JP4235244B1 - Stretch fabric - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a stretch fabric having an excellent antibacterial property and deodorizing property, particularly an aging odor deodorizing function in addition to a stretch function.
SOLUTION: (A) A spun yarn containing 100 to 5% by weight of a cellulosic fiber containing a carboxyl group with respect to a spun yarn and 0 to 95% by weight of a polyester fiber with respect to the spun yarn, and (B) polyurethane elasticity A fabric containing fibers, (A) 99 to 70% by weight of spun yarn with respect to the fabric, and (B) 1 to 30% by weight of polyurethane elastic fiber, the antibacterial agent being exhausted or supported Stretch fabric.
[Selection figure] None

Description

  The present invention relates to a stretch fabric having antibacterial and deodorant properties.

In recent years, there has been an increasing demand for comfort in everyday life. In addition to comfortable stretchability, clothes fabrics (clothing fabrics, knitted fabrics, fiber structures, etc.) have attracted attention. .
For example, a modified cellulosic fiber obtained by graft copolymerization of methacrylic acid to a cellulosic fiber such as cotton fiber is known as having excellent deodorizing properties against bad odors such as ammonia and urine odor (for example, JP-A-6-184941). On the other hand, with regard to deodorizing properties, a deodorizing function for aging odors is particularly required due to the progress of an aging society. In general, aging odor is considered to be composed of odor components of ammonia, acetic acid, isovaleric acid and nonenal. According to the evaluation standards of “deodorization processing” published by the Fiber Evaluation Technical Council. For example, the function of removing all components of ammonia, acetic acid, isovaleric acid and nonenal is essential for deodorizing the aging odor.

Various attempts have been made to obtain fabrics having various deodorizing functions. Fabrics formed by knitting fibrils to which a titanium oxide photocatalyst is attached (for example, see Patent Document 2), and fabric products themselves A method (for example, refer to Patent Document 3) or the like in which a photocatalyst-containing treatment solution is charged and processed is known.
However, to the best of the applicant's knowledge, it has not yet been reported that a fabric having a deodorizing property with excellent aging odor has been obtained.

  On the other hand, various attempts have been made to obtain a fabric having a stretching function, and stretch fabrics are known which have stretchability imparted by mixing various elastic fibers (see, for example, Patent Documents 4 to 7). ). However, a fabric obtained by treating the stretch fabric with the stretch fabric itself by a post-processing method to impart deodorizing properties has a problem that the durability to washing and the stretchability after washing are insufficient.

Japanese Patent Laid-Open No. 6-184941 JP 2002-030552 A JP 2007-126664 A Japanese Patent Laid-Open No. 09-302553 JP 09-228144 A JP 2006-028453 A JP 2004-131866 A

As described above, there has been no report on a stretch fabric having a satisfactory aging odor eliminating property.
An object of the present invention is to provide a stretch fabric having excellent antibacterial and deodorizing properties, in particular, an aging odor deodorizing function, in addition to the stretch function, in view of the problems of the conventional stretch fabric. To do.

  In the process of developing a stretch fabric having a deodorizing property, the present inventors show that a combination of a specific cellulosic fiber, a polyester fiber, and a polyurethane elastic fiber exhibits a surprising deodorizing property against an aging odor. I found Based on such knowledge, the present invention has been completed by further earnest development.

（ただし、Ｒ1は炭素原子数が好ましくは１〜３の直鎖のアルキレン基、Ｒ2は水素または炭素原子数が好ましくは１〜３のアルキル基をそれぞれ表す。）
［７］ ポリウレタン弾性繊維を構成するポリウレタンの有効末端アミン濃度が１５〜５０ｍｅｑ／ｋｇである［１］〜［６］のいずれかに記載のストレッチ布帛。
［８］ 抗菌剤が有機窒素硫黄系化合物、第４級アンモニウム系化合物、リン酸エステル系化合物および金属イオンを含有する無機系化合物のいずれか1種以上から選択されてい
る［１］〜［７］のいずれかに記載のストレッチ布帛。
［９］ 目付が１００〜１０００ｇ／ｍ^２であり、タテ方向および／またはヨコ方向の伸長率が５％以上である［１］〜［８］のいずれかに記載のストレッチ布帛。
［１０］ 紡績糸が６〜６０英式綿番手である［１］〜［９］のいずれかに記載のストレッチ布帛。
［１１］ 抗菌剤による吸尽もしくは担持処理に際し、抗菌剤を含む処理液のｐＨが５．０以上６．０以下の範囲である［１］〜［１０］のいずれかに記載のストレッチ布帛。 That is, the present invention has the following configuration.
[1] (A) A spun yarn containing 100 to 5% by weight of a cellulosic fiber containing a carboxyl group and 0 to 95% by weight of a spun yarn with respect to the spun yarn, and (B) a polyurethane elastic fiber (A) 99% to 70% by weight of spun yarn with respect to the fabric, and (B) 1% to 30% by weight of polyurethane elastic fiber, the antibacterial agent being exhausted or supported Stretch fabric.
[2] The stretch fabric according to [1], wherein the cellulose fiber containing a carboxyl group is a modified cellulose fiber obtained by graft copolymerization reaction of methacrylic acid to a cellulose fiber.
[3] The spun yarn is obtained by one or more production methods of a ring traveler method, an open end method, a bundling method, and a fine spinning and twisting method, according to [1] or [2] Stretch fabric.
[4] The stretch fabric according to any one of [1] to [3], wherein the fiber surface area per gram of the polyester fiber is about 0.1 m ² or more, or the single fiber fineness of the polyester fiber is about 3 denier or less.
[5] The stretch fabric according to any one of [1] to [4], wherein the polyurethane group concentration of the polyurethane constituting the polyurethane elastic fiber is about 0.2 mol / kg to 3.5 mol / kg.
[6] A polyalkylene ether diol having a number average molecular weight of 250 to 10,000, wherein the polyurethane elastic fiber contains 5 to 25 mol% of the following structural unit (a) and 95 to 75 mol% of the structural unit (b), and diisocyanate The stretch fabric according to any one of [1] to [5], which comprises a polyurethaneurea obtained by polymerizing a compound and a diamino compound.

(However, R1 is preferably a linear alkylene group having 1 to 3 carbon atoms, and R2 is hydrogen or an alkyl group having 1 to 3 carbon atoms.)
[7] The stretch fabric according to any one of [1] to [6], wherein the polyurethane constituting the polyurethane elastic fiber has an effective terminal amine concentration of 15 to 50 meq / kg.
[8] The antibacterial agent is selected from one or more of organic nitrogen sulfur compounds, quaternary ammonium compounds, phosphate ester compounds and inorganic compounds containing metal ions [1] to [7 ] The stretch fabric in any one of.
[9] The stretch fabric according to any one of [1] to [8], wherein the basis weight is 100 to 1000 g / m ² and the elongation in the vertical direction and / or the horizontal direction is 5% or more.
[10] The stretch fabric according to any one of [1] to [9], wherein the spun yarn is a 6-60 British cotton count.
[11] The stretch fabric according to any one of [1] to [10], wherein the pH of the treatment liquid containing the antibacterial agent is in the range of 5.0 or more and 6.0 or less during exhaustion or carrying treatment with the antibacterial agent.

  The stretch fabric of the present invention has excellent antibacterial and deodorant properties, in particular aging deodorant function, in addition to the stretch function, and further, all these functions do not decrease or decrease even after washing the fabric. Washing durability is surprisingly superior in that the degree of

Hereinafter, the present invention will be described in detail.
In the production of the stretch fabric of the present invention, (A) 100 to 5% by weight of the cellulosic fiber containing a carboxyl group is 100 to 5% by weight with respect to 100% by weight of the spun yarn, and 0 to 95% by weight with respect to 100% by weight of the spun yarn. % Spun yarn is used.

