoate,
2,2,4-trimethyl-1,3-pentanediol dibenzoate,
2,2,4-trimethyl-1,3-pentanediol benzoate isobutyrate,
1,3-butanediol dibenzoate, 2,2,4-trimethyl-1,3-pentanediol
dibenzoate, diethylene glycol di-o-toluate, triethylene glycol
di-o-toluate, dipropylene glycol di-o-toluate, 1,2-octyl
dibenzoate, tri-2-ethylhexyl trimellitate, di-2-ethylhexyl
terephthalate, bis-phenol A bis(2-ethylhexaonate), ethoxylated
nonylphenol, and mixtures thereof.
[0121] Embodiment 34 is a multiple layer polymer interlayer that
includes the features of any of Embodiments 28 to 33, wherein the
multiple layer polymer interlayer further comprises a second stiff
layer, and wherein the soft layer is disposed between the stiff
layers or a second soft layer and wherein the stiff layer is
disposed between the soft layers.
[0122] Embodiment 35 is a multiple layer panel comprising any of
the polymer interlayers of Embodiments 1 to 34.
[0123] Embodiment 36 is a method of making the polymer interlayer
of any of Embodiments 1 to 34.
EXAMPLES
[0124] The improvements (or reduction) in the level of mottle and
haze in a multilayer interlayer when using a high refractive index
plasticizer(s) or mix of plasticizers can be most readily
appreciated by a comparison of multilayer (trilayer) interlayers
having a plasticizer that is a high refractive index plasticizer(s)
or a combination of a high refractive index plasticizer(s) and a
conventional plasticizer (designated as "Disclosed Interlayers") to
a multilayer interlayer having only a conventional plasticizer,
such as triethylene glycol di-(2-ethylhexonate) ("3GEH")
(designated as "Conventional Interlayers"). The Conventional
Interlayers are shown as C1 to C7 in Table 1, and the Disclosed
Interlayers are shown in Table 2 to Table 6 below). These Examples
demonstrate the difference in refractive index (Delta RI) between
the layers can be minimized and the optical quality (mottle and
haze or clarity) improved when a high refractive index
plasticizer(s) is used either alone or in combination with one or
more plasticizers.
[0125] The Disclosed and Conventional Interlayers were produced by
mixing and melt-extruding mixtures of 100 parts poly(vinyl butyral)
resin and plasticizer, and other common additives. The types and
amounts of plasticizers used are shown in the Tables below.
Plasticizers are labeled as A, B, C, D, E or F, where C is the
Conventional Plasticizer, 3GEH, and A, B, D, E and F are each high
refractive index plasticizers or mixtures of plasticizers as shown
below and in the Tables. The poly(vinyl butyral) resin used in the
stiff (skin) layer had about 18 to 19 wt. % residual hydroxyl
content and a vinyl acetate residue of 2%, and the poly(vinyl
butyral) resin used in the soft (core) layer had about 10 to 11 wt.
% residual hydroxyl content and a vinyl acetate residue of 2%. The
amounts of plasticizer, the refractive indices, and the Delta RI
results are as shown below in Table 1 to Table 6.
[0126] Plasticizers used:
Plasticizer A: Dioctyl Terephthalate (RI--1.487)
[0127] Plasticizer B: Mixture of 30% 3GEH and 70% Benzoflex 2088*
(wt./wt.) (RI of the mixture--1.510, Benzoflex 2088 RI--1.539)
Plasticizer C: 3GEH(RI--1.442) (Conventional Plasticizer)
Plasticizer D: Nonylphenol Tetra-ethylene Glycol (RI--1.497)
[0128] Plasticizer E: Mixture of 50% 3GEH and 50% Benzoflex 2088*
(wt./wt.) (RI of the mixture--1.491, Benzoflex 2088 RI--1.539)
Plasticizer F: Mixture of 25% 3GEH and 75% Benzoflex 9-88**
(wt./wt.) (RI of the mixture--1.507, Benzoflex 9-88 RI--1.528)
TABLE-US-00001 TABLE 1 Conventional Interlayers Plasticizer C: 3GEH
(RI - 1.442) (Conventional Plasticizer) Skin Core Plasticizer
Plasticizer Sample (phr) Skin RI (phr) Core RI Delta RI C1 40 1.476
40 1.473 0.003 C2 40 1.476 50 1.471 0.005 C3 40 1.476 60 1.469
0.007 C4 40 1.476 70 1.467 0.009 C5 40 1.476 80 1.466 0.010 C6 40
1.476 90 1.465 0.011 C7 40 1.476 100 1.464 0.012
TABLE-US-00002 TABLE 2 Plasticizer A: Dioctyl Terephthalate (RI -
1.487) Skin Core Plasticizer Plasticizer Sample (phr) Skin RI (phr)
Core RI Delta RI A1 40 1.489 40 1.486 0.003 A2 40 1.489 50 1.486
0.003 A3 40 1.489 60 1.486 0.003 A4 40 1.489 70 1.486 0.003 A5 40
1.489 80 1.486 0.003 A6 40 1.489 90 1.486 0.003 A7 40 1.489 100
1.486 0.003
TABLE-US-00003 TABLE 3 Plasticizer B: Mixture of 30% 3GEH and 70%
Benzoflex 2088* (wt./wt.) (RI of the mixture - 1.510, Benzoflex
