Note: Descriptions are shown in the official language in which they were submitted.
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THERMOPLASTIC FIBERS AND FABRICS
The present invention relates to thermoplastic fibers and fabrics.
It is known to prepare fibers, yarns and fabrics from polystyrene, vinyl
polymers, nylons, polyesters, polyolefins, or fluorocarbons. See, for example,
U.S. Patents 4,181,762; 4,945,150; 4,909,975 and 5,071,917.
However, it still remains desirable to provide fibers prepared from
polymers which have not been used as starting materials for the preparation of
fibers,
yarns and fabrics. These fibers have exceptional properties with respect to
bonding,
hydrophilicity and chemical resistance which is a special feature of epoxy-
based
polymers.
In a first aspect, the present invention is a fiber comprising at least one
thermoplastic hydroxy-functionalized polyether or polyester and, optionally, a
thermoplastic polymer which is not a hydroxy-functionalized polyether or
polyester.
in a second aspect, the present invention is a bicomponent fiber having {1)
a first component comprising a thermoplastic hydroxy-functionalized polyether
or
polyester or a blend of hydroxy-functionalized polyether or polyester and (2)
a second
component comprising a thermoplastic polymer which is not a hydroxy-
functionalized
polyether or polyester.
In a third aspect, the present invention is a method of forming a non-
2 0 woven fabric by forming a web of at least one fibrous component and
heating the web to
cause bonding of fibrous components of the web, characterized in that at least
one
fibrous component comprises a thermoplastic hydro;~y-functionalized poiyether
or
polyester.
The fiber of the present invention can be a single component or a
bicomponent fiber.
The single component fiber comprises at least one thermoplastic hydroxy-
functionalized poiyether or polyester and, optionally, a thermoplastic polymer
which is not
a hydroxy-functionalized polyether or polyester.
The bicomponent fiber of the present invention has {1} a first component
3 0 comprising a thermoplastic hydroxy-functionalized polyether or polyester
or a blend of
hydroxy-functionalized polyether or polyester and {2) a second component
comprising a
thermoplastic polymer which is not a hydroxy-functionalized polyether or
polyester.
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In general, the thermoplastic hydroxy-functionalized polyethers or
polyesters are prepared by the reaction of a dinucleophilic monomer with a
diglycidyl
ether, a diglycidyf ester or epihalohydrin.
Preferably, the thermoplastic hydroxy-~functionalized polyether or polyester
is selected from
(1 ) poly(hydroxy ester ethers) or poly(hydroxy esters) having repeating
units represented by the formula:
O O
OC-R~-COR30R~0--R3
m
(2) polyetheramines having repeating units represented by the formula:
OH OH
I I
O-CH2-C-CH2-A-CH2-C-CH2-O-B II
RS
(3} hydroxy-functionalized polyethers having repeating units represented
by the formula:
OH
I
O-CH2- i -CH2-O-B - III
RS
1
or
(4) hydroxy-functionalized poly(ether sulfonamides) having repeating units
represented by the formula:
OH R~ O 8 O R~ ~H
OCH2CCH2N-i -R-S-NCH2 i.CH20B IVa ,
RS O O RS
m
or
OH OH
I I
OCH2CI CH2-N-CH2CCH20lB 1~
RS O=S=O R5 m
R9
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WO 00/32854 z PCTIUS99/28462
wherein R' is a divalent organic moiety which is primarily hydrocarbon; R2 is
independently a divalent organic moiety which is primarily hydrocarbon; R3 is
OH ~H20H
-CH2CCH2 and -~--CHz- ;
RS RS
R4 is
O O OH
-C-R6 C- or -R2 OCH2CCH20R6
R5
n
RS is hydrogen or alkyl; Rs is a divalent organic moiety which is primarily
hydrocarbon; R'
and R9are independently alkyl, substituted alkyl, aryl, substituted aryl; Re
is a divalent
organic moiety which is primarily hydrocarbon; A is an amine moiety or a
combination of
different amine moieties; B is a divalent organic moiety which is primarily
hydrocarbon; m
is an integer from 5 to 1000; and n is an integer from 0 to 100.
In the preferred embodiment of the present invention, A is 2-
hydroxyethylimino-, 2-hydroxypropyl-imino-, piperazenyl, N,N'-bis(2-
hydroxyethyl)-1,2-
ethyfenediimino; and B and R' are independently 1,3-phenylene, 1,4-phenylene;
sulfonyldiphenylene, oxydiphenylene, thiodiphenylene or isopropylidene-
diphenylene; R5
is hydrogen; R' and R9 are independently methyl, ethyl, propyl, butyl, 2-
hydroxyethyl or
phenyl; and B and Reare independently 1,3-phenylenE:, 1,4-phenylene,
sulfonyldiphenylene, oxydiphenylene, thiodiphenylene or
isopropylidenediphenylene.
The poly(hydroxy ester ethers) represented by Formula I are prepared by
reacting diglycidyl esters of aliphatic or aromatic diacids, such as
diglycidyl terephthalate,
2 0 or diglycidyl ethers of dihydric phenols with aliphatic or aromatic
diacids such as adipic
acid or isophthalic acid. These polyesters are described in U.S. Patent
5,171,820.
Alternatively, the poly(hydroxyester ethers) are prepared by reacting a
diglycidyl ester
with a bisphenof or by reacting a diglycidyl ester, diglycidyl ether, or an
epihalohydrin with
a dicarboxylic acid.
