JPH06330409A - Antistatic polyester fiber - Google Patents

Abstract

PURPOSE:To obtain the fiber having excellent washing durability and process- passability by dispersing a non-randomly copolymerized polyoxyethylene-based polyether in an aromatic polyester matrix containing an organic metal salt in a specific dispersion state. CONSTITUTION:An aromatic polyester matrix is incorporated with (A) 0.5-2.0wt.% of a non-randomly copolymerized polyoxyethylene-based polyether having an average molecular weight of 5,000-16,000 and expressed by formula (Z is organic compound residue containing 1-6 active hydrogen atoms and having a molecular weight of <=300; R1 is >=6C alkylene, etc.; R2 is H, 1-40C univalent hydrocarbon group, etc.; (k) is integer of 1-6; (n) is integer to satisfy kXn>=70; (m) is integer of >=2) and (B) 0.1-1.0wt.% of an organic metal salt. The component A is dispersed in the form of a strings continuing in the fiber axis direction to form islands on the cross-section of the fiber. The island components satisfy the formula N50g/N10>=0.2 wherein N50 and N10 are number of the island components having diameter of >=50nm and >=10nm, respectively.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antistatic polyester fiber and a method for producing the same, and more specifically, it has a high degree of antistatic property with excellent washing durability, operational stability, and high alkali weight reduction processing. TECHNICAL FIELD The present invention relates to an antistatic polyester fiber excellent in quality stability and a novel production method thereof.

[0002]

Polyester is widely used as a synthetic fiber because of its many excellent properties. However, since polyester fibers are more hydrophobic than natural fibers such as wool and silk, fibrous fibers such as rayon and acetate, acrylic fibers, etc., static electricity easily occurs,
There are drawbacks such as dust adhesion and garment clinging due to static electricity.

In order to improve such drawbacks, as a method of imparting antistatic property to polyester fiber, for example, polyoxyalkylene glycol, polyoxyalkylene glycol / polyamide block copolymer or polyoxy which is substantially incompatible with polyester is used. A method in which a polyoxyalkylene compound such as an alkylene glycol / polyester block copolymer is mixed, and further, a method in which an organic or inorganic ionic compound is added thereto (for example, JP-B-39-5).
214, JP-B-44-31828, JP-B-60-11944, JP-A-53-80497, JP-A-60-39413 and the like) are known.

However, in order to obtain an antistatic fiber by melt-spinning in a conventional method by incorporating the above antistatic agent into polyester, there are the following problems. In order to obtain sufficient antistatic property, it is necessary to add a large amount of antistatic agent, but the more antistatic agent is, the more disadvantageous the original characteristics of polyester fiber are. Therefore, the amount of antistatic agent that can be contained in the polyester is at most about 3%. Water-soluble antistatic agents are easily removed by alkali reduction, dyeing process or washing, and have low antistatic durability. on the other hand,
Increasing the hydrophobicity of the antistatic agent reduces the antistatic property. There is a problem that a portion that has been subjected to pressure before weight reduction processing becomes fibrillated during weight reduction processing and appears white when dyed (hereinafter referred to as a pressure loss whitening phenomenon).

In order to improve such a drawback, Japanese Patent Publication No. 63-
No. 64532 discloses that the opening area of a single spinning hole is 0.2.
A method for increasing the streak dispersion of the polyether component by using a large-area spinning nozzle for producing solid fibers of mm ² or more is disclosed.

However, in this method, the apparent spinning draft (spinning take-up speed / discharge linear velocity from the spinneret) is extremely high, and since the polyether component does not agglomerate, the antistatic durability is lowered and the spinning speed is increased. In this case, there are problems that the spinning tone is deteriorated, unevenness of fineness and uneven dyeing occur, and the physical properties of the obtained fiber are deteriorated.

[0007]

DISCLOSURE OF THE INVENTION The present invention overcomes the problems of the above-mentioned prior art, has a high degree of washing durability, and has good process passability in high-order processing steps such as alkali reduction and dyeing. Therefore, it is an object of the present invention to provide an antistatic polyester fiber which can be stably spun for a long time even at a high spinning speed and is excellent in operation stability and quality stability.

[0008]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that when spin-melting a polyester containing a non-random copolymerization type polyoxyethylene-based polyether, the spinneret temperature is When controlling the fiber deformation right under the mouthpiece and making the polyether into a proper dispersion form, it is possible to obtain a polyester fiber having sufficient antistatic property and excellent durability even with a small amount of antistatic agent. Investigated.