  The cellulosic fibers in the present invention are not particularly limited, and examples thereof include cellulosic natural fibers such as cotton and hemp, cellulosic regenerated fibers such as rayon, semi-synthetic cellulosic fibers, so-called undesignated fibers (lyocell, cupra), and the like. . In particular, lyocell is preferably used as a clothing material because of its soft texture and good hygroscopicity.

  The cellulose-based fiber containing a carboxyl group in the present invention is preferably a modified cellulose-based fiber obtained by graft copolymerization reaction of methacrylic acid with the cellulose-based fiber. The modified cellulosic fibers are excellent in adsorptivity to basic malodorous substances such as ammonia, amines, and urine odors, and are preferable as deodorant fibers. And the said modified cellulosic fiber is preferable from a viewpoint which can exhibit the synergistic effect with respect to deodorizing property in mixing with the below-mentioned polyurethane elastic fiber. In addition, the manufacturing method of the said modified cellulose fiber is disclosed by the patent 3239146 (Unexamined-Japanese-Patent No. 6-184941) which Nippon Kayofye dyeing company owns. For example, radiation graft polymerization is performed in a state in which a cellulosic fiber product to be treated is immersed in an aqueous methanol solution containing a monomer mixture composed of acrylic acid and sodium vinyl sulfonate or a monomer mixture composed of acrylic acid and vinylbenzyltrimethylammonium chloride.

  The polyester fiber in the present invention is not particularly limited, but is made of polyethylene terephthalate, holybutylene terephthalate, polyethylene terephthalate, polytetramethylene glycol terephthalate, or a polyester resin mainly composed of these structural units and copolymerized with other copolymer components. The obtained polyester fiber is particularly preferably a polyethylene terephthalate fiber, that is, a fiber whose main polymer is polyethylene terephthalate or copolymer polyethylene terephthalate.

  For example, polyethylene terephthalate, polybutylene terephthalate, or ethylene terephthalate unit as the main repeating component (preferably 90 mol% or more of the repeating unit), butylene terephthalate unit as the main repeating component (preferably the repeating unit A fiber comprising 90 mol% or more) can be preferably used. Especially, the fiber which consists of polyester which an ethylene terephthalate unit makes 90 mol% or more of a repeating component is preferable, and the fiber which consists of polyester which an ethylene terephthalate unit makes 95 mol% or more of a repeating component is more preferable. It is more preferable that the polyester is an ethylene terephthalate unit having 100 mol% repeating components, that is, a fiber made of polyethylene terephthalate. This polyethylene terephthalate fiber has a good texture, gloss, and easy care properties such as being less likely to wrinkle, and is suitable as a fiber material constituting a stretchable fabric. The polyethylene terephthalate fiber is suitable for use in combination with the polyurethane urea elastic fiber preferably used in the present invention, and can be a good stretch fabric.

The cross-sectional form of these polyester fibers may be round or irregular.
Further, a water-absorbing quick-drying polyester fiber yarn is preferably used. The water-absorbing and quick-drying polyester fiber includes a fiber in which many hollows are provided on the wall surface of the hollow fiber, and a number of grooves and holes are provided on the fiber surface. Use fibers with irregular cross-sections that absorb moisture in pores, grooves on the fiber surface, between fibers, and spaces between yarns, and various types of water-absorbing quick-drying fibers sold by synthetic fiber manufacturers. Is possible. For example, water-absorbing quick-drying polyester fibers include “Cool Max” manufactured by Invista, “Theo α” manufactured by Toray Industries, Inc. “Welky” manufactured by Teijin Fibers Limited, “Dry Fast” manufactured by Toyobo Co., Ltd., Asahi Kasei Fibers Co., Ltd. "Technofine" manufactured by the company can be mentioned.
In order to impart water-absorbing and quick-drying properties, as described above, a material having a low hygroscopic property, such as a polyester fiber or an acrylic fiber, is used, and a hollow fiber is formed into a fiber having many smaller holes on its wall surface. Many grooves and holes are provided on the shape and the fiber surface, etc., and the water absorption is absorbed by the minute holes of the fibers themselves, the grooves on the fiber surface, the spaces between the fibers, and the spaces between the yarns. Examples of the fiber having a modified cross-sectional shape as described above include those provided with minute holes or voids into which moisture enters.

If necessary, polyester conductive fibers may be used as antistatic synthetic fibers. Examples of the conductive fibers include composite polyester fibers using carbon black as a conductive material (for example, “Bertron” manufactured by Kanebo Gosei Co., Ltd.), white copper iodide and metal composite oxides (for example, TiO ₂ · SnO ₂ · Examples include composite polyester fibers using Sb ₂ O ₂ ), but are not limited thereto.

The polyester fiber used in the present invention preferably has a fiber surface area per gram of woven or knitted fabric of 0.1 m ² or more or a single fiber fineness of about 3 denier or less, more preferably a surface area of 0.12 m ² or more or a single fiber. Fineness is about 3 denier or less. The action of the antibacterial agent adhering to or exhausting the fiber depends on the surface area of the fiber or the single fiber fineness of the fiber. Therefore, the fiber having a surface area of 0.1 m ² or more or a fiber having a single fiber fineness of about 3 denier or less An antibacterial fiber structure (fabric) having industrial washing durability can be obtained.

In the spun yarn (A) of the present invention, the cellulosic fiber containing a carboxyl group is 100 to 5% by weight with respect to 100% by weight of the spun yarn, and the polyester fiber is 0 to 95% by weight with respect to 100% by weight of the spun yarn. It will be.
The content of the carboxyl group-containing cellulose fiber in the (A) spun yarn is 100 to 5% by weight, preferably 100 to 10% by weight, more preferably 100 to 50% by weight, and most preferably 75. -60% by weight.

  For example, a spun yarn comprising 100% by weight of a modified lyocell fiber modified by graft polymerization of 5% by weight of methacrylic acid by the above-mentioned conventional method on lyocell fiber, and 10% by weight of methacrylic acid by a conventional method. Modified yarn modified by graft polymerization of 10% by weight of methacrylic acid on a spun yarn and cotton comprising 30% by weight of modified lyocell fiber and 70% by weight of polyester fiber modified by graft polymerization. Examples thereof include spun yarn comprising 90% by weight of cotton and 10% by weight of polyester fiber. Most preferably, the spun yarn is composed of 75 to 60% by weight of modified lyocell fiber and 25 to 40% by weight of polyester fiber modified by graft polymerization of 10% by weight of methacrylic acid to the lyocell fiber by a conventional method. It is.

  Furthermore, from the viewpoint of the texture of the fabric and the like, the content ratio of the cellulose fibers containing carboxyl groups in the spun yarn is adjusted to the above content by mixing the cellulose fibers not subjected to the modification. Adjustment is also preferably performed. For example, a spun yarn comprising 10% by weight of modified lyocell fiber and 90% by weight of cotton modified by graft polymerization of 5% by weight of methacrylic acid by a conventional method on lyocell fiber, and methacrylic by a conventional method on lyocell fiber. A spun yarn consisting of 30% by weight of modified lyocell fiber and 70% by weight of cotton modified by graft polymerization of 10% by weight of acid, and modified by graft polymerization of 10% by weight of methacrylic acid on cotton. A spun yarn comprising 30% by weight of modified cotton and 70% by weight of cotton, and 50% by weight of modified rayon modified by graft polymerization of 10% by weight of methacrylic acid by a conventional method on rayon. A modified yarn modified by graft polymerization of 12% by weight of methacrylic acid on a spun yarn and cupra consisting of 50% by weight by a conventional method. A spun yarn comprising 80% by weight of plastic and 20% by weight of rayon, 10% by weight of modified lyocell fiber modified by graft polymerization of 5% by weight of methacrylic acid on a lyocell fiber and 60% by weight of cotton. %, And a spun yarn comprising 30% by weight of polyester fiber.

