JP3952554B2 - Elastic yarn excellent in heat resistance and method for producing the same - Google Patents

Description

【００２９】
実施例１〜６、比較例及び参考例
合成例１〜６で得られた弾性重合体のペレットを減圧乾燥した後、表２に示した紡糸条件で溶融紡糸し、シリコーン系油剤を付着させた後、チーズ状に巻き取った。この際、紡糸口金として孔径 0.5mmφのノズルを有するものを用い、巻き取った糸条の繊度が50ｄとなるように吐出量を調整した。
次いで、弾性糸をチーズ状に巻き取った状態で、 120℃のオーブンで２時間熱処理した。
また、参考例として、ポリブチレンテレフタレートをハードセグメントとし、分子量2000のPTMGをソフトセグメントとする融点 182℃のポリエーテルエステルを用い、同様にして弾性糸を得た。
得られた弾性糸の糸質性能を評価した結果を表２に示す。
【００３０】
【表２】

【００３１】
表２から明らかなように、実施例１〜６では、弾性回復性に優れ、高温熱セットにも十分耐え得る弾性糸が得られた。これに対し、比較例及び参考例では、融点が低くて耐熱性が悪く、編み地を熱セットする際に弾性糸が一部溶融し、風合いが硬く、ストレッチバック性に劣るものとなった。
【００３２】
【発明の効果】
本発明によれば、耐熱性に優れ、熱処理によって品位が低下することがなく、かつ優れた弾性回復性を有する弾性糸及びその製造法が提供される。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an elastic yarn having an excellent heat resistance comprising an elastic polymer composed of an aromatic dicarboxylic acid component having an aromatic amide bond and a polyalkylene glycol component, and a method for producing the same.
[0002]
[Prior art]
Conventionally, polyurethane elastic yarns (for example, Japanese Patent Publication No. 47-13789), polyetherester elastic yarns (for example, Japanese Patent Application Laid-Open No. 47-77317), etc., for imparting stretch properties to fabrics for clothing and industrial materials The elastic yarn is used. However, these elastic yarns have excellent elastic recoverability, but their melting point is low, so they are melted or rapidly shrunk by heat treatment such as dyeing or heat setting in the subsequent process, and the quality is inferior. There was a drawback of becoming something.
[0003]
In the case of polyether ester-based elastic yarn, it is possible to increase the melting point by increasing the proportion of the hard segment, but doing so results in poor elastic recovery and poor practicality as an elastic yarn. Become.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide an elastic yarn that has excellent heat resistance, does not deteriorate in quality due to heat treatment, and has excellent elastic recoverability, and a method for producing the same.
[0005]
[Means for Solving the Problems]
The present invention solves the above-mentioned problems, and the gist thereof is as follows.
1. It consists of an elastic polymer having a melting point of 195 to 235 ° C. composed of an aromatic dicarboxylic acid component represented by the general formula (1) or (2) having an aromatic amide bond and a polyalkylene glycol component, and is 100% The elastic recovery rate at elongation is 80% or more, the elastic recovery rate at 200% elongation is 70% or more, and the strong elongation product retention after heat treatment at 190 ° C. for 10 minutes is 85% or more. Elastic yarn with excellent heat resistance.
(1) ROOC-Ph-NHCO-Z-CONH-Ph-COOR '
(2) ROOC-Ph-CONH-Z-NHCO-Ph-COOR '
In the formulas (1) and (2), Ph represents a phenylene group, Z represents a divalent aromatic group, and R and R ′ represent a hydrogen atom or an alkyl group.
2. Melt spinning an elastic polymer having a melting point of 195 to 235 ° C. composed of an aromatic dicarboxylic acid component represented by the general formula (1) or (2) having an aromatic amide bond and a polyalkylene glycol component; A method for producing an elastic yarn excellent in heat resistance, which is wound into a cheese and heat-treated at a temperature of 100 ° C. or higher for 0.5 hours or longer.
(1) ROOC-Ph-NHCO-Z-CONH-Ph-COOR '
(2) ROOC-Ph-CONH-Z-NHCO-Ph-COOR '
In the formulas (1) and (2), Ph represents a phenylene group, Z represents a divalent aromatic group, and R and R ′ represent a hydrogen atom or an alkyl group.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
[0007]
In the present invention, as the aromatic dicarboxylic acid component, a compound represented by the general formula (1) or (2) is preferably used.
(1) ROOC-Ph-NHCO-Z-CONH-Ph-COOR '
(2) ROOC-Ph-CONH-Z-NHCO-Ph-COOR '
In the formulas (1) and (2) , Ph represents a phenylene group, Z represents a divalent aromatic group, and R and R ′ represent a hydrogen atom or an alkyl group.
[0008]
As specific examples of the aromatic dicarboxylic acid component, in formulas (1) and (2) , Ph is a p-phenylene group, Z is a p-phenylene group, m-phenylene group, p-diphenylene group or p-diphenylene ether. Examples thereof include compounds in which the groups R and R ′ are lower alkyl groups such as a methyl group, an ethyl group and a butyl group.
Of these, N, N′-bis (p-ethoxycarbonylphenyl) terephthalamide is most preferable from the viewpoint of the thermal properties and cost of the elastic polymer.
[0009]
On the other hand, polyethylene glycol, polypropylene glycol, polytetramethylene glycol or the like is used as the polyalkylene glycol component.
Of these, polytetramethylene glycol is most preferred because it provides an elastic polymer having excellent low-temperature characteristics and strength, and excellent oxidation resistance and hydrolysis resistance.
[0010]
The elastic polymer in the present invention is required to have a melting point higher than 190 ° C., preferably in the range of 195 to 235 ° C. When the melting point is lower than this, the characteristics as a heat-resistant elastic yarn are not exhibited. In other words, elastic yarn is knitted and woven with other fibers, dyed, and then heat set. The elastic yarn contracts or melts at the heat setting temperature (approximately 180 to 190 ° C). As a result, the texture becomes stiff and the quality is inferior. On the other hand, if the melting point is made higher than the above range, the performance as an elastic yarn such as elastic recovery is inferior.