Thus, according to the present invention, with respect to the polyester matrix, (a) a non-random copolymerization type polyoxyethylene type polyoxyethylene type polyoxyethylene type polyoxyethylene type polyoxyethylene type polymer represented by the following general formula (I) and having an average molecular weight of 5,000 to 16,000. 0.5 ether
To 2.0% by weight, and (b) the organometallic salt is 0.1 to
1.0% by weight of an aromatic polyester fiber, wherein (a) is independent in any fiber cross-section while having a continuous linear form in the fiber axis direction of the aromatic polyester fiber. It is dispersed as an island component, and the size of the largest island component is 70 to 300 nm and 5
Number of island components N ₅₀ and 10 n having a size of 0 nm or more
Ratio N ₅₀ / of the number of island components having a size of m or more and N _10.
Provided is an antistatic polyester fiber characterized by having N ₁₀ of 0.2 or more.

[0010]

[Chemical 2]

(Wherein Z is an organic compound residue having 1 to 6 active hydrogens and having a molecular weight of 300 or less, R ₁ is an unsubstituted or substituted alkylene group having 6 or more carbon atoms, R ₂ is a hydrogen atom or carbon) A monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent acyl group having 2 to 40 carbon atoms, k is an integer of 1 to 6, and n is k
X represents an integer of 70 or more and m represents an integer of 2 or more)

The constituent features of the present invention will be described in detail below. The polyester used in the present invention is an aromatic polyester having an aromatic ring in a polymer chain unit, and is obtained by reacting a difunctional aromatic carboxylic acid or its ester-forming derivative with a diol or its ester-forming derivative. Is a polymer.

Examples of the bifunctional aromatic carboxylic acid used herein include terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid, with terephthalic acid being particularly preferred. These difunctional aromatic carboxylic acids have 2
You may use together 1 or more types. It should be noted that 5-sodium sulfoisophthalic acid or the like can be used alone or in combination of two or more kinds together with these bifunctional aromatic carboxylic acids as long as the amount is small.

As the diol, preferred are aliphatic glycols such as ethylene glycol and butylene glycol, alicyclic glycols, aromatic diols and mixtures thereof. Also, if the amount is small, polyoxyalkylene glycol having both ends or one end unblocked can be copolymerized with these glycols.

Examples of preferable aromatic polyesters include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and copolymerized polyesters such as polyethylene isophthalate / terephthalate. Among them, polyethylene terephthalate and polybutylene terephthalate, which have well-balanced mechanical properties and moldability, are particularly preferable.

The aromatic polyester can be synthesized by any method. For example, polyethylene terephthalate can be described by directly reacting terephthalic acid with ethylene glycol, transesterifying a lower alkyl ester of terephthalic acid such as dimethyl terephthalate with ethylene glycol, or reacting terephthalic acid with ethylene oxide. In other words, the first step of producing a glycol ester of terephthalic acid and / or its low polymer, and then the second step of heating the product under reduced pressure to carry out a polycondensation reaction until a desired degree of polymerization is obtained. It is easily produced by the reaction.

The polyester may contain other thermoplastic polymers such as polyamides such as nylon 6 and polyolefins such as polyethylene and polystyrene as long as the original physical properties of the polyester are not impaired.

In the present invention, the above-mentioned aromatic polyester contains the non-random copolymer type polyoxyethylene-based polyether represented by the general formula (I) and an organic metal salt.

In such a non-random copolymer type polyoxyethylene-based polyether, a polyoxyethylene block composed of (CH ₂ CH ₂ O) constitutes the main chain, and at least one molecular chain terminal of the polyoxyethylene has at least one group. It is necessary that the oxyalkylene units (R ₁ O) form blocks and have a localized arrangement.

The polyether having the molecular ends blocked by the above sequence is insoluble in water and exhibits excellent durability against alkali weight loss, dyeing or washing.

On the other hand, a polyether in which polyoxyethylene and oxyalkylene units are randomly arranged cannot achieve the object of the present invention.

The non-random copolymer type polyoxyethylene-based polyether has a molecular weight of 5,000 to 16,000.
It is necessary to be 0, preferably 5,500 to 14,000. When the molecular weight is less than 5,000, it is difficult for the polyether to form a streaky dispersion form having a sufficient length in the polyester fiber, and when it exceeds 16,000, the melt miscibility in the polyester is deteriorated. As a result, the dispersion becomes non-uniform, melt spinning becomes difficult, and the physical properties and antistatic properties of the obtained fiber become poor.

