JP2008013868A - Antistatic polyester fiber and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antistatic polyester fiber excellent in antistatic property, suppressed in whitening phenomenon caused by mechanical damage in a weaving knitting step or a reduction dyeing and finishing step, and excellent in operating stability, performances and quality stability. <P>SOLUTION: The antistatic polyester fiber contains 3-10 wt.% of polyetheresteramide-based antistatic agent which is compounded with 0.05-0.8 wt.% organic electrolyte, in polyetheresteramide derived from an ethylene oxide adduct of high-molecular weight bisphenols, wherein (1) the average particle diameter D of the polyetheresteramide-based antistatic agent particle in the fiber is 14-30 nm, (2) the ratio L/D of L [fiber length in axial direction (average length)] to D [diameter in cross section (average diameter)] of the polyetheresteramide-based antistatic agent particle is ≥130 and (3) friction-charged electrostatic potential is ≤1,500 V. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an antistatic polyester fiber capable of providing an excellent antistatic property and a knitted fabric excellent in quality by controlling a dispersion state of an antistatic component having excellent compatibility, and a method for producing the same. It is.

Polyester is widely used as a synthetic fiber because it has many excellent properties. However, polyester fibers are more hydrophobic than natural fibers such as wool and silk, regenerated fibers such as rayon and acetate, and acrylic fibers, so they are more likely to generate static electricity. There is a drawback that cluttering occurs.
In order to improve such drawbacks, various means have been proposed so far, for example, a method of applying an antistatic agent to the yarn surface by post-processing, a method of graft polymerizing a hydrophilic substance on the yarn surface, or a fiber component For example, a method of incorporating an antistatic substance into the material. However, all of these methods have problems in terms of durability, heat-resistant yarn-making stability and quality defects in the knitting and knitting process, and there are problems in industrialization.

  For example, in the method of applying an antistatic agent to the yarn surface, the antistatic agent is likely to disappear by a dyeing process or washing, and also when applied at the end of the fabric process, the durability is insufficient and the texture is stiff. Or there are various problems such as inability to use together with other post-processing. Further, the method of graft polymerization of a hydrophilic substance on the yarn surface has considerably improved the disappearance of the antistatic agent by washing, but has a problem in durability and texture. Furthermore, although the method of kneading the antistatic material improves the durability, the textile process and the whitening phenomenon during wearing are problematic. This whitening phenomenon is a phenomenon in which a part that has been mechanically damaged in the textile process becomes a defect in fabric quality, or a part that receives friction when worn is whitened, and the cause is a kneaded antistatic agent. This is because interfacial delamination occurs at the interface between the substance and polyester, resulting in fibrillation.

  And many methods using a composite spinning technique are proposed as a method of improving the fault accompanying these antistaticity provision. For example, a technique has been proposed in which a polyester containing a polyalkylene ether and an anionic surfactant is used as a core component and the polyester is used as a sheath component (see Patent Document 1). However, although this technique reduces whitening, polyalkylene ether is very soluble in water, so after the high-temperature dyeing process, some of the agent passes through the polyester sheath and is distilled off. As a result, slits are formed in the fiber axis direction, the antistatic property is unstable, and a composite spinning facility is required, which is disadvantageous in terms of cost.

Therefore, as a polyester antistatic fiber blended with a polymer type antistatic component having high molecular weight and heat resistance, a technology of polyester antistatic fiber containing a block polyether ester amide composition and a sulfonic acid metal salt compound has been proposed. (Patent Documents 2 and 3). However, these fibers also have the problem of the whitening phenomenon due to the interface peeling between the antistatic agent and the polyester as described above, and the antistatic agent presumably due to insufficient viscosity of the antistatic agent is too finely dispersed. Therefore, it was necessary to increase the amount of addition, which tended to be easily whitened.
JP 2006-2258 A JP-A-63-28211 Japanese Patent No. 2990689

  The present invention solves the above problems, suppresses whitening phenomenon due to mechanical damage in the excellent antistatic property, weaving and knitting process and weight loss dyeing finishing process, and is excellent in operational stability, performance and quality stability. An object of the present invention is to provide an antistatic polyester fiber.

