JP4797905B2 - Knitted fabric containing nanofiber fibers - Google Patents

Description

  The present invention relates to a knitted fabric containing nanofiber fibers, and relates to a knitted fabric excellent in morphological stability and washing fastness which has never been obtained.

  Polyester fibers typified by polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), and polyamide fibers typified by nylon 6 (N6) and nylon 66 (N66) have been used for apparel applications. In addition to modification, studies have been actively conducted on improving the performance of the cross-sectional shape of the fiber and ultrafine yarn. One of them is the production of ultra-fine polyester yarn using sea-island composite spinning, which is also used in knitted fabrics for peach touch clothing, wiping cloth for daily use and industrial materials, etc. Was desired.

Therefore, studies have been made on fibers finer than the micron level. Patent Document 1 describes a fiber structure composed of nanofibers of 1 to 150 nm, but does not disclose a dyed knitted fabric. As the name suggests, nanofiber fibers are fibers with a nano-level single fiber diameter, which is smaller than the typical dye size in micron units, and it is difficult to dye inside the single fiber, and it is retained on the surface of the single yarn fiber. Although it has been dyed in the form, it is easy to come off, so the fastness is poor, and there is a high risk of contaminating fibers other than nanofiber fibers. Develop dyed fabrics containing nanofiber fibers It was difficult. From the above, what was dye | stained with the fabric containing a nanofiber fiber was calculated | required.
JP 2004-162244 A

  In view of the background of such conventional technology, the present invention is a knitted fabric composed of nanofiber fibers and fibers exhibiting different dyeability from nanofiber fibers, and knitted fabric dyed only fibers exhibiting different dyeability from nanofiber fibers. It is intended to provide a knitted fabric with a low dimensional change rate and excellent washing fastness characteristics.

  The present invention employs the following means in order to solve such problems.

  [1] A nanofiber fiber assembly comprising a thermoplastic polymer and having a number average single fiber diameter of 10 to 200 nm is at least 10% by weight with respect to the total weight, and exhibits a dyeability different from that of the nanofiber fiber assembly. It is a knitted fabric containing 60% by weight or more of the total weight of the fiber, and a fiber having a dyeability different from that of the nanofiber fiber assembly is dyed. A knitted fabric characterized by having + 4% or less, a fading color of washing fastness of 4th grade or more, and contamination of 4th grade or more.

  [2] The knitted fabric according to claim 1, comprising a composite yarn having the nanofiber fiber assembly as a core yarn and a fiber having a dyeability different from that of the nanofiber fiber assembly as a sheath yarn.

  [3] The nanofiber fiber assembly is obtained from a sea-island type composite fiber, wherein the island component of the sea-island type composite fiber is a polyamide fiber of 20% by weight or more, and the sea component is polylactic acid. The knitted fabric according to claim 1 or 2, wherein sea components are eluted after knitting.

  [4] The nanofiber fiber assembly is not dyed, and a fiber having a different dyeing property from the nanofiber fiber assembly is dyed with a cationic dye. The knitted fabric described in.

  [5] The fiber exhibiting dyeability different from that of the nanofiber fiber assembly is any one selected from the group consisting of cationic dyeable polyester, acrylic fiber, wool, and silk. The knitted fabric in any one of -4.

  [6] The knitted fabric according to any one of claims 1 to 5, wherein the vertical and horizontal averages of the water absorption height by the birec method are both 80 mm or more.

  According to the present invention, there is provided a knitted fabric containing nanofiber fibers which are dyed knitted fabrics and have a small dimensional change rate and excellent fastness retention characteristics and water absorption performance.

Hereinafter, the present invention will be described in detail.
The nanofiber fiber referred to in the present invention refers to a fiber having a number average single fiber diameter of 1 to 250 nm, and a collection of nanofiber fibers is referred to as a nanofiber fiber assembly. The suppleness of the fiber is greatly influenced by the single fiber diameter, and the cross-sectional secondary moment, which is an index of resistance to bending, is proportional to the fourth power of the diameter. Therefore, if the single fiber diameter becomes 1/10, the cross-sectional secondary moment is It will be 1 / 10,000. That is, if the single fiber diameter becomes 1/10, the flexibility is considered to be 10,000 times. From this point, it is preferable that the single fiber diameter by the number average of the nanofiber fibers is smaller, and in the present invention, the single fiber diameter by the number average of the nanofibers is preferably 10 to 200 nm.

  Since the single fiber diameter of the nanofiber fiber assembly is 1/10 to 1/100 or less as compared with the conventional ultrafine yarn, the fiber surface area becomes very large, and the adsorption and absorption performance increases. In particular, the adsorption of water vapor, that is, the hygroscopic performance, was about 2.0% for the polyamide nanofiber fibers, whereas the hygroscopicity for the polyamide fine fibers was about 2.0%. In addition, the deodorization performance is improved by improving the adsorption performance. That is, since nanofiber fibers have a larger surface area than ordinary fibers, they have excellent odor gas adsorptivity and the deodorization rate after 100 minutes is 80% or more.

