U.S. patent application number 17/192513 was filed with the patent office on 2021-09-09 for antimicrobial/antiviral plastics and molded products.
This patent application is currently assigned to Ascend Performance Materials Operations LLC. The applicant listed for this patent is Ascend Performance Materials Operations LLC. Invention is credited to Vikram GOPAL, Austin MAPLES, Albert ORTEGA, Bradley J. SPARKS, Joseph SURIANO, Wai-shing YUNG.
Application Number | 20210277203 17/192513 |
Document ID | / |
Family ID | 1000005445262 |
Filed Date | 2021-09-09 |
United States Patent
Application |
20210277203 |
Kind Code |
A1 |
GOPAL; Vikram ; et
al. |
September 9, 2021 |
ANTIMICROBIAL/ANTIVIRAL PLASTICS AND MOLDED PRODUCTS
Abstract
A polymer composition for molded products having antimicrobial
and/or antiviral properties comprising from 50 wt. % to 99.9 wt. %
of a polymer, from 0.01 wt % to 10 wt % zinc, optionally from a
zinc compound, less than 1 wt % of a phosphorus compound, and from
0 wt % to 20 wt % molding additives, wherein a molded product
formed from the polymer composition demonstrates a Staphylococcus
aureus log reduction greater than 1.0, as determined via ISO
22196:2011.
Inventors: |
GOPAL; Vikram; (Houston,
TX) ; YUNG; Wai-shing; (Houston, TX) ; ORTEGA;
Albert; (Houston, TX) ; SPARKS; Bradley J.;
(Houston, TX) ; SURIANO; Joseph; (Houston, TX)
; MAPLES; Austin; (Houston, TX) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Ascend Performance Materials Operations LLC |
Houston |
TX |
US |
|
|
Assignee: |
Ascend Performance Materials
Operations LLC
Houston
TX
|
Family ID: |
1000005445262 |
Appl. No.: |
17/192513 |
Filed: |
March 4, 2021 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62985091 |
Mar 4, 2020 |
|
|
|
63000717 |
Mar 27, 2020 |
|
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63105051 |
Oct 23, 2020 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08L 77/06 20130101;
B29K 2105/0011 20130101; B29K 2995/0092 20130101; C08L 2201/08
20130101; C08K 3/08 20130101; C08K 2003/0893 20130101; B29C 48/022
20190201; C08K 2201/00 20130101; C08L 2201/02 20130101; B29K
2995/0077 20130101; B29K 2077/00 20130101 |
International
Class: |
C08K 3/08 20060101
C08K003/08; C08L 77/06 20060101 C08L077/06; B29C 48/00 20060101
B29C048/00 |
Claims
1. A polymer composition for molded products having antimicrobial
and/or antiviral properties comprising: from 50 wt. % to 99.9 wt. %
of a polymer, from 0.01 wt % to 10 wt % zinc, optionally from a
zinc compound, less than 1 wt % of a phosphorus compound, and from
0 wt % to 20 wt % molding additives, wherein a molded product
formed from the polymer composition demonstrates a Staphylococcus
aureus log reduction greater than 1.0, as determined via ISO
22196:2011.
2. The polymer composition of claim 1, wherein a molded product
formed from the polymer composition demonstrates an Escherichia
coli log reduction greater than 1.0, as determined via ISO
22196:2011.
3. The polymer composition of claim 1, wherein a molded product
formed from the polymer composition demonstrates a Klebsiella
pneumonia log reduction greater than 1.0, as determined via ISO
22196:2011.
4. The polymer composition of claim 1, wherein a molded product
formed from the polymer composition demonstrates a tensile modulus
greater than 2500 MPa and/or a Charpy un-notched impact energy loss
greater than 70 kJ/m.sup.2, at 23.degree. C.
5. The polymer composition of claim 1, wherein the polymer is
hydrophilic and/or hygroscopic and is capable of absorbing greater
than 1.5 wt % water, based on the total weight of the polymer.
6. The polymer composition of claim 1, wherein the composition
comprises from 1000 ppm to 7000 wppm zinc.
7. The polymer composition of claim 1, wherein the composition
comprises from 2 wt % to 20 wt % of impact modifier.
8. The polymer composition of claim 1, wherein the composition
comprises from 2 wt % to 20 wt % flame retardant.
9. The polymer composition of claim 1, wherein the composition
comprises from 0.1 to 5 wt % heat stabilizer and/or from 0.05 wt %
to 3 wt % melt stabilizer.
10. The polymer composition of claim 1, wherein the composition
comprises PA-6,6 and PA-6.
11. The polymer composition of claim 1, wherein the composition
comprises impact modifier and heat stabilizer and wherein the
weight ratio of impact modifier to heat stabilizer ranges from 0.5
to 23.
12. A molded product having antimicrobial and/or antiviral
properties, comprising: from 50 wt. % to 99.9 wt. % of a polymer,
from 0.01 wt % to 10 wt % zinc, optionally from a zinc compound,
less than 1 wt % of a phosphorus compound, and from 0 wt % to 20 wt
% molding additives, wherein a molded product formed from the
polymer composition demonstrates a Klebsiella pneumonia log
reduction greater than 1.0, as determined via ISO 22196:2011.
13. The molded product of claim 12, wherein the molded product
demonstrates a tensile modulus greater than 2500 MPa and/or a
Charpy un-notched impact energy loss greater than 70 kJ/m.sup.2, at
23.degree. C.
14. The molded product of claim 12, wherein the polymer is
hydrophilic and/or hygroscopic is capable of absorbing greater than
1.5 wt % water, based on the total weight of the polymer.
15. The molded product of claim 12, wherein the composition
comprises from 1000 ppm to 7000 wppm zinc.
16. The molded product of claim 12, wherein the molded product has
a zinc retention rate greater than 65%.
17. The molded product of claim 12, wherein the molded product is a
cable tie.
18. The molded product of claim 12, wherein the molded product is
medical equipment.
19. The molded product of claim 18, wherein the medical equipment
is reusable.
20. The molded product of claim 12, wherein the zinc compound
comprises zinc oxide, zinc stearate, zinc ammonium adipate, zinc
acetate, or zinc pyrithione, or combinations thereof.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to U.S. Provisional
Application No. 62/985,091, filed Mar. 4, 2020, U.S. Provisional
Application No. 63/000,717, filed Mar. 27, 2020, and U.S.
Provisional Application No. 63/105,051, filed Oct. 23, 2020, each
of which is incorporated herein by reference.
FIELD
[0002] The present disclosure relates to polymer compositions and
molded products having antimicrobial and/or antiviral properties.
In particular, the present disclosure relates to antiviral products
(e.g., fibers, fabrics, high-contact products) formed from a
polymer composition comprising unique antimicrobial components.
BACKGROUND
[0003] There is a growing interest in products, e.g., molded
products, having antiviral and/or antimicrobial properties. In an
attempt to achieve such properties, conventional techniques have
applied a number of treatments or coatings to conventional products
to impart antimicrobial properties thereto. Compounds containing
copper, silver, gold, or zinc, either individually or in
combination, have been used in these applications--typically in the
form of a topical coating treatment--to effectively combat
pathogens such as bacteria, mold, mildew, virus, spores, and
fungus. These products are often in the form of coated
antimicrobial fibers and fabrics, which may be used in many
industries including healthcare, hospitality, military, and
athletics, among others. However, these coated products have not
demonstrated adequately effective and lasting antimicrobial and/or
antiviral (AM/AV) properties.
[0004] For example, in the healthcare and hospitality industries,
certain items, e.g., monitoring equipment, ventilators, or even
patient charts, are required to be sanitary at all times. Many of
these products are molded products, not spun fabrics. To comply
with these sanitation standards, the items are subject to daily
washing and, often times, bleaching. Thus, in many applications
repeated cycles of use, washing, or soaking are quite common.
Unfortunately, conventional molded products have been found to
deteriorate and lose AM/AV properties during repeated uses and/or
wash cycles. Thus, many of the conventional polymer compositions
intended for antimicrobial fabrics do not demonstrate sufficient
AM/AV properties, nor do they retain these properties after
washing. Further, conventional AM/AV treatments/coatings that may
be extracted from conventional fabrics may have undesired
environmental consequences.
[0005] As one example, U.S. Pat. No. 6,584,668 discloses durable
non-electrically conductive metal treatments applied to yarns and
textile fabrics. The durable non-electrically conductive metal
treatments are coatings or finishes applied to yarns and textile
fabrics. The metal treatments may include silver and/or silver
ions, zinc, iron, copper, nickel, cobalt, aluminum, gold,
manganese, magnesium, and the like. The metal treatments are
applied to the exterior surface of the yarn or fabric as a coating
or film.
[0006] Some synthetic fibers having antimicrobial fibers are also
known in the art. For example, U.S. Pat. No. 4,701,518 discloses an
antimicrobial nylon prepared in water with a zinc compound
phosphorus compound to form carpet fibers. The process produces
nylon fibers for carpets having 18 denier per filament (dpf), and
are prepared by conventional melt polymerization. Such carpet
fibers typically have average diameters that are well above 30
microns, which are generally unsuitable for next-to-skin
applications. Furthermore, the conventional additives added to
polymer compositions to impart antimicrobial properties in the
synthetic fibers made therefrom have been found to reduce the
relative viscosity in the polymer compositions. This reduced
relative viscosity produces processing difficulties and also would
likely not be suitable for molded products, which are produced by
entirely different processes.
[0007] As another example, US Publication No. 2020/0102673
discloses antimicrobial fibers that include antimicrobial
nanoparticles dispersed substantially uniformly in a polymer
matrix. Textiles and other materials can be formed from such
fibers. The fibers may be formed via a masterbatch process or in a
process wherein the antimicrobial nanoparticles, polymeric
component, and additive(s) are melt processed together directly.
Devices can be at least partially formed from polymer materials
that include antimicrobial nanoparticles dispersed substantially
uniformly in a polymer matrix. Again, the teachings in this
reference are not applicable to the AM/AV molded products disclosed
herein.
[0008] Although some references may teach the use of antimicrobial
agents, a need exists for antiviral polymer compositions for the
production of molded products that have AM/AV properties and that
retain these properties, while also being able to achieve
mechanical performance suitable for molded product applications,
e.g., tensile strength or impact resistance.
SUMMARY
[0009] In some cases, the present disclosure relates to a polymer
composition for molded products having antimicrobial and/or
antiviral properties comprising from 50 wt. % to 99.9 wt. % of a
polymer, e.g., PA-6,6 and/or PA-6, from 0.01 wt % to 10 wt % zinc,
e.g., from 1000 ppm to 7000 wppm, optionally from a zinc compound,
less than 1 wt % of a phosphorus compound, and from 0 wt % to 20 wt
% molding additives. A molded product formed from the polymer
composition demonstrates a Klebsiella pneumonia log reduction
greater than 1.0 and/or a Staphylococcus aureus log reduction
greater than 1.0 and/or an Escherichia coli log reduction greater
than 1.0, as determined via ISO 22196:2011 and/or a tensile modulus
greater than 2500 MPa and/or a Charpy un-notched impact energy loss
greater than 70 kJ/m.sup.2, at 23.degree. C. The polymer may be
hydrophilic and/or hygroscopic and capable of absorbing greater
than 1.5 wt % water, based on the total weight of the polymer. The
zinc compound may comprise zinc oxide, zinc stearate, zinc ammonium
adipate, zinc acetate, or zinc pyrithione, or combinations thereof.
The polymer composition may further comprise from 2 wt % to 20 wt %
of impact modifier and/or from 2 wt % to 20 wt % flame retardant
and/or from 0.1 to 5 wt % heat stabilizer and/or from 0.05 wt % to
3 wt % melt stabilizer, where in some cases, the weight ratio of
impact modifier to heat stabilizer ranges from 0.5 to 23. The
present disclosure also relates to the molded product (made from
the polymer composition) having antimicrobial and/or antiviral
properties and comprising: from 50 wt. % to 99.9 wt. % of a
polymer, from 0.01 wt % to 10 wt % zinc, optionally from a zinc
compound, less than 1 wt % of a phosphorus compound, and from 0 wt
% to 20 wt % molding additives, and having the aforementioned
performance properties. The molded product may have a zinc
retention rate greater than 65%. The molded product may be a cable
tie or medical equipment and may be reusable.
DETAILED DESCRIPTION
Introduction
[0010] As discussed above, some conventional antiviral (and/or
antimicrobial) (AM/AV) polymer compositions and fabrics utilize
antiviral (and/or antimicrobial) compounds to inhibit viruses and
other pathogens. For example, some items may include antimicrobial
additives, e.g., silver, coated or applied as a film on an exterior
layer. However, it has been found that these treatments or coatings
often present a host of problems. The inventors have found that, in
some conventional applications where antiviral additives are
components of fibers, the antiviral additives may extract out of
the fibers/fabric during the use and/or washing, which adversely
affects the AM/AV properties and detrimentally places the additives
into the environment. In addition to this problem, the inventors
have discovered that some antiviral additives may negatively impact
the relative viscosity (RV) and/or strength performance of the
resultant polymer compositions and molded products.
[0011] It has now been found that the use of a polymer composition
comprising specific components, optionally employed in particular
amounts, provides for compositions and products that strike a
synergistic balance between AM/AV properties, relative viscosity,
mechanical performance, and hydrophilicity and/or hygroscopy. These
polymer compositions may be particularly useful in producing molded
products, where such performance properties are most germane.
Without being bound by theory, the use of specific AM/AV compounds,
e.g., zinc, copper, and/or silver compounds, in combination with
other molding composition additives such as antioxidants,
stearates, waxes, etc., provides for AM/AV efficacy, while also
providing suitable RV for molding operations. In addition, it has
been discovered the that having or maintaining specific levels of
hydrophilicity and/or hygroscopy in the polymer allows for and
advantageously improves the ability of the molded products to
contact and kill microbials and/or viruses. The inventors have also
found that certain hydrophilic substrates may better attract liquid
media that carry microbials and/or viruses, e.g., saliva or mucous.
The employment of the disclosed AM/AV agents in such substrates,
e.g., in the polymer matrices thereof, can be used to more
effectively combat the microbials and/or viruses, versus a less
hydrophilic substrate. The hydrophilicity and/or hygroscopy
contributes to ability of the molded products to be water-friendly,
which promotes microbial/virus contact with water, which in turn
promotes more effective reduction/killing of microbials and/or
viruses. At least some of these benefits are achieved while still
maintaining mechanical performance suitable for molded product
applications.
[0012] In addition, it is postulated that the use of the
aforementioned components (including the molding additives) in the
specific amounts may allow the zinc compound (zinc) or copper
compound (copper) to be more stably disposed in the polymer matrix
and, as such, may retard leaching of the zinc/copper compound from
the molded products, e.g., during everyday use or washing. Stated
another way, the polymer composition may have certain amounts of a
zinc/copper and optionally phosphorus embedded in the polymer
matrix such that the polymer composition maintains a higher
relative viscosity and retains antimicrobial properties during and
after use. In addition, the use of the phosphorus compound, in some
cases, in the specific amounts may work with the zinc/copper to
improve the relative viscosity of the polymer matrix.
[0013] As a result of the composition of the polymer, the disclosed
products made from the polymer compositions advantageously
eliminate the need for a topical treatment to make product
antiviral. The present AM/AV products have "built-in" AM/AV
properties. And these properties beneficially will not extract out,
e.g., wash away, after use.
[0014] Some references, e.g., (carpet) fiber-related references,
have disclosed the use of an antimicrobial nylon prepared in water
with a zinc compound and phosphorus compound to form the carpet
fibers. These references, however, relate to higher denier carpet
fibers/filaments. These teachings (and fiber teachings generally),
however are typically not relevant to other larger, more
substantive, products, e.g., molded products, used in furniture or
medical devices. Carpet fibers are formed via entirely different,
non-analogous processes equipment, which results in entirely
different products. In view of these significant differences, the
teachings of such fiber references are not typically considered
relevant to molded products. Also, fibers do not demonstrate the
mechanical performance necessary for many molded product
applications. Further, because the fiber production process is
entirely different from the molding process, these references do
not disclose or contemplate the use of molding additives or the
complexities associated therewith.
[0015] Also, although some references directly mix antiviral and/or
antimicrobial agents with fibers, leathers, or plastics, these
references do not address/solve problems of deterioration of the
antiviral properties of the products, e.g., via extraction loss
during use or washing/cleaning and/or mechanical strength.
[0016] In addition, as a result of the formulations disclosed
herein, the disclosed polymer compositions and products do not need
to be (and are not) gelled, which adds complications to processing,
e.g., compositional requirements to achieve the gelling and/or
process requirements to do the same, as well as the inability to
achieve high throughput. Thus, the disclosed polymers and products
provide the additional advantages of not including components
necessary for gelling as well as elimination of production steps
related to the gelling process.
[0017] The disclosure also relates to processes for making AM/AV
product. The processes comprises the steps of providing the polymer
composition having antiviral properties, and forming the polymer
composition into the molded product.
High-Contact Products
[0018] The present disclosure relates to various applications of
the antiviral polymer compositions and the polymer structures
formed therefrom. As described above, these products demonstrate
lasting antiviral properties. Thus, the polymer composition can be
incorporated into any of a variety of products for which prolonged
protection from viral infection and/or pathogenesis may be
desirable. Some exemplary products, e.g., molded products
follow.
[0019] The polymer composition may be used in the preparation of a
high-contact product. A high-contact product may be any product
that is handled, e.g., touched, by a user or otherwise comes into
contact with the user during conventional use. The polymer
compositions may be utilized for high-contact products used in any
setting.
[0020] In some embodiments, a disclosed polymer composition alone
is used to prepare a high-contact product. Said another way, a
high-contact product may be entirely composed of a polymer
composition. In some embodiments, a disclosed polymer composition
is a component of the high contact product. For example, the
polymer composition may form a layer, e.g., a surface coating, on
the high-contact product.
[0021] As discussed above, the polymer compositions described
herein demonstrate antiviral properties, and these properties may
be surprisingly enhanced by certain characteristics of the polymer
composition. For example, the use of a hydrophilic and/or
hygroscopic polymer improves, e.g., increases, the antiviral
activity of the polymer composition. Moisture, e.g., moisture
present on the skin, in sweat, or in saliva, typically facilitates
viral transmission, and a hydrophilic and/or hygroscopic polymer
composition may draw in virus-containing moisture. Thus, the
polymer compositions may be especially useful for high-contact
products that come into contact with moisture during typical use.
In particular, the moisture may be attracted to the composition,
e.g., on a surface of the high-contact product, and the composition
may then kill a virus contained therein. Thus, the disclosed
polymer compositions may be used in forming (in whole or in part)
high-contact products that greatly reduce transmission of a virus.
For example, the polymer compositions may be especially useful for
medical devices, masks, e.g., medical masks, and air filters, e.g.,
HVAC filters, automobile filters, aviation filters.
[0022] The following examples are illustrative and should not be
read as limiting the definition of a high-contact product. In some
cases, the high-contact product may be a piece or portion of
furniture, e.g., for use in an academic, business, or medical
setting. For example, the polymer composition may be used in the
preparation of a chair, e.g., as a part or all of a chair base, a
chair handle, a chair seatback, or a chair leg, a table, e.g., as a
part or all of a tabletop or a table leg, a desk, e.g., as a part
or all of a desktop or a desk leg, shelving, or a bed, e.g., as a
part or all of a bedframe, a bed railing, a bed leg, a headboard,
or a footboard.
[0023] In some cases, the high-contact product may be a piece or
portion of a consumer product, e.g., consumer electronics. For
example, the polymer composition may be used in the preparation of
a housing or case for a cellular phone, a component of computer,
e.g., a housing, a display, a keyboard, or a mouse of a desktop
computer or a laptop computer, a component of a kitchen or culinary
item (e.g., a refrigerator, oven, stove, range, microwave oven,
cookware, or cooking utensil), or a component of a personal hygiene
product. e.g., a toothbrush (or the fibers/bristles thereof), hair
brush, comb, toilet seat, toilet seat cover, razor, or an air
filter.
[0024] In some cases, the high-contact product may be a piece or
portion of medical equipment. For example, the polymer composition
may be used in the preparation of monitor equipment, e.g., a blood
pressure monitor or an ultrasound probe, radiology equipment. e.g.,
a portion of an MRI machine or a CT machine, a ventilator, or a
patient transfer sheet.
[0025] In some cases, the high-contact product may be a piece or
portion of a textile product. For example, the polymer composition
may be used in the preparation of clothing, a medical gown, a
medical mask, a medical drape, a patient transfer slip sheet,
curtains, bedding, e.g., bedsheets, a duvet, a duvet cover, a
pillow, or a pillow cover, or luggage, e.g., a suitcase or a
garment bag, shoes, e.g., a shoe upper, a shoe lining, or sewing
thread for a shoe.
[0026] In some cases, the high-contact product may be a molded
article. For example, the polymer composition may be used in the
preparation of packaging, e.g., disposable or reusable food and/or
liquid packaging, automotive parts or components, mechanical parts,
toys, musical instruments, furniture, or storage containers.
[0027] As another specific example, the polymer compositions may be
employed in making AM/AV cable ties. Here, the combination of AM/AV
properties and mechanical strength is synergistic.
[0028] Methods of making the high-contact product are not
particularly limited, and conventional methods may be used. In some
embodiments, for example, a hot melt polymerization, e.g., as
discussed above with respect to fibers and nonwoven polymer
structures, may be used to prepare the polymer composition, which
may then be extruded and/or formed into the high-contact
product.
