JP2006111989A - Highly hygroscopic polyamide fiber having excellent dyeability and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyamide-based fiber which has excellent dyeability, exhibits high hygroscopicity, and has a good fiber touch, and to provide a method for producing a polyamide-based fiber, by which the polyamide-based fiber can be produced at a low cost. <P>SOLUTION: This highly hygroscopic polyamide fiber having excellent dyeability and obtained by blending polyamide 46 with at least one or more other polymer components is characterized by having a dyeing rate of ≥60% and a water vapor absorption coefficient of ≥4%. The method for producing the polyamide-based fiber having excellent dyeability is characterized by mixing polyamide 46 with polyamide 6 in a ratio of 65/35 to 35/65 and then spinning the mixture. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a polyamide fiber excellent in handleability and comfort and a method for producing the same, and relates to a highly hygroscopic polyamide fiber excellent in dyeability obtained by blending and spinning polyamide 46 with a specific polymer and a method for producing the same. Is.

  Natural fibers typified by cotton and wool are preferred because of their texture and comfort. The main factor of this comfortable wearing feeling is that the natural fiber has an appropriate hygroscopicity. However, natural fibers lack aesthetics such as suppleness and gloss, and are also insufficient in terms of a smooth surface touch, a cool feeling when worn, and the like. In addition, the wear resistance and strength are insufficient and are not suitable for sports applications.

  On the other hand, the polyamide fiber has excellent properties such as strength, flexibility, glossiness, color development, dyeing fastness, abrasion resistance, and softness. Therefore, it has been favored by textile products for clothing such as innerwear, sportswear and pantyhose.

  Conventionally, nylon 6 is well known as a polyamide-based fiber, and since it has high strength and excellent durability, it is preferably used for various textile products for clothing. However, although the equilibrium moisture content (hygroscopicity in the standard state) of nylon 6 is higher than that of polyester fiber, the hygroscopicity is inferior to that of natural fiber, and the comfortable feeling when worn is still insufficient. For this reason, various attempts have been made to improve the hygroscopic properties of polyamide fibers such as nylon 6.

For example, a method for producing hygroscopic polyamide fibers from a polyamide composition in which polyvinyl pyrrolidone is added to polyamide fibers and a reducing agent is added during polymerization is disclosed (for example, see Patent Documents 1 and 2).
JP-A-7-150415 Japanese Patent Laid-Open No. 9-188917

  However, although these methods can surely obtain hygroscopic polyamide fibers, for example, since polyvinylpyrrolidone is a water-soluble polymer, even if it is added to the polymer, the one that has bleeded out to the polymer surface can be washed. There is concern that it will elute. Moreover, since it contains a water-absorbing polymer, there is a problem that the dyeing fastness is poor.

Nylon 46 has a low maximum draw ratio due to the rapid growth of spherulites, and it is difficult to spin at a high speed or to draw sufficiently, and it is difficult to increase the strength. In order to solve the problem of spherulite generation, various attempts have been made conventionally (see, for example, Patent Document 3). In addition, studies have been made to obtain a fiber excellent in heat resistance and flexibility with a composite fiber having nylon 6 as a core component and nylon 46 as a sheath component. However, nylon 46 has a problem that it is easy to crystallize and its dyeability is very poor.
JP-A-63-112719 JP-A-8-158160

  An object of the present invention is to provide a polyamide-based fiber having excellent dyeability, high hygroscopicity, and good fiber texture, and a method for producing such a polyamide fiber at a low cost.

That is, this invention consists of the following structures.
1. A highly hygroscopic polyamide excellent in dyeability, characterized in that it is a fiber blended with polyamide 46 and at least one other polymer component, and has a dyeing speed of 60% or more and a moisture absorption of 4% or more. fiber.
2. 2. The highly hygroscopic polyamide fiber having excellent dyeability according to the first aspect, wherein the other polymer component is polyamide 6.
3. The highly hygroscopic polyamide fiber having excellent dyeability according to the first or second aspect, wherein the composition ratio of the polyamide 46 and other polymer components is 65/35 to 35/65.
4). 4. The highly hygroscopic polyamide fiber having excellent dyeability according to any one of the first to third aspects, wherein an endothermic peak temperature of melting temperature by a DSC differential scanning calorimetry apparatus appears only at 270 ° C. or higher.
5. The highly hygroscopic polyamide having excellent dyeability according to any one of the first to fourth aspects, wherein the polyamide 46 and the polyamide 6 are mixed in a composition ratio of 65/35 to 35/65 and spun. A method for producing fibers.

  ADVANTAGE OF THE INVENTION According to this invention, it became possible to provide the polyamide fiber excellent in dyeability and comfort, and the provision of the manufacturing method which can obtain the above polyamide fiber simply and at low cost was attained.