  In the present invention, the nanofiber fiber assembly having a single fiber diameter of 10 to 200 nm by number average is contained at least 10% by weight based on the total weight.

  In addition, the nanofiber fiber assembly is a collection of nanofiber fibers, and in particular, a bundle (bundle shape) is preferable. In such a form, a few nm to 100 nm between single fibers. Therefore, the water absorption performance is improved. For example, when a knitted fabric containing 10% by weight or more of bundle-like (bundle-like) nanofiber fiber aggregates, the water absorption performance by the Bayrec method was 8 cm or more. In the case of ordinary polyamide ultrafine yarn, the swelling ratio in the longitudinal direction due to water absorption is about 3%, whereas in the case of 100% by weight of the polyamide nanofiber fiber assembly, the swelling ratio may reach 7%. Moreover, since this water absorption swelling returns to its original length when dried, a reversible dimensional change occurs. Therefore, in order to set the dimensional change rate to -8% or more and + 4% or less for both vertical and horizontal, it is important that 60% by weight or more of fibers other than nanofiber fibers that do not absorb water swell are included.

  In addition, since the nanofiber fiber aggregate exhibits not only excellent water absorption characteristics but also excellent adsorption characteristics, it can carry various functional drugs and has excellent durability. A functional drug refers to a substance that can improve the function of a fiber. For example, a hygroscopic agent, a flame retardant, a water repellent, a preservative, a deodorant, a heat retention agent or a smoothing agent is also used as a target. Can do. The properties are not limited to those in the form of fine particles, and agents for promoting health and beauty such as polyphenols, amino acids, proteins, capsaicin, vitamins, and drugs for skin diseases such as athlete's foot can be used as targets. . Furthermore, pharmaceuticals such as disinfectants, anti-inflammatory agents, and analgesics can be used. Agents for adsorbing and decomposing toxic substances such as polyamines and photocatalyst nanoparticles can also be used. Also, there is no particular limitation on the method of supporting the functional drug, and it may be supported on the nanofiber fiber aggregate by post-processing by treatment in the bath or coating, or the polymer alloy fiber that is the precursor of the nanofiber fiber. It may be contained. In addition, the functional drug itself may be supported directly on the nanofiber fiber assembly, or after the functional drug precursor material is supported on the nanofiber fiber assembly, the precursor material is added to the desired functionality. It can also be converted into a drug. More specific examples of the latter method include impregnating nanofiber fiber aggregates with an organic monomer and then polymerizing it, or impregnating nanofiber fiber aggregates with an easily soluble substance by treatment in a bath. Later, there is a method of making it hardly soluble 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. .

  In addition, the nanofiber fiber according to the present invention preferably has a small variation in single fiber diameter and a small variation width in addition to the number average single fiber diameter of 10 to 200 nm. The weight ratio of the single fiber diameter of 200 nm or more is preferably 3% by weight or less. That is, in order to bring out the characteristics of the nanofiber fiber assembly, it is important that nanofibers having a single fiber diameter larger than 200 nm are close to zero. In particular, when the number average single fiber diameter is 10 to 150 nm, the weight ratio exceeding the single fiber diameter of 150 nm is preferably 3% by weight or less, more preferably 1% by weight or less. Furthermore, when the number average single fiber diameter is 10 to 100 nm, the weight ratio exceeding the single fiber diameter of 100 nm is preferably 3% by weight or less, more preferably 1% by weight or less. In other words, these mean that the presence of coarse single fibers is close to zero, and the performance of nanofiber fibers is demonstrated by the small dispersion of single fiber fibers, which stabilizes the quality of the knitted fabric. Property can also be improved.

Here, the weight ratio of the single fiber diameter variation of the nanofiber fiber is calculated by the following method. That is, the single fiber diameter was measured for each nanofiber fibers and di, the square of the sum ^{(d1 2 + d2 2 + ··} dn 2) = Σdi calculates ² (i = 1~n). Further, the diameter larger than 200 nm is set to Di, and the sum of the squares (D1 ² + D2 ² +.. Dm ² ) = ΣDi ² (i = 1 to m) is calculated. By calculating the ratio of ΣDi ² to Σdi ² , the area ratio of coarse fibers to all nanofibers, that is, the weight ratio can be obtained. Moreover, the single fiber diameter by the number average of the nanofiber was calculated as a simple average value ((d1 + d2 + .. dn) / n = Σdi / n (i = 1 to n)). In addition, what is necessary is just to measure the single fiber diameter of nanofiber fiber using commercially available image processing software etc. from the photograph image | photographed with the electron microscope.

  As an index of the dispersion of the nanofiber fibers, it is preferable that the fineness ratio of the single fibers having a single fiber diameter width difference of 30 nm is 50% or more. More preferably, it is 70% or more. The fineness ratio of the diameter difference of the single fibers means the degree of concentration of dispersion around the central fineness, and the larger the fineness ratio, the smaller the dispersion. This can also be calculated from the data used when determining the single fiber diameter.

