Note: Descriptions are shown in the official language in which they were submitted.
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TITLE
ELASTOMER FIBERS AND METHODS OF MAKING AND USING THEREOF
BACKGROUND OF THE INVENTION
[0001] The
invention relates to a fiber excellent in cool contact feeling which is
excellent in hand and skin touch and capable of preventing unpleasant feeling
in the
wet state while also having excellent elasticity. The invention also relates
to fabric,
clothing, and underwear excellent in cool contact feeling and obtainable by
using
said fiber as well as the methods of making the fibers and articles thereof.
[0002] There is a
continuing, never-ending desire for more comfortable feeling
articles and garments, particularly in the areas of underwear and sports
and/or
exercise-related apparel. Users and/or wearers of such articles and garments
want
them to be as comfortable and refreshing feeling as possible, including after
prolonged periods of use and adverse conditions. The fibers used to make such
items, specifically their composition, can have a significant impact on the
performance of the items in these areas.
[0003] There is
also a desire for such fibers, in addition to being more
comfortable, to retain or even increase their elasticity.
SUMMARY OF THE INVENTION
[0004] The present
invention provides an elastic cooling fiber with a Tg of no
more than 22 degrees C and more specifically a fiber prepared from a
composition
comprising the reaction product of: (i) a hydroxyl terminated intermediate,
comprising a polyester, a polyether, a polycarbonate or a combination thereof,
wherein the intermediate has a Tg of no more than 22 degrees C; (ii) a
diisocyanate: and (iii) a linear alkylene glycol chain extender.
[0005] The
invention provides a fabric that is made from the fibers described
herein, which in some embodiments are mixed with other fibers. The invention
provides an article that is made from the fabric described here.
[0006] The
invention provides a method of providing a cooling effect in an
article that comes into close proximity with, in some embodiments even direct
contact with, human skin, including the steps of: (1) preparing a fabric
comprising
the fibers described herein; (2) preparing an article that comprises said
fabric; (3)
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bringing said article into close proximity with, in some embodiments even
direct
contact with, human skin.
[0006a] In accordance with one aspect there is provided a fiber prepared
from a
composition comprising the reaction product of:
(i) a hydroxyl terminated intermediate, comprising a polyester, a
polyether,
a polycarbonate or a combination thereof, wherein the intermediate has a Tg of
no
more than 22 degrees C;
(ii) a diisocyanate; and
(iii) a chain extender comprising a linear alkylene glycol,
wherein the Tg of the composition from which the fiber is prepared is no more
than 22 degrees C.
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[0007] The invention provides a method of making a fiber including the
steps of:
(1) preparing an elastomer resin in an internal mixing device wherein said
elastomer
resin is prepared by reacting: (i) a hydroxyl terminated intermediate,
comprising a
polyester, a polyether, a polycarbonate or a combination thereof, wherein the
intermediate has a Tg of no more than 22 degrees C; (ii) a diisocyanate; and
(iii) a
linear alkylene glycol chain extender; and (2) melt-spinning said elastomer
resin into a
monofilament or multifilament fiber.
[0008] The invention provides a method of making a fabric including the
steps of:
(1) preparing an elastomer resin in an internal mixing device wherein said
elastomer
resin is prepared by reacting: (i) a hydroxyl terminated intermediate,
comprising a
polyester, a polyether, a polycarbonate or a combination thereof, wherein the
intermediate has a Tg of no more than 22 degrees C; (ii) a diisocyanate; and
(iii) a
linear alkylene glycol chain extender; (2) melt-spinning said elastomer resin
into a
fiber, in some embodiments a monofilament or multifilament fiber; and (3)
processing
said fiber, optionally in combination with one or more other fibers, into a
fabric.
DETAILED DESCRIPTION OF THE INVENTION
[0009] Various features and embodiments of the invention will be described
below
by way of non-limiting illustration.
The Cooling Effect
[0010] The invention provides a fiber excellent in cool contact feeling and
also
excellent in elasticity. While this cooling effect is generally observed in
fabrics and/or
articles made from the fiber, it is believed that the cooling effect is due to
the
properties of the fiber and so not dependent on the type and/or construction
of the
fabric and/or article involved, though these parameters may of course have a
relative
impact on the observed cooling effect. In other words, it is believed that the
cooling
effect is provided by the fiber, and more specifically, fibers having specific
properties
and/or chemical compositions. In this application, we often note that the
fiber can give
a cooling contact feeling when in contact with the skin, or even close to
human skin,
say on top of a layer or even two layers of clothing
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between the fiber of the invention and the human skin. In some embodiments,
the
fiber is in direct contact with human skin. It is understood that the
evaluation of the
cooling effect may be done with fibers themselves, fabrics made from such
fibers,
any article made from such fibers and/or fabrics, or various combinations
thereof.
[0011] The key factors considered responsible for the cooling effect
provided by
the invention are described below, primarily in the fiber section.
The Fibers
[0012] The invention provides a fiber excellent in cool contact feeling and
also
excellent in elasticity. The fiber can give a cooling contact feeling when in
contact
with the skin. The effect can be strong enough to be sensed in a sensory test.
[0013] The fiber may include a thermoplastic elastomer and may also include
inorganic fillers, however, in certain embodiments; the composition is free of
any
inorganic filler.
[0014] The fibers of the invention may have a Tg of no more than 22 degrees
C
and are, as well as article made from them, exceptionally elastic and are also
excellent in providing a cool contact feeling when using the fiber for
clothing.
[0015] "Elastic" and "Elasticity" as used herein means that a fiber will
recover at
least about 50 percent of its stretched length after the first pull and after
the fourth
to 100% strain (doubled the length). Elasticity can also be described by the
"permanent set" of the fiber. "Permanent Set" is the converse of elasticity. A
fiber
is stretched to a certain point, in some embodiments 50% of the fiber's known
percent elongation at break, and subsequently released to the original
position
before stretch, and then stretched again. The point at which the fiber begins
to pull
a load is designated as the percent permanent set. "Elastic materials" are
also
referred to in the art as "elastomers" and "elastomeric".
[0016] The fibers of the present invention can provide this balance of
benefits
while also avoiding any sticky or inferior skin touch feelings, in the wet
state owing
to sweat and the like and therefore, which often leads to unpleasant feelings
for the
wearer when the fiber is used in a garment. The fibers of this invention
balance all
of these factors and provide superior performance in any one or any
combination of
these factors.
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[0017] In some embodiments, the thermoplastic elastomer utilized in the
preparation of the fibers described herein is substantially free of, or even
free of, a
polyamide type elastomer and/or a polyester type elastomer. More specifically,
the
present invention may be free of polyether block amide copolymers, polyether
amide copolymers, and polyester amide copolymers, or any combination thereof.
More specifically, the compositions involved in the present invention may be
substantially free of, or even completely free of, Pebax (manufactured by
Arkema).
As used herein, the term polyamide elastomer, or polyamide block within an
elastomer, is considered in its chemical sense to be different and distinct
from a
polyurethane elastomer, or a urethane block within an elastomer. In some
embodiments, polyamide links and/or block refer to ¨N(R)-C(0)-R- units and/or
linkages in the elastomer while polyurethane links and/or blocks refer to
¨N(R)-
C(0)-0-R- units and/or linkages in the elastomer.
[0018] In other embodiments, the thermoplastic elastomer utilized in the
preparation of the fibers described herein may include polyether block amide
copolymers, polyether amide copolymers, polyester amide copolymers, or any
combination thereof.
[0019] The polyester type elastomer is not particularly limited and
examples are
polyether ester copolymers and polyester ester copolymers. They may be used
alone
or two or more of them may be used in combination.
[0020] Commercialized polyester type elastomers among them are Grilux
(manufactured by Dainippon Ink and Chemicals, Inc.), Nouvelan (manufactured by
Teijin Chemicals Ltd.), Pelprene (manufactured by Toyobo Co., Ltd.), Hytrel
(manufactured by DuPont-Toray Co., Ltd.), and Primalloy (manufactured by
Mitsubishi Chemical Corporation).
[0021] The resin component contained in the fibers of the invention
provides the
excellent cool contact feeling of the invention, and so the thermoplastic
elastomers
alone may be used. Another benefit of the invention is that the fibers
described
here, when they contain only a thermoplastic elastomer as the resin component,
generally have no sticky feeling and so do not become difficult for spinning.
While
additional resins may be used in combination with the resin described here, it
is not
required to address any stickiness or unpleasant feeling that may otherwise
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accompany more conventional fibers. In some embodiments, an additional resin
is
used. While inorganic fillers resins may be used in combination with the resin
described here, it is not required to address any stickiness or unpleasant
feeling that
may otherwise accompany more conventional fibers.
