JPS5940925B2 - polyester fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to polyester fibers, particularly melt-spun polyester textile filaments with improved acidity.

It is an object of the present invention to provide an improved polyester textile filament that has a unique crystalline microstructure and exhibits a monoacidic balance not achieved by previous polyester filaments.

According to the present invention, melt spinning, solidification and Consisting of at least 85 mole percent polyethylene terephthalate that has been heat conditioned and has a highly oriented, monocrystalline microstructure interconnected throughout the length of the filament with a substantially non-oriented amorphous acid phase dispersed therein. In the as-spun state (i.e., without further stretching after the conditioning treatment during spinning), only slight shrinkage occurs even at high forces at high temperatures, as evidenced by a modulus ratio of at least 0.1. average growth of less than 50%.

Average longitudinal shrinkage of 5% or less at 100°C, and 0
．． Improved polyester textile filaments are provided that exhibit a birefringence of 10 to 0.14.

Polyester filaments have been produced in the past using a variety of melt spinning conditions.

However, the polyester filaments obtained by the prior art cannot be spun until they are spun (including the case where the solidified filament is conditioned during the spinning process), and thus are not further drawn. None had a crystalline structure and/or material like the polyester filament of the present invention.

For example, the polyester filaments obtained by the melt spinning method described in US Pat. No. 2,604,667 have a highly amorphous orientation, and the crystal dimensions of the crystal bends are large.

The modulus ratio is less than 0.1.

The polyester filaments obtained by the melt-spinning process described in U.S. Pat. small.

Polyester filaments obtained by the melt-spinning method described in US Pat. No. 3,361,859 have a low orientation range, a modulus ratio less than 0.1, and a very high elongation (500-600%).

Japanese Patent Publication No. 42-21297 discloses that the diameter of the hole is abnormally larger than usual (about 1.5 mm at the extrusion point using a 3 mm or 9 mm nozzle).
A method for performing melt spinning at a draft ratio of 0.000 or higher is described.

In this method, no heat conditioning treatment is performed during the spinning process, nor is there any suggestion of heat conditioning treatment of the spinning yarn (ie, once the package has been wound).

The publication does not mention anything about a modulus ratio of 1, but according to the inventor's experiments, the modulus ratio is 0.1.
A much lower (0.02 or less) was observed.

Japanese Patent Publication No. 41-7892 and U.S. Patent No. 2880
No. 057 describes a method for melt spinning industrial polyester for use in tire cords and the like.

As is well known, the production of industrial polyesters uses different melt spinning conditions than those for textiles.

However, there are some points in these prior art that seem to be similar (sometimes in terms of physical properties) to the characteristics of the filament of the present invention.

These technical contents are shown in the comparison table below in comparison with the parameters of the present invention, and the differences from the present invention are clarified.

From the comparison table, it is clear that the industrial polyester filaments obtained by the method described in Japanese Patent Publication No. 41-7892 and U.S. Pat. No. 2,880,057 are very different from those of the present invention in process conditions and crystal structure. Will.

In addition, the as-spun filaments in these conventional techniques have completely different physical properties from those of the present invention (as-spun filaments), and only when drawn again after spinning, the as-spun filaments of the present invention (as-spun filaments) ), it should be noted that similar physical properties can be obtained.

The present invention will be explained in more detail below.

FIG. 1 is a schematic diagram of an apparatus for producing improved polyester filaments of the present invention.

The polyester filaments of the present invention consist primarily of polyethylene terephthalate, including at least 85 mole percent polyethylene terephthalate, and typically at least 90 mole percent polyethylene terephthalate.

In a particularly typical embodiment, the polyester filaments are substantially all polyethylene terephthalate.

On the other hand, ethylene glycol and terephthalic acid are present in the polyester structure in a proportion other than their derivatives.
Small amounts of one or more ester-forming reagents may be copolymerized.

For example, melt spinnable polyesters contain 85 to 100 mole percent (typically 90 to 100 mole percent) polyethylene terephthalate structural units;
Contains 15 mole percent (typically 0 to 10 mole percent) of copolymerized ester units other than polyethylene terephthalate.

Specific examples of other ester-forming reagents that copolymerize with polyethylene terephthalate include diethylene glycol, tetramethylene glycol, hexamethylene glycol, etc., as well as hexahytrotilefcouric acid, dibenzoic acid, adipic acid, sebacic acid, azelaic acid, etc. It is a dicarboxylic acid such as

The improved polyester filaments of the present invention are suitable for use in textiles or other commercial applications and are woven or knitted to produce fabrics, generally about 1 to 10 or about 1 to 10 or 1.5 to 5 denier/filament.