The present invention includes 3 to 10% by weight of a polyether ester amide antistatic agent in which 0.05 to 0.8% by weight of an organic electrolyte is blended with a polyether ester amide derived from an ethylene oxide adduct of a high molecular weight bisphenol. Polyester fiber,
(1) The average particle diameter D of the particles of the polyetheresteramide antistatic agent in the fiber is 14 to 30 nm,
(2) The ratio L / D of L [fiber axis direction length (average length)] and D [cross-sectional diameter (average particle diameter)] of the polyetheresteramide-based antistatic agent particles is 130 or more,
(3) The frictional voltage is 1,500 V or less,
It is related with the antistatic polyester fiber characterized by these.
Here, the polyetheresteramide is an ethylene oxide adduct (b) of a polyamide (a) having a carboxyl group at both ends and having a number average molecular weight of 500 to 5,000 and a bisphenol having a number average molecular weight of 1,600 to 3,000. ) And a relative viscosity of 1.5 to 3.5 (0.5 wt%, m-cresol solution, 25 ° C.), a polyester compatibility parameter and the polyether ester amide The difference from the compatibility parameter is preferably in the range of ± 0.5 (J / cm ³ ) ^ 1/2.
The crimp rate of the antistatic polyester fiber of the present invention is preferably 10% or more.
Furthermore, in the antistatic polyester fiber of the present invention, the ratio of the inscribed circle diameter to the circumscribed circle diameter in the cross section of the fiber is preferably 0.1 or more and less than 1.
Furthermore, the antistatic polyester fiber of the present invention preferably has a single yarn fineness of 0.3 to 5 dtex and a filament count of 12 to 288.
Next, the present invention relates to a polyether ester antistatic agent in which 0.05 to 0.8% by weight of an organic electrolyte is blended with a polyether ester amide derived from an ethylene oxide adduct of a high molecular weight bisphenol. A spinning draft in which the shear rate (shear strain rate) in the discharge nozzle hole is 400 to 9,000 and the ratio of the speed V1 extruded from the discharge hole to the take-up roller speed V2 after melting the polyester composition containing wt% The present invention relates to a method for producing the antistatic polyester fiber, wherein melt spinning is performed in a ratio = V2 / V1 of 200 to 2,000.
Next, the present invention is a woven or knitted fabric woven and knitted using the antistatic polyester fiber, and the friction withstand voltage when the woven or knitted fabric is reduced by 20% or less by an alkali weight reduction process is 1,500V or less. The present invention relates to an antistatic woven or knitted fabric characterized by being.

  The present invention provides an antistatic polyester fiber excellent in operation stability, performance, and quality stability by suppressing the whitening phenomenon due to mechanical damage in the excellent antistatic, weaving and knitting process and weight reduction dyeing process. be able to.

The antistatic agent blended with the antistatic polyester fiber of the present invention is a polyether ester amide antistatic agent containing a predetermined amount of an organic electrolyte in a polyether ester amide derived from an ethylene oxide adduct of high molecular weight bisphenols. It is an agent.
Here, as the organic electrolyte, for example, at least one sulfonic acid selected from the group of dodecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, nonylbenzenesulfonic acid, hexadecylsulfonic acid and dodecylsulfonic acid, sodium, potassium And an alkali metal salt of a sulfonic acid formed from at least one alkali metal selected from the group of lithium and / or a phosphoric acid such as distearyl phosphate, and selected from the group of sodium, potassium and lithium Examples thereof include alkali metal salts of phosphoric acid formed from at least one alkali metal, and among them, metal salts of sulfonic acid such as sodium alkyl sulfonate are preferable.
The content of the organic electrolyte is 0.05 to 0.8% by weight, preferably 0.1 to 0.4% by weight, in the above antistatic agent. On the other hand, if it exceeds 0.8% by weight, it is not preferable because it does not disperse uniformly and forms an associated state, resulting in poor dispersibility and accompanying whitening.

  Here, the polyether ester amide used in the antistatic agent of the present invention is preferably a polyamide (a) having a carboxyl group at both ends and a number average molecular weight of 500 to 5,000 and a number average molecular weight of 1,600 to 3 Derived from ethylene oxide adducts (b) of 1,000 bisphenols.

The polyamide (a) having carboxyl groups at both ends is (1) a lactam ring-opening polymer, (2) a polycondensate of aminocarboxylic acid, or (3) a polycondensate of dicarboxylic acid and diamine.
Among these, the lactam of (1) includes caprolactam, enantolactam, laurolactam, undecanolactam and the like.
Examples of the aminocarboxylic acid (2) include ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminopergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid.
Examples of the dicarboxylic acid (3) include adipic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanedioic acid, and isophthalic acid.
Examples of the diamine include hexamethylene diamine, heptamethylene diamine, octamethylene diamine, and decamethylene diamine.
Those exemplified as the amide-forming monomer may be used in combination of two or more. Among these, caprolactam, 12-aminododecanoic acid and adipic acid-hexamethylenediamine are preferable, and caprolactam is particularly preferable.

