U.S. patent application number 17/246044 was filed with the patent office on 2021-11-18 for protein polyurethane alloys and layered materials including the same.
The applicant listed for this patent is Modern Meadow, Inc.. Invention is credited to Samuel BROADBENT, Shaobo CAI, Casey CROWNHART, Lixin Dai, Dale L. HANDLIN, JR., Alexander Iain NORMAN, Zhe TAN, David WILLIAMSON, Nicholas YARAGHI.
Application Number | 20210355326 17/246044 |
Document ID | / |
Family ID | 1000005750475 |
Filed Date | 2021-11-18 |
United States Patent
Application |
20210355326 |
Kind Code |
A1 |
BROADBENT; Samuel ; et
al. |
November 18, 2021 |
PROTEIN POLYURETHANE ALLOYS AND LAYERED MATERIALS INCLUDING THE
SAME
Abstract
Protein polyurethane alloys including one or more proteins
dissolved within one or more polyurethanes. The protein
polyurethane alloy may have one or more mechanical properties that
are superior to the polyurethane in the absence of protein. The
protein polyurethane alloys may be incorporated into a layered
material including one or more protein polyurethane alloy
layers.
Inventors: |
BROADBENT; Samuel; (Hazlet,
NJ) ; HANDLIN, JR.; Dale L.; (Clifton, NJ) ;
CAI; Shaobo; (Oradell, NJ) ; TAN; Zhe;
(Secaucus, NJ) ; CROWNHART; Casey; (Hoboken,
NJ) ; YARAGHI; Nicholas; (Hoboken, NJ) ;
WILLIAMSON; David; (Towaco, NJ) ; NORMAN; Alexander
Iain; (Somerville, NJ) ; Dai; Lixin;
(Livingston, NJ) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Modern Meadow, Inc. |
Nutley |
NJ |
US |
|
|
Family ID: |
1000005750475 |
Appl. No.: |
17/246044 |
Filed: |
April 30, 2021 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
63110760 |
Nov 6, 2020 |
|
|
|
63018891 |
May 1, 2020 |
|
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08L 2201/10 20130101;
C08L 89/06 20130101; C08L 75/04 20130101 |
International
Class: |
C08L 89/06 20060101
C08L089/06; C08L 75/04 20060101 C08L075/04 |
Claims
1-29. (canceled)
30. A soy protein polyurethane alloy, comprising a soy protein
dissolved within a polyurethane, wherein the soy protein
polyurethane alloy has a Dynamic Mechanical Analysis (DMA)
tan(.delta.) peak at a temperature ranging from about -60.degree.
C. to about 30.degree. C. and a second DMA modulus transition onset
temperature ranging from about 130.degree. C. to about 200.degree.
C.
31. The soy protein polyurethane alloy of claim 30, wherein the soy
protein polyurethane alloy is transparent.
32. The soy protein polyurethane alloy of claim 30, wherein the
polyurethane has a Young's modulus in the absence of soy protein,
and wherein the soy protein polyurethane alloy has a Young's
modulus ranging from about 60% to about 570% greater than the
Young's modulus of the polyurethane in the absence of soy
protein.
33. The soy protein polyurethane alloy of claim 30, wherein the
polyurethane has a Young's modulus in the absence of soy protein,
and wherein the soy protein polyurethane alloy has a Young's
modulus ranging from about 35 MPa to about 340 MPa greater than the
Young's modulus of the polyurethane in the absence of soy
protein.
34. The soy protein polyurethane alloy of claim 30, wherein the soy
protein polyurethane alloy has a Young's modulus ranging from about
90 MPa to about 400 MPa.
35. The soy protein polyurethane alloy of claim 30, wherein the
polyurethane has a second DMA modulus transition onset temperature
in the absence of soy protein, and wherein the second DMA modulus
transition onset temperature of the soy protein polyurethane alloy
ranges from about 15.degree. C. to about 100.degree. C. greater
than the second DMA modulus transition onset temperature of the
polyurethane in the absence of soy protein.
36. The soy protein polyurethane alloy of claim 30, wherein the
polyurethane has a tensile strength in the absence of soy protein,
and wherein the soy protein polyurethane alloy has a tensile
strength ranging from about 10% to about 45% greater than the
tensile strength of the polyurethane in the absence of soy
protein.
37. The soy protein polyurethane alloy of claim 30, wherein the
polyurethane has a tensile strength in the absence of soy protein,
and wherein the soy protein polyurethane alloy has a tensile
strength ranging from about 1.5 MPa to about 5.5 MPa greater than
the tensile strength of the polyurethane in the absence of soy
protein.
38. The soy protein polyurethane alloy of claim 30, wherein the soy
protein polyurethane alloy has a tensile strength ranging from
about 14 MPa to about 19 MPa.
39. The soy protein polyurethane alloy of claim 30, comprising
about 10 wt % to about 50 wt % of the soy protein and about 50 wt %
to about 90 wt % of the polyurethane.
40. The soy protein polyurethane alloy of claim 30, comprising
about 20 wt % to about 35 wt % of the soy protein and about 65 wt %
to about 80 wt % of the polyurethane.
41. The soy protein polyurethane alloy of claim 30, wherein the
polyurethane has a moisture vapor transmission rate in the absence
of protein, and wherein the soy protein polyurethane alloy has a
moisture vapor transmission rate ranging from about 20% to about
600% greater than the moisture vapor transmission rate of the
polyurethane in the absence of protein.
42. The soy protein polyurethane alloy of claim 30, wherein the
polyurethane has a moisture vapor transmission rate in the absence
of protein, and wherein the soy protein polyurethane alloy has a
moisture vapor transmission rate ranging from about 30 g/m.sup.2/24
hr to about 500 g/m.sup.2/24 hr greater than the moisture vapor
transmission rate of the polyurethane in the absence of
protein.
43. The soy protein polyurethane alloy of claim 30, wherein the soy
protein polyurethane alloy has a moisture vapor transmission rate
ranging from about 30 g/m.sup.2/24 hr to about 1000 g/m.sup.2/24
hr.
44. The soy protein polyurethane alloy of claim 30, wherein the soy
protein is soy protein isolate.
45. The soy protein polyurethane alloy of claim 30, wherein the soy
protein is a chemically modified soy protein isolate.
Description
REFERENCE TO SEQUENCE LISTING SUBMITTED ELECTRONICALLY
[0001] The content of the electronically submitted sequence listing
in ASCII text file (Name: 4431_0680002_Seqlisting_ST25.txt; Size:
5,132 bytes; and Date of Creation: Apr. 30, 2021) filed with the
application is herein incorporated by reference in its
entirety.
FIELD
[0002] This disclosure relates to protein polyurethane alloys
comprising one or more proteins dissolved in a polyurethane. In
particular embodiments, this disclosure relates to protein
polyurethane alloys including one or more proteins dissolved only
in the hard phase of a polyurethane. In some embodiments, the
protein polymer alloys can have the look, feel, and aesthetic
and/or mechanical properties similar to natural leather, and can be
used to make goods and articles previously prepared from natural
leather.
BACKGROUND
[0003] Leather is a versatile product used across many industries,
including the furniture industry, where leather is regularly used
as upholstery, the clothing industry, where leather is used to
manufacture pants and jackets, the shoe industry, where leather is
used to prepare casual and dress shoes, the luggage industry, the
handbag and accessory industry, and in the automotive industry. The
global trade value for leather is high, and there is a continuing
and increasing demand for leather products. However, there are
variety of costs, constraints, and social concerns associated with
producing natural leather. Foremost, natural leathers are produced
from animal skins, and as such, requires raising and slaughtering
livestock. Raising livestock requires enormous amounts of feed,
pastureland, water, and fossil fuels and contributes to air and
waterway pollution, through, for example, greenhouse gases like
methane. Leather production also raises social concerns related to
the treatment of animals. In recent years, there has also been a
fairly well documented decrease in the availability of traditional
high quality hides. For at least these reasons, alternative means
to meet the demand for leather are desirable.
BRIEF SUMMARY
[0004] The present disclosure provides protein polyurethane alloys
suitable for use in a variety of applications, including as a
replacement for natural leather.
[0005] A first embodiment (1) of the present disclosure is directed
to a protein polyurethane alloy comprising a protein dissolved
within a polyurethane, where the protein is a protein other than a
soy protein.
[0006] In a second embodiment (2), the protein polyurethane alloy
of the first embodiment (1) has a Dynamic Mechanical Analysis (DMA)
tan(.delta.) peak at a temperature ranging from about -60.degree.
C. to about 30.degree. C., and a second DMA modulus transition
onset temperature ranging from about 120.degree. C. to about
200.degree. C.
[0007] In a third embodiment (3), the protein polyurethane alloy of
the first embodiment (1) or the second embodiment (2) is
transparent.
[0008] In a fourth embodiment (4), the polyurethane of the protein
polyurethane alloy of any one of embodiments (1)-(3) has a Young's
modulus in the absence of protein, and the protein polyurethane
alloy has a Young's modulus ranging from about 10% to about 600%
greater than the Young's modulus of the polyurethane in the absence
of protein.
[0009] In a fifth embodiment (5), the polyurethane of the protein
polyurethane alloy of any one of embodiments (1)-(3) has a Young's
modulus in the absence of protein, and the protein polyurethane
alloy has a Young's modulus ranging from about 40% to about 600%
greater than the Young's modulus of the polyurethane in the absence
of protein.
[0010] In a sixth embodiment (6), the polyurethane of the protein
polyurethane alloy of any one of embodiments (1)-(5) has a Young's
modulus in the absence of protein, and the protein polyurethane
alloy has a Young's modulus ranging from about 10 MPa to about 350
MPa greater than the Young's modulus of the polyurethane in the
absence of protein.
[0011] In a seventh embodiment (7), the polyurethane of the protein
polyurethane alloy of any one of embodiments (1)-(5) has a Young's
modulus in the absence of protein, and the protein polyurethane
alloy has a Young's modulus ranging from about 25 MPa to about 350
MPa greater than the Young's modulus of the polyurethane in the
absence of protein.
[0012] In an eighth embodiment (8), the polyurethane of the protein
polyurethane alloy of any one of embodiments (1)-(5) has a Young's
modulus in the absence of protein, and the protein polyurethane
alloy has a Young's modulus ranging from about 100 MPa to about 350
MPa greater than the Young's modulus of the polyurethane in the
absence of protein.
[0013] In a ninth embodiment (9), the protein polyurethane alloy of
any one of embodiments (1)-(8) has a Young's modulus ranging from
about 50 MPa to about 450 MPa.
[0014] In a tenth embodiment (10), the protein polyurethane alloy
of any one of embodiments (1)-(8) has a Young's modulus ranging
from about 75 MPa to about 450 MPa.
[0015] In an eleventh embodiment (11), the polyurethane of the
protein polyurethane alloy of any one of embodiments (1)-(10) has a
second DMA modulus transition onset temperature in the absence of
protein, and the protein polyurethane alloy has a second DMA
modulus transition onset temperature in degrees Celsius ranging
from about 5% to about 70% greater than the second DMA modulus
transition onset temperature of the polyurethane in the absence of
protein.
[0016] In a twelfth embodiment (12), the polyurethane of the
protein polyurethane alloy of any one of embodiments (1)-(10) has a
second DMA modulus transition onset temperature in the absence of
protein, and the protein polyurethane alloy has a second DMA
modulus transition onset temperature in degrees Celsius ranging
from about 15% to about 70% greater than the second DMA modulus
transition onset temperature of the polyurethane in the absence of
protein.
[0017] In a thirteenth embodiment (13), the polyurethane of the
protein polyurethane alloy of any one of embodiments (1)-(12) has a
second DMA modulus transition onset temperature in the absence of
protein, and the protein polyurethane alloy has a second DMA
modulus transition onset temperature ranging from about 5.degree.
C. to about 100.degree. C. greater than the second DMA modulus
transition onset temperature of the polyurethane in the absence of
protein.
[0018] In a fourteenth embodiment (14), the polyurethane of the
protein polyurethane alloy of any one of embodiments (1)-(12) has a
second DMA modulus transition onset temperature in the absence of
protein, and the protein polyurethane alloy has a second DMA
modulus transition onset temperature ranging from about 20.degree.
C. to about 80.degree. C. greater than the second DMA modulus
transition onset temperature of the polyurethane in the absence of
protein.
[0019] In a fifteenth embodiment (15), the polyurethane of the
protein polyurethane alloy of any one of embodiments (1)-(12) has a
second DMA modulus transition onset temperature in the absence of
protein, and the protein polyurethane alloy has a second DMA
modulus transition onset temperature ranging from about 40.degree.
C. to about 80.degree. C. greater than the second DMA modulus
transition onset temperature of the polyurethane in the absence of
protein.
[0020] In a sixteenth embodiment (16), the protein polyurethane
alloy of any one of embodiments (1)-(15) has a second DMA modulus
transition onset temperature ranging from about 130.degree. C. to
about 200.degree. C.
[0021] In a seventeenth embodiment (17), the protein polyurethane
alloy of any one of embodiments (1)-(15) has a second DMA modulus
transition onset temperature ranging from about 165.degree. C. to
about 200.degree. C.
[0022] In an eighteenth embodiment (18), the protein of the protein
polyurethane alloy of any one of embodiments (1)-(17) has an
isoelectric point ranging from about 4 to about 5 and a lysine
weight percent ranging from about 1 wt % to about 100 wt %.
[0023] In a nineteenth embodiment (19), the polyurethane of the
protein polyurethane alloy of any one of embodiments (1)-(18) has a
tensile strength in the absence of protein, and the protein
polyurethane alloy has a tensile strength ranging from about 5% to
about 55% greater than the tensile strength of the polyurethane in
the absence of protein.
[0024] In a twentieth embodiment (20), the polyurethane of the
protein polyurethane alloy of any one of embodiments (1)-(18) has a
tensile strength in the absence of protein, and the protein
polyurethane alloy has a tensile strength ranging from about 15% to
about 55% greater than the tensile strength of the polyurethane in
the absence of protein.
[0025] In a twenty-first embodiment (21), the polyurethane of the
protein polyurethane alloy of any one of embodiments (1)-(20) has a
tensile strength in the absence of protein, and the protein
polyurethane alloy has a tensile strength ranging from about 2 MPa
to about 8 MPa greater than the tensile strength of the
polyurethane in the absence of protein.
[0026] In a twenty-second embodiment (22), the polyurethane of the
protein polyurethane alloy of any one of embodiments (1)-(20) has a
tensile strength in the absence of protein, and the protein
polyurethane alloy has a tensile strength ranging from about 5 MPa
to about 8 MPa greater than the tensile strength of the
polyurethane in the absence of protein.
[0027] In a twenty-third embodiment (23), the protein polyurethane
alloy of any one of embodiments (1)-(22) has a tensile strength
ranging from about 7 MPa to about 21 MPa.
[0028] In a twenty-fourth embodiment (24), the protein polyurethane
alloy of any one of embodiments (1)-(23) comprises about 10 wt % to
about 50 wt % of the protein and about 50 wt % to about 90 wt % of
the polyurethane.
[0029] In a twenty-fifth embodiment (25), the protein polyurethane
alloy of any one of embodiments (1)-(23) comprises about 20 wt % to
about 35 wt % of the protein and about 65 wt % to about 80 wt % of
the polyurethane.
[0030] In a twenty-sixth embodiment (26), the protein of the
protein polyurethane alloy of any one of embodiments (1)-(25) is a
protein other than collagen.
[0031] In a twenty-seventh embodiment (27), the polyurethane of the
protein polyurethane alloy of any one of embodiemnts (1)-(26) has a
moisture vapor transmission rate in the absence of protein, and the
protein polyurethane alloy has a moisture vapor transmission rate
ranging from about 20% to about 600% greater than the moisture
vapor transmission rate of the polyurethane in the absence of
protein.
[0032] In a twenty-eighth embodiment (28), the polyurethane of the
protein polyurethane alloy of any one of embodiments (1)-(27) has a
moisture vapor transmission rate in the absence of protein, and the
protein polyurethane alloy has a moisture vapor transmission rate
ranging from about 30 g/m.sup.2/24 hr to about 500 g/m.sup.2/24 hr
greater than the moisture vapor transmission rate of the
polyurethane in the absence of protein.
[0033] In a twenty-ninth embodiment (29), the protein polyurethane
alloy of any one of embodiments (1)-(28) has a moisture vapor
transmission rate ranging from about 30 g/m2/24hr to about 1000
g/m.sup.2/24 hr.
[0034] A thirtieth embodiment (30) is directed to a soy protein
polyurethane alloy comprising a soy protein dissolved within a
polyurethane, where the soy protein polyurethane alloy has a
Dynamic Mechanical Analysis (DMA) tan(.delta.) peak at a
temperature ranging from about -60.degree. C. to about 30.degree.
C. and a second DMA modulus transition onset temperature ranging
from about 130.degree. C. to about 200.degree. C.
[0035] In a thirty-first embodiment (31), the soy protein
polyurethane alloy of the thirtieth embodiment (30) is
transparent.
[0036] In a thirty-second embodiment (32), the polyurethane of the
soy protein polyurethane alloy of the thirtieth embodiment (30) or
the thirty-first embodiment (31) has a Young's modulus in the
absence of soy protein, and the soy protein polyurethane alloy has
a Young's modulus ranging from about 60% to about 570% greater than
the Young's modulus of the polyurethane in the absence of soy
protein.
[0037] In a thirty-third embodiment (33), the polyurethane of the
soy protein polyurethane alloy of any one of embodiments (30)-(32)
has a Young's modulus in the absence of soy protein, and the soy
protein polyurethane alloy has a Young's modulus ranging from about
35 MPa to about 340 MPa greater than the Young's modulus of the
polyurethane in the absence of soy protein.
[0038] In a thirty-fourth embodiment (34), the soy protein
polyurethane alloy of any one of embodiments (30)-(33) has a
Young's modulus ranging from about 90 MPa to about 400 MPa.
[0039] In a thirty-fifth embodiment (35), the polyurethane of the
soy protein polyurethane alloy of any one of embodiments (30)-(34)
has a second DMA modulus transition onset temperature in the
absence of soy protein, and the second DMA modulus transition onset
temperature of the soy protein polyurethane alloy ranges from about
15.degree. C. to about 100.degree. C. greater than the second DMA
modulus transition onset temperature of the polyurethane in the
absence of soy protein.
[0040] In a thirty-sixth embodiment (36), the polyurethane of the
soy protein polyurethane alloy of any one of embodiments (30)-(35)
has a tensile strength in the absence of soy protein, and the soy
protein polyurethane alloy has a tensile strength ranging from
about 10% to about 45% greater than the tensile strength of the
polyurethane in the absence of soy protein.
[0041] In a thirty-seventh embodiment (37), the polyurethane of the
soy protein polyurethane alloy of any one of embodiments (30)-(36)
has a tensile strength in the absence of soy protein, and the soy
protein polyurethane alloy has a tensile strength ranging from
about 1.5 MPa to about 5.5 MPa greater than the tensile strength of
the polyurethane in the absence of soy protein.
[0042] In thirty-eigth embodiment (38), the soy protein
polyurethane alloy of any one of embodiments (30)-(37) has a
tensile strength ranging from about 14 MPa to about 19 MPa.
[0043] In a thirty-ninth embodiment (39), the soy protein
polyurethane alloy of any one of embodiments (30)-(38) comprises
about 10 wt % to about 50 wt % of the soy protein and about 50 wt %
to about 90 wt % of the polyurethane.
[0044] In a fortieth embodiment (40), the soy protein polyurethane
alloy of any one of embodiments (30)-(38) comprises about 20 wt %
to about 35 wt % of the soy protein and about 65 wt % to about 80
wt % of the polyurethane.
[0045] In a fourty-first embodiment (41), the polyurethane of the
soy protein polyurethane alloy of any one of embodiments (30)-(40)
has a moisture vapor transmission rate in the absence of protein,
and the soy protein polyurethane alloy has a moisture vapor
transmission rate ranging from about 20% to about 600% greater than
the moisture vapor transmission rate of the polyurethane in the
absence of protein.
[0046] In a fourty-second embodiment (42), the polyurethane of the
soy protein polyurethane alloy of any one of embodiments (30)-(41)
has a moisture vapor transmission rate in the absence of protein,
and the soy protein polyurethane alloy has a moisture vapor
transmission rate ranging from about 30 g/m.sup.2/24 hr to about
500 g/m.sup.2/24 hr greater than the moisture vapor transmission
rate of the polyurethane in the absence of protein.
[0047] In a fourty-third embodiment (43), the soy protein
polyurethane alloy of any one of embodiments (30)-(42) has a
moisture vapor transmission rate ranging from about 30 g/m.sup.2/24
hr to about 1000 g/m.sup.2/24 hr.
[0048] In a fourty-fourth embodiment (44), the protein of the soy
protein polyurethane alloy of any one of embodiments (30)-(43) is
soy protein isolate.
[0049] In a fourty-fifth embodiment (45), the protein of the soy
protein polyurethane alloy of any one of embodiments (40)-(43) is a
chemically modified soy protein isolate.
BRIEF DESCRIPTION OF THE FIGURES
[0050] The accompanying figures, which are incorporated herein,
form part of the specification and illustrate embodiments of the
present disclosure. Together with the description, the figures
further serve to explain the principles of and to enable a person
skilled in the relevant art(s) to make and use the disclosed
embodiments. These figures are intended to be illustrative, not
limiting. Although the disclosure is generally described in the
context of these embodiments, it should be understood that it is
not intended to limit the scope of the disclosure to these
particular embodiments. In the drawings, like reference numbers
indicate identical or functionally similar elements.
[0051] FIG. 1 is a dynamic mechanical analysis (DMA) graph of
storage modulus versus temperature for various materials.
[0052] FIG. 2 is a graph showing the relationship between maximum
tensile stress and gelatin weight percent for gelatin polyurethane
alloys according to some embodiments.
[0053] FIG. 3 is a graph showing the relationship between Young's
modulus and gelatin weight percent for gelatin polyurethane alloys
according to some embodiments.
[0054] FIG. 4 is a DMA graph of storage modulus versus temperature
for various materials.
[0055] FIG. 5 is a graph showing the relationship between maximum
tensile stress and soy protein isolate (SPI) weight percent for SPI
polyurethane alloys according to some embodiments.
[0056] FIG. 6 is a graph showing the relationship between Young's
modulus and SPI weight percent for SPI polyurethane alloys
according to some embodiments.
[0057] FIG. 7 is a DMA graph of storage modulus versus temperature
for various materials.
[0058] FIG. 8A is a graph comparing the maximum tensile stress of
various protein polyurethane alloys according to some
embodiments.
[0059] FIG. 8B is a graph comparing the Young's modulus of various
protein polyurethane alloys according to some embodiments.
[0060] FIG. 9 is a DMA thermogram comparing L3360 and a gelatin
L3360 alloy according to some embodiments.
[0061] FIG. 10 is a DMA thermogram comparing Hauthane HD-2001
polyurethane and a gelatin Hauthane HD-2001 polyurethane alloy
according to some embodiments.
[0062] FIG. 11 is a DMA thermogram comparing SANCURE.TM. 20025F
polyurethane and a gelatin SANCURE.TM. 20025F polyurethane alloy
according to some embodiments.
[0063] FIG. 12 is a DMA thermogram comparing IMPRANIL.RTM. DLS
polyurethane and a gelatin IMPRANIL.RTM. DLS polyurethane alloy
according to some embodiments.
[0064] FIG. 13 is a DMA thermogram comparing BONDTHANE.TM. UD-108
polyurethane and a gelatin BONDTHANE.TM. UD-108 polyurethane alloy
according to some embodiments.
[0065] FIG. 14 is a DMA thermogram comparing BONDTHANE.TM. UD-303
polyurethane and a gelatin BONDTHANE.TM. UD-303 polyurethane alloy
according to some embodiments.
[0066] FIG. 15 is a DMA thermogram comparing BONDTHANE.TM. UD-250
polyurethane and a gelatin BONDTHANE.TM. UD-250 polyurethane alloy
according to some embodiments.
[0067] FIG. 16 is a representative DMA graph illustrating the
methodology of measuring first and second DMA modulus transition
onset temperatures.
[0068] FIG. 17 illustrates a layered material according to some
embodiments.
[0069] FIG. 18 illustrates a layered material according to some
embodiments.
[0070] FIG. 19 is a block diagram illustrating a method for making
a layered material according to some embodiments.
[0071] FIGS. 20A-20F illustrate a method of making a layered
material according to some embodiments.
[0072] FIG. 21 illustrates a spacer fabric according to some
embodiments.
[0073] FIG. 22 is a DMA thermogram comparing IMPRAPERM.RTM. DL 5249
polyurethane and a soy protein isolate IMPRAPERM.RTM. DL 5249 alloy
according to some embodiments.
[0074] FIG. 23 is a graph measuring the weight of water transported
through the construction as weight change versus time for a
multi-layer protein polyurethane alloy according to some
embodiments.
DETAILED DESCRIPTION
[0075] The indefinite articles "a," "an," and "the" include plural
referents unless clearly contradicted or the context clearly
dictates otherwise.
[0076] The term "comprising" is an open-ended transitional phrase.
A list of elements following the transitional phrase "comprising"
is a non-exclusive list, such that elements in addition to those
specifically recited in the list can also be present. The phrase
"consisting essentially of" limits the composition of a component
to the specified materials and those that do not materially affect
the basic and novel characteristic(s) of the component. The phrase
"consisting of" limits the composition of a component to the
specified materials and excludes any material not specified.
[0077] Where a range of numerical values comprising upper and lower
values is recited herein, unless otherwise stated in specific
circumstances, the range is intended to include the endpoints
thereof, and all integers and fractions within the range. It is not
intended that the disclosure or claims be limited to the specific
values recited when defining a range. Further, when an amount,
concentration, or other value or parameter is given as a range, one
or more ranges, or as list of upper values and lower values, this
is to be understood as specifically disclosing all ranges formed
from any pair of any upper range limit or value and any lower range
limit or value, regardless of whether such pairs are separately
disclosed. Finally, when the term "about" is used in describing a
value or an end-point of a range, the disclosure should be
understood to include the specific value or end-point referred to.
Whether or not a numerical value or end-point of a range recites
"about," the numerical value or end-point of a range is intended to
include two embodiments: one modified by "about," and one not
modified by "about."
[0078] As used herein, the term "about" refers to a value that is
within .+-.10% of the value stated. For example, about 3 MPa can
include any number between 2.7 MPa and 3.3 MPa.
[0079] As used herein, a first layer described as "attached to" a
second layer means that the layers are attached to each other
either by direct contact and attachment between the two layers or
via one or more intermediate adhesive layers. An intermediate
adhesive layer can be any layer that serves to attach a first layer
to a second layer.
[0080] As used herein, the phrase "disposed on" means that a first
component (e.g., layer) is in direct contact with a second
component. A first component "disposed on" a second component can
be deposited, formed, placed, or otherwise applied directly onto
the second component. In other words, if a first component is
disposed on a second component, there are no components between the
first component and the second component.
[0081] As used herein, the phrase "disposed over" means other
components (e.g., layers or substrates) may or may not be present
between a first component and a second component.
[0082] As used herein, a "bio-based polyurethane" is a polyurethane
where the building blocks of polyols, such as diols and diacids
like succinic acid, are derived from a biological material such as
corn starch.
[0083] As used herein, the term "substantially free of" means that
a component is present in a detectable amount not exceeding about
0.1 wt %.
[0084] As used herein, the term "free of" means that a component is
not present in a blend or material (e.g., a protein polyurethane
alloy), even in trace amounts.
[0085] As used herein "collagen" refers to the family of at least
28 distinct naturally occurring collagen types including, but not
limited to collagen types I, II, III, IV, V, VI, VII, VIII, IX, X,
XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XIX, and XX. The term
collagen as used herein also refers to collagen prepared using
recombinant techniques. The term collagen includes collagen,
collagen fragments, collagen-like proteins, triple helical
collagen, alpha chains, monomers, gelatin, trimers and combinations
thereof. Recombinant expression of collagen and collagen-like
proteins is known in the art (see, e.g., Bell, EP 1232182B1, Bovine
collagen and method for producing recombinant gelatin; Olsen, et
al., U.S. Pat. No. 6,428,978 and VanHeerde, et al., U.S. Pat. No.
8,188,230, incorporated by reference herein in their entireties)
Unless otherwise specified, collagen of any type, whether naturally
occurring or prepared using recombinant techniques, can be used in
any of the embodiments described herein. That said, in some
embodiments, the collagen described herein can be prepared using
bovine Type I collagen. Collagens are characterized by a repeating
triplet of amino acids, -(Gly-X-Y)n-, so that approximately
one-third of the amino acid residues in collagen are glycine. X is
often proline and Y is often hydroxyproline. Thus, the structure of
collagen may consist of three intertwined peptide chains of
differing lengths. Different animals may produce different amino
acid compositions of the collagen, which may result in different
properties (and differences in the resulting leather).
[0086] In some embodiments, the collagen can be chemically modified
to promote solubility in water.
[0087] Any type of collagen, truncated collagen, unmodified or
post-translationally modified, or amino acid sequence-modified
collagen can be used as part of the protein polyurethane alloy.
[0088] In some embodiments, the collagen can be plant-based
collagen. For example, the collagen can be a plant-based collagen
made by CollPlant.
[0089] In some embodiments, a collagen solution can be fibrillated
into collagen fibrils. As used herein, collagen fibrils refer to
nanofibers composed of tropocollagen or tropocollagen-like
structures (which have a triple helical structure). In some
embodiments, triple helical collagen can be fibrillated to form
nanofibrils of collagen.
[0090] In some embodiments, a recombinant collagen can comprise a
collagen fragment of the amino acid sequence of a native collagen
molecule capable of forming tropocollagen (trimeric collagen). A
recombinant collagen can also comprise a modified collagen or
truncated collagen having an amino acid sequence at least 70, 80,
90, 95, 96, 97, 98, or 99% identical or similar to a native
collagen amino acid sequence (or to a fibril forming region thereof
or to a segment substantially comprising [Gly-X-Y]n). In some
embodiments, the collagen fragment can be a 50 kDa portion of a
native collagen. Native collagen sequences include the amino acid
sequences of CollA1, CollA2, and Col3A1, described by Accession
Nos. NP_001029211.1, NP_776945.1 and NP_001070299.1, which are
incorporated by reference. In some embodiments, the collagen
fragment can be a portion of human collagen alpha-1(III) (Col3A1;
Uniprot #P02461, Entrez Gene ID #1281). In some embodiments, the
collagen fragment can comprise the amino acid sequence listed as
SEQ ID NO: 1.
[0091] Methods of producing recombinant collagen and recombinant
collagen fragments are known in the art. For example, U.S. Pub.
Nos. 2019/0002893, 2019/0040400, 2019/0093116, and 2019/0092838
provide methods for producing collagen and collagen fragments that
can be used to produce the recombinant collagen and recombinant
collagen fragments disclosed herein. The contents of these four
publications are incorporated by reference in their entirety.
[0092] Protein polyurethane alloys described herein can comprise a
protein that is miscible with only one of a plurality of phases of
a polyurethane, or a plurality of polyurethanes, with which it is
blended. For example, in some embodiments, the protein polyurethane
alloy can include a protein that is miscible with only the hard
phase of the polyurethane, or the plurality of polyurethanes,
having both a hard phase and a soft phase. Protein polyurethane
alloys described herein can be free of or substantially free of
protein in form of particles dispersed in a polyurethane. For
example, in some embodiments, the protein polyurethane alloys can
be free of or substantially free of protein particles having an
average diameter of greater than 1 micron (.mu.m).
[0093] In some embodiments, the protein polyurethane alloys can be
free of or substantially free of soy protein particles having an
average diameter of greater than 1 micron (.mu.m). In some
embodiments, the protein polyurethane alloys can be free of or
substantially free of collagen particles having an average diameter
of greater than 1 micron (.mu.m). In some embodiments, the protein
polyurethane alloys can be free of or substantially free of gelatin
particles having an average diameter of greater than 1 micron
(.mu.m). In some embodiments, the protein polyurethane alloys can
be free of or substantially free of bovine serum albumin particles
having an average diameter of greater than 1 micron (.mu.m). In
some embodiments, the protein polyurethane alloys can be free of or
substantially free of pea protein particles having an average
diameter of greater than 1 micron (.mu.m). In some embodiments, the
protein polyurethane alloys can be free of or substantially free of
egg white albumin particles having an average diameter of greater
than 1 micron (.mu.m). In some embodiments, the protein
polyurethane alloys can be free of or substantially free of casein
protein particles having an average diameter of greater than 1
micron (.mu.m). In some embodiments, the protein polyurethane
alloys can be free of or substantially free of peanut protein
particles having an average diameter of greater than 1 micron
(.mu.m). In some embodiments, the protein polyurethane alloys can
be free of or substantially free of edestin protein particles
having an average diameter of greater than 1 micron (.mu.m). In
some embodiments, the protein polyurethane alloys can be free of or
substantially free of whey protein particles having an average
diameter of greater than 1 micron (.mu.m) In some embodiments, the
protein polyurethane alloys can be free of or substantially free of
karanj a protein particles having an average diameter of greater
than 1 micron (.mu.m). In some embodiments, the protein
polyurethane alloys can be free of, or substantially free of,
cellulase particles having an average diameter of greater than 1
micron (.mu.m). In some embodiments, the protein polyurethane
alloys can be free of, or substantially free of, recombinant
collagen fragment particles having an average diameter of greater
than 1 micron (.mu.m).
[0094] In particular embodiments, the present disclosure provides a
unique combination of a protein and a polyurethane in which the
protein is dissolved in only the hard phase of the polyurethane.
The present disclosure also provides methods of making the protein
polyurethane alloys described herein. The present disclosure also
provides layered materials including one or more of the protein
polyurethane alloy layers and methods of making the layered
materials. The protein polyurethane alloys and the protein
polyurethane alloy layers can include one or more types of protein
and one or more polyurethanes.
[0095] Proteins suitable for use in the alloys disclosed herein can
be un-modified or chemically modified. In some embodiments, the
protein can be modified to facilitate miscibility of the protein
with the hard phase of the polyurethane. In some embodiments, the
protein can be chemically modified to promote solubility in water.
In such embodiments, the chemical modification to promote
solubility in water can facilitate miscibility of the protein with
the hard phase of the polyurethane. In some embodiments, the
chemically modified protein can be a partially hydrolyzed protein.
In some embodiments, the chemically modified protein can be a
protein modified by covalent attachment of hydrophilic polymer
chains, such as polyethylene glycol (PEG) chains, to the
protein.
[0096] Suitable polyurethanes for use in the protein polyurethane
alloys described herein include those that comprise at least two
phases including a "soft phase" and a "hard phase." The soft phase
is formed from polyol segments within the polyurethane that
separate from the urethane-containing phase due to differences in
polarity. The urethane-containing phase is referred to as the hard
phase. This phase separation is well known in the art and is the
basis of the many of the properties of polyurethanes.
[0097] The soft phase is typically elastomeric at room temperature,
and typically has a softening point or glass transition temperature
(Tg) below room temperature. The Tg can be measured by Dynamic
Mechanical Analysis (DMA) and quantified by either the peak of
tan(.delta.) or the onset of the drop in storage modulus.
