JP4315009B2 - Blended yarn and textile products comprising the same - Google Patents

Description

  The present invention relates to a mixed yarn composed of a polymer alloy fiber uniformly dispersed in nano size and other fibers or a fiber product using the same, and a nanoporous fiber or uniform nanofiber having uniform nanopores obtained therefrom. The present invention relates to a fiber product using a mixed yarn made of other fibers.

  Polyamide fibers, such as nylon 6 (N6) and nylon 66 (N66), and polyester fibers, such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), have excellent mechanical properties and dimensional stability. It is widely used for interiors, vehicle interiors, and industrial applications. In addition, polyolefin fibers represented by polyethylene (PE), polypropylene (PP) and the like are widely used for industrial applications by taking advantage of lightness.

  However, since the performance of a single polymer fiber is limited, conventionally, polymer modification such as copolymerization and polymer blending, and composite functions by composite spinning and mixed fiber spinning have been studied. In particular, polymer blends do not require a new polymer design and can be produced using a single-component spinning machine, and thus have been actively studied.

  By the way, for the purpose of imparting a lightweight feeling and water absorption to the fiber, a porous fiber using a polymer blend fiber has been conventionally studied. For example, JP-A-2-175965 describes that a porous N6 fiber can be obtained by obtaining a polymer blend fiber composed of N6 and hydrophilic group copolymerized PET and then eluting the copolymerized PET therefrom. As a result, surface irregularities and pores at the sub-μm level are formed, so that a pearly luster can be obtained. On the contrary, there is a problem that the color developability is remarkably lowered. This is because the scattering of visible light increases because the pore size is at the wavelength level of visible light. In addition, there is an example (Patent Document 1) having a pore size smaller than visible light. However, in actuality, there is a coarse PET island in the blended fiber, and this coarse island is eluted to a sub-μm to 1 μm level. In the same manner as in the above-mentioned known technique, there was a problem of color development deterioration. In fact, the 7th line from the top left and right of the second page of the document “Polyester component is present in polyamide as a streak having a thickness of about 0.01 to 0.1 μm, and a cavity of about that size is still present after elution. Exists, "and conversely, the existence of PET coarse islands is implied. In addition, in JP-A-8-158251 and JP-A-8-296123, examples of porous fibers using nylon / PET blend fibers are described. The distribution is large and close to 0.1 to 1 μm, and the problem of color development deterioration due to coarse pores could not be solved.

On the other hand, high functionalization by using super extra fine yarn has been studied, and polymer blend fibers have been used here as well as in the case of porous fibers. For example, JP-A-3-113082 and JP-A-6-272114 describe that N6 extra fine yarn can be obtained by elution of PET from an N6 / PET blend fiber. The fineness of the single yarn is 0.001 dtex (equivalent to a diameter of 0.4 μm) even at the finest, and the high function by ultra-fine thinning is insufficient. In addition, the single fiber fineness of the ultrafine yarn obtained here is determined by the dispersion state of the island polymer in the polymer blend fiber, but the dispersion of the island polymer is insufficient in the polymer blend system used in the publication. For this reason, there was a large variation in single fiber fineness of the obtained ultra-fine yarn. In addition, there is a method (Patent Document 2) for obtaining ultrafine yarns from polymer blend fibers using a static kneader, but in the publication example 2, the theoretical single fiber fineness calculated from the number of divisions of the static kneader is 1 X10 ^-4 dtex (diameter of about 100 nm) and nanofibers can be obtained. When the single fiber fineness of the ultrafine yarn obtained from this is measured, 1 x 10 ^-4 dtex to 1 x 10 ^-2 dtex (diameter 1 µm) It is described that nanofibers having a single fiber diameter could not be obtained. This is considered to be because the island polymers were united in the polymer blend fiber, and the island polymers could not be uniformly dispersed in the nano size. In this way, the single fiber fineness variation of the ultrafine yarn obtained by these conventional technologies is large, and the product performance is determined by the thick single fiber group, and the merit of the ultrafine yarn is not fully exhibited, but also the quality stability etc. There was a problem.

  As in the above known technology, in a polymer blend fiber having a sea-island structure, if the island polymer is to be microdispersed to sub-μm or less, the island polymer is inherently incompatible, and therefore the surface free energy is in accordance with the basic laws of thermodynamics. In order to minimize this, it is easy to form a coarse island. As a result, problems such as a decrease in color developability and an increase in the single fiber fineness variation of the ultrafine yarn were unavoidable.

  Furthermore, when the island polymer has a melting point or softening point of 100 ° C. or less, such as an alkylene glycol derivative, and this becomes a coarse island, the fusion between single fibers is caused by heat during yarn processing such as crimping and twisting and fabric processing. Has occurred, causing problems such as yarn breakage, fluff, and quality degradation. In fact, a heater temperature of about 160-220 ° C is often used for false twisting, which is a type of crimping, and a heat-set temperature of about 160-180 ° C is often used for fabric processing. In that case, Ooshima became a fatal drawback.

  By the way, when a porous fiber or ultrafine yarn is obtained from a polymer blend fiber by weight reduction as in the known art, the opening of a woven fabric or a knitted fabric becomes large, so there is a limit to the shape stability and mechanical properties of the fabric. there were.

Thus, there is a demand for a polymer alloy fiber that is suitable as a precursor for porous fibers and ultra-fine yarns and has excellent dispersion uniformity and hardly contains coarse islands in order to suppress problems during yarn processing and fabric processing. It was. Furthermore, there has been a demand for a polymer alloy fiber that can maintain good shape stability and mechanical properties even after it is made into a porous fiber or ultrafine yarn.
Japanese Patent Laid-Open No. 56-107069 (pages 1 to 3) USP 4,686,074 (19th column)

  The present invention provides a polymer alloy fiber that is capable of obtaining a super fine yarn that has good color developability even after being made into a porous fiber or that has a small single fiber fineness variation, and that can maintain good shape stability and mechanical properties. It is to provide.

The above object is achieved by a mixed yarn characterized in that the following fiber A or fiber B and a fiber C different from these fibers are mixed.
Fiber A:
It shows a sea-island structure composed of a hardly soluble polymer and a readily soluble polymer, the blend ratio of the easily soluble polymer is 10 to 90% by weight, and the area ratio of the coarse island with a diameter of 200 nm or more is 3% or less. A polymer alloy fiber.
Fiber B:
A polymer alloy fiber comprising a hardly soluble polymer and an easily soluble polymer, the blend ratio of the easily soluble polymer is 10 to 90% by weight, and the portion where these layers show a layered structure has 50% or more per fiber cross-sectional area.
Fiber C:
A fiber made of a polymer that is less soluble than a readily soluble polymer.

  The blended yarn composed of the novel polymer alloy fiber of the present invention and other fibers can suppress the deterioration of the color developability of the porous fiber and the variation of the single fiber fineness of the ultrafine yarn, which have been problems in the past, and the form A fiber product excellent in stability and mechanical properties can be obtained.

  The polymer referred to in the present invention is preferably a thermoplastic polymer typified by polyester, polyamide or polyolefin, from the viewpoint of moldability. Among them, many polycondensation polymers represented by polyester and polyamide are more preferable because they have a high melting point. The melting point of the polymer is preferably 165 ° C. or higher because the heat resistance is good. For example, polylactic acid (PLA) is 170 ° C, PET is 255 ° C, and N6 is 220 ° C. The polymer may contain additives such as particles, flame retardant, antistatic agent and the like. In addition, other components may be copolymerized as long as the properties of the polymer are not impaired. However, as a hardly soluble polymer, the copolymerization rate is 5 mol% or 5 in order to maintain the inherent heat resistance and mechanical properties of the polymer. It is preferable that it is below wt%. The molecular weight of the polymer is preferably 10,000 to 500,000 in terms of weight average molecular weight from the viewpoint of fiber forming ability and mechanical properties. Particularly when used in clothing, interiors, vehicle interiors, etc., the hardly soluble polymer has a copolymerization rate of 5 mol% or 5 wt% or less, a relative viscosity of 2 or higher nylon 6, nylon 66, an intrinsic viscosity of 0.50 or higher. PET, polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), and PLA are more preferable. However, in consideration of removing the easily soluble polymer later, the number average molecular weight may be 3000 or more as long as the object of the present application is achieved.

  In the present invention, it is important that the mixed yarn is composed of polymer alloy fibers (fiber A, fiber B) in which a hardly soluble polymer and a readily soluble polymer are uniformly dispersed in a nano size, and other fibers C. This is to obtain porous fibers and ultra-fine fibers by removing the easily soluble polymer from the fiber A or fiber B. However, since this is insufficient in the form stability and mechanical strength of the fiber product, the fiber C is used as a reinforcing material. Are mixed. In this sense, it is important that the fiber C has a lower solubility than the easily soluble polymer. The fiber C preferably has a weight reduction rate of 50% or less, more preferably 10% or less, when the easily soluble polymer is removed from the fiber A or fiber B.

