JP4238929B2 - Polymer alloy fiber, method for producing the same, and fiber product using the same - Google Patents

Description

The present invention relates to a polymer alloy fiber suitable as a precursor of a nanofiber having a small single yarn fineness variation.

  Polycondensation polymers such as polyesters typified by polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) and polyamides typified by nylon 6 (N6) and nylon 66 (N66) have moderate mechanical properties and heat resistance. Conventionally, it has been suitably used for fibers for clothing and industrial materials. On the other hand, addition polymerization polymers represented by polyethylene (PE) and polypropylene (PP) have suitable mechanical properties, chemical resistance, and lightness, and thus have been suitably used mainly for fibers for industrial materials.

  In particular, polyester fibers and polyamide fibers have been used for apparel applications. In addition to polymer modification, studies have been actively made on improving the performance of the fibers by using the cross-sectional shape of the fibers and ultrafine yarn. One such study was the creation of ultra-fine polyester yarn using sea-island composite spinning, which resulted in a large new product called suede-like artificial leather. Moreover, this super extra fine thread is applied to general clothing, and it has also been developed to clothing having an excellent peach touch texture that cannot be obtained with ordinary fibers. Furthermore, it is being developed not only for clothing but also for daily and industrial materials such as wiping cloth, and ultrafine fibers have established a firm position in the world of synthetic fibers today. Particularly recently, as described in JP-A-2001-1252 and JP-A-2002-224945, surface polishing cloths for hard disks of computers, JP-A-2002-102332, and JP-A-2002-172163 As described, the application has been extended to medical materials such as cell adsorbents.

  For this reason, in order to obtain a higher level of artificial leather and high-quality clothing, thinner fibers have been desired. In order to support the growth of the IT industry, the increase in hard disk capacity is being promoted. To this end, it is essential to increase the recording density of the hard disk. It is necessary to further smooth the hard disk surface (the target is an average surface roughness of 0.5 nm or less). For this reason, there has been a demand for nanofibers in which the fibers used in the polishing cloth for polishing the hard disk surface are further refined.

However, the current sea-island composite spinning technology has a limit of 0.04 dtex (corresponding to a diameter of 2 μm) as the single yarn fineness, and is not at a level that can sufficiently meet the needs for nanofibers. Moreover, although the method of obtaining a super extra fine thread with a polymer blend fiber is described in Unexamined-Japanese-Patent No. 3-113082 and Unexamined-Japanese-Patent No. 6-272114, even if the single yarn fineness obtained here is the finest, it is 0.001 dtex. (Corresponding to a diameter of 0.4 μm), it was not a level that could sufficiently meet the needs for nanofibers. In addition, the single yarn fineness of the ultrafine yarn obtained here is determined by the dispersion state of the island polymer in the polymer blend fiber, but the island polymer is not sufficiently dispersed in the polymer blend system used in the publication. For this reason, the obtained ultra extra fine yarn has a large single yarn fineness variation. In addition, there is a method (Patent Document 1) for obtaining ultrafine yarn from a polymer blend fiber using a static kneader. However, in the publication example 2, the theoretical single yarn fineness calculated from the number of divisions of the static kneader is 1 × ¹⁰ -4 dtex but would have (diameter 100nm or so) and nanofibers obtained, when actually measuring the fineness of the ultrafine fibers obtained therefrom ^{1 × 10 -4 dtex~1 × 10 -2} dtex ( diameter 1μm It is described that nanofibers having a single yarn 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. Thus, the single yarn fineness variation of the ultrafine yarn obtained by these prior arts was large. For this reason, the performance of the product is determined by a group of thick single yarns, and not only the merit of ultra-fine yarn is not fully exhibited, but also there is a problem in quality stability and the like. Furthermore, when used in the surface polishing cloth for hard disks described above, due to the large variation in fineness, the abrasive grains cannot be uniformly supported on the polishing cloth, resulting in a decrease in the smoothness of the hard disk surface. There was also a problem to do.

  By the way, recently, as a method of obtaining a carbon nanotube (CNT) precursor by a polymer blend method, a core-shell fine particle having a polymer (phenol resin, etc.) that is carbonized by firing as a shell and a matrix polymer disappearing by thermal decomposition is dry-blended. A polymer alloy in which a finely dispersed structure obtained by dry blending is made into a yarn shape while being preserved by melting and extruding it at extremely low speed, and a polymer that can be carbonized by bundling and extruding again is finely dispersed in a matrix polymer. A method for producing a fibrous material is being developed (Patent Document 2). However, since the operation of baking is essential in the combination of the polymers described in the publication, only CNTs can be obtained, and it has been impossible to obtain nanofibers made of so-called organic polymers. In addition, the core-shell particles, which is the point of the method, are prepared by spraying the core polymer with the spray-dry method on the core particles. However, since the core particles with originally varying diameters are used, the variation of the particle diameter further increases. As a result, the resulting CNT diameter variation was very large (some thin but some thick). Further, although not described in detail in the publication, when a normal melt spinning used industrially in polyester, polyamide, polyolefin, etc. is applied to the method, a part where the molten polymer flow such as a filtration part is disturbed. As a result, the core-shell particles are fused together, and as a result, only a polymer having a large dispersion size that can be carbonized can be obtained. For this reason, it is necessary to devise methods that do not disturb the dispersion state obtained by dry blending as much as possible, but if this is achieved with the current spinning technology, it is usually employed industrially in polyester, polyamide, polyolefin, etc. Melt spinning is impossible, and instead a method called so-called “candle spinning”, in which the polymer is extruded directly from the barrel at a very low speed, must be used. However, in this spinning method, the spinning speed is extremely low, and the discharge amount per unit time depends on the pressure applied to the extrusion piston, so not only the discharge amount is unstable but also cooling spots are likely to occur. As a result, there is a problem in that the thick spots in the longitudinal direction of the polymer alloy filaments obtained become excessive. Thereby, the diameter variation of the obtained CNT was further expanded.

  On the other hand, a suspension of polymethyl methacrylate (PMMA) / polyacrylonitrile (PAN) core-shell particles (diameter of about 200 to 600 μm) and PMMA particle suspension prepared by two-stage soap-free polymerization to make the size of the core-shell particles as uniform as possible. There is also an example using a polymer blend obtained by lyophilization after mixing with a liquid (Non-patent Document 1). However, even in this case, it is impossible to obtain a polymer alloy fiber that is uniform in the longitudinal direction of the yarn due to the above-mentioned problems in melt spinning. Furthermore, since there is almost no difference in solubility between PMMA and PAN, the operation of firing is essential, and it has been impossible to obtain nanofibers made of so-called organic polymers. In addition, since soap-free polymerization is limited to radical polymerization, it cannot be applied to polycondensation polymers such as polyester and nylon.

As described above, there is no restriction on the shape of the fiber / fiber product and the polymer, and there is a demand for nanofibers with small variations in single yarn fineness that can be widely applied and developed, but the solubility as a precursor is different. An ultrafine dispersion polymer alloy fiber made of a polymer was not obtained.
USP 4,686,074 (19th column) JP 2002-173308 A (pages 1 to 6) Functional materials, vol. 21, no. 11, 41-46 (2001).

  The present invention is a polymer in which polymers having different solubilities are ultra-dispersed, suitable as a precursor for obtaining nanofibers having a small variation in single yarn fineness that can be widely applied and deployed without restrictions on the shape of fibers and fiber products and polymers. An alloy fiber is provided.

The above purpose is
(1)
A sea-island-structured fiber consisting only of a polymer alloy, wherein the sea-component easily soluble polymer is polyethylene terephthalate and the island-soluble polymer is polyphenylene sulfide, and the number average diameter of the island domains is 1-150 nm. A polymer alloy fiber in which 60% or more of the area ratio of the island domain is in the range of 1 to 150 nm in diameter and the Wooster spot is 15% or less.
Island domain area ratio: The area of the island domain is S _i, and the total area is the total area (S ₁ + S ₂ +... S _n ).
And In addition, the frequency (number) of domains having the same area S is counted, and the product of the area and the frequency is calculated.
The area ratio of the island domain is divided by the total area.
(2)
A sea-island structure fiber consisting only of a polymer alloy blended with at least two organic polymers having different solubilities, wherein the island component is a hardly soluble polymer and the sea component is a readily soluble polymer having a melt viscosity of 100 Pa · s or less. A polymer alloy fiber in which the number average diameter of the island domains is 1 to 150 nm, 60% or more of the area ratio of the island domains is in the range of 1 to 150 nm in diameter, and Wooster spots are 15% or less.
Area of the island domains ratio: the area of the island domains as _{S i,} to the total sum and the total area _{(S 1 + S 2 + ...} S n). Further, the frequency (number) of domains having the same area S is counted, and the product of the area and frequency divided by the total area is defined as the area ratio of the island domain.
(3)
3. The polymer alloy fiber according to claim 2, wherein the sea component easily soluble polymer is polystyrene copolymerized with 2-ethylhexyl acrylate or methyl methacrylate, and the island component hardly soluble polymer is polyester.
(4)
3. The polymer alloy fiber according to claim 2, wherein the easily soluble polymer of the sea component is polylactic acid, and the hardly soluble polymer of the island component is polyamide.
(5)
A sea-island polymer alloy fiber consisting only of a polymer alloy, wherein the sea-soluble polymer is polyethylene terephthalate copolymerized with isophthalic acid and bisphenol A, and the island-soluble polymer is polyamide. The melting point of copolymer polyethylene terephthalate as a component is -20 to + 20 ° C. of the melting point of polyamide as an island component, the number average diameter of island domains is 1 to 150 nm, and the area ratio of island domains is 60% or more. A polymer alloy fiber having a Wooster plaque of 15% or less in a range of 1 to 150 nm.
Area of the island domains ratio: the area of the island domains as _{S i,} to the total sum and the total area _{(S 1 + S 2 + ...} S n). Further, the frequency (number) of domains having the same area S is counted, and the product of the area and frequency divided by the total area is defined as the area ratio of the island domain.
(6)
The method for producing a polymer alloy fiber according to claim 1, wherein polyethylene terephthalate and polyphenylene sulfide are melted separately, blended in a stationary kneader having a million or more divisions provided in a spinning pack, and then melt-spun.
(7)
The polymer alloy fiber according to claim 5, wherein polyethylene terephthalate copolymerized with isophthalic acid and bisphenol A and polyamide are melted separately, blended in a stationary kneader of 1 million divisions or more provided in a spinning pack, and then melt-spun. Manufacturing method.
(8)
A hot kneading polymer based on polyalkylene glycol as the sea component and a polymer selected from polyester, polyamide, polypropylene, and polycarbonate as the island component are melted separately, and a stationary kneader with more than 1 million divisions in the spinning pack. A polymer alloy in which the number average diameter of the island domains is 1 to 150 nm, the area ratio of the island domains is in the range of 1 to 150 nm in diameter, and the Worcester plaque is 15% or less. The manufacturing method of the polymer alloy fiber which consists only of.
Area of the island domains ratio: the area of the island domains as _{S i,} to the total sum and the total area _{(S 1 + S 2 + ...} S n). Further, the frequency (number) of domains having the same area S is counted, and the product of the area and frequency divided by the total area is defined as the area ratio of the island domain.
(9)
The method for producing a polymer alloy fiber according to claim 3 or 4, wherein a sea-island structure is formed by blending an easily soluble polymer having a melt viscosity of 100 Pa · s or less as a sea component and melt spinning.
(10)
8. The polymer alloy according to claim 7, wherein the two kinds of polymers are kneaded with a biaxial kneader and then melt-spun, and the shear stress between the spinneret hole wall and the polymer alloy is 0.01 to 0.2 MPa · s. A method for producing fibers.
(11)
Two types of polymers are melted separately, kneaded in a static kneader of 1 million divisions or more provided in a spinning pack, and then melt-spun, the shear stress between the spinneret hole wall and the polymer alloy is set to 0.01. The manufacturing method of the polymer alloy fiber of Claim 7 which is set to -0.2MPa * s.
(12)
A hot water-soluble polymer based on polyalkylene glycol as a sea component and polyester as an island component are melted separately, kneaded in a static kneader with a million or more divisions in a spinning pack, and then melt-spun, The number average diameter of the island domains is 1 to 150 nm, with the shear stress between the pore wall and the polymer alloy being 0.01 to 0.2 MPa · s, and 60% or more of the area ratio of the island domains is 1 to 150 nm. The manufacturing method of the polymer alloy fiber which consists only of a polymer alloy which has the Wooster spot which is in the range of 15% or less.
Area of the island domains ratio: the area of the island domains as _{S i,} to the total sum and the total area _{(S 1 + S 2 + ...} S n). Further, the frequency (number) of domains having the same area S is counted, and the product of the area and frequency divided by the total area is defined as the area ratio of the island domain.
(13)
A fiber product having at least a part of the polymer alloy fiber according to any one of claims 1 to 5 or the polymer alloy fiber obtained by the production method according to claims 6 to 12.
(14)
The textile product according to claim 13, wherein the textile product is a woven or knitted fabric or a nonwoven fabric.
(15)
Elution of a sea polymer from the polymer alloy fiber according to any one of claims 1 to 5, the polymer alloy fiber obtained by the production method according to claims 6 to 12, or the fiber product according to claim 13 or 14. The manufacturing method of the textiles containing the nanofiber whose number average diameter is 1-150 nm.
Is achieved.

  With the nanofiber aggregate having a small variation in single yarn fineness according to the present invention, it is possible to obtain a fabric with a texture and a high performance polishing fabric that have never been seen before.

The organic polymer in the present invention means polyesters, polyamides, thermoplastic polymers typified by polyolefins, thermosetting polymers such as phenolic resins, and biopolymers such as DNA. From the viewpoint of sex. Among them, many polycondensation polymers represented by polyester and polyamide are more preferable because they have a high melting point. The organic polymer may contain additives such as particles, a flame retardant, and an antistatic agent. In the present invention, other components may be copolymerized as long as the properties of the polymer are not impaired. In this invention, it is possible to form a sea-island structure fiber composed only of a polymer alloy in which two organic polymers having different solubility are blended. Although important here, solubility means the difference in solubility in a certain solvent, and the solvent means an alkali solution, an acidic solution, an organic solvent, and further a supercritical fluid. . In addition, sea-island structure fibers consisting only of a polymer alloy means that a single fiber consists of only a single polymer alloy, and a core-sheath type, split type, side-by-side type, etc., consisting of the polymer alloy and another polymer. Fiber is not included.

  In the present invention, in order to easily remove the sea polymer with a solvent, it is important that the sea polymer is a readily soluble polymer and the island polymer is a hardly soluble polymer. In addition, if an easily soluble polymer that is easily soluble in an alkaline aqueous solution is selected, explosion-proof equipment is unnecessary for the dissolving equipment, which is preferable in terms of cost and versatility. Examples of the alkali-soluble polymer include polyester and polycarbonate, and copolymerized PET is particularly preferable. Furthermore, when a hot water soluble polymer is selected as the easily soluble polymer, the load of waste liquid treatment is reduced, which is more preferable. Examples of the hot water-soluble polymer include water-soluble polyamide, polyalkylene glycol, polyvinyl alcohol and derivatives thereof, and 5-sodium sulfoisophthalic acid high-copolymerized polyester. Preferred is a polymer with improved properties and PET copolymerized with 10 mol% or more of 5-sodium sulfoisophthalic acid.

Further, considering the yarn processability, knitting, and higher-order processability after the polymer alloy fiber, the melting point of the sea polymer is preferably 165 ° C. or higher. Note that having a melting point as amorphous polymer is not observed, the glass transition temperature (T _g), it is preferable Vicat softening temperature, heat distortion temperature of 165 ° C. or higher.

Further, the melting point of the island polymer is preferably 165 ° C. or more, since the heat resistance when nanofibers are obtained is favorable. Note that having a melting point as amorphous polymer is not observed, the glass transition temperature (T _g), it is preferable Vicat softening temperature, heat distortion temperature of 165 ° C. or higher.
As a specific composition of polymer alloy fibers based on the above, it is important to use the following combinations.
(1) Sea component is polyethylene terephthalate and island component is polyphenylene sulfide
(2) The sea component is a readily soluble polymer having a melt viscosity of 100 Pa · s or less, and the island component is a hardly soluble polymer.
(3) The sea component is polyethylene terephthalate copolymerized with isophthalic acid and bisphenol A, and the poorly soluble polymer of the island component is polyamide.
(4) Hot water soluble polymer based on polyalkylene glycol as sea component, and polymer selected from polyester, polyamide, polypropylene and polycarbonate as island component

  In the present invention, in order to obtain nanofibers with small single yarn fineness variation, the number average diameter and variation of island domains in the polymer alloy fiber are important. This is done by observing the cross section of the polymer alloy fiber with a transmission electron microscope (TEM) and measuring 300 or more island domain diameters randomly sampled within the same cross section. , By measuring a total of 1500 or more island domain diameters. And it is preferable to perform the measurement at positions separated from each other by 10 m or more in the longitudinal direction of the yarn.

