WO 92/13119 2 ~ Q ~ "~ $ g PCT/US92/00359
-1-
T LE
Preparing Polyester Fine Filaments
This invention concerns improvements in, and
relating to, polyester fine filaments and their
manufacture and use.
Historically, synthetic fibers for use in
apparel, including polyester fibers, have generally
been supplied to the textile industry for use in
fabrics and garments with the object of more or less
duplicating and/or improving on natural fibers, For
many years, commercial synthetic textile filaments,
such as were made and used for apparel, were mostly of
deniers per filament (dpf) in a similar range to those
of the commoner natural fibers; i.e., cotton and wool.
More recently, however, polyester filaments have been
available commercially in a range of dpf similar to
that of natural silk, i. e. of the order of 1 :dpf, and
even in subdeniers~, i.e., less than about 1 dpf,
despite the increased cost. Various reasons have been
given for the recent commercial interest in such lower
dpfs, such as about 1 dpf, or even subdeniers.
Much has been written recently about this
increasing interest in fine denier polyester filaments.
. Very little technical detail has, however, been
published about any difficulties in spinning (i.e.,
extrusion and winding) techniques that ha~~e been used,
or even would be desirable, for manufacturing such fine
filaments, although it has been well understood by
those skilled in the art that conventional preparation
and handling techniques could not be used far such fine
filaments. For instance, in Textile Month, June 1990,
pages 40-46, three approaches are discussed for making
microfibers; namely, 1) conventional spinning to fine
WO 92/13119 . 210 ~.'~ 8,8 . , ;
" ~ , .. PCT/US92/00359
2
deniers, 2) splitting bicomponent fibers (of higher
deniers), and 3) dissolving away a component from
bicomponent fibers of higher denier. It will be
understood that the 2nd and 3rd approaches involve .
bicomponent spinning to form filaments first of higher
denier, arid processing such spun higher denier .
filaments to obtain the filaments of reduced denier;
such processing techniques are not the subject of the
present invention.
The present invention is concerned with the
preparation of fine filaments by a novel direct
spinning/winding process, in contrast with a process of
first spinning and winding up bicomponent filaments of
higher denier which then must be further processed to
obtain the reduced fine denier filaments that are
desired for use in textiles. Another 2-stage
possibility of manufacturing filaments of reduced
denier is to spin filaments of greater than one denier,
and then, draw the filaments after the spinning
operation, but this possibility has important
disadvantages that have been discussed in the art; on
the one hand, there are practical limitations to the
amount of draw that can be effected; there are also
product disadvantages in the properties of drawn yarns,
as contrasted with direct spin-oriented yarns; and the
cost of such processing (i.e., drawing) has to be
considered, especially when the drawing is performed as
a separate operation, after first packaging the spun
filaments, such as single yarn or warp drawing. Such
drawing proposals may have involved conventional
drawing techniques, or may have involved other
techniques, e.g., aerodynamic effects or reheating the
filaments after they have been solidified, but still
advancing under sufficient tension to draw (sometimes
referred to as space-drawing, if performed without
WO 92/13119 2 ~ ~ ~'~ ~ ~ ' ' ~PCT/US92/00359
godets of differential speeds). Some direct spinning
processes that have been proposed have relied on use of
specific polymer compositions, for instance specific
viscosities, that have disadvantages, so it would be
desirable to use a process that does not require use of
special viscosities or other special compositional
aspects.
To summarize, previous polyester filament
manufacturing techniques that have been disclosed in
the art have not been specifically directed to and have
not been suitable in practice for producing fine denier
polyester filaments by a simple direct spinning/winding
operation, or have involved limitations and
disadvantages. So it has been desirable to provide
such a direct spinning process for manufacturing fine
polyester filaments of the desired dpf and properties
without such disadvantages. The present invention
solves this problem. The filaments of the invention
are "spin--oriented", the significance of which is
discussed in the art and hereinafter.
Commercial polyester filaments were made
initially by "split" processes that involved a separate
drawing stage after spinning and winding undrawn
filaments. In the 1950's, Hebeler suggested in U. S.
Patents Nos. 2,604,667 and 2,604,689, the possibilities
of high speed spinning of polyester melts. In the
1970's, high speed spinning of polyester melts, as
described by Petrille in U. S. Patent No. 3,771,307 and
by Piazza and Reese in U. S. Patent No. 3,772,872, were
made the basis of a process for preparing spin-oriented
yarns that have been used as draw-texturing feed yarns.
High speed spinning of polyester melts has also been
the basis of other processes that were first disclosed
in the 1970's, such as Knox in U. S. Patent No.
4,156,071, and Frankfort and Knox in U. S. Patent Nos.
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4,134,882, and 4,195,051.
The art discloses fundamental differences in
fine structure and properties between filaments that
are spin-oriented, indicating orientation of the
polyester molecules obtained from the (high speed) ,
spinning, and drawn filaments, indicating orientation
derived from drawing of the filaments as an entirely
separate process, after winding the spun filaments, or
even as a continuous process, before winding, but after
cooling the melt to form solid filaments before drawing
such filaments.
An object of the present invention is to
provide fine filaments that have the characteristics of
being spin-oriented, because of the advantageous
properties that are provided by this characteristic.
Several aspects and embodiments are provided
according to the present invention as follows:
1) a process for preparing spin-oriented
polyester fine °ilaments;
2) spin-oriented polyester fine filaments
with deniers about 1 or less, having enhanced
mechanical quality and denier uniformity making these
filaments especially suitable for high speed textile
processing;
3) spin-oriented polyester fine filaments,
especially suitable for use as draw feed yarns in high
speed texturing, crimping, and warping processes;
4) spin-oriented polyester fine filaments, '
especially suitable for use as direct-use textile
yarns, without need for additional draw or heat '
treatments, in critically dyed flat woven and knit
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fabrics; for use as feed yarns for air-jet texturing
and stuffer-box crimping, wherein no draw is required;
and may be uniformly cold drawn, if desired, to prepare
warp yarns of higher shrinkage with dye uniformity
suitable for critically dyed end-uses;
i.
5) drawn spin-oriented polyester fine
filaments, especially suitable for use as textile yarns
in critically dyed flat woven and knit fabrics; and
processes for preparing these fine drawn fine filament
yarns;
6) bulked polyester fine filament yarns
capable of being dyed uniformly under atmospheric
conditions without the use of carriers; and a grocess
for preparing these bulked fine filament yarns;
?) mixed filament yarns, wherein the fine
filaments are of this invention; and especially mixed
filament yarns, wherein, all filaments are of this
invention, but differ in denier, cross-section, and/or
shrinkage potential.
In particular according to the present
invention, the following are provided:
A process for, preparing spin-oriented
polyester fine filaments, wherein,
(i) the polyester polymer is selected to have
a relative viscosity (hRV) in the range of about 13 to
about 23, a zero-shear melting point (TM°) in the range
of about 240°C to about 265°C, and a glass transition
temperature (Tg) in the range of about 40°C to about
80°C;
(ii) said polyester is melted and heated to a
temperature (Tp) in the range of about 25°C to about
WO 92/13119 21 ~ ~ ~ PCT/US92100359
55°C, preferably in the range of about 30°C to about
50°C, above the apparent polymer melting point (TM)a%
(iii) the resulting melt is filtered
sufficiently rapidly that the residence time (tr) at
polymer melt temperature (Tp) is less than about 4
minutes;
(iv) the filtered melt is extruded through a
spinneret capillary at a mass flow rate (w) in the
range about 0.07 to about 0.7 grams per minute (g/min),
and the capillary is selected to have a cross-sectional
area (Ac) in the range about 125x10-6 cm2 (19.4 mils2)
to about 1250x10-6 cm2 (194 mils2) preferably in the
range of about 125x10-6 cm2 (19.4 mils2) to about
750x10'6 cm2 (116.3 mils2) and a length (L) and
diameter (DgNp) such that the (L/DgND)-ratio is at
least about 1.25 and preferably less than about 6, and
especially less than about 4;
(v) protecting the extruded melt from direct
cooling as it emerges from the spinneret capillary over
a distance (LDQ) of at least about 2 cm and less than
about (l2dpf~)cm, where dpf is the denier per filament
of the spin-oriented polyester fine filament,
preferably in the range of about 1 to about 0.2 dpf,
and especially in the range of about 0.8 to about 0.2
dpf; and desireably an average along-end denier spread
(DS) less than about 4%, and preferably less than about
3%, and especially less than about 2%;
(vi) cooling the attenuating spinline to
below the polymer glass-transition temperature (Tg),
preferably by radially directed air having a
temperature (Ta) less than about the polymer Tg and a
velocity (Va) in the range of about 10 to about 30
:peters per minute (m/min);
WO 92/13119 PCT/US92/00359
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210178 ~
(vii) attenuating to an apparent spinline
strain (Ea) in the range of about 5.7 to about 7.6, and
to an apparent internal spinline stress (ca) in the
range of about 0.045 to about 0.195 grams per denier
(g/d), preferably in the range of about 0.045 to about
0.105 g/d for preparing filaments especially suitable
for draw feed yarns, characterized by a tenacity-at-7%-
elangation (T7) in the range of about 0.5 to about 1
i
g/d; and to an apparent internal spinline stress (Qa) '
preferably in the range of about 0.105 to about 0.195
g/d for pregaring filaments especially suitable for
direct-use yarns, characterized by a tenacity-at-7%-
elongation (T7) in the range of about 1 to about 1.75
g/d;
(viii) converging the cooled and attenuated
filaments into a multifilament bundle by use of a low
frictian surface at a distance (Lc) in the range about
50 cm to about 140 cm, preferably in the range of about
50 cm to about (50+9odpf~)cm;
ZO (ix) winding up the multifilament bundle at a
withdrawal speed (V) in the range of about 2 to about 6
kilometers per minute (km/min), preferably in the range
of about 2 to about 5 km/min, and especially in the
range of about 2.5 to about 5 km/min;
Also, according the present invention the
following spin-oriented polyester fine filaments, and
products there from, are provided:
Spin-oriented polyester fine filaments of
denier per filament (dpf) about 1 or less, preferably
in the range of about 0.8 to about 0.2 dpf, wherein,
said polyester is characterized by having a relative
viscosity (LRV) in the range of about 13 to about 23, a
zero-shear polymer melting point (TMo) in the range of
WO 92113119 PCT/US92/0(?359
about 240°C to about 265°C, and a glass-transition
temperature (Tg) in the range of about 40°C to about
80°C; and said fine filaments are further characterized
by:
(i) boil-off shrinkage (S) less than about
the maximum shrinkage potential (Sm), wherein Sm =
[(550-Eg)/6.5],% and the percent elongation-to-break
(Eg) is in the range about 40% to about 160%;
(ii) maximum shrinkage tension, (STmax), in
the range about 0.05 to about 0.2 g/d, with a peak
temperature T(STmax), in the range about 5°C to about
30°C above the polymer glass-transition temperature
(Tg) ~
(iiij a tenacity-at-7%-elongation (T7) in the
range of about 0.5 to about 1.75 g/d, and such that the
[(Tg)n/T7]-ratio is of at least about (5/T7) and
preferably at least about (6/T~); wherein, (Tg)n is the
tenacity-at-break normalized to a reference LRV of 20.8
and % delusterant (such as Ti02) of 0%;
(iv) desireably an average along-end denier
spread (DS) of less than about 4%, preferably less than
about 3%, and especially less than about 2%.
Spin-oriented fine filaments, especially
suitable for use as draw feed yarns (DFY),
characterized by a boil-off shrinkage (S) at least
about 12%, an elongation-at-break (Eg) in the range
about 80% to about 160%, a tenacity-at-7%-elongation
(T~) in the range about 0.5 to about 1 g/d.
Spin-oriented fine filaments, especially
suitable for use as direct-use yarns (DUY),
characterized by a shrinkage differential (DS = DHS -
S) less than about +2%, wherein, boil-off shrinkage (S)
WO 92/13119 PCT/US92100359
9 . , .
2.~01.'~~~
and dry heat shrinkage (DHS) are in the range of about
2% to about 12%, such that the filament denier after
boil-off shrinkage, dpf(ABO), is about 1 or less and
preferably in the range of about 1 to about 0.2 dpf,
and more preferably in the range of about 0.8 to about
0.2 dpf; a tenacity-at-7%-elongation (T7) in the range
of about 1 to about 1.75 g/d; an elongation-at-break
(Eg) in~the range of about 40% to about 90%, and a
post-yield modulus (Mpy) in the range of about 2 to
about 12 g/d;
Spin-oriented fine filaments having the
capability of being uniformly cold drawn, characterized
by a shrinkage differential (DS = DHS - S) less than
about +2%, wherein, boil-off shrinkage (S) and dry heat
shrinkage (DHS) are in the range of about 2% to about
12%, an onset of cold crystallization, Tcc(DSC), of
less than about 105°C and an instantaneous tensile
modulus (Mi) at least about 0.
Drawn spin-oriented polyester fine filaments
ZO with deniers after boil-off shrinkage, dpf(ABO), in the
range of about 1 or less, preferably in the range of
about 0.8 to about 0.2 dpf, wherein, said drawn
filaments are further characterized by:
(i) boil-off shrinkage (S) and dry heat
shrinkage (DHS) in the range of 2% to about 12%;
(ii) a tenacity-at-7%-elongation (T~) of at
least about 1 g/d, such that the [(Tg)n/T7]-ratio is at
least about (5/T7); preferably at least about (6/T7),
wherein, (Tg)n is the tenacity-at-break normalized to a
reference LRV of 20.8 and percent delusterant (such as
Ti02) of 0%; and an elongation-at-break (Eg) in the
range of about 15% to about 55%;
(iii) a past-yield modulus (Mpy), preferably
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in the range about 5 to about 25 g/d;
(iv) desireably an average denier spread (DS)
less than about 4%, preferably less than about 3%,
especially less than about 2%.