The content of the non-random copolymer type polyoxyethylene-based polyether is 0.5 to 2.0% by weight, preferably 1.0 to 2.0, based on the aromatic polyester.
% By weight. If the amount is less than 0.5% by weight, sufficient antistatic property cannot be obtained. On the other hand, if the amount exceeds 2.0% by weight, the antistatic property is improved, but mechanical properties and light resistance of the obtained polyester fiber are not improved. The characteristics are impaired, and when the alkali is reduced, the pressure reduction and the whitening reduction are remarkable.

In the present invention, an organometallic salt is blended in combination with the non-random copolymer type polyoxyethylene-based polyether.

The organic metal salt preferably used is
Alkali metal salt of sulfonic acid formed from sulfonic acid such as dodecylbenzene sulfonic acid and tridecylbenzene sulfonic acid and alkali metal such as sodium, potassium and lithium, and alkali metal of phosphoric acid ester such as distearyl sodium phosphate Examples thereof include salts and alkali metal salts of other organic carboxylic acids.

Preferable examples of the sulfonic acid metal salt represented by the following general formula (A) include sodium dodecylbenzene sulfonate, a mixture of sodium alkyl sulfonates having an average number of carbon atoms of 14,
Alternatively, a metal salt of sulfonic acid represented by the following formulas (B) and (C) is preferable.

[0027]

[Chemical 3]

(In the formula, R'is a monovalent hydrocarbon group, R "is an alkylene group having 2 to 4 carbon atoms, a is an integer of 1 to 100, b is an integer of 2 to 4, M is Na, (Indicates alkali metals such as K and Li.)

[0029]

[Chemical 4]

[0030]

[Chemical 5]

These organic metal salts may be used alone or in combination of two or more.

The amount of the organic metal salt compounded is preferably 0.1 to 1% by weight, based on the aromatic polyester, and 0.2 to 0.7.
Weight percent is particularly preferred. If the amount is less than 0.1% by weight, sufficient antistatic property cannot be obtained. On the other hand, if the amount is more than 1.0% by weight, the antistatic property is no longer improved, and the mechanical properties and light resistance of the polyester fiber obtained on the contrary are improved. The properties such as properties are impaired, and when the alkali is reduced, the pressure reduction and the whitening reduction become remarkable.

The aromatic polyester containing the above antistatic agent may be further blended with a hindered phenol-based, sulfide-based or phosphite-based antioxidant and a benzophenone-based or benzotriazole-based UV absorber. it can. For example, when an antioxidant is added, it is possible to suppress a decrease in antistatic property due to thermal decomposition of the polyoxyethylene-based polyether due to retention in the melt spinning process.

It is preferable to mix these antioxidants and ultraviolet absorbers with the polyoxyethylene-based polyether in advance, since the above effects can be enhanced. In addition, the said antioxidant may be used individually by 1 type or may be used in mixture of 2 or more types, and compounding quantity is 0.02-3.
0% by weight is preferred.

The polyester containing the above antistatic agent includes
In addition, if necessary, flame retardants, optical brighteners, matting agents such as titanium oxide, colorants, colloidal silica, dry process silica, colloidal alumina, fine particulate alumina, inert fine particles such as calcium carbonate, calcium phosphate, etc. The additives may be added separately or premixed at any stage from the start of polyester synthesis to the spinning process.

The intrinsic viscosity [η] of the aromatic polyester is preferably 0.55 or more. [Η] is 0.55
If it is less than 1, the elongational viscosity after exiting the spinneret is too small, so that it becomes practically difficult to set the draft ratio D, which will be described later, to 4 or more.

If [η] is less than 0.55, crystallization is likely to occur due to heat, and the toughness tends to be poor, resulting in brittleness, resulting in insufficient wear resistance.

In the antistatic polyester of the present invention, the above-mentioned polyoxyethylene-based polyether and organometallic salt, and if necessary, an antioxidant and the like are added at any time from the start of polyester synthesis to the spinning step. Polyester can be produced by melt spinning using, for example, a spinning device as shown in FIG.

That is, the spun yarn 2 discharged from the spinneret 1 passes through a lower spinneret keeping zone 4 installed between the heat insulating plate 3 and the spinneret 1, and the cooling air from the cooling spinning tube 5 is cooled. After being cooled and solidified by the oil applying device 6 and the oil agent is applied by the oil applying device 6, the oil is applied by the winding device 8 via the take-up roller 7.

The polyester fibers thus obtained are non-woven
Copolymerized polyoxyethylene-based polyether is
Although it has a continuous streak form in the fiber axis direction of the steal fiber
Dispersed as an independent island component in any fiber cross section
And the size of the largest island component is 70
~ 300 nm and island component having a size of 50 nm or more
Number of N₅₀And an island component with a size of 10 nm or more
Number N_TenRatio N₅₀/ N _TenMust be 0.2 or more
Is.