Other Molded Products
[0029] The present disclosure relates to various applications of
the antiviral polymer compositions and the polymer structures
formed therefrom. As described above, these products demonstrate
lasting antiviral properties. Thus, the polymer composition can be
incorporated into any of a variety of products for which prolonged
protection from viral infection and/or pathogenesis may be
desirable.
[0030] In some aspects, a medical product or device may be prepared
using the polymer compositions described herein. In some
embodiments, for example, a medical product or device may be
prepared from the polymer composition. In some embodiments, a
medical product or device may be molded from the polymer
compositions, or the product or device may be prepared from a
nonwoven polymer structure formed from the polymer composition.
[0031] Because the polymer compositions exhibit permanent AM/AV
properties, the medical product or device may also exhibit AM/AV
antiviral properties. Thus, in some cases, the medical product or
device may be reusable. Particular examples include wound care
products, e.g., bandages, sheets, and gauzes.
[0032] Examples of medical products or devices that can be prepared
using the polymer compositions include masks, wipes, towels, gowns,
protective clothing, or protect nets.
[0033] For example, the polymer composition may be used in the
preparation of a mask, e.g., a surgical mask, a procedure mask, a
medical mask, and/or a dust mask, having AM/AV properties. The
antiviral properties of the mask may be particular useful in
protecting against the transmission and/or infection of a virus,
e.g., between and/or among healthcare workers or members of a
larger population. The structure of the mask is not particularly
limited, and any known structure may be used. Preferably, the mask
is designed so as to ensure adequate protection (e.g., against
transmission) while providing for wearer comfort and breathability.
In some cases, the mask comprises a number of layers, e.g., one or
more layers, two or more layers, or three or more layers. In some
embodiments, one or more layers of the mask may be formed by a
fabric according the present disclosure. In some embodiments, one
or more layers of the mask may be formed by a nonwoven polymer
structure according the present disclosure. In some aspects, the
mask may be formed with two or more layers of the nonwoven polymer
structure. In some aspects, the mask further comprises one or more
layers of an antiviral fabric (as disclosed herein) in combination
with one or more layers of an antiviral nonwoven polymer structure
(as disclosed herein).
[0034] By way of another example, the polymer composition may be
used in the preparation of a filter, e.g., an air filter, a HEPA
filter, an automotive cabin air filter, or an aircraft air filter.
The antiviral properties of the filter may be particular useful in
protecting against the transmission and/or infection of a virus,
e.g., by air flow units (such as HVAC). The structure of the filter
is not particularly limited, and any known structure may be used.
Preferably, the filter is designed so as to ensure adequate
protection (e.g., against transmission) while providing for
appropriate permeability. In some cases, the filter comprises a
number of layers, e.g., one or more layers, two or more layers, or
three or more layers. In some embodiments, one or more layers of
the filter may be formed by a fabric according the present
disclosure. In some embodiments, one or more layers of the filter
may be formed by a nonwoven polymer structure according the present
disclosure. In some aspects, the filter may be formed with two or
more layers of the nonwoven polymer structure. In some aspects, the
filter further comprises one or more layers of an antiviral fabric
(as disclosed herein) in combination with one or more layers of an
antiviral nonwoven polymer structure (as disclosed herein).
[0035] By way a more general example, the polymer composition may
be used in the preparation of a layered structure, which may have
any of a variety of uses. The layered structure may comprise, for
example, an antiviral nonwoven layer comprising a described polymer
composition as well as an additional layer. The incorporation of
the polymer composition into the layered structure provides the
layered structure with antiviral properties, such as limiting,
reducing, or inhibiting infection and/or pathogenesis of a virus.
In some cases, the layered structure may include an additional
antiviral agent, optionally comprising an entry inhibitor, a
reverse transcriptase inhibitor, a DNA polymerase inhibitor, an
m-RNA synthesis inhibitor, a protease inhibitor, an integrase
inhibitor, or an immunomodulator, or combinations thereof. In some
cases, the layer structure includes a fabric of nanofibers produced
from the polymer composition. In some cases, the layer structure
includes a nonwoven polymer structure produced from the polymer
composition.
[0036] Those skilled in the art will appreciate that polymer
structures and molded products exhibiting antiviral properties may
be desirably incorporated into other products, such as furniture or
textiles, for any of a variety of uses.
Polymer Composition
[0037] As noted above, the present disclosure relates to polymer
compositions that beneficially exhibit AM/AV properties. In some
embodiments, the polymer compositions comprise a polymer, zinc
(provided to the composition via a zinc compound), and/or copper
(provided to the composition via a copper compound), and/or
phosphorus (provided to the composition via a phosphorus compound).
The polymer composition may further comprise molding additives.
Such molding additives are generally not present in polymer
compositions designed for other end products, e.g., fibers/fabrics,
since there is typically no use for them. For example, the polymer
may be present in an amount ranging from 50 wt. % to 99.9 wt. %;
the zinc may be present in an amount ranging from 0.01 wt % to 10
wt %; and the phosphorus may be present in an amount less than 1
wt. %. The molding additives may be present in an amount ranging
from 0.01 wt % to 20 wt %. Additional concentration ranges and
limits are disclosed herein. The present disclosure also relates to
polymer compositions that comprise a polymer, copper (provided to
the composition via a copper compound), and phosphorus (provided to
the composition via a phosphorus compound). For example, the
polymer may be present in an amount ranging from 50 wt. % to 99.9
wt. %; the copper may be present in an amount ranging from 10 wppm
to 20,000 wppm; and the phosphorus may be present in an amount less
than 1 wt. %. The polymer compositions may be used to form molded
products, and, in addition to improved AM/AV performance, the
fibers demonstrate superior mechanical properties, e.g., tensile
strength or impact resistance (as described herein). The fibers may
demonstrate superior zinc/copper retention rates, when tested in a
dye bath test or a wash test (as described herein).
Polymer
[0038] The polymer composition comprises a polymer, which, in some
embodiments, is a polymer suitable for producing fibers and
fabrics. In one embodiment, the polymer composition comprises a
polymer in an amount ranging from 50 wt. % to 100 wt. %, e.g., from
50 wt. % to 99.99 wt. %, from 50 wt. % to 99.9 wt. %, from 50 wt. %
to 99 wt. % from 55 wt. % to 100 wt. %, from 55 wt. % to 99.99 wt.
%, from 55 wt. % to 99.9 wt. %, from 55 wt. % to 99 wt. %, from 60
wt. % to 100 wt. %, from 60 wt. % to 99.99 wt. %, from 60 wt. % to
99.9 wt. %, from 60 wt. % to 99 wt. %, from 60 wt % to 96 wt %,
from 65 wt. % to 100 wt. %, from 65 wt. % to 99.99 wt. %, from 65
wt. % to 99.9 wt. %, or from 65 wt. % to 99 wt. %, from 65 wt % to
96 wt %, from 70 wt % to 96 wt %, or from 60 wt % to 99.5 wt %. In
terms of upper limits, the polymer composition may comprise less
than 100 wt. % of the polymer, e.g., less than 99.99 wt. %, less
than 99.9 wt. %, less than 99 wt. %, less than 97%, less than 96%,
or less than 95%. In terms of lower limits, the polymer composition
may comprise greater than 50 wt. % of the polymer, e.g., greater
than 55 wt. %, greater than 60 wt. %, or greater than 65 wt. %.
[0039] The polymer of the polymer composition may vary widely. The
polymer may include but is not limited to, a thermoplastic polymer,
polyester, nylon, rayon, polyamide 6, polyamide 6,6, polyethylene
(PE), polypropylene (PP), polyethylene terephthalate (PET),
polyethylene terephthalate glycol (PETG), co-PET, polylactic acid
(PLA), and polytrimethylene terephthalate (PTT). In some
embodiments, the polymer composition may comprise PET, for its
strength, longevity during washing, ability to be made permanent
press, and ability to be blended with other fibers. In some
embodiments, the polymer may be Nylon 6,6. In some cases, nylon is
known to be a stronger fiber than PET and exhibits a non-drip
burning characteristic that is beneficial e.g., in military or
automotive textile applications, and is more hydrophilic than PET.
The polymer used in the present disclosure can be a polyamide,
polyether amide, polyether ester or polyether urethane or a mixture
thereof.
[0040] In some cases, the polymer compositions may comprise
polyethylene. Suitable examples of polyethylene include linear
low-density polyethylene (LLDPE), low-density polyethylene (LDPE),
medium-density polyethylene (MDPE), high-density polyethylene
(HDPE), and ultra-high-molecular-weight polyethylene (UHMWPE).
[0041] In some cases, the polymer compositions may comprise
polycarbonate (PC). For example, the polymer composition may
comprise a blend of polycarbonate with other polymers, e.g., a
blend of polycarbonate and acrylonitrile butadiene styrene
(PC-ABS), a blend of polycarbonate and polyvinyl toluene (PC-PVT),
a blend of polycarbonate and polybutylene terephthalate (PC-PBT), a
blend of polycarbonate and polyethylene terephthalate (PC-PET), or
combinations thereof.
[0042] In some cases, the polymer composition may comprise
polyamides. Common polyamides include nylons and aramids. For
example, the polyamide may comprise PA-4T/41; PA-4T/6I; PA-5T/51;
PA-6; PA-6,6; PA-6,6/6; long chain polyamide (such as PA-10; PA-12;
PA-6,10; PA-6,12, as well as other known long chain variants
optionally including aromatic components, e.g., T and I components,
in particular for use as brush bristles); PA-6,6/6T; PA-6T/6I;
PA-6T/6I/6; PA-6T/6; PA-6T/6I/66; PA-6T/MPMDT (where MPMDT is
polyamide based on a mixture of hexamethylene diamine and
2-methylpentamethylene diamine as the diamine component and
terephthalic acid as the diacid component); PA-6T/66; PA-6T/610;
PA-10T/612; PA-10T/106; PA-6T/612; PA-6T/10T; PA-6T/10I; PA-9T;
PA-10T; PA-12T; PA-10T/10I; PA-10T/12; PA-10T/11; PA-6T/9T;
PA-6T/12T; PA-6T/10T/6I; PA-6T/6I/6; PA-6T/61/12; and copolymers,
blends, mixtures and/or other combinations thereof. Additional
suitable polyamides, additives, and other components are disclosed
in U.S. patent application Ser. No. 16/003,528. Such polymers may
synergistically work well with the other components of the polymer
composition due to the hydrophilic and/or hygroscopic properties
thereof.
[0043] The polymer compositions surprisingly may benefit from a
polymer having increased hydrophilicity and/or hygroscopy. In
particular, the use of a hydrophilic and/or hygroscopic polymer may
increase the antiviral properties of the polymer composition. It is
postulated that viruses and/or microbials are carried by liquids
like saliva and mucous. Also, it is theorized that a polymer of
increased hydrophilicity and/or hygroscopy both may better attract
liquid media that carry microbials and/or viruses, e.g., saliva or
mucous, and may also absorb more moisture, e.g., from the air. and
that the increased moisture content allows the polymer composition
and the antiviral/antimicrobial agent to more readily limit,
reduce, or inhibit infection and/or pathogenesis of a virus. For
example, the moisture may dissolve an outer layer, e.g., capsid, of
a virus, exposing the genetic material, e.g., DNA or RNA, of the
virus. The exposed genetic material is more susceptible to
deactivation by other components of the polymer composition, e.g.,
the zinc compound, phosphorus compound, and/or copper compound
(discussed below). This is one surprising, synergistic results of
using polymers having higher levels of hydrophilicity and/or
hygroscopy. In contrast, a molded products formed from less
hydrophilic and/or hygroscopic polymers, e.g., polypropylene, may
not attract the fluids, and may not be as effective.
[0044] In some cases, conventional surface modifiers, such as
citric acid, are applied to or sprayed on the surface of the
polymer compositions (or of articles formed therefrom). By using a
hydrophilic and/or hygroscopic polymer, the polymer compositions of
the present disclosure may not require any such solubility
modifiers.
[0045] In some other embodiments however, the products formed from
the polymer compositions may be treated, e.g., with citric acid, to
make them even more hydrophilic and/or hygroscopic.
[0046] In some cases, the hydrophilicity and/or hygroscopy of a
polymer may be measured by saturation.
[0047] In some cases, the hydrophilicity and/or hygroscopy of a
polymer may be measured by the amount of water it can absorb (as a
percentage of total weight). In some embodiments, the hydrophilic
and/or hygroscopic polymer is capable of absorbing greater than 1.5
wt % water, based on the total weight of the polymer, e.g., greater
than 2.0 wt %, greater than 3.0%, greater than 5.0 wt %, or greater
than 7.0 wt %. In terms of ranges, the hydrophilic and/or
hygroscopic polymer may be capable of absorbing water in an amount
ranging from 1.5 wt % to 10.0 wt %, e.g., from 1.5 wt % to 9.0 wt
%, from 2.0 wt % to 8 wt %, from 2.0 wt % to 7 w %, of from 2.5 wt
% to 7 wt. %. The ability to absorb more moisture allows the
polymer compositions to better reduce or inhibit the growth of the
microbials and/or viruses that are contained therein (as discussed
above).
[0048] As noted above, some applications of the polymer
compositions described herein surprisingly may benefit from
increased hygroscopy. An increase in hygroscopy may be achieved in
the selection and/or modification the polymer. In some embodiments,
the polymer may be a common polymer, e.g., a common polyamide,
which has been modified to increase hygroscopy. In these
embodiments, a functional endgroup modification on the polymer may
increase hygroscopy. For example, the polymer may be PA-6,6, which
has been modified to include a functional endgroup that increases
hygroscopy.
[0049] In some preferred cases, the polyamide-based, e.g.,
nylon-based, compounds are utilized as the polymer. It has
surprisingly been found that these nylon-based polymers, when
utilized with the aforementioned zinc compound, copper compound,
and phosphorus compound additives and formed into molded products,
provide the antiviral and/or antimicrobial characteristics. In some
cases, it has been found that conventional polymers that utilize
polyester polymers harbor and allow to flourish different types of
viruses and/or bacteria, as compared to those of nylon. For
example, micrococcus bacteria have been found to flourish in
polyester-based fabrics and produce high odor levels. Thus the use
of nylon-based polymers, along with the aforementioned additives,
surprisingly has been found to yield fabrics that demonstrate
significantly low odor levels as compared to similar fabrics that
utilize polyesters.
[0050] The polymer composition may, in some embodiments, comprise a
combination of polyamides. By combining various polyamides, the
final composition may be able to incorporate the desirable
properties, e.g., mechanical properties, of each constituent
polyamides. For example, in some embodiments, the polyamide
comprises a combination of PA-6, PA-6,6, and PA-6,6/6T. In these
embodiments, the polyamide may comprise from 1 wt. % to 99 wt. %
PA-6, from 30 wt. % to 99 wt. % PA-6,6, and from 1 wt. % to 99 wt.
% PA-6,6/6T. In some embodiments, the polyamide comprises one or
more of PA-6, PA-6,6, and PA-6,6/6T. In some aspects, the polymer
composition comprises 6 wt. % of PA-6 and 94 wt. % of PA-6,6. In
some cases, the polymer comprises PA-6, and PA-6,6. In some cases,
the polymer comprises PA-6,12. In one embodiment, the polymer
comprises PA-6,6/6,12, alone or in combination with additional
polyamides. In some aspects, the polymer composition comprises
copolymers or blends of any of the polyamides mentioned herein.
[0051] The polymer composition may also comprise polyamides
produced through the ring-opening polymerization or
polycondensation, including the copolymerization and/or
copolycondensation, of lactams. Without being bound by theory,
these polyamides may include, for example, those produced from
propriolactam, butyrolactam, valerolactam, and caprolactam. For
example, in some embodiments, the polyamide is a polymer derived
from the polymerization of caprolactam. In those embodiments, the
polymer comprises at least 10 wt. % caprolactam, e.g., at least 15
wt. %, at least 20 wt. %, at least 25 wt. %, at least 30 wt. %, at
least 35 wt. %, at least 40 wt. %, at least 45 wt. %, at least 50
wt. %, at least 55 wt. %, or at least 60 wt. %. In some
embodiments, the polymer includes from 10 wt. % to 60 wt. % of
caprolactam, e.g., from 15 wt. % to 55 wt. %, from 20 wt. % to 50
wt. %, from 25 wt. % to 45 wt. %, or from 30 wt. % to 40 wt. %. In
some embodiments, the polymer comprises less than 60 wt. %
caprolactam, e.g., less than 55 wt. %, less than 50 wt. %, less
than 45 wt. %, less than 40 wt. %, less than 35 wt. %, less than 30
wt. %, less than 25 wt. %, less than 20 wt. %, or less than 15 wt.
%. Furthermore, the polymer composition may comprise the polyamides
produced through the copolymerization of a lactam with a nylon, for
example, the product of the copolymerization of a caprolactam with
PA-6,6.
[0052] In some aspects, the polymer can formed by conventional
polymerization of the polymer composition in which an aqueous
solution of at least one diamine-carboxylic acid salt is heated to
remove water and effect polymerization to form an antiviral nylon.
This aqueous solution is preferably a mixture which includes at
least one polyamide-forming salt in combination with the specific
amounts of a zinc compound, a copper compound, and/or a phosphorus
compound described herein to produce a polymer composition.
Conventional polyamide salts are formed by reaction of diamines
with dicarboxylic acids with the resulting salt providing the
monomer. In some embodiments, a preferred polyamide-forming salt is
hexamethylenediamine adipate (nylon 6,6 salt) formed by the
reaction of equimolar amounts of hexamethylenediamine and adipic
acid.
[0053] In some embodiments, the polymer compositions (and the
fibers/fabrics produced therefrom) advantageously comprise little
or no content of processing aids such as surfactants and/or
coupling agents (see discussion above). In some cases, the polymer
compositions comprise less than 100 wppm surfactant and/or coupling
agent, e.g., less than 50 wppm, less than less than 20 wppm, less
than 10 wppm, or less than 5 wppm. In terms of ranges, the polymer
compositions may comprise from 1 wppb to 100 wppm, e.g., from 1
wppb to 20 wppm, from 1 wppb to 10 wppm, or from 1 wppb to 5 wppm.
The disclosed compositions may not employ any surfactant and/or
coupling agent at all. There can be no surfactant and/or coupling
agent present after processing, which is not the case for
conventional formulations that do employ surfactant and/or coupling
agents as necessary components. Even though some of these
components may burn off during processing, some surfactant and/or
coupling agent will remain in the resultant fibers.
[0054] Common surfactants include anionic surfactants, cationic
surfactants and/or non-ionic surfactants. Specific examples are
stearic acid, sodium dodecyl sulfonate surfactants, quaternary
ammonium surfactants, amino acid surfactants, betaine surfactants,
fatty acid glyceride ester surfactants, fatty acid sorbitan
surfactants, lecithin surfactants, and/or Tween.TM. series
surfactants (e.g., polyethoxylated sorbitan ester surfactants,
nonionic polyoxyethylene surfactants, etc.).
[0055] The inventors have found that the content of amine end
groups (AEG) may have a surprising effect on the performance of the
polymer compositions and molded products. As one example, the AEGs
have been found to improve the ability to dye products. The polymer
composition may have an AEG content ranging from 1 .mu.eq/gram to
105 .mu.eq/gram, e.g., from 1 .mu.eq/gram to 75 .mu.eq/gram, from 1
.mu.eq/gram to 55 .mu.eq/gram, from 5 .mu.eq/gram to 50
.mu.eq/gram, or from 15 .mu.eq/gram to 40 .mu.eq/gram. In terms of
upper limits, the polymer composition may have an AEG content less
than 105 .mu.eq/gram, e.g., less than 100 .mu.eq/gram, less than 90
.mu.eq/gram, less than 75 .mu.eq/gram, less than 55 .mu.eq/gram,
less than 50 .mu.eq/gram, less than 45 .mu.eq/gram, less than 40
.mu.eq/gram, less than 35 .mu.eq/gram, less than 30 .mu.eq/gram, or
less than 25 .mu.eq/gram. In terms of lower limits, the polymer
composition may have an AEG content greater than 1 .mu.eq/gram,
e.g., greater than 5 .mu.eq/gram, greater than 10 .mu.eq/gram,
greater than 15 .mu.eq/gram, greater than 20 .mu.eq/gram, greater
than 25 .mu.eq/gram, greater than 35 .mu.eq/gram, greater than 40
.mu.eq/gram, or greater than 50 .mu.eq/gram.
[0056] In some cases, a higher relative viscosity may be employed.
In other cases, a lower relative viscosity may be employed. In
these cases, the inventors have found that by using particular zinc
and/or phosphorus content, along with specific polymer
characteristics, unexpected efficiencies can be achieved, while
also achieving AM/AV and mechanical performance. Examples of some
specific formulations are provided below.
Zinc Compound
[0057] As noted above, the polymer composition includes zinc in a
zinc compound and phosphorus in a phosphorus compound, preferably
in specific amounts in the polymer composition, to provide the
aforementioned structural and antiviral benefits. As used herein,
"zinc compound" refers to a compound having at least one zinc
molecule or ion (likewise for copper compounds). As used herein,
"phosphorus compound" refers to a compound having at least one
phosphorus molecule or ion. Zinc content may be indicated by zinc
or zinc ion (the same is true for copper). The ranges and limits
may be employed for zinc content and for zinc ion content, and for
other metal content, e.g., copper content. The calculation of zinc
ion content based on zinc or zinc compound can be made by the
skilled chemist, and such calculations and adjustments are
contemplated.
[0058] The inventors have found that the use of specific zinc
compounds (and the zinc contained therein) and phosphorus compounds
(and the phosphorus contained therein) at specific molar ratios
minimizes the negative effects of the zinc compound on the polymer
composition. For example, too much zinc compound in the polymer
composition can lead to decreased polymer viscosity and
inefficiencies in production processes.