2088 RI - 1.539) Skin Core Plasticizer Plasticizer Sample (phr)
Skin RI (phr) Core RI Delta RI B1 40 1.496 40 1.492 0.004 B2 40
1.496 50 1.493 0.003 B3 40 1.496 60 1.494 0.002 B4 40 1.496 70
1.495 0.001 B5 40 1.496 80 1.496 0.000 B6 40 1.496 90 1.497 0.001
B7 40 1.496 100 1.498 0.002 *Benzoflex 2088 is plasticizer that is
a mixture of benzoates
TABLE-US-00004 TABLE 4 Plasticizer D: Nonylphenol Tetra-ethylene
Glycol (RI - 1.497) Skin Core Plasticizer Plasticizer Sample (phr)
Skin RI (phr) Core RI Delta RI D1 40 1.492 40 1.488 0.004 D2 40
1.492 50 1.489 0.003 D3 40 1.492 60 1.490 0.002 D4 40 1.492 70
1.490 0.002 D5 40 1.492 80 1.490 0.003 D6 40 1.492 90 1.491 0.001
D7 40 1.492 100 1.491 0.001
TABLE-US-00005 TABLE 5 Plasticizer E: Mixture of 50% 3GEH and 50%
Benzoflex 2088* (wt./wt.) (RI of the mixture - 1.491, Benzoflex
2088 RI - 1.539) Skin Core Plasticizer Plasticizer Sample (phr)
Skin RI (phr) Core RI Delta RI E1 40 1.490 40 1.487 0.003 E2 40
1.490 50 1.487 0.003 E3 40 1.490 60 1.487 0.003 E4 40 1.490 70
1.487 0.003 E5 40 1.490 80 1.488 0.002 E6 40 1.490 90 1.488 0.002
E7 40 1.490 100 1.488 0.002 *Benzoflex 2088 is plasticizer that is
a mixture of benzoates
TABLE-US-00006 TABLE 6 Plasticizer F: Mixture of 25% 3GEH and 75%
Benzoflex 9-88** (wt./wt.) (RI of the mixture - 1.507, Benzoflex
9-88 RI - 1.528) Skin Core Plasticizer Plasticizer Sample (phr)
Skin RI (phr) Core RI Delta RI F1 40 1.495 40 1.491 0.004 F2 40
1.495 50 1.492 0.003 F3 40 1.495 60 1.493 0.002 F4 40 1.495 70
1.494 0.001 F5 40 1.495 80 1.495 0.000 F6 40 1.495 90 1.485 0.000
F7 40 1.495 100 1.496 0.001 **Benzoflex 9-88 is a dipropylene
glycol dibenzoate plasticizer
[0129] Tables 1 to 6 show that for the Conventional Interlayers,
which include conventional plasticizer (such as 3GEH) having a
refractive index of less than about 1.450, as the level of
plasticizer in the soft (core) layer is increased from 40 phr to
100 phr, the Delta RI between the soft (core) and the stiff (skin)
layers increases significantly from 0.003 at 40 phr to 0.012 at 100
phr, as shown in Table 1. This fourfold increase in the Delta RI
between the soft (core) and the stiff (skin) layers will translate
to an increased level of mottle or a higher mottle rating, as well
as higher haze, in the multilayer glazing panel, as further
discussed below.
[0130] Where a high refractive index plasticizer or mix of
plasticizers including at least one high refractive index
plasticizer is used, such that the refractive index is greater than
about 1.460 (and higher than the RI of the conventional
plasticizer), the Delta RI between the soft (core) and the stiff
(skin) layers did not increase significantly as the level of
plasticizer in the soft (core) layer increased, as shown in Tables
2 to 6. With some plasticizers, the Delta RI did not change, while
in others, the change was from 0.001 to 0.004. In some cases, the
Delta RI stayed essentially the same or was even reduced. As shown
in Table 2, when Plasticizer A (RI of 1.487) was used, the Delta RI
was the same regardless (0.003) of the amount of plasticizer in the
soft (core) layer. As shown in Table 3, when Plasticizer B (a
mixture of a conventional plasticizer and a high refractive index
plasticizer, wherein the mixture had an RI of about 1.510) was
used, the Delta RI varied slightly, from 0.004 at 40 phr
Plasticizer B in the soft (core) layer, to zero at 80 phr in the
soft (core) layer, to 0.002 at 100 phr in the soft (core) layer.
Using Plasticizer D (RI of 1.497), as shown in Table 4, had similar
results to those in Table 3, where the Delta RI varied slightly
from 0.004 to 0.001 depending on the level of Plasticizer D in the
soft (core) layer. Using a mixture having a different ratio of
conventional plasticizer to high refractive index plasticizer
(Plasticizer E) produced a more consistent, but still very low,
Delta RI, as shown in Table 5, where the Delta RI was 0.003 at
plasticizer levels of 40 to 70 phr in the soft (core) layer, and
0.002 at plasticizer levels of 80 to 100 phr in the soft (core)
layer. Finally, using a different mixture of plasticizers
(Plasticizer F) produced similar variation in Delta RI as that in
Table 3. Regardless of which high refractive index plasticizer or
mix of plasticizers having at least one high refractive index
plasticizer was used, the Delta RI was consistently lower and less
variable than when a conventional plasticizer (Plasticizer C) was
used.
