JP2010236150A - Polyurethane-based elastic fiber and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyurethane-based elastic fiber excellent in antistaticity, chlorine resistance and productivity; and to provide a method for producing the same. <P>SOLUTION: The polyurethane-based elastic fiber comprises a polyurethane-based polymer and a quaternary ammonium sulfonate salt; wherein the quaternary ammonium sulfonate salt is a compound represented by general formula (1) and is contained at 0.01-10 wt.% relative to the polyurethane-based polymer. In the genera formula (1), R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>and R<SP>4</SP>are each independently 1-22C hydrocarbon group or OH-bearing 1-18C hydrocarbon group; R<SP>5</SP>is 6-22C aliphatic hydrocarbon group or a substituted phenyl group represented by general formula (2) (wherein, R<SP>6</SP>is 6-22C aliphatic hydrocarbon group). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a polyurethane elastic fiber containing a specific sulfonic acid quaternary ammonium salt as an antistatic and chlorine resistance improver of a polyurethane elastic fiber and a method for producing the polyurethane elastic fiber.

Polyurethane elastic fibers are often used after being knitted and woven with natural fibers, other chemical fibers, and synthetic fibers. At that time, when unwinding defects and static electricity are frequently generated from the winding package, the yarn breakage occurs frequently, so that warping and knitting become difficult and productivity is lowered. Polyurethane-based elastic fibers are polyether-based polyurethane elastic fibers and polyester-based polyurethane elastic fibers. In recent years, the speed of post-processing of these polyurethane-based elastic fibers and the finer dtex of the used fineness have progressed. Troubles due to static electricity tend to increase in the post-processing process. Then, in order to suppress generation | occurrence | production of static electricity, the processing agent for elastic fibers described in patent document 1 or patent document 2 is made to adhere to a fiber. Since these treatment agents are attached to the fiber surface, the treatment agent is detached by contact between the fiber and the guide in the post-processing step, or is removed by scouring, so that it is difficult to maintain stable antistatic properties. In particular, dropout on the guide causes scum, which causes a problem that thread breakage occurs and productivity is lowered. Also, as described in Patent Document 3, there is a method of internally adding various sulfonates to the fiber, but the compatibility with the polyurethane-based elastic polymer may not be sufficient, and high antistatic properties cannot be imparted. There was a problem.
Further, when the polyurethane elastic fiber is repeatedly immersed in sterilizing chlorine water having an active chlorine concentration of 0.5 to 3 ppm such as a swimming pool, its elastic function is remarkably impaired and thread breakage occurs. For this reason, as a method for improving the chlorine resistance of polyurethane-based elastic fibers, there is a method in which a metal oxide or the like is internally added as shown in Patent Document 4, but since it is insoluble in the spinning stock solution, it is uniformly dispersed. There is also a problem that workability and productivity are reduced.

JP 2004-162187 A JP 2006-161253 A WO99 / 35314 pamphlet JP-A-57-29609

  The object of the present invention is to solve the above-mentioned problems of the prior art and provide a polyurethane elastic fiber excellent in antistatic property, chlorine resistance and productivity, and a method for producing the polyurethane elastic fiber.

  As a result of intensive studies on the above-mentioned problems, the present inventors have added a specific sulfonic acid quaternary ammonium salt, which is an antistatic agent soluble in a spinning stock solution of a polyurethane-based elastic fiber, to the polyurethane-based elastic fiber. It has been found that a polyurethane-based elastic fiber having excellent properties, antistatic properties, chlorine resistance, and productivity can be provided, and the present invention has been achieved.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４は、それぞれ独立して炭素数１〜２２の炭化水素基または水酸基を有する炭素数１〜１８の炭化水素基を示す。Ｒ^５は、炭素数６〜２２の脂肪族炭化水素基または下記一般式（２）で示される置換フェニル基を示す。）

（式中、Ｒ^６は、炭素数６〜２２の脂肪族炭化水素基を示す。） That is, the present invention is a polyurethane elastic fiber containing a polyurethane elastic polymer and a sulfonic acid quaternary ammonium salt, wherein the sulfonic acid quaternary ammonium salt is a compound represented by the following general formula (1): The polyurethane elastic fiber is contained in an amount of 0.01 to 10% by weight based on the polyurethane elastic polymer.

^{(Wherein, R 1, R 2, R} 3, R 4 , the .R ⁵ showing independently a hydrocarbon group having 1 to 18 carbon atoms having a hydrocarbon group or a hydroxyl group of 1 to 22 carbon atoms, A C6-C22 aliphatic hydrocarbon group or a substituted phenyl group represented by the following general formula (2) is shown.)

