KR20010029274A - Manufacturing method of heat resistant polyetherester elastic fiber - Google Patents

Abstract

The present invention relates to a method for producing a polyether ester elastic composite fiber having excellent heat resistance using an aromatic polyester as a hard segment and a polyoxyalkylene glycol-based polyether as a soft segment, and the technical configuration is an acid component of a hard segment component. By using 2,6-naphthalenedicarboxylate to make the hard segment content ratio of 20 to 40% by weight, the polyether ester block copolymer is a polysegment block copolymer of polyoxyalkylene glycol as a component 1) to (3) to satisfy the polyether ester-based elastic fiber at the same time characterized in that the elastic fiber of the present invention is excellent in elastic recovery rate and elongation characteristics, when subjected to dyeing processing and heat setting treatment on a woven or knitted fabric Obtain polyether ester composite elastic fiber with excellent heat resistance Can.

1.7 ≤ IV ≤ 2.2 ............... Equation (1)

Tm ≥ 190 ℃ ............... Equation (2)

2 ≤ Mw / Mn ≤ 4 .............. Equation (3)

Where IV is the intrinsic viscosity,

Tm is the melting point,

Mw is the weight average molecular weight,

Mn is the number average molecular weight.

Description

Manufacturing method of heat resistant polyetherester elastic fiber

The present invention relates to a method for producing an elastic yarn having excellent elastic recovery rate and heat resistance in the processing step using a polyether ester copolymer, more specifically, an aromatic polyester (polybutylene naphthalate) as a hard segment, polyoxyalkylene The present invention relates to a method for producing an elastic fiber having a melt recovery polystyrene ester block copolymer using a glycol-based polyether in a spin-draw method in a spin draw method and having excellent elasticity recovery and high elasticity and excellent heat resistance in dyeing and processing processes.

In general, in order to impart stretch properties to fabrics and knits, mechanical crimping such as flamming, fluid processing, and gear crimping or blending yarns such as polybutylene terephthalate / nylon are known. Because of this low, high stretch cannot be imparted. Therefore, high elastic yarns such as spandex can be used to produce high stretch fabrics and knits. However, these high elastic yarns have high coefficients of friction and low strength. Since the knitting is very bad and there is a problem in dyeing, it is inferior in workability and can be mixed with other filament yarns or supplemented with a method of weaving or covering fibers having high strength and dyeing. However, the covering process has a problem that the manufacturing cost is high because the productivity is poor and inefficient.

On the other hand, side by side and sheath-core type latent elastic fibers with polyamide have been proposed to overcome the drawbacks of the covering yarns by using the excellent high elasticity of polyurethane. That is, cis-core composite fibers of polybutylene terephthalate and polyurethane have been proposed in JP-A-55-36725 and JP-A-55-27175. However, the composite fiber using the spandex is effective to generate the micro crimp by using the heat shrinkability of the spandex, but the elastic properties inherent in the spandex is not generally used.

In order to have excellent compatibility with polyester and at the same time have excellent elastic recovery rate, a technique related to manufacturing polyurethane and polyether ester sheath-core composite elastic yarn has been disclosed in Korean Laid-Open Patent Publication No. 95-29385. As a result, spandex, which is a polyurethane elastic fiber, is manufactured by a dry spinning method, it is technically difficult to melt-spun polyether ester with polyurethane.

In addition, as mentioned in Japanese Unexamined Patent Publication No. Hei 5-5217, an elastic fiber is obtained by complex spinning a polyether polyurethane having an allophanate bond and a polyester or polycarbonate polyurethane having no allophanate bond. Processes for preparing the same are also known.

