JP2004316053A - Functional fiber structure using nanoporous fiber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a functional fiber structure different from conventional fiber structures, having good color development, durability and hand feeling after a functional processing and excellent in sustained release of medicinal agents. <P>SOLUTION: This functional fiber structure contains nanoporous fiber having ≤1.5% specific surface area of coarse pores having ≥200nm diameter over the whole cross section of the fiber, and in addition, a functional material. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention is characterized in that a functional material is contained in a fibrous structure composed of nanoporous fibers in which the area ratio of coarse pores having a diameter of 200 nm or more to the entire fiber cross section is 1.5% or less. It relates to a fiber structure.

  It is known to provide a functional agent to a fiber structure such as a woven or knitted fabric or a nonwoven fabric by post-processing. (1) The agent is exhausted to the fiber, (2) The agent is mixed with a binder and impregnated into the fiber structure And (3) mixing a drug with a resin and coating the fibrous structure. However, in the functionalization by the post-processing as described above, in the case of exhaustion, the amorphous region inside the fiber, in the case of fixation with the binder, the single fiber gap portion, and in the case of coating by coating, the surface layer portion of the fabric is used. In addition, there is a limit to the amount of drug to be applied. Further, when many chemicals are applied in order to pursue higher performance, there is a problem that the function inherent in the fiber itself, that is, bulkiness, and further the texture is impaired. In particular, in the case of fixing with a binder or the like, there is a problem that the durability is inferior due to the fixation to the surface layer portion of the cloth, and the functional agent falls off due to friction due to physical contact during use.

As one means for solving such a problem, the performance is improved by using a microporous fiber and a large amount of a functional agent (deodorant) is carried in the micropores, and at the same time, the washing durability is improved. In addition, a method of suppressing a reduction in texture is known (Patent Document 1). However, in the example described in the document, although the washing durability and the texture can be improved to some extent, the coloring property at the time of dyeing is small because the micropore diameter is on the submicron order (wavelength level of visible light). There was a problem that it was significantly reduced. Further, since the micropores are large, the surface area is not so different from that of ordinary fibers, and it cannot be said that the surface area is sufficient from the viewpoint of the loading efficiency of the functional drug. For this reason, a nanoporous fiber having a fine pore size on the nanometer order has been desired.
JP-A-1-292169 (pages 2-4)

  An object of the present invention is to provide a functional fiber structure that overcomes the above-described conventional problems, dramatically improves functional performance, has excellent texture and washing durability, and further has excellent coloring. And

  The above object is characterized in that a functional material is contained in a fibrous structure containing nanoporous fibers in which the area ratio of coarse pores having a diameter of 200 nm or more to the entire fiber cross section is 1.5% or less. This can be achieved by a functional fiber structure.

  The functional fiber structure composed of nanoporous fibers in which uniform nanopores are dispersed according to the present invention can dramatically improve the functionality as compared with the related art, and has good coloring, durability, and texture. Furthermore, a high value-added fiber product excellent in the sustained release performance of a drug can be obtained.

  The polymer constituting the nanoporous fiber of the present invention is a thermoplastic polymer such as polyester or polyamide, or a polyolefin, a thermosetting polymer such as a phenolic resin, a polyvinyl alcohol, or a polymer having poor thermoplasticity such as polyacrylonitrile. Although a biopolymer or the like is used, a thermoplastic polymer is preferred from the viewpoint of moldability. Among them, polyesters and polyamides have many high melting points and are more preferable. It is preferable that the melting point of the polymer is 165 ° C. or higher, since the heat resistance is good. For example, the temperature of polylactic acid (PLA) is 170 ° C., the temperature of polyethylene terephthalate (PET) is 255 ° C., and the temperature of nylon 6 (N6) is 220 ° C. Other components may be copolymerized as long as the properties of the polymer are not impaired, but the copolymerization ratio is 5 mol% or 5% by weight or less in order to maintain the inherent heat resistance and mechanical properties of the polymer. Is preferred. In particular, when used for clothing, interiors, vehicle interiors, etc., polyesters and polyamides are preferred in terms of melting point, mechanical properties, and texture, and nylon 6 and nylon having a copolymerization ratio of 5 mol% or less and 5 wt% or less and a relative viscosity of 2 or more. 66, PET having an intrinsic viscosity of 0.50 or more, polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), and PLA having a number average molecular weight of 50,000 or more are particularly preferable. It is preferable that these polymers constitute 80% by weight or more of the nanoporous fiber.

In the present invention, the nanoporous fiber refers to a fiber containing pores having a diameter of 100 nm or less in a cross section of the fiber at least 1 / μm ² . Thereby, the amount of exhaustion of the functional substance can be dramatically increased.

  It is important that the area ratio of the coarse pores having a diameter of 200 nm or more is 1.5% or less. Here, the area ratio is a value obtained by dividing the total area of the pores by the area of the entire fiber cross section. The wavelength of visible light is about 400 to 800 nm. However, since almost no coarse pores having a diameter of 200 nm or more are present, it is possible to remarkably reduce a decrease in the coloring property of a fiber structure containing nanoporous fibers. Here, the diameter and area of the pores can be estimated by cutting out an ultrathin section of the nanoporous fiber and observing the section with a transmission electron microscope (TEM). Since the pores may be elliptical or other distorted shapes and are not necessarily a perfect circle, the diameter is determined by converting the pore area into a circle. The entire fiber cross section refers to the area of the fiber cross section of a single fiber, and here refers to the area obtained by adding the polymer portion and the pore portion. These areas can be easily obtained by using image processing software such as WINROOF. Preferably, the area ratio of pores having a diameter of 50 nm or more is 1.5% or less, more preferably 0.1% or less.

  The average diameter of the pores of the nanoporous fiber is preferably 0.1 to 50 nm. When the average diameter of the pores is in this range, scattering of visible light hardly occurs and the pores become transparent with visible light. Furthermore, since the surface area of the fibrous structure including the nanoporous fiber is remarkably increased, a large amount of the functional substance can be exhausted, and the functionality which cannot be achieved by the conventional microporous fiber can be dramatically improved. it can. Further, it is possible to solve the problem of the post-processing such that the functional material is exhausted into the fine pores, and the property is generally hardened because the modification proceeds uniformly from the inside of the fiber, and the texture can be improved. Furthermore, it is possible to obtain a functional fiber structure excellent in sustained release properties such that the functional substance gradually seeps out of the inside of the micropores to the surface of the fiber structure. A more preferred average diameter of the pores is 0.1 to 30 nm.

  One example of the nanoporous fiber of the present invention is shown in FIG. 1 (a TEM photograph of a cross section of the N6 nanoporous fiber), and fine shading due to metal staining is observed. Here, the dark portion indicates the N6 high density region, and the light portion indicates the N6 low density region. Here, the light portion is considered to correspond to the pore. Further, these pores may be communication holes connected to each other or independent holes hardly connected. These pores can take the above-mentioned functional substance into the pores. In consideration of washing durability and sustained release properties, independent pores capable of encapsulating the taken-in functional substance to some extent are preferable.

  The functional substance in the present invention refers to a substance that positively imparts functionality to the fibrous structure, and is not particularly limited as long as it is a compound having a function. Substances that can exert their functions by post-processing are preferred. The functional substance may be an organic compound or an inorganic compound. In the case of inorganic fine particles, nanoparticles having a diameter of about 10 to 30 nm are preferable.

  The functional substance in the present invention only needs to be present in the nanoporous fiber, and the location and the state of the functional substance vary depending on the mechanism of expressing the functionality, but it is preferable that the functional substance is contained in the nanopore. The term "nanopore" as used herein refers not only to pores present inside the nanoporous fiber, but also pores (including nano-order fine irregularities on the fiber surface) present in the surface layer of the nanoporous fiber. Various forms are conceivable as a state in which the functional substance is present in the nanopores. Examples of the form include carrying by chemical bonding, exhaustion, and physical adsorption. In order to improve the functionality dramatically and improve the durability and texture, it is desirable to make use of the properties of the nanopores to make the functional substance exist, and the high number of nanopores present in the nanoporous fiber is high. The pore volume may be used to fill a large amount of the functional substance therein, or the functional substance may be supported on the surface using the high surface area of the nanopore. In the case where the functional substance is continuously present in the nanopore in the nanoporous fiber and the non-porous part adjacent thereto, the anchor effect of the functional substance by the nanopore (in the nanopore) (A state in which a functional substance is connected).

  Examples of the functionality in the present invention include UV cut, fragrance, deodorant, antibacterial, insect repellent, moisture absorption, antistatic, flame retardant, antifouling, beauty and health care, but are limited to these functions is not.

  Hereinafter, some examples of the functional substance having various functions will be specifically described, but the present invention is not particularly limited to these compounds.

  Examples of the functional substance having a function of blocking ultraviolet rays in the present invention include a benzotriazole compound, a p-aminobenzoic acid compound, a benzophenone compound, a salicylate compound, urocanic acid or a derivative thereof, arbutin or a derivative thereof, and an oxidized product. Ultrafine particles of titanium, zinc oxide, iron oxide, talc, kaolin, calcium carbonate and the like can be mentioned.

  Examples of the functional substance having an aroma function in the present invention include jasmine, lavender, aromatic substances extracted from flowers such as roses, those extracted from citrus fruits such as lemon and orange, and terpene-based substances mainly extracted from trees and the like. Compounds, substances having an aromatherapy effect as an effect and the like can be mentioned.