  Here, the number average diameter is obtained as follows. That is, a simple average value of the measured island domain diameters is obtained. It is important that the number average diameter of the island domains is 1-150 nm. This is as thin as 1/100 to 1/1000 in diameter compared to the island domain by the conventional sea-island composite spinning, and it is far more than conventional cloths for clothing having a completely different texture from conventional ultra-fine yarns. A polishing cloth that can improve the smoothness of the hard disk can be obtained. The number average diameter of the island domains is preferably 1 to 100 nm, more preferably 20 to 80 nm.

Moreover, the diameter variation of an island domain is evaluated as follows. That is, the area of the island domain is S _i , and the sum is the total area (S ₁ + S ₂ +... + S _n ). Further, the frequency (number) of the same area S is counted, and the product of the area and frequency divided by the total area is defined as the area ratio of the island domain. For example, when the number of island domains having a diameter of 60 nm is 350 and the total area is 3.64 × 10 ⁶ nm ² , the area ratio is (3.14 × 30 nm × 30 nm × 350) / (3.64 × 10 ⁶ nm ² ) × 100% = 27.2%. This corresponds to the volume fraction of the island domains of each size with respect to the entire island component in the polymer alloy fiber, and when the island domain component having a large size is a nanofiber, the contribution to the entire properties is large. It is important that 60% or more of the area ratio of the island domains in the polymer alloy fiber of the present invention is in the range of 1 to 150 nm in diameter. This means that when a nanofiber is formed, most of the single yarn can be made into an unprecedented thin nanofiber having a diameter of 150 nm or less. Thereby, the function of the nanofiber can be fully exhibited, the product quality stability can also be improved, and further, when used in the above-mentioned surface polishing cloth for hard disk, since the fineness variation is small, Even nanofibers can uniformly support abrasive grains, and as a result, the smoothness of the hard disk surface can be dramatically improved. Preferably, 60% or more of the area ratio is in the range of 1 to 100 nm in diameter. The area ratio in the range of 1 to 100 nm in diameter is preferably 75% or more, more preferably 90%, still more preferably 95% or more, and most preferably 98% or more.

  Moreover, it is preferable that the part with a high area ratio of an island domain concentrates on the component with a smaller diameter of an island domain, and 60% or more of an area ratio is the range of 1-80 nm in diameter. More preferably, 70% or more of the area ratio is in the range of 1 to 80 nm in diameter.

  Another indicator of island domain diameter variation is the area ratio of island domains where the difference in island domain diameter is 30 nm. This is the half-value width of the frequency distribution, or the concentration of variation near the center diameter. This parameter corresponds to the degree, and the higher the area ratio, the smaller the variation. In the present invention, it is preferable that the area ratio of the island domains having a diameter difference of 30 nm is 60% or more. More preferably, it is 70% or more, More preferably, it is 75% or more.

As mentioned above, the size of island domains in the polymer alloy fiber cross section and its variation are important. From the viewpoint of the stability of the quality of the fiber product after nanofiber formation, It is preferable that the spots are also small. In particular, when nanofibers are used for the polishing cloth, it greatly affects the size and number of scratches (scratches on the surface of the object to be polished). For this reason, it is important that the Worcester plaque of the polymer alloy fiber of the present invention is 15% or less, preferably 5% or less, more preferably 3% or less.

  The polymer alloy fiber of the present invention preferably has a strength of 1 cN / dtex or more and an elongation of 25% or more because there are few troubles such as generation of fuzz and yarn breakage in processes such as twisting and weaving. The strength is more preferably 2.5 cN / dtex or more, and further preferably 3 cN / dtex or more. Moreover, it is preferable that the boiling water shrinkage is 25% or less because the dimensional change of the fabric during the elution treatment of the sea polymer is small. The boiling water shrinkage is more preferably 15% or less.

  The polymer alloy fiber of the present invention can be bulked up by crimping. In the case of false twisted yarn, it is preferable that the Crimp Rigidity value (CR value), which is an index of crimpability, is 20% or more. In addition, the number of crimps, which is an index of crimping, is preferably 5 pieces / 25 mm or more for mechanical crimped yarns, air jet processed yarns, and the like. In general, the CR value can be adjusted according to false twisting conditions such as a crimping method, a crimping device, a twister rotation speed, and a heater temperature. A CR value of 20% or more can be achieved by setting the heater temperature to (polymer melting point−70) ° C. or more. In order to further improve the CR value, it is effective to increase the heater temperature.

  In addition, the number of crimps of 5/25 mm or more for mechanical crimped yarns, air jet processed yarns, etc. can be achieved by appropriately changing the conditions such as selection of the crimp imparting device and feed rate.

  The CR value is measured as follows.

  The false twisted yarn is scraped off, treated in boiling water for 15 minutes in a substantially load-free state, and air-dried for 24 hours. A load equivalent to 0.088 cN / dtex (0.1 gf / d) was applied to this sample and immersed in water, and the skein length L0 ″ after 2 minutes was measured. Next, a load equivalent to 0.088 cN / dtex in water The skein length L1 ″ after 2 minutes is measured by exchanging with a fine load equivalent to 0.0018 cN / dtex (2 mgf / d). Then, the CR value is calculated by the following formula.

CR (%) = [(L0 ″ −L1 ″) / L0 ″] × 100 (%)
The number of crimps is measured as follows.

  A fiber sample of 50 mm is sampled, the number of crimped crests is counted, the number of crests per 25 mm is obtained, and the value obtained by multiplying the value by 1/2 is defined as the number of crimps.

  The polymer alloy fiber of the present invention is useful not only as a nanofiber precursor but also as a polymer alloy fiber because polymers having different properties are uniformly dispersed in a nano size. For example, when nylon and polyester are uniformly dispersed in PLA in a nano size, it is possible to improve the heat resistance defect that is a defect of PLA. In addition, when polyester is uniformly dispersed in nylon at a nano size, it is possible to improve poor dimensional stability upon water absorption, which is a drawback of nylon. Further, when nylon or polyester is uniformly dispersed in polystyrene (hereinafter abbreviated as PS) in a nano size, brittleness, which is a defect of PS, can be improved. When nylon or polyester is uniformly dispersed in PP in a nano size, the dyeability, which is a drawback of PP, can be improved.

  The polymer alloy fiber of the present invention can be mixed with other fibers, and can be blended, blended, blended, knitted, woven, laminated, bonded, and the like. Thereby, the form stability as a fiber structure when it is made into nanofibers can be remarkably improved.

  The polymer alloy fiber of the present invention and the fiber product having at least a part thereof and the functionally processed product thereof include yarn, cotton, package, woven fabric, knitted fabric, felt, non-woven fabric, thermoformed body, artificial leather, etc. Can be an intermediate product. In addition, when a large number of nanofibers are arranged on the surface of the fiber structure and a large number of ordinary fibers are arranged inside to improve the shape stability, composite false twisting or air mixing is performed, and the polymer alloy of the present invention is used. When the fibers are arranged as sheath yarns on the outside of the processed yarn, or when weaving and knitting with other yarns, it is preferable to use a fabric form with back and front such as satin, twill, smooth or cardboard knit. In the case of felt or non-woven fabric, it is preferably laminated or bonded to another substrate.

  Furthermore, as polymer alloy fibers or nanofibers, clothing (shirts, blousons, pants, coats, etc.), clothing materials, interior products (curtains, carpets, mats, wallpaper, furniture, etc.), vehicle interior products (mats, car seats) , Ceiling materials, etc.), household materials (wiping cloths, cosmetics, health products, toys, etc.), environmental and industrial materials (building materials, abrasive cloth, filters, toxic substance removal products, etc.) and IT parts (Sensor parts, battery parts, robot parts, etc.) and medical applications (blood filters, extracorporeal circulation columns, scaffolds, wound dressing, artificial blood vessels, drug sustained release bodies, etc.) it can.

  Although the manufacturing method of the polymer alloy fiber of this invention is not specifically limited, For example, the following methods are employable.

  That is, a polymer alloy melt obtained by alloying polymers having different solubility in two or more kinds of solvents is formed, and after spinning, it is solidified by cooling and fiberized. Then, stretching and heat treatment are performed as necessary to obtain polymer alloy fibers. Since the dispersion state of the island domains directly affects the nanofiber diameter, it is very important to knead the polymer to be alloyed. In the present invention, it is preferable to perform high kneading with an extrusion kneader or a stationary kneader. It should be noted that simple chip blending (JP-A-6-272114, etc.) is insufficient for kneading, so that 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 an extrusion kneader, it is preferable to use a biaxial 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. In addition, 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 of the polymer and gelation of the polyamide component, etc. are suppressed. be able to. 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, as a vent type, the decomposition gas during kneading is sucked or the water content in the polymer is reduced to suppress polymer hydrolysis, and the amount of amine end groups in polyamide and carboxylic acid end groups in polyester is also suppressed. Can do.

Further, the b ^* value, which is an index for coloring the polymer alloy pellets, is preferably 10 or less, so that the color tone when fiberized can be adjusted, which is preferable. The hot water-soluble polymer suitable as an easily soluble component generally has poor heat resistance and is likely to be colored due to its molecular structure, but it is possible to suppress coloring by an operation for shortening the residence time as described above. is there.

  Further, in order to finely disperse the island polymer with a size of several tens of nm, a combination of polymers is also important.

In order to make the island domain (cross section of the nanofiber) close to a circle, the island polymer and the sea polymer are preferably incompatible. 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.

In addition, it is preferable that the difference in melting point between polymers is 20 ° C. or less because kneading using an extrusion kneader is easy to knead highly efficiently because a difference in melting state in the extrusion kneader hardly occurs. 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, when a melting point such as an amorphous polymer is not observed, the glass transition temperature (T _g ), Vicat softening temperature or heat distortion temperature is used instead.

Furthermore, melt viscosity is also important, and if the polymer forming the island is set lower, the island polymer is likely to be deformed by shearing force. However, if the island polymer is excessively low in viscosity, it tends to be seamed and the blend ratio with respect to the whole fiber cannot be increased. Therefore, the island polymer viscosity is preferably 1/10 or more of the sea polymer viscosity. In addition, the melt viscosity of the sea polymer may greatly affect the spinnability, and it is preferable to use a low viscosity polymer of 100 Pa · s or less as the sea polymer because the island polymer is easily dispersed. This can also significantly improve the spinnability. At this time, the melt viscosity is a value at a shear rate of 1216 sec ⁻¹ at the die surface temperature during spinning.

In the polymer alloy, since the island polymer and the sea polymer are incompatible with each other, the island polymers are more stably aggregated to be thermodynamically stable. However, in order to forcibly disperse the island polymer by ultra-fine dispersion, this polymer alloy has a much more unstable polymer interface than a normal polymer blend having a large dispersion diameter. For this reason, when this polymer alloy is simply spun, there are many unstable polymer interfaces, so the “ballus phenomenon” occurs where the polymer flow swells immediately after the polymer is discharged from the die, or the surface of the polymer alloy becomes unstable. As a result, the yarn may become unsatisfactory, resulting in an excessively large and uneven thread, and the spinning itself may become impossible (a negative effect of the ultrafine dispersion polymer alloy). In order to avoid such a problem, it is preferable to reduce the shear stress between the base hole wall and the polymer when discharging from the base. Here, the shear stress between the base hole wall and the polymer is calculated from the Hagen Poisyu equation (shear stress (dyne / cm ² ) = R × P / 2L). Here, R: radius of the nozzle discharge hole (cm), P: pressure loss at the nozzle discharge hole (dyne / cm ² ), and L: length of the nozzle discharge hole (cm). Further, P = (8LηQ / πR ⁴ ), η: polymer viscosity (poise), Q: discharge amount (cm ³ / sec), and π: circumference ratio. Further, 1 dyne / cm ² of the CGS unit system is 0.1 Pa in the SI unit system.

  In melt spinning with a single component of ordinary polyester, the shearing stress between the die hole wall and the polymer is 1 MPa or more, and meterability and spinnability can be secured. However, unlike the normal polyester, the polymer alloy of the present invention is more likely to lose the viscoelastic balance of the polymer alloy when the shear stress between the die hole wall and the polymer is large. It is necessary to reduce the shear stress. When the shear stress is 0.2 MPa or less, the flow on the die hole wall side and the polymer flow velocity at the center of the die discharge hole become uniform, and the shearing phenomenon is reduced, thereby reducing the ballast phenomenon and obtaining good spinnability. This is preferable. Generally, to make the shear stress smaller, the diameter of the nozzle discharge hole is increased and the length of the nozzle discharge hole is shortened. Therefore, it is preferable to use a die provided with a polymer measuring portion having a hole diameter smaller than that of the die discharge hole above the die discharge hole. A shear stress of 0.01 MPa or more is preferable because the polymer alloy fibers can be stably melt-spun and Wooster spots (U%), which are indicators of thick and thin threads, can be 15% or less.

  Further, from the viewpoint of sufficiently ensuring spinnability and spinning stability in melt spinning, the die surface temperature is preferably 25 ° C. or higher from the melting point of the sea polymer.

  As described above, when spinning the ultrafinely dispersed polymer alloy used in the present invention, the spinneret design is important, but the cooling condition of the yarn is also important. As described above, since the polymer alloy is a very unstable molten fluid, it is preferable to quickly cool and solidify after discharging from the die. For this reason, it is preferable that the distance from a nozzle | cap | die to the cooling start shall be 1-15 cm. Here, the start of cooling means a position where positive cooling of the yarn is started, but in the actual melt spinning apparatus, it is replaced with this at the upper end of the chimney.

  The spinning speed is not particularly limited, but high speed spinning is more preferable from the viewpoint of increasing the draft in the spinning process. The spinning draft is preferably 100 or more from the viewpoint of reducing the island domain diameter in the polymer alloy fiber.

The spun polymer alloy fiber is preferably subjected to stretching and heat treatment. However, the preheating temperature during stretching is higher than the glass transition temperature (T _g ) of the island polymer, so that the yarn unevenness can be reduced. It is possible and preferable. The polymer alloy fiber of the present invention can be freely subjected to yarn processing such as crimping, blending, and actual twisting.

In this production method, the polymer combination as described above and the spinning / drawing conditions are optimized, so that the island polymer is ultra-finely dispersed to several tens of nanometers, and the polymer alloy fibers with small yarn unevenness are also formed in the longitudinal direction of the yarn. It is possible to get.
More specifically, it is important to adopt the following production method according to the combination of polymers.
(1) When the sea component is polyethylene terephthalate and the island component is polyphenylene sulfide, these are melted separately, blended in a static kneader of 1 million divisions or more provided in a spinning pack, and then melt-spun. Method.
(2) When the sea component is polyethylene terephthalate copolymerized with isophthalic acid and bisphenol A, and the poorly soluble polymer of the island component is polyamide, these are separately melted and divided into 1 million units provided in the spin pack A method of melt spinning after blending with the above static kneader.
(3) In the case where the sea component is a hot water-soluble polymer based on polyalkylene glycol and the island component is a polymer selected from polyester, polyamide, polypropylene, and polycarbonate, these are melted separately and prepared in a spinning pack. A method of melt spinning after blending in a static kneader of 1 million divisions or more.
(4) A method in which 2-ethylhexyl acrylate or methyl methacrylate is copolymerized as a sea component and polystyrene having a melt viscosity of 100 Pa · s or less and polyester as an island component are blended and melt-spun.
(5) A method of melt spinning by blending polylactic acid having a melt viscosity of 100 Pa · s or less as a sea component and polyamide as an island component.
(6) When the sea component is polyethylene terephthalate copolymerized with isophthalic acid and bisphenol A, and the hardly soluble polymer of the island component is polyamide, the spinneret is used for melt spinning after kneading with a biaxial kneader. And a shear stress between the polymer alloy and 0.01 to 0.2 MPa · s.
(7) When the sea component is polyethylene terephthalate copolymerized with isophthalic acid and bisphenol A, and the hardly soluble polymer of the island component is polyamide, these are separately melted and divided into 1,000,000 parts provided in the spin pack A method in which the shear stress between the spinneret and the polymer alloy is set to 0.01 to 0.2 MPa · s when melt spinning after blending with the above static kneader.
(8) When the sea component is a hot water-soluble polymer based on polyalkylene glycol and the island component is polyester, these are melted separately and kneaded in a static kneader of 1 million divisions or more provided in a spinning pack. After the melt spinning, the shear stress between the spinneret hole wall and the polymer alloy is set to 0.01 to 0.2 MPa · s.