Polyester filaments can be provided in the form of continuous multifilament yarns.

1, for example, a continuous multifilament yarn of about 6 to 200 filaments, more preferably about 20 to 3 filaments, for example.
6 continuous filament yarns can be provided.

The improved polyester filaments of this invention have a unique internal structure.

The polyester filament according to the invention has 7j (1ntercon) interconnections present along its length.
nected) with a highly oriented crystalline microstructure.

The high degree of orientation of the crystalline regions of the filament is determined by standard wide-angle X-ray diffraction analysis.

The regions of the fiber between the interconnected and highly oriented crystalline curved microstructures consist of amorphous polymer chains,
The strands consist of substantially relaxed, low-order chain segments.

This is evidenced by the low amorphous orientation function exhibited by this structure at low shrinkage and high temperatures.

The relationship between low shrinkage and low amorphous orientation is well established in the literature.

See, for example, the work of Robert J. Samuel, J. Polymer Science, A2.10, 781 (1972).

The interconnects are generally amorphous and serve to further link the polymeric highly crystalline regions into one microstructure.

The presence of interconnections is inferred from the level of mechanical and thermomechanical voids exhibited by the filaments.

The internal structure of the improved polyester filaments of the present invention exhibits a balance of qualities not previously achieved in polyester filaments.

Discussed in detail below are the various qualities of these filaments.

The reported tensile and thermomechanical properties of polyester filaments of known technology are
It has been shown from this.

However, no polyester filament has so far been provided with sufficiently satisfactory elongation properties as well as the thermomechanical properties reported in the past.

Furthermore, in particular the microstructure of the polyester filaments of the invention is subject to only a certain limit of shrinkage, which occurs at high temperatures and high degrees of force.

This balance of filament properties is summarized by the ``modulus ratio'' defined below.

The balance of properties exhibited makes the polyester filaments of the present invention well suited for use in general textile or other commercial applications.

As shown below, many of the tests in which polyester filaments are tested are preferably performed by testing continuous multifilament yarns made of polyester filaments.

The number of filaments present in the yarn under test ranges from about 10 to 301, say 20, with varying force ξ convenience.

During the test, the filaments present in the yarn are not twisted.

In the areas of flexibility and initial modulus measurements, somewhat higher average values are given when the single filament test is converted to a multifilament yarn test.

The polyester filaments of the present invention generally exhibit average elongation properties of the first order at room temperature, ie, 25° C., in the presence of multifilament yarns.

Representative Examples Special Representative Examples Flexibility At Least At Least (Tenacity) Per Denier 3.25 Per Denier
Grams 3.75 grams Initial modulus value at least per denier 55 grams per denier 75 grams Elongation 75% or less 50% or less Tensile acid has a 3-1/3 inner gauge length and a strain rate of 60% per minute; ASTM D2256I compliance was determined using an Instron Stretch Tester (Model TM).

The yarn before testing is set according to ASTM D1776 at 70'F and 60% relative humidity for 48 hours.

It is noted that the flexibility and initial modulus values are comparable to those found in known commercial polyester filaments.

The polyester filaments of the present invention exhibit very desirable thermomechanical properties at elevated temperatures, which exhibit improved dimensional stability.

In the presence of multifilament yarns in air, the filaments shrink by less than 5% at 100°C.

(preferably 3.8% or less), and 8% at 175°C
or less (preferably 7.6% or less).

The above shrinkage values were determined using a DuPont Thermomechanical Analyzer (Model 941) at a heating rate of 10 with a load of 0.
It can be determined by operating at a constant gauge length of 0.5 °C/min.

Additionally, the polyester fiber filaments of the present invention exhibit unusually high internal tension or shrinkage forces at high temperatures.

Multifilament yarn + ioo℃l When strained, the filament has an average internal tension of about 0.3-0.5f! / Indicates denier.

A maximum internal tension of 0.4 g/denier is generally observed.

The internal tension values above are determined by an Instron tension tester programmed with a rapid response oven.

The thread sample is attached to the mouth of the tester and heated in air at 10°C/min to maintain a constant length.

Since this test is not sensitive to gauge length, a gauge length of about 6 inches is conveniently chosen.

The force generated by the heated yarn is monitored as a function of yarn temperature on a suitable recorder.

The force at constant temperature divided by the denier of the thread is. It is defined as the internal tension at that temperature.

Internal tension is a measure of the stress introduced into the thread during the process, indicating the stability of the molecular chain conformation in its structure and stabilizing groups of other species, especially in the interconnections and amorphous regions.