Here, the fact that the polyether has a continuous striated form in the fiber axis direction of the polyester fiber means that the side surface of the fiber obtained by reducing the polyester fiber by 20% is observed by a scanning electron microscope. It means a state where the streak-like grooves are continuous without interruption in the fiber axis direction, and may include a form in which a part of the adjoining streak-like grooves are overlapped and continuous.

The term "dispersed as an independent island component in an arbitrary fiber cross section" means that the polyether component is randomly dispersed in the fiber while having a length in the fiber axis direction. The state in which the dispersion can be identified as an island component when viewed from an arbitrary fiber cross section.

The size of the island component is a value expressed by the diameter of the circumscribing circle when the island is substantially circular or polygonal, and by the length of its major axis when it is substantially elliptical. When the size of the largest island component is less than 70 nm, the antistatic property becomes insufficient, while when it exceeds 300 nm, the antistatic property is good, but the whiteness and light resistance of the fiber deteriorate, and the whiteness of the pressure reduction whitens. The decrease becomes remarkable. The size of the largest island component is 100-2
00 nm is preferable.

Further, the ratio N ₅₀ / N ₁₀ between the number N _{50 of} island components having a size of ₅₀ nm or more and the number N _{10 of} island components having a size of 10 nm or more is less than 0.2, that is, 50n.
When the number of island components having a size of m or more is small, the amount of alkali metal loss and the loss of organometallic salts during the dyeing and washing steps are large, so that the antistatic durability deteriorates.

Particularly, in the dyeing step, 5 of the organic metal salt is used.
Since 0% or more may drop out, N ₅₀ / N _{10 is set} to 0.
It is good to set it to 2 or more, preferably 0.3 or more.

The above-mentioned polyester fiber can be obtained by carrying out melt spinning under the condition that the draft ratio D defined by the following formula is 4 or more.

D = V ₅ / V ₂₀ (where V ₅ is the linear velocity of the spun yarn when the surface temperature of the spun yarn is + 5 ° C., and V ₂₀ is the surface temperature of the spun yarn). Represents the linear velocity of the spun yarn at the melting point + 20 ° C.
The melting point mentioned here is a melting peak temperature when the polymer is measured by a differential scanning calorimeter. ) Above draft rate D
Is a linear velocity ratio obtained in a specific temperature range in which the surface temperature of the spun yarn is near the melting point, unlike the normal apparent spinning draft (spinning take-off speed / discharge linear velocity from the spinneret).

It has been conventionally known that the draft in spinning contributes to the continuity of the polyether component in the fiber axis direction, and the above-mentioned JP-B-63-64532 is one example.

However, according to this method, the draft in the temperature range of the melting point + 20 ° C. to the melting point + 30 ° C. of the spun yarn increases, and the number of island components having a size of 50 nm or more becomes extremely small. Electric durability is reduced.

On the other hand, the present inventors have found that it is extremely effective to make the draft rate D given above a certain value in the temperature range of the melting point + 5 ° C. to the melting point + 20 ° C. for the surface temperature of the spun yarn. I found it. That is, the antistatic property is improved by increasing the elongation deformation from the nozzle of the spun yarn to the solidification point, and the antistatic durability is improved by increasing the elongation deformation near the solidification point.

In order to set the draft ratio D to 4 or more, depending on the fineness of the spun yarn and the spinning speed, the opening area A of the single hole of the spinning nozzle, the spinneret temperature T _S , and the heat-retaining zone 4 installed immediately below the spinneret. This can be achieved by appropriately changing the atmospheric temperature gradient and length, and the temperature, wind speed, and blowing length of the cooling air from the cooling spinning tube 5.

It is particularly preferable that the temperature of the spinneret is lowered by adopting such a condition that the solidification point of the spun yarn is inside the heat retaining zone 4 installed just below the spinneret. Longer to increase the heat retention temperature in the upper part of the heat retention zone, reduce the opening area of the spinning nozzle single hole, decrease the polymer discharge amount per spinning nozzle single hole, or lower the cooling air temperature directly below the heat retention zone. And so on.

The spinneret temperature T _S is preferably lower than the melting point + 30 ° C. That is, since the spinnability lower limit spinneret temperature of the polyester polymer containing the polyoxyethylene-based polyether is the melting point + 15 ° C, in the present invention, it is preferable to spin at a low temperature as close as possible to the spinnable minimum spinneret temperature.

As the spinneret temperature T _S is lower, the polyether component is more likely to coagulate in the polyester fiber, and the draft effect near the solidification point is large, so that the size of the largest island component is 100 nm or more. can get.