  The polymer alloy fiber of the present invention obtained as described above is suitable as a nanofiber precursor. For example, a fiber product made of nanofibers can be easily obtained by using this to process a textile product such as a woven fabric, a knitted fabric, a nonwoven fabric, or cotton and then removing the sea polymer with a solvent. In that case, it is preferable to use an aqueous solvent as the solvent from the viewpoint of cost reduction due to the necessity of an explosion-proof device, equipment versatility, and reduction of environmental burden. Specifically, it is preferable to use an alkaline aqueous solution or hot water. For this reason, as the readily soluble polymer, a polymer that can be alkali-hydrolyzed such as polyester and polycarbonate (PC), and a hot water soluble polymer such as hot water soluble polyamide, polyalkylene glycol, polyvinyl alcohol, and derivatives thereof are preferable.

  Nanofibers obtained by the above manufacturing method have a fiber length of several tens of μm to a cm order or more in some cases, and each nanofiber is adhered or entangled in some places, and several thousand to several hundreds of thousands per cross section. Innumerable nanofibers self-aggregate to form a spun yarn-shaped nanofiber assembly in which a single yarn is formed.

  In addition, in the above production method, particularly when a stationary kneader is positioned directly above the die, a nanofiber aggregate having a long fiber shape in which nanofibers are theoretically extended infinitely may be obtained.

  Further, the nanofiber aggregate obtained by the above production method can be in the form of spun yarn or long fiber, but these are continuous aggregates in which the nanofibers are oriented one-dimensionally with a finite length, that is, One-dimensionally oriented nanofiber assembly can be obtained.

  In addition, this nanofiber aggregate has a characteristic that the specific surface area is remarkably increased because the single yarn diameter is 1/10 to 1/100 that of the conventional ultrafine yarn. For this reason, the characteristic peculiar to the nanofiber which was not seen with the usual super extra fine thread grade is shown.

  For example, a significant improvement in adsorption characteristics can be mentioned. Actually, when comparing the adsorption of water vapor, that is, the hygroscopic performance, between the polyamide nanofiber aggregate obtained by the present invention and the normal polyamide superfine yarn, the moisture absorption rate of the normal polyamide superfine yarn is about 2%. In the polyamide nanofiber aggregate obtained by the present invention, the moisture absorption rate sometimes reached 6%. Hygroscopic performance is a very important characteristic from the viewpoint of comfort in clothing applications. Of course, in addition to water vapor, it has excellent adsorption properties for harmful substances such as chlorine, trihalomethane, environmental hormones, and heavy metal compounds. Furthermore, it is excellent in the legitimacy of aromatic substances and useful substances.

  Furthermore, in the nanofiber aggregate obtained by the present invention, a large number of gaps of several nanometers to several hundred nanometers are formed between nanofibers, and thus may exhibit specific properties such as a superporous material.

  For example, the nanofiber aggregate obtained by the present invention may not only have high water content and water retention, but also exhibit the following unique properties. In other words, the polyamide nanofiber aggregate obtained by the present invention may reach a swelling rate of 7% compared to a normal polyamide superfine yarn having a swelling rate of about 3% in the longitudinal direction due to water absorption. Moreover, since this water-absorbing swelling returns to its original length when dried, it is a reversible dimensional change. The swelling in the longitudinal direction of the yarn due to reversible water absorption / drying is an important characteristic from the viewpoint of the soil release property of the fabric, and is preferably 5% or more. Here, the soil release property means a property that dirt is easily removed by washing. As described above, the nanofiber aggregate absorbs and swells in the longitudinal direction of the yarn by absorbing water and expands the inter-fiber voids (texture, stitch) in the woven fabric or knitted fabric. This is because it can be removed.

  Thus, since the nanofiber aggregate obtained from the polymer alloy fiber of the present invention exhibits excellent adsorption / absorption characteristics, it can carry various functional drugs. The functional drug as used herein refers to a substance that can improve the function of the fiber. For example, a hygroscopic agent, a moisturizing agent, a flame retardant, a water repellent, a cold insulating agent, a heat insulating agent or a smoothing agent is also used as a target. Can do. Alternatively, the properties are not limited to those in the form of fine particles, and drugs for promoting health and beauty such as polyphenols, amino acids, proteins, capsaicin, vitamins, and drugs for skin diseases such as athlete's foot should be used as targets. Can do. Furthermore, pharmaceuticals such as disinfectants, anti-inflammatory agents, and analgesics can be used. Alternatively, a chemical for adsorbing and decomposing harmful substances such as polyamines and photocatalyst nanoparticles can also be used.

  Furthermore, there is no particular limitation on the method for supporting the functional drug, and it may be supported on the nanofiber by post-processing by treatment in the bath or coating, or may be contained in the polymer alloy fiber that is the precursor of the nanofiber. Also good. In addition, the functional drug itself may be directly supported on the nanofiber assembly, or after the functional drug precursor substance is supported on the nanofiber, the precursor substance is converted into a desired functional drug. You can also. More specific examples of the latter method include impregnating the nanofiber aggregate with an organic monomer and then polymerizing it, or impregnating the nanofiber aggregate with an easily soluble substance by treatment in a bath, There are methods for making it difficult to dissolve by oxidation-reduction reaction, ligand substitution, counter ion exchange reaction, and the like. In addition, when a functional drug precursor is supported in the spinning process, it is also possible to adopt a method in which a molecular structure with high heat resistance is maintained in the spinning process and the molecular structure is returned to a functional structure by post-processing. .

  The nanofiber aggregate not only incorporates various functional molecules, but also has excellent sustained release properties. For this reason, it means that it can be applied to an excellent sustained-release base material for functional molecules and drugs, or to a drug delivery system.

  In addition, when the nanofiber aggregate obtained by the present invention is used for apparel, it is possible to obtain a fiber product having an excellent texture with a squeaky feeling like silk and a dry feeling like rayon. Furthermore, by opening the nanofibers from the nanofiber aggregate by buffing etc., it is possible to obtain a fiber product with a superb peach feeling and a moist touch like human skin that was not thought of in the past. it can. Furthermore, it may exhibit unique tackiness by absorbing liquids such as water.

  The strength of the nanofiber aggregate obtained by the present invention is preferably 1 cN / dtex or more because the mechanical properties of the fiber product can be improved. The strength of the nanofiber aggregate is more preferably 2 cN / dtex or more.

  Unlike the prior art, the nanofiber aggregate obtained by the present invention can take various fiber product forms such as long fibers, short fibers, nonwoven fabrics, and thermoformed bodies. Nanofiber aggregates obtained by the present invention and fiber products having nanofibers at least in part, and functionally processed products thereof are yarn, cotton, package, woven fabric, knitted fabric, felt, nonwoven fabric, thermoformed body, It can be an intermediate product such as artificial leather. In addition, clothing (shirts, blousons, pants, coats, etc.), clothing materials, interior products (curtains, carpets, mats, wallpaper, furniture, etc.), vehicle interior products (mats, car seats, ceiling materials, etc.), living materials (wiping cloth) , Cosmetics, health products, toys, etc.), environment / industrial materials (building materials, abrasive cloth, filters, harmful substance removal products, etc.) and IT parts (sensor parts, battery parts, robot parts, etc.) And medical applications (blood filters, extracorporeal circulation columns, scaffolds, band dressings, etc.), artificial blood vessels, sustained drug release bodies, etc.

  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 by Toyo Seiki Capillograph 1B. The polymer storage time from sample introduction to measurement start was 10 minutes.

B. Melting | fusing point The peak top temperature which shows melting | fusing of a polymer by 2nd run using Perkin Elmaer DSC-7 was made into melting | fusing point of a polymer. The temperature rising rate at this time was 16 ° C./min, and the sample amount was 10 mg.

C. Shear stress at the die discharge hole The shear stress between the die hole wall and the polymer is calculated from the Hagen-Poiseuille equation (shear stress (dyne / cm ² ) = R × P / 2L). Here, R: radius of the nozzle discharge hole (cm), P: pressure loss at the nozzle discharge hole (dyne / cm ² ), and L: length of the nozzle discharge hole (cm). Further, P = (8LηQ / πR ⁴ ), η: polymer viscosity (poise), Q: discharge amount (cm ³ / sec), and π: circumference ratio. Here, the polymer viscosity uses values at the die discharge hole temperature and shear rate.

D. Worcester spots of polymer alloy 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. Observation of fiber cross section by TEM An ultrathin section was cut in the cross section 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.

F. Number average diameter of island domains The number average diameter of island domains is obtained as follows. That is, the diameter of the island domain in terms of a circle was calculated from the fiber cross-sectional photograph by TEM using image processing software (WINROOF), and a simple average value thereof was obtained. At this time, the number of island domains used for the average was measured for 300 or more island domains randomly selected in the same cross section, and this was performed at 5 locations and calculated using a total of 1500 or more island domain diameters.

G. Island domain diameter variation The island domain diameter variation is 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 obtained by dividing the product by the total fineness is defined as the area ratio of the island domains.

H. Diameter variation width of island domains The diameter variation width of island domains is evaluated as follows. That is, the evaluation is performed based on the area ratio of the island domains in which the island domain diameter difference is within the width of 30 nm in the vicinity of the center value of the number average diameter of the island domains or in a portion where the area ratio is high. This also used the data used to determine the number average diameter. The diameter ranges described in Example Tables 2, 5, 8, and 11 indicate a range of an island domain diameter difference of 30 nm. For example, 55 to 84 nm indicates a range of an island domain diameter difference of 30 nm to 55 nm to 84 nm. Moreover, the area ratio has shown the area ratio of the island domain of this diameter range.

I. A platinum-palladium alloy was deposited on the SEM observation fiber, and the fiber side surface was observed with a scanning electron microscope.

    SEM apparatus: Hitachi S-4000 type.

J. et al. Mechanical properties 100 m for the polymer alloy fiber and 10 m for the nanofiber aggregate were measured n = 5 times, and the fineness (dtex) of the nanofiber aggregate was determined from the average value. Then, at room temperature (25 ° C.), an initial sample length = 200 mm, a pulling rate = 200 mm / min, and a load-elongation curve was obtained under the conditions shown in JIS L1013. 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.

K. 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).

L. Reversible water swellability and swelling ratio in the longitudinal direction of the yarn are dried at 60 ° C. for 4 hours, and then the original length (L0) is measured. And after immersing this fiber in 25 degreeC water for 10 minutes, it takes out from water and measures a post-process length (L1) quickly. Furthermore, after drying this fiber at 60 ° C. for 4 hours, the length after drying (L2) is measured. And if it repeats drying / water immersion 3 times and the swelling rate of the third yarn longitudinal direction is 50% or more with respect to the swelling rate of the first yarn longitudinal direction, it has reversible water swellability. did. The swelling ratio in the longitudinal direction of the yarn was calculated as follows. In addition, the length of the fiber was measured by measuring the distance between two colored yarns connected to each other. This distance was about 100 mm.

    Swelling rate (%) in the longitudinal direction of the yarn = ((L1−L0) / L0) × 100 (%).

M.M. Color of polymer (b ^* value)
B ^* was measured with a MINOLTA SPECTROTOPOMETER CM-3700d. At this time, D ₆₅ (color temperature 6504K) was used as a light source, and measurement was performed in a 10 ° visual field.

N. The boiling water shrinkage sample is made into a 10-fold roll with a measuring instrument having a circumference of 1 m. Then, the original length (L0 ′) is measured in a state where a load that is 1/10 of the total fineness is suspended from the casket. After that, the casserole is in a load-free state, treated in a boiling water bath at 98 ° C. for 15 minutes, air-dried, and then treated under a load of 1/10 of the total fineness as with the original length. The length (L1 ′) is measured. The calculation is performed according to the following formula.

    Boiling water shrinkage ratio (%) = ((L0′−L1 ′) / L0 ′) × 100 (%).

O. A 140 ° C. dry heat shrinkage rate sample is marked with a width of 10 cm, and the length (L2 ′) between the markings is measured after 15 minutes of treatment in a 140 ° C. oven in a load-free state. The calculation is performed according to the following formula.

    140 ° C. dry heat shrinkage (%) = ((L0′−L2 ′) / L0 ′) × 100 (%).

Example 1
N6 (20) having a melt viscosity of 53 Pa · s (262 ° C., a shear rate of 121.6 sec ⁻¹ ) and an amine terminal of melting point of 220 ° C. blocked with acetic acid so that the amount of amine terminal groups was 5.0 × 10 ⁻⁵ mol equivalent / g. %) And a melt viscosity of 310 Pa · s (262 ° C., shear rate 121.6 sec ⁻¹ ), a copolymerization PET (80 wt.%) Obtained by copolymerizing 8 mol% of isophthalic acid having a melting point of 225 ° C. and 4 mol% of bisphenol A. %) Was kneaded at 260 ° C. with a biaxial extrusion kneader to obtain a polymer alloy chip having a b ^* value = 4. The copolymerized PET had a melt viscosity of 180 Pa · s at 262 ° C. and 1216 sec ⁻¹ . The kneading conditions at this time were as follows.
Screw type Same direction complete meshing type Double thread screw Diameter 37mm, effective length 1670mm, L / D = 45.1
The kneading part length is 28% of the effective screw length
The kneading part was located on the discharge side from 1/3 of the effective screw length.
Polymer supply with three backflow parts in the middle N6 and copolymerized PET were weighed separately and fed separately to the kneader.
260 ° C
Two vents.

Next, this polymer alloy chip was spun using a spinning machine shown in FIG. 12 to obtain a polymer alloy fiber. The polymer alloy chip was melted from the hopper 1 in the melting part 2 at 275 ° C. and led to the spin block 3 including the spinning pack 4 having a spinning temperature of 280 ° C. The polymer alloy melt was filtered with a metal nonwoven fabric having a limit filtration diameter of 15 μm, and then melt-spun from the die 5 having a die surface temperature of 262 ° C. At this time, as the base 5, as shown in FIG. 13, a metering part 12 having a diameter of 0.3 mm provided on the upper part of the discharge hole, having a discharge hole diameter of 0.7 mm and a discharge hole length 13 of 1.75 mm was used. . And the discharge amount per single hole at this time was 1.0 g / min. At this time, the shear stress between the hole wall of the die and the polymer was 0.058 MPa (the viscosity of the polymer alloy was 140 Pa · s, 262 ° C., shear rate 416 sec ⁻¹ ) and was sufficiently low. Furthermore, the distance from the base lower surface to the cooling start point (the upper end of the chimney 6) was 9 cm. The discharged yarn 7 is cooled and solidified over 1 m with cooling air of 20 ° C., and is supplied by an oil supply guide 8 installed 1.8 m below the base 5, and then the unheated first take-up roller 9 and the second take-up roller Winding was performed at a winding speed of 900 m / min via a roller 10 to obtain a 6 kg undrawn yarn package 11. The spinnability at this time was good, and the number of breaks during continuous spinning for 24 hours was zero. And the unstretched yarn of the polymer alloy fiber was subjected to stretching heat treatment by a stretching apparatus shown in FIG. Undrawn yarn 15 was supplied by feed roller 16 and subjected to drawing heat treatment by first hot roller 17, second hot roller 18, and third roller 19 to obtain drawn yarn 20. At this time, the temperature of the 1st hot roller 17 was 90 degreeC, and the temperature of the 2nd hot roller 18 was 130 degreeC. The draw ratio between the first hot roller 17 and the second hot roller 18 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 boiling water 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. 1), 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. Histograms of the number average diameter of the island domains analyzed from the TEM photographs are shown in FIG. 2 (diameter vs number) and FIG. 3 (diameter vs area ratio). At this time, the number (frequency) and area ratio in 10 nm increments are shown. I counted. The increment of 10 nm in diameter means that, for example, a diameter of 45 to 54 nm is counted as a diameter of 50 nm, and an island domain diameter of 65 to 74 nm is counted as a diameter of 70 nm. The physical properties of the polymer alloy fiber are shown in Table 2.