[0022] In some embodiments, the fiber, and/or the resin from which it is
prepared is substantially free, to free of, any inorganic filler. When an
inorganic
filler is used, it is not particularly limited and examples may include
mineral type
pigments, such as calcium carbonate such as light calcium carbonate and heavy
calcium carbonate, barium carbonate, magnesium carbonate such as basic
magnesium carbonate, calcium sulfate, barium sulfate, titanium dioxide, iron
oxide,
tin oxide, titanium oxide, zinc oxide, magnesium oxide, ferrite powder, zinc
sulfide,
zinc carbonate, aluminum nitride, silicon nitride, Satin White, diatomaceous
earth
such as fired diatomaceous earth, calcium silicate, aluminum silicate,
magnesium
silicate, silica such as amorphous silica, amorphous synthesized silica, and
colloidal
silica, colloidal alumina, pseudo boehmite, aluminum hydroxide, magnesium
hydroxide, alumina, hydrated alumina, litopon, zeolite, hydrated halloysite,
clay,
hydrotalcite, aluminosilicate, talc, pyrophyllite, smectite such as saponite,
hectorite,
sauconite, stevensite, montmorillonite, beidellite and nontromite,
vermiculite, mica
such as phologopite, biotie, zinnwaldite, muscovite, paragonite, celadonite
and
glauconite, clinochlore, chamosite, nimite, pennantite, sudoite, donbasite,
clintonite, margarite, thulite, antigorite, lizardite, chrysotile, mesite,
cronstedite,
berthierine, greenalite, garnierite, kaolin such as kaolinite, dickite,
nacrite and
hallosite, delaminated kaolin, calcined kaolin, sepiolite, palygorskite,
imogolite,
allophane, hisingerite, penwithite, activated earth, bentonite, and sericite.
They may
be used alone or two or more kinds of them may be used in combination. In some
embodiments, the filler is titanium oxide, zinc oxide, barium oxide, silica,
or some
combination thereof. The form of the inorganic fillers is not particularly
limited
and examples are finite forms such as spherical, needle-like, plate type forms
and
the like, or nonfinite forms.
[0023] When present, the lower limit of the content of the inorganic filler
may
be 1%, 2% or 7% by weight, and the upper limit of that is 30% by weight.
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[0024] The fiber of the present invention may further comprise one or more
additional additives, and in some embodiments must contain at least one or
more
additional additives (beyond the thermoplastic elastomer and any inorganic
filler, of
present). In addition, the fiber may be twisted and/or covered with another
fiber for
improving the factors required for underwear such as skin touch within an
extent
that the aim of the invention is not inhibited. Such another fiber is not
particularly
limited and examples are polyamide type resins such as nylon 6 and nylon 12;
polyesters, cotton, and rayon.
[0025] In some embodiments, the fibers of the invention may be described by
a
qmax value. The lower limit of a qmax value of the fiber may be 0.20, 0.21 or
0.22
J/sec/cm2. If the qmax value is less than 0.20 J/sec/cm2, subjects may not
feel any
cool contact feeling even if a sensory test is performed. In other
embodiments, the
qmax value of the fiber may be less than 0.20 or even more than 0.22
J/sec/cm2.
[0026] In this description, the qmax value is defined as a peak value of
the heat
flow quantity of stored heat transferring to a sample at a lower temperature
in the
case a prescribed heat is stored in a heat plate with a specified surface area
and a
specified weight and immediately after the heat plate is brought into contact
with
the sample surface. It is supposed that the qmax value simulates the body heat
removed from the body by the sample when clothing is put on and it is supposed
that as the qmax value is higher, the body heat removed from the body is
higher and
the cool contact feeling is more excellent when the clothing is put on.
[0027] In some embodiments, the lower limit of the heat conductivity of the
fiber of the invention may be 1x10-3 degrees C/Wm2. The heat conductivity is
also
considered to be one of the important parameters to which the cool contact
feeling
is corresponding. If the heat conductivity is less than 1x10-3 degrees C./Wm2,
most
subjects may not feel any cool contact feeling even if a sensory test is
performed.
[0028] In this description, the heat conductivity can be calculated by
measuring
the heat loss speed after a heat plate is layered on a sample put on a sample
stand
and the temperature of the heat plate is stabilized at a prescribed
temperature and
performing calculation by the following formula (2).
Heat conductivity(W/cm/degrees C.)=WD/A/AT (2)
Where: W: heat flow quantity (J/sec)
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D: thickness of a sample (cm)
A: heat plate surface area (cm2)
AT: temperature difference ( C) between the sample stand and
the heat plate
[0029] The fiber of the invention may be used in the form of a composite
fiber
comprising the thermoplastic elastomer and another resin and may have a core-
sheath structure and comprises a core part containing a dyeable resin and a
sheath
part containing a thermoplastic elastomer resin, a thickness of the sheath
part being
20 micrometers or thinner (hereinafter referred to as a core-sheath type
composite
yarn in some cases). The fiber excellent in cool contact feeling of the
invention can
be a fiber having the core-sheath structure having good dyeability, keeping
excellent properties of the thermoplastic elastomer such as cool contact
feeling by
using such a dyeable resin for the core part and the thermoplastic elastomer
having
the cool contact feeling and excellent in the flexibility for the sheath part.
[0030] The faun of the core-sheath type composite yarn is not particularly
limited and the cross-sectional shape formed in the case the fiber is cut
perpendicularly to the longitudinal direction of the fiber may be true round,
elliptical and the like. Also, the fiber may have a concentric core-sheath
type
structure in which the core part and sheath part are formed concentrically or
an
eccentric core-sheath type structure in which the core part and sheath part
are
formed eccentrically. Also, the fiber may have a structure in which multiple
core
parts exist in the case the fiber is cut perpendicularly to the longitudinal
direction of
the fiber.
[0031] In some embodiments, the fiber of the invention is an elastic
cooling
fiber that has a Tg of no more than 22 C.
[0032] In some of these embodiments, the Tg of the fiber may be no more
than
22, 15, 10, 0, -10, -20, -30 or even -40 degrees C. These Tg limits may apply
to the
fiber itself, the composition from which the fiber is made (before the
composition is
spun or otherwise processed into fibers), the intermediate from which the
composition is prepared, or any combination thereof.
[0033] In some of these embodiments, the percent elongation achieved by the
fiber may be from 200% to 300%.
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[0034] The fibers
of the invention are prepared from a composition that includes
a reaction product of (i) a hydroxyl terminated intermediate, (ii) a
diisocyanate and
(iii) a linear alkylene glycol chain extender. The hydroxyl terminated
intermediate
may include a polyester, a polyether, a polycarbonate or a combination
thereof,
wherein the intermediate has a Tg of no more than 22 degrees C. In some
embodiments, the intermediate is derived from polyethylene glycol. The
diisocyanate may include diphenyl methane-4,4'-diisocyanate. The linear
alkylene
glycol may include 1,6-butanediol and similar materials. In some embodiments,
the
hydroxyl terminated intermediate used in the invention is substantially free
of, or
even free of, polyether block amide copolymers and/or units of the same.
[0035] In still
other embodiments, the fibers of the invention are prepared from
a composition itself prepared from (i) an intermediate that includes and/or is
derived from polyethylene glycol or an adipate derived from one or more
alkylene
diols and adipic acid, (ii) a diisocyanate that includes methylene diphenyl
diisocyanate; and (iii) a linear alkylene glycol chain extender that may
include 1,4-
butanediol, 1,6-hexanediol, or a combination thereof. In some of
these
embodiments, the chain extender includes 1,4-butanediol, and the adipate is
prepared from 1,4-butanediol, 1,6-hexanediol, or a combination thereof. In
some of
these embodiments, the adipate is prepared from a mixture of 1,4-butanediol
and
1,6-hexanediol. Further, in some of these embodiments, the compositions used
to
prepare the fiber are: from 40 to 80, 40 to 70, 50 to 60, or even 55 to 58 or
56 to 57
percent by weight intermediate; from 20 to 50, 30 to 40, 30 to 35, or even 31
to 34
or 32 to 33 percent by weight diisocyanate; and from 4 to 25, 5 to 20, 5 to
15, or
even from 8 to 11, or 9 to 10 percent by weight chain extender. The fibers of
the
invention may be made from compositions that contain the material described
above
and which may also contain one or more polymer additives, including any of the
additional additives described below. In some embodiments, the compositions
may
further include an antioxidant, a lubricant and/or processing aid, and may
even have
a metal containing catalyst.
[0036] In some
embodiments, the fibers of the invention are prepared from a
composition itself prepared from (i) an intermediate that includes and/or is
derived
from polyethylene glycol, (ii) a diisocyanate that includes methylene diphenyl
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diisocyanate; and (iii) a linear alkylene glycol chain extender that includes
1,4-
butanediol, 1,6-hexanediol, or a combination thereof. In some of
these
embodiments, the chain extender includes 1,4-butanediol. Further, in some of
these
embodiments, the compositions used to prepare the fiber are: from 40 to 80, 40
to
70, 40 to 60, or even 46 to 49 or 47 to 48 percent by weight intermediate;
from 20
to 50, 30 to 50, 35 to 45, or even 40 to 43 or 41 to 42 percent by weight
diisocyanate; and from 4 to 25, 5 to 20, 5 to 15, or even from 9 to 12, or 10
to 11
percent by weight chain extender.