When using a polyurethane elastic filament together with a polyester filament yarn to produce a stretchable knitted fabric, the following problems occur. In other words, polyester filament yarn in the fabric is usually dyed at a high temperature of about 130 ℃ this high dyeing temperature causes thermal decomposition of the polyurethane. In addition, the polyester filament yarn in the fabric, for example, is heat set at a high temperature of 160 ℃ or more, such high heat setting temperature causes thermal deterioration of polyurethane filament yarn and is produced when the polyurethane elastic yarn is used in combination with polyester fibers Knit fabrics have a high tissue density and have an insufficiently firm texture unless they are in tension. In order to compensate for these disadvantages, a sheath-core composite fiber having strong rigidity, good drape and high stretch-elasticity, using polyetherester as the core component and polyethylene terephthalate as the cis component, is disclosed in Korean Patent Laid-Open Publication No. 91 Proposed in -12439.

However, such composite fibers are not suitable for knitted fabrics requiring high stretch, such as sports apparel, because they have little elasticity of the sheath polyester component. Therefore, a lot of researches have been conducted to prepare a polyether ester elastic yarn having elastic properties similar to polyurethane elastic spandex and excellent chemical resistance such as alkali resistance and chlorine resistance and excellent heat resistance.

On the other hand, many studies have been conducted in Japan since the manufacturing method of polyether ester-based elastic yarn having excellent compatibility with polyester and excellent elastic recovery rate was first introduced as a patent of DuPont in the United States. 175719, Japanese Patent Application Laid-Open No. 3-206118, Japanese Patent Application Laid-Open No. 3-249211, etc., a dicarboxylic acid component mainly containing terephthalic acid, a glycol component mainly containing 1,4-butanediol, and a poly (alkyl oxide) glycol component having an average molecular weight of 400 to 4000 A method for producing an elastic yarn obtained from a polyether ester block copolymer as a component is disclosed. However, the polyether ester elastic yarn manufactured by this method is advantageous in chemical resistance or chemical resistance when used in combination with polyester yarn rather than polyurethane elastic yarn, but still does not show satisfactory heat resistance in the post-processing process of polyester fabric or knitted fabric such as dyeing. There is this.

On the other hand, the content of hard segments and soft segments is very important in order to fiberize the polyether ester to express the elastic properties. The elongation is very high when the weight ratio of soft segment in polyether ester exceeds 80, but the elastic recovery rate or strength is lowered due to insufficient physical crosslinking role in the molecular chain.If the weight ratio of soft segment is less than 50, the strength is very high but the elongation required for elastic yarn It cannot be obtained, resulting in permanent deformation due to external force, and it becomes difficult to express elasticity. For this reason, the weight ratio of the soft segment exhibiting optimum elastic properties when the fiber is polyether ester is about 60 to 70. In this content, the amount of the crystalline hard segment is relatively small, so the melting point of the polyether ester is the content of the hard segment. Much lower than this. Therefore, the polyether ester having a soft segment content exhibiting sufficient elastic properties in the yarn state is deteriorated in the heat resistance characteristics due to processing during the manufacturing process of the fabric or knitted fabric. In particular, when used with polyester filament fibers, the dyeing process is performed after refining, bleaching, and presetting process, and finally, the final setting (heat fixing) process is performed. It takes about 120 minutes, and the setting process receives heat of 160 ~ 190 ℃ for 30 ~ 120 seconds. In particular, when the heat treatment is performed at a high temperature as in the setting process, many of the crystal parts that used as physical crosslinks in the polyether ester yarn are melted and stretched to the extent that they cannot exhibit elastic properties, or trimming occurs. Has the disadvantage of deterioration.

Therefore, the present invention, while solving the above-mentioned disadvantages of the spandex to solve this problem, exhibits excellent elastic recovery rate and high elasticity, and also when used with polyester filament fibers, salt processing conditions of the polyester fiber in the woven state The present invention relates to a polyether ester elastic fiber characterized by maintaining elastic properties even after treatment with an aromatic polyester, comprising an aromatic polyester (polybutylene naphthalate) as a hard segment and a polyoxyalkylene glycol-based polyether as a soft segment. In preparing a polyetherester block copolymer, the polyetherester block copolymer which can exhibit excellent elastic properties without causing deterioration in the dyeing process due to its high melting point even when used in combination with polyester fibers After determining the composition of the polymer, synthesize the copolymer having a molecular weight, intrinsic viscosity, and melt viscosity suitable for melt spinning, and melt spinning in a spin draw method, the elastic recovery rate and high elasticity, but also excellent heat resistance in the dyeing and processing process It relates to a method for producing a fiber.

