JPH0657535A - Polyester fiber excellent in antistatic performance and its production - Google Patents

Abstract

(57) [Abstract] [Purpose] A long-lasting antistatic polyester composite hollow and thin fiber with low frictional electrification voltage and long-lasting performance without post-processing deterioration. [Structure] A polyester containing 0.1 to 10% by weight of polyalkylene glycol having an average molecular weight of 1,000 or more and a polyester containing 95% by weight or more of polyethylene terephthalate are side-by-side type in the range of 20:80 to 80:20. And the hollow ratio is 5
It is 20%, the thick portions and the details are randomly present in the longitudinal direction of each fiber constituting the yarn and between each fiber, and the initial charged voltage V ₀ measured by the triboelectrification curve measurement method is 8 kV. In the following, a polyester composite hollow cross-section thin and fine fiber having an antistatic property having a charged voltage V ₃₀ after 30 seconds of 3 kV or less.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite hollow polyester thick and thin fiber excellent in antistatic performance and a method for producing the same.

[0002]

2. Description of the Related Art Polyester fibers are widely used not only for clothing but also for industrial materials because of their excellent characteristics, but they have a problem that they have high electric resistance and are easily charged with static electricity. In the field of clothing, this is a cause of discomfort, such as a discharge phenomenon at the time of desorption and clinging to the body, which is observed particularly in the dry season of winter. In order to ameliorate the defect that the polyester fiber is apt to be charged with static electricity, attempts have been made so far to add various antistatic agents to polyester or to copolymerize them. However, it is necessary to use a relatively large amount of an antistatic agent in order to impart a practical antistatic property to the polyester fiber, and as a result, there is a problem that spinning stability or thermal stability is deteriorated. It was

As means for solving these problems, Japanese Patent Publication Nos. 57-4724, 56-134211, and 3-206120 disclose that an antistatic agent is streaked in the fiber axis direction. A method of creating a fibrous structure that is continuous is disclosed. However, although these methods have relatively improved spinning stability, they are not satisfactory from the viewpoint of industrial stable production technology and antistatic performance. That is, it is difficult to control the kneading state in the kneading technique of the antistatic polymer and the ordinary polyethylene terephthalate by the static mixer,
There are many quality-related factors such as yarn-making stability and dyeing quality, and it is an immature industrial production technology. Moreover, it cannot be said that it has excellent antistatic performance because of its electrostatic chargeability and permanence.

[0004]

DISCLOSURE OF THE INVENTION The present invention overcomes the above-mentioned problems of the prior art, enables industrially stable production, and has excellent antistatic property and its durability, and is a hollow composite hollow polyester composite. To provide the fiber.

[0005]

The gist of the present invention is that 0.1 to 10% by weight of a polyalkylene glycol having an average molecular weight of 1,000 or more, and an organic compound represented by the following general formula (1) are used. 0 to 2% by weight of sulfonic acid metal salt
The main repeating unit contained is a polyester having an ethylene terephthalate unit and the polyester containing 95% by weight or more of polyethylene terephthalate is 20: 8.
A composite hollow fiber having a hollow ratio of 5 to 20%, which is laminated in a side-by-side type in the range of 0 to 80:20, and has a thick portion and a detailed portion in the longitudinal direction of each fiber constituting the yarn and between the fibers. Are present randomly, the initial charged voltage V ₀ measured by the triboelectric discharge curve measurement method is 8 kV or less, and the charged voltage V ₃₀ after 30 seconds is 3 kV or less, which is excellent in antistatic performance. Polyester composite hollow cross section in thick fiber. _{R-SO 3 M (1)} ( wherein R is an alkyl group having 3 to 30 carbon atoms, or 7 carbon atoms
To 40 aryl groups or alkylaryl groups, and M represents an alkali metal. )

A conventional antistatic polyester fiber yarn has a voltage of 6 when charged when a woven fabric using the fiber is rubbed.
While the excellent antistatic performance is that the attenuation rate D ₆₀ after 0 seconds is large and the half-life T _1/2 of the charged voltage is short, the composite hollow cross-section thick fiber of the present invention uses the fiber. Initializes band voltage V ₀ to be charged to be very low when the textile fabric frictionally was, and, as a charged voltage damping is characterized by frictional electrification voltage V ₃₀ after 30 seconds is low. The low initial charging voltage V ₀ means that static electricity is less likely to be charged, and the good charging voltage attenuating property (the charging voltage V ₃₀ after 30 seconds is low) makes it easy to discharge static electricity. Is shown. In order to have an anti-static performance that has not been available in the past, it is necessary that the initial charging voltage is 8 kV or less and the charged voltage after 30 seconds is 3 kV or less. In the range other than this, the polyester fiber having the excellent antistatic performance and its durability, which is the object of the present invention, cannot be obtained.

