JPH0192411A - Polyester fiber and production thereof - Google Patents

Abstract

PURPOSE:To obtain the titled fiber having durable excellent frictional melt- preventive property, by adding an organic polysiloxane to a polyester fiber containing inert fine particles using a specific method and dispersing the organic polysiloxane in the fiber in a specific state. CONSTITUTION:An organic polysiloxane is added to a molten fluid of a polyester polymer containing 3-20wt.% of inert fine particles having an average particle diameter of <=3mum at a time after the completion of the polymerization of said polymer and immediately before spinning. The mixture is kneaded by dividing into layers with a static mixer containing >=15 elements and extruded through a nozzle hole to obtain the objective fiber containing the organic polysiloxane extending in the longitudinal direction of the fiber to form an independent island phase. The size of the island is finer at the outer layer than at the inner layer in the lateral cross-section of the fiber. Said islands are dispersed in high concentration at the outer circumferential part and are connected with each other with connecting channel randomly distributed at a definite ratio per unit length of the fiber.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a polyester fiber having good anti-friction properties and a method for producing the same. The present invention relates to polyester fibers containing organic polysiloxane in a certain specific state in a weight percent of polyester fibers, which have a remarkable effect on anti-friction properties, and to a method for producing the same.

(Conventional technology Polyester fiber has excellent dimensional stability.

It has become an essential material for clothing due to its chemical resistance, strength, and durability. However, depending on the intended use, the surface properties may not be sufficient, so quality improvement is desirable.
I was in b. In particular, in the case of sportswear, etc., fibers must have the ability to withstand extreme physical exertion, and conventional polyester fibers are oversized and have the ability to withstand excessive friction during sliding, etc. It was easy to have the disadvantage of putting it away.

As a means to improve drag, the general method used is to apply a silicone-based finishing agent to the fabric surface using a post-processing method to lower frictional resistance and suppress frictional heat generation.
Was. It has been found that although this method provides a fair initial performance, it does not reach a satisfactory level in terms of durability.

Particularly when worn for a long period of time, the post-processing on the fiber surface progresses and falls off, eventually resulting in a problem where it deteriorates to the same level as regular polyester fiber. Similar undesirable phenomena or problems also occurred when the number of washings increased. In addition, post-processing type silicone contains an emulsifying activator, which tends to cause disperse dyes to migrate and sublimate, often causing a problem.

Under these circumstances, there has been an increasing demand in the field of sports clothing such as training wear for the development of polyester fibers that have durable anti-friction properties without reducing color fastness.

As a result of intensive studies to solve this problem, the inventors of the present invention found that the problem can be solved by creating a polyester fiber containing a high viscosity organic silicone compound in a specific dispersed state and by incorporating inert particles into the polyester fiber. It is something.

By the way, many studies have been conducted on modifications that have various durability properties by incorporating organic polysiloxane into the polyester polymer without adhering it to the surface of the polyester fiber. Japanese Patent Publication No. 43-1778 which discovered the effect of improving whitening of polyester fibers, Japanese Patent Publication No. 194118-1980 which improved tensile knot strength and impact knot strength, and Japanese Patent Publication No. 60-104521 which aimed at improving surface abrasion properties. No., JP-A No. 61-12914 aimed at water-repellent polyester fibers, JP-A No. 50-75241 aimed at improving surface smoothness, etc., etc., etc., are known about many polyester and organic polysiloxane compositions. ing.

However, in order to impart effective and durable anti-friction properties, it is not recognized that organic polysiloxane should be dispersed and contained in polyester fibers in any form and in any state. Nor was there any knowledge of such methods.

(Problems to be Solved by the Invention) That is, an object of the present invention is to fundamentally solve the drawbacks of the conventional post-processing method in which a friction preservative is attached to the surface of fibers. When the fiber is incorporated into the fiber, in order to make it an effective fiber, the question is what kind of material should be used and which condition should be used for the structure, and the present invention has investigated this point. It is something.

(Means for Solving the Problems) The present invention includes organic polysiloxane of 1.0 ffftt%.
As mentioned above, it is contained in the polyester so that the 10-fold fi is 96 or less, and the dispersion state of the organic polysiloxane is
An independent phase with an apparent island state is formed, and on top of that, the outer layer of the fiber cross section forms a fine island state, and the inner layer or a larger high state is formed, and the outer periphery exhibits a highly concentrated dispersed state, and the islands are separated from each other. It is a polyester fiber characterized by being not completely separated but dispersed in a state in which communication paths connecting islands are randomly formed in the cross-sectional direction. % or more and 20% by weight or less.