Bulked spin-oriented polyester fine filaments '
of denier after boil-off shrinkage, dpf (ABO),in the
range of about 1 to about 0.2 dpf, preferably 0.8 to
about 0.2 dpf, wherein, said bulked filaments are
further characterized by a boil-off shrinkage (S) and
dry heat shrinkage (DHS) in the range 2% to about 12%,
an elongation-at-break (Eg) in the of range about 15%
to about 55%, a tenacity-at-7%-elongation (T~) at least
about 1 g/d, and preferably with a post-yield modulus
(Mpy) in the range about 5 to about 25 g/d and a
relative disperse dye rate (RDDR), normalized to 1 dpf,
of at least about 0.1.
Mixed filament yarns, wherein the fine
filaments are of this invention; and especially mixed
filament yarns, wherein, all filaments are of this
invention, but differ in denier, cross-section, and/or
shrinkage patential.
Preferred such spin-oriented, bulked and
drawn flat filaments are capable of being dyed with
cationic dyestuffs, on account of containing in the
range of about 1 to about 3 mole % of ethylene-5-M-
sulfo-isophthalate structural units, where M is an
alkali metal cation, such sodium or lithium.
Especially preferred such spin-oriented,
bulked, and drawn flat filaments capable of being .
disperse dyed uniformly under atmospheric conditions
without carriers, are characterized by a dynamic loss
modulus peak temperature T(E"max) of less than about
115°C, preferably less than about 110°C; and are of
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polyester polymer, essentially polyethylene
terephthalate), composed of first alternating
hydrocarbolenedioxy structural units A,
[-O-C2H4-O-], and hydrocarbolenedicarbonyl structural
units s, [-C(o)-C6H4-C(0)-], modified with minor
amounts of other hydrocarbolenedioxy structural units A
and/or hydrocarbolenedicarbonyl structural units B,
that are different from the first structural units,
such as to provide a polyester polymer with a zero-
shear melting point (TMo) in the range about 240°C to
about 265°C and a glass-transition temperature (Tg) in
the range of about 40°C to about 80°C.
The filaments of the present invention may be
nonround for enhanced tactile and visual aesthetics,
and comfort, where said nonround filaments have a shape
factor (SF) at least about 1.25, wherein the shape
factor (SF) is defined by the ratio of the measured
filament parameter (PM) and the calculated parameter
(PgND) for a round filament of equivalent cross-
sectional area. Hollow filaments may be spun via post-
coalescence from segmented spinneret capillary orifices
to provide lighter weight fabrics with greater bulk and
filament bending modulus for improved fabric drape.
Further aspects and embodiments of the
invention will appear herein.
FIG. 1 is a graphical representation of
spinline velocity (V) plotted.versus distance (x) where
the spin speed increases from the velocity at extrusion
(Vo) to the final (withdrawal) velocity after having
completed attenuation (typically measured downstream at
the point of convergence, Vc); wherein, the apparent
internal spinline stress (Qa) is taken as being
proportional to the product of the spinline viscosity
at the neck point (r~)p , (i.e., herein found to be
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PCT/US92/00359
_ 12
approximately proportional to about the ratio LRV/Tp6,
where Tp is expressed in °C),and the velocity gradient
at the neck point (dV/dx), (herein found to be
approximately proportional to about v2/dpf, especially
over the spin speed range of about 2 to 4 km/min and
proportional to about V3/2/dpf at higher spin speeds,
e.g., in the range of about 4 to 6 km/min). The spin
line temperature is also plotted versus spinline
distance (x) and is observed to decrease uniformly with
distance as compared to the sharp rise in spinline
velocity at the neck point.
FIG. 2 is a graphical representation of the
birefringence (fin) of the spin-oriented filaments
versus the apparent internal spinline stress (a)a;
wherein the slope is referred to as the "stress-optical
coefficient, SOC" and Lines A, B, and C have SOC values
of 0.75, 0.71, and 0.645 (g/d)-1, respectively; with an
average SOC of about 0.7; and wherein Lines A and C are
typical relationships found in literature for~2GT
polyester. The values of the apparent internal
spinline stress (~a) agree well with values found in
literature.
FIG. 3 is a graphical representation of the
tenacity-at-7%-elongation (T7) of the spin-oriented
filaments versus the apparent internal spinline stress
(aa). The near linear relationship of birefringence
(On) and T7 versus the apparent internal spinline
stress (va), as shown in FIGS. 2 and 3, permits the use
of T7 as a useful parameter being representative of the
filament average orientation. Birefringence (On) is
typically very difficult structural parameter to
measure for fine filaments with deniers less than 1.
F1G. 4 is a graphical representation of the
preferred values of the apparent internal spinline
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210178
stress (Qa) and the spin-oriented filament yarn
tenacity-at-7%-elongation (T~) plotted versus the spin
line extension ratio ER (= V/VO) on a natural logarithm
scale (where Eg-values of 200 and 2000, far example are
expressed on the x-axis as 0.2 and 2; i.e., ER/100o);
wherein the natural logarithm ln(ER) is called herein
as the apparent spinline strain (Ea), where V is the
final (withdrawal) spinline velocity and Vo is the
capillary extrusion velocity. The process of the
invention is described by the enclosed region ADLI with
region ADHE (II) preferred for preparing direct-use
filaments and region EHLI (I) preferred for preparing
draw feed yarns. Especially preferred processes are
represented by regions BCGF and FGKI.
FIG. 5 is a representative Instron load-
extension curve showing the graphical calculation of
the "secant" post-yield modulus (Mpy) calculated from
the tenacity-at-7%-elongation (T~), denoted by point C,
and from the tenmcity-at-20%-elongation (T2p); denoted
by point A, and defined by the expression
(1.0TT~-1.2T20)/0.13; and compares the "secant" Mpy
(herein denoted as tan B to that of the "tangential"
Mpy (herein denoted as tan a, i.e., slope of line
segment AB). For yarns which have an instantaneous
modulus Mi (= d(stress)/d(elongation) greater than
about 0, the value of tan B is about the same as tan a.
FIG. 6 is a graphical representation of the
secant Mpy (tan 8 in FIG. 5) versus birefringence (On)
of spin-oriented filaments. For yarns wherein tan a is
essentially equal to tan B, the post-yield modulus
(Mpy) becomes a useful measure of molecular
orientation.
FIG. 7 is a graphical representation of the
Relative Disperse Dye Rate (RDDR), as normalized to 1
WO 92/13119 PCT/US92/00359
g . 14
dpf, versus the average filament birefringence (fin).
FIG. 8 is a graphical representation of the
filament amorphous free-volume of the fiber (Vf~am, as
defined herein after), versus the peak temperature of
the fiber dynamic loss modulus, T(E!'max). taken herein
as a measure of the glass transition temperature which
is typically 20°C to about 50°C above the Tg of the ;
polymer. A decreasing T(E"max) value corresponds to
greater amorphous free-volume (Vf~amj, and hence to
improved dyeability, as measured herein by a Relative
Disperse Dye Rate (RDDR) value (normalized to 1 dpf) of
at least about 0.1.
FIG. 9 is a graphical representation of the
filament density (p) versus birefringence (fin); wherein
the diagonal lines represent combinations of density
(p) and (~nj of increasing fractional amorphous,
orientation (fa), used in the calculation of the free-
volume Vf~am depicted in FIG. 8.
FIG. 10 is a representative Differential
Scanning Calorimetry (DSC) spectrum showing the thermal
transitions corresponding to the glass-transition
temperature (Tg), onset of "cold" crystallization
Tcc(DSC) and the zero-shear melting point TM of the
fiber, which is higher than the zero-shear melting
point TMo of the polymer due to the effect of
orientation and crystallinity of the fiber melting
point. To measure the zero-shear melting point (TMo)
of the polymer, a second DSC heating of the previous
melted DSC fiber sample is made to provide the DSC
spectrum of the polymer rather than the fiber was
extruded.
FIG. 11 is a representative shrinkage tension
(ST)-temperature spectrum for the spin-oriented fine
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polymer filaments of the invention showing the maximum
shrinkage tension ST(max). Peak temperature T(STmax)
and the preferred "heat set" temperature Tset below
which heat setting does not appreciably adversely
affect dye ability.
FIG. 12 are representative tenacity (T = load
(gms)/original denier) versus percent elongation curves
for a typical draw feed yarn of the invention (curve
C); for a typical direct-use yarn of this invention
(curve B); and for the preferred direct-use yarns of
the invention after relaxed heat treatment (Curve A);
i.e, akin to after dyeing.
FIG. 13 is a graphical representation of the
preferred values for the tenacity-at-break (TB)n,
normalized for the affects of LRV and percent
delusterant (such as Ti02), plotted as the (TB)n/T7-
ratio versus the reciprocal of the T7 (i.e.,.versus
1/T7); wherein, Curve A: [(TB)n/T7J _ (5/T7); and curve
B: [(TB)n/T7J ~ (6/T7)~
FIG. 14 is a plat of the ratio, T7/(V2/dpf)
versus the product of the number of filaments per yarn
extrusion bundle (#c) and the ratio, (Dref/Dsprt)2,
where Dref and Dsprt are the diameters of a reference
spinneret (e. g., about 75 cm) and the test spinneret,
respectively. The slope "n" from a ln-In plot is found
to be about negative 0.7 (-0.7); that is, the tenacity-
at-7%-elongation (T7) is found to vary proportionally
to (V2/dpf) and to [(,~c)(Dref/Dsprt)2J 0'7: that is,
the tenacity-at-7%-elongation (T7) decreases
approximately linearly with an increase in the filament
extrusion density to the power of plus 0.7 (+0.7);~ and
thereby the fil~iment extrusion density may be used to
as a process parameter to spin finer denier filaments
at higher spinning speeds (V). At higher spin speeds,
WO 92/13119 PCT/US92/00359
210~'~~8 16
e.g., in the range of about 4 to 6 km/min, it is found
that the apparent spinline stress increases less
rapidly with spin speed (V); i.e., is found to be
proportional to,(V3/2/dpf).
The polyester polymer used for preparing
spin-oriented filaments of the invention is selected to
have a relative viscosity (LRV) in the range about 13
to about 23, a zero-shear melting point (TM°) in the
range about 240°C to about 265°C; and a glass-
transition temperature (Tg) in the range about 40°C to
about 80°C (wherein TMo and Tg are measured from the
second DSC heating cycle under nitrogen gas at a
hemting rate of 20°C per minute). The said polyester
polymer is a linear condensation polymer composed of
alternating A and B structural units, where, A is a
hydrocarbolenedioxy unit of the form [-O-R'-O-] and B
is a hydrocarbolenedicarbonyl unit of the form
[-C(o)-R"-C(O)-], wherein, R' is primarily [~c2H4-], as
in the ethylenedioxy (glycol) unit [-O-C2H2-o-], and R"
is primarily [-C6H4-], as in the 1,4-benzenedicarbonyl
unit [-C(O)-C6H4-C(O)-], such to provide, for example,
at least about 85 percent of the recurring structural
units as ethylene terephthalate,
[-O-C2H4-O-C(O)-C6H4-C(O)-].
Suitable polyethylene terephthalate), herein
denoted as PET or 2GT, based polymer may be formed by
the DMT-process as described by H. Ludwig in his book
"Polyester Fibers, Chemistry and Technology", John
Wiley and Sons Limited (1971), and by the TPA-process
as described in Edging U. S. Patent No. 4,110,316.
Included are also copolyesters in which, for example,
up to about 15 percent of the hydrocarbolenedioxy
and/or hydrocarbolenedicarbonyl units are replaced with
different hydrocarbolenedioxy and
hydrocarbolenedicarbonyl units to provide enhanced low
w0 92/13119 " 2 ~ ~ ~ '~ ~ ~ 17 PCT/US92l00359
temperature disperse dyeability, comfort, and aesthetic
properties. Suitable replacement units may be found in
Most U. S. Patent No. 4,444,710 (Example VI), Pacofsky
U. S. Patent No. 3,748,844 (Col. 4), and Hancock, et
al. U. S. Patent No. 4,639,347 (Col. 3).
The polyester polymer may also be modified
with ionic dye sites, such as ethylene-5-M-sulfo-
isophthalate residues, where M is an alkali metal
cation, such as sodium or lithium; for example, in the
range of 1 to about 3 mole percent ethylene-5-sodium-
sulfo-isophthalate residues may be added to provide
dyeability of the polyester filaments with cationic
dyestuffs, as disclosed by Griffing and Remington U. S.
Patent No. 3,018,272, Hagewood etal in U. S. Patent No.
4,929,698, Duncan and Scrivener U. S. Patent No.
4,041,689 (Ex. VI), and Piazza and Reese U. S. Patent.
No. 3,772,872 (Ex. VII). To adjust the dyeability or
other properties of the spin-oriented filaments and the
drawn filaments therefrom, some diethylene glycol (DEG)
may be added to the polyester polymer as disclosed by
Bosley and Duncan U. S. Patent No. 4,025,592 and in
combination with chain-branching agents as described in
Goodley and Taylar U. S. Patent No. 4,945,151.
