JP2015007297A - Polyester fiber excellent in antistatic properties and woven knitted fabric of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antistatic polyester fiber which contains an organic electrolyte in both the base polymer and an antistatic agent, exerts excellent antistatic performance even in a low-temperature, low-humidity environment and is high in toughness and its woven knitted fabric.SOLUTION: In an antistatic polyester fiber, a polyether ester amide type antistatic agent forms independent phases dispersed in a stripe form along the fiber axis, and the polyester fiber contains 0.05-10 wt.% of an organic electrolyte and 0.2-5 wt.% of the polyether ester amide type antistatic agent in the fiber and meets conditions: (1) the wt. blend ratio of the organic electrolyte is polyester phase: polyether ester amide type antistatic agent phase=5:95 to 99:1; and (2) the average diameter of the polyether ester amide type antistatic agent phase is 40-120 nm.

Description

  The present invention relates to a polyester fiber having excellent antistatic performance and toughness characteristics and a woven or knitted fabric thereof. More specifically, the present invention contains an organic electrolyte in both a base polymer and an antistatic agent, and can be used even in a low temperature and low humidity environment. The present invention relates to an antistatic polyester fiber that exhibits excellent antistatic performance and high toughness, and a woven or knitted fabric thereof.

  Polyesters typified by polyethylene terephthalate have excellent mechanical and chemical properties, and are therefore used as synthetic fibers in a wide range of fields including clothing. However, polyester fibers are more hydrophobic than natural fibers such as silk, regenerated fibers such as rayon and acetate, and acrylic fibers, so they tend to generate static electricity and easily cause dust adhesion and clinging to clothes. There is. In order to improve such drawbacks, various means have been proposed so far, such as a method of applying an antistatic agent to the yarn surface by post-processing, a method of graft polymerization of a hydrophilic substance on the yarn surface, and the like. . However, all of these methods have problems such as durability, weather resistance, and quality defects in the knitting and knitting process.

  For example, the method of applying an antistatic agent to the yarn surface is that the antistatic agent tends to disappear due to the dyeing process or washing, the durability is insufficient, the texture of the fabric becomes hard, or other post-processing There are various problems such as inability to use together. In addition, the method of graft polymerizing a hydrophilic substance on the surface of the yarn has a certain effect in preventing the disappearance of the antistatic agent by washing, but the performance degradation due to repeated washing is unavoidable, and the problems of weather resistance and texture are Remained unresolved.

  On the other hand, as a technique for improving the problems of durability and texture, there is a method of incorporating an antistatic substance into a fiber component. As a method of kneading the antistatic agent, a method of melt blending the antistatic agent at the time of melting (Patent Documents 1 and 2), a method of blending in advance in the polymerization stage (Patent Document 3), and the like have been proposed.

  For example, in Patent Document 1, a block polyether ester amide antistatic agent containing an organic sulfonic acid metal salt is blended at a high concentration in a fiber, and the antistatic function is obtained by finely dispersing these antistatic agents in a streak shape. Have gained. Moreover, in patent document 2, the antistatic function is obtained by mix | blending the polyetheresteramide type | system | group antistatic agent containing organic electrolyte with high concentration in a fiber, and finely dispersing these antistatic agents in the shape of a line. . However, in these methods, satisfactory antistatic performance cannot be obtained with a small amount of antistatic agent blended, and if the antistatic agent blending amount is increased for the purpose of improving antistatic performance, the yarn forming stability is improved. In addition, the heat resistance, raw yarn strength characteristics, and the like are lowered, and there are drawbacks in inducing deterioration of the color tone such as dullness when used as a fabric.

  In addition, in the method of kneading the organic electrolyte and the antistatic agent in the polymerization process represented by Patent Document 3, the antistatic agent streaking is closely adjacent to obtain antistatic properties. In addition to the disadvantages of inferior yarn stability, heat resistance, raw yarn strength characteristics, etc. compared to general polyester fibers, dense fibers are fibrillated and whitened by high-order processing. It has problems such as inducing a phenomenon.

  In these conventional methods, one of the reasons why sufficient antistatic performance does not appear with a small amount of antistatic agent is that, when static electricity (charge) generated in the fiber leaks out of the fiber, the formation of a charge transfer circuit is not possible. It is sufficient that the blended antistatic agent does not function effectively.

  On the other hand, as a method that can maintain the yarn strength while blending the antistatic agent at a high concentration, a technique of making the fiber itself a composite structure such as a core-sheath type has been proposed (Patent Document 4). According to this method, by forming a sufficient charge transfer circuit by disposing the antistatic agent at a high concentration in the core portion, by disposing the polyester having the property of supplementing the strength, color and the like in the sheath portion, It has improved the shortcomings. However, antistatic agents such as polyalkylene glycol and polyetheresteramide have an antistatic mechanism that utilizes moisture in the air, so that the core-sheath base yarn cannot effectively utilize moisture, and is used in an environment with low temperature and low humidity. There is a problem that the antistatic performance is remarkably deteriorated (for example, temperature 10 ° C., humidity 10% RH). In addition to the need for a special compound spinning machine, there are inherent disadvantages such as high manufacturing costs.