  The polymer of the nanofiber fibers constituting the nanofiber fiber assembly used in the knitted fabric of the present invention is polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyester represented by polytrimethylene terephthalate (PTT), A polyamide represented by N6 or N66, a thermoplastic polymer represented by polyolefin or polyphenylene sulfide (PPS) is preferred. Among these, polymerization polymers represented by polyester and polyamide have a high melting point and are more preferable. When the melting point of the polymer is 165 ° C. or higher, the heat resistance of the nanofiber fibers is improved, which is preferable. For example, polylactic acid (PLA) is 170 ° C, N6 is 220 ° C, PTT and PBT are 225 ° C, and PET is 255 ° C. The polymer may contain additives such as particles, flame retardant, antistatic agent and the like. In addition, other components may be copolymerized as long as the properties of the polymer are not impaired. In the knitted fabric for clothing, PET, N6, and N66 are more preferable from the viewpoints of melting point, mechanical properties, and texture.

  The method for producing the nanofiber fiber aggregate used in the present invention is not particularly limited. For example, a polymer alloy fiber composed of a hardly soluble polymer and an easily refractory polymer is used as a precursor, and the polymer alloy fiber is easily melted. It can be obtained by removing the polymer. Here, as the easily meltable polymer, a polymer preferable for constituting the above-described nanofiber fiber may be used. Although the manufacturing method of the said polymer alloy fiber 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. And the nanofiber fiber assembly of this invention can be obtained by removing an easily soluble polymer with a solvent. Here, in the polymer alloy fiber that is the precursor of the nanofiber fiber assembly, the easily soluble polymer is the sea (matrix) and the hardly soluble polymer is the island (domain), and it is important to control the island size. is there. Here, the island size is obtained by observing the cross section of the polymer alloy fiber with a transmission electron microscope (TEM) and evaluating it in terms of diameter. Since the diameter of the nanofiber fiber is substantially determined by the island size in the precursor, the island size distribution is designed according to the diameter distribution of the nanofiber fiber of the present invention. For this reason, kneading of the polymer to be alloyed is very important, and in the present invention, high kneading is preferably performed by a kneading extruder, a stationary kneader or the like. In addition, since kneading is insufficient with simple chip blending, it is difficult to disperse islands with a size of several tens of nm as in the present invention. Specifically, as a guide when kneading, depending on the polymer to be combined, when using a kneading extruder, it is preferable to use a 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.

In addition, a combination of polymers is also important for ultra-fine dispersion of islands with a size of several tens of nanometers. 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.

  Further, it is preferable that the difference in melting point between polymers is 20 ° C. or less because kneading with an extrusion kneader makes it difficult to produce a difference in the melting state in the extrusion kneader, so that high-efficiency kneading is easy. In addition, when a polymer which is easily decomposed or thermally deteriorated is used as one component, it is necessary to keep the kneading and spinning temperature low, which is also advantageous. Here, in the case of an amorphous polymer, since there is no melting point, it is replaced by the glass transition temperature, Vicat softening temperature or heat distortion temperature.

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). P = (8LηQ / πR ⁴ ), η: polymer viscosity (poise), Q: discharge amount (cm ³ / sec), and π: circumference. 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 diameter of the obtained nanofiber.

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.
This production method makes it possible to obtain a polymer alloy fiber with a small dispersion of islands by ultrafine dispersion of island polymers by optimizing the combination of polymers and spinning / drawing conditions as described above. To do. In this way, by using polymer alloy fibers having small yarn irregularities in the longitudinal direction of the yarn as a precursor, it is possible to obtain a nanofiber fiber assembly with small single yarn fineness variation not only in a certain cross section but also in any cross section in the longitudinal direction. It is. It is preferable that the Worcester plaque of the polymer alloy fiber which is a precursor is 15% or less, more preferably 5% or less.

  The nanofiber fiber aggregate is obtained by eluting the readily soluble polymer, which is a sea polymer, with a solvent from the polymer alloy fibers thus obtained. In this case, use an aqueous solution as the solvent. Is preferable from the viewpoint of reducing the environmental load. Specifically, it is preferable to use an alkaline aqueous solution or hot water. For this reason, as an easily soluble polymer, hot water soluble polymers, such as a polymer hydrolyzed alkali, such as polyester and polycarbonate (PC), polyalkylene glycol, polyvinyl alcohol, and derivatives thereof are preferable. With such a manufacturing method, a nanofiber fiber assembly in the form of a spun yarn in which nanofibers having a fiber length of several tens of μm or more and possibly centimeters or more are adhered or intertwined is obtained. In addition, in the above production method, particularly when a stationary kneader is positioned directly above the die, a nanofiber fiber aggregate having a long fiber shape in which nanofibers are theoretically extended infinitely may be obtained.

