U.S. patent number 3,691,748 [Application Number 05/074,913] was granted by the patent office on 1972-09-19 for textured polyethylene terephthalate yarns.
This patent grant is currently assigned to Societe Rhodiaceta. Invention is credited to Michel Buzano.
United States Patent |
3,691,748 |
Buzano |
September 19, 1972 |
TEXTURED POLYETHYLENE TEREPHTHALATE YARNS
Abstract
Textile articles comprise yarns of a synthetic thermoplastic
material, especially polyethylene terephthalate, in which the
individual filaments comprise alternating zones of increasing and
decreasing thickness, the thinner zones having the higher
crystallinity index and vica versa; the filaments have a non-spiral
three-dimensional crimp, and both they, and the yarn comprising
them, have a high apparent volume. The yarn is made by only
partially stretching the initial yarn in contact with a crack
promoting agent such as an aqueous alcohol, and subsequently giving
the yarn, before or after it is made up, a heat treatment while it
is in a relaxed state.
Inventors: |
Buzano; Michel (Villeurbanne
(Rhone), FR) |
Assignee: |
Societe Rhodiaceta (Paris,
FR)
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Family
ID: |
8646175 |
Appl.
No.: |
05/074,913 |
Filed: |
September 23, 1970 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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799795 |
Feb 17, 1969 |
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Foreign Application Priority Data
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Feb 19, 1968 [FR] |
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140,386 |
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Current U.S.
Class: |
428/369; 57/206;
57/246; 428/910; 57/208; 428/399 |
Current CPC
Class: |
D01D
5/20 (20130101); D02G 1/00 (20130101); D02J
1/223 (20130101); D02J 1/229 (20130101); Y10T
428/2976 (20150115); Y10T 428/2922 (20150115); Y10S
428/91 (20130101) |
Current International
Class: |
D02G
1/00 (20060101); D01D 5/00 (20060101); D01D
5/20 (20060101); D02J 1/22 (20060101); D02g
003/00 () |
Field of
Search: |
;161/179,173
;57/14R,14S |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Burnett; Robert F.
Assistant Examiner: Linker, Jr.; Raymond O.
Parent Case Text
CROSS REFERENCE TO RELATED APPLICATIONS
This is a division of copending application Ser. No. 799,795 filed
Feb. 17, 1969.
Claims
We claim:
1. Textile articles comprising multi-filament polyethylene
terephthalate yarns, in which each filament consists of alternating
zones whose diameter progressively increases and decreases
respectively between at least two different mean values, the parts
of lowest diameter having the highest crystallinity index and
molecular orientation, the crystallinity index in the thinner parts
of the filaments being at least 15% and the thicker parts being
substantially wholly unoriented and amorphous, each filament having
a non-spiral three-dimensional structure and a high apparent
volume.
2. Textile articles according to claim 1, in which the
crystallinity index of the thinner parts of the filaments is
between 20 and 50.
Description
This invention relates to new textile articles comprising textured
yarns of high apparent volume having a three-dimensional non-spiral
crimp and to a process and a device for the manufacture of such
yarns.
A large variety of so-called textured yarns already exists, and
these can be schematically classified into spirally crimped yarns
and non-spirally crimped yarns. The former are obtained by
twisting, setting and untwisting, generally by means of a
continuous false twist process. These yarns are noteworthy for a
high elasticity which must for certain applications be reduced by
means of a supplementary setting treatment.
The non-spirally crimped yarns have crimps of various
configurations and are generally much less elastic, which is
usually not undesirable. They are obtained by various processes
using mechanical, pneumatic or mechanical-pneumatic devices. These
processes suffer from the disadvantage of a relatively limited
production speed as a result of the fact that moving elements are
used.
Chemical processes have also been used to texture yarns. In fact it
appears logical a priori to hope to obtain reproducible results
more easily by chemical means.
However this method of texturizing has hitherto remained little
developed because the processes which have been discovered have not
given industrial results comparable to those obtained by mechanical
means such as for example by false twist.