JP 7-278946 A JP 2008-13868 A JP-A-10-96121 JP 2006-2258 A

  The present invention relates to a polyester fiber having excellent antistatic performance and toughness characteristics and a woven or knitted fabric thereof. More specifically, the present invention contains an organic electrolyte in both a base polymer and an antistatic agent, and can be used even in a low temperature and low humidity environment. An object of the present invention is to provide antistatic polyester fibers that exhibit excellent antistatic performance and have high toughness, and woven or knitted fabrics thereof.

The above-mentioned problem is a polyester fiber in which a polyether ester amide antistatic agent forms an independent phase dispersed in a streak pattern along the fiber axis, and the organic electrolyte is 0.05 to 10% by weight in the fiber, And an antistatic polyester fiber in which the polyether ester amide antistatic agent is 0.2 to 5% by weight and satisfies the following requirements (1) and (2) simultaneously.
(1) The weight ratio of the organic electrolyte is polyester phase: polyether ester amide-based antistatic phase = 5: 95 to 99: 1
(2) The average diameter of the polyetheresteramide-based antistatic agent phase can be achieved by 40 to 120 nm.

  INDUSTRIAL APPLICABILITY The present invention can provide a highly tough antistatic polyester fiber that efficiently distributes a polyetheresteramide and an organic electrolyte in a fiber and exhibits excellent antistatic performance even in a low temperature and low humidity environment.

  Hereinafter, the present invention will be described in detail.

  Examples of the polyester as the basis of the present invention include aromatic polyester fibers such as polyethylene terephthalate, polytrimethylene terephthalate, and polybutylene terephthalate, and aromatic polyester fibers obtained by copolymerizing an aromatic polyester with a third component, and L-lactic acid. Polyester fibers such as aliphatic polyester fibers represented by the main component are preferred. Such a polyester may be produced by an arbitrary method. For example, polyethylene terephthalate can be described by directly esterifying terephthalic acid and ethylene glycol, or lower alkyl ester of terephthalic acid such as dimethyl terephthalate and ethylene glycol. Of the terephthalic acid and ethylene oxide to form a glycol ester of terephthalic acid and / or a low polymer thereof, and then the product is heated under reduced pressure to obtain a desired degree of polymerization. It is easily produced by a condensation polymerization reaction until In this polyester, a part of the terephthalic acid component may be replaced with another bifunctional carboxylic acid component. Examples of such carboxylic acids include bifunctional aromatic carboxylic acids such as isophthalic acid, phthalic acid, dibromoterephthalic acid, naphthalene dicarboxylic acid, diphenylxyentanecarboxylic acid, β-oxyethoxybenzoic acid, sebacic acid, adipic acid, Bifunctional aliphatic carboxylic acids such as oxalic acid, bifunctional alicyclic carboxylic acids such as 1,4-cyclohexanedicarboxylic acid and the like can be mentioned. Further, a part of the glycol component may be replaced with another glycol component. Examples of the glycol component include cyclohexane-1,4-dimethanol, neopentyl glycol, bisphenol A, bisphenol S, 2,2-bis [3 , 5-dibromo-4- (2-hydroxyethoxy) phenyl] propane, and aliphatic, alicyclic and aromatic diols. Further, the above-described polyester may be obtained by blending and melting a small amount of another polymer as necessary, or by using a small amount of a chain branching agent such as pentaerythritol, trimethylolpropane, or trimellitic acid. In addition to the pigments such as titanium oxide and carbon black, the polyester of the present invention may be added with conventionally known antioxidants and anti-coloring agents in the same manner as ordinary polyesters. However, it is preferable to arrange an organic electrolyte in the range of 0.05 to 10% by weight in this polyester (base polymer). It is preferable that the organic electrolyte is 0.05% by weight or more because antistatic properties can be expressed, and it is preferable that the organic electrolyte is 10% by weight or less because the toughness of the fiber is maintained and the yarn-making property is not deteriorated. More preferably, it is 2 to 7% by weight.

  The organic electrolyte in the present invention is a salt formed from an alkylbenzenesulfonic acid such as dodecylbenzenesulfonic acid, tridecylbenzenesulfonic acid, nonylbenzenesulfonic acid and an alkali metal such as sodium or potassium, or an alkylsulfonic acid and sodium or potassium. A salt formed from an alkali metal such as sodium dodecylbenzenesulfonate is particularly preferable.

  The effect of arranging the organic electrolyte in the polyester base polymer is to transmit the static electricity (charge) generated in the fiber by the organic electrolyte and promote the charge transfer in the fiber. Furthermore, by adding an antistatic agent as in the prior art, a charge transfer circuit is formed in the entire fiber by the antistatic agent and the organic electrolyte in the fiber, and static electricity is likely to leak out of the fiber. That is, by arranging the organic electrolyte in the polyester base polymer, a better effect can be obtained than the antistatic performance using only the electrostatic agent. In addition, even with a small amount of antistatic agent blend that does not exhibit sufficient antistatic performance, a charge transfer circuit sufficient to leak static electricity to the outside of the fiber can be formed by adding an organic electrolyte to the polyester base polymer. Furthermore, by reducing the amount of the antistatic agent, it is possible to obtain better yarn production stability, heat resistance, and raw yarn strength characteristics compared to conventional antistatic polyester fibers, suppressing the fibrillation of the antistatic agent streak, A single yarn can be made finer.