According to the present invention there is
provided a process fox preparing spin-oriented
polyester filaments having a fineness, for example, in
the range of about 1 to about 0.2 denier per filament
(dpf), preferably in the range about 0.8 i.o about 0.2
denier per filament (dpf);
(a) by melting and heating said polyester
polymer, as described herein before, to a temperature
(TP) in the range of about 25°C to about 55°C,
preferably in the range of about 30°C to about 50°C,
above the apparent melting temperature (TM)a, wherein,
WO 92/13119 t C) p 1a PCT/US92/00359
(TM)a is greater than the zero-shear melting
temperature (TM°) as a result of the shearing action of
the polymer during extrusion and is defined, herein,
by:
(TM)a = [TMo + 2x10-4(L/D
RND ) Ga 7 .
where L is the length of the capillary and DgND is the
capillary diameter for a round capillary, or for a non-
round capillary, wherein, for a non-round capillary,
DgND (cm) is the calculated equivalent diameter of a
round capillary of equal cross-section area Ac (cm2);
and Ga (sec-1) is the apparent capillary. shear rate
defined, herein after;
(b) filtering the resulting polymer melt
through inert medium, such as described by Philligs in
U. S. Patent No. 3,965,010, in a pack cavity (similar
to that illustrated in FIG. 2-31 of Jamieson U. S.
Patent Na. 3,249,669), sufficiently rapidly that the
residence time (tr) is less than about 4 minutes,
wherein, tr is defined by ratio (VF/Q) of the free-
volume (VF, cm3) of the filter cavity (filled with the
inert filtration medium) and the polymer melt volume
Elow rate (Q, cm3/min) through the filter cavity. The
polymer melt volume flow rate (Q) through the filter
cavity is defined by the product of the capillary mass
flow rate (w, g/min) and the number of capillaries (~c)
per cavity divided by the melt density (herein taken to
be about 1.2195 g/cm3); that is, Q = ~cw/1.2195. The
free-volume (VF,cm3) of the filter cavity (filled with
the inert filtration medium) is experimentally
determined by standard liquid displacement techniques
using a low surface tension liquid, such as ethanol.
By replacing the capillary mass flow rate (w), by its
equivalent w = [(dpf~V)/9), (where V is the withdrawal
spin speed expressed as km/min), in above expression
WO 92/13119 ~ ~ ~ ~ ~ ~ 19 PCT/US92/00359
for the melt residence time tr, it is found that the
residence time tr decreases with increasing filament
denier, withdrawal speed (V) and number of filaments
per filter cavity, and decreases with a reduction
in the filter cavity free-volume (VF). The cavity
free-volume (VF) may be decreased by altering the pack
cavity dimensions and by utilizing inert material which
provides sufficient filtration capabilities with less
free-volume. The number of filaments (i.e,
capillaries) per filter cavity (#c) may be increased
for a given yarn count by extruding more than one
multifilament bundle from a single filter cavity, that
is, spinning a larger number of filaments and then
splitting (herein, called multi-ending) the filament
bundle into smaller filament bundles of desired yarn
denier, preferably by using metered finish tip
separator guides positioned between about 50 cm to
about (50+90dpf~)cm;
(c) the filtered polymer melt is extruded
through a spinneret capillary at a mass flow rate (w)
in the range of about 0.07 to about 0.7 grams per
minute (g/min) and the capillary is selected to have a
cross-sectional area, Ac = (~/4)Dg~D2, in the range of
about 125x10-6 cm2 (I9.4 mils2) to about 1250x10-6 cm2
(194 mils2), preferably in the range of about 125x10-6
cm2 (19.4 mils2) to about 750x10-6 cm2 (116 mils2), and
a length (L) and diameter (DAD) such that the L/Dg~D-
ratio is in the range of about 1.25 to about 6,
preferably in the range of about 1.25 to about 4;
wherein,
Ga (sec-1) _ ((32/60~-)(w/P)/DRND37.
and w is the capillary mass flow rate (g/min), p is the
polyester melt density (taken as 1.2195 g/cm3), and
DgND is the capillary diameter (defined herein before)
WO 92/13119 PCT/US92/00359
21f~:~ ~8~ 2°
in centimeters (cm);
(d) protecting the freshly extruded polymer
melt from direct cooling, as it emerges from the
spinneret capillary over a distance LDQ of, at least
about 2 cm and less than about (l2dpf~)cm, where dpf is
the denier per filament of the spin-oriented polyester
fine filament;
(e) carefully cooling the extruded melt to
below the polymer glass-transition temperature (Tg),
wherein, said cooling may be achieved by use of laminar
cross-flow quench fitted with a delay tube (as
described in Makansi U. S. Patent No. 4,529,368), and
preferably by radially directed air (as described in
Dauchert U. S. Patent No. 3,067,458), wherein the
temperature (Ta) of the quench air is less than about
Tg and the velocity (Va) of the quench air is in the
range of about 10 to about 30 m/min;
f) while attenuating the cooled melt to an
apparent spinline strain (aa) in the range of about 5.7
to about 7.6, preferably in the range of about 6 to
about 7.3, wherein, the apparent spinline strain Ea is
defined as the natural logarithm (ln) of the spinline
extension ratio (Eg), and Eg is the ratio of the
withdrawal speed (V) and the capillary extrusion speed
(Vo); that is, for DgND in centimeters, Ea is given by:
ln(ER) = ln(V/Vo) = In[(2.25x105~p)(D~D2/dpf)J;
g) providing during attenuation the
development of an apparent internal spinline stress
(Qa) in the range of about 0.045 to about 0.195 g/d, .
preferably in the range of about 0.045 to about 0.105
g/d for preparing spin-oriented filaments, especially
suitable for draw feed yarns (DFY), characterized with
tenacity-at-7%-e?ongation (T7) values in the range of
~.s-et.:. t UU
WO 92/13119 PCT/US92/00359
21
about 0.5 to about 1 g/d, and preferably an apparent
internal spinline stress (Qa) in the range of about
0.105 to about 0.195 g/d for preparing spin-oriented
filaments especially suitable for direct-use yarns
(DUY), characterized by tenacity-at-7%-elongation (T7)
in the range of about 1 to about 1.75 g/d; wherein, the
apparent internal spinline stress (Qa) is defined
herein by the product of the apparent viscosity of the
attenuating melt (rim) and the spinline velocity
gradient (dV/dx) at the paint that attenuation is
essentially complete (herein referred to as the 'neck-.
point'; and the apparent internal spinline stress (ca)
is found to increase with increasing polymer LRV and
withdrawal speed (V) and to decrease with increasing
filament dpf, number of filaments (~c) for a given
spinneret surface area (Ao cm2) and polymer temperature
(Tp); and herein is expressed by an empirical
analytical relationship of the form:
(0a) a k(LRV/LRV20.8)(TR/TP)6(V2/dpf)(AO/#c)0.7,
wherein k has an approximate value of 10-2(pm/SOC),
where pm is the density of the spin-oriented filaments
(e. g., in the range of about 1.345 to about 1.385
g/cm3, that is about 1.36 g/cm3) and SOC is the
"stress-optical coefficient" for the polyester polymer
(e.g., about 0.7 in reciprocal g/d for 2GT
homopolymer); Tg is the polymer reference temperature
defined by (TMo + 40°C) where TMo is the zero-shear
(DSC) polymer melting point; Tp is the polymer melt
spin temperature,°C; V is the withdrawal speed
expressed in km/min; ~c is the number of filaments
(i.e., capillaries) for a given extrusion surface, A°,
expressed as ,~c/cm2; LRV is the measured polymer (lab)
viscosity and LRV20.8 is the corresponding reference
LRV-value (where hRV is defined herein after) of the
polyester polymer having the same zero-shear
WO 92/13119 ~ ~ ~ ~ ~ $ ,; , i. , i 22 PCT/U592/00359
"Newtonian" melt viscosity (r~o) at 295°C as that of 2GT
homopolymer having an LRV-value of 20.8 (e. g.,
cationic-dyeable polyester of 15 LRV is found to have a
melt viscosity as indicated by capillary pressure drop
in the range of 2GT homopolymer of about 20 LRV and
thereby a preferred reference LRV for such modified
polymers is about 15.5 and is determined experimentally
from standard capillary pressure drop measurements);
(h) converging the cooled and fully
attenuated filaments into a multifilament bundle by use
of a low friction surface, (that is, in a manner that
does not abrade nor snub the filaments), such as by a
finish roll, and preferably by a metered finish tip
applicator (as described in Agers U. S. Patent No.
4,926,661), at a distance (Lc) from the face of the
spinneret in the range of about 50 cm to about 140 cm,
preferably in the range of about 50 cm to about
(50+90dpf~)cm, wherein the finish is usuallyran aqueous
emulsion of about 5% to about 20% by weight sdlids and
finish-on-yarn is about 0.4% to about 2% by weight
solids, depending on the end-use processing
requirements;
(i) interlacing the filament bundle using an
air jet, essentially as described by Bunting and Nelson
in U. S. Patent No. 2,985,995 and by Gray in U. S.
Patent No. 3,563,021, wherein, the degree of
interfilament entanglement (herein referred to as rapid
pin count RPC as measured according to Hitt in U. S.
Patent No. 3,290,932), is selected based on yarn
packaging and end-use requirements;
(j) winding up the multifilament bundle at a
withdrawal speed (V), herein defined as the surface
speed of the first driven roll, in the range of about 2
to about 6 km/min, preferably in the range of about 2
WO 92/13119 '~ ~ a 12"j ~ ~ . :pCT/US92/00359
to about 5 km/min, and especially in the range of about
2.5 to about 4.5 km/min; wherein the retractive forces
from aerodynamic drag are reduced by relaxing the
spinline between the first driven roll and the windup
roll by overfeeding in the range of about 0.5 to about
5%, without the application of heat (except for use of
heated interlace jet fluid (such as heated air or
water-saturated air) for preventing finish deposits
forming on the interlace jet surfaces as described by
Harris in U. S. Patent No. 4,932,109.
The polyester fine filaments. of this
invention are manufactured by a simplified direct spin-
orientation (SDSO) process which does not incorporate
drawing or heat treatment, and therein provides a
preferred balance of shrinkage and dyeability behavior
making the polyester fine filaments of the invention
especially suitable~~for replacement of natural
continuous filaments, such as silk. By careful
selection of SDSO process parameters fine filaments
with excellent mechanical quality and uniformity are
made; such that the fine filaments, having shrinkages
less than about 12%, may be used in multifilament
direct-use yarns (DUY) and processed without forming
broken filaments in high speed weaving and knitting;
and filaments, having shrinkages preferably greater
than about 12%, may be used in multifilament draw-feed
yarns (DFY) in high speed textile draw processes, such
as friction-twist texturing, air-jet texturing,
stuffer-bax crimping and warp-drawing, without forming
broken filaments.
The fine filaments of this invention are
characterized by having excellent mechanical quality
permitting yarns made from these filaments to be used
in high speed textile processes, such as draw false-
twist and air-jet texturing, warp drawing, draw gear
WO 92/13119 2 ~ g PGT/US92100359
- 24 __
and stuffer-box crimping, and air and water jet weaving
and warp knitting, without broken filaments; and the
filaments of this invention are further characterized
by having excellent denier uniformity (as defined
herein by along-end denier spread, DS) permitting use
in critically dyed fabrics. The filaments of this
invention may be used as filaments in draw feed yarns
(and tows), preferably filaments having boil-off
shrinkage (S) and dry heat shrinkage (DHS) greater than
about 12% are especially suitable for draw feed yarns;
and filaments of this invention, having shrinkages less
than about 12%, are especially suitable flat untextured
multifilament yarns, and as yarns for such texturing
processes as air-jet texturing, gear crimping, and
stuffer-box crimping, wherein, no draw need be taken,
and the flat and textured filaments of this invention
may be cut into staple fibers and flock; but the
filaments with shrinkages less than about 12% may be
uniformly cold drawn as described by Knox and Noe in U.
S. Patent No. 5,066,447.
In contrast to the polyester fine filaments
prepared according the invention, Pine filaments made
by such spinning technologies, which incorporate, fox
example, aerodynamic or mechanical draw and/or heat
treatment steps for the reduction in filament denier
and/or for the increase in molecular orientation and/or
crystallinity, which are generally characterized by: 1)
high shrinkage tension (STmax) greater than about 0.2
g/d; 2) peak shrinkage tension occurring at
temperatures, T(STmax). greater than about 100°C (i.e.,
greater than atmospheric dyeing temperatures); 3) dry
heat shrinkage (DHS) which increases with treatment
temperature over the normal textile dyeing and
finishing temFerature range of about 100°C to about
180°C (that is, having a d(DHS)/dT > 0 for T = 100°C to
WO 92113119 ~ ~ ~ ~'~ ~ ~ PCT/US92/00359
- 25
180°C) and a differential shrinkage, (DS = DHS-S),
greater than about +2%, where S is the boil-off
shrinkage and DHS is the dry heat shrinkage, and
thereby requiring high temperature treatments of the
polyester fine filaments, or textile products made
therefrom, prior to, or after dyeing, to impart
sufficient thermal dimensional stability to the textile
fabrics made from these fine filaments; and 4) inferior
dyeability, requiring dyeing under pressure at high
temperatures with chemical dye assists, called
carriers, to achieve deep shades and uniform dyed
fabrics.
