JPH11279837A - Antistatic polyester fiber and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the antistatic polyester fibers having a durable antistatic property and an excellent dyed grade, having good processability on sophisticated after-treatment process and further having excellent operation stability and quality stability by compounding a specified amount of a highly hydrophilic polymer as an antistatic agent and satisfying specified raw fiber physical properties. SOLUTION: The subject polyester fibers contain 0.2-5 wt.%, preferably 0.3-5 wt.%, of a highly hydrophilic polymer as an antistatic agent, and simultaneously satisfy raw fiber physical properties comprising a specific resistance (R) of the inequality: 10×10<8> <=R<=1,000×10<8> Ω.cm, and a single fiber fineness CV(coefficient of variation) % (X) of the inequality: X<=5.0. The antistatic agent is preferably a polyetherester amide-based antistatic agent comprising 100 pts.wt. of a polyetherester amide and 2-20 pts.wt. of a metal sulfonate compound. The polyetherester amide is obtained by copolymerizing (A) an aminocarboxylic acid, a lactam or the salt of a dicarboxylic acid with a diamine, (B) a poly(aklylene oxide) glycol and (C) a dicarboxylic acid, and contains 30-70 wt.% of the polyetherester repeating units.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyester fiber having antistatic properties and a method for producing the same.
More specifically, a polymer having high hydrophilicity is used as an antistatic agent. More specifically, an antistatic polyester fiber comprising a polymer having polyalkylene terephthalate as a main component and a polyetheresteramide-based antistatic agent having a specific composition, and a method for producing the same It is about.

[0002]

BACKGROUND OF THE INVENTION Polyesters are widely used as synthetic fibers because of their many excellent properties. However, polyester fibers are more hydrophobic than natural fibers such as wool and silk, fibrous fibers such as rayon and acetate, and acrylic fibers, so they tend to generate static electricity, causing dust to adhere to the static electricity and clinging to clothes. Has the disadvantage that

[0003] Various means have been proposed so far to improve such disadvantages, and the simplest means is to apply an antistatic agent to the fiber surface.
However, in this case, the antistatic agent is easily lost by the dyeing process and washing, and not only is it difficult to expect a permanent antistatic effect, but also there is a disadvantage that the processing cost increases.

As a method for solving these problems, there is a method in which polyester itself is modified by kneading an antistatic agent into a polymer as an antistatic component.
Japanese Patent Application Laid-Open No. 282311 and Japanese Patent Application Laid-Open No. 7-278946 propose a method in which a highly hydrophilic copolymer is contained as an antistatic component in polyester fibers.

In this case, in order to obtain good antistatic properties, it is necessary that the streaks of the antistatic agent extend sufficiently long in the direction of the fiber axis. Problems such as deterioration of mechanical properties and coloring occur.
If the antistatic agent is too finely dispersed before the spinneret discharge, the antistatic property becomes insufficient. Conversely, if the dispersion of the antistatic agent is not sufficient, the distribution of the antistatic agent in the fiber cross-sectional direction becomes non-uniform, and the variation in single-fiber fineness increases, thereby causing problems such as yarn forming property and generation of fluff in high-order processing. There were problems of dyeability such as passability and uneven dyeing. That is, it is one problem of the antistatic fiber to contain an antistatic agent without impairing the excellent properties of the polyester fiber, and to achieve both good antistatic property and uniform and moderate dispersibility in the fiber cross-sectional direction. ,
It was difficult with conventional technology.

For example, in the method disclosed in Japanese Patent Application Laid-Open No. 7-278946, there is no description about the problem of dispersibility in the cross-sectional direction of the fiber which is the object of the present invention. It was difficult to achieve both high passability and high passability.

As means for making the distribution of the antistatic agent uniform in the cross-section of the fiber, means are disclosed in JP-A-60-39413 and JP-A-3-206120. However, the method using a static mixer on the premise of melt flow mixing proposed in these methods combines independent melt spinning phases to form independent antistatic polymer phases in the fiber axis direction. It is technically different from the extruder mixing proposed in the above. Furthermore, it has been difficult to achieve the yarn-making operability and higher-order passage aimed at by the present invention, for example, when the static mixer is used, the molten polymer abnormally stays and the staying time becomes long.