The polyamide (a) is obtained by using a dicarboxylic acid component having 4 to 20 carbon atoms as a molecular weight adjusting agent and subjecting the amide-forming monomer to ring-opening polymerization or polycondensation by a conventional method in the presence thereof.
Examples of the dicarboxylic acids having 4 to 20 carbon atoms include fatty acid dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecadiic acid, dodecanedic acid; terephthalic acid, isophthalic acid, phthalic acid Aromatic dicarboxylic acids such as acid and naphthalenedicarboxylic acid; aliphatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid and dicyclohexyl-4,4-dicarboxylic acid; sodium 3-sulfoisophthalate, potassium 3-sulfoisophthalate, etc. Examples include alkali metal salts of 3-sulfoisophthalic acid.
Of these, preferred are aliphatic dicarboxylic acids, aromatic dicarboxylic acids and alkali metal salts of 3-sulfoisophthalic acid.

  The number average molecular weight of the polyamide (a) is usually 500 to 5,000, preferably 500 to 3,000. When the number average molecular weight is less than 500, the heat resistance of the polyether ester amide itself is lowered. On the other hand, when it exceeds 5,000, the reactivity is lowered, so that much time is required for producing the polyether ester amide.

In the ethylene oxide adduct (b) of bisphenols, bisphenols include bisphenol A (4,4′-dihydroxydiphenyl-2,2-propane), bisphenol F (4,4′-dihydroxydiphenylmethane), bisphenol S. (4,4′-dihydroxydiphenylsulfone) and 4,4′-dihydroxydiphenyl-2,2 butane are exemplified, and among these, bisphenol A is preferred.
The adduct (b) can be obtained by adding ethylene oxide to these bisphenols by a conventional method. In addition, other alkylene oxides (propylene oxide, 1,2-butylene oxide, 1,4-butylene oxide, etc.) can be used in combination with ethylene oxide, but the amount of other alkylene oxides is usually based on the amount of ethylene oxide. 10 weight or less.

  The number average molecular weight of the adduct (b) is usually 1,600 to 3,000, and it is particularly preferable to use one having an ethylene oxide addition mole number of 32 to 60. When the number average molecular weight is less than 1,600, the antistatic property becomes insufficient. On the other hand, when it exceeds 3,000, the reactivity is lowered, so that a great amount of time is required for producing the polyetheresteramide. The number average molecular weight is preferably 1,800 to 2,400, and the ethylene oxide addition mole number is more preferably 36 to 52.

  The above adduct (b) is used in the range of 20 to 80% by weight based on the total weight of the above (a) and (b). If the amount of the adduct (b) is less than 20% by weight, the antistatic property of the polyether ester amide is inferior. On the other hand, if it exceeds 80% by weight, the heat resistance of the polyether ester amide is lowered, which is not preferable.

  The relative viscosity of the polyether ester amide used in the present invention is 1.5 to 3.5 dl / g (0.5 wt%, m-cresol solution, 25 ° C.), preferably 2.0 to 3.0 dl / g. g. If it is less than 1.5 dl / g, the dispersed particle diameter of the antistatic agent becomes small and the antistatic property is insufficient. On the other hand, in the range exceeding 3.5 dl / g, it becomes the cause of yarn breakage.

Further, the composition of the polyether ester amide of the present invention is a very important requirement for compatibility with the polyester. In the polyether ester amide used in the present invention, the difference between the compatibility parameter of the polyester and the compatibility parameter of the polyether ester amide is within the range of ± 0.5 (J / cm ³ ) ^ 1/2. It is necessary to have an electric agent polymer composition. For example, in the case of polyethylene terephthalate, since the compatibility parameter is 20.9 (J / cm ³ ) ^ 1/2, the compatibility parameter of the polyether ester amide is in the range of 20.4 to 21.4. It is necessary to be in Beyond this range, the interfacial adhesion between the polyester and the antistatic polymer is insufficient, and a whitening phenomenon due to interfacial delamination occurs due to friction during post-processing and wearing. Preferably, it is within ± 0.3 (J / cm ³ ) ^ 1/2 with respect to the base polyester.

