JP2020070514A - Long and short composite spun yarn and woven and knitted fabric with excellent moisture absorption and desorption and abrasion resistance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a comfortable environment in clothes by exhibiting excellent hygroscopic performance under unpleasant high humidity and dissipating and radiating the absorbed moisture in a low humidity environment where moisture absorption is not required. Provided are long and short composite spun yarns having excellent wear resistance. SOLUTION: The core has a core-sheath structure including a core portion containing an acrylonitrile-based polymer as a main component and a sheath portion containing a crosslinked structure and a polymer having a carboxyl group as a main component, and a numerical value represented by the following formula. It is a long-short composite spun yarn using at least a part of an acrylate-based fiber having A of 0.050 to 0.080, and the difference in moisture absorption rate between 20 ° C. 70% RH and 20 ° C. 95% RH is 1.0. A long-short composite spun yarn characterized by having a conjugation force value of ~ 5.0% and a conjugation force value of 300 times or more. A = Amount of carboxyl group [mmol / g] / Ratio of area occupied by sheath in fiber cross section [Selection diagram] FIG. 3

Description

  TECHNICAL FIELD The present invention relates to a long-short composite spun yarn excellent in moisture absorption / release and abrasion resistance, and a woven / knitted fabric using the same.

  BACKGROUND ART Conventionally, a material using an acrylate fiber has excellent hygroscopicity and is widely used for winter clothing by taking advantage of a heat generating effect obtained at the same time as moisture absorption. Regarding hygroscopicity, which is a characteristic of acrylate fibers, it has the effect of reducing discomfort in summer, but due to the heat generation that occurs at the same time, it has not been possible to develop it as a material suitable for summer.

  Acrylate-based fibers have high hygroscopicity, but on the other hand, they have low strength, and thus fluff occurs on the surface of the spun yarn during repeated use of the final product, which lowers the product quality.

  In addition, since acrylate fiber is a short fiber, it shows high hygroscopicity, but it has a texture that leads to warmth such as fluffiness and swelling peculiar to short fiber spun yarn, so it is difficult to use for comfortable clothing in summer. Met.

  In order to improve the quality of spun yarns and products using such acrylate fibers, a long-short composite spun yarn and a method for producing the same have been proposed (see Patent Documents 1 and 2). This long-short composite spun yarn is excellent in product quality and strength, but has a filament shape in which acrylate fibers and hydrophobic filaments are uniformly mixed using an electric opening device, and the texture of the short fibers is on the surface. It is expressed, and it is comfortable clothing in winter, but not comfortable clothing in summer.

  Further, in order to improve the stickiness of sweat, which is an uncomfortable feeling in summer, using a long-short composite spun yarn, a long-short composite yarn having a three-layer structure using hydrophobic long fibers and short fibers has been proposed (Patent Document 3). reference). This long-short composite yarn has little stickiness and is excellent in quick-drying property, but it is not a material constitution which exhibits hygroscopicity under high humidity.

  On the other hand, as the spun yarn with improved abrasion resistance, a multi-layer composite yarn and a fiber bundle composed of short fibers and filaments mixed with each other, and a fiber bundle composed of only filaments A manufacturing method has been proposed (see Patent Document 4). This multilayer composite yarn is excellent in abrasion resistance and wet feeling, but is not excellent in hygroscopicity under uncomfortable high humidity.

JP, 2004-308035, A JP, 2004-308036, A JP 2012-102418 A JP-A-8-127928

  The present invention has been made in view of the current state of the prior art described above, and its purpose is to exhibit excellent hygroscopic performance under high humidity, which is uncomfortable for the human body, and in a low humidity environment that does not require moisture absorption. The purpose is to provide a long and short composite spun yarn that is excellent in wear resistance as well as providing a comfortable environment inside clothes by releasing and radiating the absorbed moisture. Furthermore, the long and short composite spun yarn is used. (EN) Provided is a woven / knitted fabric that has a refreshing feeling and is comfortable to wear with little stickiness even when a large amount of sweat is generated, and has a moisture absorbing / releasing function.

  The present inventor, as a result of diligent studies to achieve the above object, has found that a specific acrylate fiber having a moisture absorption capacity when humidity is increased under high humidity is significantly larger than that of a conventional one and at least a long-short composite spun yarn having a specific structure. It has been found that the moisture absorption / release property capable of rapidly exhibiting the moisture absorption property under unpleasant high humidity and the wear resistance capable of withstanding repeated use can be obtained by using a part thereof, and the present invention has been completed. ..

That is, the present invention has the following configurations (1) to (7).
(1) A core-sheath structure having a core part containing an acrylonitrile polymer as a main component and a sheath part containing a cross-linking structure and a polymer having a carboxyl group as a main component, and having a numerical value A represented by the following formula: Is a long-short composite spun yarn in which at least a part of acrylate-based fibers having a value of 0.050 to 0.080 is used, and the difference in moisture absorption rate between 20 ° C. 70% RH and 20 ° C. 95% RH is 1.0 to A long-short composite spun yarn having a tying force value of 300% or more at 5.0%.
A = Amount of carboxyl group [mmol / g] / Ratio of the area occupied by the sheath portion in the cross section of the fiber (2) The long-short composite spun yarn, when viewed in the cross section, has the center layer, the outermost layer, and the middle between them. The long-short composite spun yarn according to (1), characterized in that the acrylate fiber is arranged in the middle layer of the long-short composite spun yarn, and the hydrophobic filaments are arranged in the center layer and the outermost layer. .
(3) The long-short composite spun yarn is composed of a center layer and an outer layer when viewed in a cross section, the acrylate fiber is arranged in the center layer of the long-short composite spun yarn, and the hydrophobic filament is arranged in the outer layer. The long-short composite spun yarn according to (1).
(4) The long-short composite spun yarn according to (1), characterized in that the long-short composite spun yarn is formed by uniformly mixing acrylate fibers and hydrophobic filaments when viewed in a cross section.
(5) The long-short composite spun yarn according to (1), characterized in that the long-short composite spun yarn is composed of an aggregate of acrylate fibers and an aggregate of hydrophobic filaments side by side when viewed in a cross section. .
(6)
The long-short composite spun yarn is composed of a center layer and an outer layer covering the center layer when viewed in a cross section. A hydrophobic filament is arranged in the center layer of the long-short composite spun yarn, and an acrylate fiber is arranged in the outer layer. The long-short composite spun yarn according to (1).
(7) A woven or knitted fabric characterized by using the long-short composite spun yarn according to any one of (1) to (6) in at least a part thereof.

