U.S. patent number 3,650,879 [Application Number 04/852,915] was granted by the patent office on 1972-03-21 for manufacture of unique polyethylene terephthalate fiber.
This patent grant is currently assigned to Akzona Incorporated. Invention is credited to Johannes Pieter Munting.
United States Patent |
3,650,879 |
Munting |
March 21, 1972 |
MANUFACTURE OF UNIQUE POLYETHYLENE TEREPHTHALATE FIBER
Abstract
A fiber especially suitable for reinforcing bitumen-containing
materials which comprises a fiber of polyethylene terephthalate
having a tenacity of at least about 7.5 grams per denier, an
elongation at break of at least about 9 percent, an elongation of
not more than about 5 percent under a load of 5 grams per denier
and a shrinkage of less than 4 percent when kept under a tension of
0.05 grams per denier for 4 minutes at about 160.degree. C. Also a
process for producing this fiber and a bitumen-containing structure
reinforced therewith are disclosed.
Inventors: |
Munting; Johannes Pieter
(Emmen, NL) |
Assignee: |
Akzona Incorporated (Enka,
NC)
|
Family
ID: |
19804509 |
Appl.
No.: |
04/852,915 |
Filed: |
August 25, 1969 |
Foreign Application Priority Data
|
|
|
|
|
Aug 31, 1968 [NL] |
|
|
6812442 |
|
Current U.S.
Class: |
442/149 |
Current CPC
Class: |
D02G
3/447 (20130101); D06N 5/00 (20130101); D01F
6/62 (20130101); D10B 2331/04 (20130101); Y10T
442/2738 (20150401) |
Current International
Class: |
D02G
3/44 (20060101); D06N 5/00 (20060101); D01F
6/62 (20060101); D02G 3/22 (20060101); D02G
3/02 (20060101); B32b 011/02 () |
Field of
Search: |
;161/92,170,231,236
;264/290 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Van Balen; William J.
Claims
What is claimed is:
1. A fiber reinforced bitumen-containing material which comprises a
bitumen-containing layer reinforced with a fiber of polyethylene
terephthalate having a tenacity of at least about 7.5 grams per
denier, an elongation at break of at least about 9 percent, an
elongation of not more than 5 5 percent under a load of 5 grams per
denier, and a shrinkage of less than 4 percent when kept under a
tension of 0.05 grams per denier for 4 minutes at about 160.degree.
C.
2. The fiber reinforced bitumen-containing material of claim 9 in
which said fiber has a tenacity in a range of from about 7.5 to 9.5
grams per denier, an elongation at break of from about 9 to 15
percent, an elongation of about 2 to 5 percent at a load of 5 grams
per denier, and a shrinkage of from about 1 to 4 percent when being
heated for 4 minutes at 160.degree. C. under said tension.
3. The fiber reinforced bitumen-containing material of claim 1 in
which the polyethylene terephthalate from which said fiber is made
has a relative viscosity in the range of from about 1.5 to
1.70.
4. The fiber reinforced bitumen-containing material of claim 1 in
which said fiber is in the form of a fabric woven from continuous
multi-filament yarn.
5. The fiber reinforced bitumen-containing material of claim 1 in
which said fiber is adhesively bonded to said bitumen-containing
layer.
6. The fiber reinforced bitumen-containing material of claim 1 in
which said fiber is laminated between two bitumen containing
layers.
7. The fiber reinforced bitumen-containing material of claim 1 in
which said fiber is coated with an adhesive promoting substance
comprising a resinous material that has a softening point between
50.degree. and 160.degree. C., is miscible with bitumen, and acts
as a wetting agent for the fiber.
8. The fiber reinforced bitumen-containing material of claim 7 in
which said resinous material is selected from the group consisting
of montan resin, tall resin, coumarone and indene resins, maleic
resins, phenol resins, and rosin derivatives.
Description
This invention relates to reinforcing fibrillary material, e.g.,
fibers, threads, yarns or like threadlike products, of a polymer
substantially made up of ethylene terephthalate units and more
particularly to polyethylene terephthalate fibers having a
combination of properties especially suitable for the reinforcing
of bitumen-containing materials, to a process for producing such
fibers and products reinforced thereby.