[0059] The polymer composition may comprise zinc (e.g., in a zinc
compound or as zinc ion), e.g., zinc or a zinc compound, dispersed
within the polymer composition. In one embodiment, the polymer
composition comprises zinc in an amount ranging from 5 wppm to
100,000 wppm (10 wt %), e.g., 5 wppm to 20000 wppm, from 5 wppm to
17,500 wppm, from 5 wppm to 17,000 wppm, from 5 wppm to 16,500
wppm, from 5 wppm to 16,000 wppm, from 5 wppm to 15,500 wppm, from
5 wppm to 15,000 wppm, from 5 wppm to 12,500 wppm, from 5 wppm to
10,000 wppm, from 5 wppm to 5000 wppm, from 5 wppm to 4000 wppm,
e.g., from 5 wppm to 3000 wppm, from 5 wppm to 2000 wppm, from 5
wppm to 1000 wppm, from 5 wppm to 500 wppm, from 10 wppm to 20,000
wppm, from 10 wppm to 17,500 wppm, from 10 wppm to 17,000 wppm,
from 10 wppm to 16,500 wppm, from 10 wppm to 16,000 wppm, from 10
wppm to 15,500 wppm, from 10 wppm to 15,000 wppm, from 10 wppm to
12,500 wppm, from 10 wppm to 10,000 wppm, from 10 wppm to 5000
wppm, from 10 wppm to 4000 wppm, from 10 wppm to 3000 wppm, from 10
wppm to 2000 wppm, from 10 wppm to 1000 wppm, from 10 wppm to 500
wppm, from 50 wppm to 20,000 wppm, from 50 wppm to 17,500 wppm,
from 50 wppm to 17,000 wppm, from 50 wppm to 16,500 wppm, from 50
wppm to 16,000 wppm, from 50 wppm to 15,500 wppm, from 50 wppm to
15,000 wppm, from 50 wppm to 12,500 wppm, from 50 wppm to 10,000
wppm, from 50 wppm to 5000 wppm, from 50 wppm to 4000 wppm, from 50
wppm to 3000 wppm, 50 wppm to 500 wppm, from 100 wppm to 20,000
wppm, from 100 wppm to 17,500 wppm, from 100 wppm to 17,000 wppm,
from 100 wppm to 16,500 wppm, from 100 wppm to 16,000 wppm, from
100 wppm to 15,500 wppm, from 100 wppm to 15,000 wppm, from 100
wppm to 12,500 wppm, from 100 wppm to 10,000 wppm, from 100 wppm to
5000 wppm, from 100 wppm to 4000 wppm, from 100 wppm to 500 wppm,
from 200 wppm to 20,000 wppm, from 200 wppm to 17,500 wppm, from
200 wppm to 17,000 wppm, from 200 wppm to 16,500 wppm, from 200
wppm to 16,000 wppm, from 200 wppm to 15,500 wppm, from 200 wppm to
15,000 wppm, from 200 wppm to 12,500 wppm, from 200 wppm to 10,000
wppm, from 200 wppm to 5000 wppm, from 200 wppm to 4000 wppm, 5000
wppm to 20000 wppm, from 200 wppm to 500 wppm, from 500 ppm to
10000 wppm, from 1000 ppm to 7000 wppm, or from 3000 ppm to 5000
wppm.
[0060] In terms of lower limits, the polymer composition may
comprise greater than 5 wppm of zinc, e.g., greater than 10 wppm,
greater than 50 wppm, greater than 100 wppm, greater than 200 wppm,
greater than 300 wppm, greater than 350 wppm, greater than 375
wppm, greater than 400 wppm, greater than 425 wppm, greater than
480 wppm, greater than 500 wppm, greater than 600 wppm, greater
than 1000 wppm, or greater than 3000 wppm.
[0061] In terms of upper limits, the polymer composition may
comprise less than 20,000 wppm of zinc, e.g., less than 17,500
wppm, less than 17,000 wppm, less than 16,500 wppm, less than
16,000 wppm, less than 15,500 wppm, less than 15,000 wppm, less
than 12,500 wppm, less than 10,000 wppm, less than 7000 wppm, less
than 5000 wppm, less than less than 4000 wppm, less than 3000 wppm,
less than 2000 wppm, less than 1000 wppm, or less than 500 wppm. In
some aspects, the zinc compound is embedded in the polymer formed
from the polymer composition. The ranges and limits are applicable
to both zinc in elemental or ionic form and to zinc compound). In
some cases, the zinc (as the AM/AV compound) is independent of
other zinc containing materials (such as, for example, zinc borate
added as a flame retardant).
[0062] The zinc of the polymer composition is present in or
provided via a zinc compound, which may vary widely. The zinc
compound may comprise zinc oxide, zinc ammonium adipate, zinc
acetate, zinc ammonium carbonate, zinc stearate, zinc phenyl
phosphinic acid, or zinc pyrithione, or combinations thereof. In
some embodiments, the zinc compound comprises zinc oxide, zinc
ammonium adipate, zinc acetate, or zinc pyrithione, or combinations
thereof. In some embodiments, the zinc compound comprises zinc
oxide, zinc stearate, or zinc ammonium adipate, or combinations
thereof. In some aspects, the zinc is provided in the form of zinc
oxide. In some aspects, the zinc is not provided via zinc phenyl
phosphinate and/or zinc phenyl phosphonate.
[0063] The inventors have also found that the polymer compositions
surprisingly may benefit from the use of specific zinc compounds.
In particular, the use of zinc compounds prone to forming ionic
zinc (e.g., Zn.sup.2+) may increase the antiviral properties of the
polymer composition. It is theorized that the ionic zinc disrupts
the replicative cycle of the virus. For example, the ionic zinc may
interfere with (e.g., inhibit) viral protease or polymerase
activity. Further discussion of the effect of ionic zinc on viral
activity is found in Velthuis et al., Zn Inhibits Coronavirus and
Arterivirus RNA Polymerase Activity In Vitro and Zinc Ionophores
Block the Replication of These Viruses in Cell Culture, PLoS
Pathogens (November 2010), which is incorporated herein by
reference.
[0064] The amount of the zinc compound present in the polymer
compositions may be discussed in relation to the ionic zinc
content. In one embodiment, the polymer composition comprises ionic
zinc, e.g., Zn.sup.2+, in an amount ranging from 1 ppm to 30,000
ppm, e.g., from 1 ppm to 25,000 ppm, from 1 ppm to 20,000 ppm, from
1 ppm to 15,000 ppm, from 1 ppm to 10,000 ppm, from 1 ppm to 5,000
ppm, from 1 ppm to 2,500 ppm, from 50 ppm to 30,000 ppm, from 50
ppm to 25,000 ppm, from 50 ppm to 20,000 ppm, from 50 ppm to 15,000
ppm, from 50 ppm to 10,000 ppm, from 50 ppm to 5,000 ppm, from 50
ppm to 2,500 ppm, from 100 ppm to 30,000 ppm, from 100 ppm to
25,000 ppm, from 100 ppm to 20,000 ppm, from 100 ppm to 15,000 ppm,
from 100 ppm to 10,000 ppm, from 100 ppm to 5,000 ppm, from 100 ppm
to 2,500 ppm, from 150 ppm to 30,000 ppm, from 150 ppm to 25,000
ppm, from 150 ppm to 20,000 ppm, from 150 ppm to 15,000 ppm, from
150 ppm to 10,000 ppm, from 150 ppm to 5,000 ppm, from 150 ppm to
2,500 ppm, from 250 ppm to 30,000 ppm, from 250 ppm to 25,000 ppm,
from 250 ppm to 20,000 ppm, from 250 ppm to 15,000 ppm, from 250
ppm to 10,000 ppm, from 250 ppm to 5,000 ppm, from 250 ppm to 2,500
ppm, from 500 ppm to 10000 wppm, from 1000 ppm to 7000 wppm, or
from 3000 ppm to 5000 wppm. In some cases, the ranges and limits
mentioned above for zinc may also be applicable to ionic zinc
content.
[0065] In some cases, the use of zinc provides for processing and
or end use benefits. Other antiviral agents, e.g., copper or
silver, may be used, but these often include adverse effects (e.g.,
on the relative viscosity of the polymer composition, toxicity, and
health or environmental risk). In some situations, the zinc does
not have adverse effects on the relative viscosity of the polymer
composition. Also, the zinc, unlike other antiviral agents, e.g.,
silver, does not present toxicity issues (and in fact may provide
health advantages, such as immune system support). In addition, as
noted herein, the use of zinc provides for the reduction or
elimination of leaching into other media and/or into the
environment. This both prevents the risks associated with
introducing zinc into the environment and allows the polymer
composition to be reused--zinc provides surprising "green"
advantages over conventional, e.g., silver-containing,
compositions.
Phosphorus Compound
[0066] The polymer composition may comprise phosphorus (in a
phosphorus compound), e.g., phosphorus or a phosphorus compound is
dispersed within the polymer composition. In one embodiment, the
polymer composition comprises phosphorus in an amount ranging from
50 wppm to 10000 wppm, e.g., from 50 wppm to 5000 wppm, from 50
wppm to 2500 wppm, from 50 wppm to 2000 wppm, from 50 wppm to 800
wppm, 100 wppm to 750 wppm, 100 wppm to 1800 wppm, from 100 wppm to
10000 wppm, from 100 wppm to 5000 wppm, from 100 wppm to 2500 wppm,
from 100 wppm to 1000 wppm, from 100 wppm to 800 wppm, from 200
wppm to 10000 wppm, 200 wppm to 5000 wppm, from 200 wppm to 2500
wppm, from 200 ppm to 800 wppm, from 300 wppm to 10000 wppm, from
300 wppm to 5000 wppm, from 300 wppm to 2500 wppm, from 300 wppm to
500 wppm, from 500 wppm to 10000 wppm, from 500 wppm to 5000 wppm,
or from 500 wppm to 2500 wppm. In terms of lower limits, the
polymer composition may comprise greater than 50 wppm of
phosphorus, e.g., greater than 75 wppm, greater than 100 wppm,
greater than 150 wppm, greater than 200 wppm greater than 300 wppm
or greater than 500 wppm. In terms of upper limits, the polymer
composition may comprise less than 10000 wppm (or 1 wt. %), e.g.,
less than 5000 wppm, less than 2500 wppm, less than 2000 wppm, less
than 1800 wppm, less than 1500 wppm, less than 1000 wppm, less than
800 wppm, less than 750 wppm, less than 500 wppm, less than 475
wppm, less than 450 wppm, less than 400 wppm, less than 350 wppm,
less than 300 wppm, less than 250 wppm, less than 200 wppm, less
than 150 wppm, less than 100 wppm, less than 50 wppm, less than 25
wppm, or less than 10 wppm.
[0067] In some aspects, the phosphorus or the phosphorus compound
is embedded in the polymer formed from the polymer composition. As
noted above, because of the overall make-up of the disclosed
composition low amounts, if any, phosphorus may be employed, which
in some cases may provide for advantageous performance results (see
above).
[0068] The phosphorus of the polymer composition is present in or
provided via a phosphorus compound, which may vary widely. The
phosphorus compound may comprise bezene phosphinic acid,
diphenylphosphinic acid, sodium phenylphosphinate, phosphorous
acid, benzene phosphonic acid, calcium phenylphosphinate, potassium
B-pentylphosphinate, methylphosphinic acid, manganese
hypophosphite, sodium hypophosphite, monosodium phosphate,
hypophosphorous acid, dimethylphosphinic acid, ethylphosphinic
acid, diethylphosphinic acid, magnesium ethylphosphinate, triphenyl
phosphite, diphenylrnethyl phosphite, dimethylphenyl phosphite,
ethyldiphenyl phosphite, phenylphosphonic acid, methylphosphonic
acid, ethylphosphonic acid, potassium phenylphosphonate, sodium
methylphosphonate, calcium ethylphosphonate, and combinations
thereof. In some embodiments, the phosphorus compound comprises
phosphoric acid, benzene phosphinic acid, or benzene phosphonic
acid, or combinations thereof. In some embodiments, the phosphorus
compound comprises benzene phosphinic acid, phosphorous acid, or
manganese hypophosphite, or combinations thereof. In some aspects,
the phosphorus compound may comprise benzene phosphinic acid.
[0069] In one embodiment, the molar ratio of the phosphorus to the
zinc is greater than 0.01:1, e.g., greater than 0.05:1, greater
than 0.1:1, greater than 0.15:1, greater than 0.25:1, greater than
0.5:1, or greater than 0.75:1. In terms of ranges, the molar ratio
of the phosphorus to the zinc in the polymer composition may range
from 0.01:1 to 15:1, e.g., from 0.05:1 to 10:1, from 0.1:1 to 9:1,
from 0.15:1 to 8:1, from 0.25:1 to 7:1, from 0.5:1 to 6:1, from
0.75:1 to 5:1 from 0.5:1 to 4:1, or from 0.5:1 to 3:1. In terms of
upper limits, the molar ratio of zinc to phosphorus in the polymer
composition may be less than 15:1, e.g., less than 10:1, less than
9:1, less than 8:1, less than 7:1, less than 6:1, less than 5:1,
less than 4:1, or less than 3:1. In some cases, phosphorus is bound
in the polymer matrix along with zinc.
[0070] In one embodiment, the weight ratio of zinc to phosphorus in
the polyamide composition may be greater than 1.3:1, e.g., greater
than 1.4:1, greater than 1.5:1, greater than 1.6:1, greater than
1.7:1, greater than 1.8:1, or greater than 2:1. In terms of ranges,
the weight ratio of zinc to phosphorus in the polyamide composition
may range from 1.3:1 to 30:1, e.g., from 1.4:1 to 25:1, from 1.5:1
to 20:1, from 1.6:1 to 15:1, from 1.8:1 to 10:1, from 2:1 to 8:1,
from 3:1 to 7:1, or from 4:1 to 6:1. In terms of upper limits, the
weight ratio of zinc to phosphorus in the polyamide composition may
be less than 30:1, e.g., less than 28:1, less than 26:1, less than
24:1, less than 22:1, less than 20:1, or less than 15:1. In some
aspects, there is no phosphorus in the polyamide composition. In
other aspects, a very low amount of phosphorus is present. In some
cases, phosphorus is held in the polymer matrix along with
zinc.
[0071] In one embodiment, the weight ratio of zinc to phosphorus in
the polyamide composition may be less than 0.64:1, e.g., less than
0.62:1, less than 0.6:1, e.g., less than 0.5:1, less than 0.45:1,
less than 0.4:1, less than 0.3:1, or less than 0.25:1. In terms of
ranges, the weight ratio of zinc to phosphorus in the polyamide
composition may range from 0.001:1 to 0.64:1, e.g., from 0.01:1 to
0.6:1, from 0.05:1 to 0.5:1, from 0.1:1 to 0.45:1, from 0.2:1 to
0.4:1, from 0.25:1 to 0.35:1, or from 0.2:1 to 0.3:1. In terms of
lower limits, the weight ratio of zinc to phosphorus in the
polyamide composition may be greater than 0.001:1, e.g., greater
than 0.005:1, greater than 0.01:1, greater than 0.05:1, greater
than 0.1:1, greater than 0.15:1, or greater than 0.2:1.
[0072] Advantageously, it has been discovered that adding the above
identified zinc compounds and phosphorus compounds may result in a
beneficial relative viscosity (RV) of the polymer composition. In
some embodiments, the RV of the polymer composition ranges from 5
to 80, e.g., from 5 to 70, from 10 to 70, from 15 to 65, from 20 to
60, from 30 to 50, from 10 to 35, from 10 to 20, from 60 to 70,
from 50 to 80, from 40 to 50, from 30 to 60, from 5 to 30, or from
15 to 32. In terms of lower limits, the RV of the polymer
composition may be greater than 5, e.g., greater than 10, greater
than 15, greater than 20, greater than 25, greater than 27.5, or
greater than 30. In terms of upper limits, the RV of the polymer
composition may be less than 70, e.g., less than 65, less than 60,
less than 50, less than 40, or less than 35.
[0073] To calculate RV, a polymer may be dissolved in a solvent
(usually formic or sulfuric acid), the viscosity is measured, then
the viscosity is compared to the viscosity of the pure solvent.
This give a unitless measurement. Solid materials, as well as
liquids, may have a specific RV. The products produced from the
polymer compositions may have the aforementioned relative
viscosities, as well.
[0074] It has been determined that a specific amount of the zinc
compound and the phosphorus compound can be mixed in a polymer
composition, e.g., polyamide composition, in finely divided form,
such as in the form of granules, flakes and the like, to provide a
polymer composition that can be subsequently formed, e.g.,
extruded, molded or otherwise drawn, into various products (e.g.,
high-contact products, surface layers of high-contact products) by
conventional methods to produce products having substantially
improved antimicrobial activity. The zinc and phosphorus are
employed in the polymer composition in the aforementioned amounts
to provide a fiber with improved antimicrobial activity retention
(near-permanent).
Copper Compound
[0075] As noted above, the polymer composition, in some
embodiments, includes copper (provided via a copper compound). As
used herein, "copper compound" refers to a compound having at least
one copper molecule or ion.
[0076] In some cases, the copper compound may improve, e.g.,
enhance the antiviral properties of the polymer composition. In
some cases, the copper compound may affect other characteristics of
the polymer composition, e.g., antimicrobial activity or physical
characteristics.
[0077] The polymer composition may comprise copper (e.g., in a
copper compound), e.g., copper or a copper compound, dispersed
within the polymer composition. In one embodiment, the polymer
composition comprises copper in an amount ranging from 5 wppm to
20,000 wppm, e.g., from 5 wppm to 17,500 wppm, from 5 wppm to
17,000 wppm, from 5 wppm to 16,500 wppm, from 5 wppm to 16,000
wppm, from 5 wppm to 15,500 wppm, from 5 wppm to 15,000 wppm, from
5 wppm to 12,500 wppm, from 5 wppm to 10,000 wppm, from 5 wppm to
5000 wppm, from 5 wppm to 4000 wppm, e.g., from 5 wppm to 3000
wppm, from 5 wppm to 2000 wppm, from 5 wppm to 1000 wppm, from 5
wppm to 500 wppm, from 5 wppm to 100 wppm, from 5 wppm to 50 wppm,
from 5 wppm to 35 wppm, from 10 wppm to 20,000 wppm, from 10 wppm
to 17,500 wppm, from 10 wppm to 17,000 wppm, from 10 wppm to 16,500
wppm, from 10 wppm to 16,000 wppm, from 10 wppm to 15,500 wppm,
from 10 wppm to 15,000 wppm, from 10 wppm to 12,500 wppm, from 10
wppm to 10,000 wppm, from 10 wppm to 5000 wppm, from 10 wppm to
4000 wppm, from 10 wppm to 3000 wppm, from 10 wppm to 2000 wppm,
from 10 wppm to 1000 wppm, from 10 wppm to 500 wppm, from 50 wppm
to 20,000 wppm, from 50 wppm to 17,500 wppm, from 50 wppm to 17,000
wppm, from 50 wppm to 16,500 wppm, from 50 wppm to 16,000 wppm,
from 50 wppm to 15,500 wppm, from 50 wppm to 15,000 wppm, from 50
wppm to 12,500 wppm, from 50 wppm to 10,000 wppm, from 50 wppm to
5000 wppm, from 50 wppm to 4000 wppm, from 50 wppm to 3000 wppm,
from 50 wppm to 2000 wppm, from 50 wppm to 1000 wppm, from 50 wppm
to 500 wppm, from 100 wppm to 20,000 wppm, from 100 wppm to 17,500
wppm, from 100 wppm to 17,000 wppm, from 100 wppm to 16,500 wppm,
from 100 wppm to 16,000 wppm, from 100 wppm to 15,500 wppm, from
100 wppm to 15,000 wppm, from 100 wppm to 12,500 wppm, from 100
wppm to 10,000 wppm, from 100 wppm to 5000 wppm, from 100 wppm to
4000 wppm, from 100 wppm to 3000 wppm, from 100 wppm to 2000 wppm,
from 100 wppm to 1000 wppm, from 100 wppm to 500 wppm, from 200
wppm to 20,000 wppm, from 200 wppm to 17,500 wppm, from 200 wppm to
17,000 wppm, from 200 wppm to 16,500 wppm, from 200 wppm to 16,000
wppm, from 200 wppm to 15,500 wppm, from 200 wppm to 15,000 wppm,
from 200 wppm to 12,500 wppm, from 200 wppm to 10,000 wppm, from
200 wppm to 5000 wppm, from 200 wppm to 4000 wppm, from 200 wppm to
3000 wppm, from 200 wppm to 2000 wppm, from 200 wppm to 1000 wppm,
or from 200 wppm to 500 wppm.
[0078] In terms of lower limits, the polymer composition may
comprise greater than 5 wppm of copper, e.g., greater than 10 wppm,
greater than 50 wppm, greater than 100 wppm, greater than 200 wppm,
or greater than 300 wppm. In terms of upper limits, the polymer
composition may comprise less than 20,000 wppm of copper, e.g.,
less than 17,500 wppm, less than 17,000 wppm, less than 16,500
wppm, less than 16,000 wppm, less than 15,500 wppm, less than
15,000 wppm, less than 12,500 wppm, less than 10,000 wppm, less
than 5000 wppm, less than less than 4000 wppm, less than 3000 wppm,
less than 2000 wppm, less than 1000 wppm, less than 500 wppm less
than 100 wppm, less than 50 wppm, less than 35 wppm. In some
aspects, the copper compound is embedded in the polymer formed from
the polymer composition.