The present invention also provides a method for obtaining such fibers, in which a particularly high viscosity organic polysiloxane is used, and after the completion of polymerization of a polyester polymer in which 3 to 20 ffijii96 of inert fine particles are dispersed, immediately before spinning. After adding it to the molten fluid of polyester polymer and then kneading it in layers with a static mixer with 15 or more elements,
When the nozzle diameter is D and the land length is L/D, it is discharged from a nozzle hole to form fibers, and the above-mentioned fibers are produced by this method.

As the organic polysiloxane referred to in the present invention, there are various types of organic polysiloxanes.
Although it is possible to use a silicone compound, it is preferable to use a silicone compound that does not easily volatilize at the polyester spinning temperature. In particular, those with a weight loss rate of 1% or less when heat treated at 150'C for 24 hours are preferable. As specific examples, dimethylpolysiloxane, diphenylpolysiloxane, methylphenylpolysiloxane, etc. can be used alone or in combination.

The viscosity of organic polysiloxane is 10.000 at 25°C.
centistokes or more, preferably 30,000 centistokes to 10,000 centistokes. It has been found that when the viscosity is lower than 10,000 centistokes, the effect of frictional anti-fusing properties is no longer exhibited, and unless the content is increased, the frictional anti-magnetic properties will not be exhibited.

It has been found that the higher the viscosity of the organic polysiloxane, the more effective the anti-friction properties are, and in particular, the effect is dramatically improved when the viscosity is 30,000 centistokes or higher. This is a fact that has not been well known until now, and has been made clear as a result of various studies on how to incorporate it into polyester to achieve friction-proofing properties.

At present, it is not clear why high-viscosity organic polysiloxanes exhibit such remarkable effects. Although not,
This is probably because the dispersion state when incorporated into the polyester polymer tends to form a sea-island state that exhibits a remarkable friction-proofing effect as described below.

In addition, when the viscosity of the organic polysiloxane decreases, phase separation from the polyester progresses further, which not only significantly reduces spinnability and drawability, but also reduces the thermal history of the organic polysiloxane contained in the polyester during the process of manufacturing textile products. It has been found that in the process of being exposed to heat, the particles migrate to the fiber surface, which is not only unfavorable in terms of the texture of the textile product, but also significantly reduces the durability of the friction-proofing property.

Regarding plastic materials, there are many examples of compounding organic polysiloxanes to reduce the coefficient of surface friction, but it has been reported that as the viscosity of organic polysiloxanes decreases, the tendency to bleed to the surface increases [M, P, L,
nil l, etal, , Advances
in polymer friction and we
ar, Ao 88ymposium, Plenum
Press.

469 (74)], it was thought that a phenomenon similar to this might have occurred during the course of studying the present invention.

Conversely, the higher the viscosity of the organopolysiloxane, the greater the friction-proofing effect (and the better the durability); however, if it exceeds 100,000 centistokes, the viscosity becomes too large and is difficult to handle during work. It is undesirable because the quality deteriorates significantly.

The amount of organic polysiloxane in the polyester containing organic polysiloxane is 1.0% by weight as the base of the compound.
As mentioned above, it is necessary to keep the amount at most 10% by weight, and more preferably at least 2.0% by weight and not more than 8% by weight. If the content is less than 10% by weight, it is not desirable in terms of cost or the melt-proofing effect is not sufficient. 10% by weight
If this is recommended, the frictional magnetic shielding effect will improve in proportion to the total content, but the processability of forming fibers will be extremely reduced. In particular, when the single filament denier of the fiber is less than 1.5 denier, single filament breakage occurs frequently during spinning and fuzz occurs during drawing, resulting in a significantly poor pass rate. If the denier is .0 denier, the pass rate will drop to about 50% or less, and the productivity will be very poor, which is not preferable. In addition, the higher the organic polysiloxane content, the higher the raw material trade and the greater the cost increase, so we came to the conclusion that it is preferable to keep the content below 1096 based on a comprehensive evaluation.

Surprisingly, it has also been found that by incorporating inert particles in the polyester polymer in an amount of 3% by weight or more, more preferably 5% by weight or more, even higher frictional anti-fusing performance can be achieved.