The term "fibers," as used throughout this specification is meant
to include continuous monofilaments, nontwisted or entangled
multifilament yarns, staple yarns and spun yarns. Such fibers may
be used to form woven fabrics, knitted fabrics, fibrous webs, or
any other fiber-containing structures.
Also the expression "a polymer substantially made up of ethylene
terephthalate units" is meant to define polyethylene terephthalate
and copolymers which have in their polymer chains not more than 10
mole percent of units other than the ethylene terephthalate units.
For instance, the polymer may be prepared from a reaction mixture
which in addition to terephthalic acid or derivatives thereof
contains isophthalic acid or other dicarboxylic acid or derivatives
thereof. Likewise, the reaction mixture may in addition to ethylene
glycol contain one or more other diols such as propylene glycol.
These copolymers are fully documented and described in the patent
literature. The term "polyethylene terephthalate" used hereinafter
for brevity is also to be understood to include such
copolymers.
Reinforcing fibers of polyethylene terephthalate are known. These
fibers are used, inter alia, for reinforcing rubber articles such
as pneumatic tires and conveyor belts, as well as sheet material
and layered material having a base of bitumen or asphalt. In these
applications the fibers absorb part of the strain acting on the
reinforced product. The higher the force which is required to
elongate the fibers to a given extent, the smaller will be the
deformation at a given force. Products such as automobile tires and
road surfaces are subject to varying dynamic forces. The smaller
the deformations as a result of these forces, the longer will be
the service life, because the creep and fatigue properties of such
products are to a high degree negatively influenced by deformation.
For these applications it is therefore advantageous to use fibers
having a high modulus. It has been found that for the reinforcing
of asphalt road surfaces it is not the initial modulus of the
fibers which is of decisive importance, but the modulus prevailing
at a relatively high load. This modulus should be such that at a
load of 5 grams per denier, the stretch or, in other words,
elongation is not more than 5 percent.
Fibers that conform to this requirement are known, inter alia, from
the disclosure of the British Pat. specification No. 848,811.
Although the known polyethylene terephthalate fibers are in many
respects very suitable for reinforcing sheet material and layered
material having a base of bitumen, these fibers have the following
shortcoming. For many applications, it is desirable to use bitumen,
or bitumen-containing materials having a high softening point. The
application of such a material must be carried out in a liquid or
molten state at temperatures up to 160.degree. C. or higher. It has
been found that at 160.degree. C. the known polyethylene
terephthalate fibers show a relatively high degree of shrinkage,
which often gives rise to undue deformation in the reinforced
product. For instance, during road construction, when a fabric is
provided which is made of a known polyethylene terephthalate fiber
and a bitumen coating heated up to about 160.degree. C. or higher
is subsequently applied thereto, the fabric will shrink to such a
degree that undulations and cracks will be formed in the bitumen
coating.
It has been found that this drawback is not encountered when the
polyethylene terephthalate fibers satisfy particular demands as to
reduced shrinkage at high temperatures. Advantageously the present
invention provides a polyethylene terephthalate fiber having a
unique combination of properties including low shrinkage at
elevated temperatures.
Thus this invention contemplates a reinforcing fiber which
comprises a fiber of polyethylene terephthalate that has a tenacity
of at least about 7.5 grams per denier, an elongation at break of
at least about 9 percent and an elongation of not more than about 5
percent at a load of 5 grams per denier and that shrinks less than
4 percent when kept under a tension of 0.05 grams per denier for 4
minutes at a temperature of about 160.degree. C. (The tenacity and
elongation of the fibers are determined at a temperature of
20.degree. C., a relative humidity of 65 percent and at a constant
rate of extension of 30 centimeters per minute.)
The fiber of this invention is thus distinct from all known
polyester fibers in that it satisfies a combination of requirements
regarding tenacity, elongation at break, elongation at a load of 5
grams per denier, and low shrinkage at about 160.degree. C.