  It is important that the fiber A has a sea-island structure composed of a hardly soluble polymer and an easily soluble polymer. Here, the sea-island structure means a structure in which two or more kinds of polymers adopt a phase separation structure in which a major component or a low viscosity component is a matrix and a minor component or a high viscosity component is a domain. When aiming at porous fibers, it is preferable that the easily soluble polymer is an island, and when aiming at ultra-fine yarn, the easily soluble polymer is the sea. The polymer type in the polymer alloy fiber may be two or more with different solubility, and the number of difficult-to-dissolve and easily soluble polymers can be increased as needed, and of course a compatibilizer can be used in combination. It is. In addition, it is preferable that the islands have a streak-like structure because the thinning behavior during spinning can be stabilized. Here, the streak structure means that the ratio of the length in the fiber axis direction of the island to the diameter is 4 or more.

  It is important that the blend ratio of the easily soluble polymer is 10 to 90% by weight. By setting the blend ratio of the easily soluble polymer to 10% by weight, the generation efficiency of the pores of the porous fiber can be increased. Moreover, by setting it as 90 weight% or less, the excessive strength fall of a porous fiber can be avoided and the production | generation efficiency of a super extra fine thread can be made high. The blending ratio of the easily soluble polymer is preferably 10 to 30% by weight when aiming at the porous fiber, and 50 to 80% by weight when aiming at the ultrafine yarn.

  Furthermore, by making the area ratio of the whole of the large islands with a diameter of 200 nm or more in the polymer alloy fibers 3% or less, it is possible to suppress the color development deterioration due to the coarse pores when the porous fibers are made, It is possible to reduce the single fiber variation when the yarn is used. This is because the wavelength of visible light is about 400 to 800 nm, and there are almost no islands having a diameter of 200 nm or more, so that irregular reflection at the pores when the fiber is made can be significantly reduced. Further, in the polymer alloy fiber, the island may have a slightly distorted elliptical shape and is not necessarily a perfect circle. Therefore, the diameter is obtained by converting the island area into a circle. Moreover, the area with respect to the whole island is an area which totaled all the islands which exist in a fiber cross section, and can be estimated from fiber cross section observation and a polymer blend ratio. The area ratio of the coarse island with a diameter of 200 nm or more to the entire island is preferably 1% or less. More preferably, the area ratio of the islands having a diameter of 100 nm or more to the entire island is 3% or less, more preferably 1% or less, and most preferably 0.1% or less.

  Moreover, it is preferable for the number average diameter of the islands to be 1 to 100 nm because nanoporous fibers having a smaller pore size than conventional porous fibers can be obtained by removing the islands. When the pore size reaches the nano level, not only visible light scattering hardly occurs, but not only the color developability is remarkably improved, but also harmful ultraviolet rays are greatly scattered, and a new function of UV cut is exhibited. Moreover, since the nanofiber with a single fiber diameter of 1-100 nm is obtained when the sea is removed, it is preferable. With such nano-sized pores and fibers, the fiber surface area dramatically increases, and thus has a great advantage of exhibiting excellent hygroscopicity and adsorptivity that could not be expected with conventional porous fibers and ultrafine fibers. is there. In this way, from the viewpoint of color developability and adsorptivity, it is advantageous that the number average diameter of the island is small, but if it becomes too small, the polymer interface becomes too large and the interaction here becomes too great, and the spinning becomes thinning behavior Tends to destabilize. For this reason, the number average diameter of the island is more preferably 10 to 70 nm, and still more preferably 10 to 50 nm.

  It is important that the fiber B has a layered structure composed of a hardly soluble polymer and an easily soluble polymer. Here, the layered structure refers to a state in which the blended polymers form layers and are intermingled with each other (FIG. 2). Therefore, the interface between different polymers is much larger than the conventional sea-island structure, and the compatibility is improved compared to the sea-island structure, but the so-called uniform structure such as PET / PBT alloy. It is a very unique structure that is low compared to. Here, the sample of the transmission electron microscope (TEM) is metal-stained, and the dark portion is a hardly soluble polymer and the light portion is an easily soluble polymer. However, since no clear periodicity is observed in the layer, it is distinguished from a modulation structure by so-called spinodal decomposition. It is also distinct from the so-called sea-sea structure in that it forms a layer. The sea-sea structure is a very unstable structure that appears at a blend ratio in the vicinity of the sea / island reversal in the polymer blend, and naturally it is extremely difficult to perform stable spinning in this region. Further, it is important that the portion showing this layered structure is 50% or more per fiber cross-sectional area. As a result, when it is made into a porous fiber, it has sufficient pores and can improve hygroscopicity, water absorption and the like. The portion showing the layered structure is preferably 90% or more.

  It is important that the blend ratio of the easily soluble polymer is 10 to 90% by weight. By setting the blend ratio of the easily soluble polymer to 10% by weight, the generation efficiency of the pores of the porous fiber can be increased. Moreover, the excessive strength fall of a porous fiber can be avoided by setting it as 90 weight% or less. The blend ratio of the easily soluble polymer is preferably 10 to 30% by weight when aiming at porous fibers.

  Moreover, if the thickness of one layer of the easily soluble polymer in the cross section of the fiber is 1 to 100 nm, the easily soluble polymer is sufficiently ultra-finely dispersed, and sufficient pores can be formed when the porous fiber is formed. It is preferable from the point. In addition, it is preferable that this layer has a streak structure in the longitudinal direction of the fiber because the thinning behavior during spinning can be stabilized.

  As described above, the island polymer or the easily soluble polymer is uniformly dispersed in a nano size, so that even when a polymer having a low melting point or a low softening point is used as the island polymer or the easily soluble polymer, the high temperature treatment is performed. There is also an advantage that the processability of yarn processing such as shrinkage processing and twisting and fabric processing can be improved, and the quality of the obtained product can be improved.

  In fiber A and fiber B, if the readily soluble polymer is an alkali easily soluble polymer, the porous processing and ultra-thinning process by removing the easily soluble polymer utilizes the alkali treatment process, which is a post-processing process for ordinary clothing fibers. This is preferable because it is possible. For example, when an organic solvent-soluble polymer such as polystyrene is used as the easily soluble polymer, it is a great merit in view of the necessity of explosion-proof equipment. The easily soluble polymer is more preferably a hot water-soluble polymer because islands can be removed in the fiber scouring step. Examples of the alkali-soluble polymer include polyesters and polycarbonates, and examples of the hot water-soluble polymer include polyesters obtained by copolymerizing a large amount of hydrophilic groups, alkylene oxides and polyvinyl alcohols, and modified products thereof. Can do.

  Further, since the fiber A and the fiber B do not contain coarse islands, the spinning is more stable than the known polymer blend spinning, and a fiber having small yarn spots is easily obtained. Yarn spots can be evaluated by Wooster spots (U%). In the present invention, if U% is set to 0.1 to 5%, dyeing spots may appear when textile products such as apparel, interior, and vehicle interior are used. A small and high quality product is obtained and preferred. U% is more preferably 0.1 to 2%, and still more preferably 0.1 to 1.5%. In particular, in the case of producing a tone for apparel use, it is also possible to use a thick yarn with U% of 3 to 10%.

  The strength of the fiber used in the present invention is preferably 2 cN / dtex or more, which can improve process passability in twisted yarns, weaving / knitting processes, and the like. The strength is preferably 3 cN / dtex or more. In particular, the fiber C has a strength of 4 cN / dtex or more because of its role as a reinforcing material. Further, if the elongation is 15 to 70%, it is also preferable because the process passability in the twisted yarn, weaving / knitting process and the like can be improved. Further, when used as a raw yarn for sheath yarn of composite stretch false twisting, the elongation is preferably 100 to 200% from the viewpoint of increasing the yarn length difference of the blended yarn.

  Moreover, various fiber cross-sectional shapes, such as a trilobal cross section, a cross section, and a hollow cross section, can be employed. There is no restriction | limiting also about a fineness, The range of about 1-1000 dtex is employable. Further, the fineness balance between the fiber A or fiber B and the fiber C can be appropriately selected according to the use. However, when removing the easily soluble polymer from the fiber A or fiber B, the fineness after removal processing is 2: 8. It is preferable to adjust the fineness so as to be ˜8: 2. When using as a polymer alloy fiber without removing the easily soluble polymer from the fiber A or fiber B, the fineness in the mixed yarn is preferably 2: 8 to 8: 2.

  In the present invention, it is a mixed yarn of fiber A or fiber B and fiber C. When the difference in yarn length in the mixed yarn is 1 to 40%, the feeling of swelling and softness when made into a fabric is obtained. Since it improves, it is preferable. The yarn length difference is more preferably 10% or more. At this time, the fiber A or fiber B is longer than the fiber C, and the fiber A or fiber B is located on the relatively outer side of the mixed yarn to become a sheath yarn, and exhibits characteristics such as water absorption and moisture absorption. It is preferable because it is easy to do. In particular, when a super extra fine thread is obtained from the fiber A or the fiber B, a more excellent texture can be obtained.