  Copolymerization in the polymer alloy fiber is carried out by producing a circular knitting using the polymer alloy fiber obtained here and immersing it in a 3% aqueous sodium hydroxide solution (90 ° C., bath ratio 1: 100) for 2 hours. More than 99% of the PET was hydrolyzed and removed. As a result, the circular knitting made of N6 single yarn was continuous like a long fiber when the copolymer PET, which is a sea component, was removed. I kept it. This circular knitting is completely different from the circular knitting made of normal N6 fibers, and has no “smoothness” peculiar to nylon, and conversely, has a “squeaking” feeling like silk and a “dry feeling” like rayon. It was a thing.

The yarn was pulled out from the circular knitting made of this N6 single yarn, and the fiber side surface was first observed with an optical microscope. The fiber diameter was about 2/3 of the fiber before the alkali treatment, and the sea polymer was removed. Thus, it was found that shrinkage occurred in the fiber radial direction (FIG. 4). Next, when the side surface of the fiber was observed by SEM, it was found that this yarn was not a single yarn but a nanofiber aggregate of spun yarn shape in which innumerable nanofibers were aggregated and connected (FIG. 5). ). In addition, the distance between the nanofibers of this N6 nanofiber assembly was about several nanometers to several hundred nanometers, and extremely fine voids existed between the nanofibers. Further, the result of observing the fiber cross section by TEM is shown in FIG. 6, and it was found that the N6 nanofiber has a single fiber diameter of about several tens of nanometers. And the single fiber diameter by the number average of a nanofiber was 56 nm (3 * 10 < ^-5 > dtex), and the thinness which was not in the past. Moreover, the fineness ratio of the single fiber having a single fiber fineness of 1 × 10 ⁻⁷ to 1 × 10 ⁻⁴ dtex was 99%. In particular, the fineness ratio of single fibers falling between 55 and 84 nm in terms of single fiber diameter was 71%, and the single fiber fineness variation was very small. The fineness ratio is calculated from the nanofiber diameter and corresponds to the area ratio of the polymer alloy fiber. The diameter of the nanofiber is shown in Table 3.

  Further, when the moisture absorption rate (ΔMR) of the circular knitting made of N6 alone was measured, it showed an excellent moisture absorption of 6%, which surpassed that of cotton. Furthermore, the thread | yarn which consists of this N6 nanofiber aggregate was extracted from the circular knitting, and various physical properties were measured. When the swelling property in the longitudinal direction of the yarn with respect to water was examined, the water absorption swelling / drying shrinkage was reversibly repeated (FIG. 7). The water absorption swelling ratio in the longitudinal direction of the yarn was 7%, which was a much higher value than 3% of ordinary N6 fibers. Further, when the mechanical properties of the yarn comprising this N6 nanofiber aggregate were measured, the strength was 2.0 cN / dtex and the elongation was 50%.

  Furthermore, when buffing was performed on this circular knitting, it showed a super peach feeling that was not possible with conventional ultra-fine fibers and a moist and fresh texture like human skin.

Example 2
N6 having a melt viscosity of 212 Pa · s (262 ° C., shear rate of 121.6 sec ⁻¹ ), an amine terminal having a melting point of 220 ° C. blocked with acetic acid, and an amine terminal group amount of 5.0 × 10 ⁻⁵ mol equivalent / g. A polymer alloy chip having a b ^* value = 4 was obtained using a biaxial extrusion kneader in the same manner as in Example 1 except that (20 wt%) was used. The discharge rate per single hole was 1.0 g / min, and the shear stress between the cap hole wall and the polymer was 0.071 MPa (the viscosity of the polymer alloy was 170 Pa · s, 262 ° C., shear rate 416 sec ⁻¹ ). Except for the above, melt spinning was performed in the same manner as in Example 1 to obtain a polymer alloy undrawn yarn. The spinnability at this time was good, and there was no yarn breakage during continuous spinning for 24 hours. Then, the draw ratio was set to 3.0 times, and the film was drawn in the same manner as in Example 1 and 128 dtex, 36 filaments, strength 4.1 cN / dtex, elongation 37%, U% = 1.2%, boiling water A polymer alloy fiber having excellent characteristics with a shrinkage of 11% was obtained. When the cross section of the obtained polymer alloy fiber was observed with TEM, as in Example 1, copolymer PET was the sea, N6 was the island-island structure, and the number average diameter of the island N6 was 55 nm. An ultrafinely dispersed polymer alloy fiber was obtained. The physical properties of the polymer alloy fiber are shown in Table 2.

Using the polymer alloy fiber obtained here, in the same manner as in Example 1, a spun yarn-shaped nanofiber assembly was obtained by alkali treatment. Furthermore, as a result of analyzing the single yarn fineness variation of these nanofibers in the same manner as in Example 1, the single yarn diameter based on the number average of the nanofibers is 60 nm (3 × 10 ⁻⁵ dtex), which is an unprecedented fineness. The variation in fineness was very small. The diameters of the nanofibers are shown in Table 3.

  The yarn composed of this N6 nanofiber aggregate had a strength of 2.2 cN / dtex and an elongation of 50%.

  Furthermore, when buffing was performed on this circular knitting, it showed a super peach feeling that was not possible with conventional ultra-fine fibers and a moist and fresh texture like human skin.

Example 3
N6 was melt-spun in the same manner as in Example 2 with N6 (20 wt%) having a melt viscosity of 500 Pa · s (262 ° C., shear rate of 121.6 sec ⁻¹ ) and a melting point of 220 ° C. At this time, the shear stress between the die hole wall and the polymer was 0.083 MPa (the viscosity of the polymer alloy was 200 Pa · s, 262 ° C., 416 sec ⁻¹ ), melt spinning was performed in the same manner as in Example 1, and the polymer alloy was not stretched I got a thread. The spinnability at this time was good, and there was no yarn breakage during continuous spinning for 24 hours. This was also stretched and heat treated in the same manner as in Example 2 and was excellent in 128 dtex, 36 filament, strength 4.5 cN / dtex, elongation 37%, U% = 1.9%, boiling water shrinkage 12%. A polymer alloy fiber having the above characteristics was obtained. When the cross section of the obtained polymer alloy fiber was observed with a TEM, as in Example 1, the copolymer PET was sea, N6 was an island-island structure, the number average diameter of the island N6 was 60 nm, and N6 was A super finely dispersed polymer alloy fiber was obtained. The physical properties of the polymer alloy fiber are shown in Table 2.

Using the polymer alloy fiber obtained here, in the same manner as in Example 1, a spun yarn-shaped nanofiber assembly was obtained by alkali treatment. Furthermore, as a result of analyzing the variation in the single yarn fineness of these nanofibers in the same manner as in Example 1, the single yarn diameter based on the number average of the nanofibers is 65 nm (4 × 10 ⁻⁵ dtex), which is an unprecedented fineness. The variation in fineness was very small. The diameters of the nanofibers are shown in Table 3.

  The yarn comprising this N6 nanofiber aggregate had a strength of 2.4 cN / dtex and an elongation of 50%.

  Furthermore, when buffing was performed on this circular knitting, it showed a super peach feeling that was not possible with conventional ultra-fine fibers and a moist and fresh texture like human skin.

Example 4
N6 was melt-spun in the same manner as in Example 3 with a blend ratio of 50% by weight based on the entire polymer alloy. At this time, the shear stress between the die hole wall and the polymer was 0.042 MPa, and melt spinning was performed in the same manner as in Example 1 to obtain a polymer alloy undrawn yarn. The spinnability at this time was good, and there was no yarn breakage during continuous spinning for 24 hours. This was also stretched and heat-treated in the same manner as in Example 2 and was excellent in 128 dtex, 36 filament, strength 4.3 cN / dtex, elongation 37%, U% = 2.5%, and boiling water shrinkage 13%. A polymer alloy fiber having characteristics was obtained. When the cross section of the obtained polymer alloy fiber was observed with a TEM, as in Example 1, copolymer PET was the sea, N6 was an island-island structure, and the number average diameter of the island N6 was 80 nm. A super finely dispersed polymer alloy fiber was obtained.

Using the polymer alloy fiber obtained here, in the same manner as in Example 1, a spun yarn-shaped nanofiber assembly was obtained by alkali treatment. However, at this time, drying was performed at 140 ° C. under tension. Furthermore, as a result of analyzing the variation in the single yarn fineness of these nanofibers in the same manner as in Example 1, the single yarn diameter based on the number average of the nanofibers is 84 nm (6 × 10 ⁻⁵ dtex), which is an unprecedented fineness. The variation in fineness was very small.

  Further, the yarn comprising this N6 nanofiber aggregate had a strength of 2.6 cN / dtex and an elongation of 50%.

Comparative Example 1
PET having a melt viscosity of 180 Pa · s (290 ° C., shear rate of 121.6 sec ⁻¹ ) and a melting point of 255 ° C. as an island component, melt viscosity of 100 Pa · s (290 ° C., shear rate of 121.6 sec ⁻¹ ), Vicat softening temperature of 107 A sea-island composite yarn was obtained as described in Example 1 of JP-A No. 53-106872, using polystyrene (PS) at 0 ° C. as the sea component. The number average diameter of the island domains was as large as 2.0 μm. Then, as described in Examples in JP-A-53-106872, PS was removed by 99% or more by trichlorethylene treatment to obtain a super fine yarn. When the cross section of the fiber was observed with a TEM, the single yarn diameter of the ultrafine yarn was as large as 2.0 μm (0.04 dtex).

Comparative Example 2
N6 with a melt viscosity of 50 Pa · s (280 ° C., 121.6 sec ⁻¹ ), a melting point of 220 ° C. and a PET with a melt viscosity of 210 Pa · s (280 ° C., 121.6 sec ⁻¹ ) and a melting point of 255 ° C. with an N6 blend ratio of 20 wt. After blending the chips so as to be%, the melt is melted at 290 ° C., and the spinning temperature is 296 ° C., the die surface temperature is 280 ° C., the number of die holes is 36, the discharge hole diameter is 0.30 mm, and the discharge hole length is 0.50 mm. Melt spinning was performed in the same manner as in Example 1, and the undrawn yarn was wound up at a spinning speed of 1000 m / min. However, it is a simple chip blend, and since the melting point difference between polymers is large, the blend spots of N6 and PET are large, and not only a large ball is generated under the base, but also the stringiness is poor and the yarn is stably Although it could not be wound, a small amount of undrawn yarn was obtained, and the temperature of the first hot roller 17 was 85 ° C. and the draw ratio was 3 times, and the drawing was performed in the same manner as in Example 1 to draw 100 dtex and 36 filaments. I got a thread. The number average diameter of the island domain was as large as 1.0 μm.

Using this yarn, circular knitting was performed in the same manner as in Example 1, and 99% or more of the PET component was removed by alkali treatment. N6 single yarn was pulled out from the obtained circular knitting, and the cross section of the fiber was observed with TEM. As a result, the single yarn diameter was 400 nm to 4 μm (single yarn fineness 1 × 10 ⁻³ to 1 × 10 ⁻¹ dtex). It was confirmed that the yarn was formed. However, the single yarn fineness based on the number average was as large as 9 × 10 ⁻³ dtex (single yarn diameter: 1.0 μm). Furthermore, the single yarn fineness variation of the N6 ultrafine yarn was also large.

Comparative Example 3
N6 with a melt viscosity of 395 Pa · s (262 ° C., 121.6 sec ⁻¹ ), a melting point of 220 ° C. and PE with a melt viscosity of 56 Pa · s (262 ° C., 121.6 sec ⁻¹ ) and a melting point of 105 ° C. with a N6 blend ratio of 65 After blending the chips so as to be weight%, using the apparatus of FIG. 15, the temperature of the single screw extruder kneader 21 was melted at 260 ° C., then the number of nozzle holes was 12, the discharge hole diameter was 0.30 mm, the discharge hole length was 0. Melt spinning was carried out in the same manner as in Example 1 using a 50 mm barrel cap. However, the blend spots of N6 and PE were large, and not only a large ball was generated under the mouthpiece, but also the stringiness was poor, and the yarn could not be wound up stably. Then, stretching and heat treatment were performed in the same manner as in Example 1 to obtain a stretched yarn of 82 dtex and 12 filaments. The draw ratio at this time was 2.0 times. The number average diameter of the island domain was as large as 1.0 μm.

Using this yarn, circular knitting was performed in the same manner as in Example 1, and PE was eluted with toluene at 85 ° C. for 1 hour or longer to remove 99% or more of PE. The resulting drawn out N6 alone yarn from circular knit, was subjected to fiber cross-section observation by TEM, ultrafine single fiber diameter 500nm~3μm (single yarn fineness ^{2 × 10 -3 ~8 × 10 -2} dtex) It was confirmed that the yarn was formed. The number average of single yarn fineness was as large as 9 × 10 ⁻³ dtex (single yarn diameter 1.0 μm). Furthermore, the single yarn fineness variation of the N6 ultrafine yarn was also large.

Comparative Example 4
Melt viscosity 150Pa · s (262 ℃, 121.6sec -1), N6 melt viscosity 145 Pa · s melting point ^{220 ℃ (262 ℃, 121.6sec -1} ), the N6 blend ratio and the PE melting point 105 ° C. 20 Melt spinning was carried out in the same manner as in Comparative Example 3 using the apparatus shown in FIG. However, the blend spots of N6 and PE are large and not only a large ball is generated under the mouthpiece, but also the stringiness is poor.
Although the yarn could not be wound stably, a small amount of undrawn yarn was obtained and subjected to drawing and heat treatment in the same manner as in Example 1 to obtain a drawn yarn of 82 dtex and 12 filaments. The draw ratio at this time was 2.0 times. The number average diameter of the island domain was as large as 374 nm. Further, the variation of the island domain diameter is shown in FIGS. 8 and 9, which is large.

Using this yarn, circular knitting was performed in the same manner as in Example 1, and PE was eluted with toluene at 85 ° C. for 1 hour or longer to remove 99% or more of PE. N6 single yarn was pulled out from the obtained circular knitting, and the cross section of the fiber was observed with TEM. As a result, the single yarn diameter was 100 nm to 1 μm (single yarn fineness 9 × 10 ^{−5 to} 9 × 10 ⁻³ dtex). It was confirmed that the yarn was formed. However, the single yarn fineness based on the number average was as large as 1 × 10 ⁻³ dtex (single yarn diameter 384 nm).

Comparative Example 5
A sea-island composite yarn was obtained in the same manner as in Comparative Example 1 using PS and PET described in Comparative Example 1, using the spinning pack and base shown in FIG. 11 of JP-B-60-28822. At this time, a blend polymer of 2: 1 (weight ratio) of PS and PET was used as the island component of the sea-island composite yarn, and PS was used as the sea component (the sea-island composite ratio was 1: 1 by weight). Specifically, in FIG. 11 of the publication, the A component is PET and the B and C components are PS. When the cross section of the fiber was observed, there was a very small amount of island domain having a diameter of about 100 nm at the minimum, but the number average diameter was as large as 316 nm because of poor dispersion of PET in PS. Further, the variation of the island domain diameter is shown in FIGS. 10 and 11, which is large. Then, this was treated with trichlorethylene in the same manner as in Comparative Example 1 to remove 99% or more of PS to obtain a super fine yarn. When the cross section of the fiber was observed, there was a very small amount of single yarn having a single yarn diameter of about 100 nm, but the single yarn fineness based on the number average was 9 × 10 ⁻⁴ dtex (single yarn diameter 326 nm). It was a thing.

Example 5
The N6 and copolymerized PET used in Example 1 were separately melted at 270 ° C. using the apparatus of FIG. 16, and then the polymer melt was guided to the spin block 3 having a spinning temperature of 280 ° C. Then, after using the static kneader 22 (“High Mixer” manufactured by Toray Engineering Co., Ltd.) mounted in the spinning pack 4 to sufficiently mix and divide the two kinds of polymers, perform melt spinning as in Example 1. It was. The blend ratio of the polymer at this time was 20% by weight for N6 and 80% by weight for copolymerized PET. The undrawn yarn was also drawn and heat treated in the same manner as in Example 1. The resulting polymer alloy fiber exhibited excellent properties of 120 dtex, 36 filaments, strength 3.9 cN / dtex, elongation 38%, U% = 1.7%. When the cross section of this polymer alloy fiber was observed by TEM, as in Example 1, copolymer PET was the sea and N6 was the island-island structure. The number average diameter of island N6 was 52 nm, and N6 was ultrafine. A dispersed polymer alloy fiber was obtained. The physical properties of the polymer alloy fibers are shown in Table 5.