[0131] The multilayer interlayers listed in Table 7 were produced
by mixing and melt co-extruding the mixtures of 100 parts
poly(vinyl butyral) resin with a plasticizer or plasticizer mix (A,
B, C, E or F as previously described above), and other common
additives. The poly(vinyl butyral) resin used in the stiff (skin)
layer had about 18 to 19 wt. % residual hydroxyl content and a
vinyl acetate residue of 2%, and the poly(vinyl butyral) resin used
in the soft (core) layer had about 10 to 11 wt. % residual hydroxyl
content and a vinyl acetate residue of 2%. All of the multiple
layer interlayers in Table 7 were produced by co-extruding the
mixtures of resin and plasticizer for the stiff (skin) and soft
(core) layer layers to form multilayer interlayer sheets at
standard conditions. The surface roughness, Rz, for all the
interlayers in Table 7 was about 42 to 45 microns. The type and
amount of plasticizer used and the respective refractive indices of
the layers are shown in Table 7. Additionally, the level of mottle
of the multiple layer interlayer sheet in a laminated multiple
layer glass panel was measured and is shown in Table 7 below. One
Conventional and one exemplary Disclosed Interlayer (samples G1 and
G5 respectively) were also tested for Haze and Pummel Adhesion
levels, to demonstrate that other performance properties and
characteristics of the interlayer were not adversely affected by
the inclusion of a high refractive index plasticizer (or mix of
plasticizers comprising at least one high refractive index
plasticizer and having a high refractive index for the
mixture).
TABLE-US-00007 TABLE 7 Skin Core Plasticizer Skin Plasticizer Core
Delta Pummel Sample Plasticizer (phr) RI (phr) RI RI Mottle % Haze
Adhesion G1 C 38 1.477 75 1.467 0.010 >4 0.2 3 G2 E 40 1.490 80
1.488 0.002 0 NT NT G3 B 40 1.496 84 1.496 0.000 0 NT NT G4 A 38
1.489 75 1.486 0.003 <1 NT NT G5 F 42 1.495 84 1.495 0.000 0 0.2
3 NT--Not Tested
[0132] Table 7 shows that for the Disclosed Interlayer samples
(which included a high refractive index plasticizer or mixture of
plasticizers comprising at least one high refractive index and
having a high refractive index for the mixture), the difference
between the refractive indices of the skin and core layers for the
samples with the high refractive index plasticizer(s) is lower
(that is, less than 0.010, or even less than 0.004, or 0.003 or
less) than the difference between the refractive indices of the
stiff (skin) and soft (core) layers of the interlayers with the
Conventional Plasticizer. Additionally, as shown in Table 7, the
mottle of the Disclosed Interlayers was less than 1, or even rated
as 0, which is significantly lower than the mottle in the
Conventional Interlayer, which was greater than 4, thus producing
an interlayer sheet with improved optical quality and very low
mottle.
[0133] Haze and Pummel Adhesion levels were tested on one
Conventional Interlayer and one Disclosed Interlayer (Samples G1
and G5 respectively), and there was no difference between them,
showing that there is no adverse effect due to the use of a high
refractive index plasticizer.
[0134] In conclusion, the interlayers comprising high refractive
index plasticizer(s) as described herein have advantages over
interlayers using conventional plasticizer having a lower
refractive index as previously utilized in the art. In general, use
of a high refractive index plasticizer either alone or in
combination with a conventional plasticizer and/or a second high
refractive index plasticizer results in significantly decreased
levels of mottle and good clarity (i.e., low haze) therefore
improved optical quality interlayers. Other advantages will be
readily apparent to those skilled in the art.
[0135] While the invention has been disclosed in conjunction with a
description of certain embodiments, including those that are
currently believed to be the preferred embodiments, the detailed
description is intended to be illustrative and should not be
understood to limit the scope of the present disclosure. As would
be understood by one of ordinary skill in the art, embodiments
other than those described in detail herein are encompassed by the
present invention. Modifications and variations of the described
embodiments may be made without departing from the spirit and scope
of the invention.
[0136] It will further be understood that any of the ranges,
values, or characteristics given for any single component of the
present disclosure can be used interchangeably with any ranges,
values or characteristics given for any of the other components of
the disclosure, where compatible, to form an embodiment having
defined values for each of the components, as given herein
throughout. For example, an interlayer can be formed comprising
poly(vinyl butyral) having a residual hydroxyl content in any of
the ranges given in addition to comprising a plasticizers in any of
the ranges given to form many permutations that are within the
scope of the present disclosure, but that would be cumbersome to
list. Further, ranges provided for a genus or a category, such as
phthalates or benzoates, can also be applied to species within the
genus or members of the category, such as dioctyl terephthalate,
unless otherwise noted.
* * * * *