In particular, according to the present
invention, there are provided:
1. Spin-oriented polyester fine filaments of
about 1 dpf or less, preferably less than about 0.8
dpf, especially less than about o.6 dpf, and,greater
than about 0.2 dpf; wherein said polyester is of
relative viscosity (LRV) in the range of about 13 to
about 23, with a zero-shear polymer melt temperature
(TMo) in the range of about 240°C to about 265°C, and
polymer glass transition temperature (Tg) in the range
of about 40°C to about 80°C; and said filaments are
further characterized by:
(a) a shrinkage differential, (DS = DHS-S),
less than about +2%, preferably less than about +1%,
and especially less than about 0%; wherein, S is boil-
off shrinkage and DHS is dry heat shrinkage measured at
180°C,
(b) a maximum shrinkage tension, (STmax),
between about 0.05 and about 0.2 g/d, with the peak
temperature of maximum shrinkage tension, T(STmax)
between about (Tg+5°C) and about (Tg+30°C); i.e.,
WO 92/13119 ~ . PCT/US92/00359
- 26
between about 75°C and about 100°C for polyethylene
terephthalate) with a polymer Tg of about 70°C;
(c) a tenacity-at-7%-elongation (T~) in the
range of about 0.5 to about 1.75 g/d and a [(Tg)n/T7])-
ratio at least about (5/T7); preferably at least about
(6/T7), wherein, (Tg)n is the tenacity-at-break
normalized to a reference LRV of 20.8 and percent
delusterant (such as T102) of 0%, defined by: (Tg)n =
(Tg)[20.8/LRV)0~~5](1-X)-4% where tenacity-at-break,
(Tg) - T(1+Eg/100); Eg, the percent elongation-at-
break, is between about 40% and about 160%; X is the
fractional weight percent of delusterant; and T is the
tenacity defined as breaking load (grams) divided by
original undrawn denier;
(e) an average along-end denier spread (DS)
of less than about 4%, preferably less than about 3%,
and especially less than 2%.
2. Spin-oriented fine filaments, especially
suitable as use as draw feed yarns (DFY), such as for
high speed draw false-twist and air jet texturing, draw
warping, draw crimping and stuffer-box texturing,
wherein, said filaments are further characterized by:
(a) boil-off shrinkage (S) and dry heat
shrinkage (DHS) greater than about 12% and less than
about the maximum shrinkage potential, (SM = [(550-
Eg)/6.5])%, and for elongation-at-break (Eg) in the
range of about 80% to about 160%;
(b) tenacity-at-7% elongation (T7) in the
range of about 0.5 to about 1 g/d.
3. spin-oriented fine filaments, especially
suitable for use as direct-use yarns (DUY), are further
characterized by:
WO 92/13119 ~ ~ ~ ~ ~ Z~ . 'PGT/US92/00359
(a) boil-off shrinkage (S) and dry heat
shrinkage (DHS) between in the range of about 2% to
about 12%, preferably in the range of about 6% to about
12% for woven and preferably in the range of about 2%
to about 6% for knits, such that the filament denier
after boil-off, dpf(ABO) = dpf(BBO)x[(100/(100-S)], is
in the range of about 1 to about 0.2 dpf, preferably in
the range of about 0.8 to about 0.2 dpf, and especially
in the range of about 0.6 to about 0.2 dpf;
(b) tenacity-at-7%-elongation (T7) in the
range of about 1 to about 1.75 g/d with an elongation-
at-break (Eg) in the range of about 40% to about 90%;
(c) a post-yield modulus (Mpy), as defined by
the secant tan B in FIG. 5 (that is, Mpy =
(1.2T20 -1.07T7)/0.13), in the range of about 2 to
about 12 g/d.
4. Spin-oriented fine filaments, capable of
being cold drawn without heat setting to provide
textile filaments, as further characterized by:
(i) a boil-off shrinkage (S) and dry heat
shrinkage (DHS) less than about 12%;
(ii) an onset of cold crystallization, Tcc
(DCS), of less than about 105°C, as measured by
differential scanning calorimetry (DSC) at a heating
rate of 20°C per minute;
(iii) an instantaneous tensile modulus, Mi
(= d(stress)/d(elongation)]x100, greater than about 0;
wherein [d(stress)/d(elongation)] is the tangent to a
plot of stress (grams per drawn denier) versus percent
elongation; and wherein draw stress is the draw force
(grams) divided by the drawn denier, where the drawn
denier is defined the ratio of the undrawn denier and
WO 92/13119 ~ ~ ~ ~ ~ ~ ~ PCT/US92l00359
28
the residual draw-ratio, (RDR = 1+Eg~%/100);
The shrinkage (S) of said drawn filaments may
be reduced, if desired, without significant loss in
dyeability provided that the post heat set temperature
(Teat) is less than about the temperature at which the
shrinkage tension undergoes no significant further
deduction with increasing temperature; that is, it is
preferred to maintain Tset less than about the
temperature at which the onset of rapid (re)-
crystallization begins. The maximum value for Tset, is
herein, defined as the temperature, at which the slope,
[d(ST)/dT], of a shrinkage tension versus temperature
spectrum abruptly decreases in value (becoming less
negative) - see FIG. 11.
5. Preferred drawn yarns made by drawing the
said sgin-oriented filaments of this invention and said
drawn yarns are characterized by:
(a) denier per filament after boil-off
shrinkage, dpf(ABO), in the range of about 1 to about
0.2 dpf, and preferably in the range of about 0.8 to
about o.2 dpf;
(b) boil-off shrinkages (S) and dry heat
shrinkages (DHS) in the range of about 2% to about 12%,
preferably in the range of about 2% to about 6% for
knits, and in the range of about 6% to about 10% for
wovens;
(c) tenacity-at-7%-elongation (T~) at least
about 1 g/d, such that the [(Tg)n/T~]-ratio is at least
about (5/T7); preferably at least about (6/T~),
wherein, (Tg)n is the tenacity-at-break normalized to a
reference LRV of 20.8 and percent delusterant (such as
Ti02) of 0%, and having an Eg in the range of about 15%
to about 55%;
WO 92/13119 PCT/US92/00359
29
_201788
(e) post-yield modulus (Mpy) in the range of
about 5 to about 25 g/d;
(f) relative disperse dye rate (RDDR),
normalized to 1 dpf, of at least about o.i, and
preferably at least about 0.15;
(g) a dynamic loss modulus peak temperature,
T(E"max) less than about 115°C; and preferably less
than about 110°C;
(h) an average along-end denier spread (DS)
of less than about 4%, preferably less than about 3%,
especially less than about 2%.
6. Bulky fine filament yarns (or tows) are
provided by passing the fine filament yarns of this
invention through a bulking process, such as air-jet
texturing, false-twist texturing, stuffer-box and gear
crimping; wherein, said bulky filaments are
characterized by having individual filament deniers
(after shrinkage) less than about 1, preferably less
than about 0.8, with boil-off shrinkage (S) and dry
heat shrinkage (DHS) less than about 12% and
characterized by a T(E"max) of less than about 115°C,
preferably less than about 110°C, and a RDDR of at
least about 0.1, and preferably at least about 0.15.
Especially preferred filaments for use in
direct-use yarns (or tows) are also characterized by:
(a) an average crystal size (CS), as measured
from the 010 plane by wide-angle x-ray scattering
(WAXS), between about 50 and about 90 angstroms
with a fractional volume crystallinity, Xv =
(pm -1.335)/0.12, between about 0.2 and about 0.5 for
density values (pm) between about 1.355 and about 1.395
grams/cm3, corrected for percent delusterant;
WO 92/13119 , 3~ PCT/US92/00359
2~~ii788
(b) an fractional average orientation
function, f = Gn/Gn° (where ~n° is the average
intrinsic birefringence (defined herein with a value of
0.22), between about 0.25 and about 0.5, with a _ a
fractional amorphous orientation function, fa =
(f-Xvfc)/(1-Xv)), less than about 0.4, preferably less
than about 0.3, wherein (fin) is the average r
birefringence and fc is the fractional crystalline
orientation function, fc = (180-COA)/180, where COA is
the crystalline orientation angle as measured by WAXS;
(c) an amorphous free-volume (Vf~am) of at
least about 0.5x106 cubic angstroms ($r3), preferably at
least about 1x106 ~3, where Vf~am is defined herein by
(CS)3[(1-Xv)/Xv)][(1-fa)/fa], providing a dynamic loss
modulus peak temperature, T(E"max). less than about
115°C, and preferably less than about 110°C;
(d) an atmospheric relative disperse dye rate
(RDDR), normalized to 1 dpf, of at least about 0.1, and
preferably at least about 0.15.
The yarn characteristics are measured as in
U. S. Patent NOS. 4,134,882, 4,156,071, 8nd 5,066,447;
except the relative disperse dye rate (RDDR) is
normalized to 1 dpf, dry heat shrinkage (DHS) is
measured at 180C, and the lab relative viscosity (LRV)
is defined according to Broaddus in U. S. Patent No.
4,712,998 and is equal to about (HRV - 1.2), where HRV
is given in U. S. Patents Nos. 4,134,882 and 4,156,071.
The value of LRV20.8 is taken as the reference LRV of
the polyester polymer of equal zero-shear "Newtonian"
melt viscosity r~o to that of 20.8 LRV 2GT homopolymer
(e.g., providing for the same capillary pressure drop '
at the same mass flow rate and temperature). In Tables
I through VIII, alphanumerics which are "raised to the
power" of a number is expressed using the symbol '~""
WO 92/13119 ~ ~ ~ ~ ~ ~ ~ 31 PCT/11S92/00359
(such as 102 = 10"2); very small or very large numbers
(such as 0.00254 cm and 254000 cm/min, for example) are
expressed, for convenience as 0.254 and 254 where the
units are given as "cm x 10"2" and "cm/sec x 10'-3,
respectively; dashes (---) in the place of a number
denotes that the value was not measured; "NA" in the
place of a number denotes that the measured value is
not applicable; and dashed arrows (----->) are used to
denote values of a given parameter for a given item is
the same as that of the preceeding item. Spin speed
(V) was measured in yards/minute and have been
converted in the text to km/minute, rounded to the
second decimal place (e.g., 4500 ypm = 4.115 km/min =>
4.12).
The preferred embodiments of this invention
are illustrated by the following examples:
Polyethylene terephthalate) having a polymer
LRV in the range of about 13 to about 23 (which
corresponds to an [r;] in the range of about 0.5 to
about 0.7), preferably in the range of about 13 to
about 18 for sonically modified polyesters, and in the
range of about 18 to about Z3 for nonionically modified
polyesters, a zero-shear melting point (TM°) in the
range of about 240°C to about 265°C, and a glass-
transition temperature (Tg) in the range of about 40°C
to about 80°C, and containing minor amounts of
delusterants and surface friction modifiers (e. g., Ti02
and Sio2), is melted at a polymer temperature Tp (°C)
and filtered through inert medium for a residence
(hold-up) time (tr, min) and then extruded through
spinneret capillaries of diameter (DgND) with length
(L) at a capillary mass flow rate w [_ (dpf~V)/9],
g/min] providing an apparent capillary shear rate (Ga,
sec-1 = [(32/60~)(w/p)/D~D3)], where capillary
dimensions are expressed in units of centimeters and
WO 92/13119 32 PCTlUS92/00359 ,
the withdrawal spin speed (V) in units of km/min.
The filaments of most of the examples herein
were spun from spinnerets having a filament density per
extrusion surface area in the range of typically about
2.5 to about 13, while it was possible to spin and
quench filament bundles with a extrusion filament
density as high as about 25 provided capillary hole
pattern (filament array) was optimized for the type of
quench (i.e., radial vs, cross-flow) and length/profile
of the initial delay quench "shroud" and air velocity
profile (see Example T); wherein the extrusion filament
density is defined by the ratio of the number of
filaments (~c) divided by the extrusion surface area
(Ao),(i.e., ~c/Ao,cm-2), into a "shroud" which protects
the freshly extruded filaments from direct quench air
for a distance at least about 2 cm and not greater than
about (l2dpf~,cm); and then carefully cooled to a
temperature less than about polymer Tg, preferably by
radially directed air having a temperature Ta:(herein
about 22°C) less than about the polymer Tg (herein Ta
was about 70°C for 2GT homopolymer) and of linear
velocity Va (m/min) in the range of about 10 to about
m/min. Suitable spinning apparatus used are
essentially as that described in U. S. Patent Nos.
25 4,134,882, 4,156,071, and 4,529,368.
The along-end denier spread (DS) and draw
tension variation (DTV) were minimized by balancing the
values for the delay quench length (LDQ), the quench
air temperature (Ta), the quench air flow rate (Va),
30 and the convergence length (Lc), while selecting Tp for
spinning continuity. Increasing the polymer spin
temperature (Tp) (but less than about [(TM )a + 55°C]
usually increases spinning continuity and mechanical
quality (i.e., Tg, g/d), but usually decreases along-
end uniformity and increases shrinkage. To minimize
WO 92/13119 ' 2 ~ ~ ~,'~ $ ~ 33 PCT/US92/00359
loss of along-end uniformity while spinning at elevated
temperatures (Tp), as required for mechanical quality,
heat can be imparted to the extruded filaments through
use of high shear rate (Ga) capillaries (that is, small
diameter capillaries). However, the spinning
operability unexpectedly deteriorated when high shear
capillaries are used with high L/D~D ratios, such as
use of a 9x50 mil capillary (see Example III). It is
conjectured that at these low capillary mass flow rates
and high shear conditions, incipient shear-induced
molecular ordering ( e.g., lower chain entropy and
possible incipient "nucleation") of the polymer melt
occurs, especially for polymer melt filtered prior to
extrusion for residence times (tr) greater than about 4
minutes, wherein this molecular ordering (possible
incipient nucleation) is believed to increase the
apparent polymer melting point from the zero-shear
value (TMo) to an apparent value (TM)a. This has the
effect of reducing the spin temperature differential,
Tp-(TM)a. To maintain a sufficiently large enough spin
temperature differential, it is found that the bulk
polymer temperature Tp needs to be further increased as
given by the amount defined by the expression:
2x10-4(L/DgHD)Ga,°C, for the selected values of L,
DgND, and Ga.