Using the polymer alloy fiber obtained here, in the same manner as in Example 1, a spun yarn-shaped nanofiber assembly was obtained by alkali treatment. Furthermore, as a result of analyzing the variation in the single yarn fineness of these nanofibers in the same manner as in Example 1, the single yarn diameter based on the number average of the nanofibers is 54 nm (3 × 10 ⁻⁵ dtex), which is an unprecedented fineness. The variation in fineness was very small. The diameters of the nanofibers are shown in Table 6.

  Further, the moisture absorption rate (ΔMR) of the circular knitting composed of the nanofiber aggregate was 5%. Further, the yarn composed of this N6 nanofiber aggregate had a strength of 2.0 cN / dtex and an elongation of 50%.

  Furthermore, when buffing was performed on this circular knitting, it showed a super peach feeling that was not possible with conventional ultra-fine fibers and a moist and fresh texture like human skin.

Example 6
The N6 and copolymerized PET used in Example 1 were melt-kneaded with a biaxial extrusion kneader at 270 ° C. using the apparatus shown in FIG. 17, and then the polymer melt was guided to the spin block 3 at a spinning temperature of 280 ° C. Then, melt spinning was performed in the same manner as in Example 1. The blend ratio of the polymer at this time was 20% by weight for N6 and 80% by weight for copolymerized PET. The undrawn yarn was also drawn and heat treated in the same manner as in Example 1. The resulting polymer alloy fiber exhibited excellent properties of 120 dtex, 36 filaments, strength 3.9 cN / dtex, elongation 38%, U% = 1.7%. When the cross section of this polymer alloy fiber was observed by TEM, as in Example 1, copolymer PET was the sea, N6 was the island-island structure, and the number average diameter of island N6 was 54 nm, and N6 was ultrafine. A dispersed polymer alloy fiber was obtained. The physical properties of the polymer alloy fibers are shown in Table 5.

Using the polymer alloy fiber obtained here, in the same manner as in Example 1, a spun yarn-shaped nanofiber assembly was obtained by alkali treatment. Furthermore, as a result of analyzing the variation in the single yarn fineness of these nanofibers in the same manner as in Example 1, the single yarn diameter based on the number average of the nanofibers is 56 nm (3 × 10 ⁻⁵ dtex), which is an unprecedented fineness. The variation in fineness was very small. The diameters of the nanofibers are shown in Table 6.

  Further, the moisture absorption rate (ΔMR) of the circular knitting composed of the nanofiber aggregate was 5%. Further, the yarn composed of this N6 nanofiber aggregate had a strength of 2.0 cN / dtex and an elongation of 50%.

  Furthermore, when buffing was performed on this circular knitting, it showed a super peach feeling that was not possible with conventional ultra-fine fibers and a moist and fresh texture like human skin.

Example 7
“Paogen PP-15” (melting viscosity 350 Pa · s, 262 ° C., 121.6 sec ⁻¹ , melting point 60 ° C.) manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., which is a hot water-soluble polymer, is a copolymerized PET, spinning speed is 5000 m / min. As in Example 6, kneading and melt spinning were performed. The melt viscosity of this “Paogen PP-15” at 262 ° C. and 1216 sec ⁻¹ was 180 Pa · s. The obtained polymer alloy fiber showed excellent properties of 70 dtex, 36 filaments, strength 3.8 cN / dtex, elongation 50%, U% = 1.7%. When the cross section of this polymer alloy fiber was observed with a TEM, it was found that the copolymer PET was sea, N6 was an island-island structure, the number average diameter of the island N6 was 53 nm, and N6 was ultra-dispersed polymer alloy. Fiber was obtained. The physical properties of the polymer alloy fibers are shown in Table 8.

Using the polymer alloy fiber obtained here, in the same manner as in Example 1, a spun yarn-shaped nanofiber assembly was obtained by alkali treatment. Furthermore, as a result of analyzing the variation in the single yarn fineness of these nanofibers in the same manner as in Example 1, the single yarn diameter based on the number average of the nanofibers is 56 nm (3 × 10 ⁻⁵ dtex), which is an unprecedented fineness. The variation in fineness was very small. The diameters of the nanofibers are shown in Table 9.

  Further, the yarn composed of this N6 nanofiber aggregate had a strength of 2.0 cN / dtex and an elongation of 60%.

  Furthermore, when buffing was performed on this circular knitting, it showed a super peach feeling that was not possible with conventional ultra-fine fibers and a moist and fresh texture like human skin.

Example 8
Instead of N6, N66 having a melt viscosity of 100 Pa · s (280 ° C., 121.6 sec ⁻¹ ) and a melting point of 250 ° C. was used. N66 was 270 ° C. using the apparatus of FIG. Was melted at 80 ° C., and then the polymer melt was guided to the spin block 3 having a spinning temperature of 280 ° C. Then, melt spinning was performed in the same manner as in Example 5. The polymer blend ratio at this time was 20% by weight for N66, 80% by weight for the hot water soluble polymer, the discharge rate per single hole was 1.0 g / min, and the spinning speed was 5000 m / min. Then, a polymer alloy fiber having 70 dtex, 36 filaments, strength 4.5 cN / dtex, and elongation 45% was obtained. When the cross section of the obtained polymer alloy fiber was observed with a TEM, the hydrothermally soluble polymer was the sea, N66 was the island-island structure, and the number average diameter of the island N66 was 58 nm. A polymer alloy fiber was obtained. The physical properties of the polymer alloy fibers are shown in Table 8.

Using the polymer alloy fiber obtained here, in the same manner as in Example 1, a spun yarn-shaped nanofiber assembly was obtained by alkali treatment. Furthermore, as a result of analyzing the variation in the single yarn fineness of these nanofibers in the same manner as in Example 1, the single yarn diameter based on the number average of the nanofibers is 62 nm (3 × 10 ⁻⁵ dtex), which is an unprecedented fineness. The variation in fineness was very small. The diameters of the nanofibers are shown in Table 9.

  Further, the yarn composed of this N66 nanofiber aggregate had a strength of 2.5 cN / dtex and an elongation of 60%.

  Furthermore, when buffing was performed on this circular knitting, it showed a super peach feeling that was not possible with conventional ultra-fine fibers and a moist and fresh texture like human skin.

Example 9
A hot water-soluble polymer used in Example 7 and a copolymerized PET (copolymerized with 8 wt% of PEG 1000 and 7 mol% of isophthalic acid) having a melt viscosity of 300 Pa · s (262 ° C., 121.6 sec ⁻¹ ) and a melting point of 235 ° C. Kneading and melt spinning were performed in the same manner as in Example 6. At this time, the polymer blend ratio was 20% by weight for copolymerized PET, 80% by weight for hot water-soluble polymer, the discharge rate per single hole was 1.0 g / min, and the spinning speed was 6000 m / min. At this time, the shear stress between the die hole wall and the polymer was 0.11 MPa (the viscosity of the polymer alloy was 240 Pa · s, 262 ° C., shear rate 475 sec ⁻¹ ), which was sufficiently low. A polymer alloy fiber having 60 dtex, 36 filaments, a strength of 3.0 cN / dtex, and an elongation of 55% was obtained. When the cross section of the obtained polymer alloy fiber was observed with a TEM, the water-soluble polymer showed the sea and the copolymerized PET showed the island-island structure, and the number average diameter of the island-copolymerized PET was 52 nm. A polymer alloy fiber in which PET was ultrafinely dispersed was obtained. The physical properties of the polymer alloy fibers are shown in Table 8.

Using the polymer alloy fiber obtained here, circular knitting was made in the same manner as in Example 1, and then the hot water-soluble polymer was eluted with hot water at 100 ° C. A circular knitting made of a nanofiber aggregate having a “dry feeling” was obtained. As a result of analyzing the variation in the single fiber fineness of the nanofiber in the same manner as in Example 1, the single yarn diameter based on the number average of the nanofiber is 54 nm (3 × 10 ⁻⁵ dtex), which is an unprecedented fineness, and the single yarn fineness is The variation was very small. The diameters of the nanofibers are shown in Table 9.

  Further, the moisture absorption rate (ΔMR) of the circular knitting made of this nano-fabric aggregate was 2%. Moreover, the yarn comprising this copolymerized PET nanofiber aggregate had a strength of 2.0 cN / dtex and an elongation of 70%.

Example 10
PET having a melt viscosity of 190 Pa · s (280 ° C., 121.6 sec ⁻¹ ) and a melting point of 255 ° C. and the hot water-soluble polymer used in Example 7 were kneaded in the same manner as in Example 5 and melt-spun at a spinning speed of 6000 m / min. At this time, the blend ratio of the polymer was 20% by weight of PET, 80% by weight of hot water soluble polymer, the melting temperature of PET was 285 ° C., the melting temperature of hot water soluble polymer was 80 ° C., the spinning temperature was 295 ° C., and per pore. The discharge amount was 1.0 g / min. At this time, the shear stress between the hole wall of the die and the polymer was 0.12 MPa (the viscosity of the polymer alloy was 245 Pa · s, 262 ° C., shear rate 475 sec ⁻¹ ) and was sufficiently low. A polymer alloy fiber having 60 dtex, 36 filaments, a strength of 3.0 cN / dtex, and an elongation of 45% was obtained. When the cross section of the obtained polymer alloy fiber was observed with a TEM, the water-soluble polymer was the sea, and PET was the island-island structure. The number average diameter of the island PET was 62 nm, and the PET was finely dispersed. A polymer alloy fiber was obtained. The physical properties of the polymer alloy fibers are shown in Table 8.

A nanofiber assembly was obtained by the same operation as in Example 9 using the polymer alloy fiber obtained here. The number average single fiber diameter of the nanofibers is 65 nm (3 × 10 ⁻⁵ dtex), which is an unprecedented fineness, and the single fiber fineness variation is very small. The diameters of the nanofibers are shown in Table 9.

Example 11
PBT having a melt viscosity of 120 Pa · s (262 ° C., 121.6 sec ⁻¹ ) and a melting point of 225 ° C. and the hot water-soluble polymer used in Example 7 were kneaded in the same manner as in Example 5 and melt-spun at a spinning speed of 6000 m / min. The polymer blend ratio at this time was 20% by weight of PBT, 80% by weight of hot water soluble polymer, the melting temperature of PBT was 255 ° C, the melting temperature of hot water soluble polymer was 80 ° C, the spinning temperature was 265 ° C, and the single hole The per unit discharge amount was 1.0 g / min. At this time, the shear stress between the base hole wall and the polymer was as low as 0.12 MPa. A polymer alloy fiber having 60 dtex, 36 filaments, a strength of 3.0 cN / dtex, and an elongation of 45% was obtained. When the cross section of the obtained polymer alloy fiber was observed by TEM, the hydrothermally soluble polymer was the sea, the PBT was the island-island structure, the number average diameter of the island PBT was 62 nm, and the PBT was finely dispersed. A polymer alloy fiber was obtained. The physical properties of the polymer alloy fibers are shown in Table 8.

A nanofiber assembly was obtained by the same operation as in Example 9 using the polymer alloy fiber obtained here. The number average single fiber diameter of the nanofibers was 65 nm (4 × 10 ⁻⁵ dtex), which is an unprecedented fineness, and the single fiber fineness variation was very small. The diameters of the nanofibers are shown in Table 9.

Example 12
Polytrimethylene terephthalate (PTT) having a melt viscosity of 220 Pa · s (262 ° C., 121.6 sec ⁻¹ ) and a melting point of 225 ° C. and the hot water-soluble polymer used in Example 7 were kneaded and melt-spun in the same manner as in Example 11. At this time, the shear stress between the base hole wall and the polymer was as low as 0.13 MPa. A polymer alloy fiber having 60 dtex, 36 filaments, a strength of 3.0 cN / dtex, and an elongation of 45% was obtained. When the cross section of the obtained polymer alloy fiber was observed with TEM, the water-soluble polymer showed the sea-island structure, the PTT was the island-island structure, the diameter of the island PTT was 62 nm, and the PTT was very finely dispersed. A polymer alloy fiber was obtained. The physical properties of the polymer alloy fibers are shown in Table 8.

A nanofiber assembly was obtained by the same operation as in Example 9 using the polymer alloy fiber obtained here. The number average single fiber diameter of the nanofibers was 65 nm (4 × 10 ⁻⁵ dtex), which is an unprecedented fineness, and the single fiber fineness variation was very small. The diameters of the nanofibers are shown in Table 9.

Example 13
Poly L-lactic acid (PLA) having a melt viscosity of 350 Pa · s (220 ° C., 121.6 sec ⁻¹ ), a melting point of 170 ° C., an optical purity of 99.5% or more, and a weight average molecular weight of 160,000 and the hot water solubility used in Example 7 The polymer was kneaded and melt-spun as in Example 11. The weight average molecular weight of polylactic acid was determined as follows. THF (tetrohydrofuran) was mixed with the sample chloroform solution to obtain a measurement solution. This was measured at 25 ° C. using water permeation gel permeation chromatography (GPC) Waters 2690, and the weight average molecular weight was determined in terms of polystyrene. The polymer blend ratio at this time was 20% by weight of PLA, 80% by weight of a hot water soluble polymer, a spinning temperature of 235 ° C., a die surface temperature of 220 ° C., and a discharge amount per single hole was 1.0 g / min. A polymer alloy fiber having 60 dtex, 36 filaments, a strength of 2.5 cN / dtex, and an elongation of 35% was obtained. When the cross section of the obtained polymer alloy fiber was observed with TEM, the hydrothermally soluble polymer was the sea, PLA was the island-island structure, the number average diameter of the island PLA was 48 nm, and the PLA was finely dispersed. A polymer alloy fiber was obtained. The physical properties of the polymer alloy fibers are shown in Table 8.

A nanofiber assembly was obtained by the same operation as in Example 9 using the polymer alloy fiber obtained here. The number average single fiber diameter of the nanofibers was 50 nm (2 × 10 ⁻⁵ dtex), which is an unprecedented fineness, and the single fiber fineness variation was very small. The diameters of the nanofibers are shown in Table 9.

Example 14
Polycarbonate (PC) having a melt viscosity of 300 Pa · s (262 ° C., 121.6 sec ⁻¹ ) and a heat distortion temperature of 140 ° C. and the hot water-soluble polymer used in Example 7 were kneaded and melt-spun in the same manner as in Example 8. The polymer blend ratio at this time was 20% by weight for PC, 80% by weight for hot water-soluble polymer, and the discharge rate per single hole was 1.0 g / min. A polymer alloy fiber having 70 dtex, 36 filaments, strength 2.2 cN / dtex, and elongation 35% was obtained. When the cross section of the obtained polymer alloy fiber was observed by TEM, the water-soluble polymer showed the sea and the PC was the island structure of the island, the diameter by the number average of the island PC was 85 nm, and the PC was finely dispersed. A polymer alloy fiber was obtained. The physical properties of the polymer alloy fiber are shown in Table 11.

A circular knitting was produced using the polymer alloy fibers obtained here in the same manner as in Example 1, and this was treated with hot water at 40 ° C. for 10 hours to elute 99% or more of the hot water soluble polymer. Got the body. The number average single fiber diameter of the nanofibers was 88 nm (8 × 10 ⁻⁵ dtex), which is an unprecedented fineness, and the single fiber fineness variation was very small. The diameters of the nanofibers are shown in Table 12.

Reference example 1
PS having a melt viscosity of 300 Pa · s (262 ° C., 121.6 sec ⁻¹ ), a melting point of 220 ° C. polymethylpentene (PMP), a melt viscosity of 300 Pa · s (262 ° C., 121.6 sec ⁻¹ ), and a Vicat softening temperature of 105 ° C. The mixture was kneaded and melt-spun in the same manner as in Example 8 at a spinning speed of 1500 m / min, and stretched and heat-treated in the same manner as in Example 1 with a draw ratio of 1.5. The polymer blend ratio at this time was 20% by weight for PMP, 80% by weight for PS, and the discharge amount per single hole was 1.0 g / min. A polymer alloy fiber having 160 dtex, 36 filaments, a strength of 3.0 cN / dtex, and an elongation of 40% was obtained. When the cross section of the obtained polymer alloy fiber was observed with a TEM, it was found that PS is the sea, PMP is the island structure of the island, the number average diameter of the island PMP is 70 nm, and the polymer alloy in which PMP is microdispersed. A fiber was obtained. The physical properties of the polymer alloy fiber are shown in Table 11.

