CN1056543A - Drawn polyester yarn with high strength, high initial modulus and low shrinkage - Google Patents

Abstract

The present invention relates to a kind of drawn polyester yarn.This characteristics are that initial secant modulus is greater than per dawn 150 gram/100%.This characteristics also are, shrinkage factor less than 8% or intensity greater than 7.5 gram/dawn.Or this characteristics are that intensity was at least for 10 gram/dawn, and initial modulus is at least per dawn 120 gram/100%, and shrinkage factor is less than 8%.

Description

Drawn polyester yarn with high strength, high initial modulus and low shrinkage

The present invention relates to a kind of drawn polyester yarn with high strength, high initial modulus and low shrinkage.

Since but the synthetic polymer that becomes fine melt-spun came out, the fiber producer was just seeking to improve intensity and the stable method of making fiber with these polymer.These fibers need higher intensity and stability, so that can open up textiles purposes in addition for its goods.This non-textile purposes (being also referred to as " commercial Application ") comprising: tyre cord; Sewing threads; Canvas; The fabric such as fiber web or the pad that are used for road structure or other geotextiles purposes; Industrial band; Composite; Architectural fabric; The reinforcing material of flexible pipe; Laminated fabric; Rope; And similar applications.

At first, in above-mentioned these industrial uses some being arranged is to use viscose rayon.After, select for use nylon to replace viscose rayon.In the seventies, adopted conventional polyester, for example polyethylene terephthalate is competed with nylon.About 1985, adopted high performance polyester, that is, and intensity and the higher polyester of stability.

Below some previous technical patent is done concise and to the point general introduction and shows, as the possible approach of intensity that improves these synthetic fiber and stability after deliberation three general fields.These general fields comprise: at the method that stretches; Method at polymer; With method at spinning.After, " stretching " speech refers to heating and the stretching that spun is carried out." processing of polymer " was meant before spinning the processing to polymer carried out." spinning " speech is meant the process that is formed long filament by polymer, but does not comprise stretching.

As follows at the method that stretches:

At United States Patent (USP) 3,090, disclose the polyamide multistage stretching in 997, be used for tyre cord.Fiber (nylon) is melt-spun in the usual way.Then, spun fiber is stretched with three grades of technologies (stretch, heat and then stretch), to obtain having the stretching nylon of following performance: from 10.4 to the 11.1 gram/dawn of strength range (gpd); Percentage elongation from 12.9% to 17.1%; Initial modulus 48 to 71 gram/dawn/100%.

At United States Patent (USP) 3,303, a kind of single-stage drawing process that is used for polyamide is disclosed in 169, it can form the polyamide filament of high-modulus, high strength and low shrinkage.The polyamide filament that just spins drawn stretch And and be heated at least 115 ℃, the silk that obtains is had: intensity was 5 to 8.7 gram/dawn; Percentage elongation 16.2% to 30.3%; Initial modulus is 28 to 59 gram/dawn/100%; Shrinkage is 3.5% to 15%.

At United States Patent (USP) 3,966, in 867, a kind of secondary drawing technology that relative viscosity is 1.5 to 1.7 polyethylene terephthalate that is used for is disclosed.In the phase I, fiber is heated to 70 to 100 ℃, the draw ratio with 3.8 to 4.2 stretches.In second stage, fiber is heated to 210 to 250 ℃ And and stretchings, and phase I and second stage draw ratio add up to 5.6 to 6.1.The drawn yarn of gained has following performance: intensity, 7.5 to 9.5 gram/dawn; Percentage elongation is about 2% to 5% under the load of 5 gram/dawn; Elongation at break is 9% to 15%; Shrinkage 1% to 4%.

At United States Patent (USP) 4,003, in 974, the polyethylene terephthalate spun that will have 24 to 28 high relative viscosity (HRV) is heated to 75 to 250 ℃, stretches simultaneously, and is by the draw roll of a heating, at last that it is lax then.Drawn yarn has following performance: intensity, 7.5 to 9 gram/dawn; Shrinkage about 4%; Elongation at break 12% to 20%; Load capacity was 3 to 5 gram/dawn when 7% percentage elongation.