Hereinafter, the present invention will be described in more detail.

The hard segment component of the polyether ester is an aromatic dicarboxylic acid component isophthalic acid, phthalic acid, terphthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalene dicarboxylic, bis (p-carboxyphenyl) Methane and 4,4'-diphenyletherdicarboxylic acid, aliphatic dicarboxylic acid, for example adipic acid, sebacic acid, azelaic acid and dodecane dicarboxylic acid, alicyclic, for example 1,4 -Cyclohexanedicarboxylic acid and ester forming derivatives of said acids.

Low molecular weight diol compounds that are ester-forming derivatives of dicarboxylic acids include ethylene glycol, propylene glycol, tetramethylene glycol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, 1,4-cyclohexanediol And 1,4-cyclohexanedimethanol and ester-forming derivatives thereof are generally used. In the present invention, 2,6-naphthalenedicarboxylic acid is used as the dicarboxylic acid component and tetramethylene glycol is used as the glycol component. . The polyoxyalkylene glycols that can be used for the preparation of the polyetherester block copolymers include polyoxyethylene glycol, polyoxypropylene glycol, polyoxybutylene glycol, and random copolymers and block copolymers of the homopolymers, and It is preferable to select from 2 or more mixtures, More preferably, the polyoxybutylene glycol homopolymer of average molecular weights 500-3000, and the polyoxytetramethylene glycol of average molecular weight 2000 are preferable.

The polyetherester block copolymers prepared in this way can be copolymerized differently in the content of hard segments, and in this case, in order to synthesize a melt-spinable copolymer, it is preferable that the intrinsic viscosity (IV) is 1.7≤IV≤2.2 and the copolymer The melt viscosity (MV) of represents 2500 ≦ MV ≦ 4000 poise. Melting point of the copolymer analyzed by differential scanning thermal analyzer (DSC) is 190 ℃ ≤ Tm, molecular weight distribution index D expressed by weight average molecular weight (Mw) / number average molecular weight (Mn) is characterized in that 2≤D≤5 To prepare a copolymer was synthesized.

The copolymer obtained in this way can be produced elastic yarn using a conventional melt spinning capping device, the temperature of the extruder is 190 ~ 240 ℃, the temperature of the metering section is good 200 ~ 250 ℃, the melt using a gear pump The spinneret was discharged at a constant discharge rate, and spinneret was melt-spun at 250 to 270 ° C using spinning air of 8, diameter 0.2mm and L / D = 2.5, and then the temperature of the first gourd roller was 40 to 80 ° C, The temperature of the secondary high speed roller is extended to 1.5 ~ 3.2 times while setting the temperature to 100 ~ 150 ℃, and then heat set.Then, after passing through the decelerated third cold roller, it is wound with overfeed and the elastic yarn obtained is fineness of 40 denier monofilament. To manufacture.

Hag segment content ratio of polyether ester copolymer elastic yarn, a thermoplastic stretch fiber, is 20 to 40 weight is appropriate. If the content of hard segment is less than 20 weight, the elastic property is excellent, especially in terms of recovery rate, the crystalline component that causes permanent deformation by external force Although the elastic recovery rate is small, the amorphous amorphous region is relatively large, and the crystalline component that acts as a three-dimensional physical crosslinking role is weakened, so the strength of the elastic yarn is weakened, which causes frequent trimming during spinning. In addition, the heat resistance is weakened, the elastic properties due to the heat (dyeing or heat setting) received during the various steps during the fabric or knitted fabrics are reduced, so that it does not act as an elastic fiber. On the other hand, if the content of the hard segment exceeds 40 weights, the heat resistance and strength in the above-described post-processing process is improved, but the elongation and elastic recovery rate are sharply lowered, so the intrinsic properties of the elastic yarn disappear, so that the content ratio of the hard segment and the soft segment in the copolymer production Is very important and the content of hard segments suitable for elastic fibers is preferably 20 to 40 weight.