(In the formula, R ⁶ represents an aliphatic hydrocarbon group having 6 to 22 carbon atoms.)

R ¹ and R ² are each independently a hydrocarbon group having 1 to 22 carbon atoms, and R ³ and R ⁴ are each independently a hydrocarbon group having 1 to 7 carbon atoms or a carbon having a hydroxyl group. It is preferable that it is a C1-C18 hydrocarbon group. Further, R ¹ and R ² are preferably each independently a hydrocarbon group having 6 to 18 carbon atoms.

  The polyurethane-based elastic fiber of the present invention contains silicone oil and mineral oil as a base component, and the elastic fiber treatment agent having a mineral oil weight ratio of 60% by weight or less is 0.1 to 0.1% of the elastic fiber. It is preferable that 15% by weight is applied.

  The present invention is a method for producing a polyurethane elastic fiber, which comprises preparing a spinning stock solution containing the polyurethane elastic polymer and the sulfonic acid quaternary ammonium salt, and spinning the spinning stock solution.

  In the method for producing a polyurethane-based elastic fiber, it is preferable to prepare a spinning stock solution by adding the sulfonic acid quaternary ammonium salt to a solution containing the polyurethane-based elastic polymer, and spin the spinning stock solution. The sulfonic acid quaternary ammonium salt to be added preferably has a water content of 5% by weight or less and an inorganic salt content of 1% by weight or less.

  Certain sulfonic acid quaternary ammonium salts such as the present invention reduce the polarity of the salt and have good solubility and compatibility with the spinning dope. By adding such a sulfonic acid quaternary ammonium salt to a polyurethane elastic fiber, a polyurethane elastic fiber excellent in antistatic property, chlorine resistance and productivity can be obtained. Moreover, the manufacturing method of the elastic fiber excellent in antistatic property, chlorine resistance, and productivity can be provided.

The schematic diagram explaining the measuring method of roller static electricity generation amount. The schematic diagram explaining the measuring method of knitting tension, and the measuring method of the amount of static electricity generation. The schematic diagram explaining the measuring method of the friction coefficient between fibers. The schematic diagram explaining the measuring method of unwinding speed ratio. The schematic diagram explaining the evaluation method of a chlorine-resistant effect.

  The present invention relates to a polyurethane elastic fiber containing a polyurethane elastic polymer and a specific sulfonic acid quaternary ammonium salt, and a method for producing the same. The present invention will be described in further detail.

(Sulphonic acid quaternary ammonium salt)
The sulfonic acid quaternary ammonium salt used in the present invention is a compound represented by the above general formula (1). In formula (1), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrocarbon group having 1 to 22 carbon atoms or a hydrocarbon group having 1 to 18 carbon atoms having a hydroxyl group. The hydrocarbon group of R ¹ , R ² , R ³ , and R ⁴ may be an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group, and among these, an aliphatic hydrocarbon group is preferable. The aliphatic hydrocarbon group may be an alkyl group or an alkenyl group, and may be linear or branched.
R ⁵ represents an aliphatic hydrocarbon group having 6 to 22 carbon atoms or a substituted phenyl group represented by the general formula (2). In formula (2), R ⁶ represents an aliphatic hydrocarbon group having 6 to 22 carbon atoms. The aliphatic hydrocarbon group for R ⁵ and R ⁶ may be an alkyl group or an alkenyl group, and may be linear or branched.

  Thus, the sulfonic acid quaternary ammonium salt of the present invention is a quaternary ammonium, and by introducing a long-chain aliphatic hydrocarbon group having 6 to 22 carbon atoms into the sulfonate, the polarity of the salt is appropriately reduced. And good solubility and compatibility with the spinning dope can be imparted. Further, as shown in the formula (2), the hydrocarbon group of the sulfonate is a substituted phenyl group having a long-chain aliphatic hydrocarbon group having 6 to 22 carbon atoms, so that better solubility and compatibility are achieved. To have. Specifically, it can exhibit a solubility of about 30 to 50% by weight with respect to DMAC and DMF used as a solvent for the spinning stock solution of polyurethane-based elastic fibers. In addition, since the nitrogen atom of the sulfonic acid quaternary ammonium salt of the present invention has an effect of capturing active chlorine, the addition of the sulfonic acid quaternary ammonium salt of the present invention to the polyurethane elastic fiber can improve antistatic properties and resistance. Chlorine can be added at the same time.