Although the following manufacturing method (1) or manufacturing method (2) is illustrated as a manufacturing method of the polyetheresteramide of this invention, it is not specifically limited.
Production method (1): A method in which an amide-forming monomer and a dicarboxylic acid are reacted to form a polyamide (a), an ethylene oxide adduct (b) of a bisphenol is added thereto, and a polymerization reaction is performed at high temperature and under reduced pressure.
Production method (2): An amide-forming monomer and dicarboxylic acid and the above adduct (b) are simultaneously charged into a reaction vessel, and subjected to pressure reaction at high temperature in the presence or absence of water, to form a polyamide (a ) And then a polymerization reaction between (a) and (b) under reduced pressure.
Moreover, a well-known esterification catalyst is normally used for said polymerization reaction. Examples of the catalyst include antimony catalysts such as antimony trioxide, tin catalysts such as monobutyltin oxide, titanium catalysts such as tetrabutyl titanate, zirconium catalysts such as tetrabutyl zirconate, and metal acetates such as zinc acetate. And system catalysts. The usage-amount of a catalyst is 0.1 to 5 weight% normally with respect to the total weight of (a) and (b).

  The amount of the polyether ester amide antistatic agent added to the polyester needs to include 3 to 10% by weight. Preferably, it is the range of 6-9 weight%. If it is less than 3% by weight, the antistatic property is insufficient. On the other hand, if it exceeds 10% by weight, crimping performance is incurred due to deterioration in the condition of the yarn forming process, strength reduction, and heat setting property.

  Here, examples of the polyester used in the present invention include polyalkylene terephthalate and polyalkylene phthalate. Among them, the former terephthalic acid is the main acid component, and the alkylene glycol component having 2 to 6 carbon atoms, that is, ethylene glycol, triethylene. Polyesters having at least one glycol selected from methylene glycol, tetramethylene glycol, pentamethylene glycol and hexamethylene glycol as the main glycol component are targeted.

  Such polyester may be produced by any method. For example, when describing polyethylene terephthalate, terephthalic acid and ethylene glycol are directly esterified, terephthalic acid lower alkyl ester such as dimethyl terephthalate and ethylene glycol are directly esterified, or terephthalic acid and ethylene glycol are directly esterified. It is produced by reacting with an oxide to produce a glycol ester of terephthalic acid and / or its low degree of polymerization, and then subjecting this product to a polycondensation reaction until it reaches the desired degree of polymerization by heating under reduced pressure. The

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 isophthalic acid, phthalic acid, dibromoterephthalic acid, naphthalene dicarboxylic acid, diphenyl carboxylic acid, diphene ethane dicarboxylic acid, bifunctional aromatic carboxylic acid such as β-oxyethoxybenzoic acid, and sebacin. Bifunctional aliphatic dicarboxylic acid such as acid, adipic acid and oxalic acid, 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 ( Aliphatic, alicyclic and aromatic diols such as 3,5-dibromo-4- (2-hydroxyethoxy) phenyl) propane can be mentioned.

  Further, the above-mentioned polyester may be obtained by blending and melting a small amount of other polymers as required, or 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 of course contain conventionally known antioxidants and anti-coloring agents as well as ordinary polyesters.

  The intrinsic viscosity [η] (o-chlorophenol in 35 ° C.) of the polyester is usually about 0.46 to 1.0 dl / g, preferably about 0.54 to 0.92 dl / g.

The dispersion state of the polyether ester amide antistatic agent of the present invention in the polyester fiber is an important invention requirement.
That is, first, (1) the average particle diameter D of the particles of the polyetheresteramide antistatic agent in the fiber needs to be in the range of 14 to 30 nm. Preferably, it is the range of 15-20 nm. If the thickness is less than 14 nm, the friction withstand voltage exceeds 2,500 and the antistatic property is insufficient. On the other hand, if the size exceeds 30 nm, the thickness of each filament may be uneven, or the yarn may be broken or drawn. Processing yarn is a problem.
Here, the measurement of the average particle diameter D is as described later.
The average particle diameter D can be easily adjusted by the shear rate at the time of melt spinning and the spinning draft rate.

(2) L [fiber axis direction length (average length)] / D [cross-sectional diameter (average particle diameter)] in the fibers of the polyetheresteramide antistatic agent particles is 130 or more. is necessary. Preferably, it is 200-400. In order to impart antistatic properties, it is important to provide a field where the antistatic agent is in a long continuous state in the fiber and the charge easily moves. Therefore, the longer the length of the agent in the fiber axis direction, the better.
Here, the measurement of L / D is as described later.
L / D can be easily adjusted by the shear rate at the time of melt spinning and the spinning draft rate.