However, the spinneret temperature T _{S is set} to the melting point + 15 ° C.
If you lower it too much, the size of the largest island component will be 30.
In addition to large island components of 0 nm or more being scattered, the molten polymer becomes highly viscous and highly elastic, so that sudden deformation due to elongation stress near the spinneret, or in extreme cases, inside the discharge hole. As a result, the polymer flow in the spinneret becomes turbulent and becomes weak yarn, or brittle fracture occurs and spinning becomes impossible.

On the other hand, when the spinneret temperature T _S exceeds the melting point + 30 ° C., the largest island component becomes scattered with small island components having a size of less than 50 nm, and the antistatic durability deteriorates. It is considered that such a change in the dispersed state is caused by the magnitude of the difference in the interfacial energy between the molten polyester and the polyether component.

Specific spinning conditions include, for example, a target stretched yarn having a single fiber fineness of 2.75 denier,
When spinning at a single hole diameter of the spinning nozzle of 0.5φ, a spinning temperature of 280 ° C., and a spinning speed of 3000 m / min (spinning apparent draft 460), in order to set the draft ratio D to 4 or more, the length of the zone under the spinneret is 15 to 25 cm. Then, the atmosphere temperature at 5 cm below the base is 150 to 250 ° C., and the lower part is 10 to 20 ° C.
cm may be gradually cooled and then cooled in a cooling spinning tube having a cooling air temperature of 20 ° C. and a wind speed of 20 cm / sec.

The temperature of the heat-retaining zone just below the spinneret is controlled in order to control the molecular orientation of the discharged yarn and obtain a stable quality, so that it is possible to obtain a stable quality. It is preferable to strictly control by the method described in JP-A-56-140116.

The temperature, the wind speed and the blowing length of the cooling air in the cooling spinning tube are not particularly limited as long as the spinning yarn can be sufficiently cooled, but the surface temperature of the spinning yarn is less than the melting point. After that, it is preferable to efficiently cool with low-temperature cooling air.
Further, when the spun yarn has a small fineness, it is preferable to shorten the blowing length in order to reduce the tension of the yarn.

The fineness of the spun yarn is not particularly limited, but usually about 0.1 de to several de is suitable. The spinning speed is not particularly limited, and the spinning and the false twisting may be performed subsequent to the spinning. For example, a method of melt spinning at a speed of 500 to 2500 m / min, stretching and heat treatment, 1500 to
A method in which melt spinning is performed at a speed of 5000 m / min and drawing or false twisting is performed simultaneously or subsequently, melt spinning at a high speed of 5000 m / min or more, and a method in which the drawing step is omitted may be adopted.

The cross-sectional shape of the antistatic polyester fiber of the present invention can be any shape depending on the use of the woven or knitted product to be obtained. In addition to circular shape, triangular shape, flat shape, star shape, V
Atypical cross sections such as shapes or hollow cross sections thereof can be exemplified.

The obtained fiber or the woven or knitted fabric produced from this fiber may be subjected to an appropriate post-hydrophilization treatment. As the post-hydrophilization treatment, for example, a method of treating with an aqueous dispersion of a polyether ester block copolymer composed of terephthalic acid and / or isophthalic acid or a lower alkyl ester thereof and a lower alkylene glycol and a polyalkylene glycol, or acrylic A method in which a hydrophilic monomer such as acid or methacrylic acid is graft-polymerized and then this is sodium chloride is preferably employed.

[0063]

In the conventional melt spinning of polyester fibers, the condition that the draft ratio D defined in the present invention is smaller than 4 is adopted. Under such spinning conditions, the polyester polymer containing the polyoxyethylene-based polyether is controlled. In order to manufacture the electro-conductive fiber, it was necessary to incorporate the polyether in a large amount.

In the present invention, when the draft ratio D in the vicinity of the solidification point is 4 or more during melt spinning, the organometallic salt, which is one component of the antistatic agent, can be prevented from falling off, and a small amount of polyoxyethylene-based poly Sufficient antistatic property and antistatic durability can be obtained only by containing ether.

Although the details of the reason why the above-mentioned effect is exhibited are unknown, generally, in the ordinary spinneret, the shear deformation received in the process of passing through the discharge hole works in the direction of relaxation at the time of leaving the discharge hole, Subsequently, it is deformed by elongation stress and is thinned.

According to the study by the present inventors, the influence of the shear deformation in the discharge hole on the development of antistatic property and the influence of the shear deformation inside the discharge hole,
It was found that the influence of the deformation due to the elongation stress at the position where the surface temperature of the yarn is below the melting point is small.

