US 3838561 A
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 DEG C. Also a process for producing this fiber and a bitumen-containing structure reinforced therewith are disclosed.
Description (OCR text may contain errors)
United States Patent Munting Oct. 1, 1974 1 UNIQUE POLYETHYLENE TEREPIITHALATE FIBER AND YARN  Inventor: Johannes Pieter Munting, Emmen,
 Appl. No.: 187,521
Related US. Application Data  Division of Ser. No. 852,915, Aug. 25, 1969, Pat. No.
 Foreign Application Priority Data 264/290 R, 290 N, 290 T; 161/170, 172
 References Cited UNITED STATES PATENTS 3,216,187 11/1965 Chantry et al. 57/140 R 3,413,797 12/1968 Chapman 57/140 R 3,448,573 6/1969 Glen et a1. 57/140 R 3,553,307 l/197l Kovac et al 264/290 3,562,382 2/1971 Fowler .264/290 3,564,835 2/1971 Keefe, Jr. et a1 57/140 R Primary ExaminerJohn Petrakes Attorney, Agent, or FirmCraig & Antonel-li 57 3 ABSTRACT A fiber especially suitable for reinforcing bitumencontaining 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 lad 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 160C. Also a process for producing this fiber and a bitumen-containing structure reinforced therewith are disclosed.
, 6 Claims, No Drawings UNIQUE POLYETHYLENE TEREPHTHALATE FIBER AND YARN This application is a division of application Ser. No. 852,915 filed Aug. 25, 1969, now U.S. Pat. No. 3,650,879.
This invention relates to reinforcing fibrillary material, e.g., fibers, threads, yarns or like thread-like 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 bitumencontaining 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, non-twisted or entagled 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 fiberswhich 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 160C. or higher. It has been found that at 160C. 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 160C. 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 160C. (The tenacity and elongation of the fibers are determined at a temperature of 20C., a relative humidity of 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 160C.
Known fibers that show a close resemblance to the fiber of this invention are described in the British Patent Specification No. 848,81 1. However, upon heating at 160C., 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 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 C. for 4 minutes, shrink at least 9 percent. It will be noted that the British Specification also mentions the possibility of pre-shrinking 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 pre-shrunk 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, 2and 3 of the British Patent Specification.
As already mentioned, the fiber of the inventionis 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 non-twisted. 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 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 70C. to 100C, 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 210C. to 250C. 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 is metacresol to the rate of flow of the pure solvent, measured at a temperature of 30C.
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 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 160C.
A similar two-stage process for drawing yarn of synthetic polyesters is known and disclosed in US. 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 V111 in column 12, have a particularly low shrinkage at 90C. (dry) and 100C. (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 90C. the 2 SD and 4 DD yarns in Table VIII of this patent show a shrinkage of only 0.52 percent and 1.3 percent, respectively. However, it has been found that upon being heated for 4 minutes at 160C, 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 per denier are subjected to a heat treatment at 210C. to 230C, with their length being kept constant, these fibers may bemade into fibers having a shrinkage of about 4 percent when being heated up to 150C. 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 111 and IV, a fiber subjected to the proposed heat treatment of the French Patent doesnot 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 1 A melt of polyethylene terephthalate having a relative viscosity of 1.59 is extruded through a spinnerette provided with 105 orifices measuring 250 p. in diameter, at a rate of 161 grams per minute and a temperature of 285C.
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 80C. and drawn to four times their original length. Subsequently, the threads are passed through a stream box 10 meters long in which the threads are drawn at a temperature of 230C. 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 160C, and an elongation of 4.5 percent at a load of 5 grams per denier.
EXAMPLE 11 A melt of polyethylene terephthalate having a relative viscosity of 1.62 is extruded through a spinnerette with 200 orifices measuring 250 a in diameter at a rate of 325 grams per minute and a temperature of 290C.
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 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 210C. and a speed of 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 results are listed in the following table.
heated for 4 minutes at 160C., and an elongation of 4.5 percent at a load of 5 grams per denier.
EXAMPLE 111 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 230C. 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:
Yarn Properties Before Heat Treatment After 30 Minutes Heating at 230C Heat Shrinkage (4 min. at 160C.) 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 No Steam' than others. Specifically. it is advantageous to employ adhesive substances comprising resinous materials that have a softening point between 50C. and 160C., 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, resin 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 160C. 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 1 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 to 76C., an acid number between and and a saponification number between and 65.
. sand, filler and asphalt bitumen as the foundation layer is applied at a temperature of about 160C. and rolled to a thickness of about 7 cm.
Yarn 2.51 Seconds 3.2 Seconds 9.6 Seconds Properties Treatment 1 in Steam of in Steam of in Steam of Tenacity, g.p.d. 7.2 7.3 7.4 7.4 Elongation at Break 8.8% 11.3% 12.4% 13.6% Heat-Shrinkage 4 min. at 160C. 8.1% 3.5% 2.5% 1.5% Elongation at a load of 5 g.p.d. 4.8% 5.6% 5.7% 6.0%
In these runs, too, the initial modulus did not change 1 considerably. But, as appears from the data in the 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 C., i.e. 8 percent and coated with a nonresinous 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 has a tenacity at a range of about 7.5 to 9.5 grams per denier, an elongation at break of from about 9 to percent, an elongation of about 2 to 5 percent at a load of 5 grams per denier and a shrinkage of from about 1 8 to 4 percent when being heated for 4 minutes at C. under said tension.
3. The reinforcing fiber of claim 1 in which the poly-. ethylene terephthalate from which the fiber is made has a relative viscosity in the range of from about 1.50 to 1.70.
4. A yarn made up of a plurality of continuous fibers of claim 1.
5. A fabric containing the yarn of claim 4.
6. The reinforcing fiber of claim 1 in which the tenacity and elongation of said fiber are determined at a temperature of 20C., a relative'humidity of 65 percent and at a constant rate of extension of 30 centimeters per