JPH04146276A - Elastic yarn of polyether ester block copolymer - Google Patents

Abstract

PURPOSE:To obtain the title elastic yarn having excellent reeling properties from wound package and excellent handleability free from deposit of scum on yarn guide by providing elastic yarn of polyether ester block copolymer with a treating agent satisfying specific physical properties. CONSTITUTION:Elastic yarn comprising a polyether ester block copolymer is provided with 0.5-10wt.% (active ingredient) based on weight of yarn of a treating agent satisfying viscosity (eta), a degree of swelling (Rs) and a coefficient of friction shown by the formulas, preferably one which a mixture of dimethylsilicone having 10-30cst viscosity at 25 deg.C and a mineral oil having 4-21cst viscosity in the blending ratio of 100/0-40/60 as a base and further 5-20wt.% (active ingredient) phosphate-based antistatic agent liquid at 20 deg.C to give elastic yarn of polyether ester block copolymer having excellent reeling properties and extremely excellent handleability free from deposit of scum.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a polyetherester block copolymer elastic yarn. More specifically, the present invention relates to an elastic polyether ester block copolymer yarn that has excellent unwinding properties from a winding package, no scum buildup on the yarn guide even when the yarn is running, and extremely improved handling properties.

<Prior art> Rubber or polyurethane-based elastic threads have traditionally been used in fields that require a good fit to the body, such as sports clothing such as sea swimsuits, ski pants, training pants, underwear, socks, etc. It is used in many ways, including for clothing. In recent years, when such elastic yarns are used in combination with polyester fibers, or mixed fibers or knitted,
There were problems in that it had insufficient heat resistance, chemical resistance, etc., and could not withstand the post-processing conditions of polyester fibers (for example, dyeing processing, alkali weight reduction processing, etc.).

On the other hand, a polyether ester block copolymer such as polyester such as polybutylene terephthalate as a hard segment and polytetramethylene glycol as a soft segment has rubber-like elasticity, and an elastic thread can be obtained from this copolymer. is already known, and since its chemical structure is similar to that of polyester fiber, it is expected that it can be post-processed under the same conditions as polyester fiber, and in recent years, its practical application has been studied.

However, when such polyether ester block copolymer elastic threads are used experimentally in small quantities, no major problems occur, but when produced and used commercially in large quantities, the filaments tend to stick together and the raw yarn The unwinding performance of the yarn deteriorates, and scum accumulates on the yarn guiding guide when the yarn runs, contaminating the yarn guiding.

<Object of the Invention> The present invention has been made in view of the above background, and its object is to provide excellent unwinding properties from the winding package, and to provide running stability without scum accumulation on the yarn guide. An object of the present invention is to provide an excellent polyetherester block copolymer elastic thread.

<Structure of the Invention> As a result of intensive studies to achieve the above object, the present inventors found that the polyether ester block copolymer swells depending on the composition of the oil agent, and the low molecular weight compounds present in the copolymer swell in the oil agent. It was discovered that the occurrence of scum increases due to scum being eluted or being easily scraped due to friction with the thread guiding guide etc. during running of the thread, and as a result of further intensive studies, the present invention was arrived at.

That is, according to the present invention, in an elastic yarn made of a polyether ester block copolymer, a treatment agent that simultaneously satisfies the following (al~+C1 formula) is added to the elastic yarn in an amount of 0.5 to 10% based on the weight of the fiber. Polyether ester block copolymer elastic yarn attached by weight% (as an active ingredient), (a) Treatment agent stock solution viscosity (η)≦25cst<25
C) (b) Polymer swelling (Rs >610%) (c) Metal-to-metal friction coefficient (M/Mμ) ≦0.18 is provided.

The polyether ester block copolymer targeted by the present invention has a dicarboxylic acid component mainly composed of terephthalic acid,
A glycol component mainly consisting of 1.4-butanediol,
It is a copolymer containing poly(oxyalkylene) glycol having an average molecular weight of 400 to 4,000 as a constituent component.

To explain in more detail about this polyether ester block copolymer, 80 mol% or more of the dicarboxylic acid component,
Preferably, 90 mol% or more of the acid component is terephthalic acid or its ester-forming derivative, and 80 mol% or more, preferably 90 mol% or more of the glycol component is 1,4
- A low molecular weight glycol component that is butanediol or its ester-forming derivative, and a molecular weight of 400 to 40
00, preferably from 600 to 3500, particularly preferably from 1000 to 300
A copolymer obtained by a polycondensation reaction with poly(oxybutylene) glycol of 0 is preferably used.

The content of poly(oxyalkylene) glycol in the polyether ester block copolymer is 50 to 80% by weight.
It is preferably in the range of , and if it exceeds 80% by weight,
Although an elastic yarn with excellent elastic performance can be obtained, since the melting point of the copolymer is too low, the elastic performance during dry heat treatment and warm heat treatment decreases rapidly, resulting in an elastic yarn with poor durability. . On the other hand, if it is less than 50% by weight, only elastic yarns with large permanent set and poor elastic properties can be obtained.

Further, in order to improve durability such as ultraviolet ray resistance and heat resistance, it is preferable to add an antioxidant, an ultraviolet absorber, etc. to the above-mentioned polyetherester block copolymer. Examples of such antioxidants include hindered phenol compounds, hindered amine compounds, sulfur atom-containing ester compounds, and examples of ultraviolet absorbers include benzophenone compounds, benzotriazole compounds, and sacylate compounds. .

In the present invention, it is important to impart a treatment agent having specific properties to the elastic yarn made of the above-mentioned polyetherester block copolymer.

That is, the viscosity of the processing agent stock solution at 25°C (η) is 25
It needs to be less than centistokes (cst).

If it exceeds 25 cst, the problem of thread breakage due to thread tangles is likely to occur due to the characteristics of the polyether ester block copolymer elastic thread itself (adhesiveness to guides and easy stretching properties). Running friction increases, causing various process troubles.

In addition, the polymer swelling degree (Rs) of the processing agent stock solution is 10%
The content should preferably be 8% or less; if it exceeds this, the threads will be easily abraded by various thread guides during post-processes such as weaving and weaving, and the affinity between the processing agent and the polymer will be high. Since the low molecular weight compounds present in the elastic yarn are eluted during processing, the accumulation of scum increases significantly, reducing the production efficiency of weaving and knitting and lowering the quality of the finished product. Moreover, if the swelling of the polymer is large, the adhesion between the threads will become thicker, and the unwinding properties of the raw threads will also be reduced.

Furthermore, the metal 7/metal friction coefficient (M/Mμ) measured under the contact pressure of 111 Dan7'rwn2 of the treatment agent was 0.18.
It is important to do the following. Elastic threads are usually spun and handled under tension, so friction with thread guides, etc. increases, and the length of the threads becomes longer, so the thickness of the treatment agent on the surface of the elastic threads becomes thinner. Therefore, M
When /Mμ exceeds 0.18, the treatment agent component is expelled from the contact area between the elastic yarn and the yarn guide due to the contact pressure with the yarn guide (a condition where the extreme pressure lubrication ability becomes poor), the yarn The occurrence of scum due to friction becomes noticeable.

In the present invention, it is desirable that the processing agent having the above-mentioned characteristics be completely liquid in its undiluted state, and if it contains solids, the amount of scum generated will often increase.

Various processing agents having such characteristics can be considered, but examples include dimethyl silicone, low swelling smooth components such as mineral oil, and especially dimethyl silicone with a viscosity of 10 to 30 centistokes and 4 to 21 centistokes at 25°C. of mineral oil at a mixing ratio of 100:0 to 40:60.
The base material is preferably a smoothing component mixed in a ratio of 80:10 to 50:50. If the viscosity of dimethyl silicone is less than 10 centistokes,
Elastic yarn has good performance when initially manufactured, but dimethyl silicone tends to scatter during storage, which changes the composition of the treatment agent on the surface of the elastic yarn, resulting in insufficient smoothing performance. To do this, set the viscosity of the processing agent stock solution to 25
It tends to be difficult to reduce the temperature to less than centistokes.

In addition, when the viscosity of mineral oil is less than 4 centistocs, in addition to the problem of easy volatilization as in the case of dimethyl silicone, it also tends to swell the polyether ester block copolymer elastic yarn, resulting in less scum generation. This is likely to be a factor. On the other hand, if it exceeds 24 centistokes, swelling of the elastic yarn becomes difficult to occur, but the viscosity of the processing agent increases and running friction increases, causing various process troubles. In addition, if the blending amount of mineral oil exceeds 60%, it will be difficult to reduce the coefficient of friction between metals (M/Mμ) to 0.18 or less, resulting in insufficient extreme pressure lubrication ability, and the yarn will be easily rubbed during knitting and weaving. scum buildup in some parts, made & IV
A: This will cause problems such as lowering efficiency and lowering the quality of the finished product.

The processing agent in the present invention is based on the above-mentioned smoothing component, but if necessary, other additives may be added, such as an antistatic agent, an emulsifier, an antioxidant, a compatibilizer, and a stability improving agent. You may add additives such as agents to the extent that they do not impair the purpose of the present invention. In particular, the polyether ester block copolymer elastic yarn targeted by the present invention tends to generate static electricity, although the detailed reason is unknown, so it is preferable to add an antistatic agent in an amount of 5 to 20% by weight. . Preferably used antistatic agents have excellent electrostatic performance, do not swell the elastic yarn, and do not cause a decrease in smoothing performance.
Moreover, from the viewpoint that it will not cause discoloration due to interaction with antioxidants, ultraviolet absorbers, etc. that are usually added to elastic yarns, alkyl phosphate antistatic agents that are liquid at room temperature, such as potassium lauryl phosphate, are used. , Isosechi! Examples include potassium rephosphate and sodium isocetyl phosphate.

In order to make the treatment agent described above adhere to the elastic thread, an emulsion made by emulsifying it in water may be used, or the undiluted solution may be used as it is, and any method can be adopted. Among these, the method of using the undiluted solution as it is (straight type processing) has the advantage that it is not necessary to use an emulsifier, which is usually used in combination, which tends to swell the elastic threads and generate scum. preferable.

The amount of the treatment agent attached to the elastic yarn should be 0.5 to 10% by weight as an active ingredient based on the weight of the yarn. Adhesion amount is 0.
If it is less than 5% by weight, the lubricating performance of the yarn will be insufficient, causing problems such as yarn breakage and scum generation.

On the other hand, even if it exceeds 10% by weight, the scum suppressing effect will not be improved much and it is not industrially advantageous.

<Effects of the Invention> The elastic yarn of the present invention detailed above has excellent extreme pressure lubrication effect and is treated with a treatment agent that has little swelling effect.
The unwinding of the raw yarn from the winding paragauge is good, and the accumulation of scum on the yarn guiding guide during the post-processing process of the knitting/weaving hat is significantly reduced, improving operability and producing a product with extremely stable quality. be able to.

<Example> Hereinafter, the present invention will be specifically explained with reference to Examples.

In addition, each evaluation item in Examples was measured according to the following method.

1. Processing agent viscosity Measured in a constant temperature water bath set at 25° C. using an Ostwald viscosity tube in a conventional manner.

2. Polymer swelling degree The polyether ester block copolymer constituting the elastic yarn was melt-molded to obtain a sheet with a thickness of 0.5 cm, and a rectangular sample of 3 cm x 5 am was cut out from this sheet and placed in a stock solution for each treatment. Soak for 1 day at ℃. The degree of polymer swelling was calculated using the following formula.

However, Wo = sample type I before immersion in the treatment agent Wt = weight of the sample after immersion in the treatment agent Note that Wt is the sample after immersion is washed with a 0.5% aqueous solution of sodium dodecylbenzenesulfonate, and then thoroughly rinsed with water.
Dry at 05°C for 1 hour before weighing.

3. Coefficient of friction between metals (extreme pressure lubricity)
kg/rttn 2 (temperature: 20°C).

4. Thread-tapping condition During melt spinning, the yarn-tapping condition on the take-up roller was visually evaluated in three grades.

○: Runs stably without any yarn being taken up by the roller.

Δ: Some threads were removed on the roller, and slight twitching occurred.

・(: The thread is caught in the roller, causing frequent thread breakage.

5. Yarn unwinding properties Yarn winding pa... The distance from the L gauge to the first guide was set to 251, and the yarn was pulled out through this yarn guide at a speed of 10 m/min. The unravelability at this time was evaluated on three levels.

○: Can be unraveled stably without any problems.

△: There was some resistance to the thread being pulled out, but no thread breakage occurred.

×: There is a large resistance to the thread being pulled out, and thread breakage occurs frequently.

6. Status of scum generation and static electricity generation The obtained elastic yarn is passed through a warping machine using 240 frame stands, and wound up 20,000 m at a speed of 20 m/min as a warp beam.

At this time, the state of scum generation at each part of the yarn guide on the warping machine was determined with the naked eye, and the state of static electricity generation was measured using a Kasuga current collector potential measuring device. Note that the evaluation was based on the following criteria.

Scum occurrence status ○There is almost no occurrence of Niscum.

△: Some scum is generated, but it is not a problem.

×There is a lot of varnish scum occurring and the thread running stability is poor.

Static electricity generation status O: 0~Q, 5kV (charged voltage) △: 0.5~1. OkV (electrostatic voltage) X: 1. O
kV or more (electrostatic voltage) Example 1 Butylene terephthalate is used as a hard segment, and polytetramethylene glycol is used as a soft segment.
A polyether ester block copolymer with a hard segment content of 40 wt%, a block copolymer containing 0.2 wt% of a hindered amine antioxidant and 0.2 parts of a benzotriazole ultraviolet absorber. , and 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 filament. At this time, the spun yarn is passed through a metering nozzle to the first
The treatment agent listed in the table was applied to fiber type 1 in a water-free state (straight type) so as to give triple I06.

The evaluation results are also shown in Table 1.

Example 2 Example 1 except that the treatment agent listed in Table 2 was used as a 20% emulsion instead of the treatment agent used in Example 1.
Obtain elastic thread in the same manner as above. The evaluation results of the obtained elastic yarn are also shown in Table 2.

From the results shown in Table 2 and above, it can be seen that the elastic yarn of the present invention does not generate scum, has excellent unwinding properties, and has extremely improved yarn handling properties.

Claims (3)

[Claims] (1) In an elastic yarn made of a polyether ester block copolymer, a treatment agent that simultaneously satisfies the following formulas (a) to (c) is added to the elastic yarn in an amount of 0.5 to 1% based on the weight of the fiber.
Polyether ester block copolymer elastic thread with 0% by weight (as an active ingredient) attached. (a) Viscosity of processing agent stock solution (η)≦25cst (25℃) (b) Polymer swelling degree (Rs)≦10% (c) Coefficient of metal-to-metal friction (M/Mμ)≦0.18 (2) Claim (1) wherein the main active ingredient of the treatment agent is a mixture of dimethyl silicone with a viscosity of 10 to 30 cst and mineral oil with a viscosity of 4 to 21 cst at 25°C in a mixing ratio of 100/0 to 40/60. ) The polyether ester block copolymer elastic yarn described in ). (3) The polyetherester block copolymer elastic yarn according to claim (2), wherein the treatment agent contains 5 to 20% by weight (as an active ingredient) of a phosphate antistatic agent that is in a liquid state at 20°C.