Alternately, Tg can be measured by Differential Scanning
Calorimetry (DSC). In some cases, there can be crystallinity in the
soft phase, which can be seen as a melting point, typically between
0.degree. C. and about 60.degree. C. For example, the peak in the
tan(.delta.) curve at about 35.degree. C. for UD-108 polyurethane
in FIG. 13 indicates crystallinity in the soft phase of the
polyurethane.
[0098] The hard phase typically has a Tg or melting point above
room temperature, more typically above about 80.degree. C. The
softening of the hard phase can be measured by measuring the onset
of the drop in storage modulus (sometimes referred to as stiffness)
as measured by DMA.
[0099] The "soft phase" for the polyurethane or the protein
polyurethane alloy including the polyurethane comprises the polyol
component of the polyurethane. Its function is to be soft and
flexible at temperatures above its Tg to lend toughness,
elongation, and flexibility to the polyurethane. Typical soft
segments can comprise polyether polyols, polyester polyols,
polycarbonate polyols, and mixtures thereof. They typically range
in molecular weight from about 250 daltons to greater than about 5
kiloDaltons. The "hard phase" for the polyurethane or the protein
polyurethane alloy including the polyurethane comprises the
urethane segments of the polymer that are imparted by the
isocyanate(s) used to connect the polyols along with short chain
diols such as butane diol, propane diol, and the like. Typical
isocyanates useful for the present polyurethanes include, but are
not limited to, hexamethylene diisocyanate, isophorone
diisocyanate, methylene diisocyanate, phenyl diisocyanate, and the
like. These molecules are more polar and stiffer than the polyols
used to make the soft segment. Therefore, the hard segment is
stiffer and has a higher softening point compared to the soft
segment. The function of the hard phase is to provide, among other
properties, strength, temperature resistance, and abrasion
resistance to the polyurethane.
[0100] In some embodiments described herein, the protein can be
miscible with only the hard phase, leaving soft phase transitions
substantially unaltered. Without wishing to be bound particular
theory, it is believed that when the protein is dissolved in the
hard phase, it significantly increases the temperature at which the
hard phase begins to soften, thus increasing the temperature
resistance of the alloy described herein. Protein polyurethane
alloys described herein can also have increased stiffness and
increased strength relative to the base polyurethane (i.e., the
polyurethane by itself, in the absence of protein).
[0101] Protein polyurethane alloys and layers described herein can
be formed by blending one or more proteins with one or more
water-borne polyurethane dispersions in a liquid state and drying
the blend. In some embodiments, the protein polyurethane alloys and
layers described herein can be formed by blending one or more
proteins dissolved or dispersed in an aqueous solution with one or
more water-borne polyurethane dispersions in a liquid state and
drying the blend. In some embodiments, the polyurethane dispersion
can be ionic, and either anionic or cationic. In some embodiments,
the polyurethane dispersion can be nonionic. In some embodiments,
the blended protein and polyurethane can be formed into a sheet and
can, in certain embodiments, be attached to a substrate layer using
a suitable attachment process, such as direct coating, a lamination
process or a thermo-molding process. In certain embodiments, the
lamination process can include attaching the sheet to the substrate
layer using an adhesive layer. In some embodiments, the blended
protein and polyurethane can be coated or otherwise deposited over
a substrate layer to attach the blended protein and polyurethane to
the substrate layer. In some embodiments, attaching the blended
protein and polyurethane to the substrate layer can result in a
portion of the blended protein and polyurethane being integrated
into a portion of the substrate layer.
[0102] In a protein polyurethane alloy including one or more
miscible proteins and polyurethanes, the one or more proteins can
be dissolved within the hard phase of the one or more
polyurethanes. The protein polyurethane alloy can include at least
one protein miscible with the hard phase of one or more
polyurethanes in the alloy. In some embodiments, the protein
polyurethane alloy can include a plurality of proteins and/or a
plurality of polyurethane hard phases that are miscible with each
other. In all of these embodiments, and without wishing to be bound
by a particular theory, the protein, or plurality of proteins, is
believed to be dissolved in the hard phase of the polyurethane, or
plurality of polyurethanes.
[0103] One or more proteins dissolved within the hard phase of one
or more polyurethanes can form a homogenous mixture when blended.
In some embodiments, the protein polyurethane alloy can include a
plurality of proteins dissolved within or more polyurethanes such
that the proteins and the polyurethane(s) form a homogenous mixture
when blended and dried. Typically, the protein polyurethane alloy
including a homogenous mixture of protein and polyurethane does not
include a substantial amount of protein not dissolved in the
polyurethane. That said, and in some embodiments, the protein
polyurethane alloy can include a fraction of protein dispersed
within the polyurethane.
[0104] In embodiments described herein, the miscibility of the
protein with the hard phase of the polyurethane can increase the
DMA modulus transition softening onset temperature of the hard
phase in a protein polyurethane alloy without significantly
changing one or more other thermo-mechanical properties of the
alloy relative to the thermo-mechanical properties of the
polyurethane by itself. For example, the miscibility of the protein
with the hard phase of the polyurethane can increase the DMA
modulus transition onset temperature of the hard phase in the
protein polyurethane alloy without significantly changing the DMA
transition temperature of the soft phase in the alloy relative to
the DMA transition temperature of the soft phase of the
polyurethane by itself.
[0105] The DMA transition temperature of the soft phase can be
referred to as the glass transition temperature (Tg) of a
polyurethane or the protein polyurethane alloy. The DMA transition
temperature of the soft phase, or Tg, can be quantified as (i) the
DMA storage modulus transition onset temperature of the soft phase
(referred to herein as the "first DMA modulus transition onset
temperature") or (ii) the DMA tan(.delta.) peak temperature
corresponding to the soft phase. The DMA transition temperature of
the hard phase can be measured by the onset of the drop in the
storage modulus of the polyurethane or the polyurethane protein
alloy and can be quantified as the DMA modulus transition onset
temperature of the hard phase (referred to herein as the "second
DMA modulus transition onset temperature"). In some embodiments,
the second DMA modulus transition onset temperature of the protein
polyurethane alloy can be above about 80.degree. C. or above about
130.degree. C.
[0106] Although many types of proteins are contemplated for use in
the protein polyurethane alloys described herein including, for
example, collagen and soy proteins, it is understood that for all
of the embodiments disclosed herein, the protein can be a protein
other than collagen and/or a protein other than a soy protein.
Thus, in some embodiments, the protein dissolved in the protein
polyurethane alloy can be a protein other than collagen. In other
embodiments, the protein dissolved in the protein polyurethane
alloy can be a protein other than a soy protein. In some
embodiments, the protein dissolved in the protein polyurethane
alloy can be a protein other than collagen and a protein other than
a soy protein. In some embodiments, the protein polyurethane alloy
can be free of or substantially free of collagen. In some
embodiments, the protein polyurethane alloy can be free of or
substantially free of soy protein. In some embodiments, the protein
polyurethane alloy can be free of or substantially free of soy
protein and collagen.
[0107] As previously discussed, the soft phase and the hard phase
of the polyurethane can be measured using Dynamic Mechanical
Analysis (DMA). Accordingly, the one or more polyurethanes included
in the protein polyurethane alloys described herein can have at
least two DMA transition temperatures, one corresponding to the
soft phase and one corresponding to the hard phase. The DMA
transition temperature of the soft phase can be quantified as a
"first DMA modulus transition onset temperature" or DMA
tan(.delta.) peak temperature corresponding to the soft phase. The
DMA transition temperature of the hard phase can be quantified by a
"second DMA modulus transition onset temperature." The first DMA
modulus transition onset temperature or a DMA tan(.delta.) peak
temperature is a lower DMA transition temperature and the second
DMA modulus transition onset temperature is a higher DMA transition
temperature.
[0108] Similarly, the protein polyurethane alloys described herein
can have at least two phases. The at least two phases can include
the soft phase and the hard phase. Different phases of the alloys
can be measured and quantified in the same manner as described
above for the polyurethanes.
[0109] The polyurethane or the protein polyurethane alloy having
first and second DMA transition temperatures means that it has a
first DMA transition temperature that occurs at a lower temperature
than the second DMA transition temperature. However, the first and
second transition temperatures need not be sequential transition
temperatures. Other DMA transition temperatures could occur between
the first and second transitions.
[0110] In some embodiments, the first DMA modulus transition onset
temperature for a polyurethane can be below 30.degree. C. In some
embodiments, the first DMA modulus transition onset temperature for
a polyurethane can range from about -65.degree. C. to about
30.degree. C., including subranges. For example, in some
embodiments, the first DMA modulus transition onset temperature for
a polyurethane can be about -65.degree. C., about -60.degree. C.,
about -55.degree. C., about -50.degree. C., about -45.degree. C.,
about -40.degree. C., about -35.degree. C., about -30.degree. C.,
about -25.degree. C., about -20.degree. C., about -15.degree. C.,
about -10.degree. C., about -5.degree. C., about -1.degree. C.,
0.degree. C., about 1.degree. C., about 5.degree. C., about
10.degree. C., about 15.degree. C., about 20.degree. C., about
25.degree. C., or about 30.degree. C., or within a range having any
two of these values as endpoints, inclusive of the endpoints. In
some embodiments, the first DMA modulus transition onset
temperature of a polyurethane can be about -65.degree. C. to about
30.degree. C., about -65.degree. C. to about 25.degree. C., about
-65.degree. C. to about 20.degree. C., about -65.degree. C. to
about 15.degree. C., about -65.degree. C. to about 10.degree. C.,
about -65.degree. C. to about 5.degree. C., about -65.degree. C. to
about 1.degree. C., about -65.degree. C. to 0.degree. C., about
-65.degree. C. to about -1.degree. C., about -65.degree. C. to
about -5.degree. C., about -65.degree. C. to about -10.degree. C. ,
about -65.degree. C. to about -15.degree. C. , about -65.degree. C.
to about -20.degree. C., about -65.degree. C. to about -25.degree.
C., about -65.degree. C. to about -30.degree. C., about -65.degree.
C. to about -35.degree. C., about -65.degree. C. to about
-35.degree. C., about -65.degree. C. to about -40.degree. C., or
about -65.degree. C. to about -45.degree. C.
[0111] FIGS. 9-15 show DMA thermograms for various exemplary
polyurethanes. The first DMA modulus transition onset temperature
(T.sub.onset1) for each exemplary polyurethane is the temperature
at which the slope of the storage modulus (E') curve begins to
decrease significantly for a first time. The methodology of
measuring this value is exemplified in FIG. 16. DMA equipment, such
a DMA-850 from TA Instruments, can be programed to calculate this
temperature automatically. Table 4 lists the first DMA modulus
transition onset temperatures automatically calculated from the DMA
graphs in FIGS. 9-15 (see Example Nos. 1-7).
[0112] In some embodiments, the DMA tan(.delta.) peak temperature
corresponding to the soft phase of a polyurethane can be below
30.degree. C. In some embodiments, the DMA tan(.delta.) peak
temperature corresponding to the soft phase of a polyurethane can
range from about -60.degree. C. to about 30.degree. C., including
subranges. For example, in some embodiments, the DMA tan(.delta.)
peak temperature corresponding to the soft phase of a polyurethane
can be about -60.degree. C., about -55.degree. C., about
-50.degree. C., about -45.degree. C., about -40.degree. C., about
-35.degree. C., about -30.degree. C., about -25.degree. C., about
-20.degree. C., about -15.degree. C., about -10.degree. C., about
-5.degree. C., about -1.degree. C., 0.degree. C., about 1.degree.
C., about 5.degree. C., about 10.degree. C., about 15.degree. C.,
about 20.degree. C., about 25.degree. C., or about 30.degree. C.,
or within a range having any two of these values as endpoints,
inclusive of the endpoints. In some embodiments, the DMA
tan(.delta.) peak temperature corresponding to the soft phase of a
polyurethane can be about -60.degree. C. to about 30.degree. C.,
about -60.degree. C. to about 25.degree. C., about -60.degree. C.
to about 20.degree. C., about -60.degree. C. to about 15.degree.
C., about -60.degree. C. to about 10.degree. C., about -60.degree.
C. to about 5.degree. C., about -60.degree. C. to about 1.degree.
C. about -60.degree. C. to 0.degree. C., about -60.degree. C. to
about -1.degree. C., about -60.degree. C. to about -5.degree. C.,
about -60.degree. C. to about -10.degree. C. , about -60.degree. C.
to about -15.degree. C., about -60.degree. C. to about -20.degree.
C., about -60.degree. C. to about -25.degree. C., about -60.degree.
C. to about -30.degree. C., about -60.degree. C. to about
-35.degree. C., or about -60.degree. C. to about -40.degree. C.
[0113] The DMA thermograms in FIGS. 9-15 show the DMA tan(.delta.)
peak temperature corresponding to the soft phase for various
exemplary polyurethanes. Like DMA modulus transition onset
temperatures, DMA equipment, such a DMA-850 from TA Instruments,
can be programed to calculate this temperature automatically. Table
4 lists the DMA tan(.delta.) peak temperature automatically
calculated from the DMA graphs in FIGS. 9-15 (see Example Nos.
1-7).
[0114] In some embodiments, the second DMA modulus transition onset
temperature for a polyurethane can be above 30.degree. C. In some
embodiments, the second DMA modulus transition onset temperature
for a polyurethane can range from about 45.degree. C. to about
165.degree. C. For example, in some embodiments, the second DMA
modulus transition onset temperature for a polyurethane can be
about 45.degree. C., about 50.degree. C., about 55.degree. C.,
about 60.degree. C., about 65.degree. C., about 70.degree. C.,
about 75.degree. C., about 80.degree. C., about 85.degree. C.,
about 90.degree. C., about 95.degree. C., about 100.degree. C.,
about 105.degree. C., about 110.degree. C., about 115.degree. C.,
about 120.degree. C., about 125.degree. C., about 130.degree. C.,
about 135.degree. C., about 140.degree. C., about 145.degree. C.,
about 150.degree. C., about 155.degree. C., about 160.degree. C.,
or about 165.degree. C., or within any range having any two of
these values as endpoints, inclusive of the endpoints. In some
embodiments, the second DMA modulus transition onset temperature
for a polyurethane can be about 45.degree. C. to about 165.degree.
C., about 50.degree. C. to about 160.degree. C., about 55.degree.
C. to about 155.degree. C., about 60.degree. C. to about
150.degree. C., about 65.degree. C. to about 145.degree. C., about
70.degree. C. to about 140.degree. C., about 75.degree. C. to about
135.degree. C., about 80.degree. C. to about 130.degree. C., about
85.degree. C. to about 125.degree. C., about 90.degree. C. to about
120.degree. C., about 95.degree. C. to about 115.degree. C., or
about 100.degree. C. to about 110.degree. C.
[0115] The DMA thermograms in FIGS. 9-15 show the second DMA
modulus transition onset temperatures for various exemplary
polyurethanes. The second DMA modulus transition onset temperature
(T.sub.onset2) for each exemplary polyurethane is the temperature
at which the slope of the storage modulus (E') curve begins
decrease significantly for a second time. The methodology of
measuring this value is exemplified in FIG. 16. DMA equipment, such
a DMA-850 from TA Instruments, can be programed to calculate this
temperature automatically. Table 3 lists the second DMA modulus
transition onset temperatures automatically calculated from the DMA
graphs in FIGS. 9-15 (see Example Nos. 1-7).
[0116] In some embodiments, the polyurethane can exhibit
crystallinity in the soft phase. This is common in polyether soft
segments containing polytetramethylene glycol and some polyester
polyols. In such embodiments, the polyurethane can exhibit at least
three transitions: the Tg of the soft phase, the melting point of
the soft phase, and the modulus transition of the hard phase. Such
melting in the soft phase typically occurs between 0.degree. C. and
about 60.degree. C., when present. In embodiments exhibiting
crystallinity in the soft phase, the protein polyurethane alloy
will typically still exhibit the melting in the soft phase because
the protein is miscible with the hard phase, leaving the mechanical
properties of the soft phase substantially unchanged.
[0117] In typical embodiments described herein, the protein
polyurethane alloy can have a second DMA modulus transition onset
temperature higher than the second DMA modulus transition
temperature of the polyurethane in absence of protein (i.e., the
polyurethane by itself). It is believed that this increase in the
second DMA modulus transition onset temperature in the alloy is due
to the miscibility of the protein and the hard phase of the
polyurethane. This selective miscibility of the protein is
indicated by an increase in the second DMA modulus transition onset
temperature without a similar increase in DMA transition
temperature of the soft phase (quantified by a first DMA modulus
transition onset temperature or the DMA tan(.delta.) peak
temperature corresponding to the soft phase). This selective
miscibility can be utilized to control properties of the protein
polyurethane alloy, for example mechanical and thermal
properties.
[0118] In some embodiments, the protein polyurethane alloys and/or
the layered materials described herein can have a look and feel, as
well as mechanical properties, similar to natural leather. For
example, the protein polyurethane alloy layer or the layered
material including the protein polyurethane alloy layer can have,
among other things, haptic properties, aesthetic properties,
mechanical/performance properties, manufacturability properties,
and/or thermal properties similar to natural leather.
Mechanical/performance properties that can be similar to natural
leather include, but are not limited to, tensile strength, tear
strength, elongation at break, resistance to abrasion, internal
cohesion, water resistance, breathability (quantified in some
embodiments by a moisture vapor transmission rate measurement), and
the ability to be dyed with reactive dyes and to retain color when
rubbed (color fastness). Haptic properties that can be similar to
natural leather include, but are not limited to, softness,
rigidity, coefficient of friction, and compression modulus.
Aesthetic properties that can be similar to natural leather
include, but are not limited to, dyeability, embossability, aging,
color, color depth, and color patterns. Manufacturing properties
that can be similar to natural leather include, but are not limited
to, the ability to be stitched, cut, skived, and split. Thermal
properties that can be similar to natural leather include, but are
not limited to, heat resistance and resistance to stiffening or
softening over a significantly wide temperature range, for example
25.degree. C. to 100.degree. C.
[0119] Desirable properties for the protein polyurethane alloy
described herein, include but are not limited to, optical
properties, haptic properties, aesthetic properties, thermal
properties, mechanical properties, and/or breathability properties.
Exemplary thermal properties include heat resistance and resistance
to melting, and can be quantified by, for example, measuring the
second modulus transition onset temperature (T.sub.onset2) of a
material. Exemplary mechanical properties include abrasion
resistance, maximum tensile stress (also referred to as "tensile
strength"), and Young's modulus. Unless otherwise specified,
maximum tensile stress values and Young's modulus values disclosed
herein are measured according the methods provided by ASTM D638.
Exemplary breathability properties include moisture vapor
transmission rate (MVTR) measured in g/m.sup.2/24 hr (grams per
meters squared per 24 hours). Unless otherwise specified, moisture
vapor transmission rates disclosed herein are measured according to
the methods provided by ASTM E96-Method B.
[0120] In some embodiments, the protein polyurethane alloy can be
transparent. In some embodiments, a transparent protein
polyurethane alloy can indicate that the protein is miscible with
the hard phase of the polyurethane in the alloy. As used herein, a
"transparent" material means material having an opacity of about
50% or less. Opacity is measured by placing a sample of material
over a white background to measure the Y tristimulus value ("Over
white Y") in reflectance with a spectrometer using the D65 10
degree illuminant. The same sample is then placed over a black
background and the measurement is repeated, yielding "Over black
Y". Percent opacity is calculated as "Over black Y" divided by
"Over white Y" times 100. 100% opacity is defined as lowest
transparency and 0% opacity is defined as the highest
transparency.
[0121] In some embodiments, the protein polyurethane alloy can be
transparent and can have an opacity ranging from 0% to about 50%,
including subranges. For example, the transparent protein
polyurethane alloy, can have an opacity ranging from 0% to about
40%, 0% to about 30%, 0% to about 20%, 0% to about 10%, or 0% to
about 5%. The transparency of the protein polyurethane alloy is
evaluated before dying or otherwise coloring the protein
polyurethane alloy.
[0122] A transparent protein polyurethane alloy can be created by
selecting and blending the appropriate combination of one or more
proteins and one or more polyurethanes. While not all combinations
of protein and polyurethane will result in a transparent protein
polyurethane alloy, it is within the skill of the ordinarily
skilled artisan to identify whether a given blend results in a
transparent protein polyurethane alloy in view of this disclosure.
In embodiments directed to a layered material including a
transparent protein polyurethane alloy layer described herein, the
transparent protein polyurethane alloy layer can provide unique
characteristics for the layered material. For example, compared to
a non-transparent layer, the transparent protein polyurethane alloy
layer can provide unique depth of color when dyed. Likewise, the
transparent protein polyurethane alloy layer can provide its
mechanical properties to the layered material without significantly
influencing the aesthetic properties of the material.
[0123] In some embodiments, the protein polyurethane alloy can
include one or more coloring agents. In some embodiments, the
coloring agent can be a dye, for example a fiber reactive dye, a
direct dye, or a natural dye. Exemplary dyes, include but are not
limited to, Azo structure acid dyes, metal complex structure acid
dyes, anthraquinone structure acid dyes, and azo/diazo direct dyes.
In some embodiments, the coloring agent can be pigment, for example
a lake pigment.
[0124] Suitable polyurethanes for blending with one or more
proteins according to embodiments described herein include, but are
not limited to, aliphatic polyurethanes, aromatic polyurethanes,
bio-based polyurethanes, or acrylic acid modified polyurethanes.
Suitable polyurethanes are commercially available from
manufacturers including Lubrizol, Hauthaway, Stahl, and the like.
In some embodiments, a polyurethane for a protein polyurethane
alloy can be bio-polyurethane. In some embodiments, the
polyurethane is a water-dispersible polyurethane. In some
embodiments, the polyurethane can be a polyester polyurethane. In
some embodiments, the polyurethane can be a polyether polyurethane.
In some embodiments, the polyurethane can be a polycarbonate-based
polyurethane. In some embodiments, the polyurethane can be an
aliphatic polyester polyurethane. In some embodiments, the
polyurethane can be an aliphatic polyether polyurethane. In some
embodiments, the polyurethane can be an aliphatic polycarbonate
polyurethane. In some embodiments, the polyurethane can be an
aromatic polyester polyurethane. In some embodiments, the
polyurethane can be an aromatic polyether polyurethane. In some
embodiments, the polyurethane can be an aromatic polycarbonate
polyurethane.
[0125] In some embodiments, the polyurethane can have a soft
segment selected from the group consisting of: polyether polyols,
polyester polyols, polycarbonate polyols, and mixtures thereof. In
some embodiments, the polyurethane can have a hard segment
comprising diisocyanates and optionally short chain diols. Suitable
diisocyanates can be selected from the group consisting of:
aliphatic diicocyanates such as hexamethylene diisocyanate,
isophorone diisocyanate; aromatic diisocyanates such as 4,4'
diphenyl methylene diisocyanate, toluene diisocyanate, phenyl
diisocyanate, and mixtures thereof. Suitable short chain diols
include ethylene glycol, propane diol, butane diol, 2,2 methyl 1,3
propane diol, pentane diol, hexane diol and mixtures thereof. In
some embodiments crosslinkers such as multifunctional alcohols, for
example, trimethylol propane triol, or diamines such as ethylene
diamine or 4,4' diamino, diphenyl diamine.
[0126] Exemplary commercial polyurethanes, include but are not
limited to L3360 and Hauthane HD-2001 available from C.L. Hauthaway
& Sons Corporation, SANCURE.TM. polyurethanes available from
Lubrizol Corporation, BONDTHANE.TM. polyurethanes, for example
UD-108, UD-250, and UD-303 available from Bond Polymers
International, and EPOTAL.RTM. ECO 3702 and EPOTAL.RTM. P100 ECO
from BASF. L3360 is a aliphatic polyester polyurethane polymer
aqueous dispersion having a 35% solids content, a viscosity of 50
to 500 cps (centipoise), and a density of about 8.5 lb/gal (pounds
per gallon). HD-2001 is an aliphatic polyester polyurethane polymer
aqueous dispersion having a 40% solids content, a viscosity of 50
to 500 cps, and a density of about 8.9 lb/gal. BONDTHANE.TM. UD-108
is an aliphatic polyether polyurethane polymer aqueous dispersion
having a 33% solids content, a viscosity of 300 cps, and a density
of 8.7 lb/gal. BONDTHANE.TM. UD-250 is an aliphatic polyester
polyurethane polymer aqueous dispersion having a 35% solids
content, a viscosity of 200 cps, and a density of 8.8 lb/gal.
BONDTHANE.TM. UD-303 is an aliphatic polyether polyurethane polymer
aqueous dispersion having a 35% solids content, a viscosity of less
than 500 cps, and a density of 8.7 lb/gal. EPTOAL.RTM. P100 ECO is
a polyester polyurethane elastomer aqueous dispersion having
approximately 40% solids and a viscosity of about 40 mPas.
[0127] Exemplary bio-based polyurethanes include, but are not
limited to, L3360 available from C.L. Hauthaway & Sons
Corporation, IMPRANIL.RTM. Eco DLS, IMPRANIL.RTM. Eco DL 519,
IMPRANIL.RTM. Eco DLP-R, and IMPRAPERM.RTM. DL 5249 available from
Covestro. IMPRANIL.RTM. Eco DLS is an anionic, aliphatic polyester
polyurethane polymer aqueous dispersion having approximately 50%
solids content, a viscosity of less than 1,200 MPas, and a density
of about 1.1 g/cc. IMPRANIL.RTM. Eco DL 519 is an anionic,
aliphatic polyester polyurethane polymer aqueous dispersion.
IMPRANIL.RTM. Eco DLP-R is an anionic, aliphatic polyester
polyurethane polymer aqueous dispersion. IMPRAPERM.RTM. DL 5249 is
an anionic aliphatic polyester-polyurethane polymer aqueous
dispersion.
[0128] In some embodiments, the polyurethane can include reactive
groups that can be cross-linked with a protein. Exemplary reactive
groups include, but are not limited to, a sulfonate, an aldehyde, a
carboxylic acid or ester, a blocked isocyanate, or the like, and
combinations thereof. In such embodiments, the polyurethane can be
crosslinked to the protein in the protein polyurethane alloy
through the reaction of a reactive group on the protein with the
reactive group present in the polyurethane.
[0129] Suitable proteins for blending with one or more
polyurethanes according to embodiments described herein include,
but are not limited to, collagen, gelatin, bovine serum albumin
(BSA), soy proteins, pea protein, egg white albumin, casein, peanut
protein, edestin protein, whey protein, karanj a protein, and
cellulase. Suitable collagens include, but are not limited to,
recombinant collagen (r-Collagen), a recombinant collagen fragment,
and extracted collagens. Suitable soy proteins include, but are not
limited to, soy protein isolate (SPI), soymeal protein, and soy
protein derivatives. In some embodiments, the soy protein isolate
can be partially hydrolyzed soy protein isolate. Suitable pea
proteins include, but are not limited to, pea protein isolate, and
pea protein derivatives. In some embodiments, the pea protein
isolate can be partially hydrolyzed pea protein isolate.
[0130] Table 1 below lists some exemplary proteins and properties
of the proteins. The gelatin is gelatin from porcine skin, Type A
(Sigma Aldrich G2500). The collagen is extracted bovine collagen
purchased from Wuxi BIOT Biology-technology Company. The bovine
serum albumin Sigma Aldrich 5470 bovine serum albumin. The
r-Collagen is recombinant collagen from Modern Meadow. The soy
protein isolate is soy protein isolate purchased from MP Medicals
(IC90545625). The pea protein is pea protein powder purchased from
Bobs Red Mills (MTX5232). The egg white albumin protein is albumin
from chicken egg white (Sigma Aldrich A5253). The casein protein is
casein from bovine milk (Sigma Aldrich C7078). The peanut protein
is peanut protein powder purchased from Tru-Nut. The whey protein
is whey from bovine milk (Sigma Aldrich W1500). Other suitable soy
protein isolates include, but are not limited to, soy protein
isolate purchased from AMD (Clarisoy 100, 110, 150, 170, 180), or
DuPont (SUPRO.RTM. XT 55, SUPRO.RTM. XT 221D, and SOBIND.RTM.
Balance). Other suitable pea protein powders include, but are not
limited to, pea protein powder purchased from Puns (870 and
870H).
[0131] Karanj a protein is a protein found in Karanj a seeds
harvested from Pongamia pinnata trees (also known as Pongamia
glabra trees). See Rahman, M M., and Netravali, "Green Resin from
Forestry Waste Residue `Karanj a (Pongamia pinnata) Seed Cake` for
Biobased Composite Structures," ACS Sustainable Chem. Eng., 2:
2318-2328 (2014); see also Mandal et al., "Nutritional Evaluation
of Proteins from three Non-traditional Seeds with or without Amino
Acids Supplementation in Albino Rats," Proc. Indian natn. Sci.
Acad., B50, No. 1, 48-56 (1984). The protein can be extracted from
Karanja seeds using a solvent extraction process. Id. In some
embodiments, the karanja protein can be karanja protein isolate. In
such embodiments, karanja protein isolate can be obtained by
alkaline extraction and acid precipitation of defatted karanja seed
cake. See Rahman, M M., and Netravali, "Green Resin from Forestry
Waste Residue `Karanja (Pongamia pinnata) Seed Cake` for Biobased
Composite Structures," ACS Sustainable Chem. Eng., 2: 2318-2328
(2014).
[0132] Suitable cellulase proteins are listed below in Table 1. The
"Cellulase-RG" protein is Native Trichoderma sp. Cellulase
available from CREATIVE ENZYMES.RTM.. The "Cellulase-IG" protein is
laboratory grade cellulase available from Carolina Biological
Supply Company.
[0133] The 50 KDa recombinant collagen fragment (50 KDa r-Collagen
fragment) in Table 1 is a collagen fragment comprising the amino
acid sequence listed as SEQ ID NO: 1.
[0134] The "dissolution method" listed in Table 1 is an exemplary
aqueous solvent in which the protein can be dissolved in a solution
that is miscible with the hard phase of the polyurethane as
described herein. Proteins that can be at least partly dissolved in
an aqueous solution are suitable for forming protein polyurethane
alloys with polyurethane dispersions.
TABLE-US-00001 TABLE 1 Example Proteins Amino Acid Comp.: Protein
Protein Protein Dissolution Molecular Isoelectric Lysine
Thermostability Name Source Method Weight Point (g/100 g) up to
200.degree. C. Gelatin Porcine Water ~100 KDa ~4.8 2.6 Yes Collagen
Bovine Water ~120 KDa -- 2.2 -- BSA Bovine Water ~66 KDa ~4.7 11.98
-- (Bovine Serum Albumin) r-Collagen Yeast Water ~100 KDa -- 3.6 --
Soy protein Soy Water + ~30 to 60 KDa ~4.0 to 5.0 5.6 Yes isolate
NaOH Pea Protein Pea Water + ~ 60 to 80 KDa ~4.5 7.6 Yes NaOH Egg
White Chicken Egg Water ~40 KDa ~4.8 5.7 Yes Albumin Casein Bovine
Milk Water + ~24 KDa ~4.6 7.4 -- NaOH Peanut Peanut Water + ~60 KDa
~4.5 2.5 Yes Protein NaOH Whey Bovine Milk Water ~18 KDa ~4.5 to
5.2 9.7 No Karanja Karanja Seed Water -- -- 14.6 -- protein isolate
50 KDa r- Yeast Water ~50 KDa ~9.3 3.9 -- Collagen fragment
Cellulase- Trichoderma Water ~20 to 90 KDa ~4.6 to 6.9 -- -- RG
reesei Cellulase-IG Trichoderma Water -- -- -- -- reesei
[0135] In some embodiments, the protein can have one or more of the
following properties: (i) a molecular weight within a range
described herein (ii) an isoelectric point within a range described
below, (iii) an amino acid composition measured in grams of lysine
per 100 grams of protein in a range described below, and (iv)
protein thermo-stability up to 200.degree. C.
Protein Molecular Weight
[0136] In some embodiments, the protein can have a molecular weight
ranging from about 1 KDa (kilodaltons) to about 700 KDa, including
subranges. For example, the protein can have a molecular weight
ranging from about 1 KDa to about 700 KDa, about 10 KDa to about
700 KDa, about 20 KDa to about 700 KDa, about 50 KDa to about 700
KDa, about 100 KDa to about 700 KDa, about 200 KDa to about 700
KDa, about 300 KDa to about 700 KDa, about 400 KDa to about 700
KDa, about 500 KDa to about 700 KDa, about 600 KDa to about 700
KDa, about 1 KDa to about 600 KDa, about 1 KDa to about 500 KDa,
about 1 KDa to about 400 KDa, about 1 KDa to about 300 KDa, about 1
KDA to about 200 KDa, about 1 KDa to about 100 KDa, about 1 KDa to
about 50 KDa, about 1 KDa to about 20 KDa, or about 1 KDa to about
10 KDa, or within a range having any two of these values as
endpoints, inclusive of the endpoints.
Protein Isoelectric Point
[0137] In some embodiments, the protein can have an isoelectric
point ranging from about 4 to about 10, including subranges. For
example, the protein can have an isoelectric point ranging from
about 4 to about 10, about 4.5 to about 9.5, about 5 to about 9,
about 5.5 to about 8.5, about 6 to about 8, about 6.5 to about 7.5,
or about 6.5 to about 7, or within a range having any two of these
values as endpoints, inclusive of the endpoints. In some
embodiments, the protein can have an isoelectric point ranging from
about 4 to about 5.
Protein Amino Acid Composition
[0138] In some embodiments, the protein can have an amino acid
composition measured in grams of lysine per 100 grams of protein
(as referred to as a "lysine weight percent") ranging from about
0.5 wt % to about 100 wt %, including subranges. For example, the
protein can have a lysine weight percent ranging from about 0.5 wt
% to about 100 wt %, about 1 wt % to about 100 wt %, about 5 wt %
to about 100 wt %, about 10 wt % to about 100 wt %, about 20 wt %
to about 100 wt %, about 30 wt % to about 100 wt %, about 40 wt %
to about 100 wt %, about 50 wt % to about 100 wt %, about 60 wt %
to about 100 wt %, about 70 wt % to about 100 wt %, about 80 wt %
to about 100 wt %, or about 90 wt % to about 100 wt %, or within a
range having any two of these values as endpoints, inclusive of the
endpoints. In some embodiments, the protein can be a
polylysine.
[0139] In some embodiments, the protein can have a lysine weight
percent ranging from about 0.5 wt % to about 20 wt %, including
subranges. For example, the protein can have a lysine weight
percent ranging from about 0.5 wt % to about 20 wt %, about 1 wt %
to about 19 wt %, about 2 wt % to about 18 wt %, about 3 wt % to
about 17 wt %, about 4 wt % to about 16 wt %, about 5 wt % to about
15 wt %, about 6 wt % to about 14 wt %, about 7 wt % to about 13 wt
%, about 8 wt % to about 12 wt %, about 9 wt % to about 11 wt %, or
about 9 wt % to about 10 wt %, or within a range having any two of
these values as endpoints, inclusive of the endpoints. In some
embodiments, the protein can have a lysine weight percent ranging
from about 1 wt % to about 20 wt %. In some embodiments, the
protein can have a lysine weight percent ranging from about 5 wt %
to about 20 wt %. In some embodiments, the protein can have a
lysine weight percent ranging from about 1 wt % to about 12 wt %.
In some embodiments, the protein can have a lysine weight percent
ranging from about 5 wt % to about 12 wt %. In some embodiments,
the protein can have a lysine weight percent ranging from about 1
wt % to about 15 wt %. In some embodiments, the protein can have a
lysine weight percent ranging from about 5 wt % to about 15 wt
%.