As follows by polymer being handled those methods that strengthen a performance:

At United States Patent (USP) 4,690, in 866 and 4,867,963, the inherent viscosity of polyethylene terephthalate is greater than 0.90.At United States Patent (USP) 4,690, the performance of in 868, just spinning (not stretching) fiber is as follows: elongation at break, 52% to 193%; Birefringence, 0.0626 to 0.136; Degree of crystallinity, 19.3% to 36.8%.The performance of drawing of fiber is as follows: intensity, 5.9 to 8.3 gram/dawn; Percentage elongation, 10.1% to 24.4%; Contract with dry rate (at 210 ℃), 0.5% to 10.3%.At United States Patent (USP) 4,867, in 936, the performance of drawing of fiber is as follows: intensity, about 8.5 gram/dawn; Elongation at break, about 9.9%; Shrinkage (at 177 ℃), about 5.7%.

Method at spinning is as follows:

At United States Patent (USP) 3,053, in 611, polyethylene terephthalate is heated to 220 ℃ in 2 meters long spinning shafts after leaving spinnerets.In second path, cold water is sprayed on the fiber then.With the speed coiling fiber of 1600 meters of per minutes, with after-drawing, the intensity that obtains was 3.5 gram/dawn.

At United States Patent (USP) 3,291, in 880, polyamide is spun into silk by spinnerets, is chilled to about 15 ℃ then, uses the direct steam injection fiber subsequently.The degree of orientation and the birefringence of as-spun fibre are low.

At United States Patent (USP) 3,361, in 859, synthetic organic polymer is spun into fiber.When fiber is come out by spinnerets, with its " controlled delaying cooled off ".This cooling processing is being carried out in 7 inches of spinneretss.On the top (that is, near an end of spinnerets), temperature is 300 ℃, and bottom (from about 7 inches of spinnerets) locates minimum temperature is 132 ℃.The birefringence of spun is low by (11 to 35 * 10 ^-3), the performance of drawn yarn is as follows: intensity, 6.9 to 9.4 gram/dawn; Initial modulus, 107 to 140 gram/dawn/100%; Elongation at break, 7.7% to 9.9%.

At United States Patent (USP) 3,936, in 253 and 3,969,462, mentioned the serviceability temperature scope from about 115 to 460 ℃ heating muff (length is from half foot to 2 feet).In last patent, the temperature at heating muff top is than bottom height.The performance of drawn yarn is as follows: intensity, 9.25 gram/dawn; Percentage elongation, about 13.5%; Shrinkage, about 9.5%.In one patent of back, the temperature in the heating muff is constant, and the performance of drawn yarn is as follows: intensity, 8 to 11 gram/dawn; Elongation at break, 12.5% to 13.2%.

At United States Patent (USP) 3,946, in 100, fiber is spun by spinnerets, solidifies being lower than under 80 ℃ the temperature.Then the fiber that solidifies is reheated to a certain temperature between glass transition temperature of polymer (Tg) and fusion temperature.The fiber of this heating is pulled out by the thermal treatment zone with the speed of 1000 to 6000 meters of per minutes.The performance of silk is as follows: intensity, 3.7 to 4.0 gram/dawn; Initial modulus, 70 to 76 gram/dawn/100%; Birefringence, 0.1188 to 0.1240.

At United States Patent (USP) 4,491, in 657, polyester multifilament spins And and curing with high fast thawing.Be solidificated in the zone that is connected to form successively by the thermal treatment zone and cooling zone and carry out.The thermal treatment zone is a garden cartridge heater (temperature range from the fusion temperature to 400 of polymer ℃), and its length is 0.2 to 1.0 meter scope.Cool off with 10 ℃ to 40 ℃ air the cooling zone.The drawn yarn that makes in this way has following performance: initial modulus, 90 to 130 gram/dawn; Shrinkage (at 150 ℃) is less than 8.7%.

At United States Patent (USP) 4,702, in 871, the fiber that just spins is entered into a case with negative pressure.The performance of spun is as follows: intensity, 3.7 to 4.4 gram/dawn; Birefringence, 104.4 to 125.8(* 10 ^-3); Dry-hot shrinkage, 160 ℃ 15 minutes be 4.2% to 5.9%.

At United States Patent (USP) 4,869, in 958, fiber spinning under the situation that does not heat is reeled then.At this moment, the degree of crystallinity of fiber is low, but its degree of orientation height.Then fiber is heat-treated.The performance of drawing of fiber is as follows: intensity, 4.9 to 5.2 gram/dawn; Initial modulus, 92.5 to 96.6 gram/dawn/100%; Percentage elongation, 28.5% to 32.5%.