Therefore, when spinning is performed under the condition that the deformation near the melting point of the polyester polymer is within a specific range, the elongation flow of the spun yarn at the position where the elongation stress is small from the nozzle to the solidification point, and the polyether component It is considered that the phase separation results in a dispersion form that enhances the retention of the organometallic salt and improves the antistatic property and antistatic durability.

[0068]

EXAMPLES The present invention will be described in more detail below with reference to examples. The parts and% in the comparative examples are parts by weight and% by weight, respectively.

The surface temperature of the spun yarn and the draft ratio D
The frictional electrification voltage, visual infection color resistance, fibril resistance and pressure loss whitening resistance, and the dispersion state of the polyoxyethylene-based polyether of the obtained fabric composed of the antistatic polyester fiber were measured by the following methods.

(1) Surface temperature of spun yarn Infrared radiation thermometer (detection element InSb, measurement minimum yarn diameter 20
μm, measurement range 100 to 300 ° C., accuracy ± 3 ° C., response speed 2 to 10 ms), and the non-contact measurement was performed by changing the distance under the spinneret. When converting the output value corrected using the fiber diameter obtained by the outer diameter measuring device into the yarn temperature, the emissivity of the yarn was calculated as 0.67 (Fujimoto et al., Journal of the Textile Society, No. 44). Vol. 2, p. 53 (1988)).

(2) Draft rate D Zimmer external diameter measuring instrument (model 460A /
5, measuring beam width 5mm, height 10mm), fixed at the position where the yarn surface temperature is melting point + 5 ° C and melting point + 20 ° C, 60 data are sampled, and the most frequent fiber diameter is measured at each measurement point. And the fiber diameter. The linear velocity V ₅ of the spun yarn when the surface temperature becomes + 5 ° C. from the fiber diameter.
(M / min) and the linear velocity V ₂₀ (m / min) of the spun yarn when the surface temperature became the melting point + 20 ° C., and the draft ratio D was calculated by the following formula. D = V ₅ / V ₂₀

(3) Friction electrification voltage Dyed fabric (designated as L ₀ ) and JIS L-101
8-77 6.36 According to the H method, the dyed woven fabric washed for 50 times equivalent to washing (referred to as L ₅₀ ) was washed with 40 ± 2% RH.
In a desiccator of 1 day or more as a test piece, which was conditioned to a humidity of 40 ± 2% RH, using a rotary static tester, JISL-109
Friction electrification voltage was measured according to the 48.2 B method. If the frictional charge voltage is 1.5 kV or less, the antistatic effect is judged to be sufficient.

(4) Visual infection color The tubular knitted fabric was scoured and preset (180 ° C x 1
Min) was obtained knitted fabric A _0, and the knitted fabric A ₀ with aqueous sodium hydroxide solution of 30 g / l, ed in which the caustic rate (referred to as N ratio) of 20% and caustic at the boiling temperature Place B ₀ in Sumikalon Navy Blue
S-2GL (Sumitomo Chemical) 4% owf, Disper VG
(Myosei Chemical Industry Co., Ltd.) 0.5 g / l and acetic acid 0.3 g /
After dyeing in a dyeing bath containing 1 at a bath ratio of 1:50 at 130 ° C. for 60 minutes, it is reduced and washed with an aqueous solution containing 1 g / l of sodium hydroxide and 1 g / l of hydrosulfite for 20 minutes at 70 ° C. Final set (160
C. × 1 minute) to give a dyed knitted fabric A (N ratio 0%) and a weight-reduced dyed knitted fabric B (N ratio 20%). L * value (brightness index) of each dyed knitted fabric is Macbeth Color Eye MS-
2020 (Instrumental Color S
Yeast Limited). L
* The smaller the value, the higher the visual density and the more excellent the visual infection color.

(5) Fibril resistance Using a Gakushin type flat wearer for friction fastness test, a Georgette made of 100% polyethylene terephthalate was used as a friction cloth, and the weight-reduced dyed knitted fabric was loaded under a load of 500 g. After the surface was abraded 200 times, the degree of occurrence of discoloration was judged with a gray scale for discoloration. When the abrasion resistance (fibril resistance) was extremely low, it was classified as grade 1, and when it was extremely high, it was classified as grade 5. Practical level 4 or higher is required.

(6) Whitening resistance to pressure loss resistance A knitted fabric A ₀ obtained by scouring and presetting a tubular knitted fabric by a conventional method.
Was passed between calender rolls to which a linear pressure of 20 kg / cm ² was applied, and then a weight-reduced dyed fabric C having an N ratio of 20% was obtained by the same method as described above. The lightness index L * value of the weight-reduced dyed fabric B and the weight-reduced dyed fabric C was calculated using the Macbeth Color Eye M
The difference ΔL * between the L * values of the two measured with S-2020
The degree of pressure reduction whitening resistance was determined by. ΔL * = L * (knitted fabric C) -L * (knitted fabric B) The smaller the ΔL * value, the more excellent the pressure resistance whitening resistance. Practically, it should be 3.0 or less.