In the present invention, unlike conventional nanofibers, nanofibers can be stretched and heat-treated for the first time by stretching and heat-treating polymer alloy fibers as precursors. Now you can control. Here, if the strength of the nanofiber fiber assembly of the present invention is 1 cN / dtex or more, it is preferable because the mechanical properties of the fiber product can be improved. The strength of the nanofiber fiber is more preferably 2 cN / dtex or more. In addition, the shrinkage rate of the nanofiber fiber assembly of the present invention can be adjusted according to the use, but when used for clothing, 140 ° C. and dry heat shrinkage are preferably 10% or less. Furthermore, it is possible to crimp the polymer alloy fiber as a precursor.
The nanofiber fiber assembly can be dyed normally, but because the discoloration due to washing is poor, the nanofiber fiber assembly is likely to fade with each wash, causing contamination to other fibers, Until now, a dyed knitted fabric satisfying fastness using a nanofiber fiber assembly has not been realized. The inventors of the present invention knitted a nanofiber fiber assembly and a fiber having a different dyeing property from the nanofiber fiber assembly, did not dye the nanofiber fiber assembly, and exhibited a different dyeing property from the nanofiber fiber assembly. It has been found that by dyeing only the fibers, it is possible to provide a product that exhibits dyeability as a whole when knitted.

  Known fibers, semi-synthetic fibers, and natural fibers can be used as the fibers exhibiting different dyeability from the nanofiber fiber assembly.

  The combination of the nanofiber fiber aggregate used in the present invention and the fiber exhibiting different dyeability from the nanofiber fiber aggregate is not particularly limited, but the fiber exhibiting different dyeability from the nanofiber fiber aggregate is dyed. It is important that the nanofiber fiber assembly is not dyed or contaminated. In addition, when the sea component polymer is eluted and removed from the polymer alloy fiber in order to obtain a nanofiber fiber assembly, it is important that fibers having different dyeability from the nanofiber fiber assembly are not eluted.

  For example, when the island-component nanofiber fiber aggregate that has eluted and remained the sea component polylactic acid is polyamide, the other fiber is preferably a cationic dyeable polyester. By preparing a knitted knitted fabric of a nanofiber fiber assembly made of polyamide and a cationic dyeable polyester, and performing cationic dyeing, the nanofiber fiber assembly made of polyamide is not dyed, and the color fastness of washing fastness is grade 4 , Can clear pollution grade 4.

  As another example of combination, when the sea component is polylactic acid and the nanofiber fiber aggregate is PBT or PTT, the fiber showing different dyeability from the nanofiber fiber aggregate is preferably nylon or cationic dyeable polyester. When the fiber having a dyeing property different from that of the nanofiber fiber assembly is nylon, it can be dyed with an acid dye, a metal-containing acid dye or a reactive dye, but PBT or PTT is not dyed. Moreover, when the fiber which shows dyeability different from a nanofiber fiber assembly is a cationic dyeable polyester, it can be dyed with a cationic dye, but PBT and PTT are not dyed. The cationic dye is a water-soluble dye whose dye ion is a cation and is called a basic dye. Cotton, silk, acrylic, or a basic dye-dyed modified polyester (cationic dyeable polyester) is dyed. PET, PBT, and PTT are dyed with a disperse dye and not dyed with a cationic dye.

  In addition, even if the nanofiber fiber assembly is a fiber showing any dyeability, it uses an original yarn or a pre-dyed yarn as a fiber showing a dyeability different from the nanofiber fiber assembly, and does not dye after knitting. Combinations are possible.

In addition, the fiber which shows the dyeability different from a nanofiber fiber assembly needs to be 60 weight% or more with respect to the knitted fabric total weight. When it is 60% by weight or more, it can be evaluated that it is dyed when dyeing fibers showing different dyeability from the nanofiber fiber aggregate, and a knitted fabric excellent in form stability with little dimensional change can be obtained. .
There is no particular limitation on the method of knitting the nanofiber fiber assembly and the fiber exhibiting different dyeability from the nanofiber fiber assembly. As a method of knitting, as a method of compounding with yarn, in the case of a composite yarn of long fibers of a nanofiber fiber aggregate and a long fiber showing different dyeability from the nanofiber fiber aggregate, it becomes a knitted fabric and is added to the product. If it does, it will become a beautiful knitted fabric. In addition, a knitted fabric made of a long and short composite yarn of a long fiber of a nanofiber fiber assembly and a short fiber having a dyeability different from that of the nanofiber fiber assembly. In addition, a knitted fabric made of a short and long composite yarn of short fibers of a nanofiber fiber assembly and long fibers exhibiting dyeability different from that of the nanofiber fiber assembly. In addition, a knitted fabric made of spun yarns of short fibers of a nanofiber fiber assembly and short fibers exhibiting dyeability different from that of the nanofiber fiber assembly. In any case, it is more preferable that the nanofiber fiber assembly is covered on the core side and the sheath side is a fiber exhibiting dyeability different from that of the nanofiber fiber assembly because unstained nanofiber fiber assemblies are covered. Moreover, it is also possible to constitute a reversible knitted fabric in which the nanofiber fiber aggregates are formed on the back surface of the knitted fabric and the fibers exhibit dyeability different from the nanofiber fiber aggregates on the surface. Further, a knitted fabric knitted by a combination of a nanofiber fiber assembly and a fiber exhibiting a different dyeability from the nanofiber fiber assembly may be used. The knitted fabric is dyed as a knitted fabric by arranging the nanofiber fiber aggregates in 10% by weight or more of the knitted fabric, and dyeing only the fibers that do not dye the nanofiber fiber aggregates and exhibit dyeability different from the nanofiber fiber aggregates. The knitted fabric can be developed for general clothing use.

