JP2010090507A - Ultrafine fiber of antistatic sheath-core polytrimethylene terephthalate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polytrimethylene terephthalate ultrafine fiber having soft texture, excellent stretchability and high antistatic properties and a method for stably producing the fiber. <P>SOLUTION: The ultrafine fiber of antistatic sheath-core polytrimethylene terephthalate is a sheath-core conjugate fiber having a core part comprising an antistatic polytrimethylene terephthalate A and a sheath part comprising a polytrimethylene terephthalate B containing 0-10 wt.% of a delustering agent, and satisfying the following conditions (1) to (5): (1) the single fiber fineness is ≤1.5 dtex; (2) the areal ratio of the core part A and the sheath part B (A:B) is 5:95 to 80:20; (3) the strength of the single fiber is ≥3.0 cN/dtex; (4) the friction-charged electrostatic potential of the fiber is ≤2,000 V; and (5) the antistatic polytrimethylene terephthalate A contains specific amounts of a specific polyoxyalkylene polyether and an organic ionic compound and 100 pts.wt. of a polyester. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polytrimethylene terephthalate ultrafine yarn having antistatic properties and a method for producing the same. More specifically, the present invention relates to a production method capable of stably obtaining a polytrimethylene terephthalate ultrafine yarn that satisfies excellent durability, antistatic properties, soft feeling, and stretchability.

  Conventionally, when a polytrimethylene terephthalate yarn is made into a fabric, a soft texture with a low modulus is obtained, and there is also stretchability due to high elastic recovery, and it is difficult to lose shape due to wrinkle recovery and shape stability of the fiber. It is characterized by a smooth feel, and in recent years it has come to be used in a wide range of fields such as women's coats and sports outers made of high-density fabrics using yarns with fine single yarn fineness. However, since polytrimethylene terephthalate, which is a polyester, is hydrophobic, it is relatively easy to generate static electricity even in high-density fabrics using yarns with low single yarn fineness. The mainstream is providing the anti-static function. However, the application of the antistatic agent in the post-processing has low antistatic washing durability, and as a countermeasure against this, it has been required to provide the antistatic function at the polymer stage.

  Attempts have been made to develop antistatic properties in polytrimethylene terephthalate, and many proposals have been made so far. For example, as described in Patent Document 1, it is known to add polyethylene glycol and a 5-sulfonic acid metal compound to polytrimethylene terephthalate. However, since polytrimethylene terephthalate is inherently poor in thermal stability, the addition of these compounds makes it extremely poor in stability, especially when spinning yarns with small single yarn fineness, resulting in increased yarn breakage and fluff. There was a problem that the remarkably decreased. Further, as described in Patent Document 2, a polyester blended article (mixed yarn, fabric, etc.) made of antistatic core-sheath type polyethylene terephthalate fiber and polytrimethylene terephthalate fiber has been proposed. It is possible to satisfy both the stretchability and the antistatic property by mixing both, but the productivity is not good because two types of fibers are required.

Japanese Patent Laid-Open No. 11-181626 JP 2006-2258 A

  As is apparent from the above, the object of the present invention is to maintain the performance such as the soft texture and stretchability of the conventional ultrafine polytrimethylene terephthalate yarn, and to achieve excellent antistatic performance. An object of the present invention is to provide a methylene terephthalate yarn and a method for stably producing the yarn.

