JP2008001731A - Antistatic copolyester composition and textile product comprising the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an antistatic copolyester composition for providing a solid fiber composed of a homopolymer composition component with nonconventional antistatic properties, a fiber and a textile product comprising the same. <P>SOLUTION: The antistatic copolyester composition comprises a copolyester which has a main repeating unit composed of ethylene terephthalate, is copolymerized with 1-20 mass% based on the mass of the obtained copolyester of a specific diol component, has an intrinsic viscosity of ≥0.5dL/g and contains 0.2-10 mass% based on the mass of the obtained polyester composition of a polyoxyethylene glycol having a number-average molecular weight of ≥10,000 and ≤100,000 and 0.1-5 mass% based on the mass of the obtained polyester composition of a metal alkylsulfonate and/or a metal alkylbenzene sulfonate. The yarn is obtained by melt spinning the same. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an antistatic copolyester composition, a fiber and a fiber product comprising the same. More specifically, the present invention relates to a polyester composition that exhibits excellent antistatic properties, and particularly exhibits excellent antistatic properties in a solid fiber composed of a single component of the composition, and a fiber and a fiber product comprising the same.

  Polyesters, especially polyethylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate and polytetramethylene terephthalate are widely used in fibers, films or other molded products because of their excellent mechanical, physical and chemical performance. Yes. Among them, polyethylene terephthalate is particularly excellent in mechanical properties, chemical properties, moldability, etc., and has been used for polyester fibers for a long time. However, since polyester is hydrophobic, its use in fields where antistatic properties are required is limited.

  In order to meet such demands, attempts have been made to impart antistaticity by imparting hydrophilicity to polyester, and many proposals have been made so far. For example, as one of attempts to impart antistatic properties to polyester fibers, a method of blending polyoxyalkylene glycol with polyester is known (for example, see Patent Document 1). However, in order to exhibit sufficient antistatic properties to the polyester fiber by this method, a large amount of 15 to 20% by weight of polyoxyalkylene glycol is required, and the obtained antistatic polyester fiber has physical properties, particularly thermal properties. It is greatly reduced and inferior in washing fastness, so it cannot be used.

In order to eliminate such drawbacks, for example, a polyester having a small amount (about 5% or less) of an antistatic agent composed of polyoxyalkylene glycol and a sulfonic acid metal salt is melt-spun into a hollow fiber. Has proposed a method in which most of the antistatic agent is coagulated and localized around the fiber hollow portion (see, for example, Patent Document 2). However, since the fiber obtained by this method is a hollow fiber, its use has been limited.
On the other hand, although a method for localizing the antistatic agent at a high concentration in the core portion of the core-sheath composite fiber has been proposed (see, for example, Patent Documents 3 to 5), the yarn-making cost increases because it is a composite fiber. In addition, there has been a drawback that it is difficult to produce ultrafine fibers, which has been attracting attention in recent years.

Also, in place of water-soluble polyoxyethylene glycol commonly used in conventional antistatic polyester fibers, polyoxyethylene polyether made water insoluble by copolymerizing ethylene oxide with a specific higher olefin oxide. It has been proposed to solve the above problem by using (see, for example, Patent Documents 6 to 8).
However, in this method, the water-insolubilized polyoxyethylene-based polyether used is expensive and the antistatic property of the resulting fiber is not sufficient.

Japanese Examined Patent Publication No. 39-5214 Japanese Patent Publication No. 60-56802 Japanese Examined Patent Publication No. 61-6883 Japanese Patent Laid-Open No. 55-122020 JP-A 61-28016 JP-A-3-139556 JP 2002-309486 A JP 2003-129336 A

  An object of the present invention is an antistatic copolyester composition suitable for fibers, which are solid fibers composed of a single polymer composition component, and can impart an antistatic property that has not existed in the past. Is to provide fibers and textile products.