  The knitted fabric of the present invention is not particularly limited to a knitted structure or the like. For example, a circular knitted fabric may be a single circular knitted fabric, a double circular knitted fabric, or a molded circular knitted fabric, and a warp knitted fabric may be a single tricot fabric, a double tricot fabric, a single raschel fabric, or a double knitted fabric. A raschel fabric can be used, and if it is a flat knitted fabric, a single flat knitted fabric, a double flat knitted fabric, or a molded flat knitted fabric can be used.

  In addition, the knitting structure is a circular knitted fabric, tengu reversible, milling, interlock, reversible, other change, warp half, back half, quince coat, satin, satin. There is no particular limitation such as a net organization, a power net organization, or other change organization. When stretchability is required depending on the application, it is preferable to knit polyurethane-based elasticity. At that time, the polyurethane-based elastic yarn is more preferably a high-setting type polyurethane that can be set at a low temperature. The polyurethane elastic yarn may be dyed or not dyed. When the polyurethane elastic yarn is "Lycra" (registered trademark) manufactured by Operontex, the nanofiber fiber aggregate is polyamide, and the fiber showing dyeability different from the nanofiber fiber aggregate is cationic dyeable polyester, cationic dyeing is performed. As a result, the polyamide, which is a nanofiber fiber assembly, is not dyed, the cationic dyeable polyester showing dyeability different from that of the nanofiber fiber assembly is dyed, and the “Lycra” is not dyed. It is more preferable because there is not.

  In addition to the fibers exhibiting different dyeability from the nanofiber fiber aggregate and the nanofiber fiber aggregate, it is also preferable to knit with polyamide fiber, cotton, hemp or the like that does not dissolve by elution depending on the application.

  Processing such as alkali elution treatment, scouring and dyeing in the present invention may be carried out in accordance with ordinary knitting fabric processing methods, and no special equipment is required. A flexible finishing process is preferable as an incidental process at this dyeing stage.

  In the knitted fabric of the present invention, when a phenomenon called warai occurs due to an increase in the gap between yarns due to elution of sea components, it is preferable to process the fabric with a silicon-based softener. As a result, the yarn and the yarn become slippery and the cracking phenomenon is eliminated. Further, by opening the nanofibers from the nanofiber fiber assembly by light raising, buffing or fir processing, it is possible to obtain a soft and peach knitted fabric that has not been obtained conventionally. Water repellent, antifouling, antibacterial, deodorant, flame retardant, sweat-absorbing, moisture-absorbing, anti-mold, UV-absorbing, etc. It is desirable to apply appropriately according to required characteristics such as wrinkling, raising, printing, or opal processing.

  The knitted fabric of the present invention can be developed for a wide range of uses as follows. For example, it can be preferably used for athletic wear, inner wear, home wear, uniform wear, outer wear, and for supporters, socks and the like for materials. In addition, it can be used for linings, shoe materials, gloves and the like without any problems. For athletic clothing, running shirts / pants, competition shirts / pants, golf shirts, tennis shirts, cycle shirts, outdoor shirts, polo shirts, T-shirts, baseball undershirts, training wear, sweatshirts / pants, etc. For innerwear, slips, camisole, petticoats, shorts, underpants, tights, T-shirts, round neck shirts, U-neck shirts, body suits, girdles, etc. for general ladies, T-shirts for general gentlemen, U-neck shirts, running shirts, underpants, tights, briefs, trunks, etc. In addition, sports inners including diversion of these inners, outdoor, skiing, etc., outdoor work, indoor work, etc. Work inners. For homewear, indoor clothes, pajamas, nightgowns, gowns, etc. For outerwear, women's clothes, men's clothes, children's clothes, work clothes, etc. If it is a lining material, it can be preferably used for sportswear, women's clothing, men's clothing, children's clothing, dressing clothes, student clothing, work clothing lining, and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. In addition, each evaluation in this invention was performed with the following method.

(1) Single fiber diameter by number average of nanofiber fibers An ultrathin section was cut out in the cross-sectional direction of the nanofiber fibers, and a fiber cross-sectional photograph was taken with a transmission electron microscope (TEM H-7100FA type). Using an image software (WINROOF), the single fiber diameter was calculated in terms of a circle, and the simple average value was defined as “number average single fiber diameter”. The number of nanofibers measured was 100 randomly extracted within the same cross section, and was measured at five locations (a total of 500).
Note that the island diameter of the polymer alloy fiber was measured in the same manner.