(3) As the antistatic performance, the frictional voltage must be 1,500 V or less. Preferably, it is 0-1,000V. If the voltage exceeds 1,500 V, clothing clinging and static electricity are likely to occur.
The frictional voltage is a value measured according to JIS L1094 as will be described later.
The frictional voltage can be easily adjusted by the amount of the antistatic agent and its dispersion shape (average particle diameter).
Similarly to the above, the woven or knitted fabric woven and knitted using the antistatic polyester fiber of the present invention preferably has a friction withstand voltage of 1,500 V or less, more preferably 0 when it is subjected to a weight reduction process of 20% or less by an alkali weight reduction process. ~ 1,000V.

  The antistatic polyester fiber of the present invention is preferably a crimped yarn exhibiting stretch performance such as false twisted yarn in addition to flat yarn. In this case, the antistatic polyester fiber of the present invention preferably has a crimp rate of 8% or more. If it is less than 8%, the fabric swells and stretchability is insufficient. The crimp rate is more preferably 10 to 20%. With the recent trend toward casual clothing, there are many knitted products, and sports clothing, thin knitted products, and products with anti-static properties are in high demand for comfort. Further, in vehicle seats such as car seats, antistatic durability and friction resistance are required, and the antistatic crimped yarn of the present invention is suitable.

Further, the cross-section of the antistatic polyester fiber (polyester flat yarn and crimped yarn) of the present invention is preferable because it has various cross-sectional shapes in addition to the round shape, thereby providing a function. For example, as the antistatic polyester fiber of the present invention, it is possible to form various deformed / multi-lobe cross sections by combining various round holes and slit holes among the mouthpiece discharge holes in addition to the cross section.
For example, in the present invention, a modified cross-section fiber in which the ratio of the inscribed circle diameter to the circumscribed circle diameter of the fiber cross section (degree of irregularity) is 0.1 or more and less than 1 is preferable. More preferably, it is 0.2-0.5. For irregular cross-sections of less than 1, there are significant effects in terms of functionality such as water-absorbing and quick-drying and heat retention due to an increase in inter-fiber voids, as well as sensitivity and a deep color effect. Cross-sectional arrangement is possible and a requirement that can be achieved in the present invention. On the other hand, if it is less than 0.1, a discharge hole such as a narrow slit hole or a combination of a slit hole and a round hole is required, which is not preferable because discharge failure or malfunction of the spinning process due to anisotropic cooling occurs.

Further, 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. If it is less than 0.3 dtex, stability in the spinning process is lacking. On the other hand, if it exceeds 5 dtex, the texture is hard and not preferable. More preferably, it is 0.5-3 dtex.
Furthermore, the antistatic polyester fiber of the present invention preferably has a filament count of 12 to 288 in order to meet the needs for weight reduction (thinning). A technique for reducing the number of halves, such as twelve, is also important, but less than twelve is not preferable because the spinning discharge amount is small and the heat resistance stability of the polymer becomes poor. On the other hand, there is a high need for a fine denier and high multi-configuration, but if the number exceeds 288, the spinning cooling process becomes uneven among the filaments, and it is difficult to make the single yarn fineness uneven and stabilize the spinning tone. . More preferably, the number of filaments is 20-144.

In the antistatic polyester fiber of the present invention, as a requirement for determining the dispersion state of the antistatic agent, shearing in the base and spinning draft after discharging the base in the spinning process in the production method are important. This is a requirement necessary to achieve antistatic properties and quality by setting the particle size and length of the antistatic agent within a certain range. That is, when melt-spinning the antistatic polyester fiber of the present invention, a polyester composition in which the above-described antistatic agent of the present invention is blended with polyester is melted and then melt-spun, first, the following formula 1 in the discharge hole: It is necessary to set the nozzle hole diameter and the discharge amount so that the shear rate (shear rate) (formula 1) represented by the formula (1) falls within the range of 400 to 9,000. If the hole diameter is too large relative to the discharge amount, the dispersion (particle size reduction) action of the antistatic agent in the discharge hole is small, so that the dispersion of the particle diameter is large, which is likely to cause yarn breakage. On the other hand, if the discharge hole diameter is too small and the dispersion action is too large, the particle diameter becomes small and the antistatic effect is not achieved. Therefore, the shear rate needs to be in the range of 400 to 9,000, and preferably in the range of 600 to 8,000.
Shear rate: Vs (sec-1) = 4Q (cm3 / sec) / πr (cm) ^ 3
Q: Polymer discharge rate per discharge hole (cm ³ / sec)
r: Radius of the discharge hole (cm ³ )