[0037] In
addition, the composition from which the fiber is prepared may be a
polymer alloy that includes: (a) a multiphase copolymer prepared by reacting a
polymer and/or copolymer segment with at least one other polymer and/or
copolymer segment; (b) a polymer blend prepared mixing a polymer and/or
copolymer with at least one other polymer and/or copolymer, wherein each of
the
polymers and/or copolymers is compatible and/or miscible in one another; or
(c)
combinations thereof. The polymer alloy may be derived from the reaction of:
(i)(a) a polyol; (i)(b) a polyester intermediate itself derived from a polyol
and a
dicarboxylic acid; (ii) at least one diisocyanate; and (iii) at least one
chain extender.
[0038] In general,
the TPU polymer type used in this invention can be any
conventional TPU polymer that is known to the art and in the literature as
long as it
(meaning the fiber itself, the composition from which the fiber is made,
and/or the
intermediate used to prepare the composition) exhibits the Tg, percent
elongation,
and/or elasticity described above. While not wishing to be bound by theory,
Applicants consider that compositions which meet these requirements are
expected
to provide the same cooling effect demonstrated by the specific examples
included
in this application, or in the alternative, when at least one or more of the
additional
parameters described herein is met.
[0039] Suitable TPU polymers are generally prepared by reacting a
polyisocyanate with an intermediate such as a hydroxyl terminated polyester, a
hydroxyl terminated polyether, a hydroxyl terminated polycarbonate or mixtures
thereof, with one or more chain extenders, all of which are well known to
those
skilled in the art.
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[0040] The
hydroxyl terminated polyester intermediate is generally a linear
polyester having a number average molecular weight (Mn) of from about 500 to
about 10,000, from about 700 to about 5,000, or from about 700 to about 4,000,
an
acid number generally less than 1.3 and preferably less than 0.8. The
molecular
weight is determined by assay of the terminal functional groups and is related
to the
number average molecular weight. The polymers are produced by (1) an
esterification reaction of one or more glycols with one or more dicarboxylic
acids
or anhydrides or (2) by transesterification reaction, i.e., the reaction of
one or more
glycols with esters of dicarboxylic acids. Mole ratios generally in excess of
more
than one mole of glycol to acid are preferred so as to obtain linear chains
having a
preponderance of terminal hydroxyl groups. Suitable polyester intermediates
also
include various lactones such as polycaprolactone typically made from 8-
caprolactone and a bi-functional initiator such as diethylene glycol. The
dicarboxylic acids of the desired polyester can be aliphatic, cycloaliphatic,
aromatic, or combinations thereof. Suitable dicarboxylic acids which may be
used
alone or in mixtures generally have a total of from 4 to 15 carbon atoms and
include: succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic,
dodecanedioic, isophthalic, terephthalic, cyclohexane dicarboxylic, and the
like.
Anhydrides of the above dicarboxylic acids such as phthalic anhydride,
tetrahydrophthalic anhydride, or the like, can also be used. Adipic acid is a
preferred acid. The glycols which are reacted to form a desirable polyester
intermediate can be aliphatic, aromatic, or combinations thereof, and have a
total of
from 2 to 12 carbon atoms, and include ethylene glycol, 1,2-propanediol, 1,3-
propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol,
2,2-
dimethy1-1,3-propanediol, 1,4-cyclohexanedimethanol, decamethylene glycol,
dodecamethylene glycol, and the like, 1,4-butanediol is a preferred glycol.
[0041] Hydroxyl
terminated polyether intermediates are polyether polyols
derived from a diol or polyol having a total of from 2 to 15 carbon atoms, in
some
embodiments an alkyl diol or glycol which is reacted with an ether (or an
epoxide)
which comprises an alkylene oxide group having from 2 to 6 carbon atoms,
typically ethylene oxide or propylene oxide or mixtures thereof. For example,
hydroxyl functional polyether can be produced by first reacting propylene
glycol
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with propylene oxide followed by subsequent reaction with ethylene oxide.
Primary
hydroxyl groups resulting from ethylene oxide are more reactive than secondary
hydroxyl groups and thus are preferred. Useful commercial polyether polyols
include
poly(ethylene glycol) comprising ethylene oxide reacted with ethylene glycol,
poly(propylene glycol) comprising propylene oxide reacted with propylene
glycol,
poly(tetramethylene glycol) comprising water reacted with tetrahydrofuran
(PTMEG).
PTMEG is the preferred polyether intermediate. Polyether polyols further
include
polyamide adducts of an alkylene oxide and can include, for example,
ethylenediamine
adduct comprising the reaction product of ethylenediamine and propylene oxide,
diethylenetriamine adduct comprising the reaction product of
diethylenetriamine with
propylene oxide, and similar polyamide type polyether polyols. Copolyethers
can also
be utilized in the current invention. Typical copolyethers include the
reaction product
of THF and ethylene oxide or THF and propylene oxide. These are available from
BASF as Poly THF B, a block copolymer, and poly THF R, a random copolymer. The
various polyether intermediates generally have a number average molecular
weight
(Mn) as determined by assay of the terminal functional groups which is an
average
molecular weight greater than about 700, such as from about 700 to about
10,000, from
about 1000 to about 5000, or from about 1000 to about 2500. A particular
desirable
polyether intermediate is a blend of two or more different molecular weight
polyethers,
such as a blend of 2000 Mõ and 1000 Mn PTMEG.
[0042] In some embodiments, the compositions of the present invention are
prepared from polyethleneglycol (PEG). In other embodiments, the intermediate
is a
polyester made from the reaction of adipic acid with a 50/50 blend of 1,4-
butanediol
and 1,6-hexanediol.
[0043] The polycarbonate-based polyurethane resin of this invention may be
prepared by reacting a diisocyanate with a blend of a hydroxyl terminated
polycarbonate and a chain extender. The hydroxyl terminated polycarbonate can
be
prepared by reacting a glycol with a carbonate.
[0044] U.S. Patent No. 4,131,731 is of hydroxyl terminated polycarbonates
and their
preparation. Such polycarbonates are linear and have terminal hydroxyl groups
with essential
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exclusion of other terminal groups. The essential reactants are glycols and
carbonates. Suitable glycols are selected from cycloaliphatic and aliphatic
diols
containing 4 to 40, and or even 4 to 12 carbon atoms, and from polyoxyalkylene
glycols containing 2 to 20 alkoxy groups per molecule with each alkoxy group
containing 2 to 4 carbon atoms. Diols suitable for use in the present
invention
include aliphatic diols containing 4 to 12 carbon atoms such as butanedio1-
1,4,
pentanedio1-1,4, neopentyl glycol, hexanedio1-1,6, 2,2,4-trimethylhexanedio1-
1,6,
decanedio1-1,10, hydrogenated dilinoleylglycol, hydrogenated dioleylglycol;
and
cycloaliphatic diols such as cyclohexanedio1-1,3, dimethylolcyclohexane-1,4,
cyclohexanedio1-1,4, dimethylolcyclohexane-1,3, 1,4-endo methylene-2-hydroxy-5-
hydroxymethyl cyclohexane, and polyalkylene glycols. The diols used in the
reaction may be a single diol or a mixture of diols depending on the
properties
desired in the finished product. Polycarbonate intermediates which are
hydroxyl
terminated are generally those known to the art and in the literature.
Suitable
carbonates are selected from alkylene carbonates composed of a 5 to 7 member
ring. Suitable carbonates for use herein include ethylene carbonate,
trimethylene
carbonate, tetramethylene carbonate, 1,2-propylene carbonate, 1,2-butylene
carbonate, 2,3-butylene carbonate, 1,2-ethylene carbonate, 1,3-pentylene
carbonate,
1,4-pentylene carbonate, 2,3-pentylene carbonate, and 2,4-pentylene carbonate.
[0045] Also,
suitable herein are dialkylcarbonates, cycloaliphatic carbonates,
and diarylcarbonates. The dialkylcarbonates can contain 2 to 5 carbon atoms in
each alkyl group and specific examples thereof are diethylcarbonate and
dipropylcarbonate. Cyclo
aliphatic carbonates, especially dicycloaliphatic
carbonates, can contain 4 to 7 carbon atoms in each cyclic structure, and
there can
be one or two of such structures. When one group is cycloaliphatic, the other
can
be either alkyl or aryl. On the other hand, if one group is aryl, the other
can be
alkyl or cycloaliphatic. Examples of suitable diarylcarbonates, which can
contain 6
to 20 carbon atoms in each aryl group, are diphenylcarbonate,
ditolylcarbonate, and
dinaphthylcarbonate.
[0046] The
reaction is carried out by reacting a glycol with a carbonate, for
example an alkylene carbonate in the molar range of 10:1 to 1:10, but
preferably
3:1 to 1:3 at a temperature of 100 C to 300 C and at a pressure in the range
of 0.1
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to 300 mm of mercury in the presence or absence of an ester interchange
catalyst,
and may also be carried out while removing low boiling glycols by
distillation.