  Examples of the functional substance having a deodorizing function and a harmful gas removing function in the present invention include hydrogen peroxide, sodium sulfite, copper sulfate, zinc sulfate, iron sulfate, flavonoids, substances extracted from plants such as quince and mint, glyoxal. , Methacrylic acid esters, vinyl polymers such as polyacrylic acid and polymethacrylic acid in which zinc or copper is coordinated at the carboxyl group terminal, hydrazines such as diethylene triamine, adipic dihydrazide, sebacic dihydrazide, dodecane diacid dihydrazide, isophthalic dihydrazide, etc. Derivatives, polycarboxylic acid compounds, polyphenol compounds, wood vinegar, paradichlorobenzene, turpentine oil, eucalyptus oil, hydrolase, yeast, and the like.

  Examples of the functional substance having an antibacterial function in the present invention include a compound containing silver or zinc as a main component and an inorganic metal-based ultrafine particle, or a polymer compound such as a metal oxide-coordinated aminosilicon-based polymer or a zinc-coordinated acrylic acid polymer. Metal-based compounds, quaternary ammonium halide compounds such as cetyltrimethylammonium chloride and octadecyltrimethylammonium chloride, halodiallylurea-based compounds such as silicone quaternary ammonium, alkylamine derivatives, and triclocarban; chlorohexidine gluconate and polyhexamethylene biguanidine Guanidine compounds such as hydrochloride, phenolic compounds such as sodium alkylenebisphenol and parachlorometaxylenol, propylene glycol monofatty acid esters and glycerin fatty acid esters Which fatty acid ester-based compounds, chitosan, silk protein, natural-based compounds such as.

  Examples of the functional substance having an insect repellent function in the present invention include a bornyl alcohol derivative, dehydroacetic acid, N, N-diethylmethtoluamide, diphenyl ether type, phthalimide type, aromatic carboxylic acid ester type, organic phosphorus type, pyrethrins, Synthetic pyrethroid-based, pyrethroid-like, oxadiazole-based, amidinohydrazone-based compounds, and the like.

  Examples of the functional substance having the functions of absorbing moisture and absorbing water in the present invention include acrylic acid, methacrylic acid, itaconic acid, maleic acid, and a metal-substituted compound of a vinyl carboxylic acid polymer or copolymer composed of monomers such as butenetricarboxylic acid, Vinylsulfonic acid polymers and copolymers such as allylsulfonic acid, methacrylsulfonic acid and styrenesulfonic acid; polymers and copolymers such as acrylamide, methacrylamide and N-methylolmethacrylamide; higher alcohols, aqueous urethane resins and poly Examples thereof include ether epoxies, silicone compounds and emulsions thereof, hydrophilic polyester resins, polyethers of polyethylene glycol and polyethylene oxide, derivatives thereof, and polyhydric alcohols such as glycerin.

  Examples of the functional compound having an antistatic function in the present invention include anions and cations, as well as nonionic surfactants, betaine compounds, phosphate compounds, metal salts of alkyl sulfonic acids and alkyl phosphates, and alkyl salts. Amidoamine derivatives, polyamine compounds, polyacrylates / diamines / diglycidyl ethers, imidazolinium compounds, antistatic agents containing quaternary ammonium salts, condensation products such as ethylene oxide and propylene oxide, polyetheramides, polyethers Ether esters, polyether ester amides and the like can be mentioned.

  Examples of the functional substance having a flame-retardant function in the present invention include halogen-containing compounds such as hexabromobenzene, paraffin chloride, and hexabromocyclododecane; halogen-containing phosphorus compounds such as tris (2,3-dichloropropyl) phosphate; and polyphosphoric acid. Phosphorus compounds such as ammonium and trimethyl phosphate, nitrogen sulfur compounds, dibutylaminophosphate, halogen-containing polyurethane resins and their emulsions, brominated aromatic diols, calcium carbonate, magnesium hydroxide, magnesium carbonate, stannic oxide, metastannic acid And inorganic compounds such as stannous hydroxide.

  As the functional substance having an antifouling function in the present invention, a hydrophilic resin having a hydrophilic group such as polyethylene glycol, a fluorine-based resin or compound or an emulsion thereof, a silicone-based resin or compound or an emulsion thereof, wax Emulsions, fatty acid metal salts, derivatives of fatty acid amides and alkyl amides and the like can be mentioned.

  Examples of the functional substance having a beauty or health care function in the present invention include derivatives of vitamins such as vitamin C and vitamin E (provitamin), xylitol, capsaicin, raspberry ketone, mugwort, Amakusa, aloe extract, hyopia extract, and hinokitiol. Substances extracted from flowers and trees such as plants, fruits and vegetables, polyphenols such as catechin, amino acids such as arginine, glutamic acid, aspartic acid, glycine, serine, proline and cysteine, chondroitin sulfate Na, ceramide, trehalose, hyaluronic acid Drugs for promoting health and beauty such as acids, γ-linolenic acid, squalane, silk fibroin, sericin, collagen, lanolin, keratin, urea, polysaccharides, proteins, prohormones, kojic acid, γ-oryzanol And the like.

  In addition, drugs for skin diseases such as miconazole nitrate and econazole nitrate, and medicinal ingredients such as disinfectants, anti-inflammatory agents, and analgesics can also be mentioned.

  Further, by carrying a metal oxide, a metal, or the like, the catalyst can have catalytic activity.

  When processing these functional substances into nanoporous fibers, when a polar solvent or a polar dispersion medium such as water is used, it is assumed that the functional substance is hydrophobic, and that the nanoporous fibers are also composed of a hydrophobic polymer. The hydrophobic functional substance can easily migrate into the hydrophobic nanoporous fiber, which has lower polarity than the polar solvent, so that the content of the functional substance can be increased, and the hydrophobic functional substance hardly dissolves in water or the like. This is preferable because durability can be improved. Here, examples of the hydrophobic polymer include polyester and polyolefin. When used for clothing, polyester, especially PET, PTT, etc. are preferred. In addition, various substances can be exemplified as the hydrophobic functional substance, and examples thereof include oils and fats, and compounds containing an aromatic ring or a long alkyl chain.

  Further, as a preferable function processing method, the following method can be exemplified. This is a function processing method in which a nanoporous fiber is impregnated with a readily soluble functional material and then fixed to the nanoporous fiber as a hardly soluble functional material by a chemical reaction or counterion exchange. Here, the easily soluble functional substance means a substance which is easily dissolved in a solvent or easily dispersed in a dispersion medium. Then, the nanoporous fiber is impregnated with an easily soluble substance and then hardly dissolved to improve the washing durability. Here, various chemical reactions and counter ion exchange reactions can be mentioned as means for hardly solubilizing. Examples of the chemical reaction include an oxidation-reduction reaction, a substitution reaction, and a transfer reaction. For example, a method of impregnating a nanoporous fiber made of a hydrophilic polymer with an aqueous solution of silver nitrate and then making it hardly soluble in silver chloride by counter ion exchange, or a method of impregnating the nanoporous fiber with an aqueous solution of platinum chloride and reducing it to form platinum metal And a method of making it hardly soluble.

  As another method, there is a functional processing method in which a monomer is impregnated into a nanoporous fiber and then polymerized or crosslinked to fix the nanoporous fiber to the nanoporous fiber as a hardly soluble functional material. Here, the monomer includes not only the monomer but also an oligomer having a degree of polymerization of up to about 10. Examples of the monomer include not only inorganic monomers such as tetraethoxysilane (TEOS) and oils such as dimethyldiethoxysilane, but also raw materials for organic polymers such as polyurethane oligomers. Further, it is preferable that these monomers are rapidly polymerized or cross-linked by sol-gel reaction or heating and become hardly soluble.

  The strength of the nanoporous fiber used in the present invention is preferably 1.5 cN / dtex or more, since the tear strength and durability of the fiber product can be improved. The strength is more preferably 2.0 cN / dtex or more, even more preferably 2.5 cN / dtex or more. Further, it is preferable that the elongation is 20% or more because the durability of the fiber product can be improved.

  Further, the nanoporous fiber used in the present invention can adopt various fiber cross-sectional shapes such as a trilobal cross section, a cross cross section, and a hollow cross section. Further, even if the entire surface of the fiber cross section is nanoporous, the nanoporous portion may be localized on the fiber surface layer side or in the center, or on a portion deviated to eccentricity or the like. However, in order to sufficiently exhibit the excellent performance of the nanoporous fiber, it is preferable that the nanoporous portion has an area ratio of 30% or more with respect to the entire cross section of the fiber. Further, the nanoporous fiber of the present invention can be used alone, but it is possible to improve the dimensional stability of the fabric by mixing with normal synthetic fibers, synthetic fibers, and natural fibers by blending, blending, weaving, weaving and the like. Of course, it is possible to further improve the texture. Further, flat yarn or crimped yarn may be used, and various fiber product forms such as long fiber, short fiber, non-woven fabric, and thermoformed body can be adopted.

  Although the mixing ratio is not particularly limited, it is preferably 5 to 95%, and is appropriately selected depending on the purpose and the purpose of expressing the functionality.