To obtain a balance of spinning continuity,
mechanical quality and along-end uniformity, the
apparent internal spinline stress (Qa) at the "neck-
point" is controlled in the range of about 0.045 to
about 0.195 g/d while controlling the melt extension
strain ea in the range of about 5.7 to about 7.6. The
attenuated and cooled filaments are converged into a
multifilament bundle and withdrawn at a spinning speed
(V, km/min) as defined by the surface speed of the
first driven roll. The external spinline tension
CA 02101788 2001-06-20
WO 92/13119 PCT/US92/00359
34
arising from frictional surfaces (and air drag) is
removed prior to packaging by slightly over feeding the
spinline between the first driven roll and the windup,
usually between about 0.5t and 5~. Finish is applied
at the point of convergence and interlace is provided,
preferably after the first driven roll. The values for
finish-on-yarn (weight, t) and degree of filament
entanglement (RIaC) are selected to meet end-use
processing needs.
Polyester fine filaments of the invention are
of good mechanical quality and uniformity having a
linear density less than about of that of natural worm
silk, but greater than that of spider silk, that is
between about 1 and about 0.2 denier per filament, and t
having the capability of being uniformly dyed without
use of high temperatures and chemical dye assists; that
is, more akin to~ that of natural silks.
Advantageously, if desired, the fine denier
filament yarns may be treated with caustic in spin
finish (according to the invention as taught by
Grindstaff and l~eese in United States Patent No. 5,069,844
to enhance their hydrophilicity and improved
moisture-transport and comfort. Incorporating
filaments of different deniers and/or cross-sections
may be used to reduce filament-to-filament packing and
thereby improve tactile aesthetics and comfort. Unique
dyeability effects may be obtained by co-mingling
filaments of differing polymer modifications, such as
homopolymer dyeable with disperse dyes and ionic
copolymers dyeable with cationic dyes.
Fine filaments of lower shrinkage may be
obtained, if desired, by incorporating chain branching
agents, on the order of about 0.1 mole percent, as
WO 92/13119 'Z ~ j~ '~ '~ g g 3~ PGT/US92/00359
described in part in Knox U. S. Patent No. 4,156,071,
MacLean U. S. Patent No. 4,092,229, and Reese in U. S.
Patents Nos. 4,883,032, 4,996,740, and 5,034,174;
and/or increasing polymer viscosity by about +0.5 to
about +1.o LRV units.
The fine filament yarns of this invention are
suitable for warp drawing, air jet texturing, false-
twist texturing, gear crimping, and stuffer-box
crimping, for example; and the low shrinkage filament
yarns may be used as direct-use flat textile yarns and
a feed yarns for air-jet texturing and stuffer-box
crimping wherein no draw is need be taken. The
filaments (and tows made therefrom) may also be crimped
(if desired) and cut into staple and flock. The
fabrics made from these improved yarns may be surface
treated by conventional sanding and brushing to give
suede-like tactility. The filament surface frictional
characteristics may be changed by selection of cross-
section, delusterant, and thraugh such treatments as
alkali-etching. The improved combination of filament
strength and uniformity makes these filaments,
especially suited for end-use processes that require
fine filament yarns without broken filaments (and
filament breakage) and uniform dyeing with critical
dyes .
The fine denier filament polyester yarns of
the invention are especially suitable for making of
high-end density moisture-barrier fabrics, such as
rainwear and medical garments. The surface of the knit
and woven fabrics can be napped (brushed or sanded).
To reduce the denier even further, the filaments may be
treated (preferably in fabric form) with conventional
alkali procedures. The fine filament yarns, especially
those capable of being cationic dyeable, may also be
used as covering yarns of elastomeric treatments yarns
WO 92/13119 ~ ~ Q , . 3S PCT/US92/00359
(and strips), preferably by air entanglement as
described by Strachan in U. S. Patent No. 3,940,917. ..
The fine filaments of the invention may be co-mingled
on-line in spinning or off-line with higher denier
polyester (or nylon) filaments to provide for cross-
dyed effects and/or mixed shrinkage post-bulkable
potential, where the bulk may be developed off-line,
such as over feeding in presence of heat while
beaming/slashing or in fabric form, such as in the dye
bath. The degree of interlace and type/amount of
finish applied during spinning is selected based on the
textile processing needs and final desired yarn/fabric
aesthetics.
The process of this invention and the product
made therefrom is further illustrated by the following
examples:
Yarns of 100 and 300 filaments of nominal 0.5
dpf were spun from polyethylene terephthalate) of 19
LRV (corresponding to about 0.60 (r~]) and containing
0.3 weight percent c~f Ti02. The 300-filament yarns
were spun using spinnerets of varying construction;
e.g. so to provide: (i) 2 or more capillaries from a
single counterbore without inter-filament fusion by
controlling the capillary-to capillary distance greater
than about 40 mils (1 mm); (ii) 300 "equally-spaced"
single capillaries; and (iii) 300 capillaries arranged
in concentric rings occupying about "initially" 50% of
the "outer" half of the available extrusion surface
area (Ao) so to increase the effective extrusion
filament density (EFD) from about 12.5 to about 25;
however, immediately after extrusion the polymer melt
streams of spinneret (iii) converge to form a conical
bundle similar to that of spinnerets (i) and (ii); and
WO 92/13119 ~ ~ ~ 3, , ; PCT/US92/00359
therebyhaving an effective extrusion filament density
(EFD) on the order of that for the spinneret
constructions (i) and (ii); i.e. less than 25 and
larger than, 12.5, where the effective extrusion
a
filament density (EFD) for such non-equally distributed
filament configurations is experimentally determined
following the graphical procedure in Figure 14.
Experimentally, filaments equally spaced over the
entire extrusion area and filaments spaced on the
perimeter in concentric rings are found to have about
the same effective filament extrusion density since the
filaments bundles, immediately after extrusion, assume
similar configurations. The data in Table I for the
300-filament yarns were spun with capillaries arranged
in concentric rings occupying initially about 50% of
the available extrusion surface area. The freshly
extruded filaments were cooled to room temperature by
using a radial quench apparatus, essentially as
described in U. S. Patent No. 4,156,071, except for
having a protective "shroud" of length (LpQ) of about 1
inch (2.54 cm) for yarns spun at 3500 ypm (3.2 km/min)
and about 2.25 inches (5.?2 cm) for yarns spun at 4500
ypm (4.12 km/miri). The filament yarns spun at 3500 ypm
(3.2 km/min) had a high boil-off shrinkage (S), making
these yarns especially suitable, for example, as draw
feed yarns (DFY) in draw warping, draw air-jet
texturing, draw false-twist texturing, and draw
crimping. Increasing the spin speed to 4500 ypm (4.115
km/min), decreased boil-off shrinkage (S) to values
less than 12% with a differential shrinkage (OS = DHS-
S) less +2%, a maximum shrinkage tension (STmax) less
than 0.175 g/d at a peak temperatures T(STmax) less
than 100°C, and a yield tenacity (herein approximated
by the tenacity-at-7% elongation, T7) greater than 1
g/d, making these filaments fully suitable for direct-
use applications without requiring additional drawing
WO 92/13119 2 ~ ~ ~ ~ g g PCTlUS92/00359
3g
or heat treatment, such as use as filaments in flat,
air-jet textured and stuffer-box crimped textile
filament yarns.
It was observed that the filaments spun from
spinneret capillaries with a cross-sectional area (Ac)
of 176.8 mils2 (0.1140 mm2, 1.14x10-3 cm2) had a lower
tenacity-at-break (Tg) than the filaments spun from
spinneret capillaries with an Ac of 28.3 mils2 (.0182
mm2, 1.82x10-4 cm2). The lower tenacity of the yarns
of this Example I, is also ,in part, due to the lower
polymer LRV (19 vs. 20.8). The normalized values for
Tg (denoted herein by (Tg)n) are defined by the product
the measured tenacity-at-break (TB) and the factor
(20.s/LRV)0~75(1-X)-4 which for these yarns is about
1.057; thereby, the normalized break tenacities (TB)n
are about 6% higher when compared to reference LRV and
% Ti02 of 20.8 and 0%, respectively.
The fine filament yarns of this example were
capable of being dyed to deep shades at atmospheric
conditions (100°C) without use of dye carriers as given
by an Relative Disperse Dye rate (RDDR)-value
(normalized to a 1 dpf) of about 0.16 versus an RDDR-
value of 0.055 for a conventional fully drawn yarn.
To provide yarns of fewer filaments (and
lower denier), it is possible to split, for example,
the 300-filament yarn bundle into 2,3 or 4 individual
bundles of 150, 100, and 75-filament yarn bundles,
respectively, preferably by use of metered finish tip
separating guides at the exit of the radial quench
chamber. Multi-ending permits a higher mass flow rate
(w) through the filter pack cavity and thereby reducing
the residence time (tr) in the pack cavity per
threadline.
WO 92!13119 ~ ~ ~ ~ ~ ~ $ 39 PCT/US92l00359
EBAMPLE II
Fine filaments were spun from polyethylene
terephthalate) of nominal 20.8 LRV (about 0.65 [r~]) and
containing 0.1 weight percent Ti02 at a withdrawal
speed (V) of 4000 ypm (3.66 km/min) using a radial
quench apparatus, essentially as described in Example
I, except for having a delay "shroud" length (LDQ) of
about 2.25 inches (5.72 cm). Examples II-5 and II-6
had poor operability and no yarn was collected. The
low apparent shear rates (Ga) for the 0.5 dpf filaments
spun at 4000 ypm (3.66 km/min) using 15x60 mil
(0.38x1.52 mm, 0.038x0.152 cm) capillaries is believed
to contribute to the poor operability and broken
filaments. Even increasing temperatures Tp to about
299°C did not provide an acceptable process.
Temperatures higher than 299°C-300°C were not tried
because of the concern for poor along-end denier
uniformity. Process and product details are~summarized
in Table I.
ZO EXAMPLE III
In Example III, 68-and 136-(unplied and
plied) filament yarns were spun, essentially according
to Example I, except convergence was by a metered
finish tip as described in U. S. Patent No. 4,926,661
for Examples III-1 through III-9 and III-il through
III-25. Example III-10 used a metering finish roll
surface to converge the filaments as described in
Examples I and II. Other process details are
summarized in Tables I and II. The filaments of
Example III-1 through III-5 and III-12 through III-15
have T7-values greater than about l g/d making them
especially suitable for use as filaments in direct-use
textile filament yarns and as feed yarns in air-jet
textured, wherein no draw is taken; and, if desired,
CA 02101788 2001-06-20
WO 92/13119 PCT/US92/00359
can be drawn uniformly without heat (cold) in warp
drawing (and air-jet texturing) as described in Knox
and Noe U. S. Patent No. 5,066,447. The filaments of
III-6,7, and I7:I-16 through III-25 with T7-values less
5 than about 1 g/'d are especially suitable as filaments
in draw feed yarns (DFY) , such as draw !alas-twist
texturing (FTT) and draw air-jet texturing (AJT) or as
draw feed yarns in warp drawing.
In Examples III-1 through III-5, 50 denier
10 68-filament yarns were spun from a single pack cavity
and plied at the convergence guide to give a 100 denier
136-filament yarns of excellent mechanical quality.
Example III-4, for example, had a spinning continuity
of 0.39 breaks per 1000 lbs. (0.86 per 1000 kg) which
15 is equivalent t.o about 9.5 breaks per 109 meters. The
yarns of Example III-4 were wound with about 10 cm
interlace (as measured by the rapid pin count procedure
described in U. S. Patent No. 3,290,932) forvair-jet
texturing on a Barnia~;TM FK6T-80 without drawing and wound
ZO with about 5-7 RPC interlace for direct-use as a flat
textile yarn in wovens and warp knits. Example III-6
and 7 were drawn without broken filaments at 1.44X and
1.7X, respectively, to give drawn 35 denier 68-filament
yarns. Example III-6 is preferred versus III-7 since
25 the spinning productivity (spun denier x spin speed) of
III-6 is about 25~ greater than Example III-7. Yarns
of Example III-6 were successfully cold warp drawn
using a 1.44X draw-ratio.
It had been anticipated that increasing the
30 L/DgND-ratio of the 9 mil (0.229 mm, 0.0229 cm)
capillary spinnerets from 2.22 to 5.56, as per the
teaching of Frankfort and Knox in U. S. Patent No.
4,134,882, would significantly improve mechanical
quality by providing for increased shear heating of the
35 extruding polymer melt; wherein the degree of capillary
PGT/US92/00359
W(192/13119
shear heating was estimated by the expression in
Frankfort and Rnox: 660(wL/D4)0.685,0~~ wherein D is
given mils, and w is given in lbs./hr.; however, broken
filaments were observed for Examples III-8 and III-11.
Acceptable quality was obtained for Example
,
III-12; wherein the residence time (tr) during
filtration in the pack cavity was reduced by spinning
136-filaments versus 68-filaments. The yarn bundle
could be withdrawn as a~ single 136-filament bundle or
split to wind-up two 68-filament yarn bundles.
Residence times (tr) less than about 4 minutes for high
L/DgND capillary spinnerets are found to be necessary
to spin without having to use high "input" polymer
temperatures (Tp). See Example IX for a more detailed
discussion about the spinning with high shear capillary
spinnerets. In Examples III-12 through III-15, 136-
filament yarns were spun using 136-9x36 mil
(0.229x0.916 mm, 0.0229x0.0916 cm) capillaries per
spinneret, and thereby reducing the filtration
residence time (tr) by 50%, to provide yarns with good
mechanical quality. The high filament count yarns are
especially suitable for draw air-jet texturing (AJT)
and for false-twist texturing (FTT), wherein, a
straight draw-texturing machine configuration is
preferred. Yarns from Examples III-19,22,24 and 25
were used for preparing warp drawn flat yarns of
nominal 0.5 dpf as described in Example XII.
