JP2000129536A - Production of high-windability high-elongation spun yarn of polyester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the subject method, which uses a fiber elongation improver to keep residual elongation of the spun yarn, and, at the same time, solves the difficulties in yarn winding resulting from bleed-out of the additive. SOLUTION: This method produces yarns by melt spinning polyester as the base polymer incorporated with an elongation improver at a high take-off speed of 1,000 m/min or more, wherein a crystallization retardant (a), (b) or (c), defined below, is used as the elongation improver: (a) at least one metal carboxylate selected from the group consisting of alkali metal and alkaline-earth metal salts of aliphatic carboxylates, (b) p-hydroxybezoic acid and/or its ester- formable derivative, and (c) 2,6-naphthalenedicarboxylic acid and/or its ester- formable derivative.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a high elongation polyester spun yarn having improved winding properties.

[0002]

2. Description of the Related Art In the melt spinning of polyester fibers, increasing the amount of polymer discharged from a die as much as possible is an extremely effective method for increasing productivity. It is considered to be extremely desirable from the viewpoint of reduction.

[0003] As a typical means that has been taken to increase productivity, a method of increasing the spinning take-off speed and increasing the discharge amount from a die is known. However, in this method, since the take-up speed is high, the molecular composition of the individual filaments is increased, and consequently, the residual elongation (hereinafter, may be simply referred to as elongation) of the obtained spun yarn is reversed. Will drop. Therefore, as a matter of course, since the draw ratio at the time of subsequent drawing or drawing false twisting is reduced, the effect of increasing the discharge amount due to the increase in the take-up speed,
It is offset in the stretching process.

As one means for solving such a problem, an organic polymer which is incompatible with the polymer and functions as an elongation improver at the time of spinning, for example, an additive polymer comprising an unsaturated monomer is added to the polyester. A method for increasing the residual elongation of a spun yarn has been proposed in Japanese Patent Publication No. Sho 63-32885 (corresponding to European Patent No. 47466 (A ₁ )).
According to this document, the function of the additional polymer is defined as being microdispersed in the molecular order in the polyester, and the polymer plays a role of “roller” with respect to the molecular orientation of the polyester (for example, (See the above-mentioned EP Patent, page 9, line 3).

According to this method, a spun yarn (as-spun yarn) having a high residual elongation and a drawn yarn (FOY) obtained by an ultra-high speed drawing process can be obtained, including an intermediate oriented yarn (POY). Has encountered a new problem when winding the as-spun yarn having a high residual elongation disclosed in JP-B-63-32885 in a commercial base winder.

That is, the present inventors have found that the problem that the formation of a winding package is not practically possible, that is, the winding on a commercial basis is impossible. As a phenomenon relating to this problem, the filament alone or several filaments have a traverse printing defect, so that the winding end face deviates from a normal circumferential winding form, a “tear drop” or an end face “distorted”, In addition, the yarn was floated during winding, and a fatal winding defect such as reaching the purst occurred.

The reason for this is that the addition polymer acts as a "roller" in a state substantially incompatible with the polyester, so that it bleeds out predominantly on the fiber surface in the form of particles, resulting in excessive surface irregularities. , Which results in a decrease in filament / filament friction (F / F friction) and filament / metal (F / M friction), which is considered to cause a malfunction in the winding process condition.

Of course, in order to solve the above-mentioned problem of poor winding, it is only necessary to reduce the amount of the elongation improver to be added and to reduce the amount of bleed out of the agent to the fiber surface. However, this leads to a result that conflicts with the intended purpose of improving elongation.

[0009]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a polyester filament yarn to which a fiber elongation improver has been added, while keeping the residual elongation of the spun yarn at a conventional level as much as possible. However, the object of the present invention is to overcome a fatal defect of "rewinding" accompanying bleed-out of the agent, which has not been recognized at all.

[0010]

According to the present invention, an organic polymer which is incompatible with a polyester as a base polymer and functions as an elongation improver at the time of spinning is dispersed in a polyester based on the weight of the base polymer. In spinning to obtain a high-speed spun yarn at a take-up speed of 1,000 m / min or more, the following (a) is used as the base polymer:
(B) or (c), characterized by using a polyester obtained by adding a crystallization inhibitor,
A method for producing a high elongation polyester spun yarn having improved winding property is provided.

(A) at least one metal carboxylate selected from the group consisting of an alkali metal salt and an alkaline earth metal salt of an aliphatic monocarboxylic acid is added to the bifunctional carboxylic acid component constituting the polyester in an amount of 0%; Polyester added in the range of 0.001 mol% to 0.05 mol%,
(B) a polyester obtained by adding p-hydroxybenzoic acid and / or an ester-forming derivative thereof in an amount of 0.01 to 1.5 mol% with respect to an acid component constituting the polyester; A polyester in which 6-naphthalenedicarboxylic acid and / or an ester-forming derivative thereof is added in an amount of 0.1 to 5 mol% based on an acid component constituting the polyester.