[0140] In some embodiments, the protein can be thermo-stable. In
some embodiments, the protein can be non-thermo-stable. As
described herein, protein thermo-stability is determined by a
differential scanning calorimetry (DSC), where a pre-dried protein
powder (with moisture less than 3%) is scanned from 0.degree. C. to
200.degree. C. In the protein's DSC curves, an endothermic peak
larger than 10 mW/mg is determined to be a "denaturation peak", and
the temperature corresponding to the endothermic "denaturation
peak" is defined as the "denaturation temperature" of the protein.
A protein that is "thermo-stable" means that the protein has
denaturation temperature of 200.degree. C. or more. For purposes of
the present disclosure, a protein with a denaturation temperature
below 200.degree. C. is considered "non-thermo-stable." For
example, it was found that the whey from bovine milk listed in
Table 1 has a denaturation temperature at 158.degree. C. according
to DSC, and therefore the whey is considered non-thermo-stable.
Protein Dissolution
[0141] In some embodiments, before blending with one or more
polyurethanes, one or more proteins can be dissolved in an aqueous
solution to form an aqueous protein mixture. In some embodiments,
dissolving the protein in an aqueous solution before blending the
protein with one or more polyurethanes can facilitate miscibility
of the protein with the hard phase of the one or more
polyurethanes. For example, dissolving the protein in an aqueous
solution before blending the protein with one or more polyurethanes
can facilitate miscibility of the protein with the hard phase of
the polyurethane(s). Not all proteins are naturally miscible with
any phase of a polyurethane. For example, and as exemplified in
Examples 33 and 34, casein is not necessarily miscible with a
polyurethane. As shown in these two examples, casein is immiscible
with L3360 if casein, water, and L3360 are mixed. The obtained film
had an opaque look with numerous optically visible granules in the
film. However, casein is miscible with L3360's hard phase if casein
is dissolved in a sodium hydroxide solution before mixing with
L3360. The film obtained by blending these components had a
transparent and uniform look with no optically visible granules in
the film.
[0142] Suitable aqueous solutions include, but are not limited to,
water, an aqueous alkali solution, an aqueous acid solution, an
aqueous solution including an organic solvent, a urea solution, and
mixtures thereof. In some embodiments, the aqueous alkali solution
can be a basic solution such as a sodium hydroxide, ammonia or
ammonium hydroxide solution. In some embodiments, examples of an
acidic aqueous solution can be an acetic acid or hydrochloric acid
(HCl) solutions. Suitable organic solvents include, but are not
limited to, ethanol, isopropanol, acetone, ethyl acetate, isopropyl
acetate, glycerol, and the like. In some embodiments, the protein
concentration in the aqueous protein mixture can range from about
10 g/L to about 300 g/L, including subranges. For example, the
protein concentration in the aqueous protein mixture can be about
10 g/L, about 20 g/L, about 30 g/L, about 40 g/L, about 50 g/L,
about 60 g/L, about 70 g/L, about 80 g/L, about 90 g/L, about 100
g/L, about 150 g/L, about 200 g/L, about 250 g/L, or about 300 g/L,
or within a range having any two of these values as endpoints,
inclusive of the endpoints. In some embodiments, the protein
concentration in the aqueous protein mixture can range from about
10 g/L to about 300 g/L, about 20 g/L to about 250 g/L, about 30
g/L to about 200 g/L, about 40 g/L to about 150 g/L, about 50 g/L
to about 100 g/L, about 60 g/L to about 90 g/L, or about 70 g/L to
about 80 g/L.
[0143] In some embodiments, the protein can be pretreated and/or
purified to improve solubility in water. Suitable pretreatments
include, but are not limited to, an acid treatment, an alkaline
treatment, enzyme hydrolysis, and a salt treatment. An exemplary
acid treatment is acid hydrolysis with suitable acid such as acetic
acid or HCl. An exemplary alkaline treatment is alkaline hydrolysis
with suitable base such as ammonium hydroxide, NaOH, KOH, or a
mixture thereof. Exemplary enzymes for hydrolysis include, but are
not limited to, papain, bromelain, trypsin, alkaline proteases, and
the like. Suitable purification treatments include, but are not
limited to, removal of phytate with calcium salt, diafiltration,
ultrafiltration, centrifugation, and the like.
[0144] In some embodiments, adding lysine or other hydrophilic
amino acids to the protein before blending with one or more
polyurethanes can facilitate miscibility of the protein with the
hard phase of the one or more polyurethanes.
Protein Hydrolysis
[0145] In some embodiments, the protein can be
partially-hydrolyzed. Partial hydrolysis of the protein can promote
dissolution of the protein in water and/or facilitate miscibility
of the protein with the hard phase of the polyurethane.
Partial-hydrolysis of the protein can be accomplished using enzymes
or strong to moderate base. Hydrolysis can be followed by a
reduction in viscosity and/or reduction in protein molecular
weight. Characterization methods for determining a reduction in
protein molecular weight, and thus a level of protein hydrolysis,
include but are not limited to, light scattering, gel
electrophoresis, size exclusion chromatography, solution viscosity
measurement, terminal amino group detection with trinitrobenzene
sulfonic acid or ninhydrin, or particle size measurement with laser
diffraction. Example 21 describes partially-hydrolyzed soy protein
prepared using sodium hydroxide according to some embodiments.
PEG-Modification of Proteins
[0146] In some embodiments, the protein can be chemically modified
by covalent attachment of PEG polyethylene glycol (PEG) to the
protein. PEG-modification of the protein can promote dissolution of
the protein in water and/or facilitate miscibility with the protein
with the hard phase of the polyurethane. PEG-modification of a
protein can be accomplished using a method that covalently attaches
hydrophilic polyethylene glycol (PEG) chains to the protein.
[0147] In some embodiments, the amount of protein in the protein
polyurethane alloy can range from about 10 wt % to about 50 wt % of
protein, including subranges. For example, in some embodiments, the
amount of protein in the protein polyurethane alloy range from
about 10 wt % to about 50 wt %, about 15 wt % to about 50 wt %,
about 20 wt % to about 50 wt %, about 25 wt % to about 50 wt %,
about 30 wt % to about 50 wt %, about 35 wt % to about 50 wt %,
about 40 wt % to about 50 wt %, about 45 wt % to about 50 wt %,
about 10 wt % to about 45 wt %, about 10 wt % to about 40 wt %,
about 10 wt % to about 35 wt %, about 10 wt % to about 30 wt %,
about 10 wt % to about 25 wt %, about 10 wt % to about 20, or about
10 wt % to about 15%, or within a range having any two of these
values as endpoints, inclusive of the endpoints. In some
embodiments, the amount of protein in the protein polyurethane
alloy can range from about 20 wt % to about 35 wt %.
[0148] In some embodiments, the amount of polyurethane in the
protein polyurethane alloy can range from about 50 wt % to about 90
wt %, including subranges. For example, in some embodiments, the
amount of polyurethane in the protein polyurethane alloy can range
from about 50 wt % to about 90 wt %, about 55 wt % to about 90 wt
%, about 60 wt % to about 90 wt %, about 65 wt % to about 90 wt %,
about 70 wt % to about 90 wt %, about 75 wt % to about 90 wt %,
about 80 wt % to about 90 wt %, about 85 wt % to about 90 wt %,
about 50 wt % to about 85 wt %, about 50 wt % to about 80 wt %,
about 50 wt % to about 75 wt %, about 50 wt % to about 70 wt %,
about 50 wt % to about 65 wt %, about 50 wt % to about 60 wt %, or
about 50 wt % to about 55 wt %, or within a range having any two of
these values as endpoints, inclusive of the endpoints. In some
embodiments, the amount of polyurethane in the protein polyurethane
alloy can range from about 65 wt % to about 80 wt %.
[0149] In some embodiments, the above-listed weight percent values
and ranges can be based on the total weight of the protein
polyurethane alloy or protein polyurethane alloy layer. In some
embodiments, the above-listed weight percent values and ranges can
be based on the total weight of only protein and polyurethane in a
protein polyurethane alloy or protein polyurethane alloy layer.
Unless otherwise specified, a weight percent value or range for the
polyurethane and the protein is based on the total weight of only
protein and polyurethane in a protein polyurethane alloy or protein
polyurethane alloy layer.
[0150] In some embodiments, the sum of the amount of protein plus
the amount of polyurethane in the protein polyurethane alloy can be
about 80 wt % or more. For example, in some embodiments, the sum of
the amount of protein plus the amount of polyurethane in the
protein polyurethane alloy can range from about 80 wt % to 100 wt
%, about 82 wt % to 100 wt %, about 84 wt % to 100 wt %, about 86
wt % to 100 wt %, about 88 wt % to 100 wt %, about 90 wt % to 100
wt %, about 92 wt % to 100 wt %, about 94 wt % to 100 wt %, about
96 wt % to 100 wt %, or about 98 wt % to 100 wt %.
[0151] In some embodiments, the protein polyurethane alloy can
include water making up a portion of the total weight percent of
the material. In some embodiments, the amount of water in the
protein polyurethane alloy can range from about 1 wt % to about 10
wt %, including subranges. For example, in some embodiments, the
amount of water in the protein polyurethane alloy can range from
about 1 wt % to about 10 wt %, about 2 wt % to about 10 wt %, about
3 wt % to about 10 wt %, about 4 wt % to about 10 wt %, about 5 wt
% to about 10 wt %, about 6 wt % to about 10 wt %, about 7 wt % to
about 10 wt %, about 8 wt % to about 10 wt %, about 1 wt % to about
9 wt %, about 1 wt % to about 8 wt %, about 1 wt % to about 7 wt %,
about 1 wt % to about 6 wt %, about 1 wt % to about 5 wt %, about 1
wt % to about 4 wt %, or about 1 wt % to about 3 wt %, or within a
range having any two of these values as endpoints, inclusive of the
endpoints.
[0152] A protein polyurethane alloy described herein can have one
or more of (i) a second Dynamic Mechanical Analysis (DMA) modulus
transition onset temperature greater than the second DMA modulus
transition onset temperature of the unalloyed polyurethane (ii) a
first Dynamic Mechanical Analysis (DMA) modulus transition onset
temperature substantially the same as the first DMA modulus
transition onset temperature of the unalloyed polyurethane, (iii) a
DMA tan(.delta.) peak at a temperature substantially the same as
the temperature of the DMA tan(.delta.) peak corresponding to the
soft phase of the unalloyed polyurethane, (iv) a Young's modulus
greater than the Young's modulus of the unalloyed polyurethane, (v)
a tensile strength greater than the tensile strength of the
unalloyed polyurethane, or (vi) a moisture vapor transmission rate
(MVTR) greater than the MVTR of the unalloyed polyurethane.
[0153] FIGS. 1-15 illustrate the effects of dissolving various
amounts of different proteins in different polyurethanes to form
polyurethane alloys according to some embodiments. Tables 3-6 list
thermal and mechanical properties for various protein polyurethane
alloys according to some embodiments, as well as thermal and
mechanical properties for various polyurethanes. The samples tested
were prepared by blending the listed protein with an aqueous
dispersion of the listed polyurethane, casting the mixture as a
flat film, drying in oven at 45.degree. C. overnight (16 to 24
hours), and conditioning at standard reference atmosphere
(23.degree. C., 50% humidity) for 24 hours before testing. The
weight percent values in the figures and Tables 3-6 are the
relative weight percent of solids added to the blend used to create
the samples. For example, 0.825 grams of gelatin and 5.5 g of L3360
(35 wt % solids) were blended to create the sample for Example No.
9 having 30 wt % gelatin and 70 wt % L3360. The weight percentages
in the figures and Tables 3-6 can closely approximate the weight
percentages of protein and polyurethane in the dried samples of
Example Nos. 1-44, based on the total weight of the dried samples.
The dried samples included water making up a small portion (for
example, about 5% to about 10 wt %) of the total weight percent of
the sample.
[0154] Table 7 lists moisture vapor transmission rates for various
protein polyurethane alloys according to some embodiments. The
samples tested were prepared as described in Example Nos. 45-56.
The weight percent values in Table 7 are the relative weight
percent of solids added to the blend used to create the samples.
These weight percentages can closely approximate the weight
percentages of protein and polyurethane in the dried samples of
Example Nos. 45-56, based on the total weight of the dried samples.
The dried samples included water making up a small portion (for
example, about 5% to about 10 wt %) of the total weight percent of
the sample.
[0155] The DMA temperatures in Tables 3 and 4 were measured using a
DMA-850 from TA Instruments. For testing, a 1 cm.times.2.5 cm strip
was cut from a sample film using a metal die. The cut film samples
were loaded into the film and fiber tension clamp for testing.
During testing, a pre-load of 0.01 newtons (N) was applied to the
cut film samples. The instrument was cooled to -80.degree. C., held
for 1 minute, then the temperature was ramped at 4.degree. C/minute
to 200.degree. C., or until the sample was too weak to be held in
tension. During the temperature ramp, the sample was oscillated
0.1% strain at a frequency of 1 Hz. The resulting storage modulus,
loss modulus, and tan(.delta.) values were plotted with temperature
for each test. Unless otherwise specified, all DMA test data
reported herein was measured using this test methodology. The
tensile strength values and Young's modulus values in Tables 5 and
6 were measured according the method provided by ASTM D638. The
tensile strength values and Young's modulus values are an average
of at least three sample specimens tested.
[0156] The DMA graph shown in FIG. 1 shows the measured storage
modulus (E') for 100% L3360 (Example No. 1) and gelatin dissolved
within L3360 at various weight percentages, namely 5 wt %, 10 wt %,
15 wt %, 20%, and 30 wt % (Example Nos. 9 and 25-28). This graph
illustrates that blending gelatin with L3360 can create an alloy
with a second DMA modulus transition onset temperature greater than
the second DMA modulus transition onset temperature of 100% L3360.
Without wishing to be bound by a particular theory, it is believed
that as the hard phase comprising gelatin and the hard segment of
the polyurethane become continuous at higher gelatin content, the
increase in the second DMA modulus transition onset temperature
becomes more apparent in this test. This trend indicates that the
gelatin is miscible with the hard phase of L3360.
[0157] This miscibility of gelatin with the hard phase L3360 is
further exemplified in the mechanical property graphs of FIG. 2 and
FIG. 3, which compare two different mechanical properties of
Example No. 1 and Example Nos. 9 and 25-28. As shown in FIG. 2, the
maximum tensile stress ("tensile strength") of the protein
polyurethane alloys tested is greater than the maximum tensile
stress of 100% L3360. This increase in maximum tensile stress is
particularly significant at gelatin weight percentages of 10 wt %
or more. As shown in FIG. 3, the Young's modulus of the protein
polyurethane alloys tested is greater than the Young's modulus of
100% L3360. This increase in Young's modulus is particularly
significant at gelatin weight percentages of 15 wt % or more.
[0158] The DMA graph shown in FIG. 4 shows the measured storage
modulus (E') for 100% L3360 (Example No. 1) and SPI dissolved
within L3360 at various weight percentages, namely 10 wt %, 20%,
and 30 wt % (Example Nos. 21, 30, and 31). This thermogram
illustrates that blending SPI with L3360 can create a protein
polyurethane alloy with a second DMA modulus transition onset
temperature greater than the second DMA modulus transition onset
temperature of 100% L3360. As more SPI is added, the increase in
the second DMA modulus transition onset temperature increases. This
trend indicates that the SPI in miscible with the hard phase of
L3360.
[0159] This miscibility of SPI with the hard phase L3360 is further
exemplified in the mechanical property graphs of FIG. 5 and FIG. 6,
which compare two different mechanical properties of Example No. 1
and Example Nos. 21, 30, and 31. As shown in FIG. 5, the maximum
tensile stress ("tensile strength") of the protein polyurethane
alloys tested is greater than the maximum tensile stress of 100%
L3360. This increase in maximum tensile stress is particularly
significant at SPI weight percentages of 10 wt % or more. As shown
in FIG. 6, the Young's modulus of the protein polyurethane alloys
tested is greater than the Young's modulus of 100% L3360. This
increase in Young's modulus is particularly significant at SPI
weight percentages of 15 wt % or more.
[0160] The DMA graph shown in FIG. 7 shows the measured storage
modulus (E') for 100% L3360 (Example No. 1) and various proteins
dissolved within L3360 at 30 wt % (Example Nos. 9 and 17-23). This
graph illustrates that gelatin, SPI, and other proteins can be
blended with L3360 to create a protein polyurethane alloy with a
second DMA modulus transition onset temperature greater than the
second DMA modulus transition onset temperature of 100% L3360. All
the proteins, except Whey, produced protein polyurethane alloys
with a second DMA modulus transition onset temperature greater than
that of 100% L3360. It is believed Whey is miscible with L3360's
hard phase due to its ability to improve mechanical properties of a
protein polyurethane alloy relative to 100% L3360. But it is
believed that Whey did not increase the second DMA modulus
transition onset temperature because Whey has a low denaturation
temperature as determined by DSC.
[0161] Further, the graph of FIG. 7 shows that dissolving the
various proteins within L3360 did not result in a protein
polyurethane alloy having a DMA transition temperature of the soft
phase significantly different from the DMA transition temperature
of the soft phase for 100% L3360. As shown in Table 4, the Delta
1.sup.st Modulus Transition Onset for all of Example Nos. 9 and
17-23 was less than 10.degree. C. Relatedly, the Delta Tan(.delta.)
Peak Temperature for all of Example Nos. 9 and 17-23 was less than
10.degree. C. These results indicate the proteins were not miscible
with L3360's soft phase.
[0162] This selective miscibility of the proteins with the hard
phase L3360 is further exemplified in the mechanical property test
results plotted in the graphs of FIG. 8A and FIG. 8B, and reported
in Tables 5 and 6. The graphs of FIG. 8A and FIG. 8B compare the
tensile strength and Young's modulus of Example No. 1 and Example
Nos. 9 and 17-23. An increase in tensile strength and/or an
increase in Young's modulus can indicate that a protein is miscible
with the hard phase of L3360. Tables 5 and 6 report the tensile
strength and Young's modulus of the materials.
[0163] To further illustrate the selective miscibility of proteins
with the hard phase of a polyurethane having both a soft phase and
a hard phase, gelatin was blended with various exemplary
polyurethanes. FIGS. 9-15 show DMA thermograms for these exemplary
blends as well as thermograms for the polyurethanes in the absence
of gelatin. FIG. 9 compares the DMA data for a protein polyurethane
alloy made of 30 wt % gelatin and 70 wt % L3360 (Example No. 9) and
100% L3360 (Example No. 1). FIG. 10 compares the DMA data for a
protein polyurethane alloy made of 30 wt % gelatin and 70 wt %
HD-2001 (Example No. 15) and 100% HD-2001 (Example No. 7). FIG. 11
compares the DMA data for a protein polyurethane alloy made of 30
wt % gelatin and 70 wt % Sancure (Example No. 14) and 100% Sancure
(Example No. 6). FIG. 12 compares the DMA data for a protein
polyurethane alloy made of 30 wt % gelatin and 70 wt % Impranil DLS
(Example No. 12) and 100% Impranil DLS (Example No. 5). FIG. 13
compares the DMA data for a protein polyurethane alloy made of 30
wt % gelatin and 70 wt % UD-108 (Example No. 10) and 100% UD-108
(Example No. 2). FIG. 14 compares the DMA data for a protein
polyurethane alloy made of 30 wt % gelatin and 70 wt % UD-303
(Example No. 13) and 100% UD-303 (Example No. 4). FIG. 15 compares
the DMA data for a protein polyurethane alloy made of 30 wt %
gelatin and 70 wt % UD-250 (Example No. 11) and 100% UD-250
(Example No. 3).
[0164] FIG. 22 compares the DMA data for a protein polyurethane
alloy made of 30 wt % soy protein isolate (SPI) and 70 wt %
IMPRAPERM.RTM. DL 5249 and a 100% IMPRAPERM.RTM. DL 5249
polyurethane sample. Three samples of the 30 wt % soy protein
isolate (SPI) and 70 wt % IMPRAPERM.RTM. DL 5249 alloy of FIG. 22
having a mean thickness of 0.44 mm had an average Young's modulus
of 65.80 MPa. Three samples of the 100% IMPRAPERM.RTM. DL 5249
polyurethane of FIG. 22 having a mean thickness of 0.7 mm had an
average Young's modulus of 10.13 MPa. The DMA data shown in FIG. 22
and the results of this mechanical testing for the protein
polyurethane alloy illustrate the selective miscibility of the SPI
with the hard phase of IMPRAPERM.RTM. DL 5249.
[0165] Tables 3 and 4 report DMA data for the various exemplary
polyurethanes and those same polyurethanes blended with 30 wt %
gelatin. Tables 5 and 6 report the tensile strength and Young's
modulus data for the various exemplary polyurethanes and those same
polyurethanes blended with 30 wt % gelatin. The results indicate
selective miscibility of proteins tested with the hard phase of
polyurethanes tested.
[0166] In some embodiments, the protein polyurethane alloy can
comprise a polyurethane having a second DMA modulus transition
onset temperature in the absence of protein. That same protein
polyurethane alloy can have a second DMA modulus transition onset
temperature ranging from about 5.degree. C. to about 100.degree. C.
greater than the second DMA modulus transition onset temperature of
the polyurethane in the absence of protein. This relative increase
in the second DMA modulus transition onset temperature can be
referred to as "Delta 2.sup.nd Modulus Transition Onset." In some
embodiments, the Delta 2.sup.nd Modulus Transition Onset can be
about 5.degree. C. or more. In some embodiments, the Delta 2.sup.nd
Modulus Transition Onset can range from about 5.degree. C. to about
100.degree. C., about 5.degree. C. to about 95.degree. C., about
5.degree. C. to about 90.degree. C., about 5.degree. C. to about
85.degree. C., about 5.degree. C. to about 80.degree. C., about
5.degree. C. to about 75.degree. C., about 5.degree. C. to about
70.degree. C., about 5.degree. C. to about 65.degree. C., about
5.degree. C. to about 60.degree. C., about 5.degree. C. to about
55.degree. C., about 5.degree. C. to about 50.degree. C., about
5.degree. C. to about 45.degree. C., about 5.degree. C. to about
40.degree. C., about 5.degree. C. to about 35.degree. C., about
5.degree. C. to about 30.degree. C., about 5.degree. C. to about
25.degree. C., about 5.degree. C. to about 20.degree. C., about
5.degree. C. to about 15.degree. C., about 5.degree. C. to about
10.degree. C., about 10.degree. C. to about 100.degree. C., about
15.degree. C. to about 100.degree. C., about 20.degree. C. to about
100.degree. C., about 25.degree. C. to about 100.degree. C., about
30.degree. C. to about 100.degree. C., about 35.degree. C. to about
100.degree. C., about 40.degree. C. to about 100.degree. C., about
45.degree. C. to about 100.degree. C., about 50.degree. C. to about
100.degree. C., about 55.degree. C. to about 100, about 60.degree.
C. to about 100.degree. C., about 65.degree. C. to about
100.degree. C., about 70.degree. C. to about 100.degree. C., about
75.degree. C. to about 100.degree. C., about 80.degree. C. to about
100.degree. C., about 85.degree. C. to about 100.degree. C., about
90.degree. C. to about 100.degree. C., or about 95.degree. C. to
about 100.degree. C., or within an range having any two of these
values as endpoints, inclusive of the endpoints.
[0167] In some embodiments, the Delta 2.sup.nd Modulus Transition
Onset can range from about 5.degree. C. to about 80.degree. C. In
some embodiments, the Delta 2.sup.nd Modulus Transition Onset can
range from about 20.degree. C. to about 80.degree. C. In some
embodiments, the Delta 2.sup.nd Modulus Transition Onset can range
from about 40.degree. C. to about 80.degree. C. In some
embodiments, the Delta 2.sup.nd Modulus Transition Onset can be
greater than about 100.degree. C. For example, the Delta 2.sup.nd
Modulus Transition Onset can range from about 100.degree. C. to
about 150.degree. C.
[0168] In some embodiments, a soy protein polyurethane alloy can
comprise a polyurethane having a second DMA modulus transition
onset temperature in the absence of soy protein. That same soy
protein polyurethane alloy can have a second DMA modulus transition
onset temperature ranging from about 15.degree. C. to about
100.degree. C. greater than the second DMA modulus transition onset
temperature of the polyurethane in the absence of soy protein. In
some embodiments, the Delta 2.sup.nd Modulus Transition Onset for
the soy protein polyurethane alloy can be about 15.degree. C. or
more. In some embodiments, the Delta 2.sup.nd Modulus Transition
Onset for a soy protein polyurethane alloy can range from about
15.degree. C. to about 100.degree. C., about 15.degree. C. to about
95.degree. C., about 15.degree. C. to about 90.degree. C., about
15.degree. C. to about 85.degree. C., about 15.degree. C. to about
80.degree. C., about 15.degree. C. to about 75.degree. C., about
15.degree. C. to about 70.degree. C., about 15.degree. C. to about
65.degree. C., about 15.degree. C. to about 60.degree. C., about
15.degree. C. to about 55.degree. C., about 15.degree. C. to about
50.degree. C., about 15.degree. C. to about 45.degree. C., about
15.degree. C. to about 40.degree. C., about 15.degree. C. to about
35.degree. C., about 15.degree. C. to about 30.degree. C., about
15.degree. C. to about 25.degree. C., about 15.degree. C. to about
20.degree. C., about 20.degree. C. to about 100.degree. C., about
25.degree. C. to about 100.degree. C., about 30.degree. C. to about
100.degree. C., about 35.degree. C. to about 100.degree. C., about
40.degree. C. to about 100.degree. C., about 45.degree. C. to about
100.degree. C., about 50.degree. C. to about 100.degree. C., about
55.degree. C. to about 100, about 60.degree. C. to about
100.degree. C., about 65.degree. C. to about 100.degree. C., about
70.degree. C. to about 100.degree. C., about 75.degree. C. to about
100.degree. C., about 80.degree. C. to about 100.degree. C., about
85.degree. C. to about 100.degree. C., about 90.degree. C. to about
100.degree. C., or about 95.degree. C. to about 100.degree. C., or
within an range having any two of these values as endpoints,
inclusive of the endpoints.
[0169] In some embodiments, the protein polyurethane alloy can have
a second DMA modulus transition onset temperature ranging from
about 100.degree. C. to about 200.degree. C., including subranges.
For example, in some embodiments, the protein polyurethane alloy
can have a second DMA modulus transition onset temperature ranging
from about 100.degree. C. to about 200.degree. C., about
100.degree. C. to about 195.degree. C., about 100.degree. C. to
about 190.degree. C., about 100.degree. C. to about 185.degree. C.,
about 100.degree. C. to about 180.degree. C., about 100.degree. C.
to about 175.degree. C., about 100.degree. C. to about 170.degree.
C., about 100.degree. C. to about 165.degree. C., about 100.degree.
C. to about 160.degree. C., about 100.degree. C. to about
155.degree. C., about 100.degree. C. to about 150.degree. C., about
100.degree. C. to about 145.degree. C., about 100.degree. C. to
about 140.degree. C., about 100.degree. C. to about 135.degree. C.,
about 100.degree. C. to about 130.degree. C., about 100.degree. C.
to about 125.degree. C., or about 100 to about 120.degree. C.,
about 105.degree. C. to about 200.degree. C., about 110.degree. C.
to about 200.degree. C., about 115.degree. C. to about 200.degree.
C., about 120.degree. C. to about 200.degree. C., about 125.degree.
C. to about 200.degree. C., about 130.degree. C. to about
200.degree. C., about 135.degree. C. to about 200.degree. C., about
140.degree. C. to about 200.degree. C., about 145.degree. C. to
about 200.degree. C., about 150.degree. C. to about 200.degree. C.,
about 155.degree. C. to about 200.degree. C., about 160.degree. C.
to about 200.degree. C., about 165.degree. C. to about 200.degree.
C., about 170.degree. C. to about 200.degree. C., about 175.degree.
C. to about 200.degree. C., or about 180.degree. C. to about
200.degree. C., or within a range having any two of these values as
endpoints, inclusive of the endpoints. In some embodiments, the
protein polyurethane alloy can have a second DMA modulus transition
onset temperature ranging from about 120.degree. C. to about
200.degree. C. In some embodiments, the protein polyurethane alloy
can have a second DMA modulus transition onset temperature ranging
from about 130.degree. C. to about 200.degree. C. In some
embodiments, the protein polyurethane alloy can have a second DMA
modulus transition onset temperature ranging from about 165.degree.
C. to about 200.degree. C.
[0170] In some embodiments, the soy protein polyurethane alloy can
have a second DMA modulus transition onset temperature ranging from
about 130.degree. C. to about 200.degree. C., including subranges.
For example, in some embodiments, the soy protein polyurethane
alloy can have a second DMA modulus transition onset temperature
ranging from about 130.degree. C. to about 200.degree. C., about
130.degree. C. to about 195.degree. C., about 130.degree. C. to
about 190.degree. C., about 130.degree. C. to about 185.degree. C.,
about 130.degree. C. to about 180.degree. C., about 130.degree. C.
to about 175.degree. C., about 130.degree. C. to about 170.degree.
C., about 130.degree. C. to about 165.degree. C., about 130.degree.
C. to about 160.degree. C., about 130.degree. C. to about
155.degree. C., about 130.degree. C. to about 150.degree. C., about
130.degree. C. to about 145.degree. C., about 130.degree. C. to
about 140.degree. C., about 135.degree. C. to about 200.degree. C.,
about 140.degree. C. to about 200.degree. C., about 145.degree. C.
to about 200.degree. C., about 150.degree. C. to about 200.degree.
C., about 155.degree. C. to about 200.degree. C., about 160.degree.
C. to about 200.degree. C., about 165.degree. C. to about
200.degree. C., about 170.degree. C. to about 200.degree. C., about
175.degree. C. to about 200.degree. C., about 180.degree. C. to
about 200.degree. C., about 185.degree. C. to about 200.degree. C.,
or about 190.degree. C. to about 200.degree. C., or within a range
having any two of these values as endpoints, inclusive of the
endpoints.
[0171] In some embodiments, the protein polyurethane alloy can have
a first DMA modulus transition temperature below 30.degree. C. In
some embodiments, the protein polyurethane alloy can have a first
DMA modulus transition onset temperature ranging from about
-65.degree. C. to about 30.degree. C., including subranges. For
example, in some embodiments, the first DMA modulus transition
onset temperature for the protein polyurethane alloy can range from
about -65.degree. C. to about 30.degree. C., about -65.degree. C.
to about 25.degree. C., about -65.degree. C. to about 20.degree.
C., about -65.degree. C. to about 15.degree. C., about -65.degree.
C. to about 10.degree. C., about -65.degree. C. to about 5.degree.
C., about -65.degree. C. to about 1.degree. C., about -65.degree.
C. to 0.degree. C., about -65.degree. C. to about 1.degree. C.,
about -65.degree. C. to about -5.degree. C., about -65.degree. C.
to about -10.degree. C. , about -65.degree. C. to about -15.degree.
C. , about -65.degree. C. to about -20.degree. C. , about
-65.degree. C. to about -25.degree. C., about -65.degree. C. to
about -30.degree. C., about -65.degree. C. to about -35.degree. C.,
about -65.degree. C. to about -35.degree. C., about -65.degree. C.
to about -40.degree. C., or about -65.degree. C. to about
-45.degree. C., or within a range having any two of these values as
endpoints, inclusive of the end points.
[0172] In some embodiments, the protein polyurethane alloy can
comprise a polyurethane having a first DMA modulus transition onset
temperature in the absence of protein. That same protein
polyurethane alloy can have a first DMA modulus transition onset
temperature that is +/-X .degree. C. the first DMA modulus
transition onset temperature of the polyurethane in the absence of
protein. This relative increase or decrease in the first DMA
modulus transition onset temperature can be referred to as "Delta
1.sup.st Modulus Transition Onset." In some embodiments, X can be
1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.
[0173] In some embodiments, the protein polyurethane alloy can have
a DMA tan(.delta.) peak temperature below 30.degree. C. In some
embodiments, the protein polyurethane alloy can have a DMA
tan(.delta.) peak temperature ranging from about -60.degree. C. to
about 30.degree. C., including subranges. For example, in some
embodiments, the DMA tan(.delta.) peak temperature for the protein
polyurethane alloy can range from about -60.degree. C. to about
30.degree. C., about -60.degree. C. to about 25.degree. C., about
-60.degree. C. to about 20.degree. C., about -60.degree. C. to
about 15.degree. C., about -60.degree. C. to about 10.degree. C.,
about -60.degree. C. to about 5.degree. C., about -60.degree. C. to
about 1.degree. C., about -60.degree. C. to 0.degree. C., about
-60.degree. C. to about 1.degree. C., about -60.degree. C. to about
-5.degree. C., about -60.degree. C. to about -10.degree. C. , about
-60.degree. C. to about -15.degree. C. , about -60.degree. C. to
about -20.degree. C. , about -60.degree. C. to about -25.degree.
C., about -60.degree. C. to about -30.degree. C., about -60.degree.
C. to about -35.degree. C., or about -60.degree. C. to about
-40.degree. C., or within a range having any two of these values as
endpoints.
[0174] In some embodiments, the protein polyurethane alloy can
include a polyurethane having a DMA tan(.delta.) peak temperature
corresponding to the soft phase of the polyurethane in the absence
of protein. That same the protein polyurethane alloy can have a DMA
tan(.delta.) peak temperature that is +/-Y.degree. C. the DMA
tan(.delta.) peak temperature corresponding to the soft phase of
the polyurethane in the absence of protein. This relative increase
or decrease in the DMA tan(.delta.) peak temperature can be
referred to as "Delta Tan(.delta.) Peak Temperature." In some
embodiments, Y can be 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.
[0175] In some embodiments, the protein polyurethane alloy can
comprise a polyurethane having a tensile strength in the absence of
protein. That same protein polyurethane alloy can have a tensile
strength about 5% to about 55% greater than the tensile strength of
the polyurethane in the absence of protein. This relative percent
increase in tensile strength can be referred to as "% Delta Tensile
Strength." In some embodiments, % Delta Tensile Strength can be 5%
or more. In some embodiments, % Delta Tensile Strength can range
from about 5% to about 55%, about 10% to about 55%, about 15% to
about 55%, about 20% to about 55%, about 25% to about 55%, about
30% to about 55%, about 35% to about 55%, about 40% to about 55%,
about 45% to about 55%, about 50% to about 55%, about 5% to about
50%, about 5% to about 45%, about 5% to about 40%, about 5% to
about 35%, about 5% to about 30%, about 5% to about 25%, about 5%
to about 20%, about 5% to about 15%, or about 5% to about 10%, or
within a range having any two of these values as endpoints,
inclusive of the endpoints. In some embodiments, % Delta Tensile
Strength can range from about 15% to about 55%. In some
embodiments, % Delta Tensile Strength can be greater than about
55%. For example, % Delta Tensile Strength can range from about 55%
to about 1000%.