As a result of intensive studies in view of the above prior art, the present inventors have completed the present invention.
That is, the object of the present invention is that the main repeating unit is composed of ethylene terephthalate, and at least one diol component selected from the following general formula groups (I) to (III) is selected from 1 to 20% by mass copolymerized polyester having an intrinsic viscosity of 0.5 dL / g or more, and having a number average molecular weight of 10,000 or more and 100,000 or less, the polyoxyethylene glycol can be obtained in a mass of 0.2 to 10% by mass, 0.1 to 5% by mass of the antistatic copolyester composition with respect to the mass of the polyester composition from which the alkylsulfonic acid metal salt and / or the alkylbenzenesulfonic acid metal salt can be obtained. Can be achieved by things.
[Formula 1]
H- (OR) _n -OH (I)
[In the above formula, the functional group R is an alkylene group having 2 to 12 carbon atoms, and when R is 2 carbon atoms, n = 2 to 15 and when R is 3 or more carbon atoms, n = 1 to 15 is represented. ]
_{HOCH 2 CH 2 O-X-} OCH 2 CH 2 OH (II)
[In the above formula, the functional group X represents an arene group. ]
_{HOCH 2 -Y-CH 2 OH (} III)
[In the above formula, the functional group Y represents a cycloalkyl group or an arene group. ]

  According to the present invention, it is possible to impart high antistatic properties to solid fibers made of a single polymer composition component without taking the form of conventional hollow fibers and core-sheath type composite fibers. It is possible to manufacture antistatic fibers using yarns and modified yarns, and textile products using them.

  The present invention will be described in detail below. The polyester composition of the present invention comprises a copolymer polyester obtained by copolymerizing a specific amount of at least one diol component selected from the above general formula groups (I) to (III), wherein the main repeating unit is obtained from tylene terephthalate, and It is a polyester composition containing a specific amount of polyoxyethylene glycol having a specific number average molecular weight and an alkylsulfonic acid metal salt and / or an alkylbenzenesulfonic acid metal salt, respectively.

  As the copolymerized polyester in the present invention, a polyester mainly composed of an ethylene terephthalate unit obtained by a polycondensation reaction of terephthalic acid and ethylene glycol is preferably used. Here, “main” means that 70 mol% or more of all repeating units are ethylene terephthalate units.

  As a method for producing the copolyester (mainly composed of polyethylene terephthalate) used in the present invention, a generally known production method is used. That is, first, a method of directly esterifying a dicarboxylic acid component such as terephthalic acid and a glycol component such as ethylene glycol, or a transesterification of a lower alkyl ester of a dicarboxylic acid component such as dimethyl terephthalate and a glycol component such as ethylene glycol. A glycol ester of dicarboxylic acid and / or a low polymer thereof is produced by a method of transesterification in the presence of a reaction catalyst. Then, the reaction product is heated under reduced pressure in the presence of a polymerization catalyst and subjected to a polycondensation reaction until a predetermined polymerization degree is obtained, whereby a desired copolymerized polyester is produced. The timing of adding the copolymer component will be described later. Preferred examples of the transesterification reaction catalyst include calcium compounds, magnesium compounds, manganese compounds, zinc compounds, and titanium compounds. Preferred examples of the polymerization catalyst include antimony compounds, germanium compounds, titanium compounds, and aluminum compounds. Further, in the direct esterification reaction, since the raw material dicarboxylic acid itself also serves as a catalyst, it is not essential to add a catalyst compound separately from the raw material.

The copolymerized polyester used in the present invention is copolymerized with 1 to 20% by mass of one or more diol components selected from the following general formula groups (I) to (III) with respect to all repeating units of the polyester. There is a need.
[Formula 2]
H- (OR) _n -OH (I)
[In the above formula, the functional group R is an alkylene group having 2 to 12 carbon atoms, and when R is 2 carbon atoms, n = 2 to 15 and when R is 3 or more carbon atoms, n = 1 to 15 is represented. ]
_{HOCH 2 CH 2 O-X-} OCH 2 CH 2 OH (II)
[In the above formula, the functional group X represents an arene group. ]
_{HOCH 2 -Y-CH 2 OH (} III)
[In the above formula, the functional group Y represents a cycloalkyl group or an arene group. ]