  Next, the polyether ester type antistatic agent used in the present invention is preferably (1) an aminocarboxylic acid, or a salt of a lactam or diamine and a dicarboxylic acid, (2) a poly (alkylene oxide) glycol, and ( 3) A polyether ester amide composed of a dicarboxylic acid and comprising 100 parts by weight of a polyether ester amide having a polyether ester unit of 30% by weight to 70% by weight and 3 parts by weight to 10 parts by weight of an organic electrolyte. Antistatic agent.

  (1) Aminocarboxylic acid or lactam or diamine and dicarboxylic acid salt which is a constituent of polyetheresteramide includes aminocarboxylic acid having 6 or more carbon atoms, or lactam or diamine and dicarboxylic acid having 6 or more carbon atoms And more preferably ω-aminocaprylic acid, ω-aminoenanthic acid, ω-aminocaproic acid, ω-aminovelconic acid, ω-aminocaproic acid, and 11-aminoundecanoic acid, 12-aminododecanoic acid, etc. Aminocarboxylic acids or lactams such as caprolactam, enantolactam, capryllactam and laurolactam and diamine-dicarboxylic acids such as hexamethylenediamine-adipate, hexamethylenediamine-sebacate, and hexamethylenediamine-isophthalic acid Of these, caprolactam, 1,2-aminododecanoic acid, and hexamethylenediamine-adipate are more preferably used.

  (2) Poly (alkylene oxide) glycol, which is a constituent of polyether ester amide, includes polyethylene glycol, poly (1,2-propylene oxide) glycol, poly (1,3-propylene oxide) glycol, poly (tetramethylene) Oxide) glycol, poly (hexamethylene oxide) glycol, a block or random copolymer of ethylene oxide and propylene oxide, and the like are preferably used. Among these, polyethylene glycol is particularly preferably used because of excellent antistatic properties.

  (3) Dicarboxylic acid which is a constituent of polyetheresteramide is terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4′- Alicyclics such as dicarboxylic acids, diphenoxyethanedicarboxylic acids and aromatic dicarboxylic acids such as 5-sulfoisophthalic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and dicyclohexyl-4,4′-dicarboxylic acid And aliphatic carboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid and dodecanediic acid (decanedicarboxylic acid), particularly terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, Sebacic acid, adipic acid and dodecadi Acid polymerizability, is preferably used in terms of color and physical properties.

  Poly (alkylene oxide) glycol and dicarboxylic acid react with each other at a molar ratio of 1: 1 in the reaction. However, the charge ratio may be changed depending on the type of dicarboxylic acid used.

  In the polyether ester amide structural unit of the present invention, the polyether ester unit is preferably in the range of 30 wt% to 70 wt%. Setting within this range is preferable because it is easy to obtain a yarn-forming property capable of handling high-speed yarn-making, excellent antistatic properties, and good fiber properties.

  In the present invention, the amount of the polyether ester amide antistatic agent contained in the polyester is from 0.2% by weight to 5% by weight, particularly preferably from 0.5% by weight to 3% by weight, based on the polyester fiber. It is. When the content is 0.2% by weight or more, the antistatic performance of the polyester fiber obtained even in a low humidity environment is sufficient, and when the content is 5% by weight or less, the toughness of the fiber is maintained and the yarn-making property is not deteriorated.

  It is necessary to mix an organic electrolyte in the antistatic agent in the present invention. The organic electrolyte referred to here is preferably the same as the organic electrolyte blended in the above-mentioned polyester base polymer, because it increases the antistatic property, maintains the toughness of the fiber, and does not deteriorate the spinning performance.

  The blending amount of the organic electrolyte in the polyether ester amide is preferably 3 parts by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the polyether ester amide. When the amount is 3 parts by weight or more, excellent antistatic performance is easily obtained, and when the amount is 10 parts by weight or less, the toughness of the fiber is maintained and the yarn-making property is not deteriorated, which is preferable.

  In the present invention, conventionally known antioxidants, anti-coloring agents and the like may be added to the polyether ester amide antistatic agent, and the additive is controlled to be 10% by weight or less based on the antistatic agent. It is preferable without impairing the electric function and mechanical characteristics.

  The weight ratio of the organic electrolyte contained in both the base polymer and the antistatic agent needs to be base polymer: antistatic agent = 5: 95 to 99: 1. By setting the base polymer: antistatic agent = 5: 95 or more, the antistatic property can be expressed, and by setting it to 99: 1 or less, the toughness of the fiber is maintained and the yarn-making property is not deteriorated. More preferably, it is 90:10 to 99: 1.

  Note that the total amount of organic electrolyte contained in both the base polymer and the antistatic agent, that is, the total amount of organic electrolyte contained in the fiber needs to be 0.05 to 10% by weight. More preferably, it is 2 to 7% by weight. By making the organic electrolyte 0.05% by weight or more, the antistatic property can be expressed, and by making the organic electrolyte 10% by weight or less, the toughness of the fiber is maintained and the yarn-making property is not deteriorated.

  The dispersion state in the polyester fiber of the polyether ester amide antistatic agent of the present invention is important for achieving good antistatic performance and stabilizing the high toughness of the fiber and the spinning property. In this dispersed state, the melted antistatic agent preferably forms a plurality of independent streaky independent phases in the fiber longitudinal direction. The state of forming an independent phase refers to a state where adjacent muscles do not intersect. Due to the presence of streaks in the longitudinal direction, the specific interface area of the antistatic component is increased and the antistatic effect is improved.