(7) Dispersion state of polyoxyethylene-based polyether component The continuity of streak grooves was evaluated according to the criteria shown in Table 1 by observing the side faces of the fibers of the weight-reduced dyed fabric B with a scanning electron microscope. .

[0077]

[Table 1]

The size of the largest island component and 5
Number of island components N ₅₀ and 10 n having a size of 0 nm or more
Ratio N ₅₀ / of the number of island components having a size of m or more and N _10.
N ₁₀ was obtained by dyeing the fibers of the weight-loss dyed knitted fabric B with a 1% osmium tetroxide solution for 10 days and then embedding it in an epoxy resin.
The section cut to a thickness of μm was further stained with osmium tetroxide vapor for 1 hour, and then the transmission electron microscope (Hitachi TEM).
H-800, acceleration voltage 75 kV) and magnification of 2000
It was determined by observing a photograph taken at 0 times and further enlarged at 2 times. The size of the island component is represented by the diameter of the circumscribing circle when the island is substantially circular or polygonal, and the length of the major axis when the island is substantially elliptical. The above measurement was performed on a cross section containing at least 200 island components.

[0079]

Example 1 100 parts of dimethyl terephthalate, 60 parts of ethylene glycol, 0.06 part of calcium acetate monohydrate (0.066 mol% with respect to dimethyl terephthalate) and cobalt acetate tetrahydrate as a color-matching agent. 009 parts (0.007 mol% with respect to dimethyl terephthalate) were charged into a transesterification can, and the mixture was added to a transesterification can for 14 hours under a nitrogen gas atmosphere to give 14
The ester exchange reaction was carried out while the temperature was raised from 0 ° C to 220 ° C and the produced methanol was distilled out of the system.

After the transesterification reaction, trimethyl phosphate O. 58 parts of O (0.080 mol% relative to dimethyl terephthalate) and 0.024 part of dimethylpolysiloxane as a defoaming agent were added. Then, 10 minutes later, 0.04 part of antimony trioxide (0.027 mol% with respect to dimethyl terephthalate) was added, and at the same time, the temperature was raised to 240 ° C. while driving out excess ethylene glycol, and then transferred to a polymerization vessel. did.

Next, the pressure was reduced from 760 mmHg to 1 mmHg over 1 hour, and at the same time 24 hours over 1 hour 30 minutes.
The temperature was raised from 0 ° C to 280 ° C.

Two hours after the start of depressurization, it is represented by the following formula:
1.4 parts by weight of a water-insoluble polyoxyethylene-based polyether having an average molecular weight of 7106 was added in a molten state, and 0.5 parts by weight of sodium dodecylbenzenesulfonate was added as a 50% ethylene glycol solution under reduced pressure.

[0083]

[Chemical 6]

(However, j is an integer of 18 to 28 and has an average value of 21, p is an average value of 115, and m is an average value of 3.) Subsequently, polymerization was continued for 1 hour under reduced pressure of 1 mmHg or less with stirring. At that time, Sianox 1790 (manufactured by American Cyanamid) as an antioxidant was used.
15 parts and 0.15 part of Mark AO-412S (manufactured by Adeka Argus Chemical Co., Ltd.) were added under reduced pressure, and then 2 more parts were added.
Polymerization was carried out for 0 minutes, and the obtained polymer was made into chips by a conventional method.

The intrinsic viscosity of the obtained polyester is 0.6.
4, the melting point obtained from the melting peak temperature of the differential thermal measurement is 25
It was 5 ° C.

The obtained aromatic polyester was dried by a conventional method, melted at a melting temperature of 295 ° C. by a screw type extruder, and then fed to a spinning head via a gear pump. The molten polymer is discharged from a spinneret equipped with a circular spinning hole, passed through a heat-retaining zone installed directly below the spinneret, and below it, a cooling air with a temperature of 20 ° C and a wind speed of 0.2 m / sec is blown to cool it sideways. After applying the oil agent, the elongation is 38%
A drawn yarn was obtained by winding it through a 90 ° C. heated goded roller and a 130 ° C. drawn heating roller at a draw ratio such that

Spinneret Nozzle Nozzle opening area, discharge amount per single hole, spinneret temperature, spinning speed, atmosphere temperature and length of a heat-retaining zone installed immediately below the spinneret, and spinning results are shown in Table 2. Experiments N0.1 to 20 are shown.