  As described above, the nanoporous fiber used in the present invention can provide a high-quality dyed fabric that does not have a lowering of the coloring property as compared with the conventional porous fiber and that is excellent in hygroscopicity and adsorptivity. For this reason, it is not only used for comfortable clothing such as pantyhose, tights, inners, shirts, blousons, pants, and coats, but also for clothing materials such as cups and pads, interior uses such as curtains, carpets, mats, and furniture, and industrial applications such as filters. It can also be suitably used for material applications and vehicle interior applications. Furthermore, it can be used as a leading-edge material such as health and beauty related products, pharmaceutical base fabrics, fuel cell electrodes, and medical IT by adsorbing functional molecules.

  The method for producing the nanoporous fiber used in the present invention is not particularly limited. For example, the nanoporous fiber can be obtained by removing a readily soluble polymer from a polymer alloy fiber composed of a poorly soluble polymer and a readily soluble polymer.

  The method for producing the above-mentioned polymer alloy fiber is not particularly limited, but for example, the following method can be adopted.

  That is, the hardly soluble polymer and the easily soluble polymer are melt-kneaded to obtain a polymer alloy comprising the hardly soluble polymer and / or the easily soluble polymer in which the hardly soluble polymer and / or the easily soluble polymer is finely dispersed. Then, the polymer alloy fiber of the present invention can be obtained by melt-spinning this. Here, the melt kneading method is important, and the formation of coarse agglomerated polymer particles can be significantly suppressed by forcibly kneading with an extrusion kneader or a static kneader. For example, when a chip blend (dry blend) is used, the blend unevenness is large and aggregation of the island polymer cannot be prevented. From the viewpoint of forcible kneading, it is preferable to use a twin-screw extruder as an extrusion kneader, and to use a static kneader having a division number of 1,000,000 or more. When using a twin-screw kneading extruder, there are the following precautions.

  That is, when the hardly soluble polymer and the easily soluble polymer are measured and supplied independently and are melt-kneaded by the twin-screw extruder, it is preferable that the kneading part length is 20 to 40% of the effective screw length.

  Here, the method of supplying the polymer to be kneaded is important, and fluctuation of the blend ratio over time can be suppressed by separately measuring and supplying the hardly soluble polymer and the easily soluble polymer. At this time, they may be separately supplied as pellets or separately in a molten state. Further, two kinds of polymers may be supplied to the root of the extrusion kneader, or one of them may be provided as a side feed supplied from the middle of the extrusion kneader. It is also important to pay attention to the kneading conditions. In order to achieve both high kneading and suppression of the polymer residence time, it is preferable that the screw be of the same-direction completely meshing type. Further, the screw is composed of a feeding section (screw) and a kneading section (kneading disk section), and it is important that the kneading section length is 20 to 40% of the effective screw length. By setting the kneading section length to 20% or more, high kneading can be achieved, and by setting the kneading section length to 40% or less, excessive shear stress can be avoided and the residence time can be shortened. Deterioration can be suppressed. In addition, when the kneading is strengthened, a screw having a backflow function for feeding the polymer in the reverse direction in the extruder may be provided. The kneading temperature is preferably in the range of 20 ° C. to 50 ° C. higher than the melting point of the high melting point polymer from the viewpoint of suppressing the thermal degradation of the polymer alloy. Furthermore, by reducing the water content during kneading as a vent type, hydrolysis of the polymer can be suppressed, and the amount of amine end groups and carboxyl end groups and the amount of powder can be suppressed. The residence time of the polymer in the twin-screw extruder is preferably 10 minutes or less from the viewpoint of suppressing gelation, amide-ester exchange, and transesterification.

  Further, from the viewpoint of suppressing re-aggregation of the island polymer, the residence time from polymer alloy formation and melting to discharge from the spinneret is also important, and the time from the tip of the molten portion of the polymer alloy to discharge from the spinneret is 30 minutes. It is preferable to be within. In particular, in the case of an alloy of nylon and hydrophilic group-copolymerized PET, care must be taken because the hydrophilic group-copolymerized PET is likely to re-aggregate.

  Further, a combination of polymers is also important for miniaturization of the island diameter, and by increasing the affinity between the hardly soluble polymer and the easily soluble polymer, the easily soluble polymer which becomes an island can be easily microfinely dispersed. For example, when nylon is used as the poorly soluble polymer and polyethylene terephthalate (PET) is used as the easily soluble polymer, a hydrophilic group copolymerized PET obtained by copolymerizing PET with 5-sodium sulfoisophthalic acid (SSIA) as a hydrophilic component is used. When used, the affinity with nylon can be improved. In particular, it is preferable to use hydrophilic PET having an SSIA copolymerization ratio of 4 mol% or more. The melt viscosity ratio between the two is also important. As the viscosity ratio of the sea polymer / island polymer increases, a greater shearing force is applied to the island polymer, and the islands are more likely to be finely dispersed. However, an excessively large viscosity ratio causes kneading unevenness and deterioration of spinnability. Therefore, the viscosity ratio is preferably about 1/10 to 2.

  Due to the characteristics of the production method described above, the generation of coarse aggregated polymer particles is suppressed, so that the viscoelastic balance of the polymer alloy is less likely to be disrupted and the spinning discharge is stable, and the pulling is performed, as compared with the one using the chip blend. There is also an advantage that threadiness and thread spots can be significantly improved. Furthermore, if the diameter of the die hole is larger than usual, the shear stress to the polymer alloy in the die hole can be reduced and the viscoelastic balance can be maintained, so that the spinning stability is improved. Specifically, it is preferable to use a die capable of reducing the ejection linear velocity of the die of the polymer alloy to 15 m / min or less. In addition, the cooling of the yarn is also important, and the distance from the die to the active cooling start position is set to 1 to 15 cm. It can be stabilized.

  From the viewpoint of miniaturizing the island polymer, the spinning draft is preferably 100 or more. Further, in order to suppress changes with time of the dimensions and physical properties of the undrawn yarn, the spinning speed is preferably 2500 m / min or more to develop the fiber structure.

  As described above, the nanoporous fiber of the present invention can be obtained by using the polymer alloy fiber obtained by a manufacturing method different from the conventional one, which has a smaller pore size than the conventional one, and a coarse pore size. It is an excellent material that contains almost no and is applicable not only to clothing but also to various fields.

The present invention will be described in detail with reference to examples. In addition, the following method was used for the measuring method in an Example.
[Measuring method]
A. Melt viscosity of polymer The melt viscosity of the polymer was measured by Capillograph 1B manufactured by Toyo Seiki. In addition, the storage time of the polymer from the sample introduction to the measurement start was 10 minutes.

B. A 98% sulfuric acid solution having a relative viscosity of 0.01 g / ml of nylon was prepared and measured at 25 ° C.

C. Intrinsic viscosity of polyester [η]
Measured in orthochlorophenol at 25 ° C.

D. Melting point Using Perkin Elmaer DSC-7, the peak top temperature at which the polymer melted at 2nd run was defined as the melting point of the polymer. At this time, the heating rate was 16 ° C./min, and the sample amount was 10 mg.

E. FIG. Mechanical Properties At room temperature (25 ° C.), the tensile speed = 100% / min, and a load-elongation curve was determined under the conditions shown in JIS L1013. Next, the load value at break was divided by the initial fineness, which was taken as the strength, and the elongation at break was divided by the initial sample length, and the elongation curve was determined as the elongation.

F. Worcester spots of polymer alloy fiber (U%)
The measurement was performed in a normal mode at a yarn feeding speed of 200 m / min using USTER TESTER 4 manufactured by Zellbeger Worcester Co., Ltd.

G. FIG. Heat shrinkage Heat shrinkage (%) = [(L0−L1) / L0)] × 100 (%)
L0: The original length of the skein measured at an initial load of 0.09 cN / dtex after the drawn yarn was skeined. L1: The skein measured for L0 was treated in boiling water for 15 minutes in a substantially load-free state, and the initial load after air-drying Skein length under 0.09 cN / dtex Observation of cross section of fiber by TEM Ultra-thin sections were cut out in the cross section direction or the longitudinal section direction of the fiber, and the cross section of the fiber was observed with a transmission electron microscope (TEM). In addition, metal staining was performed as necessary.

TEM equipment: H-7100FA type manufactured by Hitachi, Ltd. Pore diameter or island polymer diameter The pore diameter was determined as follows. That is, the diameter of the island in terms of the circle was determined from the photograph of the fiber cross-section by TEM using image processing software (WINROOF). In addition, when the analysis was too fine or the shape was complicated and analysis by WINROOF was difficult, the analysis was performed visually and manually. The average diameter was determined from their simple number average. At this time, 300 or more randomly selected pores in the same cross section were used as the average pores. However, since the sample for TEM observation is an ultrathin section, the sample is liable to be broken or perforated. For this reason, the diameter analysis was performed carefully while checking the conditions of the sample. In addition, inorganic fine particles and hoists around the inorganic fine particles were not included in the pores. The island polymer diameter was based on the pore diameter analysis.

J. Content of functional substance The fabric before processing was dried at 110 ° C for 2 hours, and the weight was measured (W1). The fabric after functional processing was dried at 110 ° C. for 2 hours, and the weight was measured (W2). From the weight before and after processing, it was determined by the following equation.

Content = (W2−W1) / W1 × 100 (%)
K. Evaluation of Chromogenic Property The obtained sample was stained according to a conventional method, and the chromogenic property of a comparative sample stained under the same conditions was compared. As a comparative sample, a polymer formed of a nanoporous fiber by a conventional method was used. More specifically, the following method was used.