  Since the long-short composite spun yarn of the present invention uses a specific acrylate fiber that rapidly exhibits hygroscopicity under high humidity, it exhibits excellent hygroscopic performance under unpleasant high humidity, and requires moisture absorption. In a low-humidity environment where there is no humidity, the absorbed moisture can be released and released. Further, the long-short composite spun yarn of the present invention is composed of short fiber acrylate-based fibers and long fibers in a specific arrangement, and thus has excellent product quality and strength, and has abrasion resistance that can withstand repeated use. be able to. Therefore, the woven or knitted fabric using the long-short composite spun yarn of the present invention has a refreshing feeling and can have both comfortable wearing comfort and moisture absorbing / releasing function with less sticky feeling even when a large amount of sweat is generated.

1 is a schematic view of an apparatus for producing a long-short composite spun yarn according to the present invention. It is a comparative graph of the hygroscopic property of the acrylate fiber used by this invention and the conventional acrylate fiber. 1 is a schematic cross-sectional view of a long-short composite spun yarn (Example 1) of the present invention. It is a schematic transverse cross-sectional view of a long-short composite spun yarn (Example 5) of the present invention. It is a schematic transverse cross-sectional view of a long-short composite spun yarn (Example 6) of the present invention. It is a schematic transverse cross-sectional view of a long-short composite spun yarn (Example 7) of the present invention. It is a schematic transverse cross-sectional view of a long-short composite spun yarn (Example 8) of the present invention.

Hereinafter, the long-short composite spun yarn of the present invention will be described in detail.
The long-short composite spun yarn of the present invention has a core-sheath structure composed of a core part containing an acrylonitrile polymer as a main component, and a sheath part containing a cross-linking structure and a polymer having a carboxyl group as a main component, and The acrylate fiber whose numerical value A represented by the formula is within a specific numerical range is used at least in part. The acrylate fiber used in the present invention has a high hydrophilicity in the sheath portion containing a polymer having a crosslinked structure and a carboxyl group as a main component, and since the acrylonitrile-based polymer constituting the core portion has almost no hydrophilicity, it absorbs moisture. The generated water does not remain in the core of the fiber, and the moisture can be released more efficiently than the sheath. Acrylate-based fibers show the same hygroscopic properties as ordinary cellulose fibers such as rayon at around 20 ° C and 50% RH (relative humidity), which is considered comfortable for the human body, but from around 20 ° C and 70% RH. It has a characteristic that the moisture absorption capacity rapidly increases in an uncomfortable region under high humidity.

  The acrylate fiber used in the present invention is a core-sheath fiber composed of a core portion containing an acrylonitrile polymer as a main component, and a sheath portion containing a polymer having a crosslinked structure and a carboxyl group as a main component, and high humidity. It is characterized in that it has a remarkably higher absorption capacity than the conventional acrylate fiber when the humidity rises (especially when the humidity rises from 20 ° C. 70% RH to 20 ° C. 95% RH). Specifically, as shown in FIG. 2, the acrylate fiber of the present invention has an increase in the saturated moisture absorption rate when the humidity rises at a comfortable low humidity to a degree smaller than that of the conventional one, but the acrylate fiber has an uncomfortable high humidity. The increase in the saturated moisture absorption rate when the humidity rises (when changing from 20 ° C. 70% RH to 20 ° C. 95% RH) is characterized by a marked increase in the conventional acrylate. Here, the "main component" means that it is the most quantitative component in each of the sheath portion and the core portion, and in the normal case, each of the above-mentioned polymers is preferably It accounts for 90% by mass or more, and more preferably 95% by mass or more. Here, the acrylonitrile-based polymer that constitutes the core may also have a crosslinked structure.

Further, the acrylate fiber used in the present invention is characterized in that the numerical value A represented by the following formula is 0.050 to 0.080, preferably 0.055 to 0.070.
A = amount of carboxyl group [mmol / g] / ratio of area occupied by sheath in fiber cross section [%]

  Here, the numerical value A is a numerical value that correlates with the concentration of the carboxyl group in the sheath portion (surface layer portion) of the core-sheath fiber, and the larger this value, the higher the carboxyl group, which is a polar functional group, on the fiber surface. Will be present in concentration. Therefore, the larger the numerical value A is, the more moisture can be contained in the fiber surface layer portion, and the moisture can be released to the outside more quickly. In order to obtain such an effect, it is necessary that the numerical value A is at least the lower limit of the above range. On the other hand, when the numerical value A exceeds the above range, the surface layer of the fiber becomes sticky due to moisture absorption, and the fibers are apt to adhere to each other, which may cause a trouble in the spinning process or deteriorate the texture due to washing or the like. It is not preferable because there is.