(2) Dimensional change rate JIS L1909 “Measurement method of dimensional change of textile products” (1995) 6.1 is used to mark a sample of a knitted fabric. After washing in accordance with method 103 (40 ° C.) of “Display Method” (1995), flat drying was performed. The dimensional change rate was measured by the following method.
Dimensional change rate (%) = (L2−L1) / L1 × 100
L1: Length before processing (mm), L2: Length after processing (mm)
(3) Washing fastness (discoloration, contamination)
In accordance with JIS L0844 “Testing method for dyeing fastness to washing” (1997), washing treatment was carried out by the A-2 method (50 ± 2 ° C.). 10. Judgment of discoloration and contamination is based on JIS L0801, “General Rules for Dye Fastness Test Method” (1995). Grading was performed according to the determination of the fastness to dyeing. In addition, as for the judgment of contamination, the worse one of the attached white cloth cotton and nylon was described.

(4) Water absorption (Bilec method)
According to JIS L1907 “Fabricity absorption test method for textiles” (2004), the heights of 5 vertical and 5 horizontal strips after 10 minutes were determined, and the average values were calculated. (Mm)
Example 1
Melting viscosity 212 Pa · s (262 ° C., shear rate 121.6 sec ⁻¹ ), melting point 220 ° C. N6 and weight average molecular weight 120,000, melt viscosity 30 Pa · s (240 ° C., shear rate 2432 sec ⁻¹ ), melting point 170 ° C. Using poly-L lactic acid (optical purity of 99.5% or higher), the content of N6 was 40% by weight and kneaded at 220 ° C. with a biaxial extrusion kneader to obtain a polymer alloy chip. The weight average molecular weight of polylactic acid was determined as follows. The sample chloroform solution was mixed with THF (tetrahydrofuran) to obtain a measurement solution. This was measured at 25 ° C. using Water Permeation Gel Permeation Chromatography (GPC) Water 2690, and the weight average molecular weight was determined by polystyrene approximation. Moreover, the melt viscosity of this poly L lactic acid at 215 ° C. and 1216 sec ⁻¹ was 86 Pa · s. 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 was positioned on the discharge side from 1/3 of the effective screw length.
In the middle, the N6 and poly-L lactic acid were separately reduced in weight and supplied separately to the kneader.
Temperature 220 ° C
2 vents This polymer alloy was melted at 230 ° C and led to a spin block with a spinning temperature of 230 ° C. Then, the polymer alloy melt was filtered with a metal nonwoven fabric having a limit filtration diameter of 15 μm, and then melt-prevented from the die with a die surface temperature of 215 ° C. at a spinning speed of 350 m / min. At this time, a normal spinneret having a base hole 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. The single-hole discharge rate at this time was 0.94 g / min. Thereby, after obtaining a highly oriented unstretched yarn of 92 dtex and 30 filaments, it was stretched at a stretching temperature of 90 ° C., a draw ratio of 1.3 times, and a heat setting temperature of 130 ° C. The obtained drawn yarn showed excellent properties of 78 dtex, 30 filaments, strength 3.6 cN / dtex, elongation 40%, boiling water shrinkage 9%, U% = 0.7%. A polymer alloy fiber having a sea-island structure in which N6 is an island component and poly-L-lactic acid is a sea component was obtained. When the cross section of the obtained polymer alloy fiber was observed with TEM, the number average average single fiber diameter (island diameter) was 80 nm, and a polymer alloy fiber in which N6 was ultradispersed was obtained.

  A cationic dyeable polyester, which is a modified polyester fiber containing 2% by weight of 5-sodium sulfoisophthalic acid and 1% by weight of polyethylene glycol, is used as a fiber exhibiting dyeability different from that of the nanofiber fiber assembly.

A 22 gauge, 33 inch (83.82 cm) double circular knitting machine with 84 dtex, 36 filaments of cationic dyeable polyester raw yarn in the front, and 22 dtex polyurethane elastic yarn ("Lycra" (registered trademark), operon) in the middle layer Tex Corporation 127C type), and on the back is a nylon 6 nanofiber fiber aggregate precursor (including 40% by weight as an island component) polymer alloy fiber 78 dtex, 30 filaments and cationic dyeable polyester One processed yarn of 84 dtex and 72 filaments was knitted alternately to obtain a living machine with 38 wells / 2.54 cm and 48 courses / 2.54 cm. After normal scouring of polyurethane elastic yarn knitted knitted fabric, the weight was reduced with 1.5% sodium hydroxide solution at 95 ° C for 30 minutes to elute and remove 99% or more of poly-L lactic acid, which is a sea component of polymer alloy fibers. did. Thereafter, intermediate setting was performed at 185 ° C., and then staining was performed at 90 ° C. for 30 minutes with Karacryl Blue 2RL-ED 0.1% omf manufactured by Nippon Kayaku Co., Ltd., which is a cationic dye. After soaping for 10 minutes at 80 ° C. with Rakkor PSK 2 g / L, sodium hydroxide 1 g / L manufactured by Meisei Chemical Co., Ltd. The treatment was performed for 60 minutes, and finishing set was performed at 170 ° C. Only the front and back cationic dyeable yarns were dyed, and the back nanofiber fiber assembly was not dyed. The finished density was 43 wells / 2.54 cm, 65 courses / 2.54 cm, and the basis weight was 180 g / m ² .