  In addition, (A) When the cellulosic fiber containing the carboxyl group in a spun yarn is less than 5 weight%, the deodorizing effect will fall remarkably. The spun yarn (A) is composed of 100 to 5% by weight of a cellulose-based fiber containing a carboxyl group and 0 to 95% by weight of a polyester fiber, and a plurality of synthetic fibers other than the polyester fiber, such as a polyamide fiber. Polyacrylonitrile fiber and natural fibers such as wool and silk may be combined at a ratio of less than 50% by weight.

The spun yarn (A) in the present invention is a blended yarn of a cellulose-based fiber (preferably modified lyocell fiber) containing a carboxyl group and a polyester fiber, particularly a water-absorbing quick-drying polyester fiber, from the viewpoint of improving water absorption. A blended yarn is preferable, and a blended yarn of a cellulose-based fiber containing a carboxyl group and an antistatic polyester conductive fiber is preferable.
In addition, (A) the spun yarn may be produced according to a known method, for example, obtained by one or more production methods of a ring traveler method, an open end method, a bundling method, and a fine spinning and twisting method. It is preferable that

Although the fineness of the (A) spun yarn in this invention is not specifically limited, 6-60 English counts are preferable. The count is a unit of the thickness of the thread. The larger the count, the thinner the thread. In the present invention, both single yarns and twin yarns within the above-mentioned thickness range can be suitably used.
In addition, it is not preferable to use a thread thicker than 6th because the fabric becomes too thick and lacks softness. It is not preferable to use a thread thinner than 60th because it becomes too thin and easily damaged.

  The polyurethane elastic fiber in the present invention may be an elastic fiber made of any of polyurethane and polyurethane urea.

  The urethane group concentration of the polyurethane constituting the polyurethane elastic fiber is preferably about 0.2 mol / kg to 3.5 mol / kg, more preferably about 0.4 mol / kg to 1.0 mol / kg. The urethane group concentration is calculated as (polymer diol (mol) contained in polyurethane resin) × 2 / (polyurethane resin weight (kg)).

Moreover, it is preferable that the effective terminal amine density | concentration of the polyurethane which comprises a polyurethane elastic fiber is 15-50 meq / kg. The effective terminal amine concentration is calculated by the following method. First, a polyurethane or polyurethane urea solution is diluted with N, N-dimethylacetamide (hereinafter abbreviated as DMAc) to obtain a 25% solution having a concentration of 2% by weight, and potentiometric titration with p-toluenesulfonic acid (0.01 N). Then, the total content (a) of the primary amine and the secondary amine is determined. Subsequently, salicylaldehyde was added to this solution to react with the primary amine, and then the secondary amine was subjected to potentiometric titration with p-toluenesulfonic acid (0.01 N) to obtain a secondary amine concentration (b). Ask for. The effective terminal amine concentration is calculated by the following formula.
Effective terminal amine concentration (meq / kg) = (a)-(b)

  The polyurethane urea elastic fiber is preferably a polyalkylene ether having a number average molecular weight of about 250 to 10,000 and containing about 5 to 25 mol% of the following structural unit (a) and about 95 to 75 mol% of the structural unit (b). A polyurethane urea obtained by polymerizing a diol, a diisocyanate compound, a symmetric diamino compound, more preferably a symmetric aromatic diamino compound, and is produced by spinning this polyurethane urea by a usual spinning method. Elastic fiber.

（ただし、Ｒ3は炭素原子数が好ましくは１〜３の直鎖のアルキレン基、Ｒ4は水素または好ましくは炭素原子数１〜３のアルキル基をそれぞれ表す。）

(However, R3 is preferably a linear alkylene group having 1 to 3 carbon atoms, and R4 is hydrogen or preferably an alkyl group having 1 to 3 carbon atoms.)

  The structural unit (a) is for introducing a side chain into the polyalkylene ether diol, and is represented by, for example, a structural unit derived from 3-methyl-tetrahydrofuran or a structural unit derived from neopentyl glycol. The Among these, a structural unit in which R1 is a linear alkylene group having 2 carbon atoms and R2 is hydrogen is particularly preferable.

  This polyalkylene ether diol has high flexibility and high recoverability by having a side chain in the molecular chain. Furthermore, the polyurethaneurea elastic fiber manufactured using the polyether diol having a side chain as described above has improved durability against high-temperature dyeing and high-temperature heat setting, and a reduction in recovery stress is remarkably suppressed.

The copolymer composed of the structural unit (a) and the structural unit (b) is preferably block copolymerization or random copolymerization. In particular, the structural unit (a) is present at the end of the molecular chain. It is preferable to exist in a rich manner. That is, the proportion of the structural unit (a) occupying the end of the molecular chain (terminal a proportion) is larger than the proportion of the structural unit (a) in the whole molecular chain (total a proportion). It is preferable that the value of the terminal a ratio with respect to is at least twice. In this way, it is possible to further increase the retention of the recovery stress of the elastic fiber particularly during high-temperature dyeing.
Thus, in order for the structural unit (a) to be present in a rich state at the molecular chain end, a step of polymerizing the monomer that forms the structural unit (a) and the monomer that forms the structural unit (b) In the final stage, a polymerization method may be employed in which a monomer for forming the structural unit (a) is additionally supplied and reacted. The proportion of the structural unit (a) present in the terminal can be controlled to a desired level by the amount of the additionally supplied monomer, the supply timing, and the like.

  In the case where 3-methyl-tetrahydrofuran and tetrahydrofuran are used as both monomers described above, for example, a strong acid capable of ring-opening tetrahydrofuran, such as chlorosulfonic acid, 2-fluorosulfonic acid, perchloric acid, etc., is used as a catalyst. The polyalkylene ether diol which consists of the said structural unit (a) and a structural unit (b) can be manufactured by making it exist and making it copolymerize at the temperature of about 0-50 degreeC.

  In the polyalkylene ether diol, the proportion of the structural unit (a) is 5 to 25 mol%, preferably 8 to 20 mol%. The structural unit (b) is the remaining ratio. By including the structural unit (a) at such a ratio, dyeing at a high temperature can be more preferable.

  The polyurethane elastic fiber preferably used in the present invention is composed of polyurethane urea that is polymerized by using the above-mentioned specific polyalkylene ether diol as a polyol. Therefore, the elastic fiber has high elongation, increased strength, and several degrees. Can be dyed, and after dyeing, it is possible to maintain high stretchability.

Examples of the diamino compound which is an example of the diamino compound used in the present invention include ethylenediamine, hexamethylenediamine, diaminodiphenylmethane, p-phenylenediamine and the like, but diaminodiphenylmethane (hereinafter, referred to as fiber coloring prevention). (Abbreviated as MBA).
Moreover, a normal thing is used as a diisocyanate compound, for example, diphenylmethane diisocyanate (henceforth MDI) is used.