[0047] More
specifically, the hydroxyl terminated polycarbonates are prepared
in two stages. In the first stage, a glycol is reacted with an alkylene
carbonate to
form a low molecular weight hydroxyl terminated polycarbonate. The lower
boiling point glycol is removed by distillation at 100 C to 300 C, preferably
at
150 C to 250 C, under a reduced pressure of 10 to 30 mm Hg, preferably 50 to
200
mm Hg. A fractionating column may be used to separate the by-product glycol
from the reaction mixture. The by-product glycol can be taken off the top of
the
column and the unreacted alkylene carbonate and glycol reactant may be
returned to
the reaction vessel as reflux. A current of inert gas or an inert solvent can
be used
to facilitate removal of by-product glycol as it is formed. When amount of by-
product glycol obtained indicates that degree of polymerization of the
hydroxyl
terminated polycarbonate is in the range of 2 to 10, the pressure is gradually
reduced to 0.1 to 10 mm Hg and the unreacted glycol and alkylene carbonate are
removed. This marks the beginning of the second stage of reaction during which
the low molecular weight hydroxyl terminated polycarbonate is reacted by
distilling
off glycol as it is formed at 100 C to 300 C, preferably 150 C to 250 C and at
a
pressure of 0.1 to 10 mm Hg until the desired molecular weight of the hydroxyl
terminated polycarbonate is attained. Molecular weight (Mn) of the hydroxyl
terminated polycarbonates can vary from about 500 to about 10,000 but in a
preferred embodiment, it will be in the range of 500 to 2500.
[0048] The second
necessary ingredient to make the TPU polymer of this
invention is a polyisocyanate. The polyisocyanates of the present invention
generally have the formula R(NCO) õ where n is generally from 2 to 4 with 2
being
highly preferred inasmuch as the composition is a thermoplastic. Thus,
polyisocyanates having a functionality of 3 or 4 are utilized in very small
amounts,
for example, less than 5% and desirably less than 2% by weight based upon the
total weight of all polyisocyanates, inasmuch as they cause crosslinking. R
can be
aromatic, cycloaliphatic, and aliphatic, or combinations thereof generally
having a
total of from 2 to about 20 carbon atoms. Examples of suitable aromatic
diisocyanates include diphenyl methane-4, 4'-diisocyanate (MDI), H12 MDI, m-
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xylylene diisocyanate (XDI), m-tetramethyl xylylene diisocyanate (TMXDI),
phenylene-1, 4-diisocyanate (PPDI), 1,5-naphthalene diisocyanate (NDI), and
diphenylmethane-3, 3'-dimethoxy-4, 4'-diisocyanate (TODI). Examples of
suitable
aliphatic diisocyanates include isophorone diisocyanate (IPDI), 1,4-cyclohexyl
diisocyanate (CHDI), hexamethylene diisocyanate (HDI), 1,6-diisocyanato-
2,2,4,4-
tetramethyl hexane (TMDI), 1,10-decane diisocyanate, and trans-
dicyclohexylmethane diisocyanate (HMDI). A highly preferred diisocyanate is
MDI containing less than about 3% by weight of ortho-para (2,4) isomer.
[0049] The third necessary ingredient to make the TPU polymer of this
invention is the chain extender. Suitable chain extenders are lower aliphatic
or
short chain glycols having from about 2 to about 10 carbon atoms and include
for
instance ethylene glycol, diethylene glycol, propylene glycol, dipropylene
glycol,
tripropylene glycol, triethyl en e glycol, cis-trans-isomers of cyclohexyl
dimethylol,
neopentyl glycol, 1,4-butanediol, 1,6-hexandiol, 1,3-butanediol, and 1,5-
pentanediol. The present invention requires a linear alkylene glycol chain
extender,
but in some embodiments additional chain extenders may be used in combination
with the linear alkylene glycol chain extender. In such embodiments, aromatic
glycols can be used as the chain extender. Benzene glycol (HQEE) and xylylene
glycols are suitable chain extenders for use in making the TPU of this
invention.
Xylylene glycol is a mixture of 1,4-di(hydroxymethyl) benzene and 1,2-
di(hydroxymethyl) benzene. Benzene glycol is the preferred aromatic chain
extender and specifically includes hydroquinone, bis(beta-hydroxyethyl) ether
also
known as 1,4-di(2-hydroxyethoxy) benzene; resorcinol, bis(beta-hydroxyethyl)
ether also known as 1,3-di(2-hydroxyethyl) benzene; catechol, i.e., bis(beta-
hydroxyethyl) ether also known as 1,2-di(2-hydroxyethoxy) benzene; and
combinations thereof. The preferred chain extender is 1,4-butanediol.
[0050] The above three necessary ingredients (hydroxyl terminated
intermediate,
polyisocyanate, and chain extender) may be reacted in the presence of a
catalyst.
[0051] Generally, any conventional catalyst can be utilized to react the
diisocyanate with the hydroxyl terminated intermediate or the chain extender
and
the same is well known to the art and to the literature. Examples of suitable
catalysts include the various oragno compounds, such as carbonates, of bismuth
or
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tin wherein the alkyl portion has from 1 to about 20 carbon atoms with
specific
examples including bismuth octoate, bismuth laurate, and the like. Preferred
catalysts include the various tin catalysts such as stannous octoate,
dibutyltin
dioctoate, dibutyltin dilaurate, and the like. The amount of such catalyst is
generally small such as from about 20 to about 200 parts per million based
upon the
total weight of the polyurethane forming monomers.
[0052] The TPU polymers of this invention can be made by any of the
conventional polymerization methods well known in the art and literature.
[0053] In some embodiments, the polyurethanes of the invention are made via
a
"one shot" process wherein all the components are added together
simultaneously or
substantially simultaneously to a heated extruder and reacted to form the
polyurethane. The equivalent ratio of the diisocyanate to the total
equivalents of
the hydroxyl terminated intermediate and the diol chain extender is generally
from
about 0.95 to about 1.10, desirably from about 0.97 to about 1.03, and
preferably
from about 0.97 to about 1.00. In some embodiments, the Shore A hardness of
the
TPU formed will typically be from less than 80A, 85A or even 95A. Reaction
temperatures utilizing urethane catalyst may be from about 175 C to about 245
C or
even from about 180 C to about 220 C. The molecular weight (Mw) of the
thermoplastic polyurethane may be from about 100,000 to about 800,000 Daltons
or
from about 150,000 to about 400,000 or even from about 150,000 to about
350,000
as measured by GPC relative to polystyrene standards.
[0054] Useful additives can be utilized in suitable amounts in the TPU's
described herein, where such additives may be added either before, during, or
after
the preparation of the TPU. Such additional additives include opacifying
pigments,
colorants, mineral fillers, stabilizers, lubricants, UV absorbers, processing
aids, and
other additives as desired. Useful opacifying pigments include titanium
dioxide,
zinc oxide, and titanate yellow, while useful tinting pigments include carbon
black,
yellow oxides, brown oxides, raw and burnt sienna or umber, chromium oxide
green, cadmium pigments, chromium pigments, and other mixed metal oxide and
organic pigments. Useful fillers include diatomaceous earth (superfloss) clay,
silica, talc, mica, wallastonitc, barium sulfate, and calcium carbonate. If
desired,
useful stabilizers such as antioxidants can be used and include phenolic
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antioxidants, while useful photostabilizers include organic phosphates, and
organotin thiolates (mercaptides). Useful antioxidants also include
stearically
hindered phenolic antioxidants. Useful lubricants include metal stearates,
paraffin
oils and amide waxes, for example, alkylene bisstearamides such as N,N'
ethylene
bisstearamide and esters of nonanic esters. Useful UV absorbers include 2-(2'-
hydroxyphenol) benzotriazoles and 2-hydroxybenzophenones. Typical TPU flame
retardants can also be added.
[0055] Plasticizer additives can also be utilized advantageously to reduce
hardness without affecting properties, if they are used in small amounts. In
some
embodiments, no plasticizers are used.
[0056] In some embodiments, the cooling effect of the fiber may be
expressed in
terms of effective cooling power. While there are various means of measuring
the
cooling effect provided by the invention, this application includes details on
two
approaches to measure this effect. The first looks at the cooling effect
provided by
fabrics made from the fibers described herein, where the fabric and the area
of
"skin" in contact with the fabric, in this case a test surface taking the
place of a
person's skin, are both and where a constant wind is blowing across the
fabric.
While the specific conditions involved are considered to be important
primarily for
the purposes of comparing results, these type of evaluations can be of course
be
done at various ambient temperatures, levels of humidity, wind speed, starting
temperature of the "skin", whether the "skin" heat source is left on or
removed, and
various other variables. In addition, this parameter is of course measured
with
respect to a specific area. Another approach follows the basic test
methodology
described above but adds the additional variable of sweat, various rates of
moisture
release from the "skin" over the course of the test. Using these types of
tests, one
can measure the amount of energy it takes to maintain the temperature of the
"skin"
under various conditions, or in the alternative, measure the rate at which the
"skin"
temperature drops if no heat source is applied, thus giving an indication of
the
cooling power of the fabric involved. Specific test conditions and results are
provided in the examples section of this specification. It is important to
note that
regardless of the testing approach used, and the specific conditions selected,
all
testing conducted to date has shown that fabrics made from the fibers
described
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herein exhibit significantly higher cooling powers and allow for faster and
greater
temperature drops than the comparative materials also tested.