After the circular knitting was produced using the polymer alloy fiber obtained in the same manner as in Example 1, PS was embrittled with concentrated hydrochloric acid at 40 ° C., then PS was removed with methyl ethyl ketone, and a round made of PMP nanofiber aggregates. Got knitting. The number average single fiber diameter of the nanofibers was 73 nm (5 × 10 ⁻⁵ dtex), which is an unprecedented fineness, and the single fiber fineness variation was very small. The diameters of the nanofibers are shown in Table 12.

Example 15
PP having a melt viscosity of 300 Pa · s (220 ° C., 121.6 sec ⁻¹ ) and a melting point of 162 ° C. and the hot water-soluble polymer used in Example 7 were kneaded, melt-spun, stretched and heat-treated in the same manner as in Reference Example 1 . The polymer blend ratio at this time was 20 wt% for PP, 80 wt% for hot water soluble polymer, spinning temperature 235 ° C., die surface temperature 220 ° C., and the discharge rate per single hole was 1.0 g / min. A polymer alloy fiber having 160 dtex, 36 filaments, a strength of 2.5 cN / dtex, and an elongation of 50% was obtained. When the cross section of the obtained polymer alloy fiber was observed by TEM, the water-soluble polymer showed the sea and the PP was an island structure, and the number average diameter of the island PP was 48 nm, and the PP was finely dispersed. A polymer alloy fiber was obtained. The physical properties of the polymer alloy fiber are shown in Table 11.

A nanofiber assembly was obtained by the same operation as in Example 9 using the polymer alloy fiber obtained here. The number average single fiber diameter of the nanofibers was 50 nm (2 × 10 ⁻⁵ dtex), which is an unprecedented fineness, and the single fiber fineness variation was very small. The diameters of the nanofibers are shown in Table 12.

Example 16
A PPS having a melt viscosity of 200 Pa · s (300 ° C., 121.6 sec ⁻¹ ), a melting point of 280 ° C. and a PET having a melt viscosity of 200 Pa · s (300 ° C., 121.6 sec ⁻¹ ) are kneaded, melt spun, as in Reference Example 1 , Stretched and heat treated. The draw ratio at this time was 3.1 times. The polymer blend ratio is 20% by weight of PPS, 80% by weight of PET, the melting temperature of PPS is 320 ° C, the melting temperature of PET is 290 ° C, the spinning temperature is 320 ° C, the die surface temperature is 300 ° C, and the discharge amount per single hole. Was 1.0 g / min. A polymer alloy fiber having 77 dtex, 36 filaments, a strength of 5.2 cN / dtex, and an elongation of 50% was obtained. When the cross section of the obtained polymer alloy fiber was observed with a TEM, it was found that PET was the sea, PPS was the island-island structure, the number average diameter of the island PPS was 120 nm, and the polymer alloy in which PPS was ultradispersed. Fiber was obtained. The physical properties of the polymer alloy fiber are shown in Table 11.

Using the polymer alloy fibers obtained here, circular knitting was produced in the same manner as in Example 1, and PET was eluted by alkali treatment to obtain circular knitting composed of PPS nanofiber aggregates. The number average single fiber diameter of the nanofibers was 130 nm (1.5 × 10 ⁻⁴ dtex). The diameters of the nanofibers are shown in Table 12.

Example 17
A plain weave was woven using the polymer alloy fibers produced in Examples 1-6. Then, scouring was performed in 100 ° C. hot water (bath ratio 1: 100) in which the surfactant (Sanyo Kasei “Gran-up”) and sodium carbonate each had a concentration of 2 g / liter. The scouring time was 40 minutes. At this time, 99% or more of the hot water soluble polymer was dissolved and removed. And the intermediate set was performed at 140 degreeC. Thereafter, alkali treatment was performed for 2 hours with a 10% aqueous sodium hydroxide solution (90 ° C., bath ratio 1: 100) to remove 99% or more of the copolymerized PET as a sea component. Furthermore, the final set was given to this at 140 degreeC. Although the obtained fabric was dyed by a conventional method, it was a beautiful product without dyeing spots. The woven fabric comprising the nanofiber aggregate obtained here was excellent in texture with a “dry feeling” like rayon. Moreover, since ΔMR = 6% and excellent hygroscopicity, it was suitable for comfortable clothing. Furthermore, when this fabric was subjected to buffing treatment, it showed a super-peach feeling and a moist and fresh texture that could not be achieved with conventional ultra-fine fibers.

Comparative Example 6
A plain weave was produced in the same manner as in Example 17 using the N6 blend fibers produced in Comparative Examples 2 to 4, but because the spinning was unstable, there were many thick spots and fluff in the longitudinal direction of the yarn, Only woven fabrics with a lot of fluff and poor surface quality were produced. These were scoured, followed by an intermediate set. And what used the thread | yarn of the comparative example 2 performed the alkali treatment similarly to Example 17 , gave the final set, and also dye | stained according to the conventional method. On the other hand, those using the yarns of Comparative Examples 3 and 4 were immersed in toluene at 85 ° C. for 60 minutes to dissolve and remove 99% or more of PE. Then, the final set was given to these and dyeing was performed according to a conventional method. These fabrics were poor in quality with many dyed spots and fluff. Further, the texture is in the category of conventional ultra fine yarns, and there is no squeaky feeling or dry feeling, and the hygroscopicity is usually the same as that of N6 fibers (ΔMR = 2%).

Example 18
A high density plain weave was woven using the polymer alloy fibers produced in Example 4. And according to Example 17 , the plain weave which consists of nanofiber aggregates was obtained. Furthermore, as a result of analyzing the variation of the single fiber fineness of the nanofiber, the single fiber diameter based on the number average of the nanofibers is 86 nm (6 × 10 ⁻⁵ dtex), which is an unprecedented fineness, and the single fiber fineness is 1 ×. The fineness ratio of 10 ⁻⁷ to 1 × 10 ⁻⁴ dtex is 78%, especially the single fiber fineness ratio that falls between 75 to 104 nm in terms of single fiber diameter is 64%, and the single fiber fineness variation is very small. there were. And this was water-punched. This has better wiping performance than a conventional wiping cloth using ultrafine yarn, and is suitable as a wiping cloth.

Example 19
The polymer alloy fibers produced in Example 1 were combined into a 40,000 dtex tow and then subjected to mechanical crimping to obtain a crimped yarn having 8 crimps / 25 mm. This was cut into a fiber length of 51 mm, defibrated with a card, and then made into a web with a cross wrap weber. Next, 3000 needle / cm ² needle punches were applied to obtain a 750 g / m ² fiber-entangled nonwoven fabric. After adding polyvinyl alcohol to this nonwoven fabric, it was subjected to alkali treatment with 3% aqueous sodium hydroxide solution (60 ° C., bath ratio 1: 100) for 2 hours to remove 99% or more of the copolymerized PET. As a result of extracting and analyzing the nanofiber aggregate from the nanofiber structure, the single-fiber diameter based on the number average of the nanofibers is 60 nm (3 × 10 ⁻⁵ dtex), which is an unprecedented fineness, and the single-fiber fineness However, the fineness ratio of 1 × 10 ⁻⁷ to 1 × 10 ⁻⁴ dtex is 99%, particularly the single fiber fineness ratio is 70% between 55 to 84 nm in the single fiber diameter, and the single fiber fineness variation is very small. It was a thing. Further, a 13% by weight polyurethane composition (PU) mainly composed of polyether-based polyurethane and 87% by weight N, N′-dimethylformamide (DMF) are impregnated, and PU is added in a 40% by weight DMF aqueous solution. After solidification, it was washed with water to obtain a nanofiber structure having a thickness of about 1 mm composed of N6 nanofiber aggregates and PU. After buffing one surface with sandpaper to a thickness of 0.8 mm, the other surface is treated with an emery buffing machine to form a nanofiber aggregate raised surface, and after further dyeing, finishing and suede tone An artificial leather was obtained. The obtained product had a very good appearance, no staining spots, and no problem in mechanical properties. In addition, the touch was softer and finer than the conventional artificial leather using ultra-fine yarn. Moreover, since it is also excellent in hygroscopicity, it has an excellent texture that also has a freshness like human skin that cannot be possessed by conventional artificial leather.

Comparative Example 7
The N6 / PE blend fiber produced in Comparative Example 3 was subjected to mechanical crimping, then cut to a fiber length of 51 mm, defibrated with a card, and then made into a web with a cross wrap weber. Next, it was set as the fiber entangled nonwoven fabric of 500 g / m < ² > using the needle punch. Further impregnated with a liquid composed of 13% by weight polyurethane composition (PU) mainly composed of polyether polyurethane and 87% by weight N, N′-dimethylformamide (DMF), and solidified PU in a 40% by weight DMF aqueous solution. After washing with water. Further, the nonwoven fabric was subjected to a parkren treatment to obtain a nanofiber structure having a thickness of about 1 mm made of N6 superfine yarn and PU. After buffing one surface with sandpaper to a thickness of 0.8 mm, the other surface is treated with an emery buffing machine to form a nanofiber aggregate raised surface, and after further dyeing, finishing and suede tone An artificial leather was obtained. The texture of this is simply a suede imitation and does not exceed the conventional artificial leather using ultra-fine fibers.

Example 20
By using the polymer alloy fiber produced in Example 1, the same operation as in Example 19 was performed to obtain an abrasive cloth base material composed of an N6 nanofiber aggregate having a PU content of 40% by weight and a nanofiber structure composed of PU. . As a result of extracting and analyzing the nanofiber aggregate from the nanofiber structure, the single-fiber diameter based on the number average of the nanofibers is 60 nm (3 × 10 ⁻⁵ dtex), which is an unprecedented fineness, and the single-fiber fineness However, the fineness ratio of 1 × 10 ⁻⁷ to 1 × 10 ⁻⁴ dtex is 99%, particularly the single fiber fineness ratio is 70% between 55 to 84 nm in the single fiber diameter, and the single fiber fineness variation is very small. It was a thing. After cutting this into two parts, the surface was buffed with JIS # 240, # 350, # 500 sandpaper. Further, this was nipped with two upper and lower fluorinated heating rollers having a surface temperature of 150 ° C. with a gap of 1.0 mm, pressed at a pressure of 0.7 kg / cm ² , and then rapidly cooled with a cooling roller having a surface temperature of 15 ° C. A polishing cloth having a smooth surface was obtained. The results of evaluation of this polishing cloth by the following method are shown in Table 9. The polishing cloth has a higher smoothness of the object to be polished and has fewer scratches, which is a defect, as compared with the conventional method using super fine yarn. The characteristics are shown.

<Polishing Evaluation: Hard Disk Texturing>
Object to be polished: Substrate polished on Ni-P plating on a commercially available aluminum plate (average surface roughness = 0.28 nm)
Polishing conditions: The substrate was attached to a texture device and polished under the following conditions.
Abrasive grain: Free abrasive slurry dropping speed of diamond having an average particle diameter of 0.1 μm: 4.5 ml / min Rotational speed: 1000 rpm
Tape speed: 6 cm / min Polishing condition: Amplitude 1 mm-lateral vibration 300 times / min Evaluation number: 30 substrates / level.

<Average surface roughness Ra of the object to be polished>
The surface roughness of 30 substrates / level was measured using a Veeco original yarn force microscope (AFM) with a soundproofing device installed in a clean room at a temperature of 20 ° C. and a relative humidity of 50%, and the average surface roughness was measured. Find Ra. The measurement range is based on the center of the disk of each substrate, and two central points of the radius are selected symmetrically, and the measurement is performed at an area of 5 μm × 5 μm.

<Number of scratches>
The surface is observed with an interference microscope manufactured by ZYGO, and the number of surface scratches (X) of each sample is measured. Scratches with a size of 0.1 μm × 100 μm or more are counted. This is measured for 30 substrates / level, and the number of scratches β is defined from the score y based on the number of scratches.
When X ≦ 4 y = X
When X ≧ 5, y = 5
β = y ₁ + y ₂ +... + y ₂₉ + y ₃₀
Here, β is the total number of scratches for 30 samples.

Comparative Example 8
The N6 / PE blend fiber produced in Comparative Example 3 was subjected to mechanical crimping, then cut to a fiber length of 51 mm, opened with a card, and then made into a web with a cross wrap weber. Next, it was set as the fiber entangled nonwoven fabric of 500 g / m < ² > using the needle punch. Further impregnated with a liquid composed of 13% by weight polyurethane composition (PU) mainly composed of polyether polyurethane and 87% by weight N, N′-dimethylformamide (DMF), and solidified PU in a 40% by weight DMF aqueous solution. After washing with water. Further, this nonwoven fabric was subjected to Parkren treatment to obtain an abrasive base material composed of a nanofiber structure composed of N6 ultrafine yarn and PU. Using this, a polishing cloth was obtained in the same manner as in Example 22. And when this abrasive cloth was evaluated, Ra = 1.6 nm, β = 32 and the smoothness of the object to be polished was lower than that using the nanofiber assembly, and the number of scratches, which is a defect, increased. Inferior polishing characteristics.

Example 21
In the same manner as in Example 19 , using the polymer alloy fiber prepared in Example 1, a fiber entangled nonwoven fabric of 350 g / m ² was used, and then alkalinized with a 10% sodium hydroxide aqueous solution (90 ° C., bath ratio 1: 100). The treatment was performed for 2 hours to remove 99% or more of the copolymerized PET, and an N6 nanofiber nonwoven fabric was obtained. As a result of extracting the nanofiber aggregate from this nonwoven fabric and analyzing the dispersion of the single fiber fineness of the nanofiber, the single fiber diameter by the number average of the nanofibers is 60 nm (3 × 10 ⁻⁵ dtex), which is an unprecedented fineness. In addition, the fineness ratio of single fiber fineness of 1 × 10 ⁻⁷ to 1 × 10 ⁻⁴ dtex is 99%, and the single fiber fineness ratio that falls between 55 to 84 nm in terms of single fiber diameter is 70%. Yes, the single fiber fineness variation was very small. When this was cut into a circular shape with a diameter of 4.7 cm and five pieces of bovine blood containing white blood cells (5700 cells / μl) were passed through a circular filter column at a flow rate of 2 ml / min, pressure loss was reduced. The time required to reach 100 mmHg was 100 minutes, and the granulocyte removal rate at that time was 99% or more, and the lymphocyte removal rate was 60%, so that granulocytes, which are inflammatory leukocytes, can be selected. This is considered to be an effect due to the gap between the nanofibers.

Example 22
0.5 g of nanofiber nonwoven fabric prepared in Example 21 was sterilized by autoclaving, and the adsorption ability was evaluated with bovine serum containing 15 ml of endotoxin (37 ° C., 2 hours). The endotoxin concentration LPS was 10.0 ng / It decreased from ml to 1.5 ng / ml and showed excellent adsorption capacity. This is presumably because nylon nanofibers have much more active surfaces than normal nylon fibers, so that there are much more amino ends than usual.

Example 23
A spunbonded nonwoven fabric was obtained with the same polymer combination as in Example 13 using the apparatus of FIG. At this time, the melting temperature in the twin-screw extruder 23 was 225 ° C., the spinning temperature was 230 ° C., and the die surface temperature was 217 ° C. The base was the same as that used in Example 1, the single-hole discharge rate was 0.8 g / min, and the distance from the bottom of the base to the start of cooling was 12 cm. As a result of extracting fibers from the obtained nonwoven fabric and analyzing in the same manner as in Example 1, the number average diameter of the island domains in the polymer alloy fiber was 48 nm, the area ratio in the range of 1 to 80 nm in diameter was 80%, and the range in the range of 45 to 74 nm in diameter. The area ratio was 75%.

By treating the obtained polymer alloy nonwoven fabric with warm water at 60 ° C. for 2 hours, 99% or more of the hot water soluble polymer was dissolved and removed to obtain a nonwoven fabric composed of PLA nanofibers. The nanofiber single yarn diameter average is 50 nm (2 × 10 ⁻⁵ dtex), and 98% or more of the fineness ratio is in the range of single yarn fineness of 1 × 10 ⁻⁷ to 1 × 10 ⁻⁴ dtex. Although the single yarn diameter was in the range of 45 to 74 nm, the fineness ratio was 70%.