The structural properties of th.: filaments of
Example III-10 ar.e representative of spin-oriented
filaments of this invention having shr'inkages less than
6%. Example III-10 had a density ([p-measured = p
f fiber - 0.0087(%Ti02)] of 1.3667 g/cm3 (corrected for
0.03% Ti02), giving a calculated fractional volume
crystallinity [X~ _ (pm 1.335)/0.12] of 0.264, and a
weight percent crystallinity [Xw = (1.455/pc)Xy] of
WO 92/13119 PCT/US92/00359
42 --1
._
0.281; an average crystal size (CS) of 7o angstroms
an average crystal orientation angle (COA) of 12
degrees which corresponds to a crystal orientation
function [fc = (180-COA)/180] of 0.93; an average
birefringence (fin) of 0.0?44 giving an average
orientation function [f = ~n/0.22] of 0.34 and an
amarphaus orientation function [fa = (f-Xvfc)/(1-Xv)7
of o.13 and an amorphous free-volume [(Vf~am) _
[(1-Xv)/Xv][(1-fa)/fa]CS3] of about 6x106 cubic
angstroms (~3). The filaments of this example also had
a differential birefringence (~g5-5) of 0.0113, an Niso
of 1.5882, a sonic velocity (SV) of 2.72 km/sec giving
a sonic modulus (Mson) of 83.6 g/d, a maximum shrinkage
tension (STmax) of 0.143 g/d at a peak temperature,
T(STmax), of 80°C, a boil-off shrinkage (S) of 4.6%,
giving a shrinkage modulus [Ms = (STmax/S)100] of 3.1
g/d, a dry heat shrinkage (DHS) of 5.0% to give a
differential shrinkage (OS = DHS-S) of less than +1%,
an initial modulus of 71.6 g/d with a post-yield
modulus (Mpy) of 5.35 g/d, and an uncorrected disperse
dye rate (DDR) of 0.144 and relative disperse dye rate
RDDR, norrdalized to, 1 dpf, of about 0.104.
ALE I0
Polyethylene terephthalate) of nominal 21.2
LRV (about o.66 [r1]) of 0.035, 0.3 and 1 weight percent
Tio2 were spun using a radial quench spinning
apparatus, essentially as described in Example I,
except the length (LDQ) of the delay "shroud" was about
2-5/8 inches (6.7 cm), and the filament bundles were
converged by a metered finish tip at 43 inches (109 cm)
from the face of the spinneret. Other process details
are summarized in Tables III and IV. Increasing weight
percent Ti02 is observed to decrease the tenacity-at-
N-~~-~ r UO
WO 92!13119 PCT/US92/00359
43
break (Tg) of these fine filaments. The amount of Ti02
is usually varied between about 0.035% for minimum
yarn-to-metal and yarn-to-yarn frictional needs and
less than about 1.5%, more typically less than about 1%
for desired mechanical quality and visual aesthetics.
EBAMPLE 0
Polyethylene terephthalate) of nominal 21.1
LRV (about 0.655 [r;]) and containing 0.3 weight percent
Tio2 was spun using apparatus similar to Example IV.
Examples V-1 through V-4, IV-9 and IV-10 use 12x50 mil
(0.305x1.270 mm, 0.0305x0.127 cm) spinneret
capillaries. Examples V-5, 7, 8, and 11 through 13 use
9x36 mil (0.229x0.914 mm, 0.0229x0.0914 cm) spinneret
capillaries, and Example V-6 uses 6x18 mil (0.152x0.457
mm, 0.0152x0.0457 cm) spinneret capillaries to spin
100-filament 85 denier feed yarns for warp draw and
draw air-jet texturing (AJT). The length of delay
quench (LDQ) was increased from 2-5/8 inches (6.7 cm)
to 4-5/8 inches (11.7 cm) in EX. V-8 and V-10.
Increasing the length of delay (LDQ), increased along-
end non uniformity 4X and interfilament denier non
uniformity, as measured optically from yarn bundle
cross-sections, by 2X. When the delay length (LDQ) is
less than about (l2dpf~)cm, good uniformity may be
obtained.
Example V-7 was repeated for Examples V-11
through V-13 at 2400, 3000, and 3500 ypm (2.2, 3.05,
and 3.35 km/min); wherein, the capillary mass flow rate
(w) was varied to spin a draw feed yarn such that the
spun dpf would be drawn to a final denier of about 0.5
dpf [where, the drawn dpf = spun dpf/draw ratio = spun
dpf x (drawn yarn RDR/spun yarn RDR), where the
WO 92/13119 j r ; ;"~ ..~~..~ ~ . PCT/US92/00359
44
residual draw-ratio, RDR = (1+ EB,$/100)J. Examples V-
11 through V-13 have tenacity-at-7%-elongation (T~)
values less than about 1 g/d making them especially
suitable as draw feed yarns even though the shrinkages
of the undrawn yarns were less than 12%. The results
of the warp drawing are summarized in Example VII. ,
ALE vi
In Example vI, Example V-13 was repeated at
3300 ypm (3.02 km/min) for varying spun deniers, delay
quench lengths (LDQ), spinning temperatures (Tp), and
convergence guide lengths (L~). Example VI-2, with a
denier spread (DS) of 3.8% was successfully drawn 1.35X
to give a drawn 0.3 dpf 100-filament yarn with a 2.3%
denier spread, tenacity of 4.4 g/d, Eg of 32.5% and a
boil-off shrinkage(S) of 6.3%. In this example it was
observed that as total yarn bundle denier and
individual filament denier is reduced, the along-end
unifarmity deteriorates unless the process is :re-
balanced. Increasing polymer temperature to insure
good spinning continuity at these low mass flow rates
is required. The along-end denier spread (DS) was
improved from 12.1% (EX. VI-1) to less than 4% by
reducing the delay length (LDQ) to about 2.9 cm and
decreasing the convergence length (L~) from 109 cm to
81 cm. For yarns with dpf less than 0.5 it is
difficult to achieve the same DS-values as fox those of
0.5 to about 1 dpf. Process and product details are
summarized in Tables III and IV.
ERAMpLE VII
Fine trilobal filaments were spun from
polyethylene terephthalate) of nominal 21 LRV (about
0.65 [rp] containing 0.035 weight percent Ti02 using .
spinnerets with 9x36 mil (0.229x0.914 mm, 0.0229x0.0914
WO 92/13119 '~ ~ ~ ~ "~ g ~ 45 PCT/US92/00359 .
cm) and 12x50 mil (0.305x1.270 mm, 0.0305x0.127 cm)
metering capillaries and a Y-shaped exit orifices of
area (Ac) of about 197 mils2 (1.27 mm2, 0.0127 cm2),
which corresponds to a DgND of about 15.9 mils (0.40
mm, 0.04 cm) with an L/DgNp of about 1.5 (as
essentially as described in Examples 45-47 of U. S.
Patent No. 4,195,051). The 9x36 mil metering
capillaries provided better mechanical quazity and
along-end denier uniformity than the 12x50 mil metering
capillaries. The 100-filament yarns could be drawn
without forming broken filaments to nominal 50 denier,
or about 0.5 dpf.
EXAMPLE VIII
Polyethylene terephthalate) polymer modified
with about 2 mole % of ethylene 5-sodium-sulfo
isophthate having a nominal LRV of about 15.3 was spun
using a laminar cross-flow quench apparatus with a 2.2
inches (5.6 cm) delay, essentially as described in U.
S. Patent No. 4,529,638, and converging the filament
ZO bundle at about 43-inches (109 cm) with metered finish
tip guides. The lower LRV is usually preferred for
ionically modified polyesters because the ionic sites
act as cross linking agents and provide higher melt
viscosity. The 15 LRV used, herein, had a melt
viscosity about that of a 20 LRV homopolymer. If,
however, one wanted to spin low LRV homopolymer, then
typically it is advantageous to add viscosity builders,
such as tetra-ethyl silicate (as describes, in Mead and
Reese, U. S. Patent No. 3,335,211). It is generally
preferred to spin ionically modified polyesters with
LRV in the range of about 13 to about 18 and
nonionically modified polyesters with LRV in the range
of about 18 to about 23. Withdrawal speeds were
increased from 2400 ypm (2.2 km/min) to 3000 ypm (2.74
km/min). As expected the cationic copolymer yarns had
WO 92/13119 ~ ~ ~ ~ ~ ~ ~ ' P~/US92/00359
46
lower Tg-values based on their lower LRV. The lower
LRV is preferred for filaments yarns used in napped and
brushed fabrics and for tows to be cut into flock. The
as-spun yarns could be drawn without breaking filaments
to about 50 denier 100-filament yarns. The
canonically modified polyester had a RDDR value of -
0.225 versus 0.125 for the 2GT homopolymer spun under
similar conditions.
Polyethylene terephthalate) of nominal 21.9
LRV (about 0.67 [r;J) and Containing 0.3 weight percent
Ti02 was spun using apparatus similar to Example IV
with a air flow rate of about 30 m/min. Examples IX-1
through IX-3 use 12x50 mil (0.305x1.270 mm,
0.0305x0.127 cm) spinneret capillaries; Examples IX-4
through IX-8 use 9x36 mil (0.229x0.914 mm,
0.0229x0.0914 cm) spinneret capillaries; and-.Examples
IX-9 through IX-il use 6x18 mil (0.152x0.457 min,
0.0152x0.0457 cm) spinneret capillaries to spin nominal
50 denier loo-filament low-shrinkage yarns suitable as
direct-use textile yarns for warp knits and wovens and
as feed yarns for air-jet and stuffer-box texturing
wherein no draw is required.
It was expected that mechanical quality would
improve by increasing the capillary shear rate (Ga) as
taught by Frankfort and Knox in U. S. Patent No.
4,134,882. This improvement was observed for the 9x36
mil capillaries vs. the 12x50 mil capillaries; however,
unexpectedly, higher polymer temperatures were required
to spin with the 6x18 mil capillaries. From
calculations of polymer temperature increase due to the
higher shear rate (Ga), of the 6x18 mil capillaries, it
was expected the 6x18 mil capillaries would actually
require lower polymer temperatures (Tp) than that for
WO 92/13119 ~ ~ ~ ~ 4' PGT/US92/00359
the 9x36 and 12x50 mil capillaries, as per the teaching
of Frankfort and Knox. However, it was necessary to
increase polymer temperature by about 5-6°C to provide
acceptable spinning continuity for the high shear 6x18
mil capillary spinnerets. It is speculated that at
these low mass flow rates (w), the higher shear of the
6x18 mil capillaries induces molecular ordering of the
polymer melt and may even induce nucleation with the
effect of increasing the apparent polymer melting point
(TM)a as represented by the following empirical
expression for (TM)a as a function of capillary shear
(Ga): that is, (TM)a a TMo + 2x10-4[(L/DgND)(Ga),°C.
The differential polymer spin temperature, defined
herein by:
(TP"(TM)a7 = ((Tp-TMo)-(2x10-4 (L/DgND)Gal~
is effectively reduced as the product of the apparent
shear rate (Ga) and L/DgHD-ratio is increased) and
thereby requiring an increase in polymer temperature Tp
to maintain a minimum differential spin temperature at
least about 25°C and, preferably at least about 30°C
for spinning continuity. This is contrary to what is
expected from the teachings of Frankfort and Knox.
Process and product results are summarized in Tables IV
and V.
EBAMPLE 8
Polyethylene terephthalate) of nominal 21.9
LRV (about 0.67 (r~]) and containing 0.3 weight percent
Ti02 was spun using apparatus similar to Example IV
with an air flow rate varied from about 11 to about 30
m/min. Examples X-1 through X-9 use 12x50 mil
(0.305x1.270 mm, 0.0305x0.127 cm) spinneret capillaries
and Examples X-10 through X'16 use 9x36 mil
(0.229x0.914 mm, 0.0229x0.0914 cm) spinneret
WO 92/13119 '~ 1 ~ ~'~ ~ ~ ~ , PCT/US92I00359
48
capillaries to spin nominal 70 denier 100-filament low-
shrinkage yarns with T~-values greater than about 1
g/d, making these especially suitable as direct-use
textile yarns for warp knits and wovens and as feed
yarns for air-jet and stuffer-box texturing wherein no
draw is required. It was observed that mechanical
quality improved with higher polymer temperatures, and
lower air flow rates. Changing the convergence guide
distance Lc had little effect on mechanical properties,
as has been observed for higher dpf filaments (Bayer
German Patent No. 2,814,104). Unfortunately the
process changes which improve mechanical quality caused
a deterioration in the along-end denier uniformity.
Successful spinning of fine filaments with both good
mechanical quality and denier uniformity requires a
balance between "hot" polymer-for mechanical quality
and "rapid" cooling of polymer far uniformity. This in
contrary to the teachings of Frankfort and Knox which
wherein the combination of "hot" polymer with slow
quenching by use of low quench rates, delay shrouds,
and/or heated delay quench were used to provide for
good quality filaments of deniers greater than 1.
Balancing higher "input" polymer temperatures (Tp) with
shear heating via smaller diameter capillary spinnerets
and rapid quenching via short delay lengths (LDQ)
permits, in general, a better balance of yarn
properties. Shortening the convergence length (Lc)
improved the uniformity and a reduction in winding
tensions as a result of lower air drag. At the higher
spun deniers of Frankfort and Knox, no significant
improvements are found for shortening the convergence
length. Process and product results are summarized in
Tables V and VI.