  The counter ion of the carboxyl group in the polymer having a crosslinked structure and a carboxyl group is not limited to hydrogen ions, but is also an alkali metal cation such as lithium, sodium, or potassium, or an alkaline earth metal cation such as magnesium or calcium. , Cations of other metals such as manganese, copper, zinc, and silver, ammonium ions, and the like can be selected according to required characteristics. When there is a carboxyl group having a counter ion other than such hydrogen ions (hereinafter referred to as a salt-type carboxyl group), the increase in the saturated moisture absorption rate when changing to the above-mentioned high humidity becomes larger, and Since the rate of moisture release is higher, greater moisture absorption and release can be expected. The amount of such salt-type carboxyl groups is preferably 40% or more, more preferably 50% or more, still more preferably 60% or more with respect to the total amount of carboxyl groups. On the other hand, if the amount of salt-type carboxyl groups is too large, the fibers tend to become sticky or brittle during moisture absorption, so that the amount is preferably 90% or less, more preferably 80% or less, based on the total amount of carboxyl groups. Is desirable. Further, when sodium ion or potassium ion is selected as the counter ion, the moisture absorption / desorption property can be further increased.

  As a typical method for producing the acrylate fiber used in the present invention, a method of subjecting the surface layer portion of the acrylonitrile fiber to a crosslinking introduction treatment and a hydrolysis treatment can be adopted. The crosslinking introduction treatment may be performed not only on the surface layer portion (sheath portion) but also on the central portion (core portion). The acrylonitrile fiber as a raw material can be produced from an acrylonitrile polymer by a known method. The acrylonitrile-based polymer has an acrylonitrile content of preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 85% by mass or more. As will be described later, the cross-linked structure is formed by the reaction of the nitrile group of the acrylonitrile-based polymer and the cross-linking agent, so when the content of acrylonitrile in the acrylonitrile-based polymer is low, the amount of the cross-linked structure that can be introduced is small. Therefore, the fiber strength may be insufficient in terms of processing and practical use.

  A crosslinked structure is introduced into the acrylonitrile fiber as described above. A conventionally known crosslinking agent may be used for introducing the crosslinked structure, but it is preferable to use a nitrogen-containing compound from the viewpoint of the efficiency of introducing the crosslinked structure. As the nitrogen-containing compound, it is preferable to use an amino compound or a hydrazine compound having two or more primary amino groups. Examples of the amino compound having two or more primary amino groups include diamine compounds such as ethylenediamine and hexamethylenediamine, diethylenetriamine, 3,3′-iminobis (propylamine), N-methyl-3,3′-iminobis ( Propylamine) and other triamine compounds, triethylenetetramine, N, N'-bis (3-aminopropyl) -1,3-propylenediamine, N, N'-bis (3-aminopropyl) -1,4- Examples thereof include tetramine compounds such as butylenediamine, polyvinylamine, polyallylamine and the like, and polyamine compounds having two or more primary amino groups. Examples of the hydrazine-based compound include hydrazine hydrate, hydrazine sulfate, hydrazine hydrochloride, hydrazine hydrobromide, and hydrazine carbonate. The upper limit of the number of nitrogen atoms in one molecule is not particularly limited, but is preferably 12 or less, more preferably 6 or less, and particularly preferably 4 or less. If the number of nitrogen atoms in one molecule exceeds the above upper limit, the number of molecules of the crosslinking agent becomes large, and it may be difficult to introduce a crosslinked structure into the fiber. The conditions for introducing the crosslinked structure are not particularly limited, and can be appropriately selected in consideration of the reactivity between the crosslinking agent used and the acrylonitrile fiber, the amount of the crosslinked structure, and the like. For example, when a hydrazine-based compound is used as the cross-linking agent, the acrylonitrile-based fiber described above is dipped in an aqueous solution containing the hydrazine-based compound so that the hydrazine concentration is 0.1 to 10% by mass, and the acrylonitrile-based fiber is applied at 80 to 150%. Examples include a method of treating at 2 ° C. for 2 to 10 hours.

  After the introduction of the crosslinked structure, a hydrolysis treatment with an alkaline metal compound is performed to hydrolyze the nitrile group existing in the surface layer portion of the fiber to form a carboxyl group. As specific treatment conditions, various conditions such as the concentration of the treatment agent, the reaction temperature, and the reaction time may be appropriately set in consideration of the above-mentioned carboxyl group concentration and the like, but preferably 0.5 to 10% by mass, More preferably, a means for treating in a 1 to 5 mass% aqueous treatment chemical solution at a temperature of 80 to 150 ° C. for 2 to 10 hours is preferable in terms of industrial and fiber properties. Here, the above-mentioned crosslinking introduction treatment and hydrolysis treatment are preferably performed simultaneously in a lump using an aqueous solution in which the respective treatment agents are mixed, rather than sequentially performed as described above. Further, in this simultaneous treatment, it is preferable that the alkali metal compound having a lower concentration than that of the conventional treatment is performed under mild conditions, and the subsequent acid treatment is performed at a higher temperature than before and under severe conditions. The acrylate fiber thus obtained has a structure in which more carboxyl groups are present in the surface layer portion (sheath portion) than in the past, and a relatively hard acrylonitrile polymer is preserved in the central portion (core portion). You can

  Examples of the counter ion of the formed carboxyl group include those described above. As a method for adjusting to a desired counter ion, ion exchange treatment with metal salts such as nitrates, sulfates and hydrochlorides, acid treatment with nitric acid, sulfuric acid, hydrochloric acid, formic acid, etc., or pH adjustment treatment with alkaline metal compounds, etc. The method of applying is mentioned.

  The acrylate-based fiber of the present invention produced as described above has a difference in the hygroscopicity of the fiber between 20 ° C. 70% RH and 20 ° C. 95% RH obtained by the evaluation method described below of 30% or more, preferably Can indicate 35 to 45%. Further, since the core portion is made of a hard acrylonitrile polymer, the physical properties of the fiber are not deteriorated, the spinning process can be easily performed, and the durability during use can be improved.