The fibers having such characteristics include 0.1 to 10% by weight of polyalkylene glycol having an average molecular weight of 1,000 or more, and an organic sulfonic acid metal salt represented by the following general formula (1). A polyester containing 0 to 2% by weight of ethylene terephthalate as a main repeating unit and a polyester containing 95% by weight or more of polyethylene terephthalate are from 20:80 to 80: 2.
A composite hollow cross-section thick and thin fiber having a hollow ratio of 5 to 20% bonded in a side-by-side type in the range of 0, and having a thick portion and details in the longitudinal direction of each fiber constituting the yarn and between each fiber. Can be obtained by being randomly present. _{R-SO 3 M (1)} ( wherein, R represents an alkyl group having 3 to 30 carbon atoms, or an aryl group or alkyl aryl group having a carbon number of 7 to 40, M
Indicates an alkali metal. )

In the present invention, the polyalkylene glycol compounded in the polyester has an average molecular weight of 1,00.
It should be 0 or more, preferably 5,000 or more. When the average molecular weight is less than 1,000, not only it is difficult to exert a sufficient antistatic effect, but also the durability of the antistatic effect becomes poor. As long as the average molecular weight of the polyalkylene glycol is 1,000 or more, it does not matter how high the molecular weight is.

Specific examples of the polyalkylene glycol include polyethylene glycol and, for example, a copolymer of ethylene oxide and propylene oxide. The amount of polyalkylene glycol to be blended is
It should be 0.1 to 10% by weight, preferably 0.2 to 5% by weight. When it is less than 0.1% by weight, the antistatic performance of the obtained fiber is not sufficient, and when it exceeds 10% by weight, not only the stability during melt spinning is lowered, but also the strength of the obtained fiber and the like are deteriorated. It is not preferable because the physical properties also deteriorate.

The polyalkylene glycol may be used alone, but for the purpose of improving the thermal stability, it is more preferable to add a known stabilizer, an antioxidant and the like in small amounts to use. Examples of the stabilizer to be added and compounded include hindered phenol compounds and thioether compounds. Each of these may be added alone, but it is preferable to add them simultaneously in order to further improve heat resistance. The addition amount of these is 2 to polyalkylene glycol.
It is preferably in the range of 10% by weight.

Further, in the present invention, in addition to polyalkylene glycol, the organic sulfonic acid metal salt represented by the above formula (1) is blended. Specific examples of the organic sulfonic acid metal salt include sodium or potassium salt of alkylsulfonic acid having 3 to 30 carbon atoms, lithium salt, or sodium or potassium salt of toluenesulfonic acid or dodecylbenzenesulfonic acid, lithium salt, Alternatively, a mixture thereof or the like can be used. The amount of the organic sulfonic acid metal salt to be blended with the polyester is 0 to 2% by weight, and it is not necessary to add the organic sulfonic acid metal salt, but in order to exert a superior antistatic effect, it is 2% by weight. It is preferable to add it within a range not exceeding%. If the blending amount exceeds 2% by weight, the stability during melt spinning and the physical properties such as the strength of the obtained fiber are deteriorated, which is not preferable.

The polyalkylene glycol and the organic sulfonic acid metal salt may be added to the polyester by any method at any stage until the shaping of the polyester is completed. That is, a method of adding and mixing into the reaction vessel before the polymerization reaction of the polyester is completed, a method of adding and mixing at a stage after the completion of the polymerization reaction and still in a molten state, a method of adding and mixing at the melt spinning stage, etc. Is mentioned. However, when compounding the polyalkylene glycol and the metal salt of an organic sulfonic acid into the polyester, a method in which the compound and the polyester are in a mixed state at a high temperature, that is, at a temperature equal to or higher than the melting start temperature of the polyester, is not preferable. .