The composite elastic fiber of the present invention has the following advantages.

First, since polybutylene naphthalate, which is a hard segment component, has a higher melting point than polybutylene terephthalate described in the prior art, the polymer exhibits excellent heat resistance to heat received during the post-processing process. Excellent elastic properties in woven or knitted fabrics.

Second, because it is a stretch fiber manufactured by melt spinning a polyether ester copolymer, it is possible to mix high temperature and high pressure dyeing conditions of polyester, unlike polyurethane, and it is easy to dye disperse dyes. The field of use has various advantages.

The physical property measurement in an Example and a comparative example is performed by the following method.

Melting point (Tm): Perkin-Elmer DSC-7 (Differential Scanning Thermal Analyzer) was used.

(20 ℃ / min)

Elongation: Tensile length of 10 cm sample was stretched at a rate of 200 / min using an Instron tensile tester, and denier strength (g / d) and elongation () until breakage were measured.

-Elongation recovery rate: Elongate the sample of 10cm length up to 200 elongation at 200 / min. 5 times, remove the load and measure the length (L) of the sample.

-Heat resistance hot rupture time (HRZ): The heat resistance evaluation measured the time until the filament yarn was trimmed when heated to a temperature of 193.5 ° C. at 100 elongation.

On the other hand, in order to evaluate the heat resistance during the dyeing process of the elastic fibers, the fabric properties were evaluated after the general polyester processing step of the dough samples woven together with ordinary polyester yarns (DTY 150d / 48f). Silver refinement

(relaxing, tentering, weight loss, dyeing, and final setting processes were carried out continuously, and the fabric stretch of the sample was measured. It will undergo heat setting for a processing time of about 15-30 seconds at the temperature of. In the method of measuring the fabric stretch, stretching was repeated three times until a load of 900 g was applied when the fabric sample of 100 × 22 mm size was stretched in the weft direction, and stopped at a load of 900 g at the fourth stretching, and the elongation at that time was shown.

Hereinafter, the present invention will be described in detail with reference to Examples.

Example 1

To polymerize copolyetherester having a 35 weight hard segment content

129.03 parts by weight of 2,6-naphthalenedicarboxylate, 62.62 parts by weight of tetramethylene glycol, 217 parts by weight of polyoxytetramethylene glycol having a number average molecular weight of 2000, and 0.2 parts by weight of titanium tetrabutoxide were placed in a reactor under a nitrogen stream. After carrying out the transesterification reaction at 210 ° C., more than 80 theoretical methanol was distilled off, and then 0.5 parts by weight of Iganox 1010 (available from Shiva-Gaigi Co., Ltd.) and 2.3 parts by weight of tinuvin 770 (manufactured by Shiva-gai Co., Ltd.) were added as thermal oxidation stabilizer. After the temperature was raised to 210 to 250 ° C., a condensation polymerization reaction was performed for 60 minutes at low vacuum and 120 minutes at high vacuum to terminate the reaction. The inherent viscosity of the polymer thus obtained was 2.115 (measured at 30 ° C using a phenol / tetrachloroethane mixed solution). The melt viscosity was 3500 poise. The prepared copolymer was pelletized and then spun using a melt spinning equipment. At this time, the temperature of the extruder was 190-240 ° C., and the temperature of the metering part was 200-250 ° C. The spinneret is discharged at a constant discharge rate, and spinneret is airborne 8, diameter 0.2mm, L / D = 2.5, and spinning temperature is 250 ~ 270 ℃, melt spinning, and then the temperature of the first gourd roller is 40 ~ 80 ℃, 2 After setting the temperature of the secondary high speed roller to 100 ~ 150 ℃ and stretching it at 1.5 ~ 3.2 times, pass it through the decelerated tertiary cold steel roller and give overfeed of 2 ~ 5 at the spinning speed of 500 ~ 800m / min. Winding, the elastic yarn obtained at this time was prepared with a fineness of 40 denier monofilament.