  In the above formula (I), examples of the functional group R include an ethylene group, a 1-methylethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, and a 2-ethylhexyl group. Regarding the above formula (II), the functional group X represents an arene group, that is, a divalent aromatic group. Specifically, the functional group X represents an o-phenylene group, an m-phenylene group, a p-phenylene group, 4 4′-biphenyl group, 4, 4 ′, 4 ″ -terphenyl group {1,4-bis (4′-phenyl) phenyl group}, bis (4-phenyl) methane group, 2,2-bis ( 4-phenyl) propane group or 1,1-bis (4-phenyl) cyclohexane group can be exemplified. Furthermore, regarding the general formula group (III), the functional group Y represents a cycloalkyl group, an arene group {arene group, divalent aromatic group}, specifically a 1,4-cyclohexylene group, o- Phenylene group, m-phenylene group, p-phenylene group, 4,4′-biphenyl group, 4,4 ′, 4 ″ -terphenyl group {1,4-bis (4′-phenyl) phenyl group}, bis A (4-phenyl) methane group, a 2,2-bis (4-phenyl) propane group, or a 1,1-bis (4-phenyl) cyclohexane group can be mentioned. In the case of the diol component of the above formula (I), a diol component having a number average molecular weight of less than 400 is preferable.

  Examples of the compounds represented by the general formula groups (I) to (III) include diethylene glycol, triethylene glycol, tetraethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, Neopentylene glycol, 1,6-hexanediol, 1,10-decanediol, polyethylene glycol having a number average molecular weight of 1000 or less, polypropylene glycol, polytrimethylene glycol, polytetramethylene glycol, poly (2-ethylhexyleneoxy) Glycol, bis [4- (2-hydroxyethoxy) phenyl] methane, 2,2-bis [4- (2-hydroxyethoxy) phenyl] propane, 1,3-bis (2-hydroxyethoxy) benzene, 1,4 -Bis (2-hydroxyethoxy) , 1,1-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,3-bis (hydroxymethyl) benzene, 1,4-bis (hydroxymethyl) benzene, 1,3-bis (4-hydroxymethyl) Phenyl) benzene and 1,4-bis (4-hydroxymethylphenyl) benzene. Among these, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, number From the group consisting of polyethylene glycol having an average molecular weight of 650 or less, 2,2-bis [4- (2-hydroxyethoxy) phenyl] propane, 1,3-bis (2-hydroxyethoxy) benzene, and 1,4-cyclohexanedimethanol It is preferably at least one component selected. The polyethylene glycol having a number average molecular weight of 650 or less is more preferably a polyethylene glycol having a number average molecular weight of less than 400. When the compound to be copolymerized is not a compound group represented by these general formula groups (I) to (III), the antistatic property may not be good, which is not preferable.

  Moreover, the copolymerization amount of the compound represented by general formula group (I)-(III) needs to be 1-20 mass% with respect to the mass of the copolymerized polyester obtained. When the copolymerization amount is less than 1% by mass, the antistatic property of the obtained polyester fiber becomes insufficient. When the copolymerization amount exceeds 20% by mass, characteristics such as heat resistance and dimensional stability inherently possessed by the polyester are impaired. Therefore, it is not preferable. The copolymerization amount of the compounds represented by the general formula groups (I) to (III) is preferably in the range of 1 to 17% by mass, and more preferably in the range of 1 to 15% by mass.

  Here, the timing of addition of the compounds of the general formula groups (I) to (III) during the production of the copolyester is not particularly limited in the production process of the copolyester, but after the esterification reaction or transesterification reaction. Any stage may be used. In particular, after the end of the esterification reaction or transesterification reaction, or when the thermal decomposition point of the compounds of the general formula groups (I) to (III) is low, a stage in the middle of the transesterification reaction or after the end of the transesterification reaction is preferable.

  The intrinsic viscosity (solvent: orthochlorophenol, measurement temperature: 35 ° C.) of the copolyester composition of the present invention is not particularly limited, but it should be 0.5 dL / g or more, 0.5-1 It is preferably in the range of 0.0 dL / g. When the intrinsic viscosity is less than 0.5 dL / g, mechanical properties of the resulting polyester fiber become insufficient, and when it exceeds 1.0 dL / g, the melt moldability is lowered, which is not preferable. The intrinsic viscosity is more preferably in the range of 0.6 to 0.8 dL / g. In order to make the intrinsic viscosity within this range, it can be obtained by melt polymerization for a predetermined period of time in an atmosphere of an appropriate degree of vacuum at a temperature at which the copolyester is in a molten state and does not decompose. A trader can adjust the temperature, degree of vacuum (pressure), and time after trial and error. In addition, the intrinsic viscosity in the above range can be obtained by using a solid phase polymerization method.