[0057] In some embodiments, the fibers of the present invention, when
evaluated by the methods described above, specifically where the fabric is
placed
on the test skin surface, with an active heat source working to maintain skin
surface
temperature, 30% relative humidity, a 3 m/s wind speed, and an ambient
temperature of 15 degrees C, provide a cooling power of at least 31 watts for
a test
are of 629 cm2, or stated differently a cooling power of at least 49 watts per
square
meter. That is, at least 49 watts of power per square meter of area is
required to
maintain skin temperature, giving an indication of the cooling effect the
fabric
would provide to a person where the fabric against their skin, compared to
other
materials (nylon and polyester, for example, could not break the 31 watt limit
under
the exact same test conditions). This cooling power may also be at least 34
watts
for a test area of 629 cm2, at least 55 watts per square meter, where the
fiber is a
monofilament and is not semi-dull. The same limits apply to testing conducted
at
50% relative humidity and 3 m/s wind speed, as well as at 5 m/s wind speed at
50%
relative humidity.
[0058] In similar embodiments, the fiber of the present invention when
evaluated by the methods described above, specifically where the fabric is
placed
on the test skin surface, with an active heat source working to maintain skin
surface
temperature, 50% relative humidity, a 0.3 m/s wind speed, and an ambient
temperature of 15 degrees C, provide a cooling power of at least 13 or 14
watts for
a test area of 629 cm2, at least 21 or 22 watts per square meter.
[0059] A method of producing the fiber excellent in cool contact feeling of
the
invention is not particularly limited and conventionally known methods such as
a
method of producing it by producing resin pellets containing the thermoplastic
elastomer and the inorganic filler and melting and spinning, using the
obtained resin
pellets, may be employed.
[0060] The core-sheath type composite yarn may also be produced by, for
example, loading resin pellets containing the dyeable resin, the thermoplastic
elastomer, and the inorganic filler into a composite spinning apparatus and
melting
and spinning them.
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[0061] The invention provides a method of making a fiber that includes the
steps
of: (I) preparing an elastomer resin in an internal mixing device. The
elastomer
resin is prepared by reacting: (i) a hydroxyl terminated intermediate, (ii) a
diisocyanate and (iii) a linear alkylene glycol chain extender. The
intermediate may
be a polyester, a polyether, a polycarbonate or a combination thereof, wherein
the
intermediate has a Tg of no more than 22 degrees C. The second step, (II) is
melt-
spinning the elastomer resin into a fiber, for example, a monofilament or
multifilament fiber. In some embodiments, the fiber is a monofilament fiber.
All
of the various features and embodiments discussed above with regards to the
fiber
and the composition used to prepare it apply here as well.
The Fabric
[0062] The fiber of the invention may be used in form of a fabric such as a
knit,
a textile, and a bonded textile. The resulting fabric is excellent in cool
contact
feeling while also possessing the excellent elasticity of the fiber.
[0063] The fabric excellent in cool contact feeling of the invention may
solely
comprise the fiber excellent in cool contact feeling of the invention and in
other
embodiments may comprise the fiber and another fiber twisted together for
improving the factors required for specific applications. For example, in
garments
that come into direct contact with skin. Such optional co-fibers are not
particularly
limited and examples include polyamide type resins such as nylon 6 and nylon
12,
polyesters, cotton, and rayon.
[0064] The invention includes fabrics made from any of the fibers described
herein, including woven fabric, non-woven fabric, knitted fabric, and
combinations
thereof. In some embodiments, the fabrics of the invention are woven fabrics.
In
other embodiments, the fabrics of the invention are non-woven fabrics. In
still
other embodiments, the fabrics of the invention are knitted fabrics. In
addition, the
invention includes fabrics that further contain one or more additional fibers,
other
than the fibers of the invention. The fabric may be from 10 to 80 percent by
weight
of these additional fibers, or no more than 90%, 80%, 70%, 60%, 50%, 40%, 30%,
20%, or 10% of these additional fibers. In some embodiments, no additional
fibers
are present. In embodiments where there are one or more additional fibers
present
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in the fabric, these additional fibers may be nylon fibers, polyester fibers,
rayon
fibers, acrylic fibers, and combinations thereof.
[0065] The invention also includes a method of making a fabric that
includes the
steps of (I) preparing an elastomer resin in an internal mixing device wherein
said
elastomer resin is prepared as described above. The process may optionally
include
the addition of a cross-linking agent, such as the reaction product of a
polyalkylene
ether glycol or triol and a diisocyanate. Step (II) is melt-spinning said
elastomer
resin into a fiber, for example, a monofilament or multifilament fiber. In
some
embodiments, the fiber, or rather the polymer making up the fiber, has a
weight
average molecular weight of at least 700,000. Step (III) is processing the
fiber,
optionally in combination with one or more other fibers, into a fabric.
[0066] An additional benefit of the invention is the improved mold-ability
of
fabrics that contain the fibers described herein. When utilized at suitable
levels
within the fabric, the fabric of the invention can be successful molded at
lower
temperatures and/or in less time, thus improving the ability to protect the
fabric,
dye, etc of the fabric which may be damaged by the high temperatures and/or
low
exposure time required by more conventional fabrics in order to successfully
mold
them. In some embodiments, the fabrics of the invention may be molded at
temperatures of no more than 150 or even 140 degrees C, and/or where the
molding
is complete in less than 20, 15 or even 10 seconds. In some embodiments, a
minimum level of the fibers of the invention must be present in the fabric for
it to
provide these benefits. In some embodiments, this lower limit is 40%, 50%, 60%
or
even 80% where the percentage represent the percent by weight of the fibers in
the
fabric that must be the fibers of the present invention. However, it is also
understood that a much smaller amount of the fibers of the invention in a
fabric will
improve that fabric's mold-ability. It is noted that SpandexTM and similar
materials
are not moldable at low temperatures, and that fibers of these materials are
not even
knittable into fabrics unless a positive feeder is used, an expensive piece of
equipment required due to the over-elasticity of SpandexTM fibers.
The Articles
[0067] The fiber excellent in cool contact feeling of the invention and the
fabric
excellent in cool contact feeling of the invention may be used for producing
articles
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including clothing. In the case of articles that come into contact with skin,
again
for example, clothing, the articles of the invention exhibit excellent
elasticity,
provide a cooling sensation to the wearer, and have no unpleasant and/or
sticky
feeling even at times of wetting.
[0068] Since the articles, and specifically the clothing, provide excellent
cool
contact feeling, it can cause sensation of cool feeling at the time of wearing
and
give refreshing feeling. Also, the present invention does not require the
addition of
the inorganic filler to make the clothing free from a sticky feeling at the
time of
wetting, as other fibers used in clothing with similar cooling effects may do.
Thus,
the present invention is extremely suitable for underwear.
[0069] The clothing excellent in cool contact feeling of the invention may
be
produced using the fiber excellent in cool contact feeling entirely and it is
particularly preferable to be clothing excellent in cool feeling comprising a
fabric
having a reversible structure and excellent in refreshing feeling, 30 to 70%
by
number of total loops comprising the fiber excellent in cool contact feeling,
the
loops comprising the fiber excellent in cool contact feeling being arranged in
a skin
contact side (hereinafter, also referred to as refreshing clothing).
[0070] With respect to the clothing comprising a fabric having a reversible
structure as clothing excellent in cool contact feeling of the invention, the
ratio of
the number of loops comprising the fiber excellent in cool contact feeling is
controlled within a prescribed range and such loops comprising the fiber
excellent
in cool contact feeling are arranged only in the skin contact side, so that
the
clothing can have an effect of preventing unpleasant feeling caused by much
sweating.
[0071] In recent years, various kinds of clothing having improved functions
as
underwear to be put on in an occasion of sweating in summer, in the case of
exercises, sports and the like, have been developed and proposed, and such
functional clothing is suggested, for example, clothing produced from
hydrophobic
fibers such as polyester. Also, a method of increasing the air permeability by
using
a hydrophilic fiber in combination with cotton and a method of increasing the
air
permeability by forming a mesh structure for a cloth or by forming a moss
knitting
of a derivative weave of a plain knitting and warp knitting, have been
investigated,
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and Japanese Kokai Publication 2003-155669 discloses a reformed cloth by
depositing a hydrophilic chemical substance on the surface of a hydrophobic
fiber
composing the cloth. However, in
the case of clothing comprising such
hydrophobic fibers, although the generated heat can efficiently be released,
it
causes unpleasant feeling due to wet feeling in the case the skin or the
clothing is
wetted because of sweating and at the same time the fabric tends to be stuck
to the
skin to cause the problem that the clothing restrains the movement.
