U.S. patent application number 16/972228 was filed with the patent office on 2021-10-07 for reformable resin filaments and materials formed therewith.
The applicant listed for this patent is Zephyros, Inc.. Invention is credited to Jason Walker.
Application Number | 20210310157 16/972228 |
Document ID | / |
Family ID | 1000005722480 |
Filed Date | 2021-10-07 |
United States Patent
Application |
20210310157 |
Kind Code |
A1 |
Walker; Jason |
October 7, 2021 |
Reformable Resin Filaments and Materials Formed Therewith
Abstract
The present teachings contemplate forming a reformable epoxy
resin material into a monofilament having a denier of from about 50
to about 5000 and a glass transition temperature of less than about
200.degree. C.; loading one or more monofilaments onto a spool;
co-weaving the one or more monofilaments with a reinforcing fiber
to form a woven material, the reinforcing fiber having a glass
transition temperature of greater than 200.degree. C.; heating the
woven material to form a composite to a temperature so that only
the one or more monofilaments soften but the reinforcing fiber does
not.
Inventors: |
Walker; Jason; (Romeo,
MI) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Zephyros, Inc. |
Romeo |
MI |
US |
|
|
Family ID: |
1000005722480 |
Appl. No.: |
16/972228 |
Filed: |
June 11, 2019 |
PCT Filed: |
June 11, 2019 |
PCT NO: |
PCT/US2019/036615 |
371 Date: |
December 4, 2020 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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62683229 |
Jun 11, 2018 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
D03D 15/47 20210101;
D10B 2401/04 20130101; D03D 1/0052 20130101; D01F 6/66 20130101;
D03D 7/00 20130101; D03D 15/587 20210101; D10B 2505/02 20130101;
D10B 2501/04 20130101 |
International
Class: |
D01F 6/66 20060101
D01F006/66; D03D 1/00 20060101 D03D001/00; D03D 15/47 20060101
D03D015/47; D03D 15/587 20060101 D03D015/587; D03D 7/00 20060101
D03D007/00 |
Claims
1. A method comprising: i) forming the monofilament of claim 17;
ii) loading one or more of the monofilaments onto a spool; iii)
co-weaving the one or more monofilaments with a reinforcing fiber
to form a woven material, the reinforcing fiber having a glass
transition temperature of greater than 200.degree. C.; iv) heating
the woven material to form a composite to a temperature so that
only the one or more monofilaments softens but the reinforcing
fiber does not.
2. The method according to claim 1, wherein the reinforcing fiber
is selected from the group consisting of glass fibers, carbon
fibers, aramid fibers, polymer fibers (polyethylene, polypropylene,
polyamide, polyester), metallic fibers, and combinations
thereof.
3. The method according to claim 1, wherein the resulting composite
has a constant thickness as a result of the failure of the
structural fibers to soften.
4-5. (canceled)
6. The method according to claim 1, wherein one or more of the
denier or diameter of the monofilament is substantially similar to
that of the reinforcing fiber.
7. The method according to claim 1, wherein one or more of the
denier or diameter of the monofilament is less than that of the
reinforcing fiber.
8. (canceled)
9. The method according to claim 1, wherein the resulting composite
is an epoxy laminate.
10. The fibrous material product according to claim 22, wherein the
resulting composite is substantially free of any film layer.
11-12. (canceled)
13. The fibrous material product of claim 22, wherein the
monofilament develops adhesive properties upon softening.
14. (canceled)
15. The monofilament according to claim 17, wherein the
monofilament is recyclable.
16. (canceled)
17. A monofilament having a denier of from about 200-3200 and a
glass transition temperature of less than about 200.degree. C. and
comprising a reformable epoxy resin material.
18. The monofilament of claim 17, wherein the reformable epoxy
resin material is formed as a reaction product of a difunctional
epoxy resin and a primary amine.
19. The monofilament of claim 17, wherein the reformable epoxy
resin material is formed as a reaction product of bisphenol A
diglycidyl ether (BADGE) and monoethanolamine.
20. The monofilament of claim 17, wherein the monofilament is
drapable.
21. The monofilament of claim 17, wherein the monofilament is woven
to form an end product that is drapable.
22. A fibrous material product formed from the monofilament of
claim 17 woven with one or more reinforcing fibers the one or more
reinforcing fibers having a glass transition temperature of
200.degree. C. or greater.
23. The fibrous material product of claim 22, wherein the product
is drapable.
24. A ballistic composite material including one or more layers
comprising a woven material formed from a plurality of the
reformable epoxy resin monofilaments of claim 17 and a plurality of
reinforcing fibers.