It was observed a long time ago that polyamide yarns can be
cold-drawn more easily if they are moistened with water or with a
hydroxylated non-solvent such as a lower aliphatic alcohol, a
glycol or a hydroxy ester,
It has been proposed to manufacture a crimped yarn by moistening an
unstretched or partially stretched polyamide yarn with water,
stretching it in the cold, drying it in the untensioned state and
subjecting it to a heat treatment before or after the cold drawing
but before the untensioned drying.
It was later shown that stretching synthetic yarns in such baths
causes the formation of cracks or surface crazing. Starting from
this observation, a process for the manufacture of slub yarns has
been proposed in which the filaments are tensioned whilst they are
in contact with an agent which causes crazing, stretched to at
least 1.01 times, and in general to approximately 2.5 times, their
initial length, withdrawn from the influence of the crazing agent
and stretched to produce a slub yarn having an oriented
structure.
It has also been proposed to manufacture textured yarns from a yarn
whose structure has been rendered asymmetric during spinning by the
action of a cooling agent by tensioning it while it is in contact
with a crazing bath, moistening it with a liquid medium which is
free from crazing agents and stretching it in the moistened state.
Yarns of a cracked structure have also been manufactured by
maturing in a cracking bath with gentle stretching and then
withdrawing the yarns from the bath and stretching them strongly.
However, apart from the fact that this process does not produce
textured yarns but yarns having a ribbed surface, it requires
several days to carry out.
All these methods either produce a product such as a slub yarn
which cannot pretend to replace a textured yarn, or provide a
textured yarn but using, at some stage, another conventional
process for obtaining a textured yarn such as asymmetric cooling of
the yarn during spinning which is an operation which is delicate to
carry out.
The present invention provides a new textured yarn of synthetic
thermoplastic material, which can be obtained in a simple manner,
the texturizing being effected either continuously on the yarn
itself with orientation stretching of the yarn or, as is
industrially an advantage, by pretreating the yarn and bringing out
the texture during a subsequent treatment stage of the finished
product, e.g., a knitted or woven fabric or similar material.
In one aspect the invention consists in a new textile article which
comprises continuous multifilament yarns, and staple fibers
obtained from such yarns, of a synthetic thermoplastic material, in
which each filament comprises alternating zones in which its
diameter increases and decreases progressively between at least two
different mean values, the zones of lowest diameter corresponding
to the zones having highest crystallinity index and a higher
molecular orientation, each filament furthermore having a
non-spiral three-dimensional crimp and a high apparent volume. The
textile article is preferably made of a polyester.
In the case of polyethylene terephthalate, the thick zones are
practically totally amorphous and unoriented and the thin zones
have a crystallinity index exceeding 15 percent and in practice
between 20 and 50 percent, the difference in the crystallinity
indices of the different zones generally being of the order of 10
to 30 percent. Of course these figures are approximate, because the
crystallinity indices depend on the degree of the stretching and of
the subsequent heat treatment employed in the production of the
yarn.
The total crystallinity index of this yarn is low. The
crystallization and molecular orientation phenomena observed are
reversible in character, in that if the yarn obtained according to
the invention is again stretched to a total degree less than is
required to orient it completely and this yarn is then treated
thermally in the relaxed state, it re-assumes the appearance of the
yarn of the invention before this additional stretching.
The overall crystallinity index value is determined by the method
of W.O. Statton [Journal of Applied Polymer Science, Vol 7, Pages
803- 815-(1963) ] and the angle of orientation by the method of W.
A. Sisson [Journal of Textile Research, Vol 7, Page 425 (1937)].
The values of the crystallinity indices and of the orientation
angles for the various zones are determined taking into account the
crystallinity indices and the overall orientation of the yarn, the
proportions by volume of the various zones, the appearance of X-ray
crystallographs, fluoresence comparisons after dyeing the various
zones of a given yarn or of several yarns, and the morphology of
these zones.
The differences in thickness of the yarn between the various zones
and the number of different zones observed depend also on the
working conditions. New zones are considered to have appeared if
the appearance of sequences is observed wherein the variation from
the mean diameter is at least equal to one tenth thereof. The yarn
of the invention shows an alternation of at least two different
zones having a random statistical distribution of their dimensions.