The polyetheramines represented by Formula II also referred to as
poly(hydroxy amino ethers) are prepared by contacting one or more of the
diglycidyl
ethers of a dihydric phenol with an amine having two amine hydrogens under
conditions
sufficient to cause the amine moieties to react with epoxy moieties to form a
polymer
backbone having amine linkages, ether linkages and ~>endant hydroxyl moieties.
These
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WO 00/32854 4 PCT/US99/28462
polyetheramines are described in U.S. Patent 5,275,853. The polyetheramines
can also
be prepared by contacting a diglycidyl ether or an epihalohydrin with a
difunctional amine.
The hydroxy-functionalized polyethers represented by Formula III are
prepared, for example, by contacting a diglycidyl ether or a combination of
diglycidyl
ethers with a dihydric phenol or combination of dihydric phenols using the
process
described in U.S. Patent 5,164,472. Alternatively, the poly(hydroxy ethers)
are obtained
by allowing a dihydric phenol or a combination of dihlydric phenols to react
with an
epihalohydrin by the process described by Reinking, Barnabeo, and Hale in the
Journal
of Applied Polymer Science, Volume 7, page 2135 (3'963).
The hydroxy-functionalized poly(ether sulfonamides) represented by
Formulae IVa and IVb are prepared, for example, by polymerizing an N,N'-
dialkyl or
N,N'-diaryldisulfonamide with a diglycidyl ether as described in U.S. Patent
5,149,768.
The hydroxy-functionalized polyethers commercially available from
Phenoxy Associates, Inc. are also suitable for use in the present invention.
These
hydroxy-functionalized polyethers are the condensation reaction products of a
dihydric
polynuclear phenol, such as bisphenol A, and an epihalohydrin and have the
repeating
units represented by Formula III wherein B is an isopropylidene diphenylene
moiety.
These hydroxy-phenoxyether polymers and the proc~as for preparing them are
described
in U.S. Patents 3,305,528. Other hydroxy functional polyethers that are
suitable for use
in the present invention are poly(alkylene oxides), which are typically
produced through
the polymerization of ethylene oxide, propylene oxide or butylene oxide.
Specific
examples include, but are not limited to, polyethylene oxide), poly{propylene
oxide),
poly(butylene oxide), or copolymers containing varying amounts of different
poly(alkylene
oxides). These polymers also may be particularly suitable for blending with
polymers of
any of Formulas f through 1V. Advantages of blends of poly{alkylene oxides)
and
polymers of Formulas 1 through IV include the ability to manipulate the glass
transition
temperature of the blends or to modify hydrophilicity.
The polymers which are not hydroxy-functionalized polyesters or
polyethers which can be employed in the practice of ilhe present invention for
preparing
3 0 the fibers include polyolefins, polyesters, polyamides, polysaccharides,
modified
polysaccharides or naturally-occurring fibers or particulate fillers;
thermoplastic
polyurethanes, thermoplastic elastomers and glycol-rnodified copolyester
(PETG). Other
polymers of the polyester or polyamide type can also be employed in the
practice of the
present invention for preparing the fiber. Such polymers include
poly{hexamethylene
adipamide), polycaprolactone, poly(hexamethylene sebacamide), polyethylene 2,6-
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naphthalate) and polyethylene 1,5-naphthalate), poly(tetramethylene 1,2-
dioxybenzoate)
and copolymers of ethylene terephthalate and ethylene isophthalate.
The polyesters and methods for their ipreparation are well known in the art
and reference is made thereto for the purposes of thiis invention. For
purposes of
illustration and not limitation, reference is particularly made to pages 1-62
of'Volume 12
of the Encyclopedia of Polymer Science and E»gineering, 1988 revision, John
Wiley &
Sons.
The polymers which are not hydroxy-functionalized polyesters or
polyethers can be blended with the hydroxy-functionalized polyether or
polyester at levels
of less than 50 weight percent and, preferably less than 30 weight percent,
based an the
weight of the fiber. These other polymers can be blended into the hydroxy-
functionalized
pofyether ar polyester in order to reduce composition cost, to modify physical
properties,
barrier or permeability properties, or adhesion characteristics. In the case
of
bicomponent fibers, the separate non-hydroxy-functional-containing component
may be
used at levels of up to 99 percent, preferably less than 95 percent, based on
the weight
of the fiber.
The polyamides which can be employed in the practice of the present
invention for preparing the fibers include the various grades of nylon, such
as nylon 6,
nylon 6,6 and nylon 12.
2 0 By the term "polyolefin" is meant a polymer or copolymer derived from
simple olefin monomers such as ethylene, propylene, butylene, or isoprene, and
one or
more monomers copolymerizable therewith. Such polymers (including raw
materials,
their proportions, polymerization temperatures, catalysts and other
conditions) are well-
known in the art and reference is made thereto for the purpose of this
invention.
Additional comonamers which can be polymerized with ethylene include olefin
monomers
having from 3 to 12 carbon atoms, ethylenically unsaturated carboxylic acids
(both mono-
and difunctional) and derivatives of such acids such as esters (for example,
alkyl
acrylates) and anhydrides; monovinylidene aromatics and monovinylidene
aromatics
substituted with a moiety other than halogen such as styrene and
methylstyrene; and
3 0 carbon monoxide. Exemplary monomers which can be polymerized with ethylene
include
1-octene, acrylic acid, methacrylic acid, vinyl acetate and malefic anhydride.