The above thermomechanical properties of the polyester filaments of the present invention can be summarized from the calculation of the "shrinkage modulus" parameter.

It is defined as the average internal tension in the multifilament yarn at a given temperature divided by the average percent shrinkage in the multifilament yarn at that temperature times 100.

The polyester filaments of the present invention, when multifilament yarns, generally have a shrinkage modulus of at least about 9
．． 09/denier at 100°C and a shrinkage modulus of at least about 3.51/denier at 175°C.

Such values are higher than those known.

The shrinkage modulus defined here indicates the degree of tension in these molecular chains, which serve as interconnections between crystalline regions.

A high shrinkage modulus generally indicates the presence of tense interconnections coexisting with a relaxed amorphous phase.

The unique balance of tensile properties and thermomechanical acidity of the filaments of the present invention is evidenced by calculation of the filament's "modulus ratio."

It is defined as the shrinkage modulus of the filament at 100°C as a multifilament yarn divided by the average initial module of the filament as a multifilament yarn at room temperature (ie 25°C).

The polyester filaments of the present invention exhibit a module ratio of at least 0.1, or from about 0.61 to about 0.2.

Known polyester filaments exhibit substantially lower modulus ratios.

Modulus ratio indicates the relative loading capacity of a fiber structure at elevated temperatures compared to room temperature.

The polyester filaments of the present invention also generally have an average birefringence of about 0.10 to 0.14 (i.e. about 0.1
1 to 0.14).

This is a range not typically exhibited by commercial polyester fibers.

The birefringence of the filament is determined using a Berek compensator attached to a polarizing microscope and shows the difference in refractive index parallel and perpendicular to the fiber axis.

The improved polyester filaments of the present invention are also characterized by their thermomechanical integrity.

Such filaments exhibit a relatively high initial modulus, a relatively high crystalline orientation function and a relatively low amorphous orientation function.

For example, the polyester filament is a multifilament yarn with an average initial modulus of at least 55 g/denier at 25°C and a birefringence of about 0.10 to 0.14;
The crystalline orientation function (Fc) is at least 0.88 (i.e. about 0.88-0.95) and the amorphous orientation function (p
a) does not exceed 0.35') (i.e. approximately 0.15 to 0
．． 35).

As known in the art, the birefringence of a fluorinated filament is a function of the crystalline portion of the filament and the amorphous portion of the filament.

See, for example, Robert J. Samuel, J. Polymer Science A2.10, 781 (1972).

Birefringence is expressed by the following formula.

△n=XFc△nc+(I
(1) Here, △n...Birefringence X...Crystallinity ratio Fc...Crystal circumference orientation parameter △nc...Crystal's intrinsic birefringence (0.220 for polyethylene terephthalate) Fa. ...Amorphous orientation parameter △na...Amorphous intrinsic birefringence (0.275 for polyethylene terephthalate) △nf...Type birefringence (low and can be ignored in this system) Crystal ratio X is Determined by well-known density measurements.

The crystal orientation parameter Fc is calculated from the average orientation angle θ determined by wide-angle X-ray diffraction.

Photographs of the diffraction patterns are analyzed from the average angle breeze of the (010) and (100) diffraction arcs to obtain average orientation angle data.

The crystal orientation parameter Fc is calculated from the following formula.

■ Fc=-(3CO82θ-1) (2) Once △
When n, X and Fc are known, pa is calculated from equation (1).

Δn (and Δna are acids specific to a given chemical structure, and change somewhat when the chemical composition of the molecule changes, ie, due to polymerization, etc.).

The illegally used melt-spun polyester preferably has an intrinsic viscosity, i.e., I, , V, of about 0.45 to 1.
．． 0, and particularly preferably I, V are about 0.
6 to 0.95.

I, V, of meltable polyester are conveniently expressed by the formula J
It is determined by im Inη1.

Here, ηr is the "relative viscosity" obtained by dividing the viscosity of a dilute solution of the polymer by the viscosity of the solvent (measured at the same temperature).
It is.

And C is the polymer concentration of the solution expressed in g/100ml.

The fiber-forming polyester further generally has a glass transition temperature of about 75°C to 80°C and a melting point of about 250°C to 20°C.
65°C or 260°C.

The spinneret selected for illegal use has one or typically a pair of extrusion orifices.

For example, 1-200 holes (i.e. 6-200
A standard conical spinneret with a diameter of approximately 10 to 6
0 mils (i.e. 10-40 mils) are illegally used.

Approximately 20-36 continuous filament yarns are produced.

The melt-spun polyester is subjected to a spinelette at a temperature above its melting point.