WO 92/13119 PCT/US92/00359
49
EgAMPhE 8I
The fine filament feed yarns of Example V-11,
12, and 13 were uniformly drawn cold and at 155°C at
1.45X, 1.5X, and 1.55X draw-ratios, respectively, to
give nominal 50 denier 100-filament~drawn yarns that
can be used as flat textile yarns. The drawn fine
filament yarns have excellent mechanical quality and
along-end denier uniformity with boil-off shrinkages
(S) less than_about 6~. The cold drawn yarns had
slightly less shrinkage than the hot drawn yarns and
also were slightly more uniform. With less interlace
levels and a different finish, these yarns may be cold
drawn air-jet textured, consistent with the teachings
of Knox and Noe in U. S. Patent No. 5,066,447. These
fine filament spun yarns could also be used as feed
yarns for draw air-jet/stuffer-box/friction-twist
texturing. Warp draw process and product details are
summarized in Table VII. '
Examples III-20 through 25 were.repeated by
varying spin speed and spun denier to provide draw feed
yarns capable of being drawn to provide 35 denier 68-
filament yarns. Nominal 50 to 60 denier as-spun yarns
with excellent mechanical quality and denier uniformity
were drawn cold and heat set at 160°C to 180°C to
obtain low shrinkage filaments of nominal 0.5 dpf yarns
without loss in mechanical quality and along-end denier
uniformity. Spin process and product details are
summarized in Tables IV and V, and the corresponding
draw process and product details are summarized in
Table VII.
WO 92/13119 PCT/US92/00359
$BAMPI~E BIII
In Example XIII the ability to obtain high T7
fine filament yarns was explored. Spinning apparatus _
similar to that in Example X was used. Polyethylene
5 terephthalate) of nominal 20.8 LRV (0.65 (r~~) _
Containing 0.3 weight percent Ti02 was extruded through
9x36 mil (0.229x0.914 mm, 0.0229x0.0914 cm) spinneret
capillaries and cooled using a radial quench apparatus
as described in Example I, except for having a delay
10 length LDQ of about 2.25 inches (5.7 cm). The cooled
filaments were converged into yarn bundles at a
convergence length (Lc) of about 32 inches (81.3 cm)
from the face of the spinneret by use of metered finish
tip guides. The withdrawal speed (V) was varied from
15 4500 ypm (4.12 km/min) to 5300 ypm (4.85 km/min) to
provide 68 and 100-filament direct-use textile yarns
with T7-values between about 1 and 1.5 g/d. The
process and product details are summarized iri Table VI.
The tensiles of Example XIII were inferior due to use
20 of lower polymer melt temperature (Tp) and higher
quench air flow rates (Va) than in Example X.
ALE 8IV
A 91 denier 100-filament yarn made according
to Example IV was air--jet textured using a Barmag
25 FK6T80 at 300 km/min; wherein, the as-spun yarns were
-drawn cold (about 40~C) at 1.0X, 1.1X, 1.2X, and 1.32X
draw-ratios and sequentially air-jet textured using a
conventional air-jet at 125 lbs./in2 (8.8 kg/cm2) to
provide bulky yarns with filament deniers between about
30 0.7 and 0.9 (before boil-off shrinkage) and between
about 0.77 and 0.94 dpf (after boil-off shrinkage).
The denier of the textured filament yarn, wherein no
draw was taken, showed an increase in yarn denier of
about 11% due to bulk (e.g., filament loops), where the
z1~1~88
W0.92/13119 w 51 PCT/US92/00359
ratio (denier)AJT~(denier)F~T is preferably greater
than about 1.1); however, the filament denier showed no
increase in denier. Textured yarn strengths, as
expected, were lower than that of a drawn flat yarn due
to the filament loops; but are adequate for bulky
fabric end-uses. Even at a 1.32X draw-ratio, giving a
textured yarn with a 27.2% residual elongation
(corresponding to a 1.27 residual draw ratio RDR), the
boil-off (S)and dry heat (DHS) shrinkages were only
about 12.7% and 11%, respectively, with a shrinkage
shrinkage (OS = DHS-S) less than about (1.7%). with
heat setting these shrinkages can be reduced to about
2%, if desired. Example XIV-1 and 2 were uniformly
cold partially drawn, as defined herein, by providing a
RDR of at least about 1.4X in the drawn yarn. The
capability of these fine filaments to be uniformly
partially drawn is attributed to the crystalline
structure of the as-spun filaments providing a thermal
shrinkage less than about 12%, preferably less than
about 10%, and especially less than about 8%,'as per
Knox and Noe in U. S. Patent No. 5,066,447. In Example
XIV-5 through 8, 68-filament yarns were sequentially
draw cold and air-bet textured. The shrinkage
increased with draw ratio, providing a route to higher
shrinkage AJT yarns. The process and product data for
Example XIV is given in Table VIII.
Co-mingling (plying) 2 or more cold drawn AJT
yarn textile yarns, wherein at least one AJT yarn has
been heat set to shrinkages less than about 3%, and a
second AJT yarn has not been heatset, so has
significantly higher shrinkage, provides a simplified
route to a mixed shrinkage yarn. Similar mixed
shrinkage AJT yarns may be provided with the lower
shrinkage component provided by alternate techniques,
for instance by hot drawing, with or without heat
WO 92/13119 PGT/US92/00359
2~0~."r8g 52 _
setting. Alternatively, mixed shrinkage AJT yarns may
be provided by co-mingling 2 or more drawn filament
bundles wherein both bundles are drawn by cold drawing,
without post heat treatment, but the bundles are cold
drawn to different elongations, preferably by about ZO%
or more. The resulting mixed shrinkage drawn yarn may
be AJT to provide a mixed shrinkage textured (bulked)
yarn. Incorporating filaments of different deniers
and/or cross-sections may also be used to reduce
filament-to-filament packing and thereby improve
tactile aesthetics and comfort. Unique dyeability
effects may be obtained by co-mingling drawn filaments
of differing polymer modifications, such as homopolymer
dyeable with disperse dyes and ionic copolymers dyeable
with cationic dyes. AJT process and product details
are summarized in Table VIII.
In Example XV yarns were spun for use as draw
feed yarns (DFY)in false twist texturing (FTT).
Example XV-1, a nominal 58 denier 68-filament yarn was
textured at 500 m/min on a L900 PU machine with a 1.707
D/Y-ratio at a 1.628X draw to provide 68-filament
textured yarns of nominal 37 denier (0.54 dpf) with a
tenacity (T) of 4.1 g/d, an elongation-at-break (Eg) of
26.8%, a tenacity-at-7%-elongation (T7) of 2.19 g/d,
and an initial modulus (M) of 44.6 g/d. In Example XV-
2 a nominal 118 denier 200-filament draw feed yarn was
prepared for false twist texturing, as in Example XV-1,
except with a D/Y-ratio of 1.59 at a 1.461X draw-ratio
to provide 200-filament textured yarns of 83.5 nominal
denier (0.42 dpf) with a tenacity (T) of about 3.25 g/d
and an elpngation-at-break (EB) of about 23.9%. The
200-filament yarns were also successfully "partially"
warp drawn as per the teachings of Knox and Noe in U.
S. Patent No. 5,066,447 with a 1.49X draw-ratio to
W0 92/13119 ~g $ PGTlUS92/00359
provide a nominal 79.6 denier 200-filament flat yarn
having a 4.81 g/d tenacity and a 45.1% elongation-at-
break (Eg). In Example XV-3 a nominal 38 denier 100-
filament yarn was prepared for use as a draw feed yarn
in false-twist texturing and in warp drawing. The
process operability for Example XV-3 was better with
6x18 mil (0.152x0.457 mm) capillaries than with 9x36
mil (0.229x0.914 mm) capillaries. The yarns of Example
XV-3 were warp drawn over a range of conditions in
Example XVIII to provide 0.22 to 0.27 dpf 100-filament
yarns for wovens and knit fabrics.
EBAMPLE BZ1I
In Example XVI 21.2 LRV polyester polymer
containing 0.035 weight percent Ti02 was extruded at
285°C through 9x36 mil (0.229 x 0.914 mm) metering
capillaries with a four-diamond-shaped corrugated
ribbon cross-section exiting orifice of area.,318 mils2
(0.205 mm2). The 80 denier 100-filament bundles were
quenched using radial quench apparatus similar to that
used in Example III having a delay length of 2.9 cm and
converged by a metered finish tip applicator at 109 cm
from the face of the spinneret and withdrawn at a spin
speed of 2350 ypm (2.15 km/min). Yarns quenched with
47.5 mpm room temperature air had a along-end denier
spread (DS) of about 1.6-1.8%, a BOS of about 2.8%, an
average elongation-at-break (Eg) of 92.9% , an average
tenacity-at-break (Tg) of 4.56 g/d to give a (Tg)n/T7-
ratio of about 4.3. Decreasing quench air velocity to
21.7 m/min increased the Tg to about 4.64 g/d with a
(Tg)n/T7-ratio of about 4.5. The lower Tg-values
(i.e., less than about 5) are a consequence of the
corrugated filament cross-Sectional shape and such
filaments may be used in processes, such as false-twist
texturing (FTT) and air-jet texturing (AJT) where
filament fracture is desired to give even finer
WO 92f 13119 ~~ ~ ~ ~ ,.' ~ ~ 54 PCT/US92/00359
filaments (i.e., even less than about 0.2 dpf) for a
more spun-like aesthetics.
ERAMPLE BVII
In Example XVII nominal 43 denier 50-
filaments with a concentric void of about 16-17% were
spun at 3500 ypm (3.2 km/min) and at 4500 ypm (4.12
km/min). The hollow filaments were formed by post-
coalescence of nominal 21.2 LRV polymer at 290°C using
segmented capillary orifices with 15x72 mil
(0.381x1.829 mm) metering capillaries as essentially
described by Champaneria etal in U. S. Patent No.
3,745,061, Farley and Barker in Br. Patent No.
1,106,263, Hodge in U. S. Patent No. 3,924,988 (Figure
1), Most in U. S. Patent No. 4,444,?10 (Figure 3), in
Br. Pat. Nos. 838,141, and 1,106,263. The geometry of
the entrance capillary (counterbore) to the segmented
orifices was adjusted to optimize the extrudate bulge
and minimize pre-mature collapse of the hollow melt
spinline. The ratio of the inner and outer diameters
of the circular cross-section formed by the segmented
orifices was adjusted to provide percent void content
greater than about 10% and preferably greater than
about 15%. The void content is found to increase with
extrusion void area (~ID2/4), mass flow rate, polymer
melt viscosity (i.e., proportional to LRV/Tp) and with
increasing withdrawal speed (V) and the above process
parameters are selected to obtain at least about 10%
and preferably at least about 15% void content (VC).
For example the fine hollow filaments were quenched
using radial quench apparatus fitted with a short delay
shroud as described in Example XVI, except air flow was
reduced to about 16 m/min and converged via a metered
finish tip applicator at a distance less than about 140
cm. The yarns spun at 3.2 km/min had
tenacity/elongation/modulus of about 3 gpd/90%/45 gpd,
WO 92/13119 ' ~ ~ ~ ~ ~ ~ , PCT/US92100359
55 ~ , - .
respectively and a tenacity-at-7%-elongation (T7) of
about 0.88 g/d. Yarns spun at 4.115 km/min had
tenacity/elongation/modulus of about 2.65 gpd/46%/64
gpd, respectively, and a tenacity-at-7%-elongation (T7)
of about 1.5 g/d. Yarns spun at 3.2 and 4.12 km/min
had boil-off shrinkage (S) values between about 3-5%.
EYAMPLE gVIII
In Example XVIII, the spun yarns of Example
XV-3 were drawn over a range of draw-ratios from 1.4X
to 1.7X to provide drawn filament yarns of deniers 26.6
to 22.2, respectively; with tenacities increasing from
4.38 g/d to 5.61 g/d and elongations-at-break (Eg)
decreasing from 36.6% to 15.8% with increasing draw-
ratio. All the draw yarns had boil-off shrinkages (S)
of about 4%. See Table VIII for process and product
summery.
EYAMPLE 8I8
In Example XIX-1 and XIX-2, 200-filament and
168-filament yarns (feed yarns from Example XV-3 and 4,
repsectively) of nominal 0.5 dpf were spun at 4400 ypm
(4.02 km/min) for use as direct-use flat yarns in woven
and knit fabrics. These yarns can also be air-jet
textured (AJT) without draw to provide low-shrinkage
AJT yarns of nominal 3% shrinkage.
EXAMPLE %X
In Example XX mixed filament yarns were
prepared by co-spinning sub denier filaments of the
invention with higher denier filaments, such as the low
shrinkage filaments as described by Knox in U. S.
Patent No. 4,156,071 and/or the high shrinkage
filaments described by Piazza and Reese in U. S. Patent
No. 3,772,872 to provide the potential for mixed-
WO 92/13119 ~ ~ ~ ; PCT/US92/00359
56
shrinkage (e.g., post-bulking in fabric) such as in the
case when the low shrinkage filaments of this invention
are combined with the high shrinkage filaments of
Piazza and Reese. On-line thermal treatment by use of .
a heated tube or a steam jet, wherein essentially no
reduction in filament denier takes place (i.e., no
space drawing) of mixed dpf low shrinkage filament
yarns, such as those prepared by co-spinning filaments
of this invention with those as described by Ifnox in U.
S. Patent No. 4,156,071, provides a route to unique
mixed shrinkage post-bulkable filament yarns wherein
the shrinkage of the sub denier filaments of this
invention remain essentially unchanged while the
shrinkage of the higher denier filaments (e.g., 2-4
dpf) is increased from initial boil-off shrinkage (S)
of less than about 6-10% to greater than 10%, typically
about 15-35%. The mixed shrinkage yarns prepared with
the mentioned intermediate heat treatment differ from
those obtained by combining the low shrinkage filaments
of this invention with the higher shrinkage filaments
of Piazza and Reese in that the heat treated high
shrinkage filaments have significantly improved
shrinkage tension (e. g., at least about 0.15 g/d) which
permits development of the bulk from the mixed-
shrinkage even in very tightly constructed woven
fabrics .