  In the case of nylon, "Nylosan Blue N-GFL" manufactured by Clariant Japan Co., Ltd. is used as the dye, and the dye is 0.8% by weight of the fiber product and a dyeing solution adjusted to pH 5 at a bath ratio of 100 times at 90 ° C. X 40 minutes.

  In the case of polyester, "Foron Navy S-2GL" manufactured by Clariant Japan Co., Ltd. is used as the dye, and the dye is 0.8% by weight of the fiber product and a dyeing solution adjusted to pH 5 at a bath ratio of 1: 100, 130. C. (110 ° C. for polylactic acid) for 40 minutes.

  In the visual judgment, those which obtained color development properties higher than or almost equal to the comparison (○) were slightly inferior to the comparison but were sufficient for clothing (△), and those which were inferior were rejected. (X).

L. Moisture absorption (ΔMR)
A sample is weighed in a weighing bottle in an amount of about 1 to 2 g, kept at 110 ° C. for 2 hours, dried and weighed (W0). Then, the target substance is kept at 20 ° C. and a relative humidity of 65% for 24 hours and then weighed. (W65). Then, it is kept at 30 ° C. and a relative humidity of 90% for 24 hours, and then its weight is measured (W90). Then, the calculation was performed according to the following equation.

MR65 = [(W65−W0) / W0] × 100% (1)
MR90 = [(W90−W0) / W0] × 100% (2)
ΔMR = MR90-MR65 (3)
CR (%) = [(L′ 0−L′1) / L′ 0] × 100 (%)
In addition, when the base fabric after processing was improved in ΔMR by 2% or more than that before the moisture absorption processing, it was evaluated that the hygroscopicity was good.

M. Evaluation of Flame Retardancy The test was performed in accordance with JIS L1091 Method D (flame contact test) of "Testing Method for Flammability of Textile Products". The number of times of flame contact was the average value of five tests. The flame resistance was evaluated to be good when the number of times of flame contact was 5 or more.

N. Evaluation of antibacterial activity This was based on the Manual for Quantitative Antibacterial Testing Method for Textile Products, which was established by the Evaluation Committee for New Functions of Textile Products. That is, a sterilized 1/20 concentration nutrient broth is uniformly inoculated with 0.4 g of a test bacterium (Staphylococcus aureus) at a concentration of 1 ± 0.3 × 10 ⁵ cells / ml at 37 ° C. Incubated for 18 hours. After the cultivation, the test bacteria are washed out, and a pour plate agar medium is prepared from the liquid, and cultured at 37 ° C. for 24-48 hours to measure the number of viable bacteria inoculated. The antibacterial activity was evaluated by the bacteriostatic activity value according to the following formula. The higher the bacteriostatic activity value was, the better the antibacterial property was, and it was evaluated that the antibacterial property was good at 4.0 or more.

Bacteriostatic activity value = log (B) -log (C)
However, the test must meet the following conditions: log (B) -log (A)> 1.5.
A: Average value of the number of bacteria collected immediately after inoculation of the raw product B: Average value of the number of bacteria collected and cultured for 18 hours of the raw product C: Average value of the number of bacteria collected and cultured for 18 hours of the processed product Evaluation of antistatic property The antistatic property was measured in accordance with the friction withstand voltage measurement method of JIS L1094 “Testing method for chargeability of woven and knitted fabrics”. It was evaluated that the antistatic property was good when the withstand voltage against friction was 300 V or less.

P. Evaluation of deodorant and harmful substance removal performance Under a humidified environment of a temperature of 20 ° C. and a humidity of 65% RH, 1 g of a cloth is placed in a 5 L tetrabag, and a predetermined concentration of a target odor or harmful substance is placed in the tetrabag. 3 L of gas was injected, and the gas concentration in the tetrabag was measured after 10 minutes using a gas detector tube (manufactured by Gastech Co., Ltd.). When the concentration became 1/10 or less of the initial concentration, it was evaluated that the deodorizing property and the harmful substance removing performance were good.

Q. Evaluation of insect repellency The cloth was wrapped around the arm, the arm was placed in a cage containing about 1200 Aedes albopictus for 2 minutes, and the number of rednesses after 15 to 20 minutes was counted. In addition, when the number of redness was 10 or less, it was evaluated that the insect repellency was good.

R. UV cut The UV transmittance of the measurement sample was measured with a spectrophotometer in the wavelength range of 290 nm to 400 nm, and the area difference between the sample and the blank (blank) was calculated. In addition, when the ultraviolet ray cut rate was 80% or more, it was evaluated that the performance of ultraviolet ray cut was good.

S. Evaluation of antifouling property The sample was contaminated with a mixture of sauce, coffee, mayonnaise, and beer, and after standing for 10 minutes, washed in the same manner as JIS L-1045. Was evaluated in three grades of ○ (good), Δ (somewhat good), and × (poor).

T. General washing test method The processed base fabric was subjected to 25 cycles of washing (15 minutes) → dehydration (1 minute) → rinsing (6 minutes) → dehydration (1 minute) → drying. The washing conditions were a water temperature of 40 ° C., a bath ratio of 1:30, and a detergent of “top” (manufactured by Lion Corporation) 0.5 g / l. The rinsing condition was a water temperature of 20 ° C., and the bath ratio was overflow.
[Preparation of base cloth]
Reference Example 1 (Base cloth A)
Relative viscosity 2.15, melt viscosity 31 Pa · s (275 ° C., shear rate 1216 sec ⁻¹ ), N6 (80% by weight) having a melting point of 220 ° C., intrinsic viscosity 0.60, melt viscosity 200 Pa · s (275 ° C., shear rate) 1216 sec ^-1 ), melted and kneaded at 260 ° C. with a twin-screw extruder under the following conditions using a copolymerized PET (20% by weight) obtained by copolymerizing 5 mol% of 5-sodium sulfoisophthalic acid having a melting point of 250 ° C. Obtained. The copolymer PET contained 0.05% by weight of titanium oxide.

Screw model: Same direction complete meshing type 2 thread screw Screw: Diameter 37 mm, effective length 1670 mm, L / D = 45.1
Kneading part length is 28% of screw effective length
The kneading part is located on the discharge side from 1/3 of the effective screw length
There are three backflow sections on the way. Polymer supply: N6 and copolymerized PET are separately measured and separately supplied to the kneader. Temperature: 260 ° C
Vent: 2 places Then, this polymer alloy chip was melted in the melting section 2 at 270 ° C., and led to a spin block at a spinning temperature of 275 ° C. Then, the polymer alloy melt was filtered with a metal nonwoven fabric having a critical filtration diameter of 15 μm, and then melt-spun (FIG. 8). At this time, the residence time from the melting part 2 to the discharge was 10 minutes. As shown in FIG. 9, a die having a measuring portion 11 having a diameter of 0.2 mm above the discharge hole, having a discharge hole diameter 13 of 0.5 mm and a discharge hole length 12 of 1.25 mm was used. At this time, the discharge rate per single hole was 2.1 g / min, and the die discharge linear velocity of the polymer alloy was 10 m / min. The distance from the lower surface of the base to the cooling start point (upper end of the chimney 5) was 9 cm. The discharged yarn is cooled and solidified for 1 m by a cooling wind of 20 ° C., and after being refueled by a refueling guide 7 installed 1.8 m below the base 4, a first heating roller 8 and a second heating roller 8 which are not heated. 9 at 3800 m / min. The spinnability at this time was good, and the breakage during continuous spinning for 24 hours was zero. Further, there was no package collapse due to swelling of the wound package with time, which is a problem with nylon, and the handleability was excellent. Then, this was subjected to stretch false twisting using the apparatus shown in FIG. At this time, the stretching ratio was 1.3 times, the temperature of the heater 23 was 165 ° C., the urethane disk triaxial twister was used as the rotor 25, and the D / Y ratio was 1.65. The obtained 50 dtex, 12 filament false twisted yarn exhibited excellent physical properties of a strength of 3.5 cN / dtex, an elongation of 29%, a heat shrinkage of 8%, and a CR of 38% (Table 1). Further, when the cross section of the obtained polymer alloy crimped yarn was observed with a TEM, N6 showed a sea-island structure (dark portion) and copolymerized PET showed a sea-island structure (island) (FIG. 2). A polymer alloy fiber having a diameter of 25 nm and ultrafine dispersion of copolymerized PET was obtained. The area ratio of the island having a diameter of 200 nm or more to the whole island was 0.1% or less, and the area ratio of the island having a diameter of 100 nm or more was 0.9%. Here, the area ratio with respect to the entire island refers to the ratio of the area of the island component to the total area, and is a measure of the coarse aggregated polymer. In addition, it was found from the fiber longitudinal section TEM observation that the islands formed a streak structure (FIG. 3).

  A circular knit was prepared as the polymer alloy crimped yarn S-twisted / Z-twisted double yarn and immersed in a 3% aqueous sodium hydroxide solution (95 ° C., bath ratio 1: 100) for one hour to obtain a polymer alloy fiber. 99% or more of the copolymerized PET was removed by hydrolysis. Then, it was washed with water and dried. Thus, a circular knit made of N6 nanoporous fiber was obtained.

  When the cross section of the fiber of this N6 nanoporous fiber was observed by TEM (FIG. 1), there were no coarse pores having a diameter of 50 nm or more, and the average diameter of the pores was 25 nm. Here, the dark portion corresponds to the N6 polymer, and the thin portion corresponds to the pores, but the pores were found to be independent pores.