Hereinafter, the present invention will be described in detail.
The polyamide 46 of the present invention is polytetramethylene adipamide, which is a condensation polymerization product of 1,4-diaminobutane and adipic acid, and further does not impair the purpose of the present invention. You may mix | blend additives, such as a fluorescent whitening agent, a ultraviolet absorber, an antistatic agent, and a flame retardant.

  Although it does not specifically limit about the polymer component comprised with the polyamide 46, Polyesters, such as a polyethylene terephthalate, a polytrimethylene terephthalate, a polytetramethylene terephthalate, Polyamide, for example, polyamide 6, the polyamide 66, or polyethylene, a polypropylene, etc. Examples include polyolefin. In particular, polyamide is preferable from the viewpoint of affinity with polyamide 46, and among these, polyamide 6 is preferable from the viewpoint of price, ease of formation of an amorphous state, and hygroscopicity.

  As a method of blending the polyamide 46 and other polymer components, the respective polymers are mixed in a melted state, and a shearing force is applied to homogenize them, and then the strands are extruded, and the prepared chips are supplied to a general melt spinning apparatus. Method: The average surface area difference of polymer chips is set to 20% or less, each polymer is mixed in a predetermined amount in the state of chips, and a blended polymer obtained by stirring and homogenizing for 30 minutes or more in a blender is used for general melt spinning. A method of supplying to the equipment, a method of melting each polymer with a biaxial extruder, mixing them, further homogenizing with a static mixer, spinning, and a fixed amount of each polymer chip immediately before the extruder, stirring There is a method of spinning by supplying to the extruder through the apparatus, and any method may be adopted. There.

In order to make the polyamide mixed with the polyamide 46 exist in an amorphous state, it is necessary to increase the dispersion level of the polymer. Therefore, in the spinning process, the relationship between the pressure P1 at the extruder outlet and the pressure P2 in the spinneret Is preferably in the relationship of the following formula (1), and the relationship between the diameter D1 of the extruder outlet, the hole diameter D2 of the breaker plate, and the diameter D3 of the mouthpiece hole is preferably in the relationship of the following formula (2).
Formula (1) P1 <P2
Formula (2) D1>D2> D3
The reason is not clear, but for the relationship of P1 <P2, by selecting the pressure inside the spinneret to be larger than the pressure at the extruder outlet, one polymer is selected when it is pushed out of the gear pump, that is, when moving to the high pressure region It is thought that dispersibility is improved by increasing the density and facilitating movement of molecules at that moment. In addition, regarding the relationship of D1>D2> D3, it is considered that by gradually reducing the diameter of the passing orifice, a shearing force that increases stepwise is applied to the polymer, and the dispersibility between the polymers is improved.

  Although the polymer component comprised with the polyamide 46 is comprised from at least 1 or more types of polyamide compound, it is preferable that it is comprised only from a polyamide compound from an affinity viewpoint, and only 1 type of polyamide is preferable from a management viewpoint in industrial production. In particular, polyamide 6 is preferred.

  The polymer component configured with the polyamide 46 is preferably lower than the melt viscosity of the polyamide 46. This is because it is effective to concentrate the tension applied to the polymer discharged from the die in the spinning process toward the polyamide 46 in order to fiberize other polymers in an amorphous state. The relative viscosity difference is preferably 0.1 or more, and more preferably 0.3 or more. However, if the relative viscosity difference is too large, the spinning operability is deteriorated. Therefore, it is preferably 3 or less, and more preferably 2 or less.

  The relative viscosity of the polyamide fiber is preferably 2.8 or more and less than 5.0. This is because, when the polyamide 46 and other polymer are mixed, if it is within this range, it is easy to produce without problems in spinning operability. A more preferable range is 3.0 or more and less than 4.0. The relative viscosity difference is preferably 0.1 or more, and more preferably 0.3 or more. However, if the relative viscosity difference is too large, the spinning operability is deteriorated. Therefore, it is preferably 3 or less, and more preferably 2 or less.

  The amorphous state of the other polymer component in the present invention means a state in which no crystal is formed. Specifically, the polymer component does not have an endothermic peak due to melting or is melted by measurement with a DSC differential scanning calorimeter. This refers to the case where the enthalpy ΔH is 5 cal / g or less. A crystalline polymer having a melting point begins to collapse in the vicinity of the melting point during the temperature rising process, and changes from a solid state to a liquid state. However, although the fiber of the present invention is a crystalline polymer, other polymer components are present in an amorphous state in the fiber, and therefore, an important factor that brings out the important features of the present invention such as improved hygroscopicity. It has become. For example, in the case of an ordinary polyamide 6 polymer single fiber, an endothermic peak having a melting enthalpy ΔH exceeding 5 cal / g is usually shown in a temperature range of about 220 ° C. However, for example, the endothermic peak as described above does not appear in the DSC differential scanning calorimetry measurement of the blend fiber of the present invention in which polyamide 6 is selected as the other polymer component. This means that the polyamide 6 is present in an amorphous state in the fiber.