However, if the content of the inert fine particles increases, there will be more fuzz and yarn breakage during spinning and drawing, resulting in poor process performance, so the upper limit of the amount added is 20% by weight or less, and more preferably 10ifi%. It is as follows. Examples of inert fine particles include alumina, zirconia, barium sulfate, calcium carbonate, magnesium oxide, silica, titanium oxide,
Aluminum phosphate, calcium phosphate, etc. are available, but silica, titanium oxide, and barium sulfate are more preferable, considering processability such as spinnability and stretchability, and friction-proofing performance. It is not precisely known why the presence of a high addition of inert fine particles further improves the frictional melting prevention performance, but it is probably because (when fibers are subjected to strong friction, the polymer melts due to the frictional heat). Since the inert fine particles do not melt and retain their original shape, the anti-fusing properties of the fibers are not expressed, but it is also possible that the organic polysiloxane has a synergistic effect due to its coexistence with the effect of reducing frictional heat. This seems to be due to the lack of performance f'L.The average particle size is 3μ or less,
The thickness is preferably 1 μ or less from the viewpoint of processability such as spinnability, stretchability, and false twistability.

The polyester fibers referred to in the present invention include, for example, terephthalic acid, inphthalic acid, naphthalene 2,6 dicarboxylic acid, phthalic acid, α, β-(4-carboxyphenocoal)
Aromatic dicarboxylic acids such as ethane, 4,4-dicarboxydiphenyl, 5-sodium sulfoiphthalic acid or aliphatic dicarboxylic acids such as adipic acid, sebacic acid, or esters thereof, ethylene glycol, diethylene glycol, 1 It is a fiber-forming polyester synthesized from diol compounds such as 4-butanediol, neopentyl glycol, cyclohexane-1,4-dimetatool, polyethylene glycol, and polytetramethylene glycol, and contains 80 mol% or more of the constituent units. However, polyesters in which 90 mol% or more are polyethylene terephthalate units or polybutylene terephthalate units are particularly preferred. The polyester may also contain small amounts of additives, such as matting agents such as calcium carbonate, antioxidants, optical brighteners, stabilizers, or ultraviolet absorbers.

What is more important in the present invention is that the viscosity is 10.0 as described above.
1.00 centistoke or more organic polysiloxane.
03i is contained in the polyester in an amount of % or more and 10% by weight or less, and when the dispersion state of the organic polysiloxane in the polyester is maintained in a certain specific state, it exhibits a remarkable effect on frictional anti-fusing performance. be. In other words,
When viewed in the cross section of the fiber, the organopolysiloxane appears to form an island, and the outer layer of the fiber cross section is in the form of fine islands, forming an island-like layer larger than the inner layer. It was found that the fibers exhibit a highly concentrated dispersed state, and the islands are not completely separated (they must be dispersed with communication paths randomly connecting the islands in the cross-sectional direction of the fiber). This is a new fact that I was not aware of until now.

The means for realizing such a dispersion form will be explained in detail later, but it can be manufactured based on the three correlations of the viscosity of the organic polysiloxane, the content in the polyester, and the method of intermixing the organic polysiloxane and the polyester. It has become possible.

In the present invention, by containing organic polysiloxane in a finely dispersed state and at a high concentration in the outer fiber layer, the effect of organic polysiloxane kneaded into polyester can be fully exhibited even with a small amount of addition. It is presumed that there is. Finally, organic polysiloxane is 1hf.
It is natural to think that the effect will be more effective if the islands are dispersed as finely as possible without being unevenly distributed, and when comparing the number of islands, there are 8 islands per unit cross-sectional area in the outer layer and the inner layer.
The reason why the effects of the present invention are effectively exhibited can be seen from the fact that the number of products on the outer periphery is increased by a difference of more than one to one.

The method of measuring the size of the islands of organic polysiloxane present in polyester is to slice the spun fiber into a thickness of several tens of millimeters to around 100 millimeters using an ultramicrotome, and then It is possible to observe ultrathin sections under high magnification using a transmission electron microscope. As a simple method, the discharged yarn discharged from the spinning nozzle before winding can be sliced with a microtome to a thickness of about 5 microns, and the sliced yarn can be observed under high magnification with an optical microscope.

In addition, in the structure of this fiber, the organic polysiloxane is not in a high state that is completely independent of each other in the longitudinal direction of the fiber, but the islands of the polysiloxane are connected in the cross-sectional direction of the fiber. It is observed that they are connected to each other. That is, a specific method for determining the formation state of this communication path is to immerse the fiber in a 1/10 N alkaline solution and treat it at 98°C, and then remove a predetermined amount of the fiber surface. Afterwards, by observing the fiber surface with a scanning electron microscope, it can be determined that the formation of this communication path results in a finely dispersed state with a high density of organic polysiloxane islands in the outer layer of the fiber. This is not only due to the presence of polysiloxane islands in the outer peripheral portion and polysiloxane islands in the inner layer portion, but also due to the fact that 1. It is thought that the large islands in the inner layer function as a storage tank for supplying organic polysiloxane to the surface layer21. It is believed that this structure is linked to the practical effects of the fibers of the present invention.