  When the mechanical properties of N6 were measured, the strength was 2.6 cN / dtex and the elongation was 30%, indicating sufficient mechanical properties as a fiber product. Table 2 shows the physical properties of the N6 nanoporous fiber.

Reference Example 2 (Base fabric B)
Using the polymer alloy chip obtained in Reference Example 1, the melt spinning was performed in the same manner as in Reference Example 1, except that the discharge rate and the number of holes were changed, and the spinning speed was 900 m / min. At this time, the residence time from the melting part 2 to the discharge was 12 minutes. The spinnability was good, with no breakage during 24 hours of continuous spinning. Further, there was no package collapse due to swelling of the wound package with time, which is a problem with nylon, and the handleability was excellent. This was subjected to stretching heat treatment at a temperature of the first hot roller 16 of 70 ° C. and a temperature of the second hot roller 17 of 130 ° C. (FIG. 10). At this time, the stretching ratio between the first hot roller 16 and the second hot roller 17 was set to 3.2 times. The obtained polymer alloy fiber exhibited excellent properties of 70 dtex, 34 filaments, strength of 3.7 cN / dtex, elongation of 47%, U% = 1.2%, and heat shrinkage of 11%. When the cross section of the obtained polymer alloy fiber was observed with a TEM, N6 showed a sea-island structure in which the sea (dark portion) and the copolymerized PET showed an island (thin portion) (FIG. 4). A polymer alloy fiber having a diameter of 38 nm and ultra-dispersed copolymerized PET was obtained. The islands having a diameter of 200 nm or more accounted for 1.2% of the area of the entire island. A cross-sectional TEM photograph of the melt-kneaded polymer alloy chip is shown in FIG. 5, where the island polymer is ultrafinely dispersed to a particle size of 20 to 30 nm, and is equal to or less than the island polymer diameter in the fiber cross section (FIG. 4). Met. The polymer is stretched to about 500 times through the drawing from the discharge of the die, and the island polymer diameter should be reduced to 1/22 or less of that in the polymer alloy in the fiber cross section. The fact that the diameter of the island polymer is larger indicates that the island polymer has re-agglomerated from the melting of the polymer alloy to the discharge of the die. It can be seen that it is important to appropriately select spinning conditions as in this reference example. Table 1 shows the physical properties of the polymer alloy fibers. Further, it was found from the fiber longitudinal section TEM observation that the island had a streak structure.

  A circular knit is prepared using the polymer alloy fiber obtained here, and this is immersed in a 3% aqueous sodium hydroxide solution (95 ° C., bath ratio 1: 100) for 1 hour to copolymerize the polymer alloy fiber. More than 99% of PET was hydrolyzed and removed. Then, it was washed with water and dried.

  When the fiber side surface of this N6 nanoporous fiber was observed with an optical microscope, the fiber diameter was slightly reduced as compared with the fiber before the alkali treatment, and it was found that shrinkage occurred in the fiber radial direction by removing the island polymer. Do you get it. Next, when the side surface of the fiber was observed with a SEM, at a magnification of about 2000 times, no irregularities were observed on the fiber surface, and the surface was clean. When the cross section of the fiber of the N6 nanoporous fiber was observed with a TEM, the average diameter of the pores was 35 nm, and 0.3% of the pores having a diameter of 50 nm or more. When the longitudinal section of the fiber was observed, it was determined that the pores were independent pores.

  When the mechanical properties of the N6 nanoporous fiber were measured, it was found that the strength was 2.0 cN / dtex and the elongation was 70%, indicating sufficient mechanical properties as a fiber product. Table 2 shows the physical properties of the N6 nanoporous fiber.

Reference Example 3 (Base cloth C)
Melt spinning was performed in the same manner as in Reference Example 1, and direct spinning was performed using the apparatus shown in FIG. At this time, the discharge amount per single hole and the number of die holes are changed, and the peripheral speed of the first hot roller 27 is 2000 m / min, the temperature is 40 ° C., the peripheral speed of the second hot roller 28 is 4500 m / min, and the temperature is 150 ° C. and 55 dtex. , 12 filaments, a strength of 4.4 cN / dtex, an elongation of 37%, a U% of 1.2% and a heat shrinkage of 12% were obtained. The spinnability was good, and the yarn breakage was zero after 24 hours of spinning. None of the obtained polymer alloy fibers contained coarse agglomerated polymer particles, islands having a diameter of 200 nm or more were 0.1% or less in area ratio with respect to the entire island, and islands having a diameter of 100 nm or more were 1.0 in area ratio. %Met. Further, it was found from the fiber longitudinal section TEM observation that the island had a streak structure. In addition, the yarn properties were excellent as shown in Table 1.

  Circular knitting was produced using this polymer alloy fiber, and 99% or more of the copolymerized PET was removed by alkali treatment to obtain a circular knitting made of N6 nanoporous fiber.

When the cross section of the fiber of this N6 nanoporous fiber was observed by TEM, the density spots due to metal staining became finer than the original polymer alloy fiber, and the pore size became finer than the original island polymer by removing the island polymer. However, there were no large pores of 50 nm or more. From TEM observation, these pores were determined to be independent pores. When the mechanical properties of the N6 nanoporous fiber were measured, it was found that the strength was 3.4 cN / dtex and the elongation was 47%, indicating sufficient mechanical properties as a fiber product. Table 2 shows the physical properties of the N6 nanoporous fiber.
The N6 nanoporous fiber had excellent physical properties as shown in Table 2.

Reference example 4 (base cloth D)
80% by weight of homo PET having a melting point of 255 ° C., an intrinsic viscosity of 0.63, and a melt viscosity of 105 Pa · s (280 ° C., 1216 sec ^-1 ), a hot water-soluble polymer of a polyalkylene oxide derivative manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Melt kneading was performed at 275 ° C. using a twin screw extruder at 275 ° C. with 20% by weight of Paogen PP-15 ″. The melt viscosity of this hot water-soluble polymer was 128 Pa · s (280 ° C., 1216 sec ⁻¹ ). The melt spinning was performed in the same manner as in Reference Example 2 except that the temperature of the melted portion 2 was 280 ° C., the spinning temperature was 280 ° C., and the single hole discharge amount and the number of holes were changed. The number of yarn breaks during continuous spinning was zero. Then, stretching and heat treatment were performed in the same manner as in Reference Example 2 with the first hot roller temperature 16 set to 90 ° C., 90 dtex, 36 fragment, strength 3.3 cN / dtex, elongation 40%, U% 1.5%, heat A polymer alloy fiber having a shrinkage of 7% was obtained. As a result of observing the fiber cross section of the obtained polymer alloy fiber by TEM (FIG. 6), the area ratio of the island having a diameter of 200 nm or more to the whole island not including coarse aggregated polymer particles was 0.1% or less, and the diameter was 0.1% or less. The area ratio of 100 nm or more was also 0.1% or less. Here, the dark part is PET and the thin part is hot water-soluble polymer. Further, it was found from the fiber longitudinal section TEM observation that the island had a streak structure. In addition, the yarn properties were excellent as shown in Table 1.

  After circular knitting, the polymer alloy fiber was treated with hot water at 100 ° C. for 2 hours to remove 99% or more of the hot water-soluble polymer to obtain a circular knit made of PET nanoporous fiber.

  As a result of observing the fiber cross section of this PET nanoporous fiber by TEM (FIG. 7), the average diameter of the pores was 20 nm, and there were no large pores having a diameter of 50 nm or more. Here, the dark part was PET, the thin part was pores, and the pores were independent pores. When the mechanical properties of the PET nanoporous fiber were measured, the strength was 2.0 cN / dtex and the elongation was 45%, indicating sufficient mechanical properties as a fiber product. Table 2 shows the physical properties of the PET nanoporous fiber.

Reference Example 5 (Base cloth E)
In place of PET, polylactic acid (PLA) having a number average molecular weight of 70,000, a melting point of 170 ° C. and a melt viscosity of 83 Pa · s (220 ° C., 1216 sec ⁻¹ ) was melt-kneaded at 220 ° C. in the same manner as in Reference Example 4. Was done. The melt viscosity of this hot water-soluble polymer was 270 Pa · s (220 ° C., 1216 sec ⁻¹ ). When the melt spinning was performed in the same manner as in Reference Example 4 except that the temperature of the melting part 2 was set to 220 ° C. and the spinning temperature to 220 ° C., the spinnability was good and the yarn breakage during continuous spinning for 24 hours was zero. . Then, stretching and heat treatment were performed in the same manner as in Reference Example 4, except that the first hot roller temperature 16 was set to 90 ° C. As a result of observing the fiber cross section of the obtained polymer alloy fiber with a TEM, the area ratio of the island having a diameter of 200 nm or more to the entire island without containing coarse aggregated polymer particles is 0.1% or less, and the area of the island is 100 nm or more. The ratio was also 0.1% or less. Further, it was found from the fiber longitudinal section TEM observation that the island had a streak structure. In addition, the yarn properties were excellent as shown in Table 1.

  After circular knitting of this polymer alloy fiber in the same manner as in Reference Example 4, it was treated with hot water at 100 ° C. for 2 hours to remove 99% or more of the hot water-soluble polymer, thereby obtaining a circular knit made of PLA nanoporous fiber.

  As a result of observing the fiber cross section of this PLA nanoporous fiber with a TEM, the average diameter of the pores was 20 nm, and there were no large pores having a diameter of 50 nm or more. When the mechanical properties of the PLA nanoporous fiber were measured, it was found that the strength was 2.0 cN / dtex and the elongation was 45%, indicating sufficient mechanical properties as a fiber product. Table 2 shows the physical properties of the PLA nanoporous fiber.