As a result of intensive studies to achieve the above object, the present inventors have reached the present invention, that is, according to the present invention,
It is a core-sheath type composite fiber, the core part is formed of antistatic polytrimethylene terephthalate A, and the sheath part is formed of polytrimethylene terephthalate B containing 0-10 wt% matting agent. An antistatic core-sheath type polytrimethylene terephthalate ultrafine fiber that satisfies the conditions (1) to (5).
(1) The single yarn fineness is 1.5 dtex or less.
(2) The ratio A: B between the area A of the core and the area B of the sheath is in the range of 5:95 to 80:20.
(3) The strength of the single yarn is 3.0 cN / dtex or more.
(4) The frictional voltage of the fiber is 2000V or less.
(5) Antistatic polytrimethylene terephthalate A is 100 parts by weight of polyester, and as an antistatic agent, (a) 4 to 10 parts by weight of polyoxyalkylene polyether represented by the following formula and (b) An antistatic polytrimethylene terephthalate containing 2 to 8 parts by weight of an organic ionic compound that is substantially non-reactive with the polyester.
^{_{Z - [(CH 2 CH 2}} O) n (R 1 O) m-R 2] k
[Wherein, Z is an organic compound residue having 1 to 6 active hydrogen atoms, R ¹ is an alkylene group or substituted alkylene group having 6 or more carbon atoms, R ² is a hydrogen atom, having 1 to 40 carbon atoms. A monovalent hydrocarbon group, a monovalent hydroxy hydrocarbon having 2 to 40 carbon atoms or a monovalent acyl group having 2 to 40 carbon atoms, k is an integer of 1 to 6, and n is n ≧ 70 / k. Satisfied integer, m is an integer of 1 or more]
Is provided.

When the antistatic polytrimethylene terephthalate A and polytrimethylene terephthalate B are melt-spun, the ratio of the discharge speed and the take-off speed during spinning (take-off speed / discharge speed, hereinafter referred to as draft ratio) is 300 or more. The undrawn yarn was wound at 1000 to 3000 m / min with a first roller heated to 40 ° C. to 70 ° C. within a range of less than 1000, and then 1.2 to 2.5 on a second roller heated to 110 to 150 ° C. A method for producing an antistatic core-sheath type polytrimethylene terephthalate ultrafine fiber that is stretched twice and wound at a lower speed than the second roller,
Is provided.

  The anticorrosive core-sheath type polytrimethylene terephthalate ultrafine fiber of the present invention maintains the soft texture, stretch properties, etc. of conventional ultrafine polytrimethylene terephthalate yarn, and is antistatic and antistatic durability In addition, an excellent polyester fabric can be obtained.

Hereinafter, embodiments of the present invention will be described in detail.
The polytrimethylene terephthalate fiber referred to in the present invention is a fiber made of polyester having trimethylene terephthalate as a main repeating unit. This polyester may be a copolymerized polytrimethylene terephthalate obtained by copolymerizing a third component other than the component constituting the trimethylene terephthalate unit. The third component (copolymerization component) may be either a dicarboxylic acid component or a glycol component. Here, “main” means 90 mol% or more in all repeating units.

  As the component preferably used as the third component, as the dicarboxylic acid component, aromatic dicarboxylic acid such as 2,6-naphthalenedicarboxylic acid, isophthalic acid or phthalic acid, adipic acid, azelaic acid, sebacic acid or decanedicarboxylic acid, etc. Aliphatic dicarboxylic acids such as aliphatic dicarboxylic acids and cyclohexanedicarboxylic acids, and the glycol components include ethylene glycol, tetramethylene glycol, diethylene glycol, polyethylene glycol, hexamethylene glycol, cyclohexanedimethanol or 2,2-bis [4 -(2-hydroxyethoxy) phenyl] propane and the like are exemplified, and these can be used alone or in combination of two or more. Such aromatic polyester is synthesized by any method.

The polyoxymethylene polyether (a) represented by the following general formula (1) as one component of the antistatic agent used in the present invention is a single component as long as it is substantially insoluble in polytrimethylene terephthalate. The polyoxyalkylene glycol may be a polyoxyalkylene glycol comprising two oxyalkylene units or a copolymer polyoxyalkylene glycol comprising two or more oxyalkylene units.
^{_{Z - [(CH 2 CH 2}} O) n (R 1 O) m-R 2] k equation (1)
[Wherein, Z is an organic compound residue having 1 to 6 active hydrogen atoms, R ¹ is an alkylene group or substituted alkylene group having 6 or more carbon atoms, R ² is a hydrogen atom, having 1 to 40 carbon atoms. A monovalent hydrocarbon group, a monovalent hydroxy hydrocarbon having 2 to 40 carbon atoms or a monovalent acyl group having 2 to 40 carbon atoms, k is an integer of 1 to 6, and n is n ≧ 70 / k. Satisfied integer, m is an integer of 1 or more]