On the other hand, as a polyester in which 95% or more of polyethylene terephthalate is laminated with the above modified polyester in a side-by-side type, it has a melt viscosity almost equal to that of the above modified polyester. When changing in the range of 20:80 to 80:20, it is of course possible to obtain a stable cross-sectional shape,
It is important to ensure the stability of yarn production. Here, if the ratio of the modified polyester in the composite yarn is 20% or more, the desired antistatic performance is obtained, but in order to obtain good yarn stability and antistatic performance, it is preferably 30% or more. 70%
The following is desirable.

The hollow cross-section thick thin fiber yarn of the present invention is a fiber in which thick portions and details are randomly present in the longitudinal direction of each fiber constituting the yarn and between each fiber, and obtained as described above. Composite ratio of the modified polyester and the polyester whose polyethylene terephthalate is 95% or more is 2
Using a spinneret having a hollow spinneret hole as shown in FIG. 1 in the range of 0:80 to 80:20, the hollow ratio is 5 to 20.
The unstretched yarn of the hollow cross-section fiber spun so as to have a ratio of 0.1% is stretched at a temperature equal to or lower than the crystallization temperature of the unstretched yarn and at a ratio such that the residual elongation after stretching is 70 to 90%, and It can be obtained by performing heat treatment at a temperature not lower than the glass transition temperature of the undrawn yarn and not higher than the crystallization temperature and at a tension ratio of 1.001 to 1.040 times.

In the present invention, as means for randomly presenting thick portions and details in the longitudinal (axial) direction of each fiber constituting the yarn and between each fiber, there is disclosed in JP-A-60-3941.
It can be easily achieved by the methods disclosed in JP-A No. 1 and JP-A-61-146836.

The hollow ratio of the fiber of the present invention is required to be 5 to 20%. If it is less than 5%, the desired antistatic property cannot be obtained. If the hollow ratio exceeds 20%, it is normal in the spinning stage. Not only a hollow cross section cannot be obtained, but also spinning stability is reduced.
The hollow cross-section thick and thin fibers thus obtained have a relatively small amount of antistatic agent and, in terms of the modified polyester component side, exhibit excellent antistatic performance in spite of being a homogeneous system. The term "antistatic performance" as used herein means that the conventional antistatic performance is an excellent antistatic performance in which the decay time of the voltage charged when a woven fabric using the fiber is rubbed is short. The hollow cross-section thick and thin fibers are characterized in that the voltage charged when rubbing a woven fabric using the fibers is extremely low, that is, the friction electrification voltage is very low.

The antistatic polyester fiber reported so far has its antistatic performance remarkably deteriorated by the alkali reduction processing which is the most common means for improving the texture of woven fabrics. Therefore, the weight reduction rate should be set to about 5%. It is known that there is no choice but to obtain a woven fabric that is aesthetically pleasing. On the other hand, in the woven fabric using the hollow cross-section thick and thin fibers of the present invention, even if the weight is reduced to about 20% in the alkali weight reduction processing, the antistatic performance is hardly deteriorated. This point is remarkable. It is unclear why the hollow cross-section thick and thin fibers of the present invention have such characteristics, but as will be seen in Examples and Comparative Examples described later, a composite of hollow cross-section yarns and thick fibers made by a special drawing technique. It is clear that the transformation is involved.

[0018]

EXAMPLES The present invention will be described more specifically below based on examples. The characteristic values in the examples and comparative examples are measured by the following methods. [Intrinsic Viscosity] It is a value measured by dissolving a sample in a phenol / tetrachloroethane (50/50 weight ratio) mixed solvent and measuring it with an Ubbelohde viscometer at 25 ° C.