Known fibers that show a close resemblance to the fiber of this
invention are described in the British Pat. specification No.
848,811. However, upon heating at 160.degree. C., these known
fibers show a shrinkage which is considerably higher than 4
percent. From FIG. 4 of this patent specification it is evident
that upon being heated for a short time at 135.degree. C. the
fibers disclosed shrink considerably more than 5 percent. As may be
inferred by extrapolation from the data shown in FIG. 4 of the
British Specification, these fibers, heated at 160.degree. C. for 4
minutes, shrink at least 9 percent. It will be noted that the
British Specification also mentions the possibility of preshrinking
the fibers by subjecting the fibers to a heating treatment in order
to reduce the shrinkage during processing. This treatment, however,
has a very unfavorable influence on the other properties and the
resulting preshrunk product no longer meets the combination of
requirements as regards tenacity, elongation at break or elongation
at a load of 5 grams per denier. This lack of properties is clearly
demonstrated by the data illustrated in FIGS. 1, 2 and 3 of the
British patent specification.
As already mentioned, the fiber of the invention is particularly
suitable for reinforcing layered material and sheeted material
having a base of bitumen. It is preferred that the fiber should be
employed in the form of a continuous multifilament yarn. This yarn
may be twisted or nontwisted. Alternatively, if a higher coherency
of the filaments is required, use may be made of a tangled yarn. In
such case, the filaments have been interlaced by turbulent air
streams.
Another aspect of this invention is concerned with a process for
producing the unique reinforcing fibers. Thus, the fiber of this
invention may be obtained by subjecting an undrawn fiber of
polyethylene terephthalate having a relative viscosity of about
1.50 to 1.70 to a two-stage drawing procedure, the drawing in the
first stage taking place at a temperature of about 70.degree. to
100.degree. C., and at a draw ratio in the range of about 3.8 to
4.2, and the drawing in the second stage taking place in the
presence of superheated steam at a temperature of about 210.degree.
to 250.degree. C. and at such a draw ratio that the total draw
ratio is in the range of about 5.6 to 6.0.
By the term "relative viscosity" it is meant the ratio of the rate
of flow through a capillary of a 1 percent solution of the polymer
in metacresol to the rate of flow of the pure solvent, measured at
a temperature of 30.degree. C.
This process makes it possible to obtain fibers of this invention
having a tenacity in the range of about 7.5 to 9.5 grams per
denier, an elongation at break of about 9 to 15 percent, an
elongation of about 2 to 5 percent at a load of 5 grams per denier,
(determined under the heretofore-described testing conditions) and
a shrinkage of about 1 to 4 percent upon being heated for 4 minutes
at about 160.degree. C.
A similar two-stage process for drawing yarn of synthetic
polyesters is known and disclosed in U.S. Pat. No. 2,556,295. From
the disclosure of this patent it is apparent that the use of
different draw ratios and temperatures in each of the drawing
stages is known per se. However, this patent does not teach the
specific combination of drawing conditions required, including the
use of superheated steam to heat the fiber or yarn in the second
stage of drawing. Moreover, although this patent mentions that the
fibers described therein have a low shrinkage at an elevated
temperature, it does not reveal a fiber having the properties of
the fiber according to the present invention.
According to the U.S. Pat. No. 2,556,295, the yarns designated as
"1 SD" and "3 DD" in Table VIII in column 12, have a particularly
low shrinkage at 90.degree. C. (dry) and 100.degree. C. (wet).
After these yarns were drawn, they were relaxed and upon being
subjected to a load of 5 grams per denier show an elongation which
is much higher than the maximum elongation of 5 percent exhibited
by the fiber of the present invention.
It is also noted that upon being heated for 30 minutes at
90.degree. C. the "2 SD" and "4 DD" yarns in Table VIII of this
patent show a shrinkage of only 0.52 and 1.3 percent, respectively.
However, it has been found that upon being heated for 4 minutes at
160.degree. C., these yarns show a shrinkage which is considerably
higher than 6 percent.