[0079] The composition of the copper compound is not particularly
limited. Suitable copper compounds include copper iodide, copper
bromide, copper chloride, copper fluoride, copper oxide, copper
stearate, copper ammonium adipate, copper acetate, or copper
pyrithione, or combinations thereof. The copper compound may
comprise copper oxide, copper ammonium adipate, copper acetate,
copper ammonium carbonate, copper stearate, copper phenyl
phosphinic acid, or copper pyrithione, or combinations thereof. In
some embodiments, the copper compound comprises copper oxide,
copper ammonium adipate, copper acetate, or copper pyrithione, or
combinations thereof. In some embodiments, the copper compound
comprises copper oxide, copper stearate, or copper ammonium
adipate, or combinations thereof. In some aspects, the copper is
provided in the form of copper oxide. In some aspects, the copper
is not provided via copper phenyl phosphinate and/or copper phenyl
phosphonate.
[0080] In some cases, the polymer composition includes silver
(optionally provided via a silver compound). As used herein,
"silver compound" refers to a compound having at least one silver
molecule or ion. The silver may be in ionic form. The ranges and
limits for silver may be similar to the ranges and limits for
copper (discussed above).
[0081] In one embodiment, the molar ratio of the copper to the zinc
is greater than 0.01:1, e.g., greater than 0.05:1, greater than
0.1:1, greater than 0.15:1, greater than 0.25:1, greater than
0.5:1, or greater than 0.75:1. In terms of ranges, the molar ratio
of the copper to the zinc in the polymer composition may range from
0.01:1 to 15:1, e.g., from 0.05:1 to 10:1, from 0.1:1 to 9:1, from
0.15:1 to 8:1, from 0.25:1 to 7:1, from 0.5:1 to 6:1, from 0.75:1
to 5:1 from 0.5:1 to 4:1, or from 0.5:1 to 3:1. In terms of upper
limits, the molar ratio of zinc to copper in the polymer
composition may be less than 15:1, e.g., less than 10:1, less than
9:1, less than 8:1, less than 7:1, less than 6:1, less than 5:1,
less than 4:1, or less than 3:1. In some cases, copper is bound in
the polymer matrix along with zinc.
[0082] In some embodiments, the use of cuprous ammonium adipate has
been found to be particularly effective in activating copper ions
into the polymer matrix. Similarly, the use of silver ammonium
adipate has been found to be particularly effective in activating
silver ions into the polymer matrix. It is found that dissolving
copper (I) or copper (II) compounds in ammonium adipate is
particularly efficient at generating copper (I) or copper (II)
ions. The same is true for dissolving Ag (I) or Ag (III) compounds
in ammonium adipate to generate Ag1+ or Ag.sup.3+ ions.
Additives
[0083] In addition to the polymer and zinc components, the polymer
compositions may further comprise molding additives, which are
generally not employed when preparing a polymer composition for
spinning and blowing methods for fiber production.
Impact Modifier
[0084] The polyamide compositions disclosed herein include one or
more impact modifiers. The inventors have found that these impact
modifiers beneficially can be an elastomeric or rubbery material
selected to have good interaction and compatibility with, and
dispersion among, the one or more polyamide polymers of the
composition. The impact modifier can include a styrenic copolymer
such as an acrylate-butadiene-styrene or a methyl
methacrylate-butadiene-styrene. The impact modifier can include an
acrylic polymer or a polyethylene polymer such as a chlorinated
polyethylene. In some embodiments, the impact modifier includes an
ethylene-octene copolymer. In some cases, the combination of the
impact modifier and the melt stabilizers (optionally in the
disclosed amounts and ratios) provides for surprising, synergistic
combinations of performance features, e.g., tensile/flexural
performance and impact resistance.
[0085] In some cases, the impact modifier comprises olefins,
acrylates, or acrylics, or combinations thereof, including polymers
of these compounds such as polyolefins or polyacrylates. These
compounds may be modified, e.g., modified (grafted) with maleic
anhydride. In some embodiments, the impact modifier comprises a
maleic anhydride-modified olefin, acrylate, or acrylic, or
combinations thereof. In some cases, the impact modifier comprises
a modified olefin, e.g., a maleic anhydride-modified olefin. The
impact modifier may comprise a maleic anhydride-modified ethylene
octene and/or ethylene acrylate.
[0086] In some embodiments, the impact modifier has a glass
transition temperature ranging from ranging from 0.degree. C. to
-100.degree. C., e.g., from -5.degree. C. to -80.degree. C.,
-10.degree. C. to -70.degree. C., -20.degree. C. to -60.degree. C.,
or from -25.degree. C. to -55.degree. C. In terms of lower limits,
the impact modifier may have a glass transition temperature greater
than -100.degree. C., e.g., greater than -80.degree. C., greater
than -70.degree. C., greater than -60.degree. C., or greater than
-55.degree. C. In terms of upper limits, the impact modifier may
have a glass transition temperature less than 0.degree. C., e.g.,
less than -5.degree. C., less than -10.degree. C., less than
-15.degree. C., or less than -25.degree. C. It is believed that
impact modifiers having such glass transition temperatures
synergistically improve energy dissipation characteristics, e.g.,
impact resistance. These particular impact modifiers have glass
transition temperatures in temperature ranges that work with the
disclosed polyamides and glass fibers to achieve improved impact
performance, especially in the desired temperature ranges, e.g.,
-10.degree. C. to -70.degree. C.
[0087] The concentration of the impact modifier in the polyamide
composition can, for example, range from 3 wt % to 30 wt %, e.g.,
from 2 wt % to 25 wt %, from 2 wt % to 20 wt %, from 5.7 wt % to
21.9 wt %, from 4.0 wt % to 15 wt %, from 5.5 wt % to 14 wt %, from
6.0 wt % to 11.5 wt %, from 8.4 wt % to 24.6 wt %, from 11.1 wt %
to 27.3 wt %, or from 13.8 wt % to 30 wt %. In some embodiments,
the concentration of the impact modifier ranges from 6 wt % to 20
wt %, e.g., from 6 wt % to 14.4 wt %, from 7.4 wt % to 15.8 wt %,
from 8.8 wt % to 17.2 wt %, from 10.2 wt % to 18.6 wt %, or from
11.6 wt % to 20 wt %. In terms of upper limits, the impact modifier
concentration can be less than 30 wt %, e.g., less than 27.3 wt %,
less than 24.6 wt %, less than 21.9 wt %, less than 20 wt %, less
than 18.6 wt %, less than 17.2 wt %, less than 15.8 wt %, less than
15 wt %, less than 14 wt %, less than 14.4 wt %, less than 13 wt %,
less than 11.6 wt %, less than 11.5 wt %, less than 10.2 wt %, less
than 8.8 wt %, less than 7.4 wt %, less than 6 wt %, or less than
5.4 wt %. In terms of lower limits, the impact modifier
concentration can be greater than 3 wt %, greater than 4.0 wt %,
greater than 5.5 wt %, greater than 5.4 wt %, greater than 6 wt %,
greater than 7.4 wt %, greater than 8.8 wt %, greater than 10.2 wt
%, greater than 11.6 wt %, greater than 13 wt %, greater than 14.4
wt %, greater than 15.8 wt %, greater than 17.2 wt %, greater than
18.6 wt %, greater than 20 wt %, greater than 21.9 wt %, greater
than 24.6 wt %, or greater than 27.6 wt %. Lower concentrations,
e.g., less than 3 wt %, and higher concentrations, e.g., greater
than 30 wt %, are also contemplated.
[0088] The weight ratio of the one or more polyamide polymers to
the impact modifier in the polyamide composition can, for example,
range from 0.2 to 30, e.g., from 0.2 to 4, from 0.33 to 6.7, from 2
to 7, from 3 to 6, 1 to 15, from 5 to 15, from 2 to 12, from 0.54
to 11, from 0.9 to 18, or from 1.5 to 30. In terms of upper limits,
the weight ratio of the one or more polyamide polymers to the
impact modifier can be less than 30, e.g., less than 18, less than
15, less than 12, less than 11, less than 7, less than 6, less than
6.7, less than 4, less than 2.4, less than 1.5, less than 0.9, less
than 0.54, or less than 0.33. In terms of lower limits, the weight
ratio of the one or more polyamide polymers to the impact modifier
can be greater than 0.2, e.g., greater than 0.33, greater than
0.55, greater than 0.9, greater than 1.5, greater than 2, greater
than 2.4, greater than 3, greater than 5, greater than 6.7, greater
than 11, or greater than 18. Lower ratios, e.g., less than 0.2, and
higher ratios, e.g., greater than 30, are also contemplated.
Heat Stabilizer
[0089] The one or more heat stabilizers of the polyamide
composition can be selected to improve performance, e.g., at higher
operating temperatures, of the composition without significantly
negatively affecting the strength or ductility of the material. The
heat stabilizer can include, for example, hindered phenolic
stabilizers, phosphite-based stabilizers, hindered amine-based
stabilizers, triazine-based stabilizers, sulfur-based stabilizers,
copper stabilizers, or combinations thereof.
[0090] Examples of hindered phenolic stabilizers include
N,N'-hexane-1,6-diylbis[3-(3,5-ditert-butyl-4-hydroxyphenylpropionamide)]-
;
pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate-
]; N,N'-hexamethylene
bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide);
triethyleneglycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)
propionate];
3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dim-
ethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane;
3,5-di-tert-butyl-4-hydroxybenzyl phosphonate-diethyl ester;
1,3,5-trimethyl-2,4,6-tris(3,5-ditert-butyl-4-hydroxybenzyl)benzene;
and
1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate.
[0091] Examples of phosphite-based stabilizers include trioctyl
phosphite; trilauryl phosphite; tridecyl phosphite; octyldiphenyl
phosphite; trisisodecyl phosphite; phenyl diisodecyl phosphite;
phenyl di(tridecyl)phosphite; diphenyl isooctyl phosphite; diphenyl
isodecyl phosphite; diphenyl(tridecyl)phosphite; triphenyl
phosphite; tris(nonyl phenyl) phosphite; tris(2,4-di-tert-butyl
phenyl) phosphite; tris(2,4-di-tert-butyl-5-methyl phenyl)
phosphite; tris(butoxyethyl)phosphite;
4,4'-butylidene-bis(3-methyl-6-tertbutylphenyl-tetra-tridecyl)diphosphite-
; tetra(C.sub.12- to C.sub.15-mixed
alkyl)-4,4'-isopropylidenediphenyl diphosphite;
4,4'-isopropylidenebis(2-tert-butylphenyl)-di(nonylphenyl)phosphite;
tris(biphenyl)phosphite;
tetra(tridecyl)-1,1,3-tris(2-methyl-5-tertbutyl-4-hydroxyphenyl)butane
diphosphite;
tetra(tridecyl)-4,4'-butylidenebis(3-methyl-6-tert-butylphenyl)diphosphit-
e; tetra(C.sub.1- to C.sub.15-mixed
alkyl)-4,4'-isopropylidenediphenyl diphosphite; tris(mono-/di-mixed
nonylphenyl)phosphite;
4,4'-isopropylidenebis(2-tertbutylphenyl)-di(nonylphenyl)phosphite;
9,10-di-hydro-9-oxa-10-phosphorphenanthrene-10-oxide;
tris(3,5-di-t-butyl-4-hydroxyphenyl)phosphite;
hydrogenated-4,4'-isopropylidenediphenyl polyphosphite;
bis(octylphenyl)-bis(4,4'-butylidenebis(3-methyl-6-tert-butyl
phenyl)-1,6-hexanol diphosphite;
hexa(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane
triphosphite; tris(4,4'-isopropylidenebis(2-tertbutylphenyl)
phosphite; tris(1,3-stearoyloxyisopropyl)phosphite;
2,2-methylenebis(4,6-ditert-butylphenyl)octyl phosphite;
2,2-methylenebis(3-methyl-4,6-di-tert-butylphenyl)-2-ethylhexyl
phosphite;
tetrakis(2,4-di-tert-butyl-5-methylphenyl)-4,4'-biphenylene
diphosphite; and tetrakis(2,4-di-tert-butyl
phenyl)-4,4'-biphenylene diphosphite.
[0092] Phosphite-based stabilizers also include
pentaerythritol-type phosphite compounds, such as
2,6-di-tert-butyl-4-methylphenyl-phenyl-pentaerythritol
diphosphite;
2,6-di-tert-butyl-4-methylphenyl-methyl-pentaerythritol
diphosphite;
2,6-di-tert-butyl-4-methylphenyl-2-ethylhexyl-pentaerythritol
diphosphite;
2,6-di-tert-butyl-4-methylphenylisodecyl-pentaerythritol
diphosphite; 2,6-di-tert-butyl-4-methylphenyl-laurylpentaerythritol
diphosphite;
2,6-di-tert-butyl-4-methylphenyl-isotridecyl-pentaerythritol
diphosphite; 2,6-di-tert-butyl-4-methyl
phenyl-stearyl-pentaerythritol diphosphite;
2,6-ditert-butyl-4-methyl phenyl-cyclohexyl-pentaerythritol
diphosphite;
2,6-di-tert-butyl-4-methylphenyl-benzyl-pentaerythritol
diphosphite;
2,6-di-tert-butyl-4-methylphenyl-ethylcellosolve-pentaerythritol
diphosphite;
2,6-di-tert-butyl-4-methylphenyl-butylcarbitol-pentaerythritol
diphosphite;
2,6-di-tert-butyl-4-methylphenyl-octylphenyl-pentaerythritol
diphosphite;
2,6-di-tert-butyl-4-methylphenyl-nonylphenyl-pentaerythritol
diphosphite; bis(2,6-di-tert-butyl-4-methyl phenyl)pentaerythritol
diphosphite; bis(2,6-di-tert-butyl-4-ethylphenyl)pentaerythritol
diphosphite;
2,6-di-tert-butyl-4-methylphenyl-2,6-di-tertbutylphenyl-pentaerythritol
diphosphite;
2,6-di-tert-butyl-4-methylphenyl-2,4-di-tertbutylphenyl-pentaerythritol
diphosphite;
2,6-di-tert-butyl-4-methylphenyl-2,4-di-tertoctylphenyl-pentaerythritol
diphosphite;
2,6-di-tert-butyl-4-methylphenyl-2-cyclohexylphenyl-pentaerythritol
diphosphite; 2,6-di-tert-amyl-4-methylphenyl-phenyl-pentaerythritol
diphosphite; bis(2,6-di-tert-amyl-4-methylphenyl)pentaerythritol
diphosphite; and
bis(2,6-di-tert-octyl-4-methylphenyl)pentaerythritol
diphosphite.
[0093] Examples of hindered amine-based stabilizers include
4-acetoxy-2,2,6,6-tetra methyl piperidine;
4-stearoyloxy-2,2,6,6-tetramethylpiperidine;
4-acryloyloxy-2,2,6,6-tetramethylpiperidine;
4-(phenylacetoxy)-2,2,6,6-tetramethylpiperidine;
4-benzoyloxy-2,2,6,6-tetramethylpiperidine;
4-methoxy-2,2,6,6-tetramethylpiperidine;
4-stearyloxy-2,2,6,6-tetramethylpiperidine;
4-cyclohexyloxy-2,2,6,6-tetra methylpiperidine;
4-benzyloxy-2,2,6,6-tetramethylpiperidine;
4-phenoxy-2,2,6,6-tetramethylpiperidine;
4-(ethylcarbamoyloxy)-2,2,6,6-tetramethylpiperidine;
4-(cyclohexylcarbamoyloxy)-2,2,6,6-tetramethylpiperidine;
4-(phenylcarbamoyloxy)-2,2,6,6-tetramethylpiperidine;
bis(2,2,6,6-tetramethyl-4-piperidyl)-carbonate;
bis(2,2,6,6-tetramethyl-4-piperidyl)-oxalate;
bis(2,2,6,6-tetramethyl-4-piperidyl)-malonate;
bis(2,2,6,6-tetramethyl-4-piperidyl)-sebacate;
bis(2,2,6,6-tetramethyl-4-piperidyl)-adipate;
bis(2,2,6,6-tetramethyl-4-piperidyl)terephthalate;
1,2-bis(2,2,6,6-tetramethyl-4-piperidyloxy)-ethane;
.alpha.,.alpha.'-bis(2,2,6,6-tetramethyl-4-piperidyloxy)-p-xylene;
bis(2,2,6,6-tetramethyl-4-piperidyl)-tolylene-2,4-dicarbamate;
bis(2,2,6,6-tetra
methyl-4-piperidyl)-hexamethylene-1,6-dicarbamate;
tris(2,2,6,6-tetramethyl-4-piperidyl)-benzene-1,3,5-tricarboxylate;
tris(2,2,6,6-tetramethyl-4-piperidyl)-benzene-1,3,4-tricarboxylate;
1-[2-{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy}butyl]-4-[3-(3,5--
di-tert-butyl-4-hydroxyphenyl)propionyloxy]2,2,6,6-tetramethylpiperidine;
and a condensation product of 1,2,3,4-butanetetracarboxylic acid;
1,2,2,6,6-pentamethyl-4-piperidinol; and
.beta.,.beta.,.beta.',.beta.'-tetramethyl-3,9-[2,4,8,10-tetraoxaspiro(5,5-
)undecane]diethanol.
[0094] Examples of triazine-based stabilizers include
2,4,6-tris(2'-hydroxy-4'-octyloxy-phenyl)-1,3,5-triazine;
2-(2'-hydroxy-4'-hexyloxy-phenyl)-4,6-diphenyl-1,3,5-triazine;
2-(2'-hydroxy-4'-octyloxyphenyl)-4,6-bis(2',4-dimethylphenyl)-1,3,5-triaz-
ine;
2-(2',4'-dihydroxyphenyl)-4,6-bis(2',4'-dimethylphenyl)-1,3,5-triazin-
e;
2,4-bis(2'-hydroxy-4'-propyloxy-phenyl)-6-(2',4'-dimethylphenyl)-1,3,5--
triazine;
2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4'-methylphenyl)-1,3,5-tr-
iazine;
2-(2'-hydroxy-4'-dodecyloxyphenyl)-4,6-bis(2',4'-dimethylphenyl)-1-
,3,5-triazine;
2,4,6-tris(2'-hydroxy-4'-isopropyloxyphenyl)-1,3,5-triazine;
2,4,6-tris(2'-hydroxy-4'-n-hexyloxyphenyl)-1,3,5-triazine; and
2,4,6-tris(2'-hydroxy-4'-ethoxycarbonylmethoxyphenyl)-1,3,5-triazine.
[0095] Copper stabilizers include copper halides, e.g., chlorides,
bromides, iodides. Copper stabilizers also can include copper
cyanide, copper oxide, copper sulfate, copper phosphate, copper
acetate, copper propionate, copper benzoate, copper adipate, copper
terephthalate, copper isophthalate, copper salicylate, copper
nicotinate, copper stearate, and copper complex salts coordinated
to a chelating amine such as ethylenediamine and
ethylenediaminetetraacetic acid.
[0096] In some embodiments, the heat stabilizers comprise a
copper-containing heat stabilizer. In some embodiments, the first
copper-containing heat stabilizer comprises copper, a halogen, (or
a copper halide--a compound containing copper and a halogen), and
optionally an organohalo-phosphorus (organobromine-phosphorus)
compound. In some aspects, the first copper-containing heat
stabilizer comprises a mixture including copper halides,
phosphates, or phosphines, or complexes thereof. In some aspects,
the first copper-containing heat stabilizer comprises a complex
including copper iodide, bis(triphenylphosphine), and
tris(tribromoneopentyl)phosphate. Suitable first copper-containing
heat stabilizers include those described in German Patent No.
DE19847626, which is incorporated by reference in its entirety.
[0097] These copper halide and organohalo-phosphorus
(organobromine-phosphorus) compound combinations, when added to the
polyamides described herein, result in polyamide compositions that
exhibit superior heat stability while also maintaining excellent
electrical properties, thus making the polyamide compositions of
the present invention ideally suited for use in the
electrical/electronic industries. As a further benefit, this
combination of a copper halide and an organophosphorus compound
does not discolor the polyamide composition. Suitable commercial
(first) copper-containing heat stabilizers include BRUGGOLEN.RTM.
H3386 (available from Bruggemann Chemical).
[0098] In some embodiments, the polyamide composition includes a
cerium-based heat stabilizer, e.g., cerium oxide, cerium hydrate,
and/or cerium oxyhydrate.
[0099] The concentration of the heat stabilizer in the polyamide
composition can, for example, range from 0.1 to 5 wt %, e.g., from
0.1 wt % to 1 wt %, from 0.15 wt % to 1.5 wt %, from 0.22 wt % to
2.3 wt %, from 0.1 wt % to 3 wt %, from 0.15 wt % to 1 wt %, from
0.32 wt % to 3.4 wt %, or from 0.48 wt % to 5 wt %. In some
embodiments, the concentration of the heat stabilizer ranges from
0.2 wt % to 0.7 wt %. In terms of upper limits, the heat stabilizer
concentration can be less than 5 wt %, e.g., less than 3.4 wt %,
less than 3 wt %, less than 2.3 wt %, less than 1.5 wt %, less than
1 wt %, less than 0.71 wt %, less than 0.48 wt %, less than 0.32 wt
%, less than 0.22 wt %, or less than 0.15 wt %. In terms of lower
limits, the heat stabilizer concentration can be greater than 0.1
wt %, e.g., greater than 0.15 wt %, greater than 0.22 wt %, greater
than 0.32 wt %, greater than 0.48 wt %, greater than 0.71 wt %,
greater than 1 wt %, greater than 1.5 wt %, greater than 2.3 wt %,
or greater than 3.4 wt %. Lower concentrations, e.g., less than 0.1
wt %, and higher concentrations, e.g., greater than 5 wt %, are
also contemplated.