Example 24
The circular knitting made of the nanofiber assembly produced in Examples 1 to 6 was immersed in a 15% by weight aqueous solution of a polyurethane prepolymer (molecular weight 3000 to 4000) made of hexamethylene diisocyanate and a molecular weight 1000 hexamethylene polycarbonate. Thereafter, the circular knitting was pulled up to crosslink the polyurethane prepolymer at 120 ° C. for 20 minutes. By this operation, the polyurethane prepolymer that entered the voids between the nanofibers was insolubilized by the crosslinking reaction, and a composite composed of the crosslinked polyurethane and N6 nanofibers was generated. The obtained circular knitted composite had a large stretch property and a good surface touch with adhesiveness.

Example 25
The circular knitting made of the nanofiber aggregate produced in Examples 1 to 6 was immersed in ion-exchanged water, and then 1,2-bis (trimethoxysilyl) ethane was added and stirred for 3 hours. After standing at room temperature for 14 hours, the mixture was further stirred for 13 hours, further allowed to stand at room temperature for 14 hours, and further stirred for 7 hours to polymerize silica. Thereafter, the circular knitting was washed with ion-exchanged water and then air-dried. By this operation, a fabric-shaped N6 / silica composite using N6 nanofibers as a template was obtained. This was an excellent material having both sufficient rigidity and flexibility. It was also a hybrid material with excellent flame retardancy.

Example 26
By firing the N6 / silica composite obtained in Example 25 at 600 ° C., N6 used for the mold was removed, and a silica sheet having a large number of fine holes with a diameter of several tens of nm was obtained. This showed excellent adsorption and deodorization performance.

Example 27
The knitted fabric composed of the polyester nanofiber aggregates produced in Examples 9 to 12 was exhausted with “SR1000” (10% aqueous dispersion) manufactured by Takamatsu Yushi Co., Ltd. as a hygroscopic agent. The processing conditions at this time were 20% owf as the solid content of the hygroscopic agent, a bath ratio of 1:20, a processing temperature of 130 ° C., and a processing time of 1 hour. The exhaust rate of this hygroscopic agent to normal polyester fibers is almost 0%, but the exhaust rate to this polyester nanofiber aggregate is 10% or more, and ΔMR = 4% or more, which is equal to or better than cotton. A polyester knitted fabric having high hygroscopicity could be obtained.

Example 28
Methyltrimethoxysilane oligomer (n = 3-4) is dissolved in a mixed solution of isopropyl alcohol / ethylene glycol = 1/1, and 4% by weight of dibutyltin diacetate is used as a polymerization catalyst for a silicone polymer having a siloxane bond based on the silane oligomer. In addition, a silicone polymer coating solution was prepared. In this coating solution, the woven fabric composed of the N6 nanofiber assembly produced in Example 18 was immersed at 30 ° C. for 20 minutes, and sufficiently impregnated with the coating solution. The fabric is then lifted from the coating solution and dried at 60 ° C. for 2 minutes, 80 ° C. for 2 minutes, and 100 ° C. for 2 minutes, and the polymerization of silicone proceeds to obtain a fabric in which N6 nanofibers are coated with the silicone polymer. It was. This was a product showing excellent water repellency and flame retardancy.

Example 29
The knitted fabric made of the N6 nanofiber aggregate produced in Examples 1 to 4 showed a water content of 160% or more by its own weight and a water retention of 80% or more of its own weight, and was excellent in water absorption and water retention. Here, the moisture content and water retention rate were obtained by sufficiently immersing the sample in a water bath for 60 minutes, then measuring the weight (Ag) of the product from which the surface adhering water was removed and then removing it from a centrifugal dehydrator (3000 rpm for 7 minutes). The weight (Bg) of the dehydrated product was measured, and the weight (Cg) of the product dried at 105 ° C. for 2 hours was measured and calculated by the following equation.
Water content (%) = (A−C) / C × 100 (%)
Water retention rate (%) = (BC) / C × 100 (%)
Furthermore, the knitted fabric composed of this N6 nanofiber aggregate exhibited specific adhesiveness particularly in a state containing 15% or more of water.

Example 30
A patch material base fabric was prepared using the nonwoven fabric composed of the N6 nanofiber assembly prepared in Example 21 . When a medicine was applied to this, the exhaustion of the medicine was good, and excellent adhesiveness was exhibited, and an excellent patch material could be obtained.

Example 31
A bag was made from the knitted fabric made of the N6 nanofiber assembly produced in Example 1, and a cold-reserving agent wrapped in an inner bag was put therein. Since this water-cooled tool absorbs water condensed on the knitted fabric used for the bag and exhibits excellent adhesiveness, the heat-cooled tool is not easily displaced from the affected area and is excellent in handleability.

Example 32
The ability to remove chemical contaminants of the knitted fabric made of the N6 nanofiber assembly produced in Example 1 was evaluated as follows. 1 g of a sample piece was placed in a 0.005 m ³ (5 liter) Tedlar bag, and air containing chemical contaminants was introduced therein to a desired concentration. This polluted air was sampled over time, and the concentration of chemical contaminants in the Tedlar bag was monitored with a gas detector manufactured by Gastec or gas chromatography.

  Evaluation of removal of formaldehyde, trimethylamine, isovaleric acid, and dioctyl phthalate as chemical pollutants showed excellent removal ability (FIGS. 19-22).

Comparative Example 9
Using a commercially available PET nonwoven fabric, the ability to remove chemical contaminants was evaluated in the same manner as in Example 33, but there was almost no removal ability (FIGS. 19 to 22).

Example 33
Use of N6 used in Example 1, poly L lactic acid (optical purity of 99.5% or more) having a weight average molecular weight of 120,000, a melt viscosity of 30 Pa · s (240 ° C., 2432 sec ⁻¹ ) and a melting point of 170 ° C., and containing N6 The ratio was 20 wt%, the kneading temperature was 220 ° C., and melt kneading was performed in the same manner as in Example 1 to obtain a polymer alloy chip having a b ^* value = 3. The weight average molecular weight of polylactic acid was determined as follows. THF (tetrohydrofuran) was mixed with the sample chloroform solution to obtain a measurement solution. This was measured at 25 ° C. using water permeation gel permeation chromatography (GPC) Waters 2690, and the weight average molecular weight was determined in terms of polystyrene. The melt viscosity of N6 used in Example 1 at 240 ° C. and 2432 sec ⁻¹ ) was 57 Pa · s. Further, the melt viscosity of this poly L lactic acid at 215 ° C. and 1216 sec ⁻¹ was 86 Pa · s.

  This was melt-spun in the same manner as in Example 1 at a melting temperature of 230 ° C., a spinning temperature of 230 ° C. (die surface temperature of 215 ° C.), and a spinning speed of 3500 m / min. At this time, a normal spinneret having a base diameter of 0.3 mm and a hole length of 0.55 mm was used as the base, but almost no ballast phenomenon was observed, and the spinnability was greatly improved as compared with Example 1. The yarn breakage was zero in the continuous spinning for the time. The single-hole discharge rate at this time was 0.94 g / min. As a result, a highly oriented undrawn yarn of 92 dtex and 36 filaments was obtained, and the strength thereof was 2.4 cN / dtex, the elongation was 90%, the boiling water shrinkage was 43%, and U% = 0.7%. It was extremely excellent as an undrawn yarn. In particular, as the ballast was greatly reduced, the yarn spots were greatly improved.

  This highly oriented undrawn yarn was drawn and heat treated in the same manner as in 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 boiling water shrinkage of 9%, and U% = 0.7%.

  When the cross section of the obtained polymer alloy fiber was observed by TEM, PLA showed a sea-island structure where the sea (thin part) and N6 were islands (dense part), and the number average diameter of the island N6 was 55 nm. As a result, nano-sized and uniformly dispersed polymer alloy fibers were obtained.

The polymer alloy fiber obtained here was subjected to alkali treatment after circular knitting in the same manner as in Example 1 to hydrolyze and remove 99% or more of PLA in the polymer alloy fiber. As a result, a nanofiber aggregate was obtained. As a result of analyzing the single fiber fineness variation of the nanofiber in the same manner as in Example 1, the single fiber diameter based on the number average of nanofibers was 60 nm (3 × 10 ⁻⁵ dtex). The fineness of the single yarn was very small.

  The circular knitting made of this nanofiber assembly had a moisture absorption rate (ΔMR) of 6% and a water absorption swelling rate of 7% in the longitudinal direction of the yarn. Further, the yarn comprising this N6 nanofiber aggregate had a strength of 2 cN / dtex and an elongation of 45%. Further, the 140 ° C. dry heat shrinkage rate was 3%. Furthermore, when buffing was performed on this circular knitting, it showed a super-peach feeling and a moist and fresh texture like human skin that could not be achieved with conventional ultra-fine fibers.

Example 34
Polystyrene (co-PS) obtained by copolymerizing 22% of copolymerized PET and 2-ethylhexyl acrylate used in Example 9 with a content of copolymerized PET of 20% by weight and a kneading temperature of 235 ° C. Similarly, kneading was performed to obtain a polymer alloy chip having a b ^* value = 2. At this time, the melt viscosity of co-PS at 262 ° C. and 121.6 sec ⁻¹ was 140 Pa · s, and the melt viscosity at 245 ° C. and 1216 sec ⁻¹ was 60 Pa · s.

  This was melt-spun in the same manner as in Example 1 at a melting temperature of 260 ° C., a spinning temperature of 260 ° C. (die surface temperature of 245 ° C.), and a spinning speed of 1200 m / min. At this time, the same spinneret as that used in Example 1 was used as the base. The spinnability was good and the yarn breakage was 1 in 1 t spinning. The single-hole discharge rate at this time was 1.15 g / min. The obtained undrawn yarn was drawn at a temperature of 100 ° C. and a draw ratio of 2.49 times. A hot plate having an effective length of 15 cm was used instead of a hot roller as a heat setting device, and the heat setting temperature was 115 ° C., as in Example 1. Stretch heat treatment was performed. The obtained drawn yarn was 166 dtex, 36 filament, the strength was 1.2 cN / dtex, the elongation was 27%, and U% = 2.0%.

  When the cross section of the obtained polymer alloy fiber was observed with TEM, the sea-island structure in which co-PS was the sea (thin portion) and copolymerized PET was the island (dark portion), and the diameter by the number average of the copolymerized PET was A polymer alloy fiber having a size of 50 nm and having copolymerized PET uniformly dispersed in a nano size was obtained.

The polymer alloy fiber obtained here was circularly knitted in the same manner as in Example 1, and then immersed in tetrahydrofuran (THF) to elute 99% or more of the sea component co-PS. As a result, a nanofiber assembly was obtained. As a result of analyzing the single fiber fineness variation of the nanofiber in the same manner as in Example 1, the single fiber diameter based on the number average of the nanofibers was 55 nm (3 × 10 ⁻⁵ dtex). The fineness of the single yarn was very small.

  Further, this polymer alloy fiber was combined into a tow of 100,000 dtex, and then finely cut to a fiber length of 2 mm. Then, this was treated with THF, and co-PS was eluted to form nanofibers. The nanofiber-dispersed THF solution was solvent-substituted with alcohol and then water, followed by beating and papermaking to obtain a nonwoven fabric. The nonwoven fabric obtained here was a product in which nanofibers were dispersed to the single fiber level. This was optimal for medical products such as blood filters.

Example 35
The PBT used in Example 11 and the co-PS used in Example 34 were melt-kneaded in the same manner as in Example 1 at a PBT content of 20 wt% and a kneading temperature of 240 ° C., and b ^* value = 2 The polymer alloy chip was obtained.

  This was melt-spun in the same manner as in Example 1 at a melting temperature of 260 ° C., a spinning temperature of 260 ° C. (die surface temperature of 245 ° C.), and a spinning speed of 1200 m / min. At this time, the same spinneret as that used in Example 1 was used as the base. The spinnability was good and the yarn breakage was 1 in 1 t spinning. The single-hole discharge rate at this time was 1.0 g / min. The obtained undrawn yarn was subjected to drawing heat treatment in the same manner as in Example 35. The obtained drawn yarn was 161 dtex, 36 filaments, and the strength was 1.4 cN / dtex, the elongation was 33%, and U% = 2.0%.

  When the cross section of the obtained polymer alloy fiber was observed by TEM, the sea-island structure in which co-PS was the sea (thin portion), PBT was the island (dark portion), and the number average diameter of PBT was 45 nm, A polymer alloy fiber in which PBT was nano-sized and uniformly dispersed was obtained.

The polymer alloy fiber obtained here was circularly knitted in the same manner as in Example 1, and then immersed in trichlorethylene to elute 99% or more of the sea component co-PS. As a result, nanofiber aggregates were obtained. As a result of analyzing the single fiber fineness variation of the nanofibers in the same manner as in Example 1, the single fiber diameter based on the number average of the nanofibers was 50 nm (2 × 10 ⁻⁵ dtex). The fineness of the single yarn was very small.

Example 36
The PTT used in Example 12 and a copolymer PS manufactured by Nippon Steel Chemical Co., Ltd. (“Estyrene” KS-18, methyl methacrylate copolymer, melt viscosity 110 Pa · s, 262 ° C., 121.6 sec ⁻¹ ) were contained in PTT. The ratio was 20 wt%, the kneading temperature was 240 ° C., and melt kneading was performed in the same manner as in Example 1 to obtain a polymer alloy chip having a b ^* value = 2. The copolymer PS had a melt viscosity of 76 Pa · s at 245 ° C. and 1216 sec ⁻¹ .

This was melt-spun in the same manner as in Example 1 at a melting temperature of 260 ° C., a spinning temperature of 260 ° C. (die surface temperature of 245 ° C.), and a spinning speed of 1200 m / min. At this time, as shown in FIG. 13 as the base used in Example 1, as shown in FIG. 13, the metering part 12 having a diameter of 0.23 mm was provided on the upper part of the discharge hole, the discharge hole diameter 14 was 2 mm, and the discharge hole length 13 was 3 mm. A spinneret was used. The spinnability was good and the yarn breakage was 1 in 1 t spinning. The single-hole discharge rate at this time was 1.0 g / min. The obtained undrawn yarn is combined to form a tow, which is stretched 2.6 times in a 90 ° C. hot water bath to give mechanical crimps, cut to a fiber length of 51 mm, and unwound with a card. After fiber finishing, it was made into a web with a cross-wrap weber. Next, using a needle punch, a 300 g / m ² fiber-entangled nonwoven fabric was obtained. Further impregnated with a liquid composed of 13% by weight polyurethane composition (PU) mainly composed of polyether polyurethane and 87% by weight N, N′-dimethylformamide (DMF), and solidified PU in a 40% by weight DMF aqueous solution. After washing with water. Further, this non-woven fabric was treated with trichlorethylene, and the copolymer PS was eluted to obtain a nanofiber structure having a thickness of about 1 mm composed of PTT nanofibers and PU. After buffing one surface with sandpaper to a thickness of 0.8 mm, the other surface is treated with an emery buffing machine to form a nanofiber aggregate raised surface, and after further dyeing, finishing and suede tone An artificial leather was obtained. This artificial leather was not only softer and finer than conventional artificial leather, but also had an excellent texture rich in elasticity.

  When the cross section of the cut fiber was observed with a TEM, the copolymer PS showed a sea-island structure with the sea (thin part) and PTT with the island (dark part), and the number average diameter of the PTT was 50 nm. Nano-sized and uniformly dispersed polymer alloy fibers were obtained. This also had a single yarn fineness of 3.9 dtex, a strength of 1.3 cN / dtex, and an elongation of 25%.

Further, the yarn before being cut fiber was sampled, and this polymer alloy fiber was circularly knitted in the same manner as in Example 1 and then immersed in trichloroethylene to elute 99% or more of the copolymerized PS as a sea component. As a result, a nanofiber assembly was obtained. As a result of analyzing the single fiber fineness variation of the nanofiber in the same manner as in Example 1, the single fiber diameter based on the number average of the nanofibers was 55 nm (3 × 10 ⁻⁵ dtex). The fineness of the single yarn was very small.

Example 37
The co-PS used in PLA as in Example 34 used in Example 33, the content of PLA and 20 wt%, similarly melt-kneaded as in Example 34 the kneading temperature as 215 ° C., ^{b *} value = 2 The polymer alloy chip was obtained.

  This was melt-spun in the same manner as in Example 1 at a melting temperature of 230 ° C., a spinning temperature of 230 ° C. (die surface temperature of 215 ° C.), and a spinning speed of 1200 m / min. At this time, a spinneret having a discharge hole diameter of 2 mm and a measuring portion having a diameter of 0.23 mm above the discharge hole was used as the base. The spinnability was good and the yarn breakage was 1 in 1 t spinning. The single-hole discharge rate at this time was 0.7 g / min. The obtained undrawn yarn was subjected to drawing heat treatment in the same manner as in Example 35. The obtained drawn yarn was 111 dtex, 36 filaments, and the strength was 1.3 cN / dtex, the elongation was 35%, and U% = 2.0%.