[0176] In some embodiments, the soy protein polyurethane alloy can
comprise a polyurethane having a tensile strength in the absence of
soy protein. That same soy protein polyurethane alloy can have a
tensile strength about 10% to about 45% greater than the tensile
strength of the polyurethane in the absence of soy protein. In some
embodiments, % Delta Tensile Strength for the soy protein
polyurethane alloy can be 10% or more. In some embodiments, % Delta
Tensile Strength for the soy protein polyurethane alloy can range
from about 10% to about 45%, about 15% to about 45%, about 20% to
about 45%, about 25% to about 45%, about 30% to about 45%, about
35% to about 45%, about 40% to about 45%, about 10% to about 40%,
about 10% to about 35%, about 10% to about 30%, about 10% to about
25%, about 10% to about 20%, or about 10% to about 15%, or within a
range having any two of these values as endpoints, inclusive of the
endpoints.
[0177] In some embodiments, the protein polyurethane alloy can
comprise a polyurethane having a tensile strength in the absence of
protein. That same protein polyurethane alloy can have a tensile
strength ranging from about 2 MPa (megapascals) to about 8 MPa
greater than the tensile strength of the polyurethane in the
absence of protein. This relative increase in tensile strength can
be referred to as "Delta Tensile Strength." In some embodiments,
Delta Tensile Strength can be 2 MPa or more. In some embodiments,
Delta Tensile Strength can range from about 2 MPa to about 8 MPa,
about 3 MPa to about 8 MPa, about 4 MPa to about 8 MPa, about 5 MPa
to about 8 MPa, about 6 MPa to about MPa, about 7 MPa to about 8
MPa, about 2 MPa to about 7 MPa, about 2 MPa to about 6 MPa, about
2 MPa to about 5 MPa, about 2 MPa to about 4 MPa, or about 2 MPa to
about 3 MPa, or within a range having any two of these values as
endpoints, inclusive of the endpoints. In some embodiments, Delta
Tensile Strength can range from about 5 MPa to about 8 MPa. In some
embodiments, Delta Tensile Strength can be greater than about 8
MPa. For example, Delta Tensile Strength can range from about 8 MPa
to about 15 MPa.
[0178] In some embodiments, the soy protein polyurethane alloy can
comprise a polyurethane having a tensile strength in the absence of
soy protein. That same soy protein polyurethane alloy can have a
tensile strength ranging from about 1.5 MPa to about 5.5 MPa
greater than the tensile strength of the polyurethane in the
absence of soy protein. In some embodiments, Delta Tensile Strength
for the soy protein polyurethane alloy can be 1.5 MPa or more. In
some embodiments, Delta Tensile Strength for the soy protein
polyurethane alloy can range from about 1.5 MPa to about 5.5 MPa,
about 2 MPa to about 5.5 MPa, about 3 MPa to about 5.5 MPa, about 4
MPa to about 5.5 MPa, about 1.5 MPa to about 5 MPa, about 1.5 MPa
to about 4 MPa, or about 1.5 MPa to about 3 MPa, or within a range
having any two of these values as endpoints, inclusive of the
endpoints.
[0179] In some embodiments, the protein polyurethane alloy can have
a tensile strength ranging from about 7MPa to about 21 MPa,
including subranges. For example, in some embodiments, the protein
polyurethane alloy can have a tensile strength ranging from about 7
MPa to about 21 MPa, about 10 MPa to about 21 MPa, about 15 MPa to
about 21 MPa, about 7MPa to about 15 MPa, or about 7MPa to about 10
MPa, or within a range having any of these values as endpoints,
inclusive of the endpoints. In some embodiments, the protein
polyurethane alloy can have a tensile strength greater than about
21 MPa. For example, the protein polyurethane alloy can have a
tensile strength ranging from about 21 MPa to about 25 MPa.
[0180] In some embodiments, the soy protein polyurethane alloy can
have a tensile strength ranging from about 14 MPa to about 19 MPa
or about 16 MPa to about 19 MPa.
[0181] In some embodiments, the polyurethane in the absence of
protein can have a tensile strength of about 2 MPa or more. In some
embodiments, the polyurethane in the absence of protein can have a
tensile strength ranging from about 2 MPa to about 35 MPa,
including subranges. For example, in some embodiments, the
polyurethane in the absence of protein can have a tensile strength
ranging from about 2 MPa to about 35 MPa, about 5MPa to about 30
MPa, about 10 MPa to about 25 MPa, or about 15 MPa to about 20 MPa,
or within a range having any two of these values as endpoints,
inclusive of the endpoints. In some embodiments, the polyurethane
in the absence of protein can have a tensile strength ranging from
about 10 MPa to about 15 MPa. In some embodiments, the polyurethane
in the absence of protein can have a tensile strength ranging from
about 1 MPa to about 35 MPa.
[0182] In some embodiments, the protein polyurethane alloy can
comprise a polyurethane having a Young's modulus in the absence of
protein. That same protein polyurethane alloy can have a Young's
modulus ranging from about 10% to about 600% greater than the
Young's modulus of the polyurethane in the absence of protein. This
relative percent increase in Young's modulus can be referred to as
"% Delta Young's Modulus." In some embodiments, the % Delta Young's
Modulus can be about 10% or more. In some embodiments, the % Delta
Young's Modulus can range from about 10% to about 600%, about 20%
to about 600%, about 30% to about 600%, about 40% to about 600%,
about 50% to about 600%, about 60% to about 600%, about 70% to
about 600%, about 80% to about 600%, about 90% to about 600%, about
100% to about 600%, about 200% to about 600%, about 300% to about
600%, about 400% to about 600%, or about 500% to about 600%, or
within a range having any two of these values as endpoints,
inclusive of the end points. In some embodiments, the % Delta
Young's Modulus can range from about 40% to about 600%. In some
embodiments, the % Delta Young's Modulus can greater than about
600%. For example, the % Delta Young's Modulus can range from about
600% to about 2400%.
[0183] In some embodiments, the soy protein polyurethane alloy can
comprise a polyurethane having a Young's modulus in the absence of
soy protein. That same soy protein polyurethane alloy can have a
Young's modulus ranging from about 60% to about 570% greater than
the Young's modulus of the polyurethane in the absence of soy
protein. In some embodiments, the % Delta Young's Modulus for the
soy protein polyurethane alloy can be about 60% or more. In some
embodiments, the % Delta Young's Modulus for the soy protein
polyurethane alloy can range from about 60% to about 570%, about
100% to about 570%, about 200% to about 570%, about 300% to about
570%, about 400% to about 570%, or about 500% to about 570%, or
within a range having any two of these values as endpoints,
inclusive of the end points.
[0184] In some embodiments, the protein polyurethane alloy can
comprise a polyurethane having a Young's modulus in the absence of
protein. That same protein polyurethane alloy can have a Young's
modulus ranging from about 10 MPa to about 350 MPa greater than the
Young's modulus of the polyurethane in the absence of protein. This
relative increase in Young's modulus can be referred to as "Delta
Young's Modulus." In some embodiments, the Delta Young's Modulus
can be greater than 10 MPa. In some embodiments, the Delta Young's
Modulus can range from about 10 MPa to about 350 MPa, about 25 MPa
to about 350 MPa, about 50 MPa to about 350 MPa, about 100 MPa to
about 350 MPa, about 150 MPa to about 350 MPa, about 200 MPa to
about 350 MPa, about 250 MPa to about 350 MPa, about 300 MPa to
about 350 MPa, about 10 MPa to about 300 MPa, about 10 MPa to about
250 MPa, about 10 MPa to about 200 MPa, about 10 MPa to about 150
MPa, about 10 MPa to about 100 MPa, about 10 MPa to about 50 MPa,
or about 10 MPa to about 25 MPa, or within a range having any two
of these values as endpoints, inclusive of the endpoints. In some
embodiments, the Delta Young's Modulus can range from about 25 MPa
to about 350 MPa. In some embodiments, the Delta Young's Modulus
can range from about 100 MPa to about 350 MPa.
[0185] In some embodiments, the soy protein polyurethane alloy can
comprise a polyurethane having a Young's modulus in the absence of
soy protein. That same soy protein polyurethane alloy can have a
Young's modulus ranging from about 35 MPa to about 340 MPa greater
than the Young's modulus of the polyurethane in the absence of soy
protein. In some embodiments, the Delta Young's Modulus for the soy
protein polyurethane alloy can be greater than 35 MPa. In some
embodiments, the Delta Young's Modulus for the soy protein
polyurethane alloy can range from about 35 MPa to about 340 MPa,
about 50 MPa to about 340 MPa, about 100 MPa to about 340 MPa,
about 150 MPa to about 340 MPa, about 200 MPa to about 340 MPa,
about 250 MPa to about 340 MPa, about 300 MPa to about 340 MPa,
about 35 MPa to about 300 MPa, about 35 MPa to about 250 MPa, about
35 MPa to about 200 MPa, about 35 MPa to about 150 MPa, about 35
MPa to about 100 MPa, or about 35 MPa to about 50 MPa, or within a
range having any two of these values as endpoints, inclusive of the
endpoints.
[0186] In some embodiments, the protein polyurethane alloy can have
a Young's modulus ranging from about 50 MPa to about 450 MPa,
including subranges. For example, in some embodiments, the protein
polyurethane alloy can have a Young's modulus ranging from about 50
MPa to about 450 MPa, about 75 MPa to about 450 MPa, about 100 MPa
to about 450 MPa, about 150 MPa to about 450 MPa, about 200 MPa to
about 450 MPa, about 250 MPa to about 450 MPa, about 300 MPa to
about 450 MPa, about 350 MPa to about 450 MPa, about 400 MPa to
about 450 MPa, about 50 MPa to about 400 MPa, about 50 MPa to about
350 MPa, about 50 MPa to about 300 MPa, about 50 MPa to about 250
MPa, about 50 MPa to about 200 MPa, about 50 MPa to about 150 MPa,
about 50 MPa to about 100 MPa, or about 50 MPa to about 75 MPa, or
within a range having any two of these values as endpoints,
inclusive of the endpoints. In some embodiments, the protein
polyurethane alloy can have a Young's modulus ranging from about 75
MPa to about 450 MPa. In some embodiments, the protein polyurethane
alloy can have a Young's modulus greater than about 450 MPa. For
example, the protein polyurethane alloy can have a Young's modulus
ranging from about 450 MPa to about 580 MPa.
[0187] In some embodiments, the soy protein polyurethane alloy can
have a Young's modulus ranging from about 90 MPa to about 400 MPa,
including subranges. For example, in some embodiments, the soy
protein polyurethane alloy can have a Young's modulus ranging from
about 90 MPa to about 400 MPa, about 100 MPa to about 400 MPa,
about 150 MPa to about 400 MPa, about 200 MPa to about 400 MPa,
about 250 MPa to about 400 MPa, about 300 MPa to about 400 MPa,
about 350 MPa to about 400 MPa, about 90 MPa to about 350 MPa,
about 90 MPa to about 300 MPa, about 90 MPa to about 250 MPa, about
90 MPa to about 200 MPa, about 90 MPa to about 150 MPa, or about 90
MPa to about 100 MPa, or within a range having any two of these
values as endpoints, inclusive of the endpoints.
[0188] In some embodiments, the polyurethane in the absence of
protein can have a Young's modulus of about 10 MPa or more. In some
embodiments, the polyurethane in the absence of protein can have a
Young's modulus ranging from about 10 MPa to about 600 MPa,
including subranges. For example, in some embodiments, the
polyurethane in the absence of protein can have a Young's modulus
ranging from about 10 MPa to about 600 MPa, about 10 MPa to about
500 MPa, about 10 MPa to about 400 MPa, about 10 MPa to about 300
MPa, about 10 MPa to about 200 MPa, about 10 MPa to about 100 MPa,
or about 10 MPa to about 50 MPa, or within a range having any two
of these values as endpoints, inclusive of the endpoints. In some
embodiments, the polyurethane in the absence of protein can have a
Young's modulus ranging from about 50 MPa to about 100 MPa.
[0189] In some embodiments, the protein polyurethane alloy can
comprise a polyurethane having a moisture vapor transmission rate
in the absence of the protein. That same protein polyurethane alloy
can have a moisture vapor transmission rate about 20% or more
greater than the moisture vapor transmission rate in the absence of
the protein. In some embodiments, the protein polyurethane alloy
can have a moisture vapor transmission rate about 20% to about 600%
greater than the moisture vapor transmission rate of the
polyurethane in the absence of protein. This relative percent
increase in moisture vapor transmission rate can be referred to as
"% Delta MVTR." In some embodiments, % Delta MVTR can be about 20%
or more. In some embodiments, % Delta MVTR can range from about 20%
to about 600%, about 30% to about 600%, about 40% to about 600%,
about 50% to about 600%, about 75% to about 600%, about 100% to
about 600%, about 125% to about 600%, about 150% to about 600%,
about 200% to about 600%, about 20% to about 500%, about 20% to
about 400%, about 20% to about 300%, about 20% to about 200%, about
20% to about 150%, about 20% to about 125%, or about 20% to about
100%, or within a range having any two of these values as
endpoints, inclusive of the endpoints.
[0190] In some embodiments, the soy protein polyurethane alloy can
comprise a % Delta MVTR of about 20% or more. In some embodiments,
% Delta MVTR for the soy protein polyurethane alloy can range from
about 20% to about 600%, about 30% to about 600%, about 40% to
about 600%, about 50% to about 600%, about 75% to about 600%, about
100% to about 600%, about 125% to about 600%, about 150% to about
600%, about 200% to about 600%, about 20% to about 500%, about 20%
to about 400%, about 20% to about 300%, about 20% to about 200%,
about 20% to about 150%, about 20% to about 125%, or about 20% to
about 100%, or within a range having any two of these values as
endpoints, inclusive of the endpoints.
[0191] In some embodiments, the protein polyurethane alloy can
comprise a polyurethane having a moisture vapor transmission rate
in the absence of protein. That same protein polyurethane alloy can
comprise a moisture vapor transmission rate ranging from about 30
g/m.sup.2/24 hr to about 500 g/m.sup.2/24 hr greater than the
moisture vapor transmission rate of the polyurethane in the absence
of protein. This relative increase in moisture vapor transmission
rate can be referred to as "Delta MVTR." In some embodiments, the
Delta MVTR can be greater than or equal to 30 g/m.sup.2/24 hr. In
some embodiments, the Delta MVTR can range from about 30
g/m.sup.2/24 hr to about 500 g/m.sup.2/24 hr, about 40 g/m.sup.2/24
hr to about 500 g/m.sup.2/24 hr, about 50 g/m.sup.2/24 hr to about
500 g/m.sup.2/24 hr, about 75 g/m.sup.2/24 hr to about 500
g/m.sup.2/24 hr, about 100 g/m.sup.2/24 hr to about 500
g/m.sup.2/24 hr, about 150 g/m.sup.2/24 hr to about 500
g/m.sup.2/24 hr, about 200 g/m.sup.2/24 hr to about 500
g/m.sup.2/24 hr, about 300 g/m.sup.2/24 hr to about 500
g/m.sup.2/24 hr, about 30 g/m.sup.2/24 hr to about 400 g/m.sup.2/24
hr, about 30 g/m.sup.2/24 hr to about 300 g/m.sup.2/24 hr, about 30
g/m.sup.2/24 hr to about 200 g/m.sup.2/24 hr, about 30 g/m.sup.2/24
hr to about 150 g/m.sup.2/24 hr, about 30 g/m.sup.2/24 hr to about
100 g/m.sup.2/24 hr, about 30 MPa to about 75 g/m.sup.2/24 hr, or
about 30 g/m.sup.2/24 hr to about 50 g/m.sup.2/24 hr, or within a
range having any two of these values as endpoints, inclusive of the
endpoints.
[0192] In some embodiments, the soy protein polyurethane alloy can
comprise a Delta MVTR greater than or equal to 30 g/m.sup.2/24 hr.
In some embodiments, the Delta MVTR for the soy protein
polyurethane alloy can range from about 30 g/m.sup.2/24 hr to about
500 g/m.sup.2/24 hr, about 40 g/m.sup.2/24 hr to about 500
g/m.sup.2/24 hr, about 50 g/m.sup.2/24 hr to about 500 g/m.sup.2/24
hr, about 75 g/m.sup.2/24 hr to about 500 g/m.sup.2/24 hr, about
100 g/m.sup.2/24 hr to about 500 g/m.sup.2/24 hr, about 150
g/m.sup.2/24 hr to about 500 g/m.sup.2/24 hr, about 200
g/m.sup.2/24 hr to about 500 g/m.sup.2/24 hr, about 300
g/m.sup.2/24 hr to about 500 g/m.sup.2/24 hr, about 30 g/m.sup.2/24
hr to about 400 g/m.sup.2/24 hr, about 30 g/m.sup.2/24 hr to about
300 g/m.sup.2/24 hr, about 30 g/m.sup.2/24 hr to about 200
g/m.sup.2/24 hr, about 30 g/m.sup.2/24 hr to about 150 g/m.sup.2/24
hr, about 30 g/m.sup.2/24 hr to about 100 g/m.sup.2/24 hr, about 30
MPa to about 75 g/m.sup.2/24 hr, or about 30 g/m.sup.2/24 hr to
about 50 g/m.sup.2/24 hr, or within a range having any two of these
values as endpoints, inclusive of the endpoints.
[0193] In some embodiments, the protein polyurethane alloy can
comprise a moisture vapor transmission rate ranging from about 30
g/m.sup.2/24 hr to about 1000 g/m.sup.2/24 hr, including subranges.
For example, in some embodiments, the protein polyurethane alloy
can comprise a moisture vapor transmission rate ranging from about
30 g/m.sup.2/24 hr to about 1000 g/m.sup.2/24 hr, about 60
g/m.sup.2/24 hr to about 1000 g/m.sup.2/24 hr, about 100
g/m.sup.2/24 hr to about 1000 g/m.sup.2/24 hr, about 200
g/m.sup.2/24 hr to about 1000 g/m.sup.2/24 hr, about 250
g/m.sup.2/24 hr to about 1000 g/m.sup.2/24 hr, about 300
g/m.sup.2/24 hr to about 1000 g/m.sup.2/24 hr, about 400
g/m.sup.2/24 hr to about 1000 g/m.sup.2/24 hr, about 500
g/m.sup.2/24 hr to about 1000 g/m.sup.2/24 hr, about 30
g/m.sup.2/24 hr to about 900 g/m.sup.2/24 hr, about 30 g/m.sup.2/24
hr to about 800 g/m.sup.2/24 hr, about 30 g/m.sup.2/24 hr to about
700 g/m.sup.2/24 hr, about 30 g/m.sup.2/24 hr to about 600
g/m.sup.2/24 hr, about 30 g/m.sup.2/24 hr to about 500 g/m.sup.2/24
hr, about 30 g/m.sup.2/24 hr to about 400 g/m.sup.2/24 hr, about 30
g/m.sup.2/24 hr to about 300 g/m.sup.2/24 hr, about 30 g/m.sup.2/24
hr to about 250 g/m.sup.2/24 hr, about 30 g/m.sup.2/24 hr to about
200 g/m.sup.2/24 hr, or about 30 g/m.sup.2/24 hr to about 100
g/m.sup.2/24 hr, or within a range having any two of these values
as endpoints, inclusive of the endpoints. In some embodiments, the
protein polyurethane alloy can comprise a moisture vapor
transmission rate of greater than or equal to about 250
g/m.sup.2/24 hr. For example, in some embodiments, the protein
polyurethane alloy can comprise a moisture vapor transmission rate
ranging from about 250 g/m.sup.2/24 hr to about 1000 g/m.sup.2/24
hr, about 250 g/m.sup.2/24 hr to about 700 g/m.sup.2/24 hr, or
about 250 g/m.sup.2/24 hr to about 500 g/m.sup.2/24 hr.
[0194] In some embodiments, the soy protein polyurethane alloy can
comprise a moisture vapor transmission rate ranging from about 30
g/m.sup.2/24 hr to about 1000 g/m.sup.2/24 hr, including subranges.
For example, in some embodiments, the soy protein polyurethane
alloy can comprise a moisture vapor transmission rate ranging from
about 30 g/m.sup.2/24 hr to about 1000 g/m.sup.2/24 hr, about 60
g/m.sup.2/24 hr to about 1000 g/m.sup.2/24 hr, about 100
g/m.sup.2/24 hr to about 1000 g/m.sup.2/24 hr, about 200
g/m.sup.2/24 hr to about 1000 g/m.sup.2/24 hr, about 250
g/m.sup.2/24 hr to about 1000 g/m.sup.2/24 hr, about 300
g/m.sup.2/24 hr to about 1000 g/m.sup.2/24 hr, about 400
g/m.sup.2/24 hr to about 1000 g/m.sup.2/24 hr, about 500
g/m.sup.2/24 hr to about 1000 g/m.sup.2/24 hr, about 30
g/m.sup.2/24 hr to about 900 g/m.sup.2/24 hr, about 30 g/m.sup.2/24
hr to about 800 g/m.sup.2/24 hr, about 30 g/m.sup.2/24 hr to about
700 g/m.sup.2/24 hr, about 30 g/m.sup.2/24 hr to about 600
g/m.sup.2/24 hr, about 30 g/m.sup.2/24 hr to about 500 g/m.sup.2/24
hr, about 30 g/m.sup.2/24 hr to about 400 g/m.sup.2/24 hr, about 30
g/m.sup.2/24 hr to about 300 g/m.sup.2/24 hr, about 30 g/m.sup.2/24
hr to about 250 g/m.sup.2/24 hr, about 30 g/m.sup.2/24 hr to about
200 g/m.sup.2/24 hr, or about 30 g/m.sup.2/24 hr to about 100
g/m.sup.2/24 hr, or within a range having any two of these values
as endpoints, inclusive of the endpoints. In some embodiments, the
soy protein polyurethane alloy can comprise a moisture vapor
transmission rate of greater than or equal to about 250
g/m.sup.2/24 hr. For example, in some embodiments, the soy protein
polyurethane alloy can comprise a moisture vapor transmission rate
ranging from about 250 g/m.sup.2/24 hr to about 1000 g/m.sup.2/24
hr, about 250 g/m.sup.2/24 hr to about 700 g/m.sup.2/24 hr, or
about 250 g/m.sup.2/24 hr to about 500 g/m.sup.2/24 hr.
[0195] FIG. 17 shows a layered material 1700 according to some
embodiments. Layered material 1700 includes a polyurethane protein
alloy layer 1720 attached to a substrate layer 1710. Polyurethane
protein alloy layer 1720 can be directly attached to a surface of
substrate layer 1710 or attached to a surface of substrate layer
1710 via an intermediate layer, for example an adhesive layer.
Direct attachment can be achieved using, for example, a thermal
bonding process or a stitching. Polyurethane protein alloy layer
1720 can be referred to as a "first polyurethane protein alloy
layer."
[0196] Polyurethane protein alloy layer 1720 can include one or
more types of protein and one or more polyurethanes. In some
embodiments, polyurethane protein alloy layer 1720 can include one
or more proteins dissolved within one or more polyurethanes. In
some embodiments, polyurethane protein alloy layer 1720 can be
transparent. The transparency of a polyurethane protein alloy layer
is evaluated before dying or otherwise coloring a polyurethane
protein alloy layer.
[0197] A transparent protein polyurethane alloy layer can provide
unique characteristics for a layered material. For example,
compared to a non-transparent layer, a transparent protein
polyurethane alloy layer can provide unique depth of color when
dyed. Likewise, a transparent protein polyurethane alloy layer can
provide its mechanical properties to a layered material without
significantly influencing the aesthetic properties of the
material.
[0198] Protein polyurethane alloy layer 1720 includes a bottom
surface 1722, a top surface 1724, and thickness 1726 measured
between bottom surface 1722 and top surface 1724. In some
embodiments, thickness 1726 can range from about 25 microns to
about 400 microns (micrometers, .mu.m), including subranges. For
example, thickness 1726 can be about 25 microns, about 50 microns,
about 100 microns, about 125 microns, about 150 microns, about 175
microns, about 200 microns, about 250 microns, about 300 microns,
about 350 microns, or about 400 microns, or within a range having
any two of these values as endpoints, inclusive of the endpoints.
In some embodiments, thickness 1726 can range from about 50 microns
to about 350 microns, about 75 microns to about 300 microns, about
100 microns to about 250 microns, about 125 microns to about 200
microns, or about 150 microns to about 175 microns.
[0199] Protein polyurethane alloy layer 1720 can have a dry weight,
measured in grams per square meter (gsm, g/m.sup.2), ranging from
about 25 g/m.sup.2 to about 125 g/m.sup.2, including subranges. For
example, protein polyurethane alloy layer 1720 can have a dry
weight of about 25 g/m.sup.2, about 50 g/m.sup.2, about 75
g/m.sup.2, about 100 g/m.sup.2, or about 125 g/m.sup.2, or within a
range having any two of these values as endpoints, inclusive of the
endpoints. In some embodiments, protein polyurethane alloy layer
1720 can have a dry weight ranging from about 25 g/m.sup.2 to about
125 g/m.sup.2, about 25 g/m.sup.2 to about 100 g/m.sup.2, or about
50 g/m.sup.2 to about 100 g/m.sup.2.
[0200] Unless specified otherwise, the dry weight of a layer is
measured during the process of making a material using the
following method. First, before applying the layer in question to
the material, a first sample (about 10 centimeters in diameter) of
the material is cut, and the weight and dimensions are measured to
calculate a first dry weight. If a sacrificial layer is present, it
is removed before measuring the weight and dimensions. Second,
after applying and drying the layer in question, a second sample of
the same size is cut from the material, and the weight and
dimensions are measured to calculate a second dry weight. If a
sacrificial layer is present, it is removed before measuring the
weight and dimensions. Third, the first dry weight is subtracted
from the second dry weight to obtain the dry weight of the layer in
question. All the weight and dimension measurements are performed
at the same humidity level, typically the humidity level of the
manufacturing environment in which the material is made. For
purposes of calculating a dry weight, three separate dry weight
tests are performed, and the average dry weight is reported as the
dry weight of the layer.
[0201] In some embodiments, protein polyurethane alloy layer 1720
can be a non-foamed layer. A "non-foamed" layer means a layer
having a density, measured in the percent void space for the layer,
of 5% void space or less, for example 0% void space to 5% void
space. In some embodiments, protein polyurethane alloy layer 1720
can be a foamed layer. In such embodiments, protein polyurethane
alloy layer 1720 can have a density, measured in the percent void
space for layer 1720, ranging from about 5% void space to about 70%
void space, including subranges. For example, protein polyurethane
alloy layer 1720 can have about 5% void space, about 10% void
space, about 20% void space, about 30% void space, about 35% void
space, about 40% void space, about 45% void space, about 50% void
space, about 55% void space, about 60% void space, about 65% void
space, or about 70% void space, or within a range having any two of
these values as endpoints, inclusive of the endpoints. In some
embodiments, protein polyurethane alloy layer 1720 can have a
percent void space ranging from about 10% to about 65%, about 20%
to about 60%, about 30% to about 55%, about 35% to about 50%, or
about 40% to about 45%.
[0202] A percent void space (which can also be referred to as a
"percent porosity") can be measured by image analysis of a
cross-section of a layer or by measuring the bulk density of sample
of a layer using a pycnometer. Unless specified otherwise, a
percent void space reported herein is measured by image analysis of
a cross-section of a layer. The images are analyzed using ImageJ
software (or equivalent software) at 37.times. magnification. The
ImageJ software uses a trainable Weka segmentation classifier to
calculate the percent void space in the layer. For purposes of
calculating a percent void space, three to five separate images of
a cross-section are evaluated, and the average percent void space
is reported as the percent void space for the layer. In some
embodiments, protein polyurethane alloy layer 1720 can include one
or more foaming agents and/or foam stabilizers. Suitable foaming
agents and foam stabilizers include those discussed herein for
layers 1730 and 1740.
[0203] Substrate layer 1710 includes a bottom surface 1712, a top
surface 1714, and a thickness 1716 measured between bottom surface
1712 and top surface 1714. In some embodiments, thickness 1716 can
range from about 50 microns to about 1000 microns, including
subranges. For example, thickness 1716 can be about 50 microns,
about 100 microns, about 150 microns, about 200 microns, about 250
microns, about 300 microns, about 350 microns, about 400 microns,
about 500 microns, about 600 microns, about 700 microns, about 800
microns, about 900 microns, or about 1000 microns, or within a
range having any two of these values as endpoints, inclusive of the
endpoints. In some embodiments, thickness 1716 can range from about
100 microns to about 900 microns, about 150 microns to about 800
microns, about 200 microns to about 700 microns, about 250 microns
to about 600 microns, about 300 microns to about 500 microns, or
about 350 microns to about 400 microns.
[0204] Substrate layer 1710 can have a dry weight, measured in
grams per square meter (g/m.sup.2), ranging from about 50 g/m.sup.2
to about 600 g/m.sup.2, including subranges. For example, substrate
layer 110 can have a dry weight of about 50 g/m.sup.2, about 75
g/m.sup.2, about 100 g/m.sup.2, about 125 g/m.sup.2, about 150
g/m.sup.2, about 175 g/m.sup.2, about 200 g/m.sup.2, about 300
g/m.sup.2, about 400 g/m.sup.2, about 500 g/m.sup.2, or about 600
g/m.sup.2, or within a range having any two of these values as
endpoints. In some embodiments, substrate layer 1710 can have a dry
weight ranging from about 75 g/m.sup.2 to about 500 g/m.sup.2,
about 100 g/m.sup.2 to about 400 g/m.sup.2, about 125 g/m.sup.2 to
about 300 g/m.sup.2, about 150 g/m.sup.2 to about 200 g/m.sup.2, or
about 175 g/m.sup.2 to about 200 g/m.sup.2.
[0205] Substrate layer 1710 can include one or more textile layers.
The one or more textile layers can be, for example, a woven layer,
a non-woven layer, a knit layer, a mesh fabric layer, or a leather
layer. The one or more textile layer can be comprised of recycled
or virgin fibers, filaments or yarns. In some embodiments,
substrate layer 1710 can be, or can include, a polyester knit
layer, a polyester cotton spandex blend knit layer, or a suede
layer. In some embodiments, substrate layer 1710 can be made from
one or more natural fibers, for example fibers made from cotton,
linen, silk, wool, kenaf, flax, cashmere, angora, bamboo, bast,
hemp, soya, seacell, milk or milk proteins, spider silk, chitosan,
mycelium, cellulose including bacterial cellulose, or wood.
Mycelium is the vegetative part of a fungus or fungus-like
bacterial colony, composed of a mass of branching, thread-like
hyphae. Fungi are composed primarily of a cell wall that is
constantly being extended at the apex of the hyphae. Unlike the
cell wall of a plant, which is composed primarily of cellulose, or
the structural component of an animal cell, which relies on
collagen, the structural oligosaccharides of the cell wall of fungi
rely primarily on chitin and beta glucan. Chitin is a strong, hard
substance, also found in the exoskeletons of arthropods.
[0206] In some embodiments, substrate layer 1710 can be made from
one or more synthetic fibers, for example fibers made from
polyesters, nylons, aromatic polyamides, polyolefin fibers such as
polyethylene, polypropylene, rayon, lyocell, viscose, antimicrobial
yarn (A.M.Y.), Sorbtek, nylon, elastomers such as LYCRA.RTM.,
spandex, or ELASTANE.RTM., polyester-polyurethane copolymers,
aramids, carbon including carbon fibers and fullerenes, glass,
silicon, minerals, metals or metal alloys including those
containing iron, steel, lead, gold, silver, platinum, copper, zinc,
and titanium, or mixtures thereof.
[0207] In some embodiments, non-woven substrate layer 1710 can be a
staple non-woven, melt-blown non-woven, spunlaid non-woven,
flashspun non-woven, or a combination thereof. In some embodiments,
non-woven substrate layer 1710 can be made by carding, can be
air-laid, or can be wet-laid. In some embodiments, the carded,
air-laid, or wet-laid substrates can be bonded by, for example,
needle-punch, hydroentanglement, lamination, or thermal bonding. In
some embodiments, non-woven substrate layer 1710 can include one or
more natural fibers, for example fibers made from cotton, linen,
silk, wool, kenaf, flax, cashmere, angora, bamboo, bast, hemp,
soya, seacell, milk or milk proteins, spider silk, chitosan,
mycelium, cellulose including bacterial cellulose, or wood.
[0208] In some embodiments, non-woven substrate layer 1710 can
include polymeric fibers with functional particles in the polymer.
Exemplary functional particles include ceramic particles mixed in a
polymeric resin during an extrusion process for making the
polymeric fibers. Such ceramic particles can provide the polymeric
fibers with desirable heat dissipation and flame resistance
properties. In some embodiments, non-woven substrate layer 1710 can
include fibers made of fruit pulp (e.g., grape pulp or apple pulp)
or pineapple fibers. In some embodiments, non-woven substrate layer
1710 can include fibers made from recycled materials, for example
recycled plastics. In some embodiments, non-woven substrate layer
1710 can include algae fibers. In some embodiments, a non-woven
substrate layer 1710 can include cork fibers.
[0209] In some embodiments, substrate layer 1710 can be, or can
include, a spacer fabric, for example spacer fabric 2100, shown in
FIG. 21. Spacer fabric 2100 includes a first fabric layer 2110 and
a second fabric layer 2120 connected by one or more spacer yarns
2130. Spacer yarn(s) 2130 are disposed between first fabric layer
2110 and second fabric layer 2120 and define a distance between an
interior surface 2114 of first fabric layer 2110 and an interior
surface 2124 of second fabric layer 2120. Exterior surface 2112 of
first fabric layer 2110 and exterior surface 2122 of second fabric
layer 2120 can define top surface 1714 and bottom surface 1712 of
substrate layer 1710, respectively.
[0210] First fabric layer 2110 and second fabric layer 2120 can
include one or more layers of fabric material. In some embodiments,
first fabric layer 2110 and second fabric layer 2120 can include
one or more textile layers made from staple fibers, filaments, or
mixtures thereof. As used herein, "staple fibers" are fibers having
a short length, between about 0.2 mm to about 5 centimeters (cm).
Staple fibers can be naturally occurring or can be cut filaments.
As used herein, "filaments" are long fibers having a length of 5 cm
or more. In some embodiments, first fabric layer 2110 and second
fabric layer 2120 can include one or more layers of a woven
material or a knitted material. In some embodiments, exterior
surface 2112 of first fabric layer 2110 can be defined by a woven
fabric layer or a knitted fabric layer. In some embodiments,
exterior surface 2122 of second fabric layer 2120 can be defined by
a woven fabric layer or a knitted fabric layer.
[0211] In some embodiments, first fabric layer 2110 and second
fabric layer 2120 can be made from one or more natural fibers, for
example fibers made from cotton, linen, silk, wool, kenaf, flax,
cashmere, angora, bamboo, bast, hemp, soya, seacell, milk or milk
proteins, spider silk, chitosan, mycelium, cellulose including
bacterial cellulose, or wood. In some embodiments, first fabric
layer 2110 and second fabric layer 2120 can be made from one or
more synthetic fibers, for example fibers made from polyesters,
nylons, aromatic polyamides, polyolefin fibers such as
polyethylene, polypropylene, rayon, lyocell, viscose, antimicrobial
yarn (A.M.Y.), Sorbtek, nylon, elastomers such as LYCRA.RTM.,
spandex, or ELASTANE.RTM., polyester-polyurethane copolymers,
aramids, carbon including carbon fibers and fullerenes, glass,
silicon, minerals, metals or metal alloys including those
containing iron, steel, lead, gold, silver, platinum, copper, zinc,
and titanium, or mixtures thereof. Spacer yarn(s) 2130 can include
mono-filament yarn(s) composed of any of the natural or synthetic
materials listed above for first fabric layer 2110 and second
fabric layer 2120.