[0100] In some embodiments, the heat stabilizer comprises copper or
a copper-containing compound such as, for example, copper iodide.
After combining the heat stabilizer with the other polyamide
composition components, the concentration of copper in the
polyamide composition can, for example, range from 25 ppm to 700
ppm, e.g., from 25 ppm to 180 ppm, from 35 ppm to 260 ppm, from 49
ppm to 360 ppm, from 68 ppm to 500 ppm, or from 95 ppm to 700 ppm.
In terms of upper limits, the concentration of copper in the
polyamide composition can be less than 700 ppm, e.g., less than 500
ppm, less than 360 ppm, less than 260 ppm, less than 180 ppm, less
than 130 ppm, less than 95 ppm, less than 68 ppm, less than 49 ppm,
or less than 35 ppm. In terms of lower limits, the concentration of
copper in the polyamide composition can be greater than 25 ppm,
e.g., greater than 35 ppm, greater than 49 ppm, greater than 68
ppm, greater than 95 ppm, greater than 130 ppm, greater than 180
ppm, greater than 260 ppm, greater than 360 ppm, or greater than
500 ppm. Higher concentrations, e.g., greater than 700 ppm, and
lower concentrations, e.g., less than 25 ppm, are also
contemplated.
[0101] The weight ratio of the one or more polyamides to the heat
stabilizer in the polyamide composition can, for example, range
from 1 to 850, e.g., from 1 to 57, from 2 to 110, from 3.9 to 220,
from 7.6 to 430, or from 15 to 850. In terms of upper limits, the
weight ratio of the one or more polyamide polymers to the heat
stabilizer can be less than 850, e.g., less than 430, less than
220, less than 110, less than 29, less than 57, less than 15, less
than 7.6, less than 3.9, or less than 2. In terms of lower limits,
the weight ratio of the one or more polyamide polymers to the heat
stabilizer can be greater than 1, e.g., greater than 2, greater
than 3.9, greater than 7.6, greater than 15, greater than 29,
greater than 57, greater than 110, greater than 220, or greater
than 430. Lower ratios, e.g., less than 1, and higher ratios, e.g.,
greater than 850, are also contemplated.
[0102] The weight ratio of the impact modifier to the heat
stabilizer in the polyamide composition can, for example, range
from 0.5 to 300, e.g., from 0.5 to 23, from 0.95 to 44, from 1.8 to
83, from 10 to 40 from 12 to 35, from 3.4 to 160, or from 6.5 to
300. In terms of upper limits, the weight ratio of the impact
modifier to the heat stabilizer can be less than 300, e.g., less
than 160, less than 83, less than 44, less than 40, less than 35,
less than 23, less than 12, less than 6.5, less than 3.4, less than
1.8, or less than 0.95. In terms of lower limits, the weight ratio
of the impact modifier to the heat stabilizer can be greater than
0.5, e.g., greater than 0.95, greater than 1.8, greater than 3.4,
greater than 6.5, greater than 10, greater than 12, greater than
23, greater than 44, greater than 83, or greater than 160. Lower
ratios. e.g., less than 0.5, and higher ratios, e.g., greater than
300, are also contemplated.
Color Package (Nigrosine/Carbon Black)
[0103] The polyamide composition can include one or more soluble
dyes such as nigrosine or solvent black 7. The concentration of the
nigrosine in the polyamide composition can, for example, range from
0.1 to 5 wt %, e.g., from 0.1 wt % to 1 wt %, from 0.15 wt % to 1.5
wt %, from 0.22 wt % to 2.3 wt %, from 0.32 wt % to 3.4 wt %, or
from 0.48 wt % to 5 wt %. In some embodiments, the concentration of
the nigrosine ranges from 1 wt % to 2 wt %, e.g., from 1 wt % to
1.6 wt %, from 1.1 wt % to 1.7 wt %, from 1.2 wt % to 1.8 wt %,
from 1.3 wt % to 1.9 wt %, or from 1.4 wt % to 2 wt %. In terms of
upper limits, the nigrosine concentration can be less than 5 wt %,
e.g., less than 3.4 wt %, less than 2.3 wt %, less than 2 wt %,
less than 1.9 wt %, less than 1.8 wt %, less than 1.7 wt %, less
than 1.6 wt %, less than 1.5 wt %, less than 1.4 wt %, less than
1.3 wt %, less than 1.2 wt %, less than 1.1 wt %, less than 1 wt %,
less than 0.71 wt %, less than 0.48 wt %, less than 0.32 wt %, less
than 0.22 wt %, or less than 0.15 wt %. In terms of lower limits,
the nigrosine concentration can be greater than 0.1 wt %, e.g.,
greater than 0.15 wt %, greater than 0.22 wt %, greater than 0.32
wt %, greater than 0.48 wt %, greater than 0.71 wt %, greater than
1 wt %, greater than 1.1 wt %, greater than 1.2 wt %, greater than
1.3 wt %, greater than 1.4 wt %, greater than 1.5 wt %, greater
than 1.6 wt %, greater than 1.7 wt %, greater than 1.8 wt %,
greater than 1.9 wt %, greater than 2 wt %, greater than 2.3 wt %,
or greater than 3.4 wt %. Lower concentrations, e.g., less than 0.1
wt %, and higher concentrations, e.g., greater than 5 wt %, are
also contemplated. In some cases, the nigrosine is provided in a
masterbatch, and the concentration of the nigrosine in the
masterbatch and in the resultant composition can be easily
calculated.
[0104] The weight ratio of the one or more polyamide polymers to
the nigrosine in the polyamide composition can, for example, range
from 1 to 85, e.g., from 1 to 14, from 1.6 to 22, from 2.4 to 35,
from 3.8 to 55, or from 5.9 to 85. In terms of upper limits, the
ratio of the one or more polyamide polymers to the nigrosine can be
less than 85, e.g., less than 55, less than 35, less than 22, less
than 14, less than 9.2, less than 5.9, less than 3.8, less than
2.4, or less than 1.6. In terms of lower limits, the ratio of the
one or more polyamide polymers to the nigrosine can be greater than
1, e.g., greater than 1.6, greater than 2.4, greater than 3.8,
greater than 5.9, greater than 9.2, greater than 14, greater than
22, greater than 35, or greater than 55. Higher ratios, e.g.,
greater than 55, and lower ratios, e.g., less than 1, are also
contemplated.
[0105] The weight ratio of glass fiber to the nigrosine in the
polyamide composition can, for example, range from 2 to 60, e.g.,
from 2 to 15, from 2.8 to 22, from 3.9 to 30, from 5.5 to 43, or
from 7.8 to 60. In terms of upper limits, the ratio of glass fiber
to the nigrosine can be less than 60, e.g., less than 43, less than
30, less than 22, less than 15, less than 11, less than 7.8, less
than 5.5, less than 3.9, or less than 2.8. In terms of lower
limits, the ratio of glass fiber to the nigrosine can be greater
than 2, e.g., greater than 2.8, greater than 3.9, greater than 5.5,
greater than 7.8, greater than 11, greater than 15, greater than
22, greater than 30, or greater than 43. Higher ratios, e.g.,
greater than 60, and lower ratios, e.g., less than 2, are also
contemplated.
[0106] The weight ratio of the heat stabilizer to the nigrosine in
the polyamide composition can, for example, range from 0.02 to 5,
e.g., from 0.02 to 0.55, from 0.035 to 0.95, from 0.06 to 1.7, from
0.1 to 2.9, or from 0.18 to 5. In terms of upper limits, the ratio
of the heat stabilizer to the nigrosine can be less than 5, e.g.,
less than 2.9, less than 1.7, less than 0.95, less than 0.55, less
than 0.32, less than 0.18, less than 0.1, less than 0.06, or less
than 0.035. In terms of lower limits, the ratio of the heat
stabilizer to the nigrosine can be greater than 0.02, e.g., greater
than 0.035, greater than 0.06, greater than 0.1, greater than 0.18,
greater than 0.32, greater than 0.55, greater than 0.95, greater
than 1.7, or greater than 2.9. Higher ratios, e.g., greater than 5,
and lower ratios, e.g., less than 0.02, are also contemplated.
[0107] The polyamide composition can include one or more pigments
such as carbon black. The concentration of the carbon black in the
polyamide composition can, for example, range from 0.1 to 5 wt %,
e.g., from 0.1 wt % to 1.05 wt %, from 0.15 wt % to 1.55 wt %, from
0.22 wt % to 2.29 wt %, from 0.32 wt % to 3.38 wt %, or from 0.48
wt % to 5 wt %. In some embodiments, the concentration of the
carbon black ranges from 0.2 wt % to 0.8 wt %. In terms of upper
limits, the carbon black concentration can be less than 5 wt %,
e.g., less than 3.4 wt %, less than 2.3 wt %, less than 1.5 wt %,
less than 1 wt %, less than 0.71 wt %, less than 0.48 wt %, less
than 0.32 wt %, less than 0.22 wt %, or less than 0.15 wt %. In
some embodiments, the concentration of the carbon black is less
than 3 wt %. In terms of lower limits, the carbon black
concentration can be greater than 0.1 wt %, e.g., greater than 0.15
wt %, greater than 0.22 wt %, greater than 0.32 wt %, greater than
0.48 wt %, greater than 0.71 wt %, greater than 1 wt %, greater
than 1.5 wt %, greater than 2.3 wt %, or greater than 3.4 wt %.
Lower concentrations, e.g., less than 0.1 wt %, and higher
concentrations, e.g., greater than 5 wt %, are also
contemplated.
Melt Stabilizer
[0108] The polyamide composition can include one or more melt
stabilizers (lubricants). The type and relative amount of melt
stabilizer can be selected to improve processing of the
composition, and to contribute to the simultaneously high strength
and ductility of the material. The concentration of the melt
stabilizer in the polyamide composition can, for example, range
from 0.05 wt % to 5 wt %, e.g., from 0.05 wt % to 3 wt %, from 0.1
wt % to 0.6 wt %, from 0.2 wt % to 0.7 wt %, from 0.3 wt % to 0.8
wt %, from 0.1 wt % to 3 wt %, from 0.4 wt % to 0.9 wt %, from 0.5
wt % to 1 wt %, from 0.15 wt % to 1.5 wt %, from 0.22 wt % to 2.3
wt %, from 0.32 wt % to 3.4 wt %, or from 0.48 wt % to 5 wt %. In
terms of upper limits, the melt stabilizer concentration can be
less than 5 wt %, e.g., less than 3.4 wt %, less than 2.3 wt %,
less than 1.5 wt %, less than 1 wt %, less than 0.9 wt %, less than
0.8 wt %, less than 0.7 wt %, less than 0.6 wt %, less than 0.5 wt
%, less than 0.4 wt %, less than 0.3 wt %, less than 0.2 wt %, or
less than 0.1 wt %. In terms of lower limits, the melt stabilizer
concentration can be greater than 0.1 wt %, e.g., greater than 0.2
wt %, greater than 0.3 w %, greater than 0.4 wt %, greater than 0.5
wt %, greater than 0.6 wt %, greater than 0.7 wt %, greater than
0.8 wt %, greater than 0.9 wt %, greater than 1 wt %, greater than
1.5 wt %, greater than 2.3 wt %, or greater than 3.4 wt %. Lower
concentrations, e.g., less than 0.1 wt %, and higher
concentrations, e.g., greater than 5 wt %, are also
contemplated.
[0109] In some embodiments, the melt stabilizer comprises a
saturated fatty acid. For example the melt stabilizer may comprise
stearic acid, or behenic acid, or combinations thereof, or salts
thereof. In some cases, the melt stabilizer comprises a stearate.
The melt stabilizer, in some cases can include, for example,
calcium stearate, aluminum distearate, zinc stearate, calcium
stearate, N,N' ethylene bis-stearamide, stearyl erucamide. In some
cases, the melt stabilizer comprises stearic acid. In some cases
the zinc stearate (or zinc borate (see below)) is not considered
the zinc AM/AV compound.
[0110] In some embodiments, the melt stabilizer does not include an
ionic lubricant. In addition to other performance improvements, the
disclosed melt stabilizers, also significantly improve dispersion
of the components in the matrix of the polymer, e.g., the
dispersion of the impact modifiers in the polyamide matrix.
[0111] In some embodiments, the melt stabilizer may be a wax. In
some embodiments, the melt stabilizer consists of a wax. In some
embodiments, the wax includes a fatty acid. In some embodiments,
the melt stabilizer consists of a fatty acid. In some embodiments,
the wax includes a saturated fatty acid. In some embodiments, the
melt stabilizer consists of a saturated fatty acid. In some
embodiments, the wax includes stearic acid, behenic acid, or salts
or combinations thereof. In some embodiments, the wax consists of
stearic acid, behenic acid, or salts or combinations thereof.
[0112] In addition to other performance improvements, the disclosed
melt stabilizers, also significantly improve dispersion of the
components in the matrix of the polymer, e.g., the dispersion of
the impact modifiers in the polyamide matrix, which beneficially
improves impact performance.
[0113] The concentration of the melt stabilizer, e.g., stearic acid
or salt thereof, in the polyamide composition can, for example,
range from 0.03 wt % to 4 wt %, e.g., from 0.03 wt % to 0.57 wt %,
from 0.05 wt % to 0.92 wt %, from 0.08 wt % to 1.5 wt %, from 0.13
wt % to 2.5 wt %, or from 0.21 wt % to 4 wt %. In terms of upper
limits, the stearic acid or salt concentration can be less than 4
wt %, e.g., less than 2.4 wt %, less than 1.5 wt %, less than 0.92
wt %, less than 0.57 wt %, less than 0.35 wt %, less than 0.21 wt
%, less than 0.13 wt %, less than 0.08 wt %, or less than 0.05 wt
%. In terms of lower limits, the stearic acid or salt concentration
can be greater than 0.03 wt %, e.g., greater than 0.05 wt %,
greater than 0.08 wt %, greater than 0.13 wt %, greater than 0.21
wt %, greater than 0.35 wt %, greater than 0.57 wt %, greater than
0.92 wt %, greater than 1.5 wt %, or greater than 2.5 wt %. Higher
concentrations, e.g., greater than 4 wt %, and lower
concentrations, e.g., less than 0.03 wt %, are also
contemplated.
[0114] The weight ratio of the impact modifier to the melt
stabilizer in the polyamide composition can, for example, range
from 1 to 100, e.g., from 2 to 50, from 5 to 50, from 10 to 40,
from 10 to 35, from 5 to 25, from 10 to 20, from 10 to 50, from 20
to 40, or from 25 to 35. In terms of upper limits, the ratio of the
impact modifier to the melt stabilizer can be less than 100, e.g.,
less than 75, less than 50, less than 40, less than 35, less than
25, or less than 20. In terms of lower limits, the ratio of the
impact modifier to the melt stabilizer can be greater than 1, e.g.,
greater than 2, greater than 5, greater than 10, greater than 20,
or greater than 25. Higher ratios are also contemplated.
[0115] As noted above, the combination of the impact modifier and
the melt stabilizer leads to synergistic combinations of
performance features. Generally, impact modifiers are known to have
detrimental effects on tensile strength. For example a degradation
in shear of the polymer is observed (shear is detrimentally
increased and tensile performance is adversely affected). However,
when the disclosed impact modifiers and melt stabilizers are used
together, an unexpected balance is struck, the melt stabilizers
reduce or eliminate the degradation. As a result, little or no loss
in tensile performance is observed, while surprisingly impact
resilience is significantly improved.
Flame Retardants
[0116] The flame retardant package may vary widely, and many
suitable flame retardants are known. Examples of
(bromine-containing) flame retardants include
hexabromocyclododecane (HBCD), decabromodiphenyl oxide (DBDPO),
octabromodiphenyl oxide, tetrabromobisphenol A (TBBA),
bis(tribromophenoxy)ethane, bis(pentabromophenyl)ethane,
tetrabromobisphenol A epoxy resin (TBBA epoxy), tetrabromobisphenol
A carbonate (TBBA-PC), ethylene(bistetrabromophthal)imide (EBTBPI),
ethylenebispentabromodiphenyl, tris(tribromophenoxy)triazine
(TTBPTA), bis(dibromopropyl)tetrabromobisphenol A (DBP-TBBA),
bis(dibromopropyl)tetrabromobisphenol S (DBP-TBBS), brominated
polyphenylene ethers (BrPPE) (such as poly(di)bromophenylene ether,
etc.), brominated polystyrenes (BrPPE) (such as
polydibromostyrenes, polytribromostyrenes, crosslinked brominated
polystyrenes, etc.), brominated crosslinked aromatic polymers,
brominated epoxy resins, brominated phenoxy resins, brominated
styrene-maleic anhydride polymers, tetrabromobisphenol S (TBBS),
tris(tribromoneopentyl)phosphate (TTBNPP),
polybromotrimethylphenylindan (PBPI), and
tris(dibromopropyl)-isocyanurate (TDBPIC).
[0117] Halogen-based flame retardants may also be used.
Conventional flame retardant synergists include, but are not
limited to, antimony oxides (such as diantimony trioxide,
diantimony tetroxide, diantimony pentoxide and sodium antimonate),
tin oxides (such as tin monoxide and tin dioxide), iron oxides
(such as iron(II) oxide and .gamma.-iron oxide), zinc oxide and
zinc borate. Generally, non-halogenated flame retardants are used
due to a desire to avoid the potentially adverse environmental
impact of halogenated flame retardants.
[0118] Exemplary non-halogenated flame retardants include
phosphorus- or melamine-containing flame retardants. Melamine flame
retardants are known in the art and include melamine phosphates and
melamine cyanurate. Phosphate esters are especially suitable for
use. Such compounds include, for example, alkyl and aryl esters of
phosphoric acid such as trimethyl phosphate, triethyl phosphate,
tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate,
triphenyl phosphate, tricresyl phosphate, cresyldiphenyl phosphate,
octyldiphenyl phosphate, tri(2-ethylhexyl) phosphate,
di-iso-propylphenyl phosphate, trixylenyl phosphate,
tris(iso-propylphenyl) phosphate, trinaphthyl phosphate, bisphenol
A diphenyl phosphate, and resorcinol diphenyl phosphate. Commonly
used triaryl phosphates include, for example, triphenyl phosphate
(TPP), cresyl diphenyl phosphate, and tricresyl phosphate.
Inorganic phosphate flame retardants such as ammonium polyphosphate
(which acts as an intumescent flame retardant) may also be
utilized.
[0119] Phosphinate flame retardants, including those sold under the
Exolit.RTM. name, such as OP1230 and OP1400 may be used in the
composition described herein. Phosphinate flame retardants may be
desirable because of their anti-corrosive nature.
[0120] The concentration of the flame retardant in the polyamide
composition can, for example, range from 3 wt % to 30 wt %, e.g.,
from 2 wt % to 25 wt %, from 2 wt % to 20 wt %, from 5.7 wt % to
21.9 wt %, from 4.0 wt % to 15 wt %, from 5.5 wt % to 14 wt %, from
6.0 wt % to 11.5 wt %, from 8.4 wt % to 24.6 wt %, from 11.1 wt %
to 27.3 wt %, or from 13.8 wt % to 30 wt %. In some embodiments,
the concentration of the flame retardant ranges from 6 wt % to 20
wt %, e.g., from 6 wt % to 14.4 wt %, from 7.4 wt % to 15.8 wt %,
from 8.8 wt % to 17.2 wt %, from 10.2 wt % to 18.6 wt %, or from
11.6 wt % to 20 wt %. In terms of upper limits, the impact modifier
concentration can be less than 30 wt %, e.g., less than 27.3 wt %,
less than 24.6 wt %, less than 21.9 wt %, less than 20 wt %, less
than 18.6 wt %, less than 17.2 wt %, less than 15.8 wt %, less than
15 wt %, less than 14 wt %, less than 14.4 wt %, less than 13 wt %,
less than 11.6 wt %, less than 11.5 wt %, less than 10.2 wt %, less
than 8.8 wt %, less than 7.4 wt %, less than 6 wt %, or less than
5.4 wt %. In terms of lower limits, the flame retardant
concentration can be greater than 3 wt %, greater than 4.0 wt %,
greater than 5.5 wt %, greater than 5.4 wt %, greater than 6 wt %,
greater than 7.4 wt %, greater than 8.8 wt %, greater than 10.2 wt
%, greater than 11.6 wt %, greater than 13 wt %, greater than 14.4
wt %, greater than 15.8 wt %, greater than 17.2 wt %, greater than
18.6 wt %, greater than 20 wt %, greater than 21.9 wt %, greater
than 24.6 wt %, or greater than 27.6 wt %. Lower concentrations,
e.g., less than 3 wt %, and higher concentrations, e.g., greater
than 30 wt %, are also contemplated.
[0121] In cases where the flame retardant is a non-halogenated
flame retardant, the non-halogenated flame retardant may be present
in an amount of at least 5 wt. %, based on the total weight of the
composition, e.g., at least 7.5 wt. %, at least 10 wt. %, or at
least 12.5 wt. %. In terms of upper limits, the non-halogenated
flame retardant is present in an amount of less than 25 wt. %,
e.g., less than 22.5 wt. %, less than 20 wt. %, or less than 17.5
wt. %. In terms of ranges, the non-halogenated flame retardant is
present from 5 to 25 wt. %, e.g., from 7.5 to 22.5 wt. %, from 10
to 20 wt. %, or from 12.5 to 17.5 wt. %.
Other Additives
[0122] The polyamide composition can also include one or more chain
terminators, viscosity modifiers, plasticizers, e.g., diundecyl
phthalate, UV stabilizers, catalysts, other polymers, delusterants,
antimicrobial agents, antistatic agents, optical brighteners,
extenders, processing aids, talc, mica, gypsum, wollastonite and
other commonly used additives known to those of skill in the art.