Reference Example 6 (Base fabric F)
Instead of PLA, using a polypropylene (PP) manufactured by Sumitomo Mitsui Polyolefin having an MFR (melt flow rate) of 15 g / 10 min, spinning is performed in the same manner as in Reference Example 5, the yarn is drawn by air soccer, and opened. After being collected by a net, a calendar roll was applied to obtain a nonwoven fabric made of polymer alloy fibers and having a basis weight of 100 g / m ² . The single yarn fineness of the fiber taken by air soccer was 2 dtex, and the spinning speed determined from the fineness was equivalent to 4500 m / min. As a result of extracting a polymer alloy fiber from this nonwoven fabric and observing the cross section of the fiber with a TEM, the area ratio of an island having a diameter of 200 nm or more to an entire island without containing coarse aggregated polymer particles is 0.1% or less, and an island having a diameter of 100 nm or less. Was also 0.1% or less. The average diameter of the island was 30 nm.

  This nonwoven fabric was subjected to hot water treatment in the same manner as in Reference Example 5 to obtain a PP nanoporous fiber nonwoven fabric. This was excellent in water absorption. When nanoporous fibers were sampled from this nonwoven fabric and observed by TEM, no coarse pores having a diameter of 50 nm or more were found, and the average diameter of the pores was 20 nm. When the mechanical properties of the PP nanoporous fiber were measured, the strength was 2.5 cN / dtex and the elongation was 60%, indicating sufficient mechanical properties as a fiber product. Table 2 shows the physical properties of the PP nanoporous fiber.

Reference Example 7 (Base fabric G: control)
Using only N6 used in Reference Example 1, 100% circular knitting of N6 was obtained under the same spinning conditions as Reference Example 1.

Reference Example 8 (Base fabric H: control)
Using only the homo-PET used in Reference Example 4, 100% circular knitting of PET was obtained under the same spinning conditions as in Reference Example 4.

Reference Example 9 (Base fabric I: control)
Using only the PLA used in Reference Example 5, 100% circular knitting of PLA was obtained under the same yarn-making conditions as in Reference Example 5.

Reference Example 10 (Base fabric J: control)
Using only the PP used in Reference Example 6, a 100% nonwoven fabric of PP was obtained under the same spinning conditions as in Reference Example 6.

Reference Example 11 (Base fabric K)
According to Example 1 of JP-A-2001-172859, a knitted fabric comprising PTT fiber containing sodium alkyl sulfonate was obtained. Then, this was treated with a 0.5% aqueous sodium hydroxide solution at 100 ° C. for 3 hours to obtain a knitted fabric composed of PTT porous fibers having many micropores. The color development was evaluated. As a result, the area ratio of the coarse pores having a diameter of 200 nm or more in the porous fiber was as large as 5%. Therefore, the scattered light was much whitish and the color development was poor.

Reference example 12 (base cloth L)
70% by weight of N6 having a relative viscosity of 2.62; 4.5% by mole of 5-sodium sulfoisophthalic acid having an intrinsic viscosity of 0.60; 8.5% by weight of polyethylene glycol having a molecular weight of 4000; Was melted at 280 ° C., discharged from a round hole die having a hole diameter of 0.6 mm, and melt-spun at a spinning speed of 1000 m / min using the apparatus shown in FIG. However, the ejection of the polymer during spinning was not stable, and the spinnability was poor, and the yarn was frequently broken during spinning, and the yarn could not be stably wound. Using the slightly drawn undrawn yarn, drawing and heat treatment were performed at a draw ratio of 3.35 times, a temperature of the first hot roller 16 of 90 ° C., and a temperature of the second hot roller 17 of 130 ° C. Thus, a polymer alloy fiber of 85 dtex and 24 filaments was obtained. This was circular knitted, and 90% or more of the copolymerized PET was dissolved and removed therefrom by alkali treatment. The color development was evaluated. Since the area ratio of the coarse pores having a diameter of 200 nm or more in the porous fiber was as large as 2.4%, the scattered light was much whitish, and the color development was poor. .

  The base fabric in the above reference example was scoured and dried by a conventional method, and used in each example.

Examples 1 and 2, Comparative Examples 1 to 5
In Examples 1 and 2 and Comparative Examples 1 to 3, the base fabrics shown in Table 3 were used, and dyeing and the following moisture absorption processing were performed in separate baths. In Comparative Examples 4 and 5, only dyeing was performed, and no moisture absorption processing was performed. Each of the base fabrics was immersed in Takamatsu Oil & Fat Co., Ltd. product name "SR1000" (10% aqueous dispersion) as a moisture absorbent to exhaust the chemicals. At this time, the processing conditions were as follows: 20% owf as a solid content for the hygroscopic agent, a bath ratio of 1:20, a processing temperature of 130 ° C., and a processing time of 1 hour. After processing, it was washed with water and dried, and the content of the hygroscopic agent was measured. The results are as shown in Table 3. In the case where the N6 and PET nanoporous fibers of Examples 1 and 2 were used, the pores having high nanopores were obtained. By effectively utilizing the volume, the amount of exhaustion of the hygroscopic agent was significantly increased as compared with the case of using the normal N6 or PET fiber of Comparative Examples 1 and 2. When the ΔMR of each base fabric was evaluated, it was 6.0% in Example 1 using N6, and 2.8% in Comparative Example 1, and compared with unprocessed N6 of Comparative Example 4, the Example 1 used N6. 4.0% improvement in moisture absorption performance was observed. Similarly, in Example 2 using PET, it was 3.4%, and in Comparative Example 2, it was 0.4%. Compared to the unprocessed PET of Comparative Example 5, the moisture absorption performance of Example 2 was 3.2%. Improvement was seen. On the other hand, in the polyester microporous fiber of Comparative Example 3, although the moisture absorption performance was improved by the exhaustion of the drug into the microporous as compared with Comparative Example 2 using ordinary PET, the level was still insufficient. Further, when the coloring property was evaluated, in the case of Example 2 using PET nanoporous fiber, the coloring was hardly caused by visible light scattering because the micropores present inside the fiber were of the nano order. However, in Comparative Example 3, visible light was scattered because the micropores were on the submicron order, and the coloring was poor.

Examples 3 and 4, Comparative Examples 6 and 7
In Examples 3 and 4 and Comparative Examples 6 and 7, the base cloths shown in Table 4 were used, dyed by a conventional method, and then subjected to the following moisture absorption processing. These base cloths were immersed in a pad solution having the following composition, squeezed at a mangle pressure of 20 kg / cm ² , wound up in a roll shape, sealed with a polypropylene film, irradiated with microwaves while introducing saturated steam at 100 ° C. Heated for minutes.

<Pad liquid composition>
Methacrylic acid 35%
Benzoyl peroxide 2%
Octyl pyridinium chloride 20%
43% water
The contents of the monomers in the base fabrics of the examples and the comparative examples are as shown in Table 4, and in the example using the nanoporous fiber, after the methacrylic acid monomer was exhausted in a large amount into the nanopore, By the graft reaction, the content was significantly increased. After the above-mentioned base fabric was subjected to ordinary soaping and drying, it was subjected to a heating treatment at 60 ° C. for 30 minutes with an aqueous solution of sodium carbonate at a bath ratio of 1:20 at a bath ratio of 1:20, whereby a carboxyl terminal group of the monomer was subjected to sodium substitution treatment. Thereafter, washing and drying were performed, and their ΔMR was measured. As shown in Table 3, Example 3 using N6 was 8.2%, Comparative Example 6 was 2.8%, and Example 4 using PET was as follows. Was 4.4% in Comparative Example 7, and 1.4% in Comparative Example 7, indicating that good moisture absorption performance was exhibited when N6 or PET nanoporous fiber was used. In addition, it was found that in the examples, the color development was also excellent.

Example 5 and Comparative Example 8
In Example 5 and Comparative Example 8, the base cloths shown in Table 5 were used and immersed in an aqueous emulsion solution of trimethyl phosphate (effective concentration: 3%) as a flame retardant, with a bath ratio of 1:20 and a temperature of 98 ° C. for 30 minutes. Minutes. After processing, it was washed with water and dried, and the content of the flame retardant was measured. When the flame retardancy of each of the base fabrics was evaluated, in Comparative Example 8, the number of times of flame contact was two and the whole was burned. On the other hand, in Example 5, even when the number of times of flame contact was five, the base fabric hardly burned. In Example 5 using the N6 nanoporous fiber, the flame retardant was exhausted in a large amount into the nanopores, and the flame retardant was present even in the pores inside the fiber, so that the flame retardant was excellent. It was.

Example 6 and Comparative Example 9
In Example 6 and Comparative Example 9, the base cloths shown in Table 6 were used, and a diluted aqueous solution of a flame retardant (trade name: K-19A (cyclic phosphonate ester) manufactured by Meisei Chemical Industry Co., Ltd. (effective concentration: 10) %) And the excess liquid was removed with a mangle. The pickup was 80%. This sample was subjected to a dry heat treatment at a temperature of 190 ° C. for 2 minutes. After processing, it was washed with water and dried, and the content of the flame retardant was measured. When the flame retardancy was evaluated, in Comparative Example 5, the sample was completely burned with two times of flame contact. In Example 5, however, even when the number of flame contact was 6 times, the sample hardly burned and was excellent in flame retardancy. Had.