  When the polyester composition is melt-spun, the spinning draft ratio = V2 / V1, which is the ratio between the extrusion speed V1 from the discharge hole and the take-up roller speed V2, must be in the range of 200 to 2,000. It is. It has a round to oval shape with a range of particle sizes within the discharged blend polymer stream, in which the entire polymer stream is gradually stretched and accelerated while being cooled, resulting in a glass transition temperature. At this point, the take-up speed V2 has been reached. The acceleration dV / dx during that time increases as the spinning draft increases, and the polymer stream undergoes large deformation. Therefore, in order to stretch the antistatic agent, the draft needs to be in a large range, that is, 200 to 2,000. Here, when it is less than 200, the extension of the antistatic agent is insufficient, and the L / D is less than 130, and the antistatic property is insufficient. On the other hand, when it exceeds 2,000, the large deformation action is excessive and there is a problem of spinning yarn, which is insufficient. The spinning draft rate (V2 / V1) is preferably 300 to 1,000.

Hereinafter, the present invention will be described in detail using specific examples.
In Examples,% is based on weight unless otherwise specified. Moreover, each measuring method was implemented in the following ways.
(1) Measurement of particle size of antistatic agent In order to measure the polyester fiber of the present invention with a transmission electron microscope, a fiber cross section and a fiber axial section with a thickness of 100 nm were prepared and observed. At this time, the diameter of the particles in the fiber cross section was measured at n = 100, and the average value was calculated.
(2) Measurement of L / D of particles of antistatic agent In order to measure the polyester fiber of the present invention with a transmission electron microscope, a fiber axial section having a thickness of 100 nm was prepared and observed. At this time, the length of the antistatic agent particles in the fiber axis direction is measured at n = 50, and the average value is calculated. The ratio of the average L value and the average D value of (1) was calculated to obtain the L / D value.
(3) Deformation degree ratio Ratio of inscribed circle to circumscribed circle of fiber cross section = inscribed circle / circumscribed circle was calculated.

(4) Friction voltage measurement The polyester fiber of the present invention was measured according to the JIS L 1094 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. and a relative humidity of 40 ± 2%. The warp yarn direction, the weft method, and each n = 5 were measured, and the white cloth attached to cotton specified in JIS L 0803 was used as the friction cloth.

(5) Crimp rate measurement Make a small wrinkle of 3,000 or 4,000 dtex according to the fineness, apply a load of 2mg / De + 0.1g / De, and length (L ₀ ) after 1 minute, 2mg / De water at room temperature Soaked for 20 minutes and air-dried for 24 hours, then applied 2mg / De + 0.1g / De, length after 1 minute (L ₂ ), applied 2mg / De, and length after 1 minute (L ₃ ) The value of n = 2 measured by the following equation is shown.
Crimp rate (%) = {(L ₂ −L ₃ ) / L ₀ } × 100

(6) Whitening test The test cloth which finished the dyeing process was prepared. The test cloth was slid about six times using an electric iron preheated to 150 ± 5 ° C. The temperature is the surface temperature at the center of the bottom surface of the electric iron, and other temperatures may be used as necessary. Further, the weight was reduced by 15% using a hot alkaline aqueous solution. The color measurement n = 2 of the L value (whitening degree) of these two externally applied test cloth (L1) and the externally applied test cloth (L0) was performed and obtained by the following equation. The color difference value was defined as whitening.
Whitening property = L1-L0
(7) Spinning condition A single-spindle melt-spinning machine has been operated continuously for one week, except for the thread breakage caused by human or mechanical factors. The number of yarn breaks per day was calculated, and the spinning condition was judged according to the following criteria.
○: Number of yarn breaks 1 to 2 times a day Δ: Number of yarn breaks 3 to 4 times a day ×: Number of yarn breaks 5 times or more a day (8) Texture As described in Table 4.