FIG. 1 shows the friction-proofing fiber (single fiber 2.1 denier) according to the present invention immersed in a 1710N alkaline solution.

Electron micrograph (part of X5,0OOJ) of the fiber surface after being maintained at 98°C and subjected to 3096 alkali weight loss treatment.Polyethylene terephthalate was used as the polymer, and polydimethylsiloxane with a viscosity of 60, 5,000 centistokes
It is added to 0% by weight fiber. Line-like unevenness can be seen on the fiber surface, and the roughness is the part where polydimethylsiloxane existed as an aggregate. In addition, black holes can be seen here and there in the striped concave portions, but these holes are communication paths in the cross-sectional direction of the fibers as described in the present invention. This communication path is connected to a tank of polydimethylsiloxane stored in the inner layer of the fiber, and is thought to play an important role in exerting the anti-friction effect.

Figure 2 shows a photograph of the yarn spun under the same conditions as the yarn in the electron micrograph in Figure 1, which was spun out from the spinning nozzle and sliced with a microtome into 5 micron thick pieces, and observed with a transmission optical microscope. This is a partial illustration. It can be seen that the dimethylpolysiloxane islands in the outer layer of the fiber cross section are denser than those in the inner layer, and are dispersed in the polyester in a large number of fine crystals.

Figure 2 shows an example of a cross-section photo of a polyester polymer containing dimethylpolysiloxane, which has a so-called core-sheath structure and a dorsal-ventral structure in which the fiber is centered or does not contain any organic polysiloxane. Even in the case of composite fibers, if the organopolysiloxane-containing polyester has a fiber cross-sectional circumference of 4096 or more and a fiber cross-sectional area of 20% or more, it has been found that it has a similar friction-proofing effect. . It goes without saying that the lower the fiber cross-sectional circumference of the organopolysiloxane-containing polyester, the lower the anti-friction effect, but the effect was sufficient if it was 40% or more. In this case, the dispersion state of the organopolysiloxane in the organopolysiloxane-containing polyester part is
What needs to be distributed in the state explained so far is
I'll say it again: It's a no-brainer.

In the present invention, shapes similar to pentagonal or hexagonal can be obtained by high-order processing such as false twisting and crimp processing, or trilobal, T-shaped, or quadrilobal shapes can be obtained by using an irregular cross-section nozzle during spinning. Even if the organopolysiloxane has a variety of cross-sectional shapes, such as five-lobed, six-lobed, seven-lobed, seven-lobed, and eight-lobed, the dispersion in the polyester of the organopolysiloxane, which has been explained in the past, is one or almost all. It is needless to say that the effects of the present invention will not be fully realized if the conditions are kept the same.

Next, a manufacturing example of the friction-fusible polyester fiber of the present invention will be explained. To obtain fibers in which the dispersion state of organic polysiloxane in polyester is maintained, which is effective for frictional anti-melting properties as described in the present invention It has become possible to manufacture it because the content of polyester is at least a predetermined amount and because of the three-tone correlation between the kneading method of organic polysiloxane and polyester.

As mentioned above, it is necessary to incorporate 1.0% by weight or more of an organic polysiloxane having a viscosity of 10,000 centistokes or more into the polyester, and at the same time, the kneading method is also important. In other words, one of the requirements for satisfying the present invention is that the organic polysiloxane is added immediately before spinning after the polymerization of the polyester polymer containing at least 3% of inert fine particles is completed, and then after kneading, the organic polysiloxane is added to the nozzle hole. It is extruded and made into fibers.

After completion of polymerization - If the step of forming pellets is completed, the organic polysiloxane is added to the polymerization kettle after the completion of the first polymerization, and then the inert fine particles are contained at 3% by weight or more during spinning, rather than being made into pellets. Feeding a predetermined amount of organopolysiloxane into the polyester polymer melt fluid stream rL;
After that, it is preferable to knead the mixture using a static mixer and then extrude it through a spinning nozzle orifice to form fibers. Because 1
When an organic polysiloxane is added in the polymerization process, it is extremely difficult to control the production of pellets in which the dispersion state of the present invention is maintained uniformly, and it is virtually impossible.

Organic polysiloxane and polyester are not compatible or easily phase separated, so even if the organic polysiloxane is added at the final stage of polymerization and then kneaded, the residual polymer inside the polymerization pot will be absorbed during the residence time during pellet removal. Phase separation of the organopolysiloxane and polyester polymer proceeds. the result.

It is not possible to maintain the desired dispersion state (not only is it possible to produce pellets with non-uniform dispersion density, but process performance such as thread breakage when fiberized is deteriorated, and at the same time there is a problem of unevenness or pressure generation, which is undesirable) .