It goes without saying that the values of the crystallinity index
given above to characterize these zones are also statistical, but
that they correspond to an acceptable probability factor.
The yarn of the invention is noteworthy for its microporosity and
its very good dyeing affinity.
The invention also consists in a new process for the texturization
of a yarn of a synthetic thermoplastic material, especially of a
polyester which comprises partially stretching the yarn in contact
with a crazing agent, and heat treating the partially stretched
yarn in the relaxed state.
The heat treatment which may be termed "development," causes the
structure of the yarn described above to appear.
The degree of stretching must always be partial, i.e., less than
would cause a complete orientation of the yarn.
In practice, in the case of polyethylene terephthalate yarns of
usual filament deniers, such as those employed in knitting or
weaving, that is to say with filament deniers of less than 12, the
degree of stretching is between 2 and 3.5 times and advantageously
between 2.5 and 3 times. For yarns of filament denier exceeding 12
the degree of stretching should be between 3 and 4.5. This
stretching is advantageously carried out at or near ambient
temperature.
The thermal treatment can be carried out continuously with the
stretching or can be given during a subsequent treatment of the
yarn or, in the piece, during any stage of manufacture of a
finished product, such as a dyeing treatment, or on the finished
product itself. The time between this heat treatment and the
stretching in a crazing bath can be of any length without causing
problems with the resulting product and can be determined by
considerations outside the purview of the invention, such as
storage or handling times or requirements.
The heat treatment can be effected in any known manner, such as by
steam, with hot air, or by contact with or by immersion in a bath
of a liquid at a high temperature.
Known crazing agents can be used, e.g., alcohols, glycols,
dimethylformamide, kerosene, perchlorethylene, polyoxyethylenic
liquids of the "Carbowax" type, pyridine, etc. Such compounds have
frequently been described in the literature. Preferably, relatively
cheap agents are employed, such as lower alcohols.
The present invention consists further in a device for the
continuous manufacture of a textured yarn which in sequence
comprises yarn feeding means, means for immersing the yarn in a
crazing agent, means for continuously stretching the yarn in
contact with the crazing agent, a heat relaxation element
consisting of a heating means combined with means of relaxing the
yarn, and winding up means. It can also comprise means for
controlling the temperature of the crazing bath.
This device advantageously also comprises a device for interlacing
the constituent filaments of the yarn, arranged upstream from the
heat relaxation element. Such a device can be used to increase the
bulk of the yarn. An advantageous interlacing device is described
in French Pat. No. 1,492,945.
The heat relaxation element can be of a type which is in itself
known. It can for example consist of a mechanism for forwarding the
yarn, especially by means of rollers, combined with a heating box.
It can also comprise a device which serves also for the application
of another treatment for example a dyeing vat.
The invention is illustrated in the accompanying drawing, in
which
FIG. 1 is a schematic view of a device according to the
invention.
FIG. 2 is a representation of the filament obtained, and
FIG. 3 is a representation of a multifilament yarn of the
invention.
The device shown in FIG. 1 consists of a creel 1 carrying spools 2
which deliver an unstretched yarn 3 which is drawn off, over a wire
thread guide 4, by means of a system of feed rollers 5 and 6, and
then passes into a vat 7 containing a crazing bath. From this it
passes to a set of stretching rollers 8 and 9, set to run at a
higher peripheral speed than the feed rollers 5 and 6.
The yarn then passes to a heat relaxation element consisting of a
heating box 12 arranged downstream from the stretching rollers 8
and 9 and a set of relaxing rollers 13 and 14 arranged downstream
from the heating box and upstream from a wind-up device, for
example comprising a spindle. The relaxing rollers 13 and 14 are
arranged to run at a lower peripheral speed than the stretching
rollers 8 and 9.
This device can furthermore comprise a heating plate 11 located
just downstream from the vat 7.
In another variant, the last traces of crazing agent are removed in
the cold by passing the yarn into a strand interlacing device 15,
such as for example that described in the above mentioned French
Pat. No. 1,492,945, which is advantageously situated between the
stretching rollers 8 and 9 and the heating box 12.