The polyolefins which can be employed in the practice of the present
invention for preparing the fibers include polypropylene, polyethylene, and
copolymers
and blends thereof, as well as ethylene-propylene-diene terpolymers. Preferred
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WO 00!32854 6 PCTNS99/28462
polyolefins are polypropylene, such as Pro-tax T"' PF635 (Trademark of Montell
North
American Inc.) and INSPIRE T"" (Trademark of The Dow Chemical Company), linear
high
density polyethylene (HDPE), heterogeneously-branched linear low density
polyethylene
(LLDPE) such as DOWLEXT"" polyethylene resin (Trademark of The Dow Chemical
Company}, heterogeneously-branched ultra low linear density polyethylene
(ULDPE)
such as ATTANET"" ULDPE (Trademark of The Dow Chemical Company);
homogeneously-branched, linear ethylene/a-olefin copolymers such as TafmerT""
(Trademark of Mitsui Petrochemicals Company Limited) and ExactT"" (Trademark
of
Exxon Chemical Company); homogeneously branched, substantially linear
ethyienela-
olefin polymers such as AFFINITYT"' (Trademark of 'fhe Dow Chemical Company)
and
ENGAGE~ (Trademark of DuPont Dow Elastomers L..L. C) polyolefin elastomers,
which
can be prepared as disclosed in U.S. Patents 5,272,2'36 and 5,278,272; and
high
pressure, free radical polymerized ethylene polymers and copolymers such as
low
density polyethylene (LDPE), ethylene-acrylic acid (EAA} copolymers such as
25 PRIMACORT"" (Trademark of The Dow Chemical Cornpany), and ethylene-vinyl
acetate
(EVA} copolymers such as EscoreneT"" polymers (Trademark of Exxon Chemical
Company), and EIvaxT"" (Trademark of E:I. du Pont de Nemours & Co.). The more
preferred polyolefins are the homogeneously-branched linear and substantially
linear
ethylene copolymers with a density (measured in accordance with ASTM D-792) of
0.85
2 0 to 0.99 g/cm3, a weight average molecular weight to number average
molecular weight
ratio (Mw/Mn) from 1.5 to 3.0, a measured melt index (measured in accordance
with
ASTM D-1238 (i90/2.16)) of 0.01 to 100 g/10 minutes, and an 110112 of 6 to 20
(measured in accordance with ASTM D-1238 (190/10)).
In general, high density polyethylene (HDPE) has a density of at least
25 about 0.94 grams per cubic centimeter (g/cc) (ASTM 'Test Method D-1505).
HDPE is
commonly produced using techniques similar to the preparation of linear low
density
polyethyienes. Such techniques are described in U.S. Patents 2,825,721;
2,993;876;
3,250,825 and 4,204,050. The preferred HDPE employed in the practice of the
present
invention has a density of from 0.94 to 0.99 g/cc and a melt index of from
0.01 to 35
3 0 grams per 10 minutes as determined by ASTM Test Method D-1238.
The polysaccharides which can be employed in the practice of the present
invention are the different starches, celluloses, hemicellufoses, xylanes,
gums, pectins
and pullutans. Polysaccharides are known and are described, for example, in
Encyclopedia of Polymer Science and Technology, 2rrd edition, 1987. The
preferred
3 5 polysaccharides are starch and cellulose.
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The modified polysaccharides which can be employed in the practice of
the present invention are the esters and ethers of po0ysaccharides, such as,
for example,
cellulose ethers and cellulose esters, or starch ester:. and starch ethers.
Modified
polysaccharides are known and are described, for example, in Encyclopedia of
Polymer
Science and Technology, 2nd edition, 1987.
The term "starch" as used herein, refers to carbohydrates of natural
vegetable origin, composed mainly of amylose and/or amylopectin, and includes
unmodified starches, starches which have been dewatered but not dried,
physically
modified starches, such as thermoplastic, gelatinized or cooked starches,
starches with a
modified acid value (pH) where acid has been added to lower the acid value of
a starch
to a range of from 3 to 6, gelatinized starches, ungelatinized starches, cross-
linked
starches and disrupted starches (starches which are not in particulate form).
The
starches can be in granular, particulate or powder form. They can be extracted
from
various plants, such as, for example, potatoes, rice, tapioca, corn, pea, and
cereals such
as rye, oats, and wheat.
Celluloses are known and are described, for example, in Encyclopedia of
Polymer Science and Technology, 2nd edition, 1987. Celluloses are natural
carbohydrate high polymers (polysaccharides) consisting of anhydroglucose
units joined
by an oxygen linkage to form long molecular chains that are essentially
linear. Cellulose
2 0 can be hydrolyzed to form glucose. The degree of polymerization ranges
from 1000 for
wood pulp to 3500 for cotton fiber, giving a molecular weight of from 160,000
to 560,000.
Cellulose can be extracted from vegetable tissues (wood, grass, and cotton).
Celluloses
can be used in the form of fibers.
The naturally-occurring fibers or particulate fillers which can be employed
2 5 in the practice of the present invention are, for example, wood flour,
wood pulp, wood
fibers, cotton, flax, hemp, or ramie fibers, rice or wheat straw, chitin,
chitosan, cellulose
materials derived from agricultural products, nut shell flour, corn cob flour,
and mixtures
thereof.
In general, the fibers of the present invention can be formed by well known
3 0 processes such as melt spinning, wet spinning, or conjugate spinning. The
fibers of the
present invention may be extruded into any size, or length desired. They may
also be
extruded into any shape desired, such as, for example, cylindrical, cross-
shaped, trilobal
or ribbon-like cross-section.