  This dispersed state can be easily measured by observing / measuring antistatic agent streaks (described later), and the average diameter of the independent phase dispersed in the streaks needs to be in the range of 40 to 120 nm. Preferably, it is the range of 50-100 nm. When the thickness is 40 nm or more, the antistatic property is good. On the other hand, when the thickness is 120 nm or less, the thickness unevenness of each filament does not occur, the fiber physical properties do not become poor, and the occurrence of yarn breakage during yarn production can be suppressed. When the average diameter of the independent phase dispersed in the shape of the antistatic agent exceeds 120 nm, the force of the antistatic agent stretched during the discharge of the die increases the force of returning to a spherical shape due to the interfacial tension between the polymers. Immediately below the discharge hole, a bulge having a diameter several times the diameter of the discharge hole is generated, which is called a ballast effect. For this reason, thick and thin abnormalities are likely to occur in the thinning deformation process during spinning, and quality problems such as fineness unevenness occur in the longitudinal direction of the yarn, and yarn breakage occurs when the thinness is large. Therefore, it is necessary to keep the average diameter of the independent phase dispersed in a streak form at 120 nm or less. By setting the average diameter of the independent phase dispersed in a streaked state to 50 nm or more, it is possible to suppress a decrease in antistatic properties and physical properties due to muscle cutting at the time of thinning of the fiber, and by setting it to 100 nm or less, fineness spots and the like This is preferable because quality problems and yarn breakage can be further suppressed.

  As described above, the independent phase dispersed in a streak can be represented by an aspect ratio (length (L) / width (D) of a streak portion on the fiber surface), and this value is preferably 30 or more. More preferably, it is 50-120. In order to improve the antistatic property, it is important to make the movement of electric charges smooth in a state where the antistatic agent is continuous for a long time in the fiber. Therefore, the length of the antistatic agent in the fiber axis direction is preferably as long as possible. When the aspect ratio is 30 or more, the charged charge easily flows on the surface of the single fiber, and a better antistatic property is obtained. By setting the aspect ratio to 120 or less, the yarn breakage is reduced while keeping the excellent antistatic property. It is preferable because a fiber with high toughness can be obtained.

  The average interval between the streaky dispersed independent phases in the polyester fiber of the polyether ester amide antistatic agent of the present invention is preferably 0.5 μm to 2 μm. When the thickness is 0.5 μm or more and 2 μm or less, the charged electric charge flows smoothly and good antistatic performance is obtained.

The antistatic polyester fiber of the present invention preferably has a specific resistance of less than 100 × 10 ⁸ Ω · cm under conditions of a temperature of 10 ° C. and a humidity of 10% RH, which are low temperature and low humidity environments. Incidentally, the specific resistance of the raw yarn of a general polyester fiber is 1.0 × 10 ¹⁴ Ω · cm level. Static electricity depends on the amount of moisture in the air. Static electricity hardly occurs in a high humidity environment, and static electricity is likely to occur in a dry environment. In order to exhibit sufficient antistatic properties, if the yarn has a specific resistance of less than 100 × 10 ⁸ Ω · cm under severe conditions of a temperature of 10 ° C. and a humidity of 10% RH, which is a low temperature / low humidity environment It is preferable because sufficient antistatic performance can be exhibited.

In the antistatic polyester fiber of the present invention, the polyether ester amide antistatic agent forms a large number of independent and continuous streaks in the fiber axis direction, and these streaks are highly dispersed. And has a continuous phase. At this time, the average length of the independent phases is 1 μm or more, the average phase interval is within 2 μm, and the ratio of the number of continuous bars to the total number of independent phases is preferably 50% or more per 1 μm ^{2 of} the fiber longitudinal section. This ratio is preferably 50% or more because sufficient antistatic properties are exhibited.

  In the antistatic woven or knitted fabric of the present invention, the antistatic polyester fiber is preferably used for at least one of warp and weft in the fabric, and is contained in a proportion of 50% by weight or more based on the total weight of the fabric. When it is 50% by weight or more, sufficient antistatic performance can be obtained when worn. In order to cope with static electricity generated by friction, it is preferable that the antistatic polyester fiber is directly in contact with the human body, the outer surface or the lining.

  The thus obtained antistatic fabric preferably has a frictional voltage of 1500 V or less under the conditions of a temperature of 20 ° C. and a humidity of 40% RH. Furthermore, it is more preferable if the frictional voltage is 1500 V or less under an environment of a severe temperature of 10 ° C. and a humidity of 10% RH. The lower the frictional voltage is, the better the antistatic property is. However, the frictional voltage of a general polyester fiber is about 5 to 6 kV in a standard state (temperature 20 ° C., humidity 65% RH), and the antistatic property is low. It is about 3 kV for a fabric subjected to antistatic processing that is said to be good. The antistatic fabric of the present invention is preferably used as a backing. Unpleasant problems caused by the generation of static electricity include spark discharge that occurs when a lining such as a one-piece or skirt clings to a foot during walking, or friction between a jacket lining and a sweater or shirt in a garment. By using the antistatic fabric of the present invention for the lining, these problems can be solved and comfort at the time of wearing can be obtained.