More than the commentary of these patents is shown, though have some to have high strength or low shrinkage in the fiber that makes with above-mentioned the whole bag of tricks, neither one is explained a kind of method that has the silk of high strength, high initial modulus and low shrinkage simultaneously or make this drawn yarn in the above-mentioned patent.

The immediate patent of addressing this drawn yarn is a United States Patent (USP) 4,101,525 and 4,195,052, and they are the relevant patents that transfer patent assignee.In above-mentioned two parts of patents, polyester filament (inherent viscosity of polymer is 0.5 to 2.0 deciliter/gram) is by the spinnerets melt-spun.The long filament of fusion is by a curing area, and their are transformed into solid fiber by Zhou Leng And equably there.And solid fiber is pulled out from curing area with sizable stress (0.015 to 0.15 gram/dawn).These solid fibers that just spin have quite high birefringence (about 9 to 70 * 10 ^-3).The cured fiber that will just spin then stretches, and then heat-treats.The long filament performance that stretches is as follows: intensity, 7.5 to 10 gram/dawn; Initial modulus, 110 to 150 gram/dawn/100%; Aerial shrinkage is less than 8.5% under 175 ℃.

The present invention relates to a kind of drawn polyester yarn.This characteristics are that initial secant modulus is greater than 150 gram/dawn/100%.The silk characteristics also be shrinkage less than 8% or intensity greater than 7.5 gram/dawn.In other words, this characteristics are that intensity was at least for 10 gram/dawn, and initial modulus is at least 120 gram/dawn/100%, and shrinkage is less than 8%.

For example explanation the present invention, provided the process schematic representation that the application recommends, but should be appreciated that, the present invention is not subjected to the accurate arrangement of being given and the restriction of device.

Fig. 1 is the signal front elevation of spinning process.

Fig. 2 is the signal front elevation of drawing process.

The drawn yarn and the spinning process of high strength, high initial modulus and low shrinkage will be discussed below." silk " or " long filament " or " fiber " but these nouns are meant any fiber of being made by the synthetic organic polymer of melt-spun.These polymer can include, but is not limited to polyester and polyamide.But the present invention is special relevant with polyester, polyethylene terephthalate (PET) for example, the mixture of polyethylene terephthalate and polybutylene terephthalate (PBT) (PBT), and with the crosslinked polyethylene terephthalate of polyfunctional monomer (for example pentaerythrite).Above-mentioned polymer can contain conventional additive.The inherent viscosity (for being polymer based with the ethylene glycol terephthalate) of silk can be between 0.60 and 0.87.But the present invention does not rely on the inherent viscosity of polymer.

With reference to Fig. 1, provided a device for spinning 10 among the figure.Conventional extruder 12 that is used for molten polymer section usefulness and spinning manifold 14 link fluid with pipeline.In spinning manifold 14, a filament spinning component commonly used 16 is arranged.As known on the technology, filament spinning component can be a loop configuration, and polymer is filtered by the fine build-up bed therein.The spinnerets (not shown) that also comprises a routine as the part of assembly 16.Polymer can be from approximately per hour 10 to 55 pounds by the flow velocity of assembly.55 pounds of the upper limits only by the actual size decision of assembly 16, use big assembly can reach higher flow velocity.Spun filament denier (dpf) is from 3 to 20; The filament denier of finding silk is in 5 performance between 13 time and engineering properties the bests.

When fiber leaves spinnerets, can randomly use the inert gas (for example air) of heat with its quenching.Referring to United States Patent (USP) 4,378,325, the present invention quotes as a reference.In general, gas is about 230 ℃, and air feed speed is about 6 standard cubic foots of per minute.If air is too warm, that is, be higher than 260 ℃, the remarkable variation of performance of then spun silk.

Abut against below the spinning manifold 14 snugly (that is, airtightly) and load onto an elongated path 18.Length about 5 meters or a longer insulation tube are arranged in this path.It is long that the back can go through the path.The internal diameter of pipe enough big (for example 12 inches), so as to make all silks of coming out from spinnerets can be in the clear total length by pipe.Many round heaters commonly used are housed in the path, can control along the temperature on its length so that make in the pipe.The back will discuss the path temperature in more detail.The path preferably is divided into some independently temperature provinces again, so that control temperature better.Once adopted 4 to 7 temperature provinces independently of sum.Path 18 can comprise an air sparger 17 in order to temperature in the control path.The design of distributor 17 is to scatter inert gas equably around the path.