Table 1 shows the fabric stretch characteristics which are the heat resistance characteristics of the elastic yarn and the elastic properties after dyeing processing.

Example 2

Using a 2,6-naphthalenedicarboxylate as an acid component in the same manner as in Example 1 to prepare a polyether ester elastic fiber having a hard segment content of 40 weight, the physical properties of the elastic yarn thus prepared are shown in Table 1 .

Example 3

Using a 2,6-naphthalenedicarboxylate as an acid component in the same manner as in Example 1 to prepare a polyether ester elastic fiber having a hard segment content of 30 weight, the physical properties of the elastic yarn thus prepared are shown in Table 1 .

Comparative Example 1

Using a 2,6-naphthalenedicarboxylate as an acid component in the same manner as in Example 1 to prepare a polyether ester elastic fiber having a hard segment content of 45 weight, the physical properties of the elastic yarn thus prepared are shown in Table 1 .

Comparative Example 2

In the same manner as in Example 1, using 2,6-naphthalenedicarboxylate as an acid component to prepare a polyether ester elastic fiber having a hard segment content of 18 weight, the physical properties of the elastic yarn thus prepared are shown in Table 1 .

Comparative Example 3

Using a dimethyl terephthalate as an acid component in the same manner as in Example 1 to prepare a polyether ester elastic fiber having a hard segment content of 35 weight, the physical properties of the elastic yarn thus prepared are shown in Table 1.

Comparative Example 4

By using the dimethyl terephthalate as an acid component in the same manner as in Example 1 to prepare a polyether ester elastic fiber having a hard segment content of 40 weight, the physical properties of the elastic yarn thus prepared are shown in Table 1.

Comparative Example 5

By using the dimethyl terephthalate as an acid component in the same manner as in Example 1 to prepare a polyetherester elastic fiber having a hard segment content of 30 weight, the physical properties of the elastic yarn thus prepared are shown in Table 1.

Table 1 Property Measurement Results

division Strength (g / d) Shinto () Elastic recovery rate () HRZ heat resistance (sec.) Fabric Stretch () 190 ℃ 200 ℃ Example 1 1.13 434 88 102 25.2 25.1 Example 2 1.24 402 81 158 26.0 26.2 Example 3 1.02 482 90 80 24.0 24.0 Comparative Example 1 1.41 380 75 ≥ 300 20.0 20.1 Comparative Example 2 0.7 510 95 25 24.0 23.9 Comparative Example 3 1.21 458 85 ≤ 3 18.1 16.5 Comparative Example 4 1.42 361 77 ≤ 3 15.2 14.9 Comparative Example 5 1.11 447 89 ≤ 3 16.5 16.0

The present invention is a polyether ester-based elasticity having excellent elasticity and elongation characteristics, polyether ester block copolymer having excellent heat resistance properties after synthesis and melt spinning to have high elasticity and high elastic recovery rate and excellent heat resistance against heat received during dyeing process Fibers can be produced.

Claims (2)

In preparing the polyether ester elastic fiber, the content of the hard segment component is 20 to 40 weight by using 2,6-naphthalenedicarboxylate as the acid component of the hard segment component, and the polyoxyalkyl as the soft segment component. A method for producing a polyether ester elastic fiber, comprising a polyether ester block copolymer having len glycol as a component. The method for producing a polyether ester elastic fiber according to claim 1, wherein the polyether ester block copolymer simultaneously satisfies the following formulas (1) to (3). (1) 1.7 ≤ IV ≤ 2.2 (2) Tm ≥ 190 ℃ (3) 2 ≤ Mw / Mn ≤ 4 Where IV is the intrinsic viscosity, Tm is the melting point, Mw is the weight average molecular weight, and Mn is the number average molecular weight. Display)