  The above-mentioned acrylate-based fibers are used as short fibers alone or mixed with other short fibers, and are combined with long fibers to form a long-short composite spun yarn. The mixing ratio of the acrylate fiber in the long-short composite spun yarn is preferably 5 to 40%, more preferably 10 to 30%. If the mixing ratio of the acrylate fiber is less than the above range, the hygroscopicity at high humidity may not be sufficiently exhibited, and if it exceeds the above range, the thread-like quality is deteriorated and the cost is not preferable.

  The long fiber of the long-short composite spun yarn is not particularly limited as long as it is a fiber that can be used in textile applications such as polyester, nylon, triacetate, and polypropylene, but in order to effectively exhibit the moisture absorption and desorption property intended by the present invention, polyester or A hydrophobic filament such as nylon is preferable, and polyester is more preferable. From the viewpoint of spinning processability of long-short composite spinning, it is preferable to use the polyester filament.

  The long-short composite spun yarn of the present invention can take various forms, but as shown in FIG. 3, it is composed of a center layer, an outermost layer and an intermediate layer between them as seen in a cross section. It is preferable that acrylate fibers are arranged in the intermediate layer of the long-short composite spun yarn, and hydrophobic filaments are arranged in the center layer and the outermost layer.

  Since the outermost layer of the long-short composite spun yarn is composed of hydrophobic filaments, the surface layer part of the yarn and the fabric is smooth to the acrylate fiber arranged in the intermediate layer of the long-short spun yarn without retaining the absorbed water. In addition to being able to shift to, the moisture can be efficiently vaporized in the same manner even when moisture is released. In addition, even in an environment where there is a large amount of sweat or high humidity, the part that comes into direct contact with the human body retains the dry feel unique to hydrophobic fibers, and can maintain a comfortable surface touch.

  In addition, since the central layer of the long-short composite spun yarn is composed of the hydrophobic filament, the physical properties of the long-short composite spun yarn are stable, the spinning process can be easily performed, and the handleability in the knitting process can be improved. In addition, even in the moisture absorptive and desorptive property intended by the present invention, since the moisture is not retained in the central layer of the spun yarn, the moisture absorptive and desorptive property can be more effectively exhibited.

  The mixing ratio of the hydrophobic filament yarn forming the outermost layer of the long-short composite spun yarn of the above-mentioned form is preferably 15 to 50%. If the mixing ratio of the hydrophobic filament system in the outermost layer of the yarn is too low, the exposure of the fibers in the intermediate layer and the central layer to the surface increases, and thus the functionality and texture of the fibers may not be obtained. On the other hand, if the mixing ratio is too high, the ratio of the fibers forming the intermediate layer and the central layer will be small, and it will be difficult to exhibit the functionality and the spinnability as a long-short composite yarn may be significantly reduced. From the viewpoints of functionality, texture and spinnability, the mixing ratio of the hydrophobic filaments forming the outermost layer is preferably 20 to 45%, more preferably 25 to 35%.

  The mixing ratio of the hydrophobic filaments forming the central layer of the long-short composite spun yarn of the above-mentioned form is preferably 3 to 30%. If the mixing ratio is too large, the effect of stabilizing the physical properties of the long / short composite yarn becomes low, and the spinning processability may become unstable. On the other hand, if the mixing ratio is too large, the ratio of the materials arranged in the intermediate layer and the outermost layer decreases, and the fibers of the central layer are exposed to the intermediate layer and the outermost layer, which may make it difficult to exhibit the characteristics intended by the present invention. is there. The mixing ratio is preferably 5 to 20%, more preferably 8 to 20%.

  The long-short composite spun yarn of the present invention is required to have a moisture absorption difference between 20 ° C. 70% RH and 20 ° C. 95% RH of 1.0 to 5.0% and a tying force value of 300 times or more. Is. The moisture absorption difference can be achieved by incorporating the acrylate fiber having the core-sheath structure described above and adjusting the content thereof, and regarding the tying force value, the long-short composite spun yarn of the specific form described above. Can be achieved by adopting

  Next, an example of the method for producing the long-short composite spun yarn of the present invention will be described below with reference to FIG. First, acrylate fibers with a core-sheath structure and general spinning materials such as polyester, nylon, rayon, cotton, and hemp are uniformly mixed and blended in the ordinary spinning and blending cotton process, and ordinary card, kneading, A roving process is used to produce a blended roving containing the acrylate fiber. Next, spinning is carried out by a spinning process using the long-short composite spinning device shown in FIG. 1 so that the filament yarn is arranged in the center layer and the outermost layer of the yarn.

  In FIG. 1, a mixed spun roving R containing an acrylate fiber is released from the cypress M1 and supplied to the back roller 8 via the guide 3, between the back roller 8 and the second roller 7, and between the second roller 7 and the front. The draft is received between the rollers 12 and is spun from the front rollers 12. At that time, the hydrophobic filament B1 is released from the filament pan PB, and is supplied to the drafted roving F just upstream of the front roller 12 by the filament positioning guide 10 via the guides 2 and 6. On the other hand, the hydrophobic filament A1 is released from the filament pan PA, passes through the tension devices 9 through the guides 1, 4 and 5, passes through the coating control guide 11, and is wrapped around the fiber bundle K by the winding torque of the fiber bundle F to be coated. Then, it is manufactured by being twisted on the bobbin 14 as the long-short composite spun yarn Y1 after being actually twisted by a traveler (not shown) through the snell wire 13.