The truncated cone 19 that a porous is arranged in the lowermost end in path 18, that is, and a kind of device that is used for reducing air turbulence.The diameter and the caliber of preferably long 3 feet of awls 19, the top are big equally, the diameter of its bottom is about half of upper end, discharge air from the lowermost end of pipe through the exhaust outlet 21 of band valve with it, therefore the motion in the Silk Road that is caused by the air rapids is reduced greatly or is got rid of fully.

Below the lowermost end in path, the Silk Road converges.This converging can be finished with oiling device 20.This is silk contact for the first time after leaving spinnerets.

The length in path, one filament do not converge and the path in the air themperature distribution situation for particular importance of the present invention.About Temperature Distribution, should select one section very big length (for example at least 3 meters) fiber temperature will remain on its glass transition temperature Tg.Can make whole path length all remain on this more than temperature, but this can make the long filament instability of coiling.Therefore, from practicality, the temperature in the path is reduced to below the Tg, so that make long filament before reeling changes of crystal take place no longer.Preferably selected Temperature Distribution is in the Temperature Distribution of not having outer pipe planted agent formation when hot.But the situation of " not having outer heat " is unpractiaca, because many factor affecting path temperature is arranged.Therefore the path Temperature Distribution preferably is controlled to be linear distribution, just temperature can be got rid of outside state-variable.

Air themperature in the path is controlled with the cast heater.Preferably the path is divided into many zones, each regional air themperature is controlled at a predetermined numerical value.Therefore, the temperature in the path can become along path length.Temperature in the path can be up to the spinning temperature of polymer or drops to the glass transition temperature Tg (Tg of polyester is about 80 ℃) that is equal to or less than polymer.Around spinnerets, when molten polymer flows out spinnerets, promptly reach polymer spinning temperature.But the air themperature in the path preferably is controlled at from about 155 ℃ to about 50 ℃.When winding speed was lower than 14000 feet per minutes, first district of contiguous spinnerets preferably was controlled at about 155 ℃, and is controlled at about 50 ℃ from a spinnerets district farthest.

But linear temperature Fen Bu And is non-to be unique Temperature Distribution that can cause superior results disclosed in this invention.When batching (or reel) speed greater than 14000 feet per minutes (4300 meters/minute), Temperature Distribution (when being divided into four distinct area in the path) can be as following: (initial downwards by spinnerets) first district-Yue 105 ℃ to about 110 ℃; Second district-Yue 110 ℃ to about 115 ℃; The 3rd district-Yue 125 ℃ to about 130 ℃; The 4th district-115 ℃ is to about 120 ℃.

About path length, for the present invention, path length should be 5 meters (the path temperature that has 3 meters long at least is more than Tg of polymer) at least, is necessary to long filament after this converging.Path length is suitable for the present invention between 5 meters to 9 meters.9 meters the upper limit is the restriction of practical aspect, if the space allows, length can also increase.In order to make intensity property the best, long preferably about 7 meters of path.

Fiber converges after flowing out path 18.This converges and can finish by using oiling device.

Afterwards, guide silk into a pair of godet roller 22 at oil for the first time (that is, at oiling device 20 places), (that is, at oiling device 23 places) then carry out oiling the second time.Carry out oiling the first time, purpose is to reduce the static that forms on fiber.But this finish is got rid of during by godet roller sometimes at fiber.Therefore after godet roller, oil again.

Make fiber by a winding head 24 that Tension Control is arranged usually then.Winding speed is generally greater than 3000 meters/minute (9800 feet per minutes), and maximum speed is 5800 meters/minute (19000 feet per minutes).Optimum range is about 10500 to 13500 feet per minutes (about 3200 to 4100 meters/minute).Most preferred scope is between about 3200 to 3800 meters/minute (10500 to 12500 feet per minute).When speed is lower than 9800 feet per minutes (3000 meters/minute), the uniformity variation of silk.

The spun that makes in order to the top method is a feature with the less crystallization and the higher degree of orientation generally.It is believed that these character of spun make it can obtain the drawn yarn character of following uniqueness just.