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The bicomponent fibers of the present invention can have the following
fiber cross-section structures:
{1 ) Side-by-side
(2) Sheath-core
(3) Islands-in-the sea and
(4) Citrus (Segmented pie)
(1 ) Side-by-side
A method for producing side-by-side bicomponent fibers is described in
U.S. Patent 5,093,061. The method comprises (1 ) feeding two polymer streams
through
orifices separately and converging at substantially the: same speed to merge
side-by-side
as a combined stream below the face of the spinneret; or (2) feeding two
polymer
streams separately through orifices, which converge <~t the surface of the
spinneret, at
substantially the same speed to merge side-by-side as a combined stream at the
surface
of the spinneret. In both cases, the velocity of each polymer stream at the
point of merge
is determined by its metering pump speed and the size of the orifice. The
fiber cross-
section has a straight interface between two componf;nts.
Side-by-side fibers are generally used to produce self-crimping fibers. All
commercially available self-crimping fibers are produced by using a system
based on the
different shrinkage characteristics of each component.
2 0 (2) Sheath-core
Sheath-core bicomponent fibers are those fibers where one of the
components (core) is fully surrounded by a second component (sheath). Adhesion
is not
always essential for fiber integrity.
The most common way to produce sheath-core fibers is a technique in
which two polymer liquids (melts) are separately led to a position very close
to the
spinneret orifices and then extruded in sheath-core form. In the case of
concentric fibers,
the orifice supplying the "core" polymer is in the center of the spinning
orifice outlet and
flow conditions of core polymer fluid are strictly controlled to maintain the
concentricity of
both components when spinning. Modifications in spinneret orifices enable one
to obtain
3 4 different shapes of core or/and sheath within the fiber cross-section.
The sheath-core structure is employed when it is desirable for the surface
to have the property of one of the polymers such as luster, dyeability or
stability, while the
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core may contribute to strength, and reduced cost. The sheath-core fibers are
used as
crimping fibers and as bonding fibers in the non-woven industry.
The sheath-core bicomponent fiber can have a core comprising the
hydroxy-functionalized polyether or polyester and a slheath comprising a
polymer which is
not a hydroxy-functionalized polyether or polyester. Alternatively, the
hydroxy-
functionalized polyether or polyester can be the sheath and the polymer that
is not the
hydroxy-functionalized polyether or polyester the corE; of the bicomponent
fiber. The
sheath-core may be circular in cross-section or may have some other geometry,
such as
trilobal. A variant such as "tipped trilobal" can also be; constructed wherein
the sheath
component is no longer continuous about the core but exists only at the tips
of the lobes
formed by the core. Other configurations which may be utilized are illustrated
in
lnternationa! Fiber Journal, Volume 13, No, 3, June 1998 in the articles
beginning on
pages 20, 26, and 49.
Methods for producing sheath - core biicornponent fibers are described in
U.S. Patents 3,315,021 and 3,316,336.
(3) Islands-in the-sea
Islands-in-the sea fibers are also called matrix-filament fibers which
include heterogeneous bicomponent fibers. A method for producing islands-in-
the sea
fibers is described in U.S. Patent 4,445,833. The method comprises injecting
streams of
2 0 core polymer into sheath polymer streams through small tubes with one tube
for each
core stream. The combined sheath-core streams converge inside the spinneret
hole and
form one island-in-the sea conjugate stream.
Mixing the different polymer streams with a static mixer in the spinning
process also makes island-in-the-sea bicomponent fik~ers. The static mixer
divides and
redivides the polymer stream to form a matrix stream with multiple cores. This
method
for producing island-in-the-sea fibers is described in U.S. Patent 4,414,276.
The hydroxy-functionalized polyether or polyester can be the sea polymer
and the polymer which is not a hydroxy-functionalizedl polyether or polyester
can be the
island polymer. The hydroxy-functionalized polyether or polyester can also be
the island
3 0 polymer and the polymer which is not a hydroxy-functionalized polyether or
polyester, the
sea polymer.
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The islands-in-the-sea structure is employed when it is desirable to
increase the modulus of the fiber, reduce moisture regain, reduce dyeability,
improve the
texturing capability or give the fiber a unique lustrous appearance.
(4) Citrus type (Segmented pie)
The citrus type bicomponent or segmented pie bicomponent fibers can be
made by polymer distribution andlor spinneret modifications of the pack
assemblies
employed in the methods described above for producing the side-by-side, sheath-
core or
islands-in-the-sea fibers. For example, by introducing a first polymer stream
and a
second polymer stream alternately through eight radial channels toward the
spinneret
hole instead of two channels, the resultant fiber is an eight-segment citrus
type fiber. If
the spinneret orifice has the configuration of three or four slots on a circle
(a common
orifice configuration to produce hollow fibers}, the fiber is a hollow citrus
type fiber with
eight segments. The hollow citrus type fiber can also be made by the use of
special
spinneret orifice configurations with a sheath-core spin pack as described in
U-.S. Patents
4,246,219 and 4,357,290.
The fibers of the present invention can be blended with other synthetic or
natural fibers, such as carbon fibers, cotton, wool, polyester, polyolefin,
nylon, rayon,
glass fibers, fibers of silica, silica alumina, potassium titanate, silicone
carbide, silicone
nitride, boron nitride, boron, acrylic fibers, tetrafluoroethyfene fibers,
polyamide fibers,
2 0 vinyl fibers, protein fibers, ceramic fibers, such as aluminum silicate,
and oxide fibers,
such as boron oxide.
Additives such as pigments, stabilizers, impact modifiers, plasticizers,
carbon black, conductive metal particles, abrasives and lubricating polymers
may be
incorporated into the fibers. The method of incorporating the additives is not
critical. The
2 5 additives can conveniently be added to the hydroxy-functionalized
polyether or polyester
prior to preparing the fibers. If the hydroxy-functionalized polyether or
polyester is
prepared in solid form, the additives can be added to ifhe melt prior to
preparing the
fibers.