  Polyurethane urea can be produced by, for example, chain-extending a prepolymer obtained from about 1 mol of a polyalkylene ether diol and about 2 mol of a diisocyanate compound with a symmetric aromatic diamino compound. In this polyurethane urea, there is a structural unit having a urethane bond (—NHCOO—) formed from a polyalkylene ether diol and a diisocyanate compound, and further formed from a symmetric aromatic diamino compound and a diisocyanate compound. And a structural unit having a urea bond (—NHCONH—). When MDI is used as the diisocyanate compound and MBA is used as the symmetric aromatic diamino compound, a reaction in which water is added to the DMAc solution of MDI to produce MBA can also be used. That is, instead of adding MBA as a chain extender, water is added and the remaining MDI reacts with water to form MBA in the system. This MBA acts as a chain extender to produce polyurethane urea. You can also

  It is presumed that structural units having urea bonds (urea structural units) present in polyurethane urea generally have higher heat resistance when there are more hydrogen bonds. However, in reality, polyurethane urea fibers containing urea structural units formed from MDI and MBA are treated with high-temperature water treatment rather than polyurethane urea fibers containing urea structural units formed from MDI and ethylenediamine. Further, the deterioration of the polymer during the high-temperature steam treatment or the dry heat treatment is suppressed to be small, the recovery stress retention of the elastic fiber after the treatment is high, and the residual strain reduction rate is large. The reason is not clear, but when there are many hydrogen bonds, water easily penetrates into the molecule, whereas a compound having an aromatic ring is difficult to penetrate water into the molecule. When a symmetric aromatic diamino compound having an aromatic ring is used, it is considered that water penetration into the molecule is suppressed, and as a result, the hot water resistance of the resulting polyurethane urea is improved.

  Furthermore, the polyurethane elastic fibers preferably used in the present invention have high heat resistance and dry heat resistance. The reason for this is not clear, but by having an aromatic urea group in the polymer, its cohesiveness is increased, and when the elastic fiber is heated, it becomes possible to suppress the movement of the glycol component. It is estimated that dry heat resistance is improved. Therefore, it is considered that the wet heat resistance and dry heat resistance of the elastic fiber can be improved by using polyurethane urea obtained by chain extension with a symmetric aromatic diamino compound such as diaminodiphenylmethane.

  The polyurethane urea elastic fiber used in the present invention is exposed to high-temperature hot water or high-temperature steam in the high-temperature dyeing process, and is further subjected to conditions such as elongation and tension. It is presumed that the decrease in recovery force is not necessarily proportional to the number of hydrogen bonds. When the stretched elastic fiber is treated with hot water or treated with steam, it is considered that the polymer is thermally decomposed or hydrolyzed to reduce the recoverability of the elastic fiber. However, the elastic fiber preferably used in the present invention is such that the residual strain of the elastic fiber treated under such wet heat treatment conditions is lower than that of the elastic fiber before the treatment.

  The polyurethane urea elastic fiber used in the present invention preferably further has the following characteristics. That is, the retention rate of the recovery stress of the yarn treated for 60 minutes at a constant length in hot water at 130 ° C. (retention rate compared to the recovery stress of the untreated yarn, hereinafter referred to as hot water retention rate) is 55. %, And the residual strain is preferably reduced by the treatment. Here, the hot water retention rate is a recovery stress at 200% elongation that is retained by heat treatment for 60 minutes in a state where the elastic fiber is stretched twice. The recovery stress at 200% elongation is the stress at the time of the fifth recovery in which the elastic fiber is stretched and recovered five times, and the residual strain is a value obtained by dividing the deformation after this repeated elongation by the original length. is there. The hot water retention of the polyurethaneurea elastic fiber is preferably 55% or more, and particularly preferably 58% or more.

  Moreover, it is preferable that the residual strain of the elastic fiber after the hot water treatment is lower than the yarn before the treatment. Particularly preferred is that the residual strain of the elastic fiber after the treatment is reduced by 1% or more than the residual strain of the elastic fiber before the treatment. The smaller the residual strain, the better the elastic recovery characteristics. Thus, the decrease in the residual strain in this way means that the polymer itself constituting the yarn has excellent recovery characteristics even after the hydrothermal treatment. . When the polyurethane urea elastic fiber having such a hot water retention value and residual strain characteristics is used with the above-mentioned (A) spun yarn in the present invention, the antibacterial agent used in the present invention is exhausted or supported and dyed. Even when subjected to high-temperature moist heat treatment, the stretch fabric structure of the present invention has high recoverability and is rich in stretchability.

  Further, a more preferable polyurethane urea elastic fiber further has a retention rate of a recovery stress of yarn treated for 1 minute at a constant length in steam at 130 ° C. (retention rate compared to a recovery stress of an untreated yarn. The steam retention rate is 85% or more, and the residual strain is reduced by the steam treatment. More preferable fibers having such characteristics are those having a steam retention of 90% or more and a residual strain of the treated yarn of 1% or more lower than that of the untreated yarn. When a fabric as a stretchable fiber structure is produced using elastic fibers having such a steam retention value and residual strain characteristics together with the above-mentioned (A) spun yarn, a stretch that causes less trouble in high-temperature dyeing and repeated dyeing A fabric can be made.

  More preferably, the retention rate of the recovery stress of the yarn treated for 1 minute at a constant length in air at 200 ° C. (more specifically, the retention rate compared to the recovery stress of the untreated yarn. , Which is referred to as dry heat retention) is to use polyurethaneurea elastic fiber having 50% or more. The dry heat retention is more preferably 55% or more. In the case of such an elastic fiber, it is necessary to heat set at a high temperature at the time of dyeing. A stretch fabric is obtained.

  The polyurethane urea elastic fiber preferably used in the present invention is preferably composed of the specific polyurethane urea described above and further has the above-described characteristics. The production method of the polyurethane urea elastic fiber having such characteristics is not particularly limited, but can be produced by arbitrarily controlling the composition, molecular weight, spinning conditions and the like of the polyurethane urea.

  The cellulose-based fiber, polyester fiber, and polyurethane elastic fiber containing a carboxyl group used in the present invention may appropriately include various inorganic / organic additives, stabilizers, and the like. For example, hydrotalcite compounds, huntite and hydromagnesite, various minerals typified by tourmaline, etc., metal oxides typified by Ca, Mg, Zn, Al, Ba, Ti, complex oxides, hydroxylation A thing etc. may be contained in the range which does not impair the effect of this invention.

  In addition, when blending these inorganic additives, for the purpose of improving the dispersibility in the yarn and stabilizing the spinning, for example, organic substances such as fatty acids, fatty acid esters, polyol organic substances, silanes, etc. It is also preferable to use inorganic chemicals surface-treated with a base coupling agent, a titanate base coupling agent or a mixture thereof.

  Further, the cellulose-based fiber, polyester fiber, and polyurethane elastic fiber containing a carboxyl group used in the present invention contain various stabilizers, pigments, and the like as long as they do not impair the effects of the present invention. Also good. For example, as a stabilizer, an addition polymer of divinylbenzene and p-cresol (“METACROL” (registered trademark) 2390, manufactured by DuPont), t-butyldiethanolamine and methylene-bis- (4-cyclohexyl isocyanate) Polyurethane ("Metacral" (registered trademark) 2462 manufactured by DuPont) produced by the above reaction, light resistance agent, antioxidant, etc., so-called BHT and "Sumizer" GA-80 manufactured by Sumitomo Chemical Co., Ltd. Both hindered phenols such as benzotriazoles such as “Tinubin” manufactured by Ciba Geigy, benzophenone drugs, phosphorus drugs such as “Sumilyzer” P-16 manufactured by Sumitomo Chemical Co., Ltd., and various hindered amines Chemicals, inorganic pigments such as titanium oxide and carbon black, fluorine resin powder Are silicone resin powder, metal soap such as magnesium stearate, bactericides and deodorizers including silver, zinc and their compounds, lubricants such as silicone and mineral oil, barium sulfate, cerium oxide, betaine Various antistatic agents such as phosphoric acid and the like may be added, or may exist by reacting with the polymer. In order to further enhance the durability to light and various nitric oxides in particular, a nitric oxide scavenger such as HN-150 manufactured by Nippon Hydrazine Co., Ltd., a thermal oxidation stabilizer such as Sumitomo Chemical Co., Ltd. ) “Sumilyzer” GA-80, etc., and a light stabilizer such as “Sumisorb” 300 # 622, manufactured by Sumitomo Chemical Co., Ltd.