[Antistatic Performance] The obtained yarn was woven under the following conditions, and then the antistatic performance was evaluated according to the method for measuring triboelectric discharge curve, which is a reference method of JIS L 1094 (1988). Warp: Polyethylene terephthalate yarn (50 denier / 18 filaments) Weft: Yarn obtained in Examples and Comparative Examples (100 denier / 30 filaments) Warp density: 40 yarns / cm Weft yarn density: 25 yarns / cm Device used Is a friction charging voltage measuring device EST-3 manufactured by Kanebo Engineering Co., Ltd.
It was carried out in a test room at 0 ± 1 ° C. and a relative humidity of 30 ± 2%. Washing of the sample, washing of the rubbing cloth with hot water, adjustment of the sample and the rubbing cloth, etc. were in accordance with JIS L1094 (1988). Bristles were used as the friction cloth. From each triboelectric discharge curve obtained by measuring 5 times for each sample, the electrification voltage V ₃₀ after 30 seconds, the attenuation rate D ₆₀ after 60 seconds, and the half-life T _1/2 were measured 5 times each. Obtained as an average value, this operation was further performed 5 times for each sample, and the final average value V _{30 of} the charged voltage after 30 seconds, the average value D ₆₀ of the attenuation rate after 60 seconds, and the average value of the half-life. T _1/2 was determined. The unit of the charged voltage is volt (V), and the sign is minus (-).

Example 1 3.0% by weight of polyethylene glycol having an average molecular weight of 20,000, sodium alkylsulfonate (average chain length of alkyl group C _{14 to} C ₁₅ ) of 0.1.
Polyethylene terephthalate having an intrinsic viscosity of 0.63 containing 5% by weight and titanium oxide of 0.5% by weight is used as the component A,
Polyethylene terephthalate containing 95% by weight or more of ethylene terephthalate was used as the component B, and the mixing ratio of both components was 1: 1 and the outer circumference was 3 mm and the slit width was 0.
Using a hollow spinneret with 30 1 mm spinning holes,
The spinning temperatures of the A component and the B component are 285 ° C. and 290, respectively.
Spinning was carried out at a temperature of 1800 m / min and a winding speed of 1,800 m / min to obtain an undrawn yarn having a hollowness of 15% and a fineness of 160 d.

The glass transition temperature of the undrawn yarn measured by the dilatometry method was 70 ° C., and the crystallization temperature measured by a scanning calorimeter was 128 ° C. The undrawn yarn is drawn at a draw ratio of 1.590 and a drawing temperature of 110 ° C., and then heat treated at a tension ratio of 1.015 and a processing temperature of 120 ° C. to 100
A denier / 30 filament composite hollow section thick fiber yarn was obtained. An enlarged sectional view of the obtained fiber is shown in FIG. The results of the antistatic performance evaluation after weaving this composite hollow cross-section thick and thin fiber yarn into a fabric are shown in Table 1, and the frictional charging and discharging curves are shown in FIG.
It is shown in (a).

[Examples 2, 3, 4] A woven fabric obtained by using the composite hollow cross-section thick and thin fiber yarn obtained in Example 1 was subjected to weight reduction processing with a 3% NaOH aqueous solution, and a weight loss rate of 5 was obtained. % (Example 2), 10% (Example 3), and 15% (Example 4), and the antistatic performance thereof is also shown in Table 1, and the friction-charged weight-reduced fibers of Example 3 are also electrified. Figure 3 (b) shows the discharge curve
It was shown to.

[Example 5] The same polymer and spinning apparatus as in Example 1 were used, except that the mixing ratio of the components A and B was 1: 2, under the same spinning conditions as in Example 1 and hollow. Rate 15
%, And a fineness of 150 denier was obtained. The undrawn yarn was drawn at a draw ratio of 1.500, a drawing temperature of 110 ° C., and then heat-treated at a tension ratio of 1.015 and a processing temperature of 120 ° C. to obtain a 100 denier / 30 filament composite hollow cross-section thick and thin fiber yarn. . The enlarged cross-sectional view of the obtained fiber is shown in FIG.
It is shown in (b). Table 1 shows the results of evaluation of antistatic performance after weaving this composite hollow cross-section thick and thin fiber yarn into a cloth.

[Comparative Examples 1 and 2] The two types of polymers used in Example 1 were used, and a composite flow having a polymer compounding ratio of 1: 1 was prepared, and then spinning having 30 circular spinneret holes having a hole diameter of 0.25 mm. Using a spinneret, spinning temperature 290 ° C, winding speed 1,
The yarn was spun at 800 m / min to obtain an undrawn yarn having a circular cross section of 160 denier / 30 filament. This undrawn yarn was drawn and tension heat treated under the same conditions as in Example 1,
A thin fiber yarn with a circular cross section was used, and weaving and alkali weight reduction were performed in the same manner as in Example 1, and the weight loss rate was 5% (Comparative Example 1).
A 10% (Comparative Example 2) woven fabric was prepared. The antistatic performance is shown in Table 1, and the triboelectric discharge curve of the weight-reduced processed fiber of Comparative Example 1 is shown in FIG. 4 (a).