The method for mixing fiber A or fiber B and fiber C is not particularly limited, and known methods such as spinning and post-mixing (air blending, composite false twisting, combined twisting, covering, drawing, etc.) are appropriately employed. can do. Here, the spinning mixed fiber is a method in which the fiber A or the fiber B and the fiber C are spun from the same nozzle or different nozzles, and are wound together by entanglement and air entanglement. This method is excellent in that a mixed fiber can be obtained at low cost. At this time, since fiber A or fiber B and fiber C are spun under the same conditions, it is necessary to carefully select the melting point, heat resistance, viscosity, spinning temperature, cooling conditions, spinning speed, etc. of the polymer used. More specifically, the melting point difference between the polymers to be used is preferably within 40 ° C., and the polymer on the low melting point side preferably has a heat resistance that is not easily heat-denatured. Also, with respect to the viscosity, the smaller the difference between the polymers, the more stable the spinning. Therefore, it is preferable to use one having a melt viscosity difference of 300 Pa · s or less at 1216 sec ⁻¹ at the spinning temperature. Also, the spinning temperature is preferably set to the melting point of the high melting point polymer + 35 ° C. or less from the viewpoint of the heat resistance of the low melting point polymer.

  The post-mixing is a method in which the fiber A or the fiber B and the fiber C are separately prepared and then mixed. This is excellent in that the fineness, yarn quality, and mixed state can be freely selected, and various mixed yarns can be obtained. Air mixing includes air entanglement using an interlace nozzle, turbulent flow disturbance processing using a Taslan nozzle, and swirling air flow processing using a swirling nozzle. Among these, it is preferable to perform an air entanglement process in order to improve the convergence and uniformity of the blended yarn and to improve the handleability in the next step. In order to improve the bulkiness of the mixed yarn, it is preferable to perform a turbulent flow disturbance treatment. Further, in order to suppress the air entanglement hardness while obtaining a certain degree of blended yarn convergence, it is preferable to perform swirling airflow treatment.

  The composite false twist is a method in which the fiber A or the fiber B and the fiber C are combined and then false twisted together. When the elongation of the fiber A or the fiber B and the fiber C is different by 50% or more, the composite false twist is large. A feeling of swelling due to a difference in yarn length can be obtained. In addition, it is preferable to use air entanglement together at the time of synthesizing, because the converging property of the mixed yarn is improved, and defects such as fluff and nep can be suppressed. In addition, the higher the temperature of the heater during false twisting, the stronger the heat set, so the crimping becomes stronger. However, in consideration of thermal transformation and fusion of the low melting point polymer, the melting point of the low melting point polymer is not exceeded. It is preferable to be in the range. As the false twist rotor, a spinner pin, a friction disk, a belt, or the like can be used. A spinner pin is suitable for giving a strong false twist, and a friction disk or belt is preferred for a high-speed false twist.

  Synthetic twisting is a method in which fibers A or B and fibers C are aligned and then twisted together to improve the convergence of the mixed yarn. It can be done.

  Covering involves winding the fiber A or fiber B around the fiber C, and there is an example in which nylon fiber is covered with polyurethane fiber and used for pantyhose or tights.

  In order to increase the yarn length difference between fiber A or fiber B and fiber C in the mixed yarn or fiber product, fibers having greatly different elongation and heat shrinkage ratio, air mixed fiber or composite It is effective to make a difference in the overfeed rate of fiber A or fiber B and fiber C during false twisting.

  The blended yarn of the present invention can be used even with the polymer alloy fiber, but in the case of using the fiber A or fiber B in which the easily soluble polymer is an island component, by removing the easily soluble polymer, It can be used as a porous fiber (fiber D). Here, since the easily soluble polymer is uniformly dispersed in the nano size in the fiber A and the fiber B, when the polymer is removed, the pore size is uniform and smaller than that of the conventional porous fiber. A nanoporous fiber having an infinite number of pores can be obtained. Here, the nano-level pores are those having a pore diameter of 100 nm or less that can be observed by TEM. An example of the nanoporous fiber produced from the polymer alloy fiber of the present invention is shown in FIG. 6 (fiber cross-sectional TEM photograph), where the dark portion indicates the high density region and the light portion indicates the low density region. Here, it is considered that the light portion corresponds to the pore. That is, there is an advantage that the pore size can be made smaller than the dispersion size of the easily soluble polymer in the polymer alloy stage. Note that not only the pores but also the fiber diameter itself may shrink with the removal of the easily soluble polymer. It is important that the fiber D, which is a porous fiber, is a nanoporous fiber having pores having a diameter of 100 nm or less and having an area ratio of coarse pores having a diameter of 200 nm or more occupying the entire fiber cross section of 1.5% or less. is there. Thereby, irregular reflection of visible light can be controlled, a color development fall can be suppressed, and a high-quality dyed fabric can be provided. Preferably, the area ratio of pores having a diameter of 100 nm or more is 1.5% or less, more preferably 0.1% or less. More preferably, the area ratio of pores having a diameter of 50 nm or more is 1.5% or less, most preferably 0.1% or less. The pore area ratio is the area ratio of the designated pore to the entire fiber cross section, and the entire fiber cross section is the sum of the polymer and the pores in the fiber cross section. The number average pore diameter of the nanoporous fiber is preferably 80 nm or less, more preferably 50 nm or less.

  This nanoporous fiber has the merit that the specific surface area is increased by innumerable nano-level pores, and excellent moisture absorption / adsorption is exhibited. In fact, in N6 nanoporous fiber, ΔMR, which is an index of hygroscopicity, reaches 4 to 6%, and exhibits excellent hygroscopicity over cotton (ΔMR = 4%). Moreover, this nanoporous fiber is excellent not only in water vapor but also in the adsorption properties of various substances, and is useful as a deodorizing fiber. Furthermore, it may exhibit water absorbency similar to cotton, or may exhibit the function of a natural fiber while being a synthetic fiber.

  Moreover, there is no restriction | limiting in particular in the fiber combined with the fiber D, but if the fiber C does not change by operation which removes an easily soluble polymer from the fiber A or the fiber B, it will become the same as the fiber C.

  In the mixed yarn made of the fiber D, it is preferable that the fiber D is positioned on the relatively outer side of the mixed yarn and used as a sheath yarn because the characteristics of the fiber D that is a nanoporous fiber are easily developed. On the other hand, it is preferable to arrange the fiber D relatively on the inner side of the blended yarn and use it as a core yarn, because porous fibers that tend to deteriorate the wear characteristics are protected, and thus the friction durability of the fabric is improved.

  On the other hand, in the case of using the fiber A in which the easily soluble polymer is a sea component, it can be used as a super fine yarn by removing the easily soluble polymer. Here, since the hardly soluble polymer is uniformly dispersed in the nano size in the fiber A, when the polymer is removed, the dispersion of the single fiber diameter is smaller than that of the conventional ultrafine yarn, and the single fiber diameter is 200 nm or less. Fiber can be obtained. The ultra-fine yarn obtained from the fiber A has a number average single fiber diameter of 1 to 150 nm, the weight ratio of coarse single fibers having a single fiber diameter of more than 150 nm is 30% or less, and is made of a thermoplastic polymer. It is important to have a fiber assembly. That is, since there is almost no thick single fiber whose single fiber diameter exceeds 150 nm, the large specific surface area of the nanofiber can be effectively utilized. The number average single fiber diameter is preferably 10 to 100 nm, more preferably 30 to 80 nm. The single fiber variation is preferably such that the weight ratio of single fibers having a single fiber diameter exceeding 100 nm is 30% or less, more preferably 5% or less, and even more preferably 1% or less.

Such single fiber diameters and variations thereof can be determined as follows. That is, it can be determined by observing the cross section of the nanofiber assembly with a transmission electron microscope (TEM) and measuring the diameter of 300 or more single fibers randomly extracted within the same cross section. An example of a fiber cross-sectional photograph of the nanofiber of the present invention is shown in FIG. Next, the average value of the single fiber diameter is determined as follows. That is, a simple average value of the measured single fiber diameters is obtained, and this is defined as “number average single fiber diameter”. Moreover, the single fiber diameter variation of a nanofiber is evaluated as follows. That is, the single fiber fineness is calculated from the single fiber diameter of each nanofiber, and this is defined as dt _i . Then, the total sum thereof is defined as the total fineness (dt ₁ + dt ₂ +... + Dt _n ). The frequency (number) of nanofibers having the same single fiber fineness (single fiber diameter) is counted, and the product divided by the total fineness is defined as the weight ratio of the single fiber fineness (single fiber diameter). This corresponds to the weight fraction (volume fraction) of each single fiber diameter component with respect to the whole (nanofiber aggregate), and a single fiber diameter component having a large value contributes greatly to the properties of the nanofiber aggregate.

  In addition, it is important that the fiber F combined with the nanofibers has a single fiber fineness of 0.1 dtex or more, thereby obtaining a sufficient nanofiber reinforcing effect. When the single fiber fineness of the fiber F is preferably 1 to 10 dtex, not only the reinforcing effect is further improved, but the softness of the fabric is not impaired, and a fiber product having a good texture can be obtained.

  Moreover, in the mixed fiber of nanofibers and fibers F, it is preferable that the nanofibers are arranged so as to cover the surface of the fibers F because the characteristics of the nanofibers are easily developed. On the other hand, it is preferable to place the fiber E on the relatively inner side of the blended yarn because the nanofibers having a tendency to deteriorate the wear characteristics are protected, so that the friction durability of the fabric is improved.