In order to check the general characteristic of spun polyester, little crystallization is to determine by crystal size (measuring with dust), and orientation then defines with one of following term: optical birefringence; The amorphous birefringence; Or crystallization birefringence.In addition, spun polyester characterizes with crystal size and long period interval (distance between the crystallization).Put it briefly, spun polyester be characterized as crystal size less than 55 dusts, simultaneously optical birefringence greater than 0.090 or the amorphous birefringence greater than 0.060, or long period is at interval less than 300 dusts.More preferably, the crystal size of spun polyester is from about 20 to about 55 dusts, and optical birefringence is from about 0.090 to about 0.140, or the amorphous birefringence is from about 0.060 to about 0.100, or long period at interval from about 100 to about 250 dusts.Preferably, the crystal size of spun polyester is from about 43 to about 54 dusts, and optical birefringence is from about 0.100 to about 0.130, or the amorphous birefringence is from about 0.060 to about 0.085, or long period at interval from about 140 to about 200 dusts.

As may be obvious that in the general technology technology, the crystal size of spun is about 1/3 of conventional silk in best winding speed scope.Crystal size increases with winding speed and becomes big, but still keeps very little.The crystalline orientation of silk is very high, is about 2 times of regime values.The orientation of this silk is very high and contract and become very low, so that can just use without any stretching.

In addition, spun polyester has following performance: crystalline content (that is the degree of crystallinity of being determined by density) is 10% to 43%; Intensity is about 1.7 to 5.0 gram/dawn; Modulus is 10 to 140 gram/dawn/100%; It is 50% to 160% that the hot-air shrinkage is about 5% to 45% percentage elongation.

Then spun is stretched.Referring to Fig. 2.Can adopt the operation of one-level or secondary drawing.But confirmed already what other benefit second level stretched operation does not almost have.Might with spinning operation directly and stretched operation couple together (that is spinning/drawing process).Spun can be fed roll dies and can be heated to the highest about 150 ℃ from room temperature by creel 30 to feeding roll dies 34 feed.Then, fiber is fed on the draw roll 38, this roller can be heated to about 255 ℃ from room temperature.If there is not warm-up mill, can take a hot plate 36 that is allowed to warm to 180 ° to 245 ℃.Hot plate 36(has 6 inches crooked contact surface) be contained in the drawing zone, that is, feeding between roll dies 34 and the draw roll 38.The scope of draw speed is 75 to 300 meters of per minutes.Typical draw ratio is about 1.65(and is adapted at the silk that makes under about 3800 meters/minute).The best hello roll dies temperature that can obtain maximum pulling strength is about 90 ℃.Best draw roll temperature is about 245 ℃.If the use hot plate, then optimum temperature is between about 240 ° to 245 ℃.The temperature of draw roll has certain control action to the hot-air shrinkage.In general wish that shrinkage is low, because this can make the cord fabric thread stability of handling the highest.But have a kind of final use-canvas at least, require drawn yarn that higher shrinkage is arranged, this can control with the temperature that reduces draw roll.

According to above-mentioned, the performance of drawing of fiber can be controlled as follows: intensity can from 4.0 to 10.8 gram/dawn, and percentage elongation is from 7% to about 80%, initial secant modulus from 60 to 170 gram/dawn/100%, and hot-air shrinkage (at 177 ℃) is 6% to 15%.The dawn number of fibre bundle can be after 125 to 1100(a numeral can obtain by several beam filaments are merged), filament denier is 1.5 to 6.The fibre reinforced materials that silk like this can be used as rubber tyre uses.

According to polyester (that is, the polyethylene terephthalate) drawn yarn that said method makes, its initial secant modulus can be greater than 150 gram/dawn/100%.In addition, these shrinkage can be less than 8%, or its intensity is greater than 7.5 gram/dawn.

The feature of the preferred embodiment of another drawn polyester yarn is as follows: intensity was at least for 8.5 gram/dawn; Initial modulus is at least 150 gram/dawn/100%, and shrinkage is less than 6%.The feature of the preferred embodiment of another drawn polyester yarn is: intensity was at least for 10 gram/dawn; Initial modulus is at least 120 gram/dawn/100%; Shrinkage is less than 6%.Also have the characteristics of preferred embodiment of a drawn polyester yarn as follows: intensity from about 9 to about 9.5 gram/dawn; Initial modulus from about 150 to about 158 gram/dawn/100%; Shrinkage is less than 7.5%.

The drawn yarn that makes according to said method may be used to following final use: tyre cord, and sewing thread, canvas is used for fabric such as the fiber web or the pad of road structure or other geotextiles, industrial band, composite, architectural fabric, the reinforcing material of flexible pipe, laminated fabric, rope etc.