  The content of the copolymer polyester in the antistatic copolyester composition of the present invention is 85% by mass or more and 99.7% by mass or less. When the content of the copolyester is less than 85% by mass, it is difficult to maintain the strength of the finally obtained polyester fiber. On the other hand, if it exceeds 99.7% by mass, the total blending amount of polyoxyethylene glycol serving as the antistatic agent and the metal salt of alkyl sulfonic acid and / or metal salt of alkyl benzene sulfonic acid is small, so that it is sufficient. It becomes difficult to develop antistatic properties. The content of the copolymer polyester in the antistatic copolyester composition of the present invention is preferably 90% by mass or more and 99.5% by mass or less, and more preferably 95% by mass or more and 99.3% by mass or less.

  The copolymerized polyester composition of the present invention needs to contain a polyoxyethylene glycol having a number average molecular weight of 10,000 or more and 100,000 or less in a range of 0.2 to 10% by mass with respect to the mass of the entire polyester composition. . Here, when the number average molecular weight of polyoxyethylene glycol is less than 10,000, the antistatic property of the obtained polyester fiber becomes insufficient, and when it exceeds 100,000, the thermal stability of the polyester becomes insufficient, which is not preferable. The number average molecular weight of polyoxyethylene glycol is preferably in the range of 12000 to 50000, and preferably in the range of 15000 to 30000. Here, the polyoxyethylene glycol used in the present invention is a polyether polymer composed of ethylene glycol, and both ends thereof are hydroxyl groups, or one or both ends thereof are sealed with an alkyl group or an acyl group. It may be. Further, when the content of polyoxyethylene glycol is 0.2% by mass or less with respect to the mass of the whole polyester composition, the antistatic property of the obtained polyester fiber becomes insufficient, and when the content exceeds 10% by mass, copolymerization occurs. In addition to the insufficient thermal stability of the polyester, polyoxyethylene glycol bleeds out from the polyester fiber, which is not preferable because the yarn-making process characteristics are deteriorated. The content of polyoxyethylene glycol is preferably in the range of 0.3 to 7% by mass, more preferably in the range of 0.5 to 5% by mass with respect to the mass of the entire polyester composition.

  The polyester composition of this invention needs to contain 0.1-5 mass% of alkylsulfonic acid metal salt and / or alkylbenzenesulfonic acid metal salt with respect to the mass of the whole polyester composition. The alkyl chain length of the alkylsulfonic acid metal salt and / or the alkylbenzenesulfonic acid metal salt is preferably 8 to 20 carbon atoms. If the number of carbon atoms is less than 8, the compatibility with the copolyester is inferior, and sublimable foreign matter may be generated during spinning, or bleed out may occur on the surface of the polyester fiber. On the other hand, when the carbon number exceeds 20, the antistatic performance becomes inferior. Examples of the metal salt include Li, Na, K salt, and the like, but Na salt is more preferable because it is excellent in antistatic property and hardly generates agglomerated foreign matter. That is, as the alkylsulfonic acid metal salt and / or the alkylbenzenesulfonic acid metal salt, sodium alkylsulfonate and / or sodium alkylbenzenesulfonate are preferable, respectively. More specifically, examples include sodium octyl sulfonate, sodium dodecyl sulfonate, sodium tetradecyl sulfonate, sodium stearyl sulfonate, sodium octyl benzene sulfonate, sodium dodecyl benzene sulfonate, sodium tetradecyl benzene sulfonate, and the like. These may be used alone or in combination of two or more. When the content of these alkylsulfonic acid metal salts and / or alkylbenzenesulfonic acid metal salts is less than 0.1% by mass, the antistatic property of the resulting polyester fiber becomes insufficient, and when the content exceeds 5% by mass, the heat of the polyester In addition to the insufficient stability, the alkyl sulfonic acid metal salt and / or the alkyl benzene sulfonic acid metal salt bleed out from the fiber, which is not preferable. The content of the alkylsulfonic acid metal salt and / or the alkylbenzenesulfonic acid metal salt is preferably in the range of 0.2 to 4% by mass, and more preferably in the range of 0.3 to 3% by mass.