Addition of auxiliary agents such as surfactants to maintain uniform dispersibility in the polymerization pot is also being considered, but adding such auxiliary agents will certainly improve dispersibility, but it will not cause fiber formation. This is undesirable because the subsequent dyeing fastness deteriorates.

The present invention provides a polyester fiber that maintains color fastness and has friction and melting resistance.

In a continuous process in which the molten polymer is continuously fed and discharged from a spinning nozzle without going through the step of pelletizing after completion of polymerization, a polyester molten polymer stream containing 3% by weight or more of inert fine particles is used immediately before spinning. It is preferable to feed a fixed amount of organic polysiloxane to the mixture, knead it with a static mixer, and then discharge it from a spinning nozzle hole.

When spinning using an extruder using polyester polymer pellets containing inert fine particles at 3% or more, feed a predetermined amount of organic polysiloxane into the melt line of the melt-extruded polyester polymer, and then mix the line with a static mixer. It is preferable to discharge it from a post-spinning nozzle.

What is important when kneading using a static mixer is that it is necessary to knead using a static mixer with a certain number of elements or more. There are several types of static mixers that are currently in practical use, but for example, if you pass through an n element made by Kenics Co., Ltd., which has blades twisted 180 degrees left and right and arranged 90 degrees apart,
When using a static mixer that divides into n layers, it is necessary to use a mixer with at least 15 elements.

If the number is less than 15 elements, it will not be possible to collect fibers in the desired dispersed state, and the organopolysiloxane will not only be unevenly distributed in the polyester, but also will not form finely dispersed islands as shown in Figure 3, but will form large islands. Therefore, the number of products will be reduced.

Ultimately, the formation of communication paths in the cross-sectional direction of the fibers, which play an important role in exhibiting durable friction and melt prevention properties, is reduced, and sufficient friction and melt protection is not achieved.

In addition, if the number of elements is not sufficient, the organic polysiloxane and NIJ ester are not uniformly kneaded sufficiently, which increases the occurrence of yarn breakage and fluffing during spinning, and at the same time, the drawability decreases, which is unfavorable in terms of the process. From the viewpoint of improving process efficiency, it is preferable that the number of elements is at least 15 elements, that is, 215 layers or more, and more preferably 20 elements or more, that is, 220 layers or more.

21 when using a static mixer other than Koenix
Needless to say, it is necessary to use a mixer having a number of elements corresponding to five or more layer divisions. Toshisha high mixer (lli-Mixer) Yarf-Yars 7nd e Ross (Charless & Boss
) Ross ISG mixer etc., when passing through n elements, the number of layer divisions is 4 degrees, so the number of elements needs to be 8 or more, more preferably 1o or more.

What is important in producing the fibers of the present invention is to knead them using a suitable Niremen 1-45 static mixer, but at the same time, another important thing is the diameter of the spinning nozzle hole. There is a need to keep the land length ratio above a certain level. That is, if the nozzle hole diameter is D and the land length is L, then by setting L/D to 2.0 or more, a rust state is formed, which is a modern way to exhibit durable friction and melting prevention properties. I found out that it was terrible. That is, the outer layer has a concentration gradient that maintains an areal density state of more than twice that of the inner layer, and the roughness of the organopolysiloxane islands is less than 1/2 in the outer layer compared to the inner layer. It was found that fiberization occurred in a dispersed state in which the number of islands remained 8 times or more.

If L/IJ is further increased by 2.0 or more, the dispersion state of the organopolysiloxane will become more favorable for frictional melting prevention properties, but once it reaches a certain steady state, it will remain almost the same. I can't maintain it. L/D against that
As is increased, the pressure loss increases dramatically, the shear rate becomes too high, making it impossible to perform stable spinning, and the life of the spinning back becomes short, which is not preferable. After all, if stable spinnability is considered, it is better to keep the L/D within an appropriate range.

At present, it is not possible to clearly explain why the L/D of the nozzle hole has a significant effect on the dispersion state of organopolysiloxane in polyester fibers, but it is probably when the pipe is damaged. This is thought to be due to the fluid behavior of the polyester and organic polysiloxane.