  The blended yarn containing the polymer alloy fiber of the present invention or the blended yarn containing the nanoporous fiber or the blended yarn containing the nanofiber takes various fiber product forms such as woven fabric, knitted fabric, non-woven fabric, artificial leather, and thermoformed body. Can do. In particular, in order to further improve the shape stability and mechanical properties of the fiber product, it is preferable that the mixed yarn is raised only on the surface of the fiber product. For this reason, for example, in a woven fabric, it is preferable to use the mixed yarn as either a warp or a weft and to employ a structure with front and back surfaces such as twill and satin.

  Further, among the fiber products, the nanoporous fiber or nanofiber is preferably 1 to 40% in yarn length difference from the other fiber because the fiber product exhibits good bulkiness.

  In order to obtain a fiber product containing nanoporous fiber (fiber D) or nanofiber (fiber E) from a fiber product containing polymer alloy fibers (fiber A, fiber B), an easily soluble polymer is obtained from the previous fiber product. However, in the case of a fiber product containing nanofibers, it can also be obtained by stopping the removal of the readily soluble polymer from the fiber product containing fiber A alone. However, when the amount is reduced halfway, it is preferable to control the removal rate by slowing the removal rate of the easily soluble polymer so as to maintain the uniformity of the removal rate between the single fibers.

  The intermediate products obtained in this way are not only used for comfortable clothing such as shirts, blousons, pants and coats, but also used for clothing materials such as cups and pads, interiors such as curtains, carpets, mats and furniture, It can also be suitably used for industrial material applications such as filters and vehicle interior applications. Furthermore, it can be used as a state-of-the-art material for IT and medical applications such as fuel cell electrodes and blood cell separation by adsorption of functional molecules.

  Although the manufacturing method of the polymer alloy fiber (fiber A, fiber B) used by this invention is not restrict | limited in particular, For example, the following methods are employable.

  That is, the hardly soluble polymer and the easily soluble polymer are melt-kneaded to obtain a polymer alloy composed of the hardly soluble polymer / the easily soluble polymer. At this time, it is preferable to perform high kneading with a kneading extruder or a stationary kneader. Note that kneading is insufficient with a simple chip blend (for example, JP-A-6-272114), and thus it is difficult to disperse islands with a size of several tens of nm as in the present invention.

  Specifically, as a guide when kneading, depending on the polymer to be combined, when using a kneading extruder, it is preferable to use a twin-screw extrusion kneader, and when using a static kneader, the number of divisions is It is preferable to set it to 1 million or more. Moreover, in order to avoid blend spots and fluctuations in the blend ratio over time, it is preferable to measure each polymer independently and supply the polymers to the kneading apparatus independently. At this time, the polymer may be supplied separately as pellets, or may be supplied separately in a molten state. Two or more kinds of polymers may be supplied to the root of the extrusion kneader, or may be a side feed that supplies one component from the middle of the extrusion kneader.

  When a twin screw extrusion kneader is used as the kneading apparatus, it is preferable to achieve both high kneading and suppression of the polymer residence time. The screw is composed of a feeding part and a kneading part, but it is preferable that the kneading part length is 20% or more of the effective screw length, so that high kneading can be achieved. Moreover, when the kneading part length is 40% or less of the effective screw length, excessive shear stress can be avoided and the residence time can be shortened, and thermal degradation and gelation of the polymer can be suppressed. Further, the kneading part is positioned as close as possible to the discharge side of the twin-screw extruder, so that the residence time after kneading can be shortened and re-aggregation of the island polymer can be suppressed. In addition, when strengthening kneading, it is possible to provide a screw having a backflow function for sending the polymer in the reverse direction in an extrusion kneader.

  Furthermore, the hydrolysis of a polymer can be suppressed by sucking the decomposition gas at the time of kneading as a vent type, or reducing the water in the polymer, and the terminal group in the polymer can be suppressed.

  In addition, a combination of polymers is also important in order to uniformly disperse the islands in the nano size.

In particular, when aiming at nanofibers, it is preferable that the island polymer and the sea polymer are incompatible with each other in order to make the island domain (cross section of the nanofiber) close to a circle. However, it is difficult for the island polymer to be sufficiently finely dispersed by a simple combination of incompatible polymers. For this reason, it is preferable to optimize the compatibility of the polymer to be combined, but one index for this purpose is the solubility parameter (SP value). The SP value is a parameter reflecting the cohesive strength of a substance defined by (evaporation energy / molar volume) ^1/2 , and a polymer alloy having good compatibility may be obtained between materials having close SP values. The SP value is known for various polymers, and is described, for example, in “Plastic Data Book”, edited by Asahi Kasei Amidus Corporation / Plastics Editorial Department, page 189. It is preferable that the difference between the SP values of the two polymers is 1 to 9 (MJ / m ³ ) ^{1/2 because} it is easy to achieve both circularization of island domains and ultrafine dispersion due to incompatibility. For example, the difference in SP value between N6 and PET is about 6 (MJ / m ³ ) ^1/2, which is a preferable example. The difference between N6 and PE is about 11 (MJ / m ³ ) ^{1/2 in} SP value. There are some unfavorable examples.

  Further, it is preferable that the difference in melting point between polymers is 20 ° C. or less because kneading with an extrusion kneader makes it difficult to produce a difference in the melting state in the extrusion kneader, so that high-efficiency kneading is easy.

  Further, when a polymer that is easily decomposed or thermally deteriorated is used as one component, it is necessary to keep the kneading and spinning temperature low, which is also advantageous. Here, in the case of an amorphous polymer, since there is no melting point, it is replaced by the glass transition temperature, Vicat softening temperature or heat distortion temperature.

  Due to the characteristics of the production method as described above, since the formation of coarse islands is suppressed, the viscoelastic balance of the polymer alloy is less likely to be disrupted, and the spinning discharge is stable, and the spinnability and yarn unevenness can be remarkably improved. There are also advantages. Further, when a diameter larger than usual is used as the diameter of the die hole, the shear stress to the polymer alloy at the die hole can be reduced and the viscoelastic balance can be maintained, so that the spinning stability is improved. Specifically, it is preferable to use a die capable of a discharge linear velocity of 15 m / min or less at the polymer alloy die. In addition, the cooling of the yarn is also important. By setting the distance from the base to the active cooling start position to 1 to 15 cm, the polymer alloy that tends to destabilize the elongational flow can be quickly solidified to spin the yarn. It can be stabilized.

  Further, from the viewpoint of miniaturizing the island polymer, the spinning draft is preferably 100 or more. Furthermore, in order to suppress the time-dependent change in the dimensions and physical properties of the undrawn yarn, it is preferable to develop the fiber structure with a spinning speed of 2500 m / min or more.

  As described above, the mixed yarn composed of the novel polymer alloy fiber of the present invention and other fibers suppresses the deterioration of the color developability of the porous fibers and the variation of the single fiber fineness of the ultrafine yarn, which have been problems in the past. In addition, it is possible to obtain a fiber product having excellent shape stability and mechanical properties.

  Hereinafter, the present invention will be described in detail with reference to examples. In addition, the measuring method in an Example used the following method.

A. Polymer melt viscosity The polymer melt viscosity was measured with a Capillograph 1B manufactured by Toyo Seiki. The polymer storage time from sample introduction to measurement start was 10 minutes.

B. Polymer Melting Point Using Perkin Elmaer DSC-7, the peak top temperature showing the melting of the polymer at 2nd run was taken as the melting point of the polymer. At this time, the rate of temperature increase was 16 ° C./min, and the sample amount was 10 mg.

C. Mechanical properties of fiber A load-elongation curve was obtained under the conditions shown in JIS L1013 at room temperature (25 ° C.) with a pulling rate of 100% / min. Next, the load value at break was divided by the initial fineness, which was used as the strength, and the elongation at break was divided by the initial sample length to obtain a strong elongation curve.

D. Worcester spots on fibers (U%)
Measurement was performed in a normal mode at a yarn feeding speed of 200 m / min using a USTER TESTER 4 manufactured by Zervegar Worcester.

E. Thermal contraction rate of fiber Thermal contraction rate (%) = [(L0−L1) / L0)] × 100 (%)
L0: Original length of skein measured after skeining yarn and initial load of 0.09 cN / dtex L1: Skein measured with L0 was treated in boiling water for 15 minutes in a substantially load-free state, and initial load was 0 after air drying Skein length under .09 cN / dtex Fiber cross-sectional observation by TEM Ultra-thin sections were cut in the cross-sectional direction of the fiber, and the fiber cross-section was observed with a transmission electron microscope (TEM). Moreover, the metal dyeing | staining was given as needed.

TEM apparatus: H-7100FA type manufactured by Hitachi, Ltd. Number average diameter of islands and pores and single fibers The diameter of the islands in the polymer alloy and the single fiber diameter of the superfine yarn are analyzed as follows. That is, the diameter of the island diameter in terms of a circle was determined from a fiber cross-sectional photograph by TEM using image processing software (WINROOF). In addition, when the island was too fine or the shape was complicated and analysis by WINROOF was difficult, the analysis was performed by visual inspection and manual work. The average diameter was determined by their simple number average value. At this time, the average number of islands used was 300 or more randomly selected in the same cross section. However, since the sample for TEM observation is an ultrathin section, the sample is easily broken or perforated. For this reason, the diameter analysis was carried out carefully against the sample conditions. The pore diameter in the porous fiber and the single fiber diameter of the super extra fine thread conformed to the above-mentioned island diameter analysis.