  Specific examples of such polyoxyalkylene polyether include polyoxyethylene glycol having a molecular weight of 4000 or more, polyoxypropylene glycol having a molecular weight of 1000 or more, polyoxytetramethylene glycol, ethylene oxide having a molecular weight of 2000 or more, and a propylene oxide copolymer. Polymers, trimethylolpropane ethylene oxide adducts having a molecular weight of 4000 or more, nonylphenol ethylene oxide adducts having a molecular weight of 3000 or more, and compounds in which a substituted ethylene oxide having 6 or more carbon atoms is added to these terminal OH groups. However, polyoxyethylene glycol having a molecular weight of 10,000 to 100,000 and an alkyl group having 8 to 40 carbon atoms at both ends of the polyoxyethylene glycol having a molecular weight of 5000 to 16000. Compound conversion of ethylene oxide are added are preferred.

  The compounding amount of the polyoxyalkylene polyether compound is in the range of 4 to 10 parts by weight with respect to 100 parts by weight of the aromatic polyester. If the amount is less than 4 parts by weight, the antistatic property is reduced in the ultrafine fiber having a single yarn fineness of 1.5 dtex or less, whereas if it exceeds 10 parts by weight, the antistatic effect is no longer recognized. This is not preferable because the strength is lowered and the polyether is likely to bleed out, so that the biting property of the chip into the loader at the time of melt molding is lowered and the yarn forming property is deteriorated.

In the present invention, an organic ionic compound is blended as the other antistatic agent. Preferred examples of the organic ionic compound include sulfonic acid metal salts and sulfonic acid quaternary phosphonium salts represented by the following general formulas (2) and (3).
RSO ₃ M (2)
[Wherein, R represents an alkyl group having 3 to 30 carbon atoms or an aryl group having 7 to 40 carbon atoms, and M represents an alkali metal or an alkaline earth metal]

In the above formula (2), when R is an alkyl group, the alkyl group may be linear or have a branched side chain. M is an alkali metal such as Na, K, Li or the like, or an alkaline earth metal such as Mg, Ca. Among them, Li, Na, K are preferable. Such sulfonic acid metal salts may be used alone or in combination of two or more. Preferred examples include sodium stearyl sulfonate, sodium octyl sulfonate, sodium dodecyl sulfonate, a mixture of sodium alkyl sulfonate having an average of 14 carbon atoms, a mixture of sodium dodecyl benzene sulfonate, sodium dodecyl benzene sulfonate (hard type) Soft type), lithium dodecylbenzenesulfonate (hard type, soft type), magnesium dodecylbenzenesulfonate (hard type, soft type) and the like.
RSO ₃ PR ¹ R ² R ³ R ⁴ (3)
[Wherein, R is the same as the definition of R in the above formula (2), and R ¹ , R ² , R ³ , and R ⁴ are an alkyl group or an aryl group, especially a lower alkyl group, a phenyl group, or a benzyl group. Is preferred]

  Such sulfonic acid quaternary phosphonium salts may be used alone or in combination of two or more. Preferred examples include tetrabutylphosphonium alkyl sulfonate having an average of 14 carbon atoms, tetraphenyl phosphonium alkyl sulfonate having an average of 14 carbon atoms, and butyl alkyl sulfonate having an average of 14 carbon atoms. Triphenylphosphonium, tetrabutylphosphonium dodecylbenzenesulfonate (hard type, soft type), tetraphenylphosphonium dodecylbenzenesulfonate (hard type, soft type), benzyltriphenylphosphonium dodecylbenzenesulfonate (hard type, soft type), etc. Can give.

  These organic ionic compounds may be used alone or in combination of two or more, and the blending amount thereof is preferably in the range of 2 to 8 parts by weight with respect to 100 parts by weight of the aromatic polyester. If the amount is less than 2 parts by weight, the effect of improving the antistatic property is small in an ultrafine fiber having a single yarn fineness of 1.5 dtex or less. If the amount exceeds 8 parts by weight, the strength of the fiber is lowered and the ionic compound is also likely to bleed out. For this reason, the chip rudder penetration property at the time of melt molding is lowered, and the yarn production property is also deteriorated.