  The long-short composite spun yarn of the present invention is composed of a center layer and an outer layer when viewed in a cross-section in addition to the above-described form of FIG. 3, and an acrylate fiber is arranged in the center layer of the long-short composite spun yarn. The form of FIG. 4 in which the hydrophobic filaments are arranged in the outer layer can be adopted. Further, although the abrasion resistance (coupling force value) is inferior to that of the embodiment shown in FIGS. 3 and 4, the acrylate-based fiber and the hydrophobic filament are uniformly mixed in the cross-sectional view of FIG. The morphology and the cross section shown in FIG. 6 in which the acrylate fiber aggregate and the hydrophobic filament aggregate are configured side by side, and in the cross section, the central layer and the outer layer covering it It is possible to adopt the configuration of FIG. 7 in which the hydrophobic filament is arranged in the central layer of the long-short composite spun yarn and the acrylate fiber is arranged in the outer layer. The composite spun yarn in these forms can be easily manufactured by a conventionally known method.

  The long-short composite spun yarn of the present invention produced as described above is a long-short composite spun yarn using the above-mentioned acrylate fiber having a core-sheath structure, and a hydrophobic filament, thereby giving high humidity uncomfortable to a human body. It exhibits excellent hygroscopicity under the environment, and in a low-humidity environment that does not require hygroscopicity, it can dissipate and dissipate absorbed moisture, and the binding force value is 300 times or more, further 400 times or more, Can obtain abrasion resistance of 500 times or more, further 600 times or more, and further 1000 times or more. Furthermore, by using this long-short composite spun yarn for at least a part, it is possible to provide a woven or knitted fabric that has a refreshing feeling and has a comfortable wearing feeling and a moisture absorbing / releasing function with little sticky feeling even when a large amount of sweat is sweated. ..

  It is preferable to adjust the extraction pH of the long-short composite spun yarn or woven or knitted fabric of the present invention to 5 to 12. It is more preferably adjusted to 6 to 12, and even more preferably 7 to 10. By setting the extraction pH within this range, the long-short composite spun yarn in a high humidity atmosphere can sufficiently exhibit hygroscopicity. When the extraction pH is less than 5, the hygroscopic ability in a high humidity atmosphere is likely to decrease, and when the extraction pH is more than 12, even if the hygroscopic ability is sufficient, the burden on the skin is likely to be large in the portion in contact with the skin. The extraction pH is a value measured by the pH of the JIS L1096: 2010 8.37 extract.

  The long-short composite spun yarn or woven or knitted fabric of the present invention is preferably subjected to hydrophilic processing in order to enhance water absorption. When hydrophilic treatment is applied, the diffusivity of sweat is increased when a large amount of liquid phase sweat is sweated, water on the surface of the composite yarn is easily released, stickiness can be further reduced, and a refreshing feeling is improved.

  The form of the woven or knitted fabric of the present invention includes innerwear, pants, shirts, uniforms, cut-and-sews, denim, pajamas, bathrobes, leggings, stockings, supporters, belly rolls, gloves, handkerchiefs, towels, scarves, stoles, mufflers, masks, faces. Mention may be made of masks, hats, pillows, pillowcases, sheets, towelettes, floor pads, mats, rugs, carpets and the like. The long-short composite spun yarn may be contained in the woven or knitted material in a substantially uniform manner, in a concentrated manner in a specific portion, or in a specific ratio at each location. The content ratio of the long-short composite spun yarn in the woven or knitted material is preferably at least 10% by weight, more preferably at least 20% by weight.

  Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples. The measuring methods used for evaluation in the examples are as follows.

(1) Numerical value A
The sample fiber is immersed in a dyeing bath containing 2.5% of a cationic dye (Nichilon Black G 200) and 2% of acetic acid based on the weight of the fiber at a bath ratio of 1:80, and boiled for 30 minutes. After that, it is washed with water, dehydrated and dried. The obtained dyed fiber is thinly sliced perpendicular to the fiber axis, and the fiber cross section is observed with an optical microscope. At this time, the central part made of the acrylonitrile-based polymer is dyed black, and the surface layer part having a large number of carboxyl groups is not sufficiently fixed with the dye and becomes green. The diameter (L1) of the fiber in the cross section of the fiber and the diameter (L2) of the central part dyed black at the boundary where the part where the green color starts to change to black are measured, and the sheath in the cross section of the fiber is calculated by the following formula. The ratio of the area occupied by a part is calculated. The average value of 10 samples is taken.
Percentage of area occupied by sheath in fiber cross section [%] = [1-{(L2 / 2) ² π / (L1 / 2) ² π}] × 100

About 1 g of the sample fiber is immersed in 50 ml of a 1 mol / l hydrochloric acid aqueous solution for 30 minutes. The fiber sample is then immersed in water at a bath ratio of 1: 500. After 15 minutes, when it is confirmed that the bath pH is 4 or more, it is dried (if the bath pH is less than 4, wash again with water). Next, about 0.2 g of a sufficiently dried fiber sample is precisely weighed (W1 [g]), 100 ml of water is added, and further, 15 ml of 0.1 mol / l sodium hydroxide aqueous solution and 0.4 g of sodium chloride are added. And phenolphthalein are added and stirred. After 15 minutes, the sample fiber and the filtrate are separated by filtration, and then the sample fiber is washed with water until the color of phenolphthalein disappears. The combined washing water and the filtrate at this time are titrated with a 0.1 mol / l hydrochloric acid aqueous solution until the coloration of phenolphthalein disappears, and the hydrochloric acid aqueous solution consumption (V1 [ml]) is determined. The total amount of carboxyl groups is calculated from the obtained measured value by the following formula.
Amount of carboxyl group [mmol / g] = (0.1 × 15−0.1 × V1) / W1

The numerical value A is calculated by the following expression using each numerical value obtained by the above expression.
A = amount of carboxyl group [mmol / g] / ratio of area occupied by sheath in fiber cross section [%]

(2) Moisture Absorption Rate The spun yarn sample is dried in an absolutely dry state, the weight is measured, and then the moisture is absorbed at 20 ° C. and 50% RH to measure the weight after 24 hours. Then, it was made to absorb moisture in an environment of 20 ° C. and 70% RH and the weight after 24 hours was measured, and further, it was made to absorb moisture in an environment of 20 ° C. and 95% RH and the weight after 24 hours was measured. The moisture absorption rate was calculated from the weight of the spun yarn at each relative humidity and the weight of the spun yarn in an absolutely dry state.