More than opinion of the present invention is begged for the following key test of using in the example with the back, undertaken by following program:

Intensity is with reference to " fracture strength " that define among the ASTM D-2256-80

Initial modulus (or " initial secant modulus ") is pressed ASTM D-2256-80, the definition of the 10.3rd joint, difference is, representing the straight line of the initial straight line portion of load-deformation curve to be appointed as on the load-deformation curve by percentage elongation is the secant of two points of 0.5% and 1.0%.

All other tensile properties is all in accordance with the definition of ASTM D-2256-80.

Shrinkage factor (hot-air shrinkage) is defined as linear shrinkage in keeping 177 ± 1 ℃ hot-air by ASTM D-885-85.

Regulation is identical in density, crystal size, long period interval, crystallization birefringence and amorphous birefringence and the United States Patent (USP) 4,134,882, and this patent is here quoted as a reference.Specifically, above-mentioned every can be at United States Patent (USP) 4,134, find before and after 882 following paragraph or its: density-Di 8 hurdles 60 row; Crystallite size-Di 9 hurdles 6 row; Long period interval-Di 7 hurdles 62 row; 12 row amorphous birefringence-Di, 11 hurdles, crystallization birefringence-Di 11 hurdles, 27 row.

Birefringence (optical birefringence or Δ n) and United States Patent (USP) 4,101, fixed identical of 525 the 5th hurdle 4-46 professional etiquettes, this patent is here quoted as a reference." BiCV " is the coefficient of variation between the optical birefringence that is calculated by the long filament that 10 velamens are measured.

Other test mentioned in this article is carried out according to a conventional method.

Now with reference to example the present invention is described more fully.

Example 1

In following one group of experiment, with a kind of polyester polymers commonly used (polyethylene terephthalate, inherent viscosity 0.63) spinning.Spinning speed is increased to 19000 feet per minutes by 12500 feet per minutes.Path length is 6.4 meters, is divided into four temperature-controlled areas.Control temperature by measuring each district center near the air themperature at wall place, path.With per hour 22.9 pounds speed with polymer through one 285 ℃ spinning manifold and the spinnerets in 40 holes (hole is of a size of 0.009 inch * 0.013 inch) extruding come out.Fiber is without quenching.Spun fiber does not stretch, but stands heat setting.The results are shown in Table 1.

The example II

In following battery of tests, with polyester (polyethylene terephthalate, the inherent viscosity 0.63) spinning of a routine.The path variation of temperature is (air themperature of each district center) as shown in Table.Path length is 6.4 meters.With polymer with 23.1 pounds/time speed extrude by one 300 ℃ spinning manifold and the spinnerets in one 72 hole (hole is of a size of 0.009 inch * 0.012 inch).Fiber is without quenching.As-spun fibre is with after-drawing (it is as shown in the table).The results are shown in Table 2.

In above one group of experiment (that is, being listed in those experiments in the table 2), the 4th, 5,6 and 7 represent the present invention.

The example III

In following one group of experiment, with polyester (polyethylene terephthalate, the inherent viscosity 0.63) spinning of routine.Speed coiling fiber with 10500 feet of per minutes.Polymer is extruded by the spinnerets (0.009 inch * 0.012 inch of the size in hole) and 300 ℃ the spinning manifold in one 72 hole with 19.5 pounds speed per hour.Fiber through the air of 232 ℃ per minute 6.5 standard cubic foots with the fiber quenching.Long 6.4 meters of path, air themperature distributes according to following 4 zones (by descending order) in the path: each district center place is 135 ℃, 111 ℃, 92 ℃ and 83 ℃.Spun has following performance: dawn number-334, and the intensity-4.09 gram/dawn, percentage elongation-71.7%, initial modulus-55.0 gram/dawn/100%, hot air shrinkage-350 °F are 11.8%, crow this paricular value-1.10, inherent viscosity-0.647, birefringence-110 * 10 ^-3, degree of crystallinity-21.6%, FOY-0.35%.

In table 3A, illustrated that draw ratio is to the drawn yarn Effect on Performance.

In table 3B, the influence (draw ratio is 1.65, and silk is without lax) of heating means when stretching has been described.