  The antibacterial agent used in the present invention is not particularly limited, and examples thereof include various organic and inorganic antibacterial agents. Organic nitrogen sulfur compounds, quaternary ammonium compounds, phosphate ester compounds, and metals It is preferably composed of at least one of inorganic compounds containing ions.

As organic antibacterial agents, organic antibacterial agents having antibacterial metal ions such as organic nitrogen sulfur compounds, phenolic compounds, organic tin compounds, organic copper compounds, organic silver compounds, various organic silicone quaternary ammonium salts, Quaternary ammonium salts of alkyl phosphates (for example, cetyldimethylammonium chloride), benzalkonium chloride, alkylaryl sulfonates, organic antibacterial agents such as halophenol and phenol mercuric acetate, polyphenols, and chitosan .
Amino group are preferred as antimicrobial active site of the antimicrobial agent, more preferably allylamino and diallylamino, in concrete terms as an amine-based antimicrobial agent, dimethylamine and epichlorohydrin condensates and diallylamine derivatives based polymer or allylamine and vinylamine derivative polymer Is preferred. From the viewpoint of washing durability, the primary, secondary, and tertiary allylamine polymers can further enhance the intended deodorizing effect, and do not impair the fabric softness of the resulting fabric.

  In consideration of antibacterial properties, the state in which the antibacterial agent is attached to the fiber surface is most excellent because of its high contact frequency with bacteria. However, this state is not preferable from the viewpoint of washing durability because the antibacterial agent is easily peeled off. On the other hand, when the antibacterial agent is uniformly diffused inside the fiber, the antibacterial property is lowered but the washing durability is improved. From the above, the state in which the antibacterial agent is distributed in a ring shape in the vicinity of the fiber surface inside the fiber, or branched and diffused from the fiber surface to the inside is excellent in antibacterial properties and washing durability. Conceivable. In general, antibacterial processing using such organic antibacterial agents is a continuous process in which the antibacterial agent is continuously padded, dried, and cured in post-processing, batch processing in which heat treatment is performed with a liquid dyeing machine, etc. However, it is also possible to use a fiber containing an antibacterial agent in advance as a constituent fiber, and it is preferably applied so that the antibacterial agent is exposed on the surface of the fabric material. From the viewpoint of uniform deodorization performance and washing durability, batch treatment is preferred.

  The inorganic antibacterial agent is not particularly limited as long as it is water-insoluble. Copper, silver, zinc, titanium, zirconium, vanadium, molybdenum, tungsten, chromium, iron, cobalt, nickel, manganese, germanium, cerium, etc. Transition metal hydroxides, aluminum, silicon, tin, antimony and other amphoteric metal hydroxides, magnesium and other hydroxides, metal carbonates excluding alkali metals, phosphates, silicates, aluminates And zirconate. Among these metal compounds, zinc hydroxide and basic zinc carbonate are particularly suitable.

In addition, an antibacterial material prepared by impregnating a fabric into a dispersion in which a fine particle composition in which silver is supported on zeolite is dispersed in a binder, drying, and cutting to a predetermined size can also be used. As the silver carrier, hydroxyapatite, silica gel, silica / alumina, zirconium phosphate, etc. can be used in addition to zeolite.
Instead of silver supported on zeolite, antibacterial metals such as copper and zinc, or oxides, hydroxides or salts thereof, β-tujapricin (hinokitiol), polyphenones, Titry oil, benzalkonium chloride, chloride Cationic surfactants such as benzethonium, amphoteric surfactants such as alkylpolyaminoethylglycine hydrochloride, biguanide compounds such as chlorhexidine gluconate and polyhexamethylene biguanidine hydrochloride, 2- (4-thiazolyl) benzimidazole, N -(Fluorodichloromethylthio) phthalimide, 2,3,5,6-cytochloro-4- (methylsulfonyl) -pyridine, 10,10'-oxybisphenoxyarsine, trimethoxysilyl-propyloctadecylammonium chloride, 2-n- Octyl 4-isothiazolin-3-one, bis (2-pyridylthio-1-oxide) zinc, sodium dehydroacetate, salicylic acid, paraoxybenzoates, N-cocoyl-L-arginine ethyl ester / pyrrolidone carboxylate, hexachlorophene It is also preferable to use a composition impregnated with one or more kinds or supported on a carrier using a binder.

  Above all, when zinc oxide is finely divided, it not only exhibits antibacterial and deodorizing performance, but also has the ability to chemically deodorize acidic gases such as acetic acid and isovaleric acid resulting from the decomposition of sweat with body odor. Get higher. In addition, zinc oxide is used as a raw material for cosmetics and has been proven to be highly safe for the human body, and is excellent as an antibacterial agent for clothing and an acid gas deodorant that often come into direct contact with the skin.

In addition, an antibacterial agent that is sterilized and antibacterial by the photocatalytic action of the optical semiconductor powder is also preferably used. This photocatalytic action is generated as a chemical action by an electrochemical cell in which one electrode is an optical semiconductor ceramic that is an optical semiconductor powder and the other electrode is a metal. As such an optical semiconductor powder, TiO ₂ , CdS, CdSe, WO ₃ , Fe ₂ O ₃ , SrTiO ₃ , KNbO _{3 and the} like are used, and as the metal powder, various metal powders such as gold, silver, platinum and copper are used. Used.

In the present invention, the antibacterial agent is preferably exhausted or supported by about 0.1 to 10% by weight, more preferably about 0.1 to 5% by weight, based on the weight of the entire fabric.
The stretch fabric of the present invention is one that has been exhausted or supported in the range where the pH of the treatment liquid containing the antibacterial agent is 5.0 or more and 6.0 or less when exhausted or supported by the antibacterial agent. preferable.

  That is, the exhaust or supporting treatment with an antibacterial agent on a stretch fabric containing 99 to 70% by weight of (A) spun yarn and 1 to 30% by weight of (B) polyurethane elastic fiber is usually performed by a conventional method. Can be done. For example, batch processing and continuous processing performed by simultaneously adding an antibacterial agent in the dyeing solution of the fabric can be mentioned. When an independent antibacterial agent is exhausted or supported, the antibacterial agent is used as a solvent (if necessary). For example, the treatment liquid dissolved or dispersed in water, an organic solvent such as methanol) is impregnated with the above fabric or a textile product containing the fabric and heat-treated with a liquid dyeing machine or the like, or in the mangle after dipping Examples thereof include a continuous treatment method in which the resin is uniformly drawn and subjected to dry heat treatment. Among these, batch processing is preferable from the viewpoint of obtaining uniform deodorizing performance. In those cases, the treatment liquid preferably maintains acidity from the viewpoint of protecting the carboxyl group present in the fabric and exhibiting good deodorizing properties, and the pH of the preferred treatment liquid containing the antibacterial agent is 5.0 or more. A range of 6.0 or less is preferable. In this case, the prescribed amount of the antibacterial agent is uniformly absorbed by the stretch fabric and can be exhausted or supported. In the process performed by simultaneously adding an antibacterial agent in the dyeing solution of the fabric, the pH at the time of dark dyeing such as black and wrinkles is preferably 5.0 to 6.0 from the viewpoint of color development, and at the time of dyeing white or light color The pH is preferably 5.5 to 6.0 from the viewpoint of deodorizing performance and yellowing. The exhaust or dipping process time is usually preferably about 1 to 120 minutes.