(3) Tying force value Using a tying force tester (Hirada Riken Co., Ltd.), a friction plate having 11 kinds of friction pieces having different shapes was rotated at a speed of 80 rpm, and external force was repeatedly applied to the spun yarn to form a yarn. The number of times of cutting or until the short fiber portion of the long / short composite yarn is scraped and the sheath is removed is measured. In the measurement, a load of 70 g is applied to the spun yarn.

(4) Stickiness evaluation (skin release)
The stickiness evaluation was performed by using a surface property tester KES (manufactured by Kato Tech Co., Ltd.) as a skin separation property, and a wet sample to which 160 g / m ² of water was applied, and an artificial sebum composed of oleic acid, squalene, and triolein were applied. The coefficient of friction with the formed film was measured. The load was 100 g / cm ² .

(5) Wear evaluation (coolness, stuffiness)
Six subjects were asked to wear the knitted sample, and after walking for 15 minutes in an environment of 32 ° C and 65% RH, they were allowed to stand for another 15 minutes. Regarding the feeling (dryness) and the feeling of stuffiness, they were evaluated in four grades of ⊚: very good, ∘: good, Δ: normal, and ×: unpleasant, and the highest evaluation was taken as the evaluation result.

(Example 1)
An acrylonitrile-based polymer (intrinsic viscosity [η] = 1.5 in 30 ° C. dimethylformamide) containing 90% by mass of acrylonitrile and 10% by mass of acrylic acid methyl ester was dissolved in a 48% by mass aqueous solution of rhodanese to prepare a spinning solution. Prepared. The spinning solution was subjected to spinning, washing with water, stretching, crimping, and heat treatment according to a conventional method to obtain an acrylic fiber having a single fiber fineness of 1.7 dtex.

The obtained acrylic fiber was subjected to crosslinking introduction treatment and hydrolysis treatment simultaneously at 100 ° C. for 2 hours in an aqueous solution containing 0.5% by mass of hydrazine hydrate and 2.0% by mass of sodium hydroxide to obtain 8% by mass. % Nitric acid aqueous solution, treated at 100 ° C. for 3 hours and washed with water. The obtained fiber is dipped in water, sodium hydroxide is added to adjust a part of the carboxyl groups to a salt type, washed with water and dried to obtain an acrylate fiber having a core-sheath structure with a fineness of 3.0 dtex. Obtained. The ratio of the area occupied by the sheath portion in the fiber cross section of the obtained fiber was 61%, the amount of carboxyl groups was 3.7 mmol / g, and the numerical value A was 0.061. In the infrared absorption measurement of such a fiber, there is absorption near 2250 cm ⁻¹ derived from a nitrile group, and hydrolysis of the nitrile group is progressing in the fiber surface layer portion, but the nitrile group is present in the fiber central portion. It was confirmed that it remained.

  As shown in FIG. 3, a polyester filament of 17 dtex / 8 filament was arranged in the center layer of the composite spun yarn, and the acrylate fiber having the core-sheath structure and 1.0 dtex of polyester staple having a fiber length of 38 mm were used in a weight ratio of 30. A short-spun composite spun yarn of English count 30 was prepared by arranging short fibers mixed in a ratio of: 70 in the middle layer and arranging 56 dtex / 24 filament polyester filament in the outermost layer. However, in the long-short composite spun yarn, the weight ratio of the 17dtex / 8filament polyester filament spun yarn arranged in the central layer is 8%, and the weight ratio of the acrylate fiber having a core-sheath structure arranged in the intermediate layer is 20%. The weight ratio of the polyester staple having the fiber length of 1.0 dtex and the fiber length of 38 mm was 44%, and the weight ratio of the polyester filament of 56 dtex / 24 filament arranged in the outermost layer was 28%. Using this long-short composite spun yarn, a 26-inch 28-gauge knitted fabric was knitted. The finished greige was processed according to the general dyeing process of knitting. At the time of dyeing the polyester, hydrophilic processing was performed by simultaneous exhaustion treatment, and finally the fabric pH was adjusted to 7 for finishing.

(Example 2)
A long-short composite spun yarn of English cotton count 40 count was produced in the same manner as in Example 1 except that the polyester filament arranged in the outermost layer was changed to 33 dtex / 18 filament polyester filament. However, in the long-short composite spun yarn, the weight ratio of the 17 dtex / 8 filament polyester filament arranged in the central layer to the whole yarn is 11%, and the weight ratio of the acrylate fiber having a core-sheath structure arranged in the intermediate layer is 20%. %, 1.0 dtex, and the weight ratio of polyester staple having a fiber length of 38 mm was 46%, and the weight ratio of 33 dtex / 18 filament polyester filament arranged in the outermost layer was 23%. Using this long-short composite spun yarn, a milling knitted fabric was knitted with a 16-inch 19-gauge. The finished greige was finished in the same manner as in Example 1.

(Example 3)
An acrylate fiber having a core-sheath structure, a long-short composite spun yarn, and a plain knit fabric were produced in the same manner as in Example 1 except that the concentration of sodium hydroxide during the production of the acrylate fiber was 1.5% by mass. The ratio of the area occupied by the sheath portion in the fiber cross section of the acrylate fiber was 45%, the amount of carboxyl groups was 3.1 mmol / g, and the numerical value A was 0.069.