25. The composite material of claim 24, wherein the material is
used to form a helmet, body armor, or a shield.
26-27. (canceled)
28. The composite material of claim 24, wherein the composite is
formed in a heated press at a temperature below about 200.degree.
C.
29. The composite material of claim 24, wherein the reinforcing
fibers are selected from glass fibers, carbon fibers, aramid
fibers, polymer fibers (polyethylene, polypropylene, polyamide,
polyester), metallic fibers, and combinations thereof.
Description
TECHNICAL FIELD
[0001] The present invention pertains generally to reformable epoxy
resins for use in monofilament fibers, and more particularly to
drapable materials formed using said fibers and composite
structures formed therewith.
BACKGROUND
[0002] Industrial fiber materials often require means to hold or
bind materials together. Often, thermoplastic materials (e.g.,
fibers) are used to stitch or bind the materials together. However,
such current methods include a number of drawbacks including but
not limited to the incompatibility of typical thermoplastics with
secondary materials (in particular epoxy-based composite
materials), lack of sufficient blending, yarn showing through
composite surfaces, behavior of thermoplastics upon sanding or
cutting of secondary materials, rigidity of typical thermoplastics
and lack of reformability of typical thermoplastics.
[0003] Reformable thermoplastic polymers having at least one
epoxide group have been described in U.S. Pat. Nos. 5,115,075;
4,438,254; 6,011,111; and WO 98/14498 (see e.g., pages 3-8) along
with illustrative synthesis conditions, all incorporated by
reference herein (see also U.S. Pat. Nos. 3,317,471 and 4,647,648,
also incorporated by reference herein). Examples of such materials
(e.g., reformable resin materials) also can be found, without
limitation at paragraphs 15-25 of Published U.S. Patent Application
No. 20070270515 (Chmielewski et al), incorporated by reference for
all purposes.
[0004] The use of such thermoplastic polymers in a composite
material has been disclosed in PCT Publication number
WO/2008/010823 (addressing in situ reaction of an epoxy and an
amine after impregnation), incorporated by reference herein.
[0005] Yarns utilizing these reformable epoxy resin materials have
been disclosed in PCT publication number WO2016/065104. However,
this disclosure fails to identify monofilaments having the required
denier for use on the composite structures described herein.
[0006] There is thus a need for materials that have certain
thermoplastic capabilities and desirable small denier in a single
monofilament in that they can be woven with fibers having much
higher glass transition to promote constant thickness of a
composite structure formed by the woven material.
SUMMARY OF THE INVENTION
[0007] The teachings herein are directed to a method comprising
forming a reformable epoxy resin material into a monofilament
having a denier of from about 50 to about 1000 and a glass
transition temperature of less than about 200.degree. C., loading
one or more monofilaments onto a spool, co-weaving the
monofilaments with a reinforcing fiber to form a woven material,
the reinforcing fiber having a glass transition temperature of
greater than 200.degree. C., heating the woven material to form a
composite to a temperature so that only the one or more
monofilaments soften but the reinforcing fiber does not.
[0008] The reinforcing fiber may be selected from the group
consisting of glass fibers, carbon fibers, aramid fibers, polymer
fibers (e.g., polyethylene, polypropylene, polyamide, polyester)
and combinations thereof. The resulting composite may have a
constant thickness as a result of the failure of the structural
fibers to soften. The resulting composite may be utilized to form
an armor material (e.g., a composite armor material or a composite
ballistic armor material). The resulting composite may be used to
form a helmet, a jacket, a shield or the like. One or more of the
denier or diameter of the monofilament may be substantially similar
to that of the reinforcing fiber. One or more of the denier or
diameter of the monofilament may be less than that of the
reinforcing fiber. One or more of the denier or diameter of the
monofilament may be greater than that of the reinforcing fiber. The
resulting composite may be an epoxy laminate. The resulting
composite may be substantially free of any film layer.
[0009] The method may be substantially free of surface treatment
for forming class A surfaces. The resulting composite may be
paintable. The monofilament may develop adhesive properties upon
softening. The shelf life of the monofilament may be at least about
3 months, at least about 6 months, at least about 1 year, or even
at least about 5 years. The monofilament may be recyclable. The
resulting composite may be drapable.
[0010] The teachings herein are also directed to a monofilament
having a denier of from about 5 to 5000, or from about 200 to 3200
and a glass transition temperature of less than about 200.degree.
C. and comprising a reformable epoxy resin material. The reformable
epoxy resin material may be formed as a reaction product of a
difunctional epoxy resin and a primary amine. The reformable epoxy
resin material may be formed as a reaction product of bisphenol A
diglycidyl ether (BADGE) and monoethanolamine. The monofilament may
be drapable. The monofilament may be woven to form an end product
that is drapable.
[0011] The teachings herein are further directed to a fibrous
material product formed from the monofilament described herein
woven with one or more reinforcing fibers having a glass transition
temperature of 200.degree. C. or greater. The fibrous material
product may be drapable.
[0012] Also, envisioned are ballistic composite materials including
one or more layers comprising a woven material formed from a
plurality of reformable epoxy resin monofilaments and a plurality
of reinforcing fibers. The composite material may be used to form a
helmet. The composite material may be used to form body armor. The
composite material may be used to form a shield. The composite
material may be formed in a heated press at a temperature below
about 200.degree. C.
[0013] The teachings herein provide for a reformable resin
monofilament having a particular denier and glass transition
temperature so that it can be woven with a reinforcing fiber to
form a composite having a substantially constant thickness after
exposure to heat for forming the composite.
DETAILED DESCRIPTION
[0014] The present teachings meet one or more of the above needs by
the improved composite structures and methods described herein. The
explanations and illustrations presented herein are intended to
acquaint others skilled in the art with the teachings, its
principles, and its practical application. Those skilled in the art
may adapt and apply the teachings in its numerous forms, as may be
best suited to the requirements of a particular use. Accordingly,
the specific embodiments of the present teachings as set forth are
not intended as being exhaustive or limiting of the teachings. The
scope of the teachings should, therefore, be determined not with
reference to the above description, but should instead be
determined with reference to the appended claims, along with the
full scope of equivalents to which such claims are entitled. The
disclosures of all articles and references, including patent
applications and publications, are incorporated by reference for
all purposes. Other combinations are also possible as will be
gleaned from the following claims, which are also hereby
incorporated by reference into this written description.
[0015] This application is related to and claims the benefit of the
filing date of U.S. Provisional Application Ser. No. 62/683,229,
filed Jun. 11, 2018, the contents of that application being hereby
incorporated by reference herein for all purposes.
[0016] The teachings herein make advantageous use of a reformable
epoxy filament (e.g., monofilament) that adheres when cooled. The
teachings herein contemplate a method for providing composite
structures or other molded structures that are assembled (e.g.,
stitched, woven or formed with a web or mesh) with the filaments
(e.g., weavable reformable epoxy resin filaments) described herein.
The resulting structures are formable and moldable after the
reformable epoxy monofilament is heated and subsequently falls
below its glass transition temperature. The reformable epoxy
filaments are particularly compatible with dissimilar reinforcing
fibers and epoxy based secondary materials such that the
compatibility is improved over typical thermoplastic fibers (e.g.,
polyester). The glass transition temperature of the reinforcing
fibers may be higher than that of the reformable epoxy filaments
may be heated may be heated and softened while the reinforcing
fibers do not soften.
[0017] The teachings herein provide for a number of uses for the
reformable epoxy monofilaments. In one embodiment, the reformable
epoxy filaments may be woven with reinforcing fibers. Examples of
which include but are not limited to glass, carbon, aramid, and/or
polyamide fibers. The reformable epoxy filaments may be more
compatible with the reinforcing fibers as compared to typical
thermoplastic fibers. This may be due to the similarity in size,
diameter and/or denier of the reformable epoxy filaments and
reinforcing fibers. For example, the reformable epoxy monofilaments
may have a denier of from about 5 to about 6000, from about 30 to
about 4000, from about 175 to about 3800, or even from about 200 to
about 3200. The reformable epoxy monofilaments may have a denier of
from about 100 to about 1000, from about 150 to about 500, or even
from about 200 to about 400. Upon weaving the reformable epoxy
monofilaments with a reinforcing fiber, these woven structures
fibers can be used to produce drapable materials and composites
that maintain desired consistent thickness, strength and adhesion.
The flexible nature of the resulting structures are easier to form
than rigid composites, enable more complex shapes, require less
heat/energy to process, and has a higher modulus than typical
thermoplastic fibers.
[0018] In another embodiment, the reformable epoxy filament may be
combined with additional monofilaments to a desired thickness and
those combined filaments may be woven with a reinforcing fiber.
This allows for specific customization of the size of the
reformable epoxy material so that the epoxy filaments are
compatible with a selected reinforcing fiber.
[0019] The materials and methods taught herein include possible
uses for reformable epoxy filaments. It is possible that the
reformable epoxy materials may be provided initially in a pellet
form and then formed into a spooled filament. The spooled filament
and a spooled reinforcing fiber may be located adjacent one another
for simplified weaving.
[0020] The reformable epoxy monofilaments described herein may be
utilized to form composite structures that can be molded to form
helmets, body armor, shields, or protective armor (e.g., a
composite armor material or a composite ballistic armor material)
of any kind. It is desirable that these composites (or the layer of
the composite formed with the reformable epoxy monofilaments) have
a consistent cross section and/or thickness. This is made possible
by weaving the filaments with a reinforcing fiber, whereby when
exposed to elevated temperatures, the reformable epoxy filaments
soften and adhere and the reinforcing fibers do not soften and are
thus capable of maintaining the desired consistent cross section
and/or thickness.
[0021] The processing temperature may affect the yarn formation
process in that the viscosity of the reformable epoxy materials my
require adjustment to form the desired monofilaments. Specifically,
the materials may require processing at a temperature of at least
150.degree. C., at least 170.degree. C., at least 190.degree. C. or
even at least about 200.degree. C. At lower processing temperatures
the viscosity of the materials may be too high for formation into
monofilaments. In one embodiment it is possible that the material
is formulated to have a lower viscosity (sufficient for forming
into filaments) even at temperatures below 200.degree. C., below
170.degree. C., or even below 150.degree. C. However, the
temperature for processing the reformable epoxy materials may
continue to be below that of the temperature required to process
fibers formed of other materials such as typical thermoplastics.
The use of lower processing temperatures reduces the risk of
thermal stability of the filaments during processing and also
allows for easier cooling of the filaments. Cooled filaments
minimize any unwanted fiber tackiness so that the filaments are not
sticky when wound.
[0022] A key advantage of the present teachings over existing
commonly used fibers (e.g., polyester fibers) is the improved
compatibility with other materials including epoxy-based thermoset
epoxy resin matrix materials (commonly utilized in composite
structures). Specifically, the reformable monofilament may be an
amine terminated resin that can potentially react with a thermoset
resin. Further, the low glass transition temperature of the
filaments described herein are beneficial in that the disclosed
filaments can be easily softened at a low temperature without
softening the reinforcing fibers woven with the reformable epoxy
filaments. Additional benefits of the reformable epoxy filaments
include fast adhesion, and also the ability to re-form and re-mold
the filaments with the addition of heat. Adhesion and returning to
a solid state upon cooling of the reformable epoxy filaments begins
almost immediately after heating is stopped and full adhesion can
occur within about 10 seconds to about 60 seconds (e.g., about 30
seconds). In addition, a reformable epoxy filaments may be
desirable because of its long shelf life. It also may not require
storage at a refrigerated temperature, unlike some alternative
materials.
[0023] As an example, the reformable epoxy material for forming the
filaments may be and/or may include a product (e.g., a
thermoplastic condensation reaction product) of a reaction of a
mono-functional or di-functional species (i.e., respectively, a
species having one or two reactive groups, such as an amide
containing species), with an epoxide-containing moiety, such as a
diepoxide (i.e., a compound having two epoxide functionalities),
reacted under conditions for causing the hydroxyl moieties to react
with the epoxy moieties to form a generally linear backbone polymer
chain with ether linkages. Exemplary reformable epoxy materials may
be made with a difunctional epoxy resin and a primary amine which
may be bisphenol A diglycidyl ether (BADGE) and monoethanolamine.
For some applications that may require a higher glass transition
temperature (T.sub.g), it is contemplated that BADGE may be
replaced by an epoxy monomer with less mobility. Such epoxy
monomers may include diglycidylether of fluoren diphenol or 1,6
napthalene diepoxy. Also, it is contemplated that where fire
resistance is desired, BADGE can be replaced by a brominated
bisphenol A epoxy resin. Alternatively, the reformable epoxy
materials disclosed herein may also be known as poly(hydroxyamino
ether) (PHAE) as illustrated in U.S. Pat. Nos. 5,164,472;
5,275,853; 5,401,814 and 5,464,924, all incorporated by reference
herein for all purposes. Such polyethers may be prepared by
reacting a diglycidyl ether of dihydric aromatic compounds such as
the diglycidyl ether of bisphenol A, or a diepoxy-functionalized
poly(alkylene oxide) or mixture thereof with a primary amine or a
secondary diamine or a monoamine functionalized poly(alkylene
oxide) or mixture thereof. Such material generally has a relatively
high flexural strength and modulus--often much higher than typical
polyolefins (i.e. polyethylene and polypropylene)--and has the
added benefit of being melt processable at temperatures of 150 to
200.degree. C. Though other epoxide-containing moieties may be
employed, as is taught in U.S. Pat. No. 6,011,111 (incorporated by
reference; see, e.g., Cols. 5-6), and WO 98/14498 (incorporated by
reference; see, e.g., page 8) such moieties may include at least
one mono-functional epoxide and/or a di-functional epoxide
("diepoxide"). An example of a diepoxide that can be employed in
the teachings includes a diglycidyl ether of a dihydric phenol
(e.g., resorcinol, biphenol or bisphenol A). Any epoxide-containing
moiety herein may be an aliphatic and/or an aromatic epoxide.
[0024] Other examples of illustrative materials, functional species
and diepoxides are described in U.S. Pat. Nos. 5,115,075;
4,438,254; and WO 98/14498 (see e.g., pages 3-8) along with
illustrative synthesis conditions, all incorporated by reference
herein (see also U.S. Pat. Nos. 3,317,471 and 4,647,648, also
incorporated by reference herein). Examples of such materials also
can be found, without limitation at paragraphs 15-25 of Published
U.S. Patent Application No. 20070270515 (Chmielewski et al),
incorporated by reference for all purposes.
[0025] Forming the reformable epoxy materials into the desired
monofilament format may require particularly high temperatures
during the extrusion process. Accordingly, it may be necessary to
reduce the viscosity of the RER as the heat tends to increase the
viscosity to an undesirable range. This may be achieved by
modifying the ratio of the difunctional epoxy resin and primary
amine such that the molecular chain length is reduced thus reducing
the viscosity.
[0026] As used herein, unless otherwise stated, the teachings
envision that any member of a genus (list) may be excluded from the
genus; and/or any member of a Markush grouping may be excluded from
the grouping.
[0027] Unless otherwise stated, any numerical values recited herein
include all values from the lower value to the upper value in
increments of one unit provided that there is a separation of at
least 2 units between any lower value and any higher value. As an
example, if it is stated that the amount of a component, a
property, or a value of a process variable such as, for example,
temperature, pressure, time and the like is, for example, from 1 to
90, preferably from 20 to 80, more preferably from 30 to 70, it is
intended that intermediate range values such as (for example, 15 to
85, 22 to 68, 43 to 51, 30 to 32 etc.) are within the teachings of
this specification. Likewise, individual intermediate values are
also within the present teachings. For values which are less than
one, one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as
appropriate. These are only examples of what is specifically
intended and all possible combinations of numerical values between
the lowest value and the highest value enumerated are to be
considered to be expressly stated in this application in a similar
manner. As can be seen, the teaching of amounts expressed as "parts
by weight" herein also contemplates the same ranges expressed in
terms of percent by weight. Thus, an expression in the of a range
in terms of at "`x` parts by weight of the resulting polymeric
blend composition" also contemplates a teaching of ranges of same
recited amount of "x" in percent by weight of the resulting
polymeric blend composition."
[0028] Unless otherwise stated, all ranges include both endpoints
and all numbers between the endpoints. The use of "about" or
"approximately" in connection with a range applies to both ends of
the range. Thus, "about 20 to 30" is intended to cover "about 20 to
about 30", inclusive of at least the specified endpoints.
[0029] The disclosures of all articles and references, including
patent applications and publications, are incorporated by reference
for ail purposes. The term "consisting essentially of to describe a
combination shall include the elements, ingredients, components or
steps identified, and such other elements ingredients, components
or steps that do not materially affect the basic and novel
characteristics of the combination. The use of the terms
"comprising" or "including" to describe combinations of elements,
ingredients, components or steps herein also contemplates
embodiments that consist of, or consist essentially of the
elements, ingredients, components or steps.
[0030] Plural elements, ingredients, components or steps can be
provided by a single integrated element, ingredient, component or
step. Alternatively, a single integrated element, ingredient,
component or step might be divided into separate plural elements,
ingredients, components or steps. The disclosure of "a" or "one" to
describe an element, ingredient, component or step is not intended
to foreclose additional elements, ingredients, components or
steps.
[0031] It is understood that the above description is intended to
be illustrative and not restrictive. Many embodiments as well as
many applications besides the examples provided will be apparent to
those of skill in the art upon reading the above description. The
scope of the invention should, therefore, be determined not with
reference to the above description, but should instead be
determined with reference to the appended claims, along with the
full scope of equivalents to which such claims are entitled. The
disclosures of all articles and references, including patent
applications and publications, are incorporated by reference for
all purposes. The omission in the following claims of any aspect of
subject matter that is disclosed herein is not a disclaimer of such
subject matter, nor should it be regarded that the inventors did
not consider such subject matter to be part of the disclosed
inventive subject matter.
* * * * *