[0212] In some embodiments, substrate layer 1710 can be colored
with a coloring agent. In some embodiments the coloring agent can
be a dye, for example an acid dye, a fiber reactive dye, a direct
dye, a sulfur dye, a basic dye, or a reactive dye. In some
embodiments, the coloring agent can be pigment, for example a lake
pigment. In some embodiments, a first coloring agent can be
incorporated into one or more protein polyurethane alloy layers and
a second coloring agent can be incorporated into substrate layer
1710, depending on the desired aesthetic of a layered material.
[0213] A fiber reactive dye includes one or more chromophores that
contain pendant groups capable of forming covalent bonds with
nucleophilic sites in fibrous, cellulosic substrates in the
presence of an alkaline pH and raised temperature. These dyes can
achieve high wash fastness and a wide range of brilliant shades.
Exemplary fiber reactive dyes, include but are not limited to,
sulphatoethylsulphone (Remazol), triazine, vinylsulphone, and
acrylamido dyes. These dyes can dye protein fibers such as silk,
wool and nylon by reacting with fiber nucleophiles via a Michael
addition. Direct dyes are anionic dyes capable of dying cellulosic
or protein fibers. In the presence of an electrolyte such as sodium
chloride or sodium sulfate, near boiling point, these dyes can have
an affinity to cellulose. Exemplary direct dyes include, but are
not limited to, azo, stilbene, phthalocyanine, and dioxazine.
[0214] In some embodiments, layered material 1700 can include a
protein polyurethane alloy layer 1720 attached to top surface 1714
of substrate layer 1710. In some embodiments, bottom surface 1722
of protein polyurethane alloy layer 1720 can be in direct contact
with top surface 1714 of substrate layer 1710. In some embodiments,
bottom surface 1722 of protein polyurethane alloy layer 1720 can be
attached to top surface 1714 of substrate layer 1710 via an
adhesive layer (e.g., adhesive layer 1750). In some embodiments,
layered material 1700 can include a protein polyurethane alloy
layer 1720 attached to bottom surface 1712 of substrate layer 1710.
In some embodiments, top surface 1724 of protein polyurethane alloy
layer 1720 can be in direct contact with bottom surface 1712 of
substrate layer 1710. In some embodiments, top surface 1724 of
protein polyurethane alloy layer 1720 can be attached to bottom
surface 1712 of substrate layer 1710 via an adhesive layer (e.g.,
adhesive layer 1750). In some embodiments, layered material 1700
can include a protein polyurethane alloy layer 1720 attached to top
surface 1714 of substrate layer 1710 and a protein polyurethane
alloy layer 1720 attached to bottom surface 1712 of substrate layer
1710. In such embodiments, layered material 1700 includes protein
polyurethane alloy layers 1720 disposed on opposing surfaces of
substrate layer 1710.
[0215] In some embodiments, as shown for example in FIG. 18,
layered material 1700 can include a second protein polyurethane
alloy layer 1730 disposed between protein polyurethane alloy layer
1720 and substrate layer 1710. In such embodiments, second protein
polyurethane alloy layer 1730 is attached to protein polyurethane
alloy layer 1720. In some embodiments, bottom surface 1722 of
protein polyurethane alloy layer 1720 can be in direct contact with
a top surface 1734 of second protein polyurethane alloy layer
1730.
[0216] Second protein polyurethane alloy layer 1730 includes a
bottom surface 1732, top surface 1734, and a thickness 1736
measured between bottom surface 1732 and top surface 1734. In some
embodiments, thickness 1736 can range from about 25 microns to
about 600 microns, including subranges. For example, thickness 1736
can be about 25 microns, about 50 microns, about 100 microns, about
125 microns, about 150 microns, about 175 microns, about 200
microns, about 225 microns, about 250 microns, about 275 microns,
about 300 microns, about 400 microns, about 500 microns, or about
600 microns, or within a range having any two of these values as
endpoints, inclusive of the endpoints. In some embodiments,
thickness 1736 can range from about 50 microns to about 500
microns, about 75 microns to about 400 microns, about 100 microns
to about 300 microns, about 125 microns to about 275 microns, about
150 microns to about 250 microns, about 175 microns to about 225
microns, or about 200 microns to about 225 microns. In some
embodiments, thickness 1736 can be greater than thickness 1726. In
some embodiments, thickness 1736 can be less than thickness 1726.
In some embodiments, thickness 1736 can be greater than or less
than thickness 1726 by 5 microns or more.
[0217] Second protein polyurethane alloy layer 1730 can have a dry
weight, measured in grams per square meter (g/m.sup.2), ranging
from about 30 g/m.sup.2 to about 600 g/m.sup.2, including
subranges. For example, second protein polyurethane alloy layer
1730 can have a dry weight of about 30 g/m.sup.2, about 40
g/m.sup.2, about 60 g/m.sup.2, about 80 g/m.sup.2, about 100
g/m.sup.2, about 120 g/m.sup.2, about 140 g/m.sup.2, about 150
g/m.sup.2, about 200 g/m.sup.2, about 300 g/m.sup.2, about 400
g/m.sup.2, about 500 g/m.sup.2, or about 600 g/m.sup.2, or within a
range having any two of these values as endpoints, inclusive of the
endpoints. In some embodiments, second protein polyurethane alloy
layer 1730 can have a dry weight ranging from about 40 g/m.sup.2 to
about 500 g/m.sup.2, about 60 g/m.sup.2 to about 400 g/m.sup.2,
about 80 g/m.sup.2 to about 300 g/m.sup.2, about 100 g/m.sup.2 to
about 200 g/m.sup.2, about 120 g/m.sup.2 to about 150 g/m.sup.2, or
about 140 g/m.sup.2 to about 150 g/m.sup.2. In some embodiments,
protein polyurethane alloy layer 1720 can have a first weight and
second protein polyurethane alloy layer 1730 can have a second
weight, and the first weight can be less than the second weight. In
some embodiments, the first weight can be less than the second
weight by 5 g/m.sup.2 or more.
[0218] In some embodiments, second protein polyurethane alloy layer
1730 can include a foaming agent. In some embodiments, second
protein polyurethane alloy layer 1730 can include a foam
stabilizer. The foaming agent or foam stabilizer can facilitate the
formation of voids in second protein polyurethane alloy layer 1730
during blending of second protein polyurethane alloy layer 1730.
Suitable foam stabilizers include, but are not limited to, HeiQ
Chemtex 2216-T (a stabilized blend of nonionic and anionic
surfactants), HeiQ Chemtex 2241-A (a modified HEUR
(hydrophobically-modified ethylene oxide urethane) thickener), HeiQ
Chemtex 2243 (a non-ionic silicone dispersion), or HeiQ Chemtex
2317 (a stabilized blend of nonionic and anionic surfactants) foam
stabilizers available from HeiQ Chemtex. When used, a foam
stabilizer serves to stabilize mechanically created foam (air
voids). The mechanically created foam may be created by, for
example, a rotor and/or compressed air. When used, a foaming agent
can create foam (air voids) within a layer by a chemical reaction
and/or via heat generation within the layer.
[0219] In some embodiments, second protein polyurethane alloy layer
1730 can be referred to as a "foamed protein polyurethane alloy
layer" because either (i) layer 1730 includes one or more foaming
agents or foam stabilizers and/or (ii) layer 1730 includes a
density less than protein polyurethane alloy layer 1720.
[0220] Second protein polyurethane alloy layer 1730 can have a
density, measured in the percent void space for layer 1730, ranging
from about 5% void space to about 70% void space, including
subranges. For example, second protein polyurethane alloy layer
1730 can have about 5% void space, about 10% void space, about 20%
void space, about 30% void space, about 35% void space, about 40%
void space, about 45% void space, about 50% void space, about 55%
void space, about 60% void space, about 65% void space, or about
70% void space, or within a range having any two of these values as
endpoints, inclusive of the endpoints. In some embodiments, second
protein polyurethane alloy layer 1730 can have a percent void space
ranging from about 10% to about 65%, about 20% to about 60%, about
30% to about 55%, about 35%, to about 50%, or about 40% to about
45%. In some embodiments, protein polyurethane alloy layer 1720 can
have a first density and second protein polyurethane alloy layer
1730 can have a second density, and the first density can be
greater than the second density. In some embodiments, the first
density can be greater than the second density by 5% void space or
more.
[0221] Layering a plurality of protein polyurethane alloy layers
having different weights and/or densities can be used to tailor the
material properties of a layered material. For example, layers
having lighter weights and/or densities can be used to increase the
softness and/or flexibility of a layered material. On the other
hand, layers having high weights and/or densities can increase the
strength of the layered material. Additionally, using one or more
layers having relatively lighter weight and/or density can increase
the ease in which cutting, stitching, and/or shaping process steps
(e.g., skyving) can be performed on a layered material. Layering a
plurality of protein polyurethane alloy layers gives lot of freedom
in designing of a material.
[0222] In some embodiments, second protein polyurethane alloy layer
1730 can further include, in addition to any other components that
may be present, such as a foaming agent, a foam stabilizer, or one
or more coloring agents. The coloring agent type and content for
second protein polyurethane alloy layer 1730 can be any of the
types and amounts described herein for protein polyurethane alloy
layer 1720. In some embodiments, second protein polyurethane alloy
layer 1730 can be free or substantially free of a coloring
agent.
[0223] In some embodiments, as shown for example in FIG. 18,
layered material 1700 can include a third protein polyurethane
alloy layer 1740 disposed between second protein polyurethane alloy
layer 1730 and substrate layer 1710. In such embodiments, third
protein polyurethane alloy layer 1740 is attached to second protein
polyurethane alloy layer 1730. In some embodiments, bottom surface
1732 of second protein polyurethane alloy layer 1730 can be in
direct contact with a top surface 1744 of third protein
polyurethane alloy layer 1740.
[0224] Third protein polyurethane alloy layer 1740 includes a
bottom surface 1742, top surface 1744, and a thickness 1746
measured between bottom surface 1742 and top surface 1744. In some
embodiments, thickness 1746 can range from about 25 microns to
about 600 microns, including subranges. For example, thickness 1746
can be about 25 microns, about 50 microns, about 100 microns, about
125 microns, about 150 microns, about 175 microns, about 200
microns, about 225 microns, about 250 microns, about 275 microns,
about 300 microns, about 400 microns, about 500 microns, or about
600 microns, or within a range having any two of these values as
endpoints, inclusive of the endpoints. In some embodiments,
thickness 1746 can range from about 50 microns to about 500
microns, about 75 microns to about 400 microns, about 100 microns
to about 300 microns, about 125 microns to about 275 microns, about
150 microns to about 250 microns, about 175 microns to about 225
microns, or about 175 microns to about 200 microns. In some
embodiments, thickness 1746 can be greater than thickness 1726. In
some embodiments, thickness 1746 can be less than thickness 1726.
In some embodiments, thickness 1746 can be greater than or less
than thickness 1726 by 5 microns or more. In some embodiments,
thickness 1746 can be the same as thickness 1736. In some
embodiments, thickness 1746 can be greater than or less than
thickness 1736. In some embodiments, thickness 1746 can be greater
than or less than thickness 1736 by 5 microns or more.
[0225] Third protein polyurethane alloy layer 1740 can have a dry
weight, measured in grams per square meter (g/m.sup.2), ranging
from about 30 g/m.sup.2 to about 600 g/m.sup.2, including
subranges. For example, third protein polyurethane alloy layer 1740
can have a dry weight of about 30 g/m.sup.2, about 40 g/m.sup.2,
about 60 g/m.sup.2, about 80 g/m.sup.2, about 100 g/m.sup.2, about
120 g/m.sup.2, about 140 g/m.sup.2, about 150 g/m.sup.2, about 200
g/m.sup.2, about 300 g/m.sup.2, about 400 g/m.sup.2, about 500
g/m.sup.2, or about 600 g/m.sup.2, or within a range having any two
of these values as endpoints, inclusive of the endpoints. In some
embodiments, third protein polyurethane alloy layer 1740 can have a
dry weight ranging from about 40 g/m.sup.2 to about 500 g/m.sup.2,
about 60 g/m.sup.2 to about 400 g/m.sup.2, about 80 g/m.sup.2 to
about 300 g/m.sup.2, about 100 g/m.sup.2 to about 200 g/m.sup.2,
about 120 g/m.sup.2 to about 150 g/m.sup.2, or about 120 g/m.sup.2
to about 140 g/m.sup.2. In some embodiments, protein polyurethane
alloy layer 1720 can have a first weight and third protein
polyurethane alloy layer 1740 can have a third weight, and the
first weight can be less than the third weight. In some
embodiments, protein polyurethane alloy layer 1720 can have a first
weight, second protein polyurethane alloy layer 1730 can have a
second weight, and third protein polyurethane alloy layer 1740 can
have a third weight, and the first weight can be less than the
second weight and the third weight. In some embodiments, the first
weight can be less than the second weight and/or the third weight
by 5 g/m.sup.2 or more.
[0226] In some embodiments, third protein polyurethane alloy layer
1740 can include a foaming agent. In some embodiments, third
protein polyurethane alloy layer 1740 can include a foam
stabilizer. The foaming agent and/or foam stabilizer can facilitate
the formation of voids in third protein polyurethane alloy layer
1740 during blending of third protein polyurethane alloy layer
1740. Suitable foaming agents include, but are not limited to, HeiQ
Chemtex 2216-T (a stabilized blend of nonionic and anionic
surfactants), HeiQ Chemtex 2241-A (a modified HEUR
(hydrophobically-modified ethylene oxide urethane) thickener), HeiQ
Chemtex 2243 (a non-ionic silicone dispersion), or HeiQ Chemtex
2317 (a stabilized blend of nonionic and anionic surfactants) foam
stabilizers available from HeiQ Chemtex.
[0227] In some embodiments, third protein polyurethane alloy layer
1740 can be referred to as a "foamed protein polyurethane alloy
layer" because either (i) layer 1740 includes one or more foaming
agents or foam stabilizers and/or (ii) layer 1740 includes a
density less than protein polyurethane alloy layer 120.
[0228] Third protein polyurethane alloy layer 1740 can have a
density, measured in the percent void space for layer 1740, ranging
from about 5% void space to about 70% void space, including
subranges. For example, third protein polyurethane alloy layer 1740
can have about 5% void space, about 10% void space, about 20% void
space, about 30% void space, about 35% void space, about 40% void
space, about 45% void space, about 50% void space, about 55% void
space, about 60% void space, about 65% void space, or about 70%
void space, or within a range having any two of these values as
endpoints, inclusive of the endpoints. In some embodiments, third
protein polyurethane alloy layer 1740 can have a percent void space
ranging from about 10% to about 65%, about 20% to about 60%, about
30% to about 55%, about 35% to about 50%, or about 40% to about
45%. In some embodiments, protein polyurethane alloy layer 1720 can
have a first density and third protein polyurethane alloy layer
1740 can have a third density, and the first density can be greater
than the third density. In some embodiments, protein polyurethane
alloy layer 1720 can have a first density, second protein
polyurethane alloy layer 1730 can have a second density, and third
protein polyurethane alloy layer 1740 can have a third density, and
the first density can be greater than the second density and third
density. In some embodiments, the first density can be greater than
the second density and/or the third density by 5% void space or
more.
[0229] In some embodiments, layered material 1700 can include a
plurality of protein polyurethane alloy layers having the same
protein and polyurethane. In some embodiments, layered material
1700 can include a plurality of protein polyurethane alloy layers
and the different layers can have a different protein and/or a
different polyurethane.
[0230] In some embodiments, third protein polyurethane alloy layer
1740 can further include, in addition to any other components that
may be present, such as a foaming agent, a foam stabilizer, one or
more coloring agents. The coloring agent type and content for third
protein polyurethane alloy layer 1740 can be any of the types and
amounts described herein for protein polyurethane alloy layer 1720.
In some embodiments, third protein polyurethane alloy layer 1740
can be free or substantially free of a coloring agent.
[0231] In some embodiments, and as shown for example in FIG. 18,
layered material 1700 can include a basecoat layer 1760. Basecoat
layer 1760 can be disposed over top surface 1724 of protein
polyurethane alloy layer 1720. Basecoat layer 1760 can be directly
or indirectly attached to protein polyurethane alloy layer 1720. In
some embodiments, basecoat layer 1760 can be disposed on top
surface 1724 of protein polyurethane alloy layer 1720. In some
embodiments, a bottom surface 1762 of basecoat layer 1760 can be in
direct contact with top surface 1724 of protein polyurethane alloy
layer 1720.
[0232] Basecoat layer 1760 includes bottom surface 1762, a top
surface 1764, and a thickness 1766 measured between bottom surface
1762 and top surface 1764. In some embodiments, thickness 1766 can
range from about 20 microns to about 200 microns, including
subranges. For example, thickness 1766 can be about 20 microns,
about 30 microns, about 40 microns, about 50 microns, about 60
microns, about 70 microns, about 80 microns, about 90 microns,
about 100 microns, about 150 microns, or about 200 microns, or
within a range having any two of these values as endpoints,
inclusive of the endpoints. In some embodiments, thickness 1766 can
range from about 30 microns to about 150 microns, about 40 microns
to about 100 microns, about 50 microns to about 90 microns, about
60 microns to about 80 microns, or about 60 microns to about 70
microns.
[0233] In embodiments including basecoat layer 1760, basecoat layer
1760 can provide one or more of the following properties for
layered material 1700: (i) abrasion performance, color fastness, or
hydrolytic resistance. Basecoat layer 1760 may also serve to adhere
to a top-coat layer to layered material 1700 in embodiments
including a top-coat layer. In some embodiments, basecoat layer
1760 can include one or more polymeric materials. Suitable
materials for basecoat layer 1760 include, but are not limited to,
polyether polyurethanes, polycarbonate polyurethanes, polyester
polyurethanes, acrylic polymers, and cross-linkers such as
isocyanate or carbodiimide. In some embodiments, layered material
1700 can include a plurality of basecoat layers 1760. In some
embodiments, basecoat layer 1760 can be absent from layered
material 1700.
[0234] Basecoat layer 1760 can have a dry weight, measured in grams
per square meter (g/m.sup.2), ranging from about 20 g/m.sup.2 to
about 100 g/m.sup.2, including subranges. For example, basecoat
layer 1760 can have a dry weight of about 20 g/m.sup.2, about 30
g/m.sup.2, about 40 g/m.sup.2, about 50 g/m.sup.2, about 60
g/m.sup.2, about 70 g/m.sup.2, about 80 g/m.sup.2, about 90
g/m.sup.2, or about 100 g/m.sup.2, or within a range having any two
of these values as endpoints, inclusive of the endpoints. In some
embodiments, basecoat layer 1760 can have a dry weight ranging from
about 30 g/m.sup.2 to about 90 g/m.sup.2, about 40 g/m.sup.2 to
about 80 g/m.sup.2, or about 50 g/m.sup.2 to about 70
g/m.sup.2.
[0235] In some embodiments, as shown for example in FIG. 18,
layered material 1700 can include a top-coat layer 1770. Top-coat
layer 1770 can be disposed over top surface 1724 of protein
polyurethane alloy layer 1720. Top-coat layer 1770 can be directly
or indirectly attached to protein polyurethane alloy layer 1720. In
some embodiments, a bottom surface 1772 of top-coat layer 1770 can
be in direct contact with top surface 1724 of protein polyurethane
alloy layer 1720. In embodiments including basecoat layer 1760,
top-coat layer 1770 can be disposed over top surface 1764 of
basecoat layer 1760. In some embodiments, top-coat layer 1770 can
be disposed on top surface 1764 of basecoat layer 1760. In some
embodiments, a bottom surface 1772 of top-coat layer 1770 can be in
direct contact with top surface 1764 of basecoat layer 1760.
[0236] Top-coat layer 1770 includes bottom surface 1772, a top
surface 1774, and a thickness 1776 measured between bottom surface
1772 and top surface 1774. In some embodiments, thickness 1776 can
range from about 10 microns to about 80 microns, including
subranges. For example, thickness 1776 can be about 10 microns,
about 20 microns, about 30 microns, about 40 microns, about 50
microns, about 60 microns, about 70 microns, or about 80 microns,
or within a range having any two of these values as endpoints,
inclusive of the endpoints. In some embodiments, thickness 1776 can
range from about 20 microns to about 70 microns, about 30 microns
to about 60 microns, or about 30 microns to about 50 microns.
[0237] In embodiments including top-coat layer 1770, top-coat layer
1770 can provide one or more of the following properties for
layered material 1700: surface feel, stain resistance, flame
resistance, gloss level, or color appearance. In some embodiments,
top-coat layer 1770 can include one or more polymeric materials.
Suitable materials for top-coat layer 1770 include but are not
limited to, polyurethanes, acrylics, silicone-based feel agents,
matte agents, and gloss agents. In some embodiments, layered
material 1700 can include a plurality of top-coat layers 1770. In
some embodiments, top-coat layer 1770 can be absent from layered
material 1700. In some embodiments, top-coat layer 1770 can be
transparent or translucent. In some embodiments, top-coat layer
1770 can include one or more dyes, one or more pigments and/or one
or more reflective agents to affect appearance.
[0238] Top-coat layer 1770 can have a dry weight, measured in grams
per square meter (g/m.sup.2), ranging from about 10 g/m.sup.2 to
about 80 g/m.sup.2, including subranges. For example, top-coat
layer 1770 can have a dry weight of about 10 g/m.sup.2, about 20
g/m.sup.2, about 30 g/m.sup.2, about 40 g/m.sup.2, about 50
g/m.sup.2, about 60 g/m.sup.2, about 70 g/m.sup.2, or about 80
g/m.sup.2, or within a range having any two of these values as
endpoints, inclusive of the endpoints. In some embodiments,
top-coat layer 1770 can have a dry weight ranging from about 20
g/m.sup.2 to about 70 g/m.sup.2, about 30 g/m.sup.2 to about 60
g/m.sup.2, or about 30 g/m.sup.2 to about 50 g/m.sup.2.
[0239] Together, protein polyurethane alloy layer(s) 1720, 1730,
1740, basecoat layer(s) 1760, and/or top-coat layer(s) 1770 can
define a layered assembly 1780 of a layered material 1700. Layered
assembly 1780 can include any number of protein polyurethane alloy
layers as described herein. For example, layered assembly 1780 can
include 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18,
19, or 20 protein polyurethane alloy layers. In some embodiments,
layered material 1700 can include a layered assembly 1780 attached
to bottom surface 1712 of substrate layer 1710. Layered assembly
1780 attached to bottom surface 1712 of substrate layer 1710 can
include any of the layers and materials as described herein for a
layered assembly 1780 attached to top surface 1714 of substrate
layer 1710. In some embodiments, layered material 1700 can include
a layered assembly 1780 attached to top surface 1714 of substrate
layer 1710 and a layered assembly 1780 attached to bottom surface
1712 of substrate layer 1710. In such embodiments, layered material
1700 includes layered assemblies 1780 disposed over opposing
surfaces 1712 and 1714 of substrate layer 1710.
[0240] In some embodiments, a protein polyurethane alloy layer of
layered material 1700 is attached to a surface of substrate layer
1710 with an adhesive layer 1750. In such embodiments, adhesive
layer 1750 includes a bottom surface 1752, a top surface 1754, and
a thickness 1756 measured between bottom surface 1752 and top
surface 1754. In some embodiments, thickness 1756 can range from
about 10 microns to about 50 microns, including subranges. For
example, thickness 1756 can be about 10 microns, about 20 microns,
about 30 microns, about 40 microns, or about 50 microns, or within
a range having any two of these values as endpoints, inclusive of
the endpoints. In some embodiments, thickness 1756 can range from
about 20 microns to about 40 microns. Suitable adhesives for
adhesive layer 1750 include, but are not limited to, polyurethane
adhesives, hot melt adhesives, emulsion polymer adhesives, dry web
adhesives, dry laminating adhesives, or wet laminating adhesives.
Hauthane HD-2001 available from C.L. Hauthaway & Sons
Corporation is an exemplary laminating adhesive suitable for
adhesive layer 1750. Exemplary polyurethane adhesives include, but
are not limited to, L-2183, L-2245, L-2255 from Hauthaway and
IMPRANIL.RTM. DAH, DAA from Covestro. Exemplary dry web adhesives
include, but are not limited to, 9D8D20 from Protechnic. In some
embodiments, layered material 1700 does not include an adhesive
layer 1750.
[0241] Adhesive layer 1750 can have a dry weight, measured in grams
per square meter (g/m.sup.2), ranging from about 10 g/m.sup.2 to
about 50 g/m.sup.2, including subranges. For example, adhesive
layer 1750 can have a dry weight of about 10 g/m.sup.2, about 20
g/m.sup.2, about 30 g/m.sup.2, about 40 g/m.sup.2, or about 50
g/m.sup.2, or within a range having any two of these values as
endpoints, inclusive of the endpoints. In some embodiments,
adhesive layer 1750 can have a dry weight ranging from about 20
g/m.sup.2 to about 40 g/m.sup.2.
[0242] Layered material 1700 can be made by attaching one or more
protein polyurethane alloy layers, and one or more basecoat and/or
top-coat layers described herein, to substrate layer 1710. In some
embodiments, the layer(s) may be subsequently layered over a
surface of a substrate layer. Layer(s) can be attached to either
top surface 1714 and/or bottom surface 1712 of substrate layer
1710. In some embodiments, the layer(s) can be layered over a
sacrificial layer that is removed after layering and before or
after attaching the one or more layers to substrate layer 1710.
Each protein polyurethane alloy layer of a layered material can be
deposited using any suitable coating technique, including, but not
limited to, knife over roll coating, gravure coating, slot die
coating, multi-layer slot die coating, or curtain coating.
Multi-layer slot die coating can allow simultaneous coating of
multiple adjacent layers.
[0243] In some embodiments, a substrate layer 1710 can be coated
with an adhesive layer 1750 and additional layers (e.g., layers
1720, 1730, 1740, 1760, and/or 1770) can be formed over adhesive
layer 1750 in any appropriate order. In such embodiments, the
layers can be formed over adhesive layer 1750 in the same manner as
described below for method 1900 with the layers being formed over
the adhesive layer 1750 rather than a sacrificial layer. In some
embodiments, a blended mixture as described herein can be applied
directly to a surface of a substrate layer 1710, using for example,
a coating or pouring process. In such embodiments, the blended
mixture can penetrate at least a portion of substrate layer 1710.
After application, the blended mixture can be dried to form a
protein polyurethane alloy layer (e.g., layer 1720). In some
embodiments, after drying, the protein polyurethane alloy layer and
the substrate layer 1710 can be heated (e.g., heat pressed) to aid
in attaching the layers together. Before or after drying and/or
before or after attaching the protein polyurethane alloy layer and
substrate layer 1710, other layers (e.g., layers 1730, 1740, 1760,
and/or 1770) can be applied over the protein polyurethane alloy
layer in any appropriate order. In such embodiments, the other
layers can be formed over the protein polyurethane alloy layer in
the same manner as described below for method 1900 with the layers
being formed over the protein polyurethane alloy layer rather than
a sacrificial layer.
[0244] In some embodiments, decorative layers can be applied
between layers of a layered material during manufacturing. For
example, a logo, an artistic pattern, a drawing, or a symbol can be
applied to a first layer before disposing another layer over the
first layer. Decorative layers can be applied using, for example,
screen printing, digital printing, or transfer printing.
[0245] In some embodiments, the layers of a layered material can be
formed over a sacrificial layer and attached to a substrate layer
after formation. FIG. 19 illustrates a method 1900 for making a
layered material 1700 according to some embodiments. FIGS. 20A-20F
illustrate steps of method 1900. Unless stated otherwise, the steps
of method 1900 need not be performed in the order set forth herein.
Additionally, unless specified otherwise, the steps of method 1900
need not be performed sequentially. The steps can be performed
simultaneously. As one example, method 1900 need not include a
solvent removal step after the deposition of each individual
protein polyurethane alloy layer; rather the solvent (for example,
water) from a plurality of protein polyurethane alloy layers can be
removed in a single step. Method 1900 can be used to attach layers
to one or both sides of a substrate layer 1710.
[0246] In step 1902, a top-coat layer 1770 can be disposed over a
top surface 2002 of a sacrificial layer 2000, as illustrated in for
example FIG. 20A. Top-coat layer 1770 can be disposed over
sacrificial layer 2000 using any suitable coating technique, for
example, knife over roll with reverse transfer paper, spraying, or
roller coating. Sacrificial layer 2000 is a layer of material that
does not define a layer of layered material 1700. Rather,
sacrificial layer 2000 is removed during manufacturing of layered
material 1700. Sacrificial layer 2000 can be removed mechanically,
such as by peeling away, or chemically, for example, by dissolving
sacrificial layer 2000. In some embodiments, sacrificial layer 2000
can be a release liner. Suitable materials for sacrificial layer
2000 include but are not limited to grain texture release papers.
Exemplary grain texture release papers include, release papers
available from Sappi paper, for example, Matte Freeport 189,
Freeport 123, or Expresso 904. In some embodiments, method 1900
does not include step 1902. That is, step 1902 is optional. In some
embodiments, top-coat layer 1770 can be applied to a layered
material 1700 after removing sacrificial layer 2000 in step 1918.
In some embodiments, top-coat layer 1770 can be applied to a
layered material 1700 after attaching protein polyurethane alloy
layer(s) to a substrate layer 1710 in step 1920.
[0247] In step 1904, basecoat layer 1760 can be disposed over
sacrificial layer 2000, as illustrated in for example FIG. 20B. In
embodiments including top-coat layer 1770, basecoat layer 1760 can
be disposed over top-coat layer 1770. Basecoat layer 1760 can
disposed over sacrificial layer 2000 using any suitable coating
technique, for example, knife over roll with reverse transfer
paper, spraying, or roller coating. In some embodiments, method
1900 does not include step 1904. Step 1904 is optional. In some
embodiments, basecoat layer 1760 can be applied to a layered
material 1700 after removing sacrificial layer 2000 in step 1918.
In some embodiments, basecoat layer 1760 can be applied to a
layered material 1700 after attaching protein polyurethane alloy
layer(s) to a substrate layer 1710 in step 1920.
[0248] In step 1906, one or more polyurethanes dispersed or
dissolved in an aqueous solution can be blended with one or more
proteins to form a blended mixture in the aqueous solution. In some
embodiments, the one or more polyurethanes can be dispersed or
dissolved in an aqueous solution before blending with protein(s).
In some embodiments, the one or more polyurethanes can become
dispersed or dissolved in an aqueous solution during blending with
protein(s). In some embodiments, the one or more polyurethanes and
the one or more proteins can be blended in a suitable vessel until
a homogenous blend is formed. Suitable blending equipment includes,
but is not limited to, a blender, a stand mixer, an in-line mixer,
or a high shear mixer.
[0249] In some embodiments, protein(s) can be dispersed or
dissolved in an aqueous solution before blending with polyurethane
in step 1906. Suitable aqueous solutions include, but are not
limited to, water, an aqueous alkali solution, an aqueous acid
solution, an aqueous solution including an organic solvent, a urea
solution, and mixtures thereof. In some embodiments, the aqueous
alkali solution can be a basic solution such as a sodium hydroxide,
ammonia or ammonium hydroxide solution. In some embodiments,
examples of an acidic aqueous solution can be an acetic acid or
hydrochloric acid (HCl) solutions. Suitable organic solvents
include, but are not limited to, ethanol, isopropanol, acetone,
ethyl acetate, isopropyl acetate, glycerol, and the like. In some
embodiments, the protein concentration in the aqueous protein
mixture can range from about 10 g/L to about 300 g/L, including
subranges. For example, the protein concentration in the aqueous
protein mixture can be about 10 g/L, about 20 g/L, about 30 g/L,
about 40 g/L, about 50 g/L, about 60 g/L, about 70 g/L, about 80
g/L, about 90 g/L, about 100 g/L, about 150 g/L, about 200 g/L,
about 250 g/L, or about 300 g/L, or within a range having any two
of these values as endpoints, inclusive of the endpoints. In some
embodiments, the protein concentration in the aqueous protein
mixture can range from about 10 g/L to about 300 g/L, about 20 g/L
to about 250 g/L, about 30 g/L to about 200 g/L, about 40 g/L to
about 150 g/L, about 50 g/L to about 100 g/L, about 60 g/L to about
90 g/L, or about 70 g/L to about 80 g/L.
[0250] The amount of protein in a protein/polyurethane blend can
range from about 5 wt % to about 60%, based on the weight of
protein and polyurethane, including subranges. For example, the
amount of protein in a blend can be about 5 wt %, about 10 wt %,
about 15 wt %, about 20 wt %, about 25 wt %, about 30 wt %, about
35 wt %, about 40 wt %, about 45 wt %, about 50 wt %, about 55 wt
%, or about 60 wt %, or within a range having any two of these
values as endpoints. In some embodiments, the amount of protein in
a blend can be about 10 wt % to about 55 wt %, about 15 wt % to
about 50 wt %, about 20 wt % to about 45 wt %, about 25 wt % to
about 40 wt %, or about 30 wt % to about 35 wt %. In some
embodiments, the amount of protein in the protein/polyurethane
blend can range from 20 wt % to 40 wt %.
[0251] The amount of polyurethane(s) in a protein/polyurethane
blend can range from about 10 wt % to about 85 wt %, based on the
weight of protein and polyurethane, including subranges. For
example, the amount of polyurethane(s) in blend can be about 10 wt
%, about 15 wt %, about 20 wt %, about 25 wt %, about 30 wt %,
about 35 wt %, about 40 wt %, about 45 wt %, about 50 wt %, about
55 wt %, about 60 wt %, about 65 wt %, about 70 wt %, about 75 wt
%, about 80 wt %, or about 85 wt %, or within a range having any
two of these values as endpoints, inclusive of the endpoints. In
some embodiments, the amount of the polyurethane(s) in a blend can
range from about 20 wt % to about 75 wt %, about 30 wt % to about
65 wt %, or about 40 wt % to about 55 wt %.
[0252] In some embodiments, the blending temperature can range from
about room temperature (18.degree. C.) to about 100.degree. C.,
including subranges. For example, the blend temperature can be
about 18.degree. C., about 30.degree. C., about 40.degree. C.,
about 50.degree. C., about 60.degree. C., about 70.degree. C.,
about 80.degree. C., about 90.degree. C., or about 100.degree. C.,
or within a range having any two of these values as endpoints,
inclusive of the endpoints. In some embodiments, the blend
temperature can range from about 18.degree. C. to about 90.degree.
C., about 18.degree. C. to about 80.degree. C., about 18.degree. C.
to about 70.degree. C., about 18.degree. C. to about 60.degree. C.,
about 18.degree. C. to about 50.degree. C., about 18.degree. C. to
about 40.degree. C., or about 18.degree. C. to about 30.degree.
C.
[0253] In some embodiments, the blending time for step 1906 can
range from about 15 minutes to about 3 hours, including subranges.
For example, the blending time can be about 30 minutes, about 1
hour, about 90 minutes, about 2 hours, about 150 minutes, or about
3 hours, or within a range having any two of these values as
endpoints, inclusive of the endpoints. In some embodiments, the
blending time can range from about 15 minutes to about 150 minutes,
about 15 minutes to about 2 hours, about 15 minutes to about 90
minutes, or about 15 minutes to about 1 hour. In some embodiments,
the blending speed for step 1906 can range from about 150 rpm to
about 250 rpm, including subranges. For example, the blending speed
can be about 150 rpm, about 175 rpm, about 200 rpm, about 225 rpm,
or about 250 rpm. In some embodiments, the blending speed can range
from about 150 rpm to about 225 rpm, about 150 rpm to about 200
rpm, or about 150 rpm to about 225 rpm. The blending speed can
depend on the size of a blending device (e.g., size of an impeller)
and/or the size of the vessel in which the components are
blended.