  In the copolymerized polyester composition of the present invention, there are no particular limitations on the addition timing and method of polyoxyethylene glycol, metal alkyl sulfonate, metal alkyl benzene sulfonate, and esterification reaction, transesterification reaction, or polymerization reaction. Examples include addition before and after, or in the middle of these reactions, or melt blending with the obtained copolymerized polyester. From the viewpoint of heat resistance of the polyester composition, the method of adding in the latter half of the polymerization reaction is most preferable. .

  The polyester composition of the present invention contains a small amount of additives as necessary, for example, a lubricant, an antioxidant, a solid phase polymerization accelerator, a color adjuster, a fluorescent whitening agent, an antibacterial agent, an ultraviolet absorber, a light stabilizer, A heat stabilizer, a light-shielding agent or a matting agent may be included. Of these, the antioxidant is particularly preferably added in order to increase the heat resistance of the polyoxyethylene glycol to be added. As the antioxidant to be added, a hindered phenol-based antioxidant is particularly preferable, and the addition amount is preferably in the range of 0.1 to 1.0% by mass with respect to the copolymerized polyester composition.

  There is no limitation in particular as a manufacturing method of the polyester fiber of this invention, A conventionally well-known melt spinning method is used. For example, it is preferable to produce a dried polyester composition by melt spinning at a temperature in the range of 270 ° C. to 300 ° C., and the spinning speed of the melt spinning can be 400 to 9000 m / min. It is possible to increase the strength of the material.

  Further, the shape of the die used at the time of spinning is not particularly limited, and any of circular shape, irregular shape, solid shape or hollow shape can be adopted. However, in order to exhibit the characteristics of the polyester fiber of the present invention, solid and atypical are particularly preferable. Furthermore, when manufacturing a polyester product using the polyester fiber of this invention, in order to raise the feel, an alkali weight loss process is also implemented preferably.

  Using the polyester fiber of the present invention, the polyester fiber product of the present invention can be produced as a fabric such as woven fabric or knitted fabric by a conventionally known method. The polyester fiber product of the present invention has an environment of 20 ° C. and 65% RH. The surface charge half life below is preferably 10 seconds or less. When the half-life of the surface charge exceeds 10 seconds, the antistatic property of the fiber product is insufficient, which is not preferable. More preferably, the half life of the surface charge is 5 seconds or less. In order to make the half-life of the surface charge 10 seconds or less in the polyester fiber of the present invention, the copolymerized polyester can obtain at least one diol component selected from the general formula groups (I) to (III) of the present invention. Predetermined mass% with respect to the polyester composition which can be copolymerized to obtain polyoxyethylene glycol having a number average molecular weight of 10,000 to 100,000 and alkylsulfonic acid metal salt and / or alkylbenzenesulfonic acid metal salt. The contained polyester composition is used. Among them, the diol component is diethylene glycol, 1,3-propanediol, 1,4-butanediol, polyethylene glycol having a molecular weight of 650 or less, cyclohexanedimethanol, 2,2-bis [4- (2-hydroxyethoxy) phenyl] propane, It is preferable to use a polyester composition that is 1,3-bis (2-hydroxyethoxy) benzene. In the present invention, the “fiber product” refers to a processed yarn, a spun yarn, a woven or knitted fabric, a non-woven fabric, and other three-dimensional structures, without being limited to spun and drawn long fibers and short fibers.

  The present invention will be further described in the following examples, but the scope of the present invention is not limited by these examples. Various characteristics were measured by the following methods.

(A) Intrinsic viscosity:
A dilute solution obtained by dissolving a polyester composition chip in orthochlorophenol at 100 ° C. for 60 minutes was determined from a value measured at 35 ° C. using an Ubbelohde viscometer.

(I) Diol component content:
For diethylene glycol, the polyester composition chip is decomposed using hydrazine hydrate (hydrazine hydrate), and the content of diethylene glycol in the decomposition product is determined using gas chromatography (HP Hewlett Packard (HP6850 type)). It was measured.
For diol components other than diethylene glycol, which are difficult to measure by gas chromatography, a polymer sample is dissolved in deuterated trifluoroacetic acid / deuterated chloroform = 1/1 mixed solvent, and then JEOL A-600 manufactured by JEOL Ltd. A nuclear magnetic resonance spectrum ( ¹ H-NMR) was measured using superconducting FT-NMR, and the content was quantified from the spectrum pattern according to a conventional method.