At the high temperature of 280-300℃, which is the spinning temperature of polyester, the melt viscosity of polyester is much thicker than that of organic polysiloxane, so polyester reduces the resistance of the hole wall when passing through the nozzle hole diameter. Therefore, the organopolysiloxane with relatively low resistance tends to flow toward the wall, and a concentration gradient occurs due to some kind of phase separation phenomenon or during the process of passing through the nozzle hole. I think it will appear. At the same time, the organopolysiloxane that is trying to flow toward the pore walls is subjected to even finer crosstalk effects by the high melt viscosity flow of the polyester polymer that is trying to flow backwards toward the center, so that the islands of organic polysiloxane in the outer layer become smaller in the inner layer. It is estimated that the result will be that the particles will be dispersed in a thinner state. It is believed that if L/D is too small, the fibers will be discharged from the nozzle hole without sufficiently performing this action, resulting in the fibers of the present invention being unrefined.

Using an irregularly shaped nozzle, find the cross section m(X) of the irregularly shaped nozzle when spinning a yarn with irregularly shaped cross section, find the D value of the irregularly shaped nozzle corresponding to the diameter of the round hole nozzle from X=πy, and calculate the land length from the All you have to do is set .

An example of the manufacturing process of the present invention is shown in FIG. melt extruder l
The polyester polymer melt flow containing 3% by weight or more of inert fine particles extruded by the method was subjected to PR constant weighing (
! Reduce. On the other hand, the organic polysiloxane is metered in a predetermined amount by the feed colander by the additive feeder 4 and by the metering device 3, and then added into the polyester polymer melting line by the metering device 2. Thereafter, in a static mixer equipped with a predetermined number of elements, the organic polysiloxane and polyester are discharged from a mixed wire tube and a spinneret bag 6 to form fibers.

The static mixer may be located within the polymer flow in or within the spinneret bag.

There is no harm in installing it separately in the inside where the polymer flows and in the back of the spinneret.

(Examples) Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these in any way. The measured values for frictional melting resistance described in the examples are as follows:
False twisted yarn of organic polysiloxane-containing polyester fiber 15
After making 0dr-4Of and smoothly knitting the sori in 3 stages, it was brought into contact with a rotating roller with a load of 2.5#9 and the time until holes were formed was measured.

It can be judged that the longer the hole is, the thicker it is due to the effect of frictional melting prevention.

Another evaluation method, the impact method, involves placing the measurement sample and
A weight with a constant load is suspended above the sample, and the state of the sample is observed when the surface of the sample is made to reciprocate once like a pendulum in a clock.

[Examples 1 to 2] Barium sulfate (average particle size 0.58 μm, 6096 water paste) was mixed with ethylene glycol (hereinafter abbreviated as EG) at a weight ratio of 1:1, and the mixture was heated using a vibration mill (Sanei). The mixture was mixed and crushed for 10 hours using an MB-1 model (manufactured by Seisakusho). Mix this with terephthalic acid (hereinafter abbreviated as TA) and EG, and adjust each so that the molar ratio of EG and TA is 1.5 and the barium sulfate content (wt%) in the polymer is 596.10%. Add 8bzOa 4o to this slurry.
o ppm was added. This slurry was heated to an internal temperature of 240°C.
The mixture was fed to an esterification tank for 2 and a half hours to carry out esterification, and the temperature was raised to 270°C over roughly 40 minutes to complete each reaction separately, and then transferred to a polymerization tank with an internal temperature of 290°C. Then, the pressure was gradually reduced to 1 rrmkg or less and polymerization was carried out for about 3 hours, and the strands were extruded into water under nitrogen pressure and cut to obtain chips of [η)=0.65.

Obtained. Polyethylene terephthalate was extruded using a 40φ extruder, and the viscosity at 25°C, which had been completely dried at 120°C, was added to the molten polymer line.
000 centistokes of dimethylpolysiloxane was injected at a concentration of 3% by weight based on the polymer, then kneaded with a 40-element static mixer manufactured by Kenics, and spun through a Li2) 30 round hole nozzle. .

The spun yarn was drawn using a roller plate method under normal conditions, and further false twisted under normal conditions to obtain a 150 dr-4
A multifilament false twisted yarn of Of was obtained.

The spinnability, stretchability, and false twistability were good and there were no problems at all.

The obtained false twisted yarn of 150 dr-4Of was knitted smoothly in three stages and the frictional melting resistance was measured, and the time required to form a hole was 85 seconds for Example 1 and 110 seconds for Example 2. Furthermore, when the frictional melting resistance was measured after washing 100 times, there was no change at all and the number of seconds was the same.

In addition, the test results by the impact method showed that the samples of Examples 1 and 2 had no holes at all. Reference example 1.2 in which the amount of inert fine particles mixed in is less than the specified amount will be described later, but in this example,
It can be seen that the frictional anti-fusing performance is significantly improved compared to this reference example.

Furthermore, after dyeing this three-tier smooth knitted fabric using the following procedure, the color fastness was examined. As shown in Table 1, it was found that there were no problems at all.