[0011]
The melting point of the elastic polymer can be adjusted mainly by the molecular weight of the polyalkylene glycol. For example, in the case of the elastic polymer from the terephthalamide aromatic dicarboxylic acid component and the polytetramethylene glycol component, the molecular weight is 500 to 500. By using about 2000 polytetramethylene glycol, the melting point in the above range can be obtained.
[0012]
The elastic polymer in the present invention can be produced by the following two-stage polymerization method.
The first stage polymerization is carried out for the purpose of condensing an aromatic dicarboxylic acid component and a polyalkylene glycol component to obtain a low molecular weight oligomer. In the first stage polymerization, in the presence of a solvent such as N-methyl-2-pyrrolidone at normal pressure and at a temperature of 140 to 210 ° C, preferably 170 to 210 ° C, more preferably 190 to 210 ° C. After reacting for 1 to 3 hours, it is appropriate to remove the solvent by reducing the pressure and raising the temperature.
[0013]
The second-stage polymerization is performed for the purpose of obtaining a high molecular weight polymer by performing condensation between oligomers. As the conditions at this time, it is appropriate that the polymerization temperature is 210 to 270 ° C., preferably 220 to 260 ° C., the pressure is 0.1 to 2 mmHg, preferably 0.1 to 1 mmHg, and the polymerization time is 1 to 4 hours.
[0014]
It is desirable to change the polymerization temperature as appropriate depending on the structure of the polymer. However, generally, when the polymerization temperature is 210 ° C. or lower, the molten state of the polymer is often incomplete, and it is difficult to obtain a high molecular weight polymer. . On the other hand, when the polymerization temperature is 270 ° C. or higher, the polymer is likely to be colored and decomposed, and the molecular weight of the polymer may be lowered.
[0015]
A catalyst is usually used for the polymerization reaction, and metal alkoxides, particularly titanium alkoxides are preferably used as the polymerization catalyst.
[0016]
Further, it is desirable that the polymer contains a hindered phenol antioxidant generally used, and a phosphorus, sulfur, amine antioxidant or the like may be used in combination. The addition of the antioxidant may be performed by adding the antioxidant to the polymerization can at the start of polymerization or after completion of the polymerization and stirring the mixture, or by mixing and kneading the polymer pellets and the antioxidant. You may go by.
[0017]
In addition to antioxidants, if necessary, wax, antistatic agent, conductive agent, crystal nucleating agent, plasticizer, mold release agent, UV stabilizer, hydrolysis inhibitor, flame retardant, inorganic filler, inorganic Various additives such as pigments and organic pigments can be contained.
[0018]
The elastic yarn of the present invention can be produced by a normal melt spinning method. That is, after the elastic polymer pellets are dried, they are melt-extruded with an extruder, weighed with a metering pump, guided to a spinneret pack, discharged from the nozzle of the spinneret, cooled, oiled, and a constant speed winder. Wind up with.
[0019]
At this time, the spinning temperature (temperature of the spinneret) is desirably set to the melting point of the elastic polymer + 30 ° C. or higher. The winding speed is suitably 300 to 2000 m / min. When the winding speed is slow, the discharge amount is small and the productivity is inferior, and when it is too fast, the operability is lowered.
[0020]
The application of the oil agent is performed in order to prevent generation of static electricity during winding and to smoothly perform post-processing, and as the oil agent, a silicone material is preferably used.
[0021]
In order to improve elastic recovery characteristics and heat shrinkage characteristics, the elastic yarn that has been melt-spun and wound up is 100 ° C. or higher, preferably at 110 to 130 ° C. for 0.5 hour or longer, preferably in the state of being wound in cheese. Is preferably heat-treated for 1 to 3 hours.
[0022]
In the present invention, the elastic recovery rate when the elastic yarn is 100% stretched is 80% or higher, the elastic recovery rate when 200% stretched is 70% or higher, and the high elongation product retention rate after heat treatment at 190 ° C for 10 minutes. It is necessary to appropriately select the type of elastic polymer and the spinning conditions (including heat treatment conditions) so that the ratio is 85% or more.
[0023]
When the elastic recovery rate is lower than the above value, the stretch back property of the fabric is inferior, and when the high elongation product retention is lower than the above value, the heat resistance is insufficient and the heat set cannot be endured.
[0024]
[Action]