In the antistatic polyester fiber of the present invention, the single yarn fineness and the number of filaments are also important requirements for enhancing the commercial value in terms of function and feel. The single yarn fineness is preferably 0.3 to 5 dtex.
When the single yarn fineness is 0.3 dtex or more, stable yarn forming properties are obtained, and when it is 5 dtex or less, the texture is soft and preferable. More preferably, it is 0.5-2 dtex.

  The number of filaments of the antistatic polyester fiber of the present invention is preferably 12 to 144. When there are 12 or more, the spinning discharge amount is stabilized and the adverse effect of the heat resistance stability of the polymer is reduced, which is preferable. Further, it is preferable that the number of filaments is 144 or less because the spinning cooling process does not become uneven among the filaments, uniform cooling becomes possible, and the single yarn fineness becomes uniform.

  The strength is preferably 2.5 cN / dtex or more, and the toughness is preferably 20 or more. The strength is preferably from 3.0 cN / dtex to 5.0 cN / dtex and toughness of 20 to 30. When the strength is 2.5 cN / dtex or more, the strength of the fabric is high and suitable for thinning, high density and light weight of the clothing fabric. When the strength is 5.0 cN / dtex or less, the generation of fuzz due to the stretch ratio being too high can be suppressed, and the process passability is improved. Also, in order to increase the fiber strength, it is common to increase the draw ratio at the time of production, but in this way, the strength is increased, but the elongation is decreased, fluff is likely to occur, processes such as weaving Passability is poor. For this reason, in order to obtain high strength while maintaining sufficient elongation, the toughness is preferably 20 or more, and more preferably 23 or more. Further, there is a limit to the improvement in toughness by optimizing the yarn production conditions, and it is preferable that the toughness is 30 or less that can be reached with general-purpose polyester.

  Hereinafter, the matter which should be noted about the method of manufacturing preferably the antistatic polyester fiber of this invention is demonstrated.

  First, the manufacturing method of a polyester base polymer is demonstrated. In detail, as described above, it is preferable to use a polyester polymer having ethylene terephthalate as a main repeating unit as a base polymer and add 0.05 to 10% by weight of an organic electrolyte thereto. This addition time is preferably added to the reaction system before the polyester polycondensation reaction is completed, and more preferably, it is added to the system in the middle of the polycondensation reaction to complete the polycondensation reaction. It is preferable in order to ensure stability.

  Next, as the antistatic agent, 0.2 to 5% by weight of a polyether ester antistatic agent added with 3 to 10 parts by weight of the organic electrolyte as described above is added to the polyester polymer added with the organic electrolyte. There is a need.

  The timing for adding the antistatic agent will be described. The antistatic agent can be added at any stage from the polymerization step of the polyester to the spinning in the spinning step, but a method of mixing in a spinning machine is preferred. The chip blending method is preferably a method in which the chip blending is performed by supplying each chip to the supply unit of the melt extrusion apparatus by a metering supply device using a constant feeder that continuously measures and supplies the chips at a predetermined ratio.

  The antistatic agent supplied and mixed in this way can be produced by a known spinning method. It is preferable that the mixed and melted antistatic agent forms a plurality of independent streak states in the fiber longitudinal direction in the polyester fiber. The state in which independent muscle states are formed refers to a state in which adjacent muscles do not intersect. By existing in a muscle state in the longitudinal direction, the specific interface area of the antistatic component is widened and the antistatic effect is improved. Regarding the plurality of independent streak states, an aspect ratio of 30 or more is preferable, and 50 or more is preferable because a charged charge easily flows on the surface of a single fiber and better antistatic properties can be obtained. Moreover, it is preferable to set it to 120 or less because the yarn breakage is small while maintaining good antistaticity, and a high toughness fiber can be obtained.

  In the present invention, when spinning a new regulated electric polymer obtained by chip-blending a polyether ester type antistatic agent added with an organic electrolyte to a polyester polymer added with an organic sulfonic acid metal salt, in the spinning process, In order to control the dispersion diameter in the spinning pack, a high-mesh filter layer (# 100 to # 200) or a non-woven filter with a small filtration diameter (filtration diameter of 5 to 30 μm) may be disposed on the die. Among them, a multilayer filter made of a metal nonwoven fabric having a plurality of wire diameters is most effective for controlling the dispersion diameter.

  As the shape of the die discharge hole, a known round cross-section, Y cross-section, triangular cross-section, square cross-section, flat cross-section, or hollow cross-section thereof can be used, and a suitable one can be selected according to the application. .

  The cooling method under the base may be a uniflow type chimney that cools from one direction, or an annular chimney that applies cooling air from the inside to the outside of the yarn or from the outside to the inside of the yarn. At this time, it is desirable to cool the cooling air by applying a cooling gas to the multifilament from a direction orthogonal to the multifilament. The speed of the cooling air at this time is preferably 0.1 m / second or more and 1 m / second or less, and more preferably 0.2 m / second or more and 0.8 m / second or less. Further, the temperature of the cooling air is preferably low in order to achieve uniform cooling, but it is realistic and preferable to be 15 ° C. or more and 25 ° C. or less in consideration of the temperature adjustment cost of the cooling air.

  The spun multifilament is coated with a surface by supplying a known spinning oil. The amount of the oil attached at this time is 0.3 to 3% by weight as a pure oil to the yarn. As the spinning oil, a normal oil widely used as an oil for polyester fibers for clothing can be used.