H. Island diameter variation in polymer alloy fiber The island diameter variation was evaluated as follows. That is, using the data used when obtaining the number average diameter, the cross-sectional area of each island domain is S _i and the sum is the total area (S ₁ + S ₂ +... + S _n ). Further, the frequency (number) of island domains having the same diameter (area) is counted, and the product of the product divided by the total area is defined as the area ratio of the island domains.

I. Pore Diameter Variation in Porous Fiber Pore diameter variation was evaluated as follows. That is, using the data used to determine the number average diameter, count the frequency (number) of pores with the same diameter (area), and divide the product of the area and frequency by the area of the fiber cross section The area ratio of the pores. Here, inorganic fine particles and voids around them were not included in the pores.

J. et al. Single fiber diameter variation of ultrafine yarn The single fiber fineness variation of superfine yarn is evaluated as follows. That is, the single fiber fineness (dt _i ) of each of the super extra fine yarns is calculated from the data used when obtaining the single fiber diameter by the number average. Then, the sum is defined as a total fineness (dt ₁ + dt ₂ +... + Dt _n ). Further, the frequency (number) of super fine yarns having the same single fiber fineness is counted, and the product divided by the total fineness is defined as the weight ratio of the single fiber diameter.

K. Evaluation of coloring property The obtained sample was dyed according to a conventional method, and the coloring property was compared with a comparative sample dyed under the same conditions. As a comparative sample, a nanoporous fiber or a polymer constituting the nanofiber was used to produce a yarn by a conventional method. More specifically, the following method was used.

  In the case of nylon, “Nylosan Blue N-GFL” manufactured by Clariant Japan Co., Ltd. is used as the dye, and the dye is adjusted to 0.8% by weight of the fiber product and the pH is adjusted to 5. The bath ratio is 100 times, 90 ° C. Processed for 40 minutes.

  In the case of polyester, “Foron Navy S-2GL” manufactured by Clariant Japan Co., Ltd. is used as the dye, and the dye is adjusted to 0.8% by weight of the fiber product and the pH is adjusted to 5, and the bath ratio is 1: 100, 130. Treated for 40 minutes at ° C.

  A product with a color development that is equal to or higher than that of visual comparison (○) is accepted. Those that were inferior to this were considered as (Δ, ×) rejected.

L. Hygroscopicity (ΔMR)
The sample is weighed in a weighing bottle of about 1 to 2 g, dried at 110 ° C. for 2 hours, dried, and weighed (W0). Next, the target substance is held at 20 ° C. and relative humidity 65% for 24 hours and then weighed. (W65). And this is hold | maintained at 30 degreeC and relative humidity 90% for 24 hours, Then, a weight is measured (W90). The calculation is performed according to the following formula.

MR65 = [(W65−W0) / W0] × 100% (1)
MR90 = [(W90−W0) / W0] × 100% (2)
ΔMR = MR90−MR65 (3)
M.M. Yarn length difference 30 cm of the mixed yarn or the mixed yarn extracted from the fiber product was sampled, carefully divided into each fiber, and each yarn length was measured to obtain the yarn length difference.

Reference example 1
80% by weight of homo-N6 having a melt viscosity of 31 Pa · s (275 ° C., shear rate of 1216 sec ⁻¹ ) and a melting point of 220 ° C. and 5-sodium sulfone having a melt viscosity of 200 Pa · s (275 ° C., shear rate of 1216 sec ^{−1 and} a melting point of 250 ° C. 20% by weight of copolymerized PET (co-PET1) containing 5% by weight of isophthalic acid and 0.05% by weight of titanium oxide was melt-kneaded at 260 ° C. with a twin-screw extruder kneader to obtain polymer alloy pellets. The kneading conditions at this time are as follows.

Model Same direction complete meshing type Double screw Screw diameter 37mm, effective length 1670mm, L / D = 45.1
The kneading section head is 28% of the effective screw length
There are three backflow parts on the way. Polymer supply N6 and copolymerized PET were weighed separately and supplied separately to the kneader.

260 ° C
Residence time 2 minutes Vent 2 locations The polymer alloy pellets were melted in the melting part 2 at 270 ° C. and led to a spin block at a spinning temperature of 275 ° C. Then, the polymer alloy melt was filtered with a metal nonwoven fabric having a limit filtration diameter of 15 μm, and then melt-spun (FIG. 9). A base having a discharge hole diameter of 0.2 mm was used, and the distance from the bottom of the base to the cooling start point (the upper end of the chimney 6) was 5 cm. Also, a nylon monomer suction device 5 was installed just below the base. The discharged yarn is cooled and solidified with a cooling air of 20 ° C. over 1 m, and is supplied by an oil supply guide 8 installed 1.8 m below the base 4, and then the unheated first take-up roller 9 and second take-up roller Winding at a winder circumferential speed of 2950 m / min with a circumferential speed of 3000 m / min, a highly oriented undrawn yarn of 55 dtex, 48 filaments, strength 2.7 cN / dtex, elongation 130%, U% 1.2% is obtained. It was. The spinnability at this time was good, and there was no yarn breakage during continuous spinning for 24 hours. Further, there was no collapse of the package due to the time-lapse swelling of the wound package, which was a problem with nylon, and the handleability was excellent.

  As a result of observing the fiber cross section of the obtained polymer alloy highly oriented unstretched yarn with TEM (FIG. 1), the area ratio of the island having a diameter of 200 nm or more to the whole island is 0.1% or less, not including the coarse island. The area ratio of 100 nm or more in diameter was also 0.1% or less. The number average diameter of the islands was as small as 30 nm. Moreover, it was found from the fiber longitudinal section TEM photograph that the island has a streak structure.

Reference example 2
N6 and co-PET1 used in Example 1 were melted at 270 ° C. and 290 ° C. using the apparatus shown in FIG. 10, respectively, and then the stationary kneader 12 (“High Mixer” 10 manufactured by Toray Engineering Co., Ltd. 10) was installed. ) And divided and mixed. And after filtering this with the metal nonwoven fabric filter with an absolute filtration diameter of 20 micrometers, it discharged from the nozzle | cap | die hole with a hole diameter of 0.35 mm. At this time, the spinning temperature was 280 ° C., and the distance from the die 5 to the upper end of the chimney 6 was 7 cm. This was taken up at a spinning speed of 900 m / min and taken up via the second take-up roller 10. Although spinning was performed for 24 hours, there was no yarn breakage during spinning, and good spinnability was exhibited. This was stretched and heat-treated using the apparatus shown in FIG. At this time, the draw ratio was 3.2 times, the first hot roller 15 temperature was 70 ° C., and the second hot roller 16 temperature was 130 ° C. There was no yarn breakage during drawing and heat treatment, and good drawability was exhibited.

  As a result, a polymer alloy fiber of 56 dtex and 12 filaments was obtained, but the U% was 1.5%, which was sufficiently small. Moreover, when the fiber cross section of this was observed with TEM, the N6 part dyed deep by metal dyeing and the light PET part formed a special layered structure, and the thickness of the PET layer part was about 20 nm ( Figure 2). In addition, this fiber had a sea-island structure with a special layer structure collapsed from the fiber surface layer to about 150 nm, but when the area of the special layer structure part was estimated, it was 98% with respect to the entire fiber cross section, Most of the fiber cross section formed a special layered structure (FIG. 3). Moreover, when the longitudinal cross section of this polymer alloy fiber was observed with TEM, the layer became a streak shape.

Reference example 3
Instead of co-PET1, a melt viscosity of 114 Pa · s (275 ° C., 1216 sec ⁻¹ ), which is a hot water soluble polymer of a polyalkylene oxide derivative, is “Paogen PP-15” manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and the kneading temperature is 275 ° C. As in Reference Example 1, melt kneading was performed to obtain polymer alloy pellets. Using this, the discharge amount per single hole and the number of nozzle holes were changed, the spinning speed was 4000 m / min, the draw ratio was 1.2 times, the temperature of the first hot roller 19 was 40 ° C., and the second hot roller 20 The temperature was set to 130 ° C., and the spinning was directly drawn using the apparatus shown in FIG. 12 to obtain a 55 dtex, 68 filament polymer alloy fiber. The spinnability was good and the yarn breakage during 24 hours of continuous spinning was zero. As a result of observing the fiber cross section of the obtained polymer alloy fiber with TEM, the area ratio of the coarse island having a diameter of 200 nm or more to the whole island was 1.3%.