The molten polyester is preferably 11 about 270°C to 310°C.
at a temperature of approximately 285°C to 305°C (
For example, 300° C.) is the temperature at which it is extruded through the spinneret.

After extrusion through a spinneret, the resulting polyester material is subjected along its length to a gaseous atmosphere at a temperature below its glass transition temperature, for example below 80°C.

Pass through the solidification zone. There, the molten filamentary material transforms into solid filamentary material.

In the solidification zone, the molten substance changes from a molten state to a semi-solid state;
Then, it changes from a semi-solid state to a solid state.

When in the solidification zone, the material undergoes substantial orientation while in a semi-solid state.

The solidification zone is also called the "quench zone."

The gaseous atmosphere within the solidification zone is typically circulated to make heat exchange more efficient.

The gaseous atmosphere in the solidification zone is preferably between about 10°C and 40°C.
Served at a temperature of

Most preferably, the temperature is about room temperature (eg, about 25°C).

The chemical composition of the gaseous atmosphere is not critical to the illegal operation provided it does not react with the polyester filamentous material.

In most cases, the gaseous atmosphere in the solidification zone is air.

Other gaseous atmospheres selected for use in the solidification zone are inert gases such as helium, argon, nitrogen, and the like.

The gaseous atmosphere in the consolidation zone preferably hits the extruded polyester material and produces a uniform wench.

There is no substantial circumferential non-uniformity across the fiber diameter.

Quench uniformity is demonstrated by the tendency of the resulting filamentary material to not self-shrink upon application of heat.

Therefore, flat yarns are preferably produced.

The solidification zone is preferably directly below the spinneret.

and the extruded polyester material is then approximately o, o
Suspend in the axial direction for a period of 0.4 seconds, most preferably between about 0.033 and 0.14 seconds.

Generally, the solids zone has a length of about 0.25 to 20 feet, typically 1 to 7 feet.

A gaseous atmosphere is also preferably introduced at the lower end of the consolidation zone and flows along a continuous length of the polyester material moving downwardly from the spinneret.

Central flow quenching or other methods that provide the desired quenching may also be used.

A thermal shroud may be located intermediate the spinneret and the solidification zone.

The resulting filamentary material is then conditioned through a conditioning zone along its length.

This is a gaseous atmosphere above the glass transition temperature and below the melting point.
That is, usually 90 to 180°C (for example, 90 to 140°C
℃) at a temperature of about 0. The time is from oo1 to 0.8 seconds.

There occurs substantial crystallization of the previously solidified filamentary material.

The conditioning zone is preferably about 110-1
Served in a gaseous atmosphere at 20°C.

The preferred time that the moving filamentary material is in the conditioning zone is about 0.0016 to 0.6 seconds, most preferably about 0.03 to 0.09 seconds.

If the time is much lower than 0.001 seconds, stable achievement of the desired acidity level will not be achieved.

Longer residence times are not advantageous and are not used.

The chemical composition of the gaseous atmosphere in the conditioning zone is not critical to the illicit operation if it does not react with the polyester filamentary material.

Steady air or water vapor is conveniently chosen.

Other typical gaseous atmospheres used in conditioning zones include helium, argon, and nitrogen.

Bring the conditioning zone to the desired temperature with a band heater or other heating method.

The conditioning zone is generally about 0.5 to 3 in length
0 feet are typically about 5 to 12 feet in length.

The resulting filamentary material is pulled from the conditioning zone at a rate of approximately 1000 to 6000 meters per minute (preferably 2500 to 3500 meters per minute).

On the other hand, stress is approximately 0.15 to 0.6 g/denier (
Typically, the concentration is 0.2 to 0.4 grams/denier).

After extrusion, the filamentary material is maintained under constant tension and no stress isolation is used in the region of exit from the spinneret and conditioning zone during the process (ie, axially suspended without external contact).

Upon exiting the conditioning zone, the filamentary material generally exhibits a denier/filament of about 1 to 10, such as 1.5 to 5.

The improved polyester production process is carried out in an apparatus having a heated conditioning chamber of appropriate length below the quencher zone and the desired high stress extraction equipment.

The results achieved with the polyesters described herein are considered to be contrary to what is known in the polyester fiber industry.

Passage of the filamentous material through the conditioning zone surprisingly enhances its properties through a change in its internal structural morphology.

More particularly, the tensile shaping of filamentary materials has been surprisingly improved, eliminating the need for conventional thermal stretching steps.

The tensile strength and module have been improved and this shrinkage note has been lost.

When in the conditioning zone, the filamentary material is heat treated under constant tension.