Additional suitable additives may be found in Plastics Additives,
An A-Z reference, Edited by Geoffrey Pritchard (1998). The optional
addition of a stabilizer to the additive dispersion is present in
an exemplary embodiment. Stabilizers suitable for the additive
dispersion include, but are not limited to, polyethoxylates (such
as the polyethoxylated alkyl phenol Triton X-100),
polypropoxylates, block copolymeric polyethers, long chain
alcohols, polyalcohols, alkyl sulfates, alkyl-sulfonates,
alkyl-benzenesulfonates, alkylphosphates, alkyl-phosphonates,
alkyl-naphthalene sulfonates, carboxylic acids and
perfluoronates.
[0123] In some embodiments, the stain resistance of the polyamide
composition can be improved by salt-blending the polyamide
precursor with a cationic dye modifier, such as 5-sulfoisophthalic
acid or salts or other derivatives thereof.
[0124] Chain extenders can also be included in the polyamide
composition. Suitable chain extender compounds include bis-N-acyl
bislactam compounds, isophthaloyl bis-caprolactam (IBC), adipoyl
bis-caprolactam (ABC), terphthaloyl bis-caprolactam (TBS), and
mixtures thereof.
[0125] The polyamide composition can also include anti-block
agents. Inorganic solids, usually in the form of diatomaceous
earth, represent one class of materials that can be added to the
disclosed polyamide composition. Non-limiting examples include
calcium carbonate, silicon dioxide, magnesium silicate, sodium
silicate, aluminum silicate, aluminum potassium silicate, and
silicon dioxide are examples of suitable antiblock agents.
[0126] The disclosed polyamide compositions can also include a
nucleating agent to further improve clarity and oxygen barrier as
well as enhance oxygen barrier. Typically, these agents are
insoluble, high melting point species that provide a surface for
crystallite initiation. By incorporating a nucleating agent, more
crystals are initiated, which are smaller in nature. More
crystallites or higher % crystallinity correlates to more
reinforcement/higher tensile strength and a more tortuous path for
oxygen flux (increased barrier); smaller crystallites decreases
light scattering which correlates to improved clarity. Non-limiting
examples include calcium fluoride, calcium carbonate, talc and
Nylon 2,2.
[0127] The polyamide compositions can also include organic
anti-oxidants in the form of hindered phenols such as, but not
limited to, Irganox 1010, Irganox 1076 and Irganox 1098; organic
phosphites such as, but not limited to, Irgafos 168 and Ultranox
626; aromatic amines, metal salts from Groups IB, IIB, III, and IV
of the periodic table and metal halides of alkali and alkaline
earth metals.
Glass Fiber
[0128] The polyamide composition includes a reinforcing filler,
e.g., glass fiber. The glass fiber can include soda lime silicate,
zirconium silicates, calcium borosilicates, alumina-calcium
borosilicates, calcium aluminosilicates, magnesium
aluminosilicates, or combinations thereof. The glass fiber can
include long fibers, e.g., greater than 6 mm, short fibers, e.g.,
less than 6 mm, or combinations thereof. The glass fiber can be
milled.
[0129] The amount of glass fiber in the polyamide composition
relative to the amounts of the other composition components can be
selected to advantageously provide additional strength without
negatively affecting material ductility. The concentration of glass
fiber in the polyamide composition can, for example, range from 10
wt % to 60 wt %, e.g., from 10 wt % to 40 wt %, from 15 wt % to 45
wt %, from 20 wt % to 50 wt %, from 25 wt % to 55 wt %, or from 30
wt % to 60 wt %. In some embodiments, the concentration of glass
fiber ranges from 25 wt % to 40 wt % e.g., from 25 wt % to 34 wt %,
from 26.5 wt % to 35.5 wt %, from 28 wt % to 37 wt %, from 29.5 wt
% to 38.5 wt %, or from 31 wt % to 40 wt %. In certain aspects, the
concentration of glass fiber ranges from 30 wt % to 35 wt %. In
terms of upper limits, the glass fiber concentration can be less
than 60 wt %, e.g., less than 55 wt %, less than 50 wt %, less than
45 wt %, less than 40 wt %, less than 38.5 wt %, less than 37 wt %,
less than 35.5 wt %, less than 34 wt %, less than 32.5 wt %, less
than 31 wt %, less than 29.5 wt %, less than 28 wt %, less than
26.5 wt %, less than 25 wt %, less than 20 wt %, or less than 15 wt
%. In terms of lower limits, the glass fiber concentration can be
greater than 10 wt %, e.g., greater than 15 wt %, greater than 20
wt %, greater than 25 wt %, greater than 26.5 wt %, greater than 28
wt %, greater than 29.5 wt %, greater than 31 wt %, greater than
32.5 wt %, greater than 34 wt %, greater than 35.5 wt %, greater
than 37 wt %, greater than 38.5 wt %, greater than 40 wt %, greater
than 45 wt %, greater than 50 wt %, or greater than 55 wt %. Lower
concentrations, e.g., less than 10 wt %, and higher concentrations,
e.g., greater than 60 wt %, are also contemplated.
Antiviral Activity
[0130] The polymer compositions described herein exhibit antiviral
properties, e.g., antiviral activity. Furthermore, the products
formed from the polymer compositions may also exhibit antiviral
properties. In particular, by utilizing a polymer composition
having the aforementioned zinc, copper, silver and/or phosphorus
compounds in the disclosed concentrations, a polymer composition
exhibiting antiviral properties can be prepared.
[0131] In some embodiments, the polymer compositions, and the
products formed therefrom, exhibit permanent, e.g., near permanent,
antiviral properties. Said another way, the antiviral properties of
the polymer composition last for a prolonged period of time, e.g.,
longer than one or more day, longer than one or more week, longer
than one or more month, or longer than one or more years.
[0132] The antiviral properties may include any antiviral effect.
In some embodiments, for example, the antiviral properties of the
polymer composition include limiting, reducing, or inhibiting
infection of a virus. In some embodiments, the antiviral properties
of the polymer composition include limiting, reducing, or
inhibiting pathogenesis of a virus. In some cases, the polymer
composition may limit, reduce, or inhibit both infection and
pathogenesis of a virus.
[0133] The virus affected by the antiviral properties of the
polymer composition is not particularly limited. In some
embodiments, for example, the virus is an adenovirus, a
herpesvirus, an ebolavirus, a poxvirus, a rhinovirus, a
coxsackievirus, an arterivirus, an enterovirus, a morbillivirus, a
coronavirus, an influenza A virus, an avian influenza virus, a
swine-origin influenza virus, or an equine influence virus. In some
embodiments, the antiviral properties include limiting, reducing,
or inhibiting the infection or pathogenesis of one of virus, e.g.,
a virus from the above list. In some embodiments, the antiviral
properties include limiting, reducing, or inhibiting the infection
or pathogenesis of multiple viruses, e.g., a combination of two or
more viruses from the above list.
[0134] In some cases, the virus is a coronavirus, e.g., severe
acute respiratory syndrome coronavirus (SARS-CoV), Middle East
respiratory syndrome coronavirus (MERS-CoV), or severe acute
respiratory syndrome coronavirus 2 (SARS-CoV-2) (e.g., the
coronavirus that causes COVID-19). In some cases, the virus is
structurally related to a coronavirus.
[0135] In some cases, the virus is an influenza virus, such as an
influenza A virus, an influenza B virus, an influenza C virus, or
an influenza D virus, or a structurally related virus. In some
cases, the virus is identified by an influenza A virus subtype,
e.g., H1N1, H1N2, H2N2, H2N3, H3N1, H3N2, H3N8, H5N1, H5N2, H5N3,
H5N6, H5N8, H5N9, H6N1, H7N1, H7N4, H7N7, H7N9, H9N2, or H10N7.
[0136] In some cases, the virus is a the virus is a bacteriophage,
such as a linear or circular single-stranded DNA virus (e.g., phi X
174 (sometimes referred to as TX174)), a linear or circular
double-stranded DNA, a linear or circular single-stranded RNA, or a
linear or circular double-stranded RNA. In some cases, the
antiviral properties of the polymer composition may be measured by
testing using a bacteriophage, e.g., phi X 174.
[0137] In some cases, the virus is an ebolavirus, e.g., Bundibugyo
ebolavirus (BDBV), Reston ebolavirus (RESTV), Sudan ebolavirus
(SUDV), Tai Forest ebolavirus (TAFV), or Zaire ebolavirus (EBOV).
In some cases, the virus is structurally related to an
ebolavirus.
[0138] The antiviral activity may be measured by a variety of
conventional methods. For example, ISO 18184:2019 and/or AATCC
TM100 may be utilized to assess the antiviral activity. In one
embodiment, the polymer composition, e.g., products formed from the
polymer composition inhibits the pathogenesis (e.g., growth) of a
virus in an amount ranging from 60% to 100%, e.g., from 60% to
99.999999%, from 60% to 99.99999%, from 60% to 99.9999%, from 60%
to 99.999% from 60% to 99.999%, from 60% to 99.99%, from 60% to
99.9%, from 60% to 99%, from 60% to 98%, from 60% to 95%, from 65%
to 99.999999%, from 65% to 99.99999%, from 65% to 99.9999%, from
65% to 99.999% from 65% to 99.999%, from 65% to 100%, from 65% to
99.99%, from 65% to 99.9%, from 65% to 99%, from 65% to 98%, from
65% to 95%, from 70% to 100%, from 70% to 99.999999%, from 70% to
99.99999%, from 70% to 99.9999%, from 70% to 99.999% from 70% to
99.999%, from 70% to 99.99%, from 70% to 99.9%, from 70% to 99%,
from 70% to 98%, from 70% to 95%, from 75% to 100%, from 75% to
99.99%, from 75% to 99.9%, from 75% to 99.999999%, from 75% to
99.99999%, from 75% to 99.9999%, from 75% to 99.999% from 75% to
99.999%, from 75% to 99%, from 75% to 98%, from 75% to 95%, %, from
80% to 99.999999%, from 80% to 99.99999%, from 80% to 99.9999%,
from 80% to 99.999% from 80% to 99.999%, 90% to 99.999%, 99% to
99.999% or 99% to 99.9%, from 80% to 100%, from 80% to 99.99%, from
80% to 99.9%, from 80% to 99%, from 80% to 98%, or from 80% to 95%.
In terms of lower limits, a fiber formed from the polymer
composition may inhibit greater than 60% of pathogenesis of the
virus, e.g., greater than 65%, greater than 70%, greater than 75%,
greater than 80%, greater than 85%, greater than 90%, greater than
95%, greater than 98%, greater than 99%, greater than 99.9%,
greater than 99.99%, greater than 99.999%, greater than 99.9999%,
greater than 99.99999%, or greater than 99.999999%.
[0139] In some cases, the efficacy may be measured in term of log
reduction. For example, the composition/products may demonstrate a
virus log reduction greater than 0.5, as determined via ISO
18184:2019 or ASTM 2197 (current year), e.g., greater than 1.0,
greater than 1.2, greater than 1.5, greater than 2.0, greater than
2.5, greater than 3.0, greater than 4.0, or greater than 5.0.
Antimicrobial Activity
[0140] In some embodiments, the polymer compositions, and the
products formed therefrom, may also exhibit antimicrobial activity.
In some cases, the antimicrobial activity may be the result of an
additional antimicrobial additive, as described below, or a result
of the polymer composition itself. In some embodiments, the polymer
compositions, and the products formed therefrom, exhibit
antimicrobial properties. Said another way, the antimicrobial
properties of the polymer composition last for a prolonged period
of time, e.g., longer than one or more day, longer than one or more
week, longer than one or more month, or longer than one or more
years.
[0141] The antimicrobial properties may include any antimicrobial
effect. In some embodiments, for example, the antimicrobial
properties of the polymer composition include limiting, reducing,
or inhibiting infection of a microbe, e.g., a bacterium or
bacteria. In some embodiments, the antimicrobial properties of the
polymer composition include limiting, reducing, or inhibiting
growth and/or killing a bacterium. In some cases, the polymer
composition may limit, reduce, or inhibit both infection and growth
of a bacterium.
[0142] The bacterium or bacteria affected by the AM/AV properties
of the polymer composition is not particularly limited. In some
embodiments, for example, the bacterium is a Streptococcus
bacterium (e.g., Streptococcus pneumonia, Streptococcus pyogenes),
a Staphylococcus bacterium (e.g., Staphylococcus aureus,
Methicillin-resistant Staphylococcus aureus (MRSA)), a
Peptostreptococcus bacteria (e.g., Peptostreptococcus anaerobius,
Peptostreptococcus asaccharolyticus), or a Mycobacterium bacterium,
(e.g., Mycobacterium tuberculosis), a Mycoplasma bacteria (e.g.,
Mycoplasma adleri, Mycoplasma agalactiae, Mycoplasma agassizii,
Mycoplasma amphoriforme, Mycoplasma fermentans, Mycoplasma
genitalium, Mycoplasma haemofelis, Mycoplasma hominis, Mycoplasma
hyopneumoniae, Mycoplasma hyorhinis, Mycoplasma pneumoniae). In
some embodiments, the antiviral properties include limiting,
reducing, or inhibiting the infection or pathogenesis of multiple
bacteria, e.g., a combination of two or more bacteria from the
above list.
[0143] The antimicrobial activity may be measured by various test
methods. For example one standard procedure that may be utilized is
testing Staphylococcus Aureus via ISO 22196:2011. This procedure
measures antimicrobial activity by determining the percentage of a
given bacterium or bacteria, e.g. S. aureus or E. coli, inhibited
by a tested product. Other tests include ASTM E35.15 WK45351, ASTM
E2149, ISO 20743:2013, ASTM 3160 (2018), and AATC 100 (current
year).
[0144] In one embodiment, a product formed from the polymer
composition inhibits the growth (growth reduction) of
Staphylococcus Aureus, as measured by ISO 22196:2011, in an amount
ranging from 60% to 100%, e.g., from 60% to 99.999999%, from 60% to
99.99999%, from 60% to 99.9999%, from 60% to 99.999% from 60% to
99.999%, from 60% to 99.99%, from 60% to 99.9%, from 60% to 99%,
from 60% to 98%, from 60% to 95%, from 65% to 99.999999%, from 65%
to 99.99999%, from 65% to 99.9999%, from 65% to 99.999% from 65% to
99.999%, from 65% to 100%, from 65% to 99.99%, from 65% to 99.9%,
from 65% to 99%, from 65% to 98%, from 65% to 95%, from 70% to
100%, from 70% to 99.999999%, from 70% to 99.99999%, from 70% to
99.9999%, from 70% to 99.999% from 70% to 99.999%, from 70% to
99.99%, from 70% to 99.9%, from 70% to 99%, from 70% to 98%, from
70% to 95%, from 75% to 100%, from 75% to 99.99%, from 75% to
99.9%, from 75% to 99.999999%, from 75% to 99.99999%, from 75% to
99.9999%, from 75% to 99.999% from 75% to 99.999%, from 75% to 99%,
from 75% to 98%, from 75% to 95%, %, from 80% to 99.999999%, from
80% to 99.99999%, from 80% to 99.9999%, from 80% to 99.999% from
80% to 99.999%, from 80% to 100%, 90% to 99.999%, 99% to 99.999% or
99% to 99.9%, from 80% to 99.99%, from 80% to 99.9%, from 80% to
99%, from 80% to 98%, or from 80% to 95%. In terms of lower limits,
a product formed from the polymer composition may inhibit greater
than 60% growth of S. aureus, e.g., greater than 65%, greater than
70%, greater than 75%, greater than 80%, greater than 85%, greater
than 90%, greater than 95%, greater than 98%, greater than 99%,
greater than 99.9%, greater than 99.99%, greater than 99.999%,
greater than 99.9999%, greater than 99.99999%, or greater than
99.999999%.
[0145] In terms of Staphylococcus Aureus efficacy, the AM/AV
products inhibit/reduce Staph Aureus activity, as measured by ISO
22196:2011, by greater than 85%, e.g., greater than 86%, greater
than 89%, greater than 90%, greater than 92%, greater than 95%,
greater than 97%, greater than 98%, greater than 99%, greater than
99.5%, greater than 99.9%, greater than 99.99%, greater than
99.999%, greater than 99.9999%, greater than 99.99999%, or greater
than 99.999999%.
[0146] In some embodiments, the AM/AV products inhibit/reduce Staph
Aureus activity (colony forming units per milliliter), as measured
by ASTM E35.15 WK45351, where the product may be extracted with
acetone, and then extracted using boiling water for one hour. In
such cases, the antiviral product inhibit/reduces Staph Aureus
activity by greater than 75%, e.g., greater than 80%, greater than
85%, greater than 90%, greater than 95%, greater than 97%, greater
than 98%, greater than 99%, greater than 99.9%, greater than
99.99%, greater than 99.999%, greater than 99.9999%, greater than
99.99999%, or greater than 99.999999%.
[0147] In some embodiments, the products inhibit/reduces Staph
Aureus activity (colony forming units per milliliter), as measured
by ASTM E2149, where the products may be extracted with acetone,
and then extracted using boiling water for one hour. The test may
be modified to employ a single specimen (1.5 grams), 20 ml
inoculum, an 8 hour incubation time. In such cases, the AM/AV
products inhibit/reduce Staph Aureus activity by greater than 50%,
e.g., greater than 55%, greater than 60%, greater than 63%, greater
than 75%, greater than 80%, greater than 85%, greater than 90%,
greater than 92%, greater than 95%, greater than 97%, greater than
98%, greater than 99%, greater than 99.9%, greater than 99.99%,
greater than 99.999%, greater than 99.9999%, greater than
99.99999%, or greater than 99.999999%.
[0148] Efficacy may be characterized in terms of log reduction. In
terms of Staph Aureus log reduction, the composition/products may
be determined via ISO 22196:2011 and the composition/products may
demonstrate a microbial log reduction greater than 0.8, e.g.,
greater than 1.0, greater than 1.5, greater than 2.0, greater than
2.5, greater than 3.0, greater than 4.0, greater than 5.0, or
greater than 6.0.
[0149] Staph Aureus log reduction of the composition/products may
be determined via ISO 20743:2013 and the composition/products may
demonstrate a microbial log reduction greater than 0.8, e.g.,
greater than 1.0, greater than 1.5, greater than 2.0, greater than
2.5, greater than 3.0, greater than 4.0, greater than 5.0, or
greater than 6.0.
[0150] Staph Aureus log reduction of the composition/products may
be determined via ASTM 3160 (2018) and the composition/products may
demonstrate a microbial log reduction greater than 0.6, e.g.,
greater than 0.8, greater than 1.0, greater than 1.5, greater than
2.0, greater than 2.5, greater than 3.0, greater than 4.0, greater
than 5.0, or greater than 6.0.
[0151] Staph Aureus log reduction of the composition/products may
be determined via AATC 100 (current year) and the
composition/products may demonstrate a microbial log reduction
greater than 3.0, e.g., greater than 3.5, greater than 4.0, greater
than 5.5, or greater than 6.0.
[0152] Escherichia coli and/or Klebsiella pneumoniae efficacy may
also be determined using the aforementioned tests. In some
embodiments, a product formed from the polymer composition inhibits
the growth (growth reduction) of Escherichia coli and/or Klebsiella
pneumoniae, as measured by the test mentioned above. The ranges and
limits for Staph Aureus are applicable to Escherichia coli and/or
Klebsiella pneumoniae as well.
[0153] In terms of Escherichia coli and/or Klebsiella pneumoniae
log reduction, the composition/products may be determined via the
aforementioned tests, e.g., via ISO 22196:2011, and the
composition/products may demonstrate a microbial log reduction
greater than 1.5, e.g., greater than 2.0, greater than 2.15,
greater than 2.5, greater than 2.7, greater than 3.0, greater than
3.3, greater than 4.0, greater than 5.0, or greater than 6.0.
Mechanical Performance Properties
[0154] As noted above, the disclosed products synergistically
demonstrate superior mechanical performance in addition to the
aforementioned AM/AV performance.
Tensile Strength Retention
[0155] In some embodiments, when heat aged for 2500 hours over an
entire temperature range of from 190.degree. C. to 220.degree. C.
and measured at 23.degree. C., the products demonstrate a tensile
strength retention of greater than 10%, e.g., greater than 15%,
greater than 20%, greater than 25%, greater than 35%, or greater
than 50%.
[0156] In some embodiments, when heat aged for 3000 hours over an
entire temperature range of from 190.degree. C. to 220.degree. C.
and measured at 23.degree. C., the products demonstrate a tensile
strength retention of greater than 10%, e.g., greater than 15%,
greater than 20%, greater than 25%, greater than 35%, or greater
than 50%.
[0157] In some embodiments, when heat aged for 2500 hours at a
temperature of 210.degree. C. and measured at 23.degree. C., the
products demonstrate a tensile strength retention of greater than
5%, e.g., greater than 15%, greater than 20%, greater than 25%,
greater than 35%, or greater than 50%.
[0158] In some embodiments, when heat aged for 3000 hours at a
temperature of 210.degree. C. and measured at 23.degree. C., the
products demonstrate a tensile strength retention of greater than
5%, e.g., greater than 15%, greater than 20%, greater than 25%,
greater than 35%, or greater than 50%.