Reference example 4
Reference at 275 ° C. with a homo-PET having a melting point of 255 ° C., an intrinsic viscosity of 0.63, and a melt viscosity of 130 Pa · s (280 ° C., 1216 sec ⁻¹ ) at 80% by weight and the hot water-soluble polymer used in Reference Example 3 at 20% by weight. In the same manner as in Example 1, melt kneading was performed using a twin screw extrusion kneader. When the melt temperature was 280 ° C. and the spinning temperature was 280 ° C., and the melt spinning was performed in the same manner as in Reference Example 1 by changing the single-hole discharge amount and the number of nozzle holes, the spinning property was good and 24 hours. The yarn breakage during the continuous spinning was zero. Then, the first hot roller temperature 15 was set to 90 ° C., and stretching and heat treatment were performed in the same manner as in Reference Example 2, 90 dtex, 36 fragments, strength 3.3 cN / dtex, elongation 40%, U% 1.5%, heat A polymer alloy fiber having a shrinkage rate of 7% was obtained. As a result of observing the fiber cross section of the obtained polymer alloy fiber with TEM (FIG. 4), the area ratio of the island having a diameter of 200 nm or more not including the coarse island is 0.1% or less and the diameter is 100 nm or more. The area ratio was also 0.1% or less. Here, the dark part is PET and the thin part is hot water-soluble polymer. Moreover, it was found from the fiber longitudinal section TEM observation that the island has a streak structure.

Reference Example 5
N6 used in Reference Example 1, 20 wt%, melt viscosity 130 Pa · s (280 ° C., 1216 sec ⁻¹ ), melting point 225 ° C., isophthalic acid 8 mol%, bisphenol A 4 mol% copolymerized 225 ° C. Polymerized PET (co-PET2) was kneaded at 260 ° C. in the same manner as in Reference Example 1 with 80 wt% to obtain a polymer alloy chip. The co-PET2 had a melt viscosity of 180 Pa · s at 262 ° C. and 1216 sec ⁻¹ . Next, this polymer alloy chip was spun in the same manner as in Reference Example 4 to obtain a polymer alloy fiber. At this time, the distance from the lower surface of the base to the cooling start point (the upper end of the chimney 6) was 9 cm. The spinnability at this time was good, and the number of breaks during continuous spinning for 24 hours was zero. As in Reference Example 4, the temperature of the first hot roller 15 was 90 ° C., and the temperature of the second hot roller 16 was 130 ° C. The draw ratio between the first hot roller 15 and the second hot roller 16 was set to 3.2 times. The obtained polymer alloy fiber exhibited excellent properties of 120 dtex, 36 filaments, strength 4.0 cN / dtex, elongation 35%, U% = 1.7%, and heat shrinkage 11%. Moreover, when the cross section of the obtained polymer alloy fiber was observed with TEM, copolymerized PET (thin portion) showed sea and N6 (dark portion) showed island-island structure (FIG. 5), and the number of N6 island domains The average diameter was 53 nm, and a polymer alloy fiber in which N6 was nano-sized and uniformly dispersed was obtained.

Reference Example 6
Poly L-lactic acid (optical purity) having a melt viscosity of 250 Pa · s (240 ° C., 1216 sec ⁻¹ ) and 40% by weight of N6, a weight average molecular weight of 120,000, a melt viscosity of 35 Pa · s (240 ° C., 1216 sec ⁻¹ ), and a melting point of 170 ° C. 99.5% or more) was melt kneaded in the same manner as in Reference Example 1 at a kneading temperature of 235 ° C. to obtain polymer alloy pellets. The weight average molecular weight of polylactic acid was determined as follows. Tetrahydrofuran (THF) was mixed with the sample chloroform solution to obtain a measurement solution. This was measured at 25 ° C. using Waters 2690 gel permeation chromatography (GPC) Waters 2690, and the weight average molecular weight was calculated in terms of polystyrene.

  This was melt-spun in the same manner as in Reference Example 1 at a melting temperature of 240 ° C., a spinning temperature of 240 ° C., and a spinning speed of 3000 m / min. At this time, a die having a die hole diameter of 0.3 mm was used as the die. The spinnability was good and the yarn breakage was zero in 24 hours of continuous spinning. As a result, a highly oriented undrawn yarn of 92 dtex and 36 filaments was obtained, and the strength thereof was extremely excellent as a highly oriented undrawn yarn of 2.4 cN / dtex, elongation of 90%, and U% = 1.5%. It was a thing.

  This highly oriented undrawn yarn was drawn and heat treated in the same manner as in Reference Example 1 at a drawing temperature of 90 ° C., a draw ratio of 1.39 times, and a heat setting temperature of 130 ° C. The obtained drawn yarn was 67 dtex, 36 filaments, and exhibited excellent properties of a strength of 3.6 cN / dtex, an elongation of 40%, a heat shrinkage of 9%, and U% = 1.5%.

  When the cross section of the obtained polymer alloy fiber was observed with TEM, PLA showed a sea-island structure of the sea (thin part), N6 was an island (dense part), and coarse islands with a diameter of 200 nm or more were 0.1% or less, The number average diameter of the island N6 was 65 nm, and a polymer alloy fiber in which N6 was nano-sized and uniformly dispersed was obtained.

Reference Example 7
A melt viscosity of 220 Pa · s (250 ° C., 1216 sec ⁻¹ ), polytrimethylene terephthalate (PTT) having a melting point of 225 ° C. and PLA used in Reference Example 6 were melt-kneaded in the same manner as in Reference Example 1 at a kneading temperature of 245 ° C. Polymer alloy pellets were obtained.

  This was melt-spun in the same manner as in Reference Example 1 at a melting temperature of 245 ° C., a spinning temperature of 250 ° C., and a spinning speed of 1200 m / min. At this time, as shown in FIG. 13, a spinneret having a measuring part 22 having a diameter of 0.23 mm and having a discharge hole diameter of 2 mm and a discharge hole length of 3 mm was used as shown in FIG. The spinnability was good, and the yarn was broken once after continuous spinning for 24 hours. The obtained undrawn yarn was drawn and heat treated in the same manner as in Reference Example 2. At this time, the temperature of the 1st hot roller 15 was 90 degreeC, and the temperature of the 2nd hot roller 16 was 130 degreeC. The draw ratio between the first hot roller 15 and the second hot roller 16 was 3.5 times. The obtained polymer alloy fiber exhibited excellent properties of 120 dtex, 36 filaments, strength 2.5 cN / dtex, elongation 45%, U% = 1.7%, and heat shrinkage 11%.

  Further, when the cross section of this drawn yarn was observed with a TEM, it showed a sea-island structure in which PLA was the sea and PTT was the island. Coarse islands having a diameter of 200 nm or more were 0.1% or less, and the diameter by the number average of PTT was 70 nm. In addition, a polymer alloy fiber in which PTT was nano-sized and uniformly dispersed was obtained.

Reference Example 8
Melt kneading, melt spinning, stretching and heat treatment were carried out in the same manner as in Reference Example 5 with the weight ratio of N6 and co-PET2 used in Reference Example 5 being 80% by weight / 20% by weight. The obtained polymer alloy fiber is 50 dtex, 12 filaments, and the observation result of the cross section of the fiber with TEM is shown in FIG. 8, but the number average diameter of the island is 180 nm, and the area ratio of the coarse island to the whole island is 32%. Met. Moreover, it was found from the fiber longitudinal section TEM observation that the island has a streak structure.

Reference Example 9
N6 used in Reference Example 6 was 77% by weight, homo-PET used in Reference Example 4 was 20% by weight, and block polyether polyamide (polyethylene glycol part 45% by weight + poly-ε-caprolactam part 55% by weight) as a compatibilizing agent. 9) was simply subjected to chip blending and melt spinning was carried out in the same manner as in Reference Example 1 using the apparatus shown in FIG. However, the discharge of the polymer during spinning was not stable, the spinnability was poor, yarn breakage occurred frequently during spinning, and the yarn could not be wound stably. Therefore, spinning was carried out at a spinning speed of 600 m / min, but yarn breakage occurred frequently. Using slightly obtained undrawn yarn, it was drawn and heat-treated in the same manner as in Reference Example 2. As a result, 77 dtex, 24 filament polymer alloy fiber was obtained. When the cross section of this was observed by TEM, the blend spots were large, coarse islands were scattered, and the area ratio of the islands having a diameter of 200 nm or more to the whole islands was 14%.

Reference Example 10
N6 was used alone and melt spinning was carried out in the same manner as in Reference Example 1 at a spinning speed of 3000 m / min. However, the yarn swelled 20 minutes after the start of winding, and the shape of the winding package collapsed, making winding impossible. It was.

Example 1
The polymer alloy fibers prepared in Reference Examples 2, 3, and 5 and normal N6 fibers (44 dtex, 12 filaments) were air entangled with an interlace nozzle at an entanglement pressure of 0.4 MPa (FIG. 14). At this time, the fibers were over-fed and supplied to the interlace nozzle, and entangled. There was no problem in processability, and there were no yarn breakage, fluff, etc. At this time, in the case where the polymer alloy fiber side is over-fed higher than the normal N6 fiber, the polymer alloy fiber is positioned relatively on the outer layer side of the mixed fiber, and the yarn length is longer than that of the normal N6 fiber. It was possible to form a scabbard (Table 2).

  Next, a plain weave is prepared using the mixed yarn as a warp and a weft, and an alkali treatment is performed with a 3% by weight, 95 ° C. sodium hydroxide aqueous solution containing 0.1% by weight of a quaternary ammonium salt as a hydrolysis accelerator. After 1 hour, 99% or more of the easily soluble polymer was removed to obtain a nanoporous fiber or a woven fabric in which the nanofiber was relatively exposed on the surface of the woven fabric. The weight loss rate of normal N6 fiber at this time was 1% or less. The density of this woven fabric is 120 warps / inch (2.54 cm) for the reference examples 2 and 3 and 90 wefts / inch (2.54 cm) for the weft, 100 warps for the reference example 5. The inch was 2.54 cm, and the number of wefts was 83 / inch (2.54 cm).