Although some thermal elongation may occur during this heat treatment, this method differs from the stretching method due to constant tension rather than constant strain criteria.

The level of tension in the filamentary material in the conditioning zone is extremely critical to the desired structure and quality, and is dictated primarily by the rate of tension from the conditioning zone rather than by its interaction with the surrounding gas.

There is no stress separation along the filamentary material between the spinneret and the point of tension from the conditioning zone (i.e., the filamentary material has no stress separation along the filamentary material between the spinneret and the point of tension from the conditioning zone). (virtually suspended below).

Should passage of the filamentary material through the conditioning zone be omitted, the denier and cross-sectional dimensions of the filamentary material will generally be the same.

The extruded filamentous material between the point of maximum mold engraving area and the point of tension from the conditioning zone is
generally exhibiting a tensile ratio of about ioo:i to 2000:1;
Most typically exhibit a tensile ratio of about 600=1 to 1700:1.

As used above, "tensile ratio" is defined as the ratio of the maximum emplacement cross-sectional area to the cross-sectional area of the filamentary material leaving the conditioning zone.

This substantial change in cross-sectional area occurs almost unilaterally in the solidification zone before complete etching.

In some embodiments, a reduction in the cross-sectional area of the filamentary material by up to about 4:1 is observed in the conditioning zone following the heat-induced stretching described above.

The illegal theory by which polyester filamentary materials exhibiting the cited properties can be produced is believed to be complex and a simple explanation is not possible.

However, it is believed that:

In other words, the stress acting on the semisolid filamentous material in the solidification zone generates a fibrillar microstructure of oriented polyester molecules within each fiber, which helps to nucleate the growth of polymer crystals between adjacent fibrils. Seem.

As the resulting filamentary material then passes through the conditioning zone, substantial crystallization occurs spontaneously in the oriented fibrillar structure, as defined.

Such rapid crystallization creates lamellae on top of the existing fibrillar structure.

Lamellar crystals (extend between fibrils, lamellar crystals are held together by linked molecules).

The resulting filamentary material may be further processed through the use of processing equipment and used directly in applications requiring continuous filament fiber yarns.

If desired, one can change from flat yarns to textured yarns, for example by utilizing the known false twist weaving conditions.

In an illustrative example of a 150 denier yarn, the yarn speed is 1/min.
Using a speed of 25 meters, a feed roll heater plate temperature of 215° C., an overfeed to the heater of about 3.5%, and about 60 turns per inch.

The following examples are given to specifically illustrate the invention.

However, it is to be understood that the invention is not limited to the specific details shown in the examples.

The example of the device shown in the figure is shown for reference only.

The invention is not limited to the use of the apparatus shown.

On each side the polyester has an intrinsic viscosity of 0.67 (I, V,)
It is polyethylene terephthalate with

25 in orthochlorophenol with an intrinsic viscosity of 100 m7
°C o, i was measured from a crumb polymer solution.

Table 1 shows the characteristics of the polyester filament produced on each side.
The tables shown in Tables 1 and 2 follow all examples.

Example 1 Granular polyethylene terephthalate is placed in hopper 1 and 6
) and proceed to the spinneret 2 by the screw conveyor 4.

The polyethylene terephthalate particles are melted into a homogeneous phase by the heater 6 and further advanced against the spinneret 2 by the pump 8.

The spinneret 2 has a standard conical entrance and a ring of 20 extruded holes, each 20 mils in diameter.

The molten polyethylene terephthalate is extruded through a spinelette 2 at a temperature of about 300°C.

The resulting extruded polyethylene terephthalate 10 passes directly from the spinneret through a solidification zone 12.

Consolidation zone 12 is six feet long and vertically oriented.

Room temperature air (ie, about 25° C.) is continuously passed at 14 into the assimilation zone 12 .

14 is provided through conduit 16 and fan 18.

Air is continuously pumped through conduit 20.

20 is placed vertically in communication with the solidification zone 12 and the wall and is continuously fed through a conduit 22.

Upon passing through the consolidation zone, the extruded polyethylene terephthalate is converted into a continuous length of spun polyethylene terephthalate yarn.

The polymeric material first changes from a molten state to a semi-solid state and then passes from the semi-solid state through a solidification zone 12 to a solid state.

The extruded polyethylene terephthalate is approximately 0.045
It is present in the solidification zone 12 with a residence time of seconds.

When pulled from consolidation zone 12, the continuous length of polyethylene terephthalate yarn 24 then immediately passes perpendicularly through a 12 foot long conditioning zone 26.

In the conditioning zone 26, the walls are statically heated at a temperature of 120° C. by surrounding band heaters 28.
) The air atmosphere is maintained.