(C) Hue (L ^* value, b ^* value):
・ Chip:
The polymer chip was melted at 285 ° C. under vacuum for 10 minutes, formed into a plate having a thickness of 3.0 ± 1.0 mm on an aluminum plate, and immediately cooled in ice water. The plate was dried at 140 ° C. for 2 hours. Crystallization was performed.
Then, it placed on a white standard plate for color difference adjustment, and L ^* , a ^* and b ^* on the plate surface were measured using a Minolta Hunter color difference meter (CR-200 type). L ^* indicates lightness, and the larger the value, the higher the lightness, a ^* indicates that the greater the value, the greater the degree of red coloring, and b ^{* the} greater the value, the greater the degree of yellow coloring. Indicates big. Other detailed operations were performed according to JIS Z-8729.

(D) Number average molecular weight of polyoxyethylene glycol:
After dissolving polyoxyethylene glycol in chloroform, Shodex GPC-101 gel permeation chromatography manufactured by Showa Denko K.K. is used, the sample column for measurement is Shodex LF-804 manufactured by Showa Denko K.K., and the reference column is Showa. Using Shodex KF-800RH manufactured by Denko Co., Ltd., using chloroform as the developing solvent, the molecular weight distribution was measured with an RH detector. The number average molecular weight was calculated in terms of polystyrene.

(E) Polyoxyethylene glycol and alkylsulfonic acid metal salt / alkylbenzenesulfonic acid metal salt content in the polyester composition:
A polymer sample was dissolved in a deuterated trifluoroacetic acid / deuterated chloroform = 1/1 mixed solvent, and then JEOL A-600 superconducting FT-NMR manufactured by JEOL Ltd. was used to determine a nuclear magnetic resonance spectrum ( ¹ H- NMR) was measured, and the content of polyoxyethylene glycol and alkylsulfonic acid metal salt and / or alkylbenzenesulfonic acid metal salt was quantified from the spectrum pattern according to a conventional method. At the same time, the molecular structure of the alkylsulfonic acid metal salt and / or the alkylbenzenesulfonic acid metal salt was also analyzed.

(F) Tensile strength and tensile elongation of fiber:
Measurement was performed in accordance with the method described in JIS L1070.

(G) Antistatic property of the fabric The antistatic property (saturation voltage and half voltage decay time) of the fabric was measured by using a surface charge attenuation measuring device (S-5109, manufactured by Sisid Electric Co., Ltd.). The charged half-life was measured and evaluated. The half-life was measured at an ambient temperature of 20 ° C. and a relative humidity of 65% after conditioning the sample for 24 hours in an atmosphere of a temperature of 20 ° C. and a relative humidity of 65%.

[Example 1]
-Manufacture of copolymerized polyester composition chip In a mixture of 90 parts by mass of dimethyl terephthalate, 10 parts by mass of diethylene glycol and 80 parts by mass of ethylene glycol, 0.063 parts by mass of calcium acetate monohydrate, cobalt acetate tetrahydrate 0. 013 parts by mass were charged into a reactor equipped with a stirrer, a rectifying column and a methanol distillation condenser. While the reactor internal temperature was gradually raised from 140 ° C. to 240 ° C., the transesterification reaction was performed while distilling out the methanol produced as a result of the reaction to the outside of the reactor. Thereafter, 0.058 parts by mass of trimethyl phosphate was added to complete the transesterification reaction. Thereafter, 0.04 parts by mass of antimony trioxide and 1.5 parts by mass of 20% ethylene glycol slurry of titanium dioxide were added to the reaction product, and the reaction was equipped with a stirrer, nitrogen inlet, vacuum port and distillation unit. It moved to the container, heated up to 290 degreeC, and polycondensation reaction was performed by the high vacuum of 30 Pa or less. 30 minutes before the completion of the polymerization reaction, the inside of the system was once returned to normal pressure with nitrogen, 0.8 parts by mass of polyoxyethylene glycol having a number average molecular weight of 20000, 0.4 parts by mass of sodium tetradecylsulfonate, an antioxidant. After adding 0.4 parts by mass of Irganox 1010 (manufactured by Ciba Specialty Chemicals), a polycondensation reaction is performed again at a high vacuum of 30 Pa or less, and the intrinsic viscosity is 0.74 dL / g and the diethylene glycol content is 5% by mass. A polyester composition was obtained. Furthermore, it was made into a chip according to a conventional method. The results are shown in Tables 1-3.