  The polyamide fiber of the present invention preferably has an endothermic peak temperature in DSC of only 270 ° C. or higher. A fiber having an endothermic peak temperature of less than 270 ° C. is not preferable because the heat resistance is inferior. A more preferable range is 275 ° C. or higher, and further more preferably 280 ° C. or higher. Since the melting point of polyamide 46 is 290 ° C., an endothermic peak appears below 300 ° C.

  The polyamide fiber of the present invention preferably has a moisture absorption rate of 4% or more. If it is less than 4%, it is not preferable because a feeling of peeling tends to remain when it is made into a fabric. More preferably, it is 5% or more. Higher is preferable, but it is usually about 10%.

  It is preferable that the composition ratio of the polyamide 46 and the other polymer component in the fiber of the present invention is 65/35 to 35/65. If the ratio of polyamide 46 exceeds 65%, the take-up speed of 2000 m / min or more is not preferable because the spinning operability deteriorates. On the other hand, if it is less than 35%, other polymers are likely to be crystallized, and the hygroscopicity tends to be inferior. More preferably, it is 60 / 40-40 / 60, and 55 / 45-45 / 55 is still more preferable.

  The polyamide fiber of the present invention preferably has a dyeing speed of 60% or more. The polyamide fiber of the present invention tends to have a dyeing speed of 60% or more due to the presence of many amorphous polymers. If it is 60% or more, the dyeing process time can be shortened or the dyeing temperature can be lowered, so that the energy cost is reduced. More preferably, it is 70% or more, and further more preferably 80% or more. If the amount of amorphous polymer is too large, the yarn strength tends to be low, so the upper limit is preferably 95% or less.

  Next, the manufacturing method of the polyamide fiber of this invention is demonstrated.

  The polyamide fiber of the present invention is obtained by mixing and spinning polyamide 46 and another polymer, preferably polyamide 6, and blended spinning so that at least nylon 46 is 10 wt% or more, preferably 35% or more and 65% or less. To do.

  Examples of the cross-sectional shape of the fiber include, but are not limited to, a circular cross-sectional shape, a hollow shape, a star shape, a multileaf shape, a flat shape, a C shape, a V shape, a W shape, and an I shape.

  Highly hygroscopic polyamide fibers are post-processed, knitted and woven by ordinary methods, and are sewn to produce various clothing products. Among them, innerwear (lingerie, foundation, etc.) and socks (stockings, pantyhose, tights, socks, etc.) worn directly on the skin, or sportswear (windbreaker, tennis wear, Suitable for ski wear, training wear, etc.

  Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, the measurement and evaluation in an Example were performed as follows.

(A) The endothermic peak sample of the melting temperature measured by a DSC differential scanning calorimetry apparatus uses about 5 mg of finely chopped fibers, and is a DSC3100S made by Mac Science, the heating rate is 10 ° C./min from room temperature to 330 ° C., The measurement was performed under an argon gas atmosphere.

(B) A moisture absorption rate tube knitted fabric is prepared, and the oil agent is washed away with hot water of about 70 ° C. After drying at a temperature of 105 ° C. for 2 hours and measuring the weight S0, the moisture is adjusted for 24 hours under the conditions of a temperature of 20 ° C. and a humidity of 65% RH, and the weight S1 is measured.
Moisture absorption W0 (%) = {(S1-S0) / S0} × 100

(C) Recovery rate at 20% elongation Tensileon measuring device is stretched by 20% at a rate of 100% / min, and the elongation S at which it is unloaded immediately without holding time and becomes in a tension-free state is read from the chart. The recovery rate is expressed as follows.
Recovery rate (%) = {(20 −S) / 20} × 100

(D) Dyeing speed cylinder knitted fabric is prepared, and the oil agent is washed away with hot water at about 70 ° C. Use 3% owf of sianin 5R as a dye, put a sample in a bath at a bath ratio of 1:50, raise the temperature from 24 ° C. at a rate of 1 ° C./min as the initial temperature, and dye the dye exhaust rate after 10 minutes. The arrival speed.