[0254] In some embodiments, one or more additives can be added to
the blend in step 1906. The additive(s) can influence the final
properties of a protein polyurethane alloy layer, and therefore the
final properties of a layered material 1700. For example, the
additive(s) added can impact one or more of the following material
properties: stiffness, elasticity, cohesive strength, tear
strength, fire retardancy, chemical stability, or wet stability.
Suitable additives include, but are not limited to, cross-linkers,
fillers, dyes, pigments, plasticizers, waxes, rheological
modifiers, flame retardants, antimicrobial agents, antifungal
agents, antioxidants, UV stabilizers, mechanical foaming agents,
chemical foaming agents, foam stabilizers, and the like. Suitable
dyes include, but are not limited to fiber reactive dyes or natural
dyes. Suitable cross-linkers include, but are not limited to,
epoxy-based cross-linkers, (for example, poly(ethylene glycol)
diglycidyl ether (PEGDE) available from Sigma Aldridge),
isocyanate-based cross-linkers (for example, XTAN.RTM. available
from Lanxess), and carbodiimide-based cross-linkers. Suitable
foaming agents include, HeiQ Chemtex 2216-T (a stabilized blend of
nonionic and anionic surfactants), HeiQ Chemtex 2241-A (a modified
HEUR (hydrophobically-modified ethylene oxide urethane) thickener),
HeiQ Chemtex 2243 (a non-ionic silicone dispersion), or HeiQ
Chemtex 2317 (a stabilized blend of nonionic and anionic
surfactants) foam stabilizers available from HeiQ Chemtex. Suitable
antimicrobial/antifungal agents include Ultra-Fresh DW-56, or other
antimicrobial/antifungal agents used in the leather industry.
Suitable flame retardants include CETAFLAM.RTM. DB9
(organophosphorous compounds containing C--PO(OH).sub.2 or
C--PO(OR).sub.2 groups with the carbon chain containing polymers),
CETAFLAM.RTM. PD3300 (organophosphorous compounds containing
C--PO(OH).sub.2 or C--PO(OR).sub.2 groups with the carbon chain
containing polymers), or other flame retardants used for coated
textiles. Suitable fillers include, but are not limited to,
thermoplastic microspheres, for example, EXPANCEL.RTM.
Microspheres. Suitable rheological modifiers include, but are not
limited to, alkali swellable rheological modifiers,
hydrophobically-modified ethylene oxide-based urethane (HEUR)
rheological modifiers, and volume exclusion thickeners. Exemplary
alkali swellable rheological modifiers include but are not limited
to, ACRYSOL.TM. DR-106, ACRYSOL.TM. ASE-60 from Dow Chemicals,
TEXICRYL.RTM. 13-3131, and TEXICRYL.RTM. 13-308 from Scott-Bader.
Exemplary HEUR modifiers include, but are not limited to, RM-4410
from Stahl and Chemtex 2241-A from HeiQ. Exemplary volume exclusion
thickeners include, but are not limited to, WALOCEL.TM. XM 20000 PV
from Dow Chemicals and Methyl-Hydroxyethyl Cellulose from
Sigma-Aldrich.
[0255] In some embodiments, a blend can include one or more
coloring agents. In some embodiments, the coloring agent can be a
dye, for example a fiber reactive dye, a direct dye, or a natural
dye. Exemplary dyes, include but are not limited to, Azo structure
acid dyes, metal complex structure acid dyes, anthraquinone
structure acid dyes, and azo/diazo direct dyes. In some
embodiments, the coloring agent can be pigment, for example a lake
pigment. In some embodiments, a blend can include a coloring agent
content of about 2 wt % or less. For example, a blend can include
about 0.1 wt %, about 0.5 wt %, about 1 wt %, about 1.5 wt %, or
about 2 wt % coloring agent. In some embodiments, a blend can
include about 0.1 wt % to about 2 wt %, about 0.5 wt % to about 1.5
wt %, or about 0.1 wt % to about 1 wt % coloring agent. In some
embodiments, a blend can be free or substantially free of a
coloring agent. In such embodiments, a protein polyurethane alloy
layer created from the blend can be free or substantially free of a
coloring agent.
[0256] In step 1908, a layer of the blended mixture is disposed
over top surface 2002 of sacrificial layer 2000. The blended
mixture can be coated over top surface 2002 of sacrificial layer
2000. In embodiments not including steps 1902 and 1904, the blended
mixture can be coated directly on top surface 2002 of sacrificial
layer 2000. In embodiments including step 1904, the blended mixture
can be coated directly on a surface of basecoat layer 1760. In
embodiments including step 1902 but not step 1904, the blended
mixture can be coated directly on a surface of top-coat layer 1770.
In some embodiments, the blended mixture can be formed into a sheet
by coating it on a surface to a desired thickness. Coating can
include pouring, extruding, casting, and the like. In some
embodiments, the sheet can be spread to a desired thickness using,
for example, a blade, a knife, a roller, a knife over roll, curtain
coating, and slot die coating.
[0257] In some embodiments, the temperature of the blended mixture
during coating can be about 40.degree. C. or higher. For example,
the temperature of the blended mixture can range from about
40.degree. C. to about 100.degree. C., including subranges. For
example, the temperature can be about 40.degree. C., about
50.degree. C., about 60.degree. C., about 70.degree. C., about
80.degree. C., about 90.degree. C., or about 100.degree. C., or
within a range having any two of these values as endpoints,
inclusive of the endpoints. In some embodiments, the temperature of
the blended mixture during coating can range from about 40.degree.
C. to about 90.degree. C., about 40.degree. C. to about 80.degree.
C., about 40.degree. C. to about 70.degree. C., about 40.degree. C.
to about 60.degree. C., or about 40.degree. C. to about 50.degree.
C. Coating at a temperature below about 40.degree. C. can result in
the blended mixture being too viscous and can make it difficult to
form a layer of uniform thickness.
[0258] In step 1910, solvent (for example, water) can be removed
from the coated blended mixture to form protein polyurethane alloy
layer 1720, as illustrated in for example, FIG. 20C. Suitable
solvent removal methods include, but are not limited to tunnel
drying, vacuum drying, oven drying with hot air, humidity chamber
drying, flotation drying with hot air, and ovens with a combination
of medium range IR (infrared) for preheating and then hot air for
subsequent drying.
[0259] Suitable solvent removal temperatures for step 1910 can
range from about room temperature (18.degree. C.) to about
100.degree. C., including subranges. For example, solvent may be
removed at a temperature of about 18.degree. C., about 35.degree.
C., about 50.degree. C., about 60.degree. C., about 70 .degree. C.,
about 80.degree. C., about 90.degree. C., or about 100.degree. C.,
or within a range having any two of these values as endpoints,
inclusive of the endpoints. In some embodiments, solvent may be
removed at a temperature ranging from about 18.degree. C. to about
35.degree. C., about 18.degree. C. to about 50.degree. C., about
18.degree. C. to about 60.degree. C., about 18.degree. C. to about
70.degree. C., about 18.degree. C. to about 80.degree. C., about
18.degree. C. to about 90.degree. C., or about 18.degree. C. to
about 100.degree. C. Suitable humidity values for solvent removal
in step 1910 include a humidity in a range from 0% RH (relative
humidity) to about 65% RH, including subranges. For example, the
humidity can be about 10% RH, about 20% RH, about 40% RH, about 50%
RH, or about 65% RH, or within a range having any two of these
values as endpoints, inclusive of the endpoints. In some
embodiments, the humidity can be 0% RH to about 50% RH, 0% RH to
about 40% RH, 0% RH to about 20% RH, or 0% RH to about 10% RH. The
solvent removal temperature and/or humidity can affect the final
properties of a protein polyurethane alloy layer, and therefore a
layered material. The solvent removal temperature and/or humidity
in step 1910 can impact one or more of the following material
properties: stiffness, elasticity, cohesive strength, tear
strength, fire retardancy, chemical stability, and wet stability.
For example, relatively high humidity and relatively low
temperature can result in a material that is softer and more
elastic. Conversely, relatively low humidity and relatively high
temperature can result in a material that is harder and less
elastic.
[0260] In some embodiments, steps 1906-1910 can be repeated a
plurality of times to form a plurality of protein polyurethane
alloy layers 1720 over sacrificial layer 2000. In some embodiments,
steps 1906-1910 can be repeated sequentially to form a plurality of
protein polyurethane alloy layers 1720 over sacrificial layer 2000.
In some embodiments, steps 1906-1910 can be repeated after steps
1912-1916 to form one or more protein polyurethane alloy layers
1720 over one or more foamed protein polyurethane alloy layers
1730/1740. In some embodiments, method 1900 may not include steps
1906-1910.
[0261] In step 1912, one or more polyurethanes dispersed or
dissolved in an aqueous solution can be blended with protein(s) and
foamed to form a foamed blended mixture in the aqueous solution. In
some embodiments, the one or more polyurethanes can be dispersed or
dissolved in an aqueous solution before blending with protein(s)
and foaming. In some embodiments, the one or more polyurethanes can
become dispersed or dissolved in an aqueous solution during
blending with protein(s) and foaming. In some embodiments, the one
or more polyurethanes and the one or more proteins can be blended
in a suitable vessel until a homogenous blend is formed. Suitable
blending equipment includes, but is not limited to, a blender, a
stand mixer, an in-line mixer, or a high shear mixer. The blend may
be foamed using, for example, a mechanical foaming process or a
chemical foaming process. Exemplary mechanical foaming equipment
includes a Hansa Mixer or a GEMATA.RTM. foamer. Blending and
foaming can be performed separately or concurrently.
[0262] Suitable polyurethane(s) for blending and foaming in step
1912 are those discussed herein for protein polyurethane alloy
layers. In some embodiments, one or more foaming agents and/or foam
stabilizers may be added to the blend in step 1912. Suitable
foaming agents and foam stabilizers include those discussed herein
for protein polyurethane alloy layers 1730/1740.
[0263] In some embodiments, a blend can include a foaming agent or
a foam stabilizer content of about 10 wt % or less. For example, a
blend can include about 0.1 wt %, about 1 wt %, about 2.5 wt %,
about 5 wt %, about 7.5 wt %, or about 10 wt % foaming agent or
foam stabilizer. In some embodiments, a blend can include about 0.1
wt % to about 10 wt %, about 1 wt % to about 7.5 wt %, about 2.5 wt
% to about 5 wt %, about 0.1 wt % to about 5 wt %, or about 0.1 wt
% to about 2.5 wt % foaming agent or foam stabilizer. In some
embodiments, a blend can be substantially free or free of a foaming
agent and/or a foam stabilizer. In such embodiments, a protein
polyurethane alloy layer created from the blend can be
substantially free or free of a foaming agent and/or a foam
stabilizer.
[0264] Foaming in step 1912 can be used to impart a desired density
for a foamed protein polyurethane alloy layer. In some embodiments,
a foamed blended mixture can have a liquid density, before solvent
is removed in step 1916, ranging from about 300 g/L to about 900
g/L, including subranges. For example, a foamed blended mixture
formed in step 1912 can have a liquid density of about 300 g/L,
about 400 g/L, about 500 g/L, about 600 g/L, about 700 g/L, about
800 g/L, or about 900 g/L, or within a range having any two of
these values as endpoints. In some embodiments, the foamed blended
mixture can have a liquid density ranging from about 300 g/L to
about 800 g/L, about 300 g/L to about 700 g/L, about 400 g/L to
about 600 g/L, about 300 g/L to about 500 g/L, or about 300 g/L to
about 600 g/L. In some embodiments, a blended mixture formed in
step 1906 can have a liquid density, before the solvent is removed
from the blended mixture in step 1910 that is greater than the
liquid density of the foamed blended mixture formed in step 1912
before solvent is removed in step 1916.
[0265] In some embodiments, protein(s) can be dispersed or
dissolved in an aqueous solution before blending with polyurethane
and foaming in step 1912. Suitable aqueous solutions include those
discussed above for step 1906. The protein concentration in the
aqueous solution can be any value or range discussed above for step
1906. The amount of protein in a protein/polyurethane blend for
step 1912 can be any value or range discussed above for step 1906.
The blending temperature for step 1912 can be any temperature or
temperature range discussed above for step 1906. The blending time
for step 1912 can be any time or time range discussed above for
step 1906. The blending speed for step 1912 can be any speed or
speed range discussed above for step 1906. In some embodiments, one
or more additives can be added to the blend in step 1912. The
additive(s) added in step 1912 can be any of the additives
discussed above for step 1906.
[0266] In step 1914, a layer of the foamed blended mixture is
disposed over sacrificial layer 2000. In some embodiments, a layer
of the foamed blended mixture is disposed over a surface of a
protein polyurethane alloy layer 1720. In some embodiments, the
blended and foamed mixture can be coated directly on a surface of a
protein polyurethane alloy layer 1720. In some embodiments, the
foamed blended mixture can be formed into a sheet by coating it on
a surface to a desired thickness. Coating can include pouring,
extruding, casting, and the like. In some embodiments, the sheet
can be spread to a desired thickness using, for example, a blade, a
knife, a roller, a knife over roll, curtain coating, and slot die
coating.
[0267] In step 1916, solvent (for example, water) can be removed
from the coated, foamed blended mixture to form a foamed protein
polyurethane alloy layer 1730, as illustrated in for example, FIG.
20D. Suitable solvent removal methods include, but are not limited
to tunnel drying, vacuum drying, oven drying with hot air, humidity
chamber drying, flotation drying with hot air, and ovens with a
combination of medium range IR for preheating and then hot air for
subsequent drying. Suitable solvent removal temperatures for step
1916 can any of the temperature or temperature ranges discussed
above for step 1910. Humidity values for step 1916 can be any of
the humidity values or humidity ranges discussed above for step
1910
[0268] In some embodiments, steps 1912-1916 can be repeated a
plurality of times to form a plurality of foamed protein
polyurethane alloy layers over sacrificial layer 2000, for example,
foamed protein polyurethane alloy layers 1730 and 1740. In such
embodiments, the foamed blended mixtures formed in separate steps
1912 can have different liquid densities. For example, the liquid
density for one foamed blended mixture can be 10 g/L to 300 g/L
more or less than the liquid density for another foamed blended
mixture. For example, in some embodiments, a first blended mixture
can have a liquid density ranging from about 300 g/L to about 500
g/L and a second blended mixture can have a liquid density ranging
from about 600 g/L to about 700 g/L. As another example, a first
blended mixture can have a liquid density ranging from about 300
g/L to about 400 g/L and a second blended mixture can have a liquid
density ranging from about 500 g/L to about 700 g/L.
[0269] In some embodiments, steps 1912-1916 can be repeated
sequentially to form a plurality of foamed protein polyurethane
alloy layers over sacrificial layer 2000. In some embodiments, a
foamed and blended mixture formed in step 1912 can be used to form
multiple foamed protein polyurethane alloy layers in steps
1914-1916. In some embodiments, steps 1912-1916 can be performed
before performing a set of steps 1906-1910 to form one or more
foamed protein polyurethane alloy layers between a protein
polyurethane alloy layer 1720 and sacrificial layer 2000. In some
embodiments, method 1900 may not include steps 1912-1916.
[0270] In step 1918, sacrificial layer 2000 is removed from the
layer(s) formed in steps 1902-1916, as illustrated in for example
FIG. 20E. Sacrificial layer 2000 can be removed by a mechanical
process or a chemical process. For example, sacrificial layer 2000
can be removed by peeling sacrificial layer 2000 away from the
other layers. As another example, sacrificial layer 2000 can be
removed by dissolving sacrificial layer 2000. In some embodiments,
sacrificial layer 2000 can be removed in step 1918 before attaching
the layer(s) formed in steps 1902-1916 to a substrate layer 1710 in
step 1920. In some embodiments, sacrificial layer 2000 can be
removed after step 1920.
[0271] In step 1920, the layer(s) formed in steps 1902-1916 are
attached to a substrate layer 1710, as illustrated in for example
FIG. 20F. In step 1920, protein polyurethane alloy layer 1720, and
any other protein polyurethane alloy layers formed in steps
1906-1916 are attached to substrate layer 1710. In some
embodiments, attaching one or more protein polyurethane alloy
layers (e.g., protein polyurethane alloy layer 1720) to substrate
layer 1710 in step 1920 includes a heat pressing process. In such
embodiments, protein polyurethane alloy layer (e.g., protein
polyurethane alloy layer 1720) can be in direct contact with
substrate layer 1710. Also, in such embodiments, a protein
polyurethane alloy layer can partially melt into substrate layer
1710, and upon cooling the two layers are firmly attached. In some
embodiments, attaching one or more protein polyurethane alloy
layers (e.g., protein polyurethane alloy layer 1720) to substrate
layer 1710 in step 1920 includes a lamination process. In such
embodiments, lamination can be accomplished with an adhesive layer
1750. In such embodiments, substrate layer 1710 and/or a protein
polyurethane alloy layer can be coated with an adhesive by known
techniques such as slot die casting, kiss coating, a drawdown
technique, or reverse transfer coating. In some embodiments, the
lamination process can include passing substrate layer 1710 and the
other layer(s) through rollers under heat.
[0272] In some embodiments, step 1920 can be omitted from method
1900. In such embodiments, the layer(s) formed in steps 1902-1916
define a protein polyurethane alloy layer or a layered material
without a substrate layer 1710.
[0273] In some embodiments, layered materials described herein can
have a tear strength that is at least about 1% greater than that of
a natural leather of the same thickness. For example, the layered
material can have a tear strength that is about 1%, about 2%, about
3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%,
about 10%, about 15%, about 20%, about 25%, about 30%, about 35%,
about 40%, about 45%, about 50%, about 100%, about 150%, or about
200% greater than that of natural leather of the same thickness. In
some embodiments, the layered material can have a tear strength in
the range of about 20 N to about 300 N, including subranges. For
example, the tear strength of the layered material can be about 20
N, about 30 N, about 40 N, about 50 N, about 60 N, about 70 N,
about 80 N, about 90 N, about 100 N, about 125 N, about 150 N,
about 175 N, about 200 N, about 225 N, about 250 N, about 275 N, or
about 300 N, or within a range having any two of these values as
endpoints, inclusive of the endpoints. In some embodiments, the
tear strength can range from about 30 N to about 275 N, about 40 N
to about 250 N, about 50 N to about 225 N, about 60 N to about 200
N, or about 75 N to about 175 N, about 80 N to about 150 N, about
90 N to about 125 N, or about 100 N to about 125 N.
[0274] In some embodiments, a protein polyurethane alloy layer
described herein can have a tear strength in the range of about 2 N
to about 30 N, including subranges. For example, the tear strength
of the protein polyurethane alloy layer can be about 2 N, about 4
N, about 5 N, about 10 N, about 15 N, about 20 N, about 25 N, or
about 30 N, or within a range having any two of these values as
endpoints, inclusive of the endpoints. In some embodiments, the
tear strength can range from about 4 N to about 25 N, about 5 N to
about 20 N, or about 10 N to about 15 N.
[0275] Tear strength, or tear resistance, is a measure of how well
a material can withstand the effects of tearing. Tear resistance
can be measured by a variety of methods, for example the method
provided by ASTM D 412 or the method provided by ISO 3377 (also
called the "Bauman tear"). The method provided by ASTM D 624 can
also be used to measure the resistance to the formation of a tear
and the resistance to the expansion of a tear. Regardless of the
method used, first, a cut is made in the material sample tested to
induce a tear. Then, the sample is held between two grips and a
uniform pulling force is applied until sample tears in two. Tear
resistance is then calculated by dividing the force applied by the
thickness of the material. Unless specified otherwise, a tear
strength value reported herein is measured by ISO 3377.
[0276] In some embodiments, the layered materials described herein
can have a tensile strength in the range of about 1 kPa
(kilopascal) to about 100 MPa (megapascals), including subranges.
For example, the layered material can have a tensile strength of
about 1 kPa, about 50 kPa, about 100 kPa, about 200 kPa, about 300
kPa, about 400 kPa, about 500 kPa, about 600 kPa, about 700 kPa,
about 800 kPa, about 900 kPa, about 1 MPa, about 5 MPa, about 10
MPa, about 20 MPa, about 30 MPa, about 40 MPa, about 50 MPa, about
60 MPa, about 70 MPa, about 80 MPa, about 90 MPa, or about 100 MPa,
or within a range having any two of these values as endpoints,
inclusive of the endpoints. In some embodiments, the tensile
strength can range from about 50 kPa to about 90 MPa, about 100 kPa
to about 80 MPa, about 200 kPa to about 70 MPa, about 300 kPa to
about 60 MPa, about 400 kPa to about 50 MPa, about 500 kPa to about
40 MPa, about 600 kPa to about 30 MPa, about 700 kPa to about 20
MPa, about 800 kPa to about 10 MPa, or about 1MPa to about 5
MPa.
[0277] Softness, also referred to as "hand feel" of a material can
be determined by ISO 17235. In some embodiments, an exterior
surface of a layered material described herein can have a softness
ranging from about 2 mm to about 12 mm, including subranges. For
example, an exterior surface of a layered material can have a
softness of about 2 mm, about 3 mm, about 4 mm, about 5 mm, about 6
mm, about 7 mm, about 8 mm, about 9 mm, about 10 mm, about 11 mm,
or about 12 mm, or within a range having any two of these values as
endpoints, inclusive of the endpoints. In some embodiments, the
softness can be about 3 mm to about 11 mm, about 4 mm to about 10
mm, about 5 mm to about 9 mm, about 6 mm to about 8 mm, or about 6
mm to about 7 mm. Unless specified otherwise, a softness value
disclosed herein is determined by ISO 17235.
[0278] Flexibility, or strain, of a material can be determined by
measuring its elongation at failure when a tensile force is
applied, for example using the equation: .DELTA.T/L , where
.DELTA.L is the change in length of the material after the tensile
force is applied, and L is the original length of the material.
Flexibility can also be measured according to the method provided
by ASTM D 412. In some embodiments, the layered materials described
herein can have a flexibility in the range of about 100% to about
400%, including subranges. For example, the layered materials can
have a flexibility of about 100%, about 200%, about 300%, or about
400%, or within a range having any two of these values as
endpoints, inclusive of the endpoints. In some embodiments, the
flexibility can be about 100% to about 200%, about 100% to about
300%, about 200% to about 300%, or about 200% to about 400%. Unless
specified otherwise, a flexibility value disclosed herein is
measured by ASTM D 412. In some embodiments, a protein polyurethane
alloy layer described herein can have flexibility value or range as
described above for a layered material.
[0279] In some embodiments, a layered material as described herein
can have a permanent set in a hysteresis experiment of about 8% or
less. In some embodiments, a layered material can have a permanent
set of about 1%, about 2%, about 3%, about 4%, about 5%, about 6%,
about 7%, or about 8%, or within a range having any two of these
values as endpoints. In some embodiments, a layered material can
have a permanent set of about 1% to about 8%, about 2% to about 7%,
about 3% to about 6%, or about 4% to about 5%.
[0280] Unless specified otherwise, a permanent set value is
measured by the following method. A dog-bone-shaped tensile
specimen of a material is cut and the original length of the sample
is measured. The samples are cut to have a dog-bone shape with
about 110 mm length and 10 mm width (75-100 mm gauge length). Then,
the sample is stretched along its length using an INSTRON.RTM.
machine to 15% strain and returned to 0% strain, both at a constant
rate of three millimeters per second. This is repeated five times.
Then, the distance between the original sample length and the
length of the sample at which the load goes to zero on the last
return cycle is measured. The percent difference between the length
measured after repeatedly straining the material and the original
length is the permanent set %. For purposes of calculating a
permanent set value, three separate samples of a material are
evaluated, and the average permanent set value is reported as the
permanent set value for the material.
[0281] In some embodiments, layered materials described herein can
have a moisture vapor transmission rate (MVTR) of about 75
g/m.sup.2/hr or more. In some embodiments, layered materials
described herein can have a MVTR ranging from about 75 g/m.sup.2/hr
to about 200 g/m.sup.2/hr, including subranges. For example, the
layered material can have a MVTR of about 80 g/m.sup.2/hr to about
190 g/m.sup.2/hr, about 90 g/m.sup.2/hr to about 180 g/m.sup.2/hr,
about 100 g/m.sup.2/hr to about 170 g/m.sup.2/hr, about 110
g/m.sup.2/hr to about 160 g/m.sup.2/hr, about 120 g/m.sup.2/hr to
about 150 g/m.sup.2/hr, or about 130 g/m.sup.2/hr to about 140
g/m.sup.2/hr. Unless specified otherwise, a MVTR value disclosed
herein is measured using ASTM E96 ("Standard Test Methods for Water
Vapor Transmission of Materials")--Procedure B, Water Method, at
about 74.3.degree. F., at about 50% relative humidity, and with a
3/4 inch air gap.
[0282] Layered materials having a moisture vapor transmission rate
as reported herein can be suitable for use in a variety of
applications where breathability of the material is a desirable
property. Exemplary applications where breathability can be
desirable include, but are not limited to, footwear, apparel, and
upholstery. Layered materials as described herein can have a
significantly higher water vapor transmission rate compared to a
layered polymeric material having the same number of layers with
the same thicknesses and made of the same polymeric material(s),
but without protein blended in the polymeric material(s).
[0283] In some embodiments, layered materials described herein can
have a color fastness of class 4 or higher when measured according
to ISO 11640 ("Leather--Tests for color fastness--fastness to
cycles of to-and-fro rubbing") wet-rub fastness test. In some
embodiments, layered materials described herein can have a color
fastness of class 4, class 4.5, or class 5 when measured according
to ISO 11640's wet-rub fastness test. A color fastness of class 4
or higher can provide layered materials described herein with
desirable wear resistance for a variety of applications.
[0284] Layered materials described herein can achieve a color
fastness of class 4 or higher without the inclusion of a pigment in
the materials. This is a unique characteristic compared to a
layered polyurethane material made of the same polyurethane(s)
without protein(s) blended in the polyurethane(s). Protein within
layered materials described herein can adhere well to a dye used to
color the material. To achieve a high color fastness, polyurethane
materials are usually colored using a pigment because dyes do not
generally adhere to a polyurethane well. Poor adherence between a
dye and a polyurethane leads to a relatively low color fastness.
Dyed layered materials described herein can have improved depth of
color and other aesthetic features not achievable with a
polyurethane colored using a pigment.
[0285] In some embodiments, a layered material described herein, or
an individual layer of a layered material described herein, can be
subjected to the same, or similar finishing treatments as those
used to treat natural leather. In some embodiments, a layered
material described herein can be tumbled or staked to tailor
properties of the material, such as the feel of the material. In
such embodiments, traditional textile tumbling and staking methods
can be used.
[0286] In some embodiments, a layered material, or an individual
layer of a layered material, can have a rough exterior surface. For
example, top surface 1724 of protein polyurethane alloy layer 1720
can have a rough surface, top surface 1774 of top-coat layer 1770
can have a rough surface, top surface 1764 of basecoat layer 1760
can have a rough surface, top surface 1734 of protein polyurethane
alloy layer 1730 can have a rough surface, or top surface 1744 of
protein polyurethane alloy layer 1740 can have a rough surface. A
rough exterior surface can create a surface texture similar in
appearance and feel to that of a naturel leather (e.g., the grain
of pebbled natural leather). In some embodiments, top surface 2002
of sacrificial layer 2000 can have a rough surface that is
transferred onto the surface of a layer disposed directly on top
surface 2002 during method 1900.
[0287] A rough surface has a surface area per square inch of at
least about 1% greater than 1 in.sup.2. In other words, in some
embodiments, a one square inch sample of layered material 1700,
including a layer having rough exterior surface, can have a surface
area that is at least about 1% greater than a one square inch
sample of a material having a perfectly smooth surface. In some
embodiments, a rough exterior surface can have a surface area per
square inch of at least about 1% greater than 1 in.sup.2, about 10%
greater than 1 in.sup.2, about 20% greater than 1 in.sup.2, about
30% greater than 1 in.sup.2, about 40% greater than 1 in.sup.2,
about 50% greater than 1 in.sup.2, about 60% greater than 1
in.sup.2, about 70% greater than 1 in.sup.2, about 80% greater than
1 in.sup.2, about 90% greater than 1 in.sup.2, about 100% greater
than 1 in.sup.2, about 150% greater than 1 in.sup.2, about 200%
greater than 1 in.sup.2, about 250% greater than 1 in.sup.2, about
300% greater than 1 in.sup.2, about 350% greater than 1 in.sup.2,
about 400% greater than 1 in.sup.2, about 450% greater than 1
in.sup.2, or about 500% greater than 1 in.sup.2, or within a range
having any two of these values as endpoints, inclusive of the
endpoints. In some embodiments, a rough surface can have a surface
area per square inch of about 1% greater than 1 in.sup.2 to about
500% greater than 1 in.sup.2, about 10% greater than 1 in.sup.2 to
about 450% greater than 1 in.sup.2, about 20% greater than 1
in.sup.2 to about 400% greater than 1 in.sup.2, about 30% greater
than 1 in.sup.2 to about 350% greater than 1 in.sup.2, about 40%
greater than 1 in.sup.2 to about 300% greater than 1 in.sup.2,
about 50% greater than 1 in.sup.2 to about 250% greater than 1
in.sup.2, about 60% greater than 1 in.sup.2 to about 200% greater
than 1 in.sup.2, about 70% greater than 1 in.sup.2 to about 150%
greater than 1 in.sup.2, or about 80% greater than 1 in.sup.2 to
about 100% greater than 1 in.sup.2. Unless specified otherwise, a
surface area of material disclosed herein is measured using
profilometry. For non-transparent materials, optical profilometry
is used. In some embodiments, a layered material, or an individual
layer of a layered material, can have a smooth exterior surface. A
smooth surface has a surface area per square inch of less than 1%
greater than 1 in.sup.2. For example, a smooth surface can have a
surface area per square inch of 1 in.sup.2 to less than 1.01
in.sup.2. In some embodiments, top surface 2002 of sacrificial
layer 2000 can have a smooth surface that is transferred onto the
surface of a layer disposed directly on top surface 2002 during
method 1900.
[0288] In some embodiments, a layered material, or an individual
layer of a layered material, can have a textured exterior surface.
In some embodiments, top surface 2002 of sacrificial layer 2000 can
have a textured surface that is transferred onto the surface of a
layer disposed directly on top surface 2002 during method 1900. In
some embodiments, a textured exterior surface can a surface area
per square inch, or surface area per square inch range, as
discussed above for a rough surface.
[0289] In some embodiments, the texture can be a macro-scale
texture, for example, any of the many textures used on Sappi/Warren
Release Papers that are commercially available under the trademark
ULTRACAST.RTM. or tradename Classic, manufactured by S.D. Warren
Company d/b/a Sappi North America. An example of a macro-scale
texture is a replicate of a natural leather grain with feature
depths of about 50 to about 300 microns. Any other desired
macro-scale texture may also be used. In some embodiments, a
macro-scale texture can be a "leather grain texture." As used
herein, the term "leather grain texture" is a texture that mimics
the look and feel of natural leather. Exemplary "leather grain
textures" include but are not limited to, Sappi Matte Freeport 189,
Sappi Freeport 123, or Sappi Expresso 904.
[0290] In some embodiments, the texture can be a micro-scale
texture. In some embodiments, the texture can be a micro-scale
texture with surface features having a feature size of less than 50
microns, for example 1000 nanometers to less than 50 microns. An
example of a micro-scale texture is referred to in the art as
"Sharklet." Sharklet textures can be applied to provide the
products with a surface that is structured to impede bacterial
growth. The micro-scale texture of the surface replicates sharkskin
denticles, which are arranged in a diamond pattern with millions of
tiny ribs. Sharklet materials are discussed, for example, in U.S.
Pat. Nos. 7,650,848 and 8,997,672, the disclosures of which are
incorporated herein by reference.
[0291] In some embodiments, the texture can be a nanoscale texture
with surface features having a feature size of less than 1000
nanometers, for example 10 nanometers to less than 1000 nanometers.
One example of a nanoscale texture is a diffraction grating that
has a series of raised ridges about 400 nanometers wide, spaced
approximately 800 nanometers apart, with a depth of approximately
100 nanometers.
[0292] The embodiments discussed herein will be further clarified
in the following examples. It should be understood that these
examples are not limiting to the embodiments described above.
EXAMPLE 1
[0293] A sample was prepared by mixing 5.5 g of a waterborne
polyurethane dispersion L3360 from Hauthaway, with 10 mL of
de-ionized water and stirring at 1000 rpm (rotations per minute)
for 30 minutes at 50.degree. C. The solution was then pipetted into
a Teflon evaporating dish with a diameter of 10 cm. The dish was
dried in an oven at 45.degree. C. overnight. After drying, the
dried sample was conditioned at standard reference atmosphere
(23.degree. C., 50% humidity) for 24 hours, resulting in a
polyurethane film.
[0294] The film was tested using a DMA-850 from TA Instruments. A 1
cm.times.2.5 cm strip was cut from each film using a metal die. The
cut film samples were loaded into the film and fiber tension clamp
for testing. During testing, a pre-load of 0.01 N was applied to
the cut film samples. The instrument was cooled to -80.degree. C.,
held for 1 minute, then the temperature was ramped at 4.degree.
C/minute to 200.degree. C., or until the sample was too weak to be
held in tension. During the temperature ramp, the sample was
oscillated 0.1% strain at a frequency of 1 Hz. The storage modulus,
loss modulus, and tan(.delta.) were plotted with temperature for
both films. The resulting second storage modulus transition (taken
as the onset point of the last decrease in the storage modulus
measured, i.e. second DMA modulus transition onset temperature) was
114.9.degree. C. for the control sample.
[0295] Additionally, 5 tensile specimens (according to ASTM D638)
were each cut from the dried and conditioned sample film using a
metal die. The cut film samples were loaded into an INSTRON.RTM.
5960 series machine and pulled in tension at 100 millimeters/minute
until break. The average Young's modulus, average tensile strength
(maximum tensile stress), and average elongation at break were
recorded. The Young's modulus was 59 MPa, the maximum tensile
stress was 12.9 MPa, and the elongation at break was 402%.
EXAMPLES 2-8
[0296] Examples 2-8 were performed using the same method as Example
1 to show a range of polyurethane dispersions. The polyurethanes
used and the resulting properties are listed in Tables 3-6.
EXAMPLE 9
[0297] A sample was prepared by dissolving 0.825 g (grams) of
gelatin from porcine skin into 10 mL (milliliters) of de-ionized
water and stirring with a magnetic stir bar at 1000 rpm (rotations
per minute) for 1 hour at 50.degree. C. After the gelatin was fully
dissolved, the pH of the solution was adjusted to 7.0 with 0.1 N
sodium hydroxide. Then 5.5 g of L3360 was added to the solution and
stirred at 1000 rpm for 30 minutes. The polyurethane and gelatin
solution was then pipetted into a Teflon evaporating dish with a
diameter of 10 cm. The dish was dried in an oven at 45.degree. C.
overnight. After drying, the dried sample was conditioned at
standard reference atmosphere (23.degree. C., 50% humidity) for 24
hours to create a gelatin polyurethane alloy film.