The polyethylene terephthalate yarn is structurally modified in conditioning zone 26 with a residence time of about 0.09 seconds.

The resulting polyethylene terephthalate yarn was extruded under constant tension at a stress of approximately 0.2 g/denier at a speed of 2500 meters per minute in conditioning zone 2.
Stretched from 6.

The extruded filamentary material between the area of maximum engraving and the point drawn from the conditioning zone has a draw ratio of about 1400:1.

The obtained polyethylene terephthalate yarn has a denier of 2 per filament and is packaged at 30 after passing through the godets 32 right and 34.

Contact with roller 36 provides an anti-static lubricant.

The polyethylene terephthalate yarn is suspended substantially without external contact between the spinneret and the point of drawing from the conditioning zone 26.

Therefore, there is no stress separation along the length of the yarn in this region and the fibrous material is under substantial stress during the process.

The structure of this yarn was such that an interconnected, highly oriented crystalline microstructure existed along its length, and this coexisted with an amorphous phase.

Comparative Example 2 For comparison purposes, the example was repeated with the following exceptions.

That is, the static air atmosphere in conditioning zone 26 was at room temperature (ie, about 25°C) instead of 120°C.

The extruded filamentary material between the largest engraving area and the point extending from the conditioning zone is about 140
It was stretched at a ratio of 0:1.

Example 3 Example 1 was repeated with the following exception.

Specifically, gill polyethylene terephthalate yarn was drawn from the conditioning zone 26 at a speed of 3000 meters per minute under a stress of about 0.25 grams/denier.

The extruded polyethylene terephthalate yarn was present in the solidification zone 12 for a residence time of approximately 0.036 seconds.

The polyethylene terephthalate yarn was present in conditioning zone 26 for a residence time of approximately 0.07 seconds.

The extruded filamentous material between the area of maximum swelling and the point of extension from the conditioning zone is approximately 1500:
It was stretched at a ratio of i.

Comparative example 4 For comparison purposes, Example 3 was repeated with the following exceptions.

That is, the static air atmosphere in conditioning zone 26 was at room temperature (ie, about 25°C) instead of 120°C.

The extruded filamentary material between the maximum engraving area and the point of extension from the conditioning zone is 150
It was stretched at a ratio of 0:1.

Comparative Example 5 For comparative purposes, Example 1 was repeated with the following exceptions.

The spinneret has a ring of 36 extruded holes, each with 2
0 mil diameter, the conditioning zone was at room temperature (approximately 25° C.), and the yarn was drawn at a speed of 650 meters per minute and a stress of approximately 0.018 grams/denier.

Comparative Example 6 For comparative purposes, Example 1 was repeated with the following exceptions.

The spinneret shall have a ring of 36 extruded holes, each 20 mil diameter, the conditioning zone will be at room temperature (i.e., 25° C.), and the yarn will be drawn under stress of 0.038 crumbs/denier at a speed of 1100 meters per minute. It was done.

Comparative Example 7 For comparative purposes, Example 1 was repeated with the following exceptions.

The zpinelet was a ring of 36 extruded holes, each 20 mils in diameter, the conditioning zone was at room temperature (i.e., about 25°C), the thread was running at a speed of 4000 meters per minute,
It was drawn from a conditioned zone under stress of about 0.15 grams/denier.

Comparative Example 8 For comparative purposes, Example 1 was repeated with the following exceptions.

That is, the spinneret has a ring of 36 extruded holes 20 mils in diameter, and the tangled thread is drawn from the consolidation zone at a rate of 2500 meters per minute under a stress of about 0.2 crums/denier without passing through the conditioning zone. Afterwards, they were collected in a spool.

The thread was unwound from the spool and maintained at 125°C, with a temperature of about 0.2
It passed through the conditioning zone under gram/denier stress and was picked up at a speed of 200 meters per minute.

The yarn was in the conditioning zone with a residence time of about 1 second.

No stretching occurs when the yarn is in the conditioning zone.

Comparative Example 9 For comparative purposes, Example 3 was repeated with the following exceptions.

That is, the spun yarn was drawn from the consolidation zone under a stress of about 0.25 grams/denier at a speed of 3000 meters per minute without passing through a conditioning zone and then collected in a spool.

The thread was unwound from the spool and maintained at 120°C, with a temperature of approx.
It passed through a 25 g/denier strained conditioning boon and was picked up at a speed of 2000 meters per minute.

The yarn was in the conditioning zone with a residence time of about 1 second.

Once in the conditioning zone, the spun yarn was drawn at a draw ratio of approximately 2.6:1.