  The take-up step is composed of (1) a process of winding and (2) a process of further thermally drawing the wound filament. It is also possible to obtain antistatic polyester fibers directly in the process (1) above, and after stretching in the heating zone following cooling with cooling air, obtain antistatic polyester fibers through the process (1). It is also possible. In addition, the antistatic polyester fiber can be obtained by a one-step method in which the antistatic polyester fiber taken up in the process (1) is drawn by a heating roller without being wound once, and then wound up. Preferably, a one-step direct spinning method in which the spinning speed is taken up at 800 m / min or more and continuous drawing is performed. The major problems of the two-step method are the time-dependent changes in the yarn quality of the wound drum due to the storage environment such as the temperature and humidity of the wound undrawn yarn drum, and the difference in inner and outer layers of yarn quality by drum winding layer. In addition, the drum end face and the central part are prone to remarkably easily appear as thready physical property spots. On the other hand, it is preferable to employ the one-step method of the direct spinning method because the above-mentioned physical property spots can be improved. A preferable spinning speed is 1200 m / min or more and 3000 m / min or less. Spinning at 3000 m / min or less is preferable because the spinning tension can be suppressed to 0.3 cN / dtex or less and distortion of the fiber internal structure can be suppressed. A direct spinning and drawing method in which drawing is continuously performed after take-up is preferable because the quality can be stabilized and the cost can be reduced by omitting the steps.

  The drawing temperature is preferably 60 ° C. or higher and 140 ° C. or lower, which is near the glass transition temperature of the undrawn yarn. Uniform stretching can be achieved by adjusting the temperature to 60 ° C. or higher, and deterioration of operability due to fusion to a stretching roll and spontaneous elongation of fibers can be prevented by setting the temperature to 140 ° C. or lower.

  Moreover, after drawing, it is preferable to heat-set at a temperature at which the crystal speed of the undrawn yarn is maximized, preferably 100 ° C. or higher and 220 ° C. or lower, more preferably 120 ° C. or higher and 200 ° C. or lower. Heat setting promotes fiber crystallization, can increase strength, and can stabilize delayed shrinkage and boiling water shrinkage, which is preferable.

  The heat-set fiber is wound up by a winder, and the winding tension is preferably 0.02 cN / dtex to 0.15 cN / dtex. When wound on a package, it is preferable because it can reduce the difference in inner and outer layers of yarn properties, reduce saddles and bulges, and stabilize the delayed shrinkage and the boiling water shrinkage.

  By drawing under the above conditions, it is possible to obtain a drawn yarn having high process stability, high strength, high toughness and high antistatic properties.

  The antistatic polyester fiber of the present invention may be a raw yarn that has just been spun and drawn, may be a processed yarn to which crimps have been added, and may be appropriately entangled by twisting or air. The polyester-based thermoplastic synthetic fiber is preferably a multifilament. When the spun yarn is used, the friction coefficient increases due to the fluff on the fiber surface, and static electricity is likely to be generated by friction, which is not preferable.

  In the antistatic fabric of the present invention, it is preferable to use 50% or more of antistatic polyester fiber having the above characteristics for at least one of the warp and the weft. . More preferably, it is 70% or more, and particularly preferably 100%.

Next, the present invention will be described in detail by way of examples. Various evaluation methods were performed by the following methods.
(Fiber resistivity measurement method)
The sample is thoroughly scoured in a weakly alkaline aqueous solution of 0.2% by weight of an anionic surfactant to remove the oil agent, etc., and then thoroughly rinsed and dried. Next, the sample was aligned with a fiber bundle having a length (L) of 5 cm and a total fineness (D) of 2000 denier (2200 dtex), and each condition of temperature 10 ° C. and humidity 10% RH (water vapor partial pressure 0.93 mmHg). Then, after adjusting the humidity for 2 days, the resistance of the sample is measured at an applied voltage of 500 V using a vibration capacity type micro-potential measuring device, and calculated by the following equation.
ρ = (R × 0.9D) / (9 × 10 ⁵ × L × d × 10 ⁴ )
ρ: Volume resistivity (Ω · cm)
R: Resistance (Ω)
D: Fineness (dtex)
L: Sample length (cm)
d: Sample density (g / m ² ).

(Measurement method of frictional voltage)
The polyester fiber was measured in accordance with the JIS L 1094 (2008) friction voltage measurement method, and the voltage (V) 60 seconds after the start of friction was measured. The measurement was carried out in a test room at a temperature of 20 ± 1 ° C., a relative humidity of 40 ± 2% RH, a temperature of 10 ± 1 ° C., and a relative humidity of 10 ± 2% RH. Measured in the warp direction and the weft direction, each n = 5, and a white cloth attached to cotton specified in JIS L 0803 (2011) is used as the friction cloth.

(aspect ratio)
After treating the antistatic polyester fiber with a NaOH concentration 0.1 kg / L solution to dissolve the antistatic part, the streaks appearing on the fiber surface were observed with a scanning electron microscope (SEM), and the aspect ratio = fiber The length / width of the streaks on the surface is shown.