Here, the background that led to the present invention will be described.

[0013] The desired elongation of the spun yarn can be obtained by adding the elongation improver described above usually in an amount of 0.5 to 4.0% by weight based on the polyester polymer. However, at the same time, poor winding due to bleed-out of the agent is also caused as described above.

The present inventors have found that the addition amount of the elongation improver is 0.1%.
In the range of 5 to 40% by weight, while reducing the amount as much as possible to improve the winding property, the residual elongation of the spun yarn is maintained at a level comparable to the added amount before the agent is reduced. The challenge is to
Surprisingly, it has been found that the problem can be solved by employing a polyester to which a crystallization inhibitor having a different function from the elongation improver is added as a base polymer.

Before the completion of the polycondensation reaction, the crystallization inhibitor shown in (a), (b) or (c) is added to the base polymer.

In the case of (a), the agent exists as insoluble fine particles. These fine particles are ultrafine particles having a diameter of at most 50 mμ, and exhibit the crystal orientation suppressing ability at the time of spinning, and at the same time, because they are ultrafine particles, even if they bleed out to the fiber surface, there is no hindrance to the winding property. It does not bring about this property, and is used skillfully when used in combination with an elongation improver.

In the case of (b), only the carboxylic acid and its ester moiety react and are incorporated at the terminal of the polymer, so that there is no fear of bleeding out of the agent. In the case of (c), the agent, naphthalenedicarboxylic acid, is incorporated in the main chain of the polymer in the form of a copolymer, so that there is no fear of bleeding out of the agent.
When an elongation improver is added to such a copolymer, the residual elongation of the spun yarn increases in proportion to the total amount of (b) and the elongation improver.

The crystallization inhibitor may be added to the base polymer at any time before the completion of the polycondensation reaction. Before the polycondensation is completed, specifically, the number average degree of polymerization of the polymer is 30. It is preferred to add it before reaching. The adding means may optionally be added, for example, as it is with the additive, or as a solution or slurry of glycol or water. In particular, with regard to (a), it is more preferable to add in the form of a solution, disperse uniformly in the polymer, and then precipitate, since the particle size distribution is small.

Therefore, by employing such a polymer as the base polymer, the amount of the elongation improver to be added is reduced, and the problem of poor winding is eliminated.

Further, the present invention will be described in detail.

The base polymer employed in the present invention comprises terephthalic acid as a main acid component and at least one glycol, preferably at least one selected from the group consisting of ethylene glycol, trimethylene glycol and tetramethylene glycol. The main object is a polyester containing alkylene glycol as a main glycol component.

The polyester may be a polyester in which a part of the terephthalic acid component is replaced by another difunctional carboxylic acid component, and / or the above glycol or other diol in which a part of the glycol component is other than the main component. It may be a polyester substituted with a component.

Such a polyester may be synthesized by any method. For example, when polyethylene terephthalate is described, usually, terephthalic acid and ethylene glycol are directly esterified, or a lower alkyl ester of terephthalic acid such as dimethyl terephthalate is transesterified with ethylene glycol, or terephthalic acid and ethylene glycol are used. A first stage reaction of reacting with an oxide to form a glycol ester of terephthalic acid and / or a low polymer thereof, and heating the reaction product of the first stage under reduced pressure until a desired degree of polymerization is obtained. It is produced by a second stage reaction of a polycondensation reaction.

In the above-mentioned polycondensation step, (a), (b) or (c) is added alone or in combination.

Here, specific examples of the crystallization inhibitor in (a) include lithium acetate, potassium acetate, sodium acetate, rubidium acetate, lithium stearate, potassium stearate, sodium stearate, rubidium stearate, and lithium carbonate. Alkali metal salts such as potassium carbonate, sodium carbonate and rubidium carbonate; and alkaline earth metal salts such as calcium acetate, magnesium acetate, barium acetate, calcium stearate, barium stearate, calcium carbonate, magnesium carbonate and barium carbonate.

The ester-forming derivatives of parahydroxybenzoic acid (b) include methyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, propyl p-edroxybenzoate and butyl p-hydroxybenzoate. .

Further, the bifunctional ester-forming naphthalene compound (c) may be 1,2-naphthalenedicarboxylic acid,
1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,
Examples thereof include 7-naphthalenedicarboxylic acid and / or dimethyl ester and diethyl ester of these compounds. Among these, 2,6-naphthalenedicarboxylic acid, methyl 2,6-naphthalenedicarboxylate, and 2,6-naphthalenedicarboxylic acid
Diethyl naphthalenedicarboxylate is preferred.