・ Manufacture of polyester fiber After the chip is dried at 160 ° C. for 4 hours, a raw fiber having a spinning temperature of 285 ° C. and a winding speed of 400 m / min. A drawn yarn of 73 dtex / 24 fil was obtained by drawing 4.4 times at 85 ° C. and a heat setting temperature of 160 ° C. The obtained drawn yarn was further knitted into a cylinder by a conventional method. The results are shown in Table 3.

[Examples 2 to 9]
In Example 1, it implemented similarly to Example 1 except having changed into the compound kind and quantity which are shown in Table 1 instead of 10 mass parts of diethylene glycol. The results are shown in Tables 1-3.

[Example 10]
In Example 1, it implemented like Example 1 except having used sodium dodecylbenzenesulfonate instead of sodium tetradecylsulfonate. The results are shown in Tables 1-3.

[Comparative Example 1]
In Example 1, it carried out like Example 1 except not adding diethylene glycol and using 90 mass parts of ethylene glycol. The results are shown in Tables 1-3.

[Comparative Example 2]
The same procedure as in Example 1 was performed except that 70 parts by mass of ethylene glycol and 30 parts by mass of diethylene glycol were used in Example 1. The results are shown in Tables 1-3.

[Comparative Example 3]
Example 1 was carried out in the same manner as Example 1 except that polyethylene glycol having a number average molecular weight of 4000 was used instead of polyoxyethylene glycol having a number average molecular weight of 20000. The results are shown in Tables 1-3.

[Comparative Example 4]
In Example 1, it implemented like Example 1 except not having added polyoxyethylene glycol of the number average molecular weight 20000, sodium tetradecyl sulfonate, and Irganox 1010. The results are shown in Tables 1-3.

  According to the present invention, it is possible to impart high antistatic properties to solid fibers composed of a single polymer composition component.

Claims (4)

The main repeating unit is composed of ethylene terephthalate, and at least one diol component selected from the following general formula groups (I) to (III) is copolymerized in an amount of 1 to 20% by mass based on the mass of the copolymerized polyester. 0.2-10 mass% of alkyl sulfonic acid with respect to the mass of the polyester composition which is a copolyester with a viscosity of 0.5 dL / g or more, and can obtain polyoxyethylene glycol with a number average molecular weight of 10,000 or more and 100,000 or less An antistatic copolyester composition comprising 0.1 to 5% by mass based on the mass of a polyester composition from which a metal salt and / or an alkylbenzenesulfonic acid metal salt can be obtained.
[Formula 1]
H- (OR) _n -OH (I)
[In the above formula, the functional group R is an alkylene group having 2 to 12 carbon atoms, and when R is 2 carbon atoms, n = 2 to 15 and when R is 3 or more carbon atoms, n = 1 to 15 is represented. ]
_{HOCH 2 CH 2 O-X-} OCH 2 CH 2 OH (II)
[In the above formula, the functional group X represents an arene group. ]
_{HOCH 2 -Y-CH 2 OH (} III)
[In the above formula, the functional group Y represents a cycloalkyl group or an arene group. ]   The copolymer components represented by the general formula groups (I) to (III) are diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and polyethylene glycol having a number average molecular weight of 650 or less. , 2,2-bis [4- (2-hydroxyethoxy) phenyl] propane, 1,3-bis (2-hydroxyethoxy) benzene, and 1,4-cyclohexanedimethanol The antistatic copolyester composition according to claim 1.   The antistatic copolyester composition according to any one of claims 1 to 2, wherein the alkylsulfonic acid metal salt and / or the alkylbenzenesulfonic acid metal salt is sodium alkylsulfonate and / or sodium alkylbenzenesulfonate.   It consists of a polyester fiber obtained by melt spinning the antistatic copolyester composition according to any one of claims 1 to 3, and has a half-life of surface charge in an environment of 20 ° C and 65% RH. Antistatic polyester fiber product that is 10 seconds or less.