[0008]

SUMMARY OF THE INVENTION The present invention overcomes the above-mentioned problems of the prior art, has excellent antistatic durability and dyeing quality, and has good process passability in high-order processing. An object is to provide an antistatic fiber excellent in stability and quality stability.

[0009]

Means for Solving the Problems To solve the above problems, the present invention comprises the following constitutions.

A highly hydrophilic polymer is used as an antistatic agent.
An antistatic polyester fiber containing 2% by weight to 5% by weight and having physical properties satisfying the following (A) and (B) at the same time.

(A) Specific resistance (R) 10 × 10 ⁸ ≦ R
≦ 1000 × 10 ⁸ Ω · cm (B) Single yarn fineness CV% (X) X ≦ 5.0

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

Examples of the polyester which is the basis of the present invention include polyalkylene terephthalate and polyalkylene phthalate. Among them, terephthalic acid is a main acid component, and an alkylene glycol component having 2 to 6 carbon atoms, ie, ethylene glycol The present invention is directed to a polyester containing at least one kind of glycol selected from trimethylene glycol, tetramethylene glycol, pentamethylene glycol and hexamethylene glycol as a main glycol component.

In this polyester, the terephthalic acid component may be replaced with another difunctional carboxylic acid component. Examples of such carboxylic acids include bifunctional aromatic carboxylic acids such as isophthalic acid, phthalic acid, dibromoterephthalic acid, naphthalenedicarboxylic acid, diphenylcarboxylic acid, diphenoxyethanecarboxylic acid, and β-oxyethoxybenzoic acid. Can be.

Further, a part of the above glycol component may be replaced by another glycol component. Examples of such a glycol component include cyclohexane-1,4-dimethanol, neopentyl glycol, bisphenol A, bisphenol S, 2,2- Bis [3,5-dibromo-4-
Aliphatic, alicyclic and aromatic diols such as (2-hydroxyethoxy) ethoxy) phenyl] propane.

Further, the above-mentioned polyester may be blended and melted with a small amount of another polymer, if necessary, or may be a small amount of a chain branching agent such as pentaerythritol, trimethylolpropane or trimellitic acid. In addition, the polyester of the present invention may contain conventionally known pigments such as titanium oxide and carbon black, as well as pigments such as titanium oxide and carbon black, as well as conventionally known antioxidants and coloring inhibitors.

In the present invention, the amount of the antistatic agent contained in the polyester is 0.2% by weight or more based on the polyester.
% By weight or less, particularly preferably 0.3% by weight or more,
5% by weight or less. If the amount is less than 0.2% by weight, the obtained polyester fiber has insufficient antistatic properties. If the amount exceeds 5% by weight, the yarn-forming properties such as thread breakage during the yarn-forming are caused, and the object of the present invention cannot be achieved. The antistatic polyester fiber of the present invention is required to be composed of the polyester having such a composition and satisfy the following physical properties of the yarn at the same time.

(A) Specific resistance (R) 10 × 10 ⁸ ≦ R
≦ 1000 × 10 ⁸ Ω · cm (B) Single yarn fineness CV% (X) X ≦ 5.0 Specific resistance (hereinafter abbreviated as R) is a value measured and measured by a method described in Examples described later, This has a significant effect on antistatic properties after weaving and knitting. R is 10 × 10 ⁸ Ω · cm or more, 100
0 × 10 ⁸ Ω · cm or less is required, preferably 60
0 × 10 ⁸ Ω · cm or less. R is 10 × 10 ⁸ Ω · c
If it is less than m, the antistatic component in the antistatic polyester is localized, and yarn spots on the original yarn are likely to occur.In addition, when alkali treatment is performed after weaving, the weight loss spots easily occur in the greige fabric. Significantly degrade the quality of Conversely, R is 10
Those exceeding 00 × 10 ⁸ Ω · cm hardly exhibit antistatic properties and cannot achieve the object of the present invention.