Here, the addition amount of the crystallization inhibitor in (a) is mainly based on the bifunctional carboxylic acid mainly composed of terephthalic acid constituting the polyester or the lower alkyl ester of terephthalic acid such as dimethyl terephthalate. It is necessary to set the amount to 0.001 mol% to 0.05 mol% based on the dialkyl ester of a bifunctional carboxylic acid as a component.

[0029] Even if the agent is added in an amount of more than 0.05 mol%, the effect of suppressing crystallization has almost reached saturation, on the other hand, the amount of foreign substances in the polymer increases, coarse particles are formed, and the spun yarn is broken. In addition to the cause of processing thread breakage or the increase of pack pressure, there is a problem that polyester is colored by a decomposition reaction. It also has an adverse effect on winding properties.

The lower limit of the amount added is preferably 0.001 mol% in relation to the effect of suppressing crystallization during high-speed spinning.

In the case of (b), if the addition amount of the agent is too small, the effect of suppressing the orientational crystallization cannot be obtained. On the contrary, if it is too large, the melting point of the obtained polyester decreases or the yellowish color increases. It is added in an amount of 0.01 to 1.5 mol%, preferably 0.05 to 1.0 mol%, based on the bifunctional carboxylic acid constituting the polyester.

Further, in the case of (c), the addition copolymerization amount of naphthalenedicarboxylic acid is 0.1 to 0.1 with respect to terephthalic acid.
5 mol%. Here, if the amount of the added copolymer is less than 0.1 mol%, the effect of suppressing the orientation crystallization cannot be obtained. It is not preferable because the frequency increases.

Finally, the added amount of these agents is 0.03 to 6.0 w, based on the weight of the base polymer.
When it is in the range of t%, it functions in combination with the elongation improver to contribute to the improvement of the elongation of the spun yarn.

The fiber elongation improver referred to in the present invention is an additive polymer comprising an unsaturated monomer and substantially incompatible with polyester, and has a heat distortion temperature (T) of:
98 to 145 ° C, preferably 105 to 135 ° C. Specific compositions include acrylonitrile styrene copolymer, acrylonitrile butadinine styrene copolymer, polytetrafluoroethylene, high density polyethylene, low density polyethylene, linear low density polyethylene, polystyrene, polypropylene, polymethylpentene, Examples include polyacrylate, polymethyl methacrylate, and derivatives containing these polymers as main components. The molecular weight of these polymers is required to have a molecular weight (weight average) of at least 2,000 or more because the polymer needs to exhibit structural viscoelasticity as a high molecular weight material independently of polyester as a stress carrier. is there.

More specifically, the molecular weight is from 2000 to 20.
It is appropriate that it is less than 10,000. If the molecular weight is smaller than 2,000, it does not act as a stress carrier because it does not exhibit structural viscoelasticity as a high molecular weight substance. On the other hand, when it exceeds 200,000, the cohesive energy of the polymer is extremely high, and therefore, its melt viscosity is too high relative to the polyester, so that dispersion in the polyester becomes extremely difficult,
As a result, the spinnability at the time of spinning is remarkably deteriorated, winding is also difficult, and further, a negative foreign matter effect on polyester is large, so that practical properties cannot be obtained. The preferred range of the molecular weight is from 8,000 to 150,000, and such a high molecular weight polymer is more preferable because the heat resistance is also improved.

Further, as the additional polymer to be added to the polyester in the present invention, more preferred are those having a molecular weight of 8,000 to 200,000 and ASTM-D123.
8 (230 ° C., load 3.8 kgf), the melt index (MI) is 0.5 to 1
5.0 g / min of a polymethyl methacrylate copolymer or an isotactic polymer containing styrene as a main component. I. (ASTM
-According to D1238; 260 ° C, 5.0 kgf)
Polymethylpentene or a derivative thereof in the range of 0 to 40.0 g / 10 minutes, and further, in the same molecular weight range,
M. I. (Based on ASTM-D1238; 300 ° C,
2.16 kgf) is syndiotactic (crystalline) polystyrene or a derivative thereof of 6.0 to 25.0 g / 10 min. Polymers having these specific properties have excellent thermal stability and dispersion state stability at the polyester spinning temperature.

Among them, those having a heat distortion temperature (T) of 105 to 135 ° C. are particularly in a sea / island state substantially incompatible with the polyester, ie, the polyester is the sea, and the fiber elongation of the particles is The improver is discharged from the die hole as a sea component, and during the cooling and thinning process on the spinning line, it changes from a molten state to a glassy state prior to polyester, and elongates and deforms due to spinning stress (tension). Acts as a low antibody. As a result, the elongational viscosity of the blend system in a state where the polymer temperature near the mouthpiece is high causes an increase in non-linearity that does not follow the conventional elongational viscosity equation. It is considered that this has the function of causing the yarn speed to reach the final winding speed. As described above, the position at which the thinning is completed is completed at a position higher than the spinning line when the polyester containing no polymer is spun at the same speed, and is remarkable at a take-off speed of 4000 to 5000 m / min or more. No neck-like thinning accompanied by oriented crystallization is observed. From this, it can be said that the action of the elongation improver enables low-tensile spinning in high-speed spinning, and gives a polyester fiber having a high residual elongation while improving the winding property.