Temperature 80'X 20 weight light fastness; Evaluate the discoloration and fading of the sample using a carbon arc lamp according to JIS L-0842.

Washing fastness: Evaluate the degree of staining and discoloration using ester and cotton cloths as attached cloths according to JIS L-0844.

Masatsuki fastness 1lls Masatsuki cotton (contamination degree of 5 was evaluated 100 times with a load of 200g using a Gakushin type Masatsu fastness tester according to L-0849.

[Reference Example 1] [η) = 0.65 dll/g (intrinsic viscosity measured using a Uperohde viscometer in a constant knitting tank at 30°C using a mixed solvent of equal amounts of phenol and tetrachloroethane),'
1'i (Polyethylene terephthalate to which 5 wt% of J2 was added was extruded using a 40φ extruder, and the viscosity at 25°C, which had been thoroughly dried at 120°C in advance, was 60,000 centistokes). 3% by weight of dimethylpolysiloxane based on the polymer
After that, the mixture was mixed with a 40-element static mixer made by Kenix Co., Ltd., and spun through a round hole nozzle with L/D of 3.0. The spun yarn was drawn using a roller plate method under normal conditions and further pre-combusted under normal conditions to obtain a 150 dr-4Of multifilament false twisted yarn.

The spinnability, stretchability, and false twistability were good and there were no problems at all.

The obtained 15Qdr-4Of pre-combusted yarn was smoothed in 3 stages to measure its friction and anti-fusing properties, and the time at which the hole was formed was 62 seconds (I). This example is.

Compared to the case where dimethylpolysiloxane is not contained at all, it takes only 0.5 seconds to form a hole, which has a considerable effect. In addition, the test results using the impact method showed that there were some holes in the sample.

[Reference Example 2] This example is an example in which the content of inert particles is small, and fibers in which 3 wt % dimethyl polysiloxane is added to polyethylene terephthalate containing 2 wt n % barium sulfate are prepared in the same manner as in Example 1. When the material was prepared and its friction and melting resistance was measured, the perforation time was 64.5. Additionally, as a result of the impact method test, there were some holes in the sample.

[Examples 3-4] Both sides are examples of different types of inert particles.

Dispersions were prepared by separately mixing EG with TiO2 (average particle size 0.2μ) or colloidal silica (average particle size 0.045μ). Thereafter, in the same manner as in Example 1, Ti (J23wt% in Example 3 and 5% in Example 4)
A polymer was prepared so as to have an i025 wl,%, and dimethylpolysiloxane was added thereto to form fibers in the same manner. The processability and friction-proofing performance were good.

[Example 5] This example uses organic polysiloxanes with different viscosities. Barium sulfate 10Wt96, dimethylpolysiloxane 5 wt
% polyethylene terephthalate fiber was created. The processability and friction-proofing performance were good.

[Example 6] This example is an example of a composite yarn, and the intrinsic viscosity [η]=0.
Polyethylene terephthalate containing 10 wt% of barium sulfate of No. 68 was extruded using an extruder, and dimethylpolysiloxane with a viscosity at 25°C of 60.000 centistokes, which had been completely dried at 120°C in advance, was added to the molten polymer line of the polymer. The polymer was then kneaded with a 40-element static mixer manufactured by Kenix Co. as a sheath component, and extruded through another extruder to make polyethylene with [η) = 0.65. Core-sheath composite spinning was carried out using terephthalate as a core component and a core/sheath weight ratio of 40/60 using a round hole nozzle with L/D=3.0. Stretching and false twisting was carried out using a conventional method to produce a multifilament false twisted yarn with a total of xso-4or.

The spinning properties, stretchability, and false twisting properties were good and there were no problems at all. The resulting 150dr-40f false twisted yarn was smoothly knitted in 3 stages and the frictional cutting characteristics were measured, and the time required for a hole to form was 95 seconds. In addition, when the frictional melting resistance was measured after washing 100 times, it was the same number of seconds with no change. There were no holes at all in the impact method test.

The three-tier smooth knitted fabric was dyed in the same manner as in Example 1, and then the dyeing hardness was examined. As shown in Table 1, there were no problems at all.

[Example 7] This example is an example of l'BT, and a polybutylene terephthalate polymer containing 10 wt% barium sulfate was prepared by a conventional method. A fiber containing 3% dimethylpolysiloxane was prepared in the same manner as in Example 1. The anti-friction performance was good.