Next, the single yarn fineness CV% (hereinafter abbreviated as X) is a value measured and measured by the method described in Examples described later, and has a great influence on the yarn forming property and the process passability in high-order processing. . X
Must be 5.0 or less, and particularly preferably 3.5 or less. When X exceeds 5.0, yarn breakage in the yarn-making process is large and the yarn-making properties are deteriorated. In addition, the dyeing quality is deteriorated due to unevenness in the fineness of the single yarn, and fluffing in weaving and knitting frequently occurs. Cannot achieve the purpose of Examples of the polymer used as the antistatic agent in the present invention include polyalkylene ethers (polyalkylene oxides) such as condensation products of ethylene oxide and propylene oxide, and condensation products of both.
And, polycarboxylic acid component aminocarboxylic acid,
Examples include block copolymers such as polyetheramide, polyetherester, and polyetheresteramide in which lactam, diamine, dicarboxylic acid, dicarboxylic acid ester, and the like are reacted. Among them, polyetheresteramide is preferred.

Examples of the polyetheresteramide include (A) aminocarboxylic acid, which is a constituent component thereof, and salts of lactam or diamine and dicarboxylic acid, such as aminocarboxylic acid having 6 or more carbon atoms, or lactam or 6 or more carbon atoms. Preferred are salts of diamines and dicarboxylic acids, more preferably ω-aminocaprylic acid, ω-aminoverconic acid, ω-aminocaproic acid, and 11-aminoundecanoic acid, aminocarboxylic acids such as 12-aminododecanoic acid or caprolactam, Enantolactam,
Lactams such as caprylactam and laurolactam and salts of diamine-dicarboxylic acids such as hexamethylenediamine-adipate, hexamethylenediamine-sebacate, and hexamethylenediamine-isophthalic acid are used, among which caprolactam, 1, 2-Aminododecanoic acid and hexamethylenediamine-adipate are more preferably used.

The poly (alkylene oxide) glycol (B) which is a constituent of the polyetheresteramide includes polyethylene glycol, poly (1,2-propylene oxide) glycol, poly (1,2-propylene oxide) glycol and poly (alkylene oxide) glycol. (1,3-propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, poly (hexamethylene oxide) glycol, a block or random copolymer of ethylene oxide and propylene oxide, and the like are preferably used. However, among these, polyethylene glycol is particularly preferably used because of its excellent antistatic properties.

The dicarboxylic acid (C) which is a constituent component of the polyetheresteramide includes terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-
Aromatic dicarboxylic acids such as 4,4 ′ dicarboxylic acid, diphenoxyethane dicarboxylic acid and 5-sulfoisophthalic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and dicyclohexyl-4,
Aliphatic dicarboxylic acids such as 4 'dicarboxylic acid; and aliphatic carboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid, and dodecanediacid (decanedicarboxylic acid). Particularly, terephthalic acid, isophthalic acid, ,
4-cyclohexanedicarboxylic acid, sebacic acid, adipic acid and dodecadic acid are preferably used in terms of polymerizability, color tone and physical properties.

The poly (alkylene oxide) glycol and the dicarboxylic acid are reacted at a molar ratio of 1: 1 in the reaction, but are usually supplied at different charging ratios depending on the kind of the dicarboxylic acid used.

The constituent units of the polyetheresteramide of the present invention are polyetherester units in an amount of 30% by weight or more.
It is used in a range of 0% by weight or less, and has excellent mechanical properties and good spinning properties, and sufficiently satisfies the antistatic property of the obtained fiber.

The metal salt compound of sulfonic acid in the antistatic agent of the present invention includes alkylbenzenesulfonic acid such as dodecylbenzenesulfonic acid, tridecylbenzenesulfonic acid, tridecylbenzenesulfonic acid, nonylbenzenesulfonic acid and sodium, potassium, etc. Or a salt formed from an alkylsulfonic acid and an alkali metal such as sodium or potassium. Of these, sodium dodecylbenzenesulfonate is particularly preferred.

The amount of the metal sulfonic acid compound to be added to the polyetheresteramide is 2 to 20 parts by weight, preferably 3 to 10 parts by weight, per 100 parts by weight of the polyetheresteramide. Not more than parts by weight. Fibers obtained by using an antistatic agent having a compounding amount satisfying this range have more excellent antistatic properties and good yarn-making properties. In the present invention, the polyetheresteramide-based antistatic agent contained in the polyester may of course be added with a conventionally known antioxidant, coloring inhibitor and the like.