  As a result of sampling the nanoporous fiber or the part containing the nanofiber from the obtained woven fabric and analyzing the pore or single fiber diameter by TEM observation, all of the articles using the fibers of Reference Examples 2 and 3 are uniform nano. Nanoporous fibers having pores were obtained, and those using Reference Example 5 were nanofibers having a uniform single fiber diameter at the nano level (Table 2). In either case, the fibers were usually mixed with N6 fibers, so that there was no misalignment compared to the nanoporous fiber or the nanofiber alone (Comparative Example 1), and the fabric had good shape stability. Further, when the tear strength of the woven fabric was measured in accordance with D method of JIS L1096 (general woven fabric testing method), the products using Reference Examples 2 and 3 were 22N and 23N in the vertical direction, and Reference Example 5 was used. Among these, the mechanical properties were improved from 16N and 10N or less of nanoporous fiber or nanofiber alone (Comparative Example 1). Further, the moisture absorption rate (ΔMR) was 3.5%, 3.4%, and 3.0%, respectively, which were higher than those of the normal N6 fiber fabric (Comparative Example 2), and the comfort was improved. Furthermore, the color developability of the woven fabric containing nanoporous fibers using the fibers of Reference Examples 2 and 3 was good. In particular, the one using Reference Example 3 had a fine texture of softer than the one using Reference Example 2 because the single-fiber fineness of the nanoporous fiber was as thin as about 0.7 dtex.

Example 2
The polymer alloy fiber produced in Reference Example 6 and the high-shrinkage PET fiber (33 dtex, 6 filaments) having a heat shrinkage of 16% were air entangled in the same manner as in Example 1 using an interlace nozzle. There was no problem in processability, and there were no yarn breakage, fluff, etc. In the obtained blended yarn, the polymer alloy fiber was positioned on the relatively outer layer side of the blended yarn to form a sheath yarn, and the yarn length was longer than that of the high-shrinkage PET fiber (Table 1).

  Next, a circular knitting was produced using the mixed yarn, and first, hydrothermal treatment was performed at 130 ° C. for 40 minutes to sufficiently hydrolyze PLA. Thereafter, alkali treatment was performed for 30 minutes with a 3 wt% sodium hydroxide aqueous solution at 60 ° C. to remove PLA, which is a readily soluble polymer, to obtain a knitted fabric in which nanofibers appeared on the surface of the fabric relatively. At this time, the weight loss rate of the high shrinkage PET was 5% or less. The density of this knitted fabric was 48 pieces / inch (2.54 cm) for wealth and 50 pieces / inch (2.54 cm) for course.

  From the obtained knitted fabric, a portion containing nanofibers was sampled, and pore or single fiber diameter analysis was performed by TEM observation. As a result, nanofibers having a uniform single fiber diameter at the nano level were obtained (Table 3). . In addition, the knitted fabric made of N6 nanoporous fiber alone (Comparative Example 1) swells remarkably when it absorbs water, and the shape stability as a fabric is poor, but the knitted fabric made of the mixed yarn obtained in this example is supported by PET fiber. Therefore, even if the N6 nanofibers swell, the shape stability as a fabric was good. Further, when the burst strength of the circular knitting was measured according to JIS L1018 (Knit Fabric Testing Method), the mechanical properties were improved as compared with 900 kPa and 400 kPa of the knitted fabric (Comparative Example 1) made of N6 nanoporous fiber alone.

  Further, the high-shrinkage PET is greatly shrunk to form a core yarn, and the nanofibers are covered with the nanofibers so that the nanofibers are raised on the surface. For this reason, the wiping effect by the nanofiber can be fully utilized, and it is a suitable material as a wiping cloth or polishing cloth.

Example 3
Using the polymer alloy fiber produced in Reference Example 4 and the high-shrinkage PET fiber (33 dtex, 6 filaments) used in Example 2, air entanglement was performed in the same manner as in Example 2. There was no problem in processability, and there were no yarn breakage, fluff, etc.

  Next, a twisted yarn of 400 turns / m is applied to the blended yarn to be used for warp, and a normal PET fiber (78 detex, 24 filaments) is applied to a twist of 1500 turns / m to be used for weft to weave 2/1 twill. Then, scouring was performed at 90 ° C. for 30 minutes by a conventional method to remove 99% or more of the easily soluble polymer, and a woven fabric in which PET nanoporous fibers appeared relatively on the surface of the woven fabric was obtained.

  From the obtained woven fabric, a portion containing nanoporous fibers was sampled, and pore or single fiber diameter analysis was performed by TEM observation. As a result, nanoporous fibers having uniform nanopores were obtained (Table 3). Further, since it was mixed with PET fiber, it had good fabric shape stability and mechanical properties. Further, the color developability of the fabric was good.

Example 4
Using the polymer alloy fiber produced in Reference Example 7 and the high-shrinkage PET fiber used in Example 2, air entangled in the same manner as in Example 1 to obtain a mixed yarn (Table 1). There was no problem in processability, and there were no yarn breakage, fluff, etc.

  Next, a circular knitting was produced using the mixed yarn, and first, hydrothermal treatment was performed at 130 ° C. for 40 minutes to sufficiently hydrolyze PLA. Thereafter, alkali treatment was performed for 30 minutes with a 3 wt% sodium hydroxide aqueous solution at 60 ° C. to remove PLA, which is an easily soluble polymer, to obtain a knitted fabric in which nanofibers appeared relatively on the knitted surface. From the obtained knitted fabric, a portion containing nanofibers was sampled, and a single fiber diameter analysis was performed by TEM observation. As a result, it was found that the nanofiber aggregate had a uniform single fiber diameter (Table 3).

  This had good shape stability and mechanical properties of the fabric because it was mixed with PET fiber. Further, the high-shrinkage PET is greatly shrunk to form a core yarn, and the nanofibers are covered with the nanofibers so that the nanofibers are raised on the surface. For this reason, the wiping effect by the nanofiber can be fully utilized, and it is a suitable material as a wiping cloth or polishing cloth.

Comparative Example 1
Using two polymer alloy fibers prepared in Reference Examples 2 and 5, air entangled in the same manner as in Example 1. Using this, a plain weave was produced in the same manner as in Example 1, and 99% or more of the easily soluble polymer was removed to obtain a nanoporous fiber or a woven fabric composed only of nanofibers (Table 3). However, these were poor in morphological stability of the fabric and not only easily shifted, but also had low tear strength and burst strength.

Comparative Example 2
The fibers obtained in Reference Examples 8 and 9 and normal N6 fibers (78 dtex, 34 filaments) were entangled with normal N6 fibers in the same manner as in Example 1 (Table 2). Using these, a plain weave was produced in the same manner as in Example 1. Thereafter, alkali treatment was performed in the same manner as in Example 1 to obtain a woven fabric in which porous fibers were relatively exposed on the surface of the woven fabric. However, the fibers using the fibers of Reference Examples 8 and 9 had many coarse pores, so that the amount of scattered light was so white that they were whitish and poor in color developability (Table 3). Further, the moisture absorption rate (ΔMR) of the fabric was as low as 2.4%, 2.3%, and 2.0%, respectively, which was in the category of conventional N6 fiber fabrics.

Example 5
The fiber produced in Reference Example 4 is pre-twisted using a heater temperature of 180 ° C. and a rotor as a spinner pin, and air entangled using the high-shrinkage PET fiber used in Example 2 of 33 dtex and 12 filaments and an interlace nozzle. The mixed fiber was obtained (FIG. 15). At this time, the rotation speed of the spinner pin was 1700 turns / m, the overfeed rate to the interlace nozzle was 13% for the polymer alloy fiber, 4% for the high shrinkage PET fiber, the entanglement pressure was 0.3 MPa, and the processing speed was 130 m / min. It was. There was no problem in workability, and there were no yarn breakage, untwisting, fluff, etc.

  In the obtained mixed fiber, the polymer alloy fiber formed a sheath yarn, and the yarn length difference from the high-shrinkage PET fiber as the core yarn was 8%.

  Furthermore, a 400-turn / m twisted yarn was applied to the blended yarn for use as a warp, and a normal PET fiber (78 detex, 36 filaments) was applied with a 1500-turn / m twisted yarn for use as a weft. .

  Then, scouring was performed at 90 ° C. for 30 minutes by a conventional method, and 99% or more of the easily soluble polymer was removed to obtain a woven fabric in which PET nanoporous fibers appeared relatively on the surface of the woven fabric.

  As a result of sampling the portion containing the nanoporous fiber from the obtained woven fabric and conducting pore analysis by TEM observation, the average pore diameter is 30 nm, the area ratio of pores is 50 nm or more and 0.1% or less, and uniform. It became a nanoporous fiber having a nanopore. The yarn length difference between the PET nanoporous fiber and the high shrinkage PET fiber was 20%. Further, since it was mixed with PET fiber, it had good fabric shape stability and mechanical properties. Moreover, the color development property of the woven fabric was good, and it was a satin woven fabric suitable for women's outer garments having beautiful luster and color tone.