(Fiber strength, elongation at break, elastic modulus and toughness)
The sample was measured with a tensile tester ("TENSILON UCT-100" manufactured by Orientec Co., Ltd.) under the constant speed elongation conditions shown in the JIS L 1013 (2010) 8.5.1 standard time test. At this time, the holding interval was 20 cm, the pulling speed was 20 cm / min, and the number of tests was 10 times. The elongation at break was determined from the elongation at the point showing the maximum strength in the SS curve. The elastic modulus was recorded on the chart paper as a chart speed of 100 cm / min and a stress full range of 500 cN, and obtained from the slope of the initial tensile curve.
Toughness was calculated from the following equation.

Toughness = strength (cN / dtex) × (elongation (%) ^0.5 )
(Average diameter of antistatic agent streaks of antistatic polyester fiber)
A cross-sectional slice of a single yarn cut perpendicular to the length direction of the fiber was dyed with ruthenium, and the blended state was observed and photographed with an SEM. The dispersion diameter of the antistatic agent's streak is obtained by converting the antistatic agent's streak diameter into a diameter (assuming that the antistatic agent's streak is a circle, the diameter converted from the area of the antistatic agent's streak). And the average value of the 20 antistatic muscles was defined as the average diameter.

(Measuring method of connecting bars)
When the antistatic polyester fiber is treated with a NaOH concentration of 0.1 kg / L solution to dissolve the antistatic agent part, when it is cut in a direction parallel to the fiber axis, the streaks appearing in the longitudinal section of the fiber are observed with an SEM. Then, the ratio of the number of continuous bars to the total number of independent phases in the fiber axis direction per 1 μm ² was determined, and the average value of 10 measurements was taken as the ratio of the number of continuous bars to the total number of independent phases.

(Process tension)
The process tension was measured using a P / C compatible tension meter (model number: IT-NP) manufactured by Intec Corporation. From the fineness of the fiber finally obtained and the draw ratio, the fineness of the yarn at the stage of measuring the tension was calculated, and the tension was determined by the following equation.

Tension (cN / dtex) = tensometer display value (cN) / fineness (dtex)
(Spinning property)
The operation was continued for 3 weeks, and the number of yarn breaks that occurred was recorded and judged.

○○: Number of times of thread breakage is 0 to 2 times per day Pass: ○ Number of times of thread breakage is 3 to 4 times per day Pass ×: Number of times of thread breakage is 5 times or more per day

(Texture)
Sensory tests evaluated tension, waist, suppleness, ultra-fineness, slimeness, dryness, and powdery feelings by three skilled technicians.

○○: Good texture Pass ○: Somewhat inferior, but acceptable level Pass ×: Bad Overall rejection ○○: Good, acceptable ○: Somewhat inferior, acceptable level Pass ×: Bad, failed

Example 1
[Creation of polyester base polymer]
Add 100 parts by weight of dimethyl terephthalate, 65 parts by weight of ethylene glycol, 0.09 part by weight of calcium acetate as a transesterification catalyst, and 0.03 part by weight of antimony trioxide as a polycondensation reaction catalyst. After distilling the theoretical amount of methanol, 0.04 part by weight of trimethyl phosphate was added, and 30 minutes later, 2% by weight of sodium dodecylbenzenesulfonate and 1% by weight of polyethylene glycol having a molecular weight of 4000 were added as an organic electrolyte. Then, the system was gradually depressurized and the temperature was 290 ° C. under a reduced pressure of 1 mmHg, and ethylene glycol was distilled off, and the reaction was completed in 4 hours. The obtained polyester polymer was chipped and then vacuum dried at 160 ° C. for 6 hours and supplied to a spinning machine.

[Prescription of antistatic agent]
On the other hand, as an antistatic agent, dodecylbenzenesulfone as a sulfonic acid metal salt compound was added to 100 parts by weight of a polyether ester amide comprising 50% by weight of caprolactam, 47.3% by weight of polyether ester units and 2.7% by weight of adipic acid. 10 parts by weight of sodium acid was blended to prepare a polyetheresteramide antistatic chip. At the time of preparation, 1,3,5-trimethyl-2,4,6-tri (3,5-di-terbutyl-4-hydroxyl) benzene as an antioxidant is added to 5. 5 parts by weight of polyetheresteramide. 5 parts by weight were added. After the obtained polyetheresteramide antistatic chip was dried at 80 ° C. for 6 hours, the ratio of 1% by weight of the polyetheresteramide antistatic chip to the polyester polymer chip containing 2% by weight of the organic electrolyte Then, the mixture was fed with a constant feeder, blended and melted at a spinning temperature of 290 ° C., and then measured and discharged with a gear pump. The molten polymer was introduced into a built-in spinning pack and spun from a spinneret. A predetermined SUS nonwoven fabric filter was incorporated directly above the spinneret base. After spinning, the yarn was cooled and solidified with cooling air at a temperature of 20 ° C. and a speed of 0.4 m / sec, and an oil agent was applied by an oil supply device. Subsequently, the first heating roll (stretching) was drawn at 1800 m / min with a temperature of 90 ° C., and the second heating roll (heat setting) was stretched at 4617 m / min with a temperature of 155 ° C. (stretching ratio: 2). .565 times), and the yarn was cooled at a peripheral speed of 4654 m / min with the third and fourth non-heating rolls, respectively, and then wound at a winding speed of 4610 m / min. The multifilament comprised from the obtained antistatic polyester fiber was 56 dtex and 48 filaments. The single yarn fineness was 1.17 dtex, and the anti-polyester fiber was good in spinning during the period. Further, the physical properties of the drawn yarn were such that the strength was 4.0 cN / dtex, the elongation was 40%, and the toughness was 25 and there was no practical problem.