When the antistatic agent satisfies the above configuration,
It is presumed that streaks of the antistatic component are easily dispersed uniformly, and that both antistatic properties and single-fiber fineness variations are better achieved.

Next, a method for producing the antistatic polyester fiber of the present invention will be described.

In the present invention, the antistatic agent may be added at any stage from the polymerization step of the polyester to the melting in the spinning step. In particular, the pre-spinning polyester chip and the antistatic agent chip are mixed at a predetermined ratio. A method of blending and melt-mixing in a spinning machine is preferred. As a method of chip blending, there is also a means of mechanically blending with a blender or the like.However, from the viewpoint of preventing demixing at the time of transferring the blended chips, a predetermined ratio of each chip is supplied to the supply section of the melt extruder by a metering supply device. Metering and supply continuously at
Blending is more preferable.

From the standpoint of both dispersibility and antistatic properties, the spinning machine has a compression ratio represented by the following equation: compression ratio (hereinafter abbreviated as VCR) = Hf (D−Hf) / Hm
(D-Hm) Hf: Groove depth of screw supply section, Hm: Groove depth of screw fusion section D: An extruder-type melt spinning machine that satisfies the property of having a screw diameter of 2.0 or more and 3.0 or less. It is preferably, and particularly preferably 2.5 or less.

In an extruder or a screw pressure melter type melt spinning machine having a VCR of less than 2.0, the dispersibility of the antistatic component is too poor, the dispersion of single yarn fineness becomes large, and the spinning property is deteriorated. Generation of fluff,
In the case of an extruder having a VCR of more than 3.0, the antistatic component is too finely divided at the time of melt-kneading, resulting in insufficient antistatic property of the obtained polyester fiber, thereby achieving the object of the present invention. Can not.

Further, in the present invention, the extruder-type melt spinning machine has a discharge rate (kg / h) / extruder screw rotation speed (rpm) (hereinafter abbreviated as Q / N) of 1.0 or more and 2.0 or more. And preferably 1.2 or less.
The above is particularly preferred. In an extruder having a Q / N of less than 1.0, the antistatic component is too finely divided at the time of melt-kneading, resulting in insufficient antistatic properties of the obtained polyester fiber. In the screw pressure melter type melt spinning machine, the dispersibility of the antistatic component becomes too bad, the dispersion of single yarn fineness becomes large, the yarn forming property deteriorates, fluff occurs in high-order processing, the dye quality deteriorates, and the present invention Cannot achieve the purpose of

The polymer melted by the above-mentioned method can be produced by a well-known spinning method. Among them, a high-speed spinning method that does not require a drawing step improves productivity, reduces costs by omitting the drawing step, and reduces fluff. This is a preferable method because it can reduce the occurrence and can also be expected to have an effect of improving the dyeability, so that the cross-weaving with other types of fibers can be facilitated and the application can be expanded. As a high-speed spinning method for obtaining practically sufficient yarn physical properties only by the melt spinning step without going through the drawing step, for example, in melt spinning, the melt-spun polyester yarn is once cooled and solidified, and then introduced into the heating area. And stretching at a speed of 4500 m / min or more. Here, the stretching in the heating zone may be either stretching in a non-contact indirect heating zone or stretching using a heating take-off roller and a heating stretching roller.
The subsequent stretching in the heating zone after cooling is preferably carried out at a temperature from the glass transition temperature to the melting point, and if the temperature is below the glass transition point, the fiber properties are poor for practical use and the fiber is extremely poor. Conversely, if the temperature exceeds the melting point, not only will the fusion between the single yarns in the heating region and the yarn breakage not only cause operational problems, but also the texture of the fabric obtained by weaving or knitting the obtained fibers will be remarkable. It will be inferior.

