TW201120261A - Fiber, cloth, and underwear. - Google Patents

Abstract

The purpose of the present invention is to provide a fiber, cloth, and underwear with long-lasting cold-contact feeling, hand feeling, and touch feeling of skin, which can inhibit yellowing and reddening during distribution process or usage. The fiber of the present invention contains a thermoplastic elastomer, an acidic compound, and a phosphorous anti-oxidant, which characterized in that: the said acidic compound is styrene-maleic anhydride copolymer or acid anhydride and the acidic compound is contained in an amount of 0.1 parts by weight or more per 100 parts by weight of the thermoplastic elastomer.

Description

201120261 VI. Description of the Invention: [Technical Field to Which the Invention Is Applicable] The present invention relates to a feeling of contact between the cool and the touch, the feeling of the skin and the touch of the skin, and the suppression of the flow through the charging field. m% or fibers, cloth and underwear that produce yellowing and reddening when used. [Prior Art] In recent years, as a summer, the fiber having excellent cooling feeling and the fiber product using the fiber have been studied. For example, the contact cold feeling 1 which is a feeling of a cool feeling at the time of wearing is a fiber which is excellent in contact cold feeling, and is not disclosed in Patent Document 1 and Patent Document 4, for example. A fiber containing a polyamine elastomer. However, these fibers have the disadvantage that the fibers will yellow or redden during the flow or use. Specifically, there are the following problems: Due to the waste from the engine of the automobile, such as the waste of the earth, the waste of the fuel cell space heater such as a heater, etc. Change, red change. As a cause of such yellowing or redening, it is considered that the nitrogen oxide compound or moisture in the atmosphere is related to the reaction of the amine group of the polymer constituting the fiber. Further, it is also pointed out that the hindered (tetra) antioxidant or the hindered amine light stabilizer (HALS) added in the production step of the nitrogen oxide compound or moisture, and the polymer constituting the fiber. Further, when polybenzamide elastomer fibers are used as a clothing material such as underwear or sportswear, there is a problem that if the ultraviolet rays are subjected to ultraviolet rays in the state of residual sweat, the % is markedly yellowed. In such an example, the yellow change is further progressed due to repeated wearing and washing. These changes and reddening problems are particularly serious in underwear or sportswear composed of white or light-colored fibers, which significantly reduce the value of their products. For these problems, various methods have been proposed as a method of imparting resistance to yellowing of a fiber containing a polyamine elastomer. In Patent Document 3, a method of treating (4) an aqueous medium containing a surfactant is disclosed. However, in this method, there is a problem that the effect of the yellowing prevention treatment is lowered by the washing of the suic, and the abnormality in the yellowing due to the action of the residual sweat and the ultraviolet rays cannot be sufficiently suppressed. Further, in Patent Document 4, a method of mixing an acidic liquid mixture at the time of spinning is disclosed. However, there has been a problem in the method that the yarn breakage often occurs, or the physical properties of the yarn are lowered, the spinning property is remarkably lowered, and the deterioration of physical properties caused by ultraviolet rays is remarkably large. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-270075 [Patent Document 2] Japanese Patent Laid-Open Publication No. Hei. No. Hei. [Patent Document 4] Japanese Patent Application Laid-Open No. Hei. No. Hei. No. 1-22981 No. [Invention] The present invention is directed to providing a sustainable and excellent contact cold feeling, hand feeling and skin touch in view of the above-mentioned status quo. It inhibits fibers, cloth and underwear that cause yellowing and reddening of fibers during circulation or use. 5 The present invention is a fiber comprising a thermoplastic elastomer, an acidic compound, and a phosphorus-based antioxidant, the acidic compound being a styrene butadisulfonic anhydride copolymer or an acid anhydride, and having a pseudo-weight of the above-mentioned thermoplastic elastomer The body contains 〇·1 part by weight or more of the above acidic compound. Hereinafter, the present invention will be described in detail. As a result of research by the inventors of the present invention, it has been found that fibers containing a thermoplastic elastomer which are excellent in contact with cold feeling further contain a predetermined amount or more of an acidic compound and a phosphorus-based antioxidant, thereby suppressing generation of fibers during distribution or use. The yellowing and the reding change, and the excellent contact with the cold feeling, the hand feeling, and the skin touch are excellent, and therefore, it is particularly applicable to a clothing such as underwear, thereby completing the present invention. The fibers of the present invention comprise a thermoplastic elastomer. The fiber containing the above thermoplastic elastomer gives a cool feeling when it comes into direct contact with the skin when worn, and gives a refreshing feeling. The thermoplastic elastomer is preferably a polyamine-based elastomer. The polyamine-based elastomer is not particularly limited, and examples thereof include a polyether block phthalamide copolymer, a polyether phthalamide copolymer, and a poly-branched amine copolymer. These may be used alone or in combination of two or more. As a commercially available one of these polyamine-based elastomers, for example, Pebax (manufactured by Arkema Co., Ltd.), UBE Nylon (manufactured by Ube Industries Co., Ltd.), Grilon ELX, and Grilamid ELY (above by EMS Showa Denko 5 201120261) In the above thermoplastic elastomer, the polyether block phthalamide copolymer represented by the following formula (1) can obtain an extremely excellent antistatic effect, which is excellent in spinnability, and can be made small in specific gravity and light in weight. The cloth or underwear is therefore very good. The polyether block phthalamide copolymer is commercially available, and examples thereof include Pebax (manufactured by Arkema Co., Ltd.). 〇 Ο ' HO - -C-PA-C-Ο-PE-0--Η (1) -I η In the formula (1), PA represents polyamine, and PE represents polyether. The fiber of the present invention contains an acidic compound, and the above acidic compound is a strepto-maleic anhydride copolymer or an acid anhydride. In the present invention, by using such an acidic compound, the yellowing resistance and redness resistance of the fiber can be greatly improved. In the case of using the styrene-cis-butyl hydride anhydride copolymer as the above-mentioned acidic compound, even if it is washed repeatedly, it is easy to prevent yellowing and reddening, especially in the state in which the sweat component remains on the fiber. The effect of fading in a sunlit environment is greater. The above styrene-maleic anhydride copolymer has a segment derived from styrene and a segment derived from cis-T-di(tetra). The above-mentioned bond derived from stupid ethylene and upper = derived from maleic acid The ratio of the segments of the needle is preferably 1/3 to 1 with respect to the segment derived from styrene, and more preferably 201120261. The above styrene-maleic anhydride A preferred lower limit of the weight average molecular weight (Mw) of the copolymer is 1000, and a preferred upper limit is 50,000. If the weight average molecular weight of the styrene-cis succinic anhydride copolymer is less than 1 〇〇〇, there is a phenomenon of bleed out from the surface of the fiber if the weight average molecular weight of the styrene-maleic anhydride copolymer exceeds At 50000, there is a phenomenon that silk knots are easily generated on the fibers. In the case where the above styrene-maleic anhydride copolymer is used as the above acidic compound, the above-mentioned ethylene-succinic dicarboxylic acid needle copolymer in the fiber of the present month is 100 parts by weight of the thermoplastic elastomer. The lower limit of the content is 0.1 part by weight, and preferably the upper limit is 30 parts by weight. If the content of the styrene-butylene anhydride copolymer is less than 01 parts by weight, the effect of suppressing enthalpy change or red color change cannot be obtained; if the content of the above styrene maleic anhydride copolymer exceeds 3.0 parts by weight, The physical properties of the fiber are lowered, or the yarn is broken at the time of the wire, resulting in a decrease in spinnability. The content of the above styrene-maleic acid field copolymer is preferably (4) 〇 2 4 New, and the lower limit of # is 3 parts by weight; the content of the above styrene·maleic anhydride copolymer is The upper limit is preferably 2.0 parts by weight, and more preferably the upper limit is 1 to 5 parts by weight. Examples of the acid anhydride include phthalic anhydride, maleic anhydride, acetic anhydride, benzoic anhydride, succinic anhydride, nicotinic acid anhydride, propionic anhydride, n-hexanoic acid, glutaric acid needle, formic acid needle, and hydrogen. Phthalic acid, such as acetic anhydride. Among them, phthalic anhydride is preferred. When the above acid anhydride is used as the above acidic compound,

The lower limit of the content of the above-mentioned acid Xuan 7 201120261 in the fiber of the present invention is 0.1 parts by weight, and the content of the above-mentioned acid anhydride is less than 0. The upper limit is 2 for the thermoplastic elastomer 丨〇〇番县~, T ping body 100 parts by weight. 0 parts by weight. If it is ^ 77 , the effect of suppressing yellowing or k can not be obtained, and if the content of the above acid acid is more than 2.0 parts by weight, the physical property of the second is lowered, and the broken yarn is generated at the time of spinning: the lower limit of the content of the fiber itself is 〇 15 parts by weight, more preferably the content of the above-mentioned sour liver = the lower limit is preferably 上限. 2 3 1 The upper limit is 1.0 part by weight, and the upper limit is 0.6 parts by weight. Further, the fiber of the present invention contains a phosphorus-based antioxidant. In particular, by containing the above phosphorus-based antioxidant, the redness resistance can be greatly improved. Further, in the present invention, the term "phosphorus-based antioxidant" means an antioxidant having a phosphorus atom, and preferably an antioxidant having a P(〇R)3 structure. Wherein R is an alkyl group, an alkylene group, an aryl group or an extended aryl group, and three R groups may be the same or different, and any two R groups may be bonded to each other to form a cyclic structure. Examples of the phosphorus-based antioxidant include tris(nonylphenyl)phosphite (manufactured by Ouchi Shinko Chemical Co., Ltd., "N〇crac TNp"), and bisphosphite (2,4-di-second) Phenyl phenyl ester (manufactured by CIBA JApAN κ κ, "Irgaf〇S168"), three [2_[[2,4,8 ι〇_tetra-t-butyldibenzo[d,f][l,3 , 2] one. Ethylene 4Μ裒g焼-6-yl]oxy]ethyl]amine (manufactured by CIBA jApAN Κ_Κ·, "Irgafos 12"), bisphosphite bis[2,4·bis(ι,ι_dimethylethyl) -6-Methylphenyl]ethyl ester (manufactured by CIBA JAPAN KK, "Irgafos 38"), bis(2,4-di-t-butylphenyl)pentaerythritol-di- ternary acid ester (manufactured by ciba JAPAN KK, "Irgafos 126") 'tetrakis(2,4-di-t-butylphenyl)[1,1-biphenyl]-4,4'-diylbisphosphonate (manufactured by ciBA JAPAN KK, "Irgafos P -EPQj), bis(2,6-di-t-butyl-4-tolyl) 8 201120261 Pentaerythritol-diphosphite ("Adekasub'" manufactured by ADEKA), a hard moon, pentaerythritol-diphosphoric acid Ester ("Adekastab 88", manufactured by ADEKA), 2,4 81 第三tetrabutyl o-(3_f-based _4. thio-5-t-butylphenyl)propoxy]dibenzo [d,f][i,3,2] Dioxaphosphocycloheptane (manufactured by Sumitomo Chemical Co., Ltd., "-Gp"). The preferred lower limit of the content of the above-mentioned scaly antioxidant in the fiber of the present invention is 0.00 part by weight, preferably 1.5 parts by weight, per 100 parts by weight of the thermoplastic elastomer. When the content of the phosphorus-based antioxidant is less than 1 part by weight, the effect of suppressing reddening cannot be obtained, and if the amount of the above-mentioned scale antioxidant exceeds K5 parts by weight, it becomes easy to migrate from the fiber, thereby causing powder The lower limit of the content of the above phosphorus-based antioxidant is preferably 1.0 part by weight, more preferably the lower limit is 〇, and the upper limit of 2 parts by weight and more preferably 0.6 part by weight. The fiber of the present invention preferably contains titanium oxide. In recent years, there has been a tendency for fabric materials such as underwear, which use a plurality of synthetic fibers, to increase, and ammonia odor caused by such fibers. U exists in the fiber of the present invention due to sweat or urine. The right side of the fiber is decomposed by the redox action of the titanium; the purpose is to impart a deodorizing function to the odor, and the Si on the field is 'by containing the above oxidation, Available in white for underwear and transportation. Of course, it is also possible to make the white color for a certain basis and to make a light-colored fiber. The earth adds eight pigments, and then the hunter is made of oxidized, which can reduce the sticky feeling of the unique 2011 11261, which gives it a dry feel. As the titanium oxide used in the present invention, rutile-type titanium dioxide is preferred. In addition to the rutile-type titanium dioxide described above, anatase-type titanium oxide is known, and the anatase-type titanium oxide has a strong redox effect, so that it can exert a high anti-m, but disperses the precursor of the above-mentioned oxidized chin. Since the molecular chain of the polymer may also be broken, there is a tendency that the yarn breaks during spinning to cause an abnormality, or the strength of the fiber tends to deteriorate rapidly with time, which is not preferable. The average particle diameter of the above titanium oxide is preferably 015 to 0 5 em. The average particle diameter of the above titanium oxide is more preferably from 0. 18 to 0.4, and further preferably from 〇2 to 0.3 /z m. By using titanium oxide having a particle diameter within the above range, a fiber having a higher whiteness can be obtained. When the average particle diameter is less than 0.15 "m, the physical properties of the fiber are lowered by the redox reaction. When the average particle diameter exceeds 0.5 // m, the whiteness of the fiber is insufficient. The fiber is yellow, which is easy for the fiber to knot, or tends to cause breakage during spinning. It is preferable to carry out an inorganic treatment of at least one selected from the group consisting of an alumina system, a silica dioxide system, and an oxidation system on the surface of the titanium oxide. Further, it is preferred to carry out an organic treatment such as a polyol system or a siloxane system on the surface of the titanium oxide. By carrying out the above inorganic treatment and organic treatment, the dispersibility of the above titanium oxide in the polymer can be improved, and the light resistance of the polymer can be improved. The amount of the above titanium oxide added is preferably from 3 to 10 parts by weight based on 100 parts by weight of the thermoplastic elastomer. Further, the amount of the titanium oxide added is more preferably 3.5 to 8 parts by weight, still more preferably 4 to 6 parts by weight. When the polymer contained in the fiber of the present invention is formed only of a polyether block phthalamide copolymer, the amount of the above titanium oxide is set to be relative to 1 part by weight of the above polyether block 醯. The amine copolymer is preferably 4 to 6 parts by weight, and is excellent in ammonia odor resistance, yellowing resistance, and redness resistance. Further, by adding the amount of the titanium oxide to the above range, the sticky feeling peculiar to the elastomer can be improved, and the yarn breakage in the spinning can be reduced. The aspect of the fiber of the present invention is not particularly limited, and may be formed only of the thermoplastic elastomer, the acidic compound, and the phosphorus-based antioxidant. However, the fiber using the thermoplastic elastomer generally has a sticky feeling and is also spun. Difficult guess. In this case, it can also be used together with other resins. The fiber of the present invention may contain an additive such as an inorganic filler, a flame retardant, an ultraviolet absorber, an antistatic agent, a photostabilizer, an inorganic substance, or a higher fatty acid salt, within a range not impairing the effects of the present invention. In the case where the fiber of the present invention contains a resin other than the above thermoplastic elastomer, the mixture of the resins may be spun, or may be a composite fiber. The other resin is not particularly limited, and examples thereof include a polyamide resin such as nylon 6, nylon 66, nylon n, and nylon 12, a polyester resin such as ρΕτ, ρΒτ, or ruthenium, ruthenium or acrylic acid. Among them, polyamine-based resins are preferred. These resins may be used singly or in combination of two or more. In the case of using the above other resin, in order to prevent fading at the composite interface or the contact interface, it is preferred that the above acidic compound and the phosphorus-based antioxidant of the above-mentioned 201120261 are the same as those added to the thermoplastic elastomer. The ratio is added to the above other resins. The conjugate fiber is not particularly limited, and examples thereof include a core-type double-sided type (10) kiss-Slde composite fiber, a Korean-type composite fiber, and a medium-second ring-shaped composite fiber. In the case where the fiber of the present invention is the above-mentioned core-type composite fiber, the thermoplastic resin may be used in the core portion, and the other resin may be used in the yarn portion. The above-mentioned other resin may be used in the core portion, and the above-mentioned thermoplastic resin may be used in the portion. . The shape of the core-type composite fiber is not particularly limited. For example, when the vertical cutting is performed with respect to the length of the fiber, the cross-sectional shape may be a perfect circle or an ellipse, etc., and the anger and the portion may be formed as Concentrically shaped concentric core-type composite fibers may also be eccentrically formed into a core and core-sheath type composite fiber. Further, it is also possible to open the core (four) composite fiber in a part of the sheath portion. Further, it may be a structure in which a plurality of core portions are present when vertically cut with respect to the longitudinal direction of the fibers. The qmax value of the fiber of the present invention is preferably 〇·2 J/sec/cm 2 or more.