Examples 7 and 8, Comparative Examples 10 to 12
In Examples 7 and 8 and Comparative Examples 10 to 12, the respective base fabrics were impregnated with a 10% aqueous solution of miconazole nitrate, which is effective against ringworm (athlete's foot), using the base fabrics shown in Table 7, and then heated at 50 ° C. And dried. Table 7 shows the results of measurement of the content of miconazole nitrate in the base fabric. In this way, a base cloth capable of eluting the athlete's foot drug with sweat was obtained. Each of the obtained base cloths was stuck to the affected part of 50 patients with athlete's foot and was returned to a new one every day. When this was continued for one month, the symptoms were improved in 45 and 35 patients in Examples 7 and 8, respectively, but none of Comparative Examples 10 and 11 improved the symptoms. Further, in Comparative Example 12, the microporous acrylic fiber was used, so that the content of the athlete's foot drug was slightly improved by submicron-order microporosity, and the sustained release of the athlete's foot drug was improved to some extent because the symptoms of five persons were improved. However, it was still at an insufficient level. From the above, it was possible to obtain a product excellent in sustained release as well as drug exhaustion in the examples.

Examples 9 and 10, Comparative Examples 13 and 14
In Examples 9 and 10 and Comparative Examples 13 and 14, the base cloths shown in Table 8 were used, and the base cloths were impregnated with a 20% aqueous solution of provitamin C (phosphate ester of ascorbic acid), and then dried at room temperature. did. Table 8 shows the measurement results of the content of provitamin C in the base fabric. In this way, a base cloth for sustained release of a component effective for whitening, beautiful skin, and prevention of skin aging was obtained. The obtained base cloth was subjected to monitoring for one month for 10 women, where the base cloth was affixed to places where darkness and dullness of the face were concerned. When a questionnaire survey was conducted to determine whether or not the effect was obtained, when the base fabrics of Examples 9 and 10 were used, 5 and 6 persons answered that the darkening and dullness of the face were reduced, respectively. When 14 was used, only one person answered that the effect was effective.

Example 11 and Comparative Example 15
In Example 11 and Comparative Example 15, the base fabrics shown in Table 9 were used, and each base fabric was impregnated with a 10% aqueous solution of arginine and then dried at room temperature. The content of arginine in the base fabric was measured, and the results are as shown in Table 9. In this way, a base cloth for sustained release of a component effective for moisturizing the skin was obtained. A one-month monitor was applied to 10 women for applying the obtained base cloth to wrinkles on the face and dry skin parts of the body. When a questionnaire survey was conducted to determine whether or not the effect was obtained, seven people answered that the wrinkle of the face and dry skin were effective when the base cloth of Example 11 was used, whereas the base cloth of Comparative Example 15 was used. When using the cloth, only one person was not able to answer that it was effective.

Example 12 and Comparative Examples 16 and 17
In Example 12 and Comparative Examples 16 and 17, the base fabrics shown in Table 10 were used. For Example 12 and Comparative Example 16, the following antistatic processing was performed. In addition, about the comparative example 17, processing was not performed. Using a 20% aqueous solution of “Sunstat ES-15 (anion activator)” manufactured by Sanyo Chemical Industries as an antistatic agent, impregnating the base fabric under acidic conditions by pH control, and treating at 98 ° C. for 1 hour. After performing, the base fabric was dried at 50 ° C. Table 10 shows the content of the antistatic agent in the base fabric. When the friction withstand voltage of the obtained base fabric was measured, it was 55 V in Example 12 and 1500 V in Comparative Example 16. As described above, in Example 12, the amount of the antistatic agent exhausted into the nanopores was significantly increased, and a large number of the antistatic agent was dispersed in the nanometer order inside the nanoporous fiber forming the fiber structure. Therefore, the antistatic performance was excellent.

Example 13 and Comparative Examples 18 and 19
In Example 13 and Comparative Examples 18 and 19, the base fabrics shown in Table 11 were used. For Example 13 and Comparative Example 18, the following antistatic processing was performed. In addition, about the comparative example 19, processing was not performed. The base cloth is impregnated with a 20% aqueous solution of "Sunstat KT-305C (cationic activator)" manufactured by Sanyo Chemical Industries as an antistatic agent, treated at 130 ° C for 1 hour, and then treated at 50 ° C. Was dried. Table 11 shows the measurement results of the content of the antistatic agent in the base fabric. When the friction withstand voltage of the obtained base fabric was measured, it was 180 V in Example 13 and 2200 V in Comparative Example 18, and it was found that Example 13 had good antistatic performance.

Example 14 and Comparative Examples 20 and 21
In Example 14 and Comparative Examples 20 and 21, the base fabrics shown in Table 12 were used. For Examples 14 and 20, the following functional processing was performed. In addition, about the comparative example 21, processing was not performed. Using a 10% aqueous solution of dodecane diacid dihydrazide having an adsorbing ability for acetaldehyde, each base cloth is treated at a solid content of 20% owf, a bath ratio of 1:20, a treatment temperature of 130 ° C., and a treatment time of 1 hour. Was. Table 12 shows the content of dodecane diacid dihydrazide measured. When these acetaldehyde removal abilities were evaluated, in Example 14, the concentration was reduced from the initial concentration of 30 ppm to 1 ppm in 10 minutes. On the other hand, in Comparative Example 20, the concentration decreased only from the initial concentration of 30 ppm to 20 ppm. In Example 14, the concentration was 1/10 or less of the initial concentration of acetaldehyde, indicating that the acetaldehyde had excellent removal ability.

Examples 15 and 16, Comparative Examples 22 and 23
In Examples 15 and 16, and Comparative Examples 22 and 23, the base fabrics shown in Table 13 were used. These base fabrics were immersed in a 10% aqueous solution of "Nicanone RB (quaternary ammonium salt)" (trade name, manufactured by Daiwa Chemical Co., Ltd.) as an antibacterial agent, and treated at 98 ° C. for 1 hour in Example 15 and Comparative Example 22. In Example 16 and Comparative Example 23, the treatment was performed at 130 ° C. for 1 hour. Thereafter, the base fabric was dried at 50 ° C. Table 13 shows the antibacterial agent content of each base fabric measured. When the bacteriostatic activity values of these base fabrics were evaluated, 6.0 was obtained in Example 15 using N6, 1.5 in Comparative Example 22, 4.5 in Example 16 using PET, and 4.5 in Comparative Example 23. 0.9, as in Examples 15 and 16, it was found that the fiber structure using nanoporous fibers exhibited excellent antibacterial performance.

Example 17 and Comparative Example 24
In Example 17 and Comparative Example 24, the base fabrics shown in Table 14 were used. The product was immersed in a 10% ethanol solution of an insect repellent, "Martaquinone B-EC" (trade name, manufactured by Osaka Kasei Co., Ltd.), treated at 40 ° C. for 30 minutes, and then dried at room temperature. Table 14 shows the results obtained by measuring the content of the insect repellent in each of the base fabrics. When these insect repellent performances were evaluated, the number of redness was 3 in Example 17 but was 30 in Comparative Example 24. Further, after the processed base cloth was left in a hot air dryer at 80 ° C. for 500 hours, the insect repellent performance was similarly evaluated. In Example 17, the number of redness was 6 and in Comparative Example 24, the number of redness was 80. In Example 17, it was found that the insect repellent had sustainability of insect repellent performance due to the retention of the insect repellent in the nanopores and the sustained release.

Example 18 and Comparative Example 25
In Example 18, the base cloth D was used, and in Comparative Example 25, the base cloth H was used. These base fabrics were immersed in a lavender extract and dried at room temperature. The content was measured and found to be 4.0% in Example 18 and 0.2% in Comparative Example 25. When the duration of the scent of these base cloths was examined, in Comparative Example 25, the scent was hardly felt from the base cloth after one day, but in Example 18, the scent was still felt after one week. It was found that the fragrance had excellent retention and sustained release properties.

Example 19 and Comparative Example 26
In Example 19 and Comparative Example 26, the base fabrics shown in Table 15 were used. These base fabrics were immersed in a 20% benzophenone emulsion solution and dried at 98 ° C. for 30 minutes. The content of benzophenone in each of the base fabrics was measured. When the performance of the ultraviolet ray cut was evaluated, in Example 19, 98% of the ultraviolet ray was cut, whereas in Comparative Example 26, only 8% of the ultraviolet ray was cut. As described above, in Example 19, a fibrous structure having high ultraviolet ray cut performance was able to be obtained.

Examples 20 and 21, Comparative Examples 27 to 30
In Examples 20 and 21 and Comparative Examples 27 to 30, the base fabrics shown in Table 16 were used. Examples 20 and 21 and Comparative Examples 27 and 28 were subjected to the following antifouling treatment. The processing was not performed on Comparative Examples 29 and 30. The product was immersed in a 20% aqueous solution of "NK Guard FGN-860" (trade name, manufactured by Nikka Kagaku Co., Ltd.), and at 20 ° C. for 30 minutes in Example 20 and Comparative Example 27, and at 130 ° C. for 30 minutes in Example 21 and Comparative Example 28. After the treatment, it was dried at 50 ° C. Table 13 shows the results of measurement of the content. When the antifouling properties of these base fabrics were evaluated, the results were ○ (good) in Examples 20 and 21, Δ (somewhat good) in Comparative Examples 27 and 28, and × (Poor) in Comparative Examples 29 and 30. Was. Further, after the base fabrics of Examples 20 and 21 and Comparative Examples 27 and 28 were subjected to general washing (25 times), the antifouling property was evaluated again. In Examples 20 and 21, ○ (good) and Example 20 were obtained. In the example, the antifouling treatment with good washing durability was possible by the anchor effect of the antifouling agent by the nano-sized fine pores.