In the present invention, the fiber refers to a long fiber and a fiber product such as a woven or knitted fabric containing the long fiber. As is well known, polyester fibers are often subjected to alkali weight reduction for the purpose of improving the feeling, but even if the fibers according to the present invention are subjected to alkali weight reduction, the antistatic effect is almost unchanged and the performance does not decrease. In addition, in recent years, in which high-speed processing is performed at a higher order, the generation of fluff during weaving and knitting is greatly improved by the present invention. In this regard, the present invention significantly exhibits effects that were not considered in the conventional invention.

The fiber of the present invention is not limited to a single material, but may also be a blended yarn, a blended yarn, a processed yarn, or a blended fabric, a blended fiber, or a multi-layered structure with a combination of different types of fibers. Excellent antistatic effect on woven and knitted fabrics.

The present invention is used for women's blouses, women's skirts, casual shirts, dress shirts, slacks,
Men's formal wear, ladies' formal wear,
Knitwear, sportswear, coats, outwear in general, baby wear, children's clothing in general, working wear,
Household goods such as dust-free clothes, Japanese clothing, Japanese lining, Japanese clothing underwear, aprons and tablecloths, bedding or sleeping clothes such as futon sheets and pajamas, automotive interior ceiling and flooring materials, interior goods, carpets and other industries Suitable for materials and the like.

[0037]

Hereinafter, the present invention will be described in detail with reference to Examples.
These examples do not limit the scope of the present invention. In addition, each characteristic value in an Example was calculated | required by the following method.

(1) Specific resistance value of raw yarns Filament yarns are bundled to about 2,000 denier, sufficiently refined using a weak anionic detergent to remove oils and the like, and then subjected to 20 ° C., 43% RH (relative humidity). ) Was left for 24 hours, and the resistivity at both ends was measured to determine the specific resistance.

◎: 10 × 10 ⁸ Ω · cm ≦ R ≦ 600 ×
10 ⁸ Ω · cm ○: 600 × 10 ⁸ Ω · cm ≦ R ≦ 1000 × 10 ⁸ Ω ·
cm ×: 10 × 10 ⁸ Ω · cm> R or R> 1000 × 1
0 ⁸ Ω · cm

(2) Single yarn fineness CV% With a test length of 25 mm and a 0.4 g load applied, the single yarn is set in the oscillating section (1880 Hz), and the fineness of each single yarn is calculated from the resonance frequency. The rate of change (CV%) was calculated.

(3) Yarn-forming properties A total of 1000 kg of a polyester polymer and an antistatic agent was melt-spun, solidified by cooling, and then continuously stretched to obtain 4,500 m
Judgment was made based on yarn breakage obtained by winding at a speed of / min or more.

◎: 0 times of thread break ○: 1 to 3 times of thread break ×: 4 or more times of thread break

(4) Higher passability (fluff) Judgment was made based on the number of times the loom was stopped due to fluffing when an antistatic polyester fiber was driven into a plain weave at a driving width of 180 cm and a speed of 1400 m / min by 2.0 × 10 ⁶ m. .

◎: 0 to 1 time ○: 2 to 4 times ×: 5 times or more

Examples 1 to 7 and Comparative Examples 1 to 8 A polyetheresteramide-based antistatic agent chip in which the antistatic polymer composition was changed as shown in Table 1 was prepared. In addition,
At the time of preparation, 1,3,5-trimethyl-
2,4,6-tri (3,5-di-terbutyl-4-hydroxyl) benzene is converted to polyetheresteramide 1
5.5 parts by weight were added to 00 parts by weight. After drying the polyetheresteramide-based antistatic agent chip at 80 ° C. for 6 hours, it is blended with a polyethylene terephthalate (hereinafter abbreviated as PET) chip which is vacuum-dried at 160 ° C. for 6 hours.
It is melt-kneaded with an extruder-type melt spinning machine having characteristics of VCR = 2.3 and Q / N = 1.4, and a 75 denier 36 filament drawn yarn is produced by the following yarn making methods (I) and (II). Obtained.

(I) Spinning at a spinning temperature of 290 ° C. in an apparatus as shown in FIG. 1, cooling, introduction into a heating zone of 200 ° C., stretching, and 4500 through a godet roller
Wind at m / min.