[0298] At the time of pipetting, the gelatin polyurethane solution
was milky in appearance, with no particulates visible. After
drying, the gelatin polyurethane solution produced a transparent
film with uniform look with no optically visible granules. This
result, combined with the Examples of 33 and 34, show that when the
protein is miscible with the hard phase, the protein polyurethane
alloy can be transparent and have enhanced properties.
[0299] DMA testing was performed as outlined in Example 1. The
resulting second storage modulus transition (taken as the onset
point of the last decrease in the storage modulus measured, i.e.
second DMA modulus transition onset temperature) for the gelatin
polyurethane alloy was 180.6.degree. C., a 65.7.degree. C. increase
over the control sample described in Example 1.
[0300] Tensile testing was performed as outlined in Example 1. The
average Young's modulus was 344 MPa, the average tensile stress
measured was 19.8 MPa, and the average elongation at break was 197%
for the gelatin polyurethane alloy.
[0301] The increase in the second DMA modulus transition onset
temperature of this example, along with increased modulus and
strength, and decreased elongation, compared to the polyurethane
alone in Example 1, indicate that the dissolved gelatin in the
gelatin polyurethane alloy is miscible with the hard phase of the
polyurethane.
EXAMPLES 10-19
[0302] Examples 10-19 were performed using the same method as used
for Example 9 to show a range of polyurethane dispersions from
different manufacturers and different proteins. The resulting
properties of these alloys are listed in Tables 3-6.
EXAMPLE 20
[0303] A sample was prepared by dissolving 0.825 g (grams) of
Bovine Serum Albumin from Sigma (BSA) into 10 mL (milliliters) of
de-ionized water and stirring with a magnetic stir bar at 1000 rpm
(rotations per minute) for 1 hour at 20.degree. C. Then 5.5 g of
L3360 was added to the solution and stirred at 1000 rpm for 30
minutes. The polyurethane and BSA solution was then pipetted into a
Teflon evaporating dish with a diameter of 10 cm. The dish was
dried on the benchtop at 25.degree. C. overnight. After drying, the
dried sample was conditioned at standard reference atmosphere
(23.degree. C., 50% humidity) for 24 hours to create a BSA
polyurethane alloy film.
[0304] DMA testing was performed as outlined in Example 1. The
resulting second storage modulus transition (taken as the onset
point of the last decrease in the storage modulus measured, i.e.
second DMA modulus transition onset temperature) for the BSA
polyurethane alloy was 184.9.degree. C., a 70.degree. C. increase
over the control sample described in Example 1.
[0305] Tensile testing was performed as outlined in Example 1. The
average Young's modulus was 174 MPa, the average tensile stress
measured was 11.7 MPa, and the average elongation at break was 123%
for the BSA polyurethane alloy.
EXAMPLE 21
[0306] Soy protein isolate (SPI) was dispersed by adding 0.75 g SPI
into 15 mL of a sodium hydroxide solution at a 0.05 mol/L
concentration. The dispersion was stirred with a magnetic stir bar
at 600 rpm for 3 hours at 80.degree. C. Then 5 g of L3360 was added
to the solution and stirred at 600 rpm for 30 minutes. The SPI
polyurethane solution was then pipetted into a Teflon evaporating
dish with a diameter of 10 cm. The dish was dried in an oven at
45.degree. C. overnight. After drying, the dried sample was
conditioned at standard reference atmosphere (23.degree. C., 50%
humidity) for 24 hours to create a SPI polyurethane alloy film.
[0307] DMA testing was performed as outlined in Example 1. The
resulting second storage modulus transition (taken as the onset
point of the last decrease in the storage modulus measured, i.e.
second DMA modulus transition onset temperature) for the SPI
polyurethane alloy was 186.6.degree. C., a 72.degree. C. increase
over the control in Example 1.
[0308] Tensile testing was performed as outlined in Example 1. The
average Young's modulus was 396 MPa, the average tensile stress
measured was 18 MPa, and the average elongation at break was 151%
for the SPI polyurethane alloy.
[0309] The increase in the second DMA modulus transition onset
temperature, along with increased modulus and strength, and
decreased elongation, indicate that the dissolved SPI in the SPI
polyurethane alloy is miscible with the hard phase of the
polyurethane.
EXAMPLES 22-23
[0310] Examples 22-23 were preformed using the same method as
Example 21. The proteins used and the resulting properties of these
protein polymer alloys are listed in Tables 3-6.
EXAMPLES 24-29
[0311] Samples were prepared by the same method as Example 9. The
gelatin and L3360 amounts were varied to achieve various mass
ratios of the two components in the alloy samples. The masses of
gelatin and PU dispersion, as well as the resulting mass fractions,
are summarized below in Table 2.
TABLE-US-00002 TABLE 2 Gelatin L3360 Dispersion Gelatin Mass L3360
Mass Ex. No. Added (g) Added (g) Fraction Fraction 24 1.25 3.6 50%
50% 25 0.5 5.7 20% 80% 26 0.375 6.1 15% 85% 27 0.25 6.4 10% 90% 28
0.125 6.8 5% 95% 29 0.025 7.1 1% 99%
[0312] Tensile and DMA testing were performed as outlined in
Example 1. The resulting properties of the alloys are listed in
Tables 3-6.
EXAMPLE 30
[0313] Soy protein isolate (SPI) was dispersed by adding 0.25 g SPI
into 15 mL of DI Water.
[0314] The dispersion was stirred with a magnetic stir bar at 600
rpm for 3 hours at 80.degree. C. Then 6.42 g of L3360 was added to
the solution and stirred at 600 rpm for 30 minutes. The SPI
polyurethane solution was then pipetted into a Teflon evaporating
dish with a diameter of 10 cm. The dish was dried in an oven at
45.degree. C. overnight. After drying, the dried sample was
conditioned at standard reference atmosphere (23.degree. C., 50%
humidity) for 24 hours to create a SPI polyurethane alloy film.
[0315] Tensile and DMA testing were performed as outlined in
Example 1. The resulting properties of the alloy are listed in
Tables 3-6.
EXAMPLE 31
[0316] Soy protein isolate (SPI) was dispersed by adding 0.5 g SPI
into 15 mL of a sodium hydroxide solution at a 0.05 mol/L
concentration. The dispersion was stirred with a magnetic stir bar
at 600 rpm for 3 hours at 80.degree. C. Then 6.42 g of L3360 was
added to the solution and stirred at 600 rpm for 30 minutes. The
SPI polyurethane solution was then pipetted into a Teflon
evaporating dish with a diameter of 10 cm. The dish was dried in an
oven at 45.degree. C. overnight. After drying, the dried sample was
conditioned at standard reference atmosphere (23.degree. C., 50%
humidity) for 24 hours to create a SPI polyurethane alloy film.
[0317] Tensile and DMA testing were performed as outlined in
Example 1. The resulting properties of the alloy are listed in
Tables 3-6.
EXAMPLE 32
[0318] Whey protein (bovine milk whey W1500 from Sigma) was
dispersed by adding 0.75 g Whey into 15 mL of a sodium hydroxide
solution at a 0.05 mol/L concentration. The dispersion was stirred
with a magnetic stir bar at 600 rpm for 3 hours at 80.degree. C.
Then 5 g of L3360 was added to the solution and stirred at 600 rpm
for 30 minutes. The whey polyurethane solution was then pipetted
into a Teflon evaporating dish with a diameter of 10 cm. The dish
was dried in an oven at 45.degree. C. overnight. After drying, the
dried sample was conditioned at standard reference atmosphere
(23.degree. C., 50% humidity) for 24 hours to create a whey
polyurethane alloy film.
[0319] DMA testing was performed as outlined in Example 1. The
resulting second storage modulus transition (taken as the onset
point of the last decrease in the storage modulus measured, i.e.
second DMA modulus transition onset temperature) for the whey
polyurethane alloy was 100.9.degree. C., a 14.degree. C. decrease
compared to the control in Example 1.
[0320] Tensile testing was performed as outlined in Example 1. The
average Young's modulus was 105 MPa, the average tensile stress
measured was 7.6 MPa, and the average elongation at break was 224%
for the whey polyurethane alloy.
[0321] While the whey appears to be miscible with the hard phase of
the polyurethane, it is believed that the second DMA modulus
transition temperature did not increase because of the poor thermal
stability of the protein itself. As discussed above, the whey had a
denaturation temperature at 158.degree. C., and was therefore
considered non-thermo-stable.
EXAMPLE 33
[0322] 0.75 g of casein (from bovine milk, Sigma, C7078) was added
into 15 mL of DI water (pH=7) in a 20 mL glass vial without any
other additives, stirred at 600 rpm, heated to 90.degree. C., and
maintained for 3 hours.
[0323] Then 5 g of L3360 was added into the 20 mL glass vial. The
glass vial was capped and vortexed for 1 min at max speed. The
mixed casein polyurethane liquid was then transferred into a 10 cm
Teflon dish. The dish was dried in an oven at 45.degree. C.
overnight (16 to 24 hours).
[0324] After drying, the casein polyurethane alloy film had an
opaque look with numerous optically visible granules in the film.
The tensile properties of this film were measured by measuring five
tensile specimens using an INSTRON.degree. 5960 series machine. The
samples were pulled in tension at 100 millimeters/minute until
break. The average tensile strength for the film was 4.96 MPa. The
average elongation at break for the film was 12.03%. The average
Young's modulus of the film was 158 MPa. These results, along with
the results of Example 39, indicate that casein is insoluble and
not dispersible in water at pH 7, and thus does not dissolve in
L3360 when mixed.
EXAMPLE 34
[0325] 0.75 g of casein (from bovine milk, Sigma, C7078) was
dispersed into a 15 mL 0.05 mol/L NaOH DI water solution in a 20 mL
glass vial, stirred at 600 rpm, heated to 90.degree. C., and
maintained for 3 hours. A uniform dispersion was obtained.
[0326] Then 5 g of L3360 was added into the 20 mL glass vial. The
glass vial was then capped and vortexed for 1 min at max speed. The
mixed casein polyurethane liquid was then transferred into a 10 cm
Teflon dish. The dish was dried in an oven at 45.degree. C.
overnight (16 to 24 hours).
[0327] After drying, the casein polyurethane alloy film had a
transparent and uniform look with no optically visible granules in
the film. The tensile properties of this film were measured by
measuring five tensile specimens using an INSTRON.RTM. 5960 series
machine. The samples were pulled in tension at 100
millimeters/minute until break. The average tensile strength for
the film was 15.5 MPa. The average elongation at break for the film
was 160%. The average Young's modulus of the film was 160 MPa. The
increase modulus, strength, and elongation compared to Example 33
indicate that the modified casein dissolved within the polyurethane
and is miscible with the hard phase of the polyurethane.
EXAMPLE 35
[0328] 0.375 g of soy protein isolate (SPI) and 0.375 g r-Collagen
were added into 15 mL of a sodium hydroxide solution at a 0.05
mol/L concentration in a 20 mL glass vial. The soy protein isolate
was soy protein isolate purchased from MP Medicals (IC90545625).
The r-Collagen was recombinant collagen from Modern Meadow. The
solution in the vial was mixed with a magnetic stir bar at 600 rpm
for 2 hours at 80.degree. C.
[0329] Then 5 g of L3360 was added into the 20 mL glass vial. The
glass vial was capped and vortexed for 1 min at max speed. The
mixed SPI/r-col polyurethane liquid was then transferred into a 10
cm Teflon dish. The dish was dried in an oven at 45.degree. C.
overnight. After drying, the dried sample was conditioned at
standard reference atmosphere (23.degree. C., 50% humidity) for 24
hours to create a SPI/r-col polyurethane alloy film.
[0330] The tensile properties of this film were measured by
measuring five tensile specimens using an INSTRON.RTM. 5960 series
machine. The samples were pulled in tension at 100
millimeters/minute until break. The average tensile strength for
the film was 15.71 MPa. The average elongation at break for the
film was 175.9%. The average Young's modulus of the film was 247.1
MPa. The film was also tested using a DMA-850 from TA Instruments
follow the method described in Example 1. The resulting second
storage modulus transition (taken as the onset point of the last
decrease in the storage modulus measured, i.e. second DMA modulus
transition onset temperature) for the SPI/r-col polyurethane alloy
was 184.9.degree. C.
[0331] Compared with Example No. 1 and Example No. 9, these results
show the increase in the second DMA modulus transition onset
temperature, along with increased modulus and strength, and
decreased elongation, indicate that the blend of SPI and r-col in
the polyurethane alloy was miscible with the hard phase of the
polyurethane and showed the corresponding enhancement in
properties.
EXAMPLE 37
[0332] Using the same method as Example 36, a film was made with
0.375 g pea protein MTX5232 from Bobs Red Mills, 0.375 g r-Collagen
(recombinant collagen from Modern Meadow) and 5 g of L3360
polyurethane dispersion.
[0333] The resulting protein polyurethane alloy film was tested
using the same tensile and DMA testing methods as described for
Example 36. The average tensile strength for the film was 15.36
MPa. The average elongation at break for the film was 183.17%. The
average Young's modulus of the film was 231.13 MPa. The second DMA
modulus transition onset temperature for the pea protein/r-col
polyurethane alloy was 189.65.degree. C.
[0334] Compared with Example No. 1 and Example No. 9, these results
show the increase in the second DMA modulus transition onset
temperature, along with increased modulus and strength indicate
that the blend of pea protein and r-col in the protein polyurethane
alloy was miscible with the hard phase of the polyurethane and
showed the corresponding enhancement in properties.
EXAMPLE 38
[0335] A gelatin solution was prepared by dissolving 0.825 g
(grams) of gelatin from porcine skin (Sigma Aldrich G2500) into 10
mL (milliliters) of de-ionized water and stirring with a magnetic
stir bar at 1000 rpm (rotations per minute) for 1 hour at
50.degree. C. After the gelatin was fully dissolved, the pH of the
solution was adjusted to 7.0 with 0.1 N sodium hydroxide. Navy
Black #1684 fiber reactive dye was added to the gelatin solution at
4.05 parts per hundred parts of gelatin and mixed for 15 minutes at
45.degree. C. Then 5.5 g of L3360 was added to the solution and
stirred at 1000 rpm for 30 minutes. The polyurethane and gelatin
solution was then pipetted into a Teflon evaporating dish with a
diameter of 10 cm. The dish was dried in an oven at 45.degree. C.
overnight. The resulting film was evenly dyed, with no phase
separation or difference in color across the sample. A comparable
film of the same polyurethane dispersion without protein could not
be evenly dyed.
EXAMPLE 39A
[0336] Chemically modified soy protein solutions (chemically
modified SUPRO.RTM. XT 55 soy protein isolate and chemically
modified SUPRO.RTM. XT 221D soy protein isolate) were prepared by
preparing two 5 mL of 0.1 mol/L sodium hydroxide solutions. Once
prepared, 40 milligrams (mg) of DABCO
(1,4-diazabicyclo[2.2.2]octane) was added to each solution and
allowed to dissolve. Upon dissolution of the DABCO, 300 mg of
poly(ethylene glycol) monoglycidyl ether-550 Mn was added to each
solution followed by the addition of 0.75 g of SUPRO.RTM. XT 55 soy
protein isolate to one solution and 0.75 g of SUPRO.RTM. XT 221D
soy protein isolate to the other solution. The solutions were
allowed to stir at 600 rpm for 45 minutes at 65.degree. C. to
create chemically modified soy proteins with much higher solubility
in an aqueous solution compared to the individual soy proteins in
0.1 mol/L sodium hydroxide alone without modification. The
poly(ethylene glycol) monoglycidyl ether modified protein solutions
were significantly more transparent compared to identical protein
solutions without poly(ethylene glycol) monoglycidyl ether,
indicating an increase in solubility. Additionally, size-exclusion
chromatography (SEC) data indicated that the soluble modified
protein solutions showed minimal hydrolysis, indicating that the
protein solubility was due to the protein modification and not due
to hydrolysis by the basic conditions that were used
EXAMPLE 39B
[0337] Chemically modified soy protein solutions (chemically
modified SUPRO.RTM. XT 55 soy protein isolate and chemically
modified SUPRO.RTM. XT 221D soy protein isolate) were prepared by
preparing two 5 mL of 0.1 mol/L sodium hydroxide solution. Once
prepared, 40 mg of DABCO (1,4-diazabicyclo[2.2.2]octane) was added
to each solution and allowed to dissolve. Upon dissolution of the
DABCO, 300 mg of poly(ethylene glycol) diglycidly ether-550 Mn was
added to the solution followed by the addition of 0.75 g SUPRO.RTM.
XT 55 soy protein isolate to one solution and 0.75 g of SUPRO.RTM.
XT 221D soy protein isolate to the other solution. The solutions
were allowed to stir at 600 rpm for 45 minutes at 65.degree. C. to
create soy proteins with much higher solubility in an aqueous
solution compared to the individual soy proteins in 0.1 mol/L
sodium hydroxide alone without modification. The poly(ethylene
glycol) diglycidyl ether modified protein solutions were
significantly more transparent compared to identical protein
solutions without poly(ethylene glycol) diglycidyl ether indicating
an increase in solubility. Additionally, SEC data indicated that
the soluble modified soy protein solutions showed minimal
hydrolysis, indicating that the protein solubility was due to the
protein modification and not due to hydrolysis by the basic
conditions that were used.
EXAMPLE 40
[0338] SUPRO.RTM. XT55 soy protein isolate (SPI) was dispersed by
adding 0.75 g SPI into 5 mL of a sodium hydroxide solution at a 0.1
mol/L concentration. The dispersion was stirred with a magnetic
stir bar at 600 rpm for 2 hours at 65.degree. C. HeiQ Chemtex 2317
(an anionic surfactant) was added in an amount of 5 parts per 100
parts protein by mass. Then 5 g of L3360 was added to the solution
and stirred at 600 rpm for 30 minutes. The SPI polyurethane
solution was then pipetted into a Teflon evaporating dish with a
diameter of 10 cm. The dish was dried in an oven at 45.degree. C.
overnight. After drying, the dried sample was conditioned at
standard reference atmosphere (23.degree. C., 50% humidity) for 24
hours to create a SPI polyurethane alloy film.
EXAMPLE 41
[0339] A gelatin solution was prepared by dissolving 3.885 g of
gelatin from porcine skin (Sigma Aldrich G2500) into 22 mL
de-ionized water and stirring at 450 rpm using an overhead impeller
mixer for 1 hour at 50.degree. C. After the gelatin was fully
dissolved, the pH of the solution was adjusted to 7.0 with 1 N
sodium hydroxide. After the pH adjustment, antimicrobial
Ultra-Fresh DW-56 was added at 1.2 parts per hundred parts of
gelatin solution by weight. The solution was then mixed for 10
minutes at 50.degree. C. to assure good dispersion of all the
components. After 10 minutes, 15 mL of the solution was aliquoted
and Antifoam 204 (a mixture of organic polyether dispersions from
Sigma Aldrich) was added at 0.5 parts per hundred parts of the
estimated final solution weight. The aliquoted solution was mixed
for 10 minutes at 50.degree. C. to assure good dispersion of all
the components. Then, 25.885 g L3360 was added to the solution.
After the addition of L3360, the solution was mixed until a
temperature of 43.degree. C. to 45.degree. C. was reached.
[0340] To the other aliquot of the solution, HeiQ Chemtex 2216-T (a
stabilized blend of nonionic and anionic surfactants) at 5.5 parts
per hundreds parts and HeiQ Chemtex 2317 (a stabilized blend of
nonionic and anionic surfactants) at 2.2 parts per hundreds parts
of the solution weight were added along with 0.1 parts per hundreds
parts of HeiQ Chemtex 2243 (a non-ionic silicone dispersion). The
solution was then mechanically frothed cold until wet densities
between 650 g/L to 850 g/L at a temperature of 43.degree. C. to
45.degree. C. were reached, thereby forming a foamed blended
mixture.
[0341] A surface finish comprising a top-coat and basecoat was
prepared to create the pre-skin of the protein polyurethane alloy.
A top-coat blend was created by blending 9.74 parts of Stahl Melio
WF-5227. A LIQ, 100 parts of Stahl WT-42-511, 30 parts of Stahl
DI-17-701, 30 parts of Stahl XR-13-820, and 25 parts of water. A
basecoat blend was created by blending 450 parts of Stahl
RC-43-023, 50 parts of Stahl RU-3901, 150 parts of Stahl RA-30, 50
parts of Stahl FI-1208, 30 parts of Stahl XR-13-820, and 100 parts
of Stahl RA-22-063.
[0342] The blended non-foamed solution was deposited on the dried
pre-skin using a drawdown device at a target wet thickness of 200
gsm and dried for 15 minutes in a Mathis LTE-S Labcoater at
75.degree. C., 2000 rpm air speed, and 70% of the air blowing from
underneath the sample to form a protein polyurethane alloy layer.
After this first layer was dried, a second layer of the blended
foamed solution was deposited on top of the first layer at the
target wet thickness of 350 gsm and dried for 15 minutes in a
Mathis LTE-S Labcoater with a ramp-like drying procedure starting
at 75.degree. C. for 5 minutes, then 100.degree. C. for 5 minutes
and lastly, 120.degree. C. for 5 minutes at 700 rpm air speed, and
70% of the air blowing from underneath to form a first foamed
protein polyurethane alloy layer. After the foam layer was dried, a
third layer of the blended foamed solution was deposited on top of
the first foamed layer at the target wet thickness of 350 gsm and
dried for 15 minutes in a Mathis LTE-S Labcoater with a ramp-like
drying procedure starting at 75.degree. C. for 5 minutes, then
100.degree. C. for 5 minutes and lastly, 120.degree. C., 700 rpm
air speed, and 70% of the air blowing from underneath to form a
second foamed protein polyurethane alloy layer.
[0343] After the sample was fully dried and conditioned for 24
hours in a conditioning chamber at 23.degree. C. and 50% humidity
for 24 hours, the sample was cut and tested according to the DMA
and tensile mechanical property tests described herein. The
resulting second storage modulus transition (taken as the onset
point of the last decrease in the storage modulus measured, i.e.
second DMA modulus transition onset temperature) was 190.degree.
C., the Young's modulus was 88.9 MPa, the tensile stress was 5.4
MPa, and the elongation at break was 110%.
EXAMPLE 42
[0344] A sample was prepared by dissolving 1 g of 50 KDa rCol into
5 mL of de-ionized water and stirring with a magnetic stir bar at
1000 rpm for 1 hour at 20.degree. C. The 50 KDa rCol protein was a
collagen fragment prepared by Modern Meadow comprising the amino
acid sequence listed as SEQ ID NO: 1. After stirring for 1 hour,
6.7 g of L3360 was added to the solution and stirred at 1000 rpm
for 30 minutes. The polyurethane and 50 KDa rCol solution was then
pipetted into a Teflon evaporating dish with a diameter of 10 cm.
The dish was dried in an oven at 45.degree. C. overnight. After
drying, the dried sample was conditioned at standard reference
atmosphere (23.degree. C., 50% humidity) for 24 hours to create a
50 KDa rCol polyurethane alloy film.
[0345] DMA testing was performed as outlined in Example 1. The
resulting second storage modulus transition (taken as the onset
point of the last decrease in the storage modulus measured, i.e.
second DMA modulus transition onset temperature) for the 50 KDa
rCol polyurethane alloy was 177.8.degree. C., a 62.9.degree. C.
increase over the control sample described in Example 1.
[0346] Tensile testing was performed as outlined in Example 1. The
average Young's modulus was 161 MPa, the average tensile stress
measured was 17 MPa, and the average elongation at break was 173%
for the 50 KDa rCol polyurethane alloy.
EXAMPLE 43
[0347] A sample was prepared by dissolving 1 g of Native
Trichoderma sp. Cellulase available from CREATIVE ENZYMES.RTM.
(Cellulase-RG) into 5 mL of de-ionized water and stirring with a
magnetic stir bar at 1000 rpm for 1 hour at 20.degree. C. After
stirring for 1 hour, 11.4 g of L3360 was added to the solution and
stirred at 1000 rpm for 30 minutes. The polyurethane and cellulase
solution was then pipetted into a Teflon evaporating dish with a
diameter of 10 cm. The dish was dried in an oven at 45.degree. C.
overnight. After drying, the dried sample was conditioned at
standard reference atmosphere (23.degree. C., 50% humidity) for 24
hours to create a cellulase polyurethane alloy film.
[0348] DMA testing was performed as outlined in Example 1. The
resulting second storage modulus transition (taken as the onset
point of the last decrease in the storage modulus measured, i.e.
second DMA modulus transition onset temperature) for the
Celluase-RG polyurethane alloy was 153.1.degree. C., a 38.2.degree.
C. increase over the control sample described in Example 1.
[0349] Tensile testing was performed as outlined in Example 1. The
average Young's modulus was 184 MPa, the average tensile stress
measured was 14.7 MPa, and the average elongation at break was 252%
for the cellulase polyurethane alloy.
EXAMPLE 44
[0350] A sample was prepared by dissolving 1 g of laboratory grade
cellulase available from Carolina Biological Supply Company
(Cellulase-IG) into 5 mL of de-ionized water and stirring with a
magnetic stir bar at 1000 rpm for 1 hour at 20.degree. C. After
stirring for 1 hour, 11.4 g of L3360 was added to the solution and
stirred at 1000 rpm for 30 minutes. The polyurethane and cellulase
solution was then pipetted into a Teflon evaporating dish with a
diameter of 10 cm. The dish was dried in an oven at 45.degree. C.
overnight. After drying, the dried sample was conditioned at
standard reference atmosphere (23.degree. C., 50% humidity) for 24
hours to create a cellulase polyurethane alloy film.
[0351] DMA testing was performed as outlined in Example 1. The
resulting second storage modulus transition (taken as the onset
point of the last decrease in the storage modulus measured, i.e.
second DMA modulus transition onset temperature) for the
Cellulase-IG polyurethane alloy was 122.1.degree. C., a 7.2.degree.
C. increase over the control sample described in Example 1.
[0352] Tensile testing was performed as outlined in Example 1. The
average Young's modulus was 84 MPa, the average tensile stress
measured was 15.1 MPa, and the average elongation at break was 286%
for the cellulase polyurethane alloy.
EXAMPLE 45
[0353] Two control samples (Example No. 45a and Example No. 45b)
were each prepared according to the following process. 0.4 g of
AF-715 (an antifoaming agent available from Quaker Color) was mixed
into 38 g of waterborne polyurethane dispersion Hauthane HD-2001
from C.L. Hauthaway & Sons Corporation. The mixture was mixed
using an impeller at a rate of 500 rpm and allowed to stir for 5
minutes at room temperature. After the mixture was properly mixed,
0.6 g BORCHI.RTM. Gel L 75 N was added to increase the viscosity of
the mixture and the mixture was allowed to mix for 5 minutes. The
mixture was then coated using a Mathis LTE-S Labcoater coater onto
a release paper and was dried at 75.degree. C. for 10 minutes and
at 100.degree. C. for 10 minutes. The coating was then removed from
the release paper to create a polyurethane film containing no
protein.
[0354] After drying, the sample for Example 45a had a thickness of
0.4 mm and the sample for Example 45b had a thickness of 0.4 mm. As
reported in Table 7, the polyurethane film of Example 45a had a
moisture vapor transmission rate of 30 g/m.sup.2/24 hr and
polyurethane film of Example 45b had a moisture vapor transmission
rate of 38 g/m.sup.2/24 hr.
EXAMPLE 46
[0355] Two samples (Example No. 46a and Example No. 46b) were each
prepared according to the following process. 13.25 g of gelatin
from porcine skin was dissolved in a solution of 2 g of
antimicrobial Ultra-Fresh DW-56, 0.8 g of AF-715 (an antifoaming
agent available from Quaker Color), and 75 mL of water at
50.degree. C. The solution was stirred using an impeller at 500 rpm
until the gelatin was fully dissolved. The pH of the solution was
then increased using 1M NaOH until a pH of 8-9 was achieved. After
adjusting the pH, 77 g of waterborne polyurethane dispersion
Hauthane HD-2001 from C.L. Hauthaway & Sons Corporation was
added to the gelatin solution and stirred for 15 minutes. After the
gelatin and polyurethane solution was properly mixed, 1 g of
RM-4410 from Stahl was added to increase the viscosity of the
solution and the solution was mixed for 5 minutes. The solution was
then coated on a 0.35 mm thick microsuede textile having a surface
coated with a thin IMPRANIL.RTM. DLS coating layer (thickness of
0.03 mm). The gelatin polyurethane solution was coated on top of
the thin IMPRANIL.RTM. DLS coating layer using a handheld draw down
apparatus and was allowed to dry at standard reference atmosphere
(23.degree. C. and 50% humidity) to create a gelatin-polyurethane
film with a textile backing. The thin IMPRANIL.RTM. DLS coating was
used to prevent the gelatin polyurethane coating from deeply
penetrating into the microsuede textile.
[0356] After drying, the sample for Example No. 46a had a thickness
of 0.77 mm (which was the sum of the thicknesses for the
gelatin-polyurethane film, the thin IMPRANIL.RTM. DLS coating, and
the microsuede textile) and the sample for Example 46b had a
thickness of 0.82 mm (which was the sum of the thicknesses for the
gelatin-polyurethane film, the thin Impranil.RTM. DLS coating, and
the microsuede textile).
[0357] As reported in Table 7, the sample for Example No. 46a had a
moisture vapor transmission rate of 180 g/m.sup.2/24 hr, which was
a 150 g/m.sup.2/24 hr increase compared to the sample of Example
No. 45a and a 142 g/m.sup.2/24 hr increase compared to the sample
of Example No. 45b. As also reported in Table 7, the sample for
Example No. 46b had a moisture vapor transmission rate of 138
g/m.sup.2/24 hr, which was a 108 g/m.sup.2/24 hr increase compared
to the sample of Example No. 45a and a 100 g/m.sup.2/24 hr increase
compared to the sample of Example No. 45b.
[0358] Neither the thin IMPRANIL.RTM. DLS coating nor the
microsuede textile had a significant influence on the moisture
vapor transmission rates for the samples of Example Nos. 46a or
46b. In other words, the moisture vapor transmission rates reported
in Table 7 reflect the moisture vapor transmission rates for only
the gelatin-polyurethane films.
EXAMPLE 47
[0359] Two control samples (Example No. 47a and Example No. 47b)
were each prepared according to the following process. 0.4 g of
AF-715 (an antifoaming agent available from Quaker Color) was mixed
into 38 g of waterborne polyurethane dispersion L3360 from
Hauthaway. The mixture was mixed using an impeller at a rate of 500
rpm and allowed to stir for 5 minutes at room temperature. After
the mixture was properly mixed, 0.6 g BORCHI.RTM. Gel L 75 N was
added to increase the viscosity of the mixture and the mixture was
allowed to mix for 5 minutes. The mixture was then coated using a
Mathis LTE-S Labcoater coater onto a release paper and was dried at
75.degree. C. for 10 minutes and at 100.degree. C. for 10 minutes.
The coating was then removed from the release paper to create a
polyurethane film containing no protein.
[0360] After drying, the sample for Example No. 47a had a thickness
of 0.32 mm and the sample for Example No. 47b had a thickness of
0.36 mm. As reported in Table 7, the polyurethane film of Example
No. 47a had a moisture vapor transmission rate of 23 g/m.sup.2/24
hr and polyurethane film of Example No. 47b had a moisture vapor
transmission rate of 27 g/m.sup.2/24 hr.
EXAMPLE 48
[0361] Two samples (Example No. 48a and Example No. 48b) were each
prepared according to the following process. 13.25 g of gelatin
from porcine skin was dissolved in a solution of 2 g of
antimicrobial Ultra-Fresh DW-56, 0.8 g of AF-715 (an antifoaming
agent available from Quaker Color), and 75 mL of water at
50.degree. C. The solution was stirred using an impeller at 500 rpm
until the gelatin was fully dissolved. The pH of the solution was
then increased using 1M NaOH until a pH of 8-9 was achieved. After
adjusting the pH, 77 g of waterborne polyurethane dispersion L3360
from Hauthaway was added to the gelatin solution and stirred for 15
minutes. After the gelatin and polyurethane solution was properly
mixed, 1 g of RM-4410 from Stahl was added to increase the
viscosity of the solution and the solution was mixed for 5 minutes.
The solution was then coated on a 0.35 mm thick microsuede textile
having a surface coated with a thin IMPRANIL.RTM. DLS coating layer
(thickness of 0.03 mm). The gelatin and polyurethane solution was
coated on top of the thin IMPRANIL.RTM. DLS coating layer using a
handheld draw down apparatus and was allowed to dry at standard
reference atmosphere (23.degree. C. and 50% humidity) to create a
gelatin-polyurethane film with a textile backing. The thin
IMPRANIL.RTM. DLS coating was used to prevent the gelatin
polyurethane coating from deeply penetrating into the microsuede
textile.
[0362] After drying, the sample for Example No. 48a had a thickness
of 0.77 mm (which was the sum of the thicknesses for the
gelatin-polyurethane film, the thin IMPRANIL.RTM. DLS coating, and
the microsuede textile) and the sample for Example No. 48b had a
thickness of 0.84 mm (which was the sum of the thicknesses for the
gelatin-polyurethane film, the thin Impranil.RTM. DLS coating, and
the microsuede textile).
[0363] As reported in Table 7, the sample for Example No. 48a had a
moisture vapor transmission rate of 117 g/m.sup.2/24 hr, which was
a 94 g/m.sup.2/24 hr increase compared to the sample of Example No.
47a and a 90 g/m.sup.2/24 hr increase compared to the sample of
Example No. 47b. As also reported in Table 7, the sample for
Example 48b had a moisture vapor transmission rate of 74
g/m.sup.2/24 hr, which was a 51 g/m.sup.2/24 hr increase compared
to the sample of Example No. 47a and a 47 g/m.sup.2/24 hr increase
compared to the sample of Example No. 47b.
[0364] Neither the thin IMPRANIL.RTM. DLS coating nor the
microsuede textile had a significant influence on the moisture
vapor transmission rates for the samples of Example Nos. 46a or
46b. In other words, the moisture vapor transmission rates reported
in Table 7 reflect the moisture vapor transmission rates for only
the gelatin-polyurethane films.
EXAMPLE 49
[0365] Two control samples (Example No. 49a and Example No. 49b)
were each prepared according to the following process. 0.2 g of
AF-715 (an antifoaming agent available from Quaker Color) was mixed
into 38 g of waterborne polyurethane dispersion L3360 from
Hauthaway. The mixture was mixed using an impeller at a rate of 500
rpm for 5 minutes. After the mixture was properly mixed, 0.6 g
BORCHI.RTM. Gel L 75 N was added to increase the viscosity of the
mixture and the mixture was mixed again for 5 minutes. This
polyurethane mixture was then coated onto a release paper using a
Mathis LTE-S Labcoater and allowed to dry at 75.degree. C. for 10
minutes and at 100.degree. C. for 10 minutes.
[0366] Then a foam solution was then prepared by mixing waterborne
polyurethane dispersion L3360 from Hauthaway with HeiQ Chemtex
2216-T (3% based on solution weight), HeiQ Chemtex 2317 (3% based
on solution weight), HeiQ Chemtex 2241-A (1% based on solution
weight), and HeiQ Chemtex 2243 (0.1% based on solution weight).
This mixture was stirred for 5 minutes at room temperature using an
impeller at 500 rpm. The mixture was then frothed to create a
foamed mixture having a wet density between 700 g/L and 900 g/L.
