KR102400353B1 - Self-ventilated elastomer fiber by moisture sensitive mechanism - Google Patents

Abstract

The present invention provides an elastic fiber comprising a polyether ester elastomer containing polybutylene terephthalate as a hard segment and polyethylene glycol as a soft segment.

Description

Self-ventilated elastomer fiber by moisture sensitive mechanism

The present invention relates to an elastic fiber having an improved autonomous ventilation control function due to water transfer characteristics, and more particularly, to an elastic fiber having improved moisture absorption and even breathability.

In recent footwear, textile materials are mainly used for the upper, and in finished shoes, the upper material accounts for 25% of the total weight and 60% of the volume, making it the material with the highest cost ratio. Functional performance such as protection, breathability, lightness, etc., and aesthetic performance such as style, design, and color are required.

In general, the upper material of a shoe consists of an outer material for imparting friction resistance, durability, and aesthetics, an inner material for improving wearability and adhesion, and an intermediate media layer for imparting cushioning and functionality. Recently, a lot of textile materials for uppers have been developed to have excellent moisture permeability and waterproof properties by inserting and bonding a moisture permeable and waterproof membrane between the inner/outer skin of the upper.

However, when a moisture-permeable and waterproof membrane is inserted and adhered, the moisture-permeable and waterproof effect is excellent, but it is difficult to control the moisture inside the shoe, which makes it difficult to ventilate the inside of the shoe. In addition, since it is made of a non-renewable membrane, an environmental pollution problem may arise.

In Korean Patent Invention No. 344110, using a thermoplastic or thermosetting sheet as a base material, a polyurethane compounding solution for dry film (III) is applied on a release paper, and a polyurethane compounding solution for adhesion (IV) is applied thereon, and then the thermoplastic Alternatively, a bar-free polyurethane artificial leather manufactured according to the method of bonding to a thermosetting sheet and peeling a release paper is placed on the fabric and heated to melt the polyurethane artificial leather sheet and heat-seal it with the fabric, then molded by a molder A method for manufacturing a shoe by a sewing-free process of making a model of a shoe upper by removing the outside or inside of the shoe and adhering the upper and the sole of the shoe has been proposed. As described above, a method for manufacturing polyurethane artificial leather with a moisture-permeable and waterproof function is presented. Use non-renewable thermosetting sheets and polyurethane blends.

Looking at what is exemplified in the prior art, a fabric with a high waterproof effect is produced by using a thermosetting sheet to express the effect of a general moisture-permeable and waterproof function, and by carrying out the operation of performing polyurethane impregnation, but the effect of moisture permeability is insufficient. , In the case of polyurethane-impregnated fabric, it is difficult to recycle.

In order to solve the above problems, the present inventors have come to develop a method for manufacturing a recyclable polyether ester elastomer and a textile and fabric for footwear that can exhibit waterproof and moisture permeable effects by manufacturing an elastomer and polyolefin composite yarn. will be.

Korean Patent Invention No. 344110

In order to solve the above problems, an object of the present invention is to provide an elastic fiber with improved autonomous ventilation control function by water transfer characteristics through a polyether ester elastomer.

Another object of the present invention is to provide an elastic fiber with improved autonomous ventilation control function by moisture transfer characteristics by manufacturing an elastomer and polyolefin composite yarn.

In order to achieve the above object, the present invention provides an elastic fiber comprising a polyether ester elastomer having polybutylene terephthalate as a hard segment and polyethylene glycol as a soft segment.

In addition, the present invention provides a polyether ester elastic fiber wherein the fiber has a moisture absorption rate of 3 to 4% at 35° C. and 95% RH, and an absorption elongation rate of 9% or less.

The present invention also provides an elastic fiber in which an organic sulfonic acid metal salt is copolymerized with the polyether ester elastomer.

In addition, the present invention provides a polyether ester elastic fiber having a molecular weight in the range of 400 to 20,000 of the polyethylene glycol.

The present invention also provides a polyether ester elastic fiber in which the copolymerization amount of the organic sulfonic acid metal salt is in the range of 0.1 to 20 mol% based on the acid component constituting the polyether ester elastomer.

In addition, the present invention provides an elastic composite fiber composed of the elastic fiber and the polyolefin-based fiber in combination.

In addition, the present invention provides an elastic composite fiber in which the polyolefin-based fiber contains 50% of polyethylene, polypropylene, and the like.

In addition, the present invention provides a shoe made by using the elastic fiber at least in part.

When an elastic fiber with excellent moisture absorption rate and its composite yarn are used in the present invention, the characteristic of rapidly transferring and discharging the high moisture environment in shoes generated due to exercise, etc. is expressed, and tracking shoes, light It can be applied to various footwear products and uses, such as hiking boots and sports shoes.

The present invention relates to a polyether ester elastomer and a composite fiber thereof. In the process of copolymerizing an organic sulfonic acid metal salt with a polyethylene ether ester as a soft segment and ethylene glycol, butylene glycol and dimethyl terephthalate as a hard segment, the polycondensation reactor is vacuum This is to reduce the reaction time by introducing polyethylene glycol into the reactor in a state maintained in the state, and as a result, to prepare a polyether ester elastomer having excellent moisture absorption and moisture absorption elongation.

The polyether ester elastomer according to the present invention comprises the steps of esterifying ethylene glycol and butylene glycol, which are raw materials of a hard segment, with dimethyl terephthalate, under a catalyst, and adding an organic sulfonic acid metal salt and polyethylene glycol as a raw material of the soft segment to the esterification reaction product. It is prepared by the step of polycondensation. First, the esterification reaction step will be described as follows.

Esterification reaction of ethylene glycol, butylene glycol and dimethylelephthalate to form the hard segment of the polyether ester elastomer. 1 to 50 parts by weight of ethylene glycol and 50 to 99 parts by weight of butylene glycol with respect to 100 parts by weight of the low molecular weight diol component are put into a heat-resistant pressure vessel together with the esterification reaction catalyst, and the esterification reaction is performed to prepare an oligomer solution.

While the conventional polyether ester elastomer uses aromatic or aliphatic dicarboxylic acid as a copolymerization raw material to control the melting point, in the present invention, ethylene glycol is used as a diol component to maintain elastic and physical properties, which are important properties of the elastomer, At the same time, it has the advantage of being able to control the melting point characteristics required in various ways in the molding process of the final product.

As the catalyst in the esterification step, an acetic acid-based catalyst such as zinc acetate, sodium acetate, and magnesium acetate, tetranormal butoxytitanate, tetraisopropyl titanate, titanium oxido/silica oxide microcopolymer, and nano titanate and titanium-based catalysts, and these may be used alone or in combination of two or more. In addition, the esterification reaction catalyst may be added in an amount of 50 to 1000 ppm, preferably 200 to 700 ppm, based on 100 parts by weight of the polyether ester elastomer. If the amount of catalyst input is insufficient, the esterification reaction rate is slowed, and if it is excessive, the thermal stability of the elastomer is deteriorated.

The reaction temperature of the heat-resistant pressure vessel in which the esterification reaction proceeds to distill methanol produced as a by-product is in the range of 100 to 240, preferably in the range of 150 to 210. When heating for a long time at the reaction temperature of 240 or more in the presence of an esterification reaction catalyst, the amount of diethylene glycol produced increases due to the dehydration reaction of an excess of ethylene glycol. The production of diethylene glycol may cause deterioration of the physical properties of the final elastomer.

When the esterification reaction proceeds, polycondensation is then proceeded. The oligomer solution obtained by the esterification reaction, the organic sulfonic acid metal salt, the soft segment polyethylene glycol, the polycondensation catalyst, the heat stabilizer, and the U stabilizer are put into a pressure resistant heat-resistant reactor capable of vacuum decompression, and then a pressure of 760 to 1 Torr and 200 After distilling excess ethylene glycol and butylene glycol at a temperature of ~270, polycondensation is completed under a high vacuum with a final vacuum degree of 1 mmHg or less to prepare a thermoplastic elastomer.

In the present invention, copolymerizing the organic sulfonic acid metal salt is preferable in that the intrinsic viscosity of the polyether ester elastomer can be easily improved, and the moisture absorption and absorption elongation of the obtained elastic fiber can be much higher. According to the research of the present inventors, it is possible to achieve a very high level of absorption elongation of 9% level by copolymerizing such an organic sulfonic acid metal salt, so that it is possible to easily obtain a fabric with better comfort on the optimal woven and knitted structure. knew that there was

As a polycondensation catalyst, it is preferable to use a germanium compound, an antimony compound, a titanium compound, a cobalt compound, and a tin compound. The amount of the catalyst to be used is not particularly limited as long as it is an amount necessary to advance the transesterification reaction and the polycondensation reaction, and a plurality of catalysts may be used in combination.

In addition, when a hindered phenol-based compound or a hindered amine-based compound is added to the polyether ester, not only suppresses a decrease in the intrinsic viscosity of the polymer during melt spinning, but also thermal deterioration and oxidative deterioration of the obtained elastic fiber It also has the effect of suppressing , light deterioration, etc., and it is more preferable.

Among them, the use of a hindered phenol-based compound also has the effect of accelerating the polycondensation reaction of the polyether ester elastomer of the present invention, and it is easy to obtain elastic fibers with high intrinsic viscosity, and polyether ester elasticity with excellent hygroscopicity and absorption elongation It is more preferable at the point that a fiber can be manufactured easily.

The elastomer prepared according to the present invention may be prepared in the form of fibers. As a method for producing the elastomer fiber of the present invention, an in-situ spinning method or a composite spinning method may be used. The in-situ spinning method is to spin the elastomer as a single component, and the composite spinning method is to produce a composite fiber by composite spinning the elastomer with other fiber-forming components. The fiber form by the composite spinning may be a side-by-side form, or a sheath-curer form using the elastomer of the present invention as a sheath component or a core component.

The elastomeric fiber prepared according to the present invention may be used to produce a composite yarn together with polyolefin or polyethylene fibers. It can be manufactured in the form of a covering fiber with the present elastomer fiber as a core and polyolefin or polyethylene fiber as a covering.

In the present invention, it is important that the elastomeric fiber has a moisture absorption rate of 3 to 4% at 35 and 95%RH, and an absorption elongation rate of 9%. In woven and knitted fabrics made of such elastomer fibers, when sweat is absorbed, the fibers are stretched and the nose of the woven and knitted fabric is opened to release the moisture inside the clothes, and when dried, the fibers contract and return to their original length, It becomes a fabric with excellent comfort through the moisture-sensitive effect that does not allow moisture to enter the inside.

In the present invention, the elastomeric composite fiber is manufactured by covering the hydrophobic polyolefin-based fiber with the elastomeric fiber as the core part. The shoes to which the woven fabric made of such composite fiber is applied has a stable waterproof effect from external moisture, Appropriate absorption elongation is expressed so that the moisture inside can be radiated to the outside. If the absorption elongation is too high, the moisture absorption rate is preferably in the range of 3 to 4%, and the absorption elongation rate is 10% or less because the nose of the woven and knitted fabric is sufficiently widened and moisture can be introduced into the interior due to the reversible stretch and contraction characteristics by water absorption and waterproofing. range is preferred.

In the elastomeric elastic fiber, when the elongation at break is 400% or more, the hygroscopicity can be 3 to 4% and the absorbent elongation to 9%, and also to prevent the yarn breakage caused by minute deviations in the weaving and knitting process. It is preferable in that it can be done. The elongation at break is more preferably in the range of 400 to 900%, and still more preferably in the range of 400 to 800%.

Hereinafter, the present invention will be described in more detail based on examples, which are only illustrative of the present invention and do not limit the scope of the present invention.

Example 1

100 parts by weight of dimethyl terephthalate, 5 mol% of 5-Na sulfoisophthalic acid dihydroxyethyl ester, 40% by weight of ethylene glycol solution, 73.5 parts by weight of butanediol, and 0.4 parts by weight of tetrabutyl titanate were placed in a reactor and transesterified at an internal temperature of 200. made a reaction At the time when about 80% of the theoretical amount of methanol was discharged, 0.3 parts by weight of the above-mentioned hindered phenol-based compound, 114 parts by weight of polyethylene glycol, a stabilizer (Irganox 1010), and a light stabilizer (Tinuvin 770DF) were added, and then vacuum reduced pressure After adding to a heat-resistant and pressure-resistant reactor capable of stirring, tetranormal butoxytitanate, which is a polycondensation catalyst, is added. At the beginning of the polycondensation reaction, reduced pressure and heating were gradually performed to complete the polycondensation under high vacuum at a final temperature of 250 and a final vacuum of 1 mmHg or less to prepare a thermoplastic elastomer.

The elastomer prepared above was melted at 240 and discharged from a spinneret to obtain polyether ester elastomer elastic fibers. The measurement results are presented in Table 1.

Next, the elastic fiber was subjected to a composite process with polypropylene fiber at a DR of 2.5 to 3.0 using a covering machine, and then 140 g/m2 of knit was produced using a knitting machine. After leaving the knit for 24 hours under an environment of 20 65%RH, and immersing it in a 20 constant temperature water bath for 1 minute, taking it out of the water and removing the moisture adhering to the surface of the knit, the degree of openness of the nose of the knit was observed. . As a result, it was confirmed that the nose of the nit was spread after immersion in a constant temperature water bath.

Example 2

It was carried out in the same manner as in Example 1 except that polyethylene glycol 4000 was used instead of polyethylene glycol (number average molecular weight 2000).

Example 3

It was carried out in the same manner as in Example 1, except that the copolymerization ratio of polyethylene glycol was changed so that the weight ratio of the soft segment/hard segment was 60/40% by weight.

Comparative Example 1

A polyether ester elastomer was obtained in the same manner as in Example 1 except that 5-Na sulfoisophthalate dihydroxyethyl ester was not used. Melt spinning was performed in the same manner as in Example 1 using this polyether ester elastomer, and the results are shown in Table 1.

The properties of the above examples were measured in the following method, and it was derived to have the same effect as in Table 1.

(1) moisture absorption

Humidity was controlled for 24 hours in a constant temperature and humidity room in which the sample was adjusted to a predetermined condition, and the moisture absorption rate was obtained from the Joule amount of the absolutely dry sample and the weight of the humidity control sample by the following equation.

Moisture absorption rate (%) = (weight of humidity control sample, weight of absolute dry sample) *100/weight of absolute dry sample

(2) Absorption elongation, moisture absorption elongation

The fiber is wound on a spool, and after 30 minutes of non-water treatment under no tension, after drying at 2065%RH, a non-contact 160 environment and tension heat treatment for 2 minutes under no tension, the yarn is left under an environment of 2065%RH for 24 hours, and here The length of the yarn (A) measured by applying a load of 0.88*10-3 cN/dtex to the Inserted between filter papers air-dried at 65%RH, placed on a horizontal table, loaded with a weight of 1.5g/cm2, left for 2 seconds, wiped off excess moisture on the fiber surface, and after 10 seconds, 0.88*10-3cN/ Absorption elongation was calculated by the following formula for the length (B) measured by applying a load of dtex.

Absorption elongation = (B-A)/Drying length of yarn * 100%

In addition, A was measured in the same manner as above, and then the measured yarn was left for 24 hours in a constant temperature and humidity room controlled at 35 95% RH, and a load of 0.88 * 10-3 cN/dtex was applied in the constant temperature and humidity room. With the length as (C), the hygroscopic elongation was calculated by the following formula.

Moisture absorption elongation = (C-A)/Drying length of yarn*100%

(3) Comfort

The elastic fibers were made into 150 g/m2 of nits with a mini circular knitting machine, and after a day was wrapped around the elbows, knees, and backs of the feet of 10 randomly selected people, the sticky feeling and the refreshing feeling were evaluated. The results were expressed as less (0) to greater (5) for sticky feeling and refreshing feeling, respectively.

Example comparative example One 2 3 One Polyethylene glycol ratio 50 50 60 50 Polyethylene glycol average molecular weight 2000 4000 4000 4000 5-Na sulfoisophthalic acid dihydroxyethyl ester copolymerization amount (mol%) 5 5 5 0 Radiation speed (m/min) 700 700 700 700 covering fiber PP 75D/36f PP 75D/36f PP 75D/36f PP 75D/36f DR conditions 3.0 3.0 3.0 3.0 Absorption elongation (%) 9 8 7 2 sticky feeling One 0 0 3 fresh feeling 4 5 5 2

Claims (8)

It consists of a polyether ester elastomer having polybutylene terephthalate as a hard segment and polyethylene glycol as a soft segment,
An elastic fiber in which 5-Na sulfoisophthalic acid dihydroxyethyl ester is contained in an amount of 5 mol% based on the acid component constituting the polyether ester elastomer,
The elastic fiber is a polyether ester elastic fiber having a moisture absorption rate of 3 to 4% at 35°C and 95% RH, and an absorption elongation rate of 9% or less. delete delete The method of claim 1,
Polyether ester elastic fibers having a molecular weight in the range of 400 to 20,000 of the polyethylene glycol. delete An elastic composite fiber comprising the elastic fiber of claim 1 or 4 and the polyolefin-based fiber composite. delete A shoe made by using the elastic fiber of claim 1 or 4 at least in part.