Further, it was confirmed that the streaked state of the antistatic polyester fiber was good and the average diameter was 61 nm and the aspect ratio was 60 by SEM photograph determination. The specific resistance in an environment of a temperature of 10 ° C. and a humidity of 10% RH was as good as 40 × 10 ⁸ Ω · cm.

  Further, when cut in a direction perpendicular to the fiber axis, the average phase spacing of each antistatic agent in the cross section of the fiber is 1.2 μm, and when cut in a direction parallel to the fiber axis, the fiber The ratio of the number of continuous connecting bars to the total number of independent phases in the fiber axis direction per 1 μm 2 in the longitudinal section was 70%.

  The obtained antistatic polyester fiber was used for warp and weft to weave a plain fabric. The obtained raw machine was refined at 98 ° C. × 100 m / min, subsequently dried at 130 ° C. × 90 m / min, and then high-pressure dyed amber at 130 ° C. Using this dyed sample, the friction withstand voltage was measured. The friction withstand voltage under the conditions of a temperature of 20 ° C. and a humidity of 40% RH was 602 V, a temperature of 10 ° C. and a humidity of 10% RH, and 904 V, indicating good antistatic performance. The above results are shown in Table 1.

(Examples 2 to 5)
Example 1 was performed except that the amount of the organic electrolyte added to the base polymer polyester was changed as shown in Table 1. The antistatic performance, yarn properties, and antistatic performance of the fabric were also good. The results are shown in Table 1.

(Examples 6 and 7)
The same procedure as in Example 1 was performed except that the amount of the organic electrolyte added to the antistatic agent was changed as shown in Table 1. The antistatic performance, yarn properties, and antistatic performance of the fabric were also good. The results are shown in Table 1.

(Examples 8 to 11)
The same procedure as in Example 1 was performed except that the amount of the antistatic agent added to the entire fiber was changed as shown in Table 1. The antistatic performance, yarn properties, and antistatic performance of the fabric were also good. The results are shown in Table 2.

(Examples 12 and 13)
The same procedure as in Example 1 was performed except that the addition amount of the organic electrolyte to the base polymer polyester and the addition amount of the antistatic agent to the entire fiber were changed as shown in Table 1. The antistatic performance, yarn properties, and antistatic performance of the fabric were also good. The results are shown in Table 2.

(Example 14)
The same procedure as in Example 1 was performed except that the spinneret was changed to 144H. The single yarn fineness was 0.39 dtex. The antistatic performance, yarn properties, and antistatic performance of the fabric were also good. The results are shown in Table 2.

(Example 15)
The same procedure as in Example 1 was performed except that the spinneret was changed to 18H and the fineness was changed to 84 dtex. The single yarn fineness was 4.7 dtex. The antistatic performance, yarn properties, and antistatic performance of the fabric were also good. The results are shown in Table 2.

(Example 16)
The same procedure as in Example 1 was carried out except that 56 dtex, 24-filament homopolyethylene terephthalate fiber was used for the warp and the antistatic polyester fiber of the present invention was used for the weft. Although the friction withstand voltage of the fabric was somewhat increased, it was within the scope of the present invention. The results are shown in Table 2.

[Comparative Examples 1 and 2]
The same procedure as in Example 1 was performed except that the amount of the organic electrolyte added to the base polymer described in Table 3 was changed. Comparative Example 1 had poor yarn forming properties, and Comparative Example 2 had insufficient antistatic performance.
[Comparative Examples 3 and 4]
It implemented by the same method as Example 1 except having changed the addition amount of the antistatic agent to the whole fiber of Table 3. In Comparative Example 3, the toughness of the raw yarn was insufficient, and the yarn production was poor. On the other hand, Comparative Example 4 had insufficient antistatic performance.

Claims (5)

A polyester fiber in which a polyether ester amide antistatic agent forms an independent phase dispersed in a streak pattern along the fiber axis, and the organic electrolyte is 0.05 to 10% by weight in the fiber, and the polyether ester An antistatic polyester fiber having an amide antistatic agent in an amount of 0.2 to 5% by weight and satisfying the following requirements (1) and (2) at the same time.
(1) The weight ratio of the organic electrolyte is polyester phase: polyether ester amide-based antistatic phase = 5: 95 to 99: 1
(2) The average diameter of the polyetheresteramide-based antistatic agent phase is 40 to 120 nm.   2. The antistatic polyester fiber according to claim 1, wherein the polyether ester amide antistatic agent has an independent phase aspect ratio of 30 or more and an average phase spacing of 0.5 to 2 μm. 3. The antistatic polyester fiber according to claim 1, wherein the specific resistance of the raw yarn is less than 100 × 10 ⁸ Ω · cm in a measurement environment at a temperature of 10 ° C. and a humidity of 10% RH. In the fiber, the phase of the polyether ester amide antistatic agent forms an independent phase dispersed in a streak form along the fiber axis, and the ratio of the number of continuous bars to the total number of independent phases is 50 per 1 μm ^{2 of} fiber longitudinal section. % Antistatic polyester fiber according to any one of claims 1 to 3.   An antistatic woven or knitted fabric comprising 50% by weight or more of the antistatic polyester fiber according to any one of claims 1 to 4.