  When the cross section of the obtained polymer alloy fiber was observed with TEM, co-PS showed the sea-island structure of the sea (thin part), PLA was the island (dark part), and the number average diameter of PLA was 40 nm, A polymer alloy fiber in which PLA was uniformly dispersed in a nano size was obtained.

Example 38
5 g of the circular knitting composed of the nanofiber aggregate produced in Example 33 was dried at 110 ° C. for 1 hour and immersed in a treatment liquid having the following composition for 2 hours to fully impregnate the nanofiber aggregate with diphenyldimethoxysilane. The treated fabric was sufficiently washed with pure water and then cured at 140 ° C. for 3 minutes to polymerize diphenyldimethoxysilane inside the nanofiber assembly. This was subjected to home washing 10 times, dried at 110 ° C. for 1 hour and measured for weight, which was a 38% increase in weight compared to untreated. Thus, the hybrid material can be obtained by carrying diphenyl silicone on the nanofiber aggregate, and the washing durability of diphenyl silicone was also good.

<Composition of treatment liquid>
Diphenyldimethoxysilane 100ml
100ml of pure water
300 ml of ethanol
50 drops of 10% hydrochloric acid.

Example 39
Squalane, which is a natural oil component extracted from the liver of salmon, was exhausted to the knitted fabric composed of the PBT nanofiber assembly produced in Example 35 , and had a skin care effect due to moisture retention. The treatment conditions at this time are a mixture of 60% squalane and 40% emulsifying dispersant dispersed in water at a concentration of 7.5 g / liter, a bath ratio of 1:40, a temperature of 130 ° C., and a treatment time of 60 minutes. After the treatment, washing was carried out at 80 ° C. for 2 hours, and the amount of squalane attached at this time was 21% by weight based on the fabric. Thereafter, the amount of squalane adhered after 20 home washings was 12% by weight with respect to the fabric, indicating sufficient washing durability.

  A sock was produced using a circular knitting made of this PBT nanofiber aggregate subjected to squalane processing, and a 10-week wearing test was conducted on 10 subjects with extremely dry heels. There were people. This is presumably because the squalane trapped in the nanofiber aggregate was gradually extracted by the subject's sweat and contacted the skin.

Example 40
N6 content was 35% and melt spinning was performed in the same manner as in Example 33 to obtain a highly oriented unstretched yarn of 400 dtex, 144 filaments of N6 / PLA polymer alloy. This highly oriented undrawn yarn was drawn and heat treated in the same manner as in Example 34. The obtained drawn yarn was 288 dtex, 96 filaments, and exhibited excellent properties of a strength of 3.6 cN / dtex, an elongation of 40%, a boiling water shrinkage of 9%, and U% = 0.7%.

When the cross section of the obtained polymer alloy fiber was observed with a TEM, PLA showed a sea-island structure where the sea (thin part) and N6 were islands (dense part), and the number average diameter of the island N6 was 62 nm. The area ratio in the range of 1 to 100 nm was 98%, and the area ratio in the range of 55 to 84 nm in diameter was 70%. Thus, a polymer alloy fiber in which N6 was nano-sized and uniformly dispersed was obtained. This was air-mixed with 165 dtex, 96 filament N6 false twisted yarn prepared separately while applying 15% overfeed. Then, this mixed fiber was subjected to a sweet twist of 300 turns / m, and a 2/2 twill woven fabric was produced using an S twist / Z twist twin yarn for warp and weft. The obtained twill fabric was subjected to alkali treatment in the same manner as in Example 34 to obtain a curtain fabric having a basis weight of 150 g / m ² made of N6 nanofibers. In this curtain fabric, N6 nanofibers were usually positioned so as to cover the N6 false twisted yarn, and the nanofibers were mainly exposed on the fabric surface. Furthermore, as a result of analyzing the single fiber fineness variation of the nanofiber in the same manner as in Example 1, the single yarn diameter by the number average of the nanofiber is 67 nm (4 × 10 ⁻⁵ dtex), which is an unprecedented thinness. The single fiber fineness is 1 × 10 ⁻⁷ to 1 × 10 ⁻⁴ dtex, and the fineness ratio is 98%. Particularly, the single fiber fineness ratio that falls between 55 to 84 nm in terms of single fiber diameter is 68%. The variation was very small. The N6 nanofibers had a strength of 2.0 cN / dtex and an elongation of 40%.

  Further, this curtain fabric was dipped in a 10 wt% aqueous solution of Silcote PP (specially modified silicone / trade name, manufactured by Matsumoto Yushi Co., Ltd.), and a treatment solution was applied to the curtain fabric so that the pickup rate of the aqueous solution was 150%. After applying the treatment liquid, it was dried in an oven at 110 ° C. for 3 minutes in a relaxed state. After drying, a spreading treatment was performed. The resulting curtain fabric showed a delicate touch and a moist and fresh texture like human skin. Further, there was a feeling of cool contact. Moreover, the moisture absorption rate (ΔMR) of this was 4%, indicating a sufficient hygroscopicity. When an acetic acid deodorization test was conducted, the concentration decreased from 100 ppm to 1 ppm in 10 minutes, and an excellent deodorizing property was exhibited. And when this fabric was used to produce a curtain and suspended between 6 tatami mats, it was possible to create a refreshing indoor environment and to suppress condensation. The curtain was put into a washing net with a household washing machine and washed and dehydrated, but it did not deform and showed good dimensional stability.

Example 41
N6 and copolymerized PET used in Example 3 were melt-kneaded in the same manner as in Example 1 with a blend ratio of N6 and copolymerized PET of 80% by weight / 20% by weight to prepare master pellets. The master pellets and the N6 virgin pellets used for melt kneading were charged into an independent hopper 1 and weighed independently by the measuring unit 24 and supplied to the blending tank 29 (7 kg capacity) (FIG. 23). At this time, the blend ratio of the master pellet and the N6 virgin pellet is 1: 1 by weight, and 20 ppm of antistatic agent (Emalmine 40, manufactured by Sanyo Chemical Industries Co., Ltd.) is used to prevent the pellet from adhering to the wall surface of the blending tank. Contained. Then, after the pellets were stirred in this blend tank, the pellets were supplied to the twin-screw extruder kneader 23 and melt-kneaded to obtain a polymer alloy having a N6 content of 40% by weight. At this time, the kneading part length was 33% of the effective screw length, and the kneading temperature was 270 ° C. Thereafter, the polymer melt was guided to the spin block 3 having a spinning temperature of 280 ° C. Then, melt spinning was performed in the same manner as in Example 3. This undrawn yarn was also drawn and heat treated in the same manner as in Example 3. The obtained polymer alloy fiber exhibited excellent properties of 120 dtex, 36 filaments, strength 3.0 cN / dtex, elongation 30%, U% = 3.7%. When the cross section of this polymer alloy fiber was observed with a TEM, as in Example 1, copolymer PET was sea, N6 was an island-island structure, and the number average diameter of island N6 was 110 nm. The area ratio of the island domain diameter in the range of 1 to 150 nm was 70%, and the area ratio of the island domain diameter in the range of 95 to 124 nm was 50%.

A nanofiber assembly was obtained by alkali treatment in the same manner as in Example 3 using the polymer alloy fiber obtained here. Furthermore, as a result of analyzing the variation in the single yarn fineness of these nanofibers in the same manner as in Example 1, the single yarn diameter based on the number average of nanofibers was 120 nm (1.3 × 10 ⁻⁴ dtex), which is a single yarn compared to Example 3. fineness thick, single yarn fineness variation is ^{large, 1 × 10 -7 dtex~1 × 10} -4 dtex fineness ratio less than 60% of the range of the ^{1 × 10 -7 dtex~2 × 10 -4} dtex The single yarn fineness ratio in the range was 95%. The fineness ratio in the range of single fiber diameter of 105 to 134 nm was 51%.

  Further, the moisture absorption (ΔMR) of the circular knitting made of this nanofabric aggregate was 5%, and the water absorption swelling rate in the longitudinal direction of the yarn was 7%. Further, the yarn composed of this N6 nanofiber aggregate had a strength of 1.2 cN / dtex and an elongation of 50%. Furthermore, the shrinkage percentage at 140 ° C. dry heat was 3%.

2 is a TEM photograph showing a cross section of the polymer alloy fiber of Example 1. FIG. It is a figure showing the single yarn fineness variation of the nanofiber of Example 1. FIG. 3 is a diagram showing variation in island domain diameter in the polymer alloy fiber of Example 1. 2 is an optical micrograph showing the state of the fiber side surface of the nanofiber assembly of Example 1. FIG. 4 is a SEM photograph showing the state of the fiber side surface of the nanofiber assembly of Example 1. 2 is a TEM photograph showing a cross-section of an aggregate fiber of nylon nanofibers of Example 1. FIG. FIG. 3 is a diagram showing reversible water swelling properties of Example 1. It is a figure showing the dispersion | variation in the island domain diameter in the polymer blend fiber of the comparative example 4. It is a figure showing the dispersion | variation in the island domain diameter in the polymer blend fiber of the comparative example 4. It is a figure showing the dispersion | variation in the island domain diameter in the polymer blend fiber of the comparative example 5. It is a figure showing the dispersion | variation in the island domain diameter in the polymer blend fiber of the comparative example 5. It is a figure which shows a spinning machine. It is a figure which shows a nozzle | cap | die. It is a figure which shows a drawing machine. It is a figure which shows a spinning machine. It is a figure which shows a spinning machine. It is a figure which shows a spinning machine. It is a figure which shows a spun bond spinning apparatus. It is a figure which shows the removal ability of formaldehyde of Example 32 . It is a figure which shows the removal capability of the trimethylamine of Example 32 . 4 is a graph showing the ability to remove isovaleric acid in Example 32. FIG. It is a figure which shows the removal capability of the dioctyl phthalate of Example 32 . It is a figure which shows a spinning machine.

Explanation of symbols

1: Hopper 2: Melting section 3: Spin block 4: Spin pack 5: Spindle 6: Chimney 7: Yarn 8: Converging oiling guide 9: First take-up roller 10: Second take-up roller 11: Winding yarn 12: Metering Part 13: discharge hole length 14: discharge hole diameter 15: undrawn yarn 16: feed roller 17: first hot roller 18: second hot roller 19: third roller (room temperature)
20: drawn yarn 21: 1-axis extrusion kneader 22: stationary kneader 23: biaxial extrusion kneader 24: chip metering device 25: ejector 26: spreader plate 27: opened yarn 28: collection device 29: blend Tank

Claims (15)

A sea- island-structured fiber consisting only of a polymer alloy, wherein the sea-component easily soluble polymer is polyethylene terephthalate and the island-soluble polymer is polyphenylene sulfide, and the number average diameter of the island domains is 1-150 nm. A polymer alloy fiber in which 60% or more of the area ratio of the island domain is in the range of 1 to 150 nm in diameter and the Wooster spot is 15% or less .
Island domain area ratio: The area of the island domain is S _i, and the total area is the total area (S ₁ + S ₂ +... S _n ).
And In addition, the frequency (number) of domains having the same area S is counted, and the product of the area and the frequency is calculated.
The area ratio of the island domain is divided by the total area. A sea-island structure fiber consisting only of a polymer alloy blended with at least two organic polymers having different solubilities, wherein the island component is a hardly soluble polymer and the sea component is a readily soluble polymer having a melt viscosity of 100 Pa · s or less. A polymer alloy fiber in which the number average diameter of the island domains is 1 to 150 nm, 60% or more of the area ratio of the island domains is in the range of 1 to 150 nm in diameter, and Wooster spots are 15% or less .
Area ratio of island domains: Let the area of island domains be S _i , and the sum total be the total area (S ₁ + S ₂ +... S _n ). Further, the frequency (number) of domains having the same area S is counted, and the product of the area and frequency divided by the total area is defined as the area ratio of the island domain. An easily soluble polymer sea component 2-ethylhexyl acrylate or methyl methacrylate click relay bets are copolymerized polystyrene, polymer alloy fiber according to claim 2, wherein low solubility polymer of the island component is a polyester. The polymer alloy fiber according to claim 2, wherein the easily soluble polymer of the sea component is polylactic acid, and the hardly soluble polymer of the island component is polyamide . A sea- island polymer alloy fiber consisting only of a polymer alloy, wherein the sea- soluble polymer is polyethylene terephthalate copolymerized with isophthalic acid and bisphenol A, and the island-soluble polymer is polyamide. The melting point of copolymer polyethylene terephthalate as a component is -20 to + 20 ° C. of the melting point of polyamide as an island component, the number average diameter of island domains is 1 to 150 nm, and the area ratio of island domains is 60% or more. A polymer alloy fiber having a Wooster plaque of 15% or less in a range of 1 to 150 nm .
Area of the island domains ratio: the area of the island domains as _{S i,} to the total sum and the total area _{(S 1 + S 2 + ...} S n). Further, the frequency (number) of domains having the same area S is counted, and the product of the area and frequency divided by the total area is defined as the area ratio of the island domain. The method for producing a polymer alloy fiber according to claim 1 , wherein polyethylene terephthalate and polyphenylene sulfide are melted separately, blended in a static kneader having a million or more divisions provided in a spinning pack, and then melt-spun . The polymer alloy fiber according to claim 5, wherein polyethylene terephthalate and polyamide copolymerized with isophthalic acid and bisphenol A are melted separately, blended in a stationary kneader of 1 million divisions or more provided in a spinning pack, and then melt-spun. Manufacturing method. A hot kneading polymer based on polyalkylene glycol as the sea component and a polymer selected from polyester, polyamide, polypropylene, and polycarbonate as the island component are melted separately, and a stationary kneader with more than 1 million divisions in the spinning pack. A polymer alloy in which the number average diameter of the island domains is 1 to 150 nm, the area ratio of the island domains is in the range of 1 to 150 nm in diameter, and the Worcester plaque is 15% or less. The manufacturing method of the polymer alloy fiber which consists only of.
Island domain area ratio: S of island domain area _i And the sum of the total area (S ₁ + S ₂ + ... S _n ). Further, the frequency (number) of domains having the same area S is counted, and the product of the area and frequency divided by the total area is defined as the area ratio of the island domain. By melt viscosity as the sea component melt spinning a blend of easily soluble polymers of the following 100 Pa · s, Ru to form a sea-island structure, according to claim 3 or 4 manufacturing method of a polymer alloy fiber as claimed. The polymer alloy according to claim 7, wherein the shear stress between the spinneret hole wall and the polymer alloy is 0.01 to 0.2 MPa · s at the time of melt spinning after kneading the two types of polymers with a biaxial kneader. A method for producing fibers. Two types of polymers are melted separately, kneaded in a static kneader of 1 million divisions or more provided in a spinning pack, and then melt-spun, the shear stress between the spinneret hole wall and the polymer alloy is set to 0.01. The manufacturing method of the polymer alloy fiber of Claim 7 which is set to -0.2MPa * s. A hot water-soluble polymer based on polyalkylene glycol as a sea component and polyester as an island component are melted separately, kneaded in a static kneader with a million or more divisions in a spinning pack, and then melt-spun, The number average diameter of the island domains is 1 to 150 nm and the shear stress between the pore wall and the polymer alloy is 0.01 to 0.2 MPa · s, and 60% or more of the area ratio of the island domains is 1 to 150 nm. The manufacturing method of the polymer alloy fiber which consists only of a polymer alloy in which the Wooster spot is 15% or less in the range.
Island domain area ratio: S of island domain area _i And the sum of the total area (S ₁ + S ₂ + ... S _n ). Further, the frequency (number) of domains having the same area S is counted, and the product of the area and frequency divided by the total area is defined as the area ratio of the island domain. A fiber product having at least a part of the polymer alloy fiber according to any one of claims 1 to 5 or the polymer alloy fiber obtained by the production method according to claims 6 to 12. The textile product according to claim 13, wherein the textile product is a woven or knitted fabric or a nonwoven fabric. The sea polymer is eluted from the polymer alloy fiber according to any one of claims 1 to 5, the polymer alloy fiber obtained by the production method according to claims 6 to 12, or the fiber product according to claim 13 or 14. The manufacturing method of the textiles containing the nanofiber whose number average diameter is 1-150 nm.