In the sulfonic acid quaternary ammonium salt of the present invention, when 3 to 4 long-chain hydrocarbon groups are introduced into the quaternary ammonium constituting the sulfonic acid quaternary ammonium salt, the polarity may decrease and the compatibility may deteriorate. is there. For this reason, it may bleed out on the surface of the polyurethane-based elastic polymer, and the antistatic performance and chlorine resistance performance may not be stably maintained or may not be exhibited. For these reasons, R ¹ and R ² are each independently a hydrocarbon group having 1 to 22 carbon atoms, and R ³ and R ⁴ are each independently a hydrocarbon group or hydroxyl group having 1 to 7 carbon atoms. It is preferably a hydrocarbon group having 1 to 18 carbon atoms.
R ³ and R ⁴ are each a hydrocarbon group having 1 to 7 carbon atoms, and it is more preferable that no hydroxyl group is present on the hydrocarbon group. When a hydroxyl group is present on the hydrocarbon group of R ³ or R ⁴ , the polarity of the sulfonic acid quaternary ammonium salt is increased, so that antistatic properties are improved. However, bleeding out from polyurethane-based elastic fibers and elution into water are prevented. It is likely to occur, and it may be difficult to maintain productivity and antistatic performance. R ³ and R ⁴ are particularly preferably a hydrocarbon group having 1 to 3 carbon atoms.

Furthermore, when 3 to 4 relatively short-chain hydrocarbon groups are introduced into the quaternary ammonium constituting the sulfonic acid quaternary ammonium salt, the hydrophilicity increases due to the high polarity, and the polyurethane-based elastic fiber dissolves in the spinning dope. May be poor. Moreover, the compatibility with a fiber polymer may also worsen. For these reasons, R ¹ and R ² are each independently a hydrocarbon group having 6 to 18 carbon atoms, and R ³ and R ⁴ are each independently a hydrocarbon group or hydroxyl group having 1 to 7 carbon atoms. It is preferably a hydrocarbon group having 1 to 18 carbon atoms. R ¹ and R ² are more preferably a hydrocarbon group having 8 to 18 carbon atoms, and particularly preferably a hydrocarbon group having 10 to 16 carbon atoms.

Further, when ^{R 5} in the formula (1) is an aliphatic hydrocarbon group, the carbon number 6 to 20 by weight, more preferably 8 to 18, particularly preferably 10 to 16. When R ⁵ is a substituted phenyl group represented by the above formula (2), the hydrocarbon group of R ⁶ preferably has 6 to 20 carbon atoms, more preferably 8 to 18 carbon atoms, and particularly preferably 10 to 16 carbon atoms. The substitution position of R ⁶ is not particularly limited, and may be any position. Among these, R ⁵ is preferably a substituted phenyl group represented by the above formula (2).

  The sulfonic acid quaternary ammonium salt used in the present invention is prepared by stirring the corresponding sodium sulfonate and quaternary ammonium chloride in water at 80 ° C. to 90 ° C. for 3 hours, and dissolving the replicating inorganic salt in the aqueous layer. In order to reduce, the organic layer produced can be easily synthesized by washing with ion-exchanged water several times and drying at 140 ° C. until the water content is 5 wt% or less.

The water content of the sulfonic acid quaternary ammonium salt used in the present invention is preferably 5% by weight or less, more preferably 1% by weight or less, and further preferably 0.3% by weight or less. If the water content exceeds 5% by weight, it may cause a decrease in the yarn strength of the polyurethane elastic fiber. Further, the content of the inorganic salt contained as an impurity is preferably 1% by weight or less, more preferably 0.5% by weight or less, and further preferably 0.1% by weight or less. If the content of the inorganic salt is more than 1% by weight, it may cause a decrease in fiber strength or a decrease in productivity.
Examples of inorganic salts include sodium chloride, potassium chloride, magnesium chloride, calcium chloride and the like.

Examples of the quaternary ammonium cation that forms the sulfonic acid quaternary ammonium salt include dimethyldihexylammonium cation, dimethyldioctylammonium cation, dimethyldidecylammonium cation, dimethyldidodecylammonium cation, dimethyldioleylammonium cation, diethanoldidodecylammonium cation, Examples include diethanoldioleyl ammonium cation, trimethylhexyl ammonium cation, trimethyl octyl ammonium cation, trimethyl decyl ammonium cation, and trimethyl dodecyl ammonium cation.
Similarly, examples of the sulfonate anion that forms a quaternary ammonium salt of sulfonic acid include hexyl sulfonate, octyl sulfonate, dodecyl sulfonate, hexyl benzene sulfonate, octyl benzene sulfonate, and dodecyl benzene sulfonate.

(Polyurethane elastic fiber and method for producing the same)
The polyurethane elastic fiber of the present invention contains a polyurethane elastic polymer and a sulfonic acid quaternary ammonium salt, and has a polyurethane elastic polymer as a main component. Examples of the polyurethane elastic fibers include polyether polyurethane elastic fibers and polyester polyurethane elastic fibers.

Examples of the polyurethane-based elastic polymer include a polyether-based polyurethane elastic polymer using diisocyanate as a hard segment and a polyether diol as a soft segment, and a polyester-based polyurethane elastic polymer using a polyester diol.
These also use low molecular weight polyfunctional active hydrogen compounds as chain extenders. Typically, a chain extender having a polyfunctional active hydrogen atom and an end-capping agent having a monofunctional active hydrogen atom are added to an isocyanate-terminated prepolymer prepared with an organic diisocyanate and a polymer diol. A polyurethane urea elastic polymer having urethane groups in the molecule by reacting in stages or multiple stages can be mentioned. A polyurethane urea elastic fiber can be obtained by dry spinning, wet spinning or melt spinning.

  The polymer diol that is one of the raw materials for producing the polyurethaneurea elastic polymer of the present invention is a polymer having hydroxyl groups at both ends. These include, for example, polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyoxypentamethylene glycol and the like.

  The organic diisocyanate that is one of the raw materials for producing the polyurethaneurea elastic polymer of the present invention is, for example, an aliphatic, alicyclic, or aromatic diisocyanate that is dissolved or liquid under reaction conditions. All things can be applied. Examples include methylene-bis (4-phenyl isocyanate), methylene-bis (3-methyl-4-phenyl isocyanate), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and the like. Methylene-bis (4-phenyl isocyanate) is preferred.

  Examples of the chain extender having a polyfunctional active hydrogen atom that is one of the raw materials for producing the polyurethaneurea elastic polymer of the present invention include hydrazine, polyhydrazide, polyol, ethylenediamine, propylenediamine, and bis- (4-amino). (Cyclohexyl) Polyamines such as methane, m-xylylenediamine, p-xylylenediamine, polyols such as hydroxylamine, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, etc. Can be used.

  As the terminal terminator having a monofunctional active hydrogen atom, which is one of the raw materials for producing the polyurethaneurea elastic polymer of the present invention, for example, a dialkylamine such as diethylamine is used. These chain extenders and end terminators may be used alone or in combination. The polyurethane polymer composition includes an organic or inorganic compounding agent having a specific chemical structure used in known polyurethane polymer compositions, for example, ultraviolet rays such as benzophenone compounds, benzotriazole compounds, and hindered amine compounds. Absorbents; Antioxidants such as hindered phenol compounds; Antifungal agents; Inorganic fine particles such as barium sulfate, magnesium oxide, magnesium silicate, calcium silicate, zinc oxide, hydrotalcite; magnesium stearate, calcium stearate, An anti-tacking agent such as polytetrafluoroethylene and polyorganosiloxane can be appropriately blended.

  The method for producing a polyurethane elastic fiber of the present invention is to prepare a spinning stock solution containing the polyurethane elastic polymer and the sulfonic acid quaternary ammonium salt, and spin the spinning stock solution. The spinning method is not particularly limited, and a known method can be adopted. Since the sulfonic acid quaternary ammonium salt of the present invention is highly hydrophobic, it can be easily washed with water and can be sufficiently dried at high temperature or under reduced pressure. As a result, it is possible to prepare a spinning dope by mixing and reacting together with the raw material of the polyurethane elastic polymer. However, if the sulfonic acid quaternary ammonium salt of the present invention is added before the polymerization of the polyurethane elastic polymer is completed, a reaction with a trace amount of impurities generated during the synthesis of the sulfonic acid quaternary ammonium salt occurs, and the polyurethane elastic It may cause a decrease in yarn quality such as yellowing of the fiber. Therefore, it is preferable to prepare a spinning dope by adding a sulfonic acid quaternary ammonium salt to a solution containing a polyurethane-based elastic polymer, and then spin it.

  As a method for preparing a spinning dope containing a polyurethane-based elastic polymer, for example, each raw material containing the sulfonic acid quaternary ammonium salt of the present invention is put in a solvent such as DMAC or DMF, dissolved, and heated to an appropriate temperature. Then, a method for obtaining a spinning dope by reacting, or mixing the polymer diol and the organic diisocyanate in advance, reacting them at an appropriate temperature, adding a DMAC or DMF solution of a chain extender and reacting them, then the present invention There is a method of adding a sulfonic acid quaternary ammonium salt to obtain a spinning dope.

  In preparing the spinning dope, it is possible to add the sulfonic acid quaternary ammonium salt of the present invention as it is, but using a DMAC or DMF solvent used in the spinning dope, 30 to 50 sulfonic acid quaternary ammonium salt is added. A solution containing wt% can be mixed more uniformly by adding this, and the handleability is also good.

As described above, the sulfonic acid quaternary ammonium salt used in preparing the spinning dope has a water content of 5% by weight or less, and the content of the inorganic salt as an impurity is 1% by weight or less. Preferably there is.
The weight ratio of the sulfonic acid quaternary ammonium salt to the polyurethane elastic polymer (when the polyurethane elastic polymer is 100% by weight) is 0.01 to 10% by weight, preferably 0.5 to 3% by weight. More preferably, it is 1 to 3% by weight. When the amount is less than 0.01% by weight, there is no antistatic effect, and when the amount exceeds 10% by weight, precipitation on the fiber surface and a decrease in fiber strength are caused, so that productivity and yarn quality are remarkably deteriorated.

(Treatment agent for elastic fibers)
The polyurethane elastic fiber of the present invention can be provided with an elastic fiber treating agent. The elastic fiber treatment agent preferably contains silicone oil and mineral oil as base components, and the weight ratio of mineral oil to the treatment agent as a whole is preferably 60% by weight or less. The weight ratio of the mineral oil in the entire treatment agent is preferably 10 to 50% by weight, and more preferably 10 to 30% by weight. When the proportion of the mineral oil is larger than 60% by weight, the sulfonic acid quaternary ammonium salt in the polyurethane elastic fiber is likely to bleed out.

The silicone oil is not particularly limited, and examples thereof include polydimethylsiloxane, polyalkylsiloxane, and polyalkylphenylsiloxane (both silicone oils have a viscosity at 25 ° C .: ^{2 to} 100 mm ² / s). You may use a seed | species or 2 or more types together. Among these silicone oils, the viscosity at 30 ° C. of the elastic fiber treatment agent is preferable because it is easy to handle during oiling of the treatment agent, and the viscosity is too high. It is preferable to select a silicone oil that can be adjusted to 3 to 100 mm ² / s, more preferably 5 to 50 mm ² / s.

Although there is no limitation in particular as mineral oil, For example, the viscosity in 30 degreeC is 30 to 150 second,
Preferred examples include spindle oil and liquid paraffin for 60 to 100 seconds, and one kind or two or more kinds may be used in combination. When the viscosity of the mineral oil is lower than 30 seconds, the quality of the obtained elastic fiber may be deteriorated. On the other hand, if the viscosity of the mineral oil is more than 150 seconds, the viscosity of the entire elastic fiber treatment agent increases, and the resulting elastic fiber may be taken by the roller and the yarn may be broken.

  The processing agent for elastic fibers can further contain components usually used for the processing agent for elastic fibers, such as a smoothing agent, an unraveling improver, a binder, an antistatic agent, an antioxidant, and an ultraviolet absorber.

The elastic fiber treatment agent preferably has a viscosity at 30 ° C. of ² to 100 mm ² / s, and more preferably 5 to 15 mm ² / s. If the viscosity is less than 2 mm ² / s, volatilization of the oil agent may be a problem, and if it is greater than 50 mm ² / s, the wettability of the elastic fiber to the surface may be deteriorated.

  There is no limitation in particular about the method of manufacturing the processing agent for elastic fibers, A well-known method is applicable. The processing agent for elastic fibers is produced by adding and mixing the above-described constituent components in an arbitrary order. Moreover, there is no limitation in particular about the method of providing the processing agent for elastic fibers, A well-known method is applicable.

  The polyurethane-based elastic fiber of the present invention is an elastic fiber in which the above-mentioned elastic fiber treating agent is applied to the elastic fiber in an amount of 0.1 to 15% by weight (preferably 1 to 10% by weight). If it is less than 0.1% by weight, the effect of the present invention is not sufficient, and if it exceeds 15% by weight, it is uneconomical.

  The polyurethane elastic fiber of the present invention has a static electricity on the yarn of -1 KV to +1 KV, preferably -0.7 KV to +0.7 KV, more preferably -0.5 KV to +0.5 KV. When the static electricity on the yarn is smaller than -1 KV or larger than 1 KV, dust or the like may be attracted to the yarn, and the yarn quality and productivity may be lowered.

  As a use of the polyurethane elastic fiber of the present invention, it can be used as a fabric by processing yarn such as covering yarn such as CSY, single covering, PLY and air covering, circular knitting, tricot and the like. In addition, using these processed yarns and fabrics, products that require elasticity such as stockings, socks, underwear and swimwear, and outerwear such as jeans and suits are given elasticity for comfort. Also used for purposes. More recently, it has been applied to disposable diapers.

  The present invention is described in detail in the following examples and comparative examples, but the present invention is not limited thereto. In addition, the evaluation items and the evaluation method in each example and comparative example are as follows.

[Preparation of sulfonic acid quaternary ammonium salt solution]
Sodium decylbenzenesulfonate (60% by weight aqueous solution) and dimethyldihexylammonium chloride (75% by weight isopropanol solution) were mixed at a molar ratio of 1: 1, and the water in the system was the same weight as the sulfonic acid quaternary ammonium salt produced. Ion exchange water was added so that After stirring this mixed solution at 90 ° C. for 1 hour, stirring was stopped and the mixture was allowed to stand for 1 hour to separate the organic layer and the aqueous layer. The aqueous layer was discarded, ion-exchanged water having the same weight as the sulfonic acid quaternary ammonium salt produced was added, stirred at 90 ° C. for 15 minutes, allowed to stand for 1 hour, and then the aqueous layer was discarded. Further, the organic layer was washed with ion-exchanged water in the same manner once more, and the amount of sodium chloride replicated was adjusted to 0.1 wt%. Furthermore, it stirred at 140 degreeC for 3 hours, and dried until the moisture content became 0.3 weight% or less. After cooling to 100 ° C., DMAC was added so that the sulfonic acid quaternary ammonium salt would be 30% by weight, and the solution was cooled to room temperature (the sulfonic acid quaternary ammonium salt solution of Example 1). The sulfonic acid quaternary ammonium salts used in other examples were prepared in the same manner except that the corresponding sodium sulfonate and ammonium chloride were changed.

[Preparation of spinning dope]
A polyoxytetramethylene glycol having a number average molecular weight of 1800 and methylene-bis (4-phenylisocyanate) are reacted at a molar ratio of 1: 2, and then chain-extended using a propylenediamine in DMAC solution to form a DMAC having a polymer concentration of 27%. A solution was obtained. The viscosity at 30 ° C. was 1700 mPaS. To this solution, the prepared sulfonic acid quaternary ammonium salt solution is added to and mixed with the polymer (polyurethane-based elastic polymer) so that the sulfonic acid quaternary ammonium salt has a target addition amount. Was prepared.

[Preparation of polyurethane urea elastic fiber]
The above spinning solution was discharged into a nitrogen stream at 230 ° C. for dry spinning. A bobbin was wound at a speed of 500 m / min to obtain 44 dtex monofilament cheese (wound amount 400 g).

[Treatment agent for polyurethane urea elastic fiber]
When dry-spinning the above polyurethane urea elastic fiber, an oil agent obtained by mixing polydimethylsiloxane (viscosity 10 centistokes) and liquid paraffin 50 seconds at a weight ratio of 7: 3 is 5% by weight with respect to the elastic fiber by an oiling roller. It was made to adhere.

Polyurethane urea elastic fiber evaluation method (knitting tension, static electricity generation amount)
In FIG. 2, the roller (9) attached to the U gauge (8) with the elastic yarn (4) vertically taken from the cheese (3) through the compensator (5), the roller (6), and the knitting needle (7). And connected to a speedometer (10) and a take-up roller (11). The rotational speed of the take-up roller is adjusted so that the traveling speed of the speedometer (10) becomes a constant speed (for example, 10 m / min, 100 m / min), and the knitting tension at that time is taken up by the take-up roller. Is measured with a U gauge (8), and the friction (g) between the fibers / knitting needles is measured. The amount of static electricity generated (kV) is measured with a Kasuga-type potentiometer (12) at a distance of 1 cm from the running yarn.

[Friction coefficient between fibers (F / Fμs)]
In FIG. 3, a monofilament of elastic fiber to which a treatment agent has been applied is taken about 50 to 60 cm, a load T1 (13) is suspended at one end, and the other is attached to the U gauge (15) via a roller (14). Pull the end and pull at a constant speed (for example, 3 cm / min), measure the secondary tension T2 at that time with the U gauge (15), and obtain the inter-fiber friction coefficient by the following equation (1).
Friction coefficient (F / Fμs = 1 / θ · ln (T2 / T1) (1)
(In Equation 1, θ = 2π, ln = natural logarithm, T1 is 1 g per 22 dtex)

[Unwinding speed ratio]
In FIG. 4, the fiber cheese (16) to which the treatment agent is applied is set on the unwinding side of the unwinding speed ratio measuring machine, and the paper tube (17) is set on the winding side. After setting the winding speed to a constant speed, the rollers (18) and (19) are activated simultaneously. In this state, there is almost no tension on the yarn (20), so the yarn is stuck on the cheese and does not leave, so the unwinding point (21) is in the state shown in FIG. By changing the unwinding speed, the unwinding point (21) of the yarn (20) from the cheese changes, so the unwinding speed is set so that this point coincides with the contact point (22) between the cheese and the roller. The unraveling speed ratio is obtained by the following equation (2). The smaller this value is, the better the unpacking property is.
Unwinding speed ratio (%) = ((winding speed−unwinding speed) / unwinding speed) × 100 (2)

[Roller static electricity, yarn static electricity]
In FIG. 1, the heat-treated cheese (1) is set on the unwinding side of the unwinding speed ratio measuring machine, rotated at a peripheral speed of 50 m / min, the winding side is set to 100 m / min, and the cheese is 2 cm above the cheese. Using a Kasuga-type potentiometer (2), the roller static electricity (static electricity on cheese) after 1 hour from the start of rotation is measured. Measure the static electricity generated on the running thread (static electricity on the thread) when measuring the static electricity on the roller.

[Method for evaluating the effect of chlorine resistance]
In FIG. 5, 1.0 g of fiber was taken from cheese, washed and dried with 50 ml of n-hexane, immersed in 100 g of an aqueous sodium hypochlorite solution having an effective chlorine concentration of 100 ppm, and treated at 50 ° C. for 100 hours. One fiber, 20 cm, was applied to a U gauge (8), pulled at 20 cm / min until it was cut, and the load at break was measured. In addition, the breaking point load (strength) of the fiber before a process was 51g.

  The cheese used for these evaluations was processed for 48 hours in an atmosphere of 35 ° C. and 50% RH.

(Water content, inorganic salt content)
The water content and inorganic salt content of the sulfonic acid quaternary ammonium salt and the antistatic agent of the comparative example were measured by the Karl Fischer method and the ion chromatograph, respectively. In addition, the sulfonic acid quaternary ammonium salt of the example was confirmed by measurement before making the DMAC solution.

[Examples 1-7 and Comparative Examples 1-7]
The quaternary ammonium sulfonate added in each Example and the antistatic agent added in Comparative Examples are shown below. The quaternary ammonium sulfonates of Examples 1-7 were prepared as described above. About the antistatic agent of the comparative example 1, what was melt | dissolved in excess isopropanol, precipitated the inorganic salt, and then filtered and dried was used. About the antistatic agent of Comparative Examples 2-5, the corresponding sodium sulfonate and ammonium chloride were made to react in excess isopropanol, the inorganic salt was filtered, and the dried thing was used. Comparative Example 6 was used as it was because no purification or the like was required.

About Examples 1-7, as mentioned above, the sulfonic acid quaternary ammonium salt solution and the spinning dope were prepared, and the polyurethane urea elastic fiber was obtained. For Comparative Examples 1 to 6, instead of adding the sulfonic acid quaternary ammonium salt solution, except for adding the antistatic agent of each Comparative Example to prepare the spinning dope, the same as in Example 1, A polyurethaneurea elastic fiber was obtained. For Comparative Example 7, a polyurethaneurea elastic fiber was obtained in the same manner as in Example 1 except that a spinning stock solution containing no antistatic agent was prepared. The obtained polyurethane urea elastic fiber was evaluated by the above method. Tables 1 and 2 show the evaluation results and the water content and inorganic salt content of the added quaternary ammonium sulfonate / antistatic agent.
In both Examples and Comparative Examples, a spinning stock solution was prepared by adding quaternary ammonium sulfonate or antistatic agent so as to be 3% by weight based on the polymer.
Example 1: Dimethyldihexylammonium decylbenzenesulfonate Example 2: Dimethyldioctylammonium dodecyl sulfonate Example 3: Dimethyldidecylammonium dodecylbenzene sulfonate Example 4: Dimethyldidecylammonium dodecyl sulfonate Example 5: Dimethyldioleylammonium dodecylbenzene Sulfonate Example 6: Diethanol didodecyl ammonium dodecyl benzene sulfonate Example 7: Trimethyl dodecyl ammonium dodecyl benzene sulfonate Comparative example 1: Sodium dodecyl benzene sulfonate Comparative example 2: Dodecyl ammonium dodecyl sulfonate Comparative example 3: Methyl dodecyl ammonium dodecyl sulfonate Comparative example 4: Dimethyldodecyl ammonium benzene Sulfonate Comparative Example 5: Trioctylmethylammonium toluene sulfonate Comparative Example 6: Zinc oxide Comparative Example 7: No addition

[Examples 8 to 12]
In the sulfonic acid quaternary ammonium salt used in Example 3, the addition amount was examined in the range of 0.1 to 5% by weight with respect to the polymer. The sample yarn was prepared in the same manner as in Example 3 only by adjusting the amount of the sulfonic acid quaternary ammonium salt solution added to the spinning dope. The evaluation results are shown in Table 3.

  As shown in Tables 1 and 2, the sulfonates of Comparative Examples 1 to 5 have poor compatibility with the fiber polymer, and the antistatic properties are worse than those of the sulfonic acid quaternary ammonium salts of Examples. The inorganic additive of Comparative Example 6 has little effect on antistatic properties. As shown in Table 3, the addition amount is optimally 1 to 3% by weight. It can be seen that antistatic properties and chlorine resistance can be imparted to the polyurethane elastic fiber by adding the sulfonic acid quaternary ammonium salt of the example.

  According to the present invention, it is possible to provide a polyurethane-based elastic fiber having improved antistatic properties, productivity, chlorine resistance and the like.

DESCRIPTION OF SYMBOLS 1 Elastic fiber cheese 2 Kasuga type potential difference measuring device 3 Elastic fiber cheese 4 Elastic thread 5 Compensation sweater 6 Roller 7 Knitting needle 8 U gauge 9 Roller 10 Speedometer 11 Winding roller 12 Kasuga type potential difference measuring device 13 Load 14 Roller 15 U Gauge 16 Cheese 17 Winding paper tube 18 Roller 19 Roller 20 Traveling yarn 21 Unwinding point 22 Contact point of cheese and roller

Claims (7)

A polyurethane-based elastic fiber containing a polyurethane-based elastic polymer and a sulfonic acid quaternary ammonium salt,
A polyurethane-based elastic fiber, wherein the sulfonic acid quaternary ammonium salt is a compound represented by the following general formula (1) and is contained in an amount of 0.01 to 10% by weight based on the polyurethane-based elastic polymer.

^{(Wherein, R 1, R 2, R} 3, R 4 , the .R ⁵ showing independently a hydrocarbon group having 1 to 18 carbon atoms having a hydrocarbon group or a hydroxyl group of 1 to 22 carbon atoms, A C6-C22 aliphatic hydrocarbon group or a substituted phenyl group represented by the following general formula (2) is shown.)

(In the formula, R ⁶ represents an aliphatic hydrocarbon group having 6 to 22 carbon atoms.) R ¹ and R ² are each independently a hydrocarbon group having 1 to 22 carbon atoms, and R ³ and R ⁴ are each independently a carbon group having 1 to 7 carbon atoms or a hydroxyl group. The polyurethane elastic fiber according to claim 1, which is a hydrocarbon group having a number of 1 to 18. The polyurethane elastic fiber according to claim 2, wherein R ¹ and R ² are each independently a hydrocarbon group having 6 to 18 carbon atoms.   The treatment agent for elastic fibers, which contains silicone oil and mineral oil as a base component and the weight ratio of mineral oil is 60% by weight or less, is applied to the elastic fiber in an amount of 0.1 to 15% by weight. The polyurethane-type elastic fiber in any one of 1-3. It is a manufacturing method of the polyurethane-type elastic fiber in any one of Claims 1-4, Comprising:
A method for producing a polyurethane elastic fiber, comprising preparing a spinning stock solution containing the polyurethane elastic polymer and the sulfonic acid quaternary ammonium salt, and spinning the spinning stock solution.   6. The method for producing a polyurethane elastic fiber according to claim 5, wherein a spinning stock solution is prepared by adding the sulfonic acid quaternary ammonium salt to a solution containing the polyurethane elastic polymer, and the spinning stock solution is spun.   The polyurethane-based elastic fiber according to claim 6, wherein the added sulfonic acid quaternary ammonium salt has a water content of 5% by weight or less and a content of an inorganic salt as an impurity of 1% by weight or less. Manufacturing method.

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