Tensile Modulus
[0159] The products can demonstrate a tensile modulus that, for
example, ranges from 2500 MPa to 25000 MPa, e.g., from 2500 MPa to
16000 MPa, from 4750 MPa to 18250 MPa, from 7000 MPa to 20500 MPa,
from 5000 MPa to 17000 MPa, from 7000 MPa to 15000 MPa, from 8000
MPa to 12000 MPa, from 8600 MPa to 11500 MPa, from 9250 MPa to
22750 MPa, or from 11500 MPa to 25000 MPa. In terms of upper
limits, the tensile modulus can be less than 25000 MPa, e.g., less
than 22750 MPa, less than 20500 MPa, less than 18250 MPa, less than
17000 MPa, less than 16000 MPa, less than 15000 MPa, less than
13750 MPa, less than 12000 MPa, less than 11500 MPa, less than 9250
MPa, less than 7000 MPa, or less than 4750 MPa. In terms of lower
limits, the tensile modulus can be greater than 2500 MPa, e.g.,
greater than 4750 MPa, greater than 5000 MPa, greater than 7000
MPa, greater than 8000 MPa, greater than 8600 MPa, greater than
9250 MPa, greater than 11500 MPa, greater than 13750 MPa, greater
than 16000 MPa, greater than 18250 MPa, greater than 20500 MPa, or
greater than 22750 MPa. Higher tensile moduli, e.g., greater than
25000 MPa, and lower tensile moduli, e.g., less than 2500 MPa, are
also contemplated. The tensile modulus of the products can be
measured using a standard protocol such as ISO 527-1 (2019).
[0160] The polyamide products can demonstrate a tensile strength at
break that, for example, ranges from 60 MPa to 300 MPa, e.g., from
60 MPa to 204 MPa, from 84 MPa to 228 MPa, from 108 MPa to 252 MPa,
from 132 MPa to 276 MPa, from 135 MPa to 200 MPa, from 140 MPa to
190 MPa, from 145 MPa to 180 MPa, or from 156 MPa to 300 MPa. In
terms of upper limits, the tensile strength at break can be less
than 300 MPa, e.g., less than 276 MPa, less than 252 MPa, less than
228 MPa, less than 228 MPa, less than 204 MPa, less than 200 MPa,
less than 190 MPa, less than 180 MPa, less than 156 MPa, less than
132 MPa, less than 108 MPa, or less than 84 MPa. In terms of lower
limits, the tensile strength at break can be greater than 60 MPa,
e.g., greater than 84 MPa, greater than 108 MPa, greater than 132
MPa, greater than 135 MPa, greater than 140 MPa, greater than 145
MPa, greater than 156 MPa, greater than 180 MPa, greater than 204
MPa, greater than 228 MPa, greater than 252 MPa, or greater than
276 MPa. Higher tensile strengths, e.g., greater than 300 MPa, and
lower tensile strengths, e.g., less than 60 MPa, are also
contemplated. The tensile strength at break of the polyamide
products can be measure using a standard protocol such as ISO 527-1
(2019).
Tensile Elongation
[0161] The polyamide products can demonstrate an elongation
(tensile) at break that, for example, ranges from 2.5% to 67.5%,
e.g., from 2.5% to 41.5%, from 2.5% to 5%, from 2.7% to 4%, from
2.8% to 3.9%, from 9% to 48%, from 15.5% to 54.5%, from 22% to 61%,
or from 28.5% to 67.5%. The products can have an elongation at
break ranging from 2.5% to 5%, e.g., from 2.5% to 4%, from 2.75% to
4.25%, from 3% to 4.5%, from 3.25% to 4.75%, or from 3.5% to 5%. In
terms of upper limits, the elongation at break can be less than
67.5%, e.g., less than 61%, less than 54.5%, less than 48%, less
than 41.5%, less than 35%, less than 28.5%, less than 22%, less
than 15.5%, less than 9%, less than 5%, less than 4%, less than
3.9%, less than 4.75%, less than 4.5%, less than 4.25%, less than
4%, less than 3.75%, less than 3.5%, less than 3.25%, less than 3%,
or less than 2.75%. In terms of lower limits, the elongation at
break can be greater than 2.5%, e.g., greater than 2.7%, greater
than 2.75%, greater than 2.8%, greater than 3%, greater than 3.25%,
greater than 3.5%, greater than 3.75%, greater than 4%, greater
than 4.25%, greater than 4.5%, greater than 4.75%, greater than 5%,
greater than 9%, greater than 15.5%, greater than 22%, greater than
28.5%, greater than 35%, greater than 41.5%, greater than 48%,
greater than 54.5%, or greater than 61%. Larger elongations, e.g.,
greater than 67.5%, and smaller elongations, e.g., less than 2.5%,
are also contemplated. The elongation at break of the polyamide
products can be measured using a standard protocol such as ISO
527-1 (2019,
Flexural Modulus
[0162] The polyamide products can demonstrate a flexural modulus
that, for example, ranges from 2500 MPa to 30000 MPa, e.g., from
2500 MPa to 29000 MPa, from 4750 MPa to 18250 MPa, from 7000 MPa to
20500 MPa, from 8500 MPa to 12000 MPa, from 8700 MPa to 11000 MPa,
from 8900 MPa to 10000 MPa, from 9250 MPa to 22750 MPa, or from
11500 MPa to 25000 MPa. In terms of upper limits, the flexural
modulus can be less than 30000 MPa, e.g., less than 29000, less
than 28000, less than 27000, less than 25000, less than 22750 MPa,
less than 20500 MPa, less than 18250 MPa, less than 16000 MPa, less
than 13750 MPa, less than 12000 MPa, less than 11500 MPa, less than
11000 MPa, less than 10000 MPa, less than 9250 MPa, less than 7000
MPa, or less than 4750 MPa. In terms of lower limits, the flexural
modulus can be greater than 2500 MPa, e.g., greater than 4750 MPa,
greater than 7000 MPa, greater than 8500 MPa, greater than 8700
MPa, greater than 8900 MPa, greater than 9250 MPa, greater than
11500 MPa, greater than 13750 MPa, greater than 16000 MPa, greater
than 18250 MPa, greater than 20500 MPa, or greater than 22750 MPa.
Higher flexural moduli, e.g., greater than 25000 MPa, and lower
flexural moduli, e.g., less than 2500 MPa, are also contemplated.
The flexural modulus of the polyamide products can be measured
using a standard protocol such as ISO 178 (2019).
Flexural Strength at Break
[0163] The polyamide products can demonstrate a flexural strength
at break that, for example, ranges from 100 MPa to 450 MPa, e.g.,
from 100 MPa to 310 MPa, from 135 MPa to 345 MPa, from 170 MPa to
380 MPa, from 205 MPa to 415 MPa, from 225 MPa to 350 MPa, from 230
MPa to 300 MPa, from 240 MPa to 280 MPa, or from 240 MPa to 450
MPa. In terms of upper limits, the flexural strength at break can
be less than 450 MPa, e.g., less than 415 MPa, less than 380 MPa,
less than 350 MPa, less than 345 MPa, less than 310 MPa, less than
300 MPa, less than 280 MPa, less than 275 MPa, less than 240 MPa,
less than 205 MPa, less than 170 MPa, or less than 135 MPa. In
terms of lower limits, the flexural strength at break can be
greater than 100 MPa, e.g., greater than 135 MPa, greater than 170
MPa, greater than 205 MPa, greater than 225 MPa, greater than 230
MPa, greater than 240 MPa, greater than 275 MPa, greater than 310
MPa, greater than 345 MPa, greater than 380 MPa, or greater than
415 MPa. Higher strengths, e.g., greater than 450 MPa, and lower
strengths, e.g., less than 100 MPa, are also contemplated. The
flexural strength at break of the polyamide products can be
measured using a standard protocol such as ISO 178 (2019).
Impact Energy
[0164] The polyamide products can demonstrate a notched Izod impact
energy loss at 23.degree. C. that, for example, ranges from 5
kJ/m.sup.2 to "no break," e.g., from 5 kJ/m.sup.2 to 50 kJ/m.sup.2,
from 5 kJ/m.sup.2 to 32 kJ/m.sup.2, from 9.5 kJ/m.sup.2 to 36.5
kJ/m.sup.2, from 14 kJ/m.sup.2 to 41 kJ/m.sup.2, from 18.5
kJ/m.sup.2 to 45.5 kJ/m.sup.2, or from 23 kJ/m.sup.2 to 50
kJ/m.sup.2. In terms of upper limits, the notched Izod impact
energy loss at 23.degree. C. can be less than 50 kJ/m.sup.2, e.g.,
less than 45.5 kJ/m.sup.2, less than 41 kJ/m.sup.2, less than 36.5
kJ/m.sup.2, less than 32 kJ/m.sup.2, less than 27.5 kJ/m.sup.2,
less than 23 kJ/m.sup.2, less than 18.5 kJ/m.sup.2, less than 14
kJ/m.sup.2, or less than 9.5 kJ/m.sup.2. In some cases, the product
achieve "no break" performance, which, in some cases, means that
the product does not reach a break point after absorbing max
energy. In terms of lower limits, the notched Izod impact energy
loss at 23.degree. C. can be greater than 5 kJ/m.sup.2, e.g.,
greater than 9.5 kJ/m.sup.2, greater than 14 kJ/m.sup.2, greater
than 18.5 kJ/m.sup.2, greater than 23 kJ/m.sup.2, greater than 27.5
kJ/m.sup.2, greater than 32 kJ/m.sup.2, greater than 36.5
kJ/m.sup.2, greater than 41 kJ/m.sup.2, or greater than 45.5
kJ/m.sup.2. Higher Izod impact energy losses at 23.degree. C.,
e.g., greater than 50 kJ/m.sup.2, and lower Izod impact energy
losses at 23.degree. C., e.g., less than 5 kJ/m.sup.2, are also
contemplated. The notched Izod impact energy loss of the polyamide
products can be measured using a standard protocol such as ISO 180
(2019).
[0165] The polyamide products can demonstrate a notched Izod impact
energy loss at -40.degree. C. that, for example, ranges from 3
kJ/m.sup.2 to 30 kJ/m.sup.2, e.g., from 3 kJ/m.sup.2 to 19.2
kJ/m.sup.2, from 5.7 kJ/m.sup.2 to 21.9 kJ/m.sup.2, from 8.4
kJ/m.sup.2 to 24.6 kJ/m.sup.2, from 11.1 kJ/m.sup.2 to 27.3
kJ/m.sup.2, or from 13.8 kJ/m.sup.2 to 30 kJ/m.sup.2/In terms of
upper limits, the notched Izod impact energy loss at -40.degree. C.
can be less than 30 kJ/m.sup.2, e.g., less than 27.3 kJ/m.sup.2,
less than 24.6 kJ/m.sup.2, less than 21.9 kJ/m.sup.2, less than
19.2 kJ/m.sup.2, less than 16.5 kJ/m.sup.2, less than 13.8
kJ/m.sup.2, less than 11.1 kJ/m.sup.2, less than 8.4 kJ/m.sup.2, or
less than 5.7 kJ/m.sup.2. In terms of lower limits, the notched
Izod impact energy loss at -40.degree. C. can be greater than 3
kJ/m.sup.2, e.g., greater than 5.7 kJ/m.sup.2, greater than 8.4
kJ/m.sup.2, greater than 11.1 kJ/m.sup.2, greater than 13.8
kJ/m.sup.2, greater than 16.5 kJ/m.sup.2, greater than 19.2
kJ/m.sup.2, greater than 21.9 kJ/m.sup.2, greater than 24.6
kJ/m.sup.2, or greater than 27.6 kJ/m.sup.2. Higher Izod impact
energy losses at -40.degree. C., e.g., greater than 30 kJ/m.sup.2,
and lower Izod impact energy losses at -40.degree. C., e.g., less
than 3 kJ/m.sup.2, are also contemplated.
[0166] The polyamide products can demonstrate a Charpy notched
impact energy loss at 23.degree. C. that, for example, ranges from
6 kJ/m.sup.2 to 36 kJ/m.sup.2, e.g., from 6 kJ/m.sup.2 to 24
kJ/m.sup.2, from 9 kJ/m.sup.2 to 27 kJ/m.sup.2, from 10 kJ/m.sup.2
to 35 kJ/m.sup.2, from 10 kJ/m.sup.2 to 27 kJ/m.sup.2, from 11
kJ/m.sup.2 to 25 kJ/m.sup.2, from 12 kJ/m.sup.2 to 30 kJ/m.sup.2,
from 15 kJ/m.sup.2 to 33 kJ/m.sup.2, or from 18 kJ/m.sup.2 to 36
kJ/m.sup.2. In terms of upper limits, the Charpy notched impact
energy loss at 23.degree. C. can be less than 36 kJ/m.sup.2, e.g.,
less than 35 kJ/m.sup.2, less than 33 kJ/m.sup.2, less than 30
kJ/m.sup.2, less than 27 kJ/m.sup.2, less than 25 kJ/m.sup.2, less
than 24 kJ/m.sup.2, less than 21 kJ/m.sup.2, less than 18
kJ/m.sup.2, less than 15 kJ/m.sup.2, less than 12 kJ/m.sup.2, or
less than 9 kJ/m.sup.2. In terms of lower limits, the Charpy
notched impact energy loss at 23.degree. C. can be greater than 6
kJ/m.sup.2, e.g., greater than 9 kJ/m.sup.2, greater than 10
kJ/m.sup.2, greater than 11 kJ/m.sup.2, greater than 12 kJ/m.sup.2,
greater than 15 kJ/m.sup.2, greater than 18 kJ/m.sup.2, greater
than 21 kJ/m.sup.2, greater than 24 kJ/m.sup.2, greater than 27
kJ/m.sup.2, greater than 30 kJ/m.sup.2, or greater than 33
kJ/m.sup.2. Higher Charpy impact energy losses, e.g., greater than
36 kJ/m.sup.2, and lower Charpy impact energy losses, e.g., less
than 3 kJ/m.sup.2, are also contemplated. The Charpy notched impact
energy loss of the polyamide products can be measured using a
standard protocol such as ISO 179-1 (2010).
[0167] The polyamide products can demonstrate a Charpy un-notched
impact energy loss at 23.degree. C. that, for example, ranges from
70 kJ/m.sup.2 to "no break," e.g., from 70 kJ/m.sup.2 to 200
kJ/m.sup.2, from 70 kJ/m.sup.2 to 175 kJ/m.sup.2, from 70
kJ/m.sup.2 to 120 kJ/m.sup.2, from 70 kJ/m.sup.2 to 100 kJ/m.sup.2,
from 72 kJ/m.sup.2 to 98 kJ/m.sup.2, from 75 kJ/m.sup.2 to 95
kJ/m.sup.2, from 80 kJ/m.sup.2 to 95 kJ/m.sup.2, or from 84
kJ/m.sup.2 to 93 kJ/m.sup.2. In terms of upper limits, the Charpy
un-notched impact energy loss at 23.degree. C. can be less than 200
kJ/m.sup.2, e.g., less than 180 kJ/m.sup.2, less than 175
kJ/m.sup.2, less than 150 kJ/m.sup.2, less than 120 kJ/m.sup.2,
less than 100 kJ/m.sup.2, less than 98 kJ/m.sup.2, less than 95
kJ/m.sup.2, or less than 93 kJ/m.sup.2. In some cases, the product
achieve "no break" performance. In terms of lower limits, the
Charpy un-notched impact energy loss at 23.degree. C. can be
greater than 70 kJ/m.sup.2, e.g., greater than 72 kJ/m.sup.2,
greater than 75 kJ/m.sup.2, greater than 80 kJ/m.sup.2, greater
than 83 kJ/m.sup.2, or greater than 84 kJ/m.sup.2. Higher Charpy
impact energy losses, e.g., greater than 150 kJ/m.sup.2, and lower
Charpy impact energy losses, e.g., less than 70 kJ/m.sup.2, are
also contemplated. The Charpy un-notched impact energy loss of the
polyamide products can be measured using a standard protocol such
as ISO 179-1 (2010).
[0168] The polyamide products can demonstrate a Charpy notched
impact energy loss at -40.degree. C. that, for example, ranges from
5 kJ/m.sup.2 to 50 kJ/m.sup.2, e.g., from 5 kJ/m.sup.2 to 30
kJ/m.sup.2, from 6 kJ/m.sup.2 to 20 kJ/m.sup.2, from 7 kJ/m.sup.2
to 18 kJ/m.sup.2, from 8 kJ/m.sup.2 to 17 kJ/m.sup.2, or from 9
kJ/m.sup.2 to 15 kJ/m.sup.2. In terms of upper limits, the Charpy
un-notched impact energy loss at -40.degree. C. can be less than 50
kJ/m.sup.2, e.g., less than 30 kJ/m.sup.2, less than 20 kJ/m.sup.2,
less than 18 kJ/m.sup.2, less than 17 kJ/m.sup.2, or less than 15
kJ/m.sup.2. In terms of lower limits, the Charpy un-notched impact
energy loss at -40.degree. C. can be greater than 5 kJ/m.sup.2,
e.g., greater than 6 kJ/m.sup.2, greater than 7 kJ/m.sup.2, greater
than 8 kJ/m.sup.2, or greater than 9 kJ/m.sup.2. Higher Charpy
impact energy losses, e.g., greater than 50 kJ/m.sup.2, and lower
Charpy impact energy losses, e.g., less than 5 kJ/m.sup.2, are also
contemplated. The Charpy notched impact energy loss of the
polyamide products can be measured using a standard protocol such
as ISO 179-1 (2010).
[0169] The polyamide products can demonstrate a Charpy un-notched
impact energy loss at -40.degree. C. that, for example, ranges from
65 kJ/m.sup.2 to 150 kJ/m.sup.2, e.g., from 65 kJ/m.sup.2 to 120
kJ/m.sup.2, from 65 kJ/m.sup.2 to 110 kJ/m.sup.2, from 70
kJ/m.sup.2 to 110 kJ/m.sup.2, from 72 kJ/m.sup.2 to 105 kJ/m.sup.2,
from 73 kJ/m.sup.2 to 105 kJ/m.sup.2, or from 74 kJ/m.sup.2 to 98
kJ/m.sup.2. In terms of upper limits, the Charpy un-notched impact
energy loss at -40.degree. C. can be less than 150 kJ/m.sup.2,
e.g., less than 120 kJ/m.sup.2, less than 110 kJ/m.sup.2, less than
105 kJ/m.sup.2, or less than 98 kJ/m.sup.2. In terms of lower
limits, the Charpy un-notched impact energy loss at -40.degree. C.
can be greater than 65 kJ/m.sup.2, e.g., greater than 70
kJ/m.sup.2, greater than 72 kJ/m.sup.2, greater than 73 kJ/m.sup.2,
or greater than 74 kJ/m.sup.2. Higher Charpy impact energy losses,
e.g., greater than 150 kJ/m.sup.2, and lower Charpy impact energy
losses, e.g., less than 65 kJ/m.sup.2, are also contemplated. The
Charpy un-notched impact energy loss of the polyamide products can
be measured using a standard protocol such as ISO 179-1 (2010).
[0170] The polyamide products can demonstrate a tan delta (at
60.degree. C.) that, for example, ranges from 0.04 au to 0.5 au,
e.g., from 0.04 au to 0.4 au, from 0.042 au to 0.2 au, from 0.044
au to 0.15 au, or from 0.046 to 0.1 au. In terms of upper limits,
the tan delta (at 60.degree. C.) can be less than 0.5 au, e.g.,
less than 0.4 au, less than 0.2 au, less than 0.15 au, or less than
0.1 au. In terms of lower limits, the tan delta (at 60.degree. C.)
can be greater than 0.04 au, e.g., greater than 0.042 au, greater
than 0.044 au, or greater than 0.046 au. The tan delta (at
60.degree. C.) of the polyamide products can be measured using the
centerpoint beam technique.
[0171] The polyamide products can demonstrate a tan delta (at
90.degree. C.) that, for example, ranges from 0.143 au to 0.75 au,
e.g., from 0.175 au to 0.6 au, from 0.19 au to 0.5 au, from 0.2 au
to 0.4 au, or from 0.215 to 0.3 au. In terms of upper limits, the
tan delta (at 90.degree. C.) can be less than 0.75 au, e.g., less
than 0.6 au, less than 0.5 au, less than 0.4 au, or less than 0.3
au. In terms of lower limits, the tan delta (at 90.degree. C.) can
be greater than 0.143 au, e.g., greater than 0.175 au, greater than
0.19 au, greater than 0.2 au, or greater than 0.215 au. The tan
delta (at 90.degree. C.) of the polyamide products can be measured
using the centerpoint beam technique.
[0172] In some embodiments, the polyamide products demonstrate
improved maximum tan delta performance. In some cases, maximum tan
delta is greater than 0.055, e.g., greater than 0.057, greater than
0.059, greater than 0.061, or greater than 0.063. The maximum tan
delta may be measured using Dynamic Mechanical Analysis
[0173] In some embodiments, the molded products demonstrate a heat
deflection temperature ranging from 50.degree. C. to 300.degree.
C., e.g., from 65.degree. C. to 275.degree. C., from 75.degree. C.
to 270.degree. C. or from 76.degree. C. to 266.degree. C. In some
cases, where the molded product is filled, the heat deflection
temperature may range from 200.degree. C. to 300.degree. C., e.g.,
from 220.degree. C. to 280.degree. C., from 240.degree. C. to
260.degree. C., or from 250.degree. C. to 260.degree. C. In cases
where the molded product is not filled, the heat deflection
temperature may range from 50.degree. C. to 125.degree. C., e.g.,
from 55.degree. C. to 100.degree. C., from 60.degree. C. to
90.degree. C., or from 65.degree. C. to 85.degree. C. In terms of
lower limits, the molded products may demonstrate a heat deflection
temperature greater than 50.degree. C., e.g., greater than
60.degree. C., greater than 65.degree. C., greater than 75.degree.
C., greater than 76.degree. C., greater than 220.degree. C.,
greater than 240.degree. C., greater than 250.degree. C., or
greater than 260.degree. C.