The qmax value is the peak value of the heat flow rate at which the accumulated heat is moved to the sample on the low temperature side after the predetermined heat is accumulated on a constant surface or a certain mass of hot plate. Usually, the value of w is the body temperature that is captured by 4 samples when wearing clothes. The larger the qmax value, the larger the body temperature that is captured when wearing clothes, and the higher the contact coldness. If the value is less than j·2 j/sec/cm2, even if the functional test is performed, 'most people still do not feel contact with cold feeling, and the claws are more preferably 0.21 "secW or more' and thus more preferably 〇22 j/sec/::2X 12 201120261 or more. The thermal conductivity of the fiber of the present invention is preferably lxl (T3 ° C / W. m 2 or more. It is generally considered that the thermal conductivity is also an important parameter corresponding to the contact cold feeling. 1. If the thermal conductivity is less than 1X1 (Γ3 °C /W · m2, even if the functional test is performed, most people still do not feel the cold contact. In addition, the thermal conductivity can be placed on the sample stage. The hot plate was stacked on the sample, and the heat loss rate after the temperature of the hot plate was stabilized to a predetermined temperature was measured and calculated by the following formula (2). Thermal conductivity (W/cm factory C) = W · D/Α /Λ T ( 2 ) W : heat flow rate (j/sec ) D : thickness of sample (cm) A : hot plate area (cm2 ) △ T : temperature difference between sample stage and hot plate (.〇) The method of the fiber of the present invention is not particularly limited, and for example, a previously known method using a particle containing the above thermoplastic elastomer, an acidic compound, and a phosphorus-based antioxidant can be used. In the case of producing a conjugate fiber using the above other resin, particles containing a thermoplastic elastomer, an acidic compound, and a phosphorus-based antioxidant, and particles containing the other resin may be used. Method for obtaining a composite fiber by melt spinning into a composite spinning device

It feels cool and cool, and it gives a cool feeling. In addition, the white coolness 13 201120261 or light color can be maintained for a long time, so it can also be applied to underwear. A cloth made using the fiber of the present invention is also one of the present inventions. In the present specification, the cloth includes a knitted fabric, a woven fabric, a non-woven fabric, and the like. The cloth of the present invention may be formed only of the fibers of the present invention, but may be blended with other fibers to improve the requirements of underwear such as skin touch without damaging the object of the present invention. The other fibers are not particularly limited, and examples thereof include polyamine-based resins such as nylon 6 and nylon 12; and polyesters, cotton, and enamel. An underwear made using the fiber of the present invention or the cloth of the present invention is also one of the inventions. [Effects of the Invention] According to the present invention, it is possible to provide a fiber, cloth and underwear which are excellent in contact with cold feeling, hand feeling and skin feel, and which can suppress yellowing and redening of fibers during distribution or use. [Embodiment] Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to the embodiments. (Example 1) 60 parts by weight of a polyether block phthalamide copolymer ("Pebax MV1041SA01" manufactured by Arkema Co., Ltd.), which is a thermoplastic polyamine-based elastomer, and a polyether block guanamine copolymer (manufactured by Arkema Co., Ltd.) "Pebax 6333SA01") 40 parts by weight, styrene-maleic anhydride copolymer (manufactured by Sartomer Japan Co., Ltd., "SMA1000"), 1 part by weight, phosphorus 14 201120261 antioxidant (made by ADEKA Corporation, "Adekastab PEP36") 0.6 5 parts by weight of titanium oxide (manufactured by Daicel Chemical Industries, Ltd., "D-918"), UV absorber (manufactured by CIBA JAPAN KK, "TINUVIN 234"), 0.3 parts by weight, and light stabilizer (manufactured by CIBA JAPAN KK) After 0.3 parts by weight of "TINUVIN 144"), it was melt-mixed, and resin pellets were produced using a granulator. Then, using the obtained resin pellets, the yarn was produced by a melt spinning method to obtain a strand having a fineness of 120 dtex (consisting of 36 filaments) and a diameter of about 20 v m per filament. The obtained raw yarn was woven to prepare a circular rib fabric. Further, the titanium oxide "D-918" was subjected to surface treatment, specifically, inorganic treatment (alumina, cerium oxide, and zirconia treatment), followed by organic treatment. (Example 2) 60 parts by weight of a polyether block guanamine copolymer ("Pebax MV1041SA01" manufactured by Arkema Co., Ltd.) as a thermoplastic polyamine-based elastomer, and a polyether block guanamine copolymer (manufactured by Arkema Co., Ltd.) "Pebax 6333SA01") 40 parts by weight, styrene-maleic anhydride copolymer ("Sartomer Japan", "SMA1000") 1.5 parts by weight, phosphorus-based antioxidant ("Adekastab PEP36", manufactured by Adeka Co., Ltd.) 1 part by weight 5 parts by weight of titanium oxide ("D-918" manufactured by Sigma Chemical Industry Co., Ltd.), 0.3 parts by weight of a UV absorber (manufactured by CIBA JAPAN KK, "TINUVIN 234"), and a light stabilizer (manufactured by CIBA JAPAN KK, "TINUVIN 144" After 0.3 parts by weight, melt-mixing was carried out, and resin pellets were produced using a granulator. Then, using the obtained resin pellets, the yarn was produced by a melt spinning method of 201120261, and a strand having a fineness of 120 dtex (consisting of 36 filaments) and a diameter of about 20 per filament was obtained. The obtained raw yarn was woven to prepare a rib circular knitted fabric. (Example 3) A polyether block phthalamide copolymer ("Pebax MV1〇41SA〇1", manufactured by Arkema Co., Ltd.), which is a thermoplastic polyamine-based elastomer, was added, and a ruthenium-based copolymer 40 parts by weight of a styrene-butyl butyric acid-rich liver copolymer ("SMA1000" manufactured by Sartomer Japan Co., Ltd.) and a phosphorus-based antioxidant (manufactured by Arkema Co., Ltd., "pebax 6333SA01"), manufactured by CIBA JAPAN KK. "Iggafos 126") 5 parts by weight of titanium oxide (manufactured by Sigma Chemical Industry Co., Ltd., r D_918), 5 parts by weight of ultraviolet absorber (manufactured by CIBA JAPANK.K., "TINUVIN 234"), 0.3 parts by weight, and light stabilizer (ciBA JAPAN KK·manufactured '"TINUVIN 144") 3·3 parts by weight, melt-mixed, and granulated resin to prepare resin pellets. Then, the obtained resin pellets were used to obtain a resin by melt spinning. The fineness is UOdtex (consisting of 36 filaments), and the diameter of the parent filament is about 20 " m. The obtained raw yarn was woven to prepare a rib circular knitted fabric. (Example 4) 60 parts by weight of a polyether block phthalamide copolymer ("pebax MV1041SA01" manufactured by Arkema Co., Ltd.), which is a thermoplastic polyamine-based elastomer, and a polybendane-coated amine copolymer (manufactured by Arkema Co., Ltd.) "pebax 63 33SA01") 40 parts by weight of a styrene-succinic acid anhydride copolymer ("Sartomer Japan", "SMA1000") 0.3 parts by weight, 16 201120261 Scale antioxidant (Sumitomo Chemical Co., Ltd., "SumiHzer GP") )〇.2 Heavy-duty wound, Oxidized Chin (made by Chemical Industry Co., Ltd., "D_9i8") 5 weight injury, UV absorber (manufactured by CIBA JAPAN KK, "TINUVIN 234") 3.3 parts by weight and light stabilizer (ciba) After 0.3 parts by weight of JAPAN KK, "TINUVIN 144"), it was melt-mixed, and resin pellets were produced using a granulator. Then, using the obtained resin pellets, the yarn was produced by a melt spinning method to obtain a strand having a fineness of 12 〇dtex (consisting of 36 filaments) and having a diameter of about 20 # m per filament. The obtained raw yarn was woven to prepare a rib circular knitted fabric. (Example 5) 60 parts by weight of a poly-block block guanamine copolymer (manufactured by Arkema Co., Ltd.), which is a polyacrylamide-based elastomer, which is a thermoplastic polyamine-based elastomer, (polykeb MV1041SA01). "pebax 6333SA01") 40 parts by weight of styrene-maleic anhydride copolymer ("Sartomer Japan", "SMA1000") 〇. 2 parts by weight, filled with antioxidant (manufactured by Sumitomo Chemical Co., Ltd., r Sumilizer Gp) 〇, 5 parts by weight, 5 parts by weight of titanium oxide ("D_91 8" manufactured by Sigma Chemical Industry Co., Ltd.), 0.3 parts by weight of a UV absorber (manufactured by CIBA JAPAN Κ·Κ, "TINUVIN 234"), and a light stabilizer ( After 0.3 part by weight of cibA JAPAN KK manufactured and "TINUVIN 144", it was melt-mixed, and resin pellets were produced using a granulator. Then, using the obtained resin pellets, the yarn was produced by a melt spinning method to obtain a strand having a diameter of 12 〇 dtex (consisting of 36 filaments) and a mother filament having a diameter of about 20 # m. The obtained raw yarn was woven to prepare a rib circular knitted fabric. 17 201120261 (Example 6) A polyether block phthalamide copolymer ("Pebax Mvi〇 41SA〇1" manufactured by Arkema Co., Ltd.) as a thermoplastic polyamine-based elastomer was added in an amount of 1 part by weight, phthalic anhydride 0.6 parts by weight, phosphorus-based antioxidant (K, Sumilizer GP, manufactured by Sumitomo Chemical Co., Ltd.), titanium oxide (manufactured by Daicel Chemical Industry Co., Ltd., "D-918"), 5 parts by weight, ultraviolet absorber (αΒΑ) Manufactured by JAPANK.K., "TINUVIN 234") ο" parts by weight and light stabilizer (manufactured by CIBA JAPAN KK, "TINUVIN 144") 〇 3 weight loss, melt-mixing, and granulator to produce resin pellets. Then, using the obtained resin pellets, the yarn was produced by a melt spinning method to obtain a strand having a fineness of 12 〇 dtex (consisting of 36 filaments) and a diameter of about 20 per i filament. The obtained raw yarn was woven to prepare a ribbed circular braid. (Example 7) 1 part by weight of a polyether block phthalamide copolymer ("pebax MV1041SA01" manufactured by Arkema Co., Ltd.), and 6 parts by weight of o-dodiacetate, as a thermoplastic polyamine-based elastomer, 5 parts by weight of phosphorus-based industrial company, "D-918"), UV absorber (8) manufactured by ANK.K., "TINUVIN 234"), 3 parts by weight, and light-weighting agent (CIBA JAPAN κ.κ. After manufacturing, "TINUVIN 144") 〇 3 ^ parts, melt-mixing was carried out, and resin pellets were produced using a granulator. Then, the obtained resin pellets were used to make a filament by a melt spinning method, and a filament having a length of 12 〇dtex (consisting of 36 filaments) and a diameter of each of the filaments 18 201120261 of 20 μm was obtained. . The obtained raw yarn was woven to prepare a ribbed circular braid. (Example 8) A polyether block decylamine copolymer ("Pebax MV 〇 41SA01" manufactured by Arkema Co., Ltd.) as a thermoplastic polyamine-based elastomer was added in an amount of 1 part by weight, and phthalic anhydride was added! Parts by weight, phosphorus-based antioxidant (manufactured by cIBA JAPAN KK, "Irgafos 126"), 15 parts by weight, titanium oxide (manufactured by Daicel Chemical Industries, Ltd., "D-918"), 5 parts by weight, and ultraviolet absorber (CIBA JAPANK.K) Manufactured, "TINUVIN 234") 〇 3 parts by weight and 0.3 parts by weight of a light stabilizer (manufactured by CIBA JAPAN KK, "TINUVIN 144") were then "melted and mixed" to prepare resin pellets by a granulator. Then, using the obtained resin pellets, the yarn was produced by a melt spinning method to obtain a fineness of 120 dtex (consisting of 36 filaments), each! The root filament has a diameter of about 20 y m. The obtained raw yarn was woven to prepare a ribbed circular braid. (Example 9) A polyether block phthalamide copolymer ("Pebax MV1041SA01", manufactured by Arkema Co., Ltd.) as a thermoplastic polyamine-based elastomer was added in an amount of 1 part by weight, and bisphthalic anhydride was used in an amount of 2 parts by weight. 0.5 parts by weight of a phosphorus-based antioxidant ("Adekastab PEP36" manufactured by AdEKa Co., Ltd.), 5 parts by weight of titanium oxide ("D-91 8" manufactured by Nippon Chemical Industry Co., Ltd.), and a UV absorber (manufactured by cib A JAPANK.K. "TINUVIN 234") 3 parts by weight and 0.3 parts by weight of a light stabilizer (manufactured by CIBA JAPAN Co., Ltd., "TINUVIN 144"), and then "melt-mixed" using a granulator to produce resin pellets. Then, the resin pellets of 19 201120261 are "by filament spinning, and the fibers are made of % filaments", and the diameter of each filament is about the strand of the braid core. Weaving using the obtained raw yarn to prepare a rib circle (Example 1 〇) Adding a scale-blocking block amine-melt polymer (manufactured by Arkema Co., Ltd., "Pebax Mvi〇 4is A〇ij") as a thermoplastic polyamine-based elastomer Parts by weight of phthalic acid (tetra) bismuth, phosphorus-based antioxidant (made by ADEKA Co., Ltd., "AdekastabPEP36"), i parts by weight, titanium oxide (manufactured by Spiro Chemical Industries, Inc., "D-918"), 5 parts by weight, ultraviolet absorber ( Manufactured by CM Japan KK.K., "TINUVIN 234"), 3 parts by weight, and a light stabilizer (manufactured by CIBA JAPAN κ., "Tmuvi N 144"), 3 parts by weight, melt-mixed, and produced by a granulator. Resin particles. Then, using the obtained resin pellets, the yarn was produced by a melt spinning method to obtain a strand having a fineness of 120 dtex (consisting of 36 filaments) and a diameter of about 20 v per filament per i. The obtained raw yarn was woven to prepare a ribbed circular braid. (Example 11) As a resin for a sheath portion, a poly-blocking phthalamide copolymer ("Pebax MV1074SA01" manufactured by Arkema Co., Ltd.) as a thermoplastic polyamide-based elastomer was added in an amount of 1 part by weight, and styrene was used. Butene hydride copolymer ("Sartomer Japan", "SMA1000") i parts by weight, phosphorus

Antioxidant (Sumiton Chemical Co., Ltd., "Sumilizer GP") 0.3 parts by weight, UV absorber (manufactured by CIBA JAPAN KK, "TINUVIN 20 201120261 234") 〇·3 罝 parts and light stabilizer (manufactured by CIBA JAPAN KK, After 3 parts by weight of TINUVIN 144"), the mixture was melt-mixed, and a pelletizer for the sheath portion was produced using a granulator. As a resin for the core, a nylon 6 (manufactured by Yukou P., Ltd., "UBENyl〇n 1〇llFB"), a part by weight of stupid ethylene/maleic anhydride copolymer (Sart) 〇mer japan company, 〇〇〇") 1 part, 1 part of the antioxidant (Sumiton Chemical Co., Ltd. Sumillzer Gp) 0.3 parts by weight, UV absorber (manufactured by CIBA JAPANK.K., "UVIN 234" 3 parts by weight and a light stabilizer (manufactured by CIBA JAPAN κ.K., "TINUVIN 144") 〇3, which is melt-mixed after the injury, and the core resin pellets B 〇 and · domains are produced by using a granulator. The obtained resin portion A for the sheath portion and the resin particles B for the core portion are respectively heated and melted by a uniaxial extruder to perform composite spinning so that the cross section of the core portion becomes circular, and the cross section of the sheath portion becomes substantially c-shaped. A partial eccentric core-sheath composite fiber having a fineness of 120 dtex (consisting of 36 filaments) is obtained. The diameter of each filament of the quasi-composited composite fiber is about 20 # m, and the occupation ratio of the loyalty portion is relative to The fiber cross-sectional area is 8〇0/〇. The obtained composite fiber was used for knitting to make a rib circular knitted fabric. (Example 12) As a resin for a core, a polyether block phthalamide copolymer ("pebax MV1074SA01", manufactured by Arkema Co., Ltd.) as a thermoplastic polyamide-based elastomer was added in an amount of 1 part by weight, and styrene-cis was added. Butene phthalic acid copolymer ("Sarti Japan", "SMA1 〇〇〇") i parts by weight, phosphorus 21 201120261 k oxidizing agent (Sumitomo Chemical Co., Ltd., "Sumiiizer GP") 0.3 parts by weight 'UV absorber (CIBA JAPAN) 0.3 parts by weight of a light stabilizer (manufactured by ciBA JAPAN KK, "TINUVIN 144"), 0.3 parts by weight, and melt-mixed, and a core resin pellet A was produced by using a granulator. . As a resin for the sheath, 100 parts by weight of a nylon 6 ("UBE Nylon 101 1FB" manufactured by Ube Industries, Ltd.) and a styrene-maleic anhydride copolymer (Sart〇mer Japan Co., Ltd.) was added as a polyamide resin. Manufactured, "SMA1000") parts by weight, 0.3 parts by weight of a phosphorus-based antioxidant (Sumiton Chemical Co., Ltd., "Sumilizer GP"), and 0.3 parts by weight of a UV absorber (ciBA JAPAN Κ, manufactured by TIN Manufacture, "TINUVIN 234") And a light stabilizer (manufactured by CIBA JAPAN K_K., "TINUVIN 144"), 〇3, and then melt-mixed, and used a granulator to produce resin particles B for sheaths.

Then, the obtained core resin pellet A and the sheath resin pellet B are heated and melted by a uniaxial extruder to perform composite spinning so that the core portion has a circular cross section and the sheath portion has a large cross section. &. In the form of a partial eccentric core-sheath type composite fiber having a fineness of ex (composed of 36 filaments), the diameter of each filament of the composite fiber is about 2 〇" m, and the core portion is occupied. The rate is the brain relative to the cross-sectional area of the fiber. The ribbed circular braid is produced by weaving using the conjugate fiber. (Example 13) $Additional & Thermoplastic Polyamine-Based Elastomer Polycarboxylate Block Aramid Copolymer (Arkema Co., Ltd., "Old") 〇〇 〇〇 Weight 22 201120261 Injury, Benthene-Hexene 1 part by weight of a monoanhydride copolymer ("SMA1000" manufactured by Sartomer Japan Co., Ltd.), 0.3 parts by weight of a phosphorus-based antioxidant ("Sumilizer GP" manufactured by Sumitomo Chemical Co., Ltd.), and an ultraviolet absorber (manufactured by ciBA JAPAN K_K., "TINUVIN 234" 3 parts by weight and 0.3 parts by weight of a light stabilizer (manufactured by CIBA JAPAN Co., Ltd., "TINUVIN 144") were subjected to smelting and mixing, and a resin granule A was produced using a granulator. 100 parts by weight of a nylon 1 oxime ("Rilsan BESN TL" manufactured by Arkema Co., Ltd.) and 1 part by weight of a styrene-butyl succinic acid needle copolymer ("Sartomer Japan Co., Ltd.", "SMA1000")) 0.3 parts by weight of a phosphorus-based antioxidant ("Surnilizer GP" manufactured by Sumitomo Chemical Co., Ltd.), 0.3 parts by weight of a UV absorber (manufactured by ciBA JAPAN Co., Ltd., "TINUVIN 234"), and a light stabilizer (manufactured by CIBA JApAN KK, "TINUVIN") 144") After _3 parts by weight, melt-mixing was carried out. Using a granulator, resin pellets B were produced. Then, the obtained resin pellet A and resin pellet b were respectively heated and melted by a uniaxial extruder, and composite spinning was carried out so that their respective cross sections became semicircular, and the fineness was 120 dtex (consisting of 36 filaments). Side by side composite fiber. The diameter of each of the obtained composite fibers was about 20 μm' and the core portion occupied 5 〇〇/〇 with respect to the fiber cross-sectional area. The obtained composite fiber was woven to prepare a rib circular knitted fabric. (Example 14) A polyether block phthalamide copolymer (manufactured by Arkema Co., Ltd., "pebax MV1074SA01"), which is a thermoplastic polyamine-based elastomer, was added in an amount of 1 part by weight of a 'styrene-maleic anhydride copolymer ( Sartomer japan company 23 201120261, "SMA1000") 1 part by weight, phosphorus-based antioxidant (Sumiton Chemical Co., Ltd., "Sumilizer GP") 0.3 parts by weight, UV absorber (manufactured by CIBa JAPANK.K., "TINUVIN 234" 0.3 parts by weight and 0.3 parts by weight of a light stabilizer (manufactured by CIBA JAPAN KK, "TINUVIN 144") were melt-mixed, and resin pellets A were produced using a granulator. 100 parts by weight of a nylon 12 (manufactured by Ube Industries, Ltd., "UBESTA 3014B"), and a styrene-maleic anhydride copolymer (manufactured by Sartomer Japan Co., Ltd., "SMA1000"), 1 part by weight, and a scale Antioxidant ("S SumiHzer Gp" manufactured by Sumitomo Chemical Co., Ltd.) 〇3 Heavy wound, prepared as an external absorbent (manufactured by CIBA JAPAN KK, "TINUVIN 234") 0.3 parts by weight and light stabilizer (manufactured by Ciba JAPAN KK, "TINUVIN" After 0.3 parts by weight of I44"), the mixture was melt-mixed, and a resin granule B was produced using a granulator. Then, the obtained resin pellet A and resin pellet B were separately heated and melted by a uniaxial extruder, and composite spinning was carried out so that their respective cross sections became semicircular, and a fineness of 12 〇dtex (by 36 filaments) was obtained. A side-by-side type composite fiber. The diameter of each of the obtained composite fibers was about 20 // m, and the occupation ratio of the core portion was 5% by volume with respect to the cross-sectional area of the fibers. The obtained composite fiber was woven to prepare a rib circular knitted fabric. (Example 1 5) As a sheath resin, a polyether block phthalamide copolymer ("RΑη MV1074SA01" manufactured by Arkema Co., Ltd.), which is a thermoplastic polyamine-based elastomer, was added in an amount of 1 part by weight, and styrene was added. 1 part by weight of a maleic acid copolymer (manufactured by Sartomer Japan Co., Ltd., "SMA1"), phosphorus 24 201120261 anti-deuteration agent (Sumiton Chemical Co., Ltd., "Sumilizer GP") 〇 3 parts by weight, ultraviolet absorption 0.3 parts by weight of a light stabilizer (manufactured by CIBA JAPAN Co., Ltd., "TINUVIN Μ4"), 0.3 parts by weight of CIBA JAPAN (manufactured by CIBA JAPAN Co., Ltd., "TINUVIN 234"), and then melt-mixed and used for granulation. The resin particles A for the sheath portion were produced. As a resin for the core, a thermoplastic polyester elastomer ("Pelprene p_15〇B", manufactured by Sakamoto Toyobo Co., Ltd.) was added in an amount of 1 part by weight, and a styrene-butadiene anhydride copolymer (Sartomer Japan Co., Ltd.) was added. Manufactured, "SMA 1 〇〇〇") i parts by weight, phosphorus-based antioxidant (manufactured by Sumitomo Chemical Co., Ltd., "Sumilizer GP") 0.3 parts by weight, ultraviolet absorber (manufactured by ciBA JAPANK.K., "TINUVIN 234"). After adding 0.3 parts by weight of a light stabilizer and a light stabilizer (manufactured by CIBA JAPAN KK, "TINUVIN 144"), the mixture is melt-mixed, and a core resin pellet B is produced by using a granulator, and the obtained sheath resin is obtained. The pellet A and the resin pellets B for the core are heated and melted by a uniaxial extruder, and the composite spinning is performed so that the cross section of the core portion becomes a circle, the cross section of the sheath portion becomes a ring shape, and the fineness is 12 Å to obtain Concentric core-type composite fiber (consisting of 36 filaments). The resulting composite // m 'and the core fraction occupancy diameter of the filaments per fiber is about 2 〇 relative to the fiber cross-sectional area of 7 〇 %. The obtained composite fiber was woven to prepare a rib circular knitted fabric. (Example 1 6) As a core and a resin for a part, a polyfluorene-based phthalamide copolymer was added as a thermoplastic polyamine-based elastomer ("Pebax 25 201120261 MV1074SA01"), 100 parts by weight, phenylethyl 1 part by weight of a dilute-maleic acid needle copolymer ("SMA1000", manufactured by Sartomer Japan Co., Ltd.), filled with an antioxidant (manufactured by Sumitomo Chemical Co., Ltd., "Sumilizer GP j" 0.3 parts by weight, UV absorber (CIBA JAPAN KK) After 0.3 parts by weight of the production and "light stabilizer" (manufactured by CIBA JAPAN KK Co., Ltd., "TINUVIN 144"), 0.3 parts by weight, the mixture was melt-mixed, and the core resin particles A were produced using a granulator. A thermoplastic polyester-based elastomer (manufactured by Sakamoto Toyobo Co., Ltd., "Pelprene P-150B") was added as a resin for the sheath portion, and a styrene-cis-succinic acid needle copolymer (Sartomer Japan Co., Ltd.) was added. Manufactured, "SMA1 000"), 1 part by weight, 0.3 parts by weight of a phosphorus-based antioxidant ("Sumihzer GP" manufactured by Sumitomo Chemical Co., Ltd.), 0.3 parts by weight of a UV absorber (manufactured by CIBA JAPAN KK, "TINUVIN 234"), and light stable 3 parts by weight of the bismuth agent (manufactured by CIBA JAPAN KK, rTINUVIN 144) was melt-mixed, and the resin particles B for the sheath portion were produced using a granulator, and the obtained resin particles A for the core portion and the sheath portion were used. The resin pellets were respectively heated and melted by a uniaxial extruder, and composite spinning was carried out so that the core had a circular cross section, and the cross section of the sheath portion became a ring shape, and the fineness was 120 dt < (consisting of 36 filaments;) < Concentric core type composite fiber. The diameter of each of the filaments of the obtained composite fiber was about 20 iL, and the final cross-sectional area of the fiber was 70%. Weaving with a conjugated fiber to produce a ribbed circular woven fabric' (Comparative Example 1) 26 201120261 Polyether block phthalamide copolymer (available from Arkema Co., Ltd., "Pebax MV1041SA01") added as a thermoplastic polyamide-based elastomer 60 parts by weight, 40 parts by weight of a polyether-based amine copolymer ("Pebax 6333SA01" manufactured by Arkema Co., Ltd.), 0.6 parts by weight of a phosphorus-based antioxidant ("Adekastab PEP36" manufactured by Adeka Co., Ltd.), and titanium oxide (堺Chemical Industry) 5 parts by weight of the company, "D-918"), UV absorber (manufactured by CIBA JAPAN KK, "TINUVIN 234"), 0.3 parts by weight, and light stabilizer (manufactured by CIBA JAPAN Κ.Κ., "TINUVIN 144") After 0.3 parts by weight, melt mixing was carried out, and resin pellets were produced using a granulator. Then, using the obtained resin pellets, the yarn was produced by a melt spinning method to obtain a strand having a fineness of 120 dtex (consisting of 36 filaments) and a diameter of about 20 μm per filament. The obtained raw yarn was woven to prepare a ribbed circular braid. (Comparative Example 2) 60 parts by weight of a polyether block phthalamide copolymer ("Pebax MV1041SA01" manufactured by Arkema Co., Ltd.) as a thermoplastic polyamide-based elastomer, and a polyether block guanamine copolymer (manufactured by Arkema Co., Ltd.) "Pebax 6333SA01") 40 parts by weight, a phosphorus-based antioxidant ("Adekastab PEP36" manufactured by Adeka Co., Ltd.), 1 part by weight, 5 parts by weight of titanium oxide ("D-918" manufactured by Nippon Chemical Industry Co., Ltd.), and an ultraviolet absorber ( 0.3 parts by weight of a light stabilizer (manufactured by CIBA JAPAN KK, "TINUVIN 144"), 0.3 parts by weight, manufactured by CIBA JAPAN KK, "TINUVIN 234"), melt-mixed, and pelletized by a granulator. Then, using the obtained resin pellets, the yarn was produced by a melt spinning method; the fiber 27 was obtained at a temperature of 201120261 and was 120 dtex (consisting of 36 filaments), each! The root filament has a diameter of about 20 v m. The obtained raw yarn was woven to prepare a ribbed circular braid. (Comparative Example 3) A polyether block decylamine copolymer ("Pebax MV1〇41SA〇1" manufactured by Arkema Co., Ltd.) was added as a thermoplastic polyamine-based elastomer. 40 parts by weight of styrene-maleic anhydride copolymer ("SMA1000" manufactured by Sartomer Japan Co., Ltd., manufactured by Arkema Co., Ltd.), 5 parts by weight of phosphorus-based antioxidant (manufactured by CIBA JAPAN KK, " Irgaf0sl26") 0.15 parts by weight, titanium oxide ("d_918", manufactured by 堺Chemical Industries, Ltd.)

5 parts by weight, 3 parts by weight of a UV absorber (manufactured by CIBA JAPAN KK, TINUVm 234), and 3 parts by weight of a light stabilizer (manufactured by Ciba JAPAN KK, "TINUVIN 144"), melt-mixed, and granulated. The machine produces resin pellets. Then, using the obtained resin particles, the yarn was produced by a melt spinning method to obtain a strand having a fineness of 12 〇 dtex (consisting of 36 filaments) and a diameter of about 20 v m per filament. The known strands are woven to produce a ribbed circular braid. (Comparative Example 4) A polyether block decylamine copolymer (manufactured by Arkema Co., Ltd., r Pebax Mvl 〇 41SA〇1) was added as a thermoplastic polyamine-based elastomer. 40 parts by weight of a styrene-maleic anhydride copolymer (manufactured by Sartomer Japan Co., Ltd., r SMA1000) manufactured by Arkema Co., Ltd. 0.3 parts by weight ' 28 % % 201120261 Titanium oxide (manufactured by Sigma Chemical Industry Co., Ltd.) "d_9丨8") 5 parts by weight, ultraviolet light and a charge (manufactured by CIB A JAPAN KK, r tinUVIN 234"') 0.3 parts by weight and 0.3 parts by weight of a light stabilizer (manufactured by CIBA JApAN κ κ, "TINUVIN 144") The mixture was melt-mixed, and a pelletizer was used to prepare resin pellets. Then, using the obtained resin pellets, the yarn was produced by a melt spinning method to obtain a strand having a fineness of 12 〇 dtex (consisting of 36 filaments) and a diameter of about 20 μm per filament. The obtained raw yarn was woven to prepare a rib circular knitted fabric. (Comparative Example 5) 60 parts by weight of a polyether block phthalamide copolymer ("pebax MV1041SA01" manufactured by Arkema Co., Ltd.) as a thermoplastic polyamine-based elastomer, and a polyether block guanamine copolymer (manufactured by Arkema Co., Ltd.) "pebax 6333SA01") 40 parts by weight, styrene. Maleic anhydride copolymer ("Sartomer Japan", "SMA1000") 〇. 2 parts by weight, titanium oxide (manufactured by i-Chemical Industries, Ltd., "D_9181") 0.3 parts by weight of a UV absorber (manufactured by CIBA JAPAN KK, "TINUVIN 234"), and a light stabilizer (manufactured by CIBA JAPAN KK, "TINUVIN 144"), 3 parts by weight, and then melt-mixed and produced using a granulator. Resin particles. Then, using the obtained resin pellets, the yarn was produced by a melt spinning method to obtain a strand having a fineness of 12 〇 dtex (consisting of 36 filaments) and a diameter of about 20 // m per filament. The obtained raw yarn was used for knitting to produce a rib circular knitted fabric. (Comparative Example 6) 100 parts by weight of a polyether block phthalamide copolymer 29, 201120261 ("Pebax MV1041SA01" manufactured by Arkema Co., Ltd.) and a phosphorus-based antioxidant (manufactured by Sumitomo Chemical Co., Ltd.) Sumilizer GP") 0.6 parts by weight, oxidized chin (manufactured by Sigma Chemical Industry Co., Ltd., "d-918"), 5 parts by weight, ultraviolet absorbing agent (manufactured by CIB A JAPAN Κ·Κ, "TINUVIN 234"), 0.3 parts by weight, and light After the stabilizer (manufactured by CIBA JAPAN Co., Ltd., "TINUVIN 144") was 0.3 parts by weight, it was melt-mixed, and resin pellets were produced using a granulator. Then, using the obtained resin pellets, the yarn was produced by a spong spinning method to obtain a strand having a fineness of 120 dtex (consisting of 36 filaments) and a diameter of about 20 // m per filament. The obtained raw yarn was woven to prepare a rib circular knitted fabric. (Comparative Example 7) 100 parts by weight of a polymylon phthalamide copolymer ("Pebax MV1041SA01" manufactured by Arkema Co., Ltd.) and a dish-based antioxidant ("Sumihirer Gp" manufactured by Sumitomo Chemical Co., Ltd.) was added as a thermoplastic polyimide-based elastomer. 0.2 parts by weight, oxidized chin (manufactured by Chemical Industry Co., Ltd., "d_918"), 5 parts by weight, ultraviolet absorbing agent (manufactured by CIBA JAPAN KK, "TINUVIN 234"), 0.3 parts by weight, and light stabilizer (manufactured by ciba japan κ κ) After 0.3 parts by weight of TINUVIN 144"), melt mixing was carried out, and resin pellets were produced using a granulator. Then, using the obtained resin pellets, the yarn was produced by a melt spinning method to obtain a strand having a fineness of 12_ex (consisting of 36 filaments) and a diameter of about 20 per filament. The obtained raw yarn was woven to prepare a rib circular knitted fabric. (Comparative Example 8) Addition of a polyether block phthalamide copolymer 30 as a thermoplastic polyamine-based elastomer (2011: 261, manufactured by Arkema Co., Ltd., "Pebax MV1041SA01"), 100 parts by weight of o-benzoic anhydride 〇. 15 parts by weight of phosphorus-based antioxidant (manufactured by CIBA JApAN κ., "Irgaf〇s 126"), 5 parts by weight of titanium oxide ("D-918" manufactured by Nippon Chemical Industry Co., Ltd.), and UV absorber (CIBA) 3 parts by weight of a light stabilizer (manufactured by CIBA JAPAN KK, "TINUVIN 144") was added in an amount of 3 parts by weight, and then melt-mixed, and a resin pellet was produced using a granulator. Then, using the obtained resin pellets, the yarn was produced by a melt spinning method to obtain a strand having a fineness of 120 dtex (consisting of 36 filaments) and a diameter of about 20 # m per filament. The obtained raw yarn was woven to prepare a ribbed circular braid. (Comparative Example 9) A polyether block decylamine copolymer ("Pebax MV1041SA01", manufactured by Arkema Co., Ltd.), which is a thermoplastic polyamine-based elastomer, was added in an amount of 0.2 part by weight of o-dicarboxylic acid anhydride and titanium oxide ( 5 parts by weight of k, D-918"), a UV absorber (manufactured by ciBA JAPAN KK, "TINUVIN 234"), 0.3 parts by weight, and a light stabilizer (manufactured by ciba JAPAN κ.κ, "TINUVIN 144" After 0.3 parts by weight, the mixture was melted and mixed into a pelletizer to prepare resin pellets. Then, using the obtained resin pellets, the yarn was produced by a melt spinning method to obtain a fineness of 12 〇dtex (consisting of 36 filaments), and the diameter of each filament was about 2 〇β.编织°Weaving was performed using the obtained raw yarn to prepare a ribbed circular woven fabric. (Comparative Example 1 0) Addition of a polyether block phthalamide copolymer as a thermoplastic polyamine-based elastomer 31 201120261 (Manufactured by Arkema, "Pebax Mvl" 〇41SA〇1”) 1〇〇 weight

0.1 parts by weight of phthalic anhydride, 5 parts by weight of titanium oxide ("D-918" manufactured by Nippon Chemical Industry Co., Ltd.), 0.3 parts by weight of ultraviolet absorber (manufactured by CIBA JApAN, "TINUVIN 234"), and a light stabilizer 0.3 parts by weight (manufactured by Ciba JAPAN KK, "TINUVIN 144") was melt-mixed, and resin pellets were produced using a granulator. Then, using the obtained resin pellets, the yarn is produced by a melt spinning method to obtain a filament having a fineness of i 2 〇dtex (consisting of 36 filaments) and having a diameter of about 2 Å per melon. . The obtained raw yarn was used for knitting to produce a rib circular knitted fabric. (Comparative Example 11)

A polyether block phthalamide copolymer ("pebax MV1074SA01" manufactured by Arkema Co., Ltd.), which is a thermoplastic resin-based elastomer, is added as a resin for the Ley portion, and a UV absorber (JApAN Κ·Κ· Manufactured, "TINUVIN 234"), 3 parts by weight, and 3 parts by weight of a light stabilizer (manufactured by Ciba JAPANK.K., "TINUvm 144") were melt-mixed, and a resin particle for sheath was produced using a granulator. In addition, 100 parts by weight of nylon 6 ("UBE Nylon 1011FB" manufactured by Ube Industries, Ltd.) and a UV absorber (manufactured by CIBA JAPAN KK, "TINUVIN 234") 〇·3 After 0.3 part by weight of the weight loss and the light stabilizer (manufactured by CIBA JAKAN κ., TINUVIN 144), the mixture was melt-mixed, and the core resin pellets B were produced using a granulator. Then, the obtained sheath portion resin particles A and the core resin particles b are heated and sinter by a uniaxial extruder, and the composite spinning is performed so that the cross section of the portion 32 201120261 becomes a circular shape and a cross section of the sheath portion. It was roughly c-shaped, and a partially open eccentric core-sheath type composite fiber having a fineness of 120 dtex (consisting of 36 filaments) was obtained. The diameter of each filament of the obtained composite fiber was about 2 〇 v m, and the occupation ratio of the core portion was 8 〇 0 / 相对 with respect to the fiber cross-sectional area. The obtained composite fiber was woven to prepare a rib circular knitted fabric. (Comparative Example 12) As a resin for a core portion, a polyether block phthalamide copolymer (manufactured by Arkema Co., Ltd., r Pebax MV1074SA01), which is a thermoplastic polyamine-based elastomer, was added in an amount of 1 part by weight, and an ultraviolet absorber ( 3 parts by weight of a light stabilizer (manufactured by CIBA JAPANK.K., "TINUVIN 144"), 3 parts by weight, manufactured by CIBA JApAN KK, "TINUVIN 234"), melt-mixed, and a core machine using a granulator The resin particles are used for hydrazine. As a resin for the sheath, a nylon 6 (manufactured by Ube Industries, Ltd., "UBENyl〇nl〇UFB"), which is a polyamide resin, is added in an amount of 1 part by weight, and a UV absorber (manufactured by CIBA JAPANK K, "tinuvin 234") 3 parts by weight and 3 parts by weight of a light stabilizer (manufactured by CIBA JApAN κ κ, VIN 144), and then melt-mixed using a granulator to produce resin particles 勒 for the part. Further, the obtained core, the partial resin pellets, and the resin pellets for the portion are respectively heated and melted by a uniaxial extruder, and the composite yarn is subjected to composite spinning so that the cross section of the core portion becomes circular, and the cross section of the sheath portion becomes substantially c. %, the conjugate fiber obtained by the partial eccentric core-sheath type composite fiber having a fineness of 36 is composed of 36 filaments has a diameter of about 2 G μm, and the occupied portion is relative to the fiber cross-sectional area. It is 80%. 33 201120261 Weaving using the obtained composite fiber to produce a ribbed circular braid. (Comparative Example 13) 100 parts by weight of a polyether block phthalamide copolymer ("Pebax MV1074SA01" manufactured by Arkema Co., Ltd.) as a thermoplastic polyamine-based elastomer, and a UV absorber (manufactured by CIBA JAPAN Κ·Κ·, 0.3 parts by weight of TINUVIN 234") and 0.3 parts by weight of a light stabilizer (manufactured by CIBA JAPAN Co., Ltd., "TINUVIN 144") were melt-mixed, and a resin pellet A was produced using a granulator. 100 parts by weight of nylon 11 ("Rilsan BESN TL" manufactured by Arkema Co., Ltd.), UV absorber (manufactured by CIBA JAPAN KK, "TINUVIN 234"), 0.3 parts by weight, and light stabilizer (CIBA JAPAN) 0.3.Κ. Manufactured, "TINUVIN 144") 0.3 parts by weight, melt-mixed, and granulator was used to produce resin pellets B. Then, the obtained resin pellet A and resin pellet B were respectively heated and melted by a uniaxial extruder, and the composite yarn was subjected to composite spinning so that the respective cross sections thereof became semicircular, and the fineness was 120 dtex (consisting of 36 filaments). Side by side composite fiber. The diameter of each filament of the obtained composite fiber was about 20 // m, and the occupation ratio of the core portion was 50% with respect to the fiber cross-sectional area. The obtained composite fiber was woven to prepare a rib circular knitted fabric. (Comparative Example 14) 100 parts by weight of a polyether block phthalamide copolymer ("pebax MV1074SA01" manufactured by Arkema Co., Ltd.) and a UV absorber (manufactured by CIBA JAPAN KK "TINUVIN 234" was added as a thermoplastic polyimide-based elastomer. 0.3 parts by weight and a light stabilizer (manufactured by CIBA JAPAN Co., Ltd., 34 201120261 "TINUVIN 144") 〇 3 parts by weight, melt-mixed, and a resin granule A was produced using a granulator. Nylon 12 (manufactured by Ube Industries, Ltd., "UBESTA 3014B") as a polyamide resin, 1 part by weight, UV absorber (manufactured by cIBA JAPANK.K., "TINUVIN 234"), 3 parts by weight, and light Stabilizer (manufactured by CIBA JAPAN KK, "TINUVIN 144") 3·3 parts by weight and then 'melt-mixed' using a granulator to produce resin pellets. Then, the obtained resin pellets and resin pellets β were respectively heated and melted by a uniaxial extruder to perform composite spinning to make their respective cross sections semicircular, and the obtained fineness was 120 dtex (consisting of 36 filaments) Side by side composite fiber. The diameter of each filament of the obtained composite fiber was about 20 μm, and the occupation ratio of the anger portion was 5 〇 0 / 相对 with respect to the fiber cross-sectional area. The obtained composite fiber was woven to prepare a rib circular knitted fabric. (Comparative Example 15) As a resin for the sheath portion, a polyether block phthalamide copolymer ("pebax MV1074SA01" manufactured by Arkema Co., Ltd.) as a thermoplastic polyamine-based elastomer was added in an amount of 1 part by weight, and an ultraviolet absorber ( 0.3 parts by weight of CIBA JApAN K, manufactured by K., "TINUVIN 234", and 0.3 parts by weight of a light stabilizer (manufactured by CIBa JAPAN Co., Ltd., "TINUVIN 144"), and then melt-mixed to produce a sheath using a granulator. Partial resin pellet A. A thermoplastic polyester elastomer (manufactured by Toyobo Co., Ltd., "Pelprene p_l5〇B"), 1 part by weight, and a UV absorber (manufactured by CIBA JAPAN K.K_, "TINUVIN 234") is added as a resin for the core. After 0.3 parts by weight of the light stabilizer and the light stabilizer (manufactured by CIBA JAPAN KK, 35 201120261 TINUVIN 144), the mixture was melt-mixed, and the core resin pellets B were produced using a granulator. Then, the obtained resin portion A for the sheath portion and the resin particles B for the core portion are respectively heated and melted by a uniaxial extruder to perform composite spinning so that the cross section of the core portion becomes circular, and the cross section of the sheath portion becomes a ring shape. A concentric core-sheath type composite fiber having a fineness of l2〇dtex (consisting of 36 filaments) was obtained. The diameter of each filament of the obtained composite fiber is about 2 〇 "m, and the occupation ratio of the core portion is 7 〇〇 / 0 with respect to the fiber cross-sectional area. The woven fiber obtained by the woven fabric is used to produce a rib circular knitting fabric. (Comparative Example 16) As a four-part resin, 100 parts by weight of a poly-blocking phthalamide copolymer ("Pebax MV1074SA01" manufactured by Arkema Co., Ltd.), which is a thermoplastic polyamine-based elastomer, and a UV absorber (CIBA) were added. 3 parts by weight of 光·3 parts by weight and a light stabilizer (manufactured by CIBA JAPAN KK, "TINUVIN 144"), 3 parts by weight, and melt-mixed, and used to prepare core resin pellets using a granulator. Λ 作为 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI TINUVIN 234") 0.3 parts by weight and 0.3 parts by weight of a light stabilizer (manufactured by CibA JAPAN KK, "TINUVIN 144") were melt-mixed, and the resin particles B for sheath portions were produced using a granulator. Then, the obtained core resin particles A and the sheath resin particles b are respectively heated and melted by a uniaxial extruder, and the composite yarn is woven so that the cross section of the core portion 36 201120261 becomes circular, and the cross section of the sheath portion becomes Ring-shaped, a concentric core-sheath type composite fiber having a fineness of 12 〇dtex (consisting of 36 filaments) is obtained. The diameter of each filament of the obtained composite fiber was about 20 # ni, and the core portion occupied 70% with respect to the fiber cross-sectional area. The obtained composite fiber was woven to prepare a rib circular knitted fabric. (Example 17) 60 parts by weight of a polyether block phthalamide copolymer ("Pebax MV1041SA01" manufactured by Arkema Co., Ltd.), which is a thermoplastic polyamine-based elastomer, was added, and a ruthenium-methyl hydrazine copolymer (manufactured by Arkema Co., Ltd.) was added. 40 parts by weight of styrene-maleic anhydride copolymer ("SMA1000", manufactured by Sartomer Japan Co., Ltd.), and a phosphorus-based antioxidant ("Adekastab PEP36" manufactured by ADEKA Co., Ltd.) 40 parts by weight Heavy injury, titanium oxide (manufactured by Field Chemical Industry Co., Ltd., rutile type dioxide

4 parts by weight of Chin "D-918"), 0.3 parts by weight of a UV absorber (manufactured by ciBA JAPAN KK, "TINUVIN 234"), and 0.3 parts by weight of a light stabilizer (manufactured by CIBa JAPAN Co., Ltd., "TINUVIN 144") , 'melt mixing, using a granulator to make resin pellets. Then, 'the obtained resin pellets were used for the spinning by the melt spinning method' to obtain a strand having a fineness of 120 dtex (consisting of 36 filaments) and a straight twist of about 2 Å per quot. The obtained raw yarn was used for weaving to produce a ribbed circular braid. (Example 18) A polyether block decylamine copolymer ("Pebax MV1041SA01", manufactured by Arkema Co., Ltd.), which is a thermoplastic polyamine-based elastomer, was added. 60 Weight 37 201120261 parts, Polysulfonium-segmented amine copolymer (Arkema Corporation) Manufactured, "Pebax 63 33SA01") 40 parts by weight, styrene-maleic anhydride copolymer ("Sartomer Japan", "SMA1000") 1.5 parts by weight, phosphorus-based antioxidant ("Adekastab PEP36", manufactured by ADEKA) 1 part by weight, 4 parts by weight of titanium oxide ("D-918" manufactured by Nippon Chemical Co., Ltd.), 0.3 parts by weight of a UV absorber (manufactured by CIBA JAPAN KK, "TINUVIN 234"), and a light stabilizer (manufactured by CIBA JAPAN KK, After "0.3 parts by weight of "TINUVIN 144"), melt-mixing was carried out, and resin pellets were produced using a granulator. Then, the obtained resin pellets were used for the spinning by a melt spinning method to obtain a fineness of 120 dtex (from 36 filaments). It is composed of a raw yarn having a diameter of about 20 // m per filament. The obtained raw yarn was used for weaving to produce a ribbed circular braid. (Example 19) 60 parts by weight of a polyether block guanamine copolymer ("Pebax MV1041SA01" manufactured by Arkema Co., Ltd.) as a thermoplastic polyamine-based elastomer, and a polyether block guanamine copolymer (manufactured by Arkema Co., Ltd.) "Pebax 6333SA01") 40 parts by weight, styrene-maleic anhydride copolymer ("SMA1000" manufactured by Sartomer Japan Co., Ltd.), 2 parts by weight, and antioxidant (manufactured by CIBA JAPAN KK, "Irgafos 126") 0.15 by weight 4 parts by weight of titanium oxide ("D-918" manufactured by Sigma Chemical Industry Co., Ltd.), UV absorber (manufactured by CIBA JAPAN KK, "TINUVIN 234"), 0.3 parts by weight, and light stabilizer (manufactured by CIBA JAPAN KK) "TINUVIN 144") After 0 to 3 parts by weight, melt-mixing was carried out to prepare resin pellets using a 38 201120261 pellet machine. Then, using the obtained resin pellets, the filaments were subjected to a melt spinning method to obtain a fineness of 120 dteX (consisting of 36 filaments) and a diameter of about 20 / z m per t filament; Your field 4 is woven using the obtained raw silk to make a ribbed circular braid. (Example 20) 6 parts by weight, polyether block, added as A #plastic polyamide amine & && polyether block-branched amine copolymer ("Pelax mv1〇41sa〇i", manufactured by Arkema Co., Ltd.) Indoleamine copolymer ("6333SA01", manufactured by Arkema Co., Ltd.) 40 parts by weight, styrene-maleic anhydride copolymer ("Sartomer japan", "SMA1〇〇〇j" 〇3 parts by weight, phosphorus-based antioxidant ( Sumitomo Chemical Co., Ltd., "SumilizerGp") 〇 2 parts by weight, titanium oxide (manufactured by Sigma Chemical Industry Co., Ltd., "d_918j" 6 parts by weight, UV absorber (manufactured by CIBA JAPAN Κ·Κ., "TINUVIN 234") 0.3 parts by weight Further, 0.3 parts by weight of a light stabilizer (manufactured by ciBA JAPAN Co., Ltd., TINUVIN 144) was melt-mixed, and resin pellets were produced using a granulator. Using the obtained resin pellets, the filaments were subjected to a melt spinning method to obtain a strand having a fineness of 120 dtex (consisting of 36 filaments) and a diameter of about 20 // m per filament. The obtained raw yarn was used for weaving to produce a ribbed circular braid. (Example 21) A polyether block phthalamide copolymer ("Pebax MV1041SA01", manufactured by Arkema Co., Ltd.), which is a thermoplastic polyamine-based elastomer, was added. 100 Weight 39 201120261 3 parts by weight of o-benzene phthalic anhydride oxime, phosphorus system Antioxidant (Sumiton Chemical Co., Ltd., Sumillzer GP) 0.6 parts by weight, titanium oxide (manufactured by Daisei Chemical Industries, Ltd., "D-918"), parts by weight, UV absorber (manufactured by JAPANK.K., "TINUVIN 234" 〇 3 parts by weight and a light stabilizer (manufactured by CIBA JAPAN KK, "Ding INUVIN 144") 3·3 parts, and then melt-mixed, and a resin pellet was produced using a granulator. Then, using the obtained resin pellets, the yarn was produced by a melt spinning method, and the original yarn having a fineness of 12 〇dtex (consisting of 30 filaments) and having a diameter of about 20 // m per i filament was obtained. wire. The obtained raw yarn was used for weaving to produce a ribbed circular braid. (Example 22) A polyether block phthalamide copolymer ("Pebax MV1041SA01", manufactured by Arkema Co., Ltd.), which is a thermoplastic polyamine-based elastomer, was added in an amount of 100 parts by weight, and 1 part by weight of phthalic anhydride, and a phosphorus-based antioxidant. (manufactured by CIBA japan KK, "irgaf0S 126"), 0.15 parts by weight, titanium oxide (manufactured by Daicel Chemical Industry Co., Ltd., "D-91 8"), 4 parts by weight, UV absorber (manufactured by ciBA JAPANK.K., "TINUVIN 234" 3 parts by weight and a light stabilizer (manufactured by CIBA JAPAN KK, "TINUVIN 144") 3.3 parts by weight and then "melt-mixed" using a granulator to produce resin pellets. Then, using the obtained resin pellets 'by spinning by the melt spinning method', a strand having a fineness of 120 dtex (consisting of 36 filaments) and having a diameter of about 20 // m per filament was obtained. The obtained raw yarn was used for weaving to produce a ribbed circular braid. (Example 23) 40 201120261 Addition of a polyether block phthalamide copolymer (manufactured by Arkema Co., Ltd., r Pebax MVI〇41SA〇1) as a thermoplastic polyamine-based elastomer, 1 〇〇 weight loss, phthalic anhydride 2 parts by weight, 0.5 parts by weight of a phosphorus-based antioxidant ("Adekastab PEP36" manufactured by ADEKA Co., Ltd.), 4 parts by weight of titanium oxide ("D-918" manufactured by Nippon Chemical Industry Co., Ltd.), and a UV absorber (ciBA JAPAN KK) Manufactured, "TINUVIN 234") 〇 3 parts by weight and 0.3 parts by weight of a light stabilizer (manufactured by CIBA JAPAN KK, "TINUVIN 144"), melt-mixed, and a resin pellet was produced using a granulator. Then, using the obtained resin pellets, the yarn was subjected to a melt spinning method to obtain a strand having a fineness of 120 dteX (consisting of 30 filaments) and having a diameter of about 20 m per one filament. The obtained raw yarn was used for weaving to produce a ribbed circular braid. (Example 24) A polyether block phthalamide copolymer ("Pelax MV1041SA01", manufactured by Arkema Co., Ltd.), which is a thermoplastic polyamine-based elastomer, was added in an amount of 1 part by weight, and phthalic anhydride was used. 1 part by weight of a phosphorus-based antioxidant ("Adekastab PEP36" manufactured by ADEKA & A), 4 parts by weight of titanium oxide ("D-918" manufactured by Sigma Chemical Industry Co., Ltd.), and an ultraviolet absorber (manufactured by αΒΑ JAPANK.K., " TINUVIN 234") 3 parts by weight and a light stabilizer (manufactured by CIBA JAPAN Co., Ltd., "TINUVIN 144"), 3 parts by weight, were melt-mixed, and resin pellets were produced using a granulator. Then, using the obtained resin pellets, by spinning by a melt spinning method, a strand having a fineness of 12 〇 dtex (consisting of 36 filaments) and having a diameter of about 20 μm per i filament was obtained. Weaving using the obtained raw yarn, 201120261 Making a ribbed circular braid. (Example 25) As a resin for the crotch portion, 100 parts by weight of styrene-cisene was added as a polyacrylamide-based phthalamide copolymer (manufactured by Arkema Co., Ltd., r pebax MV1074SA01). Diacid anhydride copolymer (manufactured by Sartomer Japan Co., Ltd., "SMA1 〇〇〇") 1 part by weight, filled with antioxidant (manufactured by Sumitomo Chemical Co., Ltd., "Sumilizer GP") 〇.3 Heavy wounds, Oxidation Chin (manufactured by Squeeze Chemical Industry Co., Ltd.) "D_918") 5 weight damage, •, external absorbent (manufactured by CIBA JAPAN KK, "TINUVIN 2341" 0.3 parts by weight, and light stabilizer (manufactured by Ciba JAPAN κ. κ., "TINUVIN 144") 〇·3 parts by weight After that, the mixture is melt-mixed, and the granules are used to produce the resin particles A for the sheath. As the resin for the core, nylon 6 (manufactured by Ube Industries, Ltd., "UBE Nylon 1011FB"), which is a polyamide resin, is added. 〇 by weight, styrene-maleic anhydride copolymer (Sart〇mer 邛(10) company,

"SMA1000") 1 part by weight, a phosphorus-based antioxidant (manufactured by Sumitomo Chemical Co., Ltd., "Sumilizer GPj", 3 parts by weight, and titanium oxide (manufactured by Daicel Chemical Industry Co., Ltd., D-91 8)), 5 parts by weight, 3 parts by weight of a UV absorber (manufactured by CIB A JAp AN KK & TIN, TINUVIN 234), and a light stabilizer (manufactured by Ciba Japan K.K., "TINUVIN 144"), 3 parts by weight, and then melt-mixed. The core resin pellets b are produced by a granulator. The resin portion A for the sheath portion obtained and the resin particles B for the core portion are respectively heated and melted by a uniaxial extruder, and the composite yarn is woven to make the cross section of the core portion circular.纟c-shaped, obtaining a partially open eccentric (four) type composite fiber having a fineness of 42 201120261 120 dtex (consisting of 36 filaments). The diameter of each of the obtained composite fibers is about 2 〇"claw, and the heart portion The occlusion ratio was 8 〇% with respect to the cross-sectional area of the fiber, and the obtained conjugate fiber was used for knitting to prepare a rib-shaped circular woven fabric. (Example 26) As a resin for a core portion, a polymer as a thermoplastic polyamide-based elastomer was added. 1 part by weight of an ether block amide copolymer ("Pelax MV1074SA01", manufactured by Arkema Co., Ltd.), 1 part by weight of a styrene-maleic anhydride copolymer ("Sartomer Japan", "SMA1000"), and filled Antioxidant ("SumiUzer GP" manufactured by Sumitomo Chemical Co., Ltd.) ο" Parts by weight, Oxidation Chin (made by Chemical Industry Co., Ltd., "D_9i8") 5 Reset Injury UV Absorbent (manufactured by CIBA JAPAN KK, "TINUVIN 2" 34 parts) 3 parts by weight and a light stabilizer (manufactured by Ciba JAPAN K.K., "TINUVIN 144") 〇 3 parts by weight, melt-mixed, and a pelletizer for cores was produced using a granulator. As a sheath resin, a nylon 6 (manufactured by Ube Industries, Ltd., "UBE Nylon 1011FB"), which is a polyamide resin, was added in an amount of 100 parts by weight, stupid ethylene-cis-butylene-acid-acid needle copolymer (Sartomer Japan). 1 part by weight of the company, "SMA10"), 0.3 parts by weight of a phosphorus-based antioxidant ("Sumilizer GP" manufactured by Sumitomo Chemical Co., Ltd.), and 5 parts by weight of titanium oxide ("D-918" manufactured by Nippon Chemical Industry Co., Ltd.) 0.3 parts by weight of a UV absorber (manufactured by CIBA JAPAN KK, "TINUVIN 234") and 3 parts by weight of a light stabilizer (manufactured by CiBa JAPAN 、·Κ, "TINUVIN 144"), and then mixed and used in 2011 201126261 The granulator is used to form the resin particles B for the parts. Then, the core portion obtained by the use of the 榭4 曰 曰 曰 particles A and the sheath resin particles b are respectively fused by a uniaxial extruder, and the composite is spun to make the cross section of the core into a circle. In the shape of the sheath, the cross section of the sheath portion is substantially C-shaped, and a eccentric core-sheath type composite fiber having a fineness of 120 dtex (consisting of 36 filaments) is obtained. The diameter of each of the obtained composite fibers is about Μ", and the occupation ratio of the boring tool is relative to the cross-sectional area of the fiber. The obtained composite fiber is woven to produce a rib circular knitted fabric. Addition of a polyether block phthalamide copolymer ("Pebax Mvl〇74SA〇1", manufactured by Arkema Co., Ltd.) as a thermoplastic polyamide-based elastomer

1 part by weight of a succinyl-succinic acid-rich liver copolymer ("SMA1000" manufactured by Sartomer Japan Co., Ltd.), a phosphorus-based antioxidant ("Sumilizer GP" manufactured by Sumitomo Chemical Co., Ltd.), 0.3 part by weight, and titanium oxide (堺) 5 parts by weight of the "D-918" manufactured by Chemical Industry Co., Ltd., UV absorber (manufactured by CIBA JAPANK.K., "ΤιΝυνΐΝ234"), 3 parts by weight, and light stabilizer (manufactured by CIBA JAPAN Κ·Κ·, "TINUVIN" 144") 0.3 After heavy injury, 'mix and melt, and use a granulator to make resin pellets. 100 parts by weight of a nylon 11 ("Rilsan BESN TL" manufactured by Arkema Co., Ltd.) and a stupid ethylene-maleic anhydride copolymer (manufactured by Sartomer Japan Co., Ltd., "SMA 1000") Antioxidant (Sumilizer GP, manufactured by Sumitomo Chemical Co., Ltd.) 33 parts by weight, titanium oxide ("D-918", manufactured by Sigma Chemical Industry Co., Ltd.) 5 44 201120261 parts by weight, UV absorber (manufactured by CIBA JAPAN KK, "TINUVIN 234") 0.3 parts by weight and 0.3 parts by weight of a light stabilizer (manufactured by CIBa jAPan κ κ, "TINUVIN 144") were melt-mixed, and a resin granule B was produced using a granulator. Then, 'the resin pellet A and the resin pellet b obtained were respectively heated and melted by a uniaxial extruder', and the composite yarn was subjected to composite spinning so that the respective cross sections thereof became semicircular, and the fineness was 120 dtex (consisting of 36 filaments). Side by side composite fiber. The diameter of each filament of the obtained composite fiber was about 2 〇 M m, and the occupation ratio of the core portion was 50% with respect to the fiber cross-sectional area. The obtained composite fiber was woven to prepare a rib circular knitted fabric. (Example 28) 100 parts by weight of a polyether block phthalamide copolymer ("Pebax MV1074SA01" manufactured by Arkema Co., Ltd.) as a thermoplastic polyamide-based elastomer, and a styrene-maleic anhydride copolymer (Sart〇) 1 part by weight of "SMA1000" manufactured by mer Japan, 0.3 parts by weight of a phosphorus-based antioxidant ("Sumihzer GP" manufactured by Sumitomo Chemical Co., Ltd.), and 5 parts by weight of titanium oxide ("D-918" manufactured by Nippon Chemical Industry Co., Ltd.) UV absorber (manufactured by CIBA JAPAN KK, "TINUVIN 234") 3·3 parts by weight and light stabilizer (manufactured by CIBA JAPAN KK·, "TINUVIN 144") 〇.3 After heavy injury, 'melt mixing, use system Resin particles A were produced by a pelletizer. 100 parts by weight of a nylon 12 (manufactured by Ube Industries, Ltd., "UBESTA3〇14B") as a polyamide resin, and 1 part by weight of a styrene-succinic acid dilute liver copolymer ("SMA1000" manufactured by Sartomer Japan Co., Ltd.) 45 201120261 Squama Antioxidant ("SumiHzer Gp", manufactured by Sumitomo Chemical Co., Ltd.) 0.3 Heavy wounds, Oxidized Chin (manufactured by Chemical Industry Co., Ltd., "D_9丨8") 5 heavy wounds, UV absorber (manufactured by CIBA JAPAN KK, "TINUVIN 234") 0.3 parts by weight and 3 parts by weight of a light stabilizer (manufactured by Ciba JAPAN KK, TINUVIN 144) were melt-mixed, and a pelletizer was produced using a granulator. Then, the obtained resin pellets and resin pellets β are respectively heated and melted by a uniaxial extruder to perform composite spinning so that their respective cross sections are semicircular, and the fineness is UOdtex (consisting of 30 filaments) Side by side composite fiber. The diameter of the filament of the mother of the conjugated fiber is about 2 〇〆m, and the occupation ratio of the core portion is 5 〇 0 / 相对 with respect to the fiber cross-sectional area. The obtained composite fiber was woven to prepare a rib circular knitted fabric. (Example 29) As a resin for a granule, a poly-blocking phthalamide copolymer ("Pebax MV1074SA01", manufactured by Arkema Co., Ltd.), which is a thermoplastic polyamide-based elastomer, was added in an amount of 1 part by weight to styrene. 1 part by weight of a maleic anhydride copolymer ("SMA1000", manufactured by Sartomer Japan Co., Ltd.), filled with an antioxidant ("Sumihirer Gp" manufactured by Sumitomo Chemical Co., Ltd.), 3 parts by weight, and titanium oxide (manufactured by Sigma Chemical Industry Co., Ltd.) "D_918") 5 parts by weight, ultraviolet absorber (manufactured by CIBA JAPAN KK, "TINUVIN 234") 〇 '3 parts by weight, and 0.3 parts by weight of light stabilizer (manufactured by CIBA JApAN κ κ, TINUVIN 144)) The granules were mixed and the resin particles A for sheaths were produced. 46 201120261 As a resin for the core, a thermoplastic polyester elastomer (manufactured by Toyo Toyobo Co., Ltd., Γ Pelprene p l5〇B) is added in an amount of 1 part by weight, and styrene-butadiene anhydride copolymer ( 1 part by weight of a "SMA 1000" manufactured by Sartomer Japan, a phosphorus-based antioxidant ("Sumilizer GP" manufactured by Sumitomo Chemical Co., Ltd.), 3 parts by weight, and titanium oxide ("D-918", manufactured by Nippon Chemical Industry Co., Ltd.) After the weight fraction, the ultraviolet absorber (manufactured by Ciba JAPAN KK·, "TINUVIN 234"), 3 parts by weight, and the light stabilizer (manufactured by CIBA JAPAN Co., Ltd., "TINUVIN 144"), 3 parts by weight, followed by melt mixing 'The core resin pellet B was produced using a granulator. Then, the obtained resin portion A for the sheath portion and the resin particles b for the core portion are respectively heated and melted by a uniaxial extruder to perform a composite spinning so that the cross section of the core portion becomes a circular shape, and the cross section of the sheath portion becomes a ring shape. A concentric core-sheath type composite fiber having a fineness of 12 〇 dtex (consisting of 36 filaments) was obtained. The diameter of each filament of the obtained composite fiber was about 2 〇 A m , and the occupation ratio of the core portion was 7 % by weight with respect to the fiber cross-sectional area. The obtained composite fiber was woven to prepare a rib circular knitted fabric. (Embodiment 30)

As a resin for a core, a polyether block phthalamide copolymer ("Pebax MV1074SA01", manufactured by Arkema Co., Ltd.) as a thermoplastic polyimide polymer is added in an amount of 1 part by weight, and a copolymer of ethylene-maleic anhydride is added. (Sartomer Japan company, "SMA1〇〇〇j" i parts by weight, phosphorus-based antioxidant (Sumitomo Chemical Co., Ltd., "Sumilizer Gp") 〇·3 parts by weight, titanium oxide (manufactured by 堺Chemical Industries, Ltd., "D_918 ”5 weight loss, 凫 external line absorbent (manufactured by CIB A JAP AN KK, “TINUVIN 47 201120261 234”) 3·3 parts by weight, and light stabilizer (manufactured by CIBA JAPAN KK, “TINUVIN 144”) 0.3 parts by weight, The melt-mixing was carried out, and the core resin pellet A was produced using a granulator. 100 parts by weight of a thermoplastic polyester elastomer ("Pelprene P-150B" manufactured by Sakamoto Toyobo Co., Ltd.) and a styrene-cis-butylene acid needle copolymer (manufactured by Sartomer Japan Co., Ltd.) 1 part by weight, 0.3 parts by weight of a phosphorus-based antioxidant ("Sumilizer GP" manufactured by Sumitomo Chemical Co., Ltd.), and 5 parts by weight of titanium oxide ("D-918" manufactured by Sigma Chemical Industry Co., Ltd.). 0.3 parts by weight of a UV absorber (manufactured by ciBA JAPAN KK, "TINUVIN 234") and 0.3 parts by weight of a light stabilizer (manufactured by ciBA JAPAN KK, "TINUVIN 144") were melt-mixed, and a granulator was used to produce a sheath. Resin particle B. Then, the obtained core resin particles A and the sheath resin particles b are respectively heated and melted by a uniaxial extruder, and composite spinning is performed so that the cross section of the core portion is circular, and the cross section of the sheath portion is formed into a ring shape. A concentric core-sheath type composite fiber having a fineness of 12 〇 dtex (consisting of 36 filaments) was obtained. The diameter of the mother filament of the known composite fiber is about #m, and the occupation ratio of the core portion is 7〇% with respect to the fiber cross-sectional area. The obtained composite fiber was woven to prepare a rib circular knitted fabric. (Comparative Example 1 7) A polyether block decylamine copolymer (manufactured by Arkema Co., Ltd., r Pebax Mvi〇 41SA〇l) was added as a thermoplastic polyimide polymer, and 6 parts by weight of a polyether block guanamine copolymer was added. 40 parts by weight of a compound ("pebax 6333SA01" manufactured by Arkema Co., Ltd.), a phosphorus-based antioxidant (manufactured by Adeka Co., Ltd., 48 201120261, "Adekastab PEP36"), 0.6 parts by weight, and titanium oxide (manufactured by Sigma Chemical Industry Co., Ltd., "D-9 1 8") 2 parts by weight, 0.3 parts by weight of a UV absorber (manufactured by Ciba JAPANK.K., "TINUVIN 234"), and 3 parts by weight of a light stabilizer (manufactured by CIBA JAPAN KK, "TINlJVIN 144"), followed by melt mixing Using a granulator to make resin pellets. Then, using the obtained resin pellets, by spinning by a melt spinning method, a strand having a fineness of 120 dtex (consisting of 36 filaments) and having a diameter of about 20 /zm per filament was obtained. The obtained raw yarn was used for weaving to produce a ribbed circular braid. (Comparative Example 1 8) A polyether block phthalamide copolymer ("Pebax Mvl 〇 41SA〇1", manufactured by Arkema Co., Ltd.) as a thermoplastic polyamine-based elastomer was added in an amount of 6 parts by weight, and a polyether block amide copolymer was added. 40 parts by weight of a product ("6333SA01" manufactured by Arkema Co., Ltd.), 1 part by weight of a phosphorus-based antioxidant ("Adekastab PEP36" manufactured by ADEKa Co., Ltd.), and 2 parts by weight of titanium oxide ("D·918" manufactured by Nippon Chemical Industry Co., Ltd.) And a UV absorber (manufactured by CIBA JAPANK.K., "TINUVIN 234j"), 3 parts by weight, and a light stabilizer (manufactured by CIBA JAPAN κ., "TmuviN 144") 〇3, and then mixed and dissolved. Resin particles were produced using a granulator. Then, 'Using the obtained tree yue granules, making silk by melt spinning method', the fineness is 12〇dtex (consisting of 36 4 4 secret j·, _, Tiangen filament), each length The diameter of the wire is about 20 am /5 secret, ± _ ... 4. The obtained raw yarn was used for weaving to produce a ribbed circular braid. (Comparative Example 1 9) 49 201120261 A polyether block phthalamide copolymer ("pebax MV1041SA01" manufactured by Arkema Co., Ltd.), which is a thermoplastic polyamine-based elastomer, was added, and 60 parts by weight of a polyether block guanamine copolymer (Arkema) was added. 40 parts by weight of styrene-maleic anhydride copolymer ("SMA1000", manufactured by Sartomer Japan Co., Ltd.) 0_05 parts by weight, phosphorus-based antioxidant (manufactured by CIBA JAPAN K_K., "Irgafos 126" 0.15 parts by weight, 1 part by weight of titanium oxide (manufactured by Sigma Chemical Industry Co., Ltd.), 0.3 parts by weight of a UV absorber (manufactured by CIBA JAPAN KK, "TINUVIN 234"), and a light stabilizer (manufactured by CIBA JAPAN KK) After 0.3 parts by weight of "Tinuvin 144"), it was melt-mixed, and resin pellets were produced using a granulator. Then, using the obtained resin pellets, the yarn was produced by a melt spinning method to obtain a strand having a fineness of 120 dtex (consisting of 36 filaments) and a diameter of about 20 # m per filament. The obtained raw yarn was used for weaving to produce a ribbed circular braid. (Comparative Example 20) A polyether block phthalamide copolymer (manufactured by Arkema Co., Ltd., "pebax MV1041SA011"), 60 parts by weight of a polyether block-branched amine copolymer (manufactured by Arkema Co., Ltd.) was added as a thermoplastic polyimide polymer. "pebax 6333SA01") 40 parts by weight, styrene-maleic anhydride copolymer ("Sartomer Japan", "SMA1 〇〇〇") 0.3 parts by weight, UV absorber (manufactured by CIBA JAPAN Κ·Κ·, "TINUVIN 234 0.3 parts by weight and 3 parts by weight of a light stabilizer (manufactured by CIBA jAPAN κK, "TINUVIN 144") were melt-mixed, and resin pellets were produced using a 50 201120261 pellet machine. Then, using the obtained resin pellets, the filaments were subjected to a melt spinning method to obtain a strand having a fineness of 120 dtex (consisting of 36 filaments) and a diameter of about 20 μm per filament. The obtained raw yarn was used for weaving to produce a ribbed circular braid. (Comparative Example 21) 60 parts by weight of a polyether block phthalamide copolymer ("pebax MV1041SA011" manufactured by Arkema Co., Ltd.), which is a thermoplastic polyamine-based elastomer, and a scaly block amide copolymer (manufactured by Arkema Co., Ltd.) "Pebax 6333SA01") 40 parts by weight of styrene-cis-succinic anhydride copolymer ("Sartomer Japan", "SMA1000") 〇 2 parts by weight, UV absorber (CIBA JAPAN Κ.Κ·Manufacture, "TINUVIN" 234") 0.3 parts by weight and 0.3 parts by weight of a light stabilizer (manufactured by CIBA JAPAN KK Co., Ltd., "TINUVIN 144") were melt-mixed, and resin pellets were produced using a granulator. Then, using the obtained resin pellets 'filament by melt spinning method', a strand having a fineness of 120 dtex (consisting of 36 filaments) and a diameter of about 20 μm per filament was obtained. The obtained raw yarn was used for weaving to produce a ribbed circular braid. (Comparative Example 22) 100 parts by weight of a polyether block phthalamide copolymer ("Pebax MV 1041 SAO 1" manufactured by Arkema Co., Ltd.) and a phosphorus-based antioxidant (manufactured by Sumitomo Chemical Co., Ltd.) "Sumilizer GP") 0.6 parts by weight, UV absorber (Manufactured by ciBA JAPAN Κ.Κ., 51 201120261

"TINUVIN 234") 3 parts by weight and 3 parts by weight of a light stabilizer (manufactured by cIBa JApAN K.K., "TINUVIN 144"), and then melt-mixed to produce resin pellets using a granulator. Then, using the obtained resin pellets, the yarn was subjected to a melt spinning method to obtain a strand having a fineness of 120 dtex (consisting of 36 filaments) and a diameter of about 20 m per one filament. The obtained raw yarn was used for weaving to produce a ribbed circular braid. (Comparative Example 23) A polyether block phthalamide copolymer ("Pebax MV1041SA01", manufactured by Arkema Co., Ltd.), which is a thermoplastic polyamine-based elastomer, was added in an amount of 1 part by weight, and a phosphorus-based antioxidant (manufactured by Sumitomo Chemical Co., Ltd., " SumiHzej> Gp ^ ) 2·2 parts by weight, UV absorber (manufactured by CIBA jAPAN κ., manufactured by "TINUVIN 234"), 0.3 parts by weight, and light stabilizer (manufactured by CIBA JAPAN KK, "TINUVIN 144") 〇 3 After the parts by weight, melt mixing was carried out, and resin pellets were produced using a granulator. Using the obtained resin pellets, the obtained resin pellets were subjected to a spun spinning method to obtain a fineness of 120 dtex (consisting of 36 filaments), each! The root filament has a diameter of about 20 //m. The obtained raw yarn was used for weaving to produce a ribbed circular braid. (Comparative Example 24) 1 part by weight of a polyether block phthalamide copolymer ("pebax MV1041SA01" manufactured by Arkema Co., Ltd.), 0.05 parts by weight of phthalic anhydride, and a phosphorus system were added as a thermoplastic polyamide-based elastomer. Antioxidant (manufactured by CIBA JAKAN K_K., "Irgaf〇s 126"), 15 parts by weight, 2 parts by weight of titanium oxide (manufactured by Nippon Chemical Co., Ltd., 2011-2011, "D-91 8"), UV absorber (CIBA JAPANK) .K. Manufacture, "TINUVIN 234") 〇 3 parts by weight and a light stabilizer (manufactured by CIBA JAPAN KK·, "TINUVIN 144") 0.3 After heavy injury, 'melt-mixing was carried out, and resin pellets were produced using a granulator. Then, 'the obtained resin pellets' were used for the spinning by a melt spinning method to obtain a strand having a fineness of 120 dteX (consisting of 30 filaments) and a diameter of about 20 m per one filament. The obtained raw yarn was used for weaving to produce a ribbed circular braid. (Comparative Example 25) 1 part by weight of a polyether block phthalamide copolymer ("pebax MV1041SA01", manufactured by Arkema Co., Ltd.), and 2 parts by weight of o-dodecanoic anhydride were added as a thermoplastic polyamine-based elastomer. 2 parts by weight of titanium oxide ("D-918" manufactured by Seiko Chemical Industry Co., Ltd.), 0.3 parts by weight of an ultraviolet absorber (manufactured by CIBA jAPAN κK, "TINUVIN 234"), and a light stabilizer (manufactured by αΒΑ JAPAN K_K., "TINUVIN" 144") After 3 parts by weight, melt mixing was carried out, and resin pellets were produced using a granulator. Then, using the obtained resin pellets, the filaments were subjected to a melt spinning method to obtain a strand having a fineness of 120 dtex (consisting of 36 filaments) and a length of about 20 μm. The obtained raw yarn was used for weaving to produce a ribbed circular braid. (Comparative Example 26) A polyether block-branched amine copolymer ("Pebax MV1041SA01" manufactured by Arkema Co., Ltd.), which is a thermoplastic polyamide-based elastomer, was added in an amount of 1 part by weight, phthalic anhydride 〇. 2 parts by weight of titanium oxide (manufactured by Daicel Chemical Industries, Inc., 53 201120261, "D-918"), 0.3 parts by weight of UV absorber (manufactured by CIBA JAPAN Co., Ltd., "TINUVIN 234"), and a light stabilizer (CIBA JAPAN Κ) Κ·Manufactured, “TINUVIN 144”) 0.3 parts by weight, melt-mixed, and granulators were used to prepare resin pellets. Then, using the obtained resin pellets, spinning was carried out by a melt spinning method to obtain a strand having a fineness of 120 dtex (consisting of 36 filaments) and a diameter of about 20 m from each filament. The obtained raw yarn was used for weaving to produce a ribbed circular braid. (Comparative Example 27) As a resin for a Ley portion, a poly-blocking phthalamide copolymer ("Pebax MVl 〇 74SA01" manufactured by Arkema Co., Ltd.) was added as a thermoplastic polyamine-based elastomer, and a weight of titanium oxide was added. (堺Chemical Industries, Inc.

Manufactured, "D-918") 5 parts by weight, UV absorber (ciBA JAPAN KK w, "TINUVIN 234") 〇·3 parts by weight and light stabilizer (manufactured by ciBA JAPAN Κ.Κ·, "TINUVIN 144") After 3 parts by weight of ruthenium, the mixture was melt-mixed, and a pelletizer for the sheath portion was produced using a granulator. Nylon 6 ("UBE NylQn iqiifb", manufactured by Utsuka Co., Ltd.) (10) parts by weight, and titanium oxide (manufactured by Daisei Chemical Co., Ltd., "D 9i8") is added as a resin for the core. Parts, UV absorber (CIBA JAPAN Κ·Κ·Manufacture, "TINUVIN 234") 〇.3

In the case of a heavy-duty wound and a light stabilizer (manufactured by CIBA JAPAN Co., Ltd., "TINUVIN 144"), 3 parts by weight was mixed, and the resin pellets for the core were produced using a granulator. The core resin pellets β and the obtained sheath resin pellets 54 201120261 are respectively heated and melted by a uniaxial extruder to perform composite spinning so that the core portion has a circular cross section and the sheath portion has a cross section. A substantially c-shaped, partially open eccentric core-sheath type composite fiber having a fineness of 120 dtex (consisting of 36 filaments). The diameter of each filament of the obtained conjugate fiber was about 2 Å, and the enthalpy occupancy of the core portion was 8 〇% with respect to the fiber cross-sectional area. The obtained composite fiber was woven to prepare a rib circular knitted fabric. (Comparative Example 28) 100 parts by weight of a polyether block phthalamide copolymer ("Pebax MV1074SA01" manufactured by Arkema Co., Ltd.) as a thermoplastic polyamine-based elastomer, and titanium oxide (manufactured by Sigma Chemical Industry Co., Ltd., r D_9 1 8) 5 parts by weight, a UV absorber (manufactured by CIBA JAPAN KK, "TINUVIN 234"), 3 parts by weight, and a light stabilizer (manufactured by Ciba JAPAN KK, "TINUVIN M4"), 3 parts by weight, and then melt-mixed. Resin particles A were produced using a granulator. Nylon oxime (manufactured by Arkeina Co., Ltd., "Rilsan BESN TL"), 1 part by weight of titanium oxide resin, 5 parts by weight of titanium oxide ("D-918" manufactured by Nippon Chemical Industry Co., Ltd.), and an ultraviolet absorber ( 0.3 parts by weight of CIBA JAPAN KK, "TINUVIN 234") and 0.3 parts by weight of a light stabilizer (manufactured by CIBA JAPAN KK, "TINUVIN 144") were melted and mixed, and resin pellets B were produced using a granulator. Then, 'the obtained resin pellet A and resin pellet B were respectively heated and melted by a uniaxial extruder' to be composite-spun to make their respective sections semi-circular', and the fineness was 12 〇dtex (by 36 filaments) The composition of the joint 55 201120261 row type composite fiber. The diameter of each filament of the obtained composite fiber was about 20, and the occupancy of the heart 4 was 5 with respect to the fiber cross-sectional area. The obtained composite fiber was used for knitting to make a rib circular knitted fabric. (Comparative Example 29) As a resin for a Ley portion, a poly-blocking phthalamide copolymer ("Pebax MVl 〇 74SA01" manufactured by Arkema Co., Ltd.) as a thermoplastic polyamide-based elastomer was added in an amount of 1 part by weight, and titanium oxide was added. (manufactured by Kasei Chemical Industry Co., Ltd., "D-918") 5 parts by weight, UV absorber (manufactured by CIBA JAPAN KK, "TINUVIN 234") 3·3 parts by weight and light stabilizer (manufactured by CIBA JAPAN Κ·Κ·, TINUMVIN 144"), which is 0.3 parts by weight, is melt-mixed, and a resin particle for the sheath portion is used as a resin for the core portion by using a granulator, and a thermoplastic polyester-based elastomer is added (manufactured by Toyobo Co., Ltd., " Pelprene p_15〇B") 1 part by weight, 5 parts by weight of titanium oxide ("D-918" manufactured by Nippon Chemical Industry Co., Ltd.), 0.3 parts by weight of ultraviolet absorber (manufactured by CIBA JAPAN KK, "TINtJVIN 234"), and light 0.3 parts by weight of a stabilizer (manufactured by CIBA JAPAN KK., "144") was melt-mixed, and a core resin pellet B was produced using a granulator. Then, the obtained resin particles A and the core resin particles B are heated and melted by a uniaxial extruder to perform composite spinning so that the cross section of the core portion becomes circular, and the cross section of the portion becomes a ring shape. A concentric core-sheath type composite fiber having a fineness of l20 dtex (consisting of 36 filaments) was obtained. The diameter of each of the obtained composite fibers was about 2 〇 V claws, and the occupancy rate of 56 201120261 was 70% with respect to the fiber cross-sectional area. The obtained composite fiber was woven to prepare a rib circular knitted fabric. (Evaluation) ", The method below evaluated the thermoplastic elastomers used in the examples and comparative examples and the resulting cloth. The results are shown in Table 4. (1) Courtaulds yellowing test A sample of 3 CmXl0(10) cloth was prepared and held in a glass substrate with a test paper containing 〇 1% dibutyl nitrobenzene. Then, the film was sealed with a film of non-strandy toluene (BHT), and the hammer was placed so that there was no gap between the cloth sample and the test paper, and f i was kept for 6 hours at 5 〇 ± 3 t. After the pot, the sample was cooled to room temperature, the film and the glass substrate were removed, and the degree of yellow discoloration of the cloth was measured immediately by gray scale private (s L 0805 ). The evaluation was carried out in the range of 1 to 5 in units of 〇5, and the result was judged to be good in the case of level 4 or higher. (2) ΝΟχ Yellowing test to JIS L 0855 "Staining fastness to nitrogen oxides "Test method" is based on the "strong test". The degree of yellowing is measured using a colorimeter (heart_white-eyE3_), and the value of the cielab color system is changed before and after the test. 1 (Ab value) was evaluated. The larger the Ab* value, the larger the yellowing. △ b value = (value after test) _ (value before test) (3) Heater red change test After making a 5cmxl0cm cloth sample, place it in a distance (4) fog type oil heater (Mitsubishi Electric KD_25CTD) The discharge port is at a distance of (10), 57 201120261 After the heater is operated for a total of 24 hours, the redness of the cloth sample is investigated. This evaluation considers the problem of discoloration when NOx, s〇x, and high-humidity environments act simultaneously. The degree of reddening was measured using a colorimeter (Macbeth WHITE-EYE3000), and the value of the CIELAB color system was evaluated before and after the test (Δ〆 value). The larger the value, the greater the red change. △ a* value = (a* value after test) - (a* value before test) (4) Khan light resistance test by "B method" in JIS L 0888 "Test method for dyeing fastness to light and sweat" As a standard method, alkaline artificial sweat was used and measurement was carried out using a UV carbon arc lamp time tester. (5) Determination of qmax value Each cloth was placed on a sample stage set to a temperature of 20.5 ° C. After the heat storage plate was placed on the cloth at a contact pressure of 0.098 N/cm 2 and kept at a temperature of 32 5 . The peak value of the amount of heat that the accumulated heat moves toward the sample on the low temperature side is measured. A Thermo Lab II type rapid rapid thermal property measuring device (manufactured by Kato Tech Co., Ltd.) was used for the measurement. (6) Ammonia deodorization test Ammonia water was added dropwise to a glass container of 1 L so that the concentration became 1 〇〇Ppm '1 g sample was hanged in the glass container', and the sealed glass container was set at 50 ° C. In the thermostatic chamber, the concentration of ammonia in the glass vessel after 2 hours was measured using a Beichuan gas detector. The smaller the above-mentioned measured Hanta value, the more excellent the ammonia deodorizing property. 58 201120261