In the present invention, the provision of deodorizing properties includes polyurethane resins having deodorizing properties against nonenal and isovaleric acid, carboxyl groups having deodorizing properties against basic gases such as ammonia, and acetic acid and isovaleric acid. It is carried out by using an antibacterial agent which is imparted by cellulosic fibers having a deodorizing property against acid gas and which suppresses the growth of bacteria that decompose urine and sweat to generate odor. In this case, as described above, an antibacterial agent that has antibacterial and deodorant properties, such as titanium oxide, that generates active oxygen when exposed to ultraviolet rays and decomposes organic substances when exposed to ultraviolet rays may be used. It is.
In addition, if necessary, for example, activated carbon, silica gel, alumina, activated clay, molecular sieve, amorphous aluminosilicate with large bulk specific gravity, etc., high adsorption performance for odor components such as ammonia, methyl mercaptan, hydrogen sulfide, etc. A substance (deodorant) may be further added or fixed to the fiber surface. Of course, a fiber in which a deodorant is used in advance may be used.

  Deodorants include ceramic powders such as zeolite, apatite (activated apatite), activated carbon, activated alumina, activated silica gel, bentonite, or sepiolite, and silk fiber-containing materials, or metal salts such as iron and copper, and these. Can be mentioned. Since these deodorizers have not only a deodorizing action but also a moisture absorbing action, one component can impart both deodorizing and moisture absorbing functions to the fabric. Among these, zeolite is preferable. A feature of zeolite is that it has countless micron pores of amorphous or honeycomb shape and has a large specific surface area. Therefore, when in contact with moisture, moisture is sucked into the pores, and further, an inorganic gas containing four major odors (ammonia, trimethylamine, hydrogen sulfide, methyl mercapton) and organic containing isovaleric acid, phenol, etc. Even gas is inhaled.

<Stretch fabric>
The stretch fabric of the present invention is obtained by producing a fabric from the above-described (A) spun yarn and (B) polyurethane elastic fiber according to a conventional method, and may be any of a woven fabric, a knitted fabric or a nonwoven fabric. For example, (B) a polyurethane elastic fiber may be covered with (A) a spun yarn to obtain a fabric as a covering elastic fiber, or (A) a spun yarn with (B) a polyurethane elastic fiber bare yarn (bear) It is also possible to weave and weave as it is to make an interwoven fabric.

Furthermore, in the case of a woven fabric, it may be woven only with the above-described spun yarn and polyurethane elastic fiber, or fibers other than these may be woven.
Weaving organization includes plain weaving, oblique weaving, satin weaving, etc., changing plain weaving, changing weaving weaving, changing satin weaving, etc., weaving weaving, imitation weaving, satin weaving, etc. Double weave such as double weave, weft double weave, double weave weave, bag weave, double velvet such as double velvet, multi-layer structure such as belt weave, vertical pile weave such as velvet, towel, seal, velor In addition, bevel piles such as bevel, velvet, velvet, cole heaven and the like, and entangled structures such as cocoons, cocoons and crests are preferred.
Weaving is preferably carried out with a loom (such as a fly shuttle loom) or a non-weaving loom (such as a rapier loom, a gripper loom, a water jet loom, an air jet loom).

Also, in the case of a knitted fabric, it may be knitted only with the above-described spun yarn and polyurethane elastic fiber, or fibers other than these may be knitted. The type of the knitted fabric may be a weft (weft) knitted fabric or a warp (warp) knitted fabric. The weaving structure is preferably a flat knitting, rubber knitting, double-sided knitting, pearl knitting, tuck knitting, floating knitting, one-sided knitting, lace knitting, or splicing. Atlas knitting, double cord knitting, half tricot knitting, back hair knitting, jacquard knitting and the like are preferable. The number of layers may be a single layer or a multilayer of two or more layers.
The knitting is preferably performed by a flat knitting machine such as a circular knitting machine, a flat knitting machine, or a cotton knitting machine, a tricot knitting machine, a Raschel knitting machine, a Milanese knitting machine, or the like.

  Furthermore, the fabric of the present invention is particularly suitable for socks and underwear such as tights, stockings, pantyhose and socks. The stretch fabric of the present invention is a fabric in which (A) the spun yarn contains 99 to 70% by weight and (B) the polyurethane elastic fiber contains 1 to 30% by weight, and preferably (A) the spun yarn is 95 to 70%. 80% by weight, and (B) polyurethane elastic fiber contains 5 to 20% by weight.

The manufacturing method of the stretch fabric of this invention is not specifically limited, Arbitrary methods are applicable.
In addition, the fineness of (B) polyurethane elastic fiber is not specifically limited, What is necessary is just to use an arbitrary thing according to a use.
Further, stretch fabric of the present invention, basis weight is 100 to 1000 g / ^{m 2,} preferably elongation is longitudinal direction and / or transverse direction with more than 5%, basis weight is the 150~280g / ^{m 2} It is particularly preferred.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. Hereinafter, simply “%” means “% by weight”.

<Spun yarn made of cellulose fiber and polyester fiber containing carboxyl group>
A lyocell raw cotton (single yarn fineness 1.5 denier, fiber length 38 mm) manufactured by Lenzing Co. was used as the modified cellulose fiber, and carboxylation treatment with a methacrylic acid grafting rate of 12% was carried out by a conventional method. 30% of this modified cellulosic fiber raw material and polyester fiber raw material mixed with 70% by weight of Dacron (R) raw cotton (single yarn fineness 1.5 denier, fiber length 38 mm, hereinafter referred to as T702) manufactured by INVISTA, USA Then, using a ring type spinning machine manufactured by Toyota Industries Corporation, a blended yarn T702-70-SLY-30 of 30th British cotton count was produced (T702 is a polyester type, -70 is 70%, -SLY is Cellulose fiber type, -30 represents English cotton count).
Similarly, blended yarn T702-30-SLY-30 made of 70% modified cellulose fiber raw material and 30% polyester fiber raw material was produced.
Similarly, 100% of modified cellulose fiber raw cotton was used to produce spun yarn SLY-100-30, the 30th British cotton count.
<Polyurethane elastic fiber>

87.5 mol of dehydrated tetrahydrofuran and 12.5 mol of dehydrated 3-methyl-tetrahydrofuran were charged into a reactor equipped with a stirrer and the catalyst (70% by weight of perchloric acid and anhydrous was added at a temperature of 10 ° C. under a nitrogen seal. A copolymerized tetramethylene ether diol having a number average molecular weight of 2500 (by a copolymerization method in which a polymerization reaction is carried out in the presence of 30% by weight of acetic acid) for 8 hours and neutralized with an aqueous sodium hydroxide solution. The structural unit derived from 3-methyl-tetrahydrofuran (containing 12.5 mol%) was used as the polyalkylene ether diol.
The vessel was charged with 1.41 mol of MDI per 1 mol of the copolymerized tetramethylene ether diol and reacted at 90 ° C., and the resulting reaction product was sufficiently added to N, N-dimethylacetamide (DMAc). Dissolved. Next, a DMAc solution containing MBA as a chain extender was added to the solution in which the reaction product was dissolved to prepare a polyurethane urea solution having a solid content of 29% by weight in the polymer.

This polyurethane urea solution is discharged from the spinneret into a high-temperature (350 ° C.) inert gas (N ₂ ) with 4 filaments, dried by passing through the high-temperature gas, and the yarn being dried is twisted together. Through an air jet type twisting machine, 4 filaments were coalesced, wound at a speed of 540 m / min, and a polyurethane urea elastic fiber of 33 dtex was produced by 4 filaments coalescence. Hereinafter, this product may be abbreviated as Ba.
In addition, the urethane group density | concentration of the polyurethane which comprises this polyurethane elastic fiber was 0.70 mol / kg, and the effective terminal amine density | concentration was 32 meq / kg.