Since the elastic polymer in the present invention is composed of an aromatic dicarboxylic acid component (hard segment) having an aromatic amide bond and a polyalkylene glycol component (soft segment), the hard segment has a small weight ratio and hardness. Even if low, it has a high melting point.
Therefore, the elastic yarn made of this elastic polymer is flexible and excellent in heat resistance, and the quality of the fabric does not deteriorate even when heat-set at a higher temperature than the conventional polyetherester elastic yarn. , An elastic fabric having good stretch-back properties can be obtained.
[0025]
【Example】
Next, the present invention will be described specifically by way of examples.
In addition, the measurement and evaluation methods of characteristic values and the like in the examples are as follows.
1. The melting point was measured using a differential scanning calorimeter DSC-7 type manufactured by Perkin Elmer Co., Ltd., at a heating rate of 10 ° C./min.
2. Molecular weight of elastic polymer Using a GPC device CP-8000 manufactured by Tosoh Corporation, the weight average molecular weight in terms of polystyrene was measured using an eluent obtained by adding 20 mmol of lithium chloride to 1 L of N-methyl-2-pyrrolidone. Asked.
3. Melt index (MI)
Using a melt indexer L224, X416 manufactured by Takara Kogyo Co., Ltd., the load was 2.01 kg and the temperature was 230 ° C.
4). Wound 80 times with a measuring instrument with a fineness of 1.125m, let stand for 30 minutes, measure the length by applying a load of 1/300 (g / d), measure the weight, and then measure denier (d) Converted into
5). Elastic recovery rate When using Tensilon RTC-1210 type manufactured by Orientic, stretched to 100% and 200% at a sample length of 10 cm and a tensile speed of 10 cm / min, then returned to the original length at the same speed and stretched again. The length when the stress appeared was obtained, and the elastic recovery rate was obtained by the following equation.
Elastic recovery rate (%) = [(L0−L1) / L0] × 100
L0: stretched length L1: length when stress appears when stretched again High elongation and high elongation product retention The high elongation was measured using a Tensilon RTC-1210 model manufactured by Orientic Co., Ltd., with a sample length of 10 cm and a tensile speed of 10 cm / min.
The tensile strength after heat treatment was measured on yarn obtained by circular knitting of elastic yarn, heat treatment in an oven at 190 ° C. for 10 minutes, cooling to room temperature, and then unwinding.
The strength elongation product retention was calculated by calculating the ratio of the strength elongation product after the heat treatment to the strength elongation product before the heat treatment (strength × elongation).
7). Texture and stretch-back properties While stretching the elastic yarn twice, circularly knitting at the same time with 75d / 36f polyethylene terephthalate false twisted yarn, dyeing under the following conditions, and heat setting with an iron with a surface temperature of 190 ° C for 1 minute The knitted fabric obtained was evaluated in the following four stages. (◎ and ○ pass, △ and × fail)
Dyeing condition dye: Disperse dye made by Dystar Japan; Resoline Blue SGL 1% owf
Auxiliary agent: Dispersant manufactured by Meisei Chemical Co., Ltd .; Disper VG 2g / L
Bath ratio: 1/50
Dyeing temperature × time: 130 ° C. × 60 minutes texture evaluation ◎: fabric is thick and excellent in resilience ○: fabric is slightly thin, but resilience is excellent Δ: fabric is slightly thin and resilience is inferior ×: Evaluation of stretch-back property with thin fabric and inferior resilience ◎: Even if stretched by hand, it completely returns to the original state ○: Traces remain slightly when stretched by hand Δ: Traces remain clearly when stretched by hand ×: When it is stretched by hand, it almost does not return. [0026]
Synthesis example 1
Polytetramethylene glycol (PTMG) 2.06 mol (2061 g, N, N'-bis (p-ethoxycarbonylphenyl) terephthalamide 2.06 mol, molecular weight 1000) in a 15 L autoclave equipped with a nitrogen inlet tube, temperature sensor, stirrer and distillation device (949 g) and Irganox 1330 (hindered phenol antioxidant manufactured by Ciba Geigy Co., Ltd.) 0.1 wt% (3.01 g) were charged and dried at 100 ° C. under reduced pressure.
Next, 31.5 wt% (1384 g) of N-methyl-2-pyrrolidone (solvent) and 0.1 wt% (4.39 g) of tetrabutoxy titanate were added to the autoclave, and the contents were heated to 210 ° C. and reacted for 1 hour. After that, the degree of vacuum was gradually increased and the temperature was raised to 240 ° C. over 1 hour to remove the solvent almost completely. At the same time as the solvent was removed, ethanol produced by the reaction was also distilled off.
Thereafter, the mixture was further reacted at 240 ° C. under a reduced pressure of 1 mmHg for 1 hour, and the resulting high-viscosity elastic polymer was taken out under nitrogen. (The yield of the elastic polymer was 2463 g: the yield was 87.0%.)
The characteristic values of the obtained elastic polymer are shown in Table 1.
[0027]
Synthesis Examples 2-6
An elastic polymer was obtained in the same manner as in Synthesis Example 1 (with the same number of moles and weight% of each compound) except that the molecular weight of PTMG was changed as shown in Table 1.
The characteristic values of the obtained elastic polymer are shown in Table 1.
[0028]
[Table 1]