Examples 1-4, Comparative Examples 1-3
Polyethylene terephthalate chips (IV = 0) obtained by drying the polyether ester amide (PEEA) shown in Table 1 (containing 0.8% Na alkyl sulfonate as an ionic substance) at 80 ° C. and dried at 160 ° C. .64 dl / g), and melted at a melting temperature of 295 ° C., and through a pack in which a 400M filter is arranged on the upper part of the base, as shown in Table 1, the base hole diameter and hole number conditions and addition amount were changed. The polymer was discharged and wound up. The POY raw yarn (partially oriented undrawn yarn) was drawn and heat set at a draw ratio of 1.6 times with a roller having a preheating temperature of 90 ° C. and a slit heater having a set temperature of 170 ° C. to produce a drawn yarn. The fiber was put into a circular knitting state with a 20G cylinder knitting machine, refined at 80 ° C., washed with water and dried, and then high-pressure dyed at 120 ° C. with owf 4%. The friction withstand voltage was measured using the dyed sample. The results are shown in Table 1.
In Examples 1, 2, 3, and 4, the amount of polyetheresteramide (hereinafter referred to as “PEEA”) is appropriate, and the yarn forming conditions such as the shear rate in the die and the draft are within the scope of the present invention. An antistatic polyester fiber excellent in performance and quality was obtained, satisfying the particle size of the antistatic agent and the length in the fiber axis direction, without frictional voltage and whitening phenomenon.

  On the other hand, in Comparative Example 1, since the shear rate in the die is too large, the particle diameter of PEEA becomes small and the antistatic performance is insufficient. In Comparative Example 2, since the amount of PEEA added is small, the antistatic property is insufficient. On the other hand, in Comparative Example 3, since the amount of PEEA added is too large, yarn breakage frequently occurs in spinning, and the present invention. Not satisfying. In Comparative Example 4, since the number of holes was large, it was estimated that the spinning draft was mainly increased due to an increase in the spinning draft, and stable production was difficult.

Examples 5-9, Comparative Examples 4-8
Experiments were carried out in the same manner as in Example 1 using PEEAs having different molecular weights of various polyamide parts and different molecular weights of bisphenol A-containing ethylene oxide ester parts and different viscosities. The results are shown in Table 2.
In Examples 5 and 6, the molecular structure and viscosity of PEEA were optimum, and performance satisfying the present invention was obtained.
In Example 5, since the molecular weight of the polyamide was small, the heat resistance in the spinning process was insufficient and the yarn breakage occurred during spinning, but the antistatic property was good. In Example 6, because the molecular weight of the polyamide part is large, the viscosity is high and the compatibility with PET is insufficient, so that the dispersed particle size of PEEA becomes large, and there is a problem in whitening and spinning stability. The antistatic property was good. In Example 8, since the molecular weight of ethylene oxide was small, there were some problems in spinning tone and whitening due to insufficient heat resistance, but antistatic properties were good. In Example 9, since the molecular weight of ethylene oxide was large, the compatibility was insufficient, the spinning tone was not stable, and there was a problem with the whitening phenomenon, but the antistatic property was good.
On the other hand, in Comparative Example 4, since the viscosity is low, the dispersed particle size of PEEA becomes small (particles are stretched and L / D is large), and the antistatic property is insufficient, which does not satisfy the present invention. In Comparative Example 5, since the viscosity was large, the particle size of PEEA was large, whitening was large, and there was a problem in spinning stability. In Comparative Example 6, in the case of the antistatic agent using adipic acid as the ester component of the polyether ester and not containing the bisphenol A group, the viscosity was low, the particle size was small, and the antistatic property was insufficient. In Comparative Example 7, in the system in which polyethylene glycol having a molecular weight of 20,000 and sodium alkyl sulfonate were added to the antistatic agent, the particle size was small but antistatic property was sufficient, but due to lack of compatibility, whitening was large. There were problems with post-processing and durability. In Comparative Example 8, the polyether ester is used as an antistatic agent, and the compatibility is insufficient, so that the particle size is increased and consequently whitening is large.