The fibers of the present invention can be crosslinked by chemical
3 0 treatment, heating or irradiation with ultraviolet light. f=or example,
the fibers can be
chemically treated with crosslinking agents such as diiisocyanates,
glycidylmethacrylate,
bisepoxides and anhydrides.
The fibers of the present invention are suitable for use in filtration media,
binder fibers for glass or carbon fibers, binder fibers in non-woven fabrics
made of
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thermoplastic polymers which are not hydroxy-functionalized polyethers or
polyesters or
binder fibers in non-woven fabrics made of cellulosic-based materials. These
fibers are
also useful in the manufacture of medical apparels. 'They are also useful in
making
woven and non-woven fabrics which can be used in making apparels, water-
absorbent
cloths, antistatic wipes, or water-absorbent mats.
Woven fabrics are formed from the fibers of the present invention by
techniques commonly used in the woven textiles industry, such as weaving or
knitting.
Non-woven fabrics are based on a fibrous web. The fibers of the present
invention can be formed into webs using the following known technologies:
(1 ) Dry-formed, carded or air-laid and bonded - "The webs are formed from
staple
fibers by carding or air-laying, bonded overall or in a pattern with latex or
other
water-borne adhesives. In carding, clumps of staple fibers are separated
mechanically into individual fibers and formed intro a coherent web. In air-
laying,
fibers are introduced into an airstream and are captured on a screen from the
air
stream.
(2) Thermal-bonded - Dry-formed webs of staple fibers are bonded with fusible
fibers or composed entirely of fusible fibers.
(3) Air-laid - Wood pulp fibers, with or without added staple fibers, are
bonded with
latex or similar adhesives.
(4) Wet-formed - Short fibers are formed into a ~rveb by processes derived
from
paper-making technology, followed by bonding with latex or thermal binders.
(5) Spun-bonded - Webs composed of long filaments with normal textile diameter
are formed directly from bulk polymer and are usually bonded thermally.
(6) Melt-blown - Webs of long, extremely fine diameter fibers are formed
directly
2 5 from bulk polymer and are usually bonded by hot embossing processes.
(~) Spun-laced - Dry-formed webs are mechanically entangled by multiple fine,
high
pressure water jets, in most cases; without adhesive binder.
(8) Needle-punched - Fibers are mechanically entangled by multiple
reciprocating
banks of barbed needles.
(9) Laminated - Different layers are combined in composite or reinforced
fabric by
an adhesive, thermal fusion or entanglement.
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(10) Stitch-bonded - Staple fiber webs are reinforced or mechanically
entrapped by
yarns stitched or knitted through the webs.
Non-woven fabrics and processes for preparing them are described in the
Encyclopedia of Polymer Science And Engineering, Second Edition, Volume 10,
pages 204-251.
The following working examples are given to illustrate the invention and
should not be construed as limiting its scope. Unless otherwise indicated, all
parts and
percentages are by volume.
Example 1
A 318-inch (0.95 cm) single-screw extruder fitted with an 8-hole spinneret
was used to spin monofilaments based on 100 percent thermoplastic hydroxy-
functional
polyether. The melt temperature was 200°C. The fibers were rolled onto
bobbins without
further stretching.
Example 2
Bicomponent fibers containing polypropylene as the core and a
thermoplastic hydroxy-functionalized polyether as the sheath were spun. Two
single-
screw extruders, one feeding the polypropylene and another feeding the
thermoplastic
hydroxy-functionalized polyether were used. The extruders fed the molten
polymers
(melt temperature was 200°C) to a 288-holed spinneret from which the
bicomponent
2 0 fibers were spun. Fibers with polypropyleneahermoplastic hydroxy-
functionalized
polyether ratios of 90:10, 80:20, 70:30, 40:60 and 50:50 were spun. The fibers
were also
stretched after exiting the spinneret by using extender' rolls and then taken
up on
bobbins.
Example 3
A polyetheramine poly(hydroxy amino ether) (derived from the reaction of
the diglycidyl ether of bisphenol A and ethanolamine) and a polypropylene were
spun into
bicomponent fibers. The poly(hydroxy amino ether) had an MFI (Melt Flow Index)
of 8 at
230°C using a 2.16 kg weight. The polypropylene source was a 35 MFI Pro-
fax T"" PF635
3 0 polypropylene from Montell. This sheathlcore bicomponent fiber was
produced under the
conditions listed in Table I.
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Table I
GENERAL SHEATH EXTRUDER C~RE EXTRUDER
Pol mer T a Dow Polyetheramine~8 Pol ro lene 35 MFI
MF'I
Ratio w/w 20 80
Meter Pum r m 6.46 39.45
Extrusion Temps,
C
Zone1 185 210
Zone 2 200 220
Zone 3 200 220
Zone 4 210 220
S in Head 210 210
Pack Pressure 2600 1900
si
Roll Conditions SPEED Meters/Minut TEMP
e) C
Denier Roll _ Ambient
1500
Tension Roll 1500 Ambient
Draw Roll # 1400 50C
1
Draw Roll # 7575 50
2
Example 4
A 30/70 weight/weight {w/w) poly{hydroxy amino ether) (derived from the
reaction of the diglycidyl ether of bisphenol A and ethanolamine}
sheath/polypropylene
core bicomponent fiber was treated on a Tech Tex tea;turizing unit to impart a
crimp . This
equipment uses the stuffer box method of texturizing. The texturized yarn was
cut into
staple fiber of 2-inch (5 cm) length on an Ace Strip Cutter, Model C-75. After
the
crimping and staple cutting operations the fiber was olpened a 12-inch {30.5
cm} wide
microdenier metallic card in tots of 30 grams. The open fiber was then used to
produce a
batt on a sample card line. This carded batt was needled on a James Hunter
Fiberlocker
Needle machine to give a resultant needle-punched fabric.
Example 5
Cotton fibers (4 kg, 1.5 to 5 cm in length) and 7-denier bicomponent fibers
(30170 (w1w) poly(hydroxyarninoether)/polypropylene}" {0.45 kg, 2.5 cm in
length) were
2 0 manually mixed and then opened up. The blend was carded and converted into
a non-
woven web, which was thermally bonded with calender rolls at 170°C.
Example 6
Cotton linters {150 g) and 7-denier bico~mponent fibers (30/70 {w/w)
polyetheramine/polypropylene) were added to 300 L o~f water in a cylindrical
tank and the
contents were agitated for 5 minutes. The polyetheramine was derived from the
reaction
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WO 00!32854 14 PCT/US99/28462
of the diglycidyi ether of bisphenol A and ethanolamine. The ratio of
bicomponent fibers
to cotton !inters was 5 percent on a weight basis. The; slurry was then pumped
to a
moving belt made of polyester mesh and the webs formed were collected. The wet
webs
were dried by passing them through a 165°C oven with approximately one
minute of
dwell time. The dried webs were then bonded with heated calendar rolls at
temperatures
from 100°C to 180°C. The basis weight of the webs after bonding
was about 90 gsm.
Example 7
A bicomponent, sheath/core spunbond fabric was produced under the
conditions shown in Table II. The polyetheramine (derived from the reaction of
the
diglycidyl ether of bisphenol A and ethanolamine) sheath had a MFI of 15. The
polypropylene core was composed of a 35 MFI Pro-fax TM PF635. The sheath/core
ratio
was 20/80 (w/w). The system was run at slot air press>ures of 20, 25 and 30
psi and the
spunbond material was collected on perforated belt/vacuum collection system.
Collection
speeds ranged from 50 to 75 meters per minute. Calendar rolls were set to
60°C and
appeared to provide adequate bonding for dry web stock.
Table II
GENERAL SHEATH EXTRUDER CORE EXTRUDER
Pol mar T a Dow Pol etheramine Montell Polyprapylene
15 MFl (35 MFI
Ratio w/w _ 20 80
Extrusion Tem s,
C
Zone 1 180 195
Zone 2 185 215
Zone 3 184 225
Zone 4 195 223
Melt Pum Pressure 840 1030
si
Meter Pum r m 6.2 53.1
Formin Table S eed (meters/min74.8
To Calendar Roll Spd(meters/min75.4
Bott Calendar Roll S d meters/min76
Calendar Tem erature C 60~
Farce N/mm 8a~
Examples 8 Through 15 - PHAE Blends for Hydrophilic FiberlFabric Applications
The poly(hydroxy amino ether) ("PHAE") used in the following Examples 8
through 15 was produced by The Dow Chemical Company from the polymerization of
a
diglycidyl ether of Bisphenol A and ethanol amine. The PHAE had the following
2 5 properties: number average molecular weight (Mn) ~ 14,000; weight average
molecular
weight (Mw) = 35,000; melt index = 15 (measured at 190°C with a 2.16 kg
weight}; glass
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WO 00/32854 15 PCT/US99128462
transition temperature (Tg) = 78°C. In these Examples 8 through 15, PEG
refers to
polyethylene glycol) and PEO refers to polyethylene oxide). PEG and PEO have
the
same polyoxyethylene repeating unit shown below:
(-CH2CH20-)~
Designation of polymers with the above structure as PEG or PEO was based on
the
product name given in an Aldrich catalogue; that is, F'EG is used if the
number average
molecular weight (Mn) of the polyoxyethylene is 10,000 or less, and PEO if the
viscosity
average molecular weight (Mv) is 100,000 or above. .In the following examples,
the
number immediately after PEG or PEO indicates the calculated average molecular
weight
{Mn or Mv) from the Aldrich catalog.
EPE refers to a block copolymer with the general structure shown below:
H(-OCH2CH2 }X[-OCH(CH3)CH2 ]y{-OCH2CH2 )ZOH
The EPE block copolymers contain a hydrophobic block of polypropylene
oxide), having a molecular weight ranging from a minimum of 900 to a maximum
of 4000,
with two hydrophilic polyoxyethylene blocks such that: the combined weight of
the
polyoxyethylene blocks constitutes from 10 to 90 weight percent of the total
molecule.
The EPE block copolymers are nonionic surfactants [see L. G. Lundsted and LR.
Schmolka, "The Synthesis and Properties of Block Copolymer Polyol Surfactants"
in
Block and Graft Copolymerization, volume 2 (edited k>y R. J. Ceresa), John
Wiley and
Sons, New York, chapter 1, pp. 1-103]. The EPE block copolymers are marketed
under
the Trademark PLURONIC~ polyols (BASF Wyandotte Corporation} and are also sold
by The Dow Chemical Co. (for example, PolygIycol EP-1730 and EP-1660}.
The nomenclature used herein for specific EPE block copolymers gives
the weight percent ethylene glycol and the average calculated molecular weight
(Mn), as
2 5 given in the Afdrich catalog. For example, EPE-30 (Mn 5800) refers to an
EPE block
copolymer containing 30 weight percent ethylene glycol and having a calculated
number
average molecular weight of 5800.