[0029]
The elastic polymer pellets obtained in Examples 1 to 6, Comparative Examples and Reference Examples Synthesis Examples 1 to 6 were dried under reduced pressure, and then melt-spun under the spinning conditions shown in Table 2 to attach a silicone-based oil. After that, it was wound into a cheese shape. At this time, a spinneret having a nozzle having a hole diameter of 0.5 mmφ was used, and the discharge amount was adjusted so that the fineness of the wound yarn was 50 d.
Subsequently, the elastic yarn was heat-treated in an oven at 120 ° C. for 2 hours in a state of being wound in a cheese shape.
Further, as a reference example, an elastic yarn was obtained in the same manner using a polyether ester having a melting point of 182 ° C. having polybutylene terephthalate as a hard segment and PTMG having a molecular weight of 2000 as a soft segment.
Table 2 shows the results of evaluating the yarn quality of the obtained elastic yarn.
[0030]
[Table 2]

[0031]
As is apparent from Table 2, in Examples 1 to 6, elastic yarns that were excellent in elastic recovery and could withstand high temperature heat setting were obtained. On the other hand, in the comparative example and the reference example, the melting point was low, the heat resistance was poor, the elastic yarn partially melted when the knitted fabric was heat set, the texture was hard, and the stretch back property was inferior.
[0032]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the elastic yarn which is excellent in heat resistance, a quality does not fall with heat processing, and has the outstanding elastic recovery property, and its manufacturing method are provided.

Claims (2)

It consists of an elastic polymer having a melting point of 195 to 235 ° C. composed of an aromatic dicarboxylic acid component represented by the general formula (1) or (2) having an aromatic amide bond and a polyalkylene glycol component, and is 100% The elastic recovery rate at the time of elongation is 80% or more, the elastic recovery rate at the time of 200% elongation is 70% or more, and the high elongation product retention after heat treatment at 190 ° C. for 10 minutes is 85% or more. Elastic yarn with excellent heat resistance.
(1) ROOC-Ph-NHCO-Z-CONH-Ph-COOR '
(2) ROOC-Ph-CONH-Z-NHCO-Ph-COOR '
In the formulas (1) and (2), Ph represents a phenylene group, Z represents a divalent aromatic group, and R and R ′ represent a hydrogen atom or an alkyl group. Melt spinning an elastic polymer having a melting point of 195 to 235 ° C. composed of an aromatic dicarboxylic acid component represented by the general formula (1) or (2) having an aromatic amide bond and a polyalkylene glycol component; A method for producing an elastic yarn excellent in heat resistance, which is wound into a cheese and heat-treated at a temperature of 100 ° C. or higher for 0.5 hours or longer.
(1) ROOC-Ph-NHCO-Z-CONH-Ph-COOR '
(2) ROOC-Ph-CONH-Z-NHCO-Ph-COOR '
In the formulas (1) and (2), Ph represents a phenylene group, Z represents a divalent aromatic group, and R and R ′ represent a hydrogen atom or an alkyl group.