Example 22
The polymer alloy fiber produced in Reference Example 3 and ordinary N6 fiber of 70 dtex and 96 filaments were air-blended using an interlace nozzle. This was used as a warp and a weft to prepare a plain weave with a basis weight of 150 g / m ² , and subjected to an alkali treatment in the same manner as in Reference Example 3 to obtain a fabric comprising N6 nanoporous fibers and normal N6. When the N6 nanoporous fiber was observed with a TEM, no coarse pores having a diameter of 50 nm or more were found at all, the average diameter of the pores was 20 nm or less, and the yarn strength was 3.4 cN / dtex. The pores were independent pores. This fabric was subjected to the same flame retarding treatment as in Example 5, and the flame retardancy was evaluated. As a result, the base fabric hardly burned even when the number of times of flame contact was five. In addition, the base fabric had a soft and delicate touch and excellent texture as in the case of ordinary N6 fiber alone.

Example 23
Using a polymer alloy fiber obtained in Reference Example 2 as a warp and viscose rayon of 72 dtex and 27 filaments as a weft, a 2/2 twill fabric was produced so that the basis weight was 150 g / m ² . This was subjected to an alkali treatment in the same manner as in Reference Example 2. When N6 nanoporous fibers were extracted from the obtained fabric and observed by TEM, there were no coarse pores having a diameter of 50 nm or more, the average diameter of the pores was 20 nm or less, and the yarn strength was 2.0 cN / dtex. The pores were independent pores. This fabric was dyed and subjected to moisture absorption in the same manner as in Example 1, and the moisture absorption was evaluated. As a result, the ΔMR was 7%, indicating a sufficient moisture absorption. In addition, the coloring properties were good, and the base fabric had a soft and delicate touch and excellent texture.

Examples 24 and 25
The squalane, which is a natural oil component extracted from shark liver in base fabrics A (nylon nanoporous) and D (PET nanoporous) and has a skin care effect by moisturizing, was exhausted. The processing 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 processing time of 60 minutes. After the treatment, washing was performed at 80 ° C. for 2 hours. At this time, the attached amount of squalane was 6% by weight and 21% by weight based on the cloth. Thereafter, the amounts of squalane deposited after the washing test were 3% by weight and 12% by weight with respect to the fabric, respectively, indicating sufficient washing durability. From this, it was found that it is more effective to use a nanoporous fiber made of a hydrophobic polymer such as PET for a hydrophobic substance such as squalane.

  A sock was prepared using a circular knit made of this squalane-processed PET nanoporous fiber, and a 10-week wearing test was performed on 10 subjects with severely dried heels. . This is probably because squalane trapped or encapsulated in the pores was gradually extracted by the subject's sweat and came into contact with the skin.

Comparative Example 31
When squalane was exhausted to the base fabric H (usually PET) in the same manner as in Example 25, the adhesion amount after washing was 21% by weight with respect to the fabric, but the adhesion amount after the washing test was 0%. % By weight, and there was no washing durability at all.

Example 26
The base fabric A was immersed in a 5% by weight aqueous solution of silver nitrate for 1 minute, and then a 4% by weight aqueous solution of KCl was added dropwise to carry out ion exchange to fix silver ions in the fibers. Thereafter, after washing with running water for 15 minutes, a washing test was performed. At this time, the amount of AgCl attached to the fabric weight was 4% by weight.

Comparative Example 32
Using the base fabric G, silver ions were processed in the same manner as in Example 26, but the amount of adhesion after the washing test was 0.2% by weight, and a large amount could not be adhered.

Example 27
The base fabric A was immersed in a 0.5 M aqueous solution of platinum chloride to sufficiently impregnate the fabric with platinum chloride. Thereafter, this was once taken out, the fabric surface was washed with ion-exchanged water, dried, and then reduced by hydrazine treatment, to obtain a nanoporous fiber / platinum composite fabric-shaped material. It was a flexible and easy to handle material. Further, a washing test was performed on the same. At this time, the amount of platinum deposited was 3% by weight based on the weight of the fabric.

Comparative Example 33
Using the base fabric G, platinum adhesion processing was performed in the same manner as in Example 27, and a washing test was performed. At this time, the amount of platinum deposited was 0.1% by weight.

Example 28
10 ml of dimethyldimethoxysilane, 10 ml of water, 30 ml of ethanol, and 0.1 ml of 10% diluted hydrochloric acid were mixed and stirred at room temperature to prepare a working fluid. The base cloth A was immersed in this working liquid for 2 hours, and washed with running water for 1 minute. Thereafter, the cloth was heat-treated at 140 ° C. for 3 minutes to advance the polymerization of the silicone monomer, and converted into dimethyl silicone. Then, after washing with running water for 40 minutes, a washing test was further performed. The amount of dimethyl silicone carried at this time was 9% by weight based on the weight of the fabric.

Comparative Example 34
Using the base fabric G, silicone processing was performed in the same manner as in Example 29. The dimethyl silicone carried amount after the washing test was 0%.

Example 29
Processing was carried out in the same manner as in Example 28 using monotrifluoropropanetrimethoxysilane to obtain a composite composed of organized silica and nylon. The adhesion ratio of the organized silica to the fabric weight after the washing test was 12% by weight.

Comparative Example 35
Processing was performed in the same manner as in Example 29 using the base cloth G. The adhesion ratio of the organized silica to the fabric weight after the washing test was as small as 4% by weight.

Example 30
The base fabric D was exhausted with triphenylphosphoric acid as a flame retardant (Leophos TPP, Ajinomoto Fine Techno Co., Ltd.) at 20% owf, a bath ratio of 1:40, a treatment temperature of 130 ° C., and a treatment time of 1 hour. Then, this was washed with water and soaped with an aqueous sodium carbonate solution (80 ° C.). In addition, a washing test was performed. At this time, the amount of adhesion was 7% by weight with respect to the weight of the fabric.

Comparative Example 36
The base fabric H was processed with triphenylphosphoric acid in the same manner as in Example 26. However, the adhesion amount after the washing test was 1% by weight, and no self-extinguishing property was exhibited.

4 is a TEM photograph showing a cross section of the nanoporous fiber of Reference Example 1. 3 is a TEM photograph showing a cross section of the polymer alloy fiber of Example 1. 6 is a TEM photograph showing a longitudinal section of the polymer alloy fiber of Reference Example 1. 9 is a TEM photograph showing a cross section of the polymer alloy fiber of Reference Example 2. 4 is a TEM photograph showing a cross section of a polymer alloy chip. 9 is a TEM photograph showing a cross section of the polymer alloy fiber of Reference Example 4. 13 is a TEM photograph showing a cross section of the nanoporous fiber of Reference Example 4. It is a figure showing a spinning device. It is a figure which shows a base. It is a figure showing a stretching device. It is a figure which shows a stretching false twist apparatus. It is a figure which shows a spinning direct drawing apparatus.

Explanation of reference numerals

1: hopper 2: melting part 3: spinning pack 4: spinneret 5: chimney 6: thread 7: focusing lubrication guide 8: first take-up roller 9: second take-up roller 10: take-up yarn 11: measuring part 12: discharge Hole length 13: discharge hole diameter 14: undrawn yarn 15: feed roller 16: first hot roller 17: second hot roller 18: delivery roller (room temperature)
19: drawn yarn 20: undrawn yarn 21: feed roller 22: heater 23: cooling plate 24: rotor 25: delivery roller 26: false twisted yarn 27: first hot roller 28: second hot roller

Claims (8)

  A functional fiber structure comprising a nanoporous fiber having an area ratio of coarse pores having a diameter of 200 nm or more and 1.5% or less in the entire fiber cross section, wherein a functional substance is contained. object.   The functional fiber structure according to claim 1, wherein an area ratio of pores having a diameter of 50 nm or more to the entire fiber cross section of the nanoporous fiber is 1.5% or less.   3. The functional fiber structure according to claim 1, wherein the average diameter of the pores of the nanoporous fiber is 0.1 to 50 nm. 4.   The functional fiber structure according to any one of claims 1 to 3, wherein the strength of the nanoporous fiber is 1.5 cN / dtex or more.   The functional fiber structure according to any one of claims 1 to 4, wherein 80% by weight or more of the component constituting the nanoporous fiber is at least one selected from the group consisting of polyester, polyamide, and polyolefin. .   The functional fiber structure according to any one of claims 1 to 5, wherein the polymer constituting the nanoporous fiber is polyester or polyolefin, and the functional substance is hydrophobic.   A nanoporous fiber in which the area ratio of coarse pores having a diameter of 200 nm or more in the entire cross section of the fiber is 1.5% or less is impregnated with a readily soluble functional material, and then the hardly soluble functional material is subjected to a chemical reaction or counterion exchange. Function processing method of nanoporous fiber to be fixed as   A nanoporous fiber in which the area ratio of coarse pores having a diameter of 200 nm or more to the entire cross section of the fiber is 1.5% or less is impregnated with a monomer, and then polymerized or crosslinked to fix the nanoporous fiber as a hardly soluble functional material. Function processing method.

Images