[0072] On the
other hand, with respect to the refreshing clothing comprising the
fabric having a reversible structure, it can cause sensation of cool feeling
at the
time of wearing and give refreshing feeling and simultaneously it can prevent
unpleasant feeling due to wet feeling at the time of sweating and prevent
sticking of
the fabric to the skin due to deterioration of the separation from the skin by
controlling the ratio of the number of loops comprising the fiber excellent in
cool
contact feeling to be within a prescribed range. Also, the loops comprising
the fiber
excellent in cool contact feeling are arranged only in the skin side, so that
the fiber
excellent in cool contact feeling can be brought into direct contact with the
skin and
clothing with further improved refreshing feeling and cool contact feeling can
be
produced.
[0073] In the
refreshing articles and clothing of the invention, the lower limit of
the ratio of the loops of the fiber excellent in cool contact feeling may be
30% of
the total number of loops, and the upper limit may be 70% or even higher, such
as
75%, 80%, 90% or even 100% of the total number of loops. If it is less than
30%,
the effect to cause refreshing feeling and cool contact feeling may become
insufficient in some cases. The high level can be obtained with the present
invention without causing any unpleasant feeling due to wet feeling in the
case the
skin or the clothing is wetted because of sweating.
[0074] As noted
above, for the fiber and fabric, the refreshing article, for
example, the clothing, may contain the thermoplastic elastomer and an
inorganic
filler, but in other embodiments is substantially free of, to even free of,
any
inorganic filler.
[0075] In the
articles of the invention, for example, the clothing, the thickness of
the fabric is to be made as thin as possible, the fiber excellent in cool
contact
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feeling may be used in combination with another fiber. The lower limit of the
content of the thermoplastic elastomer in the fiber excellent in cool contact
feeling
may be 50% by weight. If it is less than 50% by weight, sufficient cool
contact
feeling may not be caused in some cases. In other embodiments, the content of
the
fiber of the invention is present in the fabric and articles is at least 15%,
25%, 35%,
45%, 55%, 65%, 75%, 85%, or even 95% by weight. While not wishing to be
bound by theory, it is believed that some minimum fiber content in the fabric
and/or
article in question must be the fiber of the invention for the cooling effect
to be
noticeable. This
minimum required content may vary across the various
formulations included in the present invention, but in some embodiments may be
fairly consistent across the various formulations. This minimum content may be
any of the percentages described above.
[0076] In some
embodiments, in the articles and/or clothing of the invention, the
loops comprising the fiber excellent in cool contact feeling are preferable to
be
arranged only in the skin side. Arrangement in such a manner makes the loops
comprising the fiber excellent in cool contact feeling have mainly contact
with the
skin and causes the cool contact feeling and refreshing feeling, and as
described
later, arrangement of loops comprising a hydrophobic fiber in the outside
improves
the diffusion and evaporating property of the heat and water emitted from the
skin.
[0077] In the
articles and/or clothing of the invention, the loops other than the
loops comprising the fiber excellent in cool contact feeling are preferably
the loops
comprising a hydrophobic fiber. Since the loops comprising the fiber excellent
in
cool contact feeling are arranged only in the skin side, the loops comprising
a
hydrophobic fiber are arranged mainly in the outside.
[0078] In this
description, the hydrophobic fiber means a chemical fiber having
a official water percentage of 5.0% or less. Practically, fibers comprising
polypropylenes (official water percentage: 0%), polyesters (0.4%), acrylic
resins
(2.0%), nylon (4.5%), and vinylon (5.0%) can be exemplified. They may be used
alone or two or more kinds of them may be used in combination. In this
connection, the official water percentage means water percentage at 20 degrees
C.
and 65% RH.
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[0079] The articles and/or clothing of the invention may contain natural
fibers
such as cotton and flax, and semi-synthesized fibers such as rayon and acetate
based
on the necessity besides the fiber excellent in cool contact feeling and the
hydrophobic fiber.
[0080] In some embodiments, the articles and/or clothing of the invention
has an
air permeability of the refreshing clothing from 200 cm3/cm2/sec up to 500
cm3/cm2/sec. If it is less than 200 cm3/cm2/sec, the air permeability may be
deteriorated and the diffusion of heat and evaporation of sweat emitted from
the
skin may possibly be inhibited and if it is more than 500 cm3/cm2/sec,
transfer of
the heat and water through the clothing may not be carried out sufficiently
and
contrarily the outer air may penetrate. The air permeability can be measured
by
using a air permeability tester according to JIS L 1096 A method.
[0081] In the fabric, articles and/or clothing of the invention, the upper
limit of
the weight per square-meter may be 120, 100 or even 90 g/m2. Unlike other
means
of providing such cooling feelings, if the weight per square-meter is more
than 120,
100 or even 90 g/m2, the mechanism at work may be stifled and so the cooling
feeling may possibly be deteriorated.
[0082] A method of producing the articles and/or clothing of the invention
is not
particularly limited and for example, conventionally known methods such as a
method of' producing clothing by weaving the fiber excellent in cool contact
feeling
of the invention can be employed. These materials may also be produced by the
conventionally known methods of sewing, cutting and the like, using the
fabrics
with the reversible structure obtained by the above-mentioned manner.
[0083] Underwear excellent in cool contact feeling can be produced by using
the
fiber of the invention or the fabric of the invention. Also, the clothing
excellent in
cool contact feeling of the invention can be used as underwear. In such
embodiments, the invention may provide any one or more of the benefits
described
above for the fiber, fabric, article, and/or clothing.
[0084] In addition to the underwear, the present invention includes
stockings,
gloves, face masks, mufflers and the like that may be produced by using the
fiber of
the invention or the fabric excellent in cool contact feeling of the
invention. They
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are brought into direct contact with the skin and therefore, they can cause a
particularly excellent effect.
[0085] The invention includes an article made from the fabrics described
above.
For example, various garments can be made with the fabrics of this invention.
In
some embodiments, the fabric is used in making undergarments or tight fitting
garments, for which the fabrics of this invention are well-suited due to the
comfort
and cooling effect provided by the fiber. Undergarments, such as bras and T-
shirts
as well as sport garments used for activities such as running, skiing,
cycling, or
other sports, can benefit from the properties of these fibers. Garments worn
next to
the body benefit from the elasticity and cooling effect the invention
provides. It
will be understood by those skilled in the art that any garment can be made
from the
fabric and fibers of this invention.
[0086] In other embodiments, the fibers described herein are used to make
one
or more of any number of garments and articles including but not limited to:
sports
apparel, such as shorts, including biking, hiking, running, compression,
training,
golf, baseball, basketball, cheerleading, dance, soccer and/or hockey shorts;
shirts,
including any of the specific types listed for shorts above; tights including
training
tights and compression tights; swimwear including competitive and resort
swimwear; bodysuits including wrestling, running and swimming body suits; and
footwear. Additional embodiments include work wear such as shirts and
uniforms.
Additional embodiments include intimates including bras, panties, men's
underwear, camisoles, body shapers, nightgowns, panty hose, men's undershirts,
tights, socks and corsetry. Additional embodiments include medical garments
and
articles including: hosiery such as compression hosiery, diabetic socks,
static socks,
and dynamic socks; therapeutic burn treatment bandages and films; wound care
dressings; medical garments. Additional applications include military
applications
that mirror one or more of the specific articles described above. Additional
embodiments include bedding articles including sheets, blankets, comforters,
mattress pads, mattress tops, and pillow cases.
[0087] In some embodiments, the article of the invention is a garment and
the
fibers that make up the fabric in the garment are arranged in the garment as
to be in
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direct contact with the skin of a wearer of said garment. This allows the
wearer to
gain the full benefit of the cooling effect provided by the invention.
[0088] The invention also provides a method of providing a cooling effect
in an
article, such as a garment, that comes into direct contact with human skin,
comprising the steps of: (I) preparing a fabric comprising the fiber of claim
1; (II)
preparing an article that comprises said fabric; and (II) bringing said
article into
direct contact with human skin.
[0089] It is known that some of the materials described above may interact
in
the final formulation, so that the components of the final formulation may be
different from those that are initially added. For instance, metal ions (of,
e.g., a
detergent) can migrate to other acidic or anionic sites of other molecules.
The
products formed thereby, including the products formed upon employing the
composition of the present invention in its intended use, may not be
susceptible of
easy description. Nevertheless, all such modifications and reaction products
are
included within the scope of the present invention; the present invention
encompasses the composition prepared by admixing the components described
above.
EXAMPLES
[0090] The invention will be further illustrated by the following examples,
which sets forth particularly advantageous embodiments. While the examples are
provided to illustrate the present invention, they are not intended to limit
it.
Example Set
[0091] Seven materials were evaluated to demonstrate the benefits of the
invention. These materials are summarized in the table below.