  When the cross section of the nanofiber fiber was observed with a TEM from the obtained product knitted fabric, the single fiber diameter by number average was 84 nm, and the coarse fiber having a diameter of 200 nm or more was 0.1% by weight or less. A few nanofiber fiber aggregates were obtained. The mixing ratio of the nanofiber fiber assembly was 12% by weight, the cationic dyeable polyester mixing ratio was 82% by weight as a fiber exhibiting dyeability different from the nanofiber fiber assembly, and the polyurethane mixing ratio corresponding to none was 6% by weight. . Table 1 shows the dimensional change rate, the fastness to washing, and the water absorption performance by Bilek.

Example 2
Under the same conditions as in Example 1, a 78 dtex, 30 filament polymer alloy fiber containing a nylon 6 nanofiber fiber assembly was obtained. A composite yarn was produced by fluid injection (taslan) processing using the polymer alloy fiber obtained above as a core and a raw yarn of cationic dyeable polyester 84 dtex 36 filament as a sheath. A composite processed yarn having a blend ratio of 40% by weight of the polymer alloy fiber of the core yarn and a yarn length difference of 10% from the cationic dyeable polyester, a total fineness of 162 dtex, and a surface exposure rate of the nanoalloy fiber aggregate of 30% was obtained. .

A 22 gauge, 33 inch (83.82 cm) double circular knitting machine with 162 dtex Taslan processed yarn in the front and 28 dtex polyurethane elastic yarn in the middle layer (“Lycra” (registered trademark), 178C type manufactured by Operontex) Was knitted, and a milled knitted fabric was knitted to obtain a living machine with 45 wells / 2.54 cm and 40 courses / 2.54 cm. After refining in the same manner as in Example 1, 99% or more of poly-L lactic acid, which is a sea component of the polymer alloy fiber, was eluted and removed. Thereafter, an intermediate set, dyeing with a cationic dye, soaping, perspiration treatment in bath, and finishing set were performed in the same manner as in Example 1. A toned knitted fabric dyed only on the front and back cationic dyeable yarns was obtained. The finished density was 53 wells / 2.54 cm, 40 courses / 2.54 cm, and the basis weight was 261 g / m ² .

  When the cross section of the nanofiber fiber was observed with a TEM from the obtained knitted fabric, the number average single fiber diameter was 86 nm, and the coarse fiber having a diameter of 200 nm or more was 0.1% by weight or less, and there was little variation. A nanofiber fiber assembly was obtained. The mixing ratio of the nanofiber fiber assembly was 20% by weight, the cationic dyeable polyester mixing ratio was 74% by weight as a fiber exhibiting dyeability different from that of the nanofiber fiber assembly, and the polyurethane mixing ratio corresponding to none was 6% by weight. Table 1 shows the dimensional change rate, the fastness to washing, and the water absorption performance by Bilek.

Example 3
Under the same conditions as in Example 1, a 78 dtex, 30 filament polymer alloy fiber containing a nylon 6 nanofiber fiber assembly was obtained. As a fiber having a dyeability different from that of the nanofiber fiber assembly, a 22 dtex polyurethane elastic yarn (“Lycra” (registered trademark), 127C type manufactured by Operontex) is used for the core, and 56 dtex for the sheath, 24 cations cation. FTY yarn covered with dyeable polyester and processed yarn of cationic dyeable polyester were used. 28 gauge, 30 inch (76.2cm) single circular knitting machine, F6 with cationic dyeable polyester, cationic dyeable polyester processed yarn 84 dtex, 36 filaments alternately with N6 nanofiber fibers Tendon reversible is knitted with a nanofiber fiber assembly of polymer alloy fibers, which is a precursor of the body, as a back thread. A living machine having 32 wells / 2.54 cm and 40 courses / 2.54 cm was obtained. Scouring and weight reduction were performed in the same manner as in Example 1, and 99% or more of poly-L lactic acid, which is a sea component of the polymer alloy fiber, was eluted and removed. Then, after performing an intermediate set by the same method as Example 1, it dye | stained with the cationic dye, the soap, the perspiration process in bath, and the finishing set by the same method as Example 1. Only a cationic dyeable yarn was dyed, and a knitted fabric in which the nanofiber fiber assembly was not dyed was obtained. The finished density was 45 wells / 2.54 cm, 44 courses / 2.54 cm, and the basis weight was 195 g / m ^{2 From} the obtained knitted fabric, the cross section of the nanofiber fibers was observed with TEM. The single fiber diameter was 85 nm, and coarse fibers having a diameter of 200 nm or more were 0.1% by weight or less, and nanofiber fibers with little variation were obtained. The mixing ratio of the nanofiber fibers was 22% by weight, the mixing ratio of the cationic dyeable polyester was 65% by weight as fibers exhibiting dyeability other than the nanofiber fiber aggregate, and the mixing ratio of polyurethane was 13% by weight as fibers not corresponding to any of them. Table 1 shows the dimensional change rate, the fastness to washing, and the water absorption performance by Bilek.