A further explanation will be given on this point.

Due to the concept of "elongational deformation resistor" against spinning stress, the fiber elongation improver changes from the molten state to the glassy state faster than the matrix polymer in the polymer stream being spun (discharged). It is desired.
In this sense, the heat distortion temperature (T) of the elongation improver is 9
It is preferably in the range of 8 to 145 ° C, preferably 105 to 135 ° C. The heat distortion temperature of polyester is generally about 70 ° C., and the heat distortion temperature is higher by at least 35 ° C. or more. The particulate fiber elongation improver predominantly bears spinning stress and is becoming finer. Since the polymer stream is relatively concentrated inside, the precipitation of particles on the filament surface can be reduced, and the winding property can be significantly improved. When the heat deformation temperature (T) is less than 105 ° C., the function as the conventional “roller” may be limited to the function as the elongation deformation resistor.

Next, a method for obtaining a spun yarn of the present invention will be described.

In order to realize the winding property and high residual elongation intended by the present invention, filtration and spinning draft of the molten polymer before spinning (discharge) are important as spinning conditions.

Here, a filter having a pore size of 40 μ or less is placed in a spinning pack, and a molten polyester in which a fiber elongation improver is dispersed is passed through the filter.
Apparent spinning draft (rate) in the range of 150 to 1500
It is necessary to spin under the. With a filter having a pore size exceeding 40μ, coarse particles are mixed in the discharged polymer stream, and a stable spinning condition cannot be secured.
In addition, there is a problem in the winding property due to the surface irregularities formed by the coarse particles that are bleached out on the filament surface.
On the other hand, for spinning drafts, a high draft range was found to be important. In other words, when the draft is less than 150, that is, when the diameter of the discharge hole of the spinneret is small, the polymer flow passing therethrough is subjected to high shearing force, and the particulate fiber elongation improver is torn off in the longitudinal direction of the filament, and the spinning is performed. The effect of improving the elongation of the yarn is impaired. That is, the particles
Without sufficiently fulfilling the function as a stress carrier, the frequency of precipitation on the filament surface simply increases, which impairs the winding property. On the other hand, when the draft is higher than 1500, the shredding effect by the shearing force in the discharge hole is reduced, and the residual elongation of the spun yarn is remarkably improved. Trouble is not solved.

Further, other spinning requirements are related to the spinning temperature (the spinneret temperature) and the cooling under the spinneret.

Regarding the former, lowering the die temperature when discharging the molten polyester in which the fiber elongation improver is dispersed also contributes to an increase in the residual elongation and a stable winding property. This is because the elongational viscosity of the elongation improver after discharge of the spinneret increases further upstream of the spinning line, and the function as a stress carrier is developed. As a result, the maximum point of the particle concentration in the cross section of the filament is reduced while significantly reducing the spinning tension. This is because there is a tendency to fix. Optimal base temperature is 270-29
0 ° C. If the temperature is lower than 270 ° C., depending on the type of polyester, a problem of spinnability occurs. On the other hand, if it exceeds 290 ° C., the heat resistance of the additional polymer as an elongation improver decreases.

In the latter cooling under the mouthpiece, in the case of lateral blowing cooling, by maintaining the wind speed in the range of 0.15 to 0.6 m / sec, it is possible to improve the residual elongation and the winding property. Contribute to both. When the wind speed is less than 0.15 m / sec,
The unevenness in the longitudinal direction of the filament is large, and high-quality drawn yarn and processed yarn cannot be obtained after the fact. Also, 0.
If it exceeds 6 m / sec, the elongational viscosity on the polyester side will increase, and the increase in the residual elongation will be small.

In adding the fiber elongation improver to the polyester, any method can be adopted. For example, the agent may be mixed at the final stage of the polymerization of the polyester, or the polyester and the agent may be melt-mixed, extruded and cooled, and then cut into chips. Furthermore, the agent may be introduced in a molten state from a side stream into a melt spinning apparatus for polyester via a dynamic and / or static mixer. Alternatively, both may be mixed in a chip shape and then melt-spun. Among them, a part of the polymer is pulled out from the polyester pipe of the continuous vertical connection line, and the agent is kneaded and dispersed as a matrix, and an arbitrary dynamic and / or static mixer is added to the original neat polymer line. It is most preferable to return the fluid through the pipes and distribute the fluid to each pipe.

In this case, the total amount of the elongation improver in the base polymer is from 0.3 to 3.
It is preferable to adjust to a range of 5%. At this time, the weight ratio of these agents to the elongation enhancer is 0.1 to 1000.
%, It is possible to directly wind up a mixed fiber yarn exhibiting a composite property of undrawn yarns having different elongation degrees.