[Comparative Example 3] Polyethylene glycol and polyethylene terephthalate were mixed by a kneading technique using a static mixer arranged in a spinning nozzle pack.
An antistatic fiber in which the antistatic agent forms a linear independent phase in the fiber axis direction (which is recognized in the market as having good antistatic properties) is woven in the same manner as in Example 1 to prepare a woven fabric. did. The antistatic performance is shown in Table 1 and the triboelectric discharge curve is shown in FIG. 4 (b).

[0026]

[Table 1]

As is clear from Table 1, the fibers obtained in the examples of the present invention were 30 or less with or without alkali weight loss.
The charged voltage V ₃₀ after a second is very low.

[0028]

INDUSTRIAL APPLICABILITY The polyester composite hollow thick and thin fiber of the present invention has an excellent antistatic effect in that no electrostatic spinning treatment by post-processing is required at all, although the antistatic agent is in a relatively small amount. At the same time, it is possible to industrially provide an antistatic polyester fiber having excellent durability, which does not reduce the antistatic effect even when subjected to weight reduction processing, washing treatment, and the like.

[Brief description of drawings]

FIG. 1 is a plan view showing a hole shape of a spinneret.

FIG. 2 is an enlarged sectional view of a fiber.

FIG. 3 is a triboelectrification discharge curve of the fibers of Examples 1 and 3.

FIG. 4 is a triboelectrification discharge curve of the fibers of Comparative Examples 1 and 3.

[Explanation of symbols] A A component B B component

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location D03D 15/00 A 7199-3B

Claims (2)

[Claims] 1. A polyalkylene glycol having an average molecular weight of 1,000 or more in an amount of 0.1 to 10% by weight, and an organic sulfonic acid metal salt represented by the following general formula (1) in an amount of 0 to 2:
Polyester containing ethylene terephthalate as the main repeating unit contained by weight% and polyester containing 95% by weight or more of polyethylene terephthalate are 2
A composite hollow fiber that is laminated in a side-by-side type in the range of 0:80 to 80:20 and has a hollow ratio of 5 to 20%, and has a thick portion in the longitudinal direction of each fiber constituting the yarn and between each fiber. The details are present at random, and the initial charged voltage V ₀ measured by the triboelectric discharge curve measurement method is 8
A polyester composite hollow cross-section thick fiber having excellent antistatic performance, which has a charged voltage V ₃₀ of 3 kV or less after 30 seconds at kV or less. _{R-SO 3 M (1)} ( wherein R is an alkyl group having 3 to 30 carbon atoms, or 7 carbon atoms
To 40 aryl groups or alkylaryl groups, and M represents an alkali metal. ) 2. A main repeating containing 0.1 to 10% by weight of a polyalkylene glycol having an average molecular weight of 1,000 or more, and 0 to 2% by weight of an organic sulfonic acid metal salt represented by the following general formula (1). By the composite spinning method, a polyester in which the unit is an ethylene terephthalate unit and a polyester containing 95% by weight or more of polyethylene terephthalate is used with a side-by-side type hollow cross-section composite spinneret at a ratio of 20:80 to 80:20. The unstretched yarn of the composite hollow cross-section fiber obtained by spinning so as to have a hollowness of 5 to 20% has a residual elongation of 70 to 70 at a temperature not higher than the crystallization temperature of the unstretched yarn. It is drawn at a draw ratio of 90%, then at a temperature not lower than the glass transition temperature of the unstretched yarn and not higher than the crystallization temperature, and 1.001 to 1.0.
A method for producing a polyester composite hollow cross-section fine fiber having excellent antistatic properties, which comprises heat treatment at a tension ratio of 40 times. _{R-SO 3 M (1)} ( wherein R is an alkyl group having 3 to 30 carbon atoms, or 7 carbon atoms
To 40 aryl groups or alkylaryl groups, and M represents an alkali metal. )