[0088]

[Table 2]

The drawn yarn thus obtained was made into a tubular knitted fabric and a woven fabric by a conventional method, and friction electrification voltage, visual infection color resistance, fibril resistance and pressure loss whitening resistance, and dispersion state of polyoxyethylene-based polyether were evaluated. did. The results are shown in Table 3.

[0090]

[Table 3]

[0091]

Comparative Example 1 In Experiment No. 9 of Example 1, the amount of water-insoluble polyoxyethylene-based polyether added was 2.0 parts by weight and the amount of sodium dodecylbenzenesulfonate added was 0.8 parts by weight. Except for this, the experiment was performed in the same manner as Experiment No. The results are shown in Experiment No. 21 of Tables 2 and 3.

[0092]

[Comparative Example 2] Experiment No. 9 except that water-soluble polyoxyethylene glycol having an average molecular weight of 20,000 was used in place of the water-insoluble polyoxyethylene-based polyether in Experiment No. 9 of Example 1. It carried out similarly. The results are shown in Experiment No. 22 of Tables 2 and 3.

[0093]

[Comparative Example 3] In Experiment No. 9 of Example 1, except that a water-insoluble polyoxyethylene-based polyether represented by the following formula and having an average molecular weight of 17306 was used instead of the water-insoluble polyoxyethylene-based polyether. It carried out like Experiment No. 9. The results are shown in Experiment No. 23 of Tables 2 and 3.

[0094]

[Chemical 7]

(However, j is an integer of 18 to 28 and has an average value of 21, p is an average value of 115, and m is an average value of 3.)

[0096]

EFFECTS OF THE INVENTION According to the present invention, an excellent antistatic property having sufficient antistatic property even with an extremely small amount of antistatic agent, and having such antistatic property not lost even by alkali reduction or washing. In addition to having durability, the spinning process condition can be maintained stably for a long period of time even at high spinning speeds, and antistatic polyester fibers with excellent operation stability and quality stability can be obtained. Therefore, it can be widely used not only for dust-free clothing but also for outerwear.

[Brief description of drawings]

FIG. 1 is a side view showing an example of a melt spinning apparatus used in the present invention.

[Explanation of symbols] 1 spinneret 2 spun yarn 3 heat insulating plate 4 heat retaining zone under spinneret 5 cooling spinning tube 6 oil applying device 7 take-up roller 8 winding device

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Higashi Yoshi Suzuki 77 Kitayoshida-cho, Matsuyama-shi, Ehime Prefecture Teijin Limited Matsuyama Office

Claims (3)

[Claims] 1. A non-random copolymerized polyoxyethylene-based polyether represented by the following general formula (I) having an average molecular weight of 5,000 to 16,000 relative to an aromatic polyester matrix: 0.5-2.0% by weight,
And (b) a polyester fiber containing 0.1 to 1.0% by weight of an organic metal salt, wherein (a) has a continuous striated form in the fiber axis direction of the aromatic polyester fiber. However, the number of island components N ₅₀ and 10 nm, which are dispersed as independent island components in an arbitrary fiber cross section, and in which the largest island component has a size of 70 to 300 nm and a size of 50 nm or more. A ratio N ₅₀ / N ₁₀ to the number N _{10 of} island components having the above size is 0.2 or more, and an antistatic polyester fiber. [Chemical 1] (In the formula, Z is a molecular weight of 300 having 1 to 6 active hydrogens.
The following organic compound residue, R ₁ is an unsubstituted or substituted alkylene group having 6 or more carbon atoms, R ₂ is a hydrogen atom, 1 carbon atom
To 40 monovalent hydrocarbons or C2 to C40 monovalent acyl groups, k is an integer of 1 to 6, n is an integer of k × n of 70 or more, and m is an integer of 2 or more. ) 2. The antistatic polyester fiber according to claim 1, wherein the aromatic polyester fiber is an aromatic polyester fiber melt-spun under the condition that the draft ratio D defined by the following formula is 4 or more during melt spinning. fiber. D = V ₅ / V ₂₀ (where V ₅ is the linear velocity of the spun yarn when the surface temperature of the spun yarn is + 5 ° C., V ₂₀ is the surface temperature of the spun yarn + melting point + 20 ° C. Represents the linear velocity of the spun yarn at 3. The size of the largest island component is 100 to 2
The number N _{50 of} island components having a size of 00 nm and 50 nm or more and the number N _{50 of} island components having a size of 10 nm or more
_The antistatic polyester fiber according to claim 1 or 2, wherein the ratio N ₅₀ / N ₁₀ with respect to ₁₀ is 0.3 or more.