Conventionally, the same polyester is co-spun (Co-s) from a die provided with discharge holes having extremely different discharge hole diameters.
(pun) method. However, in this case, the spinning speed for obtaining a spun yarn having a high residual elongation, specifically, a low spinning speed of around 1500 m / min, at which a yarn having an elongation of 270 to 340% is obtained, is rate-limiting. . On the other hand, when the polyester containing the fiber elongation improver and the polyester not containing the same are discharged from the same die, the spinning speed for obtaining a desired low residual elongation yarn from the latter polyester, that is, at a high speed, Because it can be rolled up, not only is it compounded, but it also leads to a dramatic improvement in productivity.

A spun yarn made of a yarn having such a difference in elongation is obtained from U.S.A. S. P2,013,746 (JP-B-61-19733) is preferably used as a raw yarn for a core-sheath type composite false twisted crimped yarn.
That is, when the spun yarn is subjected to simultaneous drawing false twisting according to the teachings of the above patent, a higher draw ratio can be adopted, so that the winding speed is increased by that amount, leading to an improvement in productivity.

In the spinning mode of the present invention, the effect is exhibited at a take-up speed of 1000 m / min or more.
At a speed of from 00 to 10000 m / min, a spun yarn having a significantly improved residual elongation can be obtained.

Furthermore, the spinning aspect of the present invention can also be preferably incorporated into a direct spinning undrawn process. Especially 8
If a high-speed high-performance winder of 000 m / min or more is realized, the speed of the take-up roller G1 (also a preheating roller: called the first godet roller in the art) is 500.
After drawing at 0-6000 m / min, the direct spinning and drawing process can be adopted at a drawing heat set roller G2 (referred to in the art as the second godet roller) speed of 7000-9000 m / min. . Also,
G1 speed is set to 7000-8000 m / min, and G2 /
G1 speed ratio is 1.10 to 1.25 at most, and after passing through a steam chamber for the purpose of eliminating the distortion of the yarn and heat setting after winding, the yarn is wound up. It is also possible to expand to.

[0052]

EXAMPLES A method for measuring physical properties employed in the present invention will be described.

(1) Heat distortion temperature (T) According to ASTM D-648.

(2) Residual elongation The spun yarn was left in a room kept at a high temperature and humidity of 25 ° C. × 60% humidity for 24 hours, and then a 100 mm sample length was set on a tensile tester Tensilon manufactured by Shimadzu Corporation. And 200mm
The tensile elongation at break is measured at a rate of / min, that is, a strain rate of 2 min-1.

(3) Melt index According to ASTM D-1238.

(4) Apparent spinning draft (Df) The ejection volume c is obtained by dividing the ejection amount g / min of the single yarn (filament) by the density of the polyester in a molten state of 1.2 g / cm ^3.
c / min is calculated, and this is divided by the discharge hole cross-sectional area to calculate the discharge linear velocity V ₀ . Df is calculated from the ratio (the following formula) to the winding speed Vw.

Df = Vw / V ₀ (5) Die Temperature The detection end is inserted into a 2 mm-depth temperature detection end insertion hole previously formed on the surface of the die in the spinning winding operation state, and the die temperature is measured.

(6) Cooling Air Velocity Under the Cap A wind speed meter was measured at n = 5 (five measurements) with the anemometer in close contact with the honeycomb surface at a position 30 cm from the upper end surface of the cooling air outlet of the honeycomb structure. Calculate the average value.

(7) Number of feathers / m The number of fluffs in a false twisted yarn of at least 25 m is visually counted and converted into fluffs per meter.

Hereinafter, the present invention will be described with reference to examples.

[Example 1] (Production of base polymer A) Dimethyl terephthalate 97
0 parts, 640 parts of ethylene glycol, 0.31 part of manganese acetate as a transesterification catalyst [25 mimole% (hereinafter referred to as mmol%) to dimethyl terephthalate] and 0.10 part of sodium acetate as a crystallization inhibitor (15 m
mol% of dimethyl terephthalate) into a reactor equipped with a stirrer, a rectification column and a methanol distillation condenser, and heated from 140 ° C. to 230 ° C., while distilling off the methanol produced as a result of the reaction outside the system. Exchange reaction was performed. 3 hours after the start of the reaction, the internal temperature reached 230 ° C.
20 parts of methanol were distilled off. Here, 0.18 parts (25 mmol% of dimethyl terephthalate) of trimethyl phosphate was added as a stabilizer, and reacted for 10 minutes. Then, 0.44 parts of antimony trioxide (30 mm) was used as a polymerization catalyst.
% of dimethyl terephthalate) and 2.91 parts of titanium dioxide as a matting agent were added, and the mixture was reacted for 20 minutes to complete the transesterification reaction. Next, the obtained reaction product was transferred to a polymerization reactor equipped with a stirrer and a glycol condenser, and the polycondensation reaction was performed while gradually raising the temperature from 230 ° C to 285 ° C and reducing the pressure from normal pressure to a high vacuum of 1 mmHg. Was. After a total polycondensation reaction time of 3 hours and 30 minutes, polyethylene terephthalate of [η] 0.64 was obtained.