It should also be realized that the French Pat. No. 1,490,211
mentions that when fibers of polyethylene terephthalate having a
relative viscosity in the range of 1.60 to 1.75 and a tenacity of 7
to 8 grams DENIER are subjected to a heat treatment at 210.degree.
to 230.degree. C., with their length being kept constant, these
fibers may be made into fibers having a shrinkage of about 4
percent when being heated up to 150.degree. C. without the heat
treatment resulting in loss of tenacity or modulus.
It has been found that, although according to the French patent the
heat setting treatment does not result in a loss of modulus, this
result does not imply that at a load of 5 grams per denier the
elongation of the fiber does not increase. As will be apparent from
the following Examples III and IV, a fiber subjected to the
proposed heat treatment of the French patent does not satisfy the
demands made on a fiber according to the present invention, because
at a load of 5 grams per denier the elongation is higher than the
maximum permissible 5 percent.
The fibers according to the invention are of particular importance
as reinforcing material of bituminous road surfaces. However, they
also may serve to reinforce other materials. The fibers are
particularly suitable for the purpose of reinforcing materials
which are subjected to high temperatures as they are being formed
into their desired shape.
Accordingly, this invention also is directed to sheet materials and
layered materials which have a base of bitumen and are reinforced
with the fibers according to the invention.
The invention will be further understood by reference to the
following examples:
EXAMPLE I
A melt of polyethylene terephthalate having a relative viscosity of
1.59 is extruded through a spinnerette provided with 105 orifices
measuring 250 .mu. in diameter, at a rate of 161 grams per minute
and a temperature of 285.degree. C.
The polymer streams issuing from the spinnerette are cooled over a
distance of 10 to 150 cm. from the spinnerette by directing a
stream of cooling air on to them. The threads are wound at a speed
of 500 meters per minute.
After having been provided with a finish, the threads obtained are
passed over a drawpin having a temperature of 80.degree. C. and
drawn to four times their original length. Subsequently, the
threads are passed through a steam box 10 meters long in which the
threads are drawn at a temperature of 230.degree. C. and a speed of
150 meters per minute to a total draw ratio of 5.8. The threads
obtained in this way is doubled by plying it into a cord having a
denier of 1,000, a tenacity of 7.8 grams per denier, an elongation
at break of 9.7 percent, a shrinkage of 3.9 percent after heating
for 4 minutes at 160.degree. C., and an elongation of 4.5 percent
at a load of 5 grams per denier.
EXAMPLE II
A melt of polyethylene terephthalate having a relative viscosity of
1.62 is extruded through a spinnerette with 200 orifices measuring
250 .mu. in diameter at a rate of 325 grams per minute and a
temperature of 290.degree. C.
The polymer streams issuing from the spinnerette are cooled over a
distance of 10 to 150 cm. from the spinnerette by directing a
stream of cooling air on to them. The threads are wound at a speed
of 500 meters per minute.
After having been provided with a usual finish, the threads
obtained are passed over a drawpin having a temperature of
80.degree. C. and drawn to four times their original length.
Subsequently, the threads are passed through a steam box 10 meters
long in which the threads are drawn at a temperature of 210.degree.
C. and a speed of 150 meters per minute to a total draw ratio of
5.8. The thread thus made has a denier of 990, a tenacity of 8.15
grams per denier, an elongation at break of 11.0 percent, a
shrinkage of 3.9 percent after being heated for 4 minutes at
160.degree. C., and an elongation of 4.5 percent at a load of 5
grams per denier.
EXAMPLE III
In order to establish whether a yarn similar to that of this
invention may also be obtained by the process proposed in the
French Pat. No. 1,490,211, a single layer of drawn polyethylene
terephthalate yarn was wound on a rigid bobbin, which was
subsequently heated for 30 minutes in air at 230.degree. C. After
this treatment the denier of the yarn had not changed. The
following table shows the values of several properties of the yarn
before and after the treatment:
Before After 30 Minutes Yarn Properties Heat treatment Heating at
230.degree. C.