  Polytrimethylene terephthalate B is blended with a known matting agent as long as the object of the present invention is not impaired. If the matting agent exceeds 10 wt%, the spinnability of the undrawn yarn that becomes the parent yarn of the present invention is deteriorated, so the range is preferably 0 to 10 wt%.

  Further, the antistatic polytrimethylene terephthalate ultrafine yarn of the present invention needs to have a single yarn fineness of 1.5 dtex or less, and when it exceeds 1.5 dtex, the softness is lowered. Preferably it is 0.5-1.5 dtex. The maximum value (Fmax) of thermal stress is preferably 0.25 cN / dtex or less. By setting it within this range, a woven or knitted fabric that is soft and has excellent stretchability can be obtained.

  Furthermore, the core-sheath area ratio of polytrimethylene terephthalate A and polytrimethylene terephthalate B needs to be in the range of 5:95 to 80:20. When the area ratio is smaller than 5:95, the expression of the antistatic performance by polytrimethylene terephthalate A becomes insufficient, and when larger than 80:20, when the alkali weight loss of 10% or more is applied, Since the antistatic polytrimethylene terephthalate A in the core is eluted, the antistatic performance is reduced, or the strength of the yarn is reduced to 2.0 cN / dtex or less, and the strength when used as a fabric is insufficient. It is not suitable for applications that require strength, such as clothing, and is not preferable because the applications are limited.

  The core-sheath type polytrimethylene terephthalate ultrafine yarn of the present invention described above has a ratio of a discharge speed and a take-off speed during spinning (take-off speed / discharge speed, hereinafter referred to as a draft) of 300 or more when melt spinning. Stable antistatic performance can be obtained by drawing an undrawn yarn taken in a range of less than 1000 as it is by 1.2 to 2.5 times. When the draft is 300 or less, the expression of the antistatic performance by the polyester A becomes insufficient, and at the same time, the polymer oozes out to the periphery of the nozzle discharge hole. In the above case, although antistatic performance is exhibited, it is not preferable because spinnability is lowered. When the draw ratio is 1.2 times or less, sufficient yarn strength cannot be obtained. When the draw ratio is 2.5 times or more, the maximum value (Fmax) of the thermal stress is 0.25 cN / dtex or more, and a woven or knitted fabric excellent in soft feel is obtained. In addition to being unable to obtain, the wound package is greatly tightened, and the appearance of the winding is significantly deteriorated, so that the process passability is lowered.

Accordingly, the nozzle discharge hole diameter, spinning speed, and draw ratio may be appropriately set within this range. However, melt spinning is performed with the discharge diameter in the range of 0.1 to 0.4 mm and the take-up speed of 1000 to 3000 m / min. A value of 2 to 2.5 is preferable because it can be easily and efficiently obtained.
The polytrimethylene terephthalate ultrafine yarn of the present invention thus obtained is a polyester excellent in antistatic performance while maintaining the soft texture, stretchability, etc. of the conventional polytrimethylene terephthalate ultrafine yarn. A fabric can be obtained.