After completion of the reaction, the polymer was formed into chips according to a conventional method.

(Production of Base Polymer B) 860 parts of terephthalic acid and 390 parts of ethylene glycol were charged into a pressure-resistant autoclave, and water generated at 220 to 260 ° C. for 3 hours under a pressure of 3 kg / cm ² with N ₂ was distilled. The mixture was subjected to an esterification reaction while leaving. After about 180 parts of water had been distilled off, 0.04 part of trimethyl phosphate (5 m
mol% of terephthalic acid), and after 10 minutes, 0.45 parts (30 mmol) of antimony trioxide as a polycondensation catalyst.
% Of terephthalic acid) and 0.7 of p-hydroxybenzoic acid
5 (0.1 mmol% based on terephthalic acid) was added, and 2.58 parts of titanium dioxide was further added as a matting agent, and the mixture was reacted for 10 minutes to complete the esterification reaction. Next, a polycondensation reaction was carried out in the same manner as in the base polymer A, and polyethylene terephthalate having an [η] of 0.64 was obtained in a total polycondensation reaction time of 3 hours.

(Production of base polymer C) 970 parts of dimethyl terephthalate, 640 parts of ethylene glycol, and 0.31 part of manganese acetate (25 m
mol% of dimethyl terephthalate) in a reactor equipped with a stirrer, a rectification column and a methanol distillation condenser, and heated from 140 ° C. to 230 ° C., while distilling off methanol produced as a result of the reaction outside the system. The transesterification reaction was performed. 3 hours after the start of the reaction, the internal temperature reached 230 ° C,
320 parts of methanol were distilled off. Here, 0.22 parts of trimethyl phosphate (30 mmol%
After adding dimethyl terephthalate) and reacting for 10 minutes, 0.44 parts (30 m) of antimony trioxide was used as a polymerization catalyst.
(mol% based on dimethyl terephthalate) and 32.4 parts of 2,6-naphthalenedicarboxylic acid (3 mmol% based on dimethyl terephthalate), and further titanium dioxide.

Next, the obtained reaction product was transferred to a polycondensation reactor equipped with a stirrer and a glycol condenser, and
While gradually raising the temperature from 30 ° C. to 285 ° C., 1 mmH
The polycondensation reaction to obtain a polymer of [η] 0.64 was carried out while reducing the pressure to a high vacuum of g.

(Production of base polymer D) 860 parts of terephthalic acid and 390 parts of ethylene glycol were charged into a pressure-resistant autoclave, and water generated at 220 to 260 ° C for 3 hours under a pressure of 3 kg / cm ² with N ₂ was distilled. While leaving, an esterification reaction was performed. After about 180 parts of water had been distilled off, 0.04 parts of trimethyl phosphate (5 mmol% relative to terephthalic acid) was added as a stabilizer, and after 10 minutes, 0.45 parts of antimony trioxide (30 m
mol% based on terephthalic acid) and sodium acetate 0.21
32.7 parts (3 mmol% to terephthalic acid) of 2,6-naphthalenedicarboxylic acid and 2.58 parts of titanium dioxide as a matting agent were added, and the mixture was reacted for 10 minutes. To terminate the esterification reaction. Next, the obtained reaction product was subjected to a polycondensation reaction. [Η] = 0.64 with a polycondensation reaction time of 3 hours and 50 minutes
Was obtained.

(Production of Spun Yarn with High Residual Elongation) The above-mentioned chips were dried at 160 ° C. for 5 hours, and then melted at 300 ° C. by a single-screw full-flight type melt extruder having a diameter of 25 m. (T) is 121 ° C .; I is 1.0g / 10m
in (230 ° C. × 3.8 kgf) with a molecular weight of 150,000
Polymethyl methacrylate (PMMA), and a heat distortion temperature (T) of 95 ° C .; I. Is 2.5g / 10m
molecular weight 60,000 in (230 ° C x 3.8 kgf)
PMMA, the heat distortion temperature (T) is 145 ° C., and M.P.
I. Is 0.6g / 10min (230 ℃ × 3.8kg
In f), the PMMA-based copolymer having a molecular weight of 70,000 was introduced into the molten polyester in the extruder in a molten state from the side stream, and then mixed and dispersed through a 20-stage static mixer.
Metal fiber filter with a pore size of 0.1
From a spinneret having 36 ejection tags having a diameter of 4 mmφ and a land length of 0.8 mm (L), a molten polymer was obtained at a nozzle temperature of 285 ° C. from No. 1 of Table 1. Discharge was performed while changing the discharge amount according to each spinning speed as shown in Nos. 1 to 12. Further, from the horizontal blown spinning cooling cylinder provided 9 cm to 100 cm below the base, 2
5 ° C. air is blown at a speed of 0.23 m / sec to cool and solidify the discharged polymer stream.
After applying the oil agent treatment in the range of 0.30 wt%, 12
It was wound up as a spun yarn of 0de / 36f. The draft in each experiment was 407.