The following test methods were used for Examples 8 through 15
Glass transition temperature (Tg) was determined using a TA Instruments
3 0 DSC 2010 Differential Scanning Calorimeter. SampiE;s {5 to 10 mg) were
prepared in
hermetically sealed pans. Two scans were made for each sample. The first scan
was
made from ambient to 200°C at i 0°C per minute. The sample was
then cooled to
ambient temperature or below using dry ice, whereupon the second scan was made
at
10°/minute to 200°C. The Tg was determined from trte second scan
inflection point.
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pH7 Buffer Contact Angle was determined for compression molded films
using a Kruss G40 Contact Angle Measuring Systerrr (Goniometer} equipped with
a
Eurometrix fiber optic light source, a Kernco model C~-1 microscope, stage,
light source,
and camera mount, and a Kruss Panasonic CCTV camera and WV-5410 monitor. A
small drop of the pH7 buffer was applied to the film and the angle formed at
the
filmldrop/air interface was measured using the systeim softvvare (G40 V1.32-
US). In the
examples that follow the terms "water contact angle" and "pH7 buffer contact
angle" are
synonymous.
Laboratory-scale fiber spinning of PHAE blends. The apparatus for
spinning fiber consisted of a Rheometrix capillary melt rheometer equipped
with a 1000
p.m die, a Rheotens attachment, and a 12 inch (30.5 cm) circumference variable
speed
roll onto which the fiber was spun.
Example 8 - PHAE Blend With 10 Weight Percent PEG 10.000
PHAE (243.0 g) and PEG 10,000 (27.1 g, Aldrich Chemical Co., Tm
63°C)
were melt blended for 20 minutes in a large capacity Haake Torque rheometer
(with roller
mixing blades) at 170°C isothermal metal temperature and 100 rpm mixing
rate. The
resulting blend had a Tg of 53°C with no crystalline melting point. A
compression
molded film of the blend was transparent and had a water contact angle of 67.
Fiber was
melt spun at 190°C with a rheometer plunger speed of 0.3 inch/minute
and a take-up roll
speed of 1780 rpm (543 mlminute). Additional blends with 5 and 25 weight
percent PEG
10,000 were also prepared and the results are included in Table III.
Example 9 - PHAE Blend With 5 Weight Percent PEO 100.000
PHAE (57.1 g) and PE0 100,000 (3.1 g, Aldrich Chemical Co., Tm
65°C)
were melt blended in a Haake Torque rheometer for 15 minutes at 180°C
isothermal
metal temperature and 100 rpm mixing rate. The resulting blend had a Tg of
66°C with
no crystalline melting point. A compression molded film of the blend was
transparent and
had a water contact angle of 68. Fiber was melt spun at 190°C with a
plunger speed of
0.3 inch/minute (8mmlminute) and a take-up speed of 1780 rpm
(543 m/minute). The denier of the fiber was 9 g (equals the weight of 9000 m
of
3 0 continuous fiber). Additional blends with 10 percent and 25 percent PEO
100,000 were
prepared and the results are included in Table III.
Example 10 - PHAE blend with 5 Weight Percent PEO 4 000 000
PHAE (57.0 g) and PEO 4,000,000 (3.0 g, Aldrich Chemical Co., Tm
65°C) were melt blended in a Haake torque rheometer for 20 minutes at
980°C
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WO 00/32854 ~7 PCT/US99/28462
isothermal metal temperature and 100 rpm mixing rate. The resulting blend had
a Tg of
67°C with na crystalline melting point. A compressian molded film of
the blend was
transparent and had a water contact angle of 65. Fiber was melt spun at i
90°C with a
plunger speed of 0.3 inch/minute {8 mm/minute) and a take-up speed of 1780 rpm
(543
m/minute}. The denier of the fiber was 10 g.
Example i 1 - PHAE Blend With 10 Weight Percent f'EO 4.000.000
PHAE (243.0 g) and PEO 4,000,000 {27.0 g, Aldrich Chemical Co., Tm
65°C} were melt blended in a Haake torque rheometer for 25 minutes at
180°C
isothermal metal temperature and 100 rpm mixing speed. The resulting blend had
a Tg
of 55°C with no crystalline melting point. A compressian molded film of
the blend was
transparent and had a water contact angle of 72. Fit>er was melt spun at
190°C with a
plunger speed of 0.3 inch/minute (8 mm/minute) and a take-up speed of 1780 rpm
(543
m/minute).
Example 12 - PHAE Blend With 15 Weioht Percent PEO 4L000.000
PHAE (51.0 g) and PEO 4,000,000 (9.0 g, Aidrich Chemical Co., Tm
85°C) wAre melt blended in a Haake torque rheometE:r for 20 minutes at
180°C
isothermal metal temperature and 100 rpm mixing raise. The resulting blend had
a Tg of
44°C with no crystalline melting point. A compression molded film of
the blend was
transparent and had a water contact angle of 42. Fiber was melt spun at
190°C with a
2 0 plunger speed of 0.3 inch/rninute (8 mm/minute) and .a take-up speed of 17
00 rpm (335
m/minute}. Additional blends with 20 and 25% PEO 4,000,000 were prepared and
the
results are included in Table Ill.