[0174] In some embodiments, the molded products demonstrate a melt
temperature ranging from 150.degree. C. to 350.degree. C., e.g.,
from 175.degree. C. to 325.degree. C., from 200.degree. C. to
300.degree. C., from 225.degree. C. to 280.degree. C., or from
245.degree. C. to 275.degree. C. In terms of lower limits, the
molded products may demonstrate a melt temperature greater than
150.degree. C., e.g., greater than 175.degree. C., greater than
200.degree. C., greater than 225.degree. C., greater than
245.degree. C., greater than 250.degree. C., or greater than
255.degree. C.
Self-Cleaning/Virus-Inactivating Fabrics
[0175] In some cases, the disclosure relates to self-cleaning
and/or microbial- or virus-inactivating products that may comprise
the compositions disclosed herein. In some embodiments, the
products are configured into masks or other personal protective
equipment (PPE). Face masks and other PPE can reduce risk of
spreading or getting infected with respiratory viruses, such as
SARS-CoV-2, the causative agent of Covid-19. However, in some
instances (where the microbial/virus is not inactivated), the
microbials/viruses can remain infectious in or on the outside of
conventional PPE for extended periods of time.
[0176] This disclosure relates to self-cleaning and/or microbial-
or virus-inactivating products that have the synergistic
combination of the ability to trap the microbial/virus and the
ability to inactivate or neutralize the microbial/virus. As such,
the disclosed fabrics are able to capture and inactivate
microbials/viruses before they reach the protected user. In some
cases, the composition of the fabric is relevant, as many
conventional fabrics, e.g., polypropylene, are unable to
effectively trap the microbial/virus (for enough time for
inactivation).
[0177] It has been discovered that respiratory microbial/viruses
can be advantageously inactivated via absorption of droplet
containing the microbials/viruses and inactivation thereof on the
surface and within the bulk of the fabric. In some embodiments, the
products may be constructed from polymers that maintain a moisture
balance, e.g., polyamides, and contain embedded zinc ions within
their matrix to inactivate any respiratory viruses.
[0178] In some specific cases, it has been found that cotton and
PA66 readily absorb microbials/viruses, and that zinc ions embedded
in the fabrics effectively inactivated the microbials/viruses,
which resulted in at least a 2-log 10 reduction in virus titer
after 30 seconds, which is more than sufficient to inactivate the
number of infectious IAV virus particles (.about.24 plaque forming
units [pfu]) present in a cough.
[0179] As shown in some of the Examples, with the disclosed
products, after addition of influenza A virus and SARS-CoV-2
thereto, inactivation rates were found to exceed the number of
virus particles present in a typical cough. It has also been
discovered that the influenza A virus surface protein
haemagglutinin and the SARS-CoV-2 surface protein spike are
destabilized on the disclosed fibers. These fibers may thus
beneficially confer "self-cleaning" and broad-spectrum viral
inactivation properties to PPE and complement existing PPE by
reducing the risk of respiratory virus transmission even
further.
[0180] Zinc/Copper Retention Rate
[0181] As noted herein, by utilizing a polymer composition having
the aforementioned zinc compound, copper compound, and/or
phosphorus compound in the disclosed concentrations, the resultant
products are capable of retaining a higher percentage of zinc
and/or copper, even after use or wiping or cleaning/scrubbing of
the products. Stated another way, the disclosed molded products are
able to maintain AM/AV compound content, e.g., zinc content,
throughout use/wiping/cleaning, and as such are able to maintain
AM/AV properties throughout use of the products.
[0182] In some embodiments, the AM/AV products formed from the
polymer composition have a zinc and/or copper retention greater
than 65% as measured by a washing/cleaning/scrubbing test or dye
bath test, e.g., greater than 75%, greater than 80%, greater than
90%, greater than 95%, greater than 97%, greater than 98%, greater
than 99%, greater than 99.9%, greater than 99.99%, greater than
99.999%, greater than 99.9999%, greater than 99.99999% or greater
than 99.999999%. In terms of upper limits, the AM/AV products have
a zinc and/or copper retention of less than 100%, e.g., less than
99.9%, less than 98%, or less than 95%. In terms of ranges, the
AM/AV products have a zinc and/or copper retention may be from 60%
to 100%, e.g., from 60% to 99.999999%, from 60% to 99.99999%, from
60% to 99.9999%, from 60% to 99.999% from 60% to 99.999%, from 60%
to 99.99%, from 60% to 99.9%, from 60% to 99%, from 60% to 98%,
from 60% to 95%, from 65% to 99.999999%, from 65% to 99.99999%,
from 65% to 99.9999%, from 65% to 99.999% from 65% to 99.999%, from
65% to 100%, from 65% to 99.99%, from 65% to 99.9%, from 65% to
99%, from 65% to 98%, from 65% to 95%, from 70% to 100%, from 70%
to 99.999999%, from 70% to 99.99999%, from 70% to 99.9999%, from
70% to 99.999% from 70% to 99.999%, from 70% to 99.99%, from 70% to
99.9%, from 70% to 99%, from 70% to 98%, from 70% to 95%, from 75%
to 100%, from 75% to 99.99%, from 75% to 99.9%, from 75% to
99.999999%, from 75% to 99.99999%, from 75% to 99.9999%, from 75%
to 99.999% from 75% to 99.999%, from 75% to 99%, from 75% to 98%,
from 75% to 95%, %, from 80% to 99.999999%, from 80% to 99.99999%,
from 80% to 99.9999%, from 80% to 99.999% from 80% to 99.999%, from
80% to 100%, from 80% to 99.99%, from 80% to 99.9%, from 80% to
99%, from 80% to 98%, or from 80% to 95%.
[0183] Stated another way, in some embodiments, the AM/AV products
formed from the polymer composition demonstrate an extraction rate
of the zinc and/or copper compound less than 35% as measured by a
washing/cleaning/scrubbing or dye bath test, e.g., less than 25%,
less than 20%, less than 10%, or less than 5%. In terms of upper
limits, the AM/AV products demonstrate an extraction rate of the
zinc and/or copper compound greater than 0%, e.g., greater than
0.1%, greater than 2% or greater than 5%. In terms of ranges, the
AM/AV products demonstrate an extraction rate of the zinc and/or
copper compound from 0% to 35%, e.g., from 0% to 25%, from 0% to
20%, from 0% to 10%, from 0% to 5%, from 0.1% to 35%, from 0.1% to
25%, from 0.1% to 20%, from 0.2% to 10%, from 0.1% to 5%, from 2%
to 35%, from 2% to 25%, from 2% to 20%, from 2% to 10%, from 2% to
5%, from 5% to 35%, from 5% to 25%, from 5% to 20%, or from 5% to
10%.
[0184] In some cases, zinc retention may be characterized in
relation to washing or cleaning cycles. The AM/AV products are
capable of retaining a higher percentage of zinc and/or copper,
even after use, as such the resulting products have AM/AV
properties.
[0185] In some embodiments, the AM/AV products formed from the
polymer composition have a zinc and/or copper retention greater
than 85% as measured in after 5 washes, e.g., greater than 90%,
greater than 92%, greater than 95%, greater than 96%, greater than
98%, greater than 99%, or greater than 99.9%.
[0186] In some embodiments, the AM/AV products formed from the
polymer composition have a zinc and/or copper retention greater
than 65% as measured in after 10 washes, e.g., greater than 70%,
greater than 72%, greater than 80%, greater than 85%, greater than
90%, greater than 95%, greater than 99%.
[0187] As used herein, "greater than" and "less than" limits may
also include the number associated therewith. Stated another way,
"greater than" and "less than" may be interpreted as "greater than
or equal to" and "less than or equal to."
Additional Components
[0188] In some embodiments, the polymer composition may comprise
additional additives. The additives include pigments, hydrophilic
or hydrophobic additives, anti-odor additives, additional antiviral
agents, and antimicrobial/anti-fungal inorganic compounds.
[0189] In some embodiments, the polymer composition can be combined
with color pigments for coloration for the use in fabrics or other
components formed from the polymer composition. In some aspects,
the polymer composition can be combined with UV additives to
withstand fading and degradation in fabrics exposed to significant
UV light. In some aspects, the polymer composition can be combined
with additives to make the surface of the product hydrophilic or
hydrophobic. In some aspects, the polymer composition can be
combined with a hygroscopic material, e.g., to make the products
formed therefrom more hygroscopic. In some aspects, the polymer
composition can be combined with additives to make the product
flame retardant or flame resistant. In some aspects, the polymer
composition can be combined with additives to make the product
stain resistant. In some aspects, the polymer composition can be
combined with pigments with the antimicrobial compounds so that the
need for conventional dyeing and disposal of dye materials is
avoided.
[0190] In some embodiments, the polymer composition may further
comprise additional additives. For example, the polymer composition
may comprise a delusterant. A delusterant additive may improve the
appearance and/or texture of the products produced from the polymer
composition. In some embodiments, inorganic pigment-like materials
can be utilized as delusterants--zinc compounds are not included as
delusterants. The delusterants may comprise one or more of titanium
dioxide, barium sulfate, barium titanate, magnesium titanate,
calcium titanate, lithopone, zirconium dioxide, calcium sulfate,
barium sulfate, aluminum oxide, thorium oxide, magnesium oxide,
silicon dioxide, talc, mica, and the like. In preferred
embodiments, the delusterant comprises titanium dioxide. It has
been found that the polymer compositions that include delusterants
comprising titanium dioxide produce products that greatly resemble
natural products, e.g., synthetic fibers and fabrics with improved
appearance and/or texture. It is believed that titanium dioxide
improves appearance and/or texture by interacting with the zinc
compound, the phosphorus compound, and/or functional groups within
the polymer.
[0191] In one embodiment, the polymer composition comprises the
delusterant in an amount ranging from 0.0001 wt. % to 3 wt. %,
e.g., 0.0001 wt. % to 2 wt. %, from 0.0001 to 1.75 wt. %, from
0.001 wt. % to 3 wt. %, from 0.001 wt. % to 2 wt. %, from 0.001 wt.
% to 1.75 wt. %, from 0.002 wt. % to 3 wt 5, from 0.002 wt. % to 2
w %, from 0.002 wt. % to 1.75 wt. %, from 0.005 wt. % to 3 wt. %,
from 0.005 wt. % to 2 wt. %, from 0.005 wt. % to 1.75 wt. %. In
terms of upper limits, the polymer composition may comprise less
than 3 wt. % delusterant, e.g., less than 2.5 wt. %, less than 2
wt. % or less than 1.75 wt. %. In terms of lower limits, the
polymer composition may comprise greater than 0.0001 wt. %
delusterant, e.g., greater than 0.001 wt. %, greater than 0.002 wt.
%, or greater than 0.005 wt. %.
[0192] In some embodiments, the polymer composition may further
comprises colored materials, such as carbon black, copper
phthalocyanine pigment, lead chromate, iron oxide, chromium oxide,
and ultramarine blue.
[0193] In some embodiments, the polymer composition may include
additional antiviral agents other than zinc. The additional
antimicrobial agents may be any suitable antiviral. Conventional
antiviral agents are known in the art and may be incorporated in
the polymer composition as the additional antiviral agent or
agents. For example, the additional antiviral agent may be an entry
inhibitor, a reverse transcriptase inhibitor, a DNA polymerase
inhibitor, an m-RNA synthesis inhibitor, a protease inhibitor, an
integrase inhibitor, or an immunomodulator, or combinations
thereof. In some aspects, the additional antimicrobial agent or
agents are added to the polymer composition.
[0194] In some embodiments, the polymer composition may include
additional antimicrobial agents other than zinc. The additional
antimicrobial agents may be any suitable antimicrobial, such as
silver, copper, and/or gold in metallic forms (e.g., particulates,
alloys and oxides), salts (e.g., sulfates, nitrates, acetates,
citrates, and chlorides) and/or in ionic forms. In some aspects,
further additives, e.g., additional antimicrobial agents, are added
to the polymer composition.
Processes for Making Products
[0195] Processes for making molded products may vary widely, and
many processes are known.
[0196] The present disclosure also relates to processes of
producing the polyamide compositions. The methods include providing
one or more polyamide polymers, zinc compound and/or copper
compound, and optionally one or more molding additives. The methods
can further include selecting the type and relative amounts of the
one or more polyamide polymers, zinc/copper, and additives to
provide desired AM/AV/mechanical properties to the resulting
polyamide composition. The methods further include combining the
components to produce the polyamide composition. In some
embodiments, the methods further include selecting, providing,
and/or combining one or more dyes such as nigrosine, one or more
pigments such as carbon black, and/or one or more melt
stabilizers.
[0197] The components of the polyamide composition can be mixed and
blended together to produce the polyamide composition, or can be
formed in situ using appropriate reactants. The terms "adding" or
"combining" without further clarification are intended to encompass
either the addition of the material itself to the composition or
the in situ formation of the material in the composition. In
another embodiment, two or more materials to be combined with the
composition are simultaneously added via masterbatch. Masterbatches
may employ higher amounts of AM/AV compound, see higher ranges
disclosed herein. Beneficially, the masterbatches may be employed
as one method to achieve the desired zinc loading levels.
[0198] The antiviral agent may be added to the polyamide during
melt polymerization, and thereafter, the fiber (or other product)
may be formed from extrusion and/or molding. Of course, other fiber
forming methods are also contemplated. The formed fibers may be
spun to form a resultant yarn to be used in knitting and/or weaving
to provide the antiviral properties in the fabrics. While polyamide
may be used to explain one aspect of the disclosure, it is
understood that numerous polymers may be used herein without
deviating from the present scope of the disclosure.
[0199] It will be appreciated that variants of the above-disclosed
and other features and functions, or alternatives thereof, may be
combined into many other different systems or applications. Various
presently unforeseen or unanticipated alternatives, modifications,
variations or improvements therein may be subsequently made by
those skilled in the art which are also intended to be encompassed
by the following claims or the equivalents thereof.
Examples
[0200] Examples 1-11 and Comparative Example A were prepared by
combining the components in the amounts shown in Table 1 and
compounding in a twin-screw extruder. The compositions were melted,
additives were added to the melt, and the resultant mixture was
extruded and pelletized.
[0201] The AM/AV additive was zinc compound, e.g., zinc oxide, or
zinc ammonium adipate, or zinc chloride. Where indicated sterically
hindered phenolic antioxidant Irganox.RTM. 1098 (available from
BASF) and/or Songnox.RTM., from Songwon were employed as
antioxidants. The copper-complex heat stabilizer used was
Bruggolen.RTM. H3386 (available from Bruggemann Chemical). The
flame retardant was melamine cyanurate and/or zinc borate. The
impact modifier was Fusabond.RTM. N493, from Dow Chemical. Where
indicated, diundecyl phthalate was employed as a plasticizer.
TABLE-US-00001 TABLE 1 AM/AV Polymer Compositions PA- FR/ Heat Melt
Addt'l Ex. 6,6 PA-6 Glass ZnO IM Stab. Plas. Antiox. stab. Adds. 1
91.9 0.5 7 0.5 0.1 2 90 0.5 7 0.5 1.8 0.5 + 0.02 0.1 0.1 3 44.35
9.0 25 0.3 20 + 1 0.25 0.1 4 78.3 0.5 18 2.25 0.35 0.25 0.35 5 78.7
0.5 20 0.3 0.5 6 80.25 2.0 0.3 12 4.5 0.35 0.25 0.35 7 82.6 0.3 12
4.5 0.25 0.35 8 95.24 0.5 0.26 4.0 9 95.23 0.5 4 0.27 10 99.5 0.5
11 66.45 31.05 0.5 0.35 1.5 + 0.15 A 95.74 -- 0.26 4.0
[0202] Panels were molded from the pellets, and the panels were
tested for AM/AV efficacy, in accordance with ISO 22196:2011. The
results are presented in Table 2.
TABLE-US-00002 TABLE 2 AM/AV Performance S. Aureus, E. Coli, S.
Aureus, E. Coli, Ex. kill rate kill rate log reduction Log
reduction 1 >99.99 >99.99 log 3 log 3 2 >99.99 >99.999
log 3 log 4 3 >99.99 >99.99 log 3 log 3 4 >99.99
>99.999 log 3 log 4 5 >99.999 >99.999 log 4 log 4 6
>99.999 >99.999 log 4 log 4 7 >99.999 >99.999 log 4 log
4 8 >99.999 >99.999 log 4 log 4 9 >99.99 >99.999 log 3
log 4 10 >99.999 >99.999 log 4 log 4 11 >99.999 >99.999
log 4 log 4 A 52 46 log 0.27 log 0.32
[0203] As shown in Table 2, the molded samples formed from the
polymer compositions described herein demonstrated excellent AM/AV
efficacy. In all cases, reduction was log 3 or better, in many
cases log 4. In contrast, Comparative Example A demonstrated log
reductions well under 1.0, e.g., 0.27 and 0.32, which indicates
little or no antimicrobial efficiency. As one direct comparison,
Example 8 and Comparative Example A have very similar components,
yet the AM/AV performance for Example 8 is surprisingly orders of
magnitude better (99.999% and log 4 vs 52%/46% and log 0.27 and
0.32). Such an increase with a minimal compositional change is
unexpected. Also, in addition to the AM/AV efficacy, the mechanical
performance was synergistically in line with the ranges and limits
discussed above.
Embodiments
[0204] As used below, any reference to a series of embodiments is
to be understood as a reference to each of those embodiments
disjunctively (e.g., "Embodiments 1-4" is to be understood as
"Embodiments 1, 2, 3, or 4").
[0205] Embodiment 1: a polymer composition for molded products
having antimicrobial and/or antiviral properties comprising: from
50 wt. % to 99.9 wt. % of a polymer, from 0.01 wt % to 10 wt %
zinc, optionally from a zinc compound, less than 1 wt % of a
phosphorus compound, and from 0 wt % to 20 wt % molding additives,
wherein a molded product formed from the polymer composition
demonstrates a Klebsiella pneumonia log reduction greater than 1.0,
as determined via ISO 22196:2011.
[0206] Embodiment 2: an embodiment of embodiment 1 wherein a molded
product formed from the polymer composition demonstrates a
Staphylococcus aureus log reduction greater than 1.0, as determined
via ISO 22196:2011.
[0207] Embodiment 3: an embodiment of embodiment 1 or 2 wherein a
molded product formed from the polymer composition demonstrates an
Escherichia coli log reduction greater than 1.0, as determined via
ISO 22196:2011.
[0208] Embodiment 4: an embodiment of any of embodiments 1-3
wherein a molded product formed from the polymer composition
demonstrates a tensile modulus greater than 2500 MPa and/or a
Charpy un-notched impact energy loss greater than 70 kJ/m.sup.2, at
23.degree. C.
[0209] Embodiment 5: an embodiment of any of embodiments 1-4
wherein the polymer is hydrophilic and/or hygroscopic is capable of
absorbing greater than 1.5 wt % water, based on the total weight of
the polymer.
[0210] Embodiment 6: an embodiment of any of embodiments 1-5
wherein the composition comprises from 1000 ppm to 7000 wppm
zinc.
[0211] Embodiment 7: an embodiment of any of embodiments 1-6
wherein the composition comprises from 2 wt % to 20 wt % of impact
modifier.
[0212] Embodiment 8: an embodiment of any of embodiments 1-7
wherein the composition comprises from 2 wt % to 20 wt % flame
retardant.
[0213] Embodiment 9: an embodiment of any of embodiments 1-8
wherein the composition comprises from 0.1 to 5 wt % heat
stabilizer and/or from 0.05 wt % to 3 wt % melt stabilizer.
[0214] Embodiment 10: an embodiment of any of embodiments 1-9
wherein the composition comprises PA-6,6 and PA-6.
[0215] Embodiment 11: an embodiment of any of embodiments 1-10
wherein the composition comprises impact modifier and heat
stabilizer and wherein the weight ratio of impact modifier to heat
stabilizer ranges from 0.5 to 23.
[0216] Embodiment 12: a molded product having antimicrobial and/or
antiviral properties, comprising: from 50 wt. % to 99.9 wt. % of a
polymer, from 0.01 wt % to 10 wt % zinc, optionally from a zinc
compound, less than 1 wt % of a phosphorus compound, and from 0 wt
% to 20 wt % molding additives, wherein a molded product formed
from the polymer composition demonstrates a Klebsiella pneumonia
log reduction greater than 1.0, as determined via ISO
22196:2011.
[0217] Embodiment 13: an embodiment of embodiment 12 wherein the
molded product demonstrates a tensile modulus greater than 2500 MPa
and/or a Charpy un-notched impact energy loss greater than 70
kJ/m.sup.2, at 23.degree. C.
[0218] Embodiment 14: an embodiment of embodiment 12 or 13 wherein
the polymer is hydrophilic and/or hygroscopic is capable of
absorbing greater than 1.5 wt % water, based on the total weight of
the polymer.
[0219] Embodiment 15: an embodiment of any of embodiments 12-14
wherein the composition comprises from 1000 ppm to 7000 wppm
zinc.
[0220] Embodiment 16: an embodiment of any of embodiments 12-15
wherein the molded product has a zinc retention rate greater than
65%.
[0221] Embodiment 17: an embodiment of any of embodiments 12-16
wherein the molded product is a cable tie.
[0222] Embodiment 18: an embodiment of any of embodiments 12-17
wherein the molded product is medical equipment.
[0223] Embodiment 19: an embodiment of any of embodiments 12-18
wherein the medical equipment is reusable.
[0224] Embodiment 20: an embodiment of any of embodiments 12-19
wherein the zinc compound comprises zinc oxide, zinc stearate, zinc
ammonium adipate, zinc acetate, or zinc pyrithione, or combinations
thereof.
* * * * *