The experiment No. With respect to 2 to 12, 14 and 15, the orientation crystallization inhibitor shown in Table 1 was added in the same manner, and the polymerization time was adjusted to prepare a polymer having η = 0.64, which was used in the spinning step. Was.

Further, in Experiment No. Nos. 16 to 17 and Nos. 1
Samples Nos. 8 to 20 were prepared in the same manner as in the base polymers B and C, respectively, by adjusting the time of weight, to prepare a polymer having η = 0.64, which was used in the spinning step.

The oil composition (Fa) used in this example is described below. Further, the emulsion concentration was 10 wt%, and the emulsion was attached using a metering oil nozzle.

The properties of the spun yarn, the state of dispersion of the fiber elongation improver, and the winding tension were de × 0.15 to 0.2
Adjusted within the range of 5, and wound as a 7 kg wound package.

Regarding the roll appearance, ◎: extremely good,
：: good, △: there was a loss, ×: rolls were broken, and each symbol was marked as a burst.

Oil composition (Fa) • Butanol PO / EO (50/50) random adduct (molecular weight 2000) 50 wt% • Glycerin PO / EO (50/50) random adduct (molecular weight 6000) 47 wt% • Sodium alkyl sulfonate Salt (alkyl group C12 to C16) 1.5 wt% EO 2 mol lauryl phosphate potassium salt l. 5wt%

[0074]

[Table 1]

Hereinafter, the results in Table 1 will be considered.

Experiment No. In a spun yarn containing a large amount of PMMA as in No. 1, the inter-fiber friction is reduced due to the large number of PMMA particles on the fiber surface, and the elongation improvement rate is very good. Dropping bursts occur and commercial packaging is difficult. In addition, No. 2
As for, the addition of the oriented crystallization inhibitor was small, so the amount of PMMA added was reduced and the winding property was ensured, but the elongation improvement rate was greatly reduced, and the winding property and elongation were improved. The rates cannot be compatible. On the other hand, No. 3, 5, 8, 9, 1
As for Nos. 1 and 12, since the amount of the oriented crystal inhibitor, the heat distortion temperature of PMMA and the amount added satisfies the requirements of the present invention, both the residual elongation and the winding property of the spun yarn were sufficiently effective. .

No. Regarding No. 4, since the heat deformation temperature of PMMA is as low as 95 ° C., it is not possible to form a particle diameter that effectively exhibits an improvement in the residual elongation, so that the number of particles that precipitate on the fiber surface increases, and winding is impossible. Become.

No. In No. 6, a large amount of PMMA was added, and at a high speed of 5500 m / min, the traverse occurred due to a decrease in the friction coefficient between fibers.

On the other hand, no. No. 7, since a large amount of Na acetate was added in excess of the requirements of the present invention, it precipitated as coarse particles in the polymer and contributed to a reduction in the friction coefficient of the fiber surface. , A rise in pack pressure was observed.

No. No. 10 contains a PMMA copolymer obtained by copolymerizing MMA, non-acrylic acid imide and styrene at a molar ratio of 25:55:20, and having a high heat deformation temperature of 150 ° C. In this case, since the heat deformation temperature difference from the polymer is so large that the effect as an elongation deformation resistor is too large, the PMMA copolymer particles cannot follow the deformation of polyethylene terephthalate, and the particle diameter is large. Neither property nor winding property is possible.

No. In the case of No. 13, when the spinning speed is as high as 8500 m / min, the spinning strain rate is remarkably high. Therefore, it is estimated that the spinning property is impaired due to the interfacial separation between the polymer and PMMA.

In addition, No. 14 is an elongation improver P
Although the MMA was reduced beyond the requirements of the present invention, the winding property and the spinning property were secured, but the improvement in the residual elongation was small and the effect was insufficient. On the other hand, No. With respect to Nos. 16 and 20, since the addition of the orientation crystallization inhibitor is small, the spinning at high speed is impaired along with the decrease in the residual elongation, and the spinning is unstable. In contrast, 15, 17, 18, 2
Samples Nos. 1 and 22 satisfied the requirements of the present invention, and thus, a sufficient effect was recognized in both the residual elongation of the spun yarn and the winding property.

On the other hand, No. Regarding 19 and 23, as an orientation crystallization inhibitor, each copolymer component is excessively added, and the copolymer is based on a copolymerized polymer.
It cannot be put to practical use due to its strong elongation characteristics. Further, the number of occurrences of feather breaks in the spinning process is large.