(Example 4)
An acrylate fiber having a core-sheath structure, a long-short composite spun yarn, and a plain knit fabric were produced in the same manner as in Example 1 except that the concentration of sodium hydroxide at the time of producing the acrylate fiber was 2.5% by mass. The ratio of the area occupied by the sheath in the fiber cross section of the acrylate fiber was 78%, the amount of carboxyl groups was 4.3 mmol / g, and the numerical value A was 0.055.

(Example 5)
As shown in FIG. 4, acrylate fibers having the same core-sheath structure as in Example 1 and polyester staples having 1.0 dtex and a fiber length of 38 mm were mixed and spun at a weight ratio of 28:72, mainly staple fibers. Layers and 56 dtex / 24 filament polyester filaments were placed in the outer layer to make English cotton count 30 count long / short composite spun yarn. However, in the long-short composite spun yarn, the weight ratio of the acrylate fiber having a core-sheath structure arranged in the central layer is 20%, 1.0 dtex, and the weight ratio of the polyester staple having a fiber length of 38 mm is 52%, and the polyester layer is arranged in the outer layer. The weight ratio of the 56 dtex / 24 filament polyester filament was 28%. Using this long-short composite spun yarn, a plain knitted fabric was produced with a 26 inch 28 gauge and finished in the same manner as in Example 1.

(Example 6)
As shown in FIG. 5, short fibers obtained by mixing acrylate fibers having the same core-sheath structure as in Example 1 and 1.0 dtex and polyester staple having a fiber length of 38 mm in a weight ratio of 28:72 were prepared. A 56 dtex / 24 filament polyester filament was opened using an electric opening device and uniformly mixed with short fibers to produce a long-short composite spun yarn of English cotton count 30 count. However, in the long-short composite spun yarn, the weight ratio of the acrylate fiber having a core-sheath structure is 20%, 1.0 dtex, the weight ratio of polyester staple having a fiber length of 38 mm is 52%, and the weight ratio of the polyester filament of 56 dtex / 24 filament is It was set to 28%. Using this long-short composite spun yarn, a plain knitted fabric was produced with a 26 inch 28 gauge and finished in the same manner as in Example 1.

(Example 7)
As shown in FIG. 6, acrylate fibers having the same core-sheath structure as in Example 1 and 1.0 dtex, polyester staple having a fiber length of 38 mm were mixed-spun to a short fiber ratio of 28:72 by weight, A long-short composite spun yarn of English cotton count 30 was produced by the intertwisting spinning method so that the polyester filament of 56 dtex / 24 filament was made side by side. However, in the long-short composite spun yarn, the weight ratio of the acrylate fiber having a core-sheath structure is 20%, 1.0 dtex, the weight ratio of polyester staple having a fiber length of 38 mm is 52%, and the weight ratio of the polyester filament of 56 dtex / 24 filament is It was set to 28%. Using this long-short composite spun yarn, a plain knitted fabric was produced with a 26 inch 28 gauge and finished in the same manner as in Example 1.

(Example 8)
As shown in FIG. 7, a polyester filament of 56 dtex / 24 filament was arranged in the center layer, and an acrylate fiber having the same core-sheath structure as in Example 1 and 1.0 dtex of polyester staple having a fiber length of 38 mm were used in a weight ratio of 28: Short fibers mixed and mixed so as to have a ratio of 72 were arranged in the outer layer, and a long-short composite spun yarn of English count 30 was produced. However, in the long-short composite spun yarn, the weight ratio of the acrylate fiber having a core-sheath structure is 20%, 1.0 dtex, the weight ratio of polyester staple having a fiber length of 38 mm is 52%, and the weight ratio of the polyester filament of 56 dtex / 24 filament is It was set to 28%. Using this long-short composite spun yarn, a plain knitted fabric was produced with a 26-inch and 28-gauge and finished in the same manner as in Example 1.

(Example 9)
Acrylic fibers having the same core-sheath structure as in Example 1 and 1.0 dtex, polyester staple having a fiber length of 38 mm were mixed-spun at a weight ratio of 47:53, and short fibers were placed in the intermediate layer. In the same manner as in Example 1, a long and short composite spun yarn with an English cotton count of 30 was produced. However, in the long-short composite spun yarn, the weight ratio of the 17dtex / 8filament polyester filaments arranged in the central layer to the whole yarn is 8%, and the weight ratio of the acrylate fiber having a core-sheath structure arranged in the intermediate layer is 30%. %, 1.0 dtex, and the weight ratio of the polyester staple having a fiber length of 38 mm was 34%, and the weight ratio of the 56 dtex / 24 filament polyester filament arranged in the outermost layer was 28%. Using this long-short composite spun yarn, a plain knitted fabric was produced with a 26 inch 28 gauge and finished in the same manner as in Example 1.

(Example 10)
Acrylic fibers having the same core-sheath structure as in Example 1 and 1.0 dtex, polyester staple having a fiber length of 38 mm were mixed-spun at a weight ratio of 16:84 to place short fibers in the intermediate layer. In the same manner as in Example 1, a long and short composite spun yarn with an English cotton count of 30 was produced. However, in the long-short composite spun yarn, the weight ratio of the 17dtex / 8filament polyester filaments arranged in the central layer to the whole yarn is 8%, and the weight ratio of the acrylate fiber having a core-sheath structure arranged in the intermediate layer is 10%. %, 1.0 dtex, fiber length 38 mm, the weight ratio of the polyester staple was 54%, and the weight ratio of the 56 dtex / 24 filament polyester filament arranged in the outermost layer was 28%. Using this long-short composite spun yarn, a plain knitted fabric was produced with a 26 inch 28 gauge and finished in the same manner as in Example 1.