Comparative example 10 Comparative Example 5 was repeated with the following exceptions.

That is, the spun yarn is continuously passed through a 12-inch heat shoe kept at 80°C under atmospheric pressure to reduce its length to 3.
It was stretched 3 times.

The spun yarn was subjected to a heat shoe at a speed of 50 meters per minute.

It was then brought into contact with the surface of the heat shoe for about 0.1 seconds.

Comparative example 11 Comparative Example 6 was repeated with the following exceptions.

That is, the spun yarn was kept at atmospheric pressure of 100°C.
Continuously pass through a 2 inch heat shoe to reduce its length to 2.2
It was stretched 7 times.

The spun yarn was subjected to a heat shoe at a speed of 50 meters per minute and was in contact with the surface of the heat shoe for about 0.1 seconds.

Comparative Example 12 For comparison purposes, Example 1 was repeated with the following exceptions.

That is, the spinneret was 20 mils in diameter with a ring of 36 extrusion holes, and the spun yarn was drawn from the consolidation zone at a rate of 1000 meters per minute under a stress of approximately 0.008 grams/denier without passing through a conditioning zone. It is later collected into a spool of thread.

The thread was unwound from the spool and kept at 90°C under atmospheric pressure.
The film was continuously passed through an inch heat shoe to be hot-stretched to 5 times its length.

The yarn was subjected to a heat shoe at a speed of 50 meters per minute.

It was then brought into contact with the surface of the heat shoe for 0.1 seconds.

Comparative Example 13 Comparative Example 12 was repeated and the yarn product of the sample was
It was passed continuously through hot rolls kept at 20°C to relax it by 20%.

The properties of the polyester filaments produced in Examples 1 to 13 are shown in Table I1 and Table II below.

Only Shiohata Nos. 1 and 3 produced polyester filaments according to the invention.

Comparative Examples 8 and 9 show the following.

That is, if the filamentary material is collected after passing through the solidification zone and passed through a conditioning zone at a similar temperature and under equal stress, the desired filaments will not be produced.

Furthermore, Comparative Examples 2, 4.5 to 7 and 10 to 13 have the result that the filaments sought do not form under various different process conditions.

Although the invention has been described in terms of representative examples, it is to be understood that obvious changes and modifications may be made to known methods.

Such changes and modifications are to be considered within the scope of this invention.

Embodiments of the invention are as follows.

(1) consisting of at least 85 mole percent polyethylene terephthalate, suitable for commercial applications, having a highly oriented crystalline microstructure over the length of the filament, and a substantially non-oriented amorphous phase with dispersed phases; An improved polyester filament, wherein the filament exhibits a tendency to undergo only mild shrinkage even under high forces at elevated temperatures, as evidenced by a modulus ratio of at least 0.1.

(2) An improved polyester filament according to (1) above comprising at least 90 mole percent polyethylene terephthalate.

(3) The improved polyester filament according to (1) above, wherein the filament is substantially entirely polyethylene terephthalate.

(4) An improved polyester filament according to (1) above, wherein about 6 to 200 of said filaments are present as threads.

(5) An improved polyester system according to (4) above, in which the threads are flat and exhibit substantially no tendency to self-shrink upon application of heat.

(6) Improved polyester filaments as described in item 1) having an average flexibility of at least 3.25 grams denier, an average initial modulus of at least 55 grams/denier and an average elongation of 75% or less at 25°C in a multifilament system. .

(7) An improved polyester according to (1) above having an average flexibility of at least 3.75 grams/denier, an average initial modulus of at least 75 grams/denier, and an average elongation of at least 50% at 25° C. in a multifilament yarn. filament.

(8) An improved polyester filament according to (1) above, wherein the filament exhibits an average birefringence in the range of about 0.10 to 60.14.

(9) A multifilament yarn with an average warp shrinkage of 5% or less when heated to 100°C.
An improved polyester filament according to the description in (1) above, which exhibits an average warp shrinkage of 8% or less at 5°C.

(10) When the filament is a multifilament yarn and is at 100°C, the average warp shrinkage is 3.8% or less and 17
(1) above, where the average warp shrinkage is 7.6% or less at 5°C
Modified polyester filament as described in.

0υ The filament has a modulus ratio of about 0.1 to 0.
2. An improved polyester filament according to (1) above.

02) An improved polyester filament as described in (1) above, wherein the filament has a denier of about 1 to 15.