The yarns used in the following illustrative Examples consist of
polyethylene terephthalate having an intrinsic viscosity, in
o-chlorophenol, of a value which is usual for textile yarns, of the
order of 0.065.
EXAMPLE 1
A 33 filament polyethylene terephthalate yarn of filament denier 7
is stretched by a factor of 3 in an aqueous bath containing 25
percent per weight of ethanol and kept at 40.degree.C. From this
bath it passes into a strand interlacing device 15 and it is then
treated in the completely relaxed state in a steam oven 12 at a
temperature of 126.degree. C. The stretching rollers 8 and 9 run at
a peripheral speed of 250 m/minute and the relaxing rollers 13 and
14 at 81 m/minute.
The yarn obtained has a bulkiness, as measured by the Konigh
method, of 2.5 cm.sup.3 g, a crimp of about 25 waves per cm and a
tensile strength of 3.5 g/denier.
For purposes of comparison, certain characteristic properties were
measured on each elementary filament before and after the heat
treatment in the relaxed state.
Before the heat treatment it is found that, if the diameter of each
elementary filament is irregular at all, the difference between the
swollen parts and the thin parts is relatively slight, their
respective diameters being 16.7 and 15.6 microns (.mu.). The
overall crystallinity index is about 3 percent. The thin parts have
a crystallinity index of about 15 while the crystallinity of the
thick parts is essentially zero, both parts being fairly well
oriented. On microscopic examination the filament shows surface
crazing or cracks.
After it has been developed by heat treatment in the completely
relaxed state, it is found that the yarn has shrunk considerably by
at least 25 percent of its initial length and usually between 50
and 80 percent of its initial length.
Microscopic observations shows the presence of narrow zones and
swollen zones very closely packed, giving the filament the
appearance of a string of slubs as illustrated in FIG. 2.
The diameter of the swollen parts has changed from 16.7 to 28 .mu.,
while that of the thin parts remains essentially unchanged.
It is furthermore observed that the crystallinity index of the thin
parts is now about 25 percent whilst that of the thick parts has
remained about zero. This difference in crystallinity is also
determined by observing the fluorescence with Rhodamine B (C.I.
45,170 ).
On the other hand the orientation is very slight, the angle of
molecular orientation p is about 75.degree. for the thin parts and
90.degree. for the thick parts.
Furthermore this yarn shows good dyeing affinity. This latter
property is demonstrated in the following manner.
The yarn is continuously dyed by passing it, after the heat
treatment in the relaxed state and before winding-up, over a dyeing
device comprising a porous partition having an essentially plane
smooth surface such as is described in French Pat. No. 1,502,746,
the said surface being impregnated with an aqueous dyeing bath
containing 15 g/l of the dispersed dyestuff Disperse Yellow 7
(C.I.26,090).
A yarn dyed yellow is obtained, though under the same conditions a
standard polyethylene terephthalate yarn does not accept the
dye.
EXAMPLE 2
The procedure of Example 1 is followed, except that the yarn is
interlaced after stretching and before the winding-up and heat
treatment. The yarn then has a bulk of 3 cm.sup.3 /g.
EXAMPLE 3
In this Example the yarn is stretched in the same way, but is
developed in a Venturi type of nozzle fed with air heated to
200.degree. C.
The yarn then has a bulk of 2.5 cm.sup.3 /g.
It is thus seen that this new texturizing process makes it possible
continuously to obtain closely reproducable yarns of high apparent
volume in the course of very simple operations using a device that
has a minimum of moving elements and chemical baths of constant
concentration. Furthermore this process makes it possible to
texture yarns at high speeds, comparable to the speeds achieved
during winding-up after spinning and stretching.
Furthermore, by virtue of the shrinkage of these yarns, it is
possible, by heat-treating in the piece, to achieve effects
comparable to those given by other shrinkable yarns.
The yarns of the invention may be used, by themselves or in
mixtures, in the form of continuous lengths or of cut fibers, in
the majority of textile applications and can in particular be
converted into woven or knitted fabrics.
* * * * *