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Table 1 ¨ Sample Descriptions and Properties
Ex Sample Descriptionl Fabric Fabric Fabric
Diameter Length Weight
[cm] [cm] [g/m2]
1 Baseline: No Material (bare test surface) NA NA NA
2 Multifilament Red Core Polyester Fiber 13.9 42.0 27
3 Multifilament Blue Core Nylon Fiber2 14.7 43.0 25
4 Monofilamcnt Fiber A3 5.3 37.5 90
Monofilament Fiber B4 8.4 35.5 65
6 Multifilament Fiber C5 9.2 29.0 66
7 Monofitament Fiber D Semi Du116 10.8 43.0 43
¨ Each fabric sample is in the form of a open sock/sleeve. The diameter refers
to the diameter of
the sleeve the fabric creates while the length is the actual length of the
sample. For the fabric
weight, each sample was weighed and then, using the other measurements
reported, a weight in
terms of grams per meter squared was calculated for each fabric.
2 This fiber is commercially available from Invistalm.
3 ¨Fiber A is prepared from a polyalkylene glycol, an alkylene diol, and MDT
4 ¨ Fiber B is prepared from alkylene diol adipate, an alkylene diol, and
AlDI.
5 ¨ Fiber C is a multifilament version of Fiber B, and is chemically identical
to Fiber B.
6 ¨ Fiber D is Fiber B but with a commercially available dulling agent added.
[0092] Comparative Example 1 is a baseline and represents no fiber and/or
fabric. Comparative Examples 2 and 3 are comparative materials that do not
represent the invention. Examples 4, 5, 6 and 7 represent various embodiments
of
the invention.
[0093] It is noted that the fabrics tested have different diameters and the
fabrics
obtained for testing are of different weights. To account for these
differences, the
testing described below has been carried out with the use of clamps to fix the
fabric
samples in such a way as to provide comparable tension and fabric density over
the
testing surface, thus allowing for a valid comparison of the materials. Any
differences not accounted for by these controls are not expected to have a
significant impact on the parameters tested.
Test Methods and Results
[0094] The examples described above were tested to determine their cooling
power. This testing was conducted in a climatic chamber at controlled
temperature
and humidity using a sweating thermal mannequin as a test surface. The test
surface of the mannequin, with a known surface area, is equipped with
thermocouples to monitor temperature and heating elements to allow the test
surface to be heated to a realistic human skin temperature for the testing. In
addition, the power demands of the heating elements could also be monitored to
see
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the amount energy required to maintain a specific skin temperature at the test
surface. The test surface is also capable of moisture release, simulating the
sweat
release of human skin. A high power fan was used as a wind source. The area of
the test surface used for all of this testing is 629 cm2.
[0095] For this testing, the sweating thermal mannequin is placed inside
the
climatic chamber, which is set to 15 degrees C. Testing was carried out at 30%
and
50% relative humidity, with winds speeds of 0.3 m/s, 3 m/s and 5 m/s. A wind
speed of 0.3 m/s is the normal condition inside the climatic chamber and so
indicates the high speed fan is in the off position. Circular knitted, open-
ended
sock samples of each material, also referred to as sleeves, are placed on the
test
surface of the sweating thermal mannequin, in this case the forearm of the
mannequin. Samples are placed on the test surface for testing and then are
removed
and replaced with the next sample. As noted above, clamps are used to secure
each
sample to the forearm of the sweating thermal mannequin and care is taken to
ensure the samples are placed with comparable levels of tension and fabric
density.
[0096] At the start of each test, the chamber is brought up to the desired
conditions. The test surface, covered with the sample of fabric being testing,
is
heated to the desired starting skin temperature of either 31 or 34 degrees C,
selected
to approximate human skin temperature, and if wind is included in the test
conditions, the fan is turned on to the desired setting. Once all of these
conditions
are set, the test period begins by monitoring the amount of power required by
the
heating element to maintain the set test surface temperature. This amount of
power
is measured in Watts and is referred to as the cooling power of the fabric
being
tested under the given conditions of the test. The reported cooling power the
power
the system stabilized at under the given test conditions. At the end of each
test, the
sample fabric was replaced with a different sample and the testing was
repeated,
changing conditions as needed.
[0097] For the Example 1 baseline, the test was carried out with a bare,
uncovered test surface, providing the effect one could expect from bare skin.
This
bare skin baseline was included in the testing for purposes of comparison.
[0098] The table below summarizes the test conditions used and the examples
tested under each set of conditions:
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Table 2 - Summary of Cooling Power Test Conditions using the Mannequin
Condition Chamber Chamber Wind Speed Target Skin Examples
Tested at
Set' Temp Humidity [m/s] Temp2
these Conditions
[C] [%] [C]
I 15 50 3.0 34 1,2,3,4,5,6,7
II 15 50 5.0 31 1,2,3,4,5,6,7
III 15 30 3.0 34 1,2,3,4,5,6,7
IV 15 50 0.3 34 1,2,3,4,5,6,7
V 15 50 0.3 34 1,2,3,4,5,6,7
VI 15 30 0.3 34 1,2,3,4,5,6,7
1 - These condition sets were carried out in the testing in the following
order: IV, I, V. II, VI, III.
Condition Sets IV and V are identical, and were not run consecutively, thus
providing a duplicate
set of data that shows the repeatability of the results and relative
difference between samples.
2 - The target skin temperature for this testing is always 34 degrees C except
for the Condition Set
where the wind is at 5 m/s. Under these conditions a 31 degrees C skin
temperature is used to
ensure the system, which has limited heating capabilities, can maintain the
desired temperature.
[0099] The results of this testing are summarized in the table below:
Table 3 - Summary of Cooling Power Test Results'
Example Condition Condition Condition Condition Condition Condition
Set I Set II Set III Set IV Set V Set VI
1 - Baseline 39.65 41.36 38.92 16.02 13.16 15.40
2 - 28.82 29.43 27.78 11.83 9.54 10.96
Comparative _
3 - 30.19 30.16 30.36 12.93 10.60 12.25
Comparative
4 - Inventive 38.18 37.03 37.19 15.42 13.10 15.14
- Inventive 36.12 34.54 34.92 15.24 13.01 15.01
6 - Inventive 31.39 31.91 33.33 14.18 11.55 14.47
7 - Inventive 31.98 34.18 31.36 14.08 12.43 14.32
1 - All reported results in this table are cooling power, measured in Watts
1W]. This is the amount
of power the heating element in the sweating thermal mannequin required in
order to maintain the
temperature of the test surface, the surface of the foreman covered with the
test fabric, at the set
point under the Apeced conditions. The higher the cooling power reported, the
more power was
required to maintain the temperature, and so the larger the cooling effect the
fabric creates. In
other words, the larger the cooling power reported, the larger the cooling
ellect one would expect
to experience when wearing a garment made of the fabric tested. These results
are all in relation
to a standard test surface area of 629 cm2. A cooling power per square meter
may be calculated by
dividing the reported result by 0.629.
[0100] The results show that the fibers of the invention, and more
specifically
fabric made from such fibers, provide a cooling effect, as measured by cooling
power, greater than that of conventional synthetic fibers, and more
specifically
fabric made from conventional synthetic fibers. In addition the results show
that
the fibers of the invention, and more specifically fabric made from such
fibers,
provide a cooling effect, as measured by cooling power, comparable to that
seen in
the baseline, bare skin example. In other words, the present invention
provides
fibers, fabrics and various garments, including the means of making such
articles
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that would give a wearer whose skin comes into contact with said articles, a
cooling
sensation similar to that felt when no fabric is in contact with the skin that
is when
the skin is bare.
[0101] An additional set of testing is also included that adds the
additional
variable of moisture release from the test surface during the testing. In
these tests,
a sweating thermal foot model was used, where the model was equipped with
similar controls to the mannequin described above. The moisture releases used
in
this testing are designed to simulate different sweat rates that a person
would
experience when wearing a garment made of the test fabric, for example, during
exercise, and to see what impact if any this has on the cooling power of the
fabric.
[0102] The same seven examples listed in Table 1 were tested here. The
conditions used in this testing are summarized in the table below. For each
test
condition, the system was allowed to stabilize for 30 minutes without any wind
or
moisture release, during which time the cooling power of the fabric was
measured.
The moisture release was then started and the system was again allowed to
stabilize
over 30 minutes, during which the cooling power was measured. Finally, the
wind
condition was added and the system was again allowed to stabilize over 30
minutes,
during which the cooling power was measured.
Table 4 ¨ Summary of Cooling Power Test Conditions Using the Foot Model
Condition Chamber Chamber Wind Target Sweat Examples Tested
Set' Temp humidity Speed Skin Rate at these
[Cl [m/s] Temp [grams/hr] Conditions
[C]
VII 15 50 3.0 34 4 2,3,4,5,6,7
VIII 15 50 3.0 34 8 2,3,4,5,6,7
IX 15 50 3.0 34 16 2,3,4,5,6,7
X 15 50 5.0 34 4 2,3,4,5,6,7
XI 15 50 5.0 34 8 2,3,4,5,6,7
1 ¨ These condition sets were carried out in the testing in the following
order: VII, VIII, IX, X, XI.