(E) Relative viscosity 96.3 ± 0.1 wt% A sample solution was prepared by dissolving the sample in a special grade concentrated sulfuric acid so that the polymer concentration was 10 mg / ml, and the temperature was 20 ° C. ± 0.05 ° C. The relative viscosity of the solution is measured using an Ostwald viscometer with a water drop time of 6 to 7 seconds at the temperature. In the measurement, using the same viscometer, the relative viscosity RV is calculated from the ratio of the drop time T0 (second) of 20 ml of sulfuric acid and the drop time T1 (second) of 20 ml of the sample solution, which is the same as when the sample solution was adjusted. Calculate using.
Relative viscosity (RV) = T1 / T0

Example 1
Chips of polyamide 46 having a relative viscosity of 3.2 and polyamide 6 having a relative viscosity of 3.5 were mixed at a ratio of 1: 1 and dried in a blender for 1 hour. The difference in the average surface area of each chip was 10%. The blended chip was melted with a uniaxial extruder and melt-spun using a die having a hole diameter of 0.24 mmφ and a hole number of 8 holes. At that time, it was taken up at a speed of 2200 m / min, and stretched 2.2 times using a heat roller having a temperature of 170 ° C. to obtain a stretched yarn of 12T / 8. When the obtained yarn was analyzed by DSC, there was no endothermic peak near the melting point (220 ° C.) of polyamide 6 and there was an endothermic peak at 286 ° C., so polyamide 6 was present in an amorphous state. I found out. Table 1 shows the physical properties of the obtained fiber.

(Example 2)
Example 1 was followed except that the mixing ratio of polyamide 6 was 25%. Since the operability was not so good, the spinning speed was changed to 1800 m / min and a sample was taken. When the obtained yarn was analyzed by DSC, there was no endothermic peak near the melting point (220 ° C.) of polyamide 6 and there was an endothermic peak at 286 ° C., so polyamide 6 was present in an amorphous state. I found out.

(Example 3)
Example 1 was followed except that polyamide 66 was used in place of the polyamide 6 chip and the mixing ratio was 40%. As a result of DSC analysis of the obtained yarn, there was no endothermic peak near the melting point (260 ° C.) of polyamide 66, and there was an endothermic peak at 286 ° C., so polyamide 66 was present in an amorphous state. I found out. Table 1 shows the physical properties of the obtained fiber.

(Comparative Example 1)
Example 1 was followed except that the mixing ratio of polyamide 6 was 75%. When the obtained yarn was analyzed by DSC, it had an endothermic peak near 286 ° C. and the melting point of polyamide 6 (220 ° C.). Table 1 shows the physical properties of the obtained fiber.

(Comparative Example 2)
Polyvinylpyrrolidone was polymerized with 8% by weight and ε-caprolactam to obtain chips, and a hygroscopic polyamide was obtained by a direct spinning drawing method with a spinning speed of 1500 m / min and a draw ratio of 1.9 times. When the obtained yarn was subjected to DSC analysis, it had an endothermic peak around 200 ° C. Table 1 shows the physical properties of the obtained fiber.

(Comparative Example 3)
A core-sheath composite fiber having a mixture of 85 parts by weight of polyamide 6 and 15 parts by weight of polyethylene glycol as a core component and polyamide 6 as a sheath component and a weight ratio of the core component / sheath component of 50/50 was melt-spun. The material was scraped once at 1200 m / min and then stretched 3.0 times. When the obtained yarn was analyzed by DSC, it had an endothermic peak around 220 ° C. Table 1 shows the physical properties of the obtained fiber.

(Comparative Example 4)
Example 1 was followed except that only polyamide 46 was melt spun. There were frequent breaks and winding was not possible.

(Comparative Example 5)
Example 1 was followed except that polyamide 66 was used instead of polyamide 46. When the obtained yarn was analyzed by DSC, it had an endothermic peak near 260 ° C. and the melting point of polyamide 6 (220 ° C.). Table 1 shows the physical properties of the obtained fiber.

  The polyamide fiber of the present invention is excellent in dyeability and hygroscopicity, and is suitable as innerwear or pantyhose worn directly on the skin, or sportswear worn in a state where sweating easily occurs.

It is a chart figure by the measurement in the DSC differential scanning calorimetry apparatus of the fiber (Example 1) of this invention.

Explanation of symbols

        1: Endothermic peak

Claims (5)

  A highly hygroscopic polyamide excellent in dyeability, characterized in that it is a fiber blended with polyamide 46 and at least one other polymer component, and has a dyeing speed of 60% or more and a moisture absorption of 4% or more. fiber.   2. The highly hygroscopic polyamide fiber having excellent dyeability according to claim 1, wherein the other polymer component is polyamide 6.   3. The highly hygroscopic polyamide fiber having excellent dyeability according to claim 1, wherein the composition ratio of the polyamide 46 and other polymer components is 65/35 to 35/65.   The highly hygroscopic polyamide fiber having excellent dyeability according to any one of claims 1 to 3, wherein an endothermic peak temperature of a melting temperature by a DSC differential scanning calorimetry apparatus appears only at 270 ° C or higher.   The highly hygroscopic polyamide fiber excellent in dyeability according to any one of claims 1 to 4, wherein the polyamide 46 and the polyamide 6 are mixed in a range of 65/35 to 35/65 as a constituent ratio and spun. Manufacturing method.

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