<How to wash>
It conforms to the washing method manual established by the Council for Evaluation of New Functionality of Textile Products. That is, using a home electric washing machine specified in JIS L0217 Washing Method 103, 40 ml of JAFET standard detergent (manufactured by the New Functional Evaluation Council for Textile Products) is dissolved in 30 liters of water at 40 ° C. to obtain a washing liquid. In this washing liquid, a 1 kg sample to be washed is put. Washing for 5 minutes, dehydration, rinsing for 2 minutes, dehydration, rinsing for 2 minutes, and dehydration were performed once, and washing was performed 50 times.

<Initial antibacterial test>
Conforms to the manual for quantitative antibacterial testing of textile products established by the Council for Evaluation of New Functionality of Textile Products. In other words, 0.4 g of the following test bacteria 1 ± 0.3 × 10 ⁵ cells / ml are uniformly inoculated into a sterilized neutral broth of 1/20 concentration and cultured at 37 ° C. for 18 hours. After completion of the culture, the test bacteria are washed out, and a pouch plate agar medium is prepared with the solution. For unprocessed products (samples not subjected to antibacterial treatment), the test bacteria are washed out immediately after inoculation, and a pouched plate agar medium is prepared with the solution, followed by culturing at 37 ° C. for 24-48 hours. Measure the number of viable bacteria. Antibacterial properties are evaluated by the bacteriostatic activity value according to the following formula. The higher the bacteriostatic activity value, the better the antibacterial property. In addition, Staphylococcus aureus (ATCC 6538P) was used as a test microbe.
Bacteriostatic activity value: Log (B) -Log (C)
However, the test establishment condition: Log (B) -Log (A)> 1.5 must be satisfied.
A: Average value of the number of bacteria recovered immediately after inoculation of the raw product B: Average value of the number of bacteria recovered and cultured for 18 hours for the raw product C: Bacteria recovered for 18 hours of the processed product (sample subjected to antibacterial treatment) The fabric after 10 washings was used as an average sample of the number. The results are shown in Table 4.

<Durable antibacterial test>
The same test as the above <Initial Antibacterial Test> was performed using the fabric after 50 washings as a sample. The results are shown in Table 5.

<Initial deodorization test>
2-nonenal (C ₉ H ₁₆ O, molecular weight 140.2, CAS number: 463-53-8 or less, simply referred to as nonenal), isovaleric acid, ammonia and acetic acid, which are the causes of aging odors as odor components A deodorization test was conducted using the four components, and the deodorization performance was evaluated by the following method. The results are shown in Table 4.
Deodorization performance evaluation According to the JAFET method, an instrumental analysis test was performed on the above four components, and a sensory test was performed on Nonenal. Washing was performed by tumble drying in accordance with JIS L 217 103 method.
Instrumental analysis test: Ammonia and acetic acid were measured by the detector method, and isovaleric acid and nonenal were measured by gas chromatography. Nonenal was judged to be acceptable (indicated by ○) when the reduction rate was 75% or more, isovaleric acid was 85% or more, ammonia was 70% or more, and acetic acid was 80% or more.
Sensory test: Out of 6 judges, 5 or more people judged that the odor was weak according to the following criteria.
Odor strength: When stronger than the judgment odor gas Odor weakness: When equal or weaker than the judgment odor gas

<Durable deodorization test>
The same test as the above <Initial deodorization test> was performed using the fabric after washing 50 times as a sample. The results are shown in Table 5.

<Elongation rate of fabric (fabric stretchability)>
The stretch rate S1 (%) at a temperature of 23 ° C. and a humidity of 65 RH% and the stretch rate S2 (%) at a temperature of 43 ° C. and a humidity of 65 RH% are determined according to the stretchability of the stretch fabric defined in JIS L1096-1998 6.14.1. Measured by method B (constant load method).

[Example 1]
(A) As a spun yarn containing a cellulose fiber and a polyester fiber containing a carboxyl group, a blended yarn of No. 30 English cotton count comprising 30% of the above modified cellulose fiber raw cotton and 70% polyester fiber raw cotton. (T702-70-SLY-30) (702 is a polyester type, -70 is 70 wt%, -SLY is a cellulosic fiber type, -30 is an English cotton count), and (B) polyurethane elastic fiber Using the above-mentioned Ba, bare-tenji circular knitted fabric (38 inch diameter, 24 gauge, 114 feeder) was prepared under the conditions shown in Table 1, and a fabric containing 5% polyurethane elastic fiber was obtained.

According to the processing steps and processing conditions shown in Table 2, the fabric was subjected to a two-bath dyeing process generally applied to polyester and cellulose fiber mixed fabrics.
As shown in Table 2, the antibacterial agent exhaustion processing was performed simultaneously with the dyeing of the polyester, and the treatment was performed at a bath ratio of 1:10, pH 5.0, and a drug concentration of 5% (% by weight relative to the dough). As the antibacterial agent, a 40% concentration aqueous solution (PAA-D41-HCl, manufactured by Nittobo Co., Ltd.) containing an allylamine / diallylamine polymer having a weight average molecular weight of about 20,000 represented by the following structural formula was used.
Next, it was confirmed that 2.5% of the antibacterial agent was exhausted with respect to the weight of the dough.

The dough density was adjusted in the final heat setting step, and finally a bare-tempered dough having a dough weight of 175 g / m ² was obtained. Table 3 shows conditions such as the configuration of the fabric and the knitting structure. Tables 4 to 5 show the evaluation results of the fabrics. Antibacterial function, deodorant function, sweat absorption, quick drying, fabric stretchability, fabric soft feeling (refers to the soft feel of the fabric by finger touch. The same applies to Examples 2-5 and Comparative Examples 1-3), and washing The stretch fabric which has the function which was excellent in all these performances after repeating 50 times was obtained.

[Example 2]
(A) A spun yarn including a cellulose-based fiber containing a carboxyl group and a polyester fiber, and (B) a polyurethane elastic fiber, the same as in Example 1, and as shown in Table 3, the yarn feeding weight of (B) The ratio was set twice that of Example 1, and a bare-tengu circular knitted fabric was prepared to obtain a fabric containing 10% polyurethane elastic fiber. The two-bath dyeing process and the antibacterial exhaust process were performed in the same manner as in Example 1.
The dough density was adjusted in the final heat setting step, and finally a bare-tempered dough having a dough weight of 175 g / m ² was obtained. Next, it was confirmed that 2.5% of the antibacterial agent was exhausted with respect to the weight of the dough.
Table 3 shows conditions such as the configuration of the fabric and the knitting structure. Tables 4 to 5 show the evaluation results of the fabrics. An antibacterial function, deodorant function, fabric stretchability, fabric softness, and a stretch fabric having functions excellent in all of these performances after repeated washing 50 times were obtained.

[Example 3]
(A) As a spun yarn containing a cellulose-based fiber containing a carboxyl group and a polyester fiber, a blended yarn T702-30, which is a 30th British cotton count consisting of 70% modified cellulose fiber raw cotton and 30% polyester fiber raw cotton. Using -SLY-30, (B) Using Ba as a polyurethane elastic fiber, a bare-tenji circular knitted fabric is prepared in the same manner as in Example 1, and a fabric containing 5% polyurethane elastic fiber is obtained. It was. The two-bath dyeing process and the antibacterial exhaust process were performed in the same manner as in Example 1.
The dough density was adjusted in the final heat setting step, and finally a bare-tempered dough having a dough weight of 175 g / m ² was obtained. Next, it was confirmed that 2.4% of the antibacterial agent was exhausted with respect to the weight of the dough.
Table 3 shows conditions such as the configuration of the fabric and the knitting structure. Tables 4 to 5 show the evaluation results of the fabrics. A stretch fabric having functions excellent in all of an antibacterial function, a deodorizing function, fabric stretchability, and fabric softness was obtained.