[Comparative Examples 1 to 3] Comparative Example 1 uses an organic polysiloxane with a low viscosity, Comparative Example 2 uses a small amount of organic polysiloxane added, and Comparative Example 3 uses a small number of static mixer elements. In this example, a 150 dr-4Of false twisted yarn was obtained using the same method as in Example 1 under the conditions shown in Table 1. Comparative Examples 1 and 2 had insufficient performance. Comparative Example 3 had poor processability.

[Comparative Example 4] This example is an example of post-processing, and a three-stage smooth knitted fabric was produced using 150clr-40f false twisted yarn of polyethylene terephthalate. Viscosity f 12.00 (1 centistoke of dimethylpolysiloxane and a surfactant were added to make a water emulsion liquid, and a commercially available fiber treatment agent -ff of 1596 solution was added to a 3-stage smooth knitted fabric using the dip nip method. 2% by weight of the active ingredient. It was attached to the fiber surface so that

When the frictional melting resistance was measured, it was 25 seconds, but after washing 1
When measured again after 00 times, the time was less than 1 second, indicating that the durability was poor. It was also found that there were problems with color fastness as shown in Table 1.

[Comparative Example 5] This comparative example is an example regarding addition and dispersion of organic polysiloxane. A polycondensation reaction was carried out at 280° C. using the polycondensation reactor a in the same manner as in Example 1 to obtain a polyethylene terephthalate polymer containing 10 wt % of barium sulfate. After the completion of polymerization, it was put into the polycondensation reactor at 25℃ for 6 hours.
5% by weight of 0,000 centistoke dimethylpolysiloxane was added and then uniformly mixed using a stirring blade.

After that, the pellet was collected for about 40 minutes. The pellets were extruded using a 40φ extruder, and L/D2. The material was discharged and spun from an O round hole nozzle. Single fiber breakage occurred frequently during spinning, and the spinnability was poor.

When we investigated the state of dispersion of dimethylpolysiloxane in the fibers, we found that it was highly uneven, making it difficult to make an accurate determination. The measured values of frictional melting resistance also varied widely within the range of 10 to 40 seconds.

Margin below

[Brief explanation of the drawing]

Figure 1 shows the friction-proofing m! of the present invention. 411, scanning type Sumireko microscope after alkali reduction? ! 1. This is a mirror photo. The second figure is a transmission optical microscope photograph of the friction-fusible fiber of the present invention immediately after being discharged from the nozzle. Figure 3 is an example of the manufacturing process of the present invention, in which 1 is a melt extruder, 2.3 is a measuring machine, 4 is an additive feeder, 5 is a static mixer, and 6 is a spinneret bag. I will show you.

Claims (1)

[Claims] 1. 3% to 20% by weight of inert fine particles with an average particle size of 3μ or less
A polyester fiber containing an organic polysiloxane extending in the length direction of the fiber to form an independent phase in an apparent island state, in which the dispersion state of the organic polysiloxane is such that the dispersion state of the organic polysiloxane is As you can see, the outer layer is in the form of fine islands, and the inner layer is in the form of larger islands, and the islands are highly concentrated and dispersed around the outer periphery. A polyester fiber with excellent friction and melting resistance characterized by a structure in which connecting paths connecting islands in the direction are randomly present at a rate of 10% per a certain length of the fiber. The polyester fiber 3 according to claim 1, wherein the active fine particles are at least one selected from TiO_2, SiO_2, and barium sulfate, and the organic polysiloxane is dimethylpolysiloxane,
At least one selected from diphenylpolysiloxane and phenylmethylpolysiloxane, and has a viscosity of 1
0,000 centistokes or more, the polyester fiber 4 according to claim 1 or 2, characterized in that the polyester is polybutylene terephthalate or a polyester containing this as a main component. The polyester fiber 5 according to any one of claims 1 to 3, wherein the organic polysiloxane is present in an amount of 1.0 to 10% of the composition.
．． 0% by weight of the polyester fiber 6 according to any one of claims 1 to 3, an organic polysiloxane, is added to the molten fluid between the completion of polymerization of the polyester polymer and immediately before spinning, and then 1
Method 7 for producing polyester fibers with excellent frictional melting resistance, characterized in that the organic polysiloxane is dimethylpolysiloxane, which is characterized in that the organic polysiloxane is kneaded in layers using a static mixer with 5 or more elements, and then discharged from a nozzle hole to form fibers. ,
At least one selected from diphenylpolysiloxane and phenylmethylpolysiloxane, and has a viscosity of 1
8. Process for producing polyester fiber according to claim 6, characterized in that the fiber has a fiber density of 0,000 centistokes or more, and the amount of organic polysiloxane added is 1.0 to 10.
．． Claim 6 characterized in that the amount is 0% by weight.
Method for producing polyester fibers as described in Section 7 or Section 7