Comparative Example 1
Under the same conditions as in Example 1, a 78 dtex, 30 filament polymer alloy fiber containing a nylon 6 nanofiber fiber assembly was obtained. Smooth was knitted with 100% polymer alloy fibers on a 40 gauge, 30 inch (76.2 cm) double circular knitting machine. After normal scouring of the nylon knitted fabric, the weight was reduced by the same method as in Example 1, and 99% or more of poly-L lactic acid, which is a sea component of the polymer alloy fiber, was eluted and removed. Metal fiber acid dye (PM Blue 2R Matsuura Corporation (manufactured)) 0.5owf% nanofiber fiber assembly, Unibadine MC New (manufactured by Ciba Specialty Chemicals) 3.0owf% as leveling agent After dyeing at 1.0 ° C./min, dyeing temperature of 90 ° C., dyeing time of 30 minutes using 1.0 ammonium sulfate (manufactured by Sumitomo Chemical Co., Ltd.) as a pH adjusting agent, the same as in Example 1 After performing soaping and perspiration treatment in the bath by the method, FIX treatment of Dimafix ESB (manufactured by Meisei Chemical Industry Co., Ltd.) 3.0 owf at 80 ° C. for 20 minutes, finish setting at 180 ° C., and well 71 A nylon 6 nanofiber fiber assembly 100% by weight of knitted fabric / 2.54 cm and 58 courses / 2.54 cm was obtained.

  When the cross section of the nanofiber fiber was observed with a TEM from the obtained knitted fabric, the number average diameter was 84 nm, and the coarse fiber with a diameter of 200 nm or more was 0.1 wt% or less, and the nanofiber with little variation Fiber was obtained. The mixing ratio of the nanofiber fibers was 100% by weight. Table 1 shows the dimensional change rate, the fastness to washing, and the water absorption performance by Bilek.

Comparative Example 2
Under the same conditions as in Example 1, a 78 dtex, 30 filament polymer alloy fiber containing a nylon 6 nanofiber fiber assembly was obtained. Same as Example 1, 22 gauge, 33 inch (83.82 cm) circular knitting machine, 84 dtex, 36 filament cationic dyeable polyester raw yarn in the front, 22 dtex polyurethane elastic yarn ("Lycra" (trademark) in the middle layer (Registered), Operontex 127C type), and on the back is a nylon 6 nanofiber fiber aggregate precursor (including 40% by weight of island component) polymer alloy fiber 78 dtex, 30 filaments and cationic dye A processed yarn of provisional polyester 84 dtex and 72 filaments was knitted at a ratio of 1: 2 to obtain a living machine having 38 wells / 2.54 cm and 46 courses / 2.54 cm. Refining by the same method as in Example 1, eluting and removing 99% or more of poly-L lactic acid, which is a sea component of polymer alloy fiber, and by using the same method as in Example 1, intermediate set, cationic dyeing, soaping, sweat absorption in bath Processing and finishing set were performed. A knitted fabric in which only the front and back cationic dyeable yarns were dyed was obtained. The finished density was 43 wells / 2.54 cm, 63 courses / 2.54 cm, and the basis weight was 175 g / m ² . The resulting knitted fabric has a nanofiber fiber mixing ratio of 8% by weight, a cationic dyeable polyester mixing ratio of 86% by weight, and a polyurethane mixing ratio of 6% by weight, which is different from the nanofiber fiber assembly. there were. In addition, Table 1 shows the dimensional change rate, the fastness to washing, and the water absorption performance by Bilek.

Claims (6)

A total weight of fibers comprising a thermoplastic polymer and containing at least 10% by weight of a nanofiber fiber assembly having a number average single fiber diameter of 10 to 200 nm with respect to the total weight and exhibiting different dyeability from the nanofiber fiber assembly The knitted fabric contains 60% by weight or more of the fiber, and the fibers exhibiting dyeability different from that of the nanofiber fiber assembly are dyed, and the dimensional change rate is -8% or more and + 4% or less for both vertical and horizontal. The knitted fabric is characterized in that the color fastness to washing is 4 or more and the contamination is 4 or more. The knitted fabric according to claim 1, comprising a composite yarn having the nanofiber fiber assembly as a core yarn and a fiber having dyeability different from that of the nanofiber fiber assembly as a sheath yarn. The nanofiber fiber assembly is obtained from a sea-island type composite fiber, the island component of the sea-island type composite fiber is a polyamide fiber of 20% by weight or more, the sea component is polylactic acid, and after knitting into a knitted fabric, The knitted fabric according to claim 1 or 2, wherein sea components are eluted. The said nanofiber fiber aggregate is not dye | stained, The fiber which shows the dyeability different from the said nanofiber fiber aggregate is dye | stained with the cationic dye, The one in any one of Claims 1-3 characterized by the above-mentioned. Knitted fabric. The fiber showing dyeability different from the nanofiber fiber assembly is any one selected from the group consisting of cationic dyeable polyester, acrylic fiber, wool, and silk. The knitted fabric according to any one of the above. The knitted fabric according to any one of claims 1 to 5, wherein the vertical and horizontal averages of the water absorption height by the Bayrek method are both 80 mm or more.