[0103] The results of this testing are summarized in the table below. As
noted
above, each test condition included three distinct measurements of the cooling
power, one with no wind or moisture release (A), one with moisture release and
no
wind (B), and one with both the target moisture release and wind (C). For each
condition set, the measured cooling power are present below:
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Table 5A - Summary of Cooling Power Test Results'
Example Condition Set VII Condition Set VIII
Condition Set IX
(A) (B) (C) (A) (B) (C) (A) (B) (C)
2- Comparative 3.9 4.9 11.0 4.2 6.5 13.0 4.1 7.8
15.3
3 - Comparative 4.3 5.3 11.6 4.3 6.9 13.4 4.7 8.6
16.2
4 - Inventive 5.2 6.4 15.2 5.2 8.1 16.8 4.9 8.6
19.7
- Inventive 4.9 6.1 14.6 4.9 6.5 16.2 5.0 6.6
17.5
6 - Inventive 4.6 5.5 12.6 4.8 7.6 15.5 4.7 10.9
19.5
7 - Inventive 4.5 5.8 13.8 4.7 7.2 15.6 4.6 7.4
18.8
1 -All reported results in this table are cooling power, Watts [WI. See also
footnote 1 of table 3.
Table 5B - Summary of Cooling Power Test Results'
Example Condition Set X Condition
Set XI Mi!!1!igiMi!!!!igi!igEi!!1!igi!in!i!Elil
(A) (B) (C) (A) (B) (C) IMEMENNERVER.
2 - Comparative 4.2 5.2 15.5 4.4 6.7 16. 7
3 - Comparative 4.3 5.7 16.9 4.8 7.0 .. 17.9 g WEMiieiaagigg
4 - Inventive 5.4 6.7 21.2 5.0 8.0 22.0 . .
5 - Inventive 5.0 6.2 19.9 5.0 6.8 22.0
!i!i!!i!!!i!iTiTi!i!il!i!i!i!!i!!i!iTil!ili!i.i!il!l!i!i!!!i!i!i!i!i;
i!!!gg
6 - Inventive 5.2 6.3 17.9 4.8 7.8 .. 19.7
iTiggEgi!i!iiallEiTiT:
7 - Inventive 4.8 6.1 18.5 4.2 6.2 21.0
1 -All reported results in this table are cooling power, Watts [W _I. See also
footnote 1 of table 3.
[0104] The results
show that the fibers of the invention, and more specifically
fabric made from such fibers, provide a cooling effect, as measured by cooling
power, greater than that of conventional synthetic fibers, and more
specifically
fabric made from conventional synthetic fibers, particularly when the both
moisture
release and wind conditions are present. As these conditions are common, and
indeed expected, when a person is wearing a garment, especially sports apparel
and
similar clothing, the results reinforce the conclusion that articles made from
the
fibers of the invention would provide a person wearing said articles, or
otherwise
bring their skin into contact with said articles, a cooling effect.
Example Set 2
[0105] Various
materials are prepared so that they may further demonstrate the
present invention. These materials are summarized in the tables below.
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Table 6 ¨ Sample Descriptions and Properties
Ex Sample Descriptionl Hydroxyl Diisocyanate Linear
Terminated Alkylene
Intermediate Glycol
8 Monofilament Fiber BDO Adipate2 MDI BDO
9 Monofilament Fiber IIDO Adipate3 MDI BDO
Monofilament Fiber BDO/IIDO Adipate4 MDI BDO
11 Monofilamcnt Fiber PTMEG MDI BDO
12 Monofilament Fiber PEG MDI BDO
13 Monofilament Fiber BDO Adipate2 HDI BDO
14 Monofilament Fiber HDO Adipate3 HDI BDO
Monofilament Fiber BDO/HDO Adipate4 HDI BDO
16 Monofilament Fiber PTMEG HDI BDO
17 Monofilament Fiber PEG HDI BDO
18 Monofilament Fiber BDO Adipate2 HMDI BDO
19 Monofilament Fiber HDO Adipate3 HMDI BDO
Monofilament Fiber BDO/HDO Adipate4 HMDI BDO
21 Monofilament Fiber PTMEG HMDI BDO
22 Monofilament Fiber PEG IIMDI BDO
23 Monofilamcnt Fiber BDO Adipatc 2 MDI HDO
24 Monofilamcnt Fiber HDO Adipatc3 MDI HDO
Monofilament Fiber BDO/HDO Adipate4 MDI HDO
26 Monofilament Fiber PTMEG MDI HDO
27 Monofilament Fiber PEG MDI HDO
28 Monofilament Fiber BDO Adipate2 HDI , HDO ,
29 Monofilament Fiber HDO Adipate3 HDI HDO
Monofilament Fiber BDO/HDO Adipate4 HDI HDO
31 Monofilament Fiber PTMEG HDI HDO
32 Monofilament Fiber PEG HDI HDO
33 Monofilarnent Fiber BDO Adipate2 HMDI HDO
34 Monofilament Fiber HDO Adipate3 HMDI HDO
Monofilament Fiber BDO/IIDO Adipate4 IIMDI IIDO
36 Monofilament Fiber PTMEG IIMDI IIDO
37 Monofilamcnt Fiber PEG HMDI HDO
1 ¨ Each fabric sample is in the form of an open sock/sleeve woven from the
described fiber.
2 ¨ BDO Adipate is an adipate prepared from 1,4-butanediol and adipic acid.
3 ¨ HDO Adipate is an adipate prepared from 1,6-hexandiol and adipic acid.
4 ¨ BDO/HDO Adipate is an adipate prepared from adipic acid and a mixture of
114-butanedial
and 1,6-hexandiol.
,
-32-
Table 7 ¨ Sample Descriptions and Properties
Ex Sample Description' Hydroxyl Diisocyanate Linear
Terminated Alkylene
Intermediate Glycol
38 Multifilament Fiber BDO Adipate2 MDI BDO
39 Multifilament Fiber HDO Adipate3 MDI BDO
40 _ Multifilament Fiber BDO/HDO Adipate4 MDI
BDO
41 Multifilament Fiber PTMEG MDI BDO
42 Multifilament Fiber PEG MDI BDO
43 Multifilament Fiber BDO Adipate2 HDI BDO
44 Multifilament Fiber HDO Adipate3 HDI BDO
45 Multifilament Fiber BDO/HDO Adipate4 HDI
BDO
46 Multifilament Fiber PTMEG HDI BDO
47 Multifilament Fiber PEG HDI BDO
48 Multifilament Fiber BDO Adipate2 HMDI BDO
49 Multifilament Fiber HDO Adipate3 HMDI BDO
50 Multifilament Fiber , BDO/HDO Adipate4 IIMDI
BDO
51 Multifilament Fiber PTMEG HMDI BDO
52 Multifilament Fiber PEG HMDI BDO
53 Multifilament Fiber BDO Adipate2 MDI HDO
54 Multifilament Fiber HDO Adipate3 MDI HDO
55 Multifilament Fiber BDO/HDO Adipate4 MDI
HDO
56 Multifilament Fiber PTMEG MDI HDO
57 Multifilament Fiber PEG MDI HDO
58 Multifilament Fiber BDO Adipate2 HDI HDO
59 Multifilament Fiber HDO Adipate3 HDI HDO
60 _ Multifilament Fiber BDO/HDO Adipate4 HDI
HDO
61 , Multifilament Fiber PTMEG HDI HDO
62 Multifilament Fiber PEG HDI HDO
63 Multifilament Fiber BDO Adipate2 HMDI HDO
64 Multifilament Fiber HDO Adipate3 HMDI HDO
65 Multifilament Fiber BDO/HDO Adipate4 HMDI
HDO
66 Multifilament Fiber PTMEG HMDI HDO
67 Multifilament Fiber PEG HMDI HDO
1 ¨ Each fabric sample is in the form of an open sock/sleeve woven from the
described fiber.
2 ¨ BDO Adipate is an adipate prepared from 1,4-butanediol and adipic acid.
3 ¨ HDO Achpate is an adipate prepared from 1,6-hexandiol and adipic acid.
4 ¨ BDO/HDO Adipate is an adipate prepared from adipic acid and a mixture of
114-butanediot and
1,6-hexandiol.
[0106] Except in the Examples, or where otherwise explicitly
indicated, all numerical
quantities in this description specifying amounts of materials, reaction
conditions, molecular
weights, number of carbon atoms, and the like, are to be understood as
modified by the word
"about." Unless otherwise indicated, all percent values, ppm values and parts
values are on a
weight basis. Unless otherwise indicated, each chemical or composition
referred to herein
should be interpreted as being a commercial grade material which may contain
the isomers,
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by-products, derivatives, and other such materials which are normally
understood to
be present in the commercial grade. However, the amount of each chemical
component is presented exclusive of any solvent or diluent oil, which may be
customarily present in the commercial material, unless otherwise indicated. It
is to
be understood that the upper and lower amount, range, and ratio limits set
forth
herein may be independently combined. Similarly, the ranges and amounts for
each
element of the invention can be used together with ranges or amounts for any
of the
other elements. As used herein, the expression "consisting essentially of'
permits
the inclusion of substances that do not materially affect the basic and novel
charac-
teristics of the composition under consideration.