Hereinafter, the present invention will be described more specifically with reference to examples. In addition, each item in an Example was measured with the following method.
(1) Intrinsic viscosity Dissolved in ortho-chlorophenol and measured at 35 ° C. using an Ubbelohde viscosity tube.
(2) Maximum value of thermal stress (Fmax)
Measurement is performed using a thermal stress measurement device (for example, trade name KE-2 manufactured by Kanebo Engineering Co., Ltd.). Cut the drawn yarn into a length of 20 cm, tie both ends of the drawn yarn to make a loop, and load it into the measuring instrument. Measure under conditions of initial load of 0.044 cN / dTex and temperature increase rate of 100 ° C./min, record the temperature change of heat shrinkage stress on a chart, and read the maximum value of heat shrinkage stress.
(3) Texture of fabric (soft feeling)
Level 1: Soft and supple feel Level 2: Slightly soft feeling but repellent feel Level 3: Rough feel or hard feel
(4) Stretch ratio of woven fabric Stretch ratio (S:%) is a 20 cm x 20 cm woven fabric sample stretched in the weft direction of the woven fabric at a pulling speed = 20 mm / sec using KES-FB1 manufactured by Cartec Co., Ltd. From the elongation under stress of 4.9 cN / cm (A: cm), the following equation was obtained.
S (%) = [(A / 20)] × 100A
(5) Chargeability test method A method (half-life measurement method)
After the composite false twisted yarn of the present invention is knitted, dyed, conditioned, and the test piece is charged in a corona discharge field, the time (seconds) until the charged voltage is attenuated to ½ Measure with a static Honestometer. The shorter the time (seconds), the better the anti-static performance.
(6) Chargeability test method B method (friction charging voltage measurement method)
While rotating the test piece, the test piece is rubbed with a friction cloth and the generated charged voltage is measured. Conforms to L1094 electrification test method B (friction band voltage measurement method). Regarding the antistatic effect, if the frictional voltage is about 2000 V or less (preferably 1500 V or less), the antistatic effect is exhibited.
(7) Spinning and severing In the compound spinning facility, melt spinning was performed for one week and the number of times of severing was recorded, and the number of times of severing per spindle per day was defined as severing. However, thread breakage due to artificial or mechanical factors was excluded from the number of breaks.

[Example 1]
The polytrimethylene terephthalate reaction mixture obtained by a conventional method was transferred to a polymerization reaction vessel, then depressurized from 760 mmHg to 1 mmHg over 1 hour and 30 minutes and heated to 260 ° C. to cause a polycondensation reaction. 4)
[Where j is an integer of 18 to 28 and average 21; P is 100 as an average value; m is 5 as an average value]
5 parts of water-insoluble polyoxyethylene-based polyether and 3 parts of sodium dodecylbenzenesulfonate were added under vacuum, followed by a polycondensation reaction for 240 minutes, and then as an antioxidant, Irganox 1010 manufactured by Ciba Kaigie Co., Ltd. Was added under a vacuum of 0.4 parts, followed by a polycondensation reaction for another 30 minutes. In the polymerization reaction step, an antistatic agent was added, and the resulting polymer was converted into a chip by a conventional method.

  The intrinsic viscosity of this polymer was 0.950, the softening point was 230 ° C., and the obtained chip was dried by a conventional method. Each dried polymer is melted in a spinning machine in the usual manner, and is introduced into a spin pack through a spin block to form a core-side polymer of a core-sheath composite fiber structure, and the sheath-side polymer is a homopolymer to which no antistatic agent is added. . The molten polymer is discharged from a spinneret with 48 circular discharge holes with a diameter of 0.30φmm incorporated in the spin pack, cooled and solidified with cooling air from a normal cross-flow type spinning cylinder, and the spinning oil is supplied. While concentrating, it is converged as one yarn, taken up at a speed of 2000 m / min, drawn into a spinning draft 420, drawn 1.35 times, and stretched with polytrimethylene terephthalate with 62 dtex / 48 filaments (average single yarn fineness 1.29 dtex) I got a thread. A comparatively high density plain woven fabric having a warp density of 200 / 2.54 cm and a weft density of 170 / 2.54 cm was woven using the drawn yarn, and its quality was evaluated. Further, a knitted fabric was manufactured using the obtained drawn yarn, and the antistatic property was measured. Table 1 shows the results of process stability and antistatic performance during melt spinning.

[Example 2]
A polytrimethylene terephthalate drawn yarn was obtained in the same manner as in Example 1 except that 4 parts by weight of water-insoluble polyoxyethylene-based polyether and 2 parts by weight of sodium dodecylbenzenesulfonate were used as antistatic agents in Example 1. Table 1 shows the results of process stability and antistatic performance during melt spinning.