Example 13 - PHAE Blend With 3.7 Weight Percent EPE-30 yMn 5800)
PHAE (73.4 g) and EPE-30 (2.8 g, Aldrich Chemical Company, Tm
39°C)
2 5 were melt blended in a Haake torque rheometer for 2t? minutes at
180°C isothemtal
metal temperature and 100 rpm mixing rate. The resulting blend had a Tg of
69°C with
no crystalline melting point. A compression molded film of the blend had a
pearlescent,
semi-transparent appearance and had a water contact angle of 24. Fiber was
melt spun
at 200°C with a plunger speed of 0.3 inch/minute and a take-up speed of
1780 rpm (543
3 0 m/minute). The denier of the fiber produced was 8g. .A small hand sample
of fabric was
made from the fiber as follows: A portion of the fiber (1.4 g) was cut into 2
inch staple
and carded to make a web. The web was folded in half and then run through a
Beloit
Wheeler Mode1700 Lab Calendar Roll. The calender rolls were set at
210°F and 1000
psi which gave a well bonded fabric. A sample of pure PHAE fiber (1.4 g) was
made into
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WO 00/32854 ~ 8 PCT/US99/28A62
fabric using a similar procedure. The ability of the fabrics to wick water was
then tested
by immersing one end of a small strip (19 by 81 mm) of each fabric into
deionized water
and measuring the time required for the water to advance up the fabric strip
to a line
drawn 25 mm from the surface of the water. The PH~4E blend with EPE-30 (Mn
5800)
wicked water to the line in 2.5 minutes whereas the pure PHAE fabric showed no
wicking
of water at all. The fabrics were redried and the wickiing test was repeated 3
times. The
same results were observed each time - the fabric made with the EPE-30 blend
wicked
water and the pure PHAE fabric did not.
Example 14 - PHAE blend with 5 Weeeee~ht Percent EPE-80 {Mn 8400
PHAE (57.0 g) and EPE-80 (3.0 g, Aldrich Chemical Co., Tm 58°C)
were
melt blended in a Haake torque rheometer for 20 minutes at 180°C
isothermal metal
temperature and 100 rpm mixing rate. The resulting blend toad a Tg of
64°C with no
crystalline melting point. A compression molded film of the blend was
transparent and
had a water contact angle of 56. Fiber was melt spun at 200°C with a
plunger speed of
0.3 inch/minute and a take-up speed of 850 rpm (259 m/minute). The denier of
the fiber
produced was 274g.
Blends of PHAE with other EPE block copolymers, including EPE-30
(Mn 4400); EPE-40 (Mn 2,900); and EPE-50 (Mn 1,900), were also prepared using
procedures analogous to those described above. The results for these blends
are listed
2 0 in Tabfe IV.
Example 15 - PHAE blend with 5 Weiaht Percent Po~yoropvlene glycol), (Aldrich.
Mn
3500
PHAE (64.9 g) and polypropylene glycol) (3.4 g} were melt blended in a
Haake torque rheometer for 40 minutes at i50°C to 1130°C
isothermal metal temperature
and 30 to 100 rpm mixing rate. The initial blend appeared to be two-phase and
mixing
was very poor. Temperature and mixing rate were adjusted until good mixing was
obtained. The resulting blend had a Tg of 76°C. A compression molded
film of the blend
was opaque.
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Table III
PHAE Blends with Polyoxyethylene (PEG or PEO)
Contact angle
PHAE blend Tg (pH7 buffer) Comment
com osition a C b c
ure PHAE 78 89 t 5
5% PEG 10,000 64 68 t 4 miscible
10% PEG 10,000 53 67 t 3 "
25% PEG 10,00_0 20 23 t 5 "
5% PEO 100,000 66 68 t 6 miscible
10% PEO 100,000 54 64 t 4 "
25% PEO 100,000 21 25 t 8 "
5% PEO 4,000,00067 65 ~ 4 miscible
10% PEO 4,000,00055 67 t 3 "
15% PEO 4,000,00044 42 t 6 "
20% PEO 4,000,00037 18 ~ 4 "
25% PEO 4,000,00021 17 t3 "
a) Weight percent of additive given with the balance being PHAE.
b) Contact angle measurement for drops of pH 7 buffer solution applied to the
surface of a compression molded film. Value reported is the average of
results for 15 drops.
c) Samples were classified as miscible if the Tg satisfied the Fox equation
and
if films of the blends were transparent.
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Table IV
PHAE blends with EPE Block. Copolymers
Contact ---_
angle
(pH7
PHAE blend Tg, buffer) Comment
com osition a C b c
Pure PHAE 78 89 t Fiber made at high line speed:
5
denier = 7,
Fabric sample does not wick
water
3.7% EPE-30 (Mn 69 24 t Immiscible blend;
2
5,800) Fiber made at high speed:
diameter
= 30p.m;
Fabric sample exhibits wicking
of
water
2% EPE-30 Mn 4,40078 46 ~ Immiscible blend
5
_
4% EPE-30 Mn 4,40076 37 t
2
2% EPE-40 Mn 2,90075 31 ~ Immiscibie blend
4
4% EPE-40 Mn 2,90073 24 t
3
2% EPE-50 Mn 1,90073 73 t Miscible blend
3
_
5% EPE-50 Mn 1,90065 34 t
5
5% EPE-80 (Mn 8,400)64 56 t Miscible blend;
4
Fiber made at medium s eed
10% EPE-80 (Mn 55 56 t
3
8,400
a) Weight percent of additive given with the balance being PHAE.
b) Contact angle measurement for drops of pH 7 buffer solution applied to the
surface
of a compression molded film. Value reported is the average of results for 15
drops.
c) Samples were classified as miscible if the Tg satisfied the Fox equation
and if films
of the blends were transparent.