Example 6
The fiber prepared in Reference Example 5 was mixed at the heater temperature of 150 ° C., and the mixed fiber was mixed as in Example 5 as the normal N6 fiber used in Example 1. There was no problem in workability, and there were no yarn breakage, untwisting, fluff, etc.

  Five back satins were woven using the mixed yarn as the weft and the normal PET fiber (33 dtex, 12 filaments) as the warp.

  And PLA was removed like Example 4, and the textile fabric from which the PTT nanofiber rose on the fabric surface was obtained.

  As a result of sampling the part containing nanofibers from the resulting woven fabric and analyzing the single fiber diameter by TEM observation, the number average single fiber diameter is 60 nm, and the weight ratio of single fibers larger than 100 nm is 1%. It was a nanofiber with a uniform diameter. Moreover, although it was difficult to separate PET nanofibers and high-shrinkage PET fibers, the difference in yarn length between these was 15% or more. Further, since it was mixed with PET fiber, it had good fabric shape stability and mechanical properties. This was suitable for wiping cloths and polishing cloths.

Example 7
The fibers obtained in Reference Example 1 and normal N6 fibers (55 dtex, 12 filaments) are entangled with air through an interlace nozzle and combined to form a drawing ratio of 1.15 times, a heater temperature of 165 ° C., and a friction disk as a rotor. Composite false twisting was performed at a speed of 400 m / min (FIG. 16). At this time, the fiber overfeed rate during air entanglement before false twisting was 5%, the entanglement pressure was 0.5 MPa, the twisting stress was 0.29 cN / dtex, and the untwisting stress was 0.19 cN / dtex. There was no problem in workability, and there were no yarn breakage, untwisting, fluff, etc. The blended yarn obtained here was a blended yarn having a so-called core-sheath structure in which polymer alloy fibers are usually entangled with N6 fibers. The yarn length difference at this time was 18%.

  A 400 T / m twisted yarn was applied to the blended yarn, and 2/1 twill was woven using normal N6 fibers (78 dtex, 34 filaments) as a weft to obtain a living machine. In accordance with a conventional method, scouring and intermediate setting were performed, followed by dyeing. Furthermore, a finishing set was applied. The mixed yarn was extracted from the woven fabric obtained here and the difference in yarn length was measured to be 22%. This woven fabric has a rich swell and tension that is not found in conventional nylon fabrics, and exhibits an excellent texture that is different from conventional nylon fabrics.

  Further, the raw machine was subjected to an alkali treatment in the same manner as in Example 1 to remove 99% or more of the easily soluble polymer to obtain a woven fabric containing nanoporous fibers. As a result of sampling the portion containing the nanoporous fiber from the obtained woven fabric and conducting pore analysis by TEM observation, the number average pore diameter is 30 nm, and the area ratio of pores having a diameter of 50 nm or more is 0.1% or less. It was a nanoporous fiber having uniform nanopores. Further, since the fibers were usually mixed with N6 fibers, there was no misalignment as compared with the nanoporous fibers alone (Comparative Example 1), and the fabric had good shape stability. Furthermore, when this was dye | stained, the favorable color development was shown.

Comparative Example 4
Instead of the fiber obtained in Reference Example 1, normal N6 fiber used in the mixed fiber of Example 7 was used, and composite false twisting was performed in the same manner as in Example 7 to obtain a mixed fiber. The yarn length difference was 1%. Using this, 2/1 twill was woven in the same manner as in Example 5, and further finished to a finishing set. However, the texture of the obtained fabric was in the category of conventional nylon fabric and was inferior to that of Example 5.

Comparative Example 5
Composite false twisting was performed in the same manner as in Example 7 using the fiber obtained in Reference Example 8. However, since the fiber of Reference Example 8 had a coarse island, the yarn did not run stably on the friction disk, and Variations in twisting / untwisting tension increased. For this reason, thread breakage frequently occurred and the processing stability was poor. Also, the obtained mixed yarn has many defects such as fuzz and untwisting.

Example 8
Using the polymer alloy pellets used in Reference Example 7 and a low melting point PET having a melting point of 225 ° C. (copolymerization of 7 mol% isophthalic acid and 3 mol% bisphenol A), mixed fiber spinning from the same die was performed in the same manner as in Reference Example 7 (FIG. 17). And the drawing heat treatment was performed in the same manner as in Reference Example 7 to obtain a mixed yarn of 120 dtex and 36 filaments on the polymer alloy fiber side and 30 dtex and 12 filaments on the low melting point PET side.

  And when the island diameter analysis of the obtained mixed fiber yarn was performed, the number average diameter of the island was 72 nm, the area ratio of the coarser island having a diameter of 200 nm or more was 0.1% or less, and the area ratio of the island having a diameter of 100 nm or more was It was 0.8%.

4 is a TEM photograph showing a fiber cross section of a polymer alloy fiber of Reference Example 1. 4 is a TEM photograph showing a fiber cross section of a polymer alloy fiber of Reference Example 2. 4 is a TEM photograph showing a fiber cross section of a polymer alloy fiber of Reference Example 2. 4 is a TEM photograph showing a fiber cross section of a polymer alloy fiber of Reference Example 4. 6 is a TEM photograph showing a fiber cross section of a polymer alloy fiber of Reference Example 5. It is a TEM photograph which shows the fiber cross section of a nanoporous fiber. It is a TEM photograph which shows the fiber cross section of a nanofiber. 10 is a TEM photograph showing a fiber cross section of a polymer alloy fiber of Reference Example 8. It is a figure which shows a spinning apparatus. It is a figure which shows a spinning apparatus. It is a figure which shows an extending | stretching apparatus. It is a figure which shows a spinning apparatus. It is a figure which shows a nozzle | cap | die. It is a figure which shows a fiber mixing apparatus. It is a figure which shows a fiber mixing apparatus. It is a figure which shows a fiber mixing apparatus. It is a figure which shows a spinning apparatus.

Explanation of symbols

1: Hopper 2: Melting part 3: Spinning pack 4: Base 5: Monomer suction device 6: Chimney 7: Yarn 8: Converging oiling guide 9: First take-up roller 10: Second take-up roller 11: Winding yarn 12: Static kneader 13: Undrawn yarn 14: Feed roller 15: First hot roller 16: Second hot roller 17: Delivery roller (room temperature)
18: drawn yarn 19: first hot roller 20: second hot roller 21: take-up yarn 22: measuring section 23: discharge hole length 24: discharge hole diameter 25: supply yarn 26: supply yarn 27: feed roller 28: interlace nozzle 29: Delivery roller 30: Mixed yarn 31: Heater 32: Cooling plate 33: Rotor

Claims (11)

A mixed yarn comprising the following fiber A or fiber B and a fiber C different from these fibers:
Fiber A:
It shows a sea-island structure composed of a hardly soluble polymer and a readily soluble polymer, the blend ratio of the easily soluble polymer is 10 to 90% by weight, and the area ratio of the coarse island with a diameter of 200 nm or more is 3% or less. A polymer alloy fiber.
Fiber B:
A polymer alloy fiber comprising a hardly soluble polymer and an easily soluble polymer, the blend ratio of the easily soluble polymer is 10 to 90% by weight, and the portion where these layers show a layered structure has 50% or more per fiber cross-sectional area.
Fiber C:
A fiber made of a polymer that is less soluble than a readily soluble polymer.   The mixed yarn according to claim 1, wherein the number average diameter of the islands of the fiber A is 1 to 100 nm or the layer thickness of the easily soluble polymer layer of the fiber B is 1 to 100 nm.   The mixed yarn according to claim 1 or 2, wherein the island in the fiber A is an easily soluble polymer.   The mixed yarn according to claim 1 or 2, wherein the island in the fiber A is a hardly soluble polymer.   The mixed yarn according to any one of claims 1 to 4, wherein the yarn length difference between the fiber A or the fiber B and the fiber C is 1 to 40%.   The mixed yarn according to any one of claims 1 to 5, wherein the fiber A or the fiber B has a longer yarn length than the fiber C.   A textile product having at least a part of the mixed yarn according to any one of claims 1 to 6.   The manufacturing method of the blended yarn which obtains the blended yarn of any one of Claims 1-6 by back blending.   The manufacturing method of the blended yarn which obtains the blended yarn of any one of Claims 1-6 by spinning blending. A fiber product having at least a part of a mixed yarn comprising the following fiber D.
Fiber D:
A nanoporous fiber having pores having a diameter of 100 nm or less, wherein the area ratio of coarse pores having a diameter of 200 nm or more occupying the entire cross section of the fiber is 1.5% or less. A fiber product having at least a part of a mixed yarn composed of the following fiber E and a different fiber F.
Fiber E:
A nanofiber assembly comprising a thermoplastic polymer having a number average single fiber diameter of 1 to 150 nm, a weight ratio of coarse single fibers having a single fiber diameter exceeding 150 nm, and 30% or less.
Fiber F:
A fiber having a single fiber fineness of 0.1 dtex or more.

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