[Example 3]
A polytrimethylene terephthalate drawn yarn was obtained in the same manner as in Example 1 except that 6 parts by weight of water-insoluble polyoxyethylene-based polyether and 4 parts by weight of sodium dodecylbenzenesulfonate were used as antistatic agents in Example 1. Table 1 shows the results of process stability and antistatic performance during melt spinning.

[Comparative Example 1]
A polytrimethylene terephthalate drawn yarn was obtained in the same manner as in Example 1 except that the water-insoluble polyoxyethylene-based polyether as an antistatic agent and sodium dodecylbenzenesulfonate were not added in Example 1. Table 1 shows the results of process stability and antistatic performance during melt spinning.

[Comparative Example 2]
A polytrimethylene terephthalate drawn yarn was obtained in the same manner as in Example 1 except that 5 parts by weight of water-insoluble polyoxyethylene-based polyether and 0 parts by weight of sodium dodecylbenzenesulfonate were used as antistatic agents in Example 1. . Table 1 shows the results of process stability and antistatic performance during melt spinning.

[Comparative Example 3]
A polytrimethylene terephthalate drawn yarn was obtained in the same manner as in Example 1 except that 0 part by weight of water-insoluble polyoxyethylene-based polyether and 3 parts by weight of sodium dodecylbenzenesulfonate were used as antistatic agents in Example 1. Table 1 shows the results of process stability and antistatic performance during melt spinning.

[Comparative Example 4]
A polytrimethylene terephthalate drawn yarn was obtained in the same manner as in Example 1 except that the spinning draft was 296 at a take-up speed of 1400 m / min and the draw ratio was 2.14 times. Table 1 shows the results of process stability and antistatic performance during melt spinning.

  It is characterized by a strong constitution for school uniforms, uniforms, and light resistance. Moreover, since the part which demonstrates antistatic property is enveloped, the polyester fabric excellent in washing durability can be provided.

Claims (2)

It is a core-sheath type composite fiber, the core part is formed of antistatic polytrimethylene terephthalate A, and the sheath part is formed of polytrimethylene terephthalate B containing 0-10 wt% matting agent. An antistatic core-sheath type polytrimethylene terephthalate ultrafine fiber that satisfies the conditions (1) to (5).
(1) The single yarn fineness is 1.5 dtex or less.
(2) The ratio A: B between the area A of the core and the area B of the sheath is in the range of 5:95 to 80:20.
(3) The strength of the single yarn is 3.0 cN / dtex or more.
(4) The frictional voltage of the fiber is 2000V or less.
(5) Antistatic polytrimethylene terephthalate A is 100 parts by weight of polyester, and as an antistatic agent, (a) 4 to 10 parts by weight of polyoxyalkylene polyether represented by the following formula and (b) An antistatic polytrimethylene terephthalate containing 2 to 8 parts by weight of an organic ionic compound that is substantially non-reactive with the polyester.
^{_{Z - [(CH 2 CH 2}} O) n (R 1 O) m-R 2] k
[Wherein, Z is an organic compound residue having 1 to 6 active hydrogen atoms, R ¹ is an alkylene group or substituted alkylene group having 6 or more carbon atoms, R ² is a hydrogen atom, having 1 to 40 carbon atoms. A monovalent hydrocarbon group, a monovalent hydroxy hydrocarbon having 2 to 40 carbon atoms or a monovalent acyl group having 2 to 40 carbon atoms, k is an integer of 1 to 6, and n is n ≧ 70 / k. Satisfied integer, m is an integer of 1 or more]   When melt spinning the antistatic polytrimethylene terephthalate A and polytrimethylene terephthalate B according to claim 1, a ratio between a discharge speed and a take-off speed at the time of spinning (take-off speed / discharge speed, hereinafter referred to as draft). In the range of 300 to 1000, the undrawn yarn was wound at 1000 to 3000 m / min with a first roller heated to 40 ° C. to 70 ° C., and then 1.2 to 2.2. The method for producing antistatic core-sheath-type polytrimethylene terephthalate ultrafine fibers according to claim 1, which is obtained by drawing and winding 5 times and winding at a lower speed than the second roller.