In table 3C, the influence (feeding roll dies is room temperature, and draw roll is 240 ℃) that improves draft temperature and draw ratio has been described

The example IV

In following one group of experiment, with a kind of normal polyester (polyethylene terephthalate, inherent viscosity 0.92) spinning.In 1-5 number experiment, fiber is according to United States Patent (USP) 4,101,525 and 4,195,052 described method spinning and stretching.6-9 number then by being prepared as follows:

With the inherent viscosity that is used for characterizing molecular weight is that 0.92 polyethylene terephthalate is dried to water content and is not more than 0.001%.Melt And and be heated to 295 ℃ this polymer is molten in extruder, then be transported to filament spinning component with measuring pump.Assembly is a loop configuration, and polymer is therein by the stacking bed filtration of thin clipped wire.After filtering, polymer is extruded by the spinnerets in one 80 hole.Each spinneret orifice all is the circular cross-section of 0.457 millimeter of diameter, and capillary pipe length is 0.610 millimeter.

Adorning one 9 meters long insulation heating tube below assembly snugly, spun multifilament bundled is being converged through ability behind the whole pipe range or is being contacted with any guide pulley surface.The whole length of this pipe is divided into 7 zones so that the control temperature.The air themperature at each district center place is all controlled in each zone with independent controller.Utilize the heat of spinning process and the outer heater devices around the pipe, adjust the setting value of each controller and distribute so that form uniform air themperature vertically downward along pipe.Air themperature in typical zone, situation next top is 155 ℃, and temperature reduces to 50 ℃ of bottom with the gradient of approximate homogeneous.

10 centimeters below pipe, synnema contacts with oiling device, and this device also works to converge thread guide ， And and is silk and extraneous contacting first.In the exit of pipe, the cross section of the silk that does not converge is owing to becoming very little near the thread guide that oils.This just might use very little hole, thereby reduces the hot-air loss in the pipe.

After applying spinning oil, guide silk into a pair of godet roller, guide the winding head of Tension Control then into.Winding speed generally is 3200 to 4100 meters/minute.

Second stage stretches this silk, and at this moment spun leads to temperature by one group of predraft roller and remains on 80 ° to 150 ℃ heating and feed roll dies.Be set in these rollers and one group of temperature between 180 to 255 ℃ the draw roll, then silk stretched.For the silk that makes under 3800 meters/minute, typical draw ratio is 1.65, higher or then require low and higher draw ratio respectively than spun sample under the low velocity.

The results are shown in table 4.

The example V

The inherent viscosity that will be used to show special molecular weight is that to be dried to moisture be 0.001% for 0.92 polyester.Melt And and be heated to 295 ℃ this polymer is molten in extruder, subsequently with measuring pump with melt Conveying in filament spinning component.Through after the finely-divided metal stacking bed filtration, with polymer by extruding by the spinnerets in 80 holes.The diameter of each spinneret orifice is 0.457 millimeter, and capillary pipe length is 0.610 millimeter.The polymer property viscosity that records when extruding is 0.84.

The polymer of extruding enters by spinning in the path inner chamber of 9 meters of length of heating.Keep the Temperature Distribution (gradient) of approximately linear along the length direction of this pipe.The center air themperature of the top area of pipe is 155 ℃, and the bottom is 50 ℃.Multifilament bundled did not converge before the thread guide that oils below abutting against the heating tube outlet contacts.Silk is guided the winding head of Tension Control into from this through a pair of godet roller.Make 4 kinds of silks with different spinning (coiling) speed under these conditions.These silks are called example A to D in table 5.A.

In another group experiment, take off some part that can remove of heating tube and heating tube is shortened.Example E and the F of table among the 5.A is path spinning by 7 meters and 5 meters long.The also spinning in this system of the polymer of other different molecular weight (inherent viscosity) obtains example G and H.Example I among the table 5.A represents to adopt the situation of low path temperature.Form linear gradient in this case in the path by 125 ℃ to 50 ℃.

Series A to all first silks that spin of I all stretch in the single-stage mode with hello the roll dies of room temperature and 245 ℃ draw roll.

In another serial experiment, adopt the different roll dies temperature of feeding to stretch the same silk described in the example A.These result of the test is listed in example A, J and the K among the table 5.B.

The example VI

In the next round experiment, the polymer-nylon spinning ， And with a kind of routine compares with the nylon silk that makes with conventional method according to method of the present invention.