(Comparative Example 1)
A polyester filament of 17 dtex / 8 filament is arranged in the center layer, and an acrylate fiber having the same core-sheath structure as in Example 1 and a polyester staple of 1.0 dtex and a fiber length of 38 mm have a weight ratio of 8:92. The mixed-spun short fibers were arranged in the middle layer, and the polyester filament of 56 dtex / 24 filament was arranged in the outermost layer to prepare a long-short composite spun yarn of English cotton count 30 count. However, in the long-short composite spun yarn, the weight ratio of 17 dtex / 8 filament polyester filaments arranged in the center layer is 8%, and in the long-short composite spun yarn, the weight ratio of acrylate fiber having a core-sheath structure is 5%. The weight ratio of the polyester staple having 0 dtex and the fiber length of 38 mm was 59%, and the weight ratio of the polyester filament of 56 dtex / 24 filament arranged in the outermost layer was 28%. Using this long-short composite spun yarn, a plain knitted fabric was produced with a 26 inch 28 gauge and finished in the same manner as in Example 1.

(Comparative example 2)
A general ordinary spun yarn of English cotton count of 30 was produced using only polyester staple having 1.0 dtex and a fiber length of 38 mm. Using this spun yarn, a 26-inch 28-gauge knitted fabric was produced and finished in the same manner as in Example 1.

(Comparative example 3)
The same method as in Example 1 was repeated except that the acrylate fiber having a core-sheath structure of Example 1 was replaced with a normal acrylate fiber having no core-sheath structure (“EX” manufactured by Japan Exlan Co., Ltd.). A long and short composite spun yarn of English count 30 was produced. Using this long-short composite spun yarn, a plain knitted fabric was produced with a 26 inch 28 gauge and finished in the same manner as in Example 1.

(Comparative example 4)
A long / short composite spun yarn of English cotton count 30 was produced in the same manner as in Example 1 except that only polyester staple having 1.0 dtex and a fiber length of 38 mm was used as the short fibers arranged in the intermediate layer. Using this long-short composite spun yarn, a plain knitted fabric was produced with a 26 inch 28 gauge and finished in the same manner as in Example 1.

(Comparative example 5)
An acrylate fiber having a core-sheath structure, a long-short composite spun yarn, and a plain knit fabric were produced in the same manner as in Example 1 except that the concentration of sodium hydroxide during the production of the acrylate fiber was 3.2 mass%. The ratio of the area occupied by the sheath portion in the fiber cross section of the acrylate fiber was 94%, the carboxyl group amount was 4.4 mmol / g, and the numerical value A was 0.046.

Table 1 shows the evaluation results of the spun yarns and knits obtained in Examples 1 to 10 and Comparative Examples 1 to 5.

  From the results of Table 1, all of Examples 1 to 10 have high moisture absorption and desorption properties according to environmental changes, and show rapid moisture absorption characteristics in an environmental region uncomfortable for a human body of 70% RH or more, and a moisture absorption action is required. In the low humidity range, which is not considered to be the case, it exerts a high moisture release cooling effect. In addition, Examples 1 to 10 have excellent wear resistance of long fibers due to the form of a specific long-short composite spun yarn, and also have a feeling of coolness and a comfortable wearing feeling without stuffiness. I understand. Particularly, in Examples 1 to 5, 9 and 10, due to the structure of the long and short composite spun yarn, very excellent properties are exhibited in abrasion resistance and stickiness evaluation. On the other hand, in Comparative Examples 1 to 5, the hygroscopic effect under high humidity (difference in hygroscopicity between A and B) was inferior to that of the example, so that there was a problem in any of abrasion resistance, stickiness evaluation, and wearing evaluation. ..

  The long-short composite spun yarn of the present invention and the woven or knitted fabric using the same have moisture absorption and desorption properties and dehumidifying and cooling properties which have not existed in the past, and at the same time have excellent wear resistance and knitting property, and have a refreshing feeling when worn. It can suppress stuffiness and is useful as a comfortable woven or knitted fabric particularly suitable for summer.

Claims (7)

It has a core-sheath structure composed of a core part containing an acrylonitrile polymer as a main component and a sheath part containing a cross-linking structure and a polymer having a carboxyl group as a main component, and the numerical value A represented by the following formula is 0. A long-short composite spun yarn in which at least a part of acrylate-based fibers of 050 to 0.080 is used, and a moisture absorption difference between 20 ° C. 70% RH and 20 ° C. 95% RH is 1.0 to 5.0. %, And a binding force value of 300 times or more, a long-short composite spun yarn.
A = amount of carboxyl group [mmol / g] / ratio of the area occupied by the sheath portion in the fiber cross section   When viewed in cross section, the long-short composite spun yarn is composed of a center layer, an outermost layer, and an intermediate layer between them, and an acrylate fiber is disposed in the middle layer of the long-short composite spun yarn, and the center layer and the outermost layer are arranged. The long-short composite spun yarn according to claim 1, wherein a hydrophobic filament is arranged in the outer layer.   The long-short composite spun yarn is composed of a central layer and an outer layer when viewed in a cross section, and the acrylate fiber is arranged in the central layer of the long-short composite spun yarn and the hydrophobic filament is arranged in the outer layer. The long-short composite spun yarn according to claim 1.   The long-short composite spun yarn according to claim 1, wherein the long-short composite spun yarn is configured by uniformly mixing acrylate fibers and hydrophobic filaments when viewed in a cross section.   The long-short composite spun yarn according to claim 1, wherein the long-short composite spun yarn is constituted by an aggregate of acrylate-based fibers and an aggregate of hydrophobic filaments side by side when viewed in a cross section.   The long-short composite spun yarn is composed of a center layer and an outer layer covering the center layer when viewed in a cross section, a hydrophobic filament is arranged in the center layer of the long-short composite spun yarn, and an acrylate fiber is arranged in the outer layer. The long-short composite spun yarn according to claim 1, characterized in that   A woven or knitted fabric comprising the long-short composite spun yarn according to any one of claims 1 to 6 in at least a part thereof.