[Example 2] Based on the production method based on the direct polymerization method shown in Base Polymer D, a polymer was prepared in which an orientation crystallization inhibitor with η = 0.61 was used in combination, and formed into chips, which were formed at 160 ° C x 5 ° C. After drying for an hour, while feeding light weight from the chip pipe, the same polyester master of 10% polystyrene having a heat distortion temperature of 109 ° C. is also dried similarly, and this is also mixed with light weight feed to reduce the polystyrene addition concentration in polyethylene to 2.5%. %, The blend polymer was introduced into the spinning pack, and the spinning conditions were the same as in Example 1 at a take-off speed of 5500 m / min.
It was wound up as a spun yarn of 5 de / 36 f.

[0085]

[Table 2]

Hereinafter, the same consideration will be given.

No. As for Nos. 24 to 26, the added amount of each oriented crystallization inhibitor and the total amount thereof satisfy the requirements of the present invention, and a sufficient effect is recognized on the residual elongation and the winding property.

Claims (11)

[Claims] 1. An organic polymer which is incompatible with a polyester as a base polymer and functions as an elongation enhancer at the time of spinning. A polyester dispersed on the basis of the weight of the base polymer is melt-spun, and the melt is spun at 1,000 m / min or more. In obtaining a high-speed spun yarn at a take-up speed, a polyester obtained by adding a crystallization inhibitor specified in the following (a), (b) or (c) as the base polymer is used. A method for producing a high-elongation polyester spun yarn having improved winding properties. (A) 0.001 mol of at least one metal carboxylate selected from the group consisting of alkali metal salts of aliphatic monocarboxylic acids and alkaline earth metal salts with respect to the bifunctional carboxylic acid component constituting the polyester % To 0.05
The polyester, (b) p-hydroxybenzoic acid and / or an ester-forming derivative thereof added in an amount of 0.01 mol% is added to the acid component constituting the polyester in an amount of 0.01%.
(C) 2,6-naphthalenedicarboxylic acid and / or its ester-forming derivative in an amount of 0.1 to 5 mol% based on the acid component constituting the polyester. Polyester added in the range. 2. The method of claim 1, wherein the metal carboxylate is an acetate of lithium, potassium, rubidium, calcium, magnesium or barium. 3. The polyester fiber of claim 1, wherein the total amount of the crystallization inhibitor is in the range of 0.03 to 6.0% by weight based on the weight of the polymer. Method for producing yarn. 4. The spun yarn of claim 1, wherein the elongation enhancer is in the range of 0.3 to 3.5% by weight, based on the weight of the polymer. Production method. 5. The production of a high elongation polyester spun yarn having improved winding properties according to claim 1, wherein the ratio of the crystallization inhibitor to the elongation improver is in the range of 0.1 to 1000% by weight. Method. 6. The heat distortion temperature (T) of the elongation improver is 105.
The method for producing a high-elongation polyester spun yarn having improved winding property according to claim 1, wherein the temperature is in the range of -130 ° C. 7. The improved winding property according to claim 1, wherein the elongation enhancer is an addition polymer comprising an unsaturated monomer, which is substantially incompatible with the polyester and has a molecular weight of at least 2,000 or more. , A method of producing a high elongation polyester spun yarn. 8. An addition polymer comprising an unsaturated monomer,
It has a molecular weight of 8,000 to 200,000 and a melt index (230 ° C., load 3.8 kg) of 0.5 to 8.0.
The method for producing a high elongation polyester spun yarn having improved winding property according to claim 6, which is a polymethyl methacrylate polymer containing methyl methacrylate as a main component in g / 10 minutes. 9. An addition polymer comprising an unsaturated monomer,
It has a molecular weight of 8,000 to 200,000 and a melt index (230 ° C., load 3.8 kg) of 0.5 to 8.0.
The method for producing a high elongation polyester spun yarn having improved winding property according to claim 6, which is an isotactic polystyrene polymer containing styrene as a main component in g / 10 minutes. 10. An additive polymer comprising an unsaturated monomer having a molecular weight of 8,000 to 200,000 and a melt index (300 ° C., load 2.16 kg) of 6 to 25.
The wound property is improved according to claim 6, which is a syndiotactic (crystalline) polystyrene-based polymer having g / 10 minutes.
Method for producing high elongation polyester spun yarn. 11. An additive polymer comprising an unsaturated monomer, having a molecular weight of 8,000 to 200,000 and a melt index (260 ° C., load 5.0 kg) of 5.0 to 4
The method for producing a high elongation polyester spun yarn having improved winding property according to claim 6, wherein the polymethylpentene polymer is a polymethylpentene-based polymer containing 4-gm-pentene-l as a main component at 0.0g / 10%.