(13) An interconnected, highly oriented crystalline microstructure is present along the length of the filament, coexisting with a substantially unoriented, dispersed amorphous surrounding phase, and the filament has a modulus ratio of about 0.1. shows a tendency to undergo only a low degree of shrinkage even under high forces at high temperatures, as evidenced by a
average softness in grams/denier, average initial modulus of at least 75 grams/denier, average elongation not more than 50%, and average warp shrinkage of 3 at 100°C.
．． 8% or less, and the average warp shrinkage is 7.6 at 175℃
% or less of modified polyethylene terephthalate filaments suitable for use in commercial applications.

(14) The improved polyethylene terephthalate according to the description in (13) above, wherein the filaments of about 3 or more are yarns.

(15) An improved polyethylene terephthalate yarn according to (14) above, wherein the yarn is flat and exhibits no tendency to self-shrink substantially upon application of heat.

(16) When an interconnected and highly oriented crystalline microstructure is present along the length of the filament, coexisting with a dispersed amorphous acid phase with a substantially stop-valve orientation, and the average initial modulus is 25 °C for multifilament yarns. , at least 55 g/denier, a birefringence of about 0.10 to 0.14, a crystalline orientation function of at least 0.88, and an amorphous orientation function not exceeding 0.35. An improved polyester filament comprising at least 85 mole percent polyethylene terephthalate suitable for use in commercial applications.

αD Improved polyester filament according to (16) above, consisting of at least 90 mole percent polyethylene terephthalate.

C8) An improved polyester yarn according to (L6) above, wherein the yarn is about 6 to 200 filaments.

C9) Improved polyester filaments according to α6) above, having an average flexibility of at least 3.25 g/denier and an average elongation of at least 75 percent at 25°C in multifilament yarns.

(20) A multifilament yarn having an average flexibility of at least 3.75 g/denier, an average initial modulus of at least 75 g/denier, and an average elongation of not more than 50 percent at 25°C (16)
) Modified polyester filament as described in ).

(4) At 100℃ for multifilament yarn, the average warp shrinkage is 5% or less and at 175℃ it is 11%.
An improved polyester filament as described in α6) above, having a warp shrinkage of 8% or less.

C2) The filament is a multifilament yarn of 100
℃, the average vertical shrinkage is less than 3.8%, and at 175℃
An improved polyester filament according to the above (16), which exhibits an average longitudinal shrinkage of 7.6% or less.

(23) An improvement according to (16) above, wherein the filament has a tendency to be resistant to a low degree of shrinkage even under high temperatures and high forces, as evidenced by a modulus ratio of at least 0.1. Polyester filament.

(24) An improved polyester filament as described in σ6) above, wherein the filament has a denier of about 1 to 15.

(e) When an interconnected highly oriented crystalline microstructure coexists with a substantially non-oriented amorphous dispersed phase over the length of the filament and the average initial modulus is 25°C for a multifilament yarn. Commercially available A modified polyethylene terephthalate filament of about 1 to 15 denier suitable for the application.

(e) An improved polyethylene terephthalate filament as described in (e) above, wherein about 6 to 200 filaments are present in the yarn.

(5) An improved polyetherene terephthalate according to (a) above, wherein the thread is flat and has substantially no tendency to self-shrink upon application of heat.

(Support) Modified polyethylene terephthalate according to the above description, wherein the filament exhibits a tendency to undergo a low degree of shrinkage at high temperatures and high forces, as evidenced by a modulus ratio of about 0.1 to 0.2.

[Brief explanation of drawings]

The accompanying drawings are examples of apparatus for carrying out the invention. 1...Hopper, 2...Spinelet, 4...Conveyor, 6...Heater, 8...Pump, 10... ... Extruded polyethylene terephthalate, 12 ... Solidification zone, 14 ... Room temperature air, 16 ... Conduit, 18 - River ... Fan, 22 ... Conduit, 24...Polyethylene terephthalate thread, 26°°°°°Conditioning knitted cord, 28.
...Band heater, 32 and 34...
・Godet, 36...Roller.

Claims (1)

[Claims] 1 undergoes melt-spinning, solidification and heat conditioning treatment while remaining suspended during the spinning process at take-up speeds of 91,000 to 6,000 m/91,000 to 6,000 m/s and tension ratios of 100:1 to 2,000:1. at least 85 mol%
of polyethylene terephthalate with a highly oriented crystalline microstructure interconnected over the length of the filament, the substantially non-oriented amorphous phase coexists in a dispersed manner and remains as spun, therefore during spinning. Tendency to undergo only mild shrinkage at high temperatures and high forces, as evidenced by a modulus ratio of at least 0.1, in the absence of further stretching after conditioning treatment of %50
%, an average longitudinal shrinkage at 100°C of less than 5%, and a birefringence of 0.10 to 0.14.