The combination of high shrinkage and high
shrinkage tension (herein called shrinkage power) was
heretofore only obtained, for example, by fully drawing
conventional LOY/MOY/POY followed by no or low
temperature annealing. The sub denier filaments of the
invention migrate to the surface on mixed shrinkage and
provide a soft luxurious tactile aesthetics even in the
most tightly constructed fabrics. The heat treatment
is typically carried out after the filaments are fully
attenuated and quenched to below their glass transition
WO 92/13119 'Z ~ ~ '~ '~ ~ g ; PCT/US92/00359
- 57
temperature and in a manner that the increase in
tension during the heat treatment is of the magnitude
equal to that of the observed increase in shrinkage
tension by said heat treatment. Selecting heat
treatment conditions greater than about the cold
crystallization temperature TCC(DSC), (typically about
95 to about 115°C) and less than about the temperature
of maximum crystallization TC (typically about 15o to
about 180°C for most polyesters) gives high shrinkage
tension filaments of excellent dyeability (e. g., high
RDDR), while treatment under temperatures greater than
TC gives high shrinkage tension filaments of reduced
dyeability. The filaments may be heated either by
passing through high pressure superheated steam (e. g.,
40-140 psi at about 245°C) or by passing through a
heated tube. The high and low dpf filaments may be
spun from separate pack cavities and then combined to
form a single mixed-dpf filament bundle or may be spun
from a single pack cavity, wherein the capillary
dimensions (L and D) and the number of capillaries
are selected to provide for differential mass flow
rates; e.g., by selecting capillaries such that the
ratio of spun filament deniers, [(dpf)b/(dpf)a], is
approximately equal to [(LaDb/LbDa)n x (Va/Vb) x
(Db/Da)3], where a and b denote filaments of differing
deniers; n = 1 for Newtonian polymer melts (and herein
determined experimentally from convetnional capillary
pressure drop tests) and that the measured average dpf
- [ (~adpfa + ,~bdpfb) / (,~a + ,fib) ] , The above heat
treatment process can also be used to increase the
lower shrinkage of the sub denier filaments of the
invention as defined by the needs of the particular
end-use, such as increasing from about 3% to about 6-8%
with higher shrinkage tension (and shrinkage power) for
tightly constructed wovens.
WO 92/13119 a
PGT/US92/00359
- 5s
E7CAMPLE 8$I
In Example XXII 50 denier 68-filament undrawn
flat textile yarns were uniformly cold drawn and heat
treated at 160, 170, and 180~C to provide nominal 36
denier 50 filament drawn yarns of about 4-5% boil-off
shrinkage (S) with a T7 of about 3.5 g/d, a tenacity of
about 4.5 g/d with an elongation-at-break (Eg) of about
27%. The drawn yarns have a percent Uster of about
2.1-2.4% and may be used for critically dyed fabrics.
ALE %8II
The fine denier filaments of this invention
may be used to cover elastomeric yarns (and tapes) by
high speed air-jet entanglement as taught by Strachan
in U. S. Patent No. 3,940,917. Polyester fine
filaments prepared from polymer modified for cationic
dyeability are especially suitable for elastomeric
yarns, such as Lycram to prevent "bleeding" of the
dyestuff from the elastomeric yarns, such as observed
for Lycra covered with homopolymer polyester dyed with
nonionic disperse dyes. The direct-use filaments of
this invention are preferred (and those with increased
shrinkage, shrinkage tension, and shrinkage power as
described in Example XX.are especially preferred) for
air-entanglement covering and permit the covered
elastomeric yarns to be dyed under atmospheric
conditions without the use of carriers, e.g., similar
to the dye bath conditions to dye nylon filament
covered elastomeric yarns (except for being dyed with
anionic acid dyes).
Some example fabrics made from the yarns of
the invention are: lj a medical barrier fabric
constructed with a low shrinkage 70 denier 100-filament
direct-use flat yarn filling and a 70 denier 34-
W0.92/13119 ~ ~ ~ ~ PGT/US92/00359
59
filament conventional warp drawn POY in the warp and
woven on a high speed water-jet loom at 420 picks per
minute to give a plain weave fabric of 164 ends per
inch in th'e warp and 92 picks per inch in the fill; 2)
a lounge wear satin constructed using the above 70
denier 100-filament direct-use yarn in the warp and
combining it with a 60 denier 100-filament false twist
textured fill to provide a satin with 172 ends per inch
in the warp and 100 picks per inch in the fill; and 3)
a crepe de chines fabric constructed with the above 70
denier 100-filament direct-use yarn in the warp and a
2-ply 60 denier 100-filament false twist textured yarn
in the fill.
For convenience the symbols, conversions, and
analytical expressions used herein before are listed
below:
PET Polyethylene terephthalate) ~;
2GT PET
Ti02 Titanium dioxide
Si02 Silicon dioxide
( )f "of the fiber"
( )p "of the polymer"
( )m "measured"
dpf Denier per Filament (1 gram/9000 meters)
dpf(ABO) DPF after boil-off shrinkage
dpf(BBO) DPF before boil-off shrinkage
DS Along-end % Denier Spread (3 sigma)
DTV Draw tension variation (%)
[r;] Intrinsic viscosity (IV)
LRV Relative Viscosity (Lab)
IV Intrinsic Viscosity
LRV20og LRV of the polyester polymer having the
same melt zero-shear Newtonian melt
viscosity as homopolymer (unmodified
WO 92/13119 _ ~ ~ PCT/US92/0(1359
. . , 60 _..
2GT) of 20.8 LRV at 295 degrees
cenitgrade (C)
C Degrees centigrade
'~a Apparent melt viscosity (poise)
Rio Melt viscosity as shear rate -> 0
X Weight fraction of delusterant
TMo Zero-shear polymer melting point (C)
(TM)a Apparent melting point of polymer (C)
Tg Polymer glass-transition temp.(c
Tp Polymer melt spin temperature (C)
Ta Quench air temperature (C)
Ts Spinline surface temperature
tr Filtration residence time (min)
w Capillary mass flow rate (gpm)
q Capillary volume flow rate (cm3/min)
S2 Spin pack flow rate (gpm)
Number of filaments per spin pack
VF Spin pack (filled) free-volume (cm3)
L Capillary Length (cm)
L/DgNp Capillary Length-Diameter Ratio
DgNp Capillary Diameter equal to round
capillary of equal x-section area (Ac)
Dreg Diameter of reference spinneret
Dsprt Diameter of test spinneret
Ac Capillary cross-sectional area (cm2)
Ga Apparent capillary shear rate (sec-1)
ea Apparent spinline strain
ER Apparent spinline extension ratio
EFD Extrusion filament density
dv/dx Velocity gradient
Apparent internal spinline stress (g/d)
Va Quench air laminar velocity (m/min)
LpQ Quench delay length (cm) '
Lc Convergence length (cm)
V~ Spin speed at convergence (km/min)
V Spin (withdrawal) speed (km/min) ,
W0 92/13119 PCT/US92/00359
23.~1'~88 6'
Vo Capillary Extrusion velocity (m/min)
Ao Spin pack extrusion area (cm2)
dV/dx Spinline velocity gradient (min-1)
Melt viscosity (poise)
DQ Delay quench
( )N Measured at the "neck" point
ypm, y/min yards per min
mpm, m/min meter per min
gpm, g/min grams per min
pm Measured fiber density (g/cm3)
pc Fiber density corrected for delusterant
pa Amorphous density (1.335 g/cm3)
px Crystal Density (1.455 g/cm3)
Xv Volume fraction crystallinity
Xw Weight fraction crystallinity
S Percent boil-off shrinkage
DHS Percent dry heat shrinkage
dS Shrinkage Differential (DHS-S)
Sm Maximum shrinkage potential (%);
ST Shrinkage Tension (g/d)
STmax Maximum shrinkage tension (g/d)
T(STmax) Shrinkage tension peak temperature
(C)
PS Shrinkage power (g/d)(%)
TSB Maximum set temperature
Mi Instantaneous tensile modulus (g/d)
M Initial (Young's) tensile modulus (g/d)
Mpy Post yield modulus (g/d)
T~ Tenacity-at-7%-elongation (g/d)
T2p Tenacity-at-20%-elongation (g/d)
T Tenacity (g/d)
Tg Tenacity-at-break (g/dd)
(Tg)n Normalized Tg (g/d)
gpdd, g/dd Grams per drawn denier
gpd, g/d Grams per (original undrawn) denier
SF Shape Factor (= PM/PgND)
PM Measured perimeter (P)
WO ~ ~ ~ S ~ ~ ~ ~ ~. ~ 62 PCT/US92/00359
92!13119
~ . ~
PgHD P of round filament of equal area
RDDR Relative Disperse Dye Rate (mini/2)
DDR Disperse Dye Rate (mini/2)
RDR Residual Draw-Ratio
l.abX Draw-ratio of value "i.ab", for example
EB Elongation-at-Break (%) .
tan a Secant poet-yield modulus (g/d)
tan B Tangent post-yield modulus (g/d)
on Birefringence
~a Birefringence of amorphous regions
oc Birefringence of crystalline regions
4 Intrinsic Birefringence
SOC Stress-Optical Coefficient (gpd)-1
fa Amorphous orientation function
fc Crystalline orientation function
COA Crystal orientation angle (WAXS)
LPS Long Period Spacing (SAXS,
CS Average (WAXS, 01.0) crystal size (~)
Tcc (DSC) DSC- cold crystallization temp:., (C)
T(E"max) E" peak temperature (Ta)
E" Dynamic loss modulus (g/d)
Mson Sonic Modulus (g/d)
MS Shrinkage Modulus (g/d)
SV Sonic velocity (km/min)
Vf~am Amorphous free-volume
Angstroms
mil 0.001 inhes = .0254 mm = 25.4 microns
Micron (10-6 m = 10-4 cm = 10-3 mm)
km/min kilometers/min = 103 meters/minute
A Hydrocarbolenedioxy units [-O-R'-O-]
B Hydrocarbolenedicarbonyl units
[-C(O)-R"-C(0)_]
R', R" hydrocarbolene group
C,H,O Carbon, hydrogen, and oxygen
-0- "Oxy" (ether) linkage
-C(0)- Carbonyl group
WO 92/13119 _ 21 U 17 8 8 63. P~/US92/00359
RPC Rapid Pin Count
FOY Percent weight finish-on-yarn
AJT Air-jet texturing
LOY Low-oriented yarns
MOY Medium-oriented yarns
HO'Y Highly oriented yarns
POY Partially-oriented yarns
SOY Spin-oriented yarns
DUY Direct-use yarns
FDY Fully drawn yarns
PBY Post-bulkable yarns
WDFY Warp draw feed yarn
DFY Draw feed yarn
DTFY Draw texturing feed yarn
FTT False-twist texturing
SHC Stufer-box crimping
SBT Stutter-box texturing
SDSO Simplified direct spin-orientation
WAXS Wide-angle x-ray scattering ~;
SAXS Small-angle x-ray scattering
OSC Differential Scanning Calorimetry
RAD Radial quench
XF Cross-flow quench
DT Draw tension (gpd)
DTV Draw tenaion variation (1;)
IFDU Interfilament denier uniformity
RND Round
TRI Trilobal
RIB Ribbon
HOL Hollow
ABO After boil-off shrinkage
BBO Before boil-off shrinkage
Rv Relative Viscosity
FVC Fractional void content
EVA Extrusion void area
ID Inner diameter
WO 92/13119 ~ ~ ~ ~ ~ ~ ~ ~ 6~ PCTIUS92/00359
OD outer diameter
d diameter of filament (cm)
Niso Isotropic index of refection
HRV LRV + 1.2
RV 1.28(HRV)
(~ia)2GT [0.0653(LRV + 1.2)333] at 295C
(~10) Tp (~10) 295C x (295/Tp) 6
ft3 0.0284 m3
~C (micron) 10-4 cm
mil (0.001") 2.54x10-3 cm = 25.4 microns
m/min 0.9144 yd/min
dpf 1 gram/9000 meters
g/min 0.132 pph
d(cm) 11.89x10'4(dpf/p)~
(TM)a (TM)a + 2x10-4(L/D)Ga, C
Ga (sec-1) (32/60~)(w/1.2195)(1/DgND)3, sec-1
tR (min) [1.2195 VF(cm3)]/(w #c), min
~a 10-3(p/SOC)(LRV/LRV20.8)(TR/TP)6
[V2/dpf]LAo(~)/~a]0.7~ g/d
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eR Ln ( ER)
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and L and D are in mils
TR (TM)a + 40C
w dpf V(mpm)/9000 = dpf V(km/min)/9, g/min
DRND 2(Ac/x)1/2~ cm
Xv (P-Pa) l (Pc-Pa)
Xw (Pc/P) Xv
Pc 1.455 g/cm3
Pa 1.335 g/cm3
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WO 92/13119 ~ ~ ~ ~ ~ ~ 6~ PCT/US92/00359
(TB)n TB x LRV0.75(1-X)-4
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fc (1 - COA/180)
f An/O _ ~(3<cos>2-1)
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OP = 4(L/DgND)~aGa, n = 1 for Newtonian
melts and as Ga -> 0
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OP 4 (L/D) r~aGa = 4 (L/D) rwall
wall naGa
Ga (32/~p)(w/D3), sec 1
Vo (w/p)/(Area), cm/min
g/d 1.0893N/dtex
1 g 0.9804x103 dynes
1 N 103 dynes
PSI 0.0703 kg/cm2
g/c~2 0. 9 (P)~9/d) (P~~ g/dtex) ~,
EVA ~(ID2/4)
FVC (ID/OD)2
PS (ST, g/d)x(S,%)
ABO BBO[100/(100-S)]
WO 92/13119 ' 66 PCT/US92/00359 .
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