Example 1 Greedy Example 2 Example 3 Example 4 - Example 5 Example 6 Lean Example 7 Example 8 Example 9 ★ Example 10 Thermoplastic PebaxMV1041SA01 60 60 60 60 60 100 100 100 100 100 Elastomer Pebax 6333SA01 40 40 40 40 40 0 0 0 0 0 Composition of acidic compound styrene-maleic anhydride copolymer 1 1.5 2 0.3 0.2 0 0 0 0 0 o-dimethic anhydride 0 0 0 0 0 0.3 0.6 1 0.2 0.1 Phosphorus-based antioxidant Adekastab PEP36 0.6 1 0 0 0 0 0 0 0.5 1 Heavy Irgafos 126 0 0 0.15 0 0 0 0 ^.15 0 0 Parts Sumilizer GP 0 0 0 0.2 0.5 Γ 0.6 0.2 0 0 0 Titanium oxide D-918 5 5 5 5 5 5 5 5 5 5 Other UV absorber (TINUVIN234) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Additive light stabilizer (TINUVIN144) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Courtaulds yellowing test 5 5 Grade S grade 5 grade 5 grade 4 grade 4 grade 4 grade 4 grade 4 grade N〇x yellowing test △b* value 0.2 0.2 0.2 0.4 0.8 1.8 1.5 1.5 2.0 2.0 Evaluation of heater red change test △a* value 0.9 0.6 1.8 1.8 0.5 0.5 2.0 2.0 0.7 0.6 Khan Lightfastness Test 5 Level 5 Level 5 Level 5 Level 5 Level 4 Level 4 Level 4 Level 4 Level 4 qmax value 0.23 0.23 0.23 0.23 0.23 0.24 0.24 0.24 0.24 0.24 0.24 59 201120261 [Table 2] Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Composite part open eccentric core part Part of the open eccentric core Side by side concentric core sheath concentric core sheath resin particles A Composition (parts by weight) Thermoplastic elastomer Pebax MV1074SA01 100 100 100 100 100 100 Acid compound styrene-maleic anhydride copolymer 1 1 1 1 1 1 Phosphorus antioxidant Sumilizer GP 0.3 0.3 0.3 0.3 0.3 0.3 Other additives UV absorber (TINUVIN 234) 0.3 0.3 0.3 0.3 0.3 0.3 Light stabilizer (TINUVIN 144) 0.3 0.3 0.3 0.3 0.3 0.3 Carrier shape roughly C-shaped (sheath) 81-shaped (core) Semi-circular semicircular ring (sheath) Round (core) Occupancy (%) relative to the cross-sectional area of the weave dimension 20 80 50 50 30 70 Resin particles B Composition (parts by weight) Other resins UBE Nylon 1011FB 100 100 — — - - Rilsan BESN TL - — 100 — — — UBESTA3014B — — — 100 — — Pelprene P-150B - - — - 100 100 Acidic compound phenyl - Maleic anhydride copolymer 1 1 1 1 1 1 Phosphorus-based antioxidant Sumilizer GP 0.3 0.3 0.3 0.3 0.3 0.3 Other additives UV absorber (TINUVIN 234) 0.3 0.3 0.3 0.3 0.3 0.3 Light stabilizer (TINUVIN 144) 0.3 0.3 0.3 0.3 0.3 0.3 Cross-sectional shape Round (core) Approximate C-shape (sheath) Semi-circular semi-circular round (core) Ring (sheath) Occupancy (%) relative to the cross-sectional area of the weave 80 20 50 50 70 30 Evaluation of Courtaulds Yellowing Test 5, 5, 5, 5, 5, 5, NOx yellowing test △ b 0.5 0.5 0.5 0.4 0.4 0.2 0.2 Heater red change test △ a 氺 value 0.5 1.2 0.7 0.8 0.6 0.9 Khan light test 5 Level 5, 5, 5, 5, 5, qmax, 0.20 0.25 0.21 0.21 0.23 0.24 60 201120261 [Table 3] Comparative Example 1 Comparative Example 2 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Component parts by weight Thermoplastic elastomer Pebax MV1041SA01 60 60 60 60 60 100 100 100 100 100 Pebax 6333SA01 40 40 40 40 40 0 0 0 0 0 Acid compound styrene-maleic anhydride copolymer 0 0 0.05 0.3 0.2 0 0 0 0 0 Phthalic anhydride 0 0 0 0 0 0 0 0.05 0.2 0,1 Phosphorus-based antioxidant Adekastab PEP36 0.6 1 0 0 0 0 0 0 0 0 Irgafos 126 0 0 0.15 0 0 0 0 0.15 0 0 Sumilizer GP 0 0 0 0 0 0.6 0.2 0 0 0 Titanium D-918 5 5 5 5 5 5 5 5 5 5 Other additives UV absorber (TINUVIN234) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Light stabilizer (TINUVIN 144 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Evaluation of Courtaulds yellowing test 2 grade 3 grade 1 grade 3 grade 2 grade 3 grade 1 grade 1 grade 2 grade 1 grade NOx yellowing test △ b* value 4.9 3.2 5.9 3.5 4.4 3.8 6.3 6.6 5.0 7.7 Heater red test △a* value 1.8 1.3 2.2 6.6 7.9 1.5 3.3 3.8 6.3 7.8 Khan light test 3 level 3 level 3 level 3 level 3 level 3 level 3 level 3 level 3 level 3 level qmax value 0.23 0.23 0.23 0.23 0.23 0.24 0.24 0.24 0.24 0.24 61 201120261 [Table 4] Comparative Example 11 Comparative Example 12 Comparative Example 13 Comparative Example 14 Comparative Example 15 Comparative Example 16 Composite type partially open eccentric core sheath partially open eccentric core sheath side by side concentric core sheath Concentric core sheath resin particles A Composition (parts by weight) Thermoplastic elastomer Pebax MV1074SAOI 10 0 100 100 100 100 100 Acidic compound styrene-maleic anhydride copolymer — — — — — Phosphorus-based antioxidant Sumilizer GP — — — — Other additives UV absorber (TINUVIN 234) 0.3 0.3 0.3 0.3 0.3 0.3 Light stabilizer (TINUVIN 144) 0.3 0.3 0.3 0.3 0.3 0.3 Carrier shape is roughly C-shaped (sheath) Round (core) Semi-circular semi-circular ring (sheath) Round (core) Relative to the cross-sectional area of the dimension Occupancy (%) 20 80 50 50 30 70 Resin particles B Composition (parts by weight) Other resins UBE Nylon 1011FB 100 100 — — — — Rilsan BESN TL — — 100 — — — UBESTA3014B — — — 100 — — Pelprene P-15 OB — — — — 100 100 Acidic compound styrene·maleic anhydride copolymer — — — — — Phosphorus-based antioxidant Sumilizer GP — — — — — — Other additives UV absorber (TINUVIN 234) 0.3 0.3 0.3 0.3 0.3 0.3 light stabilizer (TINUVIN 144) 0.3 0.3 0.3 0.3 0.3 0.3 cross-sectional shape round (core) roughly C-shaped (sheath) semi-symmetric semi-circular round (core) ring (sheath) relative to Fiber cross-sectional area occupancy (%) 80 20 50 50 70 30 Evaluation of Courtaulds yellowing test 1st grade 1st grade 1st grade 2 grade 2 grade NOx yellowing test △b* value 7.1 6.1 6.9 7.3 4.3 5.0 Heater red change Test Δa* value 3.8 7.1 3.5 3.3 3.9 7.0 Khan lightfastness test 3 grade 3 grade 3 grade 3 grade 3 grade 3 grade qmax value 0.20 0.25 0.21 0.21 0.23 0.24 62 201120261 [Table 5] Example 17 Example 18 Example 19 Implementation Example 20 Example 21 Example 22 Example 23 Example 24 Group Thermoplastic elastomer Pebax MV1041SA01 60 60 60 60 100 100 100 100 Pebax 6333SA01 40 40 40 40 0 0 0 0 Acidic compound styrene-maleic anhydride copolymer 1 1.5 2 0.3 0 0 0 0 Phthalic anhydride 0 0 0 0 0.3 1 0.2 0.1 Weight of phosphorus antioxidant Adekastab PEP36 0.6 1 0 0 0 0 0.5 1 Irgafos 126 0 0 0.15 0 0 0.15 0 0 Sumilizer GP 0 0 0 0.2 0.6 0 0 0 Titanium oxide D-918 4 4 4 6 6 4 4 4 Other additives UV absorber (TINUVIN 234) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Light stabilizer (TINUVIN 144) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Evaluation of Courtaulds yellowing test 5 Level 5, 5, 5, 4, 4, 4, 4, NOx yellowing test △b* value 0.2 0.2 0.2 0.4 1.8 1.5 2.0 2.0 Heater red test △a* value 0.9 0.6 1.8 1.8 0.5 2,0 0.7 0.6 Sweat light test 5 grade 5 grade 5 grade 5 grade 4 grade 4 grade 4 grade 4 grade Qinax value 0.23 0,23 0.23 0.23 0.24 0.24 0.24 0.24 ammonia deodorization test (ppm) 18 17 15 20 22 18 24 25 63 201120261 [Table 6 Example 25 Example 26 Example 27 Example 28 Example 29 Example 30 Composite part open eccentric core sheath part open eccentric core pin side by side concentric core sheath concentric core sheath resin particles A Composition (parts by weight) Thermoplastic elastomer PebaxMV 丨074SA01 100 100 100 100 100 100 Acidic compound styrene·maleic anhydride copolymer 1 1 1 1 1 1 Phosphorus-based antioxidant Sumilizer GP 0.3 0.3 0.3 0.3 0.3 0.3 Titanium oxide D-918 5 5 5 5 5 5 Other additives UV absorber (TINUVIN 234) 0.3 0.3 0.3 0.3 0.3 0.3 Light stabilizer (TINUVIN 144) 0.3 0.3 0.3 0.3 0.3 0.3 Cross-sectional shape wood C-shaped (sheath) Round (core) Semi-circular semi-circular ring ( Sheath) round (core) phase Occupancy in fiber cross-sectional area (%) 20 80 50 50 30 70 Resin particles B Composition (parts by weight) Other resins UBE Nylon 1011FB 100 100 — - — - Rilsan BESN TL — - 100 — - - UBESTA3014B — — — 100 — - Pelprene P-150B - - - 100 100 100 Acidic compound styrene-maleic anhydride copolymer 1 1 1 1 1 1 Phosphorus-based antioxidant Sumilizer GP 0.3 0.3 0.3 0.3 0.3 0.3 Oxidation D-918 5 5 5 5 5 5 Other additives UV absorber (TINUVIN 234) 0.3 0.3 0.3 0.3 0.3 0.3 Light stabilizer (TINUVIN 144) 0.3 0.3 0.3 0.3 0.3 0.3 Cross-sectional shape 囿 (core) Approximate C-shape (sheath) Semi-circular semi-circular circle Shape (core) Ring (sheath) Occupancy (%) relative to blazing area 80 20 50 50 70 30 Evaluation of Courtaulds yellowing test 5 5, 5 5, 5 5, NOx yellowing test △ b. Value 0.5 0.5 0.4 0.4 0.2 0.2 Heater red change test △a·value 0.5 1.2 0.7 0.8 0.6 0.9 Khan lightfastness test 5 grade 5 grade 5 grade 5 grade 5 grade 5 grade qmax value 0.20 0.25 0.21 0.21 0.23 0.24 atmosphere deodorization test (ppm ) 25 15 23 23 24 17 64 201120 261 [Table 7] Comparative Example 17 Comparative Example 18 Comparative Example 19 Comparative Example 20 Comparative Example 21 Comparative Example 22 Comparative Example 23 Comparative Example 24 Comparative Example 25 Comparative Example 26 Composition Weight Parts Thermoplastic Elastomer Pebax MV1041SA01 60 60 60 60 60 100 100 100 100 100 Pebax 6333SA01 40 40 40 40 40 0 0 0 0 0 Acidic compound styrene-maleic anhydride copolymer 0 0 0.05 0.3 0.2 0 0 0 0 0 Phthalic anhydride 0 0 0 0 0 0 0 0.05 0.2 0.1 Phosphorus-based antioxidant Adekastab PEP36 0.6 1 0 0 0 0 0 0 0 0 Irgafos 126 0 0 0.15 0 0 0 0 0.15 0 0 Sumilizer GP 0 0 0 0 0 0.6 0.2 0 0 0 Titanium oxide D-918 2 2 1 0 0 0 0 2 2 2 Other additives UV absorber (TINUVIN 234) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Light stabilizer (TINUVIN 144) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Evaluation of Courtaulds yellowing test level 2 3 level 1 level 3 level 2 level 3 level 1 level 1 level 2 level 1 level NOx yellowing test △ b * value 4.9 3.2 5.9 3.5 4.4 3.8 6.3 6.6 5.0 7.7 Heater red change test △ a * value 1.8 1.3 2.2 6.6 7.9 1.5 3.3 3.8 6.3 7.8 Khan Lightfastness Test Level 3 Level 3 Level 3 Level 3 Level 3 3 Grade 3, grade 3, grade 3, grade qmax value 0.23 0.23 0.23 0.23 0.23 0.24 0.24 0.24 0.24 0.24 ammonia deodorization test (ppm) 50 48 47 55 60 85 84 50 40 46 65 201120261 [Table 8] Comparative Example 27 Comparative Example 28 Comparison Example 29 Composite Partially Open Eccentric Core Sheath Side-by-Side Concentric Core Sheath Resin Particles A Composition (parts by Weight) Thermoplastic Elastomer Pebax MV1074SA01 100 100 100 Acidic Compound Styrene-Maleic Anhydride Copolymer — — Phosphorus-Based Antioxidant Sumilizer GP — — — Oxidation D-918 5 5 5 Other additives UV absorber (TINUVIN 234) 0.3 0.3 0.3 Light stabilizer (TINUVIN144) 0.3 0.3 0.3 Cross-sectional shape roughly C-shaped (sheath) Semi-circular ring (sheath) _ for fiber Percentage of cross-sectional area (%) 20 50 30 Resin particle B Composition (parts by weight) Other resin UBE Nylon 1011FB 100 — — Rilsan BESN TL — 100 — UBESTA3014B — — — Pelprene P-150B — — 100 Acidic compound styrene-cis Butene hydride copolymer — — Phosphorus-based antioxidant Sumilizer GP — — — Oxidation Chin D-918 5 5 5 Other additions UV absorber (TINUVIN 234) 0.3 0.3 0.3 Light stabilizer (TINUVIN 144) 0.3 0.3 0.3 Cross-sectional shape round (core) Semi-circular round (core) Occupancy with respect to fiber cross-sectional area (%) 80 50 70 Evaluation Courtaulds yellowing test 1st grade 1st grade 2 NOx yellowing test △b氺 value 7.1 6.9 4.3 Heater red change test △a氺 value 3.8 3.5 3.9 Khan light test 3 grade 3 grade 3 qmax value 0.20 0.21 0.23 ammonia deodorization test (ppm) 51 50 53 [Industrial Applicability] According to the present invention, it is possible to provide a contact excellent cold contact feeling, hand feeling and skin touch, and to suppress yellowing and redness of fibers during circulation or use. Changed fibers, cloth and underwear. 66 201120261 [Simple description of the diagram] None [Main component symbol description

Claims (1)

201120261 VII. Patent application scope: 1 · A fiber, which is a fiber containing a thermoplastic elastomer, an acidic compound and a breaking antioxidant, characterized in that: the acidic compound is a styrene-maleic anhydride copolymer or an acid anhydride, relative The thermoplastic elastomer is a polyamine-based elastomer, in the weight of the thermoplastic elastomer, in an amount of 1 part by weight or more. 3. The fiber of claim 1 or 2, wherein the thermoplastic elastomer is a polyether block phthalamide copolymer. The fiber of item 1, item 2 or item 3 of the patent application of 士申π, which comprises titanium oxide in a multi-step manner, the titanium oxide being rutile type titanium dioxide, and the wood containing the oxidation for a part by weight of the thermoplastic elastomer钦3重量份上上0 5·—cloth, characterized in that: item, item 2, item 3 or item 4 is made of fibers as claimed in item 1 of the patent application. 6. The underwear is characterized in that: a fiber such as the first, second, third or fourth fiber of the patent application or the cloth of the fifth item of the patent application is applied. Eight, none 68