[Example 4]
(A) As a spun yarn containing a cellulosic fiber containing a carboxyl group and a polyester fiber, a spun yarn SLY-100-30 of No. 30 English cotton count comprising 100% of a modified cellulosic fiber raw cotton is used, (B) Using B-a as the polyurethane elastic fiber, a bare-tenji circular knitted fabric was prepared in the same manner as in Example 2 to obtain a fabric containing 10% polyurethane elastic fiber. The two-bath dyeing process and the antibacterial agent exhaust process were also carried out in the same manner as in Example 2.
The dough density was adjusted in the final heat setting step, and finally a bare-tempered dough having a dough weight of 175 g / m ² was obtained. Next, it was confirmed that 2.5% of the antibacterial agent was exhausted with respect to the weight of the dough.
Table 3 shows conditions such as the configuration of the fabric and the knitting structure. Tables 4 to 5 show the evaluation results of the fabrics. A stretch fabric having functions excellent in all of an antibacterial function, a deodorizing function, fabric stretchability, and fabric softness was obtained.

[Example 5]
(A) A spun yarn including a cellulose-based fiber containing a carboxyl group and a polyester fiber and (B) a polyurethane elastic fiber are the same as those in Example 1, and the yarn feeding weight ratio in (B) is that of Example 1. The bare-tengu-maru knitted fabric was made 5 times to obtain a fabric containing 25% polyurethane elastic fiber. The two-bath dyeing process and the antibacterial exhaust process were performed in the same manner as in Example 1. The dough density was adjusted in the final heat setting step, and finally a bare-tempered dough having a dough weight of 175 g / m ² was obtained. Next, it was confirmed that 2.5% of the antibacterial agent was exhausted with respect to the weight of the dough.
Table 3 shows conditions such as the configuration of the fabric and the knitting structure. Tables 4 to 5 show the evaluation results of the fabrics. A stretch fabric having functions excellent in all of an antibacterial function, a deodorizing function, fabric stretchability, and fabric softness was obtained.

[Comparative Example 1]
(A) In place of a spun yarn containing a cellulose-based fiber and a polyester fiber containing a carboxyl group, an unprocessed cellulose raw cotton (a lyocell raw cotton made by Lenzing, which is not subjected to carboxylation treatment by methacrylic acid graft polymerization, a single yarn fineness of 1.5 A blended yarn T702-70-LY-30 made of denier, fiber length 38 mm, LY) and polyester fiber raw cotton (T702) was produced in the same manner as in Example 1, and this T702-70-LY-30 was produced. (B) Using Ba as the polyurethane elastic fiber, a tentacle knitted fabric was produced in the same manner as in Example 1, and a stretch fabric subjected to antibacterial agent processing was obtained in the same manner as in Example 1. Subsequently, it was confirmed that 2.6% of the antibacterial agent was exhausted with respect to the fabric weight.
Table 3 shows conditions such as the configuration of the fabric and the knitting structure. Tables 4 to 5 show the evaluation results of the fabrics. In the deodorization function, the ammonia absorption ability and the nonenal absorption ability were unsatisfactory, and the deodorization ability was rejected.

[Comparative Example 2]
(A) T702-70-SLY-30 is used as a spun yarn containing a cellulose fiber and a polyester fiber containing a carboxyl group, and (B) a knitted fabric is produced by a circular knitting machine without using a polyurethane elastic fiber. did.
Next, in the same manner as in Example 1, a fabric subjected to antibacterial agent processing was obtained. Next, it was confirmed that 2.5% of the antibacterial agent was exhausted with respect to the fabric weight.
Table 3 shows conditions such as the configuration of the fabric and the knitting structure. Tables 4 to 5 show the evaluation results of the fabrics. In the deodorization function, the nonenal absorption ability was unsatisfactory and the deodorization performance was unacceptable. Further, the fabric stretchability was unsatisfactory.

[Comparative Example 3]
(A) T702-70-SLY-30 is used as a spun yarn including a cellulosic fiber containing a carboxyl group and a polyester fiber. (B) Polyurethane elastic fiber uses Ba and is knitted with a circular knitting machine. The ground was made. Fabrics that were not subjected to antibacterial agent processing were subjected to the test.
Table 3 shows conditions such as the configuration of the fabric and the knitting structure. Tables 4 and 5 show the evaluation results of the fabrics. In the deodorization function, the nonenal absorption ability was unsatisfactory and the deodorization performance was unacceptable. In addition, the decrease in the ability to absorb nonenal after repeated washing was repeated 50 times.

Claims (12)

(A) Cellulose fibers containing a carboxyl group are added to a spun yarn obtained by any one or more of the ring traveler method, open end method, binding method and fine spinning and twisting method. wt%, and the contained spun yarn comprising polyester fibers 0 to 95 wt% with respect to the spun yarn, as well as (B) a polyurethane elastic fiber, 99 to 70 wt% with respect to the fabric (a) is spun yarn, and (B) A fabric containing 1 to 30% by weight of polyurethane elastic fiber, an organic nitrogen sulfur compound, a quaternary ammonium compound, a phosphate ester compound, a phenol compound, a polyphenol, chitosan and an amine antibacterial A stretch fabric characterized in that any one or more antibacterial agents selected from the group consisting of agents are exhausted or supported.   The stretch fabric according to claim 1, wherein the cellulose fiber containing a carboxyl group is a modified cellulose fiber obtained by graft copolymerization reaction of methacrylic acid to a cellulose fiber. The stretch fabric according to claim 1 or 2, wherein the fiber surface area per gram of the polyester fiber is about 0.1 m ² or more, or the single fiber fineness of the polyester fiber is about 3 denier or less.   The stretch fabric according to any one of claims 1 to 3, wherein a urethane group concentration of polyurethane constituting the polyurethane elastic fiber is about 0.2 mol / kg or more and 3.5 mol / kg or less. The polyurethane elastic fiber has a polyalkylene ether diol having a number average molecular weight of 250 to 10,000 containing 5 to 25 mol% of the following structural unit (a) and 95 to 75 mol% of the structural unit (b), a diisocyanate compound, The stretch fabric according to any one of claims 1 to 4, comprising polyurethane urea obtained by polymerizing a diamino compound.

(However, R1 represents an alkylene group, and R2 represents hydrogen or an alkyl group.)   The stretch fabric according to any one of claims 1 to 4, wherein an effective terminal amine concentration of polyurethane constituting the polyurethane elastic fiber is 15 to 50 meq / kg. The antibacterial agent is selected from any one or more of an organic nitrogen sulfur compound, a quaternary ammonium compound, and a phosphate ester compound , according to any one of claims 1 to 6. Stretch fabric. The stretch fabric according to any one of claims 1 to 7, wherein the antibacterial agent is an organic nitrogen sulfur compound. Basis weight is 100 to 1000 g / ^{m 2,} the longitudinal direction and / or stretch fabric according to any one of claims 1 to 8, the transverse direction of elongation is equal to or not less than 5%. The stretch fabric according to any one of claims 1 to 9 , wherein the spun yarn is 6 to 60 British cotton count. The stretch according to any one of claims 1 to 10 , wherein the pH of the treatment liquid containing the antibacterial agent is in the range of 5.0 or more and 6.0 or less during exhaustion or carrying treatment with the antibacterial agent. Fabric. (A) Cellulose fibers containing a carboxyl group are added to a spun yarn obtained by any one or more of the ring traveler method, open end method, binding method and fine spinning and twisting method. And (B) a polyurethane elastic fiber, (A) 99 to 70% by weight of the spun yarn with respect to the fabric, and (B) A fabric containing 1 to 30% by weight of polyurethane elastic fiber, an organic nitrogen sulfur compound, a quaternary ammonium compound, a phosphate ester compound, a phenol compound, a polyphenol, chitosan and an amine antibacterial Stretch cloth for deodorizing aging, characterized in that one or more antibacterial agents selected from the group consisting of agents are exhausted or supported .