(II) Spinning at a spinning temperature of 290 ° C. in an apparatus as shown in FIG. 2, cooling, and then taking up a heating take-up roller heated to 90 ° C. at a speed of 1800 m / min. Take-off roller and 140 ° C
Stretched 2.7 times with a heated stretching roller heated to
4500m / min after heat treatment with heat stretching roller
Take up with.

Table 2 shows the physical properties of the obtained fibers, the yarn forming properties, and the degree of fluff generation in the higher processing step.

Examples 8 to 10 and Comparative Examples 9 to 14 An extruder type melt spinning machine having the characteristics shown in Table 3 was prepared by blending the antistatic agent chip and the PET chip obtained in the same manner as in Example 1. And melt kneading with a screw pressure melter type melt spinning machine, and the spinning method (I), (I
In I), a drawn yarn of 75 denier and 36 filaments was obtained.
Table 4 shows the physical properties of the obtained fibers, the yarn forming properties, and the degree of fluff generation in the higher-order processing step.

[0050]

[Table 1]

[Table 2]

[Table 3]

[Table 4] As can be seen from Tables 1 and 2, those in which the content of the antistatic agent with respect to PET does not satisfy the present invention (Comparative Examples 1 to 4) and those in which the antistatic agent composition does not satisfy the present invention (Comparative Examples 5 to 8) Has a problem that the specific resistance value is high or the single yarn fineness CV% is large, and the yarn formability and the high-order passage property are poor.

Also, from Tables 3 and 4, the melt spinning machine has an extruder characteristic of VCR 2.0 or less and Q / N 2.0 or more (Comparative Examples 11 and 13), or the spinning machine type is a screw pressure melter type. (Comparative Examples 9 and 1
2) and the single-filament fineness CV% is large, and the high-order permeability is poor,
When the VCR is 3.0 or more and the Q / N is 1.0 or less (Comparative Examples 10 and 14), the specific resistance increases and the antistatic property deteriorates.

On the other hand, it can be seen that the polyester fiber of the present invention has excellent antistatic properties, and also has excellent spinning properties and high passability.

[0053]

According to the present invention, there are provided antistatic fibers having excellent antistatic durability and dyeing quality, good processability in high-order processing, excellent operation stability and quality stability, and a method for producing the same. can do.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of an apparatus used in an embodiment of the present invention.

FIG. 2 is a schematic diagram of an apparatus used in an embodiment of the present invention.

[Explanation of symbols]

 1: extruder 2: spinneret 3: cooling device 4: heating cylinder 5: lubrication device 6: entanglement treatment device 7: first godet roller 8: second godet roller 9: heat treatment device 10: heating take-off roller 11: Heat stretching roller 12: Winder 13: Surface roller Y: Yarn

Claims (3)

[Claims] 1. A polymer having a high hydrophilicity of 0.2
An antistatic polyester fiber, which contains about 5% by weight and has physical properties satisfying the following (A) and (B) at the same time. (A) Specific resistance (R) 10 × 10 ⁸ ≦ R ≦ 1000
× 10 ⁸ Ω · cm (B) Single yarn fineness CV% (X) X ≦ 5.0 2. The method according to claim 1, wherein the antistatic agent is (A) an aminocarboxylic acid, or a lactam, or a salt of a diamine and a dicarboxylic acid;
(B) A polyetheresteramide composed of a poly (alkylene oxide) glycol and (C) a dicarboxylic acid, wherein the polyetherester unit has 30 to
70% by weight of said polyetheresteramide 100
The polyester fiber according to claim 1, which is a polyetheresteramide-based antistatic agent comprising 2 parts by weight and 2 to 20 parts by weight of a metal compound of sulfonic acid. 3. An extruder which satisfies the following characteristics (A) and (B) when melt-spinning a mixture of a highly hydrophilic polymer and polyester as an antistatic agent. A method for producing the antistatic polyester fiber according to claim 1. (A) Compression ratio (VCR) 2.0 ≦ VCR ≦ 3.0 VCR = Hf (D−Hf) / Hm (D−Hm) Hf: groove depth of screw supply section, Hm: groove depth of screw fusion section D : Screw diameter (B) Discharge rate Q (kg / h) / rotation speed N (rpm)
1.0 ≦ Q / N ≦ 2.0