The nylon spinning under the following conditions that makes with the inventive method: throughput-per hour 37 pounds; Spinning speed-2362 feet per minute; Dawn number-3500; Monofilament radical-68; Spinning relative viscosity-3.21(H ₂SO ₄) or the 68.4(HCOOH equivalent); Quench air-72 standard cubic foot/minute; Winding tension-80 gram; Long-24 feet of path; 240 ℃ at temperature-top, path, 48 ℃ of bottoms.The performance of this spun is as follows: the intensity-0.95 gram/dawn; Percentage elongation-235%; Intensity

-14.6.Silk stretches under the following conditions subsequently: draw ratio 3.03; 90 ℃ of draft temperatures.The performance of drawn yarn is as follows: the 6.2 gram/dawn of intensity; Percentage elongation 70%; Intensity

52; 10% modulus was 0.87 gram/dawn; 400 following hot air shrinkages are 1.4%.

With of the nylon spinning of following usual manner with a kind of contrast: throughput-23.4 pound/time; Spinning speed-843 feet per minute; Dawn number-5556; Monofilament radical-180; Relative viscosity-the 3.3(H of spinning ₂SO ₄) or the 72.1(HCOOH equivalent); Quench air-150 standard cubic foot/minute.Under the following conditions silk is stretched then: draw ratio-2.01; Draft temperature-90 ℃.The performance of drawn yarn is as follows: the intensity-3.8 gram/dawn; Percentage elongation-89%; Intensity

-33; 10% modulus-0.55 gram/the dawn.

With following usual manner with another kind silk contrast spinning: throughput-57.5 pound/time; Spinning speed-1048 feet per minute; Dawn number-12400; Monofilament radical-240; Spinning relative viscosity-42(HCOOH equivalent); Quench air-150 standard cubic foot/minute.Under the following conditions silk is stretched then: draw ratio-3.60; Draft temperature-110 ℃.The performance of drawn yarn is as follows: the intensity-3.6 gram/dawn; Percentage elongation-70%; Intensity

-30.1; The modulus during 10% percentage elongation-0.8 gram/dawn; Hot air shrinkage (400)-2.0%.

The example VII

In next round experiment, will hang down the spun of mentioning in normal polyester (that is, the polyethylene terephthalate) spun of inherent viscosity (for example 0.63) and high inherent viscosity (for example 0.92) and the United States Patent (USP) 4,134,882 and compare.Example 1～8th, the polyester (polyethylene terephthalate) of low inherent viscosity makes by the method described in the example I.Example 9～11st, the polyester of high inherent viscosity (polyethylene terephthalate) makes by the method described in the example V.Example 12～17 is corresponding to United States Patent (USP) 4,134, the example 1,5,12,17,36 and 20 in 882.

For each example, listed spinning speed (feet per minute), density (gram/cubic centimetre), crystal size (dust, 010 crystal face), long period interval, birefringence, crystallization birefringence and the birefringent data of amorphous the results are shown in table 7.

The present invention can embody in other specific forms and not depart from spirit of the present invention or basic special, therefore, should indicate scope of the present invention with reference to appended claim rather than above-mentioned specification.

Claims (9)

1, a kind of drawn polyester yarn is characterized in that, initial secant modulus is greater than per dawn 150 gram/100%.

According to the drawn polyester yarn of claim 1, be further characterized in that 2, shrinkage factor is less than 8%.

According to the drawn polyester yarn of claim 1, be further characterized in that 3, intensity is greater than 7.5 gram/dawn.

4, a kind of drawn polyester yarn is characterized in that, intensity was at least for 7.5 gram/dawn; Initial secant modulus is at least per dawn 150 gram/100%; Shrinkage factor is less than 8%.

5, a kind of drawn polyester yarn is characterized in that, intensity was at least for 8.5 gram/dawn; Initial secant modulus is at least per dawn 150 gram/100%; Shrinkage factor is less than 8%.

6, a kind of drawn polyester yarn is characterized in that, intensity was at least for 10 gram/dawn; Initial secant modulus is at least per dawn 120 gram/100%; Shrinkage factor is less than 8%.

7, a kind of drawn polyester yarn is characterized in that, intensity is greater than 9.0 gram/dawn; Initial secant modulus is greater than per dawn 150 gram/100%, and shrinkage factor is less than 7.5%.

8, according to the silk of claim 1 or 4 or 5 or 6 or 7, wherein polyester is a polyethylene terephthalate.

9, according to the silk of claim 1 or 4 or 5 or 6 or 7, this is formed to the monofilament at 6 dawn by one group 1.5.

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