__________________________________________________________________________
Heat Shrinkage (4min. at 160.degree. C.) 8.6% 0.4% Tenacity 7.7
g.p.d. 6.8 g.p.d. Elongation at Break 10.1% 12.8% Elongation at a
load of 5 grams 5.0% 6.3% Initial Modulus 90 g.p.d. 90 g.p.d.
__________________________________________________________________________
These results show that although the heat-relaxation does not
change the initial modulus, the treatment does cause the tenacity
to decrease from 7.7 g.p.d. (grams per denier) to 6.8 g.p.d. and
also results in a considerable loss of modulus at a load of 5
grams.
EXAMPLE IV
It was also tried to obtain a yarn similar to that of the invention
by heat-relaxing a yarn (i.e., heating the yarn while keeping it at
a constant length) having a high heat-shrinkage to form a yarn
having a low heat-shrinkage, in accordance with the teachings of
the French Pat. No. 1,490,211.
To this end a polyethylene terephthalate yarn having a denier of
1,050 was passed through a chamber containing steam at 230.degree.
C. The supply rate was equal to the discharge rate. These rates
were varied in order to obtain different residence times in the hot
steam. The results are listed in the following table. ##SPC1##
In these runs, too, the initial modulus did not change
considerably. But, as appears from the data in the above table, the
heat-relaxation causes the elongation at a load of 5 g.p.d. to
increase, so that products are obtained which do not meet the
requirements for a yarn according to the present invention.
It will be understood that a fiber according to the invention may
in the usual way be provided with a finish and with a coating of a
substance which promotes adhesion to the material to be reinforced.
In the preparation of reinforced bitumen-containing structures such
as roadways, it has been found that certain adhesive promoting
substances are considerably more effective than others.
Specifically, it is advantageous to employ adhesive substances
comprising resinous materials that have a softening point between
50.degree. and 160.degree. C., are miscible with bitumen, and in
the molten state act as wetting agents on the reinforcing fiber.
Exemplary of the resinous materials that may be used as adhesive
promoting substances with the fibers of this invention are montan
resin, tall resin, the coumarone and indene resins, maleic resins,
phenol resins, rosin derivatives, and the like.
EXAMPLE V
This example illustrates the use of the fibers of this invention to
reinforce a bitumen-containing road surface. In construction of the
test road, a foundation layer of a mineral mixture of 50 percent by
weight of gravel and filler and 50 percent by weight sand with
asphalt bitumen having a high softening point is applied at a depth
of about 7 cm. to a sub-layer of compacted sand. About 5 to 6
percent by weight of the foundation layer consists of bitumen. This
layer is applied at a temperature of about 160.degree. C. and
rolled. Thereafter, an adhesive layer of an anionic 50 percent
asphalt emulsion is provided over the foundation layer and a fabric
made of the same type of polyethylene terephthalate fiber described
in Example I is then rolled out over the adhesive layer. The fabric
has a plain weave type and is charged with about 45 percent by
weight of a montan resin having a solidifying point of 75.degree.
to 76.degree. C., an acid number between 30 and 40 and a
saponification number between 55 and 65.
After the fabric is stretched longitudinally and transversely over
the foundation layer and pinned down, a second coating of the
asphalt emulsion is applied by spraying and is allowed to break up.
Then another asphalt layer having the same composition of gravel,
sand, filler and asphalt bitumen as the foundation layer is applied
at a temperature of about 160.degree. C. and rolled to a thickness
of about 7 cm.
This road surface is compared with one, made in the same manner but
using a fabric woven of a polyethylene terephthalate fiber having
suitable tenacity and elongation properties, (but a shrinkage
greater than 4 percent at 160.degree. C., i.e., 8 percent) and
coated with a non-resinous adhesive promoting substance, i.e.,
solar oil. The comparison shows that the road surface containing
the fiber of this invention has substantially no deformation caused
by shrinkage of the fabric and that there is excellent adhesion
between the reinforcing fabric and the bitumen layer; whereas the
other road surface has cracks and undulations formed by the
deformation of the bitumen-containing layer during shrinkage of the
fabric and the fabric poorly adheres to the bitumen layer.
* * * * *