The foamed mixture was coated on the previously coated polyurethane
layer using the Mathis LTE-S Labcoater and allowed to dry at
75.degree. C. for 10 minutes and at 100.degree. C. for 10 minutes.
After this first foamed coating was dried, a second foamed coating
layer made of the same foamed mixture was coated on the first
foamed coating using identical conditions. After drying of the
second foamed layer, the three-layer sample was removed from the
release paper.
[0367] The three-layer sample for Example No. 49a had a thickness
of 0.23 mm and the three-layer sample for Example No. 49b had a
thickness of 0.24 mm. As reported in Table 7, the three-layer
sample of Example No. 49a had a moisture vapor transmission rate of
83 g/m.sup.2/24 hr and the three-layer sample of Example No. 49b
had a moisture vapor transmission rate of 87 g/m.sup.2/24 hr.
EXAMPLE 50
[0368] Two samples (Example No. 50a and Example No. 50b) were each
prepared according to the following process. 5.3 g of SUPRO.RTM. XT
221D soy protein isolate was mixed with 30 g of water. The pH of
the mixture was then increased using 1M NaOH until a pH of 8-9 was
achieved. After adjusting the pH, Ultra-Fresh DW-56 (15 wt % based
on the soy protein isolate mass) and AF-715 antifoaming agent (1 wt
% based on solution weight) were added and to the mixture, and the
mixture was stirred using an impeller at 500 rpm until the soy
protein isolate was fully dissolved. Once the soy protein isolate
was fully dissolved, 32 g of waterborne polyurethane dispersion
L3360 from Hauthaway was added to the protein solution and the
solution was stirred using an impeller at a rate of 500 rpm for 10
minutes at room temperature. The protein solution was then coated
onto a release paper using a Mathis LTE-S Labcoater and allowed to
dry at 75.degree. C. for 10 minutes and at 100.degree. C. for 10
minutes.
[0369] Then a foam solution was prepared by mixing 5.3 g SUPRO.RTM.
XT 221D soy protein isolate with 30 g of water. The pH of the
mixture was increased using 1M NaOH until a pH of 8-9 was achieved.
After adjusting the pH and once the soy protein isolate was fully
dissolved, Ultra-Fresh DW-56 (15 wt % based on the soy protein
mass), HeiQ Chemtex 2216-T (3 wt % based on solution weight), HeiQ
Chemtex 2317 (3% based on solution weight), HeiQ Chemtex 2241-A (1%
based on solution weight), HeiQ Chemtex 2243 (0.1% based on
solution weight), 32 g of waterborne polyurethane dispersion L3360
from Hauthaway were added to the solution, and the solution was
stirred for 5 minutes at room temperature using an impeller at 500
rpm. This solution was then frothed to create a foam solution with
a wet density between 700 g/L and 900 g/L. The foam solution was
coated on the previously coated protein solution layer using the
Mathis LTE-S Labcoater and allowed to dry at 75.degree. C. for 10
minutes and at 100.degree. C. for 10 minutes. After this first
foamed solution coating was dried, a second foam layer was coated
on the first foamed coating using identical conditions After drying
of the second foam solution layer, the three-layer sample was
removed from the release paper.
[0370] The three-layer sample for Example No. 50a had a thickness
of 0.24 mm and the three-layer sample for Example No. 50b had a
thickness of 0.25 mm. As reported in Table 7, the sample for
Example No. 50a had a moisture vapor transmission rate of 268
g/m.sup.2/24 hr, which was a 185 g/m.sup.2/24 hr increase compared
to the sample of Example No. 49a and a 181 g/m.sup.2/24 hr increase
compared to the sample of Example No. 49b. As also reported in
Table 7, the sample for Example No. 50b had a moisture vapor
transmission rate of 277 g/m.sup.2/24 hr, which was a 194
g/m.sup.2/24 hr increase compared to the sample of Example No. 49a
and a 190 g/m.sup.2/24 hr increase compared to the sample of
Example No. 49b.
EXAMPLE 51
[0371] A control sample was prepared by mixing 0.4 g of AF-715 (an
antifoaming agent available from Quaker Color) into 38 g of
waterborne polyurethane dispersion IMPRAPERM.RTM. DL 5249 from
Covestro. The mixture was mixed using an impeller at a rate of 500
rpm and allowed to stir for 5 minutes at room temperature. After
the mixture was properly mixed, 0.6 g BORCHI.RTM. Gel L 75 N was
added to increase the viscosity of the mixture and the mixture was
allowed to mix for 5 minutes. The mixture was then coated using a
Mathis LTE-S Labcoater coater onto a release paper and was dried at
75.degree. C. for 10 minutes and at 100.degree. C. for 10 minutes.
The coating was then removed from the release paper to create a
polyurethane film containing no protein.
[0372] After drying, the sample had a thickness of 0.08 mm. As
reported in Table 7, the polyurethane film had a moisture vapor
transmission rate of 338 g/m.sup.2/24 hr.
EXAMPLE 52
[0373] Two samples (Example No. 52a and Example No. 52b) were each
prepared according to the following process. 5.3 g of SUPRO.RTM. XT
221D soy protein isolate was mixed with 30 g of water. The pH of
the mixture was then increased using 1M NaOH until a pH of 8-9 was
achieved. After adjusting the pH, Ultra-Fresh DW-56 (15 wt % based
on the soy protein isolate mass) and AF-715 antifoaming agent (1 wt
% based on solution weight) were added and to the mixture, and the
mixture was stirred using an impeller at 500 rpm until the soy
protein isolate was fully dissolved. Once the soy protein isolate
was fully dissolved, 32 g of waterborne polyurethane dispersion
IMPRAPERM.RTM. DL 5249 from Covestro was added to the protein
solution and the solution was stirred using an impeller at a rate
of 500 rpm for 10 minutes at room temperature. The protein solution
was then coated onto a release paper using a Mathis LTE-S Labcoater
and allowed to dry at 75.degree. C. for 10 minutes and at
100.degree. C. for 10 minutes.
[0374] Then a foam solution was prepared by mixing 5.3 g SUPRO.RTM.
XT 221D soy protein isolate with 30 g of water. The pH of the
mixture was increased using 1M NaOH until a pH of 8-9 was achieved.
After adjusting the pH and once the soy protein isolate was fully
dissolved, Ultra-Fresh DW-56 (15 wt % based on the soy protein
mass), HeiQ Chemtex 2216-T (3 wt % based on solution weight), HeiQ
Chemtex 2317 (3% based on solution weight), HeiQ Chemtex 2241-A (1%
based on solution weight), HeiQ Chemtex 2243 (0.1% based on
solution weight), 32 g of waterborne polyurethane dispersion
IMPRAPERM.RTM. DL 5249 from Covestro were added to the solution,
and the solution was stirred for 5 minutes at room temperature
using an impeller at 500 rpm. This solution was then frothed to
create a foamed solution with a wet density between 700 g/L and 900
g/L. The foamed solution was coated on the previously coated
protein solution layer using the Mathis LTE-S Labcoater and allowed
to dry at 75.degree. C. for 10 minutes and at 100.degree. C. for 10
minutes. After this first foamed coating was dried, a second foamed
layer was coated on the first foamed coating using identical
conditions After drying of the second foamed solution layer, the
three-layer sample was removed from the release paper.
[0375] The three-layer sample for Example No. 52a had a thickness
of 0.22 mm and the three-layer sample for Example No. 52b had a
thickness of 0.23 mm. As reported in Table 7, the sample for
Example 52a had a moisture vapor transmission rate of 626
g/m.sup.2/24 hr and the sample for Example 52b had a moisture vapor
transmission rate of 644 g/m.sup.2/24 hr. For purposes of
evaluating a change in moisture vapor transmission rate, these
moisture vapor transmission rates for Example Nos. 52a and 52b can
be compared to the moisture vapor transmission rate of Example No.
51 because all three samples included a non-foamed layer made using
IMPRAPERM.RTM. DL 5249 and having substantially the same thickness.
The foamed layers of Example Nos. 52a and 52b did not have a
significant influence on the moisture vapor transmission rates for
these samples because of their high degree of porosity. Compared to
the sample of Example No. 51, the sample of Example No. 52a showed
a 288 g/m.sup.2/24 hr increase in moisture vapor transmission and
the sample of Example No. 52b showed a 306 g/m.sup.2/24 hr increase
in moisture vapor transmission.
EXAMPLE 53
[0376] A control sample was prepared by mixing 0.2 g of AF-715 (an
antifoaming agent available from Quaker Color) into 38 g of
waterborne polyurethane dispersion IMPRAPERM.RTM. DL 5249 from
Covestro. The mixture was mixed using an impeller at a rate of 500
rpm for 5 minutes. After the mixture was properly mixed, 0.6 g
BORCHI.RTM. Gel L 75 N was added to increase the viscosity of the
mixture and the mixture was mixed again for 5 minutes. This
polyurethane mixture was then coated onto a release paper using a
Mathis LTE-S Labcoater and allowed to dry at 75.degree. C. for 10
minutes and at 100.degree. C. for 10 minutes.
[0377] Then a foam solution was then prepared by mixing waterborne
polyurethane dispersion L3360 from Hauthaway with HeiQ Chemtex
2216-T (3% based on solution weight), HeiQ Chemtex 2317 (3% based
on solution weight), HeiQ Chemtex 2241-A (1% based on solution
weight), and HeiQ Chemtex 2243 (0.1% based on solution weight).
This mixture was stirred for 5 minutes at room temperature using an
impeller at 500 rpm. The mixture was then frothed to create a
foamed mixture having a wet density between 700 g/L and 900 g/L.
The foamed mixture was coated on the previously coated polyurethane
layer using the Mathis LTE-S Labcoater and allowed to dry at
75.degree. C. for 10 minutes and at 100.degree. C. for 10 minutes.
After this first foamed coating was dried, a second foamed coating
layer made of the same L3360 foamed mixture was coated on the first
foamed coating using identical conditions. After drying of the
second foamed layer, the three-layer sample was removed from the
release paper.
[0378] The three-layer sample for Example No. 53 had a thickness of
0.32 mm. As reported in Table 7, the three-layer sample of Example
No. 53 had a moisture vapor transmission rate of 84 g/m.sup.2/24
hr.
EXAMPLE 54
[0379] A sample was prepared by mixing 5.3 g of SUPRO.RTM. XT 221D
soy protein isolate with 30 g of water. The pH of the mixture was
increased using 1M NaOH until a pH of 8-9 was achieved. After
adjusting the pH, Ultra-Fresh DW-56 (15 wt % based on the soy
protein isolate mass) and AF-715 antifoaming agent (1 wt % based on
solution weight) were added and to the mixture, and the mixture was
stirred using an impeller at 500 rpm until the soy protein isolate
was fully dissolved. Once the soy protein isolate was fully
dissolved, 53.7 g of waterborne polyurethane dispersion
IMPRAPERM.RTM. DL 5249 from Covestro was added to the protein
solution and the solution was stirred using an impeller at a rate
of 500 rpm for 10 minutes at room temperature. The protein solution
was then coated onto a release paper using a Mathis LTE-S Labcoater
and allowed to dry at 75.degree. C. for 10 minutes and at
100.degree. C. for 10 minutes.
[0380] Then a foam solution was prepared by mixing 5.3 g SUPRO.RTM.
XT 221D soy protein isolate with 30 g of water. The pH of the
mixture was increased using 1M NaOH until a pH of 8-9 was achieved.
After adjusting the pH and once the soy protein isolate was fully
dissolved, Ultra-Fresh DW-56 (15 wt % based on the soy protein
mass), HeiQ Chemtex 2216-T (3 wt % based on solution weight), HeiQ
Chemtex 2317 (3% based on solution weight), HeiQ Chemtex 2241-A (1%
based on solution weight), HeiQ Chemtex 2243 (0.1% based on
solution weight), 53.7 g of waterborne polyurethane dispersion
L3360 from Hauthaway were added to the solution, and the solution
was stirred for 5 minutes at room temperature using an impeller at
500 rpm. This solution was then frothed to create a foamed solution
with a wet density between 700 g/L and 900 g/L. The foamed solution
was coated on the previously coated protein solution layer using
the Mathis LTE-S Labcoater and allowed to dry at 75.degree. C. for
10 minutes and at 100.degree. C. for 10 minutes. After this first
foamed solution coating was dried, a second foam L3360 layer was
coated on the first foamed coating using identical conditions After
drying of the second foam solution layer, the three-layer sample
was removed from the release paper.
[0381] The three-layer sample for Example No. 54 had a thickness of
0.32 mm. As reported in Table 7, the sample for Example No. 54 had
a moisture vapor transmission rate of 166 g/m.sup.2/24 hr, which
was a 82 g/m.sup.2/24 hr increase compared to the sample of Example
No. 53. The graph of FIG. 23 shows that the breathability for the
sample of Example No. 54 is consistent over time. The amount of
water transported through the sample increased linearly with time
during the breathability test. The graph of FIG. 23 shows that the
protein in the protein polyurethane alloy does not cause any
significant fluctuations in the alloy's breathability over
time.
EXAMPLE 55
[0382] A control sample was prepared by mixing 0.4 g of AF-715 (an
antifoaming agent from Quaker Color) into 38 g of waterborne
polyurethane dispersion composed of 25 wt % IMPRAPERM.RTM. DL 5249
from Covestro and 75 wt % L3360 from Hauthaway. The mixture was
mixed using an impeller at a rate of 500 rpm and allowed to stir
for 5 minutes at room temperature. After the mixture was properly
mixed, 0.6 g BORCHI.RTM. Gel L 75 N was added to increase the
viscosity of the mixture and the mixture was allowed to mix for 5
minutes. The mixture was then coated using a Mathis LTE-S Labcoater
coater onto a release paper and was dried at 75.degree. C. for 10
minutes and at 100.degree. C. for 10 minutes. The coating was then
removed from the release paper to create a polyurethane film
containing no protein.
[0383] After drying, the sample had a thickness of 0.07 mm. As
reported in Table 7, the polyurethane film had a moisture vapor
transmission rate of 168 g/m.sup.2/24 hr.
EXAMPLE 56
[0384] A sample was prepared by mixing 5.3 g of SUPRO.RTM. XT 221D
soy protein isolate with 30 g of water. The pH of the mixture was
increased using 1M NaOH until a pH of 8-9 was achieved. After
adjusting the pH, Ultra-Fresh DW-56 (15 wt % based on the soy
protein isolate mass) and AF-715 antifoaming agent (1 wt % based on
solution weight) were added and to the mixture, and the mixture was
stirred using an impeller at 500 rpm until the soy protein isolate
was fully dissolved. Once the soy protein isolate was fully
dissolved, 53.7 g of waterborne polyurethane dispersion composed of
25 wt % IMPRAPERM.RTM. DL 5249 from Covestro and 75 wt % L3360 from
Hauthaway was added to the protein solution and the solution was
stirred using an impeller at a rate of 500 rpm for 10 minutes at
room temperature. The protein solution was then coated onto a
release paper using a Mathis LTE-S Labcoater and allowed to dry at
75.degree. C. for 10 minutes and at 100.degree. C. for 10
minutes.
[0385] After drying, the sample had a thickness of 0.05 mm. As
reported in Table 7, the sample had a moisture vapor transmission
rate of 266 g/m.sup.2/24 hr, which was a 98 g/m.sup.2/24 hr
increase compared to the sample of Example No. 55.
EXAMPLE TABLES
[0386] The following Tables 3-6 report the DMA and mechanical
property test results for Example Nos. 1-31. The "Sancure"
polyurethane in the tables is SANCURE.TM. 20025F, an aliphatic
polyester polyurethane dispersion at 47% solids in water from
Lubrizol. The "Impranil DLS" polyurethane is IMPRANIL.RTM. DLS, an
aliphatic polyester polyurethane with 50% solids content in water
from Covestro. The "L2996" polyurethane is an aliphatic
polycarbonate polyurethane dispersion with 35% solids content in
water from Hauthaway. The "Gelatin" protein is type A porcine skin
gelatin G2500 from Sigma. The "SPI" protein is soy protein isolate
IC90545625 from MP Medicals. The "Collagen" protein is bovine
collagen from Wuxi BIOT biology technology in China. The "BSA"
protein is bovine serum albumin 5470 from Sigma. The "rCol" protein
recombinant bovine collagen prepared in yeast from Modern Meadow.
The "Albumin" protein is chicken egg white albumin A5253 from
Sigma. The "Pea" protein is pea protein powder MTX5232 from Bobs
Red Mills. The "Peanut" protein is peanut protein powder from
Tru-Nut. Table 7 reports the moisture vapor transmission rate test
results for Example Nos. 45-56.
TABLE-US-00003 TABLE 3 Second DMA Modulus Transition Onset
Temperatures 2nd Modulus Delta 2nd Transition Modulus Protein PU
Onset Transition Ex. No. PU Protein (wt %) (wt %) (.degree. C.)
Onset 1 L3360 None 0% 100% 114.9 -- 2 UD-108 None 0% 100% 127.4 --
3 UD-250 None 0% 100% 160.8 -- 4 UD-303 None 0% 100% 158.1 -- 5
Impranil DLS None 0% 100% 146.4 -- 6 Sancure None 0% 100% 49.6 -- 7
HD-2001 None 0% 100% 128 -- 8 L2996 None 0% 100% 186.2 -- 9 L3360
Gelatin 30% 70% 180.6 65.7 10 UD-108 Gelatin 30% 70% 184.9 57.5 11
UD-250 Gelatin 30% 70% 186.1 25.3 12 Impranil DLS Gelatin 30% 70%
190.4 44 13 UD-303 Gelatin 30% 70% 179.5 21.4 14 Sancure Gelatin
30% 70% 188 138.4 15 HD2001 Gelatin 30% 70% 184.9 56.9 16 L2996
Gelatin 30% 70% 187.1 -- 17 L3360 Collagen 30% 70% 180.3 65.4 18
L3360 rCol 30% 70% 175.4 60.5 19 L3360 Albumen 30% 70% 168.4 53.5
20 L3360 BSA 30% 70% 184.9 70 21 L3360 SPI (pH 10) 30% 70% 186.6
71.7 22 L3360 Pea 30% 70% 186.2 71.3 23 L3360 Peanut 30% 70% 151.92
37 24 L3360 Gelatin 50% 50% -- -- 35 L3360 Gelatin 20% 80% 184 69.1
26 L3360 Gelatin 15% 85% 138.3 23.4 27 L3360 Gelatin 10% 90% 122.9
8 28 L3360 Gelatin 5% 95% 134.2 19.3 29 L3360 Gelatin 1% 99% -- --
30 L3360 SPI raw 10% 90% 133.9 19 31 L3360 SPI (pH 8) 20% 80% 187.1
72.2 42 L3360 50 KDa rCol 30% 70% 177.8 62.9 43 L3360 Cellulase-RG
20% 80% 153.1 38.2 44 L3360 Cellulase-IG 20% 80% 122.1 7.2
TABLE-US-00004 TABLE 4 First DMA Modulus Transition Onset
Temperatures & Soft Phase tan(.delta.) Peak Temperatures 1st
Delta Delta 1st Tan(.delta.) Modulus Tan(.delta.) Modulus peak
Transition Peak Transition Protein PU Temp. Onset Temp. Onset Ex.
No. PU Protein (wt %) (wt %) (.degree. C.) (.degree. C.) (.degree.
C.) (.degree. C.) 1 L3360 None 0% 100% -33 -50 -- -- 2 UD-108 None
0% 100% -46 -58 -- -- 3 UD-250 None 0% 100% -30 -- -- -- 4 UD-303
None 0% 100% -45 -59 -- -- 5 Impranil DLS None 0% 100% -29 -44 --
-- 6 Sancure None 0% 100% -39 -50 -- -- 7 HD-2001 None 0% 100% -20
-35 -- -- 8 L2996 None 0% 100% -20 -- -- -- 9 L3360 Gelatin 30% 70%
-39 -53 -6 -3 10 UD-108 Gelatin 30% 70% -47 -57 -1 1 11 UD-250
Gelatin 30% 70% -30 -- 0 -- 12 Impranil DLS Gelatin 30% 70% -36 -47
-7 -3 13 UD-303 Gelatin 30% 70% -52 -63 -7 -4 14 Sancure Gelatin
30% 70% -46 -55 -7 -5 15 HD2001 Gelatin 30% 70% -20 -36 0 -1 16
L2996 Gelatin 30% 70% 17 L3360 Collagen 30% 70% -35 -49 -2 1 18
L3360 rCol 30% 70% -33 -49 0 1 19 L3360 Albumen 30% 70% -36 -52 -3
-2 20 L3360 BSA 30% 70% -35 -49 -2 1 21 L3360 SPI (pH 10) 30% 70%
-38 -53 -5 -3 22 L3360 Pea 30% 70% -33 -52 0 -2 23 L3360 Peanut 30%
70% -41 -53 -8 -3 24 L3360 Gelatin 50% 50% -38 -52 -5 -2 25 L3360
Gelatin 20% 80% -32 -49 1 1 26 L3360 Gelatin 15% 85% -34 -51 -1 -1
27 L3360 Gelatin 10% 90% -33 -47 0 3 28 L3360 Gelatin 5% 95% -34
-49 -1 1 29 L3360 Gelatin 1% 99% -- -- -- -- 30 L3360 SPI raw 10%
90% -36 -49 -3 1 31 L3360 SPI (pH 8) 20% 80% -36 -51 -3 -1 42 L3360
50 KDa rCol 30% 70% -31 -47 2 3 43 L3360 Cellulase-RG 20% 80% -34
-48 -1 2 44 L3360 Cellulase-IG 20% 80% -33 -48 0 2
TABLE-US-00005 TABLE 5 Tensile Strength Tensile Delta % Delta
Protein PU Strength Tensile Tensile Ex. No. PU Protein (wt %) (wt
%) (MPa) Strength Strength 1 L3360 None 0% 100% 12.9 -- -- 2 UD-108
None 0% 100% 19.4 -- -- 3 UD-250 None 0% 100% 26.4 -- -- 4 UD-303
None 0% 100% 16.7 -- -- 5 Impranil DLS None 0% 100% 15.1 -- -- 6
Sancure None 0% 100% 1.4 -- -- 7 HD-2001 None 0% 100% 33 -- -- 8
L2996 None 0% 100% -- -- -- 9 L3360 Gelatin 30% 70% 19.8 6.9 53.8
10 UD-108 Gelatin 30% 70% 23.1 3.7 19.1 11 UD-250 Gelatin 30% 70%
-- -- -- 12 Impranil DLS Gelatin 30% 70% 17.9 2.8 18.5 13 UD-303
Gelatin 30% 70% 23.2 6.5 38.9 14 Sancure Gelatin 30% 70% 15.3 13.9
993 15 HD2001 Gelatin 30% 70% 17.9 -15.1 -45.8 16 L2996 Gelatin 30%
70% -- -- -- 17 L3360 Collagen 30% 70% 17.3 4.4 34.4 18 L3360 rCol
30% 70% 16.8 3.9 29.9 19 L3360 Albumen 30% 70% 14.8 1.9 14.9 20
L3360 BSA 30% 70% 11.7 -1.2 -9.1 21 L3360 SPI (pH 10) 30% 70% 18.2
5.3 41.1 22 L3360 Pea 30% 70% 15.3 2.4 18.4 23 L3360 Peanut 30% 70%
11 -1.9 -14.5 24 L3360 Gelatin 50% 50% -- -- -- 25 L3360 Gelatin
20% 80% 17.2 4.3 33.5 26 L3360 Gelatin 15% 85% 16 3.1 24.3 27 L3360
Gelatin 10% 90% 16.8 3.9 29.9 28 L3360 Gelatin 5% 95% 11.2 -1.7 -13
29 L3360 Gelatin 1% 99% 11.8 -1.1 -8.7 30 L3360 SPI raw 10% 90%
14.6 1.7 13.4 31 L3360 SPI (pH 8) 20% 80% 18 5.1 39.3 42 L3360 50
KDa rCol 30% 70% 17 4.1 31.8 43 L3360 Cellulase-RG 20% 80% 14.7 1.8
14 44 L3360 Cellulase-IG 20% 80% 15.1 2.2 17
TABLE-US-00006 TABLE 6 Young's Modulus Young's Delta % Delta
Protein PU Modulus Young's Young's Ex. No. PU Protein (wt %) (wt %)
(MPa) Modulus Modulus 1 L3360 None 0% 100% 59 -- -- 2 UD-108 None
0% 100% 23 -- -- 3 UD-250 None 0% 100% 557 -- -- 4 UD-303 None 0%
100% 27 -- -- 5 Impranil DLS None 0% 100% 13 -- -- 6 Sancure None
0% 100% 337 -- -- 7 HD-2001 None 0% 100% 20 -- -- 8 L2996 None 0%
100% - -- -- 9 L3360 Gelatin 30% 70% 344 285 478 10 UD-108 Gelatin
30% 70% 324 301 1308 11 UD-250 Gelatin 30% 70% -- -- -- 12 Impranil
DLS Gelatin 30% 70% 326 313 2407 13 UD-303 Gelatin 30% 70% 379 352
1304 14 Sancure Gelatin 30% 70% 579 242 71.8 15 HD2001 Gelatin 30%
70% 115 95 475 16 L2996 Gelatin 30% 70% -- -- -- 17 L3360 Collagen
30% 70% 226 167 280 18 L3360 rCol 30% 70% 169 110 184 19 L3360
Albumen 30% 70% 204 145 243 20 L3360 BSA 30% 70% 174 114 192 21
L3360 SPI (pH 10) 30% 70% 396 337 566 22 L3360 Pea 30% 70% 163 104
175 23 L3360 Peanut 30% 70% 87 28 47 24 L3360 Gelatin 50% 50% -- --
-- 25 L3360 Gelatin 20% 80% 129 70 117 26 L3360 Gelatin 15% 85% 93
33 56 27 L3360 Gelatin 10% 90% 71 11 19 28 L3360 Gelatin 5% 95% 51
-9 -14 29 L3360 Gelatin 1% 99% 54 -5 -9 30 L3360 SPI raw 10% 90% 95
36 60 31 L3360 SPI (pH 8) 20% 80% 223 164 275 42 L3360 50 KDa rCol
30% 70% 161 102 173 43 L3360 Cellulase-RG 20% 80% 184 125 212 44
L3360 Cellulase-IG 20% 80% 84 25 42
TABLE-US-00007 TABLE 7 Moisture Vapor Transmission Rate (MVTR)
Protein PU MVTR Delta % Delta Ex. No. PU Protein (wt %) (wt %)
(g/m.sup.2/24 hr) MVTR MVTR 45a HD-2001 None 0% 100% 30 -- -- 45b
HD-2001 None 0% 100% 38 -- -- 46a HD-2001 Gelatin 30% 70% 180
142-150 374-500 46b HD-2001 Gelatin 30% 70% 138 100-108 263-360 47a
L3360 None 0% 100% 23 -- -- 47b L3360 None 0% 100% 27 -- -- 48a
L3360 SPI 30% 70% 117 90-94 333-409 48b L3360 SPI 30% 70% 74 47-51
174-222 49a L3360 None 0% 100% 83 -- -- 49b L3360 None 0% 100% 87
-- -- 50a L3360 SPI 30% 70% 268 181-185 208-223 50b L3360 SPI 30%
70% 277 190-194 218-233 51 Impraperm None 0% 100% 338 -- -- 5249
52a Impraperm SPI 30% 70% 626 288 85 5249 52b Impraperm SPI 30% 70%
644 306 91 5249 53 Impraperm None 0% 100% 84 -- -- 5249 & L-
3360 54 Impraperm SPI 20% 80% 166 82 98 5249 & L- 3360 55
Impraperm None 0% 100% 168 -- -- 5249 & L- 3360 56 Impraperm
SPI 20% 80% 266 98 58 5249 & L- 3360
[0387] While various embodiments have been described herein, they
have been presented by way of example, and not limitation. It
should be apparent that adaptations and modifications are intended
to be within the meaning and range of equivalents of the disclosed
embodiments, based on the teaching and guidance presented herein.
It therefore will be apparent to one skilled in the art that
various changes in form and detail can be made to the embodiments
disclosed herein without departing from the spirit and scope of the
present disclosure. The elements of the embodiments presented
herein are not necessarily mutually exclusive, but can be
interchanged to meet various situations as would be appreciated by
one of skill in the art.
[0388] Embodiments of the present disclosure are described in
detail herein with reference to embodiments thereof as illustrated
in the accompanying drawings, in which like reference numerals are
used to indicate identical or functionally similar elements.
References to "one embodiment," "an embodiment," "some
embodiments," "in certain embodiments," etc., indicate that the
embodiment described can include a particular feature, structure,
or characteristic, but every embodiment can not necessarily include
the particular feature, structure, or characteristic. Moreover,
such phrases are not necessarily referring to the same embodiment.
Further, when a particular feature, structure, or characteristic is
described in connection with an embodiment, it is submitted that it
is within the knowledge of one skilled in the art to affect such
feature, structure, or characteristic in connection with other
embodiments whether or not explicitly described.
[0389] The examples are illustrative, but not limiting, of the
present disclosure. Other suitable modifications and adaptations of
the variety of conditions and parameters normally encountered in
the field, and which would be apparent to those skilled in the art,
are within the spirit and scope of the disclosure.
[0390] It is to be understood that the phraseology or terminology
used herein is for the purpose of description and not of
limitation. The breadth and scope of the present disclosure should
not be limited by any of the above-described exemplary embodiments,
but should be defined in accordance with the following claims and
their equivalents.
TABLE-US-00008 SEQUENCES Human Collagen alpha-1 (III) chain SEQ ID
NO: 1: DVKSGVAVGGLAGYPGPAGPPGPPGPPGTSGHPGSPGSPGYQGPPGEPGQA
GPSGPPGPPGAIGPSGPAGKDGESGRPGRPGERGLPGPPGIKGPAGIPGFP
GMKGHRGFDGRNGEKGETGAPGLKGENGLPGENGAPGPMGPRGAPGERGRP
GLPGAAGARGNDGARGSDGQPGPPGPPGTAGFPGSPGAKGEVGPAGSPGSN
GAPGQRGEPGPQGHAGAQGPPGPPGINGSPGGKGEMGPAGIPGAPGLMGAR
GPPGPAGANGAPGLRGGAGEPGKNGAKGEPGPRGERGEAGIPGVPGAKGED
GKDGSPGEPGANGLPGAAGERGAPGFRGPAGPNGIPGEKGPAGERGAPGPA
GPRGAAGEPGRDGVPGGPGMRGMPGSPGGPGSDGKPGPPGSQGESGRPGPP
GPSGPRGQPGVMGFPGPKGNDGAPGKNGERGGPGGPGPQGPPGKNGETGPQ
GPPGPTGPGGDKGDTGPPGPQGLQGLPGTGGPPGENGKPGEPGPKGDAGAP
GAPGGKGDAGAPGERGPP
Sequence CWU 1
1
11528PRTArtificial SequenceHuman Collagen alpha-1(III) chain 1Asp
Val Lys Ser Gly Val Ala Val Gly Gly Leu Ala Gly Tyr Pro Gly1 5 10
15Pro Ala Gly Pro Pro Gly Pro Pro Gly Pro Pro Gly Thr Ser Gly His
20 25 30Pro Gly Ser Pro Gly Ser Pro Gly Tyr Gln Gly Pro Pro Gly Glu
Pro 35 40 45Gly Gln Ala Gly Pro Ser Gly Pro Pro Gly Pro Pro Gly Ala
Ile Gly 50 55 60Pro Ser Gly Pro Ala Gly Lys Asp Gly Glu Ser Gly Arg
Pro Gly Arg65 70 75 80Pro Gly Glu Arg Gly Leu Pro Gly Pro Pro Gly
Ile Lys Gly Pro Ala 85 90 95Gly Ile Pro Gly Phe Pro Gly Met Lys Gly
His Arg Gly Phe Asp Gly 100 105 110Arg Asn Gly Glu Lys Gly Glu Thr
Gly Ala Pro Gly Leu Lys Gly Glu 115 120 125Asn Gly Leu Pro Gly Glu
Asn Gly Ala Pro Gly Pro Met Gly Pro Arg 130 135 140Gly Ala Pro Gly
Glu Arg Gly Arg Pro Gly Leu Pro Gly Ala Ala Gly145 150 155 160Ala
Arg Gly Asn Asp Gly Ala Arg Gly Ser Asp Gly Gln Pro Gly Pro 165 170
175Pro Gly Pro Pro Gly Thr Ala Gly Phe Pro Gly Ser Pro Gly Ala Lys
180 185 190Gly Glu Val Gly Pro Ala Gly Ser Pro Gly Ser Asn Gly Ala
Pro Gly 195 200 205Gln Arg Gly Glu Pro Gly Pro Gln Gly His Ala Gly
Ala Gln Gly Pro 210 215 220Pro Gly Pro Pro Gly Ile Asn Gly Ser Pro
Gly Gly Lys Gly Glu Met225 230 235 240Gly Pro Ala Gly Ile Pro Gly
Ala Pro Gly Leu Met Gly Ala Arg Gly 245 250 255Pro Pro Gly Pro Ala
Gly Ala Asn Gly Ala Pro Gly Leu Arg Gly Gly 260 265 270Ala Gly Glu
Pro Gly Lys Asn Gly Ala Lys Gly Glu Pro Gly Pro Arg 275 280 285Gly
Glu Arg Gly Glu Ala Gly Ile Pro Gly Val Pro Gly Ala Lys Gly 290 295
300Glu Asp Gly Lys Asp Gly Ser Pro Gly Glu Pro Gly Ala Asn Gly
Leu305 310 315 320Pro Gly Ala Ala Gly Glu Arg Gly Ala Pro Gly Phe
Arg Gly Pro Ala 325 330 335Gly Pro Asn Gly Ile Pro Gly Glu Lys Gly
Pro Ala Gly Glu Arg Gly 340 345 350Ala Pro Gly Pro Ala Gly Pro Arg
Gly Ala Ala Gly Glu Pro Gly Arg 355 360 365Asp Gly Val Pro Gly Gly
Pro Gly Met Arg Gly Met Pro Gly Ser Pro 370 375 380Gly Gly Pro Gly
Ser Asp Gly Lys Pro Gly Pro Pro Gly Ser Gln Gly385 390 395 400Glu
Ser Gly Arg Pro Gly Pro Pro Gly Pro Ser Gly Pro Arg Gly Gln 405 410
415Pro Gly Val Met Gly Phe Pro Gly Pro Lys Gly Asn Asp Gly Ala Pro
420 425 430Gly Lys Asn Gly Glu Arg Gly Gly Pro Gly Gly Pro Gly Pro
Gln Gly 435 440 445Pro Pro Gly Lys Asn Gly Glu Thr Gly Pro Gln Gly
Pro Pro Gly Pro 450 455 460Thr Gly Pro Gly Gly Asp Lys Gly Asp Thr
Gly Pro Pro Gly Pro Gln465 470 475 480Gly Leu Gln Gly Leu Pro Gly
Thr Gly Gly Pro Pro Gly Glu Asn Gly 485 490 495Lys Pro Gly Glu Pro
Gly Pro Lys Gly Asp Ala Gly Ala Pro Gly Ala 500 505 510Pro Gly Gly
Lys Gly Asp Ala Gly Ala Pro Gly Glu Arg Gly Pro Pro 515 520 525
* * * * *