Examples 11-14
Using a POY yarn spun in the same manner as in Example 1, a false twisted yarn was produced with a DTY processing machine under the false twist conditions of draw ratio = 1.6 and D / Y = 2.0. Moreover, POY spinning was produced using a deformed die other than the cross section, and a drawn yarn was produced in the same manner as in Example 1. The results are shown in Table 3.
In Example 11, since the heater temperature was as low as 120 ° C., the crimp rate was small, but the antistatic property was good. In Example 12, since the false twist heater temperature was appropriate at 200 ° C., an antistatic false twist yarn having a crimped stretch performance as high as 22% was obtained.
In Examples 13 and 14, respectively, a Y-shaped discharge hole with a slit width of 0.1 mm, and a discharge hole that similarly forms a multi-lobal 8-leaf section with a slit width of 0.1 mm, and a triangular section and an 8-leaf section. A POY yarn for yarn was produced at a spinning speed of 3,000 m / min and stretched in the same manner as in Example 1. These satisfied the particle size, had good spinning tone, and were able to produce deformed antistatic yarns with no whitening problem. Here, the shear rate of the irregular cross section was calculated by calculating the equivalent diameter from the cross sectional area.

Examples 15-18
Experiments with different single yarn fineness and number of filaments were performed in the same manner as in Example 1 except that the discharge amount and the number of holes in the die were changed. The results are shown in Table 4. In Examples 15 to 18, antistatic fibers excellent in antistatic properties, yarn-making stability, and quality were obtained. In Examples 15 and 18, the single yarn fineness was small, and sensibility characteristics such as extra fineness and powder touch were also obtained.

Since the antistatic polyester fiber of the present invention has excellent antistatic properties, antistatic durability and dyeing quality, it is useful for applications such as clothing.

Claims (8)

A polyester fiber containing 3 to 10% by weight of a polyetheresteramide-based antistatic agent in which 0.05 to 0.8% by weight of an organic electrolyte is blended with a polyetheresteramide derived from an ethylene oxide adduct of a high molecular weight bisphenol. And
(1) The average particle diameter D of the particles of the polyetheresteramide antistatic agent in the fiber is 14 to 30 nm,
(2) The ratio L / D of L [fiber axis direction length (average length)] and D [cross-sectional diameter (average particle diameter)] of the polyetheresteramide-based antistatic agent particles is 130 or more,
(3) The frictional voltage is 1,500 V or less,
Antistatic polyester fiber characterized by being. The polyether ester amide is derived from an ethylene oxide adduct (b) of a polyamide (a) having a carboxyl group at both ends and having a number average molecular weight of 500 to 5,000 and a bisphenol having a number average molecular weight of 1,600 to 3,000. A polyetheresteramide having a relative viscosity of 1.5 to 3.5 dl / g (0.5 wt%, m-cresol solution, 25 ° C.), the compatibility parameter of the polyester and the phase of the polyetheresteramide The antistatic polyester fiber according to claim 1, wherein the difference from the solubility parameter is in the range of ± 0.5 (J / cm ³ ) ^ 1/2.   The organic electrolyte is selected from the group of at least one sulfonic acid selected from the group of dodecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, nonylbenzenesulfonic acid, hexadecylsulfonic acid and dodecylsulfonic acid, and sodium, potassium and lithium Formed from at least one alkali metal salt of sulfonic acid and / or distearyl phosphate and at least one alkali metal selected from the group of sodium, potassium and lithium 3. The antistatic polyester fiber according to claim 1, which is an alkali metal salt of phosphoric acid.   The antistatic polyester fiber according to any one of claims 1 to 3, wherein the crimp rate of the fiber is 10% or more.   The antistatic polyester fiber according to any one of claims 1 to 4, wherein a ratio of an inscribed circle diameter to a circumscribed circle diameter in a cross section of the polyester fiber is 0.1 or more and less than 1.   The antistatic polyester fiber according to any one of claims 1 to 5, wherein the single yarn fineness is in the range of 0.3 to 5 dtex and the number of filaments is in the range of 12 to 288.   Polyester composition containing 3 to 10% by weight of a polyetheresteramide antistatic agent in which 0.05 to 0.8% by weight of an organic electrolyte is blended with a polyetheresteramide derived from an ethylene oxide adduct of high molecular weight bisphenols After the melt, the shear rate (shear strain rate) in the discharge nozzle hole is 400 to 9,000, and the spinning draft rate = V2 / V1 which is the ratio of the speed V1 pushed out from the discharge hole and the take-up roller speed V2 is The method for producing antistatic polyester fiber according to any one of claims 1 to 6, wherein the melt spinning is performed in a range of 200 to 2,000. A woven or knitted fabric woven and knitted using the antistatic polyester fiber according to any one of claims 1 to 6, wherein the woven or knitted fabric has a friction withstand voltage of 1,500 V when it is subjected to a weight reduction process of 20% or less by an alkali weight reduction process. An antistatic woven or knitted fabric characterized by: