JP3390510B2 - Polyetherester block copolymer-based elastic yarn - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyetherester block copolymer-based elastic yarn. For more information,
INDUSTRIAL APPLICABILITY The present invention is a polyetherester block copolymer system which is excellent in unwinding property from a winding package, generates less static electricity during running of a yarn, and has no scum accumulation on a yarn guide, and has excellent handling properties. It relates to elastic yarn. 2. Description of the Related Art Conventionally, rubber or polyurethane-based elastic yarns have been used as elastic yarns, and are used in various fields such as sea swimsuits, ski pants, training pants, etc., which are required to fit the body. It's being used. In recent years, elastic yarns from polyetherester block copolymers having a hard segment of polyester such as polybutylene terephthalate and a soft segment of polytetramethylene glycol have a chemical structure similar to that of polyester fibers. Therefore, it is expected that conventional elastic yarns cannot withstand post-processing (eg, dyeing processing, alkali weight reduction processing, etc.) under the same conditions as polyester fibers due to insufficient heat resistance and chemical resistance, Various practical studies have been made. [0004] However, such polyetherester block copolymer-based elastic yarns are commercially produced in large quantities.
When used, there is a problem that scum is deposited on the yarn guide during the yarn running, and the yarn guide is soiled, or static electricity is generated, causing various troubles in the knitting and weaving yarn process. Conventionally, in polyurethane-based elastic yarn,
There has been proposed an oil agent comprising polydimethylsiloxane or mineral oil as a main component, and fine particles such as talc or magnesium stearate suspended therein (for example, Japanese Patent Publication No. 44-286). Indeed, although such an oil agent has an effect of improving the unwinding property of urethane-based elastic yarn, even when applied to polyetherester copolymer-based elastic yarn, the elastic yarn itself generates static electricity compared to urethane-based elastic yarn. For this reason, the above problem cannot be completely solved. [0006] In order to solve the problem of the generation of static electricity, the present inventors have previously proposed a method of blending an alkyl phosphate-based antistatic agent with a treating agent having dimethyl silicone and mineral oil as smoothing components ( JP-A-4-146276
No.). According to such a method, sufficient lubricity and antistatic properties are imparted without swelling the polyetherester block copolymer, so that in the subsequent steps such as unwinding of the original yarn from the winding package and knitting and weaving. Although the problem of scum accumulation on the yarn guide is reduced, the scum accumulation on the yarn guide sometimes does not decrease. As a result of repeated investigations to suppress such a phenomenon, it was found that the compatibility between dimethyl silicone and the alkyl phosphate salt was insufficient, and that the scum increased when the alkyl phosphate salt was separated and precipitated over time. . It is considered that a nonionic emulsifier may be used in combination to increase the compatibility between the two.However, the above problem cannot be solved because the nonionic emulsifier generally has an action of swelling the polyetherester block copolymer. . On the other hand, Japanese Patent Laid-Open Publication No.
An oil agent containing polydimethylsiloxanediol (polymerization degree: 50 or less) as a main component instead of polydimethylsilicone has been proposed. According to this method, although the generation of scum is reduced because the compatibility between the polydimethylsiloxane diol and the anionic surfactant is improved, since the polydimethylsiloxane diol is probably reactive, the There is a problem that polymerization progresses in the state of being adhered to the surface, and the running friction increases, and the occurrence of thread breakage and scum during post-processing increases. SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and has as its object to improve the unwinding property of a winding package and reduce the friction during yarn running. Another object of the present invention is to provide a polyetherester block copolymer-based elastic yarn which is extremely excellent in handleability, in which generation of static electricity is small, and accumulation of scum on the yarn conductor is significantly reduced. The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a partial phosphate ester salt of a compound obtained by adding ethylene oxide to a branched alcohol (hereinafter referred to as an ethylene oxide-modified alkyl) (Sometimes referred to as a phosphate salt) improves the compatibility with low-viscosity polyorganosiloxanes, so it can be used as a homogeneous oil when used in combination with mineral oil, and also reduces the volatility of polyorganosiloxanes. As a result, it has been found that the stability of the smoothness performance of the elastic yarn is also improved, and the present invention has been reached. That is, according to the present invention, an elastic yarn comprising a polyetherester block copolymer has the following (A)
To (C) as essential components, and the content of each component simultaneously satisfies the following (1) to (3):
There is provided a polyetherester block copolymer-based elastic yarn, wherein 1.5 to 5.0% by weight is attached to the yarn weight. (A) a polydimethyl silicone having a viscosity of 3 to 8 centistokes at 25 ° C., (B) a mineral oil having a viscosity of 8 to 16 centistokes at 25 ° C., and (C) an ethylene oxide adduct of a branched alcohol. a partial phosphoric ester _{salts, (1) 80 ≦ W A} + W B ≦ 95 (2) 1 ≦ W A / W B ≦ 3 (3) 5 ≦ W C ≦ 20 [ _{where, W A, W B, W} C is The content ratios (wt%) of the A, B, and C components in the oil agent active ingredient are respectively shown. The polyetherester block copolymer of the present invention comprises a dicarboxylic acid component mainly composed of terephthalic acid, a glycol component mainly composed of 1,4-butanediol or ethylene glycol, and an average molecular weight of 400.
And a poly (oxyalkylene) glycol of up to 4000. Among them, poly (oxyalkylene) glycol has an average molecular weight of 100
0-3000 polytetramethylene glycol or polyethylene glycol is preferred. The poly (oxyalkylene) glycol content in the polyetherester block copolymer is 50.
８０80% by weight, preferably 80% by weight.
When the temperature exceeds the above, an elastic yarn having excellent elastic performance can be obtained, but since the melting point of the copolymer becomes too low, the elastic performance at the time of dry heat treatment and wet heat treatment is sharply reduced, and the elastic yarn has poor durability. Will be. If the content is less than 50% by weight,
Only an elastic yarn having a large permanent set and inferior elastic properties can be obtained. Further, in order to improve durability such as ultraviolet resistance and heat resistance, it is preferable to add an antioxidant, an ultraviolet absorber and the like to the above-mentioned polyetherester block copolymer. Examples of such antioxidants include hindered phenol compounds, hindered amine compounds, sulfur atom-containing ester compounds, and the like, and examples of ultraviolet absorbers include benzophenone compounds, benzotriazole compounds, sacylate compounds, and the like. . In the present invention, an oil containing polydimethylsilicone (A), mineral oil (B) and ethylene oxide-modified alkyl phosphate salt (C) is added to an elastic yarn comprising the above-mentioned polyetherester block copolymer. It is important to provide. Here, the polydimethyl silicone (A), which is the main component of the oil agent, needs to have a viscosity at 25 ° C. of 3 to 8 centistokes, preferably about 5 centistokes. If the viscosity of the polydimethyl silicone is less than 3 centistokes, the volatility of the silicone cannot be suppressed even if an ethylene oxide-modified alkyl phosphate salt described later is used, and the polydimethyl silicone is scattered during storage to be elastic. The composition of the oil agent on the yarn changes and the smoothing performance becomes insufficient. On the other hand, if it exceeds 8 centistokes, the compatibility with the ethylene oxide-modified alkyl phosphate salt becomes insufficient and phase separation is caused, and the occurrence of scum increases, which is not preferable. On the other hand, it is important that the mineral oil (B) has a viscosity at 25 ° C. in the range of 8 to 16 centistokes. When the viscosity of the mineral oil is less than 8 centistokes, it tends to swell the polyetherester block copolymer in addition to the problem of easy volatilization as in the case of the polydimethyl silicone. On the other hand, if it exceeds 16 centistokes, the viscosity of the oil agent system is increased, and the oil supply to the yarn tends to be uneven, and the smoothness of the yarn is also lowered, which is not preferable. It is important that the component (C) used in combination with the above-mentioned component is a partial phosphate salt (ethylene oxide-modified alkyl phosphate salt) obtained by adding ethylene oxide to a branched alcohol. If the alkyl group has no straight chain, the compatibility with dimethyl silicone is reduced, so that phase separation occurs,
It is not preferable because the volatility of dimethyl silicone causes a decrease in smoothness and an increase in scum generation. The addition mole number of ethylene oxide to the alcohol is not preferable because if it is too large, the hydrophilicity becomes too high and the compatibility with polydimethylsilicone decreases, while if it is too small, the polarity becomes too strong and it dissolves in the oil agent. It becomes difficult. Therefore, the preferred number of added moles is 2 to 6
Range of moles. On the other hand, the alkyl group of the alcohol is not particularly limited as long as it has a branch, but if the number of carbon atoms is small, the hydrophilicity is increased, and if the number is large, the property becomes solid. The compatibility in the oil agent decreases. Therefore, the carbon number of the alkyl group is 8
The number is preferably 18 or less, and the larger the number of branches, the more preferable it is because the property becomes closer to that of a liquid and it is easily dissolved in an oil agent. Further, as counter ions of the phosphate salt, Na, K
Examples thereof include alkali metal ions, ammonium cations, and the like, and Na and K are particularly preferable for enhancing antistatic properties. As the component (C) preferably used,
EO addition isooctyl phosphate K, added EO iso lauryl phosphate K, etc. EO addition secondary alcohol (C ₁₂ ~C ₁₄₎ phosphate K can be mentioned. In the oil agent used in the present invention, the total amount of the components (A) and (B) described above in detail (W _A +
W _B) is 95 wt% 80 wt% or more with respect to oil active ingredients or less, it is necessary to preferably contain 80 wt% to 90 wt% or less. If the content is less than 80% by weight, the smoothness becomes insufficient, the running stability of the yarn is reduced, and abnormal elongation of the yarn occurs. 9
When the content exceeds 5% by weight, the content of the component C is reduced to 5% by weight.
Since the above cannot be performed, the antistatic property becomes insufficient, which is not preferable. In the present invention, the weight ratio (W _A / W _B ) of the component (A) to the component ( _B ) is 1 or more and 3 or less.
Preferably, it must be in the range of 1.5 or more and 2.5 or less. If the weight ratio is less than 1, not only the smoothness becomes insufficient and the running stability of the elastic yarn is reduced, but also the elastic yarn is easily swelled due to an increase in the ratio of mineral oil, and the fiber properties are reduced. It is not preferable because the polymer deteriorates and the deteriorated polymer is scraped by the yarn guide and is easily deposited as scum. On the other hand, when it exceeds 3, although the smoothness is good, the compatibility of the C component is reduced and the phase is easily separated, and the effect of the present invention is hardly obtained. [0022] (C) the content W _C of the component, 20 wt% 5 wt% or more of the oil active ingredients or less, it is necessary and preferably 10 to 15 wt%. When the content W _C is less than 5% by weight, the antistatic performance becomes insufficient. On the other hand, when the content exceeds 20% by weight, no further effect of the antistatic performance is exhibited. In addition to the increase, the smoothness is reduced, and the C component is not easily dissolved in the oil agent, which is not preferable because it causes scum and the like. The oil agent in the present invention is based on the above components. If necessary, other compounding agents such as antioxidants, compatibilizers, stability improvers, fatty acids or alcohols may be used. A smoothing aid such as a silicone compound modified with the above may be added within a range not to impair the object of the present invention. In order to attach the oil agent described above to the elastic yarn, an emulsion emulsified in water may be used, or an undiluted solution may be used as it is, and any method can be adopted. Above all, in the method using the undiluted solution as it is (straight type treatment), the emulsifier, which is usually used in combination, easily swells the elastic yarn and easily generates scum,
This is advantageous because it eliminates the need to use this emulsifier in combination. The oil agent can be applied to the elastic yarn by any generally known means. Among them, a method of applying a measured amount through an oiling nozzle for reducing the resistance applied to the yarn is more preferable. It is taken as a preferred method. The amount of the oil agent adhering to the elastic yarn must be 1.5 to 5% by weight as an active ingredient based on the yarn weight. If the amount of adhesion is less than 1.5% by weight, the smoothness and antistatic performance of the yarn become insufficient, causing problems such as yarn breakage and scum. On the other hand, if it exceeds 5% by weight, the effect of suppressing scum and static electricity is little improved, and conversely, an excessive oil agent will contaminate the yarn conductor and the like, causing a new problem, which is not industrially advantageous. As described in detail above, the oil agent imparted to the elastic yarn of the present invention is obtained by mixing a relatively low-viscosity mixture of polydimethyl silicone and mineral oil with a branched alcohol. The partial reason why the partial phosphate ester salt of the ethylene oxide adduct was blended as an antistatic agent is unknown, but their compatibility is extremely good and phase separation is difficult, and It is estimated that the resulting scum is suppressed. In addition, since the compatibility is good, even if a material having a lower viscosity than conventional polydimethylsilicone is used, its volatilization is suppressed, and it is presumed that the stability over time of the smoothness performance is also improved. Therefore, the elastic yarn of the present invention has a good unwinding property of the raw yarn from the winding package, and generates static electricity and scum deposits on the yarn guide in the post-processing steps such as the yarn-making step and the knitting and weaving operation. Is stably and significantly reduced, and a very good product can be obtained. The present invention will be described below in more detail with reference to examples. In addition, each evaluation item in an Example was measured according to the following method. 1. The viscosity was measured by a conventional method using a Cannon-Fenske viscometer in a thermostatic water bath set to a treatment agent viscosity of 25 ° C. 2. 20 cc of oil in a cylindrical container with a compatible diameter of about 5 cm
After dehydration treatment at 50 ° C. for 1 hour under a reduced pressure of 40 mmHg, the degree of compatibility of the oil agent was visually determined and evaluated according to the following criteria. ：: transparent (good compatibility) △: slightly turbid x: formation of cloudy precipitate (poor compatibility) The obtained elastic yarn is subjected to a warping machine by 240 frames, and is used as a warp beam at a speed of 20 m / min.
Wind up 0 m. At this time, the state of static electricity generation was measured by a Kasuga-type current collecting potential meter. The evaluation was based on the following criteria. ：: 0 to 0.5 kV (charged voltage) Δ: 0.5 to 1.0 kV (charged voltage) ×: 1.0 kV or more (charged voltage) Oil solution volatility 2 g of oil solution is precisely weighed in a stainless steel dish with a diameter of 8 cm,
The weight loss rate (%) after standing for 24 hours in hot air drying air was measured and evaluated according to the following criteria. ：: less than 15% Δ: 15 to 30% ×: more than 30% The obtained elastic yarn is unwound at a speed of 15 m / min, and has an intermediate diameter of 6 mm.
0mm, matte chrome pin with surface roughness 11s 180 °
At a contact angle of. From the tension (T ₁ , T ₂ (g)) before and after the pin at this time, the friction coefficient (μ) was calculated by the following equation. (Note, T ₁ was adjusted to about 5g.) Μ = 1 / π [1n (T 2 / T 1)] Evaluation was rated on the following criteria than this value. ：: less than 0.35 Δ: 0.35 to 0.4 ×: more than 0.4 The polyetherester block copolymer constituting the swellable elastic yarn was melt-molded to obtain a sheet having a thickness of 0.3 mm, and a 3 cm × 5 cm rectangular sample cut out of the sheet was placed in a stock solution of oil at 50 ° C. for 1 day. Perform immersion treatment. The polymer swelling degree R was calculated by the following equation. R = (W _t −W _o ) / W _o × 100 (%) where W _o is the weight of the sample before immersion in the oil agent, and W _t is the sample after immersion in the oil agent was washed with a 0.5% aqueous solution of sodium dodecylbenzenesulfonate. Thereafter, the sample weight was measured by thoroughly washing with water, drying at 105 ° C. for 1 hour, and then weighing. Evaluation was made from these values according to the following criteria. ：: less than 5% Δ: 5 to 10% ×: more than 10% The distance from the yarn unwinding package to the first guide is 2
The yarn was drawn out at a speed of 10 m / min through this yarn guide. The unwinding property at this time was evaluated in three stages. ：: Can be unwound stably without any problem. Δ: There is no breakage of the yarn even though the yarn is slightly drawn. ×: A great sense of resistance is exerted on the drawn yarn, and the yarn breaks frequently. 8. A razor blade is applied to the yarn such that the draft between the yarn supply roller and the take-up roller has a speed ratio of 1.75 and the angle between the rollers is 110 °.
m for 3 minutes. At this time, the scum generation was evaluated as follows according to the accumulation state of the scum generated on the razor blade. ：: none to slightly wet trace Δ: Degree of being judged as a slightly whitish scum. X: It is clearly recognized as scum as white viscous or white powder. Example 1 A polyetherester block copolymer containing butylene terephthalate as a hard segment and polytetramethylene glycol as a soft segment and having a hard segment content of 40 wt%, which is a hindered amine antioxidant 0.2 w
t%, 0.2wt of benzotriazole UV absorber
% Of the block copolymer was melted at 245 ° C. and extruded from a spinneret at a speed of 1000 m / min to obtain an elastic yarn of 40 denier / 6 filaments. At this time, the oil agent shown in Table 1 was applied to the spun yarn through a measuring nozzle so that the weight of the oil agent was 3% by weight based on the fiber weight in a non-hydrated state (straight type). The evaluation results are shown in Table 1. [Table 1] Example 2 The procedure of Example 1 was repeated, except that the oil agent applied in Example 1 was changed to that shown in Table 2. No. 19 has 1.5 wt%
And The results are shown in Table 2. [Table 2]

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) D06M 13/00-15/72

Claims (1)

(57) [Claims 1] An elastic yarn comprising a polyetherester block copolymer contains the following components (A) to (C) as essential components, and the content of each component is as follows: The following (1)-
An oil agent that simultaneously satisfies (3) is 1.5 to the yarn weight.
A polyetherester block copolymer-based elastic yarn, characterized in that the elastic yarn has an adhesion of about 5.0% by weight. (A) a polydimethyl silicone having a viscosity of 3 to 8 centistokes at 25 ° C., (B) a mineral oil having a viscosity of 8 to 16 centistokes at 25 ° C., and (C) an ethylene oxide adduct of a branched alcohol. a partial phosphoric ester _{salts, (1) 80 ≦ W A} + W B ≦ 95 (2) 1 ≦ W A / W B ≦ 3 (3) 5 ≦ W C ≦ 20 [ _{where, W A, W B, W} C is The content ratio (wt%) of the A, B, and C components in the oil agent active ingredient is shown. ]